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Chapter 1

Exercise 1:


H
3
C
H
2
C
CH
3 H
3
C
H
C
CH
2
+ H
2

(C)
propane (A) propylene (B)



At equilibrium:


(

= =
tot
tot tot
A
C B
A
C B
P x a
P
P P
X
X X
K K K K

[1 atm]
-1
(1)

Assuming ideal behavior,


tot
A
C B
tot A
tot C tot B
o
A
o
C
o
B
a
P
X
X X
P X
P X P X
P
P P
K =

= (2)

(3)
C B
X X =

(4)
C B A
X X X + + = 1

Using equations (2), (3), and (4), solve for the three unknown mole fractions and find the
fractional conversion of propane at each temperature.

(5)
A A
X f = 1



Or an Alternate Solution:

Write a mole balance for the reaction.

(Where f
A
= fractional conversion of propane)


Initial Moles Change in Moles Final Moles
A n
A
o
-n
A
o
f
A
n
A
o

(1 f
A
)
B 0 n
A
o
f
A
n
A
o

(f
A
)
C 0 n
A
o
f
A
n
A
o

(f
A
)
Total n
A
o
n
A
o
f
A
n
A
o
(1 + f
A
)
1.1
Express the mole fraction of each species in terms of f
A
.


) 1 (
) 1 (
) 1 (
) 1 (
Moles) (Total
A) of (Moles
A
A
A
o
A
A
o
A
A
f
f
f n
f n
X
+

=
+

= = (6)

1
A
A
B
f
f
X
+
= (7)


A
A
C
f
f
X
+
=
1
(8)

Substitute equations (6), (7), and (8) into equation (2), above, and solve for fractional
conversion (f
A
).


tot
A A
A
P
f f
f
K
+
=
) 1 )( 1 (
2
(9)

@ 400
o
C @ 500
o
C @ 600
o
C
Conversion (f
A
) 0.0228 0.1012 0.3076


Exercise 2:

H
3
C
H
2
C
CH
3 H
3
C
H
C
CH
2
+ H
2
O
(D)
propane (A) propene (C)
+ 1/2 O
2

(B)



Assume 100% conversion of propane at each temperature, because the equilibrium
constants are so high. A major impediment is the oxidation of propane to CO
2
(not
shown).













1.2
Exercise 3:

H
3
C
H
C
H
C
CH
3
H
3
C
H
C CH
H
2
C
H
C
H
2
C CH
3
CH
3
cis-2-butene (B)
trans-2-butene (C)
1-butene (A)
k
1
k
-1
k
2
k
-2
k
-3
k
3


Part a)

Express the equilibrium constants for each step in terms of partial pressures.


A
B
P a
P
P
K K = =
1 1
(1)


B
C
P a
P
P
K K = =
2 2
(2)


C
B
B
A
C
A
P a
P
P
P
P
P
P
K K = = =
3 3
(3)

Rewrite equation (3) in terms of K
1
and K
2
.


2 1
3
1 1
P P
K K
K = (4)

Therefore, K
3
= 0.108.

Part b)

Check the independence of the 3 reactions.

For all 3 equations. (5)

=
=
3
1
0
i
i i
A

1.3
And
(
(
(

(
(
(

=
(
(
(

C
B
A
1 0 1
1 1 0
0 1 1
0
0
0
0 ) 1 1 ( ) 1 1 ( ) Det(Matrix = =

Therefore, all equations are not independent (i.e. only need 2 equations to solve).

Assuming a basis of 1 mole of 1-butene, write a mole balance for the system.

Initial Moles Change Final Moles
A 1

-
1
-
3
1-
1
-
3
B 0

1

1

C 0

3

3

Total 1

0 1

Rewrite equations (1) and (3) in terms of
1
and
2
.


3 1
1
1
1


= = =
tot A
tot B
A
B
a
P X
P X
P
P
K (6)


1
3
3

= =
B
C
a
P
P
K (7)
Solving for
1
and
3
gives an equilibrium conversion of 1-butene = 0.932.

Mole fractions at equilibrium:

X
1-butene
= 0.068
X
cis-2-butene
= 0.296
X
trans-2-butene
= 0.636


Exercise 4:

First, find K for each reaction from G
o
, using equation (1), assuming ideal behavior.


T R
G
K
g


=
0
) ln( (1)
Reaction G
0
(kJ mol
-1
) K
1 14.85 0.078
2 10.42 0.167
3 15.06 0.075


1.4




Write a mole balance on the system of reactions, assuming a basis of 1 mole toluene.

Initial Moles Change Final Moles
Toluene (A) 1 -2
1
-2
2
-2
3
1-2
1
-2
2
-2
3

Ortho-Xylene (B) 0
1

1

Meta-Xylene (C) 0
2

2

Para-Xylene (D) 0
3

3

Benzene (E) 0
1
+
2
+
3

1
+
2
+
3

TOTAL 1 0 1

Express the equilibrium constants in terms of
1
,
2
, and
3
.


2
3 2 1
3 2 1 1
2
1
) 2 2 2 1 (
) (
) (


+ +
=

=
A
E B
X
X X
K (2)


2
3 2 1
3 2 1 2
2
) 2 2 2 1 (
) (



+ +
= K (3)


2
3 2 1
3 2 1 3
3
) 2 2 2 1 (
) (



+ +
= K (4)

Solve for
1
,
2
, and
3
and calculate the equilibrium compositions of each species.

The equilibrium mole fractions are:

Toluene = 0.470
Ortho-Xylene = 0.065
Meta-Xylene = 0.138
Para-Xylene = 0.062
Benzene = 0.265

Since para-xylene has a smaller kinetic diameter than either ortho- or meta-xylene, a
shape selective catalyst that allows mostly para-xylene to diffuse out of it will shift the
product distribution.

Exercise 5:

Part a)

Assuming a basis of 1 mole of feed, write an overall mole balance.

1.5
Initial Moles Change Final Moles
Acetylene (A) 0.5 -
1
0.5
1

HCl (B) 0.5 -
1

2
0.5 -
1

2

Vinyl Chloride (C) 0
1

2

1

2

1,2 Dichloroethane (D) 0
2

2

TOTAL 1 -
1

2
1 -
1

2


Express the equilibrium constants in terms of
1
,
2
, and
3
.

For the reaction that forms vinyl chloride (C),


(

= =
tot tot
tot
B A
c
B A
c
P x a
P P
P
X X
X
K K K K

1 1 1 1
[1 atm] (1)

Assuming ideal behavior,


5
1
) 5 . 0 )( 5 . 0 (
) 1 )( ( 1
2 1 1
2 1 2 1
1



= =


tot B A
C
a
P X X
X
K (2)


Similarly for the reaction that forms 1,2 dichloroethane,


5
1
) 5 . 0 )( (
) 1 ( 1
2 1 2 1
2 1 2
2



= =


tot B C
D
a
P X X
X
K (3)

Solve for
1
,
2
, and
3
and calculate the equilibrium compositions of each species.

X
Acetylene
= 0.012
X
HCl
= 0.002
X
Vinyl chloride
= 0.976
X
1,2 Dichloroethane
= 0.010

Find the fractional conversion of acetylene.

988 . 0 1 = =
o
A
A eq
A
n
n
f (4)

Part b)

Write another mole balance similar to part (a) but now add 9 moles of inert gas.


Initial Moles Change Final Moles
Acetylene (A) 0.5 -
1
0.5
1

1.6
HCl (B) 0.5 -
1

2
0.5 -
1

2

Vinyl Chloride (C) 0
1

2

1

2

1,2 Dichloroethane (D) 0
2

2

Inert Gas (I) 9 0 9
TOTAL 10 -
1

2
10 -
1

2


Express the equilibrium constants in terms of
1
,
2
, and
3
.


5
1
) 5 . 0 )( 5 . 0 (
) 10 )( ( 1
2 1 1
2 1 2 1
1



= =


tot B A
C
a
P X X
X
K (5)


5
1
) 5 . 0 )( (
) 10 ( 1
2 1 2 1
2 1 2
2



= =


tot B C
D
a
P X X
X
K (6)

Solve for
1
,
2
, and
3
and calculate the equilibrium compositions of each species.

X
Acetylene
= 0.0014
X
HCl
= 0.0012
X
Vinyl Chloride
= 0.0510
X
1,2 Dichloroethane
= 0.0002
X
Inert
= 0.946

Find the fractional conversion of acetylene.

974 . 0 1 = =
o
A
A eq
A
n
n
f (7)


Exercise 6:

Write the rate expression for the 2-propanol (P) reaction, rearrange, and integrate.


P
P
n k
dt
dn
= (1)



=
t n
n
P
P
dt k
n
dn
P
o
P
0
(2)

kt
n
n
o
P
P
=
|
|
.
|

\
|
ln (3)

1.7
Before plotting the data, convert
Propanol
Acetone
g
g
to
o
P
P
n
n
.


P P
P
P
n
n
g
mol
mol
g
g
g
a
a
a a
58
1
1
60
= (4)

) (
1
1
a a
o
P P
o
n n n n
|
.
|

\
|
+ = (5)

y = -8.39E-06x
R
2
= 9.92E-01
-0.00160
-0.00140
-0.00120
-0.00100
-0.00080
-0.00060
-0.00040
-0.00020
0.00000
0 50 100 150 200
Time (min)
l
n
(
m
o
l
e
s

o
f

2
-
P
r
o
p
a
n
o
l
)


The first order rate constant (k) is the negative of the slope = 8.39 x 10
-6
min
-1
.


Exercise 7:

H
3
C
H
3
C
+
O
H
H
3
C
H
3
C
O
H
DMB (A) 3,4-Dimethyl-
3
-tetrahydro-benzaldehyde (C) Acrolein (B)



Assuming constant volume, write the second order rate equation for DMB.


B A
A
C C k
dt
dC
= (1)

Now find C
B
in terms of C
A
.

) (
1
1
o
A A
o
B B
C C C C
|
.
|

\
|

+ = And (2)
o
B
o
A
C C =

1.8
Therefore, C
B
= C
A
.

Rewrite the rate equation (equation (1)) in terms of f
A
.

2 2
) 1 ( ) (
A
o
A
A o
A
f C k
dt
df
C = (3)




=

t
o
o
A
f
A
A
dt kC
f
df
A
0
2
) 1 (
(4)

Solve this integral
t kC
f
f
o
A
A
A
=
1
(5)

Finally, plot
A
A
f
f
1
vs. time at each temperature and find slope, kC .
o
A

y = 0.0097x
R
2
= 0.9963
y = 0.0027x
R
2
= 0.9929
y = 0.0003x
R
2
= 0.9961
0
0.1
0.2
0.3
0.4
0.5
0.6
0 50 100 150 200 250
f
A
/
(
1
-
f
A
)
Time (hr)
T = 323 K
T=298 K
T = 278 K



Temperature (K) Rate Constant (L mol
-1
hr
-1
)
323 0.100
298 0.028
278 0.0033


1.9


Exercise 8:

This reaction can be assumed to be of the form Products. A


Assuming the reaction to be 1
st
order, write the appropriate first order rate expression and
integrate.


A
A
kC
dt
dC
= (3)

kt
C
C
o
A
A
=
|
|
.
|

\
|
ln (4)

Now a plot of
|
|
.
|

\
|
o
A
A
C
C
ln vs. time should be linear with a slope = -k.
First Order
y = -0.0081x
R
2
= 0.9922
-2
-1.5
-1
-0.5
0
0 50 100 150 200 250
time (min)
l
n

(
C
A
/
C
A
o
)

Assuming
o
A
A
C
C
is equivalent to relative absorbance, a plot of ln(relative adsorbance) vs.
time should be linear with slope = -k.

The data appear first order with a rate constant, k = 0.0081 min
-1
. Analogous attempts to
fit zero and second order reaction rate experiments failed.


Exercise 9:

Express n
A
and n
B
in terms of fractional conversion of A (f
A
).

(1)
A
o
A
o
A A
f n n n =
(2)
A
o
A
o
B B
f n n n = 2

1.10
For constant density (), and constant volume (V),
V
n
i
can be expressed as concentration
(C
i
).

(3)
A
o
A
o
A A
f C C C =
And
A
o
A
o
B B
f C C C = 2
o
A
o
B
C
C
= 3 so, (4)
(5) ) 2 3 (
A
o
A B
f C C =

Substitute equations (3) and (5) into the given rate expression.


dt
df
C
dt
f C C d
dt
dC
A o
A
A
o
A
o
A A
=

=
) (
(6)


2
2
2
) 2 3 )( 1 (
A A
o
A
o
A
B A A
f f kC
C
C kC
dt
df
= = (7)

Separate variables and integrate.



=

10
0
2
5 . 0
0
2
) 2 3 )( 1 (
dt kC
f f
df
o
A
A A
A
(8)

Solving for the rate constant (k) gives k = 120 L
2
mol
-2
min
-1
.


Exercise 10:

Calculate the total moles of gas initially in the system for N
2
:H
2
:He = 3:1:0, assuming
ideal gas behavior.


|
|
.
|

\
|
=
K
o
K
K
o
K
T
P
T P
298
298
648 648
(1)

mol 013 . 0 = =
o
g
o
o
tot
T R
V P
n (2)

Write a gas phase mole balance.

Initial Moles Change Final Moles
N
2
9.75 x 10
-3
-(t) 9.75 x 10
-3
- (t)
H
2
3.25 x 10
-3
-3(t) 3.25 x 10
-3
- 3(t)
He 0 0 0
1.11
NH
3
0 0 0
Total 0.013 -4(t) 0.013 - 4(t)

Derive the rate expression using the ideal gas law and express the rate in terms of
dt
dP
tot
.

T R n V P
g tot tot
= |
.
|

\
|
=
dt
dP
T R
V
dt
dn
tot
g
tot
(3)


dt
d
dt
dn
tot

4 = And
dt
d
dt
dn
N
=
2
(4)

Therefore,
dt
d
is the rate of reaction, and |
.
|

\
|
=
dt
dP
T R
V
dt
d
tot
g
4

. (5)

Plot Total Pressure vs. Time to find the rate of change in pressure (i.e. slope)

Rate of Change of Pressure
Determination 3:1:0
y = -1.9292x + 767.1
R
2
= 0.9984
650
700
750
800
0 20 40 6
time (min)
T
o
t
a
l

P
r
e
s
s
u
r
e

(
t
o
r
r
)

a
t

2
9
8
K
0


From the graph
dt
dP
tot
= -1.9292 torr min
-1
.

Repeat the same process for the other gas ratios and solve for
dt
d
.

Ratio
(N
2
:H
2
:He)
dt
dP
tot
(torr min
-1
)

dt
d
(mol min
-1
)
3:1:0 -1.9292 8.17 x 10
-6
1:1:2 -0.8947 3.79 x 10
-6

1:3:0 -0.5668 2.40 x 10
-6







1.12
Write the Goldberg-Waage form of the rate equation and take the natural log of both
sides.

| | | |

2 2
rate H N k
dt
d
= = (6)

(7) | | |
2 2
ln ln ) ln( ) rate ln( H N k + + = |

To find plot ln(rate) vs. ln[N
2
] at a constant [H
2
], where ln[N
2
] = ln[moles of N
2
].

rate moles N
2
moles H
2

8.17 x 10
-6
3 1
3.79 x 10
-6
1 1
2.40 x 10
-6
1 3





Constant H
2
y = 0.6992x - 12.483
R
2
= 1
-12.6
-12.4
-12.2
-12
-11.8
-11.6
0 0.2 0.4 0.6 0.8 1 1.2
ln (moles N
2
)
l
n

(
r
a
t
e
)



From the graph, = slope. Similarly, find by plotting ln(rate) vs. ln[H
2
] while holding
[N
2
] constant.

= 0.70
= -0.42

Therefore, the final rate expression is . Finally, find the rates of
ammonia synthesis for each ratio.
| | | |
42 . 0
2
70 . 0
2
rate

= H N k


dt
d
dt
dn
NH
2
3
= (8)

Therefore,

1.13

N
2
:H
2
:He |
|
.
|

\
|
min gcat
mol
3
dt
dn
NH

3:1:0 8.17 x 10
-5
1:1:2 3.79 x 10
-5
1:3:0 2.40 x 10
-5



Exercise 11:

In Example 1.5.6 the following equations for t
max
and C
B
are derived.


(
(

|
|
.
|

\
|
+

=
o
A
o
B
o
A
o
B
C
C
k
k
C
C
k
k
k
k
k k
t
2
1
2
1
2
1
2
1 2
max
ln
1
(1)


( ) ( ) ( )
|
t k t k
o
A t k o
B B
e e
k k
C k
e C C
2 1 2
1 2
1

+ = | (2)

Assuming = 0 and k
o
B
C
2
= k
1
, C
B
and
0
0
max
= t . Therefore, use LHopitals rule to find
t
max
and C
B
.


1
1
2
1
max
1
1
lim lim
1 2 1 2 k
k
k
k
t
k k k k
= =

(3)

(4)
) (
max 1
max 2
1 2 1 2
lim lim
t k o
A
k k
B
k k
e t C k C


=

Substituting for t
max
gives:


e
C
C
o
A
B
=
max
(5)

Exercise 12:

Part a)

Assign rate constants, k
i
, to equations 1,2, and 3.

(1) R G R
k
2
1
+
(2) L R L
k
2
2
+
1.14
(3) D L
k

3

Derive rate equations for each equation.

(4)
G R
C C k
1 1
r =
(5)
R L
C C k
2 2
r =
(6)
L
C k
3 3
r =

Express the accumulation rate of each species in terms of the above rates.


2 1 1
r r r 2 =
dt
dC
R
(7)

3 2 2
r r r 2 =
dt
dC
L
(8)

Substituting equations (4), (5), and (6) gives:


R L G R
R
C C k C C k
dt
dC
2 1
= (9)

L R L
L
C k C C k
dt
dC
3 2
= (10)


Part b)

Solve differential equations using most convenient solver.


L L R
L
L R R
R
C C C
dt
dC
C C C
dC
=
=
dt
With initial conditions
1 ) 0 (
20 ) 0 (
=
=
L
R
C
C













1.15



Lynxes

Rabbits
P
o
p
u
l
a
t
i
o
n


Time





Exercise 13:

Write the rate expression for DEBA, assuming constant volume.


BB DEA
DEBA
C kC
dt
dC
= = r (1)

Find C
DEA
and C
BB
in terms of C
DEBA
.

) (
1
1
o
DEBA DEBA
o
DEA DEA
C C C C |
.
|

\
|
+ = (2)

) (
1
1
o
DEBA DEBA
o
BB BB
C C C C
|
.
|

\
|
+ = (3)

Substitute equations (2) and (3) into equation (1), using the initial conditions given for
1,4-butanediol and acetonitrile, respectively.

) 5 . 0 )( 5 . 0 (
DEBA DEBA
DEBA
C C k
dt
dC
= (4)

) 1 . 0 )( 1 (
DEBA DEBA
DEBA
C C k
dt
dC
= (5)
1.16

Rearrange equations (4) and (5), and integrate to find C
DEBA
as a function of time for each
solvent.

1,4-butanediol:



=

t C
DEBA
DEBA
dt k
C
dC
DEBA
0 0
2
) 5 . 0 (
(6)

2
) 5 . 0 (
1
+ =

kt
C
DEBA
(7)

acetonitrile:



=

t C
DEBA DEBA
DEBA
dt k
C C
dC
DEBA
0 0
) 1 . 0 )( 1 (
(8)

kt
C
C
DEBA
DEBA
10
9
10 1
1
ln =
|
|
.
|

\
|

(9)

Using equations (7) and (9), find the rate constant (k) for each solvent.

1,4-butanediol: k = 0.000212 L mol
-1
min
-1


acetonitrile k = 0.00160 L mol
-1
min
-1


Exercise 14:

Write the first order rate equation for variable volume, Equation 1.5.3,


A
A
kn
dt
dn
= (1)

Rearrange and integrate equation (1) to find
o
A
A
n
n
.



=
t n
n
A
A
dt k
n
dn
A
o
A
0
(2)


( ) kt
o
A
A
e
n
n

= (3)
1.17

Use the ideal gas law to derive an expression for
o
total
total
n
n
.


RT n
RT n
V P
V P
o
tot
tot
o
tot
tot
= (4)

7 . 1
7 .
=
+
= =
o
o o
o o
tot
tot
V
V V
V
V
n
n
(5)

Define the molar expansion factor and find
o
A
A
n
n
.

2
1
1 3
1 =
|
|
.
|

\
|

=
A
(6)

7 . 1 2 1 = + =
A
o
tot
tot
f
n
n
Where
o
A
A
n
n
=1
A
f (7)

65 . 0 =
o
A
A
n
n
(8)

Solving for k in equation (3) gives k = 0.000598 sec
-1
.

To find the time needed to raise the pressure from 1.8 atm to 2.5 atm, first find
o
total
total
n
n
.

389 . 1
8 . 1
5 . 2
= = =
o o
tot
tot
P
P
n
n
(9)

Using the value from equation (9), find
o
A
A
n
n
.

389 . 1 1 = + =
A A
o
tot
tot
f
n
n
(10)

8055 . 0 =
o
A
A
n
n
(11)

Solving for time (t) in equation (3) gives t = 361.7 s.
1.18


Exercise 15:

For the constant volume reactor, express equilibrium constant (K) in terms of
concentrations.


B A
C
C C
C
k
k
K = =
2
1
(1)

Write the mole balance for the reaction.

Initial Change Equilibrium
A 1 - 1
B 2 - 2
C 0
Total 3 - 3

Rewrite equation (1) in terms of and pressure.


( )
( )( )


= =

2 1
2
1
Lmol K (2)

Solving for , gives = 0.719 mol L
-1
.

Using the ideal gas law, find in terms of .
eq
tot
P
(3) RT n V P
eq
tot
eq
tot
=

RT
V
RT n
P
eq
tot eq
tot
) 3 ( = = (4)



Therefore,

Fractional conversion of A (f
A
) = 0.719
Final pressure ( ) = 56.2 atm
eq
tot
P



Write rate equation for species A.


C B A
A
C k C C k
dt
dC
rate
2 1
= = (5)
1.19


Express all concentrations in terms of C
A.

) (
1
1
o
A A
o
B B
C C C C
|
.
|

\
|

+ = (6)

) (
1
1
o
A A
o
C C
C C C C |
.
|

\
|
+ = (7)

Substitute equations (6) and (7) into equation (5).

) 1 ( ) 1 (
2 1 A A A
A
C k C C k
dt
dC
rate + = = (8)

Solve by hand or with a computer solver for each species and plot the composition of the
reactor versus time.



Prob 15
0
0.5
1
1.5
2
2.5
0 0.2 0.4 0.6 0.8 1
Time (hr)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
o
l

/

L
)
A
B
C



Exercise 16:


For the variable volume reactor, express equilibrium constant (K) in terms of mole
fractions and total pressure.


tot B A
C
P X X
X
k
k
K
1
2
1
= = (1)
1.20

Using the mole balance from Exercise 15, express equation (1) in terms of and P
tot
.


tot
P
K

|
|
.
|

\
|

|
|
.
|

\
|

|
|
.
|

\
|

= =

3
2
3
1
3
2
mol
L
(2)
Using the ideal gas law, the equilibrium constant can be rewritten as 0.08124 atm
-1
.

Again, use the ideal gas law to find P
tot
and solve for .

atm 85 . 73 = =
o
o
tot
tot
V
RT n
P (3)

= 0.7681 (4)

Therefore, the equilibrium conversion of A = 0.7681.

Write the rate equation for species A.


C B A
A
C k C C k
dt
dn
V
rate
2 1
1
= = (5)


C
B A A
n k
V
n n k
dt
dn
rate
2
1
= = (6)

Express V in terms of V
o
and n
A
.

(7) ) 1 (
A A
o
f V V + =


3
1
1
1
3
1
=
(
(

=
A
And
o
A
A
A
n
n
f =1 (8)

Therefore, |
.
|

\
|
+ =
A
o
n V
3
1
3
2
V (9)

Express n
B
and n
C
in terms of n
A
.


A
o
A A
o
B B
n n n n n + =
|
.
|

\
|

+ = 1 ) (
1
1
(10)

1.21

A
o
A A
o
C C
n n n n n =
|
.
|

\
|
+ = 1 ) (
1
1
(11)

Substitute equations (9), (10), and (11) into equation (6).

) 1 (
) 2 (
) 1 ( 3
2
1
A
A
o
A A C B A
n k
n V
n n k
dt
dn
dt
dn
dt
dn

+
+
= = = (12)

Solve for each species by hand or with a computer solver and plot the composition of the
reactor and the volume versus time.

Problem 16
0
0.5
1
1.5
2
2.5
0 0.2 0.4 0.6 0.8 1
Time (hr)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
o
l

/

L
)
A
B
C

Problem 16
0
0.2
0.4
0.6
0.8
1
1.2
0 0.2 0.4 0.6 0.8 1
Time (hr)
V
o
l
u
m
e

(
L
)






1.22
Exercise 17:

Write a new mole balance to account for the inert gas.

Initial Change Equilibrium
A 1 - 1
B 2 - 2
C 0
Inert 3 0 3
Total 6 - 6

Solve for , using a modified form of equation (2) from Exercise 16.


tot
P
K

|
|
.
|

\
|

|
|
.
|

\
|

|
|
.
|

\
|

= =

6
2
6
1
6
atm 08124 . 0
1
(1)

Use the ideal gas law to find P
tot
and solve for .

atm 7 . 147 = =
o
o
tot
tot
V
RT n
P (2)

= 0.7417 (3)

Therefore, the equilibrium conversion of A = 0.7417.

Write the rate equation for species A as done in Exercise 16.


C
B A A
n k
V
n n k
dt
dn
rate
2
1
= = (4)

Express V in terms of V
o
and n
A
.

) (5) 1 (
A A
o
f V V + =


6
1
1
1
6
1
=
(
(

=
A
And
o
A
A
A
n
n
f =1 (6)

Therefore, |
.
|

\
|
+ =
A
o
n V
6
1
6
5
V (7)

Express n
B
and n
C
in terms of n
A
.
1.23


A
o
A A
o
B B
n n n n n + =
|
.
|

\
|

+ = 1 ) (
1
1
(8)


A
o
A A
o
C C
n n n n n =
|
.
|

\
|
+ = 1 ) (
1
1
(9)

Substitute equations (7), (8), and (9) into equation (4).

) 1 (
) 5 (
) 1 ( 6
2
1
A
A
o
A A C B A
n k
n V
n n k
dt
dn
dt
dn
dt
dn

+
+
= = = (10)

Solve for each species by hand or with a computer solver and plot the composition of the
reactor and the volume versus time.

Problem 17
0
0.5
1
1.5
2
2.5
0 0.2 0.4 0.6 0.8 1
time (hr)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
o
l

/

L
)
A
B
C

Problem 17
0
0.2
0.4
0.6
0.8
1
1.2
0 0.2 0.4 0.6 0.8 1
Time (hr)
V
o
l
u
m
e

(
L
)





1.24