Chap.

4 2nd Law & Entropy

W x Q
? Chap 1, Joule’s Experiment
→ Directionality, Irreversibility
→ Limit for Heat Engine η and Refrigerator COP

4-1 Examples to have directionality

1. Heat transfer through  (not dT)

2. Friction
3. Free expansion and Mixing
4. Hysteresis effect
2
5. i R loss
6. Combustion
Real [irreversible] process

Ideal process [rev. process]

Approximate
Examples
┌│ (1) Vibration of string in vacuum : Only internal friction
│
└ (2) } Cut into infinite pieces and lower the piston.
4-2 Statement of the 2nd Law of thermodynamics
┌ Directionality, Statements, Carnot cycle, Temperature scale
│
├ Entropy, Entropy generation, Lost work, Calculation of entropy
│
└ Diagram         , Entropy for ideal gas
1. Kelvin - Planck Statement
2. Clausius Statement
3. Statement by adiabatic process :
In the adiabatic process, in which the deformation variables that can
calculate the work of the system, such as volume, are constant, the
process does not proceed in the direction in which the internal energy of
the system decreases.

4. Proof ⇒ C K.P
by contradicting the unreasonableness method(배리법)

(4-1) C → K.P (4-2) K.P → C

TH TH

Q '- Q
Q '+Q Q Q'
Q Q'

R E W = Q '- Q Ref E
W=Q '
Q Q
Q
Q

TL
TL

5. With only one heat source, power generation is impossible and

negative heat and work transfer are possible .
6. Entropy increase in isolated systems    ≥ 
7. Heat engines for power generation must have two or more heat
sources
8. Caratheodory theorem

9. Change in entropy ≥ entropy transfer ( ≥  )

10. Entropy generation ≥ 0 ( ≥ )
11. The efficiency of the reversible heat engine is higher than that
of the irreversible heat engine.
12. For the same amount of received heat, the discharged heat
from the irreversible heat engine is greater than that of the
reversible heat engine.

4-3 Carnot cycle

Since a heat engine having a heat exchange with a single heat
source cannot be constructed, at least two heat sources having
different temperatures are required to construct the heat engine.



   QH 단열
등온 E W

   QL



 
            , max  
 
◎ Carnot’s theorem

1. Carnot Heat Engine has the highest efficiency among the heat
engines operating between two heat reservoirs.
 ≧ 
2.   
==> Carnot cycle is a function of temperature only

┌      
│
│
└      

[Proof] 1. If 
   → K-Planck

TH

QH' - QH
QH QH QH'

C E
W W '

QL
QL QL
 ′  
 ′        
TL  ′  

2. Replace E with another Carnot engine C '

And then prove ′ ≦  , next prove  ≦ ′

⇒   ′
4-4 Thermodynamic temperature
Arbitrary temp   ↔ 

※ Fig. 6-8 : Carnot cycle A, B, C

θ 1

Q 1

WA A Q 1

Q 2

θ 2 C WC

Q 2

WB B Q

～? T
3

Q
θ
3

θ 3

 
(1)             ⇒         … (a)
  


        … (b)
 

  
(a), (b) →  ․               … (c)
  
   

 
            →         … (d)
 

          ×    
         
(c), (d) →           ×    

         
Thus    Generalize ⇒  
   
      
Here, if  ≡     : thermodynamic temperature
C : Arbitrary const
 T
 
 
   (1) Q


  ․  (6-9b)
 Carnot W

If you measure  and  (or  ) in

Q
the Carnot heat engine as shown in the 0

figure, you can determine the temperature.

T0
However, since Carnot heat engines cannot
exist, other methods are used.
When taking      as the reference point,  is
called the Thermodynamic Kelvin temp. therefore

   


(2) Now, to compare the thermodynamic temperature and the

ideal gas temperature, we will analyze the Carnot cycle using the
ideal gas as the working fluid.

T id ～? T

 
1-2 process :      
   ․ ln 


2-3 process :  ․      ․   


3-4 process :    ․ ln 


4-1 process :  ․      ․   

  
∴  
 
   
     ln  ․   
     
 

∴










   
  
     
from(1)  
  
∴   

If      , then    ,   

For more general proof ⇒ refer to Chap 11.
4-5 Entropy – Drive (existence), Definition, Calculation

   
         ⇒  
    

   
⇒    
   


⇒ 


    

    

:    
  

 

Q=0
Q=0


 
 → ∞
 → 
 
 

  
   

ie ,  



 Mathematical : ┌  Inexact differential
cf│
│ 
meaning └  
 
  Existence of entropy

   
 
    
   
 



Reference → Tabulate S

┌ 1st Law : Energy ∃

│
└ 2st Law : Entropy ∃

Saturated:       
        
        

[Ex 4-1] Exact and Inexact differential

어떤 이상기체의 정적비열이      로 알려져 있다. 이상기체의 체적팽창
만을 고려할 때 에너지 식은             로 쓸 수 있다.

 는 불완전 미분량이고    는 완전 미분량임을 보여라.


(풀이)

[Ex 4-2] Calculation of changes in water vapor entropy

압력 1 bar 의 포화수증기 1 kg 이 포화액으로 응축(hfg=2257.5 kJ/kg)되면서
0oC의 얼음을 융해시켜 0oC의 물이 되도록 한다. 열전달이 없는 단열과정으로
이루어질 때 녹일 수 있는 얼음의 양과 각각 및 전체의 엔트로피 변화를 구하
라. 0oC에서 얼음의 융해열은 333.6 kJ/kg 이다.

(풀이) ×   , m=6.77kg,

  
       
    
  
       , 
    

[Ex 4-3] Calculation of solid entropy change

질량 m의 고체(또는 액체, 비열 C )가 일정한 압력하에서 온도 T1 으로부터

T2 로 변한다. 엔트로피 변화량을 구하라. (답)    ln 
 
4-6 Analysis of the actual process
Clausius inequality
Entropy generation

   
(1)               
   

∴    

TH

QH QH

W id C E W

Q id L QL

TL

  
Carnot engine :     
 
 

    
∴   
   
⇒ 


    


⇒ 


∴  ≦ :

Clausius inequality

 
(2) (Question) : How about the following approach for the   

  
  

 
   
 


   

 
⇒  ≦ 



 

      
  
 
 

 
≦ ,


  

 
     ≦ 

  
∴  
     ≧  


 
C 2
   
   
  
 
    

Ideal

  
  

 
   


  


∴  
 D
 1 Real

 
┌  ≧  →      (  ≧  ) ┐
│  
│ │ (4-27)
│    
└    ≧  

→         (  ≧ ) ┘
 

 : produced entropy (entropy generation)→ Always (+)

◎ Another approach for Eq.(4-27)


Let     


Then   



    

⇒    ≦ 
∴   ≧  ,  ≧ 
Adiabatic system in Eq.(4-27) :      ≧ 
→ Entropy increase in isolated systems
4-7 Entropy generation

(1) Heat transfer through a finite temp. diff.



T1
       
 

Q ↓   
          ≧ 
  
If     , ≧ Verified Clausius
T2 If     , ≦ statement

(2) Heat exchange with single heat source

         
Q
∴      ≤ 
E W=Q
Verified Kelvin-Planck

(3) Heat engine (2- heat sources)

    
T1  
         
 
Q

→ →
1
    
    
E

  
  
W
   
         
   
Q 2


     ≦ 
T2 
or           ≧ 
(4) Refrigeration cycle

    
 
    
  
  
 
T1

Q
→ 


 



→ 

 

  



1

  
R
      
W
    
 


Q 2    
 
    
T2    

  
   
 
   

 
or       
   

  
 
 ․        ․     
    



(5) Heat Pump
 
         
   

    
 (6) Entropy generation by friction

⓵ ↓⓶
T1 → T2

S1 → S2


∘Ideal process without friction :      
 



 ′
∘Real process with friction :      



∘For a given state change, the entropy change is the same.

  ′
     
  


 



On the other hand, in the case of friction, the work supplied is

absorbed by the internal energy of the solid system, so the amount of heat

consumed in the real process  
′ at a given temperature rise T2 -T1


is less than that of the ideal process  
 . Therefore, it can be seen

that it should be    .

[Ex 4-4] Calculation of entropy generation in a cycle

An internally reversible heat engine operating between two isothermal
heat sources of 800 K and 320 K receives 40 kJ of heat from the hot
section and generates 15 kJ of work every cycle. Find the entropy
production per cycle at this time.

   
(Sol)       ,           
   

[Ex 4-5] Calculation of COP in a refrigerator and a heat pump

온도가 각각 –20oC와 25oC인 두 열원 사이에 역 Carnot 사이클로 작동하는
냉동기와 열펌프의 성능계수를 구하라.
      
(풀이)         ,
        
    
         
        
4-8 Lost work(손실일)

T
From    1

 Q 1
      

 
         
E W

 
Q
    2

         : lost work

T 2

∘For simple heat transfer   

∴ ℓ    

∘Refrigeration cycle

From   


       

 
          
 
   
      
o Minimization of entropy production
Summing up the lost works of the above heat engine and freezer
,i.e., ℓ     and considering that the ambient temperature
is almost constant, minimization of lost work results in minimization
of entropy production.
4-9 Entropy Relation

    

     

simple system

     unit     

     mass     
Arbitrary process
 
     
 
→     
 
      →    
 

[Ex 4-6] Entropy calculation(Contact between two solids)

The temperatures of two identical solids with mass m and specific
heat C are T1 (K) and T2 (K), respectively. When contacting the two
solids and avoiding heat transfer to the outside, find the change in
entropy after lefting these for a long enough time.

 
(Ans)    ln      ln  
   
 
       ln    ln 
 
   
  ln   


[Ex 4-7] What is the entropy of saturated steam at 50oC when the
entropy is 0 at the triple point of water?
     
 
(Sol)       

  ln    
   

 

    


      
 
           
4-10 Entropy of ideal gas

   
①           
   
   
②           
   
  
  
→   
  
  
③           
  
 
     
 

From ①, ②, ③ → The entropy of an ideal gas is not a function

of temperature alone.

 
         : Ideal(Reversible) adiabatic
 
×    process

◎ Calculation for a wide temperature range

    
     
 
   ln 

        
 
 
  

 
   ln 


   

      


 Tabulate   에서의 불연속?
→ →  ≈ 
temperature range ⇒ Tablization
 as →
                 ln 

→ Choosing a pertinent ref. P in    process
     

 ≡ 

,  
 

 
   
   

     
 
    ⇒ Tabulate
Appendix A-9

[Ex 4-8] Change in air entropy v = con st process. (T1, P1)--> P2

Find the change in entropy when the pressure of 1 MPa and the
temperature of 250oC is cooled in a container with a volume of 0.1
m3 and the pressure becomes 0.5 MPa.

  × 

(Sol)       
  ×    
 
      ×   
 
 
     ln    ×  × ln    
 

[Ex 4-9] When the air is replaced by a steam with the same
v = con st process, find change in the steam entropy?

(Sol)       ==>

        
 
       
 
At       and P2 = 0.5 MPa, the state 2 is wet steam
state. The dryness at this state
   
    
  
Therefore,             ×    
                   

[Ex 4-10]        , (T1, P1)--> P2 , Change in air

entropy?

[Ex 4-11] s= c process, (T1, P1)--> P2, W 1-2=? for air

[Ex 4-12] (P 1
,T 1
) --> ( P 2
,T 2
) , Change in air entropy?
(H.W)
[Ex 4-8 & 4-9] a, b, c, d 경로에 따라 적분하여도 s 2 -s 1
은 일정함을
보여라.

P 1  ℃  Air

×


d 1
Steam
a
s= c r ev d 2

c 1
b 1

c 2 b 2
× 2   

T
4-11 Entropy diagram


   ⇒     
 
   
     

 

  

       

     ⇔     

        cos     

   
   
   sin     
      
  cos   sin
   
  
  sin   cos
  


 



 
 
    
 

  ≡   cos   sin  
     

 

* Carnot cycle in P-T diagram

    
→    
×1
s= c
P
TH
  
L
TL
       
     
2×
s= c

S V
Carnot
cycle in
∴
 


 
 
  

P-T
T      

 ∙  
  
(M1) In the case of ideal gas with s=constant process,
  
 
 
  or    

∴ 


 
      
             
     