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Chemical Engineering Thermodynamics (CHE 303)
Lecture 10: Entropy
Dr. Wael A. Fouad
Assistant Professor
Chemical Engineering Department
King Fahd University of Petroleum and Minerals
Chapter 5:
Volumetric Properties of Pure
Fluids
2
Statements of the 2nd law
1. No apparatus can operate in such a way that its only effect
(in system and surroundings) is to convert heat absorbed by
a system completely into work done by the system
2. No process is possible which consists solely in the transfer
of heat from one temperature level to a higher one
3
Heat engines
• Heat engines: devices that produce work from heat in a
cyclic process
• Example: steam power plant (working fluid = water)
QH
boiler
Win pump turbine Wout
condenser
QL 4
Carnot factor
• Carnot factor: maximum efficiency for a heat engine
(production of work from heat in a cyclic process):
QC TC QC TC
=1 − = 1− where: =
QH TH QH TH
• Real efficiencies are generally much lower (real processes
are not fully reversible)
5
Entropy
• The equation for a Carnot engine when applied to the
working fluid of the engine becomes:
QC TC QH QC QH QC
= =− + =0
QH TH TH TC TH TC
• Thus, the quantity Q/T characterizes a property whose
change is zero for a complete reversible cycle
• By making the isothermal steps infinitesimal small, we may
write: dQH dQC dQrev
+ =0 or: =0
TH TC T
• The entropy can now be defined as: dQrev
• Entropy is a state function dS =
t
(path independent) T 6
Entropy
• Entropy change of a reversible process:
dQrev
dS = S − S =
t t
B
t
A
T
• Entropy change of an irreversible process: dQrev
dQ S =
t
dS = S − S
t t
B
t
A T
T
• Entropy change of system: Integration is not carried out for
the irreversible path
• Entropy change of heat reservoir (surroundings): Q/T
(both for reversible or irreversible heat transfer)
• Total entropy change:
Stotal = S system + S surr = S Bt − S At + S surr
7
Entropy
• Second law defines the entropy change: TdS = dQrev
• dS establishes the direction of chemical processes
(dS ≥ 0)
• absolute entropy (S) can only be defined in the context
of statistical mechanics
• The entropy of a system during a reversible and adiabatic
(dQrev = 0) process is constant → isentropic process
(dSt = 0)
8
Entropy changes of an ideal gas
• For an ideal gas undergoing a mechanically reversible
process in a closed system:
dU = dQrev − pdV
• Alternatively, in terms of enthalpy (H=U+pV):
dH = dU + pdV + Vdp = dQrev + Vdp
dQrev = dH − Vdp
• For an ideal gas: dH = C P dT and V = RT / p
ig
dp
dQrev = C dT − RT
ig
P
p dT dp
dS = Cig
P −R
dQrev ig dT dp T p
= CP −R 9
T T p
Entropy changes of an ideal gas
ig dT dp dS C Pig dT dp
dS = C P −R = −
T p R R T p
• Integration from (p0,T0) to (p,T):
C Pig
S
T
C dT ig
p = A + BT + CT 2 + DT − 2
= − ln
P
with: R
R T0 R T p0 C Pig A
= + B + CT + DT −3
RT T
• Solution for integral:
C Pig dT 2 D + 1
( − 1)
T
= A ln + BT0 + CT0 + 2 2
T0 R T T0 2
whereby τ = T/T0 10
Entropy changes of an ideal gas
T
dT
P
ig
C
T
=
T0
• Mean heat capacity evaluated for entropy: C ig
ln(T / T0 )
P S
C Pig 2 D + 1
S
= A + BT0 + CT0 + 2 2 ( − 1) / ln
R T0 2
• Final solution for entropy change of an ideal gas:
S C Pig T p
= S
ln − ln
R R T0 p0
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Example 1
• Methane at 550 K and 5 bar undergoes a reversible adiabatic
expansion to 1 bar. What is the final temperature?
• Solution:
S C ig
T p C Pig T p 1
= ln = ln = −1.6094
P S
= ln − ln =0 S
ln
R R T0 p0 R T0 p0 5
− 1.6094
T = T0 exp ig with:
C /R
P S
C Pig 2 D + 1
S
= A + BT0 + CT0 + 2 2 ( − 1) / ln
R T0 2
Iteration converges on T = 411.34 K
12
Example 2
• Two adjoining containers with volume V each; one is empty,
the other one contains an ideal gas. What is the entropy
change is the wall between the 2 containers is removed?
T is constant
V V p1V1 = p2V2 = p2 2V1
p1
p2 =
2
dT dp p2
dS = C ig
P −R S = − R ln = + R ln 2
T p p1
NB. dS is positive, so the process moves to the right (from p1 to p2)
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Direction of processes
• Every process proceeds in such a direction that the total
entropy change associated with it is positive
• The limiting value of zero is attained only by a reversible
process
• No process is possible for which the total entropy
decreases
S total 0
Mathematical statement of the second law
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