Organic carbonates: experiment and ab initio calculations for prediction of thermochemical properties.
This work has been undertaken in order to obtain data on thermodynamic properties of organic carbonates and to revise the group-additivity values necessary for predicting their standard enthalpies of formation and enthalpies of vaporization. The standard molar enthalpies of formation of dibenzyl carbonate, tert-butyl phenyl carbonate, and diphenyl carbonate were measured using combustion calorimetry. Molar enthalpies of vaporization of these compounds were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. Molar enthalpy of sublimation of diphenyl carbonate was measured in the same way. Ab initio calculations of molar enthalpies of formation of organic carbonates have been performed using the G3MP2 method, and results are in excellent agreement with the available experiment. Then the group-contribution method has been developed to predict values of the enthalpies of formation and enthalpies of vaporization of organic carbonates.
Verevkin
Sergey P
SP
Department of Physical Chemistry, University of Rostock, Hermannstrasse 14, D-18051 Rostock, Germany. sergey.verevkin@uni-rostock.de
Emel'yanenko
Vladimir N
VN
Kozlova
Svetlana A
SA
D001555:Benzene Derivatives / Q000737:chemistry*; D001593:Benzyl Compounds / Q000737:chemistry*; D002151:Calorimetry; D002254:Carbonates / Q000737:chemistry*; D003198:Computer Simulation; D008956:Models, Chemical; D011237:Predictive Value of Tests; D011312:Pressure; D011789:Quantum Theory; D013816:Thermodynamics; D014835:Volatilization
D001555:Benzene Derivatives; D001593:Benzyl Compounds; D002254:Carbonates; C533774:tert-butyl phenyl carbonate