WorldWideScience

Sample records for solid solutions thermodynamic

  1. The thermodynamics and kinetics of interstitial solid solutions

    International Nuclear Information System (INIS)

    Silva, J.R.G. da.

    1976-04-01

    Studies of hydrogen metal systems where the hidrogen is disolved in a solid solution are presented. Particular items of interest are: the thermodynamics of the hydrogen-iron system; the solubility of hidrogen in super pure iron single crytals; the thermodinamic functions of hydrogen in solid solutions of Nb, Ta and V; and the solubility of hydrogen in α-manganese. The diffusion of carbon and nitrogen in BCC iron is also studied

  2. Thermodynamic properties of solid solutions in the system Ag2S–Ag2Se

    International Nuclear Information System (INIS)

    Pal’yanova, G.A.; Chudnenko, K.V.; Zhuravkova, T.V.

    2014-01-01

    We have summarized experimental data on the phase diagram of the system Ag 2 S–Ag 2 Se. Standard thermodynamic functions of four solid solutions in this system have been calculated using the model of regular and subregular solutions: a restricted fcc solid solution γ-Ag 2 S-Ag 2 S 1−x Se x (x 2 S–Ag 2 Se, monoclinic solid solution (α) from Ag 2 S to Ag 2 S 0.4 Se 0.6 , and orthorhombic solid solution (α) from Ag 2 S 0.3 Se 0.7 to the Ag 2 Se. G mix and S mix have been evaluated using the subregular model for asymmetric solution for the region Ag 2 S 0.4 Se 0.6 –Ag 2 S 0.3 Se 0.7 . The thermodynamic data can be used for modeling in complex natural systems and in matters of semiconductor materials

  3. A thermodynamic model for solid solutions and its application to the C-Fe-Co, C-Fe-Ni and Mn-Cr-Pt solid dilutions

    International Nuclear Information System (INIS)

    Tao, D.P.

    2004-01-01

    Based on the free volume theory and the lattice model, the partition functions of pure solids and their mixtures were expressed. This resulted in the establishment of a thermodynamic model for solid solutions. The model naturally combines the excess entropy and excess enthalpy of a solution by means of new expressions of the configurational partition functions of solids and their mixtures derived from statistical thermodynamics, which is approximate to real solid solutions, that is S E ≠0 (V E ≠0) and H E ≠0. It can describe the thermodynamic properties of partially miscible systems and predict the thermodynamic properties in a multicomponent solid solution system using only the related binary infinite dilute activity coefficients. The predicted activity coefficients from the model are in good agreement with the experimental data of the ternary solid dilutions. This shows that the prediction effect of the proposed model is of better stability and reliability because it has a good physical basis

  4. Thermodynamics of CoAl2O4-CoGa2O4 solid solutions

    International Nuclear Information System (INIS)

    Lilova, Kristina I.; Navrotsky, Alexandra; Melot, Brent C.; Seshadri, Ram

    2010-01-01

    CoAl 2 O 4 , CoGa 2 O 4 , and their solid solution Co(Ga z Al 1-z ) 2 O 4 have been studied using high temperature oxide melt solution calorimetry in molten 2PbO.B 2 O 3 at 973 K. There is an approximately linear correlation between lattice parameters, enthalpy of formation from oxides, and the Ga content. The experimental enthalpy of mixing is zero within experimental error. The cation distribution parameters are calculated using the O'Neill and Navrotsky thermodynamic model. The enthalpies of mixing calculated from these parameters are small and consistent with the calorimetric data. The entropies of mixing are calculated from site occupancies and compared to those for a random mixture of Ga and Al ions on octahedral site with all Co tetrahedral and for a completely random mixture of all cations on both sites. Despite a zero heat of mixing, the solid solution is not ideal in that activities do not obey Raoult's Law because of the more complex entropy of mixing. - Graphical abstract: Measured enthalpies of mixing of CoAl 2 O 4 -CoGa 2 O 4 solid solutions are close to zero but entropies of mixing reflect the complex cation distribution, so the system is not an ideal solution.

  5. Thermodynamics of oxygen in solid solution in vanadium and niobium--vanadium alloys

    International Nuclear Information System (INIS)

    Steckel, G.L.

    1977-01-01

    A thermodynamic study was made of the vanadium-oxygen and niobium-vanadium-oxygen systems utilizing the solid state galvanic cell technique. Investigations were made with a ThO 2 /Y 2 O 3 electrolyte over the temperature ranges 700 to 1200 0 C (973 to 1473 K) for the binary system and 650 to 1150 0 C (923 to 1423 K) for the ternary system. The activity of oxygen in vanadium obeys Henry's law for the temperatures of this investigation for concentrations up to 3.2 at. percent oxygen. For higher concentrations the activity coefficient shows positive deviations from Henry's law. The terminal solubility of oxygen in vanadium was determined. The activity of oxygen in Nb--V alloys obeys Henry's law for the temperatures of this study for oxygen concentrations less than approximately 2 at. percent. For certain Nb/V ratios Henry's law is obeyed for concentrations as high as 6.5 at. percent oxygen. First order entropy and enthalpy interaction coefficients have been determined to describe the effect on the oxygen activity of niobium additions to vanadium-rich alloys with dilute oxygen concentrations. Niobium causes relatively small decreases in the oxygen activity of V-rich alloys and increases the oxygen solubility limit. Vanadium additions to Nb-rich alloys also increases the oxygen solubility and causes substantial decreases in the dilute solution oxygen activities. The change in the thermodynamic properties when molecular oxygen dissolves in vanadium and niobium--vanadium alloys and the equilibrium oxygen pressure over the binary and ternary systems were also determined

  6. Simple thermodynamic model of the extension of solid solution of Cu-Mo alloys processed by mechanical alloying

    International Nuclear Information System (INIS)

    Aguilar, C.; Guzman, D.; Rojas, P.A.; Ordonez, Stella; Rios, R.

    2011-01-01

    Highlights: → Extension of solid solution in Cu-Mo systems achieved by mechanical alloying. → Simple thermodynamic model to explain extension of solid solution of Mo in Cu. → Model gives results that are consistent with the solubility limit extension reported in other works. - Abstract: The objective of this work is proposing a simple thermodynamic model to explain the increase in the solubility limit of the powders of the Cu-Mo systems or other binary systems processed by mechanical alloying. In the regular solution model, the effects of crystalline defects, such as; dislocations and grain boundary produced during milling were introduced. The model gives results that are consistent with the solubility limit extension reported in other works for the Cu-Cr, Cu-Nb and Cu-Fe systems processed by mechanical alloying.

  7. Zirconium-cerin solid solutions: thermodynamic model and thermal stability at high temperature; Solutions solides de zirconium dans la cerine: modele thermodynamique et stabilite thermique a haute temperature

    Energy Technology Data Exchange (ETDEWEB)

    Janvier, C.

    1998-04-02

    The oxides-gaseous dioxygen equilibria and the textural thermal stability of six zirconium-cerin solutions Ce{sub 1-x}Zr{sub x}O{sub 2} (0solid solutions and the gaseous oxygen by thermal gravimetric analysis at 600 degrees Celsius has shown that these solutions have not a ideal behaviour. A thermodynamic model where the point defects of solutions are included describe them the best. It becomes then possible to know the variations of the concentrations of the point defects in terms of temperature, oxygen pressure and zirconium concentration. A kinetic study (by calcination at 950 degrees Celsius of the solid solutions) of the specific surface area decrease has revealed a minima (0

  8. Modelling solid solutions with cluster expansion, special quasirandom structures, and thermodynamic approaches

    Science.gov (United States)

    Saltas, V.; Horlait, D.; Sgourou, E. N.; Vallianatos, F.; Chroneos, A.

    2017-12-01

    Modelling solid solutions is fundamental in understanding the properties of numerous materials which are important for a range of applications in various fields including nanoelectronics and energy materials such as fuel cells, nuclear materials, and batteries, as the systematic understanding throughout the composition range of solid solutions for a range of conditions can be challenging from an experimental viewpoint. The main motivation of this review is to contribute to the discussion in the community of the applicability of methods that constitute the investigation of solid solutions computationally tractable. This is important as computational modelling is required to calculate numerous defect properties and to act synergistically with experiment to understand these materials. This review will examine in detail two examples: silicon germanium alloys and MAX phase solid solutions. Silicon germanium alloys are technologically important in nanoelectronic devices and are also relevant considering the recent advances in ternary and quaternary groups IV and III-V semiconductor alloys. MAX phase solid solutions display a palette of ceramic and metallic properties and it is anticipated that via their tuning they can have applications ranging from nuclear to aerospace industries as well as being precursors for particular MXenes. In the final part, a brief summary assesses the limitations and possibilities of the methodologies discussed, whereas there is discussion on the future directions and examples of solid solution systems that should prove fruitful to consider.

  9. Geological constraints on the thermodynamic properties of the stilbite - stellerite solid solution in low-grade metabasalts

    Science.gov (United States)

    Fridriksson, Thráinn; Neuhoff, Philip S.; Arnórsson, Stefán; Bird, Dennis K.

    2001-11-01

    Standard state thermodynamic data for stilbite (Ca2NaAl5Si13O36∗16H2O) and stellerite (Ca2Al4Si14O36∗14H2O), together with mixing properties of the stilbite -stellerite solid solution (stilbite SS) are derived through assessment of geological observations of stilbite SS compositions in metabasalts, experimental phase equilibria, and calorimetric observations. Measured compositions of stilbite SS in Tertiary metabasalts in Iceland and Icelandic geothermal systems change systematically towards the stellerite endmember with increasing stratigraphic depth and temperature. Standard molal volumes, heat capacities, and entropies for the endmembers of the solid solution are derived through critical review of published crystallographic and calorimetric data for natural stilbite SS. Standard molal Gibbs energies of formation at 298.15 K and 1 bar for stilbite (-4,946,475cal mol-1) and stellerite (-4,762,036 cal mol-1) and the mixing properties of the solid solution are retrieved from observed phase- and compositional-relations in metabasalts at Berufjördur, Iceland, measured temperatures of zeolite mineral distribution in active geothermal systems, and published observations of reversed phase equilibria. Mixing in stilbite SS can be described with an athermal solid solution model. Thermodynamic data resulting from our analysis provide close correlation between compositions of stilbite SS in Icelandic geothermal systems predicted from compositions of geothermal solutions and observed compositions of these minerals in low-grade metabasalts of Iceland, as well as the observed temperature of the stilbite SS to laumontite (leonhardite) transition in Icelandic geothermal systems. Stilbite SS composition in metabasalts is a sensitive function of temperature, fluid composition, coexisting minerals (especially silica polymorphs) and geothermal gradient.

  10. Thermodynamics of dilute 3He-4He solid solutions with hcp structure

    Science.gov (United States)

    Chishko, K. A.

    2018-02-01

    To interpret the anomalies in heat capacity CV(T) and temperature-dependent pressure P(T) of solid hexagonal close-packed (hcp) 4He we exploit the model of hcp crystalline polytype with specific lattice degrees of freedom and describe the thermodynamics of impurity-free 4He solid as superposition of phononic and polytypic contributions. The hcp-based polytype is a stack of 2D basal atomic monolayers on triangular lattice packed with arbitrary long (up to infinity) spatial period along the hexagonal c axis perpendicular to the basal planes. It is a crystal with perfect ordering along the layers, but without microscopic translational symmetry in perpendicular direction (which remains, nevertheless, the rotational crystallographic axis of third order, so that the polytype can be considered as semidisordered system). Each atom of the hcp polytype has twelve crystallographic neighbors in both first and second coordination spheres at any arbitrary packing order. It is shown that the crystal of such structure behaves as anisotropic elastic medium with specific dispersion law of phonon excitations along c axis. The free energy and the heat capacity consist of two terms: one of them is a normal contribution [with CV(T) ˜ T3] from phonon excitations in an anisotropic lattice of hexagonal symmetry, and another term (an "excessive" heat) is a contribution resulted by packing entropy from quasi-one-dimensional system of 2D basal planes on triangular lattice stacked randomly along c axis without braking the closest pack between neighboring atomic layers. The excessive part of the free energy has been treated within 1D quasi-Ising (lattice gas) model using the transfer matrix approach. This model makes us possible to interpret successfully the thermodynamic anomaly (heat capacity peak in hcp 4He) observed experimentally.

  11. Kinetics and thermodynamics of the dissolution of Th1-xMxO2 solid solutions (M = U, Pu)

    International Nuclear Information System (INIS)

    Hubert, S.; Heisbourg, G.; Dacheux, N.; Moisy, Ph.; Purans, J.

    2004-01-01

    Kinetics of the dissolution of Th 1-x M x O 2 (M = U, Pu) solid solutions was investigated as a function of several chemical parameters such as pH, substitution ratio, temperature, ionic strength, and electrolyte. Several compositions of Th 1-x U x O 2 and Th 1-x Pu x O 2 were synthesized and characterized before and after leaching by using several methods such as XRD, EXAFS, BET, PIXE, SEM, and XPS. Leaching tests were performed in nitric, hydrochloric or sulfuric media and groundwater. The normalized dissolution rates were evaluated for Th 1-x U x O 2 , and Th 0.88 Pu 0.12 O 2 leading to the determination of the partial order related to the proton concentration, n, and to the corresponding normalized dissolution rate constant at pH = 0, k'T. While for Th enriched solids, the solid solutions Th 1-x U x O 2 have the same dissolution behaviour than ThO 2 with a partial order n ∼ 0.3, in the case of uranium enriched solids, Th 1-x U x O 2 has the same dissolution behaviour than UO 2 with a partial order of n = 1, indicating that uranium oxidation rate becomes the limiting step of the dissolution process. The stoichiometry of the release of both actinides (U or Pu, Th) was verified until the precipitation of thorium occurred in the leachate for pH > 2, while uranium was released in the solution as an uranyl form. For uranium enriched solid solutions, thermodynamic equilibrium was reached after 100 days, and solubility constant of secondary phase was determined. In the case of Th 1-x Pu x O 2 , the dissolution behaviour is similar to that of ThO 2 , but only kinetic aspect of the dissolution can be studied. From the analysis of XPS and EXAFS data on leached and un-leached Th 1-x U x O 2 samples, the dissolution mechanism of solid solutions was explained and will be discussed. The role of the electrolytes on the dissolution of the solid solutions is discussed. Kinetics parameters of dissolution are also given in groundwater and in neutral media

  12. A self-consistent model for thermodynamics of multicomponent solid solutions

    Czech Academy of Sciences Publication Activity Database

    Svoboda, Jiří; Fischer, F. D.

    2016-01-01

    Roč. 123, OCT (2016), s. 154-157 ISSN 1359-6462 R&D Projects: GA ČR(CZ) GA15-06390S Institutional support: RVO:68081723 Keywords : Thermodynamics * Bonding * Analytical methods Subject RIV: BJ - Thermodynamics Impact factor: 3.747, year: 2016

  13. First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

    Science.gov (United States)

    Bechtel, Jonathon S.; Van der Ven, Anton

    2018-04-01

    Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

  14. Electronic, elastic, thermodynamic properties and structure disorder of {gamma}-AlON solid solution from ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuezhong, E-mail: wyzphysics@163.com [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Tianjin Jinhang Institute of Technical Physics, Tianjin 300192 (China); Lu, Tiecheng, E-mail: lutiecheng@scu.edu.cn [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); International Center for Material Physics, Chinese Academy of Sciences, Shenyang 110015 (China); Zhang, Rongshi [Tianjin Jinhang Institute of Technical Physics, Tianjin 300192 (China); Jiang, Shengli; Qi, Jianqi; Wang, Ying [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Chen, Qingyun [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); National Defense Key Discipline Laboratory of Nuclear Waste and Environmental Safety, Southwest University of Science and Technology, Mianyang 621010 (China); Miao, Naihua [Physique Theorique des Materiaux, Universite de Liege, Sart Tilman B-4000 (Belgium); He, Duanwei [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610064 (China)

    2013-01-25

    Highlights: Black-Right-Pointing-Pointer We reassess the chemical bonding character of {gamma}-AlON which shows strong ionicity. Black-Right-Pointing-Pointer {gamma}-AlON single-crystals exhibit highly elastic anisotropy. Black-Right-Pointing-Pointer The thermodynamic properties are investigated in a wider temperature/pressure range. Black-Right-Pointing-Pointer {gamma}-AlON is an O/N partially disordered structure. - Abstract: Spinel aluminium oxynitride ({gamma}-AlON), as a kind of transparent ceramic material expectable, is studied using the ab initio density functional method, in terms of electronic, elastic, thermodynamic properties and structure disorder. The results show that {gamma}-AlON exhibits strong ionicity, as quantitatively expressed by (Al{sub O}{sup 2.43+}){sub 15}(Al{sub T}{sup 2.41+}){sub 8}(O{sup 1.64-}){sub 27}(N{sup 2.27-}){sub 5} from our reassessment of the ionic character. We summarize and speculate that the considered oxynitride single-crystals exhibit highly elastic anisotropy. The interpretation of the thermodynamic properties of {gamma}-AlON according to quasi-harmonic Debye model confirm the available experiments and are extended to a wider temperature/pressure range. This material holds high elastic strength under extreme environments, where dB/dT absolute value is less than 0.03 GPa/K, independent of the pressure. Finally, we study the O/N structure disorder character of {gamma}-AlON solid solution by investigating nine possible crystal structures. It is found that {gamma}-AlON should be partially disordered, and in fact, the O/N ordering has a significant effect on the properties.

  15. Electronic, elastic, thermodynamic properties and structure disorder of γ-AlON solid solution from ab initio calculations

    International Nuclear Information System (INIS)

    Wang, Yuezhong; Lu, Tiecheng; Zhang, Rongshi; Jiang, Shengli; Qi, Jianqi; Wang, Ying; Chen, Qingyun; Miao, Naihua; He, Duanwei

    2013-01-01

    Highlights: ► We reassess the chemical bonding character of γ-AlON which shows strong ionicity. ► γ-AlON single-crystals exhibit highly elastic anisotropy. ► The thermodynamic properties are investigated in a wider temperature/pressure range. ► γ-AlON is an O/N partially disordered structure. - Abstract: Spinel aluminium oxynitride (γ-AlON), as a kind of transparent ceramic material expectable, is studied using the ab initio density functional method, in terms of electronic, elastic, thermodynamic properties and structure disorder. The results show that γ-AlON exhibits strong ionicity, as quantitatively expressed by (Al O 2.43+ ) 15 (Al T 2.41+ ) 8 (O 1.64- ) 27 (N 2.27- ) 5 from our reassessment of the ionic character. We summarize and speculate that the considered oxynitride single-crystals exhibit highly elastic anisotropy. The interpretation of the thermodynamic properties of γ-AlON according to quasi-harmonic Debye model confirm the available experiments and are extended to a wider temperature/pressure range. This material holds high elastic strength under extreme environments, where dB/dT absolute value is less than 0.03 GPa/K, independent of the pressure. Finally, we study the O/N structure disorder character of γ-AlON solid solution by investigating nine possible crystal structures. It is found that γ-AlON should be partially disordered, and in fact, the O/N ordering has a significant effect on the properties.

  16. Calculation of thermodynamic equilibrium between bcc disordered solid solutions U and Mo

    International Nuclear Information System (INIS)

    Alonso, Paula R.; Rubiolo, Gerardo H.

    2003-01-01

    There is actually an interest to develop a new fuel with higher density for research reactors. Fuel plates would be obtained by dispersion, a method that requires both a very dense fuel dispersant (>15.0 g U/cm 3 ) and a very high volume loading of the dispersant (>55%). Dispersants based in gamma (BCC) stabilized uranium alloys are being investigated, as they are able to reach uranium densities of 17.0 g U/cm 3 . Among them, we focus in U(Mo) bcc solid solutions with the addition of ternary elements to stabilize gamma phase. Transition metals, 4d and 5d, of groups VII and VIII are good candidates for the ternary alloy U - Mo - X. Their relative power to stabilize gamma phase seems to be in close relation with bonding energies between atoms in the alloy. A first approach to the calculation of these energies has been performed by the semi empiric method of Miedema where only bonds between pairs are considered, neglecting ternary and quaternary bonds. There is also a lack of information concerning solubilities of the ternary elements in the ternary cubic phase. In this work we aim to calculate bonding energies between atoms in the alloy using a cluster expansion of the formation energy (T=0 K) of a series of bcc ordered compounds in the systems U-Mo-X. Then the calculation of the equilibrium phase diagram by the Cluster Variation Method will be done (CVM). We show here the first part of the investigation devoted to calculation of phases equilibria in the U Mo system Formation energies of the ordered compounds were obtained by the first principles methods TB-LMTO-ASA and FP-LAPW. Another set of bonding energies was calculated in order to fit the known experimental diagram and new formation energies for the ordered compounds were derived from them. Discrepancies between both sets are discussed. (author)

  17. A self-consistent model for thermodynamics of multicomponent solid solutions

    International Nuclear Information System (INIS)

    Svoboda, J.; Fischer, F.D.

    2016-01-01

    The self-consistent concept recently published in this journal (108, 27–30, 2015) is extended from a binary to a multicomponent system. This is possible by exploiting the trapping concept as basis for including the interaction of atoms in terms of pairs (e.g. A–A, B–B, C–C…) and couples (e.g. A–B, B–C, …) in a multicomponent system with A as solvent and B, C, … as dilute solutes. The model results in a formulation of Gibbs-energy, which can be minimized. Examples show that the couple and pair formation may influence the equilibrium Gibbs energy markedly.

  18. Theoretical investigations on the elastic and thermodynamic properties of Ti2AlC0.5N0.5 solid solution

    International Nuclear Information System (INIS)

    Du, Y.L.; Sun, Z.M.; Hashimoto, H.; Barsoum, M.W.

    2009-01-01

    We have performed theoretical studies on the elastic and thermodynamic properties of the solid solution: Ti 2 AlC 0.5 N 0.5 . The lattice parameters, elastic constants, bulk, shear, Young's moduli, Poisson's ratio and Debye temperature were calculated and compared with those of the end members, Ti 2 AlC and Ti 2 AlN. The temperature dependence of the bulk moduli, thermal expansion coefficient and specific heats of Ti 2 AlC 0.5 N 0.5 were obtained from the quasi-harmonic Debye model. The calculated elastic and thermodynamic properties were compared with experimental data.

  19. High temperature thermodynamics of H2 and D2 in titanium, and in dilute titanium oxygen solid solutions

    International Nuclear Information System (INIS)

    Dantzer, P.

    1983-01-01

    The Tian Calvet microcalorimetric method has been improved in order to determine ΔH-barsub(H)(D), the partial molar enthalpy of mixing of hydrogen (deuterium) in the Ti-H 2 (D 2 ) solid systems for compositions 0 2 solid solutions (y = (O/Ti)) at 745 K. The combined calorimetric and equilibrium method allows a precise evaluation of the partial molar entropies. The results of this study differ substantially from earlier published data. (author)

  20. Molecular thermodynamics using fluctuation solution theory

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela

    . The framework relates thermodynamic variables to molecular pair correlation functions of liquid mixtures. In this thesis, application of the framework is illustrated using two approaches: 1. Solubilities of solid solutes in mixed solvent systems are determined from fluctuation solution theory application......Properties of chemicals and their mutual phase equilibria are critical variables in process design. Reliable estimates of relevant equilibrium properties, from thermodynamic models, can form the basis of good decision making in the development phase of a process design, especially when access...... to relevant experimental data is limited. This thesis addresses the issue of generating and using simple thermodynamic models within a rigorous statistical mechanical framework, the so-called fluctuation solution theory, from which relations connecting properties and phase equilibria can be obtained...

  1. Synthesis, characterization, kinetic and thermodynamic studies of the dissolution of ThO2 and of solid solutions Th1-xMxO2 (M = U, Pu)

    International Nuclear Information System (INIS)

    Heisbourg, G.

    2003-12-01

    The aim of this work was to understand the mechanisms of dissolution of ThO 2 and of thorium mixed oxides such as Th 1-x U x O 2 and Th 1-x Pu x O 2 in aqueous, oxygenated or inert media. Several solids have been synthesized by precipitation in oxalic medium: Th 1-x U x O 2 (x= 0.11; 0.24; 0.37; 0.53; 0.67; 0.81 and 0.91) and Th 1-x Pu x O 2 (x= 0.13; 0.32 and 0.66). They have been characterized by XRD, SEM, TEM, XPS, XAS, PIXE and EPMA. The sintering conditions of these materials have been studied and optimized in order to obtain sintered samples with a measured density very near the theoretical densities. A kinetic study of the dissolution of ThO 2 and of solid solutions Th 1-x U x O 2 has been carried out in several aqueous media (HNO 3 , HCl, H 2 SO 4 ) in terms of several parameters: protons concentration, temperature, pH, ionic strength, nature of the electrolyte solution and uranium molar ratio for the solid solutions Th 1-x U x O 2 in order to determine the kinetic laws of dissolution of the solid solutions having different compositions comparatively to ThO 2 . The leaching tests carried out in natural waters of compositions near those of the deep geologic sites considered for the storage of nuclear wastes have shown that the dissolution of the solids was bound to the complexing effect of the constitutional ions of the water considered. The leaching tests carried out on sintered samples of the same composition have led to the same normalized dissolution velocities. The thermodynamic aspect of the dissolution of the solid solutions Th 1-x U x O 2 in nitric medium has been studied at last. (O.M.)

  2. Irreversible thermodynamics of overdriven shocks in solids

    International Nuclear Information System (INIS)

    Wallace, D.C.

    1981-01-01

    An isotropic solid capable of transporting heat and of undergoing dissipative plastic flow, is treated. The shock is assumed to be a steady wave, and any phase changes or macroscopic inhomogeneities which might be induced by the shock are neglected. Under these conditions it is established that for an overdriven shock, no solution is possible without heat transport, and when the heat transport is governed by the steady conduction equation, no solution is possible without plastic dissipation as well. Upper and lower bounds are established for the thermodynamic variables, namely the shear stress, temperature, entropy, plastic strain, and heat flux, as functions of compression through the shock

  3. Oxygen nonstoichiometry and thermodynamic quantities in solid solution SrFe1-xSnxO3-δ

    Science.gov (United States)

    Merkulov, O. V.; Markov, A. A.; Leonidov, I. A.; Patrakeev, M. V.; Kozhevnikov, V. L.

    2018-06-01

    The oxygen content (3-δ) variations in tin substituted derivatives SrFe1-xSnxO3-δ, where x = 0.05, 0.1, 0.17 and 0.25, of perovskite-like strontium ferrite, have been studied by coulometric titration measurements within oxygen partial pressure (pO2) range 10-19-10-2 atm at 800-950 °С. The obtained dependencies of (3-δ) from pO2 and temperature are used for calculations of partial molar thermodynamic functions of oxygen in the oxide structure. It is found that a satisfactory explanation of the experimental results can be attained within frameworks of the ideal solution model with ion and electron defects appearing in the result of oxidation and disproportionation of iron cations. The increase of the oxidation reaction enthalpy with tin content is consistent with the increase of the unit cell parameter, i.e., the stretch and relaxation of Fe-O chemical bonds.

  4. Equilibrium, kinetics and thermodynamics studies of chitosan-based solid phase nanoparticles as sorbent for lead (II) cations from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Shaker, Medhat A., E-mail: drmashaker@yahoo.com [Current address: Chemistry Department, Faculty of Science, University of Jeddah, Jeddah (Saudi Arabia); Permanent address: Chemistry Department, Faculty of Science, Damanhour University, Damanhour (Egypt)

    2015-07-15

    Ternary nanoparticles of chitosan, non-viable biomass (Pseudomonas sp.) and gelatin, CPG were synthesized by chemical crosslinking method and applied as a novel and cost-effective solid phase to adsorb Pb(II) cations from aqueous solution. Characterization of the fabricated CPG nanoparticles and their complexation behavior were extensively interrogated by dynamic light scattering (DLS), FTIR, TGA, XRD and SEM techniques. The extent of adsorption was found to be a function of medium pH, contact time, initial Pb(II) concentration and temperature. The Langmuir, Freundlich, Dubinin–Radushkevich and Redlich–Peterson models were used to illustrate the isotherms of the adsorption system. The adsorption of Pb(II) cations onto CPG best-fits the Langmuir isotherm model which predicts two stoichiometric temperature-independent adsorption sites, A and B with variable capacities, 35.4 and 91.1 mg g{sup −1}, respectively and removal capacity above 90%. Thermodynamic studies revealed that the adsorption process was physical, spontaneous, and endothermic. The adsorption rate is influenced by temperature and the adsorption kinetic is well confirmed with pseudo-second-order equation compared with three other investigated kinetic models. Present study indicated potential applications of CPG nanoparticles as excellent natural and promising solid phase for Pb(II) extraction in wastewater treatment. - Graphical abstract: Display Omitted - Highlights: • Kinetics and thermodynamics of Pb{sup 2+} biosorption onto CPG nanoparticles are studied. • Adsorption kinetic data are best modeled using second-order rate equations. • The Pb{sup 2}adsorption onto CPG was physical diffusion controlled reaction. • The experimental equilibrium results well fit the Langmuir model. • The thermodynamics show endothermic, favorable and spontaneous adsorption processes.

  5. Halogen bonding in solution: thermodynamics and applications.

    Science.gov (United States)

    Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

    2013-02-21

    Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

  6. Thermodynamic stability of radioactivity standard solutions

    International Nuclear Information System (INIS)

    Iroulard, M.G.

    2007-04-01

    The basic requirement when preparing radioactivity standard solutions is to guarantee the concentration of a radionuclide or a radioelement, expressed in the form of activity concentration (Ac = A/m (Bq/g), with A: activity and m: mass of solution). Knowledge of the law of radioactive decay and the half-life of a radionuclide or radioelement makes it possible to determine the activity concentration at any time, and this must be confirmed subsequently by measurement. Furthermore, when radioactivity standard solutions are prepared, it is necessary to establish optimal conditions of thermodynamic stability of the standard solutions. Radioactivity standard solutions are prepared by metrology laboratories from original solutions obtained from a range of suppliers. These radioactivity standard solutions must enable preparation of liquid and/or solid radioactivity standard sources of which measurement by different methods can determine, at a given instant, the activity concentration of the radionuclide or radioelement present in the solution. There are a number of constraints associated with the preparation of such sources. Here only those that relate to the physical and chemical properties of the standard solution are considered, and therefore need to be taken into account when preparing a radioactivity standard solution. These issues are considered in this document in accordance with the following plan: - A first part devoted to the chemical properties of the solutions: - the solubilization media: ultra-pure water and acid media, - the carriers: concentration, oxidation state of the radioactive element and the carrier element. - A second part describing the methodology of the preparation, packaging and storage of standard solutions: - glass ampoules: the structure of glasses, the mechanisms of their dissolution, the sorption phenomenon at the solid-solution interface, - quartz ampoules, - cleaning and packaging: cleaning solutions, internal surface coatings and

  7. Thermodynamic stability of radioactivity standard solutions

    Energy Technology Data Exchange (ETDEWEB)

    Iroulard, M.G

    2007-04-15

    The basic requirement when preparing radioactivity standard solutions is to guarantee the concentration of a radionuclide or a radioelement, expressed in the form of activity concentration (Ac = A/m (Bq/g), with A: activity and m: mass of solution). Knowledge of the law of radioactive decay and the half-life of a radionuclide or radioelement makes it possible to determine the activity concentration at any time, and this must be confirmed subsequently by measurement. Furthermore, when radioactivity standard solutions are prepared, it is necessary to establish optimal conditions of thermodynamic stability of the standard solutions. Radioactivity standard solutions are prepared by metrology laboratories from original solutions obtained from a range of suppliers. These radioactivity standard solutions must enable preparation of liquid and/or solid radioactivity standard sources of which measurement by different methods can determine, at a given instant, the activity concentration of the radionuclide or radioelement present in the solution. There are a number of constraints associated with the preparation of such sources. Here only those that relate to the physical and chemical properties of the standard solution are considered, and therefore need to be taken into account when preparing a radioactivity standard solution. These issues are considered in this document in accordance with the following plan: - A first part devoted to the chemical properties of the solutions: - the solubilization media: ultra-pure water and acid media, - the carriers: concentration, oxidation state of the radioactive element and the carrier element. - A second part describing the methodology of the preparation, packaging and storage of standard solutions: - glass ampoules: the structure of glasses, the mechanisms of their dissolution, the sorption phenomenon at the solid-solution interface, - quartz ampoules, - cleaning and packaging: cleaning solutions, internal surface coatings and

  8. Thermodynamic mixing properties of the UO{sub 2}–HfO{sub 2} solid solution: Density functional theory and Monte Carlo simulations

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Ke, E-mail: keyuan@umich.edu [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Becker, Udo [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States)

    2015-03-15

    HfO{sub 2} is a neutron absorber and has been mechanically mixed with UO{sub 2} in nuclear fuel in order to control the core power distribution. During nuclear fission, the temperature at the center of the fuel pellet can reach above 1300 K, where hafnium may substitute uranium and form the binary solid solution of UO{sub 2}–HfO{sub 2}. UO{sub 2} adopts the cubic fluorite structure, but HfO{sub 2} can occur in monoclinic, tetragonal, and cubic structures. The distribution of Hf and U ions in the UO{sub 2}–HfO{sub 2} binary and its atomic structure influence the thermal conductivity and melting point of the fuel. However, experimental data on the UO{sub 2}–HfO{sub 2} binary are limited. Therefore, the enthalpies of mixing of the UO{sub 2}–HfO{sub 2} binary with three different structures were calculated in this study using density functional theory and subsequent Monte Carlo simulations. The free energy of mixing was obtained from thermodynamic integration of the enthalpy of mixing over temperature. From the ΔG of mixing, a phase diagram of the binary was obtained. The calculated UO{sub 2}–HfO{sub 2} binary forms extensive solid solution across the entire compositional range, but there are a variety of possible exsolution phenomena associated with the different HfO{sub 2} polymorphs. As the structure of the HfO{sub 2} end member adopts lower symmetry and becomes less similar to cubic UO{sub 2}, the miscibility gap of the phase diagram expands, accompanied by an increase in cell volume by 7–10% as the structure transforms from cubic to monoclinic. Close to the UO{sub 2} end member, which is relevant to the nuclear fuel, the isometric uranium-rich solid solutions exsolve as the fuel cools, and there is a tendency to form the monoclinic hafnium-rich phase in the matrix of the isometric, uranium-rich solid solution phase.

  9. Introduction to the thermodynamics of solids

    International Nuclear Information System (INIS)

    Ericksen, J.L.

    1992-01-01

    This book addresses issues of thermodynamics associated with solids from a unique point of view. Professor Ericksen provides a perspective of thermodynamics which is based in material science and solid mechanics, and attempts to apply basic thermodynamics to a wide range of phenomena. The book is not written as a text-book, as it does not contain example problems or exercises, is directed primarily at researchers in solids. The author states that much of the book is controversial, and that many of his treatments of thermodynamics are not traditional. The author's assessment is accurate on both counts. However, there are several reasons to believe that many of the issues raised in the book are not so much controversial, but rather simply not well described, either by the author or by thermodynamicists, in general. The primary references for much of the thermodynamics in the book are historic in nature, and certainly worthy of consideration, but only a few current references are provided

  10. Thermodynamic characteristics of systems with solid solutions composed of crystal hydrates of lanthanide and yttrium chlorides, at 250C. III. Systems of Roozeboom's type IV, with restricted solid solutions

    International Nuclear Information System (INIS)

    Sokolova, N.P.

    1983-01-01

    The values of the activity, the activity coefficients, the free energy of mixing and the excess free energy of mixing have been calculated for CeCl 3 -LnCl 3 -H 2 O systems (where Ln identical with Sm, Gd, Dy, Ho, Er, Y) containing solid solutions of types IV and IVa. It is shown that the stability of the solid solutions decreases with increasing difference between the radii of the cations of cerium and the second lanthanide, which enter into the composition of the components of the solid solutions. The factors determining the composition of a liquid solution corresponding to the eutonic point are specified

  11. Thermodynamics of gas adsorption on solid adsorbents

    International Nuclear Information System (INIS)

    Budrugeac, P.

    1979-01-01

    Starting with several hypotheses about the adsorbtion system and the adsorption phenomenon, a thermodynamic treatment of gas adsorption on solid adsorbants is presented. The relationships for determination from isotherms and calorimetric data of thermodynamic functions are derived. The problem of the phase changes in adsorbed layer is discussed. (author)

  12. Synthesis, single crystal growth and thermodynamic properties of SrNdAlO4-CaNdAlO4 solid solutions

    International Nuclear Information System (INIS)

    Novoselov, A.; Ryumin, M.; Pushkina, G.; Spiridonov, F.; Komissarova, L.; Zimina, G.; Pajaczkowska, A.

    2005-01-01

    Continuous solid solutions in the SrNdAlO 4 -CaNdAlO 4 system are formed. Powder samples of Sr x Ca 1-x NdAlO 4 (0.0≤x≤1.0) were obtained using the carbonate coprecipitation method while single crystals of Sr x Ca 1-x NdAlO 4 (x=0.0,0.162,0.392,0.687,1.0) were grown by the Czochralski method. Structural parameters and thermodynamic properties of the samples were studied by X-ray diffraction and heat flux Calvet calorimetry. Composition dependence of lattice constants was observed to follow Vegard's low. Heat of solution of the Sr x Ca 1-x NdAlO 4 samples in molten 2PbO.B 2 O 3 were measured, and enthalpies of formation and mixing were calculated. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  13. Application of thermodynamics to silicate crystalline solutions

    Science.gov (United States)

    Saxena, S. K.

    1972-01-01

    A review of thermodynamic relations is presented, describing Guggenheim's regular solution models, the simple mixture, the zeroth approximation, and the quasi-chemical model. The possibilities of retrieving useful thermodynamic quantities from phase equilibrium studies are discussed. Such quantities include the activity-composition relations and the free energy of mixing in crystalline solutions. Theory and results of the study of partitioning of elements in coexisting minerals are briefly reviewed. A thermodynamic study of the intercrystalline and intracrystalline ion exchange relations gives useful information on the thermodynamic behavior of the crystalline solutions involved. Such information is necessary for the solution of most petrogenic problems and for geothermometry. Thermodynamic quantities for tungstates (CaWO4-SrWO4) are calculated.

  14. Thermodynamic properties of the solid solutions CuCr/sub 2/S/sub 4/ in Cu/sub 1///sub 2/M/sub 1///sub 2/Cr/sub 2/S/sub 4/ (M=Ga, In)

    Energy Technology Data Exchange (ETDEWEB)

    Titov, V.V.; Gordeev, I.V.; Kesler, Y.A.; Shchelkotunov, V.A.; Tret' yakov, Y.D.

    1985-09-01

    Using an adiabatic calorimeter and a quartz dilatometer, the temperature dependences of the heat capacity for the solid solutions CuCr/sub 2/S/sub 4/ in Cu/sub 1///sub 2/M/sub 1///sub 2/Cr/sub 2/S/sub 4/ (M - Ga, In) were determined, the different components of the heat capacity were evaluated, and the thermodynamic parameters of the magnetic transformation were calculated.

  15. Radionuclide solubility control by solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Brandt, F.; Klinkenberg, M.; Rozov, K.; Bosbach, D. [Forschungszentrum Juelich GmbH (Germany). Inst. of Energy and Climate Research - Nuclear Waste Management and Reactor Safety (IEK-6); Vinograd, V. [Frankfurt Univ. (Germany). Inst. of Geosciences

    2015-07-01

    The migration of radionuclides in the geosphere is to a large extend controlled by sorption processes onto minerals and colloids. On a molecular level, sorption phenomena involve surface complexation, ion exchange as well as solid solution formation. The formation of solid solutions leads to the structural incorporation of radionuclides in a host structure. Such solid solutions are ubiquitous in natural systems - most minerals in nature are atomistic mixtures of elements rather than pure compounds because their formation leads to a thermodynamically more stable situation compared to the formation of pure compounds. However, due to a lack of reliable data for the expected scenario at close-to equilibrium conditions, solid solution systems have so far not been considered in long-term safety assessments for nuclear waste repositories. In recent years, various solid-solution aqueous solution systems have been studied. Here we present state-of-the art results regarding the formation of (Ra,Ba)SO{sub 4} solid solutions. In some scenarios describing a waste repository system for spent nuclear fuel in crystalline rocks {sup 226}Ra dominates the radiological impact to the environment associated with the potential release of radionuclides from the repository in the future. The solubility of Ra in equilibrium with (Ra,Ba)SO{sub 4} is much lower than the one calculated with RaSO{sub 4} as solubility limiting phase. Especially, the available literature data for the interaction parameter W{sub BaRa}, which describes the non-ideality of the solid solution, vary by about one order of magnitude (Zhu, 2004; Curti et al., 2010). The final {sup 226}Ra concentration in this system is extremely sensitive to the amount of barite, the difference in the solubility products of the end-member phases, and the degree of non-ideality of the solid solution phase. Here, we have enhanced the fundamental understanding regarding (1) the thermodynamics of (Ra,Ba)SO{sub 4} solid solutions and (2) the

  16. Thermodynamic properties of potassium chloride aqueous solutions

    Science.gov (United States)

    Zezin, Denis; Driesner, Thomas

    2017-04-01

    Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.

  17. First-principles calculations of the structural and thermodynamic properties of bcc, fcc and hcp solid solutions in the Al-TM (TM = Ti, Zr and Hf) systems: A comparison of cluster expansion and supercell methods

    International Nuclear Information System (INIS)

    Ghosh, G.; Walle, A. van de; Asta, M.

    2008-01-01

    The thermodynamic properties of solid solutions with body-centered cubic (bcc), face-centered cubic (fcc) and hexagonal close-packed (hcp) structures in the Al-TM (TM = Ti, Zr and Hf) systems are calculated from first-principles using cluster expansion (CE), Monte-Carlo simulation and supercell methods. The 32-atom special quasirandom structure (SQS) supercells are employed to compute properties at 25, 50 and 75 at.% TM compositions, and 64-atom supercells have been employed to compute properties of alloys in the dilute concentration limit (one solute and 63 solvent atoms). In general, the energy of mixing (Δ m E) calculated by CE and dilute supercells agree very well. In the concentrated region, the Δ m E values calculated by CE and SQS methods also agree well in many cases; however, noteworthy discrepancies are found in some cases, which we argue originate from inherent elastic and dynamic instabilities of the relevant parent lattice structures. The importance of short-range order on the calculated values of Δ m E for hcp Al-Ti alloys is demonstrated. We also present calculated results for the composition dependence of the atomic volumes in random solid solutions with bcc, fcc and hcp structures. The properties of solid solutions reported here may be integrated within the CALPHAD formalism to develop reliable thermodynamic databases in order to facilitate: (i) calculations of stable and metastable phase diagrams of binary and multicomponent systems, (ii) alloy design, and (iii) processing of Al-TM-based alloys

  18. Interlayer growth kinetics of a binary solid-solution based on the thermodynamic extremal principle: Application to the formation of spinel at periclase-corundum contacts

    Czech Academy of Sciences Publication Activity Database

    Abart, R.; Svoboda, Jiří; Jeřábek, P.; Povoden-Karadeniz, E.; Habler, G.

    2016-01-01

    Roč. 316, č. 4 (2016), s. 309-328 ISSN 0002-9599 Institutional support: RVO:68081723 Keywords : reactive dffusion * interface migration * thermodynamic modeling * spinel Subject RIV: BJ - Thermodynamics Impact factor: 4.099, year: 2016

  19. The influence of precipitation kinetics on trace element partitioning between solid and liquid solutions: A coupled fluid dynamics/thermodynamics framework to predict distribution coefficients

    Science.gov (United States)

    Kavner, A.

    2017-12-01

    In a multicomponent multiphase geochemical system undergoing a chemical reaction such as precipitation and/or dissolution, the partitioning of species between phases is determined by a combination of thermodynamic properties and transport processes. The interpretation of the observed distribution of trace elements requires models integrating coupled chemistry and mechanical transport. Here, a framework is presented that predicts the kinetic effects on the distribution of species between two reacting phases. Based on a perturbation theory combining Navier-Stokes fluid flow and chemical reactivity, the framework predicts rate-dependent partition coefficients in a variety of different systems. We present the theoretical framework, with applications to two systems: 1. species- and isotope-dependent Soret diffusion of species in a multicomponent silicate melt subjected to a temperature gradient, and 2. Elemental partitioning and isotope fractionation during precipitation of a multicomponent solid from a multicomponent liquid phase. Predictions will be compared with results from experimental studies. The approach has applications for understanding chemical exchange in at boundary layers such as the Earth's surface magmatic systems and at the core/mantle boundary.

  20. Osmosis and thermodynamics explained by solute blocking.

    Science.gov (United States)

    Nelson, Peter Hugo

    2017-01-01

    A solute-blocking model is presented that provides a kinetic explanation of osmosis and ideal solution thermodynamics. It validates a diffusive model of osmosis that is distinct from the traditional convective flow model of osmosis. Osmotic equilibrium occurs when the fraction of water molecules in solution matches the fraction of pure water molecules that have enough energy to overcome the pressure difference. Solute-blocking also provides a kinetic explanation for why Raoult's law and the other colligative properties depend on the mole fraction (but not the size) of the solute particles, resulting in a novel kinetic explanation for the entropy of mixing and chemical potential of ideal solutions. Some of its novel predictions have been confirmed; others can be tested experimentally or by simulation.

  1. Osmosis and thermodynamics explained by solute blocking

    Science.gov (United States)

    Nelson, Peter Hugo

    2016-01-01

    A solute-blocking model is presented that provides a kinetic explanation of osmosis and ideal solution thermodynamics. It validates a diffusive model of osmosis that is distinct from the traditional convective flow model of osmosis. Osmotic equilibrium occurs when the fraction of water molecules in solution matches the fraction of pure water molecules that have enough energy to overcome the pressure difference. Solute-blocking also provides a kinetic explanation for why Raoult’s law and the other colligative properties depend on the mole fraction (but not the size) of the solute particles, resulting in a novel kinetic explanation for the entropy of mixing and chemical potential of ideal solutions. Some of its novel predictions have been confirmed, others can be tested experimentally or by simulation. PMID:27225298

  2. Thermodynamics of ionic processes in solutions

    International Nuclear Information System (INIS)

    Krestov, G.A.

    1984-01-01

    The present nitions about the mechanism of solvation of atomic-molecular particles and the structure of electrolyte and non electrolyte solutions are given. From common positions a wide range of interrelated problems (general and thermodynamic characteristic of ions, thermodynamic characteristic of ion solvation and various ionic reactions in solutions, structural changes of the solvent in the above processes etc...) is considered. The latest scientific data including those on the effect on the thermodynamio properties of low temperatures, various impurities (air, water), large ions, peculiarities of the structure of solvent molecules reflected. Considerable attention is given to new conceptions definitions, structural notions as well as theoretical and experimental methods of obtaining quantitative characteristics of ion solvation

  3. Thermodynamic properties of CuCr2S4 solid solutions in Cusub(1/2)Msub(1/2)Crsub(2)Ssub(4) (M - Ga, In)

    International Nuclear Information System (INIS)

    Titov, V.V.; Kesler, Ya.A.; Shelkotunov, V.A.; Gordeev, I.V.; Tret'yakov, Yu.D.

    1985-01-01

    By means of an adiabatic calorimeter and quartz dilatometer for CuCr 2 S 4 in Cusub(1/2)Msub(1/2)Crsub(2)Ssub(4) (M-Ga, In) temperature dependences of heat capacity are determined. The contribution of various components into heat capacity is estimated, thermodynamic parameters of magnetic transformation are calculated

  4. Thermotransport in interstitial solid solutions

    International Nuclear Information System (INIS)

    Fogel'son, R.L.

    1982-01-01

    On the basis of literature data the problem of thermotransport of impurities (H, N, O, C) in interstitial solid solutions is considered. It is shown that from experimental data on the thermotransport an important parameter of dissolved atoms can be found which characterizes atom state in these solutions-enthalpy of transport

  5. Thermodynamical description of stationary, asymptotically flat solutions with conical singularities

    International Nuclear Information System (INIS)

    Herdeiro, Carlos; Rebelo, Carmen; Radu, Eugen

    2010-01-01

    We examine the thermodynamical properties of a number of asymptotically flat, stationary (but not static) solutions having conical singularities, with both connected and nonconnected event horizons, using the thermodynamical description recently proposed in [C. Herdeiro, B. Kleihaus, J. Kunz, and E. Radu, Phys. Rev. D 81, 064013 (2010).]. The examples considered are the double-Kerr solution, the black ring rotating in either S 2 or S 1 , and the black Saturn, where the balance condition is not imposed for the latter two solutions. We show that not only the Bekenstein-Hawking area law is recovered from the thermodynamical description, but also the thermodynamical angular momentum is the Arnowitt-Deser-Misner angular momentum. We also analyze the thermodynamical stability and show that, for all these solutions, either the isothermal moment of inertia or the specific heat at constant angular momentum is negative, at any point in parameter space. Therefore, all these solutions are thermodynamically unstable in the grand canonical ensemble.

  6. A thermodynamic stability of bulk and epitaxial CdHgTe, ZnHgTe and MnHgTe solid solutions

    International Nuclear Information System (INIS)

    Dejbuk, V.G.; Dremlyuzhenko, S.G.; Ostapov, S.Eh.

    2005-01-01

    A thermodynamics of Cd 1-x Hg x Te, Zn x Hg 1-x Te and Mg x Hg 1-x Te alloys has been investigated for a delta-lattice parameter model. The phase diagrams obtained show the stability of Cd 1-x Hg x Te, Zn x Hg 1-x Te in the whole range of compositions, alongside with a miscibility gap for Mn x Hg 1-x Te being of 0.35 x Hg 1-x Te/CdTe and Mn x Hg 1-x Te/Cd 0.96 Zn 0.04 Te epitaxial films result in lowering critical temperatures and narrowing the miscibility gap [ru

  7. WATEQ3 geochemical model: thermodynamic data for several additional solids

    International Nuclear Information System (INIS)

    Krupka, K.M.; Jenne, E.A.

    1982-09-01

    Geochemical models such as WATEQ3 can be used to model the concentrations of water-soluble pollutants that may result from the disposal of nuclear waste and retorted oil shale. However, for a model to competently deal with these water-soluble pollutants, an adequate thermodynamic data base must be provided that includes elements identified as important in modeling these pollutants. To this end, several minerals and related solid phases were identified that were absent from the thermodynamic data base of WATEQ3. In this study, the thermodynamic data for the identified solids were compiled and selected from several published tabulations of thermodynamic data. For these solids, an accepted Gibbs free energy of formation, ΔG 0 /sub f,298/, was selected for each solid phase based on the recentness of the tabulated data and on considerations of internal consistency with respect to both the published tabulations and the existing data in WATEQ3. For those solids not included in these published tabulations, Gibbs free energies of formation were calculated from published solubility data (e.g., lepidocrocite), or were estimated (e.g., nontronite) using a free-energy summation method described by Mattigod and Sposito (1978). The accepted or estimated free energies were then combined with internally consistent, ancillary thermodynamic data to calculate equilibrium constants for the hydrolysis reactions of these minerals and related solid phases. Including these values in the WATEQ3 data base increased the competency of this geochemical model in applications associated with the disposal of nuclear waste and retorted oil shale. Additional minerals and related solid phases that need to be added to the solubility submodel will be identified as modeling applications continue in these two programs

  8. Uranothorite solid solutions: From synthesis to dissolution

    International Nuclear Information System (INIS)

    Costin, Dan-Tiberiu

    2012-01-01

    USiO 4 coffinite appears as one of the potential phases formed in the back-end of the alteration of spent fuel, in reducing storage conditions. A study aiming to assess the thermodynamic data associated with coffinite through an approach based on the preparation of Th 1-x U x SiO 4 uranothorite solid solutions was then developed during this work. First, the preparation of uranothorite samples was successfully undertaken in hydrothermal conditions. However, the poly-phased samples systematically formed for x ≥ 0,2 underlined the kinetic hindering linked with the preparation of uranium-enriched samples, including coffinite end-member. Nevertheless, the characterization of the various samples led to confirm the formation of an ideal solid solution and allowed the constitution of a spectroscopic database. The purification of the samples was then performed by the means of different protocols based on physical (dispersion-centrifugation) or chemical (selective dissolution of secondary phases) methods. This latter led to a complete of the impurities (Th 1-y U y O 2 mixed oxide and amorphous silica) through successive washing steps in acid then basic media. Finally, dissolution experiments were undertaken on uranothorite samples (0 ≤ xexp. ≤ 0,5) and allowed pointing out the influence of composition, pH and temperature on the normalized dissolution rate of the compounds. Also, the associated thermodynamic data, such as activation energy, indicate that the reaction is controlled by surface reactions. Once the equilibrium is reached, the analogous solubility constants were determined for each composition studied, then allowing the extrapolation to coffinite value. It was then finally possible to conclude on the inversion of coffinitisation reaction with temperature. (author) [fr

  9. Free energy of formation of Mo2C and the thermodynamic properties of carbon in solid molybdenum

    Science.gov (United States)

    Seigle, L. L.; Chang, C. L.; Sharma, T. P.

    1979-01-01

    As part of a study of the thermodynamical properties of interstitial elements in refractory metals, the free energy of formation of Mo2C is determined, and the thermodynamical properties of C in solution in solid Mo evaluated. The activity of C in the two-phase region Mo + Mo2C is obtained from the C content of iron rods equilibrated with metal + carbide powder mixtures. The free energy of formation of alpha-Mo2C is determined from the activity data. The thermodynamic properties of C in the terminal solid solution are calculated from available data on the solid solubility of C in Mo. Lattice distortion due to misfit of the C atoms in the interstitial sites appears to play a significant role in determining the thermodynamic properties of C in solid Mo.

  10. Thermodynamics, diffusion and the Kirkendall effect in solids

    CERN Document Server

    Paul, Aloke; Vuorinen, Vesa; Divinski, Sergiy V

    2014-01-01

    Covering both basic and advanced thermodynamic and phase  principles,  as well as providing stability diagrams relevant for diffusion studies, Thermodynamics, Diffusion and the Kirkendall Effect in Solids maximizes reader insights into Fick’s laws of diffusion, atomic mechanisms, interdiffusion, intrinsic diffusion, tracer diffusion and the Kirkendall effect. Recent advances in the area of interdiffusion will be introduced, while the many practical examples and large number of illustrations given will serve to aid researches working in this area in learning the practical evaluation of various diffusion parameters from experimental results. With a unique approach to the two main focal points in solid state transformations, energetics (thermodynamics) and kinetics (interdiffusion) are extensively studied and their combined use in practise is discussed. Recent developments in the area of Kirkendall effect, grain boundary diffusion and multicomponent diffusion are also covered extensively. This book will appe...

  11. Thermodynamic curvature of soft-sphere fluids and solids

    Science.gov (United States)

    Brańka, A. C.; Pieprzyk, S.; Heyes, D. M.

    2018-02-01

    The influence of the strength of repulsion between particles on the thermodynamic curvature scalar R for the fluid and solid states is investigated for particles interacting with the inverse power (r-n) potential, where r is the pair separation and 1 /n is the softness. Exact results are obtained for R in certain limiting cases, and the R behavior determined for the systems in the fluid and solid phases. It is found that in such systems the thermodynamic curvature can be positive for very soft particles, negative for steeply repulsive (or large n ) particles across almost the entire density range, and can change sign between negative and positive at a certain density. The relationship between R and the form of the interaction potential is more complex than previously suggested, and it may be that R is an indicator of the relative importance of energy and entropy contributions to the thermodynamic properties of the system.

  12. A Thermodynamic Mixed-Solid Asphaltene Precipitation Model

    DEFF Research Database (Denmark)

    Lindeloff, Niels; Heidemann, R.A.; Andersen, Simon Ivar

    1998-01-01

    A simple model for the prediction of asphaltene precipitation is proposed. The model is based on an equation of state and uses standard thermodynamics, thus assuming that the precipitation phenomenon is a reversible process. The solid phase is treated as an ideal multicomponent mixture. An activity...

  13. Surface tension and related thermodynamic quantities of aqueous electrolyte solutions

    CERN Document Server

    Matubayasi, Norihiro

    2013-01-01

    Surface tension provides a thermodynamic avenue for analyzing systems in equilibrium and formulating phenomenological explanations for the behavior of constituent molecules in the surface region. While there are extensive experimental observations and established ideas regarding desorption of ions from the surfaces of aqueous salt solutions, a more successful discussion of the theory has recently emerged, which allows the quantitative calculation of the distribution of ions in the surface region. Surface Tension and Related Thermodynamic Quantities of Aqueous Electrolyte Solutions provides a d

  14. From thermodynamics to the solutions in gravity theory

    International Nuclear Information System (INIS)

    Zhang, Hongsheng; Li, Xin-Zhou

    2014-01-01

    In a recent work, we present a new point of view to the relation of gravity and thermodynamics, in which we derive the Schwarzschild solution through thermodynamic considerations by the aid of the Misner–Sharp mass in an adiabatic system. In this Letter we continue to investigate the relation between gravity and thermodynamics for obtaining solutions via thermodynamics. We generalize our studies on gravi-thermodynamics in Einstein gravity to modified gravity theories. By using the first law with the assumption that the Misner–Sharp mass is the mass for an adiabatic system, we reproduce the Boulware–Deser–Cai solution in Gauss–Bonnet gravity. Using this gravi-thermodynamic thought, we obtain a NEW class of solution in F(R) gravity in an n-dimensional (n≥3) spacetime which permits three-type (n−2)-dimensional maximally symmetric subspace, as an extension of our recent three-dimensional black hole solution, and four-dimensional Clifton–Barrow solution in F(R) gravity

  15. From thermodynamics to the solutions in gravity theory

    Directory of Open Access Journals (Sweden)

    Hongsheng Zhang

    2014-10-01

    Full Text Available In a recent work, we present a new point of view to the relation of gravity and thermodynamics, in which we derive the Schwarzschild solution through thermodynamic considerations by the aid of the Misner–Sharp mass in an adiabatic system. In this Letter we continue to investigate the relation between gravity and thermodynamics for obtaining solutions via thermodynamics. We generalize our studies on gravi-thermodynamics in Einstein gravity to modified gravity theories. By using the first law with the assumption that the Misner–Sharp mass is the mass for an adiabatic system, we reproduce the Boulware–Deser–Cai solution in Gauss–Bonnet gravity. Using this gravi-thermodynamic thought, we obtain a NEW class of solution in F(R gravity in an n-dimensional (n≥3 spacetime which permits three-type (n−2-dimensional maximally symmetric subspace, as an extension of our recent three-dimensional black hole solution, and four-dimensional Clifton–Barrow solution in F(R gravity.

  16. Thermodynamic properties of aqueous hydroxyurea solutions

    International Nuclear Information System (INIS)

    Kumar, Shekhar; Sinha, Pranay Kumar; Kamachi Mudali, U.; Natarajan, R.

    2011-01-01

    Hydroxyurea is a novel reductant for uranium-plutonium separation in PUREX process. Little information on its thermophysical properties is available in published literature. In this work, its contributions to aqueous density, apparent molal volume, vapour pressure and thermodynamic water activity values, derived from in-house experiments, are reported. (author)

  17. A thermodynamic model for aqueous solutions of liquid-like density

    Energy Technology Data Exchange (ETDEWEB)

    Pitzer, K.S.

    1987-06-01

    The paper describes a model for the prediction of the thermodynamic properties of multicomponent aqueous solutions and discusses its applications. The model was initially developed for solutions near room temperature, but has been found to be applicable to aqueous systems up to 300/sup 0/C or slightly higher. A liquid-like density and relatively small compressibility are assumed. A typical application is the prediction of the equilibrium between an aqueous phase (brine) and one or more solid phases (minerals). (ACR)

  18. Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

    Science.gov (United States)

    André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

    2018-03-01

    The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

  19. Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III-Fe(III-Cr(III-Cl-H2O system at 25°C

    Directory of Open Access Journals (Sweden)

    André Laurent

    2018-03-01

    Full Text Available The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(IIICl3(s (M= Al, Fe, Cr minerals solubility in Na-Al(III-Cr(III-Fe(III-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III remediation. Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production. Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

  20. Thermodynamic properties of solid deuterium in premelting region

    International Nuclear Information System (INIS)

    Udovichenko, B.G.; Esel'son, V.B.; Manzhelij, V.G.

    1984-01-01

    Thermal expansion and isothermal compressibility of solid normal deuterium are measured near the melting line under pressures up to 500 atm. The earlier measurement method is improved to operate in a wider range of working pressures. The effects are discussed which are produced by zero trranslational oscillations in the thermodynamic properties of deuterium. The change in the molar volume in the range from T=0 to the melting temperature is considered as a quantum characteristic of the crystal. The molar volumes of solid deuterium observed at the melting line at moderate P are compared and specified. At P=O and T=0 the molar volume of o-D 2 is found to be V 00 =(20.03+-0.07) cm 3 /mole which follows from the thermodynamic experiment

  1. Thermodynamics Prediction of Wax Precipitation in Black Oil Using Regular Solution Model and Plus Fraction Characterization

    Directory of Open Access Journals (Sweden)

    Wei Wang

    2013-01-01

    Full Text Available The precipitation of wax/solid paraffin during production, transportation, and processing of crude oil is a serious problem. It is essential to have a reliable model to predict the wax appearance temperature and the amount of solid precipitated at different conditions. This paper presents a work to predict the solid precipitation based on solid-liquid equilibrium with regular solution-molecular thermodynamic theory and characterization of the crude oil plus fraction. Due to the differences of solubility characteristics between solid and liquid phase, the solubility parameters of liquid and solid phase are calculated by a modified model. The heat capacity change between solid and liquid phase is considered and estimated in the thermodynamic model. An activity coefficient based thermodynamic method combined with two characteristic methods to calculate wax precipitation in crude oil, especially heavy oil, has been tested with experimental data. The results show that the wax appearance temperature and the amount of weight precipitated can be predicted well with the experimental data.

  2. Synthesis, characterization, kinetic and thermodynamic studies of the dissolution of ThO{sub 2} and of solid solutions Th{sub 1-x}M{sub x}O{sub 2} (M = U, Pu); Synthese, caracterisation et etudes cinetique et thermodynamique de la dissolution de ThO{sub 2} et des solutions solides Th{sub 1-x}M{sub x}O{sub 2} (M = U, Pu)

    Energy Technology Data Exchange (ETDEWEB)

    Heisbourg, G

    2003-12-01

    The aim of this work was to understand the mechanisms of dissolution of ThO{sub 2} and of thorium mixed oxides such as Th{sub 1-x}U{sub x}O{sub 2} and Th{sub 1-x}Pu{sub x}O{sub 2} in aqueous, oxygenated or inert media. Several solids have been synthesized by precipitation in oxalic medium: Th{sub 1-x}U{sub x}O{sub 2} (x= 0.11; 0.24; 0.37; 0.53; 0.67; 0.81 and 0.91) and Th{sub 1-x}Pu{sub x}O{sub 2} (x= 0.13; 0.32 and 0.66). They have been characterized by XRD, SEM, TEM, XPS, XAS, PIXE and EPMA. The sintering conditions of these materials have been studied and optimized in order to obtain sintered samples with a measured density very near the theoretical densities. A kinetic study of the dissolution of ThO{sub 2} and of solid solutions Th{sub 1-x}U{sub x}O{sub 2} has been carried out in several aqueous media (HNO{sub 3}, HCl, H{sub 2}SO{sub 4}) in terms of several parameters: protons concentration, temperature, pH, ionic strength, nature of the electrolyte solution and uranium molar ratio for the solid solutions Th{sub 1-x}U{sub x}O{sub 2} in order to determine the kinetic laws of dissolution of the solid solutions having different compositions comparatively to ThO{sub 2}. The leaching tests carried out in natural waters of compositions near those of the deep geologic sites considered for the storage of nuclear wastes have shown that the dissolution of the solids was bound to the complexing effect of the constitutional ions of the water considered. The leaching tests carried out on sintered samples of the same composition have led to the same normalized dissolution velocities. The thermodynamic aspect of the dissolution of the solid solutions Th{sub 1-x}U{sub x}O{sub 2} in nitric medium has been studied at last. (O.M.)

  3. Thermodynamics of water intrusion in nanoporous hydrophobic solids.

    Science.gov (United States)

    Cailliez, Fabien; Trzpit, Mickael; Soulard, Michel; Demachy, Isabelle; Boutin, Anne; Patarin, Joël; Fuchs, Alain H

    2008-08-28

    We report a joint experimental and molecular simulation study of water intrusion in silicalite-1 and ferrerite zeolites. The main conclusion of this study is that water condensation takes place through a genuine first-order phase transition, provided that the interconnected pores structure is 3-dimensional. In the extreme confinement situation (ferrierite zeolite), condensation takes place through a continuous transition, which is explained by a shift of both the first-order transition line and the critical point with increasing confinement. The present findings are at odds with the common belief that conventional phase transitions cannot take place in microporous solids such as zeolites. The most important features of the intrusion/extrusion process can be understood in terms of equilibrium thermodynamics considerations. We believe that these findings are very general for hydrophobic solids, i.e. for both nonwetting as well as wetting water-solid interface systems.

  4. Thermodynamics of a model solid with magnetoelastic coupling

    Science.gov (United States)

    Szałowski, K.; Balcerzak, T.; Jaščur, M.

    2018-01-01

    In the paper a study of a model magnetoelastic solid system is presented. The system of interest is a mean-field magnet with nearest-neighbour ferromagnetic interactions and the underlying s.c. crystalline lattice with the long-range Morse interatomic potential and the anharmonic Debye model for the lattice vibrations. The influence of the external magnetic field on the thermodynamics is investigated, with special emphasis put on the consequences of the magnetoelastic coupling, introduced by the power-law distance dependence of the magnetic exchange integral. Within the fully self-consistent, Gibbs energy-based formalism such thermodynamic quantities as the entropy, the specific heat as well as the lattice and magnetic response functions are calculated and discussed. To complete the picture, the magnetocaloric effect is characterized by analysis of the isothermal entropy change and the adiabatic temperature change in the presence of the external pressure.

  5. Thermodynamical aspect of black hole solutions in heteric string theory

    CERN Document Server

    Fujisaki, H

    2003-01-01

    Thermodynamical properties of charged rotating dilatonic black holes are discussed on the basis of the general solution of Sen in the heterotic string theory compactified on a six dimensional torus. The most probable microcanonical configuration of black holes is then described in the single-massive-mode dominance scenario.

  6. Nonequilibrium thermodynamics of dilute polymer solutions in flow.

    Science.gov (United States)

    Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M

    2014-11-07

    Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

  7. Theoretical calculations of the thermodynamic stability of ionic substitutions in hydroxyapatite under an aqueous solution environment

    International Nuclear Information System (INIS)

    Matsunaga, Katsuyuki; Murata, Hidenobu; Shitara, Kazuki

    2010-01-01

    Defect formation energies in materials generally depend on chemical potentials determined by a chemical equilibrium condition. In particular, an aqueous solution environment is important for biomaterials such as hydroxyapatite studied here. Therefore, a methodology to obtain ionic chemical potentials under chemical equilibrium between solid and aqueous solution was introduced, and was applied to substitutional divalent cations formed via ion exchange with Ca 2+ in hydroxyapatite. The calculated ranking of the stability of substitutional cations in HAp was in good agreement with the experimentally observed trend. The present theoretical approach would be useful to explore the thermodynamic stability of defects in materials subjected to an aqueous solution environment.

  8. A Thermodynamic Theory Of Solid Viscoelasticity. Part 1: Linear Viscoelasticity.

    Science.gov (United States)

    Freed, Alan D.; Leonov, Arkady I.

    2002-01-01

    The present series of three consecutive papers develops a general theory for linear and finite solid viscoelasticity. Because the most important object for nonlinear studies are rubber-like materials, the general approach is specified in a form convenient for solving problems important for many industries that involve rubber-like materials. General linear and nonlinear theories for non-isothermal deformations of viscoelastic solids are developed based on the quasi-linear approach of non-equilibrium thermodynamics. In this, the first paper of the series, we analyze non-isothermal linear viscoelasticity, which is applicable in a range of small strains not only to all synthetic polymers and bio-polymers but also to some non-polymeric materials. Although the linear case seems to be well developed, there still are some reasons to implement a thermodynamic derivation of constitutive equations for solid-like, non-isothermal, linear viscoelasticity. The most important is the thermodynamic modeling of thermo-rheological complexity , i.e. different temperature dependences of relaxation parameters in various parts of relaxation spectrum. A special structure of interaction matrices is established for different physical mechanisms contributed to the normal relaxation modes. This structure seems to be in accord with observations, and creates a simple mathematical framework for both continuum and molecular theories of the thermo-rheological complex relaxation phenomena. Finally, a unified approach is briefly discussed that, in principle, allows combining both the long time (discrete) and short time (continuous) descriptions of relaxation behaviors for polymers in the rubbery and glassy regions.

  9. Theory of the thermodynamic influence of solution-phase additives in shape-controlled nanocrystal synthesis.

    Science.gov (United States)

    Qi, Xin; Fichthorn, Kristen A

    2017-10-19

    Though many experimental studies have documented that certain solution-phase additives can play a key role in the shape-selective synthesis of metal nanocrystals, the origins and mechanisms of this shape selectivity are still unclear. One possible role of such molecules is to thermodynamically induce the equilibrium shape of a nanocrystal by altering the interfacial free energies of the facets. Using a multi-scheme thermodynamic integration method that we recently developed [J. Chem. Phys., 2016, 145, 194108], we calculate the solid-liquid interfacial free energies γ sl and investigate the propensity to achieve equilibrium shapes in such syntheses. We first apply this method to Ag(100) and Ag(111) facets in ethylene glycol solution containing polyvinylpyrrolidone (PVP), to mimic the environment in polyol synthesis of Ag nanocrystals. We find that although PVP has a preferred binding to Ag(100), its selectivity is not sufficient to induce a thermodynamic preference for {100}-faceted nanocubes, as has been observed experimentally. This indicates that PVP promotes Ag nanocube formation kinetically rather than thermodynamically. We further quantify the thermodynamic influence of adsorbed solution-phase additives for generic molecules, by building a γ sl ratio/nanocrystal shape map as a function of zero-temperature binding energies. This map can be used to gauge the efficacy of candidate additive molecules for producing targeted thermodynamic nanocrystal shapes. The results indicate that only additives with a strong facet selectivity can impart significant thermodynamic-shape change. Therefore, many of the nanocrystals observed in experiments are likely kinetic products.

  10. The thermodynamical foundation of electronic conduction in solids

    Science.gov (United States)

    Bringuier, E.

    2018-03-01

    In elementary textbooks, the microscopic justification of Ohm’s local law in a solid medium starts with Drude’s classical model of electron transport and next discusses the quantum-dynamical and statistical amendments. In this paper, emphasis is laid instead upon the thermodynamical background motivated by the Joule-Lenz heating effect accompanying conduction and the fact that the conduction electrons are thermalized at the lattice temperature. Both metals and n-type semiconductors are considered; but conduction under a magnetic field is not. Proficiency in second-year thermodynamics and vector analysis is required from an undergraduate university student in physics so that the content of the paper can be taught to third-year students. The necessary elements of quantum mechanics are posited in this paper without detailed justification. We start with the equilibrium-thermodynamic notion of the chemical potential of the electron gas, the value of which distinguishes metals from semiconductors. Then we turn to the usage of the electrochemical potential in the description of near-equilibrium electron transport. The response of charge carriers to the electrochemical gradient involves the mobility, which is the reciprocal of the coefficient of the effective friction force opposing the carrier drift. Drude’s calculation of mobility is restated with the dynamical requirements of quantum physics. Where the carrier density is inhomogeneous, there appears diffusion, the coefficient of which is thermodynamically related to the mobility. Next, it is remarked that the release of heat was ignored in Drude’s original model. In this paper, the flow of Joule heat is handled thermodynamically within an energy balance where the voltage generator, the conduction electrons and the host lattice are involved in an explicit way. The notion of dissipation is introduced as the rate of entropy creation in a steady state. The body of the paper is restricted to the case of one

  11. Knudsen thermogravimetry approach to the thermodynamics of aqueous solutions

    International Nuclear Information System (INIS)

    Schiraldi, Alberto; Signorelli, Marco; Fessas, Dimitrios

    2013-01-01

    Highlights: ► Knudsen cells were designed to replace standard TG pans for desorption experiments. ► The Knudsen effusion data allow determination of water activity of aqueous solutions. ► This methods can replace the traditional isopiestic approach for aqueous solutions. ► The Gibbs–Duhem relationship was used to fit the experimental data. -- Abstract: The use of isothermal TGA with Knudsen-like cells allows determination of the thermodynamic activity of water, a W . The typical experiment implies a slow dehydration of the aqueous solution at constant temperature in dynamic vacuum conditions. The method is alternative to the classical isopiestic approach and offers the advantage of a continuous record on increasing the solute concentration. These data can be directly treated according to the classical thermodynamic relationships drawn from the Gibbs–Duhem expression to evaluate the activity and osmotic coefficient of the aqueous solutions of electrolytes and non-electrolytes, and, in the case of electrolytes, allow determination of solubility of the solute. Discrepancies with respect to the literature data are observed when the viscosity of the systems becomes too high, as in the case of sugars with a very large solubility. Such a mismatch may however be accounted for either slowing the dehydration rate with use of a narrower Knudsen orifice, or correcting the experimental a W with a calibration curve. The same approach can be applied to non-aqueous solutions

  12. Thermodynamical and structural properties of solid surfaces in the high temperature range by molecular dynamics solution: evidence for a roughening transition on the F.C.C. {110} surface

    International Nuclear Information System (INIS)

    Rosato, Vittorio

    1986-01-01

    We have studied by Molecular Dynamics simulation the thermodynamical and structural properties of the {110} solid Argon surface as a function of temperature up to T m . The following results have been obtained: 1) the Arrhenius plot indicates that for T> 0.7 T m the defect creation becomes a nearly athermal process. The measured surface diffusion coefficients are very high and are comparable with those observed in the liquid state. 2) the long range order is preserved at least up to T= 0.94 T m . The thermal disorder is related to the onset of a roughening transition on that surface at T ≅ 0.7 T m . Surface layers are not melted in the whole range of temperature we have studied. Furthermore we have investigated the influence of constraints on the surface structure for the same model system previously used at T = 0.48 T m . We have shown that both temperature and constraints induce disorder on surface: for constraints corresponding to elastic deformations of -5 pc applied along the dense axis {110}, the surface structure results to be very similar to that obtained, without constraints, at a higher temperature (T = 0.68 T m ). The implications of our bindings in several areas of Materials Science are briefly discussed. (author) [fr

  13. The thermodynamic water retention capacity of solutions and gels.

    Science.gov (United States)

    Borchard, W; Jablonski, P

    2003-01-01

    The thermodynamic water retention capacity (WRC) has been defined and applied to different heterogeneous phase equilibria. This definition includes others known from the literature for testing heterogeneous systems. For the type of a real solution it is shown that at constant values of temperature and pressure the WRC is related to the difference of the chemical potential of water between the original state and the state after having applied a constraint. The dependence of WRC on concentration of a solute is predicted to be described by an e-function which has been experimentally confirmed in the literature.

  14. Structure of water and the thermodynamics of aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nemethy, G.

    1970-10-26

    This report represents the summary of a series of lectures held at the Istituto Superiore di Sanita, Laboratori di Fisica, from 18 September to 26 October 1970. The topics discussed were: Intermolecular forces, the individual water molecule and the hydrogen bond, the structures of the solid phases of water, experimental information on the strucuture of liquid water, theoretical models of water structure, experimental properties and theoretical models of aqueous solutions of nonpolar solutes, polar solutes, and electrolytes, the conformational stability of biological macromolecules.

  15. THERMODYNAMICS OF ETHANOLAMMONIUM CATIONES DISSOCIATION IN AQUEOUS SOLUTIONS

    Directory of Open Access Journals (Sweden)

    R. E. Khoma

    2017-03-01

    Full Text Available The literature data on the thermodynamics of ethanolamines onium cations dissociation have been systematized and generalized. The correlation between these cations dissociation thermodynamic functions (DH and DS and physicochemical properties (Tmp., Tbp, Pp, lgPow et al. has been revealed. There was a correlation between lipophilicity determined experimentally and calculated by QSAR. For monoethanolammonium, diethanolammonium, and their N-methyl and N-ethyl derivatives it was found dissociation thermodynamic functions to depend on bases lgPow. Acid-base dissociation of TRIS and triethanolamine onium cations does not correspond to said relationship because TRIS (primary amine, TEA (tertiary amine act differently on aqueous solutions of SO2. TEA, unlike MEA, DEA and MMEA, has a salting out effect towards sulfur dioxide because of competing hydration that promotes sulfite «onium» salts hydrolysis. TRIS promotes S(IV → S(VI sulphooxidation, in contrast to another ethanolamines. Enthalpy–enthropy compensation with isothermodynamic temperature 303 K has been recorded. The revealed correlations may be useful in developing of procedures for air sanitary cleaning from acidic gases; chemisorbents immobilized for gas and ion exchange chromatography; potentiometric methods for fluorocomplex acids determinations. The use of monoethanolamine is most promising to obtain chemisorbents because the thermodynamic functions of its onium cation acid-base dissociation are least dependent on temperature compared to other etanolammonium cations.

  16. Theromdynamics of carbon in nickel-based multicomponent solid solutions

    International Nuclear Information System (INIS)

    Bradley, D.J.

    1978-04-01

    The activity coefficient of carbon in nickel, nickel-titanium, nickel-titanium-chromium, nickel-titanium-molybdenum and nickel-titanium-molybdenum-chromium alloys has been measured at 900, 1100 and 1215 0 C. The results indicate that carbon obeys Henry's Law over the range studied (0 to 2 at. percent). The literature for the nickel-carbon and iron-carbon systems are reviewed and corrected. For the activity of carbon in iron as a function of composition, a new relationship based on re-evaluation of the thermodynamics of the CO/CO 2 equilibrium is proposed. Calculations using this relationship reproduce the data to within 2.5 percent, but the accuracy of the calibrating standards used by many investigators to analyze for carbon is at best 5 percent. This explains the lack of agreement between the many precise sets of data. The values of the activity coefficient of carbon in the various solid solutions are used to calculate a set of parameters for the Kohler-Kaufman equation. The calculations indicate that binary interaction energies are not sufficient to describe the thermodynamics of carbon in some of the nickel-based solid solutions. The results of previous workers for carbon in nickel-iron alloys are completely described by inclusion of ternary terms in the Kohler-Kaufman equation. Most of the carbon solid solution at high temperatures in nickel and nickel-titantium alloys precipitates from solution on quenching in water. The precipitate is composed of very small particles (greater than 2.5 nm) of elemental carbon. The results of some preliminary thermomigration experiments are discussed and recommendations for further work are presented

  17. Experimental and theoretical study of solid solution stability under irradiation

    International Nuclear Information System (INIS)

    Cauvin, Richard.

    1981-08-01

    The behavior of dilute alloys (Al-Zn, Al-Ag, Al-Si, Al-Ge and Al-Mg) under 1 MeV electron irradiation has been studied in a high voltage electron microscope. A phenomenon of homogeneous precipitation induced by irradiation in undersaturated solid solutions (Al-Zn, Al-Ag and Al-Si) has been discovered; the observed precipitates are either coherent or incoherent, but never associated with point defect sinks. The solubility limit is a function of irradiation temperature and flux; but, under irradiation, it does not behave as a true thermal solubility limit (without irradiation). The existing theories (kinetic or strictly thermodynamic) do not account for this phenomenon. It is shown that the irreversibility of the mutual recombination between trapped vacancies and mixed interstitials is the driving force of this homogeneous precipitation. Using a dilute solid solution model, we show that, under irradiation, the homogeneous stationary state, stable from a strictly thermodynamic point of view, can be unstable when the recombination reaction is taken into account. The solubility limit under irradiation is calculated with a nucleation-growth model taking account for this effect; it is proportional to the thermal solubility limit without irradiation. This model explains all the experimental observations [fr

  18. Solution Thermodynamics of Lysine Clonixinate in Some Ethanol + Water Mixtures

    OpenAIRE

    Delgado, Daniel R.; Martínez, Fleming; Gutiérrez, Rahumir A.

    2012-01-01

    The solubility of lysine clonixinate (LysClon) in several ethanol + water mixtures was determined at 293.15 to 313.15 K. The thermodynamic functions, Gibbs energy, enthalpy, and entropy of solution and of mixing were obtained from these solubility data by using the van’t Hoff and Gibbs equations. In general this drug exhibit good solubility and the greatest value was obtained in the mixture 0.60 in mass fraction of ethanol. A non-linear enthalpy–entropy relationship was observed from ...

  19. Thermodynamic properties of fluids from Fluctuation Solution Theory

    International Nuclear Information System (INIS)

    O'Connell, J.P.

    1990-01-01

    Fluctuation Theory develops exact relations between integrals of molecular correlation functions and concentration derivatives of pressure and chemical potential. These quantities can be usefully correlated, particularly for mechanical and thermal properties of pure and mixed dense fluids and for activities of strongly nonideal liquid solutions. The expressions yield unique formulae for the desirable thermodynamic properties of activity and density. The molecular theory origins of the flucuation properties, their behavior for systems of technical interest and some of their successful correlations will be described. Suggestions for fruitful directions will be suggested

  20. Solid-soluted content of cerium in solid solution of sphene

    International Nuclear Information System (INIS)

    Zhao Wei; Teng Yuancheng; Li Yuxiang; Ren Xuetan; Huang Junjun

    2010-01-01

    The sphene solid solution was synthesized by solid-state method,with calcium carbonate, silica, titanium dioxide, cerium oxalate and alumina as raw materials. The solid-soluted content of cerium in sphene was researched by means of X-ray diffraction (XRD), backscattering scanning electron microscopy (BSE), energy dispersive spectroscopy (EDS) and so on. The influence of A l3+ ion introduction to sphene on the solid-soluted content of cerium in sphene solid solution was studied. The results indicate that when introducing Al 3+ to sphene as electrovalence compensation, Ce 4+ could be well solidified to Ca 1-x Ce x Ti 1-2x A l2x SiO 5 , and the solid-soluted content is approximately 12.61%. With no electrovalence compensation, Ce 4+ could be solidified to Ca 1-2x Ce x TiSiO 5 , and the solid-soluted content is approximately 10.98%. The appropriate synthesis temperature of sphene solid solution is 1 260 degree C.(authors)

  1. Thermodynamic modeling of iodine and selenium retention in solutions with high salinity

    International Nuclear Information System (INIS)

    Hagemann, Sven; Moog, Helge C.; Herbert, Horst-Juergen; Erich, Agathe

    2012-04-01

    The report on iodine and selenium retention in saline solutions includes the following chapters: (1) Introduction and scope of the work. (2) Actual status of knowledge. (3) Experimental and numerical models. (4) Thermodynamic properties of selenite and hydrogen selenite in solutions of oceanic salts. (5) Thermodynamic properties of selenate in solutions of oceanic salts. (6) Thermodynamic properties of iodide in solutions of oceanic salts. (7) Experimental studies on the retention of iodine and selenium in selected sorbents. (8) Summary and conclusions.

  2. Superhard Rhenium/Tungsten Diboride Solid Solutions.

    Science.gov (United States)

    Lech, Andrew T; Turner, Christopher L; Lei, Jialin; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

    2016-11-02

    Rhenium diboride (ReB 2 ), containing corrugated layers of covalently bonded boron, is a superhard metallic compound with a microhardness reaching as high as 40.5 GPa (under an applied load of 0.49 N). Tungsten diboride (WB 2 ), which takes a structural hybrid between that of ReB 2 and AlB 2 , where half of the boron layers are planar (as in AlB 2 ) and half are corrugated (as in ReB 2 ), has been shown not to be superhard. Here, we demonstrate that the ReB 2 -type structure can be maintained for solid solutions of tungsten in ReB 2 with tungsten content up to a surprisingly large limit of nearly 50 atom %. The lattice parameters for the solid solutions linearly increase along both the a- and c-axes with increasing tungsten content, as evaluated by powder X-ray and neutron diffraction. From micro- and nanoindentation hardness testing, all of the compositions within the range of 0-48 atom % W are superhard, and the bulk modulus of the 48 atom % solid solution is nearly identical to that of pure ReB 2 . These results further indicate that ReB 2 -structured compounds are superhard, as has been predicted from first-principles calculations, and may warrant further studies into additional solid solutions or ternary compounds taking this structure type.

  3. The elastic solid solution model for minerals at high pressures and temperatures

    Science.gov (United States)

    Myhill, R.

    2018-02-01

    Non-ideality in mineral solid solutions affects their elastic and thermodynamic properties, their thermobaric stability, and the equilibrium phase relations in multiphase assemblages. At a given composition and state of order, non-ideality in minerals is typically modelled via excesses in Gibbs free energy which are either constant or linear with respect to pressure and temperature. This approach has been extremely successful when modelling near-ideal solutions. However, when the lattice parameters of the solution endmembers differ significantly, extrapolations of thermodynamic properties to high pressures using these models may result in significant errors. In this paper, I investigate the effect of parameterising solution models in terms of the Helmholtz free energy, treating volume (or lattice parameters) rather than pressure as an independent variable. This approach has been previously applied to models of order-disorder, but the implications for the thermodynamics and elasticity of solid solutions have not been fully explored. Solid solution models based on the Helmholtz free energy are intuitive at a microscopic level, as they automatically include the energetic contribution from elastic deformation of the endmember lattices. A chemical contribution must also be included in such models, which arises from atomic exchange within the solution. Derivations are provided for the thermodynamic properties of n-endmember solutions. Examples of the use of the elastic model are presented for the alkali halides, pyroxene, garnet, and bridgmanite solid solutions. Elastic theory provides insights into the microscopic origins of non-ideality in a range of solutions, and can make accurate predictions of excess enthalpies, entropies, and volumes as a function of volume and temperature. In solutions where experimental data are sparse or contradictory, the Helmholtz free energy approach can be used to assess the magnitude of excess properties and their variation as a function

  4. Thermodynamic properties of CuCr/sub 2/S/sub 4/ solid solutions in Cusub(1/2)Msub(1/2) Crsub(2)Ssub(4) (M - Ga, In)

    Energy Technology Data Exchange (ETDEWEB)

    Titov, V.V.; Kesler, Ya.A.; Shelkotunov, V.A.; Gordeev, I.V.; Tret' yakov, Yu.D.

    1985-04-01

    By means of an adiabatic calorimeter and quartz dilatometer for CuCr/sub 2/S/sub 4/ in Cusub(1/2)Msub(1/2) Crsub(2)Ssub(4) (M-Ga, In) temperature dependences of heat capacity are determined. The contribution of various components into heat capacity is estimated, thermodynamic parameters of magnetic transformation are calculated.

  5. Solution thermodynamics of valnemulin hydrogen fumarate in different pure solvents

    International Nuclear Information System (INIS)

    Ouyang, Jinbo; Wang, Jingkang; Huang, Xin; Bao, Ying; Wang, Yongli; Yin, Qiuxiang; Liu, Ailing; Li, Xudong; Hao, Hongxun

    2015-01-01

    Highlights: • The solubility of valnemulin hydrogen fumarate in five pure solvents was experimentally determined. • The solubility data were correlated by Wilson model, NRTL model and UNIQUAC model. • Mixing thermodynamic properties of valnemulin hydrogen fumarate in five pure solvents were calculated. - Abstract: Solubility of valnemulin hydrogen fumarate in five pure solvents was determined within temperature range of (278.15 to 323.15) K by a gravimetric method. The results show that the solubility of valnemulin hydrogen fumarate in tested pure solvents increases with the increasing temperature. The solubility values were correlated by the Wilson model, NRTL model and UNIQUAC model. The UNIQUAC volume parameter, area parameter, and Wilson liquid molar volume parameter of valnemulin hydrogen fumarate were estimated by the group contribution method. It was found that the correlated results are in good agreement with the experimental results. Furthermore, the mixing thermodynamic properties of valnemulin hydrogen fumarate in solutions, including the mixing Gibbs energy, the mixing enthalpy and entropy, were determined by using the Wilson model and the experimental solubility results.

  6. Prediction of thermodynamic properties of solute elements in Si solutions using first-principles calculations

    International Nuclear Information System (INIS)

    Iwata, K.; Matsumiya, T.; Sawada, H.; Kawakami, K.

    2003-01-01

    The method is presented to predict the activity coefficients and the interaction parameters of the solute elements in infinite dilute Si solutions by the use of first-principles calculations based on density functional theory. In this method, the regular solution model is assumed. The calculated activity coefficients in solid Si are converted to those in molten Si by the use of the solid-liquid partition coefficients. Furthermore, the interaction parameters in solid Si solutions are calculated and compared with reported experimental values of those in liquid Si solutions. The results show that the calculated activity coefficients and interaction parameters of Al, Fe, Ti and Pb in Si solutions are in good agreement with the tendency of the experiments. However, the calculations have some quantitative discrepancy from the experiments. It is expected that consideration of the excess entropy would reduce this discrepancy

  7. Non-equilibrium thermodynamics of radiation-induced processes in solids

    International Nuclear Information System (INIS)

    Yurov, V.M.; Eshchanov, A.N.; Kuketaev, A.T.; Sidorenya, Yu.S.

    2005-01-01

    In the paper an item about a defect system response in solids on external action (temperature, pressure, light, etc.) from the point of view of non-equilibrium statistical thermodynamics is considered

  8. Thermodynamic Mixing Behavior Of F-OH Apatite Crystalline Solutions

    Science.gov (United States)

    Hovis, G. L.

    2011-12-01

    It is important to establish a thermodynamic data base for accessory minerals and mineral series that are useful in determining fluid composition during petrologic processes. As a starting point for apatite-system thermodynamics, Hovis and Harlov (2010, American Mineralogist 95, 946-952) reported enthalpies of mixing for a F-Cl apatite series. Harlov synthesized all such crystalline solutions at the GFZ-Potsdam using a slow-cooled molten-flux method. In order to expand thermodynamic characterization of the F-Cl-OH apatite system, a new study has been initiated along the F-OH apatite binary. Synthesis of this new series made use of National Institute of Standards and Technology (NIST) 2910a hydroxylapatite, a standard reference material made at NIST "by solution reaction of calcium hydroxide with phosphoric acid." Synthesis efforts at Lafayette College have been successful in producing fluorapatite through ion exchange between hydroxylapatite 2910a and fluorite. In these experiments, a thin layer of hydroxylapatite powder was placed on a polished CaF2 disc (obtained from a supplier of high-purity crystals for spectroscopy), pressed firmly against the disc, then annealed at 750 °C (1 bar) for three days. Longer annealing times did not produce further change in unit-cell dimensions of the resulting fluorapatite, but it is uncertain at this time whether this procedure produces a pure-F end member (chemical analyses to be performed in the near future). It is clear from the unit-cell dimensions, however, that the newly synthesized apatite contains a high percentage of fluorine, probably greater than 90 mol % F. Intermediate compositions for a F-OH apatite series were made by combining 2910a hydroxylapatite powder with the newly synthesized fluorapatite in various proportions, then conducting chemical homogenization experiments at 750 °C on each mixture. X-ray powder diffraction data indicated that these experiments were successful in producing chemically homogeneous

  9. Solution properties of solid and liquid potassium-indium alloys

    International Nuclear Information System (INIS)

    Takenaka, T.; Saboungi, M.L.

    1987-01-01

    It was recently shown by a combination of electrical resistivity, thermodynamic, and structural measurements that equiatomic alloys formed between K or Na and either Bi, Sb, Te, or Pb show pronounced deviations from ordinary metallic behavior and from ideal solution behavior, e.g., small values for the electrical conductivity and sharp peaks for the Darken excess stability function. Physical explanation of this behavior has been advanced on the basis of the formation of complex structural species similar to those reported for the corresponding solid alloys. The authors have chosen K-In alloys for several reasons. Phase diagram considerations coupled with small electronegativity differences between K and In would lead one to predict small deviations from ideal behavior, thus, this system would be suitable to test for oddities in alloy solution behavior in systems which deviate little from ideal behavior. Others have demonstrated that the position of the peak in the electrical resistivity changed in going from Li to Na and to K in the following sequence X/sub In/ ≅ 0.25, 0.40, and 0.50, respectively. The thermodynamic properties of these alloys would be expected to present similar trends

  10. Thermodynamics of dilute aqueous solutions of imidazolium based ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Tejwant [Salt and Marine Chemicals Division, Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research (CSIR), G.B. Marg, Bhavnagar 364002 (India); Kumar, Arvind, E-mail: arvind@csmcri.or [Salt and Marine Chemicals Division, Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research (CSIR), G.B. Marg, Bhavnagar 364002 (India)

    2011-06-15

    Research highlights: The thermodynamic behaviour of aqueous imidazolium ILs has been investigated. Volumetric and ultrasonic results indicated the hydrophobic hydration of ILs. Viscometric studies revealed studied ionic liquids as water-structure makers. Hydration number increased with increase in alkyl chain length of the cation. - Abstract: Experimental measurements of density {rho}, speed of sound u, and viscosity {eta} of aqueous solutions of various 1-alkyl-3-methylimidazolium based ionic liquid (IL) solutions have been performed in dilute concentration regime at 298.15 K to get insight into hydration behaviour of ILs. The investigated ILs are based on 1-alkyl-3-methylimidazolium cation, [C{sub n}mim] having [BF{sub 4}]{sup -}, [Cl]{sup -}, [C{sub 1}OSO{sub 3}]{sup -}, and [C{sub 8}OSO{sub 3}]{sup -} as anions where n = 4 or 8. Several thermodynamic parameters like apparent molar volume {phi}{sub V}, isentropic compressibility {beta}{sub s}, and viscosity B-coefficients have been derived from experimental data. Limiting value of apparent molar volume has been discussed in terms of intrinsic molar volume (V{sub int}) molar electrostriction volume (V{sub elec}), molar disordered (V{sub dis}), and cage volume (V{sub cage}). Viscosity B-coefficients have been used to quantify the kosmotropic or chaotropic nature of ILs. Hydration number of ILs obtained using elctrostriction volume, isentropic compressibility, viscosity, and differential scanning calorimetry have been found to be comparative within the experimental error. The hydrophobic hydration has found to play an important role in hydration of ILs as compared to hydration due to hydrogen bonding and electrostriction. Limiting molar properties, hydration numbers, and B-coefficients have been discussed in terms of alkyl chain length of cation or nature of anion.

  11. Thermodynamics of dilute aqueous solutions of imidazolium based ionic liquids

    International Nuclear Information System (INIS)

    Singh, Tejwant; Kumar, Arvind

    2011-01-01

    Research highlights: → The thermodynamic behaviour of aqueous imidazolium ILs has been investigated. → Volumetric and ultrasonic results indicated the hydrophobic hydration of ILs. → Viscometric studies revealed studied ionic liquids as water-structure makers. → Hydration number increased with increase in alkyl chain length of the cation. - Abstract: Experimental measurements of density ρ, speed of sound u, and viscosity η of aqueous solutions of various 1-alkyl-3-methylimidazolium based ionic liquid (IL) solutions have been performed in dilute concentration regime at 298.15 K to get insight into hydration behaviour of ILs. The investigated ILs are based on 1-alkyl-3-methylimidazolium cation, [C n mim] having [BF 4 ] - , [Cl] - , [C 1 OSO 3 ] - , and [C 8 OSO 3 ] - as anions where n = 4 or 8. Several thermodynamic parameters like apparent molar volume φ V , isentropic compressibility β s , and viscosity B-coefficients have been derived from experimental data. Limiting value of apparent molar volume has been discussed in terms of intrinsic molar volume (V int ) molar electrostriction volume (V elec ), molar disordered (V dis ), and cage volume (V cage ). Viscosity B-coefficients have been used to quantify the kosmotropic or chaotropic nature of ILs. Hydration number of ILs obtained using elctrostriction volume, isentropic compressibility, viscosity, and differential scanning calorimetry have been found to be comparative within the experimental error. The hydrophobic hydration has found to play an important role in hydration of ILs as compared to hydration due to hydrogen bonding and electrostriction. Limiting molar properties, hydration numbers, and B-coefficients have been discussed in terms of alkyl chain length of cation or nature of anion.

  12. Hydrophobicity and thermodynamic response for aqueous solutions of amphiphiles

    Science.gov (United States)

    Zemánková, Katerina; Troncoso, Jacobo; Cerdeiriña, Claudio A.; Romaní, Luis; Anisimov, Mikhail A.

    2016-06-01

    The anomalous behavior of aqueous solutions of amphiphiles in the water-rich region is analyzed via a phenomenological approach that utilizes the isobaric heat capacity Cp as an experimental probe. We report extensive data for solutions of 14 amphiphiles as a function of temperature at atmospheric pressure. Beyond that, Cp data but also isobaric thermal expansivities and isothermal compressibilities for three solutions of tert-butanol as a function of both temperature and pressure are presented. Results rule out the possibility that the observed phenomenology is associated with the anomalous thermodynamics of pure water. Indeed, our Cp data, quantitatively consistent with recent spectroscopic analyses, suggest that water-mediated interactions between the nonpolar parts of amphiphiles are at the origin of anomalies, with the effects of such "hydrophobic aggregation" being observed at mole fractions as small as 0.01. Physicochemical details like the size, the electronic charge distribution and the geometry of amphiphile molecules as well as third-order derivatives of the Gibbs energy and the associated Koga lines support the above claims while they further contribute to characterizing the role of hydrophobicity in these phenomena. Progress with a view to gain a deeper, more concrete understanding remains.

  13. Thermodynamic Calculation of the Distribution Coefficient Between the Liquid and Solid Phases of an Element in Dilute Solution in a Metal: Application to the Purification of Beryllium; Calcul Thermodynamique du Coefficient de Distribution Entre Phases Liquide et Solide d'un Element en Presence d'Autres Constituants en Solution Diluee dans un Metal: Application a la Purification du Beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Desre, P. [Ecole Nationale Superieure d' Electrochimie et d' Electrometallurgie (France); Schaub, B. [Centre d' Etudes Nucleaires de Grenoble (France); Bonnier, I. E. [Ecole Nationale Superieure d' Electrochimie et d' Electrometallurgie, Grenoble (France)

    1966-01-15

    The authors calculate the distribution coefficient {Gamma}{sub i} between the liquid and solid phases of an element i in the presence of other elements j in a solvent M ({Gamma}{sub i} = x'{sub i}/x{sub i}, where x'{sub i} and x{sub i} are the atomic fractions of i in the solid and liquid phases respectively) from the thermodynamic properties of binary systems of the type (i, M), (j, M) and (i, j). They show that the interaction of all the elements present may, under certain conditions, strongly affect the value of the coefficient {Gamma}{sub i}. This effect is pronounced if the following condition is fulfilled: {gamma}{sup {infinity}}{sub i(M)}, {gamma}{sup {infinity}}{sub j(M)} > {gamma}{sup {infinity}}{sub ij} where {gamma}{sup {infinity}}{sub i(M)}, {gamma}{sup {infinity}}{sub j(M)} and {gamma}{sup {infinity}}{sub ij} are limiting activity coefficients of the constituents i and j in the (i, M) (j, M) and (i, j) liquid state systems. It is a simple matter to deduce from this condition an application to the purification of metals by the zone-melting method; the condition enables one to choose an element j which is added deliberately to a metal in order to facilitate the elimination-of an element i (subsequent elimination of the element j being also, of course, a simple matter). For example, the authors were able to confirm that the addition of aluminium to beryllium enables one to improve the elimination of iron during the purification of the beryllium by the zone-melting technique, the aluminium acting as a carrier. (author) [French] Les auteurs calculent le coefficient de distribution Greek-Capital-Letter-Gamma {sub i} entre phases liquide et solide d'un element i en presence d'autres elements j dans un solvant M ( Greek-Capital-Letter-Gamma {sub i} = x'{sub i}/x{sub i}, x'{sub i} et x{sub i} representant respectivement les fractions atomiques de i dans les phases solide et liquide), a partir des proprietes thermodynamiques des systemes binaires de type: (i, M

  14. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    International Nuclear Information System (INIS)

    Stout, R B

    2001-01-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  15. Solid phase extraction of uranium from phosphoric acid. Kinetic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Magied, Ahmed Fawzy [Nuclear Materials Authority, Cairo (Egypt); Stockholm Univ. (Sweden). Dept. of Organic Chemistry

    2017-07-01

    There is a high interest to develop suitable solid phase extractants for uranium separation from aqueous solutions in order to reduce cost and enhance the efficiency. This paper describes solid phase extraction of uranium(VI) from aqueous phosphoric acid solution using MCM-41 based D2HEPA-TOPO organophosphorous extractants. The mixture of D2HEPA (di-2-ethyl-hexylphosphoric acid) and TOPO (tri-n-octylphosphine oxide) was impregnated into the pores of MCM-41 and the synthesized sorbent was fully characterized. The influences of different factors such as synergistic mixture ratio, phosphoric acid concentration, mixing time and temperature were investigated. The results showed that 90% of uranium(VI) extraction can be achieved within 5 min, using D2HEPA-TOPO rate at MCM-41 (mass ratio 2:1 w/w) from 1 M phosphoric acid containing 64 ppm of uranium at room temperature. High adsorption capacity of uranium(VI) have been achieved at the mentioned conditions. The rate constant for the chemical adsorption of uranium(VI) was 0.988 g mg{sup -1} min{sup -1} calculated by the pseudo-second order rate equation. The obtained thermodynamics parameters showed that uranium(VI) adsorption from H{sub 3}PO{sub 4} is an exothermic and spontaneous process.

  16. Thermodynamic properties of lithium hydride, lithium deuteride, lithium tritide, and their solutions with lithium

    International Nuclear Information System (INIS)

    Shpil'rain, E.E.; Yakimovich, K.A.

    1981-01-01

    The paper reviews briefly experimental determinations of thermodynamic properties of the LiH-Li system. Relationships fitted to the experimental data are presented and discussed, with the aim of determining a consistent set of thermodynamic properties (enthalpy, heat capacity) for the systems Li-(LiH, LiD, LiT) in the solid state and in the melt. (author)

  17. Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

    Science.gov (United States)

    Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

    1990-01-01

    Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

  18. Thermodynamic properties of aqueous solutions with citrate ions. Compressibility studies in aqueous solutions of citric acid

    International Nuclear Information System (INIS)

    Apelblat, Alexander; Korin, Eli; Manzurola, Emanuel

    2013-01-01

    Highlights: • Over a wide range of concentrations and temperatures sound velocities were measured in aqueous solutions of citric acid. • Compressibility properties of citric acid solutions are thermodynamically characterized. • Changes in the structure of water when citric acid is dissolved are discussed. -- Abstract: Sound velocities in aqueous solutions of citric acid were measured from 15 °C to 50 °C in 5 °C intervals, within the 0.1 mol · kg −1 to 5.0 mol · kg −1 concentration range. These sound velocities served to evaluate the isentropic and isothermal compressibilities, the apparent molar compressibilities, the isochoric thermal pressure coefficients, changes of the cubic expansion coefficients with pressure at constant temperature, the changes of heat capacities with volume and hydration numbers of citric acid in aqueous solutions

  19. Thermodynamic data for iron (II) in high-saline solutions at temperatures up to 90 C

    Energy Technology Data Exchange (ETDEWEB)

    Munoz, Andres G.; Scharge, Tina; Moog, Helge C.

    2013-12-15

    For natural aqueous systems in general and for the near field of underground nuclear waste repositories in particular thermodynamic properties of iron species and solid phases are of predominant importance. Regardless of the question of the host rock, nuclear waste containment in Germany will be based on massive steel canisters. The total mass of iron present in a repository can be, dependent on the applied variant, sum up to more than 100 000 tons. The overall geochemical milieu including pH and EH will be dominated by the overall abundance of metallic, ferrous, and ferric iron, their aqueous speciation and solid iron-phases. This milieu is imposed on all other equilibria of interest, including those which determine radionuclide solubility. In addition to this, iron bearing corrosion phases due to their shear mass may exhibit a significant sink for radionuclides in terms of incorporation or sorption. As to the evolution of EH it is important to note that application of the Nernst equation requires knowing the electrochemical activities of the involved reactants. Iron is present in aqueous solutions in two oxidation states: +II (ferrous iron) and +III (ferric iron). Ferric iron exhibits a much more complex speciation behavior than ferrous iron, where from a conceptual point of view many species may be neglected. Ferric iron, on the contrary, is subject to considerable complex formation with chloride, sulfate, and - most importantly - with hydroxide. For this reason, experimental and theoretical treatment of ''iron'' at GRS in high saline solutions proceeded along two strings, one for each oxidation state, with the ultimate goal to deliver a thermodynamic model for ''iron'' in high saline solutions.

  20. Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion

    International Nuclear Information System (INIS)

    Wang Peiming; Wilson, Leslie L.; Wesolowski, David J.; Rosenqvist, Joergen; Anderko, Andrzej

    2010-01-01

    To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO 2 has been determined at 80 deg. C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl 2+ ) and hydrolyzed species (MoOH 2+ , Mo(OH) 2 + , and Mo(OH) 3 0 ) in addition to the Mo 3+ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.

  1. Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters.

    Science.gov (United States)

    Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi

    2017-04-01

    Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (T g ), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔT g (≡T g  - T g0 ; where T g0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

  2. Thermodynamics of nanoadsorption from solution: Theoretical and experimental research

    International Nuclear Information System (INIS)

    Wen, Yan-Zhen; Xue, Yong-Qiang; Cui, Zi-Xiang; Wang, Yan

    2015-01-01

    Highlights: • The thermodynamic theory of nanoadsorption was proposed. • The thermodynamic relations of nanoadsorption were derived. • The results of the experiments are accord with the theory. - Abstract: In this study, the effect of nanoparticle size on adsorption thermodynamics was investigated. The results of theoretical and experimental studies show that particle size significantly affects the equilibrium constant and thermodynamic properties of nanoadsorption. Relationships between the equilibrium constant, thermodynamic properties and particle size were derived using the thermodynamic theory of nanoadsorption. The equilibrium constant and thermodynamic properties were obtained by investigating the adsorption of Cu 2+ onto different sizes of nano-ZnO and the adsorption of Ag + onto different sizes of nano-TiO 2 . Good agreement was achieved between results obtained by experiments and predicted by theoretical analyses. The equilibrium constant and the molar Gibbs free energy of nanoadsorption were found to increase with smaller nanoparticle size. However, the effects of particle size on the molar enthalpy and the molar entropy are uncertain. In addition, the molar Gibbs free energy, the molar enthalpy, the molar entropy and the logarithm of the equilibrium constant are linearly related to the reciprocal of the diameter of the nanoparticle. The thermodynamic properties revealed in this study may provide important guidelines for research and application in the field of nanoadsorption

  3. Geochemical and numerical modelling of interactions between solid solutions and an aqueous solution. Extension of a reactive transport computer code called Archimede and application to reservoirs diagenesis; Modelisation geochimique et numerique des interactions entre des solutions solides et une solution aqueuse: extension du logiciel de reaction-transport archimede et application a la diagenese des reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Nourtier-Mazauric, E.

    2003-03-15

    This thesis presents a thermodynamic and kinetic model of interactions between a fluid and ideal solid solutions represented by several end-members. The reaction between a solid solution and the aqueous solution results from the competition between the stoichiometric dissolution of the initial solid solution and the co-precipitation of the least soluble solid solution in the fluid at considered time. This model was implemented in ARCHIMEDE, a computer code of reactive transport in porous media, then applied to various examples. In the case of binary solid solutions, a graphical method allowed to determine the compositions of the precipitating solid solutions, with the aid of the end-member chemical potentials. The obtained program could be used to notably model the diagenesis of clayey or carbonated oil reservoirs, or the ground pollutant dispersion. (author)

  4. Thermodynamics. Vol. II. Proceedings of the Symposium on Thermodynamics with Emphasis on Nuclear Materials and Atomic Transport in Solids

    International Nuclear Information System (INIS)

    1966-01-01

    Knowledge of the thermodynamics of nuclear materials is vital to the design of reactor fuels and moderating and cooling systems, in fact all facets of nuclear plant operation that involve mixtures of, or contact between, two or more elements in single- or multi-phase systems. The steep thermal gradients and the high temperatures involved in nuclear technology pose special problems for engineers and thermodynamicists, who have found that extrapolation of low-temperature data to high temperatures very often proves invalid. For this reason, standard thermodynamic techniques such as calorimetry and EMF-methods have been extended into high-temperature regions. Since the Agency's last conference on this subject, also held in Vienna (Thermodynamics of Nuclear Materials, 1962), there have been notable advances in calorimetry performed at temperatures greater than 1000°C, and in the use of EMF cells with solid electrolytes operated at similar temperatures. Significant advances have also been made in measuring diffusion parameters at the higher temperatures. An important field covered in this Symposium was the correlation of such atomic transport data with thermodynamic data, a prerequisite if the nuclear engineer is to incorporate diffusion results into his normal process- assessment techniques. Finally the Symposium suggested the requirements for good critical tables. The mere compiling of such data is no longer sufficient; the compiler must have free access to all the data of a particular experiment, he must have an intimate knowledge of experimental work in this field and he must weight every figure quoted in the light of his experience. As a step in this direction, the Agency has called on the services of many well-known experts and is preparing a number of monographs giving critical assessments of thermodynamic data and phase-diagrams for many of the elements of interest in reactor design. Most of the countries engaged in research in thermodynamics were represented at

  5. Thermodynamics. Vol. II. Proceedings of the Symposium on Thermodynamics with Emphasis on Nuclear Materials and Atomic Transport in Solids

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1966-02-15

    Knowledge of the thermodynamics of nuclear materials is vital to the design of reactor fuels and moderating and cooling systems, in fact all facets of nuclear plant operation that involve mixtures of, or contact between, two or more elements in single- or multi-phase systems. The steep thermal gradients and the high temperatures involved in nuclear technology pose special problems for engineers and thermodynamicists, who have found that extrapolation of low-temperature data to high temperatures very often proves invalid. For this reason, standard thermodynamic techniques such as calorimetry and EMF-methods have been extended into high-temperature regions. Since the Agency's last conference on this subject, also held in Vienna (Thermodynamics of Nuclear Materials, 1962), there have been notable advances in calorimetry performed at temperatures greater than 1000 Degree-Sign C, and in the use of EMF cells with solid electrolytes operated at similar temperatures. Significant advances have also been made in measuring diffusion parameters at the higher temperatures. An important field covered in this Symposium was the correlation of such atomic transport data with thermodynamic data, a prerequisite if the nuclear engineer is to incorporate diffusion results into his normal process- assessment techniques. Finally the Symposium suggested the requirements for good critical tables. The mere compiling of such data is no longer sufficient; the compiler must have free access to all the data of a particular experiment, he must have an intimate knowledge of experimental work in this field and he must weight every figure quoted in the light of his experience. As a step in this direction, the Agency has called on the services of many well-known experts and is preparing a number of monographs giving critical assessments of thermodynamic data and phase-diagrams for many of the elements of interest in reactor design. Most of the countries engaged in research in thermodynamics were

  6. Thermodynamics. Vol. I. Proceedings of the Symposium on Thermodynamics with Emphasis on Nuclear Materials and Atomic Transports in Solids

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1966-01-15

    Knowledge of the thermodynamics of nuclear materials is vital to the design of reactor fuels and moderating and cooling systems, in fact all facets of nuclear plant operation that involve mixtures of, or contact between, two or more elements in single- or multi-phase systems. The steep thermal gradients and the high temperatures involved in nuclear technology pose special problems for engineers and thermodynamicists, who have found that extrapolation of low-temperature data to high temperatures very often proves invalid. For this reason, standard thermodynamic techniques such as calorimetry and EMF-methods have been extended into high-temperature regions. Since the Agency's last conference on this subject, also held in Vienna (Thermodynamics of Nuclear Materials, 1962), there have been notable advances in calorimetry performed at temperatures greater than 1000 Degree-Sign C, and in the use of EMF cells with solid electrolytes operated at similar temperatures. Significant advances have also been made in measuring diffusion parameters at the higher temperatures. An important field covered in this Symposium was the correlation of such atomic transport data with thermodynamic data, a prerequisite if the nuclear engineer is to incorporate diffusion results into his normal process- assessment techniques. Finally the Symposium suggested the requirements for good critical tables. The mere compiling of such data is no longer sufficient; the compiler must have free access to all the data of a particular experiment, he must have an intimate knowledge of experimental work in this field and he must weight every figure quoted in the light of his experience. As a step in this direction, the Agency has called on the services of many well-known experts and is preparing a number of monographs giving critical assessments of thermodynamic data and phase-diagrams for many of the elements of interest in reactor design. Most of the countries engaged in research in thermodynamics were

  7. Ab initio identified design principles of solid-solution strengthening in Al

    International Nuclear Information System (INIS)

    Ma Duancheng; Friák, Martin; Pezold, Johann von; Raabe, Dierk; Neugebauer, Jörg

    2013-01-01

    Solid-solution strengthening in six Al–X binary systems is investigated using first-principle methods. The volumetric mismatch parameter and the solubility enthalpy per solute were calculated. We derive three rules for designing solid-solution strengthened alloys: (i) the solubility enthalpy per solute is related to the volumetric mismatch by a power law; (ii) for each annealing temperature, there exists an optimal solute–volume mismatch to achieve maximum strength; and (iii) the strengthening potential of high volumetric mismatch solutes is severely limited by their low solubility. Our results thus show that the thermodynamic properties of the system (here Al–X alloys) set clear upper bounds to the achievable strengthening effects owing to the reduced solubility with increasing volume mismatch. (paper)

  8. Applying the Coupled-Cluster Ansatz to Solids and Surfaces in the Thermodynamic Limit

    Science.gov (United States)

    Gruber, Thomas; Liao, Ke; Tsatsoulis, Theodoros; Hummel, Felix; Grüneis, Andreas

    2018-04-01

    Modern electronic structure theories can predict and simulate a wealth of phenomena in surface science and solid-state physics. In order to allow for a direct comparison with experiment, such ab initio predictions have to be made in the thermodynamic limit, substantially increasing the computational cost of many-electron wave-function theories. Here, we present a method that achieves thermodynamic limit results for solids and surfaces using the "gold standard" coupled cluster ansatz of quantum chemistry with unprecedented efficiency. We study the energy difference between carbon diamond and graphite crystals, adsorption energies of water on h -BN, as well as the cohesive energy of the Ne solid, demonstrating the increased efficiency and accuracy of coupled cluster theory for solids and surfaces.

  9. Thermodynamics

    CERN Document Server

    Fermi, Enrico

    1956-01-01

    Indisputably, this is a modern classic of science. Based on a course of lectures delivered by the author at Columbia University, the text is elementary in treatment and remarkable for its clarity and organization. Although it is assumed that the reader is familiar with the fundamental facts of thermometry and calorimetry, no advanced mathematics beyond calculus is assumed.Partial contents: thermodynamic systems, the first law of thermodynamics (application, adiabatic transformations), the second law of thermodynamics (Carnot cycle, absolute thermodynamic temperature, thermal engines), the entr

  10. Thermodynamics and kinetics of solids fragmentation at severe plastic deformation

    Directory of Open Access Journals (Sweden)

    A.V. Khomenko

    2015-09-01

    Full Text Available The approach of nonequilibrium evolution thermodynamics earlier offered is developed. It helps to describe the processes of defect formation within the adiabatic approximation. The basic equations system depends on the initial defects distribution (dislocations and grain boundaries. The phase diagram is determined with the domains of the realization of different limiting structure types. The interaction effect of several defect types on the formation of limiting structure is investigated in terms of the internal energy. The conditions of the formation of two limiting structures are found. The kinetics of the steady-state values establishment of the defects density is investigated within the scope of the adiabatic approximation. The dislocations density change follows the evolution of the grain boundaries density in this approach. It is shown that grain sizes, in limiting structures, decrease with an increase of the elastic strains.

  11. Solid solution and amorphous phase in Ti–Nb–Ta–Mn systems synthesized by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzman, P. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Parra, C. [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Bejar, L. [Instituto de Investigaciones Metalúrgicas, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, Morelia C.P. 58000, Michoacán (Mexico); Medina, A. [Facultad de Ingeniería Mecánica, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, C.P. 58000, Michoacán (Mexico); Guzman, D. [Departamento de Metalurgia, Universidad de Atacama, Av. España 485, Copiapó (Chile)

    2016-06-15

    This work discusses the formation of Ti–30Nb–13Ta–xMn (x: 2, 4 and 6 wt%) solid solution by mechanical alloying using a shaker mill. A solid solution was formed after 15 h of milling and an amorphous phase was formed after 30 h of milling, according to X-ray diffraction results. Disappearance of strongest X-ray diffraction peaks of Nb, Ta and Mn indicated the formation of solid solution, while, X-ray diffraction patterns of powders milled for 30 h showed an amorphous hump with crystalline peaks in the angular range of 35–45° in 2θ. TEM image analysis showed the presence of nanocrystalline intermetallic compounds embedded in an amorphous matrix. Mn{sub 2}Ti, MnTi and NbTi{sub 4} intermetallic compounds were detected and revealed crystallites with size ranging from 3 to 20 nm. The Gibbs free energy for the formation of solid solution and amorphous phase of three ternary systems (Ti–Nb–Ta, Ti–Nb–Mn and Ti–Ta–Mn) was calculated using extended Miedema's model. Experimental and thermodynamic data confirmed that solid solution was first formed in the alloy with 6wt% Mn followed by the formation of an amorphous phase as milling time increases. The presence of Mn promoted the formation of amorphous phase because the atomic radius difference between Mn with Ti, Nb and Ta. - Highlights: • Thermodynamics analysis of extension of solid solution of the Ti–Nb–Ta–Mn system. • Formation of amorphous phase and intermetallic compounds were observed. • Nanocrystalline intermetallic compounds were formed with the sizes between 3 and 20 nm.

  12. End-Member Formulation of Solid Solutions and Reactive Transport

    Energy Technology Data Exchange (ETDEWEB)

    Lichtner, Peter C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2015-09-01

    A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed to correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.

  13. Impact of vacancy-solute clusters on the aging of α-Fe solid solutions

    International Nuclear Information System (INIS)

    Schuler, Thomas

    2015-01-01

    Understanding and monitoring the aging of steels under vacancy supersaturation is a challenge of great practical interest for many industrial groups, and most of all for those related to nuclear energy. These steels always contain interstitial solutes, either as alloying elements or as impurities, and vacancies (V) that are equilibrium structural defects of materials. We have chosen the Fe-V -X system (X = C, N or O) as a model system for ferritic steels. Vacancy-solute clusters are likely to form in such systems because, despite the very low concentrations of their components, these cluster show very high attractive bonding. First of all, we have been working on the computation of intrinsic equilibrium properties of individual clusters, both thermodynamic (free binding energies) and kinetic (mobilities, dissociation coefficients, and their relationship with continuum diffusion) properties. Thanks to this atomic-scale characterization procedure, we have been able to highlight various effects of these clusters on a macroscopic system containing different cluster types: increase of solute solubility limits and total vacancy concentrations, flux couplings between interstitial solutes and vacancies, acceleration of solute precipitation kinetics and precipitate dissolution by solid solution stabilization due to vacancies. These results would not have been obtained without the development and/or extension of analytical methods in statistical physics which are able to describe cluster's components and their interactions at the atomic scale. Finally, we have also been working on cavities in α-iron, the study of which requires a different approach. Our study highlights the impact of the atomic discrete lattice on the equilibrium shape of cavities, and describes various kinetic mechanisms of these objects at the atomic scale. (author) [fr

  14. Thermodynamic phase behavior of API/polymer solid dispersions.

    Science.gov (United States)

    Prudic, Anke; Ji, Yuanhui; Sadowski, Gabriele

    2014-07-07

    To improve the bioavailability of poorly soluble active pharmaceutical ingredients (APIs), these materials are often integrated into a polymer matrix that acts as a carrier. The resulting mixture is called a solid dispersion. In this work, the phase behaviors of solid dispersions were investigated as a function of the API as well as of the type and molecular weight of the carrier polymer. Specifically, the solubility of artemisinin and indomethacin was measured in different poly(ethylene glycol)s (PEG 400, PEG 6000, and PEG 35000). The measured solubility data and the solubility of sulfonamides in poly(vinylpyrrolidone) (PVP) K10 and PEG 35000 were modeled using the perturbed-chain statistical associating fluid theory (PC-SAFT). The results show that PC-SAFT predictions are in a good accordance with the experimental data, and PC-SAFT can be used to predict the whole phase diagram of an API/polymer solid dispersion as a function of the kind of API and polymer and of the polymer's molecular weight. This remarkably simplifies the screening process for suitable API/polymer combinations.

  15. Radiation induced homogeneous precipitation in undersaturated solid-solutions

    International Nuclear Information System (INIS)

    Cauvin, Richard; Martin, Georges.

    1978-01-01

    The stability of various types of solid solutions under irradiation is studied. In this paper, observations made on AlZn solid solutions under 1 MeV electron irradiation are reported. Al-Zn was chosen as a prototype of solid solutions with a simple miscibility gap. It is shown that under appropriate irradiation conditions undersaturated AnZn solid solutions give rise to a homogeneous precipitation of coherent G.P. zones and of incoherent Zn precipitates the atomic volume of which is smaller than that of the matrix. We propose a more general treatment of solute concentration heterogeneities in solid solutions under irradiation and suggest how it might account for the nucleation of the observed phases. The growth of the observed precipitates is studied

  16. On calculation of lattice parameters of refractory metal solid solutions

    International Nuclear Information System (INIS)

    Barsukov, A.D.; Zhuravleva, A.D.; Pedos, A.A.

    1995-01-01

    Technique for calculating lattice periods of solid solutions is suggested. Experimental and calculation values of lattice periods of some solid solutions on the basis of refractory metals (V-Cr, Nb-Zr, Mo-W and other) are presented. Calculation error was correlated with experimental one. 7 refs.; 2 tabs

  17. Thermodynamic properties of solid H2 at intermediate orthohydrogen concentration

    International Nuclear Information System (INIS)

    Haase, D.G.; Perrell, L.R.

    1983-01-01

    The authors measured the specific heat of solid hydrogen samples grown under vapor pressure for orthohydrogen molar concentrations 0.65 < X < 0.2 and between 1 and 0.15 K. A thermal relaxation technique was used for the measurements to negate the heating effect of orthohydrogen conversion and to allow examination of long time heat release. The specific heat results showed no transitions or permanence which might be associated with a glass phase, with one exception. It was found that all relaxations were exponential with a single time constant regardless of sample thermal history. Measurements were made of samples isothermally converted at T = 0.3K from the ordered fcc phase to the hcp phase, in which case a gradual disorientation of the rotational moments is seen despite the relatively sharp fcc to hcp structural transition. 14 references, 5 figures

  18. Effect of Urea on the Thermodynamics of Hexadecyltrimethylammonium Bromide Micelle Formation in Aqueous Solutions

    Science.gov (United States)

    Velikov, A. A.

    2018-02-01

    The effect of urea on the thermodynamics of hexadecyltrimethylammonium bromide (CTAB) micelle formation in aqueous urea solutions was studied by isothermal titration microcalorimetry. The thermodynamic functions of Δ H, Δ G, and Δ S of CTAB micelle formation were calculated. The critical micelle concentrations (CMC) were determined. The addition of urea to the solution decreased the micelle formation entropy. This was attributed to the "lowering" of the structural temperature of the solution, which led to an increased number of hydrogen bonds and structure formation of water.

  19. A thermodynamic solution model for calcium carbonate: Towards an understanding of multi-equilibria precipitation pathways

    OpenAIRE

    Donnet, Marcel; Bowen, Paul; Lemaître, Jacques

    2009-01-01

    Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann’s approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thu...

  20. Thermodynamic study on some alkanediol solutions: Measurement and modeling

    International Nuclear Information System (INIS)

    Moosavi, Mehrdad; Motahari, Ahmad; Omrani, Abdollah; Rostami, Abbas Ali

    2013-01-01

    Highlights: • Measuring densities and viscosities for binary mixtures of some alkanediols. • Finding excess molar volume, partial molar volume and thermal expansion coefficient. • Fitting excess molar volume values with PFP and Redlich–Kister polynomial equations. • Deducing excess Gibbs free energy of activation and other thermodynamic parameters. • Predicting viscosity values with different single parameter semi empirical equations. - Abstract: The densities ρ and viscosities η of 1,2-ethanediol with 1,2-propanediol or 1,3-propanediol, and 1,2-propanediol with 1,3-propanediol binary liquid mixtures over the entire concentration range at temperatures (298.15 to 308.15) K with 5 K interval were measured. The experimental data were used to calculate the excess molar volume V m E , partial molar volume V ¯ m,i , partial molar volume at infinite dilution V ¯ i ∞ , apparent molar volume V φi , coefficient of thermal expansion α p , excess coefficient of thermal expansion α p E , excess viscosity η E , excess Gibbs energy of activation ΔG *E , and other thermodynamic parameters. A Redlich–Kister equation and Prigogine–Flory–Patterson (PFP) model was applied to correlate the excess molar volume results. Moreover, the viscosity data were correlated with the Grunberg–Nissan, Tamura–Kurata, Hind–Ubbelohde and Katti–Chaudhary equations. Good agreement was found between experimental data and modeling results

  1. Sulfur solubility of liquid and solid Fe-Cr alloys. A thermodynamic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Waldner, Peter [Leoben Univ. (Austria). Dept. of General, Analytical and Physical Chemistry

    2015-04-15

    Gibbs energy modeling for sulfur solving liquid and solid iron-chromium phases with body- and face-centered cubic structure has been carried out using a substitutional approach. Experimental data available from the literature on sulfur potentials in the temperature range 1 525 to 1 755 C for the liquid metallic phase and 1 000 to 1 300 C for the solid alloys have been taken into consideration. Recent thermodynamic evaluations of the Fe-S and Cr-S binary subsystems served as basis for the presented work. The obtained models allow a satisfactory reproduction of the majority of the sulfur potential data as well as the prediction of an isothermal partial section at 1 300 C. Consistent embedding of the optimized Gibbs energies within a recent thermodynamic modeling of the complete Cr-Fe-S system is achieved.

  2. Purification of uranothorite solid solutions from polyphase systems

    Energy Technology Data Exchange (ETDEWEB)

    Clavier, Nicolas, E-mail: nicolas.clavier@icsm.fr [ICSM, UMR 5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule – Bât. 426, BP 17171, 30207 Bagnols/Cèze cedex (France); Szenknect, Stéphanie; Costin, Dan Tiberiu; Mesbah, Adel; Ravaux, Johann [ICSM, UMR 5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule – Bât. 426, BP 17171, 30207 Bagnols/Cèze cedex (France); Poinssot, Christophe [CEA/DEN/DRCP/DIR, Site de Marcoule – Bât. 400, BP 17171, 30207 Bagnols/Cèze cedex (France); Dacheux, Nicolas [ICSM, UMR 5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule – Bât. 426, BP 17171, 30207 Bagnols/Cèze cedex (France)

    2013-10-15

    Graphical abstract: Display Omitted -- Highlights: •Purification of Th{sub 1−x}U{sub x}SiO{sub 4} uranothorites from oxide mixture was investigated. •Repetition of centrifugation steps was discarded due to poor recovery yields. •Successive washings in acid and basic media allowed the elimination of oxide secondary phases. •Structural and microstructural characterization of the purified samples was provided. -- Abstract: The mineral coffinite, nominally USiO{sub 4}, and associated Th{sub 1−x}U{sub x}SiO{sub 4} uranothorite solid solutions are of great interest from a geochemical point of view and in the case of the direct storage of spent nuclear fuels. Nevertheless, they clearly exhibit a lack in the evaluation of their thermodynamic data, mainly because of the difficulties linked with their preparation as pure phases. This paper thus presents physical and chemical methods aiming to separate uranothorite solid solutions from oxide additional phases such as amorphous SiO{sub 2} and nanometric crystallized Th{sub 1−y}U{sub y}O{sub 2}. The repetition of centrifugation steps envisaged in first place was rapidly dropped due to poor recovery yields, to the benefit of successive washings in acid then basic media. Under both static and dynamic flow rates (i.e. low or high rate of leachate renewal), ICP-AES (Inductively Coupled Plasma – Atomic Emission Spectroscopy) analyses revealed the systematic elimination of Th{sub 1−y}U{sub y}O{sub 2} in acid media and of SiO{sub 2} in basic media. Nevertheless, two successive steps were always needed to reach pure samples. On this basis, a first cycle performed in static conditions was chosen to eliminate the major part of the accessory phases while a second one, in dynamic conditions, allowed the elimination of the residual impurities. The complete purification of the samples was finally evidenced through the characterization of the samples by the means of PXRD (Powder X-Ray Diffraction), SEM (Scanning Electron

  3. Thermodynamic study on some alkanediol solutions: Measurement and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Moosavi, Mehrdad; Motahari, Ahmad; Omrani, Abdollah, E-mail: omrani@umz.ac.ir; Rostami, Abbas Ali

    2013-06-10

    Highlights: • Measuring densities and viscosities for binary mixtures of some alkanediols. • Finding excess molar volume, partial molar volume and thermal expansion coefficient. • Fitting excess molar volume values with PFP and Redlich–Kister polynomial equations. • Deducing excess Gibbs free energy of activation and other thermodynamic parameters. • Predicting viscosity values with different single parameter semi empirical equations. - Abstract: The densities ρ and viscosities η of 1,2-ethanediol with 1,2-propanediol or 1,3-propanediol, and 1,2-propanediol with 1,3-propanediol binary liquid mixtures over the entire concentration range at temperatures (298.15 to 308.15) K with 5 K interval were measured. The experimental data were used to calculate the excess molar volume V{sub m}{sup E}, partial molar volume V{sup ¯}{sub m,i}, partial molar volume at infinite dilution V{sup ¯}{sub i}{sup ∞}, apparent molar volume V{sub φi}, coefficient of thermal expansion α{sub p}, excess coefficient of thermal expansion α{sub p}{sup E}, excess viscosity η{sup E}, excess Gibbs energy of activation ΔG{sup *E}, and other thermodynamic parameters. A Redlich–Kister equation and Prigogine–Flory–Patterson (PFP) model was applied to correlate the excess molar volume results. Moreover, the viscosity data were correlated with the Grunberg–Nissan, Tamura–Kurata, Hind–Ubbelohde and Katti–Chaudhary equations. Good agreement was found between experimental data and modeling results.

  4. Thermodynamically Consistent Algorithms for the Solution of Phase-Field Models

    KAUST Repository

    Vignal, Philippe

    2016-02-11

    Phase-field models are emerging as a promising strategy to simulate interfacial phenomena. Rather than tracking interfaces explicitly as done in sharp interface descriptions, these models use a diffuse order parameter to monitor interfaces implicitly. This implicit description, as well as solid physical and mathematical footings, allow phase-field models to overcome problems found by predecessors. Nonetheless, the method has significant drawbacks. The phase-field framework relies on the solution of high-order, nonlinear partial differential equations. Solving these equations entails a considerable computational cost, so finding efficient strategies to handle them is important. Also, standard discretization strategies can many times lead to incorrect solutions. This happens because, for numerical solutions to phase-field equations to be valid, physical conditions such as mass conservation and free energy monotonicity need to be guaranteed. In this work, we focus on the development of thermodynamically consistent algorithms for time integration of phase-field models. The first part of this thesis focuses on an energy-stable numerical strategy developed for the phase-field crystal equation. This model was put forward to model microstructure evolution. The algorithm developed conserves, guarantees energy stability and is second order accurate in time. The second part of the thesis presents two numerical schemes that generalize literature regarding energy-stable methods for conserved and non-conserved phase-field models. The time discretization strategies can conserve mass if needed, are energy-stable, and second order accurate in time. We also develop an adaptive time-stepping strategy, which can be applied to any second-order accurate scheme. This time-adaptive strategy relies on a backward approximation to give an accurate error estimator. The spatial discretization, in both parts, relies on a mixed finite element formulation and isogeometric analysis. The codes are

  5. Fluctuations and thermodynamic response functions in a Lennard-Jones solid

    International Nuclear Information System (INIS)

    Li, M.; Johnson, W.L.

    1992-01-01

    Thermodynamic response functions of a nearest-neighbor Lennard-Jones solid--heat capacity, thermal-expansion coefficient, compressibility, and elastic constants--are calculated directly from fluctuations using molecular-dynamics simulations. The algorithm used is the earlier Parrinello-Rahman molecular dynamics modified to take into account symmetry and rotation invariance of the system under investigation. The convergence is very fast and results are in good agreement with existing Monte Carlo and molecular-dynamics results

  6. Expansion of thermodynamic model of solute permeation through reverse osmosis membrane

    International Nuclear Information System (INIS)

    Nishimaki, Kenzo; Koyama, Akio

    1994-01-01

    Many studies have been performed on permeation mechanism of solute and solvent in membrane separation process like reverse osmosis or ultrafiltration, and several models of solute/solvent permeation through membrane are proposed. Among these models, Kedem and Katchalsky, based on the theory of thermodynamics of irreversible processes, formulated the one-solute permeation process in their mathematical model, which treats membrane as a black box, not giving consideration to membrane structure and to interaction between membrane material and permeates, viz. solute and solvent. According to this theory, the driving force of solute/solvent permeation through membrane is the difference of their chemical potential between both sides of membrane, and the linear phenomenological equation is applied to describing the relation between driving force and flux of solute/solvent. This equation can be applied to the irreversible process only when the process is almost in equilibrium. This condition is supposed to be satisfied in the solute/solvent permeation process through compact membrane with fine pores like reverse osmosis membrane. When reverse osmosis is applied to treatment process for liquid waste, which usually contains a lot of solutes as contaminants, we can not predict the behavior of contaminants by the above one-solute process model. In the case of multi-solutes permeation process for liquid waste, the number of parameter in thermodynamic model increases rapidly with the number of solute, because of coupling phenomenon among solutes. In this study, we expanded the above thermodynamic model to multi-solute process applying operational calculus to the differential equations which describe the irreversible process of the system, and expressed concisely solute concentration vector as a matrix product. In this way, we predict the behavior of solutes in multi-solutes process, using values of parameters obtained in two-solutes process. (author)

  7. Thermal diffusivity of samarium-gadolinium zirconate solid solutions

    International Nuclear Information System (INIS)

    Pan, W.; Wan, C.L.; Xu, Q.; Wang, J.D.; Qu, Z.X.

    2007-01-01

    We synthesized samarium-gadolinium zirconate solid solutions and determined their thermal diffusivities, Young's moduli and thermal expansion coefficients, which are very important for their application in thermal barrier coatings. Samarium-gadolinium zirconate solid solutions have extremely low thermal diffusivity between 20 and 600 deg. C. The solid solutions have lower Young's moduli and higher thermal expansion coefficients than those of pure samarium and gadolinium zirconates. This combination of characteristics is promising for the application of samarium and gadolinium zirconates in gas turbines. The mechanism of phonon scattering by point defects is discussed

  8. SOLISOL-handling of solid solutions. Version 1.1

    International Nuclear Information System (INIS)

    Boerjesson, S.; Emren, A.

    1992-09-01

    SOLISOL is a C computer program designed to model geochemical reactions involving solid solutions. The program searches equilibrium concentrations of the components in the aqueous phase and the solid solution given by limited quantities of the solid solution components. The equilibrium code PHREEQE is used as a subprogram in SOLISOL. Subprograms external to PHREEQE extract information from PHREEQE results, take care of conserved properties, calculate solubilities and produce inputdata for PHREEQE. The essential idea in this process is to calculate solubilities for the components in terms of saturation indices, and give directions to PHREEQE on how to search for the equilibrium under those constraints. (au)

  9. Biosorption of Cr(VI from AqueousSolution Using New Adsorbent: Equilibrium and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Israa G. Zainal

    2010-01-01

    Full Text Available Biosorption is one such emerging technology which utilized naturally occurring waste materials to sequester heavy metals from polluted water. In the present study cinnamon was utilized for Cr(VI removal from aqueous solutions.It was found that a time of two hours was sufficient for sorption to attain equilibrium. The optimum pH was 2 for Cr(VI removal. Temprature has little influence on the biosorption process. The Cr(VI removal decreased with increase in temperature. The biosorption data was well fitted to Dubinin - Radushkevich (D-R, Freundlich and Tempkin adsorption isotherm models, although the correlation coefficient of Langmuir model was high but the calculated adsorption capacity did not agree with the experimental. The thermodynamic study reveals that the biosorption process is spontaneous and the spontaneity decreased with temperature increase and the process is exothermic accompanied by highly ordered adsorbate at the solid liquid interface. ΔH° values were negative and lie in the range of physical adsorption.

  10. Teaching Thermodynamics of Ideal Solutions: An Entropy-Based Approach to Help Students Better Understand and Appreciate the Subtleties of Solution Models

    Science.gov (United States)

    Tomba, J. Pablo

    2015-01-01

    The thermodynamic formalism of ideal solutions is developed in most of the textbooks postulating a form for the chemical potential of a generic component, which is adapted from the thermodynamics of ideal gas mixtures. From this basis, the rest of useful thermodynamic properties can be derived straightforwardly without further hypothesis. Although…

  11. A molecular-thermodynamic model for polyelectrolyte solutions

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, J.; Liu, H.; Hu, Y. [Thermodynamics Research Laboratory, East China University of Science and Technology, Shanghai 200237 (China); Prausnitz, J.M. [Department of Chemical Engineering, University of California, Berkeley, and Chemical Sciences Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720 (United States)

    1998-01-01

    Polyelectrolyte solutions are modeled as freely tangent-jointed, charged hard-sphere chains and corresponding counterions in a continuum medium with permitivity {var_epsilon}. By adopting the sticky-point model, the Helmholtz function for polyelectrolyte solutions is derived through the r-particle cavity-correlation function (CCF) for chains of sticky, charged hard spheres. The r-CCF is approximated by a product of effective nearest-neighbor two-particle CCFs; these are determined from the hypernetted-chain and mean-spherical closures (HNC/MSA) inside and outside the hard core, respectively, for the integral equation theory for electrolytes. The colligative properties are given as explicit functions of a scaling parameter {Gamma} that can be estimated by a simple iteration procedure. Osmotic pressures, osmotic coefficients, and activity coefficients are calculated for model solutions with various chain lengths. They are in good agreement with molecular simulation and experimental results. {copyright} {ital 1998 American Institute of Physics.}

  12. Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

    Science.gov (United States)

    Schuler, Thomas; Nastar, Maylise

    2016-06-01

    We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

  13. ELECTRICAL AND THERMODYNAMIC PROPERTIES OF A COLLAGEN SOLUTION

    Directory of Open Access Journals (Sweden)

    Jaromír Štancl

    2017-06-01

    Full Text Available This paper focuses on measurements of the electrical properties, the specific heat capacity and the thermal conductivity of a collagen solution (7.19% mass fraction of native bovine collagen in water. The results of our experiments show that specific electrical conductivity of collagen solution is strongly dependent on temperature. The transition region of collagen to gelatin has been observed from the measured temperature dependence of specific electrical conductivity, and has been confirmed by specific heat capacity measurements by a differential scanning calorimetry.

  14. Low temperature kinetics of In-Cd solid solution decomposition

    Czech Academy of Sciences Publication Activity Database

    Pal-Val, P.P.; Pal-Val, L.N.; Ostapovets, A.A.; Vaněk, Přemysl

    2008-01-01

    Roč. 137, - (2008), s. 35-42 ISSN 1012-0394 Institutional research plan: CEZ:AV0Z10100520 Keywords : low temperatures * In-based alloys * solid solutions * isothermal structure instability * Young's modulus * electrical resistivity * phase diagrams Subject RIV: BM - Solid Matter Physics ; Magnetism http://www.scientific.net/3-908451-53-1/35/

  15. Synthesis and characterization of type solid solution in the binary ...

    Indian Academy of Sciences (India)

    We have investigated Bi2O3–Eu2O3 binary system by doping with Eu2O3 in the composition range from 1 to 10 mole% via solid state reactions and succeeded to stabilize -Bi2O3 ... Our experimental observations strongly suggested that oxygen deficiency type non-stoichiometry is present in doped type solid solutions.

  16. Thermodynamic Models from Fluctuation Solution Theory Analysis of Molecular Simulations

    DEFF Research Database (Denmark)

    Christensen, Steen; Peters, Günther H.j.; Hansen, Flemming Yssing

    2007-01-01

    Fluctuation solution theory (FST) is employed to analyze results of molecular dynamics (MD) simulations of liquid mixtures. The objective is to generate parameters for macroscopic GE-models, here the modified Margules model. We present a strategy for choosing the number of parameters included...

  17. Ab initio Thermodynamic Approach to Identify Mixed Solid Sorbents for CO2 Capture Technology

    Directory of Open Access Journals (Sweden)

    Yuhua eDuan

    2015-10-01

    Full Text Available Because the current technologies for capturing CO2 are still too energy intensive, new materials must be developed that can capture CO2 reversibly with acceptable energy costs. At a given CO2 pressure, the turnover temperature (Tt of the reaction of an individual solid that can capture CO2 is fixed. Such Tt may be outside the operating temperature range (ΔTo for a practical capture technology. To adjust Tt to fit the practical ΔTo, in this study, three scenarios of mixing schemes are explored by combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations. Our calculated results demonstrate that by mixing different types of solids, it’s possible to shift Tt to the range of practical operating temperature conditions. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO2 capture reactions by the mixed solids of interest, we were able to identify the mixing ratios of two or more solids to form new sorbent materials for which lower capture energy costs are expected at the desired pressure and temperature conditions.

  18. Kinetics and thermodynamics of textile dye adsorption from aqueous solutions using babassu coconut mesocarp

    International Nuclear Information System (INIS)

    Vieira, Adriana P.; Santana, Sirlane A.A.; Bezerra, Cicero W.B.; Silva, Hildo A.S.; Chaves, Jose A.P.; Melo, Julio C.P. de; Silva Filho, Edson C. da; Airoldi, Claudio

    2009-01-01

    Extracted babassu coconut (Orbignya speciosa) mesocarp (BCM) was applied as a biosorbent for aqueous Blue Remazol R160 (BR 160), Rubi S2G (R S2G), Red Remazol 5R (RR 5), Violet Remazol 5R (VR 5) and Indanthrene Olive Green (IOG) dye solutions. The natural sorbent was processed batchwise while varying several system parameters such as stirring time, pH and temperature. The interactions were assayed with respect to both pseudo-first-order and second-order reaction kinetics, with the latter the more suitable kinetic model. The maximum adsorption was obtained at pH 1.0 for all dyes due to available anionic groups attached to the structures, which can be justified by pH pzc 6.7 for the biosorbent BCM. The ability of babassu coconut mesocarp to adsorb dyes gave the order R S2G > VR 5 > BR 160 > IOG > RR 5, which data were best fit to Freundlich model, but did not well-adjusted for all dyes. The dye/biopolymer interactions at the solid/liquid interface are all spontaneous as given by free Gibbs energy, with exothermic enthalpic values of -26.1, -15.8, -17.8, -15.8 and -23.7 kJ mol -1 for BR 160, R S2G, RR 5, IOG and VR 5, respectively. In spite of the negative entropic values contribution, the set of thermodynamic data is favorable for all dyes removal. However, the results pointed to the effectiveness of the mesocarp of babassu coconut as a biosorbent for removing textile dyes from aqueous solutions.

  19. Solid solution hardening in face centered binary alloys: Gliding statistics of a dislocation in random solid solution by atomistic simulation

    International Nuclear Information System (INIS)

    Patinet, S.

    2009-12-01

    The glide of edge and screw dislocation in solid solution is modeled through atomistic simulations in two model alloys of Ni(Al) and Al(Mg) described within the embedded atom method. Our approach is based on the study of the elementary interaction between dislocations and solutes to derive solid solution hardening of face centered cubic binary alloys. We identify the physical origins of the intensity and range of the interaction between a dislocation and a solute atom. The thermally activated crossing of a solute atom by a dislocation is studied at the atomistic scale. We show that hardening of edge and screw segments are similar. We develop a line tension model that reproduces quantitatively the atomistic calculations of the flow stress. We identify the universality class to which the dislocation depinning transition in solid solution belongs. (author)

  20. Thermodynamics

    International Nuclear Information System (INIS)

    Zanchini, E.

    1988-01-01

    The definition of energy, in thermodynamics, is dependent by starting operative definitions of the basic concepts of physics on which it rests, such as those of isolated systems, ambient of a system, separable system and set of separable states. Then the definition of energy is rigorously extended to open systems. The extension gives a clear physical meaning to the concept of energy difference between two states with arbitrary different compositions

  1. The crystallization of a solid solution in a solvent and the stability of a growth interface

    International Nuclear Information System (INIS)

    Malmejac, Yves

    1971-03-01

    The potential uses of germanium-silicon alloys as thermoelectric generators in hitherto unexploited temperature ranges initiated the present study. Many delicate problems are encountered in the classical methods of preparation. An original technique was sought for crystallization in a metallic solvent. The thermodynamic equilibria between the various phases of the ternary System used were studied in order to justify the method used. The conditions (temperature and composition) were determined in which the cooling of a ternary liquid mixture induces the precipitation of a binary solid solution with the desired composition. If large crystals are to be obtained from the solid solution, metallic solvent precipitation must be replaced by a mono-directional solvent crystallization. The combined effect of a certain number of simple physical phenomena on the stability of a crystal liquid interface was studied: the morphological stability of the crystal growth interface is the first step towards obtaining perfect crystals. (author) [fr

  2. Calorimetric measurements on plutonium rich (U,Pu)O2 solid solutions

    International Nuclear Information System (INIS)

    Kandan, R.; Babu, R.; Nagarajan, K.; Vasudeva Rao, P.R.

    2008-01-01

    Enthalpy increments of U (1-y) Pu y O 2 solid solutions with y = 0.45, 0.55 and 0.65 were measured using a high-temperature differential calorimeter by employing the method of inverse drop calorimetry in the temperature range 956-1803 K. From the fit equations for the enthalpy increments, other thermodynamic functions such as heat capacity, entropy and Gibbs energy function have been computed in the temperature range 298-1800 K. The results are presented and compared with the data available in the literature. The results indicate that the enthalpies of U (1-y) Pu y O 2 solid solutions with y = 0.45, 0.55 and 0.65 obey the Neumann-Kopp's molar additivity rule

  3. Thermodynamics of hydrogen and deuterium solutions in α-zirconium

    International Nuclear Information System (INIS)

    Vinokurov, Yu.V.; Mogutnov, B.M.

    1979-01-01

    Interaction of H 2 and D 2 with α-Zr are studied in the 700-890 K temperature range using a high-temperature colorimeter. It is shown that hydrogen and deuterium partial enthalpies in zirconium do not depend on the temperature and concentration and compose -48.9+-1.0 and -46.2+-1.2 kJ/g-at. Calculated is an excess entropy of hydrogen in a solution and analyzed are contributions composing it

  4. Thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell in combined heat and power applications

    Science.gov (United States)

    Abraham, F.; Dincer, I.

    2015-12-01

    This paper presents a comprehensive steady state modelling and thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell integrated with Gas Turbine power cycle (DU-SOFC/GT). The use of urea as direct fuel mitigates public health and safety risks associated with the use of hydrogen and ammonia. The integration scheme in this study covers both oxygen ion-conducting solid oxide fuel cells (SOFC-O) and hydrogen proton-conducting solid oxide fuel cells (SOFC-H). Parametric case studies are carried out to investigate the effects of design and operating parameters on the overall performance of the system. The results reveal that the fuel cell exhibited the highest level of exergy destruction among other system components. Furthermore, the SOFC-O based system offers better overall performance than that with the SOFC-H option mainly due to the detrimental reverse water-gas shift reaction at the SOFC anode as well as the unique configuration of the system.

  5. Thermodynamics of hydrogen and deuterium solutions in. cap alpha. -zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Vinokurov, Yu V; Mogutnov, B M [Tsentral' nyj Nauchno-Issledovatel' skij Inst. Chernoj Metallurgii, Moscow (USSR)

    1979-09-01

    Interaction of H/sub 2/ and D/sub 2/ with ..cap alpha..-Zr are studied in the 700-890 K temperature range using a high-temperature colorimeter. It is shown that hydrogen and deuterium partial enthalpies in zirconium do not depend on the temperature and concentration and compose -48.9+-1.0 and -46.2+-1.2 kJ/g-at. Calculated is an excess entropy of hydrogen in a solution and analyzed are contributions composing it.

  6. Features of solid solutions composition in magnesium with yttrium alloys

    International Nuclear Information System (INIS)

    Drits, M.E.; Rokhlin, L.L.; Tarytina, I.E.

    1983-01-01

    Additional data on features of yttrium solid solutions composition in magnesium in the course of their decomposition investigation in the case of aging are obtianed. The investigation has been carried out on the base of a binary magnesium-yttrium alloy the composition of which has been close to maximum solubility (at eutectic temperature) and magnesium-yttrium alloys additionally doped with zinc. It is shown that higher yttrium solubility in solid magnesium than it has been expected, issueing from the difference in atomic radii of these metals indicates electron yttrium-magnesium atoms interaction. In oversaturated magnesium-yttrium solid solutions at earlier decomposition stages Mg 3 Cd type ordering is observed. At aging temperatures up to 250 deg C and long exposures corresponding to highest strengthening in oversaturated magnesium yttrium solid solutions a rhombic crystal lattice phase with three symmetric orientations is formed

  7. SOLUTION THERMODYNAMICS OF TRICLOSAN AND TRICLOCARBAN IN SOME VOLATILE ORGANIC SOLVENTS

    OpenAIRE

    DELGADO, Daniel R.; R. HOLGUIN, Andres; MARTÍNEZ, Fleming

    2012-01-01

    Thermodynamic functions of Gibbs energy, enthalpy, and entropy for the solution processes of the antimicrobial drugs Triclosan and Triclocarban in five volatile organic solvents were calculated from solubility values at temperatures from 293.15 to 313.15 K. Triclosan and Triclocarban solubility was determined in acetone, acetonitrile (AcCN), ethyl acetate (AcOEt), methanol (MetOH), and cyclohexane (CH). The excess of Gibbs energy and the activity coefficients of the solutes were also calculat...

  8. Thermodynamics of aqueous solutions containing poly (N-isopropylacrylamide)

    Energy Technology Data Exchange (ETDEWEB)

    Poschlad, K. [Technical University of Berlin, Chair of Thermodynamics TK 7, Strasse des 17, Juni 135, 10623 Berlin (Germany); Enders, S., E-mail: sabine.enders@tu-berlin.d [Technical University of Berlin, Chair of Thermodynamics TK 7, Strasse des 17, Juni 135, 10623 Berlin (Germany)

    2011-03-15

    Hydrogels undergo reversible and discontinuous volume changes in response to variation of solution conditions such as solvent composition, temperature, salt concentration, and pH. In this contribution we focus our attention on the experimental and theoretical investigation of these swelling equilibria of aqueous cross-linked poly (N-isopropylacrylamide) solutions as well as on the connected demixing behavior of the linear polymer dissolved in water. For the experimental study of the (liquid + liquid) equilibrium an alternative method based on refractive index measurements is suggested. In order to calculate the swelling behavior a model combining an expression for the Gibbs free energy of mixing with an expression for the elastic network is applied. As a model for the Gibbs free energy of mixing the UNIQUAC-approach and the Koningsveld-Kleintjens model are used. For the elastic network contribution again two different theories, namely the phantom network theory and the affine network theory, were applied. Whereas the type of network theory has only a small influence on the calculation results, the Gibbs free energy of mixing has a large impact. Using the UNIQUAC-approach the swelling equilibria can be correlated close to the experimental data, however, this model predicts a homogeneous mixture for linear polymer chains in water. In contrast to this situation the Koningsveld-Kleintjens model does a good job in calculating the swelling equilibria as well as the demixing curve, however, the adjustable parameter must be changed slightly.

  9. A Concise Equation of State for Aqueous Solutions of Electrolytes Incorporating Thermodynamic Laws and Entropy

    Directory of Open Access Journals (Sweden)

    Raji Heyrovská

    2004-03-01

    Full Text Available Abstract: Recently, the author suggested a simple and composite equation of state by incorporating fundamental thermodynamic properties like heat capacities into her earlier concise equation of state for gases based on free volume and molecular association / dissociation. This work brings new results for aqueous solutions, based on the analogy of the equation of state for gases and solutions over wide ranges of pressures (for gases and concentrations (for solutions. The definitions of entropy and heat energy through the equation of state for gases, also holds for solutions.

  10. Solid state synthesis, crystal growth and optical properties of urea and p-chloronitrobenzene solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Rai, R.N., E-mail: rn_rai@yahoo.co.in [Department of Chemistry, Centre of Advanced Study, Banaras Hindu University, Varanasi 221005 (India); Kant, Shiva; Reddi, R.S.B. [Department of Chemistry, Centre of Advanced Study, Banaras Hindu University, Varanasi 221005 (India); Ganesamoorthy, S. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Gupta, P.K. [Laser Materials Development & Devices Division, Raja Ramanna Centre for Advanced Technology, Indore 452013 (India)

    2016-01-15

    Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB and UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal. - Highlights: • The hygroscopic character of urea was modified by making the solid solutionSolid solution formation is support by elemental, powder- and single crystal XRD • Crystal of solid solution has higher SHG signal and mechanical stability. • Refractive index and band gap of solid solution crystal have determined.

  11. Direct and indirect effects of radiation on polar solid solutions

    International Nuclear Information System (INIS)

    Ershov, V.G.; Gaponova, I.S.

    1982-01-01

    Radiation-chemical decomposition of a solute is due to the direct effect of ionizing radiation on it and also to its reaction with radical-ion products of radiolysis of the solution. At low temperature, the movement of the reagents is limited, and thus it is possible to isolate and evaluate the contribution of direct and indirect effects of radiation on the solute. The present paper is devoted to an investigation of the mechanism of formation of radicals from a solute (LiNO 2 ) in a polar solid solution (CH 3 OH) under the effect of γ-radiation

  12. Modeling for thermodynamic activities of components in simulated reprocessing solutions

    International Nuclear Information System (INIS)

    Sasahira, Akira; Hoshikawa, Tadahiro; Kawamura, Fumio

    1992-01-01

    Analyses of chemical reactions have been widely carried out for soluble fission products encountered in nuclear fuel reprocessing. For detailed analyses of reactions, a prediction of the activity or activity coefficient for nitric acid, water, and several nitrates of fission products is needed. An idea for the predicted nitric acid activity was presented earlier. The model, designated the hydration model, does not predict the nitrate activity. It did, however, suggest that the activity of water would be a function of nitric acid activity but not the molar fraction of water. If the activities of nitric acid and water are accurately predicted, the activity of the last component, nitrate, can be calculated using the Gibbs-Duhem relation for chemical potentials. Therefore, in this study, the earlier hydration model was modified to evaluate the water activity more accurately. The modified model was experimentally examined in stimulated reprocessing solutions. It is concluded that the modified model was suitable for water activity, but further improvement was needed for the activity evaluation of nitric acid in order to calculate the nitrate activity

  13. Thermodynamic Analysis of a Woodchips Gasification Integrated with Solid Oxide Fuel Cell and Stirling Engine

    DEFF Research Database (Denmark)

    Rokni, Masoud

    2013-01-01

    Integrated gasification Solid Oxide Fuel Cell (SOFC) and Stirling engine for combined heat and power application is analysed. The target for electricity production is 120 kW. Woodchips are used as gasification feedstock to produce syngas which is utilized for feeding the SOFC stacks for electricity...... and suggested. Thermodynamic analysis shows that a thermal efficiency of 42.4% based on LHV (lower heating value) can be achieved. Different parameter studies are performed to analysis system behaviour under different conditions. The analysis show that increasing fuel mass flow from the design point results...

  14. Thermodynamic properties of a solid exhibiting the energy spectrum given by the logistic map

    International Nuclear Information System (INIS)

    Curado, E.M.F.

    2000-05-01

    We show that the infinite-dimensional representation of the recently introduced Logistic algebra can be interpreted as a non-trivial generalization of the Heisenberg or oscillator algebra. This allows to construct a quantum Hamiltonian having the energy energy spectrum given by the logistic map. We analyze the Hamiltonian of a solid whose collective modes of vibrations are described by this generalized oscillator and compute the thermodynamic properties of the model in the two-cycle and γ3.6785 chaotic region of the logistic map. (author)

  15. Surface phase transitions in cu-based solid solutions

    Science.gov (United States)

    Zhevnenko, S. N.; Chernyshikhin, S. V.

    2017-11-01

    We have measured surface energy in two-component Cu-based systems in H2 + Ar gas atmosphere. The experiments on solid Cu [Ag] and Cu [Co] solutions show presence of phase transitions on the surfaces. Isotherms of the surface energy have singularities (the minimum in the case of copper solid solutions with silver and the maximum in the case of solid solutions with cobalt). In both cases, the surface phase transitions cause deficiency of surface miscibility: formation of a monolayer (multilayer) (Cu-Ag) or of nanoscale particles (Cu-Co). At the same time, according to the volume phase diagrams, the concentration and temperature of the surface phase transitions correspond to the solid solution within the volume. The method permits determining the rate of diffusional creep in addition to the surface energy. The temperature and concentration dependence of the solid solutions' viscosity coefficient supports the fact of the surface phase transitions and provides insights into the diffusion properties of the transforming surfaces.

  16. Thermodynamics of water-solid interactions in crystalline and amorphous pharmaceutical materials.

    Science.gov (United States)

    Sacchetti, Mark

    2014-09-01

    Pharmaceutical materials, crystalline and amorphous, sorb water from the atmosphere, which affects critical factors in the development of drugs, such as the selection of drug substance crystal form, compatibility with excipients, dosage form selection, packaging, and product shelf-life. It is common practice to quantify the amount of water that a material sorbs at a given relative humidity (RH), but the results alone provide minimal to no physicochemical insight into water-solid interactions, without which pharmaceutical scientists cannot develop an understanding of their materials, so as to anticipate and circumvent potential problems. This research was conducted to advance the science of pharmaceutical materials by examining the thermodynamics of solids with sorbed water. The compounds studied include nonhygroscopic drugs, a channel hydrate drug, a stoichiometric hydrate excipient, and an amorphous excipient. The water sorption isotherms were measured over a range of temperature to extract the partial molar enthalpy and entropy of sorbed water as well as the same quantities for some of the solids. It was found that water-solid interactions spanned a range of energy and entropy as a function of RH, which was unique to the solid, and which could be valuable in identifying batch-to-batch differences and effects of processing in material performance. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

  17. Thermodynamic simulation of biomass gas steam reforming for a solid oxide fuel cell (SOFC system

    Directory of Open Access Journals (Sweden)

    A. Sordi

    2009-12-01

    Full Text Available This paper presents a methodology to simulate a small-scale fuel cell system for power generation using biomass gas as fuel. The methodology encompasses the thermodynamic and electrochemical aspects of a solid oxide fuel cell (SOFC, as well as solves the problem of chemical equilibrium in complex systems. In this case the complex system is the internal reforming of biomass gas to produce hydrogen. The fuel cell input variables are: operational voltage, cell power output, composition of the biomass gas reforming, thermodynamic efficiency, electrochemical efficiency, practical efficiency, the First and Second law efficiencies for the whole system. The chemical compositions, molar flows and temperatures are presented to each point of the system as well as the exergetic efficiency. For a molar water/carbon ratio of 2, the thermodynamic simulation of the biomass gas reforming indicates the maximum hydrogen production at a temperature of 1070 K, which can vary as a function of the biomass gas composition. The comparison with the efficiency of simple gas turbine cycle and regenerative gas turbine cycle shows the superiority of SOFC for the considered electrical power range.

  18. Solute redistribution in dendritic solidification with diffusion in the solid

    Science.gov (United States)

    Ganesan, S.; Poirier, D. R.

    1989-01-01

    An investigation of solute redistribution during dendritic solidification with diffusion in the solid has been performed using numerical techniques. The extent of diffusion is characterized by the instantaneous and average diffusion parameters. These parameters are functions of the diffusion Fourier number, the partition ratio and the fraction solid. Numerical results are presented as an approximate model, which is used to predict the average diffusion parameter and calculate the composition of the interdendritic liquid during solidification.

  19. Heterogeneous Ferroelectric Solid Solutions Phases and Domain States

    CERN Document Server

    Topolov, Vitaly

    2012-01-01

    The book deals with perovskite-type ferroelectric solid solutions for modern materials science and applications, solving problems of complicated heterophase/domain structures near the morphotropic phase boundary and applications to various systems with morphotropic phases. In this book domain state–interface diagrams are presented for the interpretation of heterophase states in perovskite-type ferroelectric solid solutions. It allows to describe the stress relief in the presence of polydomain phases, the behavior of unit-cell parameters of coexisting phases and the effect of external electric fields. The novelty of the book consists in (i) the first systematization of data about heterophase states and their evolution in ferroelectric solid solutions (ii) the general interpretation of heterophase and domain structures at changing temperature, composition or electric field (iii) the complete analysis of interconnection domain structures, unit-cell parameters changes, heterophase structures and stress relief.

  20. An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range.

    Science.gov (United States)

    Dutcher, Cari S; Ge, Xinlei; Wexler, Anthony S; Clegg, Simon L

    2013-04-18

    In previous studies (Dutcher et al. J. Phys. Chem. C 2011, 115, 16474-16487; 2012, 116, 1850-1864), we derived equations for the Gibbs energy, solvent and solute activities, and solute concentrations in multicomponent liquid mixtures, based upon expressions for adsorption isotherms that include arbitrary numbers of hydration layers on each solute. In this work, the long-range electrostatic interactions that dominate in dilute solutions are added to the Gibbs energy expression, thus extending the range of concentrations for which the model can be used from pure liquid solute(s) to infinite dilution in the solvent, water. An equation for the conversion of the reference state for solute activity coefficients to infinite dilution in water has been derived. A number of simplifications are identified, notably the equivalence of the sorption site parameters r and the stoichiometric coefficients of the solutes, resulting in a reduction in the number of model parameters. Solute concentrations in mixtures conform to a modified Zdanovskii-Stokes-Robinson mixing rule, and solute activity coefficients to a modified McKay-Perring relation, when the effects of the long-range (Debye-Hückel) term in the equations are taken into account. Practical applications of the equations to osmotic and activity coefficients of pure aqueous electrolyte solutions and mixtures show both satisfactory accuracy from low to high concentrations, together with a thermodynamically reasonable extrapolation (beyond the range of measurements) to extreme concentration and to the pure liquid solute(s).

  1. An ordered metallic glass solid solution phase that grows from the melt like a crystal

    International Nuclear Information System (INIS)

    Chapman, Karena W.; Chupas, Peter J.; Long, Gabrielle G.; Bendersky, Leonid A.; Levine, Lyle E.; Mompiou, Frédéric; Stalick, Judith K.; Cahn, John W.

    2014-01-01

    We report structural studies of an Al–Fe–Si glassy solid that is a solid solution phase in the classical thermodynamic sense. We demonstrate that it is neither a frozen melt nor nanocrystalline. The glass has a well-defined solubility limit and rejects Al during formation from the melt. The pair distribution function of the glass reveals chemical ordering out to at least 12 Å that resembles the ordering within a stable crystalline intermetallic phase of neighboring composition. Under isothermal annealing at 305 °C the glass first rejects Al, then persists for approximately 1 h with no detectable change in structure, and finally is transformed by a first-order phase transition to a crystalline phase with a structure that is different from that within the glass. It is possible that this remarkable glass phase has a fully ordered atomic structure that nevertheless possesses no long-range translational symmetry and is isotropic

  2. EFFECT SIGNIFICANCE ASSESSMENT OF THE THERMODYNAMICAL FACTORS ON THE SOLID OXIDE FUEL CELL OPERATION

    Directory of Open Access Journals (Sweden)

    V. A. Sednin

    2015-01-01

    Full Text Available Technologies of direct conversion of the fuel energy into electrical power are an upcoming trend in power economy. Over the last decades a number of countries have created industrial prototypes of power plants on fuel elements (cells, while fuel cells themselves became a commercial product on the world energy market. High electrical efficiency of the fuel cells allows predictting their further spread as part of hybrid installations jointly with gas and steam turbines which specifically enables achieving the electrical efficiency greater than 70 %. Nevertheless, investigations in the area of increasing efficiency and reliability of the fuel cells continue. Inter alia, research into the effects of oxidizing reaction thermodynamic parameters, fuel composition and oxidation reaction products on effectiveness of the solid oxide fuel cells (SOFC is of specific scientific interest. The article presents a concise analysis of the fuel type effects on the SOFC efficiency. Based on the open publications experimental data and the data of numerical model studies, the authors adduce results of the statistical analysis of the SOFC thermodynamic parameters effect on the effectiveness of its functioning as well as of the reciprocative factors of these parameters and gas composition at the inlet and at the outlet of the cell. The presented diagrams reflect dimension of the indicated parameters on the SOFC operation effectiveness. The significance levels of the above listed factors are ascertained. Statistical analysis of the effects of the SOFC functionning process thermodynamical, consumption and concentration parameters demonstrates quintessential influence of the reciprocative factors (temperature – flow-rate and pressure – flow-rate and the nitrogen N2 and oxygen O2 concentrations on the operation efficiency in the researched range of its functioning. These are the parameters to be considered on a first-priority basis while developing mathematical models

  3. The thermodynamic characteristics of ion resolvation in aqueous solutions of dimethylformamide and dimethylsulfoxide

    International Nuclear Information System (INIS)

    Parfenyuk, V.I.

    2002-01-01

    Data on thermodynamic characteristics of chlorine, bromine and iodine ion resolution in mixtures of water with dimethylformamide and dimethylsulfoxide are provided and analyzed. The values presented were calculated on the basis of the volt potential differences method. It is shown the actual thermodynamic characteristics of anion transfer have positive values in contrast to cations having the opposite sign. It stems from changes in the structure of mixed solvent when passing from water to water-organic mixtures in the solution/gas phase interface. Analysis of chemical Gibbs' energies of resolvation of the ions studied suggests that anions, which can form hydrogen bonds with proton-donor solvents, are hardly solved in aprotic solutions [ru

  4. Solubility and solution thermodynamics of 2-methyl-6-nitroaniline in ten organic solvents at elevated temperatures

    International Nuclear Information System (INIS)

    Cong, Yang; Wang, Jian; Du, Cunbin; Han, Shuo; Zhao, Hongkun

    2016-01-01

    Highlights: • Solubility of 2-methyl-6-nitroaniline in ten solvents were determined. • The solubility were correlated with four thermodynamic models. • Standard dissolution enthalpy and excess enthalpy of the solutions were computed. - Abstract: Knowledge of solubility for 2-methyl-6-nitroaniline in different solvents is essential for its purification and further theoretical studies. In this paper, the solid-liquid equilibrium for 2-methyl-6-nitroaniline in ten pure organic solvents (methanol, ethanol, n-propanol, isopropanol, toluene, ethyl acetate, acetonitrile, acetone, cyclohexane and 1,4-dioxane) was established using the isothermal saturation method at temperatures T = (278.15–313.15) K under pressure of 101.2 kPa, and the solubility of 2-methyl-6-nitroaniline in these solvents were determined by a high-performance liquid chromatography (HPLC). In general, the mole fraction solubility followed the following order from high to low in different solvents: 1,4-dioxane (0.1799–0.3390) > acetone (0.1128–0.3010) > ethyl acetate (0.08414–0.2654) > acetonitrile (0.04179–0.2027) > toluene (0.02367–0.1104) > n-propanol (0.01080–0.04514) > ethanol (0.01020–0.04202) > isopropanol (0.008595–0.03763) > methanol (0.007391–0.03198) > cyclohexane (0.001027–0.005617). The modified Apelblat equation, λh equation, Wilson model and NRTL model were employed to correlate the measured solubility data of 2-methyl-6-nitroaniline in the selected solvents. Results indicated that the largest values of RAD and RMSD acquired by the four models were less than 0.76% and 9.13 × 10"−"4, respectively. The modified Apelblat equation provided better results than the other three models. Furthermore, the standard dissolution enthalpy and excess enthalpy of the solutions were computed from the solubility values. The standard dissolution enthalpies vary within the range from (14.88 to 45.57) kJ·mol"−"1 and are all positive, the dissolution process of 2-methyl-6

  5. Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

    International Nuclear Information System (INIS)

    Minelli, Matteo; Doghieri, Ferruccio

    2014-01-01

    Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps

  6. Thermodynamics of uranium and nitric acid extraction from aqueous solution of TBP/diluent

    International Nuclear Information System (INIS)

    Souza Freitas, R.F. de.

    1982-06-01

    A thermodynamically consistent procedure for predicting distribution equilibria for uranyl nitrate and nitric acid between an aqueous solution and 30 vol % tributyl phosphate (TBP) in a hydrocarbon diluent is studied. Experimental work is developed in order to obtain equilibrium data for the system uranyl nitrate, nitric acid, water and 30 vol % TBP in n-dodecane, at 25 0 C and 40 0 C. The theoretical equilibrium data, obtained with the aid of a computer, are compared with the experimental results. (Author) [pt

  7. Surface thermodynamics

    International Nuclear Information System (INIS)

    Garcia-Moliner, F.

    1975-01-01

    Basic thermodynamics of a system consisting of two bulk phases with an interface. Solid surfaces: general. Discussion of experimental data on surface tension and related concepts. Adsorption thermodynamics in the Gibbsian scheme. Adsorption on inert solid adsorbents. Systems with electrical charges: chemistry and thermodynamics of imperfect crystals. Thermodynamics of charged surfaces. Simple models of charge transfer chemisorption. Adsorption heat and related concepts. Surface phase transitions

  8. Kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain from aqueous solutions

    International Nuclear Information System (INIS)

    Li Qingzhu; Chai Liyuan; Yang Zhihui; Wang Qingwei

    2009-01-01

    Spent grain, a main by-product of the brewing industry, is available in large quantities, but its main application has been limited to animal feeding. Nevertheless, in this study, spent grain modified with 1 M NaCl solution as a novel adsorbent has been used for the adsorption of Pb(II) in aqueous solutions. Isotherms, kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain were studied. The equilibrium data were well fitted with Langmuir, Freundlich and Dubinin-Radushkevick (D-R) isotherm models. The kinetics of Pb(II) adsorption followed pseudo-second-order model, using the rate constants of pseudo-second-order model, the activation energy (E a ) of Pb(II) adsorption was determined as 12.33 kJ mol -1 according to the Arrhenius equation. Various thermodynamic parameters such as ΔG ads , ΔH ads and ΔS ads were also calculated. Thermodynamic results indicate that Pb(II) adsorption onto modified spent grain is a spontaneous and endothermic process. Therefore, it can be concluded that modified spent grain as a new effective adsorbent has potential for Pb(II) removal from aqueous solutions.

  9. Cyanide and antimony thermodynamic database for the aqueous species and solids for the EPA-MINTEQ geochemical code

    International Nuclear Information System (INIS)

    Sehmel, G.A.

    1989-05-01

    Thermodynamic data for aqueous species and solids that contain cyanide and antimony were tabulated from several commonly accepted, published sources of thermodynamic data and recent journal article. The review does not include gases or organic complexes of either antimony or cyanide, nor does the review include the sulfur compounds of cyanide. The basic thermodynamic data, ΔG/sub f,298//sup o/, ΔH/sub f,298//sup o/, and S/sub f//sup o/ values, were chosen to represent each solid phase and aqueous species for which data were available in the appropriate standard state. From these data the equilibrium constants (log K/sub r,298//sup o/) and enthalpies of reaction (ΔH/sub r,298//sup o/) at 298 K (25/degree/C) were calculated for reactions involving the formation of these aqueous species and solids from the basic components. 34 refs., 14 tabs

  10. Structure and high-piezoelectricity in lead oxide solid solutions

    NARCIS (Netherlands)

    Noheda, B.

    2002-01-01

    A review of the recent advances in the understanding of piezoelectricity in lead oxide solid solutions is presented, giving special attention to the structural aspects. It has now become clear that the very high electromechanical response in these materials is directly related to the existence of

  11. Phase segregation in cerium-lanthanum solid solutions

    NARCIS (Netherlands)

    Belliere, V.; Joorst, G; Stephan, O; de Groot, FMF; Weckhuysen, BM

    2006-01-01

    Electron energy-loss spectroscopy (EELS) in combination with scanning transmission electron microscopy ( STEM) reveals that the La enrichment at the surface of cerium-lanthanum solid solutions is an averaged effect and that segregation occurs in a mixed oxide phase. This separation occurs within a

  12. Dynamic Aspects of Solid Solution Cathodes for Electrochemical Power Sources

    DEFF Research Database (Denmark)

    Atlung, Sven; West, Keld; Jacobsen, Torben

    1979-01-01

    Battery systems based on alkali metal anodes and solid solution cathodes,i.e., cathodes based on the insertion of the alkali cation in a "host lattice,"show considerable promise for high energy density storage batteries. Thispaper discusses the interaction between battery requirements...

  13. Turbulent solutal convection and surface patterning in solid dissolution

    International Nuclear Information System (INIS)

    Sullivan, T.S.; Liu, Y.; Ecke, R.E.

    1996-01-01

    We describe experiments in which crystals of NaCl, KBr, and KCl are dissolved from below by aqueous solutions containing concentrations of the respective salts from zero concentration to near saturation. The solution near the solid-liquid interface is gravitationally unstable, producing turbulent hydrodynamic motion similar to thermal convection from a single surface cooled from above. The coupling of the fluid flow with the solid dissolution produces irregular patterns at the solid-liquid interface with a distribution of horizontal length scales. The dissolution mass flux and the pattern length scales are compared with a turbulent boundary layer model. Remarkable agreement is found, showing that the fluid motion controls both the dissolution rate and the interface patterning. copyright 1996 The American Physical Society

  14. Kinetic and Thermodynamic Studies for the Removal of Europium Ions from Waste Solution Using Some Local Clay Minerals

    International Nuclear Information System (INIS)

    El-Kamash, A.M.; El-Masry, E.H.; El-Dessouky, M.I.

    2008-01-01

    Thermodynamic and kinetic investigations on the removal of Eu 3+ ions from aqueous waste solution using bentonite and sandstone, as local clay minerals, has been done using batch technique. The influences of ph, contact time between liquid and solid phases, initial metal ion concentration, and temperature have been evaluated. Pseudo first-order and pseudo second-order kinetic models were used to analyze the sorption rate data and the results showed that the pseudo second-order model is best correlate the kinetic data. Equilibrium isotherms were determined to assess the maximum sorption capacity of bentonite and sandstone and the equilibrium sorption data were analyzed using Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherm models. All tested models fit the data reasonably well in terms of regression coefficients. The maximum sorption capacity of bentonite was found to be greater than that of sandstone and the mean free energy is in all cases in the range corresponding to the ion exchange type of sorption. Sorption studies were also performed at different temperatures to obtain the thermodynamic parameters of the process. The numerical value of δG degree decreases with an increase in temperature, indicating that the sorption reaction is more favorable at higher temperature. The positive values of δH degree correspond to the endothermic nature of the sorption process

  15. Hydrothermal crystallization of zirconia and zirconia solid solutions

    International Nuclear Information System (INIS)

    Pyda, W.; Haberko, K.; Bucko, M.M.

    1991-01-01

    Zirconia as well as yttria-zirconia and calcia-zirconia solid-solution powders were crystallized under hydrothermal conditions from (co)precipitated hydroxides. The morphology of the power particles is strongly dependent on the crystallization conditions. The powders crystallized in a water solution of Na, K, and Li hydroxides show elongated particles of much larger sizes than those which result from the process carried out in pure water or a water solution of Na, K, or Li chlorides. The shapes of the latter particles are isometric. In this paper the growth mechanism of the elongated particles is suggested

  16. Kinetics and thermodynamics of β-carotene and chlorophyll adsorption onto acid-activated bentonite from Xinjiang in xylene solution

    International Nuclear Information System (INIS)

    Wu Zhansheng; Li Chun

    2009-01-01

    The kinetics and thermodynamics of β-carotene and chlorophyll adsorption from xylene solution onto acid-activated bentonite (AAB) within the temperature range 65-95 deg. C were investigated. Adsorption of β-carotene was described well with the Langmuir isotherm, whereas chlorophyll adsorption was determined well with the Freundlich isotherm, and the experimental data on chlorophyll adsorption were also fitted by the Langmuir isotherm to a certain extent, as reflected by correlation coefficients (R 2 ) over 0.9865. In addition, the adsorption of β-carotene and chlorophyll onto AAB are favorable. The pseudo-second-order model was found to explain the kinetics of adsorption of both pigments more effectively. Increase of temperature enhanced the adsorption rate and equilibrium adsorption capacity of β-carotene and chlorophyll on AAB. The activation energy for the sorption of β-carotene and chlorophyll on AAB was 19.808 kJ/mol and 16.475 kJ/mol, respectively. The thermodynamic parameters ΔH θ , ΔS θ and ΔG θ , computed from K F of the adsorption isotherm constant, were 21.766 kJ/mol, 92.244 J/K mol and -9.554 kJ/mol respectively for the adsorption of β-carotene on AAB at 65 deg. C, and for adsorption of chlorophyll on AAB at 65 deg. C were 31.051 kJ/mol, 93.549 J/K mol and -0.729 kJ/mol, respectively. The adsorption of β-carotene and chlorophyll in xylene solution on AAB was a spontaneous and endothermic process with increasing in the randomness at the solid-solution interface.

  17. Thermodynamic analysis of combined Solid Oxide Electrolyzer and Fischer–Tropsch processes

    International Nuclear Information System (INIS)

    Stempien, Jan Pawel; Ni, Meng; Sun, Qiang; Chan, Siew Hwa

    2015-01-01

    In this paper a thermodynamic analysis and simple optimization of a combined Solid Oxide Electrolyzer Cell and Fisher–Tropsch Synthesis processes for sustainable hydrocarbons fuel production is reported. Comprehensive models are employed to describe effects of temperature, pressure, reactant composition and molar flux and flow on the system efficiency and final production distribution. The electrolyzer model was developed in-house and validated with experimental data of a typical Solid Oxide Electrolyzer. The Fischer–Tropsch Synthesis model employed lumped kinetics of syngas utilization, which includes inhibiting effect of water content and kinetics of Water–Gas Shift reaction. Product distribution model incorporated olefin re-adsorption and varying physisorption and solubility of hydrocarbons with their carbon number. The results were compared with those reported by Becker et al. with simplified analysis of such process. In the present study an opposite effect of operation at elevated pressure was observed. Proposed optimized system achieved overall efficiency of 66.67% and almost equal spread of light- (31%wt), mid-(36%wt) and heavy-hydrocarbons (33%wt). Paraffins contributed the majority of the yield. - Highlights: • Analysis of Solid Oxide Electrolyzer combined with Fisher Tropsch process. • Efficiency of converting water and carbon dioxide into synthetic fuels above 66%. • Effects of process temperature, pressure, gas flux and compositions were analyzed

  18. An analytical longitudinal dielectric function of primitive electrolyte solutions and its application in predicting thermodynamic properties

    International Nuclear Information System (INIS)

    Xiao, Tiejun

    2015-01-01

    In this paper, the longitudinal dielectric function ϵ_l(k) of primitive electrolyte solutions is discussed. Starting from a modified mean spherical approximation, an analytical dielectric function in terms of two parameters is established. These two parameters can be related to the first two decay parameters k_1_,_2 of the dielectric response modes of the bulk system, and can be determined using constraints of k_1_,_2 from statistical theories. Furthermore, a combination of this dielectric function and the molecular Debye-Hückel theory[J. Chem. Phys. 135(2011)104104] leads to a self-consistent mean filed description of electrolyte solutions. Our theory reveals a relationship between the microscopic structure parameters of electrolyte solutions and the macroscopic thermodynamic properties, which is applied to concentrated electrolyte solutions.

  19. Families of optimal thermodynamic solutions for combined cycle gas turbine (CCGT) power plants

    International Nuclear Information System (INIS)

    Godoy, E.; Scenna, N.J.; Benz, S.J.

    2010-01-01

    Optimal designs of a CCGT power plant characterized by maximum second law efficiency values are determined for a wide range of power demands and different values of the available heat transfer area. These thermodynamic optimal solutions are found within a feasible operation region by means of a non-linear mathematical programming (NLP) model, where decision variables (i.e. transfer areas, power production, mass flow rates, temperatures and pressures) can vary freely. Technical relationships among them are used to systematize optimal values of design and operative variables of a CCGT power plant into optimal solution sets, named here as optimal solution families. From an operative and design point of view, the families of optimal solutions let knowing in advance optimal values of the CCGT variables when facing changes of power demand or adjusting the design to an available heat transfer area.

  20. Entropy production in a fluid-solid system far from thermodynamic equilibrium.

    Science.gov (United States)

    Chung, Bong Jae; Ortega, Blas; Vaidya, Ashwin

    2017-11-24

    The terminal orientation of a rigid body in a moving fluid is an example of a dissipative system, out of thermodynamic equilibrium and therefore a perfect testing ground for the validity of the maximum entropy production principle (MaxEP). Thus far, dynamical equations alone have been employed in studying the equilibrium states in fluid-solid interactions, but these are far too complex and become analytically intractable when inertial effects come into play. At that stage, our only recourse is to rely on numerical techniques which can be computationally expensive. In our past work, we have shown that the MaxEP is a reliable tool to help predict orientational equilibrium states of highly symmetric bodies such as cylinders, spheroids and toroidal bodies. The MaxEP correctly helps choose the stable equilibrium in these cases when the system is slightly out of thermodynamic equilibrium. In the current paper, we expand our analysis to examine i) bodies with fewer symmetries than previously reported, for instance, a half-ellipse and ii) when the system is far from thermodynamic equilibrium. Using two-dimensional numerical studies at Reynolds numbers ranging between 0 and 14, we examine the validity of the MaxEP. Our analysis of flow past a half-ellipse shows that overall the MaxEP is a good predictor of the equilibrium states but, in the special case of the half-ellipse with aspect ratio much greater than unity, the MaxEP is replaced by the Min-MaxEP, at higher Reynolds numbers when inertial effects come into play. Experiments in sedimentation tanks and with hinged bodies in a flow tank confirm these calculations.

  1. Solution phase thermodynamics of strong electrolytes based on ionic concentrations, hydration numbers and volumes of dissolved entities

    Czech Academy of Sciences Publication Activity Database

    Heyrovská, Raji

    2013-01-01

    Roč. 24, č. 6 (2013), s. 1895-1901 ISSN 1040-0400 Institutional support: RVO:68081707 Keywords : Solution thermodynamics * Aqueous electrolytes * Partial electrolytic dissociation Subject RIV: BO - Biophysics Impact factor: 1.900, year: 2013

  2. Solvation thermodynamics and heat capacity of polar and charged solutes in water

    Science.gov (United States)

    Sedlmeier, Felix; Netz, Roland R.

    2013-03-01

    The solvation thermodynamics and in particular the solvation heat capacity of polar and charged solutes in water is studied using atomistic molecular dynamics simulations. As ionic solutes we consider a F- and a Na+ ion, as an example for a polar molecule with vanishing net charge we take a SPC/E water molecule. The partial charges of all three solutes are varied in a wide range by a scaling factor. Using a recently introduced method for the accurate determination of the solvation free energy of polar solutes, we determine the free energy, entropy, enthalpy, and heat capacity of the three different solutes as a function of temperature and partial solute charge. We find that the sum of the solvation heat capacities of the Na+ and F- ions is negative, in agreement with experimental observations, but our results uncover a pronounced difference in the heat capacity between positively and negatively charged groups. While the solvation heat capacity ΔCp stays positive and even increases slightly upon charging the Na+ ion, it decreases upon charging the F- ion and becomes negative beyond an ion charge of q = -0.3e. On the other hand, the heat capacity of the overall charge-neutral polar solute derived from a SPC/E water molecule is positive for all charge scaling factors considered by us. This means that the heat capacity of a wide class of polar solutes with vanishing net charge is positive. The common ascription of negative heat capacities to polar chemical groups might arise from the neglect of non-additive interaction effects between polar and apolar groups. The reason behind this non-additivity is suggested to be related to the second solvation shell that significantly affects the solvation thermodynamics and due to its large spatial extent induces quite long-ranged interactions between solvated molecular parts and groups.

  3. Equilibrium, kinetic and thermodynamic studies of adsorption of Th(IV) from aqueous solution onto kaolin

    International Nuclear Information System (INIS)

    Hongxia Zhang; Zhiwei Niu; Zhi Liu; Zhaodong Wen; Weiping Li; Xiaoyun Wang; Wangsuo Wu

    2015-01-01

    The kinetics and thermodynamics of the adsorption of Th(IV) on the kaolin were studied by using batch method. In addition, the experimental data were studied by dynamic and thermodynamic models. The results showed that the adsorption capacity of the adsorbent increased with increasing temperature and solid liquid ratio, but decreased with increasing initial Th(IV) ion concentration, and the best fit was obtained for the pseudo-second-order kinetics model. The calculated activation energy for adsorption was about 45 kJ/mol, which indicated the adsorption process to be chemisorption. The adsorption isotherm data could be well described by the Langmuir as well as Dubinin-Radushkevich model. The mean free energy (E) of adsorption was calculated to be about 15 kJ/mol. The thermodynamic data calculated showed that the adsorption was spontaneous and enhanced at higher temperature. Considering kinetics and equilibrium studies, the adsorption on the sites was the rate-limiting step and that adsorption was mainly a chemisorption process through cation exchange. (author)

  4. Thermodynamic analysis of synthetic hydrocarbon fuel production in pressurized solid oxide electrolysis cells

    DEFF Research Database (Denmark)

    Sun, Xiufu; Chen, Ming; Jensen, Søren Højgaard

    2012-01-01

    A promising way to store wind and solar electricity is by electrolysis of H2O and CO2 using solid oxide electrolysis cells (SOECs) to produce synthetic hydrocarbon fuels that can be used in existing fuel infrastructure. Pressurized operation decreases the cell internal resistance and enables...... improved system efficiency, potentially lowering the fuel production cost significantly. In this paper, we present a thermodynamic analysis of synthetic methane and dimethyl ether (DME) production using pressurized SOECs, in order to determine feasible operating conditions for producing the desired......, and outlet gas composition. For methane production, low temperature and high pressure operation could improve the system efficiency, but might lead to a higher capital cost. For DME production, high pressure SOEC operation necessitates higher operating temperature in order to avoid carbon formation at higher...

  5. Thermodynamic and kinetic analysis of solid-phase interaction of alkali metal carbonates with arsenic pentoxide

    International Nuclear Information System (INIS)

    Pashinkin, A.S.; Buketov, E.A.; Isabaeva, S.M.; Kasenov, B.K.

    1985-01-01

    The thermodynamic analysis of solid-phase reactions of alkali metal carbonates with arsenic pentoxide showing the possibility of formation of all arsenates at a higher than the room temperature is performed. Energetically most advantageous is formation of meta-arsenates. It is shown that temperature increase favours the reaction process. By Gibbs standard energy decrease the reactions form the Li>Na>K>Rb>Cs series. On the base of calculation data linear dependence of Gibbs standard energy in reactions on the atomic number of alkali metalis established. By the continuous weighing method the kinetics of interaction of alkali metal carbonates with arsenic pentoxide under isothermal conditions in the 450-500 deg C range is studied. Studies is the dependence of apparent energy of interaction of carbonates wih As 2 0 5 an atomic parameters of al

  6. Investigation of samarium solubility in the magnesium based solid solution

    International Nuclear Information System (INIS)

    Rokhlin, L.L.; Padezhnova, E.M.; Guzej, L.S.

    1976-01-01

    Electric resistance measurements and microscopic analysis were used to investigate the solubility of samarium in a magnesium-based solid solution. The constitutional diagram Mg-Sm on the magnesium side is of an eutectic type with the temperature of the eutectic transformation of 542 deg C. Samarium is partly soluble in solid magnesium, the less so, the lower is the temperature. The maximum solubility of samarium in magnesium (at the eutectic transformation point) is 5.8 % by mass (0.99 at. %). At 200 deg C, the solubility of samarium in magnesium is 0.4 % by mass (0.063 at. %)

  7. Exact solution and thermodynamics of a spin chain with long-range elliptic interactions

    International Nuclear Information System (INIS)

    Finkel, Federico; González-López, Artemio

    2014-01-01

    We solve in closed form the simplest (su(1|1)) supersymmetric version of Inozemtsev's elliptic spin chain, as well as its infinite (hyperbolic) counterpart. The solution relies on the equivalence of these models to a system of free spinless fermions and on the exact computation of the Fourier transform of the resulting elliptic hopping amplitude. We also compute the thermodynamic functions of the finite (elliptic) chain and their low temperature limit and show that the energy levels become normally distributed in the thermodynamic limit. Our results indicate that at low temperatures the su(1|1) elliptic chain behaves as a critical XX model and deviates in an essential way from the Haldane–Shastry chain. (paper)

  8. Mass transfer and thermodynamic modeling of carbon dioxide absorption into MEA aqueous solution

    Directory of Open Access Journals (Sweden)

    Ghaemi Ahad

    2017-09-01

    Full Text Available In this research, thermodynamic and absorption rate of carbon dioxide in monoethanolamine (MEA solution was investigated. A correlation based on both liquid and a gas phase variable for carbon dioxide absorption rate was presented using the π-Buckingham theorem. The correlation was constructed based on dimensionless numbers, including carbon dioxide loading, carbon dioxide partial pressure, film parameter and the ratio of liquid phase film thickness and gas phase film thickness. The film parameter is used to apply the effect of chemical reactions on absorption rate. A thermodynamic model based on the extended-UNIQUAC equations for the activity coefficients coupled with the Virial equation of state for representing the non-ideality of the vapor phase was used to predict the CO2 solubility in the CO2-MEA-H2O system. The average absolute error of the results for the correlation was 6.4%, which indicates the accuracy of the proposed correlation.

  9. Extended UNIQUAC model for thermodynamic modeling of CO2 absorption in aqueous alkanolamine solutions

    DEFF Research Database (Denmark)

    Faramarzi, Leila; Kontogeorgis, Georgios; Thomsen, Kaj

    2009-01-01

    The extended UNIQUAC model [K. Thomsen, R Rasmussen, Chem. Eng. Sci. 54 (1999) 1787-1802] was applied to the thermodynamic representation of carbon dioxide absorption in aqueous monoethanolamine (MEA), methyldiethanolamine (MDEA) and varied strength mixtures of the two alkanolamines (MEA-MDEA). F......The extended UNIQUAC model [K. Thomsen, R Rasmussen, Chem. Eng. Sci. 54 (1999) 1787-1802] was applied to the thermodynamic representation of carbon dioxide absorption in aqueous monoethanolamine (MEA), methyldiethanolamine (MDEA) and varied strength mixtures of the two alkanolamines (MEA......) are included in the parameter estimation process. The previously unavailable standard state properties of the alkanolamine ions appearing in this work, i.e. MEA protonate, MEA carbamate and MDEA protonate are determined. The concentration of the species in both MEA and MDEA solutions containing CO2...

  10. Dislocation cross-slip in fcc solid solution alloys

    International Nuclear Information System (INIS)

    Nöhring, Wolfram Georg; Curtin, W.A.

    2017-01-01

    Cross-slip is a fundamental process of screw dislocation motion and plays an important role in the evolution of work hardening and dislocation structuring in metals. Cross-slip has been widely studied in pure FCC metals but rarely in FCC solid solutions. Here, the cross-slip transition path in solid solutions is calculated using atomistic methods for three representative systems of Ni-Al, Cu-Ni and Al-Mg over a range of solute concentrations. Studies using both true random alloys and their corresponding average-alloy counterparts allow for the independent assessment of the roles of (i) fluctuations in the spatial solute distribution in the true random alloy randomness and (ii) average alloy properties such as stacking fault energy. The results show that the solute fluctuations dominate the activation energy barrier, i.e. there are large sample-to-sample variations around the average activation barrier. The variations in activation barrier correlate linearly with the energy difference between the initial and final states. The distribution of this energy difference can be computed analytically in terms of the solute/dislocation interaction energies. Thus, the distribution of cross-slip activation energies can be accurately determined from a parameter-free analytic model. The implications of the statistical distribution of activation energies on the rate of cross-slip in real alloys are then identified.

  11. Thermodynamic pathways to melting, ablation, and solidification in absorbing solids under pulsed laser irradiation

    International Nuclear Information System (INIS)

    Lorazo, Patrick; Lewis, Laurent J.; Meunier, Michel

    2006-01-01

    The thermodynamic pathways involved in laser irradiation of absorbing solids are investigated in silicon for pulse durations of 500 fs and 100 ps. This is achieved by accounting for carrier and atom dynamics within a combined Monte Carlo and molecular-dynamics scheme and simultaneously tracking the time evolution of the irradiated material in ρ-T-P space. Our simulations reveal thermal changes in long-range order and state of aggregation driven, in most cases, by nonequilibrium states of rapidly heated or promptly cooled matter. Under femtosecond irradiation near the ablation threshold, the system is originally pulled to a near-critical state following rapid ( -12 s) disordering of the mechanically unstable crystal and isochoric heating of the resulting metallic liquid. The latter is then adiabatically cooled to the liquid-vapor regime where phase explosion of the subcritical, superheated melt is initiated by a direct conversion of translational, mechanical energy into surface energy on a ∼10 -12 -10 -11 s time scale. At higher fluences, matter removal involves, instead, the fragmentation of an initially homogeneous fluid subjected to large strain rates upon rapid, supercritical expansion in vacuum. Under picosecond irradiation, homogeneous and, at later times, heterogeneous melting of the superheated solid are followed by nonisochoric heating of the molten metal. In this case, the subcritical liquid material is subsequently cooled onto the binodal by thermal conduction and explosive boiling does not take place; as a result, ablation is associated with a ''trivial'' fragmentation process, i.e., the relatively slow expansion and dissociation into liquid droplets of supercritical matter near thermodynamic equilibrium. This implies a liquid-vapor equilibration time of ∼10 -11 -10 -10 s and heating along the binodal under nanosecond irradiation. Solidification of the nonablated, supercooled molten material is eventually observed on a ∼10 -11 -10 -9 s time scale

  12. System Tb-Fe-O: thermodynamic properties of ternary oxides using solid-state electrochemical cells

    International Nuclear Information System (INIS)

    Rakshit, S.K.; Parida, S.C.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

    2003-01-01

    The standard molar Gibbs free energies of formation of TbFeO 3 (s) and Tb 3 Fe 5 O 12 (s) have been determined using solid-state electrochemical cell employing different solid electrolytes. The reversible emfs of the following solid-state electrochemical cells have been measured in the temperature range 1050≤T/K≤1250. Cell (I):(-)Pt/{TbFeO 3 (s)+Tb 2 O 3 (s)+Fe(s)}//YDT/CSZ//{Fe(s)+Fe 0.95 O(s)}/Pt(+))) (Cell (II):(-)Pt/{Fe(s)+Fe 0.95 O(s)}//CSZ//{TbFeO 3 (s)+Tb 3 Fe 5 O 12 (s)+Fe 3 O 4 (s)}/Pt(+) The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the emf data. The standard molar Gibbs free energies of formation of solid TbFeO 3 and Tb 3 Fe 5 O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by {Δ f G compfn m (TbFeO 3 ,s)/(kJ·mol -1 )±3.2}=-1357.5+0.2531·(T/K); (1050≤T/K≤1548);))and({Δ f G compfn m (Tb 3 Fe 5 O 12 ,s)/(kJ·mol -1 )±3.5}=-4901.7+ 0.9997·(T/K); (1050≤T/K≤1250).)) The uncertainty estimates for Δ f G compfn m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams were computed for the system Tb-Fe-O at T=1250 K

  13. Solid solutions of hydrogen in niobium, molybdenum and their alloys

    International Nuclear Information System (INIS)

    Ishikawa, T.T.

    1981-01-01

    The solubility of hydrogen in niobium, molybdenum and niobium-molybdenum alloys with varying atomic fraction of molybdenum from 0.15 to 0.75 was measured on the temperature range of 673 0 K to 1273 0 k for one atmosphere hydrogen pressure. The experimental technique involved the saturation of the solvent metal or alloy with hydrogen, followed by quenching and analysis of the solid solution. The results obtained of hydrogen solubility are consistent with the quasi-regular model for the dilute interstitial solid solutions. The partial molar enthalpy and partial molar entropy in excess of the dissolved hydrogen atoms were calculated from data of solubility versus reciprocal doping temperature. The variation of the relative partial molar enthalpy of hydrogen dissolved in niobium-molybdenum alloys, with the increase of molybdenum content of the alloy was analized. (Author) [pt

  14. Thermodynamics of micelle formation in a water-alcohol solution of sodium tetradecyl sulfate

    Science.gov (United States)

    Shilova, S. V.; Tret'yakova, A. Ya.; Barabanov, V. P.

    2016-01-01

    The effects of addition of ethanol and propan-1-ol on sodium tetradecyl sulfate micelle formation in an aqueous solution are studied via microprobe fluorescence microscopy and conductometry. The critical micelle concentration, quantitative characteristics of micelles, and thermodynamic parameters of micelle formation are determined. Addition of 5-15 vol % of ethanol or 5-10 vol % of propan-1-ol is shown to result in a lower critical micelle concentration than in the aqueous solution, and in the formation of mixed spherical micelles whose sizes and aggregation numbers are less than those for the systems without alcohol. The contribution from the enthalpy factor to the free energy of sodium tetradecyl sulfate micelle formation is found to dominate in mixed solvents, in contrast to aqueous solutions.

  15. Magnetic clusters in ilmenite-hematite solid solutions

    DEFF Research Database (Denmark)

    Frandsen, Cathrine; Burton, B. P.; Rasmussen, Helge Kildahl

    2010-01-01

    We report the use of high-field 57Fe Mössbauer spectroscopy to resolve the magnetic ordering of ilmenite-hematite [xFeTiO3−(1−x)Fe2O3] solid solutions with x>0.5. We find that nanometer-sized hematite clusters exist within an ilmenite-like matrix. Although both phases are antiferromagnetically...

  16. Fabrication of nanocrystalline alloys Cu–Cr–Mo super satured solid solution by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzmán, D. [Departamento de Ingeniería en Metalurgia, Facultad de Ingeniería, Universidad de Atacama y Centro Regional de Investigación y Desarrollo Sustentable de Atacama (CRIDESAT), Av. Copayapu 485, Copiapó (Chile); Castro, F.; Martínez, V.; Cuevas, F. de las [Centro de Estudios e Investigaciones Técnicas de Gipuzkoa, Paseo de Manuel Lardizábal, N° 15, 20018 San Sebastián (Spain); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Muthiah, T. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile)

    2014-08-01

    This work discusses the extension of solid solubility of Cr and Mo in Cu processed by mechanical alloying. Three alloys processed, Cu–5Cr–5Mo, Cu–10Cr–10Mo and Cu–15Cr–15Mo (weight%) using a SPEX mill. Gibbs free energy of mixing values 10, 15 and 20 kJ mol{sup −1} were calculated for these three alloys respectively by using the Miedema's model. The crystallite size decreases and dislocation density increases when the milling time increases, so Gibbs free energy storage in powders increases by the presence of crystalline defects. The energy produced by crystallite boundaries and strain dislocations were estimated and compared with Gibbs free energy of mixing values. The energy storage values by the presence of crystalline defects were higher than Gibbs free energy of mixing at 120 h for Cu–5Cr–5Mo, 130 h for Cu–10Cr–10Mo and 150 h for Cu–15Cr–15Mo. During milling, crystalline defects are produced that increases the Gibbs free energy storage and thus the Gibbs free energy curves are moved upwards and hence the solubility limit changes. Therefore, the three alloys form solid solutions after these milling time, which are supported with the XRD results. - Highlights: • Extension of solid solution Cr and Mo in Cu achieved by mechanical alloying. • X-ray characterization of Cu–Cr–Mo system processed by mechanical alloying. • Thermodynamics analysis of formation of solid solution of the Cu–Cr–Mo system.

  17. Prediction of thermodynamic instabilities of protein solutions from simple protein–protein interactions

    International Nuclear Information System (INIS)

    D’Agostino, Tommaso; Solana, José Ramón; Emanuele, Antonio

    2013-01-01

    Highlights: ► We propose a model of effective protein–protein interaction embedding solvent effects. ► A previous square-well model is enhanced by giving to the interaction a free energy character. ► The temperature dependence of the interaction is due to entropic effects of the solvent. ► The validity of the original SW model is extended to entropy driven phase transitions. ► We get good fits for lysozyme and haemoglobin spinodal data taken from literature. - Abstract: Statistical thermodynamics of protein solutions is often studied in terms of simple, microscopic models of particles interacting via pairwise potentials. Such modelling can reproduce the short range structure of protein solutions at equilibrium and predict thermodynamics instabilities of these systems. We introduce a square well model of effective protein–protein interaction that embeds the solvent’s action. We modify an existing model [45] by considering a well depth having an explicit dependence on temperature, i.e. an explicit free energy character, thus encompassing the statistically relevant configurations of solvent molecules around proteins. We choose protein solutions exhibiting demixing upon temperature decrease (lysozyme, enthalpy driven) and upon temperature increase (haemoglobin, entropy driven). We obtain satisfactory fits of spinodal curves for both the two proteins without adding any mean field term, thus extending the validity of the original model. Our results underline the solvent role in modulating or stretching the interaction potential

  18. Solution thermodynamics of pyrazinamide, isoniazid, and p-aminobenzoic acid in buffers and octanol

    International Nuclear Information System (INIS)

    Blokhina, Svetlana V.; Ol’khovich, Marina V.; Sharapova, Angelica V.; Volkova, Tatyana V.; Perlovich, German L.

    2015-01-01

    Highlights: • Solubility of pyrazinamide, isoniazid, p-aminobenzoic acid were measured. • The activity coefficients of the compounds at infinite dilution were determined. • Thermodynamic functions of dissolution and solvation were calculated. - Abstract: The solubility values of pyrazinamide, isoniazid, and p-aminobenzoic acid in buffers (pH 2.0 and 7.4) and octanol were measured in the temperature range of 293.15 to 313.15 K. The dissolution Gibbs energy, enthalpy, and entropy were calculated. The dissolving process was endothermic and enthalpy-determined. The activity coefficients of the compounds at infinite dilution were determined based on the solubility data and thermophysical parameters. A positive deviation from the ideality was observed in all the solutions. A common tendency of the solubility increase with a decrease in the activity coefficients at T = 298.15 K was revealed for the investigated solute-solvent systems. The excess thermodynamic solubility functions were calculated from the temperature dependences of the activity coefficients. The solvation processes were found to have a considerable influence on the solubility of the substances in solutions studied.

  19. X-Ray Characterization of Non-Equilibrium Solid Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Brown, A; Rosdahl, Oe

    1975-07-01

    The Rudman approach to composition line broadening in X-ray diffraction patterns, originally designed for the study of diffusion in alloys, is seen to provide a basis for characterizing inhomogeneous solid solutions. Limitations, imposed on this treatment when the cell dimensions of the primary components differ by less than 0.1 A, are attributable to experimental effects such as instrument broadening. These limitations can be overcome by a rigorous numerical treatment of the measured data. Thus, separate elimination of the Kalpha{sub 2} radiation component followed by iterative deconvolution are advocated for the recovery of the intrinsic broadening. This course of action is made possible chiefly through the availability of large, fast memory computers and primary data recorded in the form of a step scan on punched paper tape. The characteristics of inhomogeneous solid solutions made available by the above treatment are the identity of closely similar, solid solution phases, the frequency distribution curve for a chosen component, and the degree of homogeneity of the X-ray sample

  20. X-Ray Characterization of Non-Equilibrium Solid Solutions

    International Nuclear Information System (INIS)

    Brown, A.; Rosdahl, Oe.

    1975-01-01

    The Rudman approach to composition line broadening in X-ray diffraction patterns, originally designed for the study of diffusion in alloys, is seen to provide a basis for characterizing inhomogeneous solid solutions. Limitations, imposed on this treatment when the cell dimensions of the primary components differ by less than 0.1 A, are attributable to experimental effects such as instrument broadening. These limitations can be overcome by a rigorous numerical treatment of the measured data. Thus, separate elimination of the Kα 2 radiation component followed by iterative deconvolution are advocated for the recovery of the intrinsic broadening. This course of action is made possible chiefly through the availability of large, fast memory computers and primary data recorded in the form of a step scan on punched paper tape. The characteristics of inhomogeneous solid solutions made available by the above treatment are the identity of closely similar, solid solution phases, the frequency distribution curve for a chosen component, and the degree of homogeneity of the X-ray sample

  1. Thermodynamic analysis of SOFC (solid oxide fuel cell)–Stirling hybrid plants using alternative fuels

    International Nuclear Information System (INIS)

    Rokni, Masoud

    2013-01-01

    A novel hybrid power system (∼10 kW) for an average family home is proposed. The system investigated contains a solid oxide fuel cell (SOFC) on top of a Stirling engine. The off-gases produced in the SOFC cycle are fed to a bottoming Stirling engine, at which additional power is generated. Simulations of the proposed system were conducted using different fuels, which should facilitate the use of a variety of fuels depending on availability. Here, the results for natural gas (NG), ammonia, di-methyl ether (DME), methanol and ethanol are presented and analyzed. The system behavior is further investigated by comparing the effects of key factors, such as the utilization factor and the operating conditions under which these fuels are used. Moreover, the effect of using a methanator on the plant efficiency is also studied. The combined system improves the overall electrical efficiency relative to that of a stand-alone Stirling engine or SOFC plant. For the combined SOFC and Stirling configuration, the overall power production was increased by approximately 10% compared to that of a stand-alone SOFC plant. System efficiencies of approximately 60% are achieved, which is remarkable for such small plant sizes. Additionally, heat is also produced to heat the family home when necessary. - Highlights: • Integrating a solid oxide fuel with a Stirling engine • Design of multi-fuel hybrid plants • Plants running on alternative fuels; natural gas, methanol, ethanol, DME and ammonia • Thermodynamic analysis of hybrid SOFC–Stirling engine plants

  2. Statistical thermodynamics

    International Nuclear Information System (INIS)

    Lim, Gyeong Hui

    2008-03-01

    This book consists of 15 chapters, which are basic conception and meaning of statistical thermodynamics, Maxwell-Boltzmann's statistics, ensemble, thermodynamics function and fluctuation, statistical dynamics with independent particle system, ideal molecular system, chemical equilibrium and chemical reaction rate in ideal gas mixture, classical statistical thermodynamics, ideal lattice model, lattice statistics and nonideal lattice model, imperfect gas theory on liquid, theory on solution, statistical thermodynamics of interface, statistical thermodynamics of a high molecule system and quantum statistics

  3. Thermodynamics of oxygen solutions in Fe-40% Ni-15% Cr melts containing Mn, Si, Ti, Al

    International Nuclear Information System (INIS)

    Dashevskij, V.Ya.; Makarova, N.N.; Grigorovich, K.V.; Kashin, V.I.; Polikarpova, N.V.

    2000-01-01

    Thermodynamic analysis and experimental studied are performed for oxygen solutions in Fe-40% Ni-15% Cr melts where Mn, Si, Ti, Al are used as reducing agents. It is revealed that in the alloys studied the affinity of reducing agents to oxygen essentially lower than in liquid iron, nickel and Fe-40% Ni alloy. This is explained by the fact that the oxygen activity in melts noticeably decreases due to a high chromium content whereas the activity of reducing elements increases in a rather less degree. The agreement between analytical and experimental results confirms the validity of the calculation technique [ru

  4. Thermodynamic stabilization of colloids

    NARCIS (Netherlands)

    Stol, R.J.; Bruyn, P.L. de

    An analysis is given of the conditions necessary for obtaining a thermodynamically stable dispersion (TSD) of solid particles in a continuous aqueous solution phase. The role of the adsorption of potential-determining ions at the planar interface in lowering the interfacial free energy (γ) to

  5. Thermodynamic modeling of La2O3-SrO-Mn2O3-Cr2O3 for solid oxide fuel cell applications

    DEFF Research Database (Denmark)

    Povoden-Karadeniz, E.; Chen, Ming; Ivas, Toni

    2012-01-01

    The thermodynamic La–Sr–Mn–Cr–O oxide database is obtained as an extension of thermodynamic descriptions of oxide subsystems using the calculation of phase diagrams approach. Concepts of the thermodynamic modeling of solid oxide phases are discussed. Gibbs energy functions of SrCrO4, Sr2.67Cr2O8......, Sr2CrO4, and SrCr2O4 are presented, and thermodynamic model parameters of La–Sr–Mn–Chromite perovskite are given. Experimental solid solubilities and nonstoichiometries in La1xSrxCrO3d and LaMn1xCrxO3d are reproduced by the model. The presented oxide database can be used for applied computational...... thermodynamics of traditional lanthanum manganite cathode with Cr-impurities. It represents the fundament for extensions to higher orders, aiming on thermodynamic calculations in noble symmetric solid oxide fuel cells...

  6. Formation and thermodynamic stability of (polymer + porphyrin) supramolecular structures in aqueous solutions

    International Nuclear Information System (INIS)

    Costa, Viviana C.P. da; Hwang, Barrington J.; Eggen, Spencer E.; Wallace, Megan J.; Annunziata, Onofrio

    2014-01-01

    Highlights: • Thermodynamic stability of a (polymer + porphyrin) supramolecular structure was characterized. • Isothermal titration calorimetry provided two ways to determine reaction enthalpies. • Exothermic (polymer + porphyrin) binding competes with porphyrin self-association. • (Polymer + porphyrin) binding is entropically favored with respect to porphyrin self-association. • Spectral shifts show importance of porphyrin central hydrogens in polymer binding. - Abstract: Optical properties of porphyrins can be tuned through (polymer + porphyrin) (host + guest) binding in solution. This gives rise to the formation of supramolecular structures. In this paper, the formation, thermodynamic stability and spectroscopic properties of (polymer + porphyrin) supramolecular structures and their competition with porphyrin self-association were investigated by both isothermal titration calorimetry (ITC) and absorption spectroscopy. Specifically, reaction enthalpies and equilibrium constants were measured for meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) self-association and TPPS binding to the polymer poly(vinylpyrrolidone) (PVP, 40 kg/mol) in aqueous solutions at pH 7 and three different temperatures (12, 25 and 37 °C). ITC, compared to spectroscopic techniques, provides two independent means to determine reaction enthalpies: direct measurements and Van’t Hoff plot. This was used as a criterion to assess that (1) self-association of TPPS is limited to the formation of dimers and (2) TPPS binds to PVP in its monomeric state only. The formation of TPPS dimers and (PVP + TPPS) supramolecular structures are both enthalpically driven. However, (polymer + porphyrin) binding was found to be entropically favored compared to dimerization. Furthermore, the reaction enthalpies of these two processes significantly depend on temperature. This behavior was attributed to hydrophobic interactions. Finally, the limiting absorption spectra of monomeric, dimeric and polymer

  7. A metallic solution model with adjustable parameter for describing ternary thermodynamic properties from its binary constituents

    International Nuclear Information System (INIS)

    Fang Zheng; Qiu Guanzhou

    2007-01-01

    A metallic solution model with adjustable parameter k has been developed to predict thermodynamic properties of ternary systems from those of its constituent three binaries. In the present model, the excess Gibbs free energy for a ternary mixture is expressed as a weighted probability sum of those of binaries and the k value is determined based on an assumption that the ternary interaction generally strengthens the mixing effects for metallic solutions with weak interaction, making the Gibbs free energy of mixing of the ternary system more negative than that before considering the interaction. This point is never considered in the models currently reported, where the only difference in a geometrical definition of molar values of components is considered that do not involve thermodynamic principles but are completely empirical. The current model describes the results of experiments very well, and by adjusting the k value also agrees with those from models used widely in the literature. Three ternary systems, Mg-Cu-Ni, Zn-In-Cd, and Cd-Bi-Pb are recalculated to demonstrate the method of determining k and the precision of the model. The results of the calculations, especially those in Mg-Cu-Ni system, are better than those predicted by the current models in the literature

  8. Self-association and thermodynamic behavior of etilefrine hydrochloride in aqueous electrolyte solution

    International Nuclear Information System (INIS)

    Elmasry, Manal S.; Hassan, Wafaa S.; Elazazy, Marwa S.

    2014-01-01

    Highlights: • The self-association of etilefrine HCl in aqueous solution has been studied. • Conductivity and 1 H NMR measurements were used to study the self association. • The critical micelle concentrations and the degree of ionizations were calculated. • The effect of different temperatures and NaCl concentrations were studied. • The thermodynamic parameters of self association of etilefrine HCl were evaluated. - Abstract: The self-association (micellization) behavior of etilefrine HCl, an amphiphilic drug, in aqueous electrolyte solution has been investigated as a function of temperature and sodium chloride (NaCl) concentration by conductivity and 1 H NMR measurements. The critical micelle concentration (CMC) was calculated from the inflection in the data obtained from both techniques. The CMC and the degree of ionization (α) values were determined over the temperature range (298.15 to 313.15) K in water and in presence of different concentrations of NaCl. The thermodynamic parameters of micellization for etilefrine HCl i.e. the standard Gibbs free energy change ΔG° m , the standard enthalpy change, ΔH° m , and the standard entropy change, ΔS° m , were evaluated according to the pseudo-phase model. The obtained CMC values, in presence and absence of electrolyte, showed an inverted U-shaped behavior. While the degree of micelle ionization (α) showed a linear response to the increase in temperature in absence of electrolyte, addition of NaCl did not cause a specific response

  9. Synthesis and characterization of solid solutions in ABCO 4 system

    Science.gov (United States)

    Novoselov, A.; Zimina, G.; Komissarova, L.; Pajaczkowska, A.

    2006-01-01

    Formation of continuous solid solutions with a tetragonal structure of K 2NiF 4-type was investigated by direct solid-state synthesis, carbonate precipitations, the freeze-drying method and the Czochralski crystal growth technique. In the systems of SrLaAlO 4-CaLaAlO 4, SrNdAlO 4-CaNdAlO 4, SrPrAlO 4-CaPrAlO 4, SrLaAlO 4-SrLaGaO 4 and SrLaAlO 4-SrLaFeO 4 solid solutions are formed in the whole concentration range (0.0⩽ x⩽1.0) and in the systems of SrLaAlO 4-SrLaMnO 4 and SrLaAlO 4-SrLaCrO 4 in the limited compositional interval of (0.0⩽ x⩽0.20) and (0.0⩽ x⩽0.25), respectively, with composition dependency of lattice constants following Vegard's law.

  10. THERMODYNAMIC PROPERTIES OF NONAQUEOUS SINGLE SALT SOLUTIONS USING THE Q-ELECTROLATTICE EQUATION OF STATE

    Directory of Open Access Journals (Sweden)

    A. Zuber

    2015-09-01

    Full Text Available AbstractThe correlation of thermodynamic properties of nonaqueous electrolyte solutions is relevant to design and operation of many chemical processes, as in fertilizer production and the pharmaceutical industry. In this work, the Q-electrolattice equation of state (EOS is used to model vapor pressure, mean ionic activity coefficient, osmotic coefficient, and liquid density of sixteen methanol and ten ethanol solutions containing single strong 1:1 and 2:1 salts. The Q-electrolattice comprises the lattice-based Mattedi-Tavares-Castier (MTC EOS, the Born term and the explicit MSA term. The model requires two adjustable parameters per ion, namely the ionic diameter and the solvent-ion interaction energy. Predictions of osmotic coefficient at 298.15 K and liquid density at different temperatures are also presented.

  11. Direct internal steam reforming of ethanol in a solid oxide fuel cell (SOFC) - A thermodynamic analysis

    International Nuclear Information System (INIS)

    Lima da Silva, Aline; De Fraga Malfatti, Celia; Heck, Nestor Cesar; Melo Halmenschlager, Cibele

    2003-01-01

    Among the various types of fuel cells, the solid oxide fuel cell (SOFC) has attracted considerable interest due to the possibility for operation with an internal reformer and higher system efficiency. In SOFC, high operative temperature allows the direct conversion of ethanol into H 2 and CO to take place in the electrochemical cell. Ethanol is considered to be an attractive fuel because it is a renewable energy source and presents some advantages over other green fuels such as safety in storage and handling. Direct internal reforming of ethanol, however, can produce undesirable products that diminish system efficiency and, in the case of carbon deposition over the anode, promote the growth of carbon filaments attached to the anode crystallites which generate massive forces within the electrode structure leading to its rapid breakdown. In this context, a thermodynamic analysis is fundamental to predict the product distribution as well as the conditions favorable for carbon to precipitate inside the cell. Despite of such importance, there are few works in literature dealing with thermodynamic analysis of the direct internal steam reforming of ethanol in fuel cell systems. Hence, the aim of this work is to find appropriate ranges for operating conditions where carbon deposition in SOFC with direct internal reforming operation is not feasible, in temperature range of 500- 1200K. The calculation here is more complicated than that for a reformer because the disappearance of hydrogen and the generation of H 2 O from electrochemical reaction must be taken into account. In the present study, the effects of hydrogen consumption on anode components and on carbon formation are investigated. Equilibrium determinations are performed by the Gibbs energy minimization method, considering the following species: H 2 , H 2 O, CH 4 , CO, CO 2 and C gr . (graphite). The effect of the type of solid electrolyte (oxygen-conducting and hydrogen-conducting) on carbon formation is also

  12. Experimental Thermodynamics of [Na-Mg-Cl-SO4] Aqueous Solutions at GPa Pressure With Application to Icy Worlds.

    Science.gov (United States)

    Brown, J. M.; Bollengier, O.; Vance, S.

    2017-12-01

    Water competes with silicates as the main constituent of solid bodies in the outer solar system. Ganymede and Titan, the Mercury-sized satellites of Jupiter and Saturn, are made up half of water present as massive hydrospheres where pressure can reach up to 1.5 GPa. Geophysical data and planetary models unequivocally support the existence of global aqueous oceans trapped in these hydrospheres. However, the extent of these oceans and their role in the processes governing the internal structure of these moons remain unresolved. At issue is the poor to non-existent characterization, at the relevant pressures, of the properties of the aqueous fluids of significance to the outer solar system (with notably the Na-Mg-Cl-SO4 salts found in primitive chondrites), forcing current models to rely on pure water only. Our team at the University of Washington has developed an experimental apparatus to acquire the speed of sound of aqueous solutions in the 0 - 0.7 GPa and 250 - 350 K pressure and temperature ranges covering most of the conditions of existence of these extra-terrestrial oceans. Speeds of sound measured over a grid of pressures and temperatures allow calculation of the thermodynamic quantities (G, ρ, μ...) required for planetary science. Early analysis of pure water samples indicates our experimental results are on par with (at lower pressures), or better than, the IAPWS water laboratory standard, with sound speeds determined to 0.02% over our entire pressure range. For the first time at the high pressures of interest for large icy moons, we achieved the exploration of H2O-NaCl, H2O-MgSO4, H2O-Na2SO4 and H2O-MgCl2 solutions, from dilute concentrations to saturation. We are now in the process of acquiring the first data for H2O-NaCl-MgSO4 mixtures. We will briefly present our experimental setup and the underlying sound speed theory, and will then compare our results for the four endmembers, with an emphasis on their different association behavior under pressure as

  13. Determination and correlation of solubility and solution thermodynamics of oxiracetam in three (alcohol + water) binary solvents

    International Nuclear Information System (INIS)

    Li, Kangli; Du, Shichao; Wu, Songgu; Cai, Dongchen; Wang, Jinxu; Zhang, Dejiang; Zhao, Kaifei; Yang, Peng; Yu, Bo; Guo, Baisong; Li, Daixi; Gong, Junbo

    2016-01-01

    Highlights: • The solubility of racemic oxiracetam in three binary solvents were determined. • The experimental solubility of racemic oxiracetam were correlated by four models. • The dissolution thermodynamic properties of racemic oxiracetam were calculated. - Abstract: In this paper, we proposed a static analysis method to experimentally determine the (solid + liquid) equilibrium of racemic oxiracetam in (methanol + water), (ethanol + water) and (isopropanol + water) binary solvents with alcohol mole fraction ranging from 0.30 to 0.90 at atmosphere pressure (p = 0.1 MPa). For the experiments, the temperatures range from (283.15 to 308.15) K. The results showed that the solubility of oxiracetam increased with the increasing temperature, while decreased with the increasing organic solvent fraction in all three tested binary solvent systems. The modified Apelblat model, the CNIBS/Redlich–Kister model, the combined version of Jouyban–Acree model and the NRTL model were employed to correlate the measured solubility values, respectively. Additionally, some of the thermodynamic properties which can help to evaluate its dissolution behavior were obtained based on the NRTL model.

  14. Thermodynamic nonequilibrium phase change behavior and thermal properties of biological solutions for cryobiology applications.

    Science.gov (United States)

    Han, Bumsoo; Bischof, John C

    2004-04-01

    Understanding the phase change behavior of biomaterials during freezing/thawing including their thermal properties at low temperatures is essential to design and improve cryobiology applications such as cryopreservation and cryosurgery. However, knowledge of phase change behavior and thermal properties of various biomaterials is still incomplete, especially at cryogenic temperatures (solutions--either water-NaCl or phosphate buffered saline (PBS)--with various chemical additives were investigated. The chemical additives studied are glycerol and raffinose as CPAs, an AFP (Type III, molecular weight = 6500), and NaCl as a cryosurgical adjuvant. The phase change behavior was investigated using a differential scanning calorimeter (DSC) and a cryomicroscope. The specific and latent heat of these solutions were also measured with the DSC. The saline solutions have two distinct phase changes--water/ice and eutectic phase changes. During freezing, eutectic solidification of both water-NaCl and PBS are significantly supercooled below their thermodynamic equilibrium eutectic temperatures. However, their melting temperatures are close to thermodynamic equilibrium during thawing. These eutectic phase changes disappear when even a small amount (0.1 M glycerol) of CPA was added, but they are still observed after the addition of an AFP. The specific heats of these solutions are close to that of ice at very low temperatures (< or = -100 degrees C) regardless of the additives, but they increase between -100 degrees C and -30 degrees C with the addition of CPAs. The amount of latent heat, which is evaluated with sample weight, generally decreases with the addition of the additives, but can be normalized to approximately 300 J/g based on the weight of water which participates in the phase change. This illustrates that thermal properties, especially latent heat, of a biomaterial should be evaluated based on the understanding of its phase change behavior. The results of the present

  15. Thorium-d-metals compounds and solid solutions

    International Nuclear Information System (INIS)

    Chachkhiani, Z.B.; Chechernikov, V.I.; Chachkhiani, L.G.

    1986-01-01

    Thorium compounds with Fe, Co, Ni dependence of their magnetic properties on temperature, pressure and concentration of the second element are considered. Anomalous magnetic behaviour of alloys in the Th-Fe system is noted. Special attention is paid to compounds with CaCu 5 type hexagonal structure and their solid solutions. Th-Co-Ni specimens containing up to 25% Ni are ferromagnetics and the rest are paramagnetics. Specimens with 60% cobalt content do not display ferromagnetic properties up to 4.2 K. Hydrides of Th 7 M 3 H 30 type (M - Fe, Co, Ni) are also considered. Highly hydrogenized specimens (under high pressure) appear to be stronger ferromagnetics

  16. Study of Mururoa's basaltic massif alteration (French Polynesia): solid and fluid phases analysis and thermodynamical modeling

    International Nuclear Information System (INIS)

    Destrigneville, Christine

    1991-01-01

    The alteration processes occurring in the volcanics of Mururoa have been studied using petrological data on secondary minerals, chemical analyses of the interstitial fluids and isotopic analyses on both minerals and fluids. Chemical and isotopic exchanges were first modelled, then thermodynamical modeling characterized the chemical evolution during the alteration of the secondary assemblage and of the fluid. The main secondary sequences which have been observed in Mururoa volcanics result from the alteration occurring during the lavas setting. Two different processes have been evidenced. The first one is the deuteric alteration with the CO_2-rich magmatic fluid exsolved from the magma and trapped in the vesicles and the olivine microcracks of the lava intrusions. This alteration in a closed system is dominated by the solid phases when the CO_2 molar fraction in the fluid is higher than 0.25. The second process is the alteration of the lavas by seawater or a meteoric fluid. The basaltic flows present alteration assemblages composed of clay minerals and zeolites whose chemical composition has been forced by the fluid composition. Shallowness emissions of lavas result in completely argillized levels. The present interstitial fluids chemistry result from the percolation of seawater in the volcano. In the argillized levels the fluids have interacted with the clay minerals and their chemical compositions have been modified. The important chemical changes in the present interstitial fluids show that the present alteration in the volcano is higher than the fluids circulation. (author) [fr

  17. Thermodynamic analysis of solid oxide fuel cell gas turbine systems operating with various biofuels

    Energy Technology Data Exchange (ETDEWEB)

    Patel, H.C.; Woudstra, T.; Aravind, P.V. [Process and Energy Laboratory, Delft University of Technology, Section Energy Technology, Leeghwaterstraat 44, 2628 CA Delft (Netherlands)

    2012-12-15

    Solid oxide fuel cell-gas turbine (SOFC-GT) systems provide a thermodynamically high efficiency alternative for power generation from biofuels. In this study biofuels namely methane, ethanol, methanol, hydrogen, and ammonia are evaluated exergetically with respect to their performance at system level and in system components like heat exchangers, fuel cell, gas turbine, combustor, compressor, and the stack. Further, the fuel cell losses are investigated in detail with respect to their dependence on operating parameters such as fuel utilization, Nernst voltage, etc. as well as fuel specific parameters like heat effects. It is found that the heat effects play a major role in setting up the flows in the system and hence, power levels attained in individual components. The per pass fuel utilization dictates the efficiency of the fuel cell itself, but the system efficiency is not entirely dependent on fuel cell efficiency alone, but depends on the split between the fuel cell and gas turbine powers which in turn depends highly on the nature of the fuel and its chemistry. Counter intuitively it is found that with recycle, the fuel cell efficiency of methane is less than that of hydrogen but the system efficiency of methane is higher. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Np(V) carbonates in solid state and aqueous solution

    International Nuclear Information System (INIS)

    Meinrath, G.

    1994-01-01

    The solubility of NaNpO 2 CO 3 (s) in 0.1M perchlorate solution at 25 deg C in equilibrium with 1.0% CO 2 /N 2 atmosphere has been investigated as a function of pH/lg [CO 3 2- ]. The solid phase was found hexagonal with a=1008.1±0.3 pm and c=991.1±0.2 pm. A solubility product of lg Ksp(NaNpO 2 CO 3 ) = -10.22±0.02 and a formation constant of the first Np(V) carbonato species of lg β 01 = 4.52±0.02 was evaluated. For the dicarbonato species an upper limit of lg lg β 02 2 partial pressure gave evidence that carbonato species are prevailing in solutions at both 1% and 0.03% CO 2 partial pressures. (author) 26 refs.; 4 figs.; 3 tabs

  19. Nonelectrolyte NRTL-NRF model to study thermodynamics of strong and weak electrolyte solutions

    Energy Technology Data Exchange (ETDEWEB)

    Haghtalab, Ali, E-mail: haghtala@modares.ac.i [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of); Shojaeian, Abolfazl; Mazloumi, Seyed Hossein [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of)

    2011-03-15

    An electrolyte activity coefficient model is proposed by combining non-electrolyte NRTL-NRF local composition model and Pitzer-Debye-Hueckel equation as short-range and long-range contributions, respectively. With two adjustable parameters per each electrolyte, the present model is applied to correlation of the mean activity coefficients of more than 150 strong aqueous electrolyte solutions at 298.15 K. Also the results of the present model are compared with the other local composition models such as electrolyte-NRTL, electrolyte-NRTL-NRF and electrolyte-Wilson-NRF models. Moreover, the present model is used for prediction of the osmotic coefficient of several aqueous binary electrolytes systems at 298.15 K. Also the present activity coefficient model is adopted for representation of nonideality of the acid gases, as weak gas electrolytes, soluble in alkanolamine solutions. The model is applied for calculation of solubility and heat of absorption (enthalpy of solution) of acid gas in the two {l_brace}(H{sub 2}O + MDEA + CO{sub 2}) and (H{sub 2}O + MDEA + H{sub 2}S){r_brace} systems at different conditions. The results demonstrate that the present model can be successfully applied to study thermodynamic properties of both strong and weak electrolyte solutions.

  20. Major Source of Error in QSPR Prediction of Intrinsic Thermodynamic Solubility of Drugs: Solid vs Nonsolid State Contributions?

    Science.gov (United States)

    Abramov, Yuriy A

    2015-06-01

    The main purpose of this study is to define the major limiting factor in the accuracy of the quantitative structure-property relationship (QSPR) models of the thermodynamic intrinsic aqueous solubility of the drug-like compounds. For doing this, the thermodynamic intrinsic aqueous solubility property was suggested to be indirectly "measured" from the contributions of solid state, ΔGfus, and nonsolid state, ΔGmix, properties, which are estimated by the corresponding QSPR models. The QSPR models of ΔGfus and ΔGmix properties were built based on a set of drug-like compounds with available accurate measurements of fusion and thermodynamic solubility properties. For consistency ΔGfus and ΔGmix models were developed using similar algorithms and descriptor sets, and validated against the similar test compounds. Analysis of the relative performances of these two QSPR models clearly demonstrates that it is the solid state contribution which is the limiting factor in the accuracy and predictive power of the QSPR models of the thermodynamic intrinsic solubility. The performed analysis outlines a necessity of development of new descriptor sets for an accurate description of the long-range order (periodicity) phenomenon in the crystalline state. The proposed approach to the analysis of limitations and suggestions for improvement of QSPR-type models may be generalized to other applications in the pharmaceutical industry.

  1. Thermodynamics of protonation of amines in aqueous solutions at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Inna, E-mail: inna.kim@sintef.no [SINTEF Materials and Chemistry, N-7465 Trondheim (Norway); Jens, Christian M., E-mail: chrijens@stud.ntnu.no [Norwegian University of Science and Technology (NTNU), N-7491 Trondheim (Norway); Grimstvedt, Andreas, E-mail: andreas.grimstvedt@sintef.no [SINTEF Materials and Chemistry, N-7465 Trondheim (Norway); Svendsen, Hallvard F., E-mail: hallvard.svendsen@chemeng.ntnu.no [Norwegian University of Science and Technology (NTNU), N-7491 Trondheim (Norway)

    2011-11-15

    Highlights: > Effect of ionic strength and temperature on dissociation constants of amines. > Effect of ionic strength of temperature on enthalpies of protonation of amines. > Measured dissociation constants and enthalpies of protonation used for fitting. > Coefficients for thermodynamically consistent correlations given for 5 amines. - Abstract: The dissociation constants, pK{sub a}, of monoethanolamine (MEA), N-methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP), 2(2-aminoethyl)etanolamine (AEEA), and piperazine (Pz) were measured by potentiometric titration over the temperature range (298.15 to 363.15) K. Enthalpies of protonation, {Delta}H{sub p}, were measured calorimetrically at temperatures from (298.15 to 393.15) K for MEA, MDEA, and AMP, and from (298.15 to 353.15) K for AEEA and Pz. In addition, the effect of the ionic strength of the solutions on the protonation of MDEA was studied using NaCl as background salt {l_brace}(0 to 5.5) mol/kg-H{sub 2}O){r_brace}. Correlations for the reaction equilibrium constants for proton dissociation are proposed for the studied amines based on the experimental data from literature and from this work. Both experimental enthalpy data and dissociation constants were used for fitting. The results from this work may be used for thermodynamic modeling of CO{sub 2} capture processes using amines.

  2. Thermodynamics of mixed-ligand complex formation of mercury (II) ethylenediaminetetraacetate with amino acids in solution

    Energy Technology Data Exchange (ETDEWEB)

    Pyreu, Dmitrii, E-mail: pyreu@mail.ru [Department of Inorganic and Analytic Chemistry, Ivanovo State University, Ermak 39, Ivanovo 153025 (Russian Federation); Kozlovskii, Eugenii [Department of Inorganic and Analytic Chemistry, Ivanovo State University, Ermak 39, Ivanovo 153025 (Russian Federation); Gruzdev, Matvei; Kumeev, Roman [Institute of Solution Chemistry, Ivanovo (Russian Federation)

    2012-11-20

    Highlights: Black-Right-Pointing-Pointer Stable mixed ligand complexes of HgEdta with amino acids at physiological pH value. Black-Right-Pointing-Pointer The thermodynamic and NMR data evident the ambidentate coordination mode of arginine. Black-Right-Pointing-Pointer Participation of the guanidinic group of Arg in coordination process. Black-Right-Pointing-Pointer Binuclear complexes (HgEdta){sub 2}L with the bridging function of amino acid. - Abstract: The mixed-ligand complex formation in the systems Hg{sup 2+} - Edta{sup 4-} - L{sup -}(L = Arg, Orn, Ser) has been studied by means of calorimetry, pH-potentiometry and NMR spectroscopy in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO{sub 3}). The thermodynamic parameters of formation of the HgEdtaL, HgEdtaHL and (HgEdta){sub 2}L complexes have been determined. The most probable coordination mode for the complexone and the amino acid in the mixed-ligand complexes was discussed.

  3. A thermodynamic solution model for calcium carbonate: Towards an understanding of multi-equilibria precipitation pathways.

    Science.gov (United States)

    Donnet, Marcel; Bowen, Paul; Lemaître, Jacques

    2009-12-15

    Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann's approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thus possible equilibrium precipitation pathways can be evaluated by calculating the evolution of surface charge, particle size and/or interfacial energy during the ongoing reaction. The approach includes the use of the Kelvin's law to express the influence of particle size on the solubility constant of precipitates, the use of Nernst's law to calculate surface potentials from solubility calculations and relate this to experimentally measured zeta potentials. Calcium carbonate precipitation and zeta potential measurements of well characterised high purity calcite have been used as a model system to validate the calculated values. The clarification of the change in zeta potential on titration illustrates the power of this approach as a tool for reaction pathway prediction and hence knowledge based tailoring of precipitation reactions.

  4. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    Science.gov (United States)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  5. Isopiestic investigation of the osmotic coefficients of MgBr{sub 2}(aq) and study of bromide salts solubility in the (m{sub 1}KBr + m{sub 2}MgBr{sub 2})(aq) system at T = 323.15 K. Thermodynamic model of solution behaviour and (solid + liquid) equilibria in the MgBr{sub 2}(aq), and (m{sub 1}KBr + m{sub 2}MgBr{sub 2})(aq) systems to high concentration and temperature

    Energy Technology Data Exchange (ETDEWEB)

    Christov, Christomir, E-mail: christov@svr.igic.bas.b [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, ul. ' Acad. G. Bonchev' , bl. 11, 1113 Sofia (Bulgaria)

    2011-03-15

    The isopiestic method has been used to determine the osmotic coefficients of the binary solutions MgBr{sub 2}(aq) (from 0.4950 to 2.5197 mol {center_dot} kg{sup -1}) at the temperature T = 323.15 K. Sodium chloride solutions have been used as isopiestic reference standards. The solubility of the bromide minerals in the mixed system (m{sub 1}KBr + m{sub 2}MgBr{sub 2})(aq) has been investigated at T = 323.15 K by the physico-chemical analysis method. In addition to simple salts {l_brace}KBr(cr) and MgBr{sub 2} . 6H{sub 2}O(cr){r_brace}, equilibrium crystallization of the highly incongruent double salt with stoichiometric composition 1:1:6 {l_brace}bromcarnallite: KBr . MgBr{sub 2} . 6H{sub 2}O(cr){r_brace} was also established. The results obtained from the isopiestic and solubility measurements have been combined with all other experimental thermodynamic quantities available in the literature (osmotic coefficients, and solubility of the bromide mineral) to construct a chemical model that calculates solute and solvent activities and (solid + liquid) equilibria in the MgBr{sub 2}(aq) binary, and (m{sub 1}KBr + m{sub 2}MgBr{sub 2})(aq) mixed systems from dilute to high solution concentration within the (273.15 to 438.15) K temperature range. The solubility modelling approach based on fundamental Pitzer specific interaction equations is employed. It was found, that the standard for 2-1 type of electrolytes approach with three ({beta}{sup (0)}, {beta}{sup (1)}, and C{sup {phi}}) single electrolyte ion interaction parameters gives excellent agreement with osmotic coefficients from T = (298.15 to 373.45) K; up to saturation at 298.15 K, and up to m(MgBr{sub 2}) = 5.83 mol {center_dot} kg{sup -1} at 373.45 K, and with MgBr{sub 2} {center_dot} 6H{sub 2}O(cr) equilibrium pure water solubility data within the (273.15 to 438.15) K temperature range and up to {approx}8.5 mol {center_dot} kg{sup -1} used in parameterization. The model for the ternary system gives very good

  6. Thermodynamic characteristics of the acid dissociation of dopamine hydrochloride in water-ethanol solutions

    Science.gov (United States)

    Ledenkov, S. F.; Vandyshev, V. N.; Molchanov, A. S.

    2012-06-01

    Enthalpies of the interaction of protonated dopamine with a hydroxide ion in water-ethanol mixtures in the concentration range of 0-0.8 EtOH mole fractions are measured calorimetrically. The neutralization process of dopamine hydrochloride is shown to occur endothermally in solvents with an ethanol concentration of ≥0.5 mole fractions. Standard thermodynamic characteristics (Δr H ○, Δr G ○, and Δr S ○) of the first-step acid dissociation of dopamine hydrochloride in solutions are calculated with regard to the autoprotolysis enthalpy of binary solvents. It is found that dissociation enthalpies vary within 9.1-64.8 kJ/mol, depending on the water-ethanol solvent composition.

  7. Thermodynamics of the interaction between antihistamines with native and hydroxypropyl-cyclodextrin derivatives in aqueous solutions

    International Nuclear Information System (INIS)

    Alvarez-Lopez, Enrique; Perez-Casas, Silvia

    2013-01-01

    Highlights: • The complexes formation between cyclodextrins and pheniramines were studied by ITC. • In all the cases, the process is enthalpy driven. • The interactions between cyclodextrins and pheniramines are discussed. -- Abstract: The interactions of native and hydroxypropyl-cyclodextrin derivatives with pheniramine, (±)-brompheniramine, (+)-brompheniramine, (±)-chlorpheniramine, (+)-chlorpheniramine, carbinoxamine maleate salts and doxylamine succinate salt have been studied by isothermal titration calorimetry at T = 298.15 K in aqueous solution. The enthalpies and association constants for the complex formation were obtained, from which the Gibbs energy and entropy changes were derived. The thermodynamic parameters corresponding to the transfer process of the guest from the native to the modified CD are also calculated. The results show that the hydrophobic interactions are important in this process, but the size of the guest and the nature of the substituent are also of some importance

  8. Chitosan metal-crosslinked beads applied for n-alkylmonoamines removal from aqueous solutions – a thermodynamic study

    International Nuclear Information System (INIS)

    Oliveira, Margarete; Simoni, Jose A.; Airoldi, Claudio

    2014-01-01

    Highlights: • Chitosan beads were successfully synthesized with divalent cations. • Well-formed bead structures containing cations act as acceptor electron sites. • n-Alkylmonoamine/bead interactions are favorably sorbed at the solid/liquid interface. • The thermodynamic data were favorably obtained from calorimetric titrations. • Crosslinked metal–chitosan beads can remove amine-like substances from an ecosystem. - Abstract: Chitosan has ability in coordinating divalent cations when immersed in crosslinked beads, after dripping: (i) chitosan gel into a copper solution, (ii) nickel chitosan gel into sodium hydroxide and (iii) chitosan/cobalt gel into sodium tripolyphosphate. The amounts of (1.82; 1.27 and 0.44) mmol · g −1 for copper, nickel and cobalt cations in these well-formed structures were determined, to give nitrogen/metal ratios of 3.52; 2.09 and 8.51, indicating the least effectiveness for cobalt in the coordination. Copper cation is well-adjusted in the coordination model through free amino and hydroxyl electron pairs, while amino and acetamino groups for nickel and cobalt were used. The chitosan–hydrogen bond breaking in bead formation caused decreases in crystallinity to yield amorphous structures for cobalt and nickel. The water mass fraction released during heating depends on the hydration of the cations, with the highest value of 0.20 for cobalt. The quantitative aspects of the interaction among cations on beads and basic n-alkylmonoamines determined via sorption batch methodology adjusted to the Langmuir isothermal model, with maximum sorption quantities to saturate nickel of (2.50; 2.38; 2.03; 1.79) mmol · g −1 and copper of (2.59; 2.29; 2.28; 1.92) mmol · g −1 for ethyl- propyl-, butyl- and pentylamines, respectively. The interaction energies quantitatively determined from isothermal titration calorimetry (ITC) at the solid/liquid interface resulted in exothermic enthalpic values. These negative enthalpy values combined to

  9. Evaluation of selectivity and thermodynamic characteristics of doubly charged cations on zirconium titanate from aqueous and alcoholic solutions

    International Nuclear Information System (INIS)

    Zakaria, E.S.; Ali, I.M.; El-Naggar, I.M.

    2005-01-01

    The ion exchange of Ni 2+ /H + and Co 2+ /H + have been determined using solution of 0.1 ionic strength for both forward and backward reactions at 25 degree C by batch technique. The thermodynamic equilibrium constants for the exchange process have been calculated using Gains Thomas equation. The preference series Ni 2+ >Co 2+ was determined. The ion exchange selectivity for exchange of Ni 2 + and Co 2+ ions with hydrogen ions on zirconium titanate have been investigated for aqueous and 25% of methanol and ethanol solutions. The values of thermodynamic functions for the studied systems have been calculated

  10. Dissolution of britholites and monazite / brabantite solid solutions doped with actinides; Etude de la dissolution de britholites et de solutions solides monazite / brabantite dopees avec des actinides

    Energy Technology Data Exchange (ETDEWEB)

    Du Fou De Kerdaniel, E

    2007-12-15

    In the field of the radwaste storage in underground repository, several matrices were considered as promising ceramics for the specific immobilization of actinides. Two of them, britholites and monazite/ brabantite solid solution, have been considered during this work. In order to examine the dissolution mechanisms occurring at the solid liquid interface, several leaching experiments have been conducted on (Ln{sup III}PO{sub 4} ), brabantite (Ca{sup II}An{sup IV}(PO{sub 4}){sub 2}: An = Th, U) and britholites (Ca{sub 9}Nd{sub 0.5}An{sub 0.5}{sup IV} (PO{sub 4}){sub 4.5}(SiO{sub 4}){sub 1.5}F{sub 2}: An = Th, U). Some steady experiments, performed in under saturation conditions for various pH and temperature conditions allowed to evaluate the long term behaviour of such matrices through their chemical durability. On the contrary, the thermodynamic equilibria were examined through the leaching experiments performed near the saturation conditions. By the way, various secondary phases, precipitated onto the surface of altered samples have been identified and characterized. Among them, the (Nd, Ca, Th) - rhabdophane, novelly prepared in over- saturation experiments for a thorium weight loading lower than 11 % appeared to be metastable. Indeed, it turns into TPHPH (Th{sub 2}(PO{sub 4}){sub 2}HPO{sub 4}.H{sub 2}O) and Nd - rhabdophane (NdPO{sub 4}.1/2H{sub 2}O) when increasing leaching time. (author)

  11. Thermodynamic studies on the interaction between some amino acids with some rare earth metal ions in aqueous solutions

    International Nuclear Information System (INIS)

    Mohamed, AbdAllah A.; Bakr, Moustafa F.; Abd El-Fattah, Khaled A.

    2003-01-01

    The interactions between the amino acids (glycine and L-threonine) with some rare earth metal ions (Pr 3+ , Nd 3+ , Eu 3+ , Gd 3+ , Dy 3+ , Ho 3+ and Yb 3+ ) were studied at a wide range from ionic strengths (0.07-0.32 M KNO 3 ) and temperatures (25-45 deg. C) in aqueous solutions by using Bjerrum potentiometric method. The stoichiometric and thermodynamic stability constants were calculated as well as the standard thermodynamic parameters (ΔG deg., ΔH deg. and ΔS deg. ) for all possible reactions that occur. The degree of formation (n-bar) for all studied systems was determined and discussed. The thermodynamic parameters differences (ΔΔG deg., ΔΔH deg. and ΔΔS deg. ) were calculated and discussed to determine the factors which control these complexation processes from the thermodynamic point of view

  12. Phase stability in wear-induced supersaturated Al-Ti solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Y.; Yokoyama, K. [Dept. of Functional Machinery Mechanics Shinshu Univ., Ueda (Japan); Hosoda, H. [Precision and Intelligence Lab., Tokyo Inst. of Tech., Nagatsuta, Midori-ku, Yokohama (Japan)

    2002-07-01

    Al-Ti supersaturated solid solutions were introduced by wear testing and the rapid quenching of an Al/Al{sub 3}Ti composite (part of an Al/Al{sub 3}Ti functionally graded material) that was fabricated using the centrifugal method. The phase stability of the supersaturated solid solution was studied through systematic annealing of the supersaturated solid solution. It was found that the Al-Ti supersaturated solid solution decomposed into Al and Al{sub 3}Ti intermetallic compound phases during the heat treatment. The Al-Ti supersaturated solid solutions fabricated were, therefore, not an equilibrium phase, and thus decomposed into the equilibrium phases during heat treatment. It was also found that heat treatment leads to a significant hardness increase for the Al-Ti supersaturated solid solution. Finally, it was concluded that formation of the wear-induced supersaturated solid solution layer was a result of severe plastic deformation. (orig.)

  13. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    Energy Technology Data Exchange (ETDEWEB)

    Mutz, M. [University of Tennessee, Department of Chemistry (United States); Eastwood, Eric [Honeywell Kansas City Plant (United States); Lee, Mark E. [University of Missouri (United States); Bowen, Daniel E. [Honeywell Kansas City Plant (United States); Dadmun, M. D., E-mail: dad@utk.edu [University of Tennessee, Department of Chemistry (United States)

    2012-11-15

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A{sub 2}. A{sub 2} obtained from these measurements was then used to calculate {chi}, the solute-solvent interaction parameter, and the Hildebrand solubility parameter, {delta}, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a {chi} less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, {chi}, and {delta}. For instance, lower values of {chi} correspond to a smaller radius of gyration (R{sub g}). A list of suitable solvents based on {delta} is also presented.

  14. Soil solid-phase controls lead activity in soil solution.

    Science.gov (United States)

    Badawy, S H; Helal, M I D; Chaudri, A M; Lawlor, K; McGrath, S P

    2002-01-01

    Lead pollution of the environment is synonymous with civilization. It has no known biological function, and is naturally present in soil, but its presence in food crops is deemed undesirable. The concern regarding Pb is mostly due to chronic human and animal health effects, rather then phytotoxicity. However, not much is known about the chemistry and speciation of Pb in soils. We determined the activity of Pb2+, in near neutral and alkaline soils, representative of alluvial, desertic and calcareous soils of Egypt, using the competitive chelation method. Lead activity ranged from 10(-6.73) to 10(-4.83) M, and was negatively correlated with soil and soil solution pH (R2 = -0.92, P soil solution from the equation: log(Pb2+) = 9.9 - 2pH. A solubility diagram for the various Pb minerals found in soil was constructed using published thermodynamic data obtained from the literature, and our measured Pb2+ activities compared with this information. The measured Pb2+ activities were undersaturated with regard to the solubility of PbSiO3 in equilibrium with SiO2 (soil). However, they were supersaturated with regard to the solubilities of the Pb carbonate minerals PbCO3 (cerussite) and Pb3(CO3)2(OH)2 in equilibrium with atmospheric CO2 and hydroxide Pb(OH)2. They were also supersaturated with regard to the solubilities of the Pb phosphate minerals Pb3(PO4)2, Pb5(PO4)3OH, and Pb4O(PO4)2 in equilibrium with tricalcium phosphate and CaCO3. The activity of Pb2+ was not regulated by any mineral of known solubility in our soils, but possibly by a mixture of Pb carbonate and phosphate minerals.

  15. Radiation induced homogeneous precipitation in undersaturated solid-solutions

    International Nuclear Information System (INIS)

    Cauvin, R.; Martin, G.

    1979-01-01

    A TEM study of 1 MeV electron irradiated Al 1.9 at% Zn solid solution shows that Zn precipitates form, under irradiation at temperatures well above the Zn solvus temperature outside irradiation. The corresponding upward shift of this temperature is dose rate dependent. This new example of radiation-induced precipitation exhibits unexpected features, which are not accounted for by the available models: (1) no correlation exists between the location of the precipitates and that of the point defects sinks; (2) the precipitation of incoherent β-phase with atomic volume smaller than that of the matrix, and of coherent G.P. zones both occurs; (3) the size of the coherent β precipitates saturates at large dose. A general mechanism for solute concentration fluctuations under irradiation is proposed which qualitatively accounts for the formation of coherent G.P. zones and for the nucleation of solute clusters with more complex structures. A reanalysis of Russell's model (1977) for the growth of incoherent precipitates shows that it may qualitatively account for the observed behavior of the β phase precipitates. (Auth.)

  16. Diffuse neutron scattering study of metallic interstitial solid solutions

    International Nuclear Information System (INIS)

    Barberis, P.

    1991-10-01

    We studied two interstitial solid solutions (Ni-C(1at%) and Nb-O(2at%) and two stabilized zirconia (ZrO2-CaO(13.6mol%) and ZrO2-Y2O3(9.6mol%) by elastic diffuse neutron scattering. We used polarized neutron scattering in the case of the ferromagnetic Ni-based sample, in order to determine the magnetic perturbation induced by the C atoms. Measurements were made on single crystals in the Laboratoire Leon Brillouin (CEA-CNRS, Saclay, France). An original algorithm to deconvolve time-of-flight spectra improved the separation between elastically and inelastically scattered intensities. In the case of metallic solutions, we used a simple non-linear model, assuming that interstitials are isolated and located in octahedral sites. Results are: - in both compounds, nearest neighbours are widely displaced away from the interstitial, while next nearest neighbours come slightly closer. - the large magnetic perturbation induced by carbon in Nickel decreases with increasing distance on the three first neighbour shells and is in good agreement with the total magnetization variation. - no chemical order between solute atoms could be evidenced. Stabilized zirconia exhibit a strong correlation between chemical order and the large displacements around vacancies and dopants. (Author). 132 refs., 38 figs., 13 tabs

  17. Dissolution of britholites and monazite / brabantite solid solutions doped with actinides

    International Nuclear Information System (INIS)

    Du Fou De Kerdaniel, E.

    2007-12-01

    In the field of the radwaste storage in underground repository, several matrices were considered as promising ceramics for the specific immobilization of actinides. Two of them, britholites and monazite/ brabantite solid solution, have been considered during this work. In order to examine the dissolution mechanisms occurring at the solid liquid interface, several leaching experiments have been conducted on (Ln III PO 4 ), brabantite (Ca II An IV (PO 4 ) 2 : An = Th, U) and britholites (Ca 9 Nd 0.5 An 0.5 IV (PO 4 ) 4.5 (SiO 4 ) 1.5 F 2 : An = Th, U). Some steady experiments, performed in under saturation conditions for various pH and temperature conditions allowed to evaluate the long term behaviour of such matrices through their chemical durability. On the contrary, the thermodynamic equilibria were examined through the leaching experiments performed near the saturation conditions. By the way, various secondary phases, precipitated onto the surface of altered samples have been identified and characterized. Among them, the (Nd, Ca, Th) - rhabdophane, novelly prepared in over- saturation experiments for a thorium weight loading lower than 11 % appeared to be metastable. Indeed, it turns into TPHPH (Th 2 (PO 4 ) 2 HPO 4 .H 2 O) and Nd - rhabdophane (NdPO 4 .1/2H 2 O) when increasing leaching time. (author)

  18. Thermodynamics analysis of the rare earth metals and their alloys with indium in solid state

    International Nuclear Information System (INIS)

    Vassiliev, V.P.; Benaissa, Ablazeze; Taldrik, A.F.

    2013-01-01

    Graphical abstract: Gibbs energies of formation vs. RE atomic numbers in REIn 3 . Highlights: •Set of experimental values was collected for REIn 3 phases. •Thermodynamic functions of formation were calculated at 298 K and 775 K. •Experimental and calculated values were compared. -- Abstract: Nonlinear correlative analyses between thermodynamic and some physico-chemical properties of rare-earth metals (RE) and their alloys with indium are performed for the isostructural phases RE and REIn 3 . The thermodynamics values (Gibbs energies of formation, enthalpies of formation, and entropies of formation at 298 K and 775 K and standard entropies) of LnIn 3 phases are calculated on the basis of calorimetry and potentiometry results. The proposed correlation between physico-chemical and thermodynamic properties agrees for all the isostructural phases REX (X are others elements of the periodic table). The resulting thermodynamic data are recommended for metallurgical handbook

  19. Engineering solutions to the management of solid radioactive waste

    International Nuclear Information System (INIS)

    1991-01-01

    The management of radioactive waste, its safe handling and ultimate disposal, is of vital concern to engineers in the nuclear industry. The international conference 'Engineering Solutions to the Management of Solid Radioactive Waste', organized by the Institution of Mechanical Engineers and held in Manchester in November 1991, provided a forum for the discussion and comparison of the different methods of waste management used in Europe and America. Papers presented and discussed included: the interaction between the design of containers for low level radioactive waste and the design of a deep repository, commercial low level waste disposal sites in the United States, and the development of radioactive waste monitoring systems at the Sellafield reprocessing complex. This volume is a collection of 22 papers presented at the conference. All are indexed separately. (author)

  20. Applicability of Solid Solution Heat Treatments to Aluminum Foams

    Directory of Open Access Journals (Sweden)

    Miguel Rodríguez-Pérez

    2012-12-01

    Full Text Available Present research work evaluates the influence of both density and size on the treatability of Aluminum-based (6000 series foam-parts subjected to a typical solid solution heat treatment (water quenching. The results are compared with those obtained for the bulk alloy, evaluating the fulfilment of cooling requirements. Density of the foams was modeled by tomography analysis and the thermal properties calculated, based on validated density-scaled models. With this basis, cooling velocity maps during water quenching were predicted by finite element modeling (FEM in which boundary conditions were obtained by solving the inverse heat conduction problem. Simulations under such conditions have been validated experimentally. Obtained results address incomplete matrix hardening for foam-parts bigger than 70 mm in diameter with a density below 650 kg/m3. An excellent agreement has been found in between the predicted cooling maps and final measured microhardness profiles.

  1. Thermodynamic assessment of the zirconia-urania system

    International Nuclear Information System (INIS)

    Yashima, Masatomo; Koura, Toshiaki; Du, Y.; Yoshimura, Masahiro

    1996-01-01

    An optimal thermodynamic data set for the zirconia-urania system is devaluated by the CALPHAD (CALculation of PHAse Diagrams) method. A regular solution model is applied to all phases of the cubic, tetragonal, and monoclinic solid solutions and the liquid. Comparisons between calculated and measured phase diagrams show that most of the experimental information is satisfactorily accounted for by thermodynamic calculations

  2. Crystal-chemical features of the solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Titov, V.V.; Kesler, Ya.A.; Gordeev, I.V.; Mozhaev, A.P.

    1988-04-01

    The unusual magnetic properties of the solid solutions of CuCr/sub 2/S/sub 4/ in Cu/sub 0.5/Mo/sub 0.5/Cr/sub 2/S/sub 4/ (M = Al, Ga, In) are closely related to the crystal chemistry of these compounds. Specimens for structural investigation were obtained by solid-phase synthesis in evacuated quartz capsules. X-ray phase analysis of all the compounds was made by the powder method in a DRON-1 diffractometer with Cu K..cap alpha.. filtered radiation. The experimental confirmation of the ordering of the cations in the tetrahedral sublattice of the investigated spinels was obtained by the authors from their IR absorption spectra taken in the range 400-33 cm/sup /minus/1/. The presence of seven intense absorption bands in the spectra of the specimens indicates that these materials belong to the space group F/anti/43m, i.e., that there is ordering in the A sublattice. Their investigation led them to the conclusion that in a number of cases the vibrational spectra of the crystals are more sensitive in the investigation of atomic ordering than the spectra of x-ray and neutron diffraction, in agreement with the theoretical predictions.

  3. Physico-chemical properties of aqueous drug solutions: From the basic thermodynamics to the advanced experimental and simulation results.

    Science.gov (United States)

    Bellich, Barbara; Gamini, Amelia; Brady, John W; Cesàro, Attilio

    2018-04-05

    The physical chemical properties of aqueous solutions of model compounds are illustrated in relation to hydration and solubility issues by using three perspectives: thermodynamic, spectroscopic and molecular dynamics simulations. The thermodynamic survey of the fundamental backgrounds of concentration dependence and experimental solubility results show some peculiar behavior of aqueous solutions with several types of similar solutes. Secondly, the use of a variety of experimental spectroscopic devices, operating under different experimental conditions of dimension and frequency, has produced a large amount of structural and dynamic data on aqueous solutions showing the richness of the information produced, depending on where and how the experiment is carried out. Finally, the use of molecular dynamics computational work is presented to highlight how the different types of solute functional groups and surface topologies organize adjacent water molecules differently. The highly valuable contribution of computer simulation studies in providing molecular explanations for experimental deductions, either of a thermodynamic or spectroscopic nature, is shown to have changed the current knowledge of many aqueous solution processes. While this paper is intended to provide a collective view on the latest literature results, still the presentation aims at a tutorial explanation of the potentials of the three methodologies in the field of aqueous solutions of pharmaceutical molecules. Copyright © 2018. Published by Elsevier B.V.

  4. Theoretical Application of Irreversible (Nonequilibrium) Thermodynamic Principles to Enhance Solute Fluxes across Nanofabricated Hemodialysis Membranes

    Science.gov (United States)

    Hedayat, Assem; Elmoselhi, Hamdi; Shoker, Ahmed

    2012-01-01

    Objective. Nanotechnology has the potential to improve hemodialysis membrane technology. Thus, a major objective is to understand how to enhance toxic solute fluxes across these membranes. The aim of this concept building study is to review the application of irreversible thermodynamic (IT) to solute fluxes. Methods. We expanded the application of the Nernst-Planck equation to include the Kedem-Katchalsky equation, pH, membrane thickness, pore size, and electric potential as variables. Results. (1) Reducing the membrane's thickness from 25 μm to 25 nm increased the flux of creatinine, β2-microglobulin, and tumor necrosis factor-α (TNF-α) by a thousand times but prevented completely albumin flux, (2) applying an electric potential of 50–400 mV across the membrane enhanced the flux of the respective molecules by 71.167 × 10−3, 38.7905 × 10−8, and 0.595 × 10−13 mol/s, and (3) changing the pH from 7.35 to 7.42 altered the fluxes minimally. Conclusions. The results supported an argument to investigate the application of IT to study forces of fluxes across membranes. Reducing the membrane's thickness—together with the application of an electrical potential—qualities achievable by nanotechnology, can enhance the removal of uremic toxins by many folds. However, changing the pH at a specific membrane thickness does not affect the flux significantly. PMID:23209903

  5. Kinetic and Thermodynamic Studies on Biosorption of Direct Red 81 from Aqueous Solutions by Chamomilla Plant

    Directory of Open Access Journals (Sweden)

    M. Momen Heravi

    2013-01-01

    Full Text Available In this study, Chamomilla plant biomass used as a sorbent for biosorption of a textile dye, direct red 81, from an aqueous solution. The batch sorption was studied with respect to dye concentration, adsorbent dose and temperature. Also, kinetic and isotherm parameters were determined for biosorption of Direct red 81 by Chamomilla plant. The maximum biosorption capacity (qm of Direct red 81 10 mg g-1 was obtained at 25oC. The kinetic and isotherm studies indicated that the biosorption process obeys a pseudo-second order and Langmuir isotherm models. In addition, various thermodynamic parameters, such as changes in Gibbs free energy (ΔG, enthalpy (ΔH and entropy (ΔS have been calculated. The biosorption process of Direct Red 81 dye onto activated carbon prepared from Chamomilla plant was found to be spontaneous and exothermic. The findings of this investigation suggest that this procces is a physical biosorption. The experimental studies indicated that Chamomilla plant had the potential to act as an alternative biosorbent to remove the Direct Red 81 dye from an aqueous solution.

  6. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    International Nuclear Information System (INIS)

    Mutz, M.; Eastwood, Eric; Lee, Mark E.; Bowen, Daniel E.; Dadmun, M. D.

    2012-01-01

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A 2 . A 2 obtained from these measurements was then used to calculate χ, the solute–solvent interaction parameter, and the Hildebrand solubility parameter, δ, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a χ less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, χ, and δ. For instance, lower values of χ correspond to a smaller radius of gyration (R g ). A list of suitable solvents based on δ is also presented.

  7. The thermodynamic stability induced by solute co-segregation in nanocrystalline ternary alloys

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Tao; Chen, Zheng; Zhang, Jinyong; Zhang, Ping [China Univ. of Mining and Technology, Xuzhou (China). School of Mateial Science and Engineering; Yang, Xiaoqin [China Univ. of Mining and Technology, Xuzhou (China). School of Chemical Engineering and Technology

    2017-06-15

    The grain growth and thermodynamic stability induced by solute co-segregation in ternary alloys are presented. Grain growth behavior of the single-phase supersaturated grains prepared in Ni-Fe-Pb alloy melt at different undercoolings was investigated by performing isothermal annealings at T = 400 C-800 C. Combining the multicomponent Gibbs adsorption equation and Guttmann's grain boundary segregation model, an empirical relation for isothermal grain growth was derived. By application of the model to grain growth in Ni-Fe-Pb, Fe-Cr-Zr and Fe-Ni-Zr alloys, it was predicted that driving grain boundary energy to zero is possible in alloys due to the co-segregation induced by the interactive effect between the solutes Fe/Pb, Zr/Ni and Zr/Cr. A non-linear relationship rather than a simple linear relation between 1/D* (D* the metastable equilibrium grain size) and ln(T) was predicted due to the interactive effect.

  8. Adsorption of reactive dye from an aqueous solution by chitosan: isotherm, kinetic and thermodynamic analysis

    International Nuclear Information System (INIS)

    Annadurai, Gurusamy; Ling, L.Y.; Lee, J.-F.

    2008-01-01

    The adsorption of Remazol black 13 (Reactive) dye onto chitosan in aqueous solutions was investigated. Experiments were carried out as function of contact time, initial dye concentration (100-300 mg/L), particle size (0.177, 0.384, 1.651 mm), pH (6.7-9.0), and temperature (30-60 deg. C). The equilibrium adsorption data of reactive dye on chitosan were analyzed by Langmuir and Freundlich models. The maximum adsorption capacity (q m ) has been found to be 91.47-130.0 mg/g. The amino group nature of the chitosan provided reasonable dye removal capability. The kinetics of reactive dye adsorption nicely followed the pseudo-first and second-order rate expression which demonstrates that intraparticle diffusion plays a significant role in the adsorption mechanism. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption. The positive value of the enthalpy change (0.212 kJ/mol) indicated that the adsorption is endothermic process. The results indicate that chitosan is suitable as adsorbent material for adsorption of reactive dye form aqueous solutions

  9. A thermodynamic model of the hydrolysis of microcline in acid sulfate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Dedolph, R.E.; Parry, W.T.

    1976-12-01

    A theoretical model of the hydrolysis of microcline by a hydrothermal solution has been determined for a closed system at constant temperature. Hypothetical solution compositions and temperatures were chosen to match the known geothermal system at Roosevelt Hot Springs, Utah. The calculated reaction paths indicate that the overall reaction process is an exchange of potassium from the reactant mineral, microcline, for hydrogen from the solution. Aluminum is nearly conserved among solid phases. The amount of microcline reacted per kilogram of solution before overall equilibrium is reached is a function of temperature and initial solution pH. Since the system is closed and at constant temperature natural conditions are not reproduced well enough to apply the model as a geothermometer. The reaction paths suggest qualitative models of alteration mineral zoning patterns that are similar to zoning at Roosevelt Hot Springs, utah; Steamboat Springs, Nevada, and Butte, Montana. The models presented view alteration zoning as a function of temperature and pH gradients within homogeneous host rocks where microcline and quartz are abundant.

  10. Solution thermodynamics and preferential solvation of sulfamethazine in (methanol + water) mixtures

    International Nuclear Information System (INIS)

    Delgado, Daniel R.; Almanza, Ovidio A.; Martínez, Fleming; Peña, María A.; Jouyban, Abolghasem; Acree, William E.

    2016-01-01

    Highlights: • Solubility of sulfamethazine (SMT) was measured in (methanol + water) mixtures. • SMT solubility was correlated with Jouyban–Acree model. • Gibbs energy, enthalpy, and entropy of dissolution of SMT were calculated. • Non-linear enthalpy–entropy relationship was observed for SMT. • Preferential solvation of SMT by methanol was analyzed by using the IKBI method. - Abstract: The solubility of sulfamethazine (SMT) in {methanol (1) + water (2)} co-solvent mixtures was determined at five different temperatures from (293.15 to 313.15) K. The sulfonamide exhibited its highest mole fraction solubility in pure methanol (δ 1 = 29.6 MPa 1/2 ) and its lowest mole fraction solubility in water (δ 2 = 47.8 MPa 1/2 ) at each of the five temperatures studied. The Jouyban–Acree model was used to correlate/predict the solubility values. The respective apparent thermodynamic functions Gibbs energy, enthalpy, and entropy of solution were obtained from the solubility data through the van’t Hoff and Gibbs equations. Apparent thermodynamic quantities of mixing were also calculated for this drug using values of the ideal solubility reported in the literature. A non-linear enthalpy–entropy relationship was noted for SMT in plots of both the enthalpy vs. Gibbs energy of mixing and the enthalpy vs. entropy of mixing. These plots suggest two different trends according to the slopes obtained when the composition of the mixtures changes. Accordingly, the mechanism for SMT transfer processes in water-rich mixtures from water to the mixture with 0.70 in mass fraction of methanol is entropy driven. Conversely, the mechanism is enthalpy driven in mixtures whenever the methanol composition exceeds 0.70 mol fraction. An inverse Kirkwood–Buff integral analysis of the preferential solvation of SMT indicated that the drug is preferentially solvated by water in water-rich mixtures but is preferentially solvated by methanol in methanol-rich mixtures.

  11. Friedel's salt profiles from thermogravimetric analysis and thermodynamic modelling of Portland cement-based mortars exposed to sodium chloride solution

    DEFF Research Database (Denmark)

    Shi, Zhenguo; Geiker, Mette Rica; Lothenbach, Barbara

    2017-01-01

    Thermogravimetric analysis (TGA), powder X-ray diffraction (XRD) and thermodynamic modelling have been used to obtain Friedel's salt profiles for saturated mortar cylinders exposed to a 2.8 M NaCl solution. Comparison of the measured Friedel's salt profiles with the total chloride profiles...

  12. Phase-separation phenomena in solutions of poly(2,6-dimethyl-1,4-phenylene oxide). I. Thermodynamic parameters of solutions in toluene

    NARCIS (Netherlands)

    Koenhen, D.M.; Smolders, C.A.

    1977-01-01

    New experimental data have been collected on thermodynamic properties of solutions of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) in toluene. The Flory-Huggins interaction parameters g have been determined from light scattering measurements. These values are in agreement with values obtained by

  13. Thermodynamic model of a solid with RKKY interaction and magnetoelastic coupling

    Science.gov (United States)

    Balcerzak, T.; Szałowski, K.; Jaščur, M.

    2018-04-01

    Thermodynamic description of a model system with magnetoelastic coupling is presented. The elastic, vibrational, electronic and magnetic energy contributions are taken into account. The long-range RKKY interaction is considered together with the nearest-neighbour direct exchange. The generalized Gibbs potential and the set of equations of state are derived, from which all thermodynamic functions are self-consistently obtained. Thermodynamic properties are calculated numerically for FCC structure for arbitrary external pressure, magnetic field and temperature, and widely discussed. In particular, for some parameters of interaction potential and electron concentration corresponding to antiferromagnetic phase, the existence of negative thermal expansion coefficient is predicted.

  14. Fabrication and Application of (1-x) NaCl+xKCl Solid Solution

    International Nuclear Information System (INIS)

    Kyi Kyi Lwin

    2011-12-01

    (1-X)NaCl+xKCl solid solution are prepared by the starting materials NaCl (0.9, 0.95) in equal molar ratio. The solid solutions are heat-treated at various temperature and XRD analyses are carried out for the solid solutions to examine the crystalline phase, crystallographic orientation and lattice parameters. The electrical properties of the solutions are determined by using the conductometer. The solid solutions are utilized as crystal oscillator and outcoming frequencies, capacitances and dielectric constants are also investigated.

  15. Determination of the thermodynamic state of concentrated hemoglobin solutions by means of small angle X-ray scattering

    International Nuclear Information System (INIS)

    Zinke, M.

    1979-01-01

    Exemplified by hemoglobin, the thermodynamic equilibrium properties of the dissolved macromolecular system could be determined solely from the small angle X-ray scattering of concentrated macromolecular solutions via the intermolecular structure of the dissolved macromolecules and their intermolecular potentials. From the scattering experiment on concentrated Hb solutions the concentration dependence of the following properties of the dissolved Hb system were determined: fluctuation, isothermic compressibility, internal energy, surface tension, and osmotic pressure. (author)

  16. Effect of the additives on clouding behavior and thermodynamics of coenzyme Q10-Kolliphor HS15 micelle aqueous solutions

    Science.gov (United States)

    Hu, Li; Zhang, Jing; Zhu, Chao; Pan, Hong-chun; Liu, Hong

    2017-11-01

    Herein we investigate the effect of different additives (electrolytes, amino acids, PEG, and sugars) on the cloud points (CP) of coenzyme Q10 (CoQ10) - Kolliphor HS15 (HS15) micelle aqueous solutions. The CP values were decreased with the increase of electrolytes and sugars, following: CPAl3+ reduced the CP. A depression of CP for CoQ10-HS15 micelle solution with PEG was molecular weight of PEG dependent. The significant thermodynamic parameters were also evaluated and discussed.

  17. Thermodynamics of two component gaseous and solid state plasmas at any degeneracy

    International Nuclear Information System (INIS)

    Kraeft, W.D.; Stolzmann, W.; Fromhold-Treu, I.; Rother, T.

    1988-10-01

    We give the results of thermodynamical calculations for two component plasmas which are of interest for dense hydrogen, noble gas and alkali plasmas and for electron hole plasmas in optically excited semiconductors as well. 25 refs, 4 figs

  18. A thermodynamically consistent constitutive theory for a rigid solid-stokesian fluid mixture

    International Nuclear Information System (INIS)

    Mattos, H.C.; Costa, M.L.M.; Sampaio, R.; Gama, R.M.S. da.

    1992-01-01

    This work is concerned with the modelling for the flow of a stokesian fluid through a rigid porous medium, using a Theory of Mixtures viewpoint. A systematic procedure to obtain constitutive relations that verify automatically the principle of objectivity and a local version of the second law of Thermodynamics is proposed. The prescription of two thermodynamic potentials for each constituent is sufficient to define a complete set of constitutive relations. (author)

  19. An optics-based variable-temperature assay system for characterizing thermodynamics of biomolecular reactions on solid support

    Energy Technology Data Exchange (ETDEWEB)

    Fei, Yiyan; Landry, James P.; Zhu, X. D., E-mail: xdzhu@physics.ucdavis.edu [Department of Physics, University of California, One Shields Avenue, Davis, California 95616 (United States); Li, Yanhong; Yu, Hai; Lau, Kam; Huang, Shengshu; Chokhawala, Harshal A.; Chen, Xi [Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616 (United States)

    2013-11-15

    A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400–10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven, entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.

  20. Studies on mixed metal oxides solid solutions as heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    H. R. Arandiyan

    2009-03-01

    Full Text Available In this work, a series of perovskite-type mixed oxide LaMo xV1-xO3+δ powder catalysts (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0, with 0.5 < δ < 1.5, prepared by the sol-gel process and calcined at 750ºC, provide an attractive and effective alternative means of synthesizing materials with better control of morphology. Structures of resins obtained during the gel formation process by FT-IR spectroscopy and XRD analysis showed that all the LaMo xV1-xO3+δ samples are single phase perovskite-type solid solutions. The surface area (BET between 2.5 - 5.0 m²/g (x = 0.1 and 1.0 respectively increases with increasing Mo ratio in the samples. They show high purity, good chemical homogeneity, and lower calcinations temperatures as compared with the solid-state chemistry route. SEM coupled to EDS and thermogravimetric analysis/differential thermal analyses (TGA/DTA have been carried out in order to evaluate the homogeneity of the catalyst. Finally, the experimental studies show that the calcination temperature and Mo content exhibited a significant influence on catalytic activity. Among the LaMo xV1-xO3+δ samples, LaMo0.7V0.3O4.2 showed the best catalytic activity for the topic reaction and the best activity and stability for ethane reforming at 850ºC under 8 bar.

  1. Life cycle assessment integrated with thermodynamic analysis of bio-fuel options for solid oxide fuel cells.

    Science.gov (United States)

    Lin, Jiefeng; Babbitt, Callie W; Trabold, Thomas A

    2013-01-01

    A methodology that integrates life cycle assessment (LCA) with thermodynamic analysis is developed and applied to evaluate the environmental impacts of producing biofuels from waste biomass, including biodiesel from waste cooking oil, ethanol from corn stover, and compressed natural gas from municipal solid wastes. Solid oxide fuel cell-based auxiliary power units using bio-fuel as the hydrogen precursor enable generation of auxiliary electricity for idling heavy-duty trucks. Thermodynamic analysis is applied to evaluate the fuel conversion efficiency and determine the amount of fuel feedstock needed to generate a unit of electrical power. These inputs feed into an LCA that compares energy consumption and greenhouse gas emissions of different fuel pathways. Results show that compressed natural gas from municipal solid wastes is an optimal bio-fuel option for SOFC-APU applications in New York State. However, this methodology can be regionalized within the U.S. or internationally to account for different fuel feedstock options. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

    Energy Technology Data Exchange (ETDEWEB)

    Jacob, K.T., E-mail: katob@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Prusty, Debadutta [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Kale, G.M. [Institute for Materials Research, University of Leeds, Leeds, LS2 9JT (United Kingdom)

    2012-02-05

    Highlights: Black-Right-Pointing-Pointer Refinement of phase diagram for the system Mg-Rh-O and thermodynamic data for spinel compounds MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} is presented. Black-Right-Pointing-Pointer A solid-state electrochemical cell is used for thermodynamic measurement. Black-Right-Pointing-Pointer An advanced design of the solid-state electrochemical cell incorporating buffer electrodes is deployed to minimize polarization of working electrode. Black-Right-Pointing-Pointer Regular solution model for the spinel solid solution MgRh{sub 2}O{sub 4} - Mg{sub 2}RhO{sub 4} based on ideal mixing of cations on the octahedral site is proposed. Black-Right-Pointing-Pointer Factors responsible for stabilization of tetravalent rhodium in spinel compounds are identified. - Abstract: Pure stoichiometric MgRh{sub 2}O{sub 4} could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh{sub 2}O{sub 3} in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh{sub 2}O{sub 3}. The spinel phase can be considered as a solid solution of Mg{sub 2}RhO{sub 4} in MgRh{sub 2}O{sub 4}. The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg{sub 1+x}Rh{sub 2-x}O{sub 4} was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured

  3. Adsorption of 4-chlorophenol from aqueous solutions by xad-4 resin: Isotherm, kinetic, and thermodynamic analysis

    International Nuclear Information System (INIS)

    Bilgili, M. Sinan

    2006-01-01

    Removal of 4-chlorophenol (4-CP) from synthetic aqueous solutions through adsorption on Amberlite XAD-4 resin, a non-ionic macroreticular resins, under batch equilibrium experimental conditions at 298, 308 and 318 K was investigated. It is necessary to propose a suitable model to a better understanding on the mechanism of 4-CP adsorption. For this purpose, Langmiur, Freundlich, Toth, and Redlich-Peterson (RP) isotherm models were compared. The two and three parameters in the adopted adsorption isotherm models were determined by the help of MATLAB package program. It was determined that best fitted adsorption isotherm models were obtained to be in the order: Redlich-Peterson > Langmuir > Toth > Freundlich isotherms. The pseudo-second-order kinetic model provided the best correlation to the experimental results. Results of the intra-particle diffusion model show that the pore diffusion is not the only rate limiting step. The lower correlation of the data to the Bangham's equation also represents that the diffusion of the adsorbate into pores of the sorbent is not the only rate-controlling step. The thermodynamic constants of adsorption phenomena; ΔG o , ΔH o , and ΔS o were found as -4.17 (at 298 K) kJ/mol, -42.01 kJ/mol, and -0.127 kJ/(mol K), respectively. The results showed that adsorption of 4-CP on Amberlite XAD-4, a nonionic polymeric resin was exothermic and spontaneous

  4. Determination of thermodynamic parameters of Cr(VI) adsorption from aqueous solution onto Agave lechuguilla biomass

    Energy Technology Data Exchange (ETDEWEB)

    Romero-Gonzalez, J. [Environmental Science and Engineering, University of Texas at El Paso, El Paso, TX 79968 (United States); Peralta-Videa, J.R. [Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968 (United States); Rodriguez, E. [Environmental Science and Engineering, University of Texas at El Paso, El Paso, TX 79968 (United States); Ramirez, S.L. [Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968 (United States); Gardea-Torresdey, J.L. [Environmental Science and Engineering, University of Texas at El Paso, El Paso, TX 79968 (United States) and Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968 (United States)]. E-mail: jgardea@utep.edu

    2005-04-15

    The temperature dependence of the Cr(VI) bioadsorption and its possible reduction to Cr(III) by Agave lechuguilla biomass were studied. The experimental data obtained in batch experiments at different temperatures were fitted to the Langmuir and Freundlich isotherms to obtain the characteristic parameters of each model. The adsorption equilibrium data fitted well with the Freundlich model. The average model parameters calculated from Freundlich's isotherms (adsorption capacity K{sub F} = 4 . 10{sup -2} mol . g{sup -1} and an average adsorption intensity value n = 13.07) showed that A. lechuguilla can be considered as an effective biomaterial for Cr(VI) removal from aqueous solution. Thermodynamic parameters ({delta}G{sup .}, {delta}H{sup .}, and {delta}S{sup .}) for Cr(VI) adsorption determined in the temperature range from (283 to 313) K suggest that a portion of Cr(VI) may be bound to functional groups on the surface of the adsorbent and then reduced to Cr(III). Additionally, the parameters of the Dubinin-Radushkevick equation indicated that the sorption of chromium species onto lechuguilla biomass mainly proceeds through binding surface functional groups.

  5. Adsorption of cationic dye from aqueous solution by clay as an adsorbent: thermodynamic and kinetic studies

    International Nuclear Information System (INIS)

    Fil, B.A.; Ozmetn, C.

    2012-01-01

    In the study, montmorillonite was used as an adsorbent for the removal of methylene blue (MB) from aqueous solutions. Batch studies were performed to address various experimental parameters like contact time, pH, temperature, stirring speed, ionic strength, adsorbent dosage and initial concentration for the removal of this dye. Adsorption rate increased with the increase in initial dye concentration, ionic strength, stirring speed, pH and temperature. Kinetic study showed that the adsorption of dye on montmorillonite was a gradual process. Quasi-equilibrium reached in 3 h. Pseudo-first-order, pseudo-second-order, Elovich, Bangham, mass transfer and intra-particle particle diffusion models were used to fit the experimental data. Pseudo-second-order rate equation was able to provide realistic description of adsorption kinetics. Intra-particle diffusion process was identified as the main mechanism controlling the rate of the dye sorption. The diffusion coefficient, D, was found to increase when the stirring speed, ionic strength and temperature were raised. Thermodynamic activation parameters such as delt G, delt S and del H were also calculated. (author)

  6. Fenton-Like Oxidation of Malachite Green Solutions: Kinetic and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Saeedeh Hashemian

    2013-01-01

    Full Text Available Oxidation by Fenton-like (Fe3+/H2O2 reactions is proven to be an economically feasible process for destruction of a variety of hazardous pollutants in wastewater. In this study, the degradation and mineralization of malachite green dye are reported using Fenton-like reaction. The effects of different parameters like pH of the solution, the initial concentrations of Fe3+, H2O2, and dye, temperature, and added electrolytes (Cl− and on the oxidation of the dye were investigated. Optimized condition was determined. The efficiency of 95.5% degradation of MAG after 15 minutes of reaction at pH 3 was obtained. TOC removal indicates partial and insignificant mineralization of malachite green dye. The results of experiments showed that degradation of malachite green dye in Fenton-like oxidation process can be described with a pseudo-second-order kinetic model. The thermodynamic constants of the Fenton oxidation process were evaluated. The results implied that the oxidation process was feasible, spontaneous, and endothermic. The results will be useful for designing the treatment systems of various dye-containing wastewaters.

  7. Thermodynamic functions for solubility of 3-nitro-o-toluic acid in nine organic solvents from T = (283.15 to 318.15) K and apparent thermodynamic properties of solutions

    International Nuclear Information System (INIS)

    Li, Xinbao; Wang, Mingju; Du, Cunbin; Cong, Yang; Zhao, Hongkun

    2017-01-01

    Highlights: • Solubilities of 3-nitro-o-toluic acid in nine organic solvents were determined. • The solubilities were correlated by using four thermodynamic models. • The mixing properties of solution were computed based on Wilson model. - Abstract: Separation of 3-nitro-o-toluic acid from its isomeric mixtures has essential significance in industry. In this work, by using isothermal saturation method, the solid-liquid equilibrium for 3-nitro-o-toluic acid in nine organic solvents (acetonitrile, methanol, ethanol, n-propanol, isopropanol, ethyl acetate, acetone, 1,4-dioxane and 2-butanone) were obtained experimentally within a temperature range from (283.15 to 318.15) K under atmosphere pressure of 101.2 kPa, and the solubility values of 3-nitro-o-toluic acid in these solvents were determined by a high-performance liquid chromatography. Within the studied temperature range, the mole fraction solubility of 3-nitro-o-toluic acid in selected organic solvents increased with increasing temperature. Except for ethyl acetate, the descending order of the mole fraction solubility values were as follow: 1,4-dioxane > acetone > 2-butanone > methanol > ethanol > isopropanol > n-propanol > acetonitrile. The solubility values determined for 3-nitro-o-toluic acid in the selected solvents were correlated and back calculated with the modified Apelblat equation, λh equation, Wilson model and NRTL model. The largest values of RAD and RMSD obtained with the four models were 0.67% and 4.02 × 10 −4 , respectively. In general, the four thermodynamic models were all acceptable for describing the solubility behaviour of 3-nitro-o-toluic acid in these solvents. In addition, the apparent mixing Gibbs energy, mixing enthalpy, mixing entropy, activity coefficient at infinitesimal concentration and reduced excess enthalpy were calculated. The acquired solubility data and thermodynamic studies would be very important in optimizing the separation process of 3-nitro-o-toluic acid from

  8. Sustainable solutions for solid waste management in Southeast Asian countries

    International Nuclear Information System (INIS)

    Uyen Nguyen Ngoc; Schnitzer, Hans

    2009-01-01

    Human activities generate waste and the amounts tend to increase as the demand for quality of life increases. Today's rate in the Southeast Asian Nations (ASEANs) is alarming, posing a challenge to governments regarding environmental pollution in the recent years. The expectation is that eventually waste treatment and waste prevention approaches will develop towards sustainable waste management solutions. This expectation is for instance reflected in the term 'zero emission systems'. The concept of zero emissions can be applied successfully with today's technical possibilities in the agro-based processing industry. First, the state-of-the-art of waste management in Southeast Asian countries will be outlined in this paper, followed by waste generation rates, sources, and composition, as well as future trends of waste. Further on, solutions for solid waste management will be reviewed in the discussions of sustainable waste management. The paper emphasizes the concept of waste prevention through utilization of all wastes as process inputs, leading to the possibility of creating an ecosystem in a loop of materials. Also, a case study, focusing on the citrus processing industry, is displayed to illustrate the application of the aggregated material input-output model in a widespread processing industry in ASEAN. The model can be shown as a closed cluster, which permits an identification of opportunities for reducing environmental impacts at the process level in the food processing industry. Throughout the discussion in this paper, the utilization of renewable energy and economic aspects are considered to adapt to environmental and economic issues and the aim of eco-efficiency. Additionally, the opportunities and constraints of waste management will be discussed.

  9. Thermodynamic and thermoeconomic analysis of a system with biomass gasification, solid oxide fuel cell (SOFC) and Stirling engine

    DEFF Research Database (Denmark)

    Rokni, Masoud

    2014-01-01

    Thermodynamic and thermoeconomic investigations of a small-scale integrated gasification solid oxide fuel cell (SOFC) and Stirling engine for combined heat and power (CHP) with a net electric capacity of 120kWe have been performed. Woodchips are used as gasification feedstock to produce syngas......Wh. Furthermore, hot water is considered as a by-product, and the cost of hot water is found to be 0.0214$/kWh. When compared to other renewable systems of similar scales, this result shows that if both SOFC and Stirling engine technology enter the commercialization phase, then they can deliver electricity...

  10. Theoretical Application of Irreversible (Nonequilibrium Thermodynamic Principles to Enhance Solute Fluxes across Nanofabricated Hemodialysis Membranes

    Directory of Open Access Journals (Sweden)

    Assem Hedayat

    2012-01-01

    Full Text Available Objective. Nanotechnology has the potential to improve hemodialysis membrane technology. Thus, a major objective is to understand how to enhance toxic solute fluxes across these membranes. The aim of this concept building study is to review the application of irreversible thermodynamic (IT to solute fluxes. Methods. We expanded the application of the Nernst-Planck equation to include the Kedem-Katchalsky equation, pH, membrane thickness, pore size, and electric potential as variables. Results. (1 Reducing the membrane’s thickness from 25 μm to 25 nm increased the flux of creatinine, β2-microglobulin, and tumor necrosis factor-α (TNF-α by a thousand times but prevented completely albumin flux, (2 applying an electric potential of 50–400 mV across the membrane enhanced the flux of the respective molecules by 71.167 × 10-3, 38.7905 × 10-8, and 0.595 × 10-13 mol/s, and (3 changing the pH from 7.35 to 7.42 altered the fluxes minimally. Conclusions. The results supported an argument to investigate the application of IT to study forces of fluxes across membranes. Reducing the membrane’s thickness—together with the application of an electrical potential—qualities achievable by nanotechnology, can enhance the removal of uremic toxins by many folds. However, changing the pH at a specific membrane thickness does not affect the flux significantly.

  11. Solid on liquid deposition, a review of technological solutions

    OpenAIRE

    Homsy, Alexandra; Laux, Edith; Jeandupeux, Laure; Charmet, Jérôme; Bitterli, Roland; Botta, Chiara; Rebetez, Yves; Banakh, Oksana; Keppner, Herbert

    2015-01-01

    Solid-on-liquid deposition (SOLID) techniques are of great interest to the MEMS and NEMS (Micro- and Nano Electro Mechanical Systems) community because of potential applications in biomedical engineering, on-chip liquid trapping, tunable micro-lenses, and replacements of gate oxides. However, depositing solids on liquid with subsequent hermetic sealing is difficult because liquids tend to have a lower density than solids. Furthermore, current systems seen in nature lack thermal, mechanical or...

  12. A new self-consistent model for thermodynamics of binary solutions

    Czech Academy of Sciences Publication Activity Database

    Svoboda, Jiří; Shan, Y. V.; Fischer, F. D.

    2015-01-01

    Roč. 108, NOV (2015), s. 27-30 ISSN 1359-6462 R&D Projects: GA ČR(CZ) GA14-24252S Institutional support: RVO:68081723 Keywords : Thermodynamics * Analytical methods * CALPHAD * Phase diagram * Self-consistent model Subject RIV: BJ - Thermodynamics Impact factor: 3.305, year: 2015

  13. Solid solution cermet: (Ti,Nb)(CN)-Ni cermet.

    Science.gov (United States)

    Kwon, Hanjung; Jung, Sun-A

    2014-11-01

    Solid solution powders without W, (Ti,Nb)(CN) powders with a B1 structure (NaCl like), were synthesized by high energy milling and carbothermal reduction in nitrogen. The range of molar ratios of Ti/Nb for forming complete (Ti,Nb)(CN) phase was broader than that of Ti/W for the (Ti,W)(CN) phase because carbide or carbonitride of Nb had a B1 crystal structure identical to Ti(CN) while WC had a hexagonal crystal structure. The results revealed that the hardness of (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,W)(CN)-Ni cermets. The lower density of the (Ti,Nb)(CN) powder contributed to the higher hardness compared to (Ti,W)(CN) because the volumetric ratio of (Ti,Nb)(CN) in the (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,Nb)(CN) in the (Ti,W)(CN)-Ni cermets at the same weight ratio of Ni. Additionally, it was assumed that intrinsic the properties of (Ti,Nb)(CN) could also be the cause for the high hardness of the (Ti,Nb)(CN)-Ni cermets.

  14. Partitioning of rhodium and ruthenium between Pd–Rh–Ru and (Ru,Rh)O{sub 2} solid solutions in high-level radioactive waste glass

    Energy Technology Data Exchange (ETDEWEB)

    Sugawara, Toru, E-mail: toru@gipc.akita-u.ac.jp [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Ohira, Toshiaki [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Komamine, Satoshi; Ochi, Eiji [Research and Development Department, Reprocessing Business Division, Japan Nuclear Fuel Limited, 4-108, Okitsuke, Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

    2015-10-15

    The partitioning of rhodium and ruthenium between Pd–Rh–Ru alloy with a face-centered cubic (FCC) structure and (Ru,Rh)O{sub 2} solid solution has been investigated between 1273 and 1573 K at atmospheric oxygen fugacity. The rhodium and ruthenium contents in FCC increase, while the RhO{sub 2} content in (Ru,Rh)O{sub 2} decreases with increasing temperature due to progressive reduction of the system. Based on the experimental results and previously reported thermodynamic data, the thermodynamic mixing properties of FCC phase and (Ru,Rh)O{sub 2} have been calibrated in an internally consistent manner. Phase equilibrium of platinum grope metals in an HLW glass was calculated by using the obtained thermodynamic parameters.

  15. A unified approach to model uptake kinetics of trace elements in complex aqueous – solid solution systems

    International Nuclear Information System (INIS)

    Thien, Bruno M.J.; Kulik, Dmitrii A.; Curti, Enzo

    2014-01-01

    Highlights: • There are several models able to describe trace element partitioning in growing minerals. • To describe complex systems, those models must be embedded in a geochemical code. • We merged two models into a unified one suitable for implementation in a geochemical code. • This unified model was tested against coprecipitation experimental data. • We explored how our model reacts to solution depletion effects. - Abstract: Thermodynamics alone is usually not sufficient to predict growth-rate dependencies of trace element partitioning into host mineral solid solutions. In this contribution, two uptake kinetic models were analyzed that are promising in terms of mechanistic understanding and potential for implementation in geochemical modelling codes. The growth Surface Entrapment Model (Watson, 2004) and the Surface Reaction Kinetic Model (DePaolo, 2011) were shown to be complementary, and under certain assumptions merged into a single analytical expression. This Unified Uptake Kinetics Model was implemented in GEMS3K and GEM-Selektor codes ( (http://gems.web.psi.ch)), a Gibbs energy minimization package for geochemical modelling. This implementation extends the applicability of the unified uptake kinetics model to accounting for non-trivial factors influencing the trace element partitioning into solid solutions, such as the changes in aqueous solution composition and speciation, or the depletion effects in closed geochemical systems

  16. Free energies of formation of WC and WzC and the thermodynamic properties of carbon in solid tungsten

    Science.gov (United States)

    Gupta, D. K.; Seigle, L. L.

    1974-01-01

    The activity of carbon in the two-phase regions - W + WC and W + W2C was obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W2C were calculated. The temperature of the invariant reaction W2C = W + WC was fixed at 1570 + or - 5K. Using available solubility data for C in solid W, the partial molar free energy of C in the dilute solid solution was also calculated. The heat of solution of C in W, and the excess entropy for the interstitial solid solution, were computed, assuming that the carbon atoms reside in the octahedral interstices of bcc W.

  17. Atomistic simulation of solid solution hardening in Mg/Al alloys: Examination of composition scaling and thermo-mechanical relationships

    International Nuclear Information System (INIS)

    Yi, Peng; Cammarata, Robert C.; Falk, Michael L.

    2016-01-01

    Dislocation mobility in a solid solution was studied using atomistic simulations of an Mg/Al system. The critical resolved shear stress (CRSS) for the dislocations on the basal plane was calculated at temperatures from 0 K to 500 K with solute concentrations from 0 to 7 at%, and with four different strain rates. Solute hardening of the CRSS is decomposed into two contributions: one scales with c 2/3 , where c is the solute concentration, and the other scales with c 1 . The former was consistent with the Labusch model for local solute obstacles, and the latter was related to the athermal plateau stress due to the long range solute effect. A thermo-mechanical model was then used to analyze the temperature and strain rate dependences of the CRSS, and it yielded self-consistent and realistic results. The scaling laws were confirmed and the thermo-mechanical model was successfully parameterized using experimental measurements of the CRSS for Mg/Al alloys under quasi-static conditions. The predicted strain rate sensitivity from the experimental measurements of the CRSS is in reasonable agreement with separate mechanical tests. The concentration scaling and the thermo-mechanical relationships provide a potential tool to analytically relate the structural and thermodynamic parameters on the microscopic level with the macroscopic mechanical properties arising from dislocation mediated deformation.

  18. Comparative solution and solid-phase glycosylations toward a disaccharide library

    DEFF Research Database (Denmark)

    Agoston, K.; Kröger, Lars; Agoston, Agnes

    2009-01-01

    A comparative study on solution-phase and solid-phase oligosaccharide synthesis was performed. A 16-member library containing all regioisomers of Glc-Glc, Glc-Gal, Gal-Glc, and Gal-Gal disaccharides was synthesized both in solution and on solid phase. The various reaction conditions for different...

  19. Crystal chemical analysis of formation of solid solutions on the basis of compounds with garnet structure

    International Nuclear Information System (INIS)

    Kuz'micheva, G.M.; Kozlikin, S.N.

    1989-01-01

    Crystal chemical formulas permitting to evaluate the character of changes in interatomic distances during isomorphous substitution and, hence, the probability of formation of internal solid solutions and successive isomorphous substitution, are presented. The possibility of formation of introduction solid solutions is considered, using as an example Sc, Y oxides, rare earths with garnet structure

  20. Theoretical Predictions of the thermodynamic Properties of Solid Sorbents Capture CO2 Applications

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Yuhua; Sorescu, Dan; Luebke David; Pennline, Henry

    2012-05-02

    We are establishing a theoretical procedure to identify most potential candidates of CO{sub 2} solid sorbents from a large solid material databank to meet the DOE programmatic goal for energy conversion; and to explore the optimal working conditions for the promising CO{sub 2} solid sorbents, especially from room to warm T ranges with optimal energy usage, used for both pre- and post-combustion capture technologies.

  1. The calcium oxide influence on formation of manganese, calcium pyrovanadate solid solutions

    International Nuclear Information System (INIS)

    Vatolin, N.A.; Volkova, P.I.; Sapozhnikova, T.V.; Ovchinnikova, L.A.

    1988-01-01

    The X-ray graphic, derivatographic, microscopic and chemical methods are used to study solid solutions of manganese, calcium pyrovanadates containing 1-10 mass% CaO and the products of interaction of reprocessing charges of vanadium-containing converter slags intended for he formation of manganese and calcium pyrovanadates with additions of calcium oxide within 10-90 mass%. It is established that in the case of 1-6 mass% CaO content in manganese pyrovanadate solid interstitial solutions appear, while at 6-20 mass% CaO - solid substitution solutions form. The results of calculating elementary cell parameters as well as melting temperatures and pyrovanadate solid solution solubility depending on CaO content are presented. The best solubility of introduction solid solutions during vanadium extraction according to the lime technology is found

  2. Thermodynamic modelling of unloaded and loaded N,N-diethylethanolamine solutions

    Directory of Open Access Journals (Sweden)

    Monica Garcia

    2016-10-01

    Full Text Available Chemical absorption is a crucial step for several chemical processes such as ammonia production, coal gasification, methane reforming, ethylene oxide manufacturing and treatment of associated gas streams [1]. It is considered one of the main processes to eliminate CO2 emissions from power plants by post-combustion.Use of new solvents are of high interest in chemical absorption for carbon capture. For the design of the absorption and desorption columns it is essential to know the vapour–liquid equilibrium (VLE, heat of absorption and densities. N,N-diethylethanolamine (DEEA appeared as one of the amines with the lowest amount of energy needed for its regeneration [2], which would directly decrease the operation costs. DEEA has a high CO2 loading of 1 mol/mol of amine compared to the traditional MEA solvent (0.5 mol/mol amine and is obtained from renewable sources [1]. The main weakness is its low absorption rate and consequently the use of promoters is desirable.In this work, a thermodynamic model based on the electrolyte non-random two-liquid theory (eNRTL was created and fitted to correlate and predict the partial and total pressures of the unloaded and loaded aqueous DEEA solutions. New interaction parameters were obtained for the binary and tertiary system. This model represents the vapour pressures of the pure components, DEEA and H2O, with AARD of 1.9% and 1.73% respectively. Furthermore, the fitted model predicts the total pressure above the binary system, H2O-DEEA, with AARD of 0.05%. The excess of enthalpy and densities are predicted with AARD of 5.63% and 1.38% respectively. The tertiary system, H2O-DEEA-CO2, is fitted for 2 M and 5 M DEEA solutions with loading between 0.042 and 0.9 mol CO2/mol amine up to 80 °C. Results of CO2 partial pressures and total pressures are reproduced, with AARD of 19.45% and 16.18% respectively. Densities are predicted with an AARD of 1.52%. Keywords: DEEA, CO2 capture, Chemical

  3. Dissolution of carbon dioxide in aqueous electrolyte solutions, in the context of geological storage: A thermodynamic approach

    International Nuclear Information System (INIS)

    Liborio, Barbara

    2017-01-01

    This thesis studies the enthalpy of solution of carbon dioxide in electrolyte aqueous solutions. To develop theoretical models describing the systems (CO 2 -water-salt) under the geological storage conditions of carbon dioxide, it is necessary to have experimental data, namely solubility and enthalpy. In this study, a customized flow mixing unit was adapted to a SETARAM C-80 calorimeter to measure the enthalpy of CO 2 solution in aqueous electrolyte solutions (NaCl, CaCl 2 and Na 2 SO 4 ) at the ionic strengths between 2 and 6 and at temperatures between 323.1 K and 372.9 K and pressures ranging from 2 to 16 MPa. Data from the literature were used to adjust the thermodynamic phase equilibrium model in the Y-φ approach. The thermodynamic model reproduces the experimental enthalpies to plus or minus 10%. The calculation of the enthalpy in the rigorous model is strongly dependent on the data of the literature. An experimental device has been set up for the determination of the molar volume of CO 2 at infinite dilution, which is necessary for thermodynamic modeling. The carbon dioxide to be stored may contain impurities such as annexes (O 2 , N 2 , SO x , H 2 S, N y O x , H 2 , CO and Ar). Under the objective of studying the influence of these impurities, an experimental apparatus has been set up for the measurement of enthalpies of solution of SO 2 in water and aqueous solutions of NaCl and the first results are promising. (author)

  4. A computationally effective formulation of the thermodynamic properties of LiBr-H2O solutions from 273 to 500 K over full composition range

    Czech Academy of Sciences Publication Activity Database

    Pátek, Jaroslav; Klomfar, Jaroslav

    2006-01-01

    Roč. 29, č. 4 (2006), s. 566-578 ISSN 0140-7007 Institutional research plan: CEZ:AV0Z20760514 Keywords : water-lithium bromide * aqueous solution * thermodynamic properties Subject RIV: BJ - Thermodynamics Impact factor: 0.936, year: 2006

  5. Thermodynamic properties of LiCl solutions in N-methylacetamide at 308.15-328.15 K

    Science.gov (United States)

    Manin, N. G.; Kolker, A. M.

    2017-12-01

    Enthalpies of dissolution of crystalline LiCl and enthalpies of dilution of LiCl solutions in N-methylacetamide (NMA) with electrolyte concentrations no greater than 0.32 m are measured on an isoperibolic calorimeter at 308.15, 318.15, and 328.5 K. Standard enthalpies of the dissolution of LiCl in NMA are calculated at different temperatures. The thermodynamic properties of the solution and its components are calculated and analyzed in the investigated range of concentrations and temperatures.

  6. Laser-irradiated thermodynamic behaviors of spallation and recombination at solid-state interface

    International Nuclear Information System (INIS)

    Lai, H.-Y.; Huang, P.-H.

    2008-01-01

    A microscopic insight of interfacial spallation and recombination behaviors at multilayer thin-film interface induced by incident femtosecond pulsed laser is presented in this paper. Such two different aforementioned behaviors are investigated via the thermodynamic trajectories obtained by using standard Lennard-Jones (L-J) molecular dynamics (MD) simulation. Based on the simulation results, the interfacial damages of multilayer thin film are dominated by a critical threshold that induces an extraordinary expansive dynamics and phase transitions leading to the structural softened and tensile spallation at interface. The critical damage threshold is evaluated at around 8.5 J/m 2 which governs the possible occurrence of two different regimes, i.e. interfacial spallaiton and recombination. In interfacial damage region, quasi-isothermal thermodynamic trajectories can be observed after the interfacial spallation occurs. Moreover, the result of thermodynamic trajectories analyses indicates that, the relaxation of pressure wave may cause the over-heated interfacial zone to reduce volumetric density, thus leading to structural softness and even weaken interfacial structural strength. The crucial effect leading to the phenomenon of low tension spallation is identified

  7. A Local Composition Model for Paraffinic Solid Solutions

    DEFF Research Database (Denmark)

    Coutinho, A.P. João; Knudsen, Kim; Andersen, Simon Ivar

    1996-01-01

    The description of the solid-phase non-ideality remains the main obstacle in modelling the solid-liquid equilibrium of hydrocarbons. A theoretical model, based on the local composition concept, is developed for the orthorhombic phase of n-alkanes and tested against experimental data for binary sy...... systems. It is shown that it can adequately predict the experimental phase behaviour of paraffinic mixtures. This work extends the applicability of local composition models to the solid phase. Copyright (C) 1996 Elsevier Science Ltd....

  8. Thermodynamic analyses of municipal solid waste gasification plant integrated with solid oxide fuel cell and Stirling hybrid system

    DEFF Research Database (Denmark)

    Rokni, Masoud

    2015-01-01

    the plant efficiency in terms of operating conditions. Compared with modern waste incinerators with heat recovery, the gasification process integrated with SOFC and Stirling engine permits an increase in electricity output up of 50%, which means that the solid waste gasification process can compete......Municipal solid waste (MSW) can be considered a valid biomass to be used in a power plant. The major advantage is the reduction of pollutants and greenhouse gases emissions not only within large cities but also globally. Another advantage is that by their use it is possible to reduce the waste...... storage in landfills and devote these spaces to other human activities. It is also important to point out that this kind of renewable energy suffers significantly less availability which characterizes other type of renewable energy sources such as in wind and solar energy.In a gasification process, waste...

  9. Quantitative Assessment of Thermodynamic Constraints on the Solution Space of Genome-Scale Metabolic Models

    Science.gov (United States)

    Hamilton, Joshua J.; Dwivedi, Vivek; Reed, Jennifer L.

    2013-01-01

    Constraint-based methods provide powerful computational techniques to allow understanding and prediction of cellular behavior. These methods rely on physiochemical constraints to eliminate infeasible behaviors from the space of available behaviors. One such constraint is thermodynamic feasibility, the requirement that intracellular flux distributions obey the laws of thermodynamics. The past decade has seen several constraint-based methods that interpret this constraint in different ways, including those that are limited to small networks, rely on predefined reaction directions, and/or neglect the relationship between reaction free energies and metabolite concentrations. In this work, we utilize one such approach, thermodynamics-based metabolic flux analysis (TMFA), to make genome-scale, quantitative predictions about metabolite concentrations and reaction free energies in the absence of prior knowledge of reaction directions, while accounting for uncertainties in thermodynamic estimates. We applied TMFA to a genome-scale network reconstruction of Escherichia coli and examined the effect of thermodynamic constraints on the flux space. We also assessed the predictive performance of TMFA against gene essentiality and quantitative metabolomics data, under both aerobic and anaerobic, and optimal and suboptimal growth conditions. Based on these results, we propose that TMFA is a useful tool for validating phenotypes and generating hypotheses, and that additional types of data and constraints can improve predictions of metabolite concentrations. PMID:23870272

  10. Quantitative assessment of thermodynamic constraints on the solution space of genome-scale metabolic models.

    Science.gov (United States)

    Hamilton, Joshua J; Dwivedi, Vivek; Reed, Jennifer L

    2013-07-16

    Constraint-based methods provide powerful computational techniques to allow understanding and prediction of cellular behavior. These methods rely on physiochemical constraints to eliminate infeasible behaviors from the space of available behaviors. One such constraint is thermodynamic feasibility, the requirement that intracellular flux distributions obey the laws of thermodynamics. The past decade has seen several constraint-based methods that interpret this constraint in different ways, including those that are limited to small networks, rely on predefined reaction directions, and/or neglect the relationship between reaction free energies and metabolite concentrations. In this work, we utilize one such approach, thermodynamics-based metabolic flux analysis (TMFA), to make genome-scale, quantitative predictions about metabolite concentrations and reaction free energies in the absence of prior knowledge of reaction directions, while accounting for uncertainties in thermodynamic estimates. We applied TMFA to a genome-scale network reconstruction of Escherichia coli and examined the effect of thermodynamic constraints on the flux space. We also assessed the predictive performance of TMFA against gene essentiality and quantitative metabolomics data, under both aerobic and anaerobic, and optimal and suboptimal growth conditions. Based on these results, we propose that TMFA is a useful tool for validating phenotypes and generating hypotheses, and that additional types of data and constraints can improve predictions of metabolite concentrations. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  11. Solid lipid nanoparticles suspension versus commercial solutions for dermal delivery of minoxidil.

    Science.gov (United States)

    Padois, Karine; Cantiéni, Céline; Bertholle, Valérie; Bardel, Claire; Pirot, Fabrice; Falson, Françoise

    2011-09-15

    Solid lipid nanoparticles have been reported as possible carrier for skin drug delivery. Solid lipid nanoparticles are produced from biocompatible and biodegradable lipids. Solid lipid nanoparticles made of semi-synthetic triglycerides stabilized with a mixture of polysorbate and sorbitan oleate were loaded with 5% of minoxidil. The prepared systems were characterized for particle size, pH and drug content. Ex vivo skin penetration studies were performed using Franz-type glass diffusion cells and pig ear skin. Ex vivo skin corrosion studies were realized with a method derived from the Corrositex(®) test. Solid lipid nanoparticles suspensions were compared to commercial solutions in terms of skin penetration and skin corrosion. Solid lipid nanoparticles suspensions have been shown as efficient as commercial solutions for skin penetration; and were non-corrosive while commercial solutions presented a corrosive potential. Solid lipid nanoparticles suspensions would constitute a promising formulation for hair loss treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Review: Water recovery from brines and salt-saturated solutions: operability and thermodynamic efficiency considerations for desalination technologies.

    Science.gov (United States)

    Vane, Leland M

    2017-03-08

    When water is recovered from a saline source, a brine concentrate stream is produced. Management of the brine stream can be problematic, particularly in inland regions. An alternative to brine disposal is recovery of water and possibly salts from the concentrate. This review provides an overview of desalination technologies and discusses the thermodynamic efficiencies and operational issues associated with the various technologies particularly with regard to high salinity streams. Due to the high osmotic pressures of the brine concentrates, reverse osmosis, the most common desalination technology, is impractical. Mechanical vapor compression which, like reverse osmosis, utilizes mechanical work to operate, is reported to have the highest thermodynamic efficiency of the desalination technologies for treatment of salt-saturated brines. Thermally-driven processes, such as flash evaporation and distillation, are technically able to process saturated salt solutions, but suffer from low thermodynamic efficiencies. This inefficiency could be offset if an inexpensive source of waste or renewable heat could be used. Overarching issues posed by high salinity solutions include corrosion and the formation of scales/precipitates. These issues limit the materials, conditions, and unit operation designs that can be used.

  13. Chemistry and Thermodynamics of Solid Waste Streams used in Waste-to-Energy (WTE) Systems

    Data.gov (United States)

    National Aeronautics and Space Administration — In spite of our best efforts to minimize the amount of disposable supplies (and the associated packaging) used during space missions, the accumulation of solid...

  14. Precipitation in Al–Mg solid solution prepared by solidification under high pressure

    International Nuclear Information System (INIS)

    Jie, J.C.; Wang, H.W.; Zou, C.M.; Wei, Z.J.; Li, T.J.

    2014-01-01

    The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al 12 Mg 17 phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solution appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β

  15. User's guide to PROTOCOL, a numerical simulator for the dissolution reactions of inorganic solids in aqueous solutions

    International Nuclear Information System (INIS)

    Pickrell, G.; Jackson, D.D.

    1984-10-01

    This report provides a user's manual for PROTOCOL, a comprehensive coupled kinetic/equilibrium computer program for analyzing the dissolution reactions of solids with aqueous solutions, specifically applied to the potential corrosion of vitrified nuclear waste by groundwater. The capabilities and available options are summarized as well as instructions for setting up and running problems. Also described in this report and included in the PROTOCOL software package are MASTER, a master file of species thermodynamic data, MANEQL, a preprocessor program and POSTP, a postprocessor. POSTP provides offline plotting using the CRAY-1 DISSPLA 9.0 graphics library. PROTOCOL is operational on the CDC-7600 and CRAY-1 computers at the Lawrence Livermore National Laboratory. 7 references, 10 figures, 2 tables

  16. Comparisons of kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide adsorption in aqueous solution with graphene oxide, zeolite and activated carbon

    Science.gov (United States)

    Chang, Shenteng; Lu, Chungsying; Lin, Kun-Yi Andrew

    2015-01-01

    Graphene oxide (GO), sodium Y-type zeolite (NaY) and granular activated carbon (GAC) are selected as adsorbents to study their kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide (TMAH) adsorption from water. The adsorption kinetics follows the pseudo-second-order rate law while the adsorption thermodynamics shows an exothermic reaction with GO and GAC but displays an endothermic reaction with NaY. The adsorbed TMAH can be readily desorbed from the surface of GO and NaY by 0.05 M NaCl solution. A comparative study on the cyclic TMAH adsorption with GO, NaY and GAC is also conducted and the results reveal that GO exhibits the greatest TMAH adsorption capacity as well as superior reversibility of TMAH adsorption over 10 cycles of adsorption and desorption process. These features indicate that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment.

  17. Thermodynamic Characteristics of Reactions of the Formation of Complexes between Triglycine and Ni2+ Ions in Aqueous Solution

    Science.gov (United States)

    Gorboletova, G. G.; Metlin, A. A.; Bychkova, S. A.

    2018-05-01

    Thermal effects of reactions of the formation of complexes between Ni(II) and triglycine are determined via direct calorimetry in aqueous solutions at 298.15 K and ionic strengths of 0.2, 0.5, and 1.0 (KNO3). Standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°) of complexing processes in the investigated systems are calculated. The structures of triglycinate complexes NiL+, NiH-1L, NiL2, NiH-2L2- 2, NiL- 3, and NiH-3L4- 3 are introduced to compare the obtained values and data on the thermodynamics of triglycinate complexes of Ni(II).

  18. Thermodynamics of aqueous carbonate solutions including mixtures of sodium carbonate, bicarbonate, and chloride

    Energy Technology Data Exchange (ETDEWEB)

    Peiper, J.C.; Pitzer, K.S.

    1982-01-01

    Recently the authors examined electrochemical-cell data leading to values of the activity coefficient for aqueous sodium bicarbonate. Since that preliminary analysis, new experimental measurements have been published which contribute significantly to the overall thermodynamic understanding of (sodium carbonate + sodium bicarbonate + carbonic acid). In this more extensive examination we consider a wide variety of measurements leading to activity coefficients of Na/sub 2/CO/sub 3/ and NaHCO/sub 3/ from 273 to 323 K and to relative molar enthalpies and heat capacities at 298.15 K. Tables of thermodynamic quantities at selected temperatures are included. 47 references, 2 figures, 6 tables.

  19. Computationally efficient and quantitatively accurate multiscale simulation of solid-solution strengthening by ab initio calculation

    International Nuclear Information System (INIS)

    Ma, Duancheng; Friák, Martin; Pezold, Johann von; Raabe, Dierk; Neugebauer, Jörg

    2015-01-01

    We propose an approach for the computationally efficient and quantitatively accurate prediction of solid-solution strengthening. It combines the 2-D Peierls–Nabarro model and a recently developed solid-solution strengthening model. Solid-solution strengthening is examined with Al–Mg and Al–Li as representative alloy systems, demonstrating a good agreement between theory and experiments within the temperature range in which the dislocation motion is overdamped. Through a parametric study, two guideline maps of the misfit parameters against (i) the critical resolved shear stress, τ 0 , at 0 K and (ii) the energy barrier, ΔE b , against dislocation motion in a solid solution with randomly distributed solute atoms are created. With these two guideline maps, τ 0 at finite temperatures is predicted for other Al binary systems, and compared with available experiments, achieving good agreement

  20. Face-centered-cubic Nb-Si solid solutions produced by picosecond pulsed laser quenching

    International Nuclear Information System (INIS)

    Wang, W.K.; Spaepen, F.

    1985-01-01

    Face-centered-cubic Nb/sub 100-x/Si/sub x/ solid solutions (10 2 . The lattice parameters of these solutions suggest that the solute atoms can be interstitial or substitutional, probably as a result of a change in the quenching conditions

  1. Nanometric solid solutions of the fluorite and perovskite type crystal structures: Synthesis and properties

    Directory of Open Access Journals (Sweden)

    Snežana Bošković

    2012-09-01

    Full Text Available In this paper a short review of our results on the synthesis of nanosized CeO2, CaMnO3 and BaCeO3 solid solutions are presented. The nanopowders were prepared by two innovative methods: self propagating room temperature synthesis (SPRT and modified glycine/nitrate procedure (MGNP. Different types of solid solutions with rare earth dopants in concentrations ranging from 0–0.25 mol% were synthesized. The reactions forming solid solutions were studied. In addition, the characteristics of prepared nanopowders, phenomena during sintering and the properties of sintered samples are discussed.

  2. Thermodynamics of geothermal brines. I. Thermodynamic properties of vapor-saturated NaCl (aq) solutions from 0-300 {sup 0}C

    Energy Technology Data Exchange (ETDEWEB)

    Silvester, L.F.; Pitzer, K.S.

    1976-01-01

    Osmotic and activity coefficient data, enthalpy data, and heat capacity data on aqueous sodium chloride solutions from various sources have been fitted to a thirteen parameter equation. The equation reproduces the osmotic coefficient data to +-0.005 over the composition range 0-6M and temperature range 0-300{sup 0}C, enthalpy data to +-5-10 cal/mole for compositions of 0-5M at temperatures from 25-100{sup 0}C, and heat capacity data to +-0.5 cal/{sup 0}K for compositions of 0-2M at temperatures from 25-200{sup 0}C. Tabulated values of the total Gibbs energy, enthalpy, and heat capacity, plus partial molal and excess thermodynamic quantities of sodium chloride solutions for compositions of 0-6M at 25{sup 0}C intervals from 0-300{sup 0}C are given along with the same quantities in graphical form for compositions of 0-6M at temperatures of 100-350{sup 0}C.

  3. Thermodynamically Consistent Algorithms for the Solution of Phase-Field Models

    KAUST Repository

    Vignal, Philippe

    2016-01-01

    of thermodynamically consistent algorithms for time integration of phase-field models. The first part of this thesis focuses on an energy-stable numerical strategy developed for the phase-field crystal equation. This model was put forward to model microstructure

  4. On the thermodynamics of the liquid-solid transition in a small cluster

    International Nuclear Information System (INIS)

    Zhukov, Alexander V.; Kraynyukova, Anastasiya S.; Cao Jianshu

    2007-01-01

    Physics of phase transformations in finite systems has a long history, but there are many unresolved issues. Although there is a satisfactory qualitative picture of the phase transformations within an isolated small cluster, the experimentally observed dependence of the melting temperature on the cluster size contradicts the prediction of classical results. No clear physical picture of such a transformation exists for a condensed cluster in contact with gaseous environment. We propose a thermodynamic theory, which generalize previous results to the case of cluster with fluctuating number of constituent particles (open cluster). In this case, phase transition occurs because of size change during the nucleation/evaporation process. This allows us to explain the underlying physics of recent simulations and experiments. Although we used the grand canonical approach, our main results can be applied to isolated clusters. Particularly, we give simple arguments to explain the deviations of the cluster melting temperature dependence on cluster size from classical results

  5. Thermodynamic relations in high temperature and high pressure physics of solids

    International Nuclear Information System (INIS)

    Kumar, Munish

    1998-01-01

    Various possible simple relations based on the exact and approximate thermodynamic relations are derived. These relations can be used to investigate the variation of unit cell volume under the effect of pressure and temperature. Thermal expansivity and compressibility can be investigated directly at any pressure or temperature, or through the knowledge of equation of state (EOS). A relation to determine Anderson-Grueneisen parameter δ T under the effect of pressure is predicted. It is discussed that δ T is independent of pressure and thus Murnaghan equation of state works well in low pressure ranges, while the variation of δ T under high pressure should be taken into account. The product of coefficient of volume thermal expansion and bulk modulus remains constant, is correct at high pressure, provided that the pressure dependence of δ T is considered. (author)

  6. Thermodynamic Performance Study of Biomass Gasification, Solid Oxide Fuel Cell and Micro Gas Turbine Hybrid Systems

    DEFF Research Database (Denmark)

    Bang-Møller, Christian; Rokni, Masoud

    2010-01-01

    A system level modelling study of three combined heat and power systems based on biomass gasification is presented. Product gas is converted in a micro gas turbine (MGT) in the first system, in a solid oxide fuel cell (SOFC) in the second system and in a combined SOFC–MGT arrangement in the third...

  7. Alloying Solid Solution Strengthening of Fe-Ga Alloys: A First-Principle Study

    National Research Council Canada - National Science Library

    Chen, Kuiying; Cheng, Leon M

    2006-01-01

    ... and Co in cubic solid solution of Fe-Ga alloys. Mayer bond order "BO" values were used to evaluate the atomic bond strengths in the alloys, and were then used to assess the alloying strengthening characteristics...

  8. The growth and tensile deformation behavior of the silver solid solution phase with zinc

    International Nuclear Information System (INIS)

    Wu, Jiaqi; Lee, Chin C.

    2016-01-01

    The growth of homogeneous silver solid solution phase with zinc are conducted at two different compositions. X-ray diffraction (XRD) and Scanning electron microscope/Energy dispersive X-ray spectroscopy (SEM/EDX) are carried out for phase identification and chemical composition verification. The mechanical properties of silver solid solution phase with zinc are evaluated by tensile test. The engineering and true stress vs. strain curves are presented and analyzed, with those of pure silver in comparison. According to the experimental results, silver solid solution phase with zinc at both compositions show tempered yield strength, high tensile strength and large uniform strain compared to those of pure silver. Fractography further confirmed the superior ductility of silver solid solution phase with zinc at both compositions. Our preliminary but encouraging results may pave the way for the silver based alloys to be applied in industries such as electronic packaging and structure engineering.

  9. Synthesis of (U,Zr)C solid solutions under exothermic conditions

    International Nuclear Information System (INIS)

    Wang, L.L.; Moore, H.G.; Gladson, J.W.

    1993-01-01

    The reactions of forming (U,Zr)C solid solutions from their elemental components or similarly less stable reactants such as UC 2 are strongly exothermic due to the high stability of these solid solutions. A simple approach of utilizing this heat of formation energy to assist the solid solution reaction process is to intimately mix the less stable reactant powders and then pressed them into a compact. The compact is then heated to the ignition temperature of the reaction. The feasibility of this reaction method to synthesize (U,Zr)C solid solutions has been demonstrated in this study. The preliminary results also show that both the initial composition and the heating rate have a significant effect on the nature of the reaction process. As expected the degree of powder mixing was also found to affect the completeness of the reaction

  10. Prediction of heat capacity of amine solutions using artificial neural network and thermodynamic models for CO2 capture processes

    Science.gov (United States)

    Afkhamipour, Morteza; Mofarahi, Masoud; Borhani, Tohid Nejad Ghaffar; Zanganeh, Masoud

    2018-03-01

    In this study, artificial neural network (ANN) and thermodynamic models were developed for prediction of the heat capacity ( C P ) of amine-based solvents. For ANN model, independent variables such as concentration, temperature, molecular weight and CO2 loading of amine were selected as the inputs of the model. The significance of the input variables of the ANN model on the C P values was investigated statistically by analyzing of correlation matrix. A thermodynamic model based on the Redlich-Kister equation was used to correlate the excess molar heat capacity ({C}_P^E) data as function of temperature. In addition, the effects of temperature and CO2 loading at different concentrations of conventional amines on the C P values were investigated. Both models were validated against experimental data and very good results were obtained between two mentioned models and experimental data of C P collected from various literatures. The AARD between ANN model results and experimental data of C P for 47 systems of amine-based solvents studied was 4.3%. For conventional amines, the AARD for ANN model and thermodynamic model in comparison with experimental data were 0.59% and 0.57%, respectively. The results showed that both ANN and Redlich-Kister models can be used as a practical tool for simulation and designing of CO2 removal processes by using amine solutions.

  11. Colloidal quantum dot solids for solution-processed solar cells

    KAUST Repository

    Yuan, Mingjian; Liu, Mengxia; Sargent, Edward H.

    2016-01-01

    Solution-processed photovoltaic technologies represent a promising way to reduce the cost and increase the efficiency of solar energy harvesting. Among these, colloidal semiconductor quantum dot photovoltaics have the advantage of a spectrally

  12. Computationally efficient and quantitatively accurate multiscale simulation of solid-solution strengthening by ab initio calculation

    Czech Academy of Sciences Publication Activity Database

    Ma, D.; Friák, Martin; von Pezold, J.; Raabe, D.; Neugebauer, J.

    2015-01-01

    Roč. 85, FEB (2015), s. 53-66 ISSN 1359-6454 Institutional support: RVO:68081723 Keywords : Solid-solution strengthening * DFT * Peierls–Nabarro model * Ab initio * Al alloys Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 5.058, year: 2015

  13. Formation of solid solution during mutual diffusion of tungsten and molybdenum in the process of sintering

    International Nuclear Information System (INIS)

    Timofeeva, A.A.; Bulat, I.B.; Voronin, Yu.V.; Fedoseev, G.K.; Karasev, V.M.

    1984-01-01

    A process of a solid solution homogenization during sintering of W-15Mo and W-5Mo alloys is studied by the methods of density measurements, analysis of the X-ray lines physical broadening and determination of crystalline lattice constant. Study of the process of solid solution formation under conditions of powder composite sintering is shown to be conducted with account of peculiarities of tungsten and molybdenum mutual diffusion in the investigated temperature range of concentrations

  14. Thermal expansion studies on uranium-neodymium mixed oxide solid solutions

    International Nuclear Information System (INIS)

    Panneerselvam, G.; Venkata Krishnan, R.; Antony, M.P.; Nagarajan, K.

    2012-01-01

    Uranium-Neodymium mixed oxides solid solutions (U 1-y Nd y ) O 2 (y=0.2-0.95) were prepared by combustion synthesis using citric acid as fuel. Structural characterization and computation of lattice parameter was carried out from room temperature X-ray diffraction measurements. Single-phase fluorite structure was observed up to y=0.80. For solid solutions with y>0.80 additional Nd 2 O 3 lines were visible

  15. Numerical Thermodynamic Analysis of Two-Phase Solid-Liquid Abrasive Flow Polishing in U-Type Tube

    Directory of Open Access Journals (Sweden)

    Junye Li

    2014-08-01

    Full Text Available U-type tubes are widely used in military and civilian fields and the quality of the internal surface of their channel often determines the merits and performance of a machine in which they are incorporated. Abrasive flow polishing is an effective method for improving the channel surface quality of a U-type tube. Using the results of a numerical analysis of the thermodynamic energy balance equation of a two-phase solid-liquid flow, we carried out numerical simulations of the heat transfer and surface processing characteristics of a two-phase solid-liquid abrasive flow polishing of a U-type tube. The distribution cloud of the changes in the inlet turbulent kinetic energy, turbulence intensity, turbulent viscosity, and dynamic pressure near the wall of the tube were obtained. The relationships between the temperature and the turbulent kinetic energy, between the turbulent kinetic energy and the velocity, and between the temperature and the processing velocity were also determined to develop a theoretical basis for controlling the quality of abrasive flow polishing.

  16. Thermodynamic investigations of the Mn-Ni-C-N quarternary alloys by solid-state galvanic cell technique

    International Nuclear Information System (INIS)

    Teng Lidong; Aune, Ragnhild; Seetharaman, Seshadri

    2005-01-01

    In view of the important applications of carbides and nitrides of transition metals in the hard materials industries, the thermodynamic activities of manganese in Mn-Ni-C-N alloys have been studied by solid-state galvanic cell technique with CaF 2 as the solid electrolyte. The phase compositions and microstructure of various alloys have been analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Nitrogen was introduced into the alloy by equilibrating with N 2 gas. It was established during the experiments that the solubility of nitrogen in the alloys was affected by the carbon content. A (Mn,Ni) 4 (N,C) nitride was formed during the nitriding procedure in the alloys. The electromotive force (EMF) measurements were carried out in the temperature range 940-1127 K in order to determine the activities of Mn in the alloys. The activities of manganese were calculated and compared with those of the corresponding Mn-Ni-C ternary alloys

  17. High-temperature thermodynamic data for species in aqueous solution. Final report

    International Nuclear Information System (INIS)

    Cobble, J.W.; Murray, R.C. Jr.; Turner, P.J.; Chen, K.

    1982-05-01

    This final report summarizes the results of experimental and theoretical research on the high temperature thermodynamic properties of aqueous species important to nuclear reactor water chemistry. Methods of predicting thermodynamic functions are included for electrolytes up to 300 0 C where experimental data are lacking. Data in the literature are evaluated and tables of important equilibrium constants for 78 reactions encountered in corrosion and precipitation in nuclear reactors are listed up to 300 0 C. Finally, tables of free energy functions from 0 to 300 0 C are given for 56 individual species. These data represented form a major compilation resulting from the most advanced experimental and theoretical methods. Illustrations of the use of the tables are given for problems involving pH control, precipitation, and corrosion. 11 figures, 100 tables

  18. Experimental solid state NMR of gas hydrates : problems and solutions

    Energy Technology Data Exchange (ETDEWEB)

    Moudrakovski, I.; Lu, H.; Ripmeester, J. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences; Kumar, R.; Susilo, R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Luzi, M. [GeoForschungsZentrum Potsdam, Potsdam (Germany)

    2008-07-01

    Solid State NMR is a suitable spectroscopic technique for hydrate research for several reasons, including its capability to distinguish between different structural types of hydrates, its quantitative nature and potential for both in-situ and time resolved experiments. This study illustrated the applications of solid state NMR for compositional and structural studies of clathrate hydrates, with particular emphasis on experimental techniques and potential ways to overcome technical difficulties. In order to use the method to its full capacity, some instrumental developments are needed to adapt it to the specific experimental requirements of hydrate studies, such as very low temperatures and high pressures. This presentation discussed the quantification of the Carbon-13 spectra with examples from natural and synthetic hydrates prepared from multi-component mixtures of hydrocarbons. The main approach used for the first two examples was Carbon-13 NMR with Magic Angle Spinning (MAS) at -100 degrees C. The detailed characterization of mixed hydrogen hydrates required low temperature hydrogen MAS. The quantification problems encountered during these experiments were also discussed. The purpose of these recent experimental developments was to prompt wider application of Solid State NMR in hydrate research. NMR proved to be a viable method for analyzing the composition and structure of multi-component mixed gas hydrates; characterizing natural gas hydrates; and, evaluating the formation conditions and properties of mixed hydrogen hydrates. The limitations of the method were highlighted and sensible choices of experimental conditions and techniques that ensure accurate results were discussed. 34 refs., 10 figs.

  19. Thermodynamic and structural properties of high temperature solid and liquid EuBr2

    DEFF Research Database (Denmark)

    Rycerz, L.; Gadzuric, S.; Ingier-Stocka, E.

    2005-01-01

    Heat capacity of solid and liq. EuBr2 was measured by differential scanning calorimetry in the temp. range 300-1100 K. The temp. and enthalpy of fusion were also detd. exptl. By combination of these results with the literature data on the entropy at 298.15 K, S(o,m) (EuBr2, s, 298.15 K) , and the...

  20. Cefuroxime axetil solid dispersions prepared using solution enhanced dispersion by supercritical fluids.

    Science.gov (United States)

    Jun, Seoung Wook; Kim, Min-Soo; Jo, Guk Hyun; Lee, Sibeum; Woo, Jong Soo; Park, Jeong-Sook; Hwang, Sung-Joo

    2005-12-01

    Cefuroxime axetil (CA) solid dispersions with HPMC 2910/PVP K-30 were prepared using solution enhanced dispersion by supercritical fluids (SEDS) in an effort to increase the dissolution rate of poorly water-soluble drugs. Their physicochemical properties in solid state were characterized by differential scanning calorimeter (DSC), powder X-ray diffraction (PXRD), Fourier transform infrared spectrometry (FT-IR) and scanning electron microscopy. No endothermic and characteristic diffraction peaks corresponding to CA were observed for the solid dispersions in DSC and PXRD. FTIR analysis demonstrated the presence of intermolecular hydrogen bonds between CA and HPMC 2910/PVP K-30 in solid dispersions, resulting in the formation of amorphous or non-crystalline CA. Dissolution studies indicated that the dissolution rates were remarkably increased in solid dispersions compared with those in the physical mixture and drug alone. In conclusion, an amorphous or non-crystalline CA solid dispersion prepared using SEDS could be very useful for the formulation of solid dosage forms.

  1. Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis

    International Nuclear Information System (INIS)

    Zaitseva, Ksenia V.; Varfolomeev, Mikhail A.; Solomonov, Boris N.

    2012-01-01

    Highlights: ► Solution enthalpies and activity coefficients of amines in methanol were measured. ► Thermodynamic functions of H-bonding of amines with methanol were determined. ► Specific interaction entropy of amines in methanol can be about zero or positive. ► Cooperativity of H-bonds in methanol media is smaller than in water solutions. ► A new view on analysis of specific interaction of solute with methanol is presented. - Abstract: Reactivity and equilibrium properties of organic molecules in self-associated liquids greatly depend on the hydrogen bonding with solvent. This work contains comprehensive thermodynamic analysis of hydrogen bonding of aliphatic and aromatic amines in self-associated solvent methanol. Enthalpies of solution at infinite dilution and limiting activity coefficients for the studied systems were measured experimentally. Enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol were determined. These values were found to be decreased compared with hydrogen bond energy in equimolar complexes “methanol–amine” determined in inert solvent or base media. A linear dependence between enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol was observed. It was firstly revealed that the entropy of specific interactions of amines with neat methanol can be about zero or positive. Disruption of solvent–solvent hydrogen bonds can be regarded as the most important step during dissolution of amine in methanol. It was found that the cooperative effect influences on the Gibbs energies of hydrogen bonding of amines in methanol, but in a lesser extent than in aqueous solutions. The new results show that the hydrogen bonding process in the self-associated solvents differs significantly from equimolar complexation in aprotic media.

  2. Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zaitseva, Ksenia V., E-mail: zaitseva.ksenia@gmail.com [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Varfolomeev, Mikhail A., E-mail: vma.ksu@gmail.com [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Solomonov, Boris N., E-mail: boris.solomonov@ksu.ru [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation)

    2012-05-10

    Highlights: Black-Right-Pointing-Pointer Solution enthalpies and activity coefficients of amines in methanol were measured. Black-Right-Pointing-Pointer Thermodynamic functions of H-bonding of amines with methanol were determined. Black-Right-Pointing-Pointer Specific interaction entropy of amines in methanol can be about zero or positive. Black-Right-Pointing-Pointer Cooperativity of H-bonds in methanol media is smaller than in water solutions. Black-Right-Pointing-Pointer A new view on analysis of specific interaction of solute with methanol is presented. - Abstract: Reactivity and equilibrium properties of organic molecules in self-associated liquids greatly depend on the hydrogen bonding with solvent. This work contains comprehensive thermodynamic analysis of hydrogen bonding of aliphatic and aromatic amines in self-associated solvent methanol. Enthalpies of solution at infinite dilution and limiting activity coefficients for the studied systems were measured experimentally. Enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol were determined. These values were found to be decreased compared with hydrogen bond energy in equimolar complexes 'methanol-amine' determined in inert solvent or base media. A linear dependence between enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol was observed. It was firstly revealed that the entropy of specific interactions of amines with neat methanol can be about zero or positive. Disruption of solvent-solvent hydrogen bonds can be regarded as the most important step during dissolution of amine in methanol. It was found that the cooperative effect influences on the Gibbs energies of hydrogen bonding of amines in methanol, but in a lesser extent than in aqueous solutions. The new results show that the hydrogen bonding process in the self-associated solvents differs significantly from equimolar complexation in aprotic media.

  3. Contribution to the study of the structure of silver krypton solid solutions; Contribution a l'etude de la structure des solutions solides argent-krypton

    Energy Technology Data Exchange (ETDEWEB)

    Levy, V; Tullairet, J; Delaplace, J; Antolin-Baudier, J; Adda, Y [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    The silver-krypton solid solutions formed by electrical discharge have been studied by X-rays, electrical resistivity and electronic transmission microscopy. The crystalline parameter and residual resistivity measurements have shown that the krypton atom behaves very differently to those of other elements of the periodic classification when dissolved in silver. The recovery of the crystalline parameter and of the electrical resistivity has been studied as a function of temperature. (authors) [French] Les solutions solides argent, krypton, realisees par decharges electrique ont ete etudiees par Rayons X, resistivite electrique et microscopie electronique en transmission. Les mesures de parametre cristallin et de resistivite residuelle ont montre que le comportement de l'atome de krypton est tres different de celui des autres elements de la classification periodique en solution dans l'argent. La restauration du parametre cristallin et de la resistivite electrique en fonction de la temperature a ete etudiee. (auteurs)

  4. Precipitation of Nd-Ca carbonate solid solution at 25 degrees C

    International Nuclear Information System (INIS)

    Carroll, S.A.

    1993-01-01

    The formation of a Nd-Ca carbonate solid solution was studied by monitoring the reactions of calcite with aqueous Nd, orthorhombic NdOHCO 3 (s) with aqueous Ca, and calcite with hexagonal Nd-carbonate solid phase as a function of time at 25 degrees C and controlled pCO 2 (g). All experiments reached steady state after 200 h of reaction. The dominant mechanism controlling the formation of the solid solution was precipitation of a Nd-Ca carbonate phase from the bulk solution as individual crystals or at the orthorhombic NdOHCO 3 (s)-solution interface. The lack of Nd adsorption or solid solution at the calcite-solution interface suggests that the solid solution was orthorhombic and may be modeled as a mixture of orthorhombic NdOHCO 3 (s) and aragonite. Orthorhombic NdOHCO 3 (s) was determined to be the stable Nd-carbonate phase in the Nd-CO 2 -H 2 O system at pCO 2 (g) 0.1 atmospheres at 25 degrees C. The equilibrium constant corrected to zero ionic strength for orthorhombic NdOHCO 3 (s) solubility is 10 10.41(±0.29) for the following: NdOHCO 3 (s) + 3H + = Nd 3+ + CO 2 (g) + H 2 O. Results are discussed in relation to radioactive waste disposal by burial, and specifically in relation to americium chemistry

  5. Thermodynamic analysis of an open cycle solid desiccant cooling system using Artificial Neural Network

    International Nuclear Information System (INIS)

    Koronaki, I.P.; Rogdakis, E.; Kakatsiou, T.

    2012-01-01

    Highlights: ► A neural network model based on experimental data was developed. ► Description of the experimental setup. ► Prediction of the state conditions of air at the process and regeneration stream. ► Sensitivity Analysis performed on these predicted results. ► Predicted output values in line with correlation model based on data from industry. - Abstract: This paper examines the performance of an installed open cycle air-conditioning system with a silica gel desiccant wheel which uses a conventional heat pump and heat exchangers for the improvement of the outlet air of the system. A neural network model based on the training of a black box model with experimental data was developed as a method based on experimental results predicting the state conditions of air at the process and regeneration stream. The model development was followed by a Sensitivity Analysis performed on these predicted results. The key parameters were the thermodynamic condition of process and regeneration air streams, the sensible heat factor of the room, and the mass air flow ratio of the regeneration and process streams. The results of this analysis revealed that all investigated parameters influenced the performance of the desiccant unit. Predicted output values of the proposed Neural Network Model for Desiccant Systems are in line with results from other correlation models based on the interpolation of experimental data obtained from industrial air conditioning installations.

  6. Multiferroic properties in NdFeO3-PbTiO3 solid solutions

    Science.gov (United States)

    Kumar, Sunil; Pal, Jaswinder; Kaur, Shubhpreet; Agrawal, P.; Singh, Mandeep; Singh, Anupinder

    2018-05-01

    The x(NdFeO3) - 1-x(PbTiO3) where x = 0.2 solid solution was prepared using solid state reaction route. The X-ray diffraction (XRD) data reveals the single phase formation. The microstructure shows grain growth with lesser porosity. The energy dispersive analysis confirms the presence of elements in stochiometric proportion. The polarization vs. Electric field loop estabilished a ferroelectric type behavior but lossy in nature. This lossy nature may be due to the presence of large leakage current in solid solution. The Magnetization vs. Magnetic field plot exhibits a unsaturated hysteriss loop indicates that the sample is not purely ferromagnetic.

  7. Municipal solid waste management. Strategies and technologies for sustainable solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ludwig, C.; Hellweg, S.; Stucki, S. (eds.)

    2002-10-01

    The way municipal solid waste is handled greatly determines its impact on the local as well as the global environment. New technologies habe emerged for the treatment of waste, for the recovery of raw materials and energy, and for safe final disposal. The environmental performance of technologies, their social acceptance and their economic viability are key issues to be considered in sustainable waste management. This book provides an overview of current practices in waste management and a synthesis of new developments achieved through interdisciplinary discussions of recent research results. (orig.)

  8. Experimental and theoretical investigation of Cr1-xScxN solid solutions for thermoelectrics

    DEFF Research Database (Denmark)

    Kerdsongpanya, Sit; Sun, Bo; Eriksson, Fredrik

    2016-01-01

    The ScN- and CrN-based transition-metal nitrides have recently emerged as a novel and unexpected class of materials for thermoelectrics. These materials constitute well-defined model systems for investigating mixing thermodynamics, phase stability, and band structure aiming for property tailoring......-factor improvement by Sc3d orbital delocalization on Cr3d electrons giving decreasing electrical resistivity, while localized Cr3d orbitals with a large DOS slope may yield an improved Seebeck coefficient. Sc-rich solid solutions show a large improvement in power factor compared to pure ScN, and all films have power...

  9. Synthesis, characterization and thermal expansion studies on thorium-praseodymium mixed oxide solid solutions

    International Nuclear Information System (INIS)

    Panneerselvam, G.; Antony, M.P.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2010-01-01

    Full text: Thorium-praseodymium mixed oxide solid solutions containing 15, 25, 40 and 55 mole percent of praseodymia were synthesized by mixing the solutions of thorium nitrate in water and praseodymium oxide (Pr 6 O 11 ) in conc. HNO 3 . Subsequently, their hydroxides were co-precipitated by the addition of aqueous ammonia. Further the precipitate was dried at 50 deg C, calcined at 600 deg C for 4 hours and sintered at 1200 deg C for 6 h in air. X-ray diffraction measurements were performed for phase identification and lattice parameter derivation. Single-phase fluorite structure was observed for all the compositions. Bulk and theoretical densities of solid solutions were also determined by immersion and X-ray techniques. Thermal expansion coefficients and percentage linear thermal expansion of the solid solutions were determined using high temperature X-ray diffraction technique in the temperature range 300 to 1700 K for the first time. The room temperature lattice constants estimated for above compositions are 0.5578, 0.5565, 0.5545 and 0.5526 nm, respectively. The mean linear thermal expansion coefficients for the solid solutions are 15.48 x 10 -6 K -1 , 18.35 x 10 -6 K -1 , 22.65 x 10 -6 K -1 and 26.95 x 10 -6 K -1 , respectively. The percentage linear thermal expansions in this temperature range are 1.68, 1.89, 2.21 and 2.51 respectively. It is seen that the solid solutions are stable up to 1700 K. It is also seen that the effect and nature of the dopant are the important parameters influencing the thermal expansion of the ThO 2 . The lattice parameter of the solid solutions exhibited a decreasing trend with respect to praseodymia addition. The percentage linear thermal expansion of the solid solutions increases steadily with increasing temperature

  10. Subdiffusion kinetics of nanoprecipitate growth and destruction in solid solutions

    Science.gov (United States)

    Sibatov, R. T.; Svetukhin, V. V.

    2015-06-01

    Based on fractional differential generalizations of the Ham and Aaron-Kotler precipitation models, we study the kinetics of subdiffusion-limited growth and dissolution of new-phase precipitates. We obtain the time dependence of the number of impurities and dimensions of new-phase precipitates. The solutions agree with the Monte Carlo simulation results.

  11. Thermodynamic analysis of SOFC (solid oxide fuel cell) - Stirling hybrid plants using alternative fuels

    DEFF Research Database (Denmark)

    Rokni, Masoud

    2013-01-01

    A novel hybrid power system (∼10 kW) for an average family home is proposed. The system investigated contains a solid oxide fuel cell (SOFC) on top of a Stirling engine. The off-gases produced in the SOFC cycle are fed to a bottoming Stirling engine, at which additional power is generated...... to that of a stand-alone Stirling engine or SOFC plant. For the combined SOFC and Stirling configuration, the overall power production was increased by approximately 10% compared to that of a stand-alone SOFC plant. System efficiencies of approximately 60% are achieved, which is remarkable for such small plant sizes...

  12. Thermodynamic Investigation of an Integrated Gasification Plant with Solid Oxide Fuel Cell and Steam Cycles

    DEFF Research Database (Denmark)

    Rokni, Masoud

    2012-01-01

    A gasification plant is integrated on the top of a solid oxide fuel cell (SOFC) cycle, while a steam turbine (ST) cycle is used as a bottoming cycle for the SOFC plant. The gasification plant was fueled by woodchips to produce biogas and the SOFC stacks were fired with biogas. The produced gas...... generator (HRSG). The steam cycle was modeled with a simple single pressure level. In addition, a hybrid recuperator was used to recover more energy from the HRSG and send it back to the SOFC cycle. Thus two different configurations were investigated to study the plants characteristic. Such system...

  13. Thermodynamic Analysis of an Integrated Solid Oxide Fuel Cell Cycle with a Rankine Cycle

    DEFF Research Database (Denmark)

    Rokni, Masoud

    2010-01-01

    Hybrid systems consisting of Solid Oxide Fuel Cells (SOFC) on the top of a Steam Turbine (ST) are investigated. The plants are fired by natural gas (NG). A desulfurization reactor removes the sulfur content in the fuel while a pre-reformer breaks down the heavier hydrocarbons. The pre-treated fuel......% are achieved which is considerably higher than the conventional Combined Cycles (CC). Both ASR (Adiabatic Steam Reformer) and CPO (Catalytic Partial Oxidation) fuel pre-reformer reactors are considered in this investigation....

  14. Applied Thermodynamics: Grain Boundary Segregation

    Directory of Open Access Journals (Sweden)

    Pavel Lejček

    2014-03-01

    Full Text Available Chemical composition of interfaces—free surfaces and grain boundaries—is generally described by the Langmuir–McLean segregation isotherm controlled by Gibbs energy of segregation. Various components of the Gibbs energy of segregation, the standard and the excess ones as well as other thermodynamic state functions—enthalpy, entropy and volume—of interfacial segregation are derived and their physical meaning is elucidated. The importance of the thermodynamic state functions of grain boundary segregation, their dependence on volume solid solubility, mutual solute–solute interaction and pressure effect in ferrous alloys is demonstrated.

  15. Kinetics, isotherms, and thermodynamic studies of lead, chromium, and cadmium bio-adsorption from aqueous solution onto Picea smithiana sawdust.

    Science.gov (United States)

    Mahmood-Ul-Hassan, Muhammad; Yasin, Muhammad; Yousra, Munazza; Ahmad, Rizwan; Sarwar, Sair

    2018-05-01

    Lead (Pb), chromium (Cr), and cadmium (Cd) removal capacity of sawdust (Picea smithiana) from aqueous solution was investigated by conducting batch experiments. Thermodynamic parameters, like change in standard free energy (ΔG Θ ), enthalpy (ΔH Θ ) and entropy (ΔS Θ ) during bio-adsorption process were estimated using the Van't Hoff equation. The maximum metals adsorption was observed at pH 8, 20 g L -1 bio-adsorbent and at 60 min of contact time. The metal adsorption kinetics was examined by fitting the pseudo-first-order as well as four forms of pseudo-second-order kinetic models. Type 1 pseudo-second-order equation described adsorption kinetics better than others. Langmuir model and Freundlich equations were used for calculation of sorption parameters. The Langmuir maximum adsorption capacity of Pb, Cr, and Cd was 6.35, 3.37, and 2.87 mg g -1 at room temperature, respectively. The values of the separation factor (RL) were in between 0 and 1, indicating that bio-adsorption was favorable. Thermodynamics study revealed that the Pb, Cr, and Cd uptake reactions were endothermic and spontaneous. Results of the study asserted that the removal of heavy metal ions from aqueous solution is viable and the sawdust could be used in the treatment of effluents from industries, thereby reducing the level of water pollution.

  16. Thermodynamics and kinetics of adsorption of Cu(II from aqueous solutions onto multi-walled carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Iman Mobasherpour

    2014-12-01

    Full Text Available Release of heavy metals into water as a result of industrial activities may pose a serious threat to the environment. The objective of this study is to assess the uptake of Cu2+ from aqueous solutions onto multi-walled carbon nanotubes (MWCNT. The potential of the t-MWCNT to remove Cu2+ cations from aqueous solutions was investigated in batch reactor under different experimental conditions. The processing parameters such as initial concentration of Cu2+ ions, temperature, and adsorbent mass were also investigated. Copper uptake was quantitatively evaluated using the Langmuir, Freundlich and Dubinin–Kaganer–Radushkevich (DKR models. In addition, the adsorption equilibrium was described well by the Langmuir isotherm model with maximum adsorption capacity of 12.34 mg/g of Cu2+ cations on t-MWCNT. Various thermodynamic parameters, such as ΔG0, ΔH0 and ΔS0 were calculated. The thermodynamics of Cu2+ cations adsorption onto t-MWCNT system pointed at spontaneous and endothermic nature of the process. Using the second-order kinetic constants, the activation energy of adsorption (Ea was determined as 27.187 kJ/mol according to the Arrhenius equation.

  17. Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

    Science.gov (United States)

    Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

    2015-10-01

    We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

  18. The complex synthesis and solid state chemistry of ceria-lanthana solid solutions prepared via a hexamethylenetetramine precipitation

    International Nuclear Information System (INIS)

    Fleming, P.G.; Holmes, J.D.; Otway, D.J.; Morris, M.A.

    2011-01-01

    Mixed oxide solid solutions are becoming ever more commercially important across a range of applications. However, their synthesis can be problematical. Here, we show that ceria-lanthana solid solutions can be readily prepared via simple precipitation using hexamethylenetetramine. However, the solution chemistry can be complex, which results in the precipitated particles having a complex structure and morphology. Great care must be taken in both the synthesis and characterisation to quantify the complexity of the product. Even very high heat treatments were not able to produce highly homogeneous materials and X-ray diffractions reveals the non-equilibrium form of particles prepared in this way. Unexpected crystal structures are revealed including a new metastable cubic La 2 O 3 phase. - Graphical abstract: The suggested mechanism for the formation of dual fluorite phase particles, where Step 1 corresponds to room temperature aging, Step 2; heating the solution to 90 deg. C, Step 3; cooling of the solution to room temperature, Step 4; calcination to 500 deg. C, Step 5; calcination to 700 deg. C and Step 6; calcination to 1300 deg. C. The terminology of e.g. La 1-x Ce x (OH) 3 is used to indicate the formation of a mixed oxy-hydroxy participate rather than a definitive assignment of stoichiometry. Similarly, La 1-y Ce y O 2 only implies a mixed solid solution. Highlights: → Mol% of prepared Ce-La oxides did not follow that of reactant mol%. → Complex reaction pathway found to be dependent on metal solution concentrations. → At certain concentrations core shell particles were found to form. → A reaction model was produced based on cationic solubility. → Report lanthana solubility higher than previously reported in CeO 2 .

  19. Application of thermodynamic models to study micellar properties of sodium perfluoroalkyl carboxylates in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Perez, Alfredo [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain)], E-mail: alf@usc.es; Ruso, Juan M. [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Romero, Maria J. [Department of Inorganic Chemistry, Faculty of Chemistry, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Blanco, Elena [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Prieto, Gerardo [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Sarmiento, Felix [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain)

    2005-06-27

    Sodium perfluoroalkyl carboxylates (CnFONa) with n = 6, 9, 10 have been studied by conductivity measurements at different temperatures. The Krafft point was determined for C9FONa and C10FONa at the highest concentration studied by measuring the temperature dependence of the specific conductivity. The critical micelle concentration (cmc) and the ionization degree of the micelle ({beta}) were estimated from conductivity vs. molality plots at different temperatures. Using these data and previous results on temperature dependence of cmc and {beta} of sodium perfluoroheptanoate and perfluorooctanoate, different models were applied to obtain the thermodynamic properties of micellization. The results are discussed in terms of alkyl chain length.

  20. Application of thermodynamic models to study micellar properties of sodium perfluoroalkyl carboxylates in aqueous solutions

    International Nuclear Information System (INIS)

    Gonzalez-Perez, Alfredo; Ruso, Juan M.; Romero, Maria J.; Blanco, Elena; Prieto, Gerardo; Sarmiento, Felix

    2005-01-01

    Sodium perfluoroalkyl carboxylates (CnFONa) with n = 6, 9, 10 have been studied by conductivity measurements at different temperatures. The Krafft point was determined for C9FONa and C10FONa at the highest concentration studied by measuring the temperature dependence of the specific conductivity. The critical micelle concentration (cmc) and the ionization degree of the micelle (β) were estimated from conductivity vs. molality plots at different temperatures. Using these data and previous results on temperature dependence of cmc and β of sodium perfluoroheptanoate and perfluorooctanoate, different models were applied to obtain the thermodynamic properties of micellization. The results are discussed in terms of alkyl chain length

  1. Colloidal quantum dot solids for solution-processed solar cells

    KAUST Repository

    Yuan, Mingjian

    2016-02-29

    Solution-processed photovoltaic technologies represent a promising way to reduce the cost and increase the efficiency of solar energy harvesting. Among these, colloidal semiconductor quantum dot photovoltaics have the advantage of a spectrally tuneable infrared bandgap, which enables use in multi-junction cells, as well as the benefit of generating and harvesting multiple charge carrier pairs per absorbed photon. Here we review recent progress in colloidal quantum dot photovoltaics, focusing on three fronts. First, we examine strategies to manage the abundant surfaces of quantum dots, strategies that have led to progress in the removal of electronic trap states. Second, we consider new device architectures that have improved device performance to certified efficiencies of 10.6%. Third, we focus on progress in solution-phase chemical processing, such as spray-coating and centrifugal casting, which has led to the demonstration of manufacturing-ready process technologies.

  2. High temperature thermodynamic studies on the transuranium oxides and their solid solutions

    NARCIS (Netherlands)

    Gotcu-Freis, P.

    2011-01-01

    A growing demand for energy supply worldwide, coupled with the necessity to reduce emission of greenhouse gases, has led to a renewed interest in nuclear energy as an alternative to fossil fuels for electricity production in the last years. One of the main drawbacks to the development of nuclear

  3. Thermal conductivities of (ZrxPu(1-x)/2Am(1-x)/2)N solid solutions

    International Nuclear Information System (INIS)

    Nishi, Tsuyoshi; Takano, Masahide; Akabori, Mitsuo; Arai, Yasuo

    2011-01-01

    The thermal conductivity of Zr-based transuranium (TRU) nitride solid solutions is important for designing subcritical cores in nitride-fueled ADS. Some results have been reported concerning the thermal conductivities of (Zr,Pu)N. However, there have been no experimental data on the thermal conductivities of Zr-based nitride solid solutions containing MA. In this study, the authors prepared sintered samples of (Zr x Pu (1-x)/2 Am (1-x)/2) N (x=0.0, 0.58, 0.80) solid solutions. The thermal diffusivity and heat capacity of (Zr x Pu (1-x)/2 Am (1-x)/2) N solid solutions were measured using a laser flash method and drop calorimetry, respectively. Thermal conductivities were determined from the measured thermal diffusivities, heat capacities and bulk densities over a temperature range of 473 to 1473 K. The thermal conductivities of (Zr 0.58 Pu 0.21 Am 0.21 )N and (Zr 0.80 Pu 0.10 Am 0.10 )N solid solutions were found to be higher than that of (Pu 0.5 Am 0.5 )N due to the high thermal conductivity of ZrN as the principal component, although they were lower than that of ZrN due to the impurifying effect of the transuranium elements. Thus, the thermal conductivities of (Zr x Pu (1-x)/2 Am (1-x)/2) N solid solutions increased with increasing ZrN concentration. Moreover, in order to help to promote the design study of nitride-fueled ADS, the thermal conductivity of the (Zr x Pu (1-x)/2 Am (1-x)/2) N solid solutions were fitted to an equation using the least squares method. (author)

  4. Structural Relaxations and Thermodynamic Properties of Molecular Amorphous Solids by Mechanical Milling

    Science.gov (United States)

    Tsukushi, I.; Yamamuro, O.; Matsuo, T.

    The organic crystals of tri-O-methyl-β-cyclodextrin (TMCD) and its three clathrate compounds containing benzoic acid (BA), p-nitrobenzoic acid (NBA) and p-hydroxybenzoic acid (HBA), sucrose (SUC), salicin (SAL), phenolphthalein (PP), 1,3,5-tri-α-naphthylbenzene (TNB) were amorphized by milling with a vibrating mill for 2 ˜ 16 hours at room temperature. The amorphization was checked by differential scanning calorimetry (DSC) and X-ray powder diffraction. The heat capacities of crystals, liquid quenched glasses (LQG), and mechanically-milled amorphous solid (MMAS) of TMCD and TNB were measured with an adiabatic calorimeter in the temperature range between 12 and 375 K. For both compounds, the enthalpy relaxation of MMAS appeared in the wide temperature range below Tg and the released configurational enthalpy was much larger than that of LQG, indicating that MMAS is more disordered and strained than LQG.

  5. Thermodynamic and topochemical aspects of the adsorption of some gaseous fluorides and solid fluorides

    International Nuclear Information System (INIS)

    Le Gressus, Claude

    1968-01-01

    This research thesis addresses the study of chemical adsorption. Such an adsorption is limited to a mono-molecular layer. As the Order Disorder Theory (ODT) allows adsorption isotherms to be calculated while taking interaction between adsorbed molecules into account, this research reports a comparison between the shape of experimental isotherms and that of theoretical isotherms. The knowledge of the involved phenomena is completed by the measurement of adsorption differential heats. After some generalities and a brief presentation of the ODT, the author presents experimental installations and techniques (micro-calorimeter, Mac-Bain balance), describes the adsorbent pre-treatment, reports the analysis performed by micro-sublimation, reports the study of the adsorption of hydrofluoric acid on CaF 2 , highlights the existence of different cases of energies increasing with the overlay rate, reports the detailed study of adsorption isotherms of ClF 3 and UF 6 on various solid fluorides. Results are finally interpreted and discussed

  6. Thermodynamic Analysis of an Integrated Gasification Solid Oxide Fuel Cell Plant with a Kalina Cycle

    DEFF Research Database (Denmark)

    Pierobon, Leonardo; Rokni, Masoud

    2015-01-01

    % is achieved; plant size and nominal power are selected based on the required cultivation area. SOFC heat recovery with SKC is compared to a Steam Cycle (SC). Although ammonia-water more accurately fits the temperature profile of the off-gases, the presence of a Hybrid Recuperator enhances the available work......-treated fuel then enters the anode side of the SOFC. Complete fuel oxidation is ensured in a burner by off-gases exiting the SOFC stacks. Off-gases are utilized as heat source for a SKC where a mixture of ammonia and water is expanded in a turbine to produce additional electric power. Thus, a triple novel......A hybrid plant that consists of a gasification system, Solid Oxide Fuel Cells (SOFC) and a Simple Kalina Cycle (SKC) is investigated. Woodchips are introduced into a fixed bed gasification plant to produce syngas, which is then fed into an integrated SOFC-SKC plant to produce electricity. The pre...

  7. Thermodynamic analysis of an integrated solid oxide fuel cell cycle with a rankine cycle

    International Nuclear Information System (INIS)

    Rokni, Masoud

    2010-01-01

    Hybrid systems consisting of solid oxide fuel cells (SOFC) on the top of a steam turbine (ST) are investigated. The plants are fired by natural gas (NG). A desulfurization reactor removes the sulfur content in the fuel while a pre-reformer breaks down the heavier hydro-carbons. The pre-treated fuel enters then into the anode side of the SOFC. The remaining fuels after the SOFC stacks enter a burner for further burning. The off-gases are then used to produce steam for a Rankine cycle in a heat recovery steam generator (HRSG). Different system setups are suggested. Cyclic efficiencies up to 67% are achieved which is considerably higher than the conventional combined cycles (CC). Both adiabatic steam reformer (ASR) and catalytic partial oxidation (CPO) fuel pre-reformer reactors are considered in this investigation.

  8. Uncertainties associated with lacking data for predictions of solid-solution partitioning of metals in soil

    International Nuclear Information System (INIS)

    Le, T.T. Yen; Hendriks, A. Jan

    2014-01-01

    Soil properties, i.e., pH and contents of soil organic matter (SOM), dissolved organic carbon (DOC), clay, oxides, and reactive metals, are required inputs to both mechanistic and empirical modeling in assessing metal solid-solution partitioning. Several of these properties are rarely measured in site-specific risk assessment. We compared the uncertainties induced by lacking data on these soil properties in estimating metal soil solution concentrations. The predictions by the Orchestra framework were more sensitive to lacking soil property data than the predictions by the transfer functions. The deviations between soil solution concentrations of Cd, Ni, Zn, Ba, and Co estimated with measured SOM and those estimated with generic SOM by the Orchestra framework were about 10 times larger than the deviations in the predictions by the transfer functions. High uncertainties were induced by lacking data in assessing solid-solution partitioning of oxy-anions like As, Mo, Sb, Se, and V. Deviations associated with lacking data in predicting soil solution concentrations of these metals by the Orchestra framework reached three-to-six orders of magnitude. The solid-solution partitioning of metal cations was strongly influenced by pH and contents of organic matter, oxides, and reactive metals. Deviations of more than two orders of magnitude were frequently observed between the estimates of soil solution concentrations with the generic values of these properties and the estimates based on the measured data. Reliable information on these properties is preferred to be included in the assessment by either the Orchestra framework or transfer functions. - Highlights: • Estimates of metal solid-solution partitioning sensitive to soil property data. • Uncertainty mainly due to lacking reactive metal contents, pH, and organic matter. • Soil solution concentrations of oxy-anions highly influenced by oxide contents. • Clay contents had least effects on solid-solution partitioning

  9. Uncertainties associated with lacking data for predictions of solid-solution partitioning of metals in soil

    Energy Technology Data Exchange (ETDEWEB)

    Le, T.T. Yen, E-mail: YenLe@science.ru.nl; Hendriks, A. Jan

    2014-08-15

    Soil properties, i.e., pH and contents of soil organic matter (SOM), dissolved organic carbon (DOC), clay, oxides, and reactive metals, are required inputs to both mechanistic and empirical modeling in assessing metal solid-solution partitioning. Several of these properties are rarely measured in site-specific risk assessment. We compared the uncertainties induced by lacking data on these soil properties in estimating metal soil solution concentrations. The predictions by the Orchestra framework were more sensitive to lacking soil property data than the predictions by the transfer functions. The deviations between soil solution concentrations of Cd, Ni, Zn, Ba, and Co estimated with measured SOM and those estimated with generic SOM by the Orchestra framework were about 10 times larger than the deviations in the predictions by the transfer functions. High uncertainties were induced by lacking data in assessing solid-solution partitioning of oxy-anions like As, Mo, Sb, Se, and V. Deviations associated with lacking data in predicting soil solution concentrations of these metals by the Orchestra framework reached three-to-six orders of magnitude. The solid-solution partitioning of metal cations was strongly influenced by pH and contents of organic matter, oxides, and reactive metals. Deviations of more than two orders of magnitude were frequently observed between the estimates of soil solution concentrations with the generic values of these properties and the estimates based on the measured data. Reliable information on these properties is preferred to be included in the assessment by either the Orchestra framework or transfer functions. - Highlights: • Estimates of metal solid-solution partitioning sensitive to soil property data. • Uncertainty mainly due to lacking reactive metal contents, pH, and organic matter. • Soil solution concentrations of oxy-anions highly influenced by oxide contents. • Clay contents had least effects on solid-solution partitioning

  10. Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

    Science.gov (United States)

    Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

    2018-06-01

    The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

  11. Thermodynamic properties of ethanol solution of chiral camphors and its derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Kimura, Takayoshi [Department of Chemistry, Kinki University, Kowakae, Higashi-Osaka 577-8502 (Japan)], E-mail: kimura@chem.kindai.ac.jp; Iwama, Sekai; Kido, Satoko; Khan, Mohammad Abdullah [Department of Chemistry, Kinki University, Kowakae, Higashi-Osaka 577-8502 (Japan)

    2009-10-15

    Enthalpies of mixing and the densities of ethanol solution of R- and S-enantiomers of camphor, 10-camphorsulfonamide, 10-camphorsulfonic acid, camphorquinone, and 10-camphorsulfonyl chloride have been measured for a wide range of mole fractions of heterochiral components at 298.15 K. Enthalpies of mixing were exothermic for all concentrations and heterochiral solutions were more stable than each of the homochiral solutions. Enthalpic stabilization of mixing of heterochiral solutions was increased with a decreasing concentration of all the camphor derivatives measured. The sequence of enthalpic stabilization on mixing was 10-camphorsulfonyl chloride, 10-camphorsulfonic acid, 10-camphorsulfonamide, camphor, and camphorquinone. Apparent molar volumes were determined and excess volumes of mixing of heterochiral solutions were small and negative. Enthalpic stabilizations were found to be dependent on dipole-dipole interaction between solutes and solvents.

  12. Concentrated aqueous sodium chloride solution in clays at thermodynamic conditions of hydraulic fracturing: Insight from molecular dynamics simulations

    Science.gov (United States)

    Svoboda, Martin; Lísal, Martin

    2018-06-01

    To address a high salinity of flow-back water during hydraulic fracturing, we use molecular dynamics (MD) simulations and study the thermodynamics, structure, and diffusion of concentrated aqueous salt solution in clay nanopores. The concentrated solution results from the dissolution of a cubic NaCl nanocrystal, immersed in an aqueous NaCl solution of varying salt concentration and confined in clay pores of a width comparable to the crystal size. The size of the nanocrystal equals to about 18 Å which is above a critical nucleus size. We consider a typical shale gas reservoir condition of 365 K and 275 bar, and we represent the clay pores as pyrophyllite and Na-montmorillonite (Na-MMT) slits. We employ the Extended Simple Point Charge (SPC/E) model for water, Joung-Cheatham model for ions, and CLAYFF for the slit walls. We impose the pressure in the normal direction and the resulting slit width varies from about 20 to 25 Å when the salt concentration in the surrounding solution increased from zero to an oversaturated value. By varying the salt concentration, we observe two scenarios. First, the crystal dissolves and its dissolution time increases with increasing salt concentration. We describe the dissolution process in terms of the number of ions in the crystal, and the crystal size and shape. Second, when the salt concentration reaches a system solubility limit, the crystal grows and attains a new equilibrium size; the crystal comes into equilibrium with the surrounding saturated solution. After crystal dissolution, we carry out canonical MD simulations for the concentrated solution. We evaluate the hydration energy, density profiles, orientation distributions, hydrogen-bond network, radial distribution functions, and in-plane diffusion of water and ions to provide insight into the microscopic behaviour of the concentrated aqueous sodium chloride solution in interlayer galleries of the slightly hydrophobic pyrophyllite and hydrophilic Na-MMT pores.

  13. Chemical thermodynamics of uranium

    International Nuclear Information System (INIS)

    Grenthe, I.; Fuger, J.; Lemire, R.J.; Muller, A.B.; Nguyen-Trung Cregu, C.; Wanner, H.

    1992-01-01

    A comprehensive overview on the chemical thermodynamics of those elements that are of particular importance in the safety assessment of radioactive waste disposal systems is provided. This is the first volume in a series of critical reviews to be published on this subject. The book provides an extensive compilation of chemical thermodynamic data for uranium. A description of procedures for activity corrections and uncertainty estimates is given. A critical discussion of data needed for nuclear waste management assessments, including areas where significant gaps of knowledge exist is presented. A detailed inventory of chemical thermodynamic data for inorganic compounds and complexes of uranium is listed. Data and their uncertainty limits are recommended for 74 aqueous complexes and 199 solid and 31 gaseous compounds containing uranium, and on 52 aqueous and 17 solid auxiliary species containing no uranium. The data are internally consistent and compatible with the CODATA Key Values. The book contains a detailed discussion of procedures used for activity factor corrections in aqueous solution, as well as including methods for making uncertainty estimates. The recommended data have been prepared for use in environmental geochemistry. Containing contributions written by experts the chapters cover various subject areas such a s: oxide and hydroxide compounds and complexes, the uranium nitrides, the solid uranium nitrates and the arsenic-containing uranium compounds, uranates, procedures for consistent estimation of entropies, gaseous and solid uranium halides, gaseous uranium oxides, solid phosphorous-containing uranium compounds, alkali metal uranates, uncertainties, standards and conventions, aqueous complexes, uranium minerals dealing with solubility products and ionic strength corrections. The book is intended for nuclear research establishments and consulting firms dealing with uranium mining and nuclear waste disposal, as well as academic and research institutes

  14. Comparisons of kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide adsorption in aqueous solution with graphene oxide, zeolite and activated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Shenteng; Lu, Chungsying, E-mail: clu@nchu.edu.tw; Lin, Kun-Yi Andrew

    2015-01-30

    Graphical abstract: A comparison of TMAH adsorption capacity with GO, NaY and GAC is conducted and the result reveals that the magnitude of qe follows the order of GO > NaY > GAC. The adsorption capacity of GO is significantly higher than those of zeolite and activated carbon in this and reported studies, showing its encouraging potential. GO also exhibits good reversibility of TMAH adsorption through 10 cycles of adsorption and desorption process. This reflects that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment. - Highlights: • Adsorption kinetics and isotherms of TMAH to GO, NaY and GAC are compared. • Thermodynamics of TMAH adsorption to GO, NaY and GAC is determined. • GO exhibits the highest TMAH adsorption capacity, followed by NaY and GAC. • Recyclabilities of NaY and GO remain above 95% but that of GAC dropped to 70%. - Abstract: Graphene oxide (GO), sodium Y-type zeolite (NaY) and granular activated carbon (GAC) are selected as adsorbents to study their kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide (TMAH) adsorption from water. The adsorption kinetics follows the pseudo-second-order rate law while the adsorption thermodynamics shows an exothermic reaction with GO and GAC but displays an endothermic reaction with NaY. The adsorbed TMAH can be readily desorbed from the surface of GO and NaY by 0.05 M NaCl solution. A comparative study on the cyclic TMAH adsorption with GO, NaY and GAC is also conducted and the results reveal that GO exhibits the greatest TMAH adsorption capacity as well as superior reversibility of TMAH adsorption over 10 cycles of adsorption and desorption process. These features indicate that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment.

  15. Active Edge Sites Engineering in Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution

    KAUST Repository

    Xia, Chuan

    2017-01-06

    An effective multifaceted strategy is demonstrated to increase active edge site concentration in NiCoSe solid solutions prepared by in situ selenization process of nickel cobalt precursor. The simultaneous control of surface, phase, and morphology result in as-prepared ternary solid solution with extremely high electrochemically active surface area (C = 197 mF cm), suggesting significant exposure of active sites in this ternary compound. Coupled with metallic-like electrical conductivity and lower free energy for atomic hydrogen adsorption in NiCoSe, identified by temperature-dependent conductivities and density functional theory calculations, the authors have achieved unprecedented fast hydrogen evolution kinetics, approaching that of Pt. Specifically, the NiCoSe solid solutions show a low overpotential of 65 mV at -10 mV cm, with onset potential of mere 18 mV, an impressive small Tafel slope of 35 mV dec, and a large exchange current density of 184 μA cm in acidic electrolyte. Further, it is shown that the as-prepared NiCoSe solid solution not only works very well in acidic electrolyte but also delivers exceptional hydrogen evolution reaction (HER) performance in alkaline media. The outstanding HER performance makes this solid solution a promising candidate for mass hydrogen production.

  16. Hydrothermal synthesis of pollucite, analcime and their solid solutions and analysis of their properties

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Zhenzi, E-mail: zzjing@tongji.edu.cn [Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, Tongji University, 4800 Cao' an Road, Shanghai 201804 (China); Cai, Kunchuan; Li, Yan; Fan, Junjie; Zhang, Yi; Miao, Jiajun; Chen, Yuqian [Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, Tongji University, 4800 Cao' an Road, Shanghai 201804 (China); Jin, Fangming [School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China)

    2017-05-15

    Pollucite, as a perfect long-term potential host for radioactive Cs immobilization, barely exists in pure form naturally but in an isomorphism form between pollucite and analcime due to coexistence of Cs and Na. Pollucite could be hydrothermally synthesized with Cs-polluted soil or clay minerals which contain Cs and Na, and it is necessary to study the properties of the synthesis if Cs and Na contained. Pure pollucite, analcime and their solid solutions were hydrothermally synthesized with chemicals, and it was found that the most formed pollucite analcime solid solutions with Cs/(Cs + Na) ratios of 2/6–5/6 had very similar properties in mineral composition, morphology and size, structural water (Cs cations) and coordination environment to pollucite. This also suggests that even coexistence of Cs and Na in nature, pollucite favors to form due to site preference for Cs over Na, which leads to the property and the structure of the most solid solutions similar to that of pollucite. - Highlights: •Pure pollucite barely exists in nature due to coexistence of Cs and Na. •Pollucite, analcime and their solid solutions could be hydrothermally synthesized. •Most formed solid solutions were found to have similar properties to pollucite. •Even coexistence in nature, pollucite favors to form due to site preference for Cs over Na.

  17. Green Synthesis of Zinc Oxide Nanoparticles for Enhanced Adsorption of Lead Ions from Aqueous Solutions: Equilibrium, Kinetic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Susan Azizi

    2017-06-01

    Full Text Available In the present study, ZnO nanoparticles (NPs were synthesized in zerumbone solution by a green approach and appraised for their ability to absorb Pb(II ions from aqueous solution. The formation of as-synthesized NPs was established by X-ray diffraction (XRD, Transmission Electron Microscopy (TEM, and UV–visible studies. The XRD and TEM analyses revealed high purity and wurtzite hexagonal structure of ZnO NPs with a mean size of 10.01 ± 2.6 nm. Batch experiments were performed to investigate the impact of process parameters viz. Pb(II concentration, pH of solution, adsorbent mass, solution temperature, and contact time variations on the removal efficiency of Pb(II. The adsorption isotherm data provided that the adsorption process was mainly monolayer on ZnO NPs. The adsorption process follows pseudo-second-order reaction kinetic. The maximum removal efficiencies were 93% at pH 5. Thermodynamic parameters such as enthalpy change (ΔH0, free energy change (ΔG0, and entropy change (ΔS0 were calculated; the adsorption process was spontaneous and endothermic. The good efficiency of the as-synthesized NPs makes them attractive for applications in water treatment, for removal of heavy metals from aqueous system.

  18. Removal of thorium (IV) ions from aqueous solution by a novel nanoporous ZnO: Isotherms, kinetic and thermodynamic studies.

    Science.gov (United States)

    Kaynar, Ümit H; Ayvacıklı, Mehmet; Hiçsönmez, Ümran; Kaynar, Sermin Çam

    2015-12-01

    The adsorption of thorium (IV) from aqueous solutions onto a novel nanoporous ZnO particles prepared by microwave assisted combustion was studied using batch methods under different experimental conditions. The effect of contact time, solution pH, initial concentration and temperature on adsorption process was studied. The ability of this material to remove Th (IV) from aqueous solution was characterises by Langmuir, Freunlinch and Temkin adsorption isotherms. The adsorption percent and distribution coefficient for nanoporous ZnO powders in optimum conditions were 97% ± 1.02; 8080 L kg(-1)for Th (IV), respectively. Based on the Langmuir model, the maximum adsorption capacity of nanoporous ZnO for Th (IV) was found to be 1500 g kg(-1). Thermodynamic parameters were determined and discussed. The results indicated that nanoporous ZnO was suitable as sorbent material for recovery and adsorption of Th (IV) ions from aqueous solutions. The radioactive Th (VI) in surface water, sea water and waste waters from technologies producing nuclear fuels, mining (uranium and thorium) and laboratories working with radioactive materials (uranium and thorium) can be removed with this nanoporous ZnO. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. A thermodynamic and kinetic study of trace iron removal from aqueous cobalt sulfate solutions using Monophos resin.

    Science.gov (United States)

    Wang, Guangxin; Zhao, Yunchao; Yang, Bin; Song, Yongfa

    2018-01-01

    High purity cobalt has many important applications, such as magnetic recording media, magnetic recording heads, optoelectronic devices, magnetic sensors, and integrated circuits, etc. To produce 5N or higher purity cobalt in an electro-refining process, one of the challenges is to effectively reduce the Fe content of aqueous cobalt salt solution before electrolysis. This paper describes thermodynamic and kinetic investigations of the Fe adsorption process of a new sulfonated monophosphonic resin with the trade mark Monophos. Five cobalt sulfate solutions of different Co concentrations were prepared. Fe ions were removed from the solutions by ion exchange method using Monophos resin. Chemical analysis was carried out using a Perkin Elmer ICP-OES. The initial Fe concentrations of about 0.9-2.0 mg/L can be reduced to about 0.3-0.8 mg/L, which is equivalent to an Fe removal rate of 60-67%. The Langmuir isothermal adsorption model applies well to the Fe removal process. A second-order type based on McKay equation fits better with experimental data than other kinetic models. The kinetic curve can be divided into two sections. For t 30 min. Monophos resin is effective for the removal of trace Fe from cobalt sulfate solution. This ion exchange process obeys the Langmuir isothermal adsorption model and the McKay equation of second-order kinetics.

  20. Thermodynamic investigation of an integrated gasification plant with solid oxide fuel cell and steam cycles

    Energy Technology Data Exchange (ETDEWEB)

    Rokni, Masoud [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Mechanical Engineering, Thermal Energy System

    2012-07-01

    A gasification plant is integrated on the top of a solid oxide fuel cell (SOFC) cycle, while a steam turbine (ST) cycle is used as a bottoming cycle for the SOFC plant. The gasification plant was fueled by woodchips to produce biogas and the SOFC stacks were fired with biogas. The produced gas was rather clean for feeding to the SOFC stacks after a simple cleaning step. Because all the fuel cannot be burned in the SOFC stacks, a burner was used to combust the remaining fuel. The off-gases from the burner were then used to produce steam for the bottoming steam cycle in a heat recovery steam generator (HRSG). The steam cycle was modeled with a simple single pressure level. In addition, a hybrid recuperator was used to recover more energy from the HRSG and send it back to the SOFC cycle. Thus two different configurations were investigated to study the plants characteristic. Such system integration configurations are completely novel and have not been studied elsewhere. Plant efficiencies of 56% were achieved under normal operation which was considerably higher than the IGCC (Integrated Gasification Combined Cycle) in which a gasification plant is integrated with a gas turbine and a steam turbine. Furthermore, it is shown that under certain operating conditions, plant efficiency of about 62 is also possible to achieve. (orig.)

  1. Thermodynamic analysis of a combined gas turbine power plant with a solid oxide fuel cell for marine applications

    Directory of Open Access Journals (Sweden)

    Yousri M.A. Welaya

    2013-12-01

    Full Text Available Strong restrictions on emissions from marine power plants (particularly SOx, NOx will probably be adopted in the near future. In this paper, a combined solid oxide fuel cell (SOFC and gas turbine fuelled by natural gas is proposed as an attractive option to limit the environmental impact of the marine sector. It includes a study of a heat-recovery system for 18 MW SOFC fuelled by natural gas, to provide the electric power demand onboard commercial vessels. Feasible heat-recovery systems are investigated, taking into account different operating conditions of the combined system. Two types of SOFC are considered, tubular and planar SOFCs, operated with either natural gas or hydrogen fuels. This paper includes a detailed thermodynamic analysis for the combined system. Mass and energy balances are performed, not only for the whole plant but also for each individual component, in order to evaluate the thermal efficiency of the combined cycle. In addition, the effect of using natural gas as a fuel on the fuel cell voltage and performance is investigated. It is found that a high overall efficiency approaching 70% may be achieved with an optimum configuration using SOFC system under pressure. The hybrid system would also reduce emissions, fuel consumption, and improve the total system efficiency.

  2. Thermodynamic and thermoeconomic analysis of a system with biomass gasification, solid oxide fuel cell (SOFC) and Stirling engine

    International Nuclear Information System (INIS)

    Rokni, Masoud

    2014-01-01

    Thermodynamic and thermoeconomic investigations of a small-scale integrated gasification solid oxide fuel cell (SOFC) and Stirling engine for combined heat and power (CHP) with a net electric capacity of 120 kW e have been performed. Woodchips are used as gasification feedstock to produce syngas, which is then utilized to feed the anode side of the SOFC stacks. A thermal efficiency of 0.424 LHV (lower heating value) for the plant is found to use 89.4 kg/h of feedstock to produce the above mentioned electricity. Thermoeconomic analysis shows that the production price of electricity is 0.1204 $/kWh. Furthermore, hot water is considered as a by-product, and the cost of hot water is found to be 0.0214 $/kWh. When compared to other renewable systems of similar scales, this result shows that if both SOFC and Stirling engine technology enter the commercialization phase, then they can deliver electricity at a cost that is competitive with the corresponding renewable systems of the same size. - Highlights: • A 120 kW e integrated gasification SOFC–Stirling CHP is presented. • Effect of important parameters on plant characteristic and economy are studied. • A modest thermal efficiency of 0.41 is found after thermoeconomic optimization. • Reducing stack numbers cuts cost of electricity at expense of thermal efficiency. • The plant cost is estimated to be about 3433 $/kW when disposal costs are neglected

  3. A thermodynamic approach for selecting operating conditions in the design of reversible solid oxide cell energy systems

    Science.gov (United States)

    Wendel, Christopher H.; Kazempoor, Pejman; Braun, Robert J.

    2016-01-01

    Reversible solid oxide cell (ReSOC) systems are being increasingly considered for electrical energy storage, although much work remains before they can be realized, including cell materials development and system design optimization. These systems store electricity by generating a synthetic fuel in electrolysis mode and subsequently recover electricity by electrochemically oxidizing the stored fuel in fuel cell mode. System thermal management is improved by promoting methane synthesis internal to the ReSOC stack. Within this strategy, the cell-stack operating conditions are highly impactful on system performance and optimizing these parameters to suit both operating modes is critical to achieving high roundtrip efficiency. Preliminary analysis shows the thermoneutral voltage to be a useful parameter for analyzing ReSOC systems and the focus of this study is to quantitatively examine how it is affected by ReSOC operating conditions. The results reveal that the thermoneutral voltage is generally reduced by increased pressure, and reductions in temperature, fuel utilization, and hydrogen-to-carbon ratio. Based on the thermodynamic analysis, many different combinations of these operating conditions are expected to promote efficient energy storage. Pressurized systems can achieve high efficiency at higher temperature and fuel utilization, while non-pressurized systems may require lower stack temperature and suffer from reduced energy density.

  4. Thermodynamic analysis of a combined gas turbine power plant with a solid oxide fuel cell for marine applications

    Science.gov (United States)

    Welaya, Yousri M. A.; Mosleh, M.; Ammar, Nader R.

    2013-12-01

    Strong restrictions on emissions from marine power plants (particularly SOx, NOx) will probably be adopted in the near future. In this paper, a combined solid oxide fuel cell (SOFC) and gas turbine fuelled by natural gas is proposed as an attractive option to limit the environmental impact of the marine sector. It includes a study of a heatrecovery system for 18 MW SOFC fuelled by natural gas, to provide the electric power demand onboard commercial vessels. Feasible heat-recovery systems are investigated, taking into account different operating conditions of the combined system. Two types of SOFC are considered, tubular and planar SOFCs, operated with either natural gas or hydrogen fuels. This paper includes a detailed thermodynamic analysis for the combined system. Mass and energy balances are performed, not only for the whole plant but also for each individual component, in order to evaluate the thermal efficiency of the combined cycle. In addition, the effect of using natural gas as a fuel on the fuel cell voltage and performance is investigated. It is found that a high overall efficiency approaching 70% may be achieved with an optimum configuration using SOFC system under pressure. The hybrid system would also reduce emissions, fuel consumption, and improve the total system efficiency.

  5. Cutting solid figures by plane - analytical solution and spreadsheet implementation

    Science.gov (United States)

    Benacka, Jan

    2012-07-01

    In some secondary mathematics curricula, there is a topic called Stereometry that deals with investigating the position and finding the intersection, angle, and distance of lines and planes defined within a prism or pyramid. Coordinate system is not used. The metric tasks are solved using Pythagoras' theorem, trigonometric functions, and sine and cosine rules. The basic problem is to find the section of the figure by a plane that is defined by three points related to the figure. In this article, a formula is derived that gives the positions of the intersection points of such a plane and the figure edges, that is, the vertices of the section polygon. Spreadsheet implementations of the formula for cuboid and right rectangular pyramids are presented. The user can check his/her graphical solution, or proceed if he/she is not able to complete the section.

  6. Thermodynamic, Kinetic, and Equilibrium Parameters for the Removal of Lead and Cadmium from Aqueous Solutions with Calcium Alginate Beads

    Directory of Open Access Journals (Sweden)

    Ruth Alfaro-Cuevas-Villanueva

    2014-01-01

    Full Text Available The sorption of cadmium (Cd and lead (Pb by calcium alginate beads (CAB from aqueous solutions in batch systems was investigated. The kinetic and thermodynamic parameters, as well as the sorption capacities of CAB in each system at different temperatures, were evaluated. The rate of sorption for both metals was rapid in the first 10 minutes and reached a maximum in 50 minutes. Sorption kinetic data were fitted to Lagergren, pseudo-second-order and Elovich models and it was found that the second-order kinetic model describes these data for the two metals; comparing kinetic parameters for Cd and Pb sorption a higher kinetic rate (K2 for Pb was observed, indicating that the interaction between lead cations and alginate beads was faster than for cadmium. Similarly, isotherm data were fitted to different models reported in literature and it was found that the Langmuir-Freundlich (L-F and Dubinin-Radushkevich (D-R models describe the isotherms in all cases. CAB sorption capacity for cadmium was 27.4 mg/g and 150.4 mg/g for lead, at 25°C. Sorption capacities of Cd and Pb increase as temperature rises. According to the thermodynamic parameters, the cadmium and lead adsorption process was spontaneous and endothermic. It was also found that pH has an important effect on the adsorption of these metals by CAB, as more were removed at pH values between 6 and 7.

  7. Thermodynamics of mixed-ligand complex formation of zinc nitrilotriacetate with amino acids and dipeptides in solution

    International Nuclear Information System (INIS)

    Pyreu, Dmitrii; Gruzdev, Matvey; Kumeev, Roman; Gridchin, Sergei

    2014-01-01

    Highlights: • Stable mixed ligand complexes of ZnNta with amino acids and dipeptides. • Histamine-like coordination mode of His in the complex ZnNtaHis. • Glycine-like coordination of Lys and Orn in the complexes ZnNtaL and ZnNtaHL • NH 2 , CO-coordination mode of GlyGly in the complex ZnNtaGG. • NH 2 , N − or NH2, N − , COO-coordination modes of GlyGly in the complex ZnNtaGGH −1 . - Abstract: The isothermal calorimetry, pH-potentiometric titration and 1 H and 13 C NMR methods has been used to study the mixed-ligand complex formation in the systems Zn 2+ –Nta 3– –L − (L = His, Orn, Lys, GlyGly, AlaAla) in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO 3 ). The thermodynamic parameters of formation of the mixed complexes have been determined. The relationship between the probable coordination modes of the complexone and amino acid or dipeptide molecules in the mixed-ligand complex and the thermodynamic parameters has been discussed

  8. Thermodynamics of mixed-ligand complex formation of zinc nitrilotriacetate with amino acids and dipeptides in solution

    Energy Technology Data Exchange (ETDEWEB)

    Pyreu, Dmitrii, E-mail: pyreu@mail.ru [Department of Inorganic and Analytic Chemistry, Ivanovo State UniversityErmak 39, Ivanovo 153025 (Russian Federation); Gruzdev, Matvey; Kumeev, Roman [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); Gridchin, Sergei [Ivanovo State University of Chemistry and Technology, Ivanovo (Russian Federation)

    2014-10-20

    Highlights: • Stable mixed ligand complexes of ZnNta with amino acids and dipeptides. • Histamine-like coordination mode of His in the complex ZnNtaHis. • Glycine-like coordination of Lys and Orn in the complexes ZnNtaL and ZnNtaHL • NH{sub 2}, CO-coordination mode of GlyGly in the complex ZnNtaGG. • NH{sub 2}, N{sup −} or NH2, N{sup −}, COO-coordination modes of GlyGly in the complex ZnNtaGGH{sub −1}. - Abstract: The isothermal calorimetry, pH-potentiometric titration and {sup 1}H and {sup 13}C NMR methods has been used to study the mixed-ligand complex formation in the systems Zn{sup 2+}–Nta{sup 3–}–L{sup −} (L = His, Orn, Lys, GlyGly, AlaAla) in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO{sub 3}). The thermodynamic parameters of formation of the mixed complexes have been determined. The relationship between the probable coordination modes of the complexone and amino acid or dipeptide molecules in the mixed-ligand complex and the thermodynamic parameters has been discussed.

  9. Modelling uranium solubilities in aqueous solutions: Validation of a thermodynamic data base for the EQ3/6 geochemical codes

    International Nuclear Information System (INIS)

    Puigdomenech, I.; Bruno, J.

    1988-01-01

    Experimental solubilities of U 4+ and UO 2 2+ that are reported in the literature have been collected. Data on oxides, hydroxides and carbonates have been selected for this work. They include results both at 25 degrees C and at higher temperatures. The literature data have been compared with calculated uranium solubilities obtained with the EQ3/6 geochemical modelling programs and an uranium thermodynamic data base selected for the Swedish nuclear waste management program. This verification/validiation exercise has shown that more experimental data is needed to determine the chemical composition of anionic uranyl hydroxo complexes as well as their equilibrium constants of formation. There is also a need for more solubility data on well characterised alkaline or alkaline-earth uranates. For the uranyl carbonate system, the calculated results agree reasonably well with the experimental literature values, which span over a wide range of pH, (CO 3 2- ) T , CO 2 (g)-pressure, and T. The experimental solubility of UO 2 (s) agrees also well with the EQ3/6 calculations for pH greater than 6. However, in more acidic solutions the experimental solubilities are higher than the calculated values. This is due to the formation of polynuclear hydroxo complexes of uranium, which are not well characterised, and are not included in the thermodynamic data base used in this study. (authors)

  10. Thermodynamic analysis of carbon formation in solid oxide fuel cells with a direct internal reformer fueled by ethanol, methanol, and methane

    International Nuclear Information System (INIS)

    Laosiripojana, N.; Assabumrungrat, S.; Pavarajarn, V.; Sangtongkitcharoen, W.; Tangjitmatee, A.; Praserthdam, P.

    2004-01-01

    'Full text:' This paper concerns a detailed thermodynamic analysis of carbon formation for a Direct Internal Reformer (DIR) Solid Oxide Fuel Cells (SOFC). The modeling of DIR-SOFC fueled by ethanol, methanol, and methane were compared. Two types of fuel cell electrolytes, i.e. oxygen-conducting and hydrogen-conducting, are considered. Equilibrium calculations were performed to find the ranges of inlet steam/fuel ratio where carbon formation is thermodynamically unfavorable in the temperature range of 500-1200 K. It was found that the key parameters determining the boundary of carbon formation are temperature, type of solid electrolyte and extent of the electrochemical reaction of hydrogen. The minimum requirements of H2O/fuel ratio for each type of fuel in which the carbon formation is thermodynamically unfavored were compared. At the same operating conditions, DIR-SOFC fueled by ethanol required the lowest inlet H2O/fuel ratio in which the carbon formation is thermodynamically unfavored. The requirement decreased with increasing temperature for all three fuels. Comparison between two types of the electrolytes reveals that the hydrogen-conducting electrolyte is impractical for use, regarding to the tendency of carbon formation. This is due mainly to the water formed by the electrochemical reaction at the electrodes. (author)

  11. Experimental and theoretical studies of thermodynamics of lithium halide solutions - ethanol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Nasehzadeh, Asadollah E-mail: nasehzadeh@mail.uk.ac.ir; Noroozian, Ebrahim; Omrani, Hengameh

    2004-03-01

    The vapor pressures of lithium halide solutions in ethanol have been determined in the range of concentration from (0.01 to 2.0) mol {center_dot} kg{sup -1} at 298.15 K. The activity of solvent was obtained directly and the osmotic coefficients of solutions were then calculated. An accurate reference osmotic coefficient (phi{sup 0}) was obtained in a more diluted solution at a reference molality, m{sup 0} (=10{sup -3} kg {center_dot} mol{sup -1}). The ionic activity coefficient, the excess, and the change in partial molal free energy of solutions were calculated by using Gibbs-Duhem equation. The values of osmotic coefficient that obtained in this work were fitted to MSA-NRTL and Pitzer's models and the values of characteristic adjustable parameters were calculated. It is shown that the goodness and the overall quality of the fit for both models are excellent.

  12. Experimental and theoretical studies of thermodynamics of lithium halide solutions - ethanol mixtures

    International Nuclear Information System (INIS)

    Nasehzadeh, Asadollah; Noroozian, Ebrahim; Omrani, Hengameh

    2004-01-01

    The vapor pressures of lithium halide solutions in ethanol have been determined in the range of concentration from (0.01 to 2.0) mol · kg -1 at 298.15 K. The activity of solvent was obtained directly and the osmotic coefficients of solutions were then calculated. An accurate reference osmotic coefficient (phi 0 ) was obtained in a more diluted solution at a reference molality, m 0 (=10 -3 kg · mol -1 ). The ionic activity coefficient, the excess, and the change in partial molal free energy of solutions were calculated by using Gibbs-Duhem equation. The values of osmotic coefficient that obtained in this work were fitted to MSA-NRTL and Pitzer's models and the values of characteristic adjustable parameters were calculated. It is shown that the goodness and the overall quality of the fit for both models are excellent

  13. Thermodynamic characteristics of viscous flow activation in aqueous solutions of alkali metal iodides

    International Nuclear Information System (INIS)

    Renskij, I.A.; Rudnitskaya, A.A.; Fialkov, Yu.A.

    2003-01-01

    The Gibbs activation energy of the viscous flow of the alkali metal iodides aqueous solutions MI (M = Li, Na, K, Cs) and from its temperature dependence - the enthalpy and entropy of this process are calculated by the Eyring modified equation. The kinetic compensation effects, related to the viscous flow of the unbound water and to the ion-hydrate complexes are established. The relative contribution of the enthalpy and entropy constituents for these solution components is analyzed [ru

  14. Regularities in electroconductivity and thermo-emf in systems of binary continuous solid solutions of metals

    International Nuclear Information System (INIS)

    Vedernikov, M.V.; Dvunitkin, V.G.; Zhumagulov, A.

    1978-01-01

    Given are new experimental data about specific electric resistance of 10 systems of binary continuous solid metal solutions at the temperatures of 293 and 4.2 K: Cr-V, Mo-Nb, Mo-V, Cr-Mo, Nb-V, Ti-Zr, Hf-Zr, Hf-Ti, Sc-Zr, Sc-Hf. For the first time a comparative analysis of all available data on the resistance dependence on the composition of systems of continuous solid solutions, which covers 21 systems, is carried out. The ''resistance-composition'' dependence for such alloy systems is found to be of two types. The dependence of the first type is characteristic of the systems, formed by two isoelectronic metals, the dependence of the second type - for the systems, formed by non-isoelectronic metals. Thermo-emf of each type of solid solutions differently depends on their compositions

  15. The Systematics of Activity-Composition Relations in Mg-Fe2+ Oxide and Silicate Solid Solutions

    Science.gov (United States)

    O'Neill, H. S.

    2006-12-01

    The need to quantify activity-composition relations of mineral solid solutions for petrologic modelling has prompted many experimental studies, but different studies on the same system often appear to show a startling lack of consistency. A good example is Mg-Fe2+ mixing in garnet (the pyrope-almandine join). This is understandable because the energies of mixing in solid solutions are often obtained experimentally as small difference between large numbers. In particular, the fallacy of using a sequential approach to data fitting to a thermodynamic model leads to the accumulated errors being artificially concentrated onto the last step of the fitting process, which is usually that part of the model dealing with the excess energies of mixing. This gives rise to erroneous activity-composition relations, often apparently showing complex deviations from ideality. Systemizing the results of many studies can reveal underlying patterns of behaviour while also identifying outliers and anomalies that may be worth reinvestigating. Davies and Navrotsky [1] showed that the energies of mixing of many different pairs of ions with the same charge correlated well with the difference in molar volumes of the end-members, within a particular crystal structure. This empirical work is now supported by theoretical calculations. It underlies the modern approach to melt/crystal trace-element partitioning. Provided an internally consistent dataset is used, an analogous correlation may be demonstrated across different crystal structures for the mixing of one pair of ions, such as Mg and Fe2+. Activity-composition relations in MgO-"FeO" magnesiowuestite solutions in equilibrium with iron metal were used to obtain the properties of Mg-Fe olivine solutions from magnesiowuestite/olivine partitioning [2]. New results at 1400 K, 1 bar and 1473 K, 25 kb (O'Neill and Pownceby, in prep.) confirm previous work that mixing in Mg-Fe olivine is regular (symmetrical) with W Mg-Fe = 2.5 kJ/mol, with an

  16. A thermodynamic approach to assess organic solute adsorption onto activated carbon in water

    KAUST Repository

    De Ridder, David J.; Verliefde, Arne R. D.; Heijman, Bas G J; Gelin, Simon; Pereira, Manuel Fernando Ribeiro; Rocha, Raquel P.; Figueiredo, José Luí s M; Amy, Gary L.; Van Dijk, Hans C.

    2012-01-01

    In this paper, the hydrophobicity of 13 activated carbons is determined by various methods; water vapour adsorption, immersion calorimetry, and contact angle measurements. The quantity and type of oxygen-containing groups on the activated carbon were measured and related to the methods used to measure hydrophobicity. It was found that the water-activated carbon adsorption strength (based on immersion calorimetry, contact angles) depended on both type and quantity of oxygen-containing groups, while water vapour adsorption depended only on their quantity. Activated carbon hydrophobicity measurements alone could not be related to 1-hexanol and 1,3-dichloropropene adsorption. However, a relationship was found between work of adhesion and adsorption of these solutes. The work of adhesion depends not only on activated carbon-water interaction (carbon hydrophobicity), but also on solute-water (solute hydrophobicity) and activated carbon-solute interactions. Our research shows that the work of adhesion can explain solute adsorption and includes the effect of hydrogen bond formation between solute and activated carbon. © 2012 Elsevier Ltd. All rights reserved.

  17. A thermodynamic approach to assess organic solute adsorption onto activated carbon in water

    KAUST Repository

    De Ridder, David J.

    2012-08-01

    In this paper, the hydrophobicity of 13 activated carbons is determined by various methods; water vapour adsorption, immersion calorimetry, and contact angle measurements. The quantity and type of oxygen-containing groups on the activated carbon were measured and related to the methods used to measure hydrophobicity. It was found that the water-activated carbon adsorption strength (based on immersion calorimetry, contact angles) depended on both type and quantity of oxygen-containing groups, while water vapour adsorption depended only on their quantity. Activated carbon hydrophobicity measurements alone could not be related to 1-hexanol and 1,3-dichloropropene adsorption. However, a relationship was found between work of adhesion and adsorption of these solutes. The work of adhesion depends not only on activated carbon-water interaction (carbon hydrophobicity), but also on solute-water (solute hydrophobicity) and activated carbon-solute interactions. Our research shows that the work of adhesion can explain solute adsorption and includes the effect of hydrogen bond formation between solute and activated carbon. © 2012 Elsevier Ltd. All rights reserved.

  18. The LiBH4-LiI Solid Solution as an Electrolyte in an All-Solid-State Battery

    DEFF Research Database (Denmark)

    Sveinbjörnsson, Dadi Þorsteinn; Christiansen, Ane Sælland; Viskinde, Rasmus

    2014-01-01

    The charge and discharge performance of an all-solid-state lithium battery with the LiBH4-LiI solid solution as an electrolyte is reported. Lithium titanate (Li4Ti5O12) was used as the positive electrode and lithium metal as the negative electrode. The performance of the all-solid-state cell...

  19. Influence of additives (inorganic/organic on the clouding behavior of amphiphilic drug solutions: Some thermodynamic studies

    Directory of Open Access Journals (Sweden)

    Malik Abdul Rub

    2015-05-01

    Full Text Available Herein we provide a detailed result about the effect of various additives, viz. inorganic salts, quaternary ammonium bromides (QABs and amino acids on clouding behavior of amphiphilic drug amitriptyline hydrochloride (AMT. The continuous increase in the cloud point (CP of drug by increase in inorganic salt concentration and the magnitude of increases rely upon the position of the salts in Hofmeister series and hydrated radii. The QABs also influence continuous increase in the CP, which is illustrated in terms of the alkyl chain length of peculiar QAB. The effect of amino acids on CP of the drug solution is dependent upon the characteristics (acidic, basic, polar or nonpolar of particular amino acids. The overall behavior of additives has been analyzed and discussed on the basis of electrostatic repulsion or interaction, micellar growth, and mixed micelle formation between the ingredients. In addition to this, thermodynamic parameters are also evaluated.

  20. Aspects récents de la thermodynamique des solutions de polymères Recent Aspects of the Thermodynamics of Polymer Solutions

    Directory of Open Access Journals (Sweden)

    Dayantis J.

    2006-11-01

    Full Text Available On examine dans cet article différentes approches de la thermodynamique des solutions de polymères placées dans leur contexte historique. On rappelle d'abord le modèle du réseau de Flory-Huggins et on en souligne les déficiences. On traite ensuite brièvement de la mécanique statistique des solutions de polymères introduite par Prigogine en 1957 et on montre qu'elle constitue un progrès qualitatif par rapport à la théorie du réseau, mais qu'elle ne prévoit cependant pas de manière quantitative les propriétés de ces solutions. On montre ensuite que le concept de volume libre, qui permet un traitement simplifié de certaines quantités, permet également d'expliquer tout naturellement l'existence d'une deuxième température de séparation en phase lorsque l'on élève la température, propriété qui différencie les solutions de polymères des mélanges de liquidés simples. Enfin, dans une dernière partie, on mentionne brièvement les travaux récents de l'École de Paris, qui traite les solutions de polymères par analogie avec les transitions magnétiques. This article examines différent approaches ta the thermodynamics of polymer solutions set in their historical context. First of all, the Flory-Huggins network model is described and ifs deficiencies are pointed out. Then attention is briefly drawn to the statistical mechanics of polymer solutions as introduced by Prigogine in 1957, and this mechanics is shown to be a qualitative advance compared with the network theory, but it nonetheless does not quantitatively predict the properties of such solutions. It is then shown that the concept of free volume, enabling some quantifies to be treated in a simplified way, also serves to provide a quite natural explanation for the existence of a second phase separation temperature when the temperature is raised, i. e. a property that differentiates polymer solutions from simple liquid mixtures. In the final part, brief mention is made

  1. Determination of thermodynamic properties and stability limit from fluorite phase of uranium and lanthanide mixed oxides, using galvanic cells with solid electrolytes

    International Nuclear Information System (INIS)

    Santiago, T.N.

    1980-10-01

    A method for thermodynamic properties determination for oxygen solubility in oxide systems at temperature interval 973 ≤ T [K] ≤ 1773 is described. A galvanic cell using as solid electrolytes zircon dioxide doped with 15% of calcium oxide is presented. This method was used for determining the phase change, temperature dependent, of uranium-lanthanides-oxygen Ln U O 4 stoichiometric system. (C.G.C.)

  2. A Moessbauer study on the photolysis of potassium trisoxalatoferrate(III) in solid and solutions

    International Nuclear Information System (INIS)

    Sato, H.; Tominaga, T.

    1977-01-01

    The photolysis of potassium trisoxalatoferrate(III) in solid and aqueous solutions was studied by Moessbauer spectroscopy. A ferrous species was mainly detected as an intermediate product in the photoirradiated solutions. A tentative mechanism was proposed for the overall reactions in and after the photolysis of this compound. The Moessbauer spectra were measured with a Hitachi AA-40 or Shimadzu MEG-2 Moessbauer spectrometer against Co-57 in copper foil. Acrylic holders (32 mm in diameter) were used for measurements of solutions: the irradiated solution was quickly frozen before measurement by adding it dropwise into the acrylic holder which had been cooled with liquid nitrogen or dry-ice. (T.I.)

  3. Chemical thermodynamic representation of

    International Nuclear Information System (INIS)

    Lindemer, T.B.; Besmann, T.M.

    1984-01-01

    The entire data base for the dependence of the nonstoichiometry, x, on temperature and chemical potential of oxygen (oxygen potential) was retrieved from the literature and represented. This data base was interpreted by least-squares analysis using equations derived from the classical thermodynamic theory for the solid solution of a solute in a solvent. For hyperstoichiometric oxide at oxygen potentials more positive than -266700 + 16.5T kJ/mol, the data were best represented by a [UO 2 ]-[U 3 O 7 ] solution. For O/U ratios above 2 and oxygen potentials below this boundary, a [UO 2 ]-[U 2 O 4 . 5 ] solution represented the data. The data were represented by a [UO 2 ]-[U 1 / 3 ] solution. The resulting equations represent the experimental ln(PO 2 ) - ln(x) behavior and can be used in thermodynamic calculations to predict phase boundary compositions consistent with the literature. Collectively, the present analysis permits a mathematical representation of the behavior of the total data base

  4. Light refractive index in indium phosphide and InP-containing solid solutions

    International Nuclear Information System (INIS)

    Yas'kov, A.D.

    1983-01-01

    Spectral and temperatUre dependences of the InP and Gasub(x)Insub(1-x)P refractive indexes in the range of 0.98-1.3 μm are measured. The obtained in this case and published earlier experimental data on refractive index dispersion of the InP and solid solutions with its participation are generalized within the framework of a simple model approach based on a consecutiVe account of measured parameters of zone structure with the solid solution composition

  5. Phase coexistence in ferroelectric solid solutions: Formation of monoclinic phase with enhanced piezoelectricity

    Directory of Open Access Journals (Sweden)

    Xiaoyan Lu

    2016-10-01

    Full Text Available Phase morphology and corresponding piezoelectricity in ferroelectric solid solutions were studied by using a phenomenological theory with the consideration of phase coexistence. Results have shown that phases with similar energy potentials can coexist, thus induce interfacial stresses which lead to the formation of adaptive monoclinic phases. A new tetragonal-like monoclinic to rhombohedral-like monoclinic phase transition was predicted in a shear stress state. Enhanced piezoelectricity can be achieved by manipulating the stress state close to a critical stress field. Phase coexistence is universal in ferroelectric solid solutions and may provide a way to optimize ultra-fine structures and proper stress states to achieve ultrahigh piezoelectricity.

  6. Specific features of kinetics of He3-He4 solid solution transformations at superlow temperatures

    International Nuclear Information System (INIS)

    Mikheev, V.A.; Majdanov, V.A.; Mikhin, N.P.

    1986-01-01

    The NMR data on the phase transition kinetics of 3 He- 4 He solid solutions at T=100 mK are considered. Studied are solid helium samples of a molecular volume of 20.55 cm 2 /mol with a 3 He content of 0.54 %. An unusually long phase transition time is found which is dependent on the prehistory of sample. The spin diffusion of 3 He in the transformated solution concentrated phase is found to be of a quasi-one-dimensional nature with the diffusion coefficient value typical of liquid

  7. Characterization of solid-solution interface by potentiometric titration and electrophoretic mobility

    International Nuclear Information System (INIS)

    Lindecker, C.; Drot, R.; Fourest, B.; Simoni, E.

    1999-01-01

    The study of nuclear waste storage in deep geological sites involves the understanding of processes which could produce a possible dispersion or retention of radioelements. The dispersion of solid particles in aqueous solution is consequently important to be characterized. In this bi-phased system it is necessary to determine the characteristics of the solid-solution interface. The method used of this study is the techniques of potentiometric titration applied to heterogeneous systems. The material studied were phosphate matrices which were synthesized in the laboratory. The dependence of their surface change upon the nature of the electrolytes was investigated

  8. Decomposition features of a supersaturated solid solution in the Mg-3.3 wt. % Yb alloy

    International Nuclear Information System (INIS)

    Dobromyslov, A.V.; Kajgorodova, L.I.; Sukhanov, V.D.; Dobatkina, T.V.

    2007-01-01

    Methods of electron microscopy, hardness measuring and X-ray diffraction analysis are applied to study decomposition kinetics for a supersaturated solid solution in a Mg-3.3 mas. % alloy on aging within a temperature range of 150-225 deg C. The mechanism of supersaturation solid solution decomposition is revealed along with the nature of phases precipitated at various stages of aging: on incomplete and extended aging as well as at maximum hardness. The types of structural constituents responsible for changes of hardness on aging are determined [ru

  9. Adsorptive removal of phenol from aqueous solutions on activated carbon prepared from tobacco residues: Equilibrium, kinetics and thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Kilic, Murat; Apaydin-Varol, Esin [Department of Chemical Engineering, Anadolu University, Eskisehir 26470 (Turkey); Puetuen, Ayse E., E-mail: aeputun@anadolu.edu.tr [Department of Chemical Engineering, Anadolu University, Eskisehir 26470 (Turkey)

    2011-05-15

    This study consists of producing high surface area activated carbon from tobacco residues by chemical activation and its behavior of phenol removal from aqueous solutions. K{sub 2}CO{sub 3} and KOH were used as chemical activation agents and three impregnation ratios (50, 75 and 100 wt.%) were applied on biomass. Maximum BET surface areas of activated carbons were obtained from impregnation with 75 wt.% of K{sub 2}CO{sub 3} and 75 wt.% of KOH as 1635 and 1474 m{sup 2}/g, respectively. Optimum adsorption conditions were determined as a function of pH, adsorbent dosage, initial phenol concentration, contact time and temperature of solution for phenol removal. To describe the equilibrium isotherms the experimental data were analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherm models. Pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models were used to find out the kinetic parameters and mechanism of adsorption process. The thermodynamic parameters such as {Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o} were calculated for predicting the nature of adsorption. According to the experimental results, activated carbon prepared from tobacco residue seems to be an effective, low-cost and alternative adsorbent precursor for the removal of phenol from aqueous solutions.

  10. Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: Equilibrium, kinetic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Senturk, Hasan Basri; Ozdes, Duygu; Gundogdu, Ali; Duran, Celal [Department of Chemistry, Karadeniz Technical University, Faculty of Arts and Sciences, 61080 Trabzon (Turkey); Soylak, Mustafa, E-mail: soylak@erciyes.edu.tr [Department of Chemistry, Erciyes University, Faculty of Arts and Sciences, 38039 Kayseri (Turkey)

    2009-12-15

    A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1 h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g{sup -1}. Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R{sup 2} > 0.99). Thermodynamic parameters including the Gibbs free energy ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}), and entropy ({Delta}S{sup o}) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0-40 {sup o}C.

  11. Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: Equilibrium, kinetic and thermodynamic study

    International Nuclear Information System (INIS)

    Senturk, Hasan Basri; Ozdes, Duygu; Gundogdu, Ali; Duran, Celal; Soylak, Mustafa

    2009-01-01

    A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1 h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g -1 . Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R 2 > 0.99). Thermodynamic parameters including the Gibbs free energy (ΔG o ), enthalpy (ΔH o ), and entropy (ΔS o ) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0-40 o C.

  12. Thermodynamic analysis of energy density in pressure retarded osmosis: The impact of solution volumes and costs

    International Nuclear Information System (INIS)

    Reimund, Kevin K.

    2015-01-01

    A general method was developed for estimating the volumetric energy efficiency of pressure retarded osmosis via pressure-volume analysis of a membrane process. The resulting model requires only the osmotic pressure, π, and mass fraction, w, of water in the concentrated and dilute feed solutions to estimate the maximum achievable specific energy density, uu, as a function of operating pressure. The model is independent of any membrane or module properties. This method utilizes equilibrium analysis to specify the volumetric mixing fraction of concentrated and dilute solution as a function of operating pressure, and provides results for the total volumetric energy density of similar order to more complex models for the mixing of seawater and riverwater. Within the framework of this analysis, the total volumetric energy density is maximized, for an idealized case, when the operating pressure is π(1+√w -1 ), which is lower than the maximum power density operating pressure, Δπ/2, derived elsewhere, and is a function of the solute osmotic pressure at a given mass fraction. It was also found that a minimum 1.45 kmol of ideal solute is required to produce 1 kWh of energy while a system operating at "maximum power density operating pressure" requires at least 2.9 kmol. Utilizing this methodology, it is possible to examine the effects of volumetric solution cost, operation of a module at various pressure, and operation of a constant pressure module with various feed.

  13. Thermodynamic analysis of energy density in pressure retarded osmosis: The impact of solution volumes and costs

    Energy Technology Data Exchange (ETDEWEB)

    Reimund, Kevin K. [Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemical and Biomolecular Engineering; McCutcheon, Jeffrey R. [Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemical and Biomolecular Engineering; Wilson, Aaron D. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-08-01

    A general method was developed for estimating the volumetric energy efficiency of pressure retarded osmosis via pressure-volume analysis of a membrane process. The resulting model requires only the osmotic pressure, π, and mass fraction, w, of water in the concentrated and dilute feed solutions to estimate the maximum achievable specific energy density, uu, as a function of operating pressure. The model is independent of any membrane or module properties. This method utilizes equilibrium analysis to specify the volumetric mixing fraction of concentrated and dilute solution as a function of operating pressure, and provides results for the total volumetric energy density of similar order to more complex models for the mixing of seawater and riverwater. Within the framework of this analysis, the total volumetric energy density is maximized, for an idealized case, when the operating pressure is π/(1+√w⁻¹), which is lower than the maximum power density operating pressure, Δπ/2, derived elsewhere, and is a function of the solute osmotic pressure at a given mass fraction. It was also found that a minimum 1.45 kmol of ideal solute is required to produce 1 kWh of energy while a system operating at “maximum power density operating pressure” requires at least 2.9 kmol. Utilizing this methodology, it is possible to examine the effects of volumetric solution cost, operation of a module at various pressure, and operation of a constant pressure module with various feed.

  14. Thermodynamic behavior of erythritol in aqueous solutions and in gelatine gels and its quantification

    International Nuclear Information System (INIS)

    Tyapkova, Oxana; Bader-Mittermaier, Stephanie; Schweiggert-Weisz, Ute

    2013-01-01

    Highlights: • Differential scanning calorimetry as a method to determine erythritol crystallization. • Determination of crystallization using solution enthalpy. • Erythritol crystallization influenced by area of air–water-interfaces. • DSC method is applicable for both aqueous solutions and gels. • Adaption of DSC method to other, more complex food matrices is possible. - Abstract: As crystallization of erythritol can cause a sandy mouth-feel in sugar-free products, strategies to avoid crystallization or adaption of food formulation should be elucidated. However, until now erythritol crystallization was only quantified in aqueous solutions, but not in model food systems. Differential scanning calorimetry (DSC) is a simple method for the quantification of phase transition in various systems. However, no methods for the quantification of crystallization from aqueous systems based on DSC have been published until now. In the present study DSC was found to be suitable for the quantification of crystallization using supersaturated aqueous solutions of erythritol and erythritol containing gelatine gels for the first time. The developed method was validated by comparing the crystallization values determined by gravimetric measurement of erythritol crystals and the values obtained by DSC. No significant differences (p < 0.05) have been obtained between the results of the two methods if an appropriate design of measurements was applied. Additionally, the method was adapted to gelatine gels to elucidate the transferability to model food systems. Hence, the method is suitable for quantification of the amount of erythritol crystals present in aqueous solutions and gels, respectively

  15. Thermodynamics phase transition and Hawking radiation of the Schwarzschild black hole with quintessence-like matter and a deficit solid angle

    Science.gov (United States)

    Rodrigue, Kamiko Kouemeni Jean; Saleh, Mahamat; Thomas, Bouetou Bouetou; Kofane, Timoleon Crepin

    2018-05-01

    In this paper, we investigate the thermodynamics and Hawking radiation of Schwarzschild black hole with quintessence-like matter and deficit solid angle. From the metric of the black hole, we derive the expressions of temperature and specific heat using the laws of black hole thermodynamics. Using the null geodesics method and Parikh-Wilczeck tunneling method, we derive the expressions of Boltzmann factor and the change of Bekenstein-Hawking entropy for the black hole. The behaviors of the temperature, specific heat, Boltzmann factor and the change of Bekenstein entropy versus the deficit solid angle (ɛ 2) and the density of static spherically symmetric quintessence-like matter (ρ 0) were explicitly plotted. The results show that, when the deficit solid angle (ɛ 2) and the density of static spherically symmetric quintessence-like matter at r=1 (ρ 0) vanish (ρ 0=ɛ =0), these four thermodynamics quantities are reduced to those obtained for the simple case of Schwarzschild black hole. For low entropies, the presence of quintessence-like matter induces a first order phase transition of the black hole and for the higher values of the entropies, we observe the second order phase transition. When increasing ρ 0, the transition points are shifted to lower entropies. The same thing is observed when increasing ɛ 2. In the absence of quintessence-like matter (ρ 0=0), these transition phenomena disappear. Moreover the rate of radiation decreases when increasing ρ 0 or (ɛ ^2).

  16. Adsorption of cadmium from aqueous solution onto untreated coffee grounds: Equilibrium, kinetics and thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Azouaou, N., E-mail: azouaou20@yahoo.fr [Laboratory of Reaction Genius, Faculty of Mechanical and Processes Genius, University of Sciences and Technology Houari - Boumediene, USTHB, BP no 32 El Alia bab ezzouar, 16111 Algiers (Algeria); Sadaoui, Z. [Laboratory of Reaction Genius, Faculty of Mechanical and Processes Genius, University of Sciences and Technology Houari - Boumediene, USTHB, BP no 32 El Alia bab ezzouar, 16111 Algiers (Algeria); Djaafri, A. [Central laboratory, SEAAL, 97 Parc ben omar, Kouba, Algiers (Algeria); Mokaddem, H. [Laboratory of Reaction Genius, Faculty of Mechanical and Processes Genius, University of Sciences and Technology Houari - Boumediene, USTHB, BP no 32 El Alia bab ezzouar, 16111 Algiers (Algeria)

    2010-12-15

    Adsorption can be used as a cost effective and efficient technique for the removal of toxic heavy metals from wastewater. Waste materials with no further treatment such as coffee grounds from cafeterias may act as adsorbents for the removal of cadmium. Batch kinetic and equilibrium experiments were conducted to study the effects of contact time, adsorbent dose, initial pH, particle size, initial concentration of cadmium and temperature. Three adsorption isotherm models namely, Langmuir, Freundlich and Dubinin-Radushkevich were used to analyse the equilibrium data. The Langmuir isotherm which provided the best correlation for Cd{sup 2+} adsorption onto coffee grounds, shows that the adsorption was favourable and the adsorption capacity found was equal to 15.65 mg g{sup -1}. Thermodynamic parameters were evaluated and the adsorption was exothermic. The equilibrium was achieved less than 120 min. The adsorption kinetic data was fitted with first and second order kinetic models. Finally it was concluded that the cadmium adsorption kinetic onto coffee grounds was well fitted by second order kinetic model rather than first order model. The results suggest that coffee grounds have high possibility to be used as effective and economical adsorbent for Cd{sup 2+} removal.

  17. Efficient removal of cobalt from aqueous solution by zinc oxide nanoparticles. Kinetic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Khezami, L.; Modwi, A. [Al Imam Mohammad Ibn Saud Islamic Univ. (IMSIU), Riyadh (Saudi Arabia). Dept. of Chemistry; Taha, Kamal K. [Al Imam Mohammad Ibn Saud Islamic Univ. (IMSIU), Riyadh (Saudi Arabia). Dept. of Chemistry; Univ. of Bahri, Khartoum (Sudan). College of Applied and Industrial Sciences

    2017-08-01

    This article deals with the removal of cobalt ions using zinc oxide nanopowder. The nanomaterial was prepared via the sol-gel method under supercritical drying. The nanomaterial was characterised via XRD, SEM, EDX, FTIR, and BET surface area techniques. The kinetics, equilibrium, and thermodynamic studies of the metal ions adsorption on the nanomaterial were conducted in batch mode experiments by varying some parameters such as pH, contact time, initial ion concentrations, nanoparticles dose, and temperature. The data revealed significant dependence of the adsorption process on concentration, and the temperature was found to enhance the adsorption rate indicating an endothermic nature of the adsorption. The adsorption complied well with the pseudo-second-order kinetics model. The adsorption process was found to match the Langmuir adsorption isotherm. The ZnO nanoparticles could successfully remove up to 125 mg.g{sup -1} of Co(II) ions at elevated temperature. The metal ions adsorption could be described as an endothermic, spontaneous physisorption process. A mechanism for the metal ions adsorption was proposed.

  18. A new model for predicting thermodynamic properties of ternary metallic solution from binary components

    International Nuclear Information System (INIS)

    Fang Zheng; Zhang Quanru

    2006-01-01

    A model has been derived to predict thermodynamic properties of ternary metallic systems from those of its three binaries. In the model, the excess Gibbs free energies and the interaction parameter ω 123 for three components of a ternary are expressed as a simple sum of those of the three sub-binaries, and the mole fractions of the components of the ternary are identical with the sub-binaries. This model is greatly simplified compared with the current symmetrical and asymmetrical models. It is able to overcome some shortcomings of the current models, such as the arrangement of the components in the Gibbs triangle, the conversion of mole fractions between ternary and corresponding binaries, and some necessary processes for optimizing the various parameters of these models. Two ternary systems, Mg-Cu-Ni and Cd-Bi-Pb are recalculated to demonstrate the validity and precision of the present model. The calculated results on the Mg-Cu-Ni system are better than those in the literature. New parameters in the Margules equations expressing the excess Gibbs free energies of three binary systems of the Cd-Bi-Pb ternary system are also given

  19. Thermodynamic and spectroscopic studies of alanine and phenylalanine in aqueous β-cyclodextrin solutions

    Directory of Open Access Journals (Sweden)

    Anwar Ali

    2017-01-01

    Full Text Available Ultrasonic speed, u and density, ρ have been measured for dl-alanine (Ala and l-phenylalanine (Phe in aqueous β-cyclodextrin (β-CD at 298.15, 303.15, 308.15, and 313.15 K. The complexation of Ala and Phe with β-CD has been studied by means of UV–vis and thermodynamic (ultrasonic speed and density studies. Using the measured ultrasonic speed and density data the apparent molar compressibility (κS,φ, apparent molar volume (Vφ, limiting apparent molar compressibility (κS,φ0, limiting apparent molar volume (Vφ0, their constants (SK and Sv, and hydration number (nH have been obtained. The positive values of transfer properties at infinite dilution for Ala and Phe in β-CD is the outcome of the balance between released water molecules from β-CD cavity and hydrophobic groups of Ala and Phe that enter into the macrocycle β-CD cavity. The experimental results have also been discussed on the basis of UV–vis absorbance. The results indicate the formation of a more stable host–guest complex between Phe-β-CD than between Ala-β-CD.

  20. Adsorption of cadmium from aqueous solution onto untreated coffee grounds: Equilibrium, kinetics and thermodynamics

    International Nuclear Information System (INIS)

    Azouaou, N.; Sadaoui, Z.; Djaafri, A.; Mokaddem, H.

    2010-01-01

    Adsorption can be used as a cost effective and efficient technique for the removal of toxic heavy metals from wastewater. Waste materials with no further treatment such as coffee grounds from cafeterias may act as adsorbents for the removal of cadmium. Batch kinetic and equilibrium experiments were conducted to study the effects of contact time, adsorbent dose, initial pH, particle size, initial concentration of cadmium and temperature. Three adsorption isotherm models namely, Langmuir, Freundlich and Dubinin-Radushkevich were used to analyse the equilibrium data. The Langmuir isotherm which provided the best correlation for Cd 2+ adsorption onto coffee grounds, shows that the adsorption was favourable and the adsorption capacity found was equal to 15.65 mg g -1 . Thermodynamic parameters were evaluated and the adsorption was exothermic. The equilibrium was achieved less than 120 min. The adsorption kinetic data was fitted with first and second order kinetic models. Finally it was concluded that the cadmium adsorption kinetic onto coffee grounds was well fitted by second order kinetic model rather than first order model. The results suggest that coffee grounds have high possibility to be used as effective and economical adsorbent for Cd 2+ removal.

  1. Efficient removal of cobalt from aqueous solution by zinc oxide nanoparticles. Kinetic and thermodynamic studies

    International Nuclear Information System (INIS)

    Khezami, L.; Modwi, A.; Taha, Kamal K.; Univ. of Bahri, Khartoum

    2017-01-01

    This article deals with the removal of cobalt ions using zinc oxide nanopowder. The nanomaterial was prepared via the sol-gel method under supercritical drying. The nanomaterial was characterised via XRD, SEM, EDX, FTIR, and BET surface area techniques. The kinetics, equilibrium, and thermodynamic studies of the metal ions adsorption on the nanomaterial were conducted in batch mode experiments by varying some parameters such as pH, contact time, initial ion concentrations, nanoparticles dose, and temperature. The data revealed significant dependence of the adsorption process on concentration, and the temperature was found to enhance the adsorption rate indicating an endothermic nature of the adsorption. The adsorption complied well with the pseudo-second-order kinetics model. The adsorption process was found to match the Langmuir adsorption isotherm. The ZnO nanoparticles could successfully remove up to 125 mg.g -1 of Co(II) ions at elevated temperature. The metal ions adsorption could be described as an endothermic, spontaneous physisorption process. A mechanism for the metal ions adsorption was proposed.

  2. Solution structure, dynamics and thermodynamics of the three SH3 domains of CD2AP

    Energy Technology Data Exchange (ETDEWEB)

    Roldan, Jose L. Ortega [Universidad de Granada, Departamento de Quimica Fisica e Instituto de Biotecnologia, Facultad de Ciencias (Spain); Blackledge, Martin [Institut de Biologie Structurale Jean-Pierre Ebel, CEA, CNRS, UJF UMR 5075, Protein Dynamics and Flexibility by NMR (France); Nuland, Nico A. J. van, E-mail: nvnuland@vub.ac.be [Vrije Universiteit Brussel, Structural Biology Brussels (Belgium); Azuaga, Ana I. [Universidad de Granada, Departamento de Quimica Fisica e Instituto de Biotecnologia, Facultad de Ciencias (Spain)

    2011-06-15

    CD2 associated protein (CD2AP) is an adaptor protein that plays an important role in cell to cell union needed for the kidney function. It contains three N-terminal SH3 domains that are able to interact among others with CD2, ALIX, c-Cbl and Ubiquitin. To understand the role of the individual SH3 domains of this adaptor protein we have performed a complete structural, thermodynamic and dynamic characterization of the separate domains using NMR and DSC. The energetic contributions to the stability and the backbone dynamics have been related to the structural features of each domain using the structure-based FoldX algorithm. We have found that the N-terminal SH3 domain of both adaptor proteins CD2AP and CIN85 are the most stable SH3 domains that have been studied until now. This high stability is driven by a more extensive network of intra-molecular interactions. We believe that this increased stabilization of N-terminal SH3 domains in adaptor proteins is crucial to maintain the necessary conformation to establish the proper interactions critical for the recruitment of their natural targets.

  3. High temperature thermodynamics of solutions of oxygen in zirconium and hafnium

    International Nuclear Information System (INIS)

    Boureau, G.; Gerdanian, P.

    1984-01-01

    The Tian-Calvet microcalorimetric method has been applied to the determination at 1323 Kelvin of ΔH(O 2 ), the partial molar enthalpy of mixing of oxygen in zirconium and in hafnium. No measurable departure from Henry's law has been found for dilute solutions (ratio oxygen over metal smaller than 0.1). For concentrated solutions repulsive interactions are found in agreement with the existence of ordered structures at lower temperatures. The domain of homogeneity of zirconium has been found larger than previously assumed. (author)

  4. Direct measurements of the enthalpy of solution of solid solute in supercritical fluids: study on the CO2-naphthalene system.

    Science.gov (United States)

    Zhang, X; Han, B; Zhang, J; Li, H; He, J; Yan, H

    2001-10-01

    A setup for a calorimeter for simultaneously measuring the solubility and the solution enthalpy of solid solutes in supercritical fluids (SCFs) has been established. The enthalpy of solution of naphthalene in supercritical CO2 was measured at 308.15 K in the pressure range from 8.0-11.0 MPa. It was found that the enthalpy of solution (deltaH) was negative in the pressure range from 8.0 to 9.5 MPa, and the absolute value decreased with increasing pressure. In this pressure range, the dissolution of the solute was enthalpy driven. However, the deltaH became positive at pressures higher than 9.5 MPa, and the dissolution was entropy driven. Monte Carlo simulation was performed to analyze the local structural environment of the solvated naphthalene molecules in supercritical CO2 under the experimental conditions for the calorimetric measurements. By combining the enthalpy data and the simulation results, it can be deduced that the energy level of CO2 in the high compressible region is higher than that at higher pressures, which results in the large negative enthalpy of solution and the larger degree of solvent-solute clustering in the high compressible region.

  5. Estimation of the thermodynamic parameters of hydrogen bonding in alcohol solutions by the method of infrared spectroscopy

    Science.gov (United States)

    Vedernikova, E. V.; Gafurov, M. M.; Ataev, M. B.

    2011-01-01

    Hydrogen bonding (H-bonding) is a specific type of intermolecular interaction being formed for favorable mutual orientations of the interacting molecules. One of the authors had developed a model concept relating the H-bonding energy with the change of stretching vibrations Δν = νOH - νOH-NC of the alcohol OH-group in acetonitrile and acetone solutions: Δ H = 89.24Δν/ν0. The calculated H-bond energy was 10.45 kJ/mole for acetonitrile and Δ H = 12.12 kJ/mole for acetone. The results obtained are compared with the data calculated using the equilibrium constant of H-bonding reaction; they can also be used to calculate all other thermodynamic H-bond parameters by measuring the equilibrium constant K c in a certain temperature interval. The equilibrium constant is calculated from the Lambert-Bouguer-Beer law: {K_c} = {{C_{{text{OH}} \\cdots {text{NC}}}}}/{{C_{text{OH}} \\cdot {C_{text{NC}}}}} , ∆ F = - RT ṡ ln K c , ∆ H = RT 2 ṡ d(ln K c )/ dT, and Δ S = {Δ H - Δ F}/T . For the methanol solution in acetonitrile, Δν = 115 cm-1, Δ H = 10.87 kJ/mole, and K c = 42 L/mole. For the ethanol solution in acetonitrile, Δν = 118 cm-1, Δ H = 10.01 kJ/mole, and K c = 34 L/mole. For the propanol solution in acetonitrile, Δν = 110 cm-1, Δ H = 8.36 kJ/mole, and K c = 13 L/mole. All calculations are performed using the developed programs. The spectra are recorded on Perkin-Elmer-180 and Specord-84 IR-spectrometers. The values of the thermodynamic parameters calculated and estimated from K c - f( T) are in good agreement with each other and with the available literature data.

  6. Diffusion kinetics and spinodal decay of quasi-equilibrium solid solutions

    International Nuclear Information System (INIS)

    Zakharov, M.A.

    2000-01-01

    Phenomenological theory for rearrangement of solid solutions with the hierarchy of the component atomic mobilities is elaborated in the approximation of the local equilibrium. The hydrodynamic stage of the evolution of these solutions is studied as a sequence of quasi-equilibrium states characterized by implementation of some conditions of the total equilibrium. On the basis of separation of fast and slow constituents of diffusion and on the basis of the method of reduced description one derived equation for evolution of separations of fast components in quasi-equilibrium solid solutions at the arbitrary stages of rearrangement in terms of the generalized lattice model taking account of the proper volumes of the components. The conditions of the stability of quasi-equilibrium solutions to the spinodal decomposition are determined and the equations of metastability boundaries of such systems are derived [ru

  7. Localized solid-state amorphization at grain boundaries in a nanocrystalline Al solid solution subjected to surface mechanical attrition

    Energy Technology Data Exchange (ETDEWEB)

    Wu, X [State Key Laboratory of Nonlinear Mechanics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100080 (China); Tao, N [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China); Hong, Y [State Key Laboratory of Nonlinear Mechanics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100080 (China); Lu, J [LASMIS, University of Technology of Troyes, 10000, Troyes (France); Lu, K [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China)

    2005-11-21

    Using high-resolution electron microscopy, localized solid-state amorphization (SSA) was observed in a nanocrystalline (NC) Al solid solution (weight per cent 4.2 Cu, 0.3 Mn, the rest being Al) subjected to a surface mechanical attrition treatment. It was found that the deformation-induced SSA may occur at the grain boundary (GB) where either the high density dislocations or dislocation complexes are present. It is suggested that lattice instability due to elastic distortion within the dislocation core region plays a significant role in the initiation of the localized SSA at defective sites. Meanwhile, the GB of severely deformed NC grains exhibits a continuously varying atomic structure in such a way that while most of the GB is ordered but reveals corrugated configurations, localized amorphization may occur along the same GB.

  8. Cementation of the solid radioactive waste with polymer-cement solutions using the method of impregnation

    International Nuclear Information System (INIS)

    Gorbunova, O.

    2015-01-01

    Cementation of solid radioactive waste (SRW), i.e. inclusion of solid radioactive waste into cement matrix without cavities - is one of the main technological processes used for conditioning low and intermediate level radioactive waste. At FSUE 'Radon' the industrialized method of impregnation has been developed and since 2003 has been using for cementation of solid radioactive waste. The technology is that the polymer-cement solution, having high penetrating properties, is supplied under pressure through a tube to the bottom of the container in which solid radioactive waste has preliminarily been placed. The polymer-cement solution is evenly moving upwards through the channels between the particles of solid radioactive waste, fills the voids in the bulk volume of the waste and hardens, forming a cement compound, the amount of which is equal to the original volume. The aim of the investigation was a selection of a cement solution suitable for SRW impregnation (including fine particles) without solution depletion and bottom layers stuffing. It has been chosen a polymer: PHMG (polyhexamethylene-guanidine), which is a stabilizing and water-retaining component of the cement solution. The experiments confirm that the polymer increases the permeability of the cement solution by a 2-2.5 factor, the viscosity by a 1.2 factor, the stability of the consistency by a 1.5-1.7 factor, and extends the operating range of the W/C ratio to 0.5-1.1. So it is possible to penetrate a volume of SRW bigger by a 1.5-2.0 factor. It has been proved, that PHMG polymer increases strength and frost-resistance of the final compounds by a 1.8-2.7 factor, and contributes to fast strength development at the beginning of hardening and it decreases Cs-137 leashing rate by a 1.5-2 factor

  9. Systems Ln-Fe-O ( Ln=Eu, Gd): thermodynamic properties of ternary oxides using solid-state electrochemical cells

    Science.gov (United States)

    Parida, S. C.; Rakshit, S. K.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

    2003-05-01

    The standard molar Gibbs energies of formation of LnFeO 3(s) and Ln3Fe 5O 12(s) where Ln=Eu and Gd have been determined using solid-state electrochemical technique employing different solid electrolytes. The reversible e.m.f.s of the following solid-state electrochemical cells have been measured in the temperature range from 1050 to 1255 K. Cell (I): (-)Pt / { LnFeO 3(s)+ Ln2O 3(s)+Fe(s)} // YDT/CSZ // {Fe(s)+Fe 0.95O(s)} / Pt(+); Cell (II): (-)Pt/{Fe(s)+Fe 0.95O(s)}//CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+); Cell (III): (-)Pt/{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}//YSZ//{Ni(s)+NiO(s)}/Pt(+); and Cell(IV):(-)Pt/{Fe(s)+Fe 0.95O(s)}//YDT/CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+). The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the e.m.f. data. The standard Gibbs energies of formation of solid EuFeO 3, Eu 3Fe 5O 12, GdFeO 3 and Gd 3Fe 5O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by Δ fG°m(EuFeO 3, s) /kJ mol -1 (± 3.2)=-1265.5+0.2687( T/K) (1050 ⩽ T/K ⩽ 1570), Δ fG°m(Eu 3Fe 5O 12, s)/kJ mol -1 (± 3.5)=-4626.2+1.0474( T/K) (1050 ⩽ T/K ⩽ 1255), Δ fG°m(GdFeO 3, s) /kJ mol -1 (± 3.2)=-1342.5+0.2539( T/K) (1050 ⩽ T/K ⩽ 1570), and Δ fG°m(Gd 3Fe 5O 12, s)/kJ·mol -1 (± 3.5)=-4856.0+1.0021( T/K) (1050 ⩽ T/K ⩽ 1255). The uncertainty estimates for Δ fG°m include the standard deviation in the e.m.f. and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagrams for the systems Eu-Fe-O and Gd-Fe-O and chemical potential diagrams for the system Gd-Fe-O were computed at 1250 K.

  10. Magnetic susceptibilities of Ca/sub y/U/sub 1-y/O/sub 2+x/ solid solutions

    International Nuclear Information System (INIS)

    Hinatsu, Y.; Fujino, T.

    1988-01-01

    Magnetic susceptibilities of Ca/sub y/U/sub 1-y/O/sub 2+x/ solid solutions with fluorite structure were measured from 4.2 K to room temperature. An antiferromagnetic transition was observed for all the solid solutions examined in this study (y ≤ 0.33). The Neel temperature of the oxygen-hypostoichiometric solid solutions (x 2 solid solutions, but different from that of (U,Th)O 2 solid solutions. The effective magnetic moment decreased with increasing calcium concentration, which indicates the oxidation of uranium in the solid solutions. From the analysis of the magnetic susceptibility data, it was found that the oxidation state of uranium was either tetravalent or pentavalent. The Neel temperature of the hyperstoichiometric solid solutions (x > 0) did not change appreciably with calcium concentrations. From the comparison of the magnetic susceptibility data of the hypostoichiometric solid solutions with those of the hyperstoichiometric solid solutions, the effect of oxygen vacancies is more significant than that of interstitial oxygens on the decrease of magnetic interactions between uranium ions

  11. Thermodynamic characteristics of solutions of Bu4NI in dimethylsulfoxide over a wide concentration range

    International Nuclear Information System (INIS)

    Safonova, L.P.; Shmukler, L.Eh.; Kolker, A.M.

    2008-01-01

    The integral heats of solution of Bu 4 NI in dimethylsulfoxide (DMSO) were measured at 298.15, 313.15, and 328.15 K and concentrations from dilute to saturation. The standard enthalpies and heat capacities of solution and solvation of Bu 4 NI in DMSO at various temperatures and the C-bar p 0 (Bu 4 N + ) value at 298.15 K were calculated. The obtained and literature data were used to consider the influence of the nature of solvents on Δ sol H m (Bu 4 NI) and of the electrolyte on Δ sol H m in dimethylsulfoxide at 298.15 K. The dynamic viscosity and density of the Bu 4 NI-DMSO system were determined at various concentrations and temperatures. The Eyring equation was used to calculate the activation energy of viscous flow at all the concentrations studied [ru

  12. The thermodynamic characteristics of solutions of Bu4NI in dimethylsulfoxide over a wide concentration range

    Science.gov (United States)

    Safonova, L. P.; Shmukler, L. E.; Kolker, A. M.

    2008-05-01

    The integral heats of solution of Bu4NI in dimethylsulfoxide (DMSO) were measured at 298.15, 313.15, and 328.15 K and concentrations from dilute to saturation. The standard enthalpies and heat capacities of solution and solvation of Bu4NI in DMSO at various temperatures and the bar C_p^o (Bu_4 N^ + ) value at 298.15 K were calculated. The obtained and literature data were used to consider the influence of the nature of solvents on Δsol H m (Bu4NI) and of the electrolyte on Δsol H m in dimethylsulfoxide at 298.15 K. The dynamic viscosity and density of the Bu4NI-DMSO system were determined at various concentrations and temperatures. The Eyring equation was used to calculate the activation energy of viscous flow at all the concentrations studied.

  13. Thermodynamic behavior of {ethanol + butylpyridinium tetrafluoroborate} binary solution in the critical region

    International Nuclear Information System (INIS)

    Tao, Xiaoyi; Yin, Tianxiang; Xu, Chen; Shen, Weiguo

    2017-01-01

    Highlights: • Coexistence curve, heat capacity and turbidity measurements were performed. • RTIL solution showed solvophobic criticality. • Universal critical amplitude ratios were testified. • Asymmetric behavior of the diameter of coexistence curve was discussed. - Abstract: The liquid-liquid coexistence curve, heat capacity, and turbidity of binary solution {ethanol + butylpyridinium tetrafluoroborate]} have been precisely measured. The critical exponents and critical amplitudes corresponding to the heat capacity, width of coexistence curve, osmotic compressibility, and correlation length were obtained. The critical exponents and critical amplitude ratios showed well agreements with the theoretical values of the 3D-Ising universality class. The asymmetric behavior of the coexistence curve diameter was found to be well described by the complete scaling theory with the consideration of the heat capacity related term.

  14. Thermodynamically accurate modeling of the catalytic cycle of photosynthetic oxygen evolution: a mathematical solution to asymmetric Markov chains.

    Science.gov (United States)

    Vinyard, David J; Zachary, Chase E; Ananyev, Gennady; Dismukes, G Charles

    2013-07-01

    Forty-three years ago, Kok and coworkers introduced a phenomenological model describing period-four oscillations in O2 flash yields during photosynthetic water oxidation (WOC), which had been first reported by Joliot and coworkers. The original two-parameter Kok model was subsequently extended in its level of complexity to better simulate diverse data sets, including intact cells and isolated PSII-WOCs, but at the expense of introducing physically unrealistic assumptions necessary to enable numerical solutions. To date, analytical solutions have been found only for symmetric Kok models (inefficiencies are equally probable for all intermediates, called "S-states"). However, it is widely accepted that S-state reaction steps are not identical and some are not reversible (by thermodynamic restraints) thereby causing asymmetric cycles. We have developed a mathematically more rigorous foundation that eliminates unphysical assumptions known to be in conflict with experiments and adopts a new experimental constraint on solutions. This new algorithm termed STEAMM for S-state Transition Eigenvalues of Asymmetric Markov Models enables solutions to models having fewer adjustable parameters and uses automated fitting to experimental data sets, yielding higher accuracy and precision than the classic Kok or extended Kok models. This new tool provides a general mathematical framework for analyzing damped oscillations arising from any cycle period using any appropriate Markov model, regardless of symmetry. We illustrate applications of STEAMM that better describe the intrinsic inefficiencies for photon-to-charge conversion within PSII-WOCs that are responsible for damped period-four and period-two oscillations of flash O2 yields across diverse species, while using simpler Markov models free from unrealistic assumptions. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Investigation of Different Colloidal Porous Silicon Solutions and Their Composite Solid Matrix Rods by Optical Techniques

    Science.gov (United States)

    Khan, M. Naziruddin; Aldalbahi, Ali; Almohammedi, Abdullah

    2018-03-01

    Colloidal porous silicon (PSi) in different solvents was synthesized by simple chemical etching. Colloidal solutions were then prepared using different quantities of silicon wafer pieces (Pcs) and chloroplatinic (Pt) acid in catalyst solution. The effect on the properties of the colloidal solutions and composite rods were investigated using various optical characterization techniques. Absorption and photoluminescence (PL) intensity of the colloidal PSi solutions are observed to depend on the quantity of wafer Pcs, the Pt-solution, and the porosity formation on the wafer surface. The morphological structure of the PSi in a solvent and the solid-rod environments were studied using field-emission scanning electron microscopy (FE-SEM) and were observed to have different structures. A mono-oriented structure of PSi exists in tetrahydrofuran, which has stereo orientation in dioxane and dimethylsulfoxide (approximately 5-8 nm as confirmed using high resolution transmission electron microscopy). Subsequently, some colloidal PSi solutions were directly embedded in three types of sol-gel-based matrices, silica, ormosils (or organically modified silica) and polymer, which easily generated solid rods. Spontaneous emission (SE) of the PSi solutions and their composite rods were examined using a high power picosecond 355 nm laser source. The emitted PL and SE signals of the colloidal PSi solutions were dependent on the Pt volume, nature of the solvent, quantity of Si wafer piece, and pumping energy. The response of SE signals from the PSi composites rods is an interesting phenomenon, and such nanocomposites may be used for future research on light amplification.

  16. An Evaluation of Four Electrolyte Models for the Prediction of Thermodynamic Properties of Aqueous Electrolyte Solutions

    Directory of Open Access Journals (Sweden)

    Kamalodin Momeni

    2017-04-01

    Full Text Available In this work, the performance of four electrolyte models for prediction the osmotic and activity coefficients of different aqueous salt solutions at 298 K, atmospheric pressure and in a wide range of concentrations are evaluated. In two of these models, (electrolyte Non-Random Two-Liquid e-NRTL and Mean Spherical Approximation-Non-Random Two-Liquid MSA-NRTL, association between ions of opposite charges for simplification purposes is ignored and in the other two ones, (Associative Mean Spherical Approximation-Non-Random Two-Liquid AMSA-NRTL and Binding Mean Spherical Approximation BiMSA association and solvation effects are considered. The predictions of these four models for the osmotic and activity coefficients of electrolyte solutions at 298 K and atmospheric pressure are compared with the experimental data reported in the literature. This comparison includes, 28 different aqueous salt solutions including thio-cyanates, perchlorates, nitrates, hydroxides, quaternary ammonium salts and others. The results show, the performance of models that consider association effects are better than others especially for higher salt concentrations. However, the best performance belongs to BiMSA model which has some parameters with physical meaning.

  17. Influence of Ce 0.68 Zr 0.32 O 2 solid solution on depositing ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 29; Issue 1. Influence of Ce0.68Zr0.32O2 solid solution on depositing -alumina washcoat on FeCrAl foils. Mei-Qing Shen Li-Wei Jia Wen-Long Zhou Jun Wang Ying Huang. Composites Volume 29 Issue 1 February 2006 pp 73-76 ...

  18. Contribution of Lattice Distortion to Solid Solution Strengthening in a Series of Refractory High Entropy Alloys

    Science.gov (United States)

    Chen, H.; Kauffmann, A.; Laube, S.; Choi, I.-C.; Schwaiger, R.; Huang, Y.; Lichtenberg, K.; Müller, F.; Gorr, B.; Christ, H.-J.; Heilmaier, M.

    2018-03-01

    We present an experimental approach for revealing the impact of lattice distortion on solid solution strengthening in a series of body-centered-cubic (bcc) Al-containing, refractory high entropy alloys (HEAs) from the Nb-Mo-Cr-Ti-Al system. By systematically varying the Nb and Cr content, a wide range of atomic size difference as a common measure for the lattice distortion was obtained. Single-phase, bcc solid solutions were achieved by arc melting and homogenization as well as verified by means of scanning electron microscopy and X-ray diffraction. The atomic radii of the alloying elements for determination of atomic size difference were recalculated on the basis of the mean atomic radii in and the chemical compositions of the solid solutions. Microhardness (μH) at room temperature correlates well with the deduced atomic size difference. Nevertheless, the mechanisms of microscopic slip lead to pronounced temperature dependence of mechanical strength. In order to account for this particular feature, we present a combined approach, using μH, nanoindentation, and compression tests. The athermal proportion to the yield stress of the investigated equimolar alloys is revealed. These parameters support the universality of this aforementioned correlation. Hence, the pertinence of lattice distortion for solid solution strengthening in bcc HEAs is proven.

  19. Defect structure of cubic solid solutions of alkaline earth and rare earth fluorides

    NARCIS (Netherlands)

    DenHartog, HW

    1996-01-01

    In this paper we will consider the disorder in some cubic solid solutions consisting of one of the alkaline earth fluorides and one of the rare earth fluorides. This is an attractive group of model materials, because these materials have a rather simple overall cubic structure. We will discuss the

  20. Thermal expansion of TRU nitride solid solutions as fuel materials for transmutation of minor actinides

    International Nuclear Information System (INIS)

    Takano, Masahide; Akabori, Mitsuo; Arai, Yasuo; Minato, Kazuo

    2009-01-01

    The lattice thermal expansion of the transuranium nitride solid solutions was measured to investigate the composition dependence. The single-phase solid solution samples of (Np 0.55 Am 0.45 )N, (Pu 0.59 Am 0.41 )N, (Np 0.21 Pu 0.52 Am 0.22 Cm 0.05 )N and (Pu 0.21 Am 0.18 Zr 0.61 )N were prepared by carbothermic nitridation of the respective transuranium dioxides and nitridation of Zr metal through hydride. The lattice parameters were measured by the high temperature X-ray diffraction method from room temperature up to 1478 K. The linear thermal expansion of each sample was determined as a function of temperature. The average thermal expansion coefficients over the temperature range of 293-1273 K for the solid solution samples were 10.1, 11.5, 10.8 and 8.8 x 10 -6 K -1 , respectively. Comparison of these values with those for the constituent nitrides showed that the average thermal expansion coefficients of the solid solution samples could be approximated by the linear mixture rule within the error of 2-3%.

  1. The preparation method of solid boron solution in silicon carbide in the form of micro powder

    International Nuclear Information System (INIS)

    Pampuch, R.; Stobierski, L.; Lis, J.; Bialoskorski, J.; Ermer, E.

    1993-01-01

    The preparation method of solid boron solution in silicon carbide in the form of micro power has been worked out. The method consists in introducing mixture of boron, carbon and silicon and heating in the atmosphere of inert gas to the 1573 K

  2. Solid solution in Al-4.5 wt% Cu produced by mechanical alloying

    International Nuclear Information System (INIS)

    Fogagnolo, J.B.; Amador, D.; Ruiz-Navas, E.M.; Torralba, J.M.

    2006-01-01

    Mechanical alloying has been used to produce oxide dispersion strengthened alloys, intermetallic compounds, aluminium alloys and to obtain nanostructured and amorphous materials, as well as to extend the solid solution limit. In this work, Al and Cu elemental powders were subjected to high-energy milling to produce Al-4.5 wt% Cu powder alloy. The powders obtained were characterized by scanning electron microscopy, X-ray diffraction (XRD) and differential scanning calorimetry (DSC), aiming to explore if the copper is present in solid solution or as small particles after high-energy milling. Related to the formation of a supersaturated solid solution, the results of scanning electron microscopy and X-ray diffraction are non-conclusive: the copper could be dispersed with a very small size, undetectable to both techniques. The Al 2 Cu precipitation at temperatures between 160 and 230 deg. C, verified by DSC and XRD analyses, substantiated that mechanical alloying had produced a supersaturated solid solution of copper in aluminium. The crystallite size as a function of milling time and annealing temperature was also determined by X-ray techniques

  3. Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

    Science.gov (United States)

    Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

    2015-01-28

    (1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

  4. Fine interstitial clusters as recombinators in decomposing solid solutions under irradiation

    International Nuclear Information System (INIS)

    Trushin, Yu.V.

    1991-01-01

    Behaviour of interstitial clusters and their roll in processes of radiation swelling of metals are described. It is shown that occurrence of coherent advanced precipitations during decomposition of solid solutions under irradiation leads to matrix supersaturation over interstitial atoms. This enhances recombination of unlike defects due to vacancy precipitation on fine interstitial clusters. Evaluation of cluster sizes was conducted

  5. Bridging phases at the morphotropic boundaries of lead oxide solid solutions

    NARCIS (Netherlands)

    Noheda, Beatriz; Cox, DE

    2006-01-01

    Ceramic solid solutions of PbZr1-xTixO3 (PZT) with compositions x similar or equal to 0.50 are well-known for their extraordinarily large piezoelectric responses. The latter are highly anisotropic, and it was recently shown that, for the rhombohedral compositions (x less than or similar to 0.5), the

  6. Study of reaction sequences for formation of solid solution: 0,48 ...

    African Journals Online (AJOL)

    ... of a low concentration of ions forming the perovskite structure PZT (Pb2+, Zr4+ et Ti4+) by other ions (Zn2+, Cr3+ et Sb+5 in our study) alters the reaction sequences training of the solid solution PZT and especially the formation of intermediate phase. Keywords: PZT / Calcination / TGA / DTA / RX / Piezoelectric Ceramics ...

  7. Exact Solution of the Two-Level System and the Einstein Solid in the Microcanonical Formalism

    Science.gov (United States)

    Bertoldi, Dalia S.; Bringa, Eduardo M.; Miranda, E. N.

    2011-01-01

    The two-level system and the Einstein model of a crystalline solid are taught in every course of statistical mechanics and they are solved in the microcanonical formalism because the number of accessible microstates can be easily evaluated. However, their solutions are usually presented using the Stirling approximation to deal with factorials. In…

  8. Dynamic nuclear polarization methods in solids and solutions to explore membrane proteins and membrane systems.

    Science.gov (United States)

    Cheng, Chi-Yuan; Han, Songi

    2013-01-01

    Membrane proteins regulate vital cellular processes, including signaling, ion transport, and vesicular trafficking. Obtaining experimental access to their structures, conformational fluctuations, orientations, locations, and hydration in membrane environments, as well as the lipid membrane properties, is critical to understanding their functions. Dynamic nuclear polarization (DNP) of frozen solids can dramatically boost the sensitivity of current solid-state nuclear magnetic resonance tools to enhance access to membrane protein structures in native membrane environments. Overhauser DNP in the solution state can map out the local and site-specific hydration dynamics landscape of membrane proteins and lipid membranes, critically complementing the structural and dynamics information obtained by electron paramagnetic resonance spectroscopy. Here, we provide an overview of how DNP methods in solids and solutions can significantly increase our understanding of membrane protein structures, dynamics, functions, and hydration in complex biological membrane environments.

  9. First-Principles Modeling of ThO2 Solid Solutions with Oxides of Trivalent Cations

    Science.gov (United States)

    Alexandrov, Vitaly; Asta, Mark; Gronbech-Jensen, Niels

    2010-03-01

    Solid solutions formed by doping ThO2 with oxides of trivalent cations, such as Y2O3 and La2O3, are suitable for solid electrolyte applications, similar to doped zirconia and ceria. ThO2 has also been gaining much attention as an alternative to UO2 in nuclear energy applications, the aforementioned trivalent cations being important fission products. In both cases the mixing energetics and short-range ordering/clustering are key to understanding structural and transport properties. Using first-principles atomistic calculations, we address intra- and intersublattice interactions for both cation and anion sublattices in ThO2-based fluorite-type solid solutions and compare the results with similar modeling studies for related trivalent-doped zirconia systems.

  10. Thermodynamic Equations of State for Aqueous Solutions Applied to Deep Icy Satellite and Exoplanet Oceans

    Science.gov (United States)

    Vance, S.; Brown, J. M.; Bollengier, O.; Journaux, B.; Sotin, C.; Choukroun, M.; Barnes, R.

    2014-12-01

    Supporting life in icy world or exoplanet oceans may require global seafloor chemical reactions between water and rock. Such interactions have been regarded as limited in larger icy worlds such as Ganymede and Titan, where ocean depths approach 800 km and GPa pressures (>10katm). If the oceans are composed of pure water, such conditions are consistent with the presence of dense ice phases V and VI that cover the rocky seafloor. Exoplanets with oceans can obtain pressures sufficient to generate ices VII and VIII. We have previously demonstrated temperature gradients in such oceans on the order of 20 K or more, resulting from fluid compressibility in a deep adiabatic ocean based on our experimental work. Accounting for increases in density for highly saline oceans leads to the possibility of oceans perched under and between high pressure ices. Ammonia has the opposite effect, instead decreasing ocean density, as reported by others and confirmed by our laboratory measurements in the ammonia water system. Here we report on the completed equation of state for aqueous ammonia derived from our prior measurements and optimized global b-spline fitting methods We use recent diamond anvil cell measurements for water and ammonia to extend the equation of state to 400°C and beyond 2 GPa, temperatures and pressures applicable to icy worlds and exoplanets. Densities show much less temperature dependence but comparabe high-pressure derivatives to previously published ammonia-water properties derived for application to Titan (Croft et al. 1988). Thermal expansion is in better agreement with the more self-consistent equation of state of Tillner-Roth and Friend (1998). We also describe development of a planetary NaCl equation of state using recent measurements of phase boundaries and sound speeds. We examine implications of realistic ocean-ice thermodynamics for Titan and exoplanet interiors using the methodology recently applied to Ganymede for oceans dominated by MgSO4. High

  11. Eggshell Powder as an Adsorbent for Removal of Fluoride from Aqueous Solution: Equilibrium, Kinetic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    R. Bhaumik

    2012-01-01

    Full Text Available A new medium, eggshell powder has been developed for fluoride removal from aqueous solution. Fluoride adsorption was studied in a batch system where adsorption was found to be pH dependent with maximum removal efficiency at 6.0. The experimental data was more satisfactorily fitted with Langmuir isotherm model. The kinetics and the factor controlling adsorption process fully accepted by pseudo-second-order model were also discussed. Ea was found to be 45.98 kJmol-1 by using Arrhenius equation, indicating chemisorption nature of fluoride onto eggshell powder. Thermodynamic study showed spontaneous nature and feasibility of the adsorption process with negative enthalpy (∆H0 value also supported the exothermic nature. Batch experiments were performed to study the applicability of the adsorbent by using fluoride contaminated water collected from affected areas. These results indicate that eggshell powder can be used as an effective, low-cost adsorbent to remove fluoride from aqueous solution as well as groundwater.

  12. Thermodynamic analysis of unimer-micelle and sphere-to-rod micellar transitions of aqueous solutions of sodium dodecylbenzenesulfonate

    International Nuclear Information System (INIS)

    Valente, Artur J.M.; López Cascales, J.J.; Fernández Romero, Antonio J.

    2014-01-01

    Highlights: • Unimer-micelle and sphere-to-rod micellar transitions were observed to sodium dodecylbenzenesulfonate in aqueous solutions. • Two micellar transitions were seen by electrical conductivity and surface tension. • An anomalous ΔS 0 and ΔH 0 increase with T was found for the second critical transition. • More stable aggregates are evidenced for spherical micelles than for the other shapes. - Abstract: Temperature dependence of specific conductivity of sodium dodecylbenzenesulfonate (NaDBS) aqueous solutions was analyzed. Two breaks on the plot appeared for all temperature, which suggest two micellar transitions. This has been corroborated by surface tension measurements. The first transition concentration occurs at the critical micelle concentration (CMC), whilst the second critical concentration (so-called transition micellar concentration, TMC) is due to a sphere-to-rod micelles transition. The dependence of CMC and TMC on the temperature allows the computation of the corresponding thermodynamic functions: Gibbs free energy, enthalpy and entropy changes. For the CMC, enthalpy and entropy increments were found that decrease with the temperature values. However, an anomalous behavior was obtained for the TMC, where both ΔS 0 and ΔH 0 values raised with the temperature increase. However, for both transitions, an (enthalpy + entropy) compensation is observed. These results will be compared with similar systems reported in the literature

  13. Adsorption of uranium(VI) from sulphate solutions using Amberlite IRA-402 resin: Equilibrium, kinetics and thermodynamics study

    International Nuclear Information System (INIS)

    Solgy, Mostafa; Taghizadeh, Majid; Ghoddocynejad, Davood

    2015-01-01

    Highlights: • Adsorption of uranium from sulphate solutions by an anion exchange resin. • The effects of pH, contact time and adsorbent dosage were investigated. • The adsorption equilibrium is well described by the Freundlich isotherm model. • The adsorption kinetics can be predicted by the pseudo second-order model. • The adsorption is a physical, spontaneous and endothermic process. - Abstract: In the present study, adsorption of uranium from sulphate solutions was evaluated using Amberlite IRA-402 resin. The variation of adsorption process was investigated in batch sorption mode. The parameters studied were pH, contact time and adsorbent dosage. Langmuir and Freundlich isotherm models were used in order to present a mathematical description of the equilibrium data at three different temperatures (25 °C, 35 °C and 45 °C). The final results confirmed that the equilibrium data tend to follow Freundlich isotherm model. The maximum adsorption capacity of Amberlite IRA-402 for uranium(VI) was evaluated to be 213 mg/g for the Langmuir model at 25 °C. The adsorption of uranium on the mentioned anion exchange resin was found to follow the pseudo-second order kinetic model, indicating that chemical adsorption was the rate limiting-step. The values of thermodynamic parameters proved that adsorption process of uranium onto Amberlite IRA-402 resin could be considered endothermic (ΔH > 0) and spontaneous (ΔG < 0)

  14. Equilibrium, Kinetic and Thermodynamic Study of Removal of Eosin Yellow from Aqueous Solution Using Teak Leaf Litter Powder.

    Science.gov (United States)

    Oyelude, Emmanuel O; Awudza, Johannes A M; Twumasi, Sylvester K

    2017-09-22

    Low-cost teak leaf litter powder (TLLP) was prepared as possible substitute for activated carbon. The feasibility of using the adsorbent to remove eosin yellow (EY) dye from aqueous solution was investigated through equilibrium adsorption, kinetic and thermodynamic studies. The removal of dye from aqueous solution was feasible but influenced by temperature, pH, adsorbent dosage and contact time. Variation in the initial concentration of dye did not influence the equilibrium contact time. Optimum adsorption of dye occurred at low adsorbent dosages, alkaline pH and high temperatures. Langmuir isotherm model best fit the equilibrium adsorption data and the maximum monolayer capacity of the adsorbent was 31.64 mg g -1 at 303 K. The adsorption process was best described by pseudo-second order kinetic model at 303 K. Boundary layer diffusion played a key role in the adsorption process. The mechanism of uptake of EY by TLLP was controlled by both liquid film diffusion and intraparticle diffusion. The values of mean adsorption free energy, E (7.91 kJ mol -1 ), and standard enthalpy, ΔH° (+13.34 kJ mol -1 ), suggest physical adsorption. The adsorption process was endothermic and spontaneous. Teak leaf litter powder is a promising low-cost adsorbent for treating wastewaters containing eosin yellow.

  15. Reactive-site hydrolyzed Cucurbita maxima trypsin inhibitor-V: function, thermodynamic stability, and NMR solution structure.

    Science.gov (United States)

    Cai, M; Gong, Y; Prakash, O; Krishnamoorthi, R

    1995-09-26

    Reactive-site (Lys44-Asp45 peptide bond) hydrolyzed Cucurbita maxima trypsin inhibitor-V (CMTI-V*) was prepared and characterized: In comparison to the intact form, CMTI-V* exhibited markedly reduced inhibitory properties and binding affinities toward trypsin and human blood coagulation factor XIIa. The equilibrium constant of trypsin-catalyzed hydrolysis, Khyd, defined as [CMTI-V*]/[CMTI-V], was measured to be approximately 9.4 at 25 degrees C (delta G degrees = -1.3 kcal.mol-1). From the temperature dependence of delta G degrees, the following thermodynamic parameters were estimated: delta H degrees = 1.6 kcal.mol-1 and delta S degrees = 9.8 eu. In order to understand the functional and thermodynamic differences between the two forms, the three-dimensional solution structure of CMTI-V* was determined by a combined approach of NMR, distance geometry, and simulated annealing methods. Thus, following sequence-specific and stereospecific resonance assignments, including those of beta-, gamma-, delta-, and epsilon-hydrogens and valine methyl hydrogens, 809 interhydrogen distances and 123 dihedral angle constraints were determined, resulting in the computation and energy-minimization of 20 structures for CMTI-V*. The average root mean squared deviation in position for equivalent atoms between the 20 individual structures and the mean structure obtained by averaging their coordinates is 0.67 +/- 0.15 A for the main chain atoms and 1.19 +/- 0.23 A for all the non-hydrogen atoms of residues 5-40 and residues 48-67.(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Thermodynamic and spectroscopic study of Al3+ interaction with glycine, l-cysteine and tranexamic acid in aqueous solution.

    Science.gov (United States)

    Cardiano, Paola; Giacobello, Fausta; Giuffrè, Ottavia; Sammartano, Silvio

    2017-11-01

    In this paper a thermodynamic and spectroscopic study on the interaction between Al 3+ and glycine (Gly), l-cysteine (Cys), tranexamic acid (Tranex) is reported. Speciation models have been obtained by processing potentiometric titration data to determine stability constants of the species formed in aqueous solution at T=298.15K, 0.15≤I/molL -1 ≤1 in NaCl. Thermodynamic formation parameters have been obtained from calorimetric titration data, at T=298.15K, I=0.15molL -1 using NaCl as ionic medium. Al 3+ -Cys system was also investigated by spectrophotometric and 1 H NMR measurements. 1 H NMR experiments were performed on Al 3+ -Tranex system as well. Different speciation models have been observed for the three systems. The results showed the formation of MLH, ML and M 2 L 2 (OH) 2 species for Gly, ML, M 2 L and MLOH for Cys, MLH and MLOH for Tranex. The formed species are quite stable, i.e. for ML, logβ=7.18, 11.91 for Gly and Cys, respectively, at I=0.15molL -1 and T=298.15K. For all the systems the dependence of formation constants on ionic strength over the range 0.1-1molL -1 is reported. The sequestering ability of the ligands under study was also evaluated by pL 0.5 empiric parameter. For Gly, Cys and Tranex, pL 0.5 =2.51, 3.74, 3.91 respectively, at pH=5, I=0.15molL -1 and T=298.15K. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Phase separation in polymer solutions. II. Determination of thermodynamic parameters of poly (2,6-dimethyl-1,4-phenylene oxide) toluene mixtures

    NARCIS (Netherlands)

    van Emmerik, P.T.; Smolders, C.A.

    1972-01-01

    In liquid systems where it is possible to perform light scattering experiments at the melting points of polymer solutions without nucleation taking place because of undercooling, the thermodynamic parameters necessary to calculate the correction parameter g in the Flory-Huggins equation as modified

  18. Investigation of water and saline solution drops evaporation on a solid substrate

    Directory of Open Access Journals (Sweden)

    Orlova Evgenija G.

    2014-01-01

    Full Text Available Experimental investigation water and saline solution drops evaporation on a solid substrate made of anodized aluminum is presented in the paper. Parameters characterizing drop profile have been obtained (contact angle, contact diameter, height. The specific evaporation rate has been calculated from obtained values. It was found that water and saline solution drops with concentration up to 9.1% evaporate in the pinning mode. However, with increasing the salt concentration in the solution up to 16.7% spreading mode was observed. Two stages of drop evaporation depending on change of the evaporation rate have been separated.

  19. Steric structure and thermodynamic aspects of Dy3+ complexes with aminobenzoic acids in aqueous solutions

    International Nuclear Information System (INIS)

    Kondrashina, Yu.G.; Mustafina, A.R.; Vul'fson, S.G.

    1994-01-01

    Stability and structure of dysprosium(3) aminobenzoate complexes with molar ratios Dy:L 1:1 and 1:2 (HL-aminobenzoic acid) in aqueous solutions are determined on the basis of pH-metric and paramagnetic birefringence data. The increase of conjugation effect in the series of benzoic, meta- ortho-, and para-aminobenzoic acid results in the increase of stability of 1:1 and 1:2 complexes. Features of the structure and coordination of ligands in dysprosium complexes with meta-, ortho-, and para-aminobenzoic acid are considered. 11 refs.; 4 figs.; 2 tabs

  20. Failure criterion effect on solid production prediction and selection of completion solution

    Directory of Open Access Journals (Sweden)

    Dariush Javani

    2017-12-01

    Full Text Available Production of fines together with reservoir fluid is called solid production. It varies from a few grams or less per ton of reservoir fluid posing only minor problems, to catastrophic amount possibly leading to erosion and complete filling of the borehole. This paper assesses solid production potential in a carbonate gas reservoir located in the south of Iran. Petrophysical logs obtained from the vertical well were employed to construct mechanical earth model. Then, two failure criteria, i.e. Mohr–Coulomb and Mogi–Coulomb, were used to investigate the potential of solid production of the well in the initial and depleted conditions of the reservoir. Using these two criteria, we estimated critical collapse pressure and compared them to the reservoir pressure. Solid production occurs if collapse pressure is greater than pore pressure. Results indicate that the two failure criteria show different estimations of solid production potential of the studied reservoir. Mohr–Coulomb failure criterion estimated solid production in both initial and depleted conditions, where Mogi–Coulomb criterion predicted no solid production in the initial condition of reservoir. Based on Mogi–Coulomb criterion, the well may not require completion solutions like perforated liner, until at least 60% of reservoir pressure was depleted which leads to decrease in operation cost and time.

  1. A decontamination system for chemical weapons agents using a liquid solution on a solid sorbent.

    Science.gov (United States)

    Waysbort, Daniel; McGarvey, David J; Creasy, William R; Morrissey, Kevin M; Hendrickson, David M; Durst, H Dupont

    2009-01-30

    A decontamination system for chemical warfare agents was developed and tested that combines a liquid decontamination reagent solution with solid sorbent particles. The components have fewer safety and environmental concerns than traditional chlorine bleach-based products or highly caustic solutions. The liquid solution, based on Decon Greentrade mark, has hydrogen peroxide and a carbonate buffer as active ingredients. The best solid sorbents were found to be a copolymer of ethylene glycol dimethacrylate and n-lauryl methacrylate (Polytrap 6603 Adsorber); or an allyl methacrylate cross-linked polymer (Poly-Pore E200 Adsorber). These solids are human and environmentally friendly and are commonly used in cosmetics. The decontaminant system was tested for reactivity with pinacolyl methylphosphonofluoridate (Soman, GD), bis(2-chloroethyl)sulfide (Mustard, HD), and S-(2-diisopropylaminoethyl) O-ethyl methylphosphonothioate (VX) by using NMR Spectroscopy. Molybdate ion (MoO(4)(-2)) was added to the decontaminant to catalyze the oxidation of HD. The molybdate ion provided a color change from pink to white when the oxidizing capacity of the system was exhausted. The decontaminant was effective for ratios of agent to decontaminant of up to 1:50 for VX (t(1/2) decontamination solution were measured to show that the sorbent decreased the vapor concentration of GD. The E200 sorbent had the additional advantage of absorbing aqueous decontamination solution without the addition of an organic co-solvent such as isopropanol, but the rate depended strongly on mixing for HD.

  2. Solubility and hydrolysis of Np(V) in dilute to concentrated alkaline NaCl solutions. Formation of Na-Np(V)-OH solid phases at 22 C

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, Vladimir G. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; Fellhauer, David; Gaona, Xavier; Dardenne, Kathy; Rothe, Joerg; Altmaier, Marcus [Karlsruhe Institute of Technology (Germany). Inst. for Nuclear Waste Disposal; Kalmykov, Stepan N. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; NRC Kurchatov Institute, Moscow (Russian Federation)

    2017-03-01

    The solubility of Np(V) was investigated at T=22±2 C in alkaline NaCl solutions of different ionic strength (0.1-5.0 M). The solid phases controlling the solubility at different -log{sub 10} m{sub H{sup +}}(pH{sub m}) and NaCl concentration were characterized by XRD, quantitative chemical analysis, SEM-EDS and XAFS (both XANES and EXAFS). Aqueous phases in equilibrium with Np(V) solids were investigated for selected samples within 8.9≤pH{sub m}≤10.3 by UV-vis/NIR absorption spectroscopy. In 0.1 M NaCl, the experimental solubility of the initial greenish NpO{sub 2}OH(am) solid phase is in good agreement with previous results obtained in NaClO{sub 4} solutions, and is consistent with model calculations for fresh NpO{sub 2}OH(am) using the thermodynamic data selection in NEA-TDB. Below pH{sub m}∝11.5 and for all NaCl concentrations studied, Np concentration in equilibrium with the solid phase remained constant during the timeframe of this study (∝2 years). This observation is in contrast to the aging of the initial NpO{sub 2}OH(am) into a more crystalline modification with the same stoichiometry, NpO{sub 2}OH(am, aged), as reported in previous studies for concentrated NaClO{sub 4} and NaCl. Instead, the greenish NpO{sub 2}OH(am) transforms into a white solid phase in those systems with [NaCl]≥1.0 M and pH{sub m}≥11.5, and into two different pinkish phases above pH{sub m}∝13.2. The solid phase transformation is accompanied by a drop in Np solubility of 0.5-2 log{sub 10}-units (depending upon NaCl concentration). XANES analyses of green, white and pink phases confirm the predominance of Np(V) in all cases. Quantitative chemical analysis shows the incorporation of Na{sup +} in the original NpO{sub 2}OH(am) material, with Na:Np ≤ 0.3 for the greenish solids and 0.8 ≤ Na:Np ≤ 1.6 for the white and pinkish phases. XRD data confirms the amorphous character of the greenish phase, whereas white and pink solids show well-defined but discrepant XRD patterns

  3. Thermodynamic study of the adsorption of chromium ions from aqueous solution on waste corn cobs material

    Directory of Open Access Journals (Sweden)

    Rafael A. Fonseca-Correa

    2014-12-01

    Full Text Available The paper shows the results of a study obtaining activated carbon from corn cobs and determining its use as an adsorbent for the removal of Cr3+ from aqueous solutions. The finely ground precursor was subjected to pyrolysis at 600 and 900 °C in a nitrogen atmosphere and chemical activation with H2O2 and HNO3. The effects of pyrolysis conditions and activation method on the physicochemical properties of the materials obtained were tested. The samples were characterised chemically and texturally. Were obtained microporous activated carbons of well-developed surface area varying from 337 to 1213 m2/g and exhibited differences acid-base character of the surface. The results obtained shows that a suitable good option of the activation procedure for corncobs permits the production of economic adsorbents with high sorption capacity for Cr3+ from aqueous solutions. A detailed study of immersion calorimetry was performed with carbons prepared from corn cobs to establish possible relationships with these materials between the enthalpies of immersion and textural and chemical parameters.

  4. Current state in adsorption from multicomponent solutions of nonelectrolytes on solids

    International Nuclear Information System (INIS)

    Borowko, M.; Jaroniec, M.

    1983-01-01

    This paper surveys the research carried out on the adsorption from multicomponent liquid mixtures of nonelectrolytes on solids with emphasis on the work performed by the authors. The consistent theoretical treatment of adsorption from concentrated and dilute multicomponent solutions and its application to the liquid adsorption chromatography with the mixed mobile phase are presented. This treatment involved nonideality of the bulk and surface phases, energetic heterogeneity of the adsorbent surface and it may be extended to multilayer adsorption from solutions. The multicomponent liquid/solid adsorption systems, studied experimentally, are reviewed. Many of them have been examined by means of the equations derived for liquid adsorption on heterogeneous surfaces. These studies are summarized in this paper. Moreover, the model studies illustrating the influence of solution nonideality and adsorbent heterogeneity on the excess adsorption isotherms and the distribution coefficient are discussed. (orig.)

  5. Thermodynamics of the complex formation between thorium(IV) and some polydentate ligands in aqueous solution

    International Nuclear Information System (INIS)

    Di Bernado, P.; Cassol, A.; Tomat, G.; Bismondo, A.; Magon, L.

    1983-01-01

    The changes in free energy, enthalpy, and entropy for the formation of thorium(IV)-oxydiacetate, -iminodiacetate, -thiodiacetate, and -succinate complexes have been determined by potentiometric and calorimetric titrations at 25 deg C in aqueous 1 mol dm - 3 sodium perchlorate. All the ligands form 1:1 chelate complexes with the thorium(IV) ion the stability of which is dependent on both the chelate ring dimensions and the nature of the donor group in the chain. The order of the relative stabilities (iminodiacetate > oxydiacetate > thiodiacetate > succinate) is mainly dependent on the reaction enthalpies, since the δS values are close to each other. In the thorium(IV)-oxydiacetate system the maximum number of three ligands for every metal ion was reached. Because of precipitation of solid compounds in the other systems, it was only possible to define complexes with a lower number of co-ordinated ligands: two for succinate and thiodiacetate, and one for iminodiacetate. Owing to the lower stability of the chelate ring of thiodiacetate and succinate complexes and the high basicity of the amino-group of iminodiacetate, these ligands form also unchelated protonated complexes. (author)

  6. System DyFeO: thermodynamic properties of ternary oxides using Calvet calorimetry and solid-state electrochemical cell

    Science.gov (United States)

    Parida, S. C.; Jacob, K. T.; Venugopal, V.

    2002-10-01

    The enthalpy increments and the standard molar Gibbs energies of formation of DyFeO 3(s) and Dy 3Fe 5O 12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A co-operative phase transition, related to anti-ferromagnetic to paramagnetic transformation, is apparent from the heat capacity data for DyFeO 3 at ˜648 K. A similar type of phase transition has been observed for Dy 3Fe 5O 12 at ˜560 K which is related to ferrimagnetic to paramagnetic transformation. Enthalpy increment data for DyFeO 3(s) and Dy 3Fe 5O 12(s), except in the vicinity of the second-order transition, can be represented by the following polynomial expressions: {H 0m(T)-H 0m(298.15 K)} ( J mol-1) (±1.1%)=-52754+142.9×(T ( K))+2.48×10 -3×(T ( K)) 2+2.951×10 6×(T ( K)) -1;(298.15⩽ T ( K)⩽1000) for DyFeO 3(s), and {H 0m(T)-H 0m(298.15 K)} ( J mol-1) (±1.2%)=-191048+545.0×(T ( K))+2.0×10 -5×(T ( K)) 2+8.513×10 6×(T ( K)) -1;(298.15⩽T ( K)⩽1000) for Dy 3Fe 5O 12(s). The reversible emfs of the solid-state electrochemical cells: (-)Pt/{DyFeO 3(s) + Dy 2O 3(s) + Fe(s)}//YDT/CSZ//{Fe(s) + Fe 0.95O(s)}/Pt(+) and (-)Pt/{Fe(s) + Fe 0.95O(s)}//CSZ//{DyFeO 3(s) + Dy 3Fe 5O 12(s) + Fe 3O 4(s)}/Pt(+), were measured in the temperature range from 1021 to 1250 K and 1035 to 1250 K, respectively. The standard Gibbs energies of formation of solid DyFeO 3 and Dy 3Fe 5O 12 calculated by the least squares regression analysis of the data obtained in the present study, and data for Fe 0.95O and Dy 2O 3 from the literature, are given by: Δ fG 0m( DyFeO3, s) ( kJ mol-1) (±3.2)=-1339.9+0.2473×(T ( K));(1021⩽T ( K)⩽1548) and Δ fG 0m( Dy3Fe5O12, s) ( kJ mol-1) (±3.5)=-4850.4+0.9846×(T ( K));(1035⩽T ( K)⩽1250). The uncertainty estimates for Δ fG 0m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams for

  7. High temperature thermodynamics of solutions of oxygen in vanadium, niobium and tantalum

    International Nuclear Information System (INIS)

    Boureau, G.; Gerdanian, P.

    1981-01-01

    The Tian-Calvet microcalorimetric method has been applied to the determination at 1323 K of ΔH(O 2 ), the partial molar enthalpy of mixing of oxygen in vanadium, niobium and tantalum. The present results are in good agreement with earlier studies using e.m.f. techniques. Nevertheless in the first two solutions, ΔH(O 2 ) has been found somewhat more negative than previously reported. The partial molar entropies of mixing have been recalculated. The low values of the excess entropies are explained by a strong increase of the Debye temperature and a decrease of the electronic density of states at the Fermi level as the oxygen content increases. (author)

  8. Thermodynamic analysis of engineering solutions aimed at raising the efficiency of integrated gasification combined cycle

    Science.gov (United States)

    Gordeev, S. I.; Bogatova, T. F.; Ryzhkov, A. F.

    2017-11-01

    Raising the efficiency and environmental friendliness of electric power generation from coal is the aim of numerous research groups today. The traditional approach based on the steam power cycle has reached its efficiency limit, prompted by materials development and maneuverability performance. The rival approach based on the combined cycle is also drawing nearer to its efficiency limit. However, there is a reserve for efficiency increase of the integrated gasification combined cycle, which has the energy efficiency at the level of modern steam-turbine power units. The limit of increase in efficiency is the efficiency of NGCC. One of the main problems of the IGCC is higher costs of receiving and preparing fuel gas for GTU. It would be reasonable to decrease the necessary amount of fuel gas in the power unit to minimize the costs. The effect can be reached by raising of the heat value of fuel gas, its heat content and the heat content of cycle air. On the example of the process flowsheet of the IGCC with a power of 500 MW, running on Kuznetsk bituminous coal, by means of software Thermoflex, the influence of the developed technical solutions on the efficiency of the power plant is considered. It is received that rise in steam-air blast temperature to 900°C leads to an increase in conversion efficiency up to 84.2%. An increase in temperature levels of fuel gas clean-up to 900°C leads to an increase in the IGCC efficiency gross/net by 3.42%. Cycle air heating reduces the need for fuel gas by 40% and raises the IGCC efficiency gross/net by 0.85-1.22%. The offered solutions for IGCC allow to exceed net efficiency of analogous plants by 1.8-2.3%.

  9. Thermodynamic and structural description of europium complexation in 1-octanol - H2O solutions

    International Nuclear Information System (INIS)

    Vu, T.H.; Charbonnel, M.C.; Boubals, N.; Couston, L.; Arnaud, F.

    2008-01-01

    Polydentate N-bearing ligands such as bis-triazinyl-pyridines (BTPs) are interesting extractants for actinide(III)/lanthanide(III) separation. A description of europium complexation in 1-octanol solutions was undertaken to enhance the knowledge of the extraction mechanisms. The first solvation shell for europium(III) nitrate, chloride, and perchlorate with different amounts of water was determined by Time-Resolved Laser-Induced Fluorescence (TRLIF) spectroscopy. Europium nitrate complexation by iPr-BTP was then studied by TRLIF and micro-calorimetry; similar stability constants related to the formation of Eu(BTP) 2 3+ and Eu(BTP) 3 3+ were obtained by both techniques (log(β 2 ) = 9.0 ± 0.3 and log(β 3 ) = 13.8 ± 0.2). The presence of water in the octanol diluent has an influence on solvation of europium and also on the [Eu(BTP) 2 3+ ] / [Eu(BTP) 3 3+ ] ratio. (authors)

  10. Thermodynamic and structural description of europium complexation in 1-octanol - H{sub 2}O solutions

    Energy Technology Data Exchange (ETDEWEB)

    Vu, T.H.; Charbonnel, M.C.; Boubals, N.; Couston, L. [CEA Marcoule, DEN/DRCP/SCPS/LCAM, BP 17171, 30207 Bagnols-sur-Ceze (France); Arnaud, F. [Laboratoire de Chimie Physique, IPHC, 25 rue Becquerel, 67087 Strasbourg (France)

    2008-07-01

    Polydentate N-bearing ligands such as bis-triazinyl-pyridines (BTPs) are interesting extractants for actinide(III)/lanthanide(III) separation. A description of europium complexation in 1-octanol solutions was undertaken to enhance the knowledge of the extraction mechanisms. The first solvation shell for europium(III) nitrate, chloride, and perchlorate with different amounts of water was determined by Time-Resolved Laser-Induced Fluorescence (TRLIF) spectroscopy. Europium nitrate complexation by iPr-BTP was then studied by TRLIF and micro-calorimetry; similar stability constants related to the formation of Eu(BTP){sub 2}{sup 3+} and Eu(BTP){sub 3}{sup 3+} were obtained by both techniques (log({beta}{sub 2}) = 9.0 {+-} 0.3 and log({beta}{sub 3}) = 13.8 {+-} 0.2). The presence of water in the octanol diluent has an influence on solvation of europium and also on the [Eu(BTP){sub 2}{sup 3+}] / [Eu(BTP){sub 3}{sup 3+}] ratio. (authors)

  11. Solid solution strengthening and diffusion in nickel- and cobalt-based superalloys

    Energy Technology Data Exchange (ETDEWEB)

    Rehman, Hamad ur

    2016-07-01

    Nickel and cobalt-based superalloys with a γ-γ{sup '} microstructure are known for their excellent creep resistance at high temperatures. Their microstructure is engineered using different alloying elements, that partition either to the fcc γ matrix or to the ordered γ{sup '} phase. In the present work the effect of alloying elements on their segregation behaviour in nickel-based superalloys, diffusion in cobalt-based superalloys and the temperature dependent solid solution strengthening in nickel-based alloys is investigated. The effect of dendritic segregation on the local mechanical properties of individual phases in the as-cast, heat treated and creep deformed state of a nickel-based superalloy is investigated. The local chemical composition is characterized using Electron Probe Micro Analysis and then correlated with the mechanical properties of individual phases using nanoindentation. Furthermore, the temperature dependant solid solution hardening contribution of Ta, W and Re towards fcc nickel is studied. The room temperature hardening is determined by a diffusion couple approach using nanoindentation and energy dispersive X-ray analysis for relating hardness to the chemical composition. The high temperature properties are determined using compression strain rate jump tests. The results show that at lower temperatures, the solute size is prevalent and the elements with the largest size difference with nickel, induce the greatest hardening consistent with a classical solid solution strengthening theory. At higher temperatures, the solutes interact with the dislocations such that the slowest diffusing solute poses maximal resistance to dislocation glide and climb. Lastly, the diffusion of different technically relevant solutes in fcc cobalt is investigated using diffusion couples. The results show that the large atoms diffuse faster in cobalt-based superalloys similar to their nickel-based counterparts.

  12. Solid solution strengthening and diffusion in nickel- and cobalt-based superalloys

    International Nuclear Information System (INIS)

    Rehman, Hamad ur

    2016-01-01

    Nickel and cobalt-based superalloys with a γ-γ ' microstructure are known for their excellent creep resistance at high temperatures. Their microstructure is engineered using different alloying elements, that partition either to the fcc γ matrix or to the ordered γ ' phase. In the present work the effect of alloying elements on their segregation behaviour in nickel-based superalloys, diffusion in cobalt-based superalloys and the temperature dependent solid solution strengthening in nickel-based alloys is investigated. The effect of dendritic segregation on the local mechanical properties of individual phases in the as-cast, heat treated and creep deformed state of a nickel-based superalloy is investigated. The local chemical composition is characterized using Electron Probe Micro Analysis and then correlated with the mechanical properties of individual phases using nanoindentation. Furthermore, the temperature dependant solid solution hardening contribution of Ta, W and Re towards fcc nickel is studied. The room temperature hardening is determined by a diffusion couple approach using nanoindentation and energy dispersive X-ray analysis for relating hardness to the chemical composition. The high temperature properties are determined using compression strain rate jump tests. The results show that at lower temperatures, the solute size is prevalent and the elements with the largest size difference with nickel, induce the greatest hardening consistent with a classical solid solution strengthening theory. At higher temperatures, the solutes interact with the dislocations such that the slowest diffusing solute poses maximal resistance to dislocation glide and climb. Lastly, the diffusion of different technically relevant solutes in fcc cobalt is investigated using diffusion couples. The results show that the large atoms diffuse faster in cobalt-based superalloys similar to their nickel-based counterparts.

  13. Thermodynamic Modeling of a Solid Oxide Fuel Cell to Couple with an Existing Gas Turbine Engine Model

    Science.gov (United States)

    Brinson, Thomas E.; Kopasakis, George

    2004-01-01

    The Controls and Dynamics Technology Branch at NASA Glenn Research Center are interested in combining a solid oxide fuel cell (SOFC) to operate in conjunction with a gas turbine engine. A detailed engine model currently exists in the Matlab/Simulink environment. The idea is to incorporate a SOFC model within the turbine engine simulation and observe the hybrid system's performance. The fuel cell will be heated to its appropriate operating condition by the engine s combustor. Once the fuel cell is operating at its steady-state temperature, the gas burner will back down slowly until the engine is fully operating on the hot gases exhausted from the SOFC. The SOFC code is based on a steady-state model developed by The U.S. Department of Energy (DOE). In its current form, the DOE SOFC model exists in Microsoft Excel and uses Visual Basics to create an I-V (current-voltage) profile. For the project's application, the main issue with this model is that the gas path flow and fuel flow temperatures are used as input parameters instead of outputs. The objective is to create a SOFC model based on the DOE model that inputs the fuel cells flow rates and outputs temperature of the flow streams; therefore, creating a temperature profile as a function of fuel flow rate. This will be done by applying the First Law of Thermodynamics for a flow system to the fuel cell. Validation of this model will be done in two procedures. First, for a given flow rate the exit stream temperature will be calculated and compared to DOE SOFC temperature as a point comparison. Next, an I-V curve and temperature curve will be generated where the I-V curve will be compared with the DOE SOFC I-V curve. Matching I-V curves will suggest validation of the temperature curve because voltage is a function of temperature. Once the temperature profile is created and validated, the model will then be placed into the turbine engine simulation for system analysis.

  14. phase formation and thermal stability of fcc (fluorite) Ce1-xTbxO2-d solid solutions

    NARCIS (Netherlands)

    de Vries, Karel Jan; de Vries, K.J.; Meng, G.Y.

    1998-01-01

    Ce1−xTbxO2−δ solid solutions (x = 0.3, 0.4, and 0.5) were synthesized by a coprecipitation method, using ammonia. The formation process of the solid solutions was studied as a function of temperature up to 1200°C by X-ray diffraction, thermogravimetric analysis, and differential scanning

  15. Ionic thermocurrents and ionic conductivity of solid solutions of SrF2 and YbF3

    NARCIS (Netherlands)

    Meuldijk, J.; Hartog, den H.W.

    1983-01-01

    We report dielectric [ionic thermocurrent (!TC)] experiments and ionic conductivity of cubic solid solutions of the type Sr1-xYbxF2+x. These combined experiments provide us with new information concerning the ionic conductivity mechanisms which play an important role in solid solutions Sr1-xRxF2+x

  16. Local structure of Th1-xMO2 solid solutions (M = U, Pu)

    International Nuclear Information System (INIS)

    Hubert, S.; Heisbourg, G.; Moisy, Ph.; Dacheux, N.; Purans, J.E.

    2004-01-01

    X-ray absorption spectroscopy of Th 1-x U x O 2 and Th 1-x Pu x O 2 solid solutions was carried out on the Th, U L 3 -edges, and Pu L 3 edge to study the local structure environment of actinide mixed oxides. Various compositions of Th 1-x M x O 2 solid solutions have been prepared through the coprecipitation of the mixed oxalates from chloride or nitrate solutions: x = 0.11, 0.24, 0.37, 0.53, 0.67, 0.81, 0.91 and 1 for Th 1-x U x O 2 , and x = 0.13, 0.32, 0.66 and 1 for Th 1-x Pu x O 2 . They were characterized using X- ray diffraction. XRD analysis allowed to confirm that the variation of the lattice parameters varies linearly with the composition between the end members, suggesting that the atomic volume was conserved regardless of the details of the local distortions of the lattice, following the Vegard's law. Extending X-ray absorption fine structure (EXAFS) provides a direct characterization of the local distortions present in solid solutions. We found that opposite to the lattice parameter obtained by XRD, the interatomic distances given by EXAFS do not follow completely to neither the Vegard's law nor the virtual crystal approximation (VCA). However, the average lattice parameter obtained from EXAFS data for the first and the second shells agrees well with the one calculated from XRD data. (authors)

  17. Studies on Al-Mg solid solutions using electrical resistivity and microhardness measurements

    Energy Technology Data Exchange (ETDEWEB)

    Gaber, A.; Afify, N.; El-Halawany, S.M.; Mossad, A. [Assiut Univ. (Egypt). Dept. of Physics

    1999-08-01

    Al-C at% Mg alloys (C = 0.82, 1.84, 3.76, 5.74 and 12.18) have been selected for this study. From the electrical resistivity measurements it is concluded that the resistivity increment of Al-Mg alloys (in a solid solution state) is proportional to the atomic fractional constituents (Mg and Al) as {delta}{rho}{sub all} = 64.66 c(1-c) {mu}{omega} cm. In addition, both the temperature coefficient of resistivity, {alpha}{sub all} and the relaxation time of the free electrons {tau}{sub all} in the alloys diminish with increasing the solute Mg concentration. The increase of the scattering power, {eta}, with increasing C is interpreted to be due to the contribution of electron-impurity scattering. The percentage increase due to electron-impurity scattering per one atomic percent Mg has been determined as 12.99%. The Debye temperature {theta} decreases as the Mg concentration increases. The microhardness results showed that the solid solution hardening obeys the relation {delta}HV{sub s} = 135.5C{sup 0.778} MPa which is comparable to the theory of solid solution hardening for all alloys; {delta}HV{sub s} {approx} C{sup 0.5-0.67} MPa. (orig.)

  18. EPR of gamma irradiated solid sucrose and UV spectra of its solution. An attempt for calibration of solid state/EPR dosimetry

    International Nuclear Information System (INIS)

    Yordanov, N.D.; Karakirova, Y.

    2007-01-01

    A simple new approach for independent calibration of solid state/EPR (SS/EPR) dosimetry system is reported. It is based on the fact that: (i) gamma-irradiation of solid sucrose (sugar) induces stable EPR detectable free radicals accompanied by UV detectable brown colour stable in the solid state and in solution; (ii) both the EPR intensity of gamma-irradiated solid sucrose and its solution UV absorbance linearly depend on the absorbed dose high energy radiation and may be independently used for dosimetric purpose; (iii) UV spectrometers are calibrated. The correlation between EPR response and absorbed dose radiation of solid sucrose and UV absorption of its solutions is used in the present communication for calibration purpose. The procedure of sucrose extraction from sucrose-paraffin dosimeters is described. The calibration procedure may be applied to any other (alanine, self-calibrated, etc.) SS/EPR dosimeters, simultaneously irradiated with sucrose

  19. Application of mathematical experimental planning in the investigation of thermodynamic properties of three- component alloys

    International Nuclear Information System (INIS)

    Sokolovskaya, E.M.; Guzej, L.S.; Tikhankin, G.A.; Meshkov, L.L.

    1977-01-01

    Thermodynamic properties of solid solutions of niobium and tungsten in nickel have been investigated by the method of electromotive forces with the use of simplex-matrix experiment planning techniques. The planning matrix and the results of investigating the thermodynamic properties of alloys of the nickel-niobium-tungsten system at 1250 deg are presented. The application of experiment planning has made it possible to obtain sufficient information concerning the thermodynamics of solid solutions of niobium and tungsten in nickel from the experimental data for six ternary alloys only

  20. Thermodynamic stability of binary systems involving metal ions and the 4-methoxy benzylidenepyruvate in aqueous solution

    International Nuclear Information System (INIS)

    Redigolo, H.

    1989-01-01

    A review on studies previously carried out in this laboratory involving metal ions and benzylidene-pyruvate, in aqueous solutions, is presented; emphasis is mainly placed on complexes comprising 4-Dimethyl-amino-benzylidene-pyruvate (DMBP, p K a 3.79) and 2-Chloro-4-Dimethyl-amino-benzylidene-pyruvate (2 Cl-DMBP, p k a = 3.08). In an endeavour to extend the previous work, the dissociation constant of 4-methoxy-benzylidene-pyruvic acid (H-4-Me O-BP) was determined spectrophotometrically at 25.0 +- 0.1 0 C and ionic strength 0.500 M, held with sodium perchlorate (p k a = 1.473). The complex formation equilibria in M-4-Me O-BP systems, where M = Cu(II), La(III), Pr(III), Sm(III), Lu(III), Sc (III), In(III), Ga(III) or Th(IV) were investigated, also spectrophotometrically, in the above mentioned experimental conditions. In addition, the system involving Sm(III) was reinvestigated at ionic strengths 0.100 and 2.00 M, the remaining experimental conditions being maintained. The study is mostly concerned with the determination of formation constants of 1:1 complex species (β 1 ) and spectrophotometric parameters associated with these species. The investigation of possible higher binary complexes (ML n , n > 1) was prevented by solubility limitations. For all considered metal ions, log β 1 (DMBP) > log β 1 (4-Me O-BP) indicating that the stability is governed, at least in part, by ligand basicity. (author). 121 refs, 36 figs, 20 tabs

  1. Two stage fluid bed-plasma gasification process for solid waste valorisation: Technical review and preliminary thermodynamic modelling of sulphur emissions

    International Nuclear Information System (INIS)

    Morrin, Shane; Lettieri, Paola; Chapman, Chris; Mazzei, Luca

    2012-01-01

    Highlights: ► We investigate sulphur during MSW gasification within a fluid bed-plasma process. ► We review the literature on the feed, sulphur and process principles therein. ► The need for research in this area was identified. ► We perform thermodynamic modelling of the fluid bed stage. ► Initial findings indicate the prominence of solid phase sulphur. - Abstract: Gasification of solid waste for energy has significant potential given an abundant feed supply and strong policy drivers. Nonetheless, significant ambiguities in the knowledge base are apparent. Consequently this study investigates sulphur mechanisms within a novel two stage fluid bed-plasma gasification process. This paper includes a detailed review of gasification and plasma fundamentals in relation to the specific process, along with insight on MSW based feedstock properties and sulphur pollutant therein. As a first step to understanding sulphur partitioning and speciation within the process, thermodynamic modelling of the fluid bed stage has been performed. Preliminary findings, supported by plant experience, indicate the prominence of solid phase sulphur species (as opposed to H 2 S) – Na and K based species in particular. Work is underway to further investigate and validate this.

  2. Equilibrium, kinetic and thermodynamic studies of adsorption of Pb(II) from aqueous solution onto Turkish kaolinite clay

    International Nuclear Information System (INIS)

    Sari, Ahmet; Tuzen, Mustafa; Citak, Demirhan; Soylak, Mustafa

    2007-01-01

    The adsorption of Pb(II) onto Turkish (Bandirma region) kaolinite clay was examined in aqueous solution with respect to the pH, adsorbent dosage, contact time, and temperature. The linear Langmuir and Freundlich models were applied to describe equilibrium isotherms and both models fitted well. The monolayer adsorption capacity was found as 31.75 mg/g at pH 5 and 20 deg. C. Dubinin-Radushkevich (D-R) isotherm model was also applied to the equilibrium data. The mean free energy of adsorption (13.78 kJ/mol) indicated that the adsorption of Pb(II) onto kaolinite clay may be carried out via chemical ion-exchange mechanism. Thermodynamic parameters, free energy (ΔG o ), enthalpy (ΔH o ) and entropy (ΔS o ) of adsorption were also calculated. These parameters showed that the adsorption of Pb(II) onto kaolinite clay was feasible, spontaneous and exothermic process in nature. Furthermore, the Lagergren-first-order, pseudo-second-order and the intraparticle diffusion models were used to describe the kinetic data. The experimental data fitted well the pseudo-second-order kinetics

  3. Effective Remediation of Lead Ions from Aqueous Solution by Chemically Carbonized Rubber Wood Sawdust: Equilibrium, Kinetics, and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Swarup Biswas

    2015-01-01

    Full Text Available Rubber wood sawdust was carbonized into charcoal by chemical treatment which was used for removal of lead ion from aqueous solution. The work involves batch experiments to investigate the pH effect, initial concentration of adsorbate, contact time, and adsorbent dose. Experimental data confirmed that the adsorption capacities increased with increasing inlet concentration and bed height and decreased with increasing flow rate. Adsorption results showed a maximum adsorption capacity of 37 mg/g at 308 K. Langmuir, Freundlich, and Temkin model adsorption isotherm models were applied to analyze the process where Temkin was found as a best fitted model for present study. Simultaneously kinetics of adsorption like pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were investigated. Thermodynamic parameters were used to analyze the adsorption experiment. Fourier transform infrared spectroscopy, scanning electron microscope, and energy dispersive X-ray spectroscopy confirmed the batch adsorption of lead ion onto chemically carbonized rubber wood sawdust.

  4. Kinetics and Thermodynamics of Sorption of 4-Nitrophenol on Activated Kaolinitic Clay and Jatropha Curcas Activated Carbon from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Samsudeen Olanrewaju Azeez

    2016-06-01

    Full Text Available Adsorption behaviour of 4-nitrophenol (4-NP on activated kaolinitic clay and Jatropha curcas activated carbon was investigated. The kaolinitic clay and Jatropha curcas were activated with 1 M HNO3 and 0.5 M NaOH respectively and were characterized by XRF, XRD, BET, SEM and FTIR techniques. The effects of processing parameters, such as initial 4-NP concentration, temperature, pH, contact time and adsorbent dosage on the adsorption process were investigated. The results obtained showed that Jatropha curcas activated carbon exhibited higher performance than activated kaolinitic clay for the removal of 4-nitrophenol from aqueous solution. Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models were used to describe the adsorption isotherms. The adsorption data were best fitted with Freundlich model. The experimental data of the two adsorbate-adsorbent systems fitted very well with the pseudo-second order kinetic model with r2 values of 0.999 respectively. Adsorption thermodynamic parameters were also estimated. The results revealed that the adsorption of 4-nitrophenol onto both adsorbents were exothermic processes and spontaneous for Jatropha curcas activated carbon but non spontaneous for activated kaolinitic clay.

  5. Kinetics and thermodynamics of sorption of 4-nitrophenol on activated kaolinitic clay and jatropha curcas activated carbon from aqueous solution

    International Nuclear Information System (INIS)

    Azeez, S.O.; Adekola, F.A.

    2016-01-01

    Adsorption behaviour of 4-nitrophenol (4-NP) on activated kaolinitic clay and Jatropha curcas activated carbon was investigated. The kaolinitic clay and Jatropha curcas were activated with 1 M HNO/sub 3/ and 0.5 M NaOH respectively and were characterized by XRF, XRD, BET, SEM and FTIR techniques. The effects of processing parameters, such as initial 4-NP concentration, temperature, pH, contact time and adsorbent dosage on the adsorption process were investigated. The results obtained showed that Jatropha curcas activated carbon exhibited higher performance than activated kaolinitic clay for the removal of 4-nitrophenol from aqueous solution. Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models were used to describe the adsorption isotherms. The adsorption data were best fitted with Freundlich model. The experimental data of the two adsorbate-adsorbent systems fitted very well with the pseudosecond order kinetic model with r2 values of 0.999 respectively. Adsorption thermodynamic parameters were also estimated. The results revealed that the adsorption of 4-nitrophenol onto both adsorbents were exothermic processes and spontaneous for Jatropha curcas activated carbon but non spontaneous for activated kaolinitic clay. (author)

  6. Kinetics, equilibrium and thermodynamic studies on biosorption of Ag(I) from aqueous solution by macrofungus Pleurotus platypus.

    Science.gov (United States)

    Das, Devlina; Das, Nilanjana; Mathew, Lazar

    2010-12-15

    Reports are available on silver binding capacity of some microorganisms. However, reports on the equilibrium studies on biosorption of silver by macrofungi are seldom known. The present study was carried out in a batch system using dead biomass of macrofungus Pleurotus platypus for the sorption of Ag(I). P. platypus exhibited the highest silver uptake of 46.7 mg g(-1) of biomass at pH 6.0 in the presence of 200 mg L(-1) Ag(I) at 20°C. Kinetic studies based on fractional power, zero order, first order, pseudo-first order, Elovich, second order and pseudo-second order rate expressions have been carried out. The results showed a very good compliance with the pseudo-first order model. The experimental data were analyzed using two parameter isotherms (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Halsey), three parameter isotherms (Redlich-Peterson, Sips, Khan, Koble-Corrigan, Hill, Toth, Radke-Prausmitz, Jossens, Langmuir-Freundlich), four parameter isotherms (Weber-van Vliet, Fritz-Schlunder, Baudu) and five parameter isotherm (Fritz-Schlunder). Thermodynamic parameters of the biosorption (ΔG, ΔH and ΔS) were also determined. The present study confirmed that macrofungus P. platypus may be used as a cost effective efficient biosorbent for the removal of Ag(I) ions from aqueous solution. Copyright © 2010 Elsevier B.V. All rights reserved.

  7. Kinetics, isothermal and thermodynamics studies of electrocoagulation removal of basic dye rhodamine B from aqueous solution using steel electrodes

    Science.gov (United States)

    Adeogun, Abideen Idowu; Balakrishnan, Ramesh Babu

    2017-07-01

    Electrocoagulation was used for the removal of basic dye rhodamine B from aqueous solution, and the process was carried out in a batch electrochemical cell with steel electrodes in monopolar connection. The effects of some important parameters such as current density, pH, temperature and initial dye concentration, on the process, were investigated. Equilibrium was attained after 10 min at 30 °C. Pseudo-first-order, pseudo-second-order, Elovich and Avrami kinetic models were used to test the experimental data in order to elucidate the kinetic adsorption process; pseudo-first-order and Avrami models best fitted the data. Experimental data were analysed using six model equations: Langmuir, Freudlinch, Redlich-Peterson, Temkin, Dubinin-Radushkevich and Sips isotherms and it was found that the data fitted well with Sips isotherm model. The study showed that the process depends on current density, temperature, pH and initial dye concentration. The calculated thermodynamics parameters (Δ G°, Δ H° and Δ S°) indicated that the process is spontaneous and endothermic in nature.

  8. The thermodynamic characteristics of the reaction between vanadium(5) and hydrogen peroxide in concentrated solutions of perchloric acid

    International Nuclear Information System (INIS)

    Vorob'ev, P.N.; Dmitrieva, N.G.; Poteshonkova, T.A.

    2001-01-01

    Stability constants of vanadium(5) complex with hydrogen peroxide and enthalpy of vanadium(5) complexing with hydrogen peroxide are determined at acidity of solution c(H + ) = 5.00 mol/l, temperature T = 298.15 K and values of ionic force: I = 5, 6 and 7. Standard thermodynamic characteristics of vanadium(5) peroxide complex formation were calculated. At zeroth ionic force the value of complexing enthalpy Δ r H 298.15 deg is equal to -48.59 ± 0.33 kJ/mol, standard enthalpy of peroxide vanadium(5) complex formation Δ f H 298.15 deg is equal to -895.49 ± 1.51 kJ/mol; Δ r G 298.15 deg = -36.51 kJ/mol, Δ r S 298.15 deg -40.51 J/(mol K). As it is shown by calculations, standard change in entropy of the reaction has a minus sign, that is unique to complexation with neutral ligand [ru

  9. Sorption performance of activated nkaliki clay in removing chromium (vi) ion from aqueous solution: kinetics, isotherm, and thermodynamic studies

    International Nuclear Information System (INIS)

    Ajemba, R.O.; Ugonabo, V.I.; Okafor, V.N.

    2017-01-01

    Bentonite from Nkaliki was modified by acid activation using different concentrations of sulphuric acid. The physicochemical properties of the raw and modified samples were analyzed. The sorption performance of the modified and raw bentonite was studied in the removal of chromium (VI) ion from aqueous solution. Effect of key process parameters on the adsorption process was studied. Results of the physicochemical analyses showed that the acid activation altered the structural arrangements of the bentonite. The surface area and adsorption capacity increased from 37.6m/sup 2//g to 74m/sup 2//g and 45 to 98%, respectively, after activating with 6mol/l of H/sub 2/SO/sub 4/. The chromium (VI) ion adsorption increased with increase in process parameters studied. The kinetics analysis of the adsorption data follows the pseudo second-order kinetics, while equilibrium analysis conformed to the Langmuir isotherm. The thermodynamic parameters revealed that adsorption process is spontaneous and endothermic. This study shows that modified Nkaliki bentonite could be used for wastewater treatment. (author)

  10. The removal of Tartrazine dye by modified Alumina with sodium dodecyl sulfate from aqueous solutions: equilibrium and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    A. Parchebaf Jadid

    2017-11-01

    Full Text Available Edible colors are materials which in the case of adding to food and drinks cause transferring color to them. Most of these colors are not acceptable in terms of applying in human food and underlies various diseases like gastrointestinal disorders, renal, liver and blood toxicity. The goal of this study was investigating the efficiency of improved alumina by sodium dodecyl sulfate (SDS in eliminating Tartrazine from aqueous environments. In this research, the impact of effective parameters such as initial concentration of Tartrazine, time, pH, alumina dose and SDS value were studied in order to approach an optimal condition for eliminating the color. Also, absorption behavior was evaluated by Freundlich and Langmuir isotherms. The highest efficiency of Tartrazine elimination in the solution resulted in optimal pH of 2, the amount of adsorbent 1.5 g/L, 16 min duration and value 0.04 SDS g/l which was obtained for dye concentration 5 mg/L about 94.13%. Also, results suggested that Tartrazine absorption follows Langmuir isotherm (R2 = 0.9867. Obtained results from thermodynamic studies such as Gibbs free energy (-5.728 Kj/mol and enthalpy (-85.86 Kj/mol and entropy (-271.102 J/mol.K also suggested that the absorption process was exothermic. The results of this research suggested that improved alumina by sodium dodecyl sulfate had a relative good capability in Tartrazine elimination from aqueous environments. Thus

  11. Study of the coupling of geochemical models based on thermodynamic equilibrium with models of component transfer as solutions in porous media or fractures

    International Nuclear Information System (INIS)

    Coudrain-Ribstein, A.

    1985-01-01

    This study is a contribution of analyses possibilities of modelling the transfer of components in the underground taking into account complexes geochemical phenomena. In the first part, the aim and the methodology of existing codes are presented. The transfer codes describe with a great precision the physical phenomena of transport but they are based on a very simple conceptualisation of the geochemical phenomena of retention by the rock. The geochemical models are interested by a stable unity of volume. They allow to compute the equilibrium distribution of the components between the chemical species of the solution, and the solid and gaseous phases. They use important thermodynamic data bases corresponding to each possible reaction. To sum up the situation about the geochemical codes in Europe and United States, a list of about thirty codes describe their method and potentialities. The mathematical analysis of the different methods used in both types of codes is presented. Then, the principles of a modelisation associating the potentialities of the transport codes and the geochemical codes are discussed. It is not possible to think of a simple coupling. A general code must be established on the bases of the existing codes but also on new concepts and under new constraints. In such studies one must always deal with the problem of the reactions kinetics. When the velocity of the reactions is big enough versus the velocity of transport processes, the assumption of local geochemical equilibrium can be retained. A general code would be very cumbersome, expensive and difficult to use. The results would be difficult to analyse and exploit. On the other hand, for each case study, a detailed analysis can point out many computing simplifications without simplifying the concepts [fr

  12. A fluorescent chemosensor for Zn(II). Exciplex formation in solution and the solid state.

    Science.gov (United States)

    Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Lima, Joao C; Lodeiro, Carlos; Melo, Maria J; de Melo, J Seixas; Parola, Antonio Jorge; Pina, Fernando; Pina, Joao; Valtancoli, Barbara

    2004-07-21

    The macrocyclic phenanthrolinophane 2,9-[2,5,8-triaza-5-(N-anthracene-9-methylamino)ethyl]-[9]-1,10-phenanthrolinophane (L) bearing a pendant arm containing a coordinating amine and an anthracene group forms stable complexes with Zn(II), Cd(II) and Hg(II) in solution. Stability constants of these complexes were determined in 0.10 mol dm(-3) NMe(4)Cl H(2)O-MeCN (1:1, v/v) solution at 298.1 +/- 0.1 K by means of potentiometric (pH metric) titration. The fluorescence emission properties of these complexes were studied in this solvent. For the Zn(II) complex, steady-state and time-resolved fluorescence studies were performed in ethanol solution and in the solid state. In solution, intramolecular pi-stacking interaction between phenanthroline and anthracene in the ground state and exciplex emission in the excited state were observed. From the temperature dependence of the photostationary ratio (I(Exc)/I(M)), the activation energy for the exciplex formation (E(a)) and the binding energy of the exciplex (-DeltaH) were determined. The crystal structure of the [ZnLBr](ClO(4)).H(2)O compound was resolved, showing that in the solid state both intra- and inter-molecular pi-stacking interactions are present. Such interactions were also evidenced by UV-vis absorption and emission spectra in the solid state. The absorption spectrum of a thin film of the solid complex is red-shifted compared with the solution spectra, whereas its emission spectrum reveals the unique featureless exciplex band, blue shifted compared with the solution. In conjunction with X-ray data the solid-state data was interpreted as being due to a new exciplex where no pi-stacking (full overlap of the pi-electron cloud of the two chromophores - anthracene and phenanthroline) is observed. L is a fluorescent chemosensor able to signal Zn(II) in presence of Cd(II) and Hg(II), since the last two metal ions do not give rise either to the formation of pi-stacking complexes or to exciplex emission in solution.

  13. Thermodynamics of Highly Supersaturated Aqueous Solutions of Poorly Water-Soluble Drugs-Impact of a Second Drug on the Solution Phase Behavior and Implications for Combination Products.

    Science.gov (United States)

    Trasi, Niraj S; Taylor, Lynne S

    2015-08-01

    There is increasing interest in formulating combination products that contain two or more drugs. Furthermore, it is also common for different drug products to be taken simultaneously. This raises the possibility of interactions between different drugs that may impact formulation performance. For poorly water-soluble compounds, the supersaturation behavior may be a critical factor in determining the extent of oral absorption. The goal of the current study was to evaluate the maximum achievable supersaturation for several poorly water-soluble compounds alone, and in combination. Model compounds included ritonavir, lopinavir, paclitaxel, felodipine, and diclofenac. The "amorphous solubility" for the pure drugs was determined using different techniques and the change in this solubility was then measured in the presence of differing amounts of a second drug. The results showed that "amorphous solubility" of each component in aqueous solution is substantially decreased by the second component, as long as the two drugs are miscible in the amorphous state. A simple thermodynamic model could be used to predict the changes in solubility as a function of composition. This information is of great value when developing co-amorphous or other supersaturating formulations and should contribute to a broader understanding of drug-drug physicochemical interactions in in vitro assays as well as in the gastrointestinal tract. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  14. Forced intrusion of water and aqueous solutions in microporous materials: from fundamental thermodynamics to energy storage devices.

    Science.gov (United States)

    Fraux, Guillaume; Coudert, François-Xavier; Boutin, Anne; Fuchs, Alain H

    2017-12-07

    We review the high pressure forced intrusion studies of water in hydrophobic microporous materials such as zeolites and MOFs, a field of research that has emerged some 15 years ago and is now very active. Many of these studies are aimed at investigating the possibility of using these systems as energy storage devices. A series of all-silica zeolites (zeosil) frameworks were found suitable for reversible energy storage because of their stability with respect to hydrolysis after several water intrusion-extrusion cycles. Several microporous hydrophobic zeolite imidazolate frameworks (ZIFs) also happen to be quite stable and resistant towards hydrolysis and thus seem very promising for energy storage applications. Replacing pure water by electrolyte aqueous solutions enables to increase the stored energy by a factor close to 3, on account of the high pressure shift of the intrusion transition. In addition to the fact that aqueous solutions and microporous silica materials are environmental friendly, these systems are thus becoming increasingly interesting for the design of new energy storage devices. This review also addresses the theoretical approaches and molecular simulations performed in order to better understand the experimental behavior of nano-confined water. Molecular simulation studies showed that water condensation takes place through a genuine first-order phase transition, provided that the interconnected pores structure is 3-dimensional and sufficiently open. In an extreme confinement situations such as in ferrierite zeosil, condensation seem to take place through a continuous supercritical crossing from a diluted to a dense fluid, on account of the fact that the first-order transition line is shifted to higher pressure, and the confined water critical point is correlatively shifted to lower temperature. These molecular simulation studies suggest that the most important features of the intrusion/extrusion process can be understood in terms of equilibrium

  15. Adsorption of ammonium ion by coconut shell-activated carbon from aqueous solution: kinetic, isotherm, and thermodynamic studies.

    Science.gov (United States)

    Boopathy, Ramasamy; Karthikeyan, Sekar; Mandal, Asit Baran; Sekaran, Ganesan

    2013-01-01

    Ammonium ions are one of the most encountered nitrogen species in polluted water bodies. High level of ammonium ion in aqueous solution imparts unpleasant taste and odor problems, which can interfere with the life of aquatics and human population when discharged. Many chemical methods are developed and being used for removal of ammonium ion from aqueous solution. Among various techniques, adsorption was found to be the most feasible and environmentally friendly with the use of natural-activated adsorbents. Hence, in this study, coconut shell-activated carbon (CSAC) was prepared and used for the removal of ammonium ion by adsorption techniques. Ammonium chloride (analytical grade) was purchased from Merck Chemicals for adsorption studies. The CSAC was used to adsorb ammonium ions under stirring at 100 rpm, using orbital shaker in batch experiments. The concentration of ammonium ion was estimated by ammonia distillate, using a Buchi distillation unit. The influence of process parameters such as pH, temperature, and contact time was studied for adsorption of ammonium ion, and kinetic, isotherm models were validated to understand the mechanism of adsorption of ammonium ion by CSAC. Thermodynamic properties such as ∆G, ∆H, and ∆S were determined for the ammonium adsorption, using van't Hoff equation. Further, the adsorption of ammonium ion was confirmed through instrumental analyses such as SEM, XRD, and FTIR. The optimum conditions for the effective adsorption of ammonium ion onto CSAC were found to be pH 9.0, temperature 283 K, and contact time 120 min. The experimental data was best followed by pseudosecond order equation, and the adsorption isotherm model obeyed the Freundlich isotherm. This explains the ammonium ion adsorption onto CSAC which was a multilayer adsorption with intraparticle diffusion. Negative enthalpy confirmed that this adsorption process was exothermic. The instrumental analyses confirmed the adsorption of ammonium ion onto CSAC.

  16. Phosphorus removal from aqueous solution in parent and aluminum-modified eggshells: thermodynamics and kinetics, adsorption mechanism, and diffusion process.

    Science.gov (United States)

    Guo, Ziyan; Li, Jiuhai; Guo, Zhaobing; Guo, Qingjun; Zhu, Bin

    2017-06-01

    Parent and aluminum-modified eggshells were prepared and characterized with X-ray diffraction, specific surface area measurements, infrared spectroscopy, zeta potential, and scanning electron microscope, respectively. Besides, phosphorus adsorptions in these two eggshells at different temperatures and solution pH were carried out to study adsorption thermodynamics and kinetics as well as the mechanisms of phosphorus adsorption and diffusion. The results indicated that high temperature was favorable for phosphorus adsorption in parent and aluminum-modified eggshells. Alkaline solution prompted phosphorus adsorption in parent eggshell, while the maximum adsorption amount was achievable at pH 4 in aluminum-modified eggshell. Adsorption isotherms of phosphorus in these eggshells could be well described by Langmuir and Freundlich models. Phosphorus adsorption amounts in aluminum-modified eggshell were markedly higher compared to those in parent eggshell. Adsorption heat indicated that phosphorus adsorption in parent eggshell was a typically physical adsorption process, while chemical adsorption mechanism of ion exchange between phosphorus and hydroxyl groups on the surface of eggshells was dominated in aluminum-modified eggshell. The time-resolved uptake curves showed phosphorus adsorption in aluminum-modified eggshell was significantly faster than that in parent eggshell. Moreover, there existed two clear steps in time-resolved uptake curves of phosphorus in parent eggshell. Based on pseudo-second order kinetic model and intraparticle diffusion model, we inferred more than one process affected phosphorus adsorption. The first process was the diffusion of phosphorus through water to external surface and the opening of pore channel in the eggshells, and the second process was mainly related to intraparticle diffusion.

  17. Giant asymmetry of separation and homogenization processes in solid 3He-4He solutions

    International Nuclear Information System (INIS)

    Grigor'ev, V.N.; Majdanov, V.A.; Penzev, A.A.; Polev, A.V.; Rubets, S.P.; Rudavskij, Eh.Ya.; Rybalko, A.S.; Syrnikov, E.V.

    2005-01-01

    The kinetics of the processes of separation and homogenization of solid 3 He- 4 He solutions is compared by using the precision barometry. The experiments were made with the initial specimens of three types: weak 3 He- 4 He and 4 He- 3 He solutions and concentrated 3 He- 4 He ones. It is found that the homogenization rate at the initial stage may be more than 500 times higher that the rate of separation. This is the case for all types of the solutions studied. The appreciable rate of phase separation in the concentrated solutions where, according to the modern concepts, impurity atoms in quantum crystals should be localized, suggests that in such conditions there is a new unknown mechanism of mass-transfer, while the fast homogenization points to a nondiffusion nature of the process

  18. Phase separation phenomena in solutions of poly(2,6-dimethyl-1,4-phenylene oxide). IV. Thermodynamic parameters for solutions in a series of homologous solvents: Toluene to hexylbenzene

    NARCIS (Netherlands)

    Koenhen, D.M.; Bakker, A.; Broens, L.; van den Berg, J.W.A.; Smolders, C.A.

    1984-01-01

    Melting-point curves for solutions of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) in a series of homologous solvents (toluene to n-hexylbenzene) have been obtained from visual and differential scanning calorimetry measurements. The measured melting points were used to calculate thermodynamic

  19. The investigation of solid solutions thin interlayers in CdS/CdTe film heterosystems

    International Nuclear Information System (INIS)

    Khrypunov, G.; Boyko, B.; Chernykh, O.

    1999-01-01

    The photo-response spectral dependence of ITO/CdTe/Au/Cu and ITO/CdS/CdTe/Au/Cu film heterosystems were investigated. At illuminations ITO/CdS/CdTe/Au/Cu heterosystems on ITO side a photo-response maximum was observed for photon absorption with a wavelength of 0.87 μm that is stipulated by formation of CdS x Te 1-x solid solutions interlayer with band gap width less than in CdTe layer. By use optical measurement transmittance spectra was selected a spectral photosensitivity interval appropriate to the contribution of non-equilibrium charge carriers generated in solid solutions interlayer by photon absorption with energy less than CdTe film band gap

  20. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

    International Nuclear Information System (INIS)

    Zhang, Yanwen; Wang, Lumin; Caro, Alfredo; Weber, William J.; Univ. of Tennessee, Knoxville, TN

    2015-01-01

    A long-standing objective in materials research is to understand how energy is dissipated in both the electronic and atomic subsystems in irradiated materials, and how related non-equilibrium processes may affect defect dynamics and microstructure evolution. Here we show that alloy complexity in concentrated solid solution alloys having both an increasing number of principal elements and altered concentrations of specific elements can lead to substantial reduction in the electron mean free path and thermal conductivity, which has a significant impact on energy dissipation and consequentially on defect evolution during ion irradiation. Enhanced radiation resistance with increasing complexity from pure nickel to binary and to more complex quaternary solid solutions is observed under ion irradiation up to an average damage level of 1 displacement per atom. Understanding how materials properties can be tailored by alloy complexity and their influence on defect dynamics may pave the way for new principles for the design of radiation tolerant structural alloys

  1. Influence of chemical heterogeneity of solid solutions on brittleness in chromium steels

    International Nuclear Information System (INIS)

    Madyanov, S.A.; Sedov, V.K.; Apaev, B.A.

    1985-01-01

    The role of chemical heterogeneity of solid solutions in formation of mechanical properties of Kh09, Kh15, Kh20, Kh19N2G5T chromium steels has been investigated. It is established that besides the known regioA of chemical heterogeneity in the vicinity of 475 deg C exists a high-temperature region (1000-1050 deg C), where maximum heteroge=- neity of chromium distribution in solid solution, is observed. Both types of chemical heterogeneity cause essential hardening of alloys, which becomes apparent in abrupt change of capability to microplastic deformation The mechanism of occurrence of the given temper brittleness consists in carbon diffusion into microvolunes enriched in carbide-forming elements

  2. Formation of soft magnetic high entropy amorphous alloys composites containing in situ solid solution phase

    Science.gov (United States)

    Wei, Ran; Sun, Huan; Chen, Chen; Tao, Juan; Li, Fushan

    2018-03-01

    Fe-Co-Ni-Si-B high entropy amorphous alloys composites (HEAACs), which containing high entropy solid solution phase in amorphous matrix, show good soft magnetic properties and bending ductility even in optimal annealed state, were successfully developed by melt spinning method. The crystallization phase of the HEAACs is solid solution phase with body centered cubic (BCC) structure instead of brittle intermetallic phase. In addition, the BCC phase can transformed into face centered cubic (FCC) phase with temperature rise. Accordingly, Fe-Co-Ni-Si-B high entropy alloys (HEAs) with FCC structure and a small amount of BCC phase was prepared by copper mold casting method. The HEAs exhibit high yield strength (about 1200 MPa) and good plastic strain (about 18%). Meanwhile, soft magnetic characteristics of the HEAs are largely reserved from HEAACs. This work provides a new strategy to overcome the annealing induced brittleness of amorphous alloys and design new advanced materials with excellent comprehensive properties.

  3. Microstructure and Mechanical Strengths of Metastable FCC Solid Solutions in Al-Ce-Fe System

    OpenAIRE

    A., Inoue; H., Yamaguchi; M., Kikuchi; T., Masumoto; Institute for Materials Research; Institute for Materials Research; Institute for Materials Research; Institute for Materials Research

    1990-01-01

    A metastable fcc solid solution (SS) with high mechanical strengths and good bending ductility was found to be formed in rapidly solidified Al-Ce-Fe alloys containing the solute elements below about 6 at%. The SS consists of equiaxed grains with a size of about 2μm and contains a high density of internal defects. The highest hardness (H_v) and tensile fracture strengtn (σ_f) are 440 and 860 MPa in the as-quenched state and remain almost unchanged up to about 600 K for 1 h, though fine compoun...

  4. Photoelectrochemical properties of CdSesub(x)Tesub(1-x) semiconducting solid solutions

    International Nuclear Information System (INIS)

    Kolbasov, G.Ya.; Karpov, I.I.; Pavelets, A.M.; Khanat, L.N.

    1985-01-01

    Photoelectrochemical properties of polycrystalline films of solid solutions CdSesub(x)Tesub(1-x) at x=0.5-0.8 are studied. Films from 5 to 30 μm thickness had hexagonal or mixed cubic and hexogonal structures depending on the compositions. All compositions had the electron type of conductivity. Alkali solutions of Na 2 S and S were used as electrolyte. Polarization characteristics of the CdSesub(0.5)Tesub(0.5) photoelectrode, curves of spectral dependence of photo electrochemical current and of the changes of photo-e.m.f. on electrode potential are plotted

  5. Phase transitions in solid Kr-CH4 solutions and rotational excitations in phase II

    International Nuclear Information System (INIS)

    Bagatskii, M.I.; Mashchenko, D.A.; Dudkin, V.V.

    2007-01-01

    The heat capacity C p of solid Kr-n CH 4 solutions with the CH 4 concentrations n=0.82, 0.86, 0.90 as well as solutions with n=0.90, 0.95 doped with 0.002 O 2 impurity has been investigated under equilibrium vapor pressure over the internal 1-24 K. The (T,n)-phase diagram was refined and the region of two-phase states was determined for Kr-n CH 4 solid solutions. The contribution of the rotational subsystem, C r ot, to the heat capacity of the solutions has been separated. Analysis of C r ot(T) at T 1 and E 2 between the tunnel levels of the A-, T- and A-, E--nuclear-spin species of CH 4 molecules in the orientationally ordered subsystem, and to determine the effective energy gaps E 1 between lowest levels of the A- and T- species. The relations τ(n) and E 1 (n) stem from changes of the effective potential field caused as the replacement of CH 4 molecules by Kr atoms at sites of the ordered sublattices. The effective gaps E L between a group of tunnel levels of the ground-state liberation state and the nearest group of excited levels of the liberation state of the ordered CH 4 molecules in the solutions with n=0.90 (E L =52 K) and 0.95 (E L =55 K) has been estimated

  6. Tensometrical properties of volumetric crystals of germanium-silicon solid solutions irradiated by fast electrons

    International Nuclear Information System (INIS)

    Abbasov, Sh.M.

    2002-01-01

    Full Text: In the present work the tensometrical properties of Ge1-xSix solid solution monocrystal contended of up to 15 at. % Si were investigated. The radiation-proof strain gauges of researched crystals were made. For this purpose the site was cutted out from a sample, perpendicularly or in parallel of a crystal axes. After polishing the samples had thickness of 30-40 microns, and length of 2 mm

  7. First-principles investigations of solid solution strengthening in Al alloys

    OpenAIRE

    Ma, Duancheng

    2012-01-01

    Any material properties, in principle, can be reproduced or predicted by performing firstprinciples calculations. Nowadays, however, we are dealing with complex alloy compositions and processes. The complexities cannot be fully described by first-principles, because of the limited computational power. The primary objective of this study is to investigate an important engineering problem, solid solution strengthening, in a simplified manner. The simplified scheme should allow fast and reliable...

  8. Studying the Super-cooled Solid Solution Breakdown of V-1341 Aluminum Alloy

    Directory of Open Access Journals (Sweden)

    Yu. A. Puchkov

    2017-01-01

    Full Text Available Deformable alloys of the Al-Mg-Si system are widely used in aviation industry, rocket engineering, shipbuilding, as well as on railway and highway transport. These alloys are characterized by high stamping ability, weld-ability, and machinability with a comparatively high strength and corrosion resistance in a heat-strengthened state. A promising alloy of the Al-Mg-Si system with increased structural strength and manufacturability is on par with foreign analogues in properties is the V-1341 alloy [1, 2].The properties of heat-treatable aluminum alloys strongly depend on the cooling rate of the product during quenching [3-12], which determines the structure and level of residual stresses. Decrease in structural strength, tendency to pitting and inter-crystalline corrosion with slow cooling from the quenching temperature is caused by formation of coarse unequiaxed precipitate, precipitates-free zones, and also by decreasing proportion of inclusions of the strengthening phase [3-12].Thus, the relevant task is to study the effect of isothermal quenching modes on the structure of deformable V-1341 aluminum alloy thermally hardened.The paper studies the impact of isothermal time in quenching on the composition and morphology of breakdown products of the V-1341 alloy solid solution. It is shown that at isothermal time under the solid solution breakdown, at first on the dispersoid surface and then in the solid solution are formed and grow large needle-like crystals of the β'-phase which are structural concentrators of stresses. An increasing isothermal time leads to decreasing solid solution super-saturation by doping elements and vacancies. This leads to a decrease in the fraction of the coherent finely dispersed hardening β '' phase, and also to an increase in the width of the precipitates-free zone.

  9. Long-term behavior of refractory thorium-plutonium dioxide solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Claparede, Laurent, E-mail: laurent.claparede@umontpellier.fr [ICSM, UMR 5257 CNRS/CEA/Univ. Montpellier/ENSCM, Site de Marcoule, Bât. 426, BP 17171, 30207 Bagnols/Cèze (France); Guigue, Mireille [CEA, Nuclear Energy Division, RadioChemistry & Processes Department, BP 17171, 30207 Bagnols/Cèze (France); Jouan, Gauthier [CEA, Nuclear Energy Division, DTEC Department, BP 17171, 30207 Bagnols/Cèze (France); Nadah, Nassima [CEA, Nuclear Energy Division, RadioChemistry & Processes Department, BP 17171, 30207 Bagnols/Cèze (France); Dacheux, Nicolas [ICSM, UMR 5257 CNRS/CEA/Univ. Montpellier/ENSCM, Site de Marcoule, Bât. 426, BP 17171, 30207 Bagnols/Cèze (France); Moisy, Philippe [CEA, Nuclear Energy Division, RadioChemistry & Processes Department, BP 17171, 30207 Bagnols/Cèze (France)

    2017-01-15

    The long-term behavior of Th{sub 0.87}Pu{sub 0.13}O{sub 2} was examined in nitric acid concentrations. The normalized dissolution rates after 3380 days, range from (1.4 ± 0.2) × 10{sup −6} g m{sup −2} d{sup −1} in 5 M HNO{sub 3} down to (3.2 ± 0.4) × 10{sup −8} g m{sup −2} d{sup −1} in 10{sup −3} M HNO{sub 3}, which confirms the high chemical durability of this solid solution. The amounts of plutonium measured in solution lead to 0.9% and 2.1% of dissolved solid in 1 M and 5 M HNO{sub 3}, respectively. In such conditions, the time required to reach the full dissolution of the material varies from 430 years (5 M HNO{sub 3}) to 18,000 years (10{sup −3} M HNO{sub 3}). Moreover, the partial order related to the proton activity (n = 0.45 ± 0.03) suggests that the dissolution is mainly driven by surface reactions occurring at the solid/liquid interface. The characterization of the leached samples by SEM shows small microstructural modifications (i.e. detachment of crystallites) and the absence of neoformed phase while from PXRD, the unit cell parameter and crystallite size are not significantly affected. - Highlights: • Leaching tests of Th{sub 0.87}Pu{sub 0.13}O{sub 2} were performed for 9 years in several nitric acid solutions. • The high chemical durability of thorium-plutonium oxide solid solutions was confirmed. • The solubility of plutonium(IV) was not controlled by the precipitation of plutonium tetrahydroxide in these experiments.

  10. Mesoporous yttria-zirconia and metal-yttria-zirconia solid solutions for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Mamak, M.; Coombs, N.; Ozin, G. [Toronto Univ., ON (Canada). Dept. of Chemistry

    2000-02-03

    A new class of binary mesoporous yttria-zirconia (YZ) and ternary mesoporous metal-YZ materials (M = electroactive Ni/Pt) is presented here that displays the highest surface area of any known form of yttria-stabilized zirconia. These mesoporous materials form as solid solutions and retain their structural integrity to 800 C, which bodes well for their possible utilization in fuel cells. (orig.)

  11. Structural transformation in mechanosynthesized bcc Fe-Al-Si(Ge) solid solutions during heating

    International Nuclear Information System (INIS)

    Kubalova, L.M.; Sviridov, I.A.; Vasilyeva, O.Ya.; Fadeeva, V.I.

    2007-01-01

    X-ray diffractometry and Moessbauer spectroscopy study of Fe 50 Al 25 Si 25 and Fe 50 Al 25 Ge 25 alloys obtained by mechanical alloying (MA) of elementary powders was carried out. Phase transformation during heating of synthesized products was studied using differential scanning calorimetry (DSC). After 2.5 h of MA monophase alloys containing bcc Fe(Al, Ge) solid solutions Fe(Al, Si) are formed. Fe(Al, Si) is partially ordered B2 type and Fe(Al, Ge) is completely disordered. DSC curves of synthesized alloys displayed the presence of exothermal peaks caused by phase transformation. The metastable Fe(Al, Si) solid solution transformed into FeAl 1-x Si x (B2) and FeSi 1-x Al x (B20) equilibrium phases. The Fe(Al, Ge) solid solution transformed into equilibrium phases through intermediate stage of Fe 6 Ge 3 Al 2 metastable phase formation. The Fe 6 Ge 3 Al 2 phase dissociated into three equilibrium phases: FeAl 1-x Ge x (B2), χ-Fe 6 Ge 5 and η-Fe 13 (Ge, Al) 8 (B8 2 ). The structure of Fe 6 Ge 3 Al 2 was calculated by Rietveld method, the distribution of Al and Ge in the elementary cell and its parameters were calculated. Moessbauer study showed that Fe(Al, Si) and Fe(Al, Ge) solid solutions are paramagnetic. In the equilibrium state the alloy containing Si is also paramagnetic while the alloy with Ge showed ferromagnetic properties

  12. Electron paramagnetic resonance response and magnetic interactions in ordered solid solutions of lithium nickel oxides

    Energy Technology Data Exchange (ETDEWEB)

    Azzoni, C.B. [Istituto Nazionale di Fisica della Materia, Dipartimento di Fisica ' Alessandro Volta' , Universita di Pavia, Pavia (Italy); Paleari, A. [Istituto Nazionale di Fisica della Materia, Dipartimento di Fisica, Universita di Milano, Milan (Italy); Massarotti, V.; Capsoni, D. [Dipartimento di Chimica-Fisica, Universita di Pavia, Pavia (Italy)

    1996-09-23

    EPR data of ordered solid solutions of lithium nickel oxides are reported as a function of the lithium content. The features of the signal and the EPR centre density are analysed by a model of dynamical trapping of holes in [(Ni{sup 2+}-O-Ni{sup 2+})-h{sup +}] complexes. The possible origin of the interactions responsible for the magnetic ordering and some features of the transport properties are also discussed. (author)

  13. Contribution to the study of the structure of silver krypton solid solutions

    International Nuclear Information System (INIS)

    Levy, V.; Tullairet, J.; Delaplace, J.; Antolin-Baudier, J.; Adda, Y.

    1964-01-01

    The silver-krypton solid solutions formed by electrical discharge have been studied by X-rays, electrical resistivity and electronic transmission microscopy. The crystalline parameter and residual resistivity measurements have shown that the krypton atom behaves very differently to those of other elements of the periodic classification when dissolved in silver. The recovery of the crystalline parameter and of the electrical resistivity has been studied as a function of temperature. (authors) [fr

  14. Small interstitial clusters as opposite defect recombinators in decomposing solid solutions under irradiation

    International Nuclear Information System (INIS)

    Orlov, A.N.; Trushin, Yu.V.

    1988-01-01

    An attempt was made to make allowance for the role of binary and ternary interstitials in the kinetics of radiation point defects both in the presence and in the absence of coherent preseparation. It is shown that in solid solutions, decomposing under irradiation, recombination with binary and ternary interstitials proceeds more quickly than directly, and this difference is more pronounced (from 2 up to 20 time growth) due to defect flow for preseparation at the stage of coherent preseparation formation

  15. Solid solution inhomogeneity in DC-cast AlMn(Fe,Si) ingots

    International Nuclear Information System (INIS)

    Lakner, J.; Kovacs-Csetenyi, E.; Lal, K.

    1990-01-01

    The aim of this work was to characterize the structure in cast state of the AlMn1 alloy containing different Fe and Si concentration. The casting parameters were intended to keep constant and the effect of impurities was studied. The inhomogeneity along the diameter of cast billet was characterized by the dendrite arm spacing and by the solid solution content. To explain the results the model developed for binary AlFe and AlMn alloys was applied

  16. Decomposition of supersaturated solid solutions Mg-Ho and Mg-Gd

    International Nuclear Information System (INIS)

    Sukhanov, V.D.; Dobromyslov, A.V.; Rokhlin, L.L.; Dobatkina, T.V.

    2002-01-01

    Methods of electron microscopy and X-ray diffraction analysis are applied to study ageing magnesium base alloys with holmium and gadolinium. It is shown that the precipitation of supersaturated Mg base solid solutions goes through several subsequent stages and is accompanied by a considerable precipitation hardening effect at the stage of metastable phase precipitation. The influence of aging time and temperature on precipitation kinetics is established [ru

  17. Photophysical processes study for poly (P-substituted styrenes) in solid films and in solutions

    International Nuclear Information System (INIS)

    Al-Hakeem, I.A.

    1985-01-01

    In this work, the absorption and emission spectra of poly (P-NN dimethyl amino styrene), poly (P-Fluoro Styrene), poly (P-CH2OCH3 styrene), poly (P-Methyl (styrene), poly(P-Tertiary butyl styrene) have been studied in solid films and solutions. The effect of added dimethylterph-thalate as a quencher to the fluorescence emission of the polymers used in this work were studied.(5 tabs., 39 figs., 60 refs.)

  18. Effect of the hydrophilic block length on the surface-active and micellar thermodynamic properties of oxyethylene-oxybutylene diblock copolymers in aqueous solution

    International Nuclear Information System (INIS)

    Khan, A.; Usman, M.; Siddiq, M.; Fatima, G.; Harrison, W.

    2009-01-01

    The effect of hydrophilic block length on the surface and micellar thermodynamic properties of aqueous solution of E/sub 40/B/sub 8/, E/sub 80/B/sub 8/ and E/sub 120/B/sub 8/ diblock copolymers, were studied by surface tension measurements over a wide concentration and temperature range; where E stands for an oxyethylene unit and B for an oxybutylene unit. Like conventional surfactants, two breaks (change in the slope) were observed in the surface tension vs logarithm of concentration curve for all the three copolymers. Surface tension measurements were used to estimate surface excess concentrations (r m), area per molecule at air/water interface a and thermodynamic parameters for all adsorption of the pre-micellar region in the temperature range 20 to 50 degree C. Likewise the critical micelle concentration, CMC and thermodynamic parameters for micellization were also calculated for the post-micellar solutions at all temperatures. For comparison the thermodynamic parameters of adsorption and micellization are discussed in detail. The impact of varying E-block length and temperature on all calculated parameters are also discussed. This study shows the importance of hydrophobic-hydrophilic-balance (HHB) of copolymers on various surface and micellar properties. (author)

  19. Hydrogen storage in TiCr1.2(FeV)x BCC solid solutions

    International Nuclear Information System (INIS)

    Santos, Sydney F.; Huot, Jacques

    2009-01-01

    The Ti-V-based BCC solid solutions have been considered attractive candidates for hydrogen storage due to their relatively large hydrogen absorbing capacities near room temperature. In spite of this, improvements of some issues should be achieved to allow the technological applications of these alloys. Higher reversible hydrogen storage capacity, decreasing the hysteresis of PCI curves, and decrease in the cost of the raw materials are needed. In the case of vanadium-rich BCC solid solutions, which usually have large hydrogen storage capacities, the search for raw materials with lower cost is mandatory since pure vanadium is quite expensive. Recently, the substitutions of vanadium in these alloys have been tried and some interesting results were achieved by replacing vanadium by commercial ferrovanadium (FeV) alloy. In the present work, this approach was also adopted and TiCr 1.2 (FeV) x alloy series was investigated. The XRD patterns showed the co-existence of a BCC solid solution and a C14 Laves phase in these alloys. SEM analysis showed the alloys consisted of dendritic microstructure and C14 colonies. The amount of C14 phase increases when the amount of (FeV) decreases in these alloys. Concerning the hydrogen storage, the best results were obtained for the TiCr 1.2 (FeV) 0.4 alloy, which achieved 2.79 mass% of hydrogen storage capacity and 1.36 mass% of reversible hydrogen storage capacity

  20. Vaporization study on vanadium-oxygen solid solution by mass spectrometric method

    International Nuclear Information System (INIS)

    Banchorndhevakul, W.; Matsui, Tsuneo; Naito, Keiji

    1986-01-01

    The vapor pressures over vanadium-oxygen solid solution (0.001 ≤ O/V ≤ 0.145) were measured by mass-spectrometric method in the temperature range of 1,855 ∼ 2,117 K. The main vapor species were observed to be V(g) and VO(g). The vapor pressure of V(g) is higher than that of VO(g) over the solid solutions with all O/V ratios except for O/V = 0.145. The vapor pressure of V(g) is nearly independent of O/V ratio. The vapor pressure of VO(g) decreases with decreasing O/V ratio. The oxygen partial pressure was calculated as a function of temperature and O/V ratio from the vapor pressures of V(g) and VO(g), from which the partial molar enthalpy and entropy of oxygen in the solid solution were determined. The partial molar enthalpy of oxygen was observed to be independent of composition, suggesting the presence of very weak interaction between interstitial oxygens. The compositional dependence of the partial molar entropy of oxygen can be explained by assuming the occupation of the octahedral site in bcc vanadium lattice by the interstitial oxygens. The excess partial molar entropy of oxygen was compared with the value derived from the sum of the contributions from the volume expansion, electronic heat capacity and vibrational terms. (author)