Research Article | Open Access | 10.31586/Chemistry.0402.04
Orientation on Electron-Transfer Nature for Oxidation of Some Water-Soluble Carbohydrates: Kinetics and Mechanism of Hexacholroiridate (IV) Oxidation of Methyl Cellulose in Aqueous Perchlorate Solutions
Received October 24, 2018
Revised January 12, 2019
Accepted January 22, 2019
Published February 1, 2019
AbstractThe kinetics and mechanism of oxidation of methyl cellulose (MC) polysaccharide by hexacholroiridate (IV) in aqueous perchlorate solutions at a constant ionic strength of 0.1 mole dm-3 has been investigated, spectrophotometrically. The experimental results showed first-order dependence in [IrCl6]2- and fractional first-order kinetics with respect to the MC concentration. The reaction rate was found to increase with decreasing the [H+]. A kinetic evidence for formation of 1:1 intermediate complex was revealed. The reaction kinetics seems to be of considerable complexity where one chloride ion from hexacholoiridate (IV) oxidant may act as a bridging ligand between the oxidant and the substrate within the formed intermediate complex. However the added chloride ions and oxidation products were found to have negligible effects on the reaction rate, the added acrylonitrile indicated the intervention of free-radical mechanism during the oxidation process. The kinetic parameters have been evaluated and a tentative reaction mechanism consistent with the kinetic results is discussed.
McAllister JW, Lott JR, Schmidt PW, Sammler RL, Bates FS, Lodge TP (2015) Linear and nonlinear rheological behavior of febrile methylcellulose hydrogels. ACS Macro Lett 4: 538-542.
Lee JY, Kwak HW, Yun H, Kim YW, Lee KH (2016) Methyl cellulose nanofibrous mat for lipase immobilization via cross-linked enzyme aggregates. Macromolecular Research 24: 218-225.
Shaker AM (2001) Base catalyzed oxidation of carboxymethyl cellulose polymer by permanganate. I- Kinetics and mechanism of formation of manganate (VI) transient species complexes. J Colloid Interface Sci 233: 197-204.
Shaker AM (2001) . J Colloid Interface Sci 244: 254-261.
Hassan RM (2016) “ ”Edited by” Vijay K. Thakur & Manju K. Thakur “Pan Stanford Publishing, Pre Ltd. Publication City/Country Singapore, Singapore 411-454; Hassan RM, Dahy A, Ibrahim SM, Zaafarany IA, Fawzy A(2012) Oxidation of some macromolecules. Kinetics and mechanism of oxidation of methyl cellulose by permanganate ion in acid perchlorate solutions. Ind Eng Chem Res 51: 5424-5432.
Hassan RM, Ibrahim SM, Zaafarany IA, Fawzy A, Takagi HD (2011) Base-catalyzed oxidation: Kinetics and mechanism of hexacyanoferrate (III)oxidation of methyl cellulose polysaccharide in alkaline solutions. J Mol Cat A 344: 93-98.
Hassan RM, Fawzy A, Ahmed GA, Zaafarany IA, Asghar BH, Khairou KS (2009) Acid-catalyzed oxidation of some sulfated macromolecules. Kinetics and mechanism of permanganate oxidation of kappa-carrageenan polysaccharides in acid perchlorate solutions. J Mol Cat A 309: 95-102.
Zaafarany IA, Khairou KS, Hassan RM (2009) Acid-catalysis of chromic acid oxidation of kappa-carrageenan polysaccharide in aqueous perchlorate solutions. J Mol Cat 302: 112-118.
Hassan RM, Ibrahim SM, Dahy A, Zaafarany IA, Tirkistani F, Takagi HD (2013) Kinetics and mechanism of oxidation of chondroitin-4-sulfate polysaccharide by chromic acid in aqueous perchlorate solutions. Carbohyd Poly 92: 2321-2326.
Hassan RM (1993) Alginate polyelectrolyte ionotropic gels. XVIII. Oxidation of alginate polysaccharide by potassium permanganate in alkaline solutions. Kinetics of decomposition of the intermediate complex. J Poly Sci 5A, 31: 1147-1151.
Hassan RM (1993) New coordination polymers. III. Oxidation of poly (vinyl alcohol) by permanganate ion in alkaline solutions. Kinetics and mechanism of formation of an intermediate complex with a spectrophotometric detection of manganate(VI) transient species. Poly Inter 30: 5-9.
Abdel-Hamid MI, Khairou KS, Hassan RM (2003) Kinetics and mechanism of permanganate oxidation of pectin in acid perchlorate media. Eur Poly 39: 381-387.
Ahmed GA, Khairou KS, Hassan RM (2003) Kinetics and mechanism of oxidation of chitosan polysaccharide by permanganate ion in aqueous perchlorate solutions. J Chem Res 182-183.
Hassan RM, Fawzy A, Ahmed GA, Zaafarany IA, Asghar BH, Takagi HD, Ikeda Y (2011) Kinetics and mechanism of permanganate oxidation of iota- and lambda- carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions. Carbohydrate Research 346: 2260-2267.
Hassan RM, Zaafarany IA, Takagi HD (2013) Oxidation of some water-soluble anionic polyelectrolytes: Oxidation of carboxymethyl cellulose polysaccharide by hexachloroiridate(IV) in aqueous perchlorate solutions. A Kinetic and mechanistic approach to electron transfer process. Indust & Eng Chem Res 52 : 1531-1537; Ahmed G A, Hassan RM (2001) Kinetics and mechanism of reduction of hexachloroiridate(IV) by kojic acid in aqueous perchlorate solutions. Bull Polish Acad Sci 49: 235-244.
El-Korshy MA, Hassan R M (1998)Kinetics and mechanism of oxidation of ADA by hexachloroiridate (IV) in aqueous perchloric acid. Bull Polish Acad Sci 46: 147-155.
Hassan RM, Zaafarany IA, Takagi HD, Ikeda Y (2013) Kinetics and mechanism of hexachloroiridate(IV) oxidation of tellurium(IV) in aqueous solutions. New J Chem 37: 2700-2707; Hassan RM (1991) Kinetics of reaction of uranium (IV) and hexachloroiridate(IV) in acid perchlorate solutions. J Chem Soc Dalton Trans 3003-3008.
Hassan RM (1992) Kinetics and mechanism of hexachloroiridate(IV) oxidation of arsenic(III) in acidic perchlorate solutions. Collect Czech Chem Commun 57: 1451.
Poulson I A, Garner CS (1962) A thermodynamic and kinetic study of hexachloro and aquopentachloro complexes of iridium(III) in aqueous solutions. J Am Chem Soc 84: 2032-2037.
Thornley RNF, Sykes SA (1970) Kinetics of the one-equivalent reactions of vanadium(II), vanadium(III), and iron(II) with hexachloroiridate(IV). J Chem Soc A 1036-1037.
Morris DFC, Ritter TJ (1979) Oxidation of hydrazine by halogeno complexes of iridium (IV) in acidic perchloric solutions. J Chem Soc Dalton Trans 216-219.
Malik MA, Ilyas M, Khan Z (2009) Kinetics of permanganate oxidation of synthetic macromolecule poly(vinyl alcohol). Ind J Chem 48 A : 189-193.
Khairou KS, Hassan RM, Shaker MA(2002) Novel synthesis of diketocarboxymethyl cellulose as biopolymer precursors. J Appl Poly Sci 85: 1019-1023.
Hassan RM, Abd-Alla MA(1992) New coordination polymers. I. Novel synthesis of poly (vinyl alcohol) and characterization as chelating agent. J Mater Sci 2: 609-611.
Pretch E, Clerc T, Seibl J, Simon W, Tables of Spectral Data for Structure Determination of Organic Compounds, Springer-Verlag, Berlin, Heidelberg, New York, Tokyo, 1983 (Translation).
Hassan RM(1991) Kinetics and mechanism of oxidation of DL-α-alanine by permanganate ion in acid perchlorate media. Can J Chem 69: 2018-2023.
Sen Gubta KK, Chatterjee U, Sen PK(1978) Kinetics and mechanism of oxidation of glyoxylate ion by Ir (IV). Ind J Chem 16B: 767-770.
Sen Gubta KK, Bhattacharjee N(2002) Oxidative behavior and relative reactivities of some unsaturated compounds towards hexachloroiridate(IV) in perchloric acid medium. Int J Chem Kinet 34: 411-417.
Sen Gubta KK, Uma Chatterjee (1981) Kinetics of oxidation of methanol, ethanol and isopropanol by hexachloroiridate(IV). J Inorg Nucl Chem 43: 2491-2497.
Ogino H, Bailar Jr. JC (1978) Stereochemistry of complex inorganic compounds. 36. Ammoniation reactions of some optically active 1,2-dihalobis(ethylenediamine) complexes of rhodium(III) and iridium(III) ions. Inorg Chem 17: 1118-1124.
Po HN, Lo CF, Jones N, Lee RW (1980) The oxidation of 2-thiopyrimidine and 2-thiouracil by Ir(IV) complexes. Inorg Chim Acta 46: 185-189.
Kottapalli KK, Adari KK, Vani P, Govindan SK (2005) Mechanism of Oxidation of L-Cysteine by Hexachloroiridate(IV) - A Kinetic Study. Trans Metal Chemistry 30 : 773-777; Ayoko GA, Lyun JF, Ekubo T (1992) Kinetics of the reduction of hexachloroiridate (IV) by L-methionine in aqueous-solutions. Ind J Chem 31 A: 975-980.
Sykes AG, Thornley RNF(1970) Identification of inner- and outer-sphere paths in the reaction of chromium(II) with hexachloroiridate(IV), and the kinetics of the decomposition of the binuclear intermediate. J Chem Soc A 232-238.
San Gupta K K, Deg S, Sen Gupta S, Banerjee A (1984) Kinetics and mechanism of the oxidation of aromatic aldehydes by hexachloroiridate(IV). J Org Chem 49: 5054-5057.
Scurlock RD, Gilbert DD, Dekorte IM (1985) Oxidation of ascorbic acid by aquopentabromoiridate(IV): an assessment of the effect of aquation on rates of oxidation by bromo- and chloroiridium(IV) complexes. Inorg Chem 24: 2393-2397.
Pirk JP (1977) Mechanism of the reversible oxidation of vanadium(IV). Inorg Chem 16: 1381-1383.
Newton TW (1986) The kinetics of oxidation-reduction reactions - an alternative derivation of Marcus’ cross relation. J Chem Educ 45: 571-576.
Gordon BJ, Williams LL, Sutin N (1961) The kinetics of oxidation of iron(II) ions and coordination complexes. J Am Chem Soc 83: 2061-2064.
Wharton RK, Ojo JF, Sykes AG (1975) Mechanism of the oxidation of the molybdenum(V)-ethylenediaminetetra-acetato dimer by hexachloroiridate(IV) and tris(1,10-phenanthroline)iron(III). J Am Chem Soc Dalton Trans 1526-1530.
Adedinsewo CO, Adgite A (1979) Linear free energy relations in redox reactions. Oxidation of iodide ion by poly(pyridine)-iron(III) complexes and hexachloroiridate(IV) ion. Inorg Chem 18: 3597-3601.
Hurwitz P, Kustin K (1964) Kinetics of fast electron-transfer reactions. Inorg Chem 3: 823-826.
Sen-Gupta KK, Chatterjee U (1981) Kinetics of oxidation of methanol, ethanol and isopropanol by hexachloroiridate(IV). J Inorg Nucl Chem 43: 2491-2497.
Moggi L, Varani G, Manfrin MF, Balazani V (1970) Photochemical-reactions of hexachloroiridate(IV) ion. Inorg Chem Acta 4: 335-341.
AL-Ajlouni, Bakac A, Esponson JH (1994) Hydride abstraction from 1,2-diols by the pentaaqua(oxo)chromium(IV) ion. Inorg Chem 33: 1011-1014.
Chimatdar SA, Nandibewoor ST, Sambrani MI, Raju JR (1987) Chromium(III)-catalysed cerium(IV) oxidation of arsenic(III) in aqueous sulphuric acid. J Chem Soc Dalton Trans 573.
Sutin N (1968) Free energies, barriers and reactivity patterns in electron transfer reactions. Acc Chem Res1: 225-231.
Hassan RM(1992) A review on oxidation of uranium (IV) by polyvalent metal ions. A linear free-energy correlation. J Coord Chem 27: 255-266.