Heats of Mixing of Mixed Solvent Solutions of Alkali Metal Salts of Substituted Benzenesulfonic Acids

The enthalpy change on mixing solutions of methyl-substituted benzenesulfonic acids and their salts, with salts having a common cation or anion, at constant ionic strength in mixtures of 1,4-dioxane with water, were measured at 25°C. The heat effects of mixing solutions having a common anion increase almost linearly with the reciprocal value of the dielectric constant of the solvent. The heat effects of mixing solutions having a common cation, which are all negative in water-rich solutions, become endothermic after a certain value of the dielectric constant is passed. The results are discussed in terms of the solute-solvent structural properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

Approximation of enthalpy of formation by Fourier series

A possible approximation of the enthalpy of formation of C,H,N,O-containing compounds by trigonometric Fourier series has been shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1389–1390, August, 1994.     

微孔和介孔材料中的热化学

这篇论文综述了美国加州大学戴维斯分校科学院院士Navrotsky课题组多年来在多孔材料上取得的一系列热化学研究结果。讨论了热化学对微孔、介孔材料的结构稳定性和合成过程的影响。借助多种测热手段对影响骨架结构的热焓、热熵和自由能进行了系统的测量和计算。研究数据表明一系列纯硅分子筛、介孔材料和磷酸铝多孔材料同相应的石英相和块磷铝矿相相比能量上最多只高出15 kJ·mol-1。一系列纯硅分子筛的熵值比石英相高出3.2—4.2 J·K-1·mol-1；在0—12.6 J·K-1·mol-1范围内相对应的自由能几乎没有差别。因此，对不同微孔、介孔材料，其骨架结构在能量上是几乎没有区别的。另外，本文通过介绍一种新型测热方法——原位测热，揭示了分子筛合成过程中的动力学和成核/结晶机理。     

Enthalpies of adsorption of methylene blue and crystal violet to montmorillonite

Calorimetric measurements of the enthalpy of adsorption on montmorillonite indicate different patterns for methylene blue (MB) and crystal violet (CV). The enthalpy of adsorption of MB is endothermic up to 73% of the cation exchange capacity (CEC) (i.e., about 0.6 mmol g^-1 clay), whereas at higher adsorption ratios the adsorption reaction becomes exothermic. The enthalpy of adsorption of CV is exothermic for all amounts adsorbed. These results were confirmed with adsorption experiments that prove that adsorption of MB increase with temperature, whereas CV adsorption decreases. This behavior indicates changes in the equilibrium coefficient according to Van't Hoff's equation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Determination of thermodynamic functions of sorption for cyclohexyl-, piperidyl-, morpholyl-, and thiomorpholyl-n-alkanes by capillary gas-liquid chromatography

The values of partial molar free energy (G), enthalpy (H), and entropy (S) of sorption in the homologous series ofN-alkylpiperidines,N-alkylmorpholines,N-alkyl thiomorpholines, and alkylcyclohexanes were determined. It was found that the free energy of sorption is determined to a greater extent by the enthalpy term than by the entropy one. The free energy of sorption of the first homolog decreases when then-alkyl chain is attached directly to the carbon atom of the cycle and increases in the case ofN-alkylsubstituted heterocycles. The influence of the heteroatom nature on intermolecular interactions of homologs with the nonpolar stationary phase was quantitatively estimated on the basis of thermodynamic data.Dead time necessary for calculation of the retention factor was determined by the retention of methane injected into the column simultaneously with the sample.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2030–2032, August, 1996.     

Thermodynamics of mixtures of hexane and heptane isomers with normal and branched hexadecane

Molar excess mixing enthalpies h ^E , Gibbs free energies g ^E and hence entropies s ^E have been obtained using calorimetry and the vapor sorption method at 25°C for hexane isomers+2,2,4,4,6,8,8-heptamethylnonane, a highly branched C ₁₆ . The h ^E and g ^E are negative while Ts ^E are positive, but small. The values are explained by the Prigogine-Flory theory through negative free volume contributions to h ^E and Ts ^E , counterbalanced in the case of Ts ^E by the positive combinatiorial Ts ^E for mixing molecules of different size. No contribution is seen from the interaction between methyl and methylene groups. The excess quantities are also obtained for hexane and heptane isomers mixed with n-hexadecane. Values of h ^E and Ts ^E are now strongly positive, while those of g ^E are only slightly less negative. The interpretation requires two recently advanced contributions in addition to those of the Prigogine-Flory theory: 1) a decrease of order when correlations of orientations between n-C ₁₆ molecules in the pure liquid are replaced in the solution by weaker correlations whose strengths depend on the shapes of the lower alkane isomers. For lower alkane isomers of the same shape, but highly sterically hindered, h ^E and Ts ^E are small, manifesting, 2) a negative contribution, ascribed to a rotational ordering of n-C ₁₆ segments on the sterically-hindered molecule. Enthalpy-entropy compensation is observed for these new contributions, arising from their rapid fall-off with increase of temperature.     

Paradigms and Paradoxes: Thoughts on the Enthalpy of Formation of Guanidine and Its Monosubstituted Derivatives

Despite their seeming simplicity, substituted guanidines have not particularly caught the attention of the thermochemical community. The current paper compares the enthalpy of formation of solid substituted guanidines with correspondingly substituted benzenes, also as solids.     

Adsorption enthalpy and desorption enthalpy during displacement of adsorbate to solvent in a liquid-solid system

The adsorption heat of the stoichiometric displacement process for the adsorption of a solute in a liquid-solid system was investigated. On the basis of the SDM-A and the rule of the additivity of energy, an expression which describes the dependence of the adsorption enthalpy on the nature and concentration of the solute, and on the solvent and adsorbent, was derived. The adsorption heat determined for the solute with the traditional method can be divided into two independent fractions, relating to the adsorption of the solute and to the desorption of the solvent. Experimental data on both isotherms from the literatures and precise calorimetry were used to test the adsorption heat and its fractions computed quantitatively via the equations presented in this study, and a satisfactory degree of conformity between them was obtained. Supported by the Natural Science Foundation of Shaanxi Province in China.     

Excess molar enthalpies of the ternary mixtures: (diisopropyl ether or 2-methyltetrahydrofuran) + cyclohexane + n-heptane at 298.15 K

Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the two ternary systems formed by mixing either diisopropyl ether or 2-methyltetrahydrofuran with binary mixtures of cyclohexane and n-heptane. Smooth representations of the results are presented and used to construct constant excess molar enthalpy contours on Roozeboom diagrams. It is shown that useful estimates of the ternary enthalpies can be obtained from the Liebermann and Fried model, using only the physical properties of the components and their binary mixtures.     

The calorimetric investigation of phosphoric acid-N,N-dimethylformamide system

Solution and mixing enthalpies for the orthophosphoric acid (H₃PO₄)-N,N-dimethylformamide (DMF) system were measured over the whole concentration range at 25 °C. The standard value of solution enthalpy of phosphoric acid in DMF and the standard transference enthalpy of H₃PO₄ from water to DMF were calculated. The mixing enthalpy concentration dependence permitted making assumptions on complex formation in the system under investigation.