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Chapter 6

Phase transitions

6.1 Concept of

Phases are states of characterized by distinct macroscopic properties. Typical phases we will discuss in this chapter are , and . Other important phases are superconducting and magnetic states. First and second order phase transitions. States of matter come with their stability regions, the . The properties of the microscopic state change by definition at the phase boundary. This change is

discontinuous first order for a continuous second order � � �

The appropriate variables for phase diagram of are the pressureP and the temper- atureT. critical point : Thefirst-order phase boundary between gas and liquid becomes second order right at the critical point. The two phases have then equal and specific ( per ). � There is no critical point for the liquid-solid transition.

: The point at which gas, liquid and solid coexist.

63 64 CHAPTER 6. PHASE TRANSITIONS

Skating on . The curve of water has negative slope. Ice does hence melt at constant temperatureT

6.2 First-order phase transition

When water starts , it undergoes a phase transition from a liquid to a gas phase. For both phases independently, the 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 offirst-order. Gibbs . Phase transitions in theP T phase diagram are described by the Gibbs enthalpyG(T,P,N), as defined by ( 5.11−), which is itself a function of the P and of the temperatureT.G(T,P,N) changes continuously across the phase boundary when the transition is offirst order. The entropyS and volumeV , which are given by the derivatives ∂G ∂G S= ,V= , dG= SdT+ V dP+ µdN − ∂T ∂P − � �P � �T of the Gibbs potential, are in contrast discontinuous.

Latent . Let us consider an instead of theP T theP V diagram, which is a projection of the equation of state for water. − −

Two phases1 and2 coexisting at a temperatureT 0 have different entropiesS 1 andS 2. The system must therefore absorb or release heat, the latent heatΔQ L,

ΔQ =T (S S ), L 0 2 − 1 during a phase transition offirst order.

6.2.1 Condition for phase coexistence We consider a system composed by one species of at given conditions ofP and T (constant). Let us assume coexistence of two phases in our system. In this case, the 6.2. FIRST-ORDER PHASE TRANSITION 65

Gibbs potential is the sum of Gibbs potentials of the two phases,

G(T,P,N) =G 1(T,P,N1) +G 2(T,P,N2)

=N 1µ1(T,P)+N 2µ2(T,P),

where we have used the Gibbs-Duhem relation (5.17).N i andµ i are the number of particles and the in phasei andN=N 1 +N 2. Principle of minimal Gibbs . The principle of minimal Gibbs energy discussed in Sect. 5.5.2 states that Gibbs potential has to be at its minimum, i.e. dG = 0, when P,T andN=N 1 +N 2 arefixed.G has to be therefore in equilibrium with respect to particle transfer from one phase to the other. This implies that

dG=µ 1dN1 +µ 2dN2 = 0, µ1(T,P)=µ 2(T,P) , (6.1)

with dN1 = dN 2. The condition of coexistence( 6.1), tells us that the two phases1 and 2 must have− identical chemical potentials.

6.2.2 Clausius-Clapeyron equation We denote the discontinuities across the phase boundary with

ΔG=G (T,P,N ) G (T,P,N ) (6.2) 2 1 − 1 2 ∂(ΔG) ∂(ΔG) ΔS=S S = ,ΔV=V V = , 2 − 1 − ∂T 2 − 1 ∂P � �P � �T

where we assume thatS 2 > S1. Cyclic chain rule. The discontinuitiesΔG,ΔS andΔV are functions ofV,T andP, which are in turn related by the equation of statef(P,V,T ) = 0. There must hence exist a function f˜ such that f˜(ΔG, T, P)=0. This condition allows to apply the cyclic chain rule discussed in Sect. 4.5. It to

∂(ΔG) ∂T ∂P = 1, (6.3) ∂T ∂P ∂(ΔG) − � �P � �ΔG � �T ΔS 1/ΔV − � �� � � �� � 66 CHAPTER 6. PHASE TRANSITIONS where we have used (6.2). pressure. We note thatP is the (Dampfdruck) for the gas-liquid transition. It changes with along the phase transition line as

dP ∂P , (6.4) dT ≡ ∂T � �ΔG=0 where we have used withΔG = 0 when the two phases are in equilibrium with each other. (∂P/∂T) is hence slope of the transition line in theP T diagram. ΔG=0 −

The slopeΔP/ΔT along the solid-liquid is positive when the substance contract upon , the standard situation. Water does however expands upon freezing due to the bonding between .ΔP/ΔT is in this case negative. Clausius-Clapeyron relation. We rewrite (6.3) as

dP ΔS dP ΔQ = , = L , (6.5) dT ΔV dT TΔV � �ΔG=0 whereΔQ L =TΔS is the . All quantities entering the Clausius-Clapeyron relation (6.5) can be measured. It can be used either as a consistency check or to determine the latent heatΔQ by measuringT,ΔV and the slope dP/dT. Second order transitions. In a second-order phase transition thefirst derivatives ofG vanish and the Clapeyron equation is replaced by a condition involving second derivatives.

6.3 Ehrenfest classification of phase transitions

For the following discussion, let us denote the two phases in equilibrium at a given co- existence curve asα andβ. Following Ehrenfest we define next the order of the phase transition.

The order of the lowest derivative of the Gibbs enthalpyG showing a discontinuity upon crossing the coexistence curve is the order of a phase transition. 6.3. EHRENFEST CLASSIFICATION OF PHASE TRANSITIONS 67

This definition quantifies the preliminary discussion of Sect. 6.1. Phase transitions of ordern. Explicitly, a phase transition between phasesα andβ is of ordern if ∂mG ∂mG ∂mG ∂mG α = β , α = β ∂T m ∂T m ∂P m ∂P m � �P � �P � �T � �T form=1,2, . . . , n 1 and if − ∂nG ∂nG ∂nG ∂nG α = β , α = β ∂T n � ∂T n ∂P n � ∂P n � �P � �P � �T � �T In practice, only phase transitions offirst- and second-order are of importance. Their properties are listed below. 1st order: 1)G(T,P ) continuous; ∂G ∂G 2)S= andV= discontinuous; − ∂T ∂P � �P � �T 3) latent heat. ∃ 2nd order: 1)G(T,P ) continuous; 2)S(T,P ) andV(T,P ) continuous; 3) the discontinuities in the second order derivative ofG(T,P,N) leads to discontinu- ities of the response functions ∂S ∂2G C =T = T P ∂T − ∂T 2 � �P � �P 1 ∂V 1 ∂2G κ = = T − V ∂P − V ∂P 2 � �T � �T 1 ∂V 1 ∂2G α= = V ∂T V ∂T∂P � � � � (susceptibilities) across the transition Here we have used the definition (4.19) for the heatC P at constant pressure.κ T is the isothermal ,α the coefficient, as defined in Sect. 4.5, and dG= SdT+ V dP+ µdN. − 68 CHAPTER 6. PHASE TRANSITIONS

Specific heat jump. Phase transitions of the second order show afinite discontinuity in the specific heatC P . An example is the transition to a superconducting state a at zero magneticfield . H Diverging correlation length at criticality. The Ehrenfest classification is only valid if the motion of far away particles is not correlated, viz that the correlation length isfinite. The correlation length diverges however at criticality for second order phase transition i.e. whenT T c. This leads in turn also to diverging response functions. The → χ of a magnetic system diverges f.i. as

∂M 1 χ= ,χ(T) , (6.6) ∂H ∼ (T T )γ � �T − c whereγ is the . Critical exponents are evaluated using advanced statis- tical methods, such as the theory. Note, however, that (6.6) is observed in most cases only very close to the transition. The entropy for a discontinuous transition. Discounting the exact order of transition we may classify a phase transition in any case with regard to the continuity of the entropy. For a discontinuous transition we have:

(i)ΔS= 0 ; latent heat; � ∃

∂2G (ii)C P = T ∂T 2 isfinite forT=T 0; no condition exists forT=T 0. − P � � �

The entropy for a continuous transition. In this case wefind:

(i)S continuous no latent heat; ⇒ (ii) critical pointT ; ∃ c

(iii) singularities inC V ,κ T ,χ T

Density jumps. Consider afluid system for which the volumeV=(∂G/∂P) T shows a finite discontinuityΔV at a 1 st order phase transition, such as the liquid-gas line below the critical point. The corresponding densities particle densityρ=N/V is then likewise discontinuous. 6.4. OF STATE 69

The jumpΔρ diminishes along the liquid-gas transition line, when the temperature is increased, until it vanishing atT c. The transition becomes continuous at the critical pointT=T c. Spontaneous magnetic ordering. The magnetizationM of a magnetic compound is in part induced by an external magneticfield and in part due to the spontaneous ordering, viz by the alignment of the microscopic moments.

The magnetic entering the dU=δQ+δW isδW= dM, as defined by (3.15). With the Gibbs enthalpyG(T, ) being the (two-fold) LegendreH transform of the internal energyU(S,M), we then haveH that

∂G M= , dG= SdT Md . − ∂ − − H � H �T The magnetizationM is discontinuous when spontaneous ordering is present, i.e. when the transition is of 1st order. Following the transition line, by increasing the temperature T T , the jump 2M decreases until spontaneous ordering disappears and the phase → c s transition becomes second-order atT 0 =T c.

6.4 Van der Waals equation of state

The equation of state for an ,

PV=Nk BT,PV= nRT , (6.7) is only valid for very small densities of particles and, therefore, cannot describe the gas- liquid phase transition. This phase transition is due to intermolecular interactions. In 70 CHAPTER 6. PHASE TRANSITIONS this section, we will derive an equation of state for a gas which includes intermolecular interaction in a phenomenological way. Renormalized ideal gas. We consider with

Peff Veff = nRT (6.8) the ansatz that a gas of interacting molecules obeys the ideal gas equation of state (6.7), albeit with yet to determine effective variables, where theeffective pressure and temperature,P eff andT eff , are are functions of the physical pressureP and temperature T respectively. One can regard (6.8) as a renormalized ideal gas equation of state.

Interaction potential. The interaction between molecules is generically composed of a repulsive core (due to the Fermi repulsion between the electrons) and an attractive tail (due to the van der Waals dipole-dipole interaction). The depth of the attractiveU(r) is about 1 eV (changes with the gas species). This minimum is responsible for the chemical valence and for the structure of . Effective . The repulsive core of the intermolecular interaction leads to a volume exclusion, which can be modeled by considering the individual molecules as hard spheres of radiusr 0. The effective Volume entering (6.8) is then

3 3 1 4π(2r0) 16πr0 V =V b �N , b� = , (6.9) eff − ≈ 2 3 3 whereN=n(R/k B) is the overall number of molecules. Note that two hard-core particle of radiusr 0 cannot come closer than 2r0, with the factor 1/2 in (6.9) correcting for double counting. Effective pressure. The interaction between molecules is pairwise and therefore proportional to the square of the densityN/V . The van der Waals interaction mediated by induced dipoles in furthermore attractive. We may hence assume with N 2 P=P a � , a� > 0 (6.10) eff − V 2 that the physical pressureP is smaller than the effective pressureP eff by an amount propor- tional to (N/V) 2. 6.4. VAN DER WAALS EQUATION OF STATE 71

Van der Waals equation. We use

2 a=N a a�, b=N ab�,N=N an,

whereN A is Avogadro’s constant, together with the expressions (6.9) and (6.10) for the effective volumeV eff =V Nb � and respectively for the effective pressureP eff =P+ 2 2 − a�N /V . We then obtain the van der Waals equation

n 2 P V = nRT, P+a (V bn) = nRT . (6.11) eff eff V − � � � � 6.4.1 Virial expansion Inter-particle interactions become irrelevant in the low density limit (N/V) 0, for which the the van der Waals equation 6.11), reduces consequently to the ideal-gas→ equation of statePV= nRT . It is hence of interest to evaluate the corrections to the ideal-gas equation of state by expanding (6.11) forfixed particle numberN systematically in 1/V. Rescaling. We start by rescaling the parameters of the van der Waals equation:

an2 =A,B= bn, R¯= nR .

We then obtain

1 RT¯ A PV B − A P= , = 1 . (6.12) (V B) − V 2 RT¯ − V − RTV¯ − � � for (6.11), Virial expansions. With the Taylor expansion

1 2 B − B B 1 = 1 + + +... − V V V � � � � of thefirst term in ( 6.12) with respect to 1/V we obtain

PV 1 A B 2 B 3 = 1 + B + + +.... (6.13) RT¯ V − RT¯ V V � � � � � � This expression has the form of a virial expansion:

PV C C A = 1 + 2 + 3 +..., C =B , (6.14) RT¯ V V 2 2 − RT¯

th 2 whereC n is the n virial coefficient. MeasuringC 2 andC 3 =B by observing experimen- tally the deviations from the on can extract the parametersA andB of the van der Waals gas. The virial expansion is also important for microscopic calculations. 72 CHAPTER 6. PHASE TRANSITIONS

6.4.2 Critical point The the isotherms of the pressureP are uniquely defined via the van der Waals equation (6.12) by the VolumeP . The reverse is however not true. Rewriting ( 6.11) we obtain

PV 2 + an2 (V bn) = nRT V 2 , (6.15) − which shows thatV(P ) is given� by the roots� of a 3 rd-order polynomial.

Roots of the Van der Waals equation. For givenT andP there exist either three real roots or one real and two complex roots of (6.15). There exists hence a critical point (Pc,Vc,Tc) such that (6.15) has

T < Tc P < Pc : three different real roots

T=T c P=P c : one three-fold degenerate real root

T > Tc P > Pc : one real root The van der Waals of equation of the state must be then proportional to

(V V )3 = 0, V 3 3V V 2 + 3V 2V V 3 = 0 (6.16) − c − c c − c at the critical point (Pc,T c,V c). Comparing (6.15) with (6.16) wefindV c,P c, andT c:

nRTc Vc = 3bn 3Vc = nb+ Pc a 2   2 an Pc = 2 (6.17) 3Vc =   27b Pc     8a 3 abn3 RT = Vc = P c c   27b     Comparison with the ideal gas. Combining the roots found in (6.17) we can define with

PcVc 3 Zc = = = 0.375 nRTc 8 a universal parameter measuring the deviation of a from the ideal gas limit Zc 1. For water we haveZ c = 0.226 andT c = 324 ◦C. Real are generically further away→ from the ideal gas limit than the van der Waals theory would predict. 6.4. VAN DER WAALS EQUATION OF STATE 73

6.4.3 Maxwell construction

The van der Waals isotherm is a monotonic function ofV forT>T c. ForT0. (6.18) T − V ∂P ∂V � �T � �T Negative compressibility, if existent for a real gas, would however to a collapse of the system, with a decreasing volumeV and pressureP inducing each other. The system would not be thermodynamically stable. . The working substance avoids the collapse by separating sponta- neously into two phases, with each of the two phases being located in a point in the V P state phase characterized by a positive compressibilityκ T . These two phase will hence− have different densities, corresponding respectively to a liquid and to a gas phase. Coexistence condition. The two phases1 and2 are in equilibrium at the vapor pressure PV , as discussed in Sect. 5.5.2, if the differentitials of the Gibbs coincide for contantN 1 +N 2 =N andV 1 +V 2 =V:

dG1(T,PV ,N1) = dG2(T,PV ,N2),

dF1(T,V1,N1) +P V dV1 = dF2(T,V2,N2) +P V dV2 , (6.19) where we used thatG(T,P,N)=F(T,V,N)+PV . Note that both the temperatureT and the vapor pressureP V are constant in (6.19). Free energy. The free energyF(T,V,N) defined by ( 5.12), ∂F F(V,T)= P dV, P= , (6.20) − − ∂V �isotherm � �T,N can be obtained as the area under the isotherm.

Integrating the coexistence condition (6.19) one obtains

F F =P (V V ), (6.21) 1 − 2 V 2 − 1 which implies that the volumesV 1 andV 2 are defined by a double tan- gent construction. – The free energy is is a weighted of two phases1 and2 at any point along the tangent between1 and2. The resulting non-uniform state has the same P andT as the uniform state 3, but a lower free energy. 74 CHAPTER 6. PHASE TRANSITIONS

Maxwell construction. We note that

V2 V3 V2 F F = ( P)dV= ( P)dV+ ( P)dV 2 − 1 − − − �V1 �V1 �V3 along any isotherm, according to (6.20). Rewriting the coexistence condition (6.21) as

F F =P (V V +V V ) 2 − 1 V 1 − 3 3 − 2 we then obtain with

V3 V2 P (V V ) P dV = P dV P (V V ) (6.22) V 3 − 1 − − V 2 − 3 �V1 �V3 area A area B � �� � � �� � the Maxwell construction. Eq. (6.22) determines the vapor pressureP V =P(V 3) as the pressure for which the areasA andB are equal to each other.