The Effect of Pressure and Temperature on the Second-Order Derivatives of the Free Energy Functions for Lower Alkanediols

The second-order derivatives of the free energy functions, i.e., isochoric molar heat capacities, isentropic and isothermal molar compressibility, and isobaric and isentropic molar thermal expansion, were calculated in the temperature range from (293.15 to 318.15) K and at pressures up to 100 MPa for 1,2- and 1,3-propanediol; 1,2-, 1,3, and 1,4-butanediol; and 2-methyl-2,4-pentanediol. The data for calculations were obtained by means of the acoustic method. The pressure and temperature dependencies for the above mentioned properties are analyzed and discussed together with the literature data on isobaric molar heat capacities. The observed marked difference between isobaric and isentropic thermal expansion is analyzed as well. The differences in behavior of linear 1,2-diols and $$\upalpha ,\upomega $$ -diols as well as a diol with a branched carbon chain are emphasized. The isentropic and isothermal molar compressibilities are used to evaluate the dimensionality and relative rigidity of H-associates.