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Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis

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2018
Authors
Spasojević, Miroslav
Marković, D.
Trišović, Tomislav
Spasojević, Milica
Article (Published version)
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Abstract
The effect of chromium(VI) on the kinetics of disproportionation of hypochlorous acid and hypochlorite was established in the solution for the electrolytic production of chlorate. The hexavalent chromium species Cr2O7 2-, HCrO4 - and CrO4 2- present in the solution catalyze the disproportionation reaction. In both the absence and presence of chromium(VI), disproportionation is a third-order reaction with respect to HClO and ClO-P, and a first-order reaction with respect to the hexavalent chromium species. In the presence of chromium(VI) ions, four parallel reactions probably take place in the solution i.e. uncatalyzed disproportionation and three parallel reactions catalyzed by Cr2O7 2-, HCrO4 - and CrO4 2-ions. Most likely, the hexavalent chromium species do not change the sequence of elementary reactions in the disproportionation mechanism but only speed up the rate-determining step through interaction with its reactants. In the chlorate production process, as chromium(VI) concentrat...ion increases, the optimum pH which ensures the maximum rate of disproportionation is shifted to an acid environment. This is due to an increase in the concentration of the catalytically most active species HCrO4 - with increasing acidity of the solution. A mathematical model of the kinetics of the chromium(VI)-catalyzed disproportionation of hypochlorite and hypochlorous acid into chlorate was set up. Good agreement was obtained between theoretical and experimental data. © 2018 The Electrochemical Society.

Source:
Journal of the Electrochemical Society, 2018, 165, 2, E8-E19
Publisher:
  • Pennington N.J. : Electrochemical Society
Funding / projects:
  • Directed synthesis, structure and properties of multifunctional materials (RS-172057)
Note:
  • Peer-reviewed manuscript: https://hdl.handle.net/21.15107/rcub_dais_8970

DOI: 10.1149/2.0291802jes

ISSN: 0013-4651

WoS: 000431786800089

Scopus: 2-s2.0-85043601638
[ Google Scholar ]
9
8
Handle
https://hdl.handle.net/21.15107/rcub_dais_3750
URI
https://dais.sanu.ac.rs/123456789/3750
Collections
  • ИТН САНУ - Општа колекција / ITS SASA - General collection
Institution/Community
Институт техничких наука САНУ / Institute of Technical Sciences of SASA
TY  - JOUR
AU  - Spasojević, Miroslav
AU  - Marković, D.
AU  - Trišović, Tomislav
AU  - Spasojević, Milica
PY  - 2018
UR  - https://dais.sanu.ac.rs/123456789/3750
AB  - The effect of chromium(VI) on the kinetics of disproportionation of hypochlorous acid and hypochlorite was established in the solution for the electrolytic production of chlorate. The hexavalent chromium species Cr2O7 2-, HCrO4 - and CrO4 2- present in the solution catalyze the disproportionation reaction. In both the absence and presence of chromium(VI), disproportionation is a third-order reaction with respect to HClO and ClO-P, and a first-order reaction with respect to the hexavalent chromium species. In the presence of chromium(VI) ions, four parallel reactions probably take place in the solution i.e. uncatalyzed disproportionation and three parallel reactions catalyzed by Cr2O7 2-, HCrO4 - and CrO4 2-ions. Most likely, the hexavalent chromium species do not change the sequence of elementary reactions in the disproportionation mechanism but only speed up the rate-determining step through interaction with its reactants. In the chlorate production process, as chromium(VI) concentration increases, the optimum pH which ensures the maximum rate of disproportionation is shifted to an acid environment. This is due to an increase in the concentration of the catalytically most active species HCrO4 - with increasing acidity of the solution. A mathematical model of the kinetics of the chromium(VI)-catalyzed disproportionation of hypochlorite and hypochlorous acid into chlorate was set up. Good agreement was obtained between theoretical and experimental data. © 2018 The Electrochemical Society.
PB  - Pennington N.J. : Electrochemical Society
T2  - Journal of the Electrochemical Society
T1  - Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis
SP  - E8
EP  - E19
VL  - 165
IS  - 2
DO  - 10.1149/2.0291802jes
UR  - https://hdl.handle.net/21.15107/rcub_dais_3750
ER  - 
@article{
author = "Spasojević, Miroslav and Marković, D. and Trišović, Tomislav and Spasojević, Milica",
year = "2018",
abstract = "The effect of chromium(VI) on the kinetics of disproportionation of hypochlorous acid and hypochlorite was established in the solution for the electrolytic production of chlorate. The hexavalent chromium species Cr2O7 2-, HCrO4 - and CrO4 2- present in the solution catalyze the disproportionation reaction. In both the absence and presence of chromium(VI), disproportionation is a third-order reaction with respect to HClO and ClO-P, and a first-order reaction with respect to the hexavalent chromium species. In the presence of chromium(VI) ions, four parallel reactions probably take place in the solution i.e. uncatalyzed disproportionation and three parallel reactions catalyzed by Cr2O7 2-, HCrO4 - and CrO4 2-ions. Most likely, the hexavalent chromium species do not change the sequence of elementary reactions in the disproportionation mechanism but only speed up the rate-determining step through interaction with its reactants. In the chlorate production process, as chromium(VI) concentration increases, the optimum pH which ensures the maximum rate of disproportionation is shifted to an acid environment. This is due to an increase in the concentration of the catalytically most active species HCrO4 - with increasing acidity of the solution. A mathematical model of the kinetics of the chromium(VI)-catalyzed disproportionation of hypochlorite and hypochlorous acid into chlorate was set up. Good agreement was obtained between theoretical and experimental data. © 2018 The Electrochemical Society.",
publisher = "Pennington N.J. : Electrochemical Society",
journal = "Journal of the Electrochemical Society",
title = "Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis",
pages = "E8-E19",
volume = "165",
number = "2",
doi = "10.1149/2.0291802jes",
url = "https://hdl.handle.net/21.15107/rcub_dais_3750"
}
Spasojević, M., Marković, D., Trišović, T.,& Spasojević, M.. (2018). Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis. in Journal of the Electrochemical Society
Pennington N.J. : Electrochemical Society., 165(2), E8-E19.
https://doi.org/10.1149/2.0291802jes
https://hdl.handle.net/21.15107/rcub_dais_3750
Spasojević M, Marković D, Trišović T, Spasojević M. Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis. in Journal of the Electrochemical Society. 2018;165(2):E8-E19.
doi:10.1149/2.0291802jes
https://hdl.handle.net/21.15107/rcub_dais_3750 .
Spasojević, Miroslav, Marković, D., Trišović, Tomislav, Spasojević, Milica, "Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis" in Journal of the Electrochemical Society, 165, no. 2 (2018):E8-E19,
https://doi.org/10.1149/2.0291802jes .,
https://hdl.handle.net/21.15107/rcub_dais_3750 .

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