New insights into the decomposition mechanism of chlorine dioxide at alkaline pH
-
Jennifer Marcon
,
Gérard Mortha
Abstract
The mechanism of chlorine dioxide (ClO2) decomposition in an alkaline medium has been investigated. The formation of radicals and chlorinated species was studied in aqueous solutions containing ClO2 and simple model compounds of lignin or cellulose (vanillin, vanillyl alcohol, veratryl alcohol, methylglucoside and cellobiose) at acidic and alkaline pHs. Because hypochlorite (ClO−) is an intermediate occurring in the course of the reaction mechanism, similar experiments were carried out with solutions of sodium hypochlorite (NaClO) at alkaline and acidic pHs. Electron paramagnetic resonance (EPR) spectroscopy based on the spin-trapping technique revealed the presence of hydroxyl radicals (HO˙) at alkaline pH with ClO2 alone or with model compounds. At the same pH, only a small amount of HO˙ was detected with ClO−. Chlorite (ClO2−) and chlorate (ClO3−) ions were dosed with iodometric titrations, both during ClO2 alkaline decomposition and during reactions with model compounds. Vanillin and vanillyl alcohol were oxidized by ClO2. The intermediate ClO2− was either inert or reacted with the aldehyde function of vanillin. Cellobiose was attacked only in an alkaline medium, either directly by ClO2 or indirectly by HO˙ radicals. This resulted in the formation of glucose, which was then degraded by ClO2− ions. The generation of HO˙ could be one reason for cellulose degradation by ClO2 at alkaline pH, but possibly not the unique one, as it was not proved in this article, whether or not ClO2 is able to directly attach the OH functions of anhydrosugars at alkaline pH.
Acknowledgments
The authors acknowledge the Centre Technique du Papier and the Région Auvergne-Rhône-Alpes for the funding of this study and the Réseau National de RPE interdisciplinaire IR CNRS FR3443 for the EPR measurements. This research was made possible thanks to the facilities of the TekLiCell platform funded by the Région Rhône-Alpes (ERDF: European regional development fund).
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©2017 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- Editorial
- Editorial
- Original Articles
- About structural changes of lignin during kraft cooking and the kinetics of delignification
- Utilization of lignin powder for manufacturing self-binding HDF
- Consecutive determination of softwood kraft lignin structure and molar mass from NMR measurements
- Production of hemicellulose oligomers from softwood chips using autohydrolysis followed by an enzymatic post-hydrolysis
- Morphological features of aerogels and carbogels based on lignosulfonates
- Wood based activated carbons for supercapacitor electrodes with sulfuric acid electrolyte
- New insights into the decomposition mechanism of chlorine dioxide at alkaline pH
- Upgrading of commercial pulps to high-purity dissolving pulps by an ionic liquid-based extraction method
- Hardwood kraft pulp structural features affecting refinability
- Brightness stability of eucalyptus-dissolving pulps: effect of the bleaching sequence
- Cellulose fiber based fungal and water resistant insulation materials
- Biomass conversion into blow-in heat insulation materials by steam explosion
- Effect of cationic polyelectrolytes in contact-active antibacterial layer-by-layer functionalization
- Nanocelluloses obtained by ammonium persulfate (APS) oxidation of bleached kraft pulp (BKP) and bacterial cellulose (BC) and their application in biocomposite films together with chitosan
- Volatile terpene extraction of spruce, fir and maritime pine wood: supercritical CO2 extraction compared to classical solvent extractions and steam distillation
- Protective effects of proanthocyanidins extracts from the bark of deciduous trees in lipid systems
- Short Notes
- Steam explosion treatments of technical hydrolysis lignin
- Moisture absorption properties of hardwood veneers modified by a sol-gel process
Articles in the same Issue
- Frontmatter
- Editorial
- Editorial
- Original Articles
- About structural changes of lignin during kraft cooking and the kinetics of delignification
- Utilization of lignin powder for manufacturing self-binding HDF
- Consecutive determination of softwood kraft lignin structure and molar mass from NMR measurements
- Production of hemicellulose oligomers from softwood chips using autohydrolysis followed by an enzymatic post-hydrolysis
- Morphological features of aerogels and carbogels based on lignosulfonates
- Wood based activated carbons for supercapacitor electrodes with sulfuric acid electrolyte
- New insights into the decomposition mechanism of chlorine dioxide at alkaline pH
- Upgrading of commercial pulps to high-purity dissolving pulps by an ionic liquid-based extraction method
- Hardwood kraft pulp structural features affecting refinability
- Brightness stability of eucalyptus-dissolving pulps: effect of the bleaching sequence
- Cellulose fiber based fungal and water resistant insulation materials
- Biomass conversion into blow-in heat insulation materials by steam explosion
- Effect of cationic polyelectrolytes in contact-active antibacterial layer-by-layer functionalization
- Nanocelluloses obtained by ammonium persulfate (APS) oxidation of bleached kraft pulp (BKP) and bacterial cellulose (BC) and their application in biocomposite films together with chitosan
- Volatile terpene extraction of spruce, fir and maritime pine wood: supercritical CO2 extraction compared to classical solvent extractions and steam distillation
- Protective effects of proanthocyanidins extracts from the bark of deciduous trees in lipid systems
- Short Notes
- Steam explosion treatments of technical hydrolysis lignin
- Moisture absorption properties of hardwood veneers modified by a sol-gel process
