CHE3044F, 2013

TUTORIAL 3

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CHE3044F, 2013 : Reactor Design 1 : TUTORIAL 3

1. (from Fogler, 2006, P3-10). (a) Write a rate equation for the following reactions assuming that they are elementary (1) (2) (3) (4) (5) C6 H6 C2 H4 + H2 C2 H4 + 1 2 O2 CH2 OCH2 (CH3 )3 COOC (CH3 )3 C2 H6 + 2CH3 COCH3 nC4 H10 i C4 H10 CH3 COOC5 H5 + C4 H9 OH CH3 COOC4 H9 + C2 H5 OH

(b) Write a rate equation for the reaction 2A + B C if the reaction is (1) (2) (3) (4) second order in B and third order overall is zero order in in A and rst order in B is zero order in both A and B is rst order in A and overall zero order

2. The reaction mechanism for cracking of cumene (A) C6 H5 CH (CH3 )2 C6 H6 + C3 H6

to yield benzene (B) and propene (P) yield the following rate expressions depending on the assumptions that are made kA Ct PC (A) rC = 1+ PP PB Kp

KB PP PB + KB PB KS

kS Ct KC PC (B) rC =

PP PB Kp 1 + KB PB + KC PC

(C)

PP PB Kp rC = PP + PC K C K S + K C PC PP kD Ct KS KC PC

(a) Verify that each of these expressions obeys the thermodynamic constraint given in terms of the concentration based equilibrium constant, Ke = function(concentrations). Locate the reaction rate constant in each equation and determine its units (note : 1 is dimensionless and thus the terms in the denominator are dimensionless too) (b) Simplify these equations for the case of low conversion and comment of the reaction orders (c) Simplify these equations when the reaction is carried out in excess propene and comment on the reaction orders.

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3. (Muhammad Parak, MSc thesis, 2011). Literature reports a number of dierent rate equations for the water has shift reaction CO + H2 O (A) (B) (C) (C) rCO = kPCO PH2 O (1 ) where =
0.78 0.15 PH2 O (1 ) rCO = kPCO 0.28 0.0 PH2 O (1 ) rCO = kPCO

CO2 + H2 PH2 PCO2 Ke PCO PH2 O

rCO = kPCO PH2 O PH2 PCO2 (1 )

In each case comment on the reaction order with respect to all the reacting species and indicate whether all these equations are consistent with the concentration based equilibrium constant. 4. (Schreiber et al., 1994). One of the most well reported octane combustion mechanisms has the following reactions steps (1) (2) and the following rate equations r1 = k1 CF CO2 r2 = k2 CI p p0 p RT
3 .5

F + 2O2 I I F + 2O2

p p0

2 .2

where p is the total pressure, p0 is the initial total pressure. Determine whether this equation obeys the chemical equilibrium constraint and comment on the forward and backward reaction rate constants. The heat of reaction at 300 K has been reported for the forward reaction as Hr xn,1 = 53.9 [kJ.mol 1 ] and for the backward reaction Hr xn,2 = 53.9 [kJ.mol 1 ]. The activation energies for the forward and backward reactions E2 E1 = 19500 [K ] and = 37500 [K ], respectively. are R R 5. (Class Test, 2012, Q4). An irreversible aqueous reaction gave 90% conversion in a batch reactor at 40o C in 10 min and required 3 min to achieve this conversion at 50o C. (a) Assuming rst order kinetics, nd the rate coecient at each temperature (b) What is the activation energy for this reaction (3) (4)

(c) Assuming rst order kinetics, at what temperature can 90% conversion be obtained in 1 min (4) (d) Assuming rst order kinetics, nd the times for 99% conversion at 40 and 50o C
1

(2)

(e) Assuming second order kinetics with CA0 = 1 mol.L , nd the times for 99% conversion at 40 and 50o C (8) (f) Assuming second order kinetics with CA0 = 1 mol.L1 , nd the temperature to obtain 99% conversion in a time of 1 min. (HINT : is the activation energy the same for rst and second order reactions) (4)

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6. The reaction rate equation of a gas phase reaction has been reported at 400 K to be dpA 2 = 3.66pA [atm.hr 1 ] dt

(a) What are the units of the rate constant (b) What is the value of the rate constant when the reaction is expressed as rA = 1 dNA 2 = kCA V dt mol.m3 .s 1

7. At 1100 K, n-nonane thermally cracks (breaks down into to smaller molecules) 20 times faster than at 1000 K. Find the activation energy for this reaction. 8. The maximum allowable temperature for a reactor is 800 K. At present the operating set point is 780 K, the 20 K safety margin accounting for sluggish control, uctuating feed ow rate, etc. Now with more sophisticated control, it is possible to raise the temperature to 792 K without compromising safety. By how much will the reaction rate increase, and hence also the production rate if the activation energy of the reaction is 175 [kJ.mol 1 ].