Reduction of [PtCl 6 ] 2− by L-ascorbic acid (H 2 ASc) in 0.1 M aqueous acid medium has been investigated spectrophotometrically under pseudo-first order condition at [PtCl 6 The redox reaction follows the rate law:, where k is the second-order rate constant and [H 2 ASc] is the total concentration of ascorbic acid. Electron transfer from [H 2 ASc] to Pt(IV) center leading to the release of two halide ions and formation of the reaction products, square planner Pt(II) halide complex, and dehydrated ascorbic acid is suggested. This redox reaction follows an outersphere mechanism as Pt(IV) complex is substituted inert. Activation parameters were calculated corresponding to rate of electron transfer reaction k. Activation parameters favor the electron transfer reaction.

Kinetics and mechanism of electron transfer to pyridinium chlorochromate (VI) from sulfur containing amino acid, L-cysteine in aqueous and micellar media The electron transfer reaction of L-cysteine (RSH) with pyridinium chlorochromate (PCC) has been studied spectrophotometrically over the range 2.0 ≤ 103 [RSH] ≤ 6.0; 0.01 ≤ [H+] ≤ 0.2; 298 ≤ T ≤ 318 K and I = 0.3 mol dm-3 (NaClO4). The electron transfer reaction has also been carried out in the presence of anionic, cationic and neutral micelle. The reaction in acid medium is strongly catalyzed by changing [SDS]T (sodium dodecyl sulfate) up to 3 × 10-2 mol dm-3, beyond this concentration of SDS, the rate is retarded. The cationic and neutral micelle has a small effect on the rate. ΔH≠ (kJ mol-1) and ΔS≠ (JK-1 mol-1) values for the k1 and k2 paths are 30.20 ± 0.25, -159.65 ± 0.83 and 29.60 ± 0.62, -127.09 ± 2.17, respectively. The negative activation entropy is indicative of the ordered transition state for the electron transfer reaction. Formation of 2-amino-3-(2-amino-2-carboxy-ethyl) disulfanyl-propanoic acid as product is strongly supported by IR spectra.

No abstract

No abstract