Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium

Ismail Althagafi; Ahmed Fawzy; Ishaq A. Zaafarany; Fahd A. Tirkistani; Khalid S. Khairou

doi:doi:10.11648/j.ajpc.20160505.11

| Peer-Reviewed

Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium

Ismail Althagafi, Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Khalid S. Khairou

Published in American Journal of Physical Chemistry (Volume 5, Issue 5)

Received: 7 September 2016 Accepted: 23 September 2016 Published: 11 October 2016

Views: Downloads:

Download PDF

Share This Article

Twitter
Linked In
Facebook

Abstract

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.

Published in	American Journal of Physical Chemistry (Volume 5, Issue 5)
DOI	10.11648/j.ajpc.20160505.11
Page(s)	87-93
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, Kinetics, Mechanism, Oxidation, Cerium(IV)

References

[1]	Michell RH (2007) Evolution of the diverse biological roles of inositols. BiochemSoc Symp. 74: 223-246.
[2]	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.
[3]	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.
[4]	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.
[5]	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.
[6]	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.
[7]	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.
[8]	Kumar A, Rain M (1974) Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium (pages. Int J ChemKinet. 6:15-28.
[9]	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.
[10]	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.
[11]	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.
[12]	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.
[13]	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.
[14]	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.
[15]	Richardson W H (1965) Oxidation of organic chemistry, In K B Wiberg (ed.) (Academic Press: London) p. 244.
[16]	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.
[17]	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.
[18]	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.
[19]	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.
[20]	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.
[21]	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.
[22]	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
[23]	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.
[24]	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.
[25]	Hardwick TJ, Robertson E (1951) Ionic species in ceric perchlorate solutions. Can. J. Chem., 29: 818-828
[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 A I (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]	Sherill MS, King CB, Spooner RC (1943) The oxidation potential of cerous-ceric perchlorates. J. Am. Chem. Soc. 65:170-179.
[30]	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
[31]	King EL, Pandow ML (1952) The spectra of cerium (IV) in perchloric acid. Evidence for polymeric species. J. Am. Chem. Soc. 74:1966-1969
[32]	Offner HG, Skoog DA (1966) Hydrolysis constant of quadrivalent cerium from spectrometric measurements. Anal. Chem. 38:1520-1521
[33]	Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z., 49:333–369
[34]	Frost AA, Person RG (1973) Kinetics and mechanism, p. 147, Wiley Eastern, New Delhi
[35]	Amis ES (1966) Solvent effect on reaction rates and mechanism, p. 28, Academic Press, New York
[36]	Weissberger A (1974) In Investigation of rates and mechanism of reactions in techniques of chemistry, (New York: John Wiley & Sons), p. 421.

Cite This Article

Plain Text BibTeX RIS

APA Style

Ismail Althagafi, Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Khalid S. Khairou. (2016). Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium. American Journal of Physical Chemistry, 5(5), 87-93. https://doi.org/10.11648/j.ajpc.20160505.11

Copy | Download

ACS Style

Ismail Althagafi; Ahmed Fawzy; 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. Am. J. Phys. Chem. 2016, 5(5), 87-93. doi: 10.11648/j.ajpc.20160505.11

Copy | Download

AMA Style

Ismail Althagafi, Ahmed Fawzy, 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. Am J Phys Chem. 2016;5(5):87-93. doi: 10.11648/j.ajpc.20160505.11

Copy | Download

@article{10.11648/j.ajpc.20160505.11,
  author = {Ismail Althagafi and Ahmed Fawzy and Ishaq A. Zaafarany and Fahd A. Tirkistani and Khalid S. Khairou},
  title = {Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium},
  journal = {American Journal of Physical Chemistry},
  volume = {5},
  number = {5},
  pages = {87-93},
  doi = {10.11648/j.ajpc.20160505.11},
  url = {https://doi.org/10.11648/j.ajpc.20160505.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20160505.11},
  abstract = {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.},
 year = {2016}
}

Copy | Download

TY  - JOUR
T1  - Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium
AU  - Ismail Althagafi
AU  - Ahmed Fawzy
AU  - Ishaq A. Zaafarany
AU  - Fahd A. Tirkistani
AU  - Khalid S. Khairou
Y1  - 2016/10/11
PY  - 2016
N1  - https://doi.org/10.11648/j.ajpc.20160505.11
DO  - 10.11648/j.ajpc.20160505.11
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 87
EP  - 93
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20160505.11
AB  - 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.
VL  - 5
IS  - 5
ER  -

Copy | Download

Author Information

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
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

Download PDF

Sections

Plain Text BibTeX RIS

APA Style

Ismail Althagafi, Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Khalid S. Khairou. (2016). Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium. American Journal of Physical Chemistry, 5(5), 87-93. https://doi.org/10.11648/j.ajpc.20160505.11

Copy | Download

ACS Style

Ismail Althagafi; Ahmed Fawzy; 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. Am. J. Phys. Chem. 2016, 5(5), 87-93. doi: 10.11648/j.ajpc.20160505.11

Copy | Download

AMA Style

Ismail Althagafi, Ahmed Fawzy, 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. Am J Phys Chem. 2016;5(5):87-93. doi: 10.11648/j.ajpc.20160505.11

Copy | Download

@article{10.11648/j.ajpc.20160505.11,
  author = {Ismail Althagafi and Ahmed Fawzy and Ishaq A. Zaafarany and Fahd A. Tirkistani and Khalid S. Khairou},
  title = {Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium},
  journal = {American Journal of Physical Chemistry},
  volume = {5},
  number = {5},
  pages = {87-93},
  doi = {10.11648/j.ajpc.20160505.11},
  url = {https://doi.org/10.11648/j.ajpc.20160505.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20160505.11},
  abstract = {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.},
 year = {2016}
}

Copy | Download

TY  - JOUR
T1  - Kinetics and Mechanistic Approach to the Oxidation of Inositol by Cerium(IV) in Aqueous Perchlorate Medium
AU  - Ismail Althagafi
AU  - Ahmed Fawzy
AU  - Ishaq A. Zaafarany
AU  - Fahd A. Tirkistani
AU  - Khalid S. Khairou
Y1  - 2016/10/11
PY  - 2016
N1  - https://doi.org/10.11648/j.ajpc.20160505.11
DO  - 10.11648/j.ajpc.20160505.11
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 87
EP  - 93
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20160505.11
AB  - 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.
VL  - 5
IS  - 5
ER  -

Copy | Download