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Type of Document	Dissertation
Author	Jenkins, Wilmer Atkinson
URN	etd-04242003-090233
Persistent URL	http://resolver.caltech.edu/CaltechETD:etd-04242003-090233
Title	The kinetics of the exchange of radioactive hydrogen between hypophosphorous acid and water. An investigation of some aspects of the chemistry of hypophosphorous acid and thallous hypophosphite. A new assay method for tritiated water
Degree	PhD
Option	Chemistry
Advisory Committee	Advisor Name Title Unknown Committee Member
Keywords	None
Date of Defense	1953-01-01
Availability	unrestricted
Abstract The kinetics of the exchange of radioactive hydrogen between hypophosphorous acid and water have been studied in acid, neutral, and basic solution. In acid solution the kinetics of the exchange were found to be the same as the kinetics of the oxidation of hypophosphorous acid by certain oxidizing agents. The mechanism common to both of these reactions is formulated and discussed. The isotope effect found in acid solution is explained, and a general theory of isotope effects in exchange reactions is presented. Exchange was found to be extremely slow in neutral solution and a little faster in basic solution; the results in basic solution, however, were complicated by the decomposition of the hypophosphite ion. A new method for the purification of hypophosphorous acid is described. Experiments on the preparation and thermal stability of thallous hypophosphite were conducted. These experiments are presented and discussed, along with some data on the reaction of hypophosphorous acid with persulfate and dichromate. A new, rapid assay method for tritiated water, involving the use of solid samples and a windowless flow counter, is described.
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