Stopped-flow acid-base catalysis

In a semi-quantitative stopped-flow study, based only on yields of chlorine dioxide, (15) was found to be faster than (16), with (17) always occurring but of most significance for low concentrations of chlorous acid. With excess sodium chlorite, the yield of chlorine dioxide could be in excess of that predicted by (15) so that catalysis (by CI2 or by HCIO) of a chlorite reaction seems probable. Reactions (15) and (16) are both approximately second order. The mechanism, suggested to be consistent with Dodgen and Taube s results , involves the steps... 

Pocket, Y. and D. W. Bjorkquist (1977) Stopped-flow studies of carbon dioxide hydration and bicarbonate dehydration in H2O and D2O. Acid-base and metal ion catalysis./. Am. Chem. Soc. 99, 6537-43. 

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