Chapter 9

Exercise 1:
As in example 9.3.2, the material balance on the batch reactor is:
df A
4
= k (1 f A ) = 10 4 exp[10 ( RgT )](1 f A )
dt

(1)

where T is given by the energy balance:

T =To +

H r

To

n Ao f A

(2)

A (ni C pi )
i

For this problem, Hr = -40,000 cal/mol. Therefore the energy balance becomes:
T = 300 +

40000(2381) f A
1(944288 192862 f A )

(3)

After substituting equation (3) into equation (1) and solving the differential equation
(initial condition is fA = 0 at t = 0) the time required to achieve 50% conversion is 417 s.
The final temperature is 347oC. This is a very short time for a large scale system, since
loading and unloading must be considered.
Exercise 2:
The same energy balance and material balance are used here as in exercise 1. The time to
reach 90% conversion is 531 s while the final temperature is 392oC.
Exercise 3:
The material and energy balances for the adiabatic system are shown below, respectively:
df A
1
1
= 5 10 3 exp[ 20000
Rg ( 300 T )] (0.5) (1 f A )(1.2 f A )
dt
df
(15000)(100) A
dT
dt
=
dt 100(1 f A )65 + (100)(1.2 f A )(65) + (100 f A )(150)

9.1

(1)

The only difference between example 9.3.3 and this exercise is that here UAH = 0.
Solution to this set of differential equations is shown below (@ t = 0, T = 300 K and fA =
0). The dashed curves are solutions to example 9.3.3.

0.8

fA

0.6
0.4
0.2

100

200

300

400

500

400

500

Time (s)

380

T (K)

360
340
320

100

200

300

Time (s)

The amount of energy that is removed from the reactor can be calculated with the
following formula from the energy balance:
energy removed = H r n Ao f A + [n Ao (1 f A )C p A + n Ao (1.2 f A )C pB + n Ao f AC pC ]T
For example, with T = 31.6 at fA = 0.8 the amount of energy removed is 698,000 J.

9.2

Exercise 4:
After substituting the following relationship for the wall temperature into the energy
balance in example 9.3.3 and solving the set of differential equations, the following
conversion and temperature profiles were found. The dashed lines correspond to the
constant wall temperature case.

0.8

fA

0.6
0.4
0.2

100

200

300

400

500

400

500

Time (s)

T (K)

350
340
330
320
310
100

200

300

Time (s)
Exercise 5:
The exit temperature is calculated from the energy balance. The energy balance is not a
function of B. Therefore, the equation for the exit temperature does not change from that
in example 9.4.2. The exit temperature is calculated with the following formula:

9.3

30000 f B
(1)
57 + 2.5 f B
However the material balance changes slightly. The new material balance is the
following:
0.1
df B
(2)
= o
2 723 2
kC
1

f
(
)
[
]
0
B
B
T
T = 723 +

where C Bo = 8.42x10 3 mol/L and the rate constant is the same as in example 9.4.2. After
substituting the rate constant and equation (1) into equation (2) and solving, the space
time is 49.2 s and at 10% conversion the temperature is 775 K. If molar expansion is
taken into account, as in example 9.4.2, the space time is 47.1 s. Therefore, about 4%
error is introduced by not taking into account molar expansion.
Exercise 6:
If exit temperature effects are ignored in the reactor described in example 9.4.2, the
material balance reduces to:

0.1

df B

kC [
0

(1)

o 1 f B 2
B 10.5 f B

where C Bo = 8.42x10 3 mol/L . The energy balance is the same as that in example 9.4.2.
After substituting the expression for the rate constant and the energy balance into
equation (1) and solving, the space time is 44.5 s. If exit temperature effects were
included, then the space time is 47.1 s. Therefore, 6% error was introduced by excluding
exit temperature effects (due to low conversion).

9.4

Exercise 7:
The following plots show the solution of the set of equations that described the adiabatic
PFR:
1
0.8

0.6
0.4
0.2

0.2

0.4

0.6

0.8

0.8

1.1
1.08

1.06
1.04
1.02

0.2

0.4

0.6

x
The dashed lines are for the case when the heat of reaction is doubled. The energy
balance changes when the heat of reaction is doubled. The new energy balance is the
following:

[ ( )]

d
= 0.4 y exp 18 1 1
dx

(1)

9.5

Exercise 8:
First write a material balance on A in the CSTR:
FAo f A
= ( A )r
V

(1)

The rate expression for this reversible reaction is the following:

r = k1C A2 k 2 C P2

(2)

Since the conversion of A in the CSTR is 0.4, the concentrations of P and A at the outlet
of the CSTR can be determined.
C A = C Ao (1 f A ) = 1.5(1 0.4) = 0.9 M
C P = C Po + ( 22 )(C A C Ao ) = 1(0.9 1.5) = 0.6 M
Now substitute equation (2) into equation (1) along with CA and CP and solve for V.
V = 0.824 L
Use the energy balance on the CSTR to determine the rate of heat removed.
The energy balance on the CSTR is the following:
F o H r f A
Q& = A
+ FAC PA (T T o ) + FP C PP (T T o )
( A )

(3)

Note that T-To = 60 K, (-A) = 2, FA = 60 mol min-1 and FP = 40 mol min-1. Therefore, the
heat transfer rate can be determined:
cal
Q& = 58000 min

Now write a mass balance on the PFR:

FAo

df A
= A r
dVR

(4)

Write r in terms of fA:

9.6

r = k1C A2 k 2 C P2 = 30(1.5 2 (1 f A ) 2 ) 0.1(1.5 1.5(1 f A )) 2

(5)
r = 67.5(1 f A ) 2 0.225 f A2
Substitute the rate equation into equation (4) and simplify:
0.9

df A
V
= R
2
2
100
A ) 2.7 f A

67.5(1 f

0.4

V required is 6.90 L
The heat removed can be calculated from the energy balance on an isothermal PFR:
dQ& =

H r

FAo df A

(1)

Therefore the change in heat removed in the PFR is 250,000 cal min-1.
It is not reasonable to remove this much heat from vessels so small in any conventional
way.
Exercise 9:
Part a)
First mix the stream of ester (E) and the stream of base (B). A material balance leads to
the following concentrations at the inlet of the reactor:
C Eo = 0.67 M, C Bo = 1.33M
Note that E is the limiting reactant and the total volumetric flow rate is 30 L s-1.
A material balance on E in the CSTR is:
0 = vC Eo vC E E rV

(1)

where r = kC E C B = 1014 exp(11000 303)C E C B

Write equation (1) in terms of fractional conversion of E:

9.7

0 = vCEo vCEo (1 f E ) 1014 exp(11000303)CEo (1 f E )(CBo CEo f E )V

(2)

After substituting the known initial concentrations, the volume of the reactor, and the
volumetric flow rate, the fractional conversion of E is 0.755.
Part b)
The energy balance for the CSTR is the following:
Q& = H r (rV ) + o vCp (T T o )

(3)

However, the reactor operates isothermally. Therefore, T = To.

Since the rate can be expressed as
r = kC E C B = 1014 exp(11000 303)C E C B

(4)

and the fractional conversion of E is 0.755 (from part a),

r = 0.00232 mol L-1 s-1
Therefore, the heat removed is 670 kcal s-1.
Sincethe rate of heat removed is known, the following equation can be used to determine
the area required.
Q& = UAH (T TC )

(5)

Therefore, the area required is 3.77 m2.

part c)
If the coolant supply fails, Q& = 0
Therefore the energy balance reduces to the following equation:
0 = H r (rV ) + o vCp (T T o )

(6)

From the material balance:

rV = v(C Eo C E )

(7)

substitute equation (7) into equation (6)

9.8

0 = H r v(C Eo C E ) + o vCp (T To )

(8)

From part (a) (at 30oC) CE = 0.163 M. However, if the temperature goes up it will cause
CE to go even lower.
Therefore C Eo >> C E . Equation (8) is simplified to the following:
0 = H r v(C Eo ) + o vCp (T To )

(9)

Now substitute the known values,

mol
kcal
L
L
0 = (45 kcal
mol )(30 s )(0.67 L ) + (30 s )(1 L o C )(T 30)

(10)

Therefore, the temperature is 60oC.

Exercise 10:
First write a material balance on A in the reactor:
vC Ao vC A rV = 0

(1)

The first-order rate expression is the following:

12500
r = kC A = 1013 exp
C A
T

(2)

After substituting equation (2) into equation (1), notice that there are two unknowns, T
and CA. Therefore the energy balance is needed. The energy balance is:
Q& = 0 = H r (rV ) + o vCp (T T o )

(3)

Equation (3) becomes:

kJ
m
0 = (70 mol
)1013 exp(12500 T )C A (10000L) + (1000 mkg3 )(10 Ls )(1 kgkcalK )(T T o )(1 1000L
)( 4.18kJ
kcal )
3

where To is the feed temperature.

After simplification, the material and energy balances reduce to the following:
50 10C A 1017 exp( 12500 T )C A = 0

(4)

9.9

 7 1018 exp( 12500 T )C A + 41.8(T T o ) = 0

(5)

Solve equation (4) for CA and substitute it into equation (5).

7 1018 exp(12500T )(50)
+ 41.8(T T o ) = 0
17
12500

10 + 10 exp(
T)
Q& g

(6)

Q& r

where the subscript g denotes the heat generated and the subscript r denotes heat
removed.
Plot the heat generated and heat removed curves vs. T for each condition.

5000

4000

Qr or Qg

3000

Qr at
T = 300K
o

2000

Qg

Qr at
To = 280K

Qr at
To = 320K

1000

0
250

270

290

310

330

350

-1000
Exit Temperature (K)

9.10

370

390

410

430

If To = 280 K, then the reactor temperature at the outlet is approximately 280 K.

If To = 300 K, then the reactor temperature at the outlet can be 301 K or 382 K (it cannot
be 337 K-this state is unstable). The temperature of the reactor will depend on the startup
of the reactor.
If To = 320 K, then the reactor temperature at the outlet is 403 K.
Now use equation (4) to find the exit concentrations:
If To = 280 K, T = 280 K and CA = 4.99 mol L-1
If To = 320 K, T = 403 K and CA = 0.015 mol L-1
If To = 300 K, T = 301 K and CA = 4.95 mol L-1
If To = 300 K, T = 337 K and CA = 2.81 mol L-1 however this state is unstable.
If To = 300 K, T = 382 K and CA = 0.080 mol L-1
part b)
The energy balance on the reactor is the following:
Q& = UAH (T TC ) = H r (rV ) + o vCp (T T o )

(7)

where the coolant is at 290 K (TC).

Use the material balance to find T.
Since the fractional conversion of A is 0.9, the concentration of A out of the reactor is
0.5M.
The material balance is:
0 = vC Ao vC A rV

(8)

Substitute the known values

0 = (10 Ls )(5 mol

) (10 Ls )(0.5 mol
) 1013 exp(12500T )(0.5 mol
)(104 L) (9)
L
L
L
Therefore, the exit temperature is 361 K. This is below 373 K, so it is possible to get
90% conversion.
In order to evaluate start up problems, use the energy balance from equation (7) and solve
for UAH since the exit temperature is now known.

9.11

UAH = 21.04

kJ
sK

Plot the energy balance to see if there are multiple steady states. Note that the material
balance yields the following expression for the concentration of A as a function of
temperature:
CA =

50
10 + 10 exp(12500T )

(10)

17

Substitute the concentration of A into the energy balance:

21(T 290) + 41.8(T 320) =

3.5 10 20 exp(12500T )
10 + 1017 exp(12500T )

(11)

Qg

Qr

4000
3500
3000

Qr or Qg

2500

Qg

2000

Qr

1500
1000
500
0
250
-500

270

290

310

330

350

-1000

Exit Temperature

9.12

370

390

410

Since there are 3 steady states, in order to reach 90% conversion, you must start up the
reactor hot.
Exercise 11:
Write the material balance on A in the CSTR
C Ao C A r = 0

(1)

where r = k1C A k 2 C B
Rewrite the concentrations in terms of the fractional conversion of A:
C A = C Ao (1 f A )

(2)

C B = C Ao f A

(3)

The equilibrium constant, K, is the ratio of the forward rate constant over the reverse rate
constant (k1 at 300 K is 0.240 s-1). Therefore, k2 = 0.03 s-1.
Substitute the rate expression and equations (2) and (3) into equation (1).
Therefore, the fractional conversion of A is 0.88.
In order to find the conversion at 500 K, the rate constants at 500 K must be determined.
k1 = 10 3 exp(2500 500) = 6.74 s 1
Since k 2 =

k1
, the equilibrium constant at 500 K must be determined in order to find k2.
K

The equilibrium constant is related to the Gibbs free energy in the following way:
G = RT ln K

(4)

In addition the Gibbs free energy is related to the heat of reaction:

G = H TS

(5)

After substitution of equation (5) into equation (4) and assuming that the entropy and heat
of reaction are not functions of temperature, the equilibrium constant is the following:
H r
K = K o exp
RT
g

(6)

9.13

where Ko is a constant.
Therefore if K is known at one temperature, Ko can be determined. Then, K can be
determined at a second temperature.
K at 500 K is 0.00975 and k2 is 691.3 s-1.
Substitute the new rate constants into the material balance and solve for fA.
The fractional conversion of A at 500 K is 0.0097.
part b)
The energy balance on the reactor is

o Cp (T To )
Q&
= H r r +
V

(7)

where r is the following:

r = k1C A k 2 C B = 0.240C Ao (1 f A ) 0.03C Ao f A

(8)

From part (a) the fractional conversion is 0.88, therefore r = 0.012 mol
sL .
Substitute all known quantities into the energy balance and solve for

Therefore,

Q&
kcal
= 0.17 kcal
Ls or 0.17 Ls of heat is removed.
V

9.14

Q&
V