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- W2940624596 abstract "The partial molar volume of the hydrated electron was investigated with pulse radiolysis and transient absorption by measuring the pressure dependence of the equilibrium constant for e-aq + NH4+ ⇔ H + NH3. At 2 kbar pressure, the equilibrium constant decreases relative to 1 bar by only 6%. Using tabulated molar volumes for ammonia and ammonium, we have the result V̅(e-aq) - V̅(H) = 11.3 cm3/mol at 25 °C, confirming that V̅(e-aq) is positive and even larger than the hydrophobic H atom. Assuming on the basis of recent molecular dynamics simulations that the molar volume of the H atom is somewhat less than that of H2, we estimate V̅(e-aq) = 26 ± 6 cm3/mol. The positive molar volume is consistent with an electron that exists largely in a small solvent void (cavity), ruling out a recent model ( Larsen , R. E. ; Glover , W. J. ; Schwartz , B. J. Science 2010 , 329 , 65 - 69 ) that suggests a noncavity structure with negative molar volume." @default.
- W2940624596 created "2019-05-03" @default.
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- W2940624596 date "2019-04-22" @default.
- W2940624596 modified "2023-09-24" @default.
- W2940624596 title "Partial Molar Volume of the Hydrated Electron" @default.
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- W2940624596 doi "https://doi.org/10.1021/acs.jpclett.9b00445" @default.
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