390 Kontny and Zografi ll. THE WATER SORPTION ISOTHERM ‘The most fundamental manner of demonstrating the relationship between sorbed water vapor and a solid is the water sorption-desorption isotherm. The water sorptiondesorption isotherm describes the relationship between the equilibrium amount of water vapor sorbed to a solid (usually expressed as amount per unit ‘mass or'per unit surface area of solid) and the thermodynamic quantity, water activity (aw), at constant temperature and pressure. At equilibrium the chemical potential of water sorbed to the solid must equal the chemical potential of water in the vapor phase. Water activity in the vapor phase is related to chemical potential by w= Bo + RT In ay a) where j1 is the chemical potential of water in the system at equilibrium, 42° is the standard chemical potential of water at a specific reference temperature and pressure, R is the gas constant, and 7 is absolute temperature. Lewis et al. (2] defined the relative activity of any pure substance or component (such as water) as a ratio of fugacities: fu fw where fy is the fugacity of water in the system at equilibrium and f,° is the fugacity of pure water at a standard temperature and pressure. For ali practical purposes, the fugacity (or “escaping tendency”) of water vapor can be approxi- ‘mated by the water vapor pressure in the system. This assumption is valid as Jong as the water vapor behaves as an ideal gas. For the water pressure range of usual interest at temperatures less than 50°C, this approximation is excellent (0.2% relative error) (3]. Thus, the relative pressure of water vapor, P/P®, is usually employed as an estimate of the relative water activity in the system: ank @ ay = @ where P is the water vapor pressure in the system and P° is the vapor pressure above pure water at the temperature of interest. Relative humidity (RH) is defined as the relative pressure expressed on a percentage basi P xs 4 100 x @ The sorption branch of the isotherm is obtained experimentally by ‘measuring the equilibrium amount of water sorbed to a solid at known relative pressure, beginning with a known mass of absolutely dry solid and then Progressively increasing the relative pressure in the system. Drying the solid RH