Abstract
This thesis is divided into three sections. After the General Introduction, Chapter 1 describes an attempt to show that the primary kinetic hydrogen isotope effect for a weak carbon acid - (d)-alpha,alpha-phenylmethylacetophenone -is dependent upon the difference in basic strength between the acid and catalysing base. Isotope effects were determined from the ratio of the rate of racemisation to the rate of detritiation for the selected ketone, and reactions were carried out in ethanol-ethoxide-dimethyl sulphoxide solutions. Chapter 2 is an account of the development of a novel method for determining the equilibrium acidity constant of weak carbon or nitrogen acids, using the difference obtained in the rate of detritiation of a standard weak acid, when the detritiation reaction is carried out in the presence, and absence, of another non-tritiated weak acid. The acidities of some weak carbon and nitrogen acids were determined in water-dimethyl sulphoxide solutions containing tetramethylammonium hydroxide. Chapter 3 describes a further attempt to show a relationship between the kinetic hydrogen isotope effect for a weak nitrogen acid - nitramide - and the difference in basic strength between the acid and catalysing base. Isotope effects were determined from a ratio of the rate of decomposition of nitramide when the reaction was conducted in water to that obtained when the reaction was conducted in deuterium oxide.