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Kinetics and Mechanism of Permanganate Oxidation of Inositol in Perchloric and Sulfuric Acids Solutions

Received: 29 August 2016     Accepted: 5 September 2016     Published: 24 September 2016
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Abstract

The kinetics of oxidation of inositol (INOS) by permanganate ion in both perchloric and sulfuric acids solutions was studied using a spectrophotometric technique at a constant ionic strength of 1.0 mol dm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [INOS] were found to be less than unity. The effect of acids concentrations suggests that the reactions were acid-catalyzed with fractional-second order kinetics in [H+]. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of inositol were identified by spectral and chemical tools as the corresponding monoketone derivative, namely inosose. Under comparable experimental conditions, the oxidation rate in sulfuric acid was approximately three times higher than that in perchloric acid. Regarding to the second order rate constants of these reactions, the activation parameters have been evaluated and discussed.

Published in American Journal of Chemical Engineering (Volume 4, Issue 5)
DOI 10.11648/j.ajche.20160405.12
Page(s) 98-104
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), 2016. Published by Science Publishing Group

Keywords

Inositol, Oxidation, Acid, Permanganate, Kinetics, Mechanism

References
[1] Stewart R (1965) Oxidation in Organic Chemistry, Part A (ed.) Wiberg KB, New York, Academic Press.
[2] Jose TP, Nandibewoor ST, Tuwar SM (2005) Mechanism of oxidation of L-histidine by heptavalent manganese in alkaline medium. E-J. Chem. 2: 75-85.
[3] Fawzy A, Ashour SS, Musleh MA, (2014) Base-catalyzed oxidation of L-asparagine by alkaline permanganate and the effect of alkali-metal ion catalysts: kinetics and mechanistic approach, React. Kinet. Mech. Catal. 111:443-460.
[4] Fawzy A, Shaaban MR (2014) Kinetic and mechanistic investigations on the oxidation of N’-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium. Transition Met. Chem. 39: 379-386.
[5] Fawzy A, Zaafarany IA, Alfahemi J, Tirkistani FA (2015) Base-catalyzed oxidation of aminotriazole derivative by permanganate ion in aqueous alkaline medium: a kinetic study. Int. J. Inn. Res. Sci. Eng. Tech. 4: 6802-6814.
[6] Asghar BH, Fawzy A (2014) Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese(II). J. Saudi Chem. Soc., in press.
[7] Fawzy A, Ashour SS, Musleh MA (2014) Kinetics and mechanism of oxidation of L-histidine by permanganate ions in sulfuric acid medium. Int. J. Chem. Kinet. 46: 370-381.
[8] Ahmed GA, Fawzy A, Hassan RM (2007) Spectrophotometric evidence for the formation of short-lived hypomanganate(V) and manganate(VI) transient species during the oxidation of K-carrageenan by alkaline permanganate. Carbohydr. Res. 342: 1382-1386.
[9] Zaafarany IA, Fawzy A, Ahmed GA, Ibrahim SA, Hassan RM, Takagi HD (2010) Further evidence for detection of short-lived transient hypomanganate(V) and manganate(VI) intermediatesduring oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometeric techniques. Carbohydr. Res. 345:1588-1593.
[10] Hassan RM, Fawzy A, Alarifi A, Ahmed GA, Zaafarany IA, Takagi HD (2011) Base-catalyzed oxidation of some sulfated macromolecules: kinetics and mechanism of formation of intermediate complexes of short-lived manganate (VI) and/or hypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganate. J. Mol. Catal. A, 335:38-45.
[11] Hassan RM, Dahy A, Ibrahim S, Zaafarany IA, Fawzy A (2012) Oxidation of some macromolecules. Kinetics and mechanism of oxidation of methyl cellulose polysaccharide by permanganate ion in acid perchlorate solutions. Ind. Eng. Chem. Res. 51:5424–5432.
[12] Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate:  oxidations of arylalkanes in organic solvents. Inorg. Chem. 36: 2069-2078.
[13] Perez-Benito JF (2009) Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways. J. Phys. Chem. 113:15982-5989.
[14] Babatunde OAA (2008) study of the kinetics and mechanism of oxidation L-ascorbic acid by permanganate ion in acidic medium. World J. Chem. 3:27-35.
[15] Day MC, Selbin J (1985) Theoretical Inorganic Chemistry, Reinhold Publishing Corporation, New York, p. 344.
[16] Michell RH (2007) Evolution of the diverse biological roles of inositols. Biochem Soc Symp. 74: 223-246.
[17] Shen X, Xiao H, Ranallo R, Wu WH, Wu C (2003) Modulation of ATP-dependent chromatin-remodeling complexes by inositol polyphosphates. Science 299: 112-114.
[18] Rapiejko PJ, Northup JK, Evans T, Brown JE, Malbon CC (1986) G proteins of fat cells role in hormonal regulation of intracellular inositol 1,4,5-trisphosphate. Biochem. J. 240: 35-40.
[19] Larner J (2002) D-chiro-inositol –iIts functional role in insulin action and its deficit in insulin resistance. Int. J. Exp. Diabetes Res.3:47-60.
[20] Kumar YL, Nadh RV, Radhakrisinami PS (2012) Kinetics of oxidation of myo-inositol by potassium periodate in alkaline medium. Asian J. Chem. 24:5869-5872.
[21] Nayak GT, Hadmani CC, Harihar AL (2015) Kinetic and mechanistic investigations of oxidation of myo-inositol by diperiodatocuprate(III) in aqueous alkaline medium. Chem. Sci. Trans. 4:199-207.
[22] Nayak GT, Hadmani CC, Harihar AL (2014) Oxidation of myo-inositol by alkaline permanganate and the effect of alkali metal ion catalysts: kinetic and mechanistic approach. Know Res. 1:33-39.
[23] Kumar A, Rain M (1974) Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium (pages). Int J ChemKinet. 6:15-28.
[24] Santoro M, Caffaratti E, Salas-Peregrin GM, Korecz L, Rockenbauer A, Sala LF, Signorella F (2007) Kinetics and mechanism of the chromic oxidation of myo-inositol. Polyhedron 26:169–177.
[25] Vogel IAA (1978) Text Book of Quantitative Inorganic Analysis. 4th Ed. ELBS and Longman, New York, p. 352.
[26] Furniss BS, Hannaford AJ, Smith WG, Tatchell AR (2004) In Vogel’s textbook of practical organic chemistry, 5th (ed.) (Pearson Education Ltd).
[27] Vogel AI (1973) In Text book of practical organic chemistry, 3rd (ed.) (London: Longman) p. 332.
[28] Feigl F (1975) Spot tests in organic analysis, p. 195, Elsevier, New York.
[29] Bailey N, Carrington A, Lott T, Symons MCRJ (1960) Structure and reactivity of the oxyanions of transition metals. Part VIII. Acidities and spectra of protonated oxyanions. J. Chem. Soc. 290-297.
[30] Carrington A, Symons MCRJ (1963) Structure and reactivity of the oxyanions of transition metals. Chem. Rev. 63:443-460
[31] Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z., 49: 333–369.
[32] Amis ES (1966) Solvent effect on reaction rates and mechanism, p. 28, Academic Press, New York.
[33] Frost AA, Person RG (1973) Kinetics and mechanism, p. 147, Wiley Eastern, New Delhi.
[34] Weissberger A (1974) In Investigation of rates and mechanism of reactions in techniques of chemistry, (New York: John Wiley & Sons), p. 421.
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    Ahmed Fawzy, Ishaq A. Zaafarany, Hatem M. Altass, Moataz H. Morad, Jabir Alfahemi. (2016). Kinetics and Mechanism of Permanganate Oxidation of Inositol in Perchloric and Sulfuric Acids Solutions. American Journal of Chemical Engineering, 4(5), 98-104. https://doi.org/10.11648/j.ajche.20160405.12

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    ACS Style

    Ahmed Fawzy; Ishaq A. Zaafarany; Hatem M. Altass; Moataz H. Morad; Jabir Alfahemi. Kinetics and Mechanism of Permanganate Oxidation of Inositol in Perchloric and Sulfuric Acids Solutions. Am. J. Chem. Eng. 2016, 4(5), 98-104. doi: 10.11648/j.ajche.20160405.12

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    AMA Style

    Ahmed Fawzy, Ishaq A. Zaafarany, Hatem M. Altass, Moataz H. Morad, Jabir Alfahemi. Kinetics and Mechanism of Permanganate Oxidation of Inositol in Perchloric and Sulfuric Acids Solutions. Am J Chem Eng. 2016;4(5):98-104. doi: 10.11648/j.ajche.20160405.12

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  • @article{10.11648/j.ajche.20160405.12,
      author = {Ahmed Fawzy and Ishaq A. Zaafarany and Hatem M. Altass and Moataz H. Morad and Jabir Alfahemi},
      title = {Kinetics and Mechanism of Permanganate Oxidation of Inositol in Perchloric and Sulfuric Acids Solutions},
      journal = {American Journal of Chemical Engineering},
      volume = {4},
      number = {5},
      pages = {98-104},
      doi = {10.11648/j.ajche.20160405.12},
      url = {https://doi.org/10.11648/j.ajche.20160405.12},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajche.20160405.12},
      abstract = {The kinetics of oxidation of inositol (INOS) by permanganate ion in both perchloric and sulfuric acids solutions was studied using a spectrophotometric technique at a constant ionic strength of 1.0 mol dm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [INOS] were found to be less than unity. The effect of acids concentrations suggests that the reactions were acid-catalyzed with fractional-second order kinetics in [H+]. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of inositol were identified by spectral and chemical tools as the corresponding monoketone derivative, namely inosose. Under comparable experimental conditions, the oxidation rate in sulfuric acid was approximately three times higher than that in perchloric acid. Regarding to the second order rate constants of these reactions, the activation parameters have been evaluated and discussed.},
     year = {2016}
    }
    

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  • TY  - JOUR
    T1  - Kinetics and Mechanism of Permanganate Oxidation of Inositol in Perchloric and Sulfuric Acids Solutions
    AU  - Ahmed Fawzy
    AU  - Ishaq A. Zaafarany
    AU  - Hatem M. Altass
    AU  - Moataz H. Morad
    AU  - Jabir Alfahemi
    Y1  - 2016/09/24
    PY  - 2016
    N1  - https://doi.org/10.11648/j.ajche.20160405.12
    DO  - 10.11648/j.ajche.20160405.12
    T2  - American Journal of Chemical Engineering
    JF  - American Journal of Chemical Engineering
    JO  - American Journal of Chemical Engineering
    SP  - 98
    EP  - 104
    PB  - Science Publishing Group
    SN  - 2330-8613
    UR  - https://doi.org/10.11648/j.ajche.20160405.12
    AB  - The kinetics of oxidation of inositol (INOS) by permanganate ion in both perchloric and sulfuric acids solutions was studied using a spectrophotometric technique at a constant ionic strength of 1.0 mol dm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [INOS] were found to be less than unity. The effect of acids concentrations suggests that the reactions were acid-catalyzed with fractional-second order kinetics in [H+]. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of inositol were identified by spectral and chemical tools as the corresponding monoketone derivative, namely inosose. Under comparable experimental conditions, the oxidation rate in sulfuric acid was approximately three times higher than that in perchloric acid. Regarding to the second order rate constants of these reactions, the activation parameters have been evaluated and discussed.
    VL  - 4
    IS  - 5
    ER  - 

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Author Information
  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

  • Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt

  • Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt

  • Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt

  • Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt

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