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Sample records for bond dissociation enthalpy

  1. Computational Study of Bond Dissociation Enthalpies for Lignin Model Compounds. Substituent Effects in Phenethyl Phenyl Ethers

    Energy Technology Data Exchange (ETDEWEB)

    Beste, Ariana [ORNL; Buchanan III, A C [ORNL

    2009-01-01

    Lignin is an abundant natural resource that is a potential source of valuable chemicals. Improved understanding of the pyrolysis of lignin occurs through the study of model compounds for which phenethyl phenyl ether (PhCH2CH2OPh, PPE) is the simplest example representing the dominant -O-4 ether linkage. The initial step in the thermal decomposition of PPE is the homolytic cleavage of the oxygen-carbon bond. The rate of this key step will depend on the bond dissociation enthalpy, which in turn will depend on the nature and location of relevant substituents. We used modern density functional methods to calculate the oxygen-carbon bond dissociation enthalpies for PPE and several oxygen substituted derivatives. Since carbon-carbon bond cleavage in PPE could be a competitive initial reaction under high temperature pyrolysis conditions, we also calculated substituent effects on these bond dissociation enthalpies. We found that the oxygen-carbon bond dissociation enthalpy is substantially lowered by oxygen substituents situated at the phenyl ring adjacent to the ether oxygen. On the other hand, the carbon-carbon bond dissociation enthalpy shows little variation with different substitution patterns on either phenyl ring.

  2. Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry.

    Science.gov (United States)

    Ruscic, Branko

    2015-07-16

    Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C-H, C-C, C-O, and O-H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4-0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6-0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4-0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species. PMID:25760799

  3. Enthalpy of Formation and O-H Bond Dissociation Enthalpy of Phenol: Inconsistency between Theory and Experiment.

    Science.gov (United States)

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2016-04-21

    Gas-phase O–H homolytic bond dissociation enthalpy in phenol, DH298°(C6H5O–H), is still disputed, despite a large number of experimental and computational studies. In estimating this value, the experimental enthalpy of formation of phenol, ΔfH298°(C6H5OH, g) = −96.4 ± 0.6 kJ/mol (Cox, J. D. Pure Appl. Chem. 1961, 2, 125−128), is often used assuming high accuracy of the experimental value. In the present work a substantially less negative value of ΔfH298°(C6H5OH, g) = −91.8 ± 2.5 kJ/mol was calculated combining G4 theory with an isodesmic reaction approach. A benchmark quality of this result was achieved by using a large number of reliable reference species in isodesmic reaction calculations. Among these are the most accurate ΔfH298° values currently available from the Active Thermochemical Tables (ATcT) for 36 species (neutral molecules, radicals, and ions), anisole with recently reassessed enthalpy of formation, and 13 substituted phenols. The internal consistency of the calculated ΔfH298°(C6H5OH, g) value with the experimental enthalpies of formation of more than 50 reference species suggests that the reported experimental enthalpy of formation of phenol is in error. Taking into account that the enthalpy of formation of phenol has not been investigated experimentally since 1961, the new measurements would be extremely valuable. Using the accurate enthalpies of formation of C6H5OH and C6H5O• calculated in the present work, we obtained DH298°(C6H5O–H) = 369.6 ± 4.0 kJ/mol. This value is in satisfactory agreement with that determined from the most precise experimental measurement.

  4. 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).

  5. Homolytic Bond Dissociation Enthalpies of C C and C-H Bonds in Highly Crowded Alkanes

    Institute of Scientific and Technical Information of China (English)

    ZHU Chen; RUI Lei; FU Yao

    2008-01-01

    The homolytic C-C and C--H bond dissociation enthalpyies (BDE) of highly crowded alkanes were calcu- lated by using an ONIOM-G3B3 method. Geometric parameters such as bond length, bond angle and molecular volume were carefully investigated, as most of the acyclic alkanes in this study were not yet synthesized. These pa-rameters reflect the influence of steric effect on BDE. Good correlations were found between the rapid decrease of BDE and the increase of molecular volumes. The correlations can be applied to the prediction of the possible exis-tence of many highly strained compounds.

  6. A theoretical study on C-COOH homolytic bond dissociation enthalpies.

    Science.gov (United States)

    Shi, Jing; Huang, Xiong-Yi; Wang, Jun-Peng; Li, Run

    2010-06-01

    The knowledge of C-COOH homolytic bond dissociation enthalpies (BDEs) is of great importance in understanding various chemical and biochemical processes involving the decarboxylation reaction. In the present study, the density functional theory (DFT method), B3P86/6-311++G(2df,2p)//B3LYP/6-31+G(d), is found to be reliable to predict the C-COOH BDE of various structurally unrelated carboxylic acids. The mean absolute deviation (MAD) and root-mean-square deviation (rmsd) of this optimal method are equal to 2.0 and 2.5 kcal/mol, respectively. With the authorized theoretical protocol in hand, an extensive C-COOH BDE scale containing over 100 carboxylic acids has been established. The availability of this body of data enabled a detailed investigation of remote substituent effect on four types of carboxylic acids, including para-substituted benzoic acid, beta-substituted cis-propenoic acid, beta-substituted trans-propenoic acid, and substituted propiolic acid. Also with the C-COOH BDE data obtained in this work, an excellent linear relationship has been found between the C-COOH BDE of carboxylic acids and the C-H BDE of their hydrocarbon analogues. After comparing the energy barrier of the Pd-catalyzed decarboxylation reaction (DeltaG(decarboxylation)++) with the related C-COOH BDE, a negative correlation between the DeltaG(decarboxylation)++ and the C-COOH BDE was found.

  7. The C-H bond dissociation enthalpies in fused N-heterocyclic compounds

    Science.gov (United States)

    Wang, Ying-Xing; Zheng, Wen-Rui; Ding, Lan-Lan

    2016-03-01

    The C-H bond dissociation enthalpies (BDEs) of the 26 N, O, S-containing mono-heterocyclic compounds were evaluated using the composite high-level ab initio methods G3 and G4. The C-H BDEs for 32 heterocyclic compounds were calculated using 8 types of density functional theory (DFT) methods. Comparing with the experimental values, the BMK method gave the lowest root mean square error (RMSE) of 7.2 kJ/mol. Therefore, the C-H BDEs of N-fused-heterocyclic compounds at different positions were investigated by the BMK method. By NBO analysis two linear relationships between the C-H BDEs of quinoline and isoquinoline with natural charges qC/ e in molecules and with natural charges qC/ e in radicals were found. The substituent effects on C(α)-H BDEs in N-fused-heterocyclic compounds were also discussed. It was found that there are two linear relationships between the C(α)-H BDEs of quinoline and isoquinoline derivatives with natural charges qC(α)/ e for the EDGs and CEGs substituents.

  8. Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies.

    Science.gov (United States)

    Treesuwan, Witcha; Suramitr, Songwut; Hannongbua, Supa

    2015-06-01

    Radical scavenging potential is the key to anti-oxidation of hydroxyflavones which generally found in fruits and vegetables. The objective of this work was to investigate the influence of hydroxyl group on the O-H bond dissociation enthalpies (BDE) from a series of mono- and dihydroxyflavones. Calculation at the B3LYP/6-31G(d,p) level reveals the important roles of an additional one hydroxyl group to boost the BDE of hydroxyflavones that were a stabilization of the generated radicals through attractive H-bond interactions, an ortho- and para-dihydroxyl effect, and a presence of the 3-OH in dihydroxyflavones. On the other hand, the meta-dihydroxyl effect and range-hydroxyl effect especially associated with the either 5-OH or 8-OH promoted greater BDE. Results did not only confirm that dihydroxyflavones had lower BDE than monohydroxyflavones but also suggest the selective potent hydroxyflavone molecules that are the 6'-hydroxyflavone (for monohydroxyflavone) and the 5',6'-, 7,8- and 3',4'-dihydroxyflavone which the corresponding radical preferable generated at C6'-O•, C8-O• and C4'-O•, respectively. Electron distribution was limited only over the two connected rings of hydroxyflavones while the expansion distribution into C-ring could be enhanced if the radical was formed especially for the 2',3'- and 5',6'dihydroxyflavone radicals. The delocalized bonds were strengthened after radical was generated. However the 5-O• in 5,6-dihydroxyflavone and the 3-O• in 3,6'-dihydroxyflavone increased the bond order at C4-O11 which might interrupt the conjugated delocalized bonds at the keto group.

  9. 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.

  10. PM6 study of free radical scavenging mechanisms of flavonoids: why does O-H bond dissociation enthalpy effectively represent free radical scavenging activity?

    Science.gov (United States)

    Amić, Dragan; Stepanić, Višnja; Lučić, Bono; Marković, Zoran; Dimitrić Marković, Jasmina M

    2013-06-01

    It is well known that the bond dissociation enthalpy (BDE) of the O-H group is related to the hydrogen atom transfer (HAT) mechanism of free radical scavenging that is preferred in gas-phase and non-polar solvents. The present work shows that the BDE may also be related to radical scavenging processes taking place in polar solvents, i.e., single electron transfer followed by proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET). This is so because the total energy requirements related to the SET-PT [sum of the ionization potential (IP) and proton dissociation enthalpy (PDE)] and the SPLET [sum of the proton affinity (PA) and electron transfer enthalpy (ETE)] are perfectly correlated with the BDE. This could explain why the published data for polyphenolic antioxidant activity measured by various assays are better correlated with the BDE than with other reaction enthalpies involved in radical scavenging mechanisms, i.e., the IP, PDE, PA and ETE. The BDE is fairly well able to rank flavonoids as antioxidants in any medium, but to conclude which radical scavenging mechanism represents the most probable reaction pathway from the thermodynamic point of view, the IP and PA (ETE) should also be considered. This is exemplified in the case of the radical scavenging activity of 25 flavonoids.

  11. Thermochemistry of 2,2'-dipyridil N-oxide and 2,2'-dipyridil N,N'-dioxide. The dissociation enthalpies of the N-O bonds

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Ana Filipa L.O.M.; Monteiro, Andre R.; Goncalves, Jorge M. [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); Acree, William E. [Department of Chemistry, University of North Texas, Denton, TX 76203-5070 (United States); Ribeiro da Silva, Maria D.M.C., E-mail: mdsilva@fc.up.pt [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)

    2011-07-15

    Research highlights: > The standard enthalpies of formation of two crystalline 2,2'-dipyridil N-oxides were measured by combustion calorimetry. > The standard enthalpies of sublimation of two 2,2'-dipyridil N-oxides were derived from Knudsen effusion experiments. > First, second and mean (N-O) bond dissociation enthalpies (BDEs) for 2,2'-dipyridil N,N'-dioxide were derived. > The (N-O) bond dissociation enthalpy (BDE) for 2,2'-dipyridil N-oxide was calculated. - Abstract: In this paper, the first, second and mean (N-O) bond dissociation enthalpies (BDEs) were derived from the standard (p{sup o} = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, {Delta}{sub f}H{sub m}{sup 0}(g), at T = 298.15 K, of 2,2'-dipyridil N-oxide and 2,2'-dipyridil N,N'-dioxide. These values were calculated from experimental thermodynamic parameters, namely from the standard (p{sup o} = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, {Delta}{sub f}H{sub m}{sup 0}(cr), at T = 298.15 K, obtained from the standard molar enthalpies of combustion, {Delta}{sub c}H{sub m}{sup 0}, measured by static bomb combustion calorimetry, and from the standard molar enthalpies of sublimation, at T = 298.15 K, determined from Knudsen mass-loss effusion method.

  12. Estimating the value of the metal-ligand bond dissociation enthalpy (M-L for adducts using empirical equations supported by TG data

    Directory of Open Access Journals (Sweden)

    Farias Robson Fernandes

    1999-01-01

    Full Text Available In this work is presented and tested (for 106 adducts, mainly of the zinc group halides two empirical equations supported in TG data to estimate the value of the metal-ligand bond dissociation enthalpy for adducts: (M-O = t i / g if t i < 420 K and (M-O = (t i / g - 7,75 . 10-2 . t i if t i > 420 K. In this empirical equations, t i is the thermodynamic temperature of the beginning of the thermal decomposition of the adduct, as determined by thermogravimetry, andg is a constant factor that is function of the metal halide considered and of the number of ligands, but is not dependant of the ligand itself. To half of the tested adducts the difference between experimental and calculated values was less than 5%. To about 80% of the tested adducts, the difference between the experimental (calorimetric and the calculated (using the proposed equations values are less than 15%.

  13. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  14. Comparative anti-inflammatory activities of curcumin and tetrahydrocurcumin based on the phenolic O-H bond dissociation enthalpy, ionization potential and quantum chemical descriptor.

    Science.gov (United States)

    Murakami, Yukio; Ishii, Hiroaki; Takada, Naoki; Tanaka, Shoji; Machino, Mamoru; Ito, Shigeru; Fujisawa, Seiichiro

    2008-01-01

    Curcumin and its reduced derivative tetrahydrocurcumin have been shown to exhibit chemopreventive activity. Cyclooxygenase-2 (COX-2) inhibition in lipopolysaccharide (LPS)- or Porphyromonas gingivalis fimbria-stimulated RAW 264.7 cells was investigated using Northern blot analysis. The fimbria-stimulated expression of the COX-2 gene was inhibited by curcumin but not by tetrahydrocurcumin. LPS-stimulated COX-2 gene expression was completely inhibited by curcumin, but an increase in the concentration of tetrahydrocurcumin did not cause complete inhibition of COX-2 expression. The inhibitory effect of curcumin on nuclear factor kappa B (NF-kappaB) activation in the cells was clearly observed, but that of tetrahydrocurcumin was incomplete even at a concentration of 20 microM. To explain the difference in effect between the two compounds, analysis of the frontier orbital was performed using ab initio 6-31G* wave function. The calculated chemical hardness (eta) for curcumin was clearly smaller, whereas its electronegativity (chi) and electrophilicity (omega) were clearly greater than the corresponding values for the curcumin-related compounds tetrahydrocurcumin, isoeugenol and eugenol. This suggested that the anti-inflammatory activities of curcumin may be related to eta-, chi- and/or omega-controlled enzymes. In addition, the bond dissociation enthalpy (BDE) of the phenolic OH was calculated using the density function theory (DFT)/B3LY. The total BDE values of curcumin and tetrahydrocurcumin were almost identical, but the BDE of one-electron oxidation and ionization potential (IP) for curcumin were lower than those for tetrahydrocurcumin, suggesting the highly pro-oxidative activity of curcumin. Curcumin has both oxidant and antioxidant properties. A causal link between the anti-inflammatory activities and molecular properties of phenolic antioxidants is suggested. PMID:18507010

  15. Theoretical investigation on the bond dissociation enthalpies of phenolic compounds extracted from Artocarpus altilis using ONIOM(ROB3LYP/6-311++G(2df,2p):PM6) method

    Science.gov (United States)

    Thong, Nguyen Minh; Duong, Tran; Pham, Linh Thuy; Nam, Pham Cam

    2014-10-01

    Theoretical calculations have been performed to predict the antioxidant property of phenolic compounds extracted from Artocarpus altilis. The Osbnd H bond dissociation enthalpy (BDE), ionization energy (IE), and proton dissociation enthalpy (PDE) of the phenolic compounds have been computed. The ONIOM(ROB3LYP/6-311++G(2df,2p):PM6) method is able to provide reliable evaluation for the BDE(Osbnd H) in phenolic compounds. An important property of antioxidants is determined via the BDE(Osbnd H) of those compounds extracted from A. altilis. Based on the BDE(Osbnd H), compound 12 is considered as a potential antioxidant with the estimated BDE value of 77.3 kcal/mol in the gas phase.

  16. A DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola;

    2003-01-01

    DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP)....

  17. 取代基效应对褐煤模型化合物离解焓影响的理论研究%Theoretical Study of Substituent Effects on Bond Dissociation Enthalpies in Lignite Model Compounds

    Institute of Scientific and Technical Information of China (English)

    王新华; 冯莉; 曹泽星; 刘祥春; 汤海燕; 张曼

    2013-01-01

    为了探究褐煤热解过程中氧桥键C-O均裂这一重要反应,选取a-O-4和-O-4类结构单元作为褐煤模型化合物,运用不同密度泛函计算了部分模型化合物中C-O的离解焓,并以CBS-QB3作为理论基准值进行比较,最后选取M05-2X进行离解焓计算.结果显示,对于选定的a-O-4和-O-4类模型化合物,其平均离解焓分别为51.0 kcal/mol和66.1kcal/mol.周围取代环境能显著影响C-O离解焓,芳环上存在给电子基团(OH,OCH3和CH3)能降低C-O离解焓,而吸电子基团COOH则能增加其离解焓.然后深层次分析了取代基效应对C-O离解焓的影响.此外,分子内氢键的形成对离解焓也有很大的影响.C-O的离解焓与其键长没有特定的相关性,不能简单的通过C-O键长来预测其离解焓.%Lignite is an abundant natural resource that is a potential source of clean fuel and value-added chemicals.The mechanisms by which thermal and catalytic treatments deconstruct lignite remain elusive,which is where quantum mechanical calculations can offer fundamental insights.In order to investigate the cleavage of C-O bridge bond,which is the critical step in the thermal decomposition of lignite,the α-O-4 and β-O-4 types of structural units are selected as lignite model compounds to calculate the C-O bond dissociation enthalpies using several kinds of density functional theory methods (B3PW91,B3P86,PBE1PBE,BMK,M06-2X and M05-2X) at 6-3 l+G(d,p) level.By the comparison between the results and the theoretical benchmark values provided by CBS-QB3 method,M05-2X functional was applied for the calculations on C-O bond dissociation enthalpies.The present results indicate that the C-O average bond dissociation enthalpies are 51.0 kcal/mol and 66.1 kcal/mol for the α-O-4 and β-O-4 types of model compounds,respectively.Local substituents have a great effect on the C-O bond dissociation enthalpies,the C-O bond dissociation enthalpies will decrease when the adjacent arene rings are

  18. Thermal dissociation behavior and dissociation enthalpies of methane-carbon dioxide mixed hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, T.H.; Kneafsey, T.J.; Rees, E.V.L.

    2011-02-15

    Replacement of methane with carbon dioxide in hydrate has been proposed as a strategy for geologic sequestration of carbon dioxide (CO{sub 2}) and/or production of methane (CH{sub 4}) from natural hydrate deposits. This replacement strategy requires a better understanding of the thermodynamic characteristics of binary mixtures of CH{sub 4} and CO{sub 2} hydrate (CH{sub 4}-CO{sub 2} mixed hydrates), as well as thermophysical property changes during gas exchange. This study explores the thermal dissociation behavior and dissociation enthalpies of CH{sub 4}-CO{sub 2} mixed hydrates. We prepared CH{sub 4}-CO{sub 2} mixed hydrate samples from two different, well-defined gas mixtures. During thermal dissociation of a CH{sub 4}-CO{sub 2} mixed hydrate sample, gas samples from the head space were periodically collected and analyzed using gas chromatography. The changes in CH{sub 4}-CO{sub 2} compositions in both the vapor phase and hydrate phase during dissociation were estimated based on the gas chromatography measurements. It was found that the CO{sub 2} concentration in the vapor phase became richer during dissociation because the initial hydrate composition contained relatively more CO{sub 2} than the vapor phase. The composition change in the vapor phase during hydrate dissociation affected the dissociation pressure and temperature; the richer CO{sub 2} in the vapor phase led to a lower dissociation pressure. Furthermore, the increase in CO{sub 2} concentration in the vapor phase enriched the hydrate in CO{sub 2}. The dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate was computed by fitting the Clausius-Clapeyron equation to the pressure-temperature (PT) trace of a dissociation test. It was observed that the dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate lays between the limiting values of pure CH{sub 4} hydrate and CO{sub 2} hydrate, increasing with the CO{sub 2} fraction in the hydrate phase.

  19. Choice of Bond Dissociation Enthalpies on which to Base the Stabilization Energies of Simple Radicals: DH(R-H)is Preferred because DH(R-Me) is Perturbed by Changes in Chain Branching

    Energy Technology Data Exchange (ETDEWEB)

    Poutsma, Marvin L [ORNL

    2008-01-01

    The relative stabilization energies of radicals, SE(R ), along the simple series methyl/ethyl/i-propyl/t-butyl are known to vary in spread and even direction dependent on which dissociation enthalpies, DH(R-X), they are based on. Using a highly electronegative X is recognized as unwise, but it is not clear whether a choice of X = Me or X = R might not be preferred over the almost universal use of R = H. The enthalpies of isomerization of C4 radical pairs that vary only in the substitution pattern at the radical center but not in carbon skeleton illustrate that R = H is indeed the better choice. Comparisons in the context of recent predictive models for alkane and radical stability indicate that, while relative DH(R-H) values highlight the desired difference in substitution pattern at the radical center, relative DH(R-Me) values are perturbed by differences in skeletal branching or protobranching which are well-known to affect thermochemistry. As a result, SE(R ) values derived from relative DH(R-Me) values are consistently too small. The same pattern is illustrated for prim, sec, and tert allylic and benzylic radicals (larger SE(R )) and for the parent vinyl, phenyl, and ethynyl radicals (negative SE(R )).

  20. Enthalpy Costs of Making and Breaking Bonds: A Game of Generating Molecules with Proper Lewis Structures

    Science.gov (United States)

    Bell, Peter T.; Adkins, Alyssa D.; Gamble, Rex J.; Schultz, Linda D.

    2009-01-01

    "Enthalpy Costs" is a simple card game created to assist students in developing proper Lewis structure drawing skills. Score keeping is accomplished by tracking the enthalpy changes associated with bond-making and bond-breaking processes during formation of molecules represented by proper Lewis structures. Playing the game requires the student to…

  1. Thermodynamics of Aβ16-21 dissociation from a fibril: Enthalpy, entropy, and volumetric properties.

    Science.gov (United States)

    Rao Jampani, Srinivasa; Mahmoudinobar, Farbod; Su, Zhaoqian; Dias, Cristiano L

    2015-11-01

    Here, we provide insights into the thermodynamic properties of A β16-21 dissociation from an amyloid fibril using all-atom molecular dynamics simulations in explicit water. An umbrella sampling protocol is used to compute potentials of mean force (PMF) as a function of the distance ξ between centers-of-mass of the A β16-21 peptide and the preformed fibril at nine temperatures. Changes in the enthalpy and the entropic energy are determined from the temperature dependence of these PMF(s) and the average volume of the simulation box is computed as a function of ξ. We find that the PMF at 310 K is dominated by enthalpy while the entropic energy does not change significantly during dissociation. The volume of the system decreases during dissociation. Moreover, the magnitude of this volume change also decreases with increasing temperature. By defining dock and lock states using the solvent accessible surface area (SASA), we find that the behavior of the electrostatic energy is different in these two states. It increases (unfavorable) and decreases (favorable) during dissociation in lock and dock states, respectively, while the energy due to Lennard-Jones interactions increases continuously in these states. Our simulations also highlight the importance of hydrophobic interactions in accounting for the stability of A β16-21.

  2. Enthalpy of cooperative hydrogen bonding in complexes of tertiary amines with aliphatic alcohols: Calorimetric study

    International Nuclear Information System (INIS)

    Research highlights: → Solution enthalpies of aliphatic alcohols in tertiary amines and vice versa were measured. → The enthalpies of specific interaction of amines in aliphatic alcohols are lower than the enthalpies of hydrogen bonding in 1:1 complexes amine-alcohol determined in base media. → Hydrogen bond cooperativity factors in multi-particle complexes of alcohols with aromatic amines are approximately equal for all alcohols. → Hydrogen bond cooperativity factors in multi-particle complexes of alcohols with trialkylamines decrease with increasing of alkyl radical length in alcohol and amine molecules. - Abstract: The work is devoted to the investigation of thermodynamics of specific interaction of the tertiary aliphatic and aromatic amines with associated solvents as which aliphatic alcohols were taken. Solution enthalpies of aliphatic alcohols in amines (tri-n-propylamine, 2-methylpyridine, 3-methylpyridine, N-methylimidazole) as well as amines in alcohols were measured at infinite dilution. The enthalpies of specific interaction (H-bonding) in systems studied were determined based on experimental data. The enthalpies of specific interaction of amines in aliphatic alcohols significantly lower than the enthalpies of hydrogen bonding in complexes amine-alcohol of 1:1 composition determined in base media due to the reorganization of aliphatic alcohols as solvents. The determination of solvent reorganization contribution makes possible to define the hydrogen bonding enthalpies of amines with clusters of alcohols. Obtained enthalpies of hydrogen bonding in multi-particle complexes are sensitive to the influence of cooperative effect. It was shown, that hydrogen bond cooperativity factors in multi-particle complexes of alcohols with amines are approximately equal for all alcohols when pyridines and N-methylimidazole as solutes are used. At the same time, H-bonding cooperativity factors in complexes of trialkylamines with associative species of alcohols

  3. Thermochemical study of 1-acetyl vinyl p-nitrobenzoate: vinyl bond enthalpy in captodative olefins.

    Science.gov (United States)

    Rojas, Aarón; Valdés-Ordoñez, Alejandro; Martínez-Herrera, Melchor; Torres, Luis Alfonso; Campos, Myriam; Hernández-Obregón, Javier; Herrera, Rafael; Tamariz, Joaquín

    2015-05-21

    Captodative olefins are highly reactive and selective substrates in Diels-Alder and 1,3-dipolar cycloadditions. Seeking an explanation of this fact based on molecular energetics, the thermochemical analysis of 1-acetyl vinyl p-nitrobenzoate, a captodative olefin, has been performed using semi-micro-combustion calorimetry, effusion measurements through a quartz crystal microbalance, and differential scanning calorimetry. The molar standard combustion energy and enthalpy as well as the molar standard formation enthalpy are reported along with sublimation and melting enthalpies. From these data, experimental formation enthalpy of the gas-phase is derived and compared with the theoretical value calculated through the density functional theory procedure. The olefinic bond enthalpy is also computed from experimental data, and the relevance of the results is discussed.

  4. Standard enthalpy of formation of L-glutamine and the products of its dissociation in aqueous solutions

    Science.gov (United States)

    Kochergina, L. A.; Lytkin, A. I.; Krutova, O. N.; Damrina, K. V.

    2014-03-01

    Heat effects of the dissolution of crystalline L-glutamine in water and lithium hydroxide solutions were determined by direct calorimetry at 298.15 K. Standard enthalpies of formation of L-glutamine and the products of its dissociation in aqueous solution were calculated.

  5. Standard enthalpies of formation of α-aminobutyric acid and products of its dissociation in an aqueous solution

    Science.gov (United States)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.

    2016-08-01

    Heats of solution of crystalline α-aminobutyric acid in water and in aqueous solutions of potassium hydroxide at 298.15 K are measured by means of direct calorimetry. Standard enthalpies of formation of the amino acid and products of its dissociation in an aqueous solution are calculated.

  6. Standard enthalpies of formation of γ-aminobutyric acid and the products of its dissociation in aqueous solution

    Science.gov (United States)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Skvortsov, I. A.; Korchagina, A. S.

    2016-09-01

    Heat effects of the dissolution of crystalline γ-aminobutyric acid in water and potassium hydroxide solutions are determined by direct colorimetry at 298.15 K. Standard enthalpies of formation of γ-aminobutyric acid and the products of its dissociation in aqueous solution are calculated.

  7. Standard enthalpies of formation for crystalline serine and isoserine and products of their dissociation in aqueous solutions

    Science.gov (United States)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Damrina, K. V.; Skvortsov, I. A.

    2016-02-01

    The heats of solution of crystalline serine and isoserine in water and potassium hydroxide solutions are measured via direct calorimetry at 298.15 K. The standard enthalpies of formations of amino acids and products of their dissociation in aqueous solution are calculated.

  8. Influence of charge and coordination number on bond dissociation energies, distances, and vibrational frequencies for the phosphorus-phosphorus bond.

    Science.gov (United States)

    Chitnis, Saurabh S; Whalen, J Marc; Burford, Neil

    2014-09-01

    We report a comprehensive and systematic experimental and computational assessment of the P-P bond in prototypical molecules that represent a rare series of known compounds. The data presented complement the existing solid-state structural data and previous computational studies to provide a thorough thermodynamic and electronic understanding of the P-P bond. Comparison of homolytic and heterolytic bond dissociation for tricoordinate-tricoordinate, tricoordinate-tetracoordinate, and tetracoordinate-tetracoordinate P-P bonds in frameworks 1-6 provides fundamental insights into covalent bonding. For all types of P-P bond discussed, homolytic dissociation is favored over heterolytic dissociation, although the distinction is small for 2(1+) and 6(1+). The presence of a single cationic charge in a molecule substantially strengthens the P-P bond (relative to analogous neutral frameworks) such that it is comparable with the C-C bond in alkanes. Nevertheless, P-P distances are remarkably independent of molecular charge or coordination number, and trends in values of d(PC) and νsymm(PC) imply that a molecular cationic charge is distributed over the alkyl substituents. In the gas phase, the diphosphonium dication 3(2+) has similar energy to two [PMe3](+) radical cations, so that it is the lattice enthalpy of 3[OTf]2 in the solid-state that enables isolation, highlighting that values from gas-phase calculations are poor guides for synthetic planning for ionic compounds. There are no relationships or correlations between bond lengths, strengths, and vibrational frequencies.

  9. Dissociation Energies of Sulfur-Centered Hydrogen-Bonded Complexes.

    Science.gov (United States)

    Ghosh, Sanat; Bhattacharyya, Surjendu; Wategaonkar, Sanjay

    2015-11-01

    In this work we have determined dissociation energies of O-H···S hydrogen bond in the H2S complexes of various phenol derivatives using 2-color-2-photon photofragmentation spectroscopy in combination with zero kinetic energy photoelectron (ZEKE-PE) spectroscopy. This is the first report of direct determination of dissociation energy of O-H···S hydrogen bond. The ZEKE-PE spectra of the complexes revealed a long progression in the intermolecular stretching mode with significant anharmonicity. Using the anharmonicity information and experimentally determined dissociation energy, we also validated Birge-Sponer (B-S) extrapolation method, which is an approximate method to estimate dissociation energy. Experimentally determined dissociation energies were compared with a variety of ab initio calculations. One of the important findings is that ωB97X-D functional, which is a dispersion corrected DFT functional, was able to predict the dissociation energies in both the cationic as well as the ground electronic state very well for almost every case.

  10. Accurate bond dissociation energies (D 0) for FHF- isotopologues

    Science.gov (United States)

    Stein, Christopher; Oswald, Rainer; Sebald, Peter; Botschwina, Peter; Stoll, Hermann; Peterson, Kirk A.

    2013-09-01

    Accurate bond dissociation energies (D 0) are determined for three isotopologues of the bifluoride ion (FHF-). While the zero-point vibrational contributions are taken from our previous work (P. Sebald, A. Bargholz, R. Oswald, C. Stein, P. Botschwina, J. Phys. Chem. A, DOI: 10.1021/jp3123677), the equilibrium dissociation energy (D e ) of the reaction ? was obtained by a composite method including frozen-core (fc) CCSD(T) calculations with basis sets up to cardinal number n = 7 followed by extrapolation to the complete basis set limit. Smaller terms beyond fc-CCSD(T) cancel each other almost completely. The D 0 values of FHF-, FDF-, and FTF- are predicted to be 15,176, 15,191, and 15,198 cm-1, respectively, with an uncertainty of ca. 15 cm-1.

  11. The reaction enthalpy of hydrogen dissociation calculated with the Small System Method from simulation of molecular fluctuations.

    Science.gov (United States)

    Skorpa, Ragnhild; Simon, Jean-Marc; Bedeaux, Dick; Kjelstrup, Signe

    2014-09-28

    We show how we can find the enthalpy of a chemical reaction under non-ideal conditions using the Small System Method to sample molecular dynamics simulation data for fluctuating variables. This method, created with Hill's thermodynamic analysis, is used to find properties in the thermodynamic limit, such as thermodynamic correction factors, partial enthalpies, volumes, heat capacities and compressibility. The values in the thermodynamic limit at (T,V, μj) are then easily transformed into other ensembles, (T,V,Nj) and (T,P,Nj), where the last ensemble gives the partial molar properties which are of interest to chemists. The dissociation of hydrogen from molecules to atoms was used as a convenient model system. Molecular dynamics simulations were performed with three densities; ρ = 0.0052 g cm(-3) (gas), ρ = 0.0191 g cm(-3) (compressed gas) and ρ = 0.0695 g cm(-3) (liquid), and temperatures in the range; T = 3640-20,800 K. The enthalpy of reaction was observed to follow a quadratic trend as a function of temperature for all densities. The enthalpy of reaction was observed to only have a small pressure dependence. With a reference point close to an ideal state (T = 3640 K and ρ = 0.0052 g cm(-3)), we were able to calculate the thermodynamic equilibrium constant, and thus the deviation from ideal conditions for the lowest density. We found the thermodynamic equilibrium constant to increase with increasing temperature, and to have a negligible pressure dependence. Taking the enthalpy variation into account in the calculation of the thermodynamic equilibrium constant, we found the ratio of activity coefficients to be in the order of 0.7-1.0 for the lowest density, indicating repulsive forces between H and H2. This study shows that the compressed gas- and liquid density values at higher temperatures are far from those calculated under ideal conditions. It is important to have a method that can give access to partial molar properties, independent of the ideality of

  12. Calorimetric and computational study of thiacyclohexane 1-oxide and thiacyclohexane 1,1-dioxide (thiane sulfoxide and thiane sulfone). Enthalpies of formation and the energy of the S=O bond.

    Science.gov (United States)

    Roux, María Victoria; Temprado, Manuel; Jiménez, Pilar; Dávalos, Juan Zenón; Notario, Rafael; Guzmán-Mejía, Ramón; Juaristi, Eusebio

    2003-03-01

    A rotating-bomb combustion calorimeter specifically designed for the study of sulfur-containing compounds [J. Chem. Thermodyn. 1999, 31, 635] has been used for the determination of the enthalpy of formation of thiane sulfone, 4, Delta(f)H(o) m(g) = -394.8 +/- 1.5 kJ x mol(-1). This value stands in stark contrast with the enthalpy of formation reported for thiane itself, Delta(f)H(o) m(g) = -63.5 +/- 1.0 kJ x mol(-1), and gives evidence of the increased electronegativity of the sulfur atom in the sulfonyl group, which leads to significantly stronger C-SO2 bonds. Given the known enthalpy of formation of atomic oxygen in the gas phase, Delta(f)H(o) m(O,g) = +249.18 kJ x mol(-1), and the reported bond dissociation energy for the S=O bond in alkyl sulfones, BDE(S=O) = +470.0 kJ x mol(-1), it was possible to estimate the enthalpy of formation of thiane sulfoxide, 5, a hygroscopic compound not easy to use in experimental calorimetric measurements, Delta(f)H(o) m(5) = -174.0 kJ x mol(-1). The experimental enthalpy of formation of both 4 and 5 were closely reproduced by theoretical calculations at the G2(MP2)+ level, Delta(f)H(o) m(4) = -395.0 kJ x mol(-1) and Delta(f)H(o) m(5) = -178.0 kJ x mol(-1). Finally, calculated G2(MP2)+ values for the bond dissociation energy of the S=O bond in cyclic sulfoxide 5 and sulfone 4 are +363.7 and +466.2 kJ x mol(-1), respectively.

  13. Accurate measurement of phase equilibria and dissociation enthalpies of HFC-134a hydrates in the presence of NaCl for potential application in desalination

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Dongyoung; Lee, Yohan; Choi, Wonjung; Seo, Yongwon [Ulsan National Institute of Science and Technology, Ulsan (Korea, Republic of); Lee, Seungmin [Korea Institute of Industrial Technology, Busan (Korea, Republic of)

    2016-04-15

    Phase equilibria, structure identification, and dissociation enthalpies of HFC-134a hydrates in the presence of NaCl are investigated for potential application in desalination. To verify the influence of NaCl on the thermodynamic hydrate stability of the HFC-134a hydrate, the three-phase (hydrate (H) - liquid water (L{sub W}) - vapor (V)) equilibria of the HFC-134a+NaCl (0, 3.5, and 8.0 wt%)+water systems are measured by both a conventional isochoric (pVT) method and a stepwise differential scanning calorimeter (DSC) method. Both pVT and DSC methods demonstrate reliable and consistent hydrate phase equilibrium points of the HFC-134a hydrates in the presence of NaCl. The HFC- 134a hydrate is identified as sII via powder X-ray diffraction. The dissociation enthalpies (ΔH{sub d}) of the HFC-134a hydrates in the presence of NaCl are also measured with a high pressure micro-differential scanning calorimeter. The salinity results in significant thermodynamic inhibition of the HFC-134a hydrates, whereas it has little effect on the dissociation enthalpy of the HFC-134a hydrates. The experimental results obtained in this study can be utilized as foundational data for the hydrate-based desalination process.

  14. Selectivity of peptide bond dissociation on excitation of a core electron: Effects of a phenyl group

    Science.gov (United States)

    Tsai, Cheng-Cheng; Chen, Jien-Lian; Hu, Wei-Ping; Lin, Yi-Shiue; Lin, Huei-Ru; Lee, Tsai-Yun; Lee, Yuan T.; Ni, Chi-Kung; Liu, Chen-Lin

    2016-09-01

    The selective dissociation of a peptide bond upon excitation of a core electron in acetanilide and N-benzylacetamide was investigated. The total-ion-yield near-edge X-ray absorption fine structure spectra were recorded and compared with the predictions from time-dependent density functional theory. The branching ratios for the dissociation of a peptide bond are observed as 16-34% which is quite significant. This study explores the core-excitation, the X-ray photodissociation pathways, and the theoretical explanation of the NEXAFS spectra of organic molecules containing both a peptide bond and a phenyl group.

  15. Enthalpy-entropy compensation in biomolecular halogen bonds measured in DNA junctions.

    Science.gov (United States)

    Carter, Megan; Voth, Andrea Regier; Scholfield, Matthew R; Rummel, Brittany; Sowers, Lawrence C; Ho, P Shing

    2013-07-23

    Interest in noncovalent interactions involving halogens, particularly halogen bonds (X-bonds), has grown dramatically in the past decade, propelled by the use of X-bonding in molecular engineering and drug design. However, it is clear that a complete analysis of the structure-energy relationship must be established in biological systems to fully exploit X-bonds for biomolecular engineering. We present here the first comprehensive experimental study to correlate geometries with their stabilizing potentials for fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) X-bonds in a biological context. For these studies, we determine the single-crystal structures of DNA Holliday junctions containing halogenated uracil bases that compete X-bonds against classic hydrogen bonds (H-bonds), estimate the enthalpic energies of the competing interactions in the crystal system through crystallographic titrations, and compare the enthalpic and entropic energies of bromine and iodine X-bonds in solution by differential scanning calorimetry. The culmination of these studies demonstrates that enthalpic stabilization of X-bonds increases with increasing polarizability from F to Cl to Br to I, which is consistent with the σ-hole theory of X-bonding. Furthermore, an increase in the X-bonding potential is seen to direct the interaction toward a more ideal geometry. However, the entropic contributions to the total free energies must also be considered to determine how each halogen potentially contributes to the overall stability of the interaction. We find that bromine has the optimal balance between enthalpic and entropic energy components, resulting in the lowest free energy for X-bonding in this DNA system. The X-bond formed by iodine is more enthalpically stable, but this comes with an entropic cost, which we attribute to crowding effects. Thus, the overall free energy of an X-bonding interaction balances the stabilizing electrostatic effects of the σ-hole against the competing

  16. Generation of pyridyl coordinated organosilicon cation pool by oxidative Si-Si bond dissociation

    Directory of Open Access Journals (Sweden)

    Itami Kenichiro

    2007-02-01

    Full Text Available Abstract An organosilicon cation stabilized by intramolecular pyridyl coordination was effectively generated and accumulated by oxidative Si-Si bond dissociation of the corresponding disilane using low temperature electrolysis, and was characterized by NMR and CSI-MS.

  17. Mechanical switching and coupling between two dissociation pathways in a P-selectin adhesion bond

    Science.gov (United States)

    Evans, Evan; Leung, Andrew; Heinrich, Volkmar; Zhu, Cheng

    2004-08-01

    Many biomolecular bonds exhibit a mechanical strength that increases in proportion to the logarithm of the rate of force application. Consistent with exponential decrease in bond lifetime under rising force, this kinetically limited failure reflects dissociation along a single thermodynamic pathway impeded by a sharp free energy barrier. Using a sensitive force probe to test the leukocyte adhesion bond P-selectin glycoprotein ligand 1 (PSGL-1)-P-selectin, we observed a linear increase of bond strength with each 10-fold increase in the rate of force application from 300 to 30,000 pN/sec, implying a single pathway for failure. However, the strength and lifetime of PSGL-1-P-selectin bonds dropped anomalously when loaded below 300 pN/sec, demonstrating unexpectedly faster dissociation and a possible second pathway for failure. Remarkably, if first loaded by a "jump" in force to 20-30 pN, the bonds became strong when subjected to a force ramp as slow as 30 pN/sec and exhibited the same single-pathway kinetics under all force rates. Applied in this way, a new "jump/ramp" mode of force spectroscopy was used to show that the PSGL-1-P-selectin bond behaves as a mechanochemical switch where force history selects between two dissociation pathways with markedly different properties. Furthermore, replacing PSGL-1 by variants of its 19-aa N terminus and by the crucial tetrasaccharide sialyl LewisX produces dramatic changes in the failure kinetics, suggesting a structural basis for the two pathways. The two-pathway switch seems to provide a mechanism for the "catch bond" response observed recently with PSGL-1-P-selectin bonds subjected to small-constant forces.

  18. Substituent Effect on the C-NO2 and N-NO2 Bond Dissociation Energies of Nitroaromatic Molecules

    Institute of Scientific and Technical Information of China (English)

    FANG,Ming; LI,Zhe; FU,Yao

    2008-01-01

    Six density function theory methods (B3LYP,B3P86,MPWB1K1,MPWPW91,PBEPBE,TPSS1KCIS3) were used to calculate bond dissociation enthalpies of nitro compounds,where the B3P86 method was found to give the most accurate predictions.Using the B3P86 method meta-and para-substituted nitroaromatics were systematically studied for the first time.The remote substituent effects,Hammett relationships,and the origin of the substituent effects were discussed on the basis of the calculated results.Both meta-and para-substituted nitromethyl-benzenes showed significant substituent effects and a fair correlation against substituent constants (σ+p).The ground state effects were found to play the major role in determining the overall substituent effects.Meanwhile,nitroaminobenzenes showed irregular substituent effects and a poorer Hammett correlation,where both ground and radical state effects contributed to the overall substituent effects.

  19. Computation of Bond Dissociation Energies for Removal of Nitrogen Dioxide Groups in Certain Aliphatic Nitro Compounds

    Institute of Scientific and Technical Information of China (English)

    SHAO Ju-Xiang; CHENG Xin-Lu; YANG Xiang-Dong; XIANG Shi-Kai

    2006-01-01

    @@ Bond dissociation energies for removal of nitrogen dioxide groups in 10 aliphatic nitro compounds, including nitromethane, nitroethylene, nitroethane, dinitromethane, 1-nitropropane, 2-nitropropane, 1-nitrobutane,2-methyl-2-nitropropane, nitropentane, and nitrohexane, are calculated using the highly accurate complete basis set (CBS-Q) and the three hybrid density functional theory (DFT) methods B3LYP, B3PW91 and B3P86 with 6-31G** basis set.

  20. Computational study of the enthalpies of formation, DeltafH degrees, and mean bond enthalpies, mBEs, of H4-nEXn0/- and H3-nEXn+/0 (E=C, B; X=F-I).

    Science.gov (United States)

    Raabe, Ines; Himmel, Daniel; Krossing, Ingo

    2007-12-20

    To compensate for lacking experimental standard enthalpies of formation DeltafH degrees of haloboranes/-boranates as well as the isoelectronic halocarbenium ions and halomethanes, high-level quantum chemical calculations up to the ccsd(t)/(SDB-)aug-cc-pVQZ level have been performed to establish these values. Very reliable experimental data (e.g., DeltafH degrees of HCl, F, and CH4) or at the G3 level established values (e.g., DeltafH degrees of CF3+=410 kJ mol(-1)) were used as anchor points to obtain accurate absolute DeltafH degrees and mean bond enthalpy (mBE) values. To further minimize systematic errors of the protocol, all derived quantities were assessed in isodesmic reactions at the G3 and ccsd(t) level using the (SDB-)aug-cc-PVTZ basis set. The obtained DeltafH degrees values are in very good agreement to (scarcely available) accurate experimental and computational data. Almost all B-containing compounds have been assessed for the first time. We derived "best" DeltafH degrees values and used them to determine the mean E-X bond enthalpies in H4-nEXn-/0 and H3-nEXn0/+ (with n=1-3, E=B, C, and X=F-I). In each of the series, the DeltafH degrees values increase from fluorine to iodine, and except for the iodine-containing carbenium ions and the bromo- and iodomethanes, the DeltafH degrees values become lower with the more halogen atoms that are present in the particle. The boron containing species always have a lower DeltafH degrees than the isoelectronic carbenium ions and methanes, and the H4-nEXn-/0 are lower in energy than the parent H3-nEXn+/0. This reflects the greater average B-X bond strengths.

  1. Theoretical study of GeH sub n , AsH sub n , and SeH sub n : Bond dissociation energies

    Energy Technology Data Exchange (ETDEWEB)

    Binning, R.C. Jr. (Department of Chemistry and Physics, Carlow College, Pittsburgh, Pennsylvania 15213 (USA)); Curtiss, L.A. (Chemical Technology Division/Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439-4837 (USA))

    1990-02-01

    {ital Ab} {ital initio} molecular orbital theory (Moller--Plesset perturbation theory to fourth order and new basis sets developed for Ge, As, and Se) is used to calculate the atomization energies of GeH{sub {ital n}}({ital n}=1--4), AsH{sub {ital n}}({ital n}=1--3), and SeH{sub {ital n}}({ital n}=1--2). Good agreement is found with the experimental bond dissociation energies of these hydrides derived from recent photoionization studies. The theoretical energies are combined with experimental data on the isolated atoms to determine ideal enthalpies of formation at 0 K for these hydrides, which are expected to have an accuracy of about {plus minus}3 kcal/mol ({plus minus}0.15 eV).

  2. Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

    Science.gov (United States)

    Rožman, Marko

    2016-01-01

    Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

  3. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    Energy Technology Data Exchange (ETDEWEB)

    Domin, D.; Braida, Benoit; Lester Jr., William A.

    2008-05-30

    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  4. Density Functional Calculations of C-NO2 Bond Dissociation Energies for Nitroalkanes Molecules

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Bond dissociation energies for the removal of nitrogen dioxide group in some nitroalkane energetic materials have been calculated by using the three hybrid density functional theory (DFT) methods B3LYP, B3PW91 and B3P86 with 6-31g** and 6-311g** basis sets. The computed BDEs have been compared with the available experimental results. It is found that the B3P86 method with 6-31g** and 6-311g** basis sets can obtain satisfactory bond dissociation energies (BDEs), which are in extraordinary agreement with the experimental data. Considering the smaller mean absolute deviation and maximum difference, the reliable B3P86/6-311g** method was recommended to compute the BDEs for the removal of nitrogen dioxide group in the nitroalkane energetic materials. Using the method, the BDEs of 8 other nitroalkane energetic materials have been calculated and the maximum difference from experimental value is 1.76 kcal·mol-1 (for the BDE of tC4H9-NO2), which further proves the reliability of B3P86/6-311g** method. In addition, it is noted that the BDEs of C-NO2 bond change slightly for main chain nitroalkane compounds with the maximum difference of only 3.43 kcal mol-1.

  5. Hydrogen Dissociation in Generalized Hartree-Fock Theory: Breaking the diatomic bond

    Science.gov (United States)

    Jerke, Jonathan; Masood, Samina; Tymczak, Cj

    Generalized Hartree Fock theory predicts molecular Hydrogen dissociation without correlation. A variational Gaussian-Sinc linear superposition is the basis of 50 calculations with 3-4 significant digits of quality. The spin singlet covalent bond spontaneously breaks into a pair of uncorrelated doublets at atomic separation of 1.22 Angstroms. Quantum spin numbers and energetic comparison with Configuration Interaction theory--correlation--point to a first order phase transition in the molecular Hydrogen bond without correlation. Welch Foundation (Grant J-1675), the ARO (Grant W911Nf-13-1-0162), the Texas Southern University High Performance Computing Center (http:/hpcc.tsu.edu/; Grant PHY-1126251) and NSF-CREST CRCN project (Grant HRD-1137732).

  6. Molecular dissociation in the presence of catalysts: interpreting bond breaking as a quantum dynamical phase transition

    International Nuclear Information System (INIS)

    In this work we show that molecular chemical bond formation and dissociation in the presence of the d-band of a metal catalyst can be described as a quantum dynamical phase transition (QDPT). This agrees with DFT calculations that predict sudden jumps in some observables as the molecule breaks. According to our model this phenomenon emerges because the catalyst provides for a non-Hermitian Hamiltonian. We show that when the molecule approaches the surface, as occurs in the Heyrovsky reaction of H2, the bonding H2 orbital has a smooth crossover into a bonding molecular orbital built with the closest H orbital and the surface metal d-states. The same occurs for the antibonding state. Meanwhile, two resonances appear within the continuous spectrum of the d-band, which are associated with bonding and antibonding orbitals between the furthest H atom and the d-states at the second metallic layer. These move toward the band center, where they collapse into a pure metallic resonance and an almost isolated H orbital. This phenomenon constitutes a striking example of the non-trivial physics enabled when one deals with non-Hermitian Hamiltonian beyond the usual wide band approximation. (paper)

  7. Molecular dissociation in presence of catalysts: Interpreting bond breaking as a quantum dynamical phase transition

    CERN Document Server

    Ruderman, A; Santos, E; Pastawski, H M

    2015-01-01

    In this work we show that the molecular chemical bond formation and dissociation in presence of the d-band of a metal catalyst can be described as a Quantum Dynamical Phase Transition (QDPT). This agree with DFT calculations that predict sudden jumps in some observables as the molecule breaks. According to our model this phenomenon emerges because the catalyst provides for a non- Hermitian Hamiltonian. We show that when the molecule approaches the surface, as occurs in the Heyrovsky reaction of H 2, the bonding H 2 orbital has a smooth crossover into a bonding molecular orbital built with the closest H orbital and the surface metal d-states. The same occurs for the antibonding state. Meanwhile, two resonances appear within the continuous spectrum of the d- band which are associated with bonding and antibonding orbitals between the furthest H atom and the d-states at the second metallic layer. These move towards the band center where they collapse into a pure metallic resonance and an almost isolated H orbital...

  8. C-H and N-H bond dissociation energies of small aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Barckholtz, C.; Barckholtz, T.A.; Hadad, C.M.

    1999-01-27

    A survey of computational methods was undertaken to calculate the homolytic bond dissociation energies (BDEs) of the C-H and N-H bonds in monocyclic aromatic molecules that are representative of the functionalities present in coal. These include six-membered rings (benzene, pyridine, pyridazine, pyrimidine, pyrazine) and five-membered rings (furan, thiophene, pyrrole, oxazole). By comparison of the calculated C-H BDEs with the available experimental values for these aromatic molecules, the B3LYP/6-31G(d) level of theory was selected to calculate the BDEs of polycyclic aromatic hydrocarbons (PAHs), including carbonaceous PAHs (naphthalene, anthracene, pyrene, coronene) and heteroatomic PAHs (benzofuran, benzothiophene, indole, benzoxazole, quinoline, isoquinoline, dibenzofuran, carbazole). The cleavage of a C-H or a N-H bond generates a {sigma} radical that is, in general, localized at the site from which the hydrogen atom was removed. However, delocalization of the unpaired electron results in {approximately} 7 kcal {center{underscore}dot} mol{sup {minus}1} stabilization of the radical with respect to the formation of phenyl when the C-H bond is adjacent to a nitrogen atom in the azabenzenes. Radicals from five-membered rings are {approximately} 6 kcal {center{underscore}dot} mol{sup {minus}1} less stable than those formed from six-membered rings due to both localization of the spin density and geometric factors. The location of the heteroatoms in the aromatic ring affects the C-H bond strengths more significantly than does the size of the aromatic network. Therefore, in general, the monocyclic aromatic molecules can be used to predict the C-H BDE of the large PAHs within 1 kcal {center{underscore}dot} mol{sup {minus}1}.

  9. Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids

    Institute of Scientific and Technical Information of China (English)

    Zeng Hui; Zhao Jun; Xiao Xun

    2013-01-01

    Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies (BDEs) for 15 acids.These compounds are studied by utilizing the hybrid density functional theory (DFT) (B3LYP,B3PW91,B3P86,PBE1PBE) and the complete basis set (CBS-Q) method in conjunction with the 6-31 lG** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.

  10. Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids

    International Nuclear Information System (INIS)

    Quantum chemical calculations are performed to investigate the equilibrium C—COOH bond distances and the bond dissociation energies (BDEs) for 15 acids. These compounds are studied by utilizing the hybrid density functional theory (DFT) (B3LYP, B3PW91, B3P86, PBE1PBE) and the complete basis set (CBS—Q) method in conjunction with the 6-311G** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work. Comparisons between the computational results and the experimental values reveal that CBS—Q method, which can produce reasonable BDEs for some systems in our previous work, seems unable to predict accurate BDEs here. However, the B3P86 calculated results accord very well with the experimental values, within an average absolute error of 2.3 kcal/mol. Thus, B3P86 method is suitable for computing the reliable BDEs of C—COOH bond for carboxylic acid compounds. In addition, the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of studied compounds are estimated, based on which the relative thermal stabilities of the studied acids are also discussed. (atomic and molecular physics)

  11. Heterolytic and Homolytic N-NO Bond Dissociation Energies of N-Nitroso-benzenesulfonylmethylamines in Acetonitrile

    Institute of Scientific and Technical Information of China (English)

    HAO Wei-Fang; Tang Hui; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Great interests have been accumulated in recent years in the chemistry and biochemistry of nitric oxide (NO) since the remarkable discoveries of its key roles in a wide range of human physiological processes. To elucidate the mechanistic details of NO migration from its donor to its acceptor, it is necessary to determine the Y-NO bind energy that registers the thermodynamic driving force for NO release and capture. In this paper the heterolytic and homolytic N-NO bond dissociation energies [ i. e., △Hhet(N-NO) and △Hhomo(N-NO)] for ten N-nitroso-p-substituted-benzensulfonyl methylamines in acetonitrile are offered, which were obtained from titration calorimetry and thermodynamic cycles, respectively (Scheme 1).

  12. Quantum dynamics of polyatomic dissociative chemisorption on transition metal surfaces: mode specificity and bond selectivity.

    Science.gov (United States)

    Jiang, Bin; Yang, Minghui; Xie, Daiqian; Guo, Hua

    2016-06-27

    Dissociative chemisorption is the initial and often rate-limiting step in many heterogeneous processes. As a result, an in-depth understanding of the reaction dynamics of such processes is of great importance for the establishment of a predictive model of heterogeneous catalysis. Overwhelming experimental evidence has suggested that these processes have a non-statistical nature and excitations in various reactant modes have a significant impact on reactivity. A comprehensive characterization of the reaction dynamics requires a quantum mechanical treatment on a global potential energy surface. In this review, we summarize recent progress in constructing high-dimensional potential energy surfaces for polyatomic molecules interacting with transition metal surfaces based on the plane-wave density functional theory and in quantum dynamical studies of dissociative chemisorption on these potential energy surfaces. A special focus is placed on the mode specificity and bond selectivity in these gas-surface collisional processes, and their rationalization in terms of the recently proposed Sudden Vector Projection model. PMID:26100606

  13. The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

    International Nuclear Information System (INIS)

    A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H2O, HOD, and D2O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociative sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D2O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate

  14. The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Farjamnia, Azar; Jackson, Bret, E-mail: jackson@chem.umass.edu [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States)

    2015-06-21

    A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H{sub 2}O, HOD, and D{sub 2}O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociative sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D{sub 2}O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate.

  15. Trends in bond dissociation energies of alcohols and aldehydes computed with multireference averaged coupled-pair functional theory.

    Science.gov (United States)

    Oyeyemi, Victor B; Keith, John A; Carter, Emily A

    2014-05-01

    As part of our ongoing investigation of the combustion chemistry of oxygenated molecules using multireference correlated wave function methods, we report bond dissociation energies (BDEs) in C1-C4 alcohols (from methanol to the four isomers of butanol) and C1-C4 aldehydes (from methanal to butanal). The BDEs are calculated with a multireference averaged coupled-pair functional-based scheme. We compare these multireference BDEs with those derived from experiment and single-reference methods. Trends in BDEs for the alcohols and aldehydes are rationalized by considering geometry relaxations of dissociated radical fragments, resonance stabilization, and hyperconjugation. Lastly, we discuss the conjectured association between bond strengths and rates of hydrogen abstraction by hydroxyl radicals. In general, abstraction reaction rates are higher at sites where the C-H bond energies are lower (and vice versa). However, comparison with available rate data shows this inverse relationship between bond strengths and abstraction rates does not hold at all temperatures.

  16. The solvent and substituent effects on bond dissociation energies of NO-donor molecules containing the N-NO bond

    Indian Academy of Sciences (India)

    Li Xiao-Hong; Li Wei-Bin; Zhang Xian-Zhou

    2010-07-01

    Quantum chemical calculations are used to estimate the equilibrium N-NO bond dissociation energies (BDEs) for 15 NO-donor molecules in acetonitrile. These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86) methods together with 6-31G∗∗ basis set. The basis set superposition error (BSSE) and zero-point vibrational energy (ZPVE) are considered. The results are compared with the available experimental results. It is demonstrated that B3LYP/6-31G** is accurate to compute the reliable BDEs for the NO-donor molecules. The solvent effects on the N-NO BDEs are analysed and the result shows that the N-NO BDEs in a vacuum computed by B3P86/6-31G∗∗ method are the closest to the computed values in acetontrile and the average solvent effect is 0.78 kcal/mol. Subsequently, the substituent effects on the N-NO BDEs are further analysed and it is found that electron donating group stabilizes the radical and as a result BDE decreases; whereas electron withdrawing group stabilizes the ground state of the molecule and thus increases the BDE.

  17. Theoretical Study of the N-NO2 Bond Dissociation Energies for Energetic Materials with Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    LI Xiao-Hong; TANG Zheng-Xin; Abraham F.Jalbout; ZHANG Xian-Zhou; CHENG Xin-Lu

    2008-01-01

    The N-NO2 bond dissociation energies (BDEs) for 7 energetic materials were computed by means of accurate density functional theory (B3LYP, B3PW91 and B3P86) with 6-31G** and 6-311G** basis sets. By comparing the computed energies and experimental results, we find that the B3P86/6-311G** method can give good results of BDE, which has the mean absolute deviation of 1.30 kcal/mol. In addition, substituent effects were also taken into account. It is noted that the Hammett constants of substituent groups are related to the BDEs of the N-NO2 bond and the bond dissociation energies of the energetic materials studied decrease when increasing the number of NO2 group.

  18. Bond dissociation mechanism of ethanol during carbon nanotube synthesis via alcohol catalytic CVD technique: Ab initio molecular dynamics simulation

    Science.gov (United States)

    Oguri, Tomoya; Shimamura, Kohei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

    2014-03-01

    Dissociation of ethanol on a nickel cluster is investigated by ab initio molecular dynamics simulation to reveal the bond dissociation mechanism of carbon source molecules during carbon nanotube synthesis. C-C bonds in only CHxCO fragments are dissociated on the nickel cluster, whereas there is no preferential structure among the fragments for C-O bond dissociation. The dissociation preference is uncorrelated with the bond dissociation energy of corresponding bonds in freestanding molecules but is correlated with the energy difference between fragment molecules before and after dissociation on the nickel surface. Moreover, carbon-chain formation occurs after C-C bond dissociation in a continuous simulation. What determines the chirality of CNTs? What happens at the dissociation stage of carbon source molecules? Regarding the former question, many researchers have pointed out the good epitaxial relationship between a graphite network and a close-packed facet (i.e., fcc(1 1 1) or hcp(0 0 0 1)) of transition metals [17-19]. Therefore, the correlation between the chirality of CNTs and the angle of the step edge on metal (or metal carbide) surfaces has been closely investigated [20-22]. In association with this geometric matching, the epitaxial growth of graphene on Cu(1 1 1) and Ni(1 1 1) surfaces has recently been achieved via CCVD technique [23-25], which is a promising technique for the synthesis of large-area and monolayer graphene.Regarding the latter question, it is empirically known that the yield and quality of CNT products strongly depend on the choice of carbon source molecules and additives. For example, it is well known that the use of ethanol as carbon source molecules yields a large amount of SWNTs without amorphous carbons (called the alcohol CCVD (ACCVD) technique) compared with the CCVD process using hydrocarbons [4]. Moreover, the addition of a small amount of water dramatically enhances the activity and lifetime of the catalytic metal (called the

  19. Hydrogen Bonding in Thermoplastic Polyurethane Elastomers: IR Thermal Analysis

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The hydrogen bond percentage and its temperature dependence of the three TPU samples synthesized from polytetrahydrofuran, 4,4-diphenylmethane diisocyanate, N-methyl diethanol amine or 1,4-butane diol were studied by means of IR thermal analysis. The enthalpy and the entropy of the hydrogen bond dissociation were determined by the Vant Hoff plot.

  20. Ⅱ型二元氢气水合物相边界条件测定及分解焓计算%Measurement of Phase Boundary Conditions and Calculation of Dissociation Enthalpy of sⅡ Binary Hydrogen Hydrate

    Institute of Scientific and Technical Information of China (English)

    杜建伟; 李栋梁; 陈玉凤; 梁德青; 李新军

    2011-01-01

    Experiments on Sii binary hydrogen hydrate phase boundary conditions of the cyclo-pentane/tetrahydrofuran/tert-butylamine/acetone-hydrogen-water system were conducted in a high pressure visual sapphire reactor to obtain the phase equilibrium data for hydrogen hydrate. On the basis of the experimental data, the dissociation enthalpy of Sii binary hydrogen hydrate was calculated with the Clausius-Clapeyron equation. The results show that the phase equilibrium pressure of Sii binary hydrogen hydrate is one-tenth or even more lower that of hydrogen hydrate without additives. The dissociation enthalpy of Sii binary hydrogen hydrate is related to the additives and the phase equilibrium temperature, and with the same kind of additives the dissociation enthalpy of the binary hydrogen hydrate increases with the phase equilibrium temperature. The results of this study may lead to the development of hydrogen storage by hydrate technique.%针对水合物法储氢存在相平衡数据较少及其分解焓直接实验测定非常困难的问题,在已有的高压可视蓝宝石反应釜中测定了环戊烷/丙酮/叔丁胺/四氢呋喃-水-氢气三组分体系中的水合物相边界条件,并结合Clausius-Clapeyron方程计算确定了4种Ⅱ型二元氢气水合物的分解焓.结果表明:含环戊烷/丙酮/叔丁胺/四氢呋喃的Ⅱ型二元氢气水合物的相平衡压力可降低至纯氢气水合物同温度下相平衡压力的1/10甚至更多.二元氢气水合物的分解焓与添加剂和相平衡温度有关,对于同一种添加剂,随着相平衡温度的升高,所得到的二元氢气水合物分解焓增加.二元氢气水合物相平衡边界和分解焓的测定对进一步研究和开发水合物法储氢技术具有重要价值.

  1. Force modulating dynamic disorder: A physical model of catch-slip bond transitions in receptor-ligand forced dissociation experiments

    Science.gov (United States)

    Liu, Fei; Ou-Yang, Zhong-Can

    2006-11-01

    Recent experiments found that some adhesive receptor-ligand complexes have counterintuitive catch-slip transition behaviors: the mean lifetimes of these complexes first increase (catch) with initial application of a small external force, and then decrease (slip) when the force is beyond some threshold. In this work we suggest that the forced dissociation of these complexes might be a typical rate process with dynamic disorder. The one-dimensional force modulating Agmon-Hopfield model is used to describe the transitions in the single-bond P-selectin glycoprotein ligand 1-P-selectin forced dissociation experiments, which were respectively performed in the constant force [Marshall , Nature (Landon) 423, 190 (2003)] and the ramping force [Evans , Proc. Natl. Acad. Sci. U.S.A 98, 11281 (2004)] modes. We find that, an external force can not only accelerate the bond dissociation, but also modulate the complex from the lower-energy barrier to the higher one; the catch-slip bond transition can arise from a particular energy barrier shape. The agreement between our calculation and the experimental data is satisfactory.

  2. Nuclear enthalpies

    OpenAIRE

    Rozynek Jacek

    2015-01-01

    Even small departures from a nuclear equilibrium density with constant nucleon masses require an increase of a nucleon enthalpy. This process can be described as volume corrections to a nucleon rest energy, which are proportional to pressure and absent in a standard Relativistic Mean Field (RMF) with point-like nucleons. Bag model and RMF calculations show the modifications of nucleon mass, nucleon radius and a Parton Distribution Function (PDF) of Nuclear Matter (NM) above the saturation poi...

  3. Strength of hydrogen bond network takes crucial roles in the dissociation process of inhibitors from the HIV-1 protease binding pocket.

    Directory of Open Access Journals (Sweden)

    Dechang Li

    Full Text Available To understand the underlying mechanisms of significant differences in dissociation rate constant among different inhibitors for HIV-1 protease, we performed steered molecular dynamics (SMD simulations to analyze the entire dissociation processes of inhibitors from the binding pocket of protease at atomistic details. We found that the strength of hydrogen bond network between inhibitor and the protease takes crucial roles in the dissociation process. We showed that the hydrogen bond network in the cyclic urea inhibitors AHA001/XK263 is less stable than that of the approved inhibitor ABT538 because of their large differences in the structures of the networks. In the cyclic urea inhibitor bound complex, the hydrogen bonds often distribute at the flap tips and the active site. In contrast, there are additional accessorial hydrogen bonds formed at the lateral sides of the flaps and the active site in the ABT538 bound complex, which take crucial roles in stabilizing the hydrogen bond network. In addition, the water molecule W301 also plays important roles in stabilizing the hydrogen bond network through its flexible movement by acting as a collision buffer and helping the rebinding of hydrogen bonds at the flap tips. Because of its high stability, the hydrogen bond network of ABT538 complex can work together with the hydrophobic clusters to resist the dissociation, resulting in much lower dissociation rate constant than those of cyclic urea inhibitor complexes. This study may provide useful guidelines for design of novel potent inhibitors with optimized interactions.

  4. Strength of hydrogen bond network takes crucial roles in the dissociation process of inhibitors from the HIV-1 protease binding pocket.

    Science.gov (United States)

    Li, Dechang; Ji, Baohua; Hwang, Keh-Chih; Huang, Yonggang

    2011-01-01

    To understand the underlying mechanisms of significant differences in dissociation rate constant among different inhibitors for HIV-1 protease, we performed steered molecular dynamics (SMD) simulations to analyze the entire dissociation processes of inhibitors from the binding pocket of protease at atomistic details. We found that the strength of hydrogen bond network between inhibitor and the protease takes crucial roles in the dissociation process. We showed that the hydrogen bond network in the cyclic urea inhibitors AHA001/XK263 is less stable than that of the approved inhibitor ABT538 because of their large differences in the structures of the networks. In the cyclic urea inhibitor bound complex, the hydrogen bonds often distribute at the flap tips and the active site. In contrast, there are additional accessorial hydrogen bonds formed at the lateral sides of the flaps and the active site in the ABT538 bound complex, which take crucial roles in stabilizing the hydrogen bond network. In addition, the water molecule W301 also plays important roles in stabilizing the hydrogen bond network through its flexible movement by acting as a collision buffer and helping the rebinding of hydrogen bonds at the flap tips. Because of its high stability, the hydrogen bond network of ABT538 complex can work together with the hydrophobic clusters to resist the dissociation, resulting in much lower dissociation rate constant than those of cyclic urea inhibitor complexes. This study may provide useful guidelines for design of novel potent inhibitors with optimized interactions.

  5. Communication: The highest frequency hydrogen bond vibration and an experimental value for the dissociation energy of formic acid dimer

    DEFF Research Database (Denmark)

    Kollipost, F.; Larsen, René Wugt; Domanskaya, A.V.;

    2012-01-01

    The highest frequency hydrogen bond fundamental of formic acid dimer, ν24 (Bu), is experimentally located at 264 cm−1. FTIR spectra of this in-plane bending mode of (HCOOH)2 and band centers of its symmetric D isotopologues (isotopomers) recorded in a supersonic slit jet expansion are presented...... thermodynamics treatment of the dimerization process up to room temperature. We obtain D0 = 59.5(5) kJ/mol as the best experimental estimate for the dimer dissociation energy at 0 K. Further improvements have to wait for a more consistent determination of the room temperature equilibrium constant....

  6. 1, 4-Pyrone Effects on O-H Bond Dissociation Energies of Catechols in Flavonoids: A Density Functional Theory Study

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Through B3LYP/6-31G** calculations, the 1, 4-pyrone effects on O-H bond dissociation energies (BDEs) of catechols in rings A or B of flavonoids were investigated. For the catechol in ring A, although 1, 4-pyrone enlarged the conjugation system, its electron-withdrawing property increased the O-H BDE 3 ( 4.184 kJ/mol compared with that of catechol. However, for the catechol in ring B, 1, 4-pyrone was poorly conjugated with the moiety, and therefore, had little effect on the O-H BDE.

  7. The application of Guided Ion Beam Tandem Mass Spectrometer; Bond dissociation energies of bare and ligated copper group cluster anions

    International Nuclear Information System (INIS)

    Threshold energies, fragmentation patterns, and integral cross sections for the reactions of collision induced dissociations of bare and ligated copper group cluster anions are determined using a Guided Ion Beam Tandem Mass Spectrometer (GIB-MS). The bond breaking patterns for the copper cluster anions show dramatic even/odd tendencies, e.g., all copper group anions generate as the predominant reaction product, Carbon monoxide is weakly bound to copper group cluster anions. Cohesive energies of the bare copper and silver cluster anions are determined and exhibit a good correspondence with estimate cohesive energies by the model of Miedema.

  8. Ion-Induced Dipole Interactions and Fragmentation Times : C$\\alpha$ -C$\\beta$ Chromophore Bond Dissociation Channel

    CERN Document Server

    Soorkia, Satchin; Kumar, Sunil; Pérot-Taillandier, Marie; Lucas, Bruno; Jouvet, Christophe; Barat, Michel; Fayeton, Jacqueline A

    2015-01-01

    The fragmentation times corresponding to the loss of the chromophore (C$\\alpha$-- C$\\beta$ bond dissociation channel) after photoexcitation at 263 nm have been investigated for several small peptides containing tryptophan or tyrosine. For tryptophan-containing peptides, the aromatic chromophore is lost as an ionic fragment (m/z 130), and the fragmentation time increases with the mass of the neutral fragment. In contrast, for tyrosine-containing peptides the aromatic chromophore is always lost as a neutral fragment (mass = 107 amu) and the fragmentation time is found to be fast (\\textless{}20 ns). These different behaviors are explained by the role of the postfragmentation interaction in the complex formed after the C$\\alpha$--C$\\beta$ bond cleavage.

  9. Hydrogen bonding of the dissociated histidine ligand is not required for formation of a proximal NO adduct in cytochrome c'.

    Science.gov (United States)

    Ghafoor, Dlzar D; Kekilli, Demet; Abdullah, Gaylany H; Dworkowski, Florian S N; Hassan, Hamid G; Wilson, Michael T; Strange, Richard W; Hough, Michael A

    2015-09-01

    Cytochromes c', that occur in methanotrophic, denitrifying and photosynthetic bacteria, form unusual proximal penta-coordinate NO complexes via a hexa-coordinate distal NO intermediate. Their NO binding properties are similar to those of the eukaryotic NO sensor, soluble guanylate cyclase, for which they provide a valuable structural model. Previous studies suggested that hydrogen bonding between the displaced proximal histidine (His120) ligand (following its dissociation from heme due to trans effects from the distally bound NO) and a conserved aspartate residue (Asp121) could play a key role in allowing proximal NO binding to occur. We have characterized three variants of Alcaligenes xylosoxidans cytochrome c' (AXCP) where Asp121 has been replaced by Ala, Ile and Gln, respectively. In all variants, hydrogen bonding between residue 121 and His120 is abolished yet 5-coordinate proximal NO species are still formed. Our data therefore demonstrate that the His120-Asp121 bond is not essential for proximal NO binding although it likely provides an energy minimum for the displaced His ligand. All variants have altered proximal pocket structure relative to native AXCP. PMID:26100643

  10. Dynamical potential approach to dissociation of H-C bond in HCO highly excited vibration

    Institute of Scientific and Technical Information of China (English)

    Fang Chao; Wu Guo-Zhen

    2009-01-01

    The highly excited vibrational levels of HCO in the electronic ground state, X1A', are employed to determine the coefficients of an algebraic Hamiltonian, by which the dynamical potential is derived and shown to be very useful for interpreting thc intramolecular vibrational relaxation (IVR) which operates via the HCO bending motion. The IVR inhibits the dissociation of H atom and enhances the stochastic degree of dynamical character. This approach is from a global viewpoint on a series of levels classified by the polyad number which is a constant of motion in a certain dynamical domain. In this way, the seemingly complicated level structure shows very regular picture, dynamically.

  11. Models for calculation of dissociation energies of homonuclear diatomic molecules

    International Nuclear Information System (INIS)

    The variation of known dissociation energies of the transition metal diatomics across the Periodic Table is rather irregular like the bulk sublimation enthalpy, suggesting that the valence-bond model for bulk metallic systems might be applicable to the gaseous diatomic molecules and the various intermediate clusters. Available dissociation energies were converted to valence-state bonding energies considering various degrees of promotion to optimize the bonding. The degree of promotion of electrons to increase the number of bonding electrons is smaller than for the bulk, but the trends in bonding energy parallel the behavior found for the bulk metals. Thus using the established trends in bonding energies for the bulk elements, it was possible to calculate all unknown dissociation energies to provide a complete table of dissociation energies for all M2 molecules from H2 to Lr2. For solids such as Mg, Al, Si and most of the transition metals, large promotion energies are offset by strong bonding between the valence state atoms. The main question is whether bonding in the diatomics is adequate to sustain extensive promotion. The most extreme example for which a considerable difference would be expected between the bulk and the diatomics would be that of the Group IIA and IIB metals. The first section of this paper which deals with the alkaline earths Mg and Ca demonstrates a significant influence of the excited valence state even for these elements. The next section then expands the treatment to transition metals

  12. Bond-specific dissociation following excitation energy transfer for distance constraint determination in the gas phase.

    Science.gov (United States)

    Hendricks, Nathan G; Lareau, Nichole M; Stow, Sarah M; McLean, John A; Julian, Ryan R

    2014-09-24

    Herein, we report chemistry that enables excitation energy transfer (EET) to be accurately measured via action spectroscopy on gaseous ions in an ion trap. It is demonstrated that EET between tryptophan or tyrosine and a disulfide bond leads to excited state, homolytic fragmentation of the disulfide bond. This phenomenon exhibits a tight distance dependence, which is consistent with Dexter exchange transfer. The extent of fragmentation of the disulfide bond can be used to determine the distance between the chromophore and disulfide bond. The chemistry is well suited for the examination of protein structure in the gas phase because native amino acids can serve as the donor/acceptor moieties. Furthermore, both tyrosine and tryptophan exhibit unique action spectra, meaning that the identity of the donating chromophore can be easily determined in addition to the distance between donor/acceptor. Application of the method to the Trpcage miniprotein reveals distance constraints that are consistent with a native-like fold for the +2 charge state in the gas phase. This structure is stabilized by several salt bridges, which have also been observed to be important previously in proteins that retain native-like structures in the gas phase. The ability of this method to measure specific distance constraints, potentially at numerous positions if combined with site-directed mutagenesis, significantly enhances our ability to examine protein structure in the gas phase. PMID:25174489

  13. Force-dependent bond dissociation govern rolling of HL-60 cells through E-selectin.

    Science.gov (United States)

    Li, Quhuan; Fang, Ying; Ding, Xiaoru; Wu, Jianhua

    2012-08-15

    E-selectin-mediated rolling on vascular surface of circulating leukocyte on vascular surface is a key initial event during inflammatory response and lymphocyte homing. This event depends not only on the specific interactions of adhesive molecules but also on the hemodynamics of blood flow. Little is still understood about whether wall shear stress or shear rate regulates the rolling. With flow chamber techniques, we here measured the effects of transport, shear stress and cell deformation on rolling of both unfixed and fixed HL-60 cells on E-selectin either in the absence or in the presence of 3% Ficoll in medium at various wall shear stresses from 0.05 to 0.7 dyn/cm(2). The results demonstrated a triphasic force-dependent rolling, that is, as increasing of force, the rolling would be accelerated firstly, then followed a decelerating phase occurred at the initial shear threshold of about 0.1 dyn/cm(2), and lastly returned to an accelerating process starting at the optimal shear threshold of 0.35 dyn/cm(2) approximately. The catch bond regime was completely reflected to rolling behaviors, such as tether lifetime, cell stop time and rolling velocity, meaning that the dominant factor to govern rolling is force. The initial shear threshold might be the minimum level of wall shear stress to sustain a stationary rolling, and the optimal shear threshold would make rolling to the most stable and regular. These findings strongly elucidate the catch bond mechanism for flow-enhanced rolling through E-selectin since longer bond lifetimes led to slower and stabler rolling.

  14. Improved Optimization for the Cluster Jastrow Antisymmetric Geminal Power and Tests on Triple-Bond Dissociations

    CERN Document Server

    Neuscamman, Eric

    2016-01-01

    We present a novel specialization of the variational Monte Carlo linear method for the optimization of the recently introduced cluster Jastrow antisymmetric geminal power ansatz, achieving a lower-order polynomial cost scaling than would be possible with a naive application of the linear method and greatly improving optimization performance relative to the previously employed quasi-Newton approach. We test the methodology on highly multi-reference triple-bond stretches, achieving accuracies superior to traditional coupled cluster theory and multi-reference perturbation theory in both the typical example of N$_2$ and the transition-metal-oxide example of [ScO]$^+$.

  15. Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations

    Energy Technology Data Exchange (ETDEWEB)

    Filatov, Michael, E-mail: mike.filatov@gmail.com [Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, Texas 75275-0314 (United States); Huix-Rotllant, Miquel; Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, D-60438 Frankfurt am Main (Germany)

    2015-05-14

    State-averaged (SA) variants of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, SA-REKS and state-interaction (SI)-SA-REKS, implement ensemble density functional theory for variationally obtaining excitation energies of molecular systems. In this work, the currently existing version of the SA-REKS method, which included only one excited state into the ensemble averaging, is extended by adding more excited states to the averaged energy functional. A general strategy for extension of the REKS-type methods to larger ensembles of ground and excited states is outlined and implemented in extended versions of the SA-REKS and SI-SA-REKS methods. The newly developed methods are tested in the calculation of several excited states of ground-state multi-reference systems, such as dissociating hydrogen molecule, and excited states of donor–acceptor molecular systems. For hydrogen molecule, the new method correctly reproduces the distance dependence of the lowest excited state energies and describes an avoided crossing between the doubly excited and singly excited states. For bithiophene–perylenediimide stacked complex, the SI-SA-REKS method correctly describes crossing between the locally excited state and the charge transfer excited state and yields vertical excitation energies in good agreement with the ab initio wavefunction methods.

  16. Probing the Conformational and Functional Consequences of Disulfide Bond Engineering in Growth Hormone by Hydrogen-Deuterium Exchange Mass Spectrometry Coupled to Electron Transfer Dissociation

    DEFF Research Database (Denmark)

    Seger, Signe T; Breinholt, Jens; Faber, Johan H;

    2015-01-01

    spectrometry (HDX-MS) to map the impact of the new disulfide bond on the conformational dynamics of this new hGH variant. Compared to wild type hGH, the variant exhibits reduced loop dynamics, indicating a stabilizing effect of the introduced disulfide bond. Furthermore, the disulfide bond exhibits longer...... ranging effects, stabilizing a short α-helix quite distant from the mutation sites, but also rendering a part of the α-helical hGH core slightly more dynamic. In the regions where the hGH variant exhibits a different deuterium uptake than the wild type protein, electron transfer dissociation (ETD...

  17. Computational methods for the description of pharmacologically relevant platinum complexes--molecular structure and bond dissociation.

    Science.gov (United States)

    Kokoschka, Malte; Galgonek, Jakub; Vondrasek, Jiri; Hobza, Pavel

    2016-02-01

    Cancer is after cardiovascular disease the most frequent cause of death in Europe. In 28 of 53 countries considered in this area it is already the leading cause of death and expected to gain even more importance until the year 2020. Amongst the large arsenal of different anti-cancer drugs, platinum drugs belong to the first developed anticancer drugs and still have a large impact on cancer therapy. Nevertheless therapy with platinum-anticancer drugs is accompanied by severe adverse effects caused by frequent interactions with the amino acids of different human proteins. Computational chemistry offers methods to study such interactions and even those of not yet synthesized drugs in silico. For such studies a profound knowledge of the prediction quality of various computational methods towards platinum-drug-like complexes is necessary. By this article we are aiming on delivering important accuracy information of the frequently used computational methods. Most important findings are the high performance of the double hybrid functional B2PLYP for the calculation of geometries, even in small basis sets, followed by BP86 and PBE and the still acceptable performance of the semi-empirical Method PM6-D3H4X for extremely large systems. To follow absolute energies of the dissociation process, LPNO-CEPA and B3LYP-D3 can be suggested while SCS-MP2 shows an extremely narrow standard deviation and a low maximum error, which make it an ideal candidate for relative energy calculations in the exploration of reaction mechanisms. PMID:26777459

  18. Crystal Structure, Thermal Decomposition Behavior and the Standard Molar Enthalpy of Formation of a Novel 3D Hydrogen Bonded Supramolecular [Co(HnicO)2·(H2O)2

    Institute of Scientific and Technical Information of China (English)

    ZENG,Ming-Hua; WU,Mei-Chun; ZHU,Li-Hong; LIANG,Hong; YANG Xu-Wu

    2007-01-01

    Hydrothermal synthesis and X-ray characterized 3D supramolecular networks were constructed by [Co(HnicO)2·(H2O)2] (HnicOH=2-hydroxynicotinic acid) (1) as building block via abundant dimeric homomeric (N-H…O) and unusually cyclic tetrameric heteromeric (O-H…O) hydrogen-bonds. It is noted that there exist unusually linear metal-water chains comprised of tetrameric units linked by vertexes sharing cobalt centers through hydrogen-bonding. TG-DTG curves illustrated that thermal decomposition was completed by two steps, one is the loss of two terminal water molecules in the range of 156-234 ℃, and the other is the pyrolysis of HnicO ligand in the range of 234-730 ℃. The standard molar enthalpy of formation of the complex was determined to be (-1845.43±2.77) kJ·mol-1 by a rotary-bomb combustion calorimeter.

  19. Density Functional Method Studies of X-H (X=C, N, O, Si, P, S) Bond Dissociation Energies

    Institute of Scientific and Technical Information of China (English)

    FU Yao; DONG Xiao-Yu; WANG Yi-Min; LIU Lei; GUO Qing-Xiang

    2005-01-01

    The performances of the density functional theory (DFT) methods in calculating X-H bond dissociation energies (BDE, X=C, N, O, Si, P, S) were evaluated. It was found that most DFT methods including B3LYP, B3PW91,G96LYP, PBE1PBE and BH&HLYP significantly underestimated the X-H BDE by as much as 13-24 kJ/mol.The underestimation is not due to the use of finite basis set, because the DFT methods still significantly underestimate the X-H BDE with the complete basis set. Therefore, these DFT methods can not be used to calculate the BDE directly. Nevertheless, the B3P86 method shows very small underestimation for the X-H BDE. Further analysis suggests that there be no advantage for using the restricted open-shell DFT methods. The unrestricted DFT methods actually perform slightly better than the restricted open-shell DFT methods in most cases. Finally, it was found that the underestimation by the DFT methods was largely systematic. The use of the calibrated UDFT/6-311+ + G(d, p) method was recommended to calculate the X-H BDE.

  20. Calorimetric Determination of Enthalpy of Formation of Natural Gas Hydrates

    Institute of Scientific and Technical Information of China (English)

    高军; KennethN.Marsh

    2003-01-01

    This paper reports the measurements of enthalpies of natural gas hydrates in typical natural gas mixture containing methane, ethane, propane and iso-butane at pressure in the vicinity of 2000 kPa (300 psi) and 6900 kPa(1000psi). The measurements were made in a multi-cell differential scanning calorimeter using modified high pressure cells. The enthalpy of water and the enthalpy of dissociation of the gas hydrate were determined from the calorimeter response during slow temperature scanning at constant pressure. The amount of gas released from the dissociation of hydrate was determined from the pumped volume of the high pressure pump. The occupation ratio (mole ratio) of the water to gas and the enthalpy of hydrate formation are subject to uncertainty of 1.5%.The results show that the enthalpy of hydrate formation and the occupation ratio are essentially independent of pressure.

  1. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics.

    Science.gov (United States)

    Bhagan, Salome; Wayland, Bradford B

    2011-11-01

    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  2. Molecular Dissociation in Presence of a Catalyst II: The bond breaking role of the transition from virtual to localized states

    CERN Document Server

    Ruderman, Andres; Santos, Elizabeth; Pastawski, Horacio Miguel

    2016-01-01

    We address a molecular dissociation mechanism that is known to occur when a H 2 molecule approaches a catalyst with its molecular axis parallel to the surface. It is found that molecular dissociation is a form of quantum dynamical phase transition associated to an ana- lytic discontinuity of quite unusual nature: the molecule is destabilized by the transition from non-physical virtual states into actual local- ized states. Current description complements our recent results for a molecule approaching the catalyst with its molecular axis perpendicu- lar to the surface. Also, such a description can be seen as a further successful implementation of a non-Hermitian Hamiltonian in a well defined model.

  3. Dissociation constants of weak acids from ab initio molecular dynamics using metadynamics: influence of the inductive effect and hydrogen bonding on pKa values.

    Science.gov (United States)

    Tummanapelli, Anil Kumar; Vasudevan, Sukumaran

    2014-11-26

    The theoretical estimation of the dissociation constant, or pKa, of weak acids continues to be a challenging field. Here, we show that ab initio Car-Parrinello molecular dynamics simulations in conjunction with metadynamics calculations of the free-energy profile of the dissociation reaction provide reasonable estimates of the pKa value. Water molecules, sufficient to complete the three hydration shells surrounding the acid molecule, were included explicitly in the computation procedure. The free-energy profiles exhibit two distinct minima corresponding to the dissociated and neutral states of the acid, and the difference in their values provides the estimate for pKa. We show for a series of organic acids that CPMD simulations in conjunction with metadynamics can provide reasonable estimates of pKa values. The acids investigated were aliphatic carboxylic acids, chlorine-substituted carboxylic acids, cis- and trans-butenedioic acid, and the isomers of hydroxybenzoic acid. These systems were chosen to highlight that the procedure could correctly account for the influence of the inductive effect as well as hydrogen bonding on pKa values of weak organic acids. In both situations, the CPMD metadynamics procedure faithfully reproduces the experimentally observed trend and the magnitudes of the pKa values.

  4. Disruption of the H-bond network in the main access channel of catalase-peroxidase modulates enthalpy and entropy of Fe(III) reduction.

    Science.gov (United States)

    Vlasits, Jutta; Bellei, Marzia; Jakopitsch, Christa; De Rienzo, Francesca; Furtmüller, Paul G; Zamocky, Marcel; Sola, Marco; Battistuzzi, Gianantonio; Obinger, Christian

    2010-06-01

    Catalase-peroxidases are the only heme peroxidases with substantial hydrogen peroxide dismutation activity. In order to understand the role of the redox chemistry in their bifunctional activity, catalatically-active and inactive mutant proteins have been probed in spectroelectrochemical experiments. In detail, wild-type KatG from Synechocystis has been compared with variants with (i) disrupted KatG-typical adduct (Trp122-Tyr249-Met275), (ii) mutation of the catalytic distal His123-Arg119 pair, and (iii) altered accessibility to the heme cavity (Asp152, Ser335) and modified charge at the substrate channel entrance (Glu253). A valuable insight into the mechanism of reduction potential (E degrees ') modulation in KatG has been obtained from the parameterization of the corresponding enthalpic and entropic components, determined from the analysis of the temperature dependence of E degrees '. Moreover, model structures of ferric and ferrous Synechocystis KatG have been computed and used as reference to analyze and discuss the experimental data. The results, discussed by reference to published resonance Raman data on the strength of the proximal iron-imidazole bond and catalytic properties, demonstrate that E degrees ' of the Fe(III)/Fe(II) couple is not strongly correlated with the bifunctional activity. Besides the importance of an intact Trp-Tyr-Met adduct, it is the architecture of the long and constricted main channel that distinguishes KatGs from monofunctional peroxidases. An ordered matrix of oriented water dipoles is important for H(2)O(2) oxidation. Its disruption results in modification of enthalpic and entropic contributions to E degrees ' that reflect reduction-induced changes in polarity, electrostatics, continuity and accessibility of solvent to the metal center as well as alterations in solvent reorganization.

  5. Molecular dissociation in presence of a catalyst: II. The bond breaking role of the transition from virtual to localized states

    Science.gov (United States)

    Ruderman, A.; Dente, A. D.; Santos, E.; Pastawski, H. M.

    2016-08-01

    We address a molecular dissociation mechanism that is known to occur when a H2 molecule approaches a catalyst with its molecular axis parallel to the surface. It is found that molecular dissociation is a form of quantum dynamical phase transition associated to an analytic discontinuity of quite unusual nature: the molecule is destabilized by the transition from non-physical virtual states into actual localized states. Current description complements our recent results for a molecule approaching the catalyst with its molecular axis perpendicular to the surface (Ruderman et al 2015 J. Phys.: Condens. Matter 27 315501). Also, such a description can be seen as a further successful implementation of a non-Hermitian Hamiltonian in a well defined model.

  6. 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

  7. Excitation energies with linear response density matrix functional theory along the dissociation coordinate of an electron-pair bond in N-electron systems.

    Science.gov (United States)

    van Meer, R; Gritsenko, O V; Baerends, E J

    2014-01-14

    Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ωα and oscillator strengths fα for two-electron systems if extended to the so-called phase including natural orbital (PINO) theory. The Löwdin-Shull expression for the energy of two-electron systems in terms of the natural orbitals and their phases affords in this case an exact phase-including natural orbital functional (PILS), which is non-primitive (contains other than just J and K integrals). In this paper, the extension of the PILS functional to N-electron systems is investigated. With the example of an elementary primitive NO functional (BBC1) it is shown that current density matrix functional theory ground state functionals, which were designed to produce decent approximations to the total energy, fail to deliver a qualitatively correct structure of the (inverse) response function, due to essential deficiencies in the reconstruction of the two-body reduced density matrix (2RDM). We now deduce essential features of an N-electron functional from a wavefunction Ansatz: The extension of the two-electron Löwdin-Shull wavefunction to the N-electron case informs about the phase information. In this paper, applications of this extended Löwdin-Shull (ELS) functional are considered for the simplest case, ELS(1): one (dissociating) two-electron bond in the field of occupied (including core) orbitals. ELS(1) produces high quality ωα(R) curves along the bond dissociation coordinate R for the molecules LiH, Li2, and BH with the two outer valence electrons correlated. All of these results indicate that response properties are much more sensitive to deficiencies in the reconstruction of the 2RDM than the ground state energy, since derivatives of the functional with respect to both the NOs and the occupation numbers need to be accurate. PMID:24437859

  8. Influence of steric and intramolecular inductive effects on the variable trends in R-X (R=Alkyl) bond dissociation energy

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The question "why are the variation trends of R-X bond dissociation energy different?" is answered. The R-X bond dissociation energy (BDE) may be influenced by three main factors: the C-X intrinsic bond energy, the 1,3 geminal repulsion, and the intramolecular charge-induced dipole. In the presence of atom X, the variation trend of BDE in R-X (R= Me, Et, i-Pr, t-Bu) is dominated by two factors, the 1,3 geminal repulsion and the intramolecular charge-induced dipole. The former decreases the R-X BDE, and the latter either increases or decreases the R-X BDE. For the series of R-X with the R-C bond (such as R-Me, R-CH == CH2, R-C≡CH, and R-CN), the 1,3 geminal repulsion decreases the R-X BDE, and the variation trends of R-C BDE decrease from Me to t-Bu. As regards the series of R-X (such as R-H, R-BH2, and R-SiH2) in which the electronegativity of atom X is smaller than that of the carbon atom, the above two factors decrease the R-X BDE, and the variation trends of the R-X BDE decrease from Me to t-Bu. As to the series of R-X (such as R-F, R-OH, R-Cl, R-Br, R-I, and R-NH2) in which the electronegativity of atom X is larger than that of the carbon atom, the 1,3 geminal repulsion decreases the R-X BDE, while the intramolecular charge-induced dipole increases the R-X BDE. In this case, the variation trends of R-X BDE depend on the competition of the two factors. As a result, some of them (e. g., R-F, R-OH) increase from Me to t-Bu, some (e. g., R-I) decrease from Me to t-Bu, and some (e. g., R-Br) change very little.

  9. Influence of steric and intramolecular inductive effects on the variable trends in R-X (R=Alkyl) bond dissociation energy

    Institute of Scientific and Technical Information of China (English)

    CAO ChenZhong

    2009-01-01

    The question "why are the variation trends of R-X bond dissociation energy different?" is answered.The R-X bond dissociation energy (BDE) may be influenced by three main factors:the C-X intrinsic bond energy,the 1,3 geminal repulsion,and the intramolecular charge-induced dipole.In the presence of atom X,the variation trend of BDE in R-X (R=Me,Et,i-Pr,t-Bu) is dominated by two factors,the 1,3 geminal repulsion and the intramolecular charge-induced dipole.The former decreases the R-X BDE,and the latter either increases or decreases the R-X BDE.For the series of R-X with the R-C bond (such as R-Me,R-CH-CH2,R-C-CH,and R-CN),the 1,3 geminal repulsion decreases the R-X BDE,and the variation trends of R-C BDE decrease from Me to t-Bu.As regards the series of R-X (such as R-H,R-BH2,and R-SiH2) in which the electronegativity of atom X is smaller than that of the carbon atom,the above two factors decrease the R-X BDE,and the variation trends of the R-X BDE decrease from Me to t-Bu.As to the series of R-X (such as R-F,R-OH,R-CI,R-Br,R-I,and R-NH2) in which the electronegativity of atom X is larger than that of the carbon atom,the 1,3 geminal repulsion decreases the R-X BDE,while the intramolecular charge-induced dipole increases the R-X BDE.In this case,the variation trends of R-X BDE depend on the competition of the two factors.As a result,some of them (e.g.,R-F,R-OH) increase from Me to t-Bu,some (e.g.,R-I) decrease from Me to t-Bu,and some (e.g.,R-Br) change very little.

  10. The Cr+-D2 cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parameters

    Science.gov (United States)

    Dryza, V.; Bieske, E. J.

    2009-10-01

    The infrared spectrum of the T-shaped C52r+-D2 complex is measured over the 2742-2820 cm-1 range by detecting Cr+ photofragments. The main band, due to the D-D stretch excitation, is shifted at 215 cm-1 to lower energy from the Q01 transition of the free D2 molecule and displays clearly resolved rovibrational transitions. Observation of a photodissociation onset for the N'=8 rotational level is used to infer that the dissociation energy of Cr+-D2, with respect to ground-state Cr+ and D2 fragments, lies between 2839.7 and 2856.9 cm-1. Perturbations to the upper state levels are presumed to arise from interactions with quasibound combination levels involving the intermolecular stretch and bend vibrational modes. A vibrationally averaged Cr+⋯D2 separation of 2.023 Å and an estimate of 394 cm-1 for the intermolecular harmonic stretching frequency are derived from the measured rotational constants.

  11. The Cr(+)-D(2) cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parameters.

    Science.gov (United States)

    Dryza, V; Bieske, E J

    2009-10-28

    The infrared spectrum of the T-shaped (52)Cr(+)-D(2) complex is measured over the 2742-2820 cm(-1) range by detecting Cr(+) photofragments. The main band, due to the D-D stretch excitation, is shifted at 215 cm(-1) to lower energy from the Q(0) (1) transition of the free D(2) molecule and displays clearly resolved rovibrational transitions. Observation of a photodissociation onset for the N(')=8 rotational level is used to infer that the dissociation energy of Cr(+)-D(2), with respect to ground-state Cr(+) and D(2) fragments, lies between 2839.7 and 2856.9 cm(-1). Perturbations to the upper state levels are presumed to arise from interactions with quasibound combination levels involving the intermolecular stretch and bend vibrational modes. A vibrationally averaged Cr(+)...D(2) separation of 2.023 A and an estimate of 394 cm(-1) for the intermolecular harmonic stretching frequency are derived from the measured rotational constants.

  12. Compact two-electron wave function for bond dissociation and Van der Waals interactions: A natural amplitude assessment

    International Nuclear Information System (INIS)

    Electron correlations in molecules can be divided in short range dynamical correlations, long range Van der Waals type interactions, and near degeneracy static correlations. In this work, we analyze for a one-dimensional model of a two-electron system how these three types of correlations can be incorporated in a simple wave function of restricted functional form consisting of an orbital product multiplied by a single correlation function f (r12) depending on the interelectronic distance r12. Since the three types of correlations mentioned lead to different signatures in terms of the natural orbital (NO) amplitudes in two-electron systems, we make an analysis of the wave function in terms of the NO amplitudes for a model system of a diatomic molecule. In our numerical implementation, we fully optimize the orbitals and the correlation function on a spatial grid without restrictions on their functional form. Due to this particular form of the wave function, we can prove that none of the amplitudes vanishes and moreover that it displays a distinct sign pattern and a series of avoided crossings as a function of the bond distance in agreement with the exact solution. This shows that the wave function ansatz correctly incorporates the long range Van der Waals interactions. We further show that the approximate wave function gives an excellent binding curve and is able to describe static correlations. We show that in order to do this the correlation function f (r12) needs to diverge for large r12 at large internuclear distances while for shorter bond distances it increases as a function of r12 to a maximum value after which it decays exponentially. We further give a physical interpretation of this behavior

  13. Dynamics of N-OH bond dissociation in cyclopentanone and cyclohexanone oxime at 193 nm: laser-induced fluorescence detection of nascent OH (v'', J'').

    Science.gov (United States)

    Kawade, Monali N; Saha, Ankur; Upadhyaya, Hari P; Kumar, Awadhesh; Naik, Prakash D

    2010-12-01

    Cyclohexanone oxime (CHO) and cyclopentanone oxime (CPO) in the vapor phase undergo N-OH bond scission upon excitation at 193 nm to produce OH, which was detected state selectively employing laser-induced fluorescence. The measured energy distribution between fragments for both oximes suggests that in CHO the OH produced is mostly vibrationally cold, with moderate rotational excitation, whereas in CPO the OH fragment is also formed in v'' = 1 (~2%). The rotational population of OH (v'' = 0, J'') from CHO is characterized by a rotational temperature of 1440 ± 80 K, whereas the rotational populations of OH (v'' = 0, J'') and OH (v'' = 1, J'') from CPO are characterized by temperatures of 1360 ± 90 K and 930 ± 170 K, respectively. A high fraction of the available energy is partitioned to the relative translation of the fragments with f(T) values of 0.25 and 0.22 for CHO and CPO, respectively. In the case of CHO, the Λ-doublet states of the nascent OH radical are populated almost equally in lower rotational quantum levels N'', with a preference for Π(+) (A') states for higher N''. However, there is no preference for either of the two spin orbit states Π(3/2) and Π(1/2) of OH. The nascent OH product in CPO is equally distributed in both Λ-doublet states of Π(+) (A') and Π(-) (A'') for all N'', but has a preference for the Π(3/2) spin orbit state. Experimental work in combination with theoretical calculations suggests that both CHO and CPO molecules at 193 nm are excited to the S(2) state, which undergoes nonradiative relaxation to the T(2) state. Subsequently, molecules undergo the N-OH bond dissociation from the T(2) state with an exit barrier to produce OH (v'', J'').

  14. Kinetic, spectroscopic, and theoretical assessment of associative and dissociative methanol dehydration routes in zeolites.

    Science.gov (United States)

    Jones, Andrew J; Iglesia, Enrique

    2014-11-01

    Mechanistic interpretations of rates and in situ IR spectra combined with density functionals that account for van der Waals interactions of intermediates and transition states within confining voids show that associative routes mediate the formation of dimethyl ether from methanol on zeolitic acids at the temperatures and pressures of practical dehydration catalysis. Methoxy-mediated dissociative routes become prevalent at higher temperatures and lower pressures, because they involve smaller transition states with higher enthalpy, but also higher entropy, than those in associative routes. These enthalpy-entropy trade-offs merely reflect the intervening role of temperature in activation free energies and the prevalence of more complex transition states at low temperatures and high pressures. This work provides a foundation for further inquiry into the contributions of H-bonded methanol and methoxy species in homologation and hydrocarbon synthesis reactions from methanol.

  15. Relationship between molecular descriptors and the enthalpies of sublimation of natural amino acids

    Science.gov (United States)

    Badelin, V. G.; Tyunina, V. V.; Girichev, G. V.; Tyunina, E. Yu.

    2016-07-01

    A multiparameter correlation between the enthalpies of sublimation and molecular descriptors of natural amino acids is proposed, based on generalized experimental and literature data on the heat effects of sublimation. The contributions from Van der Waals interactions, hydrogen bond formation, and electrostatic effects into enthalpy of sublimation has been evaluated using regression coefficients.

  16. Surface-Controlled Mono/Diselective ortho C-H Bond Activation.

    Science.gov (United States)

    Li, Qing; Yang, Biao; Lin, Haiping; Aghdassi, Nabi; Miao, Kangjian; Zhang, Junjie; Zhang, Haiming; Li, Youyong; Duhm, Steffen; Fan, Jian; Chi, Lifeng

    2016-03-01

    One of the most charming and challenging topics in organic chemistry is the selective C-H bond activation. The difficulty arises not only from the relatively large bond-dissociation enthalpy, but also from the poor reaction selectivity. In this work, Au(111) and Ag(111) surfaces were used to address ortho C-H functionalization and ortho-ortho couplings of phenol derivatives. More importantly, the competition between dehydrogenation and deoxygenation drove the diversity of reaction pathways of phenols on surfaces, that is, diselective ortho C-H bond activation on Au(111) surfaces and monoselective ortho C-H bond activation on Ag(111) surfaces. The mechanism of this unprecedented phenomenon was extensively explored by scanning tunneling microscopy, density function theory, and X-ray photoelectron spectroscopy. Our findings provide new pathways for surface-assisted organic synthesis via the mono/diselective C-H bond activation. PMID:26853936

  17. Why Static O-H Bond Parameters Cannot Characterize the Free Radical Scavenging Activity of Phenolic Antioxidants: ab initio Study

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The static O-H bond parameters including O-H bond length, O-H charge difference, O-H Mulliken population and O-H bond stretching force constant (k) for 17 phenols were calculated by ab initio method HF/6-31G**. In combination with the O-H bond dissociation enthalpies (BDE) of the phenols determined by experiment, it was found that there were poor correlationships between the static O-H bond parameters and O-H BDE. Considering the good correlationship between O-H BDE and logarithm of free radical scavenging rate constant for phenolic antioxidant, it is reasonable to believe that the ineffectiveness of static O-H bond parameters in characterizing antioxidant activity arises from the fact that they cannot measure the O-H BDE.

  18. Accurate Enthalpies of Formation of Astromolecules: Energy, Stability and Abundance

    CERN Document Server

    Etim, Emmanuel E

    2016-01-01

    Accurate enthalpies of formation are reported for known and potential astromolecules using high level ab initio quantum chemical calculations. A total of 130 molecules comprising of 31 isomeric groups and 24 cyanide/isocyanide pairs with atoms ranging from 3 to 12 have been considered. The results show an interesting, surprisingly not well explored, relationship between energy, stability and abundance (ESA) existing among these molecules. Among the isomeric species, isomers with lower enthalpies of formation are more easily observed in the interstellar medium compared to their counterparts with higher enthalpies of formation. Available data in literature confirm the high abundance of the most stable isomer over other isomers in the different groups considered. Potential for interstellar hydrogen bonding accounts for the few exceptions observed. Thus, in general, it suffices to say that the interstellar abundances of related species are directly proportional to their stabilities. The immediate consequences of ...

  19. Enthalpy screen of drug candidates.

    Science.gov (United States)

    Schön, Arne; Freire, Ernesto

    2016-11-15

    The enthalpic and entropic contributions to the binding affinity of drug candidates have been acknowledged to be important determinants of the quality of a drug molecule. These quantities, usually summarized in the thermodynamic signature, provide a rapid assessment of the forces that drive the binding of a ligand. Having access to the thermodynamic signature in the early stages of the drug discovery process will provide critical information towards the selection of the best drug candidates for development. In this paper, the Enthalpy Screen technique is presented. The enthalpy screen allows fast and accurate determination of the binding enthalpy for hundreds of ligands. As such, it appears to be ideally suited to aid in the ranking of the hundreds of hits that are usually identified after standard high throughput screening.

  20. Performance of a Nonempirical Density Functional on Molecules and Hydrogen-Bonded Complexes

    CERN Document Server

    Mo, Yuxiang; Car, Roberto; Staroverov, Viktor N; Scuseria, Gustavo E; Tao, Jianmin

    2016-01-01

    Recently, Tao and Mo (TM) derived a new meta-generalized gradient approximation based on a model exchange hole. In this work, the performance of this functional is assessed on standard test sets, using the 6-311++G(3df,3pd) basis set. These test sets include 223 G3/99 enthalpies of formation, 58 electron affinities, 8 proton affinities, 96 bond lengths, 82 harmonic vibrational frequencies, and 10 hydrogen-bonded molecular complexes. Our calculations show that the TM functional can achieve remarkable accuracy for most molecular properties, improving upon non-empirical density functionals considered here. In particular, it delivers the best accuracy for proton affinities, harmonic vibrational frequencies, and hydrogen-bonded dissociation energies and bond lengths, compared to other semilocal density-functional approximations considered in this work.

  1. The Evaluation of Empirical Resonance Energies as Reaction Enthalpies with Particular Reference to Benzene.

    Science.gov (United States)

    George, Philip; And Others

    1984-01-01

    Discusses the nature of experimental resonance energy, explaining how its magnitude depends upon choice of reference molecules from which bond energies are derived. Also explains how it can be evaluated more simply, without recourse to bond energies, as enthalpy change for a reaction predetermined by choice of reference molecules. (JN)

  2. Enthalpy-entropy compensation in protein unfolding

    Institute of Scientific and Technical Information of China (English)

    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.

  3. Quantum Chemistry Study on Dissociation of Oxalyl Bromide

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    The multi-bond dissociation dynamics of oxalyl bromide ((BrCO)2) has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at the ground state (S0) is of barrierless. After the absorption of a photon, (BrCO)2 is excited to the first excited state and one of its C-Br bonds is broken to yield dissociate.

  4. Calorimetric Determination of Enthalpy of Formation of Natural Gas Hydrates%天然气水合物生成焓的实验研究

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    This paper reports the measurements of enthalpies of natural gas hydrates in typical natural gas mixturecontaining methane, ethane, propane and iso-butane at pressure in the vicinity of 2000 kPa (300 psi) and 6900 kPa(1000psi). The measurements were made in a multi-cell differential scanning calorimeter using modified highpressure cells. The enthalpy of water and the enthalpy of dissociation of the gas hydrate were determined fromthe calorimeter response during slow temperature scanning at constant pressure. The amount of gas released fromthe dissociation of hydrate was determined from the pumped volume of the high pressure pump. The occupationratio (mole ratio) of the water to gas and the enthalpy of hydrate formation are subject to uncertainty of 1.5%.The results show that the enthalpy of hydrate formation and the occupation ratio are essentially independent of pressure.

  5. C---lH...O and O...H...O bonded intermediates in the dissociation of low energy methyl glycolate radical cations

    Science.gov (United States)

    Suh, Dennis; Kingsmill, Carol A.; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    1995-08-01

    Low energy methyl glycolate radical cations HOCH2C(=O)OCH3+, 1, abundantly lose HCO, yielding protonated methyl formate H---C(OH)OCH3+. Tandem mass spectrometry based experiments on 2H, 13C and 18O labelled isotopologues show that this loss is largely (about 75%) atom specific. Analysis of the atom connectivity in the product ions indicates that the reaction proceeds analogously to the loss of HCO and CH3CO from ionized acetol HOCH2C(=O)CH3+ and acetoin HOCH(CH3)C(=O)CH3+, respectively. The mechanism, it is proposed, involves isomerization of 1 to the key intermediate CH2=O... H---C(=O)OCH3+, an H-bridged ion-dipole complex of neutral formaldehyde and ionized methyl formate. Next, charge transfer takes place to produce CH3OC(H)=O...HC(H)=O+, an H-bridged ion-dipole complex of ionized formaldehyde and neutral methyl formate, followed by proton transfer to generate the products. Preliminary ab initio calculations executed at the UMP3/6-31G*//6-31G*+ZPVE level of theory are presented in support of this proposal. The non-specific loss of HCO from 1 (about 25%) is rationalized to occur via the same mechanism, but after communication with isomeric dimethyl carbonate ions CH3OC(=O)OCH3+, 2, via the O...H...O bonded intermediate [CH2=O...H...O=C---OCH3]+. The latter pathway is even more important in the formation of CH2OH+ ions from 1 which, it is shown, is not a simple bond cleavage reaction, but may involve consecutive or concerted losses of CH3 and CO2 from the above O...H...O bonded species. Ionized methyl lactate HOCH(CH3)C(=O)OCH3+, the higher homologue of 1, shows a unimolecular chemistry which is akin to that of 1.

  6. Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Andrew J.; Iglesia, Enrique

    2014-11-03

    Mechanistic interpretations of rates and in situ IR spectra combined with density functionals that account for van der Waals interactions of intermediates and transition states within confining voids show that associative routes mediate the formation of dimethyl ether from methanol on zeolitic acids at the temperatures and pressures of practical dehydration catalysis. Methoxy-mediated dissociative routes become prevalent at higher temperatures and lower pressures, because they involve smaller transition states with higher enthalpy, but also higher entropy, than those in associative routes. These enthalpy–entropy trade-offs merely reflect the intervening role of temperature in activation free energies and the prevalence of more complex transition states at low temperatures and high pressures. This work provides a foundation for further inquiry into the contributions of H-bonded methanol and methoxy species in homologation and hydrocarbon synthesis reactions from methanol.

  7. Dissociation of ozonide in water

    Energy Technology Data Exchange (ETDEWEB)

    Bentley, J.; Collins, J.Y.; Chipman, D.M.

    2000-05-18

    The free energy of bond dissociation for ozonide ion radical is found to be lowered in aqueous solution by about 20 kcal/mol relative to that in the gas phase, based on electronic structure calculations. Explicit treatment of anion-water clusters indicates that the stronger hydrogen bonds to first-shell water molecules formed by O{sup {minus}} relative to O{sub 3}{sup {minus}} account for much of the lowering. Reaction field methods show that nonspecific electrostatic polarization of the bulk solvent further contributes noticeably to the lowering. The study clearly demonstrates that the aqueous free energy of ozonide bond dissociation is small, and probably endothermic. The best semitheoretical prediction of the actual value is 5 {+-} 5 kcal/mol.

  8. Electron Capture Dissociation of Weakly Bound Polypeptide Polycationic Complexes

    DEFF Research Database (Denmark)

    Haselmann, Kim F; Jørgensen, Thomas J D; Budnik, Bogdan A;

    2002-01-01

    We have previously reported that, in electron capture dissociation (ECD), rupture of strong intramolecular bonds in weakly bound supramolecular aggregates can proceed without dissociation of weak intermolecular bonds. This is now illustrated on a series of non-specific peptide-peptide dimers as w...

  9. Polymer-Polymer Miscibility and Enthalpy Relaxations

    NARCIS (Netherlands)

    Bosma, Martin; Brinke, Gerrit ten; Ellis, Thomas S.

    1988-01-01

    Annealing of polymers below the glass transition temperature results in a decrease in enthalpy that is recovered during heating. The enthalpy recovery is visible as an endothermic peak in a differential scanning calorimetry (DSC) scan. The position of this peak depends on the thermal treatment given

  10. Enthalpy damping for the steady Euler equations

    Science.gov (United States)

    Jespersen, D. C.

    1985-01-01

    For inviscid steady flow problems where the enthalpy is constant at steady state, it was previously proposed to use the difference between the local enthalpy and the steady state enthalpy as a driving term to accelerate convergence of iterative schemes. This idea is analyzed, both on the level of the partial differential equation and on the level of a particular finite difference scheme. It is shown that for the two-dimensional unsteady Euler equations, a hyperbolic system with eigenvalues on the imaginary axis, there is no enthalpy damping strategy which moves all the eigenvalues into the open left half plane. For the numerical scheme, however, the analysis shows and examples verify that enthalpy damping is potentially effective in accelerating convergence to steady state.

  11. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    Science.gov (United States)

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  12. 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....

  13. Enthalpy-Entropy Compensation in the Binding of Modulators at Ionotropic Glutamate Receptor GluA2.

    Science.gov (United States)

    Krintel, Christian; Francotte, Pierre; Pickering, Darryl S; Juknaitė, Lina; Pøhlsgaard, Jacob; Olsen, Lars; Frydenvang, Karla; Goffin, Eric; Pirotte, Bernard; Kastrup, Jette S

    2016-06-01

    The 1,2,4-benzothiadiazine 1,1-dioxide type of positive allosteric modulators of the ionotropic glutamate receptor A2 (GluA2) are promising lead compounds for the treatment of cognitive disorders, e.g., Alzheimer's disease. The modulators bind in a cleft formed by the interface of two neighboring ligand binding domains and act by stabilizing the agonist-bound open-channel conformation. The driving forces behind the binding of these modulators can be significantly altered with only minor substitutions to the parent molecules. In this study, we show that changing the 7-fluorine substituent of modulators BPAM97 (2) and BPAM344 (3) into a hydroxyl group (BPAM557 (4) and BPAM521 (5), respectively), leads to a more favorable binding enthalpy (ΔH, kcal/mol) from -4.9 (2) and -7.5 (3) to -6.2 (4) and -14.5 (5), but also a less favorable binding entropy (-TΔS, kcal/mol) from -2.3 (2) and -1.3 (3) to -0.5 (4) and 4.8 (5). Thus, the dissociation constants (Kd, μM) of 4 (11.2) and 5 (0.16) are similar to those of 2 (5.6) and 3 (0.35). Functionally, 4 and 5 potentiated responses of 10 μM L-glutamate at homomeric rat GluA2(Q)i receptors with EC50 values of 67.3 and 2.45 μM, respectively. The binding mode of 5 was examined with x-ray crystallography, showing that the only change compared to that of earlier compounds was the orientation of Ser-497 pointing toward the hydroxyl group of 5. The favorable enthalpy can be explained by the formation of a hydrogen bond from the side-chain hydroxyl group of Ser-497 to the hydroxyl group of 5, whereas the unfavorable entropy might be due to desolvation effects combined with a conformational restriction of Ser-497 and 5. In summary, this study shows a remarkable example of enthalpy-entropy compensation in drug development accompanied with a likely explanation of the underlying structural mechanism.

  14. Standard Enthalpies of Formation of Solid Complexes of Lanthanide Nitrates with Alanine

    Institute of Scientific and Technical Information of China (English)

    杨旭武; 陈三平; 高胜利; 刘晓华; 史启祯

    2002-01-01

    The combustion energies of fourteen solid complexes of lanthanide nitrate with alanine were determined. The standard enthalpies of combustion, Δc,coor(s)H°, and standard enthalpies of formation, Δf,coor(s)H°, were calculated for these complexes. The relationship of Δc,coor(s)H° and Δf,coor(s)H° with the atomic numbers of the elements in the lanthanide series were examined. The results show that a certain amount of covalence is present in the chemical bond between the lanthanide cations and alanine.

  15. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  16. A computational study on the enhanced stabilization of aminophenol derivatives by internal hydrogen bonding

    Science.gov (United States)

    Gomes, José R. B.; Ribeiro da Silva, Manuel A. V.

    2006-05-01

    The stabilization of aminophenol derivatives and their radicals due to internal hydrogen bonding has been analyzed by means of density functional theory and by topological electron density analysis. The calculations have been carried out at the B3LYP level of theory, using several basis sets, and by means of the CBS-4M composite approach. A strong O-H⋯NH 2 hydrogen bond is found to stabilize the aminophenol with the lone-pair of the nitrogen atom co-planar with the aromatic ring, contrasting with the optimized structure found for aniline. The effect of electron donors and electron acceptors on the strength of the internal hydrogen bond is also analyzed. For one of the species studied, 2,6-diaminophenol, the computed O-H bond dissociation enthalpy is only 300 kJ/mol, the lowest value found so far for phenol and other compounds containing the O-H bond, almost 25 kJ/mol lower than those found experimentally for pyrogallol and for vitamin E. The explanation for such a small value comes from the enhanced stabilization of the corresponding radical species by internal hydrogen bonding, combined with a decrease of the steric effects caused by rotation of the amino groups.

  17. A computational study on the enhanced stabilization of aminophenol derivatives by internal hydrogen bonding

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Jose R.B. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Ribeiro da Silva, Manuel A.V. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)], E-mail: risilva@fc.up.pt

    2006-05-31

    The stabilization of aminophenol derivatives and their radicals due to internal hydrogen bonding has been analyzed by means of density functional theory and by topological electron density analysis. The calculations have been carried out at the B3LYP level of theory, using several basis sets, and by means of the CBS-4M composite approach. A strong O-H...NH{sub 2} hydrogen bond is found to stabilize the aminophenol with the lone-pair of the nitrogen atom co-planar with the aromatic ring, contrasting with the optimized structure found for aniline. The effect of electron donors and electron acceptors on the strength of the internal hydrogen bond is also analyzed. For one of the species studied, 2,6-diaminophenol, the computed O-H bond dissociation enthalpy is only 300 kJ/mol, the lowest value found so far for phenol and other compounds containing the O-H bond, almost 25 kJ/mol lower than those found experimentally for pyrogallol and for vitamin E. The explanation for such a small value comes from the enhanced stabilization of the corresponding radical species by internal hydrogen bonding, combined with a decrease of the steric effects caused by rotation of the amino groups.

  18. Estimation of Solvation Entropy and Enthalpy via Analysis of Water Oxygen-Hydrogen Correlations.

    Science.gov (United States)

    Velez-Vega, Camilo; McKay, Daniel J J; Kurtzman, Tom; Aravamuthan, Vibhas; Pearlstein, Robert A; Duca, José S

    2015-11-10

    A statistical-mechanical framework for estimation of solvation entropies and enthalpies is proposed, which is based on the analysis of water as a mixture of correlated water oxygens and water hydrogens. Entropic contributions of increasing order are cast in terms of a Mutual Information Expansion that is evaluated to pairwise interactions. In turn, the enthalpy is computed directly from a distance-based hydrogen bonding energy algorithm. The resulting expressions are employed for grid-based analyses of Molecular Dynamics simulations. In this first assessment of the methodology, we obtained global estimates of the excess entropy and enthalpy of water that are in good agreement with experiment and examined the method's ability to enable detailed elucidation of solvation thermodynamic structures, which can provide valuable knowledge toward molecular design.

  19. Enthalpy relaxation and annealing effect in polystyrene.

    Science.gov (United States)

    Sakatsuji, Waki; Konishi, Takashi; Miyamoto, Yoshihisa

    2013-07-01

    The effects of thermal history on the enthalpy relaxation in polystyrene are studied by differential scanning calorimetry. The temperature dependence of the specific heat in the liquid and the glassy states, that of relaxation time, and the exponent of the Kohlrausch-Williams-Watts function are determined by measurements of the thermal response against sinusoidal temperature variation. A phenomenological model equation previously proposed to interpret the memory effect in the frozen state is applied to the enthalpy relaxation and the evolution of entropy under a given thermal history is calculated. The annealing below the glass transition temperature produces two effects on enthalpy relaxation: the decay of excess entropy with annealing time in the early stage of annealing and the increase in relaxation time due to physical aging in the later stage. The crossover of these effects is reflected in the variation of temperature of the maximum specific heat observed in the heating process after annealing and cooling.

  20. Cooperativity, partially bound states, and enthalpy-entropy compensation.

    Science.gov (United States)

    Hunter, Christopher A; Tomas, Salvador

    2003-11-01

    Efforts to develop a quantitative understanding of molecular recognition rely on the additivity of individual intermolecular interactions, and cooperativity represents one of the major potential stumbling blocks. A chemical double-mutant cycle has been used to experimentally measure cooperativity between functional group interactions within a complex framework. The interaction between two aromatic groups varies by 0.2 +/- 0.4 kJ mol(-1) in synthetic H-bonded complexes that differ by 8-13 kJ mol(-1) in overall stability. In these systems, the free energies associated with individual intermolecular interactions can therefore be reliably treated in an additive fashion. The results suggest that alternative explanations should be considered for cooperative phenomena observed in other systems, and a rationale based on the population of partially bound states in flexible molecules is proposed to account for the enthalpic chelate effect and enthalpy-entropy compensation. PMID:14652069

  1. Dissociation dynamics of methylal

    Energy Technology Data Exchange (ETDEWEB)

    Beaud, P.; Frey, H.-M.; Gerber, T.; Mischler, B.; Radi, P.P.; Tzannis, A.-P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The dissociation of methylal is investigated using mass spectrometry, combined with a pyrolytic radical source and femtosecond pump probe experiments. Based on preliminary results two reaction paths of methylal dissociation are proposed and discussed. (author) 4 fig., 3 refs.

  2. Calculations for axial compressor blading with uniform inlet enthalpy and radial enthalpy gradient

    OpenAIRE

    Schlachter, W

    1981-01-01

    A computer program was used to calculate the radial distribution of flow parameters in an axial compressor stage designed to have a symmetrical velocity diagram at the mean radius and particular variations of reaction from hub to tip. Uniform energy addition was assumed to occur in the rotor. Both cases of uniform enthalpy and uniform radial enthalpy gradient at the entrance to the stage were considered. Advantages were found in the selection of fully symmetric blading and in the use of the i...

  3. Kinetic evidence of an apparent negative activation enthalpy in an organocatalytic process

    KAUST Repository

    Han, Xiao

    2013-08-30

    A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity.

  4. 与蛋白质调控DNA空穴迁移相关的具有负离解能特征的亚稳态氢键%Metastable Hydrogen-bonds Featuring Negative Dissociation Energies in Protein-bound DNA in Hole Migration

    Institute of Scientific and Technical Information of China (English)

    王梅; 王军; 步宇翔

    2015-01-01

    利用密度泛函理论方法研究了作为空穴迁移载体的蛋白质复合的DNA三聚体( Protonated arginine…guanine…cytosine, ArgH+-GC)的氢键性质.结果表明,空穴迁移通过该载体单元时此类氢键表现为亚稳态,且具有明显的负离解能.正常情况下ArgH+基团在大小沟均能与GC碱对形成氢键,且具有正的离解能.然而,当空穴转移至此将削弱氢键至亚稳态,使之具有一定的离解势垒和负的离解能.这种势垒抑制的负离解能现象意味着由于空穴俘获导致此三聚体结构单元在它的 ArgH+…N7/O6键区储存了一定的能量(约108.78 kJ/mol).该氢键离解通道受控于此键区两个相关组分之间的静电排斥和氢键吸引之间的平衡以及这两个相反作用随氢键距离不同的衰减速率.基于电子密度分布的拓扑性质以及键临界点的Laplacian数值分析澄清了此类特殊的能量现象主要源自通过高能氢键(ArgH+…N7/O6)连接的授受体间的静电排斥.进一步空穴俘获诱导的G→C质子转移可扩展负离解能区至ArgH+…N7/O6和Watson-Crick( WC)氢键区.另外, ArgH+结合到GC的大小沟增加其电离势,因此削弱其空穴传导能力,削弱程度取决于ArgH+与GC的距离.推而广之,在protonated lysine-GC和protonated histidine-GC体系也可观察到类似的现象.显然,此类性质可调的亚稳态氢键可调控DNA空穴迁移机理.此工作为理解蛋白质调控的DNA空穴迁移机理提供了重要的能量学信息.%We theoretically investigated the properties of hydrogen bonds in the protein-bound DNA trimer( protona-ted arginine…guanine…cytosine, ArgH+-GC) units as hole migration carriers using density functional theory calcula-tions. Results suggest these hydrogen bonds are metastable and feature considerable negative dissociation energies up-on hole migration through the ArgH+-GC units of the carriers. Normally, the ArgH+ group can H-bond with the gua-nine-cytosine( GC

  5. DFT Study on the Co-Xe Bond in the HCo(CO3Xe Adduct

    Directory of Open Access Journals (Sweden)

    Tamás Kégl

    2014-01-01

    Full Text Available The metal-xenon interaction has been studied in hydrido-cobalt-carbonyl complexes by means of density functional methods. The method of choice has been selected after testing various functionals including dispersion correction on the bond dissociation enthalpy of Xe in the Cr(CO5Xe adduct. In general, the long range corrected versions of popular gradient-corrected functionals performed well. In particular, LC-mPWPW91 resulted in a perfect match with available experimental data; therefore this functional was selected for the computation of HCo(CO3Xe adducts. For HCo(CO3Xe two isomers have been located; the structure with CS symmetry has proved to be more stable by 5.3 kcal/mol than the C3V adduct in terms of free energy. The formation of HCo(CO3Xe is, however, endergonic by 3.5 kcal/mol for the CS isomer.

  6. High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formation of nickel carbide (NiC) and its cation (NiC+).

    Science.gov (United States)

    Lau, Kai-Chung; Chang, Yih Chung; Shi, Xiaoyu; Ng, C Y

    2010-09-21

    The ionization energy (IE) of NiC and the 0 K bond dissociation energies (D(0)) and heats of formation at 0 K (ΔH(o)(f0)) and 298 K (ΔH(o)(f298)) for NiC and NiC(+) are predicted by the wavefunction based CCSDTQ(Full)/CBS approach and the multireference configuration interaction (MRCI) method with Davidson correction (MRCI+Q). The CCSDTQ(Full)/CBS calculations presented here involve the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations along with the zero-point vibrational energy (ZPVE), high-order correlation, core-valence electronic (CV), spin-orbit coupling (SO), and scalar relativistic effect (SR) corrections. The present calculations provide the correct symmetry predictions for the ground states of NiC and NiC(+) to be (1)∑(+) and (2)∑(+), respectively. The CCSDTQ(Full)/CBS IE(NiC)=8.356 eV is found to compare favorably with the experimental IE value of 8.372 05±0.000 06 eV. The predicted IE(NiC) value at the MRCI+Q/cc-pwCV5Z level, including the ZPVE, SO, and SR effects is 8.00 eV, which is 0.37 eV lower than the experimental value. This work together with the previous experimental and theoretical investigations supports the conclusion that the CCSDTQ(Full)/CBS method is capable of providing reliable IE predictions for 3d-transition metal carbides, such as FeC and NiC. Furthermore, the CCSDTQ(Full)/CBS calculations give the prediction of D(0)(Ni-C)-D(0)(Ni(+)-C)=0.688 eV, which is also consistent with the experimental determination of 0.732 21±0.000 06 eV, whereas the MRCI+Q calculations (with relativistic and CV effects) predict a significantly lower value of 0.39 eV for D(0)(Ni-C)-D(0)(Ni(+)-C). The analysis of the correction terms shows that the CV and valence-valence electronic correlations beyond CCSD(T) wavefunction and the relativistic effect make significant contributions to the calculated thermochemical properties of NiC/NiC(+). For the experimental D(0) and ΔH(o)(f0) values of

  7. Gas phase enthalpies of formation of monobromophenols

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro da Silva, Manuel A.V. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)], E-mail: risilva@fc.up.pt; Lobo Ferreira, Ana I.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)

    2009-10-15

    The standard (p{sup 0}=0.1MPa) molar enthalpies of formation of the liquid 2-bromophenol and crystalline 4-bromophenol, respectively, {delta}{sub f}H{sub m}{sup 0}(l)=-(133.5{+-}1.4)kJ.mol{sup -1}and{delta}{sub f}H{sub m}{sup 0}(cr)=-(152.4{+-}1.4)kJ.mol{sup -1}, were derived from the standard molar energies of combustion, in oxygen, to yield CO{sub 2}(g) and HBr . 600H{sub 2}O(l), at T = 298.15 K, measured by rotating-bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpy of vaporization or sublimation of the compounds, {delta}{sub 1}{sup g}H{sub m}{sup 0}=(55.5{+-}1.3)kJ.mol{sup -1}and{delta}{sub cr}{sup g}H{sub m}{sup 0}=(83.1{+-}1.6)kJ.mol{sup -1}. These two thermodynamic parameters yielded the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, of 2- and 4-bromophenol, respectively, {delta}{sub f}H{sub m}{sup 0}(g)=-(78.0{+-}1.9)kJ.mol{sup -1}and{delta}{sub f}H{sub m}{sup 0}(g)=-(69.3{+-}2.1)kJ.mol{sup -1}. The experimental values of the gas-phase enthalpies of formation of each compound were compared with estimates using the empirical scheme developed by Cox and with the calculated values based on high-level density functional theory calculations using the B3LYP hybrid exchange-correlation energy functional at the 6-311++G(d,p) basis set.

  8. High enthalpy hypersonic boundary layer flow

    Science.gov (United States)

    Yanow, G.

    1972-01-01

    A theoretical and experimental study of an ionizing laminar boundary layer formed by a very high enthalpy flow (in excess of 12 eV per atom or 7000 cal/gm) with allowance for the presence of helium driver gas is described. The theoretical investigation has shown that the use of variable transport properties and their respective derivatives is very important in the solution of equilibrium boundary layer equations of high enthalpy flow. The effect of low level helium contamination on the surface heat transfer rate is minimal. The variation of ionization is much smaller in a chemically frozen boundary layer solution than in an equilibrium boundary layer calculation and consequently, the variation of the transport properties in the case of the former was not essential in the integration. The experiments have been conducted in a free piston shock tunnel, and a detailed study of its nozzle operation, including the effects of low levels of helium driver gas contamination has been made. Neither the extreme solutions of an equilibrium nor of a frozen boundary layer will adequately predict surface heat transfer rate in very high enthalpy flows.

  9. A computational study on structure, stability and bonding in Noble Gas bound metal Nitrates, Sulfates and Carbonates (Metal = Cu, Ag, Au)

    Indian Academy of Sciences (India)

    MANAS GHARA; SUDIP PAN; JYOTIRMOY DEB; ANAND KUMAR; UTPAL SARKAR; PRATIM KUMAR CHATTARAJ

    2016-10-01

    A density functional theory based study is performed to investigate the noble gas (Ng = Ar-Rn) binding ability of nitrates, sulfates and carbonates of noble metal (M). Their ability to bind Ng atoms is assessed through bond dissociation energy and thermochemical parameters like dissociation enthalpy and dissociation free energy change corresponding to the dissociation of Ng bound compound producing Ngand the respective salt. The zero-point energy corrected dissociation energy values per Ng atom for the dissociation process producing Ng atom(s) and the corresponding salts range within 6.0–13.1 kcal/mol in NgCuNO₃, 3.1–9.8 kcal/mol in NgAgNO₃, 6.0–13.2 kcal/mol in NgCuSO₄, 3.2–10.1 kcal/mol in NgAgSO₄, 5.1–11.7 kcal/mol in Ng₂Cu₂SO₄, 2.5–8.6 kcal/mol in Ng₂Ag₂SO₂, 8.1–19.9 kcal/mol in Ng₂Au2SO₂, 5.7–12.4 kcal/mol in NgCuCO₃, 2.3–8.0 kcal/mol in Ng₂Ag₂CO₃ and 7.3–18.2 kcal/mol in Ng₂Au₂CO₃, with a gradual increase in moving from Ar to Rn. For a given type of system, the stability of Ng bound analogues follows the order as Au > Cu > Ag. All dissociation processes are endothermic in nature whereas they become endergonic as well in most of the cases of Kr-Rn bound analogues at 298 K. Natural population analysis along with the computation of Wiberg bond indices, and electron density analyses provide insights into the nature of the Ng-M bonds. The Ng-M bonds can be represented as partial covalent bonds as supported by the different electron density descriptors.

  10. Enthalpy of sublimation in the study of the solid state of organic compounds. Application to erythritol and threitol.

    Science.gov (United States)

    Lopes Jesus, A J; Tomé, Luciana I N; Eusébio, M Ermelinda; Redinha, J S

    2005-09-29

    The enthalpies of sublimation of erythritol and L-threitol have been determined at 298.15 K by calorimetry. The values obtained for the two diastereomers differ from one another by 17 kJ mol(-1). An interpretation of these results is based on the decomposition of this thermodynamic property in a term coming from the intermolecular interactions of the molecules in the crystal (delta(int)H degrees) and another one related with the conformational change of the molecules on going from the crystal lattice to the most stable forms in the gas phase (delta(conf)H degrees). This last term was calculated from the values of the enthalpy of the molecules in the gas state and of the enthalpy of the isolated molecules with the crystal conformation. Both quantities were obtained by density functional theory (DFT) calculations at the B3LYP/6-311G++(d,p) level of theory. The results obtained in this study show that the most important contribution to the differences observed in the enthalpy of sublimation are the differences in the enthalpy of conformational change (13 kJ mol(-1)) rather than different intermolecular forces exhibited in the solid phase. This is explained by the lower enthalpy of threitol in the gas phase relative to erythritol, which is attributed to the higher strength of the intramolecular hydrogen bonds in the former. The comparison of the calculated infrared spectra obtained for the two compounds in the gas phase supports this interpretation.

  11. Enthalpy-driven interactions with sulfated glycosaminoglycans promote cell membrane penetration of arginine peptides.

    Science.gov (United States)

    Takechi-Haraya, Yuki; Nadai, Ryo; Kimura, Hitoshi; Nishitsuji, Kazuchika; Uchimura, Kenji; Sakai-Kato, Kumiko; Kawakami, Kohsaku; Shigenaga, Akira; Kawakami, Toru; Otaka, Akira; Hojo, Hironobu; Sakashita, Naomi; Saito, Hiroyuki

    2016-06-01

    The first step of cell membrane penetration of arginine peptides is thought to occur via electrostatic interactions between positive charges of arginine residues and negative charges of sulfated glycosaminoglycans (GAGs) on the cell surface. However, the molecular interaction of arginine peptides with GAG still remains unclear. Here, we compared the interactions of several arginine peptides of Tat, R8, and Rev and their analogues with heparin in relation to the cell membrane penetration efficiency. The high-affinity binding of arginine peptides to heparin was shown to be driven by large favorable enthalpy contributions, possibly reflecting multidentate hydrogen bondings of arginine residues with sulfate groups of heparin. Interestingly, the lysine peptides in which all arginine residues are substituted with lysine residues exhibited negligible binding enthalpy despite of their considerable binding to heparin. In CHO-K1 cells, arginine peptides exhibited a great cell-penetrating ability whereas their corresponding lysine peptides did not penetrate into cells. The degree of cell penetration of arginine peptides markedly decreased by the chlorate treatment of cells which prevents the sulfation of GAG chains. Significantly, the cell penetration efficiency of arginine peptides was found to be correlated with the favorable enthalpy of binding to heparin. These results suggest that the enthalpy-driven strong interaction with sulfated GAGs such as heparan sulfate plays a critical role in the efficient cell membrane penetration of arginine peptides.

  12. Dissociative Adsorption of Molecules on Graphene and Silicene

    CERN Document Server

    Gurel, H Hakan; Ciraci, S

    2014-01-01

    We study the interaction of H$_2$, O$_2$, CO, H$_2$O and OH molecules with the vacancy defects of graphene and silicene. Atoms around the bare vacancy reconstruct and specific chemically active sites are created. While H$_2$, O$_2$ and CO remain intact on both pristine graphene and silicene, these molecules can dissociate when they are placed at the close proximity of these chemically active sites and nucleate centers for the hydrogenation and oxygenation. Saturation of the dangling bonds at the defect sites by constituent atoms of dissociated molecules gives rise to significant modification of electronic and magnetic properties. We analyzed the mechanism of the dissociation and revealed a concerted action of surrounding host atoms together with dissociated molecules to lower the energy barrier needed for dissociation. The dissociations of H$_2$O and OH are hindered by high energy barriers. Our study suggests that graphene and silicene can be functionalized by creating meshes of single vacancy, where specific...

  13. Is uracil aromatic? The enthalpies of hydrogenation in the gaseous and crystalline phases, and in aqueous solution, as tools to obtain an answer.

    Science.gov (United States)

    Galvão, Tiago L P; Rocha, Inês M; da Silva, Maria D M C Ribeiro; da Silva, Manuel A V Ribeiro

    2013-07-18

    The enthalpy of hydrogenation of uracil was derived from the experimental enthalpies of formation, in the gaseous phase, of uracil and 5,6-dihydrouracil, in order to analyze its aromaticity. The enthalpy of formation of 5,6-dihydrouracil was obtained from combustion calorimetry, Knudsen effusion technique and Calvet microcalorimetry results. High-level computational methods were tested for the enthalpy of hydrogenation of uracil, but only with G3 was possible to obtain results in agreement with the experimental ones. It was found that uracil possesses 30.0% of aromatic character in the gaseous phase. Using both implicit, explicit, and hybrid solvation methods, it was possible to obtain a reference value for the enthalpy of hydrogenation of uracil in the aqueous solution and the effect of polarity and hydrogen bonds on the aromaticity of uracil was analyzed. The value of the hydrogenation enthalpy of uracil in aqueous solution was compared with the experimental value in the crystal phase, also dominated by polarity and hydrogen bonds, derived from combustion calorimetry results. The supramolecular effects on the crystal lattice were explored by the computational simulation of π-π staking dimers and hydrogen bonded dimers.

  14. Methane hydrate formation and dissociation in synthetic seawater

    Institute of Scientific and Technical Information of China (English)

    Vikash Kumar Saw; Iqbal Ahmad; Ajay Mandal; G.Udayabhanu; Sukumar Laik

    2012-01-01

    The formation and dissociation of methane gas hydrate at an interface between synthetic seawater (SSW) and methane gas have been experimentally investigated in the present work.The amount of gas consumed during hydrate formation has been calculated using the real gas equation.Induction time for the formation of hydrate is found to depend on the degree of subcooling.All the experiments were conducted in quiescent system with initial cell pressure of 11.14 MPa.Salinity effects on the onset pressure and temperature of hydrate formation are also observed.The dissociation enthalpies of methane hydrate in synthetic seawater were determined by Clausius-Clapeyron equation based on the measured phase equilibrium data.The dissociation data have been analyzed by existing models and compared with the reported data.

  15. Enthalpy Probe Technique for Thermal Plasma Diagnostics

    Institute of Scientific and Technical Information of China (English)

    冯晓珍

    2003-01-01

    The measuring principle and experimental results of the enthalpy probe techniquefor thermal plasma diagnostics are presented. Its calibration and errors are discussed. Typicalresults are presented for the system operation in an Ar/H2(5 % H2) plasma arc jet under a reactorchamber pressure of 101.3 kPa. The plasma temperature and velocity profiles are measured. Thecenter temperature and velocity are 6600 K and 850 m/s for plasma power 9 kW at axial locationof 17 mm.

  16. Effects of partitioned enthalpy of mixing on glass-forming ability.

    Science.gov (United States)

    Song, Wen-Xiong; Zhao, Shi-Jin

    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 (ΔEnn), strain part (ΔEstrain), and non-bond part (ΔEnnn). We find that a large negative ΔEnn 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 (ΔEnn/2 + ΔEstrain) 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.

  17. Effects of partitioned enthalpy of mixing on glass-forming ability

    Science.gov (United States)

    Song, Wen-Xiong; Zhao, Shi-Jin

    2015-04-01

    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 Enn), strain part (Δ Estrain), and non-bond part (Δ Ennn). We find that a large negative Δ Enn 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 Enn/2 + Δ Estrain) 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.

  18. Molal Enthalpy of Solution of Ionic Liquid [C2mim][GaCl4

    Institute of Scientific and Technical Information of China (English)

    GUAN,Wei; LIU,Li; WANG,Caixia; YANG,Jiazhen

    2009-01-01

    An ionic liquid (IL),[C2mim][GaCl4](l-ethyl-3-methylimidazolium chlorogallate),was prepared by directly mixing 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and anhydrous GaCI3 with a molar ratio of 1/1 under dry argon.The molal enthalpies of solution,△sHm,of [C2mim][GaCl4],were measured over a molality range of about 0.008-0.1 mol·kg 1 by a solution reaction isoperibol calorimeter at 298.15 K.Considering the hydrolization of anion [GaCl4]- in dissolution process of the IL,a new method of determining the standard molal enthalpy of solution,△sH(⊙)m,was put forward on the basis of Pitzer's mixed electrolyte solution theory so that △sH(⊙)m = -132kJ·mol-1 and the sum of Pitzer's parameters;4β(0)GaCl + 4β(0)[C2mim].Cl + ΦGa,[C2mim]= -0.1373076,β(1)LGa,Cl + β(1)L[C2mim].C=0.3484209 were obtained.In terms of thermodynamic cycle and Glasser's theory of lattice energy for IL,the dissociation enthalpy of [GaCl4]-(g),△Hdis([GaCl4]-)≈5855 kJ·mol-1,that is enthalpy change for the reaction:[GaCl4]-(g)→Ga3+(g) +4Cl- (g),was estimated.

  19. Thermal dissociation and unfolding of insulin

    DEFF Research Database (Denmark)

    Huus, Kasper; Havelund, Svend; Olsen, Helle B;

    2005-01-01

    The thermal stability of human insulin was studied by differential scanning microcalorimetry and near-UV circular dichroism as a function of zinc/protein ratio, to elucidate the dissociation and unfolding processes of insulin in different association states. Zinc-free insulin, which is primarily...... dimeric at room temperature, unfolded at approximately 70 degrees C. The two monomeric insulin mutants Asp(B28) and Asp(B9),Glu(B27) unfolded at higher temperatures, but with enthalpies of unfolding that were approximately 30% smaller. Small amounts of zinc caused a biphasic thermal denaturation pattern...... of insulin. The biphasic denaturation is caused by a redistribution of zinc ions during the heating process and results in two distinct transitions with T(m)'s of approximately 70 and approximately 87 degrees C corresponding to monomer/dimer and hexamer, respectively. At high zinc concentrations (>or=5 Zn(2...

  20. Prediction of saturated liquid enthalpy of refrigerant mixtures

    Institute of Scientific and Technical Information of China (English)

    CHEN ZeShao; CHEN JianXin; HU Peng

    2007-01-01

    New corresponding temperature and corresponding enthalpy of refrigerant mixtures were defined. The relationship between saturated liquid corresponding enthalpy and corresponding temperature of refrigerant mixtures accorded with that of pure components. The characteristic parameters of saturated liquid enthalpy difference of refrigerant mixtures were calculated by three methods according to the different application conditions. The generalized equation of saturated liquid enthalpy of refrigerant mixtures was presented. The calculated values were compared with the values in literature for five ternary and binary refrigerant mixtures, namely R404A, R407A, R407B, R32/R134a, and R410A. The overall average absolute deviation was less than 1.0%.

  1. Experimental evaluation of enthalpy efficiency and gas-phase contaminant transfer in an enthalpy recovery unit with polymer membrane foils

    DEFF Research Database (Denmark)

    Nie, Jinzhe; Yang, Jianrong; Fang, Lei;

    2015-01-01

    Experimental studies were conducted in a laboratory setting to investigate the enthalpy efficiency and gas-phase contaminant transfer in a polymer membrane enthalpy recovery unit. One commercially available polymer membrane enthalpy recovery unit was used as a reference unit. Simulated indoor air...... and downstream of the unit, the temperature efficiencies, humidity efficiencies, enthalpy efficiencies, and contaminant transfer ratios were calculated. The results showed that over 60% of enthalpy recovery efficiency could be achieved and that the contaminant transfer ratios were in the range of 5.4% to 9.......0%. The enthalpy efficiency in cold-dry climate conditions was slightly higher than in hot-humid climate conditions. The contaminant transfer ratio were independent of any hygrothermal difference between indoor and outdoor air and was unrelated to its molecule size or water solubility. The conclusion indicated...

  2. Vacancy Formation Enthalpy in Polycrystalline Depleted Uranium

    Science.gov (United States)

    Lund, K. R.; Lynn, K. G.; Weber, M. H.; Okuniewski, M. A.

    2013-06-01

    Positron Annihilation Spectroscopy was performed as a function of temperature and beam energy on polycrystalline depleted uranium (DU) foil. Samples were run with varying heat profiles all starting at room temperature. While collecting Doppler-Broadening data, the temperature of the sample was cycled several times. The first heat cycle shows an increasing S-parameter near temperatures of 400K to 500K much lower than the first phase transition of 941K indicating increasing vacancies possibly due to oxygen diffusion from the bulk to the surface. Vacancy formation enthalpies were calculated fitting a model to the data to be 1.6± 0.16 eV. Results are compared to previous work [3,4].

  3. Controllable dissociations of PH3 molecules on Si(001)

    Science.gov (United States)

    Liu, Qin; Lei, Yanhua; Shao, Xiji; Ming, Fangfei; Xu, Hu; Wang, Kedong; Xiao, Xudong

    2016-04-01

    We demonstrate for the first time to our knowledge that controllable dissociation of PH3 adsorption products PH x (x = 2, 1) can be realized by STM (scanning tunneling microscope) manipulation techniques at room temperature. Five dissociative products and their geometric structures are identified via combining STM experiments and first-principle calculations and simulations. In total we realize nine kinds of controllable dissociations by applying a voltage pulse among the PH3-related structures on Si(001). The dissociation rates of the five most common reactions are measured by the I-t spectrum method as a function of voltage. The suddenly increased dissociation rate at 3.3 V indicates a transition from multivibrational excitation to single-step excitation induced by inelastic tunneling electrons. Our studies prove that selectively breaking the chemical bonds of a single molecule on semiconductor surface by STM manipulation technique is feasible.

  4. Partial molar enthalpies and reaction enthalpies from equilibrium molecular dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Schnell, Sondre K. [Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft (Netherlands); Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim (Norway); Skorpa, Ragnhild; Bedeaux, Dick [Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim (Norway); Kjelstrup, Signe [Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim (Norway); Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft (Netherlands); Vlugt, Thijs J. H. [Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft (Netherlands); Simon, Jean-Marc, E-mail: jmsimon@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303, CNRS-Université de Bourgogne, 9, av. Savary, 21000 Dijon (France)

    2014-10-14

    We present a new molecular simulation technique for determining partial molar enthalpies in mixtures of gases and liquids from single simulations, without relying on particle insertions, deletions, or identity changes. The method can also be applied to systems with chemical reactions. We demonstrate our method for binary mixtures of Weeks-Chandler-Anderson particles by comparing with conventional simulation techniques, as well as for a simple model that mimics a chemical reaction. The method considers small subsystems inside a large reservoir (i.e., the simulation box), and uses the construction of Hill to compute properties in the thermodynamic limit from small-scale fluctuations. Results obtained with the new method are in excellent agreement with those from previous methods. Especially for modeling chemical reactions, our method can be a valuable tool for determining reaction enthalpies directly from a single MD simulation.

  5. Vapor Pressure, Vaporization Enthalpy, Standard Enthalpy of Formation and Standard Entropy of n-Butyl Carbamate

    Institute of Scientific and Technical Information of China (English)

    Zuoxiang Zeng⁎; Zhihong Yang; Weilan Xue⁎; Xiaonan Li

    2014-01-01

    The vapor pressures of n-butyl carbamate were measured in the temperature range from 372.37 K to 479.27 K and fitted with Antoine equation. The compressibility factor of the vapor was calculated with the Virial equation and the second virial coefficient was determined by the Vetere model. Then the standard enthalpy of vaporization for n-butyl carbamate was estimated. The heat capacity was measured for the solid state (299.39–324.2 K) and liquid state (336.65–453.21 K) by means of adiabatic calorimeter. The standard en-thalpy of formationΔfHϴ[crystal (cr),298.15 K] and standard entropy Sϴ(crystal,298.15 K) of the sub-stance were calculated on the basis of the gas-phase standard enthalpy of formationΔfHϴ(g,298.15 K) and gas-phase standard entropy Sϴ(g,298.15 K), which were estimated by the Benson method. The results are acceptable, validated by a thermochemical cycle.

  6. Enthalpy of solution of rubidium sulphate in water

    Energy Technology Data Exchange (ETDEWEB)

    Apelblat, A. (Ben-Gurion Univ. of the Negev, Beersheba (Israel). Dept. of Chemical Engineering)

    1984-11-01

    Molar enthalpies of solution of Rb/sub 2/SO/sub 4/ in water at 298.15 K were measured in an LKB calorimeter. The molar enthalpy of solution extrapolated to infinite dilution is (23509 +- 38) J.mol/sup -1/.

  7. 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.

  8. Enthalpy: A Metaphor for a Design Guide for Conversations.

    Science.gov (United States)

    Dyer, Gordon

    1996-01-01

    Provides insights into the design of effective educational planning conversations derived from the metaphor of enthalpy (the amount of heat energy released when chemical reactions occur). Interprets enthalpy changes in the context of energy and the dynamics necessary to sustain an effective systems design conversation. (AEF)

  9. Standard molar enthalpy of formation of methoxyacetophenone isomers

    International Nuclear Information System (INIS)

    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 (po = 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

  10. 天然气水合物生成焓的测定%Measurement of the Molar Enthalpies of Formation of Natural Gas Hydrates

    Institute of Scientific and Technical Information of China (English)

    高军; Kenneth N.Marsh

    2003-01-01

    实验测定了在压力2 000 kPa和6 700 kPa条件下,含有甲烷、乙烷、丙烷和异丁烷等典型组成的天然气其水合物的生成焓.实验所用水合物是在微分扫描量热仪里直接生成,且在指定的压力下进行恒压温度扫描,同时测定水合物中的水气比和生成焓.其误差小于1.5%.实验结果表明,在不同的实验压力条件下,水合物的生成焓与水气比变化较小.%This paper reports the measurement of the molar enthalpies of natural gas hydrates for typical natural gas mixtures containing methane, ethane, propane and iso-butaneat pressures in the vicinity of 2 000 kPa and 6 700 kPa, in a multicell differential scanningcalorimeter using modified high pressure cells. The natural gas hydrate was formed by cycling the solution in the vicinity of the ice point. The mass of hydrate formed was calculatedfrom the measurement of the enthalpy of fusion of water after the hydrate was formed andafter the hydrate was dissociated. The enthalpy of fusion of water and the enthalpy of gashydrate dissociation were determined from the calorimeter response during a slow temperature scan at a constant pressure. The amount of gas released from the dissociation of the by-drate was determined from the volume change of the high pressure pump required to maintainthe constant pressure, and the amount of the hydrate formed was determined from the mea-surement of the enthalpies of fusion of water before and after the dissociation of the hydrate.The occupation number (the ratio of the water to gas) and the enthalpy of the hydrate formation have an uncertainty of 1.5 %. The results show that the enthalpies of the hydrateformation and the occupation number are essentially independent of pressure.

  11. Calorimetric Studies on Enthalpy Relaxation in Maltitol Glass Transition Based on Phenomenological Models

    Institute of Scientific and Technical Information of China (English)

    YE Bin; GAO Cai; YANG Suo; LIU Xiang-nong; JIANG Bin

    2012-01-01

    To investigate the enthalpy relaxation behavior of maltitol glass system,differential scanning calorimetry (DSC) was used to obtain the specific heat capacity[Cp(T)] near the glass transition temperature(Tg) at different cooling rates ranged between 1 and 20 K/min.Three phenomenological models of enthalpy relaxation,ToolNarayanaswamy-Moynihan(TNM) model,Adam-Gibbs-Vogel(AGV) model and Gómez Ribelles(GR) model,were used to simulate the experimental data.The models' parameters were obtained via a curve-fitting method.The results indicate that TNM and AGV models gave the almost identical prediction powers and can reproduce the curves of experimental Cp(T) very well.However,the prediction power of GR model evolved from configurational entropy approach is not so good as those of TNM and AGV models.In particular,the metastable limit state parameter(δ) introduced by Gómez Ribelles has insignificant effect on the enthalpy relaxation of the small molecular hydrogen-bonding glass system.

  12. Constant enthalpy change value during pyrophosphate hydrolysis within the physiological limits of NaCl.

    Science.gov (United States)

    Wakai, Satoshi; Kidokoro, Shun-ichi; Masaki, Kazuo; Nakasone, Kaoru; Sambongi, Yoshihiro

    2013-10-11

    A decrease in water activity was thought to result in smaller enthalpy change values during PPi hydrolysis, indicating the importance of solvation for the reaction. However, the physiological significance of this phenomenon is unknown. Here, we combined biochemistry and calorimetry to solve this problem using NaCl, a physiologically occurring water activity-reducing reagent. The pyrophosphatase activities of extremely halophilic Haloarcula japonica, which can grow at ∼4 M NaCl, and non-halophilic Escherichia coli and Saccharomyces cerevisiae were maximal at 2.0 and 0.1 M NaCl, respectively. Thus, halophilic and non-halophilic pyrophosphatases exhibit distinct maximal activities at different NaCl concentration ranges. Upon calorimetry, the same exothermic enthalpy change of -35 kJ/mol was obtained for the halophile and non-halophiles at 1.5-4.0 and 0.1-2.0 M NaCl, respectively. These results show that solvation changes caused by up to 4.0 M NaCl (water activity of ∼0.84) do not affect the enthalpy change in PPi hydrolysis. It has been postulated that PPi is an ATP analog, having a so-called high energy phosphate bond, and that the hydrolysis of both compounds is enthalpically driven. Therefore, our results indicate that the hydrolysis of high energy phosphate compounds, which are responsible for biological energy conversion, is enthalpically driven within the physiological limits of NaCl.

  13. Cold-induced precipitation of a monoclonal IgM: a negative activation enthalpy reaction.

    Science.gov (United States)

    Meliga, Stefano C; Farrugia, William; Ramsland, Paul A; Falconer, Robert J

    2013-01-17

    Cold-induced precipitation of a monoclonal IgM cryoglobulin isolated from a patient with Waldenström's macroglobulinemia was observed to have a negative activation enthalpy. The rate of the reaction increased, as the temperature decreased. Differential scanning calorimetry of the monoclonal IgM showed precipitation as an inverted peak during a downward temperature scan. The transition temperature was between 14 and 15 °C and was possibly concentration dependent. At temperatures below the transition the precipitation was best described by second-order kinetics. The difference in change in enthalpy between precipitation and disassociation suggests that cold-induced precipitation had a fast precipitation stage followed by a slower consolidation reaction. Negligible curvature of the Eyring plot suggested the precipitation reaction was dominated by van der Waal forces and hydrogen bonding. Conversely, during an upward temperature scan, disassociation was observed as a positive enthalpy peak. This reaction had two stages, a reaction undoing consolidation followed by heat-induced disassociation that had first-order kinetics.

  14. Dynamics of unimolecular dissociation of silylene

    Science.gov (United States)

    NoorBatcha, I.; Raff, Lionel M.; Thompson, Donald L.; Viswanathan, R.

    1986-04-01

    The semiempirical valence-bond surface formulated by Viswanathan et al. [J. Phys. Chem. 89, 1428 (1985)] for the unimolecular dissociation of SiH2 has been fitted to an analytical function of the type suggested by Murrell and co-workers [J. Phys. Chem. 88, 4887 (1984)]. The fitted surface accurately represents most of the experimental and CI results. The dynamics of the unimolecular dissociation of SiH2 to form Si and H2 have been investigated by classical trajectory methods on this fitted surface. The effect of describing the initial state of the molecule using normal and local mode approximations has been studied. In spite of the presence of the heavier atom, no bond or mode specificity is observed. The product energy distribution is found to be statistical. Using the RRK model, the high-pressure limiting rate coefficient is found to be k(T,∞)=3.38×1012 exp[-61.6 kcal mol-1/RT] s-1, which is less than the dissociation rate for SiH4. This has been attributed to the higher activation energy for SiH2 and to a statistical factor.

  15. Dissociative charge exchange of H2+

    International Nuclear Information System (INIS)

    This thesis is devoted to molecular dissociation, in particular the dissociation of the hydrogen molecule H2 arising from electron capture of its ion H2+ in a collision. Thereby the important practical question how a chemical bond can be broken is implicitly addressed. This thesis opens (chapter I) with an overview of the available experimental approaches in molecular physics. Further the simple Demkov model for NRCE is described. In chapter II a novel experimental technique for measurements on dissociative processes is introduced which combines a high efficiency with a high energy resolution. A detailed description of the techniques applied in the detector, which has a high spatial and timing resolution with 30 μm and 350 psec FWHM respectively for the detection of one particle, is given in chapter III. A semi-classical theory for NRCE in the medium energy range between a diatomic molecular ion and an atom is developed in chapter IV. The experiments on dissociative charge exchange of H2+ with Ar, Mg, Na and Cs targets at keV energies are described in Chapter V. The predissociation of the c3PIsub(u)-state of H2 populated after charge exchange of H2 with several targets at keV energies; is the subject of chapter VI. In chapter VII, orientational oscillations in the cross section for charge exchange of H2+ with alkali targets are discussed. The last chapter deals with predissociation of highly excited states in H2. (Auth.)

  16. Infrared multiphoton dissociation processes of some halogenated hydrocarbons

    International Nuclear Information System (INIS)

    We review our studies on mechanisms and dynamics of infrared multiphoton dissociation of CF3CHClF, C2HCl3, CBrF2CHClF, CBrF2CHBrF, CBrF2CBrClF, and c-C4F8 using a photofragmentation translational spectroscopy and ab initio MO calculations. In the case of CF3CHClF, three-centered HCl elimination and C-Cl bond rupture occurred competitively as primary dissociation processes. The center-of-mass translational energy distribution of the products produced by the HCl elimination indicates that an exit barrier of several kcal/mol exists in the potential energy surface of the reaction. In the case of C2HCl3, three- and four-centered eliminations of HCl occurred competitively. Halogenated ethanes containing bromine atoms dissociated through a C-Br bond rupture channel. The halogenated ethyl radicals produced by the C-Br bond ruptures subsequently dissociated through a C-halogen bond rupture channel. The translational energy distributions for the C-halogen bond ruptures observed are almost consistent with those calculated by RRKM theory. In the case of c-C4F8, dissociation of c-C4F8 to two C2F4 molecules was observed as a primary process. About 30% of the exit barrier for this reaction is converted to the translational energy of the products. This indicates that the dissociation proceeds through a loose transition state. This conclusion is supported by the transition state structure calculated by an ab initio MO method. (author)

  17. Enthalpy of formation for Cu-Zn-Sn-S (CZTS)

    OpenAIRE

    Baryshev, Sergey V.; Thimsen, Elijah

    2014-01-01

    Herein we report an analytical procedure to calculate the enthalpy of formation for thin film multinary compounds from sputtering rates measured during ion bombardment. The method is based on Sigmund's sputtering theory and the Born-Haber cycle. Using this procedure, an enthalpy of formation for a CZTS film of the composition Cu$_{1.9}$Zn$_{1.5}$Sn$_{0.8}$S$_4$ was measured as -930$\\pm$98 kJ/mol. This value is much more negative than the sum of the enthalpies of formation for the constituent ...

  18. Vapor pressures and enthalpies of vaporization of azides

    Energy Technology Data Exchange (ETDEWEB)

    Verevkin, Sergey P., E-mail: sergey.verevkin@uni-rostock.de [Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, D-18059 Rostock (Germany); Emel' yanenko, Vladimir N. [Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, D-18059 Rostock (Germany); Algarra, Manuel [Centro de Geologia do Porto, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Manuel Lopez-Romero, J. [Department of Organic Chemistry, University of Malaga. Campus de Teatinos s/n, 29071 Malaga (Spain); Aguiar, Fabio; Enrique Rodriguez-Borges, J.; Esteves da Silva, Joaquim C.G. [Centro de Investigacao em Quimica (CIQ-UP), Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal)

    2011-11-15

    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 {Delta}{sub l}{sup g}H{sub 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.

  19. Transition-state enthalpy and entropy effects on reactivity and selectivity in hydrogenolysis of n-alkanes.

    Science.gov (United States)

    Flaherty, David W; Iglesia, Enrique

    2013-12-11

    Statistical mechanics and transition state (TS) theory describe rates and selectivities of C-C bond cleavage in C2-C10 n-alkanes on metal catalysts and provide a general description for the hydrogenolysis of hydrocarbons. Mechanistic interpretation shows the dominant role of entropy, over enthalpy, in determining the location and rate of C-C bond cleavage. Ir, Rh, and Pt clusters cleave C-C bonds at rates proportional to coverages of intermediates derived by removing 3-4 H-atoms from n-alkanes. Rate constants for C-C cleavage reflect large activation enthalpies (ΔH(‡), 217-257 kJ mol(-1)) that are independent of chain length and C-C bond location in C4+ n-alkanes. C-C bonds cleave because of large, positive activation entropies (ΔS(‡), 164-259 J mol(-1) K(-1)) provided by H2 that forms with TS. Kinetic and independent spectroscopic evidence for the composition and structure of these TS give accurate estimates of ΔS(‡) for cleavage at each C-C bond. Large differences between rate constants for ethane and n-decane (~10(8)) reflect an increase in the entropy of gaseous alkanes retained at the TS. The location of C-C bond cleavage depends solely on the rotational entropies of alkyl chains attached to the cleaved C-C bond, which depend on their chain length. Such entropy considerations account for the ubiquitous, but previously unexplained, preference for cleaving nonterminal C-C bonds in n-alkanes. This mechanistic analysis and thermodynamic treatment illustrates the continued utility of such approaches even for hydrogenolysis reactions, with complexity seemingly beyond the reach of classical treatments, and applies to catalytic clusters beyond those reported here (0.6-2.7 nm; Ir, Rh, Pt).

  20. Dissociative Identity Disorder

    Science.gov (United States)

    Schmidt, Tom

    2007-01-01

    Few psychological disorders in the Diagnostic Statistical Manual have generated as much controversy as Dissociative Identity Disorder (DID). For the past 35 years diagnoses of DID, previously referred to as Multiple Personality Disorder (MPD), have increased exponentially, causing various psychological researchers and clinicians to question the…

  1. Pathological Dissociation as Measured by the Child Dissociative Checklist

    Science.gov (United States)

    Wherry, Jeffrey N.; Neil, Debra A.; Taylor, Tamara N.

    2009-01-01

    The component structure of the Child Dissociative Checklist was examined among abused children. A factor described as pathological dissociation emerged that was predicted by participants being male. There also were differences in pathological dissociation between groups of sexually abused and physically abused children. Replication of this factor…

  2. Migration Enthalpy of Thermal Vacancies by Positron Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Emad A. Badawi

    2005-01-01

    @@ The trapping of positrons at vacancy site in some materials provide a new and sensitive method for the equilibrium determination of point defect migration enthalpy. Data are presented for commercial Al-Mg alloys and fitted to a model allowing presentation in the form of Arrhenius plots, hence the migration enthalpy H m iv can bedetermined by the positron annihilation lifetime technique. The results show that the value of Hm iv increases as the concentration of Mg increases.

  3. A General Theoretical Model of Enthalpy-EntropyCompensation

    Institute of Scientific and Technical Information of China (English)

    LIU,Lei; GUO, Qing-Xiang

    2001-01-01

    Enthalpy-entropy compensation remains a mystery in chemistry and biophysics.recent study suggested that the solventreorganization might constitute the physical orihin of the compensation, which was unforumstely not wisely applicable because compensation was also observeserved in solid phade reactions.In this study,a general theoretical model based upon strictmathematical deduction was presented,which indicated thatthe redistribution of the distinguishable subspecies might bethe physical origin of the enthalpy-intropy compensations in solvation and surface adsorption weue discussed.

  4. Enthalpy and Heat Capacity Data for 1,2-Cyclohexanediol

    Institute of Scientific and Technical Information of China (English)

    周彩荣; 章亚东; 蒋登高

    2003-01-01

    The thermodynamic properties of different geometric structures of 1,2-cyclohexanediol which were rarely reported in literature, such as combustion enthalpy, formation enthalpy, melting enthalpy and heat capacities, were determined by NETZSCH DSC 204 Scanning Calorimeter. The relationship between the melting point and the composition for the mixture system of cis-l,2-cyclohexanediol and trans-l,2-cyclohexanediol was investigated and corresponding phase diagram was obtained. "The melting enthalpies of both cis-l,2-cyclohexanediol and trans-l,2-cyclohexanediol are 20.265 kJ·mo1-1 and 16.368 kJ·mo1-1 respectively. The standard combustion enthalpies of cis- and trans-l,2-cyclohexaneddiol were determined by calorimeter. They are respectively -3507.043kJ·mo1-1 and -3497.8kJ·mo1-1 at 298.15 K.The standard formation enthalpies are respectively 568.997kJ·mol-1 and 578.240kJ·mol-1 for cis- and trans-1,2-cyclohexaneddiol.

  5. On the computation of moist-air specific thermal enthalpy

    CERN Document Server

    Marquet, Pascal

    2014-01-01

    The specific thermal enthalpy of a moist-air parcel is defined analytically following a method in which specific moist entropy is derived from the Third Law of thermodynamics. Specific thermal enthalpy is computed by integrating specific heat content with respect to absolute temperature and including the impacts of various latent heats (i.e., solid condensation, sublimation, melting, and evaporation). It is assumed that thermal enthalpies can be set to zero at $0$ K for the solid form of the main chemically inactive components of the atmosphere (solid-$\\alpha$ oxygen and nitrogen, hexagonal ice). The moist thermal enthalpy is compared to already existing formulations of moist static energy (MSE). It is shown that the differences between thermal enthalpy and the thermal part of MSE may be quite large. This prevents the use of MSE to evaluate the enthalpy budget of a moist atmosphere accurately, a situation that is particularly true when dry-air and cloud parcels mix because of entrainment/detrainment processes...

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

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro da Silva, Manuel A.V., E-mail: risilva@fc.up.pt [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); 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. [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)

    2011-09-15

    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{sup 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.

  7. Enthalpy of mixing of liquid Co-Sn alloys.

    Science.gov (United States)

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

    2014-07-01

    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.

  8. Ionic dissociations of chlorosulfonic acid in microsolvated clusters: A density functional theory and ab initio MO study

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Ionic dissociation of chlorosulfonic acid (HSO3Cl) in the molecular clusters HSO3Cl-(H2O)n (n = 1-4) and HSO3Cl-NH3-(H2O)n (n = 0-3) was investigated by density functional theory and ab initio molecular orbital theory. The equilibrium structures, binding energies, and thermodynamic properties, such as relative enthalpy and relative Gibbs free energy, and were calculated using the hybrid density func- tional (B3LYP) method and the second order M?ller-Plesset approximation (MP2) method with the 6-311++G** basis set. Chlorosulfonic acid was found to require a minimum of three water molecules for ionization to occur and at least one water molecule to protonate ammonia. The corresponding clusters with fewer water molecules were found to be strongly hydrogen-bonded. The related properties and acid strength of chlorosulfonic acid were discussed and compared to the acid strengths of perchloric acid and sulfuric acid in the context of clusters with ammonia and water. The relative stabilities of these clusters were also investigated.

  9. Ionic dissociations of chlorosulfonic acid in microsolvated clusters: A density functional theory and ab initio MO study

    Institute of Scientific and Technical Information of China (English)

    LI ShuJin; TAO FuMing; GU RenAo

    2008-01-01

    lonic dissociation of chlorosulfonic acid (HSO3Cl) in the molecular clusters HSO3Cl-(H2O)n (n=1-4) and HSO3Cl-NH3-(H2O)n (n=0-3) was investigated by density functional theory and ab initio molecular orbital theory. The equilibrium structures, binding energies, and thermodynamic properties, such as relative enthalpy and relative Gibbs free energy, and were calculated using the hybrid density func-tional (B3LYP) method and the second order Moller-Plesset approximation (MP2) method with the 6-311++G** basis set. Chlorosulfonic acid was found to require a minimum of three water molecules for ionization to occur and at least one water molecule to protonate ammonia. The corresponding clusters with fewer water molecules were found to be strongly hydrogen-bonded. The related properties and acid strength of chlorosulfonic acid were discussed and compared to the acid strengths of perchloric acid and sulfuric acid in the context of clusters with ammonia and water. The relative stabilities of these clusters were also investigated.

  10. Free-flight measurement technique in the free-piston high-enthalpy shock tunnel.

    Science.gov (United States)

    Tanno, H; Komuro, T; Sato, K; Fujita, K; Laurence, S J

    2014-04-01

    A novel multi-component force-measurement technique has been developed and implemented at the impulse facility JAXA-HIEST, in which the test model is completely unrestrained during the test and thus experiences free-flight conditions for a period on the order of milliseconds. Advantages over conventional free-flight techniques include the complete absence of aerodynamic interference from a model support system and less variation in model position and attitude during the test itself. A miniature on-board data recorder, which was a key technology for this technique, was also developed in order to acquire and store the measured data. The technique was demonstrated in a HIEST wind-tunnel test campaign in which three-component aerodynamic force measurement was performed on a blunted cone of length 316 mm, total mass 19.75 kg, and moment of inertia 0.152 kgm(2). During the test campaign, axial force, normal forces, and pitching moment coefficients were obtained at angles of attack from 14° to 32° under two conditions: H0 = 4 MJ/kg, P0 = 14 MPa; and H0 = 16 MJ/kg, P0 = 16 MPa. For the first, low-enthalpy condition, the test flow was considered a perfect gas; measurements were thus directly compared with those obtained in a conventional blow-down wind tunnel (JAXA-HWT2) to evaluate the accuracy of the technique. The second test condition was a high-enthalpy condition in which 85% of the oxygen molecules were expected to be dissociated; high-temperature real-gas effects were therefore evaluated by comparison with results obtained in perfect-gas conditions. The precision of the present measurements was evaluated through an uncertainty analysis, which showed the aerodynamic coefficients in the HIEST low enthalpy test agreeing well with those of JAXA-HWT2. The pitching-moment coefficient, however, showed significant differences between low- and high-enthalpy tests. These differences are thought to result from high-temperature real-gas effects.

  11. Excess enthalpy of monoethanolamine + ionic liquid mixtures: how good are COSMO-RS predictions?

    Science.gov (United States)

    Gonzalez-Miquel, Maria; Massel, Marjorie; DeSilva, Aruni; Palomar, Jose; Rodriguez, Francisco; Brennecke, Joan F

    2014-10-01

    Mixtures of ionic liquids (ILs) and molecular amines have been suggested for CO2 capture applications. The basic idea is to replace water, which volatilizes in the amine regeneration step and increases the parasitic energy load, with a nonvolatile ionic liquid solvent. To fully understand the thermodynamics of these systems, here experimental excess enthalpies for binary mixtures of monoethanolamine (MEA) and two ILs: 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [hmim][NTf2], and 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [OHemim][NTf2], were obtained by calorimetry, using a Setaram C80 calorimeter, over the whole range of compositions at 313.15 K. Since it is the temperature derivative of the Gibbs energy, enthalpy is a sensitive measure of intermolecular interactions. MEA + [hmim][NTf2] is endothermic and MEA + [OHemim][NTf2] is exothermic. The reliability of COSMO-RS to predict the excess enthalpy of the (MEA+IL) systems was tested based on the implementation of two different molecular models to define the structure of the IL: the IL as separate cation and anion [C+A] and the IL as a bonded single specie [CA]. Quantum-chemical calculations were performed to gain additional insight into the intermolecular interactions between the components of the mixture. For MEA + [hmim][NTf2] both the [C+A] and [CA] models predict endothermic behavior, but the [CA] model is in better agreement with the experimental results. For MEA + [OHemim][NTf2] the [C+A] model provides the best match to the experimental exothermic results. However, what is really surprising is that two different conformations of the cation-anion pair with nearly identical energies in the [CA] model result in completely different (exothermic vs endothermic) predictions of the excess enthalpy. Nonetheless, the results do show that the influence of the structure of the IL on the thermodynamic behavior of the mixture (endothermic vs exothermic) can be attributed

  12. Relationship between the Standard Enthalpy of Formation and the Ratio of Standard Enthalpy of Formation and Exothermic Denitration Decomposition Peak Temperature of M(NTO)n

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A relationship is established, using the least-squares method, between the standard enthalpy of formation and the standard enthalpy of formation divided by the exothermic denitration decomposition peak absolute temperature corresponding to β→0.

  13. Entropy and enthalpy of polyelectrolyte complexation: Langevin dynamics simulations.

    Science.gov (United States)

    Ou, Zhaoyang; Muthukumar, M

    2006-04-21

    We report a systematic study by Langevin dynamics simulation on the energetics of complexation between two oppositely charged polyelectrolytes of same charge density in dilute solutions of a good solvent with counterions and salt ions explicitly included. The enthalpy of polyelectrolyte complexation is quantified by comparisons of the Coulomb energy before and after complexation. The entropy of polyelectrolyte complexation is determined directly from simulations and compared with that from a mean-field lattice model explicitly accounting for counterion adsorption. At weak Coulomb interaction strengths, e.g., in solvents of high dielectric constant or with weakly charged polyelectrolytes, complexation is driven by a negative enthalpy due to electrostatic attraction between two oppositely charged chains, with counterion release entropy playing only a subsidiary role. In the strong interaction regime, complexation is driven by a large counterion release entropy and opposed by a positive enthalpy change. The addition of salt reduces the enthalpy of polyelectrolyte complexation by screening electrostatic interaction at all Coulomb interaction strengths. The counterion release entropy also decreases in the presence of salt, but the reduction only becomes significant at higher Coulomb interaction strengths. More significantly, in the range of Coulomb interaction strengths appropriate for highly charged polymers in aqueous solutions, complexation enthalpy depends weakly on salt concentration and counterion release entropy exhibits a large variation as a function of salt concentration. Our study quantitatively establishes that polyelectrolyte complexation in highly charged Coulomb systems is of entropic origin.

  14. Enthalpy Differences of the n-Pentane Conformers.

    Science.gov (United States)

    Csontos, József; Nagy, Balázs; Gyevi-Nagy, László; Kállay, Mihály; Tasi, Gyula

    2016-06-14

    The energy and enthalpy differences of alkane conformers in various temperature ranges have been the subject for both experimental and theoretical studies over the last few decades. It was shown previously for the conformers of butane [G. Tasi et al., J. Chem. Theory Comput. 2012, 8, 479-486] that quantum chemical results can compete with spectroscopic techniques and results obtained even from the most carefully performed experiments could be biased due to the improper statistical model utilized to evaluate the raw experimental data. In the current study, on one hand, the experimental values and their uncertainties for the enthalpy differences for pentane conformers are re-evaluated using the appropriate statistical model. On the other hand, a coupled-cluster-based focal-point analysis has been performed to calculate energy and enthalpy differences for the conformers of pentane. The model chemistry defined in this study includes contributions up to the perturbative quadruple excitations augmented with further small correction terms beyond the Born-Oppenheimer and nonrelativistic approximations. Benchmark quality energy and enthalpy differences for the pentane conformers are given at temperatures 0 and 298.15 K as well as for the various temperature ranges used in the gas-phase experimental measurements. Furthermore, a slight positive shift for the experimental enthalpy differences is also predicted due to an additional Raman active band belonging to the gauche-gauche conformer.

  15. INFLUENCE OF ORGANIC SOLVENTS ON WATER DISSOCIATION IN BIPOLAR MEMBRANE

    Directory of Open Access Journals (Sweden)

    Sheldeshov N. V.

    2015-12-01

    Full Text Available The article discusses results of experimental research of the influence of aprotic and proton solvents on reaction rate of water molecules dissociation in the bipolar membrane MB-1 by the method of electrochemical impedance frequency spectrum. It was discovered, that addition of organic component in aqueous solutions results in significant influence on the parameters of water dissociation in a bipolar region of the membrane. The reason for this influence is the reduction of the mass fraction of water in solution and, consequently, in a bipolar region of the membrane, which itself reduces the rate of the dissociation reaction. Another reason for the influence of the organic solvent is its effect on the network of hydrogen bonds existing in water and aqueous solutions. Depending on the nature of organic solvent and its concentration, the network of hydrogen bonds may be strengthened, or destroyed, thus facilitating removal of the proton involved in the reactions between water molecules and catalytic centers in cation-exchange and anion-exchange layer of bipolar membrane, or retarding removal of proton. This leads respectively to speed up or slow down the rate of dissociation in the bipolar region of the membrane, as well as changing the constants of the dissociation reaction of water. Introduction of organic solvent in solutions, which are in the contact with bipolar membrane, is a convenient method of investigating the role of solution composition on the rate of proton transfer between water molecules and catalytic centers in the membranes

  16. Prediction of solvation enthalpy of gaseous organic compounds in propanol

    Science.gov (United States)

    Golmohammadi, Hassan; Dashtbozorgi, Zahra

    2016-09-01

    The purpose of this paper is to present a novel way for developing quantitative structure-property relationship (QSPR) models to predict the gas-to-propanol solvation enthalpy (Δ H solv) of 95 organic compounds. Different kinds of descriptors were calculated for each compound using the Dragon software package. The variable selection technique of replacement method (RM) was employed to select the optimal subset of solute descriptors. Our investigation reveals that the dependence of physical chemistry properties of solution on solvation enthalpy is nonlinear and that the RM method is unable to model the solvation enthalpy accurately. The results established that the calculated Δ H solv values by SVM were in good agreement with the experimental ones, and the performances of the SVM models were superior to those obtained by RM model.

  17. Enthalpy and Mechanical Relaxation of Glassy Gelatin Films

    Directory of Open Access Journals (Sweden)

    F Badii

    2005-10-01

    Full Text Available Glassy materials are not thermodynamically stable and during storage below the glass transition temperature (Tg, they are subjected to the time dependent changes towards the equilibrium. These changes are known as physical ageing, which is the basic feature of glassy materials below Tg. During ageing process, physical properties such as enthalpy and volume decrease and these changes are accompanied by important changes in mechanical properties such as change to modulus, compliance and mechanical relaxation, which are of great technological importance. The aim of this study is to investigate the occurrence of the mechanical relaxation in the glassy gelatin and compare it to the enthalpy relaxation phenomenon and try to correlate the rate of mechanical relaxation to the rate of enthalpy relaxation, which is the more reliable and frequent way for studying physical ageing. The extent of enthalpy relaxation of gelatin films with different water contents of 8%, 12 and 17%, measured by differential scanning calorimetry (DSC, was found to increase with increasing the ageing time. The mechanical behaviour of the gelatin films was measured, using dynamic mechanical thermal analysis (DMTA. The mechanical behaviour of gelatin showed time and frequency-dependent changes. Storage modulus increased during isothermal ageing and gelatin became harder and stiffer at higher frequency than that at low frequency. In order to assess the rate of mechanical relaxation, the classical time-ageing time superposition was applied to the results. The rate and extent of mechanical ageing were increased at higher water contents. A good agreement was found between the rate of the enthalpy relaxation and the changes to the mechanical properties at different water contents, suggesting that DSC measurements of enthalpy relaxation, which can be more easily implemented, can be used as indicator of mechanical changes.

  18. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  19. Reaction pathways of the dissociation of methylal: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Frey, H.-M.; Beaud, P.; Gerber, T.; Mischler, B.; Radi, P.P.; Tzannis, A.-P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Schemata for modelling combustion processes do not yet include reaction rates for oxygenated fuels like methylal (DMM) which is considered as an additive or replacement for diesel due to its low sooting propensity. Density functional theory (DFT) studies of the possible reaction pathways for different dissociation steps of methylal are presented. Cleavage of a hydrogen bond to the methoxy group or the central carbon atom were simulated at the BLYP/6-311++G{sup **} level of theory. The results are compared to the experiment when dissociating and/or ionising DMM with femtosecond pulses. (author) 1 fig., 1 tab., 1 ref.

  20. Correlation between standard enthalpy of formation, structural parameters and ionicity for alkali halides

    Directory of Open Access Journals (Sweden)

    Nasar Abu

    2013-01-01

    Full Text Available The standard enthalpy of formation (ΔHo has been considered to be an interesting and useful parameter for the correlation of various properties of alkali halides. The interrelation between ΔHo and structural parameters for the halides of Li, Na, K and Rb has been thoroughly analyzed. When cationic component element is kept constant in a homologous series of alkali halides, the negative value of ΔHo has been observed to decrease linearly with increase of interionic distance (d and accordingly following empirical equation ΔHo = α + βd (where α and β are empirical constants has been established. However, for common anionic series of alkali halides an opposite nonlinear trend has been observed with the exception of common fluorides. The correlation study on the standard enthalpy of formation has been extended in term of radius ratio and also discussed in the light of ionization energy of the metal, electron affinity of the halogen, size of the ions, ionic character of bond and lattice energy of the compound.

  1. Control of arc plasma torches: compensation of operational enthalpy drifts

    Energy Technology Data Exchange (ETDEWEB)

    Oliver, D H; Alexieva, J; Djakov, B E; Enikov, R [Institute of Electronics, Bulgarian Academy of Sciences, 72 Tzarigradsko Chaussee, 1784 Sofia (Bulgaria); Dimitrov, D [Centre of Biomedical Engineering, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bl. 105, 1113 Sofia (Bulgaria)], E-mail: dick.oliver@gmail.com

    2008-05-01

    In arc plasma torches electrode wear is the main reason for slow changes in the electrical and thermal torch characteristics. Such effects hinder technological applications of this type of plasma torches whenever the enthalpy must be maintained at a fixed level, or varied as needed. To solve this problem, a new method and algorithm for torch control are proposed. The time evolution of the arc current, voltage and thermal power loss of the torch are recorded. The values measured are used to find the required value of the enthalpy.

  2. Metal-Ligand Bonds of Second- and Third-Row d-Block Metals Characterized by Density Functional Theory

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2009-01-01

    metal-ligand bond lengths, and bond enthalpies for many as yet uncharacterized diatomics, of interest to researchers in the field of second- and third-row d-block chemistry. We stress that the success of TPSSh cannot be naively extrapolated to other special situations such as, e.g., metal-metal bonds...

  3. Dissociation Energies of Diatomic Molecules

    Institute of Scientific and Technical Information of China (English)

    FAN Qun-Chao; SUN Wei-Guo

    2008-01-01

    Molecular dissociation energies of 10 electronic states of alkali molecules of KH, 7LID, 7LiH, 6LiH, NaK, NaLi and NaRb are studied using the highest three accurate vibrational energies of each electronic state, and an improved parameter-free analytical formula which is obtained starting from the LeRoy-Bernstein vibrational energy expression near the dissociation limit. The results show that as long as the highest three vibrational energies are accurate, the current analytical formula will give accurate theoretical dissociation energies Detheory, which are in excellent agreement with the experimental dissociation energies Dexpte.

  4. PbCNN: A molecule containing Pb≡C bonding

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    In order to predict potential molecules with Pb≡C bonding, we investigated the potential energy sur-face of a tetra-atomic system [PbCN2] at the CCSD(T)//B3LYP level. We found that the linear isomer PbCNN possesses good thermodynamic and kinetic stability. The combined molecular orbital analysis, hydrogenation heat, bond energy and bond dissociation energy all proved that PbCNN is composed of Pb≡ C triple bonding.

  5. PbCNN: A molecule containing Pb≡C bonding

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wen-Bin; SHI Guo-Sheng; DING Yi-Hong; SUN Chia-Chung

    2009-01-01

    In order to predict potential molecules with Pb≡C bonding, we investigated the potential energy sur-face of a tetra-atomic system [PbCN2] at the CCSD(T)//B3LYP level. We found that the linear isomer PbCNN possesses good thermodynamic and kinetic stability. The combined molecular orbital analysis, hydrogenation heat, bond energy and bond dissociation energy all proved that PbCNN is composed of Pb≡C triple bonding.

  6. Predicting hydrogen-bond strengths from acid-base molecular properties. The pK(a) slide rule: toward the solution of a long-lasting problem.

    Science.gov (United States)

    Gilli, Paola; Pretto, Loretta; Bertolasi, Valerio; Gilli, Gastone

    2009-01-20

    :A proton acceptors most frequently involved in D-H...:A bond formation. Allowing the two scales to shift so to bring selected donor and acceptor molecules into coincidence, the ruler permits graphical evaluation of DeltapK(a) and then empirical appreciation of the D-H...:A bond strength according to the pK(a) equalization principle. Reliability of pK(a) slide rule predictions has been verified by extensive comparison with two classical sources of H-bond strengths: (i) the gas-phase dissociation enthalpies of charged [X...H...X](-) and [X...H...X](+) bonds derived from the thermodynamic NIST Database and (ii) the geometries of more than 9500 H-bonds retrieved from the Cambridge Structural Database. The results attest that the pK(a) slide rule provides a reliable solution for the long-standing problem of H-bond-strength prediction and represents an efficient and practical tool for making such predictions directly accessible to all scientists. PMID:18921985

  7. A Calorimeter for Measuring the Enthalpy of Solution of Solid A Calorimeter for Measuring the Enthalpy of Solution of Solid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    An apparatus for measuring the enthalpy of solution of solids in supercritical fluids (SCFs) was constructed. The enthalpy of solution (ΔH) of naphthalene in supercritical (SC) CO2 was measured at 308.15 K in the pressure range from 8~11 MPa. It was found that ΔH was negative in the pressure range from 8 to 10 MPa, and the absolute value of ΔH decreases with increasing pressure. However, ΔH became positive at the pressures higher than 10 MPa. This unusual phenomenon can be explained by clustering between CO2 and naphthalene.

  8. Methane Hydrate Formation and Dissociation in the Presence of Silica Sand and Bentonite Clay

    Directory of Open Access Journals (Sweden)

    Kumar Saw V.

    2015-11-01

    Full Text Available The formation and dissociation of methane hydrates in a porous media containing silica sand of different sizes and bentonite clay were studied in the presence of synthetic seawater with 3.55 wt% salinity. The phase equilibrium of methane hydrate under different experimental conditions was investigated. The effects of the particle size of silica sand as well as a mixture of bentonite clay and silica sand on methane hydrate formation and its dissociation were studied. The kinetics of hydrate formation was studied under different subcooling conditions to observe its effects on the induction time of hydrate formation. The amount of methane gas encapsulated in hydrate was computed using a real gas equation. The Clausius-Clapeyron equation is used to estimate the enthalpy of hydrate dissociation with measured phase equilibrium data.

  9. Cohesive Energies and Enthalpies: Complexities, Confusions, and Corrections.

    Science.gov (United States)

    Glasser, Leslie; Sheppard, Drew A

    2016-07-18

    The cohesive or atomization energy of an ionic solid is the energy required to decompose the solid into its constituent independent gaseous atoms at 0 K, while its lattice energy, Upot, is the energy required to decompose the solid into its constituent independent gaseous ions at 0 K. These energies may be converted into enthalpies at a given temperature by the addition of the small energies corresponding to integration of the heat capacity of each of the constituents. While cohesive energies/enthalpies are readily calculated by thermodynamic summing of the formation energies/enthalpies of the constituents, they are also currently intensively studied by computational procedures for the resulting insight on the interactions within the solid. In supporting confirmation of their computational results, authors generally quote "experimental" cohesive energies which are, in fact, simply the thermodynamic sums. However, these "experimental" cohesive energies are quoted in many different units, atom-based or calorimetric, and on different bases such as per atom, per formula unit, per oxide ion, and so forth. This makes comparisons among materials very awkward. Additionally, some of the quoted values are, in fact, lattice energies which are distinctly different from cohesive energies. We list large numbers of reported cohesive energies for binary halides, chalcogenides, pnictogenides, and Laves phase compounds which we bring to the same basis, and identify a number as incorrectly reported lattice energies. We also propose that cohesive energies of higher-order ionic solids may also be estimated as thermodynamic enthalpy sums.

  10. THE THERMAL CHARACTERIZATION OF MULTICOMPONENT SYSTEMS BY ENTHALPY RELAXATION

    NARCIS (Netherlands)

    TENBRINKE, G; OUDHUIS, L; ELLIS, TS

    1994-01-01

    The phenomenon of enthalpy relaxation of amorphous glassy polymers has been developed into an analytical tool which can be applied to elucidate phase behavior and morphologically related phenomena of multi-component systems. We have both reviewed the experimental details concerning its application,

  11. Experimental standard molar enthalpies of formation of some methylbenzenediol isomers

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro da Silva, Manuel A.V. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P 4169-007 (Portugal)], E-mail: risilva@fc.up.pt; Lobo Ferreira, Ana I.M.C. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P 4169-007 (Portugal)

    2009-10-15

    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{sup 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{sup 0}=0.1MPa) molar enthalpies, entropies, and Gibbs energies of sublimation, at T = 298.15 K, were derived for the four isomers of methylbenzenediols.

  12. Protein Transfer Free Energy Obeys Entropy-Enthalpy Compensation.

    Science.gov (United States)

    Mills, Eric A; Plotkin, Steven S

    2015-11-01

    We have found significant entropy-enthalpy compensation for the transfer of a diverse set of two-state folding proteins from water into water containing a diverse set of cosolutes, including osmolytes, denaturants, and crowders. In extracting thermodynamic parameters from experimental data, we show the potential importance of accounting for the cosolute concentration-dependence of the heat capacity change upon unfolding, as well as the potential importance of the temperature-dependence of the heat capacity change upon unfolding. We introduce a new Monte Carlo method to estimate the experimental uncertainty in the thermodynamic data and use this to show by bootstrapping methods that entropy-enthalpy compensation is statistically significant, in spite of large, correlated scatter in the data. We show that plotting the data at the transition midpoint provides the most accurate experimental values by avoiding extrapolation errors due to uncertainty in the heat capacity, and that this representation exhibits the strongest evidence of compensation. Entropy-enthalpy compensation is still significant at lab temperature however. We also find that compensation is still significant when considering variations due to heat capacity models, as well as typical measurement discrepancies lab-to-lab when such data is available. Extracting transfer entropy and enthalpy along with their uncertainties can provide a valuable consistency check between experimental data and simulation models, which may involve tests of simulated unfolded ensembles and/or models of the transfer free energy; we include specific applications to cold shock protein and protein L.

  13. Enthalpy of Vaporization and Vapor Pressures: An Inexpensive Apparatus

    Science.gov (United States)

    Battino, Rubin; Dolson, David A.; Hall, Michael A.; Letcher, Trevor M.

    2007-01-01

    A simple and inexpensive method to determine the enthalpy of vaporization of liquids by measuring vapor pressure as a function of temperature is described. The vapor pressures measured with the stopcock cell were higher than the literature values and those measured with the sidearm rubber septum cell were both higher and lower than literature…

  14. 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)

  15. Enthalpy and heat capacity of solid UO2

    International Nuclear Information System (INIS)

    Equations have been derived based upon a reevaluation of the enthalpy and heat-capacity data of UO2. We recommend a three-term nonlinear equation below 2670 K, with terms representing contributions from phonons, volumetric thermal expansion, and electrons, and a linear equation above 2670 K

  16. Hydrolyzable polyureas bearing hindered urea bonds.

    Science.gov (United States)

    Ying, Hanze; Cheng, Jianjun

    2014-12-10

    Hydrolyzable polymers are widely used materials that have found numerous applications in biomedical, agricultural, plastic, and packaging industrials. They usually contain ester and other hydrolyzable bonds, such as anhydride, acetal, ketal, or imine, in their backbone structures. Here, we report the first design of hydrolyzable polyureas bearing dynamic hindered urea bonds (HUBs) that can reversibly dissociate to bulky amines and isocyanates, the latter of which can be further hydrolyzed by water, driving the equilibrium to facilitate the degradation of polyureas. Polyureas bearing 1-tert-butyl-1-ethylurea bonds that show high dynamicity (high bond dissociation rate), in the form of either linear polymers or cross-linked gels, can be completely degraded by water under mild conditions. Given the simplicity and low cost for the production of polyureas by simply mixing multifunctional bulky amines and isocyanates, the versatility of the structures, and the tunability of the degradation profiles of HUB-bearing polyureas, these materials are potentially of very broad applications.

  17. Dissociation energy and dynamics of water clusters

    Science.gov (United States)

    Ch'ng, Lee Chiat

    The state-to-state vibrational predissociation (VP) dynamics of water clusters were studied following excitation of a vibrational mode of each cluster. Velocity-map imaging (VMI) and resonance-enhanced multiphoton ionization (REMPI) were used to determine pair-correlated center-of-mass translational energy distributions. Product energy distributions and dissociation energies were determined. Following vibrational excitation of the HCl stretch fundamental of the HCl-H2O dimer, HCl fragments were detected by 2 + 1 REMPI via the f 3□2(nu' = 0) ← X 1Sigma+(nu'' = 0) and V1Sigma + (nu' = 11 and 12) ← X1Sigma+ (nu'' = 0) transitions. REMPI spectra clearly show HCl from dissociation produced in the ground vibrational state with J'' up to 11. The fragments' center-of-mass translational energy distributions were determined from images of selected rotational states of HCl and were converted to rotational state distributions of the water cofragment. All the distributions could be fit well when using a dimer dissociation energy of bond dissociation energy D0 = 1334 +/- 10 cm--1. The rotational distributions in the water cofragment pair-correlated with specific rotational states of HCl appear nonstatistical when compared to predictions of the statistical phase space theory. A detailed analysis of pair-correlated state distributions was complicated by the large number of water rotational states available, but the data show that the water rotational populations increase with decreasing translational energy. H2O fragments of this dimer were detected by 2 + 1 REMPI via the C˜1B1(000) ← X˜1A1(000) transition. REMPI clearly shows that H2O from dissociation is produced in the ground vibrational state. The fragment's center-of-mass translational energy distributions were determined from images of selected rotational states of H2O and were converted to rotational state distributions of the HCl cofragment. The distributions gave D0 = 1334 +/- 10 cm --1 and show a clear

  18. Dissociation Patterns in Evolving Populations

    Science.gov (United States)

    Moreno, F. J.; Hernández, J. A.; Sánchez, F.

    2011-09-01

    The recent explosion and availability of mobility based technologies such as geographic information systems, cell phones equipped with built-in GPS, among others, are a valuable source of spatio-temporal data. However, only recently there have been works focused on identifying movement patterns in groups of moving entities. We focus on a particular movement pattern: dissociation. A dissociation pattern occurs when an entity that was once associated to a population, eventually separated from it and subsequently reintegrated it again. The backwarding and forwarding patterns are a type of dissociation where an entity stays behind or ahead of another entity, respectively. Dissociation really is a diversity generator, so instead avoiding it, taking advantage could be better to prevent premature convergence in evolutionary algorithms. In this work, we present formal mathematical definitions for these patterns. A discussion of how to use dissociation patterns as a mean to preserve diversity in evolutionary algorithms is also shown.

  19. 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.

    2014-06-01

    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.

  20. Enthalpy-Entropy Compensation in the Binding of Modulators at Ionotropic Glutamate Receptor GluA2

    DEFF Research Database (Denmark)

    Krintel, Christian; Francotte, Pierre; Pickering, Darryl S;

    2016-01-01

    modulators BPAM97 (2) and BPAM344 (3) into a hydroxyl group (BPAM557 (4) and BPAM521 (5), respectively), leads to a more favorable binding enthalpy (ΔH, kcal/mol) from −4.9 (2) and −7.5 (3) to −6.2 (4) and −14.5 (5), but also a less favorable binding entropy (−TΔS, kcal/mol) from −2.3 (2) and −1.3 (3) to −0...... of 5 was examined with x-ray crystallography, showing that the only change compared to that of earlier compounds was the orientation of Ser-497 pointing toward the hydroxyl group of 5. The favorable enthalpy can be explained by the formation of a hydrogen bond from the side-chain hydroxyl group of...... Ser-497 to the hydroxyl group of 5, whereas the unfavorable entropy might be due to desolvation effects combined with a conformational restriction of Ser-497 and 5. In summary, this study shows a remarkable example of enthalpy-entropy compensation in drug development accompanied with a likely...

  1. 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. PMID:24985659

  2. 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.

  3. A comparison of pathway-independent and pathway-dependent methods in the calculation of conformational free enthalpy differences.

    Science.gov (United States)

    Lin, Zhixiong; van Gunsteren, Wilfred F

    2016-01-01

    The multistep umbrella sampling method, which belongs to pathway-dependent methods to calculate conformational free enthalpy differences, is used to calculate the free enthalpy difference between a right-handed 2.710/12 -helix and a left-handed 314 -helix of a hexa-β-peptide in methanol solution. The same conformational free enthalpy difference was previously investigated using pathway-independent methods such as direct counting and enveloping distribution sampling. Our results show that the pathway-dependent simulations are sensitive to the choice of the pathway and its parameter values. A pathway based on restraining distances of hydrogen-bonding atom pairs shows poor sampling for two different values of the restraining force constant. Another pathway based on restraining backbone dihedral angles did smoothly sample the transition between the two helical conformations, but only with a proper choice of the restraining force constant. The results illustrate that if, and only if, a proper pathway and proper parameters are chosen, the multistep umbrella sampling can be almost 50 times more efficient than the pathway-independent methods in this case. The analysis illustrates the advantages and pitfalls of the much used multistep umbrella sampling methodology.

  4. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  5. Theoretical Investigation of the Bond Dissociation of Hydroxyl Terminated Polybutadiene Binder and Effect on Mechanical Properties%理论研究丁羟粘合剂化学键解离及其对力学性能的影响

    Institute of Scientific and Technical Information of China (English)

    武文明; 张炜; 陈敏伯; 强洪夫; 史良伟

    2012-01-01

    The binder of hydroxyl terminated polybutadiene(HTPB) cured by toluene diisocyanate(TDI) is usually used in solid propellants,in which the crucial issue involved in the storage and use is aging problem.The quantum chemistry calculation was used to analyze the relationship between homolytic bond dissociation energy(BDE) of two HTPB-TDI binder models and bond decomposition caused by aging.The computational results were proved to be reliable and suitable for comparative analysis.The BDE values of C—O bonds connected with CH2 group were calculated to be minima,suggesting that they are the weakest bonds resulting in decomposition during thermal aging.The main degradation product is CO2.In the binder formed by the reaction of allylic primary hydroxyl of HTPB and TDI,the α-C—H is the weakest X—H(X=C,N) bond,suggesting that it is vulnerable to free radical attack accompanying the hydrogen transfer.The possible mechanism of aging for the easy-cleavage C—O bonds was proposed.The calculated activation energies of C—O bonds cleavage are approximately equal to the corresponding BDE values,indicating that the formation of radicals accompanies a barrier-free release of CO2 during thermal aging.The half-life time of such aging process was described by an exponential decay function of temperature.The aging of HTPB-TDI binder accelerates with increasing temperature.The radical recombination reactions of decomposed amino radicals and alkyl radicals are supported by thermodynamic data calculated.Molecular dynamic simulations were used to analyze the variation in the network structures and effect on mechanical properties of HTPB-TDI binder models before and after aging.It is found that the density of the system decreases with release and diffusion of CO2,and the corresponding tensile modulus and shear modulus increase with aging.%异腈酸酯固化的端羟基聚丁二烯(HTPB)粘合剂常用于固体推进剂中,老化是其贮存和使用中的重要

  6. Dissociation of gaseous zwitterion glycine-betaine by slow electrons.

    Science.gov (United States)

    Kopyra, J; Abdoul-Carime, H

    2010-05-28

    In this work, we investigate dissociation processes induced by low-energy electrons to gas phase N,N,N-trimethylglycine [glycine-betaine, (CH(3))(3)N(+)CH(2)COO(-)] molecules. Glycine-betaine represents a model system for zwitterions. All negative fragments are observed to be produced only at subelectronic excitation energies (<4 eV). With the exception of the loss of a neutral H atom that could arise from any C[Single Bond]H bond breaking, we tentatively suggest that the zwitterion dissociates exclusively from the fragmentation of the cation site of the molecule, subsequent to the attachment of the excess electron. Within the context of radiation induced damage to biological systems, the present findings contribute to a more complete description of the fragmentation mechanism occurring to amino acids, peptides, and proteins since they adopt usually a zwitterion structure. PMID:20515090

  7. Experimental investigation of the complete inner shell hydration energies of Ca2+: threshold collision-induced dissociation of Ca(2+)(H2O)x Complexes (x = 2-8).

    Science.gov (United States)

    Carl, Damon R; Armentrout, P B

    2012-04-19

    The sequential bond energies of Ca(2+)(H(2)O)(x) complexes, where x = 1-8, are measured by threshold collision-induced dissociation (TCID) in a guided ion beam tandem mass spectrometer. From an electrospray ionization source that produces an initial distribution of Ca(2+)(H(2)O)(x) complexes where x = 6-8, complexes down to x = 2 are formed using an in-source fragmentation technique. Ca(2+)(H(2)O) cannot be formed in this source because charge separation into CaOH(+) and H(3)O(+) is a lower energy pathway than simple water loss from Ca(2+)(H(2)O)(2). The kinetic energy dependent cross sections for dissociation of Ca(2+)(H(2)O)(x) complexes, where x = 2-9, are examined over a wide energy range to monitor all dissociation products and are modeled to obtain 0 and 298 K binding energies. Analysis of both primary and secondary water molecule losses from each sized complex provides thermochemistry for the sequential hydration energies of Ca(2+) for x = 1-8 and the first experimental values for x = 1-4. Additionally, the thermodynamic onsets leading to the charge separation products from Ca(2+)(H(2)O)(2) and Ca(2+)(H(2)O)(3) are determined for the first time. Our experimental results for x = 1-6 agree well with previously calculated binding enthalpies as well as quantum chemical calculations performed here. Agreement for x = 1 is improved when the basis set on calcium includes core correlation.

  8. Threshold collision-induced dissociation of hydrated magnesium: experimental and theoretical investigation of the binding energies for Mg(2+)(H2O)x complexes (x=2-10).

    Science.gov (United States)

    Carl, Damon R; Armentrout, Peter B

    2013-03-18

    The sequential bond energies of Mg(2+)(H2O)x complexes, in which x=2-10, are measured by threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. From an electrospray ionization source that produces an initial distribution of Mg(2+)(H2O)x complexes in which x=7-10, complexes down to x=3 are formed by using an in-source fragmentation technique. Complexes smaller than Mg(2+)(H2O)3 cannot be formed in this source because charge separation into MgOH(+)(H2O) and H3O(+) is a lower-energy pathway than simple water loss from Mg(2+)(H2O)3. The kinetic energy dependent cross sections for dissociation of Mg(2+)(H2O)x complexes, in which x=3-10, are examined over a wide energy range to monitor all dissociation products and are modeled to obtain 0 and 298 K binding energies. Analysis of both primary and secondary water molecule losses from each sized complex provides thermochemistry for the sequential hydration energies of Mg(2+) for x=2-10 and the first experimental values for x=2-4. Additionally, the thermodynamic onsets leading to the charge-separation products from Mg(2+)(H2O)3 and Mg(2+)(H2O)4 are determined for the first time. Our experimental results for x=3-7 agree well with quantum chemical calculations performed here and previously calculated binding enthalpies, as well as previous measurements for x=6. The present values for x=7-10 are slightly lower than previous experimental results and theory, but within experimental uncertainties.

  9. 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.

  10. Blunt-Body Aerothermodynamic Database from High-Enthalpy CO2 Testing in an Expansion Tunnel

    Science.gov (United States)

    Hollis, Brian R.; Prabhu, Dinesh K.; Maclean, Matthew; Dufrene, Aaron

    2016-01-01

    An extensive database of heating, pressure, and flow field measurements on a 70-deg sphere-cone blunt body geometry in high-enthalpy, CO2 flow has been generated through testing in an expansion tunnel. This database is intended to support development and validation of computational tools and methods to be employed in the design of future Mars missions. The test was conducted in an expansion tunnel in order to avoid uncertainties in the definition of free stream conditions noted in previous studies performed in reflected shock tunnels. Data were obtained across a wide range of test velocity/density conditions that produced various physical phenomena of interest, including laminar and transitional/turbulent boundary layers, non-reacting to completely dissociated post-shock gas composition and shock-layer radiation. Flow field computations were performed at the test conditions and comparisons were made with the experimental data. Based on these comparisons, it is recommended that computational uncertainties on surface heating and pressure, for laminar, reacting-gas environments can be reduced to +/-10% and +/-5%, respectively. However, for flows with turbulence and shock-layer radiation, there were not sufficient validation-quality data obtained in this study to make any conclusions with respect to uncertainties, which highlights the need for further research in these areas.

  11. Modeling Proton Dissociation and Transfer Using Dissipative Particle Dynamics Simulation.

    Science.gov (United States)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V

    2015-09-01

    We suggest a coarse-grained model for dissipative particle dynamics (DPD) simulations of solutions with dissociated protons. The model uses standard short-range soft repulsion and smeared charge electrostatic potentials between the beads, representing solution components. The proton is introduced as a separate charged bead that forms dissociable bonds with proton receptor base beads, such as water or deprotonated acid anions. The proton-base bonds are described by Morse potentials. When the proton establishes the Morse bonds with two bases, they form an intermediate complex, and the proton is able to "hop" between the bases artificially mimicking the Grotthuss diffusion mechanism. By adjusting the Morse potential parameters, one can regulate the potential barrier associated with intermediate complex formation and breakup and control the hopping frequency. This makes the proposed model applicable to simulations of proton mobility and reaction equilibria between protonated and deprotonated acid forms in aqueous solutions. The proposed model provides quantitative agreement with experiments for the proton self-diffusion coefficient and hopping frequency, as well as for the degree of dissociation of benzenesulfonic acid. PMID:26575931

  12. Formation and Dissociation of Methane Hydrates from Seawater in Consolidated Sand: Mimicking Methane Hydrate Dynamics beneath the Seafloor

    Directory of Open Access Journals (Sweden)

    Prasad B. Kerkar

    2013-11-01

    Full Text Available Methane hydrate formation and dissociation kinetics were investigated in seawater-saturated consolidated Ottawa sand-pack under sub-seafloor conditions to study the influence of effective pressure on formation and dissociation kinetics. To simulate a sub-seafloor environment, the pore-pressure was varied relative to confining pressure in successive experiments. Hydrate formation was achieved by methane charging followed by sediment cooling. The formation of hydrates was delayed with increasing degree of consolidation. Hydrate dissociation by step-wise depressurization was instantaneous, emanating preferentially from the interior of the sand-pack. Pressure drops during dissociation and in situ temperature controlled the degree of endothermic cooling within sediments. In a closed system, the post-depressurization dissociation was succeeded by thermally induced dissociation and pressure-temperature conditions followed theoretical methane-seawater equilibrium conditions and exhibited excess pore pressure governed by the pore diameter. These post-depressurization equilibrium values for the methane hydrates in seawater saturated consolidated sand-pack were used to estimate the enthalpy of dissociation of 55.83 ± 1.41 kJ/mol. These values were found to be lower than those reported in earlier literature for bulk hydrates from seawater (58.84 kJ/mol and pure water (62.61 kJ/mol due to excess pore pressure generated within confined sediment system under investigation. However, these observations could be significant in the case of hydrate dissociation in a subseafloor environment where dissociation due to depressurization could result in an instantaneous methane release followed by slow thermally induced dissociation. The excess pore pressure generated during hydrate dissociation could be higher within fine-grained sediments with faults and barriers present in subseafloor settings which could cause shifting in geological layers.

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

    Science.gov (United States)

    Zhang, Lei; Wang, Rongcheng; Tao, Xiaoma; Guo, Hui; Chen, Hongmei; Ouyang, Yifang

    2015-04-01

    Formation enthalpy is important for the phase stability and amorphous forming ability of alloys. The formation enthalpies of Fe17RE2 (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 (AlxFe1-x)17Nd2 have been calculated by Miedema's theory and the geometric model. The solid solubility of Al in (AlxFe1-x)17Nd2 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.

  14. CO dissociation on magnetic Fen clusters

    KAUST Repository

    Jedidi, Abdesslem

    2014-01-01

    This work theoretically investigates the CO dissociation on Fen nanoparticles, for n in the range of 1-65, focusing on size dependence in the context of the initial step of the Fischer-Tropsch reaction. CO adsorbs molecularly through its C-end on a triangular facet of the nanoparticle. Dissociation becomes easier when the cluster size increases. Then, the C atom is bonded to a square facet that is generated as a result of the adsorption if it does not yet exist in the bare cluster, while the O atom is adsorbed on a triangular facet. In the most stable situation, the two adsorbed atoms remain close together, both having in common one shared first-neighbor iron atom. There is a partial spin quenching of the neighboring Fe atoms, which become more positively charged than the other Fe atoms. The shared surface iron atom resembles a metal-cation from a complex. Despite the small size of the iron cluster considered, fluctuations due to specific configurations do not influence properties for n > 25 and global trends seem significant.

  15. Enthalpy-Entropy Compensation (EEC) Effect: A Revisit.

    Science.gov (United States)

    Pan, Animesh; Biswas, Tapas; Rakshit, Animesh K; Moulik, Satya P

    2015-12-31

    A short account of the developments and perspectives of IKR (iso-kinetic relation) and EEC (enthalpy (H) - entropy (S) compensation) has been presented. The IKR and EEC are known to be extra thermodynamic or empirical correlations though linear H-S correlation can be thermodynamically deduced. Attempt has also been made to explain the phenomena in terms of statistical thermodynamics. In this study, we have briefly revisited the fundamentals of both IKR and EEC from kinetic and thermodynamic grounds. A detailed revisit of the EEC phenomenon on varied kinetic and equilibrium processes has been also presented. Possible correlations among the free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes of different similar and nonsimilar chemical processes under varied conditions have been discussed with possible future projections.

  16. Prediction of saturated liquid enthalpy of refrigerant mixtures

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    New corresponding temperature and corresponding enthalpy of refrigerant mix- tures were defined. The relationship between saturated liquid corresponding en- thalpy and corresponding temperature of refrigerant mixtures accorded with that of pure components. The characteristic parameters of saturated liquid enthalpy dif- ference of refrigerant mixtures were calculated by three methods according to the different application conditions. The generalized equation of saturated liquid en- thalpy of refrigerant mixtures was presented. The calculated values were compared with the values in literature for five ternary and binary refrigerant mixtures, namely R404A, R407A, R407B, R32/R134a, and R410A. The overall average absolute devia- tion was less than 1.0%.

  17. Flow enthalpy effects on scramjet mixing and combustion

    Science.gov (United States)

    Riggins, D. W.; Mcclinton, C. R.; Rogers, R. C.

    1992-01-01

    The present analysis of the 3D characteristics of the mixing processes in a scramjet combustor gives attention to the streamwise, vorticity-driven macromixing, as well as shear-driven small-scale mixing, in both an unconfined Mach 6 airstream and a high-enthalpy (Mach-17) confined, Mach 6 airstream. The results obtained indicate that mixing is substantially lower for the high-enthalpy case. The effect of residence time on jet mixing is discussed in view of the production and decay of the axial vorticity, cross-flow velocities, and mean-flow velocities of these confined flows. The effective distance travelled by a fluid particle in the cross-flow, over the combustor length, is used to explain axial vorticity's contribution to mixing.

  18. Enthalpy-Entropy Compensation upon Molecular Conformational Changes.

    Science.gov (United States)

    Ahmad, Mazen; Helms, Volkhard; Lengauer, Thomas; Kalinina, Olga V

    2015-04-14

    The change in free energy is the dominant factor in all chemical processes; it usually encompasses enthalpy-entropy compensation (EEC). Here, we use the free energy perturbation formalism to show that EEC is influenced by the molecular conformational changes (CCs) of the entire system comprising the solute and by the already known solvent reorganization. The internal changes of enthalpy and the entropy due to CCs upon modifying the interactions (perturbation) cancel each other exactly. The CCs influence the dissipation of the modified interactions and their contributions to the free energy. Using molecular simulations, we show that, for solvation of six different HIV-1 protease inhibitors, CCs in the solute cause EEC as large as 10-30 kcal/mol. Moreover, the EEC due to CCs in HIV-1 protease is shown to vary significantly upon modifying its bound ligand. These findings have important implications for understanding of EEC phenomena and for interpretation of thermodynamic measurements.

  19. Symmetry-enthalpy correlations in Diels-Alder reactions.

    Science.gov (United States)

    Tuvi-Arad, Inbal; Avnir, David

    2012-08-01

    Woodward-Hoffmann (WH) rules provide strict symmetry selection rules: when they are obeyed, a reaction proceeds; when they are not obeyed, there is no reaction. However, the voluminous experimental literature provides ample evidence that strict compliance to symmetry requirements is not an obstacle for a concerted reaction to proceed, and therefore the idea has developed that it is enough to have a certain degree of the required symmetry to have reactivity. Here we provide quantitative evidence of that link, and show that as one deviates from the desired symmetry, the enthalpy of activation increases, that is, we show that concerted reactions slow down the further they are from the ideal symmetry. Specifically, we study the deviation from mirror symmetry (evaluated with the continuous symmetry measure (CSM)) of the [4+2] carbon skeleton of the transition state of a series of twelve Diels-Alder reactions in seven different solvents (and in the gas phase), in which the dienes are butadiene, cyclopentadiene, cyclohexadiene, and cycloheptadiene; the dienophiles are the 1-, 1,1-, and 1,1,2-cyanoethylene derivatives; the solvents were chosen to sample a range of dielectric constants from heptane to ethanol. These components provide twenty-four symmetry-enthalpy DFT-calculated correlation lines (out of which only one case is a relatively mild exception) that show the general trend of increase in enthalpy as symmetry decreases. The various combinations between the dienophiles, cyanoethylenes, and solvents provide all kinds of sources for symmetry deviations; it is therefore remarkable that although the enthalpy of activation is dictated by various parameters, symmetry emerges as a primary parameter. In our analysis we also bisected this overall picture into solvent effects and geometry variation effects to evaluate under which conditions the electronic effects are more dominant than symmetry effects.

  20. Corollary from the Exact Expression for Enthalpy of Vaporization

    Directory of Open Access Journals (Sweden)

    A. A. Sobko

    2011-01-01

    Full Text Available A problem on determining effective volumes for atoms and molecules becomes actual due to rapidly developing nanotechnologies. In the present study an exact expression for enthalpy of vaporization is obtained, from which an exact expression is derived for effective volumes of atoms and molecules, and under certain assumptions on the form of an atom (molecule it is possible to find their linear dimensions. The accuracy is only determined by the accuracy of measurements of thermodynamic parameters at the critical point.

  1. Enthalpy and Mechanical Relaxation of Glassy Gelatin Films

    OpenAIRE

    Badii, F; IA Farhat

    2005-01-01

    Glassy materials are not thermodynamically stable and during storage below the glass transition temperature (Tg), they are subjected to the time dependent changes towards the equilibrium. These changes are known as physical ageing, which is the basic feature of glassy materials below Tg. During ageing process, physical properties such as enthalpy and volume decrease and these changes are accompanied by important changes in mechanical properties such as change to modulus, compliance and mechan...

  2. Electronic-enthalpy functional for finite systems under pressure

    OpenAIRE

    Cococcioni, Matteo; Mauri, Francesco; Ceder, Gerbrand; Marzari, Nicola

    2005-01-01

    We introduce the notion of electronic enthalpy for first-principles structural and dynamical calculations of finite systems under pressure. An external pressure field is allowed to act directly on the electronic structure of the system studied via the ground-state minimization of the functional $E+PV_{q}$, where $V_{q}$ is the quantum volume enclosed by a charge isosurface. The Hellmann-Feynman theorem applies, and assures that the ionic equations of motion follow an isoenthalpic dynamics. No...

  3. 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.

  4. Enthalpy benchmark experiments for numerical ice sheet models

    Directory of Open Access Journals (Sweden)

    T. Kleiner

    2014-06-01

    Full Text Available We present benchmark experiments to test the implementation of enthalpy and the corresponding boundary conditions in numerical ice sheet models. The first experiment tests particularly the functionality of the boundary condition scheme and the basal melt rate calculation during transient simulations. The second experiment addresses the steady-state enthalpy profile and the resulting position of the cold–temperate transition surface (CTS. For both experiments we assume ice flow in a parallel-sided slab decoupled from the thermal regime. Since we impose several assumptions on the experiment design, analytical solutions can be formulated for the proposed numerical experiments. We compare simulation results achieved by three different ice flow-models with these analytical solutions. The models agree well to the analytical solutions, if the change in conductivity between cold and temperate ice is properly considered in the model. In particular, the enthalpy gradient at the cold side of the CTS vanishes in the limit of vanishing conductivity in the temperate ice part as required from the physical jump conditions at the CTS.

  5. Global exploration of the enthalpy landscape of calcium carbide.

    Science.gov (United States)

    Kulkarni, A; Doll, K; Schön, J C; Jansen, M

    2010-12-01

    The enthalpy landscape of CaC(2) was investigated on the ab initio level, and possible (meta)stable structures are predicted. Simulated annealing was used as a global exploration method for the determination of the local minima on the enthalpy landscapes, where the only information supplied was the number of atoms per unit cell. Subsequently, the structure candidates found were locally optimized. At all stages of the search, the energy calculations were performed on the ab initio level. Furthermore, we investigated the enthalpies of different modifications as a function of pressure, and we found that, at a transition pressure of about 30 GPa, CaC(2) should transform from a 6-fold coordinated structure resembling a rock-salt structure to an 8-fold coordinated one similar to the CsCl structure. At standard pressure, two new energetically low-lying (metastable) structures were found, and at high pressure an additional new metastable structure was also predicted to be capable of existence.

  6. Dissociative Tendencies and Traffic Incidents

    Directory of Open Access Journals (Sweden)

    Valle, Virginia

    2012-01-01

    Full Text Available This paper analyses the relationship between dissociative experiences and road traffic incidents (crashes and traffic tickets in drivers (n=295 from Mar del Plata (Argentina city. A self-report questionnaire was applied to assess traffic crash involvement and sociodemographic variables. Dissociative tendencies were assessed by a modified version of the DES scale. To examine differences in DES scores tests of the difference of means were applied. Drivers who reported to be previously involved in traffic incidents obtained higher puntuations in the dissociative experiences scale than drivers who did not report such events. This result is observed for the total scale and for the three sub-scales (absorption, amnesia and depersonalization. However, differences appeared mainly for minor damage collisions. Further studies are needed to evaluate the role of dissociative tendencies as a risk factor in road traffic safety.

  7. Estimation of Enthalpy of Formation of Liquid Transition Metal Alloys: A Modified Prescription Based on Macroscopic Atom Model of Cohesion

    Science.gov (United States)

    Raju, Subramanian; Saibaba, Saroja

    2016-09-01

    The enthalpy of formation Δo H f is an important thermodynamic quantity, which sheds significant light on fundamental cohesive and structural characteristics of an alloy. However, being a difficult one to determine accurately through experiments, simple estimation procedures are often desirable. In the present study, a modified prescription for estimating Δo H f L of liquid transition metal alloys is outlined, based on the Macroscopic Atom Model of cohesion. This prescription relies on self-consistent estimation of liquid-specific model parameters, namely electronegativity ( ϕ L) and bonding electron density ( n b L ). Such unique identification is made through the use of well-established relationships connecting surface tension, compressibility, and molar volume of a metallic liquid with bonding charge density. The electronegativity is obtained through a consistent linear scaling procedure. The preliminary set of values for ϕ L and n b L , together with other auxiliary model parameters, is subsequently optimized to obtain a good numerical agreement between calculated and experimental values of Δo H f L for sixty liquid transition metal alloys. It is found that, with few exceptions, the use of liquid-specific model parameters in Macroscopic Atom Model yields a physically consistent methodology for reliable estimation of mixing enthalpies of liquid alloys.

  8. Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; North, S.W.; Stranges, D. [Lawrence Berkeley National Lab., CA (United States)] [and others

    1997-04-01

    When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH{sub 3}SOCH{sub 3}) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH{sub 3} intermediate prior to dissociation to define a stepwise dissociation: (1) CH{sub 3}SOCH{sub 3} {r_arrow} 2CH{sub 3} + SO; (2a) CH{sub 3}SOCH{sub 3} {r_arrow} CH{sub 3} + SOCH{sub 3}; and (2b) SOCH{sub 3} {r_arrow} SO + CH{sub 3}. Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH{sub 3} and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 9.0.2.1. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH{sub 3} intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2.

  9. Molecular dynamics simulations of the hydration of poly(vinyl methyl ether): Hydrogen bonds and quasi-hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    WU RongLiang; JI Qing; KONG Bin; YANG XiaoZhen

    2008-01-01

    Atomistic detailed hydration structures of poly(vinyl methyl ether) (PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution func-tions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain, and there still exists a significant amount (10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentra-tion as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer, which leads to inefficient con-tacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds, but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry (DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME, which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition, at the concentration of 86%, each ether oxygen atom bonded with water is assigned 1.56 water molecules on average, and 'free' water molecules emerge at the concentration of around 54%.

  10. Molecular dynamics simulations of the hydration of poly(vinyl methyl ether):Hydrogen bonds and quasi-hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Atomistic detailed hydration structures of poly(vinyl methyl ether)(PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution functions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain,and there still exists a significant amount(10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentration as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer,which leads to inefficient contacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds,but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry(DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME,which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition,at the concentration of 86%,each ether oxygen atom bonded with water is assigned 1.56 water molecules on average,and ’free’ water molecules emerge at the concentration of around 54%.

  11. Investigation of intense femto-second laser ionization and dissociation of methane with time-dependent density-functional approach

    Science.gov (United States)

    Irani, E.; Sadighi-Bonabi, R.; Anvari, A.

    2014-06-01

    Three dimensional calculations of electronic dynamics of CH4 in a strong laser field are presented with time-dependent density-functional theory. Time evolution of dipole moment and electron localization function is presented. The dependence of dissociation rate on the laser characters is shown and optimal effective parameters are evaluated. The optimum field leads to 76% dissociation probability for GAUSSIAN envelope and 40 fs (FWHM) at 1016 W cm-2. The dissociation probability is calculated by optimum convolution of dual short pulses. By combining of field assisted dissociation process and Ehrenfest molecular dynamics, time variation of bond length, velocity and orientation effect are investigated.

  12. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  13. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  14. Enthalpies of combustion, vapour pressures, and enthalpies of sublimation of the 1,5- and 1,8-diaminonaphthalenes

    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, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 (Portugal); Lobo Ferreira, Ana I.M.C.; Santos, Ana Filipa L.O.M.; Ferreira, Cristiana M.A.; Barros, Delfina C.B.; Reis, Joana A.C.; Costa, Jose C.S.; Calvinho, Maria Miguel G.; Rocha, Sonia I.A.; Pinto, Sonia P.; Freire, Sonia S.L.; Almeida, Suzete M.; Guimaraes, Vanessa S.; Almeida, Vasco N.M. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 (Portugal)

    2010-03-15

    The standard (p{sup 0} = 0.1 MPa) molar enthalpies of formation, in the crystalline state, of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static-bomb combustion calorimetry. The Knudsen mass-loss effusion technique was used to measure the dependence of the vapour pressure of the solid isomers of diaminonaphthalene with the temperature, from which the standard molar enthalpies of sublimation were derived using the Clausius-Clapeyron equation. Combining these two experimental values, the gas-phase standard molar enthalpies of formation, at T = 298.15 K, were derived and compared with those estimated using two different empirical methods of DELTA{sub f}H{sub m}{sup 0}(g) estimation: the Cox scheme and the Benson's Group Method. Moreover, the standard (p{sup 0} = 0.1 MPa) molar entropies and Gibbs energies of sublimation, at T = 298.15 K, were derived for the two diaminonaphthalene isomers.

  15. Direct molecular simulation of nitrogen dissociation based on an ab initio potential energy surface

    Energy Technology Data Exchange (ETDEWEB)

    Valentini, Paolo, E-mail: vale0142@umn.edu; Schwartzentruber, Thomas E., E-mail: schwart@aem.umn.edu; Bender, Jason D., E-mail: jbender73@gmail.com; Nompelis, Ioannis, E-mail: nompelis@umn.edu; Candler, Graham V., E-mail: candler@umn.edu [Department of Aerospace Engineering and Mechanics, College of Science and Engineering, University of Minnesota, Minneapolis, Minnesota 55455 (United States)

    2015-08-15

    The direct molecular simulation (DMS) approach is used to predict the internal energy relaxation and dissociation dynamics of high-temperature nitrogen. An ab initio potential energy surface (PES) is used to calculate the dynamics of two interacting nitrogen molecules by providing forces between the four atoms. In the near-equilibrium limit, it is shown that DMS reproduces the results obtained from well-established quasiclassical trajectory (QCT) analysis, verifying the validity of the approach. DMS is used to predict the vibrational relaxation time constant for N{sub 2}–N{sub 2} collisions and its temperature dependence, which are in close agreement with existing experiments and theory. Using both QCT and DMS with the same PES, we find that dissociation significantly depletes the upper vibrational energy levels. As a result, across a wide temperature range, the dissociation rate is found to be approximately 4–5 times lower compared to the rates computed using QCT with Boltzmann energy distributions. DMS calculations predict a quasi-steady-state distribution of rotational and vibrational energies in which the rate of depletion of high-energy states due to dissociation is balanced by their rate of repopulation due to collisional processes. The DMS approach simulates the evolution of internal energy distributions and their coupling to dissociation without the need to precompute rates or cross sections for all possible energy transitions. These benchmark results could be used to develop new computational fluid dynamics models for high-enthalpy flow applications.

  16. Dissociative experiences and dissociative minds: Exploring a nomological network of dissociative functioning.

    Science.gov (United States)

    Schimmenti, Adriano

    2016-01-01

    In this study, the psychometric properties of the Dissociative Experiences Scale-II (DES-II) were tested in a sample of Italian adults, and a nomological network of dissociative functioning based on current psychodynamic research was examined. A total of 794 participants (55% females) ranging in age from 18 to 64 completed the DES-II and other measures of theory of mind, alexithymia, attachment style, and empathy. The Italian translation of the DES-II showed high internal consistency, adequate item-to-scale homogeneity, and good split-half reliability. A single-factor solution including the 8 items of pathological dissociation (DES-T) adequately fit the data. Participants who reported higher levels of dissociative experiences showed significantly lower scores on theory of mind and empathy than other participants. They also showed significantly higher scores on alexithymia, preoccupied attachment, and fearful attachment. Results of the study support the view that people who suffer from severe dissociative experiences may also have difficulties mentalizing and regulating affects and that they may feel uncomfortable in close relationships because they have a negative view of the self. This can inform clinical work with dissociative individuals, who could benefit from therapies that consider their potential problems with mentalization, empathy, affect regulation, and attachment.

  17. Laboratory Measurement of Enthalpy Flux in High Winds

    Science.gov (United States)

    Jeong, D.; Haus, B. K.; Donelan, M. A.; Zhang, J.

    2006-12-01

    The intensity of tropical cyclones is sensitive to the rates at which enthalpy and momentum are transferred between sea and air in the high-wind core of the storm. Present models of the wind dependence of these transfer rates, does not allow for storms of greater than marginal hurricane intensity. Recent studies have shown that there is a saturation of the bulk drag coefficient in high winds, however more information on the enthalpy flux is required. In particular the role that sea spray plays in enhancing the enthalpy transfer at very high wind speeds is not known. The coefficients for sensible and latent heat transfer (Stanton and Dalton numbers) were measured in the 15-m wind-wave facility at the University of Miami's Air-Sea Interaction Saltwater Tank (ASIST). The wind speed (referred to 10m) was explored over a range of 0 to 45 m/s, covering a full range of aerodynamic conditions from smooth to fully rough. Experiments were designed with water temperatures set between 2 and 5° C above/below the air temperature, with precision thermistors (± 0.002° C) to monitor temperature and Li-Cor infra-red absorption devices to monitor specific humidity changes at upstream and downstream ends of the wave tank during the experiment. The calorimetric use of a wind-wave tank gave precise flux estimates, and experiments were repeated at different Bowen ratios to allow the separation of the heat and moisture parts of the transfer. The effect of spray on the moisture flux was reflected in the drop in temperature along the air path from upstream to downstream and this made it possible to estimate the total spray evaporated in the air column.

  18. Geophysical techniques for low enthalpy geothermal exploration in New Zealand

    Science.gov (United States)

    Soengkono, Supri; Bromley, Chris; Reeves, Robert; Bennie, Stewart; Graham, Duncan

    2013-05-01

    Shallow warm water resources associated with low enthalpy geothermal systems are often difficult to explore using geophysical techniques, mainly because the warm water creates an insufficient physical change from the host rocks to be easily detectable. In addition, often the system also has a limited or narrow size. However, appropriate use of geophysical techniques can still help the exploration and further investigation of low enthalpy geothermal resources. We present case studies on the use of geophysical techniques for shallow warm water explorations over a variety of settings in New Zealand (mostly in the North Island) with variable degrees of success. A simple and direct method for the exploration of warm water systems is shallow temperature measurements. In some New Zealand examples, measurements of near surface temperatures helped to trace the extent of deeper thermal water. The gravity method was utilised as a structural technique for the exploration of some warm water systems in New Zealand. Our case studies show the technique can be useful in identifying basement depths and tracing fault systems associated with the occurrence of hot springs. Direct current (DC) ground resistivity measurements using a variety of electrode arrays have been the most common method for the exploration of low enthalpy geothermal resources in New Zealand. The technique can be used to detect the extent of shallow warm waters that are more electrically conductive than the surrounding cold groundwater. Ground resistivity investigations using the electromagnetic (EM) techniques of audio magnetotellurics (AMT or shallow MT), controlled source audio magnetotellurics (CSAMT) and transient electromagnetic (TEM) methods have also been used. Highly conductive clays of thermal or sedimentary origin often limit the penetration depth of the resistivity techniques and can create some interpretation difficulties. Interpretation of resistivity anomalies needs to be treated in a site specific

  19. 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.

  20. Enthalpy of formation of (In, Gd)-doped barium cerate

    Energy Technology Data Exchange (ETDEWEB)

    Matskevich, N.I., E-mail: nata.matskevich@yandex.ru [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk (Russian Federation); Karlsruhe Institute of Technology, Institute of Solid State Physics, D-76334 Karlsruhe (Germany); Wolf, Th. [Karlsruhe Institute of Technology, Institute of Solid State Physics, D-76334 Karlsruhe (Germany); Adelmann, P.; Semerikova, A.N.; Anyfrieva, O.I. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk (Russian Federation)

    2015-09-10

    Highlights: • BaCe{sub 0.7}Gd{sub 0.2}In{sub 0.1}O{sub 2.85} was prepared by solid-state reaction. • The standard formation enthalpy was determined. • The stabilization energy (Δ{sub st}H°) was calculated. • Δ{sub st}H° of BaCe{sub 0.7}Gd{sub 0.2}In{sub 0.1}O{sub 2.85} is higher than BaCe{sub 0.7}Nd{sub 0.2}In{sub 0.1}O{sub 2.85} and BaCeO{sub 3}. - Abstract: Solution enthalpies of barium cerate doped by gadolinium and indium and a mixture of BaCl{sub 2} + 0.7CeCl{sub 3} + 2GdCl{sub 3} + 0.1InCl{sub 3} have been measured in 1 mol dm{sup −3} HCl with 0.1 mol dm{sup −3} KI. For the first time the standard molar formation enthalpy of BaCe{sub 0.7}Gd{sub 0.2}In{sub 0.1}O{sub 2.85} has been determined by solution calorimetry as follows: Δ{sub f}H° (298.15 K) = −1615.84 ± 9.01 kJ mol{sup −1}. The stabilization energy for above-mentioned compound has been calculated as well. It has been shown that barium cerate doped gadolinium and indium has higher stabilization energy than BaCe{sub 0.7}Nd{sub 0.2}In{sub 0.1}O{sub 2.85} and BaCeO{sub 3}. The reaction enthalpy with CO{sub 2} interaction has been calculated for BaCe{sub 0.7}Gd{sub 0.2}In{sub 0.1}O{sub 2.85}.

  1. Determination of melting and solidification enthalpy of hypereutectic silumins

    OpenAIRE

    J. Piątkowski; J. Szymszal

    2008-01-01

    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 particu...

  2. Temperature-dependent enthalpy of oxygenation in Antarctic fish hemoglobins

    DEFF Research Database (Denmark)

    Fago, A.; Wells, R.M.G.; Weber, Roy E.

    1997-01-01

    The effect of temperature on the oxygen-binding properties of the hemoglobins of three cold-adapted Antarctic fish species, Dissostichus mawsoni, Pagothenia borchgrevinki and Trematomus, sp., has been investigated under different pH values and buffer conditions. A clear non linear van't Hoff plot...... literature data for the enthalpy of oxygenation in Antarctic fish hemoglobins derives from the use of the nonintegrated (linearized) form of the van't Hoff equation over different temperature ranges. The general assumption that a low heat of oxygenation in hemoglobins from polar animals represents...

  3. Dissociation of methanol in intense femtosecond laser field

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Methanol was irradiated by 80 fs laser pulse, intensity range of 1013-1014 W/cm2. A TOF-mass spectrometer was coupled to the laser system and used to detect the ions produced. The parent ions CH3OH+ appeared firstly at the laser intensity of 1.4×1013 W/cm2. While the laser intensity was gradually increased, the parent ions were dissociated and the primary ions CH2OH+ were given as verified from the irradiation of deuterated methanol (CH3OD) showing the C-H bond cracking firstly. While the laser intensity was further increased to 2.0 ×1013 W/cm2, the C-O bonds of the parent ions also broke to give CH3+. When the laser intensity was higher, smaller fragment ions like CH+, C+, OH+ and O+ also appeared. Among the fragment ions, only H+ ion yield had anisotropic angular distribution dependence on the laser polarization vector in the dissociation of methanol. All the experimental observations show that the dissociation of methanol proceeds through stepwise mechanism but not Coulomb explosion.

  4. Multiphoton dissociative ionization of CS+

    Science.gov (United States)

    Rajput, Jyoti; Jochim, Bethany; Zohrabi, M.; Betsch, K. J.; Ablikim, U.; Berry, Ben; Severt, T.; Summers, A. M.; Armstrong, G. S. J.; Esry, B. D.; Carnes, K. D.; Ben-Itzhak, I.

    2015-05-01

    We have studied the dissociative photoionization of a CS+ molecular ion beam in the strong-field regime using <50 fs IR laser pulses (λ ~ 790 nm) from a 10 kHz, ~2 mJ (per pulse) Ti:Sapphire laser system. A coincidence three-dimensional momentum imaging method was used to measure all ions and neutrals formed during this multiphoton process. Two prominent channels were observed: charge-symmetric dissociation, yielding C+ + S+, and charge-asymmetric dissociation, yielding C + S2+. The differences between these two channels with reference to their relative production probability, energetics, and angular distributions is the focus of this work. This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy. BJ is also supported by DOE-SCGF (DE-AC05-06OR23100).

  5. Towards simple orbital-dependent density functionals for molecular dissociation

    Science.gov (United States)

    Zhang, Igor Ying; Richter, Patrick; Scheffler, Matthias

    2015-03-01

    Density functional theory (DFT) is one of the leading first-principles electronic-structure theories. However, molecular dissociation remains a challenge, because it requires a well-balanced description of the drastically different electronic structure at different bond lengths. One typical and well-documented case is the dissociation of both H2+ and H2, for which all popular DFT functionals fail. We start from the Bethe-Goldstone equation to propose a simple orbital-dependent correlation functional which generalizes the linear adiabatic connection approach. The resulting scheme is based on second-order perturbation theory (PT2), but includes the self-consistent coupling of electron-hole pairs, which ensures the correct H2 dissociation limit and gives a finite correlation energy for systems with a (near)-degenerate energy gap. This coupling PT2-like (CPT2) approximation delivers a significant improvement over all existing functionals for both H2 and H2+ dissociation. We will demonstrate the reason for this improvement analytically for H2 in a minimal basis.

  6. Electron-impact dissociative ionization of CClF{sub 3} and CCl{sub 3}F

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Roberto [Facultad de Farmacia, Departamento de Quimica Fisica, Universidad del Pais Vasco, Paseo de la Universidad 7. 01006 Vitoria (Spain); Sierra, Borja [Facultad de Ciencia y Tecnologia, Departamento de Quimica Fisica, Universidad del Pais Vasco, Apdo. 644. 48080 Bilbao (Spain); Basterretxea, Francisco J. [Facultad de Ciencia y Tecnologia, Departamento de Quimica Fisica, Universidad del Pais Vasco, Apdo. 644. 48080 Bilbao (Spain); Sanchez Rayo, Maria N. [Facultad de Ciencia y Tecnologia, Departamento de Quimica Fisica, Universidad del Pais Vasco, Apdo. 644. 48080 Bilbao (Spain); Castano, Fernando [Facultad de Ciencia y Tecnologia, Departamento de Quimica Fisica, Universidad del Pais Vasco, Apdo. 644. 48080 Bilbao (Spain)], E-mail: f.castano@ehu.es

    2006-11-08

    A crossed-beam experiment of well characterized kinetic energy (KE) electrons and supersonic halomethanes CCl{sub 3}F and CClF{sub 3} in Ar carrier has been carried out in order to quantify the kinetic energy distributions (KEDs), the appearance energies (AEs) and the channels involved in the production of nascent ions. The ion KEDs were derived from the band profiles of the time-of-flight mass spectrum and the total KEDs computed using conservation laws. Heavier ions are created with KED peaked at thermal energies in contrast with low mass atoms or other fragments, where the distribution is broader and the maximum is at much higher energies. A discussion of the dissociative ionization pathways derived from the appearance energies, total average KEDs, thermodynamic enthalpies and computed electron dissociation energies is reported. The role of the vibrational and rotational energies into the dissociative processes is also discussed.

  7. Kinetics and enthalpy of crystallization of uric acid dihydrate

    Energy Technology Data Exchange (ETDEWEB)

    Sádovská, Galina, E-mail: galina.sadovska@upce.cz; Honcová, Pavla; Sádovský, Zdeněk

    2013-08-20

    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{sup −3} NaCl and at thermodynamic and physiological temperature (25 and 37 °C) was studied using isoperibolic reaction twin calorimeter. The enthalpy of crystallization Δ{sub cr}H = −47.3 ± 0.9 and −46.2 ± 1.4 kJ mol{sup −1}and kinetic constant k{sub g} = 2.0 × 10{sup −8} and 9.6 × 10{sup −8} m{sup 4} s{sup −1} mol{sup −1} were determined at 25 and 37 °C, respectively.

  8. Modified enthalpy method for the simulation of melting and solidification

    Indian Academy of Sciences (India)

    Niranjan N Gudibande; Kannan N Iyer

    2013-12-01

    Enthalpy method is commonly used in the simulation of melting and solidification owing to its ease of implementation. It however has a few shortcomings. When it is used to simulate melting/solidification on a coarse grid, the temperature time history of a point close to the interface shows waviness. While simulatingmelting with natural convection, in order to impose no-slip and impermeability boundary conditions, momentum sink terms are used with some arbitrary constants called mushy zone constants. The values of these are very large and have no physical basis. Further, the chosen values affect the predictions and hence have to be tuned for satisfactory comparison with experimental data. To overcome these deficiencies, a new cell splitting method under the framework of the enthalpy method has been proposed. This method does not produce waviness nor requires mushy zone constants for simulating melting with natural convection. The method is then demonstrated for a simple onedimensional melting problem and the results are compared with analytical solutions. The method is then demonstrated to work in two-dimensions and comparisons are shown with analytical solutions for problems with planar and curvilinear interfaces. To further benchmark the present method, simulations are performed for melting in a rectangular cavity with natural convection in the liquid melt. The solid–liquid interface obtained is compared satisfactorily with the experimental results available in literature.

  9. Relaxation of enthalpy fluctuations during sub-T(g) annealing of glassy selenium.

    Science.gov (United States)

    Gulbiten, Ozgur; Mauro, John C; Lucas, Pierre

    2013-06-28

    The relaxation behavior of glass is influenced by the presence of dynamical heterogeneities, which lead to an intrinsically non-monotonic decay of fluctuations in density and enthalpy during isothermal annealing. This is apparently a universal feature of fragile glass forming systems associated with localized spatial variations in relaxation time. Here we present direct experimental observation of the nonmonotonic evolution of enthalpy fluctuations in glassy selenium annealed near room temperature. The nonmonotonic change in the distribution of enthalpy fluctuations measured by heat capacity spectroscopy offers direct evidence for the presence of dynamical heterogeneity in this glass. An enthalpy landscape model of selenium is then used to simulate annealing under identical conditions. The simulation results closely follow the evolution of enthalpy fluctuations observed experimentally. The close match between model and experiment demonstrate that enthalpy and density fluctuations are sources of dynamical heterogeneities in glassy materials.

  10. Determination of the enthalpy of solute-solvent interaction from the enthalpy of solution: aqueous solutions of erythritol and L-threitol.

    Science.gov (United States)

    Lopes Jesus, A J; Tomé, Luciana I N; Eusébio, M Ermelinda S; Redinha, J S

    2006-05-11

    In this work the enthalpy of the solute-solvent interaction of erythritol and L-threitol in aqueous solution was determined from the values obtained for the enthalpy of solvation. The values for this property were calculated from those determined for the enthalpies of solution and sublimation. To determine the values of the enthalpy of solute-solvent interaction, the solvation process is considered as taking place in three steps: opening a cavity in the solvent to hold the solute molecule, changing the solute conformation when it passes from the gas phase into solution, and interaction between the solute and the solvent molecules. The cavity enthalpy was calculated by the scaled particle theory and the conformational enthalpy change was estimated from the value of this function in the gas phase and in solution. Both terms were determined by DFT calculations. The solvent effect on the solute conformation in solution was estimated using the CPCM solvation model. The importance of the cavity and conformational terms in the interpretation of the enthalpy of solvation is noted. While the cavity term has been used by some authors, the conformational term is considered for the first time. The structural features in aqueous solution of erythritol and L-threitol are discussed.

  11. Dissociative symptoms and dissociative disorders comorbidity in obsessive compulsive disorder: Symptom screening, diagnostic tools and reflections on treatment

    OpenAIRE

    Belli, Hasan

    2014-01-01

    Borderline personality disorder, conversion disorder and obsessive compulsive disorder frequently have dissociative symptoms. The literature has demonstrated that the level of dissociation might be correlated with the severity of obsessive compulsive disorder (OCD) and that those not responding to treatment had high dissociative symptoms. The structured clinical interview for DSM-IV dissociative disorders, dissociation questionnaire, somatoform dissociation questionnaire and dissociative expe...

  12. Hydrogen dissociation on metal surfaces

    NARCIS (Netherlands)

    Wijzenbroek, M.

    2016-01-01

    Dissociative chemisorption is an important reaction step in many catalytic reactions. An example of such a reaction is the Haber-Bosch process, which is used commercially to produce ammonia, an important starting material in the production of fertilisers. In theoretical descriptions of such chemical

  13. [Gender differences in dissociative disorders].

    Science.gov (United States)

    Spitzer, C; Freyberger, H J

    2008-01-01

    The relationship between mental illness, on the one hand, and sex and gender, on the other hand, has received interest since the beginning of medicine in antique times. A prototypical example of a seemingly woman-specific disease is hysteria. The term itself, which is derived from the Greek word for womb, denotes a psychosexual dimension comprising the current attitude towards sexuality and the dominating gender relationship. In addition, the colourful history of hysteria indicates that illness is not exclusively determined by biological factors, but also significantly by socio-cultural influences, for example in the treatment of hysterical women. Even nowadays, there is a wide-spread belief that dissociative symptoms and disorders, which have succeeded hysteria in current classification systems, are predominantly seen in women. However, empirical studies in the general population and in different clinical samples using sound instruments have indicated that dissociative symptoms do not differ between the genders. The seemingly dominance of dissociative disorders in women may also depend on the socio-cultural context, because men with dissociative disorders usually do not enter the general health system, but rather the legal system, i.e. they can be found in jail or forensic institutions. PMID:18185968

  14. Dissociative disorders in DSM-5

    NARCIS (Netherlands)

    Spiegel, David; Loewenstein, Richard J.; Lewis-Fernandez, Roberto; Sar, Vedat; Simeon, Daphne; Vermetten, Eric; Cardena, Etzel; Dell, Paul F.

    2011-01-01

    Background: We present recommendations for revision of the diagnostic criteria for the Dissociative Disorders (DDs) for DSM-5. The periodic revision of the DSM provides an opportunity to revisit the assumptions underlying specific diagnoses and the empirical support, or lack of it, for the defining

  15. DISSOCIATIVE DISORDERS IN DSM-5

    NARCIS (Netherlands)

    Spiegel, David; Loewenstein, Richard J.; Lewis-Fernandez, Roberto; Sar, Vedat; Simeon, Daphne; Vermetten, Eric; Cardena, Etzel; Dell, Paul F.

    2011-01-01

    Background: We present recommendations for revision of the diagnostic criteria for the Dissociative Disorders (DDs) for DSM-5. The periodic revision of the DSM provides an opportunity to revisit the assumptions underlying specific diagnoses and the empirical support, or lack of it, for the defining

  16. Analytic calculation of formation enthalpies directly from interatomic potentials for binary and ternary refractory metal systems

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    An analytic method is proposed to calculate the formation enthalpy directly from empirical n-body potential and applied to the binary and ternary systems consisting of the refractory metals Mo, Nb, Ta and W. It turns out that the calculated enthalpies are in overall agreement with experimental observations and some other theoretical calculations. Interestingly, it shows that the formation enthalpies of the ternary systems are significantly affected by those of the constituent binary systems.

  17. Enthalpies of Solution of Complexes of Rare Earth Nitrate with L-α-Histidine in Water

    Institute of Scientific and Technical Information of China (English)

    刘洋; 房艳; 高胜利; 陈三平; 史启祯

    2002-01-01

    The enthalpies of solution in water of complexes of RE(NO3)3 (RE=La~Nd, Sm~Lu, Y) with L-α-Histidine (His) were measured at 298.15 K. The standard enthalpies of formation of RE(His)3+(aq) were calculated. The "tetrad effect" regularity was observed from the curve, which is the enthalpies of solution plotted against the atomic numbers of the elements in lanthanide series.

  18. Significant discrepancies between van't Hoff and calorimetric enthalpies. II.

    OpenAIRE

    Liu, Y; Sturtevant, J. M.

    1995-01-01

    Isothermal calorimetric titration of 18-crown-6 ether with BaCl2 in pure aqueous solution over the temperature range 7-40 degrees C gives precise binding constants and enthalpy changes. Nonlinear least-squares fitting of the binding constants to the integrated van't Hoff equation, including a temperature-independent change in heat capacity, leads to van't Hoff enthalpies that differ significantly from the observed calorimetric enthalpies. This perplexing discrepancy appears at present to be v...

  19. Theoretical investigation of the competitive mechanism between dissociation and ionization of H₂⁺ in intense field.

    Science.gov (United States)

    Yao, Hongbin; Zhao, Guangjiu

    2014-10-01

    The competitive mechanism between dissociation and ionization of hydrogen molecular ion in intense field has been theoretically investigated by using an accurate non-Born-Oppenheimer method. The relative yield of fragments indicates that the dissociation and ionization channels are competitive with the increasing laser intensity from 5.0 × 10(13) to 2.0 × 10(14) W/cm(2). In the case of intensity lower than 1.0 × 10(14) W/cm(2), the dissociation channel is dominant, with a minor contribution from ionization. The mechanism of dissociation includes the contributions from the bond softening, bond hardening, below-threshold dissociation, and above-threshold dissociation, which are strongly dependent on the laser intensity and initial vibrational state. Furthermore, the ionization dominates over the dissociation channel at the highest intensity of 2.0 × 10(14) W/cm(2). The reasonable origin of ionization is ascribed as the above-threshold Coulomb explosion, which has been demonstrated by the space-time dependent ionization rate. Moreover, the competition mechanism between dissociation and ionization channels are displayed on the total kinetic energy resolved (KER) spectra, which could be tested at current experimental conditions.

  20. Enthalpy and entropy interaction parameters of sodium chloride with some monosaccharides in water

    Institute of Scientific and Technical Information of China (English)

    ZHUO; Kelei; WANG; Jianji; BAI; Guangyue; YAN; Haike; WANG

    2004-01-01

    Dilution enthalpies of sodium chloride and some monosaccharides (glucose, galactose, xylose, arabinose, and fructose) in water and mixing enthalpies of aqueous sodium chloride and these monosaccharide solutions were measured by using an improved precision semimicro-titration calorimeter. Transfer enthalpies of sodium chloride from water to aqueous saccharide solutions were evaluated as well as enthalpy interaction parameters of sodium chloride with these monosaccharides in water. Combined with Gibbs energy interaction parameters, entropy interaction parameters were also obtained. The results show that interactions of the saccharides with sodium chloride depend on the stereochemistry of saccharide molecules. These interaction parameters can identify stereochemical structure of saccharide molecules.

  1. EFFECT OF CROSS-LINKING ON THE EXCESS ENTHALPY RELAXATION OF EPOXY

    Institute of Scientific and Technical Information of China (English)

    CHEN Yuping; QI Zongneng

    1987-01-01

    A method of comparative DSC technique is proposed for excess enthalpy relaxation study. The essential of the comparative DSC technique consists of comparing the enthalpy relaxation behavior of an aged sample with a quenched sample as reference. The accuracy of comparison is improved because of simultaneous measuring of the sample and reference which makes noise of the apparatus subtractive. This technique has been applied to studying the influence of crosslinking on the enthalpy relaxation behavior of epoxy resins. The effect of crosslinking on the kinetics of enthalpy relaxation of epoxy resins is discussed.

  2. Dissociating Prediction Failure: Considerations from Music Perception

    DEFF Research Database (Denmark)

    Ross, Suzi; Hansen, Niels Christian

    2016-01-01

    Dissociating Prediction Failure: Considerations from Music Perception The Journal of Neuroscience, 16 March 2016, 36(11): 3103-3105;......Dissociating Prediction Failure: Considerations from Music Perception The Journal of Neuroscience, 16 March 2016, 36(11): 3103-3105;...

  3. Consequences of metal-oxide interconversion for C-H bond activation during CH4 reactions on Pd catalysts.

    Science.gov (United States)

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-10-16

    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH4 react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to H-abstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cation-lattice oxygen pairs (Pd(2+)-O(2-)) in PdO. The charges in the CH3 and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*-covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd(2+)-O(2-) pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H3C···Pd···H)(‡) transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3(•)···*OH)(‡) that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd(2+) and vicinal O(2-), Pd(ox)-O(ox), cleave C-H bonds heterolytically via σ-bond metathesis, with Pd(2+) adding to the C-H bond, while O(2-) abstracts the H-atom to form a four-center (H3C(δ-)···Pd(ox)···H(δ+)···O(ox))(‡) transition state without detectable Pd(ox) reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH4 oxidation turnover rates at oxygen chemical potentials leading to Pd to PdO transitions. These distinct mechanistic pathways for C-H bond activation, inferred from theory

  4. Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH₄ Reactions on Pd Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chin, Ya-Huei; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-10-01

    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH₄ react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to Habstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cationlattice oxygen pairs (Pd2+-O2-) in PdO. The charges in the CH₃ and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*- covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd2+-O2- pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H₃C···Pd···H)‡ transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3 •···*OH)‡ that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd2+ and vicinal O2-, Pdox-Oox, cleave C-H bonds heterolytically via σ-bond metathesis, with Pd2+ adding to the C-H bond, while O2- abstracts the H-atom to form a four-center (H3Cδ-···Pdox···Hδ+···Oox) transition state without detectable Pdox reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH₄ oxidation turnover rates at oxygen chemical

  5. Diffusion bonding

    Science.gov (United States)

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  6. BEP-relations for N2 dissociation over stepped transition metal and alloy surfaces

    DEFF Research Database (Denmark)

    Fronczek-Munter, Ture Rønved; Bligaard, Thomas; Christensen, Claus H.;

    2008-01-01

    We present density functional theory (DFT) calculations for N(2) dissociation on stepped face-centred cubic (211) surface slabs. By using the same crystal structure, the same adsorption site for atomic nitrogen, and the same transition-state bond length of N(2) over a range of pure metal surfaces...

  7. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    Science.gov (United States)

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi

    2015-02-01

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O-/OH- and CH3- are recorded, indicating the low kinetic energies of O-/OH- for ethanol while the low and high kinetic energy distributions of O- ions for acetaldehyde. The CH3- image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O- ion via the dehydrogenated intermediate, CH3CHO- (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH3- is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  8. Electronic bond tuning with heterocyclic carbenes

    KAUST Repository

    Falivene, Laura

    2013-01-01

    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  9. Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.

    Science.gov (United States)

    Uddin, M; Coombe, D

    2014-03-20

    Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to

  10. 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.)

  11. Changes of enthalpy slope in subcooled flow boiling

    Science.gov (United States)

    Collado, Francisco J.; Monné, Carlos; Pascau, Antonio

    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.

  12. Sulfide scaling in low enthalpy geothermal environments; A survey

    Energy Technology Data Exchange (ETDEWEB)

    Criaud, A.; Fouillac, C. (Bureau de Recherches Geologiques et Minieres (BRGM), 45 - Orleans (France))

    1989-01-01

    A review of the sulfide scaling phenomena in low-temperature environments is presented. While high-temperature fluids tend to deposit metal sulfides because of their high concentrations of dissolved metals and variations of temperature, pressure and fluid chemistry, low temperature media are characterized by very low metal content but much higher dissolved sulfide. In the case of the goethermal wells of the Paris Basin, detailed studies demonstrate that the relatively large concentrations of chloride and dissolved sulfide are responsible for corrosion and consequent formation of iron sulfide scale composed of mackinawite, pyrite and pyrrhotite. The effects of the exploitation schemes are far less important than the corrosion of the casings. The low-enthalpy fluids that do not originate from sedimentary aquifers (such as in Iceland and Bulgaria), have a limited corrosion potential, and the thin sulfide film that appears may prevent the progress of corrosion.

  13. Standard molar enthalpies of formation of hydroxy-, chlor-, and bromapatite

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, Fernando J.A.L. [Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico 1049-001 Lisbon (Portugal); Minas da Piedade, Manuel E. [Departamento de Quimica e Bioquimica, Faculdade de Ciencias, Universidade de Lisboa, 1749-016 Lisbon (Portugal); Calado, Jorge C.G. [Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico 1049-001 Lisbon (Portugal)]. E-mail: jcalado@ist.utl.pt

    2005-10-15

    The standard (p{sup 0} =0.1MPa) molar enthalpies of formation in the crystalline state of hydroxyapatite, chlorapatite and a preliminary value for bromapatite, at T=298.15K, were determined by reaction-solution calorimetry as: {delta}{sub f}H{sub m}{sup 0} [Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2},cr]=-(13399+/-11)kJ.mol{sup -1},{delta}{sub f}H{sub m}{sup 0} [Ca{sub 10}(PO{sub 4}){sub 6}Cl{sub 2},cr]=-(13231+/-82)kJ.mol{sup -1},and{delta}{sub f}H{sub m}{sup 0} [Ca{sub 10}(PO{sub 4}){sub 6}Br{sub 2},cr]=-(13063+/-81)kJ.mol{sup -1}. A critical assessment of these results and of previously published data is made. Finally, the standard molar enthalpy of formation of iodapatite is estimated as {delta}{sub f}H{sub m}{sup 0} [Ca{sub 10}(PO{sub 4}){sub 6}I{sub 2},cr]=-12949kJ.mol{sup -1}, from a linear correlation of {delta}{sub f}H{sub m}{sup 0} [Ca{sub 10}(PO{sub 4}){sub 6}X{sub 2},cr] (X=OH, F, Cl, Br) against the corresponding {delta}{sub f}H{sub m}{sup 0} [CaX{sub 2},cr].

  14. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1 - C10

    Science.gov (United States)

    Acree, William; Chickos, James S.

    2016-09-01

    A compendium of phase change enthalpies published in 2010 is updated to include the period 1880-2015. Phase change enthalpies including fusion, vaporization, and sublimation enthalpies are included for organic, organometallic, and a few inorganic compounds. Part 1 of this compendium includes organic compounds from C1 to C10. Part 2 of this compendium, to be published separately, will include organic and organometallic compounds from C11 to C192. Sufficient data are presently available to permit thermodynamic cycles to be constructed as an independent means of evaluating the reliability of the data. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T = 298.15 K, and a protocol for doing so are briefly discussed.

  15. A Novel Topological Index F* and Its Correlation With Standard Formaton Enthalpies of ABn(g) Molecules

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The topological index F* is defined and obtained by the method of a non-dimensional unit calculation in which three matrices multiply with each other. These matrices represent the connective cases of atoms in a molecule, the structural features of atoms on top and the bonded cases of the adjacent atoms respectively. The standard formation enthalpies of ABn(g) molecules were correlated with F* (A= C, Al, Si, Ti, Zr, B =F, Cl, Br, I, H, n=1-4) and these correlation coefficients are all more than 0.96.Some molecules (e.g CH4, SiH4,etc.)can be preferably handled by F* but can not be dealt with by other topological indices.By contrast to traditional hydrogen suppressed graph,the contribution of hydrogen atoms to structures and properties of molecules is considered.

  16. Investigation of vinyl phosphonic acid/hydroxylated α-Al 2O 3( 0 0 0 1 ) reaction enthalpies

    Science.gov (United States)

    Hector, L. G., Jr.; Opalka, S. M.; Nitowski, G. A.; Wieserman, L.; Siegel, D. J.; Yu, H.; Adams, J. B.

    2001-11-01

    The eleven ion vinyl phosphonic acid (VPA) molecule consists of a phosphorus ion that serves as a cationic anchor for two electron-rich functional groups, viz., a tripodal oxygen-rich base and vinyl hydrocarbon tail. Recent inelastic tunneling experiments have implied that VPA binds in a tridentate coordination though its base leaving the vinyl tail free to react with a resin in adhesive bonding applications. Using first-principles total energy calculations, the reaction enthalpies for bonding of a single VPA molecule to selected threefold sites on hydroxylated α-Al 2O 3(0 0 0 1) are investigated. Tridentate, bidentate and unidentate coordinations, both with and without liberated water molecules, are examined to determine if the tridentate coordination is favored over the others and the extent to which the VPA molecule is sensitive to surface site geometry. The electron localization function is used to examine the extent of covalent character between the P-O bonds that anchor the VPA fragment to the oxide surface. Some comments on the entropic contributions of the VPA and H 2O molecules to the binding energetics are offered, along with a discussion of the effects of H 2O placement on the oxide surface and aluminum alloying agents.

  17. Coulomb dissociation of N,2120

    Science.gov (United States)

    Röder, Marko; Adachi, Tatsuya; Aksyutina, Yulia; Alcantara, Juan; Altstadt, Sebastian; Alvarez-Pol, Hector; Ashwood, Nicholas; Atar, Leyla; Aumann, Thomas; Avdeichikov, Vladimir; Barr, M.; Beceiro, Saul; Bemmerer, Daniel; Benlliure, Jose; Bertulani, Carlos; Boretzky, Konstanze; Borge, Maria J. G.; Burgunder, G.; Caamaño, Manuel; Caesar, Christoph; Casarejos, Enrique; Catford, Wilton; Cederkäll, Joakim; Chakraborty, S.; Chartier, Marielle; Chulkov, Leonid; Cortina-Gil, Dolores; Crespo, Raquel; Datta Pramanik, Ushasi; Diaz-Fernandez, Paloma; Dillmann, Iris; Elekes, Zoltan; Enders, Joachim; Ershova, Olga; Estrade, A.; Farinon, F.; Fraile, Luis M.; Freer, Martin; Freudenberger, M.; Fynbo, Hans; Galaviz, Daniel; Geissel, Hans; Gernhäuser, Roman; Göbel, Kathrin; Golubev, Pavel; Gonzalez Diaz, D.; Hagdahl, Julius; Heftrich, Tanja; Heil, Michael; Heine, Marcel; Heinz, Andreas; Henriques, Ana; Holl, Matthias; Ickert, G.; Ignatov, Alexander; Jakobsson, Bo; Johansson, Hâkan; Jonson, Björn; Kalantar-Nayestanaki, Nasser; Kanungo, Rituparna; Kelic-Heil, Aleksandra; Knöbel, Ronja; Kröll, Thorsten; Krücken, Reiner; Kurcewicz, J.; Kurz, Nikolaus; Labiche, Marc; Langer, Christoph; Le Bleis, Tudi; Lemmon, Roy; Lepyoshkina, Olga; Lindberg, Simon; Machado, Jorge; Marganiec, Justyna; Mostazo Caro, Magdalena; Movsesyan, Alina; Najafi, Mohammad Ali; Nilsson, Thomas; Nociforo, Chiara; Panin, Valerii; Paschalis, Stefanos; Perea, Angel; Petri, Marina; Pietri, S.; Plag, Ralf; Prochazka, A.; Rahaman, Md. Anisur; Rastrepina, Ganna; Reifarth, Rene; Ribeiro, Guillermo; Ricciardi, M. Valentina; Rigollet, Catherine; Riisager, Karsten; Rossi, Dominic; Sanchez del Rio Saez, Jose; Savran, Deniz; Scheit, Heiko; Simon, Haik; Sorlin, Olivier; Stoica, V.; Streicher, Branislav; Taylor, Jon; Tengblad, Olof; Terashima, Satoru; Thies, Ronja; Togano, Yasuhiro; Uberseder, Ethan; Van de Walle, J.; Velho, Paulo; Volkov, Vasily; Wagner, Andreas; Wamers, Felix; Weick, Helmut; Weigand, Mario; Wheldon, Carl; Wilson, G.; Wimmer, Christine; Winfield, J. S.; Woods, Philip; Yakorev, Dmitry; Zhukov, Mikhail; Zilges, Andreas; Zuber, Kai; R3B Collaboration

    2016-06-01

    Neutron-rich light nuclei and their reactions play an important role in the creation of chemical elements. Here, data from a Coulomb dissociation experiment on N,2120 are reported. Relativistic N,2120 ions impinged on a lead target and the Coulomb dissociation cross section was determined in a kinematically complete experiment. Using the detailed balance theorem, the 19N (n ,γ )20N and 20N (n ,γ ) 21N excitation functions and thermonuclear reaction rates have been determined. The 19 (n ,γ )20N rate is up to a factor of 5 higher at T <1 GK with respect to previous theoretical calculations, leading to a 10% decrease in the predicted fluorine abundance.

  18. Dissociative symptoms and REM sleep.

    Science.gov (United States)

    van Heugten-van der Kloet, Dalena; Merckelbach, Harald; Lynn, Steven Jay

    2013-12-01

    Llewellyn has written a fascinating article about rapid eye movement (REM) dreams and how they promote the elaborative encoding of recent memories. The main message of her article is that hyperassociative and fluid cognitive processes during REM dreaming facilitate consolidation. We consider one potential implication of this analysis: the possibility that excessive or out-of-phase REM sleep fuels dissociative symptomatology. Further research is warranted to explore the psychopathological ramifications of Llewellyn's theory. PMID:24304772

  19. Effect of the initial stage of annealing on modeling of enthalpy relaxation in a hyperquenched glass

    DEFF Research Database (Denmark)

    Zhang, Yanfei; Guo, Xiaoju; Yue, Yuanzheng

    2013-01-01

    One of the major challenges in glass relaxation study is to establish a universal model describing the enthalpy relaxation in both the hyperquenched glass (HQG) (i.e., far from equilibrium) and the partially annealed hyperquenched glass(AHQG). In particular, the detailed features of the enthalpy...

  20. 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.

  1. Two-temperature models for nitrogen dissociation

    Science.gov (United States)

    da Silva, M. Lino; Guerra, V.; Loureiro, J.

    2007-12-01

    Accurate sets of nitrogen state-resolved dissociation rates have been reduced to two-temperature (translational T and vibrational Tv) dissociation rates. The analysis of such two-temperature dissociation rates shows evidence of two different dissociation behaviors. For Tv 0.3 T dissociation proceeds predominantly form the near-dissociative vibrational levels, with an abrupt change of behavior at Tv = 0.3 T. These two-temperature sets have then been utilized as a benchmark for the comparison against popular multitemperature dissociation models (Park, Hansen, Marrone-Treanor, Hammerling, Losev-Shatalov, Gordiets, Kuznetsov, and Macheret-Fridman). This has allowed verifying the accuracy of each theoretical model, and additionally proposing adequate values for any semi-empirical parameters present in the different theories. The Macheret-Fridman model, who acknowledges the existence of the two aforementioned dissociation regimes, has been found to provide significantly more accurate results than the other models. Although these different theoretical approaches have been tested and validated solely for nitrogen dissociation processes, it is reasonable to expect that the general conclusions of this work, regarding the adequacy of the different dissociation models, could be extended to the description of arbitrary diatomic dissociation processes.

  2. Impurity migration and effects on vacancy formation enthalpy in polycrystalline depleted uranium

    Science.gov (United States)

    Lund, K. R.; Lynn, K. G.; Weber, M. H.; Macchi, C.; Somoza, A.; Juan, A.; Okuniewski, M. A.

    2015-11-01

    We have used Doppler-broadening of the positron-electron annihilation radiation technique and VASP calculations to verify the previously reported vacancy formation enthalpy Hvf in polycrystalline depleted uranium. Experimentally we have confirmed a Hvf of (1.6 ± 0.2) eV. VASP calculations using GGA and LDA approximations gave vacancy formation enthalpies values of 1.98 eV and 2.22 eV respectively. We found residual oxygen in the sample diminished these values by 50% or more. Our new experimental and theoretical data supports the notion that oxygen impurities in the sample are responsible for lower values of vacancy formation enthalpies. Measured and calculated vacancy formation enthalpies, as well as the obtained oxygen migration enthalpy of (0.6 ± 0.1) eV, are compared and discussed with values reported in the literature.

  3. Effect of pulping variables on enthalpy of kraft black liquors: Empirical predictive models

    Energy Technology Data Exchange (ETDEWEB)

    Zaman, A.A.; Fricke, A.L. [Univ. of Florida, Gainesville, FL (United States). Dept. of Chemical Engineering

    1996-07-01

    The effects of pulping variables on enthalpy of slash pine kraft black liquors from a 2{sup k} + 2k + 1 (k = 4) central composite design pulping experiments that were performed in a large pilot scale digester have been studied. The four cooling variables were effective alkali, sulfidity, cooking temperature, and time at temperature. In all cases, the white liquor was adjusted to a causticizing efficiency of 85% and a reduction of 93% with Na{sub 2}CO{sub 3} and Na{sub 2}SO{sub 4}. The enthalpy of these liquors was determined over wide ranges of temperature and solids concentrations using a Setaram C-80 calorimeter. In this work, previous models for enthalpy-concentration relations were used to perform a systematic study on the effects of pulping conditions on enthalpy and to develop statistically based quantitative models for enthalpy as a function of pulping variables. These results are presented, and their utility is discussed.

  4. Bulk Enthalpy Calculations in the Arc Jet Facility at NASA ARC

    Science.gov (United States)

    Thompson, Corinna S.; Prabhu, Dinesh; Terrazas-Salinas, Imelda; Mach, Jeffrey J.

    2011-01-01

    The Arc Jet Facilities at NASA Ames Research Center generate test streams with enthalpies ranging from 5 MJ/kg to 25 MJ/kg. The present work describes a rigorous method, based on equilibrium thermodynamics, for calculating the bulk enthalpy of the flow produced in two of these facilities. The motivation for this work is to determine a dimensionally-correct formula for calculating the bulk enthalpy that is at least as accurate as the conventional formulas that are currently used. Unlike previous methods, the new method accounts for the amount of argon that is present in the flow. Comparisons are made with bulk enthalpies computed from an energy balance method. An analysis of primary facility operating parameters and their associated uncertainties is presented in order to further validate the enthalpy calculations reported herein.

  5. Effect of cure cycle on enthalpy relaxation and post shrinkage in neat epoxy and epoxy composites

    DEFF Research Database (Denmark)

    Jensen, Martin; Jakobsen, Johnny

    2016-01-01

    The effect of cure cycle on enthalpy relaxation and warpage is studied for both neat epoxy and glass/epoxy composites. An approach for determining the enthalpy relaxation in the matrix of composite materials combining modulated differential scanning calorimetry and thermogravimetry is presented....... The enthalpy relaxation is coupled to structural dimension changes upon reheating by performing modulated thermo mechanical analysis. The enthalpy relaxation is affected by the cooling rate and the presence of the fibrous reinforcement, but is unaffected by variation between a 1-stage and 2-stage cure cycle....... Enthalpy recovery is found to exert a minor impact on the sample dimension during reheating since a non-reversing shrinkage is observed during reheating. This shrinkage is ascribed to structural changes on molecular level in the specimen and it is inferred that samples with a high initial disorder only...

  6. 结构优化的焓与熵%Enthalpy and entropy in drug optimization

    Institute of Scientific and Technical Information of China (English)

    郭宗儒

    2012-01-01

    ) and,therefore,serves as a principal indicator of ligand quality. The affinity or dissociation constant of a ligand can be translated into the binding free-energy, which can be measured and dissected into enthalpy and entropy contributions using ITC experiment. During lead optimization, the determination of the free-energy, enthalpy and entropy would allow more accurate and quantitative understanding of the structure-activity relationships in terms of characteristics, orientations, positions and distances of atoms and groups. Combined with the structural biology information derived from the ligand-protein complex, the thermodynamic signatures are conductive to reveal the binding mode and the pharmacophoric features of the ligands. The recognition of structure-activity relationships through the quantitative changes in enthalpy-entropy benefits the elucidation of mechanism of drug action and the guidance to molecular design. This mini-review also illustrates the application of thermodynamics in lead optimization with exemplary cases.

  7. COTHERM: Geophysical Modeling of High Enthalpy Geothermal Systems

    Science.gov (United States)

    Grab, Melchior; Maurer, Hansruedi; Greenhalgh, Stewart

    2014-05-01

    In recent years geothermal heating and electricity generation have become an attractive alternative energy resource, especially natural high enthalpy geothermal systems such as in Iceland. However, the financial risk of installing and operating geothermal power plants is still high and more needs to be known about the geothermal processes and state of the reservoir in the subsurface. A powerful tool for probing the underground system structure is provided by geophysical techniques, which are able to detect flow paths and fracture systems without drilling. It has been amply demonstrated that small-scale features can be well imaged at shallow depths, but only gross structures can be delineated for depths of several kilometers, where most high enthalpy systems are located. Therefore a major goal of our study is to improve geophysical mapping strategies by multi-method geophysical simulations and synthetic data inversions, to better resolve structures at greater depth, characterize the reservoir and monitor any changes within it. The investigation forms part of project COTHERM - COmbined hydrological, geochemical and geophysical modeling of geoTHERMal systems - in which a holistic and synergistic approach is being adopted to achieve multidisciplinary cooperation and mutual benefit. The geophysical simulations are being performed in combination with hydrothermal fluid flow modeling and chemical fluid rock interaction modeling, to provide realistic constraints on lithology, pressure, temperature and fluid conditions of the subsurface. Two sites in Iceland have been selected for the study, Krafla and Reykjanes. As a starting point for the geophysical modeling, we seek to establish petrophysical relations, connecting rock properties and reservoir conditions with geophysical parameters such as seismic wave speed, attenuation, electrical conductivity and magnetic susceptibility with a main focus on seismic properties. Therefore, we follow a comprehensive approach involving

  8. Quantum entanglement and the dissociation process of diatomic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Esquivel, Rodolfo O; Molina-Espiritu, Moyocoyani [Departamento de Quimica, Universidad Autonoma Metropolitana, 09340-Mexico DF (Mexico); Flores-Gallegos, Nelson [Unidad Profesional Interdisciplinaria de IngenierIa, Campus Guanajuato del Instituto Politecnico Nacional, 36275-Guanajuato (Mexico); Plastino, A R; Angulo, Juan Carlos; Dehesa, Jesus S [Instituto Carlos I de Fisica Teorica y Computacional, and Departamento de Fisica Atomica, Molecular y Nuclear, Universidad de Granada, 18071-Granada (Spain); Antolin, Juan, E-mail: esquivel@xanum.uam.mx, E-mail: arplastino@ugr.es [Departamento de Fisica Aplicada, EUITIZ, Universidad de Zaragoza, 50018-Zaragoza (Spain)

    2011-09-14

    In this work, we investigate quantum entanglement-related aspects of the dissociation process of some selected, representative homo- and heteronuclear diatomic molecules. This study is based upon high-quality ab initio calculations of the (correlated) molecular wavefunctions involved in the dissociation processes. The values of the electronic entanglement characterizing the system in the limit cases corresponding to (i) the united-atom representation and (ii) the asymptotic region when atoms dissociate are discussed in detail. It is also shown that the behaviour of the electronic entanglement as a function of the reaction coordinate R exhibits remarkable correspondences with the phenomenological description of the physically meaningful regimes comprising the processes under study. In particular, the extrema of the total energies and the electronic entanglement are shown to be associated with the main physical changes experienced by the molecular spatial electronic density, such as charge depletion and accumulation or bond cleavage regions. These structural changes are characterized by several selected descriptors of the density, such as the Laplacian of the electronic molecular distributions (LAP), the molecular electrostatic potential (MEP) and the atomic electric potentials fitted to the MEP.

  9. Charge-dependent dissociation of insulin cations via ion/ion electron transfer

    Science.gov (United States)

    Liu, Jian; Gunawardena, Harsha P.; Huang, Teng-Yi; McLuckey, Scott A.

    2008-10-01

    The dissociation reactions of various charge states of insulin cations obtained directly from nano-electrospray were investigated as a result of ion/ion electron transfer from azobenzene anions. Data were collected with and without simultaneous ion trap collisional excitation of the first generation charge-reduced product during the ion/ion reaction period. Neither separation of the two constituent chains nor cleavages within the loop defined by the disulfide bridges were observed under normal electron transfer dissociation (ETD) conditions for any of the charge states studied. However, substantial sequence coverage (exocyclic region: 82.6%; entire protein: 38.8%) outside the ring structure was obtained for insulin +6, while only limited coverage (exocyclic: 43.5%; entire protein: 20.4%) was observed for insulin +5 and no dissociation, aside from low abundance side-chain losses, was noted for insulin +4 and +3 in the normal ETD spectra. When the first generation charge-reduced precursor ions were subjected to collisional activation during the ion/ion reaction period, higher sequence coverages were obtained for both insulin +5 (entire protein: 34.7%) and +4 (entire protein: 20.4%) with backbone cleavages occurring within the loop defined by the disulfide bonds. Dissociation of insulin +3 was not significantly improved by the additional activation. Separation of the two constituent chains resulting from cleavages of both of the two disulfide bridges that link the chains was observed for insulin +6, +5, and +4 when the charge-reduced species were activated. The dissociation of disulfide linkages in this study suggests that as the charge state decreases, disulfide bond cleavages dominate over N-C[alpha] bond cleavages in the electron transfer dissociation process.

  10. Energy conservation enthalpy control system and sensor therefor

    Energy Technology Data Exchange (ETDEWEB)

    Nickell, G.T.; Alexander, J.L. Sr.

    1978-01-17

    An energy conservation enthalpy control system utilizes a sensing unit for sensing the wet bulb temperature of sampled air, both outside air and return air, under conditions which approximate adiabatic saturation. The unit includes a housing adapted to pass filtered air through the unit. Water circulated throughout from a sump in the housing is intimately contacted and mixed with the air by a spray or an evaporative pad. A temperature sensing element located in the sump or in the airstream provides a signal indicating the wet bulb temperature of the air under adiabatic saturation conditions. The unit provides the inputs to a control system which operates to coordinate the operations of return air dampers, outside air dampers, and air conditioning equipment. When outside air reaches a wet bulb condition lower than the wet bulb condition of return air in the system, the control system operates to open or modulate the outside air dampers, close or modulate the return air dampers, and modulate or shutoff the chilled water in the system.

  11. Protein stabilization by macromolecular crowding through enthalpy rather than entropy.

    Science.gov (United States)

    Senske, Michael; Törk, Lisa; Born, Benjamin; Havenith, Martina; Herrmann, Christian; Ebbinghaus, Simon

    2014-06-25

    The interior of the cell is a densely crowded environment in which protein stability is affected differently than in dilute solution. Macromolecular crowding is commonly understood in terms of an entropic volume exclusion effect based on hardcore repulsions among the macromolecules. We studied the thermal unfolding of ubiquitin in the presence of different cosolutes (glucose, dextran, poly(ethylene glycol), KCl, urea). Our results show that for a correct dissection of the cosolute-induced changes of the free energy into its enthalpic and entropic contributions, the temperature dependence of the heat capacity change needs to be explicitly taken into account. In contrast to the prediction by the excluded volume theory, we observed an enthalpic stabilization and an entropic destabilization for glucose, dextran, and poly(ethylene glycol). The enthalpic stabilization mechanism induced by the macromolecular crowder dextran was similar to the enthalpic stabilization mechanism of its monomeric building block glucose. In the case of poly(ethylene glycol), entropy is dominating over enthalpy leading to an overall destabilization. We propose a new model to classify cosolute effects in terms of their enthalpic contributions to protein stability.

  12. Mixing Enthalpy for Binary Mixtures Containing Ionic Liquids.

    Science.gov (United States)

    Podgoršek, A; Jacquemin, J; Pádua, A A H; Costa Gomes, M F

    2016-05-25

    A complete review of the published data on the mixing enthalpies of mixtures containing ionic liquids, measured directly using calorimetric techniques, is presented in this paper. The field of ionic liquids is very active and a number of research groups in the world are dealing with different applications of these fluids in the fields of chemistry, chemical engineering, energy, gas storage and separation or materials science. In all these fields, the knowledge of the energetics of mixing is capital both to understand the interactions between these fluids and the different substrates and also to establish the energy and environmental cost of possible applications. Due to the relative novelty of the field, the published data is sometimes controversial and recent reviews are fragmentary and do not represent a set of reliable data. This fact can be attributed to different reasons: (i) difficulties in controlling the purity and stability of the ionic liquid samples; (ii) availability of accurate experimental techniques, appropriate for the measurement of viscous, charged, complex fluids; and (iii) choice of an appropriate clear thermodynamic formalism to be used by an interdisciplinary scientific community. In this paper, we address all these points and propose a critical review of the published data, advise on the most appropriate apparatus and experimental procedure to measure this type of physical-chemical data in ionic liquids as well as the way to treat the information obtained by an appropriate thermodynamic formalism.

  13. Enthalpy versus Entropy: the Thermodynamic Origin of Hard Particle Ordering

    Science.gov (United States)

    Anthamatten, Mitchell; Chen, Shaw; Ou, Jane; Weinfeld, Jeffrey; Department of Chemical Engineering Team

    The topic of hard particle ordering transitions is important in the development of molecular to mesoscale materials with potential applications in biomedicine, catalysis, optoelectronics, and renewable energy. The first step toward deterministic materials design rests on understanding the thermodynamic nature of ordering transitions involving two phases in equilibrium. We apply classical thermodynamics to show that (i) first-order, hard particle ordering transitions are forbidden at constant volume; and that (ii) hard-particle ordering is driven by a loss in enthalpy through volume reduction that outweighs a concomitant entropy loss upon ordering. The traditional approach considers minimization of Helmholtz energy, at constant volume, whereas the current study exclusively focuses on equilibrium phase transitions and, therefore, targets minimization of Gibbs energy at constant pressure. The Gibbs energy platform offers physically intuitive interpretations consistent with existing computation and experiments. The prevalent idea of entropy-driven ordering at constant V is restricted to transitions from non-equilibrium initial states that have yet to be properly defined for quantification. Laboratory of Laser Energetics, DE-FC52-08NA28302.

  14. Heat Capacity and Enthalpy of Fusion of Fenoxycarb

    Institute of Scientific and Technical Information of China (English)

    SUN Xiao-Hong; LIU Yuan-Fa; TAN Zhi-Cheng; JIA Ying-Qi; YANG Jian-Wu; WANG Mei-Han

    2005-01-01

    Fenoxycarb was synthesized and its heat capacities were precisely measured with an automated adiabatic calorimeter over the temperature range from 79 to 360 K. The sample was observed to melt at (326.31±0.14) K. The molar enthalpy and entropy of fusion as well as the chemical purity of the compound were determined to be (26.98±0.04) kJ·mol-1, (82.69±0.09) J·K-1·mol-1 and 99.53% ±0.01%, respectively. The thermodynamic functions relative to the reference temperature (298.15 K) were calculated based on the heat capacity measurements in the temperature range between 80 and 360 K. The extrapolated melting temperature for the absolutely pure compound obtained from fractional melting experiments was (326.62 ± 0.06) K. Further research on the melting process of this compound was carried out by means of differential scanning calorimetry technique. The result was in agreement with that obtained from the measurements of heat capacities.

  15. Entropy and enthalpy contributions to the kinetics of proton coupled electron transfer to the Mn4O4(O2PPh2)6 cubane.

    Science.gov (United States)

    Carrell, Thomas G; Smith, Paul F; Dennes, Joseph; Dismukes, G Charles

    2014-06-28

    The dependence of rate, entropy of activation, and ((1)H/(2)H) kinetic isotope effect for H-atom transfer from a series of p-substituted phenols to cubane Mn4O4L6 (L = O2PPh2) (1) reveals the activation energy to form the transition state is proportional to the phenolic O-H bond dissociation energy. New implications for water oxidation and charge recombination in photosystem II are described.

  16. Hydrolyzable polyureas bearing hindered urea bonds.

    Science.gov (United States)

    Ying, Hanze; Cheng, Jianjun

    2014-12-10

    Hydrolyzable polymers are widely used materials that have found numerous applications in biomedical, agricultural, plastic, and packaging industrials. They usually contain ester and other hydrolyzable bonds, such as anhydride, acetal, ketal, or imine, in their backbone structures. Here, we report the first design of hydrolyzable polyureas bearing dynamic hindered urea bonds (HUBs) that can reversibly dissociate to bulky amines and isocyanates, the latter of which can be further hydrolyzed by water, driving the equilibrium to facilitate the degradation of polyureas. Polyureas bearing 1-tert-butyl-1-ethylurea bonds that show high dynamicity (high bond dissociation rate), in the form of either linear polymers or cross-linked gels, can be completely degraded by water under mild conditions. Given the simplicity and low cost for the production of polyureas by simply mixing multifunctional bulky amines and isocyanates, the versatility of the structures, and the tunability of the degradation profiles of HUB-bearing polyureas, these materials are potentially of very broad applications. PMID:25406025

  17. Dissociative melting of ice VII at high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Goncharov, Alexander F.; Sanloup, Chrystele; Goldman, Nir; Crowhurst, Jonathan C.; Bastea, Sorin; Howard, W.M.; Fried, Laurence E.; Guignot, Nicolas; Mezouar, Mohamed; Meng, Yue; (UPMC); (LLNL); (CIW); (ESRF)

    2009-04-02

    We have used x-ray diffraction to determine the structure factor of water along its melting line to a static pressure of 57 GPa (570 kbar) and a temperature of more than 1500 K, conditions which correspond to the lower mantle of the Earth, and the interiors of Neptune and Uranus up to a depth of 7000 km. We have also performed corresponding first principles and classical molecular dynamics simulations. Above a pressure of 4 GPa the O-O structure factor is found to be very close to that of a simple soft sphere liquid, thus permitting us to determine the density of liquid water near the melting line. By comparing these results with the density of ice, also determined in this study, we find that the enthalpy of fusion ({Delta}H{sub f}) increases enormously along the melting line, reaching approximately 120 kJ/mole at 40 GPa (compared to 6 kJ/mole at 0 GPa), thus revealing significant molecular dissociation of water upon melting. We speculate that an extended two-phase region could occur in planetary processes involving the adiabatic compression of water.

  18. Positive and Negative Contributions in the Solvation Enthalpy due to Specific Interactions in Binary Mixtures of C1-C4 n-Alkanols and Chloroform with Butan-2-one.

    Science.gov (United States)

    Varfolomeev, Mikhail A; Rakipov, Ilnaz T; Solomonov, Boris N; Lodowski, Piotr; Marczak, Wojciech

    2015-06-25

    In the paper, results of calorimetric measurements, IR spectra, and calculated ab initio stabilization energies of dimers are reported for binary systems butan-2-one + (methanol, ethanol, propan-1-ol, butan-1-ol, and chloroform). Changes in the total enthalpy of specific interactions due to dissolution of butan-2-one in the alcohols, calculated using equations derived in previous works, are positive. That results from the endothermic breaking of the O-H···O-H bonds not completely compensated by the exothermic effects of formation of the O-H···O═C ones. Moreover, the concentration of nonbonded molecules of butan-2-one is significant even in dilute solutions, as is evidenced by the shape of the C═O stretching vibrations band in the IR spectra. Apart from that, the spectra do not confirm 1:2 complexes in spite of two lone electron pairs in the carbonyl group of butan-2-one capable of forming the hydrogen bonds. The changes in enthalpy of specific interactions are negative for dilute solutions of alcohols and chloroform in butan-2-one and of butan-2-one in chloroform, because no hydrogen bonds occur in pure butan-2-one. The experimental results are positively correlated with the enthalpies estimated from the ab initio energies using a simple "chemical reaction" approach. PMID:26012694

  19. Positive and Negative Contributions in the Solvation Enthalpy due to Specific Interactions in Binary Mixtures of C1-C4 n-Alkanols and Chloroform with Butan-2-one.

    Science.gov (United States)

    Varfolomeev, Mikhail A; Rakipov, Ilnaz T; Solomonov, Boris N; Lodowski, Piotr; Marczak, Wojciech

    2015-06-25

    In the paper, results of calorimetric measurements, IR spectra, and calculated ab initio stabilization energies of dimers are reported for binary systems butan-2-one + (methanol, ethanol, propan-1-ol, butan-1-ol, and chloroform). Changes in the total enthalpy of specific interactions due to dissolution of butan-2-one in the alcohols, calculated using equations derived in previous works, are positive. That results from the endothermic breaking of the O-H···O-H bonds not completely compensated by the exothermic effects of formation of the O-H···O═C ones. Moreover, the concentration of nonbonded molecules of butan-2-one is significant even in dilute solutions, as is evidenced by the shape of the C═O stretching vibrations band in the IR spectra. Apart from that, the spectra do not confirm 1:2 complexes in spite of two lone electron pairs in the carbonyl group of butan-2-one capable of forming the hydrogen bonds. The changes in enthalpy of specific interactions are negative for dilute solutions of alcohols and chloroform in butan-2-one and of butan-2-one in chloroform, because no hydrogen bonds occur in pure butan-2-one. The experimental results are positively correlated with the enthalpies estimated from the ab initio energies using a simple "chemical reaction" approach.

  20. The bond length and bond energy of gaseous CrW.

    Science.gov (United States)

    Matthew, Daniel J; Oh, Sang Hoon; Sevy, Andrew; Morse, Michael D

    2016-06-01

    Supersonically cooled CrW was studied using resonant two-photon ionization spectroscopy. The vibronically resolved spectrum was recorded over the region 21 100 to 23 400 cm(-1), showing a very large number of bands. Seventeen of these bands, across three different isotopologues, were rotationally resolved and analyzed. All were found to arise from the ground (1)Σ(+) state of the molecule and to terminate on states with Ω' = 0. The average r0 bond length across the three isotopic forms was determined to be 1.8814(4) Å. A predissociation threshold was observed in this dense manifold of vibronic states at 23 127(10) cm(-1), indicating a bond dissociation energy of D0(CrW) = 2.867(1) eV. Using the multiple bonding radius determined for atomic Cr in previous work, the multiple bonding radius for tungsten was calculated to be 1.037 Å. Comparisons are made between CrW and the previously investigated group 6 diatomic metals, Cr2, CrMo, and Mo2, and to previous computational studies of this molecule. It is also found that the accurately known bond dissociation energies of group 5/6 metal diatomics Cr2, V2, CrW, NbCr, VNb, Mo2, and Nb2 display a qualitative linear dependence on the sum of the d-orbital radial expectation values, r; this relationship allows the bond dissociation energies of other molecules of this type to be estimated. PMID:27276956

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

    International Nuclear Information System (INIS)

    Highlights: • LiCoO2 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 LiCoO2 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 LiCoO2 (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 LiCoO2 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 LiCoO2 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

  2. On the photostability of peptides after selective photoexcitation of the backbone: Prompt versus slow dissociation

    DEFF Research Database (Denmark)

    Byskov, Camilla Skinnerup; Jensen, Frank; Jørgensen, Thomas J D;

    2014-01-01

    , which is remote from the initial site of excitation. Hence loss of CE serves as direct proof that energy has reached the charge-site end, leaving the backbone intact. Our work demonstrates that excitation of tertiary amide moieties (proline linkages) results in both prompt dissociation and statistical...... present a protocol to disentangle slow and non-hazardous statistical dissociation from prompt cleavage of peptide bonds by 210 nm light based on experiments on protonated peptides isolated in vacuo and tagged by 18-crown-6 ether (CE). The weakest link in the system is between the charged site and CE...

  3. Dissociative Electron Attachment to Polyatomic Molecules - V : Formic Acid and Propyl Amine

    CERN Document Server

    Ram, N Bhargava

    2010-01-01

    In this paper, we discuss the dissociative electron attachment process in Formic Acid and Propyl Amine. These are molecules containing more than one functional group and have low symmetry (Cs group). We measured the kinetic energy and angular distributions of fragment H^{-} ions from the resonances observed in these molecules and compared with that in the precursor molecules, namely - Water, Ammonia and Methane. Measurements suggest that the dissociation dynamics in bigger molecules are independent of overall symmetry of the molecule, rather depend only on the local symmetry of functional group and bond orientation factors.

  4. Mirror Writing and a Dissociative Identity Disorder

    OpenAIRE

    Catherine Le; Joyce Smith; Lewis Cohen

    2009-01-01

    Individuals with dissociative identity disorder (DID) have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam—mirror writing. It is not known whether her mirror...

  5. A Thermodynamic Approach to Predict Formation Enthalpies of Ternary Systems Based on Miedema's Model

    Science.gov (United States)

    Mousavi, Mahbubeh Sadat; Abbasi, Roozbeh; Kashani-Bozorg, Seyed Farshid

    2016-07-01

    A novel modification to the thermodynamic semi-empirical Miedema's model has been made in order to provide more precise estimations of formation enthalpy in ternary alloys. The original Miedema's model was modified for ternary systems based on surface concentration function revisions. The results predicted by the present model were found to be in excellent agreement with the available experimental data of over 150 ternary intermetallic compounds. The novel proposed model is capable of predicting formation enthalpies of ternary intermetallics with small discrepancies of ≤20 kJ/mol as well as providing reliable enthalpy variations.

  6. Proton-transfer tautomerism and enthalpies of formation of some isoquinoline derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Namazian, Mansoor [ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200 (Australia)], E-mail: namazian@yazduni.ac.ir; Coote, Michelle L. [ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200 (Australia)], E-mail: mcoote@rsc.anu.edu.au

    2009-12-15

    Ab initio molecular orbital theory has been used to calculate enthalpies of formation of the keto tautomers of 1-hydroxyisoquinoline, 5-hydroxyisoquinoline, and 1,5-dihydroxyisoquinoline. The high-level composite method G3//B3LYP has been used for this study, and the results have been compared with available experimental values. The keto tautomer is more favourable for 1-hydroxyisoquinoline and 1,5-dihydroxyisoquinoline, and the experimental enthalpies of formation are in better agreement with the theoretical enthalpies of formation of the keto forms.

  7. Effect of organic solvent properties on enthalpies of their mixing with uranyl nitrate

    International Nuclear Information System (INIS)

    Results of studying dissolution enthalpies of anhydrons uranyl nitrate and its hexahydrate in different organic solvents and water are generalized. Analysis of different solvation effects during uranyl nitrate and its hexahydrate dissolution in 26 solvents shows that the main contribution to dissolution enthalpy is made by acidic-basic interaction of uranyl-nitrates with donor lone electron pairs. The obtained equations permit to predict with acceptable accuracy the values of dissolution enthalpies of the mentioned compounds in other midea on the basis of their physico-chemical properties

  8. Use of Computed X-ray Tomographic Data for Analyzing the Thermodynamics of a Dissociating Porous Sand/Hydrate Mixture

    Science.gov (United States)

    Freifeld, Barry M.; Kneafsey, Timothy J.; Tomutsa, Liviu; Stern, Laura A.; Kirby, Stephen H.

    2002-02-28

    X-ray computed tomography (CT) is a method that has been used extensively in laboratory experiments for measuring rock properties and fluid transport behavior. More recently, CT scanning has been applied successfully to detect the presence and study the behavior of naturally occurring hydrates. In this study, we used a modified medical CT scanner to image and analyze the progression of a dissociation front in a synthetic methane hydrate/sand mixture. The sample was initially scanned under conditions at which the hydrate is stable (atmospheric pressure and liquid nitrogen temperature, 77 K). The end of the sample holder was then exposed to the ambient air, and the core was continuously scanned as dissociation occurred in response to the rising temperature. CT imaging captured the advancing dissociation front clearly and accurately. The evolved gas volume was monitored as a function of time. Measured by CT, the advancing hydrate dissociation front was modeled as a thermal conduction problem explicitly incorporating the enthalpy of dissociation, using the Stefan moving-boundary-value approach. The assumptions needed to perform the analysis consisted of temperatures at the model boundaries. The estimated value for thermal conductivity of 2.6 W/m K for the remaining water ice/sand mixture is higher than expected based on conduction alone; this high value may represent a lumped parameter that incorporates the processes of heat conduction, methane gas convection, and any kinetic effects that occur during dissociation. The technique presented here has broad implications for future laboratory and field testing that incorporates geophysical techniques to monitor gas hydrate dissociation.

  9. A DFT Study on Intramolecular Hydrogen Bond in Substituted Catechols and Their Radicals

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Density functional theory (DFT) at B3LYP/6-31G(d,p) level was employed to calculate intramolecular hydrogen bond enthalpies (HIHB), O-H charge differences, O-H bond lengths and bond orders for various substituted catechols and their radicals generated after H-abstraction. It was found that although the charge difference between hydrogen-bonded H and O played a role in determining HIHB, HIHB was mainly governed by the hydrogen bond length. As the oxygen-centered radical has great tendency to form a chemical bond with the H atom, hydrogen bond lengths in catecholic radicals are systematically shorter than those in catechols. Hence, the HIHB for the former are higher than those for the latter.

  10. Charmonium dissociation cross sections and charmonium dissociation rates in hadronic matter

    CERN Document Server

    Liu, Feng-Rong; Xu, Xiao-Ming

    2016-01-01

    K*-charmonium dissociation reactions in hadronic matter are studied in the Born approximation, in the quark-interchange mechanism, and with a temperature-dependent quark potential. We obtain the temperature dependence of unpolarized cross sections for K*-charmonium dissociation reactions which produce charmed mesons and charmed strange mesons. We use the cross sections for charmonium dissociation in collisions with pion, rho meson, kaon, vector kaon, and eta meson to calculate dissociation rates of charmonium with the five types of mesons. Because of the temperature dependence of the meson masses, dissociation cross sections, and meson distribution functions, the charmonium dissociation rates generally increase with the increase of temperature and decrease with the increase of charmonium momentum from 2.2 GeV/c. We find that the first derivative of the dissociation rate with respect to the charmonium momentum is zero when the charmonium is at rest. While the eta + psi' and eta + chi_c dissociation reactions c...

  11. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    KAUST Repository

    Falivene, Laura

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  12. Direct dissociative chemisorption of propane on Ir(110)

    International Nuclear Information System (INIS)

    We have employed molecular beam techniques to investigate the initial probability of direct dissociative chemisorption, Pd, and the intrinsic trapping probability, ξ, of C3H8, C3D8, and (CH3)2CD2 on Ir(110) as a function of beam translational energy, Ei, from 1.5 to 59 kcal/mol. For C3H8 and (CH3)2CD2, a measurable (≥0.02) initial probability of direct dissociative chemisorption is observed above a beam energy of approximately 7 kcal/mol. For C3D8 this energy is roughly 10 kcal/mol. Above these energies the initial probability of direct chemisorption of each of the isotopomers of propane increases nearly linearly with Ei, approaching a value of approximately Pd=0.48 at Ei=52 kcal/mol for C3H8 and (CH3)2CD2, and Pd=0.44 at Ei=59 kcal/mol for C3D8. This kinetic isotope effect for the direct chemisorption of C3D8 relative to C3H8 is smaller than that expected for a mechanism of H (or D) abstraction by tunneling through an Eckart barrier, suggesting a contribution of C endash C bond cleavage to direct chemisorption. The lack of a kinetic isotope effect for the direct chemisorption of (CH3)2CD2 relative to C3H8 indicates that 1 degree C endash H bond cleavage dominates over 2 degree C endash H bond cleavage during the direct chemisorption of propane on Ir(110). The trapping behavior of each of these isotopomers of propane is approximately identical as a function of Ei, with ξ>0.9 at Ei=1.5 kcal/mol, ξ=0.3 at Ei=20 kcal/mol, and ξi=40 kcal/mol. copyright 1996 American Institute of Physics

  13. 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.

  14. Estimating the melting point, entropy of fusion, and enthalpy of fusion of organic compounds via SPARC.

    Science.gov (United States)

    Whiteside, T S; Hilal, S H; Brenner, A; Carreira, L A

    2016-08-01

    The entropy of fusion, enthalpy of fusion, and melting point of organic compounds can be estimated through three models developed using the SPARC (SPARC Performs Automated Reasoning in Chemistry) platform. The entropy of fusion is modelled through a combination of interaction terms and physical descriptors. The enthalpy of fusion is modelled as a function of the entropy of fusion, boiling point, and flexibility of the molecule. The melting point model is the enthalpy of fusion divided by the entropy of fusion. These models were developed in part to improve SPARC's vapour pressure and solubility models. These models have been tested on 904 unique compounds. The entropy model has a RMS of 12.5 J mol(-1) K(-1). The enthalpy model has a RMS of 4.87 kJ mol(-1). The melting point model has a RMS of 54.4°C.

  15. 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.

  16. The size-effect on the formation enthalpy of nanosized binary ti based alloy

    International Nuclear Information System (INIS)

    The effects of grain size and composition on the formation enthalpy of nano binary Ti-based alloy are investigated by taking the surface effect into account within the modified Miedema model. It is demonstrated that the formation enthalpy of binary Ti based alloy with nano grains is size-dependent and exhibits evident size-effects. The formation enthalpy increases with the size decrease, and its value turns from negative to positive at a critical size, which will weaken the thermal stability of the nano grains. Furthermore, the composition segregation taking place in the nano grains of the Ti based alloy is obvious when the grain size is less than 10 nm and the tendency of segregation is dependent on the surface formation enthalpy of nanoparticle. (authors)

  17. Enthalpy and Phase Relations in Saline Geothermal Fluids to "Supercritical" Conditions

    Science.gov (United States)

    Driesner, T.

    2013-12-01

    Some of the world's largest geothermal systems contain saline fluids (e.g., Salton Sea), and 'supercritical' geothermal resources are targeted for the IDDP-2 well at saline system at Reykjanes, Iceland. Saline aqueous fluids have, however, phase relations of steam and liquid (+/- solid salt) that are much more complex than those for pure water (Fig. 1). These phase relations affect both the multiphase flow behavior in the system (impacting rock alteration) and the enthalpy of fluids that can be produced. This contribution introduces the phase diagram of H2O-NaCl in enthalpy-pressure-composition space. Various isobaric sections illustrate the phase states and enthalpies that can be expected in the deeper ('supercritical') parts of high-enthalpy, saline geothermal systems.

  18. Estimating the melting point, entropy of fusion, and enthalpy of fusion of organic compounds via SPARC.

    Science.gov (United States)

    Whiteside, T S; Hilal, S H; Brenner, A; Carreira, L A

    2016-08-01

    The entropy of fusion, enthalpy of fusion, and melting point of organic compounds can be estimated through three models developed using the SPARC (SPARC Performs Automated Reasoning in Chemistry) platform. The entropy of fusion is modelled through a combination of interaction terms and physical descriptors. The enthalpy of fusion is modelled as a function of the entropy of fusion, boiling point, and flexibility of the molecule. The melting point model is the enthalpy of fusion divided by the entropy of fusion. These models were developed in part to improve SPARC's vapour pressure and solubility models. These models have been tested on 904 unique compounds. The entropy model has a RMS of 12.5 J mol(-1) K(-1). The enthalpy model has a RMS of 4.87 kJ mol(-1). The melting point model has a RMS of 54.4°C. PMID:27586365

  19. Partial and integral enthalpies of mixing of Cu-Fe-Ti melts at 1873 K

    Science.gov (United States)

    Abdulov, A. R.; Dreval', L. A.; Agraval, P. G.; Turchanin, M. A.

    2009-10-01

    The partial enthalpy of mixing of titanium in Cu-Fe-Ti melts are studied by high-temperature isoperibolic calorimetry at 1873 K in the composition range x Ti = 0-0.6 along three sections with a ratio x Fe / x Cu = 1/3, 1, and 3. The integral enthalpy of mixing of the ternary melts is calculated by integrating the Gibbs-Duhem equation and is described in terms of the Redlich-Kister-Muggianu model. Function Δ H demonstrates negative values over a wide concentration range. The contribution of a ternary interaction to the enthalpy of mixing of Cu-Fe-Ti melts is mainly positive. The first partial enthalpies of mixing of Al, Sn, Si, Y, Zr, Hf, and Ni with Cu-Fe-Ti melts are negative and indicate an increase of the thermodynamic stability of the liquid phase upon the dissolution of these additions.

  20. Initial results on high enthalpy plasma generation in a magnetized coaxial source

    International Nuclear Information System (INIS)

    Initial investigation on high enthalpy plasma stream generation in the North Carolina State University Coaxial Plasma Source (CPS) facility is presented. Tenuous, yet high enthalpy, flows are produced from this Magnetized Coaxial plasma Gun (MCG) which allow laboratory study of plasma streams with a wide variety of applications. The applicability includes, but is not limited to, advanced thrusters for electric space propulsion, astrophysical jets and critical ionization phenomena, magnetic fusion compact toroid devices and tokamak fueling, large scale plasma etching and deposition, etc

  1. Skin Friction Sensor Design Methodology and Validation for High-Speed, High-Enthalpy Flow Applications

    OpenAIRE

    Meritt, Ryan James

    2014-01-01

    This investigation concerns the design, build, and testing of a new class of skin friction sensor capable of performing favorably in high-speed, high-enthalpy flow conditions, such as that found in atmospheric re-entry vehicles, scramjets, jet engines, material testing, and industrial processes. Fully understanding and optimizing these complex flows requires an understanding of aerodynamic properties at high enthalpies, which, in turn, requires numerical and analytical modeling as well as re...

  2. Standard formation enthalpies of some yttrium-containing high-temperature ceramics

    International Nuclear Information System (INIS)

    Enthalpies of YBa2Cu3O6.96, YBa2Cu3O6.97, Y0.98Ca0.02Ba2Cu3O6.90 and Y0.95Ba2Cu3O6.57 reactions with 2.19 n hydrochloric acid were measured at 298.15 K in a sealed pendulum calorimeter. On the basis of the data obtained and using literature ones standard formation enthalpies were calculated

  3. A Statistical Examination on the Compensation between the Enthalpies and Entropies Obtained from the Calorimetric Methods

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The validity of the compensation between the enthalpies and entropies obtained from the calorimetric methods was statistically examined for the first time based on computer simulations. It turned out that the several claimed enthalpy-entropy compensations in literature based upon the calorimetric measurements were statistically correct. Interestingly, a linear relationship between the slopes and correlation coefficients of the TDS-DH plots of different supramolecular systems was found, which indicated that the solvent reorganization was the physical origin of the compensation behavior.

  4. Enthalpy relaxations in polymer blends and block copolymers: Influence of domain size

    OpenAIRE

    Brinke, G. ten; Grooten, R.

    1989-01-01

    It is now well known that enthalpy relaxation measurements can be used to establish polymer-polymer blend phase behavior when the glass transition temperatures of the two polymers are virtually coincident. In the most simple cases, the aging kinetics of an immiscible blend will be representative of the pure polymers superimposed upon each other. However, in many cases the situation is more complicated because of the presence of interface material. In this paper the relation between enthalpy r...

  5. Molecular dissociation in dilute gas

    International Nuclear Information System (INIS)

    The charge state distributions (CSD) produced during molecular dissociation are important to both Trace Element Accelerator Mass Spectrometry (TEAMS) and the ion implantation industry. The CSD of 1.3 - 1.7 MeV SiN+, SiMg+, SiMn+, and SiZn+ molecules have been measured for elements that do not form atomic negative ions (N, Mg, Mn, and Zn) using a NEC Tandem Pelletron accelerator. The molecules were produced in a Cs sputter negative ion source, accelerated, magnetically analyzed, and then passed through an N2 gas cell. The neutral and charged breakups where analyzed using an electrostatic deflector and measured with particle detectors. Equilibrium CSD were determined and comparisons made between molecular and atomic ion data. copyright 1999 American Institute of Physics

  6. Theory of dissociative tunneling ionization

    CERN Document Server

    Svensmark, Jens; Madsen, Lars Bojer

    2016-01-01

    We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees freedom. In the regime where the BO approximation is applicable imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fiel...

  7. Bond breaking in a Morse chain under tension: Fragmentation patterns, higher index saddles, and bond healing

    Science.gov (United States)

    Mauguière, F. A. L.; Collins, P.; Ezra, G. S.; Wiggins, S.

    2013-04-01

    We investigate the fragmentation dynamics of an atomic chain under tensile stress. We have classified the location, stability type (indices), and energy of all equilibria for the general n-particle chain, and have highlighted the importance of saddle points with index >1. We show that for an n = 2-particle chain under tensile stress the index 2 saddle plays a central role in organizing the dynamics. We apply normal form theory to analyze phase space structure and dynamics in a neighborhood of the index 2 saddle. We define a phase dividing surface (DS) that enables us to classify trajectories passing through a neighborhood of the saddle point using the values of the integrals associated with the normal form. We also generalize our definition of the dividing surface and define an extended dividing surface (EDS), which is used to sample and classify all trajectories that pass through a phase space neighborhood of the index 2 saddle at total energies less than that of the saddle. Classical trajectory simulations are used to study fragmentation patterns for the n = 2 chain under tension. That is, we investigate the relative probability for breaking one bond versus concerted fission of several (two, in this case) bonds. Initial conditions for trajectories are obtained by sampling the EDS at constant energy. We sample trajectories at fixed energies both above and below the energy of the saddle. The fate of trajectories (single versus multiple bond breakage) is explored as a function of the location of the initial condition on the EDS, and a connection made to the work of Chesnavich on collision-induced dissociation. A significant finding is that we can readily identify trajectories that exhibit bond healing. Such trajectories pass outside the nominal (index 1) transition state for single bond dissociation, but return to the potential well region, possibly several times, before ultimately dissociating.

  8. Dissociative Electron Attachment to Hydrocarbons. A Laboratory Study

    Science.gov (United States)

    Szymanska, E.; Mason, N. J.

    2011-05-01

    Laboratory studies of PAHs continue to be essential if we are to interpret the wealth and variety of processes contributing to star formation. In the realm of gas-phase kinetics reactions involving negative ions are being studied to help modellers understand the role of these species in interstellar chemistry. Observations have shown that PAHs molecules are abundant and ubiquitous in the interstellar medium of galaxies, play an important role in its physical and chemical characteristics and form a key link between small hydrocarbon species and large carbonaceous grains. There is therefore considerable interest in the mechanisms by which these molecules and their anions may form. One method is electron induced chemistry within the icy mantles on the surface of dust grains. In particular it has been recently shown that functional group dependence exists in electron attachment processes giving rise to site selective fragmentation of molecules at the C-H, O-H and N-H bonds at energies well beyond the threshold for the breaking of any of these bonds allowing novel forms of chemistry that have little or no activation barriers, such as are necessary in the ISM. In this poster we present the results of recent studies on dissociative electron attachment (DEA) to PAHs using an improved version of a Velocity Map Imaging (VMI) spectrometer comprised of a magnetically collimated and low energy pulsed electron gun, a Faraday cup, an effusive molecular beam, a pulsed field ion extraction, a time of flight analyzer and a two-dimensional position sensitive detector consisting of microchannel plate and a phosphor screen. The VMI spectrometer measures the kinetic energy and angular distribution of the fragment anions produced in the dissociative electron attachment process. Kinetic energy measurements provide information on the internal energies of the fragment anions and determine the dissociation limits of the parent negative ion resonant states responsible for the dissociative

  9. Sedation and dissociative anaesthesia in the horse

    OpenAIRE

    Marntell, Stina

    2004-01-01

    The overall aim of this investigation was to study the effects of different drug combinations for premedication and dissociative anaesthesia, to examine their suitability for field conditions and their ability to maintain cardiorespiratory function and provide sufficient analgesia for common, but challenging procedures such as castration. Haemodynamic parameters, pulmonary ventilation-perfusion relationships, and clinical effects were studied during sedation and dissociative anaesthesia. The ...

  10. [Dissociative disorder and self-injury].

    Science.gov (United States)

    Noma, Shun'ichi

    2011-01-01

    Both the number of patients with dissociative disorder and that of those with self-injury have been increasing since the end of the twentieth century, suggesting that dissociation and self-injury might be closely related. When dissociative disorder coexists with self-injury, it implies self-punishment and a wish to be understood by others. Although many cases of self-injury observed since 2000 lacked traumatic experiences and were not accompanied by pathological dissociative symptoms, the patients did have dissociative tendencies. According to the results of our study examining self-injury in patients with eating disorders, we observed that self-injury, dissociative tendency and insulation from others are related to each other. This suggests that affects, sensations and representations are dissociated, losing their normal response order, and that the pervasive idea that "pain=secure" is formed in a patient from childhood based on influence from their parents. Self-injury appears to be an activation of this pervasive idea that is triggered by a stressful situation, when the dissociative psychological segmentation of effects and their representations are present in the background.

  11. In Situ Raman Spectroscopy Study on Dissociation of Methane at High Temperatures and at High Pressures

    Institute of Scientific and Technical Information of China (English)

    CHEN Jin-Yang; JIN Lu-Jiang; DONG Jun-Ping; ZHENG Hai-Fei

    2008-01-01

    We investigate the stability and dissociation of methane,which is the most abundant organic molecule in the universe,using diamond anvil cell(DAC)with in situ Raman spectroscopy up to 903K and 21GPa.At the temperatures of 793 and 723K and the corresponding pressures of 16.15 and 20.30 GPa,methane dissociates to very high,methane remains stability up to the highest temperature of 903 K of the work.The four symmetricC-H bonds of methane split at high temperatures and at high pressures,and there is at least one phase transitionof crystalline symmetry from face centred cubic (fce) to hexagonal dose packed (hcp) before dissociation.

  12. Dissociation dynamics of ethylene molecules on a Ni cluster using ab initio molecular dynamics simulations

    International Nuclear Information System (INIS)

    The atomistic mechanism of dissociative adsorption of ethylene molecules on a Ni cluster is investigated by ab initio molecular-dynamics simulations. The activation free energy to dehydrogenate an ethylene molecule on the Ni cluster and the corresponding reaction rate is estimated. A remarkable finding is that the adsorption energy of ethylene molecules on the Ni cluster is considerably larger than the activation free energy, which explains why the actual reaction rate is faster than the value estimated based on only the activation free energy. It is also found from the dynamic simulations that hydrogen molecules and an ethane molecule are formed from the dissociated hydrogen atoms, whereas some exist as single atoms on the surface or in the interior of the Ni cluster. On the other hand, the dissociation of the C-C bonds of ethylene molecules is not observed. On the basis of these simulation results, the nature of the initial stage of carbon nanotube growth is discussed. (paper)

  13. Water adsorption and dissociation on BeO (001) and (100) surfaces

    CERN Document Server

    Gómez, M A; Kress, J D; Pratt, L R; Gomez, Maria A.; Kress, Joel D.; Pratt, Lawrence R.

    2007-01-01

    Plateaus in water adsorption isotherms on hydroxylated BeO surfaces suggest significant differences between the hydroxylated (100) and (001) surface structures and reactivities. Density functional theory structures and energies clarify these differences. Using relaxed surface energies, a Wulff construction yields a prism crystal shape exposing long (100) sides and much smaller (001) faces. This is consistent with the BeO prisms observed when beryllium metal is oxidized. A water oxygen atom binds to a single surface beryllium ion in the preferred adsorption geometry on either surface. The water oxygen/beryllium bonding is stronger on the surface with greater beryllium atom exposure, namely the less-stable (001) surface. Water/beryllium coordination facilitates water dissociation. On the (001) surface, the dissociation products are a hydroxide bridging two beryllium ions and a metal coordinated hydride with some surface charge depletion. On the (100) surface, water dissociates into a hydroxide ligating a Be ato...

  14. Revealing Dissociative Electron Attachment Dynamics in Polyatomic Molecules Using Momentum Imaging Experiments and Electron Scattering Calculations

    Science.gov (United States)

    Belkacem, Ali; Slaughter, Daniel

    2015-05-01

    Understanding electron-driven chemical reactions is important for improving a variety of technological applications such as materials processing and the important role they play in the radiation damage in bulk matter. Furthermore, dissociative electron attachment often exhibits site-selective bond cleavage, which holds promise for prediction and precise control of electron-driven chemical reactions. Recent dynamical studies of these reactions have demonstrated that an understanding of anion dissociation dynamics beyond simple one-dimensional models is crucial in interpreting the measured fragment angular distributions. We combine ion fragment momentum imaging experiments with electron attachment entrance amplitude calculations to interrogate the non-Born-Oppenheimer dynamics of dissociative electron attachment in polyatomic molecules. We will report recent experimental developments in molecules of technological interest including methanol, methane and uracil. Work supported by Chemical Sciences, Geosciences and Biosciences division of BES/DOE.

  15. Kinetics of enthalpy relaxation of milk protein concentrate powder upon ageing and its effect on solubility.

    Science.gov (United States)

    Haque, Enamul; Whittaker, Andrew K; Gidley, Michael J; Deeth, Hilton C; Fibrianto, Kiki; Bhandari, Bhesh R

    2012-10-01

    Kinetics of enthalpy relaxation of milk protein concentrate (MPC) powder upon short-term (up to 67 h) storage at 25 °C and aw 0.85, and long-term (up to 48 days) storage at 25 °C and a range of aw values (0-0.85) were studied by differential scanning calorimetry (DSC). The short-term study showed a rapid recovery of enthalpy for the first 48 h, followed by a slower steady increase with time. The non-exponential β parameter was calculated using the Kohlrausch-Williams-Watts function and found to be 0.39. Long-term storage showed that enthalpy relaxation depends on both storage period and water activity. The enthalpy value was much less for lower moisture content (mc) (aw ≤ 0.23, mc ≤ 5.5%) than for higher mc (aw ≥ 0.45, mc ≥ 8%) samples for a particular storage period. The results suggest that the presence of more water molecules, in close proximity to the protein surface facilitates kinetic unfreezing and subsequent motion of molecular segments of protein molecules towards thermodynamic equilibrium. Although de-ageing of stored samples did not reverse storage-induced solubility losses, the timescale of enthalpy relaxation was similar to that of solubility loss. It is suggested that enthalpy relaxation within stored samples allows structural rearrangements that are responsible for subsequent solubility decreases.

  16. The Role of Partial Enthalpy in Thermal Conductivity Calculations for Nanofluids

    Science.gov (United States)

    Edwards, Matthew; Shelton, John

    2014-03-01

    Over the past decade, reports of significantly enhanced thermal conductivity in solutions of nanoscale particles (nanofluids) have elicited a great deal of interest due to the large number of applications for efficient heat transfer fluids. A common method for calculating the thermal conductivity of a nanofluid uses the autocorrelation of the microscopic heat flux (Green-Kubo formalism), which contains a correction for the net transport of enthalpy due to species diffusion. The partial enthalpy component of the correction term cannot be found from microscopic quantities and is often approximated by the partitioned enthalpy. Using NPT molecular dynamics simulations over a wide range of interaction energies, we show that this approximation leads to spurious enhancements with magnitudes similar to those reported in the literature. The discrepancy arises because the partitioned enthalpy neglects the change in fluid-fluid interaction enthalpy which occurs around solid particles; in systems with strong fluid-solid interactions this can be a substantial portion of the total enthalpy. This work suggests that the standard method for calculating thermal conductivity in nanofluids may be invalid and that actual conductivity enhancements are comparable to those predicted by Maxwell's theory.

  17. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  18. The expectancy of threat and peritraumatic dissociation

    Directory of Open Access Journals (Sweden)

    Pamela McDonald

    2013-12-01

    Full Text Available Background: Peritraumatic dissociation is one of the most critical acute responses to a traumatic experience, partly because it predicts subsequent posttraumatic stress disorder. Despite this, there is little understanding about the factors that influence peritraumatic dissociation. This study investigated the extent to which peritraumatic dissociation is predicted by the amount of perceived warning that participants had of the impact of the trauma. Method: Randomized eligible admissions to four major trauma hospitals (N =243 were assessed during hospital admission with the Peritraumatic Dissociation Experiences Questionnaire (PDEQ and the perceived warning that participants had before the trauma impact occurred. Results: Whereas female gender predicted both Awareness and Derealization subscale scores on the PDEQ, perceived warning also predicted scores on the Derealization subscale. Conclusions: This finding suggests that the degree of anticipated threat may contribute to peritraumatic dissociation.

  19. The Shutdown Dissociation Scale (Shut-D

    Directory of Open Access Journals (Sweden)

    Inga Schalinski

    2015-05-01

    Full Text Available The evolutionary model of the defense cascade by Schauer and Elbert (2010 provides a theoretical frame for a short interview to assess problems underlying and leading to the dissociative subtype of posttraumatic stress disorder. Based on known characteristics of the defense stages “fright,” “flag,” and “faint,” we designed a structured interview to assess the vulnerability for the respective types of dissociation. Most of the scales that assess dissociative phenomena are designed as self-report questionnaires. Their items are usually selected based on more heuristic considerations rather than a theoretical model and thus include anything from minor dissociative experiences to major pathological dissociation. The shutdown dissociation scale (Shut-D was applied in several studies in patients with a history of multiple traumatic events and different disorders that have been shown previously to be prone to symptoms of dissociation. The goal of the present investigation was to obtain psychometric characteristics of the Shut-D (including factor structure, internal consistency, retest reliability, predictive, convergent and criterion-related concurrent validity.A total population of 225 patients and 68 healthy controls were accessed. Shut-D appears to have sufficient internal reliability, excellent retest reliability, high convergent validity, and satisfactory predictive validity, while the summed score of the scale reliably separates patients with exposure to trauma (in different diagnostic groups from healthy controls.The Shut-D is a brief structured interview for assessing the vulnerability to dissociate as a consequence of exposure to traumatic stressors. The scale demonstrates high-quality psychometric properties and may be useful for researchers and clinicians in assessing shutdown dissociation as well as in predicting the risk of dissociative responding.

  20. Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb(Et2dtc)3(phen)

    Institute of Scientific and Technical Information of China (English)

    Song Weiming; Hu Qilin; Chang Xuan; Chen Sanping; Xie Gang; Gao Shengli

    2006-01-01

    A ternary solid complex Yb(Et2dtc)3(phen) was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1, 10-phenanthroline (o-phen·H2O) in absolute ethanol.The bonding characteristics of the complex were characterized by IR.The result shows Yb3+ bands with two sulfur atoms in the Na(Et2dtc)3 and two nitrogen atoms in the o-phen.The enthalpy change of liquid-phase reaction of formation of the complex ΔrHθm (l), was determined as being (-24.838±0.114) kJ·mol-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter.The enthalpy change of the solid-phase reaction of formation of the complex ΔrHθm (s), was calculated as being (108.015±0.479) kJ·mol-1 on the basis of an appropriate thermochemistry cycle.The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction.Fundamental parameters, the activation enthalpy, ΔHθ≠, the activation entropy, ΔSθ≠, the activation free energy, ΔGθ≠, the apparent reaction rate constant k, the apparent activation energy E, the pre-exponential constant A, and the reaction order n, were obtained by a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic experiments.At the same time, the molar heat capacity of the complex cm, p, was determined to be (86.34±1.74) J·mol-1·K-1 by the same microcalormeter.The constant-volume combustion energy of the complex, ΔcU, was determined to be (-17954.08±8.11) kJ·mol-1 by an RBC-Ⅱ type rotating-bomb calorimeter at 298.15 K.Its standard enthalpy of combustion, ΔcHθm, and standard enthalpy of formation, ΔfHθm, were calculated to be (-17973.29±8.11) kJ·mol-1 and (-770.36±9.02) kJ·mol-1, respectively.

  1. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  2. Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

    Science.gov (United States)

    Luo, Xuan; Jiang, Bin; Juaristi, J. Iñaki; Alducin, Maite; Guo, Hua

    2016-07-01

    The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH4/CH3D/CHD3 on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH4/CH3D/CHD3 have been carried out on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.

  3. Unified description of hydrogen bonding by a two-state effective Hamiltonian

    CERN Document Server

    McKenzie, Ross H

    2011-01-01

    An effective Hamiltonian is considered for hydrogen bonding between two molecules due to the quantum mechanical interaction between the orbitals of the H-atom and the donor and acceptor atoms in the molecules. The Hamiltonian acts on two diabatic states and has a simple chemically motivated form for its matrix elements. The model gives insight into the "H-bond puzzle", describes different classes of bonds, and empirical correlations between the donor-acceptor distance $R$ and binding energies, bond lengths, and the softening of vibrational frequencies. A key prediction is the UV photo-dissociation of H-bonded complexes via an excited electronic state with an exalted vibrational frequency.

  4. The Effect of Carbon Monoxide Co-Adsorption on Ni-Catalysed Water Dissociation

    OpenAIRE

    Abas Mohsenzadeh; Anders Borjesson; Jeng-Han Wang; Tobias Richards; Kim Bolton

    2013-01-01

    The effect of carbon monoxide (CO) co-adsorption on the dissociation of water on the Ni(111) surface has been studied using density functional theory. The structures of the adsorbed water molecule and of the transition state are changed by the presence of the CO molecule. The water O–H bond that is closest to the CO is lengthened compared to the structure in the absence of the CO, and the breaking O–H bond in the transition state structure has a larger imaginary frequency in the presence of C...

  5. From state dissociation to status dissociatus.

    Science.gov (United States)

    Antelmi, Elena; Ferri, Raffaele; Iranzo, Alex; Arnulf, Isabelle; Dauvilliers, Yves; Bhatia, Kailash P; Liguori, Rocco; Schenck, Carlos H; Plazzi, Giuseppe

    2016-08-01

    The states of being are conventionally defined by the simultaneous occurrence of behavioral, neurophysiological and autonomic descriptors. State dissociation disorders are due to the intrusion of features typical of a different state into an ongoing state. Disorders related to these conditions are classified according to the ongoing main state and comprise: 1) Dissociation from prevailing wakefulness as seen in hypnagogic or hypnopompic hallucinations, automatic behaviors, sleep drunkenness, cataplexy and sleep paralysis 2) Dissociation from rapid eye movement (REM) sleep as seen in REM sleep behavior disorder and lucid dreaming and 3) Dissociation from NREM sleep as seen in the disorders of arousal. The extreme expression of states dissociation is characterized by the asynchronous occurrence of the various components of the different states that prevents the recognition of any state of being. This condition has been named status dissociatus. According to the underlying disorders/diseases and to their severity, among status dissociatus we may recognize disorders in which such an extreme dissociation occurs only at night time or intermittently (i.e., autoimmune encephalopathies, narcolepsy type 1 and IgLON5 parasomnia), and others in which it occurs nearly continuously with complete loss of any conventionally defined state of being, and of the circadian pattern (agrypnia excitata). Here, we render a comprehensive review of all diseases/disorders associated with state dissociation and status dissociatus and propose a critical classification of this complex scenario. PMID:26431902

  6. On Bond Portfolio Management

    OpenAIRE

    Vladislav Kargin

    2002-01-01

    This paper describes a new method of bond portfolio optimization based on stochastic string models of correlation structure in bond returns. The paper shows how to approximate correlation function of bond returns, compute the optimal portfolio allocation using Wiener-Hopf factorization, and check whether a collection of bonds presents arbitrage opportunities.

  7. Analyzing angular distributions for two-step dissociation mechanisms in velocity map imaging.

    Science.gov (United States)

    Straus, Daniel B; Butler, Lynne M; Alligood, Bridget W; Butler, Laurie J

    2013-08-15

    Increasingly, velocity map imaging is becoming the method of choice to study photoinduced molecular dissociation processes. This paper introduces an algorithm to analyze the measured net speed, P(vnet), and angular, β(vnet), distributions of the products from a two-step dissociation mechanism, where the first step but not the second is induced by absorption of linearly polarized laser light. Typically, this might be the photodissociation of a C-X bond (X = halogen or other atom) to produce an atom and a momentum-matched radical that has enough internal energy to subsequently dissociate (without the absorption of an additional photon). It is this second step, the dissociation of the unstable radicals, that one wishes to study, but the measured net velocity of the final products is the vector sum of the velocity imparted to the radical in the primary photodissociation (which is determined by taking data on the momentum-matched atomic cophotofragment) and the additional velocity vector imparted in the subsequent dissociation of the unstable radical. The algorithm allows one to determine, from the forward-convolution fitting of the net velocity distribution, the distribution of velocity vectors imparted in the second step of the mechanism. One can thus deduce the secondary velocity distribution, characterized by a speed distribution P(v1,2°) and an angular distribution I(θ2°), where θ2° is the angle between the dissociating radical's velocity vector and the additional velocity vector imparted to the product detected from the subsequent dissociation of the radical. PMID:23464815

  8. Discovering Chemistry With Natural Bond Orbitals

    CERN Document Server

    Weinhold, Frank

    2012-01-01

    This book explores chemical bonds, their intrinsic energies, and the corresponding dissociation energies which are relevant in reactivity problems. It offers the first book on conceptual quantum chemistry, a key area for understanding chemical principles and predicting chemical properties. It presents NBO mathematical algorithms embedded in a well-tested and widely used computer program (currently, NBO 5.9). While encouraging a "look under the hood" (Appendix A), this book mainly enables students to gain proficiency in using the NBO program to re-express complex wavefunctions in terms of intui

  9. Theory of dissociative tunneling ionization

    Science.gov (United States)

    Svensmark, Jens; Tolstikhin, Oleg I.; Madsen, Lars Bojer

    2016-05-01

    We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees of freedom. In the regime where the BO approximation is applicable, imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally, the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fields, where the BO approximation does not apply, the weak-field asymptotic theory describes the spectrum accurately.

  10. Chemical and thermochemical aspects of the ozonolysis of ethyl oleate: decomposition enthalpy of ethyl oleate ozonide.

    Science.gov (United States)

    Cataldo, Franco

    2013-01-01

    Neat ethyl oleate was ozonized in a bubble reactor and the progress of the ozonolysis was followed by infrared (FT-IR) spectroscopy and by the differential scanning calorimetry (DSC). The ozonolysis was conducted till a molar ratio O3/C=C≈1 when the exothermal reaction spontaneously went to completion. A specific thermochemical calculation on ethyl oleate ozonation has been made to determine the theoretical heat of the ozonization reaction using the group increment approach. A linear relationship was found both in the integrated absorptivity of the ozonide infrared band at 1110 cm(-1) and the ozonolysis time as well as the thermal decomposition enthalpy of the ozonides and peroxides formed as a result of the ozonation. The DSC decomposition temperature of ozonated ethyl oleate occurs with an exothermal peak at about 150-155 °C with a decomposition enthalpy of 243.0 kJ/mol at molar ratio O3/C=C≈1. It is shown that the decomposition enthalpy of ozonized ethyl oleate is a constant value (≈243 kJ/mol) at any stage of the O3/C=C once an adequate normalization of the decomposition enthalpy for the amount of the adsorbed ozone is taken into consideration. The decomposition enthalpy of ozonized ethyl oleate was also calculated using a simplified thermochemical model, obtaining a result in reasonable agreement with the experimental value.

  11. Definition of Total Energy budget equation in terms of moist-air Enthalpy surface flux

    CERN Document Server

    Marquet, Pascal

    2015-01-01

    Uncertainty exists concerning the proper formulation of surface heat fluxes, namely the sum of "sensible" and "latent" heat fluxes, and in fact concerning these two fluxes if they are considered as separate fluxes. In fact, eddy flux of moist-air energy must be defined as the eddy transfer of moist-air specific enthalpy ($\\overline{w' h'}$), where the specific enthalpy ($h$) is equal to the internal energy of moist air plus the pressure divided by the density (namely $h = e_{\\rm int} + p/\\rho$). The fundamental issue is to compute this local (specific) moist-air enthalpy ($h$), and in particular to determine absolute reference value of enthalpies for dry air and water vapour $(h_d)_{\\rm ref}$ and $(h_v)_{\\rm ref}$. New results shown in Marquet (QJRMS 2015, arXiv:1401.3125) are based on the Third-law of Thermodynamics and can allow these computations. In this note, this approach is taken to show that Third-law based values of moist-air enthalpy fluxes is the sum of two terms. These two terms are similar to wha...

  12. Chemical and thermochemical aspects of the ozonolysis of ethyl oleate: decomposition enthalpy of ethyl oleate ozonide.

    Science.gov (United States)

    Cataldo, Franco

    2013-01-01

    Neat ethyl oleate was ozonized in a bubble reactor and the progress of the ozonolysis was followed by infrared (FT-IR) spectroscopy and by the differential scanning calorimetry (DSC). The ozonolysis was conducted till a molar ratio O3/C=C≈1 when the exothermal reaction spontaneously went to completion. A specific thermochemical calculation on ethyl oleate ozonation has been made to determine the theoretical heat of the ozonization reaction using the group increment approach. A linear relationship was found both in the integrated absorptivity of the ozonide infrared band at 1110 cm(-1) and the ozonolysis time as well as the thermal decomposition enthalpy of the ozonides and peroxides formed as a result of the ozonation. The DSC decomposition temperature of ozonated ethyl oleate occurs with an exothermal peak at about 150-155 °C with a decomposition enthalpy of 243.0 kJ/mol at molar ratio O3/C=C≈1. It is shown that the decomposition enthalpy of ozonized ethyl oleate is a constant value (≈243 kJ/mol) at any stage of the O3/C=C once an adequate normalization of the decomposition enthalpy for the amount of the adsorbed ozone is taken into consideration. The decomposition enthalpy of ozonized ethyl oleate was also calculated using a simplified thermochemical model, obtaining a result in reasonable agreement with the experimental value. PMID:23969233

  13. Development of equations for differential and integral enthalpy change of adsorption for simulation studies.

    Science.gov (United States)

    Do, D D; Nicholson, D; Fan, Chunyan

    2011-12-01

    We present equations to calculate the differential and integral enthalpy changes of adsorption for their use in Monte Carlo simulation. Adsorption of a system of N molecules, subject to an external potential energy, is viewed as one of transferring these molecules from a reference gas phase (state 1) to the adsorption system (state 2) at the same temperature and equilibrium pressure (same chemical potential). The excess amount adsorbed is the difference between N and the hypothetical amount of gas occupying the accessible volume of the system at the same density as the reference gas. The enthalpy change is a state function, which is defined as the difference between the enthalpies of state 2 and state 1, and the isosteric heat is defined as the negative of the derivative of this enthalpy change with respect to the excess amount of adsorption. It is suitable to determine how the system behaves for a differential increment in the excess phase adsorbed under subcritical conditions. For supercritical conditions, use of the integral enthalpy of adsorption per particle is recommended since the isosteric heat becomes infinite at the maximum excess concentration. With these unambiguous definitions we derive equations which are applicable for a general case of adsorption and demonstrate how they can be used in a Monte Carlo simulation. We apply the new equations to argon adsorption at various temperatures on a graphite surface to illustrate the need to use the correct equation to describe isosteric heat of adsorption.

  14. Comparative Study of the Dissociative Ionization of 1,1,1 Trichloroethane Using Nanosecond and Femtosecond Laser Pulses

    OpenAIRE

    Lourens Botha; Christien Strydom; Anton du Plessis

    2010-01-01

    Changes in the laser induced molecular dissociation of 1,1,1-trichloroethane (TCE) were studied using a range of intensities and standard laser wavelengths with nanosecond and femtosecond pulse durations. TCE contains C-H, C-C and C-Cl bonds and selective bond breakage of one or more of these bonds is of scientific interest. Using laser ionization time of flight mass spectrometry, it was found that considerable variation of fragment ion peak heights as well as changes in relative peak ratios ...

  15. Comparative Study of the Dissociative Ionization of 1,1,1-Trichloroethane Using Nanosecond and Femtosecond Laser Pulses

    OpenAIRE

    Du Plessis, Anton; Strydom, Christien; Botha, Lourens

    2010-01-01

    Changes in the laser induced molecular dissociation of 1,1,1-trichloroethane (TCE) were studied using a range of intensities and standard laser wavelengths with nanosecond and femtosecond pulse durations. TCE contains C-H, C-C and C-Cl bonds and selective bond breakage of one or more of these bonds is of scientific interest. Using laser ionization time of flight mass spectrometry, it was found that considerable variation of fragment ion peak heights as well as changes in relative peak ratios ...

  16. Direct dissociative chemisorption of alkanes on Pt(111): Influence of molecular complexity

    International Nuclear Information System (INIS)

    The direct dissociative chemisorption of ethane, propane, n-butane, isobutane, and neopentane on Pt(111) was investigated as a function of the initial translational energy, ET, polar angle of incidence, θi, initial vibrational temperature, and surface temperature using supersonic molecular beam techniques. For each alkane, the initial probability for direct dissociative chemisorption scales with the initial normal energy of the alkanes, En=ET cos2 θi, and is independent of both the surface temperature and initial vibrational energy of the alkanes under the experimental conditions employed. Above initial normal energies of approximately 125 kJ/mol, at constant En, the dissociation probability decreases with increasing chain length of the C2-C4 linear alkanes; however, the dissociation probability of neopentane is greater than that of isobutane, and both isobutane and neopentane are more reactive than n-butane. By assuming that cleavage of primary C-H bonds is the dominant reaction pathway for all of the alkanes investigated here, the trends in reactivity are best explained by considering the differences in the steric factors for primary C-H bond cleavage for these alkanes. Secondary C-H bond cleavage does appear to contribute to the reactivity of propane and n-butane but only at the highest energies examined. Additionally, the reaction probabilities of each of these alkanes were estimated using a statistical model recently proposed by Ukrainstev and Harrison [J. Chem. Phys. 101, 1564 (1994)]. Assuming cleavage of only primary C-H bonds, the trends in reactivity for ethane, propane, n-butane, and isobutane were qualitatively reproduced by the statistical model; however, except for ethane, which was used to obtain the necessary parameters for the theory, there was poor quantitative agreement, and the predictions for neopentane were significantly lower than the measured values. The model also predicts that the dissociation probability is enhanced by increasing the

  17. Research Reports: Hallucinogens and Dissociative Drugs

    Science.gov (United States)

    ... dangerous behavior. Hallucinogens such as LSD, psilocybin, peyote, DMT, and ayahuasca cause emotions to swing wildly and ... Dissociative Drugs? How Do Hallucinogens (LSD, Psilocybin, Peyote, DMT, and Ayahuasca) Affect the Brain and Body? What ...

  18. 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.

  19. Comparison of collision-induced dissociation and electron-induced dissociation of phillyrin using FT-ICR MS

    Science.gov (United States)

    Lin, Zhenguang; Lin, Zhiwei; Mu, Yingdi; Yan, Dong

    2016-10-01

    Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry using collision-induced dissociation (CID) and electron capture dissociation (ECD) at high mass resolution was first applied to investigate the characteristic fragment ions of phillyrin. The CID experimental results demonstrated the elemental composition of fragment ions unambiguously, so a reasonable fragmentation pathway of phillyrin was proposed. The ECD fragmentation mechanism was believed to be fundamentally different from the CID method. ECD could be used not only in the biological field but also as a powerful complement to the structural identification of small molecular compounds. The characteristic fragmentation pathways were helpful in analyzing and interpreting the stability and property of the parent ion. The ESI FT-ICR MS using CID and ECD methods was applied to investigate the characteristic fragment ions of Phillyrin for the first time. The fragmentation process of phillyrin which formation of the peroxide bond by CID, was discussed in detail. These characteristic fragmentation pathways were helpful to analyze and interpret the stability and property of the parent ion. It was clearly demonstrated that ECD can be not only used to Biological field but also a powerful complement to the structure identification of small molecules.

  20. Alteration of the flexible loop in 1-deoxy-D-xylulose-5-phosphate reductoisomerase boosts enthalpy-driven inhibition by fosmidomycin.

    Science.gov (United States)

    Kholodar, Svetlana A; Tombline, Gregory; Liu, Juan; Tan, Zhesen; Allen, C Leigh; Gulick, Andrew M; Murkin, Andrew S

    2014-06-01

    1-Deoxy-d-xylulose-5-phosphate reductoisomerase (DXR), which catalyzes the first committed step in the 2-C-methyl-d-erythritol 4-phosphate pathway of isoprenoid biosynthesis used by Mycobacterium tuberculosis and other infectious microorganisms, is absent in humans and therefore an attractive drug target. Fosmidomycin is a nanomolar inhibitor of DXR, but despite great efforts, few analogues with comparable potency have been developed. DXR contains a strictly conserved residue, Trp203, within a flexible loop that closes over and interacts with the bound inhibitor. We report that while mutation to Ala or Gly abolishes activity, mutation to Phe and Tyr only modestly impacts kcat and Km. Moreover, pre-steady-state kinetics and primary deuterium kinetic isotope effects indicate that while turnover is largely limited by product release for the wild-type enzyme, chemistry is significantly more rate-limiting for W203F and W203Y. Surprisingly, these mutants are more sensitive to inhibition by fosmidomycin, resulting in Km/Ki ratios up to 19-fold higher than that of wild-type DXR. In agreement, isothermal titration calorimetry revealed that fosmidomycin binds up to 11-fold more tightly to these mutants. Most strikingly, mutation strongly tips the entropy-enthalpy balance of total binding energy from 50% to 75% and 91% enthalpy in W203F and W203Y, respectively. X-ray crystal structures suggest that these enthalpy differences may be linked to differences in hydrogen bond interactions involving a water network connecting fosmidomycin's phosphonate group to the protein. These results confirm the importance of the flexible loop, in particular Trp203, in ligand binding and suggest that improved inhibitor affinity may be obtained against the wild-type protein by introducing interactions with this loop and/or the surrounding structured water network.

  1. Spontaneous exciton dissociation in carbon nanotubes

    OpenAIRE

    Kumamoto, Y.; Yoshida, M.; Ishii, A; Yokoyama, A.; Shimada, T; Kato, Y. K.

    2013-01-01

    Simultaneous photoluminescence and photocurrent measurements on individual single-walled carbon nanotubes reveal spontaneous dissociation of excitons into free electron-hole pairs. Correlation of luminescence intensity and photocurrent shows that a significant fraction of excitons are dissociating during their relaxation into the lowest exciton state. Furthermore, the combination of optical and electrical signals also allows for extraction of the absorption cross section and the oscillator st...

  2. Dissociative Identity Disorder: A Controversial Diagnosis

    OpenAIRE

    Gillig, Paulette Marie

    2009-01-01

    A brief description of the controversies surrounding the diagnosis of dissociative identity disorder is presented, followed by a discussion of the proposed similarities and differences between dissociative identity disorder and borderline personality disorder. The phenomenon of autohypnosis in the context of early childhood sexual trauma and disordered attachment is discussed, as is the meaning of alters or alternate personalities. The author describes recent neurosciences research that may r...

  3. Compulsive symptoms in dissociative (conversion) disorder

    OpenAIRE

    Agarwal, Arun Lata

    2006-01-01

    According to Mayer-Gross, Slater and Roth's classical textbook Clinical psychiatry, obsessive-compulsive symptoms are rarely seen in hysteria. The release of obsessive-compulsive symptoms is said to occur only in those who are constitutionally predisposed. In this context, the case of a young woman with dissociative (conversion) disorder, who presented with compulsive symptoms, is reported. In her case, the dissociative phenomena manifested as compulsive symptoms without concomitant predispos...

  4. Quantum chemical study of chlorine-dissociation of oxalyl chloride (ClCO)2→2Cl + 2CO

    Institute of Scientific and Technical Information of China (English)

    戴年珍; 李宗和

    2003-01-01

    The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a photon, (ClCO)2 is excited to the first excited state and one of its C-Cl bonds is broken toyield Cl and ClCOCO* free radicals. In addition, ClCOCO* with high energy is prone to release energy (Q), and to turn into ClCOCO in the ground state. The energy (Q) is adequate for ClCOCO to break down into ClCO and CO, and even for ClCO into Cl and CO. The result is consistent with the experimental data that Kong reported.

  5. 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.

  6. Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0(2,6)]decane.

    Science.gov (United States)

    Hudzik, Jason M; Castillo, Álvaro; Bozzelli, Joseph W

    2015-09-24

    Exo-tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is an interesting strained ring compound and the single-component high-energy density hydrocarbon fuel known as JP-10. Important initial reactions of TCD at high temperatures could cleave a strained carbon-carbon (C-C) bond in the ring system creating diradicals also constrained by the remaining ring system. This study determines the thermochemical properties of these diradicals (TCD-H2 mJ-nJ where m and n correspond to the cleaved carbons sites) including the carbon-carbon bond dissociation energy (C-C BDE) corresponding to the cleaved TCD site. Thermochemical properties including enthalpies (ΔH°f298), entropies (S(T)), heat capacities (Cp(T)), and C-H and C-C BDEs for the parent (TCD-H2 m-n), radical (TCD-H2 mJ-n and m-nJ), diradical (TCD-H2 mJ-nJ), and carbene (TCD-H2 mJJ-n and m-nJJ) species are determined. Structures, vibrational frequencies, moments of inertia, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level of theory. Standard enthalpies of formation in the gas phase for the TCD-H2 m-n parent and radical species are determined using the B3LYP density functional theory and the higher level G3MP2B3 and CBS-QB3 composite methods. For singlet and triplet TCD diradicals and carbenes, M06-2X, ωB97X-D, and CCSD(T) methods are included in the analysis to determine ΔH°f298 values. The C-C BDEs are further calculated using CASMP2(2,2)/aug-cc-pvtz//CASSCF(2,2)/cc-pvtz and with the CASMP2 energies extrapolated to the complete basis set limit. The bond energies calculated with these methods are shown to be comparable to the other calculation methods. Isodesmic work reactions are used for enthalpy analysis of these compounds for effective cancelation of systematic errors arising from ring strain. C-C BDEs range from 77.4 to 84.6 kcal mol(-1) for TCD diradical singlet species. C-H BDEs for the parent TCD-H2 m-n carbon sites range from 93 to 101 kcal mol(-1) with a

  7. 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.

  8. Enthalpy of Mixing of Liquid Al-Cr and Cr-Ni Alloys

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The partial and the integral enthalpies of mixing of liquid Al-Cr and Ni-Cr binary alloys have been determined by high temperature isoperibolic calorimetry at 1723±5 K and 1729±5 K, respectively. The results were analytically described by the thermodynamically adapted power series (TAPS). The enthalpies of mixing values for both binary liquid melts are small and negative and in good agreement with the available literature data. Minima of the mixing enthalpies of liquid Al-Cr and Ni-Cr alloys are -7.0 kJ.mol-1 at 46 at. pct Cr and -3.0 k J@mol-1 at 37 at. pct Cr,respectively.

  9. Enthalpies of formation of compounds in Al-Ni-Y system

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The enthalpies of formation of the ternary compounds Al4NiY, Al2NiY, Al2Ni6Y3, Al16 Ni3Y, AlNiY, Al3Ni2Y, AlNi8Y3, Al7Ni3Y2, and of the binary comp ounds Al2Y containing nickel and Ni5Y containing aluminum have been determined by high temperature reaction calorimetry. The enthalpy values measured are compared to previously published results where available as well as extended Miedema model predictions. The melting points of the compounds were determined by DTA and X-ray diffraction was used to confirm the crystal structures of the compounds. The enthalpi es of formation of the ternary compounds show a maximum along the 50%Al (mole fr action) section. The ternary compounds appear along lines of constant yttrium content consistent with binary compound solubility extensions.

  10. Double hidden layer RBF process neural network based online prediction of steam turbine exhaust enthalpy

    Institute of Scientific and Technical Information of China (English)

    GONG Huanchun

    2014-01-01

    In order to diagnose the unit economic performance online,the radial basis function (RBF) process neural network with two hidden layers was introduced to online prediction of steam turbine exhaust enthalpy.Thus,the model reflecting complicated relationship between the steam turbine exhaust enthalpy and the relative operation parameters was established.Moreover,the enthalpy of final stage extraction steam and exhaust from a 300 MW unit turbine was taken as the example to perform the online calculation. The results show that,the average relative error of this method is less than 1%,so the accuracy of this al-gorithm is higher than that of the BP neutral network.Furthermore,this method has advantages of high convergence rate,simple structure and high accuracy.

  11. Estimation of Formation Enthalpies of Organic Pollutants from a New Structural Group Contribution Method

    Institute of Scientific and Technical Information of China (English)

    Mehdi Bagheri; Afshin Bakhtiari; Masoume Jaberi

    2013-01-01

    Chemical stability and reactivity of organic pollutants is dependent to their formation enthalpies.The main objective of this study is to provide simple straightforward strategy for prediction of the formation enthalpies of wide range organic pollutants only from their structural functional groups.Using such an extended dataset comprising 1694 organic chemicals from 77 diverse material classes benefits the generalizability and reliability of the study.The new suggested collection of 12 functional groups and a simple linear regression lead to promising statistics of R2=0.958,Q2Loo =0.956,and δAEE=57 kJ·mol-1 for the whole dataset.Moreover,unknown experimental formation enthalpies for 27 organic pollutants are estimated by the presented approach.The resultant model needs no technical software/calculations,and thus can be easily applied by a non-specialist user.

  12. An Implicit Mixed Enthalpy-Temperature Method For Phase-Change Problems

    DEFF Research Database (Denmark)

    Krabbenhoft, Kristian; Damkilde, Lars; Nazem, M.

    2007-01-01

    Abstract A finite element procedure for phase-change problems is presented. Enthalpy and temperature are interpolated separately and subsequently linked via the appropriate relation in the nodes of the mesh during the solution phase. A novel technique is here used where, depending on the characte......Abstract A finite element procedure for phase-change problems is presented. Enthalpy and temperature are interpolated separately and subsequently linked via the appropriate relation in the nodes of the mesh during the solution phase. A novel technique is here used where, depending...... on the characteristics of the problem, either temperature or enthalpy may be considered as primary variable. The resulting algorithm is both efficient and robust and is further easy to implement and generalize to arbitrary finite elements. The capabilities of the method are illustrated by the solution both isothermal...

  13. Thermodynamic and ab initio analysis of the controversial enthalpy of formation of formaldehyde.

    Science.gov (United States)

    da Silva, Gabriel; Bozzelli, Joseph W; Sebbar, Nadia; Bockhorn, Henning

    2006-05-12

    There are two values, -26.0 and -27.7 kcal mol(-1), that are routinely reported in literature evaluations for the standard enthalpy of formation, Delta(f) H(o)(298), of formaldehyde (CH(2)=O), where error limits are less than the difference in values. In this study, we summarize the reported literature for formaldehyde enthalpy values based on evaluated measurements and on computational studies. Using experimental reaction enthalpies for a series of reactions involving formaldehyde, in conjunction with known enthalpies of formation, its enthalpy is determined to be -26.05+/-0.42 kcal mol(-1), which we believe is the most accurate enthalpy currently available. For the same reaction series, the reaction enthalpies are evaluated using six computational methods: CBS-Q, CBS-Q//B3, CBS-APNO, G2, G3, and G3B3 yield Delta(f) H(o)(298)=-25.90+/-1.17 kcal mol(-1), which is in good agreement to our experimentally derived result. Furthermore, the computational chemistry methods G3, G3MP2B3, CCSD/6-311+G(2df,p)//B3LYP/6-31G(d), CCSD(T)/6-311+G(2df,p)//B3LYP/6-31G(d), and CBS-APNO in conjunction with isodesmic and homodesmic reactions are used to determine Delta(f) H(o)(298). Results from a series of five work reactions at the higher levels of calculation are -26.30+/-0.39 kcal mol(-1) with G3, -26.45+/-0.38 kcal mol(-1) with G3MP2B3, -26.09+/-0.37 kcal mol(-1) with CBS-APNO, -26.19+/-0.48 kcal mol(-1) with CCSD, and -26.16+/-0.58 kcal mol(-1) with CCSD(T). Results from heat of atomization calculations using seven accurate ab initio methods yields an enthalpy value of -26.82+/-0.99 kcal mol(-1). The results using isodesmic reactions are found to give enthalpies more accurate than both other computational approaches and are of similar accuracy to atomization enthalpy calculations derived from computationally intensive W1 and CBS-APNO methods. Overall, our most accurate calculations provide an enthalpy of formation in the range of -26.2 to -26.7 kcal mol(-1), which is within

  14. Do enthalpy and entropy distinguish first in class from best in class?

    Science.gov (United States)

    Freire, Ernesto

    2008-10-01

    A drug molecule should bind to its target with high affinity and selectivity. Because the binding affinity is a combined function of the binding enthalpy and the binding entropy, extremely high affinity requires that both terms contribute favorably to binding. The binding enthalpy, however, is notoriously more difficult to optimize than the binding entropy, a fact that has resulted in thermodynamically unbalanced molecules that do not achieve optimal potency. In fact, with current technologies, the enthalpic optimization of drug candidates may take years and only appear in second-generation products. Within that context, it is not surprising that structure/activity relationships (SARs) that explicitly incorporate the interplay between enthalpy and entropy and accelerate the optimization process are being developed and gaining popularity.

  15. Hydrogen bonded supramolecular structures

    CERN Document Server

    Li, Zhanting

    2015-01-01

    This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems  made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to b

  16. Computational Investigation of Enthalpy-Entropy Compensation in Complexation of Glycoconjugated Bile Salts with β-Cyclodextrin and Analogs

    DEFF Research Database (Denmark)

    Tidemand, Kasper Damgaard; Schonbeck, Christian; Holm, Rene;

    2014-01-01

    of water molecules in the cavity increased with the DS. Release of water from the cavity resulted in a positive enthalpy change, which correlates qualitatively with the experimentally determined increase in complexation enthalpy and contributes to the enthalpy-entropy compensation. The positive change...... in complexation entropy with DS was not able to compensate for this unfavorable change in enthalpy induced by the HP substituents, resulting in a destabilizing effect. This was found to originate from fixation of the HP substituents and decreased free rotation of the bile salts within the CD cavities....

  17. Dissociative Spectrum Disorders in the Primary Care Setting

    OpenAIRE

    Elmore, James L.

    2000-01-01

    Dissociative disorders have a lifetime prevalence of about 10%. Dissociative symptoms may occur in acute stress disorder, posttraumatic stress disorder, somatization disorder, substance abuse, trance and possession trance, Ganser's syndrome, and dissociative identity disorder, as well as in mood disorders, psychoses, and personality disorders. Dissociative symptoms and disorders are observed frequently among patients attending our rural South Carolina community mental health center. Given the...

  18. Primary retention following nuclear recoil in β-decay: Proposed synthesis of a metastable rare gas oxide (38ArO4) from (38ClO4−) and the evolution of chemical bonding over the nuclear transmutation reaction path

    International Nuclear Information System (INIS)

    Argon tetroxide (ArO4) is the last member of the N=50 e– isoelectronic and isosteric series of ions: SiO44−, PO43−, SO42−, and ClO4−. A high level computational study demonstrated that while ArO4 is kinetically stable it has a considerable positive enthalpy of formation (of ∼298 kcal/mol) (Lindh et al., 1999. J. Phys. Chem. A 103, pp. 8295–8302) confirming earlier predictions by Pyykkö (1990. Phys. Scr. 33, pp. 52–53). ArO4 can be expected to be difficult to synthesize by traditional chemistry due to its metastability and has not yet been synthesized at the time of writing. A computational investigation of the changes in the chemical bonding of chlorate (ClO4−) when the central chlorine atom undergoes a nuclear transmutation from the unstable artificial chlorine isotope 38Cl to the stable rare argon isotope 38Ar through β-decay, hence potentially leading to the formation of ArO4, is reported. A mathematical model is presented that allows for the prediction of yields following the recoil of a nucleus upon ejecting a β-electron. It is demonstrated that below a critical angle between the ejected β-electron and that of the accompanying antineutrino their respective linear momentums can cancel to such an extent as imparting a recoil to the daughter atom insufficient for breaking the Ar–O bond. As a result, a primary retention yield of ∼1% of ArO4 is predicted following the nuclear disintegration. The study is conducted at the quadratic configuration interaction with single and double excitations [QCISD/6−311+G(3df)] level of theory followed by an analysis of the electron density by the quantum theory of atoms in molecules (QTAIM). Crossed potential energy surfaces (PES) were used to construct a PES from the metastable ArO4 ground singlet state to the Ar–O bond dissociation product ArO3+O(3P) from which the predicted barrier to dissociation is ca. 22 kcal/mol and the exothermic reaction energy is ca. 28 kcal/mol [(U)MP2/6–311+G

  19. Standard molar enthalpies of formation of 3'- and 4'-nitroacetophenones

    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)

    2011-06-15

    Research highlights: The standard molar enthalpies of formation, in the condensed phase, of 3'- and 4'-nitroacetophenones have been determined by combustion calorimetry. The vapor pressures of the crystalline 3'- and 4'-nitroacetophenones were measured as function of temperature by the Knudsen effusion mass loss technique. The standard molar enthalpies, entropies and Gibbs functions of sublimation, at T = 298.15 K, were calculated for both compounds. - Abstract: The standard (p{sup o} = 0.1 MPa) molar enthalpies of formation, in the condensed phase, of 3'- and 4'-nitroacetophenones, presented in this work, were obtained from measurements of their combustion energies, at T = 298.15 K, using a static bomb calorimeter. The vapor pressures of the two crystalline 3'- and 4'-nitroacetophenones were measured as a function of temperature by the Knudsen effusion mass loss technique. The standard molar enthalpies of sublimation, at T = 298.15 K, were derived from the Clausius-Clapeyron equation. The standard molar enthalpies, entropies, and Gibbs functions of sublimation, at T = 298.15 K, were calculated for the two compounds. The experimental values obtained were used to calculate the standard molar enthalpies of formation of 3'- and 4'-nitroacetophenones, in the gaseous phase, as {Delta}{sub f}H{sub m}{sup 0}(g)=-(99.4{+-}1.6)kJ{center_dot}mol{sup -1} and {Delta}{sub f}H{sub m}{sup 0}(g)=-(99.1{+-}1.7)kJ{center_dot}mol{sup -1}, respectively, and these derived values are analyzed in terms of structural enthalpic increments.

  20. A moist "available enthalpy" norm: definition and comparison with existing "energy" norms

    CERN Document Server

    Marquet, Pascal

    2015-01-01

    Moist-air norms and inner-products are currently used in atmospheric science for computing dry or moist singular vectors and for determining forecast errors or sensitivity to observations based on tangent linear and adjoint models. A new moist-air norm is defined starting from old results published in Marquet (QJRMS 1993) and based on the "Available Enthalpy" approach, namely one of the Exergy function defined in general thermodynamics. Some interesting and promising impacts of this new "Available Enthalpy" norm are described in this brief version of a paper to be submitted to the QJRMS.

  1. Direct determination of enthalpies of solid phase reactions by immersion method

    International Nuclear Information System (INIS)

    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 Al2O3 samples irradiated at variable dose at a temperature of under 100 deg. C. (authors)

  2. A semi-empirical approach to accurate standard enthalpies of formation for solid hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Klaveness, A. [Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo (Norway)], E-mail: arnekla@kjemi.uio.no; Fjellvag, H.; Kjekshus, A.; Ravindran, P. [Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo (Norway); Swang, O. [SINTEF Materials and Chemistry, P.O. Box 124, Blindern, N-0314 Oslo (Norway)

    2009-02-05

    A semi-empirical method for estimation of enthalpies of formation of solid hydrides is proposed. The method is named Ionic for short. By combining experimentally known enthalpies of formation for simple hydrides and reaction energies computed using band-structure density functional theory (DFT) methods, startling accurate results can be achieved. The approach relies on cancellation of errors when comparing DFT energies for systems with similar electronic structures. The influence of zero-point energies, polaritons, and vibrational excitations on the results has been examined and found to be minor.

  3. A Topological Approach to the Correlation of Standard Formation Enthalpy with Path Index of Benzenes Derivatives

    Institute of Scientific and Technical Information of China (English)

    Li Liang-chao; Ni Cai-hua; Lin Qiu-yue

    2003-01-01

    A mathematical model formulated as △fHφm(g)= a + 5∑i=1 bipi (i ≠ 2) was constructed for the relationship between standard formation enthalpy △fH m (g) and path in-dex Pi of substituted benzenes derivatives. An empiric equation for the calculation of △f H0m(g) was worked out. The cal-culated values of standard formation enthalpy based on this model are excellently consistent with those from experimental for 55 organic compounds. The model is shown to be simple and of practical usefulness, particularly when required experimental data are unavailable.

  4. Entropy-enthalpy Compensation of Biomolecular Systems in Aqueous Phase: a Dry Perspective.

    Science.gov (United States)

    Movileanu, Liviu; Schiff, Eric A

    2013-01-01

    We survey thermodynamic measurements on processes involving biological macromolecules in aqueous solution, which illustrate well the ubiquitous phenomenon of entropy-enthalpy compensation. The processes include protein folding/unfolding and ligand binding/unbinding, with compensation temperatures varying by about 50 K around an average near 293 K. We show that incorporating both near-exact entropy-enthalpy compensation (due to solvent relaxation) and multi-excitation entropy (from vibrational quanta) leads to a compensation temperature in water of about 230 K. We illustrate a general procedure for subtracting solvent and environment-related terms to determine the bare Gibbs free energy changes of chemical processes.

  5. A Topological Approach to the Correlation of Standard Formation Enthalpy with Path Index of Benzenes Derivatives

    Institute of Scientific and Technical Information of China (English)

    LiLiang-chao; NiCai-hua; LinQiu-yue

    2003-01-01

    A mathematical model formulated as Δf/HmO-,(g) = a+∑5i=1bipi (i≠2) was constructed for the relationship between standard formation enthalpy ΔfHmO (g) and path index P, of substituted benzenes derivatives. An empiric equation for the calculation of ΔfHmO, (g) was worked out. The calculated values of standard formation enthalpy based on this model are excellently consistent with those from experimental for 55 organic compounds. The model is shown to be simple and of practical usefulness, particularly when required experimental data are unavailable.

  6. Formation Enthalpy Calculation of Oxygen Vacancy Defect in Doped Lithium Niobate Crystals

    Institute of Scientific and Technical Information of China (English)

    QIANG Liang-sheng; LI Yao; TANG Dong-yan; XU Chong-quan; WEI Yong-de

    2004-01-01

    The relationship between temperature and oxygen vacancy concentration is deduced in this paper. Based on the data of thermal weight-loss experiment, the formation enthalpies of congruent and several doped LN crystals have been calculated. It was found that the formation enthalpy of oxygen vacancies can be decreased evidently by doping valence-changeable ions. The experimental results were discussed and a new reduction process of the photorefractive LN crystal at a relatively low temperature was proposed, and the reduced crystals showed a good effect in practical use.

  7. Definition of Total Energy budget equation in terms of moist-air Enthalpy surface flux

    OpenAIRE

    Marquet, Pascal

    2015-01-01

    Uncertainty exists concerning the proper formulation of surface heat fluxes, namely the sum of "sensible" and "latent" heat fluxes, and in fact concerning these two fluxes if they are considered as separate fluxes. In fact, eddy flux of moist-air energy must be defined as the eddy transfer of moist-air specific enthalpy ($\\overline{w' h'}$), where the specific enthalpy ($h$) is equal to the internal energy of moist air plus the pressure divided by the density (namely $h = e_{\\rm int} + p/\\rho...

  8. Studies on plasma dissociation of zircon

    International Nuclear Information System (INIS)

    Zircon (zirconium silicate) is a major source of zirconium metal. Extraction of zirconium involves chlorination step to convert zirconium silicate to ZrCl4 and SiCl4. SiCl4 is separated and zirconium tetrachloride is reduced with magnesium to yield zirconium metal. Instead of this direct chlorination of zircon, it can be converted to zirconia by thermal plasma dissociation followed by alkali leaching process to separate silica. The resulting zirconium oxide can be used for zirconium extraction. This would result in considerable savings of chlorine consumption and also would eliminate the SiCl4 separation step. The Laser and Plasma Technology Division has developed a 20 kW laboratory 1 scale plasma reactor, which consists of a DC plasma torch mounted on a water cooled reaction chamber, DC power source, water cooling and gas feed system and a powder feeder. The system has been used to study in-flight dissociation of zircon in the thermal plasma jet. Dissociation studies were carried out over 5-16 kW power range. The plasma processed product was characterized by x-ray diffraction technique, which showed that it consisted of zirconium dioxide and silica. The extent of dissociation was estimated by gravimetric method involving alkali leaching of silica. Results of the study indicate that the extent of dissociation strongly depends on input power and other parameters such as plasma gas flow rate. Complete dissociation could be achieved at an input power of 12 kW. The average temperature at the nozzle exit of the plasma torch has been calculated for various input power levels. Calculations on heat transfer to the particles and residence time required to effect dissociation of zircon particles injected in the plasma jet have been carried out for various input power levels and particle sizes ranging from 20-150 microns. Details of the experiments and results will be discussed in the paper. (author)

  9. Australia's Bond Home Bias

    OpenAIRE

    Mishra, Anil V; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  10. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  11. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...

  12. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  13. Dissociation of CO induced by He2+ ions : II. Dissociation pathways and states

    NARCIS (Netherlands)

    Schlatholter, T; Hoekstra, R; Morgenstern, R

    1997-01-01

    The dissociation of COq+ ions (q less than or equal to 3) produced in collisions of 2-10 keV amu(-1) He2+ ions with CO has been studied by time-of-flight methods. From the time-of-flight spectra the energy released in the dissociation process is determined. Our results for the kinetic energy release

  14. K*-charmonium dissociation cross sections and charmonium dissociation rates in hadronic matter

    Science.gov (United States)

    Liu, Feng-Rong; Ji, Shi-Tao; Xu, Xiao-Ming

    2016-08-01

    K*-charmonium dissociation reactions in hadronic matter are studied in the Born approximation, in the quark-interchange mechanism, and with a temperature-dependent quark potential. We obtain the temperature dependence of the unpolarized cross sections for the reactions K^* J/ψ to bar DD_s^ + ,bar D^* D_s^ + ,bar DD_s^{* + } , and bar D^* D_s^{* + } ; K^* χ _c to bar DD_s^ + ,bar D^* D_s^ + ,bar DD_s^{* + } , and bar D^* D_s^{* + } . We use the cross sections for charmonium dissociation in collisions with pions, ρ mesons, kaons, vector kaons, and η mesons to calculate the dissociation rates of charmonium with five types of mesons. Because of the temperature dependence of the meson masses, dissociation cross sections, and meson distribution functions, the charmonium dissociation rates generally increase with increasing temperature and decrease with increasing charmonium momentum from 2.2 GeV/c. We find that the first derivative of the dissociation rate with respect to the charmonium momentum is zero when the charmonium is at rest. While the η + ψ' and the η + χ c dissociation reactions can be neglected, the J/ ψ, ψ', and χ c dissociations are caused by collisions with pions, ρ mesons, kaons, vector kaons, and η mesons.

  15. On optimal designing of low frequency polychromatic fields for facile photo-dissociation of model diatomic molecules

    Indian Academy of Sciences (India)

    S Ghosh; K Maji; R Sharma; S P Bhattacharyya

    2009-09-01

    The dissociation of a diatomic molecule in low frequency polychromatic fields of moderate intensities is studied. Genetic Algorithm is invoked to search out a set of four optimal non-resonant frequencies (1 - 4), intensities (1 - 4) the and phase angles (1 - 4), for achieving a facile photo dissociation. Time-dependent Hellmann-Feynman theorem is used to gain insight into the frequency resolved energy absorption pattern. The ‘quantum phase space’ structures indicate occurrence of bond breaking dynamics akin to the classical one.

  16. The co-occurrence of PTSD and dissociation: differentiating severe PTSD from dissociative-PTSD

    DEFF Research Database (Denmark)

    Armour, C.; Karstoft, K. I.; Richardson, J. D.

    2014-01-01

    A dissociative-posttraumatic stress disorder (PTSD) subtype has been included in the DSM-5. However, it is not yet clear whether certain socio-demographic characteristics or psychological/clinical constructs such as comorbid psychopathology differentiate between severe PTSD and dissociative...... were assessed with the Clinician Administered PTSD Scale (CAPS) and self-report measures of traumatic life events, depression, and anxiety. CAPS severity scores were created reflecting the sum of the frequency and intensity items from each of the 17 PTSD and 3 dissociation items. The CAPS severity...... constituted a severe PTSD group (30.5 %), and one of which constituted a dissociative-PTSD group (13.7 %). None of the included, demographic, trauma, or clinical covariates were significantly predictive of membership in the dissociative-PTSD group compared to the severe PTSD group. In conclusion...

  17. The Influence of Interatomic Bonding Potentials on Detonation Properties

    OpenAIRE

    Heim, Andrew J.; Grønbech-Jensen, Niels; Germann, Timothy C.; Kober, Edward M.; Holian, Brad Lee; Lomdahl, Peter S.

    2006-01-01

    The dependence of macroscopic detonation properties of a two-dimensional diatomic (AB) molecular system on the fundamental properties of the molecule were investigated. This includes examining the detonation velocity, reaction zone thickness, and critical width as a function of the exothermicity of the gas-phase reaction and the gas-phase dissociation energy for. Following previous work, molecular dynamics (MD) simulations with a reactive empirical bond-order potential were used to characteri...

  18. Primary retention following nuclear recoil in β-decay: Proposed synthesis of a metastable rare gas oxide ((38)ArO4) from ((38)ClO4(-)) and the evolution of chemical bonding over the nuclear transmutation reaction path.

    Science.gov (United States)

    Timm, Matthew J; Matta, Chérif F

    2014-12-01

    Argon tetroxide (ArO4) is the last member of the N=50 e(-) isoelectronic and isosteric series of ions: SiO4(4-), PO4(3-), SO4(2-), and ClO4(-). A high level computational study demonstrated that while ArO4 is kinetically stable it has a considerable positive enthalpy of formation (of ~298kcal/mol) (Lindh et al., 1999. J. Phys. Chem. A 103, pp. 8295-8302) confirming earlier predictions by Pyykkö (1990. Phys. Scr. 33, pp. 52-53). ArO4 can be expected to be difficult to synthesize by traditional chemistry due to its metastability and has not yet been synthesized at the time of writing. A computational investigation of the changes in the chemical bonding of chlorate (ClO4(-)) when the central chlorine atom undergoes a nuclear transmutation from the unstable artificial chlorine isotope (38)Cl to the stable rare argon isotope (38)Ar through β-decay, hence potentially leading to the formation of ArO4, is reported. A mathematical model is presented that allows for the prediction of yields following the recoil of a nucleus upon ejecting a β-electron. It is demonstrated that below a critical angle between the ejected β-electron and that of the accompanying antineutrino their respective linear momentums can cancel to such an extent as imparting a recoil to the daughter atom insufficient for breaking the Ar-O bond. As a result, a primary retention yield of ~1% of ArO4 is predicted following the nuclear disintegration. The study is conducted at the quadratic configuration interaction with single and double excitations [QCISD/6-311+G(3df)] level of theory followed by an analysis of the electron density by the quantum theory of atoms in molecules (QTAIM). Crossed potential energy surfaces (PES) were used to construct a PES from the metastable ArO4 ground singlet state to the Ar-O bond dissociation product ArO3+O((3)P) from which the predicted barrier to dissociation is ca. 22kcal/mol and the exothermic reaction energy is ca. 28kcal/mol [(U)MP2/6-311+G(d)].

  19. Bonding thermoplastic polymers

    Science.gov (United States)

    Wallow, Thomas I.; Hunter, Marion C.; Krafcik, Karen Lee; Morales, Alfredo M.; Simmons, Blake A.; Domeier, Linda A.

    2008-06-24

    We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

  20. The Relationship between Lattice Enthalpy and Melting Point in Magnesium and Aluminium Oxides. Science Notes

    Science.gov (United States)

    Talbot, Christopher; Yap, Lydia

    2013-01-01

    This "Science Note" presents a study by Christopher Talbot and Lydia Yap, who teach IB Chemistry at Anglo-Chinese School (Independent), Republic of Singapore, to pre-university students. Pre-university students may postulate the correlation between the magnitude of the lattice enthalpy compound and its melting point, since both…

  1. FORMATION (DECOMPOSITION) ENTHALPY CALCULATIONS FOR CRYSTAL LATTICES OF ALKALINE-EARTH FLUORIDES

    OpenAIRE

    Gruba, O.; Germanyuk, N.; Ryabukhin, A.

    2015-01-01

    A series of calculations of structural and thermochemical properties has been carried out for the alkaline-earth fluorides. The calculations have been carried out using the modified model of effective ionic radii and the model of enthalpy calculation for the crystal lattice. The results of the calculations are in accordance with the known experimental data within confidence intervals.

  2. Fractured Anhydrite as a Geothermal Source in a Low Enthalpy Context (Southern Permian Basin, Netherlands)

    NARCIS (Netherlands)

    Daniilidis, Alexandros; Herber, Marinus

    2015-01-01

    Increased heat flow associated with the presence of salt domes could be beneficial for geothermal energy applications in a low enthalpy nvironment. Anhydrite layers within such salt domes could be a potential geothermal target. These layers are known to undergo brittle deformation, which in turn can

  3. Effect of Spacers on CMCs and Micelle-forming Enthalpies of Gemini Surfactants by Titration Microcalorimetry

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The critical micelle concentrations (CMC) and the micelle-forming enthalpies (D Hmic) of gemini surfactants were first measured by the precise titration microcalorimetry. The results showed that D Hmic values are negative, and there is an exothermal minimum between s=4 and s=6. Furthermore, the CMCs of the surfactants are in good agreement with literature values.

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

    Energy Technology Data Exchange (ETDEWEB)

    Fima, Przemysław, E-mail: p.fima@imim.pl [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, ul. Reymonta 25, 30-059 Krakow (Poland); Flandorfer, Hans [Department of Inorganic Chemistry/Materials Chemistry, University of Vienna, Waehringer Street 42, A-1090 Vienna (Austria)

    2014-01-10

    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.

  5. The thermal characterization of multi-component systems by enthalpy relaxation

    NARCIS (Netherlands)

    Brinke, Gerrit ten; Oudhuis, Lizette; Ellis, Thomas S.

    1994-01-01

    The phenomenon of enthalpy relaxation of amorphous glassy polymers has been developed into an analytical tool which can be applied to elucidate phase behavior and morphologically related phenomena of multi-component systems. We have both reviewed the experimental details concerning its application,

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

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Margarida S., E-mail: msmirand@fc.up.p [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); Centro de Geologia da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Morais, Victor M.F., E-mail: vmmorais@icbas.up.p [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); Instituto de Ciencias Biomedicas Abel Salazar, ICBAS, Universidade do Porto, P-4099-003 Porto (Portugal); Matos, M. Agostinha R., E-mail: marmatos@fc.up.p [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); Liebman, Joel F., E-mail: jliebman@umbc.ed [Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250 (United States)

    2010-09-15

    The energetics of 1-benzosuberone was studied by a combination of calorimetric techniques and computational calculations. The standard (p{sup 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{sup 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{sup -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.

  7. A method to estimate the enthalpy of formation of organic compounds with chemical accuracy

    DEFF Research Database (Denmark)

    Hukkerikar, Amol; Meier, Robert J.; Sin, Gürkan;

    2013-01-01

    . The model which is group-contribution (GC) based, estimates gas phase standard enthalpy of formations (ΔfH°gas) of organic compounds. To achieve the chemical accuracy, a systematic property-data-model analysis, which allows efficient use of knowledge of the experimental data of ΔfH°gas and the molecular...

  8. The Correlation of Standard Entropy with Enthalpy Supplied from 0 to 298.15 K

    Science.gov (United States)

    Lambert, Frank L.; Leff, Harvey S.

    2009-01-01

    As a substance is heated at constant pressure from near 0 K to 298 K, each incremental enthalpy increase, dH, alters entropy by dH/T, bringing it from approximately zero to its standard molar entropy S degrees. Using heat capacity data for 32 solids and CODATA results for another 45, we found a roughly linear relationship between S degrees and…

  9. Sub-Tg enthalpy relaxation in an unstable oxide glass former: insights into the structural heterogeneity

    DEFF Research Database (Denmark)

    Yue, Yuanzheng; Zhang, Yanfei

    Structural heterogeneity plays a crucial role in determining functionality of glasses. In this work we have found that the sub-Tg enthalpy relaxation pattern in a hyperquenched glass is highly sensitive to structural heterogeneity. As a consequence, the former can be used as an effective approach...

  10. Experimental study on mass transfer of contaminants through an enthalpy recovery unit with polymer membrane foils

    DEFF Research Database (Denmark)

    Nie, Jinzhe; Fang, Lei

    2014-01-01

    could transfer from exhaust air to supply air through the enthalpy recovery unit. The mass transfer efficiency of contaminants was independent of the hygro-thermal differences between indoor and outdoor climate conditions. The mass transfer ratio of the chemical contaminants in the total heat recovery...

  11. Thermal diffusion and partial molar enthalpy variations of n-butane in silicalite-1.

    Science.gov (United States)

    Inzoli, I; Simon, J M; Bedeaux, D; Kjelstrup, S

    2008-11-27

    We report for the first time the heat of transfer and the Soret coefficient for n-butane in silicalite-1. The heat of transfer was typically 10 kJ/mol. The Soret coefficient was typically 0.006 K(-1) at 360 K. Both varied with the temperature and the concentration. The thermal conductivity of the crystal with butane adsorbed was 1.46 +/- 0.07 W/m K. Literature values of the isosteric enthalpy of adsorption, the concentration at saturation, and the diffusion coefficients were reproduced. Nonequilibrium molecular dynamics simulations were used to find these results, and a modified heat-exchange algorithm, Soft-HEX, was developed for the purpose. Enthalpies of butane were also determined. We use these results to give numerical proof for a recently proposed relation, that the heat of transfer plus the partial molar enthalpy of butane is constant at a given temperature. The proof is offered for a regime where the partial molar enthalpy can be approximated by the molar internal energy. This result may add to the understanding of the sign of the Soret coefficient. The technical importance of the heat of transfer is discussed.

  12. Experimental-numerical study of heat flow in deep low-enthalpy geothermal conditions

    NARCIS (Netherlands)

    Saeid, S.; Al-Khoury, R.; Nick, H.M.; Barends, F.

    2014-01-01

    This paper presents an intensive experimental-numerical study of heat flow in a saturated porous domain. A temperature and a flow rate range compared to that existing in a typical deep low-enthalpy hydrothermal system is studied. Two main issues are examined: the effect of fluid density and viscosit

  13. High Temperature Heat Capacity of Alloy D9 Using Drop Calorimetry Based Enthalpy Increment Measurements

    Science.gov (United States)

    Banerjee, Aritra; Raju, S.; Divakar, R.; Mohandas, E.

    2007-02-01

    Alloy D9 is a void-swelling resistant nuclear grade austenitic stainless steel (SS) based on AISI type 316-SS in which titanium constitutes an added predetermined alloying composition. In the present study, the high-temperature enthalpy values of alloy D9 with three different titanium-to-carbon mass percent ratios, namely Ti/C = 4, 6, and 8, have been measured using inverse drop calorimetry in the temperature range from 295 to 1323 K. It is found that within the level of experimental uncertainty, the enthalpy values are independent of the Ti-C mass ratio. The temperature dependence of the isobaric specific heat C P is obtained by a linear regression of the measured enthalpy data. The measured C P data for alloy D9 may be represented by the following best-fit expression: C_P(J \\cdot kg^{-1}\\cdot K^{-1})= 431 + 17.7 × 10^{-2}T + 8.72 × 10^{-5}/T^2. It is found that the measured enthalpy and specific heat values exhibit good agreement with reported data on 316 and other related austenitic stainless steels.

  14. SGC method for predicting the standard enthalpy of formation of pure compounds from their molecular structures

    Energy Technology Data Exchange (ETDEWEB)

    Albahri, Tareq A., E-mail: toalbahri@gmail.com; Aljasmi, Abdulla F.

    2013-09-20

    Highlights: • ΔH°{sub f} is predicted from the molecular structure of the compounds alone. • ANN-SGC model predicts ΔH°{sub f} with a correlation coefficient of 0.99. • ANN-MNLR model predicts ΔH°{sub f} with a correlation coefficient of 0.90. • Better definition of the atom-type molecular groups is presented. • The method is better than others in terms of combined simplicity, accuracy and generality. - Abstract: A theoretical method for predicting the standard enthalpy of formation of pure compounds from various chemical families is presented. Back propagation artificial neural networks were used to investigate several structural group contribution (SGC) methods available in literature. The networks were used to probe the structural groups that have significant contribution to the overall enthalpy of formation property of pure compounds and arrive at the set of groups that can best represent the enthalpy of formation for about 584 substances. The 51 atom-type structural groups listed provide better definitions of group contributions than others in the literature. The proposed method can predict the standard enthalpy of formation of pure compounds with an AAD of 11.38 kJ/mol and a correlation coefficient of 0.9934 from only their molecular structure. The results are further compared with those of the traditional SGC method based on MNLR as well as other methods in the literature.

  15. Sequential bond energies and structures of the Cr+·(N2), n =1−4

    Indian Academy of Sciences (India)

    Jamal N Dawoud

    2014-11-01

    DFT calculations, with an effective core potential for the chromium ion and large polarized basis set functions have been used to calculate the sequential bond dissociation energies of the Cr+·(N2) (n = 1—4) complexes. A linear configuration was obtained for the Cr+·N2 and Cr+·(N2)2 complexes with sequential bond dissociation energies of 14.6 and 16.4 kcal mol-1, respectively. For the Cr+·(N2)3 and Cr+·(N2)4 complexes, distorted trigonal pyramidal and tetrahedral geometries were optimized with sequential bond dissociation energies of 6.5 and 5.5 kcal mol-1, respectively. - back-donation in side-on approach of the Cr+·N2 leads to the formation of a tilted structure with the Cr+ ion in central position. The di-ligated complex exhibits the strongest bond dissociation energy among these four Cr+·(N2) (n = 1—4) complexes since it has the largest Cr+—N bond order.

  16. Dissociative ionization of methanol in medium intense femtosecond laser field using time-of-flight mass spectrometry

    International Nuclear Information System (INIS)

    800 nm 100 fs laser combined with TOF mass spectrometer was used to investigate the dissociative ionization of methanol, CH3OH in the laser intensity less than 4×1013 W/cm2. The results showed that the dissociation follows a sequential step-wise dissociation pattern, with no sign for Coulomb explosion. At very low intensity 1.4×1013 W/cm2, only the parent ion CH3OH+ appears. At 1.7×1013 W/cm2, the dissociation products are mainly due to hydrogen elimination from the O–H or C–H bonds forming CH3O+ and CH2OH+ primary ions. At 2.0×1013 W/cm2, the C–O bond starts to break forming CH3+, which simultaneously dissociates to CH2+. The primary fragment ions CH3O+ and CH2OH+ start to dissociate into lower secondary fragments as CH2O+ and CHO+ for the former and CHOH+ and COH+ for the latter. At 2.8×1013 W/cm2, secondary dissociation fragments dominate the spectrum including C+, CH+, CH2+, OH+, and O+ and the H+ is detected. At 3.0×1013 W/cm2, H2+ is detected. For all ions formed, the ion yield increases with laser intensity till it reaches maximum, after which it drops down manifesting the dissociation of these ions into smaller fragments. Among all ions, only H+ was found to have angular anisotropic distribution. - Highlights: • Dissociation follows step-wise dissociation with no sign for Coulomb explosion. • CH3OH+, CH3O+, CH3+ form at 1.4×1013, 1.7×1013, 2.0×1013 W/cm2, respectively. • C+, CH+, CH2+, OH+, and O+ and the H+ is detected at 2.8⁎1013 W/cm2. • H2+ is detected at 3.0×1013 W/cm2. • Among all ions, only H+ was found to have angular anisotropic distribution

  17. Application of the numerical density-enthalpy method to the multi-phase flow through a porous medium

    NARCIS (Netherlands)

    Ibrahim, D.; Vermolen, F.J.; Vuik, C.

    2010-01-01

    In this paper we apply a new method to solve multi-phase fluid flow problem for 1D1D and 2D2D fluid systems. This method is developed at TNO and presented in [1] for spatially homogeneous systems. We call this method the numerical density-enthalpy method (or ρρ-hh method) because density-enthalpy ph

  18. The effect of carbon monoxide Co-adsorption on Ni-catalysed water dissociation.

    Science.gov (United States)

    Mohsenzadeh, Abas; Borjesson, Anders; Wang, Jeng-Han; Richards, Tobias; Bolton, Kim

    2013-01-01

    The effect of carbon monoxide (CO) co-adsorption on the dissociation of water on the Ni(111) surface has been studied using density functional theory. The structures of the adsorbed water molecule and of the transition state are changed by the presence of the CO molecule. The water O-H bond that is closest to the CO is lengthened compared to the structure in the absence of the CO, and the breaking O-H bond in the transition state structure has a larger imaginary frequency in the presence of CO. In addition, the distances between the Ni surface and H2O reactant and OH and H products decrease in the presence of the CO. The changes in structures and vibrational frequencies lead to a reaction energy that is 0.17 eV less exothermic in the presence of the CO, and an activation barrier that is 0.12 eV larger in the presence of the CO. At 463 K the water dissociation rate constant is an order of magnitude smaller in the presence of the CO. This reveals that far fewer water molecules will dissociate in the presence of CO under reaction conditions that are typical for the water-gas-shift reaction.

  19. The Effect of Carbon Monoxide Co-Adsorption on Ni-Catalysed Water Dissociation

    Directory of Open Access Journals (Sweden)

    Abas Mohsenzadeh

    2013-11-01

    Full Text Available The effect of carbon monoxide (CO co-adsorption on the dissociation of water on the Ni(111 surface has been studied using density functional theory. The structures of the adsorbed water molecule and of the transition state are changed by the presence of the CO molecule. The water O–H bond that is closest to the CO is lengthened compared to the structure in the absence of the CO, and the breaking O–H bond in the transition state structure has a larger imaginary frequency in the presence of CO. In addition, the distances between the Ni surface and H2O reactant and OH and H products decrease in the presence of the CO. The changes in structures and vibrational frequencies lead to a reaction energy that is 0.17 eV less exothermic in the presence of the CO, and an activation barrier that is 0.12 eV larger in the presence of the CO. At 463 K the water dissociation rate constant is an order of magnitude smaller in the presence of the CO. This reveals that far fewer water molecules will dissociate in the presence of CO under reaction conditions that are typical for the water-gas-shift reaction.

  20. Collision induced dissociation study of azobenzene and its derivatives: computational and experimental results

    Science.gov (United States)

    Rezaee, Mohammadreza; Compton, Robert

    2015-03-01

    Experimental and computational investigation have been performed in order to study the bond dissociation energy of azobenzene and its derivatives using collision induced dissociation method as well as other energy and structural characteristics. The results have been verified by comparing with results obtained from computational quantum chemistry. We used different density functional methods as well as the Möller-Plesset perturbation theory and the coupled cluster methods to explore geometric, electronic and the spectral properties of the sample molecules. Geometries were calculated and optimized using the 6-311 + + G(2d,2p) basis set and the B3LYP level of theory and these optimized structures have been subjected to the frequency calculations to obtain thermochemical properties by means of different density functional, Möller-Plesset, and coupled cluster theories to obtain a high accuracy estimation of the bond dissociation energy value. The results from experiments and the results obtained from computational thermochemistry are in close agreement. Physics and Astronomy Department

  1. Quarkonium suppression: Gluonic dissociation vs. colour screening

    Indian Academy of Sciences (India)

    Binoy Krishna Patra; Dinesh Kumar Srivastava

    2003-05-01

    We evaluate the suppression of / production in an equilibrating quark gluon plasma for two competing mechanisms: Debye screening of colour interaction and dissociation due to energetic gluons. Results are obtained for S + S and Au + Au collisions at RHIC and LHC energies. At RHIC energies the gluonic dissociation of the charmonium is found to be equally important for both the systems while the screening of the interaction plays a significant role only for the larger systems. At LHC energies the Debye mechanism is found to dominate both the systems. While considering the suppression of directly produced $\\Upsilon$ at LHC energies, we find that only the gluonic dissociation mechanism comes into play for the initial conditions taken from the self screened parton cascade model in these studies.

  2. Enthalpies of mixing of liquid systems for lead free soldering: Al-Cu-Sn system

    Energy Technology Data Exchange (ETDEWEB)

    Flandorfer, Hans, E-mail: hans.flandorfer@univie.ac.at [University of Vienna, Department of Inorganic Chemistry/Materials Chemistry, Waehringer Str. 42, A-1090 Wien (Austria); Rechchach, Meryem; Elmahfoudi, A. [University of Vienna, Department of Inorganic Chemistry/Materials Chemistry, Waehringer Str. 42, A-1090 Wien (Austria); Faculte des Sciences, Universite Mohammed V, Laboratoire de Chimie Physique Generale, Av. Ibn Batouta, B.P. 1014, Rabat (Morocco); Bencze, Laszlo [Eoetvoes Lorand University, Dept. of Physical Chemistry, Pazmany Peter setany 1/A, H-1117 Budapest (Hungary); Popovic, Arkadij [Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana (Slovenia); Ipser, Herbert [University of Vienna, Department of Inorganic Chemistry/Materials Chemistry, Waehringer Str. 42, A-1090 Wien (Austria)

    2011-11-15

    Highlights: > First paper providing enthalpy of mixing determined by calorimetry for Al-Cu-Sn. > . > Comparative discussion of values derived from KEMS data published before. > Enthalpy of mixing at 1000 {sup o}C described for the entire ternary system Al-Cu-Sn. > New experimental enthalpy of mixing values for the binary Al-Cu system. - Abstract: The present work refers to high-temperature drop calorimetric measurements on liquid Al-Cu, Al-Sn, and Al-Cu-Sn alloys. The binary systems have been investigated at 973 K, up to 40 at.% Cu in case of Al-Cu, and over the entire concentrational range in case of Al-Sn. Measurements in the ternary Al-Cu-Sn system were performed along the following cross-sections: x{sub Al}/x{sub Cu} = 1:1, x{sub Al}/x{sub Sn} = 1:1, x{sub Cu}/x{sub Sn} = 7:3, x{sub Cu}/x{sub Sn} = 1:1, and x{sub Cu}/x{sub Sn} = 3:7 at 1273 K. Experimental data were used to find ternary interaction parameters by applying the Redlich-Kister-Muggianu model for substitutional solutions, and a full set of parameters describing the concentration dependence of the enthalpy of mixing was derived. From these, the isoenthalpy curves were constructed for 1273 K. The ternary system shows an exothermic enthalpy minimum of approx. -18,000 J/mol in the Al-Cu binary and a maximum of approx. 4000 J/mol in the Al-Sn binary system. The Al-Cu-Sn system is characterized by considerable repulsive ternary interactions as shown by the positive ternary interaction parameters.

  3. Preliminary Results from Electric Arc Furnace Off-Gas Enthalpy Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Nimbalkar, Sachin U [ORNL; Thekdi, Arvind [E3M Inc; Keiser, James R [ORNL; Storey, John Morse [ORNL

    2015-01-01

    This article describes electric arc furnace (EAF) off-gas enthalpy models developed at Oak Ridge National Laboratory (ORNL) to calculate overall heat availability (sensible and chemical enthalpy) and recoverable heat values (steam or power generation potential) for existing EAF operations and to test ORNL s new EAF waste heat recovery (WHR) concepts. ORNL s new EAF WHR concepts are: Regenerative Drop-out Box System and Fluidized Bed System. The two EAF off-gas enthalpy models described in this paper are: 1.Overall Waste Heat Recovery Model that calculates total heat availability in off-gases of existing EAF operations 2.Regenerative Drop-out Box System Model in which hot EAF off-gases alternately pass through one of two refractory heat sinks that store heat and then transfer it to another gaseous medium These models calculate the sensible and chemical enthalpy of EAF off-gases based on the off-gas chemical composition, temperature, and mass flow rate during tap to tap time, and variations in those parameters in terms of actual values over time. The models provide heat transfer analysis for the aforementioned concepts to confirm the overall system and major component sizing (preliminary) to assess the practicality of the systems. Real-time EAF off-gas composition (e.g., CO, CO2, H2, and H2O), volume flow, and temperature data from one EAF operation was used to test the validity and accuracy of the modeling work. The EAF off-gas data was used to calculate the sensible and chemical enthalpy of the EAF off-gases to generate steam and power. The article provides detailed results from the modeling work that are important to the success of ORNL s EAF WHR project. The EAF WHR project aims to develop and test new concepts and materials that allow cost-effective recovery of sensible and chemical heat from high-temperature gases discharged from EAFs.

  4. DFT study of hydrogen-bonded dimers and tetramer of glyoxilic acid oxime

    International Nuclear Information System (INIS)

    DFT study of hydrogen-bonded dimers and tetramer of glyoxilic acid oxime (GAO) has been performed at B3LYP/6-31G* and B3LYP/6-31++G** levels of the theory. The N...H---O and O...H---O hydrogen bondings in the self-assembling structures studied have been estimated from intermolecular distances, enthalpy of stabilization, hydrogen-bonding energies and AIM electron density at the hydrogen bond critical points. The calculated hydrogen-bonding energies of various GAO dimers suggested a cooperative interaction in the cyclic dimers and tetramer. The comparative study of chain aggregate with both head-to-head and tail-to-tail bondings and chain aggregate only with head-to-tail bondings, showed that the latter is enthalpically preferred in agreement with the crystal structure of GAO. Harmonic frequencies for the monomer, five dimers and tetramer have been calculated and discussed as to the changes in the most sensitive to the complexation vibrations and as to the strengths of the O...H---O and N...H---O hydrogen bondings. Vibrational analysis at B3LYP/6-31G* level confirmed the suggestion for a cooperativity in the cyclic H-bonded complexes. Natural population analysis was performed to predict electrostatic interactions in the cyclic H-bonded complexes. The π-delocalization was estimated on the basis of the calculated AIM ellipticity

  5. Weak bond screening system

    Science.gov (United States)

    Chuang, S. Y.; Chang, F. H.; Bell, J. R.

    Consideration is given to the development of a weak bond screening system which is based on the utilization of a high power ultrasonic (HPU) technique. The instrumentation of the prototype bond strength screening system is described, and the adhesively bonded specimens used in the system developmental effort are detailed. Test results obtained from these specimens are presented in terms of bond strength and level of high power ultrasound irradiation. The following observations were made: (1) for Al/Al specimens, 2.6 sec of HPU irradiation will screen weak bond conditions due to improper preparation of bonding surfaces; (2) for composite/composite specimens, 2.0 sec of HPU irradiation will disrupt weak bonds due to under-cured conditions; (3) for Al honeycomb core with composite skin structure, 3.5 sec of HPU irradiation will disrupt weak bonds due to bad adhesive or oils contamination of bonding surfaces; and (4) for Nomex honeycomb with Al skin structure, 1.3 sec of HPU irradiation will disrupt weak bonds due to bad adhesive.

  6. Performance of a Nonempirical Density Functional on Molecules and Hydrogen-Bonded Complexes

    OpenAIRE

    Mo, Yuxiang; Tian, Guocai; Car, Roberto; Viktor N. Staroverov; Scuseria, Gustavo E.; Tao, Jianmin

    2016-01-01

    Recently, Tao and Mo (TM) derived a new meta-generalized gradient approximation based on a model exchange hole. In this work, the performance of this functional is assessed on standard test sets, using the 6-311++G(3df,3pd) basis set. These test sets include 223 G3/99 enthalpies of formation, 58 electron affinities, 8 proton affinities, 96 bond lengths, 82 harmonic vibrational frequencies, and 10 hydrogen-bonded molecular complexes. Our calculations show that the TM functional can achieve rem...

  7. Carbon monoxide dissociative attachment and resonant dissociation by electron-impact

    Science.gov (United States)

    Laporta, V.; Tennyson, J.; Celiberto, R.

    2016-02-01

    Low-energy dissociative electron attachment and resonant electron impact dissociation of CO molecule are considered. Ro-vibrationally resolved cross sections and rate coefficients for both the processes are calculated using an ab-initio model based on the low-lying \\text{X}{{}2}\\Pi resonance of CO-. Final results show that the cross sections increases very rapidly as a function of the ro-vibrational level; these cross sections should be useful for understanding kinetic dissociation of CO in strongly non-equilibrium plasmas.

  8. Protonolysis of Dialkyl- and Alkylarylplatinum(II) Complexes and Geometrical Isomerization of the Derived Monoorgano-Solvento Complexes: Clear-Cut Examples of Associative and Dissociative Pathways in Platinum(II) Chemistry.

    Science.gov (United States)

    Romeo, Raffaello; Plutino, Maria Rosaria; Elding, Lars I.

    1997-12-01

    Protonolysis of the complexes cis-[PtR(2)(PEt(3))(2)] (R = Me, Et, Pr(n)(), Bu(n)(), CH(2)C(Me)(3), CH(2)Si(Me)(3)) and cis-[Pt(R)(R')(PEt(3))(2)] (R = Ph, 2-MeC(6)H(4), 2,4,6-Me(3)C(6)H(2); R' = Me) in methanol selectively cleaves one alkyl group, yielding cis-[Pt(R)(PEt(3))(2)(MeOH)](+) and alkanes. The reactions occur as single-stage conversions from the substrate to the product. There is no evidence by UV and by low-temperature (1)H and (31)P NMR spectroscopy for the presence of significant amounts of Pt(II) or Pt(IV) intermediate species. Reactions are first order with respect to complex and proton concentrations and are strongly retarded by steric congestion at the Pt-C bond, varying from k(2) = (2.65 +/- 0.08) x 10(5) M(-)(1) s(-)(1) for R = R' = Et to k(2) = 9.80 +/- 0.44 M(-)(1)s(-)(1) for R = R'= CH(2)Si(Me)(3). Low enthalpies of activation and largely negative volumes of activation are associated with the process. The mechanism involves a rate-determining proton transfer either to the metal-carbon sigma bond (S(E)2 mechanism) or to the metal center (S(E)(oxidative) mechanism), followed by fast extrusion of the alkane and simultaneous blocking of the vacant coordination site by the solvent to generate cis-[Pt(R)(PEt(3))(2)(MeOH)](+) species. The subsequent slower process, cis to trans isomerization of cis-[Pt(R)(PEt(3))(2)(MeOH)](+), is characterized by high values of enthalpies of activation, positive entropies of activation, and largely positive volumes of activation. The reaction is shown to proceed through the dissociative loss of the weakly bonded molecule of solvent and the interconversion of two geometrically distinct T-shaped 14-electron 3-coordinate intermediates. The presence of beta-hydrogens on the residual alkyl chain produces a great acceleration of the rate (R = Me, k(i) = 0.0026 s(-)(1); R = Et, k(i) = 44.9 s(-)(1)) as a consequence of the stabilization of the 3-coordinate [Pt(R)(PEt(3))(2)](+) transition state through an incipient agostic

  9. Spectroscopic evidence for the partial dissociation of H2O on ZnO(1010).

    Science.gov (United States)

    Wang, Y; Muhler, M; Wöll, Ch

    2006-04-01

    The interaction of water with the non-polar ZnO(1010) surface has been studied by high resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). Adsorption of water at room temperature leads to the partial dissociation of water molecules giving rise to a well defined (2x1) superstructure. This observation was confirmed by the HREELS data which show the water-induced O-H stretching modes at 396 and 460 meV (3193 and 3709 cm-1) as well as the peak at 456 meV (3677 cm-1) arising from the OH species. The large red shift of the loss at 396 meV indicates unusually strong hydrogen bonding interactions of water to both neighbouring adsorbate molecules and the surface O atoms which are responsible for the partial dissociation of water molecules on the perfect ZnO(1010) surface.

  10. Ionization and Dissociation of Nitrosyl Chloride Molecule in the Intense Femtosecond Laser Field

    Institute of Scientific and Technical Information of China (English)

    YAO, Li; GE, Mao-Fa; WANG, Dian-Xun; WU, Cheng-Yin; XU, Nan; GONG, Qi-Huang

    2006-01-01

    Ionization and dissociation of nitrosyl chloride ClNO were studied using femtosecond laser mass spectra technique. Strong fragmental ions NO+and Cl+were observed with the laser intensity varied from 3.2 × 1014 to 2.5 ×1015 W/cm2. These fragmental ions were attributed to the direct dissociation of the parent ions. Electronic structure calculations were also carried out with Hartree-Fock, density functional and correlated levels of theory to understand the possible fragmentation pathways. The very low N-Cl bond energy in the parent ion of nitrosyl chloride is a clear reason for the absence of ClNO+ and ClN+ ion peaks from the femtosecond laser mass spectrum.

  11. Density function theory study of the adsorption and dissociation of carbon monoxide on tungsten nanoparticles.

    Science.gov (United States)

    Weng, Meng-Hsiung; Ju, Shin-Pon; Chen, Hsin-Tsung; Chen, Hui-Lung; Lu, Jian-Ming; Lin, Ken-Huang; Lin, Jenn-Sen; Hsieh, Jin-Yuan; Yang, Hsi-Wen

    2013-02-01

    The adsorption and dissociation properties of carbon monoxide (CO) molecule on tungsten W(n) (n = 10-15) nanoparticles have been investigated by density-functional theory (DFT) calculations. The lowest-energy structures for W(n) (n = 10-15) nanoparticles are found by the basin-hopping method and big-bang method with the modified tight-binding many-body potential. We calculated the corresponding adsorption energies, C-O bond lengths and dissociation barriers for adsorption of CO on nanoparticles. The electronic properties of CO on nanoparticles are studied by the analysis of density of state and charge density. The characteristic of CO on W(n) nanoparticles are also compared with that of W bulk.

  12. Thermal dissociation of copper chalcogenides during melting

    Science.gov (United States)

    Pavlova, L. M.; Glazov, V. M.; Asryan, A. A.

    1998-01-01

    An attempt was undertaken to describe the mechanism of dissociation of copper chalcogenides during melting. Two-stage schemes of the dissociation of the Cu2BVI compounds (BVI is S, Se, or Te) were proposed. It was suggested that in the copper-sulfur and copper-selenium melts, Cu2BVI and CuBVI associates exist, whereas in the copper tellurium systems, Cu2Te and Cu5Te3 associates exist. The interpretation of available data on magnetic susceptibility was given in terms of suggested associates in Cu-Te alloys. Nous avons essayé de décrire le mécanisme de dissociation des chalcogénures de cuivre pendant la fusion. Nous proposons des schémas à deux étapes de dissociation pour les composés Cu2BVI (BVI est S, Se, ou Te). Nous suggérons l'existence dans le bain fondu cuivre-soufre et cuivre-sélénium des associés du type Cu2BVI et CuBVI et dans le système cuivre-tellure Cu2Te et Cu5Te3. L'interprétation des données disponibles de susceptibilité magnétique est réalisée en termes de formation d'associés dans les alliages Cu-Te.

  13. Nucleon-XcJ Dissociation Cross Sections

    Institute of Scientific and Technical Information of China (English)

    冯又层; 许晓明; 周代翠

    2002-01-01

    Nucleon-XcJ dissociation cross sections are calculated in a constituent interexchange model in which quark-quark potential is derived from the Buchmüller-Tye quark-anti-quark potential. These new cross sections for dominant reaction channels depend on the centre-of-mass energy of the nucleon and the charmonium.

  14. Visuomotor Dissociation in Cerebral Scaling of Size

    NARCIS (Netherlands)

    Potgieser, Adriaan R E; de Jong, Bauke M

    2016-01-01

    Estimating size and distance is crucial in effective visuomotor control. The concept of an internal coordinate system implies that visual and motor size parameters are scaled onto a common template. To dissociate perceptual and motor components in such scaling, we performed an fMRI experiment in whi

  15. Coherent dissociation of relativistic 12N nuclei

    International Nuclear Information System (INIS)

    The dissociation of relativistic 12N nuclei having a momentum of 2 GeV/c per nucleon and undergoing the most peripheral interactions in a track emulsion is studied. The picture of charged topology of product ensembles of relativistic fragments and special features of their angular distributions are presented

  16. From dissociated hegemony towards embedded hegemony

    NARCIS (Netherlands)

    Gaay Fortman, B. de; Dhanrajgir, Nikhil

    2005-01-01

    An earlier paper by the second author, entitled ‘Bella Americana: Some Consequences for the International Community’ [1], dealt with the background and consequences of the American dissociation from the international legal and political order created after World War II. The current article examines

  17. 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.

  18. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  19. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  20. The Bond Market's q

    OpenAIRE

    Thomas Philippon

    2006-01-01

    I propose an implementation of the q-theory of investment using bond prices instead of equity prices. Credit risk makes corporate bond prices sensitive to future asset values, and q can be inferred from bond prices. The bond market's q performs much better than the usual measure in standard investment equations. With aggregate data, the fit is three times better, cash flows are driven out and the implied adjustment costs are reduced by more than an order of magnitude. The new measure also imp...

  1. Experimental Dissociation of Methane Hydrates Through Depressurization

    Science.gov (United States)

    Borgfeldt, T.; Flemings, P. B.; Meyer, D.; You, K.

    2015-12-01

    We dissociated methane hydrates by stepwise depressurization. The initial hydrates were formed by injecting gas into a cylindrical sample of brine-saturated, coarse-grained sand at hydrate-stable conditions with the intention of reaching three-phase equilibrium. The sample was initially at 1°C with a pore pressure of 1775 psi and a salinity of 7 wt. % NaBr. The depressurization setup consisted of one pump filled with tap water attached to the confining fluid port and a second pump attached to the inlet port where the methane was injected. Depressurization was conducted over sixteen hours at a constant temperature of 1°C. The pore pressure was stepwise reduced from 1775 psi to atmospheric pressure by pulling known volumes of gas from the sample. After each extraction, we recorded the instantaneous and equilibrium pore pressure. 0.503 moles of methane were removed from the sample. The pore pressure decreased smoothly and nonlinearly with the cumulative gas withdrawn from the sample. We interpret that hydrate began to dissociate immediately with depressurization, and it continued to dissociate when the pressure decreased below the three-phase pressure for 1°C and 0 wt. % salinity. Two breaks in slope in the pressure vs. mass extracted data are bounded by smooth, nonlinear curves with differing slopes on either side. We attribute the breaks to dissociation of three zones of hydrate concentration. We created a box model to simulate the experimental behavior. For a 10% initial gas saturation (estimated from the hydrate formation experiment and based on mass conservation), an initial hydrate saturation of 55% is required to match the total methane extracted from the sample. Future experiments will be conducted over a longer timespan while monitoring hydrate dissociation with CT imaging throughout the process.

  2. Use of an intense microwave laser to dissociate a diatomic molecule: Theoretical prediction of dissociation dynamics

    Indian Academy of Sciences (India)

    Amita Wadehra; B M Deb

    2012-01-01

    By employing an intense microwave laser of wavelength 116.65 m with intensities 1 × 1013 and 5 × 1018Wcm−2, respectively, the conclusion is reached theoretically and computationally that it is possible to dissociate the CO molecule, modelled as a Morse oscillator. It is predicted that for above-threshold dissociation (ATD), the molecule should absorb 1044 photons of the given wavelength in order to reach the lowest edge of the vibrational continuum. A consistent analysis of the predicted dissociation process is provided though the time-dependent probability density, dissociation probability, norm, potential function, HHG and ATD spectra, obtained by numerically solving the time-dependent vibrational Schödinger equation.

  3. Psychobiological characteristics of dissociative identity disorder : A symptom provocation study

    NARCIS (Netherlands)

    Reinders, A. A. T. Simone; Nijenhuis, Ellert R. S.; Quak, Jacqueline; Korf, Jakob; Haaksma, Jaap; Paans, Anne M. J.; Willemsen, Antoon T. M.; den Boer, Johan A.

    2006-01-01

    Background: Dissociative identity disorder (DID) patients function as two or more identities or dissociative identity states (DIS), categorized as 'neutral identity states' (NIS) and 'traumatic identity states' (TIS). NIS inhibit access to traumatic memories thereby enabling daily life functioning.

  4. Thermodynamics of hydrogen bonding of weak bases in alcohol solutions: Calorimetry of solution, IR-spectroscopy and vapor pressure analysis

    Science.gov (United States)

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

    2012-06-01

    The properties of solutes and their reactivity in aliphatic alcohols significantly depend on the formation of hydrogen bonds. In this work, calorimetric, FTIR-spectroscopic and gas chromatographic vapor pressure studies of hydrogen bonds of weak bases in solution of aliphatic alcohols were carried out. Enthalpies of solutions at infinite dilution of ketones, nitriles and acetates in methanol and octan-1-ol were measured. Obtained from the calorimetric data, the enthalpies of specific interaction of weak bases in aliphatic alcohols unexpectedly found to be positive. IR spectra of solutions of ketones in aliphatic alcohols at infinite dilution were measured at different temperatures. Enthalpies of specific interaction in studied systems obtained from the spectroscopic data confirmed the endothermic process and are in good agreement with calorimetric results. Gibbs energies and entropies of specific interaction of weak bases in aliphatic alcohols were determined. Obtained results show, that the hydrogen bonding process of weak bases in aliphatic alcohols differs substantially from the formation of complexes 1:1 ROH⋯B (B - weak proton acceptor) in aprotic media. The complicated process of hydrogen bonding of weak bases in aliphatic alcohols apparently is controlled by the entropy factor, because these values are above zero.

  5. What contributes to predicting change in the treatment of dissociation: initial levels of dissociation, PTSD, or overall distress?

    Science.gov (United States)

    Brand, Bethany L; Stadnik, Ryan

    2013-01-01

    Individuals with dissociative disorders (DDs) suffer from high levels of dissociation as well as posttraumatic stress disorder (PTSD) and general distress. No research has investigated how changes in dissociation relate to changes in other symptoms over the course of treatment in patients with DD. Using a prospective, naturalistic design, we collected reports of symptoms from a sample of therapists and their patients diagnosed with dissociative identity disorder or dissociative disorder not otherwise specified who participated in the Treatment Outcome of Patients with Dissociative Disorders study. The patients completed surveys at intake (Time 1) into the study and at 30-month follow-up (Time 4). We found that dissociative symptoms, including amnesia, depersonalization/derealization, and absorption, at the initial assessment of the study ("initial") were related to initial levels of PTSD and general distress and that changes in dissociative symptoms were related to changes in PTSD and general distress. Initial dissociation was a significant predictor of change in dissociation at 30 months when we controlled for length of time for follow-up, length of time practicing therapy, and length of time treating dissociative patients. Our results suggest that a reduction in dissociative symptoms in DD patients is associated with reductions in the overall severity of dissociative, posttraumatic stress, and distress symptoms. PMID:23627481

  6. Effect of Water Content in N-Methylmorpholine N-Oxide/Cellulose Solutions on Thermodynamics, Structure, and Hydrogen Bonding.

    Science.gov (United States)

    Rabideau, Brooks D; Ismail, Ahmed E

    2015-12-01

    Native crystalline cellulose is notoriously difficult to dissolve due to its dense hydrogen bond network between chains and weaker hydrophobic forces between cellulose sheets. N-Methylmorpholine N-oxide (NMMO), the solvent behind the Lyocell process, is one of the most successful commercial solvents for the nonderivatized dissolution of cellulose. In this process, water plays a very important role. Its presence at low concentrations allows NMMO to dissolve substantial amounts of cellulose, while at much higher concentrations it precipitates the crystalline fibers. Using all-atom molecular dynamics, we study the thermodynamic and structural properties of ternary solutions of cellulose, NMMO, and water. Using the two-phase thermodynamic method to calculate solvent entropy, we estimate the free energy of dissolution of cellulose as a function of the water concentration and find a transition of spontaneity that is in excellent agreement with experiment. In pure water, we find that cellulose dissolution is nonspontaneous, a result that is due entirely to strong decreases in water entropy. Although the combined effect of enthalpy on dissolution in water is negligible, we observe a net loss of hydrogen bonds, resulting in a change in hydrogen bond energy that opposes dissolution. At lower water concentrations, cellulose dissolution is spontaneous and largely driven by decreases in enthalpy, with solvent entropy playing only a very minor role. When searching for the root causes of this enthalpy decrease, a complex picture emerges in which not one but many different factors contribute to NMMO's good solvent behavior. The reduction in enthalpy is led by the formation of strong hydrogen bonds between cellulose and NMMO's N-oxide, intensified through van der Waals interactions between NMMO's nonpolar body and the nonpolar surfaces of cellulose and unhindered by water at low concentrations due to the formation of efficient hydrogen bonds between water and cellulose.

  7. Direct non-dissociative and dissociative ionization of CO2 by positron impact

    International Nuclear Information System (INIS)

    Detailed measurements of the cross-section for non-dissociative ionization of CO2 are presented and compared with available experimental and theoretical results. An excellent agreement is found with the energy dependence of another experimental determination; however, uncertainties exist over the magnitude. Also presented are the preliminary results for the combined cross-section for direct dissociative ionization of CO2 into O+ or C+

  8. Near-exact enthalpy-entropy compensation governs the thermal unfolding of protonation states of oxidized cytochrome c.

    Science.gov (United States)

    Soffer, Jonathan B; Schweitzer-Stenner, Reinhard

    2014-10-01

    This paper reports the first quantitative analysis of the thermal transitions of all protonation states of oxidized horse heart cytochrome c at low anion concentration. Changes of secondary and tertiary structure were probed by ultraviolet (UV) as well as visible circular dichroism and absorption spectroscopy, respectively. The temperature dependence of spectra were recorded at pH values assignable to a set of different protonation states which encompass the canonical Theorell-Åkesson states and the recently discovered III* state. Our experimental data suggest a two-step process of thermal unfolding for all protonation states. The respective thermodynamic parameters were obtained from a global analysis of the temperature dependence of corresponding visible circular dichroism (CD) and absorption spectra. The results of this analysis revealed a statistically significant enthalpy-entropy compensation with different apparent compensation temperatures for the two consecutive thermal transitions (319 and 357 K). This reflects the narrow distribution of the respective folding temperatures. UVCD spectra suggest that even the thermal transitions of protonation states occupied at acidic and alkaline pH cause only a very modest unfolding of the protein's helical structure. Our data indicate the protonation-induced unfolding at room temperatures predominantly affects the Ω-loops of the protein. The two thermal transitions involve changes of two foldons, i.e. the unfolding of two short β-strand segments (associated with the yellow foldon) followed by the unfolding of the 60' helix (green foldon) that connects the two Ω-loops of the protein. Apparently, intra-backbone hydrogen bonding is strong enough to mostly protect the terminal N- and C-helices from unfolding even at rather extreme conditions.

  9. Wild-type and molten globular chorismate mutase achieve comparable catalytic rates using very different enthalpy/entropy compensations

    Institute of Scientific and Technical Information of China (English)

    HU Hao

    2014-01-01

    The origin of the catalytic power of enzymes with a meta-stable native state,e.g.molten globular state,is an unsolved challenging issue in biochemistry.To help understand the possible differences between this special class of enzymes and the typical ones,we report here computer simulations of the catalysis of both the well-folded wild-type and the molten globular mutant of chorismate mutase.Using the ab initio quantum mechanical/molecular mechanical minimum free-energy path method,we determined the height of reaction barriers that are in good agreement with experimental measurements.Enzyme-substrate interactions were analyzed in detail to identify factors contributing to catalysis.Computed angular order parameters of backbone N–H bonds and side-chain methyl groups suggested site-specific,non-uniform rigidity changes of the enzymes during catalysis.The change of conformational entropy from the ground state to the transition state revealed distinctly contrasting entropy/enthalpy compensations in the dimeric wild-type enzyme and its molten globular monomeric variant.A unique catalytic strategy was suggested for enzymes that are natively molten globules:some may possess large conformational flexibility to provide strong electrostatic interactions to stabilize the transition state of the substrate and compensate for the entropy loss in the transition state.The equilibrium conformational dynamics in the reactant state were analyzed to quantify their contributions to the structural transitions enzymes needed to reach the transition states.The results suggest that large-scale conformational dynamics make important catalytic contributions to sampling conformational regions in favor of binding the transition state of substrate.

  10. Structure and Reactivity of Homocysteine Radical Cation in the Gas Phase Studied by Ion-Molecule Reactions and Infrared Multiple Photon Dissociation

    NARCIS (Netherlands)

    Osburn, S.; Burgie, T.; G. Berden,; Oomens, J.; O' Hair, R. A. J.; Ryzhov, V.

    2013-01-01

    The reactivity of the cysteine (Cys) and homocysteine (Hcy) radical cation was studied using ion molecule reactions. The radical cations were generated via collision-induced dissociation (CID) of their S-nitrosylated precursors. Cleavage of the S-NO bond led to the formation of the radical initially

  11. Does phasic trauma treatment make patients with dissociative identity disorder treatment more dissociative?

    Science.gov (United States)

    Brand, Bethany; Loewenstein, Richard J

    2014-01-01

    Proponents of the iatrogenic model of the etiology of dissociative identity disorder (DID) have expressed concern that treatment focused on direct engagement and interaction with dissociated self-states harms DID patients. However, empirical data have shown that this type of DID treatment is beneficial. Analyzing data from the prospective Treatment of Patients With Dissociative Disorders (TOP DD) Study, we test empirically whether DID treatment is associated with clinically adverse manifestations of dissociated self-states: acting so differently that one feels like different people, hearing voices, and dissociative amnesia. We show that, over the course of the study, there were significant decreases in feeling like different people and hearing voices. These results indicate that this form of DID treatment does not lead to symptomatic worsening in these dimensions, as predicted by the iatrogenic model. Indeed, treatment provided by TOP DD therapists reduced, rather than increased, the extent to which patients experienced manifestations of pathological dissociation. Because severe symptomatology and impairment are associated with DID, iatrogenic harm may come from depriving DID patients of treatment that targets DID symptomatology. PMID:24377972

  12. Accurate Computed Enthalpies of Spin Crossover in Iron and Cobalt Complexes

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta; Cirera, J

    2009-01-01

    Despite their importance in many chemical processes, the relative energies of spin states of transition metal complexes have so far been haunted by large computational errors. By the use of six functionals, B3LYP, BP86, TPSS, TPSSh, M06L, and M06L, this work studies nine complexes (seven with iron...... and two with cobalt) for which experimental enthalpies of spin crossover are available. It is shown that such enthalpies can be used as quantitative benchmarks of a functional's ability to balance electron correlation in both the involved states. TPSSh achieves an unprecedented mean absolute error...... of similar to 11 kJ/mol in spin transition energies, with the local functional M06L a distant second (25 kJ/mol). Other tested functionals give mean absolute errors of 40 kJ/mol or more. This work confirms earlier suggestions that 10% exact exchange is near-optimal for describing the electron correlation...

  13. The influence of facies heterogeneity on the doublet performance in low-enthalpy geothermal sedimentary reservoirs

    DEFF Research Database (Denmark)

    Crooijmans, R. A.; Willems, C. J L; Nick, Hamid;

    2016-01-01

    A three-dimensional model is used to study the influence of facies heterogeneity on energy production under different operational conditions of low-enthalpy geothermal doublet systems. Process-based facies modelling is utilised for the Nieuwerkerk sedimentary formation in the West Netherlands Basin...... and the energy recovery rate for different discharge rates and the production temperature (Tmin) above which the doublet is working. With respect to the results, we propose a design model to estimate the life time and energy recovery rate of the geothermal doublet. The life time is estimated as a function of N...... errors in predicting the life time of low-enthalpy geothermal systems for N/G values below 70%....

  14. The influence of facies heterogeneity on the doublet performance in low-enthalpy geothermal sedimentary reservoirs

    DEFF Research Database (Denmark)

    Crooijmans, R. A.; Willems, C. J L; Nick, Hamid;

    2016-01-01

    A three-dimensional model is used to study the influence of facies heterogeneity on energy production under different operational conditions of low-enthalpy geothermal doublet systems. Process-based facies modelling is utilised for the Nieuwerkerk sedimentary formation in the West Netherlands Basin...... life time and the energy recovery rate for different discharge rates and the production temperature (Tmin) above which the doublet is working. With respect to the results, we propose a design model to estimate the life time and energy recovery rate of the geothermal doublet. The life time is estimated...... lead to significant errors in predicting the life time of low-enthalpy geothermal systems for N/G values below 70%....

  15. Evaluation of zeotropic refrigerants based on nonlinear relationship between temperature and enthalpy

    Institute of Scientific and Technical Information of China (English)

    ZHAO; Li

    2006-01-01

    In order to evaluate cycling characters of zeotropic refrigerants in air-conditioning operation, and to reveal distribution rules of temperature difference between refrigerants and heat transfer fluids in condenser and evaporator, theoretical researches were carried out based on nonlinear relationship between temperature and enthalpy in period of refrigerants' phase change. Firstly, a phase changing model of refrigerants was built, and refrigerants state parameters were decided in the air-conditioning operation.Secondly, the state equation of refrigerants was applied for computing relationship between temperature and enthalpy, else based on some suppositions, temperature differences between 15 sorts of refrigerants and heat-transfer fluids were gotten too. Through concluding those temperature differences changing in condenser and evaporator, some rules were found. Lastly, after calculating and comparing the additive exergy loss among15 sorts of refrigerants, which resulted from the changing of temperature difference, their cycling characters evaluation were presented.

  16. Enthalpy-entropy correlations as chemical guides to unravel self-assembly processes.

    Science.gov (United States)

    Piguet, Claude

    2011-08-28

    Intermolecular connections play a crucial role in biology (recognition, signalling, binding), in physics (material cohesion) and in chemistry ((supra)molecular engineering). While a phenomenological thermodynamic free-energy approach for modelling self-assemblies is now at hand, a more satisfying description based on the chemically-intuitive enthalpic and entropic contributions remains elusive. On the other hand, the innumerable reports of empirical enthalpy/entropy correlations characterizing intermolecular interactions justify a questioning about the emergence and exploitation of an apparent 'fourth law of thermodynamics', which could provide a simple manipulation of intermolecular binding processes. This tutorial Perspective aims at highlighting the current level of non-quantum rationalization of enthalpy-entropy correlations and their chemical consequences on the tuning and on the programming of intermolecular interactions in pure materials, and in diluted solutions. PMID:21629958

  17. Down-Hole Heat Exchangers: Modelling of a Low-Enthalpy Geothermal System for District Heating

    Directory of Open Access Journals (Sweden)

    M. Carlini

    2012-01-01

    Full Text Available In order to face the growing energy demands, renewable energy sources can provide an alternative to fossil fuels. Thus, low-enthalpy geothermal plants may play a fundamental role in those areas—such as the Province of Viterbo—where shallow groundwater basins occur and conventional geothermal plants cannot be developed. This may lead to being fuelled by locally available sources. The aim of the present paper is to exploit the heat coming from a low-enthalpy geothermal system. The experimental plant consists in a down-hole heat exchanger for civil purposes and can supply thermal needs by district heating. An implementation in MATLAB environment is provided in order to develop a mathematical model. As a consequence, the amount of withdrawable heat can be successfully calculated.

  18. 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.

  19. Enthalpy Distributions of Arc Jet Flow Based on Measured Laser Induced Fluorescence, Heat Flux and Stagnation Pressure Distributions

    Science.gov (United States)

    Suess, Leonard E.; Milhoan, James D.; Oelke, Lance; Godfrey, Dennis; Larin, Maksim Y.; Scott, Carl D.; Grinstead, Jay H.; DelPapa, Steven

    2011-01-01

    The centerline total enthalpy of arc jet flow is determined using laser induced fluorescence of oxygen and nitrogen atoms. Each component of the energy, kinetic, thermal, and chemical can be determined from LIF measurements. Additionally, enthalpy distributions are inferred from heat flux and pressure probe distribution measurements using an engineering formula. Average enthalpies are determined by integration over the radius of the jet flow, assuming constant mass flux and a mass flux distribution estimated from computational fluid dynamics calculations at similar arc jet conditions. The trends show favorable agreement, but there is an uncertainty that relates to the multiple individual measurements and assumptions inherent in LIF measurements.

  20. Development, Reliability, and Validity of a Child Dissociation Scale.

    Science.gov (United States)

    Putnam, Frank W.; And Others

    1993-01-01

    Evaluation of the Child Dissociative Checklist found it to be a reliable and valid observer report measure of dissociation in children, including sexually abused girls and children with dissociative disorder and with multiple personality disorder. The checklist, which is appended, is intended as a clinical screening instrument and research measure…

  1. Effect of cooling rate on enthalpy and volume relaxation of polystirene

    OpenAIRE

    Slobodian, Petr; Rychwalski, Rodney W.; Kubát, Josef; Hadač, J.; Sáha, Petr; Emri, Igor; Riha, Pavel

    2015-01-01

    This paper presents the results of measurements of physical aging on polystyrene with a narrow molecular weight distribution (Mw/Mn = 1.03). The evolution of the aging process was followed by recording the relaxed enthalpy and the accompanying decrease in volume, using differential scanning calorimetry and mercury-in-glass dilatometry, respectively. The measurements were carried out after cooling the sample at constant rate to the aging temperature. The cooling rate varied between 0.0037 and ...

  2. Outlook on principles for designing integrated and cascade use of low enthalpy geothermal energy in Albania

    International Nuclear Information System (INIS)

    In the countries of Western Europe, USA and Japan, the technologies of a new generation evolved to exploit high and low enthalpy geothermal sources and mineral waters. There are great experiences for modern complex exploitation of these resources, which increase natural wealth values, in European Community Countries. In Albania, rich in geothermal resources of low enthalpy and mineral waters, similar new technologies have been either partly developed or remain still untouched. Modern complex exploitation is very rare phenomena. Large numbers of geothermal energy of high and low enthalpy resources, a lot of mineral water sources and some CO2 gas reservoirs represent the base for successfully application of modern technologies in Albania, to achieve economic effectively and success of complex exploitation. Actuality, there are many geothermal, hydrogeological, hydrochemical, biological and medical investigations and studies of thermal and mineral water resources carried out in Albania. Generally, these investigations and studies are separated each from the other. Their information and data will serve for studies and evaluations in Albania regional scale. These studies and evaluations are necessary to well know in regional plane the thermal and mineral water resources potential and geothermal market of the Albania. According to results of these new studies, the evaluation for the perspective level of the best areas in country will be necessary. After the evaluation is possible to start investments in these areas. These investments will be profitable in a short period of time. Integrated and cascade use of geothermal energy of low enthalpy it is important condition for profitable investment. In Albania, there are several geothermal energy sources that can be used. Such geothermal energy sources are natural thermal water springs and deep wells with a temperature of up to 65,5oC. Deep abandoned oil wells can be used as 'Vertical Earth Heat Probe'. The integrated and

  3. 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.

  4. 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

    2015-04-30

    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 a 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.

  5. 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....

  6. Abnormal three-steplike sub-Tg enthalpy relaxation pattern in hyperquenched metallic glasses

    DEFF Research Database (Denmark)

    Hu, Lina; Yue, Yuanzheng

    the dependence of thermal history on the sub-Tg enthalpy relaxation pattern (ERP) of Cu46Zr46Al8 glasses, as well as La55Al25Ni20 for comparisons. It has been found that the presence of the three-steplike sub-Tg ERP of Cu46Zr46Al8 closely relates to the fictive temperature Tf, whereas no such anomaly is observed...

  7. The free energy, enthalpy and entropy of native and of partially denatured closed circular DNA.

    Science.gov (United States)

    Bauer, W R; Benham, C J

    1993-12-20

    We have used gel electrophoresis to measure the progress of local denaturation in closed circular pBR322 DNA as a function of temperature and linking deficiency, delta Lk. Local denaturation is closely coupled to supercoiling in closed DNA, requiring statistical mechanical methods for analysis. We have applied these methods to the experimental data to evaluate the free energies for three associated molecular processes. These processes are changes in the residual linking deficiency, delta Lkr, initiation of local denaturation, and twisting of denatured strands about one another. Our results confirm the quadratic dependence of the supercoiling free energy upon delta Lk, with a free energy coefficient of 740/N kcal/mol at 37 degrees C, where N is the number of base-pairs. The free energy of initiation of denaturation is 10.2(+/- 0.7) kcal/mol. The free energy of interstrand twisting of denatured regions varies with the square of the twist density, with proportionality coefficient C tau = 1.62 (+/- 0.11) kcal/rad2 at 37 degrees C. We have also calculated the entropy and enthalpy of these three processes, using the temperature dependence of the respective free energies. We find that both the entropy and the enthalpy of supercoiling are positive and vary quadratically with delta Lk. The free energy of initiation of denaturation is independent of temperature, hence arises primarily from a change in enthalpy. The entropy and enthalpy of interstrand twisting of denatured regions are both positive, and the twisting force constant decreases with temperature. These results differ considerably from expectations based solely upon considerations of chain configuration in vacuo, indicating the importance of solvent-dependent factors in determining the structure of closed circular DNA.

  8. Retrogradation enthalpy does not always reflect the retrogradation behavior of gelatinized starch

    OpenAIRE

    Shujun Wang; Caili Li; Xiu Zhang; Les Copeland; Shuo Wang

    2016-01-01

    Starch retrogradation is a term used to define the process in which gelatinized starch undergoes a disorder-to-order transition. A thorough understanding of starch retrogradation behavior plays an important role in maintaining the quality of starchy foods during storage. By means of DSC, we have demonstrated for the first time that at low water contents, the enthalpy change of retrograded starch is higher than that of native starch. In terms of FTIR and Raman spectroscopic results, we showed ...

  9. Investigating ultra high-enthalpy geothermal systems: a collaborative initiative to promote scientific opportunities

    Science.gov (United States)

    Elders, W. A.; Nielson, D.; Schiffman, P.; Schriener, A., Jr.

    2014-12-01

    Scientists, engineers, and policy makers gathered at a workshop in the San Bernardino Mountains of southern California in October 2013 to discuss the science and technology involved in developing high-enthalpy geothermal fields. A typical high-enthalpy geothermal well between 2000 and 3000 m deep produces a mixture of hot water and steam at 200-300 °C that can be used to generate about 5-10 MWe of electric power. The theme of the workshop was to explore the feasibility and economic potential of increasing the power output of geothermal wells by an order of magnitude by drilling deeper to reach much higher pressures and temperatures. Development of higher enthalpy geothermal systems for power production has obvious advantages; specifically higher temperatures yield higher power outputs per well so that fewer wells are needed, leading to smaller environmental footprints for a given size of power plant. Plans for resource assessment and drilling in such higher enthalpy areas are already underway in Iceland, New Zealand, and Japan. There is considerable potential for similar developments in other countries that already have a large production of electricity from geothermal steam, such as Mexico, the Philippines, Indonesia, Italy, and the USA. However drilling deeper involves technical and economic challenges. One approach to mitigating the cost issue is to form a consortium of industry, government and academia to share the costs and broaden the scope of investigation. An excellent example of such collaboration is the Iceland Deep Drilling Project (IDDP), which is investigating the economic feasibility of producing electricity from supercritical geothermal reservoirs, and this approach could serve as model for future developments elsewhere. A planning committee was formed to explore creating a similar initiative in the USA.

  10. Calorimetric and Computational Study of Enthalpy of Formation of Diperoxide of Cyclohexanone

    Directory of Open Access Journals (Sweden)

    Alicia H. Jubert

    2007-07-01

    Full Text Available A thermochemical rather simple experimental technique is applied to determinethe enthalpy of formation of Diperoxide of ciclohexanone. The study is complemented withsuitable theoretical calculations at the semiempirical and ab initio levels. A particularsatisfactory agreement between both ways is found for the ab initio calculation at the 6-311G basis This set level. Some possible extensions of the present procedure are pointedout.

  11. Methanol wetting enthalpy on few-layer graphene decorated hierarchical carbon foam for cooling applications

    Energy Technology Data Exchange (ETDEWEB)

    Paul, R., E-mail: paul24@purdue.edu [Birck Nanotechnolgy Center, Purdue University, West Lafayette, IN 47907 (United States); Zemlyanov, D. [Birck Nanotechnolgy Center, Purdue University, West Lafayette, IN 47907 (United States); Voevodin, A.A.; Roy, A.K. [Materials and Manufacturing Directorate, Air Force Research Laboratory, WPAFB, OH 45433 (United States); Fisher, T.S. [Birck Nanotechnolgy Center, Purdue University, West Lafayette, IN 47907 (United States); Department of Mechanical Engineering, Purdue University, West Lafayette, IN 47907 (United States)

    2014-12-01

    Vertical few-layer thick graphene petals are grown on macro-porous carbon foam surfaces having an intrinsic open porosity of 75%. This provides a hierarchical porous structure with a potential for surface adsorption/desorption or wetting/dewetting based thermal energy storage applications. Carbon foams have a combined advantage of large surface area and high thermal conductivity critical for thermal energy storage, but they are prone to oxidation and exhibit low adsorption enthalpies for lightweight hydrocarbons. Here we report graphene petal decoration of carbon foam surfaces and subsequent chemical modification through boron nitride incorporation in hexagonal carbon planes of both carbon foams and graphene petals. This chemically reactive hierarchical structure is characterized with FESEM, Raman, XRD, and XPS measurements. Methanol wetting enthalpy of this three-dimensional hierarchical material was measured with a solution calorimeter, and had shown a six fold increase (from 78 to 522 J/g of foam) as compared to the carbon foam prior to the surface modification. Influences of petal decoration on the surface morphology of carbon foam, BN chemical modification, structure and stoichiometry of the hierarchical material surface, and methanol wetting enthalpy improvement are discussed in detail. The applicability of this hierarchical porous material for thermal energy applications is established. - Highlights: • 500 nm thick few layer graphene petals decoration vertically on macroporous carbon foam surface. • Microwave heating assisted chemical treatment for boron-nitride modification. • Defective petals edges due to boron nitride domain formation. • 20 at. % boron and nitrogen incorporation. • Six fold increase in methanol wetting enthalpy on boron-nitride modification.

  12. Lifetime of the P-selectin-carbohydrate bond and its response to tensile force in hydrodynamic flow

    Science.gov (United States)

    Alon, Ronen; Hammer, Daniel A.; Springer, Timothy A.

    1995-04-01

    SELECTINS tether to the blood vessel wall leukocytes that are flowing in the bloodstream and support subsequent labile rolling interactions as the leukocytes are subjected to hydrodynamic drag forces1,2. To support this rolling, selectins have been proposed to have rapid bond association and dissociation rate constants, and special mechanical properties linking tensile forces and bond dissociation3-6. We have visualized transient tethering and release of neutrophils in hydrodynamic flow on lipid bilayers containing densities of P-selectin below those required to support rolling. We report here that transient tethers had first-order kinetics and other characteristics suggesting a unimolecular interaction between P-selectin and its glycoprotein ligand (PSGL-1). The unstressed dissociation constant (off rate) was 1 s-1. Hydrodynamic shear stresses of up to 1.1 dyn cm-2, corresponding to a force on the bond of up to HOpN, increased the off rate only modestly, to 3.5 s-1. The data was adequately matched by a proposed equation7 relating off rate to the exponential of tensile force on the bond and the bond interaction distance, and gave a bond interaction distance of 0.5Å. This distance is compatible with hydrogen and metal coordination bonds between P-selectin and PSGL-1. Fast on and off rates, together with the high tensile strength of the selectin bond, appear necessary to support rolling at physiological shear stresses.

  13. Rate coefficients for dissociative attachment and resonant electron-impact dissociation involving vibrationally excited O{sub 2} molecules

    Energy Technology Data Exchange (ETDEWEB)

    Laporta, V. [Istituto di Metodologie Inorganiche e dei Plasmi, CNR, Bari, Italy and Department of Physics and Astronomy, University College London, London WC1E 6BT (United Kingdom); Celiberto, R. [Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica, Politecnico di Bari, Italy and Istituto di Metodologie Inorganiche e dei Plasmi, CNR, Bari (Italy); Tennyson, J. [Department of Physics and Astronomy, University College London, London WC1E 6BT (United Kingdom)

    2014-12-09

    Rate coefficients for dissociative electron attachment and electron-impact dissociation processes, involving vibrationally excited molecular oxygen, are presented. Analytical fits of the calculated numerical data, useful in the applications, are also provided.

  14. Coupled valence bond theory

    NARCIS (Netherlands)

    Havenith, R.W.A.

    2005-01-01

    In this Letter, the formulation and implementation of a parallel response property code for non-orthogonal, valence bond wave-functions are described. Test calculations on benzene and cyclobutadiene show that the polarisability and magnetisability tensors obtained using valence bond theory are compa

  15. Bonded labour in Pakistan

    OpenAIRE

    Ercelawn, Aly; Nauman, Muhammad

    2001-01-01

    Examines the continuing prevalence of debt bondage in the 1990s despite the introduction of national legislation banning the practice. Makes recommendations to the Government and the international community for actions to be taken to eliminate bonded labour and provide rehabilitation for freed workers. Includes texts of Land Reforms Regulations, 1972, the Sindh Tenancy Act, 1950 and the Bonded Labour System (Abolition) Act, 1992.

  16. Hydrogen bonding in polyanilines

    Energy Technology Data Exchange (ETDEWEB)

    Bahceci, S. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Toppare, L. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Yurtsever, E. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey))

    1994-11-29

    Hydrogen bonding between poly(bisphenol A carbonate) (PC) and polyaniline (PAn) is analyzed using semi-empirical quantum methodology. Fully optimized AM1 molecular orbital calculations are reported for various aniline structures (monomer, dimer and trimer), the monomer of the PC and the hydrogen-bonded model of PAn-PC oligomer. ((orig.))

  17. The samurai bond market

    OpenAIRE

    Frank Packer; Elizabeth Reynolds

    1997-01-01

    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  18. Spatial variability of enthalpy in broiler house during the heating phase

    Directory of Open Access Journals (Sweden)

    Patrícia F. P. Ferraz

    2016-06-01

    Full Text Available ABSTRACT The thermal environment inside a broiler house has a great influence on animal welfare and productivity during the production phase. Enthalpy is a thermodynamic property that has been proposed to evaluate the internal broiler house environment, for being an indicator of the amount of energy contained in a mixture of water vapor and dry air. Therefore, this study aimed to characterize the spatial variability of enthalpy in a broiler house during the heating phase using geostatistics. The experiment was conducted in the spring season, in a commercial broiler house with heating system consisting of two furnaces that heat the air indirectly, in the first 14 days of the birds' life. It was possible to characterize enthalpy variability using geostatistical techniques, which allowed observing the spatial dependence through kriging maps. The analyses of the maps allowed observing problems in the heating system in regions inside the broiler house, which may cause a thermal discomfort to the animals besides productive and economic losses.

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

    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. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)], E-mail: risilva@fc.up.pt; 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; Temprado, Manuel; 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); Elguero, Jose [Instituto de Quimica Medica, C.S.I.C., Juan de la Cierva, 3, E-28006 Madrid (Spain)

    2009-12-15

    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{sup 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{sup -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{sup -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{sup -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.

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

    Science.gov (United States)

    Giorgi, Lara De; 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

  1. Water networks contribute to enthalpy/entropy compensation in protein-ligand binding.

    Science.gov (United States)

    Breiten, Benjamin; Lockett, Matthew R; Sherman, Woody; Fujita, Shuji; Al-Sayah, Mohammad; Lange, Heiko; Bowers, Carleen M; Heroux, Annie; Krilov, Goran; Whitesides, George M

    2013-10-16

    The mechanism (or mechanisms) of enthalpy-entropy (H/S) compensation in protein-ligand binding remains controversial, and there are still no predictive models (theoretical or experimental) in which hypotheses of ligand binding can be readily tested. Here we describe a particularly well-defined system of protein and ligands--human carbonic anhydrase (HCA) and a series of benzothiazole sulfonamide ligands with different patterns of fluorination--that we use to define enthalpy/entropy (H/S) compensation in this system thermodynamically and structurally. The binding affinities of these ligands (with the exception of one ligand, in which the deviation is understood) to HCA are, despite differences in fluorination pattern, indistinguishable; they nonetheless reflect significant and compensating changes in enthalpy and entropy of binding. Analysis reveals that differences in the structure and thermodynamic properties of the waters surrounding the bound ligands are an important contributor to the observed H/S compensation. These results support the hypothesis that the molecules of water filling the active site of a protein, and surrounding the ligand, are as important as the contact interactions between the protein and the ligand for biomolecular recognition, and in determining the thermodynamics of binding.

  2. Enthalpy versus entropy-driven binding of bisphosphonates to farnesyl diphosphate synthase.

    Science.gov (United States)

    Yin, Fenglin; Cao, Rong; Goddard, Amanda; Zhang, Yonghui; Oldfield, Eric

    2006-03-22

    We report the results of an ITC (isothermal titration calorimetry) investigation of the binding of six bisphosphonates to the enzyme farnesyl diphosphate synthase (FPPS; EC 2.5.1.10) from Trypanosoma brucei. The bisphosphonates investigated were zoledronate, risedronate, ibandronate, pamidronate, 2-phenyl-1-hydroxyethane-1,1-bisphosphonate, and 1-(2,2-bisphosphonoethyl)-3-iodo pyridinium. At pH = 7.4, both risedronate and the phenylethane bisphosphonate bind in an enthalpy-driven manner (DeltaH approximately -9 to 10 kcal mol-1), but the other four bisphosphonates bind in an entropy-driven manner (DeltaS varying from 31.2 to 55.1 cal K-1 mol-1). However, at pH = 8.5, zoledronate binding switches from entropy to enthalpy-driven. The DeltaG results are highly correlated with FPPS inhibition results obtained using a radiochemical assay (R2 = 0.85, N = 11, P enthalpy-driven, with the enhanced activity of the basic side chain containing species being attributable to their becoming protonated in the active site. Given the large size of the bisphosphonate market and the potential importance of the development of these compounds for cancer immunotherapy and anti-parasitic chemotherapy, these results are of broad general interest in the context of the development of new, potent, and selective FPPS inhibitors.

  3. Calculation of the enthalpies of formation and proton affinities of some isoquinoline derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Namazian, Mansoor [ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200 (Australia)], E-mail: namazian@rsc.anu.edu.au; Coote, Michelle L. [ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200 (Australia)], E-mail: mcoote@rsc.anu.edu.au

    2008-12-15

    Ab initio molecular orbital theory has been used to calculate enthalpies of formation of isoquinoline, 1-hydroxyisoquinoline, 5-hydroxyisoquinoline, and 1,5-dihydroxyisoquinoline as well as some pyridine and quinoline derivatives. The proton affinities of the four isoquinoline derivatives were also obtained. The high-level composite methods G3(MP2), G3(MP2)//B3LYP, G3//B3LYP, and CBS-QB3 have been used for this study, and the results have been compared with available experimental values. For six of the eight studied compounds, the theoretical enthalpies of formation were very close to the experimental values (to within 4.3 kJ . mol{sup -1}); where comparison was possible, the theoretical and experimental proton affinities were also in excellent agreement with one another. However, there is an extraordinary discrepancy between theory and experiment for the enthalpies of formation of 1-hydroxyisoquinoline and 1,5-dihydroxyisoquinoline, suggesting that the experimental values for these two compounds should perhaps be re-examined. We also show that popular low cost computational methods such as B3LYP and MP2 show very large deviations from the benchmark values.

  4. Vapor pressures and vaporization enthalpy of codlemone by correlation gas chromatography

    International Nuclear Information System (INIS)

    Highlights: • The vaporization enthalpy of codlemone has been evaluated. • The vapor pressure of codlemone has been evaluated from T = (298.15 to Tb) 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 TB = 389 K at p = 267 Pa is within the temperature range reported in the literature. A normal boiling temperature of TB = (549.1 ± 0.1) K is also estimated by extrapolation

  5. Wood Bond Testing

    Science.gov (United States)

    1989-01-01

    A joint development program between Hartford Steam Boiler Inspection Technologies and The Weyerhaeuser Company resulted in an internal bond analyzer (IBA), a device which combines ultrasonics with acoustic emission testing techniques. It is actually a spinoff from a spinoff, stemming from a NASA Lewis invented acousto-ultrasonic technique that became a system for testing bond strength of composite materials. Hartford's parent company, Acoustic Emission Technology Corporation (AET) refined and commercialized the technology. The IBA builds on the original system and incorporates on-line process control systems. The IBA determines bond strength by measuring changes in pulsar ultrasonic waves injected into a board. Analysis of the wave determines the average internal bond strength for the panel. Results are displayed immediately. Using the system, a mill operator can adjust resin/wood proportion, reduce setup time and waste, produce internal bonds of a consistent quality and automatically mark deficient products.

  6. Water's Hydrogen Bond Strength

    CERN Document Server

    Chaplin, Martin

    2007-01-01

    Water is necessary both for the evolution of life and its continuance. It possesses particular properties that cannot be found in other materials and that are required for life-giving processes. These properties are brought about by the hydrogen bonded environment particularly evident in liquid water. Each liquid water molecule is involved in about four hydrogen bonds with strengths considerably less than covalent bonds but considerably greater than the natural thermal energy. These hydrogen bonds are roughly tetrahedrally arranged such that when strongly formed the local clustering expands, decreasing the density. Such low density structuring naturally occurs at low and supercooled temperatures and gives rise to many physical and chemical properties that evidence the particular uniqueness of liquid water. If aqueous hydrogen bonds were actually somewhat stronger then water would behave similar to a glass, whereas if they were weaker then water would be a gas and only exist as a liquid at sub-zero temperature...

  7. Cold inactivation and dissociation into dimers of Escherichia coli tryptophanase and its W330F mutant form.

    Science.gov (United States)

    Erez, T; Gdalevsky GYa; Torchinsky, Y M; Phillips, R S; Parola, A H

    1998-05-19

    The kinetics and mechanism of reversible cold inactivation of the tetrameric enzyme tryptophanase have been studied. Cold inactivation is shown to occur slowly in the presence of K+ ions and much faster in their absence. The W330F mutant tryptophanase undergoes rapid cold inactivation even in the presence of K+ ions. In all cases the inactivation is accompanied by a decrease of the coenzyme 420-nm CD and absorption peaks and a shift of the latter peak to shorter wavelengths. The spectral changes and the NaBH4 test indicate that cooling of tryptophanase leads to breaking of the internal aldimine bond and release of the coenzyme. HPLC analysis showed that the ensuing apoenzyme dissociates into dimers. The dissociation depends on the nature and concentration of anions in the buffer solution. It readily occurs at low protein concentrations in the presence of salting-in anions Cl-, NO3- and I-, whereas salting-out anions, especially HPO4(2-), hinder the dissociation. K+ ions do not influence the dissociation of the apoenzyme, but partially protect holotryptophanase from cold inactivation. Thus, the two processes, cold inactivation of tryptophanase and dissociation of its apoform into dimers exhibit different dependencies on K+ ions and anions.

  8. Dissociation of RDX at 532 nm Laser%532nm激光作用下RDX的解离

    Institute of Scientific and Technical Information of China (English)

    张伟; 沈瑞琪; 吴立志; 秦钊; 叶迎华; 胡艳; 朱朋

    2012-01-01

    采用飞行时间质谱仪(TOFMS)研究了532 nm激光作用下RDX的解离过程,得到RDX解离过程中的正、负离子飞行时间质谱图.根据离解产物离子的可能分布,提出了RDX的3种解离途径.结果表明,N-N和C-N键断裂竞争反应呈现在532 nm激光作用下RDX的解离过程中.%The dissociation process of hexahydro-l,3,5-trinitro-l,3 , 5-triazine(RDX) under 532nm laser was studied by time of flight mass spectrometer(TOFMS). The mass spectra of both positive and negative ions in the dissociation process of RDX were obtained. Three possible dissociation paths of RDX were proposed based on the possible ion distribution of the dissociation products. The results indicated that the competing reactions of cracking the N - N and C-N bond occurred in the dissociation of RDX when it was irradiated by 532 nm laser.

  9. Theoretical Study of the Ozonolysis of C60: Primary Ozonide Formation, Dissociation, and Multiple Ozone Additions

    OpenAIRE

    Chapleski, Robert C., Jr.; Morris, John R.; Troya, Diego

    2014-01-01

    We present an investigation of the reaction of ozone with C60 fullerene using electronic structure methods. Motivated by recent experiments of ozone exposure to a C60 film, we have characterized stationary points in the potential energy surface for the reactions of O3 with C60 that include both the formation of primary ozonide and subsequent dissociation reactions of this intermediate that lead to C_C bond cleavage. We have also investigated the addition of multiple O3 molecules to the C60 ca...

  10. Thermal Dissociation and Roaming Isomerization of Nitromethane: Experiment and Theory.

    Science.gov (United States)

    Annesley, Christopher J; Randazzo, John B; Klippenstein, Stephen J; Harding, Lawrence B; Jasper, Ahren W; Georgievskii, Yuri; Ruscic, Branko; Tranter, Robert S

    2015-07-16

    The thermal decomposition of nitromethane provides a classic example of the competition between roaming mediated isomerization and simple bond fission. A recent theoretical analysis suggests that as the pressure is increased from 2 to 200 Torr the product distribution undergoes a sharp transition from roaming dominated to bond-fission dominated. Laser schlieren densitometry is used to explore the variation in the effect of roaming on the density gradients for CH3NO2 decomposition in a shock tube for pressures of 30, 60, and 120 Torr at temperatures ranging from 1200 to 1860 K. A complementary theoretical analysis provides a novel exploration of the effects of roaming on the thermal decomposition kinetics. The analysis focuses on the roaming dynamics in a reduced dimensional space consisting of the rigid-body motions of the CH3 and NO2 radicals. A high-level reduced-dimensionality potential energy surface is developed from fits to large-scale multireference ab initio calculations. Rigid body trajectory simulations coupled with master equation kinetics calculations provide high-level a priori predictions for the thermal branching between roaming and dissociation. A statistical model provides a qualitative/semiquantitative interpretation of the results. Modeling efforts explore the relation between the predicted roaming branching and the observed gradients. Overall, the experiments are found to be fairly consistent with the theoretically proposed branching ratio, but they are also consistent with a no-roaming scenario and the underlying reasons are discussed. The theoretical predictions are also compared with prior theoretical predictions, with a related statistical model, and with the extant experimental data for the decomposition of CH3NO2, and for the reaction of CH3 with NO2. PMID:25886024

  11. Polarization induced water molecule dissociation below the first-order electronic-phase transition temperature.

    Science.gov (United States)

    Das Arulsamy, Andrew; Kregar, Zlatko; Eleršič, Kristina; Modic, Martina; Subramani, Uma Shankar

    2011-09-01

    Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O-H covalent bonds within a single water molecule adsorbed on the MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on the MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the first-order electronic-phase transition temperature.

  12. Polarization induced water molecule dissociation below the first-order electronic-phase transition temperature

    CERN Document Server

    Arulsamy, Andrew Das; Elersic, Kristina; Modic, Martina; Subramani, Uma Shankar

    2011-01-01

    Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O$-$H covalent bonds within a single water molecule adsorbed on MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the...

  13. Reevaluation of fuel enthalpy in NSRR test for high burnup fuels

    International Nuclear Information System (INIS)

    This paper describes the recent procedure of evaluation of the fuel enthalpy in the reactivity initiated accident (RIA) simulating tests performed at the nuclear safety research reactor (NSRR), and reports some important updates of the fuel enthalpies in the tests with high burnup PWR fuels. Previously, the fuel enthalpy had been evaluated by the procedure based on the short-life fission product measurement, i.e. a pellet slice was sampled from the test fuel rod after the NSRR test, a chemical separation process was applied to the solution of the pellet slice to separate barium, and the amount of Ba-140 was measured by gamma spectrometry on the separated barium. But a part of the results showed significant scattering even within the similar tests with similar fuels, which should have showed similar fuel enthalpies. The scattering appears to indicate the difficulty in treatment of the short-life nuclides after the completion of the NSRR test and unsuccessful measurement of the amount of fuel dissolved in the specimen preparation. Another difficulty of the procedure is that it is not repeatable for a specimen and so double check of an evaluation is not possible. Hence, an alternative procedure, which is based on the total amount of fissile materials evaluated by mass analysis, was developed and has been applied for the tests after 2003; the amount of fissile materials is input to a well-verified neutron transport calculation model for the NSRR reactor core to calculate a coupling factor of power densities between the test fuel rod and the NSRR driver fuel rods. This procedure does not require quickness and is repeatable, so it is applicable even many years later if the fuel sample is available. The recent procedure was thus applied to the tests before 2003, whose burnups are below 60 GWd/tU. It was shown that the fuel enthalpy had been significantly underestimated in the tests with high burnup PWR fuels: the test series HBO and TK. In this paper, the procedure

  14. Coulomb dissociation of $^{20,21}$N

    CERN Document Server

    Röder, Marko; Aksyutina, Yulia; Alcantara, Juan; Altstadt, Sebastian; Alvarez-Pol, Hector; Ashwood, Nicholas; Atar, Leyla; Aumann, Thomas; Avdeichikov, Vladimir; Barr, M; Beceiro, Saul; Bemmerer, Daniel; Benlliure, Jose; Bertulani, Carlos; Boretzky, Konstanze; Borge, Maria J G; Burgunder, G; Caamano, Manuel; Caesar, Christoph; Casarejos, Enrique; Catford, Wilton; Cederkall, Joakim; Chakraborty, S; Chartier, Marielle; Chulkov, Leonid; Cortina-Gil, Dolores; Crespo, Raquel; Pramanik, Ushasi Datta; Diaz-Fernandez, Paloma; Dillmann, Iris; Elekes, Zoltan; Enders, Joachim; Ershova, Olga; Estrade, A; Farinon, F; Fraile, Luis M; Freer, Martin; Freudenberger, M; Fynbo, Hans; Galaviz, Daniel; Geissel, Hans; Gernhäuser, Roman; Göbel, Kathrin; Golubev, Pavel; Diaz, Diego Gonzalez; Hagdahl, Julius; Heftrich, Tanja; Heil, Michael; Heine, Marcel; Heinz, Andreas; Henriques, Ana; Holl, Matthias; Ickert, G; Ignatov, Alexander; Jakobsson, Bo; Johansson, Hakan; Jonson, Björn; Kalantar-Nayestanaki, Nasser; Kanungo, Rituparna; Kelic-Heil, Aleksandra; Knöbel, Ronja; Kröll, Thorsten; Krücken, Reiner; Kurcewicz, J; Kurz, Nikolaus; Labiche, Marc; Langer, Christoph; Bleis, Tudi Le; Lemmon, Roy; Lepyoshkina, Olga; Lindberg, Simon; Machado, Jorge; Marganiec, Justyna; Caro, Magdalena Mostazo; Movsesyan, Alina; Najafi, Mohammad Ali; Nilsson, Thomas; Nociforo, Chiara; Panin, Valerii; Paschalis, Stefanos; Perea, Angel; Petri, Marina; Pietri, S; Plag, Ralf; Prochazka, A; Rahaman, Md Anisur; Rastrepina, Ganna; Reifarth, Rene; Ribeiro, Guillermo; Ricciardi, M Valentina; Rigollet, Catherine; Riisager, Karsten; Rossi, Dominic; Saez, Jose Sanchez del Rio; Savran, Deniz; Scheit, Heiko; Simon, Haik; Sorlin, Olivier; Stoica, V; Streicher, Branislav; Taylor, Jon; Tengblad, Olof; Terashima, Satoru; Thies, Ronja; Togano, Yasuhiro; Uberseder, Ethan; Van de Walle, J; Velho, Paulo; Volkov, Vasily; Wagner, Andreas; Wamers, Felix; Weick, Helmut; Weigand, Mario; Wheldon, Carl; Wilson, G; Wimmer, Christine; Winfield, J S; Woods, Philip; Yakorev, Dmitry; Zhukov, Mikhail; Zilges, Andreas; Zuber, Kai

    2016-01-01

    Neutron-rich light nuclei and their reactions play an important role for the creation of chemical elements. Here, data from a Coulomb dissociation experiment on $^{20,21}$N are reported. Relativistic $^{20,21}$N ions impinged on a lead target and the Coulomb dissociation cross section was determined in a kinematically complete experiment. Using the detailed balance theorem, the $^{19}\\mathrm{N}(\\mathrm{n},\\gamma)^{20}\\mathrm{N}$ and $^{20}\\mathrm{N}(\\mathrm{n},\\gamma)^{21}\\mathrm{N}$ excitation functions and thermonuclear reaction rates have been determined. The $^{19}\\mathrm{N}(\\mathrm{n},\\gamma)^{20}\\mathrm{N}$ rate is up to a factor of 5 higher at $T<1$\\,GK with respect to previous theoretical calculations, leading to a 10\\,\\% decrease in the predicted fluorine abundance.

  15. The charmonium dissociation in an "anomalous wind"

    CERN Document Server

    Sadofyev, Andrey V

    2016-01-01

    We study the charmonium dissociation in a strongly coupled chiral plasma in the presence of magnetic field and axial charge imbalance. This type of plasma carries ``anomalous flow" induced by the chiral anomaly and exhibits novel transport phenomena such as chiral magnetic effect. We found that the ``anomalous flow" would modify the charmonium color screening length by using the gauge/gravity correspondence. We derive an analytical expression quantifying the ``anomalous flow" experienced by a charmonium for a large class of chiral plasma with a gravity dual. We elaborate on the similarity and {\\it qualitative} difference between anomalous effects on the charmonium color screening length which are {\\it model-dependent} and those on the heavy quark drag force which are fixed by the second law of thermodynamics. We speculate on the possible charmonium dissociation induced by chiral anomaly in heavy ion collisions.

  16. Grammatical category dissociation in multilingual aphasia.

    Science.gov (United States)

    Faroqi-Shah, Yasmeen; Waked, Arifi N

    2010-03-01

    Word retrieval deficits for specific grammatical categories, such as verbs versus nouns, occur as a consequence of brain damage. Such deficits are informative about the nature of lexical organization in the human brain. This study examined retrieval of grammatical categories across three languages in a trilingual person with aphasia who spoke Arabic, French, and English. In order to delineate the nature of word production difficulty, comprehension was tested, and a variety of concomitant lexical-semantic variables were analysed. The patient demonstrated a consistent noun-verb dissociation in picture naming and narrative speech, with severely impaired production of verbs across all three languages. The cross-linguistically similar noun-verb dissociation, coupled with little evidence of semantic impairment, suggests that (a) the patient has a true "nonsemantic" grammatical category specific deficit, and (b) lexical organization in multilingual speakers shares grammatical class information between languages. The findings of this study contribute to our understanding of the architecture of lexical organization in bilinguals.

  17. Multiphoton dissociative ionization of molecular deuterium

    International Nuclear Information System (INIS)

    The kinetic energy spectra of deuterium ions produced from D2 arising from collision-free subpicosecond irradiation at 248 nm with intensities spanning the 10/sup 13/--10/sup 16/-W/cm2 range have been measured by time-of-flight analysis. The behaviors of the kinetic energy distributions of the fragments and the relative abundances of atomic (D+) and molecular (D2+) ions reveal the presence of two mechanisms of multiphoton dissociative ionization. Calibration of the energy scale for D+ is facilitated by comparison with He/sup 2+/. For intensities in the 10/sup 13/--10/sup 15/-W/cm2 region, intermediate three-photon resonances and the optical Stark shift play important roles. At an intensity /similar to/0/sup 16/ W/cm2, a direct transition from the molecular ground state to the dissociative ionic level appears as a significant channel. No evidence of direct double ionization was observed

  18. Coulomb dissociation studies for astrophysical thermonuclear reactions

    Energy Technology Data Exchange (ETDEWEB)

    Motobayashi, T. [Dept. of Physics, Rikkyo Univ., Toshima, Tokyo (Japan)

    1998-06-01

    The Coulomb dissociation method was applied to several radiative capture processes of astrophysical interest. The method has an advantage of high experimental efficiency, which allow measurements with radioactive nuclear beams. The reactions {sup 13}N(p,{gamma}){sup 14}O and {sup 7}Be(p,{gamma}){sup 8}B are mainly discussed. They are the key reaction in the hot CNO cycle in massive stars and the one closely related to the solar neutrino problem, respectively. (orig.)

  19. Dissociations between developmental dyslexias and attention deficits

    OpenAIRE

    Limor eLukov; Naama eFriedmann; Lilach eShalev; Lilach eKhentov-Kraus; Nir eShalev; Rakefet eLorber; Revital eGuggenheim

    2015-01-01

    We examine whether attention deficits underlie developmental dyslexia, or certain types of dyslexia, by presenting double dissociations between the two. We took into account the existence of distinct types of dyslexia and of attention deficits, and focused on dyslexias that may be thought to have an attentional basis: letter position dyslexia (LPD), in which letters migrate within words, attentional dyslexia (AD), in which letters migrate between words, neglect dyslexia, in which letters on o...

  20. Three competitive dissociation pathways of glyoxalate

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Three possible lower barrier dissociation pathways of the deportonated glyoxylic acid in aqueous solution axe predicated by means of B3LYP and CCSD(T) (single-point) methods. The calculated results suggest that the formation of formate ion is the energetically most favorable process, and that the decomposition reaction is occurring through nucleophilic attack of negatively charged carboxylic oxygen on the a-carbon. This is in good agreement with the proposed mechanisms of the mass spectrometry experiment.