The kinetics of the spontaneous, proton- and AlIII-catalysed hydrolysis of 1,5-anhydrocellobiitol — Models for cellulose depolymerization in paper aging and alkaline pulping, and a benchmark for cellulase efficiency

Abstract

The kinetics of the spontaneous, proton- and AlIII-catalysed hydrolyses of the C1—O4′ bond in 1,5-anhydrocellobiitol have been measured at elevated temperatures (125.0–220.0 °C). Data for the first two processes extrapolate to the expression k = (8.6 ± 2.1 × 10–16) + (1.4 ± 0.2 × 10–9-pH) s–1 at 25 °C. These room-temperature figures were used to model cellulose depolymerization by the af Ekenstam equation. The spontaneous process is too slow to contribute to loss of paper strength on aging, and even the acid-catalysed process is significant only below ~pH 4.0. However, the spontaneous hydrolysis readily accounts for the reduction of cellulose degree of polymerization (DP) during alkaline (e.g., kraft) pulping of cellulose fibres. Efficient electrophilic catalysis by AlIII was observed at 150.0 °C in 0.1 mol/L succinate buffers of room temperature pH 3.05 and 3.35 (k2 = 8.1 ± 0.4 × 10–3 and 4.2 ± 0.2 × 10–3 (mol/L) –1 s–1, respectively). The apparent activation energy of the AlIII-catalysed process was 31 ± 4 kJ mol-1, lower than that of the proton-catalysed path, suggesting the electrophilic catalysis increases in importance as the temperature approaches ambient. Consequently, it appears that the culprit in the impermanence of “rosin-alum” -sized paper is AlIII, directly acting as a Lewis acid, not the AlIII hydration sphere as a Brønsted acid. Conservation measures should either address this or be generic (e.g., low-temperature storage). Key words: cellulose, hydrolysis, kraft pulping, paper conservation, rosin-alum sizing.