Temperature dependence of limiting activity coefficients, Henry's law constants, and related infinite dilution properties of branched (C3 and C4) alkanols in water. Measurement, critical compilation, correlation, and recommended data

摘要

Limiting activity coefficients (gamma(infinity)(1)) of lower branched alkanols (2-propanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol) in water were measured at several temperatures covering the range from the melting to the normal boiling point of water. Four experimental techniques ( namely, headspace analysis, inert gas stripping, Rayleigh distillation, and the method of circulation still) were employed for the purpose. A comprehensive review is further presented of experimental data on the limiting activity coefficients (gamma(infinity)(1)), infinite dilution partial molar excess enthalpies ((H) over bar (E,infinity)(1)), and heat capacities ((C) over bar (E,infinity)(p,1)) of these aqueous solutes. For each alkanol, the compiled data were critically evaluated and together with the data measured in this work correlated with a suitable model equation providing adequate simultaneous description of the equilibrium measurements and the calorimetric information. As a result, a recommended thermodynamically consistent temperature dependence of gamma(infinity)(1), (H) over bar (E,infinity)(1), and (C) over bar (E,infinity)(p,1) of superior accuracy was established in the range from the melting point to the normal boiling point of water. In addition, by employing literature data on the respective residual properties of the pure alkanols, analogous recommendations were derived also for the temperature dependence of the Henry's law constants, hydration enthalpies, and hydration heat capacities. Variation of these various infinite dilution thermodynamic properties of aqueous branched alkanols with temperature and alkanol branching is briefly discussed.