Kinetics of the Initial Reaction of Nitrite Ion in Bisulfite Solutions

The kinetics of the reaction of nitrite ion in bisulfite solutions to form hydroxylamine disulfonate have been investigated. Evidence has been presented that nitrososulfonic acid is an intermediate in this reaction, and it can undergo sulfonation or hydrolysis reactions. The hydrolysis reaction yields N20 under the present conditions of study (acid solutions) which complicates the determination of the rate of formation of hydroxylamine disulfonate. The ratio of the rate constants for sulfonation and hydrolysis (kA/k8) is 1.7 ± 0.5. The previously determined rate law for the formation of the disulfonate has been verified, although one term has been shown to be dependent on which buffer solution is chosen to maintain the desired acidity. t Also Department of Chemistry, University of California, Berkeley, California 94720. This work was supported by the Assistant Secretary for the Environment, Office of Health and Environmental Research, Pollutant Characterization and Safety Research Division of the U.S. Department of Energy under contract No. W-7405-ENG-48 and the Morgantown Energy Technology Center, U.S. Department of Energy, under contract No. 80MC14002.