Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

Science.gov (United States)

Acree, William; Chickos, James S.

2017-03-01

The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

Solid–liquid phase equilibrium and dissolution properties of ethyl vanillin in pure solvents

International Nuclear Information System (INIS)

Wu, Hao; Wang, Jingkang; Zhou, Yanan; Guo, Nannan; Liu, Qi; Zong, Shuyi; Bao, Ying; Hao, Hongxun

2017-01-01

Highlights: • Solubility of ethyl vanillin in eight pure solvents were determined by a static analytical method. • The experimental solubility data of ethyl vanillin were correlated and analyzed by four thermodynamic models. • Dissolution thermodynamic properties of ethyl vanillin were calculated and discussed. - Abstract: The solubility of ethyl vanillin (EVA) in eight pure solvents were determined in different temperature ranges from (273.15 to 318.15) K by a static analytical method. In the temperature ranges investigated, it was found that the solubility of EVA in all the selected solvents increased with the rising of temperature. Furthermore, four thermodynamic models were used to correlate the experimental solubility data and the calculation results showed that selected models can be used to correlate the solubility data with satisfactory accuracy. Finally, the dissolution thermodynamic properties, including dissolution Gibbs energy, dissolution enthalpy and dissolution entropy of EVA in the eight selected solvents were calculated.

Formation enthalpy of alkali-borosilicate glass

International Nuclear Information System (INIS)

Borisova, N.V.; Ushakov, V.M.

1991-01-01

Temperature dependence of formation enthalpy of glass of the composition 0.0438Na 2 O-0.0385K 2 O-0.3394B 2 O 3 -0.5783SiO 2 was determined using the method of high-temperature colorimetry-dissolution, mixing and differential scanning calorimetry. The glass considered has liquation nature-two-vitrification ranges at 713 K and 817 K are detected. The brightening point is 922 K. The calculation of formation enthalpy using the method of partial heat capacities is made in the temperature range of 973-1473 K. Formation enthalpy does not depend on temperature in the temperature range of 298-1273 K

Direct determination of enthalpies of solid phase reactions by immersion method; Determination directe des enthalpies de reaction en phase solide par une methode de plongee

Energy Technology Data Exchange (ETDEWEB)

Roux, A; Richard, M; Eyraud, L; Stevanovic, M; Elston, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1967-07-01

It is not generally possible to measure the enthalpy change corresponding to solid phase reactions using the dynamic differential thermal analysis method because these reactions are usually too slow at the temperature of operation of present equipment. A ballistic differential thermal analysis apparatus has been developed which is based on an immersion-compensation method; it overcomes the difficulties previously encountered. This apparatus has been used after calibration for determining the enthalpies of formation of calcium and cadmium titanates. and also the Wigner energies of BeO, MgO and Al{sub 2}O{sub 3} samples irradiated at variable dose at a temperature of under 100 deg. C. (authors) [French] Il n'est generalement pas possible de mesurer la variation d'enthalpie correspondant aux reactions en phase solide par la methode d'analyse thermique differentielle dynamique. En effet, ces reactions sont le plus souvent trop lentes aux temperatures d'utilisation des dispositifs actuels. Un appareil d'analyse thermique differentielle balistique, base sur une methode de plongee avec compensation, a ete mis au point et permet de surmonter les difficultes precedentes. Apres etalonnages, cet appareil a ete utilise pour la determination des enthalpies de formation du titanate de calcium et du titanate de cadmium ainsi que pour celle des energies Wigner emmagasinees dans des echantillons de BeO, MgO et Al{sub 2}O{sub 3} irradies a une temperature inferieure a 100 deg. C et a differentes doses. (auteurs)

New experimental heat capacity and enthalpy of formation of lithium cobalt oxide

International Nuclear Information System (INIS)

Gotcu-Freis, Petronela; Cupid, Damian M.; Rohde, Magnus; Seifert, Hans J.

2015-01-01

Highlights: • LiCoO 2 heat capacity was measured in the temperature range (160 to 953) K using DSC. • Continuous/discontinuous methods were applied on different types of calorimeters. • Enthalpy increment of LiCoO 2 was determined using drop calorimetry at T = 974 K. • Enthalpies of formation were evaluated from oxide melt drop solution calorimetry. - Abstract: The heat capacity of LiCoO 2 (O3-phase), constituent material in cathodes for lithium-ion batteries, was measured using two differential scanning calorimeters over the temperature range from (160 to 953) K (continuous method). As an alternative, the discontinuous method was employed over the temperature range from (493 to 693) K using a third calorimeter. Based on the results obtained, the enthalpy increment of LiCoO 2 was derived from T = 298.15 K up to 974.15 K. Very good agreement was obtained between the derived enthalpy increment and our independent measurements of enthalpy increment using transposed temperature drop calorimetry at 974.15 K. In addition, values of the enthalpy of formation of LiCoO 2 from the constituent oxides and elements were assessed based on measurements of enthalpy of dissolution using high temperature oxide melt drop solution calorimetry. The high temperature values obtained by these measurements are key input data in safety analysis and optimisation of the battery management systems which accounts for possible thermal runaway events

Standard enthalpy of formation of Sm6UO12 acid dissolution calorimetry

International Nuclear Information System (INIS)

Venkata Krishnan, R.; Jogeswararao, G.; Ananthasivan, K.

2016-01-01

The standard molar enthalpies of formation of Δ f (298 K) of Sm 6 UO 12 have been determined by using an indigenously developed isoperibol acid solution calorimeter. The water equivalent of this calorimeter was determined by electrical calibration. The accuracy of measurement were determined by using standard materials KCl and tris(hydroxyl methyl) amino-methane (TRIS) and was found to be within ±2%. The enthalpies of solution at 298 K of Sm 2 O 3 , UO 3 and Sm 6 UO 12 were measured by using this calorimeter. From these experimental results the enthalpies of formation of Sm 6 UO 12 at 298 K were computed by using Hess's law of summation. (author)

Formation enthalpy of NiBe and Ni5Be21

International Nuclear Information System (INIS)

Ivanov, M.I.; Karpova, T.F.; Dalago, N.Yu.

1981-01-01

The method of dissolution calorimetry is used to determine standard enthalpies of NiBe and Ni 5 Be 21 formation, which are 84.8+-2.2 and (-669+-37)kJ/mol. The enthalpy values of NiBe and Ni 5 Be 21 at 331 K are shown to coincide (within the limits of errors of these values) with the values at the standard temperature of 298.15 K [ru

Water as a solute in aprotic dipolar solvents. 2. D2O-H2O solute isotope effects on the enthalpy of water dissolution in nitromethane, acetonitrile and propylene carbonate at 298.15 K

International Nuclear Information System (INIS)

Ivanov, Evgeniy V.; Smirnov, Valeriy I.

2010-01-01

The enthalpies of solution of ordinary (H 2 O) and heavy (D 2 O) water in nitromethane (NM), acetonitrile (ACN) and propylene carbonate (PC) were measured calorimetrically at 298.15 K. Standard (at the infinite dilution) enthalpies of solution and solvation, along with D 2 O-H 2 O solute isotope effects on the quantities in question, were calculated. The enthalpies of solution of water H/D isotopologues were found to be positive by sign and substantially increasing in magnitude on going from ACN and PC to NM, whereas the corresponding positive solute H/D isotope effect changes in a consequence: NM > ACN > PC. The qualitative interrelations between the enthalpy-isotopic effect of dissolution (solvation) of water and the electron-accepting/donating ability of aprotic dipolar solvent (within a series considered) were found.

The enthalpy of sublimation of cubane

International Nuclear Information System (INIS)

Bashir-Hashemi, A.; Chickos, James S.; Hanshaw, William; Zhao Hui; Farivar, Behzad S.; Liebman, Joel F.

2004-01-01

The sublimation enthalpy of cubane, a key reference material for force field and quantum mechanical computations, was measured by combining the vaporization enthalpy at T = 298.15 K to the sum of the fusion enthalpy measured at T = 405 K and a solid-solid phase transition that occurs at T 394 K. The fusion and solid-solid phase transitions were measured previously. A sublimation enthalpy value of (55.2 ± 2.0) kJ mol -1 at T = 298.15 K was obtained. This value compares quite favorably the value obtained by comparing the sublimation enthalpy of similar substances as a function of their molar masses but is at odds with earlier measurements

The enthalpy of sublimation of cubane

Energy Technology Data Exchange (ETDEWEB)

Bashir-Hashemi, A.; Chickos, James S.; Hanshaw, William; Zhao Hui; Farivar, Behzad S.; Liebman, Joel F

2004-12-15

The sublimation enthalpy of cubane, a key reference material for force field and quantum mechanical computations, was measured by combining the vaporization enthalpy at T = 298.15 K to the sum of the fusion enthalpy measured at T = 405 K and a solid-solid phase transition that occurs at T 394 K. The fusion and solid-solid phase transitions were measured previously. A sublimation enthalpy value of (55.2 {+-} 2.0) kJ mol{sup -1} at T = 298.15 K was obtained. This value compares quite favorably the value obtained by comparing the sublimation enthalpy of similar substances as a function of their molar masses but is at odds with earlier measurements.

Enthalpy of phase transition and prediction of phase Equilibria in systems of glycols and glycol ethers

OpenAIRE

Esina, Zoya; Miroshnikov, Aleksandr; Korchuganova, Margarita

2014-01-01

The PCEAS model was used to study the liquid-solid and liquid-vapor phase transitions at constant pressure in systems containing glycols and glycol ethers. This method is based on minimizing the excess Gibbs energy over the solvation parameter, which takes into account the processes of association of molecules in various phases. To compute the diagrams, the data on enthalpy and phase transition temperatures of pure components are required, while the information about the interactions in the b...

Influence of the composition of aqueous-alcohol solvents on the thermodynamic characteristics of L-phenylalanine dissolution at 298.15 K

International Nuclear Information System (INIS)

Badelin, Valentin G.; Smirnov, Valeriy I.

2011-01-01

Highlights: ► Enthalpies of L-phenylalanine dissolution have been measured in aqueous methanol, ethanol, 1-propanol and 2-propanol. ► The measured data were reported as functions of composition of water + alcohol mixtures. ► Enthalpy coefficients of pair-wise interactions have been analyzed in terms of McMillan-Mayer theory. ► A comparative analysis of the characteristics of dissolution of L-phenylalanine and some other L-amino acids in the similar systems has been made. - Abstract: The enthalpies of L-phenylalanine dissolution in aqueous methanol, ethanol, 1-propanol and 2-propanol have been determined by calorimetry at 298.15 K and alcohol mole fractions up to x 2 ∼0.4. The standard enthalpies of solution Δ sol H° and transfer Δ tr H° from water to the mixed solvent as well as the enthalpy coefficients of L-phenylalanine–alcohol pair-wise interactions were calculated. The interrelation of the enthalpies of dissolution and transfer for L-phenylalanine with structural features of alcohols has been determined. A comparative analysis of the thermodynamic characteristics of dissolution of L-phenylalanine and some other amino acids (glycine, L-alanine, L-threonine and L-valine) in the mixtures studied has been made.

Standard molar enthalpy of formation of methoxyacetophenone isomers

International Nuclear Information System (INIS)

Amaral, Luísa M.P.F.; Morais, Victor M.F.; Ribeiro da Silva, Manuel A.V.

2014-01-01

Highlights: • Experimental and computational energetic study of methoxyacetophenone isomers. • Enthalpies of formation and phase transition determined by calorimetric techniques. • Quantum chemical calculations allowed estimation of enthalpies of formation. • Structure and energy correlations were established. - Abstract: Values of the standard (p o = 0.1 MPa) molar enthalpy of formation of 2′-, 3′- and 4′-methoxyacetophenones were derived from their standard molar energy of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpies of sublimation/vaporization of the compounds studied. The standard molar enthalpies of formation of the three compounds, in the gaseous phase, at T = 298.15 K, have been derived from the corresponding standard molar enthalpies of formation in the condensed phase and the standard molar enthalpies for the phase transition. The results obtained are −(232.0 ± 2.5), −(237.7 ± 2.7) and −(241.1 ± 2.1) kJ · mol −1 for 2′-, 3′- and 4′-methoxyacetophenone, respectively. Standard molar enthalpies of formation were also estimated from different methodologies: the Cox scheme as well as two different computational approaches using density functional theory-based B3LYP and the multilevel G3 methodologies

A Mixed Enthalpy-Temperature Finite Element Method For Generalized Phase-Change Problems

DEFF Research Database (Denmark)

krabbenhøft, Kristian; Damkilde, Lars

2003-01-01

In a large number of problems of engineering interest the transition of the material from one phase to another is of vital importance in describing the overall physical behaviour. Common applications include metal casting, freezing and thawing of foodstuffs and other biological materials, ground ...... freezing and solar energy storage. The phase-change problem is characterized by an abrupt change in enthalpy per unit temperature in a narrow temperature range around the freezing point....

A Mixed Enthalpy-Temperature Finite Element Method For Generalized Phase-Change Problems

DEFF Research Database (Denmark)

krabbenhøft, Kristian; Damkilde, Lars

2003-01-01

In a large number of problems of engineering interest the transition of the material from one phase to another is of vital importance in describing the overall physical behaviour. Common applications include metal casting, freezing and thawing of foodstuffs and other biological materials, ground...... freezing and solar energy storage. The phase-change problem is characterized by an abrupt change in enthalpy per unit temperature in a narrow temperature range around the freezing point....

In situ measurement of solvent-mediated phase transformations during dissolution testing

DEFF Research Database (Denmark)

Aaltonen, Jaakko; Heinänen, Paula; Peltonen, Leena

2006-01-01

In this study, solvent-mediated phase transformations of theophylline (TP) and nitrofurantoin (NF) were measured in a channel flow intrinsic dissolution test system. The test set-up comprised simultaneous measurement of drug concentration in the dissolution medium (with UV-Vis spectrophotometry......) and measurement of the solid-state form of the dissolving solid (in situ with Raman spectroscopy). The solid phase transformations were also investigated off-line with scanning electron microscopy. TP anhydrate underwent a transformation to TP monohydrate, and NF anhydrate (form beta) to NF monohydrate (form II......). Transformation of TP anhydrate to TP monohydrate resulted in a clear decrease in the dissolution rate, while the transformation of NF anhydrate (form beta) to NF monohydrate (form II) could not be linked as clearly to changes in the dissolution rate. The transformation of TP was an order of magnitude faster than...

Mechanistic analysis of solute transport in an in vitro physiological two-phase dissolution apparatus.

Science.gov (United States)

Mudie, Deanna M; Shi, Yi; Ping, Haili; Gao, Ping; Amidon, Gordon L; Amidon, Gregory E

2012-10-01

In vitro dissolution methodologies that adequately capture the oral bioperformance of solid dosage forms are critical tools needed to aid formulation development. Such methodologies must encompass important physiological parameters and be designed with drug properties in mind. Two-phase dissolution apparatuses, which contain an aqueous phase in which the drug dissolves (representing the dissolution/solubility component) and an organic phase into which the drug partitions (representing the absorption component), have the potential to provide meaningful predictions of in vivo oral bioperformance for some BCS II, and possibly some BCS IV drug products. Before such an apparatus can be evaluated properly, it is important to understand the kinetics of drug substance partitioning from the aqueous to the organic medium. A mass transport analysis was performed of the kinetics of partitioning of drug substance solutions from the aqueous to the organic phase of a two-phase dissolution apparatus. Major assumptions include pseudo-steady-state conditions, a dilute aqueous solution and diffusion-controlled transport. Input parameters can be measured or estimated a priori. This paper presents the theory and derivation of our analysis, compares it with a recent kinetic approach, and demonstrates its effectiveness in predicting in vitro partitioning profiles of three BCS II weak acids in four different in vitro two-phase dissolution apparatuses. Very importantly, the paper discusses how a two-phase apparatus can be scaled to reflect in vivo absorption kinetics and for which drug substances the two-phase dissolution systems may be appropriate tools for measuring oral bioperformance. Copyright © 2012 John Wiley & Sons, Ltd.

A molecular dynamics study of ambient and high pressure phases of silica: structure and enthalpy variation with molar volume.

Science.gov (United States)

Rajappa, Chitra; Sringeri, S Bhuvaneshwari; Subramanian, Yashonath; Gopalakrishnan, J

2014-06-28

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase.

The thermochemistry of 2,4-pentanedione revisited: observance of a nonzero enthalpy of mixing between tautomers and its effects on enthalpies of formation.

Science.gov (United States)

Temprado, Manuel; Roux, Maria Victoria; Umnahanant, Patamaporn; Zhao, Hui; Chickos, James S

2005-06-30

The enthalpies of formation of pure liquid and gas-phase (Z)-4-hydroxy-3-penten-2-one and 2,4-pentanedione are examined in the light of some more recent NMR studies on the enthalpy differences between gas-phase enthalpies of the two tautomers. Correlation gas chromatography experiments are used to evaluate the vaporization enthalpies of the pure tautomers. Values of (51.2 +/- 2.2) and (50.8 +/- 0.6) kJ.mol(-1) are measured for pure 2,4-pentanedione and (Z)-4-hydroxy-3-penten-2-one, respectively. The value of (50.8 +/- 0.6) kJ.mol(-1) can be contrasted to a value of (43.2 +/- 0.2) kJ.mol(-1) calculated for pure (Z)-4-hydroxy-3-penten-2-one when the vaporization enthalpy is measured in a mixture of tautomers. The difference is attributed to an endothermic enthalpy of mixing that destabilizes the mixture relative to the pure components. Calculation of new enthalpies of formation for (Z)-4-hydroxy-3-penten-2-one and 2,4-pentanedione in both the gas, Delta(f)H degrees (m)(g) = (-378.2 +/- 1.2) and (-358.9 +/- 2.5) kJ.mol(-1), respectively, and liquid phases, Delta(f)H degrees (m)(l) = (-429.0 +/- 1.0) and (-410.1 +/- 1.2) kJ.mol(-1), respectively, results in enthalpy differences between the two tautomers both in the liquid and gas phases that are identical within experimental error, and in excellent agreement with recent gas-phase NMR studies.

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.

Melting temperature and enthalpy variations of phase change materials (PCMs): a differential scanning calorimetry (DSC) analysis

Science.gov (United States)

Sun, Xiaoqin; Lee, Kyoung Ok; Medina, Mario A.; Chu, Youhong; Li, Chuanchang

2018-06-01

Differential scanning calorimetry (DSC) analysis is a standard thermal analysis technique used to determine the phase transition temperature, enthalpy, heat of fusion, specific heat and activation energy of phase change materials (PCMs). To determine the appropriate heating rate and sample mass, various DSC measurements were carried out using two kinds of PCMs, namely N-octadecane paraffin and calcium chloride hexahydrate. The variations in phase transition temperature, enthalpy, heat of fusion, specific heat and activation energy were observed within applicable heating rates and sample masses. It was found that the phase transition temperature range increased with increasing heating rate and sample mass; while the heat of fusion varied without any established pattern. The specific heat decreased with the increase of heating rate and sample mass. For accuracy purpose, it is recommended that for PCMs with high thermal conductivity (e.g. hydrated salt) the focus will be on heating rate rather than sample mass.

Standard molar enthalpies of formation of monochloroacetophenone isomers

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Amaral, Luisa M.P.F.

2010-01-01

The standard (p 0 =0.1MPa) molar enthalpies of formation of the liquids 2'-, 3'-, and 4'-chloroacetophenones were derived from the standard molar energies of combustion, in oxygen, to yield CO 2 (g) and HCl . 600H 2 O(l), at T = 298.15 K, measured by rotating-bomb combustion calorimetry. The Calvet microcalorimetry was used to measure the enthalpies of vaporization of the three compounds. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the chloroacetophenone isomers, in the gaseous phase, at T = 298.15 K. (table) An empirical scheme, developed by Cox, was used to estimate the gas-phase enthalpies of formation and the obtained values were compared with the experimental ones.

The enthalpies of formation of two dibenzocyclooctadienones

Energy Technology Data Exchange (ETDEWEB)

Perisanu, St.; Contineanu, Iulia; Banciu, M.D.; Liebman, Joel F.; Farivar, Behzad S.; Mullan, Melissa A.; Chickos, James S.; Rath, Nigam; Hillesheim, Dorothea M

2003-04-17

The standard molar enthalpies of formation ({delta}{sub f}H{sub m}{sup 0}(s)/kJ mol{sup -1}) for 2,3:6,7-dibenzocycloocta-2,6-dien-1-one and 2,3:7,8-dibenzocycloocta-2,7-dien-1-one [6H-11,12-dihydro-dibenzo[a,e]cycloocten-5-one (ketone 1) and 10H-11,12-dihydrodibenzo[a,d]-cycloocten-5-one (ketone 2), respectively] were derived from enthalpies of combustion, measured by means of a microbomb calorimeter. The fusion and vaporization enthalpies of these compounds were obtained from DSC and correlation gas chromatography measurements. The standard molar enthalpies of formation in the gas phase were calculated by combining the condensed phase standard molar enthalpies of formation with the fusion and vaporization enthalpies adjusted to 298.15 K. Values for {delta}{sub f}H{sub m}{sup 0}(g) of (-39.9{+-}5.5) and (-14.8{+-}5.3) kJ mol{sup -1} were obtained for 2,3:6,7-dibenzocycloocta-2,6-dien-1-one and 2,3:7,8-dibenzocycloocta-2,7-dien-1-one, respectively. Quantum chemical calculations are reported for the compounds investigated experimentally and an additional four isomers. Isomerization enthalpies are derived from computed energies. The enthalpies of formation are also calculated by group additivity, compared with the experimental values and then correlated with the structure of the molecules investigated. The X-ray analysis of ketone 1 is also reported.

The enthalpies of formation of two dibenzocyclooctadienones

International Nuclear Information System (INIS)

Perisanu, St.; Contineanu, Iulia; Banciu, M.D.; Liebman, Joel F.; Farivar, Behzad S.; Mullan, Melissa A.; Chickos, James S.; Rath, Nigam; Hillesheim, Dorothea M.

2003-01-01

The standard molar enthalpies of formation (Δ f H m 0 (s)/kJ mol -1 ) for 2,3:6,7-dibenzocycloocta-2,6-dien-1-one and 2,3:7,8-dibenzocycloocta-2,7-dien-1-one [6H-11,12-dihydro-dibenzo[a,e]cycloocten-5-one (ketone 1) and 10H-11,12-dihydrodibenzo[a,d]-cycloocten-5-one (ketone 2), respectively] were derived from enthalpies of combustion, measured by means of a microbomb calorimeter. The fusion and vaporization enthalpies of these compounds were obtained from DSC and correlation gas chromatography measurements. The standard molar enthalpies of formation in the gas phase were calculated by combining the condensed phase standard molar enthalpies of formation with the fusion and vaporization enthalpies adjusted to 298.15 K. Values for Δ f H m 0 (g) of (-39.9±5.5) and (-14.8±5.3) kJ mol -1 were obtained for 2,3:6,7-dibenzocycloocta-2,6-dien-1-one and 2,3:7,8-dibenzocycloocta-2,7-dien-1-one, respectively. Quantum chemical calculations are reported for the compounds investigated experimentally and an additional four isomers. Isomerization enthalpies are derived from computed energies. The enthalpies of formation are also calculated by group additivity, compared with the experimental values and then correlated with the structure of the molecules investigated. The X-ray analysis of ketone 1 is also reported

Standard molar enthalpies of formation of monochloroacetophenone isomers

Energy Technology Data Exchange (ETDEWEB)

Ribeiro da Silva, Manuel A.V., E-mail: risilva@fc.up.p [Centro de Investigacao em Quimica, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Amaral, Luisa M.P.F. [Centro de Investigacao em Quimica, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

2010-12-15

The standard (p{sup 0}=0.1MPa) molar enthalpies of formation of the liquids 2'-, 3'-, and 4'-chloroacetophenones were derived from the standard molar energies of combustion, in oxygen, to yield CO{sub 2}(g) and HCl . 600H{sub 2}O(l), at T = 298.15 K, measured by rotating-bomb combustion calorimetry. The Calvet microcalorimetry was used to measure the enthalpies of vaporization of the three compounds. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the chloroacetophenone isomers, in the gaseous phase, at T = 298.15 K. (table) An empirical scheme, developed by Cox, was used to estimate the gas-phase enthalpies of formation and the obtained values were compared with the experimental ones.

Enthalpies of solution, enthalpies of fusion and enthalpies of solvation of polyaromatic hydrocarbons: Instruments for determination of sublimation enthalpy at 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Solomonov, Boris N., E-mail: boris.solomonov@ksu.ru; Varfolomeev, Mikhail A.; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.; Novikov, Vladimir B.

2015-12-20

Graphical abstract: - Highlights: • Solution enthalpies of aromatic hydrocarbons were measured at 298.15 K. • Solution enthalpy of aromatic hydrocarbons in benzene is equal to their fusion enthalpy. • Method for calculation of solvation enthalpy of aromatic hydrocarbons was proposed. • Approach for estimation of aromatic hydrocarbons sublimation enthalpy was developed. • Obtained sublimation enthalpies coincide well with the recommended literature data. - Abstract: In this work a simple method for calculation of solvation enthalpies of polyaromatic hydrocarbons (PAHs) in various solvents at 298.15 K was proposed. According to this method the enthalpy of solvation of any polyaromatic hydrocarbon in a particular solvent can be calculated on the basis of the general formula of the compound, the solvation enthalpy of benzene in the same solvent and parameter related to the contribution of hydrogen atom into solvation enthalpy. The validity of the proposed method was confirmed by the comparison of calculated and experimentally measured values of solvation enthalpies of PAHs in benzene, tetrahydrofuran and acetonitrile. This method was used for determination of the sublimation enthalpy of PAHs at 298.15 K based on the general relationship between the enthalpy of sublimation/vaporization of the compound of interest and its enthalpies of solution and solvation in the same solvent at 298.15 K. Enthalpies of solution at infinite dilution of several PAHs were measured in acetonitrile, benzene and tetrahydrofuran at 298.15 K. It was shown that solution enthalpies of PAHs in benzene at 298.15 K are approximately equal to their fusion enthalpies at the melting temperature. Solvation enthalpies of 15 PAHs at 298.15 K calculated according to the proposed method together with corresponding fusion enthalpy values (at the melting temperature) were used to calculate the sublimation enthalpy values at 298.15 K. Comparison of the obtained results with recommended values of

Analysis of phase formation in Ni-rich alloys of the Ni-Ta-W system by calorimetry, DTA, SEM, and TEM

Energy Technology Data Exchange (ETDEWEB)

Witusiewicz, V.T.; Hecht, U.; Warnken, N.; Fries, S.G. [Access e.V., Aachen (Germany); Hu Weiping [Inst. fuer Metallkunde und Metallphysik der RWTH Aachen (Germany)

2006-04-15

The partial enthalpies of dissolution of pure Ni, W and Ta in liquid ternary Ni-Ta-W alloys have been determined at (1773 {+-} 5) K using a high temperature isoperibolic calorimeter. Measurements were performed in Ni-rich alloys (from 80 to 100 at.% Ni) along sections with constant Ta:W atomic ratios 1:0, 2:1, 1:2, and 0:1. The partial enthalpies and thereby the integral enthalpy of mixing of these ternary alloys are calculated from the partial enthalpies of dissolution using SGTE Gibbs energies for pure elements as reference. The obtained thermochemical data confirm that in the investigated Ni-rich alloys the binary interactions between Ta and W as well as the ternary Ni-Ta-W interactions are negligibly small. Due to this the variation of the integral enthalpy of mixing of the ternary alloys is well described as linear combination of the constituent Ni-Ta and Ni-W binaries. Such behaviour of the ternary liquid alloys is related to a very low probability of new ternary stable phases to occur in solid state. This prediction is confirmed by differential thermal analysis, scanning electron microscopy, and transmission electron microscopy of the as-solidified and annealed samples obtained as last alloy compositions in the series of calorimetric dissolution. (orig.)

Enthalpies of Formation of Hydrazine and Its Derivatives.

Science.gov (United States)

Dorofeeva, Olga V; Ryzhova, Oxana N; Suchkova, Taisiya A

2017-07-20

Enthalpies of formation, Δ f H 298 ° , in both the gas and condensed phase, and enthalpies of sublimation or vaporization have been estimated for hydrazine, NH 2 NH 2 , and its 36 various derivatives using quantum chemical calculations. The composite G4 method has been used along with isodesmic reaction schemes to derive a set of self-consistent high-accuracy gas-phase enthalpies of formation. To estimate the enthalpies of sublimation and vaporization with reasonable accuracy (5-20 kJ/mol), the method of molecular electrostatic potential (MEP) has been used. The value of Δ f H 298 ° (NH 2 NH 2 ,g) = 97.0 ± 3.0 kJ/mol was determined from 75 isogyric reactions involving about 50 reference species; for most of these species, the accurate Δ f H 298 ° (g) values are available in Active Thermochemical Tables (ATcT). The calculated value is in excellent agreement with the reported results of the most accurate models based on coupled cluster theory (97.3 kJ/mol, the average of six calculations). Thus, the difference between the values predicted by high-level theoretical calculations and the experimental value of Δ f H 298 ° (NH 2 NH 2 ,g) = 95.55 ± 0.19 kJ/mol recommended in the ATcT and other comprehensive reference sources is sufficiently large and requires further investigation. Different hydrazine derivatives have been also considered in this work. For some of them, both the enthalpy of formation in the condensed phase and the enthalpy of sublimation or vaporization are available; for other compounds, experimental data for only one of these properties exist. Evidence of accuracy of experimental data for the first group of compounds was provided by the agreement with theoretical Δ f H 298 ° (g) value. The unknown property for the second group of compounds was predicted using the MEP model. This paper presents a systematic comparison of experimentally determined enthalpies of formation and enthalpies of sublimation or vaporization with the results of

Enthalpies of fusion and enthalpies of solvation of aromatic hydrocarbons derivatives: Estimation of sublimation enthalpies at 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Solomonov, Boris N., E-mail: boris.solomonov@kpfu.ru; Nagrimanov, Ruslan N.; Varfolomeev, Mikhail A.; Buzyurov, Aleksey V.; Mukhametzyanov, Timur A.

2016-03-20

Graphical abstract: - Highlights: • Solution enthalpies of aromatic hydrocarbons derivatives (ArHD) were measured at 298.15 K. • Solution enthalpies of ArHD in benzene at 298.15 K are equal to their fusion enthalpy at melting point. • Sublimation enthalpies of 80 ArHD were calculated as a sum of fusion and solvation enthalpies. • Obtained sublimation enthalpies are in good agreement with the recommended literature data. - Abstract: Enthalpy of sublimation of solid compound can be found using the values of solution enthalpy and solvation enthalpy in any solvent. In this work enthalpies of solution at infinite dilution of a number of aromatic hydrocarbons derivatives in benzene were measured at 298.15 K. Comparison between experimental and literature solution enthalpies in benzene at 298.15 K and fusion enthalpies at melting temperature of aromatic hydrocarbon derivatives showed, that these values are approximately equal. Thereby, fusion enthalpies at melting temperature can be used instead of their solution enthalpies in benzene at 298.15 K for calculation of sublimation enthalpies at 298.15 K. Solvation enthalpies in benzene at 298.15 K required for this procedure were calculated using group additivity scheme. The sublimation enthalpies of 80 aromatic hydrocarbons derivatives at 298.15 K were evaluated as a difference between fusion enthalpies at melting temperature and solvation enthalpies in benzene at 298.15 K. Obtained in this work values of sublimation enthalpy at 298.15 K for studied compounds were in a good agreement with available literature data.

Enthalpy of Formation of N2H4 (Hydrazine) Revisited.

Science.gov (United States)

Feller, David; Bross, David H; Ruscic, Branko

2017-08-17

In order to address the accuracy of the long-standing experimental enthalpy of formation of gas-phase hydrazine, fully confirmed in earlier versions of Active Thermochemical Tables (ATcT), the provenance of that value is re-examined in light of new high-end calculations of the Feller-Peterson-Dixon (FPD) variety. An overly optimistic determination of the vaporization enthalpy of hydrazine, which created an unrealistically strong connection between the gas phase thermochemistry and the calorimetric results defining the thermochemistry of liquid hydrazine, was identified as the probable culprit. The new enthalpy of formation of gas-phase hydrazine, based on balancing all available knowledge, was determined to be 111.57 ± 0.47 kJ/mol at 0 K (97.42 ± 0.47 kJ/mol at 298.15 K). Close agreement was found between the ATcT (even excluding the latest theoretical result) and the FPD enthalpy.

Revision of standard molar enthalpies of formation of glycine and L-alanine in the gaseous phase on the basis of theoretical calculations

International Nuclear Information System (INIS)

Dorofeeva, Olga V.; Ryzhova, Oxana N.

2009-01-01

The standard molar enthalpies of formation of urea, glycine, and L-alanine in the gaseous phase at 298.15 K were calculated by the high-level Gaussian-3X method. The agreement with the available experimental data is very good for urea and glycine and, thus, supports the high accuracy of calculated values. A significant discrepancy between theoretical and experimental enthalpy of formation values for L-alanine provides a reason to reconsider the experimental data previously used to derive the standard molar enthalpy of formation of L-alanine in the gaseous phase at 298.15 K. To obtain a more reliable value of enthalpy of sublimation at 298.15 K, the heat capacity values of gaseous L-alanine were calculated by standard statistical thermodynamics formulae using molecular parameters determined from B3LYP/cc-pVTZ calculations. With the obtained value of C p,m 0 (L-alanine, g, 298.15 K) = 112.6 ± 4.0 J . K -1 . mol -1 the original published experimental values of enthalpy of sublimation of L-alanine were readjusted to the reference temperature: Δ cr g H m (L-alanine, 298.15 K) = 135.2 ± 2.0 kJ . mol -1 . This value, together with the experimental enthalpy of formation of solid L-alanine, Δ f H m 0 (L-alanine, cr, 298.15 K) = -560.0 ± 1.0 kJ . mol -1 [S.N. Ngauv, R. Sabbah, M. Laffitte, Thermochim. Acta 20 (1977) 371-380; I. Contineanu, D.I. Marchidan, Rev. Roum. Chim. 29 (1984) 43-48], gives a new value for the enthalpy of formation of L-alanine in the gaseous phase, Δ f H m 0 (L-alanine, g, 298.15 K) = -424.8 ± 2.0 kJ . mol -1 , which is in good agreement with our theoretical G3X result, -427.6 ± 4.0 kJ . mol -1 . The same procedure for glycine allowed us to improve the literature value of the enthalpy of formation for this compound, Δ f H m 0 (glycine, g, 298.15 K) = -393.7 ± 1.5 kJ . mol -1 . As a result a set of self-consistent thermochemical data for glycine and L-alanine is proposed

Influence of processing-induced phase transformations on the dissolution of theophylline tablets

OpenAIRE

Debnath, Smita; Suryanarayanan, Raj

2004-01-01

The object of this investigation was to evaluate the influence of (1) processing-induced decrease in drug crystallinity and (2) phase transformations during dissolution, on the per-formance of theophylline tablet formulations. Anhydrous theophylline underwent multiple transformations (anhydrate »hydrate»anhydrate) during processing. Although the crystallinity of the anhydrate obtained finally was lower than that of the unprocessed drug, it dissolved at a slower rate. This decrease in dissolut...

Predicting the enthalpies of melting and vaporization for pure components

Science.gov (United States)

Esina, Z. N.; Korchuganova, M. R.

2014-12-01

A mathematical model of the melting and vaporization enthalpies of organic components based on the theory of thermodynamic similarity is proposed. In this empirical model, the phase transition enthalpy for the homological series of n-alkanes, carboxylic acids, n-alcohols, glycols, and glycol ethers is presented as a function of the molecular mass, the number of carbon atoms in a molecule, and the normal transition temperature. The model also uses a critical or triple point temperature. It is shown that the results from predicting the melting and vaporization enthalpies enable the calculation of binary phase diagrams.

Standard molar enthalpies of formation of 2-, 3- and 4-cyanobenzoic acids

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Amaral, Luisa M.P.F.; Boaventura, Cristina R.P.; Gomes, Jose R.B.

2008-01-01

The standard (p 0 = 0.1 MPa) molar enthalpies of formation of 2-, 3- and 4-cyanobenzoic acids were derived from their standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpies of sublimation of 2- and 3-cyanobenzoic acids. The standard molar enthalpies of formation of the three compounds, in the gaseous phase, at T = 298.15 K, have been derived from the corresponding standard molar enthalpies of formation in the condensed phase and standard molar enthalpies for phase transition. The results obtained are -(150.7 ± 2.0) kJ . mol -1 , -(153.6 ± 1.7) kJ . mol -1 and -(157.1 ± 1.4) kJ . mol -1 for 2-cyano, 3-cyano and 4-cyanobenzoic acids, respectively. Standard molar enthalpies of formation were also estimated by employing two different methodologies: one based on the Cox scheme and the other one based on several different computational approaches. The calculated values show a good agreement with the experimental values obtained in this work

Standard molar enthalpies of formation of 2-furancarbonitrile, 2-acetylfuran, and 3-furaldehyde

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Amaral, Luisa M.P.F.

2009-01-01

The standard (p 0 = 0.1 MPa) molar energies of combustion of 2-furancarbonitrile, 2-acetylfuran, and 3-furaldehyde were measured by static bomb combustion calorimetry; the Calvet high-temperature microcalorimetry was used to measure the enthalpies of vaporization of these liquid compounds. The standard molar enthalpies of formation of the three compounds, in the gaseous phase, at T = 298.15 K, have been derived from the corresponding standard molar enthalpies of formation in the liquid phase and the standard molar enthalpies of phase transition, as (106.8 ± 1.1) kJ . mol -1 , -(207.4 ± 1.3) kJ . mol -1 , and -(151.9 ± 1.1) kJ . mol -1 , for 2-furancarbonitrile, 2-acetylfuran, and 3-furaldehyde, respectively. Standard molar enthalpies of formation are discussed in terms of the isomerization ortho meta. Enthalpic increment values of the introduction of the functional groups -CN, -CHO, and -COCH 3 were also compared with some other heterocycles; i.e. thiophene and pyridine

Enthalpies of formation of dihydroxybenzenes revisited: Combining experimental and high-level ab initio data

International Nuclear Information System (INIS)

Gonçalves, Elsa M.; Agapito, Filipe; Almeida, Tânia S.; Martinho Simões, José A.

2014-01-01

Highlights: • Thermochemistry of hydroxyphenols probed by experimental and theoretical methods. • A new paradigm for obtaining enthalpies of formation of crystalline compounds. • High-level ab initio results for the thermochemistry of gas-phase hydroxyphenols. • Sublimation enthalpies of hydroxyphenols determined by Calvet microcalorimetry. - Abstract: Accurate values of standard molar enthalpies of formation in condensed phases can be obtained by combining high-level quantum chemistry calculations of gas-phase enthalpies of formation with experimentally determined enthalpies of sublimation or vapourization. The procedure is illustrated for catechol, resorcinol, and hydroquinone. Using W1-F12, the gas-phase enthalpies of formation of these compounds at T = 298.15 K were computed as (−270.6, −269.4, and −261.0) kJ · mol −1 , respectively, with an uncertainty of ∼0.4 kJ · mol −1 . Using well characterised solid samples, the enthalpies of sublimation were determined with a Calvet microcalorimeter, leading to the following values at T = 298.15 K: (88.3 ± 0.3) kJ · mol −1 , (99.7 ± 0.4) kJ · mol −1 , and (102.0 ± 0.9) kJ · mol −1 , respectively. It is shown that these results are consistent with the crystalline structures of the compounds

Interface Enthalpy-Entropy Competition in Nanoscale Metal Hydrides

Directory of Open Access Journals (Sweden)

Nicola Patelli

2018-01-01

Full Text Available We analyzed the effect of the interfacial free energy on the thermodynamics of hydrogen sorption in nano-scaled materials. When the enthalpy and entropy terms are the same for all interfaces, as in an isotropic bi-phasic system, one obtains a compensation temperature, which does not depend on the system size nor on the relative phase abundance. The situation is different and more complex in a system with three or more phases, where the interfaces have different enthalpy and entropy. We also consider the possible effect of elastic strains on the stability of the hydride phase and on hysteresis. We compare a simple model with experimental data obtained on two different systems: (1 bi-phasic nanocomposites where ultrafine TiH2 crystallite are dispersed within a Mg nanoparticle and (2 Mg nanodots encapsulated by different phases.

Standard molar enthalpies of formation of 2-, 3-, and 4-piperidinomethanol isomers

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Cabral, Joana I.T.A.

2006-01-01

The standard (p o =0.1MPa) molar energies of combustion in oxygen of 2-piperidinemethanol, 3-piperidinemethanol, and 4-piperidinemethanol, all in the crystalline phase, were measured, at T=298.15K, by static bomb calorimetry. These values were used to derive the standard molar enthalpies of combustion and the standard molar enthalpies of formation, in the condensed phase, for these compounds. Further, the standard molar enthalpies of sublimation, at T=298.15K, of these three piperidinomethanol isomers were determined by Cavet microcalorimetry. The combustion calorimetry results together with those from the Calvet microcalorimetry, were used to derive the standard molar enthalpies of formation, at T=298.15K, in the gaseous phase, of the three piperidinemethanol studied. -Δ c H m o (cr)Δ cr g H m o kJ.mol -1 kJ.mol -1 2-Piperidinemethanol3890.70+/-0.9293.02+/-0.503- Piperidinemethanol3895.3+/-1.195.9+/-1.44-Piperidinemethanol3891.3+/- 1.198.31+/-0.69

Simultaneous UV Imaging and Raman Spectroscopy for the Measurement of Solvent-Mediated Phase Transformations During Dissolution Testing

DEFF Research Database (Denmark)

Ostergaard, Jesper; Wu, Jian; Naelapää, Kaisa

2014-01-01

The current work reports the simultaneous use of UV imaging and Raman spectroscopy for detailed characterization of drug dissolution behavior including solid-state phase transformations during dissolution. The dissolution of drug substances from compacts of sodium naproxen in 0.1 HCl as well as t...... of UV imaging and Raman spectroscopy offers a detailed characterization of drug dissolution behavior in a time-effective and sample-sparing manner. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 103:1149-1156, 2014....

Standard molar enthalpies of formation of three N-benzoylthiocarbamic-O-alkylesters

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Santos, Luis M.N.B.F.; Schroeder, Bernd; Dietze, Frank; Beyer, Lothar

2004-01-01

The standard (p 0 =0.1 MPa) molar enthalpies of combustion in oxygen of three crystalline N-benzoylthiocarbamic-O-alkylesters, PhCONHCSOR, R=Et (Hbtcee), n-Bu (Hbtcbe), n-Hex (Hbtche), were measured at T=298.15 K by rotating bomb calorimetry. The standard molar enthalpies of sublimation of the three compounds were measured using Calvet microcalorimetry. These values were used to derive the standard molar enthalpies of formation of the compounds in their crystalline and gaseous phases, respectively

Standard molar enthalpy of formation of 1-benzosuberone: An experimental and computational study

International Nuclear Information System (INIS)

Miranda, Margarida S.; Morais, Victor M.F.; Matos, M. Agostinha R.; Liebman, Joel F.

2010-01-01

The energetics of 1-benzosuberone was studied by a combination of calorimetric techniques and computational calculations. The standard (p o = 0.1 MPa) molar enthalpy of formation of 1-benzosuberone, in the liquid phase, was derived from the massic energy of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The standard molar enthalpy of vaporization, at T = 298.15 K, was measured by Calvet microcalorimetry. From these two parameters the standard (p o = 0.1 MPa) molar enthalpy of formation, in the gaseous phase, at T = 298.15 K, was derived: -(96.1 ± 3.4) kJ . mol -1 . The G3(MP2)//B3LYP composite method and appropriate reactions were used to computationally calculate the standard molar enthalpy of formation of 1-benzosuberone, in the gaseous phase, at T = 298.15 K. The computational results are in very good agreement with the experimental value.

Determination of melting and solidification enthalpy of hypereutectic silumins

Directory of Open Access Journals (Sweden)

J. Piątkowski

2008-04-01

Full Text Available The study was related with determination of the values of enthalpy of melting and solidification of hypereutectic AlSi18, AlSi21 and AlSi24 silumins modified with phosphorus in the form of Cu-P. The calorimetry, preceded by thermal analysis and derivative thermal analysis (TA and DTA, respectively was carried out on a high-temperature scanning calorimeter, model MHTC-96, made by SETARAM, applying the method of direct determination of parameters of the high-temperature process, and in particular of the enthalpy of phase transformations. Modern control and measuring instruments coupled with PC computer provide a very precise tool for determination of these transformations. An additional advantage was development of appropriate software called „SETSOFT”, owing to which it was possible to determine in an easy way the enthalpy of the investigated phase transformations. Moreover, an additional thermal effect, related most probably with pre-eutectic crystallization of primary silicon, was observed and confirmed by calorimetric examinations.

Development and application of a biorelevant dissolution method using USP apparatus 4 in early phase formulation development.

Science.gov (United States)

Fang, Jiang B; Robertson, Vivian K; Rawat, Archana; Flick, Tawnya; Tang, Zhe J; Cauchon, Nina S; McElvain, James S

2010-10-04

Dissolution testing is frequently used to determine the rate and extent at which a drug is released from a dosage form, and it plays many important roles throughout drug product development. However, the traditional dissolution approach often emphasizes its application in quality control testing and usually strives to obtain 100% drug release. As a result, dissolution methods are not necessarily biorelevant and meaningful application of traditional dissolution methods in the early phases of drug product development can be very limited. This article will describe the development of a biorelevant in vitro dissolution method using USP apparatus 4, biorelevant media, and real-time online UV analysis. Several case studies in the areas of formulation selection, lot-to-lot variability, and food effect will be presented to demonstrate the application of this method in early phase formulation development. This biorelevant dissolution method using USP apparatus 4 provides a valuable tool to predict certain aspects of the in vivo drug release. It can be used to facilitate the formulation development/selection for pharmacokinetic (PK) and clinical studies. It may also potentially be used to minimize the number of PK studies, and to aid in the design of more efficient PK and clinical studies.

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

Science.gov (United States)

Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

2006-04-01

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir

Enthalpy of Formation of N ₂ H ₄ (Hydrazine) Revisited

Energy Technology Data Exchange (ETDEWEB)

Feller, David [Department; Bross, David H. [Chemical; Ruscic, Branko [Chemical; Computation

2017-08-02

In order to address the accuracy of the long-standing experimental enthalpy of formation of gas-phase hydrazine, fully confirmed in earlier versions of Active Thermochemical Tables (ATcT), the provenance of that value is re-examined in light of new high-end calculations of the Feller-Peterson-Dixon (FPD) variety. An overly optimistic determination of the vaporization enthalpy of hydrazine, which created an unrealistically strong connection between the gas phase thermochemistry and the calorimetric results defining the thermochemistry of liquid hydrazine was identified as the probable culprit. The new enthalpy of formation of gas-phase hydrazine, based on balancing all available knowledge, was determined to be 111.57 ± 0.47 kJ/mol at 0 K (97.41 kJ/mol at 298.15 K). Close agreement was found between the ATcT (even excluding the latest theoretical result) and FPD enthalpies.

Standard molar enthalpies of formation of three methyl-pyrazole derivatives

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Cabral, Joana I.T.A.

2012-01-01

Highlights: ► Combustion calorimetry was used to determine Δ f H m ∘ (cr) of methyl-pyrazole derivatives. ► Vapour pressures were determined by the Knudsen mass-loss effusion technique. ► Gas-phase Δ f H m ∘ of the studied compounds have been derived. - Abstract: The standard (p ° = 0.1 MPa) molar enthalpies of formation of the crystalline 3-methyl-1-pyrazolecarboxamide; 3-methyl-3-pyrazoline-5-one; and 4-methyl-2-pyrazoline-5-one were derived from the standard massic energies of combustion, in oxygen, to yield CO 2 (g), H 2 O (l) and N 2 (g), at T = 298.15 K, measured by static bomb combustion calorimetry. The standard molar enthalpies of sublimation were calculated from the variation of the vapour pressures of each compound with temperature, measured by the Knudsen effusion technique. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the pyrazole derivatives, in the gaseous phase, at T = 298.15 K. The derived standard molar enthalpies of formation, in gaseous state, are analyzed in terms of enthalpic increments and interpreted in terms of molecular structure.

Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.

Science.gov (United States)

Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

2014-11-20

Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ΔfHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ΔfHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ΔfHmo(PhOCH3, l) = −(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ΔvapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ΔfHmo(PhOCH3, g) = −(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ΔfHmo(PhOCH3, g) = −(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ΔfHmo(PhOCH3, g) here recommended leads to ΔfHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1).

Etude cinetique et thermodynamique de la dissolution de la fluorapatite dans l'acide phosphorique

International Nuclear Information System (INIS)

Brahim, K.; Khattech, I.; Dubes, J.P.; Jemal, M.

2005-01-01

A modification on the reversal cells of a C-80 SETARAM calorimeter allows a Joule effect in the reaction cells to determine a transfer function in experimental conditions close to those of dissolution of a solid in a liquid. The calorimeter was then used to determine in isothermal conditions both thermodynamic and kinetic parameters associated with dissolution of synthetic fluorapatite in phosphoric acid solutions. Due to the rapidity of reaction, the heat flow recordings were deconvoluted and the resulting curves were analyzed iteratively to obtain the rates of digestion and the enthalpy of dissolution at 298 K of fluorapatite in phosphoric acid solution containing 10, 18 or 30 wt% P 2 O 5 . The results agree with a two-step dissolution mechanism. The first step is the dissolution of the solid in phosphoric acid, and the second is the formation of the complex Ca(H 2 PO 4 ) +

Final Report of Tank 241-C-105 Dissolution, the Phase 2 Study

International Nuclear Information System (INIS)

Meznarich, Huei K.; Bolling, Stacey D.; Cooke, Gary A.; Ely, Thomas M.; Herting, Daniel L.; Lachut, James S.; LaMothe, Margaret E.

2016-01-01

Three clamshell grab samples were taken from Tank 241-C-105 in October 2015 in accordance with RPP-PLAN-60011. Analytical results of those samples were issued in the report RPP-RPT-59115 by Wastren Advantage, Inc., Hanford Laboratory. Solid phase characterization results were reported separately in LAB-RPT-15-00011 and in RPP-RPT-59147. The major solid phases reported to be present were dawsonite [NaAlCO 3 (OH) 2 ], trona [Na 3 (HCO 3 )(CO 3 )⋅2H 2 O], cejkaite [Na 4 (UO 2 )(CO 3 ) 3 ], and an unidentified organic solid, with minor amounts of gibbsite [Al(OH) 3 ], natrophosphate [Na 7 F(PO 4 ) 2 ⋅19H 2 O], and traces of unidentified iron-rich and manganese-rich phases. Note that the presence of dawsonite, trona, and cejkaite requires a relatively low pH, likely around pH 9 to 10. One aliquot of each grab sample was provided to 222-S Laboratory Process Chemistry for dissolution studies. Phase 1 of the dissolution testing followed the approved test plan, WRPS-1404813, Rev. 3, and examined the behavior of the Tank 241-C-105 solids treated with water, 19M sodium hydroxide, 2M nitric acid, and 0.5M oxalic acid/2M nitric acid. Phase 2 of the testing was conducted in accordance with instructions from the client and emphasized treatment with 19M sodium hydroxide followed by water washing. This is the report of the Phase 2 testing.

Experimental standard molar enthalpies of formation of some methylbenzenediol isomers

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Lobo Ferreira, Ana I.M.C.

2009-01-01

The present work is part of a research program on the energetics of formation of alkyl substituted benzenediols, aiming the study of the enthalpic effect of the introduction of methyl substituents into benzenediols. In this work we present the results of the thermochemical research on 2-methylresorcinol, 3-methylresorcinol, 4-methylresorcinol, and methylhydroquinone. The standard (p 0 =0.1MPa) molar enthalpies of formation, in the crystalline phase, at T = 298.15 K, of the compounds mentioned above were derived from their standard massic energies of combustion, measured by static-bomb combustion calorimetry, while the standard molar enthalpies of sublimation of those compounds were obtained by the temperature dependence of their vapour pressures determined by the Knudsen effusion technique. From experimental values, the standard molar enthalpies of formation of the studied methylbenzenediols in the gaseous phase, at T = 298.15 K were then derived. The results are interpreted in terms of structural contributions to the energetics of the substituted benzenediols and compared with the same parameters estimated from the Cox Scheme. Moreover, the standard (p 0 =0.1MPa) molar enthalpies, entropies, and Gibbs energies of sublimation, at T = 298.15 K, were derived for the four isomers of methylbenzenediols.

Standard molar enthalpies of formation and of sublimation of the terphenyl isomers

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Santos, Luis M.N.B.F.; Lima, Luis M. Spencer S.

2008-01-01

The standard (p 0 = 0.1 MPa) molar enthalpies of formation in the crystalline phases of ortho, meta and para-terphenyl isomers, at T = 298.15 K, were derived from the standard molar energies of combustion, measured by mini-bomb combustion calorimetry. The Knudsen mass-loss effusion technique was used to measure the dependence of the vapour pressure of the crystals with the temperature, thus deriving their standard molar enthalpies of sublimation by means of the Clausius-Clapeyron equation. Combining the standard molar enthalpies of formation and sublimation of the crystalline terphenyls, the standard molar enthalpies of formation in the gaseous state, at T = 298.15 K, were derived for the three isomers. Results are provided in a table. The results show small but detectable isomerization enthalpies between the terphenyls, indicating the following relative enthalpic stabilities: m- > p- ∼ o-terphenyl

Final Report of Tank 241-C-105 Dissolution, the Phase 2 Study

Energy Technology Data Exchange (ETDEWEB)

Meznarich, Huei K. [Washington River Protection Solutions LLC., Richland, WA (United States); bolling, Stacey D. [Washington River Protection Solutions LLC., Richland, WA (United States); Cooke, Gary A. [Washington River Protection Solutions LLC., Richland, WA (United States); Ely, Thomas M. [Washington River Protection Solutions LLC., Richland, WA (United States); Herting, Daniel L. [Washington River Protection Solutions LLC., Richland, WA (United States); Lachut, James S. [Washington River Protection Solutions LLC., Richland, WA (United States); LaMothe, Margaret E. [Washington River Protection Solutions LLC., Richland, WA (United States)

2016-10-01

Three clamshell grab samples were taken from Tank 241-C-105 in October 2015 in accordance with RPP-PLAN-60011. Analytical results of those samples were issued in the report RPP-RPT-59115 by Wastren Advantage, Inc., Hanford Laboratory. Solid phase characterization results were reported separately in LAB-RPT-15-00011 and in RPP-RPT-59147. The major solid phases reported to be present were dawsonite [NaAlCO₃(OH)₂], trona [Na₃(HCO₃)(CO₃)·2H₂O], cejkaite [Na₄(UO₂)(CO₃)₃], and an unidentified organic solid, with minor amounts of gibbsite [Al(OH)₃], natrophosphate [Na₇F(PO₄)₂·19H₂O], and traces of unidentified iron-rich and manganese-rich phases. Note that the presence of dawsonite, trona, and cejkaite requires a relatively low pH, likely around pH 9 to 10. One aliquot of each grab sample was provided to 222-S Laboratory Process Chemistry for dissolution studies. Phase 1 of the dissolution testing followed the approved test plan, WRPS-1404813, Rev. 3, and examined the behavior of the Tank 241-C-105 solids treated with water, 19M sodium hydroxide, 2M nitric acid, and 0.5M oxalic acid/2M nitric acid. Phase 2 of the testing was conducted in accordance with instructions from the client and emphasized treatment with 19M sodium hydroxide followed by water washing. This is the report of the Phase 2 testing.

Standard molar enthalpies of formation of 1- and 2-cyanonaphthalene

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Lobo Ferreira, Ana I.M.C.; Barros, Ana L.M.; Bessa, Ana R.C.; Brito, Barbara C.S.A.; Vieira, Joana A.S.; Martins, Silvia A.P.

2011-01-01

Highlights: → Enthalpies of formation of 1- and 2-cyanonaphthalene were measured by combustion calorimetry. → Vapor pressures of crystalline 1- and 2-cyanonaphthalene obtained by Knudsen effusion mass loss technique. → Enthalpies, entropies and Gibbs functions of sublimation at T = 298.15 K were calculated. - Abstract: The standard (p o = 0.1 MPa) molar enthalpies of formation, in the crystalline state, of the 1- and 2-cyanonaphthalene were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static-bomb combustion calorimetry. Vapor pressure measurements at different temperatures, using the Knudsen mass loss effusion technique, enabled the determination of the enthalpy, entropy, and Gibbs energy of sublimation, at T = 298.15 K, for both isomers. The standard molar enthalpies of sublimation, at T = 298.15 K, for 1- and 2-cyanonaphthalene, were also measured by high-temperature Calvet microcalorimetry. (table) Combining these two experimental values, the gas-phase standard molar enthalpies, at T = 298.15 K, were derived and compared with those estimated by employing two different methodologies: one based on the Cox scheme and the other one based on G3MP2B3 calculations. The calculated values show a good agreement with the experimental values obtained in this work.

Experimental investigation of the dissolution of fractures. From early stage instability to phase diagram

Science.gov (United States)

Osselin, Florian; Budek, Agnieszka; Cybulski, Olgierd; Kondratiuk, Pawel; Garstecki, Piotr; Szymczak, Piotr

2016-04-01

Dissolution of natural rocks is a fundamental geological process and a key part of landscape formation and weathering processes. Moreover, in current hot topics like Carbon Capture and Storage or Enhanced Oil Recovery, mastering dissolution of the host rock is fundamental for the efficiency and the security of the operation. The basic principles of dissolution are well-known and the theory of the reactive infiltration instability has been extensively studied. However, the experimental aspect has proved very challenging because of the strong dependence of the outcome with pore network, chemical composition, flow rate... In this study we are trying to tackle this issue by using a very simple and efficient device consisting of a chip of pure gypsum inserted between two polycarbonate plates and subjected to a constant flow rate of pure water. Thanks to this device, we are able to control all parameters such as flow rate, fracture aperture, roughness of the walls... but also to observe in situ the progression of the dissolution thanks to the transparency of the polycarbonate which is impossible with 3D rocks. We have been using this experimental set-up to explore and investigate all aspects of the dissolution in a fracture, such as initial instability and phase diagram of different dissolution patterns, and to compare it with theory and simulations, yielding very good agreement and interesting feedbacks on the coupling between flow and chemistry in geological media

JSS project phase 4: Experimental and modelling studies of HLW glass dissolution in repository environments

International Nuclear Information System (INIS)

1987-10-01

A goal of the JSS project was to develop a scientific basis for understanding the effects of waste package components, groundwater chemistry, and other repository conditions on glass dissolution behaviour, and to develop and refine a model for the processes governing glass dissolution. The fourth phase of the project, which was performed by the Hahn-Meitner-Institut, Berlin, FRG, dealt specifically with model development and application. Phase 4 also adressed whether basaltic glasses could serve as natural analogues for nuclear waste glasses, thus providing a means to test the capability of the model for long-term predictions. Additional experiments were performed in order to complete the data base necessary to model interactions between the glass and bentonite and between glass and steel corrosion products. More data on temperature, S/V, and pH dependence of the glass/water reaction were also collected. In this report, the data acquired during phase 4 are presented and discussed. (orig./DG)

Thermodynamics of Dissolution for Crystalline Racemic Tartaric and Glutaric Acids and Isatin in KOH Aqueous Solutions at 298.15 K

Science.gov (United States)

Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Litvinenko, V. E.; Volkov, A. V.; Bychkova, S. A.; Skvortsov, I. A.

2018-01-01

Enthalpies of dissolution are found for crystalline racemic tartaric and glutaric acids and isatin in water and in potassium hydroxide solutions at 298.15 K via direct calorimetry. The protolytic equilibria in isatin aqueous solutions are studied at 298.15 K and ionic strengths of 0.5 (relative to potassium nitrate) by potentiometric means. Standard enthalpies of formation are calculated for racemic tartaric and glutaric acids, isatin, and the products of their dissociation in aqueous solutions.

What is the enthalpy of formation of pyrazine-2-carboxylic acid?

International Nuclear Information System (INIS)

Miranda, Margarida S.; Duarte, Darío J.R.; Liebman, Joel F.

2016-01-01

There are two contemporary conflicting, indeed, incompatible determinations of measurements of the enthalpies of combustion and of formation of pyrazine-2-carboxylic acid in the literature, (−2268.0 ± 0.9 and −271.2 ± 1.1 kJ · mol −1 ) and (−2211.4 ± 0.9 and −327.8 ± 1.1 kJ · mol −1 ). The current paper discusses these two sets of values and from the use of a measurement of the enthalpy of sublimation, a newly evaluated enthalpy of formation of pyrazine itself, and of the quantum chemical calculations at the G3(MP2)//B3LYP level, the former results are accepted and the derived gas phase enthalpy of formation, −(167.6 ± 3.1) kJ · mol −1 , suggested.

Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

International Nuclear Information System (INIS)

Solomonov, Boris N.; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

2016-01-01

Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Solomonov, Boris N., E-mail: boris.solomonov@kpfu.ru; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

2016-06-10

Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

Status on high enthalpy geothermal resources in Greece

International Nuclear Information System (INIS)

Koutinas, G.A.

1990-01-01

Greece is privileged to have many high and medium enthalpy geothermal resources. Related activities during the last 5 years were conducted mainly on the previously discovered geothermal fields of Milos, Nisyros and Lesvos islands, without any deep geothermal drilling. Most efforts were focused on the demonstration of a high enthalpy geothermal reservoir on Milos, by generating electricity from high salinity fluid, with a 2 MW pilot plant. Significant experience has been gained there, by solving technical problems, but still site specific constraints have to be overcome in order to arrive at a comprehensive feasibility study, leading to the development phase. A pre-feasibility study has been carried out in the Nisyros geothermal field. Moreover, a detailed geoscientific exploration program has been completed on Lesvos island, where very promising geothermal areas have been identified. In this paper, reference is made to the most important data concerning high enthalpy geothermal resources by emphasizing the Milos geothermal field

Vaporization, fusion and sublimation enthalpies of the dicarboxylic acids from C4 to C14 and C16

International Nuclear Information System (INIS)

Roux, Maria Victoria; Temprado, Manuel; Chickos, James S.

2005-01-01

The fusion enthalpies of the series butanedioic acid through to tetradecanedioic acid and hexadecanedioic acids have been measured by DSC. In addition to fusion, a number of solid-solid phase transitions have also been detected in these diacids. The vaporization enthalpies of these compounds have been measured by correlation gas chromatography using the vaporization enthalpies of butanedioic, hexanedioic and decanedioic acids as standards. The vaporization enthalpies of the diacids from C 4 to C 10 correlated linearly with the number of methylene groups present. Above C 10 , the vaporization enthalpies of C 11 -C 14 and C 16 begin to deviate from linearity. The vaporization enthalpies for these compounds are dependent on the temperature of the GC column used. Similar departure from linearity has also been observed previously in the sublimation enthalpies for these compounds. The results are discussed in terms of formation of a cyclic intramolecular hydrogen bonded network in the gas phase similar to the bimolecular association observed in smaller mono-carboxylic acids at ambient temperatures

A kinetic model for borosilicate glass dissolution based on the dissolution affinity of a surface alteration layer

International Nuclear Information System (INIS)

Bourcier, W.L.; Peiffer, D.W.; Knauss, K.G.; McKeegan, K.D.; Smith, D.K.

1989-11-01

A kinetic model for the dissolution of borosilicate glass is used to predict the dissolution rate of a nuclear waste glass. In the model, the glass dissolution rate is controlled by the rate of dissolution of an alkali-depleted amorphous surface (gel) layer. Our model predicts that all components concentrated in the surface layer, affect glass dissolution rates. The good agreement between predicted and observed elemental dissolution rates suggests that the dissolution rate of the gel layer limits the overall rate of glass dissolution. The model predicts that the long-term rate of glass dissolution will depend mainly on ion concentrations in solution, and therefore on the secondary phases which precipitate and control ion concentrations. 10 refs., 5 figs., 1 tab

Structure of metal β-diketonates and their enthalpies of vaporization

International Nuclear Information System (INIS)

Domrachev, G.A.; Sevast'yanov, V.G.; Zakharov, L.N.; Krasnodubskaya, S.V.; AN SSSR, Moscow. Inst. Obshchej i Neorganicheskoj Khimii)

1987-01-01

Using the method of additive schemes in combinaion with the structural estimation of the degree of screening of the central atom and other elements of β-diketonate molecule while analyzing the experimental enthalpies of vaporization, the contributions of separate fragments of complexes into the enthalpy of vaporization are found. It is shown that energies of intermolecular interaction in a condensed phase of monomeric metal β-diketonates with identical substituents do not depend on the central atom type. The enthalpies of dimer dissociation in a series of rare earth dipivaloylmethanates calculated. The proposed approach is advisable fo selecting forms of metal β-diketonates, the most suitable for the purposes of deep purificaion, which are characterized by maximum chemical and physico-chemical selectivity with respect to impurities, chemical inertness to equipment material, container, etc

Optimization of Dissolution Compartments in a Biorelevant Dissolution Apparatus Golem v2, Supported by Multivariate Analysis

Directory of Open Access Journals (Sweden)

Ivan Stupák

2017-11-01

Full Text Available Biorelevant dissolution instruments represent an important tool for pharmaceutical research and development. These instruments are designed to simulate the dissolution of drug formulations in conditions most closely mimicking the gastrointestinal tract. In this work, we focused on the optimization of dissolution compartments/vessels for an updated version of the biorelevant dissolution apparatus—Golem v2. We designed eight compartments of uniform size but different inner geometry. The dissolution performance of the compartments was tested using immediate release caffeine tablets and evaluated by standard statistical methods and principal component analysis. Based on two phases of dissolution testing (using 250 and 100 mL of dissolution medium, we selected two compartment types yielding the highest measurement reproducibility. We also confirmed a statistically ssignificant effect of agitation rate and dissolution volume on the extent of drug dissolved and measurement reproducibility.

Calorimetric measurement of the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate

International Nuclear Information System (INIS)

Srinivasan, T.G.; Vasudeva Rao, P.R.; Venugopal, V.; Sood, D.D.

2002-01-01

Enthalpy of extraction of uranyl nitrate by tri n-amyl phosphate (TAP) and its solutions in n-dodecane has been directly measured by solution calorimetry for the first time. Measurements have been made at 303±1 K, in both forward as well as the reverse extraction modes. The enthalpies of the accompanying reactions such as the dilution of the uranyl nitrate in the aqueous phase, the hydration of TAP, the mixing of TAP and n-dodecane, the mixing of the metal-solvate (UO 2 (NO 3 ) 2 ·2TAP) and n-dodecane and mixing of the metal-solvate and TAP have also been independently measured and used to derive both the equilibrium state enthalpies and the standard state enthalpies for the extraction. Two distinct standard states have been used for the organic phase, viz., 1) all solutes infinitely diluted in diluent (ΔH*) and 2) all solutes infinitely diluted in the water saturated extractant (ΔH 0 ). The results have been compared with the enthalpies of extraction measured by employing the temperature dependence of the distribution ratio as well as calorimetry reported in the literature for extraction of uranyl nitrate by TAP and TBP. (author)

Determination of vapor pressures, enthalpies of sublimation, and enthalpies of fusion of benzenetriols

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Schick, Christoph

2004-01-01

Molar enthalpies of sublimation of 1,2,4-, 1,2,3-, and 1,3,5-tri-hydroxy-benzene, were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. The molar enthalpies of fusion and molar heat capacities of these compounds were measured by DSC. The measured data sets of vaporization, sublimation and fusion enthalpies were checked for internal consistency. Strength of the inter- and intra-molecular hydrogen bonding in di- and tri-hydroxy-benzenes have been assessed

Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products

KAUST Repository

Minenkov, Yury; Sliznev, Valery V.; Cavallo, Luigi

2017-01-01

predicted the ΔHf values of a series of these compounds having a group 4, 6, or 14 metal. The ΔHf values in question were derived within a composite Feller-Dixon-Peterson (FDP) scheme based protocol that combines the DLPNO-CCSD(T) enthalpy of ad hoc designed

Enthalpy-entropy compensation in protein unfolding

Institute of Scientific and Technical Information of China (English)

无

2000-01-01

Enthalpy-entropy compensation was found to be a universal law in protein unfolding based on over 3 000 experimental data. Water molecular reorganization accompanying the protein unfolding was suggested as the origin of the enthalpy-entropy compensation in protein unfolding. It is indicated that the enthalpy-entropy compensation constitutes the physical foundation that satisfies the biological need of the small free energy changes in protein unfolding, without the sacrifice of the bio-diversity of proteins. The enthalpy-entropy compensation theory proposed herein also provides valuable insights into the Privalov's puzzle of enthalpy and entropy convergence in protein unfolding.

Interaction Between Second-Phase Particle Dissolution and Abnormal Grain Growth in an Austenitic Stainless Steel

Directory of Open Access Journals (Sweden)

Dutra J.C.

2002-01-01

Full Text Available The continuing development of stainless steels has resulted in complex steel compositions with substantial amounts of alloying elements. The benefits of such additions invariably come attached to unavoidable disadvantages. One of the most critical item is the potential microstructural instability of the material. Alloying elements may be in a supersaturated solid solution, in which the precipitation of carbides, nitrides, borides and intermetallic phases occurs in a wide range of temperatures. In order to dissolve the mentioned precipitates, solution annealing is commonly performed. However, at the temperature range in which this treatment is carried out, the onset of abnormal grain growth can occur. The interaction between the dissolution of these second-phase particles and the occurrence of abnormal grain growth is investigated in this work. This study also shows that the thermodynamics and the kinetics of dissolution of precipitates may be used to predict whether abnormal grain growth takes place.

Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products

KAUST Repository

Minenkov, Yury

2017-01-17

Accurate gas phase formation enthalpies, ΔHf, of metal oxides and halides are critical for the prediction of the stability of high temperature materials used in the aerospace and nuclear industries. Unfortunately, the experimental ΔHf values of these compounds in the most used databases, such as the NIST-JANAF database, are often reported with large inaccuracy, while some other ΔHf values clearly differ from the value predicted by CCSD(T) methods. To address this point, in this work we systematically predicted the ΔHf values of a series of these compounds having a group 4, 6, or 14 metal. The ΔHf values in question were derived within a composite Feller-Dixon-Peterson (FDP) scheme based protocol that combines the DLPNO-CCSD(T) enthalpy of ad hoc designed reactions and the experimental ΔHf values of few reference complexes. In agreement with other theoretical studies, we predict the ΔHf values for TiOCl2, TiOF2, GeF2, and SnF4 to be significantly different from the values tabulated in NIST-JANAF and other sources, which suggests that the tabulated experimental values are inaccurate. Similarly, the predicted ΔHf values for HfCl2, HfBr2, HfI2, MoOF4, MoCl6, WOF4, WOCl4, GeO2, SnO2, PbBr4, PbI4, and PbO2 also clearly differ from the tabulated experimental values, again suggesting large inaccuracy in the experimental values. In the case when largely different experimental values are available, we point to the value that is in better agreement with our results. We expect the ΔHf values reported in this work to be quite accurate, and thus, they might be used in thermodynamic calculations, because the effects from core correlation, relativistic effects, and basis set incompleteness were included in the DLPNO-CCSD(T) calculations. T1 and T2 values were thoroughly monitored as indicators of the quality of the reference Hartree-Fock orbitals (T1) and potential multireference character of the systems (T2).

Experimental standard molar enthalpies of formation of some 4-alkoxybenzoic acids

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Lobo Ferreira, Ana I.M.C.; Maciel, Fabrice M.

2010-01-01

The present work is part of a research program on the energetics of the linear 4-n-alkoxybenzoic acids, aiming the study of the enthalpic effect of the introduction of an alkoxy chain in the position 4- of the benzoic acid ring. In this work, we present the results of the thermochemical research on 4-n-alkoxybenzoic acids with the alkoxy chain length n = 2, 4, and 8. The standard (p 0 =0.1MPa) molar enthalpy of formation of crystalline 4-ethoxybenzoic acid, 4-butoxybenzoic acid, and 4-(octyloxy)benzoic acid was measured, at T = 298.15 K, by static-bomb calorimetry. These values, combined with the values of standard molar enthalpies of sublimation, were used to derive the standard molar enthalpies of formation in the gaseous phase.

A combined experimental and computational investigation of excess molar enthalpies of (nitrobenzene + alkanol) mixtures

International Nuclear Information System (INIS)

Neyband, Razieh Sadat; Zarei, Hosseinali

2015-01-01

Highlights: • Excess molar enthalpies for the binary mixtures of nitrobenzene + alkanols mixtures were measured. • The infinite dilution excess partial molar enthalpies were calculated using the ab initio methods. • The PCM calculations were performed. • The computed excess partial molar enthalpies at infinite dilution were compared to experimental results. - Abstract: Excess molar enthalpies (H m E ) for the binary mixtures of {(nitrobenzene + ethanol), 1-propanol, 2-propanol, 1-butanol and 2-butanol} have been measured over the entire composition range at ambient pressure (81.5 kPa) and temperature 298 K using a Parr 1455 solution calorimeter. From the experimental results, the excess partial molar enthalpies (H i E ) and excess partial molar enthalpies at infinite dilution (H i E,∞ ) were calculated. The excess molar enthalpies (H m E ) are positive for all {nitrobenzene (1) + alkanol (2)} mixtures over the entire composition range. A state-of-the-art computational strategy for the evaluation of excess partial molar enthalpies at infinite dilution was followed at the M05-2X/6-311++G ∗∗ level of theory with the PCM model. The experimental excess partial molar enthalpies at infinite dilution have been compared to the computational data of the ab initio in liquid phase. Integrated experimental and computational results help to clarify the nature of the intermolecular interactions in {nitrobenzene (1) + alkanol (2)} mixtures. The experimental and computational work which was done in this study complements and extends the general research on the computation of excess partial molar enthalpy at infinite dilution of binary mixtures

Dissolution rates of DWPF glasses from long-term PCT

International Nuclear Information System (INIS)

Ebert, W.L.; Tam, S.W.

1996-01-01

We have characterized the corrosion behavior of several Defense Waste Processing Facility (DWPF) reference waste glasses by conducting static dissolution tests with crushed glasses. Glass dissolution rates were calculated from measured B concentrations in tests conducted for up to five years. The dissolution rates of all glasses increased significantly after certain alteration phases precipitated. Calculation of the dissolution rates was complicated by the decrease in the available surface area as the glass dissolves. We took the loss of surface area into account by modeling the particles to be spheres, then extracting from the short-term test results the dissolution rate corresponding to a linear decrease in the radius of spherical particles. The measured extent of dissolution in tests conducted for longer times was less than predicted with this linear dissolution model. This indicates that advanced stages of corrosion are affected by another process besides dissolution, which we believe to be associated with a decrease in the precipitation rate of the alteration phases. These results show that the dissolution rate measured soon after the formation of certain alteration phases provides an upper limit for the long-term dissolution rate, and can be used to determine a bounding value for the source term for radionuclide release from waste glasses. The long-term dissolution rates measured in tests at 20,000 per m at 90 degrees C in tuff groundwater at pH values near 12 for the Environmental Assessment glass and glasses made with SRL 131 and SRL 202 frits, respectively

Ionic liquids. Combination of combustion calorimetry with high-level quantum chemical calculations for deriving vaporization enthalpies.

Science.gov (United States)

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas; Schick, Christoph

2008-07-10

In this work, the molar enthalpies of formation of the ionic liquids [C2MIM][NO3] and [C4MIM][NO3] were measured by means of combustion calorimetry. The molar enthalpy of fusion of [C2MIM][NO3] was measured using differential scanning calorimetry. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the G3MP2 theory. We have used a combination of traditional combustion calorimetry with modern high-level ab initio calculations in order to obtain the molar enthalpies of vaporization of a series of the ionic liquids under study.

Study of the thorium phosphate-diphosphate (TPD) dissolution: kinetic aspect - thermodynamic aspect: analysis of the neo-formed phases; Etude de la dissolution du phosphate diphosphate de thorium: - aspect cinetique - aspect thermodynamique: analyse des phases neoformees

Energy Technology Data Exchange (ETDEWEB)

Thomas, A.Ch

2000-10-06

The aim of this work is to study the aqueous corrosion of the thorium phosphate-diphosphate (TPD), of the formula Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, in the framework of the actinides immobilization. In order to complete the anterior studies concerning solid solutions where thorium is substituted by a tetravalent ion (uranium (IV) or plutonium (IV)) in the TPD structure, compounds of thorium and neptunium phosphate-diphosphate, of formula Th{sub 4-x}Np{sub x}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, have been prepared. Furthermore, a new chemical way of synthesis has been investigated in order to sinter solids solution of thorium and uranium phosphate-diphosphate (TUPD) in good conditions. The TPD dissolution study showed two principals steps. The first one corresponds to the control of element concentration by the material dissolution whereas the second corresponds to the formation of secondary precipitates for which thermodynamic equilibrium controls the concentration of the species in solution. Leaching tests have been performed varying several independent parameters in order to determine the TPD dissolution rate. The partial orders related to the protons or to the hydroxide ions have been found between 0.35 and 0.45 whereas the apparent dissolution rate constants are in the range 1.10{sup -5} for 9.10{sup -5} g.m{sup -2}.j{sup -1} for acidic and basic media. The neo-formed phases have been characterized after the dissolution of TPD and TUPD. We found that the TPD leaching in acidic medium leads to the formation of the crystallized thorium phosphate-hydrogen-phosphate (TPHP), of formula Th{sub 2}(PO{sub 4}){sub 2}(HPO{sub 4}), x H{sub 2}O, whereas the TUPD dissolution leads to the TPHP and an other compound, of formula (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}, 5 H{sub 2}O. We calculated its solubility product which is in good agreement with those found in the literature. The phases formed during the leaching of solids containing plutonium; americium or curium (Th

The enthalpies of formation of alkyl carbamates: Experimental and computational redetermination

International Nuclear Information System (INIS)

Santos, Ana Filipa L.O.M.; Ribeiro da Silva, Manuel A.V.

2013-01-01

Highlights: ► Combustion calorimetry was used to redetermine Δ f H m o (cr) of methyl and ethyl carbamates. ► Δ cr g H m o of methyl and ethyl carbamates were redetermined by Calvet Microcalorimetry. ► Gas-phase Δ f H m o of the studied compounds have been derived from the experimental values of Δ f H m o (cr) and Δ cr g H m o . ► Gas-phase Δ f H m o of the studied compounds have been calculated by computational thermochemistry. ► The obtained Δ f H m o (g) for the alkylcarbamates are discussed versus literature values for the same compounds. - Abstract: In the present work, a redetermination of thermochemical data of methyl carbamate and ethyl carbamate was performed by both experimental and computational techniques. Their gas-phase standard (p o = 0.1 MPa) molar enthalpies of formation, Δ f H m o (g), at T = 298.15 K, were derived from the standard molar enthalpies of formation, in the crystalline phase, Δ f H m o (cr), and from the standard molar enthalpies of sublimation, Δ cr g H m o at T = 298.15 K, measured, respectively, by static bomb combustion calorimetry and high temperature Calvet microcalorimetry. The experimental results were compared with computational data, calculated at the G3(MP2)//B3LYP level, as well as with values reported in the literature. At the B3LYP/6-31G(d) level of theory, the molecular structure of both carbamates was obtained.

Enthalpies of sublimation of fullerenes by thermogravimetry

Energy Technology Data Exchange (ETDEWEB)

Martínez-Herrera, Melchor; Campos, Myriam; Torres, Luis Alfonso; Rojas, Aarón, E-mail: arojas@cinvestav.mx

2015-12-20

Graphical abstract: - Highlights: • Enthalpies of sublimation of fullerenes were measured by thermogravimetry. • Results of enthalpies of sublimation are comparable with data reported in literature. • Not previously reported enthalpy of sublimation of C{sub 78} is supplied in this work. • Enthalpies of sublimation show a strong dependence with the number of carbon atoms in the cluster. • Enthalpies of sublimation are congruent with dispersion forces ruling cohesion of solid fullerene. - Abstract: The enthalpies of sublimation of fullerenes, as measured in the interval of 810–1170 K by thermogravimetry and applying the Langmuir equation, are reported. The detailed experimental procedure and its application to fullerenes C{sub 60}, C{sub 70}, C{sub 76}, C{sub 78} and C{sub 84} are supplied. The accuracy and uncertainty associated with the experimental results of the enthalpy of sublimation of these fullerenes show that the reliability of the measurements is comparable to that of other indirect high-temperature methods. The results also indicate that the enthalpy of sublimation increases proportionally to the number of carbon atoms in the cluster but there is also a strong correlation between the enthalpy of sublimation and the polarizability of each fullerene.

The Dissolution of Uranium Oxides in HB-Line Phase 1 Dissolvers

International Nuclear Information System (INIS)

Gray, J.H.

2003-01-01

A series of characterization and dissolution studies has been performed to define flowsheet conditions for the dissolution of uranium oxide materials in dissolvers. The samples selected for analysis were uranium oxide materials. The selection of these uranium oxide materials for characterization and dissolution studies was based on high enriched uranium content and trace levels of plutonium. Test results from the characterization study identified ferric oxide (Fe2O3) and iron/chromium/nickel (Fe/Cr/Ni) particles as impurities along with the tri-uranium oxide (U3O8) and uranium trioxide (UO3). The weight percent uranium in this material was found to vary depending on the impurity content. The trace impurity plutonium appears to be associated with the Fe/Cr/Ni particles. A small amount of absorbed moisture and waters of hydration is present. Most of the uranium oxides easily dissolved in low-molar nitric acid solutions without fluoride within one to two hours at solution temperature s between 60-80 degrees C. A small amount of residue remained following this dissolution step. To assure complete dissolution of uranium from these oxide materials, an additional dissolution step at 90 degrees C to boiling for at least one to two hours has been suggested. Only trace amounts of iron associated with Fe2O3 and Fe/Cr/Ni particles will dissolve during the dissolution steps. Neither hydrogen nor heat will be generated during the dissolution of these uranium oxide materials in nitric acid solutions. Some brown nitrogen dioxide (NO2) fumes will be generated during the dissolution of U3O8

Thermochemistry of the Dissolution of Dipeptides Containing DL-α-Alanine in Aqueous Solutions of Sodium Dodecyl Sulfate at 298.15 K

Science.gov (United States)

Smirnov, V. I.; Badelin, V. G.

2018-05-01

Enthalpies of the dissolution of DL-α-alanylglycine (AlaGly), DL-α-alanyl-DL-α-alanine (AlaAla), DL-α-alanyl-DL-α-valine (AlaVal), and DL-α-alanyl-DL-norleucine (AlaNln) in an aqueous solution of sodium dodecyl sulfate (SDS) at SDS concentration of m = 0-0.07 mol kg-1 and temperature T = 298.15 K are measured via calorimetry. The standard values of the enthalpy of dissolution (Δsol H m ) and the transfer of dipeptides (Δtr H m ) from water to aqueous SDS solutions are calculated using the experimental data. The dependences of Δsol H m and Δtr H m the SDS concentration at a constant concentration of dipeptide are established. Thermochemical characteristics of the transfer of AlaGly, AlaAla, AlaVal, and AlaNln in the investigated range of SDS concentrations are compared. The results are interpreted by considering ion-ion, ion-polar, and hydrophobic-hydrophobic interactions between SDS and dipeptide molecules.

Enthalpy of dissociation and hydration number of methane hydrate from the Clapeyron equation

International Nuclear Information System (INIS)

Anderson, Graydon K.

2004-01-01

The enthalpies of the reactions in which methane hydrate is dissociated to methane vapor and either (1) water, or (2) ice are determined by a new analysis using the Clapeyron equation. The difference in enthalpies of the two reactions is used to infer the hydration number at the quadruple point where hydrate, ice, liquid water, and methane vapor coexist. By appropriate corrections, the hydration number at points removed from the quadruple point is also determined. The most important feature of the new analysis is the direct use of the Clapeyron equation. The method avoids the use of certain simplifying assumptions that have compromised the accuracy of previous analyses in which the Clausius-Clapeyron equation was used. The analysis takes into account the finite volumes of all phases, the non-ideality of the vapor phase, and the solubility of methane in water. The results show that the enthalpy of dissociation and hydration number are constant within experimental error over the entire (hydrate, liquid, vapor) coexistence region. The results are more accurate than but entirely consistent with almost all previous studies

Enthalpies of formation of 5,6-dihydro-5-methyluracil and 5,6-dihydro-6-methyluracil

International Nuclear Information System (INIS)

Amaral, Luísa M.P.F.; Szterner, Piotr; Ribeiro da Silva, Manuel A.V.

2013-01-01

Highlights: • Δ c H m ° of two methyl-5,6-dihydrouracils have been determined by combustion calorimetry. • Vapor pressures were measured by the Knudsen effusion technique. • Gas phase enthalpies of formation of methyl-5,6-dihydrouracils, have been derived. -- Abstract: The standard (p° = 0.1 MPa) molar enthalpy of combustion, Δ c H m ° , of two crystalline compounds, 5,6-dihydro-5-methyluracil and 5,6-dihydro-6-methyluracil, were determined, at T = 298.15 K, using a static bomb combustion calorimeter. The vapor pressures as a function of the temperature were measured for those compounds, by the Knudsen effusion technique, and the standard molar enthalpies of sublimation at the mean temperature of the vapor pressure measurements were derived from the Clausius–Clapeyron equation, and corrected to T = 298.15 K using an estimated value for Δ cr g C p,m ° . These values were used to derive the standard molar enthalpies of formation of the two compounds studied, in the condensed and gaseous phases. Some considerations about the relative stability of the two isomers were made and compared with similar compounds

Formation enthalpies of Al–Fe–Zr–Nd system calculated by using geometric and Miedema's models

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lei [Department of Mathematics and Information Science, Guangxi College of Education, Nanning 530023 (China); Wang, Rongcheng; Tao, Xiaoma; Guo, Hui; Chen, Hongmei [College of Physical Science and Technology, Guangxi University, Nanning 530004 (China); Ouyang, Yifang, E-mail: ouyangyf@gxu.edu.cn [College of Physical Science and Technology, Guangxi University, Nanning 530004 (China)

2015-04-15

Formation enthalpy is important for the phase stability and amorphous forming ability of alloys. The formation enthalpies of Fe{sub 17}RE{sub 2} (RE=Ce, Pr, Nd, Gd and Er) obtained by Miedema's theory are in good agreement with those of the experiments. The dependence of formation enthalpy on concentration of Al for intermetallic (Al{sub x}Fe{sub 1−x}){sub 17}Nd{sub 2} have been calculated by Miedema's theory and the geometric model. The solid solubility of Al in (Al{sub x}Fe{sub 1−x}){sub 17}Nd{sub 2} is coincident with the concentration dependence of formation enthalpy. The mixing enthalpies of liquid alloys and formation enthalpies of alloys for Al–Fe–Zr–Nd system have been predicted. The calculated mixing enthalpy indicates that the adding of Fe or Nd decreases monotonously the magnitude of enthalpy. The formation enthalpies of Al–Fe–Zr–Nd system indicate that the shape of the enthalpy contour map changes when the content of Al is less than 50.0 at% and then it remains unchanged except the decrease of magnitude. The formation enthalpy of Al–Fe–Zr–Nd increases with the increase of Fe and/or Nd content. The negative formation enthalpy indicates that Al–Fe–Zr–Nd system has higher amorphous forming ability and wide amorphous forming range. The certain contents of Zr and/or Al are beneficial for the formation of Al–Fe–Zr–Nd intermetallics.

Enthalpy of mixing of liquid Ag–Bi–Cu alloys at 1073 K

International Nuclear Information System (INIS)

Fima, Przemysław; Flandorfer, Hans

2014-01-01

Highlights: • Partial and integral mixing enthalpies of liquid Ag–Bi–Cu alloys were determined. • Integral mixing enthalpies are small and endothermic, similar to limiting binaries. • The ternary data were fitted on the basis of Redlich–Kister–Muggianu model. - Abstract: The Ag–Bi–Cu system is among those ternary systems which have not been fully studied yet, in particular the thermodynamic description of the liquid phase is missing. Partial and integral enthalpies of mixing of liquid ternary Ag–Bi–Cu alloys were determined over a broad composition range along six sections: x(Ag)/x(Bi) = 0.25, 1, 4; x(Ag)/x(Cu) = 1.5; x(Bi)/x(Cu) = 1.86, 4. Measurements were carried out at 1073 K using two Calvet type microcalorimeters and drop calorimetric technique. It was found that integral enthalpies of mixing are small and endothermic, similarly to limiting binary alloys. The ternary data were fitted on the basis of an extended Redlich–Kister–Muggianu model for substitutional solutions. There are no significant additional ternary interactions

On the Sensitivity of Peptide Nucleic Acid Duplex Formation and Crystal Dissolution to a Variation of Force-Field Parameters.

Science.gov (United States)

Bachmann, Stephan J; Lin, Zhixiong; Stafforst, Thorsten; van Gunsteren, Wilfred F; Dolenc, Jožica

2014-01-14

The technique of one-step perturbation to explore the relation between particular force-field parameters on the one hand and particular properties of a biomolecular system on the other hand from one or a few molecular dynamics simulations is applied to investigate the dependence of the free enthalpy of dimer formation and of crystal dissolution of a self-complementary fragment (H-CGTACG-NH2) of peptide nucleic acid, PNA, a mimic of DNA. The simulations show that PNA dimer formation in aqueous solution is favored by a decrease in the base charges with respect to values of the GROMOS 45A4 force field, while it is disfavored by a decrease in the backbone charges. In contrast, crystal dissolution of the PNA dimer is favored by a decrease in base charges, while a variation of backbone charges has a minor effect on this free enthalpy change. These opposite effects in a crystalline versus aqueous solution environment can be understood from the different water contents for these systems and have consequences for biomolecular force-field development.

Aluminum Target Dissolution in Support of the Pu-238 Program

Energy Technology Data Exchange (ETDEWEB)

McFarlane, Joanna [ORNL; Benker, Dennis [ORNL; DePaoli, David W [ORNL; Felker, Leslie Kevin [ORNL; Mattus, Catherine H [ORNL

2014-09-01

Selection of an aluminum alloy for target cladding affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the caustic dissolution step, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. We present a study to maximize dissolution of aluminum metal alloy, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. These data have been compared with published calculations of aluminum phase diagrams. Temperature logging during the transients has been investigated as a means to generate kinetic and mass transport data on the dissolution process. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

Short Pulsed Laser Methods for Velocimetry and Thermometry in High Enthalpy Facilities, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — A suite of laser-based diagnostics is proposed to measure velocity and temperature simultaneously using unseeded techniques in high enthalpy flows relevant to...

A two-phase model to describe the dissolution of ZrO2 by molten Zr

International Nuclear Information System (INIS)

Belloni, J.; Fichot, F.; Goyeau, B.; Gobin, D.; Quintard, M.

2007-01-01

In case of a hypothetical severe accident in a nuclear Pressurized Water Reactor (PWR), the fuel elements in the core may reach very high temperatures (more than 2000 K). UO 2 (Uranium dioxide) pellets are enclosed by a cladding mainly composed of Zircaloy (Zr). If the temperature became higher than 2100 K (melting temperature of Zr), the UO 2 pellets would be in contact with molten Zr, resulting in the dissolution and liquefaction of UO 2 at a lower temperature than its melting points (3100 K). Several experimental and numerical investigations have led to a better understanding of this phenomenon but a comprehensive and consistent modeling is still missing. The goal of this paper is to propose a two-phase macroscopic model describing the dissolution of a solid alloy by a liquid. The model is limited to binary alloys and it is applied to the particular case of the dissolution of ZrO 2 by liquid Zr, for which experimental data are available (Hofmann et al., 1999). The model was established by using a volume averaging method. Numerical simulations are compared to experimental results and show a good agreement. (authors)

Anomalous enthalpy relaxation in vitreous silica

DEFF Research Database (Denmark)

Yue, Yuanzheng

2015-01-01

scans. It is known that the liquid fragility (i.e., the speed of the viscous slow-down of a supercooled liquid at its Tg during cooling) has impact on enthalpy relaxation in glass. Here, we find that vitreous silica (as a strong system) exhibits striking anomalies in both glass transition and enthalpy...... relaxation compared to fragile oxide systems. The anomalous enthalpy relaxation of vitreous silica is discovered by performing the hyperquenching-annealing-calorimetry experiments. We argue that the strong systems like vitreous silica and vitreous Germania relax in a structurally cooperative manner, whereas...... the fragile ones do in a structurally independent fashion. We discuss the origin of the anomalous enthalpy relaxation in the HQ vitreous silica....

Determination of the free enthalpies of formation of borosilicate glasses

International Nuclear Information System (INIS)

Linard, Y.

2000-01-01

This work contributes to the study of the thermochemical properties of nuclear waste glasses. Results are used to discuss mechanisms and parameters integrated in alteration models of conditioning materials. Glass is a disordered material defined thermodynamically as a non-equilibrium state. Taking into account one order parameter to characterise its configurational state, the metastable equilibrium for the glass was considered and the main thermochemical properties were determined. Calorimetric techniques were used to measure heat capacities and formation enthalpies of borosilicate glasses (from 3 to 8 constitutive oxides). Formation Entropies were measured too, using the entropy theory of relaxation processes proposed by Adam and Gibbs (1965). The configurational entropy contribution were determined from viscosity measurements. This set of data has allowed the calculation of Gibb's free energies of dissolution of glasses in pure water. By comparison with leaching experiments, it has been demonstrated that the decreasing of the dissolution rate at high reaction progress cannot be associated to the approach of an equilibrium between the sound glass and the aqueous solution. The composition changes of the reaction area at the glass surface need to be considered too. To achieve a complete description of the thermodynamic stability, the equilibrium between hydrated de-alkalinized glass and/or the gel layer with the aqueous solution should also be evaluated. (author)

Effect of the composition of a solution on the enthalpies of solvation of piperidine in methanol-acetonitrile and dimethylsulfoxide-acetonitrile mixed solvents

Science.gov (United States)

Kuz'mina, I. A.; Volkova, M. A.; Sitnikova, K. A.; Sharnin, V. A.

2014-01-01

Heat effects of dissolution of piperidine (ppd) are measured by calorimetry at 298.15 K over the range of composition of acetonitrile-methanol (AN-MeOH) mixed solvents. Based on the Δsol H ○(ppd)AN-MeOH values obtained using the literature data on Δsol H ○ (ppd) in acetonitrile-dimethylsulfoxide (AN-DMSO) mixed solvents and the vaporization enthalpy of ppd, the enthalpies of solvation of amine in AN-MeOH and AN-DMSO binary mixtures are calculated. A rise in the exothermicity of solvation of piperidine is observed upon the transition from AN to DMSO and MeOH, due mainly to the enhanced solvation of the amino group of ppd as a result of changes in the acid-base properties of the mixed solvent.

Dissolution studies of synthetic soddyite and uranophane

International Nuclear Information System (INIS)

Casas, I.; Perez, I.; Torrero, E.; Bruno, J.; Cera, E.; Duro, L.

1997-09-01

The dissolution of synthetically obtained soddyite and uranophane has been studied in solutions of low ionic strength. These are the likely final phases of the oxidative alternation pathway of uranium dioxide. The thermodynamic and kinetic dissolution properties of these phases have been determined at different bicarbonate concentrations. The solubilities determined in the experiments with soddyite correspond fairly well to the theoretical model calculated with a log K 0 s0 =3.9±0.7. For uranophane, the best fitting was obtained for a log K 0 s0 =11.7±0.6. The dissolution rate in the presence of bicarbonate gave for soddyite an average value of 6.8(±4.4) 10 -10 mol m -2 s -1 . For uranophane, under the same experimental conditions, the following dissolution rate equation has been derived: r 0 (mol m -2 s -1 )=10 -9±2. [HCO 3 - ] 0.69±0.09 2

Enthalpy measurement of lithium meta-titanate by drop calorimetry and its derived heat capacity

International Nuclear Information System (INIS)

Ishioka, Rika; Mukai, Keisuke; Terai, Takayuki; Suzuki, Akihiro

2013-01-01

Highlights: • Li 2 TiO 3 was synthesized by a neutralizing method. • Enthalpy of Li 2 TiO 3 was measured by a drop calorimeter. • Heat capacity of Li 2 TiO 3 was derived as a function of temperature. -- Abstract: Enthalpy of Li 2 TiO 3 , which was synthesized by a neutralizing method and its Li/Ti ratio was determined to be Li/Ti ratio (mol/mol) = 1.97, was measured by a drop calorimeter, and its heat capacity was derived as a function of temperature. XRD (X-ray diffraction) analysis of the sample before and after the enthalpy measurement indicated no phase change during the measurement and a single phase of Li 2 TiO 3 was observed. The enthalpy data were expressed as H(T) − H(323.17) (J/g) = 2.2 × 10 −5 ·T 2 + 1.4·T + 2.7 × 10 4 /T − 5.6 × 10 2 (373–1273 K), where T is temperature in K. The heat capacity was calculated as C p (J/g K) = 2.2 × 2 × 10 −5 ·T + 1.4–2.7 × 10 4 /T 2 by differentiating the equation by temperature. These equations have accuracy of 3%

Structural studies of cyclic ureas: 3. Enthalpy of formation of barbital

International Nuclear Information System (INIS)

Ribeiro da Silva, Maria das Dores M.C.; Ribeiro da Silva, Manuel A.V.; Freitas, Vera L.S.; Roux, Maria Victoria; Jimenez, Pilar; Temprado, Manuel; Davalos, Juan Z.; Cabildo, Pilar; Claramunt, Rosa M.; Elguero, Jose

2009-01-01

A thermochemical and thermophysical study has been carried out for crystalline barbital [5,5'-diethylbarbituric acid]. The thermochemical study was made by static bomb combustion calorimetry, from which the standard (p 0 =0.1MPa) molar enthalpy of formation of the crystalline barbital, at T = 298.15 K, was derived as -(753.0 ± 1.8) kJ . mol -1 . The thermophysical study was made by differential scanning calorimetry over the temperature interval (265 to 470) K. A solid-solid phase transition was found at T = 413.3 K. The vapour pressures of the crystalline barbital were measured at several temperatures between T = (355 and 377) K, by the Knudsen mass-loss effusion technique, from which the standard molar enthalpy of sublimation, at T = 298.15 K was derived as (117.3 ± 0.6) kJ . mol -1 . The combination of the experimental results yielded the standard molar enthalpy of formation of barbital in the gaseous phase, at T = 298.15 K, as -(635.8 ± 1.9) kJ . mol -1 . This value is compared and discussed with our theoretical calculations by several methods (Gaussian-n theories G2 and G3, complete basis set CBS-QB3, density functional B3P86 and B3LYP) by means of atomization and isodesmic reaction schemes.

Solubility and dissolution kinetics study of uranium phosphates and vanadates: implications for the front end of the electronuclear cycle

International Nuclear Information System (INIS)

Cretaz, F.

2013-01-01

solubility constants. Similarly, the dissolution of meta-ankoleite was preceded by a cation exchange step between K + and H 3 O + leading to the formation of (H 3 O) 2x K 2x-2 (UO 2 ) 2 (PO 4 ) 2.6 H 2 O (0 ≤ x ≤ 2) solid solutions, whose solubility constant have been evaluated. Finally, meta-torbernite and carnotite presented congruent dissolutions which allowed the determination of thermodynamic data of interest such as solubility products and standard enthalpy, Gibbs free energy and entropy associated with the dissolution reaction (Δ r H 0 , Δ r G 0 et Δ r S 0 ) and formation of each phase (Δ f H 0 , Δ f G 0 and Δ f S 0 ). The results obtained evidenced very low and similar solubility constants for the three phosphate phases studied (10 -53 ≤ K s,0 0 ≤ 10 -45 ). Such small variation directly came from the closely related crystal structures previously described. In addition, the difference in composition of the sheets between phosphate and vanadate phases led to greater stability of carnotite (K s,0 0 = 10 -63 ) compared to phosphates phases. The solubility values derived from this study for phosphates and vanadates uranium(VI) allowed estimating values for similar phases. These data were also used in a geochemical model for the prediction of neo-formed phases in a real case (water of a lake near an uranium deposit). (author) [fr

Calculation of Five Thermodynamic Molecular Descriptors by Means of a General Computer Algorithm Based on the Group-Additivity Method: Standard Enthalpies of Vaporization, Sublimation and Solvation, and Entropy of Fusion of Ordinary Organic Molecules and Total Phase-Change Entropy of Liquid Crystals

Directory of Open Access Journals (Sweden)

Rudolf Naef

2017-06-01

Full Text Available The calculation of the standard enthalpies of vaporization, sublimation and solvation of organic molecules is presented using a common computer algorithm on the basis of a group-additivity method. The same algorithm is also shown to enable the calculation of their entropy of fusion as well as the total phase-change entropy of liquid crystals. The present method is based on the complete breakdown of the molecules into their constituting atoms and their immediate neighbourhood; the respective calculations of the contribution of the atomic groups by means of the Gauss-Seidel fitting method is based on experimental data collected from literature. The feasibility of the calculations for each of the mentioned descriptors was verified by means of a 10-fold cross-validation procedure proving the good to high quality of the predicted values for the three mentioned enthalpies and for the entropy of fusion, whereas the predictive quality for the total phase-change entropy of liquid crystals was poor. The goodness of fit (Q2 and the standard deviation (σ of the cross-validation calculations for the five descriptors was as follows: 0.9641 and 4.56 kJ/mol (N = 3386 test molecules for the enthalpy of vaporization, 0.8657 and 11.39 kJ/mol (N = 1791 for the enthalpy of sublimation, 0.9546 and 4.34 kJ/mol (N = 373 for the enthalpy of solvation, 0.8727 and 17.93 J/mol/K (N = 2637 for the entropy of fusion and 0.5804 and 32.79 J/mol/K (N = 2643 for the total phase-change entropy of liquid crystals. The large discrepancy between the results of the two closely related entropies is discussed in detail. Molecules for which both the standard enthalpies of vaporization and sublimation were calculable, enabled the estimation of their standard enthalpy of fusion by simple subtraction of the former from the latter enthalpy. For 990 of them the experimental enthalpy-of-fusion values are also known, allowing their comparison with predictions, yielding a correlation

Calculation of Five Thermodynamic Molecular Descriptors by Means of a General Computer Algorithm Based on the Group-Additivity Method: Standard Enthalpies of Vaporization, Sublimation and Solvation, and Entropy of Fusion of Ordinary Organic Molecules and Total Phase-Change Entropy of Liquid Crystals.

Science.gov (United States)

Naef, Rudolf; Acree, William E

2017-06-25

The calculation of the standard enthalpies of vaporization, sublimation and solvation of organic molecules is presented using a common computer algorithm on the basis of a group-additivity method. The same algorithm is also shown to enable the calculation of their entropy of fusion as well as the total phase-change entropy of liquid crystals. The present method is based on the complete breakdown of the molecules into their constituting atoms and their immediate neighbourhood; the respective calculations of the contribution of the atomic groups by means of the Gauss-Seidel fitting method is based on experimental data collected from literature. The feasibility of the calculations for each of the mentioned descriptors was verified by means of a 10-fold cross-validation procedure proving the good to high quality of the predicted values for the three mentioned enthalpies and for the entropy of fusion, whereas the predictive quality for the total phase-change entropy of liquid crystals was poor. The goodness of fit ( Q ²) and the standard deviation (σ) of the cross-validation calculations for the five descriptors was as follows: 0.9641 and 4.56 kJ/mol ( N = 3386 test molecules) for the enthalpy of vaporization, 0.8657 and 11.39 kJ/mol ( N = 1791) for the enthalpy of sublimation, 0.9546 and 4.34 kJ/mol ( N = 373) for the enthalpy of solvation, 0.8727 and 17.93 J/mol/K ( N = 2637) for the entropy of fusion and 0.5804 and 32.79 J/mol/K ( N = 2643) for the total phase-change entropy of liquid crystals. The large discrepancy between the results of the two closely related entropies is discussed in detail. Molecules for which both the standard enthalpies of vaporization and sublimation were calculable, enabled the estimation of their standard enthalpy of fusion by simple subtraction of the former from the latter enthalpy. For 990 of them the experimental enthalpy-of-fusion values are also known, allowing their comparison with predictions, yielding a correlation coefficient R

The Substitution Effect on Reaction Enthalpies of Antioxidant Mechanisms of Juglone and Its Derivatives in Gas and Solution Phase: DFT Study

Directory of Open Access Journals (Sweden)

Aymard Didier Tamafo Fouegue

2018-01-01

Full Text Available We examined the structure-reaction enthalpies-antioxidant activity relationship of the molecule library built around juglone and its derivatives at B3LYP/6-31+G(d,p level. Three major antioxidant mechanisms (hydrogen atom transfer (HAT, single electron transfer-proton transfer (SET-PT, and sequential proton loss electron transfer (SPLET have been investigated in five solvents and in the gas phase. The delocalization of the unpaired electrons in the radicals or cation radicals has been explored by the natural bond orbital analysis and the interpretation of spin density maps. The results obtained have proven that the HAT mechanism is the thermodynamically preferred mechanism in the gas phase. But, in the solution phase, the SPLET mechanism has been shown to be more predominant than HAT. The reactivity order of compounds towards selected reactive oxygen species has also been studied.

Status report on dissolution model development

International Nuclear Information System (INIS)

Jackson, D.D.

1983-07-01

The computer program PROTOCOL models the dissolution reactions of chemical species in water. It is being developed particularly to study the dissolution of proposed nuclear waste forms and related phases. Experimentally derived leaching rate functions are coupled to thermochemical equilibrium calculations and water flow rates. The program has been developed over a period of years. This report describes improvements that have been done in the past year

Fabrication of a Porous Metal via Selective Phase Dissolution in Al-Cu Alloys

Directory of Open Access Journals (Sweden)

Juan Vargas-Martínez

2018-05-01

Full Text Available Through free corrosion, a new low cost porous material was successfully fabricated by removing a single phase of a binary aluminum-copper alloy. This selective phase dissolution was carried out an Al-Al2Cu eutectic alloy of the Al-Cu binary system and additionally for two hypereutectic compositions. The porosity of the material depends on the microstructure formed upon solidification. For this reason, several solidification methods were studied to define the most convenient in terms of uniformity and refinement of the average pore and ligament sizes. The samples were corroded in a 10% v/v NaOH aqueous solution, which demonstrated to be the most convenient in terms of time involved and resulting porosity conditions after the corrosion process. The porosity was measured through analysis of secondary electron images. The effectiveness of the process was verified using X-ray diffraction, which showed that, under the proposed methodology, there was complete removal of one of the phases, namely the aluminum one.

Standard molar enthalpies of formation of 1-methyl-2-piperidinemethanol, 1-piperidineethanol, and 2-piperidineethanol

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Cabral, Joana I.T.A.

2006-01-01

The standard (p o =0.1MPa) molar enthalpies of combustion, Δ c H m o , for the liquid compounds 1-methyl-2-piperidinemethanol, 1-piperidineethanol, and 2-piperidineethanol, were measured by static bomb calorimetry, in oxygen, at T=298.15K. The standard molar enthalpies of vaporization, at T=298.15K, of these three liquid compounds were determined by Calvet microcalorimetry. -Δ c H m o (l)/(kJ.mol -1 )Δ l g H m o /(kJ.mol -1 )1-Methyl-2-piperidinemethanol4598.3+/-1.868. 22+/-0.711-Piperidineethanol4595.2+/-1.764.18+/-0.812 -Piperidineethanol4566.2+/-1.375.24+/-0.52 These values, were used to derive the standard molar enthalpies of formation of the compounds, at T=298.15K, in their liquid and gaseous phase, respectively. The derived standard molar enthalpies of formation, in the gaseous state, are analyzed in terms of enthalpic increments and interpreted in terms of molecular structure.

Enthalpy-based equation of state for highly porous materials employing modified soft sphere fluid model

Science.gov (United States)

Nayak, Bishnupriya; Menon, S. V. G.

2018-01-01

Enthalpy-based equation of state based on a modified soft sphere model for the fluid phase, which includes vaporization and ionization effects, is formulated for highly porous materials. Earlier developments and applications of enthalpy-based approach had not accounted for the fact that shocked states of materials with high porosity (e.g., porosity more than two for Cu) are in the expanded fluid region. We supplement the well known soft sphere model with a generalized Lennard-Jones formula for the zero temperature isotherm, with parameters determined from cohesive energy, specific volume and bulk modulus of the solid at normal condition. Specific heats at constant pressure, ionic and electronic enthalpy parameters and thermal excitation effects are calculated using the modified approach and used in the enthalpy-based equation of state. We also incorporate energy loss from the shock due to expansion of shocked material in calculating porous Hugoniot. Results obtained for Cu, even up to initial porosities ten, show good agreement with experimental data.

Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

International Nuclear Information System (INIS)

Kubatko, K.; Helean, K.; Navrotsky, A.; Burns, P.C.

2005-01-01

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO 2 ) 4 O(OH) 6 ](H 2 O) 5 , metaschoepite; β-UO 2 (OH) 2 ; CaUO 4 ; Ca(UO 2 ) 6 O 4 (OH) 6 (H 2 O) 8 , becquerelite; Ca(UO 2 ) 4 O 3 (OH) 4 (H 2 O) 2 ; Na(UO 2 )O(OH), clarkeite; Na 2 (UO 2 ) 6 O 4 (OH) 6 (H 2 O) 7 , the sodium analogue of compreignacite and Pb 3 (UO 2 ) 8 O 8 (OH) 6 (H 2 O) 2 , curite. The enthalpy of formation from the binary oxides, ΔH f-ox , at 298 K was calculated for each compound from the respective drop solution enthalpy, ΔH ds . The standard enthalpies of formation from the elements, ΔH f o , at 298 K are -1791.0 ± 3.2, -1536.2 ± 2.8, -2002.0 ± 3.2, -11389.2 ± 13.5, -6653.1 ± 13.8, -1724.7 ± 5.1, -10936.4 ± 14.5 and -13163.2 ± 34.4 kJ mol -1 , respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments

Enthalpies of a binary alloy during solidification

Science.gov (United States)

Poirier, D. R.; Nandapurkar, P.

1988-01-01

The purpose of the paper is to present a method of calculating the enthalpy of a dendritic alloy during solidification. The enthalpies of the dendritic solid and interdendritic liquid of alloys of the Pb-Sn system are evaluated, but the method could be applied to other binaries, as well. The enthalpies are consistent with a recent evaluation of the thermodynamics of Pb-Sn alloys and with the redistribution of solute in the same during dendritic solidification. Because of the heat of mixing in Pb-Sn alloys, the interdendritic liquid of hypoeutectic alloys (Pb-rich) of less than 50 wt pct Sn has enthalpies that increase as temperature decreases during solidification.

Probing the Production of Extreme-ultraviolet Late-phase Solar Flares Using the Model Enthalpy-based Thermal Evolution of Loops

Science.gov (United States)

Dai, Yu; Ding, Mingde

2018-04-01

Recent observations in extreme-ultraviolet (EUV) wavelengths reveal an EUV late phase in some solar flares that is characterized by a second peak in warm coronal emissions (∼3 MK) several tens of minutes to a few hours after the soft X-ray (SXR) peak. Using the model enthalpy-based thermal evolution of loops (EBTEL), we numerically probe the production of EUV late-phase solar flares. Starting from two main mechanisms of producing the EUV late phase, i.e., long-lasting cooling and secondary heating, we carry out two groups of numerical experiments to study the effects of these two processes on the emission characteristics in late-phase loops. In either of the two processes an EUV late-phase solar flare that conforms to the observational criteria can be numerically synthesized. However, the underlying hydrodynamic and thermodynamic evolutions in late-phase loops are different between the two synthetic flare cases. The late-phase peak due to a long-lasting cooling process always occurs during the radiative cooling phase, while that powered by a secondary heating is more likely to take place in the conductive cooling phase. We then propose a new method for diagnosing the two mechanisms based on the shape of EUV late-phase light curves. Moreover, from the partition of energy input, we discuss why most solar flares are not EUV late flares. Finally, by addressing some other factors that may potentially affect the loop emissions, we also discuss why the EUV late phase is mainly observed in warm coronal emissions.

High enthalpy gas dynamics

CERN Document Server

Rathakrishnan, Ethirajan

2014-01-01

This is an introductory level textbook which explains the elements of high temperature and high-speed gas dynamics. written in a clear and easy to follow style, the author covers all the latest developments in the field including basic thermodynamic principles, compressible flow regimes and waves propagation in one volume covers theoretical modeling of High Enthalpy Flows, with particular focus on problems in internal and external gas-dynamic flows, of interest in the fields of rockets propulsion and hypersonic aerodynamics High enthalpy gas dynamics is a compulsory course for aerospace engine

Grain boundary corrosion and alteration phase formation during the oxidative dissolution of UO2 pellets

International Nuclear Information System (INIS)

Wronkiewicz, D.J.; Buck, E.C.; Bates, J.K.

1996-01-01

Alteration behavior of UO 2 pellets following reaction under unsaturated drip-test conditions at 90 C for up to 10 years was examined by solid phase and leachate analyses. Sample reactions were characterized by preferential dissolution of grain boundaries between the original press-sintered UO 2 granules comprising the samples, development of a polygonal network of open channels along the intergrain boundaries, and spallation of surface granules that had undergone severe grain boundary corrosion. The development of a dense mat of alteration phases after 2 years of reaction trapped loose granules, resulting in reduced rates of particulate U release. The paragenetic sequence of alteration phases that formed on the present samples was similar to that observed in surficial weathering zones of natural uraninite (UO 2 ) deposits, with alkali and alkaline earth uranyl silicates representing the long-term solubility-limiting phases for U in both systems

Spectral emissivities at wavelengths in the range 500--653 nm, enthalpies, and heat capacities of the liquid phases of cobalt, titanium, and zirconium

International Nuclear Information System (INIS)

Qin, J.; Roesner-Kuhn, M.; Drewes, K.; Thiedemann, U.; Kuppermann, G.; Camin, B.; Blume, R.; Frohberg, M.G.

1997-01-01

A review is given of the literature data for spectral emissivities at wavelengths (λ) in the range 500--653 nm, the enthalpies, and heat capacities of the liquid phases of cobalt, titanium, and zirconium. Emissivity measurements were carried out by means of electromagnetic levitation at the solid-to-liquid transition with a partial-radiation pyrometer operating at λ = 547 and 650 nm. Considering the sensitivity of the optical properties to surface impurities, investigations on the surfaces of several titanium and zirconium samples by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) were performed that confirmed a nitrogen- and oxygen-free process atmosphere during the measurements. Liquid phase normal emissivities obtained were var-epsilon n,547 = 0.365 and var-epsilon n,650 = 0.331 for cobalt, var-epsilon n,547 = 0.409 and var-epsilon n,650 = 0.393 for titanium, and var-epsilon n,547 = 0.365 and var-epsilon n,650 = 0.355 for zirconium. Enthalpy measurements on the liquid metals were carried out by means of levitation-drop calorimetry in the range 1591--2159 K for cobalt, 1847--2430 K for titanium, and 2025--2897 K for zirconium. The resulting heat capacities (values in J·mol -1 ·K -1 ) obtained were 42.78 for cobalt, 43.79 for titanium, and 39.81 for zirconium

Enthalpy of mixing of liquid Co–Sn alloys

International Nuclear Information System (INIS)

Yakymovych, A.; Fürtauer, S.; Elmahfoudi, A.; Ipser, H.; Flandorfer, H.

2014-01-01

Highlights: • The enthalpies of mixing of liquid Co–Sn alloys between T = (673 and 1773) K. • The temperature dependence of the enthalpies of mixing was described. • Full report of measured values including polynomial coefficients. - Abstract: A literature overview of enthalpy of mixing data for liquid Co–Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co–Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich–Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co–Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. −7820 J/mol at T = 1173 K to −1350 J/mol at T = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process

Dissolution process of atmospheric aerosol particles into cloud droplets; Processus de dissolution des aerosols atmospheriques au sein des gouttes d'eau nuageuses

Energy Technology Data Exchange (ETDEWEB)

Desboeufs, K

2001-01-15

Clouds affect both climate via the role they play in the Earth's radiation balance and tropospheric chemistry since they are efficient reaction media for chemical transformation of soluble species. Cloud droplets are formed in the atmosphere by condensation of water vapour onto aerosol particles, the cloud condensation nuclei (CCN). The water soluble fraction of these CCN governs the cloud micro-physics, which is the paramount factor playing on the radiative properties of clouds. Moreover, this soluble fraction is the source of species imply in the oxidation/reduction reactions in the aqueous phase. Thus, it is of particular importance to understand the process controlling the solubilization of aerosols in the cloud droplets. The main purpose of this work is to investigate experimentally and theoretically the dissolution of particles incorporated in the aqueous phase. From the studies conducted up to now, we have identify several factors playing on the dissolution reaction of aerosols. However, the quantification of the effects of these factors is difficult since the current means of study are not adapted to the complexity of cloud systems. First, this work consisted to perform a experimental system, compound by an open flow reactor, enabling to follow the kinetic of dissolution in conditions representative of cloud. This experimental device is used to a systematic characterisation of the known factors playing on the dissolution, i.e. pH, aerosol nature, aerosol weathering... and also for the identification and the quantification of the effects of other factors: ionic strength, acid nature, clouds processes. These experiments gave quantitative results, which are used to elaborate a simple model of aerosol dissolution in the aqueous phase. This model considers the main factors playing on the dissolution and results in a general mechanism of aerosol dissolution extrapolated to the cloud droplets. (author)

A mass spectrometric study of the neutral and ionic vapor components of ytterbium chlorides; formation enthalpies of YbCl2 and YbCl3 molecules, and YbCl3- and YbCl4- ions in the gas phase

International Nuclear Information System (INIS)

Kuznetsov, F.Yh.; Kudin, L.S.; Pogrebnoj, A.M.; Butman, M.F.; Burdukovskaya, G.G.

1997-01-01

Ionic and neutral components of saturated vapour over the ytterbium di-and trichloride is studied through the Knudsen effusive method with mass-spectromic registration of evaporated products within the temperature range of 1000-1300 K. It is found that ytterbium trichloride is subjected to thermal decomposition with formation of ytterbium dichloride and molecular chloride. Sublimation enthalpy and enthalpy of YbCl 2 and YbCl 3 molecules formation in a gaseous phase at 298 K, comprising 356±6, 293±8, -425±6 and -667±6 kJ/mole correspondingly, are determined with application of 2 and 3 thermodynamical laws. Enthalpies of YbCl 3 - and YbCl 4 - negative ions formation in a gaseous phase at 298 K equal to -895 and -1211±30 kJ/mole correspondingly are calculated by measured equilibrium constants ion-molecular reaction. 30 refs., 3 figs., 3 tabs

Transition from Endothermic to Exothermic Dissolution of Hydroxyapatite Ca5(PO43OH–Johnbaumite Ca5(AsO43OH Solid Solution Series at Temperatures Ranging from 5 to 65 °C

Directory of Open Access Journals (Sweden)

Bartosz Puzio

2018-06-01

Full Text Available Five crystalline members of the hydroxyapatite (HAP; Ca5(PO43OH–johnbaumite (JBM; Ca5(AsO43OH series were crystallized at alkaline pH from aqueous solutions and used in dissolution experiments at 5, 25, 45, and 65 °C. Equilibrium was established within three months. Dissolution was slightly incongruent, particularly at the high-P end of the series. For the first time, the Gibbs free energy of formation ΔGf0, enthalpy of formation ΔHf0, entropy of formation Sf0, and specific heat of formation Copf were determined for HAP–JBM solid solution series. Based on the dissolution reaction, Ca5(AsO4m(PO43−mOH = 5Ca2+(aq + mAsO43−(aq + (3 − mPO43−(aq + OH−(aq, their solubility product Ksp,298.15 was determined. Substitution of arsenic (As for phosphorus (P in the structure of apatite resulted in a linear increase in the value of Ksp: from HAP logKsp,298.15 = −57.90 ± 1.57 to JBM logKsp,298.15 = −39.22 ± 0.56. The temperature dependence of dissolution in this solid solution series is very specific; in the temperature range of 5 °C to 65 °C, the enthalpy of dissolution ΔHr varied around 0. For HAP, the dissolution reaction at 5 °C and 25 °C was endothermic, which transitioned at around 40 °C and became exothermic at 45 °C and 65 °C.

Calibration of a T-History calorimeter to measure enthalpy curves of phase change materials in the temperature range from 40 to 200 °C

International Nuclear Information System (INIS)

Rathgeber, Christoph; Schmit, Henri; Hennemann, Peter; Hiebler, Stefan

2014-01-01

Thermal energy storage using phase change materials (PCMs) provides high storage capacities in small temperature ranges. For the design of efficient latent heat storage, the enthalpy curve of a PCM has to be measured with high precision. Measurements are most commonly performed with differential scanning calorimetry (DSC). The T-History method, however, proved to be favourable for the characterization of typical PCMs due to large samples and a measuring procedure close to conditions found in applications. As T-History calorimeters are usually individual constructions, performing a careful calibration procedure is decisive to ensure optimal measuring accuracy. We report in this paper on the calibration of a T-History calorimeter with a working range from 40 to 200 °C that was designed and built at our institute. A three-part procedure, consisting of an indium calibration, a measurement of the specific heat of copper and measurements of three solid–liquid PCMs (stearic acid, dimethyl terephthalate and d-mannitol), was performed and an advanced procedure for the correction of enthalpy curves was developed. When comparing T-History enthalpy curves to literature data and DSC step measurements, good agreement within the uncertainty limits demanded by RAL testing specifications was obtained. Thus, our design of a T-History calorimeter together with the developed calibration procedure provides the measuring accuracy that is required to identify the most suitable PCM for a given application. In addition, the dependence of the enthalpy curve on the sample size can be analysed by comparing results obtained with T-History and DSC and the behaviour of the bulk material in real applications can be predicted. (paper)

Calculating the enthalpy of vaporization for ionic liquid clusters.

Science.gov (United States)

Kelkar, Manish S; Maginn, Edward J

2007-08-16

Classical atomistic simulations are used to compute the enthalpy of vaporization of a series of ionic liquids composed of 1-alkyl-3-methylimidazolium cations paired with the bis(trifluoromethylsulfonyl)imide anion. The calculations show that the enthalpy of vaporization is lowest for neutral ion pairs. The enthalpy of vaporization increases by about 40 kJ/mol with the addition of each ion pair to the vaporizing cluster. Non-neutral clusters have much higher vaporization enthalpies than their neutral counterparts and thus are not expected to make up a significant fraction of volatile species. The enthalpy of vaporization increases slightly as the cation alkyl chain length increases and as temperature decreases. The calculated vaporization enthalpies are consistent with two sets of recent experimental measurements as well as with previous atomistic simulations.

A DFT study on the enthalpies of thermite reactions and enthalpies of formation of metal composite oxide

Science.gov (United States)

Zhang, Yu-ying; Wang, Meng-jie; Chang, Chun-ran; Xu, Kang-zhen; Ma, Hai-xia; Zhao, Feng-qi

2018-05-01

The standard thermite reaction enthalpies (ΔrHmθ) for seven metal oxides were theoretically analyzed using density functional theory (DFT) under five different functional levels, and the results were compared with experimental values. Through the comparison of the linear fitting constants, mean error and root mean square error, the Perdew-Wang functional within the framework of local density approximation (LDA-PWC) and Perdew-Burke-Ernzerhof exchange-correlation functional within the framework of generalized gradient approximation (GGA-PBE) were selected to further calculate the thermite reaction enthalpies for metal composite oxides (MCOs). According to the Kirchhoff formula, the standard molar reaction enthalpies for these MCOs were obtained and their standard molar enthalpies of formation (ΔfHmθ) were finally calculated. The results indicated that GGA-PBE is the most suitable one out of the total five methods to calculate these oxides. Tungstate crystals present the maximum deviation of the enthalpies of thermite reactions for MCOs and these of their physical metal oxide mixtures, but ferrite crystals are the minimum. The correlation coefficients are all above 0.95, meaning linear fitting results are very precise. And the molar enthalpies of formation for NiMoO4, CuMoO4, PbZrO3 (Pm/3m), PbZrO3 (PBA2), PbZrO3 (PBam), MgZrO3, CdZrO3, MnZrO3, CuWO4 and Fe2WO6 were first obtained as -1078.75, -1058.45, -1343.87, -1266.54, -1342.29, -1333.03, -1210.43, -1388.05, -1131.07 and - 1860.11 kJ·mol-1, respectively.

The Calculation of Standard Enthalpies of Formation of Alkanes: Illustrating Molecular Mechanics and Spreadsheet Programs

Science.gov (United States)

Hawk, Eric Leigh

1999-02-01

How group increment methods may be used to predict standard enthalpies of formation of alkanes is outlined as an undergraduate computational chemistry experiment. The experiment requires input and output data sets. Although users may create their own data sets, both sets are provided. The input data set contains experimentally determined gas-phase standard enthalpies of formation and calculated steric energies for 10 alkanes. The steric energy for an alkane is calculated via a Molecular Mechanics approach employing Allinger's MM3 force field. Linear regression analysis on data contained in the input data set generates the coefficients that are used with the output data set to calculate standard enthalpies of formation for 15 alkanes. The average absolute error for the calculated standard enthalpies of formation is 1.22 kcal/mol. The experiment is highly suited to those interested in incorporating more computational chemistry in their curricula. In this regard, it is ideally suited for a physical chemistry laboratory, but it may be used in an organic chemistry course as well.

Dissolution process of atmospheric aerosol particles into cloud droplets; Processus de dissolution des aerosols atmospheriques au sein des gouttes d'eau nuageuses

Energy Technology Data Exchange (ETDEWEB)

Desboeufs, K.

2001-01-15

Clouds affect both climate via the role they play in the Earth's radiation balance and tropospheric chemistry since they are efficient reaction media for chemical transformation of soluble species. Cloud droplets are formed in the atmosphere by condensation of water vapour onto aerosol particles, the cloud condensation nuclei (CCN). The water soluble fraction of these CCN governs the cloud micro-physics, which is the paramount factor playing on the radiative properties of clouds. Moreover, this soluble fraction is the source of species imply in the oxidation/reduction reactions in the aqueous phase. Thus, it is of particular importance to understand the process controlling the solubilization of aerosols in the cloud droplets. The main purpose of this work is to investigate experimentally and theoretically the dissolution of particles incorporated in the aqueous phase. From the studies conducted up to now, we have identify several factors playing on the dissolution reaction of aerosols. However, the quantification of the effects of these factors is difficult since the current means of study are not adapted to the complexity of cloud systems. First, this work consisted to perform a experimental system, compound by an open flow reactor, enabling to follow the kinetic of dissolution in conditions representative of cloud. This experimental device is used to a systematic characterisation of the known factors playing on the dissolution, i.e. pH, aerosol nature, aerosol weathering... and also for the identification and the quantification of the effects of other factors: ionic strength, acid nature, clouds processes. These experiments gave quantitative results, which are used to elaborate a simple model of aerosol dissolution in the aqueous phase. This model considers the main factors playing on the dissolution and results in a general mechanism of aerosol dissolution extrapolated to the cloud droplets. (author)

Enthalpy model for heating, melting, and vaporization in laser ablation

Directory of Open Access Journals (Sweden)

Vasilios Alexiades

2010-09-01

Full Text Available Laser ablation is used in a growing number of applications in various areas including medicine, archaeology, chemistry, environmental and materials sciences. In this work the heat transfer and phase change phenomena during nanosecond laser ablation of a copper (Cu target in a helium (He background gas at atmospheric pressure are presented. An enthalpy model is outlined, which accounts for heating, melting, and vaporization of the target. As far as we know, this is the first model that connects the thermodynamics and underlying kinetics of this challenging phase change problem in a self-consistent way.

Enthalpy of mixing and heat of vaporization of ethyl acetate with benzene and toluene at 298.15 k and 308.15 k

OpenAIRE

K. L. Shivabasappa; P. Nirguna Babu; Y. Jagannadha Rao

2008-01-01

The present work was carried out in two phases. First, enthalpy of mixing was measured and then the heat of vaporization for the same mixtures was obtained. The data are useful in the design of separation equipments. From the various designs available for the experimental determination of enthalpy of mixing, and heat of vaporization, the apparatus was selected, modified and constructed. The apparatus of enthalpy of mixing was tested with a known system Benzene - i-Butyl Alcohol and the data o...

Grain boundary corrosion and alteration phase formation during the oxidative dissolution of UO{sub 2} pellets

Energy Technology Data Exchange (ETDEWEB)

Wronkiewicz, D.J.; Buck, E.C.; Bates, J.K.

1996-12-31

Alteration behavior of UO{sub 2} pellets following reaction under unsaturated drip-test conditions at 90 C for up to 10 years was examined by solid phase and leachate analyses. Sample reactions were characterized by preferential dissolution of grain boundaries between the original press-sintered UO{sub 2} granules comprising the samples, development of a polygonal network of open channels along the intergrain boundaries, and spallation of surface granules that had undergone severe grain boundary corrosion. The development of a dense mat of alteration phases after 2 years of reaction trapped loose granules, resulting in reduced rates of particulate U release. The paragenetic sequence of alteration phases that formed on the present samples was similar to that observed in surficial weathering zones of natural uraninite (UO{sub 2}) deposits, with alkali and alkaline earth uranyl silicates representing the long-term solubility-limiting phases for U in both systems.

Experimental Determination of the Formation Enthalpy of Calcium Cobaltate from Sol–Gel Precursors

DEFF Research Database (Denmark)

Holgate, Tim C.; Wu, NingYu; Van Nong, Ngo

2017-01-01

Calcium cobaltate (Ca3Co4O9) remains one of the most promising p-type oxide materials for high-temperature thermoelectric energy conversion. While much progress has been made in refining our understanding of the unique structure of the material, as well as optimization of the transport properties...... as observations of its decomposition into the Ca3Co2O6 phase. The reaction enthalpy of forming Ca3Co4O9 from CaCO3 and Co3O4 sol–gel precursors was determined to be +284 (±2%) kJ/mol, leading to a standard enthalpy of Ca3Co4O9 of −3307 (±3.5%) kJ/mol....

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Science.gov (United States)

Osten, Julia; Milkereit, Benjamin; Schick, Christoph; Kessler, Olaf

2015-01-01

In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181) in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed) was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC) was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Directory of Open Access Journals (Sweden)

Julia Osten

2015-05-01

Full Text Available In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181 in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

Energy Technology Data Exchange (ETDEWEB)

K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

2005-05-11

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

Standard enthalpies of formation of selected Rh2YZ Heusler compounds

International Nuclear Information System (INIS)

Yin, Ming; Nash, Philip

2015-01-01

The standard enthalpies of formation (Δ f H°) of selected ternary Rh-based Rh 2 YZ (Y = Cu, Fe, Mn, Ni, Ru, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) compounds were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation (in kJ/mol of atoms) are, for the Heusler compound Rh 2 MnSn (−40.1 ± 3.6), for the B2-structured compounds: Rh 2 FeAl (−48.5 ± 2.9); Rh 2 MnAl (−72.4 ± 2.7); Rh 2 MnGa (−55.3 ± 2.0); Rh 2 MnIn (−35.3 ± 1.9), for the tetragonal compounds: Rh 2 FeSn (−28.9 ± 1.3); Rh 2 TiAl (−97.6 ± 2.2); Rh 2 TiGa (−79.0 ± 1.8); Rh 2 TiSn (−74.7 ± 3.1). Values are compared with those from first principles calculations in published papers and the Open Quantum Materials Database (OQMD). Lattice parameters of these compounds are determined using X-ray diffraction analysis (XRD). Microstructures were characterized using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). - Highlights: • Standard enthalpies of formation of Rh 2 YZ were measured using a drop calorimeter. • Measured enthalpies agree with first principles data in general. • Lattice parameters and related phase relationships were consistent with literature data. • Rh 2 TiSn of tI8 structure were reported for the first time.

Understanding cellulose dissolution: energetics of interactions of ionic liquids and cellobiose revealed by solution microcalorimetry.

Science.gov (United States)

de Oliveira, Heitor Fernando Nunes; Rinaldi, Roberto

2015-05-11

In this report, the interactions between fifteen selected ionic liquids (ILs) and cellobiose (CB) are examined by high-precision solution microcalorimetry. The heat of mixing (Δmix H) of CB and ILs, or CB and IL/molecular solvent (MS) solutions, provides the first ever-published measure of the affinity of CB with ILs. Most importantly, we found that there is a very good correlation between the nature of the results found for Δmix H(CB) and the solubility behavior of cellulose. This correlation suggests that Δmix H(CB) offers a good estimate of the enthalpy of dissolution of cellulose even in solvents in which cellulose is insoluble. Therefore, the current findings open up new horizons for unravelling the intricacies of the thermodynamic factors accounting for the spontaneity of cellulose dissolution in ILs or IL/MS solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enthalpy-entropy compensation: the role of solvation.

Science.gov (United States)

Dragan, Anatoliy I; Read, Christopher M; Crane-Robinson, Colyn

2017-05-01

Structural modifications to interacting systems frequently lead to changes in both the enthalpy (heat) and entropy of the process that compensate each other, so that the Gibbs free energy is little changed: a major barrier to the development of lead compounds in drug discovery. The conventional explanation for such enthalpy-entropy compensation (EEC) is that tighter contacts lead to a more negative enthalpy but increased molecular constraints, i.e., a compensating conformational entropy reduction. Changes in solvation can also contribute to EEC but this contribution is infrequently discussed. We review long-established and recent cases of EEC and conclude that the large fluctuations in enthalpy and entropy observed are too great to be a result of only conformational changes and must result, to a considerable degree, from variations in the amounts of water immobilized or released on forming complexes. Two systems exhibiting EEC show a correlation between calorimetric entropies and local mobilities, interpreted to mean conformational control of the binding entropy/free energy. However, a substantial contribution from solvation gives the same effect, as a consequence of a structural link between the amount of bound water and the protein flexibility. Only by assuming substantial changes in solvation-an intrinsically compensatory process-can a more complete understanding of EEC be obtained. Faced with such large, and compensating, changes in the enthalpies and entropies of binding, the best approach to engineering elevated affinities must be through the addition of ionic links, as they generate increased entropy without affecting the enthalpy.

Aqueous dissolution rates of uranium oxides

International Nuclear Information System (INIS)

Steward, S.A.; Mones, E.T.

1994-10-01

An understanding of the long-term dissolution of waste forms in groundwater is required for the safe disposal of high level nuclear waste in an underground repository. The main routes by which radionuclides could be released from a geological repository are the dissolution and transport processes in groundwater flow. Because uranium dioxide is the primary constituent of spent nuclear fuel, the dissolution of its matrix in spent fuel is considered the rate-limiting step for release of radioactive fission products. The purpose of our work has been to measure the intrinsic dissolution rates of uranium oxides under a variety of well-controlled conditions that are relevant to a repository and allow for modeling. The intermediate oxide phase U 3 O 8 , triuranium octaoxide, is quite stable and known to be present in oxidized spent fuel. The trioxide, UO 3 , has been shown to exist in drip tests on spent fuel. Here we compare the results of essentially identical dissolution experiments performed on depleted U 3 O 8 and dehyrated schoepite or uranium trioxide monohydrate (UO 3 ·H 2 O). These are compared with earlier work on spent fuel and UO 2 under similar conditions

Enthalpies of formation of selected Co{sub 2}YZ Heusler compounds

Energy Technology Data Exchange (ETDEWEB)

Yin, Ming, E-mail: myin1@hawk.iit.edu; Chen, Song; Nash, Philip

2013-11-15

Highlights: •Enthalpies of formation of selected Co{sub 2}YZ were measured by drop calorimeters. •Enthalpy decreases as the Z element approaches the top right corner of the periodic table. •For the Y element, enthalpy increases on increasing the number of d electrons. •Result of L2{sub 1} structured compounds agrees with first principles data. •Lattice parameters and related phase relationships were consistent with literature data. -- Abstract: Standard enthalpies of formation at 298 K of selected ternary Co{sub 2}-based Heusler compounds Co{sub 2}YZ (Y = Fe, Hf, Mn, Ti, V, Zr; Z = Al, Ga, In, Si, Ge, Sn) were measured by high temperature direct synthesis calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the L2{sub 1} compounds are: Co{sub 2}FeGa (−25.8 ± 2.6); Co{sub 2}FeSi (−38.4 ± 2.2); Co{sub 2}FeGe (−11.6 ± 2.1); Co{sub 2}MnGa (−30.1 ± 2.3); Co{sub 2}MnSi (−42.4 ± 1.2); Co{sub 2}MnGe (−31.6 ± 3.0); Co{sub 2}MnSn (−15.6 ± 2.8); Co{sub 2}TiAl (−55.0 ± 3.7); Co{sub 2}TiGa (−54.2 ± 2.6); Co{sub 2}TiSi (−61.4 ± 1.7); Co{sub 2}TiGe (−59.3 ± 3.8); Co{sub 2}TiSn (−38.4 ± 2.0); Co{sub 2}VGa (−28.4 ± 1.1) and for the B2 compounds: Co{sub 2}FeAl (−22.5 ± 2.5), Co{sub 2}MnAl (−27.6 ± 2.7). Values are compared with those from first principles calculation when available and the extended semi-empirical model of Miedema. Trends in enthalpy of formation with element atomic number are discussed. Lattice parameters of the compounds with L2{sub 1} structure are determined by X-ray diffraction analysis.

Enthalpy generation from mixing in hohlraum-driven targets

Science.gov (United States)

Amendt, Peter; Milovich, Jose

2016-10-01

The increase in enthalpy from the physical mixing of two initially separated materials is analytically estimated and applied to ICF implosions and gas-filled hohlraums. Pressure and temperature gradients across a classical interface are shown to be the origin of enthalpy generation from mixing. The amount of enthalpy generation is estimated to be on the order of 100 Joules for a 10 micron-scale annular mixing layer between the solid deuterium-tritium fuel and the undoped high-density carbon ablator of a NIF-scale implosion. A potential resonance is found between the mixing layer thickness and gravitational (Cs2/ g) and temperature-gradient scale lengths, leading to elevated enthalpy generation. These results suggest that if mixing occurs in current capsule designs for the National Ignition Facility, the ignition margin may be appreciably eroded by the associated enthalpy of mixing. The degree of enthalpy generation from mixing of high- Z hohlraum wall material and low- Z gas fills is estimated to be on the order of 100 kJ or more for recent NIF-scale hohlraum experiments, which is consistent with the inferred missing energy based on observed delays in capsule implosion times. Work performed under the auspices of Lawrence Livermore National Security, LLC (LLNS) under Contract No. DE-AC52-07NA27344.

Enthalpies of vaporization of organometallic compounds

International Nuclear Information System (INIS)

Kuznetsov, N.T.; Sevast'yanov, V.G.; Mitin, V.A.; Krasnodubskaya, S.V.; Zakharov, L.N.; Domrachev, G.A.; AN SSSR, Gor'kij. Inst. Khimii)

1987-01-01

A possibility to use the method of additive schemes for the calculation of vaporizaton enthalpies of uranium organometallic compounds is discussed while comparing the values obtained using the method with experimental data. The possibility of apriori evaluation of evaporation enthalpy values of different uranium compounds using the method of additive schemes and structural characteristics of molecules, such as the sum of ligand solid angles, is shown

Study on the enthalpy of solution and enthalpy of dilution for the ionic liquid [C3mim][Val] (1-propyl-3-methylimidazolium valine)

International Nuclear Information System (INIS)

Guan Wei; Li Long; Ma Xiaoxue; Tong Jing; Fang Dawei; Yang Jiazhen

2012-01-01

Graphical abstract: The thermodynamic cycle for estimation of the hydration enthalpy of ionic liquid [C 3 mim][Val]. Highlights: ► A new amino acid ionic liquid [C 3 mim][Val] was prepared. ► The molar enthalpies of solution of the ionic liquid. ► The hydration enthalpy of the cation [C 3 mim] + was estimated. ► The molar enthalpies of dilution, of aqueous [C 3 mim][Val] were measured. - Abstract: A new amino acid ionic liquid (AAIL) [C 3 mim][Val] (1-propyl-3-methylimidazolium valine) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar solution enthalpies of the ionic liquid [C 3 mim][Val] with known amounts of water and with different concentrations in molality were measured at T = 298.15 K. In terms of standard addition method (SAM) and Archer’s method, the standard molar enthalpy of solution for [C 3 mim][Val] without water, Δ s H m ∘ = (−55.7 ± 0.4) kJ · mol −1 , was obtained. The hydration enthalpy of the cation [C 3 mim] + , ΔH + ([C 3 mim] + ) = −226 kJ · mol −1 , was estimated in terms of Glasser’s theory. Using the RD496-III heat conduction microcalorimeter, the molar enthalpies of dilution, Δ D H m (m i → m f ), of aqueous [C 3 mim][Val] with various values of molality were measured. The values of Δ D H m (m i → m f ) were fitted to Pitzer’s ion-interaction model and the values of apparent relative molar enthalpy, φ L, calculated using Pitzer’s ion-interaction model.

Uranium carbide dissolution in nitric solution: Sonication vs. silent conditions

International Nuclear Information System (INIS)

Virot, Matthieu; Szenknect, Stéphanie; Chave, Tony; Dacheux, Nicolas; Moisy, Philippe; Nikitenko, Sergey I.

2013-01-01

The dissolution of uranium carbide (UC) in nitric acid media is considered by means of power ultrasound (sonication) or magnetic stirring. The induction period required to initiate UC dissolution was found to be dramatically shortened when sonicating a 3 M nitric solution (Ar, 20 kHz, 18 W cm −2 , 20 °C). At higher acidity, magnetic stirring offers faster dissolution kinetics compared to sonication. Ultrasound-assisted UC dissolution is found to be passivated after ∼60% dissolution and remains incomplete whatever the acidity which is confirmed by ICP–AES, LECO and SEM–EDX analyses. In general, the kinetics of UC dissolution is linked to the in situ generation of nitrous acid in agreement with the general mechanism of UC dissolution; the nitrous acid formation is reported to be faster under ultrasound at low acidity due to the nitric acid sonolysis. The carbon balance shared between the gaseous, liquid, and solid phases is strongly influenced by the applied dissolution procedure and HNO 3 concentration

Uranium carbide dissolution in nitric solution: Sonication vs. silent conditions

Science.gov (United States)

Virot, Matthieu; Szenknect, Stéphanie; Chave, Tony; Dacheux, Nicolas; Moisy, Philippe; Nikitenko, Sergey I.

2013-10-01

The dissolution of uranium carbide (UC) in nitric acid media is considered by means of power ultrasound (sonication) or magnetic stirring. The induction period required to initiate UC dissolution was found to be dramatically shortened when sonicating a 3 M nitric solution (Ar, 20 kHz, 18 W cm-2, 20 °C). At higher acidity, magnetic stirring offers faster dissolution kinetics compared to sonication. Ultrasound-assisted UC dissolution is found to be passivated after ∼60% dissolution and remains incomplete whatever the acidity which is confirmed by ICP-AES, LECO and SEM-EDX analyses. In general, the kinetics of UC dissolution is linked to the in situ generation of nitrous acid in agreement with the general mechanism of UC dissolution; the nitrous acid formation is reported to be faster under ultrasound at low acidity due to the nitric acid sonolysis. The carbon balance shared between the gaseous, liquid, and solid phases is strongly influenced by the applied dissolution procedure and HNO3 concentration.

Relationships between fusion, solution, vaporization and sublimation enthalpies of substituted phenols

International Nuclear Information System (INIS)

Yagofarov, Mikhail I.; Nagrimanov, Ruslan N.; Solomonov, Boris N.

2017-01-01

Highlights: • Method for determination of sublimation and vaporization enthalpies of phenols was developed. • Vaporization enthalpies of 28 phenols at 298 K were calculated. • Sublimation enthalpies of 26 phenols at 298 K were calculated using fusion enthalpies at melting temperatures. • Obtained values are in good agreement with the results of conventional methods. - Abstract: In this work a method for determination of sublimation and vaporization enthalpies of substituted phenols was developed. This method is a modification of solution calorimetry approach. Modification is based on the novel relations, which bind solution, vaporization and sublimation enthalpies at 298.15 K and fusion enthalpy at the melting temperature. According to novel relations the equations for calculating sublimation and vaporization enthalpies at 298.15 K were offered. Calculated values of sublimation and vaporization enthalpies of phenol derivatives containing alkyls, halogens, –OCH 3 , –NO 2 , –COCH 3 , –COOCH 3 groups, and dihydroxybenzenes were compared with literature data (298.15 K) obtained by conventional methods. In most of the cases divergence does not exceed 2–3%.

Accelerated dissolution of iron oxides in ice

Directory of Open Access Journals (Sweden)

D. Jeong

2012-11-01

Full Text Available Iron dissolution from mineral dusts and soil particles is vital as a source of bioavailable iron in various environmental media. In this work, the dissolution of iron oxide particles trapped in ice was investigated as a new pathway of iron supply. The dissolution experiments were carried out in the absence and presence of various organic complexing ligands under dark condition. In acidic pH conditions (pH 2, 3, and 4, the dissolution of iron oxides was greatly enhanced in the ice phase compared to that in water. The dissolved iron was mainly in the ferric form, which indicates that the dissolution is not a reductive process. The extent of dissolved iron was greatly affected by the kind of organic complexing ligands and the surface area of iron oxides. The iron dissolution was most pronounced with high surface area iron oxides and in the presence of strong iron binding ligands. The enhanced dissolution of iron oxides in ice is mainly ascribed to the "freeze concentration effect", which concentrates iron oxide particles, organic ligands, and protons in the liquid like ice grain boundary region and accelerates the dissolution of iron oxides. The ice-enhanced dissolution effect gradually decreased when decreasing the freezing temperature from −10 to −196 °C, which implies that the presence and formation of the liquid-like ice grain boundary region play a critical role. The proposed phenomenon of enhanced dissolution of iron oxides in ice may provide a new pathway of bioavailable iron production. The frozen atmospheric ice with iron-containing dust particles in the upper atmosphere thaws upon descending and may provide bioavailable iron upon deposition onto the ocean surface.

TANK 12 SLUDGE CHARACTERIZATION AND ALUMINUM DISSOLUTION DEMONSTRATION

International Nuclear Information System (INIS)

Reboul, S.; Hay, Michael; Zeigler, Kristine; Stone, Michael

2009-01-01

A 3-L sludge slurry sample from Tank 12 was characterized and then processed through an aluminum dissolution demonstration. The dominant constituent of the sludge was found to be aluminum in the form of boehmite. The iron content was minor, about one-tenth that of the aluminum. The salt content of the supernatant was relatively high, with a sodium concentration of ∼7 M. Due to these characteristics, the yield stress and plastic viscosity of the unprocessed slurry were relatively high (19 Pa and 27 cP), and the settling rate of the sludge was relatively low (∼20% settling over a two and a half week period). Prior to performing aluminum dissolution, plutonium and gadolinium were added to the slurry to simulate receipt of plutonium waste from H-Canyon. Aluminum dissolution was performed over a 26 day period at a temperature of 65 C. Approximately 60% of the insoluble aluminum dissolved during the demonstration, with the rate of dissolution slowing significantly by the end of the demonstration period. In contrast, approximately 20% of the plutonium and less than 1% of the gadolinium partitioned to the liquid phase. However, about a third of the liquid phase plutonium became solubilized prior to the dissolution period, when the H-Canyon plutonium/gadolinium simulant was added to the Tank 12 slurry. Quantification of iron dissolution was less clear, but appeared to be on the order of 1% based on the majority of data (a minor portion of the data suggested iron dissolution could be as high as 10%). The yield stress of the post-dissolution slurry (2.5 Pa) was an order of magnitude lower than the initial slurry, due most likely to the reduced insoluble solids content caused by aluminum dissolution. In contrast, the plastic viscosity remained unchanged (27 cP). The settling rate of the post-dissolution slurry was higher than the initial slurry, but still relatively low compared to settling of typical high iron content/low salt content sludges. Approximately 40% of the

Effect of wet and dry cycles on dissolution of relatively insoluble particles containing Pu

International Nuclear Information System (INIS)

Mewhinney, J.A.; Eidson, A.F.; Wong, V.A.

1987-01-01

Dissolution of gross alpha emitter radioactivity from particles composed of mixed uranium and plutonium oxides or of plutonium dioxide continually immersed in solvent typically display at least a two-phase dissolution pattern. Rapid dissolution of a small fraction of the total particulate mass is followed by much slower dissolution for the majority of the particulate mass. In this study, respirable particles of (U, Pu)O 2 and PuO 2 were subjected to dissolution using an alternate wetting and drying cycle. Particles were continuously immersed in solvent for 4 d and then dried in air for 3 d. This cycle was repeated weekly for 7 wk. Four solvents were used to represent a range of potential environmental conditions and a fifth solvent was used for comparison to other continuous immersion studies. In contrast to dissolution studies involving continuous immersion over periods of two or more weeks that exhibit a three-phase dissolution process, the alternate wet-dry cycling resulted in repetition of the first two phases of the dissolution pattern for each cycle. This led to significantly enhanced dissolution of both particulate materials. The enhancement in total dissolution ranged from two to ten times larger during each wet-dry cycle compared to studies involving continuous immersion. The results indicate a potential need to re-evaluate environmental models of actinide element bioavailability for particulate materials released to environments where wet-dry cycling may be routine, i.e. intermittent rainfall in an otherwise arid climate or in stream beds with intermittent flow

Oxidation and dissolution of UO{sub 2} in bicarbonate media: Implications for the spent nuclear fuel oxidative dissolution mechanism

Energy Technology Data Exchange (ETDEWEB)

Gimenez, J. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain)]. E-mail: francisco.javier.gimenez@upc.edu; Clarens, F. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Casas, I. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Rovira, M. [CTM Centre Tecnologic, Avda. Bases de Manresa 1. 08240 Manresa (Spain); Pablo, J. de [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Bruno, J. [Enresa-Enviros Environmental Science and Waste Management Chair, UPC, Jordi Girona 1-3 B2, 08034 Barcelona (Spain)

2005-10-15

The objective of this work is to study the UO{sub 2} oxidation by O{sub 2} and dissolution in bicarbonate media and to extrapolate the results obtained to improve the knowledge of the oxidative dissolution of spent nuclear fuel. The results obtained show that in the studied range the oxygen consumption rate is independent on the bicarbonate concentration while the UO{sub 2} dissolution rate does depend on. Besides, at 10{sup -4} mol dm{sup -3} bicarbonate concentration, the oxygen consumption rate is almost two orders of magnitude higher than the UO{sub 2} dissolution rate. These results suggest that at low bicarbonate concentration (<10{sup -2} mol dm{sup -3}) the alteration of the spent nuclear fuel cannot be directly derived from the measured uranium concentrations in solution. On the other hand, the study at low bicarbonate concentrations of the evolution of the UO{sub 2} surface at nanometric scale by means of the SFM technique shows that the difference between oxidation and dissolution rates is not due to the precipitation of a secondary solid phase on UO{sub 2}.

Prediction of the vapor pressure and vaporization enthalpy of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids.

Science.gov (United States)

Diedenhofen, Michael; Klamt, Andreas; Marsh, Kenneth; Schäfer, Ansgar

2007-09-07

The vapor pressures and vaporization enthalpies of a series of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids have been predicted with two different approaches using the COSMO-RS method and quantum chemical gas phase calculations. While the calculated enthalpies are in good agreement with the experimental data, COSMO-RS seems to underestimate the vapor pressures by roughly 0.5-4 log units dependent on the IL and approach used.

Thermodynamic study of phase transitions of imidazoles and 1-methylimidazoles

Energy Technology Data Exchange (ETDEWEB)

Almeida, Ana R.R.P., E-mail: ana.figueira@fc.up.pt [Centro de Investigacao em Quimica, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Monte, Manuel J.S., E-mail: mjmonte@fc.up.pt [Centro de Investigacao em Quimica, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

2012-01-15

Highlights: > Sublimation vapor pressures of imidazole, N-methylimidazole and four derivatives were measured. > Liquid vapor pressures were also measured for four of the compounds studied. > Vapor pressure results enabled determination of sublimation, vaporization, and fusion enthalpy. > From enthalpies of sublimation, enthalpies of intermolecular N-H...N bonds were estimated. - Abstract: The vapor pressures of imidazole, N-methylimidazole and of their dichloro and dicyano substituted compounds were measured at different temperatures, in the crystalline phase for two of them, and in crystalline and liquid phases for the other four. From these measurements, enthalpies and standard entropies of sublimation and vaporization were derived. The results allowed the determination of the triple points (p, T) coordinates of the four compounds studied in both condensed phases as well as the calculation of their enthalpy of fusion. Enthalpies and temperatures of fusion were also determined using d.s.c. The experimental results enabled the estimation of the enthalpy of the intermolecular N-H...N bonds in the imidazoles studied.

Crystal structure and thermochemical properties of a novel coordination compound sodium pyruvate C3H3O3Na(s)

International Nuclear Information System (INIS)

Gao, Zhen-Fei; Di, You-Ying; Liu, Su-Zhou; Lu, Dong-Fei; Dou, Jian-Min

2014-01-01

Graphical abstract: A novel coordination compound sodium pyruvate C 3 H 3 O 3 Na(s) is synthesised. Elemental analysis and X-ray crystallography are used to characterise the composition and crystal structure of the compound. The lattice potential energy and ionic volume of the anion are obtained from crystallographic data. The standard molar enthalpy of formation of the compound is calculated by an isoperibol solution-reaction calorimeter. Molar enthalpies of dissolution of the compound at various molalities are measured at T = 298.15 K. According to Pitzer’s theory, molar enthalpy of dissolution of the title compound at infinite dilution is calculated. The values of relative apparent molar enthalpies and relative partial molar enthalpies of the solvent and the compound at different concentrations m/(mol · kg −1 ) are derived. - Highlights: • The sodium pyruvate was synthesised and crystal structure was determined. • The enthalpy change of the synthesis reaction was obtained. • Standard molar enthalpy of formation was obtained. • Molar enthalpy of dissolution at infinite dilution was calculated. - Abstract: A novel coordination compound sodium pyruvate C 3 H 3 O 3 Na(s) is synthesised by a liquid phase reaction. The compound has an obvious bioactivity and can be used as the biological carbon source and the chemical identification of primary and secondary alcohols. It can be also used to determinate transaminase. Elemental analysis and X-ray crystallography are used to characterise the composition and crystal structure of the compound. Single crystal X-ray analysis reveals that the compound is formed by one CH 3 COCOO − anion and one Na + cation. An obvious feature of the crystal structure is the formation of the five-membered chelate ring by the coordination of O1 of carboxylate and O3 of keto form with Na + cation, and it is good for the stability of the compound in structure. The lattice potential energy and ionic volume of the anion are obtained

Enthalpy model for heating, melting, and vaporization in laser ablation

OpenAIRE

Vasilios Alexiades; David Autrique

2010-01-01

Laser ablation is used in a growing number of applications in various areas including medicine, archaeology, chemistry, environmental and materials sciences. In this work the heat transfer and phase change phenomena during nanosecond laser ablation of a copper (Cu) target in a helium (He) background gas at atmospheric pressure are presented. An enthalpy model is outlined, which accounts for heating, melting, and vaporization of the target. As far as we know, this is the first model th...

Applicability of the theory of thermodynamic similarity to predict the enthalpies of vaporization of aliphatic aldehydes

Science.gov (United States)

Esina, Z. N.; Korchuganova, M. R.

2015-06-01

The theory of thermodynamic similarity is used to predict the enthalpies of vaporization of aliphatic aldehydes. The predicted data allow us to calculate the phase diagrams of liquid-vapor equilibrium in a binary water-aliphatic aldehyde system.

The relationship between vapour pressure, vaporization enthalpy, and enthalpy of transfer from solution to gas: An extension of the Martin equation

International Nuclear Information System (INIS)

Srisaipet, A.; Aryusuk, K.; Lilitchan, S.; Krisnangkura, K.

2007-01-01

Martin's equation, Δ sln g G=Δ sln g G o +zδ sln g G, is extended to cover vaporization free energy (Δ l g G). The extended equation is further expanded in terms of enthalpy and entropy and then used to correlate vaporization enthalpy (Δ l g H) and enthalpy of transfer from solution to gas (Δ sln g H). Data available in the literatures are used to validate and support the speculations derived from the proposed equation

Energetic studies of urea derivatives: Standard molar enthalpy of formation of 3,4,4'-trichlorocarbanilide

Energy Technology Data Exchange (ETDEWEB)

Ribeiro da Silva, Maria das Dores M.C. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Ribeiro da Silva, Manuel A.V., E-mail: risilva@fc.up.p [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Freitas, Vera L.S. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Roux, Maria Victoria; Jimenez, Pilar; Davalos, Juan Z. [Instituto de Quimica Fisica ' Rocasolano' , C.S.I.C., Serrano, 119, E-28006 Madrid (Spain); Cabildo, Pilar; Claramunt, Rosa M. [Departamento de Quimica Organica y Bio-Organica, Facultad de Ciencias, UNED, Senda del Rey, 9, E-28040 Madrid (Spain); Pinilla, Elena; Rosario Torres, M. [Departamento de Quimica Inorganica I, Laboratorio de Difraccion de Rayos X, Facultad de Ciencias Quimicas, E-28040 Madrid (Spain); Elguero, Jose [Instituto de Quimica Medica, C.S.I.C., Juan de la Cierva, 3, E-28006 Madrid (Spain)

2010-04-15

Thermochemical and thermophysical studies have been carried out for crystalline 3,4,4'-trichlorocarbanilide. The standard (p{sup o} = 0.1 MPa) molar enthalpy of formation, at T = 298.15 K, for the crystalline 3,4,4'-trichlorocarbanilide (TCC) was experimentally determined using rotating-bomb combustion calorimetry, as -(234.6 +- 8.3) kJ . mol{sup -1}. The standard enthalpy of sublimation, at the reference temperature of 298.15 K, was measured by the vacuum drop microcalorimetric technique, using a High Temperature Calvet Microcalorimeter as (182.1 +- 1.7) kJ . mol{sup -1}. These two thermochemical parameters yielded the standard molar enthalpy of formation of the studied compound, in the gaseous phase, at T = 298.15 K, as -(52.5 +- 8.5) kJ . mol{sup -1}. This parameter was also calculated by computational thermochemistry at M05-2X/6-311++G** and B3LYP/6-311++G(3df, 2p) levels, with a deviation less than 4.5 kJ . mol{sup -1} from experimental value. Moreover, the thermophysical study was made by differential scanning calorimetry, DSC, over the temperature interval between T = 263 K and its onset fusion temperature, T = (527.5 +- 0.4) K. A solid-solid phase transition was found at T = (428 +- 1) K, with the enthalpy of transition of (6.1 +- 0.1) kJ . mol{sup -1}. The X-ray crystal structure of TCC was determined and the three-centred N-H...O=C hydrogen bonds present analyzed.

Determination of molar enthalpy of sublimation in case of orotic acid as obtained from experimental and computational data

Science.gov (United States)

Marochkin, Ilya I.; Altova, Ekaterina P.; Chilingarov, Norbert S.; Vilkova, Anna L.; Shishkov, Igor F.

2018-03-01

Saturated vapor pressure, ln(p/Pa) = (-21316 ± 511)/(T/K)+(41.64 ± 0.11), and enthalpy of sublimation of orotic acid, Δsub Hm0 (Tm) = 177 ± 4 kJ/mol, were determined by means of Knudsen effusion mass spectrometry in the temperature range of 423÷493 K. The computational approaches supported the experimental results reported. The theoretical estimation of the gas-phase enthalpy of formation for orotic acid was done with different working reactions used.

Dissolution of crystalline ceramics

International Nuclear Information System (INIS)

White, W.B.

1982-01-01

The present program objectives are to lay out the fundamentals of crystalline waste form dissolution. Nuclear waste ceramics are polycrystalline. An assumption of the work is that to the first order, the release rate of a particular radionuclide is the surface-weighted sum of the release rates of the radionuclide from each crystalline form that contains it. In the second order, of course, there will be synergistic effects. There will be also grain boundary and other microstructural influences. As a first approximation, we have selected crystalline phases one at a time. The sequence of investigations and measurements is: (i) Identification of the actual chemical reactions of dissolution including identification of the solid reaction products if such occur. (ii) The rates of these reactions are then determined empirically to give what may be called macroscopic kinetics. (iii) Determination of the rate-controlling mechanisms. (iv) If the rate is controlled by surface reactions, the final step would be to determine the atomic kinetics, that is the specific atomic reactions that occur at the dissolving interface. Our concern with the crystalline forms are in two areas: The crystalline components of the reference ceramic waste form and related ceramics and the alumino-silicate phases that appear in some experimental waste forms and as waste-rock interaction products. Specific compounds are: (1) Reference Ceramic Phases (zirconolite, magnetoplumbite, spinel, Tc-bearing spinel and perovskite); (2) Aluminosilicate phases (nepheline, pollucite, CsAlSi 5 O 12 , Sr-feldspar). 5 figures, 1 table

Phase behavior and reactive transport of partial melt in heterogeneous mantle model

Science.gov (United States)

Jordan, J.; Hesse, M. A.

2013-12-01

The reactive transport of partial melt is the key process that leads to the chemical and physical differentiation of terrestrial planets and smaller celestial bodies. The essential role of the lithological heterogeneities during partial melting of the mantle is increasingly recognized. How far can enriched melts propagate while interacting with the ambient mantle? Can the melt flow emanating from a fertile heterogeneity be localized through a reactive infiltration feedback in a model without exogenous factors or contrived initial conditions? A full understanding of the role of heterogeneities requires reactive melt transport models that account for the phase behavior of major elements. Previous work on reactive transport in the mantle focuses on trace element partitioning; we present the first nonlinear chromatographic analysis of reactive melt transport in systems with binary solid solution. Our analysis shows that reactive melt transport in systems with binary solid solution leads to the formation of two separate reaction fronts: a slow melting/freezing front along which enthalpy change is dominant and a fast dissolution/precipitation front along which compositional changes are dominated by an ion-exchange process over enthalpy change. An intermediate state forms between these two fronts with a bulk-rock composition and enthalpy that are not necessarily bounded by the bulk-rock composition and enthalpy of either the enriched heterogeneity or the depleted ambient mantle. The formation of this intermediate state makes it difficult to anticipate the porosity changes and hence the stability of reaction fronts. Therefore, we develop a graphical representation for the solution that allows identification of the intermediate state by inspection, for all possible bulk-rock compositions and enthalpies of the heterogeneity and the ambient mantle. We apply the analysis to the partial melting of an enriched heterogeneity. This leads to the formation of moving precipitation

Enthalpy of sublimation as measured using a silicon oscillator

Science.gov (United States)

Shakeel, Hamza; Pomeroy, J. M.

In this study, we report the enthalpy of sublimation of common gases (nitrogen, oxygen, argon, carbon dioxide, neon, krypton, xenon, and water vapor) using a large area silicon oscillator with a sub-ng (~0.027 ng/cm2) mass sensitivity. The double paddle oscillator design enables high frequency stability (17 ppb) at cryogenic temperatures and provides a consistent technique for enthalpy measurements. The enthalpies of sublimation are derived from the rate of mass loss during programmed thermal desorption and are detected as a change in the resonance frequency of the self-tracking oscillator. These measured enthalpy values show excellent agreement with the accepted literature values.

Crystal structure and thermochemical properties of n-decylammonium ethyl sulfate (C10H21NH3SO4C2H5)(s)

International Nuclear Information System (INIS)

Zhang, Li-Jun; Di, You-Ying; Dou, Jian-Min

2013-01-01

Graphical abstract: Crystal structure of n-decylammonium ethyl sulfate was determined by X-ray crystallography. Lattice potential energy and molar volume of the solid compound and its anion were respectively obtained. Molar enthalpies of dissolution of the compound at different concentrations were measured by an isoperibol solution–reaction calorimeter. According to the Pitzer’s electrolyte solution theory, molar enthalpy of dissolution of the compound at infinite dilution and Pitzer parameters were obtained. The values of apparent relative molar enthalpies of the title compound and relative partial molar enthalpies of the solute and the solvent at different concentrations were derived. Finally, enthalpies of hydration of the compound and its anion were calculated. Highlights: ► Crystal structure of n-decylammonium ethyl sulfate was determined. ► Lattice potential energy was calculated. ► Molar enthalpy of dissolution at infinite dilution was determined. ► Enthalpies of hydration of the compound and its anion were derived. - Abstract: Crystal structure of n-decylammonium ethyl sulfate was determined by X-ray crystallography. Lattice potential energy and molar volume of the solid compound and its anion were respectively obtained. Ionic radius of the anion was calculated from the corresponding effective volume of the anion. Molar enthalpies of dissolution of the compound at different concentrations m /(mol · kg –1 ) were measured by an isoperibol solution–reaction calorimeter at T = 298.15 K. According to the Pitzer’s electrolyte solution theory, molar enthalpy of dissolution of the compound at infinite dilution (Δ sol H m ∞ ) was determined to be (21.284 ± 0.042) kJ·mol –1 , and enthalpy of hydration of the anion SO 4 C 2 H 5 − was calculated to be ΔH – = −340.68 kJ·mol –1 . The values of apparent relative molar enthalpies ( Φ L) of the title compound and relative partial molar enthalpies (L 2 ¯ and L 1 ¯ ) of the solute and

Dissolution mechanism of aluminum hydroxides in acid media

Science.gov (United States)

Lainer, Yu. A.; Gorichev, I. G.; Tuzhilin, A. S.; Gololobova, E. G.

2008-08-01

The effects of the concentration, temperature, and potential at the hydroxide/electrolyte interface on the aluminum hydroxide dissolution in sulfuric, hydrochloric, and perchloric acids are studied. The limiting stage of the aluminum hydroxide dissolution in the acids is found to be the transition of the complexes that form on the aluminum hydroxide surface from the solid phase into the solution. The results of the calculation of the acid-base equilibrium constants at the oxide (hydroxide)/solution interface using the experimental data on the potentiometric titration of Al2O3 and AlOOH suspensions are analyzed. A mechanism is proposed for the dissolution of aluminum hydroxides in acid media.

Effect of dissolution on the load–settlement behavior of shallow foundations

KAUST Repository

Cha, Minsu

2016-03-10

Mineral dissolution and solid-liquid phase change may cause settlement or affect the bearing capacity of shallow foundations. The effect of gradual grain dissolution on small-scale shallow foundation behavior is investigated using the discrete element method. Results show that dissolution is most detrimental during early stages, as initially contacting particles shrink and force chains must reform throughout the medium. Porosity tends to increase during dissolution and force chains evolve into strong localized forces with a honeycomb topology. Higher settlements are required to mobilize bearing resistance in postdissolution sediments than in pre-dissolution ones. Subsurface mineral dissolution beneath a footing under load is the worst condition; in fact, settlements in such cases are higher than when a foundation load is applied on a sediment that has already experienced dissolution. © the author(s) or their institution(s).

Effect of dissolution on the load–settlement behavior of shallow foundations

KAUST Repository

Cha, Minsu; Santamarina, Carlos

2016-01-01

Mineral dissolution and solid-liquid phase change may cause settlement or affect the bearing capacity of shallow foundations. The effect of gradual grain dissolution on small-scale shallow foundation behavior is investigated using the discrete element method. Results show that dissolution is most detrimental during early stages, as initially contacting particles shrink and force chains must reform throughout the medium. Porosity tends to increase during dissolution and force chains evolve into strong localized forces with a honeycomb topology. Higher settlements are required to mobilize bearing resistance in postdissolution sediments than in pre-dissolution ones. Subsurface mineral dissolution beneath a footing under load is the worst condition; in fact, settlements in such cases are higher than when a foundation load is applied on a sediment that has already experienced dissolution. © the author(s) or their institution(s).

Vapor pressures and enthalpies of vaporization of azides

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Emel'yanenko, Vladimir N.; Algarra, Manuel; Manuel Lopez-Romero, J.; Aguiar, Fabio; Enrique Rodriguez-Borges, J.; Esteves da Silva, Joaquim C.G.

2011-01-01

Highlights: → We prepared and measured vapor pressures and vaporization enthalpies of 7 azides. → We examined consistency of new and available in the literature data. → Data for geminal azides and azido-alkanes selected for thermochemical calculations. - Abstract: Vapor pressures of some azides have been determined by the transpiration method. The molar enthalpies of vaporization Δ l g H m of these compounds were derived from the temperature dependencies of vapor pressures. The measured data sets were successfully checked for internal consistency by comparison with vaporization enthalpies of similarly structured compounds.

Direct Determination Of γ′ / γ′+γ / γ Phase Boundaries In Ni-Al-Cr System Based On Enthalpy Of Formation Results Obtained By Calorimetric Solution Method

Directory of Open Access Journals (Sweden)

Maciąg T.

2015-09-01

Full Text Available The work is a continuation of the research carried out on a high-temperature calorimeter solution type on alloys from Ni-Al-Cr system. Thanks to the construction innovation introduced by authors the device allows the determination of the formation enthalpy of alloys at ambient and elevated temperatures. Experiments described in this article were carried out at three temperatures: 873K, 996K and 1150K on the alloys of the chemical compositions from the Ni75Al25 ÷ Ni87Cr13 section of the Ni-Al-Cr system. On the basis of changes in the enthalpy of formation with increasing chromium content of the alloys, points corresponding to places of phase boundaries γ′ / γ′+γ / γ in Ni-Al-Cr system were determined. A similar relationship was observed in previous studies of alloys from Ni75Al25÷Ni75Cr25 section. For precise determination of these characteristic points a statistical model was applied

Evaluation of Influence of Various Polymers on Dissolution and Phase Behavior of Carbamazepine-Succinic Acid Cocrystal in Matrix Tablets

Directory of Open Access Journals (Sweden)

Majeed Ullah

2015-01-01

Full Text Available The aim of current study was to explore the influence of three commonly used polymers, that is, cellulosics and noncellulosics, for example, Methocel K4M, Kollidon VA/64, and Soluplus, on the phase disproportionation and drug release profile of carbamazepine-succinic acid (CBZ-SUC cocrystal at varying drug to polymer ratios (1 : 1 to 1 : 0.25 in matrix tablets. The polymorphic phase disproportionation during in-depth dissolution studies of CBZ-SUC cocrystals and its crystalline properties were scrutinized by X-ray powder diffractrometry and Raman spectroscopy. The percent drug release from HPMC formulations (CSH showed inverse relation with the concentration of polymer; that is, drug release increased with decrease in polymer concentration. On contrary, direct relation was observed between percent drug release and polymer concentrations of Kollidon VA 64/Soluplus (CSK, CSS. At similar polymer concentration, drug release from pure carbamazepine was slightly lower with HPMC formulations than that of cocrystal; however, opposite trend in release rate was observed with Kollidon VA/64 and Soluplus. The significant increase in dissolution rate of cocrystal occurred with Kollidon VA/64 and Soluplus at higher polymer concentration. Moreover, no phase change took place in Methocel and Kollidon formulations. No tablet residue was left for Soluplus formulation so the impact of polymer on cocrystal integrity cannot be predicted.

Evaluation of Influence of Various Polymers on Dissolution and Phase Behavior of Carbamazepine-Succinic Acid Cocrystal in Matrix Tablets

Science.gov (United States)

Ullah, Majeed; Ullah, Hanif; Mahmood, Qaisar; Hussain, Izhar

2015-01-01

The aim of current study was to explore the influence of three commonly used polymers, that is, cellulosics and noncellulosics, for example, Methocel K4M, Kollidon VA/64, and Soluplus, on the phase disproportionation and drug release profile of carbamazepine-succinic acid (CBZ-SUC) cocrystal at varying drug to polymer ratios (1 : 1 to 1 : 0.25) in matrix tablets. The polymorphic phase disproportionation during in-depth dissolution studies of CBZ-SUC cocrystals and its crystalline properties were scrutinized by X-ray powder diffractrometry and Raman spectroscopy. The percent drug release from HPMC formulations (CSH) showed inverse relation with the concentration of polymer; that is, drug release increased with decrease in polymer concentration. On contrary, direct relation was observed between percent drug release and polymer concentrations of Kollidon VA 64/Soluplus (CSK, CSS). At similar polymer concentration, drug release from pure carbamazepine was slightly lower with HPMC formulations than that of cocrystal; however, opposite trend in release rate was observed with Kollidon VA/64 and Soluplus. The significant increase in dissolution rate of cocrystal occurred with Kollidon VA/64 and Soluplus at higher polymer concentration. Moreover, no phase change took place in Methocel and Kollidon formulations. No tablet residue was left for Soluplus formulation so the impact of polymer on cocrystal integrity cannot be predicted. PMID:26380301

Enthalpy-entropy compensation and the isokinetic temperature in ...

Indian Academy of Sciences (India)

Enthalpy-entropy compensation supposes that differences in activation enthalpy delta-H-++ for different reactions (or, typically inbiochemistry, the same reaction catalysed by enzymes obtained from different species) may be compensated for bydifferences in activation entropy delta-S-++. At the isokinetic temperature the ...

Examination of Uranium(VI) Leaching During Ligand Promoted Dissolution of Waste Tank Sludge Surrogates

Energy Technology Data Exchange (ETDEWEB)

Powell, Brian; Powell, Brian A.; Rao, Linfeng; Nash, Kenneth. L.

2008-06-10

The dissolution of synthetic boehmite (?-AlOOH) by 1-hydroxyethane-1,1-diphosphonic acid (HEDPA) was examined in a series of batch adsorption/dissolution experiments. Additionally, the leaching behavior of {sup 233}U(VI) from boehmite was examined as a function of pH and HEDPA concentration. The results are discussed in terms of sludge washing procedures that may be utilized during underground tank waste remediation. In the pH range 4 to 10, complexation of Al(III) by HEDPA significantly enhanced dissolution of boehmite. This phenomenon was especially pronounced in the neutral pH region where the solubility of aluminum, in the absence of complexants, is limited by the formation of sparsely soluble aluminum hydroxides. At pH higher than 10, dissolution of synthetic boehmite was inhibited by HEDPA, likely due to sorption of Al(III):HEDPA complexes. Addition of HEDPA to equilibrated U(VI)-synthetic boehmite suspensions yielded an increase in the aqueous phase uranium concentration. Partitioning of uranium between the solid and aqueous phase is described in terms of U(VI):HEDPA speciation and dissolution of the boehmite solid phase.

Thermodynamic study of phase transitions of imidazoles and 1-methylimidazoles

International Nuclear Information System (INIS)

Almeida, Ana R.R.P.; Monte, Manuel J.S.

2012-01-01

Highlights: → Sublimation vapor pressures of imidazole, N-methylimidazole and four derivatives were measured. → Liquid vapor pressures were also measured for four of the compounds studied. → Vapor pressure results enabled determination of sublimation, vaporization, and fusion enthalpy. → From enthalpies of sublimation, enthalpies of intermolecular N-H...N bonds were estimated. - Abstract: The vapor pressures of imidazole, N-methylimidazole and of their dichloro and dicyano substituted compounds were measured at different temperatures, in the crystalline phase for two of them, and in crystalline and liquid phases for the other four. From these measurements, enthalpies and standard entropies of sublimation and vaporization were derived. The results allowed the determination of the triple points (p, T) coordinates of the four compounds studied in both condensed phases as well as the calculation of their enthalpy of fusion. Enthalpies and temperatures of fusion were also determined using d.s.c. The experimental results enabled the estimation of the enthalpy of the intermolecular N-H...N bonds in the imidazoles studied.

Enthalpy of mixing and heat of vaporization of ethyl acetate with benzene and toluene at 298.15 k and 308.15 k

Directory of Open Access Journals (Sweden)

K. L. Shivabasappa

2008-03-01

Full Text Available The present work was carried out in two phases. First, enthalpy of mixing was measured and then the heat of vaporization for the same mixtures was obtained. The data are useful in the design of separation equipments. From the various designs available for the experimental determination of enthalpy of mixing, and heat of vaporization, the apparatus was selected, modified and constructed. The apparatus of enthalpy of mixing was tested with a known system Benzene - i-Butyl Alcohol and the data obtained was in very good agreement with literature values. Experiments were then conducted for mixtures of Ethyl Acetate with Benzene and Toluene. The experimental data was fitted to the standard correlations and the constants were evaluated. Heat of vaporization data were obtained from a static apparatus and tested for accuracy by conducting experiments with a known system Benzene - n-Hexane and the data obtained were found to be in agreement with literature values. Experiments were then conducted to measure heat of vaporization for the mixtures of Ethyl Acetate with Benzene and Toluene. Using experimental data of enthalpy of mixing from the first phase, and heat capacity data, the heat of vaporization were calculated.

Enthalpy of solution of rubidium nitrate in water

International Nuclear Information System (INIS)

Weintraub, R.; Apelblat, A.; Tamir, A.

1984-01-01

Molar enthalpies of solution of RbNO 3 in water at 298.15 K were measured in an LKB calorimeter. The molar enthalpies of solution extrapolated to infinite solution are: (36788 +- 30)J. mol -1 (Alfa) and (36539 +- 52)J.mol -1 (Aldrich). (author)

Dissolution processes

International Nuclear Information System (INIS)

Silver, G.L.

1976-01-01

This review contains more than 100 observations and 224 references on the dissolution phenomenon. The dissolution processes are grouped into three categories: methods of aqueous attack, fusion methods, and miscellaneous observations on phenomena related to dissolution problems

Vapor pressure and enthalpy of vaporization of linear aliphatic alkanediamines

International Nuclear Information System (INIS)

Pozdeev, Vasiliy A.; Verevkin, Sergey P.

2011-01-01

Highlights: → We measured vapor pressure of diamines H 2 N-(CH 2 ) n -NH 2 with n = 3 to 12. → Vaporization enthalpies at 298 K were derived. → We examined consistency of new and available in the literature data. → Enthalpies of vaporization show linear dependence on numbers n. → Enthalpies of vaporization correlate linearly with Kovat's indices. - Abstract: Vapor pressures and the molar enthalpies of vaporization of the linear aliphatic alkanediamines H 2 N-(CH 2 ) n -NH 2 with n = (3 to 12) have been determined using the transpiration method. A linear correlation of enthalpies of vaporization (at T = 298.15 K) of the alkanediamines with the number n and with the Kovat's indices has been found, proving the internal consistency of the measured data.

Chemical alteration of cement hydrates by dissolution

International Nuclear Information System (INIS)

Sugiyama, Daisuke; Fujita, Tomonari; Nakanishi, Kiyoshi

2000-01-01

Cementitious material is a potential waste packaging and backfilling material for the radioactive waste disposal, and is expected to provide both physical and chemical containment. In particular, the sorption of radionuclides onto cementitious material and the ability to provide a high pH condition are very important parameters when considering the release of radionuclides from radioactive wastes. For the long term, in the geological disposal environment, cement hydrates will be altered by, for example, dissolution, chemical reaction with ions in the groundwater, and hydrothermal reaction. Once the composition or crystallinity of the constituent minerals of a cement hydrate is changed by these processes, the pH of the repository buffered by cementitious material and its sorption ability might be affected. However, the mechanism of cement alteration is not yet fully understood. In this study, leaching experiments of some candidate cements for radioactive waste disposal were carried out. Hydrated Ordinary Portland Cement (OPC), Blast Furnace Slag blended cement (OPC/BFS) and Highly containing Flyash and Silicafume Cement (HFSC) samples were contacted with distilled water at liquid:solid ratios of 10:1, 100:1 and 1000:1 at room temperature for 200 days. In the case of OPC, Ca(OH) 2 dissolved at high liquid:solid ratios. The specific surface area of all cement samples increased by leaching process. This might be caused by further hydration and change of composition of constituent minerals. A model is presented which predicts the leaching of cement hydrates and the mineral composition in the hydrated cement solid phase, including the incongruent dissolution of CSH gel phases and congruent dissolution of Ca(OH) 2 , Ettringite and Hydrotalcite. Experimental results of dissolution of Ca-O-H and Ca-Si-O-H phases were well predicted by this model. (author)

[Enthalpy stabilization of chicken egg lysozyme in aqueous dimethylsulfoxide solutions].

Science.gov (United States)

Kovrigin, E L; Kirkitadze, M D; Potekhin, S A

1996-01-01

Scanning microcalorimetry data have been used to plot the dependences of the denaturation enthalpy of hen egg lysozyme on dimethylsulfoxide concentration at fixed temperatures. It has been shown that at dimethylsulfoxide concentrations below 40% (v/v) the enthalpy does not depend on pH of the medium. An increase of dimethylsulfoxide concentrations in this range leads to a linear growth of enthalpy. The rate of enthalpy growth decreases with the temperature increase. The denaturation enthalpy begins to considerably depend on pH at dimethylsulfoxide concentrations more than 40%. Spectroscopy data indicate that conformational changes occur in the protein in this range of concentrations already at room temperature, whereas according to scanning microcalorimetry, they take place at much higher temperatures. This difference is probably due to a decrease of the real temperature of protein melting below room temperature and a very inhibited character of the denaturational transition. This results in a decrease of calorimetric enthalpy at acidic pH owing to incomplete protein renaturation upon calorimeter cooling to the starting point.

Accounting for apparent deviations between calorimetric and van't Hoff enthalpies.

Science.gov (United States)

Kantonen, Samuel A; Henriksen, Niel M; Gilson, Michael K

2018-03-01

In theory, binding enthalpies directly obtained from calorimetry (such as ITC) and the temperature dependence of the binding free energy (van't Hoff method) should agree. However, previous studies have often found them to be discrepant. Experimental binding enthalpies (both calorimetric and van't Hoff) are obtained for two host-guest pairs using ITC, and the discrepancy between the two enthalpies is examined. Modeling of artificial ITC data is also used to examine how different sources of error propagate to both types of binding enthalpies. For the host-guest pairs examined here, good agreement, to within about 0.4kcal/mol, is obtained between the two enthalpies. Additionally, using artificial data, we find that different sources of error propagate to either enthalpy uniquely, with concentration error and heat error propagating primarily to calorimetric and van't Hoff enthalpies, respectively. With modern calorimeters, good agreement between van't Hoff and calorimetric enthalpies should be achievable, barring issues due to non-ideality or unanticipated measurement pathologies. Indeed, disagreement between the two can serve as a flag for error-prone datasets. A review of the underlying theory supports the expectation that these two quantities should be in agreement. We address and arguably resolve long-standing questions regarding the relationship between calorimetric and van't Hoff enthalpies. In addition, we show that comparison of these two quantities can be used as an internal consistency check of a calorimetry study. Copyright © 2017 Elsevier B.V. All rights reserved.

Standard enthalpies of formation of uranium compounds

International Nuclear Information System (INIS)

Cordfunke, E.H.P.; Ouweltjes, W.

1977-01-01

Enthalpies of solution of β-UO 2 SO 4 and α-UO 2 SeO 4 in H 2 SO 4 (aq) and of UO 2 SeO 3 in H 2 SO 4 (aq) + Ce(SO 4 ) 2 have been measured calorimetrically. Together with measurements of the enthalpy of solution of γ-UO 3 in these solvents, the standard enthalpies of formation of anhydrous β-UO 2 SO 4 , α-UO 2 SeO 4 , and UO 2 SeO 3 have been derived. The results obtained are: ΔHsub(f) 0 (s, 298.15 K)/ kcalsub(th) mol -1 : β-UO 2 SO 4 , -(440.9 +- 0.2); α-UO 2 SeO 4 , -(367.9 +- 0.8); UO 2 SeO 3 , -(363.8 +- 0.2). (author)

Standard enthalpies of formation of selected Rh{sub 2}YZ Heusler compounds

Energy Technology Data Exchange (ETDEWEB)

Yin, Ming, E-mail: myin1@hawk.iit.edu; Nash, Philip

2015-11-25

The standard enthalpies of formation (Δ{sub f}H°) of selected ternary Rh-based Rh{sub 2}YZ (Y = Cu, Fe, Mn, Ni, Ru, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) compounds were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation (in kJ/mol of atoms) are, for the Heusler compound Rh{sub 2}MnSn (−40.1 ± 3.6), for the B2-structured compounds: Rh{sub 2}FeAl (−48.5 ± 2.9); Rh{sub 2}MnAl (−72.4 ± 2.7); Rh{sub 2}MnGa (−55.3 ± 2.0); Rh{sub 2}MnIn (−35.3 ± 1.9), for the tetragonal compounds: Rh{sub 2}FeSn (−28.9 ± 1.3); Rh{sub 2}TiAl (−97.6 ± 2.2); Rh{sub 2}TiGa (−79.0 ± 1.8); Rh{sub 2}TiSn (−74.7 ± 3.1). Values are compared with those from first principles calculations in published papers and the Open Quantum Materials Database (OQMD). Lattice parameters of these compounds are determined using X-ray diffraction analysis (XRD). Microstructures were characterized using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). - Highlights: • Standard enthalpies of formation of Rh{sub 2}YZ were measured using a drop calorimeter. • Measured enthalpies agree with first principles data in general. • Lattice parameters and related phase relationships were consistent with literature data. • Rh{sub 2}TiSn of tI8 structure were reported for the first time.

Jarosite dissolution rates in perchlorate brine

Science.gov (United States)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

Enthalpy-entropy compensation for the solubility of drugs in solvent mixtures: paracetamol, acetanilide, and nalidixic acid in dioxane-water.

Science.gov (United States)

Bustamante, P; Romero, S; Pena, A; Escalera, B; Reillo, A

1998-12-01

In earlier work, a nonlinear enthalpy-entropy compensation was observed for the solubility of phenacetin in dioxane-water mixtures. This effect had not been earlier reported for the solubility of drugs in solvent mixtures. To gain insight into the compensation effect, the behavior of the apparent thermodynamic magnitudes for the solubility of paracetamol, acetanilide, and nalidixic acid is studied in this work. The solubility of these drugs was measured at several temperatures in dioxane-water mixtures. DSC analysis was performed on the original powders and on the solid phases after equilibration with the solvent mixture. The thermal properties of the solid phases did not show significant changes. The three drugs display a solubility maximum against the cosolvent ratio. The solubility peaks of acetanilide and nalidixic acid shift to a more polar region at the higher temperatures. Nonlinear van't Hoff plots were observed for nalidixic acid whereas acetanilide and paracetamol show linear behavior at the temperature range studied. The apparent enthalpies of solution are endothermic going through a maximum at 50% dioxane. Two different mechanisms, entropy and enthalpy, are suggested to be the driving forces that increase the solubility of the three drugs. Solubility is entropy controlled at the water-rich region (0-50% dioxane) and enthalpy controlled at the dioxane-rich region (50-100% dioxane). The enthalpy-entropy compensation analysis also suggests that two different mechanisms, dependent on cosolvent ratio, are involved in the solubility enhancement of the three drugs. The plots of deltaH versus deltaG are nonlinear, and the slope changes from positive to negative above 50% dioxane. The compensation effect for the thermodynamic magnitudes of transfer from water to the aqueous mixtures can be described by a common empirical nonlinear relationship, with the exception of paracetamol, which follows a separate linear relationship at dioxane ratios above 50%. The

Thermochemistry of adducts of some bivalent transition metal bromides with aniline

International Nuclear Information System (INIS)

Dunstan, Pedro Oliver

2006-01-01

The compounds [MBr 2 (an) 2 ] (where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II) or Zn(II); an=aniline) were synthesized and characterized by melting points, elemental analysis, thermal studies, and electronic and IR spectroscopy. The enthalpies of dissolution of the adducts, metal(II) bromides and aniline in methanol, aqueous 1.2M HCl or 25% (v/v) aqueous 1.2M HCl in methanol were measured. The following thermochemical parameters for the adducts have been determined by thermochemical cycles: the standard enthalpies for the Lewis acid/base reactions (Δ r H o ), the standard enthalpies of formation (Δ f H o ), the standard enthalpies of decomposition (Δ D H o ), the lattice standard enthalpies (Δ M H o ) and the standard enthalpies of the Lewis acid/base reactions in the gaseous phase (Δ r H o (g)). The mean bond dissociation enthalpies of the M(II)-nitrogen bonds (D-bar (M?N) ) and the enthalpies of formation of the adducts from the ions in the gaseous phase: M 2+ (g) +Br - (g) +an (g) ->[MBr 2 (an) 2 ] (g) (Δ fi H o ) have been estimated

Excess molar enthalpies for binary mixtures of different amines with water

International Nuclear Information System (INIS)

Zhang, Ruilei; Chen, Jian; Mi, Jianguo

2015-01-01

Highlights: • Isothermal excess molar enthalpies for binary mixtures of different amines with water. • The Redlich–Kister equation and the NRTL model was used to fit the experimental data. • The excess molar enthalpies were discussed with different structures of amines. - Abstract: The isothermal excess molar enthalpies for binary mixtures of different amines with water were measured with a C-80 Setaram calorimeter. The experimental results indicate that the excess molar enthalpy is related to the molecular structure. The experimental excess molar enthalpies were satisfactorily fitted with the Redlich–Kister equation. They were also used to test the suitability of the NRTL model, and the deviations are a little larger than the R–K equation

Effect of the mineral precipitation-dissolution at tunnel walls during the operational and post-operational phases

Energy Technology Data Exchange (ETDEWEB)

Domenech, Cristina; Arcos, David; Duro, Lara; Grandia, Fidel [Enviros Consul ting, Valldoreix, Barcelona (Spain)

2007-11-15

The extent of reversibility of the geochemical conditions disturbed during the construction and operational phases is of importance in order to assess the chemical evolution of the repository system. In this regard, it is essential to have a deep understanding of the chemical status of the repository system at closure in order to describe its immediate geochemical evolution beyond this point. This project assesses the dissolution and precipitation of minerals due to the interaction with groundwater in the deposition tunnel wall-rock during the operational phase (prior to tunnel backfilling) and during the saturation phase, also considering the effect on the backfill material. We have performed a 2D model in which a fracture intersecting the main tunnel has been considered. The project has been developed in two consecutive stages. The first stage simulates the precipitation and dissolution of minerals in the tunnel wall rock during the operational phase (100 years after excavation) when the tunnel is empty and filled with air. During this stage, water flows through fractures into the tunnel. The results of the model suggest that the interaction between groundwater, fracture-filling minerals, and atmospheric O{sub 2}(g) and CO{sub 2}(g) present in the tunnel leads to the precipitation of secondary minerals (calcite and iron(III) oxy-hydroxide) that do not significantly affect the porosity of the area surrounding the tunnel. The second stage starts after the operational phase, once the tunnel is backfilled, and simulates the interaction of groundwater with fracture-filling minerals and the backfill material. The model implemented assumes that the backfill is already water saturated and that water flows following the regional head gradient. Moreover, it also assumes that O2(g) is still present in the tunnel wall, as a result of the operational phase disturbances. The results show that oxygen will oxidise pyrite in the backfill and promote the precipitation of Fe

Vacancy formation enthalpies in bcc and fcc FeCo by positron annihilation

International Nuclear Information System (INIS)

Jackman, J.A.; Kim, S.M.; Buyers, W.J.L.

1982-01-01

A long slit angular correlation apparatus was used to measure the peak coincidence count rate in stoichiometric FeCo from 290 K to 1510 K. The count rate did not change significantly at the order-disorder phase transition (1008 K), but decreased sharply by 3.2% at the bcc-fcc phase transition at 1258 K. The threshold temperatures for the trapping of positrons in vacancies are measured to be 1125 K for the bcc phase and 1260 K for the fcc phase. The vacancy formation enthalpies in the bcc and fcc phases are determined to be 1.45 +- 0.05 eV and 1.63 +- 0.05 eV. The activation energies for self-diffusion have been estimated from the threshold temperatures, and are found to be 2.45 eV and 2.74 eV for the bcc and fcc phases respectively. (Auth.)

Dissolution studies of natural analogues spent fuel and U(VI)-Silicon phases of and oxidative alteration process

International Nuclear Information System (INIS)

Perez Morales, I.

2000-01-01

In order to understand the long-term behavior of the nuclear spent fuel in geological repository conditions, we have performed dissolution studies with natural analogues to UO 2 as well as with solid phases representatives of the oxidative alteration pathway of uranium dioxide, as observed in both natural environment and laboratory studies. In all cases, we have studied the influence of the bicarbonate concentration in the dissolution process, as a first approximation to the groundwater composition of a granitic environment, where carbonate is one of the most important complexing agents. As a natural analogue to the nuclear spent fuel some uraninite samples from the Oklo are deposit in Gabon, where chain fission reactions took place 2000 millions years ago, as well as a pitchblende sample from the mine Fe ore deposit, in Salamanca (spain) have been studied. The studies have been performed at 25 and 60 deg C and 60 deg C, and they have focussed on the determination of both the thermodynamic and the kinetic properties of the different samples studied, using batch and continuous experimental methodologies, respectively. (Author)

Immersion enthalpies of activated carbon cloths as physical chemistry characterization parameter

International Nuclear Information System (INIS)

Rodriguez, Giovanny; Giraldo, Liliana; Moreno Juan Carlos

2009-01-01

The immersion enthalpies of five activated carbon cloths in carbon, CCl 4 , H 2 O and NaOH and HCl 0.1 M solutions are determined. The surface area values of the cloths are between 243 and 848 m 2 g-1 and exhibit a linear relationship with the immersion enthalpies in CCl 4 . The immersion enthalpies of carbon cloths are between 5.49 and 42.3 Jg-1 for CCl 4 and 3.83 and 7.54 Jg-1 for H 2 O. The immersion enthalpies in the solutions are related to the contents of acidic and basic groups and find that in the first case to increase the immersion enthalpy in NaOH increases the total acidity. Hydrophobic factor is calculated from the immersion enthalpies in CCl 4 and H 2 O, that indicate the interaction with polar and a polar compounds, and also relates to pHPZC each sample.

Dissolution of aluminium

International Nuclear Information System (INIS)

Uriarte Hueda, A.; Berberana Eizmendi, M.; Pereira Sanchez, G.

1968-01-01

The dissolution of aluminum with acid solutions ( nitric acid-mercuric nitrate) and alkaline solutions (sodium hydroxide-sodium nitrate) has been studied. The instantaneous dissolution rate (IDR) has been studied in function of the concentration of the used reagents and the dissolution temperature. The complete dissolution has been included in the second part of this report, to know the total dissolution time, the consume of reagents and the stability of the resultant solutions. (Author)

Mechanisms and kinetics laws of inactive R7T7 reference glass dissolution in water at 90 deg C: initial dissolution rate measurements

International Nuclear Information System (INIS)

Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-02-01

The initial dissolution rate of inactive R7T7 reference glass was measured at 90 deg C in dilute aqueous solutions first at unspecified pH, then with imposed pH values. In distilled water, R7T7 glass corrosion initially involved preferential extraction of boron and network modifier elements (Li, Na, Ca) as long as the solution pH remained acid. When the solution pH became alkaline, glass dissolution was stoichiometric. These two mechanisms were confirmed by dissolution tests in aqueous solutions at imposed pH values under acid and alkaline conditions. The initial dissolution rate r 0 in mole.cm -3 .s -1 also increased significantly in alkaline media when the pH of the aqueous phase increased: in slightly acid media, selective glass dissolution formed a residual, de-alkalinized, hydrated glass that was characterized by transmission electron microscopy and secondary ion mass spectrometry. Under steady-state dissolution conditions, the initial glass corrosion rate (in mole.cm -3 .s -1 ) was: in acid and alkaline media, amorphous and crystallized alteration products formed after complete dissolution of the silicated glass network. The first products formed consisted mainly of Zr, Rare Earths, Fe and Al. (author). 67 refs., 29 figs., 26 tabs., 21 plates

The determination of the enthalpy of formation and the enthalpy increment of Cd0.5 Te0.5 by Calvet calorimetry

International Nuclear Information System (INIS)

Agarwal, R.; Venugopal, V.; Sood, D.D.

1993-01-01

In the present study the enthalpy of formation of Cd 0.5 Te 0.5 compound at 785 K were determined from the two elements by direct reaction calorimetry using two different types of set-ups. The enthalpy increment values were measured by drop technique in Calvet calorimetry. (author). 3 refs., 4 tabs

Determination of the free enthalpies of formation of borosilicate glasses; Determination des enthalpies libres de formation des verres borosilicates. Application a l'etude de l'alteration des verres de confinement de dechets radioactifs

Energy Technology Data Exchange (ETDEWEB)

Linard, Y

2000-07-01

This work contributes to the study of the thermochemical properties of nuclear waste glasses. Results are used to discuss mechanisms and parameters integrated in alteration models of conditioning materials. Glass is a disordered material defined thermodynamically as a non-equilibrium state. Taking into account one order parameter to characterise its configurational state, the metastable equilibrium for the glass was considered and the main thermochemical properties were determined. Calorimetric techniques were used to measure heat capacities and formation enthalpies of borosilicate glasses (from 3 to 8 constitutive oxides). Formation Entropies were measured too, using the entropy theory of relaxation processes proposed by Adam and Gibbs (1965). The configurational entropy contribution were determined from viscosity measurements. This set of data has allowed the calculation of Gibb's free energies of dissolution of glasses in pure water. By comparison with leaching experiments, it has been demonstrated that the decreasing of the dissolution rate at high reaction progress cannot be associated to the approach of an equilibrium between the sound glass and the aqueous solution. The composition changes of the reaction area at the glass surface need to be considered too. To achieve a complete description of the thermodynamic stability, the equilibrium between hydrated de-alkalinized glass and/or the gel layer with the aqueous solution should also be evaluated. (author)

Dissolution Coupled Biodegradation of Pce by Inducing In-Situ Biosurfactant Production Under Anaerobic Conditions

Science.gov (United States)

Dominic, J.; Nambi, I. M.

2013-12-01

Biosurfactants have proven to enhance the bioavailability and thereby elevate the rate of degradation of Light Non Aqueous Phase Liquids (LNAPLs) such as crude oil and petroleum derivatives. In spite of their superior characteristics, use of these biomolecules for remediation of Dense Non Aqueous Phase Liquids (DNAPLs) such as chlorinated solvents is still not clearly understood. In this present study, we have investigated the fate of tetrachloroethylene (PCE) by inducing in-situ biosurfactants production, a sustainable option which hypothesizes increase in bioavailability of LNAPLs. In order to understand the effect of biosurfactants on dissolution and biodegradation under the inducement of in-situ biosurfactant production, batch experiments were conducted in pure liquid media. The individual influence of each process such as biosurfactant production, dissolution of PCE and biodegradation of PCE were studied separately for getting insights on the synergistic effect of each process on the fate of PCE. Finally the dissolution coupled biodegradation of non aqueous phase PCE was studied in conditions where biosurfactant production was induced by nitrate limitation. The effect of biosurfactants was differentiated by repeating the same experiments were the biosurfactant production was retarded. The overall effect of in-situ biosurfactant production process was evaluated by use of a mathematical model. The process of microbial growth, biosurfactant production, dissolution and biodegradation of PCE were translated as ordinary differential equations. The modelling exercise was mainly performed to get insight on the combined effects of various processes that determine the concentration of PCE in its aqueous and non-aqueous phases. Model simulated profiles of PCE with the kinetic coefficients evaluated earlier from individual experiments were compared with parameters fitted for observations in experiments with dissolution coupled biodegradation process using optimization

Micromechanics of transformation fields in ageing linear viscoelastic composites: effects of phase dissolution or precipitation

Science.gov (United States)

Honorio, Tulio

2017-11-01

Transformation fields, in an affine formulation characterizing mechanical behavior, describe a variety of physical phenomena regardless their origin. Different composites, notably geomaterials, present a viscoelastic behavior, which is, in some cases of industrial interest, ageing, i.e. it evolves independently with respect to time and loading time. Here, a general formulation of the micromechanics of prestressed or prestrained composites in Ageing Linear Viscoelasticity (ALV) is presented. Emphasis is put on the estimation of effective transformation fields in ALV. The result generalizes Ageing Linear Thermo- and Poro-Viscoelasticity and it can be used in approaches coping with a phase transformation. Additionally, the results are extended to the case of locally transforming materials due to non-coupled dissolution and/or precipitation of a given (elastic or viscoelastic) phase. The estimations of locally transforming composites can be made with respect to different morphologies. As an application, estimations of the coefficient of thermal expansion of a hydrating alite paste are presented.

Biorelevant dissolution media

DEFF Research Database (Denmark)

Ilardia-Arana, David; Kristensen, Henning G; Müllertz, Anette

2006-01-01

Biorelevant dissolution media containing bile salt and lecithin at concentrations appropriate for fed and fasted state are useful when testing oral solid formulations of poorly water-soluble drugs. Dilution of amphiphile solutions affects the aggregation state of the amphiphiles because bile salt...... is partitioned between the aqueous phase and the aggregates. The aim of the investigation was to study the effect of dilution on the size distribution of aggregates and its effect on the solubilization capacity. Clear buffered solutions of four intestinal amphiphiles (sodium glycocholate, lecithin, monoolein...

Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration

Science.gov (United States)

Min, Yujia

Geologic CO2 sequestration (GCS) is considered a promising method to reduce anthropogenic CO2 emission. Assessing the supercritical CO2 (scCO2) gas or liquid phase water (g, l)-mineral interactions is critical to evaluating the viability of GCS processes. This work contributes to our understanding of geochemical reactions at CO 2-water (g, l)-mineral interfaces, by investigating the dissolution of aluminosilicates in CO2-acidified water (l). Plagioclase and biotite were chosen as model minerals in reservoir rock and caprock, respectively. To elucidate the effects of brine chemistry, first, the influences of cations in brine including Na, Ca, and K, have been investigated. In addition to the cations, the effects of abundant anions including sulfate and oxalate were also examined. Besides the reactions in aqueous phase, we also examine the carbonation of silicates in water (g)-bearing supercritical CO2 (scCO2) under conditions relevant to GCS. For the metal carbonation, in particular, the effects of particle sizes, water, temperature, and pressure on the carbonation of wollastonite were systematically examined. For understanding the cations effects in brine, the impacts of Na concentrations up to 4 M on the dissolution of plagioclase and biotite were examined. High concentrations of Na significantly inhibited plagioclase dissolution by competing adsorption with proton and suppressing proton-promoted dissolution. Ca has a similar effect to Na, and their effects did not suppress each other when Na and Ca co-existed. For biotite, the inhibition effects of Na coupled with an enhancing effect due to ion exchange reaction between Na and interlayer K, which cracked the basal surfaces of biotite. The K in aqueous phase significantly inhibited the dissolution. If the biotite is equilibrated with NaCl solutions initially, the biotite dissolved faster than the original biotite and the dissolution was inhibited by Na and K in brine. The outcomes improve our current knowledge of

Changes of enthalpy slope in subcooled flow boiling

Energy Technology Data Exchange (ETDEWEB)

Collado, Francisco J.; Monne, Carlos [Universidad de Zaragoza-CPS, Departamento de Ingenieria Mecanica-Motores Termicos, Zaragoza (Spain); Pascau, Antonio [Universidad de Zaragoza-CPS, Departamento de Ciencia de los Materiales y Fluidos-Mecanica de Fluidos, Zaragoza (Spain)

2006-03-01

Void fraction data in subcooled flow boiling of water at low pressure measured by General Electric in the 1960s are analyzed following the classical model of Griffith et al. (in Proceedings of ASME-AIChE heat transfer conference, 58-HT-19, 1958). In addition, a new proposal for analyzing one-dimensional steady flow boiling is used. This is based on the physical fact that if the two phases have different velocities, they cannot cover the same distance - the control volume length - in the same time. So a slight modification of the heat balance is suggested, i.e., the explicit inclusion of the vapor-liquid velocity ratio or slip ratio as scaling time factor between the phases, which is successfully checked against the data. Finally, the prediction of void fraction using correlations of the net rate of change of vapor enthalpy in the fully developed regime of subcooled flow boiling is explored. (orig.)

Dilution physics modeling: Dissolution/precipitation chemistry

International Nuclear Information System (INIS)

Onishi, Y.; Reid, H.C.; Trent, D.S.

1995-09-01

This report documents progress made to date on integrating dilution/precipitation chemistry and new physical models into the TEMPEST thermal-hydraulics computer code. Implementation of dissolution/precipitation chemistry models is necessary for predicting nonhomogeneous, time-dependent, physical/chemical behavior of tank wastes with and without a variety of possible engineered remediation and mitigation activities. Such behavior includes chemical reactions, gas retention, solids resuspension, solids dissolution and generation, solids settling/rising, and convective motion of physical and chemical species. Thus this model development is important from the standpoint of predicting the consequences of various engineered activities, such as mitigation by dilution, retrieval, or pretreatment, that can affect safe operations. The integration of a dissolution/precipitation chemistry module allows the various phase species concentrations to enter into the physical calculations that affect the TEMPEST hydrodynamic flow calculations. The yield strength model of non-Newtonian sludge correlates yield to a power function of solids concentration. Likewise, shear stress is concentration-dependent, and the dissolution/precipitation chemistry calculations develop the species concentration evolution that produces fluid flow resistance changes. Dilution of waste with pure water, molar concentrations of sodium hydroxide, and other chemical streams can be analyzed for the reactive species changes and hydrodynamic flow characteristics

Physicochemical characterization and dissolution properties of ...

African Journals Online (AJOL)

calorimetry (DSC), powder x-ray diffractometry (PXRD) and Fourier transform infrared (FT-IR) spectroscopy. Phase solubility studies revealed an AL-type diagram indicating a 1:1 stoichiometric inclusion complex and a stability constant value of 914 M-1. Solubility and dissolution rates of PYR and the binary systems were ...

Effects of alteration product precipitation on glass dissolution

Energy Technology Data Exchange (ETDEWEB)

Strachan, Denis M.; Neeway, James J.

2014-06-01

formation of the zeolitic phase. Therefore, the kinetics of secondary phase formation is an important parameter that should be taken into account in future glass dissolution modeling efforts. Secondly, the results indicate that, in the absence of a gel layer, the glass dissolution rate controls the rate of analcime precipitation in the long term. Finally, the meaning of these results pertinent to long-term glass durability is discussed.

Study of the distributions of flow rate and enthalpy in the sub-channels of a bundle geometry of nuclear reactors in one and two-phase flow

International Nuclear Information System (INIS)

Bayoumi, M.A.A.

1976-10-01

A bibliographic study shows that the experimental studies examined, have been developed to understand the phenomenon acting on the mixing between the sub-channels of which geometries are such these of rod bundles used in some nuclear reactors. Experimental devices and tests have been developed to study the influence of the following parameters, operating conditions, pressure, flow rate, power brought to the bundle and inlet temperature on the distribution of flow rates and vapor content among the different sub-channels. By means of non isokinetic sampling, one has determined the enthalpy of the fluid participating to the mixing between the communicating sub-channels and it has been shown that the value of this enthalpy depends strongly on the type of fluid flow and that this enthalpy cannot be either the enthalpy of one of the two sub-channels, nor (always) an average of these two enthalpies. The experimental results have been compared with calculations developed with the code FLICA, concerning the mass velocity distribution, the exchange term of linear momentum, and the variation of the transversal enthalpy with regard to the type of fluid flow. A study of local void ratio measurement, by means of optical probes, has been proposed. The present study has been carried out with a smooth geometry [fr

Development and validation of a dissolution test with reversed-phase high performance liquid chromatographic analysis for Candesartan cilexetil in tablet dosage forms

Directory of Open Access Journals (Sweden)

Vairappan Kamalakkannan

2016-09-01

Full Text Available A simple, rapid, selective and reproducible reversed-phase high performance liquid chromatographic (RP-HPLC method has been developed and validated for the estimation of release of Candesartan cilexetil (CC in tablets. Analysis was performed on an Agilent, Zorbax C8 column (150mm × 4.6mm, 5μm with the mobile phase consisting of phosphate buffer (pH2.5–acetonitrile (15:85, v/v at a flow rate of 1.0mL/min. UV detection was performed at 215nm and the retention time for CC was 2.2. The calibration curve was linear (correlation coefficient = 1.000 in the selected range of analyte. The optimized dissolution conditions include the USP apparatus 2 at a paddle rotation rate of 50rpm and 900mL of phosphate buffer (pH7.2 with 0.03% of polysorbate 80 as dissolution medium, at 37.0 ± 0.5°C. The method was validated for precision, linearity, specificity, accuracy, limit of quantitation and ruggedness. The system suitability parameters, such as theoretical plate, tailing factor and relative standard deviation (RSD between six standard replicates were well within the limits. The stability result shows that the drug is stable in the prescribed dissolution medium. Three different batches (A, B and C of the formulation containing 8mg of Candesartan cilexetil was performed with the developed method and the results showed no significant differences among the batches.

Study of anodic dissolution of Fe-Ru alloy with the aid of mossbauer spectroscopy

International Nuclear Information System (INIS)

Khlystov, A.S.; Fasman, A.B.; Kil'dibekova, G.A.

1986-01-01

This paper uses Fe 57 Mossbauer spectroscopy, whereby iron compounds may be identified quantitatively and their composition and structure can be determined, for the study of the relationships of slime formation from Fe-Ru binary alloys. Both the products of dissolution and the composition and state of intermediate phases formed at various stages of anodic dissolution were studied simultaneously. It was found that the slimes formed both during chemical and during electrochemical destruction of ruthenium-iron alloys are finely dispersed systems of complex composition, analogous to those formed in the course of electrochemical dissolution of Ni-Ru alloys, which were found to contain oxide phases of ruthenium (by x-ray spectroscopy and ESCA) and of nickel (by x-ray phase analysis). The difference between the slime compositions is determined mainly by kinetic factors

Thermodynamics of R-(+)-2-(4-Hydroxyphenoxy)propanoic Acid Dissolution in Methanol, Ethanol, and Methanol-Ethanol Mixture

Science.gov (United States)

Liu, Wei; Ma, Jinju; Yao, Xinding; Fang, Ruina; Cheng, Liang

2018-05-01

The solubilities of R-(+)-2-(4-hydroxyphenoxy)propanoic acid (D-HPPA) in methanol, ethanol and various methanol-ethanol mixtures are determined in the temperature range from 273.15 to 323.15 K at atmospheric pressure using a laser detecting system. The solubilities of D-HPPA increase with increasing mole fraction of ethanol in the methanol-ethanol mixtures. Experimental data were correlated with Buchowski-Ksiazczak λ h equation and modified Apelblat equation; the first one gives better approximation for the experimental results. The enthalpy, entropy and Gibbs free energy of D-HPPA dissolution in methanol, ethanol and methanol-ethanol mixtures were also calculated from the solubility data.

An empirical equation for the enthalpy of vaporization of quantum liquids

International Nuclear Information System (INIS)

Kuz, Victor A.; Meyra, Ariel G.; Zarragoicoechea, Guillermo J.

2004-01-01

An empirical equation for the enthalpy of vaporization of quantum fluids is presented. Dimensionless analysis is used to define enthalpy of vaporization as a function of temperature with a standard deviation of about 1%. Experimental data represented in these variables show two different behaviours and exhibit different maximum values of the enthalpy of vaporization, one corresponding to fluids with a triple point and the other to fluids having a lambda point. None of the existing empirical equations are able to describe this fact. Also enthalpy of vaporization of helium-3, n-deuterium and n-tritium are estimated

Crystal structure and thermochemical properties of 1-decylammonium hydrobromide (C10H21NH3Br)(s)

International Nuclear Information System (INIS)

Zhang Lijun; Di Youying; Lu Dongfei

2011-01-01

Highlights: → Crystal structure of 1-decylammonium hydrobromide was reported. → Lattice potential energy of the compound was obtained. → Molar volumes of the compound and its cation were obtained. → Ionic radius of its cation of the compound was calculated. → Molar enthalpy of dissolution at infinite dilution was determined. → Hydration enthalpies of the compound and its cation were calculated. - Abstract: The crystal structure of 1-decylammonium hydrobromide was determined by X-ray crystallography. Lattice potential energy and molar volumes of the solid compound and its cation were obtained respectively. The ionic radius of the cation can be calculated from the corresponding effective volume of the cation. The molar enthalpies of dissolution of the compound at different concentrations m/(mol . kg -1 ) at T = 298.15 K were measured by an isoperibol solution-reaction calorimeter at T = 298.15 K. According to the Pitzer's electrolyte solution theory, the molar enthalpy of dissolution of the compound at infinite dilution (Δ s H m ∞ ) and Pitzer parameters (β MX (0)L and β MX (1)L ) were obtained. The values of apparent relative molar enthalpies ( Φ L) of the title compound and relative partial molar enthalpies (L 2 -bar and L 1 -bar) of the solute and the solvent at different concentrations were derived from the experimental values of the enthalpy of dissolution of the compound. Finally, hydration enthalpies of the compound and its cation were calculated by designing a thermochemical cycle in accordance with lattice potential energy and the molar enthalpy of dissolution of the title compound at infinite dilution.

Entalpía de disolución de sulfacetamida sódica en agua: comparación entre la calorimetría isoperibólica de solución y el método de van't Hoff Dissolution enthalpy of sodium sulfacetamide in water: comparison between solution isoperibolic calorimetry and the van't Hoff method

Directory of Open Access Journals (Sweden)

Daniel R. Torres

2008-01-01

Full Text Available The dissolution enthalpy (ΔH0soln of sodium sulfacetamide in water was determined by means of isoperibolic solution calorimetry. It was found that ΔH0soln diminishes as the drug concentration increases. Otherwise, the calorimetric values obtained as a function of the drug concentration were significantly different than those predicted by the van't Hoff method. It was demonstrated that the later is not a fully reliable method for the determination of ΔH0soln values in the specific case of highly soluble sodium salts. The observed phenomenon could be explained by the presence of strong solute-solute interactions at high salt concentrations, in addition to solute-solvent and solvent-solvent interactions.

Vapor pressure and enthalpy of vaporization of aliphatic propanediamines

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Chernyak, Yury

2012-01-01

Highlights: ► We measured vapor pressure of four aliphatic 1,3-diamines. ► Vaporization enthalpies at 298 K were derived. ► We examined consistency of new and available data in the literature. ► A group-contribution method for prediction was developed. - Abstract: Vapor pressures of four aliphatic propanediamines including N-methyl-1,3-propanediamine (MPDA), N,N-dimethyl-1,3-propanediamine (DMPDA), N,N-diethyl-1,3-propanediamine (DEPDA) and N,N,N′,N′-tetramethyl-1,3-propanediamine (4MPDA) were measured using the transpiration method. The vapor pressures developed in this work and reported in the literature were used to derive molar enthalpy of vaporization values at the reference temperature 298.15 K. An internal consistency check of the enthalpy of vaporization was performed for the aliphatic propanediamines studied in this work. A group-contribution method was developed for the validation and prediction vaporization enthalpies of amines and diamines.

Standard molar enthalpies of formation of 2-chloroquinoline, 4-chloroquinoline, 6-chloroquinoline and 4,7-dichloroquinoline by rotating-bomb calorimetry

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Matos, Maria Agostinha R.; Amaral, Luisa M.P.F.

2006-01-01

The standard (p o =0.1MPa) molar enthalpies of combustion, Δ c H m - bar , for crystalline 2-, 4-, 6-chloroquinoline and 4,7-dichloroquinoline were determined at the temperature 298.15K using a rotating-bomb combustion calorimeter. The standard molar enthalpies of sublimation, Δ cr g H m o , at T= 298.15K, were determined by Calvet microcalorimetry. The results were as follows: -Δ c H m o (cr)/(kJ.mol -1 )Δ cr g H m o /(kJ.mol -1 )2-Chloroquinoline4492.5+/-1.684.3+/-2.64-Chloroquinoline4508.4 +/ -1.678.6+/-1.76-Chloroquinoline4508.2+/-1.680.8+/-1.94,7-Dichloroquinoline 4353.3+/-1.389.5+/-2.3 These values were used to derive the standard molar enthalpies of formation of the compounds in their crystalline and gaseous phases, respectively. The derived standard molar enthalpies of formation, in the gaseous state, are analysed in terms of enthalpic increments and interpreted in terms of molecular structure

Hypervelocity Expansion Facility for Fundamental High-Enthalpy Research

Science.gov (United States)

2017-02-27

ii Final Technical Report of Contract ONR N00014-15-1-2260 Entitled: HYPERVELOCITY EXPANSION FACILITY FOR FUNDAMENTAL HIGH-ENTHALPY...previous DoD investments in high-energy pulsed laser diagnostics for instantaneous planar velocimetry and thermometry to perform scientific studies of...capability for fundamental and applied studies of hypervelocity high enthalpy flows. In this document, we report on the progress over the 18-month

Calcite Dissolution Kinetics

Science.gov (United States)

Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

2016-12-01

A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

Non-Boussinesq Dissolution-Driven Convection in Porous Media

Science.gov (United States)

Amooie, M. A.; Soltanian, M. R.; Moortgat, J.

2017-12-01

Geological carbon dioxide (CO2) sequestration in deep saline aquifers has been increasingly recognized as a feasible technology to stabilize the atmospheric carbon concentrations and subsequently mitigate the global warming. Solubility trapping is one of the most effective storage mechanisms, which is associated initially with diffusion-driven slow dissolution of gaseous CO2 into the aqueous phase, followed by density-driven convective mixing of CO2 throughout the aquifer. The convection includes both diffusion and fast advective transport of the dissolved CO2. We study the fluid dynamics of CO2 convection in the underlying single aqueous-phase region. Two modeling approaches are employed to define the system: (i) a constant-concentration condition for CO2 in aqueous phase at the top boundary, and (ii) a sufficiently low, constant injection-rate for CO2 from top boundary. The latter allows for thermodynamically consistent evolution of the CO2 composition and the aqueous phase density against the rate at which the dissolved CO2 convects. Here we accurately model the full nonlinear phase behavior of brine-CO2 mixture in a confined domain altered by dissolution and compressibility, while relaxing the common Boussinesq approximation. We discover new flow regimes and present quantitative scaling relations for global characters of spreading, mixing, and dissolution flux in two- and three-dimensional media for the both model types. We then revisit the universal Sherwood-Rayleigh scaling that is under debate for porous media convective flows. Our findings confirm the sublinear scaling for the constant-concentration case, while reconciling the classical linear scaling for the constant-injection model problem. The results provide a detailed perspective into how the available modeling strategies affect the prediction ability for the total amount of CO2 dissolved in the long term within saline aquifers of different permeabilities.

A study of the dissolution mechanism by chemical and electrochemical oxidation-reduction of actinide dioxides (UO2, NpO2, PuO2, and AmO2) in an acid aqueous medium

International Nuclear Information System (INIS)

Berger, P.

1991-01-01

The plan followed to describe our study will be as follows: In a first part, we will review the general properties of MO 2 oxides (M = U, Np, Pu, and Am), as well as the dissolution methods known so far. We will emphasize, in particular, the great similarities in their structures, properties, and methods of dissolution, which justifies a parallel study of these oxides using an electrochemical method. The second part will concern the experimental study of the dissolution under electrolysis. We will, first of all, investigate its thermodynamic aspect, with the calculation of the free enthalpies of dissolution; and we will next show the phenomena of oxidizing dissolution and reducing dissolution using carbon paste electrodes. In a third part, we will present the test results on oxidizing dissolution in solutions that are highly enriched with oxygen-18. The isotopic analysis of the oxygen in the actinyl ions formed, deduced from the Raman spectra of the solutions, will make it possible to demonstrate the existence of a first oxidation step involving the participation of the solid. In the fourth part, we will summarize the experimental observations that might contribute to a better understanding of the mechanisms of oxidizing dissolution. A fifth and last part will be devoted to the presentation of a simple model of the dissolution of oxides in a carbon paste electrode under a constant current

Facing the challenge of predicting the standard formation enthalpies of n-butyl-phosphate species with ab initio methods

Science.gov (United States)

Saab, Mohamad; Réal, Florent; Šulka, Martin; Cantrel, Laurent; Virot, François; Vallet, Valérie

2017-06-01

Tributyl-phosphate (TBP), a ligand used in the PUREX liquid-liquid separation process of spent nuclear fuel, can form an explosive mixture in contact with nitric acid that might lead to a violent explosive thermal runaway. In the context of safety of a nuclear reprocessing plant facility, it is crucial to predict the stability of TBP at elevated temperatures. So far, only the enthalpies of formation of TBP are available in the literature with rather large uncertainties, while those of its degradation products, di-(HDBP) and mono-(H2MBP), are unknown. In this goal, we have used state-of-the art quantum chemical methods to compute the formation enthalpies and entropies of TBP and its degradation products di-(HDBP) and mono-(H2MBP) in gas and liquid phases. Comparisons of levels of quantum chemical theory revealed that there are significant effects of correlation on their electronic structures, pushing for the need of not only high level of electronic correlation treatment, namely, local coupled cluster with single and double excitation operators and perturbative treatment of triple excitations, but also extrapolations to the complete basis to produce reliable and accurate thermodynamics data. Solvation enthalpies were computed with the conductor-like screening model for real solvents [COSMO-RS], for which we observe errors not exceeding 22 kJ mol-1. We thus propose with final uncertainty of about 20 kJ mol-1 standard enthalpies of formation of TBP, HDBP, and H2MBP which amounts to -1281.7 ± 24.4, -1229.4 ± 19.6, and -1176.7 ± 14.8 kJ mol-1, respectively, in the gas phase. In the liquid phase, the predicted values are -1367.3 ± 24.4, -1348.7 ± 19.6, and -1323.8± 14.8 kJ mol-1, to which we may add about -22 kJ mol-1 error from the COSMO-RS solvent model. From these data, the complete hydrolysis of TBP is predicted as an exothermic phenomena but showing a slightly endergonic process.

A multiphase interfacial model for the dissolution of spent nuclear fuel

Energy Technology Data Exchange (ETDEWEB)

Jerden, James L., E-mail: jerden@anl.gov [Argonne National Laboratory, 9700 South Cass Ave., Argonne, IL 60439 (United States); Frey, Kurt [University of Notre Dame, Notre Dame, IN 46556 (United States); Ebert, William [Argonne National Laboratory, 9700 South Cass Ave., Argonne, IL 60439 (United States)

2015-07-15

Highlights: • This model accounts for chemistry, temperature, radiolysis, U(VI) minerals, and hydrogen effect. • The hydrogen effect dominates processes determining spent fuel dissolution rate. • The hydrogen effect protects uranium oxide spent fuel from oxidative dissolution. - Abstract: The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO{sub 2} and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO{sub 2} and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO{sub 2} and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H{sub 2}O{sub 2} and O{sub 2}). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit

Determination of vaporization enthalpies of polychlorinated biphenyls by correlation gas chromatography.

Science.gov (United States)

Puri, S; Chickos, J S; Welsh, W J

2001-04-01

The vaporization enthalpies of 16 polychlorinated biphenyls have been determined by correlation gas chromatography. This study was prompted by the realization that the vaporization enthalpy of the standard compounds used in previous studies, octadecane and eicosane, were values measured at 340 and 362 K, respectively, rather than at 298 K. Adjustment to 298 K amounts to a 7-8 kJ/mol increment in the values. With the inclusion of this adjustment, vaporization enthalpies evaluated by correlation gas chromatography are in good agreement with the values determined previously in the literature. The present results are based on the vaporization enthalpies of several standards whose values are well established in the literature. The standards include a variety of n-alkanes and various chlorinated hydrocarbons. The vaporization enthalpies of PCBs increased with the number of chlorine atoms and were found to be larger for meta- and para-substituted polychlorinated biphenyls.

Thermodynamic and structural models compared with the initial dissolution rates of SON glass samples

International Nuclear Information System (INIS)

Tovena, I.; Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-01-01

The experimentally determined initial dissolution rate R 0 of nuclear glass was correlated with thermodynamic parameters and structural parameters. The initial corrosion rates of six ''R7T7'' glass samples measured at 100 deg C in a Soxhlet device were correlated with the glass free hydration energy and the glass formation enthalpy. These correlations were then tested with a group of 26 SON glasses selected for their wide diversity of compositions. The thermodynamic models provided a satisfactory approximation of the initial dissolution rate determined under Soxhlet conditions for SON glass samples that include up to 15 wt% of boron and some alumina. Conversely, these models are inaccurate if the boron concentration exceeds 15 wt% and the glass contains no alumina. Possible correlations between R 0 and structural parameters, such as the boron coordination number and the number of nonbridging oxygen atoms, were also investigated. The authors show that R 0 varies inversely with the number of 4-coordinate boron atoms; conversely, the results do not substantiate published reports of a correlation between R 0 and the number of nonbridging oxygen atoms. (authors). 13 refs., 2 figs., 4 tabs

Integral enthalpy of mixing of the liquid ternary Au-Cu-Sn system

International Nuclear Information System (INIS)

Knott, S.; Li, Z.; Mikula, A.

2008-01-01

The integral enthalpy of mixing of the ternary Au-Cu-Sn has been determined with a Calvet type calorimeter at 6 different cross sections at 1273 K. The substitutional solution model of Redlich-Kister-Muggianu was used for a least square fit of the experimental data in order to get an analytical expression for the integral enthalpy of mixing. The ternary extrapolation models of Kohler, Muggianu and Toop were used to calculate the integral enthalpy of mixing and to compare measured and extrapolated values. Additional calculations of the integral enthalpy of mixing using the Chou model have been performed. With the calculated data, the iso-enthalpy lines have been determined using the Redlich-Kister-Muggianu model. A comparison of the data has been made

Solvation molar enthalpies and heat capacities of n-alkanes and n-alkylbenzenes on stationary phases of wide-ranging polarity.

Science.gov (United States)

Lebrón-Aguilar, Rosa; Quintanilla-López, Jesús Eduardo; Santiuste, José María

2010-12-03

A comparison of the most usual gas chromatographic methods for the calculation of partial molar enthalpies of solvation (Δ(sol)H(o)) has been carried out. Those methods based on the fitting of lnV(g) or ln(k/T) vs. 1/T and ln(k/T) vs. (1/T and the temperature arrangement, T(a)) are the most adequate ones for obtaining Δ(sol)H(o) values. However, the latter is the only reliable option for Δ(sol)H(o) estimation when commercial WCOT capillary columns are used, since in this case the estimation of some variables involved in the V(g) determination is less accurate or even impossible. Consequently, in this paper, Δ(sol)H(o) obtained from ln(k/T) vs. (1/T+T(a)) fitting at 373.15 and 298.15K for n-alkanes and n-alkylbenzenes on 12 commercial capillary columns coated with stationary phases covering the 203-3608 McReynolds polarity range are reported. Moreover, molar heat capacities of solvation at constant pressure (Δ(sol)C(p)(o)) have also been calculated using this method. A clear influence on Δ(sol)H(o) of the type and content of the substitution group in the stationary phase was observed. In addition, a linear relationship of Δ(sol)C(p)(o) with the van der Waals volume of the n-alkanes and the temperature gradient of density of the stationary phase was found. The effect of the size of the hydrocarbon on both thermodynamic variables was also investigated. Copyright © 2010 Elsevier B.V. All rights reserved.

Thermochemistry of certain rare earth and ammonium double chlorides

International Nuclear Information System (INIS)

Usubaliev, D.U.; Abramtsev, V.A.; Kydynov, M.K.; Vilyaev, A.N.

1987-01-01

In a calorimeter with isothermal casing at 25 deg C dissolution enthalpies of double chlorides of rare earths and ammonium LnCl 3 x2NH 4 Cl (Ln=La, Sm) and LnCl 3 x3NH 4 Cl (Ln=Gd, Tb, Ho) in water, as well as dissolution enthalpy of rare earth chlorides in solution of ammonium chloride and NH 4 Cl in solution of rare earth chloride, have been measured. Formation enthalpies, standard formation enthalpies, dissociation enthalpies of the above-mentioned double chlorides are calculated

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

A multiphase interfacial model for the dissolution of spent nuclear fuel

Science.gov (United States)

Jerden, James L.; Frey, Kurt; Ebert, William

2015-07-01

The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO2 and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO2 and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO2 and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H2O2 and O2). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit fuel degradation to chemical dissolution, which results in radionuclide source term values that are four or five orders of magnitude lower than when oxidative dissolution processes are operative. This paper presents the scientific basis of the model, the approach for modeling used fuel in a disposal system, and preliminary

Simulation study of effects of initial particle size distribution on dissolution

International Nuclear Information System (INIS)

Wang, G.; Xu, D.S.; Ma, N.; Zhou, N.; Payton, E.J.; Yang, R.; Mills, M.J.; Wang, Y.

2009-01-01

Dissolution kinetics of γ' particles in binary Ni-Al alloys with different initial particle size distributions (PSD) is studied using a three-dimensional (3D) quantitative phase field model. By linking model inputs directly to thermodynamic and atomic mobility databases, microstructural evolution during dissolution is simulated in real time and length scales. The model is first validated against analytical solution for dissolution of a single γ' particle in 1D and numerical solution in 3D before it is applied to investigate the effects of initial PSD on dissolution kinetics. Four different types of PSD, uniform, normal, log-normal and bimodal, are considered. The simulation results show that the volume fraction of γ' particles decreases exponentially with time, while the temporal evolution of average particle size depends strongly on the initial PSD

Dissolution of artemisinin/polymer composite nanoparticles fabricated by evaporative precipitation of nanosuspension.

Science.gov (United States)

Kakran, Mitali; Sahoo, Nanda Gopal; Li, Lin; Judeh, Zaher

2010-04-01

An evaporative precipitation of nanosuspension (EPN) method was used to fabricate composite particles of a poorly water-soluble antimalarial drug, artemisinin, with a hydrophilic polymer, polyethylene glycol (PEG), with the aim of enhancing the dissolution rate of artemisinin. We investigated the effect of polymer concentration on the physical, morphological and dissolution properties of the EPN-prepared artemisinin/PEG composites. The original artemisinin powder, EPN-prepared artemisinin nanoparticles and artemisinin/PEG composites were characterised by scanning electron microscopy, Fourier-transform infrared spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), dissolution testing and HPLC. The percentage dissolution efficiency, relative dissolution, time to 75% dissolution and mean dissolution time were calculated. The experimental drug dissolution data were fitted to various mathematical models (Weibull, first-order, Korsemeyer-Peppas, Hixson-Crowell cube root and Higuchi models) in order to analyse the release mechanism. The DSC and XRD studies suggest that the crystallinity of the EPN-prepared artemisinin decreased with increasing polymer concentration. The phase-solubility studies revealed an A(L)-type curve, indicating a linear increase in drug solubility with PEG concentration. The dissolution rate of the EPN-prepared artemisinin and artemisinin/PEG composites increased markedly compared with the original artemisinin powder. EPN can be used to prepare artemisinin nanoparticles and artemisinin/PEG composite particles that have a significantly enhanced dissolution rate. The mechanism of drug release involved diffusion and erosion.

Formation enthalpy of iron, chromium and aluminium vanadates

International Nuclear Information System (INIS)

Kesler, Ya.A.; Cheshnitskij, S.M.; Fotiev, A.A.; Tret'yakov, Yu.D.

1985-01-01

The enthalpies of formation of FeVO 4 , CrVO 4 and AlVO 4 orthovanadates are determined. The method for measuring reaction heats of direct synthesis of oxide compounds is used. All experiments have been conducted at 973 K. The measurements have been performed by the drop-calorimetry method using high temperature differential microcalorimeter. The specified enthalpy values of FeVO 4 , CrVO 4 , AlVO 4 and FeCr(VO 4 ) 2 formation are obtained

Lattice potential energies and thermochemical properties of triethylammonium halides (Et3NHX) (X = Cl, Br, and I)

International Nuclear Information System (INIS)

Liu Yupu; Tan Zhicheng; Di Youying; Xing Yiting; Zhang Peng

2012-01-01

Highlights: ► The crystal structures of (Et 3 NHX) (X = Cl, Br, and I) were determined. ► Lattice potential energies and ionic radius of the common cation were obtained. ► Molar enthalpies of dissolution at infinite dilution were derived. ► Relative partial molar enthalpies were derived. ► Hydration enthalpy of Et 3 NH + was calculated. - Abstract: A series of triethylammonium halides (Et 3 NHCl, Et 3 NHBr, and Et 3 NHI) was synthesized. The crystal structures of the three compounds were characterized by X-ray crystallography. The lattice potential energies and ionic radius of the common cation of the three compounds were obtained from crystallographic data. Molar enthalpies of dissolution of the compounds at various values of molality were measured in the double-distilled water at T = 298.150 K by means of an isoperibol solution-reaction calorimeter. According to Pitzer’s theory, the values of molar enthalpies of dissolution at infinite dilution and Pitzer’s parameters of the compounds were obtained. The values of apparent relative molar enthalpies, relative partial molar enthalpies of the solvent and the compounds at different molalities were derived from the experimental values of molar enthalpies of dissolution of the compounds. Finally, hydration enthalpy of the common cation Et 3 NH + was calculated to be ΔH + = −(150.386 ± 4.071) kJ · mol −1 by designing a thermochemical cycle.

Enthalpies of vaporization of some acetylene peroxy derivatives of carboranes-12

International Nuclear Information System (INIS)

Dibrivnyj, V.N.; Pistun, Z.E.; Van-Chin-Syan, Yu.Ya.; Yuvchenko, A.P.; Zvereva, T.D.

1999-01-01

Temperature dependences of saturated vapor pressure and vaporization enthalpies of five acetylene peroxy derivatives of carboranes-12 are determined by the Knudsen effusion method. Enthalpies and melting points of crystals, as well as temperatures of liquid compounds decomposition start are determined by the method of differential scanning calorimetry. Comparison of evaporation enthalpies determined in the study confirms the conclusions on non-additive character of intermolecular interaction in carboranes and their derivatives, which have been made previously [ru

Dissolution rates of over-the-counter painkillers: a comparison among formulations.

Science.gov (United States)

Alemanni, Matteo; Gatoulis, Sergio C; Voelker, Michael

2016-06-01

We wanted to compare the dissolution profile of several over-the-counter analgesics to understand whether the different formulation techniques employed to enhance absorption were associated with variations in the dissolution rate, a parameter known to affect drug absorption. We considered 5 formulations currently marketed in Italy: aspirin tablets (Aspirina Dolore e Infiammazione®), ibuprofen tablets and liquid capsules (Moment®), ibuprofen lysine tablets (Nurofenimmedia®) and dexketoprofen trometamol tablets (Enantyum®). Dissolution tests were performed according to the current USP/NF monograph dissolution procedure. Drug dissolution was evaluated at 1, 3, 6, 15, and 30 minutes since the start of the test. Dissolution was evaluated at three different pH: 1.2, 4.5 and 6.8. Every test was repeated 12 times. The aspirin formulation was by far the most rapid dissolving formulation, among those tested, with more than 80% of the tablet dissolved at 6 minutes for every pH considered. At pH 1.2 and 4.5, only the dexketoprofen formulation was able to reach the dissolution level of aspirin at 30 minutes, but had lower levels of dissolution at the previous time points. Instead, at pH 6.8, most of the formulations approached aspirin dissolution level, but only after 15 minutes. Ibuprofen capsules had the slowest kinetics, with a lag phase the first 6 minutes. Different formulation strategies can lead to great differences in the dissolution rates even among drugs of the same class, suggesting that enhancements in the formulation of painkillers can lead to improvements in drug absorption, and thus in the onset of analgesia.

Dissolution and alteration of uraninite under reducing conditions

International Nuclear Information System (INIS)

Janeczek, J.; Ewing, R.C.

1992-01-01

The behavior of uraninite under hydrothermal, reducung conditions is discussed on the basis of data in the literature and the authors' investigation of samples from two natural analogue sites: Oklo, Gabon and Cigar Lake, Canada. Uraninite under reducing conditions, in the presence of saline hydrothermal solutions may be altered through dissolution, preferential loss of lead and/or Y + HREE, and coffinitization. Textural features indicative of dissolution or uraninite include embayed grain boundaries, corroded relicts of uraninite embedded in a clay matrix, and replacement of uraninite by clays and sulfides. The alteration textures and phase chemistries at Oklo and Cigar Lake are remarkably similar. Dissolution of uraninite at Cigar Lake and Oklo was associated with the precipitation or illite and was probably caused by saline, uraninite moderately acidic solutions at approximately 200deg C. Increased oxygen fugacity may have occured locally due to release of excess oxygen from uraninite during dissolution or by α-radiolysis of the solution. The formation of Pb-rich (up to 18 wt% Pb, uraninite-I) and Pb-depleted (approximately 7-8 wt% Pb, uraninite-II) uraninites at both Oklo and Cigar Lake resulted from the loss of Pb due to predominantly episodic volume diffusion related to regional geologic events. Lead loss was not associated with U mobilization. In addition to uraninite dissolution, coffinitization resulted in U, Pb and REE release. (orig.)

Dissolution without disappearing: multicomponent gas exchange for CO2 bubbles in a microfluidic channel.

Science.gov (United States)

Shim, Suin; Wan, Jiandi; Hilgenfeldt, Sascha; Panchal, Prathamesh D; Stone, Howard A

2014-07-21

We studied the dissolution dynamics of CO2 gas bubbles in a microfluidic channel, both experimentally and theoretically. In the experiments, spherical CO2 bubbles in a flow of a solution of sodium dodecyl sulfate (SDS) first shrink rapidly before attaining an equilibrium size. In the rapid dissolution regime, the time to obtain a new equilibrium is 30 ms regardless of SDS concentration, and the equilibrium radius achieved varies with the SDS concentration. To explain the lack of complete dissolution, we interpret the results by considering the effects of other gases (O2, N2) that are already dissolved in the aqueous phase, and we develop a multicomponent dissolution model that includes the effect of surface tension and the liquid pressure drop along the channel. Solutions of the model for a stationary gas bubble show good agreement with the experimental results, which lead to our conclusion that the equilibrium regime is obtained by gas exchange between the bubbles and liquid phase. Also, our observations from experiments and model calculations suggest that SDS molecules on the gas-liquid interface form a diffusion barrier, which controls the dissolution behaviour and the eventual equilibrium radius of the bubble.

Enthalpy changes when passing from simple to complex perovskite-like oxides

International Nuclear Information System (INIS)

Reznitskij, L.A.

1999-01-01

Formation enthalpies of complex perovskite-like oxides and their hexagonal analogs of the composition: Ba 2 ReFeO 6 , Sr 2 ReFeO 6 , Sr 2 ReMnO 6 , Ca 2 ReMnO 6 , Sr 2 WCrO 6 , Sr 2 MoCrO 6 , Ca 2 MoCrO 6 , Ca 2 WCrO 6 , Ba 3 Fe 2 ReO 9 , Ba 3 Cr 2 ReO 9 , Ba 2 RhTaO 6 and B 2 ScIrO 6 from simple oxides were calculated by approximate method using enthalpies of the cations coordination change in oxygen medium. The conclusion was made that enthalpy stabilization of the oxide with regard to simple oxides is mainly determined by the change in enthalpies of alkaline earth metal cations [ru

Synthesis, characterization, and thermochemistry of the solid state coordination compound Zn(Nic){sub 2} . H{sub 2}O(s) (Nic = nicotinic acid)

Energy Technology Data Exchange (ETDEWEB)

Di Youying [College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong (China)], E-mail: yydi@lcu.edu.cn; Hong Yuanping; Kong Yuxia; Yang Weiwei [College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong (China); Tan Zhicheng [Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

2009-01-15

A novel compound, viz. zinc nicotinate monohydrate, was synthesized by the method of room temperature solid phase synthesis. The techniques of FT-IR chemical and elemental analyses and X-ray powder diffraction were applied to characterise the structure and composition of the complex. In accordance with Hess' law, a thermochemical cycle was designed and the enthalpy change of the solid phase reaction of nicotinic acid with hydrated zinc acetate was determined to be {delta}{sub r}H{sub m}{sup 0}=(46.71{+-}0.21)kJ.mol{sup -1} by use of an isoperibol solution-reaction calorimeter. The standard molar enthalpy of formation of the title complex Zn(Nic){sub 2} . H{sub 2}O(s) was calculated as -(1062.3 {+-} 2.0) kJ . mol{sup -1} by use of the enthalpies of dissolution and other auxiliary thermodynamic data.

Enthalpy of formation of titanium diboride

International Nuclear Information System (INIS)

Akhachinskij, V.V.; Chirin, N.A.

1975-01-01

The values given in the literature for the enthalpy of the formation of titanium diboride, as obtained experimentally and by theoretical estimation, range between -32 and -74.4 kcal/mol. In this paper the authors use the method of direct synthesis from elements in a Calvet calorimeter to determine the enthalpy of formation, ΔHsub(f) 0 , sub(298), of titanium diboride with the composition Tisub(1.000+-0.002)Bsub(2.056+-0.006)Csub(0.009)Nsub(0.003), which was found to be -76.78+-0.83 kcal/mol. They calculate that ΔHsub(f,298) (TiBsub(2.056)=-76.14+-0.85 kcal/mol. The procedure employed makes it possible to carry out the titanium diboride synthesis reaction with the calorimeter at room temperature

Formation enthalpy of iron, chromium and aluminium vanadates

Energy Technology Data Exchange (ETDEWEB)

Kesler, Ya.A.; Cheshnitskij, S.M.; Fotiev, A.A.; Tret' yakov, Yu.D.

1985-04-01

The enthalpies of formation of FeVO/sub 4/, CrVO/sub 4/ and AlVO/sub 4/ orthovanadates are determined. The method for measuring reaction heats of direct synthesis of oxide compounds is used. All experiments have been conducted at 973 K. The measurements have been performed by the drop-calorimetry method using high temperature differential microcalorimeter. The specified enthalpy values of FeVO/sub 4/, CrVO/sub 4/, AlVO/sub 4/ and FeCr(VO/sub 4/)/sub 2/ formation are obtained.

Theoretical calculation of enthalpy of formation of multiconformational molecules: 1,2-ethanediol, propanediols, and glycerol

Science.gov (United States)

Dorofeeva, Olga V.; Suchkova, Taisiya A.

2018-04-01

The gas-phase enthalpies of formation of four molecules with high flexibility, which leads to the existence of a large number of low-energy conformers, were calculated with the G4 method to see whether the lowest energy conformer is sufficient to achieve high accuracy in the computed values. The calculated values were in good agreement with the experiment, whereas adding the correction for conformer distribution makes the agreement worse. The reason for this effect is a large anharmonicity of low-frequency torsional motions, which is ignored in the calculation of ZPVE and thermal enthalpy. It was shown that the approximate correction for anharmonicity estimated using a free rotor model is of very similar magnitude compared with the conformer correction but has the opposite sign, and thus almost fully compensates for it. Therefore, the common practice of adding only the conformer correction is not without problems.

Solubility limits on radionuclide dissolution

Energy Technology Data Exchange (ETDEWEB)

Kerrisk, J.F.

1984-12-31

This paper examines the effects of solubility in limiting dissolution rates of a number of important radionuclides from spent fuel and high-level waste. Two simple dissolution models were used for calculations that would be characteristics of a Yucca Mountain repository. A saturation-limited dissolution model, in which the water flowing through the repository is assumed to be saturated with each waste element, is very conservative in that it overestimates dissolution rates. A diffusion-limited dissolution model, in which element-dissolution rates are limited by diffusion of waste elements into water flowing past the waste, is more realistic, but it is subject to some uncertainty at this time. Dissolution rates of some elements (Pu, Am, Sn, Th, Zr, Sm) are always limited by solubility. Dissolution rates of other elements (Cs, Tc, Np, Sr, C, I) are never solubility limited; their release would be limited by dissolution of the bulk waste form. Still other elements (U, Cm, Ni, Ra) show solubility-limited dissolution under some conditions. 9 references, 3 tables.

Improved algorithm based on equivalent enthalpy drop method of pressurized water reactor nuclear steam turbine

International Nuclear Information System (INIS)

Wang Hu; Qi Guangcai; Li Shaohua; Li Changjian

2011-01-01

Because it is difficulty to accurately determine the extraction steam turbine enthalpy and the exhaust enthalpy, the calculated result from the conventional equivalent enthalpy drop method of PWR nuclear steam turbine is not accurate. This paper presents the improved algorithm on the equivalent enthalpy drop method of PWR nuclear steam turbine to solve this problem and takes the secondary circuit thermal system calculation of 1000 MW PWR as an example. The results show that, comparing with the design value, the error of actual thermal efficiency of the steam turbine cycle obtained by the improved algorithm is within the allowable range. Since the improved method is based on the isentropic expansion process, the extraction steam turbine enthalpy and the exhaust enthalpy can be determined accurately, which is more reasonable and accurate compared to the traditional equivalent enthalpy drop method. (authors)

Enhancing Entropy and Enthalpy Fluctuations to Drive Crystallization in Atomistic Simulations

Science.gov (United States)

Piaggi, Pablo M.; Valsson, Omar; Parrinello, Michele

2017-07-01

Crystallization is a process of great practical relevance in which rare but crucial fluctuations lead to the formation of a solid phase starting from the liquid. As in all first order first transitions, there is an interplay between enthalpy and entropy. Based on this idea, in order to drive crystallization in molecular simulations, we introduce two collective variables, one enthalpic and the other entropic. Defined in this way, these collective variables do not prejudge the structure into which the system is going to crystallize. We show the usefulness of this approach by studying the cases of sodium and aluminum that crystallize in the bcc and fcc crystalline structures, respectively. Using these two generic collective variables, we perform variationally enhanced sampling and well tempered metadynamics simulations and find that the systems transform spontaneously and reversibly between the liquid and the solid phases.

Enthalpy of Vaporization by Gas Chromatography: A Physical Chemistry Experiment

Science.gov (United States)

Ellison, Herbert R.

2005-01-01

An experiment is conducted to measure the enthalpy of vaporization of volatile compounds like methylene chloride, carbon tetrachloride, and others by using gas chromatography. This physical property was measured using a very tiny quantity of sample revealing that it is possible to measure the enthalpies of two or more compounds at the same time.

Aerosol volatility and enthalpy of sublimation of carboxylic acids.

Science.gov (United States)

Salo, Kent; Jonsson, Asa M; Andersson, Patrik U; Hallquist, Mattias

2010-04-08

The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.

Dissolution of methane bubbles with hydrate armoring in deep ocean conditions

Science.gov (United States)

Kovalchuk, Margarita; Socolofsky, Scott

2017-11-01

The deep ocean is a storehouse of natural gas. Methane bubble moving upwards from marine sediments may become trapped in gas hydrates. It is uncertain precisely how hydrate armoring affects dissolution, or mass transfer from the bubble to the surrounding water column. The Texas A&M Oilspill Calculator was used to simulate a series of gas bubble dissolution experiments conducted in the United States Department of Energy National Energy Technology Laboratory High Pressure Water Tunnel. Several variations of the mass transfer coefficient were calculated based on gas or hydrate phase solubility and clean or dirty bubble correlations. Results suggest the mass transfer coefficient may be most closely modeled with gas phase solubility and dirty bubble correlation equations. Further investigation of hydrate bubble dissolution behavior will refine current numeric models which aid in understanding gas flux to the atmosphere and plumes such as oil spills. Research funded in part by the Texas A&M University 2017 Undergraduate Summer Research Grant and a Grant from the Methane Gas Hydrates Program of the US DOE National Energy Technology Laboratory.

Evaluating the role of re-adsorption of dissolved Hg(2+) during cinnabar dissolution using isotope tracer technique.

Science.gov (United States)

Jiang, Ping; Li, Yanbin; Liu, Guangliang; Yang, Guidi; Lagos, Leonel; Yin, Yongguang; Gu, Baohua; Jiang, Guibin; Cai, Yong

2016-11-05

Cinnabar dissolution is an important factor controlling mercury (Hg) cycling. Recent studies have suggested the co-occurrence of re-adsorption of the released Hg during the course of cinnabar dissolution. However, there is a lack of feasible techniques that can quantitatively assess the amount of Hg re-adsorbed on cinnabar when investigating cinnabar dissolution. In this study, a new method, based on isotope tracing and dilution techniques, was developed to study the role of Hg re-adsorption in cinnabar dissolution. The developed method includes two key components: (1) accurate measurement of both released and spiked Hg in aqueous phase and (2) estimation of re-adsorbed Hg on cinnabar surface via the reduction in spiked (202)Hg(2+). By adopting the developed method, it was found that the released Hg for trials purged with oxygen could reach several hundred μgL(-1), while no significant cinnabar dissolution was detected under anaerobic condition. Cinnabar dissolution rate when considering Hg re-adsorption was approximately 2 times the value calculated solely with the Hg detected in the aqueous phase. These results suggest that ignoring the Hg re-adsorption process can significantly underestimate the importance of cinnabar dissolution, highlighting the necessity of applying the developed method in future cinnabar dissolution studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Enthalpy and void distributions in subchannels of PHWR fuel bundles

Energy Technology Data Exchange (ETDEWEB)

Park, J W; Choi, H; Rhee, B W [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

1999-12-31

Two different types of the CANDU fuel bundles have been modeled for the ASSERT-IV code subchannel analysis. From calculated values of mixture enthalpy and void fraction distribution in the fuel bundles, it is found that net buoyancy effect is pronounced in the central region of the DUPIC fuel bundle when compared with the standard CANDU fuel bundle. It is also found that the central region of the DUPIC fuel bundle can be cooled more efficiently than that of the standard fuel bundle. From the calculated mixture enthalpy distribution at the exit of the fuel channel, it is found that the mixture enthalpy and void fraction can be highest in the peripheral region of the DUPIC fuel bundle. On the other hand, the enthalpy and the void fraction were found to be highest in the central region of the standard CANDU fuel bundle at the exit of the fuel channel. This study shows that the subchannel analysis is very useful in assessing thermal behavior of the fuel bundle that could be used in CANDU reactors. 10 refs., 4 figs., 2 tabs. (Author)

Enthalpy and void distributions in subchannels of PHWR fuel bundles

Energy Technology Data Exchange (ETDEWEB)

Park, J. W.; Choi, H.; Rhee, B. W. [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

1998-12-31

Two different types of the CANDU fuel bundles have been modeled for the ASSERT-IV code subchannel analysis. From calculated values of mixture enthalpy and void fraction distribution in the fuel bundles, it is found that net buoyancy effect is pronounced in the central region of the DUPIC fuel bundle when compared with the standard CANDU fuel bundle. It is also found that the central region of the DUPIC fuel bundle can be cooled more efficiently than that of the standard fuel bundle. From the calculated mixture enthalpy distribution at the exit of the fuel channel, it is found that the mixture enthalpy and void fraction can be highest in the peripheral region of the DUPIC fuel bundle. On the other hand, the enthalpy and the void fraction were found to be highest in the central region of the standard CANDU fuel bundle at the exit of the fuel channel. This study shows that the subchannel analysis is very useful in assessing thermal behavior of the fuel bundle that could be used in CANDU reactors. 10 refs., 4 figs., 2 tabs. (Author)

Enhancement of dissolution of Telmisartan through use of solid dispersion technique surface solid dispersion

Directory of Open Access Journals (Sweden)

Bhumika Patel

2012-01-01

Full Text Available The present study was aimed to increase the solubility of the poorly water soluble drug Telmisartan by using Surface solid dispersion (SSD made of polymers like Poloxamer 407, PEG 6000 by Solvent evaporation method. The drug was solubilized by surfactants and/or polymers then adsorbed onto the surface of extremely fine carriers to increase its surface area and to form the SSD which give the more Surface area for absorption of the drug. A 2 2 full factorial design was used to investigate for each carrier the joint influence of formulation variables: Amount of carrier and adsorbent. Saturation solubility studies shows the improvement in solubility of drug batch SSD 8 give more solubility improvement than the other batch, in-vitro dissolution of pure drug, physical mixtures and SSDs were carried out in that SSDs were found to be effective in increasing the dissolution rate of Telmisartan in form of SSD when compared to pure drug. Also FT-IR spectroscopy, differential scanning calorimetry and X-ray diffractometry studies were carried out in order to characterize the drug and Surface solid dispersion. Furthermore, both DSC and X-ray diffraction showed a decrease in the melting enthalpy and reduced drug crystallinity consequently in SSDs. However, infrared spectroscopy revealed no drug interactions with the carriers.

Vapour pressure and enthalpy of vaporization of aliphatic poly-amines

International Nuclear Information System (INIS)

Efimova, Anastasia A.; Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Chernyak, Yury

2010-01-01

Molar enthalpies of vaporization of aliphatic poly-amines: 1,4-dimethylpiperazine [106-58-1], 1-(2-aminoethyl)-piperazine, [140-31-8], 1-(2-aminoethyl)-4-methyl-piperazine [934-98-5], and triethylenetetramine [112-24-3] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures of the parent compounds have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of poly-amines at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for poly-amines studied in this work.

Calcination/dissolution residue treatment

International Nuclear Information System (INIS)

Knight, R.C.; Creed, R.F.; Patello, G.K.; Hollenberg, G.W.; Buehler, M.F.; O'Rourke, S.M.; Visnapuu, A.; McLaughlin, D.F.

1994-09-01

Currently, high-level wastes are stored underground in steel-lined tanks at the Hanford site. Current plans call for the chemical pretreatment of these wastes before their immobilization in stable glass waste forms. One candidate pretreatment approach, calcination/dissolution, performs an alkaline fusion of the waste and creates a high-level/low-level partition based on the aqueous solubilities of the components of the product calcine. Literature and laboratory studies were conducted with the goal of finding a residue treatment technology that would decrease the quantity of high-level waste glass required following calcination/dissolution waste processing. Four elements, Fe, Ni, Bi, and U, postulated to be present in the high-level residue fraction were identified as being key to the quantity of high-level glass formed. Laboratory tests of the candidate technologies with simulant high-level residues showed reductive roasting followed by carbonyl volatilization to be successful in removing Fe, Ni, and Bi. Subsequent bench-scale tests on residues from calcination/dissolution processing of genuine Hanford Site tank waste showed Fe was separated with radioelement decontamination factors of 70 to 1,000 times with respect to total alpha activity. Thermodynamic analyses of the calcination of five typical Hanford Site tank waste compositions also were performed. The analyses showed sodium hydroxide to be the sole molten component in the waste calcine and emphasized the requirement for waste blending if fluid calcines are to be achieved. Other calcine phases identified in the thermodynamic analysis indicate the significant thermal reconstitution accomplished in calcination

The excess enthalpies of liquid Ge-Pb-Te alloys

International Nuclear Information System (INIS)

Blachnik, R.; Binder, J.; Schlieper, A.

1997-01-01

The excess enthalpies of liquid alloys in the ternary system Ge-Pb-Te were determined at 1210 K in a heat flow calorimeter for five sections Ge y Pb 1-y -Te with y = 0.2, 0.4, 0.5, 0.6 and 0.8 and at 1153 K for Ge 0.5 Pb 0.5 -Te. The enthalpy surface in the ternary system is determined by a valley of exothermic minima, stretching from an exothermic minimum at the composition GeTe to one at the composition PbTe in the respective binaries. The excess enthalpies in the limiting metallic binary were adapted with the Redlich-Kister formalism. For the description of the thermodynamic functions in the ternary system the equation of Bonnier was taken using ternary coefficients. The calculated curves are in good agreement with the experimental data. (orig.)

Magnesite dissolution and precipitation rates at hydrothermal conditions

International Nuclear Information System (INIS)

Saldi, Giuseppe

2009-01-01

Magnesite (MgCO 3 ) is the stable anhydrous member of a series of Mg-carbonates with different degrees of hydration. Despite its relative scarcity in the natural environments, it constitutes an important mineral phase for the permanent sequestration of CO 2 as carbonate minerals. Experimental determination of magnesite precipitation and dissolution rates at conditions representative of the storage sites is therefore fundamental for the assessment of magnesite sequestration potential in basaltic and ultramafic rocks and the optimization of the techniques of CO 2 storage. Magnesite precipitation rates have been measured using mixed-flow and batch reactors as a function of temperature (100 ≤ T ≤ 200 deg. C), solution composition and CO 2 partial pressure (up to 30 bar). Rates were found to be independent of aqueous solution ionic strength at 0.1 M 3 2- activity at pH > 8. All rates obtained from mixed flow reactor experiments were found to be consistent with the model of Pokrovsky et al. (1999) where magnesite precipitation rates are proportional to the concentration of the >MgOH 2 + surface species. The study of magnesite crystallization using hydrothermal atomic force microscopy (HAFM) demonstrated the consistency of the rates derived from microscopic measurements with those obtained from bulk experiments and showed that these rates are also consistent with a spiral growth mechanism. According to AFM observations this mechanism controls magnesite growth over a wide range of temperatures and saturation states (15≤ Ω ≤200 for 80 ≤T 2 to accelerate the rate of the overall carbonation process, avoiding the inhibiting effect of carbonate ions on magnesite precipitation and increasing the rates of Mg-silicate dissolution via acidification of reacting solutions. Determination of magnesite dissolution rates by mixed flow reactor at 150 and 200 deg. C and at neutral to alkaline conditions allowed us to improve and extend to high temperatures the surface

Laboratory Experiments and Modeling of Pooled NAPL Dissolution in Porous Media

Science.gov (United States)

Copty, N. K.; Sarikurt, D. A.; Gokdemir, C.

2017-12-01

The dissolution of non-aqueous phase liquids (NAPLs) entrapped in porous media is commonly modeled at the continuum scale as the product of a chemical potential and an interphase mass transfer coefficient, the latter expressed in terms of Sherwood correlations that are related to flow and porous media properties. Because of the lack of precise estimates of the interface area separating the NAPL and aqueous phase, numerous studies have lumped the interfacial area into the interphase mass transfer coefficient. In this paper controlled dissolution experiments from a pooled NAPL were conducted. The immobile NAPL mass is placed at the bottom of a flow cell filled with porous media with water flowing on top. Effluent aqueous phase concentrations were measured for a wide range of aqueous phase velocities and for two types of porous media. To interpret the experimental results, a two-dimensional pore network model of the NAPL dissolution was developed. The well-defined geometry of the NAPL-water interface and the observed effluent concentrations were used to compute best-fit mass transfer coefficients and non-lumped Sherwood correlations. Comparing the concentrations predicted with the pore network model to simple previously used one-dimensional analytic solutions indicates that the analytic model which ignores the transverse dispersion can lead to over-estimation of the mass transfer coefficient. The predicted Sherwood correlations are also compared to previously published data and implications on NAPL remediation strategies are discussed.

Energetics of the molecular interactions of L-alanine and L-serine with xylitol, D-sorbitol, and D-mannitol in aqueous solutions at 298.15 K

Science.gov (United States)

Mezhevoi, I. N.; Badelin, V. G.

2013-04-01

Integral enthalpies of dissolution Δsol H m of L-alanine and L-serine are measured via the calorimetry of dissolution in aqueous solutions of xylitol, D-sorbitol, and D-mannitol. Standard enthalpies of dissolution (Δsol H ○) and the transfer (Δtr H ○) of amino acids from water to binary solvent are calculated from the experimental data. Using the McMillan-Mayer theory, enthalpy coefficients of pairwise interactions h xy of amino acids with molecules of polyols are calculated that are negative. The obtained results are discussed within the theory of the prevalence of different types of interactions in mixed solutions and the effect of the structural features of interacting biomolecules on the thermochemical parameters of dissolution of amino acids.

Enthalpy of sublimation/vaporization of trans-cyclohexyl-1,4-diamine and cis-cyclohexyl-1,2-diamine

International Nuclear Information System (INIS)

Tome, Luciana I.N.; Rosado, Mario T.S.; Nunes, Sandra C.C.; Maria, Teresa M.R.; Canotilho, Joao; Eusebio, M. Ermelinda S.

2007-01-01

The molar enthalpy of sublimation, Δ cr g H m 0 , of trans-cyclohexyl-1,4-diamine and the molar enthalpy of vaporization, Δ l g H m 0 , of cis-cyclohexyl-1,2-diamine, at the temperature 298.15 K, were determined by calorimetry. Δ cr g H m 0 (T=298.15K)=(105.0±0.8)kJ.mol -1 was obtained for the trans-isomer and Δ l g H m 0 (T=298.15K)=(62.2±1.0)kJ.mol -1 for the cis form. The molar enthalpy of fusion of the first compound, at T = 342.1 K, was determined by differential scanning calorimetry. The molar enthalpy of vaporization of the 1,4-isomer was estimated by combining the value of the enthalpy of sublimation with that of the enthalpy of fusion. The values obtained for molar standard enthalpy of vaporization and those available for the enthalpy of the diamines in the gas state were used to calculate the difference between the enthalpies of both compounds in the liquid state

Influence of tribomechanical micronization and hydrocolloids addition on enthalpy and apparent specific heat of whey protein model solutions

Directory of Open Access Journals (Sweden)

Zoran Herceg

2002-01-01

Full Text Available Knowledge of thermophysical properties, especially the phase transitions temperature, specific heat and enthalpy, are essential in defining the freezing process parameters as well as storage conditions of frozen food. In this work thermophysical properties of 10% model solutions prepared with 60% whey protein concentrate (WPC with various hydrocolloids addition (HVEP, YO-EH, YO-L i YO-M were investigated. Powdered whey protein concentrate was treated in equipment for tribomechanical micronization and activation at 40000 rpm (Patent: PCT/1B99/00757 just before model solutions preparation. Particle size analysis was performed using Frich –laser particle sizer “analysette 22”. The phase transition temperatures were determined by differential thermal analysis (DTA, while specific heat and enthalpy were calculated according to several mathematical equations. The results have shown that, due to tribomechanical treatment, certain changes in thermophysical and energetic properties of materials occurred. Tribomechanical treatment affects changes in granulometrical composition of WPC which result in higher abilities of reactions with hydrocolloids in model solutions and significant changes in thermophysical properties of the mentioned models.

Enthalpy estimation for thermal comfort and energy saving in air conditioning system

International Nuclear Information System (INIS)

Chu, C.-M.; Jong, T.-L.

2008-01-01

The thermal comfort control of a room must consider not only the thermal comfort level but also energy saving. This paper proposes an enthalpy estimation that is conducive for thermal comfort control and energy saving. The least enthalpy estimator (LEE) combines the concept of human thermal comfort with the theory of enthalpy to predict the load for a suitable setting pair in order to maintain more precisely the thermal comfort level and save energy in the air conditioning system

Enthalpy of formation of zircon

International Nuclear Information System (INIS)

Ellison, A.J.G.; Navrotsky, A.

1992-01-01

Using high-temperature solution calorimetry in molt 2PbO · B 2 O 3 , the enthalpy of reaction of the formation of zircon, ZrSiO 4 , from its constituent oxides has been determined: Δ 4 H 977 (ZrSiO 4 ) = -27.9 (±1.9) kJ/mol. With previously reported data for the heat contents of ZrO 2 SiO 2 and ZrSiO 4 and standard-state enthalpies of formation of ZrO 2 and SiO 2 , we obtain Δ f H 298 degrees. (ZrSiO 4 ) = -2034.2 (±3.1) kJ/mol and Δ t G 298 degrees (ZrSiO 4 ) = -1919.8 kJ/mol. The free energy value is in excellent agreement with a range previously estimated from solid-state reaction equilibria. At higher temperature also the data are in close agreement with existing data, though the data sets diverge somewhat with increasing T. In this paper the limitations of the data for predicting the breakdown temperature of zircon into its constituent oxides are discussed

Ionic liquids: differential scanning calorimetry as a new indirect method for determination of vaporization enthalpies.

Science.gov (United States)

Verevkin, Sergey P; Emel'yanenko, Vladimir N; Zaitsau, Dzmitry H; Ralys, Ricardas V; Schick, Christoph

2012-04-12

Differential scanning calorimetry (DSC) has been used to measure enthalpies of synthesis reactions of the 1-alkyl-3-methylimidazolium bromide [C(n)mim][Br] ionic liquids from 1-methylimidazole and n-alkyl bromides (with n = 4, 5, 6, 7, and 8). The optimal experimental conditions have been elaborated. Enthalpies of formation of these ionic liquids in the liquid state have been determined using the DSC results according to the Hess Law. The ideal-gas enthalpies of formation of [C(n)mim][Br] were calculated using the methods of quantum chemistry. They were used together with the DSC results to derive indirectly the enthalpies of vaporization of the ionic liquids under study. In order to validate the indirect determination, the experimental vaporization enthalpy of [C(4)mim][Br] was measured by using a quartz crystal microbalance (QCM). The combination of reaction enthalpy measurements by DSC with modern high-level first-principles calculations opens valuable indirect thermochemical options to obtain values of vaporization enthalpies of ionic liquids.

Development of in situ ion selective sensors for dissolution

International Nuclear Information System (INIS)

Bohets, Hugo; Vanhoutte, Koen; De Maesschalck, Roy; Cockaerts, Paul; Vissers, Bert; Nagels, Luc J.

2007-01-01

The dissolution of formulations of the drugs dapoxetine, paliperidone, cinnarizine, tetrazepam, mebeverine, loperamide, galantamine and ibuprofen was studied by an in-line potentiometric measurement system. The transpose of a Nikolskii-Eisenman type function performed the conversion of potential to percentage of dissolution. A novel gradient membrane electrode was developed especially for dissolution, varying continuously in composition from an ionically conducting rubber phase to an electronically conducting solid state PVC/graphite composite. The gradient part had a thickness of 200 μm. The electrodes life span exceeded 6 months. An ion exchange procedure was used to prepare them for one specific drug. This enabled us to use one universal electrode built to measure a wide array of drugs. The system parameters such as accuracy, reproducibility and linearity were presented with the data obtained for the drug dapoxetine. In dissolution, accurate measurements were possible from 10 -9 to 10 -3 M concentrations, for high log P drugs. The effect of t 90 response times on the measurement error was estimated. The t 90 response times of the electrodes were concentration dependent, and varied between 50 and 10 s for, respectively, 10 -6 and 10 -3 M concentrations. Potential drift was studied in detail. The measurements performed with these electrodes showed an accuracy of 1%, and inter- and intra electrode variabilities of 0.6 and 1.7%, respectively. The electrodes were successfully applied in colloidal media containing suspended matter, typically formed during dissolution of tablets. The advantages and pitfalls of potentiometry over the presently used techniques for dissolution testing are discussed

Aqueous Dissolution of Silver Iodide and Associated Iodine Release Under Reducing Conditions with Sulfide

International Nuclear Information System (INIS)

Yaohiro Inagaki; Toshitaka Imamura; Kazuya Idemitsu; Tatsumi Arima; Osamu Kato; Hidekazu Asano; Tsutomu Nishimura

2007-01-01

Aqueous dissolution tests of silver iodide (AgI) were performed in Na 2 S solutions in order to evaluate, empirically, dissolution of AgI to release iodine under reducing conditions with sulfide. The results indicated that AgI dissolves to release iodine being controlled by mainly precipitation of Ag 2 S. However, the dissolution of AgI can be depressed to proceed, and the thermodynamic equilibrium cannot be attained easily. Solid phase analysis for the reacted AgI suggested that a thin layer of solid silver forming at AgI surface may evolve to be protective against transportation of reactant species, which can lead to the depression in the dissolution of AgI. (authors)

Low-temperature heat capacities and standard molar enthalpy of formation of N-methylnorephedrine C211H17NO(s)

Institute of Scientific and Technical Information of China (English)

Di You-Ying; Wang Da-Qi; Shi Quan; Tan Zhi-Cheng

2008-01-01

This paper reports that low-temperature heat capacities of N-methylnorephedrine C11H17NO(s) have been mea- sured by a precision automated adiabatic calorimeter over the temperature range from T=78 K to T=400 K. A solid to liquid phase transition of the compound was found in the heat capacity curve in the temperature range of T=342- 364 K. The peak temperature, molar enthalpy and entropy of fusion of the substance were determined. The experimental values of the molar heat capacities in the temperature regions of T=78-342 K and T=364-400 K were fitted to two poly- nomial equations of heat capacities with the reduced temperatures by least squares method. The smoothed molar heat capacities and thermodynamic functions of N-methylnorephedrine C11H17NO(s) relative to the standard refer- ence temperature 298.15 K were calculated based on the fitted polynomials and tabulated with an interval of 5 K. The constant-volume energy of combustion of the compound at T=298.15 K was measured by means of an isoperibol preci- sion oxygen-bomb combustion calorimeter. The standard molar enthalpy of combustion of the sample was calculated. The standard molar enthalpy of formation of the compound was determined from the combustion enthalpy and other auxiliary thermodynamic data through a Hess thermochemical cycle.

Going full circle: phase-transition thermodynamics of ionic liquids.

Science.gov (United States)

Preiss, Ulrich; Verevkin, Sergey P; Koslowski, Thorsten; Krossing, Ingo

2011-05-27

We present the full enthalpic phase transition cycle for ionic liquids (ILs) as examples of non-classical salts. The cycle was closed for the lattice, solvation, dissociation, and vaporization enthalpies of 30 different ILs, relying on as much experimental data as was available. High-quality dissociation enthalpies were calculated at the G3 MP2 level. From the cycle, we could establish, for the first time, the lattice and solvation enthalpies of ILs with imidazolium ions. For vaporization, lattice, and dissociation enthalpies, we also developed new prediction methods in the course of our investigations. Here, as only single-ion values need to be calculated and the tedious optimization of an ion pair can be circumvented, the computational time is short. For the vaporization enthalpy, a very simple approach was found, using a surface term and the calculated enthalpic correction to the total gas-phase energy. For the lattice enthalpy, the most important constituent proved to be the calculated conductor-like screening model (COSMO) solvation enthalpy in the ideal electric conductor. A similar model was developed for the dissociation enthalpy. According to our assessment, the typical error of the lattice enthalpy would be 9.4 kJ mol(-1), which is less than half the deviation we get when using the (optimized) Kapustinskii equation or the recent volume-based thermodynamics (VBT) theory. In contrast, the non-optimized VBT formula gives lattice enthalpies 20 to 140 kJ mol(-1) lower than the ones we assessed in the cycle, because of the insufficient description of dispersive interactions. Our findings show that quantum-chemical calculations can greatly improve the VBT approaches, which were parameterized for simple, inorganic salts with ideally point-shaped charges. In conclusion, we suggest the term "augmented VBT", or "aVBT", to describe this kind of theoretical approach. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluating the role of re-adsorption of dissolved Hg{sup 2+} during cinnabar dissolution using isotope tracer technique

Energy Technology Data Exchange (ETDEWEB)

Jiang, Ping [Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199 (United States); Li, Yanbin [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education/Qingdao Collaborative Innovation Center of Marine Science and Technology, Ocean University of China, Qingdao 266100 (China); Liu, Guangliang [Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199 (United States); Southeast Environmental Research Center, Florida International University, Miami, FL 33199 (United States); Yang, Guidi [College of Life Sciences, Fujian Agriculture and Forestry University, Fuzhou 350002 (China); Lagos, Leonel [Applied Research Center, Florida International University, Miami, FL 33199 (United States); Yin, Yongguang [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Gu, Baohua [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 (United States); Jiang, Guibin [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Cai, Yong, E-mail: cai@fiu.edu [Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199 (United States); Southeast Environmental Research Center, Florida International University, Miami, FL 33199 (United States)

2016-11-05

Highlights: • Develop a new method to study Hg re-adsorption in cinnabar. • Both isotope dilution and tracer techniques were adopted. • The presence of O{sub 2} can significantly enhance the dissolution of cinnabar. • Prove the necessity of including re-adsorption in estimating cinnabar dissolution. - Abstract: Cinnabar dissolution is an important factor controlling mercury (Hg) cycling. Recent studies have suggested the co-occurrence of re-adsorption of the released Hg during the course of cinnabar dissolution. However, there is a lack of feasible techniques that can quantitatively assess the amount of Hg re-adsorbed on cinnabar when investigating cinnabar dissolution. In this study, a new method, based on isotope tracing and dilution techniques, was developed to study the role of Hg re-adsorption in cinnabar dissolution. The developed method includes two key components: (1) accurate measurement of both released and spiked Hg in aqueous phase and (2) estimation of re-adsorbed Hg on cinnabar surface via the reduction in spiked {sup 202}Hg{sup 2+}. By adopting the developed method, it was found that the released Hg for trials purged with oxygen could reach several hundred μg L{sup −1}, while no significant cinnabar dissolution was detected under anaerobic condition. Cinnabar dissolution rate when considering Hg re-adsorption was approximately 2 times the value calculated solely with the Hg detected in the aqueous phase. These results suggest that ignoring the Hg re-adsorption process can significantly underestimate the importance of cinnabar dissolution, highlighting the necessity of applying the developed method in future cinnabar dissolution studies.

Specification and comparative calculation of enthalpies and Gibbs formation energies of anhydrous lanthanide nitrates

International Nuclear Information System (INIS)

Del' Pino, Kh.; Chukurov, P.M.; Drakin, S.I.

1980-01-01

Analyzed are the results of experimental depermination of formation enthalpies of waterless nitrates of lanthane cerium, praseodymium, neodymium and samarium. Using method of comparative calculation computed are enthalpies of formation of waterless lanthanide and yttrium nitrates. Calculated values of enthalpies and Gibbs energies of waterless lanthanide nitrate formation are tabulated

Dissolution Methods Database

Data.gov (United States)

U.S. Department of Health & Human Services — For a drug product that does not have a dissolution test method in the United States Pharmacopeia (USP), the FDA Dissolution Methods Database provides information on...

Thermodynamic and structural models compared with the initial dissolution rates of open-quotes SONclose quotes glass samples

International Nuclear Information System (INIS)

Tovena, I.; Advocat, T.; Ghaleb, D.; Vernaz, E.; Larche, F.

1994-01-01

The experimentally determined initial dissolution rate R 0 of nuclear glass was correlated with thermodynamic parameters and structural parameters. The initial corrosion rates of six open-quotes R7T7close quotes glass samples measured at 100 degrees C in a Soxhlet device were correlated with the glass free hydration energy and the glass formation enthalpy. These correlations were then tested with a group of 26 SON glasses selected for their wide diversity of compositions. The thermodynamic models provided a satisfactory approximation of the initial dissolution rate determined under Soxhlet conditions for SON glass samples that include up to 15 wt% of boron and some alumina. Conversely, these models are inaccurate if the boron concentration exceeds 15 wt% and the glass contains no alumina. Possible correlations between R 0 and structural parameters, such as the boron coordination number and the number of nonbridging oxygen atoms, were also investigated. The authors show that R 0 varies inversely with the number of 4-coordinate boron atoms; conversely, the results do not substantiate published reports of a correlation between R 0 and the number of nonbridging oxygen atoms

The gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide from combustion calorimetry, vapor pressure measurements, and ab initio calculations.

Science.gov (United States)

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas

2007-04-04

Ionic liquids are attracting growing interest as alternatives to conventional molecular solvents. Experimental values of vapor pressure, enthalpy of vaporization, and enthalpy of formation of ionic liquids are the key thermodynamic quantities, which are required for the validation and development of the molecular modeling and ab initio methods toward this new class of solvents. In this work, the molar enthalpy of formation of the liquid 1-butyl-3-methylimidazolium dicyanamide, 206.2 +/- 2.5 kJ.mol-1, was measured by means of combustion calorimetry. The molar enthalpy of vaporization of 1-butyl-3-methylimidazolium dicyanamide, 157.2 +/- 1.1 kJ.mol-1, was obtained from the temperature dependence of the vapor pressure measured using the transpiration method. The latter method has been checked with measurements of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, where data are available from the effusion technique. The first experimental determination of the gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide, 363.4 +/- 2.7 kJ.mol-1, from thermochemical measurements (combustion and transpiration) is presented. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for 1-butyl-3-methylimidazolium dicyanamide using the G3MP2 theory. Excellent agreement with experimental results has been observed. The method developed opens a new way to obtain thermodynamic properties of ionic liquids which have not been available so far.

Studies of the thermal dissolution process of the Suzuki phase of the Eu2+ ion in KBr single crystals by analysis of photoacoustic signals

International Nuclear Information System (INIS)

MejIa-Uriarte, E V; Castaneda-Guzman, R; Villagran-Muniz, M; Camarillo, E; A, J Hernandez; S, H Murrieta; Navarrete, M

2003-01-01

An experimental investigation of the thermal behaviour of the dissolution process of the Suzuki phase (SP) by continuous heating (1 deg. C min -1 ) of KBr:Eu 2+ crystals is reported in this work. The thermal profiles were determined by the correlation functions between subsequent photoacoustic (PA) signals registered during the dissolution process. The behaviour of the thermal profile is directly related to the absorption coefficient of the Eu 2+ ion in precipitated states that are present in the crystal. The PA signal is detected as a consequence of the non-radiative processes that take place after the excitation of the low-energy band of the Eu 2+ ion by means of a focused laser pulse at 355 nm. The results obtained by this method are compared with those simultaneously obtained by the photoluminescence (PL) technique. The samples were heated from room temperature to 205 deg. C. The PA signal and PL spectrum were obtained every 6 deg. C. The temperature range of the SP dissolution process was from 77 to 115 deg. C. These results are in agreement with those obtained by the PL technique and with the data reported in the literature

Enhanced dissolution of TCE in NAPL by TCE-degrading bacteria in wetland soils

International Nuclear Information System (INIS)

Lee, Sangjin

2007-01-01

The influence of trichloroethene (TCE) dechlorinating mixed cultures in dissolution of TCE in nonaqueous phase liquid (NAPL) via biodegradation was observed. Experiments were conducted in batch reactor system with and without marsh soils under 10 and 20 deg. C for 2 months. The dissolution phenomenon in biotic reactors containing mixed cultures was showed temporal increases compared to abiotic reactors treated with biocide. Effective NAPL-water transfer rate (K m ) calculated in this study showed more than four times higher in biotic reactors than that in abiotic reactors. The results might be attributed to the biologically enhanced dissolution process via dechlorination in reactors. Temperature would be a factor to determine the dissolution rate by controlling bacterial activity. The TCE dechlorination occurred even in an interface of TCE-NAPL that demonstrated no previous TCE biodegradation, suggesting that microbes may be useful in developing source-zone bioremediation system. In conclusion, dechlorinating mixed culture could enhance dissolution in NAPL that may be useful in the application of source zone bioremediation

Effects of electric fields in polymerization on enthalpy of PMAA anhydridization

Energy Technology Data Exchange (ETDEWEB)

Chang Zhenqi; Liu Gang; Zhang Zhicheng

2004-02-19

PMAA (polymethacrylic acid) polymerized by {gamma}-irradiation in electric field forms six-membered cyclic anhydride during heating process and the enthalpy of PMAA anhydridization was determined by DSC. Why the endothermic peak of PMAA anhydridization in DSC curve between 200 and 300 deg. C appears is particularly explained by calculation. The relations between applied electric field and the enthalpy of PMAA anhydridization are studied. The results show that, with the increases of the intensity of electric field in polymerization, the enthalpy of PMAA forming anhydrides nonlinearly increase, which might be related to orientation of carboxylic acid groups of the PMAA in an electric field.

Study of the dissolution velocity of dispersed solid particles. Development of a calculation method for analyzing the kinetic curves. Extension to the study of composed kinetics

International Nuclear Information System (INIS)

Jorda, Michel.

1976-01-01

The dissolution of a solid in an aqueous phase is studied, the solid consisting of dispersed particles. A continuous colorimetric analysis method is developed to study the dissolution process and a two-parameter optimization method is established to investigate the kinetic curves obtained. This method is based on the differential equation dx/dt=K(1-x)sup(n). (n being the decrease in the dissolution velocity when the dissolved part increases and K a velocity parameter). The dissolution of SO 4 Cu and MnO 4 K in water and UO 3 in SO 4 H 2 is discussed. It is shown that the dissolution velocity of UO 3 is proportional to the concentration of the H + ions in the solution as far as this one is not higher than 0.25N. The study of the temperature dependence of the UO 3 dissolution reaction shows that a transition phase takes place from 25 to 65 0 C between a phase in which the dissolution is controlled by the diffusion of the H + ions and the chemical reaction at the interface and a phase in which the kinetics is only controlled by the diffusion [fr

High-temperature enthalpies of plutonium monocarbide and plutonium sesquicarbide

International Nuclear Information System (INIS)

Oetting, F.L.

1979-01-01

The high-temperature enthalpies of plutonium monocarbide and plutonium sesquicarbide have been determined with a copper-block calorimeter of the isoperibol type. The experimental enthalpy data, which was measured relative to 298 K, covered the temperature range from 400 to 1500 K. The calculation of the temperature rise of the calorimeter takes into account the added heat evolution from the radioactive decay of the plutonium samples. These enthalpy results, combined with the heat capacity and entropy of the respective carbide at 298 K available from the literature, has made it possible to generate tables of thermodynamic functions for the plutonium carbides. The behavior of the heat capacity of both of the plutonium carbides, i.e., a relatively steep increase in the heat capacity as the temperature increases, may be attributed to a premelting effect with the formation of vacancies within the crystal lattice although a theoretical treatment of this phenomenon is not given

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.

A correct enthalpy relationship as thermal comfort index for livestock.

Science.gov (United States)

Rodrigues, Valéria Cristina; da Silva, Iran José Oliveira; Vieira, Frederico Márcio Corrêa; Nascimento, Sheila Tavares

2011-05-01

Researchers working with thermal comfort have been using enthalpy to measure thermal energy inside rural facilities, establishing indicator values for many situations of thermal comfort and heat stress. This variable turned out to be helpful in analyzing thermal exchange in livestock systems. The animals are exposed to an environment which is decisive for the thermoregulatory process, and, consequently, the reactions reflect states of thermal comfort or heat stress, the last being responsable for problems of sanity, behavior and productivity. There are researchers using enthalpy as a qualitative indicator of thermal environment of livestock such as poultry, cattle and hogs in tropical regions. This preliminary work intends to check different enthalpy equations using information from classical thermodynamics, and proposes a direct equation as thermal comfort index for livestock systems.

Boron isotope fractionation in magma via crustal carbonate dissolution.

Science.gov (United States)

Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

2016-08-04

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Boron isotope fractionation in magma via crustal carbonate dissolution

Science.gov (United States)

Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

2016-08-01

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to -41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

An autoclave system for uranium oxide dissolution experiments

International Nuclear Information System (INIS)

Nykyri, Mikko

1985-05-01

According to the decision in principle of the Council of State of Finland the nuclear energy producers must provide preparedness for carrying out the final disposal of spent nuclear fuel in Finland. By the present principal concept the spent fuel will be disposed deep into the granitic bedrock. A parameter needed by risk analysis models is the dissolution rate of the uranium oxide matrix in the fuel pellets. In order to approach conditions prevailing deep in the groundwater, and autoclave system for dissolution experiments was developed at the Technical Research Centre of Finland. The low oxygen content and high pressure at elevated temperatures are simulated in the system. 20 MPa and 100 deg C are the upper operation limits of pressure and temperature. Water can be changed in the experiment autoclave without remarkable pressure and temperature variations. This has been arranged by using three pressure vessels: a supply vessel, a dissolution vessel and a depletion vessel. The extreme vessels serve pressure balancing purposes during water exchange. The water is deoxygenated during a preparation phase in the supply vessel by flushing it with nitrogen gas. Polytetrafluoroethylene is the principal material in contact with the water. A redox electrode couple was developed for potential measurements inside the dissolution vessel. The reference electrode is of Ag/AgCl-type with saturated KC1 electrolyte. A platinum wire operates as a measuring electrode

Development of in situ ion selective sensors for dissolution

Energy Technology Data Exchange (ETDEWEB)

Bohets, Hugo [Antwerp University, Chemistry Department, Groenenborgerlaan 171, B-2020 Antwerpen (Belgium); Vanhoutte, Koen [Johnson and Johnson Pharmaceutical Research and Development, Turnhoutseweg 30, B-2340 Beerse (Belgium); De Maesschalck, Roy [Johnson and Johnson Pharmaceutical Research and Development, Turnhoutseweg 30, B-2340 Beerse (Belgium); Cockaerts, Paul [Johnson and Johnson Pharmaceutical Research and Development, Turnhoutseweg 30, B-2340 Beerse (Belgium); Vissers, Bert [Antwerp University, Chemistry Department, Groenenborgerlaan 171, B-2020 Antwerpen (Belgium); Nagels, Luc J. [Antwerp University, Chemistry Department, Groenenborgerlaan 171, B-2020 Antwerpen (Belgium)]. E-mail: luc.nagels@ua.ac.be

2007-01-02

The dissolution of formulations of the drugs dapoxetine, paliperidone, cinnarizine, tetrazepam, mebeverine, loperamide, galantamine and ibuprofen was studied by an in-line potentiometric measurement system. The transpose of a Nikolskii-Eisenman type function performed the conversion of potential to percentage of dissolution. A novel gradient membrane electrode was developed especially for dissolution, varying continuously in composition from an ionically conducting rubber phase to an electronically conducting solid state PVC/graphite composite. The gradient part had a thickness of 200 {mu}m. The electrodes life span exceeded 6 months. An ion exchange procedure was used to prepare them for one specific drug. This enabled us to use one universal electrode built to measure a wide array of drugs. The system parameters such as accuracy, reproducibility and linearity were presented with the data obtained for the drug dapoxetine. In dissolution, accurate measurements were possible from 10{sup -9} to 10{sup -3} M concentrations, for high log P drugs. The effect of t {sub 90} response times on the measurement error was estimated. The t {sub 90} response times of the electrodes were concentration dependent, and varied between 50 and 10 s for, respectively, 10{sup -6} and 10{sup -3} M concentrations. Potential drift was studied in detail. The measurements performed with these electrodes showed an accuracy of 1%, and inter- and intra electrode variabilities of 0.6 and 1.7%, respectively. The electrodes were successfully applied in colloidal media containing suspended matter, typically formed during dissolution of tablets. The advantages and pitfalls of potentiometry over the presently used techniques for dissolution testing are discussed.

Enthalpy of sublimation/vaporization of trans-cyclohexyl-1,4-diamine and cis-cyclohexyl-1,2-diamine

OpenAIRE

Tomé, Luciana I. N.; Rosado, Mário T. S.; Nunes, Sandra C. C.; Maria, Teresa M. R.; Canotilho, João; Eusébio, M. Ermelinda S.

2007-01-01

The molar enthalpy of sublimation, , of trans-cyclohexyl-1,4-diamine and the molar enthalpy of vaporization, , of cis-cyclohexyl-1,2-diamine, at the temperature 298.15 K, were determined by calorimetry. was obtained for the trans-isomer and for the cis form. The molar enthalpy of fusion of the first compound, at T = 342.1 K, was determined by differential scanning calorimetry. The molar enthalpy of vaporization of the 1,4-isomer was estimated by combining the value of the enthalpy of sublimat...

Calibration models for high enthalpy calorimetric probes.

Science.gov (United States)

Kannel, A

1978-07-01

The accuracy of gas-aspirated liquid-cooled calorimetric probes used for measuring the enthalpy of high-temperature gas streams is studied. The error in the differential temperature measurements caused by internal and external heat transfer interactions is considered and quantified by mathematical models. The analysis suggests calibration methods for the evaluation of dimensionless heat transfer parameters in the models, which then can give a more accurate value for the enthalpy of the sample. Calibration models for four types of calorimeters are applied to results from the literature and from our own experiments: a circular slit calorimeter developed by the author, single-cooling jacket probe, double-cooling jacket probe, and split-flow cooling jacket probe. The results show that the models are useful for describing and correcting the temperature measurements.

Vaporization thermodynamics and enthalpy of formation of aluminum silicon carbide

International Nuclear Information System (INIS)

Behrens, R.G.; Rinehart, G.H.

1984-01-01

The vaporization thermodynamics of aluminum silicon carbide was investigated using Knudsen effusion mass spectrometry. Vaporization occurred incongruently to give Al(g), SiC(s), and graphite as reaction products. The vapor pressure of aluminum above (Al 4 SiC 4 + SiC + C) was measured using graphite effusion cells with orifice areas between 1.1 X 10 -2 and 3.9 X 10 -4 cm 2 . The vapor pressure of aluminum obtained between 1427 and 1784 K using an effusion cell with the smallest orifice area, 3.9 X 10 -4 cm 2 , is expressed as log p (Pa) = - (18567 + or - 86) (K/T) + (12.143 + or - 0.054) The third-law calculation of the enthalpy change for the reaction Al 4 SiC 4 (s) = 4Al(g) + SiC(hex) + 3C(s) using the present aluminum pressures gives ΔH 0 (298.15 K) = (1455 + or - 79) kJ /SUP ./ mol -1 . The corresponding second-law result is ΔH 0 (298.15 K) = (1456 + or - 47) kJ /SUP ./ mol -1 . The standard enthalpy of formation of Al 4 SiC 4 (s) from the elements calculated from the present vaporization enthalpy (third-law calculation) and the enthalpies of formation of Al(g) and hexagonal SiC is ΔH 0 /SUB f/ (298.15 K) = -(221 + or - 85) kJ /SUP ./ mol -1 . The standard enthalpy of formation of Al 4 SiC 4 (s) from its constituent carbides Al 4 C 3 (s) and SiC(c, hex) is calculated to be ΔH 0 (298.15 K) = (38 + or - 92) KJ /SUP ./ mol -1

Validation and Application of a New Reversed Phase HPLC Method for In Vitro Dissolution Studies of Rabeprazole Sodium in Delayed-Release Tablets

Directory of Open Access Journals (Sweden)

Md. Saddam Nawaz

2013-01-01

Full Text Available The purpose of this study was to develop and validate a new reversed phase high performance liquid chromatographic (RP-HPLC method to quantify in vitro dissolution assay of rabeprazole sodium in pharmaceutical tablet dosage form. Method development was performed on C 18, 100×4.6 mm ID, and 10 μm particle size column, and injection volume was 20 μL using a diode array detector (DAD to monitor the detection at 280 nm. The mobile phase consisted of buffer: acetonitrile at a ratio of 60 : 40 (v/v, and the flow rate was maintained at 1.0 mL/min. The method was validated in terms of suitability, linearity, specificity, accuracy, precision, stability, and sensitivity. Linearity was observed over the range of concentration 0.05–12.0 μg/mL, and the correlation coefficient was found excellent >0.999. The method was specific with respect to rabeprazole sodium, and the peak purity was found 99.99%. The method was precise and had relative standard deviations (RSD less than 2%. Accuracy was found in the range of 99.9 to 101.9%. The method was robust in different variable conditions and reproducible. This proposed fast, reliable, cost-effective method can be used as quality control tool for the estimation of rabeprazole sodium in routine dissolution test analysis.

Method of determining the enthalpy and moisture content of wet steam

International Nuclear Information System (INIS)

Silvestri, G.J. Jr.

1991-01-01

This patent describes a nuclear powered multi-stage steam turbine system wherein steam at higher than atmospheric pressure is introduced into the turbine system at a high pressure turbine element and thereafter flows through a series of turbine elements at successively decreasing pressures, wherein portions of the steam are extracted from the turbine elements at a plurality of lower pressure points and the steam is finally exhausted at a lowest pressure point, the method of determining moisture content and enthalpy of steam at a selected pressure point. It comprises sampling a small quantity of steam at the selected pressure point; super heating the steam sample to a single-phase state by reducing its pressure and bottling it in a closed measuring chamber whereby the flow energy of the sample is converted into internal energy; measuring the pressure of the steam sample within the chamber; determining the sonic velocity of the steam sample by passing a sound wave through the sample from a transmitter to a receiver located at a known distance from the transmitter and measuring the time required for the sound wave to travel from transmitter to receiver; and utilizing the measured pressure and sonic velocity of the steam sample to calculate the moisture content and enthalpy of the steam at the selected pressure point

Effect of Calcium chloride and Cadmium chloride on the enthalpy of ...

African Journals Online (AJOL)

This paper presents the effect of two dissolved inorganic salts, CaCl2 and CdCl2 on the enthalpy of mixing of the binary 1,4 dioxane + water system has been investigated at 303.15 K in an isothermal displacement calorimeter with vapour space. A significantly increasing trend in the endothermic excess enthalpy values for ...

Vapour pressures and enthalpies of vaporization of a series of the ferrocene derivatives

International Nuclear Information System (INIS)

Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Krol, Olesya V.; Varushchenko, Raisa M.; Chelovskaya, Nelly V.

2007-01-01

Vapour pressures of the ferrocene, ferrocene-methanol, benzyl-ferrocene, and benzoyl-ferrocene have been determined by the transpiration method. The molar enthalpies of sublimation Δ cr g H m and of vaporization Δ l g H m have been determined from the temperature dependence of the vapour pressure. The molar enthalpies of fusion of these compounds were measured by d.s.c. The measured data sets of vaporization, sublimation, and fusion enthalpies were checked for internal consistency

In Vitro-In Vivo Predictive Dissolution-Permeation-Absorption Dynamics of Highly Permeable Drug Extended-Release Tablets via Drug Dissolution/Absorption Simulating System and pH Alteration.

Science.gov (United States)

Li, Zi-Qiang; Tian, Shuang; Gu, Hui; Wu, Zeng-Guang; Nyagblordzro, Makafui; Feng, Guo; He, Xin

2018-05-01

Each of dissolution and permeation may be a rate-limiting factor in the absorption of oral drug delivery. But the current dissolution test rarely took into consideration of the permeation property. Drug dissolution/absorption simulating system (DDASS) valuably gave an insight into the combination of drug dissolution and permeation processes happening in human gastrointestinal tract. The simulated gastric/intestinal fluid of DDASS was improved in this study to realize the influence of dynamic pH change on the complete oral dosage form. To assess the effectiveness of DDASS, six high-permeability drugs were chosen as model drugs, including theophylline (pK a1  = 3.50, pK a2  = 8.60), diclofenac (pK a  = 4.15), isosorbide 5-mononitrate (pK a  = 7.00), sinomenine (pK a  = 7.98), alfuzosin (pK a  = 8.13), and metoprolol (pK a  = 9.70). A general elution and permeation relationship of their commercially available extended-release tablets was assessed as well as the relationship between the cumulative permeation and the apparent permeability. The correlations between DDASS elution and USP apparatus 2 (USP2) dissolution and also between DDASS permeation and beagle dog absorption were developed to estimate the predictability of DDASS. As a result, the common elution-dissolution relationship was established regardless of some variance in the characteristic behavior between DDASS and USP2 for drugs dependent on the pH for dissolution. Level A in vitro-in vivo correlation between DDASS permeation and dog absorption was developed for drugs with different pKa. The improved DDASS will be a promising tool to provide a screening method on the predictive dissolution-permeation-absorption dynamics of solid drug dosage forms in the early-phase formulation development.

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

Science.gov (United States)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system

Dissolution of nuclear fuels

International Nuclear Information System (INIS)

Uriarte Hueda, A.; Berberana Eizmendi, M.; Rainey, R.

1968-01-01

A laboratory study was made of the instantaneous dissolution rate (IDR) for unirradiated uranium metal rods and UO 2 , PuO 2 and PuO 2 -UO 2 pellets in boiling nitric acid alone and with additives. The uranium metal and UO 2 dissolved readily in nitric acid alone; PuO 2 dissolved slowly even with the addition of fluoride; PuO 2 -UO 2 pellets containing as much as 35% PuO 2 in UO 2 gave values of the instantaneous dissolution rate to indicate can be dissolved with nitric acid alone. An equation to calculate the time for complete dissolution has been determinate in function of the instantaneous dissolution rates. The calculated values agree with the experimental. Uranium dioxide pellets from various sources but all having a same density varied in instantaneous dissolution rate. All the pellets, however, have dissolved ved in the same time. The time for complete dissolution of PuO 2 -UO 2 pellets, having the same composition, and the concentration of the used reagents are function of the used reagents are function of the fabrication method. (Author) 8 refs

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)

Low-temperature heat capacity and standard molar enthalpy of formation of 9-fluorenemethanol (C14H12O)

International Nuclear Information System (INIS)

Di, You-Ying; Tan, Zhi-Cheng.; Sun, Xiao-Hong; Wang, Mei-Han; Xu, Fen; Liu, Yuan-Fa; Sun, Li-Xian; Zhang, Hong-Tao

2004-01-01

Low-temperature heat capacities of the 9-fluorenemethanol (C 14 H 12 O) have been precisely measured with a small sample automatic adiabatic calorimeter over the temperature range between T=78 K and T=390 K. The solid-liquid phase transition of the compound has been observed to be T fus =(376.567±0.012) K from the heat-capacity measurements. The molar enthalpy and entropy of the melting of the substance were determined to be Δ fus H m =(26.273±0.013) kJ · mol -1 and Δ fus S m =(69.770±0.035) J · K -1 · mol -1 . The experimental values of molar heat capacities in solid and liquid regions have been fitted to two polynomial equations by the least squares method. The constant-volume energy and standard molar enthalpy of combustion of the compound have been determined, Δ c U(C 14 H 12 O, s)=-(7125.56 ± 4.62) kJ · mol -1 and Δ c H m compfn (C 14 H 12 O, s)=-(7131.76 ± 4.62) kJ · mol -1 , by means of a homemade precision oxygen-bomb combustion calorimeter at T=(298.15±0.001) K. The standard molar enthalpy of formation of the compound has been derived, Δ f H m compfn (C 14 H 12 O,s)=-(92.36 ± 0.97) kJ · mol -1 , from the standard molar enthalpy of combustion of the compound in combination with other auxiliary thermodynamic quantities through a Hess thermochemical cycle

Enthalpy and interfacial free energy changes of water capillary condensed in mesoporous silica, MCM-41 and SBA-15.

Science.gov (United States)

Kittaka, Shigeharu; Ishimaru, Shinji; Kuranishi, Miki; Matsuda, Tomoko; Yamaguchi, Toshio

2006-07-21

The effect of confinement on the solid-liquid phase transitions of water was studied by using DSC and FT-IR measurements. Enthalpy changes upon melting of frozen water in MCM-41 and SBA-15 were determined as a function of pore size and found to decrease with decreasing pore size. The melting point also decreased almost monotonically with a decrease in pore size. Analysis of the Gibbs-Thomson relation on the basis of the thermodynamic data showed that there were two stages of interfacial free energy change after the constant region, i.e., below a pore size of 6.0 nm: a gradual decrease down to 3.4 nm and another decrease after a small jump upward. This fact demonstrates that the simple Gibbs-Thomson relation, i.e., a linear relation between the melting point change and the inverse pore size, is limited to the range not far from the melting point of bulk water. FT-IR measurements suggest that the decrease in enthalpy change and interfacial free energy change with decreasing pore size reflect the similarity of the structures of both liquid and solid phases of water in smaller pores at lower temperatures.

Determination of the enthalpy of fusion and thermal diffusivity for ternary Cu_6_0_−_xSn_xSb_4_0 alloys

International Nuclear Information System (INIS)

Zhai, W.; Zhou, K.; Hu, L.; Wei, B.

2016-01-01

Highlights: • The increasing Sn content reduces the liquidus temperature. • High Sn content results in lower enthalpy of fusion by polynomial functions. • The thermal diffusivity drops from the solid toward the semi-solid state. • Undercoolability of alloys with primary Cu_2Sb phase is stronger than others. - Abstract: The liquidus and solidus temperatures, enthalpy of fusion, and the temperature dependence of thermal diffusivity for ternary Cu_6_0_−_xSn_xSb_4_0 alloys were systematically measured by DSC and laser flash methods. It is found that both the liquidus temperature and the enthalpy of fusion decrease with the rise of Sn content, and their relationships with alloy composition were established by polynomial functions. The thermal diffusivity usually drops from the solid toward the semi-solid state. The undercoolability of those liquid Cu_6_0_−_xSn_xSb_4_0 alloys with primary Cu_2Sb solid phase is stronger than the others with primary β(SnSb) intermetallic compound, and the increase of cooling rate facilitates further undercooling. Microstructural observation indicates that both of the primary Cu_2Sb and β(SnSb) intermetallic compounds in ternary Cu_6_0_−_xSn_xSb_4_0 alloys grow in faceted mode, and develop into coarse flakes and polygonal blocks.

Insights on activation enthalpy for non-Schmid slip in body-centered cubic metals

International Nuclear Information System (INIS)

Hale, Lucas M.; Lim, Hojun; Zimmerman, Jonathan A.; Battaile, Corbett C.; Weinberger, Christopher R.

2015-01-01

We use insights gained from atomistic simulation to develop an activation enthalpy model for dislocation slip in body-centered cubic iron. Using a classical potential that predicts dislocation core stabilities consistent with ab initio predictions, we quantify the non-Schmid stress-dependent effects of slip. The kink-pair activation enthalpy is evaluated and a model is identified as a function of the general stress state. Our model enlarges the applicability of the classic Kocks activation enthalpy model to materials with non-Schmid behavior

Evaluation of a three compartment in vitro gastrointestinal simulator dissolution apparatus to predict in vivo dissolution.

Science.gov (United States)

Takeuchi, Susumu; Tsume, Yasuhiro; Amidon, Gregory E; Amidon, Gordon L

2014-11-01

In vitro dissolution tests are performed for new formulations to evaluate in vivo performance, which is affected by the change of gastrointestinal (GI) physiology, in the GI tract. Thus, those environmental changes should be introduced to an in vitro dissolution test. Many studies have successfully shown the improvement of in vitro-in vivo correlations (IVIVC) by introducing those physiological changes into dissolution tests. The gastrointestinal simulator (GIS), a multicompartment in vitro dissolution apparatus, was developed to evaluate in vivo drug dissolution. A gastric-emptying rate along with transit rate are key factors to evaluate in vivo drug dissolution and, hence, drug absorption. Dissolution tests with the GIS were performed with Biopharmaceutical Classification System class I drugs at five different gastric-emptying rates in the fasted state. Computational models were used to determine in vivo gastric-emptying time for propranolol and metoprolol based on the GIS dissolution results. Those were compared with published clinical data to determine the gastric half-emptying time. In conclusion, the GIS is a practical tool to assess dissolution properties and can improve IVIVC. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Unexpectedly normal phase behavior of single homopolymer chains

International Nuclear Information System (INIS)

Paul, W.; Strauch, T.; Rampf, F.; Binder, K.

2007-01-01

Employing Monte Carlo simulations, we show that the topology of the phase diagram of a single flexible homopolymer chain changes in dependence on the range of an attractive square well interaction between the monomers. For a range of attraction larger than a critical value, the equilibrium phase diagram of the single polymer chain and the corresponding polymer solution phase diagram exhibit vapor (swollen coil, dilute solution), liquid (collapsed globule, dense solution), and solid phases. Otherwise, the liquid-vapor transition vanishes from the equilibrium phase diagram for both the single chain and the polymer solution. This change in topology of the phase diagram resembles the behavior known for colloidal dispersions. The interplay of enthalpy and conformational entropy in the polymer case thus can lead to the same topology of phase diagrams as the interplay of enthalpy and translational entropy in simple liquids

Standard molar enthalpies of formation of sodium alkoxides

International Nuclear Information System (INIS)

Chandran, K.; Srinivasan, T.G.; Gopalan, A.; Ganesan, V.

2007-01-01

The molar enthalpies of solution of sodium in methanol, ethanol, and n-propanol and of sodium alkoxides in their corresponding alcohols were measured at T=298.15K using an isoperibol solution calorimeter. From these results and other auxiliary data, the standard molar enthalpies of formation, Δ f H m o (RONa,cr) of sodium methoxide, sodium ethoxide, and sodium n-propoxide were calculated and found to be {(-366.21+/-1.38) (-413.39+/-1.45), and (-441.57+/-1.18)}kJ.mol -1 , respectively. A linear correlation has been found between Δ f H m o (RONa)andΔ f H m o (ROH) for R=n-alkyl, enabling the prediction of data for other sodium alkoxides

Chemistry of application of calcination/dissolution to the Hanford tank waste inventory

International Nuclear Information System (INIS)

Delegard, C.H.; Elcan, T.D.; Hey, B.E.

1994-05-01

Approximately 330,000 metric tons of sodium-rich radioactive waste originating from separation of plutonium from irradiated uranium fuel are stored in underground tanks at the Hanford Site in Washington State. Fractionation of the waste into low-level waste (LLW) and high-level waste (HLW) streams is envisioned via partial water dissolution and limited radionuclide extraction operations. Under optimum conditions, LLW would contain most of the chemical bulk while HLW would contain virtually all of the transuranic and fission product activity. Calcination at around 850 C, followed by water dissolution, has been proposed as an alternative initial treatment of Hanford Site waste to improve waste dissolution and the envisioned LLW/HLW split. Results of literature and laboratory studies are reported on the application of calcination/dissolution (C/D) to the fractionation of the Hanford Site tank waste inventory. Both simulated and genuine Hanford Site waste materials were used in the lab tests. To evaluation confirmed that C/D processing reduced the amount of several components from the waste. The C/D dissolutions of aluminum and chromium allow redistribution of these waste components from the HLW to the LLW fraction. Comparisons of simple water-washing with C/D processing of genuine Hanford Site waste are also reported based on material (radionuclide and chemical) distributions to solution and solid residue phases. The lab results show that C/D processing yielded superior dissolution of aluminum and chromium sludges compared to simple water dissolution. 57 refs., 26 figs., 18 tabs

Chemistry of application of calcination/dissolution to the Hanford tank waste inventory

Energy Technology Data Exchange (ETDEWEB)

Delegard, C.H.; Elcan, T.D.; Hey, B.E.

1994-05-01

Approximately 330,000 metric tons of sodium-rich radioactive waste originating from separation of plutonium from irradiated uranium fuel are stored in underground tanks at the Hanford Site in Washington State. Fractionation of the waste into low-level waste (LLW) and high-level waste (HLW) streams is envisioned via partial water dissolution and limited radionuclide extraction operations. Under optimum conditions, LLW would contain most of the chemical bulk while HLW would contain virtually all of the transuranic and fission product activity. Calcination at around 850 C, followed by water dissolution, has been proposed as an alternative initial treatment of Hanford Site waste to improve waste dissolution and the envisioned LLW/HLW split. Results of literature and laboratory studies are reported on the application of calcination/dissolution (C/D) to the fractionation of the Hanford Site tank waste inventory. Both simulated and genuine Hanford Site waste materials were used in the lab tests. To evaluation confirmed that C/D processing reduced the amount of several components from the waste. The C/D dissolutions of aluminum and chromium allow redistribution of these waste components from the HLW to the LLW fraction. Comparisons of simple water-washing with C/D processing of genuine Hanford Site waste are also reported based on material (radionuclide and chemical) distributions to solution and solid residue phases. The lab results show that C/D processing yielded superior dissolution of aluminum and chromium sludges compared to simple water dissolution. 57 refs., 26 figs., 18 tabs.

Plutonium oxide dissolution

International Nuclear Information System (INIS)

Gray, J.H.

1992-01-01

Several processing options for dissolving plutonium oxide (PuO 2 ) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO 2 typically generated by burning plutonium metal and PuO 2 produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO 2 in canyon dissolvers. The options involve solid solution formation of PuO 2 With uranium oxide (UO 2 ) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO 2 with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO 2 materials may warrant further study

Spent fuel dissolution mechanisms

International Nuclear Information System (INIS)

Ollila, K.

1993-11-01

This study is a literature survey on the dissolution mechanisms of spent fuel under disposal conditions. First, the effects of radiolysis products on the oxidative dissolution mechanisms and rates of UO 2 are discussed. These effects have mainly been investigated by using electrochemical methods. Then the release mechanisms of soluble radionuclides and the dissolution of the UO 2 matrix including the actinides, are treated. Experimental methods have been developed for measuring the grain-boundary inventories of radionuclides. The behaviour of cesium, strontium and technetium in leaching tests shows different trends. Comparison of spent fuel leaching data strongly suggests that the release of 90 Sr into the leachant can be used as a measure of the oxidation/dissolution of the fuel matrix. Approaches to the modelling UO 2 , dissolution are briefly discussed in the next chapter. Lastly, the use of natural material, uraninite, in the evaluation of the long-term performance of spent fuel is discussed. (orig.). (81 ref., 37 figs., 8 tabs.)

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

Science.gov (United States)

Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

2001-01-01

The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

Energy Technology Data Exchange (ETDEWEB)

Chen Zhu

2006-08-31

Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between laboratory and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO2 injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the second year of the project, we completed CO{sub 2}-Navajo sandstone interaction batch and flow-through experiments and a Navajo sandstone dissolution experiment without the presence of CO{sub 2} at 200 C and 250-300 bars, and initiated dawsonite dissolution and solubility experiments. We also performed additional 5-day experiments at the

Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

Science.gov (United States)

Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong

2015-11-03

Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

Effects of gastric pH on oral drug absorption: In vitro assessment using a dissolution/permeation system reflecting the gastric dissolution process.

Science.gov (United States)

Kataoka, Makoto; Fukahori, Miho; Ikemura, Atsumi; Kubota, Ayaka; Higashino, Haruki; Sakuma, Shinji; Yamashita, Shinji

2016-04-01

The aim of the present study was to evaluate the effects of gastric pH on the oral absorption of poorly water-soluble drugs using an in vitro system. A dissolution/permeation system (D/P system) equipped with a Caco-2 cell monolayer was used as the in vitro system to evaluate oral drug absorption, while a small vessel filled with simulated gastric fluid (SGF) was used to reflect the gastric dissolution phase. After applying drugs in their solid forms to SGF, SGF solution containing a 1/100 clinical dose of each drug was mixed with the apical solution of the D/P system, which was changed to fasted state-simulated intestinal fluid. Dissolved and permeated amounts on applied amount of drugs were then monitored for 2h. Similar experiments were performed using the same drugs, but without the gastric phase. Oral absorption with or without the gastric phase was predicted in humans based on the amount of the drug that permeated in the D/P system, assuming that the system without the gastric phase reflected human absorption with an elevated gastric pH. The dissolved amounts of basic drugs with poor water solubility, namely albendazole, dipyridamole, and ketoconazole, in the apical solution and their permeation across a Caco-2 cell monolayer were significantly enhanced when the gastric dissolution process was reflected due to the physicochemical properties of basic drugs. These amounts resulted in the prediction of higher oral absorption with normal gastric pH than with high gastric pH. On the other hand, when diclofenac sodium, the salt form of an acidic drug, was applied to the D/P system with the gastric phase, its dissolved and permeated amounts were significantly lower than those without the gastric phase. However, the oral absorption of diclofenac was predicted to be complete (96-98%) irrespective of gastric pH because the permeated amounts of diclofenac under both conditions were sufficiently high to achieve complete absorption. These estimations of the effects of

Dissolution mechanism of UO2 at various parametric conditions

International Nuclear Information System (INIS)

Ollila, K.

1988-04-01

The aim of this experimental study is to investigate the solubility and dissolution mechanism of uranium dioxide under simulated disposal conditions of spent fuel. Unirradiated UO 2 is used as a surrogate for spent fuel. Two types of synthetic groundwaters were used in these experiments, on simulating the natural conditions deep in granitic bedrock (synthetic groundwater I) and the other simulating the effects of bentonite on groundwater (synthetic groundwater II). The effect of carbonate concentration was investigated by following dissolution in sodium bicarbonate solution as a function of bicarbonate concentration. Deionized wate was used as a reference water. All the experiments were carried out under both air-saturated, oxidizing and anoxic, reducing conditions. A separate test series under anoxic conditions was initiated in order to study the oxidation state of uranium. The experimental uranium solubilities are compared with the solubilities obtained from theoetical calculations by applying the geochemical code PHREEQ. The theoretical solubility values of uranium under oxidizing conditions calculated by PHREEQE are higher when compared to the corresponding experimental solubility values. The reason for the lower solubility values may be the mechanism of dissolution leading for example either to a situation where low dissolution rate is a limiting factor or to formation of some solid phase of uranium with lower solubility. Formation of a surface layer was observed on the pellet after dissolution in synthetic groundwater II. The theoretical solubility values under educing conditions calculated for uranium by PHREEQE appear to be in good agreement with the experimental solubility values

Vaporization thermodynamics of Pd-rich intermediate phases in the Pd–Yb system

Energy Technology Data Exchange (ETDEWEB)

Ciccioli, A., E-mail: andrea.ciccioli@uniroma1.it [Dipartimento di Chimica, Sapienza Università di Roma, p.le Aldo Moro 5, 00185 Roma (Italy); Balducci, G.; Gigli, G. [Dipartimento di Chimica, Sapienza Università di Roma, p.le Aldo Moro 5, 00185 Roma (Italy); Provino, A. [Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, via Dodecaneso 31, 16146 Genova (Italy); Istituto SPIN-CNR, Corso Perrone 24, 16152 Genova (Italy); Palenzona, A. [Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, via Dodecaneso 31, 16146 Genova (Italy); Manfrinetti, P. [Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, via Dodecaneso 31, 16146 Genova (Italy); Istituto SPIN-CNR, Corso Perrone 24, 16152 Genova (Italy)

2016-02-20

Highlights: • Vaporization equilibria of Pd–Yb intermediate phases investigated by effusion techniques. • Heats of formation of Pd–Yb compounds determined from decomposition/atomization enthalpies. • Phase diagram of the Pd–Yb system re-drawn. • Influence of the Yb valence state on the thermodynamic properties observed. - Abstract: The vaporization thermodynamics of several intermediate phases in the Pd–Yb system was investigated by means of vaporization experiments performed under Knudsen conditions (KEML, Knudsen Effusion Mass Loss). The following thermal decomposition processes were studied in the overall temperature range 819–1240 K and their enthalpy changes determined: 4 PdYb(s) = Pd{sub 4}Yb{sub 3}(s) + Yb(g); 5/3 Pd{sub 4}Yb{sub 3}(s) = 4/3 Pd{sub 5}Yb{sub 3}(s) + Yb(g); 21/13 Pd{sub 5}Yb{sub 3}(s) = 5/13 Pd{sub 21}Yb{sub 10}(s) + Yb(g); 1/3 Pd{sub 21}Yb{sub 10}(s) = 21/9 Pd{sub 3}Yb(s) + Yb(g). Additional measurements were performed by KEMS (Knudsen Effusion Mass Spectrometry) on a Pd-rich two-phase sample, which allowed to detect both Yb(g) and Pd(g) in the vapor phase and to determine the atomization enthalpy of the Pd{sub 3}Yb phase (Pd-rich composition boundary, Pd{sub 3.08}Yb{sub 0.92}): Pd{sub 3.08}Yb{sub 0.92}(s) = 0.92 Yb(g) + 3.08 Pd(g). The enthalpy of formation of this compound was thereafter determined as −68 ± 2 kJ/mol at. and, by combining this value with the decomposition enthalpies derived by KEML, the enthalpies of formation of the studied Pd–Yb intermediate phases were evaluated (kJ/mol at.): −75 ± 4 (Pd{sub 21}Yb{sub 10}), −75 ± 3 (Pd{sub 5}Yb{sub 3}), −73 ± 3 (Pd{sub 4}Yb{sub 3}), and −66 ± 3 (PdYb). A modified version of the Pd–Yb phase diagram is also reported, re-drawn on the basis of literature data and of new experimental information recently become available.

Attenuation of glass dissolution in the presence of natural additives

Energy Technology Data Exchange (ETDEWEB)

Sang, Jing C.; Barkatt, Aaron [Department of Chemistry, The Catholic University of America, Washington, DC (United States); O`Keefe, John A. [National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, MD (United States)

1996-11-01

The dissolution kinetics of silicate glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase are reported. The results demonstrate the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. This study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses, as well as to better understanding of the environmental degradation of natural and ancient glasses.

Dissolution of aluminium; Disolucion de aluminio

Energy Technology Data Exchange (ETDEWEB)

Uriarte Hueda, A; Berberana Eizmendi, M; Pereira Sanchez, G

1968-07-01

The dissolution of aluminum with acid solutions ( nitric acid-mercuric nitrate) and alkaline solutions (sodium hydroxide-sodium nitrate) has been studied. The instantaneous dissolution rate (IDR) has been studied in function of the concentration of the used reagents and the dissolution temperature. The complete dissolution has been included in the second part of this report, to know the total dissolution time, the consume of reagents and the stability of the resultant solutions. (Author)

Critical and subcritical parameters of the system simulating plutonium metal dissolution

International Nuclear Information System (INIS)

Vasilev, Yury Yu.; Ryazanov, Boris G.; Sviridov, Victor I.; Mozhayeva, Lubov I.

2003-01-01

Dissolution of plutonium metal was simulated using the Monte Carlo computer code to calculate criticality safety limits for the process. Calculations were made for the constant masses of plutonium charged to the dissolving vessel considering distribution of plutonium in metal and solution phases. Critical parameters and limits were calculated as a function of dissolving vessel volume and plutonium metal mass. 240 Pu content was assumed to be from 0% to 10% (mass). Critical parameters were evaluated for the system with a water reflector. Results of this paper may be used in the designing process equipment for plutonium metal dissolution. (author)

Enthalpy of solution of potassium iodide in the water-formamide-dimethyl sulfoxide mixtures

International Nuclear Information System (INIS)

Belova, L.N.; Solov'ev, S.N.; Vorob'ev, A.F.

1985-01-01

Solution enthalpies are measured for potassium iodide in the water-formamide-dimethyl sulfoxide mixtures in a sealed oscillating calorimeter with an isothermal shell at a constant water molar fraction equal to 0.3; 0.5 and 0.7 at 298.15 K. A diagram of the dependence of solution enthalpies on the of mixed solvent composition is plotted. Deviations of experimental solution enthalpies from the calculated ones are negative over the entire concentration range studied, which testifies to the preferable solvatation of electrolyte by the formid and dimthyl sulfoxide molecules

Recommended sublimation pressure and enthalpy of benzene

Czech Academy of Sciences Publication Activity Database

Růžička, K.; Fulem, Michal; Červinka, C.

2014-01-01

Roč. 68, Jan (2014), s. 40-47 ISSN 0021-9614 Institutional support: RVO:68378271 Keywords : benzene * vapor pressure * heat capacity * ideal - gas thermodynamic properties * sublimation enthalpy * recommended vapor pressure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.679, year: 2014

Biopharmaceutical characterisation of ciprofloxacin-metallic ion interactions: comparative study into the effect of aluminium, calcium, zinc and iron on drug solubility and dissolution.

Science.gov (United States)

Stojković, Aleksandra; Tajber, Lidia; Paluch, Krzysztof J; Djurić, Zorica; Parojčić, Jelena; Corrigan, Owen I

2014-03-01

Ciprofloxacin bioavailability may be reduced when ciprofloxacin is co-administered with metallic ion containing preparations. In our previous study, physicochemical interaction between ciprofloxacin and ferrous sulphate was successfully simulated in vitro. In the present work, comparative in vitro ciprofloxacin solubility and dissolution studies were performed in the reactive media containing aluminium hydroxide, calcium carbonate or zinc sulphate. Solid phases collected from the dissolution vessel with aluminium hydroxide, calcium carbonate and zinc sulphate were investigated for their properties. The results obtained indicate that different types of adducts may form and retard ciprofloxacin solubility and dissolution. In the case of aluminium, no phase changes were observed. The solid phase generated in the presence of calcium carbonate was identified as hydrated ciprofloxacin base. Similarly to iron, a new complex consistent with Zn(SO4)2(Cl)2(ciprofloxacin)2 × nH2O stoichiometry was generated in the presence of relatively high concentrations of ciprofloxacin hydrochloride and zinc sulphate, indicating that small volume dissolution experiments can be useful for biorelevant dissolution tests.

Biopharmaceutical characterisation of ciprofloxacin-metallic ion interactions: Comparative study into the effect of aluminium, calcium, zinc and iron on drug solubility and dissolution

Directory of Open Access Journals (Sweden)

Stojković Aleksandra

2014-03-01

Full Text Available Ciprofloxacin bioavailability may be reduced when ciprofloxacin is co-administered with metallic ion containing preparations. In our previous study, physicochemical interaction between ciprofloxacin and ferrous sulphate was successfully simulated in vitro. In the present work, comparative in vitro ciprofloxacin solubility and dissolution studies were performed in the reactive media containing aluminium hydroxide, calcium carbonate or zinc sulphate. Solid phases collected from the dissolution vessel with aluminium hydroxide, calcium carbonate and zinc sulphate were investigated for their properties. The results obtained indicate that different types of adducts may form and retard ciprofloxacin solubility and dissolution. In the case of aluminium, no phase changes were observed. The solid phase generated in the presence of calcium carbonate was identified as hydrated ciprofloxacin base. Similarly to iron, a new complex consistent with Zn(SO42(Cl2(ciprofloxacin2 × nH2O stoichiometry was generated in the presence of relatively high concentrations of ciprofloxacin hydrochloride and zinc sulphate, indicating that small volume dissolution experiments can be useful for biorelevant dissolution tests.

Enthalpy of vaporization and vapor pressure of whiskey lactone and menthalactone by correlation gas chromatography

International Nuclear Information System (INIS)

Simmons, Daniel; Chickos, James

2017-01-01

Highlights: • The vapor pressure and vaporization enthalpies of cis and trans-whiskey lactone have been evaluated. • Enthalpies of vaporization and vapor pressures of (+)-isomintlactone and (−)-mintlactone were also evaluated. • The sublimation enthalpy and corresponding vapor pressure of (+) -isomintlactone at T = 298.15 K is estimated. - Abstract: Enthalpies of vaporization at T = 298.15 K of cis and trans-whiskey lactone have been evaluated by correlation gas chromatography to be (68.4 ± 1.7) kJ·mol −1 and (67.5 ± 1.7) kJ·mol −1 , respectively. The enthalpies of vaporization of isomintlactone and mintlactone also evaluated by correlation gas chromatography have been found to have vaporization enthalpies of (74.2 ± 1.8) kJ·mol −1 and (73.2 ± 1.8) kJ·mol −1 respectively. The vapor pressures for cis and trans-whiskey lactone at T = 298.15 K have been evaluated as (1.5 ± 0.09) Pa and (2.0 ± 0.1) Pa using vapor pressures of a series of lactones as standards. Vapor pressures for isomintlactone and mintlactone were evaluated as (0.26 ± 0.012) Pa and (0.33 ± 0.02) Pa, respectively. Fusion and sublimation enthalpies for (+)-isomintlactone as well as the vapor pressure of the solid have been estimated.

Effect of sodium lauryl sulfate in dissolution media on dissolution of hard gelatin capsule shells.

Science.gov (United States)

Zhao, Fang; Malayev, Vyacheslav; Rao, Venkatramana; Hussain, Munir

2004-01-01

Sodium lauryl sulfate (SLS) is a commonly used surfactant in dissolution media for poorly water soluble drugs. However, it has occasionally been observed that SLS negatively impacts the dissolution of drug products formulated in gelatin capsules. This study investigated the effect of SLS on the dissolution of hard gelatin capsule shells. The USP paddle method was used with online UV monitoring at 214 nm (peptide bond). Empty size #0 capsule shells were held to the bottom of the dissolution vessel by magnetic three-prong sinkers. SLS significantly slowed down the dissolution of gelatin shells at pH < 5. Visually, the gelatin shells transformed into some less-soluble precipitate under these conditions. This precipitate was found to contain a higher sulfur content than the gelatin control sample by elemental analysis, indicating that SLS is part of the precipitate. Additionally, the slowdown of capsule shell dissolution was shown to be dependent on the SLS concentration and the ionic strength of the media. SLS interacts with gelatin to form a less-soluble precipitate at pH < 5. The use of SLS in dissolution media at acidic pH should be carefully evaluated for gelatin capsule products.

Dissolution of thorium/uranium mixed oxide in nitric acid-hydrofluoric acid solution

International Nuclear Information System (INIS)

Filgueiras, S.A.C.

1984-01-01

The dissolution process of thorium oxide and mixed uranium-thorium oxide is studied, as a step of the head-end of the fuel reprocessing. An extensive bibliography was analysed, concerning the main aspects of the system, specially the most important process variables. Proposed mechanisms and models for the thorium oxide dissolution are presented. The laboratory tests were performed in two phases: at first, powdered thoria was used as the material to be dissolved. The objective was to know how changes in he concentrations of the dissolvent solution components HNO 3 , HF and Al(NO 3 ) 3 affect the dissolution rate. The tests were planned according to the fractional factorial method. Thes results showed that it is advantageous to work with powdered material, since the reaction occurs rapidly. And, if the Thorex solution (HNO 3 13M, HF 0.05M and Al(NO 3 ) 3 0.10M) is a suitable dissolvent, it was verified that it is possible to reduce the concentration of either nitric or fluoridric acid, without reducing the reaction rate to an undesirable value. It was also observed significant interaction between the components of the dissolvent solution. In the second phase of the tests, (Th, 5%U)O 2 sintered pellets were used. The main goals were to know the pellets dissolution behaviour and to compare the results for different pellets among themselves. It was observed that the metallurgical history of the material strongly influences its dissolution, specially the density and the microstructure. It was also studied how the (Th,U)O 2 mass/Thorex solution volume ratio affects the time needed to obtain an 1 M Th/liter solution. The activation energy for the reaction was obtained. (Author) [pt

Enthalpy of mixing of liquid Cu-Fe-Hf alloys at 1873 K

Energy Technology Data Exchange (ETDEWEB)

Agraval, Pavel; Turchanin, Mikhail [Donbass State Engineering Academy, Kramatorsk (Ukraine). Metallurgical Dept.; Dreval, Liya [Donbass State Engineering Academy, Kramatorsk (Ukraine). Metallurgical Dept.; Materials Science International Services GmbH (MSI), Stuttgart (Germany)

2016-12-15

In the ternary Cu-Fe-Hf system, the mixing enthalpies of liquid alloys were investigated at 1873 K using a high-temperature isoperibolic calorimeter. The experiments were performed along the sections x{sub Cu}/x{sub Fe} = 3/1, 1/1 at x{sub Hf} = 0-0.47 and along the section x{sub Cu}/x{sub Fe} = 1/3 at x{sub Hf} = 0-0.13. The limiting partial enthalpies of mixing of undercooled liquid hafnium in liquid Cu-Fe alloys, Δ{sub mix} anti H{sub Hf}{sup ∞}, are (-122 ± 9) kJ mol{sup -1} (section x{sub Cu}/x{sub Fe} = 3/1), (-106 ± 9) kJ mol{sup -1} (section x{sub Cu}/x{sub Fe} = 1/1), and (-105 ± 2) kJ mol{sup -1} (section x{sub Cu}/x{sub Fe} = 1/3). In the investigated composition range, the integral mixing enthalpies are sign-changing. For the integral mixing enthalpy, an analytical expression was obtained by the least squares fit of the experimental results using the Redlich-Kister-Muggianu polynomial.

Enthalpies of combustion and formation of {alpha}-D-glucoheptono-1,4-lactone and {alpha},{beta}-glucooctanoic-1,4-lactone

Energy Technology Data Exchange (ETDEWEB)

Amador, Patricia [Facultad de Ciencias Qui' micas, Benemerita Universidad Autonoma de Puebla, 14 Sur y Av. San Claudio, Col. Manuel, C.P. 72570 Puebla Pue (Mexico)], E-mail: cs000721@siu.buap.mx; Mata, Marian Y.; Flores, Henoc [Facultad de Ciencias Qui' micas, Benemerita Universidad Autonoma de Puebla, 14 Sur y Av. San Claudio, Col. Manuel, C.P. 72570 Puebla Pue (Mexico)

2008-05-15

The standard molar energies of combustion, {delta}{sub c}U{sub m}{sup 0}(cr,298.15K), of {alpha}-D-glucoheptono-1,4-lactone (GH) and {alpha},{beta}-glucooctanoic-1,4-lactone (GO) were obtained by micro-combustion calorimetry. The obtained values are -(2924.6 {+-} 2.3) kJ . mol{sup -1} and -(3459.5 {+-} 2.5) kJ . mol{sup -1}, respectively. From combustion energies, the standard molar enthalpies of formation in crystalline phase, {delta}{sub f}H{sub m}{sup 0}(cr,298.15K), for GH and GO were determined as -(1546.2 {+-} 2.5) kJ . mol{sup -1} and -(1690.6 {+-} 2.7) kJ . mol{sup -1}, respectively. Also it was found that when the hydroxyl group number increases in the aldonolactones their standard molar enthalpies of formation increase too.

Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

KAUST Repository

Minenkov, Yury; Chermak, Edrisse; Cavallo, Luigi

2015-01-01

The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

KAUST Repository

Minenkov, Yury

2015-08-27

The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

Science.gov (United States)

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

The enthalpy of sublimation and thermodynamic functions of fermium

International Nuclear Information System (INIS)

Haire, R.G.; Gibson, J.K.

1989-01-01

The enthalpy of sublimation of fermium (Fm), element 100, has now been determined directly by measuring the partial pressure of Fm over alloys, for the temperature range of 642 to 905 K. The partial pressures were determined using Knudsen effusion and target collection techniques. Dilute (10 -5 --10 -7 atom %) solid alloys of Fm and mixtures of Fm and Es in both Sm and Yb solvents were studied. The presence of Es in two of the alloys allowed a direct comparison of the behavior of Fm and Es, where the latter could be used as a reference. It was possible to calculate enthalpies of sublimation and a hypothetical vapor pressure/temperature relationship for pure Fm metal by selecting Yb as the solvent most likely to form a nearly ideal alloy with Fm. From the experimental vapor pressure data, we derived average Second Law values of 33.8±3 kcal/mol and 23.5±3 cal/mol deg for the enthalpy and entropy of sublimation of Fm at 298 K. Third Law enthalpy values were also calculated using the experimental partial pressure data and entropies estimated from derived free energy functions and heat capacities for the solid and gaseous forms of Fm. The average Third Law values (34.8 kcal/mol and 25.1 cal/mol deg, respectively, at 298 K) are in agreement with those obtained via the Second Law. These results establish that Fm, like Es (element 99), is a divalent metal. The finding that Fm metal is the second divalent actinide element experimentally establishes the trend towards metallic divalency expected in the second half of the actinide series

Dissolution kinetics of purified and synthetic smectites at 25°C and PH∼9

International Nuclear Information System (INIS)

Marty, Nicolas C.M.; Tournassat, Christophe; Gaucher, Eric C.; Chino, Daisuke; Sato, Tsutomu; Villieras, Frederic; Giffaut, Eric; Cama, Jordi; Soler, J.M.

2010-01-01

to edge surface area (ESA), obtained by AFM observations and low-pressure gas adsorption method. ESA normalized dissolution rates of synthetic and natural clay dissolution rates are similar at pH∼9. Si-based dissolution rate law at pH∼9 and 25 deg. C that take into account the effect of the degree of saturation can be proposed either using a rate-law expression as that used by Cama et al. (2000). However, the dissolution rates based on release of Si, Al and Mg were different, indicating non-congruent dissolution reaction and/or formation of new phases. Post mortem AFM and TEM observations of reacted synthetic smectite show (1) significant decrease in particle size and (2) sporadically occurrence of pits on basal surfaces. Hence, it is not possible to definitively assess that dissolution mainly occurs at the edge surface, similarly to dissolution in high pH conditions. Moreover, the EDX analyses indicate decrease in the amount of Mg and Al in the reacted samples. Precipitation of silicate-bearing phases is also observed, although the nature of the precipitates is to be confirmed. Such formations may affect the Si-based dissolution law

Mathematical modeling of drug dissolution.

Science.gov (United States)

Siepmann, J; Siepmann, F

2013-08-30

The dissolution of a drug administered in the solid state is a pre-requisite for efficient subsequent transport within the human body. This is because only dissolved drug molecules/ions/atoms are able to diffuse, e.g. through living tissue. Thus, generally major barriers, including the mucosa of the gastro intestinal tract, can only be crossed after dissolution. Consequently, the process of dissolution is of fundamental importance for the bioavailability and, hence, therapeutic efficacy of various pharmaco-treatments. Poor aqueous solubility and/or very low dissolution rates potentially lead to insufficient availability at the site of action and, hence, failure of the treatment in vivo, despite a potentially ideal chemical structure of the drug to interact with its target site. Different physical phenomena are involved in the process of drug dissolution in an aqueous body fluid, namely the wetting of the particle's surface, breakdown of solid state bonds, solvation, diffusion through the liquid unstirred boundary layer surrounding the particle as well as convection in the surrounding bulk fluid. Appropriate mathematical equations can be used to quantify these mass transport steps, and more or less complex theories can be developed to describe the resulting drug dissolution kinetics. This article gives an overview on the current state of the art of modeling drug dissolution and points out the assumptions the different theories are based on. Various practical examples are given in order to illustrate the benefits of such models. This review is not restricted to mathematical theories considering drugs exhibiting poor aqueous solubility and/or low dissolution rates, but also addresses models quantifying drug release from controlled release dosage forms, in which the process of drug dissolution plays a major role. Copyright © 2013 Elsevier B.V. All rights reserved.

Dissolution of two NWCF calcines: Extent of dissolution and characterization of undissolved solids

International Nuclear Information System (INIS)

Brewer, K.N.; Herbst, R.S.; Tranter, T.J.

1995-01-01

A study was undertaken to determine the dissolution characteristics of two NWCF calcine types. A two-way blended calcine made from 4 parts nonradioactive aluminum nitrate and one part WM-102 was studied to determine the extent of dissolution for aluminum-type calcines. A two-way blend of 3.5 parts fluorinel waste from WM-187 and 1 part sodium waste from WM-185 was used to determine the extent of dissolution for zirconium-type calcines. This study was necessary to develop suitable aqueous separation flowsheets for the partitioning of actinides and fission products from ICPP calcines and to determine the disposition of the resulting undissolved solids (UDS). The dissolution flowsheet developed by Herbst was used to dissolve these two NWCF calcine types. Results show that greater than 95 wt% of aluminum and zirconium calcine types were dissolved after a single batch contact with 5 M HNO 3 . A characterization of the UDS indicates that the weight percent of TRU elements in the UDS resulting from both calcine type dissolutions increases by approximately an order of magnitude from their concentrations prior to dissolution. Substantial activities of cesium and strontium are also present in the UDS resulting from the dissolution of both calcine types. Multiple TRU, Cs, and Sr analyses of both UDS types show that these solids are relatively homogeneous. From this study, it is estimated that between 63.5 and 635 cubic meters of UDS will be generated from the dissolution of 3800 M 3 of calcine. The significant actinide and fission product activities in these UDS will preclude their disposal as low-level waste. If the actinide and fission activity resulting from the UDS is the only considered source in the dissolved calcine solutions, an estimated 99.9 to 99.99 percent of the solids must be removed from this solution for it to meet non-TRU Class A low-level waste

UO2 dissolution rates: A review

International Nuclear Information System (INIS)

McKenzie, W.F.

1992-09-01

This report reviews literature data on UO 2 dissolution kinetics and provides a framework for guiding future experimental studies as well as theoretical modeling studies. Under oxidizing conditions, UO 2 dissolution involves formation of an oxidized surface layer which is then dissolved by formation of aqueous complexes. Higher oxygen pressures or other oxidants are required at higher temperatures to have dissolution rates independent of oxygen pressure. At high oxygen pressures (1-5 atm, 25-70 C), the dissolution rate has a one-half order dependence on oxygen pressure, whereas at oxygen pressures below 0.2 atm, Grandstaff (1976), but nobody else, observed a first-order dependence on dissolution rate. Most people found a first-order dependence on carbonate concentration; Posey-Dowty (1987) found independence of carbonate at pH 7 to 8.2. Dissolution rates increase with temperature except in experiments involving granitic groundwater. Dissolution rates were generally greater under acid or basic conditions than near neutral pH

An Enthalpy of Dissolution of Potassium Chloride

OpenAIRE

鈴木, 隆

2013-01-01

When substances have changed chemically or physically, the heat of the chemical and physical change is obtained as exothermic and endothermic behavior. Therefore, it is very effective to measure the heat energy of the chemical and physical change of the substance. The heat energy can be obtained by calorimetry. There are three types of calorimeters.The adiabatic calorimeter is used mainly for the measurement of heat capacity. The isoperibolic calorimeter is suitable for the measurement of lar...

Modelling of high-enthalpy, high-Mach number flows

International Nuclear Information System (INIS)

Degrez, G; Lani, A; Panesi, M; Chazot, O; Deconinck, H

2009-01-01

A review is made of the computational models of high-enthalpy flows developed over the past few years at the von Karman Institute and Universite Libre de Bruxelles, for the modelling of high-enthalpy hypersonic (re-)entry flows. Both flows in local thermo-chemical equilibrium (LTE) and flows in thermo-chemical non-equilibrium (TCNEQ) are considered. First, the physico-chemical models are described, i.e. the set of conservation laws, the thermodynamics, transport phenomena and chemical kinetics models. Particular attention is given to the correct modelling of elemental (LTE flows) and species (chemical non-equilibrium-CNEQ-flows) transport. The numerical algorithm, based on a state-of-the-art finite volume discretization, is then briefly described. Finally, selected examples are included to illustrate the capabilities of the developed solver. (review article)

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

Science.gov (United States)

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

Investigation of enthalpy and specific heat of the gallium-indium-tin eutectic alloy

International Nuclear Information System (INIS)

Roshchupkin, V.V.; Migaj, L.L.; Fordeeva, L.K.; Perlova, N.L.

1978-01-01

Enthalpy and specific heat of the fusible (melting point is 10.6 deg C) eutectic alloy (67% Ga - 20.5% In - 12.5% Sn according to mass) are determined by the mixing method. The determination was carried out in vacuum at the residual pressure of >= 1x10 -5 torr in the temperature range from 59.3 to 437.0 deg C. It is established that temperature dependence of alloy enthalpy is described by the equation: Hsub(t) - Hsub(0degC)=1.014+0.0879t-0.0000129 t 2 , where (Hsub(t) - Hsub(0degC)) is enthalpy, cal/g; t-temperature, deg C. Mean-square dispersion is +-0.6%. Temperature dependence of alloy specific heat in the temperature range under study was determined by differentiation of the equation obtained for enthalpy: Csub(p)=0.0879-0.000026t, where Csub(p)-specific heat, cal/gx deg. It is supposed that temperature increase makes it possible to decrease slightly specific heat

Thermodynamic study of phase transitions in methyl esters of ortho- meta- and para-aminobenzoic acids

International Nuclear Information System (INIS)

Almeida, Ana R.R.P.; Monte, Manuel J.S.

2012-01-01

Highlights: ► Vapor pressures of liquid and crystalline phases of methyl esters of the aminobenzoic acids were measured. ► Accurate values of enthalpies of sublimation, vaporization, and fusion were derived. ► The enthalpy of intermolecular NH–O hydrogen bonds in methyl p-aminobenzoate was determined. ► The volatility of the methyl benzoates was compared with the volatility of the parent acids. - Abstract: A static method based on capacitance gauges was used to measure the vapor pressures of the condensed phases of the methyl esters of the three aminobenzoic acids. For methyl o-aminobenzoate the vapor pressures of the liquid phase were measured in the range (285.4 to 369.5) K. For the meta and para isomers vapor pressures of both crystalline and liquid phases were measured in the ranges (308.9 to 376.6) K, and (332.9 to 428.0) K, respectively. Vapor pressures of the latter compound were also measured using the Knudsen effusion method in the temperature range (319.1 to 341.2) K. From the dependence of the vapor pressures on the temperature, the standard molar enthalpies and entropies of sublimation and of vaporization were derived. Differential scanning calorimetry was used to measure the temperatures and molar enthalpies of fusion of the three isomers. The results enabled the estimation of the enthalpy of the intermolecular (N−H … O) hydrogen bond in the crystalline methyl p-aminobenzoate. A correlation relating the temperature of fusion and the enthalpy and Gibbs energy of sublimation of benzene, methyl benzoates and benzoic acids was derived.

High Enthalpy Effects on Two Boundary Layer Disturbances in Supersonic and Hypersonic Flow

Science.gov (United States)

Wagnild, Ross Martin

The fluid flow phenomenon of boundary layer transition is a complicated and difficult process to model and predict. The importance of the state of the boundary layer with regard to vehicle design cannot be understated. The high enthalpy environment in which high speed vehicles operate in further complicates the transition process by adding several more degrees of freedom. In this environment, the internal properties of the gas can stabilize or destabilize the boundary layer as well as modify the disturbances that cause transition. In the current work, the interaction of two types of disturbances with the high enthalpy flow environment are analyzed. The first is known as a second mode disturbance, which is acoustic in nature. The second type is known as a transient growth disturbance and is associated with flows behind roughness elements. Theoretical analyses, linear stability analyses, and computation fluid dynamics (CFD) are used to determine the ways in which these disturbances interact with the high enthalpy environment as well as the consequences of these interactions. First, acoustic wave are directly studied in order to gain a basic understanding of the response of second mode disturbances in the high enthalpy boundary layer. Next, this understanding is used in interpreting the results of several computations attempting to simulate the flow through a high enthalpy flow facility as well as experiments attempting to take advantage of the acoustic interaction with the high enthalpy environment. Because of the difficulty in modeling these experiments, direct simulations of acoustic waves in a hypersonic flow of a gas with molecular vibration are performed. Lastly, compressible transient growth disturbances are simulated using a linear optimal disturbance solver as well as a CFD solver. The effect of an internal molecular process on this type of disturbance is tested through the use of a vibrational mode. It is the goal of the current work to reinforce the

Thermal Stability Test of Sugar Alcohols as Phase Change Materials for Medium Temperature Energy Storage Application

OpenAIRE

Solé, Aran; Neumann, Hannah; Niedermaier, Sophia; Cabeza, Luisa F.; Palomo, Elena

2014-01-01

Sugar alcohols are potential phase change materials candidates as they present high phase change enthalpy values, are non-toxic and low cost products. Three promising sugar-alcohols were selected: D-mannitol, myo-inositol and dulcitol under high melting enthalpy and temperature criterion. Thermal cycling tests were performed to study its cycling stability which can be determining when selecting the suitable phase change material. D-mannitol and dulcitol present poor thermal stability...

Energy and enthalpy distribution functions for a few physical systems.

Science.gov (United States)

Wu, K L; Wei, J H; Lai, S K; Okabe, Y

2007-08-02

The present work is devoted to extracting the energy or enthalpy distribution function of a physical system from the moments of the distribution using the maximum entropy method. This distribution theory has the salient traits that it utilizes only the experimental thermodynamic data. The calculated distribution functions provide invaluable insight into the state or phase behavior of the physical systems under study. As concrete evidence, we demonstrate the elegance of the distribution theory by studying first a test case of a two-dimensional six-state Potts model for which simulation results are available for comparison, then the biphasic behavior of the binary alloy Na-K whose excess heat capacity, experimentally observed to fall in a narrow temperature range, has yet to be clarified theoretically, and finally, the thermally induced state behavior of a collection of 16 proteins.

CHARACTERIZATION AND ALUMINUM DISSOLUTION DEMONSTRATION WITH A 3 LITER TANK 51H SAMPLE

International Nuclear Information System (INIS)

Hay, M; John Pareizs, J; Cj Bannochie, C; Michael Stone, M; Damon Click, D; Daniel McCabe, D

2008-01-01

A 3-liter sludge slurry sample was sent to SRNL for demonstration of a low temperature aluminum dissolution process. The sludge was characterized before and after the aluminum dissolution. Post aluminum dissolution sludge settling and the stability of the decanted supernate were also observed. The characterization of the as-received 3-liter sample of Tank 51H sludge slurry shows a typical high aluminum HM sludge. The XRD analysis of the dried solids indicates Boehmite is the predominant crystalline form of aluminum in the sludge solids. However, amorphous phases of aluminum present in the sludge would not be identified using this analytical technique. The low temperature (55 C) aluminum dissolution process was effective at dissolving aluminum from the sludge. Over the three week test, ∼42% of the aluminum was dissolved out of the sludge solids. The process appears to be selective for aluminum with no other metals dissolving to any appreciable extent. At the termination of the three week test, the aluminum concentration in the supernate had not leveled off indicating more aluminum could be dissolved from the sludge with longer contact times or higher temperatures. The slow aluminum dissolution rate in the test may indicate the dissolution of the Boehmite form of aluminum however; insufficient kinetic data exists to confirm this hypothesis. The aluminum dissolution process appears to have minimal impact on the settling rate of the post aluminum dissolution sludge. However, limited settling data were generated during the test to quantify the effects. The sludge settling was complete after approximately twelve days. The supernate decanted from the settled sludge after aluminum dissolution appears stable and did not precipitate aluminum over the course of several months. A mixture of the decanted supernate with Tank 11 simulated supernate was also stable with respect to precipitation

Skin-friction measurements in high-enthalpy hypersonic boundary layers

Science.gov (United States)

Goyne, C. P.; Stalker, R. J.; Paull, A.

2003-06-01

Skin-friction measurements are reported for high-enthalpy and high-Mach-number laminar, transitional and turbulent boundary layers. The measurements were performed in a free-piston shock tunnel with air-flow Mach number, stagnation enthalpy and Reynolds numbers in the ranges of 4.4 6.7, 3 13 MJ kg(-1) and 0.16× 10(6) 21× 10(6) , respectively. Wall temperatures were near 300 K and this resulted in ratios of wall enthalpy to flow-stagnation enthalpy in the range of 0.1 0.02. The experiments were performed using rectangular ducts. The measurements were accomplished using a new skin-friction gauge that was developed for impulse facility testing. The gauge was an acceleration compensated piezoelectric transducer and had a lowest natural frequency near 40 kHz. Turbulent skin-friction levels were measured to within a typical uncertainty of ± 7%. The systematic uncertainty in measured skin-friction coefficient was high for the tested laminar conditions; however, to within experimental uncertainty, the skin-friction and heat-transfer measurements were in agreement with the laminar theory of van Driest (1952). For predicting turbulent skin-friction coefficient, it was established that, for the range of Mach numbers and Reynolds numbers of the experiments, with cold walls and boundary layers approaching the turbulent equilibrium state, the Spalding & Chi (1964) method was the most suitable of the theories tested. It was also established that if the heat transfer rate to the wall is to be predicted, then the Spalding & Chi (1964) method should be used in conjunction with a Reynolds analogy factor near unity. If more accurate results are required, then an experimentally observed relationship between the Reynolds analogy factor and the skin-friction coefficient may be applied.

A simple and rational numerical method of two-phase flow with volume-junction model. 2. The numerical method for general condition of two-phase flow in non-equilibrium states

International Nuclear Information System (INIS)

Okazaki, Motoaki

1997-11-01

In the previous report, the usefulness of a new numerical method to achieve a rigorous numerical calculation using a simple explicit method with the volume-junction model was presented with the verification calculation for the depressurization of a saturated two-phase mixture. In this report, on the basis of solution method above, a numerical method for general condition of two-phase flow in non-equilibrium states is presented. In general condition of two-phase flow, the combinations of saturated and non-saturated conditions of each phase are considered in the each flow of volume and junction. Numerical evaluation programs are separately prepared for each combination of flow condition. Several numerical calculations of various kinds of non-equilibrium two-phase flow are made to examine the validity of the numerical method. Calculated results showed that the thermodynamic states obtained in different solution schemes were consistent with each other. In the first scheme, the states are determined by using the steam table as a function of pressure and specific enthalpy which are obtained as the solutions of simultaneous equations. In the second scheme, density and specific enthalpy of each phase are directly calculated by using conservation equations of mass and enthalpy of each phase, respectively. Further, no accumulation of error in mass and energy was found. As for the specific enthalpy, two cases of using energy equations for the volume are examined. The first case uses total energy conservation equation and the second case uses the type of the first law of thermodynamics. The results of both cases agreed well. (author)

Measuring the enthalpies of interaction between glycine, L-cysteine, glycylglycine, and sodium dodecyl sulfate in aqueous solutions

Science.gov (United States)

Badelin, V. G.; Mezhevoi, I. N.; Tyunina, E. Yu.

2017-03-01

Calorimetric measurements of enthalpies of solution Δsol H m for glycine, L-cysteine, and glycylglycine in aqueous solutions of sodium dodecyl sulfate (SDS) with concentrations of up to 0.05 mol kg-1 are made. Standard enthalpy of solution Δsol H 0 and enthalpy of transfer Δtr H 0 of the dipeptide from water into mixed solvent are calculated. The calculated enthalpy coefficients of paired interactions of amino acids and dipeptide with SDS prove to be positive. Hydrophobic interactions between the biomolecules and SDS are found to have a major impact on the enthalpies of interaction in the three-component systems under study, within the indicated range of concentrations.

Enthalpies of Formation of Transition Metal Diborides: A First Principles Study

Directory of Open Access Journals (Sweden)

Catherine Colinet

2015-11-01

Full Text Available The enthalpies of formation of transition metals diborides in various structures have been obtained from density functional theory (DFT calculations in order to determine the ground state at T = 0 K and p = 0. The evolution of the enthalpies of formation along the 3D, 4D, and 5D series has been correlated to the considered crystal structures. In the whole, the calculated values of the enthalpies of formation of the diborides in their ground state are in good agreement with the experimental ones when available. The calculated values of the lattice parameters at T = 0 K of the ground state agree well with the experimental values. The total and partial electronic densities of states have been computed. Special features of the transition metal electronic partial density of states have been evidenced and correlated to the local environment of the atoms.

Enthalpies of solution of ampicillin, amoxycillin and their binary mixtures at 310.15 K.

Science.gov (United States)

Jain, D V; Kashid, N; Kapoor, S; Chadha, R

2000-05-15

Enthalpies of solutions of ampicillin, amoxycillin and their binary mixtures have been determined at pH 2, 5, and 7 using C-80 calorimeter. The systems showed endothermic behaviour; molar enthalpies of solutions of ampicillin were determined to be 13.32, 15.89 and 23.21 kJ mol(-1) and amoxycillin were 16.32, 18.45 and 26. 25 kJ mol(-1) at pH 2, 5, and 7, respectively. The excess molar enthalpies of solution have also been calculated to find any interaction between these two drugs.

Coamorphous drug systems: enhanced physical stability and dissolution rate of indomethacin and naproxen

DEFF Research Database (Denmark)

Löbmann, Korbinian; Laitinen, Riikka; Grohganz, Holger

2011-01-01

. In this study, a coamorphous drug/drug combination between the two nonsteroidal anti-inflammatory drugs, naproxen and ¿-indomethacin, was prepared and investigated. At molar ratios of 2:1, 1:1 and 1:2, the drugs were quench cooled in order to obtain a coamorphous binary phase. Physical stability was examined...... at 277.15 and 298.15 K under dry conditions (phosphorus pentoxide) and analyzed with X-ray powder diffraction (XRPD). Intrinsic dissolution testing was carried out to identify dissolution advantages of the coamorphous form over its crystalline counterparts or amorphous indomethacin. Fourier transform...

Six-membered ring aliphatic compounds: A search for regularities in phase transitions

International Nuclear Information System (INIS)

Nagrimanov, Ruslan N.; Solomonov, Boris N.; Emel’yanenko, Vladimir N.; Verevkin, Sergey P.

2016-01-01

Highlights: • Thermodynamics of sublimation and solution of halogen adamantanes is studied. • Sublimation enthalpies derived from transpiration and solution calorimetry in agreement. • Enthalpies of fusion measured by DSC and used to derive vaporization enthalpies. • Structure-property analysis of vaporization enthalpies was performed. - Abstract: Absolute vapor pressures of 1-Cl-adamantane, 2-Cl-adamantane, 1-Br-adamantane, 2-Br-adamantane, as well as of Br-cyclohexane were measured by using the transpiration method. Standard molar enthalpies of sublimation of halogen substituted adamantanes at 298.15 K were derived from vapor pressure temperature dependences. Standard molar enthalpies of solution of adamantane and halogen adamantanes in cyclohexane were measured with a high-precision solution calorimeter. A theoretical procedure based on the solution calorimetry was applied to derive sublimation enthalpies of halogen adamantanes independently. Molar enthalpies of fusion were measured with help of DSC. The consistent data set of phase transitions for each compound was evaluated and used for discussion of structure-property relations in adamantane and cyclohexane derivatives. A simple way to predict enthalpies of vaporization of compounds containing six-membered rings was suggested for practical thermochemical calculations.

The dissolution phenomenon of lysozyme crystals

Energy Technology Data Exchange (ETDEWEB)

Mueller, C.; Ulrich, J. [Martin Luther University Halle-Wittenberg, Department of Thermal Separation Processes, Centre of Engineering Science, Halle/Saale (Germany)

2012-02-15

Dissolution studies on lysozyme crystals were carried out since the observed dissolution pattern look different from non-protein dissolved crystals. The Tetragonal, High Temperature and Low Temperature Orthorhombic morphologies, crystallized using sodium chloride, were chosen and the influence of different pH, salt and protein concentration on their dissolution was investigated. An increase in pH and/or salt concentration can modify the dissolution behaviour. The pattern of the crystals during the dissolution process will, therefore, develop differently. Frequently a skeleton like crystal pattern followed by a falling apart of the crystals is observed. The multi-component character of the lysozyme crystal (protein, water, buffer, salt) as well as ''solvatomorphism'' gives first insights in the phenomena happening in the dissolution process. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

An Examination of the Phase Transition Thermodynamics of (S)- and (RS)-Naproxen as a Basis for the Design of Enantioselective Crystallization Processes.

Science.gov (United States)

Buchholz, Hannes; Emel'yanenko, Vladimir N; Lorenz, Heike; Verevkin, Sergey P

2016-05-01

A detailed experimental analysis of the phase transition thermodynamics of (S)-naproxen and (RS)-naproxen is reported. Vapor pressures were determined experimentally via the transpiration method. Sublimation enthalpies were obtained from the vapor pressures and from independent TGA measurements. Thermodynamics of fusion which have been well-studied in the literature were systematically remeasured by DSC. Both sublimation and fusion enthalpies were adjusted to one reference temperature, T = 298 K, using measured heat capacities of the solid and the melt phase by DSC. Average values from the measurements and from literature data were suggested for the sublimation and fusion enthalpies. In order to prove consistency of the proposed values the vaporization enthalpies obtained by combination of both were compared to vaporization enthalpies obtained by the group-additivity method and the correlation-gas chromatography method. The importance of reliable and precise phase transition data for thermochemical calculations such as the prediction of solid/liquid phase behaviour of chiral compounds is highlighted. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Dissolution Flowsheet for High Flux Isotope Reactor Fuel

Energy Technology Data Exchange (ETDEWEB)

Daniel, W. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Rudisill, T. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); O' Rourke, P. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Karay, N. S [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2016-09-27

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U₃O₈) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H₂. The HFIR fuel cores will be dissolved and the recovered U will be down-blended into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H₂) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy, and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H₂ and other permanent gases in the dissolution offgas, allowing the development of H₂ generation rate profiles. The H₂ generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the

Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

International Nuclear Information System (INIS)

Riveros, Diana C.; Martínez, Fleming; Vargas, Edgar F.

2012-01-01

Highlights: ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. ► Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute–solvent interactions.

Enthalpy recovery in glassy materials: Heterogeneous versus homogenous models

Science.gov (United States)

Mazinani, Shobeir K. S.; Richert, Ranko

2012-05-01

Models of enthalpy relaxations of glasses are the basis for understanding physical aging, scanning calorimetry, and other phenomena that involve non-equilibrium and non-linear dynamics. We compare models in terms of the nature of the relaxation dynamics, heterogeneous versus homogeneous, with focus on the Kovacs-Aklonis-Hutchinson-Ramos (KAHR) and the Tool-Narayanaswamy-Moynihan (TNM) approaches. Of particular interest is identifying the situations for which experimental data are capable of discriminating the heterogeneous from the homogeneous scenario. The ad hoc assumption of a single fictive temperature, Tf, is common to many models, including KAHR and TNM. It is shown that only for such single-Tf models, enthalpy relaxation of a glass is a two-point correlation function in reduced time, implying that experimental results are not decisive regarding the underlying nature of the dynamics of enthalpy relaxation. We also find that the restriction of the common TNM model to a Kohlrausch-Williams-Watts type relaxation pattern limits the applicability of this approach, as the particular choice regarding the distribution of relaxation times is a more critical factor compared with isothermal relaxation experiments. As a result, significant improvements in fitting calorimetry data can be achieved with subtle adjustments in the underlying relaxation time distribution.

Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

Science.gov (United States)

Tournier, Robert F.

2018-01-01

Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

Thermodynamic and kinetic characterization of polycyclic aromatic hydrocarbons in reversed-phase liquid chromatography.

Science.gov (United States)

Howerton, Samuel B; McGuffin, Victoria L

2003-07-15

The retention of six polycyclic aromatic hydrocarbons (PAHs) was characterized by reversed-phase liquid chromatography. The PAHs were detected by laser-induced fluorescence at four points along an optically transparent capillary column. The profiles were characterized in space and time using an exponentially modified Gaussian equation. The resulting parameters were used to calculate the retention factors, as well as the concomitant changes in molar enthalpy and molar volume, for each PAH on monomeric (2.7 micromol/m2) and polymeric (5.4 micromol/m2) octadecylsilica. The changes in molar enthalpy become more exothermic as ring number increases and as annelation structure becomes less condensed. The changes in molar volume become more negative as ring number increases for the planar PAHs, but are positive for the nonplanar solutes. In addition, the rate constants, as well as the concomitant activation enthalpy and activation volume, are calculated for the first time. The kinetic data demonstrate that many of the PAHs exhibit very fast transitions between the mobile and stationary phases. The transition state is very high in energy, and the activation enthalpies and volumes become greater as ring number increases and as annelation structure becomes less condensed. The changes in thermodynamic and kinetic behavior are much more pronounced for the polymeric phase than for the monomeric phase.

Excess Enthalpies of Mixing of Binary Mixtures of NaCl, KCl, NaBr ...

African Journals Online (AJOL)

NJD

2004-07-01

Jul 1, 2004 ... NaBr and KBr in Mixed Ternary Solvent Systems at 298.15 K. Bal Raj Deshwala* ... industrial waters and their thermodynamic properties are of practical interest for .... The enthalpy of mixing (∆Hm) is the difference between the excess enthalpy of the ..... tural (categorized by softness, open- ness, and ...

Solution enthalpies of alkali metal halides in water and heavy water mixtures with dimethyl sulfoxide

International Nuclear Information System (INIS)

Egorov, G.I.

1994-01-01

Solution enthalpies of CsF, LiCl, NaI, CsI and some other halides of alkali metals and tetrabutylammonium have been measured by the method of calorimetry. Standard solution enthalpies of all alkali metals (except rubidium) halides in water and heavy water mixtures with dimethylsulfoxide at 298.15 K have been calculated. Isotopic effects in solvation enthalpy of the electrolytes mentioned in aqueous solutions of dimethylsulfoxide have been discussed. 29 refs., 2 figs., 4 tabs

On the Enthalpy and Entropy of Point Defect Formation in Crystals

Science.gov (United States)

Kobelev, N. P.; Khonik, V. A.

2018-03-01

A standard way to determine the formation enthalpy H and entropy S of point defect formation in crystals consists in the application of the Arrhenius equation for the defect concentration. In this work, we show that a formal use of this method actually gives the effective (apparent) values of these quantities, which appear to be significantly overestimated. The underlying physical reason lies in temperature-dependent formation enthalpy of the defects, which is controlled by temperature dependence of the elastic moduli. We present an evaluation of the "true" H- and S-values for aluminum, which are derived on the basis of experimental data by taking into account temperature dependence of the formation enthalpy related to temperature dependence of the elastic moduli. The knowledge of the "true" activation parameters is needed for a correct calculation of the defect concentration constituting thus an issue of major importance for different fundamental and application issues of condensed matter physics and chemistry.

Study of Shallow Low-Enthalpy Geothermal Resources Using Integrated Geophysical Methods

Science.gov (United States)

De Giorgi, Lara; Leucci, Giovanni

2015-02-01

The paper is focused on low enthalpy geothermal exploration performed in south Italy and provides an integrated presentation of geological, hydrogeological, and geophysical surveys carried out in the area of municipality of Lecce. Geological and hydrogeological models were performed using the stratigraphical data from 51 wells. A ground-water flow (direction and velocity) model was obtained. Using the same wells data, the ground-water annual temperature was modeled. Furthermore, the ground surface temperature records from ten meteorological stations were studied. This allowed us to obtain a model related to the variations of the temperature at different depths in the subsoil. Integrated geophysical surveys were carried out in order to explore the low-enthalpy geothermal fluids and to evaluate the results of the model. Electrical resistivity tomography (ERT) and self-potential (SP) methods were used. The results obtained upon integrating the geophysical data with the models show a low-enthalpy geothermal resource constituted by a shallow ground-water system.

Assessing the effect of dissolved organic ligands on mineral dissolution rates: An example from calcite dissolution

International Nuclear Information System (INIS)

DeMaio, T.; Grandstaff, D.E.

1997-01-01

Experiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or protect the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation. To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22 C in Na-Ca-HCO 3 -Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 microM) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (<50 microM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid

Enthalpies of mixing in binary liquid alloys of lutetium with 3d metals

Energy Technology Data Exchange (ETDEWEB)

Ivanov, Michael; Berezutski, Vadim [National Academy of Sciences, Kyiv (Ukraine). I. Frantsevich Institute for Problems of Materials Science; Usenko, Natalia; Kotova, Natalia [Taras Shevchenko National Univ., Kyiv (Ukraine). Dept. of Chemistry

2017-01-15

The enthalpies of mixing in binary liquid alloys of lutetium with chromium, cobalt, nickel and copper were determined at 1 773 - 1 947 K by isoperibolic calorimetry. The enthalpies of mixing in the Lu-Cr melts (measured up to 40 at.% Cr) demonstrate endothermic effects (ΔH = 6.88 ± 0.66 kJ . mol{sup -1} at x{sub Lu} = 0.60), whereas significant exothermic enthalpies of mixing have been established within a wide composition region for the Co-Lu, Ni-Lu and Cu-Lu liquid alloys. Minimum values of the integral enthalpy of mixing are as follows: ΔH{sub min} = -23.57 ± 1.41 kJ . mol{sup -1} at x{sub Lu} = 0.38 for the Co-Lu system; ΔH{sub min} = -48.65 ± 2.83 kJ . mol{sup -1} at x{sub Lu} = 0.40 for the Ni-Lu system; ΔH{sub min} = -24.63 ± 1.52 kJ . mol{sup -1} at x{sub Lu} = 0.37 for the Cu-Lu system.

Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

Energy Technology Data Exchange (ETDEWEB)

Riveros, Diana C. [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia); Martinez, Fleming [Grupo de Investigaciones Farmaceutico-Fisicoquimicas, Departamento de Farmacia, Facultad de Ciencias, Universidad Nacional de Colombia, Bogota D.C. (Colombia); Vargas, Edgar F., E-mail: edvargas@uniandes.edu.co [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia)

2012-11-20

Highlights: Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. Black-Right-Pointing-Pointer Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute-solvent interactions.

Enthalpy of mixing of Sn-Cd system using high temperature Calvet microcalorimeter

International Nuclear Information System (INIS)

Jayanthi, K.; Iyer, V.S.; Venugopal, V.

1993-01-01

The integral enthalpy of mixing of Sn + Cd alloys were determined at 690 K for mole fraction of cadmium (X Cd ) from 0.06 to 0.958. In the present study, the use of small quantities of metals and the determination of enthalpy of mixing of an endothermic reaction without stirring the bath solution. This was possible due to the high sensitivity of the Calvet calorimeter. (author). 3 refs., 3 tabs

Borate-polyol complexes in aqueous solution: determination of enthalpies by thermometric titrimetry.

Science.gov (United States)

Aruga, R

1985-06-01

Enthalpies for the reaction of borate with 1,2-ethanediol, 1,2-propanediol, 1,2,3-propanetriol and d-mannitol have been determined by thermometric titrimetry. From these enthalpies and equilibrium constants taken from the literature, corresponding entropies have been calculated. The data refer to aqueous solutions at 25 degrees and I = 1.0M (NaNO(3)). The results indicate reasons for the differences in the stabilities of the complexes.

A potentiostatic and galvanostatic study of the selective dissolution of Cd/Pb eutectic alloy

International Nuclear Information System (INIS)

Sokharev, N.P.; Rabdel, A.A.; Zhadanov, V.V.

1986-01-01

The authors consider the selective dissolution (SD) of the electronegative component of a two-phase, eutectic alloy (Cd/Pb) under galvanostatic conditions. Treating this process as the extraction of a solid substance from a porous matrix, the distribution of the concentration of EC ions, c(x, t), can be described by a differential equation (presented). Experimental data are presented in two equations which are applicable for the description of the selective dissolution process of the electronegative component of a eutectic alloy under conditions of concentration polarization

Consistency in thermophysical properties: enthalpy, heat capacity, thermal conductivity and thermal diffusivity of solid UO2

International Nuclear Information System (INIS)

Fink, J.K.; Chasanov, M.G.; Leibowitz, L.

Equations have been derived for the enthalpy, heat capacity, thermal conductivity, and thermal diffusivity of UO 2 . In selection of these equations, we considered the traditional criterion of lowest relative standard deviation between experimental data and the function chosen to fit these data as well as consistency between the thermophysical properties. In the latter case, we considered consistency in (1) thermodynamic relations among properties, (2) the choice of physical phenomena on which to base the theoretical formulation of the equations, and (3) the existence and temperature of phase transitions

Surface studies of feldspar dissolution using surface replication combined with electron microscopic and spectroscopic techniques

Energy Technology Data Exchange (ETDEWEB)

Fung, P C [Petro-Canada, Calgary, Alberta; Sanipelli, G G

1982-04-01

The replica of a microcline cleavage surface was examined before and at various stages of interaction with water and acid solutions at 70/sup 0/C, as part of basic geochemical research for the Canadian Nuclear Fuel Waste Management Program to investigate the feasibility of disposal of these wastes in repositories mined in crystalline rocks. The objective of the report presented was to investigate the mechanism for Al and Si removal during incongruent dissolution of feldspars and its effect on dissolution rate. It was found that phase transformation, like dissolution occured preferentially along crystal defects on the surfaces of the feldspars. Secondary minerals always occured as discrete particles occupying only a very small fraction of the total parent surface, and hence, their presence would not affect the bulk composition or, in this regard, the overall dissolution rate of the feldspars by the formation of diffusion barriers.

Knudsen cell vaporization of rare earth nitrides: enthalpy of vaporization of HoN098

International Nuclear Information System (INIS)

Brown, R.C.; Clark, N.J.

1975-01-01

The enthalpy of vaporization of HoN 0 . 98 was measured by the weight-loss Knudsen cell technique using Motzfeldt-Whitman extrapolations to zero orifice area. A third-law enthalpy of vaporization of HoN 0 . 98 of 155.9 +- 5 kcal mole -1 was obtained compared to a second-law value of 162.0 +- 5 kcal mole -1 . Similar measurements on the nitrides of samarium, erbium, and ytterbium gave third-law enthalpies of vaporization of 126.8 +-- 5 kcal mole -1 ; 159.6 +- 5 kcal mole -1 , and 121.0 +- 5 kcal mole -1 , respectively. 7 tables

Modelling of the UO2 dissolution mechanisms in synthetic groundwater solutions. Dissolution experiments carried out under oxic conditions

International Nuclear Information System (INIS)

Cera, E.; Grive, M.; Bruno, J.; Ollila, K.

2001-02-01

The analytical data generated during the last three years within the 4th framework program of the European Community at VTT Chemical Technology concerning UO 2 dissolution under oxidising conditions have been modelled in the present work. The modelling work has been addressed to perform a kinetic study of the dissolution data generated by Ollila (1999) under oxidising conditions by using unirradiated uranium dioxide as solid sample. The average of the normalised UO 2 dissolution rates determined by using the initial dissolution data generated in all the experimental tests is (6.06 ± 3.64)* 10 -7 mol m -2 d -1 . This dissolution rate agrees with most of the dissolution rates reported in the literature under similar experimental conditions. The results obtained in this modelling exercise show that the same bicarbonate promoted oxidative dissolution processes operate for uranium dioxide, as a chemical analogue of the spent fuel matrix, independently of the composition of the aqueous solution used. (orig.)

Surface controlled dissolution rates of gypsum in aqueous solutions exhibit nonlinear dissolution kinetics

Science.gov (United States)

Jeschke, Alexander A.; Vosbeck, Katrin; Dreybrodt, Wolfgang

2001-01-01

The effective dissolution rates of gypsum are determined by mixed kinetics, where the rate constants of dissolution at the surface and the transport constant of molecular diffusion of dissolved material are similar. To obtain the surface reaction rate law it is necessary to know the transport constant. We have determined the surface rate law for monocrystalline selenite by using a rotating disc set-up, where the transport coefficients are well known. As a result, up to a calcium concentration of 0.6 · ceq, we find a nearly linear rate law Rs = ksl (1- cs/ ceq) n1, where cs is the total calcium concentration at the surface and ceq the equilibrium concentration with respect to gypsum, n1 = 1.2 ± 0.2, and ksl = 1.1 · 10 -4 mmol cm -2 s -1 ± 15%. We also employed batch-experiments for selenite, alabaster and gypsum rock samples. The result of these experiments were interpreted by using a transport constant determined by NaCl dissolution experiments under similar physical conditions. The batch experiments reveal a dissolution rate law Rs = ksl (1- cs/ ceq) n1, ksl = 1.3 · 10 -4 mmol · cm -2 s -1, n1 = 1.2 ± 0.2 for c ≤ 0.94 · ceq. Close to equilibrium a nonlinear rate law, Rs = ks2 (1- cs/ ceq) n2, is observed, where ks2 is in the order of 10 mmol · cm -2 s -1 and n2 ≈ 4.5. The experimentally observed gypsum dissolution rates from the batch experiments could be accurately fitted, with only minor variations of the surface reaction constant obtained from the rotating disk experiment and the transport coefficient from the NaCl dissolution batch experiment. Batch experiments on pure synthetic gypsum, reveal a linear rate law up to equilibrium. This indicates inhibition of dissolution in natural samples close to equilibrium, as is known also for calcite minerals.

Use of the co-grinding method to enhance the dissolution behavior of a poorly water-soluble drug: generation of solvent-free drug-polymer solid dispersions.

Science.gov (United States)

Yang, Caiqin; Xu, Xiujuan; Wang, Jing; An, Zhiqian

2012-01-01

The solid dispersion (SD) technique is the most effective method for improving the dissolution rate of poorly water-soluble drugs. In the present work, SDs of the Ca2+ channel blocker dipfluzine (DF) with polyvinylpyrrolidone K30 (PVP) and poloxamer 188 (PLXM) were prepared by the powder solid co-grinding method under a solvent-free condition. The properties of all SDs and physical mixtures were investigated by X-ray diffraction, Fourier-transform infrared, differential scanning calorimetry, scanning electron microscopy, dissolution test, and particles size determination. Eutectic compounds were produced between the DF and PLXM matrix during the co-grinding process, whereas glass suspension formed in the SDs with PVP carrier. Hydrogen bond formation was not observed between DF and carriers and DF was microcrystalline state in the PVP and PLXM matrices. The solubility of DF in different concentration of carriers at 25, 31, and 37°C was investigated; the values obtained were used to calculate the thermodynamic parameters of interaction between DF and carriers. The Gibbs free energy (ΔrGθ) values were negative, indicating the spontaneous nature of dispersing DF into the carriers. Moreover, entropy is the drive force when DF disperses into the matrix of PVP, while, enthalpy-driven dispersing encounters in the PLXM carrier. All the SDs of DF/carriers showed a considerably higher dissolution rate than pure DF and the corresponding physical mixtures. The cumulative dissolution rate at 10 min of the SD with a 1 : 3 DF/carrier ratio increased 5.1-fold for PVP and 5.5-fold for PLXM.

Prediction of failure enthalpy and reliability of irradiated fuel rod under reactivity-initiated accidents by means of statistical approach

International Nuclear Information System (INIS)

Nam, Cheol; Choi, Byeong Kwon; Jeong, Yong Hwan; Jung, Youn Ho

2001-01-01

During the last decade, the failure behavior of high-burnup fuel rods under RIA has been an extensive concern since observations of fuel rod failures at low enthalpy. Of great importance is placed on failure prediction of fuel rod in the point of licensing criteria and safety in extending burnup achievement. To address the issue, a statistics-based methodology is introduced to predict failure probability of irradiated fuel rods. Based on RIA simulation results in literature, a failure enthalpy correlation for irradiated fuel rod is constructed as a function of oxide thickness, fuel burnup, and pulse width. From the failure enthalpy correlation, a single damage parameter, equivalent enthalpy, is defined to reflect the effects of the three primary factors as well as peak fuel enthalpy. Moreover, the failure distribution function with equivalent enthalpy is derived, applying a two-parameter Weibull statistical model. Using these equations, the sensitivity analysis is carried out to estimate the effects of burnup, corrosion, peak fuel enthalpy, pulse width and cladding materials used

Effects of partitioned enthalpy of mixing on glass-forming ability

Energy Technology Data Exchange (ETDEWEB)

Song, Wen-Xiong; Zhao, Shi-Jin, E-mail: shijin.zhao@shu.edu.cn [Institute of Materials Science, Shanghai University, Shanghai 200072 (China)

2015-04-14

We explore the inherent reason at atomic level for the glass-forming ability of alloys by molecular simulation, in which the effect of partitioned enthalpy of mixing is studied. Based on Morse potential, we divide the enthalpy of mixing into three parts: the chemical part (Δ E{sub nn}), strain part (Δ E{sub strain}), and non-bond part (Δ E{sub nnn}). We find that a large negative Δ E{sub nn} value represents strong AB chemical bonding in AB alloy and is the driving force to form a local ordered structure, meanwhile the transformed local ordered structure needs to satisfy the condition (Δ E{sub nn}/2 + Δ E{sub strain}) < 0 to be stabilized. Understanding the chemical and strain parts of enthalpy of mixing is helpful to design a new metallic glass with a good glass forming ability. Moreover, two types of metallic glasses (i.e., “strain dominant” and “chemical dominant”) are classified according to the relative importance between chemical effect and strain effect, which enriches our knowledge of the forming mechanism of metallic glass. Finally, a soft sphere model is established, different from the common hard sphere model.

Determination of enthalpy–temperature–composition relations in incongruent-melting phase change materials

International Nuclear Information System (INIS)

Desgrosseilliers, Louis; Allred, Paul; Groulx, Dominic; White, Mary Anne

2013-01-01

This paper demonstrates that liquidus line (T-x) data can be obtained from calorimetric determinations of phase transition enthalpy profiles (H-T) for incongruent-melting phase change materials (PCMs) more efficiently than using traditional cooling curves. An accurate and reliable equilibrium mixture enthalpy model bridges the H-T and T-x gap to provide a full suite of high density H-T-x data to assist latent heat energy storage researchers to evaluate composition-dependent two-phase equilibrium processes. The proposed method is validated for T-history method H-T determinations of 1:1 diluted sodium acetate trihydrate in water, and can also be used with other laboratory calorimetric techniques used to determine the phase transition enthalpy profiles of incongruent-melting compounds. -- Highlights: • H-T data can also be used to obtain valuable liquidus region T-x data. • Applies to all incongruent-melting compounds with known thermodynamic properties. • Reduces the effort and cost of assessing full suite H-T-x data for PCMs. • Uses existing T-x or H-T data of incongruent-melting PCMs to determine the other

Standard molar enthalpies of formation of copper(II) β-diketonates and monothio-β-diketonates

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Santos, Luis M.N.B.F.

2006-01-01

The standard (p o =0.1MPa) molar enthalpies of formation of the crystalline complexes of dibenzoylmethane (Hdbm), thenoyltrifluoroacetone (Httfa), monothiodibenzoylmethane (HdbmS), and monothiothenoyltrifluoroacetone (HttfaS) of copper(II) were determined, at T=298.15K, by high precision solution-reaction calorimetry. The standard molar enthalpies of sublimation of the copper(II) β-diketonate complexes were measured by high-temperature Calvet microcalorimetry. From the standard molar enthalpies of formation of the complexes in the gaseous state, the mean molar dissociation enthalpies copper(II)-ligand, m >(Cu-L), were derived. Δ f H m o (cr)Δ cr g H m o kJ.mol -1 kJ.mol -1 Bis(dibenzoylmethanate)copper(II), Cu(dbm) 2 -364.0+/-3.9230.7+/-8.2Bis(thenoyltrifluoroacetonate)copper(II), Cu(ttfa) 2 -1824.3+/-8.3167.9+/-7.4Bis(monothiodibenzoylmethanate)copper(II), Cu(dbmS) 2 35.6+/-7.7[241+/-15]Bis(monothiothenoyltrifluoroacetonate) copper(II), Cu(ttfaS) 2 -1405.7+/-8.3[177+/-15

In-vitro dissolution rate and molecular docking studies of cabergoline drug with β-cyclodextrin

Science.gov (United States)

Shanmuga priya, Arumugam; Balakrishnan, Suganya bharathi; Veerakanellore, Giri Babu; Stalin, Thambusamy

2018-05-01

The physicochemical properties and dissolution profile of cabergoline drug (CAB) with β-cyclodextrin (β-CD) inclusion complex were investigated by the UV spectroscopy. The inclusion complex has used to calculate the stability constant and gives the stoichiometry molar ratio is 1:1 between CAB and β-CD. The phase solubility diagram and the aqueous solubility of CAB (60%) was found to be enhanced by β-CD. In addition, the phase solubility profile of CAB with β-CD was classified as AL-type. Binary systems of CAB with β-CD were prepared by Physical mixture, Kneading and solvent evaporation methods. The solid-state properties of the inclusion complex were characterized by Fourier transformation-infrared spectroscopy, Differential scanning calorimetry, Powder X-ray diffractometric patterns and Scanning electron microscopic techniques. Theoretically, β-CD and CAB inclusion complex obtained by molecular docking studies, it is in good correlation with the results obtained through experimental methods using the Schrödinger software program. In-vitro dissolution profiles of the inclusion complexes were carried out and obvious increase in dissolution rate was observed when compared with pure CAB drug and the complexes.

Dissolution of minerals with rough surfaces

Science.gov (United States)

de Assis, Thiago A.; Aarão Reis, Fábio D. A.

2018-05-01

We study dissolution of minerals with initial rough surfaces using kinetic Monte Carlo simulations and a scaling approach. We consider a simple cubic lattice structure, a thermally activated rate of detachment of a molecule (site), and rough surface configurations produced by fractional Brownian motion algorithm. First we revisit the problem of dissolution of initial flat surfaces, in which the dissolution rate rF reaches an approximately constant value at short times and is controlled by detachment of step edge sites. For initial rough surfaces, the dissolution rate r at short times is much larger than rF ; after dissolution of some hundreds of molecular layers, r decreases by some orders of magnitude across several time decades. Meanwhile, the surface evolves through configurations of decreasing energy, beginning with dissolution of isolated sites, then formation of terraces with disordered boundaries, their growth, and final smoothing. A crossover time to a smooth configuration is defined when r = 1.5rF ; the surface retreat at the crossover is approximately 3 times the initial roughness and is temperature-independent, while the crossover time is proportional to the initial roughness and is controlled by step-edge site detachment. The initial dissolution process is described by the so-called rough rates, which are measured for fixed ratios between the surface retreat and the initial roughness. The temperature dependence of the rough rates indicates control by kink site detachment; in general, it suggests that rough rates are controlled by the weakest microscopic bonds during the nucleation and formation of the lowest energy configurations of the crystalline surface. Our results are related to recent laboratory studies which show enhanced dissolution in polished calcite surfaces. In the application to calcite dissolution in alkaline environment, the minimal values of recently measured dissolution rate spectra give rF ∼10-9 mol/(m2 s), and the calculated rate

Determination of the vacancy formation enthalpy for high purity Ni

International Nuclear Information System (INIS)

Lynn, K.G.; Snead, C.L. Jr.; Hurst, J.J.; Farrell, K.

1979-01-01

Positron-annihilation lifetime measurements have been made on Ni over a temperature range of 4.2 to 1700 K. We find a small change in the lifetime from 4.2 to 900 K indicating a very small thermal-expansion effect. A small precursor effect is observed before the onset of significant vacancy trapping. A monovacancy formation enthalpy of 1.54/sub +0.2//sup -0.1/ eV is extracted without taking divacancies into consideration in the analysis. No detrapping from mono-vacancies is observed even at the higher temperatures. The vacancy formation enthalpy extracted from the lifetime data is compared to values obtained by Doppler-broadening and angular-correlation techniques

The vapor pressure and enthalpy of vaporization of M-xylene

International Nuclear Information System (INIS)

Rothenberg, S.J.; Seiler, F.A.; Bechtold, W.E.; Eidson, A.F.

1988-01-01

We measured the vapor pressure of m-xylene over the temperature range 273 to 293 deg K with a single-sided capacitance manometer. The enthalpy of vaporization was 42.2 ± 0.1 (SE) kj/ g·mol. Combining our own data with previously published data, we recommend using the values 42.0, 40.6, and 39.1 (± 0.1) (SE) kjg·mol for the enthalpy of vaporization of m-xylene at 300, 340, and 380 deg. K, respectively, and a value for the change in heat capacity on vaporization (ΔCpdeg.) of 35 ± 3 (SE) J/g·mol·K over the temperature range studied. (author)

Determination of the vacancy formation enthalpy for high purity Ni

International Nuclear Information System (INIS)

Lynn, K.G.; Snead, C.L. Jr.; Hurst, J.J.; Farrell, K.

1979-01-01

Positron-annihilation lifetime measurements have been made on Ni over a temperature range of 4.2 to 1700 K. We find a small change in the lifetime from 4.2 - 900 K indicating a very small thermal-expansion effect. A small precursor effect is observed before the onset of significant vacancy trapping. A monovacancy formation enthalpy of 1.54sub(+0.2)sup(-0.1) eV is extracted without taking divacancies into consideration in the analysis. No detrapping from mono-vacancies is observed even at the higher temperatures. The vacancy formation enthalpy extracted from the lifetime data is compared to values obtained by Doppler-broadening and angular-correlation techniques. (author)

Dissolution process for advanced-PWR-type fuels

International Nuclear Information System (INIS)

Black, D.E.; Decker, L.A.; Pearson, L.G.

1979-01-01

The new Fluorinel Dissolution Process and Fuel Storage (FAST) Facility at ICPP will provide underwater storage of spent PWR fuel and a new head-end process for fuel dissolution. The dissolution will be two-stage, using HF and HNO 3 , with an intermittent H 2 SO 4 dissolution for removing stainless steel components. Equipment operation is described

Affinity functions for modeling glass dissolution rates

Energy Technology Data Exchange (ETDEWEB)

Bourcier, W.L. [Lawrence Livermore National Lab., CA (United States)

1997-07-01

Glass dissolution rates decrease dramatically as glass approach ''saturation'' with respect to the leachate solution. Most repository sites are chosen where water fluxes are minimal, and therefore the waste glass is most likely to dissolve under conditions close to ''saturation''. The key term in the rate expression used to predict glass dissolution rates close to ''saturation'' is the affinity term, which accounts for saturation effects on dissolution rates. Interpretations of recent experimental data on the dissolution behaviour of silicate glasses and silicate minerals indicate the following: 1) simple affinity control does not explain the observed dissolution rate for silicate minerals or glasses; 2) dissolution rates can be significantly modified by dissolved cations even under conditions far from saturation where the affinity term is near unity; 3) the effects of dissolved species such as Al and Si on the dissolution rate vary with pH, temperature, and saturation state; and 4) as temperature is increased, the effect of both pH and temperature on glass and mineral dissolution rates decrease, which strongly suggests a switch in rate control from surface reaction-based to diffusion control. Borosilicate glass dissolution models need to be upgraded to account for these recent experimental observations. (A.C.)

The dissolution of chalcopyrite in chloride media

International Nuclear Information System (INIS)

Ibanez, T.; Velasquez, L.

2013-01-01

The aim of this investigation is to determinate the effects of parameters and additives on the kinetics of dissolution of chalcopyrite on moderated conditions by means of dissolutions test with chalcopyrite concentrate and pure chalcopyrite in shake flasks and instrumented stirred reactors. A study of the dissolution of chalcopyrite in chloride solutions has demonstrated that the rate of dissolution of chalcopyrite is strongly dependent on the potential of the solution within a range of 540 to 630 mV (versus SHE). Leaching at pH around 2.5 results in increased rates of copper dissolution suggesting the possibility to keep the solution potential within the range. Both pyrite and silver ions enhance the dissolution of chalcopyrite and this effect increases when both species are present. The MnO 2 has a negative effect on the dissolution increasing the solution potential to values where the rate decreases considerably. (Author)

A Study on Thermal Properties and α( hcp) → β( bcc) Phase Transformation Energetics in Ti-5 mass% Ta-1.8 mass% Nb Alloy Using Inverse Drop Calorimetry

Science.gov (United States)

Behera, Madhusmita; Raju, S.; Jeyaganesh, B.; Mythili, R.; Saroja, S.

2010-12-01

Accurate measurements of enthalpy increment ( H T - H 298.15) values have been made on a Ti-5 mass% Ta-1.8 mass% Nb alloy using the inverse drop calorimetry technique in the temperature range from 463 K to 1457 K. The measured enthalpy increment values show a steady increase with temperature in both α- hcp and β- bcc solid solution regions. It is found that both the onset as well the completion of the α → β phase change are demonstrated by a marked deviation of the enthalpy increment behavior from the otherwise smooth variation encountered in the respective low-temperature α- and high-temperature β-phase domains. The transformation start ( T s) and finish ( T f) temperatures of the α → β phase change are found to be (1072±10) K and (1156±10) K, respectively. In the actual α → β phase transformation region, the variation of the enthalpy with the progress of transformation is found to follow a sigmoidal shape which is in line with the diffusive nature of the phase transformation. An estimation of the total enthalpy change associated with the α → β phase transformation (Δ° H tr) has been made by assuming a simple diffusion limited kinetic model for the phase change. The net enthalpy change for the α → β transformation is found to be 76 J · g-1. The measured temperature variation of the enthalpy increment in both α- and β-phase regimes are fitted to simple analytical functional forms to obtain temperature-dependent estimates of the specific heat, C P . The total specific heat change associated with the α → β phase transformation {Δ^{circ}{CP^{α}}^{→{β}}} is estimated to be 904 J · kg-1 · K-1.

Quartz dissolution and silica deposition in hot-dry-rock geothermal systems

Energy Technology Data Exchange (ETDEWEB)

Robinson, B.A.

1982-07-01

The kinetics of quartz dissolution control the produced fluid dissolved silica concentration in geothermal systems in which the downhole residence time is finite. The produced fluid of the Phase I, Run Segment 5 experimental Hot Dry Rock (HDR) geothermal system at Fenton Hill, NM, was undersaturated with respect to quartz in one pass through the reservoir, suggesting that the rate of granite dissolution governed the outlet dissolved silica concentration in this system. The literature data for the rate of quartz dissolution in water from 65 to 625/sup 0/C is correlated using an empirical rate law which is first order in quartz surface area and degree of undersaturation of the fluid. The Arrhenius plot (ln k vs T/sup -1/) is linear over eight orders of magnitude of the rate constant, verifying the validity of the proposed rate expression. Carefully performed quartz dissolution experiments in the present study duplicated the literature data and completed the data base in the temperature range from 150 to 250/sup 0/C. Identical experiments using crushed granite indicate that the rate of quartz dissolution in the presence of granite could be as much as 1 to 2 orders of magnitude faster than the rates observed in the pure quartz experiments. A temperature dependent HDR reservoir model incorporates the quartz dissolution rate law to simulate the dissolved silica behavior during the Fenton Hill Run Segment 5 experiment. For this low-permeability, fracture-dominated reservoir, the assumptions of one-dimensional plug flow through a vertically-inclined rectangular fracture and one-dimensional rock heat conduction perpendicular to the direction of flow are employed. These simplifications lead to an analytical solution for the temperature field in the reservoir.

Dissolution glow curve in LLD

International Nuclear Information System (INIS)

Haverkamp, U.; Wiezorek, C.; Poetter, R.

1990-01-01

Lyoluminescence dosimetry is based upon light emission during dissolution of previously irradiated dosimetric materials. The lyoluminescence signal is expressed in the dissolution glow curve. These curves begin, depending on the dissolution system, with a high peak followed by an exponentially decreasing intensity. System parameters that influence the graph of the dissolution glow curve, are, for example, injection speed, temperature and pH value of the solution and the design of the dissolution cell. The initial peak does not significantly correlate with the absorbed dose, it is mainly an effect of the injection. The decay of the curve consists of two exponential components: one fast and one slow. The components depend on the absorbed dose and the dosimetric materials used. In particular, the slow component correlates with the absorbed dose. In contrast to the fast component the argument of the exponential function of the slow component is independent of the dosimetric materials investigated: trehalose, glucose and mannitol. The maximum value, following the peak of the curve, and the integral light output are a measure of the absorbed dose. The reason for the different light outputs of various dosimetric materials after irradiation with the same dose is the differing solubility. The character of the dissolution glow curves is the same following irradiation with photons, electrons or neutrons. (author)

Low-enthalpy geothermal resources for electricity production: A demand-side management study for intelligent communities

DEFF Research Database (Denmark)

Xydis, George A.; Nanaki, Evanthia A.; Koroneos, Christopher J.

2013-01-01

The geological conditions in Greece contributed to the creation of important low-enthalpy geothermal energy resources (LEGERs). The resources are divided into low, medium and high enthalpy, or temperature, based on criteria that are generally based on the energy content of the fluid. LEGERs...... and northern part of the country, as well as in many of the Aegean Islands. The aim of this work is to review the options for managing wind load by using low-enthalpy geothermal energy for electricity (through heat pump utilisation) according to the local energy demand....... are those sources of the hot water whose temperature is between 25 and 100°C, which are used for heating residences and in the agricultural or industrial sector. The investigation for the exploitation of low-enthalpy geothermal fluids, which began around 1980, intensified in the last two decades. The low...

Building blocks for ionic liquids: Vapor pressures and vaporization enthalpies of 1-(n-alkyl)-imidazoles

International Nuclear Information System (INIS)

Emel'yanenko, Vladimir N.; Portnova, Svetlana V.; Verevkin, Sergey P.; Skrzypczak, Andrzej; Schubert, Thomas

2011-01-01

Highlights: → We measured vapor pressures of the 1-(n-alkyl)-imidazoles by transpiration method. → Variations on the alkyl chain length n were C 3 , C 5 -C 7 , and C 9 -C 10 . → Enthalpies of vaporization were derived from (p, T) dependencies. → Enthalpies of vaporization at 298.15 K were linear dependent on the chain length. - Abstract: Vapor pressures of the linear 1-(n-alkyl)-imidazoles with the alkyl chain C 3 , C 5 -C 7 , and C 9 -C 10 have been measured by the transpiration method. The molar enthalpies of vaporization Δ l g H m of these compounds were derived from the temperature dependencies of vapor pressures. A linear correlation of enthalpies of vaporization Δ l g H m (298.15 K) of the 1-(n-alkyl)-imidazoles with the chain length has been found.

Composition and Dissolution of a Migratory, Weathered Coal Tar Creosote DNAPL

Directory of Open Access Journals (Sweden)

Kerstin E. Scherr

2016-09-01

Full Text Available Opaque, viscous tars derived from the carbonization of fossile carbon feedstocks, such coal tars and creosote, are long-term sources of groundwater contamination, predominantly with poly- and heterocyclic aromatic hydrocarbons (PAH. The dissolution, ageing and migratory behavior of dense, non aqueous phase liquid (DNAPL coal tar blobs and pools forming at the aquitard is not sufficiently understood to estimate the risk and adequately design groundwater treatment measures at a contaminated site. In this study, we investigate the composition and dissolution of a migrated, aged creosote DNAPL and corresponding experimental and groundwater profiles using comprehensive two-dimensional gas chromatography (GCxGC-MS. GC-FID unresolved compounds were attributed to methylated homocyclic species using GCxGC-MS in the Methylanthracene weight range. Equilibrium concentrations were estimated using Raoult’s law, assuming non-ideal behavior. Low molecular weight compounds were found to be prevalent even after decades of weathering, with Naphthalene (8% by mass representing the most abundant identified compound, contrary to the expected preferential depletion of hydrophilic compounds. Morevoer, dimethylnaphthalenes were relatively more abundant in the aqueous boundary layer than in the DNAPL. DNAPL migration over 400m with the groundwater flow effected lower viscosity and specific gravity of the migrated phase body in a superposition of weathering, transport and aquifer chromatography effects. Based on a decomposition of analysed and estimated constituents using the group contribution approach, reference DNAPL values for activity coefficients γi were used to model aqueous solubilities for selected compounds. Anthracene was close to its theoretical precipitation limit in the bulk DNAPL. While laboratory and modelled DNAPL dissolution behavior agree well, field data imply the presence of specific interfacial in situ processes significantly impacting dissolution

Determinations of enthalpy and partial molar enthalpy in the alloys Bi–Cd–Ga–In–Zn, Bi–Cd–Ga–Zn and Au–Cu–Sn

International Nuclear Information System (INIS)

Arslan, Hüseyin

2015-01-01

In the present study, the relations of thermodynamic associated with Chou's general solution model (GSM), the models of Muggianu and Toop have been used in order to calculate the mixing enthalpy and partial molar mixing enthalpy of mixing of Bi–Cd–Ga–In–Zn, Bi–Cd–Ga–Zn with equimolar section at a temperature of 730 K and Au–Cu–Sn with the section x Au /x Cu = 1/1 on the entire molar fraction range as a function of alloy composition at a temperature of 900 K. Some negativities are reported in the selected alloys mentioned above, particularly at high temperatures for the human health as well as difficulties in experimental measurement and high costs. Moreover, aim of us is to close the current article gap seen in the literature. In order to close the current gap seen in the literature, the article on the thermodynamic properties of the Bi–Cd–Ga–In–Zn alloys are presented in this study. - Highlights: • Thermodynamic properties of alloys in the study in given conditions were treated. • The activity of Bi seen in all models shows greatly positive deviation from ideality. • The enthalpy of Sn shows small negative values in x Au /x Cu = 1 at 900 K. • The activity of Sn shows negative deviation from ideality in the same conditions

Modified enthalpy method for the simulation of melting and ...

Indian Academy of Sciences (India)

These include the implicit time stepping method of Voller & Cross. (1981), explicit enthalpy method of Tacke (1985), centroidal temperature correction method ... In variable viscosity method, viscosity is written as a function of liquid fraction.

PREDICTION OF THE MIXING ENTHALPIES OF BINARY LIQUID ALLOYS BY MOLECULAR INTERACTION VOLUME MODEL

Institute of Scientific and Technical Information of China (English)

H.W.Yang; D.P.Tao; Z.H.Zhou

2008-01-01

The mixing enthalpies of 23 binary liquid alloys are calculated by molecular interaction volume model (MIVM), which is a two-parameter model with the partial molar infinite dilute mixing enthalpies. The predicted values are in agreement with the experimental data and then indicate that the model is reliable and convenient.

Structure determination of electrodeposited zinc-nickel alloys: thermal stability and quantification using XRD and potentiodynamic dissolution

International Nuclear Information System (INIS)

Fedi, B.; Gigandet, M.P.; Hihn, J-Y; Mierzejewski, S.

2016-01-01

Highlights: • Quantification of zinc-nickel phases between 1,2% and 20%. • Coupling XRD to partial potentiodynamic dissolution. • Deconvolution of anodic stripping curves. • Phase quantification after annealing. - Abstract: Electrodeposited zinc-nickel coatings obtained by electrodeposition reveal the presence of metastable phases in various quantities, thus requiring their identification, a study of their thermal stability, and, finally, determination of their respective proportions. By combining XRD measurement with partial potentiodynamic dissolution, anodic peaks were indexed to allow their quantification. Quantification of electrodeposited zinc-nickel alloys approximately 10 μm thick was thus carried out on nickel content between 1.2% and 20%, and exhibited good accuracy. This method was then extended to the same set of alloys after annealing (250 °C, 2 h), thus bringing the structural organization closer to its thermodynamic equilibrium. The result obtained ensures better understanding of crystallization of metastable phases and of phase proportion evolution in a bi-phasic zinc-nickel coating. Finally, the presence of a monophase γ and its thermal stability in the 12% to 15% range provides important information for coating anti-corrosion behavior.

Determination of the protonation enthalpy of humic acid by calorimetric titration technique

International Nuclear Information System (INIS)

Kimuro, Shingo; Kirishima, Akira; Sato, Nobuaki

2015-01-01

Graphical abstract: The thermodynamic quantities of protonation of humic acid were determined by the combination of potentiometric titration and calorimetric titration. It was observed that the protonation enthalpy and Gibbs free energy had been affected by pH of solution. As a result, the thermodynamics of the protonation reaction of humic acid is influenced by the polyelectrolyte effect and the heterogeneity. - Highlights: • We applied calorimetric titration technique to the protonation of humic acid. • The thermodynamic quantities of protonation of humic acid were determined. • The protonation enthalpy of humic acid is affected by the heterogeneity. • Gibbs free energy of the protonation is affected by the polyelectrolyte effect. - Abstract: In this study, the calorimetric titration technique was used to determine the protonation enthalpy of two reference humic acids and polyacrylic acid. First, we obtained the apparent protonation constant of two kinds of humic acid purchased from IHSS (International Humic Substances Society) and polyacrylic acid by potentiometric titration. Second, we obtained the protonation enthalpy of them by calorimetric titration. The protonation enthalpy of humic acid was affected by pH and the ionic strength of bulk solution. From the comparison of ΔH between humic acid and polyacrylic acid, it was concluded that the pH dependence of ΔH is attributed to the heterogeneity of humic acid. And ΔH of phenolic hydroxyl group in humic acid is strongly influenced by the electric double layer of humic acid’s surface. This is considered to be a reason of the ionic strength dependence of ΔH. On the other hand, Gibbs free energy of the protonation of humic acid is affected by the electrostatic attraction with the progress of dissociation of functional groups such as carboxyl group and phenolic hydroxyl group. Consequently, the thermodynamics of the protonation of humic acid is affected by the polyelectrolyte effect and the

Intercomparative tests on phase change materials characterisation with differential scanning calorimeter

International Nuclear Information System (INIS)

Lazaro, Ana; Peñalosa, Conchita; Solé, Aran; Diarce, Gonzalo; Haussmann, Thomas; Fois, Magali; Zalba, Belén; Gshwander, Stefan; Cabeza, Luisa F.

2013-01-01

Highlights: ► Advances in intercomparative tests of enthalpy of phase change material (PCM). ► Enthalpy of PCM determined by DSC is influenced by certain factors. ► The influence factors were identified. ► A methodology to avoid these influences for heating measurements is proposed. ► Forthcoming steps are focused on calibration and cooling measurements. - Abstract: For the correct design of thermal storage systems using phase change materials (PCMs) in any application, as well as for their simulation, it is essential to characterise the materials from thermophysical and rheological standpoints (phase change enthalpy, thermal conductivity in solid and liquid phases, viscosity and density in function of temperature). Taking advantage of the different research groups facilities available in two international networks: within the IEA (International Energy Agency), the ECES Implementing Agreement (Energy Conservation through Energy Storage IA) and SHC Programme (Solar Heating and Cooling) Task 42/Annex 24 “Compact Thermal Energy Storage – Material Development for System Integration”, and the COST Action TU0802 “Next generation cost effective phase change materials for increased energy efficiency in renewable energy systems in buildings (NeCoE-PCM)” a set of Round Robin Tests (RRTs) was proposed. The objective was to come to comparable results for PCMs using Differential Scanning Calorimetry (DSC) to determine their melting enthalpy as well as their melting and solidification behaviour. The first RRT was without defining the procedure, the second one with a predefined procedure for the measurements, but not for calibration and the third one with a predefined procedure for calibration, for the measurements and also for the data evaluation. This paper presents the conclusions after the three RRT. The main conclusion of the paper is that enthalpy in function of temperature determined using a dynamic method for DSC can be influenced by certain reasons

Vapor pressures and vaporization enthalpy of codlemone by correlation gas chromatography

International Nuclear Information System (INIS)

Schultz, Shannon M.; Harris, Harold H.; Chickos, James S.

2015-01-01

Highlights: • The vaporization enthalpy of codlemone has been evaluated. • The vapor pressure of codlemone has been evaluated from T = (298.15 to T b ) K. • Vapor pressures for the 1-alkanols standards are available from T = (298.15 to 500) K. - Abstract: The vapor pressure and vaporization enthalpy of codlemone (trans, trans 8,10-dodecadien-1-ol), the female sex hormone of the codling moth is evaluated by correlation gas chromatography using a series of saturated primary alcohols as standards. A vaporization enthalpy of (92.3 ± 2.6) kJ · mol −1 and a vapor pressure, p/Pa = (0.083 ± 0.012) were evaluated at T = 298.15 K. An equation for the evaluation of vapor pressure from ambient temperature to boiling has been derived by correlation for codlemone. The calculated boiling temperature of T B = 389 K at p = 267 Pa is within the temperature range reported in the literature. A normal boiling temperature of T B = (549.1 ± 0.1) K is also estimated by extrapolation

The use of commercial microwave dissolution equipment for the fast and reliable dissolution of high-fired POX and MOX samples

International Nuclear Information System (INIS)

Tushingham, J.; McInnes, C.; Firkin, S.

1998-09-01

The use of commercially available microwave dissolution equipment for the fast and reliable dissolution of high-fired plutonium dioxide (POX) and mixed oxide (MOX) samples has been evaluated for application to Safeguards Analysis. Under the auspices of the UK R and D Support Programme to the IAEA, equipment has been purchased and tested for the high-pressure microwave dissolution of POX samples fired to 1250 deg. C and MOX samples fired to 1600 deg. C, in concentrated nitric acid and hydrofluoric acid mixture. Considerable problems were encountered during development of procedures for microwave dissolution, resulting largely from sudden changes in pressure within dissolution vessels, which resulted in actuation of safety interlocks designed to prevent overpressurisation. These difficulties were alleviated by controlling the microwave power to reduce the reaction temperature and pressure, and also by introducing additional safety valves into the digestion vessels. Using microwave digestion, dissolution times for high fired POX and MOX samples were substantially reduced. Samples which required ca. 10 hours to dissolve by conventional means could be dissolved in ca. 80 minutes by microwave digestion. Whilst a similar performance in terms of plutonium recovery was achieved for some materials by microwave and conventional dissolution, for other materials microwave dissolution gave higher plutonium recoveries but with poorer precision. This suggests the possible presence of some plutonium oxide within high-fired materials which is more difficult to dissolve than the bulk, and which is perhaps dissolved to an additional but variable degree by the current microwave dissolution procedure. Microwave dissolution has been demonstrated to increase the speed of dissolution of high-fired POX and MOX materials, compared with conventional dissolution. However, the technique has not yet proved satisfactory for the complete dissolution of all high-fired materials tested because of

Self-inhibition can limit biologically enhanced TCE dissolution from a TCE DNAPL.

Science.gov (United States)

Haest, P J; Springael, D; Seuntjens, P; Smolders, E

2012-11-01

Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3-6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19-55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3-2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Determination of formation enthalpies of incongruently fusing compounds

Energy Technology Data Exchange (ETDEWEB)

Kesler, Ya.A.; Cheshnitskij, S.M.; Fotiev, A.A.; Tret' yakov, Yu.D.

1985-04-01

Using the method of drop-calorimetry i.e. drop into the calorimeter cell being at the specified temperature of the specimen thermostated at 298 K, for studying reactions of peritectic decomposition of compounds for determining their formation enthalpies is considered. The measurements have been performed at 973 K using high temperature double microcalorimeter. The values ..delta..H/sub 1/=(367.0 +- 2.8) kJ/mol and ..delta..H/sub 2/=)343.9 +- 3.1) kJ/mol are obtained as a result of two series of measurements (6 experiments in each). The advantage of the described technique consists in the fact that the value of enthalpy of compound formation is obtained as a result of direct calorimetric measurements while in the e.m.f. method this value is determined as a coefficient in the Gibbs energy temperature dependence. The method is simple and does not require much time (one measurement takes 30-40 min).

Determination of formation enthalpies of incongruently fusing compounds

International Nuclear Information System (INIS)

Kesler, Ya.A.; Cheshnitskij, S.M.; Fotiev, A.A.; Tret'yakov, Yu.D.

1985-01-01

Using the method of drop-calorimetry i.e. drop into the calorimeter cell being at the specified temperature of the specimen thermostated at 298 K, for studying reactions of peritectic decomposition of compounds for determining their formation enthalpies is considered. The measurements have been performed at 973 K using high temperature double microcalorimeter. The values ΔH 1 =(367.0+-2.8) kJ/mol and ΔH 2 =)343.9+-3.1) kJ/mol are obtained as a result of two series of measurements (6 experiments in each). The advantage of the described technique consists in the fact that the value of enthalpy of compound formation is obtained as a result of direct calorimetric measurements while in the e.m.f. method this value is determined as a coefficient in the Gibbs energy temperature dependence. The method is simple and does not require much time (one measurement takes 30-40 min)

Validation of a dissolution method with RP-HPLC analysis for Perindopril erbumine and Indapamide combination tablet

Directory of Open Access Journals (Sweden)

Jain P.S.

2012-01-01

Full Text Available A Dissolution method with high performance liquid chromatography (HPLC analysis was validated for perindopril erbumine and indapamide in combination tablet formulation. The method was validated to meet requirements for a global regulatory filing and this validation included specificity, linearity, accuracy, precision, range, robustness and solution stability studies. The dissolution method, which uses USP apparatus 1 with basket rotating at 100 rpm, 1000 ml of phosphate buffer pH 6.8 as the dissolution medium, and reversed-phased HPLC was carried out at 50⁰C on a 4.6mm×250mm 5μm cyano column that contained USP packing L1 with acetonitrile: buffer pH 2.8::40:60 (v/v, as mobile phase. UV detector was set at 225 nm. A method was found to be selective, linear, accurate and precise in the specified ranges. Intra-day and inter-day variability for method was <2% RSD. This method was successfully used for quantification of perindopril erbumine and indapamide combination tablet formulations.

Development of Dissolution Test Method for Drotaverine ...

African Journals Online (AJOL)

Development of Dissolution Test Method for Drotaverine ... Methods: Sink conditions, drug stability and specificity in different dissolution media were tested to optimize a dissolution test .... test by Prism 4.0 software, and differences between ...

Vaporization enthalpies of imidazolium based ionic liquids. A thermogravimetric study of the alkyl chain length dependence

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Zaitsau, Dzmitry H.; Emel’yanenko, Vladimir N.; Ralys, Ricardas V.; Yermalayeu, Andrei V.; Schick, Christoph

2012-01-01

Highlights: ► Enthalpies of vaporization of ionic liquids were measured with thermogravimetry. ► We studied 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide. ► The linear alkyl chain length was 4, 6, 8, 10, 12, 14, 16, and 18 C-atoms. ► A linear dependence on the chain length of the alkyl-imidazolium cation was found. - Abstract: Vaporization enthalpies for a series of ten ionic liquids (ILs) 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide [C n mim][NTf 2 ], with the alkyl chain length n = 4, 6, 8, 10, 12, 14, 16, and 18 were determined using the thermogravimetric method. An internally consistent set of experimental data and vaporization enthalpies at 540 K was obtained. Vaporization enthalpies at 540 K have shown a linear dependence on the chain length of the alkyl-imidazolium cation in agreement with the experimental results measured previously with a quartz crystal microbalance. Ambiguity of Δ l g C pm o -values required for the extrapolation of experimental vaporization enthalpies to the reference temperature 298 K has been discussed.

Mechanistic Basis of Cocrystal Dissolution Advantage.

Science.gov (United States)

Cao, Fengjuan; Amidon, Gordon L; Rodríguez-Hornedo, Naír; Amidon, Gregory E

2018-01-01

Current interest in cocrystal development resides in the advantages that the cocrystal may have in solubility and dissolution compared with the parent drug. This work provides a mechanistic analysis and comparison of the dissolution behavior of carbamazepine (CBZ) and its 2 cocrystals, carbamazepine-saccharin (CBZ-SAC) and carbamazepine-salicylic acid (CBZ-SLC) under the influence of pH and micellar solubilization. A simple mathematical equation is derived based on the mass transport analyses to describe the dissolution advantage of cocrystals. The dissolution advantage is the ratio of the cocrystal flux to drug flux and is defined as the solubility advantage (cocrystal to drug solubility ratio) times the diffusivity advantage (cocrystal to drug diffusivity ratio). In this work, the effective diffusivity of CBZ in the presence of surfactant was determined to be different and less than those of the cocrystals. The higher effective diffusivity of drug from the dissolved cocrystals, the diffusivity advantage, can impart a dissolution advantage to cocrystals with lower solubility than the parent drug while still maintaining thermodynamic stability. Dissolution conditions where cocrystals can display both thermodynamic stability and a dissolution advantage can be obtained from the mass transport models, and this information is useful for both cocrystal selection and formulation development. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Progress in development of a source term for sphene glass-ceramic dissolution under vault conditions

International Nuclear Information System (INIS)

Hayward, P.J.; Tait, J.C.; George, I.M.; Carmichael, A.A.; Ross, J.M.P.

1986-01-01

This report describes the results of ongoing leaching experiments, involving aluminosilicate glass and sphene (CaTiSiO/sub 5/) ceramics, doped with /sup 22/Na or /sup 45/Ca, and leached in a simulated Ca-NA-Cl brine at 25 0 or 100 0 C. The experiments are designed to aid development of separate models for the dissolution of the glass and the ceramic phase in a sphene glass-ceramic, and to help evaluate a composite model for the dissolution of the glass-ceramic

Dominant Alcohol-Protein Interaction via Hydration-Enabled Enthalpy-Driven Binding Mechanism

Science.gov (United States)

Chong, Yuan; Kleinhammes, Alfred; Tang, Pei; Xu, Yan; Wu, Yue

2015-01-01

Water plays an important role in weak associations of small drug molecules with proteins. Intense focus has been on binding-induced structural changes in the water network surrounding protein binding sites, especially their contributions to binding thermodynamics. However, water is also tightly coupled to protein conformations and dynamics, and so far little is known about the influence of water-protein interactions on ligand binding. Alcohols are a type of low-affinity drugs, and it remains unclear how water affects alcohol-protein interactions. Here, we present alcohol adsorption isotherms under controlled protein hydration using in-situ NMR detection. As functions of hydration level, Gibbs free energy, enthalpy, and entropy of binding were determined from the temperature dependence of isotherms. Two types of alcohol binding were found. The dominant type is low-affinity nonspecific binding, which is strongly dependent on temperature and the level of hydration. At low hydration levels, this nonspecific binding only occurs above a threshold of alcohol vapor pressure. An increased hydration level reduces this threshold, with it finally disappearing at a hydration level of h~0.2 (g water/g protein), gradually shifting alcohol binding from an entropy-driven to an enthalpy-driven process. Water at charged and polar groups on the protein surface was found to be particularly important in enabling this binding. Although further increase in hydration has smaller effects on the changes of binding enthalpy and entropy, it results in significant negative change in Gibbs free energy due to unmatched enthalpy-entropy compensation. These results show the crucial role of water-protein interplay in alcohol binding. PMID:25856773

Standard enthalpies of formation of selected Ru{sub 2}YZ Heusler compounds

Energy Technology Data Exchange (ETDEWEB)

Yin, Ming, E-mail: myin1@hawk.iit.edu; Nash, Philip

2015-06-15

Highlights: • Standard enthalpies of formation of Ru{sub 2}YZ were measured using a drop calorimeter. • Result of L2{sub 1} structured compounds agrees with first principles data. • Lattice parameters and related phase relationships were consistent with literature data. • Ru{sub 2}HfSn, Ru{sub 2}TiSn, Ru{sub 2}VGa, Ru{sub 2}VSi, Ru{sub 2}VSn of L2{sub 1} structure were reported for the first time. - Abstract: The standard enthalpies of formation of selected ternary Ru-based Heusler compounds Ru{sub 2}YZ (Y = Fe, Hf, Mn, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) were measured using high temperature direct reaction calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the Heusler compounds are, Ru{sub 2}FeGe (−19.7 ± 3.3); Ru{sub 2}HfSn (−24.9 ± 3.6); Ru{sub 2}MnSi (−46.0 ± 2.6); Ru{sub 2}MnGe (−29.7 ± 1.0); Ru{sub 2}MnSn (−20.6 ± 2.4); Ru{sub 2}TiSi (−94.9 ± 4.0); Ru{sub 2}TiGe (−79.1 ± 3.2); Ru{sub 2}TiSn (−60.6 ± 1.8); Ru{sub 2}VSi (−55.9 ± 1.7);for the B2-structured compounds, Ru{sub 2}FeSi (−28.5 ± 0.8); Ru{sub 2}HfAl (−70.8 ± 1.9); Ru{sub 2}MnAl (−32.3 ± 1.9); Ru{sub 2}MnGa (−25.3 ± 3.0); Ru{sub 2}TiAl (−62.7 ± 3.5); Ru{sub 2}VAl (−30.9 ± 1.6); Ru{sub 2}ZrAl (−64.5 ± 1.5). Values were compared with those from published first principles calculations and the OQMD (Open Quantum Materials Database). Lattice parameters of these compounds were determined using X-ray diffraction analysis (XRD). Microstructures were identified using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS)

The vapor pressure and enthalpy of vaporization of M-xylene

Energy Technology Data Exchange (ETDEWEB)

Rothenberg, S J; Seiler, F A; Bechtold, W E; Eidson, A F

1988-12-01

We measured the vapor pressure of m-xylene over the temperature range 273 to 293 deg K with a single-sided capacitance manometer. The enthalpy of vaporization was 42.2 {+-} 0.1 (SE) kj/ g{center_dot}mol. Combining our own data with previously published data, we recommend using the values 42.0, 40.6, and 39.1 ({+-} 0.1) (SE) kjg{center_dot}mol for the enthalpy of vaporization of m-xylene at 300, 340, and 380 deg. K, respectively, and a value for the change in heat capacity on vaporization ({delta}Cpdeg.) of 35 {+-} 3 (SE) J/g{center_dot}mol{center_dot}K over the temperature range studied. (author)

Enthalpy - entropy compensation effect in grain boundary phenomena

Czech Academy of Sciences Publication Activity Database

Lejček, Pavel

2005-01-01

Roč. 96, č. 10 (2005), s. 1129-1133 ISSN 0044-3093 R&D Projects: GA MPO(CZ) FF-P2/053 Institutional research plan: CEZ:AV0Z10100520 Keywords : compensation effect * enthalpy * entropy * thermodynamics * grain boundary Subject RIV: BJ - Thermodynamics Impact factor: 0.842, year: 2005

Standard molar enthalpies of formation of copper(II) {beta}-diketonates and monothio-{beta}-diketonates

Energy Technology Data Exchange (ETDEWEB)

Ribeiro da Silva, Manuel A.V. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)]. E-mail: risilva@fc.up.pt; Santos, Luis M.N.B.F. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

2006-07-15

The standard (p{sup o}=0.1MPa) molar enthalpies of formation of the crystalline complexes of dibenzoylmethane (Hdbm), thenoyltrifluoroacetone (Httfa), monothiodibenzoylmethane (HdbmS), and monothiothenoyltrifluoroacetone (HttfaS) of copper(II) were determined, at T=298.15K, by high precision solution-reaction calorimetry. The standard molar enthalpies of sublimation of the copper(II) {beta}-diketonate complexes were measured by high-temperature Calvet microcalorimetry. From the standard molar enthalpies of formation of the complexes in the gaseous state, the mean molar dissociation enthalpies copper(II)-ligand, (Cu-L), were derived. {delta}{sub f}H{sub m}{sup o} (cr){delta}{sub cr}{sup g}H{sub m}{sup o} kJ.mol{sup -1}kJ.mol{sup -1}Bis(dibenzoylmethanate)copper(II), Cu(dbm){sub 2}-364.0+/-3.9230.7+/-8.2Bis(thenoyltrifluoroacetonate)copper(II), Cu(ttfa){sub 2}-1824.3+/-8.3167.9+/-7.4Bis(monothiodibenzoylmethanate)copper(II), Cu(dbmS){sub 2}35.6+/-7.7[241+/-15]Bis(monothiothenoyltrifluoroacetonate) copper(II), Cu(ttfaS){sub 2}-1405.7+/-8.3[177+/-15].

A new self-emulsifying formulation of mefenamic acid with enhanced drug dissolution

Directory of Open Access Journals (Sweden)

Pornsak Sriamornsak

2015-04-01

Full Text Available To enhance the dissolution of poorly soluble mefenamic acid, self-emulsifying formulation (SEF, composing of oil, surfactant and co-surfactant, was formulated. Among the oils and surfactants studied, Imwitor® 742, Tween® 60, Cremophore® EL and Transcutol® HP were selected as they showed maximal solubility to mefenamic acid. The ternary phase diagram was constructed to find optimal concentration that provided the highest drug loading. The droplet size after dispersion and drug dissolution of selected formulations were investigated. The results showed that the formulation containing Imwitor® 742, Tween® 60 and Transcutol® HP (10:30:60 can encapsulate high amount of mefenamic acid. The dissolution study demonstrated that, in the medium containing surfactant, nearly 100% of mefenamic acid were dissolved from SEF within 5 min while 80% of drugs were dissolved from the commercial product in 45 min. In phosphate buffer (without surfactant, 80% of drug were dissolved from the developed SEF within 5 min while only about 13% of drug were dissolved in 45 min, from the commercial product. The results suggested that the SEF can enhance the dissolution of poorly soluble drug and has a potential to enhance drug absorption and improve bioavailability of drug.

Enthalpies of mixing in the ternary system aluminium chloride - potassium chloride - aluminium chloride monoamine

Energy Technology Data Exchange (ETDEWEB)

Hatem, G.; Gaune-Escard, M.; Bros, J.P. (Aix-Marseille-2 Univ., 13 - Marseille (France). Centre de Saint Jerome); Ostvold, T. (Norges Tekniske Hoegskole, Trondheim (Norway). Inst. for Uorganisk Kjemi)

1988-06-01

Quasi binary enthalpy of mixing experiments have been performed in the ternary liquid system AlCl{sub 3}-AlCl{sub 3}NH{sub 3}-KCl by mixing AlCl{sub 3} + KCl with AlCl{sub 3}NH{sub 3} keeping the ratio X{sub AlCl3}/X{sub KCl} = 1.125, 1.5 and 2.0, respectively. At X{sub AlCl3}NH{sub 3} = 0.5 and T = 270deg C the enthalpies of mixing were {approx equal} -430 J mol{sup -1} for all the quasi-binaries studied. The new enthalpy data are not fully consistent with published vapour pressure data and thermodynamic model calculations. (orig.).

Simulation benchmark based on THAI-experiment on dissolution of a steam stratification by natural convection

Energy Technology Data Exchange (ETDEWEB)

Freitag, M., E-mail: freitag@becker-technologies.com; Schmidt, E.; Gupta, S.; Poss, G.

2016-04-01

Highlights: . • We studied the generation and dissolution of steam stratification in natural convection. • We performed a computer code benchmark including blind and open phases. • The dissolution of stratification predicted only qualitatively by LP and CFD models during the blind simulation phase. - Abstract: Locally enriched hydrogen as in stratification may contribute to early containment failure in the course of severe nuclear reactor accidents. During accident sequences steam might accumulate as well to stratifications which can directly influence the distribution and ignitability of hydrogen mixtures in containments. An international code benchmark including Computational Fluid Dynamics (CFD) and Lumped Parameter (LP) codes was conducted in the frame of the German THAI program. Basis for the benchmark was experiment TH24.3 which investigates the dissolution of a steam layer subject to natural convection in the steam-air atmosphere of the THAI vessel. The test provides validation data for the development of CFD and LP models to simulate the atmosphere in the containment of a nuclear reactor installation. In test TH24.3 saturated steam is injected into the upper third of the vessel forming a stratification layer which is then mixed by a superposed thermal convection. In this paper the simulation benchmark will be evaluated in addition to the general discussion about the experimental transient of test TH24.3. Concerning the steam stratification build-up and dilution of the stratification, the numerical programs showed very different results during the blind evaluation phase, but improved noticeable during open simulation phase.

Effect of Mineral Dissolution/Precipitation and CO2 Exsolution on CO2 transport in Geological Carbon Storage.

Science.gov (United States)

Xu, Ruina; Li, Rong; Ma, Jin; He, Di; Jiang, Peixue

2017-09-19

Geological carbon sequestration (GCS) in deep saline aquifers is an effective means for storing carbon dioxide to address global climate change. As the time after injection increases, the safety of storage increases as the CO 2 transforms from a separate phase to CO 2 (aq) and HCO 3 - by dissolution and then to carbonates by mineral dissolution. However, subsequent depressurization could lead to dissolved CO 2 (aq) escaping from the formation water and creating a new separate phase which may reduce the GCS system safety. The mineral dissolution and the CO 2 exsolution and mineral precipitation during depressurization change the morphology, porosity, and permeability of the porous rock medium, which then affects the two-phase flow of the CO 2 and formation water. A better understanding of these effects on the CO 2 -water two-phase flow will improve predictions of the long-term CO 2 storage reliability, especially the impact of depressurization on the long-term stability. In this Account, we summarize our recent work on the effect of CO 2 exsolution and mineral dissolution/precipitation on CO 2 transport in GCS reservoirs. We place emphasis on understanding the behavior and transformation of the carbon components in the reservoir, including CO 2 (sc/g), CO 2 (aq), HCO 3 - , and carbonate minerals (calcite and dolomite), highlight their transport and mobility by coupled geochemical and two-phase flow processes, and consider the implications of these transport mechanisms on estimates of the long-term safety of GCS. We describe experimental and numerical pore- and core-scale methods used in our lab in conjunction with industrial and international partners to investigate these effects. Experimental results show how mineral dissolution affects permeability, capillary pressure, and relative permeability, which are important phenomena affecting the input parameters for reservoir flow modeling. The porosity and the absolute permeability increase when CO 2 dissolved water is

In vitro dissolution methodology, mini-Gastrointestinal Simulator (mGIS), predicts better in vivo dissolution of a weak base drug, dasatinib.

Science.gov (United States)

Tsume, Yasuhiro; Takeuchi, Susumu; Matsui, Kazuki; Amidon, Gregory E; Amidon, Gordon L

2015-08-30

USP apparatus I and II are gold standard methodologies for determining the in vitro dissolution profiles of test drugs. However, it is difficult to use in vitro dissolution results to predict in vivo dissolution, particularly the pH-dependent solubility of weak acid and base drugs, because the USP apparatus contains one vessel with a fixed pH for the test drug, limiting insight into in vivo drug dissolution of weak acid and weak base drugs. This discrepancy underscores the need to develop new in vitro dissolution methodology that better predicts in vivo response to assure the therapeutic efficacy and safety of oral drug products. Thus, the development of the in vivo predictive dissolution (IPD) methodology is necessitated. The major goals of in vitro dissolution are to ensure the performance of oral drug products and the support of drug formulation design, including bioequivalence (BE). Orally administered anticancer drugs, such as dasatinib and erlotinib (tyrosine kinase inhibitors), are used to treat various types of cancer. These drugs are weak bases that exhibit pH-dependent and high solubility in the acidic stomach and low solubility in the small intestine (>pH 6.0). Therefore, these drugs supersaturate and/or precipitate when they move from the stomach to the small intestine. Also of importance, gastric acidity for cancer patients may be altered with aging (reduction of gastric fluid secretion) and/or co-administration of acid-reducing agents. These may result in changes to the dissolution profiles of weak base and the reduction of drug absorption and efficacy. In vitro dissolution methodologies that assess the impact of these physiological changes in the GI condition are expected to better predict in vivo dissolution of oral medications for patients and, hence, better assess efficacy, toxicity and safety concerns. The objective of this present study is to determine the initial conditions for a mini-Gastrointestinal Simulator (mGIS) to assess in vivo

Determination of standard molar enthalpies of formation of SrMoO4 micro/nano structures

International Nuclear Information System (INIS)

Guo, Yunxiao; Fan, Gaochao; Huang, Zaiyin; Sun, Jilong; Wang, Lude; Wang, Tenghui; Chen, Jie

2012-01-01

Graphical abstract: Schematic illustration of thermochemical cycle between the nano and bulk reaction systems. Highlights: ► A thermochemical cycle was designed. ► Relationship of standard molar enthalpies of formation between micro/nano and bulk SrMoO 4 was gained. ► Microcalorimetry was used as a supplementary technology. ► Standard molar enthalpies of formation of the synthesized micro/nano SrMoO 4 were obtained. ► This novel approach can be used to other micro/nano materials. - Abstract: SrMoO 4 micro/nano structures were prepared by a simple reverse microemulsion method and were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscope (SEM). In order to associate standard molar enthalpies of formation of nano SrMoO 4 with bulk SrMoO 4 , the relationship of them was obtained through designing a thermochemical cycle according to thermodynamic potential function method. Combined with microcalorimetry, the standard molar enthalpies of formation of the synthesized micro/nano SrMoO 4 at 298.15 K were gained in this paper. And the variation of standard molar enthalpies of formation of micro/nano SrMoO 4 with different morphologies and sizes was discussed.

The role of anodic dissolution in the stress corrosion cracking of Al-Li-Cu alloy 2090

International Nuclear Information System (INIS)

Buchheit, R.G. Jr.; Wall, F.D.; Stoner, G.E.; Moran, J.P.

1991-01-01

The short-transverse (S-T) stress corrosion cracking (SCC) behavior of Al-Li-CU alloy 2090 was studied using a static load SCC test technique. Time to failure was measured as a function of applied potential in several different environments. Rapid SCC failures ( br, T1 applied br, matrix where potentials refer to the breakaway potentials of the subgrain boundary T 1 (Al 2 CuLi) phase and the α-Al matrix phase. E br values were measured using potentiodynamic polarization of bulk materials intended to simulate the individual phases found in the subgrain boundary region. Results strongly suggest an anodic dissolution based SCC mechanism for this alloy where selective dissolution of T 1 on the subgrain boundary is a critical step. The unusual pre-exposure embrittlement phenomenon demonstrated by Al- Li alloys is also shown to be consistent with these simple SCC criteria. 21 refs., 9 figs., 6 tabs

Modified solution calorimetry approach for determination of vaporization and sublimation enthalpies of branched-chain aliphatic and alkyl aromatic compounds at T = 298.15 K

International Nuclear Information System (INIS)

Varfolomeev, Mikhail A.; Novikov, Vladimir B.; Nagrimanov, Ruslan N.; Solomonov, Boris N.

2015-01-01

Highlights: • Solution enthalpies of 18 branching-chain alkyl aromatic and aliphatic compounds in cyclohexane were measured. • Group contributions to the enthalpy of solvation due to branching and substitution in carbon chain were evaluated. • Modified solution calorimetry based approach for determination of vaporization/sublimation enthalpies was proposed. • This approach provides vaporization/sublimation enthalpies directly at T = 298.15 K. • Vaporization/sublimation enthalpies of 35 branched-chain alkyl aromatic and aliphatic compounds were determined. - Abstract: The enthalpies of solution, solvation and vaporization/sublimation are interrelated values combined in the simplest thermodynamic circle. Hence, experimental determination of vaporization/sublimation enthalpy can be substituted by experimentally simpler determination of solution enthalpy when solvation enthalpy is known. Previously it was found that solvation enthalpies of a wide range of unbranched aliphatic and aromatic solutes in saturated hydrocarbons are in good linear correlation with their molar refraction values. This allows to estimate the vaporization/sublimation enthalpy of any unbranched organic compound from its solution enthalpy in saturated hydrocarbon and molar refraction. In the present work this approach was modified for determination of vaporization/sublimation enthalpy of branched-chain alkyl aromatic and aliphatic compounds. Group contributions to the enthalpy of solvation due to the branching of carbon chain were evaluated. Enthalpies of solution at infinite dilution of 18 branched-chain aliphatic and alkyl aromatic compounds were measured at T = 298.15 K. Vaporization/sublimation enthalpies for 35 branched aliphatic and alkyl aromatic compounds were determined by using modified solution calorimetry approach. These values are in good agreement with available literature data on vaporization/sublimation enthalpies obtained by conventional methods.

Enhanced ferrihydrite dissolution by a unicellular, planktonic cyanobacterium: a biological contribution to particulate iron bioavailability.

Science.gov (United States)

Kranzler, Chana; Kessler, Nivi; Keren, Nir; Shaked, Yeala

2016-12-01

Iron (Fe) bioavailability, as determined by its sources, sinks, solubility and speciation, places severe environmental constraints on microorganisms in aquatic environments. Cyanobacteria are a widespread group of aquatic, photosynthetic microorganisms with especially high iron requirements. While iron exists predominantly in particulate form, little is known about its bioavailability to cyanobacteria. Some cyanobacteria secrete iron solubilizing ligands called siderophores, yet many environmentally relevant strains do not have this ability. This work explores the bioavailability of amorphous synthetic Fe-oxides (ferrihydrite) to the non-siderophore producing, unicellular cyanobacterium, Synechocystis sp PCC 6803. Iron uptake assays with 55 ferrihydrite established dissolution as a critical prerequisite for iron transport. Dissolution assays with the iron binding ligand, desferrioxamine B, demonstrated that Synechocystis 6803 enhances ferrihydrite dissolution, exerting siderophore-independent biological influence on ferrihydrite bioavailability. Dissolution mechanisms were studied using a range of experimental conditions; both cell-particle physical proximity and cellular electron flow were shown to be important determinants of bio-dissolution by Synechocystis 6803. Finally, the effects of ferrihydrite stability on bio-dissolution rates and cell physiology were measured, integrating biological and chemical aspects of ferrihydrite bioavailability. Collectively, these findings demonstrate that Synechocystis 6803 actively dissolves ferrihydrite, highlighting a significant biological component to mineral phase iron bioavailability in aquatic environments. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Kinetics and enthalpy of crystallization of uric acid dihydrate

International Nuclear Information System (INIS)

Sádovská, Galina; Honcová, Pavla; Sádovský, Zdeněk

2013-01-01

Highlights: • The kinetic constant and growth order of crystallization of uric acid dihydrate was calculated. • The equation describing first-order crystal growth was derived. • The enthalpy of crystallization of uric acid dihydrate was determined. - Abstract: The kinetics of crystallization of uric acid dihydrate in aqueous solution with a constant ionic strength 0.3 mol dm −3 NaCl and at thermodynamic and physiological temperature (25 and 37 °C) was studied using isoperibolic reaction twin calorimeter. The enthalpy of crystallization Δ cr H = −47.3 ± 0.9 and −46.2 ± 1.4 kJ mol −1 and kinetic constant k g = 2.0 × 10 −8 and 9.6 × 10 −8 m 4 s −1 mol −1 were determined at 25 and 37 °C, respectively

Vaporization study on vanadium monoxide and two-phase mixture of vanadium and vanadium monoxide by mass-spectrometric method

International Nuclear Information System (INIS)

Banchorndhevakul, W.; Matsui, Tsuneo; Naito, Keiji

1986-01-01

The vapor pressures over single phase vanadium monoxide VO 1.022 (s) and the two-phase mixture of vanadium metal (β phase) and vanadium monoxide were measured by mass-spectrometric method in the temperature range of 1,803 ∼ 1,990 and 1,703 ∼ 1,884 K, respectively. The main gas species over both systems were found to be VO(g) and V(g). The vapor pressure of VO(g) over the two-phase mixture of V(s) and VO(s) was a little lower than that over single phase VO(s). The vapor pressure of V(g) over the two-phase mixture was nearly equal to that over single phase. From the vapor pressure data, the enthalpies of vaporization, the enthalpies of formation for VO(g) and V(g) and the dissociation energy of VO(g) were determined. The oxygen partial pressure was calculated as a function of temperature from the vapor pressures of VO(g) and V(g), from which the partial molar enthalpies and entropies of oxygen in both systems were obtained. (author)

HB-Line Dissolution of Glovebox Floor Sweepings

International Nuclear Information System (INIS)

Gray, J.H.

1998-02-01

Two candidate flowsheets for dissolving glovebox floor sweepings in the HB-Line Phase I geometrically favorable dissolver have been developed.Dissolving conditions tested and modified during the laboratory program were based on the current processing scheme for dissolving high-fired Pu-238 oxide in HB-Line. Subsequent adjustments made to the HB-Line flowsheet reflected differences in the dissolution behavior between high-fired Pu-238 oxide and the MgO sand/PuF 4 /PuO 2 mixture in glovebox floor sweepings. Although both candidate flowsheets involved two separate dissolving steps and resulted incomplete dissolution of all solids, the one selected for use in HB-Line will require fewer processing operations and resembles the initial flowsheet proposed for dissolving sand, slag, and crucible material in F-Canyon dissolvers. Complete dissolution of glovebox floor sweepings was accomplished in the laboratory by initially dissolving between 55 and 65 degree in a 14 molar nitric acid solution. Under these conditions, partial dissolution of PuF 4 and complete dissolution of PuO 2 and MgO sand were achieved in less than one hour. The presence of free fluoride in solution,uncomplexed by aluminum, was necessary for complete dissolution of the PuO 2 .The remaining PuF 4 dissolved following addition of aluminum nitrate nonahydrate (ANN) to complex the fluoride and heating between 75 and 85 degree C for an additional hour. Precipitation of magnesium and/or aluminum nitrates could occur before, during, and after transfer of product solutions. Both dilution and/or product solution temperature controls may be necessary to prevent precipitation of these salts. Corrosion of the dissolver should not be an issue during these dissolving operations. Corrosion is minimized when dissolving at 55-65 degree C for one to three hours at a maximum uncomplexed free fluoride concentration of 0.07 molar and by dissolving at 75-85 degree C at a one to one aluminum to fluoride mole ratio for another

Dissolution of metallic uranium and its alloys. Part 1. Review of analytical and process-scale metallic uranium dissolution

International Nuclear Information System (INIS)

Laue, C.A.; Gates-Anderson, D.; Fitch, T.E.

2004-01-01

This review focuses on dissolution/reaction systems capable of treating uranium metal waste to remove its pyrophoric properties. The primary emphasis is the review of literature describing analytical and production-scale dissolution methods applied to either uranium metal or uranium alloys. A brief summary of uranium's corrosion behavior is included since the corrosion resistance of metals and alloys affects their dissolution behavior. Based on this review, dissolution systems were recommended for subsequent screening studies designed to identify the best system to treat depleted uranium metal wastes at Lawrence Livermore National Laboratory (LLNL). (author)

Thermochemical characteristics of La n+1Ni nO3n+1 oxides

International Nuclear Information System (INIS)

Bannikov, D.O.; Safronov, A.P.; Cherepanov, V.A.

2006-01-01

Lanthanum nickelates: La 2 NiO 4+δ , La 3 Ni 2 O 7-δ , La 4 Ni 3 O 10-δ and LaNiO 3-δ the members of Ruddlesden-Popper series La n+1 Ni n O 3n+1 were prepared using citrate route. Dissolution enthalpies of complex oxides as well as a number of subsidiary substances were measured by means of Calvet calorimeter in 1 M solution of hydrochloric acid at 25 deg. C. The dissolution scheme of complex oxides in hydrochloric acid was proposed and enthalpies of formation of the complex oxides from binary oxides were calculated considering oxygen nonstoichiometry of these substances. Enthalpies of step-by-step oxidation were evaluated. Partial enthalpy contribution of LaO layers was calculated endothermic equals to 30.9 J/mol while partial enthalpy contribution of perovskite LaNiO 3 layers was negative equals to -97.0 J/mol. Enthalpy of formation of any complex oxide of Ruddlesden-Popper series fits very well to the linear regression based on these values

Dissolution of uranium oxide TBP-HNO3 complex

International Nuclear Information System (INIS)

Mizuno, Mineo; Kosaka, Yuji; Mori, Yukihide; Shimada, Takashi

2002-12-01

As a head end process for the pulverization of the spent fuel, the mechanical method (the shredder method) and the pyro-chemical method (oxidisation heat-treatment) have been examined. UO 2 is a main ingredient of Uranium oxide powder by the mechanical method, and U 3 O 8 is that by the pyro-chemical method. Moreover, the particle size of the pulverized powder depend on the conditions of the pulverizing process. As it was considered that the difference of dissolution rates of samples was caused by the difference of sample chemical forms and dissolution temperature, parametric surveys on chemical form and particle size of powder and dissolution temperature were carried out, and the following results were obtained. 1) The remarkable difference of dissolution rate between U 3 O 8 powder (average particle size 3.7 μm) and UO 2 powder (average particle size 2.4 μm) which have comparatively similar particle size was not observed. 2) It was confirmed that the dissolution rate became lower according to the particle size increase (average particle size 2.4 μm-1 mm). And it was considered that dissolution rate had strong dependency on particle size, according to the results that the powder with 1 mm particle size did not dissolute completely after 5 hours test. 3) The temperature dependency of the dissolution rate was confirmed by dissolution test with UO 2 powder (average particle size 2.4 μm-1 mm). The higher dissolution rate was obtained in the higher dissolution temperature, and 11 kcal/mol was obtained as activation energy of dissolution. 4) In the dissolution test of UO 2 powder, the nitric acid concentration started to change earlier than that of U 3 O 8 powder and concentration change range became larger compared with that in the dissolution test of U 3 O 8 powder. It was considered that those differences were caused by difference in mole ratio of Uranium and nitric acid which are consumed in the dissolution reaction (3:7 for U 3 O 8 , 3:8 for UO 2 ). 5) In case

Dissolution rate enhancement of piroxicam by ordered mixing.

Science.gov (United States)

Saharan, Vikas Anand; Choudhury, Pratim Kumar

2012-07-01

Micronized piroxicam was mixed with lactose, mannitol, sorbitol, maltitol and sodium chloride to produce ordered mixture in a glass vial by manual hand shaking method. The effect of excipients, surfactant, superdisintegrant, drug concentration and carrier particle size on dissolution rate was investigated. Dissolution rate studies of the prepared ordered mixtures revealed that all water soluble excipients increased the dissolution rate of piroxicam when compared to the dissolution rate of piroxicam or its suspension. Ordered mixture formulation PLF4, consisting of lactose as water soluble excipient, SSG (8% w/s) and SLS (1% w/w), released piroxcam at a very fast rate so much so that about 90% of the composition had passed into solution within 2 min. The order of the dissolution rate enhancement for ordered mixtures of various water soluble excipients was: lactose > mannitol > maltitol > sorbitol > sodium chloride. Carrier granules of size 355-710 µm were most effective in increasing the dissolution rate of drug from ordered mixtures. Decreasing the carrier particle size reduced drug dissolution from ordered mixtures. The dissolution rate of ordered mixtures consisting of 1-5% w/w piroxicam was superior to dissolution rate of piroxicam suspension. The dissolution data fitting and the resulting regression parameters indicated Hixson Crowell, cube root law, as the best fit to drug release data of ordered mixtures.

The mixing enthalpy of the Pb-Te system

International Nuclear Information System (INIS)

Blachnik, R.; Gather, B.

1983-01-01

The thermodynamic properties of molten Pb-Te alloys were measured at 1210 K in a Setaram-Calvet-type calorimeter. It was found that the enthalpy of mixing has a pronounced minimum of -26250 +- 950 J mol - 1 at 52 mol.%Te. The results obtained are discussed in terms of an ionic model. (Auth.)

Extension of the segment-based Wilson and NRTL models for correlation of excess molar enthalpies of polymer solutions

International Nuclear Information System (INIS)

Sadeghi, Rahmat

2005-01-01

The polymer Wilson model and the polymer NRTL model have been extended for the representation of the excess enthalpy of multicomponent polymer solutions. Applicability of obtained equations in the correlation of the excess enthalpies of polymer solutions has been examined. It is found that the both models are suitable models in representing the published excess enthalpy data for the tested polymer solutions

Improvement of database on glass dissolution

International Nuclear Information System (INIS)

Hayashi, Maki; Sasamoto, Hiroshi; Yoshikawa, Hideki

2008-03-01

In geological disposal system, high-level radioactive waste (HLW) glass is expected to retain radionuclide for the long term as the first barrier to prevent radionuclide release. The advancement of its performance assessment technology leads to the reliability improvement of the safety assessment of entire geological disposal system. For this purpose, phenomenological studies for improvement of scientific understanding of dissolution/alteration mechanisms, and development of robust dissolution/alteration model based on the study outcomes are indispensable. The database on glass dissolution has been developed for supporting these studies. This report describes improvement of the prototype glass database. Also, this report gives an example of the application of the database for reliability assessment of glass dissolution model. (author)

Generalized enthalpy model of a high-pressure shift freezing process

KAUST Repository

Smith, N. A. S.

2012-05-02

High-pressure freezing processes are a novel emerging technology in food processing, offering significant improvements to the quality of frozen foods. To be able to simulate plateau times and thermal history under different conditions, in this work, we present a generalized enthalpy model of the high-pressure shift freezing process. The model includes the effects of pressure on conservation of enthalpy and incorporates the freezing point depression of non-dilute food samples. In addition, the significant heat-transfer effects of convection in the pressurizing medium are accounted for by solving the two-dimensional Navier-Stokes equations. We run the model for several numerical tests where the food sample is agar gel, and find good agreement with experimental data from the literature. © 2012 The Royal Society.

Low-enthalpy geothermal resources for electricity production: A demand-side management study for intelligent communities

International Nuclear Information System (INIS)

Xydis, George A.; Nanaki, Evanthia A.; Koroneos, Christopher J.

2013-01-01

The geological conditions in Greece contributed to the creation of important low-enthalpy geothermal energy resources (LEGERs). The resources are divided into low, medium and high enthalpy, or temperature, based on criteria that are generally based on the energy content of the fluid. LEGERs are those sources of the hot water whose temperature is between 25 and 100 °C, which are used for heating residences and in the agricultural or industrial sector. The investigation for the exploitation of low-enthalpy geothermal fluids, which began around 1980, intensified in the last two decades. The low-enthalpy geothermal potential in Greece is rather significant as most of the geothermal fields have been found in regions with favourable developmental conditions, and it seems that they do not present serious environmental or technical exploitation problems. LEGER areas are abundant in Greece, mainly in the eastern and northern part of the country, as well as in many of the Aegean Islands. The aim of this work is to review the options for managing wind load by using low-enthalpy geothermal energy for electricity (through heat pump utilisation) according to the local energy demand. -- Highlights: •Approximately 45.43 GWh per year of electricity can be covered from low-enthalpy geothermal energy resources (LEGERs). •In particular, 10% of the electricity demand can be covered from the LEGER N. Kessani (NK). •The needs for LEGER contribution were increased when wind turbine (WT) production was low. •In winter, where there is abundance of wind, LEGER can be used mostly for heating. •During summer, LEGER can assist more in electricity when heating is not needed

Equivalent Temperature-Enthalpy Diagram for the Study of Ejector Refrigeration Systems

Directory of Open Access Journals (Sweden)

Mohammed Khennich

2014-05-01

Full Text Available The Carnot factor versus enthalpy variation (heat diagram has been used extensively for the second law analysis of heat transfer processes. With enthalpy variation (heat as the abscissa and the Carnot factor as the ordinate the area between the curves representing the heat exchanging media on this diagram illustrates the exergy losses due to the transfer. It is also possible to draw the paths of working fluids in steady-state, steady-flow thermodynamic cycles on this diagram using the definition of “the equivalent temperature” as the ratio between the variations of enthalpy and entropy in an analyzed process. Despite the usefulness of this approach two important shortcomings should be emphasized. First, the approach is not applicable for the processes of expansion and compression particularly for the isenthalpic processes taking place in expansion valves. Second, from the point of view of rigorous thermodynamics, the proposed ratio gives the temperature dimension for the isobaric processes only. The present paper proposes to overcome these shortcomings by replacing the actual processes of expansion and compression by combinations of two thermodynamic paths: isentropic and isobaric. As a result the actual (not ideal refrigeration and power cycles can be presented on equivalent temperature versus enthalpy variation diagrams. All the exergy losses, taking place in different equipments like pumps, turbines, compressors, expansion valves, condensers and evaporators are then clearly visualized. Moreover the exergies consumed and produced in each component of these cycles are also presented. The latter give the opportunity to also analyze the exergy efficiencies of the components. The proposed diagram is finally applied for the second law analysis of an ejector based refrigeration system.

Dissolution of UO2 in redox conditions

International Nuclear Information System (INIS)

Casas, I.; Pablo de, J.; Rovira, M.

1998-01-01

The performance assessment of the final disposal of the spent nuclear fuel in geological formations is strongly dependent on the spent fuel matrix dissolution. Unirradiated uranium (IV) dioxide has shown to be very useful for such purposes. The stability of UO 2 is very dependent on vault redox conditions. At reducing conditions, which are expected in deep groundwaters, the dissolution of the UO 2 -matrix can be explained in terms of solubility, while under oxidizing conditions, the UO 2 is thermodynamically unstable and the dissolution is kinetically controlled. In this report the parameters which affect the uranium solubility under reducing conditions, basically pH and redox potential are discussed. Under oxidizing conditions, UO 2 dissolution rate equations as a function of pH, carbonate concentration and oxidant concentration are reported. Dissolution experiments performed with spent fuel are also reviewed. The experimental equations presented in this work, have been used to model independent dissolution experiments performed with both unirradiated and irradiated UO 2 . (Author)

Instability of the layered orthorhombic post-perovskite phase of SrTiO3 and other candidate orthorhombic phases under pressure

Science.gov (United States)

Bhandari, Churna; Lambrecht, Walter R. L.

2018-06-01

While the tetragonal antiferro-electrically distorted (AFD) phase with space group I 4 / mcm is well known for SrTiO3 to occur below 105 K, there are also some hints in the literature of an orthorhombic phase, either at the lower temperature or at high pressure. A previously proposed orthorhombic layered structure of SrTiO3, known as the post-perovskite or CaIrO3 structure with space group Cmcm is shown to have significantly higher energy than the cubic or tetragonal phase and to have its minimum volume at larger volume than cubic perovskite. The Cmcm structure is thus ruled out. We also study an alternative Pnma phase obtained by two octahedral rotations about different axes. This phase is found to have slightly lower energy than the I 4 / mcm phase in spite of the fact that its parent, in-phase tilted P 4 / mbm phase is not found to occur. Our calculated enthalpies of formation show that the I 4 / mcm phase occurs at slightly higher volume than the cubic phase and has a negative transition pressure relative to the cubic phase, which suggests that it does not correspond to the high-pressure tetragonal phase. The enthalpy of the Pnma phase is almost indistinguishable from the I 4 / mcm phase. Alternative ferro-electric tetragonal and orthorhombic structures previously suggested in literature are discussed.

Effects of ions traces on the dissolution of bioceramics composed of hydroxyapatite and β-tricalcium phosphate

Directory of Open Access Journals (Sweden)

Mohamed Jamil

2015-02-01

Full Text Available The aim of this work is to study the effect of trace ions as Mg2+, Sr2+, (SiO44- and Al3+, brought by the raw material, on the dissolution of the calcium-phosphate bioceramics.  The precursor powders prepared by aqueous precipitation with molar ratio Ca / P = 1.630 ± 0.002, were calcined at 1100°C resulting in the formation of a mixture of hydroxyapatite (Ca10(PO46(OH2 and β-tricalcium phosphate (β-Ca3(PO42.  Two mixtures which differ by the content of trace ions were characterized for phase purity, chemical composition and morphology.  The dissolution tests were performed at 37 °C in acidic buffers solution at pH 4.8.  The results showed that the dissolution of calcium ions is more important in the presence of ions trace while the phosphor ions were not affected.  The dissolution and dissolution-reprecipitation observed of various ions trace can modify the surface properties of calcium phosphate bioceramics and therefore the properties of biological products, such as resorbtion and reactivity can be affected.

Dissolution rate of BTEX contaminants in water