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On the kinetics of cellulose degradation: looking beyond the pseudo zero order rate equation

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Abstract

The kinetics of cellulose degradation was analysed by means of a two-stage model, characterised by an autoretardant and autocatalytic regime, later tempered by the consumption of glycosidic bonds in the amorphous regions. The proposed model explains the effects on the kinetic equations of different modes of ageing (acid hydrolysis, ageing in ventilated oven or sealed vessels), initial oxidation of cellulose and experimental procedures (with or without reduction of oxidised groups). The autoretardant branch can be analysed in a quantitative way, while the integration of the non-linear autocatalytic branch is allowed in some cases, characterised by the decrease of pH and/or emission of acid volatile organic compounds (VOCs). Most of the controversial results of the literature can be easily explained, but the proposed model offers also a guide for further studies on the kinetics of cellulose degradation.

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Abbreviations

α:

Excess of produced acidity

A:

Rearranged product of cellulose hydrolysis (in general)

C:

Cellulose (in general)

c°:

Initial amount of non-oxidised scissile units

DP:

Degree of polymerisation (with suffixes w, weight average; n, number average)

h:

Acidity produced by the degradation

H:

Acidity (in general)

O:

Oxidised cellulose (in general)

k:

Rate constant of the hydrolytic mechanism (with suffixes a, amorphous regions of cellulose; c, crystalline regions of cellulose; w, weak links)

kA :

Rate constant of the autocatalytic mechanism

ko :

Rate constant of oxidation

LODP:

Levelling-off degree of polymerisation

n°:

Initial amount of overall scissile units (with suffixes a, glycosidic bonds in the amorphous domain; c, glycosidic bonds in the crystalline domain; w, weak links)

ox°:

Initial amount of scissile units activated by the presence of oxidised groups in the adjacent anhydroglucose rings

P:

Product of cellulose hydrolysis (in general)

S:

Number of scissions per cellulose chain

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Authors and Affiliations

  1. Ministero Beni Culturali, S.B.A.P., Via Balbi 10, Genova, 16126, Italy

    Paolo Calvini

  2. Dipartimento di Storia e Tutela dei Beni Culturali, Università di Udine, Palazzo Caiselli – Vicolo Florio 2/B, Udine, 33100, Italy

    Andrea Gorassini

  3. Ministero Beni Culturali, I.C.P.L., Via Milano 76, Roma, 00184, Italy

    Antonio Luigi Merlani

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  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. & Merlani, A.L. On the kinetics of cellulose degradation: looking beyond the pseudo zero order rate equation. Cellulose 15, 193–203 (2008). https://doi.org/10.1007/s10570-007-9162-8

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