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Surface and bulk reactions of cellulose oxidation by periodate. A simple kinetic model

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Abstract

The kinetics of periodate oxidation of cellulose was followed by exploiting the β-alkoxy degradation of oxidised units in alkaline medium, that brings about a decrease of viscometric degree of polymerisation. The parallel strong weight loss after NaOH treatment indicates a non-random mechanism of oxidation. The obtained results are interpreted on the basis of an appositely derived kinetic model that can be applied to other mechanisms of bulk and surface degradation.

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Abbreviations

CED:

Cupriethylenediamine

DP:

Degree of polymerisation, with suffixes w weigth-average, v viscometric-average, n number-average

GPC:

Gel permeation chromatography

hmw:

High molecular weight

kr:

First-order rate constant of the random scissions

ks:

First-order rate constant of the surface erosion

λ:

Fractional weight loss

LODP:

Leveling-off degree of polymerisation

lmw:

Low molecular weight

n°:

Number of scissile units per chain (DP°/LODP−1)

Rw:

Random scissions per chain of the high-molecular weight fraction

Sw:

Experimental number of scissions per chain (DPw°/DPw−1)

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Acknowledgments

The authors wish to acknowledge the anonymous referee who underlined the differences and the similarities between the viscometric and the GPC analyses of periodate oxidised samples, allowing a better picture of the suggested mechanism for further specific analyses.

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Authors and Affiliations

  1. Istituto per la Tutela delle opere Grafiche (ITOG), Via Pietro Sola 29, 31059, Zero Branco, Treviso, Italy

    Paolo Calvini

  2. Dipartimento di Storia e Tutela dei Beni Culturali, Università degli Studi di Udine, Via Petracco 8, 33100, Udine, Italy

    Andrea Gorassini

Authors
  1. Paolo Calvini
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  2. Andrea Gorassini
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Correspondence to Paolo Calvini.

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Calvini, P., Gorassini, A. Surface and bulk reactions of cellulose oxidation by periodate. A simple kinetic model. Cellulose 19, 1107–1114 (2012). https://doi.org/10.1007/s10570-012-9717-1

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  • DOI: https://doi.org/10.1007/s10570-012-9717-1

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