Abstract
RuCl3 can further catalyze the reaction between hexacyanoferrate(III) and iodide ions, which is already catalyzed by the hydrogen ions obtained from perchloric acid. Rate, when the reaction is catalyzed only by the hydrogen ions, was separated graphically from the rate when ruthenium(III) and H+ ions both catalyze the reaction. Reactions studied separately in the presence as well as in the absence of RuCl3 under similar conditions were found to follow second order kinetics w.r.t. [I−]. While the rate showed direct proportionality w.r.t. [Fe(CN)6]3− and [RuCl3]. At low concentrations the reaction shows direct proportionality with respect to [H+] which tends to become proportional to the square of hydrogen ion concentrations. External addition of [Fe(CN)6]4− ions retards the reaction velocity while change in ionic strength of the medium has no effect on the rate. With the help of the intercept of the catalyst graph, extent of the reaction, which takes place without adding ruthenium(III) was calculated and it was in accordance with the values obtained from the separately studied reaction in which only H+ ions catalyze the reaction. It is proposed that ruthenium forms a complex, which slowly disproportionates into the rate-determining step. Arrhenius parameters at four different temperatures were also calculated.
Similar content being viewed by others
References
V.N. Singh A.C. Grover B.B.L. Saxena M.P. Singh (1969) Can. J. Chem. 47 1051 Occurrence Handle10.1139/v69-165 Occurrence Handle1:CAS:528:DyaF1MXos1Oqsg%3D%3D
M.P. Singh H.S. Singh M.K. Verma (1980) J. Phys. Chem. 84 256 Occurrence Handle10.1021/j100440a006 Occurrence Handle1:CAS:528:DyaL3cXhtVSjt7w%3D
(a) P.K. Tandon, Manibala, H.S. Singh and B. Krishna, Z. Phys. Chemie. Leipzig, 265, 609 (1984); (b) H.S. Singh, P.K. Tandon, B.K. Singh and A. Mehrotra, Proc. Indian Natn. Sci. Acad., 56 A, 447 (1990).
Manibala P.K. Tandon B. Krishna (1985) Z. Phys. Chemie. Leipzig 266 1153 Occurrence Handle1:CAS:528:DyaL28XnsF2jsg%3D%3D
M.K. Verma P.K. Tandon M.P. Singh (1987) Z. Phys. Chemie. Leipzig 268 565 Occurrence Handle1:CAS:528:DyaL1cXnsVKjtw%3D%3D
P.K. Tandon B. Krishna (1985) Kinetics and Catalysis USSR 26 607 Occurrence Handle1:CAS:528:DyaL28XjtlOjsw%3D%3D
S. Wolfe, S.K. Hasan and J.R. Campbell, Chem. Commun., 1420 (1970)
M.T. Nufiez V.S. Martin (1990) J. Org. Chem. 55 1928 Occurrence Handle10.1021/jo00293a044
H.S. Singh A. Gupta A.K. Singh (1998) Transition Met. Chem. 23 277 Occurrence Handle10.1023/A:1015756732447
H.S. Singh B. Singh A.K. Singh (1991) Carbohydr. Res. 211 235 Occurrence Handle10.1016/0008-6215(91)80094-4 Occurrence Handle1:CAS:528:DyaK3MXisVOmu7Y%3D
P.M. Henry (1966) J. Am. Chem. Soc. 86 3246 Occurrence Handle10.1021/ja01070a009
C. Wagner (1924) Z. Phys. Chem 113 261 Occurrence Handle1:CAS:528:DyaB2MXlsF2m
A. Kiss ParticleVon (1933) Rec. Trav. Chim 52 289 Occurrence Handle10.1002/recl.19330520404
A. Indelli and G.C. Guaraldi, J. Chem. Soc., 36 (1964).
H.B. Friedman B.E. Anderson (1939) J. Am. Chem. Soc. 61 116 Occurrence Handle10.1021/ja01870a039
B. Krishna and H.S. Singh, Chemie Analytique, 48, 658 (1966); ibid., 49, 330 (1967).
M. Grätzel (2001) Nature 414 338 Occurrence Handle10.1038/35104607
M. Grätzel (2004) J. Photochem. Photobiol. A 164 3 Occurrence Handle10.1016/j.jphotochem.2004.02.023 Occurrence Handle1:CAS:528:DC%2BD2cXktFKqtbY%3D
M. Grätzel (2005) Inorg. Chem. 44 6841 Occurrence Handle10.1021/ic0508371 Occurrence Handle1:CAS:528:DC%2BD2MXhtVGis77M
M.K. Nazeeruddin A. Kay I. Rodicio R.H. Baker E. Müller P. Liska N. Vlachopoulos M. Grätzel (1993) J. Am. Chem. Soc. 115 6382 Occurrence Handle10.1021/ja00067a063 Occurrence Handle1:CAS:528:DyaK3sXkvVeku7o%3D
S. Ferrere (2000) Chem. Mater. 12 1083 Occurrence Handle10.1021/cm990713k Occurrence Handle1:CAS:528:DC%2BD3cXhslentrw%3D
S. Ferrere (2002) Inorg. Chim. Acta. 329 79 Occurrence Handle10.1016/S0020-1693(01)00743-5 Occurrence Handle1:CAS:528:DC%2BD38XhsFamsrk%3D
S. Ferrere B.A. Gregg (1998) J. Am. Chem. Soc. 120 843 Occurrence Handle10.1021/ja973504e Occurrence Handle1:CAS:528:DyaK1cXms1Oqtg%3D%3D
I. Stefanic K.-D. Asmus M. Bonifacic (2005) J. Phys. Org. Chem. 18 408 Occurrence Handle10.1002/poc.885 Occurrence Handle1:CAS:528:DC%2BD2MXjslaiu7w%3D
X. Wang D.M. Stanbury (2004) J. Phys. Chem. A 108 7637 Occurrence Handle10.1021/jp046782q Occurrence Handle1:CAS:528:DC%2BD2cXmvFWmt74%3D
X. Wang D.M. Stanbury (2006) Inorg. Chem. 45 3415 Occurrence Handle10.1021/ic052022y Occurrence Handle1:CAS:528:DC%2BD28XislCjtL8%3D
P.K. Tandon (2003) Transition Met. Chem. 28 494 Occurrence Handle10.1023/A:1025049402032 Occurrence Handle1:CAS:528:DC%2BD3sXmtVWhsbo%3D
P.K. Tandon A. Mehrotra A.K. Singh R. Baboo P.B. Dwivedi (2004) Int. J. Chem. Kinet. 36 545 Occurrence Handle10.1002/kin.20030 Occurrence Handle1:CAS:528:DC%2BD2cXns1OqsL0%3D
(a) A.I. Vogel, Quantitative Inorganic Analysis, ELBS, London, 1961, p. 371.; (b) K.J. Laidler, Chemical Kinetics, TMH, NY, 1976, p. 11.
(a) H.H. Cady and R.F. Connik, J. Am. Chem. Soc., 80, 2646 (1958); (b) R.F. Connik and D.A. Fine, J. Am. Chem. Soc., 83, 3416 (1961); (c) ibid., 82, 4187 (1960); (d) W.P. Griffith, The Chemistry of the Rare Platinum Metals, Interscience, NY, 1967, p. 141.
(a) J. Halpern, B.H. Janes and A.L.W. Kemp, J. Am. Chem. Soc., 83, 4097 (1961); (b) J.F. Harrod, S. Coccone and J. Halpern, Can. J. Chem., 39, 1372 (1961).
A.J. Elliot S. Geertsen G.V. Buxton (1988) J. Chem. Soc. Faraday Trans. I 84 1101 Occurrence Handle10.1039/f19888401101 Occurrence Handle1:CAS:528:DyaL1cXitFWisrc%3D
J.L. Atwood S.G. Bott C.M. Means A.W. Coleman H. Zhangand M.T. May (1990) Inorg. Chem. 29 467 Occurrence Handle10.1021/ic00328a025 Occurrence Handle1:CAS:528:DyaK3cXptVahsA%3D%3D
L.W. Schroeder J.A. Ibers (1968) Inorg. Chem. 7 594 Occurrence Handle10.1021/ic50061a042 Occurrence Handle1:CAS:528:DyaF1cXntlajtA%3D%3D
M. Spiro, J. Chem. Soc., 3678 (1960) and refs cited therein.
I.M. Kolthoff W.J. Tomsicek (1935) J. Phys. Chem. 39 955 Occurrence Handle10.1021/j150367a005 Occurrence Handle1:CAS:528:DyaA28XpvVOn
(a) S. Prasad, Transition Met. Chem., 28, 1 (2003); (b) W.A. Eaton, P. George and G.I. Hanaria, J. Phys. Chem., 71, 2016 (1967).
(a) J. Jordan and G.J. Ewing, Inorg. Chem., 1, 587 (1962); (b) L.D. Pedro, G. Begona and M.L. Jose, Can. J. Chem., 68, 228 (1990); (c) S.A. Chimatadar, M.S. Salunke and S.T. Nandibewoor, Transition Met. Chem., 29, 743 (2004).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Tandon, P.K., Mehrotra, A., Srivastava, M. et al. Ruthenium(III) catalysis in the reaction of hexacyanoferrate(III) and iodide ions in perchloric acid medium. Transition Met Chem 32, 74–80 (2007). https://doi.org/10.1007/s11243-006-0136-8
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s11243-006-0136-8