Chapter -6

Multiphase Systems
Multiphase separation processes
 Leaching
 Absorption
 Distillation
 Extraction
 Crystallization
 Single-Component Phase Equilibrium

Phase Diagram: a plot that shows conditions under which a pure substance exists in
a particular phase – e.g. a liquid, a solid, or a gas. Often, the y-axis indicates
pressure and the x-axis the temperature.

H2O

critical point

Solid
Phase
72.9 atm Super-critical (fluid) phase
Pc
Liquid * Terminology
triple Phase • Vapor Pressure
Phase Diag. CO2 point • Boiling Point
• Sublimation Pressure
Vapor Gas • Freezing Point
Phase • Triple Point

31°C
 Single-Component Phase Equilibrium

All transition temperatures (Tm, Tb, Ts, etc.) are functions of pressure
• To condense water: convert vapor to liquid by decreasing T, or increasing P
• To evaporate water: convert liquid to vapor by increasing T, or decreasing P
• To freeze water: convert liquid to solid by decreasing T, or increasing P
 Equilibrium
• Chemical equilibrium, the state in which the concentrations of the reactants and products have no net
change over time

• Diffusion equilibrium, when the concentrations of the diffusing substance in the two compartments
are equal

• Donnan equilibrium, the distribution of ion species between two ionic solutions separated by a
semipermeable membrane or boundary

• Dynamic equilibrium, the state in which two reversible processes occur at the same rate

• Equilibrium constant, a quantity characterizing a chemical equilibrium in a chemical reaction

• Solubility equilibrium, any chemical equilibrium between solid and dissolved states of a compound
at saturation

• Thermodynamic equilibrium, the state of a thermodynamic system which is in thermal, mechanical,

and chemical equilibrium

• Vapor-liquid equilibrium, where the rates of condensation and vapourization of a material are equal
 Single-Component Phase Equilibrium
Vapor-liquid equilibrium (VLE) curve: the locus of points for which liquid and vapor
can coexist.

Vapor pressure: the pressure of vapor when it is in equilibrium with the liquid or solid
phase. For a point (T,P) on the vapor-liquid equilibrium curve, P is the vapor pressure
of the liquid. For a point (T,P) on the solid-vapor equilibrium curve, P is
the vapor pressure of the solid.

Boiling point temperature: for a point (T,P) on the VLE curve, T is the boiling point
of the substance at the pressure P. The normal boiling point is the boiling point
temperature for P = 1 atm.

Freezing/melting point temperature: for a point (T,P) on the solid-liquid equilibrium

curve, T is the freezing (equivalently, melting) temperature of the substance at the
pressure P.

Sublimation point temperature: for a point (T,P) on the solid-vapor equilibrium

curve, T is the sublimation point temperature of the substance at the pressure P.

A vapour is a gaseous species below its critical temperature, and a gas is a species above its
critical temperature at a pressure low enough for the species to be more like a vapour than a
liquid (i.e., a density closer to 1 g/L than 1000 g/L)
• To condense water:
convert vapor to liquid
by decreasing T, or increasing P
• To evaporate water:
convert liquid to vapor
by increasing T, or decreasing P
• To freeze water:
convert liquid to solid
by decreasing T, or increasing P
 The Vapor Pressure of a Liquid
Vapor pressure is the pressure of a vapor in equilibrium with its non-
vapor phases. All liquids and solids have a tendency to evaporate
(escape) to a gaseous form, and all gases have a tendency to condense
back into their original form (either liquid or solid). Vapor
pressure

At any given temperature, for a particular substance, there is a

pressure at which the gas of that substance is in dynamic equilibrium
with its liquid or solid forms. This is the vapor pressure of that
substance at that temperature.
Liquid or
Dynamic equilibrium, the state in which two reversible processes occur at the same
solid rate

Volatility of a species is the degree to which the species tends to transfer from liquid (or
solid) state to vapor phase. Vapor pressure of a species is a measure of its volatility.

Estimation of Vapor Pressure

Clausius-Clapeyron Equation
Cox Charts
Antoine Equation 7
 Clausius-Clapeyron Equation
Estimation of Vapor Pressure

Clapeyron Equation

dP H v Enthalpy of Vaporization

dT TVˆ Volume change of Vaporization
(V(gas)-V(liquid))
d ln P* H v

d (1 / T ) R
Integration
H v
ln P  
*
B Clausius-Clapeyron Equation
RT
This equation can be used as fitting equation for vapor pressure data.

 p v   H v  1 1 
ln v      
 p1   R  T1 T 
 Cox charts:
These charts plot log p* vs T. The axes are scaled so as to make the plots come out linear.

Duhring plots
 Antoine equation:
Estimation of Vapor Pressure
An empirical but accurate equation for correlating p*(T) data. The equation has three
parameters (A, B, and C) that have been tabulated for many substances (e.g. see table
B.4 in the text):

Components Range of A B C
Temperature (T),
K
Acetone 241-350 21.5439 2940.46 -35.93
Ammonia 179-261 21.8407 2132.50 -32.98
Benzene 280-377 20.7934 2788.51 -52.36
Ethanol 270-369 21.8045 3803.98 -41.68
Methanol 257-364 23.4801 3626.55 -34.29
Toluene 280-410 20.9063 3096.52 -53.67
Water 284-441 23.1962 3816.44 -46.13
 The Gibbs Phase Rule
Extensive variables: Extensive variables depend on, and reflect, the size of a chemical
“system.” The system could be a liquid solution, for example.
Extensive variables include the total volume, the total mass, and the total energy
contained in the system, among others.

Intensive variables: Variables that do not depend on system size. Examples are
temperature, pressure, chemical potential, density, specific volume, viscosity, thermal
conductivity, mass fractions, mole fractions, among others.

Degree of freedom for intensive variables

F  2 m The number of phases at

equilibrium
The number of chemical species
The number of degree of
freedom
Assumptions: No reactions
 Gibbs Phase Rule - Examples

F  2 m
• Pure Water
F=2+1–1=2

• Mixture of Ice and liquid water and water vapor

F=2+1–3=0

• VLE of acetone + nitrogen

F = 2 + 2 –2 = 2

Other intensive variables can be calculated using thermodynamic relations

 Examples of vapor pressure
1. The vapor pressure of 1-propanol is 10.0 torr at 14.7 °C. Calculate the vapor pressure at
52.8 °C. Given: Heat of vaporization of 1-propanol = 47.2 kJ/mol

ln[10 torr/PT2,vap] = (47.2 kJ/mol/0.008314 kJ/K·mol)[1/325.95 K - 1/287.85 K]

ln[10 torr/PT2,vap] = 5677(-4.06 x 10-4)
ln[10 torr/PT2,vap] = -2.305  p v   H v  1 1 
ln v      
take the antilog of both sides 10 torr/PT2,vap = 0.997  p1   R  T1 T 
PT2,vap/10 torr = 10.02
PT2,vap = 100.2 torr
Single Component system
 Solid/Liquid/Gas
 Ideal and Non-Ideal Gas
 Phase Diagram
 Vapor Pressure

Gibbs Phase Rule

 Solid/Liquid/Gas
 Raoult’s Law
Gas-liquid systems with a single condensable component
• Ideal solution: mixture whose properties can be calculated based on the knowledge of
the corresponding properties of the pure components and the composition of the solution
Assumptions:
• molecules are similar in size
• molecules have similar intermolecular interactions

If i is the condensable component, then at equilibrium the partial pressure of i in the gas
mixture must equal the vapor pressure of the pure i liquid. This is called Raoult’s Law. In
equation form,

Where
• P is the total pressure
• pi is the partial pressure of species i
• Pi*(T) is the vapor pressure of species i at T
• Raoult’s Law applied when the mole fraction in the liquid phase approaches unity, or for solutions
very similar in chemical nature; relates the partial pressure with the mole fraction in the liquid
phase
 Example of Raoult’s Law
What is the change in vapor pressure when 164 g of glycerin (C3H8O3) is added to 338
mL of H2O at 39.8 °C.

The vapor pressure of pure H2O at 39.8 °C is 54.74 torr

The density of H2O at 39.8 °C is 0.992 g/mL.

Solution:

164 g of glycerin =1.78 mol

338 mL of H2O = 18.63 mol

Χwater = nwater/(nwater + nglycerin) = 1.78/(1.78+18.63) = 0.91

Pwater = ΧwaterP0water = 0.91 x 54.74 torr = 49.8 torr

Change in pressure is Pfinal - PO

Change = 49.8 torr - 54.74 torr

change = -4.94 torr

Some Useful Definitions

Saturation – refers to any gas-vapor combination

Humidity – specific to air-water system

Saturation
Saturation
Relative Saturation and Relative Humidity
Molal Saturation and Molal Humidity

Note:
[ni/ni-freegas]actual = [pi/(P-pi]actual and
[ni/ni-free gas]sat = [pi/(P-pi)]sat
 Multi-component systems

These are systems or processes in which gas and liquid phases that contain multiple
chemical species are brought into contact. One usually wants to know how each
chemical species distributes itself between the phases; e.g. in order to design a liquid-
liquid extraction process you would need to know to what extent the solubility of the
extract species varies between the two liquid phases (you want its solubility to be high
in the extract phase, and low in the raffinate phase).
To determine the compositions of phases in equilibrium, one can resort to tabulated
data (if available) or to calculations based on phase-equilibrium thermodynamics.
 Raoult’s Law
Saturation: A phase at equilibrium is saturated with a chemical species if it holds as
much of the species as it maximally can. For example, air at a given temperature and
pressure will only hold so much water vapor. If more water vapor were somehow
introduced into the air, condensation would occur and the extra water vapor would
come out of the air as liquid water. When a gas that is saturated with a species A is in
contact with a liquid of pure A, the rate at which molecules of A evaporate from the liquid
into the gas equals the rate at which molecules of A from the gas condense into the liquid.
On the other hand, if the amount of A in the gas is below saturation, the evaporation rate
of A will be greater than its rate of condensation. This will continue unless the gas
becomes saturated with A and equilibrium is established, at which point the two rates
(evaporation and condensation) would become equal. Note that a liquid species that
evaporates is referred to as being volatile, one that does not is nonvolatile.
 Raoult’s Law for multi-component gas-liquid systems

Given a liquid solution (note: we no longer have a pure liquid as in the

“single-condensable species” scenario) with one or more volatile
components i, the partial pressure Pi in a gas that is in equilibrium with
the liquid is assumed to be given by

where P is the total pressure, yi is mole fraction of i in the gas phase, xi

is mole fraction of i in the liquid phase, and pi* is the vapor pressure of
pure liquid i. Note this equation is an approximation that has to work
well when xi approaches 1, i.e. when the liquid is almost pure i. It may
be reasonably accurate for certain mixtures over a larger range in
composition, e.g. if the liquid mixture consists of substances of similar
polarity and molecular weights.
 The Dry Bulb, Wet Bulb temperatures
• Dry Bulb Temperature - Tdb
– The Dry Bulb temperature, usually referred to as air temperature
– It is called "Dry Bulb" because the air temperature is indicated by a thermometer not affected by the
moisture of the air.
– Dry-bulb temperature - Tdb, can be measured using a normal thermometer freely exposed to the air but
shielded from radiation and moisture.

• Wet Bulb Temperature - Twb

– The Wet Bulb temperature is the temperature of adiabatic saturation. This is the temperature indicated by
a moistened thermometer bulb exposed to the air flow.
– The rate of evaporation from the wet bandage on the bulb, depends on the humidity of the air. The
evaporation is reduced when the air contains more water vapor.
– The wet bulb temperature is always lower than the dry bulb temperature but will be identical with 100%
relative humidity (the air is at the saturation line).

• Dew Point Temperature - Tdp

– The Dew Point is the temperature at which water vapor starts to condense out of the air (the temperature
at which air becomes completely saturated). Above this temperature the moisture will stay in the air.
– if the dew-point temperature is close to the dry air temperature - the relative humidity is high
– if the dew point is well below the dry air temperature - the relative humidity is low
 Ideal Solutions
A Solution is any homogeneous phase that contains more than one component. These
components can’t be physically differentiated.

A Solvent is the component with the larger proportion or quantity in the solution. A Solute
is the component with the smaller proportion or quantity in the solution.

The idea of Ideal Solutions is used to simplify the study of the phase equilibrium for
solution. The solution is considered to be ideal when:
 its components are assumed to have similar structures and sizes, and when
 it represents complete uniformity of molecular forces (basically attraction forces).

30
 Relative volatility
• Relative volatility is a measure of the differences in volatility between two
components, and hence their boiling points. Ratio of pure component vapor
pressures

pA / xA y A / xA  ave x
 AB   AB  y
p B / xB y B / xB 1  ( ave  1) x

More volatile component Less boiling component Relative volatility

(normal boiling point oC) (normal boiling point, oC)

Benzene (80.1) Toluene (110.6) 2.34

Toluene (110.6) p-Xylene (138.3) 2.31

Benzene (80.6) p-Xylene (138.3) 4.82

m-Xylene (139.1) p-Xylene (138.3) 1.02

Pentane (36.0) Hexane (68.7) 2.59

Hexane (68.7) Heptane (98.5) 2.45

 Henry’s Law
 For a mixture of gases dissolved in a solution. Henry’s law can be applied
for each gas independently.

 The more commonly used forms of Henry’s law are:

P2 = k’ x2
P2 = k” c2

 The mass of a gas (m2) dissolved by a given volume of solvent at

constant T is proportional to the pressure of the gas (P2) above and in
equilibrium with the solution.

m2 = k 2 P 2

where k2 is the Henry’s law constant.

32
 Henry’s Law

where Hi(T) is Henry’s Law constant at T. It generally increases with increase

in temperature. More soluble, less H. At high pressures or for gases of high
solubility the law looses its validity. For amonia in water at 20oc, H = 2.7
atm/mol fraction.

Henry’s Law applies for dilute solutions of any compound i (i.e., xi ≈ 0);
relates partial pressure in the gaseous phase with the mole fraction in the
liquid phase. e.g., air dissolved in water
 Example of application of Henry’s Law
Example: How many grams of carbon dioxide gas is dissolved in a 1 L bottle of
carbonated water if the manufacturer uses a pressure of 2.4 atm in the bottling
process at 25 °C?

Given: H of CO2 in water = 1.65 x 10^3 atm/(mol fraction) at 25 °C

Solution:

Mole fraction of CO2 dissolved in water = x= p/H = 2.4/ (1.65*10^3)= 0.001452

Moles of CO2/moles of water =x /(1-x) = 0.00145
1 lit of water = 1000/18 = 55.55 moles
Therefore mole of CO2 dissolved = 0.00145*55.55 = 0.081 moles
= 0.081*44 = 3.553 gms
VLE-curve: Benzene-Toluene mixture
at 1 atmosphere
1

0.9

0.8 Equilibrium curve

Mole fraction of benzene in vapour, y

0.7

0.6

0.5

0.4

0.3
45o diagonal line
0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of benzene in liquid , x
 VLE in binary systems
• More than one component can be transferred from one phase to another
• Each phase may (or may not) contain some of each component
• Occurs in separation processes such as distillation, adsorption, stripping, and
scrubbing
VLE in binary system
Vapor-liquid Equilibrium Ratio
 Bubble-point and Dew-point Calculations

Bubble-point: If pure liquid i is heated its vapor pressure will rise. Eventually, the vapor
pressure of the pure liquid equals the external pressure P of the gas above it.

At this point, the liquid will start to boil – bubbles of pure i will form and the liquid will be at
its boiling temperature at the pressure P. As long as P remains constant, the boiling temperature
of the liquid will not change.

What happens if a liquid solution, containing multiple chemical species, is heated? Again,
eventually a temperature is reached at which bubbles start to form in the liquid solution and
boiling sets in. This temperature is called the bubble point temperature Tbp (in contrast to
boiling point temperature, which is for pure liquids).
• In the case of a liquid solution, the composition of the vapor in the bubbles that form is
not the same as that of the liquid. In fact, the vapor will be more enriched in the more
volatile components of the liquid, as you may suspect.

• In turn, this implies that as these vapor bubbles, enriched in the more volatile species,
transport molecules from the liquid to the gas above, the liquid left behind will become
progressively depleted in the more volatile species – the composition of the liquid will
change.

• As the liquid composition changes, so will the bubble point temperature. Thus, in contrast
to the boiling of a pure liquid, for which boiling occurs at a fixed T as long as P is fixed,
for a liquid solution Tbp changes as boiling proceeds because of the change in the liquid’s
composition.
 Calculation of bubble-point and dew-point temperatures and pressures

In general, calculation of bubble-point/dew point conditions is a complex task. However, the

task simplifies considerably if the composition of the liquid solution is in a regime in which
Raoult’s and/or Henry’s Laws apply (i.e. the solution behaves ideally).

To illustrate such a calculation, we will assume to have a liquid solution containing q volatile
species. We want to calculate its bubble-point when the external pressure of the gas above the
solution is P. At the bubble point, the sum of the vapor pressures from the q volatile species
must sum to P if vapor bubbles are to form. Moreover, the composition of the vapor bubbles
that form in the liquid can be assumed to be in equilibrium with the liquid, e.g. as given by
Raoult’s or Henry’s laws.
 For definiteness, we will assume the liquid solution follows Raoult’s law for each of
the q volatile species present. Then, the partial pressure Pi of species i in a vapor
bubble, formed at the bubble-point temperature Tbp, is

where xi is the mole fraction of i in the liquid solution, and where we explicitly
indicated that the vapor pressure pi* is to be evaluated at the bubble-point temperature
Tbp. Then, at the bubble-point, we must have
Txy and Pxy diagrams: These diagrams are used to correlate bubble-point temperature
and bubble-point pressure data for binary (two-component) gas-liquid systems.
Examples for the benzene-toluene system are shown below.

 Txy diagram  Pxy diagram

T P
vapor liquid
Bubble P

V+L Dew T

Bubble T Dew P
V+L
liquid
vapor

x1 y1 x1 y
1

x or y x or y
 Solution of Solids in Liquids

Solubility: of a solid in a liquid is the maximum amount of that substance that can
be dissolved in a specified amount of the liquid at equilibrium.

A solution that contains as much of a dissolved species as it can is said to be

saturated with that species. A solution in equilibrium with solid solute must be
saturated with that solute; if it were not, more solute would dissolve.

Colligative Solution Properties.

 Equilibrium Between Two Liquid Phases

Miscibility and Distribution Coefficients.

Phase Diagram for Ternary Systems
Triangular Phase Diagram.

Tie Line.
 Adsorption on Solid Surfaces

 Adsorbent
 Adsorbate
 Adsorption isotherms
Some problems
Basis:
100 mole
product gas