AbstractsChemistry

Although the study of reaction kinetics really originated when Guldberg and Waage enunciated the Mass Law in 1867, little progress was made for many years. Early workers investigated whether a reaction would or would not go and what yield of products it would give but they gave little consideration to the mechanism of the reaction. [...] In many cases, moreover, the products of the primary decomposition would also decompose so that the final products gave little information about the primary processes. [...] The industrial importance of the hydrocarbons has aroused great interest in their thermal decomposition mechanisms. Unfortunately, however, the thermal decomposition reactions of these compounds generally involve a great many steps that are extremely hard to untangle and the choice of a mechanism, in many cases, becomes one of pure speculation. Consequently, attempts have been made to supplement the information obtained from thermal studies by independent methods. The present investigation is concerned with the applicability of the free radical theory to hydrocarbon decompositions. Information is obtained by an independent method: mercury photosensitization. However, since contemporary knowledge of the subject comes from a variety of sources, it will be advantageous to review the theory of free radicals and to point out the information that can be obtained by the various independent methods before proceeding to specific reactions. [...]