Kinetics of the Reaction of Iodate Ion with Hypophosphorous Acid

Author: Hayward, Philip

Year: 1948

Degree: Dissertation (Ph.D.)

Advisor: Yost, Don M.

Committee Member: Unknown, Unknown

Option: Chemistry; Mathematics

DOI: 10.7907/epfx-ve54

Abstract

The hypothesis that a normal and an active form of hypophosphorous acid coexist in aqueous solution, and that the conversion of the normal to the active form can be a rate-determining step in its reactions, is supported by a study of the kinetics of its reaction with iodate ion.

The rate law [Formula. See abstract in scanned thesis for details] is found to be in agreement with observation, the best values of the constants at 30° being 9.7 moles-1 1 hr-1 for k1 and 0.44 for k2 /k3. The respective activation energies are 17 kcal. and 4.5 kcal.

It is probable that the iodate ion reacts with the active form of hypophosphorous acid at a much lower rate than do other substances conforming to this rate law. No evidence could be detected for a reaction involving the hypophosphite ion.

The addition of small amounts of n-propanol to the reaction mixtures is found to be helpful, in that some side reactions are thereby suppressed.

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