Problem Session 1

CHEN623: Fundamentals and Applications of
Thermodynamics to Chemical Engineers
Problem session 1
14 August 2022
CHEN 623: Thermodynamics for Fall 2022

Fall 2022
Problem session 1
Chemical Engineers 1
Problem 1. Mathematical Preliminaries
True or False
 ∂U   ∂U   ∂U   ∂U   ∂T   ∂V 
a)   =0 d)   ≠   g)       = −1
 ∂T U  ∂T V  ∂T  P  ∂T V  ∂V U  ∂U T
 ∂U   ∂S   ∂S   ∂U  h) In a one component one phase system,

b)   =1 e)   =    
 ∂U V  ∂T V  ∂U V  ∂T V  ∂h 
  =0
 ∂T υ , P
 ∂U  1 ∂  ∂S  ∂  ∂S 
c)   = f)   =  
 ∂T V  ∂T  ∂V T  ∂T V ∂T V  ∂V T
 
 ∂U V
If the total energy (U ) can be considered to be a function of temperature T , total volume V
and number of moles N , write the expression for
a) Total differential of U .
b) Total derivative of U with respect to T
c) Partial derivative of U with respect to T at constant N
U = U (T ,V , N )
 ∂U   ∂U   ∂U 
a) dU =   dT +   dV +   dN
 ∂T V , N  ∂V T , N  ∂N T ,V
dU  ∂U  dT  ∂U  dV  ∂U  dN
b) =  +  + 
dT  ∂T V , N dT  ∂V T , N dT  ∂N T ,V dT
 ∂U   ∂U  dV  ∂U  dN
=
  +  + 
 ∂T V , N  ∂V T , N dT  ∂N T ,V dT
 ∂U   ∂U   ∂T   ∂U   ∂V   ∂U   ∂N 
c)   =    +    +   
 ∂T N  ∂T V , N  ∂T N  ∂V T , N  ∂T  N  ∂N T ,V  ∂T  N
 ∂U   ∂U   ∂V 
=   +   
 ∂T V , N  ∂V T , N  ∂T  N
taking N as a constant is equivalent to having a closed system. Using the equations from Table 2-1, we get
 ∂U    ∂P    ∂V 
  C
=υ + T
   − P  
 ∂T  N   ∂T V , N   ∂T  N
Problem 2
From the first homework, it was shown that the enthalpy change between two states is
T2 P2   ∂υ  
∆h
= ∫T1
cP dT + ∫
P1 υ − T  ∂T   dP.
  P 
Propose a convenient path of integration to incorporate ideal gas cP*
in the calculation of enthalpy change between two states. Ideal gas cP*
are readily available in the literature for most components.
Derivation of the enthalpy change from state (1) to state (2) - HW problem
H (T , P) (2)
 ∂H   ∂H  (1)
dH   dT +   dP
 ∂T  P  ∂P T P
From table 2.1
 ∂H   ∂H   ∂V  0
  = CP   = V −T  
 ∂T P  ∂P T  ∂T  P T
  ∂V  
dH= CP dT + V − T    dP
  ∂T  P 
T2 P2   ∂V  
H 2 −=
H1 ∫T1
CP dT + ∫ V − T 
P1
  ∂T
  dP
P 
(a) Isothemal expansion: ( P1 , T1 ) → ( P =
0, T1 )
(b) Isobaric heating: ( P= 0, T1 ) → ( P= 0, T2 )
( P 0, T2 ) → ( P2 , T2 )
(c) Isothemal compression:= (2)
h2 - h1 = ∆ha + ∆hb + ∆hc

(1)
From previous slide we know that
P (c)
(a)
T2 P2   ∂υ   (b)
h2=
− h1
T1
cP dT + ∫ υ − T 
∫ P1

  dP
 ∂T  P  0
We can use this expression to obtain the following: T
P = 0,T1   ∂υ  
∆ha =0 + ∫ υ − T  ∂T   dP
P1 ,T1
  P 
P = 0,T2
∆hb
= ∫ P = 0,T1
c*p dT + 0

P2 ,T2  ∂υ  
∆hc = 0 + ∫ υ − T    dP
P = 0,T2
  ∂T  P 
Therefore the enthalpy change from state (1) to state (2)
in terms of ideal gas heat capacity is as follows:
P 0,=
T1 
P 0,T2  ∂υ   P2 ,T2   ∂υ  
h2 - h1 = ∫P1 ,T1 υ − T  ∂T=
 
  dP + ∫P
P 
c*p dT + ∫
0,=
T1 P 0,T2 

υ − T    dP
 ∂T  P 
Problem 3
= Tds − Pdυ
du  ∂u   R 2a   RT 
  =
−T  + 3 
− P − 2 
 ∂u   ∂s   ∂υ  ∂P
 T  P T   P 
=
  T   − P  
 ∂P T  ∂P T  ∂P T  ∂u  2a
  = −
From Maxwell Relation  ∂P T T3
 ∂s   ∂υ  π 2a
  = −   ∆u =− ∫ dP
 ∂P T  ∂T  P 0 T3
 ∂u   ∂υ   ∂υ  2aπ
  = −T   − P  ∆u =−
 ∂P T  ∂T  P  ∂P T T3
From the given equation of state

 Pυ  BP
z=  = 1+
 RT  RT
RT RT a
υ= + B= +b− 2
P P T
 ∂υ  R 2a
 = + 3
 ∂T P P T
 ∂υ  RT
  = −
 ∂P T P2
Problem 4 – From previous exam question
Most carbonated waters are only carbonated to approximately

2 g/L (8.2x10-4 mol fraction). Assuming that carbonated water
contains only CO2 and H2O, determine the composition of the
vapor and the pressure in a sealed bottle at 25 oC. At this
temperature, the saturation pressure of water is 0.032 bar and
Henry’s constant of CO2 in H2O is 1670 bar. Also, calculate the
fugacity of each component in the vapor and liquid phase.
State all your assumptions in your solution.
Assumptions: fugacity of CO 2 (1) is described by Henry's law
while the fugacity of H 2 O (2) is described by Raoult's Law
f i L = f iV
y1 P = x1 H1
y2 P = x2 p2sat
P x1 H1 + x2 p2sat
=
=P 0.00082 × 1670 + (1 − 0.00082)0.032
P = 1.4 bar
0.00082 ×1670
y1 = 0.978
1.4
1 − 0.978 =
y2 = 0.022
2 = f CO 2 = 0.00082 × 1670 = 1.37 bar
L V
fCO
f HL20 = (1 − 0.00082)0.032 =
f HV 2O = 0.031 bar
Problem 5
Solubility of water in oil: f1 = H (T ) x1
f1 1 bar
and H (T=
) = = 286 bar @140 o C
x1 35 ×10−4
We need f1 at 140 o C and 410 bar
There are two option two get f1 at 140 o C and 410 bar
(a) From steam tables, (webbook.nist.gov)
(b) Get f at saturation (3.613 bar) and use Poynting correction for 410 bar.
(a) @140 o C RT ln f1 =∆g1→410 bar =∆h1→410 bar − T ∆s1→410 bar
T (oC) P (bar) h (J/g) s (J/g-K) ρ kg/m3

140 1 2756.7 7.5672 0.52936
140 400 615.53 1.7006 946.20
f1  J g
RT ln 0
∆g1→410 bar =
= ∆h1→410 bar − T ∆s1→410 bar =
 ( 615.53 − 2756.7 ) − (140 + 273.15)(1.7006 − 7.5672 )  18
f1  g  mol
f 282.6
ln 1 = 1.478
1 bar 8.314 (140 + 273.15 )
f1 = 4.38 bar
4.38
x1
= = 0.0153
286
(b)
 υic ( P − Pi s ) 
f = P ϕ exp 
1
c s s
1 1

 RT 
 
 1/ 946.2 × 0.018 ( 410 − 3.613) ×105 
f = 3.613exp 
c

1
 8.314 (140 + 273.15 ) 
f1c = 3.613 (1.25 )
f1 = 4.52 bar
4.52
x1
= = 0.0158
286

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CHEN623: Fundamentals and Applications of

Thermodynamics to Chemical Engineers

CHEN 623: Thermodynamics for Fall 2022

 ∂U   ∂S   ∂S   ∂U  h) In a one component one phase system,

h2 - h1 = ∆ha + ∆hb + ∆hc

From the given equation of state

Most carbonated waters are only carbonated to approximately

(a) @140 o C RT ln f1 =∆g1→410 bar =∆h1→410 bar − T ∆s1→410 bar

T (oC) P (bar) h (J/g) s (J/g-K) ρ kg/m3

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