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81.
82.
Experimental data of excess molar enthalpy of binary mixtures of acetonitrile + diethylamine or S-butylamine mixtures as a function of composition at 288.15, 293.15, 298.15 and 303.15 K at atmospheric pressure have been used to calculate excess partial molar enthalpy and partial molar enthalpy of each component as a function of composition as well as partial molar enthalpy properties at infinite dilution. The Flory and Prigogine–Flory–Patterson (PFP) theories were applied to correlate the data. The results of the calculations as well as the influence of temperature and isomers chain on the partial molar enthalpy properties are discussed. 相似文献
83.
84.
Summary The generator contains diffusion tubes of known length and internal diameter. Once produced, the mixture of the carrier gas and acetone, the reference material, is sent through a chromatographic flame ionisation detector. Its signal reaches a constant level after a time corresponding to the stabilization time of the generator. The technique described is simple and gives repeatable results. 相似文献
85.
The concentration dependence of the apparent molar volumes of lithium halides (and electrolytes in general) in alcohols (and
solvents permitting association in general) is, in the first instance, due to changes in the degree of association and to
the inherent difference between the apparent molar volumes of the ions and of the ion pairs. Previous publications on the
molar volumes of electrolytes in organic solvents, disregarding altogether ion pairing, appear to be incorrect. Data from
the literature for lithium chloride and lithium bromide in normal primary alcohols and several branched alcohols from C1 to C8 and data from our laboratory for lithium halides in 1-hexanol and 2-ethyl-1-hexanol served for the determination of φ
V
and φ
E
. Electrical and structural contributions to the values of these functions for the ions and for the ion pairs are discussed. 相似文献
86.
Attempts to theoretically address the problems involved in transferring linear gradient elution methods have been somewhat ad hoc due to the simplifying assumptions usually made in conventional gradient elution theory. Until now, all equations based on the k* parameter of linear gradient elution theory used as the basis for predicting the separation selectivity have not explicitly included the effect of the dwell volume (VD). Using an exact equation for predicting k*, that is, one which fully accounts in an a priori fashion for VD, we find a set of simple yet exact equations which unequivocally must be satisfied to transfer an optimized linear gradient elution method from one system (column or instrument or both) to another. These relationships absolutely mandate that a change in the instrument dwell volume requires a proportional change in the column volume; in turn, a change in the column volume requires a proportional change in the flow rate and/or gradient time to maintain a constant gradient steepness. Although we are not the first to suggest these guidelines, this work provides a complete theoretical foundation for these exact guidelines for the maintenance of gradient selectivity for the case of transferring a linear gradient elution method between different columns packed with the same particles and/or between different instruments. 相似文献
87.
H.-L. Liu S.-J. Liu Z.-L. Xiao Q.-Y. Chen D.-W. Yang 《Journal of Thermal Analysis and Calorimetry》2006,85(3):541-544
Excess molar enthalpies of binary mixtures for tributyl
phosphate (TBP)+methanol/ethanol were measured with a TAM air Isothermal calorimeter
at 298.15 K and ambient. The results for xTBP+(1–x)CH3OH
are negative in the whole range of composition, while the values for xTBP+(1–x)C2H5OH
change from positive values at low x to
small negative values at high x. The experimental
results have been correlated with the Redlich–Kister polynomial. IR
spectra of the mixtures were measured to investigate the effect of hydrogen
bonding in the mixture. 相似文献
88.
The densities of H2O, D2O, and MeOH solutions in acetonitrile with the solute concentrations up to 0.07 molar fractions at 278.15, 288.15, 298.15, 308.15, and 318.15 K were measured using vibrating-tube densimetry with an error 8·10–6 g cm–3. The limiting partial molar volumes for the H/D isotopomers of water and IaII in acetonitrile (V–
2
) and the isotope effects in V–
2
and in excess molar volumes of acetonitrile—water mixtures were calculated. Molecules of H2O, D2O, and IaII form associates with acetonitrile molecules via hydrogen bonds. The associates have the packing volumes close to those in the individual solute. The water and methanol molecules were assumed to be incorporated into the acetonitrile structure without substantial changes in the latter. However, this process results in some compression of the system with a simultaneous increase in its expansibility. 相似文献
89.
Using a precise technique of scanning microcalorimetry the heat capacity differences between water and dilute aqueous solutions of ethanol, n-propanol, n-butanol and n-pentanol were measured from 5 to 125°C and the partial molar heat capacities of these substances in water were determined. It was found that the heat capacity increment for alcohol disolved in water is proportional to the number of the-CH
2
–
groups and decrease with a temperature increase. The heat capacity increment of hydration of non-polar groups is shown to be positive and large at room temperature and decreases in magnitude as the temperature increases. In contrast, the heat capacity increment of hydration of polar groups is negative at room tempreature and increases as the temperature increases. From the temperature dependence of the heat capacity increment one can assume that the water molecules solvated by the non-polar groups of the alcohols behave in a non-cooperative manner. 相似文献
90.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether. 相似文献