© Proc. Indian natn. Sct. Acad., 49, A, No 5, 1983, pp. 545-549. Printed in India. Chemical Kinetics ACTIVATION ENERGY STUDIES IN OXIDATION OF p-XYLENE Prem NatH Tiwari* Department of Chemical Engineering and Technology, Institute of Technology, Banaras Hindu University, Varanasi-221 005, India (Received 9 March 1982; after revision 31 January 1983) The value of activation energy in the reaction of oxidation of p-xylene to terephthalic acid obtained (Tiwari, 1971; and Tiwari & Tripathi, 1978) has ‘been examined in the light of collision theory, absolute theory of reaction rates and other considerations, The change in activation enthalpy of this reaction has also been studied. Keywords : p-Xylene; Terephthalic acid; Polyethylene Terephthalate: p-Toluic Acid; p-Tolualdehyde INTRODUCTION THe reaction of oxidation of p-xylene to terephthalic acid is an important industrial process, because terephthalic acid is the starting material in the manu- facture of synthetic fibre polyethylene terepthalate. The available literature on this reaction process is mostly in form of patents and its kinetic data has rarely been studied. So, an attempt has been made in the present paper to study the value of activation energy and change in activation enthalpy of this reaction process obtained elsewhere (Tiwari, 1971; and Tiwari & Tripathi, 1978). EXPERIMENTAL The oxidation of p-xylene to terephthalic acid was done in the temperature range of 50 to 90°C at atmospheric pressure in the presence of cobalt acetate tetrahydrate as catalyst and ammonium bromide as promoter in acetic acid medium in a semibatch stirred reactor. The experimetal portion is described in detail elsewhere (Tiwari, 1971; and Tiwari & Tripathi, 1978). RESULTS AND DISCUSSION The activation energy was found to be 6.7 k. cal/g.mole. The change in the activa- tion enthalpy was calculated to be 6.07, 6.05, 6.04 and 6.03 K.cal/g.mole at tempera- tures 333, 343, 348 and 353°K, respectively. The details of analytical data are shown in the Tables [and II. The plot of log k versus 1/T has been shown “Present address : Manager (R&D), Reichhold Chemicals India Ltd., Kannabiran Koil Street, P. O. Bag No. 3, Madhavaram, Madras-600 060.546 PREM NATH TIWARI Tape I Analytical data semibatch process with stirring Activation Energy, E ~ 6.732 k. cal./g.mole AH* = change in activation enthalpy, k.cal/g.mole PTA = p-toluic acid, k = reaction rate constant, sec™* Feed rate of air = 0.0226 liters/sec Amount of acetic acid taken = 300 ml Concentration _of catalyst _ [Co(AcO): 4.0] _ 9 65 (NB, Br] : Agitation velocity 800 rpm Amount of p-xylene 0.406 g. mole Initial concentration of p-xylene 1.35 molar Temperature *A Concentration of Promoter ~ Time in 343 hours -————_-____— -a —— PTA yield Unreacted k x 10° AH* PTA yield Unreacted. k x 10 — AH* in p-xylene sec“ in p-xylene sec“ g. mole Molarity g. mole Molarity 1 = 1.300 - 1.295 2 0.028 1.260 0.029 1.257 4 0.037 1.230 0.039 1.224 6 004s 1,208 0.089 1.191 8 0.054 = «1.175 0.318 6.073, «0.058 1.160 0.373 6.053, 10 0.062 1.148 0.067 1.129 12 0.069 1.123 0.076 1.100 4 0.077 1.097 - - Taste I ‘Temperature °A Time in 348 hours. ———-— — — PTA yield Unreacted kx 10* AH* PTA yield Unreacted k x 10* 4H* in p-xylene sec™* in p-xylene sec mole Molarity gmole — Molarity 1 - 1.290 - 1.280 2 0.035 1.238 0.037 1.231 4 0.049 «1.192 0543 6.043 0.044 L.ITS 0.638 6.033 6 0.062 1.147 0.070 1,122 8 0.065 1,103 0.085 1.071 10 0.088 1.060 0.099 1.024 12 _ - 0.137 0.897ACTIVATION ENERGY STUDIES IN OXIDATION OF p-XYLENE 547 elsewhere (Tiwari, 1971; and Tiwari & Tripathi, 1978). The greater the value of E, the less the efficiency of collision and the less the rate of reaction, also, the greater the value of E, the greater is the relative effect of a change in temperature, (Ritchie, 1966). It can therefore, be said that the smaller the value of E, the greater is the effi- ciency of collision and the less is the relative effect of a change in temprature on the rate of reaction, which is an observed experimental fact. Also collision theory views the rate to be governed by the number of energetic collisions between reactants (Levenspiel, 1962). Hence, the value of activation energy appears to be justified in the view of collison theory. The lowering of the energy of activation is attributed to the effect of the acetic acid solvent. The appropriate solvent changes the activation energy considerably. (Hinshelwood, 1949). It is quite evident from the phenomenon of solubility that in general the molecules exert influences on one another. So, is the case with acetic acid solvent when the reactants p-xylene, oxygen, catalyst, promoter and the p-toluic acid get dissolved in the acid to form a homogencous liquid-phase, the distance bet- ween the various molecules of the system is of the order of one molecular diameter. Therefore, an appreciable amount of change in potential energy occurs due to which activation energy also records a change. The activation energy was interpreted by Arrhenius as the excess over the aver- age energy that the reactants must possess in order for the reaction to occur. (Smith, 1956). This energy is supplied by external agencies in order to activate the mole- cules of reactants. Although, Arrhenius theory can give no information about the numerical value of activation energy, yet it is clear that the low value of activation energy gives some indication about the exothermic nature of the reaction. The value of activation energy, however, suggests that the energy supplied from the external agencies were quite nominal. Low reaction temperature is consistent with this inter- pretation. Moreover, oxidation reactions are generally quite exothermic and irreversible (Emmet, 1955). Also, it is reported elsewhere that the activation energy of exothermic reactions is not large (not more than 10-15 k.cal/mole) (Shtern, 1964). Due to formation of realatively stable intermediate complexes like p-tolualdehyde and p-toluic acid which give rise to induction periods, there occurs lowering of total energy in the intermi- diate stage. This is in accordance with the law that the lower the energy the more stable the system. Again, if Moelwyn-Hughes suggestion (Moclwyn-Hughes, 1947) that the simple collision theory fails in predicting the rate of reaction in the case of molecules which exert strong forces upon one another is true, the state of affairs can be considered on the basis of the absolute theory of reaction rates. One of the basic postulates of the absolute theory is that in going from the initial state of relative stability to the final state of greater stability, the reactants pass through a succession of configurations. Some of the steps in the kinetic model and mechanism proposed elsewhere involve configuration like a-isomerisation, intermediate and activated complexes which support the theory of absolute reaction rates. (Tiwari, 1971; and Tiwari & Tripathi, 1978, 1981).548 PREM NATH TIWARI Although Arrhenius, interpreted E as the energy of activation, yet it may be taken as enthalpy change (Levenspiel, 1962; Smith, 1956; and Hougen & Watson, 1957). The values of the change in activation enthalpy are very close to the experimen- tal value of activation energy. This closeness in the two values activation energy and change in activation enthalpy could be explained by using analogy arguments from thermodyanmics on the basis of which we have E = SH* + RT for liquids and solids and E=AH*— — (molecularity-1) RT for gases (1) + Q) We have studied kinetics of this reaction process with respect to p-xylene concentra- tion only, as such equation (1) could be considered suitable for present explanation. It is evident from equation (1) that the difference between the activation energy and the change in activation enthalpy is of the order of RT only which comes to be very small quantity as compared to activation energy, explaining thereby the closeness in the above said two values. Also, on this basis we can predict from transition state theory approximately that k oc Te-E/RT (Levenspiel, 1962) .-3) or k= kyTe-8 RT a4) Again considering temperature dependency from collison theory for all bimolecular collision we have k oc [UA eo BIRT (Levenspiel, 1962) (5) or Ke= kT eB iRT +6) Further, since exponential term is highly temperature sensitive, so the variation of k caused by T and T¥ can be neglected as compared to exponential terms and equations (4) and (6) conform to Arrhenius law k= Ac ERT This again gives justification of values of activation energy on the basis of transition state theory and collison theory, as we have proceeded with the argument of closeness in the values of activation energy and change in activation enthalpy. ConcLusion It is possible to conclude that the value of activation energy is justified both on the grounds of collision theory and absolute theory of reaction rates. ACKNOWLEDGEMENT Author wishes to express his gratefulness to Professor Gopal Tripathi for guiding the research work on above studied reaction process. REFERENCES Emmet, P. H. (1955) Catalysts Vol. 11 Fundamental Principles (Part 2). Book Division, Reinhold Publishing Corporation, 430, Park Avenue, New York, pp. 6 .ACTIVATION ENERGY STUDIES IN OXIDATION OF p-XYLENE 549 Hinshelwood, C. N. (1949) The Kinetics of Chemical Change. University Press, Oxford, pp. 196. Levenspiel, O. (1962) Chemical Reaction Engineering, An Introduction to Design of Chemical Reactors. John Wiley and Sons, Inc., New York, pp. 27. ‘Hougen, Olaf A., and Watson Kenneth, M. (1957) Chemical Process Principles Part Il Kinetic and Catalysis. John Wiley and Sons Inc., New York, pp. 843, 839, 889-890. Molwyen-Huges, E. A. (1947) Kinetics of Reactions in Solutions. Oxford University Press, London, pp. 75-76. Ritchie, M. (1966) Chemical Kinetics in Homogeneous Systems, Oliver and Boyd Ltd., Edinburgh & London, pp. 15. Shtern, V. Ya. (1964) The Gas Phase Oxidation of Hydrocarbons. Pergamon Press, London, pp. 130. ‘Smith, J. M. (1956) Chemical Engineering Kinetics. McGraw Hill Book Company Inc., New York, pp. 196. Tiwari, P..N. (1971) Thesis, Studies on Liguid-Phase Catalytic Air-Oxidation of p-xylene to Tereph- thalic Acid. Ph.D. (Chemistry Chemical Engineering), Chemical Engineering Department, Institute of Technology, Banaras Hindu University, Varanasi Tiwari, P. N., and Tripathi, G. (1978) Liquid-Phase Catalytic Air-Oxidation of p-xylene to Tereph- thalic Acid. IV Respublikanskaya Konferensiya PO Okislitelnomu Giteragennomu Katalizu, Tezisi Dokladov, Baku, USSR, Vol. IT, pp. 140-147. —--(1981) Oxidation of p-xylene to Terephthalic Acid—Some Probable Mechanisms, Poster Session. 34th Annual Session of the Indian Institute of Chemical Engineers, Indian Institute of Technology, Madras