CHEG 211 Chemical EngineeringThermodynamics

Solution to Internal Exam #2

July18, 2018

Question 1)

(1.1)
The vapor pressure of tert-butyl ether ( ) equals the system pressure at x1 = 1.0000:
49.624 kPa.
The vapor pressure of dichloromethane ( ) equals the system pressure at x2 = 1.0000 (or
x1=0.0000): 85.265 kPa

(1.2)
  =   
 = 1 −  = 1 − 0.2457 = 0.7543
 = 1 −  = 1 − 0.3880 = 0.6120
P = 65.096 kPa
 = 85.265 
  0.7543 × 65.096
 =  = = 0.94
  0.6120 × 85.265
(1.3)
P = 56.833 kPa,
x1= 0.5749

(1.4)

=    +   

  0.8238 × 50.455
 =  = = 0.9882
  0.8476 × 49.624
  (1 − 0.8238) × 50.455
 =  = = 0.6842
  (1 − 0.8476) × 85.265
  = (   +   )

= 8.314 × (35 + 273.15)(0.8476 0.9882 + 0.1524 0.6842)
  ∙ 

= −175.0
 

Question 2)

(2.1)
 
Molar volume of pure water = 18.102 + 18.491 × 0 + 4.1506 × 0 =18.102
 
  
Molar volume of pure methanol = 18.102 + 18.491 × 1.0 + 4.1506 × 1.0 = 40.7436  
(2.2)
Draw a tangential line at x1=0.5. The intercept of the line at x1=1 is the partial molar volume
of methanol at x1=0.5.
  
The slope of the tangential line = 
│ . = 18.491 + 2 × 4.1506 × 0.5 = 22.6416  
The molar volume of the mixture at x1=0.5 is 18.102 + 18.491 × 0.5 + 4.1506 × 0.5 =
 
28.385  
Let the tangential line be expressed by y = a + bx .
b=22.6416
28.385 = a + b x 0.5
a= 17.0642
y = 17.0642 + 22.6416x1
 
The intercept at x1 = 1.0 is (17.0642 + 22.6416 x 1.0) = 39.706  
, which is the partial
molar volume of methanol at x1=0.5.

(2.3)
   = 0
  +   = 0
   
  +   = 0should be met if the equation satisfies the Gibbs/Duhem equation.
 
V = 18.102 + 18.491 + 4.1506
 
V = 18.102 + 18.491 + 4.1506( )
 

nV = 18.102n + 18.491 + 4.1506

( )    
 = [ ] = 18.102 + 18.491 + 4.1506  
    
2 
= 18.102 + 18.491 + 4.1506  −   = 36.593 + 4.1506(2 −  )
 

V = 18.102 + 18.491 + 4.1506 = 18.102 + 18.491(1 −  ) + 4.1506(1 −  )
 
= 40.7436 − 26.7922 + 4.1506 = 40.7436 − 26.7922 + 4.1506 
 

nV = 40.7436 − 26.7922 + 4.1506


( )    
 = [ ] = 40.7436 − 26.7922 + 4.1506  
     
2 
= 40.7436 − 26.7922 + 4.1506  −   = 13.9514 + 4.1506(2 −  )
 
 
 +  =  (8.3012 − 8.3012 ) +  (−8.3012 + 8.3012 )
 
= 8.3012 (1 −  ) − 8.3012 (1 −  ) = 8.301  − 8.3012  = 0
Thus, the molar volume equation satisfies the Gibbs/Duhem equation.

Problem 3)

First calculate by interpolation Φ and Φ at Tr =0.82 for Pr=0.1000 and Pr=0.2000

 Tr Φ Φ
Pr=0.1000 Pr=0.2000 Pr=0.1000 Pr=0.2000
0.82 0.9397 0.8811 0.9648 0.9184

Next, calculate by interpolation Φ and Φ at Tr =0.82 and Pr=0.13.

Tr Φ Φ
Pr=0.1300 Pr=0.1300
0.82 0.9221 0.9509

Φ = (Φ )(Φ ) = 0.9221 × 0.9509. = 0.9062

Problem 4)

(4.1)
 (, ): The molar Gibbs energy of pure component i at given temperature (T) and pressure
(P).
 : The fugacity of component i in the mixture at given temperature (T) and pressure (P).

 : The fugacity of pure component i at given temperature (T) and pressure (P).

(4.2)

, =  − ,
 
 = ( () +   ) − ( (, ) +   )

= ( () +   ) − [( () +   ) +   ] = 
 
(4.3)
 =   
   
 = =
   
  
=
  

(4.4)
At low pressures and in an ideal solution,  = 1,  =  , and  = 1.
   
= =
   

  =  
 =   (Raoult’s law)

Problem 5)

(5.1)

  = 1,  = 1,  =  
(5.2)

∆   = (−1) × (−1,128,790 + (1) × (−604,030) + (1) × (−394,359) = 130,401
 
 
 ,
 
∆  
  
K =   = .
 ∙
× . 
= 1.42 × 10

(5.3)


∆H (1000) = ∆H (298.15 K) +   υ C, dT
 .

∆H (298.15 K) = (−1)x(−1,206,920) + 1x(−635,090) + (−1) x(−393,509)

J
= 178,321
mol
 

 υ C, dT = [(−1) × 81.88 + (1) × 42.05 + (1) × 37.14)]dT
 .  .

= −2.69 × (1000 − 298.15) = −1,888.0
 

∆H (1000) = 178,321 − 1,888 = 176,433
 


∆S (1000) = ∆S (298.15 K) +   (υ C, /T) dT
 .

∆H (298.15 K) − ∆ G (298.15 K) 178,321 − 130,401

∆S (298.15 K) = =
T 298.15
J
= 160.724
mol • K
 
 1000 
  (υ C, /T) dT =  (−2.69/T) dT = −2.69 = −3.25
 .  . 298.15   ∙ 

∆S (1000) = 160.724 − 3.25 = 157.47
  ∙ 

∆G (1000) = ∆H (1000) − T x ∆S (1000) = 176,433 − 1000 × 157.47 = 18,963
 

∆G (T) −18,963  
lnK = − =  = −2.2808
RT 8.314  ∙ × 1000
K = 0.102

(5.4)
a a p
K = = 
a  P
p p
0.102 =  =
P 1 bar
p ≤ 0.102 