Limitations of the First law of Thermodynamics

• The first law of thermodynamics deals with energy

changes involved in a process.

• But it cannot tell us whether a proposed change

would actually occur or not?

• The first major limitation of the first law of

thermodynamics is therefore its inability to deal
with the direction of the process and the extent of
change.
• For example: Transfer of heat between to bodies.

• Another Example: Water falling from the top of

mountain.

• Second limitation is it fails to recognise the

qualitative differences between various forms of
energy.

• This difference is apparent when we attempt to

convert heat into work by means of heat engine.
Heat Engine
Heat Pump
 General Statements of Second Law
• Heat cannot by itself pass from a cold body to a hot
body.
• All spontaneous processes are to some extent,
irreversible and are accompanied by a degradation
of energy.
• Kelvin–Planck statement It is impossible to
construct an engine that, operating continuously (in
a cycle), will produce no effect other than the
transfer of heat from a single thermal reservoir at a
uniform temperature and the performance of an
equal amount of work.
• Clausius statement: It is impossible to construct a heat
pump that operating continuously will produce no effect
other than the transfer of heat from a lower temperature
body to a higher temperature one.
 Entropy
• The second law of thermodynamics states that all
spontaneous processes are, to some extent, irreversible
and are accompanied by a degradation of energy.

• The function that is fundamental in the development of

the second law is Entropy.

• Entropy means transformability (change) in Greek,

introduced by Clausius in 1851. The total energy gets
degraded with the corresponding increase in the entropy
of the system.

• Entropy is the thermodynamic property, which serves as a

measure of the unavailability or degradation of energy.
• An increase in unavailability of the total energy of a
system is quantitatively expressed by a corresponding
increase in its entropy.

• Entropy, being an intrinsic property of matter, is not

affected by the external position of the body or its
motion relative to other bodies.

• For ex: The entropy of unit mass of water at the top of

the mountain is equal to the entropy of the same
amount of water at the bottom of the fall, if the
temperature and pressure are the same.

• The entropy of a system is affected only by the nature

of matter under consideration and by the state in
which it exists.
Entropy and Heat
• In general, an increase in entropy results from the
addition of heat into the system through the
degradation of energy in any form or, by the direct
supply of heat to the system.

• In short, the entropy of the system is increased by the

addition of heat through any mechanism or from any
source.

• The increase in entropy is proportional to the heat

exchanged but not equal to it, since, it is necessary to
consider the temperature of the system when the heat
is transferred.
 Entropy and Temperature
• Consider a system consisting of a weight
and two separate reservoirs, one at Weight W
temperature TH and the other at a lower
temperature Tc .

• The weight is first allowed to fall to the

high-temperature reservoir, transferring High Low
to it certain quantity of heat in the
process. The heat so transferred is then Temp Temp
made to flow into the reservoir at Tc .

• These two irreversible processes result

in a net increase in entropy which would
be the same as the increase in entropy
that would result if the weight were
allowed to fall directly to the reservoir at
Tc as entropy is a state function.
• It means that the transfer of energy to a low
temperature leads to a greater degradation than
that resulted by the transfer of the same quantity
to a higher temperature.

• The greater the degradation of the energy, the

greater would be the irreversibility of the process.

• Entropy, being a thermodynamic function, used to

measure the degree of degradation or the extent of
irreversibility, should therefore, be related not to Q,
but to Q/T, where Q is the heat received by the
reservoir and T is its temperature.
Entropy and Nature of Process
• Maximum possible degradation of higher forms of
energy into heat, which is possible only in a
reversible process.

• Entropy change should therefore be measured as

𝑄𝑅
where QR, the heat transferred when the
𝑇
process occurs reversibly.
• Hence entropy change in a process is
dQR
dS =
T
 Carnot Cycle
• Nicolas Sadi Carnot (1824) introduced the concept of cyclic
operations and was among the first to study the principles
of the second law of thermodynamics.

• He devised a classical ideal cycle named after him that

formed the basis for the mathematical statement of
second law of thermodynamics.

• The Carnot cycle consists of an alternate series of two

reversible isothermal processes and two reversible
adiabatic processes.
The Carnot cycle is represented in the figure below
• During the process AB, heat is transferred reversibly
and isothermally to the working substance from the
high-temperature reservoir (HTR) at temperature T1
and the system performs an amount of work which
is given by the area under the curve AB on the PV
diagram.

• During the reversible adiabatic expansion (BC), the

temperature of the system decreases from T1 to T2 .
The area under the curve BC gives the net work
obtained from this step.
• During process CD, the system rejects heat Q2 to a low
temperature reservoir (LTR) at a constant temperature T2.
The area on the PV diagram under the curve CD is the net
work done on the system during this step.

• The final step is a reversible adiabatic compression (DA)

during which the temperature rises from T2 to T1 and the
original conditions are restored to the system.

• The area under the curve DA is the work done on the system
for this change. The enclosed area ABCD represents the net
work delivered by the engine.
The Carnot principle involves the following two propositions.
1. No heat engine operating in a cycle between two constant
temperature reservoirs can be more efficient than a
reversible engine working between the same two
reservoirs.

2. All reversible engines working between two constant

temperature reservoirs have the same efficiency
irrespective of the working substance, and this efficiency
is dependent only on the temperature levels.
• For Carnot engine we have
𝑄1 𝑇1
=
𝑄2 𝑇2

• Efficiency of Carnot Engine

𝑊𝑜𝑟𝑘 𝑜𝑢𝑡𝑝𝑢𝑡 𝑄1 −𝑄2 𝑇1 −𝑇2 𝑇2

𝜂= = = =1−
𝐻𝑒𝑎𝑡 𝐼𝑛𝑝𝑢𝑡 𝑄1 𝑇1 𝑇1

• Carnot engine gives the maximum efficiency as the

processes considered are reversible.
Ideal gas as the Carnot working substance
• Consider an ideal Carnot engine cycle with an ideal gas as
the working substance.
• Let PA, PB, PC and PD denote the pressures of the gas at the
various states represented by points A, B, C and D
respectively.
• The isothermal expansion step AB and isothermal
compression step CD are carried out at constant
temperatures T1 and T2 respectively.

• The net work done by the engine

• The work done during the reversible adiabatic
operations BC and DA are equal and opposite.
𝑇
𝑊𝐵𝑐 = ∆𝑈𝐵𝐶 = ‫ 𝑇׬‬2 𝐶𝑉 𝑑𝑇
1
𝑇1
𝑊𝐷𝐴 = ∆𝑈𝐷𝐴 = ‫𝑇𝑑 𝑉𝐶 𝑇׬‬
2

• Hence 𝑊𝑛𝑒𝑡 = 𝑊𝐴𝐵 + 𝑊𝐶𝐷

• During isothermal expansion process (AB) work

done and heat are related as
𝑃𝐴
−𝑊𝐴𝐵 (𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑠𝑦𝑠𝑡𝑒𝑚) = 𝑄1 = 𝑅𝑇1 𝑙𝑛
𝑃𝐵
• During isothermal heat rejection process (CD) work
done and heat are related as
𝑃𝑐
−𝑊𝐶𝐷 (𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑠𝑦𝑠𝑡𝑒𝑚) = 𝑄2 = 𝑅𝑇2 𝑙𝑛
𝑃𝐷

• Hence net work done

• Now efficiency of heat engine

• For the adiabatic processes BC and DA

• Comparing above equations,

 Entropy – A State function

Where, Q1 = Heat absorbed ( positive sign)

Q2 = Heat rejected by the system ( negative sign)

For a reversible heat engine,

Any reversible cyclic operation like the one represented on the

P-V diagram in figure may be regarded as made up of a large
number of imaginary Carnot cycles.
For each such cycle we can write
equation similar to above
equation as,

Combining all such equations

that are written for the separate
Carnot cycles,

where R represents reversible

process
where S is the entropy of the system, the thermodynamic property
of a system as a quantity that undergoes no net change in a cyclic
operation is a state function.

The heat transferred in a process is a path function, the ratio of the

heat transferred to the temperature at which it is transferred is a
state function.
 Calculation of Entropy Changes
• The entropy change accompanying a process is applicable
for a reversible process. Entropy being a state function
depends only on the end states.

• The entropy change in an irreversible process occurring

between any two states would be the same as the entropy
change in a reversible process occurring between them.

• Thus entropy change in any irreversible process can be

evaluated by devising an imaginary reversible process for
accompanying the same change of states.
Phase Change
The entropy change in phase transition like fusion, vaporization or
transition from one crystalline form to further can be evaluated
from the values of the latent heat of phase change and the
temperature at which the change is carried out.

Phase change can be treated as changes occurring reversibly at

constant temperature.
For ex.

Where, ΔSV = Entropy of vaporization

 Process involving Ideal Gases
For a differential change in the thermodynamic state of a closed
system , first law can be written as,
dU = dQ + dW

For reversible work

dU = d𝑄𝑅 − P dV

Or dQR = dU + P dV

Since this infinitesimal change in the state of the system can be

assumed to occur at constant temperature T, the entropy
change,
dQR dU+PdV
dS = =
T T
For an ideal gas,
RT
𝑑𝑈 = 𝐶𝑣 𝑑𝑇 𝑎𝑛𝑑 𝑃 =
V

CV dT + (RTdV / V) dT d𝑉
dS = = CV +R
T T V

Assuming that CV is independent of temperature, and

integrating,
Above equation can be used for the evaluation of entropy change
accompanying the change in states of ideal gases.

It can be put in another form also,

For a constant volume process,

For a constant pressure process,

For an isothermal process,

Above equations can also be used for irreversible processes.

Problems
1. Determine the change in entropy when 2 kg of gas at
277 K is heated at constant volume to a temperature of
368 K. Take the specific heat at constant volume = 1.42
kJ/kg K.
Examples
Solution: Entropy change accompanying a constant
volume process is given by,

For m = 2 kg,
Examples
2. Calculate the entropy change when 1 kmol of an ideal
gas at 300 K and 10 bar expands through a throttle to a
pressure of 1 bar, both pressures being maintained
constant during the process by suitable means.

Solution: During throttling enthalpy is unchanged.

For an ideal gas enthalpy being a function of temperature

alone, the temperature remains unchanged during the
process. Hence the process can be taken as isothermal.
Examples
Therefore, entropy change accompanying the process can
be computed by Equation
Adiabatic Mixing Process
• When two substances at different temperatures are
mixed together adiabatically, both will attain an
intermediate temperature, say, T.

• The change in entropy of each is calculated as,

• where T1 denotes its initial temperature and T

denotes equilibrium or steady state temperature.

• For hot body the temperature decreases from T1 to

T and for cold it increases from T2 to T.
Adiabatic Mixing Process
• The total entropy change is then obtained by
adding the individual changes.

 Application
Above equation can be used for the calculation of
change in entropy in processes like mixing of two
fluid streams or quenching of metallic bodies in
liquids.
Problem
Ten kilograms water at 375 K is mixed adiabatically with 30
kg water at 275 K. What is the change in entropy?
Assume that the specific heat of water is 4.2 kJ/kg K and is
independent of temperature.
Solution: Let T be the final temperature attained by the
system. Then the heat balance can be applied
Heat lost = Heat gained
10(375 - T) = 30 (T - 275)
Solving this, T = 300 K.
Let ΔS1 be change in entropy of the hot water and let ΔS2
be that of cold water.

Then, the Total Entropy Change is,

Problems
1. An inventor claims to have developed a
refrigeration unit which maintains the
refrigerated space at 270 K while operating in a
room where the temperature is 300 K and which
has a coefficient of performance of 9.5. How do
you evaluate his claim?

2. A new engine is claimed to be having a power

output of 4.5 hp while receiving a heat input of
6.25 kW and working between the source and
sink temperature limits of 1000 K and 500 K.
Determine the efficiency of the proposed engine.
Is the claim for the engine admissible?
Unsolved Problem ( Ref: 4.8 K V Narayan)

3. One mole of an ideal gas is compressed isothermally at 400

K from an initial pressure of 1 bar to a final pressure of 10
bar. The work required for this irreversible process is 20 per
cent more than that required for a reversible compression.
The heat liberated during compression is absorbed by a
heat reservoir at 300 K. Determine:
a. The entropy change of the gas
b. The entropy change of the reservoir
c. The total entropy change.
Answers
a. –19.1437 J/mol K
b. 30.63 J/K
c. 11.49 J/K
4. The heat capacity of chloroform in the range 240 K
to 330 K is given by
CP = 91.47 + 7.5*10–2 T
where CP is in J/mol K and T in K. Calculate the
change in molar entropy of chloroform when it is
heated from 273 K to 300 K.

Ans: 10.65 J/K .mol

 Mathematical Statement of the Second Law of Thermodynamics

First, let us consider the entropy change in a closed

adiabatic system.
• Referring to Figure, the path AB may be treated
as an irreversible adiabatic operation.

• That is, the curve AB is the pressure-volume

relationship of a spontaneous process occurring in
a closed system for which there is no net heat
interaction.

• The work associated with this process is WAB . Let

the system be brought back to the original
condition along the reversible path BA.
• Let 𝑄𝐵𝐴 and 𝑊𝐵𝐴 be the heat and work associated
with this process.

• In the combination of these two processes the

system has undergone a cycle of changes so that
the overall energy and entropy changes must be
zero.
• Since dU is zero, the first law of thermodynamics
demands that the net heat interaction must be
equal to the net work interaction. That is,
• If QBA were positive, the above equation would
mean that the system receives heat and converts it
completely to work, which would be a violation of
the second law of thermodynamics.

• The second law therefore requires that QBA be

either negative or zero.

• QBA and the net work cannot be zero, as these

would then correspond to a reversible cyclic
process. But the cycle is irreversible.
Therefore, QBA is negative and since the entropy
change ∆S𝐵𝐴 for the reversible step can be
calculated as the ratio of heat transferred to the
temperature,
∆SBA < 0

Or, the process BA is accompanied by a decrease in

entropy. As the entropy change for the cycle as a
whole is zero, the entropy change along path AB
must be positive.
∆SAB > 0
• Thus, we see that a spontaneous process
occurring in a closed adiabatic system is
accompanied by an increase in entropy.

• For a reversible process occurring in a closed

adiabatic system the entropy change must be
zero, as there is no heat exchange. An isolated
system is a closed adiabatic system.

• Therefore we can conclude that the entropy

change of an isolated system in any process
must be equal to or greater than zero.
• Isolated system can be treated as one made up of
the system and its surroundings.
(∆S)System + (∆S)Surrounding ≥ 0

• The processes for which entropy changes are

positive are possible, and processes for which
these are negative are impossible.

(∆S)total ≥ 0
Example
Oil at 500 K is to be cooled at a rate of 5000 kg/h in a
counter-current exchanger using cold water available at
295 K. A temperature approach of 10 K is to be main-
tained at both ends of the exchanger. The specific heats of
oil and water are respectively 3.2 and 4.2 kJ/kg K.
Determine the total entropy change in the process.

Solution: Assume that the oil is cooled to the minimum

permissible temperature.
Example

Inlet temperature of oil = 500 K

Outlet temperature of oil = 305 K

Inlet temperature of water = 295 K

Outlet temperature of water = 490K

The mass flow rate m of water can be determined by an

enthalpy balance.
Example
The mass flow rate m of water can be determined by an
enthalpy balance.

m = 3809.5 kg/h
Example
Entropy change,

Total Entropy Change = 8118.8 – 7908.7 = 210.1 kJ/K