Entropy

1. Definition: Entropy is the measure of molecular disorder.

Higher the disorder, higher is the entropy of the system.

Entropy term came into existence from second law of Thermodynamics and is
expressed as follows.

δQ
dS= kJ / K
T

Entropy is a Thermodynamic Property and a state or point function (Exact

differential),

δQ
∮ T
=0

2. Carnot theorem for second law of thermodynamics states that:

- No heat engine operating on a cycle between two heat reservoirs at different fixed temperatures
can be more efficient than reversible engine OR

- Two reversible heat engines operating between two reservoirs or same end states will have
same efficiency.

Efficiency or Reversible Engine > Efficiency of Irreversible Engine

-Second law efficiency for heat engines = (Efficiency of Actual engine / Carnot efficiency).

Where, Carnot efficiency for heat engines = 1- T2/T1

- Second law efficiency for refrigerator or heat pumps,

Second law = (Actual COP / COP Carnot)

Carnot COP for refrigerators = T2 / (T1 – T2)

Carnot COP for Heat Pumps = T1 / (T1 – T2)

-Carnot cycle is the theoretical cycle.

-All the processes in Carnot cycle are reversible processes and hence the efficiency of Carnot
cycle is maximum among all the cycles.

-The efficiency of the Carnot cycle depends only on the temperatures of the two reservoirs (Heat
Sink and Heat source).

- Efficiency of the Carnot cycle does not depend on the fluid properties.

-As per the Carnot theorem for second law,

❑Irrversible cycle<❑r eversible cycle

Comparison of actual and Carnot Efficiency is given in following table.

Actual Efficiency for Heat Carnot Efficiency for Second law

Engine: Heat Engine: efficiency
❑ Q L
❑ T L
❑ ❑ actual
Actual=¿1− ¿ Carnot=¿1− ¿ II =¿ ¿
QH TH ❑ carnot

Actual COP for

Refrigerator: Carnot COP for ❑ COP actual
II =¿ ¿
Refrigerator: COPcarnot

COP QL COP T L
Actual =¿ ¿ Carnot=¿ ¿
QH −¿Q ¿L
T H −¿T ¿L

Actual COP for Heat Pump: Carnot COP for heat ❑ COP actual
II =¿ ¿
Pump: COPcarnot

COP QH COP T H
Actual =¿ ¿ Carnot=¿ ¿
QH −¿Q ¿L
T H −¿T ¿L

Carnot cycle efficiency is bench mark efficiency second law efficiency is nothing but
Second law efficiency = (Actual efficiency / Carnot efficiency).

3. Law of Degradation of energy or Law of increase of entropy principle:

With every irreversible process the change in entropy of the universe always increases.

Entropy change for isolated system is also 0 or positive or all other real cases it is always
positive i.e. entropy of the universe always keeps on increasing.
 As per second law quantity of the energy is conserved but its quality degrades
(Ability of a given system to produce maximum work output keeps on decreasing)

4. Two intersecting constant property lines as shown in following figure is not

possible.

5. As per Clausius Theorem:

From Clausius Theorem,

Any reversible process can be replaced by two reversible adiabatic with one reversible isotherm
between them.

Clausius Inequality states that:

The different process can be categorized for a Thermodynamic cycle as follows,

Clausisus Inequality Increase of Entropy Principle

δQ S=0 for revesible process
∮ =0 for revesible process
T

δQ S>0 For irreversible process

∮ T
<0 For irreversible process

δQ S<0 For impossible process

∮ >0 For impossible process
T

6. Entropy is a Thermodynamic Property (Point or state function and exact

differential):
R1 and R2 are two reversible processes with same end states but different process path followed.

Change in entropy ds=dQ/T for the two process is expressed as,

Since R1 and R2 are two processes following two different paths with same end states.

But the change in entropy for both the processes is equal as expressed in the above
equation. Hence change in entropy is same for both the processes and is independent of the path
followed hence Entropy is a state or point function and is exact differential.

7. Entropy Change during heat and work transfers:

a. Entropy Change of Heat source reservoir (as the source supplies heat its entropy
decreases):

dSsource = -Q/T or dSsource <0

Since the source reservoir supplies or rejects heat to the system the heat transfer of the source
reservoir is negative and hence the change in entropy is also negative.

b. Entropy Change of Heat sink reservoir (As the sink absorbs heat from engine its
entropy change is positive):

dSsource = Q/T or dS > 0

Since the sink reservoir accepts or absorbs heat from the system the heat transfer for the sink
reservoir is positive and hence the change in entropy is also positive.
 c. Change in entropy during work transfer or for work reservoir:

Entropy only depends on heat transfer and does not depend at all on work transfer.

For work transfer,

dS = 0 for work transfer as it is not related to work transfer.

8. Principle of Increase of Entropy or Law of Degradation of Energy:

The entropy change of the system and its surrounding i.e. for universe during any process
between two equilibrium states is always equal to or greater than zero. This is known as principal
or increase of entropy.

Ssystem+Ssurrounding ≥ 0

i.e. Suniverse ≥ 0

or Suniverse = 0 for reversible process and

Suniverse > 0 for real or irreversible process

Entropy of the system or surrounding can increase (if heat is added) or decrease (if heat is
rejected) but the total entropy of the universe increases always. This is also known as law of
degradation of energy. Higher the increase in the entropy greater are the losses and hence the
efficiency of the system decreases.

9. T-dS relations:

T.dS=PdV+dU………………………….(A)

Equation A represents first TdS relation.

TdS=dH-VdP……………………………(B)

10. Change in entropy for any general process:

S2-S1=mRln(V2/V1)+mCvln(T2/T1)………………………………….1 OR

S2-S1=mCpln(T2/T1) + m R ln(P1/P2)………………………………….2 OR

S2-S1= mCpln(V2/V1)+mCvln(P2/P1)………………………………….3

1. For Constant volume process: V1/V2 = 1 and ln(V1/V2)=0

Hence the entropy equation becomes:

S2-S1= m Cv ln (T2/T1) = m Cv ln(P2/P1)

 2. For Constant Pressure process: P1/P2 = 1 and ln(P1/P2)=0

Hence the entropy equation becomes:

S2-S1= m Cp ln(T2/T1) = mCpln(V2/V1)

3. For Constant Temperature process: T2/T1 = 1 and ln(T2/T1)=0

Hence the entropy equation becomes:

S2-S1= m R ln(V2/V1) = m R ln(P1/P2)

If the isoproperty (isochoric, isobaric, isothermal) is mentioned use one of the relation above
mentioned to solve the numerical.

In case of Thermal reservoirs at constant temperature change in entropy is expressed as,

S=Heat transferred by the reservoir / Reservoir Temperature

If the heat is supplied by the reservoir, its entropy decreases and system entropy i

12. Entropy change in case of heating of pure substance:

For Sensible heating (no Phase change) of pure substance,
S=m Cp ln(T2/T2)
For Latent heating (Phase change) of pure substance,
S=(Mass * Latent heat) / (Temperature of Phase change)
 Entropy Change of pure substance:

1–2: Sensible heating of water (T2=100 C).

2-4: Boiling of water into steam.
4-5: Super heating

Change in entropy during 1-2: (Sensible heating)

S=m*Cpw*ln(T2/T1)
Cpw-Specific heat of water

Change in entropy during 3-4: (Latent heat of evaporation)

S=m*(h4-h2)/373
(h4-h2) – Latent heat of evaporation

Change in entropy during 4-5: (Sensible heating)

S= m*Cps*ln(T5/T4)
Cps – Specific heat of steam

13. Third Law of Thermodynamics:

The entropy of all homogenous crystalline solid substances is zero at absolute zero temperature.
As T tends to 0 K, S tends to 0 kJ/K

Or at T= 0 K, S= 0 kJ/K.

Entropy Availability or Exergy (A=Q-U = Q - T0.S)

δQ Unavailability or Anergy (U=T0.S)
dS= kJ / K
T
- Entropy is the measure of degree of - Energy can be classified as high grade
molecular disorder or randomness. and low grade.
Higher the disorder higher is the - High grade is energy available from
entropy. work reservoir, KE, PE, Shaft work etc
which can be directly utilized.
- Area under the process curve on T-s - Low grade energy which needs to be
Diagram gives the heat transferred converted into high grade before
during the process. utilization viz. Heat, IE, Nuclear
energy, Chemical energy, Molecular
- Entropy is the property of the system energy etc.
and is a point or state function or exact - Low grade energy = AE + UE
differential. (Please Note: Only Heat - AE = Available energy / Exergy
and work are path functions or inexact - UE=Unavailable energy /Anergy
differential).
- High grade energy = AE / Exergy
- Concept of entropy was born from the (UE=0).
second law of thermodynamics. -
- As per first law for a Thermodynamic
- Entropy of the universe always cycle Q=W.
increases. - As per second law total conversion of
heat into work is not possible. The
- Energy always degrades and entropy of maximum possible output as per the
the universe or disorder always second law is called as Exergy.
increases.
- Exergy / AE is nothing but maximum
- On a P-V diagram two isentropic lines possible theoretical work available
(Reversible adiabatic process) do not from a reversible cycle without
intersect each other. violating the laws of thermodynamics.

- For a system if the heat is rejected by - Exergy is not actual work out put.
the system entropy decreases.
- Exergy is not Canrot work also.
i.e. dSsystem < 0 if Q is –ve
- Exergy is the limiting case of Carnot
- If the surrounding rejects heat to the work.
system its entropy also decreases.
- Carnot efficiency or Carnot work
- If the heat is added to the system would be maximum when TH is
entropy of the system increases. maximum or TL is minimum for same
 heat input.
i.e. dSsystem > 0 if Q is +ve
- We do not have control on the
- If the surrounding accepts heat from temperature of source (TH).
the system its entropy also increases.
- The minimum possible or limiting
- But in all the above cases net change in condition for TL is atmospheric
entropy of the universe always temperature T0 (We can expand till
increases T0).
(dSuniverse=dSsystem+dSsurrounding)
- Carnot efficiency = 1 – T0/TH=AE/QH
dSuniverse > 0 always
- Anergy is the unavailable energy (UE)
- Only for reversible adiabatic or part of the input energy
isentropic process
- S1=S2 or dSuniverse=0 or isentropic - UE=T0.S (Heat rejection QL in carnot
process. cycle at T0).

- For irreversible adiabatic process due to T0-Atm. Temperature, K.

internal friction heat is generated within
the system boundary dSuniverse >0 . - Exergy is the maximum possible useful
or available energy
- As per third law absolute entropy of the - A = QH - UE = QH - T0.S.
system is zero at 0 K i.e. there is no - QH=Heat supplied by the source.
molecular disorder at absolute 0 K. The - T0-Atmospheric temperature.
molecules have a perfect order at 0 K. - S-Rise in entropy during heat
addition.
- S=0 kJ/K at T= 0 K – 3rd law of - Exergy is the property of the system
thermodynamics. and is a point or state function.
- Exergy or Availability concept was
- Entropy of saturated liquid condition born from the second law of
for water is randomly assumed to be 0 thermodynamics.
kJ/K at 0 C for the sake of ease of - Exergy or Availability of a given
calculation of change in entropy during system or substance always keeps on
different processes (sf =0 kJ/kg K). decreasing.
- Second law of thermodynamics is also - Energy always degrades i.e. its useful
called as law of degradation of energy output or exergy always decreases / is
or law entropy destruction. destroyed.
- dSuniverse > 0 ----------Irreversible - Heat, Internal energy, Chemical energy,
process Nuclear energy etc are a low grade
- dSuniverse = 0 ----------Reversible energy as it needs to be converted into
process useful work and cannot be directly
- dSuniverse < 0 ----------Impossible utilized.
process.
- Entropy is not associated with work - K.E., P.E. mechanical work are high
transfer i.e. entropy change would be
 zero for work transfer (S=0 for W>0) grade energy which can be directly
- As per the second law of utilized for doing useful work.
Thermodynamics no actual cycle
between the same temperature limits - Second law is also called as law of
can be more efficient than Carnot cycle. exergy destruction / entropy
T2 production.
- ¿ 1−
T1
- T2 = Minimum temperature of the - The more we move away from
cycle, K atmospheric conditions in terms of
- T1 = Maximum temperature of the pressure and temperature higher and
cycle, K higher exergy output is possible.
- OR Efficiency of Reversible engine is
always greater than irreversible engine - Atmosphere has infinite energy but
(Due to losses occurring in irreversible zero Availability or Exergy (A=0).
processes).
- Atmosphere has infinite Anergy
(Unavailability).

- Hence Atmospheric conditions is also

called as dead state.

- The more system reaches closer and

closer to atmospheric conditions the
availability from the supply energy
keeps on decreasing and becomes
finally zero when the system comes in
equilibrium with the surrounding.

- No Availability is possible when the

system and the surrounding are in
Thermodynamic equilibrium with each
other.

For non-flow system:

- Availability function = U-T0S+P0V
- Helmholtz function = U-TS
- Gibbs Function = U-TS+PV
For flow system:
- Availability function = H-T0S