FLUID PHASE EQUILIBRIA Phase rule, Stability of

thermodynamic systems, first order phase transitions and

critical phenomenon, single component phase diagrams,
thermodynamic properties of single phase and
multicomponent system
• Criteria for Phase Equilibrium
• Gibbs energy is the key property for characterizing phase equilibria.
• GL = GV is a constraint for phase equilibrium. None of our other
thermodynamic properties, U, H, S, and A is equivalent in both phases.
• The Clausius-Clapeyron Equation
• We can apply these concepts of equilibrium to obtain a remarkably
simple equation for the vapor-pressure dependence on temperature at
low pressures
• Changes in Gibbs Energy with Pressure
 Gibbs Energy in the Low-Pressure Limit

• The calculation of ΔG is illustrated where the shaded area represents the integral.
The slope of a G versus P plot at constant temperature is equal to the molar volume.
• For a real fluid, the ideal-gas approximation is valid only at low pressures. The
volume is given by V = ZRT/P;
• For an ideal gas, we may substitute Z = 1
• as a real fluid state approaches zero pressure, Z will approach the ideal gas limit and
dG approaches dGig. Thus, the difference dG – dGig will remain finite, and goes to
zero as P goes to zero. Thus,dG – dG = d(G – G )
ig ig
Fugacity and Fugacity Coefficient
• The fugacity has one advantage over the Gibbs energy in that its application to mixtures is a
straightforward extension of its application to pure fluids.
• the fugacity of an ideal gas equals the pressure and the fugacity of a liquid equals the vapor
pressure under common conditions
• The vapor pressure was the original property used for characterization of phase equilibrium by
experimentalists
• Integrating from low pressure, at constant temperature, we have for the left hand side,

• because (G – Gig) approaches z ero at low pressure. Integrating the right-hand side
• To complete the definition of fugacity, we define the low-pressure limit,

• and we define the ratio f/P to be the fugacity coefficient, ϕ.

Fugacity Criteria for Phase Equilibria

• The integral of above eqn is represented by the negative value of the

shaded region between the real gas isotherm and the ideal gas
isotherm. The fugacity coefficient is a measure of non-ideality.
• Under most common conditions, the fugacity coefficient is less than
one. At very high pressures, the fugacity coefficient can become
greater than one.

• we may subtract Gig from both sides and divide by RT, giving
Calculation of Fugacity (Gases)
• Equations of State
• Equations of state are the dominant method used in process
simulators because the EOS can be solved rapidly by computer. We
consider two equations of state, the virial equation and the Peng-
Robinson equation. We also consider the generalized compressibility
factor charts as calculated with the Lee-Kesler equation.
• Ideal Gas
• The Virial Equation
• Writing the virial coefficient in reduced temperature and pressure,
The Peng-Robinson Equation

Generalized Charts
 Calculation of Fugacity (Liquids)
• The shape of an isotherm below the critical temperature differs significantly from an ideal-gas
isotherm. Such an isotherm is illustrated which begins in the vapor region at low pressure, intersects
the phase boundary where vapor and liquid coexist, and then extends to higher pressure in the liquid
region.
• Point A represents a vapor state,
• point B represents saturated vapor,
• point C represents
• saturated liquid, and
• point D represents a liquid.

Poynting Method
The Poynting method applies between saturation (points B, C) and point D. The integral is

Since liquids are fairly incompressible for Tr < 0.9, the volume is approximately constant, and may be removed from the integral, with the resultant Poynting correction
becoming

The fugacity is then calculated by

Equation of State Method

• When Tr < 1, the equation of state predicts an isotherm with “humps” in the vapor/liquid region
• the shaded area above line is equal to the shaded area below, and that the pressure where the line
is located represents the saturation condition (vapor pressure)
• In fig (b) the molar Gibbs energy is indeed continuous as the fluid transforms from the vapor to the
liquid. The Gibbs energy first increases according to
based on the vapor volume.

• During the transition from vapor to liquid, the “humps” lead to the triangular region associated
with the name of van derWaals loop.
Calculation of Fugacity (Solids)
• Fugacities of solids are calculated using the Poynting method, with the
exception that the volume in the Poynting correction is the volume of
the solid phase.

• Equations of state are generally not applicable for calculation of solid

phases because they are used only to represent liquid and vapor phases.
• However, they may be used to calculate the fugacity of a vapor phase in
equilibrium with a solid, given by ϕsatPsat. As for liquids, the Poynting
correction may be frequently set to unity with negligible error.
Saturation Conditions from an Equation of
State
• The only thermodynamic specification that is required for
determining the saturation temperature or pressure is that the Gibbs
energies (or fugacities) of the vapor and liquid be equal.
• This involves finding the pressure or temperature where the vapor and
liquid fugacities are equal. The interesting part of the problem comes
in computing the saturation condition by iterating on the temperature
or pressure.
Introduction to Phase Diagrams
• For a pure fluid, the Gibbs phase rule shows vapor-liquid equilibrium occurs with only one degree of freedom, F = C – P + 2 = 1
– 2 + 2 = 1.
• At one atmosphere pressure, vapor-liquid equilibria will occur at only one temperature—the normal boiling point temperature.
• However, with a binary mixture, there are two degrees of freedom, F = 2 – 2 + 2 = 2.
• For a system with fixed pressure, phase compositions and temperature can both be varied over a finite range when two phases
coexist.
• Experimental data for experiments of this type are usually presented as a function of T and composition on a plot known as a T-
x-y Diagram
• At fixed temperature, pressure and composition may vary in a binary mixture and obtain data to createa P-x-y diagram
• The region where two phases coexist is shown by the area enclosed by the curved lines on either plot and is known as the
phase envelope
• On the T-x-y diagram, the vapor region is at the top
(raising T at fixed P causes vaporization of liquid).
• On the P-x-y diagram, the vapor region is at the
bottom (lowering P at fixed T causes vaporization of
liquid).
• Note that the intersections of the phase envelope with
the ordinate scale sat the pure component
compositions give the pure component saturation
temperatures on the T-x-y diagram, and the pure
component vapor (saturation)pressures on the P-x-y
diagram.
• Therefore, significant information about the shape of
the diagram can often be deduced with a single
mixture data point when combined with the pure
component end points.
• Qualitatively, the shape of the Px-y diagram can be
found by inverting the T-x-y, and vice versa.
• Customarily, for binary systems in the separations
literature, the more volatile component composition is
plotted along the abscissa in mole fraction or percent.
The lower curve on the T-x-y diagram is next to the
liquid region, and it is known as the bubble line. he
bubble-temperature line gives the boiling
temperature of the mixture as a function of
composition at the specified pressure.
The upper curve is next to the vapor region, and is
known as the dew line. The two lines meet at the
axes if the conditions are below the critical pressure
of both components.
At a given composition, the temperature along the
bubble line is the temperature where an infinitesimal
bubble of vapor coexists with liquid. Thus, at an over-
all composition of 50 mole% A, the system of Fig. 10.1
at fixed pressure is 100% liquid below 300 K at the
pressure of the diagram.
As the temperature is raised, the overall composition
is constrained to follow the vertical dashed line
constructed on the diagram, and the first vapor
bubble forms at the intersection of the bubble line at
300 K at point a, which is known as the bubble
temperature for a 50 mole% mixture at the system
pressure.
The lower curve on the T-x-y diagram is next to the
liquid region, and it is known as the bubble line. he
bubble-temperature line gives the boiling
temperature of the mixture as a function of
composition at the specified pressure.
The upper curve is next to the vapor region, and is
known as the dew line. The two lines meet at the
axes if the conditions are below the critical pressure
of both components.
At a given composition, the temperature along the
bubble line is the temperature where an infinitesimal
bubble of vapor coexists with liquid. Thus, at an over-
all composition of 50 mole% A, the system of Fig. 10.1
at fixed pressure is 100% liquid below 300 K at the
pressure of the diagram.
As the temperature is raised, the overall composition
is constrained to follow the vertical dashed line
constructed on the diagram, and the first vapor
bubble forms at the intersection of the bubble line at
300 K at point a, which is known as the bubble
temperature for a 50 mole% mixture at the system
pressure.
Phase compositions at a given P and T may be found by
reading the compositions from intersections of the bubble
and dew lines with horizontal lines constructed on the
diagram, such as the dashed line at 300 K.
For our example at the bubble temperature, the liquid
phase will be 50 mole% A because the first bubble of
vapor has not yet caused a measurable change in the
liquid composition. The vapor phase composition
coexisting at the bubble-point temperature will be 80
mole% A (point b). As the temperature is increased to 320
K, the overall mixture is at point d, the liquid phase will be
30 mole% A (point c), and the vapor phasewill be 70 mole
% A (point e).
Suppose we start an experiment with a 50 mole% mixture
at 350 K, where the mixture is 100% vapor. As the
temperature is lowered, the dew temperature is
encountered at 340 K for the 50 mole% mixture at system
pressure (point g), and the first drop of liquid is formed
which is about 20 mole% A (point f). Note that the bubble
and dew temperatures are composition-dependent.
For example, the bubble temperature of a 30 mole%
mixture is 320 K (point c), and the bubble temperature of
a 20 mole% mixture is 340 K (point f). The bubble and
dew-point discussions could also be presented on the
pressure diagram, but in this case we would refer to the
bubble and dew pressures. Note that the relative vertical
locations of the bubble- and dew lines are flipped on
thetwo diagrams. The horizontal dotted lines connecting
coexisting compositions are tie lines.
 Vapor-Liquid Equilibrium (VLE)
Calculations
• Depending on the information
provided, one may perform one of
several types of vapor-liquid
equilibrium (VLE) calculations to
model the vapor-liquid partitioning.
• These are: bubble-point pressure
(BP), dew-point pressure (DP),
bubble-point temperature (BT), dew-
point temperature (DT), and
isothermal flash (FL) and adiabatic
flash (FA).
• Principles of Calculations
• Standard approaches to solving VLE
problems utilize the ratio of vapor
mole fraction to liquid mole fraction,
known as the VLE K-ratio:
Binary VLE Using Raoult’s Law
• For a small class of mixtures where the components
have very similar molecular functionality and
molecular size, the bubble-pressure line is found to
be a linear function of composition
• the T-x-y and P-x-y diagram shapes are related
qualitatively by inverting one of the diagrams.
Because the bubble pressure is a linear function of
composition, we may write for a binary system,

• Dividing by P, we find the form of the bubble

objective function

• Therefore, we conclude that the K-ratio for Raoult’s

law is
• Bubble Pressure
• For a bubble-pressure calculation, writing as which is
• Multiplying by P, we may write
• Dew Pressure

• Bubble Temperature
• To solve this equation, it is necessary to iterate on temperature (which changes Pi sat) until
P equals the specified pressure. Then the vapor phase mole fractions are calculated
• Dew Temperature
• To solve this equation, it is necessary to iterate on temperature (which changes Pi sat) until
P equals the specified pressure. Then the liquid phase mole fractions
Multicomponent VLE Raoult’s Law
Calculations
• Extending our equations to multicomponent systems is
straightforward. For a bubble calculation
• For a dew calculation we have
• These equations may be used for bubble- or dew-pressure
calculations without iterations. For bubble- or dew-point
temperatures, iteration is required. A first guess may be obtained
from one of the following formulas:
Concepts for Generalized Phase Equilibria
• Generalization of pure-component principles to multicomponent systems requires
that we consider how the thermodynamic properties change with respect to changes
in the amounts of individual components. For a pure fluid, the natural properties
were simply a function of two state variables. In multicomponent mixtures, these
energies and the entropy also depend on composition.

• At constant moles and composition of material, the mixture must follow the same
constraints as a pure fluid. That is, the state is dependent on only two state variables
if we keep the composition constant.
• ⇒ (∂G/∂P)T,n = V and (∂G/∂T)P,n = – S;
• These complicated-looking derivatives are really fundamental properties; therefore,
we can rewrite
chemical potential
• The quantity (∂G/∂ni)P, T, nj ≠ i tells us how the total Gibbs energy of
the mixture changes with an infinitesimal change in the number of
moles of species i, when the number of moles of all other species
fixed, and at constant P and T.
• The quantity (∂G/∂ni)P, T, nj ≠ i called the chemical potential,
Partial Molar Properties
• For any extensive thermodynamic property M, we may write
• .Note that T, P, and nj ≠ i are always held constant for a partial molar
property. The overbar indicates a partial molar quantity, that is, for
total volume V, the quantity (∂V/∂ni)T,P,nj≠i is called the partial molar
volume and given the symbol .
Equilibrium Criteria
• For equilibrium at constant T and P, the Gibbs energy is minimized and
mathematically the minimum means dG = 0 at equilibrium.

• Suppose we define our system to consist of two components (e.g,. EtOH +

H2O) distributed between two phases (e.g., vapor and liquid), dG = dGL + dGV
= 0, and at constant T and P, the moles may redistribute between the two
phases,

• But if component 1 leaves the liquid phase then it must enter the vapor phase
(and similarly for component 2) because the overall system is closed.
Chemical Potential of a Pure Fluid

• For a pure fluid, there is only one component, so dni = dn, and since
G(T,P) is intensive, then n(∂G/∂n)T,P = 0. Also (∂n/∂ni)T,P = 1
• The chemical potential of a pure fluid is simply the molar Gibbs
energy.
Component Fugacity
• When phases are in equilibrium, the component moves (“escapes”) from the
phase where it has the higher fugacity to the phase where it has the lower
fugacity until the fugacities are equal in both phases
• At constant T, we defined RTdlnf ≡ dG which can be generalized to define the
fugacity of a component in a mixtures as

• where is the fugacity of component i in a mixture and μi is the chemical

potential of the component. In the limit as the composition approaches purity,
these properties become equal to the pure component values. A caret(^) is
used in the symbol for the fugacity of a component. The component fugacity is
not a partial molar property, so the over bar cannot be used
Equality of Fugacities as Equilibrium
Criteria
• The equality of chemical potentials at equilibrium can easily be
reinterpreted in terms of fugacity in a manner analogous to our
methods for pure components
• By integrating as a function of composition at fixed T from
a state of pure i to a mixed state, we find
• where μi,pure and fi are for the pure fluid at the system temperature.
Writing an analogous expression for the liquid phase, and equating
the chemical potentials
Mixture Properties for Ideal Gases
• The partial molar quantities for ideal gases must be the same as the
pure component properties.
• The entropy of an ideal gas is calculated by the sum of the entropies
of the components plus the entropy of mixing

• the entropy of mixing is nonzero and positive:

• and the partial molar entropy is

• The Gibbs energy and the fugacity will be at the core of phase
equilibria calculations. The Gibbs energy of an ideal gas is obtained
from the definition, G ≡ H – TS. Using Hig and Sig

• Therefore, the Gibbs energy of mixing is nonzero and negative:

chemical potential of an ideal-gas component: fugacity of an ideal-gas component:

Mixture Properties for Ideal Solutions
• Ideal solutions are similar to ideal-gas mixtures, but they to not follow the ideal-gas law
• The internal energy and enthalpy for ideal solutions , Since these properties are additive,
the partial molar properties are equal to the pure component properties,

• a general expression for the ideal entropy change of mixing,

• The reason is that changes in entropy are related to the change in accessible volume.
• Even though a significant volume is occupied by the molecules themselves in a dense
liquid, the void space in one liquid is very similar to the void space in another liquid if the
molecules are similar in size and polarity.
• That means that the accessible volume for each component doubles when we mix equal
parts of two equal-sized components. That is essentially the same situation that we had
when mixing ideal gases. The partial molar entropy of mixing is
• The general relationship for ΔGmix gives a relationship for fugacity. We
can extend our definition of the enthalpy of mixing to the Gibbs
energy of mixing,

• Thus, comparing
• By comparing the relations in the logarithms, we obtain the Lewis-
Randall rule for ideal solutions:
The Ideal Solution Approximation and
Raoult’s
Law
• By our equilibrium constraint,
• By our ideal solution approximation in both phases, the equilibrium
criteria becomes
• The fugacity of the pure vapor
• The fugacity of the liquid comes
• Combining
• Writing in terms of the Ki ratio,
• at reasonably low pressures,
• resulting in Raoult’s Law,
Bubble Pressure

where no iterations are required because temperature, and therefore vapor pressures, are known. Once the
bubble pressure is found, the value can be
Dew Pressure
Bubble Temperature

• To solve this equation, it is necessary to iterate on temperature

(which changes Pi sat) until P equals the specified pressure. Then the
vapor phase mole fractions are calculated using
Dew Temperature

To solve this equation, it is necessary to iterate on temperature (which changes Pi sat) until P equals the
specified pressure. Then the liquid phase mole fractions are calculated using
Flash Drum
• Flash drums are frequently used in chemical processes. For an isothermal drum, the
temperature and pressure of the drum are known. Consider that a feed stream is liquid
which becomes partially vaporized after entering the drum
• The name of the flash procedure implies that it is applicable only for flashing liquids, but in
fact, the procedure is also valid for vapor entering a partial condenser or for any number of
incoming vapor and/or liquid streams with overall compositions specified by {zi} with
overall flow rate F.
• To apply the procedure, the overall composition of the components, zi, total feed flow rate,
F, and outlet T and P just need to be known before the procedure is started. Though the
method is introduced using flowing streams, flow is not required for a flash calculation; the
calculation can be performed for any overall composition constrained at a particular
temperature and pressure even within a closed system.
• Also, the inlet stream temperature does not need to match the outlet temperature; the two
outlet streams are at the specified temperature.
• If z is the feed composition and V/F is the liquid-to-feed ratio, then L/F
= 1 – V/F, and the component balance is
• zi = xi(L/F) + yi(V/F).
• Substituting for L/F from the overall balance, and using yi = xiKi, the
component balance becomes zi = xi[(1 –V/F) + Ki(V/F)], which can be
solved for xi:

• using yi = xiKi, we may multiply above eqn by Ki to obtain yi.