Temperature Dependences of Limiting Activity Coefficients, Henry’s Law Constants, and Derivative Infinite Dilution Properties of Lower (C1–C5) 1-Alkanols in Water. Critical Compilation, Correlation, and Recommended Data

Abstract

A comprehensive review is presented of experimental data on the limiting activity coefficients γ1∞, infinite dilution partial molar excess enthalpies H¯1E,∞ and heat capacities C¯p,1E,∞ of lower 1-alkanols (C1–C5) in water. For each alkanol, the compiled data are critically evaluated and correlated with a suitable model equation providing adequate simultaneous description of the equilibrium measurements and the calorimetric information. As a result, recommended thermodynamically consistent temperature dependences of γ1∞, H¯1E,∞, and C¯p,1E,∞ of superior accuracy are 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 1-alkanols, analogous recommendations are also derived for the temperature dependences of the Henry’s law constants, hydration enthalpies, and hydration heat capacities. Evolution of the various infinite dilution thermodynamic properties of aqueous 1-alkanols with temperature and homologous series is briefly discussed.

Liquid Water Scavenging of PEMFC Contaminants

“…This value favorably compares to H = 0.0032 and 0.0058 m 3 mol −1 . 55,56 The H = 0.0019 m 3 mol −1 value is also consistent with calculations completed for 80…”

Measurement of infinite dilution activity coefficients of 1-alkanols (C1–C5) in water as a function of temperature (273–373 K)

“…Since in contrast to the linear temperature dependence ofC E,∞ P,1 , Eq. (3) describesC E,∞ P,1 (T ) data for these systems adequately [17], Eq. (1) is preferred here to ln γ ∞ 1 = A + B/τ + C ln τ + Dτ, a more conventional γ ∞ 1 (T ) representation stemming from the assumption of linearC E,∞ P,1 (T ).…”

“…For each system, parameters C, D were evaluated by a weighted least squares fit of Eq. (3) to all availableC E,∞ P,1 (T ) data collected, yielding their representation within experimental errors assigned in the critical evaluation [17]. The respective weighted standard deviations of fit, which correspond approximately to the average (residual/experimental error) ratio, were from 0.6 to 0.83.…”

“…a Uncertainties given correspond to standard errors. For the literature values these uncertainties are based on the critical data evaluation [17] and for the values derived from fits they were calculated using the error propagation law. b Ref.…”

“…As a result, any inconsistency of γ ∞ 1 (T ) with the calorimetric information is reflected then in the deviations of experimental and fitted ln γ ∞ 1 values. The underlying calorimetric information was taken from our comprehensive collection of critically evaluated data on infinite dilution properties for the systems under study which has been presented elsewhere [17]. For each system, parameters C, D were evaluated by a weighted least squares fit of Eq.…”