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Keywords = peroxycarbonic

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11 pages, 3354 KB  
Article
Kinetics of Grape Seed Oil Epoxidation in Supercritical CO2
by Juan Catalá, Jesús Manuel García-Vargas, María Jesús Ramos, Juan Francisco Rodríguez and María Teresa García
Catalysts 2021, 11(12), 1490; https://doi.org/10.3390/catal11121490 - 6 Dec 2021
Cited by 7 | Viewed by 3317
Abstract
The epoxidation of grape seed oil in supercritical CO2, to the best of our knowledge, has been only superficially described in the literature, apart from a short communication and our own previous published work on the topic. In this work, a [...] Read more.
The epoxidation of grape seed oil in supercritical CO2, to the best of our knowledge, has been only superficially described in the literature, apart from a short communication and our own previous published work on the topic. In this work, a thorough study of the performance of the supercritical epoxidation of grape seed oil is performed in a wide range of conditions, and the kinetic parameters of the supercritical epoxidation of vegetable oils are reported for the first time in the literature. The experimental work has covered a 40–60 °C temperature range at 150 bar, sampling during a period of 48 h. The nature and extent of the side reactions and secondary products obtained have been evaluated, being hydrolysis products and their oligomerization derivatives the major by-products. Reaction rate constants (10−2 h−1 order) and activation energy parameters were finally calculated from the experimental conversion and epoxy yield data to establish the effect of temperature on the kinetics of the process. Full article
(This article belongs to the Special Issue Catalytic Epoxidation Reaction)
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15 pages, 4095 KB  
Article
Design and Fine-Tuning Redox Potentials of Manganese(II) Complexes with Isoindoline-Based Ligands: H2O2 Oxidation and Oxidative Bleaching Performance in Aqueous Solution
by Bashdar I. Meena and József Kaizer
Catalysts 2020, 10(4), 404; https://doi.org/10.3390/catal10040404 - 7 Apr 2020
Cited by 7 | Viewed by 3483
Abstract
A series of divalent manganese complexes [MII(HL1–6)Cl2] with the 1,3-bis(2’-Ar-imino)isoindolines (HLn, n = 1–6, Ar = pyridyl, 4-methylpyridyl, imidazolyl, thiazolyl, benzimidazolyl and N-methylbenzimidazolyl, respectively) including the previously reported ligands (HL1–2, 4–6) and [...] Read more.
A series of divalent manganese complexes [MII(HL1–6)Cl2] with the 1,3-bis(2’-Ar-imino)isoindolines (HLn, n = 1–6, Ar = pyridyl, 4-methylpyridyl, imidazolyl, thiazolyl, benzimidazolyl and N-methylbenzimidazolyl, respectively) including the previously reported ligands (HL1–2, 4–6) and complexes ([MII(HL1,5)Cl2]) have been prepared and characterized by electrochemical and spectroscopic methods. In these complexes, it was possible to control the redox potential of the metal center by varying the aryl substituent on the bis-iminoisoindoline moiety, and investigate its effect in a catalase-like reaction, and oxidative bleaching process in buffered aqueous solution. The kinetics of the dismutation of H2O2 into H2O and O2, and the oxidative degradation of morin by H2O2 were investigated in buffered water, where the reactivity of the catalysts in both systems was markedly influenced by the redox and Lewis acidic properties of the metal centers and the concentration of the bicarbonate ions. Both the catalase-like and bleaching activity of the catalysts showed a linear correlation with the MnIII/MnII redox potentials. The E1/2 spans a 561 mV range from 388 mV (Ar = benzymidazolyl) to 948 mV (Ar = 4-methylpyridyl) vs. the SCE. The amount of bicarbonate is a critical issue for the in situ formation of peroxycarbonate as a versatile oxidant, and its participation in the formation of high valent MnIV = O species. Full article
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