1 - 2nd Law

ME 211 (Thermodynamics) Lecture 1
Department of Mechanical Engineering Second Law of Thermodynamics
Thermodynamics: Thermodynamics is the science of energy in which the storage, the transformation
and the transfer of energy are studied. Or, Thermodynamics is the science of energy dealing various
forms of energy. Or, The mist of science clarifying the relationship of energy is called
Thermodynamics[12].
Thermodynamics includes all aspects of energy and energy transformations, including power
generation, refrigeration, and relationships among the properties of matter.
Classification of Thermodynamics
Thermodynamics can be classified as follows
I. Classical Thermodynamics (Macroscopic Thermodynamics)
II. Statistical Thermodynamics (Microscopic Thermodynamics)
III.Quantum thermodynamics (Quantum Mechanics)
Page # 1 M. A. Islam
1) Macroscopic Thermodynamics or Classical Thermodynamics: The branch of thermodynamics

that does not consider the molecular level for analysis. (A macroscopic consideration addresses
the appropriate observable averages of the microscopic phenomena)
2) Microscopic Thermodynamics or Statistical Thermodynamics: The branch of thermodynamics

that considers the molecular level for analysis. (A microscopic viewpoint is used to understand a
process or system by considering the particle nature of matter)
Thermodynamic equilibrium: A system is said to be in thermal equilibrium if it satisfies mechanical,

thermal, and chemical equilibrium. Or, Any thermodynamic system satisfying thermal, mechanical and
chemical equilibrium is called thermodynamic equilibrium.
Classification of Thermodynamic equilibrium
3) Mechanical equilibrium: Any system having no unbalanced force inside the system is said to have
Mechanical equilibrium
4) Thermal equilibrium: Any system having no temperature difference among its constituents is said
to have Thermal equilibrium
5) Chemical equilibrium : Any system having no chemical reaction occurring among its constituents
is said to have Chemical equilibrium
Laws of Thermodynamics
1) First Law of Thermodynamics
2) Second Law of Thermodynamics
3) Third Law of Thermodynamics
4) Zeroth Law of Thermodynamics
First Law of Thermodynamics

Whenever a system undergoes a cycle the net amount of heat transferred is equal to the net amount
of work produced or vice versa [1]
Zeroth Law of Thermodynamics
A temperature scale exists for all substances in nature and provides an absolute measure of their
tendencies to exchange heat.
Or, If two systems are in equilibrium with a third system, then the two systems are in equilibrium
with each other[8] A B
Source: A reservoir that supplies energy in the form of heat is called a source.
Sink: A reservoir that absorbs energy in the form of heat is called a sink .
Thermal Energy Reservoir (TER): A hypothetical body with a relatively large thermal energy capacity
(mass specific heat) that can supply or absorb finite amounts of heat without undergoing any change in
temperature.
TER are often referred to as Heat reservoirs as they supply or absorb energy in the form of heat
Mechanical Energy Reservoir (MER): A large body enclosed by adiabatic impermeable wall capable
of storing work potential and kinetic energy (All processes within MER are quasistatic).
Heat Engine: A device which performs work using heat operating through a cycle.
Characteristics of Heat Engines
1) They receive heat from a high-temperature source (solar energy, oil furnace, nuclear reactor, etc.)
2) They convert part of this heat to work (usually in the form of a rotating shaft).
3) They reject the remaining waste heat to a low-temperature sink (the atmosphere, rivers, etc.)
4) They operate on a cycle.
TH
W
Heat Engine
TL
Thermal Efficiency: The ratio of work output to heat input is called thermal efficiency. Or, The fraction
of the heat input that is converted to net work output is a measure of the performance of a heat engine
and is called the thermal efficiency[].
Heat Pump: A device which maintains a body at a temperature higher than the temperature of the
surroundings operating through a cycle
TH
TH
W
W
Refrigerator
Heat Pump
TL TL
Refrigerator: A device which maintains a body at a temperature lower than the temperature of the
surroundings operating through a cycle.
Air conditioners are basically refrigerators whose refrigerated space is room or a building instead of
the food compartment.
Coefficient of Performance (COP): The ratio of Desired Effect to work input is called COP.
Energy efficiency rating (EER): The amount of heat removed from the cooled space in Btu’s for 1
Wh (watt-hour) of electricity consumed.
TH TH TH
W W W
Heat Engine Heat Pump Refrigerator
TL TL TL
Class Problems
Heat is transferred to a heat engine from a furnace at a rate of 80 MW. If the rate of waste heat
rejection to a nearby river is 50 MW, determine the net power output and the thermal efficiency for
this heat engine.
Solution:
Class Problems
A car engine with a power output of 65 hp has a thermal efficiency of 24 percent. Determine the fuel
consumption rate of this car if the fuel has a heating value of 19,000 Btu/lbm (that is, 19,000 Btu of
energy is released for each lbm of fuel burned).
Solution:
Class Problems
A heat pump is used to meet the heating requirements of a house and maintain it at 20°C. On a day
when the outdoor air temperature drops to 2°C, the house is estimated to lose heat at a rate of 80,000
kJ/h. If the heat pump under these conditions has a COP of 2.5, determine (a) the power consumed by
the heat pump and (b) the rate at which heat is absorbed from the cold outdoor air.
Solution:
Class Problems
The food compartment of a refrigerator, shown in Figure, is maintained at 4°C by removing heat from
it at a rate of 360 kJ/min. If the required power input to the refrigerator is 2 kW, determine (a) the
coefficient of performance of the refrigerator and (b) the rate of heat rejection to the room that houses
the refrigerator.
Solution:
Limitations of 1st Law of Thermodynamics

1) The law does not give any direction of flow of heat and Work
2) Does not give the condition in which energy transfer occurs
3) Heat and work are not mutually convertible
4) Only concerned with the quantity of energy interactions with no regard to its quality
Second Law of Thermodynamics

It is impossible to construct a system which will operate in a cycle, extract heat from a reservoir,
and do an equivalent amount of work on the surroundings.
Advantages of 2nd Law of Thermodynamics

5) It identifies the direction of processes
6) Energy has quality as well as quantity
7) Used to determine the theoretical limits for the performance of commonly used engineering
systems, such as heat engines and refrigerators
8) Can be used to predict the degree of completion of chemical reactions.
Processes Limited by 1st Law
Processes Limited by 2nd Law
A process cannot occur unless it satisfies both the first and the second laws of thermodynamics
Two statements of 2nd Law of Thermodynamics
1. It is impossible to construct a system which will operate in a cycle and transfer heat from a cooler
to a hotter body without work being done on the system by the surroundings. (Clausius Statement)
2. It is impossible to construct a system which will operate in a cycle and produces no other effect
than the production of work and the transfer heat from a single body. (Kelvin Plank Statement)
Equivalence of 2 statements of 2nd Law of Thermodynamics
TH TH TH
𝑸𝑨 𝑸𝑨
𝑾=𝑸 𝑨 −𝑸 𝑩
+ ∮ ∮
𝑸𝑩 𝑸 𝑨 −𝑸 𝑩
TL TL TL
(a) (b) (c)

Suppose, it is possible to transfer heat without any device violating the Clausius statement as in
figure a.
If any reversible engine is added as figure b, the work output of the engine . So, net result is
figure c where no heat is exchanged with the reservoir TH .
Figure c is the violation of Kelvin-Plank statement.
Therefore the violation of Clausius statement is the violation of Kelvin Planks statement
Perpetual motion machine of the first kind (PMM1) (A PMM1 violates the first law)
 A machine producing a continuous supply of work without absorbing energy from the
surroundings is called perpetual motion machine of the first kind.
 A PMM1 violates the 1st Law by operating in a cycle by producing a greater net work output
than the net amount of heat input into the machine.
Perpetual motion machine of the second kind (PMM2) (A PMM2 violates the 2nd law)
 A machine which would preform work solely by absorbing energy as heat from a single
reservoir.
 A PMM2 violates the 2nd Law by producing work in a cycle and exchange heat only with bodies
at a single fixed temperature.
Perpetual motion machine of the third kind (PMM3) (A PMM3 eliminates friction)
 A device set in motion will remain in motion indefinitely without slowing down.
Carnot Engine: A hypothetical Engine which is 100% efficient is called Carnot engine. or An engine
that converts heat into work with the highest possible efficiency[5]
Carnot Cycle:
1) A reversible isothermal process in which heat is transferred
to or from the high temperature reservoir.
2) A reversible adiabatic process in which the temperature of
the working fluid decreases from the high temperature to
the low temperature.
3) A reversible isothermal process in which heat is transferred
to or from the low temperature reservoir.
4) A reversible adiabatic process in which the temperature of
the working fluid increases from the low temperature to the
high temperature
Thermal efficiency of a Carnot cycle
Figure: P-V & T-S diagram of the Carnot cycle [1]
Carnot cycle consists of 2 isothermal & 2 adiabatic processes

Process 1-2: Reversible Isothermal expansion
Process 2-3: Reversible Adiabatic expansion
Process 3-4: Reversible Isothermal compression
Process 4-1: Reversible Adiabatic compression
Carnot cycle consists of 2 isothermal & 2 adiabatic processes

Process 1-2: Heat transferred
Process 2-3: Heat transferred ; Work done
Process 3-4: Heat transferred ,
Process 4-1: Heat transferred ; Work done
Thermal efficiency
Thermal efficiency
For reversible adiabatic processes 2-3 & 4-1: and
[= &=
The thermal efficiency of a Carnot cycle
Therefor e, the thermal efficiency of a Carnot cycle depends upon the highest and lowest
temperatures
The reversed Carnot cycle
Figure: P-V & T-S diagram of the reversed Carnot cycle [1]
The Carnot heat-engine cycle just described is a totally reversible cycle. Therefore, all the processes
that comprise it can be reversed, in which case it becomes the Carnot refrigeration cycle.
Process 1-2: Reversible Isothermal compression
Process 2-3: Reversible Adiabatic condensation
Process 3-4: Reversible Isothermal expansion
Process 4-1: Reversible Adiabatic evaporation
Carnot’s Theorem: It is impossible to construct an engine operating between two given temperature
reservoir that is more efficient than the Carnot engine.
Proof: Consider the converse of the statement is true , the engine is more efficient than Carnot
refrigerator.
TH
𝑸𝑯
𝑸𝑯 𝑸𝑯
𝑾 ′ −𝑾
𝑾′ 𝑾 𝑬𝒏𝒈𝒊𝒏𝒆 𝑹 𝑪𝒂𝒓𝒏𝒐𝒕
𝑬𝒏𝒈𝒊𝒏𝒆 𝑹 𝑪𝒂𝒓𝒏𝒐𝒕
𝑸 𝒓𝒆𝒗 𝑸𝑳
𝑸′ 𝑳 𝑸𝑳
TL
TL
From 1st Law,

Considering ; ;
For the combined plant, net amount of work leaving the system from single reservoir violating the 2nd
Law. So, the original statement must be true.
Corollary 1( Carnot’s Theorem)
The efficiency of Carnot’s engine is not dependent on the working substance.
Proof: Suppose a Carnot engine drives a Carnot refrigerator such that

TH
TH
𝑸𝑯 𝑸′ 𝑯
𝑸𝑯 𝑸′ 𝑯
𝑾 −𝑾 ′ 𝑬 𝑾′
𝑾 𝑾′ 𝑪𝒂𝒓𝒏𝒐𝒕 𝑹 𝑪𝒂𝒓𝒏𝒐𝒕
𝑬 𝑪𝒂𝒓𝒏𝒐𝒕 𝑹 𝑪𝒂𝒓𝒏𝒐𝒕
𝑸𝑳 𝑸𝑳 𝑸𝑳
TL
TL
From 1st Law,

Considering indicating =
For the combined plant, net amount of heat leaving the system from single reservoir violating the 2 nd
Law. So, the efficiency of a Carnot engine is not dependent on the working substance.
Corollary 2 ( Carnot’s Theorem)
All reversible engine working between two reservoirs have same efficiency.
Corollary 1 (2nd Law of Thermodynamics)
It is impossible to construct a system which will operate in a cycle and transfer heat from a cooler to
a hotter body without work being done on the system by the surroundings. (Clausius Statement)
Proof: Assume the converse of the postulation is true for the heat
Hot Reservoir
pump (HP) and Q and W represents heat and work respectively.
|𝑸| |𝑾 |+|𝑸|
|𝑾 |
According to the 1st law, for HP of cold reservoir = of hot 𝑾 =𝟎 HP HE
reservoir
|𝑸| |𝑸|
If an heat Engine (HE) operates between the 2 reservoirs and
Cold Reservoir
supplies units of heat. Again from 1 Law,
st
to cold reservoir == from hot reservoir
For the combined plant, Exactring amount of heat = doing W amount of work
But, according to 2nd Law which is impossible. So, the original statement must be true.

It is impossible to construct an engine operating between only two heat reservoirs which will
have a higher efficiency than a reversible engine operating between the same two reservoirs.
Hot Reservoir Hot Reservoir

𝑸𝟏 𝑸𝟏 𝑸𝟏 𝑸𝟏
𝑾𝑿 𝑾𝑹 𝑾 𝑿 −𝑾 𝑹 𝑾𝑹
X R X R
𝑸 𝟏 −𝑾 𝑿 𝑸 𝟏 −𝑾 𝑹 𝑸 𝟏 −𝑾 𝑿 𝑸 𝟏 −𝑾 𝑹
Cold Reservoir Cold Reservoir
Proof: Consider a heat engine X and reversible engine R working between 2 reservoirs rejecting heat
to cols reservoir as shown in figure.

Assume the converse of the postulation is true. then
So, the heat rejected
Again if the engine R act as HP, For the combined plant, Exactring amount of heat = doing amount
of work
But, according to 2nd Law which is impossible. So, the original statement must be true.

All reversible engines operating between the same two reservoirs have the same efficiency.

A scale of temperature can be defined which is independent of any particular thermometric
substance, and which provides an absolute zero of temperature.
Proof: Energy reservoirs are characterized by their temperatures, the

thermal efficiency of reversible heat engines is a function of the
reservoir temperatures only.
We know,
In terms of new function
Likewise for Reversible engines A, B & C
; ;
Now considering the identity,
Proof: Continued
Now considering the identity,
L. H. S is a function of = R. H. S must also be a function of
For a reversible heat engine operating between two reservoirs at

temperatures TH and TL
Lord Kelvin first proposed taking to define a thermodynamic temperature

scale
(Kelvin Temperature scale)

The efficiency of any reversible engine operating between more than two reservoirs must be less
than that of a reversible engine operating between two reservoirs which have temperatures equal
to the highest and lowest temperatures of fluid in the original engine
Proof:
Whenever a system undergoes a cycle, is zero if the cycle is reversible and negative if
irreversible, i.e. in general 0 (Clausius Inequality)
Proof: The figure shows one Carnot engine and one irreversible engine operating between same
reservoirs.
For the same amount of heat addition ) :
From 1st Law, TH
Assume that 𝑸𝑯 𝑸𝑯
Then 𝑾 𝒓𝒆𝒗 𝑾 𝒊𝒓𝒓
For irreversible cycle, 𝑬 𝑪𝒂𝒓 𝑬 𝒊𝒓𝒓
For reversible cycle , 𝑸 𝒓𝒆𝒗 𝑸𝑳
Combining irreversible and reversible cycle
TL
Corollary 7 (2nd Law of Thermodynamics)/ Entropy is a property
There exists a property of a closed system such that a change in its value is equal to for any reversible
process undergone by the system between state 1 and state 2.
Proof: Suppose a system(control mass) undergoes a reversible process from state 1 to state 2 along
path A and C, and returns along path B to complete cycles.
For reversible cycle, …….. (1)
……….. (2)
Subtracting the equations (2) – (1)
Since is the same for all reversible paths between states 1 and 2,
is independent of the path and is a function of the end states only.
Therefore ,it is a property which is called entropy and is designated S and defined by the relations as
follows. or Integrating

The entropy of any closed system which is thermally isolated from the surroundings either
increases or, if the process undergone by the system is reversible, remains constant.
Proof: Case 1: For thermally isolated system dQ=0 and for any reversible process . So for any
reversible adiabatic process dS= 0.
Case 2: Consider a cycle that is made up of two processes: process 1-2, which is arbitrary
(reversible or irreversible), and process 2-1, which is internally reversible, as shown in Figure
From the Clausius inequality 0
(The equality holds for an internally reversible process and the inequality for an irreversible
process)
For isolated system dQ=0, is known as the increase of entropy principle.
Various properties
The Internal Energy (U): The portion of energy stored in the chemical bonds of substances.
In general, internal energy consists of sensible, latent, chemical, and nuclear energies.
The Entropy (S): The randomness of a system is expressed in quantity is called entropy which is written as.
Entropy is small in ordered systems like crystals and large in disordered systems like solutions, melts, vapors.
Free Energy (G): The portion of substances internal energy which is available to perform
M. A. Islam would like to thank the following for preparing the lecture materials and have no
intention to plagiarize other than teaching students and use as reference materials.
Sl Books Authors
1 Engineering Thermodynamics Gordon Rogers & Yon Mayhew
2 Engineering Thermodynamics P. K. Nag
3 Thermal Engineering R. S. Khurmi
4 Thermodynamics M. C. Potter & C. W. Somerton
5 Engineering Thermodynamics J. B. Jones & R. E. Dugan
6 Engineering Thermodynamics Yunus A. Cengel& Michael A. Boles
7 Engineering Thermodynamics G. J. Van Wylen, R.. E. Sonntag & C. Brognakke
8 Physical Chemistry P. Atkins & J. Paula
9 Principles of Chemistry Mercer
10 Chemical Thermodynamics Smith
11 Thermal Physics R. F. Sekara
12 Thermodynamics for Materials
R. T. Hoff
Science
Lecture 1 ME 211 (Thermodynamics)
2nd Law of Department of Mechanical Engineering
thermodynamics
Page # 38
M. A. Islam
Lecture 1 ME 211 (Thermodynamics)
2nd Law of Department of Mechanical Engineering
thermodynamics
Page # 39
M. A. Islam

1 - 2nd Law

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ME 211 (Thermodynamics) Lecture 1

Department of Mechanical Engineering Second Law of Thermodynamics

Thermodynamics can be classified as follows

I. Classical Thermodynamics (Macroscopic Thermodynamics)

II. Statistical Thermodynamics (Microscopic Thermodynamics)

III.Quantum thermodynamics (Quantum Mechanics)

1) Macroscopic Thermodynamics or Classical Thermodynamics: The branch of thermodynamics

2) Microscopic Thermodynamics or Statistical Thermodynamics: The branch of thermodynamics

Thermodynamic equilibrium: A system is said to be in thermal equilibrium if it satisfies mechanical,

First Law of Thermodynamics

Limitations of 1st Law of Thermodynamics

Second Law of Thermodynamics

Advantages of 2nd Law of Thermodynamics

Processes Limited by 1st Law

Processes Limited by 2nd Law

Two statements of 2nd Law of Thermodynamics

Equivalence of 2 statements of 2nd Law of Thermodynamics

(a) (b) (c)

Thermal efficiency of a Carnot cycle

Figure: P-V & T-S diagram of the Carnot cycle [1]

Carnot cycle consists of 2 isothermal & 2 adiabatic processes

Thermal efficiency of a Carnot cycle

Carnot cycle consists of 2 isothermal & 2 adiabatic processes

Thermal efficiency of a Carnot cycle

The reversed Carnot cycle

From 1st Law,

Corollary 1( Carnot’s Theorem)

The efficiency of Carnot’s engine is not dependent on the working substance.

Proof: Suppose a Carnot engine drives a Carnot refrigerator such that

From 1st Law,

Corollary 2 ( Carnot’s Theorem)

to cold reservoir == from hot reservoir

Corollary 2 (2nd Law of Thermodynamics)

Hot Reservoir Hot Reservoir

to cols reservoir as shown in figure.

Corollary 3 (2nd Law of Thermodynamics)

Corollary 4 (2nd Law of Thermodynamics)

Proof: Energy reservoirs are characterized by their temperatures, the

Corollary 4 (2nd Law of Thermodynamics)

L. H. S is a function of = R. H. S must also be a function of

For a reversible heat engine operating between two reservoirs at

Lord Kelvin first proposed taking to define a thermodynamic temperature

Corollary 5 (2nd Law of Thermodynamics)

Corollary 6 (2nd Law of Thermodynamics)

Corollary 8 (2nd Law of Thermodynamics)

From the Clausius inequality 0

For isolated system dQ=0, is known as the increase of entropy principle.

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