Thermodynamics of Water Interaction with Human Stratum Corneum I: Measurement by Isothermal Calorimetry

A thermodynamic study of water interaction with human stratum corneum (SC) is presented. The procedure consisted of conjoint water vapor sorption and heat flow measurements. Heat of sorption of water in excised human SC at various relative humidities was measured in an isothermal calorimeter at 32°C using back and thigh skin from three different donors. These measurements, combined with the gravimetric sorption isotherm, were used to calculate the integral and differential enthalpies and entropies associated with binding of water to SC. Differential enthalpy values suggest hydrogen‐bonding interactions similar to those for water in wool keratin. The changes in differential enthalpy and entropy with increasing water content followed a pattern similar to that seen in wool and other hydrophilic polymers. The results are partially interpreted in terms of a BET isotherm with monolayer volume vm = 0.022 g H2O/g dry SC and binding parameter C = 6.5 × 108.