Entropy

Dr. C. R. Sonawane
Practical Conditions:

When a reversible engine uses more than two reservoirs the

third or higher numbered reservoirs will not be equal in
temperature to the original two.
The efficiency of the engine indicates that for maximum efficiency,
all the heat transfer should take place at maximum or minimum
reservoir temperatures.
Any intermediate reservoir used will, therefore, lower the
efficiency of the heat engine.
Practical engine cycles often involve continuous changes of
temperature during heat transfer.
CLAUSIUS INEQUALITY
It was first stated by the German physicist R. J. E. Clausius (18221888), one
of the founders of thermodynamics, and is expressed as

That is, the cyclic integral of dQ/T is always less than or equal to zero.
This inequality is valid for all cycles, reversible or irreversible.

To demonstrate the validity of the Clausius inequality, consider a system

connected to a thermal energy reservoir at a constant thermodynamic
(i.e.,absolute) temperature of TR through a reversible cyclic device.
The cyclic device receives heat QR from the reservoir and supplies heat
Q to the system whose temperature at that part of the boundary is T (a
variable) while producing work Wrev. The system produces work Wsys as
a result of this heat transfer.
CLAUSIUS INEQUALITY
Applying the energy balance to the
combined system identified by dashed
lines yields

Considering that the cyclic device is a

reversible one, we have

Eliminating QR from the two relations

above yields
CLAUSIUS INEQUALITY
We now let the system undergo a cycle while the cyclic device undergoes an
integral number of cycles. Then the preceding relation becomes

since the cyclic integral of energy (the net change in the energy, which is a property,
during a cycle) is zero.
Here WC is the cyclic integral of WC, and it represents the net work for the
combined cycle.
It appears that the combined system is exchanging heat with a single thermal energy
reservoir while involving (producing or consuming) work WC during a cycle. On the
basis of the KelvinPlanck statement of the second law, which states that no system
can produce a net amount of work while operating in a cycle and exchanging heat
with a single thermal energy reservoir, we reason that WC cannot be a work output,
and thus it cannot be a positive quantity. we must have
Entropy
Clausius realized in 1865 that he had discovered a new thermodynamic property,
and he chose to name this property entropy. It is designated S and is defined as

The entropy change of a system during a process can be determined by integrating

above Eq. between the initial and the final states

Engineers are usually concerned with the changes in entropy. Therefore, the entropy of
a substance can be assigned a zero value at some arbitrarily selected reference state,
and the entropy values at other states can be determined from above Eq.
Entropya Property of a System
Let us consider a system undergoing a
reversible process from state 1 to state
2 along path L and then from state 2 to
the original state 1 along path M or N.
Applying the Clausius theorem to this
reversible cyclic process

For cycle 1-L-2-M-1, we have

For cycle 1-L-2-N-1

Entropya Property of a System
Subtracting equation (2) from equation (1), we have

As no restriction is imposed on paths L and M, except that

they must be reversible, the quantity is a function of the
initial and final states of the system and is independent of the
path of the process.
Hence it represents a property of the system.
This property is known as the entropy.
THE INCREASE OF ENTROPY PRINCIPLE
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,

The second integral in the previous relation is

recognized as the entropy change S1 - S2.Therefore,
THE INCREASE OF ENTROPY PRINCIPLE
which can be rearranged as

It can also be expressed in differential form as

where the equality holds for an internally reversible process and the inequality for
an irreversible process.
We may conclude from these equations that the entropy change of a closed system
during an irreversible process is greater than the integral of Q/T evaluated for that
process.
In the limiting case of a reversible process, these two quantities become equal.
THE INCREASE OF ENTROPY PRINCIPLE
The inequality sign in the preceding relations is a constant reminder that
the entropy change of a closed system during an irreversible process is
always greater than the entropy transfer.
That is, some entropy is generated or created during an irreversible
process, and this generation is due entirely to the presence of
irreversibilities.
The entropy generated during a process is called entropy generation and is
denoted by Sgen.
Noting that the difference between the entropy change of a closed system
and the entropy transfer is equal to entropy generation, hence previous Eq.
can be rewritten as an equality as

Note that the entropy generation Sgen is always a positive quantity or zero.
THE INCREASE OF ENTROPY PRINCIPLE
Its value depends on the process, and thus it is not a property of the system.
Also, in the absence of any entropy transfer, the entropy change of a system is equal
to the entropy generation.
For an isolated system (or simply an adiabatic closed system), the heat transfer is
zero

This equation can be expressed as the entropy of an isolated system during a process
always increases or, in the limiting case of a reversible process, remains constant. In other
words, it never decreases.This is known as the increase of entropy principle.
Note that in the absence of any heat transfer, entropy change is due to
irreversibilities only, and their effect is always to increase entropy.
The increase of entropy principle can be summarized as
TEMPERATURE-ENTROPY DIAGRAM

Entropy may also be

defined as the thermal
property of a substance
which remains constant
when substance is
expanded or compressed
adiabatically in a cylinder.
ENTROPY CHANGES FOR A CLOSED SYSTEM :
General Case for Change of Entropy of a Gas
Let 1 kg of gas at a pressure p1, volume v1, absolute temperature T1 and entropy s1, be
heated such that its final pressure, volume, absolute temperature and entropy are p2,
v2, T2 and s2 respectively.
Then by law of conservation of energy,
ENTROPY CHANGES FOR A CLOSED SYSTEM :
General Case for Change of Entropy of a Gas

Or we can re-produce

Or we can re-produce
Heating a Gas at Constant Volume
Let 1 kg of gas be heated at constant volume and let
the change in entropy and absolute temperature be
from s1 to s2 and T1 to T2 respectively.

Differentiating to find small increment of heat dQ

corresponding to small rise in temperature dT.
Heating a Gas at Constant Pressure
Let 1 kg of gas be heated at constant pressure and let
the change in entropy and absolute temperature be
from s1 to s2 and T1 to T2 respectively.

Differentiating to find small increase in heat, dQ of this

gas when the temperature rise is dT.
Isothermal Process
Entropy changes from s1 to s2 when gas absorbs
heat during expansion. The heat taken by the gas is
given by the area under the line 1-2 which also
represents the work done during expansion. In
other words, Q = W.
But

Hence
Adiabatic Process (Reversible)
During an adiabatic process as heat is neither
supplied nor rejected
Numerical :
1) 0.04 m3 of nitrogen contained in a cylinder behind a piston is
initially at 1.05 bar and 15C.The gas is compressed
isothermally and reversibly until the pressure is 4.8 bar.
Calculate :
(i) The change of entropy,
(ii) The heat flow, and
(iii) The work done.
Sketch the process on a p-v and T-s diagram.
Assume nitrogen to act as a perfect gas. Molecular weight of
nitrogen = 28.
Solution :
For Nitrogen
Initial pressure, p1 = 1.05 bar
= 1.05 105 N/m2
Initial volume, V1 = 0.04 m3
Temperature, T1 = 15 + 273
= 288 K
Final pressure, p2 = 4.8 bar =
4.8 105 N/m2
Final temprature, T2 = T1 =
288 K.
Solution :
Numerical :
2) Air at 20C and 1.05 bar occupies 0.025 m3.The air is
heated at constant volume until the pressure is 4.5 bar, and
then cooled at constant pressure back to original temperature.
Calculate :
(i) The net heat flow from the air.
(ii) The net entropy change.
Sketch the process on T-s diagram.
Solution :
For air :
Temperature, T1 = 20 + 273 = 293 K
Volume, V1 = V2 = 0.025 m3
Pressure, p1 = 1.05 bar
= 1.05 105 N/m2
Pressure, p2 = 4.5 bar
= 4.5 105 N/m2.
Solution :
Solution :
Numerical :
3) 0.04 kg of carbon dioxide (molecular weight = 44) is
compressed from 1 bar, 20C, until the pressure is 9 bar, and
the volume is then 0.003 m3. Calculate the change of entropy.

Take cp for carbon dioxide as 0.88 kJ/kg K, and assume carbon

dioxide to be a perfect gas
Solution :
For carbon dioxide :
Mass of carbon dioxide, m = 0.04 kg
Molecular weight, M = 44
Initial pressure, p1 = 1 bar
= 1 105 N/m2
Initial temperature, T1 = 20 + 273
=293 K
Final pressure, p2 = 9 bar
Final volume, V2 = 0.003 m3
cp for carbon dioxide = 0.88 kJ/kg K
Solution :
Numerical :
4) An iron cube at a temperature of 400C is dropped into an
insulated bath containing 10 kg water at 25C.The water
finally reaches a temperature of 50C at steady state.

Given that the specific heat of water is equal to 4186 J/kg K.

Find the entropy changes for the iron cube and the water.?

Is the process reversible ? If so why ?

Solution :
Solution :
Solution :
Numerical :
5) An insulated cylinder of volume capacity 4 m3 contains 20 kg
of nitrogen. Paddle work is done on the gas by stirring it till the
pressure in the vessel gets increased from 4 bar to 8 bar.
Determine :
(i) Change in internal energy,
(ii) Work done,
(iii) Heat transferred, and
(iv) Change in entropy.
Take for nitrogen : cp = 1.04 kJ/kg K, and cv = 0.7432 kJ/kg K.
Solution :
Solution :