Chapter 6 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 dierent 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 dierent values. Example: water.

Figure 6.1: P T diagram for water.

The P T diagram for water shows phase boundaries, or lines of coexistence. 57

58 Critical point:

CHAPTER 6. PHASE TRANSITIONS at this point, the gas and the liquid have equal densities and specic 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: at this point (line), gas, liquid and solid coexist.

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

First-order phase transition

Since we have already started discussing the {P, T } phase diagram for water, let us continue and concentrate rst on phase transitions of rst 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-dened 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 rst-order phase transition. The rst-order phase transition can be dened more systematically by considering the Gibbs thermodynamic potential. In a rst-order phase transition, the rst 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).

Figure 6.2: An isotherm in the P V diagram for water.

6.3. CONDITION FOR PHASE COEXISTENCE

59

This P V diagram is a projection onto P V of the equation of state surface for water (Fig. 6.3).

Figure 6.3: The equation of state surface for water. Compare Figure 6.3 with the cut P T shown in Fig. 6.1. Important properties: latent heat. Since the coexisting phases have dierent entropies, the system must absorb or release heat during a phase transition.

When an amount of phase 1 is converted into phase 2, an amount of latent heat QL is released: l = T0 (s2 s1 ), QL = lN = T0 (S2 S1 ). (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 (specic entropy) and N is the number of particles that have undergone the transition.

6.3

Condition for phase coexistence

We consider a system composed by one species of particles at given conditions of P and T (constant). Let us assume coexistence of two phases in our system. In this case, the Gibbs potential is the sum of Gibbs potentials of the two phases: G(T, P ) = G1 (T, P ) + G2 (T, P ) = N1 1 (T, P ) + N2 2 (T, P ), where Ni and i are the number of particles and the chemical potential in phase i. The condition of equilibrium is that the Gibbs potential has to be at its minimum, i.e., dG = 0,

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CHAPTER 6. PHASE TRANSITIONS

with N = N1 + N2 xed. In other words, in equilibrium, G is at a minimum with respect to particle transfer from one phase to the other. Therefore, dG = 1 dN1 + 2 dN2 = 0, with dN1 = dN2 . 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).

Figure 6.4: The equilibrium condition, 1 (T, P ) = 2 (T, P ), in the G T diagram. The derivatives of G are discontinuous across the phase transition: S = S2 S1 = V (G) >0 T (G) >0 = V2 V1 = P

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.

6.4. CLAPEYRON EQUATION Let us derive such a relation. We apply the chain rule: (G) T T P
(G) T (G) P

61

P (G) P T

= 1
T

(6.4)

In equilibrium, G = 0 and diagram, i.e.,

P T

.
G

P T G= 0

gives the slope of the transition line in the P T P T .

G=0

dP dT

(6.5)

P is called vapor pressure (Dampfdruck) for the gas-liquid transition. We substitute eq. (6.5) into eq. (6.4) and obtain dP S = dT V or dP QL = dT T V where QL = T S is the latent heat. Depending on the sign of V , the slope dP may be positive or negative. Figure 6.5 shows dT the P T diagram for CO2 , which contracts upon freezing. Clapeyron equation

Figure 6.5: The slope of the liquid(2)-solid(1) boundary is positive the liquid contracts upon freezing.

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CHAPTER 6. PHASE TRANSITIONS

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 rst derivatives of G vanish, and the Clapeyron equation is replaced by a condition involving second derivatives.

6.5

Ehrenfest classication of phase transitions

For the following discussion, let us denote the two phases in equilibrium at a given coexistence curve as and . Then, following Ehrenfest, we dene 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 T m m G P m 2) n G T n n G P n =
P

=
P

=
T

m G T m m G P m

for m = 1, 2, . . . , n 1,
P

for m = 1, 2, . . . , n 1;
T

=
T

n G T n n G P n

6.5. EHRENFEST CLASSIFICATION OF PHASE TRANSITIONS

63

In practice, only phase transitions of rst- and second -order are of importance. Their properties are listed below. 1st order: 1) G(T, P ) continuous; 2) S = G T and V =
P

G P

discontinuous;
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: CP = T 1 V 2G T 2 2G P 2 2G P T ,
P

T = = 1 V

, .

Figure 6.7: Second-order phase transition following Ehrenfest.

There are not many phase transitions of the second order that, following Ehrenfest classication, show a nite discontinuity in the specic heat. A superconductor at zero magnetic eld is an example of such 2nd -order phase transitions (Fig. 6.8).

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CHAPTER 6. PHASE TRANSITIONS

Figure 6.8: Second-order phase transition in a superconductor at zero magnetic eld.

Note: in practice, though, many systems with phase transitions which are not of the rst order show divergences (not nite discontinuities) in the response functions. For instance, the susceptibility of a magnetic system is of the form = M H ,
T

(T )

1 , (T Tc )

with being called critical exponent. For systems with such properties, the Ehrenfest classication is not anymore valid. For a more general classication, one considers only the behavior of the entropy at the phase boundary as a function of T . Within this classication, 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 = 0; latent heat; (ii) CP = T

2G T 2 P

is nite for T = T0 ; no condition exists for T = T0 .

2) continuous phase transitions have the following properties: (i) S continuous no latent heat; (ii) critical point Tc ; (iii) singularities in CV , T , T

6.5. EHRENFEST CLASSIFICATION OF PHASE TRANSITIONS

65

Consider a uid system whose phase transition is depicted in Fig. 6.9. Since, as seen from

Figure 6.9: T diagram for a uid system.

G Fig. 6.9, V = P T0 shows a nite discontinuity, the phase transition is of 1st order. If we now increase temperature, diminishes (Fig. 6.10) and at Tc the transition is not

Figure 6.10: T0 diagram. anymore discontinuous (1st order) but continuous (2nd order). This phenomenon happens for many systems. As another example, let us also consider a magnet (Fig. 6.11). Since G M = , B0 = 0 H B0 T0 is discontinuous, this transition is of 1st order. However, as in the previous example, by increasing temperature the phase transition becomes second-order at T0 = Tc (Fig. 6.12).

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CHAPTER 6. PHASE TRANSITIONS

Figure 6.11: Phase transition of a magnet.

Figure 6.12: MS T0 dependence for a magnet.

6.6

Van der Waals equation of state

P V = NkB T // P V = nRT,

The equation of state for an ideal gas,

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.

6.6. VAN DER WAALS EQUATION OF STATE

67

Figure 6.13: Intermolecular potential.

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 eects 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 eective volume of the gas is reduced: Vef f = V bn . V : total volume of the system;
3 b: total excluded volume, b Nr0 /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

Figure 6.14: Attraction between molecules in a real gas. pairs of interacting molecules near the wall: P = Pef f 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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CHAPTER 6. PHASE TRANSITIONS

Van der Waals made an assumption that, for n mole of gas, Pef f Vef f = nRT, (V bn) P + a n V
2

= nRT .

(6.6)

6.6.1

Virial expansion

The van der Waals equation of state approaches that of the ideal gas in the low density limit: V , for xed N . The successive corrections to the ideal gas equation are obtained by expanding in powers of V 1 . We dene an2 = A, B = bn, and R = nR. Then, from eq. (6.6), P+ RT P = V PV = RT A V2 = RT , (V B)
1

B 1 V B 1 V
1

A , V2 (6.7)

A . RT V

After expanding the rst term in (6.7), 1 for large V , we get PV 1 =1+ V RT A B RT + B V
2

B V

=1+

B + V

B V

+ ...,

B V

+ ...

(6.8)

This expression has the form of a virial expansion: C2 C3 PV =1+ + 2 + ..., V V RT where Cn is the nth virial coecient. Comparing eq. (6.8) and (6.9), we have A C2 = B . RT This coecient 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. (6.9)

6.6. VAN DER WAALS EQUATION OF STATE

69

Figure 6.15: Isotherms for the van der Waals system

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: V 3 V 2 nb + nRT P +V n3 an2 ab = 0 . 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 nd Vc , Pc , and Tc : nRTc solution : 3Vc = nb + Pc Vc = 3bn an2 a 2 3Vc = Pc = 27b2 Pc abn3 RTc = 8a 3 Vc = 27b Pc Zc = 3 Pc Vc = . nRTc 8 (6.11)

From this solution we can dene the parameter

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CHAPTER 6. PHASE TRANSITIONS

3 Experimentally, one nds that almost all real gases have Zc < 8 , 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: T = 1 V V P P V <0
T

> 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 rst-order phase transition by breaking up into a mixture of phases of dierent densities. Solution: according to the Maxwell relation, P = F V ,
T

where F is the Helmholtz free energy, the free energy can be obtained as the area under the isotherm: F (V, T ) =
isotherm

P dV.

We perform the integration graphically (Fig. 6.16). The volumes V1 and V2 are dened by the double tangent construction. At any point along the tangent, like X, the free energy is a linear combination of the free energy at 1 and 2 and, therefore, represents a mixture of two phases. This non-uniform state has the same P and T as the uniform state 3, but it has lower free energy as it is seen from Figure 6.16. The phase-separated state is the equilibrium state; the states 1 and 2 are dened by the conditions: two phases in equilibrium G1 (T, PV ) = G2 (T, PV ), where PV is the vapor pressure; U1 T S1 + PV V1 = U2 T S2 + PV V2 F1 F2 = PV (V2 V1 ).

6.6. VAN DER WAALS EQUATION OF STATE

71

Figure 6.16: Maxwell construction.

For T = const, dF = P dV,

V1 V2

F1 F2 =
V2

dV P (V ) =
V1 V2

dV P (V )

V1

P dV = PV (V2 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.

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CHAPTER 6. PHASE TRANSITIONS