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- W2020004811 abstract "The nearly diffusion controlled reaction rate constants k2 of solvated electrons with efficient electron capturers in butanol/water mixtures are examined according to the Smoluchowski, Debye, and trap-depth models. The k2 values depend on the diffusion rates of the reactants and the solvation energies of the electrons. Both these factors are affected by the rigidity of the alkyl group on the alcohol. Increased rigidity decreases the diffusion rate, which tends to decrease k2, and decreases the electron solvation energy, which tends to increase k2. Rate constants of efficient electron capturing solutes are dominated by the former, those of inefficient capturers by the latter. The free energy of activation ΔG‡13 for electron capture by an inefficient electron scavenger (solute) is empirically related to Er/ f(μ), where Er is a representative optical absorption energy of the solvated electrons (related to the solvation energy) and f(μ) is a function of the dipole moment of the scavenger. It is also related to the polarizability of the solvent molecules. Capture by an inefficient solute has a large negative entropy of activation attributed to solvent rearrangement about the reaction site." @default.
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- W2020004811 date "1987-12-15" @default.
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- W2020004811 title "Solvent structure effects on electron reactivity in isomeric butanol/water mixtures" @default.
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- W2020004811 doi "https://doi.org/10.1063/1.453398" @default.
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