Abstract

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.

Degree

PhD

College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry

Rights

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