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- W2066424871 abstract "Gas−liquid scattering, D → H exchange, and time-dependent uptake measurements are used to follow HCl, DCl, and HBr as they strike the surface of the neutral, hydrogen-bonding liquid glycerol. In this and the following paper, we report studies of gas−liquid energy transfer and trapping, the nature of HCl and HBr interfacial and bulk phase dissociation and recombination, and the thermodynamics of HCl solvation. We find that most HCl and HBr molecules readily dissipate their excess kinetic energy and thermalize at the surface of glycerol, even at impact energies up to 100 kJ mol-1 and glancing angles of incidence up to 60°. Nearly all thermally accommodated HBr molecules dissolve in glycerol for longer than 10 s. HCl is less acidic and dissolves reversibly for times of 0.1 to 1 s at incident HCl fluxes of (2 to 0.2) × 1015 cm-2 s-1, respectively. Experiments utilizing DCl show that this reversible solvation is accompanied by dissociation into D+ and Cl-, D+ → H+ exchange, and HCl desorption. The residence times of HCl in glycerol and their temperature dependences yield = −19 ± 2 kJ mol-1, = −67 ± 4 kJ mol-1, and = −165 ± 20 J mol-1 K-1 for HCl(g) ⇌ H+(gly) + Cl-(gly) at 294 K." @default.
- W2066424871 created "2016-06-24" @default.
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- W2066424871 date "2002-04-23" @default.
- W2066424871 modified "2023-10-11" @default.
- W2066424871 title "Collisions of HCl, DCl, and HBr with Liquid Glycerol: Gas Uptake, D → H Exchange, and Solution Thermodynamics" @default.
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- W2066424871 doi "https://doi.org/10.1021/jp013960w" @default.
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