4.

0 PHASE EQUILIBRIUM IN PURE SUBSTANCES

Goal: Understand the general phenomenology of phase transitions and phase

coexistence conditions for a single component system

• Phase - a distinct part of a system, uniform in chemical composition and physical

properties that is separated from other homogeneous parts of the system by boundary
surfaces.
E.g.
✓ gas or gaseous mixture is a single phase
✓ pure liquid (e.g., water) or totally miscible liquids constitute a single phase
✓ a crystal (e.g., NaCl) is a single phase
✓ ice is a single phase
✓ a slurry of ice and water is a two-phase system
✓ an alloy of two metals has P = 2 if immiscible and P =1 if miscible
✓ a solution of solid A and solid B is uniform and therefore P = 1
✓ a dispersion (which may be uniform on a macroscopic scale) is not uniform at the molecular
level and therefore P = 2 if two solids (or liquids) are involved

• Component– minimum number of independent species necessary to define the composition

of all the phases present in the system.
E.g.
✓ pure water is one component (C=1)
✓ mixture of ethanol and water (C=2)
✓ if species do react and are at equilibrium, then the phrase “all the phases” must be
emphasized

NH4Cl (l) = NH3 (g) + HCl (g): C = 1, since both phases have the formal composition
“NH4Cl”.

However, if HCl (g) is added, then C= 2 since now relative amounts of HCl and NH3 are
arbitrary
CaCO3 (s) = CaO (s) + CO2 (g): in this case, the two phases (s and g) do not have the
same formal composition. We shall have to specify the CO2 in the gas phase and CaCO3 in
the solid phase (the concentration of CaO (s) is not independent). Therefore C=2

The method of deducing the number of components is based on the equation:

C = S – R where S = # of different species; R = # of relations

For the CaCO3 example above: S = 3 and R = 1, hence C = 2

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 ✓ Sucrose in water: C = 2 (R = 0)
✓ NaCl in water: S = 3, R = 1 for balancing charges, hence C= 2

4.1 The Gibbs Phase Rule

The Phase Rule gives the number of independent variables needed to describe a system where
different phases coexist in equilibrium.

• At equilibrium, in the absence of chemical reaction:

P+F =C+2

C = number of components present

P = number of phases present
F = number of degrees of freedom

e.g., Consider Vapour Liquid Equilibrium (VLE)

What is the saturated vapour pressure, PSAT of a pure liquid at a given temperature?

Gibbs Phase Rule: ⇨ P + F = C + 2  F = 1

• Implication: If we specify the temperature, the vapour pressure is automatically defined.

This fits with common experience.

• E.g., at fixed p, liquids have unique boiling temperature e.g., 100 oC for water at 1 atm.

We want to be able to calculate this fixed (saturated) vapour pressure, PSAT, for any temperature, for
any pure liquid.

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4.2. Phase Diagrams for Pure Substances
Describe the phase properties as a function of state variables, for example in terms of (T, p).

The phase diagram of a substance shows the regions of pressure and temperature at which its
various phases are thermodynamically stable (Figure below).

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 ✓ The lines separating the regions, called phase boundaries, show the values of p and T at
which two phases coexist in equilibrium.

✓ The pressure of a vapour in equilibrium with the liquid (or solid) is called the vapour
pressure of the substance, Pvap, Psat, P*

✓ The vapour pressure of a substance increases with temperature because at higher

temperatures more molecules have sufficient energy to escape from their neighbours.

✓ For the melting line, for example, solid and liquid coexist: μs(T, p) = μl(T, p)

One equation [μs (T, p) = μl (T, p)], two variables (T, p). This means that coexistence of
two phases is described by T (p) or p (T). E.g. a line in the (T, p) phase diagram.

The phase rule: P = 2, C = 1  F = 1, i.e. fixing T fixes P on the phase co-existence curve

✓ At the triple point, the chemical potential of all three phases are the same… solid, liquid
and gas coexist: GL (T , P) = GS (T , P) = GV (T , P)

The phase rule: P = 3, C = 1  F = 0,

i.e. this defines a unique point (Tt, pt) in the (T, p) phase diagram.
e.g., for H2O: T = 0.01oC; P = 0.006112 bar

✓ In the single phase (planar) regions of the diagram, one of the chemical potentials is lower
than the other two. T and p can be changed independently without changing phases.

Therefore, for a single component system (see phase diagram on the P-T plane above), the Gibbs
phase rule gives:

P = 1  F = 2 (T, p) defines a coexistence plane

P = 2  F = 1 (T, p) defines a coexistence line

P = 3  F = 0 Tt, pt uniquely defines a triple point

P = 4  F = -1 IMPOSSIBLE!

4.2 Phase equilibrium

For a closed system, the Gibbs free energy is minimized at chemical equilibrium. We now consider
how this condition impinges on Vapour-Liquid Equilibrium (VLE).

Consider a closed system of one mole of vapour and let that mole of vapour condense (at constant T
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and P).

L V
nTotal = n + n
• Liquid has some molar Gibbs free energy, GL (T, P )

• Vapour has some molar Gibbs free energy, GV (T, P )

It follows then that if

• GL  GV ⇒ spontaneous to move liquid into vapour  d G = GV − GL  0

• GV  GL ⇒ spontaneous to move vapour into liquid  d G = GL − GV  0

• GV = GL ⇒ Equilibrium  d G = GV − GL = 0

Therefore, to find condition of chemical equilibrium, we need to calculate G as we go from vapour

to liquid, so that we can ensure that it is zero.

For equilibrium between the vapour and liquid phases

• Thermal equilibrium: TV = TL

• Mechanical equilibrium: PV = PL (i.e., liquid will not expand into gas and vice versa)

• Chemical equilibrium: GV = GL  (Gibbs free energy is minimized, dG = 0)

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 • (b) P-V phase diagrams
Example: Vapour Liquid Equilibrium (VLE)

What is the saturated vapour pressure, PSAT of a pure liquid at a given temperature?

• Recall the Gibbs Phase Rule: P + F = C + 2  F = 1

Implication: If we specify the temperature, the vapour pressure is automatically defined. This fits
with common experience.

• E.g. At fixed p, liquids have unique boiling temperature e.g. 100oC for water at 1 atm.

We want to be able to calculate this fixed (saturated) vapour pressure, PSAT, for any temperature, for
any pure liquid.

Remember the isotherms (from a cubic equation of state, or experiment) – see, for example, van der
Waals equation of state from the previous handouts. Consider an isotherm below the critical
temperature:

Consider compressing the gas (isothermally) from infinite expansion:

dP
is initially negative, as we expect for a gas.
dV
dP
A point is reached, V2, at which is zero and then becomes positive – the gas is compressed and
dV
the pressure drops! The molecules have started to attract each other – liquefaction.

dP
Beyond V2 the pressure will drop automatically until is negative again (V1) i.e. the molecules
dV
are in such close proximity that they start to repel – the liquid has formed.
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The fluid cannot exist between V1 and V2 (at the temperature we have chosen).

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The meaning of the critical point is now clear: it is the maximum temperature and pressure at which
vapour and liquid can coexist at equilibrium (because it is the lowest temperature isotherm for
which there is only one specific volume for all pressures). At the critical point, the vapour and
liquid have the same specific volume – they are indistinguishable.

Over the range of pressures P1 → P2, both liquid and vapour (gas) can exist. This would appear to
contradict the Gibbs Phase Rule and our intuition about boiling points described about.

Fig. 6.2. Calculated isotherms are shown for CO2, modelled as a van der Waals gas. The gas and liquid
(blue) regions and the gas–liquid (yellow) coexistence regions are shown. The isotherm at 304.12 K is at the
critical temperature and is called the critical isotherm.

Consider the isotherm at T = 258 K and gradually decrease the pressure from a very high value (Fig.
6.2).

• the liquid begins to expand as we follow the isotherm down (point d). Liquids are relatively
incompressible, so the isotherm is very steep.

• When we reach the binodal curve, the first bubble of vapor appears as the liquid boils. For
this reason, the left branch of the binodal curve is called the bubble line.

• Instead of following the curved line of the equation of state (see andout 5), the real fluid
now follows the horizontal line, called a tie line (c to b). The right side of the coexistence
curve is called the dew line because it represents the case where we have all vapor and the
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 first drops of liquid just begin to form if we try to increase the pressure.

• The binodal curve encloses the region where two phases (liquid and vapor) will coexist. As
long as we are in this two-phase region (c to b), the pressure and temperature will be
constant, and we simply evaporate more liquid or condense more vapor when we try to
expand or compress, respectively, the system.

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 • When we have vaporized all of the liquid and the molar volume is now that of the saturated
vapor (on the dew line), then when we try to lower the pressure again, we find that the
pressure will again go down and the volume will increase as the gas expands (point a).

• The tie line connects the bubble point of the fluid to the dew point, divides the isotherm into
equal areas (compare with Fig. 6.3). Therefore, the binodal curve is the locus of all such
points where the tie line bisects the isotherms.

• The ends of these tie lines represent the liquid and vapor molar volumes at the chosen
temperature and pressure.

Application to Vapour Liquid Equilibrium (VLE)

Consider (again) the isotherms of the van der Waals equation of state:

Fig. 6.3: Isotherms of the van der Waals equation of state.

• Recall: d G = −SdT + V dP
• Along the isotherm: dT = 0  d G = V dP

VL

Hence, at chemical equilibrium  G(vapour →liquid ) =

 V dp = 0
VV

⇒ Maxwell construction: To find the value of pressure for the "liquid-vapour" equilibrium state
(PSAT) for the given temperature, find the value of P for which the areas given by (ABC) and (CDE)
are equal (Figure 6.3).

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 • (c) The P-V-T surface for a one-component system

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