期刊
JOURNAL OF CHEMICAL PHYSICS
卷 131, 期 4, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.3187544
关键词
adsorption; amorphous state; chemical exchanges; dissociation; heavy water; ice; monolayers; reaction rate constants; sputtering; surface chemistry
资金
- Korea government (MEST) [R11-2007-012-02001-0]
- National Research Foundation of Korea [2007-0056333, 과06A1501, R11-2007-012-02001-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
The effect of hydroxide ions on proton transfer and H/D isotopic exchange of water molecules was examined at the surface of amorphous ice films at temperatures of 92-140 K. Excess hydroxide ions were provided onto a D2O-ice film by the hydrolysis of Na atoms, and H2O was adsorbed onto the surface for a submonolayer coverage. The H/D isotopic exchange between H2O and D2O molecules on the ice film surface was monitored as a function of reaction time and temperature by using the techniques of reactive ion scattering and low-energy sputtering. The result was compared with that obtained on a hydroxide-free ice film. At a temperature of 92 K, proton transfer occurred from water mostly to adjacent hydroxide ions. The proton transfer distance and the H/D exchange reaction rate increased with increase in temperature above 105 K. The H/D exchange reaction propagated to several water molecules on the surface at 100-120 K. Kinetic measurement in this temperature range deduced the Arrhenius activation energy for the reaction, E-a=9.6 +/- 2.0 kJ mol(-1). The study shows that hydroxide ions promote the H/D exchange reaction on the ice surface compared with that on a hydroxide-free ice surface, but the promotion effect is moderate and the H/D exchange occurs on a substantial energy barrier. It is suggested that the stabilization of hydroxide ions at the ice surface produces an energy barrier for the proton transfer.
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