Mechanism of Cellulose Reactions

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Abstract
A cellulose molecule is, and reacts as, a polytrihydric alcohol, containing one primary and two different secondary hydroxyls per unit of polymerization. Reaction may be by disrupting the linkages holding the units together, or it may be any of the usual reactions of hydroxyl groups. The tendency for one hydroxyl of a glucose unit to react before the others is slight in esterification or other reactions in acid medium, but may assume importance in alkaline reactions, such as xanthation, etherification or oxidation. In most reactions, the distribution of substituents along the cellulose chain is governed by the laws of chance. The reaction of cellulose in the fibrous or any other solid state is governed by the rate of diffusion of reagent to the individual hydroxyls. This, in turn, is governed by the peculiarities of structure of the fiber and the degree of swelling of the cellulose. Increase of volume due to swelling may proceed to a considerable extent without essential loss of the previous orderly arrangement. The greater the extent of swelling, the greater is the rapidity of reaction; the greater the uniformity of swelling, the greater is the uniformity of reaction.

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