84319-22-2Relevant articles and documents
Solvent hydrogen bonding and structural influences on the CrVI oxidation of anilines in aqueous acetic acid medium
Bhuvaneshwari,Elango
experimental part, p. 242 - 249 (2010/04/26)
The oxidation of meta- and para-substituted anilines by CrVI oxidant, imidazolium fluorochromate (IFC), in aqueous acetic acid mixtures of varying compositions in the presence of p-toluenesulfonic acid (PTS) is first order in IFC and PTS. Michaelis-Menten type kinetics is observed with all of the anilines. The IFC oxidation of 15 meta- and para-substituted anilines at 299-322 K complies with the isokinetic relationship but not to any of the linear free energy relationships. The isokinetic temperature lies within the experimental range. The rate data failed to correlate with macroscopic solvent parameters such as relative permittivity, εr, and ionizing power, Y, correlation of rate data with Kamlet-Taft solvatochromic parameters (hydrogen bond donor acidity, α, hydrogen bond acceptor basicity, β, and dipolarity/polarizability, π*) is linear which suggests that the specific solute-solvent interactions play a dominating role in governing the reactivity.
Mechanism and reactivity in perborate oxidation of anilines in acetic acid
Karunakaran, Chockalingam,Kamalam, Ramasamy
, p. 2011 - 2018 (2007/10/03)
Perborate but not percarbonate in acetic acid generates peracetic acid on standing and the peracetic acid oxidation of anilines is fast. The oxidation with a fresh solution of perborate in acetic acid is smooth and second order but the specific oxidation rate increases with increasing [perborate]0 or [boric acid]. Perborate on dissolution affords hydrogen peroxide and a borate; the latter assists the former in the oxidation. The oxidation rates of anilines under identical conditions do not conform to any of the linear free energy relationships but the reaction rates of molecular anilines do. Perborate oxidation proceeds via two reaction paths but the overall oxidation rates of molecular anilines conform to structure reactivity relationships; the transition states do not differ significantly. Analysis of the oxidation rates of perborate and percarbonate reveals that while perborate oxidation is faster than percarbonate it is at least as selective as the latter.
Polarographic Behaviour of Nitroacetanilides in Presence of some Ionic and Non-ionic Surfactants vis-a-vis their Effect on Kinetics of the Electrode Reaction
Singh, Mukhtar
, p. 93 - 97 (2007/10/02)
Polarographic behaviour of o-, m- and p-nitroacetanilides (in 25percent ethanolic solution) has been studied at 25+/-0.1 deg in Britton-Robinson (BR) buffer of pH 6.1 in the presence of increasing amounts of nine different ionic and non-ionic surfactants.Each depolariser gives a single 4-electron reduction wave which has been found to be diffusion-controlled and irreversible.A decrease in the value of kinetic parameters (αna and k0f,h) with the increasing concentrations of ionic and non-ionic surfactants shows that the irreversible electrode reactions of o-, m- and p-nitroacetanilides tend to become increasingly more irreversible.This is supported by a decrease in id abd a negative shift in E1/2 with increasing concentrations of the surfactants.A tentative mechanism of the polarographic reduction of nitroacetanilides has also been proposed at pH 6.1.The ease of reduction of the three isomers at d.m.e. is in the order, ortho > meta > para.
