Abstract
The mutarotation rates of glucose in aqueous mixtures of tetrahydrofuran andtert-butanol in the mole fraction (xi) range 0<xi<0.2 have been measured at 5° intervals in the range 5–35°C. The kinetic deuterium isotope effects have been determined for the same solvent compositions at 25 and 35°C. A statistical analysis of the Arrhenius plots indicates that the experimental errors, although small, are too large for the establishment of any compensation behavior between ΔH ‡ and ΔS ‡ which has often been claimed for reactions in mixed aqueous solvents. Nevertheless, it appears that ΔH ‡ exhibits a complex solvent composition dependence, and the solvent effects on the measured rate constants differ markedly from those found for aqueous solutions ofN,N-dimethyl-formamide and dimethyl sulfoxide. There is a deuterium isotope rate effect for solvent mixtures in which 0<xi<0.1, over and above the usually observed kinetic isotope effect. This additional effect decreases with rising temperature. The results are discussed in terms of competing water ordering effects in ternary mixtures containing water, a hydrophilic solute, and a hydrophobic solute.
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Livingstone, G., Franks, F. & Aspinall, L.J. The effects of aqueous solvent structure on the mutarotation kinetics of glucose. J Solution Chem 6, 203–216 (1977). https://doi.org/10.1007/BF00646739
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DOI: https://doi.org/10.1007/BF00646739