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Chemical Engineering Thermodynamics (CHE 303)

Lecture 12: Entropy balance for an open system
Dr. Wael A. Fouad
Assistant Professor
Chemical Engineering Department
King Fahd University of Petroleum and Minerals
 Chapter 5:

Volumetric Properties of Pure

Fluids

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 Entropy
dQrev dT dp
• Entropy: dS = t
and dS = C P −R
T T p
• Every process proceeds in such a direction that the total
entropy change associated with it is positive
Stotal = S system + S surr = S Bt − S At + S surr  0
• Entropy change of a reversible adiabatic ( = isentropic)
process: B
dQrev
S = S − S = 
t t
B
t
A=0
A
T
• Entropy change of an irreversible process:
B
dQ
S = S − S  
t t
B
t
A 3
A
T
 Heat engine

• Total entropy change of cyclic heat engine:

QH QC
Stotal = S t
system + S + S = 0 −
t
H
t
C +
TH TC
(cycle)
TC
QC = TC Stotal + QH
TH

• Work produced by the engine (1st law): W = QH − QC

 TC 
W = −TC Stotal + QH 1 − 
 TH 
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 Heat engine
 TC 
• Work produced: W = −TC Stotal + QH 1 − 
 TH 

• Two extreme cases:

• Wmin = 0: Engine completely inefficient and process is
simple irreversible heat transfer between the two
reservoirs
• Wmax is obtained for fully reversible engine, so ΔStotal = 0
(Carnot engine)

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 Entropy balance for open systems

• Just like an energy balance, an entropy balance can be

written for an open system
• However, entropy is not conserved
• So, an entropy-generation term should be included to account for the
irreversibilities of the process

t
(Sm ) fs +
d (mS ) CV dS surr
+ = SG  0
dt dt

Net rate of Time rate of Time rate of Total rate

change in change of change of of entropy
entropy of entropy in entropy in generation
flowing streams control volume surroundings
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 Entropy balance for open systems
t
dS surr Q j
• Entropy change in surroundings: = −
dt j T , j

(as +𝑄ሶ is heat transfer to/from the working fluid from a reservoir with
temperature Tσ, the sign for the entropy change of the surroundings/
reservoir itself is negative)

d (mS ) CV
• Steady state: =0
dt

• Entropy balance for open systems:

Q j Qj
(Sm ) fs − 
1 entrance + 1 exit
= SG  0 S −  = SG  0
j T , j 𝑚ሶ is constant j T , j
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 Example 1

• In a steady-state flow process at 1 bar, 1 mole/s of air (Cp =

3.5R) at 600 K is continuously mixed with 2 mole/s of air at
450 K. The product stream is 400 K and 1 bar. The
surroundings are at 300 K.
• What is the rate of heat transfer of the process?
• What is the rate of entropy generation of the process?

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 Example 1

• Heat transfer rate of the process:

Q = (n A + n B )H − n A H A − n B H B = n A (H − H A ) + n B (H − H B )
= n AC p (T − TA ) + n B C p (T − TB )
= 3.5  8.3145  (1  (400 − 600) + 2  (400 − 450)) = −8730 J/s
• Rate of entropy generation of the process:
 
SG = (n A + n B )S − n A S A − n B S B − = n A (S − S A ) + n B (S − S B ) −
Q Q
T T
T   T  Q
= n AC p ln  + n B C p ln  −
 TA   TB  T
  400   400   8730
= 3.5  8.3145  1  ln  + 2  ln   + = 10.45 J/K/s
  600   450   300 9
 Calculation of ideal work
 1 2  .  
• Energy balance:   H + u + zg  m = Q + Ws
 2  
• If heat is supplied by a reservoir with temperature Tσ in
a completely reversible way:
Q rev = T ( Sm )
• Ideal work: maximum possible work done by the system:
  
Wideal =   H + u + zg m  − T (Sm )
 1 2
 2  

Wideal = m (H − T S ) Wideal = H − T S

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 Example 2

• What is the maximum work that can be obtained in a steady-

state flow process from 1 mole of nitrogen at 800 K and 50
bar?
• Given:
• The surroundings are at 300 K and 1.0133 bar
• Heat capacity of nitrogen:
C p,N2
= 3.280 + 0.593 10 −3 T + 0.040 105 T − 2
R

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 Example 2

• Maximum work is achieved when temperature and pressure

are reduced to conditions of surroundings in a completely
reversible way:
Wideal = H − T S

• where:
T2
 p2 
T2
H =  C p , N 2 dT dT
and S =  C p , N 2 − R ln 
T1 T1
T  p1 
C p,N2
with: = 3.280 + 0.593 10 −3 T + 0.040 105 T − 2
R
T1 = 800 K, T2 = 300 K, p1 = 50 bar, p2 = 1.0133 bar 12
 Example 2
T2 T1
C p,N2 C p,N2
H = R  dT = − R  dT
T1
R T2
R

 D
( )
T
Cp
dT = R   AT0 + T0 ( + 1) + T0  +  + 1 +  ( − 1)
B 2 C 3 2
remember: R 
T0
R  2 3 T0 
Here: A = 3.280, B = 0.593 10 −3 , C = 0, D = 0.040 105
800
R = 8.3145 J/(mol  K), T0 = 300 K and  = = 2.67
300
 0.593 10 −3 2 0.040 105 
H = − R  3.280  T0 + T0 ( + 1) + 0 +  ( − 1)
 2 T0 
= −15060 J/mol
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 Example 2

 p2   p2 
T2 T
dT 1
C p , N 2 dT
S =  C p , N 2 − R ln  = − R  − R ln 
T1
T  p1  T2
R T  p1 
C Pig dT   2 D   + 1 
 ( − 1)
T
remember:  = A ln  +  BT0 +  CT0 + 2 2 
T0 R T    T0  2 

Here: A = 3.280, B = 0.593 10 −3 , C = 0, D = 0.040 105

800
R = 8.3145 J/(mol  K), T0 = 300 K and  = = 2.67
300
   0.040 105   + 1    1.0133 
S = − R 3.280 ln  + 0.593 10 T0 +  0 +
−3

 2  ( − 1) − R ln  
    2
T0
2
    50 
= 3.042 J/(mol  K)
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 Example 2

Ideal work:
Wideal = H − T S
= (− 15060) − 300  (3.042) = −15973 J/mol

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