Kinetics and mechanism of the reduction of n-(2-hydroxyethyl)ethylenediaminetriacetatoiron(III) complex by thioglycol in bicarbonate buffer medium

  • Authors

    • I U. Nkole Ahmadu Bello University Zaria
    • C R. Osunkwo Ahmadu Bello University Zaria
    • A D. Onu Federal University of Education, Zaria, Nigeria
    • O D. Onu Ahmadu Bello University Zaria
    2018-06-05
    https://doi.org/10.14419/ijac.v6i1.10902
  • Kinetics, N-(2-Hydroxyethyl)ethylenediaminetriacetatoiron(III) Complex, Mechanism, Thioglycol, Reduction
  • Abstract

    The kinetics and mechanism of reduction of N-(2-hydroxyethyl) ethylenediaminetriacetatoiron (III) complex (hereafter [Fe(III)HEDTAOH2]) by thioglycol (hereafter RSH) has been studied spectrophotometrically in a bicarbonate buffer medium. The study was carried out under pseudo-first order conditions of an excess of thioglycol concentration at 28 ± 1℃, I = 0.44 mol dm-3 (KNO3) and λmax = 490 nm. The reaction is first order in [Fe(III)HEDTAOH2] and half order in [RSH] and a stoichiometric mole ratio of [Fe(III)HEDTAOH2]: RSH is 2:1. Reaction rates increased with increase in ionic strength (I) and dielectric constant (D) of the reaction medium of the reaction. The reaction displayed positive primary salt effect, which suggests the composition of activated complex are likely charged reactants ions. Test for possibility of an intermediate complex formation shows negative as Michaelis-Menten plot was linear with very negligible intercept. Based on the findings, outer-sphere mechanism is proposed for the reaction. The experimental rate law obtained is; - = k2 [Fe(III)HEDTAOH2][RSH]½

     

     

     

  • References

    1. [1] Aitken, C.E., Marshall, R.A. and Puglisi, J.D. (2008). An Oxygen Scavenging System for Improvement of Dye Stability in Single-molecule Fluorescence Experiments.Biophysical Journal, 94(5): 1826 – 1835.https://doi.org/10.1529/biophysj.107.117689.

      [2] Verduyn, C., Van Kleef, R., Frank, J., Schreuder, H., Van Dijken, J.P. and Scheffers, W. A. (1985). Properties of the NAD(P)H-dependent Xylose Reductase from the Xylose-Fermenting Yeast Pichia stipitis. The Biochemical Journal. 226(3): 669 – 77..https://doi.org/10.1042/bj2260669.

      [3] Nelson, D.R., Lehninger, A.L. and Cox, M. (2005). Lehninger Principles of Biochemistry. New York: W.H. Freeman, 148. ISBN 0-7167-4339-6.

      [4] Stevens, R., Stevens, L. and Price, N.C. (1983). The Stabilities of Various Thiol Compounds used in Protein Purifications. Biochemical Education. 11(2): 70.https://doi.org/10.1016/0307-4412(83)90048-1.

      [5] Chakrabarty, S. and Banerjee, R. (2014). Kinetics and Mechanism of Oxidation of 2-Mercaptoethanol by the Heteropolyoxovanadate [MnV13O38]7-. International Journal of Chemical Kinetics, 47: 13 – 18. https://doi.org/10.1002/kin.20887.

      [6] Chakraborty, M., Mandal, P.C. and Mukhopadhyay, S. (2012). Kinetic Studies on Oxidation of L-Cysteine and 2-mercaptoethanol by a TrinuclearMn(II) Species in Aqueous Acid media. Inorganic ChimicaActa, 398: 77 – 82.https://doi.org/10.1016/j.poly.2012.07.011.

      [7] Shanmugaprabha, T., Selvakumar, K., Rajasekaram, K. and Sami, P. (2016). A Kinetic Study of the Oxidations of 2-mercaptoethanol and 2-mercaptoethylamine by Heteropoly 11-tungsto-1-vanadophosphate in Aqueous Acid Medium. Transition Metal Chemistry, 41: 177 – 185.https://doi.org/10.1007/s11243-015-9998-y.

      [8] Chakraborty, M., Mandal, P.C. and Mukhopadhyay, S. (2013). Kinetic Studies on Oxidation of L-cysteine and 2-mercaptoethanol by a TrinuclearMn(IV) Species in Aqueous Acidic Media. InorganicaChimicaActa, 398: 77 – 82. https://doi.org/10.1016/j.ica.2012.12.015.

      [9] Goswami, S., Shaikh, N., Panja, A. and Banerjee, P. (2003). A Comparative Kinetics Study for the Oxidation of 2-mercaptoethanol by di-µ-oxo-bis(1,4,7,10-tetraazacyclododecane)-dimanganese(III, IV) and di-µ-oxo-bis(1,4,8,11-tetraazacyclotetradecane)-dimanganese(III, IV) Complexes: Influence of Copper(II). Indian Association of Cultivation of Science, 129 – 137. https://doi.org/10.1002/kin.10182.

      [10] Messmore, J.M., Holmgren, S.K., Grilley, J.E. and Raines, R.T. (2000). Sulfur Shuffle: Modulating Enzymatic Activity by Thiol – Disulfide Interchange. Bioconjugate Chemistry, 11(3): 408 – 413.https://doi.org/10.1021/bc990142m.

      [11] Wang, Z., Liu, C., Wang, X., Matthew, J.M., Zachara, J.M., Rosso, K.M., Dupuis, M., Fredrickson, J.K., Heald, S. and Shi, L. (2008). Kinetics of Reduction of Fe III) Complexes by Outer Membrane Cytochromes MtrC and OmcA of Shewanellaoneidensis MR-1. Applied & Environmental Microbiology, 74(21): 6746 – 6755. https://doi.org/10.1128/AEM.01454-08.

      [12] Balahura, R.J. and Johnson, M.D. (1987). Outer-Sphere Dithionite Reductions of Metal Complexes. Inorganic Chemistry, 26: 3860 – 3863..https://doi.org/10.1021/ic00270a010.

      [13] Buettner, G.R., Doherty, T.P. and Patterson, R.K. (1983). The Kinetics of the Reaction of Superoxide Radical with Fe (II1) Complexes of EDTA, DETAPAC, and HEDTA. Federation of European Biochemical Societies, 158(1): 143 – 146.https://doi.org/10.1016/0014-5793(83)80695-4.

      [14] Xiao-juan, Y., Lin, Y., Li, D., Xiang-Li, L. and Wei-Kang, Y. (2011). Kinetics of the [Fe (III) EDTA] - Reduction by Sulfite under the Catalysis of Activated Carbon. Journal of American Chemical Society. 25: 4248 – 4255. https://doi.org/10.1021/ef2006063.

      [15] Francis, K.C., Cummins, D. and Oakes, J. (1985). Kinetics and Structural Investigations of [FeIII(edta)]- [edta= Ethylenediaminetetraacetate(4-)] Catalyzed Decomposition of Hydrogen Peroxide. Journal of Chemical Society, Dalton Transtion. 4:493 – 501.https://doi.org/10.1039/DT9850000493.

      [16] Bull, C., McClune, G.J. and Fee, J.A. (1983). The Mechanism of Fe-EDTA Catalyzed Superoxide Dismutation. Journal of American Chemical Society, 105(16): 5290 – 5300.https://doi.org/10.1021/ja00354a019.

      [17] Suchecki, T.T., Mathews, B., Augustyniak, A.W. and Kumazawa, H. (2014). Applied Kinetics Aspects of Ferric EDTA Complex Reduction with Metal Powder. Industrial & Engineering Chemistry Research, 53: 14234 – 14240...https://doi.org/10.1021/ie502100h.

      [18] Mshelia, M.S., Iyun, J.F., Uzairu, A. and Idris S.O. (2014). Kinetics and Mechanisms of the Oxidation of [FeEDTA]2- by Aqueous Iodine. International Journal of Engineering & Science Inventory, 3: 2319 – 6726.

      [19] Dellert-Ritter, M. and Eldik, R. (1992). Kinetics and Mechanism of the Redox Behavior of the Ethylenediamintetraacetatoferrate(III) – Sulfite System in Aqueous Solution. Journal of Chemical Society, Dalton Transition, 1045 – 1049.https://doi.org/10.1039/DT9920001045.

      [20] Onu, A.D. Iyun, J.F. Idris, S.O. (2016). Oxidation of Ethylenediamine-tetraactatocobaltate(II) Complex by Hydrogen Peroxide in Aqueous Acidic Medium: A Kinetic Study. Journal of Nigerian Chemical Society, 41(2): 81 – 86.

      [21] Iyun, J.F. (2004). The Oxidation of some Tris-(diimine) iron (II) and Tris-(substituted diimine) iron (II) Complexes by Aqueous Acidic Bromine Solution. An Assessment of the Marcus Model for Non - Complimentary Reactions. ChemClass Journal. 59 - 63.

      [22] Idris, S.O., Iyun, J.F. and Agbaji, E.B. (2008). Kinetics and Mechanism of Oxidation of Thiosulfate Ion by Tetrakis(2,2-Bipyridine)-µ-oxodiiron(III) Ion in Aqueous Acidic Medium. ChemClass Journal, 103 – 108.

      [23] Ellis, K.J., Lappin, G. and McAuley, A. (1975). Metal-Ion Oxidation in Solution: Rate- determining Dimerizations in Redox Reactions of Iron (III) with some α-mercaptocarboxylic Acids. Journal of American Chemical Society. Dalton Transition, 1931 – 1934.

      [24] Saurin, A.T., Neubert, H., Brennan, J.P. and Eaton, P. (2004). Widespread Sulfenic Acid Formation in Tissues in Response to Hydrogen Peroxide. Proceedings of the National Academy of Sciences, USA, 101: 17982 – 17987.https://doi.org/10.1073/pnas.0404762101.

      [25] Kettenhofen, N.J. and Wood, M.J. (2010). Formation, Reactivity, and Detection of Protein Sulfenic Acids. Chemical Research Toxicology, 23:1633 – 1646. https://doi.org/10.1021/tx100237w.

      [26] Eaton, P. (2006). Protein Thiol Oxidation in Health and Disease: Techniques for Measuring Disulfides and Related Modifications in Complex Protein Mixtures. Free Radical Biology Medical, 40: 1889 – 1899. Gupta, V. and Carroll, K.S. (2014). Sulfenic Acid Chemistry, Detection and Cellular Lifetime. BiochimicaETBiophysicaActa, 1840: 847 – 875. https://doi.org/10.1016/j.freeradbiomed.2005.12.037.

      [27] Gupta, V. and Carroll, K.S. (2014). Sulfenic Acid Chemistry, Detection and Cellular Lifetime. BiochimicaETBiophysica Ac-ta, 1840: 847 – 875.https://doi.org/10.1016/j.bbagen.2013.05.040.

      [28] Shi, T., Berglund, J. and Elding, L.I. (1996). Kinetics and Mechanism for Reduction of Trans-dichlorotetracyanoplatinate(IV) by Thioglycolic Acid, L-Cysteine, DL-Penicillamine, and Glutathione in Aqueous Solution. Inorganic Chemistry, 35(12): 3498 -3503.https://doi.org/10.1021/ic951598s.

      [29] Wilkins, R.G. (2002). Kinetics and Mechanism of Reactions of Transition Metal Complexes. Second Edition, Wiley-VCH Verlag GmbH & Co., 65 – 75.ISBNs: 3-527-28253-X (Hardback); 3-527-60082-5 (Electronic).

      [30] Fawzy, A., Gluesmi, N., Althagafi, I.I. and Asghar, B.H. (2017). A Study of Kinetics and Mechanism of Chromic Acid Oxidation of Isosorbide, a Chiral Biomass-derived Substrate in Aqueous Perchlorate Solution. Transition Metal Chemistry, 42: 229 – 236

      [31] Berry, R.S., Rice, S.A. and Ross, J. (1980). Physical Chemistry. John Wiley & Son Inc.New York, 1179 – 1185.

      [32] Misra, G.S. and Dubey, G.P. (1981). Aqueous Polymerization of Acrylamide Initiated by Ce (IV) - Thioglycolic Acid Redox System. Journal of Macromolecular Science Chemistry, A16 (3): 601 – 613. https://doi.org/10.1080/00222338108056808.

      [33] Sami, P., Venkateshwari, K., Mariselvi, N., Sarathi, A. and Rajasekaram, K. (2009). Studies on Electron Transfer Reaction of Heteropoly 11-tungstophosphosphovanadate (V) by L-cysteine and Thioglycolic Acid in Aqueous Acid Medium. Transition Metal Chemistry, 34: 733 – 737.https://doi.org/10.1007/s11243-009-9255-3.

      [34] Ghosh, G.K., Misra, K., Baskim, M., Linert, W. and Moi, S.C. (2013). Kinetics and Mechanism of the Interaction of di-µ-hydroxo-bis(1,10-phenanthroline)dipalladium(II) Perchlorate with Thioglycolic Acid and Glutathione in Aqueous Solution. Journal of Solution Chemistry, 42: 526 – 543.https://doi.org/10.1007/s10953-013-9973-1.

      [35] Gangopahyay, S., Ali, M., Dutta, A. and Banerjee, P. (1994). Oxidation of Thioglycolic Acid and Glutathione by (trans-cyclohexane-1, 2-diamine-N, N, N1, N1-tetraacetato) manganese (III) in Aqueous Media. Journal of American Chemical Society.Dalton Transition, 3: 841 – 845.https://doi.org/10.1039/DT9940000841.

      [36] Weaver, M.J. and Yee, E.L. (1980). Activation Parameters for Homogenous Outer-sphere Electron Transfer Reactions. Comparison between Self –Exchange, and Cross-Reactions using Marcus Theory. Inorganic Chemistry, 19: 1936.https://doi.org/10.1021/ic50209a023.

      [37] Osunlaja, A.A., Idris, S.O. and Iyun, J.F. (2012). Mechanism of the Reduction of Methylene Blue by Thiourea in Aqueous Acid Medium. International Journal of ChemTecch Research, 4(2): 609 – 617.

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    U. Nkole, I., R. Osunkwo, C., D. Onu, A., & D. Onu, O. (2018). Kinetics and mechanism of the reduction of n-(2-hydroxyethyl)ethylenediaminetriacetatoiron(III) complex by thioglycol in bicarbonate buffer medium. International Journal of Advanced Chemistry, 6(1), 102-107. https://doi.org/10.14419/ijac.v6i1.10902

    Received date: 2018-04-01

    Accepted date: 2018-05-19

    Published date: 2018-06-05