화학공학소재연구정보센터
Journal of Chemical Thermodynamics, Vol.36, No.7, 575-582, 2004
Calorimetric investigations of hydrogen bonding in binary mixtures containing pyridine and its methyl-substituted derivatives. II. The dilute solutions of methanol and 2-methyl-2-propanol
Enthalpies of solution of methanol and 2-methyl-2-propanol (tert-butanol) in pyridine and its methyl derivatives were investigated in the range of mole fractions of alcohol x less than or equal to 0.02 at temperature 298.15 K by a titration calorimeter. Dissolution of methanol is an exothermic process, with heat effects very close to those for water reported in part I of this study. The negative enthalpy of solution increases in the following order: pyridine < 3-methylpyridine < 4-methylpyridine < 2-methylpyridine < 2,6-dimethylpyridine < 2,4,6-trimethylpyridine. Positive enthalpies of solution of 2-methyl-2-propanol increase as follows: 2-methylpyridine < 2,4,6-trimethylpyridine < 4-methylpyridine < 2,6-dimethylpyridine < 3-methylpyridine < pyridine. The propensity of pyridine derivatives to hydrogen bonding is enhanced by the ortho effect. Methyl groups are probably too small to prevent the nitrogen atom in the pyridine ring from hydrogen bonding. However, spacious hydrocarbon group in 2-methyl-2-propanol molecule makes the bonding difficult for 2,6-dimethylpyridine and 2,4,6-trimethylpyridine, thus the number of O-(HN)-N-... bonds is smaller than that in the solutions of methanol or water. The two latter seem to be very close to each other. (C) 2004 Elsevier Ltd. All rights reserved.