Che 211 – Spring ’05 – Yaros-Ramos

Problem Set 1 -- Solutions

1. The volume coefficient of expansion of mercury at 0°C is 18 x 10-5 (°C)-1. The

coefficient of compressibility β is 5.32 x 10-6 bar-1. If mercury were heated
from 0°C to 1°C in a constant volume system, what pressure would be
developed?
 V   V 
V    T    P
 T  P  P T
Constant V; V  0
1  V  1  V 
       
V  T  P V  P T
0  VT V P
 P   18x 10 5 C 1
     33.8 bar/C
 T V  5.32x 10 6 bar 1
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
2. Find expressions for  S V  T ,  S  P  T ,  U V  T , and  H P  T for a gas
whose behavior can be described by the equation
V 
P   b   RT
n 

 S   P    nRT  nR
      
 V T  T V T V  nb  V  nb
 S   V    nRT   nR
        nb  
 P T  T  P T  P  P
 U   P   nR 
  T   P T  P  P P  0
 V T  T V V  nb 
 H   V    nR  nRT
  V T   V T   V   V V  nb  nb
 P T  T  P  P  P

Also find expressions for ΔS, ΔU, ΔH, ΔG and ΔA for an isothermal change.

 S   P 
   
 V T  T V
 P 
S2 V2   V
S 1
S  V 1
 T V

V2 nR V  nb 
S  V 1 V  nb
V  nR ln 2 
V 1  nb 

 U   P 
  T   P
 V T  T V
U2 V2   nR  
U  U 1
U  V 2
T    P  V  0
 V  nb  

 H   V 
  V T  
 P T  T  P
H2 P2   V   P2
H  H H  P V  T    P  P nb P  nb P 2  P1 
1 1   T  P  1

V  nb  P 
G  H  TS  nb  P 2  P1   TnR ln 2   nb P 2  P1   nRT ln 1 
V 1  nb   P2 

P  P 
A  U  TS  0  nRT ln 1   nRT ln 1 
 P2   P2 

3. If the standard entropy of liquid water is 298.15 K is 69.96 J K-1mol-1,

calculate the entropy of water vapor in its standard state (i.e. an ideal gas at
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
298.15 K and 1.01325 bar). The vapor pressure of water is 3168 Pa at
298.15 K and its enthalpy of vaporization is 2.436 kJ g-1.

S1  S2  S3
sat liq sat vap vapor  ideal gas 
T  298.15 K T  298.15 K T  298.15 K
P  3168 Pa P  3168 Pa P  1.01 bar
S 1  69.96 J/kmol

S3  S 3  S 2   S 2  S 1   S 1
H vap 2.436 kJ/g  1000 J  18.02 g 
S 12   S 2  S 1        147.2 J/mol K
T 298.15 K  1 kJ  1mol 

P2  V 
S 23   S 3  S 2   P   P ; PV  RT
1  T  P
P2 R  P   1.01 bar 
S 23  P1
 P  R ln 3   8.314 J/mol K ln
 P   P2 
  28.8 J/mol K
 0.03168 bar 

S 3  28.8  147.2  69.96  188.4 J/mol K

 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions

4. A gas at 350°C and molar volume ν = 600 cm3 mol-1 is expanded in an

isentropic turbine. The exhaust pressure is atmospheric. What is the
exhaust temperature?
The ideal-gas heat capacity at constant pressure is cp0 = 33.5 J mol-1 K-1.
The P-V-T properties of the gas are given by the van der Waals equation,
with a = 56 x 105 bar (cm3 mol-1)2 and b= 45 cm3 mol-1.

S1  S2  S3
Isothermal expansion Isochoric cooling (ideal gas) Isothermal compression

 S   S  RT a
S    V    T P 
 V T  T V V-b V 2
 P  C    P  R
S    V   v T   
 T V T   T V V b
 
  P  T2 C v V2  P 
S  V 1
  V 
 T V T 1 T
T  
  V  0
 T V
For an ideal gas : C P  C v  R
  R  T2  C P  R  V2  R 
S  V 1
 V 
V  b  T 1

 T

T 



 V  0
V  b 
V  b 
R ln 2  T
  C P  R ln 2  0 
V 1  b  T1
Rearranging and substituting into van der Waals EOS...
R C P R
V  b 
T2  T 1  1 
V 2  b 
R C P R
RT 1 V 1  b  a
P  1.01bar    
V2  b V 2  b  V 22
Iterate to solve for V2 . V2  317.8 cm 3 /mol.
Plug into EOS to solve for T2 . T2  188 K
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
5. Consider the equation of state
 
 P  n  v  m   RT
 1 
 v 2T 2 
where n and m are constants for any gas. Assume that carbon dioxide
follows this equation Calculate the compressibility factor of carbon dioxide at
100°C and at a volume of 6.948 dm3 kg-1.

 n 
 P  2 0.5  V  m   RT
 V T 
can be written as
PT V  PmT V
0.5 3 0.5 2
 nV  nm  RT 1.5 V 2
 RT  2  n  nm
V3  m  V   0.5
V  0 (1)
 P   PT  PT 0.5

At the critical point, there are 3 roots for V  VC or

 P   2P 
    0
 V  TC  V 2 
  TC
 V  VC  3  V 3  3VC V 2  3VC2 V  VC3  0 (2)

Comparing (1) and (2)

RT c
m  3Vc
Pc
n
 3Vc2
Pc Tc0.5
nm
 Vc3
Pc Tc0.5

therefore... m  Vc 3
3RT c RT c
Vc  or m 
8Pc 8Pc
27R 2 Tc2.5
n  3Vc2 Pc Tc0.5 
64Pc

EOS may be rewritten...

 
RT  1 n  PV 1 n
P    or z   
V 1  m 1.5
RT V  RT 1 m RT 1.5 V
 V  V
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
From Smith & van Ness
Tc  304.K Pc  73.8 bar Vc  94.0 cm 3 /mol

m  0.0428 L/mol
n  63.78 bar/(L mol)2K 0.5

dm 3  1 kg  1 L  44 g 
At 100 C , V  6.948      0.3057 L/mol
kg 3
 1000 g  1 dm  mol 
z  0.815
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
Consider an aqueous mixture of sugar at 25°C and 1 bar pressure. The
activity coefficient of water is found to obey a relation of the form
ln  w  A1  x w  ,
2

where γw is normalized such that γw  1 as xw  1 and A ia an empirical

constant dependent only on temperature.
Find an expression for γs, the activity coefficient of sugar normalized such
that γs  1 as xw  1 (or as xs  0). The mole fractions xw and xs refer to
water and sugar, respectively.

Gibbs  Duhem : SdT - VdP   x dμ

i i 0
at constant T & P :  x dμ i i 0
x w dμ w  x s dμ s  0
xw  xs  1 dx w  dx s
μ w  μ w  RTln γ w x w
μ s  μ s  RTln γ s x s
 lnγ w 1 
dμ w  RT  x w  x w 
 x w xw 
 lnγ s 1 
dμ s  RT  x s  x s 
 x s xs 
 lnγ w 1   lnγ s 1 
x w RT   x w  x s RT 
   x s  0
 x w xw   x s x s 
 lnγ w   lnγ s 
xw
  1 x w   x s  1   x w   0
 x w   x s 
lnγ w lnγ s
xw  xs
x w x s
ln  w  A 1  x w 2
lnγ w 
 A 1  x w 2  2 A 1  x w   1  2 A 1  x w 
x w x w
lnγ s
x w  2 A 1  x w   x s
x s
lnγ s
 2 Ax w
x s
lnγ s  2 Ax w x s  2 Ax w x w
1 1
 s
lnγ s  x w
2 Ax w x w

ln1  lnγ s  2 A 1 - x 2  
 
w

lnγ s  2 A x 2  1
w
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
6. Using only data given in the steam tables, compute the fugacity of steam at
320°C and 70 bar.

fi
G  RT ln where f i  is an ideal gas @ P  , choose P   1 kPa
f i
T  320C  593.15K
G  H - TS

From the steam tables in Smith & van Ness :

@ 70 bar (7000 kPa) 300C 325C
H(kJ/kg) 2839.4 2936.3
S(kJ/kg K) 5.9327 6.0982

@ 1 kPa 300C 350C

H(kJ/kg) 3076.8 3177.5
S(kJ/kg K) 10.3450 10.5133

Extrapolating...
2936.3 - 2839.4 H - 2839.4 6.0982  5.9327 S  5.9327
@ 70 bar  
325K - 300K 320K - 300K 325K  300K 320K  300K
H  2916.9 kJ/kg S  6.0651kJ/kg K
3177.5  3076.8 H  3076.8 10.5133  10.3450 S  10.3450
@ 1kPA  
350  300 320  300 350  300 320  300
H  3117.1kJ/kg S  10.4123kJ/kg K

 1000 J  1 kg  18.02 g 
ΔG   2916.9  3117.1   593.15K 6.0651 10.4123  2378 kJ/kg    
 1 kJ  1000 g  mol 
f f ΔG 42851J/mol
ln i  ln i    8.68
fi 1 kP RT 8.314 J/mol K  593.15 K 
f i  5884 kPa  58.8 bar
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
7. A gas, designated by the subscript 1, is to be dissolved in a nonvolatile liquid.
At a certain pressure and temperature the solubility of the gas in the liquid is
x1 (where x is the mole fraction). Assume Henry’s law holds. Show that the

d ln x1   h1
change in solubility with temperature is given by 
d 1 T  R
  
where  h1  h1( in liquid solution )  h1( pure gas ) at the same pressure and
temperature. On the basis on physical reasoning alone, would you expect to
be positive or negative?
f 1L  f 1G 1 : solute
at constant P :
  ln f 1L   G 
  T    ln f 1  T
 T   T 
 P  P

the solute is not volatile. Its composition is independent of T.

the solute concentration in the liquid phase does depend on T.

  ln f 1L    ln f 1L    ln f 1G 
  T     ln x 1    T
 T    ln x 1   T 
  P ,x  T ,P  P

fi
G i  G i  RT ln
f i
 G i  G i 
    1 dG  G dT  1 VdP  SdT    H  TS dT
T  RT  RT RT 2 RT  RT 2 
 
 G i  G i 
    V dP  S dT  H dT  S dT
T  RT  RT RT RT 2 RT
 
 G i  G i 
    V dP  H dT
T  RT  RT RT 2
 
 Che 211 – Spring ’05 – Yaros-Ramos
Problem Set 1 -- Solutions
at constant P
 G i  G i    
     H i  H i dT
T  RT   RT 2 
   
  f i   H  Hi 

ln    i dT
T  f i   RT 2 
 

Substituti ng...
H 1  H 1L   ln f 1L  H 1  H 1G
  ln x 
RT 2   ln x  1
RT 2
 1 T ,P

Henry' s law : fi  x i k wher e k is a constant

lnfi  ln x i k
 ln f i
1
 ln x i
H 1  H 1L H 1  H 1G
 1  ln x 1 
RT 2 RT 2

 ln x 1  1
H L  H 1G
RT 2

T
 
1  1
T2
 ln x 1 H L  H 1G
 1
1  
T
RT 2
 ln x 1  H
 
1
T

RT 2
where ΔH  H1L  H1G

Physically H1G  H1L . Thus, x1 decreases with increasing T.