The Determination of a Solvolysis Rate with Tritium Labeling

The Determination of a Solvolysis Rate with Tritium Labeling 

An attempt, by means of tritium-labeling kinetic techniques, to solve a difference in opinion between Swain and Kreevoy (1956) and Hughes et al., and Pocker (1957a, b, c), concerning the mechanism of methanolysis of trityl chloride (85) makes interesting reading not only on scientific grounds, but also for the Biblical references therein 

The problem is not simply solved by conventional procedures, for low concentrations of methanol are difficult to measure, and determinations of loss of trityl chloride (85) or formation of hydrogen chloride do not provide directly the change in methanol concentration. Further, Swain believes that some base must be present to remove the hydrogen chloride as it is formed otherwise, the methanolysis is reversible. This circumstance presents additional difficulties for measurement of specific reaction rate constants. 

Tice and co-workers (1963) have used a similar technique to study the kinetics of hydrogen exchange in dialkylanilines. 

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