NOTE 2 2021/10/4

Chapter 2 Heat and Entropy

The internal energy can be described as a function of any two of the variables;

dU ( P,V )  UP V dP  UV P dV

dU (P, T )  UP T dP  UT P dT

dU (V , T )  UV T dV  UT V dT (2.1)

The heat absorbed by the system can be obtained from the first law, i.e. dQ  dU  dW ;

dQ  UP V dP  UV P dV  PdV  UP V dP  [UV P  P]dV

dQ  UP T dP  UT P dT  PdV

dQ  UV T dV  UT V dT  PdV  [UV T  P]dV  UT V dT (2.2)

dV  VP T dP  VT P dT (2.3)

dQ  UP T dP  UT P dT  PdV  UP T dP  UT P dT  P[VP T dP  VT P dT ]

 [UP T  PVP T ]dP  [UT P  PVT P ]dT

 [ UP T  P VP T ]dP    dT

 (U  PV )
T P (2.4)

It is convenient to define a state function called the enthalpy;

H  U  PV (2.5)

Then, (2.2) can be rewritten as;

dQ  UP V dP  [UV P  P]dV

dQ  [ UP T  P VP T ]dP    (U  PV )

T
 dT  [   P  ]dP    dT
P
U
P T
V
P T
H
T P

dQ  [UV T  P]dV  UT V dT (2.6)

We can immediately read off the heat capacities [ C 

dQ
dT , (1.6)] at constant V and P ;

CV  UT V ; CP  HT P (2.7)

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Applications to Ideal Gas

A thermally insulated ideal gas was allowed to expand freely into an insulated chamber, which was
initially vacuous. The final temperature was found to be the same as the initial temperature, i.e.
T1=T2.

T1 T2
Vacuum

Before After

Fig. 2.1 Free expansion of ideal gas

W  0 (since the gas pushed into a vacuum)

Q  0 (since the temperature was unchanged)

U  0 (by the first law)

Choosing V, T as independent variables, we conclude U (V1 , T )  U (V2 , T ) . That is U is

independent of V:
U  U (T ) (2.8)

CV  UT V  dU
dT or dU  CV dT (2.9)

Assuming that CV is a constant, we can integrate the above to obtain

T T
0
dU   CV dT , U (T )  U (0)  CV T , U (T )  CV T
0
(2.10)

C P   HT P   T
     
 (U  PV )
P
U
T P
 ( PV )
T P
 dU
dT
  T

 ( Nk B T )
P
 dU
dT

 ( Nk B T )
T (2.11)

 CV  Nk B (2.12)

CP  CV  Nk B (for an ideal gas) (2.13)

Consider a reversible adiabatic transformation, i.e. dQ  0 ,

dU  dW   pdV , dU  CV dT

CV dT  PdV  0 (2.14)

Using PV  NkBT

dT  dNk
( PV )
B
 PdVNkBVdP (2.15)

2
(2.14) CV ( PdVNkBVdP )  PdV  0 ,

CV ( PdV  VdP)  Nk B PdV  0

CVVdP  CP PdV  0 (2.16)

 CVP 0, 
C
or
dP
P
dV
V
dP
P
dV
V
0 (   CVP )
C
(2.17)

Assuming that  is a constant, we obtain through an integration,

dP
P
  dV
V ,  dP
P
   dVV
ln P   ln V  constant (2.19)

or ln P  ln V   constant, ln VP  ln PV   constant

PV   constant (2.20)
Using PV  NkBT

PV   ( )V   Nk BTV  1  constant
NkBT
V

or TV  1  constant or VT 1 /( 1)  constant (2.21)

Adiabatic
P

Isotherm

V
Fig. 2.2 An adiabatic line has a steeper slope than an isotherm.

Carnot Cycle
In a cyclic transformation, the final state is the same as the initial state, and therefore U  0 . A
reversible cyclic process can be represented by a closed loop in the PV diagram;

W  Q   PdV  area enclosed (2.22)

The working substance is arbitrary, but we illustrate it for an ideal gas in Fig. 2.3, where T2 > T1.
The system absorbs heat Q2 along the isotherm T2 and reject heat Q1 along T1. By the first law, the
net work output is

3
 W  Q  Q2  Q1 (2.23)
In one cycle of operation, the efficiency of the Carnot engine is defined as

  QW  Q QQ  1  QQ
2
2
2
1 1
2
(2.24)

which is 100% if there is no waste heat, i.e. Q1=0. But, as we shall see, the second law of
thermodynamics states that this is impossible.

Q2, T2

Q1, T1
V
Fig. 2.3 Carnot cycle on the PV diagram of an ideal gas.

T2
Q2

T1
Q1
Fig. 2.4 Schematic representation of a Carnot engine.

We can run the engine in reverse as a Carnot refrigerator.

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Second Law of Thermodynamics
It is stated by Clausius:

There does not exist a thermodynamic transformation whose sole effect is to deliver heat from a
reservoir of low temperature to a reservoir of higher temperature.

An equivalent statement by Kelvin:

There does not exist a thermodynamic transformation whose sole effect is to extract heat from a
reservoir and convert it entirely into work.

Absolute Temperature

The second law implies that a Carnot engine cannot be 100% efficient, for otherwise all the heat
absorbed from the upper reservoir would be converted into work in one cycle of operation.

We can show that no engines working between two given temperatures can be more efficient than a
Carnot engine. Since only two reservoirs are present, a Carnot engine means a reversible engine.

Consider a Carnot engine C and engine X working between the reservoirs T2 and T1, with T2 > T1,
as shown in Fig. 2.5. The total work output is

Wtot  (Q2'  Q1' )  (Q2  Q1 ) (2.25)

Now arrange to have Q2  Q2 , i.e. no net heat was extracted from the reservoir T2.
'
An amount of
heat Q1  Q1 was extracted from the reservoir T1 and converted entirely into work with no other
'

effect. This would violate the second law, unless Q1  Q1' . Dividing both sides of this inequality
by Q2 , and using the fact Q2  Q2 , we have
'

Q1'
Q1
Q2  Q2' (2.26)

Q'
1  Q12  1  Q1' C  X
Q
Therefore 2
or (2.27)

5
 Q’2 Q2
T2

X W W C

T1
Q’1 Q1
Fig. 2.5 Driving a Carnot refrigerator C with an arbitrary engine X.

As a corollary, all Carnot engines have the same efficient, since X may be a Carnot engine. This
shows that the Carnot engine is universal, in that it depends only on the temperatures involved, and
not the working substance.

We define the absolute temperature θ of a heat reservoir such that the ratio of the absolute
temperatures of two reservoirs is given by [form (2.24)]

1
 Q12  1 
Q
2 (2.28)

where  is the efficiency of a Carnot engine operating between the two reservoirs. Since Q1  0
according to the second law, the absolute temperature is bounded from the below:

 0 (2.29)

The absolute zero θ=0 is a limiting value which we can never reach, according to the second law.

Temperature as Integrating Factor

In an arbitrary cyclic process P, the following inequality holds:

 0
dQ
P T (2.30)

where the equality holds if P is reversible. To prove the assertion, divide the cycle P into K
segments labeled i = 1, … , K. Let the ith segment be in contact with a reservoir of temperature Ti,
from which it absorbs an amount of heat Qi. The total work output of P is, by the first law and
∆U=0,
K
W   Qi (2.31)
i 1

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Note that not all the Qi can be positive, for otherwise heat would have been converted to work with
no other effect, in contradiction to the second law.

Qo1 Qo2

Reservoir To
C2
C1

T1 T2 T3
Q1 Q2
T4
Closed cycle P

Fig. 2.6 Construction to prove Clausius’ theorem.

Image a reservoir at a temperature To > Ti (all i), with Carnot engines Ci operating between To and
each temperatue Ti, as illustrated in Fig. 2.6.
As (2.28), we have

Qi( o )

To
Qi Ti (2.32)
In one cycle of operation of the joint operations {P+C1+ … + CK}

▲ The reservoir Ti experience no net change, for it receives Qi, and delivers same to the system.

▲ The heat extracted from the To reservoir is given by (according to (2.32))

K K
Qtot   Qi( o )  To  QTii (2.33)
i 1 i 1

▲ The total work output is

outside of the loop
K K
Wtot  W   [Q  Qi ]   Qi( o )  Qtot
i
(o)
(2.34)
i 1 i 1
K

(2.31): W   Qi
i 1

An amount of heat Qtotal would be entirely converted to work with no other effect, and thus violate
the second law, unless Qtot  0 , or

7
 K


i 1
Qi
Ti
0 (according to (2.33)) (2.35)

In the limit K   , this becomes

 0
dQ
P T (2.36)

This proves the first part of the theorem, i.e. (2.30)

 0.
dQ
If P is reversible, the sign for Qi are then reversed, and we conclude that P T
Combining
this with (2.36). We have

 0
dQ
P T (if P is reversible) (2.37)


dQ
For a reversible open path P, the integral P T
depends only on the endpoints.

     0
dQ dQ dQ dQ dQ
T P T P' T P T P' T

 
dQ dQ P
Thus, P T P' T (2.38)

-P’

Entropy

The exact differential

dS  dQ
T (2.39)

defines a state function S called the entropy. The entropy difference between any two states B and
A is given by

B dQ
S ( B )  S ( A)   (along any reversible path) (2.40)
A T

What if we integrate along an irreversible path? Let P be an arbitrary path from A to B. Let R
8
be a reversible path with the same endpoint. The combined process P-R is a closed cycle, and

P (arbitrary path)

A B

-R (reversible path)

 0 ,
dQ
therefore by Clausius’s theorem PR T
or

 
dQ dQ
P T R T (2.41)

Since the right side is the definition of the entropy difference between final state B and the initial
state A, we have

B dQ
S ( B)  S ( A)   (2.42)
A T

where the equality holds if the process is reversible. For an isolated system, which does not
exchanges heat with the external world, we have dQ  0 , and therefore

S  0 (2.43)

That is, the entropy of an isolated system never decreases and it remain constant during a reversible
transformation.

Remarks for entropy:

▲ The principle that the entropy never decreases applies to the “universe” consisting of a system
and its environment.
▲ Since the entropy is a state function, the entropy change of the system in going from state A to

state B is SB  S A regardless of the path, which may be reversible or irreversible. For an

irreversible path, the entropy of the environment changes, whereas for a reversible path it does
not change.

SB  S A is not necessarily equal to the integral

B
▲ The entropy difference  dQ / T .
A
It is equal

to the integral only if the path from A to B is reversible. Otherwise, it is generally larger than
the integral.
9
Entropy of Ideal Gas
In Fig. 2.7, we approach point A along two alternative paths, with V kept fixed along path 1. T
kept fixed along path 2 (isothermal). Along path 1, we have (from (2.40))

T dQ
S (V , T )  S (V , To )   ( dW  PdV  0 along path 1, dQ  dU )
T T
o

T
S (V , T )  S (V , To )  CV  dT
 S (V , To )  CV ln TTo (2.44)
To T

To determine S (V , To ) , we integrate dS  dQ / T along the isothermal path 2. Since

dU  CV dT  0 along path 2)

dQ  dW  PdV  Nk BT dVV (using PV  NkBT ) (2.45)

V
S (V , T )  S (Vo , T )  Nk B  dV
 S (Vo , T )  Nk B ln VVo (2.46)
Vo V

Comparing the two expressions [(2.44) & (2.46)] at T1 , i.e. for S (V , T1 ) ,

S (V , T1 )  S (V , To )  CV ln T1o
T
(2.44)

(2.46) S (V , T1 )  S (Vo , T1 )  Nk B ln VVo

i.e.
S (V , To )  CV ln T1o  S (Vo , T1 )  Nk B ln VVo
T

Therefore, we conclude

S (V , To )  Co  Nk B lnV (2.47)

From (2.44)
S (V , T )  Co  Nk B lnV  CV ln T (2.48)

For a monatomic gas we have CV  32 Nk B , then

S (V ,T )  Co  Nk B ln(VT 3 / 2 ) (2.49)

P
Path 2 (isothermal)

A
T1
Path 1
To
V
Fig. 2.7 Calculating the entropy at point A.
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