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Oxidation of thallium(I) by hexacyanoferrate(III) in aqueous acetic acid
Author(s) -
Gokavi G. S.,
Raju J. R.
Publication year - 1988
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550200503
Subject(s) - chemistry , acetic acid , hydrochloric acid , protonation , thallium , aqueous solution , chloride , inorganic chemistry , reaction rate constant , ion , hydrogen chloride , medicinal chemistry , nuclear chemistry , kinetics , organic chemistry , physics , quantum mechanics
The hexacyanoferrate(III)‐thallium(I) reaction in aqueous acetic acid containing large concentrations of hydrochloric acid is considerably accelerated both by hydrogen and chloride ions as well as increasing acetic acid in the medium. The experimental results obey the rate law (1) where β 1 to β 6\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{rcl} {{\rm (1)}} & {- \frac{{{\rm d[Fe(CN)}_{\rm 6} ^{{\rm 3 -}}]}}{{dt}} = \frac{{\{\beta _4 k_a [{\rm H}^ +] + \beta _5 k_b [{\rm H}^ +]^2 \} \beta _2 [{\rm Cl}^ -]^2 [{\rm Fe(CN)}_{\rm 6} ^{{\rm 3 -}}]_T [Tl^ +]_T}}{{\{1 + \beta _4 [{\rm H}^ +] + \beta _5 [{\rm H}^ +]^2 + \beta _6 [{\rm H}^ +]^3 \} \{1 + \beta _1 [{\rm Cl}^ -] + \beta _2 [{\rm Cl}^ -]^2 + \beta _2 [{\rm Cl}^ -]^3 \}}}}\end{array}$$\end{document} are the cumulative stability constants of the species TlCl, TlCl 2 − , TlCl 3 2− , HF e (CN) 6 2− , H 2 Fe(CN) 6 −and H 3 Fe(CN) 6 respectively and k a and k b are the rate constants associated with the mono‐ and di‐protonated oxidant species. The main active species are H 2 Fe(CN) 6 −and TlCl 2 − .