Monomolecular adsorption and crystallite diameters of cellulose from structural and adsorption considerations

Calculations of the monomolecular water vapor adsorption by three different celluloses (cotton, wood pulp and cellophane) from structural considerations are in agreement with the BET determined values for crystallite diameters of 16 to 200 on the basis of adsorption being confined to the fraction f of the three hydroxyl groups per anhydroglucose unit that are available on the surface of the crystallites and within the amorphous zones, when f ranges from 0.16 to 0.29. These low values of f are compatible with the fact that the void volume of the amorphous zones does not exceed about 6%. More exact values for f are needed before more definite values for the crystallite diameters can be estimated. A modified fringe micelle diagram containing a considerable amount of chain association in the amorphous zones is given that meets the requirement dictated by the calculations. Another approach, involving direct estimation of the adsorbing surface areas of crystallites and amorphous zones, on the basis of adjacent surfaces being shared by water molecules adsorbed between them, gives surface areas somewhat larger than the BET values using the same f values. Agreement with values from the former approach is obtained if only 75% of the surface per anhydroglucose unit is considered effective for adsorption.