Molecular geometry and boiling related thermodynamic properties

Boiling related thermodynamic properties are important parameters in research. In this study, a model integrating both additive groups and non-additive molecular geometric factors has been developed for the calculation of boiling enthalpy, entropy and temperature. The calculated values are in good agreement with the measured values of 470 compounds. This model provides a simple and accurate estimation of enthalpy of boiling, entropy of boiling and boiling temperatures with absolute average errors of 0.62 kJ/mol, 1.15 J/K · mol and 7.13 K respectively.

► Molecular geometric factors were found to be important determinants for boiling entropy and thus the boiling temperature. ► Only four molecular geometric factors were used in the study. ► A group contribution method was used to calculate enthalpy of boiling. ► The proposed method is simple and the estimations are in good agreement with experimental values.