TY - JOUR
T1 - Reactions of aliphatic free radicals with copper cations in aqueous solutions. Part 3. - Reactions with cuprous ions
T2 - A pulse radiolysis study
AU - Freiberg, Mira
AU - Mulac, William A.
AU - Schmidt, Klaus H.
AU - Meyerstein, Dan
N1 - Funding Information:
D. Walsh and R. M. Clarke in performing the experiments isgratefully acknowledged. This study was supported in part by the United States-Israel Binational Science Foundation (B.S.F.) Jerusalem, Israel and by the IsraelCommission for Basic Research, and was performed in part under the auspices ofthe Division of Basic Energy Sciences of the U.S. Department of Energy.(a) M. Freiberg and D. Meyerstein, J.C.S. Chem. Comm., 1977, 934. (b) M. Freiberg andD. Meyerstein, J.C.S. Faruday I, 1980, 76, 1825.(a) J. K. Kochi, in Free Radicals, ed. J. K. Kochi (Wiley, New York, 1973), vol. I, chap. 11 ;(b) J. K. Kochi, Accounts Chern. Res., 1974, 7, 351 ; (c) C. Walling, Accounts Chem.
PY - 1980
Y1 - 1980
N2 - Helium-saturated solutions containing copper sulphate and an aliphatic alcohol (methanol, ethanol or propan-2-ol) were pulse irradiated. The kinetics of the reactions thus initiated were followed by the spectrophotometric and conductometric techniques. The results indicate that all three radicals, ·CR1R2OH, react with Cuaq2+ to yield Cuaq+ + CR1 R2O + H3O+. ·CH2OH radicals react with Cuaq2+ according to Cuaq+ + ·CH2OH ⇄ CuII-CH2OH+, K ≈ 5 × 103 dm3 mol-1. The corresponding equilibrium constants for CuII-CH(CH3)OH+ and CuII-C(CH3)2OH+ are too low to be measured and the corresponding intermediates are not observed. Cuaq+ reacts with the β radicals, ·CH2CH2OH and ·CH2CH(CH3)OH, according to Cuaq2+ + ·CH2CR1R2OH → CuII-CH2CR1R2OH+. The latter intermediates decompose via acid catalysed reactions to yield Cuaq2+ + H2C=CR1R2 + H2O.
AB - Helium-saturated solutions containing copper sulphate and an aliphatic alcohol (methanol, ethanol or propan-2-ol) were pulse irradiated. The kinetics of the reactions thus initiated were followed by the spectrophotometric and conductometric techniques. The results indicate that all three radicals, ·CR1R2OH, react with Cuaq2+ to yield Cuaq+ + CR1 R2O + H3O+. ·CH2OH radicals react with Cuaq2+ according to Cuaq+ + ·CH2OH ⇄ CuII-CH2OH+, K ≈ 5 × 103 dm3 mol-1. The corresponding equilibrium constants for CuII-CH(CH3)OH+ and CuII-C(CH3)2OH+ are too low to be measured and the corresponding intermediates are not observed. Cuaq+ reacts with the β radicals, ·CH2CH2OH and ·CH2CH(CH3)OH, according to Cuaq2+ + ·CH2CR1R2OH → CuII-CH2CR1R2OH+. The latter intermediates decompose via acid catalysed reactions to yield Cuaq2+ + H2C=CR1R2 + H2O.
UR - http://www.scopus.com/inward/record.url?scp=37049091938&partnerID=8YFLogxK
U2 - 10.1039/F19807601838
DO - 10.1039/F19807601838
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AN - SCOPUS:37049091938
SN - 0300-9599
VL - 76
SP - 1838
EP - 1848
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
ER -