Abstract
The decomposition of sodium dithionite in concentrated bisulphite buffer solutions follows first-order kinetics with an activation energy of 18 kcal/mole. The rate is also first order in bisulphite ion, variable fractional order in hydrogen ion and shows zero salt effect. The reaction ˙HSO2+˙SO 2+HSO 3→intermediate products (3) is proposed as the rate-determining step. Two sets of stable products, (½Na2S2O3+NaHSO3) and (Na2S3O6), found in ratios between 9 : 1 and 1 : 1, probably result from common intermediates in reaction (3). These results are combined with those of hydrolysis to give a unified account of dithionite decomposition.
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