Statistical rate theory examination of ethanol evaporation.

A series of low-temperature (246 < T(I)(L) < 267 K) steady-state ethanol evaporation experiments have been conducted to determine the saturation vapor pressure of metastable ethanol. The measured interfacial conditions have been used with statistical rate theory (SRT) to develop an expression for the saturation vapor pressure as a function of temperature, f(srt)(eth). This expression is shown to be thermodynamically consistent because it gives predictions of both the evaporative latent heat and the liquid constant-pressure specific heat that are in agreement with independent measurements of these properties. In each experiment, the interfacial vapor temperature was measured to be greater than the interfacial liquid temperature, [triple bond]DeltaT(I)(LV). When f(srt)(eth) is used in SRT to predict DeltaT(I)(LV), the results are shown to be consistent with the measurements. Other expressions for the saturation vapor pressure that are in the literature are examined and found to be thermodynamically inconsistent and do not lead to valid predictions of DeltaT(I)(LV).