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Solution Dynamics in Aqueous Monohydric Alcohol Systems

William S. PriceDepartment of Chemistry, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachioji, Tokyo 192-0397, Japan, FLW, Food Research & Development Laboratories, Ajinomoto Co., Inc. 1-1, Suzuki-cho, Kawasaki-ku, Kawasaki-shi 210-8681, Japan, and Water Research Institute, Sengen 2-1-6, Tsukuba, Ibaraki 305-004, JapanHiroyuki IdeDepartment of Chemistry, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachioji, Tokyo 192-0397, Japan, FLW, Food Research & Development Laboratories, Ajinomoto Co., Inc. 1-1, Suzuki-cho, Kawasaki-ku, Kawasaki-shi 210-8681, Japan, and Water Research Institute, Sengen 2-1-6, Tsukuba, Ibaraki 305-004, JapanYoji ArataDepartment of Chemistry, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachioji, Tokyo 192-0397, Japan, FLW, Food Research & Development Laboratories, Ajinomoto Co., Inc. 1-1, Suzuki-cho, Kawasaki-ku, Kawasaki-shi 210-8681, Japan, and Water Research Institute, Sengen 2-1-6, Tsukuba, Ibaraki 305-004, Japan

2003en

ABI

Annotatsiya

The associative behavior of aqueous methanol, ethanol, and tert-butyl alcohol solutions at mole fractions ranging from 0 to 1 at 273, 283, and 298 K was examined using PGSE NMR measurements of the self-diffusion coefficients of the alkyl group, water and, depending on the exchange rate, hydroxyl protons. The results show that tert-butyl alcohol has the greatest ability to stabilize water through hydrophobic hydration than methanol or ethanol due to the more ideal fit of the tert-butyl group to the structure of water. However, at higher concentrations tert-butyl alcohol is the least able to cohesively interact with water through hydrogen bonding. The results provide compelling evidence for alcohol self-association (methanol < ethanol < tert-butyl alcohol) in very dilute solution. The alcohol molecules can be likened to very short lipid molecules undergoing complicated solution interactions due to their amphiphilic nature.

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DOI: 10.1021/jp027257z

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