Thermodynamics of Multicomponent Systems 3C04

Assignment 2 Solutions

1. A rigid container is divided into two compartments of equal volume by a partition. One
compartment contains 1 mole of ideal gas at 1 atm, and the other contains 1 mole of ideal
gas B at 1 atm. Calculate the increase in entropy which occurs when the partition between
the two compartments is removed. If the first compartment had contained 2 moles of
ideal gas A, what would have been the increase in entropy when the partition was
removed? Calculate the corresponding increases in entropy in each of the above two
situations if both compartments contained ideal gas A.
ANSWER:
1. A) i) Partition Removed:
The volume occupied by 1 mole of A doubles - ln 2
A
S R =
The volume occupied by 1 mole of B doubles - ln 2
B
S R =
2 ln 2
TOT
S R =
ii) First Compartment - 2 Moles of Ideal Gas A:
The volume occupied by 2 mole of A doubles - 2 ln 2
A
S R =
The volume occupied by 1 mole of B doubles - ln 2
B
S R =
3 ln 2
TOT
S R =
iii) Partition Removed All Ideal Gas A:
0
TOT
S =
iv) First Compartment - 2 Moles of Ideal Gas A All Ideal Gas A:
The volume occupied by 2 mole of A doubles - 2 ln 2 S R =
Remove the partition - 0 S =
The volume occupied by 3 moles of A - ( ) 3 ln 2 3 S R =
( ) ( ) 2 ln 2 3 ln 2 3 ln 32 27
TOT
S R R R = + =

*ANSWER FROM THE BACK OF THE BOOK DOESNT MAKE A LOT OF
SENSE TO ME!

B) i) Partition Removed:

( )!
ln ln
! !
A B
A B
N N
S k k
N N
| | +
= =
|
|
\

( ) ( ) ( ) ln
A B A B A B
S k N N N N N N = + + + ln
A A A
N N N + ln
B B B
N N N +
( ) ( )
( )
( )
ln ln ln
ln ln
ln ln
A B A B A A B B
A A B B
A B
A B A B A B A B
A A B B
A B
A B A B A B A B
S k N N N N N N N N
N N N N
S k N N
N N N N N N N N
X X X X
S R N N
X X X X X X X X


= + +

| | | | | | | |
= + +
| | | |
+ + + +
\ \ \ \


| | | | | | | |
= + +
| | | |
+ + + +
\ \ \ \

2 ln 2
TOT
S R =

ii) First Compartment - 2 Moles of Ideal Gas A:
( ) ln ln
A A B B
A B
A B A B A B A B
X X X X
S R N N
X X X X X X X X

| | | | | | | |
= + +
| | | |
+ + + +
\ \ \ \


3 ln 2
TOT
S R =
iii) Partition Removed All Ideal Gas A:
( ) ( ) ln 1
A
S R N =
0
TOT
S =
iv) First Compartment - 2 Moles of Ideal Gas A All Ideal Gas A:
( ) ( ) 2 ln 2 3 ln 2 3 ln 32 27
TOT
S R R R = + =
*ANSWER FROM THE BACK OF THE BOOK DOESNT MAKE A LOT OF
SENSE TO ME!

2. An adiabatic vessel contains 1000g of liquid aluminum at 700
o
C. Calculate the mass of
Cr
2
O
3
at room temperature, which, when added to the liquid aluminum (with which it
reacts to form Cr and Al
2
O
3
) raises the temperature of the resulting mixture of Al
2
O
3
,
Cr
2
O
3
, and Cr to 1600K.

ANSWER:
2. Reaction -->
2 3 2 3
2 2 Al Cr O Cr Al O + = +
** All aluminum reacts with Cr
2
O
3


Thermodynamic Data:
( ) ( ) ( )
( ) ( ) ( )
( ) ( )
( )
( )
( )
2 2 3 298
2 2 3 298
934
3
3 5 2
2 3
3
2 1, 676, 700
2
3
2 1,134, 700
2
10, 700
20.67 12.38 10 / .
31.76 / .
106.6 17.78 10 28.53 10 / .
24.43 9
o
S g S
o
S g S
o
S l
p S
p l
p
p S
Al O Al O H J
Cr O Cr O H J
Al Al H J
Al c x T J mole K
Al c J mole K
Al O c x T x T J mole K
Cr c

+ = =
+ = =
= =
= +
=
= +
= +
3 5 2
3 5 2
2 3
.87 10 3.68 10 / .
119.37 9.30 10 15.65 10 / .
p
x T x T J mole K
Cr O c x T x T J mole K

= +


Using the thermodynamic data above one can solve for the thermodynamic values for the
reaction
( ) ( ) 2 3 2 3
2 2
S S
Al Cr O Cr Al O + = + as:


298
3 5 2
1, 676, 700 1,134, 700 541, 000
5.25 3.46 10 20.24 10 / .
o
p
H J
c x T x T J mole K

= + =
= +


and
( ) ( ) 2 3 2 3
2 2
l S
Al Cr O Cr Al O + = + as:
3 5 2
27.43 28.22 10 20.24 10 / .
p
c x T x T J mole K

= +


Solving for
973K
H for the reaction
( ) ( ) 2 3 2 3
2 2
l S
Al Cr O Cr Al O + = + :
( ) ( ) ( )
( ) ( )
3
2 2 5
973
3
2 2 5
3.46 10 1 1
541, 000 5.25 934 298 934 298 20.24 10 2 10700
2 934 298
28.22 10 1 1
27.43 973 934 973 934 20.24 10
2 974 934
K
x
H x
x
x

| |
| |
= + +
|
|
\
\
| |
| |
+ +
|
|
\
\

973
569,116
K
H J =


Heat required to raise temperature of 1mol Cr
2
O
3
to 973K:
( ) ( )
3
2 2 5
973
973
9.30 10 1 1
119.37 973 298 973 298 15.65 10
2 973 298
80, 920
K
K
x
H x
H J

| |
| |
= + +
|
|
\
\
=


Therefore, total heat available at 973K is:
973
569,116 80, 920 -488,197
K
H J = + =

Heat required to raise Cr, Al
2
O
3
, and Cr
2
O
3
to 1600K:
1mol Cr:
( ) ( )
3
2 2 5
1600
1600
9.87 10 1 1
24.43 1600 973 1600 973 3.68 10
2 1600 973
23,130
K
K
x
H x
H J

| |
| |
= + +
| |
\
\
=


1mol Al
2
O
3:
( ) ( )
3
2 2 5
1600
1600
17.78 10 1 1
106.6 1600 973 1600 973 28.53 10
2 1600 973
80, 031
K
K
x
H x
H J

| |
| |
= + +
| |
\
\
=

1mol Cr
2
O
3
:
( ) ( )
3
2 2 5
1600
1600
9.30 10 1 1
119.37 1600 973 1600 973 15.65 10
2 1600 973
81, 716
K
K
x
H x
H J

| |
| |
= + +
|
|
\
\
=


Therefore, the heat available at 1600K to increase the temperature of excess Cr
2
O
3
is:

1600
488,197-2*23,130 80, 031 361, 906
K
H J = =

Number of excess moles of Cr
2
O
3
heated:

2 3
361, 906
4.43
81, 716
excess moles of Cr O = =


5.43moles * 151.9904 g/mol = 825.3 g of Cr
2
O
3
per 53.96g of Al
2
O
3

15.3kg of Cr
2
O
3
per kg of Al
2
O
3


3. Calculate the value of G for the reaction:
( )
3 4 2 2 2
3 3 2
quartz
Si N O SiO N + = +
At 800K. What percentage error occurs if it is assumed that
p
c for the reaction is zero?
ANSWER:
Thermodynamic Data:
( ) ( ) ( )
( ) ( ) ( )
( )
( )
( )
( )
2 3 4 298 298
2 2 298 298
2 298
2 298
3
3 4
2
3 2 744, 800 113 / .
910, 900 41.5 / .
191.5 / .
205.1 / .
70.54 98.74 10 / .
43.
o o
S g S
o o
S g Quartz
o
g
o
g
p S
p Quartze
Si N Si N H J S J mole K
Si O SiO H J S J mole K
N S J mole K
O S J mole K
Si N c x T J mole K
SiO c

+ = = =
+ = = =
=
=
= +
=
( )
( )
3 5 2
3
2
3 5 2
2
89 1.00 10 6.02 10 / .
27.87 4.27 10 / .
29.96 4.18 10 1.67 10 / .
p g
p g
x T x T J mole K
N c x T J mole K
O c x T x T J mole K

+
= +
= +

Using the thermodynamic data above one can solve for the thermodynamic values for the
reaction
( )
3 4 2 2 2
3 3 2
quartz
Si N O SiO N + = + as:

298
298
3 5 2
3*910, 900 744, 800 1, 987, 900
2*191.5 3*41.5 3*205.1 113 220.8 /
26.99 99.74 10 13.05 10 / .
o
o
p
H J
S J K
c x T x T J mole K

= + =
= + =
=

Therefore at 800K the free energy can be calculated as follows:
( ) ( )
3
2 2 5
800
800
99.74 10 1 1
1, 987, 900 26.99 800 298 800 298 13.05 10
2 800 298
2, 004, 587
o
o
x
H x
H J

| |
| |
= + +
| |
\
\
=

( )
5
3
800
2 2
800
800 13.05 10 1 1
220.8 26.99ln 99.74 10 800 298
298 2 800 298
250.5 /
o
o
x
S x
S J K

| |
| | | |
= + +
| | |
\ \
\
=

( )
800
2, 004, 587 250.5 800 1, 804,187
o
G J = =
( )
800
0
1, 987, 900 220.8 800 1, 811, 260
p
o
assume c
G J
=
= =


1, 811, 260 1, 804,187
% 100 0.4%
1, 804,187
error x

= =
4. One mole of SiCl
4
vapor is contained in a 1atm pressure and 350K in a rigid container of
fixed volume. The temperature of the container and its contents is cooled to 280K. At
what temperature does condensation of the SiCl
4
vapor begin and what fraction of the
vapor has condensed when the temperature is 280K?
ANSWER:
Assume that SiCl
4
vapor behaves ideally. Therefore, the volume of the container can be
calculated as follows:

0.802057 *350
28.72
1
nRT
V l
P
= = =


Cooling of the container and its contents changes the gas pressure as:

3
0.802057 *
2.857 10
28.72
nRT T
P x T
V

= = =

The saturated vapor pressure of liquid SiCl
4
is:
( )
3620
ln 10.96 p atm
T
= +
3
3620
exp 10.96
3620
2.857 10 exp 10.96
328
P
T
x T
T
T K

| |
= +
|
\
| |
= +
|
\
=


Therefore condensation will begin at 328K.
At 280K the saturated vapor pressure is:
3620
exp 10.96 0.1396
280
P atm
| |
= + =
|
\


The number of moles of SiCl
4
in the vapor phase is therefore:

0.1396* 28.72
0.175
0.802057 * 280
PV
n moles
RT
= = =

The number of moles in the liquid phase is therefore = 1- 0.175 = 0.825.
82.5% of the vapor has condensed.
5. Below the triple point (-56.2
o
C) the vapor pressure of solid CO
2
is given as:
( )
3116
ln 16.01 p atm
T
= +
The molar latent heat of melting of CO
2
is 8330 joules. Calculate the vapor pressure
exerted by liquid CO
2
at 25
o
C and explain why solid CO
2
is referred to as dry ice.
ANSWER:
At 216.8K the triple point pressure is:
3116
exp 16.01 5.14
216.8
P atm
| |
= + =
|
\

For vapor in equilibrium with the solid phase:
( )
2 2
ln 3116 s v
H
d P
dT T RT

= =
( )
8.314*3116 25, 907
s v
H J

= =
( )
8, 330
s l
H J

=
( )
25, 907 8, 330 17, 577
l v
H J

= =

For liquid CO
2
:
( )
17, 577
ln 5.14 constant
216.
constant 11.39
R
= +
=


At 298K:
( )
17, 577
ln 11.39
8.314* 298
73.3
P
P atm
= +
=


The vapor pressure of CO
2
at 25
o
C is therefore 73.3atm.
The 1atm isobar does not pass through the stability field for liquid CO
2
.