Pulse radiolysis studies of Zn+ reactions

Joseph Rabani*, W. A. Mulac, Max S. Matheson

*Corresponding author for this work

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29 Scopus citations

Abstract

The chemical reactivity of Zn+ toward a number of radicals and molecules was determined using the technique of pulse radiolysis to produce Zn+ in aqueous solutions containing ZnSO4 and one or more of the following: H2, methanol, 2-propanol, 2-methyl-2-propanol, N2O, H2O2, H+, and sodium formate. The following rate constants were measured, all in units M-1 s-1: k(Zn+ + Zn+) = (3.5 ± 1.0) × 108, -d(Zn+)/dt = 2k(Zn+)2; k(Zn+ + H) = (1.9 ± 0.5) × 109; k(Zn+ + CH2OH) = (2.5 ± 0.3) × 109; k(Zn+ + (CH3)2COH) = (1.3 ± 0.25) × 109; k(Zn+ + N2O) = (1.6 ± 0.15) × 107, assuming 0.02 M N2O/atm; k(Zn+ + H2O2) = (2.45 ± 0.2) × 109; k(Zn+ + CO2-) ≃ 4 × 109; k(Zn+ + acetone) < 108 and maybe much smaller; k(CO2- + Zn2+) < 2 × 104; k(eaq- + Zn2+) = (9.5 ± 0.3) × 108 × 10-2.04μ1/2/(1 + μ1/2); where μ is the ionic strength due to ZnSO4, MgSO4, or MnSO4 in the range 0-0.2 M. A number of extinction coefficients at 310 nm were determined: εZn+ = 13 000 ± 1 000, εCH2OH = 270 ± 15, ε(CH3)2COH = 353 ± 15, and εCH2C(CH3)2OH < 10 M-1 cm-1. Except for εZn+ these agree with previously published values. Our measurements of the rate constants for two alcohol radicals reacting also agree with earlier results: k(CH2OH + CH2OH) = (1.5 ± 0.1) × 109 and k((CH3)2COH + (CH3)2COH) = (6.5 ± 0.5) × 108. The Zn+ reactions and the relation of this work to earlier work are discussed. Atomically dispersed Zn0, from Zn+ + Zn+, reacts with water at pH 3 in less than 1 s.

Original languageEnglish
Pages (from-to)99-104
Number of pages6
JournalJournal of Physical Chemistry
Volume81
Issue number2
DOIs
StatePublished - 1977

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