Kinetic and equilibrium studies of the acid dissociation of the copper(II) and nickel(II) complexes of 5,7-dioxo-1,4,8,11-tetra-azacyclotetradecane期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

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Kinetic and equilibrium studies of the acid dissociation of the copper(II) and nickel(II) complexes of 5,7-dioxo-1,4,8,11-tetra-azacyclotetradecane

Authors:

Robert W Hay Mansour M Hassan

Institution:

1. Chemistry Department, University of St Andrews, K Y169ST, St Andrews, UK

Abstract:

The acid catalysed dissociation of the copper(II) and nickel(II) complexes of 5,7-dioxo-1,4,8,11-tetra-azacyclo-tetradecane (dioxocyclam = LH₂) has been studied using nitric acid solutions over a range of temperatures at I = 1.0 mol dm si-³. The kinetic data for the copper complex can be fitted to the rate expression k _obs = k K ₂H⁺]/(1 + K ₂ H⁺] with K = 24.7s⁻¹ and K ₂ = 65dm³mol⁻¹ at 25° C. The analogous constants for the nickel(II) complex are K = ³.³s⁻¹ and K ₂ = 45dm³mol⁻¹. The acid dissociation can be rationalized in terms of the kinetic scheme

$\begin{gathered} ML + H^ + MLH^ + \hfill \\ MLH^ + + H^ + MLH_2^{2 + } \hfill \\ MLH_2^{2 + } \xrightarrow{k}M^{2 + } + LH_2 \hfill \\ \end{gathered}$

Keywords:
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