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Entropy

Entropy
Recall Carnot engine:

Hot Reservoir, TH
QH

W
QH

Cold Reservoir, TC
Recall Carnot equation:

QH
TH

QC
TC

W.r.t the engine, the numerical value of

QH QC

TH
TC

QH

is positive and that of

QC

is negative:

Q H QC

0 (5.9)
TH TC

Recall: the principle characteristics of a property is that the sum of its change in a complete
cycle is zero.
Thus, eq 5.9 suggests the existence of a property whose changes are given by the quantities
Q/T.

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Entropy
Consider reversible cyclic process shown in the following PV diagram:

QH
TH
P

TC
QC
V
We divide the path by a series of reversible adiabatic curves and isothermal curves. The
spacing of the isothermal steps is very close (infinitesimal) so that the heat quantities become
dQH and dQC so that eq. 5.9 becomes:
dQ H dQ C

0
TH
TC

The sum of dQ/T for the entire cycles give:

dQ rev
0
T

(5.10)

rev means the equation is valid only for reversible process.


From this we infer the existence of a property of the system whose differential changes are
given by dQrev/T
The property is called: ENTROPY (symbol: S) and its differential changes is given by:
dQ
dS t rev
(5.11)
T
dQ rev TdS t

(5.12)

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Entropy
Consider arbitrary reversible paths from A to B:

D
B

P
A
C
V
dQ rev
t
dan S
T
ACB

t
The entropy changes: S

These two integrals must be equal (according to

ADB

dQ rev
T

dQ rev
0)
T

Therefore:
St is independent of path and St = property change given by (StB - StA).
If A to B is irreversible, the entropy change must still: St = StB - StA (because S is a state
function). However, St is not given by dQ/T evaluated for irreversible process.
The entropy changes of a heat reservoir is always given by Q/T, because the effect of the
heat transfer is the same regardless of the temperature of the source or sink of the heat.
When a process is reversible and adiabatic, dQrev =0
process is said to be ISENTROPIC

For mechanically reversible process, S t

dQ
T

dSt=0 (constant entropy); the

even though the heat transfer between

system and surrounding is irreversible.

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Entropy
St of a system caused by the transfer of heat can always be calculated by S t

dQ
T

whether the heat transfer is accomplished reversibly or irreversibly.


However, when a process is irreversible on account of other driving forces, such as
pressure, the entropy change is not SOLELY by the heat transfer, and for its calculation one
must devise a reversible means of accomplishing the same change of state.
Entropy Changes of an Ideal-Gas
Recall first law :

dU = dQ + dW

For reversible process:

dU = (dQrev P dV)

Recall enthalpy definition: H = U +PV dH = dU + P dV + V dP


Substitute dU into dH eq.:

dH = (dQrev P dV ) + P dV + V dP
dQrev = dH V dP

For ideal gas: dH = Cpig dT and V = RT/P; then division by T gives:


dQ rev
dP
ig dT
CP
R
T
T
P

Recall

dQ rev
dS
T

ig
C dT dP
1 dQ rev
P

R
T
R T
P

ig
dS C P dT

d ln P
R
R T

ig
C P dT
S
P
T

ln
T
R
Po
o R T

(5.13)
(5.14)

ig
Recall that for ideal gas: Cp = A + BT + CT2 + DT2

Combining the two equations, the first term of RHS can be expressed as:
ig

T C P dT A ln BT CT 2 D
T
0
o

0 R T
2 To2

1

1
2

(5.15)

where T
o
Define mean heat capacity: Cig
P

T ig
To C P dT / T

ln T To
S

(5.16)

Subscript S denote a mean value specific to entropy calculation.

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Entropy
ig
T CP dT

S To R T
R
ln

ig
CP

Divide 5.16 by R:

Recall:

ig

T C P dT A ln BT CT 2 D
T
0
o

0 R T
2 To2

1

1
2

(5.16a)

(5.15)

Substitute 5.15 to 5.16a we get:

ig
CP

Recall: Cig
P

S A BT CT 2 D
0
o
R

2 To2

1 1

2 ln

T ig
To C P dT / T

ln T To
S

(5.16)

dT

ig
T ig
Rearrange: T C P T C P ln T
o
S
o

Divide by R:

ig
T C P dT
T
o R T

(5.17)

ig
CP
R

S ln T
To

ig
C
Recall S T P dT ln P
To R T
R
Po

(5.16b)
(5.16c)
(5.14)

Substitute 5.16c to 5.14 we get:


S

ig
CP
R

S ln T ln P
To
Po

(5.18)

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Entropy
Mathematical Statement of The Second Law
Consider:

TH
QH
TC
Entropy change at hot reservoir:

t Q
S H
TH

Entropy change at hot reservoir:

t Q
SC
TC

t S t Q Q
STotal SH
C T
H TC

T T
STotal Q H C
TH TC

Because TH>TC total entropy = positive


When TH - TC gets smaller, Stotal becomes smaller.
When TH is only infinitesimally higher than TC (the heat transfer is reversible) then Stotal
approaches zero.
Thus: irreversible Stotal = positive
reversible Stotal = 0

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Entropy

Consider: adiabatic irreversible process from A to B and restored to A by a reversible path

Qrev
Reversible
path

P
A
Irreversible
adiabatic

B
V

If A-B process results in an entropy change, then there must be heat transfer during B-A
process that:
t S t A dQ rev
S t SA
B B T

Irreversible + reversible = cycle U=0 Q = - W


Therefore: W ( Wirr Wrev ) Wirr Wrev Q rev BA dQ rev
According to 2nd law, Qrev cannot be directed into the system, for the cycle would then be a
process for the complete conversion of heat into work.
A dQ
Thus B
rev is negative;

t St
SA
B

is also negative

t St
SB
A

Since A-B is adiabatic Ssurr = 0


then Stotal = Ssurr + SAB = 0 + (StB StA) = positive
If we assume A-B process produces no entropy change of the fluid then we can restore the
system by a simple adiabatic reversible process. The cycle is accomplished with no heat
transfer and no net work. The system is restored without leaving any change elsewhere.
This implies that A-B is reversible rather than irreversible.
Conclusion: Stotal is always positive, approaching zero as a limit when the process becomes
reversible.
Stotal 0

(5.19)

Mathematical statement of 2nd law


No process is possible for which the TOTAL entropy decreases.

70

Entropy
Recall:
Hot Reservoir, TH

QH

QH

Cold Reservoir, TC

The engine operate in cycle: no net change in its properties.


Stotal = Stres,TH + Sengine + Stres,TC = Stres,TH + + Stres,TC
t
Recall: Entropy changes of reservoirs: SH

STotal
Work of the engine:

W Q H QC

Substitute Qc into Stotal eq.:


Rearrange: STotal
STotal QH (

QH
TH

QH
TC

W
1
1

)
TC TH
TC

QH
TH
QH
TH

t
and SC

QC
TC

QC
TC

QC Q H W

STotal

QH QH W

TH
TC

W
TC

or

T
W TC STotal Q H 1 C
TH

TC

Recall: W TC STotal Q H 1
TH

General eq. for work of HE operating between 2 heat reservoirs

71

Entropy
Hot Reservoir, TH

QH

QH

Cold Reservoir, TC

T
Recall: W TC STotal Q H 1 C
TH

Minimum work = 0 (completely inefficient, the system become simple irreversible heat
transfer between TH and TC)

T
0 TC STotal Q H 1 C
TH

T T
STotal Q H H C
TH TC

Maximum work is obtained when the engine is reversible (Stotal = 0):

T
W 0 Q H 1 C
TH

T
W Q H 1 C
TH

work of a Carnot engine

The Third Law of Thermodynamics


The absolute entropy is zero for all perfect crystalline substance at absolute zero temperature
(0 K).
Absolute entropy of a gas at other temperature can be calculated from:
S oTf

CP
CP
g
S dT H f T
t dT H T
dT
T
T
T
Tf
T
T
T
f

CP

(assumption: no solid state transition, no heat of transition)

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