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The kinetics of the spontaneous proton- and Al(III)-catalysed hydrolysis of 1,5-anhydrocellobiitol – models for cellulose depolymerisation in paper aging and alkaline pulping, and a benchmark for cellulase efficiency.

Baty, John and Sinnott, Michael L. (2005) The kinetics of the spontaneous proton- and Al(III)-catalysed hydrolysis of 1,5-anhydrocellobiitol – models for cellulose depolymerisation in paper aging and alkaline pulping, and a benchmark for cellulase efficiency. Canadian Journal of Chemistry, 83. pp. 1516-1524. ISSN 0008-4042

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    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).

    Item Type: Article
    Additional Information: UoA 18 (Chemistry) Reproduced from the Canadian Journal of Chemistry, with permission from NRC Research Press © 2005 NRC Canada
    Subjects: Q Science > QD Chemistry
    Schools: School of Applied Sciences
    School of Applied Sciences > Biomolecular Sciences Research Centre
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    1524 Can. J. Chem. Vol. 83, 2005

    Depositing User: Briony Heyhoe
    Date Deposited: 13 Jul 2007
    Last Modified: 28 Jul 2010 19:20
    URI: http://eprints.hud.ac.uk/id/eprint/265

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