Reversible Process

A reversible process is one which can be retracted in opposite direction by changing the external
conditions infinitesimally.
If heat is absorbed by the substance in the direct process, the same quantity of heat will be given
out by it in the reverse process, and if work is done by the substance in the direct process, an equal
amount of work done on the substance in the reverse process. Thus, there is no wastage or loss of
energy at all in the reversible process.
The infinitesimally slow isothermal expansion and compression of a gas is reversible process. In
fact, all isothermal and adiabatic operations are reversible when carried out slowly.
The process will not be reversible if there is any loss of heat due to friction, radiation, or
conduction. If the changes take place rapidly, the process will not be reversible. The energy used
in overcoming friction cannot be retraced.
The conditions of reversibility for any heat engine or process can be stated as follows,
1. The pressure and temperature of the working substance must not differ appreciably from those
of the surrounding at any stage of the cycle of operation.
2. All the processes taking place in the cycle of operation must be infinitely slow,
3. The working parts of the engine must be completely free from friction.
4. There should not be any loss of energy due to conduction, convection, or radiation during the
cycle of operation.
Irreversible Process
All changes are irreversible in nature due to the following reasons
1. The conditions of thermodynamic equilibrium are not satisfied because a natural process does
not take place quasi-statically.
2. Dissipative effects, such as friction, viscosity, inelasticity, electric resistance, eddy formation
etc. are always present.
Heat engines
Any practical machine which converts heat into mechanical work is called a heat engine. Heat
engines in their operation absorb 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 vapor, and in all gas
engines the working substance is a combustible mixture of gases.
In any heat engine, the working substance goes through certain changes of pressure, volume, and
temperature, and then returns to the initial state. The complete changes through which the working
substance undergoes from its initial state and back to its starting state constitute one cycle.
Carnot’s Ideal Heat Engine
Such an engine cannot be realized in practice. It has maximum efficiency and its an ideal heat
engine.

1. A cylinder having perfectly non-conducting walls, perfectly 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.
2. Source- A reservoir maintained at a constant temperature T1 from which the engine can draw
heat by perfect conduction. It has infinite thermal capacity, and any amount of heat can be drawn
from it at constant temperature T1.
3. Heat insulating stand- A perfectly non-conducting platform acts as a stand for adiabatic
processes.
4. Sink- A reservoir maintained at a constant lower temperature T2 (T2 < T1) to which the heat
engine can reject any amount of heat. The thermal capacity of the sink is infinite so that’s its
temperature remains constant at T2, no matter how much heat is given to it.
Carnot’s Cycle
1. Isothermal expansion
𝑉2
ⅆ𝑉 𝑉2
𝑄1 = 𝑊1 = ∫ = 𝑅𝑇1 ln = 𝐴𝑟𝑒𝑎 𝐴𝐵𝐺𝐸𝐴
𝑉1 𝑉 𝑉1

2. Adiabatic expansion
 𝑅(𝑇1 − 𝑇2 )
𝑊2 = = 𝐴𝑟𝑒𝑎 𝐵𝐶𝐻𝐺𝐵
𝛾−1
3. Isothermal Compression
𝑉3
𝑄2 = −𝑅𝑇2 ln = 𝐴𝑟𝑒𝑎 𝐶𝐻𝐹𝐷𝐶
𝑉4
4. Adiabatic compression
𝑅(𝑇1 − 𝑇2 )
𝑊4 = − = 𝐴𝑟𝑒𝑎 𝐷𝐹𝐸𝐴𝐷
𝛾−1

Q. Describe the Carnot’s Cycle. Include detailed calculations for each operation (isothermal expansion,
adiabatic expansion, isothermal compression, and adiabatic compression) and a diagram.
Efficiency
The efficiency of a heat engine is the rate of quantity of heat converted into work (output) per
cycle to the total amount of heat absorbed per cycle.
Efficiency depends only upon temperature of the source and sink and is always less than unity. It
is independent of the nature of the working substance.
If T2 = 0, 𝜂 = 1 which means temperature of sink at absolute zero which is not possible in practice.
Again, the efficiency is minimum or zero when T1=T2, i.e., the temperature of the source is equal
to the temperature of sink, then 𝜂 = 0 i.e., the engine does not work. The Carnot’s engine is
perfectly reversible. It can be operated in the reverse direction also. Then it works as a refrigerator.
Q. Explain how Carnot’s engine can work in the reverse direction and hence, how a refrigerator
works.
Moreover, in Carnot’s heat engine the process of isothermal and adiabatic expansions and
compressions are carried out very slowly, quasi-static. This is an ideal case. Any practical engine
can not satisfy these conditions. Therefore, all practical engines have an efficiency less than the
Carnot’s engine.
Second law of thermodynamics
First law of thermodynamics states the equivalence of heat and energy. It simply says that whatever
work is obtained, an equivalent amount of heat is used up and vice versa.
It does not say anything about the direction in which the change might occur or about the range or
limit to which it can be possible.
Lord Kevin’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 will work in a complete cycle and produce no effect
except the raising of a weight and cooling of a heat reservoir.”
Kevin-Planck Statement
“It is impossible to construct an engine which, operating in a cycle, has the sole effect of extracting
heat from a reservoir and performing an equivalent amount of work.”
Clausius’s Statement
“It is impossible for a self-acting machine working in a cyclic process, unaided by external agency,
to transfer heat from a body at a lower temperature to a body at a higher temperature.”
“Heat cannot flow of itself from a colder body to a hotter body”

Carnot’s theorem
Statement:
From the second law of thermodynamics two important results are derived; these conclusions are
taken together to constitute Carnot’s theorem which may be stated in the following forms,
(a) ‘No engine can be more efficient than a perfectly reversible engine working between the same
two temperatures.’
(b) ‘The efficiency of all reversible engines, working between the same two temperatures is the
same, whatever the working substance.’
Suppose I is more efficient than R. Suppose in each cycle, R absorbs the quantity of heat Q1 from
the source at T1 and rejects the quantity of heat Q2 to the sink at T2. Suppose in each cycle I absorbs
the quantity of heat Q1’ from the source at T1 and gives up the quantity of heat Q2’ to the sink at T2.
Let the two engines do the same amount of work W in each cycle. According to the assumption I
is more efficient than R,
 𝑄1′ − 𝑄2′ 𝑄1 − 𝑄2
>
𝑄1′ 𝑄1
𝑊 𝑊
>
𝑄1′ 𝑄1
𝑄1 > 𝑄1′
𝑄1′ − 𝑄2′ = 𝑄1 − 𝑄2
𝑄2 − 𝑄2′ = 𝑄1 − 𝑄1′
𝑄1 > 𝑄1′
𝑄2 > 𝑄2′
Now suppose the two engines are coupled together so that I drives r backwards and suppose they
use the same source and sink. The combination forms a self-acting machine in which I supplies
external work W and R absorbs this amount of work in its reverse cycle. I in its cycle absorbs
heat 𝑄1′ from the source and gives up heat 𝑄2′ to the sink. R in its reverse cycle, absorbs heat 𝑄2
from the sink and gives up heat 𝑄1to the source.
The net result of the complete cycle of the coupled engines is given by
Gain of heat by the source at 𝑇1 = 𝑄1 − 𝑄1′
Loss of heat by the sink at 𝑇2 = 𝑄2 − 𝑄2′
External work done on the system = 0
Thus, the coupled engines form a self-acting machine unaided by any external agency transfer heat
continuously from a body at low temperature to a body at a higher temperature.
This conclusion is contrary to the second law of thermodynamics, according to which in a cyclic
process heat cannot be transferred from one body to another at a higher temperature by a self-
acting machine. Hence our assumption is incorrect, and we conclude that no engine can be more
efficient than a perfectly reversible engine working between the same temperatures.
Second part: The second part of the theorem may be proved by the same arguments as before. For
this purpose, we consider two reversible engines R1 and R2 and assume that R2 is more efficient
than R1. Proceeding in the same way we can show that R2 cannot be more efficient than R1.
Therefore, all reversible engines working between the same two temperatures have the efficiency.
Thus, the efficiency of a perfectly reversible engine depends only on the temperatures between
which the engine work and is independent of the nature of the working substance.

Entropy
Entropy is a measure of the degree of randomness of energy in a system. The lower the entropy
the more the order and less randomness. Entropy of a substance is a thermodynamic property which
remains constant when the substance undergoes a reversible adiabatic process. Natural process
take place in such a direction along which the entropy increases. Entropy is a state function-change
in entropy depends only on the two state and does not depend on the path along which it reaches
to the final state.
Change in Entropy
𝑄1 − 𝑄2 𝑇1 − 𝑇2
𝜂= =
𝑄1 𝑇1
𝑄2 𝑇2
1− =1−
𝑄1 𝑇1
𝑄2 𝑇2
=
𝑄1 𝑇1
𝑄1 𝑄2
=
𝑇1 𝑇2
Considering Carnot’s cycle DCEF in which amount of heat 𝑄2 is absorbed at constant temperature
𝑇2 and heat 𝑄3 is rejected at constant temperature 𝑇3 .
𝑄2 𝑄3
=
𝑇2 𝑇3
𝑄1 𝑄2 𝑄3
= = = ⋯ 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇1 𝑇2 𝑇3
In general, if Q is the amount of heat absorbed or rejected at a temperature T in going from one
adiabatic to another,
𝑄
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇
If two adiabatic curves are very close to each other and if 𝛿𝑄 is the small quantity of heat absorbed
at constant temperature T in going from one adiabatic to another, then
𝛿𝑄
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇
Change in entropy,
𝛿𝑄
𝛿𝑆 =
𝑇
𝑆𝐵 𝐵
ⅆ𝑄
∫ ⅆ𝑆 = ∫
𝑆𝐴 𝐴 𝑇
 𝐵
ⅆ𝑄
𝑆𝐴 − 𝑆𝐵 = ∫
𝐴 𝑇
𝐵 𝑆𝐵
ⅆ𝑄
∫ = ∫ ⅆ𝑆
𝐴 𝑇 𝑆𝐴

is a function of the thermodynamic coordinates of a system. This function is represented by symbol

S and called entropy. Entropy can be defined as the thermal property of a working substance which
remains constant during an adiabatic process.
Unit of Entropy: Joule/Kelvin
Change in Entropy in a Reversible Cycle

Consider a complete reversible Carnot’s cycle ABCD as shown.

(i) Isothermal Expansion AB: Let Q1 be the amount of heat absorbed by the working substance in
going from state A to state B during isothermal expansion AB at a constant temperature T1. The
increase in entropy of the working substances is given by,
𝐵
𝑄1
∫ ⅆ𝑆 = +
𝑇1
𝐴

(ii) Adiabatic Expansion BC: in going from state B to state C along the adiabatic BC, there is no
change in entropy of the working substance, but the temperature falls from T1 to T2 due to
expansion,
𝐶

∫ ⅆ𝑆 = 0
𝐵

(iii) Isothermal Compression CD: In going from state C to state D along the isothermal CD, the
working substance rejects heat Q2 to the sink at temperature T2. The entropy of the working
substance decreases and change in entropy is given by
 𝐷
𝑄2
∫ ⅆ𝑆 = −
𝑇2
𝐶

(iv) Adiabatic Compression DA: In going from D to A along the adiabatic DA, there is no change
in entropy, but temperature rises from T2 to T1.
𝐴

∫ ⅆ𝑆 = 0
𝐷

Thus, the net gain in entropy of the working substance in the whole cycle ABCDA,
𝐵 𝐶 𝐷 𝐴

= ∫ ⅆ𝑆 + ∫ ⅆ𝑆 + ∫ ⅆ𝑆 + ∫ ⅆ𝑆
𝐴 𝐵 𝐶 𝐷

𝑄1 𝑄2
∮ ⅆ𝑆 = −
𝑇1 𝑇2
But for a reversible Carnot’s cycle
𝑄1 𝑄2 𝑄1 𝑄2
= ⇒ − =0
𝑇1 𝑇2 𝑇1 𝑇2
Therefore,
𝑄1 𝑄2
∮ ⅆ𝑆 = − =0
𝑇1 𝑇2
where the integral sign with a circle refers to a complete cycle.
Thus, in a cycle of reversible process, the entropy of the system remains unchanged or remains
constant. In other words, the total change in entropy is always zero in a reversible process.
Entropy is a state function
Consider a reversible process from state 1 to state 2 it can be depicted by a PV diagram as shown.
It is possible to bring back the system to its initial position by more than one path.
ⅆ𝑄
∮ =0
𝑇
2𝐴 1𝐵
ⅆ𝑄 ⅆ𝑄
∮ + ∮ =0
𝑇 𝑇
1𝐴 2𝐵
2𝐴 1𝐶
ⅆ𝑄 ⅆ𝑄
∮ + ∮ =0
𝑇 𝑇
1𝐴 2𝐶
We get,
1𝐵 1𝐶
ⅆ𝑄 ⅆ𝑄
∮ = ∮
𝑇 𝑇
2𝐵 2𝐶

ⅆ𝑄
This shows ∫ has the same value for all reversible paths from state 2 to state1. Thus, the quantity
𝑇
ⅆ𝑄
∫ is independent of the path and is a function of the end states only. Therefore, this quantity
𝑇
is a thermodynamic quantity and is called entropy.
2
ⅆ𝑄
𝑆2 − 𝑆1 = ∫
1 𝑇
Ref Books: Heat, Thermodynamics, and Statistical Physics—Brijlal
Physics for Engineers-Part I—Dr. Gias Uddin Ahmad