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Phase transitions
6.1
Concept of phase
Consider a system described by the variables P and T . For a given P and T , the equilibrium state of the system does not necessarily have to be homogeneous. The system can
show different state forms (f. i., for water the possible state forms are liquid/solid/gas).
These state forms are called phases. In each phase certain macroscopic properties can
show very different values.
Example: water.
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Critical point:
at this point, the gas and the liquid have equal densities and specific
entropies (entropy per particle). The phase transition becomes
second-order at this point.
There is no critical point for the liquid-solid transition.
Triple point:
Note: the melting curve has negative slope, which means that at constant temperature
T < T0 ice melts under increasing pressure (we observe this during ice-skating).
6.2
Since we have already started discussing the {P, T } phase diagram for water, let us
continue and concentrate first on phase transitions of first order.
When water starts boiling, it undergoes a phase transition from a liquid to a gas phase.
For both phases independently, the equation of state is a well-defined regular function,
continuous, with continuous derivatives. However, while going from liquid to gas one
function abruptly changes to the other function. Such a transition is the first-order
phase transition.
The first-order phase transition can be defined more systematically by considering the
Gibbs thermodynamic potential. In a first-order phase transition, the first derivative of
the Gibbs potential is discontinuous across the phase boundary. Also, according to the
relations:
G
G
V =
and S =
,
P T
T P
volume V and entropy S are discontinuous as well.
Let us consider an isotherm drawn in the P V diagram (Fig. 6.2).
57
This P V diagram is a projection onto P V of the equation of state surface for water
(Fig. 6.3).
(6.1)
(6.2)
In eq. (6.1) and (6.2), T0 is the absolute temperature at which the two phases coexist,
si is the entropy per particle of the ith phase (specific entropy) and N is the number of
particles that have undergone the transition.
6.3
58
1 (T, P ) = 2 (T, P )
(6.3)
The condition of coexistence, eq. (6.3), tells us that both phases must have equal chemical
potential (Fig. 6.4).
S = S2 S1 =
V
6.4
Clapeyron equation
Since the variables G, S, and V are functions of V , T , and P , there must exist a
relation among them:
f (G, S, V ) = 0.
59
In equilibrium, G = 0 and
diagram, i.e.,
(G)
T
(G)
P
P
T G= 0
P
P
T
(6.4)
.
G
dP
dT
P
T
(6.5)
G=0
Clapeyron equation
Figure 6.5: The slope of the liquid(2)-solid(1) boundary is positive the liquid contracts
upon freezing.
60
Figure 6.6 shows the P T diagram for water, which expands upon freezing (due to the
Hydrogen bonding between molecules).
Figure 6.6: The slope of the liquid(2)-solid(1) boundary is negative the liquid expands
upon freezing.
In a second-order phase transition the first derivatives of G vanish, and the Clapeyron
equation is replaced by a condition involving second derivatives.
6.5
For the following discussion, let us denote the two phases in equilibrium at a given coexistence curve as and . Then, following Ehrenfest, we define the order of the phase
transition as
the order of the lowest derivative of G, which shows a discontinuity
upon crossing the coexistence curve.
Explicitly, a phase transition between phases and is of order n if
1)
m
G
m G
=
m
T
T m
m P
m P
G
G
=
m
P
P m T
T
for m = 1, 2, . . . , n 1,
for m = 1, 2, . . . , n 1;
2)
n
n G
G
6=
n
T
T n
n P
n P
G
G
6=
n
P
P n T
T
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In practice, only phase transitions of first- and second -order are of importance. Their
properties are listed below.
1st order:
1) G(T, P ) continuous;
G
G
and V =
discontinuous;
2) S =
T P
P T
3) latent heat.
2nd order:
1) G(T, P ) continuous;
2) S(T, P ) and V (T, P ) continuous;
3) response functions (susceptibilities) discontinuous:
2
G
CP = T
,
T 2 P
1 2G
,
T =
V P 2
2
1
G
=
.
V P T
There are not many phase transitions of the second order that, following Ehrenfest classification, show a finite discontinuity in the specific heat. A superconductor at zero magnetic
field is an example of such 2nd -order phase transitions (Fig. 6.8).
62
Note: in practice, though, many systems with phase transitions which are not of the first
order show divergences (not finite discontinuities) in the response functions. For instance,
the susceptibility of a magnetic system is of the form
M
1
=
, (T )
,
H T
(T Tc )
with being called critical exponent. For systems with such properties, the Ehrenfest
classification is not anymore valid.
For a more general classification, one considers only the behavior of the entropy at the
phase boundary as a function of T . Within this classification, discontinuous and continuous phase transitions are distinguished as discussed below.
1) discontinuous phase transitions are equivalent to phase transitions of the 1st order.
Properties:
(i) S 6= 0; latent heat;
2
(ii) CP = T TG2
is finite for T 6= T0 ; no condition exists for T = T0 .
P
63
Consider a fluid system whose phase transition is depicted in Fig. 6.9. Since, as seen from
64
6.6
// P V = nRT,
is only valid for very small densities of particles and, therefore, cannot describe the gasliquid phase transition. This phase transition is due to intermolecular interactions. In
this section, we will derive an equation of state for a gas which includes intermolecular
interaction in a phenomenological way.
For that purpose, we consider the following ansatz:
Pef f Vef f = nRT.
In order to derive explicit expressions for Vef f and Pef f , we assume that the potential
energy U (r) between two molecules as a function of their separation r0 has the form as
shown in Figure 6.13.
In particular,
- U (r) has a repulsive core with radius r0 (a few angstroms) due to the electrostatic
repulsion of the electron cloud;
- U (r) has an attractive tail at r > r0 due to the mutual electrostatic polarization of
two interacting molecules.
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The depth of attractive U (r) is about 1 eV (changes with the gas species). This minimum
is responsible for the chemical valence and for the crystal structure of solids.
In order to consider these effects qualitatively, we separate them.
a) The hard core excludes a certain volume around a molecule so that other molecules
have less room in which to move. As a consequence, the effective volume of the gas
is reduced:
Vef f = V bn .
V : total volume of the system;
b: total excluded volume, b N r03 /6;
n: number of moles.
b) The pressure of the gas comes from the molecules hitting the walls of the container.
A real gas hits the walls with less kinetic energy than an ideal gas since in the real gas
the molecules are held back by the attraction of neighboring molecules (attractive
tail) (Fig. 6.14). The reduction in the pressure is proportional to the number of
a 2
n.
V2
A particle at the wall experiences a resulting force directed towards the containers
interior, which reduces the pressure of the gas on the containers wall,
Pef f > wall pressure P.
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(V bn) P + a
6.6.1
n 2
V
= nRT .
(6.6)
Virial expansion
The van der Waals equation of state approaches that of the ideal gas in the low density
limit:
V , for fixed N .
The successive corrections to the ideal gas equation are obtained by expanding in powers
of V 1 . We define
= nR.
an2 = A,
B = bn, and R
Then, from eq. (6.6),
A
RT
P+ 2 =
,
V
(V B)
1
A
B
RT
2,
1
P =
V
V
V
1
B
A
PV
=
1
V.
V
RT
RT
(6.7)
V
RT
A
B
RT
2 3
B
B
+
+ ...
+
V
V
(6.8)
V
V
RT
(6.9)
where Cn is the nth virial coefficient. Comparing eq. (6.8) and (6.9), we have
A
C2 = B .
RT
This coefficient can be obtained experimentally by observing deviations from the ideal
gas law. From measuring these deviations at varying temperature, one can extract the
parameters A and B.
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6.6.2
Critical point
The van der Waals isotherms have the shape given in Fig. 6.6.2.
The isotherms are solutions of the van der Waals equation:
n3
an2
nRT
3
2
ab = 0 .
+V
V V
nb +
P
P
P
(6.10)
Eq. (6.10) is a polynomial of the 3rd order and, hence, for given T and P there would
exist three real roots or only one real root. For T < Tc and P < Pc , we have three real
roots. As we increase T , these roots move closer and merge at T = Tc , the critical point.
For T > Tc , there is only one real solution and two complex conjugate ones.
At the critical point (Pc , Tc , Vc ), the equation of the state must be
(V Vc )3 = 0
since all three solutions are the same. Then,
V 3 3Vc V 2 + 3Vc2 V Vc3 = 0 .
By compare eq. (6.10) with eq. (6.11), we find Vc , Pc , and Tc :
nRTc solution :
3Vc = nb +
Pc
Vc = 3bn
2
an
a
2
3Vc =
P
c =
Pc
27b2
3
8a
abn
RTc =
Vc3 =
27b
Pc
3
Pc V c
= .
nRTc
8
(6.11)
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Experimentally, one finds that almost all real gases have Zc < 83 , while for the ideal gas
Zc = 1. Therefore, the van der Waals equation is an improvement with respect to the
ideal gas equation.
6.6.3
Maxwell construction
The van der Waals isotherm is a monotonic function of V for T > Tc . For T < Tc , it has
a kink with negative compressibility:
1 V
<0
T =
V P T
P
V
> 0.
T
Negative compressibility is not realistic since a decrease of volume dV < 0 would mean
a decrease of pressure dP < 0, which does not make sense since such a behavior leads to
the collapse of the system. This unphysical result originates from the implicit assumption
that the density of the system is always uniform. In fact, it is possible to show (and we
are going to do this now) that the system at T < Tc prefers to undergo a first-order phase
transition by breaking up into a mixture of phases of different densities.
Solution: according to the Maxwell relation,
F
P =
,
V T
where F is the Helmholtz free energy, the free energy can be obtained as the area under
the isotherm:
Z
F (V, T ) =
P dV.
isotherm
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For T = const,
F1 F2 =
V1
V2
dF = P dV,
Z
dV P (V ) =
V2
dV P (V )
V1
V2
P dV = PV (V2 V1 ) .
V1
This means that the areas A and B are equal to each other. The horizontal line in Fig.
6.16 (F, V ) is the Maxwell construction.