The oxidation of
l-valine (
l-val) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 3.0 × 10
−3 mol dm
−3 was studied spectrophotometrically at 298 K and follows the rate law;
|
$ {\text{Rate}} = -
\frac{{{\text{d}}[{\text{DPC}}]}}{{{\text{d}}t}} = \frac{{kK_{4}K_{5} K_{6}[{\hbox{{\sc{l}}-val}}][{\text{DPC}}]}}{{[{\text{OH}}^{ - }][{\text{H}}_{3} {{\text{IO}}_{6}}^{2 - } ] + K_{4}[{\text{H}}_{3} {{\text{IO}}_{6}}^{2 - } ] + K_{4} K_{5} + K_{4}K_{5} K_{6} [{\hbox{{\sc{l}}-val}}]}} $ {\text{Rate}} = -
\frac{{{\text{d}}[{\text{DPC}}]}}{{{\text{d}}t}} = \frac{{kK_{4}K_{5} K_{6}[{\hbox{{\sc{l}}-val}}][{\text{DPC}}]}}{{[{\text{OH}}^{ - }][{\text{H}}_{3} {{\text{IO}}_{6}}^{2 - } ] + K_{4}[{\text{H}}_{3} {{\text{IO}}_{6}}^{2 - } ] + K_{4} K_{5} + K_{4}K_{5} K_{6} [{\hbox{{\sc{l}}-val}}]}}
|
where
K
4,
K
5 and
K
6 are the equilibrium constants for the different steps involved in the mechanism,
k is the rate constant for the slow step of the reaction. The appearance of [
l-val] term in both numerator and denominator explains the observed less than unit order in [
l-val]. Similarly the appearances of [H
3IO
6
2−] and [OH
−] in the denominator obey the experimental negative less than unit order in [H
3IO
6
2−] and [OH
−], respectively. The oxidation reaction in alkaline medium proceeds via a DPC-
l-valine complex, which decomposes slowly in a rate determining step followed by other fast steps to give the products. The
main products were identified by spot test and spectroscopic studies.