The heterogeneous character of the dilute acid hydrolysis of crystalline cellulose. III. Kinetic and X-ray data

Thirteen prehydrolyzed samples of cellulose, including native, mercerized, and regenerated materials were hydrolyzed in 1% and 1.5% sulfuric acid at 160, 170, and 180°C. Pseudo first‐order rate constants and weight average degrees of polymerization were determined for each sample. For all cellulose samples, data from several experiments were used to determine the dependence of the rate of hydrolysis on sulfuric acid concentration. The results obtained in this study indicate that Sharples' end‐attack model is consistent with kinetic data for the hydrolysis of cellulose II samples, but is not applicable to the hydrolysis of cellulose I samples. X‐ray diffraction analyses indicated that, for native and mercerized cellulose samples, structural changes during dilute acid hydrolysis are not significant. However, data for rayon indicated that such changes may need to be taken into account in analysis of the reaction kinetics.