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Electrocatalytic Reduction of 2, 2, 2–Trichloro-1, 1-Bis (4-Chlorophenyl) Ethanol (Dicofol) in Acetonitrile-Aqueous Solution Using Cyanocobalamin as a Catalyst

Received: 5 December 2014     Accepted: 23 December 2014     Published: 20 January 2015
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Abstract

This paper reports on the catalytic behaviour of cyanocobalamin (VB12) towards the reduction of polyhalogenated organic pollutant 2, 2, 2–trichloro-1,1-bis (4-chlorophenyl) ethanol (dicofol) in acetonitrile-aqueous solution containing 0.1M KNO3 supporting electrolyte. Dicofol is a persistent, toxic organochlorine acaricide used in agriculture and horticulture to control spider mites and soft-bodied mites. Due to the chronic toxicity, bioaccumulation and carcinogenity, determination of persistent organochlorine pesticides like dicofol has become very important. The available methods are disfavored as they lack necessary simplicity, inexpensiveness and environmentally friendliness for routine analysis, and consequently, electrochemical methods have shown to be possible alternatives. Cyanocobalamin being one of the most nucleophilic species known in aqueous solution can undergo nucleophilic reactions which are efficient for dehalogenation of various organic halides. Direct reduction of cyanocobalamin exhibited a quasi-reversible two-electron reduction with the oxidation state of the central cobalt species going from +3 to +1 and E½ of 0.696 ± 0.009 V. Dicofol exhibited a single two-electron reduction peak at -1.182±0.029 V vs SCE. The E½ was -1.074 V and the diffusion coefficient was 2.21x10-5 cm2s-1. Addition of dicofol to solution of cyanocobalamin resulted in a large reduction peak at around the reduction peak potential of cyanocobalamin (-0.732±0.018V versus SCE for six scan rates). This makes it clear that when cyanocobalamin is adsorbed on pyrolytic graphite electrode, it causes the lowering of overpotential for the reductive decomposition of dicofol by approximately 0.45 V and therefore ΔG was about 1½ times lowered. The decrease in ΔG implies that electrocatalysis is more kinetically favourable compared to direct electrochemical activation of carbon–halogen bonds.

Published in Science Journal of Chemistry (Volume 3, Issue 1)
DOI 10.11648/j.sjc.20150301.11
Page(s) 1-10
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2015. Published by Science Publishing Group

Keywords

Catalytic Activity, Current Density, Current Efficiency, Cyanocobalamin, Dicofol, Diffusion Coefficient, Electrocatalysis, Pesticides, Pollutants

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    Wanjau Tabitha Wangui, Geoffrey Njuguna Kamau, Mwaniki Silas Ngari, Muya Catherine Njambi. (2015). Electrocatalytic Reduction of 2, 2, 2–Trichloro-1, 1-Bis (4-Chlorophenyl) Ethanol (Dicofol) in Acetonitrile-Aqueous Solution Using Cyanocobalamin as a Catalyst. Science Journal of Chemistry, 3(1), 1-10. https://doi.org/10.11648/j.sjc.20150301.11

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    ACS Style

    Wanjau Tabitha Wangui; Geoffrey Njuguna Kamau; Mwaniki Silas Ngari; Muya Catherine Njambi. Electrocatalytic Reduction of 2, 2, 2–Trichloro-1, 1-Bis (4-Chlorophenyl) Ethanol (Dicofol) in Acetonitrile-Aqueous Solution Using Cyanocobalamin as a Catalyst. Sci. J. Chem. 2015, 3(1), 1-10. doi: 10.11648/j.sjc.20150301.11

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    Wanjau Tabitha Wangui, Geoffrey Njuguna Kamau, Mwaniki Silas Ngari, Muya Catherine Njambi. Electrocatalytic Reduction of 2, 2, 2–Trichloro-1, 1-Bis (4-Chlorophenyl) Ethanol (Dicofol) in Acetonitrile-Aqueous Solution Using Cyanocobalamin as a Catalyst. Sci J Chem. 2015;3(1):1-10. doi: 10.11648/j.sjc.20150301.11

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  • @article{10.11648/j.sjc.20150301.11,
      author = {Wanjau Tabitha Wangui and Geoffrey Njuguna Kamau and Mwaniki Silas Ngari and Muya Catherine Njambi},
      title = {Electrocatalytic Reduction of 2, 2, 2–Trichloro-1, 1-Bis (4-Chlorophenyl) Ethanol (Dicofol) in Acetonitrile-Aqueous Solution Using Cyanocobalamin as a Catalyst},
      journal = {Science Journal of Chemistry},
      volume = {3},
      number = {1},
      pages = {1-10},
      doi = {10.11648/j.sjc.20150301.11},
      url = {https://doi.org/10.11648/j.sjc.20150301.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20150301.11},
      abstract = {This paper reports on the catalytic behaviour of cyanocobalamin (VB12) towards the reduction of polyhalogenated organic pollutant 2, 2, 2–trichloro-1,1-bis (4-chlorophenyl) ethanol (dicofol) in acetonitrile-aqueous solution containing 0.1M KNO3 supporting electrolyte. Dicofol is a persistent, toxic organochlorine acaricide used in agriculture and horticulture to control spider mites and soft-bodied mites. Due to the chronic toxicity, bioaccumulation and carcinogenity, determination of persistent organochlorine pesticides like dicofol has become very important. The available methods are disfavored as they lack necessary simplicity, inexpensiveness and environmentally friendliness for routine analysis, and consequently, electrochemical methods have shown to be possible alternatives. Cyanocobalamin being one of the most nucleophilic species known in aqueous solution can undergo nucleophilic reactions which are efficient for dehalogenation of various organic halides. Direct reduction of cyanocobalamin exhibited a quasi-reversible two-electron reduction with the oxidation state of the central cobalt species going from +3 to +1 and  E½ of 0.696 ± 0.009 V. Dicofol exhibited a single two-electron reduction peak at -1.182±0.029 V vs SCE. The E½ was -1.074 V and the diffusion coefficient was 2.21x10-5 cm2s-1. Addition of dicofol to solution of cyanocobalamin resulted in a large reduction peak at around the reduction peak potential of cyanocobalamin (-0.732±0.018V versus SCE for six scan rates). This makes it clear that when cyanocobalamin is adsorbed on pyrolytic graphite electrode, it causes the lowering of overpotential for the reductive decomposition of dicofol by approximately 0.45 V and therefore ΔG was about 1½ times lowered. The decrease in ΔG implies that electrocatalysis is more kinetically favourable compared to direct electrochemical activation of carbon–halogen bonds.},
     year = {2015}
    }
    

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  • TY  - JOUR
    T1  - Electrocatalytic Reduction of 2, 2, 2–Trichloro-1, 1-Bis (4-Chlorophenyl) Ethanol (Dicofol) in Acetonitrile-Aqueous Solution Using Cyanocobalamin as a Catalyst
    AU  - Wanjau Tabitha Wangui
    AU  - Geoffrey Njuguna Kamau
    AU  - Mwaniki Silas Ngari
    AU  - Muya Catherine Njambi
    Y1  - 2015/01/20
    PY  - 2015
    N1  - https://doi.org/10.11648/j.sjc.20150301.11
    DO  - 10.11648/j.sjc.20150301.11
    T2  - Science Journal of Chemistry
    JF  - Science Journal of Chemistry
    JO  - Science Journal of Chemistry
    SP  - 1
    EP  - 10
    PB  - Science Publishing Group
    SN  - 2330-099X
    UR  - https://doi.org/10.11648/j.sjc.20150301.11
    AB  - This paper reports on the catalytic behaviour of cyanocobalamin (VB12) towards the reduction of polyhalogenated organic pollutant 2, 2, 2–trichloro-1,1-bis (4-chlorophenyl) ethanol (dicofol) in acetonitrile-aqueous solution containing 0.1M KNO3 supporting electrolyte. Dicofol is a persistent, toxic organochlorine acaricide used in agriculture and horticulture to control spider mites and soft-bodied mites. Due to the chronic toxicity, bioaccumulation and carcinogenity, determination of persistent organochlorine pesticides like dicofol has become very important. The available methods are disfavored as they lack necessary simplicity, inexpensiveness and environmentally friendliness for routine analysis, and consequently, electrochemical methods have shown to be possible alternatives. Cyanocobalamin being one of the most nucleophilic species known in aqueous solution can undergo nucleophilic reactions which are efficient for dehalogenation of various organic halides. Direct reduction of cyanocobalamin exhibited a quasi-reversible two-electron reduction with the oxidation state of the central cobalt species going from +3 to +1 and  E½ of 0.696 ± 0.009 V. Dicofol exhibited a single two-electron reduction peak at -1.182±0.029 V vs SCE. The E½ was -1.074 V and the diffusion coefficient was 2.21x10-5 cm2s-1. Addition of dicofol to solution of cyanocobalamin resulted in a large reduction peak at around the reduction peak potential of cyanocobalamin (-0.732±0.018V versus SCE for six scan rates). This makes it clear that when cyanocobalamin is adsorbed on pyrolytic graphite electrode, it causes the lowering of overpotential for the reductive decomposition of dicofol by approximately 0.45 V and therefore ΔG was about 1½ times lowered. The decrease in ΔG implies that electrocatalysis is more kinetically favourable compared to direct electrochemical activation of carbon–halogen bonds.
    VL  - 3
    IS  - 1
    ER  - 

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Author Information
  • Kisii University, School of Health Sciences, P.O. Box 408-40200 Kisii, Kenya

  • School of Physical Sciences, University of Nairobi, P.O. Box 30197 Nairobi, Kenya

  • Faculty of Science, Egerton University, Department of Chemistry, P.O. Box, 536 Njoro, Kenya

  • Faculty of Environmental Science, Technical University of Kenya, P.O. Box Nairobi, Kenya

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