ChE 101 Chemical Reaction Engineering Winter 2014 Homework #2 Solutions 1.

. Consider the following reversible elementary reaction: A 2B The rate coefficient of the forward reaction is kf = 25 hr-1, and the rate coefficient of the reverse reaction is kb = 4M-1 hr-1. The aqueous phase reaction is carried out in a constant volume batch reactor. The reactor is initially charged with 1 mole of pure A and 1 mole of pure B at 1 atm. The reactor volume is 1 L. (a) (b) (c) (d) (e) Write the rates of reaction for A and B. Write rA as a function of the conversion of A. What is the equilibrium conversion of A? Find the conversion of A as a function of time. How long does it take for the system to reach 90% of the equilibrium conversion?

2 2 (a) = = 4 25 2 2 = 2 2 = 50 8 (b) Let X be the fractional conversion of A, and make an ICM table.

Species Initial(mol) Change(mol) Final(mol) A 1 -X 1-X B 1 +2X 1+2X Total 2 X 2+X Given that the reactor volume is 1L, we know = = 1 = = 1 + 2 Thus the rate of change of A is given by: = 4(1 + 2)2 25(1 )
(c) Recall that = =1 = exp (

)Where aj

is the activity of species j and vj is the

stoichiometric coefficient of species j. We also know that = 25 = 4

=1

. When working with ideal

solutions, the activity is equal to the concentration of the species, thus: = =

2 (1 + 2 ) = = 1

Where Xeq is the equilibrium conversion of A. Equating and solving these two expersions, we find that: (1 + 2 ) 25 = 1 4 = 0.4375 (d) We need simply to integrate the rate expression from part b. (1 ) = = = = 4(1 2)2 25(1 ) This can be solved by separating and integration. = 4(1 + 2)2 + 25(1 ) = 16 2 41 + 21 = ( + 3)(16 7) = ( + 3)(16 7)
= =0 ( + 3)(16 7) =0 2

1 16 + = 55 =0 + 3 55 =0 16 + 7

1 7 (ln|16 7| ln| + 3| ln ( )) = 55 3 ln ( 7 16 7 ) = 55 + ln ( ) + 3 3 7 16 7 = exp(55) + 3 3 = 21(1 exp(55)) 48 + 7 exp(55)

Note: at the equilibrium conversion, 16X-7 =0. All conversions of interest will be below this value, thus |16X-7| = 7-16X for this reaction. In addition, |X+3| = X+3 for all X of interest. (e) We want to reach 90% of the equilibrium conversion found previously, thus X = 0.9X 0.4375 = 0.39375. Reorganizing the result from part d, we find: 90% = 1 7 (ln(7 16 0.39375) ln(0.39375 + 3) ln ( )) = .0441 = 2.65 min = 159 55 3

2. In a batch reactor the following reaction takes place: A+2B 2C+ D The reactor is initially charged with CAo and CBo and CBo/CAo = 3.0. Find the value of k

if CAo is 0.01 M and after 10 min of reaction the conversion of A is 0.5. To find the rate constant, we first need to know the values of CA and CB in the reactor. A + 2B 2C + D Given our definition for conversion, and a simple stoichiometric argument, we know that CA = CAo*(1-XA) CB = CBo 2*CAo*XA By the law of mass action, the rate of change of A is given by : 2 = = = (1 )( 2 )2 = (1 )( 2 )2
.5

10 = (1 )( 2 )2 0

Integrating gives = 1.2 102 1 2

3. Consider the following gas phase reaction, which is carried out in a constant pressure batch reactor: A+BC It is found that starting with 1 mole of A and 2 moles of B, the volume after 20 minutes decreased by 20% from an initial volume of 1 L at a pressure of 1 atm. If the same reaction is to be carried out in a constant volume reactor with an initial volume of 1L and an initial pressure of 1 atm, calculate the conversion after 20 minutes.

For a batch reactor at constant pressure,

= . From a TCF table, it can be found that:

= 1 = 2 = 1 = 3 = 3(1 ) 3 Because all species are at constant pressure with an initial volume Vo, and assuming they are ideal gasses, 1 = (1 ) 3

1 . 8 = (1 ) 3 = .6 By definition, we know that: = 1 = 1 1 3 2 = 1 1 3

= From the rate law above,

1 1 2 = = (1 ) 1 1 3 1 3 1 3 (1 )(2 ) = 1 1 3 (1 )(2 ) = 3 3 Separate and integrate. (3 ) = 3 =0 (1 )(2 ) =0 1 2 ( ) = 3 1 =0 2 ln(2 ) 2 ln(1 ) ln(2) = 3 1 2 = (ln ( ) ln(2)) (1 )2 3 Plugging in numbers, 1 2 0.6 = (ln ( ) ln(2)) = 0.0246 1 1 (1 0.6)2 3 20 In a constant volume reactor, this simplifies to: = = = 1 = 2

= (1 )(2 ) Separate and integrate as before:

= =0 (1 )(2 ) =0 1 1 ( ) = 1 =0 2

ln(2 ) ln(1 ) ln(2) = 2 ln ( ) = ln(2) + 1 1 1+ = 2 exp() 1 1 = 1 2 exp() 1 1 = 0.560 2 exp(0.246 20) 1 4. An aqueous reaction gave the following data in a batch experiment: = 1 t 10 20 10000 10 T(C) 50 50 50 80 X 0.5 0.666 0.999 0.8 Plugging in numbers,

What residence time would be required for 90% conversion at 80C in a pressurized CSTR starting with the same initial composition? Step 1: We need to look at the reaction data to determine the order of the reaction. If the reaction were first order, = = = = (1 ) = (1 ) ln(1 ) = Solve for k in the case of each reaction. @ = 10: = 0.0693 @ = 20: = 0.0548 @ = 10000: = 0.000691 This indicates that the reaction is not first order. Next say the reaction is second order: = = = 2 = (1 )2 = (1 )2 1 = 1 1 1 1 = ( 1) 1 Solve for kCo in each case again: @ = 10: = 0.1 @ = 20: = 0.0997

@ = 10000: = 0.0999 As these are all in agreement, this must be a second order reactor. Using the data at 80C, kCo=0.4 will be used in the calculation of the residence time. In a CSTR, =

0.90 = = = = 225 2 2 2 () (1 ) 0.4(1 0.90)2

5. Transient of Cell Culture growth in a CSTR. While the traditional role of chemical engineers is heavily focused on the very simple chemical processes and reactions of the petrol industry, the field continues to grow in to new and developing fields. One such area is the use of biological organisms to facilitate the creation of desirable products. This includes metabolites such as yeasts production of ethanol, enzymes, heavily used throughout the world both for research and medicinal purposes, and even wholecell catalytic systems that require the immobilization of living cells within a reactor system to perform otherwise difficult to achieve catalytic conversions. Imagine that as a chemical engineer, youre asked to continuously produce these cells in a bioreactor. Your client has told you that the cells require only sucrose as a limiting substrate, and grow at a specific growth rate described by = + Where S is the sucrose concentration, = 0.05 1/min, and Km = 2 g/L. This form of a growth rate is very similar to those found in enzyme kinetics, which will be covered later in the class. In addition, you are told that the metabolic needs of the cells consume half of the sucrose for energy during growth without providing additional cell mass (This is called a growth yield). (a) Write down the differential equations governing the transient startup of this CSTR. (b) The volume of the reactor is one liter. Given a feed sucrose concentration of 10 grams per liter, an initial charge of .1 g/L cells in this solution, and flow rate of .01 L/min model the transient concentrations of both Sucrose and Cells in the system. Approximately how long does it take for this system to reach steady state? (c) Use your simulation to evaluate a range of flow rates through the system. Briefly describe how the behavior of the system changes with flow rate, and what considerations should be taken into account when attempting to optimize this reactor.

(a) Use a simple mass balance: accumulation = in out + generation. The feed contains no cells, thus: = + = + + For the sucrose substrate, keep in mind that twice the amount of substrate is consumed. = 2 = ( ) 2

= ( ) 2

(b) The following code was used to simulate this reactor:

%Define Adjustable Parameters V=1; %L mumax=.05; %1/min Yield = 0.5; Km = 2; %g/L Sin=10; %g/L v=.05; %L/min tmax=250; %min %Define initial conditions Xo=0.1; %g/L So=10; %g/L ode_system = @(t,y) [-y(1)*v+mumax*y(2)/(Km+y(2))*y(1)*V; v*(Sin-y(2))(1/Yield)*mumax*y (2)/(Km+y(2))*y(1)*V]; options = odeset('InitialStep', 1, 'Maxstep', 1); [T,Y]=ode45(ode_system,[0,tmax],[Xo,So],options); Cells=Y(:,1); Sucrose=Y(:,2); plot(T,Cells, T, Sucrose) xlabel('Time(min)') ylabel('Concentration (g/L)')legend('Cells', 'Sucrose')

(c) v= .02:

v=.03:

v=.04:

v=.05: As the flow rate through the system increases, the overall conversion of glucose to cells decreases. Due to the higher flow rate, however, a greater total number of cells are produced as the flow rate increases. This is balanced by the greater feed costs due to wasted substrate. At sufficiently high flow rates, the initial charge of cells are no longer capable of growing fast enough to avoid being washed out of the reactor completely.