U = 0
since the internal energy U is a state function. A reversible cyclic process can be repre-
sented by a closed loop in the P V diagram (Fig. 4.1).
Figure 4.1: Reversible cyclic process. The shaded area of the loop is the total work done
by the system in one cycle.
It follows from the first law of thermodynamics that, since U = 0, the work done by the
system during a cycle is equal to the heat absorbed, i. e.,
I
W = Q = P dV = Area enclosed.
In a cyclic process, work is converted into heat and in the end of each cycle the
system returns to its original state. We will introduce the heat engine which is
based on the properties of a cyclic process.
23
24 CHAPTER 4. ENTROPY AND SECOND LAW OF THERMODYNAMICS
Let us consider the operation of a heat engine in more detail (Fig. 4.2).
Part of the heat that is transferred to the system
from a heat bath with temperature T1 , Q1 , is con-
verted into work, W , and the rest, Q2 , is delivered
to a second bath with T2 < T1 (condenser). Follow-
ing the first law of thermodynamics,
|Q1 | |Q2 | = |W |.
The Carnot process can be realized with an arbi- Figure 4.2: Heat engine.
trary working substance, but we shall consider here
an ideal gas (Fig. 4.3).
Figure 4.3: Ideal gas as a working substance for the Carnot process.
In the P V diagram the Carnot process can be represented as shown in Fig. 4.4.
One Carnot cycle consists of four consecutive thermodynamic processes, which are
1. A B: isothermal expansion at T = T1 ; the volume changes as
VA VB ,
while heat Q1 is absorbed from a bath and the system performs work.
4.2. SECOND LAW OF THERMODYNAMICS 25
where W is the work performed by the system, equal to the area enclosed in the loop
(shaded area in Fig. 4.4).
Definition by Kelvin:
There is no thermodynamic transformation whose sole effect is to extract heat
from a reservoir and convert it entirely to work.
Summary: a perpetuum mobile of second type does not exist.
26 CHAPTER 4. ENTROPY AND SECOND LAW OF THERMODYNAMICS
In these terms, heat being converted entirely into work means chaos changing sponta-
neously to order, which is a very improbable process.
Usually,
ii) No engine working between two given temperatures can be more efficient than a
Carnot engine.
A Carnot engine is a reversible engine between two baths. The previous statement means
as well that an irreversible engine cannot be more efficient than a reversible one. In order
to show this, we consider two engines C and X (with X not necessarily a Carnot one)
working between baths at T1 (warm) and T2 (cold). We run the Carnot engine C in
and feed the work output of X to C (Fig. 4.6).
reverse, as a refrigerator C,
Figure 4.6: Linked engine X and Carnot refrigerator C.
If we adjust the two engines so that |Q1 | = |Q1 |, no net heat is extracted from the heat
bath at T1 . In this case, an amount of heat |Q2 | |Q2 | is extracted from the heat bath
at T2 and converted entirely to work, with no other effect. This would violate the second
law of thermodynamics unless
|Q2 | |Q2 |.
We divide this inequality by |Q1 | and, using the fact that |Q1 | = |Q1 |, get
|Q2 | |Q |
2
|Q1 | |Q1 |
and
|Q2 | |Q |
1 1 2 .
|Q1 | |Q1 |
28 CHAPTER 4. ENTROPY AND SECOND LAW OF THERMODYNAMICS
Consequence: all Carnot engines have the same efficiency since X can be, as a special
case, a Carnot engine.
The Carnot engine is universal, i.e., it depends only on the temperatures involved
Definition: absolute temperature of a heat reservoir (bath) is defined such that the ratio
of the absolute temperatures of two reservoirs is given by
2 |Q2 | Q2
=1 = ,
1 |Q1 | Q1
where is the efficiency of a Carnot engine operating between the two reservoirs. Since
|Q2 | is strictly greater than zero, |Q2 | > 0, according to the second law of thermodynamics,
the absolute temperature is bounded from below:
>0.
This means that the absolute zero = 0 is a limiting value that can never be reached
since this would violate the second law of thermodynamics.
Q
I
0;
P T
Proof. Let us divide the cycle P into n segments so that on each segment
its temperature Ti (i = 1, . . . , n) is constant. We consider now a reservoir
at temperature T0 > Ti (i) (Fig. 4.7) and introduce Carnot engines
between the reservoir at T0 and Ti .
(0)
Qi QC
+ i =0 (definition of absolute temperature).
T0 Ti
For cycle P ,
n
X
W+ Qi = 0 (first law of thermodynamics),
i=1
with
Qi = QC
i .
(0)
If QT > 0, the combined machine would convert completely the heat from reservoir at
T0 into mechanical work. This would violate Kelvins principle and therefore
(0)
QT 0,
i.e.,
n
X Qi
T0 0.
i=1
Ti
For n ,
Q
I
0.
P T
The theorem of Clausius is proved.
P T
depends only on the end points and not on the particular path.
4.5 Entropy
dQ Q
I
Since = 0 for a reversible process, is an exact differential:
T T
Q
dS = . (4.1)
T
Eq. (4.1) implies that there exists a state function S.
Q
dS =
T
is called entropy.
4.5. ENTROPY 31
Q Q
Z Z
= S(B) S(A) .
I T R T
Therefore, in general
B
Q
Z
S(B) S(A) , Figure 4.8: I R (irreversible-
A T reversible) cycle.
and the equality holds for a reversible process.
In particular, for an isolated system, which does not exchange heat with a reservoir,
Q = 0 and therefore
S 0 .
This means that the entropy of an isolated system never decreases and remains constant
during a reversible transformation.
Note:
i) The joint system of a system and its environment is called universe. Defined in this
way, the universe is an isolated system and, therefore, its entropy never decreases.
However, the entropy of a non-isolated system may decrease at the expense of the
systems environment.
ii) Since the entropy is a state function, S(B) S(A) is independent of the path, re-
gardless whether it is reversible or irreversible. For an irreversible path, the entropy
of the environment changes, whereas for a reversible one it does not.
iii) Remember that the entropy difference
B
Q
Z
S(B) S(A) =
A T
only when the path is reversible; otherwise the difference is larger that the integral.
32 CHAPTER 4. ENTROPY AND SECOND LAW OF THERMODYNAMICS
S = S(T, V ),
U = U (T, V ) caloric equation of state,
P = P (T, V ) thermic equation of state.
Since usually the internal energy U is not directly measurable, it is more practical to
consider dS = Q/T . We will make use of one of the heat equations derived in section
3.5:
U U
Q = dT + + P dV
T V V T
U
= CV dT + + P dV (4.2)
V T
In the energy equation, the derivative of the internal energy is written in terms of mea-
surable quantities.
U = U (T ) = CV T + const.
Gay-Lussac experiment:
3
U = N kB T gas of monoatomic molecules,
2
5
U = N kB T gas of diatomic molecules.
2
f f f
df = dx + dy + dz,
x y z
x f /y
= ,
y z f /x
y f /z
= ,
z x f /y
34 CHAPTER 4. ENTROPY AND SECOND LAW OF THERMODYNAMICS
z f /x
= .
x y f /z
We substitute in
U
Q = T dS = CV dT + + P dV
V T
expressions (4.7) and (4.5) and get the following useful relations.
Q = T dS = CV dT + T dV , (4.8)
kT
where T and V are independent variables.
T dS = CP dT T V dP (4.9)
There is also an important connection between CP and CV (which follows from eq.
(4.8) and (4.9)):
V 2
2
CP CV = T V = T T V
P > 0 . (4.11)
kT P T
4.8. ENTROPY AND DISORDER 35
it is possible to rewrite CP CV as
2 T V kT P 2 .
Indeed,
1
= = P kT
P kT
2 2 P 2 kT2
CP CV = TV = T V = 2 T V kT P 2 .
kT kT
S kB ln (multiplicity) .
We shall see in statistical mechanics that this definition is equivalent to the phe-
nomenological concept we have learnt previously in this section.
3. With the above definition of entropy at hand, we can formulate the second law of
thermodynamics in this way:
If an isolated system of many particles is allowed to change, then, with large prob-
ability, it will evolve to the macrostate of largest entropy and will remain in that
macrostate.
4.
(energy input by heating)
Sany system ,
T
where T is the temperature of the reservoir.
5. If two macroscopic systems are in thermal equilibrium and in thermal contact, the
entropy of the composite system equals the sum of the two individual entropies.
36 CHAPTER 4. ENTROPY AND SECOND LAW OF THERMODYNAMICS
As an illustration, let us consider a class in the school, where all kids sit always in
the same place. This situation can be defined as ordered since there is a strong
correlation between the kids positions. For example, if Peter sits in the first row,
you know straight away who is sitting behind and besides him: there is only one
possibility (multiplicity is very low).
Looking now at a class in the kindergarten, we will find that the children there are
all mixed, sitting and moving all the time. Now, if Peter sits in the first row, you
have no idea where the other kids are sitting. There are no correlations between the
kids positions and there are many options to have the children in the class. Such a
system of kids is in a disordered state, with very high multiplicity. The entropy
of the kindergarten class is high!
Consequences:
1) The heat capacities of all substances disappear at T = 0:
S
lim CV = lim T = 0,
T 0 T 0 T V
S
lim CP = lim T = 0.
T 0 T 0 T P
Note that an ideal gas provides a contradiction to the previous statement since in
that case CV = const and CP = const:
3
CV = N kB ,
2
5
CP = CV + N kB = N k B ,
2
CP CV = N kB 6= 0. (4.12)
4.9. THIRD LAW OF THERMODYNAMICS (NERNST LAW) 37
But, for T 0 the ideal gas is not anymore a realistic system because a real gas
undergoes at low temperatures a phase transition - condensation.
2)
1 V
lim = lim =0
T 0 T 0 V T
In order to show the validity of the last statement, let us analyze what happens when we
are trying to reach low temperatures by subsequently performing adiabatic and isothermal
transformations. If a gas is used as a working substance (Linde method), such a sequence
of transformations looks in the P V diagram as shown in Fig. 4.9.
Figure 4.9: Linde method: sequence of adiabatic and isothermal transformations in a gas.
A B: isothermic compression.
Work is performed on the gas and an amount of heat Q1 < 0 is given to the reservoir
in a reversible process. As a result, S = QT1 diminishes.
B C: adiabatic expansion.
The gas performs work. Since Q = 0, the entropy remains constant and the
temperature diminishes.
38 CHAPTER 4. ENTROPY AND SECOND LAW OF THERMODYNAMICS
In principle, by repeating this process many times, one could reach the T = 0 point.
But, according to the third law of thermodynamics, all entropy curves must end at 0 for
T 0, which means that only through an infinite number of steps is it possible to reach
T = 0.