AbstractThe endwise depolymerization (unzipping reaction) of hydrolyzed cotton cellulose (x= 200) in water under a nitrogen atmosphere was followed at 98°C at several alkalinities in the pH range of 8.0–10.5. The observed apparent first‐order rate constantk1was invariable at low alkalinity (k1=k0), while above pH 8.5,k1increased with pH. The data conform with the expressiondocumentclass{article}pagestyle{empty}begin{document}$ {rm rate} = (k_0 + k_{{rm OH}^ - } {rm OH}^ - ){rm SH} = (0.3 + 2.1 times 10^3 {rm OH}^ - ){rm SH} $end{document}where SH denotes substrate concentration. The specific hydroxide ion catalysis is considered to involve ionization of the anomeric hydroxyl group at the reducing chain end that leads to elimination of the glucosidic oxygen atom bearing the polymer chain from C4 of the terminal D‐glucose residue. In this initiation process, the glucosidic oxygen is eliminated as an anion so that rapid propagation of the unzipping along the polymer chain may occur. Thus, entire chains will depolymerize. The kinetic chain lengthvis defined as the ratiok1:kt, wherektis the pseudofirst‐order rate constant for chain terminations, and a value ofv∼ 100 D‐glucose residues was found at all the alkalinities
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