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Critical Review of Rate Constants for Reactions of Transients from Metal Ions and Metal Complexes in Aqueous Solution

George V. Buxton

University of Leeds,
Cookridge Radiation Research Centre,
Leeds, LS16 6QB, U.K.

Quinto G. Mulazzani

Istituto di Fotochimica e Radiazioni d'Alta Energia,
Consiglio Nazionale delle Ricerche,
Via P. Gobetti 101, 40129 Bologna, Italy

Alberta B. Ross

Radiation Chemistry Data Center,
Radiation Laboratory, University of Notre Dame, Notre Dame, IN 46556

J. Phys. Chem. Ref. Data 24: 1055-1349 (1995)

Kinetic data for transient metal species in aqueous solution have been critically reviewed. The compilation covers over 2000 measurements of rate constants involving 660 metal ions and metal complexes from Groups 4-15; lanthanides and actinides are not included. Most of the data have been obtained by the methods of pulse radiolysis or flash photolysis. Data have been collected from 500 publications through 1993.

Arrangement of Data:

These data have not been arranged for browsing, but may be searched by the name of either of the reactants.

Values of k are in units of L mol^–1 s^–1. The unit of s^–1 is included with the value of k when it refers to a first-order reaction or a bimolecular reaction with water. pH is included in the entry when it is reported by the authors or if it can be calculated from the concentration of H⁺ or OH^– in the solution. The ionic strength is entered only when it is reported by the authors. The number of significant figures quoted by the authors has been retained. Most data have been obtained at ambient temperature which is not always reported. Unless the temperature was specified it has been omitted, but in those cases it can be taken to be the room temperature.

The comments contains detailed information in abbreviated form in the following order: The wavelength of measurement if appropriate; the composition of the solution; values of k obtained under other specified conditions. Where a reaction is reversible and the rate constant for the reverse reaction is also known it is reported as k_r. When a value of k has been obtained by computer fitting this is stated. Activation parameters, E_a, DH^‡ and DS^‡, are quoted if they are known. Also included in this column are rate constants for further changes in the primary product.

Abbreviations and Symbols.

Introduction to Transients from Metal Ions.