Cellulose

, 15:193 | Cite as

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

  • Paolo Calvini
  • Andrea Gorassini
  • Antonio Luigi Merlani
Article

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.

Keywords

Accelerated ageing Acid hydrolysis Autocatalysis Degree of polymerisation Kinetic models Random degradation Sigmoidal kinetics 

Abbreviations

α

Excess of produced acidity

A

Rearranged product of cellulose hydrolysis (in general)

C

Cellulose (in general)

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

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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Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  • Paolo Calvini
    • 1
  • Andrea Gorassini
    • 2
  • Antonio Luigi Merlani
    • 3
  1. 1.Ministero Beni Culturali, S.B.A.P.GenovaItaly
  2. 2.Dipartimento di Storia e Tutela dei Beni CulturaliUniversità di UdineUdineItaly
  3. 3.Ministero Beni Culturali, I.C.P.L.RomaItaly

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