Hailwood-Horrobin solution sorption theory

Hailwood-Horrobin Solution Sorption Theory. The Hailwood-Horrobin (57) model treats moisture sorption as hydration of the polymer, taken here to be dry wood, by some of the sorbed water called water of hydration, m. The hydrate forms a partial solution with the remaining sorbed water, called water of solution, m,. An equilibrium is assumed to exist between the dry wood and water and the hydrated wood with an equilibrium constant K. Equilibrium is also assumed to exist between the hydrated wood and water vapor at relative vapor pressure h, with equilibrium constant K2. A third constant is defined as the moisture content corresponding to com-... 

Most subsequent sorption theories, including those discussed here, have followed this general approach and postulate two forms of sorbed water. These theories may be classified into at least two general types based on the sorption mechanism assumed. One type assumes sorption on internal surfaces and is represented by the Dent theory (52), which is a modification of the classic Brunauer, Emmett, and Teller (BET) theory (53). The second type assumes that the wood-water system forms a solution, exemplified by the Hailwood-Horrobin theory. There have been other theories, not discussed here, that have also been applied to explain water sorption by hygroscopic materials (JO, 54, 55). 

Hailwood and Horrobin ( ) develqped an equation for water sorption of cellulose based on a solution theory. It permits the calculation of the fraction of the san )le inaccessible to water vapor. However, Hailwood and Horrobin assumed in the development of their equation that an ideal solid solution of polymer, hydrated polymer and water is formed. This assutrption has laeen questioned in the general discussion following the presentation of their paper and also by McLaren and Rcwen (29). 

Water vapor at room temperature will not penetrate well-defined crystallites but will be adsorbed in the amorphous regions. Consequently, moisture sorption measured gravimetrically at a given relative vapor pressure and temperature has been used to determine order in cellulosic materials. In the case of Valentine [252] and Jeffries [253], the fraction of ordered material was obtained by correlating moisture sorption with values obtained by the deuterium oxide method. Hailwood and Horrobin [254] developed an equation for water sorption of cellulose based on a solution theory that allowed the calculation of the fraction of the sample inaccessible to water. 

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