Abstract
A strong 1:1 inclusion complex is formed (Kα= 4 690 dm3 mol–1) between Br2 and α-cyclodextrin (cd). The reaction kinetics between HCOOH and Br2(aq)([H+]= 0.1 mol dm–3) with bromide present in large excess, have been studied potentiometrically both in the presence and absence of cd. It is shown that Br2 with cd is about half as reactive as aqueous Br2, and it would appear from the activation parameters that Br2 should be released from inclusion during the rate-limiting step. However, despite the stabilization of Br2 by cd, addition of the latter makes the experimental rate constant increase. The reason for this apparent contradiction is that non-reactive tribromide is transformed by cyclodextrin into mildly reactive Br2cd. The rate constants (25 °C, I= 0.2 mol dm–3) for the oxidation of HCOO– by Br2 and Br2cd are 27 and 15 dm3 mol–1 s–1, respectively.
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