Reactivity of solvated electrons in tetrahydrofuran

Abdul Amir H. Kadhum, G. Arthur Salmon

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The rates of reaction of solvated electrons (es -) with 23 solutes have been measured in tetrahydrofuran at 22±1 °C. The values range form (1.5±0.4) × 109 dm3 mol-1 s-1 for phenol to (1.56±0.01) × 1011 dm3 mol-1 s-1 for benzonitrile. It is concluded that the diffusion-controlled rate constant for reactions of es - in this solvent is ca. 1.7 × 1011 dm3 mol-1 s-1, which indicates that the sum of the reaction radii of es - and the solute is ca. 1.67 nm. This value is close to the value of 1.38 nm, estimated for the maximum reaction radius of e- in the gas phase. The effect of ΔG for the reaction on the rate constant is investigated and evidence is presented for an inversion in the rate in the highly exergonic region, although a few solutes deviate from the general trend. The temperature dependence of the rate constants for five solutes has been measured and the values of the activation energy lie in the range 11.7-15.4 kJ mol-1. It is concluded that the rate constants for the electron-scavenging process qualitatively conform to the predictions of quantum-mechanical theories for electron-transfer reactions.

Original languageEnglish
Pages (from-to)2521-2530
Number of pages10
JournalJournal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
Volume82
Issue number8
DOIs
Publication statusPublished - 1986
Externally publishedYes

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tetrahydrofuran
reactivity
Rate constants
Electrons
solutes
electrons
Scavenging
Phenol
radii
scavenging
phenols
Activation energy
Gases
electron transfer
inversions
vapor phases
activation energy
trends
temperature dependence
predictions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Reactivity of solvated electrons in tetrahydrofuran. / Kadhum, Abdul Amir H.; Salmon, G. Arthur.

In: Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 82, No. 8, 1986, p. 2521-2530.

Research output: Contribution to journalArticle

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