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The kinetics and mechanism of a free radical decay in aqueous solution

The decomposition of nitrosyl disulfonate ion was studied in strongly alkaline solution of 10-2 to 5 m sodium hydroxide. The decomposition was found to be first-order in both hydroxide and nitrosyl disulfonate ions. A multi-step mechanism involving sulfite ion, sulfite ion radical and nitrosyl monosulfonate ion radical as intermediates was proposed, with the initiating step being the SN2 replacement of a sulfite ion by a hydroxide ion. The rate constant for the initiating step ranged from 1.2 x 10-7 to 2.25 x 10-5 M-1s-1 for the solution concentration range of the study. The products of the decomposition were identified as hydroxylamine disulfonate ion, hydroxylamine trisulfonate ion, and nitrite ion. The proposed mechanism was applied to the previously studied decomposition in mildly alkaline to slightly acidic, and nonaqueous solutions and found to explain all the reported observations if the side reactions involving the hydrolysis and reversion of hydroxylamine disulfonate ion were included.

Identiferoai:union.ndltd.org:BGMYU2/oai:scholarsarchive.byu.edu:etd-9208
Date01 April 1975
CreatorsFillmore, Denzel Lee
PublisherBYU ScholarsArchive
Source SetsBrigham Young University
Detected LanguageEnglish
Typetext
Formatapplication/pdf
SourceTheses and Dissertations
Rightshttp://lib.byu.edu/about/copyright/

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