MODULE III

ME/AU 010 506 THERMODYNAMICS

Abstract
Second law of thermodynamics- Various statements and their equivalence-
Reversible process and reversible cycles- Carnot cycles- Corollaries of the
second law – thermodynamic temperature scales – Clausius inequality-
Concept of entropy – Calculation of change in entropy in various
thermodynamic processes – Reversibility and irreversibility – Available and
unavailable energy – Third law of thermodynamics.

Noel Joseph Gomez

noel@scmsgroup.org
Contents
Introduction ............................................................................................................................................ 2
Thermal Energy Reservoir ....................................................................................................................... 2
Quality of Energy..................................................................................................................................... 2
Heat Engines ........................................................................................................................................... 3
Thermal Efficiency............................................................................................................................... 3
Introduction to Second Law of Thermodynamics ................................................................................... 4
Second Law of Thermodynamics ............................................................................................................ 4
Perpetual Motion Machine of the 2nd Kind (PMM2) .............................................................................. 4
Thermodynamic Temperature Scale ....................................................................................................... 4
Introduction
 No process is known to have taken place in violation of the first law of thermodynamics
 However, Satisfying the first law alone does not ensure that the process will actually take
place

Thermal Energy Reservoir

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.

A reservoir that

 supplies energy in the form of heat is called a source

 that absorbs energy in the form of heat is called a sink

Quality of Energy
Work can easily be converted to other forms of energy, but converting other forms of energy to
work is not that easy.

Work can always be converted to heat directly and completely, but the reverse is not true.

Therefore work can be converted to Heat directly and completely. Converting heat to work requires
the use of some special devices. These devices are called heat engines.
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.
5. Heat engines and other cyclic devices usually involve a fluid
to and from which heat is transferred while undergoing a
cycle.
6. This fluid is called the working fluid.

Thermal Efficiency
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 𝜂𝑡ℎ
𝑊𝑛𝑒𝑡 𝑄𝑜𝑢𝑡
𝜂𝑡ℎ = =1−
𝑄𝑖𝑛 𝑄𝑖𝑛
Introduction to Second Law of Thermodynamics
 Applies only for a cycle – not a process !!
 Not limited to identifying the direction of processes
 Asserts that energy has quality as well as quantity.
 Used in determining the theoretical limits for the performance of commonly used
engineering systems, such as heat engines and refrigerators

Second Law of Thermodynamics

The second law of thermodynamics is given by the 2 statements, viz.

1. Kelvin-Planck Statement (Heat Engine)

It is impossible for a heat engine to produce net work in a complete cycle if it exchanges heat
only with a body at single fixed temperature.
2. Clausius Statement(Refrigerator)
It is impossible to construct a device which operating in a cycle will produce no effect other
than the transfer of heat from a cooler to a hotter body.

Perpetual Motion Machine of the 2nd Kind (PMM2)

 If 𝑄2 = 0, then 𝑊𝑛𝑒𝑡 = 𝑄1 or 𝜂 = 1.00
 The heat engine will produce net work in a complete cycle by
exchanging heat with only one reservoir
 Such a heat engine is called PMM2

Thermodynamic Temperature Scale

Thermodynamics Temperature scale whose thermometric property does
not depend on the physical property of the working fluid.

To define a temperature scale that does not depend on the thermometric property of a substance,
Carnot principle can be used since the Carnot engine efficiency does not depend on the working
fluid. It depends on the temperatures of the reservoirs between which it operates.
Consider the operation of three reversible engines 1, 2 and 3. The engine 1 absorbs energy Q1 as heat
from the reservoir at T1, does work W1 and rejects energy Q2 as heat to the reservoir at T2.

Let the engine 2 absorb energy Q2 as heat from the reservoir at T2 and does work W2 and rejects energy
Q3 as heat to the reservoir at T3.

The third reversible engine 3, absorbs energy Q1as heat from the reservoir at T1, does work W3 and
rejects energy Q3 as heat to the reservoir at T3.
𝑊1 𝑄2
𝜂1 = =1− = 𝑓(𝑇1 , 𝑇2 )
𝑄1 𝑄1
𝑄1
∴ = 𝐹(𝑇1 , 𝑇2 )
𝑄2
𝑊2 𝑄3
𝜂2 = =1− = 𝑓(𝑇2 , 𝑇3 )
𝑄2 𝑄2
𝑄2
∴ = 𝐹(𝑇2 , 𝑇3 )
𝑄3
𝑊3 𝑄3
𝜂3 = =1− = 𝑓(𝑇1 , 𝑇3 )
𝑄3 𝑄1
𝑄1
∴ = 𝐹(𝑇1 , 𝑇3 )
𝑄3
 𝑄1
𝑄1 ⁄𝑄
3
=
𝑄2 𝑄2⁄
𝑄3
𝐹(𝑇1 , 𝑇3 )
∴ 𝐹(𝑇1 , 𝑇2 ) =
𝐹(𝑇2 , 𝑇3 )
Since T3 does not appear on the left side, on the RHS also T3 should cancel out. This is possible if the
function 𝐹 can be written as

𝐹(𝑇1 , 𝑇2 ) = 𝜙(𝑇1 )𝜓(𝑇2 )

𝜙(𝑇1 )𝜓(𝑇3 )
∴ 𝜙(𝑇1 )𝜓(𝑇2 ) =
𝜙(𝑇2 )𝜓(𝑇3 )
𝜙(𝑇1 )𝜓(𝑇3 )
𝜙(𝑇1 )𝜓(𝑇2 ) =
𝜙(𝑇2 )𝜓(𝑇3 )
1
∴ 𝜓(𝑇2 ) =
𝜙(𝑇2 )
𝑄1 𝜙(𝑇1 )
∴ = 𝐹(𝑇1 , 𝑇2 ) =
𝑄2 𝜙(𝑇2 )
Now, there are several functional relations that will satisfy this equation. For the thermodynamic scale
of temperature, Kelvin selected the relation
𝑄1 𝑇1
=
𝑄2 𝑇2
That is, the ratio of energy absorbed to the energy rejected as heat by a reversible engine is equal to
the ratio of the temperatures of the source and the sink.

The equation can be used to determine the temperature of any reservoir by operating a reversible
engine between that reservoir and another easily reproducible reservoir and by measuring efficiency
(heat interactions). The temperature of easily reproducible thermal reservoir can be arbitrarily
assigned a numerical value (the reproducible reservoir can be at triple point of water and the
temperature value assigned 273.16 K).

The efficiency of a Carnot engine operating between two thermal reservoirs the temperatures of
which are measured on the thermodynamic temperature scale, is given by
𝑄2 𝑇2
𝜂1 = 1 − =1−
𝑄1 𝑇1