It is shown that there is a linear relationship between the activation energy for a thermal cis–trans isomerization and the heat of hydrogenation of the C=C bond. There is also a linear relationship between the entropy of activation and the heat of activation, there being a partial compensation effect. It is pointed out that the activation energy for these processes is very close to the π-bond energy of the C=C bond. The significance of these relationships is discussed in terms of the reaction mechanisms.