380 LITERATURE CITATIONS 1. W.C. Reynolds, Thermodynamics, McGraw-Hill, New York, 1965, 1. Smith, J. M.. and Van Ness, H.C. Introduction to Chemical Engineering Thermodynamies, Third Edition, McGraw-Hill, New York, 1975. 3. Modell, M., and Reid, R. C., Thermodynamics and its Applications, Prentice-Hall, Englewood Cliffs, NJ. 1974. 4. Adlington, D. G., “Reactor Design,” in Chemical Engi- neering Practice, Volume 8, Chemical Kinetics, p. 181, edited by H. W. Cremer, Butterworths, London, 1965, 5. Kladko, M., Chemical Technology, 1 (141), 1971 6. Wasserman, A., Diels-Alder Recetions, pp. 42, 50, and 52, Elsevier, London, 1965. 7. Perlmutter, D.D., Stability of Chemical Reactors, Prentice Hall, Englewood Cliffs, N.J., 1971 8. Van Heerden, C., dnd. Eng. Chem, 45 (124), 1953, 9. Kramers, H., and Westerterp, K.R., Elements of Chemical Reactor Design and Operation, pp. 124-128, Academic Press, New York, 1963, 10, Bilous, ©., and Amundson, N. R., Chem. Eng. Sei.. 5 (81, 115), 1956. IL. Levenspiel, O., Chemical Reaction Engineering, Second Edition, p. 239, Wiley, New York, copyright © 1972. Used with permission. 12, Ibid., p. 240. Ibid. p. 24 PROBLEMS 1. Your design group has been asked to con- sider certain aspects of the preliminary design ofa reactor for the production of vinyl chloride by reacting chlorine with ethylene. C)H, + Cl, 3 CJH,CI + HCI In order to minimize the production of the undesirable addition product GHy + Ch, 5 C,H,Cl, it is suggested that the reaction be carried out in the temperature range 320 to 380 °C. The effect of the addition reaction is negligible in this range. In order to minimize the formation ‘Temperature and Energy Effects in Chemical Reactors of multiple substitution products, an ethylene/ chlorine feed ratio of 30:1 will also be used. The following values of the pseudo first-order rate constant k, have been reported by Subbotin, Antonov, and Etlis [Kinetics and Catalysis, 7 (183), 1966] Temperature, TC) 340 360 380 ky (see™) 223 673 143 326 For your preliminary considerations, assume that the following values of product and reactant heat capacities are constant over the tempera- ture range of interest. C, (cal/g mole"K) Ethylene 17.10 Chlorine 8.74 HCI 707 Vinyl chloride 10.01 ‘The standard enthalpy change for the reaction at 25°C may be taken as —23 keal/g mole. (a) Calculate the space time necessary to obtain 50% conversion of the chlorine in a PFR if the reactor is maintained isothermal at 320°C. (b) Calculate the spqce time necessary to obtain 50% conversion of the chlorine in a PFR if the feed enters at 320 °C and the reactor is operated adiabatically. The reactor is to be designed to operate at 1 atm. Deviations from ideal gas behavior may be neglected. Note that while the volume changes associated with changes in mole numbers are negligible, you may wish to consider the effect of thermal expansion. 2. Acetic anhydride reacts with ethanol to form ethyl acetate according to the reaction (CH,CO),0 + 2C,H,OH + 2CH,COOC,H; + H,0Problems In ethanol this reaction proceeds stepwise (CH;CO),0 + C,H;OH > CH;COOH + CH;COOC,Hs CH;COOH + C,H;OH > H,0 + CHyCOOC;Hs Since the second reaction rate constant is orders of magnitude greater than the first at tempera- tures near room temperature, the first reaction may be regarded as the rate controlling step Since ethanol is used as the solvent, the reaction will follow pseudo first-order kinetics. The rate of this liquid phase reaction can be expressed as r= 6 x 108e"®857/TC,Cy where T is temperature in degrees Kelvin, and where A and B refer to anhydride and alcohol, respectively. The concentrations are expressed in kilomoles per cubic meter, and the rate in kilomoles per cubic meter per second. On the basis of the data presented below, determine the times necessary to achieve 20% decomposi- tion of a 1 molal anhydride solution by iso- thermal operation at 20 °C and by adiabatic operation starting from the same temperature. AG?29, AHB.250 Compound (kJ/mole) (kJ/mole) Acetic anhydride (4) 509.65 — 649.50 Ethanol (¢) =17481 —277.77 Ethyl acetate (¢) -31860 —463.47 Water (4) = 23730 — 285.98 The density of ethanol at 20 °C is 0.789 g/cm’, and its heat capacity is 2.85 J/g:°K. These prop- erties may be assumed to be constant over the temperature range of interest. The solution is so dilute that one may assume that its property values are essentially equal to those of pure ethanol. Batch reactor operation is assumed. 3. The decomposition of phosphine is a first order reaction that proceeds according to the following stoichiometric equation. 381 PH,(g) > 3P.(9) + 1.5H2(9) Pure phosphine is to be admitted to a con- stant volume batch reactor and allowed to undergo decomposition according to the above reaction. If pure phosphine enters at 672 °C and the initial pressure is 1 atm, determine the times necessary to decompose 20% of the original phosphine for both isothermal and adiabatic operation. ‘The rate constant for this first-order reaction is given in the International Critical Tables as 18,963 log k >t 2log T + 12.130 (1) where the temperature is expressed in degrees Kelvin and the time in seconds. The standard enthalpy change for the gaseous reaction at 25 °C is approximately 5665 cal/g mole. The following values may be used for the molal heat capacities (at constant pressure) of the species involved in the reaction. P(g) C, = 5.90 + 0.0096T PHA) C, = 6.70 + 0.0063T Hg) C, ~ 720 where T is expressed in degrees Kelvin C, is expressed in calories per gram mole per degree Kelvin For temperatures from 800 to 1000 °K the following values may be used to represent average C, values, Palg) PH3(9) 4, Consider the reaction used as the basis for Illustrations 10.1 to 10.3. Determine the volume that would be required to produce 2 million Ib of B annually in a plug flow reactor operating isothermally at 163 °C. Assume that 97% of theA fed to the reactor is to be converted to B and that the reactor can be operated for 7000 hr annually. Determine the manner in which the heat transfer requirement is distributed along the length of the reactor (ie., what fraction of the heat evolved must be removed in the first 10% of the reactor length, the second 10%, the third 10% etc.). 5. A reactor designer proposes to carry out a reaction with the stoichiometry A+B+C in the liquid phase in two ideal CSTR’s operating in series. Since species B is very expensive, the designer has chosen the reaction conditions so that a vast excess of species A will be present and the rate expression becomes pseudo first- order in species B. = kCy The reaction is exothermic, and temperature control in both reactors is to be accomplished by heat exchange with water boiling at 1 atm (T = 100 °C), The contents of the first reactor will be at 106 °C; those of the second reactor will be at 117 °C. At these temperatures the values of the apparent rate constant are: T = 117°C T = 106°C k = 2.79 ksec™* k = 0.93 ksec”! For the proposed design the reactor volumes are both 0.8 m‘, the input volumetric flow rate is 1.10 m*/ksec, and the overall fraction con- version of the initial B is to be 0.80. Since the reaction is carried out in dilute liquid solution, the effective heat capacity of the liquid mixture is substantially unaffected by the reaction and may be regarded as a constant that is equal to 3.47 Jfem?°K. If the initial concentration of species B is 5.6 kmole/m? and the feed stream enters at 70 °C, determine the required heat transfer area for each reactor. ‘Temperature and Energy Effects in Chemical Ree cors Additional data: AH = —69 kJ/molefor the reaction as written. The variation of this quantity with temperature may be neglected. U = 68 J/kseccem?*K in each reactor. 6. Consider the sequential first-order reactions Av 5 W where V is the desired product. These liquid phase reactions are to be carried out in a cascade consisting of two equal-volume CSTR’s in series. The reactors are operated at the same temperature and so as to maximize the concentration of species V in the effluent from the second reactor. When the feed rate is 0.5 m3/ksec and the rate constants are each equal to 0.125 ksec™?, the volume of an in- dividual reactor that gives rise to the maximum is equal to 2 m°, Both reactors will operate at the same temperature (93 °C). a. If the fluid density is equal to 0.95 g/cm}, the heat capacity of the fluid is equal to 3 J/g°K, and the first reactor operates adiabatically, determine the temperature at which the feed must enter. The feed contains 1.5 kmoles/m? of reactant A. b. Atwhat rate must thermal energy be removed (or supplied) in order to maintain the second reactor at 93 °C? AH, = —60 kJ/mole AH, = 20kI/mole 7. The hydrogenation of cottonseed oil pro- ceeds by the following irreversible steps A by D LE A: Linoleic acid B: cis-oleic acid D: C: Iso-oleic acid tearic acid