Journal of Chemical and Engineering Data, Vol.47, No.4, 700-714, 2002
Thermodynamic properties and ideal-gas enthalpies of formation for trans-methyl cinnamate, alpha-methyl cinnamaldehyde, methyl methacrylate, 1-nonyne, trimethylacetic acid, trimethylacetic anhydride, and ethyl trimethyl acetate
The results of a study aimed at improvement of group-contribution methodology for estimation of thermodynamic properties of organic substances are reported. Specific weaknesses where particular group-contribution terms were unknown, or estimated because of lack of experimental data, are addressed by experimental studies of enthalpies of combustion in the condensed phase, vapor-pressure measurements, and differential scanning calorimetzic heat-capacity measurements. Ideal-gas and condensed-phase enthalpies of formation of trans-methyl cinnamate, a-methyl cinnamaldehyde, methyl methacrylate, 1-nonyne, trimethylacetic acid, trimethylacetic anhydride, and ethyl trimethyl acetate are reported. Enthalpies of fusion were determined for trans-methyl cinnamate and trimethylacetic acid. Two-phase (solid + vapor) or (liquid + vapor) heat capacities were determined from 300 K to the critical region or earlier decomposition temperature for all the compounds. For ethyl trimethyl acetate, the values of the critical temperature and critical density were determined from the DSC results and the corresponding critical pressure was derived from the fitting procedures. The results of all the measurements were combined to derive a series of thermophysical properties including critical temperature, critical density, critical pressure, acentric factor, enthalpies of vaporization (restricted to within 50 K of the temperature range of the vapor pressures), and heat capacities along the saturation line. Wagner-type vapor-pressure equations were derived for each compound. Group-additivity enthalpy of formation parameters and strain energies useful in the application of ideal-gas group-contribution correlations were derived.