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• W2022869079 abstract "The rate constant ks of solvated electron reaction with a solute S in an alcohol can depend strongly upon the electron solvation energy (trap depth) and on the liquid viscosity η (diffusion coefficients). The rate constant tends to be smaller when either the solvation energy or the viscosity is larger. An appropriate indicator of solvation energy in this context is Er, the energy at 0.5 Amax on the low energy side of the optical absorption band. Differences in solvent viscosity are normalized by taking the ratio ks/kN, where N is nitrobenzene and kN is nearly diffusion controlled. There is an enormous difference between kS/kN for an inefficient S such as toluene in monohydric and dihydric alcohols. At Er= 146 kJ/mol the value of k (toluene)/kN is 200 fold greater in a di-ol than in a mono-ol. This remarkable difference between reactivity in di- and mono-ols is smaller for more reactive solutes; the factor is 60 for allyl alcohol and 2 for acetone. In both di- and mono-ols differences in solute reactivity are associated with entropy of activation, not with energy of activation. The entropy of activation is related to the extent of solvent rearrangement that is needed about the reaction site to give a stable product. The value of kS for the efficient scavenger nitrobenzene varies approximately as η−-0.6 for a series of both mono- and di-ols. The value of kS for an inefficient scavenger such as toluene is relatively insensitive to viscosity. The value of the ratio k (toluene)/kN≃10-3 indicates that the probability of reaction per encounter between e-s and toluene at 298 K is ≲ 10−3. For such inefficient reactions the lower encounter rate in a more viscous solvent is largely compensated by the longer duration of each encounter, with little net change in overall reaction efficiency. There is need of dielectric relaxation time information about diols in the single component liquid phase." @default.
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• W2022869079 date "1984-01-01" @default.
• W2022869079 modified "2023-09-27" @default.
• W2022869079 title "Solvent effects on solvated electron reaction rates in diols" @default.
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• W2022869079 doi "https://doi.org/10.1016/0146-5724(84)90097-9" @default.
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