Relationship between partial and average atomic volumes of components in Au-Ni alloys

In the framework of systematic science of alloys,the average molar property（volume and potential energy） functions of disordered alloys were established.From these functions,the average molar property functions,partial molar property functions,derivative functions with respect to composition,general equation of relationship between partial and average molar properties of components,difference equation and constraining equation of different values between partial and average molar properties,as well as general Gibbs-Duhem formula were derived.It was proved that the partial molar properties calculated from various combinative functions of average molar properties of alloys are equal,but in general,the partial molar properties are not equal to the average molar properties of a given component.This means that the partial molar properties cannot represent the corresponding properties of the component.All the equations and functions established in this work were proved to be correct by calculating the results of partial and average atomic volumes of components as well as average atomic volumes of alloys in the Au-Ni system.

Determination of Partial Molar Volumes of EPA and DHA Ethyl Esters in Supercritical Carbon Dioxide

The use of supercritical-fluid chromatography for determining partial molar volumes of ethyl esters of cis-5,8,11,14,17-eicosapentaenoic acid (EPA) and cis -4,7,10,13,16,19- docosa-hexaenoic acid (DHA) in supercritical carbon dioxide is presented and discussed. Partial molar volumes of EPA and DHA esters are obtained from the variation of the retention properties with the density of mobile phase at 313.15 K, 323.15 K, 333.15 K and in the pressure range from 9 MPa to 21 MPa.

Studies on Partial Molar Volumes of Some Amino Acids and Their Groups in Aqueous Solutions from 293.15K to 333.15K

Densities of aqueous solutions of eight amino acids, glycine, L-alanine, L-valine, L-isoleucine, L-serine, L-threonine, L-arginine and L-phenylalanine, are measured as a function of amino acid concentration from 293.15K to 333.15K. These data are used to calculate the apparent molar volume Vφ and infinite dilution apparent molar volume Vφo (partial molar volume). Data of five amino acids are used to correlate partial molar volume Vφo usinggroup contribution method to estimate the contributions of the zwitterionic end groups (NH3+,COO-) and CH2 group, OH group, CNHNHNH2 group and C6H5(phenyl) group of amino acids. The results show that Vφo values for all kinds of groups of amino acids studied increase with increase of temperature except those for CH2 group, which are almost constant within the studied temperature range. Data of other amino acids, L-valine, L-isoleucine and L-threonine, are chosen for comparison with the predicted partial molar volume Vφo using the group additivity parameters obtained. The results confirm that this group additivity method has excellent predictive utility.

A Prediction of the Excess Partial Molar Free Energies of MgCl_2 in the KCI-MgCl_2-LiCl Molten Salt System Containing MgCl_2 below 0.5 from Thermodynamic Properties of Binary Systems

The thermodynamical properties of MgCl_2 in KCI-MgCl_2-LiCl molten electrolytes containing MgCl_2 below 0.5 (mole fraction, the same below) have been determined from the interchange energies of two binary systems KCI-MgCl_2 and LiCI-MgCl_2, by means of a model on the assumptions that the electrolytes in the solution are treated as independent particles instead of their ion forms and the interchange energy between the component pair KCI-LiCl is ignored when compared with those of component pairs KCl-MgCl_2 and MgCl_2-LiCl. The interchange energies, wKCl-MgCl_2 and wMgcCl_2-Licl, are obtained as-70000 and -13800 J.mol-1, from the corresponding binary solutions, respectively.

Partial Molar Entropy and Partial Molar Heat Capacity of Electrons in Metals and Superconductors

There are at least two valid approaches to the thermodynamics of electrons in metals. One takes a microscopic view, based on models of electrons in metals and superconductor and uses statistical mechanics to calculate the total thermodynamic functions for the model-based system. Another uses partial molar quantities, which is a rigorous thermodynamic method to analyze systems with components that can cross phase boundaries and is particularly useful when applied to a system composed of interacting components. Partial molar quantities have not been widely used in the field of solid state physics. The present paper will explore the application of partial molar electronic entropy and partial molar electronic heat capacity to electrons in metals and superconductors. This provides information that is complementary information from other approaches to the thermodynamics of electrons in metals and superconductors and can provide additional insight into the properties of those materials. Furthermore, the application of partial molar quantities to electrons in metals and superconductors has direct relevance to long-standing problems in other fields, such as the thermodynamics of ions in solution and the thermodynamics of biological energy transformations. A unifying principle between reversible and irreversible thermodynamics is also discussed, including how this relates to the completeness of thermodynamic theory.

Volumetric and Viscometric Studies of 4-Aminobutyric Acid in Aqueous Solutions of Salbutamol Sulphate at 308.15, 313.15 and 318.15K

Density （ρ） and viscosity （η） measurements were carried out for 4-aminobutyric acid in 0.0041,0.0125 and 0.0207 mol·L-1 aqueous salbutamol sulphate at T=308.15,313.15 and 318.15K.The measured values of density and viscosity were used to estimate some important parameters such as apparent molar volume Vφ,limiting apparent molar volume Vφ0,transfer volume △Vφ0,hydration number Hn,second derivative of infinite dilution of partial molar volume with temperature 2Vφ0/T2,viscosity B-coefficients,variation of B with temperature dB/dT,free energy of activation per mole of solvent △μ10＊ and solute △μ20＊,activation entropy △S20＊ and activation enthalpy △H20＊ of the amino acids.These parameters have been interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.

Vapor-liquid Phase Equilibria for CO_2+Tertpentanol Binary System at Elevated Pressures

Vapor-liquid phase equilibrium data of tertpentanol in carbon dioxide were measured at temperatures of 313.4, 323.4, 333.5 and 343.5 K and in the pressure range of 4.56--11.44 MPa. The phase equilibium apparatus used in the work was a variable-volume high-pressure cell. The experimental data were reasonably correlated with Peng-Robinson equation of state（PR-EOS） together with van der Waals-2 two-parameter mixing rules. Henry＇s Law constants and partial molar volumes of CO2 at infinite dilution were estimated with Krichevsky-Kasarnovsky equa- tion, and Henry＇s Law constants increase with increasing temperature, however, partial molar volumes of CO2 at infinite dilution are negative whose magnitudes decrease with temperature. Partial molar volumes of CO2 and tertpentanol in liquid phase at equilibrium were calculated.

Densities and viscosities of binary mixtures of n-decane + 1-pentanol,+1-hexanol,+1-heptanol at temperatures from 293.15 to 363.15 K and atmospheric pressure

Densities(ρ) and dynamic viscosities(η) for three binary mixtures of n-decane with 1-pentanol,1-hexanol and1-heptanol are presented at temperatures from 293.15 to 363.15 K and atmospheric pressure over the entire composition range.The density and viscosity are measured using a vibrating tube densimeter and a cylindrical Couette type rotating viscometer,respectively.Excess molar volumes(V^E),viscosity deviations(△η) and excess Gibbs energy of activation of viscous flow(△G^(*E)) are calculated from the experimental measurements.Intermolecular and structural interactions are indicated by the sign and magnitude of these properties.Partial molar volumes and infinity dilution molar partial volumes are also calculated for each binary system.These results are correlated using Redlich-Kister type equations.

Internal Rotation of Cyclopentadienyl Rings in Ferrocene Derivatives

The relaxation time of several ferrocene derivatives was measured, and the internal rotation was discussed. For almost all the derivatives, the degree of the internal rotation was constant in spite of the different molecular weights. However, for (triphenylmethyl)ferrocene, the rotation of the unsubstituted ring would be slower due to the bulkiness of the substituent. Furthermore, the derivatives that have a hydroxyl- or acetyl group on the substituent were also discussed. Their rotation would be influenced by the location of these substituents.

Density of supercritical CO_2-tetrahydrofuran binary mixture and the partial molar volume of the cosolvent

The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from 0 to 0.57 mol/L.The partial molar volume of tetrahydrofuran was calculated based on the relationship between the density of the mixture and the concentration of the cosolvent.It is observed that the partial molar volume of the cosolvent is negative and the absolute value decreases with increasing pressure and the concentration of the cosolvent.

Atomic volumes and volume functions for Ag-Cu alloys

Nine functions of atomic volume interaction have been established. The values of average atomic volumes and lattice constants of Ag-Cu alloys obtained from each V-function are, respectively, equal to each other and in good agreement with experimental values. But the average atomic volumes of components and the volumes of characteristic atoms obtained from each V-function are different from each other. Only after the correlative study of energy, volume and electronic structure is carried out, can the V-function be correctly chosen, can a knowledge system about the alloys be established, thus providing the base for scientific design of new alloys. The relationships between lattice parameters of metastable phases of Ag-Cu alloys and composition and between average properties and partial molar properties of components are discussed.