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DOI: 10.1039/A707377A (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1998, 94, 653-657

Reactivity of chlorine atoms in aqueous solution Part 1The equilibrium ClMNsbd+Cl-Cl2-

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George V. Buxton, Mark Bydder and G. Arthur Salmon

Abstract

The equilibrium constant for reaction (1) has been determined in neutral solution to be (1.4±0.1)×105 d mol-1, with forward and reverse rate constants, k1 and k-1, of (8.5±0.7)×109 d mol-1 s-1 and (6.0±0.5)×104 s-1, respectively.

At 25°C the rate constants for the reactions of ClNsbd and Cl2- were measured to be (2.5±0.3)×105 s-1 and (1.3±0.1)×103 s-1 with water and (6.5±0.6)×108 d mol-1 s-1 and ca. 0, within experimental error, with 2-methyl-propan-2-ol. Deviation from the equilibrium values of [ClNsbd] and [Cl2-] in the early stages of the reactions was investigated and shown to account for the discrepancy between the value of K1 determined here and a previous estimate from our laboratory.

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