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

Wanjau Tabitha Wangui; Geoffrey Njuguna Kamau; Mwaniki Silas Ngari; Muya Catherine Njambi

doi:doi:10.11648/j.sjc.20150301.11

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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

Wanjau Tabitha Wangui, Geoffrey Njuguna Kamau, Mwaniki Silas Ngari, Muya Catherine Njambi

Published in Science Journal of Chemistry (Volume 3, Issue 1)

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

References

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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

Wanjau Tabitha Wangui

Kisii University, School of Health Sciences, P.O. Box 408-40200 Kisii, Kenya
Geoffrey Njuguna Kamau

School of Physical Sciences, University of Nairobi, P.O. Box 30197 Nairobi, Kenya
Mwaniki Silas Ngari

Faculty of Science, Egerton University, Department of Chemistry, P.O. Box, 536 Njoro, Kenya
Muya Catherine Njambi

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

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APA Style

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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AMA 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

Copy | Download

@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}
}

Copy | Download

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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