𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Formation and decay of N, N, N′, N′-tetraethyl-p-phenylenediamine radical cation in aqueous solution. A kinetic study by stopped-flow technique

✍ Scribed by Ponnu Aravindan; Pichai Maruthamuthu; Periyasamy Dharmalingam


Publisher
John Wiley and Sons
Year
1995
Tongue
English
Weight
735 KB
Volume
27
Category
Article
ISSN
0538-8066

No coin nor oath required. For personal study only.

✦ Synopsis


A kinetic study has been carried out on the oxidation of N , N , N', N'-tetraethyl-p-phenylenediamine (TEPD) by metal ion like Ce4+, oxoanions viz., MnO, and CrZO:-; peroxides such as peroxomonosulphate (PMS), peroxodisulphate (PDS), and HzOz; and halogens namely Clz, Brz, and 12. The fast kinetics of the formation and decay of the radical cation TEPD" have been analyzed at 565 nm by the stoppedflow technique under pseudo-first-order conditions. From the kinetic data, it has been inferred that the reactions were found to be of first-order with respect to [TEPD] and [oxidant] but over all it has been of second-order. The observed second-order rate constants in both the formation and decay of TEPD'+ has been correlated with the oxidation potentials of the various oxidants employed in this study. The effect of pH on the oxidation has been investigated in the formation and decay of TEPD'+ as well as reduction studies have also been carried out using dithionite which has been found to regenerate the TEPD from the TEPD'' and the corresponding rate constant has also been determined. Besides these, this article also explains how the TEPD, which forms TEPD'+ acts as a better electron relay than TMPD(N, N , N', N'tetramethyl-p-phenylenediamine) which forms TMPD'+ , even though both of them undergo one-electron oxidation and are used in the chemical routes to solar energy conversions. The observed rate constants for electron transfer were correlated theoretically using Marcus theory. The observed and calculated rate constants have good correlation.


📜 SIMILAR VOLUMES


Kinetic simulation studies on the transi
✍ Tapan Kumar Saha; Subarna Karmaker; Keietsu Tamagake 📂 Article 📅 2003 🏛 John Wiley and Sons 🌐 English ⚖ 279 KB 👁 3 views

High-valent oxo-iron(IV) species are commonly proposed as the key intermediates in the catalytic mechanisms of iron enzymes. Water-soluble iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin (Fe(III)TMPyP) has been used as a model of heme-enzyme to catalyse the hydrogen peroxide (H 2 O 2 ) o