Summary
The kinetics of oxidation of malonic acid, studied in aqueous acid perchlorate, conform to the rate law
where [CrVI]T and [H2ma]T are the gross analytical concentrations of CrVI and malonic acid respectively. The stoichiometry of the reaction is variable as the initial oxidation product of the organic acid undergoes further partial oxidation. The rate is also inhibited by anions and the quantitative effect of Cl− in particular has been analysed, suggesting a chloro-chromium(VI) complex. A reaction mechanism is suggested.
Similar content being viewed by others
References
F. H. Westheimer,Chem. Rev.,45, 419 (1949).
W. A. Waters,Mechanism of Oxidation of Organic Compounds, Methuen, London, 1964.
R. Stewart,Oxidation Mechanism, W. A. Benjamin, New York, 1964.
K. B. Wiberg in K. B. Wiberg (Ed.),Oxidation in Organic Chemistry, Part A, Academic Press, New York, 1965.
J. Rocek in S. Patai (Ed.),Chemistry of Carbonyl Group, Interscience Publishers, London, 1966.
F. Freeman in S. Dayagi (Ed.),Reviews on Reactive Species in Chemical Reactions, Freund Publishing House, Tel Aviv, 1973, p. 36.
J. K. Beattie and G. P. Haight (Jr),Prog. Inorg. Chem.,17, 93 (1972).
S. Sundaram, N. Venkatasubramanian and S. V. Anatakrishnan,J. Sci. & Ind. Res.,35, 518 (1976).
G. V. Bokore and C. L. Jain,J. Inorg. Nucl. Chem.,31, 805 (1969).
D. A. Durham,J. Inorg. Nucl. Chem.,31, 3549 (1969).
D. A. Durham,Magy. Kem. Foly.,76, 275 (1970).
V. Srinivasan and J. Rocek,J. Amer. Chem. Soc.,96, 534 (1974).
A. Y. Drummond and W. A. Waters,J. Chem. Soc., 2456 (1954); K. K. Sengupta and S. Aditya,Z. Phys. Chem. (Frankfurt),38, 23 (1963); J. Jwo and R. M. Noyes,J. Amer. Chem. Soc.,97, 5422 (1975); Z. Ahmad and A. McAuley,J. Chem. Soc., Dalton Trans., 304 (1977).
T. J. Kemp and W. A. Waters,J. Chem. Soc.,1489, 1610 (1964); K. K. Sengupta and A. K. Chatterjee,Z. Phys. Chem. (Frankfurt),75, 15 (1971) and refs therein; B. S. Maritz and R. vanElik,Chim. Acta.,20, 43 (1976); F. Mata and M. P. Alvarez,Z. Phys. Chem. (Frankfurt),120, 155 (1980).
G. Calvaruso, A. I. Carbone and F. P. Cavasino,J. Chem. Soc., Dalton Trans., 1683 (1985).
M. Senapati, G. P. Panigrahi and S. N. Mahapatro,J. Org. Chem.,50, 3651 (1985).
Indu Rao, S. K. Mishra and P. D. Sharma,Ind. J. Chem.,30A, 773 (1991).
J. Y. Tong and E. L. King,J. Amer. Chem. Soc.,75, 618 (1955); J. H. Espenson and R. J. Kinny,Inorg. Chem.,10, 1376 (1976).
A. A. Frost and R. G. Pearson,Kinetics and Mechanism, Wiley, New York, 1953, p. 140.
P. Holloway,J. Amer. Chem. Soc.,74, 224 (1952).
D. G. Lee and R. Stewart,J. Amer. Chem. Soc.,86, 3051 (1964).
M. Cohen and F. H. Westheimer,J. Amer. Chem. Soc.,54, 4387 (1957).
H. Jayaraman,Ind. J. Chem.,2, 94 (1964).
V. Sathyabama and S. V. Anantakrishnan,Ind. J. Chem.,10, 168 (1972).
S. V. Anantakrishnan and R. Varadrajan,Proc. Ind. Acad. Sci.,72A, 197 (1970).
E. S. Amis,J. Chem. Educ.,30, 351 (1953).
Stability Constants of Metal Ion Complexes, Special Publication No. 17, The Chemical Society, London, 1964, p. 440; R. J. Bruchlman and F. H. Verhock,J. Amer. Chem. Soc.,70, 1401 (1948).
S. Sundaram and N. Venkatasubramanian,J. Inorg. Nucl. Chem.,31, 1761 (1969).
J. Rocek and J. Krupicka,Coll. Czech. Chem. Comm.,23, 2068 (1958).
L. S. Levitt,J. Org. Chem.,20, 1297 (1955).
F. P. Cavasino and E. Di Dio,J. Chem. Soc. A., 3176 (1971).
A. E. Martell and R. M. Smith,Critical Stability Constants, Vol. 3, Plenum, New York, 1977.
C. F. Huber and G. P. Haight,J. Amer. Chem. Soc.,98, 4128 (1976).
J. H. Espension and E. L. King,J. Amer. Chem. Soc.,85, 3325 (1963); J. H. Espension,J. Amer. Chem. Soc.,92, 1880 (1970);Accts. Chem. Res.,3, 347 (1970).
J. Rocek and A. E. Radkowsky,J. Amer. Chem. Soc.,90, 2986 (1968);
F. Hasan and J. Rocek,J. Amer. Chem. Soc.,94, 9073 (1972); V. Srinivasan and J. Rocek,J. Amer. Chem. Soc.,96, 127 (1974).
J. Rocek and A. Riehl,Tetrahedron letters, 1437 (1966).
K. B. Wiberg and H. Sehafer,J. Amer. Chem. Soc.,91, 927, 933 (1969).
J. K. Beattle and G. P. Haight (Jr) in J. O. Edwards (Ed.),Inorganic Reaction Mechanism, Part II, Interscience, New York, 1972, p. 98; G. P. Haight, D. C. Richardson and N. H. Colburn,Inorg. Chem.,3, 1777 (1969).
Author information
Authors and Affiliations
Additional information
TMC 2660
Rights and permissions
About this article
Cite this article
Rao, I., Mishra, S.K. & Sharma, P.D. Kinetics and mechanism of oxidation of malonic acid by chromium(VI) in aqueous perchlorate medium. Transition Met. Chem. 17, 449–454 (1992). https://doi.org/10.1007/BF02910730
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02910730