Physical Chemistry II

School of Chemical Science and Engineering

Phase Equilibrium
 Heterogeneous
Phase Equilibrium
System
Two or more phases
1,2…, π
are phases Each phase corresponds to a
Homogeneous Open Systems
Thermal
Equilibrium
Mechanical The conditions for which the Heterogeneous
Equilibrium System is in a State of Internal Equilibrium
have to consider equilibrium with respect:
Chemical
or Mass Heat Transfer
Equilibrium Boundary Displacement
Mass Transfer
 •  It does not undergoes any tendency to depart spontaneously,
having in mind certain permissible changes or processes, i.e.,
heat transfer, work of volume displacement and, mass transfer
(for open systems) across a phase boundary.
•  The properties are independent of time and of previous history
Equilibrium of the system.
State •  They are stable, that is, not subject to "catastrophic” changes
on slight variations of external conditions.
•  We distinguish an equilibrium state from a steady state, insisting
that in an equilibrium state there are no net fluxes of the kind
under consideration (heat transfer, etc.) across a plane surface
placed anywhere in the system.
Phase Equilibrium Phase equilibrium of a Heterogeneous System considers
internal equilibrium with respect to three processes:

1.  Heat transfer between any two phases within

the heterogeneous system.

2. Displacement of a phase boundary.

3. Mass transfer of any component in the system

across a phase boundary.

The potential for the third process, is

The governing potentials in the first
two processes are temperature and
pressure, respectively, and we assume
prior knowledge of their existence
considered not to be known a priori, and it
is one of the prime responsibilities of
classical ther modynamics of phase
equilibria to "discover” and exploit the
appropriate "chemical potential”.
Phase Equilibrium

The function μi is an intensive quantity and we expect

it to depend on T, P, and composition of the system.

The most important or common

expression for μi
⎛ ∂M ⎞
M i ≡ ⎜⎜ ⎟⎟
⎝ ∂ni ⎠T ,P,n j≠i
Partial Molar Gibbs Energy
 ⎛ ∂M ⎞ Represents the change in the total property M due
M i ≡ ⎜⎜ ⎟⎟ to the addition of a differential quantity of species i
(at constant T and P) to a finite amount of solution
⎝ ∂ni ⎠T ,P,n j≠i
“Partial Molar Quantities” are defining for
choosing T and P as independent variables
⎛ ∂V ⎞
For the case of Volume, the partial molar volume can be expressed by: vi ≡ ⎜⎜ ⎟⎟
⎝ ∂ni ⎠T ,P,n j≠i

To evaluate the volume

change of the solution it is
Δnw
necessary to consider:

Equimolar mixture ΔV ≠ vw Δnw

Vmix H2O and methanol Vmix
Molar Volume Mole of H2O
T, P T, P Pure H2O at T,P added
 This is because the effective molar volume of H2O added in the
ΔV ≠ vw Δnw solution is less than the molar volume of pure H2O at the same T,P
Molar Volume Intermolecular
Mole of H2O
Forces
of Pure H2O of
T,P
added vw ≠ vw
Packing degree

Increase in the volume of the

solution when H2O is added
ΔV = vw Δnw
The properties of species i in the original
equimolar solution should be based on
Partial Molar Volume of ΔV data for a solution to the given composition
H2O in solution vw =
Δnw
In case the solution consists of pure H2O
⎛ ΔV ⎞ ⎛ dV ⎞
vw = lim ⎜⎜ ⎟ = ⎜⎜ ⎟⎟ vw = vw
Δnw →0 Δn ⎟
⎝ w ⎠T ,P,na ⎝ dnw ⎠T ,P,na
dV = vw Δnw
 For Ideal Gases
At constant T, the change in the abstract
thermodynamic quantity μ is a simple log
function of pressure !!!

For include systems non-ideal, Lewis

generalized this equation in terms on:
f è fugacity

•  It comes from the Latin for the “fleetness”

in the sense of “escaping tendency”
•  It has the same dimensions as pressure
•  It is a “corrected pressure” due to non
idealities that can be interpreted by
molecular interactions
μ0 (or f0)
Is arbitrary.
Both may not be chosen independently.
When one is chosen, the other is fixed.
 Rault’s Law Henry’s Law
For the Liquid – Vapor Equilibrium
(Ideal-dilute solution) y A P = x A PAS yB P = xB K B

Lewis Fugacity Rule

f1V = y1 f pure,1
V
f1L = x1 f pure,1
L

How is the relationship between fugacity of a

f AV = f AL
component and the measurable quantities such
as temperature, pressure, and composition?

For any substance, most thermodynamic properties of interest in Phase

Equilibrium can be calculated from Thermal and Volumetric Measurements
It is useful to express a thermodynamic function of a
substance relative to that which the same substance Residual Functions
has as an ideal gas at the same temperature and
composition and at some specified pressure or density.

M R = M − M IG
R IG R IG The mathematical
G T ,P
= GT ,P − G T ,P V =V −V formalism of the excess
functions is analogous to
that of residual functions.
Residual Gibbs Energy Residual Volume

Liquid solutions are preferably treated by the properties

that measure their deviations, not from the behavior of Excess Functions
an ideal gas, but from the behavior of an ideal solution
Thermodynamic Properties with Independent Variables P and T
P
µio = hio − Tsio
o fi ⎡ RT ⎤
µi − µ = RT ln o = ∫ ⎢vi −
i ⎥dP + RT ln( yi P) Reference Value
fi Po ⎣
P ⎦ Standard State Value

fi P⎡
RT ⎤ f o = 1bar
RT ln f i − RT ln( yi P) = RT ln = ∫ ⎢vi − ⎥dP
yi P P o ⎣ P ⎦

fi For a mixture of Ideal Gas

Fugacity Coefficient φ≡
yi P φ =1
P
⎡ RT ⎤
RT ln φ = ∫ ⎢vi − ⎥dP Allow to calculate Thermodynamic Properties
Po ⎣
P ⎦ of interest for any substance if F is known

For calculate this integral it is required the volumetric V = F(T , P,n1 ,n2 ,...,nm )
information in the function F for all interval of P Equation of State
For a Pure Component For a component in a mixture

f P ⎡ RT ⎤ fi P⎡
RT ⎤
RT ln φ = RT ln = ∫ ⎢v − ⎥dP RT ln φi = RT ln = ∫ ⎢v − ⎥dP
P Po ⎣ P ⎦ yi P P o ⎣ i P ⎦

f P⎡ v 1⎤ P⎡
Pv RT −1⎤
ln = ∫ ⎢ − ⎥dP = ∫ ⎢ ⎥dP V = F(T , P,n1 ,n2 ,...,nm )
P P o ⎣ RT P ⎦ Po ⎣
P ⎦
It is necessary to know the relation of V
with independent variables through
f P ⎡ z −1⎤ the function F
ln = ∫ ⎢ ⎥dP
P Po ⎣ P ⎦ Analytical Function Tabulated (limited )
(only for a limited class volumetric data
of substances and for
Compressibility Factor
limited conditions)
Equation of State
Thermodynamic Properties with Independent Variables V and T

∞ ⎡⎛ ⎞ ⎤
fi ∂P RT
RT ln φi = RT ln = ∫ ⎢⎜⎜ ⎟⎟ − ⎥ dV − RT ln z
yi P V ⎢⎣⎝ ∂ni ⎠T ,V ,nj≠i V ⎥⎦

For a pure component i

∞⎡
⎛f⎞ P RT ⎤
RT ln φ pure,i = RT ln ⎜ ⎟ = ∫⎢ − ⎥ dV − RT ln z + RT (z −1)
⎝ P ⎠ pure,i V ⎣ ni V ⎦

Equation of State of van der Waals

P = F(T ,V ,n1 ,n2 ,...,nm )
Most equations of state are pressure
explicit rather than volume explicit
Equation of State of Redlich-Kwong
Equation of State of Soave-Redlich-Kwong
…..
Exercise 1 Phase Equilibrium for a Single Component System
Specific Properties for Saturated Water

Show that a mixture of saturated liquid water and saturated water vapor at 120ºC
satisfies the phase equilibrium criterion.
Exercise 1.b

Specific Properties for Saturated Water

Show that a mixture of saturated liquid water and saturated water vapor at 300 kPa
satisfies the phase equilibrium criterion.
Exercise 1.c Specific Properties for Saturated Refrigerant 134a

Show that a mixture of liquid and vapor saturated with refrigerant 134a at -20°C satisfies
the phase equilibrium criterion.
Exercise 2
In a laboratory the need arises to prepare 2000 cm3 of an antifreeze consisting of a solution of
30 % (mol) methanol in water. What volumes of pure methanol and pure water at 25°C should
be mixed to to form 2000 cm3 of antifreeze, also at 25ºC?
The partial molar volumes for methanol and water in a methanol solution at 30 % (mol) at 25ºC
are: v
metOH = v1 = 30.632 cm /mol
3
For the pure species: vmetOH = v1 = 40.727 cm3/mol
vH2O = v2 = 17.765 cm3/mol vH2O = v2 = 18.068 cm3/mol

Exercise 3
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented by the
equation
(
H = 400x1 + 600x2 + x1 x2 40x1 + 20x2 )
where H is in J/mol. Determine:
•  the expressions for H1 and H2, as functions of x1
•  the numerical values for the enthalpies of the pure species, H1 and H2, and
•  the numerical values for the partial enthalpies to infinite dilution H1∞ and H2∞.
Exercise 4
Consider a mixture of m gases and assume that the Lewis fugacity rule is valid for this mixture.
For this case, show that the fugacity of the mixture fmixt is given by
!
!!
!!"#$ = !!"#$,!
!!!
where yi is the mole fraction of component i and fpure,i is the fugacity of pure component i at
the temperature and total pressure of the mixture.

Exercise 5
A binary gas mixture contains 25 mol% A and 75 mol% B. At 50 bar total pressure and 100°C
the fugacity coefficients of A and B in this mixture are, respectively, 0.65 and 0.90. What is
the fugacity of the gaseous mixture?
Exercise 6
At 25°C and 1 bar partial pressure, the solubility of ethane in water is very small; the equilibrium
mole fraction is xC2H6 = 0.33x10-4.
What is the solubility of ethane at 25°C when the partial pressure is 35 bar?
At 25°C, the compressibility factor of ethane is given by the empirical relation:

! = 1 − 7.63×10!! ! − 7.22×10!! !!
where P is in bar. At 25°C, the saturation pressure of ethane is 42.07 bar and for water it is
0.0316 bar.
 The vapor pressure diagram of a carbon
disulfide/dimethoxymethane solution at 25°C

Positive Deviation from Raoult’s Law behavior

It occurs because CS2 / CH3OCH3OCH3 (DMM)
are more repulsive than either CS2-CS2 or DMM-
DMM interactions.
The vapor pressure diagram of a
trichloromethane/acetone solution at 25°C

Negative Deviation from Raoult’s Law behavior

It is due to stronger unlike molecule interactions
than like-molecule interactions
Exercise 7
Oil reservoirs below ground frequently are in contact with underground water and, in
connection with an oil drilling operation, you are asked to compute the solubility of water in a
heavy oil at the underground conditions. These conditions are estimated to be 140°C and 410
bar. Experiments at 140°C and 1 bar indicate that the solubility of steam in the oil is x1 = 35x10-4.
Assume Henry's Law in the form f1 = H(T)x1 where H(T) is dependent only on the temperature,
and f1 is the fugacity of H2O. Also assume that the vapor pressure of the oil is negligible at 140°C.

Specific Properties for Compressed Liquid Water

Exercise 8
A certain cryogenic process is concerned with an equimolar mixture of argon (1) and
ethane (2) at 110 K. To design a separation process, a rough estimate is required for the
enthalpy of mixing for this liquid mixture. Make this estimate using the equation of state of
van der Waals with the customary mixing rules,
!/!
!!"#$ = !! !! and !!"#$ = !! !! !!" , with !!" = !! !! 1 − !!"
! ! !

Assume that: !!"#$ = !! !! and, because pressure is low, that ∆ U = ∆ H, where U is

mix mix
!
the internal energy and H is the enthalpy. Data are:
Exercise 9
Calculate the pressure of steam at a temperature of 500°C and a density of 24 kg/m3
using:
(a) The Ideal Gas Equation
(b) The van der Waals Equation
(c)  The Redlich-Kwong Equation
(d) The compressibility factor
(e)  The steam table.

van der Walls Equation Redlich-Kwong Equation

RT a RT a
P= − 2 P= −
v−b v v − b v v + b T 0.5
( )
van der Waals Equation Redlich-Kwong Equation