Abstract
The kinetics of base hydrolysis of the trans-[Cr(NH3)2(NCS)4]− anion follows the rate law: -d[complex]/dt = k0 + k1[OH−] (50–70 °C, [OH−] = 0.1–1.9 M and μ = 2.0 M). The specific salt effect has been investigated for eight aqueous media: NaCl, NaBr, NaI, NaClO4, KCl, KBr, CsCl and CsBr. The alkali-independent path (k0) does not show any specific effect of inert electrolyte ions, the activation parameters: ΔH‡ = 113.5 ± 0.4 kJ mol−1 and ΔS‡ = 24.1 ± 1.3 J mol−1 K−1 are interpreted in the frame of a dissociative interchange mechanism (Id). For the alkali-dependent path (k1) the specific salt effect is observed for cations of the inert electrolyte, showing an important role for ion-pair formation between the cations and reagent complex anion in the activation process. A linear correlation between lnk1 and lnK0 (K0 – ion-pair formation constant) has been found for the cations studied. The dissociative, via conjugate base, mechanism (DCB) has been proposed for the alkali-dependent path.
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