C. W. Beckett, K. Pitzer, R. Spitzer
Oct 1, 1947
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Journal
Journal of the American Chemical Society
Abstract
This paper is a continuation of studies on the structural and thermodynamic properties of hydrocarbons. As compared to cyclopentane,b in which a large number of configurations with nearly equal stability result from the opposition of torsional forces about single bonds against forces tending to maintain tetrahedral angles, cyclohexane has one predominant stable configuration, the chair form, since it lies at the minimum in potential energy of each type. Other, higher energy tautomers exist in quite small amounts at room temperature. The energies of these, however, are low enough so that they may contribute to thermal properties. We' have recently measured the heat capacity of gaseous cyclohexane and methylcyclohexane and these data are compared with calculated values in the present paper. In the course of our study very interesting effects of geometrical tautomerism in disubstituted cyclohexanes became apparent. These have been mentioned briefly in a communication to the editor,sa but further details are given in this paper. These compounds are important as constituents of petroleum hence their properties should have considerable practical interest. We shall first discuss the work on cyclohexane in some detail and then briefly describe the less detailed calculations on its derivatives.