Vapor-Liquid Phase Equilibrium at Low Pressures Raoults Law

Consider a system with two phases (vapor and liquid) at given values of pressure
and temperature.

T
V
L

What we want to know is the equilibrium relationship between the measurable

variables P, T, yi, xi in this system.
The simplest relationship is Raoults law, which is based on assumptions of ideal
gas for the vapor phase and ideal liquid solution for the liquid phase:
Pyi Pi sat xi

Calculations Using Raoult's Law

Bubble-point pressure problem -- T,x given -- P,y unknown.
This is a straight-forward calculation. The vapor pressures are found at the
given temperature, which allows direct calculation of the pressure and
vapor mole fractions:

yi

Pyi P Pi sat xi
Pi sat x i
P

Bubble-point temperature problem -- P,x given -- T,y unknown.

A trial and error procedure must be followed, where T is assumed, the
vapor pressures calculated, and then see if the correct total pressure is
obtained (or the vapor mole fractions sum to unity).

Pi sat xi
P

Dew-point pressure problem -- T,y given -- P,x unknown.

No trial and error is needed, as P can be directly calculated.
Py i
Pi sat

xi
P

x
1
i

/ Pi sat

Dew-point temperature problem -- P,y given -- T,x unknown.

Guess a T, find the vapor pressures, and see if the liquid mole fractions sum
to unity.

Pyi
Pi sat

Discuss calculation of a y-x diagram for this system at fixed P.

K-values, flash calculations, and relative volatilities
Discuss the T-x-y diagram (Fig. 10.12, p. 346). It represents all possible
dew and bubble points for this system at the pressure given.
Discuss the P-x-y diagram (Fig. 10.11, p. 344). It represents all possible
bubble and dew points for this system at the T given.
A vapor-liquid equilibrium ratio (K-value) is defined for a component as the
ratio of mole fraction in the vapor to mole fraction in the liquid for that
component.
The criteria for flash calculations can be written if various forms. A useful
one is given below.
Ki

yi Pi sat

f ( P, T )
xi
P

zi Ki 1
0
i 1)

1 V (K

T, P, and feed compositions (zis) are know. A trial and error for V must be
done (fraction to vapor stream). See Sec. 10.6 for the derivation.

According to Raoults law, the relative volatility (defined below) is just the
ratio of component vapor pressures.
Relative volatility:

ij

yi / xi Ki Pi sat

y j / x j K j Pjsat

Modified Raoults Law - Low Pressures

At low pressure, where gases can be considered ideal, it may be necessary
to correct for liquid-phase nonidealities, using a Modified Raoults Law
Py i Pi sat xi i
Ki

y i Pi sat i

f T , P, xi ' s
xi
P

See pp. 349-54 for calculations of various phase equilibrium problems.

Activity coefficients come from experimental data (using empirical
equations), or from estimation techniques, such as the UNIFAC method
presented in Append. H.
High Pressures - K-Values for Light Hydrocarbon Systems
Discuss P-T diagrams for mixtures -- refer to Fig. 10.5, p. 336.
For any given mixture, there is a unique bubble-point curve and a unique dewpoint curve, connected at the critical point.
Retrograde condensation can occur for some systems, particularly petroleum gases
containing heavy hydrocarbons, found as single-phase fluids in deep reservoirs at
high pressure and temperature (gas condensate fluids). If the pressure is reduced
at constant temperature, it is possible to hit the dew-point curve, resulting in liquid
drop-out or retrograde condensation.
The ethane-heptane system is a simple demonstration of this. Note that retrograde
condensation can occur for an 88.7 mol % ethane mixture, but not for a 26.5 mol
% ethane mixture.
DePriester Charts for estimation of K-values.
The assumption of ideal gas for the vapor phase restricts the use of
Raoults law to low pressures. If instead, the vapor phase is assumed to
form an ideal solution, then the vapor-liquid equilibrium relations can be
written in terms of K-values, as indicated below:

K i K i P, T

This is the basis for the DePriester Charts (pp. 356-7).

Bubble-point calculations:

Dew-point calculations:

1
1

K x

/ Ki

Both require trial and error for the unknown T or P.

Example Problem: Estimate the vapor pressure curves and the dew- and
bubble-point curves for the ethane + n-heptane system (58.7 mole %
ethane). Compare with Fig. 10.5, p. 336.
The General Nature of Phase Equilibria
Phase equilibria categories:
Positive deviations from Raoult's law due to nonideal solution behavior
unlike molecules do not have the same attractions as like molecules P-x
curve lies above straight line between vapor pressures.
Negative deviations from Raoult's law due to nonideal solution behavior
unlike molecules attract each other strongly compared to like molecules
(maybe form a weak complex) P-x curve lies below straight line between
vapor pressures.
.
If deviations become large enough, azeotropic behavior can occur.
Discuss Figs. 10.8-9, pp. 339-40.
If positive deviations become large enough, partial miscibility can occur
(i.e., liquid breaks into two separate phases).
Discuss Figs. 14.16-18, pp. 570-1.

General Phase Equilibrium Relations

Phase equilibrium variables: T, P, moles of each component
Consider a closed system with no chemical reactions. The fundamental property
relation with T and P as independent variables involves the Gibbs free energy:

dG t V t dP S t dT
G t

Vt

T
t

S t

Note that only the 1st and 2nd laws are involved in deriving this property relation,
plus the definition of G (G = H-TS).
If the system can exchange mass with its surroundings (another phase), then it
becomes an open system. The fundamental property relationship must be
modified, because the total Gibbs free energy will depend on the amount of each
substance present in the system (phase of interest). Thus, the number of moles of
each component become independent variables, in addition to P and T:
N

dG t V t dP S t dT i dni
i 1

ni
t

nG

ni

T , P ,n j ' s

T , P ,n j ' s

This new defined property is called the chemical potential for component i in a
mixture.
At equilibrium, the temperature and pressure must be the same in all phases, for
thermal and mechanical equilibrium considerations (i.e., no driving forces to cause
fluxes of heat or fluid movement).
Consider a system containing two phases (vapor and liquid, V and L) at
temperature T and pressure P. Each phase is an open system, because it can
exchange energy and mass with the other phase. The entire system is considered
to be isolated from the surroundings.
In the vapor and liquid phases we can write the following fundamental property
relations

d G

dP S

d Gt

Vt

dP S t

dT Vi dniV

dT iL dniL

We can add these to get the total change in Gibbs free energy for the entire system
dG t V t dP S t dT Vi dniV iL dniL

But, since this is a closed system, the last two terms must sum to zero. Also, any
mass leaving one phase must enter the other.

V
i

dniV iL dniL 0

dniV dniL

V
i

iL dniV 0

Since the dn's are arbitrary independent variables, we conclude that

Vi iL

i 1,2,3,...., N

This can be expanded to any number of phases.

Thus, in addition to thermal and mechanical equilibrium, the chemical potential for
any given component must be the same in all phases at equilibrium.
This is phase equilibrium (i.e., no driving forces for diffusion).
At equilibrium in a system of phases and N components,

i i .... i

i 1,2,...., N

Thus, we have derived the phase equilibrium relations without any new concepts
being introduced, in addition to the 1st and 2nd laws.
Fugacities
Our problem with chemical potentials is that we have no real feelings about how
they behave.
Thus, it is traditional to throw them away, in favor of another defined property,
fugacity.
i io RT ln

fi
f o
i

fi Pyi

as

P0

The hat over the symbol for fugacity means for a component (i) in a mixture. For
pure fluids, the hat is left off. In this expression, both chemical potentials are at the
same temperature (T), thus, so are the fugacities. The superscript o means in
some arbitrarily defined standard state.

For an ideal gas mixture, fugacity is equal to partial pressure. This is at least some
progress! We know about ideal gases, and both P and yi are measurable
properties.
In terms of fugacities, the phase equilibrium relations do not change:
fi fi ...... fi

i 1,2,...., N

Thermodynamic Properties of Mixtures

Ideal gas mixtures

Py
H y H
S y S R y ln y
G y G RT y ln y
P

Ideal solutions
V xiVi

H xi H i

S xi S i R xi ln xi

G xi Gi RT xi ln xi

i Gi RT ln xi
f f x
i

Thus, ideal solutions exhibit no volume change on mixing and no heat of

mixing.
Read Liquid Mixtures -- Partial Molar and Excess Properties
Partial molar properties are defined by
nM

ni

Mi

T , P ,n j

Thus, the partial molar Gibbs free energy is the chemical potential:
nG

ni

Gi
T , P ,n j

Excess properties are defined by

M E M M id
where the ideal solution value is at the same T , P, and composition as the
actual mixture.
Thus, the volume and enthalpy of a real mixture can be calculated from the
excess volume and excess enthalpy by the following:
V V id V E xiVi V E

H H id H E xi H i H E

Enthalpies of real liquid mixtures are also represented by data on heats of

solution, or graphically on H-x diagrams (see Sec. 12.4, p. 442).
Fugacities in Mixtures - Ideal Behavior
Gas Phase -- Ideal Gases
fiV Py i

Liquid Phase -- Ideal Solutions

fi L f i L xi

The coefficient on the RHS is the fugacity of the pure liquid at the same
T and P as the actual liquid mixture.
Below, we will find that it is closely approximated by the vapor pressure of
component i at temperature T.
The above relation is called the Lewis/Randall rule (see p. 401 in text).

Fugacities in Mixtures - Real Gas and Liquid Behavior

Gas phase fugacity coefficients
fiV Pyi Vi
V 1 as
i

P0

ln i

n Z 1

ni

P ,T ,n j

dP
P

Liquid phase activity coefficients

fi L f i L xi i

Vi L ( P Pi sat )

RT

f i L Pi sat isat exp

Henry's law approach for dilute components

The activity coefficient can be very large near infinite dilution for a
component (f-x slope quite different).
fi L k i xi
k i f i L i

This can be taken as the ideal dilute solution (Henry's law), and corrected
with a different activity coefficient:
fi L k i xi i HL

i HL

i
i

The liquid-phase activity coefficients can be related to the excess Gibbs free
energy

Gi Gi

id
i

Gi E RT ln

id

fi L
RT ln L
RT ln
f i xi

It can also be shown that the following hold

G E RT xi ln

x d ln
i

at

const . T , P

The first of these equations is used to calculate excess Gibbs energies from
VLE data.

The latter is used to test VLE data for thermodynamic consistency.

Fugacities in Liquid Mixtures - Empirical Relations
Empirical equations are often used to fit excess Gibbs free energy as a function of
composition.
GE
x1 x 2 A21 x1 A12 x 2
RT
ln 1 x 22 A12 2 A21 A12 x1

Margules:

ln

x A
2
1

21

2 A12 A21

x
2

Note that the constants are equal to the limiting values of the logrithms of the
activity coefficients for the Margules equations.

Redlich-Kister:

GE
x1 x 2 A B x1 x 2
RT
ln 1 ?
ln 2 ?

Note that the Redlich-Kister equation is identical to the two-suffix Margules

equations given above:
GE
A x1 x 2 B x1 x 2
RTx1 x 2
A B x1 A B x 2

A21 A B
A12 A B

***********************************************************
Discuss the VLE data for MEK(1)+Toluene(2) -- Table 12.1, Figs. 12.2-3,
pp. 417-8. Draw a picture of the system. This system exhibits positive deviations
from Raoult's law.
Class exercise: Determine A12 and A21 from these data.
Class exercise: Derive the activity coefficient expressions for these data.
Discuss the VLE data for Chloroform(1)+1,4-dioxane(2) -- Table 12.3, Figs. 12.6,
pp. 425-6. This system exhibits negative deviations from Raoult's law.

Class exercise: Determine A and B from these data.

*************************************************************
Phase Equilibrium - Raoult's Law
Consider two phases, vapor and liquid, where the gas phase is an ideal gas
mixture, and the liquid phase is an ideal liquid solution.
The phase equilibrium relations become
fiV fi L

i 1,2,...., N

Pyi f i x i
L

Assume that the effect of pressure is negligible on the pure liquid fugacity, so that
it can be evaluated at the vapor pressure for component i rather than at P.

f i L P, T f i L Pi sat , T

Since we are assuming that the gas phase behaves like an ideal gas, and since the
mole fraction of component i is unity

f i L Pi sat , T f iV Pi sat , T Pi sat

Substituting this above, gives Raoults law:

Pyi Pi sat xi

If the assumption of ideal liquid solutions is relaxed, but all other assumptions
remain, then the Modified Raoults law is obtained:
Pyi Pi sat xi i

Basis for DePriester Charts for Light Hydrocarbons

In general, the expressions for K-values are

Vi L P Pi sat
yi
P sat isat i

i
exp
xi
RT
P Vi

Ki Ki P , T , y , x
Ki

Assume ideal solutions in both phases

Vi L P Pi sat
yi
P sat sat
i Vi exp
xi
RT
P i

Ki Ki P , T
Ki

This is the basis for the DePriester Charts (pp. 356-7).

Equations of State for K-values
In modern practice, VLE calculations for light-hydrocarbon systems are done using
computer calculations based on equations of state, such as the Soave-RedlichKwong (SRK) equation or the Peng-Robinson (PR) equation.
In this approach, fugacity coefficients are used to express the fugacity of both the
liquid and vapor phases relative to the ideal gas.
The following phase equilibrium relations result:
Pyi Vi Pxi iL
L
Ki Vi

The same equation of state is used to evaluate the two fugacity coefficients, which
are functions of (T, P, xis) and (T, P, yis), respectively.