CHEN 64442 Two hours ‘THE UNIVERSITY OF MANCHESTER Reaction Systems Design Thursday 2™ June 2011 09:45-11:45 ‘Answer TWO questions only All numerical working must be shown. Graph paper is available. Electronic calculators may be used, provided that they cannot store text. ‘The question paper must be submitted with the answer book. (Student number: —_____________) Page 1 of 6CHEN 64442 Question 1 [25 marks} (a) What are the four main assumptions, which can be used to derive a single ‘overall reaction from a reaction mechanism? Give conditions where each of these assumptions is valid, [4 marks) (b) Two alternative mechanisms have been proposed to explain the formation of gaseous phosgene (COCI,) from carbon monoxide (CO) and chlorine (Cl) and also the decomposition of phosgene into these species: Mechanism1 Mechanism 2 Cl > 2CI (at equil. with const K1) Cl>2Cl (at equil. with const K1) Cl#CO>COC! (at equil. with constK2) __Cl#Cl->Cl (at equi. with const K2) COCI + Cl >COCK, + Cl (rate coeff k3) —-Cls#CO->COCI,+CI (rate coeff k3) CH#COCI>COCHCh (rate coeff k4) CH#COCH>Ch+CO (rate coeff k4) () Which species in the above two mechanisms are stable and which are reactive intermediates? Fully explain your answer. [2 marks] (i) Derive expressions for the net rate of formation/consumption of COCl including only stable species for each of the two mechanisms above. Fully justify your derivations. The reactions that are at equilibrium as well as equilibrium and rate constants are given above. [8 marks] (ji) Can simple kinetic measurements be used to determine which mechanism is correct? Fully justify your answer [2 marks] (0)(i) Write the equations, which can be used to calculate a reaction exotherm for an adiabatic reactor and explain how this is done. How are exotherms measured experimentally? [3 marks] (i) Plot qualitatively a reaction exotherm, indicating its main features and use it to explain the concept of a runaway reaction [3 marks} (iil) Describe three situations in which stochastic simulations might be used for Page 2 of 6CHEN 64442 modelling reactions. What is the relationship between the results of stochastic simulations and of macroscopic simulations for the same reaction system? {3 marks] {End of Question 1) Page 3 of 6CHEN 64442 Question 2 [25 marks] (a) Consider a reaction at the gas phase A> 8 + C taking place in a PFR with diameter 2.5 cm. The reactor temperature is 500°C and the pressure is 2 atm and all gases can be assumed ideal. The reaction rate is first order with respect to the reactant, A, and the corresponding rate constant is k= 0.05 s* at the reactor operating conditions. For a feed flowrate of 0.5 Us, calculate the length of the reactor required to achieve 40% conversion of the reactant. [12 marks] (b) Describe the main characteristics of three different 1-dimensional packed- bed reactor models, including the phenomena each model addresses. Do not give any modelling equations. [8 marks] (©) Fora gas-liquid spray column: (i) How can it be modelled using a combination of simpier ideal reactors? Use a diagram to aid your explanation and clearly state all the underlying assumptions. (2 marks] (i) Write the equations for the model in (i). Make sure that you have as many equations as unknowns and that you account for all the phenomena taking place, but do not attempt to solve any equations. [5 marks} (End of Question 2) Page 4 of 6CHEN 64442 Question 3 [25 marks] (a) n-pentane isomerisation on a dual function PYAlOs reforming catalyst, is carried out in the presence of Hz. The reaction involves a 3-step sequence consisting of dehydrogenation, isomerisation and hydrogenation. The dehydrogenation and hydrogenation steps occur on platinum sites (\), the isomerisation step occurs on acidic alumina sites (s). The mechanism including adsorption, surface reaction and desorption, for A=n-pentane, M=n-pentene, N=iso-pentene, B=iso-pentane can be written as: - Dehydrogenation iL AtIEDAD Ki= Gul Pacy A+} ©> M+ Hal Kp = Cuca / Cac fil, Hol © Hy #1 Ky = PizG; /Cr21 i. MED M4I Ka = Pm C11 Cw - Isomerisation v. M+s€> Ms vi. Ms © > Ns vi, Ns €>N+58 - Hydrogenation vil, N+1€3 NI ix, He+1€> Hol x. Ni+ Hel €> B+! Kio = Cat / CueHar x, BIE> B+! Kit = pay / Cay If desorption of isopentene (reaction vii) is the rate controlling step then the rate of reaction vii, 7, becomes: Pty ty = K(Cus — FI In this case derive the following final result for the overall reaction rate: 7 FKKpKls~ Ps! K) Pu, +KKo(l+ Ke) Pa where Kp=KiKoKoKs [10 marks] {b) Considering the change in Gibbs free energy at constant pressure and for a constant reaction extent dG= -SdT as well as the relationship between Page 6 of 6(CHEN 64442 enthalpy, H, and G, G=H-TS, (i) Derive the relation between equilibrium constant K, and temperature. 15 marks} (ii) The gas-phase equilibrium reaction AC P, takes place at pressure equal to 1 atm, where AG®= -2.6 kcal/mol and AH, 299=-15 kcal/mol, Also R= 1.99 cal mof'K". At what temperature will 70% conversion of A be achieved? You can assume ideal gas behaviour. [6 marks] (©) Consider the economic evaluation of a chemical process () What are the 3 most important types of costs to be taken into account? {1 mark] (ii) Give at least for 3 examples of fixed costs and 3 examples of variable costs. [3 marks] (End of Question 3) (End of paper) Page 6 of 6