1 Express the volume expansibility and the isothermal compressibility as function of

density and its partial derivatives for water at 50and 1bar ,K=44.18X10-6/bar
To what pressure must water be compressed at 50 to change its density by 1%?
Assume that K is independent of P.
Solution :
1 V V d
( ) P ( ) P -
Volume expansibility: V T T dT

dV 1 d
K - ( )T
isothermal compressibility: dP dP
if k is assumed constant in the 50
d d
k KdP ln 2 k ( p 2 p1 )
dP 1

2
1.01andP1 1bar
1

Yield to P2 =226.22bar

2.Generally, volume expansibility and isothermal compressibility k depend on

K
T and P. Prove that : ( ) T ( ) P
P T
solution :
the definition of k and are as follows :

1 V
( )P
V T
1 V
K ( )T
V P
So
V 1
( ) P
V
( ) T ( T ) T ( V ) P ( ) P
1
P V P P T
V
( ) P
1 V V
( T ) T 2 ( ) P ( ) T
1
V P V T P

1
 The same method, we can see
V
( )T
k 1 p 1 V V
( )P ( ) P 2 ( ) P ( )T
T V T V T P
K
So ( ) T ( ) P
P T
AP
3.The equation for liquid is written for an isotherm as: V V0 (1 ) .where v is
BP
molar or specific volume ,vis the hypothetical() molar or specific volume at
zero pressure, and A and B are positive constants. Find an expression for the
isothermal compressibility consistent() with this equation.
V AB
Solution : V
P T B P
2 0

1 V
K
V P T
1 V

AP P T
V0 (1 )
BP
BP AB

B P AP B P 2
AB

B P B P AP

V
4.For liquid ,the isothermal compressibility is given by k .where C and b
V ( P b)
are function of temperature only. If 1kg water is compressed isothermally and
reversibly from 1 to 500 bar at 60,how much work is required ?at
60,b=2700bar,c=0.125 cm 3 / g .
Solution :
1 V
The definition of isothermal compressibility is k ( )T
V P
1 V V V c
k ( )T ( )T
V P V ( P b) P Pb
C
For liquild ,the P is independent of T ,then dV dP
P b
C
And dW PdV P dP
Pb

2
 So
500 C 500 b
W P dP C (1 )dP
1 Pb 1 Pb
0.125(500 1 2700[ln(500 2700) ln(1 2700)]
5.16bar.cm 3 / g
1kg water : W 5.16 * 101.325 523 J

5.Calculate Z and V for sulfur hexafluoride at 75 and 15 bar by the following equa-
tions:
(a) The truncated virial equation [Eq. (3.39)] with the following experimental
values of
virial coefficients:
B 194 cm3mol-1 C15,300 cm6 mol-2
(b) The truncated virial equation [Eq. (3.37)]with a value of B from the
generalized
Pitzer correlation [Eq. (3.59)]
(c) The Redlich/Kwong equation.
(d) The Soave/Redlich/Kwong equation.
(e) The Peng/Robinson equation.
For sulfur hexafluoride, Tc318.7 K, Pc37.6 bar, Vc198 cm3 mol-1
and
m0.286.

Solution:(a)The equation [Eq(3.39)] is :

PV B C
Z 1 2 (1)
RT V V
156.7 9650
So Z 1 2 (2)
V V
Combine eq(1) and eq(2) can yield :
RT B C 83.14 323.15 156.7 9650
V (1 2 ) (1 2 )
P V V 15 V V
The result of V is calculated via the computer
V=1624.91cm3mol-1
PV 15 1624.91
whence Z 0.9072
RT 83.14 323.15
(b) Solving eq(3.37) for V gives
RT 83.14 323.15
V B 156.7 1634.41cm3 mol 1
P 15
PV 15 1634.41
Whence Z 0.9125
RT 83.14 323.15
(c)The pressure as given by the Redlich/Kwong equation is
RT a(T )
P
V b V (V b)

3
 Looking up for the document: T c =305.33 P c =48.70bar
T 323.15
Tr 1.06
Tc 305.33

1.060.5 83.142 305.332

a 0.42748 5494053.73bar cm6
48.70
83.14 305.33
b 0.08664 45.16cm3
48.70

83.14 323.15 5494053.73

So 15
V 45.16 V (V 45.16)
Yield V=1622.79cm3mol-1
PV 15 1622.79
Whence Z 0.9060
RT 83.14 323.15
(d) The SRK equation is
RT a RT ac
P
V b V (V b) V b V (V b)

R 2Tc2 (83.14) 2 (305.33) 2

ac 0.42748 0.42748 5656474.52bar cm6
pc 48.70

RTc
b 0.08664 45.16cm3
pc

0.5 1 (0.48 1.574w 0.176 w2 )(1 Tr0.5 ) 0.98125 (w=0.099)

Yields =0.9629 Then a ac 5446619.32

83.14 323.15 5446619.32

15
V 45.16 V (V 45.16)
Yields V=1624.894 cm3mol-1
PV 15 1624.89
Whence Z 0.9072
RT 83.14 323.15
(e)The PR equation is
RT a
P
V b V (V b) b(V b)

R 2Tc2 (83.14) 2 (305.33) 2

ac 0.457235 0.457235 6050196.80bar cm6
pc 48.70

RTc
b 0.077796 40.55cm3
pc

4
 0.5 1 (0.37646 1.54226 w 0.26992w2 )(1 Tr0.5 ) 0.9844

Yields =0.9690 Then a ac 5862640.70

83.14 323.15 5862640.70

15
V 40.55 V (V 40.55) 40.55(V 40.55)
Yields V=1605.67 cm3mol-1
PV 15 1605.67
Whence Z 0.8965
RT 83.14 323.15
6.For a gas described by the Redlich/Kwong equation and for a temperature greater
than
TCdevelop expressions for the two limiting slopes,
Z Z
lim lim
P 0 P
T P
P T
Note that in the limit as P0Vand that in the limit asPV b.

Solution:
(a)By the R-k equation
RT a
P 0.5 (1)
V b T V (V b)
The compressibility factor is defined by the equation
PV
Z (2)
RT
The other expression of Z is yielded include Eq(1) and Eq(2):
V a
Z (3)
V b RT (V b)
2.5

Z b a V
So ( )T [ ]( )T (4)
P (V b) 2
RT (V b) P
2

V 1 1
Then ( )T = (5)
P P RT a a
( )T
V V-b bV
2 2
b(V b) 2

1
If we assume t2 so that we can yield
(V b) 2

1 t2 1 t2
and
(V b) 2 (1 2bt ) 2 V (1 bt ) 2
Then combine these equation ,we can yield the equation :

5
 a
b
Z RT (1 2bt ) 2
2.5
( )T
P RT
a

a
b(1 bt ) b(1 2bt ) 2
2

V
When P 0 and T cons tan t so ,Then t 0
t0
On the basis of the aboved equation ,we can yield :
a
b
Z Z Z RT (1 2bt ) 2 2.5
lim( )T lim( )T lim( )T lim
P P V 0 P t P t a a
RT
b(1 bt ) b(1 2bt ) 2
2

a
b
Z Z Z RT (1 2bt ) 2 2.5
b a
lim( )T lim( )T lim( )T lim = 2 2.5
P 0 P V P t 0 P t 0 a a RT R T
RT
b(1 bt ) b(1 2bt )
2 2

(b)When P and T cons tan t , so V 0 .Then t

a
b
Z Z Z RT (1 2bt ) 2 2.5
b
So lim( )T lim( )T lim( )T lim =
P P V 0 P t P t a a RT
RT
b(1 bt ) b(1 2bt )
2 2

7.The Boyle temperature is the temperature for which:

Z
lim 0
P 0 P
T
(a) Show that the second virial coefficient B is zero at the Boyle temperature.
(b) Use the generalized correlation for BEq. (3.59), to estimate the reduced
Boyle
temperature for simple fluids.
Solution:
BP
Z 1
RT

( Z 1) Z BPc

B
lim 0 B=0, While, B 0 B1
lim
p 0 P T RT p T RTC

So, B 0 B1 0 ,
At boyle temperature , simple fluid, 0 ,then

6
 0.422 0.172
0.083 1.6
(0.139 4.2 ) 0
Tr Tr

0.422
0.083 1.6
0
Tr

1
0.422 1.6
Tr ( ) 2.763
0.083
8. (a)Making use of the fact that Eq6.20 is an exact differential expression, show that:
C P 2V
( ) T T ( 2 ) P
P T
What is the result of application of this equation to an ideal gas?
(b) CV and C P are defined as temperature derivatives respectively of U and H.
because these properties are related, one expects the heat capacities also to be related.
show that the general expression connecting C P to CV is

P V
C p CV T ( )V ( ) P
T T
Solution :
H
(a) The definition of C p is C p = ( )P
T

So

C P H H V
( )T = [ ( ) P ]T [ ( ) T ] P [ (V - T( ) P )] P
P p T T p T T

V V 2V 2V
( ) P ( ) P T ( 2 ) P T ( 2 ) P
T T T T
RT
ideal gas PV=RT V
P
V R
so dH C P dT [V T ( ) P ]dP C P dT [V T ]dP C P dT
T p
H (U PV ) U V
(b) The definition of C p is C p = ( )P [ ]P ( ) p P( ) P .......(1)
T T T T

7
 U U (T , V )
U U U
dU ( )V dT ( ) T dV CV dT ( ) T dV
T V V
U U V
( ) P CV ( ) T ( ) P .......(2)
T V T
U V
(1)-(2) C P CV (( ) T P)( ) P
V T
U A TS
U ( A TS ) P
( )T ( ) T P T ( )V
V V T
P V
C p CV T ( )V ( ) P
T T

9.The PVT behavior of a certain gas is described by the equation of state:

P V b RT

where b is a constant. If in addition C V is constant, show that:

(a) U is a function of T only.
(b) const.
(c) For a mechanically reversible process, PV-b)const.
Solution:
p V b RT
P R
(a)
T V V b
P RT
dU CV dT T P dV CV dT p dV CV dT
T V V b

CV is constant So U is a function of T only

RT V R
V b
P T P P
(b)
V P RT R R 2T
C P CV T R
T P T V P V b PV b

CP
Because CV is constant C P CV R const const
CV

(c) A mechanically reversible process can be considered as an adiabatic

process : dU PdV

8
 CV R
CV dT PdV dT dV
T V b
C CV
1
dT R dV dV dV
P
T CV V b CV V b V b
V b P T
1 ln 2 1 ln( 2 1 ) 1 ln 1 ln 2
T2 T P
ln
T1 V1 b P2 T1 P2 T1
T2 1 P1
ln ln
T1 P2
1
T2 P1 P2 V2 b

T1 P2 P1 V1 b
1
V2 b P1

V1 b P2

P1 V1 b P2 V2 b P1 V1 b P2 V2 b
1 1

So PV b const

sat sat
10.Let p1 and p1 be values of the saturation vapor pressure of a pure liquid at

absolute temperatures T1 and T2 .testify the following interpolation formula for

estimation of the vapor pressure p sat at intermediate temperature T:

T (T T1 ) p2
sat
ln P1 2
sat sat
ln P ln
T (T2 T1 ) p1sat
Solution:
B
The equation 6.70 is ln p sat A
T
B
A
sat
ln p1
T1
So
B
A
sat
ln p 2
T2
sat
T2 p
A ln p1
sat
ln 1 sat
T1 T2 p 2
sat
T1T2 p
B ln 2 sat
T1 T2 p1
Then

9
 sat sat
T2 p T1T2 p
ln p sat ln p1 ln 1 sat
sat
ln 2 sat
T1 T2 p 2 T (T1 T2 ) p1
T (T T1 ) p 2
sat

ln P1 2
sat
ln
T (T2 T1 ) p1 sat

11.Assuming the validity of Eq. (6.70), derive Edmister's formula- for estimation
of the
acentric factor:
3
log Pc 1
7 1
where =T n T c T n is the normal boiling point, and P C is in (atm)

B
Solution: Antoine equation : ln p s A (1)
T
B
ln pc A (valid from triple point to critical point) (2)
Tc

B B
(1)-(2): ln p s ln pc
T Tc

T 0.7Tc

3 B
ln p s ln pc
7 Tc

ps 3B
lg lg e 3
pc 7 Tc

B
Rearrangement of Equation2gives: log Pc ( A ) log e ,that is
Tc

1
lg e lg Pc 4
B
A
Tc

ps 3B 3B 1
Substitution of (4) into (3) gives: lg lg e = (5)
pc 7 Tc 7Tc A B
Tc

ps
w log( Prs )Tr 0.7 1 log( )T 0.7 1 (6)
pc r

10
Normal boiling point implies the pressure is 1atm.,
B B
ln Pns A 0 Ps n =1atm So A ;
Tn Tn

Tn
Considering Substitution of (5) into (6) leads to :
Tc
3 B 1 3
w log Pc 1 log p c 1
7 Tc B

B 7 1
Tn Tc

12.A liquid mixture of species 1/ species 2 for which 1 =0.6 is in equilibrium with
its vapor at 150 . Determine the equilibrium pressure p and vapor

composition 1 from the following information:

GE
A x 1 x2
RT

78 and P2sat 34 kPa.

sat
At 150, P1

The system forms an azeotrope at 150 for which x1 y1 0.3 .

az az

Solution:
(nG E / RT )
ln 1 ( )T , P ,n2 Ax2
2

n1

(nG E / RT )
ln 2 ( ) T , P ,n1 Ax1
2

n2

Since the system forms an azetrope at 144,then xi y i ;

According to phase equilibrium equation:

py i i xi iis pis ( PF ) i
V

iV is 1 (low pressure),(PF) i =1

py i xi i pis , pi xi i pis (1)

p ipis 1 p1s 2 p 2s
ln 1 ln p1s ln 2 ln p 2s
Azeotrope :
Ax 22 ln p1s Ax12 ln p 2s
A( x 2 x1 ) ln p 2s ln p1s ......(2)

11
At azeotrope point, substitution for x1az 0.3 to equation(2) yields:

ln p 2s ln p1s ln p 2s ln p1s 0.830

A 2.075
x 2az x1az 1 2 x1az 0.4

When x1 0.6 ,

p p1 p 2 x1 1 p1s x 2 2 p 2s 0.6 expAx 22 p1s 0.4 expAx12 p 2s 40.02 kPa

The corresponding value of y 1 is then found from equation (1):
x1 1 p1s 0.6 exp(2.075 * 0.4 2 ) * 78
y1 0.839
p 40.02
13.If the molar density of a binary mixture is given by the empirical expression:
a 0 a1 x1 a 2 x1 2

Find the corresponging expression for V 1 and V2 .
Solution:
1 1
V
a 0 a1 x1 a 2 x1
2

Then
dV a1 2a1 X 1
V1 V X 2 V X2
(a 0 a1 x1 a 2 x1 ) 2
2
dX 1
1 a X 2a1 X 1 X 2
1 1
a 0 a1 x1 a 2 x1 (a 0 a1 x1 a 2 x1 2 ) 2
a 0 a1 ( X 1 X 2 ) 2a1 X 1 X 2 a 2 x1
2

(a 0 a1 x1 a 2 x1 ) 2
2

dV a1 2a1 X 1
V2 V X 1 V X1
(a 0 a1 x1 a 2 x1 ) 2
2
dX 1
1 a X 2a1 X 1 X 2
1 1
a 0 a1 x1 a 2 x1 (a0 a1 x1 a 2 x1 2 ) 2
a 0 2a1 X 1 3a 2 x1
2

(a 0 a1 x1 a 2 x1 ) 2
2

14.The excess Gibbs energy of a binary liquid mixture at T and P is given by:
GE/RT-2.6x 1 -1.8X 2 )x l x 2
(a) Find expressions for In y 1 and Iny 2 at T and P

12
 (b) Show that when these expressions are combined in accord with Eq.11.95)
the given equation for GE/RT is recovered.
(c) Show that these expressions satisfy Eq. 11.96), the Gibbs/Duhem
equation.
(d) Show that (d lny 1 /dx l )x 11 (d ln y 2 /dx l )x l=0 0.
(e) Plot GE/RTln y 1 and ln y 2 as calculated by the given equation for GE/RT

and by the equations developed in (a) vs. x 1 Label points ln 1 and

ln 2 and show

their values.
Solution:
GE
M (2.6 X 1 1.8 X 2 ) X 1 X 2
RT

dM dM
M1 M X 2 M 2 M X1
dX 1 dX 1

1
ln r1 (2.6 X 1 1.8 X 2 ) X 1 X 2 X 2 [(2.6 1.8) X 1 X 2 ( 2.6 X 1 1.8 X 2 )(1 2 X 1 )]
( 2.6 X 1 1.8 X 2 ) X 1 X 2 [ 0.8 X 1 X 2 ( 2.6 X 1 1.8 X 2 5.2 X 1 3.6 X 1 X 2 )
2

X 2 ( 2.6 X 1 1.8 X 1 X 2 1.8 0.8 X 1 2.6 X 1 2.8 X 1 X 2 )

2 2

X 2 ( 1 . 8 0 . 2 X 1 1 . 6 X 1 )
2

1.8 X 2 1.6 X 1 X 2
2 2

ln r2 2.6 X 1 1.6 X 1 X 2
2 2

d ln r1
4.8 X 1 2.8 X 1 2
2

dX 1
d ln r2
4 . 8 X 1 2 X 1
2

dX 1

13
GE
X 1 ln r1 X 2 ln r2
RT
(1.8 X 2 1.6 X 1 X 2 ) X 1 X 2 (2.6 X 1 1.6 X 1 X 2 )
2 2 2 2

X 1 X 2 (1.6 X 1 1.6) 0.2 X 1 X 2 X 2 X 1 (1.6 1.6 X 2 ) X 2 X 1

2 2 2 2

1.8 X 1 X 2 1.6 X 1 X 2 2.6 X 2 X 1 1.6 X 1 X 2

2 2 2 2 2 2

1.8 X 1 X 2 2.6 X 2 X 1
2 2

(2.6 X 1 1.8 X 2 ) X 1 X 2
3

X d ln r ( 4.8 X 1 2.8 X 1 2) X 1 4.8 X 1 2 X 1X 1

2 2
i i
i

4 . 8 X 1 2 . 8 X 1 2 X 1 - 2 X 1 X 2
2 2

2 X
1 - X 1 1 - X 2

2 X
1 - X 1 X 1

d ln r1
X 1 -4.8 2.8 2 0
dX 1 1
d ln r2
X1 0 0
dX 1
X 2 1

lnr1 lim lnr1 1.8
X 1 0
X 1 1

lnr2 lim lnr2 2.6
X 2 0

0 .0
C

-0 .5 A

-1 .0
B
Y

-1 .5
E 3 2
A :G /R T = 0 .8 X 1 + X 1 -1 .8 X 1
-2 .0 2 3
B :ln 1 = 1 .4 x 1 -1 .6 x 1 + 2 x 1 -1 .8
3 2
C :ln 2 = -1 .6 x 1 -x 1
-2 .5

0 .0 0 .2 0 .4 0 .6 0 .8 1 .0
X

14