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Solvent effects on the rate of reaction of Cl 2 ˙− and SO 4 ˙− radicals with unsaturated alcohols
Author(s) -
Alfassi Z. B.,
Padmaja S.,
Neta P.,
Huie R. E.
Publication year - 1993
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550250303
Subject(s) - chemistry , reaction rate constant , solvent , radical , solvation , aqueous solution , solvent effects , solvatochromism , atmospheric temperature range , reaction rate , organic chemistry , kinetics , thermodynamics , catalysis , physics , quantum mechanics
Rate constants have been measured in several aqueous/organic solvent mixtures for the addition reaction of Cl 2 ˙− radicals with 2‐propen‐1‐o1 and 2‐buten‐1‐o1 as a function of temperature and with 2, 3‐dimethyl‐2‐butene at room temperature. The rate constants were in the range of 10 6 –10 9 L mol −1 s −1 , the activation energies were relatively low (1–10 kJ mol −1 ), and the pre‐exponential factors varied over the range log A = 7.9 to 9.4. The rate constants ( k ) decreased (by up to a factor of 30) upon increasing the fraction of organic solvent and log k correlated linearly with the dielectric constant for a given water/organic solvent system, but the lines for the different solvent systems had different slopes. A better correlation of log k was found with a combination of the solvatochromic factor, E T (30), and the hydrogen‐bond donor acidity factor, α. This suggests that the rate of reaction is influenced by the solvent polarity and also by specific solvation of the ionic reactant and product. Solvent effect on the reaction of SO 4 ˙− with 2‐propen‐1‐o1 was studied for comparison. © 1993 John Wiley & Sons, Inc.