ChE 344

Winter 2011
Final Exam + Solution
Monday, April 25, 2011

Open Book, Notes, and Web

Name_______________________________

Honor Code (Please sign in the space provided below)

“I have neither given nor received unauthorized aid on this examination, nor have I
concealed any violations of the Honor Code.”

_____________________________________
(Signature)

The Basics
1) ____/ 5 pts
2) ____/ 5 pts
3) ____/ 5 pts
4) ____/ 5 pts
5) ____/ 5 pts
6) ____/ 5 pts
7) ____/ 5 pts
Applications
8) ____/ 5 pts
9) ____/10 pts
10) ____/10 pts
11) ____/10 pts
Professional
12) ____/10 pts
13) ____/20 pts

Total ____/100 pts

(5 pts) 1) Mole Balances, Chapter 1
The reaction
A + B → 2C
takes place in an unsteady CSTR. The feed is only A and B in equimolar proportions.
Which of the following set of equations gives the correct mole balances on A, B
and C. Species A and B are disappearing and Species C is being formed.
€
Circle the correct answer where all the mole balances are correct
(a)
V dN A
FB0 −F A − ∫ rAdV =
dt
V dN B V
FB0 −F B − ∫ rAdV = Wrong sign for rA , should be + ∫ rAdV
dt
V dNC
−FC + 2 ∫ rAdV =
dt
€ €
(b)
V dN A
FA0 −F A + ∫ rAdV =
€ dt
V dN B
FA0 −F B + ∫ rAdV = All are correct.
dt
V dNC
−FC − 2 ∫ rAdV =
dt
(c)
V dN A
FA0 −F A + ∫ rAdV =
€ 0 dt
V dN B
FA0 −F B + ∫ rAdV = Wrong sign for FC , should be −FC
dt
V dNC
FC + ∫ rC dV =
dt
€ €
(d)
V dN A
FB0 −F A − ∫ rAdV =
€ dt
V dN B V
FB0 −F B − ∫ rAdV = Wrong sign for −rA , should be + ∫ rAdV
dt
V dNC
−FC + ∫ rC dV =
dt
€ €
Solution

€ Answer is (b).

1
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(5 pts) 2) Circle the correct answer, true (T), False (F) or (CT) Can’t tell from the information
given.

T F CT (a) Multiple steady states can exist for an irreversible endothermic

first order reactions.
T F CT (b) A steady-state CSTR operates at 150°C. The reactor effluent is
at the same temperature as the reactor contents. Is the reactor
operating isothermally?
T F CT (c) Multiple steady states can only exist for adiabatic reactions.
T F CT (d) Reactor staging is only used for irreversible reactions.
T F CT (e) The detrimental effect of pressure drop in gas phase reactions
is more pronounced for adiabatic- exothermic reactions than
for adiabatic endothermic reactions.

Solution
(a) False.
R

G
T
(b) Insufficient information to answer definitively. Need to know the feed
temperature.
T0 = 300 K

T = 300 K
T = 300 K

(c) False. See Equation 12-8

(d) False. See Figure 11-4
dy α T
(e) True. = (1+ εX)
dW −2y T0
Exothermic T ↑ y ↓

Endothermic T↓ y ↑
€

2
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(5 pts) 3) Circle the correct answer.
Consider the following Levenspiel plot

(1 pt) (a) The equilibrium conversion is

(1) X < 0.6

e (2) X = 0.8
e (3) X > 0.8
e (4) Can’t tell from the information given

(1 pt) (b) The flow rate to an 8 dm CSTR corresponding to Figure E4-1 where 80%
3

conversion is achieved is

(1) F = 0.8 mol/s

A0 (2) F = 10 mol/s
A0

(3) F = 1 mol/s
A0 (4) Can’t tell from the information given

(1 pt) (c) If the conversion achieved in a single 8 dm CSTR is 80%, what would the
3

conversion be if the flow is equally divided into to two CSTRs in parallel with
first reactor having a volume of 4 dm each (same total volume).
3

"0
"0 "0 "0
2 2
vs.
3
8 dm X=0.8 ! 4 dm3 3
4 dm
!
! !
X=_?_ X=_?_

The total reactor volume is constant at 8 dm . 3

The conversion for the two reactors in parallel is

(1) X > 0.8 (2) X < 0.8 (3) X = 0.8 (4) Can’t tell from the information given

(2 pts) (d) If the conversion achieved in a single 8 dm CSTR is 80%, what would the
3

conversion be if two CSTRs are connected in series with first reactor having a
volume of approximately 3.0 dm and the second reactor having a volume of
3

0.6 dm . 3

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 υ0

vs. 3
3
3.0 dm
€ 8 dm X=0.8
3
0.6 dm X=_?_
The conversion for the two reactors in series is
(1) X > 0.8 (2) X < 0.8 (3) X = 0.8 (4) Can’t tell from the information given

Solution
(a) Ans. (3) X > 0.8
e

(b) Ans. (d) Can’t tell from information given

(c) Ans. (3) X = 0.8. See p161.
(d) Ans. (2) X < 0.8. Try X = 0.6
3 dm = 5 dm x 0.6 = 3 dm checks
3 3 3

Try ΔV = 0.1 between X = 0.6 and 0.7 V = 0.1 x 6 dm = 0.6 dm checks 3 3

10
9
8
FA0 7
6
–rA 5
(dm3) 4
3
2
1
3dm 3
0.2 0.4 0.6 0.8
X

4
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(5 pts) 4) Consider the following reaction for parts (a), (b) and (c)
→C
2A + B←

Write the rate law in terms of the specific reaction rate and species concentration
when
(a) The reaction is irreversible
€ and second order in A, and independent of the
concentration of C, and overall first order.
–r = ________________
A

(b) The reaction is elementary and reversible

–r = ________________
A

(c) Now consider the case when the reaction is first order in A and first order in B
at high concentrations of A and B and is first order in A and second order in B at
low concentrations of B. The rate law is

–r = ________________
A

(d) What is the rate law for the reaction CH 3 CHO → CH 4 + CO ?

−rCH 3CHO = ________________

€
Solution
B C €
A+ →
2 2
C 2A
(a) −rA = k A
CB
€
⎡ C ⎤
(b) −rA = k A ⎢C 2AC B − C ⎥
⎣ KC ⎦
€
k 1C AC 2B
(c) −rA =
1+ k 2C B
€
(d) −rA = kC 3A 2 (see page 80)

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(5 pts) 5) The following figure shows the energy distribution function at 300 K for the reaction
A+B→C
0.25

f(E,T) 0.2
–1 0.15
(kcal)
0.1
0.05

0 1 2 3 4 5 6 7 8
E (kcal)
(a) What fraction of the collisions have energies between 3 and 5 kcal?

(b) What fraction of collisions have energies greater than 5 kcal?

Solution
(a) Between 0 and 4 k cal Between 4 and 8 kcal
⎛ 0.25 ⎞ 0.5 − 0.25
f (E,T) = ⎜ ⎟E f (E,T) = E
⎝ 4 ⎠ 4

0.25

f(E,T) 0.2 € 3
€ at E = 3 f (E,T) = .25 = 0.188
–1 0.15 4
(kcal)
0.1 3
at E = 5 f (E,T) = .25 = 0.188
0.05 4
3
0 Area = 1× (0.25) + (1) .25
1 2 3 4 5 6 7 8 4
E (kcal) = 0.44 = 44%
⎛ 3⎞
(b) ⎜ ⎟(.25)
⎝4⎠
0.25 €
f(E,T) 0.2
–1 0.15 ⎛ 3⎞ 1
€ (kcal) Area = ⎜ ⎟(.25) × 3 × =
0.1 ⎝ 4⎠ 2
0.05 = 0.28 = 28%
0 1 2 3 4 5 6 7 8
E (kcal)
€

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(5 pts) 6) Consider the following elementary gas phase reaction
→C
2A + B←

Write –r solely as a function of conversion (i.e., evaluating all symbols) when the
A

reaction is an elementary, reversible, gas phase, isothermal reaction with no pressure

drop with an equal molar feed
€ with C = 2.0, k = 2 and K = 0.5 all in proper units.
A0 A C

–r = ________________
A

Solution
Elementary
⎡ C ⎤
−rA = k⎢C 2AC B − C ⎥
⎣ KC ⎦
A is the limiting reactant
B C
€ A+ →
2 2
1
y A0 = (Equimolar)
2
1⎛1 1 ⎞ 1
ε = y A0δ = ⎜ − −1⎟ = −
2⎝2 2 ⎠ 2
⎛ X⎞ X
C A0 ⎜Θ B − ⎟ C A0
C A0 (1− X) ⎝ 2⎠ 2
CA = , CB = , CC =
(1+ εX) (1+ εX) (1+ εX)
⎡ 3 2⎛ X⎞ ⎤
⎢ C A0 (1− X) ⎜ Θ B − ⎟ C A0 X ⎥
⎝ 2⎠
−r A = k⎢ 3
− ⎥
⎢ (1+ εX ) 2K C (1+ εX ) ⎥
⎢⎣ ⎥⎦
⎡ ⎛ 1 ⎞ ⎤
⎢ 2 2 C A0 ⎜1− X ⎟ ⎥
⎢ C A0 (1− X) ⎝ 2 ⎠ C A0 X ⎥
€ −rA = k • −
⎢ ⎛ 1 ⎞2 ⎛ 1 ⎞ ⎛ 1 ⎞⎥
⎢ ⎜1− X⎟ ⎜1− X⎟ 2KC ⎜1− X⎟ ⎥
⎣ ⎝ 2 ⎠ ⎝ 2 ⎠ ⎝ 2 ⎠⎦

⎡ ⎤
⎢ 3 2 ⎥
⎢ C A0 (1− X) C A0 X ⎥
€ −rA = 2 −
⎢ ⎛ 1 ⎞2 ⎛ 1 ⎞⎥
⎢ ⎜1− X⎟ 2KC ⎜1− X⎟ ⎥
⎣ ⎝ 2 ⎠ ⎝ 2 ⎠⎦

€ 7
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 ⎛ dm3 ⎞ 2 mol ⎛ dm3 ⎞ 2
k=2 ⎜ ⎟ , C A0 = 2 3 , Θ B = 1 , KC = 0.5⎜ ⎟
⎝ mol⋅ s ⎠ dm ⎝ mol ⎠
⎡ ⎤
⎢ 2 ⎥
⎢ 8(1− X) 2X ⎥
€ −rA = 2 −
⎢⎛ 1 ⎞ 2 ⎛ 1 ⎞ ⎥
⎢⎜1− X⎟ ⎜⎝1− 2 X⎟⎠ ⎥
⎣⎝ 2 ⎠ ⎦

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(5 pts) 7) The elementary gas phase isomerization exothermic reaction
⎯⎯→ B
A←⎯⎯ cat

is carried out isothermally at 400K in a PBR where the pressure drop occurs with
α = 0.001 kg . The flow is laminar. Currently 50% conversion is achieved. The
–1

equilibrium constant at this

€ temperature is 3.0.
˙ , if the reactor diameter is increased by a factor of 4,
(a) For a fixed mass flow rate m
the conversion X is

(1) X > 0.5 (2) X < 0.5 (3) X = 0.5 (4) insufficient information to tell.
€
˙ , the equilibrium conversion X is
(b) For a fixed mass flow rate m e

(1) X = 0.5
e (2) X = 0.667
e (3) X = 0.75
e (4) insufficient information to tell.

(c) For a fixed mass € ˙ , if the reactor diameter is increased by a factor of 2,

flow rate m
the equilibrium conversion X will e

(1) increase (2) decrease (3) remain the same (4) insufficient information to tell
€
˙ , if the particle size is increased the equilibrium
(d) For a fixed mass flow rate m
conversion X will e

(1) increase (2) decrease (3) remain the same (4) insufficient information to tell
€
(e) Consider the case where an adiabatic endothermic reaction becomes “frozen” in
a PFR [cf. p.541]. The actual conversion, X, can be greater than the equilibrium
conversion, X , near the point where the reaction becomes frozen.
e

(1) True (2) False (3) Depends on feed condition

Solution
(a) Ans. (1) X > 0.5
1
α~
D2
Increase D, decrease α, increase X.

(b) Ans. (3) X = 0.75

e

€ KC 3
Xe = = = 0.75
1+ K C 1+ 3

€ 9
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 (c) Ans. (3) remain the same
C A C A0 (1− X e )y 1− X e
KC = = =
C Ae C A0 X e y Xe
X is not a function of pressure drop parameter α.
e

(d) Ans. (3) or

€(4)
Exothermic D ↑ then K ↓ then X ↓
P e

X is not a function of particle size or any other geometry. But will a change in
e

pressure drop affect the achievable conversion, and therefore temperature? X is

e

a function of temperature. So probably accept unchanged OR Can’t tell

(e) Ans. (2)

X can never be less than X, (i.e., X can never be greater than X ).
e e

10
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(5 pts) 8) Suppose inerts are added to the system in Example 13-2. The dashed line represents
the relationship after the inerts were added. Which figure represents how the
relationship between the line the reactor failed after start up, t , and the down time,
s

t , would change? The solid line represents the case without inerts?
d

Solution
Answer: B
Explanation:
dT Qg − Qr Qg − Qr
= =
dt ∑N iC Pi N AC PA + N BC PB + NC C PC + N I C PI
We see the rate of temperature increase, , decreases as the amount of inert, N ,
I

increases. Therefore, the temperature will not rise as rapidly during the adiabatic
period (down
€ time, t ) and we can have longer down times without having an
d

explosion.

11
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(10 pts) 9) P10-5 A Study Problem. The rate law for the hydrogenation (H) of ethylene (E) to
form ethane (A)
H 2 + C 2H 4 ⎯⎯→ C 2H 6
cat
over a cobalt-molybdenum catalyst [Collection Czech. Chem. Commun., 51,
2760 (1988)] is
€ kPE PH
−rEʹ =
1+ K E PE
Suggest a mechanism and rate-limiting step consistent with the rate law
and then derive the rate law.
€
Solution
H = H2

E = Ethylene

A = Ethane

H 2 + C 2H 4 ⎯cat
⎯→ C 2H 6

H+E⎯
⎯→ A
Because neither H or C H are not in the denominator of the rate law they are either
2 2 6

not adsorbed or weakly adsorbed. Assume H in the gas phase reacts with C H
2 2 6

€ adsorbed on the surface and ethane goes directly into the gas phase. Then check to
see if this mechanism agrees with the rate law

Eley Rideal

⎯⎯→ ⎡ C ⎤
E + S←
⎯ ⎯ E •S rAD = k AD ⎢PE C V − E•S ⎥
⎣ KE ⎦

E •S + H ⎯
⎯→ A + S rS = k SC E•SPH 2

€ ⎯⎯→ €
E •S ←
⎯⎯ A + S
€ €
Assume surface reaction
C E•S = K E PE C V
€
rS = k S [C E•SPH ]

C T = C V + C E•S

⎡ P P ⎤
−rAʹ = k SK E C T ⎢ E H ⎥
⎣1+ K E PE ⎦

€ 12
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(10 pts) 10) P7-10B Study Problem. In order to study the photochemical decay of aqueous
bromine in bright sunlight, a small quantity of liquid bromine was
dissolved in water contained in a glass battery jar and placed in direct
sunlight. The following data were obtained at 25°C:

Time (min) 0 10 20 30 40 50 60

Ppm Br , C
2 A 3.45 2.45 1.74 1.23 0.88 0.62 0.44

(a) Determine whether the reaction rate is zero, first, or second order in
bromine, and calculate the reaction rate constant in units of your
choice. (Hint: Preliminary calculations suggest the reaction may be
first order.)
(b) Assuming identical exposure conditions, calculate the required hourly
rate of injection of bromine (grams per hour) into a very large sunlit
body of water, 25,000 gal (94,600 dm ) in volume, in order to maintain
3

a sterilizing level of bromine of 1.0 ppm.

Note: ppm = parts of bromine per million parts of brominated water by
weight. In dilute aqueous solutions, 1 ppm = 1 milligram per liter.)
(From California Professional Engineers’ Exam.)

13
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 Solution
P7-10 (a)
Photochemical decay of bromine in bright sunlight:
t (min) 0 10 20 30 40 50 60
CA (ppm) 3.45 2.45 1.74 1.23 0.88 0.62 0.44

Mole balance: constant V

dC A
= rA = −kCαA
dt
dC A
α = 1, therefore = −kC A
dt
dC A C
€ = −kC A , ln A0 = kt
dt CA
After plotting and differentiating by equal area
€
Time (min) 0 10 20 30 40 50 60
Ppm Br2, CA 3.45 2.45 1.74 1.23 0.88 0.62 0.44
€
–dCA/dt 0.082 0.061 0.042 0.030 0.0215 0.014
ln(–dCA/dt) -2.501 -2.797 -3.170 -3.507 -3.840 -4.269
ln CA 0.896 0.554 0.207 -0.128 -0.478 -0.821
ln CA0/CA 0 0.34 0.68 1.03 1.34 1.72 2.05

First order

C A0
ln
CA

14
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 Slope of Plot of ln (C /C ) versus t
A0 A

2.0
Slope =
58 min
k = 0.0345 min−1

P7-10 (b)
€ dN A
= VrA
dt
dN A
= FA0 − 0 + rAV
dt
dN A
Steady state =0
dt
€ FA0 = −rAV
at C = 1 ppm
A

€
ppm mg
€ rA = −0.344 = −0.344
min l min
⎛ mg ⎞ 1g ⎛ 60m ⎞ g
( ⎝
)
FA0 ≡ 94,600 dm3 ⎜ 0.034 3 ⎟ × × ⎜
dm min ⎠ 1,000mg ⎝ h ⎠
⎟ = 195
h
€

15
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This problem is continued from Problem (6) on MidTerm Exam II (Complete parts (e) and (f))
(10 pts) 11) The temperature and conversion in a virtually infinitely long PFR are shown below
as a function of the reactor volume. The reactor is surrounded by a jacket for heat
transfer. The value of Ua is 100 cal/(sec • m • K) with T being constant. The gas-
3
a

phase, reversible reaction is

2A →B+C
←
and pure A is fed to the reactor at a concentration C = 1.0 mol/m and a molar flow
A0
3

rate of 10 mol/s. The absolute value of the heat of reaction is 5,000 cal/mol of A at
500K, and the heat capacities of A, B, and C are each 10 cal/mol/K.
800 €
1.0
700 0.9
0.8
600
0.7
0.6 X
T(K)
0.5
500
0.4
0.3
400
0.2
0.1
300
0 10 20 30 100
3
V(m )
(a) Using what is the equilibrium constant at 500 K?
K (500) = ____0.11____ (From MidTerm Exam II solution)
e

(b) What is the rate of disappearance of A, –r , at 10 m ?

A
3

–r = __2 mol/m •s__ (From MidTerm Exam II solution)

A
3

(6 pt) (c) What is the equilibrium constant at 400 K?

K (400) = ____________
e

(8 pt) (d) What is the specific reaction rate at V = 10 m ? 3

k = ____________
(6 pt) (e) What is the total amount of heat added/removed to the entire reactor per mol of
A feed? Include proper sign in your numerical answer if possible.
˙
Q
= ____________
FA0

16
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 Solution

800
1.0
700 0.9
0.8
600
0.7
0.6 X
T(K)
0.5
500
0.4
0.3
400
0.2
0.1
300
0 10 20 30 100
3
V(m )
at V = 10 m Q = Q
3
g r

(a) K (500) = _?__________

e

1 1
A → B+ C
2 2
δ = 0∴ε = 0

C A = C A0 (1− X)

C B = CC = C A0 X 2
2
C C C 2A0 X 2e (0.4 ) = 0.16 = 0.11
at 500 K X = X = 0.4 K e = B 2 C =
e
2
= 2
CA C 2A0 4 (1− X e ) 4 (1− 0.4 ) 4 (0.36)
€ K = 0.11
e

(b) –r = _?__________
A

€
dX −rA
=
dW FA0
Q Qr
!#"g #$ !#" #$
dT (rA )(ΔH Rx ) − Ua( T − Ta )
€ =
dV ∑FiC Pi

dT
At minimum =0
dV
€ Q =Q
g r

At large V no further change in temperature so assume T = T = 500 K and that T

a

€
at minimum is 400 K.
At minimum
17
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 ˙ r = Ua (T – T ) = 100 (400 – 500) = –10,000 cal/s•m
Q a
3

Q g = (−rA )(−ΔH Rx )
cal
€ (−rA )(−ΔH Rx ) = (−rA )(−5,000) = Q r = –20,000
m3 ⋅ s
€ cal
−10,000
−rA = s • m3 = 2 mol
€ cal m3 • s
−5,000
mol
(c) K (400) = _?__________
e

⎡ΔH ⎛ 1 1 ⎞⎤
€ K e ( 400) = KC (500) exp⎢ Rx ⎜ − ⎟⎥
⎣ R ⎝ T1 T2 ⎠⎦
⎡ 5,000 ⎛ 1 1 ⎞⎤
K e ( 400) = 0.11exp⎢ ⎜ − ⎟⎥
⎣1.987 ⎝ 500 400 ⎠⎦
⎡ −100 5,000 ⎤
= 0.11exp⎢ ⎥
⎣ ( 400)(500) 1.987 ⎦
K e = 0.11exp(−1.25) = (0.11)(0.28) = 0.031
(d) k = _?__________
€
⎡ C C ⎤
€ −rA = k⎢C 2A0 − B C ⎥
⎣ Ke ⎦

B C
A→ +
2 2
C A = C A0 (1− X)

€ C A0 X
C B = CC =
2
at V = 10 m T = 400, X = 0.2, K = 0.031
3
e

18
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 ⎡ 2
2 C X
2⎤
−rA = k⎢C 2A0 (1− X) − A0 ⎥
⎣ 4KC ⎦

⎡ 2 X2 ⎤
= kC 2A0 ⎢(1− X) − ⎥
⎣ 4K e ⎦

⎡ 0.2) ⎤
2
2
= k ⋅1⋅ ⎢(1− 0.2) −
( ⎥
⎢⎣ (4 )(0.031) ⎥⎦
⎡ 0.04 ⎤
= k⎢0.64 − = k [0.64 − 0.32]
⎣ 0.124 ⎥⎦

mol ⎛ mol ⎞ 2
−rA = 2 3 = 0.32⎜ 3 ⎟ k
m •s ⎝m ⎠
€
2 m3
k= = 6.25
0.32 mol• s
€ ˙
Q
(e) = ?
FA0
€
˙ − FA0 ∑Θ i C P (T − T0 ) − ΔH !Rx + ΔC P (T − Ta ) FA0 X = 0
Q [ ] Eqn. (11-28)
i
€
Per Mole A
˙
Q
€ = C PA [ T − T0 ] + [ΔH Rx + ΔC P (T − TR )X]
FA0
→ B C
A← +
2 2
€ C PC C PB 10 10
ΔC P = + − C PA = + −10 = 0
2 2 2 2
€
=0
˙
Q cal
= 10(500 − 600) + [+5,000][0.4 ] = −1,000 + 2,000 = 1,000
FA0 mol

19
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(10 pts) 12) Let’s revisit homework Problem P12-3 where the reaction
B

→ 2C
A + B←

is carried out in a packed bed reactor. Match the following temperature and
conversion profiles for the 4 different heat exchange cases adiabatic, constant T ,
a

co-current exchange and counter

€ current exchange.

Figure 1 Figure 2

Figure 3 Figure 4

20
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 Figure A Figure B

Figure C Figure D

(a) Figure 1 matches Figure ___

(b) Figure 2 matches Figure ___
(c) Figure 3 matches Figure ___
(d) Figure 4 matches Figure ___

Solution
(a) Figure 1 matches Figure _C_
(b) Figure 2 matches Figure _A_
(c) Figure 3 matches Figure _D_
(d) Figure 4 matches Figure _B_

21
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In Class Problem 14 Solution
(a) Adiabatic

22
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 ← Constant T a

In Class Problem 14 Solution

(b) Constant T Heat Exchange
a

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In Class Problem 14 Solution
(c) Variable T Co-Current Heat Exchange
a

24
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In Class Problem 14 Solution
(d) Variable T Counter Current Heat Exchange
a

Matches

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(20 pts) 13) The following reactions are taking place in a 2,000 dm liquid phase batch reactor 3

under a pressure of 400 psig

k
1A
A + 2B ⎯ ⎯
⎯ →C ΔH Rx1B = −5,000 cal mol −r1A = k 1AC AC 2B

2A k
3C + 2A ⎯ ⎯
⎯ →D ΔH Rx2C = +10,000 cal mol −r2A = k 2AC ACC

3C k
B + 3C ⎯ ⎯
⎯ →E ΔH Rx3B = −50,000 cal mol −r3C = k 3C C BCC
The initial temperture is 450 K and the initial concentrations of A, B and C are 1.0,
0.5 and 0.2 mol/dm respectively. The coolant flow rate was at it’s maximum value
3

so that T = T = T = 400 K so that the product the exchange area and overall heat
€ a1 a2 a

transfer coefficient, UA, is UA = 100 cal/s•K.

(a) What is Q at t = 0?
r

(b) What is Q at t = 0?
g

(c) If Q > Q at time t = 0, and there is no failure of the heat exchange system, is
r g

there any possibility that reactor will run away? Explain

(d) What is the initial rate of increase in temperature, (dT/dt) at t = 0?

dT
= ____________
dt
(e) Suppose that the ambient temperature T is lowered from 400 K to 350 K, what is
a

the initial rate of reactor temperature change?

dT
€ = ____________
dt
(f) A suggestion was made to add 50 mole of inerts at a temperature of 450 K. Will
the addition of the inerts make runaway more likely or less likely?
How? Show quantitatively.
€
Additional information
As a first approximation, assume all heats of reaction are constant (ΔC P ≅ 0)
Specific reaction rates at 450 K are
2
k 1A = 1×10−3 dm3 mol ( ) s
€
1 2
k 2A = ×10−3 dm3 mol
3
( ) s

2
k 3C = 0.6 ×10−3 dm3 mol ( ) s

€
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 C PA = 10cal mol K C PD = 80cal mol K

C PB = 10cal mol K C PE = 50cal mol K

C PC = 50cal mol K

Solution

€ Part (a)
cal cal
Q r = UA( T − Ta ) = 100 [ 450 − 400]K = 5,000
5•K s
Part (b)
Q g = V[r1BΔH Rx1B + r2C ΔH Rx2C + r3BΔH Rx3B ]
€
Initially T = 350 K
r1A r1B r1C
€ Reaction 1: = = r1B = 2r1A
−1 −2 1
r2A r2C r2D 3
Reaction 2 : = = r2C = r2A
−2 −3 1 2
r3B r3C r3E 1
Reaction 3 : = = −r3B = r3C
−1 −3 1 3
⎡3 ⎤ ⎡1 ⎤
[ ]
Q g = V 2k 1AC AC 2B [−ΔH Rx1B ] + V⎢ k 2AC ACC ⎥[−ΔH Rx2C ] + V⎢ k 3C C BCC ⎥[−ΔH Rx 3C ]
⎣2 ⎦ ⎣3 ⎦
€
⎡ ⎤
⎢ ⎛
3 1 ⎞ ⎥
[ ( )
!####"####
2

$
]
= (2,000) (2) 10−3 (1)(0.5) 5,000 + 2,000⎢ ⎜ ×10−3 ⎟(1)(0.2)[10,000]⎥ +
⎢! 2 ⎝#3 ###
⎠ "####$⎥
5,000 ⎢⎣ −2,000 ⎥⎦

⎡1 ⎤
( )
+2,000⎢ 0.6 ×10−3 (0.5)(0.2)⎥ • [50,000] = 5,000
⎣3 ⎦
!######"###### $
+2,000

Q g = 5,000cal s

dT Qr − Q g 5,000 − 5,000
= = =0
dt N A0C PA + N B0C PB + NC0C PC N A0C PA + N B0C PB + NC 0C PC
Part (c)
dT Q g − Qr
€ =
dt N AC PA + N BC PB + NC C PC

If Q > Q then the temperature can only decrease causing the specific reaction
r g

rates k to decrease, hence runaway is unlikely.

i

€
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 Part (d)
N A0 C PA = C A0VC PA = (1)(2,000)(10) = 20,000

N B0 C PB = C B0VC PB = (0.5)(2,000)(10) = 10,000

NC0 C PC = CC 0VC PC = (0.2)(2,000)(50) = 20,000

dT Q g − Q r
=
dt 50,000
€
Part (e)
Drop Ta by 50
€
Q r = UA( T − Ta ) = 100( 450 − 350) = 10,000

dT 5,000 −10,000
= = −0.1
dt 50,000
Part (f)
dT Q g − Q r [r VΔH Rx1B + r2C VΔH Rx 2C + r3AVΔH Rx 3A ] − UA(T − Ta )
€ = = 1B
dt ∑N iC Pi N AC PA + N BC PB + NC C PC + N DC PD + N E C PE + N InertsC PInerts

Inerts (N ) will not change Q or Q , they will only show the rate of
Inerts g r

temperature increase or decrease.

€

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