Dependence of the rate constant and activation energy of aromatic nitration on mixed acid composition

Field, John P.; Strachan, Alec N.

doi:10.1021/i300007a003

Cited by 9 publications

(2 citation statements)

References 2 publications

(2 reference statements)

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“…H R is determined from the ionization of tri‐aryl carbinols and H o relates to indicators ionizing according to the different schemes. Field and Strachan have analyzed the dependence of kinetics on acidity function in detail 14 …”

Section: Rate Constant Prediction Methodologiesmentioning

confidence: 99%

“…Field and Strachan have analyzed the dependence of kinetics on acidity function in detail. 14 The expressions for the rate constant reported in the literature (Equation. 5) show a relationship between equilibrium constant (K) of dissociation of acids towards the generation of NO 2 + ions, the rate constant related to the mechanism (k′), activity and activity coefficients, acidity function (H R ), and the observed rate constant (k obs ):…”

Section: Rate Constant Prediction Methodologiesmentioning

confidence: 99%

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Estimation of reaction kinetics for aromatic and heterocycles nitration in mixed acids through computational chemistry approach

Jadhav

Pandey

Kulkarni

2020

Int J of Chemical Kinetics

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Nitration of aromatic compounds and heterocycles in mixed acid environment is one of the regularly performed large‐scale reactions in the chemical industry. Although the reaction mechanism of nitration of aromatics in mixed acid is well established, the development of a methodology for the evaluation of kinetics of exothermic aromatic nitrations in a simplified and accurate way is necessary. Here we evaluate the applicability of a kinetic evaluation methodology based on Hammett's acidity function, acidity function, and empirical activity coefficient for the nitration reaction. The contributions from the functional groups on the aromatic ring and quantitative structure‐activity relationships technique are considered for these evaluations. Natural bond orbital and magnetic index nucleus independent chemical shift analyses were carried out to obtain the substitution constants. The rate constant and activation energy values were evaluated at various temperatures and sulfuric acid strengths. The results were validated by comparing with the experimental data from the literature for several molecules. The effect of various functional groups (viz carbonyl, carboxyl, methyl, and amine) substituted on the benzene ring was also evaluated. For a few identified substrates, the data were used for estimation of residence time needed for complete conversion in continuous stirred tank reactor and in a plug flow reactor to quantify the effect of substitution constant and strength of sulfuric acid. The approach will help select a suitable reactor.

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Section: Rate Constant Prediction Methodologiesmentioning

confidence: 99%

Section: Rate Constant Prediction Methodologiesmentioning

confidence: 99%

Estimation of reaction kinetics for aromatic and heterocycles nitration in mixed acids through computational chemistry approach

Jadhav

Pandey

Kulkarni

2020

Int J of Chemical Kinetics

View full text Add to dashboard Cite

show abstract

Thermally safe operation of a semibatch reactor for liquid‐liquid reactions–fast reactions

Steensma

Westerterp

1991

Chem Eng & Technol

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Accumulation of the reactant supplied to a cooled semibatch reactor (SBR) will occur if the mass transfer rate across the interface is insufficient to keep pace with the supply rate. Then, due to a low starting temperature or supercooling, the reaction temperature does not rise fast enough to the desired value. This accumulation may eventually lead to a temperature runaway. We investigated the possibility of such an event for reactions of the type "chemically enhanced mass transfer" or "fast" and found that only low distribution coefficients, i.e. or lower, can lead to accumulation. At higher distribution coefficients, the mass transfer rate across the interface of a well-mixed dispersion is generally sufficient to prevent accumulation. A thermal runaway in the fast regime exerts a moderate effect, because the effective activation energy is halved. Calculations for the "instantaneous" reaction regime, regarded as a special case of fast reactions, show that there is no runaway possible.

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The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

et al. 2007

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Dependence of the rate constant and activation energy of aromatic nitration on mixed acid composition

Cited by 9 publications

References 2 publications

Estimation of reaction kinetics for aromatic and heterocycles nitration in mixed acids through computational chemistry approach

Estimation of reaction kinetics for aromatic and heterocycles nitration in mixed acids through computational chemistry approach

Thermally safe operation of a semibatch reactor for liquid‐liquid reactions–fast reactions

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

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