1134
K. CHOLKAR ET AL.
ꢁ=
the negative ꢀS suggests that the redox reaction is controlled 11. Singh, B.; Singh, N.B.; Saxena, B.B.L. Ru(III) catalysis in oxidation of
n-propanol and n-butonol by acididc solutions of bromamine. Tetrahedron
by entropy instead of enthalpy.
1
994, 40, 5203.
1
1
1
2. Moelwyn-Hughes, E.A. Kinetics of Reactions in Solutions; Oxford Univer-
sity Press: London, 1947, p. 297.
CONCLUSIONS
3. Campbell, M.M.; Johnson, G. Chloramine-T and related N-halogeno-N-
metallo reagents. Chem. Rev. 1978, 78, 65.
4. Mallamma, S.; Rangaswamy, A.; Made Gowda, N.M. Kinetic and mech-
anistic studies of Pd(II) catalyzed oxidation of some α-hydroxy acids
by sodium N-bromobenzenesulphonamide in hydrochloric acid solutions.
Synth. React. Inorg, Met.-Org. Chem. 2003, 33, 1555.
5. Thomas, K.J.; Made Gowda, N.M.; Mayanna, S.M. Hydrogen ion catalyzed
oxidation of acetylcholine by chromaine-B—A kinetic and mechanistic
study. Oxid. Commun. 2003, 26, 567.
The redox reaction involving CAB oxidation of IC in the
presence of the Os(VIII) catalyst in basic solutions has been
investigated. The reaction stoichiometry has been found to be
1
:4 (mol/mol).
The Os(VIII)–IC complex formation in the IC–CAB reaction
1
in NaOH solutions has been monitored spectrophotometrically
at the IC λmax of 610 nm at constant temperature to generate
kinetic data.
16. Kondarasaiah, M.H.; Ananda, S.; Puttaswamy; Made Gowda, N.M. Palla-
dium(II) catalyzed oxidation of primary amines by bromamine-T in alkaline
medium: A kinetic and mechanistic study. Synth. React. Inorg. Met.-Org.
Chem. 2003, 33, 1145.
ꢀ
The experimental rate law has been found to be: rate = k
−
0.40
0.64
[
IC][OH ]
[Os(VIII)] . A suitable mechanism consistent
with the experimental data has been proposed, based on which
a rate law has been derived.
1
7. Saldanha, R.J.D.; Ananda, S.; Venkatesha, B.M.; Made Gowda, N.M. Ox-
idation of psychotropic drugs by chormaine-T in acid medium: A kinetic
study using spectrometry. J. Mol. Struct. 2002, 606, 147.
ꢁ
ꢁ
ꢁ=
The activation parameters Ea, ꢀH , ꢀS , and ꢀG have
been determined to understand whether the reaction is controlled 18. Ananda, S.; Jagadeesh, M.B.; Venkatesha, B.M.; Made Gowda, N.M. Kinet-
ꢁ
ics of oxidation of indigo carmine by N-Sodio-N-bromotoulenesulfonamide
in acidic buffer medium. Int. J. Chem. Kinet. 1999, 29, 453.
9. Venkatesha, B.M.; Ananda, S.; Mahadevappa, D.S.; Made Gowda, N.M.
Kinetic and mechanistic studies of indigo carmine oxidation by chloramine-
T and chlorine in acidic buffer media. Int. J. Chem. Kinet. 1995, 27, 663.
by entropy or enthalpy. The negative ꢀS indicates the rigid
transition-state formation and the entropy-controlled reaction.
1
REFERENCES
1
2
3
. Rassaeia, L.; Sillanpaa, M.; Markenb, F. Modified carbon nanoparticle- 20. Puttaswamy, N.; Mahadevappa, D.S.; Made Gowda, N.M. Kinetics and
chitosan film electrodes: Physisorption versus chemisorptions. Elec-
trochem. Acta 2008, 53, 5732.
mechanism of oxidation of indigo carmine by hypohalites. Int. J. Chem.
Kinet. 1991, 23, 27.
21. Made Gowda, N.M.; Mahadevappa, D.S. Oxidation of indigo carmine, isatin
and 5-nitroisatin by chloramine-T and dichloramine-T. Curr. Sci. 1975, 44,
757.
. Singh, G.; Sharma, P.; Capalash, N. Performance of an alkalophilic and
halotolerant laccase from γ -proteobacterium JB in the presence of industrial
pollutants. J. Gen. Appl. Microbiol. 2009, 55, 283.
. Wang, H.-Y.; Zhao, J.-F. Interaction of indigo carmine with cetyltrimethy-
lammonium bromide and application to determination of cationic surfactant
in waste water. Bull. Korean Chem. Soc. 2003, 24, 1444.
. Farah, M.E.; Maia, M.; Rodrigues, E.B. Dyes in ocular surgery: Principles
for use in chromovitrectomy. Am. J. Ophthalmol. 2009, 148, 332.
. Hunt, I.V. The indigo carmine reaction as a test for chlorates and hypochlo-
rites in milk. Analyst 1939, 64, 653.
. Dweck, A.C. Natural ingredients for colouring and styling. Int. J. Cosmet.
Sci. 2002, 24, 287.
. Komboonchoo, S.; Bechtold, T. Natural dyeing of wool and hair with indigo
carmine (C.L. Natural Blue 2), a renewable resource based blue dye. J.
Cleaner Production 2009, 17, 1487.
22. Sushashini, M.; Subramanian, M.; Rao, V.R.S. Determination of protona-
tion constant of chormaine-B. Talanta 1985, 32, 1082.
23. Jagadeesh, R.V.; Puttaswamy Vaz, N.; Made Gowda, N.M. Ru(III)-
catalyzed oxidative conversion of isatins to anthranilic acids by sodium
N-bromo-p-toluenesulfonamide in hydrochloric acid medium: A mecha-
nistic approach and kinetic modeling. AICHE J. 2008, 54, 756.
24. Laidler, K.J. Reaction Kinetics, 2nd ed.; Tata McGraw-Hill: New Delhi,
India, 1995.
25. House, J.E. Principles of Chemical Kinetics; Wm. C. Brown: Boston, 1997.
26. Entelis, S.G.; Tiger, R.P. Reaction Kinetics in Liquid Phase; John Wiley
and Sons: New York, 1976, p. 362.
27. (a) Amis, E.S. Solvent Effects on Reaction Rates and Mechanism; Academic
Press: New York, 1966. (b) Amis, E.S.; Jaffe, G. J. Chem. Phys. 1942, 10,
598.
4
5
6
7
8
9
. Rodd, E.H. Chemistry of Carbon Compounds; Elsevier: Amsterdam, 1960,
vol. IVB, p. 1093.
. Keyvanfard, M. Kinetic-photometric determination of iodide based on its
inhibitory effect on the bromated oxidation of indigo carmine in micellar
medium. Asian J. Chem. 2009, 21, 2715.
28. Richardt, C. Solvent and Solvent Effects in Organic Chemistry, 3rd ed.;
Wiley-Vett: New York, 2003.
29. Collins, C.J.; Bowmann, N.S. Isotope Effect in Chemical Reactions; Van
Nostrand-Reinhold: New York, 1970.
1
0. Zaprozhets, O.A.; Biokon, S.L. A visual test method for determining sele-
nium(IV) with indigo carmine immobilized on silica. J. Anal. Chem. 2007, 30. Kohen, A.; Limbach, H.H. Isotope Effects in Chemistry and Biology; CRC
6
2, 188.
Press: Boca Raton, FL, 2006.