ENTROPY

Entropy is denoted by S. It is defined in terms of differential equation for ds, the

infinitesimal small change in entropy. If dqrev is the amount of heat absorbed by the
system in a reversible manner at a constant temperature T, then the entropy change
dS is given by
ds= dqrev /T (1)
For finite changes
∆S = dqrev /T (2)
Thus, entropy change may be defined as the amount of heat absorbed by the
system in a reversible manner divided by the absolute temperature at which the
heat is absorbed.
Entropy is a State Function.
In the definition of entropy the quantity dqrev is not a state function and depends
on the path of the change. There may be number of ways in which the process can
be performed reversibly and in each case the value of dqrev will be different. Hence
dqrev is not a perfect differential. However, dqrev /T is a perfect differential. This
can be shown in the following way
Suppose 1 mole of an ideal gas is undergoing a reversible expansion. From the first
law
dqrev = dE+PdV
=CvdT+ꭍRTdV/V
ꭍ dqrev = ꭍ CvdT + ꭍ RTdV/V (3)
we know that dqrev is not an exact differential, hence integrated. This is confirmed
by observing the right-hand side of eq (3) where the quantity ꭍ RTdv/V
cannot be evaluated unless we specify the path, or in other words, the relation
between T and V is known. For different values of T, V will have different values.
Thus dqrev depends on the path by which the expansion is carried out. Now dividing
Eq. (3) by T on both the sides, we get
dq rev CvdT RTdV
ꭍ T
=ꭍ T + ꭍ V
dT dV
= ꭍCv T + ꭍ R V
Cv ln T + Rln V + constant (4)
 dq rev dq rev
It follows that ꭍ T
can be evaluated, hence T
is an exact differential. It
may, therefore, be concluded that entropy change dS is an exact or perfect
differential and hence entropy S is a state function.
Thus, if a system changes from initial state 1 to final state 2, the entropy change is
expressed by integrating Eq. (4:1) between the limits of initial state 1 and final
state 2,
2 2 dq rev
ꭍ1 dS = ꭍ1 T
2 dq rev
∆S = S2-S1= ꭍ 1 T
(5)

Where S1 and S2 are the entropies of the system in the initial and final states
respectively.
It should be clearly borne in mind that the entropy change ds equal to the amount
of heat absorbed divided by the absolute temperature only when the process is
carried out reversibly. If the process is carried out irreversibly the quantity of heat
absorbed dqirrevdivided by temperature T i.e., dqirre v/T will not be equal to
ds , the change in the entropy, because

The amount of heat absorbed in irreversible manner will be indefinite and

uncertain and hence cannot be used in evaluating the entropy changes.
From Eq. (1) it is evident that when heat is absorbed by the system dq is positive
and hence dS is also positive. Thus, the entropy of the system increases with the
absorption of heat and decreases with the evolution of heat. In an adiabatic
reversible change dqrev=0, the entropy change ds is also zero. Hence adiabatic
reversible processes are associated with no entropy change and are called
isoentropic processes.
Units of Entropy. Entropy has dimensions of energy×temperature-1 and is
generally expressed in cal deg-1 .It is also referred to as entropy unit or eu. Thus,
1 eu= 1 cal deg-1 . Entropy also depends on the amount of the substance ,hence the
amount should also be specified in the units. For 1 mole of a substance the units of
entropy are cal deg-1 mole-1. This is called molar entropy. For 1 gm of a
substance the entropy units are cal deg-1 gm-1.
Entropy calculations
Entropy is a state function and the change in entropy for given process is
independent of the path between the initial and in final states. The process may
occur by any path, reversible or irreversible, but the entropy change will be the
same. To compute the value of ∆S, a path for which a calculation is as simple
possible is chosen. The most convenient path frequently chosen is the reversible
path, because Eq. (1) is applicable to reversible processes and employed in entropy
change calculations.
(i) Entropy changes for an Ideal Gas.
Consider a system consisting of n moles of an ideal gas occupying a volume V
at a pressure P and temperature T. If dąrev amount of heat is absorbed by the
system reversibly, then the increase in entropy dS is given by
ds = dqrev /T (6)
From the first law of thermodynamics, for a reversible process in which only
pressure-volume work is involved
dqrev = dE+PdV (7)
Substituting for dqrev from Eq. (7) in Eq. (6), we get

where Cv is the molar heat at constant volume. Substituting values of P and dE in

above Eq. we get

(8)
If the entropy, volume and temperature of the system in the initial state are S 1, V1
and T1 and in the final state are S 2, V2, and T2 respectively, then integrating Eq. (8)
between these limits we get

Assuming C to be independent of temperature over the temperature range

considered, we obtain
∆S = S2-S1 = nCv In T2/T1+nR In V2/V1 (9)
For 1 mole of an ideal gas
∆S = Cv In T2/T1+R In V2/V1 (10)

An alternate form of Eq. (9) involving pressure terms can be obtained in the
following manner :
If P1 is the pressure of the system in the initial state and P2 in the final state, then
from the gas equation

Substituting in Eq. (9), we obtain

(11)

From Eq. (9) and (11) entropy changes for an ideal gas can be calculated. These
equations take different forms under different
(i) For an Isothermal Process i.e. when T1 = T2. For such
processes Eqs. (9) and (11). are reduced to

The subscript T in ∆S, indicates that the process is occurring at constant

temperature. In an expansion V2>V1, or P1>P2 hence ∆ST, is positive but in
contraction V1> V2, or P2> P1 and hence ∆ST, is negative. From this it is concluded
that in an isothermal expansion entropy increases and in contraction it decreases

(ii) For an Isobaric Process i.e., when P1 = P2. For such process Eq. (11)
reduces to
 ∆ Sp= nCp ln T2/T1

(iii) For an Isochoric Process i.e., when V1= V2. For

such a process Eq. (9) reduces to
∆Sv = nCv lnT2/T1

Example . Calculate the entropy change when 2 moles of an ideal gas are allowed
to expand from a volume of 1 litre to a volume of 10 litres at 27°C.

Solution.
We know that for an isothermal expansion of an ideal gas
∆ST= nRln V2/V1
Here
V1= 1 lit V2 = 10 lit
N= 2 moles
R = l.987 cal deg-1 mole-1
∆ST = 2.303 x2 x 1.987 log 10/1
= 9.152 cal deg-1
Example . Calculate the entropy change when 1 mole of an ideal gas is heated
from 20°C to 40°C at a constant pressure.The molar heat at constant pressure of
the gas over this temperature range is 6.189 cal deg-1.

Solution. We know that for an isobaric process

∆ Sp= nCp ln T2/T1
= 2.303 nCp log T2/T1
Here n=1 mole
Cp = 6·189 cal deg-1 .
T1 = 273+20 = 2930K
T2 = 273+40 = 3130K
∆ Sp = 2.303 x 1 x6.189x log 313/293
= 0.4077 cal deg-1.

(2) Entropy Change in Heating a Solid or a Liquid

When a solid or a liquid is heated without producing change in state, the heat
change is given by
Quantity of heat absorbed=Mass x Specific heat X Temperature rise
=No. of moles x Molar heat X Temperature rise,
Thus, if m gm of a solid or a liquid of specific heat s is heated reversibly through
temperature dt, the amount of heat absorbed is given by
 dqrev = msdt
:. The entropy change dS= dqrev/T = msdt/T

(12)
Assuming that s remains constant within the temperature limits T1 and T2, Eq(12) on
integration gives
∆ S = ms ln T2/T1
= 2.303 ms logT2/T1
Example . Calculate the change in entropy when 2 moles of lead are heated from
27°C to 28°C. The specific heat of lead over this temperature range is 0.03 cal.
gm-1 and the atomic weight of lead is 207.
Solution. We know that
∆ S = 2.303 ms logT2/T1
m = 2 x 207 = 414 gm
s = 0.03 cal gm-1
T1 = 273+27 = 3000K
T2 = 273+28 = 3010K
∆S = 2.303 x 414 x 0.03 x log301/300
= 0·0428 cal deg-1. :

Entropy Change Accompanying Change of Phase

A process of change of state e.g., melting of solid or vaporization of liquid may
be carried out at constant temperature reversibly as the two phases are in
equilibrium for all times during the change. Suppose the process of change of state
of 1 mole of substance is carried out reversibly, the amount of heat absorbed will
be equal to molar heat of fusion or vaporization and the temperature will be the
melting or boiling point. Thus, the molar entropy change accompanying a fusion
process is given by .
∆S = Lf /Tf
where Lf is the molar heat of fusion and T f is the freezing or melting point on the
absolute scale. Similarly, the molar entropy change accompanying a vaporization
process is given by
∆S = Lv /Tb

where Lv , is the molar heat of vaporization and T b is the boiling point on the
absolute scale.
In the same way the molar entropy change accompanying transition of one
allotrope into another is given by
∆S = Lt /Tt

Where Lt is the molar heat of transition and T t is the transition temperature on the
absolute scale.

Example . Calculate the total entropy change when 5 moles of ice at 0°C. and 1
atm. Pressure is converted into steam at 100 °C. The molar heat of fusion of ice
and the molar heat of vaporization of water are 1440 and 9720 cal mol -1. The
molar heat capacity of water over this temperature range may be taken equal to 18
cal mole-1

Solution :

The process is irreversible. To compute the entropy change in the given process
may be imagined to be carried out reversibly in the following three steps:
(i) H2O (s) at 0°C → H2O (l) at 0°C
(ii) H2O(l) at 0°C → H2O (l) at 100°C
(iii) H2O (2) at 100°C H20 (g) at 100°C
The molar entropy change in process (i) is given by
∆S1 = Lf /Tf
= 1440/273= 5.274 cal deg-1 mole-1
The molar entropy change in process (ii) is given by
∆S2 = 2.303 Cp logT2/T1
= 2.303 x 18 x log 373/273
= 5.616 cal deg-1 mole-1
The molar entropy change in process (iii) is given by
∆S3 = Lv /Tb
= 9720/373
= 26.06 cal deg-1 mole-1
The total molar entropy change ∆S = ∆S1 + ∆S2 +∆S3
= 5.274 +5.616 + 26.06
The entropy change per mole = 36.95 cal deg-1 mole-1
= 36.95 cal deg-1 .
.. The total entropy change for 5 moles = 5 x 36.95
= 184.75 cal deg
Example : Calculate the total entropy change when 5 moles of ice is converted
into water at 0oC. The latent heat of fusion of ice is 80 cal gm-1

Solution : We know that molar entropy change

∆S = Lf /Tf

Here latent heat of ice = 80 cal gm-1

Molar heat of fusion Lf= 80x18 cal mole-1

Tf= 273°K
∆S=80 x 18/273
= 5.274 cal deg-1 mole-1
The entropy change per mole = 5.274 cal deg-1
:. The total entropy change for 5 moles = 5x5.274
= 26.37 cal deg-1

Entropy Changes in Reversible Processes

To evaluate the total entropy change of the universe.. entropy change of the system
as well as of the surroundings should be considered. When a system gains heat. the
surroundings loses heat and hence their entropies also change. The total change in
entropy will, therefore, be equal to the algebraic sum of entropy changes of the
system and the surroundings, i.e.,
∆S = ∆Ssystem + ∆Ssurroundings.
Consider an isothermal reversible expansion of an ideal gas. The gas absorbs q rev
heat at temperature T. The entropy change of the gas i.e, system is given by
∆Ssystem = qrev/T
Since the expansion is reversible, the system is in equilibrium with its
surroundings at all times during the expansion. Hence, the surroundings loses an
amount of heat equal to qrev or we can say that the surroundings absorbs - qrev of
heat. The entropy change of the surroundings is given by
∆Ssurroundings = – qrev/T

.: The total entropy change of the universe,

∆S = ∆Ssystem + ∆Ssurroundings.
= qrev/T - qrev/T
∆S = 0
It is concluded that for a reversible process the total entropy change of the
universe is zero.
Entropy Changes in Irreversible Processes
Suppose an irreversible process is occurring at temperature T. and let qirrev be the
amount of heat absorbed by the system from its surroundings. The total entropy
change of the system ∆Ssystem will be greater than the quantity q irrev/T._This can be
shown as follows:
Consider a system changes from state 1 to state 2 once reversibly and again
irreversibly. From the first law of thermodynamics,the heat changes for the two
processes may be written as
qrev =∆E+Wrev (1)
qirrev = ∆E+wirrev (2)
since initial and final states are same, subtracting Eq. (2) from Eq.(1) we obtain
qrev - qirrev = Wrev - wirrev (3)
We know that between the same two states the work done by the system
in a reversible process is greater than the work done in irreversible process, i.e.
Wrev > Wirrev (4)

Applying Eq. (4) in Eq. (3), we get

qrev — qirrev > 0
or qrev > qirrev (5)
Dividing Eq. (5) by T on both the sides, we get
qrev/T > qirrev/T (6)
Since qrev/T = ∆Ssystem
:. ∆Ssystem > qirrev/T (7)

Now we shall calculate the total entropy change of the universe in an irreversible
process. When qirrev amount of heat is absorbed by the system from its
surroundings to carry out the process, the entropy increase of the system ∆S system
will be same whether the process is carried out reversibly or irreversibly, because
the entropy is a state property. However, the entropy change of the surroundings
does not depend on the change in the state of the system and vary with the process
by which the change is brought about. The entropy change of the surroundings
may be best ascertained by supposing that the initial state of the surroundings can
be restored by supplying qirrev amount of heat in a reversible manner at temperature
T i.e., by increasing the entropy of the surroundings by the amount q irrev/T. Thus, in
the process under consideration the entropy change of the surroundings
∆Ssurroundings will be numerically equal but opposite in sign of the above value i.e.,
∆Ssurroundings = — qirrev/T
The total entropy change of the universe
 ∆S = ∆Ssystem +∆Ssurroundings
= ∆Ssystem – qirrev/T
Since ∆Ssystem > qirrev/T vide Eq. (7)
∆S > 0
Thus, in an irreversible or spontaneous process, the entropy of the universe
increases. This can be illustrated by taking the following examples :
(i) Isothermal Expansion of an Ideal Gas. Consider an irreversible isothermal
expansion of an ideal gas. Suppose n moles of an ideal gas expands irreversibly
from a volume V1 to a volume V2 .Since System is independent of the path of the
change, it is given by
∆Ssystem = nR In V2/V1

The entropy change of the surroundings will, however, be different. Let us take
the extreme case of isothermal free expansion i.e., expansion in vacuum. In this
case no work is done by the gas i.e.,w=0 . For an isothermal process ∆E = 0.
According to the first law of thermodynamics,
q = ∆E+w
= 0+0=0
This shows that no heat is absorbed by the system and as such no heat will be
given up by the surroundings and consequently
∆Ssurroundings = 0
The total entropy change of the universe
∆S = ∆Ssystem + ∆Ssurroundings
= nR In V2/V1 +0

or ∆S = nR In V2/V1

since V2 > V1, the value of ∆S is positive. Hence in an irreversible expansion of an

ideal gas the entropy of the universe increases.
(ii) Flow of heat from a Higher to a Lower Temperature.
These changes are mostly spontaneous in nature . All the natural process occurring
are irreversible in nature
Suppose a system is kept at higher temperature say T 1oK . It looses energy
according to second law of thermodynamics and approaches the temperature T 2 oK

Entropy change in first position ∆S1 = -q/T1

Entropy change in final position∆S2 = q/T2
 Total entropy change is
∆S2 -∆S1 = q/T2+ q/T1
q[1/T2+ 1/T1]
∆Stotal = q[T1 + T2]
T1T2
Here T1> T2
∆Stotal is always positive value.
It is said that for irreversible change the value of entropy increases
For reversible change , the value of entropy is zero.

Entropy and The Second Law of Thermodynamics

We have seen that in an irreversible process the total entropy of the system and the
surroundings, ie., universe increases. Since all spontaneous processes are
irreversible, we can say that spontaneous processes occur with the increase in
entropy. Conversely, it can be said that a process may occur spontaneously in the
direction in which the entropy of the universe increases. This forms a criterion for
a spontaneous change. Thus, the definition of entropy and its general behaviour
constitute another expression for the second laws of thermodynamics. The formal
statement of the Second Law of Thermodynamics in terms of entropy may be
given as follows:

There is a thermodynamic function, called entropy S. The change in entropy is

given by ds = dqrev/T where dqrev is amount of heat absorbed by the system
reversibly at T°K. In all reversible processes, the entropy of the universe remains
unchanged whereas in all irreversible processes, the entropy of the universe
increases.

This expression of the second law is most useful from chemists point of view. It
immediately tells us that a chemical reaction would occur spontaneously in a
direction characterised by the entropy increase. The change will continue until the
entropy reaches maximum as permitted by the system under consideration and
finally equilibrium is established.

Physical Significance of Entropy

(i) Entropy and unavailable energy

The second law of thermodynamics tells us that whole amount of internal energy
of any substance is not convertible into useful work. A portion of this energy
which is used for doing useful work is called available energy. The remaining part
of the energy which cannot be converted into useful work is called unavailable
energy. Entropy is a measure of this unavailable energy. In fact, the entropy may
be regarded as the unavailable energy per unit temperature.

Therefore Entropy = Unavailable energy /Temperature

The concept of entropy is of great -value and it provides the information regarding
structural changes accompanying a given process.

(ii) Entropy as a Measure of degree of Chaos or Disorder Randomness.

We have already seen that spontaneous or natural processes gradually pass into
equilibrium state. The equilibrium state is the state of maximum randomness or
disorder. To illustrate this let us take an example of the mixing of two gases-
hydrogen and oxygen as shown in fig. . The two gases are contained in

Fig. Mixing of Two Gases.

closed container and separated by a shutter S [Fig.]. When the shutter is removed,
the gases diffuse into one another spontaneously and eventually mix up as shown
in Fig.
What we observe in this process? At the start, the molecules of two gases were
occupied in separate compartments and after removing the shutter they diffused
and become more mixed or in other words, the system has become more chaotic or
disordered.
Similarly, in the dissolution of NaCl in water as shown in fig, we see that at the
beginning, water molecules are occupied in one part of the vessel and the ions of
salt in the other part. The dissolution process is spontaneous and after some time
the molecules of water and ions of the salt are mixed up and the system becomes
more chaotic.

Fig. Dissolution of NaCl in Water.

From these examples, it is clear that when spontaneous process occurs the system
becomes more chaotic or in other words the degree of disorder or chaos or
randomness increases. On the other hand, in spontaneous processes the entropy
also increases. Thus, the entropy may be regarded as a measure of degree of
disorder or randomness.
By definition it is clear that when heat is given to the system the entropy of the
system increases and hence the disorder or chaos also increases. Thus, when a solid
is melted or a liquid is evaporated the entropy of the system increases. This is
illustrated in Fig. A piece of copper is composed of Cu atoms arranged in regular
manner when it is in solid state. The atoms have fixed positions

Increase in degree of chaos

and their vibrations are small. When heat is supplied to melt it, the atoms remain
no longer fixed to a particular location as shown by marked atoms A and B and
move from one place to another. Thus, chaos has increased. Continue heating the
copper till it boils and converts into gaseous state. The atoms are now more free to
move at random and the disorder has further increased. Since the randomness of a
substance increases from solid to gaseous state, the entropy also increases in the
same order. Thus, the entropy of a substance is higher in gaseous state and lower
in solid state.
(iii) Entropy as a Function of Thermodynamic Probability.
The thermodynamic probability of a system is defined as the maximum number
of different ways in which a system in the given state may exist. To understand the
meaning of thermodynamic probability let us take four indistinguishable coins in
a box and shake them. There are, in all, the following five possible state,
(complexions or microstates) in which the coins may be found arranged in the
box..

(i)All the four coins showing heads.

(ii)Three coins showing heads and one showing tail.
(iii) Two coins showing heads and two showing tails.
(iv) One coin showing head and three showing tails.
(v) All the four coins showing tails.

On the other hand, if the coins are distinguishable, then the possible number of
ways (microstates) or the probability of getting the above five states would be as
given below. Here, H and T stand for head and tail showing respectively and
subscripts 1, 2, 3, and 4 distinguish the four coins.

States Arrangements Total number of

arrangements
(microstates)
4 heads H1H2H3H4 1
3 heads, 1 tail H1H2H3T4, H1H2T3H4, 4
H1T2H3H4, T1H2H3H4
2 heads, 2 tails H1H2T3T4, H1T2H3T4, 6
H1T2T3H4, T1H2H3T4,
T1H2T3H4, T1T2H3H4
1 head, 3 tails T1T2T3H4, T1T2H3T4, 4
T1H2T3T4, H1T2T3T4
4 tails T1T2T3T4 1
The probability of getting 2 heads and 2 tails is highest and is six times as great as
of getting either 4 heads or 4 tails. Now, if a large number of such boxes
containing four distinguishable coins are shaken, the number of boxes showing 2
heads and 2 tails would be maximum because this state has large number of
arrangements or higher probability.

We know that in a spontaneous process, the entropy increases and becomes

maximum at equilibrium. Equilibrium position, as already stated, is a state of
maximum disorder or chaos. The maximum disorder is attained when the
molecules are distributed in maximum possible ways i.e., when the thermodynamic
probability becomes high. Thus, we see that the system moves from a less
probable state to a more probable state. Entropy, on the other hand, also changes
from a lower value to a higher value. Hence entropy may be taken as the function
of thermodynamic probability i.e.,

S=f(W)

where W is the thermodynamic probability.

Consider two systems having entropies S1, and S2, and thermodynamic
probabilities W1 and W2. Then
S1 = f (W1)
S2 = f(W2)
The two systems are now mixed and let the resulting entropy and the
thermodynamic probability of the combined system be S and W respectively, then
S = f (W)
Since entropy is an additive property, the total entropy of the combined system is
given by
S = S1+S2 = f (W1)+f (W2)
The probability is a multiplicative factor hence the resulting thermodynamic
probability of the combined system is given by
W = W1xW2
Substituting for S and W , we obtain
f (W1)+f (W2) = f (W1x W2).
This condition can be satisfied only when the function is logarithmic Hence, it
may be written that
S = k In W+C
where k and C are constants. The constant k is found to be Boltzmann constant.
Further in case of a perfect crystal the entropy is zero at 0°K, (third law). The
perfect crystal has only one arrangement at 0°K, hence the value of S can be zero
only when the value of C is zero. Hence, the value of C is zero and Eq. takes the
form
 S = k in W
This is called the Plancks-Boltzmann equation and gives a quantitative
relationship between the entropy and the thermodynamic probability of a system.