Liquid-Phase Oxidation of Oxygen-Containing Compounds

Денисов, Е. Т.; Mitskevich, N. I.; Агабеков, В. Е.

doi:10.1007/978-1-4684-8517-2

Cited by 62 publications

(91 citation statements)

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“…A number of authors have tried to elucidate the kinetics and mechanism of the ozonolysis of alcohols and their application to the selective preparation of ketones and aldehydes in high yields under mild conditions [3,[39][40][41][42][43][44][45][46]. The basic concepts of such reactions are discussed in several references [1,2,25,34,35,39].…”

Section: Alcoholsmentioning

confidence: 99%

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Kinetics and Mechanism of the Ozone Reaction with Alcohols, Ketones, Ethers and Hydroxybenzenes

Rakovsky¹,

Anachkov²,

Belitskii³

et al. 2016

ChChT

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Abstract. The review, based on 92 references, is focused on degradation of organics by ozonation and it comprises various classes of oxygen-containing organic compounds -alcohols, ketones, ethers and hydroxybenzenes. The mechanisms of a multitude of ozone reactions with these compounds in organic solvents are discussed in details, presenting the respective reaction schemes. The corresponding kinetic parameters are given and some thermodynamic parameters are also listed. The dependences of the kinetics and the mechanism of the ozonation reactions on the structure of the compounds, on the medium and on the reaction conditions are revealed. Various possible applications of ozonolysis are specified and discussed. All these reactions have practical importance for the protection of the environment.

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Section: Alcoholsmentioning

confidence: 99%

“…The basic concepts of such reactions are discussed in several references [1,2,25,34,35,39]. It has been established that the rate of ethanol ozonolysis does not change when the hydroxyl group is deuterated [43] and its value is 4.17 times higher than in case the methylene group is deuterated.…”

Section: Alcoholsmentioning

confidence: 99%

Kinetics and Mechanism of the Ozone Reaction with Alcohols, Ketones, Ethers and Hydroxybenzenes

Rakovsky¹,

Anachkov²,

Belitskii³

et al. 2016

ChChT

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“…Upon altering the copper ion concentration by a factor of nearly 700 at 116°C and a constant pD, there was no significant impact upon the rate of enolization (see expts. 6 and 7, Table 4). Similarly, at 145°C the addition of copper ion had little effect upon the reaction rate at a constant pD (see expts.…”

Section: Effect Of Copper Ion On the Rate Of Enolizationmentioning

confidence: 99%

High temperature–pressure aqueous oxidations. IV. A kinetic study of the oxidation and enolization of cyclohexanone in the presence of catalytic metal ions

Taylor¹

1989

Can. J. Chem.

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. 67, 165 (1989).The aqueous high pressure-temperature oxidation of cyclohexanone was found to be strongly catalyzed by silver, iron(III), and copper ions but not by aluminum, cobalt, manganese@), or nickel ions. The reactivities of the catalytic ions were inhibited by the acidic oxidation products. Accordingly, initial reaction velocities were determined and used to correlate the kinetic data. A detailed kinetic study of copper ion catalysis has shown that in the presence of that ion the reaction was first order in cyclohexanone, one-half order in copper ion, and zero order in oxygen. The rate of enolization of cyclohexanone appeared to be unaffected by the presence of copper ion under conditions of constant acidity but was strongly catalyzed by both deuterium ion and acetate ion. Further, the rate of oxidation exceeded the rate of enolization at higher copper ion concentrations. These data contrast with the uncatalyzed oxidation, for which the kinetic reaction was first order in cyclohexanone, one-half order in oxygen, and the rate of oxidation was much less than the rate of enolization. The activation energies for the catalyzed and uncatalyzed oxidations were about the same, but the entropies of activation were quite different. From these data it is concluded that the en01 is not a major intermediate for the catalyzed reaction. It is suggested that the copper ion may form an active peroxy complex with the oxygen molecule to serve as the reactive oxidant.Key words: metal ion catalysis, kinetics, cyclohexanone, high temperature oxidation, high pressure oxidation.JOHN W. THOMAS et JAY E. TAYLOR. Can. J. Chem. 67, 165 (1989).On a trouvt que I'oxydation de la cyclohexanone, en milieu aqueux et h des tempkratures et des pressions ClevCes, est fortement catalyste par les ions de l'argent, du fer(II1) et du cuivre, mais pas par les ions du aluminum, du cobalt, du manganbse(I1) et du nickel. Le rtactivitt des ions catalytiques est inhibCe par les produits acides de l'oxydation. On a donc determint les vitesses initiales des rCactions et on les a utilisCes pour Ctablir une corrklation avec les donnCes cinCtiques. Une Ctude cinttique dttaillte de la catalyse par l'ion du cuivre a montrk que, en prCsence de cet ion, la rCaction est du premier ordre en cyclohexanone, d'ordre un demi en ion du cuivre et d'ordre zero en oxygene. I1 semble que, h acidite constante, la vitesse d'Cnolisation de la cyclohexanone n'est pas affectke par la prCsence des ions du cuivre; toutefois, elle est fortement catalyste par l'ions deutCrium et acCtate. De plus, h des concentrations ClevCes d'ions du cuivre, la vitesse d'oxydation est plus ClevCe que la vitesse d'Cnolisation. Ces donnCes sont en opposition avec ceux obtenus lors de l'oxydation non-catalysCe de la cyclohexanone alors que la rCaction cinCtique Ctait du premier ordre en cyclohexanone, d'ordre un demi en oxygitne et que la vitesse d'oxydation Ctait beaucoup plus faible que la vitesse dlCnolisation. Les tnergies d'activation pour les reactions catalystes et non-catalystes sont appr...

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“…Cellulose is a polyalcohol that can be oxidized during pulp bleaching giving rise to carbonyl and carboxyl groups . 1 The oxidations lead to reduction of cellulose molecular weight through autocatalytic reactions 2 and new water-insoluble aromatic structures are formed 3 from cellulose chain. All these phenomena may contribute to pulp brightness reversion.…”

Section: Introductionmentioning

confidence: 99%

“…7 Wood type has also been cited as a source of pulp brightness instability. [7][8][9] Pulp bleaching stages based on chlorine and oxygen derived chemicals give rise to a number of oxidative species, including radicals such as Cl•, ClO•, •O 2 -, HO•, HO 2 • and H• and cations such as Cl + , HO + , O 3 + and H + . 10 These species react preferentially with electron-rich aromatic and olefin structures, but might also react with carbohydrate species.…”

Section: Introductionmentioning

confidence: 99%

The role of bound chlorine in the brightness reversion of bleached hardwood kraft pulp

2009

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Our previous paper showed fragmentary evidence that pulp brightness reversion may be negatively affected by its organically bound chlorine (OX) content. A thorough investigation on eucalyptus kraft pulp led to the conclusion that OX increases reversion of certain pulps but this trend is not universal. Alkaline bleaching stages decrease reversion regardless of pulp OX content. Pulps bleached with high temperature chlorine dioxide revert less than those bleached with conventional chlorine dioxide in sequences ending with a chlorine dioxide stage but similarly in sequences ending with a final peroxide stage. The use of secondary condensate for pulp washing decreases reversion

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Liquid-Phase Oxidation of Oxygen-Containing Compounds

Cited by 62 publications

References 0 publications

Kinetics and Mechanism of the Ozone Reaction with Alcohols, Ketones, Ethers and Hydroxybenzenes

Kinetics and Mechanism of the Ozone Reaction with Alcohols, Ketones, Ethers and Hydroxybenzenes

High temperature–pressure aqueous oxidations. IV. A kinetic study of the oxidation and enolization of cyclohexanone in the presence of catalytic metal ions

The role of bound chlorine in the brightness reversion of bleached hardwood kraft pulp

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