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6 Entropy PDF
6 Entropy PDF
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)
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Entropy
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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
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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• 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)
• 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
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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)
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)
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?
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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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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