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ISSN 1070-4272, Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 1, pp. 168−170. © Pleiades Publishing, Ltd., 2010.

Original Russian Text © S.M. Danov, V.A. Kolesnikov, A.L. Esipovich, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 1, pp. 170−171.

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Kinetics of Benzene Nitration by Nitric Acid
S. M. Danov, V. A. Kolesnikov, and A. L. Esipovich

Nizhnii Novgorod State Technical University, Dzerzhinsk Division, Dzerzhinsk, Russia

Received May 12, 2009

Abstract—The kinetics of benzene mononitration in excess of 45–70 wt % nitric acid in a homogeneous liquid
phase was studied. The data on the effects of temperature and nitric acid concentration on the reaction rate were
obtained.
DOI: 10.1134/S1070427210010337

Despite of 150-year history of the process, in industry 60–90°C. Typical kinetic curves of benzene consumption
benzene is nitrated by a mixture of nitric and sulfuric are given in Fig. 1.
acids [1]. A shortcoming of this method is the formation The obtained experimental data were treated on the
of abundant waste sulfuric acid. Increasing importance hypothesis that the rate of the benzene nitration reaction
of ecologically safety technologies requires creating new in an excess of nitric acid is described by a first-order
nitrating methods excluding the sulfuric acid application. equation with respect to benzene
One of ways of solving this problem is the application
of only nitric acid as the nitrating agent. However as yet r = kcB.
the nitration of benzene by only a mixture of nitric and
sulfuric acids was widely studied [1–3]. Here k is the effective rate constant of the nitration
In this work we studied the kinetics of benzene reaction and cB, molar concentration of benzene in
nitration by an excess of 45–70 wt % nitric acid in a reaction mixture (M).
a homogeneous liquid phase in a glass temperature- The linear form of the first order logarithmic
controlled batch reactor in the temperature range of anamorphoses (Fig. 2), observed up to the deep degrees
of benzene conversion, confirms the validity of the above-
mentioned assumption.

Values of rate constants (k ×105 s–1) and effective activation
energies of benzene nitration in nitric acid

Fig. 1. Kinetic curves of benzene consumption in benzene
nitration by 56.7% nitric acid. cτ is benzene concentration at the
time instant τ (M), τ, time (min). Temperature of nitration (°C):
(1) 60.1, (2) 70.5, (3) 80.1, (4) 88.1; the same for Fig. 2.

168

and the limiting stage is the interaction of an aromatic substrate with the nitronium cation. Special-purity grade 27-5 nitric acid containing 70% of the main substance column (5% Phenyl Polysilphenylene–siloxane).J. containing no less than 99. (2) Effective values of the process activation energy using a 15% Carbowax 1500 sorbent on a Cromaton-N- have been calculated from the temperature dependence AW carrying agent. −log k Values of acidity functions Н0 and НR of the reaction medium were taken from the works [6. The chromatograph was equipped of the reaction rate constants. REFERENCES respectively. 3). Orlova. Khimiya i tekhnologiya brizantnykh GCMS QP-2010 mass spectrometer with a TR-5MS vzryvchatykh veshchestv (Chemistry and Technology of RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. E. the second isotherm 230°C. Kinetics was studied in a batch reactor temperature. and the thermostat of the columns were 120 and 90°C. C0.6 × (1) The reaction of benzene nitration in excess of 10–3 M. 7]. and dehydrated. experimental data also fit a straight line in the coordinates log k–acidity functions Н0 and НR (Fig. 5] is observed. Logarithmic anamorphoses of the curves of benzene logarithm of the rate constant on the acidity function НR consumption in benzene nitration by 56. Nitration products were identified on a SHIMADZU 1. heating rate 10 deg min–1. n = 2. n = 1. preliminary distilled k is rate constant (s−1). Concentration of the acid was checked by Temperature of a column: the first isotherm 60°C. A flame ionization detector and nitrogen of a mathematical model of the process of benzene as a gas-carrier were used. The obtained instant τ. n. log k linearly depending on the acidity function by the GLC method on a “Khromas GKh1000” НR with a slope close to unity. 1 2010 . No traces of dinitrobenzene and products of benzene controlled accurate to ±0. Chemically-pure grade benzene. 2.69 wt the benzene nitration reaction.35–66. The nitration was carried out oxidation were found under the aforesaid conditions of in excess of nitric acid of the concentration 44. Gas-carrier helium. 3. length. 4 min. According to the available concepts of the mechanism of nitrating organic aromatic compounds by a mixture of sulfuric and nitric acids. EXPERIMENTAL −H Fig. 45–70 wt % nitric acid is of the first order with respect to Components of the reaction mixture were analyzed benzene. Therewith the linear dependence of the decimal Fig. respectively. KINETICS OF BENZENE NITRATION BY NITRIC ACID 169 The resulting values of rate constants and effective activation energies are given in the table. (2) НR.25 mm. chromatograph with a metal column (1 m × 3 mm). Column was diluted at 0°C with distilled water up to a required diameter was 0. % in the temperature range of 60–88. the active nitrating agent is the nitronium ion NO2+. 83 No. Dependences of log k on acidity functions Н0 and НR.09. concentration. cτ are benzene concentrations at the initial instant and at the time with a slope equal to unity [4. with a precolumn (1 m × 3 mm) filled with a mixture of sodium hydrocarbonate and a Cromaton N-AW inert (3) The data obtained can be used in the development carrying agent.. Temperatures of the evaporator nitration by nitric acid. 60 m. It points to a similarity of the benzene nitration mechanisms by a mixture of acids and by nitric acid only at its excess.1°C so that the reaction mixture was homogeneous.7% nitric acid. Initial concentration CONCLUSIONS of benzene in all experiments was approximately 3. Acidity function: (1) Н0. the acid-base titration.1°.57. slope ratio of a straight line.9% of the main substance was used in the work.

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