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Sorption isotherm models are frequently used to understand the interactions of water with cellulosic materials. Many commonly used models, such as the Guggenheim-Anderson-de Boer, Hailwood-Horrobin, and Dent isotherm models, are based on idealized physical systems. In the scientific literature, these models are often used to predict properties of wood such as the monolayer capacity, which is a representation of the number of available sorption sites in the material. Reporting such properties assumes that an idealized system adequately represents actual wood-water interactions. These models can be reduced to the same form, where the ratio of water activity, aw, to equilibrium moisture content (EMC), is a second-order polynomial function of aw. Here we review twelve models that have a parabolic form, fit these models to high quality water vapor sorption isotherm data for wood at multiple temperatures, and calculate physical properties from the model parameters. Moreover, variability in model predictions arising from measurement uncertainties in aw and EMC values is propagated using a Monte Carlo method. Predicted physical properties are tested against independently measured values of hydroxyl accessibility, relative amounts of primary and secondary water, and enthalpy of sorption. None of the models accurately predicts any of the physical properties, even when the reported measurement uncertainties are increased by a factor of three. Therefore, it must be concluded that parabolic sorption isotherm models are not valid for water in wood cell walls., Sorption isotherm models are frequently used to understand the interactions of water with cellulosic materials. Many commonly used models, such as the Guggenheim-Anderson-de Boer, Hailwood-Horrobin, and Dent isotherm models, are based on idealized physical systems. In the scientific literature, these models are often used to predict properties of wood such as the monolayer capacity, which is a representation of the number of available sorption sites in the material. Reporting such properties assumes that an idealized system adequately represents actual wood-water interactions. These models can be reduced to the same form, where the ratio of water activity, aw, to equilibrium moisture content (EMC), is a second-order polynomial function of aw. Here we review twelve models that have a parabolic form, fit these models to high quality water vapor sorption isotherm data for wood at multiple temperatures, and calculate physical properties from the model parameters. Moreover, variability in model predictions arising from measurement uncertainties in aw and EMC values is propagated using a Monte Carlo method. Predicted physical properties are tested against independently measured values of hydroxyl accessibility, relative amounts of primary and secondary water, and enthalpy of sorption. None of the models accurately predicts any of the physical properties, even when the reported measurement uncertainties are increased by a factor of three. Therefore, it must be concluded that parabolic sorption isotherm models are not valid for water in wood cell walls.

Sorption of water vapor in cellulosic materials has been studied for more than 100 years. However, the last 2 decades have seen a surge in studies of sorption kinetics due to the adoption of automated sorption balances in laboratories worldwide. Sorption kinetic data is commonly fitted with the parallel exponential kinetics (PEK) model, which is the sum of two exponential functions. The PEK model parameters are often interpreted as representing physical quantities or material properties, but their exact definition remains undetermined. Nonetheless, PEK fitting of sorption data has been widely used to identify various physical properties. Recent work has called into question the protocols used to collect sorption data with automated sorption balances and the methods used to analyze the data. Typically, data acquisition is interrupted before equilibrium when the rate of mass change fulfills a user-specified criterion, and this has been shown to severely mischaracterize both the equilibrium moisture content and the full kinetic behavior. The objective of this work is to examine whether interrupting data acquisition before equilibrium affects the PEK model parameters and further explore whether PEK model interpretations have physical significance as claimed in the literature. The analysis shows that the PEK model cannot capture the actual form of the sorption curves for loblolly pine and microcrystalline cellulose across a range of relative humidity (RH) steps in both absorption and desorption. PEK model parameters depend not only on the mass stability criterion that controls the measurement hold time, but also on the RH step making even qualitative comparisons of a single sample across different RH steps meaningless. The PEK model cannot be used to derive physically meaningful properties from water vapor sorption measurements and its use as a tool for exploring the properties of cellulosic materials interacting with water is not recommended.