Second Law of

Thermodynamics
Dr. Rohit Singh Lather

Limitations of First Law of Thermodynamics

Heat flows from a system of higher temperature to a system of lower temperature and never from
lower temperature system to higher temperature system
Why does energy
travel always
from higher value
to lower value?

hotter side

colder side

Heat is transferred from hotter side to the colder side of the rod
But never from colder to hotter side by itself by itself

From first law of thermodynamics, Heat lost and heat gain must be equal in both the
processes
According to first law, it is assumed that the energy transfer can take place in either
direction, it does not specify the direction of energy transfer

 All work can be converted into heat but all heat cannot be converted into work
- For example: In internal combustion engine, all heat generated from combustion of fuel
is not converted into work, but a portion of input heat has to be rejected
to exhaust gases, oil, cooling water

QFuel
QFriction

QCooling Water

QOil

Image source: http://teamspeed.com

QExhaust

- Example : In power plants, all heat generated from combustion of coal is not converted

into work, but a portion of input heat has to be rejected in the condenser

Image source: http://google.com

What First Law of Thermodynamics Tells Us Interpretations

First law of thermodynamics states work can be converted into heat and heat into work
First law makes no distinction between forms of energy, silent about the possibility of
energy conversion
First law is not sufficient to predict weather a system will or will not under go a particular
change
First law of thermodynamics is a necessary condition but not sufficient condition for a
process to take place

What Second Law of Thermodynamics Tells Us Interpretations

Second law of thermodynamics indicates that, all heat cannot be converted into work
According to second law of thermodynamics, heat will only be transferred from high
temperature to lower temperature and not vice versa
Second law states that whether it is possible for energy transfer to proceed along a
particular direction or not
A cycle can only occur if it satisfies both the first law and second law of thermodynamics
First law of thermodynamics, is a quantitative statement and Second law of
thermodynamics, is a qualitative statement

Energy Reservoirs
Thermal Energy reservoirs (TER): is defined as a large
body of infinite heat capacity, which is capable of
absorbing or rejecting an unlimited quantity of heat
without
suffering
appreciable
change
in
its
thermodynamic coordinates. All process are quasi-static

TERH
(SOURCE)

Constant Temperature

Q1
WT

Boiler
Wp

Pump

Turbine

Condenser
Q2
Mechanical Energy reservoirs (MER): is a large body
enclosed by an adiabatic impermeable wall capable of
storing work as kinetic energy or potential energy. All
process are quasi-static

TERL
(SINK)

Constant Temperature

Wnet

MER

Heat Engine

Heat Engine is a device which working in a cycle converts energy in form of heat into work
- Heat engines convert heat to work

There are several types of heat engines, but they are characterized by the following:
- They all receive heat from a high-temperature source (oil furnace, nuclear reactor, etc.)
- They convert part of this heat to work
- They reject the remaining waste heat to a low-temperature sink
- They operate in a cycle

Heat Engine
Heat Source: Furnace

QB / Q1

Steam
Turbine
Water

Boiler

WT

Net work output of the

system during cyclic process

WT - WP

Steam

Boiler
Condenser

WP

Condenser

Water
Water

QC / Q2

Pump

Turbine

Pump

Heat Sink: Lake/River


=
Q B Q C = WT - WP
Q 1 Q 2 = WT - WP
"#$%#$ '()* WT WP
= Q
+,%#$ -./$
1

Q Q
= 1Q 2
1

Q
= 1 - Q2
1

Q2 = 60%- 70% Q1
= 30% - 40%

Source
T1 = 500C
Q1
Heat
Engine

Q W = Q2
T2 = 20C

Sink
(atmosphere)

Q. Is it possible to save the rejected heat QC in a power cycle?

Answer: NO, because without the cooling in condenser the cycle cannot be completed
- Every heat engine must waste some energy by transferring it to a low-temperature
reservoir in order to complete the cycle, even in idealized cycle

Refrigerator
In nature, heat flows from high-temperature regions to low-temperature ones
The reverse process, however, cannot occur by itself
The transfer of heat from a low- temperature region to a high-temperature one requires special
devices called refrigerators
Refrigerator

Compressor

QR/Q2
W

Throttle

Condenser

QC/Q1

Refrigerators are cyclic devices, and the working fluids used in the cycles are called refrigerant

Objectives of Refrigerator & Heat Pump

Desired Output

Warm Environment
T = T atm.

Condenser

Q1

Q1
Expansion
Valve

Compressor

Wc

Refrig
erator

Win

Q2
Evaporator

Refrigerated Space
T < T atm.

Desired Output

Warm House
T > T atm.

Heat
Pump

Win

Q2
Cold Environment
T = T atm.

In a refrigerator, the desired effect is the amount of heat

removed Q2 from the space being heated
The performance of refrigerators and heat pumps is
expressed in terms of the coefficient of performance (COP)

Q
= Q RQ
C
R
Q
= Q 2Q
1
2

T1 = 35C

Heat
Engine

Q2
T2 = - 4C

Refrigerator

COPR =

COPR =

(atmosphere)

Q1

W = Qc - QR
= Q1 - Q2

Sink

Q
= W2

Heat Pump
Heat pumps transfer heat from a low-temperature medium to a high-temperature
Refrigerators and heat pumps are essentially the same devices; they differ in their objectives
only
Refrigerator is to maintain the refrigerated space at a low temperature
On the other hand, a heat pump absorbs heat from a low-temperature source and supplies the
heat to a warmer medium

In a heat Pump, the desired effect is the amount of heat supplied

Q1 to the space being heated

COPHP =

Q
= W1

Q
= Q 1Q
1
2
Q
= 1 + Q 2Q
1
2
= 1 + COPR

The COP of a heat pump operating as a heat pump is higher that

the COP of the same machine operating as a refrigerator by unity

Heated Space
T1 = 25C

Q1
Heat
Pump

Q2
T2 = 4C

Atmoshpere

Performance of Refrigerators, Air-Conditioners, and Heat Pumps

The performance of air conditioners and heat pumps is often expressed in terms of the energy
efficiency ratio (EER) or seasonal energy efficiency ratio (SEER) determined by following
certain testing standards

- SEER : is the ratio the total amount of heat removed by an air conditioner or heat pump during a
normal cooling season (in Btu) to the total amount of electricity consumed (in watt-hours, Wh), and
it is a measure of seasonal performance of cooling equipment
- EER : is a measure of the instantaneous energy efficiency, and is defined as the ratio of the rate
of heat removal from the cooled space by the cooling equipment to the rate of electricity
consumption in steady operation

Therefore, both EER and SEER have the unit Btu/Wh

- 1 kWh = 3.412 Btu (1 Wh = 3.412 Btu, a device that removes 1 kWh of heat from the cooled
space for each kWh of electricity it consumes (COP = 1) will have an EER of 3.412)
- Therefore, the relation between EER and COP, EER = 3.412.COPR
The heat transfer rate is often given in terms of tones of heating or cooling
One ton = 12,000 Btu = 211 kJ/min

Air conditioners or heat pumps SEER: 13 to 21, which correspond to COP values of 3.8 to 6.2.
- Most air conditioners have an EER between 8 to 12 (COP of 2.3 to 3.5)
Best performance is achieved using units equipped with variable-speed drives (also called
inverters)

- Variable-speed compressors and fans allow the unit to operate at maximum efficiency for varying
heating/cooling needs and weather conditions as determined by a microprocessor
- In the air-conditioning mode, for example, they operate at higher speeds on hot days and at lower speeds
on cooler days, enhancing both efficiency and comfort

The EER or COP of a refrigerator decreases with decreasing refrigeration temperature

- Therefore, it is not economical to refrigerate to a lower temperature than needed

The COPs of refrigerators (range): 2.6 to 3.0 for cutting and preparation rooms
2.3 to 2.6 for meat, deli, dairy, and produce
1.2 to 1.5 for frozen foods
1.0 to 1.2 for ice cream units

Note: COP of freezers is about half of the COP of meat refrigerators

- It costs twice as much to cool the meat products with refrigerated air that is cold
enough to cool frozen foods
- It is good energy conservation practice to use separate refrigeration systems to meet
different refrigeration needs

Second Law of Thermodynamics: Kelvin Planks Statement

It is impossible for any system to operate in a thermodynamic cycle and deliver a net amount of
work to its surroundings while receiving an energy transfer by heat from a single thermal reservoir
- It is impossible for any device that operates on a cycle to receive
heat from a single reservoir and produce a net amount of work
- In other words, no heat engine can have a thermal efficiency of
100%
A heat engine that violates the Kelvin-Planck
statement of the second law cannot be built

Source (TH)
Qin
Heat
Engine

Qout = 0
Wnet = Qin
Thermal efficiency of 100%

Second Law of Thermodynamics: Clausius Statement

Heat cannot, of itself, pass from a colder to a hotter body
It is impossible for a self acting machine working in a cyclic process unaided by any external
agency, to convey heat from a body at a lower temperature to a body at a higher temperature

- Heat cannot flow from itself from a system low temperature to a

system at high temperature.
- COP = Q/W = Q/0 = ( a condition not possible)
- The only alternative is that some external work must be
supplied to the machine

System (T1)
Qin
Heat
Pump

Q2
System (T2)

A heat engine that violates the Kelvin-Planck

statement of the second law cannot be built

Perpetual Motion Machine of the Second Kind (PMMK2)

Without violating the first law, a machine can be imagined which would continuously absorb heat
from a single thermal reservoir and would convert this heat completely into work

- The efficiency of such a machine would be 100%

- This machine is called the perpetual motion machine of the second kind (PMM2)
Source (TH)
Qin
Heat
Engine

Qout = 0
Wnet = Qin

When the thermal energy is equivalent to the work done, this does not violate the law of
conservation of energy. However it does violate the more subtle second law of thermodynamics

Carnot Cycle

The cycle was first suggested by Sadi Carnot, in 1824, which works on reversible cycle

Any fluid may be used to operate the Carnot cycle, which is performed in an engine cylinder the
head of which is supposed alternatively to be perfect conductor or a perfect insulator of a heat
Heat is caused to flow into the cylinder by the application of high temperature energy source to
the cylinder head during expansion, and to flow from the cylinder by the application of a lower
temperature energy source to the head during compression
Source, T1

Cylinder Head

Heat Insulation
Piston

Diathermic Cover

Adiabatic Cover

Working
Substance

Sink, T2
Heat Insulation

Piston motion

The assumptions made for describing the working of the Carnot engine are as follows :
1. The piston moving in a cylinder does not develop any friction during motion
2. The walls of piston and cylinder are considered as perfect insulators of heat
3. The cylinder head is so arranged that it can be a perfect heat conductor or perfect heat insulator
4. The transfer of heat does not affect the temperature of source or sink
5. Working medium is a perfect gas and has constant specific heat
6. Compression and expansion are reversible

Source, T1

Diathermic Cover
Adiabatic Cover

Stage 1 Isothermal Expansion

(Process 1-2)
- Hot energy source at temperature T1 is applied
- Heat Q1 is taken in whilst the fluid expands
isothermally and reversibly at constant high
temperature T1

Q1

Working
Substance

Piston motion

Stage 2 Adiabatic Expansion

(Process 2-3)
- The cylinder becomes a perfect insulator so
that no heat flow takes place
- The fluid expands adiabatically and reversibly
whilst temperature falls from T1 to T2

Sink, T2

Diathermic Cover
Adiabatic Cover

Working
Substance

Q2

Stage 3 Isothermal Compression

(Process 3-4)
- Cold energy source at temperature T2 is applied
- Heat Q2 flows from the fluid whilst it is
compressed isothermally and reversibly at
constant lower temperature T2

Stage 4 - Adiabatic Compression

(Process 4-1)
- Cylinder head becomes a perfect insulator so
that no heat flow occurs
- The compression is continued adiabatically and
reversibly during which temperature is raised
from T2 to T1

2
= 1 - Q
Q1

Q1 = W1-2 = P1 V1 In
Q2 = W3-4

= - P3 V3 In

Q1 = W1-2 = mRT1 In
Q2 = W3-4

= mRT2 In

Heat Added
Heat Rejected


= =

P2 V2 = P3 V3

P4 V4 = P1 V1

PV= nRT

; PV/T = nR =C

P2V2/T1 = P3V3/T2

P4V4/T2 = P1V1/T1

Dividing 1/3 and 2/4

Dividing 5/6

T1 V2 ( -

1) =

T2 V3 ( -

1)

T1 V1 ( -

1) =

T2 V4 ( -

1)

(V2/V1) = (V3/V4)
Q
= 1 - Q2
1

= 1 -

T2
T1

Temperature

Isotherms
T1

Q1

Q2

T2
4
S1 =S4

2
Frictionless
Adiabats
3

S2 = S3

Entropy

Area of the rectangle a-b-c-d represents work output per cycle and it equals
Q1 Q2 = (T1 T2).dS

Efficiency of a Reversible Heat Engine

From the above expression, it may be noted that as T2 decreases and T1 increases, efficiency of
the reversible cycle increases
Since is always less than unity, T2 is always greater than zero and positive (+ ve)

An engine, which consists entirely of reversible processes, can operate in the reverse direction,
so that it follows the cycle as shown and operates as a heat pump
Q1

Q2

(process 2-1)
Q1 is being rejected at
the upper temperature T1
Work (W) will be needed
to drive the pump

(process 4-3)
Q2 is being taken in at the lower
temperature T2 during the
isothermal expansion
Carnot Heat Pump
The enclosed area represents this work which is exactly equal to that flowing from it when used as engine

Carnot cycle cannot be performed in practice because of the following reasons

1. It is impossible to perform a frictionless process
2. It is impossible to transfer the heat without temperature potential
3. Isothermal process can be achieved only if the piston moves very slowly to allow heat transfer so
that the temperature remains constant
- Adiabatic process can be achieved only if the piston moves as fast as possible so that the heat
transfer is negligible due to very short time available
- The isothermal and adiabatic processes take place during the same stroke therefore the piston
has to move very slowly for part of the stroke and it has to move very fast during remaining
stroke
- This variation of motion of the piston during the same stroke is not possible

Equivalence of Clausius Statement to the Kelvin-Planck Statement

The Kelvins and Clausiuss statements of the second law are equivalent. i.e. if we violate Kelvins statement, then
we will automatically violate the Clausiuss statement of the second law (and vice-versa)
High Temperature Reservoir T1

A heat pump which requires no

work and transfers an amount of
Q2 from a low temperature to a
higher temperature reservoir No Work

Q1 > Q2

Q1

Q1

Heat
Pump

Heat
Engine

Net Work
(W) = Q1 Q2

(violation of the Clausius statement)

Q2

Q2 Heat rejected

Low Temperature Reservoir T 2

W = Q1 Q2; Since, there is no heat interaction with the low temperature, it can be eliminated
The combined system of the heat engine and heat pump acts then like a heat engine exchanging heat
with a single reservoir, which is the violation of the Kelvin-Planck statement

Violation of Kelvin Plank Statement leads to violation of Clausiuss statements

High Temperature Reservoir T1

Q1

Q1
A heat engine which converts all
heat to work, without rejecting
heat to low temperature

Heat
Engine

Q1 > Q2

W = Q1
W = Q1

(Violation of the Kelvin Plank statement)

Q2 = 0

Heat
Pump

Q2

Low Temperature Reservoir T 2

The combined system constitutes a device which transfers heat from low temperature reservoir to
high temperature without any work from external agency, which is the violation of the Clausius
statement

Can you beat Second Law

Can you cool your
room by leaving the
refrigerator door
open ?

The heat removed from the interior of the refrigerator is

deposited back into the kitchen by the coils on the back!
Second Law of Thermodynamics says that work is needed to
move the heat from cold to hot, so the actual amount of heat
added to the kitchen is MORE than the amount removed from
the refrigerator

Thermodynamic Temperature

The second corollary to the Kelvin-Planck statement holds that All reversible engines operating
between the same thermal reservoirs have the same
- This is independent of any details of the cycle or the materials involved
- The thermal efficiency, , should depend only on the character of the reservoirs involved

Consider a case of reversible heat engine operating between two reservoirs

- Its thermal efficiency is given by =

Q1 Q2
Q2
=
1
Q1
Q1

The temperature of a reservoir remains uniform and fixed irrespective of heat transfer

- This means that reservoir has only one property defining its state and the heat transfer from a reservoir
is some function of that property, temperature.
Thus Q = (K), where K is the temperature of reservoir

Q1 (K1)
Q1 T1
=
=>
Q2 (K2)
Q2 = T2 ; T1 and T2 are the thermodynamic temperatures of the reservoirs
Zero thermodynamic temperature (that temperature to which T2 tends, as the heat transfer Q2 tends to zero)
has never been attained and one form of third law of thermodynamics is the statement :

The temperature of a system cannot be reduced to zero in a finite number of processes

The amounts of heat rejected by engines B and C must

be the same since engines A and B can be combined into
one reversible engine operating between the same
reservoirs as engine C and thus the combined engine will
have the same efficiency as engine C.
Since the heat input to engine C is the same as the heat
input to the combined engines A and B, both systems
must reject the same amount of heat

After establishing the concept of a zero thermodynamic temperature, a reference reservoir is

chosen and assigned a numerical value of temperature
Any other thermodynamic temperature may now be defined in terms of reference value and the
heat transfers that would occur with reversible engine,

T = Tref.

Q
Qref.

Let us make an arbitrary choice to avoid ratios. We take, for convenience, the temperature of the
triple point of water to be 273.15 K. Thus for any system, the local T is
Q
T = 273.3.
Qref.
This implies we can connect our heat engine to a reservoir maintained at the triple point temperature
of water, and measure the associated Qs for the heat engine

We would like to drive our efficiency to be as close to unity as possible, nature limits us
Generally, we have little to no control over the environmental temperature TL, so it is a lower bound, usually
around TL 300 K. And material properties for engines limit TH . For many metals, TH 1500 K is approaching
values where material strength is lost
So a practical upper bound based on these numbers tell us
1 (300K)/(1500K) = 0.8 is may be the most we can expect. We plot as a function of TH for fixed TL =
300 K For real systems, with irreversible features, the values are much lower

The determination of thermodynamic temperature cannot be made in this way as it is not possible
to build a reversible engine
Temperatures are determined by the application of thermodynamic relations to other
measurements
The SI unit of thermodynamic temperature is the kelvin (K)
The relation between thermodynamic temperature and Celsius scale
- Thermodynamic temperature = Celsius temperature + 273.15
- The kelvin unit of thermodynamic temperature is the fraction 1 temperature of Triple point of
water

Carnot Theorem
It states that of all engines operating between a given constant temperature source and a
given constant temperature sink, none has a higher efficiency than a reversible engine
Let HEA be any heat engine and HEB be any reversible heat engine
We have to prove that efficiency of HEB is more than that of HEA
Let us assume that A > B
Q1A = Q1B = Q1
A = B

WA > WB

Source, T1

Q1A

Q1B
WA

HEA

Q2A
Sink, T2

HEB

Q2B

WB

Source, T1

Q1A
WB
WA

Q2A

HB

HEA

Q1B

Q2B

Sink, T2

HEB is reversed
Since HEB is a reversible heat engine, the magnitudes of heat and work transfer quantities will
remain the same, but their directions will be reversed
Since WA > WB, some part of WA (equal to WB) may be fed to drive the reversed heat engine HB.
Since Q1A = Q1B = Q1, the heat discharged by HB may be supplied to HEA
The source may, therefore, be eliminated

HEA

Q2A

Q1B = Q1
WB
WA

WA = WB

HB

Q1A = Q1

Q2B

Sink, T2

The net result is that HEA and H B together constitute a heat engine which, operating in a cycle
produces net work WA WB while exchanging heat with a single reservoir at T2
This violates the Kelvin-Planck statement of the second law Hence the assumption that A> B is
wrong
The combined system of heat pump HEB and engine HEA, becomes a PMM2

A cannot be greater than B

HEA and HB together violate the Kelvin-Planck statement, B > A

Similarly, if we assume B > A and reverse the engine HEA, we observe that B cannot be greater
than A, B = A

Since, the efficiencies of all reversible engines operating between the same heat reservoirs are the
same, the efficiency of a reversible engine is independent of the nature or amount of the working
substance undergoing the cycle
The efficiency of all reversible heat engines operating between the same temperature levels is
the same

Hopefully, you understand todays lesson.

Otherwise, youll end up like this cow.