Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium
American Journal of Physical Chemistry
Volume 5, Issue 5, October 2016, Pages: 87-93
Received: Sep. 7, 2016;
Accepted: Sep. 23, 2016;
Published: Oct. 11, 2016
Views 3652 Downloads 159
Ismail Althagafi, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Ahmed Fawzy, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Ishaq A. Zaafarany, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Fahd A. Tirkistani, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Khalid S. Khairou, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Oxidation kinetics of inositol (INOS) by cerium(IV) has been studied spectrophotometrically in perchlorate medium at fixed ionic strength and temperature. The reaction showed a first order dependence with respect to [Ce(IV)] and less than unit order kinetics in both [H+] and [INOS]. Increasing both ionic strength and dielectric constant of the reaction medium increased the oxidation rate. Addition of Ce(III) product had no any significant effect on the oxidation rate. The oxidation product of inositol was identified by both spectroscopic and chemical tools as inosose. A plausible mechanistic scheme for oxidation reaction has been proposed and the rate law associated with the reaction mechanism was derived. The activation parameters of the second order rate constant were calculated and discussed.
Ishaq A. Zaafarany,
Fahd A. Tirkistani,
Khalid S. Khairou,
Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium, American Journal of Physical Chemistry.
Vol. 5, No. 5,
2016, pp. 87-93.
Michell RH (2007) Evolution of the diverse biological roles of inositols. BiochemSoc Symp. 74: 223-246.
Shen X, Xiao H, Ranallo R, Wu W H and Wu C (2003) Modulation of ATP-dependent chromatin-remodeling complexes by inositol polyphosphates. Science 299:112-114.
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.
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.
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.
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.
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.
Kumar A, Rain M (1974) Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium (pages. Int J ChemKinet. 6:15-28.
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.
Hassan RM, Alaraifi A, Fawzy A, Zaafarany IA, Khairou KS, Ikeda Y and Takagi HD (2010) Acid-catalyzed oxidation of some sulfated polysaccharides. Kinetics and mechanism of oxidation of kappa-carrageenan by cerium (IV) in aqueous perchlorate solutions. J. Mol. Cat. A, 332:138–144.
Fawzy A (2016) Oxidation of alginate and pectate biopolymers by cerium (IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study. Carbohydr. Polym. 138: 356-364.
Fawzy A (2016) Kinetic and mechanistic aspects of oxidation of aminotriazoleformamidine by cerium (IV) in aqueous perchloric and sulfuric acid solutions: a comparative study. J. Solution Chem. 45:46-264.
Fawzy A, Hassan R M, Althagafi I, Morad M (2016) Cerium (IV) oxidation of sulfated polysaccharides in aqueous perchlorate solutions. A Kinetic and mechanistic approach. Adv. Mater. Lett. 7: 122-128.
Fawzy A, Zaafarany I A, Tirkistani F A, Al-Benayan A and Aljiffrey F A (2016) Kinetics and mechanistic study of oxidation of pyridine derivative by cerium (IV) in aqueous perchloric acid, Am. J. Phys. Chem. 5:10-16.
Richardson W H (1965) Oxidation of organic chemistry, In K B Wiberg (ed.) (Academic Press: London) p. 244.
Adari KK, Nowduri A, Parvataneni V (2008) Kinetics and mechanism of oxidation of L-cystine by cerium (IV) in sulphuric acid medium. ActaChim. Slov. 55:425–429.
Sumathi T, Shanmugasundaram P and Chandramohan G (2013) A kinetic and mechanistic study on the silver (I) catalyzed oxidation of L-Serine by cerium (IV) in sulfuric acid medium. J. Saudi Chem. Soc. 17:227-233.
Thabaj KA, Chimatadar SA, Nandibewoor ST (2006) Mechanistic study of oxidation of palladium (II) by cerium (IV) in aqueous acid. Transition Met. Chem., 31:186-193.
Datt N, Nagori RR, Mehrotra RN (1986) Kinetics and mechanisms of oxidations by metal ions. Part VI. Oxidation of α-hydroxy acids by cerium (IV) in aqueous nitric acid. Can. J. Chem. 64: 19-23.
McCurdy, Jr WH, Guilbault GG (1960) Catalysts for cerium (IV) oxidimetry: determination of mixtures of mercury (I) and mercury (II). Anal. Chem. 32:647-650.
Mishra SK, Gupta YK (1970) Kinetics of oxidation of antimony (III) by cerium (IV) in media containing perchloric acid. J. Chem. Soc. A, 260-264.
Yadav MB, Derva V, Rani A (2009) Kinetics and mechanism of uncatalyzed and silver (I) catalyzed oxidation of lysine by cerium (IV) in acid perchlorate medium. J. Indian Chem. Soc. 86: 600-604
Mathur S, Yadav MB, Devra V (2013) Kinetics and mechanism of uncatalyzed and Ag (I) catalyzed oxidation of hydroxylysine by cerium (IV) in acid medium. J. Phys. Chem. Biophys. 3:5-12.
Mathur S, Yadav MB, Devra V (2015) Kinetics and mechanism of uncatalyzed and Ag (I) catalyzed oxidation of serine by cerium (IV) in acid medium. Int. J. Res. Phys. Chem. 5:1-6.
Hardwick TJ, Robertson E (1951) Ionic species in ceric perchlorate solutions. Can. J. Chem., 29: 818-828
Furniss BS, Hannaford AJ, Smith WG, Tatchell AR (2004) In Vogel’s textbook of practical organic chemistry, 5th (ed.) (Pearson Education Ltd)
Vogel A I (1973) In Text book of practical organic chemistry, 3rd (ed.) (London: Longman) p. 332
Feigl F (1975) Spot tests in organic analysis, p. 195, Elsevier, New York.
Sherill MS, King CB, Spooner RC (1943) The oxidation potential of cerous-ceric perchlorates. J. Am. Chem. Soc. 65:170-179.
Heidt LJ, Smith ME (1948) Quantum yields of the photochemical reduction of ceric ions by water and evidence for the dimerization of ceric ions. J. Am. Chem. Soc., 70: 2476-2481
King EL, Pandow ML (1952) The spectra of cerium (IV) in perchloric acid. Evidence for polymeric species. J. Am. Chem. Soc. 74:1966-1969
Offner HG, Skoog DA (1966) Hydrolysis constant of quadrivalent cerium from spectrometric measurements. Anal. Chem. 38:1520-1521
Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z., 49:333–369
Frost AA, Person RG (1973) Kinetics and mechanism, p. 147, Wiley Eastern, New Delhi
Amis ES (1966) Solvent effect on reaction rates and mechanism, p. 28, Academic Press, New York
Weissberger A (1974) In Investigation of rates and mechanism of reactions in techniques of chemistry, (New York: John Wiley & Sons), p. 421.