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

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2018
10.1149@2.0291802jes-postprint.pdf (1.427Mb)
Authors
Spasojević, Miroslav
Marković, D.
Trišović, Tomislav
Spasojević, Milica
Article (Accepted Version)
,
Electrochemical Society
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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
Projects:
  • Directed synthesis, structure and properties of multifunctional materials (RS-172057)
Note:
  • This is the peer-reviewed version of the paper: Spasojević, M., Marković, D., Trišović, T., Spasojević, M., 2018. Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis. Journal of the Electrochemical Society 165, E8–E19. https://doi.org/10.1149/2.0291802jes

DOI: 10.1149/2.0291802jes

ISSN: 0013-4651

WoS: 000431786800089

Scopus: 2-s2.0-85043601638
[ Google Scholar ]
5
5
URI
http://dais.sanu.ac.rs/123456789/8970
Collections
  • ITN SANU - Opšta kolekcija / ITS SASA - General collection
Institution
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  - http://dais.sanu.ac.rs/123456789/8970
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
ER  - 
@article{
author = "Spasojević, Miroslav and Marković, D. and Trišović, Tomislav and Spasojević, Milica",
year = "2018",
url = "http://dais.sanu.ac.rs/123456789/8970",
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"
}
Spasojević M, Marković D, Trišović T, Spasojević M. Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis. Journal of the Electrochemical Society. 2018;165(2):E8-E19
Spasojević, M., Marković, D., Trišović, T.,& Spasojević, M. (2018). Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis.
Journal of the Electrochemical SocietyPennington N.J. : Electrochemical Society., 165(2), E8-E19.
https://doi.org/10.1149/2.0291802jes
Spasojević Miroslav, Marković D., Trišović Tomislav, Spasojević Milica, "Mathematical model of the catalytic effect of chromium(VI) on hypochlorite disproportionation in chlorate electrolysis" 165, no. 2 (2018):E8-E19,
https://doi.org/10.1149/2.0291802jes .

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