Thermodynamic nitration rates of aromatic compounds. Part 4. Temperature dependence in sulfuric acid of HNO3→NO2+ equilibrium, nitration rates and acidic properties of the solvent †

Marziano, Nunziata Clara; Tomasin, Alberto; Tortato, Claudio; Zaldı́var, J.M.

doi:10.1039/a802521e

Cited by 32 publications

(31 citation statements)

References 25 publications

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“…3a and 3b clearly shows the progressive involvement of sulfuric acid as specific catalytic species of the reaction. Indeed, in the range 80-100 wt%, the molecular species of sulfuric acid increases with the acid concentration according to equilibrium [H 2 SO 4 HSO 4 − + H + ] and the variation of [H 2 SO 4 ] becomes significant and experimentally available [13,14]. iii.…”

Section: Kinetic Behaviour Of Oximesmentioning

confidence: 99%

“…The latter were evaluated by the "activity coefficient functions" as parameters related to variations of activity coefficients of the different acidic mixtures [11][12][13][14]. Indeed, a number of studies in concentrated aqueous solutions of strong acids (HA) applied both to dissociation of HA (equilibrium 1) and to protonation of weak bases (B) (equilibrium 2) shows that the activity coefficient terms of thermodynamic Eqs.…”

Section: Kinetic Behaviour Of Oximesmentioning

confidence: 99%

“…Such a procedure, widely tested in the studies of equilibria [10][11][12][13][14] and reactivity [14,21,22] allows to obtain a reliable description of a process in nonideal acid systems and rate constants (k o ) referred to water as standard state, the latter to be used, especially, for comparing solutes in different acids.…”

Section: Kinetic Behaviour Of Oximesmentioning

confidence: 99%

“…The values were obtained by taking into account: (i) the effective concentrations of the reacting species involved in the rearrangement, (ii) the acidic properties of the medium described by "an activity coefficient function," and (iii) the interactions between solutes and solvents described by "the protonating ability" of the acid systems under investigation [11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

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On the Beckmann rearrangement of ketoximes: A kinetic study in trifluoromethanesulfonic acid

Marziano¹,

Ronchin²,

Tortato³

et al. 2004

Int J of Chemical Kinetics

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The formation and the destruction of an intermediate involved in the Beckmann rearrangement of 2,4,6-trimethylacetophenone oxime have been studied in concentrated trifluoromethanesulfonic acid by kinetic and spectroscopic measurements. Observed (k obs ) and thermodynamic rate constants (k o ) have been estimated and the values compared with the ones obtained in perchloric, sulfuric, and methanesulfonic acids. In the range 80-100 wt% of sulfuric acid, combined analysis of k obs and k o rates shows a specific catalysis due to [H 2 SO 4 ] species. In trifluoromethanesulfonic acid, lower rate constants, compared to the values in sulfuric acid, have been observed which differ at 99 wt% by a factor of 10 3 ca. The catalytic effect of different strong acids, the structure of the intermediate inferred from Raman and NMR spectra, and the role of the ion-pairs involved in the reaction are discussed. C

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Section: Kinetic Behaviour Of Oximesmentioning

confidence: 99%

Section: Kinetic Behaviour Of Oximesmentioning

confidence: 99%

Section: Kinetic Behaviour Of Oximesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

On the Beckmann rearrangement of ketoximes: A kinetic study in trifluoromethanesulfonic acid

Marziano¹,

Ronchin²,

Tortato³

et al. 2004

Int J of Chemical Kinetics

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“…Considering the importance of NO ＋ judged by some experimental and theoretical results. 5 It was reported that HA could be converted to DPT by AcONO 2 in the presence of HOAc, but hardly reacted to form DPT (1,5-endomethylene-3,7-dinitro-1,3,5,7-tetrazacyclooctane) when only AcONO 2 was used, 6 so the acidic reagents, Ac 2 O and HOAc, are the key factors for the nitrolysis of HA. Other acidic mixing reagents, e.g., HNO 3 -Ac 2 O, HNO 3 -HOAc, and HNO 3 -NH 4 NO 3 -Ac 2 O, are also often used in the nitration or nitrolysis reaction.…”

Section: Nomentioning

confidence: 99%

Theoretical Investigation on the Mechanism and Design of Catalysts for Nitrolysis of Hexamine

Shi

Zhao²,

Zhang

et al. 2010

Chin. J. Chem.

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Nitration of nitrobenzene at high‐concentrations of sulfuric acid: Mass transfer and kinetic aspects

2009

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This article reports studies on mass transfer and kinetics of nitration of nitrobenzene at high concentrations of sulfuric acid in a batch reactor at different temperatures. The effects of concentration of sulfuric acid, speed of stirring, and temperature on mass transfer coefficient were investigated. The kinetics of nitration under homogenized conditions was studied at different sulfuric acid concentrations at these temperatures. The reaction rate constants were determined. The variation of rate constant with sulfuric acid concentration was explained by the M c function. The activation energies of the reactions were determined from the Arrhenius plots. The regimes of the reactions were determined using the values of the mass transfer coefficients and the reaction rate constants. A model was developed for simultaneous mass transfer and chemical reaction in the aqueous phase. The yields of the three isomers of dinitrobenzene were determined, and the variation of isomer distribution with sulfuric acid concentration and temperature was analyzed. This work demonstrates that more than 90% conversion of nitrobenzene is possible at high-sulfuric acid concentrations resulting in high yield of the product even at moderate temperatures and at low speeds of stirring.

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Thermodynamic nitration rates of aromatic compounds. Part 4. Temperature dependence in sulfuric acid of HNO3→NO2+ equilibrium, nitration rates and acidic properties of the solvent †

Cited by 32 publications

References 25 publications

On the Beckmann rearrangement of ketoximes: A kinetic study in trifluoromethanesulfonic acid

On the Beckmann rearrangement of ketoximes: A kinetic study in trifluoromethanesulfonic acid

Theoretical Investigation on the Mechanism and Design of Catalysts for Nitrolysis of Hexamine

Nitration of nitrobenzene at high‐concentrations of sulfuric acid: Mass transfer and kinetic aspects

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