Thermodynamics

Thermodynamics
Thermodynamic is a branch of physics which mainly deals with the transformation of
heat into mechanical work.
Thermodynamic System: A system may be defined as a definite quantity of matter
(solid, liquid or gases) bounded by some closed surface.
The simplest example of a system is a gas contained in a cylinder with a movable
piston.
There are three classes of system:
Open System:
A system which can exchange matter and energy with the surroundings is called an
open system.e.g. Air compressor.
Air at low pressure enters and air at high pressure leaves the system i.e., there is an
exchange of matter and energy with the surroundings.
Closed System:
A system which can exchange only energy (and not matter) with the surroundings is
called a closed system.e.g. Gas enclosed in a cylinder expands when heated and
drives the piston outwards. The boundary of the system moves but the matter (here
gas) in the system remains constant.
Isolated system:
A system which is thermally insulated and has no communication of heat or work
with the surroundings is called isolated system.

Zeroth Law of Thermodynamics(Thermodynamic Equilibrium):

Statement:
The zeroth law of thermodynamics states that if two bodies A and B are each
separately in thermal equilibrium with a third body C, then A and B are also in
thermal equilibrium with each other.

Explanation:
We consider two systems A and B insulated from each other but in good thermal
contact with a common system C. Systems A and B will attain thermal equilibrium
with third system C (Fig.-01).
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First Law of Thermodynamics:
Statement:
The heat added to the system is equal to the change in internal energy of the system
plus the external work done by the system.
Explanation:
Let the quantity of heat added to the system be δH, the change in internal energy of
the molecules be dU and the amount of external work done be δW.
Mathematically
δH=dU+δW……………….(1)
Equation (1) represents the first law of thermodynamics. All the quantities are
measured in heat units.
Second Law of Thermodynamics:
The second law of thermodynamics is a general principle which places constraints
upon the direction of heat transfer and attainable effiencies of heat engine.
Clausius’s Statement:
It is impossible to make heat flow from a body at a lower temperature to a body at a
higher temperature without doing external work on the working substance.
Kelvin’s Statement:
It is impossible to get a continuous supply of work from a body by cooling it to a
temperature lower than that of its surroundings.
Planck’s Statement:
It is impossible to construct an engine which, working in a complete cycle, will
produce no effect other than the raising of a weight and the cooling of a heat
reservoir.
Kelvin-Plank Statement:
It is impossible to extract an amount of heat from a hot reservoir and use it all to do
work.
Edser’s Statement:
Heat flows of itself from higher to lower temperature.

Reversible Process:
A process which can be retraced in the opposite direction so that the working
substance passes through exactly the same states in all respects as in the direct
process is called a reversible process.
Example: A given mass of ice changes to water when a certain amount of heat is
absorbed by it and the same mass of water changes to ice when the same quantity of
heat is removed from it.
Irreversible Process:
A process which cannot be retraced in the opposite direction is called an
irreversible process. In an irreversible process the system with the surroundings can
never be completely restored to its initial condition by reversing the controlling
factors.

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Example: Exchange of heat between bodies at different temperatures by conduction
or radiation.
Isothermal Process:
If a system is perfectly conducting to the surrounding and the temperature remains
constant throughout the process is called an isothermal process.

A(P1,V1)
Isothermal

B(P2,V2)
P

V
Fig.-1

Consider a working substance at a certain pressure and temperature and having a

volume represented by the point A (Fig.-01).
Pressure is decreased and work is done by the working substance at the cost of its
internal energy and there should be fall in temperature. But, the system is perfectly
conducting to the surroundings. It absorbs heat from the surrounding and maintains
a constant temperature. Thus from A to B the temperature remains constant .The
curve AB is called the isothermal curve or isothermal.
Adiabatic Process:
When a system undergoes from an initial state to a final state in such a way that no
heat leaves or enters the system, the process is called adiabatic process.

A(P1,V1,T1)

B(P2,V2,T3)

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Thus, during an adiabatic process, the working substance is perfectly insulated from
the surroundings. All along the process, there is change in temperature .A curve
between pressure and volume during the adiabatic process is called an adiabatic
curve or an adiabatic.
Heat Engines:
Any practical machine which converts heat into mechanical work is called a heat
engine.
Heat engines in their operation absorbs heat at a higher temperature, converts part
of it into mechanical work ,and rejects the remaining heat at a low temperature.
In this process, a working substance is used.In steam engines, the working substance
is water vapour, and in all gas engines the working substance is a combustible
mixture of gases.

Definition of Efficiency:
The efficiency,η of a heat engine is defined as the ratio of mechanical work done by
the engine in one cycle to the heat absorbed from the high temperature source. Thus,
if W be the amount of work obtainable from a heat engine in one cycle at the expense
of Q amount of heat, then its efficiency, η is given by
𝑊
𝜂= ,
𝑄

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Carnot’s Ideal Heat Engine:
In 1824 the French engineer Sadi Carnot conceived a theoretical engine which is
free from all practical imperfections. Such an engine can not be realized in practice.
It has maximum efficiency and it is an ideal heat engine. Sadi Carnot’s heat engine
requires the following important parts (Fig.-01)

Cylinder

Working Substanc

Conducting Insulating Conducting

Source Sink
Stand

Cylinder: A cylinder having perfectly non-conducting walls, a perfect conducting

base and is provided with a perfectly non-conducting piston which moves without
friction in the cylinder. The cylinder contains one mole of perfect gas as the working
substance.

Source:
A reservoir maintained at a constant temperature T1 from which the engine can draw
heat perfect conduction. It has infinite thermal capacity and any amount of heat can
be drawn from it at constant temperature T1.

Heat Insulating Stand:

A perfectly non-conducting platform acts as a stand for adiabatic process.

Sink:
A reservoir maintained at a constant temperature T2 (T2 ‹T1) to which the heat engine
can reject any amount of heat. The thermal capacity of sink is infinite so that its
temperature remains constant at T2, no matter how much heat is given to it.

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The Carnot Cycle:
A cycle in which the working substance starting from a given condition of
temperature, pressure and volume is made to undergo two successive expansion (one
isothermal and another adibatic ), and then brought back finally to its initial
condition, is called Carnot’s Cycle (Fig.-1).

Carnot’s Cycle ((Heat and thermodynamics- N. Subrahmanyam, Brijlal))

In order to obtain continuous supply of work, the working substance is subjected to
the following cycle of quasi-static operations known as Carnot’s cycle
1. Isothermal expansion:
The cylinder is first placed on the source, so that the gas acquires the
temperature 𝑇1 of the source. It is then allowed to undergo quasi-static expansion. As
the gas expands, its temperature tends to fall. Heat passes into the cylinder through
the perfectly conducting base which is in contact with the source. The gas therefore,
undergoes slow isothermal expansion at the constant temperature𝑇1 .

A(P1,V1)

Isothermal
B(P2,V2)

P Adiabatic
D(P4,V4) Adiabatic

Isothermal C(P3,V3)

O E F G H
V

Fig.-1
Let the working substance during isothermal expansion goes from its initial
state 𝐴 𝑃1 , 𝑉1 , 𝑇1 to the state 𝐵 𝑃2 , 𝑉2 , 𝑇1 at constant temperature 𝑇1 along AB. In
this process, the substance absorbs heat 𝑄1 from he source at 𝑇1 and does work 𝑊1
given by
𝑉2
𝑉2
𝑄1 = 𝑊1 = 𝑃𝑑𝑉 = 𝑅𝑇1 𝑙𝑜𝑔𝑒 = 𝑎𝑟𝑒𝑎 𝐴𝐵𝐺𝐸𝐴
𝑉1
𝑉1

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2. Adiabatic expansion:
The cylinder is now removed from the source and is placed on the insulating stand.
The gas is allowed to undergo slow adiabatic expansion, performing external work
at the expense of its internal energy, until its temperature falls to T 2, the same as that
of the sink.
This operation is represented by the adiabatic BC, starting from the state B (P2, V2,
T2) to the state C (P3, V3, T3). In this process, there is no transfer of heat, the
temperature of the substance falls to T2 and it does some external work W2 given by
𝑉 𝑉 𝑑𝑉
𝑊2 = 𝑉 3 𝑃𝑑𝑉 = 𝐾 𝑉 3 𝛾
2 2 𝑉
(∴During adiabatic process, 𝑃𝑉 𝛾 =constant=K
1−𝛾 1−𝛾
𝐾𝑉3 −𝐾𝑉2
=
1−𝛾
𝑃3 𝑉3 −𝑃2 𝑉2 𝛾 𝛾
= ∴ 𝑃2 𝑉2 = 𝑃3 𝑉3 = 𝐾
1−𝛾
𝑅𝑇2 −𝑅𝑇1
=
1−𝛾
𝑅 𝑇2 −𝑇1
= = 𝐴𝑟𝑒𝑎 𝐵𝐶𝐻𝐺𝐵
1−𝛾
3. Isothermal Compression:
The cylinder is now removed from the insulating stand and is placed on the sink
which is at a temperature T2. The piston is now very slowly moved inwards so that
the work is done on gas. The temperature tends to increase due to heat produced by
compression since the conducting base of the cylinder is in contact with the sink, the
heat developed passes to the sink and the temperature of the gas remains constant at
T2. Thus the gas undergoes isothermal compression at a constant temperature T2 and
gives up some heat to the sink.
This operation is represented by the isothermal CD, starting from the state C (P3, V3,
T2) to the state D (P4, V4, T2). In this process, the substance rejects heat Q2 to the sink
at T2 and work W3 is done on the substance given by
𝑉4
𝑉4
𝑄2 = 𝑊3 = 𝑃𝑑𝑉 = 𝑅𝑇2 𝑙𝑜𝑔𝑒 = 𝑎𝑟𝑒𝑎 𝐶𝐻𝐹𝐷𝐶
𝑉3
𝑉3
(-ve sign indicates that work is done on the working substance)

4. Adiabatic Compression
The cylinder is now removed from sink and again placed on the insulating stand. The
piston is slowly moved inwards so that the gas is adiabatically compressed and the
temperature rises. The adiabatic compression is continued till the gas comes back to
its original condition i.e., state 𝐴 𝑃1 , 𝑉1 , 𝑇1 , thus completing one full cycle.
This operation is represented by adiabatic DA, starting D (P4, V4, T2) to the final
state 𝐴 𝑃1 , 𝑉1 , 𝑇1 . In this process, work W4 is done on the substance and is given by

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 𝑉1

𝑊3 = 𝑃𝑑𝑉
𝑉4
𝑅 𝑇1 − 𝑇2
=− = 𝐴𝑟𝑒𝑎 𝐷𝐹𝐸𝐴𝐷
𝛾−1
(-ve sign indicates that work is done on the working substance. Since W2 and W4 are
equal and opposite, they cancel each other)

Work done by the engine per cycle:

See-Lecture.(( Heat and thermodynamics- N. Subrahmanyam, Brijlal))

Efficiency:
See-Lecture. Heat and thermodynamics- N. Subrahmanyam, Brijlal))

Entropy:
In thermodynamical processes we must search for a quantity which tells about the
direction of flow of heat and which could efficiently define the thermodynamical state
of any working substance. The required quantity was supplied by Clausius who
called it entropy.
It is denoted by the symbol S. For infinitesimal small change in entropy is given by,
𝑑𝑄
𝑆= .
𝑇
The total change in entropy is given by
𝑑𝑄
𝑆= .
𝑇