Chemical Engineering Thermodynamics (CHE181403)

MODULE 3
LIMITATIONS OF THE FIRST LAW OF THERMODYNAMICS
The first law of thermodynamics deals with energy changes involved in a process. The first law specifies only this: if
energy is produced during a process, it must be compensated with a loss of an exactly equal quantity, so that the total
energy before and after the process are the same. The major limitation of the first law of thermodynamics is its inability
to deal with the direction of the process and the extent of change.
GENERAL STATEMENTS OF THE SECOND LAW OF THERMODYNAMICS
The second law of thermodynamics is just the generalization of our experiences with spontaneous processes and can be
stated in a number of ways:
1. Heat cannot by itself pass from a cold to a hot body.

2. All spontaneous processes are, to some extent, irreversible and are accompanied by a degradation of energy.

3. Every system, when left to itself, will on the average, change toward a system of maximum probability.

4. 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. This statement implies that at least two thermal reservoirs of different
temperatures are necessary for a heat engine to operate. This is because only part of the heat transferred to the
engine from a high temperature reservoir is converted to work; the rest is rejected to a low temperature reservoir.

5. 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. In other words, any
process, which consists solely in the transfer of heat from one temperature to a higher one, is impossible. It means
that energy in the form of work must be supplied to the heat pump in order to transfer heat from a cold body to a
hot body. Therefore, the coefficient of performance of a heat pump can never be infinity.

Heat Engine
𝑜𝑢𝑡𝑝𝑢𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑖𝑚𝑒𝑑 𝑎𝑡
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 (𝜂) = =
𝑖𝑛𝑝𝑢𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑡ℎ𝑎𝑡 𝑐𝑜𝑠𝑡𝑠

𝑊
=
𝑄𝐻
𝑄𝐻 − 𝑄𝐿
=
𝑄𝐻
𝑄𝐿
=1−
𝑄𝐻

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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

𝑜𝑢𝑡𝑝𝑢𝑡 𝑒𝑛𝑟𝑔𝑦 𝑎𝑖𝑚𝑒𝑑 𝑎𝑡

𝑅𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟: 𝐶𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝑃𝑒𝑟𝑓𝑜𝑟𝑚𝑎𝑛𝑐𝑒 (𝐶. 𝑂. 𝑃) = =
𝑖𝑛𝑝𝑢𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑡ℎ𝑎𝑡 𝑐𝑜𝑠𝑡
𝑄𝐿 𝑄𝐿
= =𝑄
𝑊 𝐻 −𝑄𝐿

𝑜𝑢𝑡𝑝𝑢𝑡 𝑒𝑛𝑟𝑔𝑦 𝑎𝑖𝑚𝑒𝑑 𝑎𝑡

𝐻𝑒𝑎𝑡 𝑃𝑢𝑚𝑝: 𝐶𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝑃𝑒𝑟𝑓𝑜𝑟𝑚𝑎𝑛𝑐𝑒 (𝐶. 𝑂. 𝑃) = =
𝑖𝑛𝑝𝑢𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑡ℎ𝑎𝑡 𝑐𝑜𝑠𝑡
𝑄𝐻 𝑄𝐻
= =𝑄
𝑊 𝐻 −𝑄𝐿

(𝐶. 𝑂. 𝑃)ℎ𝑒𝑎𝑡 𝑝𝑢𝑚𝑝 = 1 + (𝐶. 𝑂. 𝑃)𝑟𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟

Entropy
Why the Concept of Entropy?
The second law of thermodynamics states that all spontaneous processes are, to some extent, irreversible and are
accompanied by a degradation of energy. It also means that it is impossible for any self-acting machine to transfer energy
from a given state to a higher state of availability. To make these statements quantitative there is required some function
that always changes in a certain way during a spontaneous process and therefore, will characterise such a change. Internal
energy was defined to give quantitative significance to the first law. Internal energy does not change in any characteristic
way in a spontaneous process, and it does not help in any way in the development of the second law. The function that is
fundamental in the development of the second law is entropy, which means transformability (change) in Greek, introduced
by Clausius in 1851.
All spontaneous processes result in an increase in the entropy and no process is possible that results in a decrease in
entropy.
Entropy is a thermodynamic property that increases when heat is supplied, decreases when heat is rejected and remains
constant if no heat supplied or rejected.

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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

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 Golaghat Engineering College
Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

CALCULATION OF ENTROPY CHANGES

Phase Change
The entropy changes in phase transitions like fusion, vaporization, or transition from one crystalline form to another can
be evaluated from the values of the latent heat of phase change and the temperature at which the change is carried out.
HV
SV 
T
HV  latent.heat.of .vaporization

Processes involving Ideal Gases

For a differential change in the thermodynamic state of a closed system, the first law of thermodynamics can be written
as
dQ = dU + dW
When the process is reversible and the work involved is only work of expansion (P dV), the above equation can be
modified as
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
dU  PdV
dS 
T
For an ideal gas: dU  CV dT
P  RT / V
Assuming that CV is independent of temperature, this equation can be integrated for a finite change from state 1 to state
2 giving for one mole of an ideal gas.
T2 V
S  CV ln  R ln 2 ............(1)
T1 V1

It can be put in another form also. We know that for ideal gases,
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Sanjay Paul

CV  CP  R.........(2)
V2 PT
 1 2 ...........(3)
V1 P2T1

Substituting Eqs. (2) and (3) into Eq. (1), we obtain the following:
T2 P
S  CP ln  R ln 2 ............(4)
T1 P1

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
T
dQ
S  
Ti
T
where Ti denotes its initial temperature. The total entropy change is then obtained by adding the individual changes.
EXAMPLE 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 gives

10c p (375  T )  30c p (T  275)

T  300

300
300
S1  m  C p dT  10C p ln  2.23C p
375
375
300
300
S 2  m  C p dT  30C p ln  2.61C p
275
275
Stotal  S1  S 2  0.38C p  1.59kJ / K

Isothermal Mixing of Ideal Gases

Consider a mixture of two or more ideal gases at pressure P and temperature T. Let the mole fraction of the components
in the mixture be represented by xi. The entropy change resulting from the irreversible process of mixing of ideal gases in
their pure state at temperature T and pressure P to form the mixture at the same temperature and pressure can be computed
by the following equation

S   R xi ln xi

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Sanjay Paul

Example: A vessel is divided into two equal compartments by a membrane: where one contains oxygen at 50 oC and 2
atm pressure, while the other contains nitrogen at the same temperature and pressure. Calculate the change in entropy of
the system if the membrane is ruptured and the system attains equilibrium.
Solution: since P, T and V are same for both compartment, it will be an equimolar mixture.

S   R xi ln xi   R(0.5ln 0.5  0.5ln 0.5)   R ln 0.5  R ln 2

THE CARNOT PRINCIPLE
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 as shown in Fig. (next page). 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.
Carnot Cycle
A reversible cycle is an ideal hypothetical cycle in which all the processes constituting the cycle are reversible. 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 –
1. Reversible isothermal heat supply/absorption
Q1 enters the system at 𝑇1 reversibly from a constant temperature source at 𝑇1 .The internal energy of the system
increases. From First law,
Q1  U 2  U1 1 W2 ..............(1)[U 2  U1 for.ideal g as]

2. Reversible adiabatic expansion

work 2W3 is done by the system adiabatically and reversibly at the
expense of its internal energy, and the temperature of the system
decreases from T1 to T2 . Using the first law,

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0  U 3  U 2  2 W3 ................(2)

3. Reversible isothermal heat rejection

heat Q2 leaves the system at 𝑇2 to a
constant temperature sink at 𝑇2 reversibly,
and the internal energy of the system
further decreases. From the first law,
Q2  U 4  U 3 3 W4 ...............(3)

4. Reversible adiabatic compression

work 4 W1 is done upon the system
reversibly and adiabatically, and the internal energy of the system increases and the temperature rises from T2 to
T1 . Applying the first law,

0  U1  U 4  4 W1.................(4)

Summing up Eqs (1) to (4)

Q1  Q2  (1W2  2 W3 )  (3W4  4 W1 )

Q net Wnet

MATHEMATICAL STATEMENT OF THE SECOND LAW OF THERMODYNAMICS

Entropy is a property of the system that determines the direction of change. All spontaneous processes are accompanied
by an increase in the entropy, and for reversible processes, entropy doesn’t change.
First, let us consider the entropy change in a closed adiabatic system. Referring to Fig, 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 ΔU is zero, the first law of thermodynamics demands that
the net heat interaction must be equal to the net-work interaction. That is: QBA = WAB + WBA
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
ΔSBA for the reversible step can be calculated as the ratio of heat
transferred to the temperature,
ΔSBA < 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 changes
along path AB must be positive.

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ΔSAB > 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.

S(isolated .system )  0.....................(1)

S system  Ssurrounding  0............(2)
As a spontaneous process occurring in a closed adiabatic system is accompanied by an increase in entropy, for such a
system it can be said that entropy is that property of the system that determines the direction of change. The processes for
which entropy changes are positive are possible, and processes for which these are negative are impossible.
Equations (1) and (2) are the general mathematical statements of second law of thermodynamics. These statements apply
to the total change in entropy; in an irreversible process, a decrease in entropy may occur either in the system or in the
surroundings. These statements require only that the sum of the entropy changes of the system and the surroundings
together be positive in an irreversible process like the isothermal expansion of a gas. If the same expansion were carried
out reversibly, the increase in the entropy of the gas will be compensated by a decrease in the entropy of the surroundings
that results because of the withdrawal of heat. If this heat exchange also were accomplished reversibly, the net change in
entropy would be zero. Equation (2) is also known as the principle of increase in entropy.
The principle of increase in entropy with reference to an isolated system means that the only processes that can occur in
an isolated system are those that have an increase in entropy associated with them. The universe is a perfect example of
an isolated system and all naturally occurring processes in the universe are accompanied by an increase in entropy and are
irreversible. Hence we can say that the entropy of the universe goes on increasing. The statements for the first and second
laws of thermodynamics can now be combined: The energy of the universe is conserved whereas the entropy is increasing.
THIRD LAW OF THERMODYNAMICS
Statement: The absolute entropy is zero for a perfect crystalline substance at absolute zero of temperatures.