BG 2142 HW#1 (2014) Solution by David Lou

1

Q1:
Using ideal gas law:
P
Ideal
=
V
nRT
=
3
10 1.42
300K 8.314
-
= 17.5610
5
Pa = 17.56 bar
Using Van der Waals Equation:
P=
nb V
nRT

- a (
v
n
)
2

=
3 - 3 -
10 0.032 - 10 1.42
300 8.314

2 3 -
) 10 (1.43
0.1355

=1796974.06 - 67198.97 Pa (note: here I convert all units to SI unit)
a =1.355 bar dm
6
mol
-2

=1.35510
5
10
-6
Pa m
6
mol
-2

=0.1355 P
a
m
6
mol
-2

b =0.0320 dm
3
mol
-1

=0.3210
-4
m
3
mol
-1

P
vdw
= 17.30 10
5
Pa = 17.30 bar
P
vdw
< P
Ideal

Attractive force dominant










BG 2142 HW#1 (2014) Solution by David Lou
2

Q2:
V=20 L 60
o
C 1 atm
P
H2O
= 0.120 atm 78 mol%N
2

21 mol%O
2
dry air
1 mol%Ar
a):
atm
atm
P
P
x
Total
O H
O H
1
12 . 0
2
2
= = = 12%
% 64 . 68
1
% 78 88 . 0
2
2
=

= =
Total
N
N
P
P
x
% 48 . 18
1
% 21 88 . 0
2
2
=

= =
Total
O
O
P
P
x
% 88 . 0
1
% 1 88 . 0
=

= =
Total
Ar
Ar
P
P
x
b): at %RH=100% P
H2O
= 0.197 atm
At constant temperature, apply the ideal gas law PV=nRT to the water vapor
( )
f
f
O H i i O H
V P V P
2 2
) ( =

L L V
P
P
V
i
f O H
i O H
f
2 . 12 20
197 . 0
12 . 0
) (
) (
2
2
= = =

c): initially 1364 . 0
88 . 0
12 . 0
2 2
= = =
air
O H
air
O H
P
P
n
n

at the total final pressure of 200 atm, condensation has occurred, therefore
atm P P
O H O H
197 . 0
2 2
= =
-

And P
air
=200 0.197= 199.803 atm
000986 . 0
803 . 199
197 . 0
2 2
= = =
air
O H
air
O H
P
P
n
n

Therefore, % condensed =
air
air
n
n
1364 . 0
) 000986 . 0 1364 . 0 (
= 99.3%
BG 2142 HW#1 (2014) Solution by David Lou
3

Q3:
(a):
( ) b V V T
a
b V
RT
P
m m m
+

=
1
(A)
At T=T
C
, 0 ) ( =
c
c
c
T
m
V
P
, 0 ) (
2
2
=
c
c
c
T
m
V
P

c
T
m
V
P
) (
c
c
= -
2 2 2
) (
) 2 (
) ( b V V
b V
T
a
b V
RT
m m
m
c m
c
+
+

=0 (1)
c
T
m
V
P
) (
2
2
c
c
=
4 4
2 2 3 2 2
3
) (
) 2 6 4 )( 2 ( ) ( 2
) (
2
b V V
b V b V V b V b V V
T
a
b V
RT
m m
m m m m m m
c m
c
+
+ + + +
+

=0
=
4 4
2 2
3
) (
) 2 )( ( 2 ) 2 ( ) ( 2
) (
2
b V V
b V b V V b V b V V
T
a
b V
RT
m m
m m m m m m
c m
c
+
+ + + +
+

=0 (2)
From Equ (1):
2 2 2
) (
) 2 (
) ( b V V
b V
T
a
b V
RT
m m
m
c m
c
+
+
=

(3)
From (2):
3 3
2
2
) (
) 2 ( ) (
) (
) ( b V V
b V b V V
T
a
b V
b V
RT
m m
m m m
c
m
m
c
+
+ +
=

(4)
) (
) 2 ( ) (
) ( ) 2 (
2
b V V
b V b V V
b V b V
m m
m m m
m m
+
+ +
= +
Re-arrange to get:
3 3 2 2 3
2 3 3
m m m m
V b b V b V V = + + +

3 3
2 ) (
m m
V b V = +

m
V +b=
m
V
3
2
y

m m
y
V V b 26 . 0 ) 1 2 (
3
= =
or:
m
V = 3.8473 b (5)

BG 2142 HW#1 (2014) Solution by David Lou
4

Now substitute (5) into Equations (3) & (A):
( )
2 2
2
2
3
) 8473 . 3 ( ) 8473 . 3 (
8473 . 3 2
8473 . 8
b b b
b b
b b a RT
c
+
+
=


= 20268 . 0
2 2
2
b b
b b
a
b
a
RT
c
202677 . 0
2
3
= (6)
P
c
=
b
RT
c
8473 . 2
-
2
64902 . 18
1
b
T
a
c

Both sides, multiply by b and move P
c
to the right, put (a/b) from Equ (6) to get:
b = ]
202677 . 0 64902 . 18
1 1
8473 . 2
[
1
2
3
c
c
c
c
RT
T
RT
P

b = 0.08664
c
c
P
RT

From Equ (6)
a=
202677 . 0
2
3
c
RT
c
c
P
RT
08664 . 0
a = 0.42748
c
c
P
T R
2
5
2


x=0.42748
y=0.08664
From the example, the analytical a =
c
c
y
P
T R
2
5
2
) 1 2 ( 9
1
3

BG 2142 HW#1 (2014) Solution by David Lou
5

(b)



(c):
(i) for V
m
= 0.1L
from ideal gas law
PV=n RT
PV
m
=RT
P=
m
V
RT
=
3
10 1 . 0
) 40 15 . 273 ( 314 . 8

+
=26035291Pa
=260.35 bar
=256.95 atm
From R. K. Equation

( ) b V V T
a
b V
RT
P
m m m
+

=
1

=
3 3
5 6
3
10 ) 02971 . 0 1 . 0 )( 10 1 . 0 ( 15 . 313
10 10 63 . 64
10 ) 02971 . 0 1 . 0 (
15 . 313 314 . 8

BG 2142 HW#1 (2014) Solution by David Lou
6

=37039822.165 2.8156910
7

P = 88.83 bar
P
RK
<P
ideal
Attractive interaction is dominant
(ii) For V
m
= 100 L
From ideal gas law:
P
ideal
=
m
c
V
RT
= bar Pa 2604 . 0 3 . 26035
10 100
15 . 313 314 . 8
3
= =

From R. K. Equation
P
R.K.
=
3 3
5 6
3
10 ) 02971 . 0 100 )( 10 1 . 0 ( 15 . 313
10 10 63 . 64
10 ) 02971 . 0 100 (
15 . 313 314 . 8

= 0.2604310
5
-0.00030510
5

P
RK
= 0.26006bar
P
RK
P
ideal
Under such a large molar volume,
The CO
2
gases can be approximately as ideal gas.











BG 2142 HW#1 (2014) Solution by David Lou
7

Q4.
( )
( )
( )
( ) ( )
( )
( )
( ) ( )
( )
( )
( )( )
( )
2
2
2
2
2
0
2
2
2
0
1
;
1
1 0
1 1 4
2
1 1 4
lim
2
2 1 4
2 1
lim
f i f i
i i
i f
i f f i f i
f i f i i i f
i i i i i f i
f
i
i i i i i f i
i
i i i i f
i i
i i
P V P P
PV
T T
PT P T P P
P T P T P PT
T P T P TT P
P
T
d T P T P TT P d
df d
dg d d T d
T P P TT P
T P
T P

( +

=
( = +

+ =
+
=
+
=
+
+
+
=
( )
2
2 4
4
2
2 2
2
2
i i i f
i i
i f i
i
i i
i i i i i f i f
i i
T P TT P
T P
TT P
T
T T
T P PT T P T P
T T

+
+
=
+ +
= =