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Third law of Thermodynamics

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PERPETUAL MOTION MACHINE OF THE SECOND KIND

A machine which violates the first law of thermodynamics is called the perpetual motion
machine of the first kind (PMM1).
Such a machine creates its own energy from nothing and does not exist.

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 percent. This machine is called the perpetual
motion machine of the second kind (PMM2).
THIRD LAW OF THERMODYNAMICS
• It is stated as “The entropy of all perfect crystalline solids is zero at absolute zero
temperature”.
• The third law of thermodynamics, often referred to as Nernst Law, provides the basis for
the calculation of absolute entropies of substances.
• According to this law, if the entropy is zero at T = 0, the absolute entropy, sab of a
substance at any temperature T and pressure p, is expressed by:
𝐓𝐬 =𝐓𝐟 𝟏 𝐓𝐟 𝟐 =𝐓𝐠
𝐝𝐓 𝐡𝐬𝐟 𝐝𝐓 𝐡𝐟𝐠 𝐓 𝐝𝐓
𝐬𝐚𝐛 = ∫ 𝐜𝐩𝐬 + +∫ 𝐜𝐩𝐟 + ∫ 𝐜𝐩𝐠
𝟎 𝐓 𝐓𝐬 𝐓𝐬 𝐓 𝐓𝐠 𝐓𝐠 𝐓

Where, Ts = Tf1 = Tsf = Tsat………….(for fusion)

Tf2 = Tg = Tfg = Tsat …………(for vaporization)
cps = cpf = cpg = constant pressure specific heats for solids liquids and gases
hsf = hfg = Latent heats of fusion and vaporization
Thus, by putting s = 0 at T = 0, one may integrate zero kelvin and standard state of 278.15 K and
1 atm, and find the entropy difference.
• Entropy of crystalline substance at T = 0 is not a function of pressure;

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Third law of Thermodynamics

𝛛𝐬
( ) =𝟎
𝛛𝐩 𝐓=𝟎

Latent Heat of Fusion:

• It's the heat energy needed to transform a substance from a solid to a liquid (or vice
versa) at its melting point.
• This heat breaks the bonds holding the molecules together in the solid state, allowing
them to move more freely as a liquid.
• The latent heat of fusion of water is 334 J/g.
Latent Heat of Vaporization:
• It's the heat energy required to change a substance from a liquid to a gas (or vice versa) at
its boiling point.
• This heat overcomes the intermolecular forces in the liquid, enabling molecules to escape
into the gaseous phase.
• The latent heat of vaporization of water is 2260 J/g
THERMODYNAMIC TEMPERATURE

Take the case of reversible heat engine operating between two reservoirs. Its thermal efficiency
is given by the eqn.

ηth=(Q1−Q2)/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 φ of that property, temperature. Thus,

Q=ϕ(T), where T is the temperature of reservoir

The choice of the function is universally accepted to be such that

Q1/Q2 = ϕ(T1)/ϕ(T2) = T1/T2

One form of the third law of thermodynamics is the statement:
"The temperature of a system cannot be reduced to zero in a finite number of processes."

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

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Third law of Thermodynamics

may now be defined in terms of reference value and the heat transfers that would occur with
reversible engine,

T=Tref⋅(Q/Qref)

The SI unit of thermodynamic temperature is the kelvin (K). The relation between
thermodynamic temperature and Celsius scale, which is in common use is:

Thermodynamic temperature=Celsius temperature+273.15

The kelvin unit of thermodynamic temperature is the fraction 1/273.15 of thermodynamic

temperature of ‘Triple point’ of water.
GAS POWER CYCLES
CARNOT CYCLE
• This cycle has the highest possible efficiency and consists of four simple operations
namely,
(a) Isothermal expansion
(b) Adiabatic expansion
(c) Isothermal compression
(d) Adiabatic compression
Working principle:
• One kg of a air is enclosed in the cylinder which (except at the end) is made of perfect
non- conducting material.
• A source of heat ‘H’ is supposed to provide unlimited quantity of heat, non- conducting
cover ‘C’ and a sump ‘S’ which is of infinite capacity so that its temperature remains
unchanged irrespective of the fact how much heat is supplied to it.
• The temperature of source H is T1 and the same is of the working substance.
• The working substance while rejecting heat to sump ‘S’ has the temperature T2 i.e. the
same as that of sump S.
The four stages of Carnot cycle are:
1. Stage (1): Line 1-2 represents the isothermal expansion, which takes place at temperature T1
when source of heat H is applied to the end of cylinder.

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Third law of Thermodynamics

• Heat supplied in this case is given by RT1 loger where r is the ratio of expansion.
2. Stage (2): Line 2-3 represents the application of non- conducting cover to the end of the
cylinder. This is followed by the adiabatic expansion and the temperature falls from T1 to T2.
3. Stage (3): Line 3-4 represents the isothermal compression which takes place when sump ‘S’ is
applied to the end of cylinder. Heat is rejected during this operation whose value is given by RT2
loger where r is the ratio of compression.
4. Stage (4): Line 4-1 represents repeated application of non- conducting cover and adiabatic
compression due to which temperature increases from T2 to T1.
NOTE: Ratio of expansion during isotherm 1-2 and ratio of compression during isotherm 3-4
must be equal to get a closed cycle.
According to law of conservation of energy:
Heat supplied = Work done + Heat rejected
Work done = Heat supplied – Heat rejected
= RT1 loger – R𝑇2 loger
𝐖𝐨𝐫𝐤 𝐝𝐨𝐧𝐞 𝐑𝐥𝐨𝐠 𝐞 𝐫(𝐓𝟏 −𝐓𝟐 ) 𝐓𝟏 −𝐓𝟐
Efficiency of cycle = 𝐇𝐞𝐚𝐭 𝐬𝐮𝐩𝐩𝐥𝐢𝐞𝐝 = =
R𝐓𝟏 .𝐥𝐨𝐠 𝐞 𝐫 𝐓𝟏

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Third law of Thermodynamics

RANKINE CYCLE
• Rankine cycle is the theoretical cycle on which the steam turbine (or engine) works.

• The Rankine cycle comprises of the following processes:

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Third law of Thermodynamics

1. Process 1-2: Reversible adiabatic expansion in the turbine (or steam engine).
2. Process 2-3: Constant- pressure transfer of heat in the condenser.
3. Process 3-4: Reversible adiabatic pumping process in the feed pump.
4. Process 4-1: Constant- pressure transfer of heat in the boiler
STEADY FLOW ENERGY EQUATIONS
Considering 1 kg of fluid:
1. For boiler (as control volume):
hf4 + Q1 = h1

Q1 = h1 − hf4

2. For turbine (as control volume):

h1 = WT + h2 (where WT = Turbine work)
WT = h1 – h2
3. For condenser:
h2 = Q2 + hf3

Q2 = h2 − hf3

4. For the feed pump:

hf3 + WP = hf4 (Where WP = Pump Work)

WP = hf4 − hf3

Efficiency of Rankine cycle is given by:

𝐖𝐧𝐞𝐭 𝐖𝐓 − 𝐖𝐏
𝛈𝐑𝐚𝐧𝐤𝐢𝐧𝐞 = =
𝐐𝟏 𝐐𝟏
(𝐡𝟏 − 𝐡𝟐 ) − (𝐡𝐟𝟒 − 𝐡𝐟𝟑 )
=
(𝐡𝟏 − 𝐡𝐟𝟒 )

• hf4: Enthalpy of feedwater entering boiler.

• Q1: Heat added in boiler.
• h1: Enthalpy of steam leaving boiler.
• WT: Work output from turbine.
• h1: Enthalpy of steam entering turbine.

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Third law of Thermodynamics

• h2h: Enthalpy of steam after expansion.
• h2: Enthalpy of steam entering condenser.
• hf3: Enthalpy of condensate (saturated liquid) exiting.
• Q2: Heat removed in condenser (rejected to cooling medium).
The feed pump term (𝐡𝐟𝟒 - 𝐡𝐟𝟑 ) being a small quantity in comparison with turbine work, WT , is
usually neglected, especially when the boiler pressure are low.
𝐡 −𝐡
Thus, 𝛈𝐑𝐚𝐧𝐤𝐢𝐧𝐞 = 𝐡 𝟏−𝐡 𝟐
𝟏 𝐟𝟒

COMPARISON BETWEEN RANKINE CYCLE AND CARNOT CYCLE

1. Between the same temperature limits, Rankine cycle provides a higher specific work
output than a Carnot cycle, consequently Rankine cycle requires a smaller steam flow
rate resulting in smaller size plant for a given power output. However, Rankine cycle
calls for higher rate of heat transfer in boiler and condenser.
2. Since in Rankine cycle, only part of the heat is supplied isothermally at constant higher
temperature, T1, therefore, its efficiency is lower than that of Carnot cycle.
The efficiency of the Rankine cycle will approach that of the Carnot cycle more nearly if the
superheat temperature rise is reduced.
3. The advantage of using pump to feed liquid to the boiler instead to compressing a wet
vapour is obvious that the work for compression is very large compared to the pump.
EFFECT OF OPERATING CONDITIONS ON RANKINE CYCLE EFFICIENCY
The Rankine cycle efficiency can be improved by:
1. Increasing the average temperature at which heat is supplied.
2. Decreasing/ reducing the temperature at which heat is rejected.

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Third law of Thermodynamics

This can be achieved by making suitable changes in the conditions of steam generation or
condensation:
1. Increasing boiler pressure
2. Super heating
3. Reducing condenser pressure
EFFECT OF OPERATING CONDITIONS ON THE THERMAL EFFICIENCY OF THE
RANKINE CYCLE

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Third law of Thermodynamics

The thermal efficiency of the Rankine cycle is also improved by the following methods:
1. By regenerative feed heating
2. By reheating of steam
3. By water extraction
4. By using binary- vapour

OTTO CYCLE
• This cycle is also termed as “Constant Volume cycle”.
• This cycle is so named as it was conceived by ‘Otto’.
• On this cycle, petrol, gas and many types of oil engines work.
• It is the standard of comparison for internal combustion engines.
• In below shown figures,
1. The point 1 represents that cylinder is full of air with volume V1, pressure p1 and absolute
temperature T1.
2. Line 1 – 2 represents the adiabatic compression of air due to which p1, V1 and T1 change
to p2, V2 and T2 respectively.

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Third law of Thermodynamics

3. Line 2 – 3 shows the supply of heat to the air at constant volume so that p2 and T2 change to p3
and T3 (V3 being the same as V2).
4. Line 3 – 4 represents the adiabatic expansion of the air. During expansion, p3, V3 and T3
change to a final value of p4, V4 or V1 and T4, respectively.
5. Line 4 – 1 shows the rejection of heat by air at constant volume till original state (point 1)
reaches.
Consider 1 kg of air (working substance):
Heat supplied at constant volume = cv (T3 – T2)
Heat rejected at constant volume = cv (T4 – T1)
Work done = Heat supplied – Heat rejected
=cv (T3 – T2) - cv (T4 – T1)
Work done
Efficiency =
Heat supplied
cv (T3 − T2 ) − cv (T4 − T1 )
=
cv (T3 − T2 )
𝐓𝟒 − 𝐓𝟏
𝛈=𝟏−
𝐓𝟑 − 𝐓𝟐

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Third law of Thermodynamics

v1
Let compression ratio, rc (=r) = v
2

v4
Expansion ratio, re (=r) = v
3

NOTE: These two ratios are same in this cycle

T2 v1 γ−1
=( )
T1 v2
T2 = T1 . (r)γ−1
T3 v4 γ−1
=( )
T4 v3
T3 = T4 . (r)γ−1
Thus,
T4 − T1 T4 − T1
ηOtto = 1 − γ−1 γ−1
= 1 − γ−1
T4 . (r) − T1 . (r) r (T4 − T1 )
𝟏
𝛈𝐎𝐭𝐭𝐨 = 𝟏 −
𝐫 𝛄−𝟏
This expression is known as the ‘air standard efficiency of the Otto cycle’.
NOTE: From above expression, it is clear that efficiency increases with the increase in the value
of r. But, practically, maximum value of r is limited upto 8.
If p is expressed in bar, i.e. 105 N/m2, then work done
p3 v3 −p4 v4 p2 v2 −p1 v1
W=( − ) × 102 kJ
γ−1 γ−1

p3 p2
= rγ =
p4 p1
p3 p4
= = rp
p2 p1
Where, rp stands for pressure ratio
v1 = rv2 = v4 = rv3
𝐩𝟏 𝐯𝟏
𝐖= [(𝐫 𝛄−𝟏 − 𝟏)(𝐫𝐩 − 𝟏)]
𝛄−𝟏
Mean effective pressure is given by:

𝐩𝟏 𝐫[(𝐫 𝛄−𝟏 − 𝟏)(𝐫𝐩 − 𝟏)]

𝐩𝐦 =
(𝛄 − 𝟏)(𝐫 − 𝟏)

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Third law of Thermodynamics

CONSTANT PRESSURE OR DIESEL CYCLE

• This cycle was introduced by Dr. R. Diesel in 1897.
• It differs from Otto cycle in that heat is supplied at constant pressure instead of at
constant volume.
• This cycle comprises of the following operations:
a) 1 – 2: Adiabatic compression
b) 2 – 3: Addition of heat at constant pressure
c) 3 – 4: Adiabatic expansion
d) 4 – 1: Rejection of heat at constant volume

• Point 1 represents that the cylinder is full of air.

• Let p1, V1 and T1 be the corresponding pressure, volume and absolute temperature.
• The piston then compresses the air adiabatically (i.e. p𝑉 𝛾 = constant) till the value
becomes p2, V2 and T2 respectively (at the end of the stroke) at point 2.
• Heat is then added from a hot body at a constant pressure.
• During this addition of heat, let volume increases from V2 to V3 and temperature T2 to T3,
corresponding to point 3.
• This point (3) is called the point of cut- off.
• The air then expands adiabatically to the conditions p4, V4 and T4 respectively
corresponding to point 4.

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Third law of Thermodynamics

• Finally, the air rejects the heat to the cold body at constant volume till the point 1 where
it returns to its original state.
Consider 1 kg of air:
Heat supplied at constant pressure = cp (T3 – T2)
Heat rejected at constant volume = cv (T4 – T1)
Work done = Heat supplied – heat rejected
= cp (T3 – T2) - cv (T4 – T1)
Work done cp (T3 − T2 ) − cv (T4 − T1 )
ηdiesel = =
Heat supplied cp (T3 − T2 )
(T −T )
= 1 − γ(T4 −T1 )
3 2

v
Let compression ratio, r = v1
2

v Volume at cut−off
Let cut- off ratio, ρ = v3 =
2 Clearance volume

1. During adiabatic compression 1 – 2,

T2 v1 γ−1
=( ) = r γ−1
T1 v2
T2 = T1. (r γ−1 )
2. During constant pressure process 2 – 3:
T3 v3
= =ρ
T2 v2
T3 = ρ. T2 = ρ. T1 . (r)γ−1
3. During adiabatic expansion 3 – 4:
T3 v4 γ−1 r γ−1
=( ) =( )
T4 v3 ρ
T3
T4 = = T1 . ργ
r γ−1
(ρ)

By inserting values of T2, T3 and T4,

(ργ − 1)
ηdiesel =1−
γ(r)γ−1 (ρ − 1)

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Third law of Thermodynamics

𝟏 𝛒𝛄 − 𝟏
𝛈𝐝𝐢𝐞𝐬𝐞𝐥 =𝟏− [ ]
𝛄(𝐫)𝛄−𝟏 𝛒 − 𝟏
• It may be observed that for a given compression ratio, Otto cycle is more efficient than
Diesel cycle.
• The net work for Diesel cycle can be expressed as:
p3 v3 − p4 v4 p2 v2 − p1 v1
W = p2 (v3 − v2 ) + −
γ−1 γ−1
𝐩𝟏 𝐯𝟏 𝐫 𝛄−𝟏 [𝛄(𝛒 − 𝟏) − 𝐫 𝟏−𝛄 (𝛒𝛄 − 𝟏)]
𝐖=
(𝛄 − 𝟏)
Mean effective pressure is given by:
𝐩𝟏 𝐫 𝛄 [𝛄(𝛒 − 𝟏) − 𝐫 𝟏−𝛄 (𝛒𝛄 − 𝟏)]
𝐩𝐦 =
(𝛄 − 𝟏)(𝐫 − 𝟏)

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