The Role of the Medium in Chain-initiation Reactions

Emanuel, N.M.; Заиков, Г. Е.; Maizus, Z. K.

doi:10.1016/b978-0-08-022067-3.50011-9

Cited by 3 publications

(23 citation statements)

References 103 publications

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“…In* + RH -InH + R* (10) InH + ROOH -products (11) InH + 02 In' + H02* (12) InOOR InO* + RO* (13) In'…”

Section: Kinetics Of Inhibited Oxidation Of Hydrocarbons a Mechanisms...mentioning

confidence: 99%

“…Aromatic amines react faster with hydroperoxides than phenols. As with benzoyl peroxide, the reaction apparently involves electron transfer3 ArNHAr + ROOH -ArN+HAr +ROOH'--Ar2N' + H20 + RO' (11) Both 02 and ROOH are normally present in oxidizing RH, and InH is attacked by both these agents. Compare the rates of these reactions: vn/v12 = fcn[02]/ fe12 [ROOH].…”

Section: Inh + 02mentioning

confidence: 99%

“…

2D0a-1[l -(1 -a't)1/2]''5 IX 2,7,8,11 fe2*u [RH][ROOH]//fe7[ROOH]0[1 -exp(0t)]'"A mechanism is defined by corresponding key reactions; see section IX. A also.

…”

mentioning

confidence: 99%

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Mechanisms of action and reactivities of the free radicals of inhibitors

Denisov¹,

Khudyakov²

1987

Chem. Rev.

282

189

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“…In* + RH -InH + R* (10) InH + ROOH -products (11) InH + 02 In' + H02* (12) InOOR InO* + RO* (13) In'…”

Section: Kinetics Of Inhibited Oxidation Of Hydrocarbons a Mechanisms...mentioning

confidence: 99%

Section: Inh + 02mentioning

confidence: 99%

See 1 more Smart Citation

Mechanisms of action and reactivities of the free radicals of inhibitors

Denisov¹,

Khudyakov²

1987

Chem. Rev.

282

189

View full text Add to dashboard Cite

“…Tables 5-8 list some literature values for the collision factor A, activation energy E a and rate constant k for the initiation of the elementary reaction, peroxide decomposition (branching), propagation, and termination [340,341,[351][352][353][354] (Because autoxidation is generally initiated by the decomposition of added peroxides, peroxide decomposition frequently is designated "initiation" in the literature, which is incorrect and may lead to confusion. )…”

Section: Kinetics Of Autoxidationmentioning

confidence: 99%

“…For low-conversion reactions, which are required for the precise determination of the kinetics, the sensitivity limits of all analytical methods are quickly reached. For a review of experimental methods for the determination of the kinetics of radical chain oxidations see [341], and for analytical methods for peroxide determination see [372].…”

Section: Kinetics Of Autoxidationmentioning

confidence: 99%

Oxidation

Teles

Hermans

Franz³

et al. 2015

Ullmann's Encyclopedia of Industrial Chemistry

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The article contains sections titled: 1. Introduction 2. Overview of industrial oxidation processes 2.1. Inorganic chemicals 2.1.1. Sulfur derivatives 2.1.2. Carbon derivatives 2.1.3. Nitrogen derivatives 2.1.4. Chlorine derivatives 2.2. Organic chemicals 2.2.1. Olefins and alkynes 2.2.2. Epoxides 2.2.3. Hydroperoxides 2.2.4. Alcohols 2.2.5. Aldehydes 2.2.6. Ketones 2.2.7. Phenols and derivatives 2.2.8. Carboxylic acids, saturated 2.2.9. Carboxylic acids and anhydrides, unsaturated 2.2.10. Carboxylic acids and anhydrides, aromatic 2.2.11. Esters, lactones and carbonates 2.2.12. Nitriles 2.2.13. Oxidized nitrogen compounds 2.2.14. Chlorinated compounds 2.2.15. Sulfur compounds 3. Thermodynamics; Stability of Hydrocarbons 4. Reaction Types 5. Homolytic Oxidation 5.1. Historical Development; Reaction Mechanism; Radical Reactivity 5.2. Kinetics of Autoxidation 5.3. Differences between Liquid‐ and Gas‐Phase Autoxidations 5.4. Homolytic Oxidation in the Liquid Phase 5.4.1. Secondary Reactions of Radicals, Peroxides, and other Intermediates 5.4.2. Metal Catalysis in Homolytic Liquid‐Phase Oxidation 5.4.3. Inhibitors of Homolytic Liquid‐Phase Oxidation 5.4.4. Special Cases of Homolytic Oxidation 5.4.5. Process Technology of Homolytic Liquid‐Phase Oxidation 5.5. Homolytic Gas‐Phase Oxidation 5.6. Gas Explosions and Safety Data 6. Heterolytic Oxidation 6.1. Heterolytic Oxidation in the Liquid Phase 6.2. Heterogeneously Catalyzed Gas‐Phase Oxidation 6.2.1. Oxidation Catalysts 6.2.2. Process Technology of Heterogeneously Catalyzed Oxidations

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Understanding the Co/Mn/Br Synergistic Catalysis in Liquid Phase Oxidation of 5-Hydroxymethyl Furfural to 2,5-Furandicarboxylic Acid Based on the Effective Collision Theory

Wei

et al. 2023

Ind. Eng. Chem. Res.

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2,5-Furandicarboxylic acid (FDCA) is an important monomer for the bio-based degradable polymer polyethylene 2,5-furandicarboxylate. Current kinetic studies on the preparation of FDCA by the liquid-phase oxidation of 5-hydroxymethyl furfural (HMF) have failed to quantitatively consider the effect of the ratio and concentration of Co/Mn/Br ternary catalysts, although they play an important role in the oxidation reaction rate and selectivity. In this work, an effective collision theory was introduced into the kinetic modeling, and then, a kinetic model of HMF oxidation with nine parameters was developed. The fitting results of this model using experimental data of HMF liquid phase oxidation with different catalysts and temperatures were satisfactory. The relative collision frequency coefficients α and β successfully describe the reactivity of Co and Mn, respectively, and they are only influenced by the water content in the solvent and do not vary with temperatures. The chain initiation rate constants are only temperature-dependent, and the other rate constants remain constant over the studied range. The kinetic model developed in this work would bring valuable insights into the synergistic effects of the Co/Mn/Br ternary catalyst components on the oxidation of HMF.

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The Role of the Medium in Chain-initiation Reactions

Cited by 3 publications

References 103 publications

Mechanisms of action and reactivities of the free radicals of inhibitors

Mechanisms of action and reactivities of the free radicals of inhibitors

Oxidation

Understanding the Co/Mn/Br Synergistic Catalysis in Liquid Phase Oxidation of 5-Hydroxymethyl Furfural to 2,5-Furandicarboxylic Acid Based on the Effective Collision Theory

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