UNIT 3

UNIT III
Limitations of the First Law Thermal Reservoir, Heat Engine, Heat pump, Parameters
of performance, Second Law of Thermodynamics, Kelvin-Planck and Clausius
Statements and their Equivalence / Corollaries, PMM of Second kind, Carnots principle,
Carnot cycle and its specialties, Thermodynamic scale of Temperature,
Clausius Inequality, Entropy, Principle of Entropy Increase Energy Equation, Availability
and Irreversibility Thermodynamic Potentials, Gibbs and Helmholtz Functions, Maxwell
Relations Elementary Treatment of Third Law of Thermodynamics
Limitations of first law
The first law of thermodynamics has its own limitations
in actual practice. Some situations are given below.
1. According to the first law of thermodynamics, heat and work
are mutually convertible .complete conversion is not possible in
real practice.
2. According to the first law of thermodynamics, there is no
restriction on the direction of flow of work and heat, which is
not true.
3. According to the first law of thermodynamics, in energy
cyclic process work and heat are exchangeable completely but
from experience it is not.
4. In natural way heat is not completely converted to work, but
reverse is not automatically true.
5. Heat flows from hot to cold region, but reverse is not
automatically true.
6. high pressure gas expands to low pressure but reverse is not
atomatically true.
7. from the above cases some external source of energy is
required for reverse processto occur which again violates the
1st law of thermodynamics.
8.Joules experiment amply demonstrate that energy, when supplied to a
system in the form of work, can be completely converted into heat(work
transfer -+ internal energy increase -+ heat transfer). But the complete
conversion of heat into work in a cycle is not possible. So heat and work are
not completely interchangeable forms of energy
. When work is converted into heat, we always have

but when heat is converted into work in a complete closed cycle process

ENERGY RESERVOIRS
A thermal energy reservoir (TER) is defined as a large body of infinite
heat capacity. which is capable of absorbing or rejecting an unlimited quantity
of heat without suffering appreciable changes in its thermodynamic coordinates.
The changes that do take place in the large body as heat enters or leaves
are so very slow and so very minute that all processes within it are quasi-static.
The thermal energy reservoir TERH from which heat QI is transferred to
the system operating in a heat engine cycle is called the source.
The thermal energy reservoir TERL to which heat Q2 is rejected from the
system during a cycle is the sink.
A typical source is a constant temperature furnace where fuel is
continuously burnt, and a typical sink is a river or sea or the atmosphere itself.
A mechanical energy reservoir (MER) is a large body enclosed by an
adiabatic impermeable wall capable of storing work as potential energy (such as
a raised weight or wound spring) or kinetic energy (such as a rotating flywheel).
All processes of interest within an MER are essentially quasi-static. An MER
receives and delivers mechanical energy quasi-statically,

Cyclic heat engine with source and sink

Kelvin planck statement of Second law and PMM2 :
IT is impossible for a heat engine to produce net work in a complete
cycle if it exchanges heal only with bodies at a single fixed temperature.

If Q2 =0, the heat engine will produce net work in a complete cycle
by exchanging heat with only one reservoir, thus violating the Kelvin-Planck
statement fig 1 Such a heat engine is called a perpetual motion machine of the
second kind, abbreviated to PMM2. A PMM2 is impossible
.A heat engine has, therefore, to exchange heat with two thermal energy
reservoirs at two different temperatures to produce net work in a complete cycle
fig 2 .So long as there is a difference in temperature, motive power(i.e. work)
can be produced. If the bodies with which the heat engine exchange heat are of
finite heat capacities, work will be produced by the heat engine till the
temperatures of the two bodies are equalized.

FIG 1 A PMM2

If the second law were not true, it would be possible to drive a ship
across theocean by extracting heat from the ocean or to run a power plant by
extracting heat from the surrounding air. Neither of these impossibilities
violates the first law of thermodynamics. Both the ocean and the surrounding air
contain an enormous store of internal energy, which, in principle, may be
extracted in the form of a flow of beat. There is nothing in the first law to
preclude the possibility of converting this heat completely into work. The
second law is, therefore, a separate law of nature, and not a deduction of the
first law ".The first law denies the possibility of creating or destroying energy;
the second denies the possibility of utilizing energy in a particular way. The
continual operation of a machine that creates its own energy and thus violates
the first law is called the PMMI. The operation of a machine that utilizes the
internal energy of only one TER, thus violating the second law, is called the
PMM2.
Clausius Statement of the second law

Heat always flows from a body at a higher temperature to a body

at a lower temperature. The reverse process never occurs spontaneously.
Clausius' statement of the second law gives: It is impossible to
construct a device which, operating in a cycle, will produce no effect other than
tile transfer of heat from a cooler to a hotter body.
Heat canot flow of itself from a body at a lower temperature to a body at a
higher temperature. Some work must be expended to achieve this.
REFRIGERATOR AND HEAT PUMP:
A refrigerator is a device which, operating in a cycle, maintains a
body at a temperature lower than the temperature of the surroundings.
Let the body A FIG 1 be maintained at t2, which is lower than
the ambient temperature t1
Even though A is insulated, there will always be heat leakage Q2 into the body
from the surroundings by virtue of the temperature difference.
In order to maintain, body A at the constant temperature t2, heat
has to be removed from the body at the same rate at which heat is leaking into
the body. This heat (Q2) is absorbed !by a working fluid, called the refrigerant,
which evaporates in the evaporator EI at a temperature lower than t2 absorbing
the latent heat of vaporization from the.body A which is cooled or refrigerated
(Process 4-1).
The vapour is first compressed in the cornpressor C, driven by a
motor which absorbs work Wc (process 1-2), and is then condensed in the
condenser C2, rejecting the latent heat of condensation Q1 at a temperature
higher than that of the atmosphere (at t1) for heat transfer to take place (Process
2-3). The condensate then expands adiabatically through an expander (an engine
or turbine) producing work (We),when the temperature drops to a value lower
than t2 such that heat Q2 flows from the body A to make the refrigerant
evaporate (process 3-4). Such a cyclic device of flow through E1-C1-C2-E2 is
called a refrigerator.
In a refrigerator cycle,attention is concentrated on the body A.
Q2 and W are of primary interest. Just like efficiency in a heat engine cycle,
there is a performance parameter in a refrigerator cycle, called the coefficient of
performance, abbreviated to COP, which is defined as

Fig1 :A cyclic refrigeration plant

A heat pump is a device which, operating in a cycle, maintains a body, say
B(Fig.2), at a temperature higher than the temperature of the surroundings. By
virtue of the temperature difference, there will be heat leakage Q1 from the
body to the surroundings. The body will be maintained at the constant
temperature t1, if heat is discharged into the body at the same rate at which heat
leaks out of the body. The heat is extracted from the low temperature reservoir,
which is nothing but the atmosphere, and discharged into the high temperature
body 0, with the expenditure of work W in a cyclic device called a heat pump.
The working fluid operates in a cycle flowing through the evaporator
E1',compressor C1, condenser C2 and expander E2, similar to a refrigerator,
but the attention is here focussed onthe high temperature body B. Here Q1 and
W are of primary interest, and the COP is defined as

Fig 2 A Cyclic heat pump

. 2

..3

From the above equations 1 & 3

4
T he COP of a heat pump is greater than the COP of a refrigerator by unity.
.5

Q1 is always greater than W.

EXAMPLE:
For an electrical resistance heater, if W is the electrical energy consumption,
then the heat transferred to the space at steady state is W only, i.e., QI = W.
A 1 kW electric heater can give I kW of heat at steady state and nothing more.In
other words, 1 kW of work (high grade energy) dissipates to give 1 kW of heat
(low grade energy), which is thermodynamically inefficient.
However, if this electrical energy W is used to drive the compressor of a heat
pump, the heat supplied QI will always be more than W, or Q1 > W. Thus, a
heat pump provides a thermodynamic advantage over direct heating. For heat to
flow from a cooler to a hotter body, W cannot be zero, and hence,the COP (both
for refrigerator and heat pump) canot be infinity. Therefore, W> 0, and COP <
.

EQUIVALENCE
STATEMENTS :

OF

KELVIN

PLANCK

AND

CLAUSIUS

Kelvin-Planck's and Clausius' statements are two parallel

statements of the second law and are equivalent in all respects.
The equivalence of the two statements will be proved if it can be shown that the
violation of one statement implies the violation of the second, and vice versa.
(a). Let Us first consider a cyclic heat pump P which transfers heat from a low
temperature reservoir (t2 to a high temperature reservoir (t1)with no other
effect, i.e., with no expenditure of work, violating Clausius statement .

FIG 1 : VIOLATION OF THE CLAUSIS STATEMENT

Let us assume a cyclic heat engine E operating between the same thermal
energy reservoirs, producing W net , in one cycle. The rate of working of the
heat engine is such that it draws an amount of heat Q1 from the hot reservoir
equal to that discharged by the heat pump. Then the hot reservoir may be
eliminated and the heat Q1 discharged by the heat pump is fed to the heat
engine. So we see that the heat pump P and the heat engine E acting together
constitute a heat engine operating in cycles and producing net work while
exchanging heat only with one body at a single fixed temperature. This violates
the Kelvin-Planck statement.
(b) Let us now consider a perpetual motion machine of the second kind
(E)which produces net work in a cycle by exchanging heat with only one
thermal energy reservoir (at t1) and thus violates the Kelvin-Planck statement
(Fig. 2).

Let us assume a cyclic heat pump (P) extracting heat Q2 from a low
temperature reservoir at t2 and discharging heat to the high temperature
reservoir at t1 with the expenditure of work W equal to what the PMM2
delivers in a complete cycle. So E and P together constitute a heat pump
working in cycles and producing the sole effect of transferring heat from a
lower to a higher temperature body, thus violating the Clausius statement.

FIG 2: VIOLATION OF THE KELVIN-PLANCK STATEMENT

CARNOT CYCLE:
The carnot cycle was 1 st suggested by a French engineer sadi carnot in 1842
which works on reversible cycle and is known as carnots cycle.
Carnot cycle is a reversible cycle. For a stationary system, as in a
piston and cylinder machine, the cycle consists of the following four successive
processes fig 1

FIG 1:CARNOT HEAT ENGINE STATIONARY SYSTEM

(a) A reversible isothermal process in which heat Q, enters the system at

t1reversibly from a constant temperature source at t1, when the cylinder cover is
in contact with the diathermic cover A. The internal energy of the system
increases.
From First law,
..1
(For an ideal gas only , U1=U2)
(b) A reversible adiabatic process in which the diathermic cover A is replaced
by the adiabatic cover B, and work WE is done by the system adiabatically and
reversibly at the expense of its internal energy, and the temperature of the
system decreases from t1to t2.
using 1 st law,
..2
(c) A reversible isothermal process in which B is replaced by A and heat Q2
leaves the system at '2 to a constant temperature sink at 12 reversibly, and theinternal energy of the system further decreases
.From the first law,
..3
only for an ideal gas, U3 = U4
(d) A reversible adiabatic process in which B again replaces A, and work Wp is
done upon the system reversibly and adiabatically, and the internal energy of
Applying the first law,
.4
Two reversible isotherms and two reversible adiabatics constitute a Carnot
cycle, which is represented in p-v coordinates in fig 2
Or

A cyclic heat engine operating on the Carnot cycle is called a Carnot heat
engine.

FIG 2 CARNOT CYCLE

Performance of carnots cycle :
The carnots cycle cannot be performed in practice because of the
following reasons
1. It is impossible to perform frictionless process.
2. Isothermal process can be achieved only if the piston moves as fast as
possible, so that the heat transfer is negligible due to very short time.
3. The isothermal process and adiabatic process takes place during the same
stroke. Therefore the piston has to move very slowly for part of the stroke
and it has to move very fast during remaining stroke.
4. It is impossible to transfer the heat with out temperature difference.
5. This variation of mition of the piston is not possible.
Carnots theorem:
It stales that of all heat engines operating between a given constant
temperature source and a given constant temperature sink, none has a higher
efficiency than a reversible engine.
Let two heat engines Ea and Eb operate between the given source at
temperature t1 and the given sink at temperature t2 as shown in Fig. 3
Let Ea be any heat engine and Eb be any reversible heat engine. We have to
prove that the efficiency of Eb is more than that of Ea Let us assume that this is
not true and a > b. Let the rates of working of the engines be such that
since

Fig 3 two cyclic heat engine Ea and Eb operating between the same source and
sink, of which Eb is revesible
Therefore,
Now, let Eb be reversed. Since Eb is a reversible heat engine, the magnitudes
of heat and work transfer quantities will remain the same, but their directions
will be reversed, as shown in Fig.4. Since Wa> Wb, some part of WA (equal to
(Wa) may be fed to drive the reversed heat engine

Fig 4 Eb reversed
Since Q1 A = Q1b= Q1 the heat discharged by

may be supplied to EA. The

source may, therefore, be eliminated (Fig. 6.27). The net result is thatEA and3B
together constitute a heat engine which, operating in a cycle, produces net work
WA - W0' while exchanging heat with a single reservoir at (2' This violates the
Kelvin-Planck statement of the second law. Hence the assumption that
is

wrong.
Therefore

Corollary of Carnot's Theorem

The efficiency of all reversible heat engines operating between the same
temperature levels is the same.
Let both the beat engines Ea and Eb (Fig. 3) be reversible. Let us assume
Similar to the procedure outlined in the preceding article, if Eb is
reversed to run, say, as a heat pump using some part of the work output (Wa) of
engine Ea, we see that the combined system of heat pump Eb and engine Ea
becomes a PMM2. So
cannot be greater than
Similarly, if we assume
and reverse the engine E a we observe that

cannot be greater than

Therefore
Since the efficiencies of all reversible heat engines operating between the same
heat reservoirs are the same, the efficiency of a reversible engine is independent
of the nature or amount of the working substance undergoing the cycle.
Absolute Thermodynamic Temperature Scale :
The efficiency of any heat engine cycle receiving heatQI and rejecting heat
Q2 is
given by
.1

By the second law, it is necessary to have a temperature difference (t1-t2 ) to

obtain work of any cycle. We know that the efficiency of all heat engines
operating between the same temperature levels is the same, and it is
independent
of the working substance. Therefore, for a reversible cycle (Carnot cycle), the
efficiency will depend solely upon the temperatures t1and t2' at which heat is
transferred, or
.2
where f signifies some function of the temperatures. From Eqs1 &2

In terme of new function F

.3

If some functional relationship is assigned between t1 ,t2 and Q1/Q2, the

equation becomes the definition of a temperature scale.
Let us consider two reversible heat engines. E1 receiving heat from the source
at t1, and rejecting heat at t2 to E2 which, in turn, rejects heat to the sink at t3
fig 1

Fig 1 three carnot engines

..4

The temperatures

are arbitrarily chosen. The ratio Q1/Q2

dependsonly on t1. and t2, and is independent of t3.So t3 will drop out from the
ratio on the right in equation 4. After it has been cancelled, the numerator can be
writtenas
and the denominator as
where is another unknown
function.
Thus

Since

is an arbitrary function, the simplest possible way to define the

absolute thermodynamic temperature T is to let

as proposed by Kelvin.

Then, by definition
5

The absolute thermodynamic temperature scale is also known as the

Kelvin scale. Two temneratures on the Kelvin scale bear the same relationship
to each other as do the heats absorbed and rejected respectively by a Carnot
engine operating between two reservoirs at these temperatures. The Kelvin
temperature scale is, therefore, independent of the peculiar characteristics of any
particular substance.
The heat absorbed Q1 and the heat rejected Q2 during the two reversible
isothermal processes bounded by two reversible adiabatics in a Carnot engine

can be measured. In defining the Kelvin temperature scale also, the triple point
of water is taken as the standard reference point. For a Carnot engine operating
between reservoirs at temperatures T and Tt, Tt being the triple point of water
fig 2, arbitrarily assigned the value 273.16 K,
6

If this equation is compared it is seen that in the Kelvin scale. Q plays the role
of thermometric property. The amount of heat supply Q changes with change in
temperature.just like the thermal emf in a thermocouple.
It follows from the Eq6

that the heat transferred isothermally between the given adiabatics decreases as
the temperature decreases. Conversely, the smaller the value of Q, the lower
the corresponding T. The smallest possible value of Q is zero, and the
corresponding T is absolute zero. Thus, if a system undergoes a reversible
isothermal process without transfer of heat, the temperature at which this
process takes place is called the. absolute zero. Thus, at absolute zero. an
isotherm and an adiabatic are identical.
That the absolute thermodynamic temperature scale has a definite zero
point can be shown by imagining a series of re versible engines, extending from
a source at T1 to lower temperatures fig 3
Since

fig 3

at equal temperature intervals. A scale having one hundred equal intervals

between the steam point and the ice point could be realized by a series of one
hundred Carnot engines operating as in Fig.3. Such a scale would be
independent of the working substance.
If enough engines are placed in series to make the total work output equal to
Q1, then by the first law the heat rejected from the last engine will be zero. By
the second law, however, the operation of a cyclic heat engine with zero heat
rejection cannot be achieved, although it may be approached as a limit. When
the heat rejected approaches zero, the temperature of heat rejection also
approaches zero as a limit. Thus it appears that a definite zero point exists on
the absolute
temperature scale but this point cannot be reached without a violation 0f the
second law.
ENTROPY
First law of thermodynamics was stated in teerms of cycles. First ,and it was
shown that
Q= w
When the first law was applied for thermodynamic processes, the existence of a
property, the internal energy, was found.
Similarly, the second law was also first stated in terms of cycles executed by
systems. When applied to processes, the second law also leads to the definition
ofa new property, known as entropy. If the first law is said to be the law of
internal energy, then second law may be stated to be the law of entropy. In fact,
thermodynamics is the study of three E's, namely ,energy, equilibrium and
entropy.
Two Reversible Adiabatic Paths Cannot Intersect Each Other

Assume AC and BC (two reversible adiabatics) intersect each other at

point C in fig . Let a reversible isotherm AD be drawn in such a way that it

intersects the reversible adiabatics at A and B. The three reversible processes

AD, BC, and CA together constitute a reversible cycle, and the area included
represents the net work output in a cycle. But such a cycle is impossible, since
net work is being produced in a cycle by a heat engine by exchanging heat with
a single reservoir in the process AD, which violates the Kelvin-Planck statement
of the second law. Therefore, the assumption of the intersection of the reversible
adiabatics is wrong. Through one point. there can pass only one reversible
adiabatic.
Since two constant property lines can never intersect each other, it is
inferred that a reversible adiabatic path must represent some property, which is
yet to be identified.
CLAUSIUS THEOREM
Let a system be taken from an equilibrium state i to another equilibrium
state f by following the reversible path i-f (Fig. 2).
Let a reversible adiabatic i-a be drawn through i and another reversible
adiabatic b-f be drawn through f.
Then a reversible isotherm a-b is drawn in such a way that the area under i-a-b-j
is equal to the area under i-f. Applying the first law for

Fig 2
..1

Therefore Eqs 1&2

Heat transferred in the process i-f is equal to the heat transferred in the
isothermal process a-b.
Thus any reversible path may be substituted by a reversible zigzag path,
between the same end states, consisting of a reversible adiabatic followed by a
reversible isotherm and then by a reversible adiabatic, such that the heat
transferred during the isothermal process is the same as that transferred during
the original process.
Let a smooth closed curve representing a reversible cycle (Fig. 3) be
considered. Let the closed cycle be divided into a large number of strips by
means of reversible adiabatics. Each strip may be closed at the top and bottom
by reversible isotherms.
The original closed cycle is thus replaced by a zigzag closed path consisting of
alternate adiabatic and isothermal processes, such that the heat transferred
during all the isothermal processes is equal to the heat transferred in the original
cycle. Thus the original cycle is replaced by a large number of Carnot cycles. If
the 'adiabatics are close to one another and the number ofCarnot cycles is large.
the saw-toothed zigzag line will coincide with the original cycle.
For the cycle abcd,
heat is
rejected reversibly at T2

Fig 3

If heat supplied is taken as positive and heat rejected as negative

Similarly, for the elemental cycle efgh

If similar equations are written for all the elemental Carnot cycles, then for
the whole original cycle
3

The cyclic integral of

for a reversible cycle is eqal to zero . This is known

as Clausiustheorem. The letter R emphasizes the fact that the equation is valid
only for a reversible cycle.
CLAUSIUS INEQUALITY:
Let us consider a cycle ABCD (Fig.1). Let AB be a general process, either
reversible or irreversible, while the other processes in the cycle are reversible.
Let the cycle be divided into a number of elementary cycles, as shown. For one
of these elementary cycles

Fig 1

Now, the efficiency of a general cycle will be equal to or less than the
efficiency of a reversible cycle.

.1
......2

Since entropy is a property and the cyclic integral of any property is zero
..3

This equation is known as the inequality of Clausius. It provides the criterion

Of the reversibility of a cycle.

Entropy Principle
For any infinitesimal process undergone by a system, we have Eq
for the total mass

For an isolated system which does not undergo any energy interaction with
the surroundings,
Therefore, for an isolated system

For an irreversible process

It is thus proved that
the entropy of an isolated system can never
decrease. It
always increases and remains constant only when the process is reversible.
This is known as the principle of increase of entropy. or simply the entropy
principle. It is the quantitative general statement of second law from the
macroscopic viewpoint..

An isolated system can always be formed by including any system and its
surroundings within a single boundary (Fig. 1). Sometimes the original
system which is then only a part of the isolated system is called a 'subsystem'.

Fig 1
The system and the surroundings together (the universe or the isolated
system) include everything which is affected by the process. For all possible
processes that a system in the given surroundings can undergo

Entropy may decrease locally at some region within the isolated system, but
it must be compensated by a greater increase of entropy somewhere within the
system so that the net effect of an irreversible process is an entropy increase
ofthe whole system. The entropy increase of an isolated system is a measure of
the extent of irreversibility of the process undergone by the system.
Rudolf Clausius summarized the first and second laws of thermodynamics in
the following words:
(a) Die Energie der Welt ist Constant.
(b) Die Entropie der Welt strebt einem Maximum zu.
[(a) The energy of the world (universe) is constant.
(b) The entropy of the world tends towards a maximum.]
The entropy of an isolated system always increases and becomes a maximum
at the state of equilibrium. If the entropy of an isolated system varies with some
parameter x, then there is a certain value of xe. which maximizes the entropy
and represents the equilibrium stateThe system is .

then said to exist at the peak of the entropy hill, and dS = O. When the system is
at equilibrium. any conceivable change in entropy would be zero.

Applications of Entropy Principle

The principle of increase of entropy is one of the most important laws of
physical' science. It is the quantitative statement of the second law of
thermodynamics. Every irreversible process is accompanied by entropy
increase of the universe, and this entropy increase quantifies the extent of
irreversibility of the process. The higher the entropy increase of the universe,
the higher will be the irreversibility of the process. A few applications of the
entropy principle are illustrated in the following,
Transfer of heat through a Finite Temperature Difference
Let Q be the rate of heat transfer from reservoir A at T1 to reservoir B at T2,
T1 > T2 fig 1
For reservoir A,
It is negative because heat Q flows out of the reservoir. For reservoir B,
It is positive because heat flows into the reservoir.

Fig 1
The rod connecting the reservoirs suffers no entropy change
. because, once in the steady state, its coordinates do not change.
Therefore, for the isolated system comprising the reservoirs and the rod, and
since entropy is an additive property

since
If

is positive, and the process is irreversible and possible.

is zero, and the process is reversible. If

negative

and the process is impossible.

ENTROPY TRANSFER MECHANISMS
A. ENTROPY TRANEFER IN THE FORM OF HEAT TRANSFER:
Since

when heat is added to a system

is

positive, and the entropy of the system increases. When heat is removed from
the system, dQ is negative, and the entropy of the system decreases.
Heat transferred to the system of fixed mass increases the internal energy of
the system, as a result of which the molecules (of a gas) move with higher
kinetic energy and collide more frequently, and so the disorder in the system
increases. Heat is thus regarded as disorganised or disordered energy transfer
which increases molecular state. If heat Q flows reversibly
from the system to the surroundings at (To) fig ,the entropy increase of the
surroundings is

The entropy of the system is reduced by

The temperature of the boundary where heat transfer occurs is the constant
temperature To. It may be said that the system has lost entropy to the
surroundings. Alternatively, one may state that the surroundings have gained
entropy from the system. Therefore, there is entropy transfer from the system
to the surroundings along with heat flow. In other words, since the heat inflow
increases the molecular disorder, there is flow of disorder along with heat. The

sign of entropy transfer is the same as the sign of heat transfer: positive, if into
the system, and negative, if out of the system.

On the other hand, there is no entropy transfer associated with work. In

Fig. 2, the system delivers work to a flywheel, where energy is stored in a
fully recoverable form. The flywheel molecules are simply put into rotation
around the axis in a perfectly organised manner, and there is no dissipation and
hence no entropy increase of the flywheel. The same can be said about work
transfer in the compression of a spring or in the raising of a weight by a certain
height. There is thus no entropy transfer along with work. Ifwork is dissipated
adiabatically into internal energy increase of the system ,there is an entropy
increase in the system, but there is as such no entropy transfer to it.
Work is thus entropy-free, and no entropy is transferred with work. Energy
is transferred with both heat and work, whereas entropy is transferred only
with heat. The first law of thermodynamics makes no distinction between heat
transfer and work. It considers them as equals. The distinction between heat
transfer and work is brought about by the second law: an energy interaction
which is accompanied by entropy transfer is heat transfer. and an energy
interaction which is not accompanied by entropy transfer is work. Thus. only
energy is exchanged during work interaction, whereas both energy and entropy
are exchanged during heat transfer.
(b)Entropy transfer through Mass Flow Mass contains entropy as well as
energy, and the entropy and energy of a system are proportional to the mass.
When the mass of a system is doubled, so are the entropy and energy of the
system. Both entropy and energy are carried into or out of a system by streams
of matter, and the rates of entropy and energy transport into or out of a system
are proportional to the mass flow rate. Closed systems do not involve any mass
flow and thus any entropy transport. When an amount of mass m enters or
leaves a system, an entropy of amount ms, s being the specific entropy,
accompanies it. Therefore, the entropy of a system increases by ms when the
mass of amount m enters it, and decreases by by same amount when it leaves it
at by same state.

Entropy Change in an Irreversible Process

For any process undergone by a system,
1

Consider the cycles as shown in fig 1

where A and B are reversible processes and C is an irreversible process. For the
reversible cycle consisting of A and B

For the irreversible cycle consisting of A and C, by the inequality of Clausius,

.3

From eqs 2&3 ,

.4

Since the path B is reversible,

..5

Since entropy is a property,entropy changes for the paths B and C would be

the same. Therefore,
6

From eqs 4 & 6

Thus, for any irreversible process,

Whereas for a reversible process

Therefore, for the general case, we can write

The equality sign holds good for a reversible process and the inequality sign
for an irreversible process.
AVAILABLE ENREGY , AVAILABILITY & IRREVERSIBILITY:
Available energy is also called exergy . Unavailable energy is also called anergy
The sources of energy can be divided into two groups, viz. high grade energy
and low grade energy.
High grade energy
Low grade energy
The conversion of high grade energy Conversion of low grade energy is
to shaft work is exempted
subject to limitations of 2nd law
from the limitations of the second law
Ex:
Ex:
Mechanical work, electrical work,
Heat or thermal energy , Heat derived
water power, wind power, kinetic
from nuclear fission or fusion, Heat
energy of a jet, tidal power
derived from combustion of fossil
fuels
The bulk of the high grade energy in the form of mechanical work or electrical
energy is obtained from sources of low grade energy, such as fuels, through the

medium of the cyclic heat engine. The complete conversion of low grade
energy,heat, into high grade energy, shaft-work, is impossible by virtue of the
second law of thermodynamics. That part of the low grade energy which is
available for conversion is referred to as available energy, while the part which,
according to the second law, must be rejected, is known as unavailable energy.
The originator of availability concept is Josiah Willard Gibbs. He indicated that
environment plays an important part in evaluating the available energy.
Available Energy referred to a Cycle
The maximum work output obtainable from a certain heat input in a cyclic heat
engine (Fig. .1) is called the available energy (A.E.), or the available' part of the
energy supplied. The minimum energy that has to be rejected to the sink by the
second law is called the unavailable energy (U.E), or the unavailable part of the
energy supplied.
Therefore,

For the given T1 and T2,

For a given T1,

will increase with the decrease of T2 . The lowest

practicable temperature of heat rejection is the temperature of the surroundings,

To

Let us consider a finite process x-y, in which heat is supplied reversibly to a

heat engine (fig 2). Taking an elementary cycle, if
is the heat received by
the engine reversibly at T1,then

Fig 1

fig 2

For the heat engine receiving heat for the whole process x-y, and rejecting heat
at To

1
The unavailable energy is thus the
product of the lowest temperature of heat
rejection, and the change of entropy of the system during the process of
supplying heat (fig 3)

Fig 3
Reversible Work by an Open System Exchanging Heat only with the
Surroundings
Let us consider an open system exchanging energy only with the surroundings
at

constant temperature To and at constant pressure Po (Fig). A mass dm1

enters the system at state 1, a mass dm2 leaves the system at state 2, an amount
of heat
is absorbed by the system, an amount of work
is delivered by
the system, and the energy of the system (control volume) changes by an
amount
, applying 1st law we have

For the maximum work, the process must be entirely reversible. There is a
temperature difference between the control volume and the surroundings. To
make the heat transfer process reversible, let us assume a reversible heat engine
E operating between the two. Again, the temperature of the fluid in the control
volume may be different at different points. It is assumed that heat transfer
occurs at points of the control surface where the temperature is T. Thus in an
infinitesimal reversible process an amount of heat
is absorbed by the engine
E from the surroundings at temperature

,an amount of heat

is rejected by

the engine reversibly to the system where the temperature is T, and an amount
of work
is done by the engine. For a reversible engine,

.2

The work

is always positive and is independent of the direction of heat

flow. When

heat will flow from the surroundings to the system,

positive and hence

the system surroundings,

in eqn 2 positive and hence

is negative, and hence

heat will flow from

would

be positive.
Now, since the process is reversible, the entropy change of the system will be
equal to the net entropy transfer, and
Therefore,
3

.4
5

Substituting eq 1 for

in eq.5

is

.6

On substituting the value of

from eq.3

.7

Eqn 7 is the general expression for the maximum work of an open system which
exchanges heat only with the surroundings at
THERMODYNAMIC POTENTIAlS
The thermodynamical state of a system can be described in terms of the
basic independent coordinates p,v,T & s. These four coordinates are insufficient
to obtain complete knowledge of the system we use certain energy terms which
are easily measurable, known as thermodynamics potentials.
Thermodynamic energy potentials are energy functions that are
mathematically formed by combining basic thermodynamic coordinates p,v,T&
s in different ways .

We adopt H,F,G for the thermodynamic functions giving extensive values

and h.f.g. for their specific values (per unit mass).
The four important thermodynamic potentials,
u specific internal energy
f.specific Helmholtz function
gspecific gibbs free energy
hspecific enthalpy.
Internal energy:
Form 1st law and 2nd law of thermodynamics dQ=du+ dW..1
If we allow only pdv work then dQ=du+pdv.2
dQ=Tds

(if it is reversible from 2nd )3

form equ 2 and 3

du+pdv= Tds
du=Tds- pdv4
Or Tds=du+pdv.5
Equations 2&3 contains path function dQ and in exact differentials
Equation 4 all are exact differentials (point function representing the
thermodynamic state)
From eqn 4 du=Tds-pdv..6
du is increment of energy in system )
Enthalpy:
(specific enthalpy h)
H = U +PV
WE know h = u + pv.. 7
To express h is terms of p,v,T and s
We eliminate u from eqn 7 can be written as in the following differential form
dh = du+pdv+vdp
from 5 du = T ds pdv
dh = tds- pdv +pdv+vdp

dh= Tds+vdp .. 8
Tds =dh vdp
Helmholt Free energy (f):
Consider a real isothermal process at constant volume which is always
irreversible .The entropy increses in an irreversible process never decreases.
Therefore ds dQ/T
Tds dQ
d(Ts) dQ ( since T is constant)
d(Ts) du + pdv

d(Ts) du pdv.9
Since isothermal process is taking place at constant volume ,
Therefore d(Ts-u) 0

d(u-Ts) 0 10

u-ts is thus a physical quantity representing energy which never increses during
an Isothermal iso volumic process.
This u-Ts is called Helmholtz free energy or Helmholtz free energy function f
this f= u-Ts
df =du-(Tds+sdT)
df= -pdv-sdt
df=-pdv-sdt
Gibbs free energy:
Considering a real isothermal process at constant pressure (isobaric) which is
always irreversible , from eqn 9
d(Ts) du d(pv)
d (Ts-u-pv) 0
d(u+pv-Ts) 0
this physical quantity representing energy which never increases in a isothermal
process isobaric process is called Gibbs free energy (g)
g=u+pv-Ts

dg= du+pdv +vdp-tds-sdt

dg=tds-pdv+pdv+vdp-tds-sdt
dg = vdp-sdt
Gibbs free energy (g) :
Let us now consider a system which is in both pressure and temperature
equilibrium with the surroundings before and after the process. When the
volume of the system increases some work is done by the system against the
surroundings (pdVwork), and this is not available for doing useful work. The
availability of the system, as defined by neglecting the Ke and Pe changes
can be expressed in the form

the maximum work obtainable during a change of state is the decrease in

availability of the system,as given

If the initial and final equilibrium states of the system are at the same pressure
and temperature of the surroundings, say
Then,

11

The Gibbs function G is defined as

12

Then for two equilibrium states at the same pressure P and temperature T
..13
From eqs 12 &13
..14
...15
The decrease in the Gibbs function of a system sets an upper limit to the work

that can be performed, exclusive of pdV work, in any process between two
equilibrium states at the same temperature and pressure, provided the system
exchanges heat only with the environment which is at the same temperature and
pressure as the end states of the system If theprocess is irreversible, the useful
work is less than the maximum.
MAXWELLS EQUATION :
These equations are differential relations among the basic thermodynamic
coordinates from thermodynamics potentials