A Study of the Kinetics and Mechanism of Oxidation of Fluorene by Alkaline Hexacyanoferrate(III)
American Journal of Physical Chemistry
Volume 6, Issue 3, June 2017, Pages: 42-48
Received: Apr. 12, 2017;
Accepted: Apr. 21, 2017;
Published: Jun. 14, 2017
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Ahmed Fawzy, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Rabab S. Jassas, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Saleh A. Ahmed, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Hazim M. Ali, Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt; Chemistry Department, Faculty of Science, Aljouf University, Aljouf, Saudi Arabia
Nermeen S. Abbas, Chemistry Department, Faculty of Science, Helwan University, Cairo, Egypt; Chemistry Department, Faculty of Science, Taibah University, Al Madinah, Saudi Arabia
Ishaq A. Zaafarany, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Kinetics of hexacyanoferrate (III) (HCF) oxidation of fluorene (Fl) in organic alkaline medium has been studied by spectrophotometric technique at a constant ionic strength of 0.15 mol dm-3 and at a temperature of 25°C. The reaction showed a first order kinetics with respect to [HCF] and fractional-first order dependences on both [Fl] and [OH-]. The oxidation rate was increased with the increase in the ionic strength of the reaction medium. The oxidation mechanism was suggested which involves formation of a 1:1 intermediate complex between fluorene and HCF species in a pre-equilibrium step. The final oxidation product of fluorene was identified by spectroscopic and chemical tools as 9H-fluorenone. The appropriate rate law expression was deduced and the reaction constants involved in the mechanism were evaluated. The activation parameters of the rate constant of the slow step along with the thermodynamic quantities of the equilibrium constants were evaluated and discussed.
Rabab S. Jassas,
Saleh A. Ahmed,
Hazim M. Ali,
Nermeen S. Abbas,
Ishaq A. Zaafarany,
A Study of the Kinetics and Mechanism of Oxidation of Fluorene by Alkaline Hexacyanoferrate(III), American Journal of Physical Chemistry.
Vol. 6, No. 3,
2017, pp. 42-48.
Thormann T, Rogojerov M, Jordanov B, Thulstrup EW (1999) Vibrational polarization spectroscopy of fluorene: alignment in stretched polymers and nematic liquid crystals, J. Mol. Str. 509: 93-99.
Environmental contaminants encyclopedia fluorene entry July 1, 1997.
Li X, Lu H, Wang S, Guo J, Li J (2011) Sensitizers of dye-sensitized solar cells, Prog. Chem., 23: 569-588.
Ma Z, Ding J, Cheng Y, Xie Z, Wang L, Jing X, Wang F (2011) Synthesis and characterization of red lightemitting electrophosphorescent polymers with different triplet energy main chain, Polymer, 52: 2189-2197.
Wang HY, Qian Q, Lin KH, Peng B, Huang W, Liu F, Wei W (2012) Stable and good color purity white lightemitting devices based on random fluorene/spirofluorene copolymers doped with iridium complex, J. Polym. Sci. B, 50: 180-188.
Yang XH, Wu FI, Neher D, Chien CH, Shu CF (2008) Polyfluorene-based semiconductors combined with various periodic table elements for organic electronics, Chem. Mater., 20: 1629-1635.
Kucherak OA, Didier P, Mely Y, Klymchenko AS (2010) Fluorene analogues of prodan with superior fluorescence brightness and solvatochromism, J. Phys. Chem. Lett., 1: 616-620.
Cheng YJ, Yang SH, Hsu CS (2009) Synthesis of conjugated polymers for organic solar cell applications, Chem. Rev., 109: 5868-5923.
Xing X, Zhang L, Liu R, Li S, Qu B, Chen Z (2012) A deep-blue emitter with electron transporting property to improve charge balance for organic light-emitting device, ACS Appl. Mater. Interf., 4: 2877-2883.
Pina J de, Melo JSS, Egkert A, Scherf U (2015) Unusual photophysical properties of conjugated, alternating indigo–fluorene copolymers, J. Mater. Chem. A, 3: 6373-6381.
Fromm R, Ahmed SA, Hartmann Th, Huch V, Abdel-Wahab AA, Durr A (2001) Eur. J. Org. Chem., 21: 4077-4085.
Ahmed SA, Abdel-Wahab AA, Durr H (2003) CRC Handbook of organic photochemistry and photobiology, Horspool WM, Lenci F edn, CRC press, New York, 2nd edn, Chapter 96, p 1.
Ahmed SA, Hartmann Th, Durr H (2008) Photochromism of dihydroindolizines: Part VIII. First holographic image recording based on di- & tetrahydroindolizines photochromes, J. Photochem. Photobiol., 200: 50-56.
Ahmed SA, Pozzo JL (2008) Photochromism of dihydroindolizines Part IX. First attempts towards efficient self-assembling organogelators based on photochromicdihydroindolizines and N-acyl-I, w-amino acid units, J. Photochem. Photobiol., 200: 57-67.
Fawzy A, Zaafarany IA, Alfahemi J, Althagafi I, Morad M (2015) Oxidation of pectate biopolymer by hexacyanoferrate(III) in aqueous alkaline medium. A kinetic and mechanistic study, Chem. Sci. Rev. Lett., 4: 985-996.
Fawzy A (2016) Palladium(II)-catalyzed oxidation of l-tryptophan by hexacyanoferrate(III) in perchloric acid medium: a kinetic and mechanistic approach, J. Chem. Sci., 128: 247-256.
Fawzy A (2016) Kinetics and mechanism of uncatalyzed and ruthenium(III)-catalyzed oxidation of formamidine derivative by hexacyanoferrate(III) in aqueous alkaline medium, J. Chem. Sci., 128: 733-743.
Fawzy A, Zaafarany IA, Yarkandi N, Al-Bonayan A, Almallah Z (2016) Kinetic and mechanism of oxidation of methylaminopyrazole formamidine by alkaline hexacyanoferrate(III) and the effect of divalent transition metal ions, Sci. J. Chem., 1: 1-8.
Fawzy A, Zaafarany IA, Tirkistani F, Alfahemi J, Morad M (2016) Palladium(II)-catalyzed oxidation of pyrimidine derivative by hexacyanoferrate(III) in aqueous alkaline medium: a kinetic study, Am. J. Chem. Eng., 4: 38-45.
Asghar BH, Altass HM, Fawzy A (2015) Copper(II) catalysis for oxidation of l-tryptophan by hexacyanoferrate(III) in alkaline medium: a kinetic and mechanistic approach, J. Saudi Chem. Soc., in press.
Kelson EP, Phengsy PP (2000) Kinetic study of 2-propanol and benzyl alcohol oxidation by alkaline hexacyanoferrate(III) catalysed by a terpyridyl ruthenium complex. Int. J. Chem. Kinet., 32: 760–770.
Vovk AI, Muraveva IV, Kukhar VP, Baklan VF (2000) Kinetics of oxidation of vitamin B1 and its Oacyl analogs with ferricyanide. A mechanistic model of thiamin-binding protein. Russ. J. Gen. Chem., 70: 1108–1112.
Speakman PT, Waters WA (1955) Kinetic features of the oxidation of aldehydes, ketones and nitroparaffins with alkaline ferricyanide. J. Chem. Soc., 40–50.
Jose TP, Nandibewoor ST, Tuwar SM (2006) Kinetics and mechanism of oxidation of vanillin by hexacyanoferrate(III) in aqueous alkaline medium. J. Solution Chem., 35: 51–62; (2006) Osmium(VIII) catalyzed oxidation of a sulfur containing amino acid – A kinetic and mechanistic Approach. J. Sulfur Chem., 27: 25-36.
Singh VN, Singh MP, Saxena BBL (1970) Kinetics and mechanism of alkaline ferricyanide oxidation of acetone and ethyl methyl ketone. Indian J. Chem., 8: 529–532.
Leal JM, Garcia B, Domingo PL (1998) Outer-sphere hexacyanoferrate(III) oxidation of organic substrates. Coord. Chem. Rev., 173: 79–131.
Farokhi SA, Nandibewoor ST (2003) Kinetic, mechanistic and spectral studies for the oxidation of sulfanilic acid by alkaline hexacyanoferrate(III). Tetrahedron, 59: 7595-7601.
Ahmed SA (2004) Photochromism of dihydroindolizines. III: synthesis and photochromic behavior of novel photochromic dihydroindolizines incorporating a cholesterol moiety, Monatsh. Chem., 135: 1173-1181.
Ahmed SA, Khairou KS, Asghar BH, Muathen HA, Nahas NMA, Al Shreef HF (2014) Photochromism of tetrahydroindolizines. Part XIV: Synthesis of cis-fixed conjugated photochromic pyridazinopyrrolo [1, 2-b] isoquinolines incorporating carbon-rich linkers, Tetrahderon Lett., 55: 2190-2197.
Vogel AI (1973) Text book of practical organic chemistry including quantitative organic analysis, 3rd edn, p 332, ELBS, Longman.
Feigl F (1975) Spot tests in organic analysis, p 195, Elsevier, New York.
Leal JM, Domingo PL, Garcla B, Ibeas S (1993) Alkali metal ion catalysis of the oxidation of L-ascorbic acid by hexacyanoferrate(III) in strongly acidic media. J. Chem. Soc. Faraday Trans., 89: 3571–3577.
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.
Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z., 49: 333–369.
Hicks, K. W., Toppen, D. L., Linck, R. G.: In: Inner-sphere electron-transfer reactions of vanadium(II) with azidoamine complexes of cobalt(III). Inorg. Chem. 1, 310–315 (1972).
Sutin, N (1968) Free energies, barriers, and reactivity patterns in oxidation-reduction reactions. Acc. Chem. Res., 1: 225–231.
Freeman F (1981) Permanganate ion oxidations. 13. Soluble manganese(IV) species in the oxidation of 2,4(1H,3H)-pyrimidinediones (uracils). J. Am. Chem. Soc., 103: 1154–1158.