Module 2 - Second Law of Thermodynamics

Limitations of First Law:

 It does not ensure that the process will take place.

 It does not provide means for predicting the direction of processes

Second law
 provide means for predicting the direction of processes,
 establishing conditions for equilibrium,
 determining the best theoretical performance of cycles, engines and other devices.

Kelvin-Planck statement
It states that “It is impossible to construct a device which operates on a cycle and produces
no other effect than the transfer of heat from a single body to produce work.” This means
that it is impossible to construct an engine whose sole purpose is to convert the heat from
a high-temperature source/reservoir into an equal amount of work.

Clausius Statement
Heat cannot flow from body at lower temperature to body at higher temperature
spontaneously but it can be made possible with an external work.

Heat Engine:
o they receive heat from a high-temperature source
o they convert part of this heat to work
o they reject the remaining waste heat to a low temperature
sink atmosphere
o they operate on a cycle

Thermal efficiency:
 Represent the magnitude of the energy wasted in order to
complete the cycle.
 A measure of the performance that is called the thermal
efficiency.
 Can be expressed in terms of the desired output and the required input
Desired Result
 th 
Required Input
 For a heat engine the desired result is the net work done and the input is the heat supplied
to make the cycle operate.

The thermal efficiency is always less than 1 or less than 100 percent.

Wnet , out
th 
Qin
 where Wnet , out  Wout  Win
Qin  Qnet
 Applying the first law to the cyclic heat engine

𝑄𝑛𝑒𝑡,𝑖𝑛 − 𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = 0

𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = 𝑄𝑛𝑒𝑡,𝑖𝑛

𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡

 The cycle thermal efficiency may be written as

Wnet , out
 th 
Qin
Q  Qout
 in
Qin
Q
 1  out
Qin
 A thermodynamic temperature scale related to the heat transfers between a reversible
device and the high and low-temperature reservoirs by
QL TL

QH TH
 The heat engine that operates on the reversible Carnot cycle is called the Carnot Heat
Engine in which its efficiency is

TL
th, rev  1 
TH
Heat Pumps and Refrigerators

 A device that transfers heat from a low temperature medium to a high temperature one is
the heat pump.
 Refrigerator operates exactly like heat pump except that the desired output is the amount
of heat removed out of the system
 The index of performance of a heat pumps or refrigerators are expressed in terms of the
coefficient of performance.
 Q QH QH
COPR  L COPHP  
Wnet , in Wnet , in QH  QL

Carnot Cycle

Process Description
1-2 Reversible isothermal heat addition at high temperature
2-3 Reversible adiabatic expansion from high temperature to low
temperature
3-4 Reversible isothermal heat rejection at low temperature
4-1 Reversible adiabatic compression from low temperature to high
temperature
Execution of Carnot cycle in a piston cylinder device
 Carnot’s Theorem: Among the many heat engines operating between the same temperature
limits, only reversible heat engine (Carnot Engine) will have highest efficiency.

The thermal efficiencies comparison are as follows

The coefficients of performance of actual and reversible refrigerators operating between the
same temperature limits compare as follows

Problem #2.1: A power station contains a heat engine operating between two heat reservoirs, one
consisting of steam at C and the other consisting of water at C. What is the maximum
amount of electrical energy which can be produced for every Joule of heat extracted from the
steam?

Solution:
The maximum efficiency comes from using a Carnot (reversible)
𝑄𝐻 𝑇
engine, for which = 𝐻 , and so
𝑄𝐶 𝑇𝐶

With TH =373 K and TH =293 K;

For every Joule of heat extracted from the hot reservoir (QH = 1 J)

293
𝑊 = 1𝑥 (1 − 373) = 0.2144 𝐽

Problem #2.2: When a fridge stands in a room at C, the motor has to extract 500W of heat
from the cabinet, at C, to compensate for less than perfect insulation. How much power must
be supplied to the motor if its efficiency is 80% of the maximum achievable?
Solution:
The maximum efficiency comes from using a Carnot (reversible)
𝑄𝐻 𝑇
fridge, for which = 𝐻. Here QC is known, and so
𝑄𝐶 𝑇𝐶

(In this question W, QC, and QH will refer to energy transfer per
second, measured in Watts.) With TH =293 K and TC = 277 K, QC
= 500 W gives Wmax = 29 W.

However the real fridge works at 80% of the maximum efficiency,

29
so 𝑊 = = 36 𝑊
0.8

Problem #2.3: Two reversible engines A & B are arranged in series, EA rejecting heat directly to
engine, EB. EA receives 200 kJ at a temperature of 421 ͦ C from a hot source, while EB is in
communication with a cold sink at a temperature of 4.4 ͦ C. If the work output of EA is twice that
of EB, find the efficiency of each engine.

Solution:
From Thermodynamic temperature scale we know that,

𝑄1 𝑇1 𝑄2 𝑇2
= ; =
𝑄2 𝑇2 𝑄3 𝑇3

𝑄1 𝑄1 𝑄2 𝑇1
But = 𝑥 =
𝑄3 𝑄2 𝑄3 𝑇3

 Q3 = 79.94 kJ
Since, WA = 2 WB

𝑄1 − 𝑄2 = 2(𝑄2 − 𝑄3 )  Q2 = 119.96 kJ
𝑄1 𝑇1
=  T2 = 143.26 ͦ C ;
𝑄2 𝑇2

𝑾𝑨
𝜼𝑨 = = 𝟒𝟎% where WA = Q1 –Q2
𝑸𝟏

𝑾𝑩
𝜼𝑩 = = 𝟑𝟑. 𝟑𝟔% where WB = Q2 –Q3
𝑸𝟐
 ENTROPY – A Measure of Disorder

 Derivation of Entropy from Second Law

Consider the following combined system consisting of a Carnot heat engine and a
piston cylinder system

First Law applied to the combined system

dEC  Qrev  WC ; WC  Qrev  dEC
For a Carnot Engine (reversible cycle)
Qrev TR TR
  Qrev  Q 
Q T T
Q
Substituting WC   TR  dEC
T
Let the system undergo a cycle while the Carnot cycle undergoes one or more cycles. Integrate
over entire cycle. (Recall, system energy is a state property)
Q
 WC    TR   dEC
T
The net work for one cycle is
Q
WC  TR   
 T boundary

The combined system (cycle) draws heat from a single reservoir while involving work WC
Based on K-P statement the combined system cannot produce net work output  WC 
0
 Q  0
 
 T boundary
 This is the Clausius Inequality which is valid for all thermodynamic cycles, reversible or
irreversible.

For a reversible cycle (no irreversibilities in the system)  Q   0

  Int
 T  rev

Since the cycle integral of (dQ/T) is 0, the quantity dQ/T is a state property, it does not
depend on the path (similar to  dE  0 ).

Q
dS   
We call this as new property entropy, S,
units : kJ/K
 T int
rev

For a process where the system goes from state 1 to 2; S2  S1    Q 

2

1
 T int
rev

Specific entropy s= S/m

2  Q / m  2  q 
s 2  s1       
1
 T  int rev
1
 T  int
rev

The entropy change between two specified states is the same whether the process is reversible
or irreversible

Irreversible 2
T process
Internally reversible
process
1

S
To calculate S2-S1 evaluate  Q / T for the reversible path. Consider a cycle made up of an
irreversible process followed by a reversible process

Applying Clausius Inequality to the cycle

 Q Q Q
  12    21    0
T  T b  T int rev

2  Q 
1   S1  S 2   0
 T b
Q
S 2  S1  12  
 T b
Remove inequality sign to get the entropy balance equation for a closed system

Q
S 2  S1  12    S gen
 T b

Change in entropy Entropy transfer to the Entropy generated in the

of the system system by heat transfer system due to irreversibilities
 0 irreversible process

S gen  0 reversible process
 0 impossible process


For an isolated system (adiabatic closed system)

Q
Sisol  12  S gen
T

Since Sgen 0  Sisol 0

This is the Increase in Entropy Principle which simply stated says that for an isolated system
the entropy always increases or remains the same

A process that is both adiabatic and reversible is referred to as isentropic, and for a closed
Q
system, Sisentropic  12  S gen  0 .
T
Therefore, entropy is constant, S1=S2.
Evaluation of Entropy Change in a Closed System

System
Q W

Apply First Law neglecting KE and PE effects, no shaft work

In differential form du  q  w  q  Pdv

q  du  Pdv
q so
For an internally reversible process ds 
T

Tds  du  Pdv ----------------- (1)

recall h  u  Pv  du  d (h  Pv)  dh  Pdv  vdP

substitute du into the above equation

Tds  (dh  Pdv  vdP)  Pdv ------------------- (2)

Tds  dh  vdP
These are the Gibb’s equations (or simply Tds equations)

For a system undergoing a process from state 1 to state 2

du 2 P
s2  s1  12 ds  12  1 dv
T T
dh v
s2  s1  12 ds  12  12 dP
T T
 Entropy Change for an Ideal Gas

For an ideal gas du  cV dT , dh  c P dT , Pv  RT

du 2 P 2 c dT 2 dv
s2  s1     dv   V  R
2

1 T 1 T 1 T 1 v

and
dh 2 v 2 c dT 2 dP
s 2  s1     dP   P  R
2

1 T 1 T 1 T 1 P

If the specific heats cP and cV are taken as constant

dT v 
s2  s1  cV 
2
 R ln  2 
1 T  v1 
T  v 
s2  s1  cV ln  2   R ln  2 
 T1   v1 

dT P 
s2  s1  cP 
2
 R ln  2 
1 T  P1 
T  P 
s2  s1  cP ln  2   R ln  2 
 T1   P1 

 Isentropic Efficiency for Turbine

  Isentropic Efficiency for Compressor:

Problem#2.4: Air enters a compressor and is compressed adiabatically from 0.1 MPa, 27 ͦ C to a
final state of 0.5 MPa. Find the work done on the compressor with an isentropic efficiency of 80
%.

Solution:
Applying SFEE for compressor,
𝑊̇
𝑊̇𝑐 = 𝑚̇(ℎ2𝑠 − ℎ1 )  𝑊𝑐 = 𝑚𝑐̇ = (ℎ2𝑠 − ℎ1 )

𝑊𝑐 = 𝑐𝑝 (𝑇2𝑠 − 𝑇1 )
𝛾−1
𝑇2𝑠 𝑝2 𝛾
For isentropic process;( ) = (𝑝 )  T2s = 475.4 K
𝑇1 1

Then,
𝑊𝑐 = 1.005(475.4 − 300) = 176 𝑘𝐽/𝑘𝑔

𝑾𝒄
(𝑾𝒄 )𝒂𝒄𝒕 = = 𝟐𝟐𝟎 𝒌𝑱/𝒌𝒈
𝜼𝒄
Problem #2.5: A piston–cylinder device contains 1.2 kg of nitrogen gas at 120 kPa and 27°C. The
gas is now compressed slowly in a polytropic process during which PV1.3= constant. The process
ends when the volume is reduced by one-half. Determine the entropy change of nitrogen during
this process.

Solution:
T  v 
Entropy Change, s2  s1  cV ln  2   R ln  2 
 T1   v1 
For a Polytropic process,

k 1
 T2   v1 
     So, T2 = T1 * (2)0.3 = 369 K
 T1   v2 
 369 
s2  s1  0.718* ln    0.287 * ln 0.5
 300 
s2 – s1 = 0.0596 kJ/kgK

Problem #2.6: Air at 20 ͦ C and 1.05 bar occupies 0.025 m3. The air is heated at constant
volume until the pressure is 4.5 bar, and then cooled at constant pressure back to original
temperature. Calculate a) the net heat flow from the air, b) the net entropy change.

Solution:

cp = 1.005kJ/kgK; cv = 0.718 kJ/kgK ------- Assumed

𝑝1 𝑣1 1.05𝑥105 𝑥0.025
From gas equation, 𝒎 = = = 𝟎. 𝟎𝟑𝟏𝟐 𝒌𝒈
𝑅𝑇1 287𝑥293

For Process 1-2 (Constant Volume Process):

𝑇2 𝑝
= 𝑝2 == T2 = 1255.7 K (Q)v=c = m cv (T2 – T1) = 21.56 kJ
𝑇1 1
For Process 2-3 (Constant Pressure Process):
(Q)p=c = m cp (T3 – T2) = - 30.18 kJ where T3 = T1 and –‘ve sign indicates heat loss
𝑇
Entropy change in process 1-2, 𝑠2 − 𝑠1 = 𝑚𝑐𝑣 ln 𝑇2 = 0.0326 𝑘𝐽/𝐾
1

𝑇
Entropy change in process 2-3, 𝑠3 − 𝑠2 = 𝑚𝑐𝑝 ln 𝑇3 = −0.0456 𝑘𝐽/𝐾
2

Net entropy change, (∆s) = s1 –s3 = - 0.013 kJ/K

Supplementary Problems for Practice

1. A reversible heat engine operates between two reservoirs at temperatures of 600 ͦ C and 40 ͦ
C. The engine drives a reversible refrigerator which operates between reservoirs at
temperatures of 40 ͦ C and -20 ͦ C. The heat transfer to the engine is 2 MJ and the net output
of the combined engine and refrigerator plant is 360 kJ. Find the heat transfer to the
refrigerant and the net heat transfer to the reservoir at 40 C. Also find these values if the
efficiency of the heat engine and COP of the refrigerator are each 40% of their maximum
possible values.

2. A reversible engine as shown in Figure below

during a cycle of operation draws 5 MJ from
the 400 K reservoir and does 840 kJ of work.
Find the amount and direction of heat
interaction with other reservoirs.

3. The scales are so chosen that a reversible cycle plots clockwise as a circle on T-s plane,.
The minimum and maximum values of the temperature are 305 and 627 K and the entropy
1.23 and 2.85 kJ/k respectively. Find the cycle work and efficiency.

4. A gas initially at 603 K expands until its volume is 5.2 times the initial volume according
to pvn = constant. If the initial and final pressures are observed to be 8.5 bar and 1 bar,
determine i) index of expansion, ii) workdone per kg of gas, iii) heat exchange per kg of
gas, and iv) entropy change per kg of gas. Assume cv = 0.712 kJ/kgK and γ = 1.4.

5. One kg of water at 273 K is brought into contact with a heat reservoir at 373 K. When the
water has reached 373 K, find the entropy change of the water, the heat reservoir and the
universe.