http://rua.ua.es/dspace/bitstream/10045/43029/2/2015_Rodriguez_etal_Electrochimica-Acta.pdf

New insight on the behavior of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes

The kinetics of the oxidation of 2-furancarboxaldehyde by thallic perchlorate at 50°C obeys the rate law

$$ - \frac{{d[T1 (III)]}}{{dt}} = k[T1 (III)] [Substrate]$$

(1)

k has a value of 4.5±0.2×10−3 dm3 mol−1s−1 at 50°C. The rate of the reaction does not depend on [H+] and the oxidation product is 2-furancarboxylic acid.

Kinetics and mechanism of the oxidation of 2-furancarbox-aldehyde by thallium(III) in perchloric acid solutions

The rate of the oxidation of formic acid by thallium(III) in (Li, H)ClO4 solutions is not affected by variation in hydrogen ion concentration and the experimental rate law,

$$\frac{{ - d\left[ {T\left( {III} \right)} \right]}}{{d t}} = \frac{{k_1 K\left[ {T\left( {III} \right)} \right]\left[ {HCOOCH} \right]}}{{1 + K\left[ {HCOOH} \right]}}$$

is consistent with the mechanism which requires the formation of intermediate complex [HCOOHTl]3+ in a rapid preequilibrium followed by its slow decomposition to yield the final products. At 75°,k1 andK have the values of 16±1×10−5 sec−1 and 7.3±0.5M−1 resp.

Kinetics and Mechanism of the Oxidation of Formic Acid by Thallium(III). Reinvestigation of Hydrogen Ion Dependence

The rate of the oxidation of formic acid by thallium(III) in (Li, H)ClO4 solutions is not affected by variation in hydrogen ion concentration and the experimental rate law,
 
$$\frac{{ - d\left[ {T\left( {III} \right)} \right]}}{{d t}} = \frac{{k_1 K\left[ {T\left( {III} \right)} \right]\left[ {HCOOCH} \right]}}{{1 + K\left[ {HCOOH} \right]}}$$

 is consistent with the mechanism which requires the formation of intermediate complex [HCOOHTl]3+ in a rapid preequilibrium followed by its slow decomposition to yield the final products. At 75°,k
1 andK have the values of 16±1×10−5 sec−1 and 7.3±0.5M
−1 resp.

S. D. Saxena

Papers

Kinetics and mechanism of the oxidation of formic acid by thallium(III). Reinvestigation of hydrogen ion dependence

Kinetics and Mechanism of the Oxidation of Formic Acid by Thallium(III). Reinvestigation of Hydrogen Ion Dependence