Kinetics and Mechanisms of Permanganate Oxidations of Cadaverine in Different Media
American Journal of Physical Chemistry
Volume 5, Issue 6, December 2016, Pages: 108-117
Received: Nov. 16, 2016;
Accepted: Nov. 23, 2016;
Published: Dec. 23, 2016
Views 3495 Downloads 120
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
Metwally Abdallah, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Benha University, Benha, Egypt
Rabab S. Jassas, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Rami J. Obaid, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
The kinetics of oxidation of cadaverine (CAD) by permanganate ion in acidic, neutral and alkaline media has been investigated spectrophtometrically at constant ionic strengths and temperature. The reactions in different media exhibited a first order kinetics in [MnO4-] and less than unit order dependences with respect to [CAD]. The oxidation of cadaverine showed less than unit order dependences with respect to [H+] and [OH-] in acidic and alkaline media, respectively. Variation of ionic strengths in both acidic and alkaline media had no significant effect on the oxidation rates. The proposed oxidations mechanisms in all media involve formation of 1:1 intermediate complexes between the kinetically active species of both cadaverine and permanganate ion. The final oxidation products of cadaverine were identified as 5-aminopentanal and ammonia. The appropriate rate laws in all media were deduced. The reaction constants involved in the different steps of the mechanisms were evaluated.
Ishaq A. Zaafarany,
Rabab S. Jassas,
Rami J. Obaid,
Kinetics and Mechanisms of Permanganate Oxidations of Cadaverine in Different Media, American Journal of Physical Chemistry.
Vol. 5, No. 6,
2016, pp. 108-117.
Lewis, Robert Alan (1998). Lewis' Dictionary of Toxicology. CRC Press, p. 212.
Yeoman CJ, et al (2013). A multi-omic systems-based approach reveals metabolic markers of bacterial vaginosis and insight into the disease, PloS one 8: e56111.
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.
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.
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.
Asghar BH, Fawzy A (2016) Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese (II). J. Saudi Chem. Soc. 20: 561-569.
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.
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.
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) intermediates during oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometeric techniques. Carbohydr. Res. 345: 1588-1593.
Hassan RM, Fawzy A, Alarifi A, Ahmed GA, Zaafarany IA, Takagi HD (2011)Base-catalyzed oxidationof 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.
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.
Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate: oxidations of arylalkanes in organic solvents. Inorg. Chem. 36: 2069-2078.
Kini AK, Farokhi SA, Nandibewoor ST (2002) A comparative study of ruthenium (III) catalysed oxidation of L-leucine and L-isoleucine by alkaline permanganate. A kinetic and mechanistic approach. Transition Met Chem. 27: 532–540.
Halligudi LL, Desai SM, Mavalangi AK, Nandibewoor ST (2000) Kinetics of the oxidative degradation of rac-serine by aqueous alkaline permanganate. Monatsh Chem. 131: 321–332.
Verma RS, Reddy JM, Shastry VR (1974) Kinetic study of homogeneous acid-catalyzed oxidation of certain amino-acids by potassium permanganate in moderately concentrated acidic media. J. Chem. Soc. Perkin Trans. 124: 469–473.
Mohanty B, Behera J, Acharya S, Mohanty P, Pantaik AK (2013) Metal ion catalyzed oxidation of L-lysine by alkaline permanganate Ion-A kinetic and mechanistic approach. Chem. Sci. Trans. 2: 51–60.
Cotton FA, Wilkinson G. Advanced Inorganic Chemistry, p. 747, John Wiley and Sons, New York (1980).
Vogel IA (1978) A Text Book of Quantitative Inorganic Analysis. 4th edn, p. 352. ELBS, Longman.
Feigl F (1975) Spot Tests in Organic Analysis, p. 195. Elsevier, New York.
Vogel AI (1973) Text Book of Practical Organic Chemistry Including Quantitative Organic Analysis, 3rd edn, p. 332. ELBS, Longman.
Zahedi M, Bahrami H (2004) Kinetics and mechanism of the autocatalytic oxidation of L-asparagine in a moderately concentrated sulfuric acid medium. Kinet. Catal. 45: 351–358.
Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z. 49: 333–369.
Amis ES (1966) Solvent Effect on Reaction Rates and Mechanism, Academic Press, New York, p. 28.
Frost AA, Person RG (1970) Kinetics and mechanism, Wiley Eastern, New Delhi, p. 147.
Hosahalli RV, Savanur AP, Nandibewoor ST, Chimatadar SA (2012) Kinetics and mechanism of the autocatalyzed oxidation of theophylline by permanganate in aqueous perchloric acid medium. J. Solution Chem. 41: 567–580.
Farokhi SA, Nandibewoor ST (2004) The kinetic and mechanism of the oxidative decarboxylation of benzilic acid by acid permanganate (stopped flow technique)-autocatalytic study. Can. J. Chem. 82: 1372–1380.
Panari RG, Chougale RB, Nandibewoor ST (1998) Oxidation of mandelic acid by alkaline potassium permanganate. A kinetic study. J. Phys. Org. Chem. 11: 448–454.
De Oliveira LA, Toma HE, Giesbrecht E (1976) Kinetics of oxidation of free and coordinated dimethylsulfoxide with permanganate in aqueous solution. Inorg. Nucl. Chem. Lett. 2: 195–203.