An Empirical Correlation and Method of Calculation of Barriers Hindering Internal Rotation

Abstract
The barriers hindering internal rotation of methyl groups can be calculated by assuming that they are solely due to repulsion between hydrogen atoms according to the law Vij=4.99 ×105/rij5. For dimethyl ether, dimethyl sulfide, and propylene the empirically calculated values are low. This discrepancy is discussed. This treatment is applied to ethyl and isopropyl alcohol and several normal paraffins. The resulting entropies, heat capacities, and equilibrium constants are compared with the available experimental data.

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