Entropy

heat engine

Lets consider the efficiency of a Carnot engine again

C 1

Q1C
Q 2C

T
1 1
T2

Q1C
Q2C

Q2C Q2C

Th=T2

T1

T2

Tc=T1
Q1C Q1C
C
C
C
C
Taking into account Q2 Q2 and Q1 Q1

Q1C Q 2 C

0
T1
T2

Generalization of the above considerations

Clausius Theorem

Clausius Theorem:

The heats Qi exchanged at absolute temperatures Ti

by a cyclic process of N steps satisfy
N Q
i 0 .
i 1 Ti

Note: the Qi might be irreversibly exchanged

Theorem applies to any real engine cycle

Proof of the Clausius theorem: Consider a general cyclic device

in thermal contact with a single heat reservoir

General cyclic Device

T2

T1
Q1

C1

TN
Q2

W1
Q1R

WD

C2

QN

W2
QR
2

CN

WN
Q RN

TR

R
With a particular sign convention for work and heat we obtain: Wi Q i Q i

R
Consider convention for the case Ci is a Carnot engine: Wi Q i Q i

Ti

Heat Q i 0 Flowing from the Carnot engine into the device

at the lower temperature Ti

Qi

Ci

Wi

Work Wi 0 done by the engine on the surrounding

Q iR

TR

Heat

Q iR 0 Flowing from the hot reservoir to the engine

Consider our combined system as a black box

General cyclic Device
T2

T1
Q1

C1
Q1R

TN
Q2

W1

WD

C2

QN

W2
QR
2

TR

CN

WN
QR
N

The net effect is:

Exchange work

WD Wi
i 1

Exchange heat

Qi R
i 1

TR
Kelvin statement:

R
Q
i 0

i 1

It is impossible to take heat from a single reservoir and

change it entirely into work

(we are allowed to do nothing or to do work on the

device and transfer it entirely into heat)

R
Q
i 0
i 1

Qi R
T 0
i 1 R
N

According to our above sign convention we have

Qi R Qi

TR
Ti

Heat exchanged by
Carnot cycles

Qi
T 0
i 1 i

Proof of Clausius Theorem

Holds in general also for irreversible devices

What happens in the particular case of a reversible device

Corollary (of Clausius theorem): For an arbitrary reversible process

Qi
T 0
i 1 i

Proof:
Let device operate in reversed direction and apply the Clausius theorem

Q i reversed
0
T
i
i 1
N

Qi

0
i 1 Ti

while

Q i reversed Q i
N

Qi
T 0
i 1 i

Apply Clausius theorem to the device in forward direction yields original

result

Qi
T 0
i 1 i
With

Qi
T 0
i 1 i

and

Qi
T 0
i 1 i
N

Qi
T 0
i 1 i

Lets consider now a reversible cyclic process (represented as closed contour in state space)

isotherms
adiabats

V
Reversible cyclic process can be represented by subsequent Carnot cycles

inner isothermal expansion and compression processes cancel mutually out

Approximation of the closed contour by N steps with

Qi
T 0
i 1 i

In the limit N

Qi
T 0
i 1 i

dQ
T 0

From the exact differential theorem we conclude

dQ
dS
T

is exact

dS is the differential of a state function called entropy S.

Entropy determined up to an additive constant ( which will be specified later by the 3rd law)

Since dQ is extensive, S and dS are extensive

In some cases an inexact differential can be changed into an exact one by

multiplying with an integrating factor
1
is the integrating factor which makes dQ exact (for more info go to
T
Exact differentials and theory of differential equations)

Consequences of Existence of Entropy

Relationship between the internal energy and the equation of state

U
dQ

U
dT

V
V

P dV

dQ
dS
T

dS exact

1
dT
T
V

1 U

V T T

P dV

1 U

T T V

Calculation of the derivatives yields

1 2U
1

T VT
T 2

1 2 U 1 P
U

T TV T T V
V T

U
P

T
P
V T
T V

Obviously:

U=U(T,V)

and

P=P(T,V)

not independent

Example:
We show for the ideal gas:
1

P T is a consequence of U=U(T)
U=U(T)
From

0
V T
dP 1 P

P P T

dT
V

1 P

P V

dP
dT

P T f (V)
2

U=U(T) is derived from

1 P
1

P T V T
dV
T

ln P ln T f (V)

PV nRT

nR
U
P

T
P PP 0

T
P
V
V T
T V
U independent of V

U=U(T)

P ( T , V ) C( V ) T

Heat capacity in terms of entropy

P

U
U
dU
P dv
dT
dV C V dT T

V
T V
V T

CV

With

U
P

P
V T
T V

dU dQ dW

and dS

dQ
T

0
P
CV
P
dS
dT
dV PdV
T
T
T V T

dS

CV
P
dT
dV
T

Lets take advantage of the new notation using differential forms

@ V=const.

dV=0

C
S
V

T
T V

T V

C V T

Lets summarize the various representations of heat capacities for PVT systems

Constant volume

Q
Q0 T V const.

C V lim

dQ T S

T
dT V

V=const.

Constant pressure
m

P=const.

where H=U+PV

Q
H
S
dQ

Q0 T P const.

P dT P

C P lim

Explicit expression for the entropy of an ideal gas

C V n c v const. for the ideal gas

dS

dS

CV
nR
dT
dV
T
V

in general

nR
for the ideal gas
V
S(T, V )

CV

dT g (V ) h C V ln T g (V) h

T
nR
S(T, V )
dV f (T ) k
V

nR ln V f (T ) k

Comparison

CV
P
dT
dV
T
T V
P

S(T, V ) C V ln T nR ln V const. (in order to obtain dimensionless argument of

the logarithm introduce a reference state (Tr,Vr) )
S(Tr , Vr ) C V ln Tr nR ln Vr const.

S(T, V ) C V ln

T
V
nR ln
S(Tr , Vr )
Tr
Vr

Change from (T,V)

Easily done with

(T,P)
(P,V)
PV=nRT

Isentropic processes

Reversible adiabatic processes are isentropic processes that is, processes

in which the entropy is constant.

dQ TdS 0
Isentropic processes in ideal gases
T
ln
Tr

T
V
S(T, V ) S(Tr , Vr ) const. n c V ln
nR ln
Tr
Vr

n cV

V
ln
Vr

nR

const.

isentropic

T
ln
Tr

T
ln
Tr

n cV

Vr

V

Vr

nR

const.

n cV

cP c V
cV

const.

ln
Tr

T
ln
Tr

Vr

n cV

R
cV

V

Vr

const.

n cV

const.

T V 1 ~c onst.

Adiabatic bulk modulus

We know already the isothermal bulk modulus

B T V

Reminder:

P2=P1+P

V P V
Proportionality
constant
defines BT

T=const.
We now define the adiabatic bulk modulus
and the adiabatic compressibility

BS V
S

1
BS

Lets calculate BS V
Since PV const.
P

derived for dQ TdS 0

P
d const.
d 1
1

PV

PV
V
dV V
dV V
V 1
P

BS P

Summary of important measurable properties of PVT systems

Thermal expansion Isothermal bulk
volume coefficient
modulus

1 V

V T

B T V
P

Adiabatic bulk
modulus

BS V

measured in experiment from speed of sound

Constant volume Constant pressure

heat capacity
heat capacity

C V T

C P T
V

Easier to measure than CV

Existence of entropy provides relationships between material properties

S
S
S V

T P T V V T T P

Consider S (T, P) S(T, V(T, P))

S V
C P C V T

V T T P

with

CV
P
dT
dV
T

dS

S
P

V T T V

P V

T V T P

C P C V T

P V T


1
V T T P P V

Remember:

P
C P C V T

P
P V

T
P

CP CV TV BT V 2

with
V

1 V
P
B T V

V T P
V T

derived from general considerations

Second relationship looking for CP/CV expressed in terms of BS and BT

Consider again S (T, P) S(T, V(T, P)) and lets calculate

S
S V

P T V T P T

Applying
S

for

P T

T
S

and
S

V T

S
S

1
V

T S

CP
CV

T S

P V
V

S
T P

S
T

T
S

B
CP
S
C V BT

P
V

T S

T S

P T V

S
S

Entropy and the Second Law

We are going to show the meaning of the sloppy phrase: Entropy never decreases
Therefore:
Reminder:

Clausius theorem

In a cyclic process of N steps

Heat exchanged

Qi
T 0
i 1 i

absolute temperatures
How to calculate the entropy change involved in a real (irreversible) process

Answer: Find a reversible equilibrium process that takes the system between
the initial and the final states of the actual processes.

Consider a cyclic process (hence we can later take advantage of Clausiustheorem )

State space spanned by (P,V) for instance but not necessarily
P
real process
1

cannot be represented by a line

In state space

2
reversible
process

V
Now lets apply Clausius theorem

( real) Qi

i
Ti

( rev) Q j
0
j
Tj

Consider the reversible equilibrium part of the total cyclic process

P

final
of rev

reversible heat exchange at T

(rev )
j

start 0 of real
1

Qj
Tj

dQ
dS
T
L

System with single temperature

final f of real
2

reversible
process

start
of rev

S1 S2

S0 Sf

adiabatic:
Qi=0
Consider the real process
Restrict to an adiabatic process

( real) Qi

i
Ti

( real) Qi
0
i
Ti

( rev) Q j
0S0 Sf

j
Tj

Clausius

Sf S0

Entropy statement of the second law:

The total entropy of an adiabatically isolated system never decreases.

The idea that entropy will increase, if it can is emphasized in

Clausius summary of the second law:

The entropy of the universe* tends toward a maximum.

Universe is a synonym for a completely isolated system (in contrast to

adiabatically isolated systems of the above statement )
*

Clausius statement and

the principle of increase of entropy
adiabatically isolated
-Entropy change of the high temperature bath.
Q
S H
TH

-Entropy change of the low temperature bath.

S C

Q
TC Heat is leaving the low temperature bath
1

0
Total entropy change S SC S H Q
T
H TC

because

TH TC

Existence of a non-Clausius device violates entropy statement of 2nd law

Kelvin statement and the entropy

statement of the 2nd law
adiabatically isolated
-Entropy change of the high temperature bath:

S H

Q
TH

-Device: only effect is to accept heat from the reservoir

and transform it entirely into work
Device in the same state at the start and finish
Sdevice 0
of the process
Total entropy change

S S device S H

Q
TH

Existence of a non-Kelvin device violates entropy statement of 2nd law

Entropy and Irreversibility

Consider a process in an adiabatically isolated system where

Sf S0

process allow by 2nd law

Reversed process: Start and final state become exchanged

S0 Sf

Reversed process forbidden by 2nd law

Entropy concept allows to quantify irreversibility

Times arrow

S1

S1

t1

<

S2

t2

S2

Two examples for irreversible processes with corresponding entropy increase

1

Free expansion of an ideal gas

V0 ,T0

Vf ,Tf

Thermal insulation

gas
no heat flow

fixed walls
U=U(Tf)-U(T0)=0
With

Q0

no work done by the container W=0

Tf T0

T
V
and Vf 2V0
nR ln
S(Tr , Vr )
Tr
Vr
T
V
S S(Tf , Vf ) S(T0 , V0 ) C V ln f nR ln f nR ln 2
T0
V0

S(T, V) C V ln

ln1=0

ln2

Fast free expansion is certainly not a sequence of reversible equilibrium processes

only initial and final states can be represented in state space
Lets calculate S via an integral dQ / T in state space using a path, L, of reversible
equilibrium processes taking the system from the initial to the final states of the actual
process.
L

We know that free expansion of the ideal gas takes place at

T=const.=T0=Tf
We can therefore bring the system from (T0,V0) to (Tf,Vf)
via an isothermal expansion

dU 0 dQ PdV

S
L

dQ PdV

Vf

Vf
dQ
PdV
dV

nR
nR ln
T
T
V
V0
L
V0

T=const.

Temperature equalization
In order to have a specific example consider:

No heat exchange with

surrounding

Cu
1kg
T0Cu=80C
=353.15K
kJ
c Cu

0
.
385
P
kgK

T0W=10C
=283.15K
kJ
c PW 4.18
kgK

2kg

Final equilibrium temperature

Cu
M W c PW Tf T0W M Cu c Cu
0
P Tf T0

no heat exchange with surrounding

heat flow into the water>0 heat flow out of the Cu block<0

Tf

Cu
M W c PW T0W M Cu c Cu
T
P 0

Tf

M W c PW M Cu c Cu
P

with

c Cu
P
c PW

kJ
kgK

0.092
kJ
4.18
kgK
0.385

2 kg 283.15K 0.092 353.15K

286.23K
2 kg 0.092kg

Total entropy change

S SCu S W
S

Mc PW

Tf

T0

T
dT
kJ
286.23
kJ
Mc Pw ln f 2.0 kg 4.18
ln
0.0904
T
kg K
283.15
K
T0w

Entropy of the Cu block decreases

S

Cu

dQ

Mc Cu
P
T
L

Tf

Cu

T0

Tf
dT
kJ
286.23
kJ
Mc Cu
ln
0.0809
P ln Cu 1.0 kg 0.385
T
kg K 353.15
K
T0

S SCu S W 0.0095

kJ
0 Total entropy of the isolated system increases
K

Stability of thermodynamic systems

According to Clausius: entropy is at maximum in systems in equilibrium at
Constant U and V.
Consider two systems in equilibrium with S( U U, V)

S( U U, V)

and

S( U U, V )

entropy of combined system

(not in equilibrium) is

S( U U, V)

S( U U, V) + S( U U, V)

Compare with

Internal energy: 2U
volume: 2V

entropy of combined system is

S( U, V )

S( U, V )

S( U, V) S( U, V) 2S( U, V)

Internal energy: 2U
volume: 2V

We know entropy is extensive

S(U, V) S( U, V)

Combined system with internal energy 2U and volume 2V,

has entropy 2S( U, V ) in equilibrium which is at maximum

S( U U, V) S( U U, V) 2S( U, V )

otherwise system with 2S( U, V) would evolve into 2 systems with U U

Alternative formal approach:
We know:

Absolute temperature T>0

1
S

0
U V T

Moreover, we want S=S(U,V) be a concave function of U

S S(U0,V)

Equation of the linear function

S( U 0 U, V)

S( U 0 , V) S( U 0 U, V)

S( U 0 U, V ) S( U 0 U, V)
U (U 0 U)
2U

S( U 0 U, V) S( U 0 U, V)
U
2U

S( U U, V) S( U U, V) 2S( U, V )

U0-U

U0

U0+U

Consider the limit U->0

S
S( U U, V) S( U, V)

1 2S
U
2 U 2
V

With
S( U U, V ) S( U U, V) 2S( U, V ) 0

and for U->0

2S

U 2

U
V

2S

U 2

0
V

U 2 ...
V

Lets apply the same consideration for the volume

S( U, V V) S( U, V V ) 2S( U, V )

Consider the limit V->0

S
S( U, V V) S( U, V)

With

1 2S
V
2 V 2
U

S( U, V V ) S( U, V V) 2S( U, V ) 0

For V->0
2S

V 2

V
U

2S

V 2

0
U

V 2 ...
U

Finally lets consider the small changes U and V together

S( U U, V V) S( U U, V V) 2S( U, V)
S( U U, V V) S( U U, V V ) 2S( U, V)

Consider the limit U->0, V->0 (both inequalities yield the same result)
2
1 2S
S
S
2 1 S
U 2
S( U U, V V ) S( U, V)
U
V
2

V
2
2 V

U
U V

V 2
U

2S

VU...
UV

With e.g., S( U U, V V) S( U U, V V) 2S( U, V) 0

2S

U 2

U
V

2S
2S

2
VU
2

UV
V

V 2 0
U

For all U, V
in the vicinity of (U, V)=(0,0)

Remember from math: sufficient condition for a maximum of f(x,y) at (x0,y0)

 2 f
2 f
0,
0

2
2
x
y

2 f
x 2

& determinant of Hesse-matrix>0

2 f
xy

2 f
yx

For more background

about the
Hesse-matrix
click here

2 f 2 f 2 f
2

0
2
2
x y xy
f
y 2
2S

Our problem: in order to make sure

2
U

U
V

2S
2S

2
VU
V 2
UV

V 2 0
U

(U, V)=(0,0) has to be a maximum of

f (U, V)

2S

U 2

U
V

2S
2S

2
VU
2

UV
V

V 2

since f(0,0)=0

with
2S
f (U, V)

2
2
2

U
U V

f (U, V)
2S
2
VU
VU

f (U, V)
2S
2
UV
UV
2S
f (U, V)

2
2
2

V
V U

2S

2
U 2

2S
2
UV

>0
2S
2
VU

2S

2
V 2

 2S

2
U 2

2S
2
VU

2S
2
UV

2S

4
U 2

2S

V 2

2S
4
UV

2S
VU

>0

2S

2
V 2

2S

2S

U 2
V 2

V
U

2S
UV

>0

While the necessary conditions read

2S

U 2

0
V

2S

V 2

0
U

What are the physical implications

2S

U 2

From

0
<
V

dU dQ pdV TdS pdV

S V

dQ TdS

2S

U 2

1
1

U T( U, V)
T2

1 1
T

T 2 CV
U V

CV 0

2S

2S

2S

2
U 2

V V U UV

>0

see textbook

BT 0

1
S

U V T

>0

Consider a volume fluctuation V>0

x

Intuitive meaning of BT V

with

BT 0

P B T

V
0
V

Pressure decreases

External pressure drives system back to equilibrium

otherwise

T=const.