11/7/2011

Chapter‐6
Entropy

Clausius Inequality
For a Carnot cycle or a reversible engine,
Q1/Q2 = T1/T2
Q1/T1 = Q2/T2
Q1/T1 – Q2/T2 = 0
=0
Q1/T1 + Q2/T2 = 0  (use of algebraic sum)
Σ Qi / Ti = 0 ………….(a)

Now let us consider an irreversible engine which absorbs energy as

heat (Q1) from a reservoir at T1 and rejects energy as heat (Q’2) to a
reservoir at T2.
Now, ηirreversible < ηreversible
or, 1 – Q’2/Q1 < 1 – Q2/Q1
1 – Q’2/Q1 < 1 – T2/T1
Q’2/Q1 > T2/T1
Q’2/T2 > Q1/T1

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Q1/T1 – Q’2/T2 < 0

Q1/T1 + Q’2/T2 < 0 (use algebric sum)
Σ Qi / Ti < 0 ……………(b) 
From above equations (a) and (b), it can be stated that,

Σ Qi / Ti ≤ 0 or 

(Clausius inequality)

The Clausius inequality states that whenever the system

undergoes a cyclic change, however complex the cycle may be
(as
( long
l as it involves
i l heat
h t and d workk interactions),
i t ti ) theth algebraic
l b i
sum of all the heat interactions divided by the absolute
temperature at which the heat interactions are taking place
considered over the entire cycle is less than or equal to zero. The
equality sign holds for reversible and inequality for irreversible.

Entropy

• Qualitative judgement of feasibility of a process by IInd law

• Quantitative judgement of feasibility of a process by clausius
inequality.
• Clausius introduced a property called entropy which stipulates
feasibility of a process.
• Consider a reversible cycle,

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Applying the Clausius inequality to above cycle,

∫dQ/ T has same value for path IA2 or 1B2, irrespective of path
as long as path is reversible. So, (dQ / T)Rev is an exact differential
of some function which we now identify as entropy.

Therefore, the entropy is defined as,

S2 – S1 = ∆S

So, dS = (dQ/T)
So, dS (dQ/T)R for a reversible process only.
for a reversible process only.

• Change in entropy for a irreversible process = ?

• Calculation of Entropy change ?

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Entropy change for heat interaction with a reservoir

• Suppose a certain amount of heat is added to a reservoir.

• Heat addition may be reversible or irreversible with contact

with another reservoir or by performing work.

• Actual irreversible process may be replaced by an imaginary

reversible path.

• Entropy change of the reservoir,

∆S = ∫(dQ/T)R = Q / T

Entropy change for heating or cooling of a matter

• Consider heating of matter by bringing it into contact with a 
body at higher temperature (irreversible process)

• Replace irreversible process with imaginary reversible process 
with same initial and final conditions.

• Heating may be carried out at constant pressure or constant 
volume or combination of both

• For constant pressure process,  
∆Sp = ∫(dQ/T)R = ∫(dH/T)R  
= ∫mCPdT/T = mCPln(T2/T1)  (If Cp is constant)

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otherwise, If CP = a + bT + CT2

∆Sp = ∫mCPdT/T = ∫m(a + bT + CT2) dT/T

• Also, for constant volume process,  
∆SV = ∫(dQ/T)
∫(dQ/T)R = ∫(dU/T)
∫(dU/T)R  
= ∫mCVdT/T = mCVln(T2/T1)  (If CV is constant)

otherwise, If CV = a + bT + CT2

∆SV = ∫mCVdT/T = ∫m(a + bT + CT2) dT/T

• Total entropy change for heating of matter at constant 
pressure followed by constant volume,
∆S = ∆Sp + ∆SV

Entropy change for Phase change

• Pure substance phase change at constant T and P.

• Phase
Phase change are generally at finite temperature differences 
change are generally at finite temperature differences
(irreversible)

• Replace with a imaginary reversible process

• Solid to liquid entropy change = ∆S
q py g sf = ∫(dQ/T)
∫( Q/ )R =  hsf // Tsf

• Liquid to gas entropy change = ∆Sfg = ∫(dQ/T)R =  hfg / Tfg

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Entropy change for Adiabatic mixing

• Hot substance is adiabatically mixed with a cold one.
(Irreversible system)

• Hot substance cools down and cold substance heat up.

• Determine final temperature with energy balance

• Calculate entropy change for each substance with use of 
∆S = ∫(dQ/T)R

• Total entropy change = ∆S = ∆S1 + ∆S2

Entropy change for an ideal gas

• Consider an ideal gas undergoes a state change from (P1,v1,T1) 
to (P2,v2,T2).

• Replace process with a reversible path (1a2 or 1b2 etc.)

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• Consider path 1a2 (1‐a: reversible constant pressure heating 
and a‐2: reversible isothermal compression)
∆s1a = ∫dq/T = ∫CPdT/T = CP ln(T2/T1) 
∆sa2 = ∫dq/T = ∫dw/T =∫Pdv/ T = R ln(v2/va)

Since, P2v2 = Pava = P1va or v2/va = P1/P2

So, ∆sa2 = – R ln(P2/P1)

Therefore, molar entropy change, ∆s =  ∆s1a + ∆sa2
= CP ln(T2/T1) – R ln(P2/P1)

Or

CV ln(T2/T1) + R ln(V2/V1)

Mixing of Non‐identical ideal gases

• Suppose a rigid and insulated container is divided into two 
compartments by a partition. 
Partition is removed and gases are allowed to mix
• Partition is removed and gases are allowed to mix.
• Replace actual process with a imaginary reversible process

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• For gas A, entropy change in isothermal expansion,
(∆S1)A = ∫dQ/T = ∫dW/T = ∫PdV/T = ∫nARdV/V 
= nARln(Vf/Vi) = nAR ln(P/PA) = ‐ nAR ln(PA/P)

Similarly for gas B (∆S1)B = ‐

Similarly for gas B, (∆S = ‐ nBR ln(PB/P)

Where, PA = [nA/(nA +nB)]P = XAP and PB = XBP

XA and XB = mole fractions of A and B in final mixture

Hence ∆S1 = ‐ nAR ln(XA) ‐ nBR ln(XB) = ‐ ΣniR ln(Xi)

Also, ∆S
l 2 = 0

Therefore, Total entropy change after mixing
∆S = ∆S1 + ∆S2 =  ‐ ΣniR ln(Xi) (∆S > 0, as Xi < 1)
or  molar entropy change = ‐ ΣXiR ln(Xi)

Principle of Entropy Increase

Consider a state change as following,
A and B: reversible paths
C: irreversible path
p

Writing Clausius inequality for
reversible cycle 1A2B1,

Again Clausius inequality for 1A2C1,

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From equation (a) and (b), we have,

Since process 2B1 is reversible, replace above with,

So,  We have

In general one can write,

(For a process of any system)

Equality for reversible and inequality sign for irreversible. 

• What is entropy change of universe when a system interact with 
its surroundings and exchanges heat with surroundings?

• Let Tsys and Tsur = temperatures (Tsur > Tsys )

dQ =  heat transfer (Irreversible)

Then, dSsys = dQ/Tsys
dSsur = ‐ dQ/Tsur
dSuni = dSsys + dSsur
= dQ/Tsys ‐ dQ/Tsur > 0

∆Suni > 0
If the system is not interacted with
surroundings,  Then,  ∆Suni = 0  

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Therefore,  ∆S >= 0  (For an isolated system)

The entropy of an isolated system either increases or remains

constant.

The equality sign holds good when the process undergone by

system is reversible; The inequality sign holds good if there is any
irreversibility present in the process. This statement is called
principle of entropy increase.

This principle dictates the direction of a spontaneous process.

process
If ∆S < 0, process is not possible.

Second law Analysis of a Control Volume
We know that the change in entropy  of a system is given by,
dS ≥ dQ/T
This can be expressed as,  ∆S = dQ/T + SG
Where SG represents entropy generation in the system such that 
Where, S represents entropy generation in the system such that
SG=0 for reversible process and SG > 0 for an irreversible process. 

Consider  a control 
volume,

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At time t, the entropy of the system =

At time (t + dt), the entropy of the system =

Then,

This can also be stated as,
[Rate of accumulation of entropy] = [Rate of entropy inflow] ‐
[Rate of entropy outflow] + [Rate of entropy generation]

Steady state flow processes
At steady state conditions, dS/dt =0,
Then above equation reduces to,

For an adiabatic process, 
However, if process is adiabatic and reversible,  
These processes are known as isentropic.

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