54 Second Law of Thermodynamics

TC
(iv)  is one only when T is zero. i.e. when TC  0K or TH   K . Both these temperature are impossible
H
to obtain. Therefore, the efficiency of an engine can never be one or 100%. That is heat can’t be transformed
completely into work.
(v) For all reversible cycle operating between the same source and sink temperature, the efficiency is the
same.

Comparison of efficiencies of reversible and irreversible engine.

The efficiency of a reversible Carnot cycle is the theoretically possible maximum value which an
engine can have. Since the various processes of this type of engine are to be carried out reversibly,
therefore, such type of an engine does not have any realistic basis because reversible processes
are idealized concepts which can never be realized. A real heat engine, which is irreversible in
nature, will have efficiency smaller than the reversible heat engine.
Let us have two cycles, one operating reversibly and the other irreversibly. Let both of
them operate between the same two temperature TC and TH and involve ideal gas as the working
substance. These two cycles along with q values, are shown in the figure below.

(A) Isothermal expansion form volume V1 to V2. The expressions for the work involved are
V2
 w1  rev   q1  rev   RTH ln
V1
And w1  irr   q1  irr   popp V2  V1 

TH TH
q1(rev) q1(irr)

rev wrev irr wirr

q2(rev) q2(irr)

TC TC

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Since we know that w1  rev   w1  irr  , therefore,
q1  rev   q1  irr 
(B) Isothermal compression from volume V3 to V4. The expressions for the work involved are
V4
 w3  rev   q2  rev   RTC ln
V3
w3  irr   q2  irr   P 'ext V4  V3 
Now, since in the irreversible process, more work is done as compared to that in the reversible
process, we have
w3  irr   w3  rev 
It follows that
q2  irr   q2  rev 
Now the efficiencies of the two cycles are
Second Law of Thermodynamics 55

q1  rev   q2  rev  q2  rev 

  rev    1
q1  rev  q1  rev 

q1  irr   q2  irr  q2  irr 

  irr    1
q1  irr  q1  irr 

Now since q1  rev   q1  irr  and q2  rev   q2  irr  , therefore, it follows that
q2  rev  q2  irr   q2  rev    q2  irr  
 or 1  q  rev    1  
q1  irr  
q1  rev  q1  irr   1  
i.e.   rev     irr 

Basic Conclusion from Efficiency of a Carnot Cycle :

For a reversible Carnot cycle operating between two temperatures TH and TC, the efficiency is
given as
q1  q2 TH  TC
 
q1 TH
where q1 and q2 are the heats exchanged with the thermal reservoirs at temperatures TH and TC,
respectively. Rewriting the above expression, we have
q2 T q T
Or, 1  1  C or 2   C
q1 TH q1 TH
q1 q2
Or,  0
TH TC
that is, the sum of the ratios of the heat involved and the corresponding temperature is zero for a
Carnot cycle.

Carnot Refrigerator:
It is the reverse of Carnot engine i.e. the energy flow from
low temperature body to a high temperature body by T2
providing energy in the form of work to the system. It is
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the energy transfer device therefore, the ratio of its output
W
q2
to input is represented by coefficient of Ref
performance which can be greater than 1.
In case of Carnot refrigerator system absorbed q1
heat from low temperature body and transfer it to the high
temeprature body. In carnot engine heat is input work is T1
output. In refrigerator heat is output and work is input.

Co-efficient of performance () of Carnot refrigerator:

It is defined as the ratio of heat transferred from a lower temperature to a higher temperature to the work done
qC
on the system, i.e.  
w
The lesser the work done the more efficient the operation and greater the coefficient of performance.
qC TC
 
qh  qC TH  TC
 56 Second Law of Thermodynamics

At TC  0K ,   0

 w
qC

 qC   
 0
Thus as the temperature of a system is lowered the amount of work required to lower the temperature further
increases rapidly and approaches infinity as the zero kelvin temperature is attained.

TC
Efficiency of Carnot cycle () = 1 
TH
For adiabatic curve TV  1
 TH V2 1  TC V3  1 (V1)
A
1 TH
TC  V2  TC 1 1 B(V2)


     1
  1
TH  V3  TH  V   P
2
 
 V3  (V4)D
TC C(V3)
 1
1  V3 V4 
   1   where,    
V

   V2 V1 
Relation between η and β :
TC
  TH  TC
TH  TC
TH  TC 1 TH 1 TH 1   TH  TH  1 TC
Again.   TH  
 TH  TC  
1 
TH  TC
1 


TH  TC

TH  TC
1  1
 or  
  1

Problem-1: A certain engine which operates in a Carnot cycle absorbs 4 kJ at 527ºC how much work is done
on the engine per cycle and how much heat is evolved at 127ºC in each cycle?
Soln. The efficiency of the Carnot cycle is given by
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TH  TC q1  q2
 
TH q1

TC q2 T 
Thus,   and hence q2    C  q1
TH q1  TH 
Thus, the heat evolved in the present case is

 400 K 
q2      4kJ   2kJ
 800 K 
and the work done on the engine is

w    q1  q2   4  2  2kJ
The negative sign indicates that the work is actually done by the engine.
Second Law of Thermodynamics 57
Problem-2: What % of T2 should be T1 for a 10% efficiency?
TC 10 TC
Soln.   1  T  100  1  T
H H

TC 10 90
  1   0.9
TH 100 100
TC  0.9TH

 TC %  90%TH
Problem-3: Calculate the maximum efficiency of an engine operating between 110ºC and 25ºC.
Soln. Maximum efficiency of an engine working is

   TH  TC  / TH   383K  298K  / 383K  0.222  22.2%

Problem-4: Heat supplied to a Carnot engine is 1897.8 kJ. How much useful work can be done by the engine
which operates between 0ºC and 100ºC?

Soln. TH  100  273  373K ; TC  0  273  273K ; q1  1897.8 kJ

TH  TC 373  273
   0.268
TH 373

w
  w  0.268  1897.8  508.7 kJ
q1
Problem-5: A Carnot cycle operates on a temperature difference of 200K. One-third of the heat absorbed
from the source at T2 is discharged as waste heat to the sink at T1. The cycle does 400J of work. Calculate q1,
q2, T1 and T2.

Soln. Given, q1  Q
Q
q2 
3
w  400 J and T  200 K

   1
q2 www.careerendeavour.com
 1
Q
 
2
q1 3Q 3
TH  TC 2 200
  
TH or 3 TH or TH  300
T  TH  TC
200  300  TC
 TC  100
w 2 400
Since,   
q1  3 q1  q1  600
200
 q2   200 J
3
Problem-6: A Carnot engine operates between 600K and 800K and absorbs 2, 000 calories from the source
per cycle. The work done (in Cal) per cycle is
(a) 1, 000 (b) 500 (c) 666 (d) 2, 000
 58 Second Law of Thermodynamics

TH  TC
Soln. Since,  
TH
800  600 200 1 w
    
800 800 4 q1
 w

4 2000 or w  500 cal
Correct option is (b)
Problem-7: The coefficient of performance of a perfect refrigerator working reversibly between the temperatures
Tc and Th is given by
Tc  Th Th  Tc Tc Th
(a) T (b) T (c) T  T (d) T  T
c c h c h c
Soln. The ratio of heat transferred from a lower temperature to a higher temperature to the work done on the
qC
machine to cause this removal, i.e.  
w
The less the work done the more efficient the operation and greater the coefficient of performance.
 w irr  w rev ,  rev  irr
qC Tc
 
qh  qC Th  Tc
Correct option is (c)
Problem-8: In a carnot engine 200 cal heat is given to the sink by a reservoir at 27°C. If temperature of the
source is 57°C, then find:
(i) How much heat flows from the source.
(ii) Efficiency of the engine
(iii) Work done by the reservoir.
Soln : q2 = 200 cal, q1 = ?
TC = 27°C = (27 + 273) = 300K
TH = 57°C = (57 + 273)  330K;  = ? and w = ?
q1 q2
(i) T = T
H C
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q1 200cal q
1 200
 =  11 = 10 cal  q1= 220 cal
330K 300K
q2 200 10 1
(ii) = 1 – q  = 1 –  = 1 – 11  = 11  0.091
1 220
(iii) |w| = q1 – q2= (220 –200)cal= 20cal
Problem-9: Temperature of the sink of a carnot engine is 7°C and efficiency is 50%. Calculate change in
temperature of the source to increase the efficiency of the same engine 70%.
Tsink
Soln. = 1– T ... (i)
source

Case-I:= 0.5, Tsink= 7°C = 280K

280K
from equation (i), 0.5 = 1 – T
source

280K 280
Tsource
= 1 –0.5 = 0.5  Tsource= = 560K
0.5
Second Law of Thermodynamics 59

7
Case-II: = 0.7 = , Tsink= 7°C = 280K
10
from equation (i)
7 280K 280K 7 3
 = 1– T or T =1– =
10 source source 10 10

280K ×10
 Tsource= or Tsource= 933.33K
3×1
Therefore, change in temperature of the source = (933.33 – 560)K = 373.33K
Problem-10: The efficiency of a carnot’s cycle is 1/6. If on reducing the temperature of the sink by 75K,
1
efficiency becomes . Calculate the initial and final temperature between which the cycle is working.
3
TC 1 1  TC TC 1 TC 5
Soln: We have,  = 1  T or = T  T = 1  T =
H 6 H H 6 H 6

C T  75 1 T
C 75
1 5 75
Now, = 1  T  = 1– T  T  = 1– 6  T [Using equation (i)]
H 3 H H 3 H

1 1 75 75 1 1 75 1
 = + T  T =   T = TH= 450 k
3 6 H H 3 6 H 6

5
(ii)  TC= 6 × 450 K= 5 × 75 K= 375 K
Problem-11: A Carnot refrigerator takes heat from water at 0ºC and discard it to a room at 27ºC. 1 kg of
water is to be changed into ice at 0°C. How many calories of heat is discarded to the room? Calculate the
work done by the refrigerator and coefficient of performance. [Given: H fussion  80 cal g 1 ]

(Hot)
T1 > T2
Source T1
q1

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w =|q1| –|q2| SYSTEM

Soln:

q2
Sink T2
(Cold)

Here T1= 27°C = 300K, T2= 0°C = 273K

For the process, H 2O    
 H 2O  s  H  80 calg 1

Cal
 Q2= 1 × 103 g × 80 g  Q2= 8 × 104 Cal
 60 Second Law of Thermodynamics

Q1 T1 300
We have, Q = T  Q1= 8 × 104 cal ×
2 2 273

300
 Work done = Q1 – Q2= 8 × 104 × Cal – 8 × 104 Cal = 7.9×103 cal
273

T2 273
and    10.11
T1  T2 27
Problem-12: A Carnot engine operates at 55% efficiency. If the temperature of reject steam is 105ºC, then the
absolute temperature of input steam is ___________K.
Soln. Efficiency of carnot engine,
TC
  1 ... (1)
TH
Given,   55%  0.55
And T1  105  273  378 K
From equation (1),
378 378
0.55  1  K  0.55  1   K
TH TH
378 378
 0.45    TH   840 K
TH 0.45
Problem-13: A heat engine operates between 1000 K and 600 K. The heat discharged into the cold sink in a
reversible process when 5 kJ of heat is supplied by the hot source, is
(a) 2 kJ (b) 2.5 kJ (c) 3 kJ (d) 5.5 kJ
q1 TH 5kJ 1000 K
Soln.   
q2 TC q2 600 K

 q2  3kJ
Correct option is (b)
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Problem-14: Suppose the coldest reservoir we have at hand is at 10ºC. If we want a heat engine that is
at least 90% efficient, the minimum temperature required for the hot reservoir is
(a) 1800K (b) 2880K
(c) 2800K (d) 2830K
Soln. TC  10C  283K ,   90% , TH  ?
TH  TC T  283 283
  0.9  H  1
TH TH TH  TH  2830 K
Correct option is (d)
Problem-15: A heat engine operates between 1000 K and 600 K. The heat discharged into the cold sink
in a reversible process when 5 kJ of heat is supplied by the hot source, is
(a) 2 kJ (b) 2.5 kJ (c) 3 kJ (d) 5.5 kJ
Second Law of Thermodynamics 61

Soln. TH  1000 K , T1  600 K , q1  5kJ , q2  ?

q1 TH 600
   q2  5   3kJ
q2 TC 1000
Correct option is (c)
Problem-16: Liquid He boils at about –269ºC and liquid H2 boils at about –253ºC. The efficiency of a
reversible engine operating between heat reservoirs at these temperatures
(a) 20% (b) 80% (c) 10% (d) 90%
Soln. TC  269C  269  273  4 K

TH  253C  253  273  20 K

The efficiency of a reversible engine .
TH  TC 20  4
   80%
TH 20
Correct option is (b)
ENTROPY

For Carnot cycle,

dq rev q1 q
 T
 0 2 0  0
Th Tc
dq rev
 is a state function which is called the change in entropy
T
dq rev
  dS or  dS  0
T
The entropy is a function of the independent variables which are used to define the state of a
system. It is an extensive function. The change in the value of the entropy in going from one state
to another, is independent of the path.
The unit of entropy is JK–1 or cal K–1.
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dq  irr 
 T
for an irreversible cyclic process :

If there is any irreversibility at any stage of a cycle, the net work obtained wnet in the cycle is less
than the maximum work obtainable from the reversible cycle operating between the same two
temperatures. Consequently, the efficiency of an irreversible cycle is always less than the efficiency
of the corresponding reversible cycle. It follows that
wtotal Th  Tc q1  q2 Th  Tc
 or 
q1 Th q1 Th
q2 T q q
Or,   c or 1  2  0
q1 Th Th Tc
It shows that for irreversible cyclic process,
dq  irr  q1 q
 T
 0 2 0 0
Th Tc
62 Second Law of Thermodynamics

dq  irr 
Hence,  T
0

Spontaneous (irreversible) process and non-spontaneous (irreversible) process:

The process which proceed by themselves and bring the system closer to the equilibrium are called spontaneous
process. All natural process are spontaneous.
The process which can’t proceed by themselves are called non-spontaneous process. These require
external force and brings the system away from equilibrium.
• In spontaneous processes entropy of universe is increasing i.e. unavailable energy goes on increasing
and the workable energy is continuously decreasing. A spontaneous process comes to an end at
equilibrium, and since at equilibrium the entropy is maximum, it can be remarked that nature is trying to
attain the state of maximum entropy.
• Entropy is an extensive property.
• Entropy of reaction: m1 A  m2 B 
 n1C  n2 D

Product Reactant
S reaction    n S  mS

S = absolute entropies of respective substances.

n and m = moles of products and reactants respectively
S reaction    n1S C  n 2S D    m1S A   m 2SB  

Entropy changes of universe for reversible process:

Let us consider an isothermal reversible process. In this the system absorbs heat q from surroundings at
temperature T. This results in an increase in the entropy of system given by.
q
Ssystem 
T
q
Ssurroundings 
T
Total entropy of the process = Ssystem  Ssurroundings
q  q 
Suniverse   
T  T 
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Suniverse  0
Entropy change of universe for an irreversible processes:
Let q amount of heat is transferred from system which is at higher temperature (T2) to the surroundings which
is at lower temperature (T1)
q
 Decrease in entropy of system 
T2

Incease in entropy of surroundings   q

T1
 Total entropy change  Ssystem  Ssurrounding
q q 1 1  T  T 
Suniversel   q   q 2 1
T2 T1  T1 T2   T1.T2 
 T2  T1  0
 Suniverse  0