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The kinetics of the homogeneous acylation of microcrystalline cellulose, MCC, with carboxylic acid anhydrides with different acyl chain-length (Nc; ethanoic to hexanoic) in LiCl/N,N-dimethylacetamide have been studied by conductivity measurements from 65 to 85°C. We have employed cyclohexylmethanol, CHM, and trans-1,2-cyclohexanediol, CHD, as model compounds for the hydroxyl groups of the anhydroglucose unit of cellulose. The ratios of rate constants of acylation of primary (CHM; Prim-OH) and secondary (CHD; Sec-OH) groups have been employed, after correction, in order to split the overall rate constants of the reaction of MCC into contributions from the discrete OH groups. For the model compounds, we have found that k (Prim-OH) /k (Sec-OH) [ 1, akin to reactions of cellulose under heterogeneous conditions; this ratio increases as a function of increasing Nc. The overall, and partial rate constants of the acylation of MCC decrease from ethanoic-to butanoic-anhydride and then increase for pentanoic-and hexanoic anhydride, due to subtle changes in-and compensations of the enthalpy and entropy of activation.

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