CHE-201: Introduction to

Chemical Engineering

Chapter 6: Multiphase Systems

By:
Dr. Nabeel Salim Abo-Ghander
Introductory Statement:

A Phase is a state of matter.

Do you believe that:

All chemical processes involve
operations in which material is
transferred from one phase (gas, solid,
liquid) to another.
Examples on Multiphase Systems:

1. Brewing a cup of Coffee

2. Removal of Sulfur dioxide from a gas stream.
3. Recovery of Methanol from an aqueous Solution.
4. Separation of paraffinic and aromatic compounds.

There are other systems which can be looked at!

Brewing a cup of Coffee (leaching):

+ =
Removal of Sulfur dioxide from a gas stream
(Scrubbing):

2 SO2 g O2 g 2 SO3 g

SO3 g H 2O l H 2 SO4 aq
Separation:
Rate of transportation:

A species transfers from one phase to another until the

second phase is saturated, i.e. holding as much as it can
hold at the prevailing process condition. When the
concentration of all species in each phase no longer change
with time, the phase are said to be in phase equilibrium.

http://www.youtube.com/watch?v=gbUTffUsXOM
Phase Diagram:

Phase diagram of a pure species is defined as a plot of one system

variable versus another showing the conditions at which the

substances exist as a solid, a liquid and a gas.

Phase Diagram:

rv e
m Cu
Equil iquid
ibriu
-L
Solid
po r ve
-Va Cur
or u id m
p Liq ibriu
id -Va um
l
So ilibri u il
u Eq
Eq ve
r
Cu

Crossing Phases doesnt occur instantaneously but

gradually in which the substance passes through three

main stages, i.e. phase 1, phase 1 & 2, then phase 2.

Main points on the phase diagram:
Normal boiling point temperature is the point at

which liquids start to boil at one atmospheric

pressure.

Triple point is the point at which the three phases,

i.e. solid, liquid and vapor coexist in equilibrium.

Critical temperature is the temperature at which

a substances cant coexist in two phases

whatever pressure is applied.

6.1b Estimation of Vapor Pressures:

Vapor pressure is the equilibrium pressure of the vapor above its liquid.

It indicates the tendency of a species to transfer from one phase to

another.
Volatility of a species is the degree to which the species tends to
transfer from liquid (or solid) to state to the vapor state.
Four methods can be used to estimate the component vapor pressures:

1. Vapor pressure tables in references

2. Clapeyron equation.

3. Cox chart.

4. Antoine equation.
Clapeyron equation:
It is an empirical equation given as:

dp H


v
dT T Vg Vl
Where:

p vapor pressure of pure substance

T absolute temperature

Vg , Vl specific molar volumes of vapor and liquid

H v latent heat of vaporization

Clapeyron equation (Cont.):
At low pressure,
Vl 0.0 Vg Vl Vg and substitutingVfor
g
from
ideal gas low yields the Clausius-Clapeyron equation:
dp * H v dT
*

p R T2

d ln p *

H v
d
1
T
R

H v 1

ln p *

R T
B
It is a straight line equations where a minimum of one
point is needed to obtain the value of B.
Example 6.1-1: Vapor Pressure Using
the Clausius-Clapeyron Equation:
The vapor pressure of benzene is measured at two
temperatures, with the following results:

T 1 7.6o C p1* 40 mmHg

T 2 15.4o C p2* 60 mmHg

Calculate the latent heat of vaporization and the parameter B

in the Clausius-Clapeyron equation
p* and then estimate at
42.2oC using this equation.
Cox Plot:
Antoine Equation:

It is an empirical equation expressed as:

log10 p * A
B
T C
where:

A, B, C are constant picked up from references

Table of Constant (Table B.4):
 6.2 The Gibbs Phase Rule:

V A V
A
A

A L L
A A
A A A
A
A A

At the beginning of contact, different T, P, At equilibrium, T, P,

and mass or molar composition and no driving forces for
mass or molar between
phases
6.2 The Gibbs Phase Rule (Conti):
Variables can be divided into:

1. Extensive variables: depend on the system

size. Examples, mass and volume.

2. Intensive variables: dont depend on the

system size. Example, temperature,
pressure, density, mole fractions, mass
fractions.
6.2 The Gibbs Phase Rule (Cont.):
To correctly specify a system, only intensive variables are
considered, mainly temperature, pressure and mole or mass
fractions.
The number of intensive variables which should be specified
for a given system at equilibrium is calculated for nonreactive
system by: DF 2 c

where: DF
: Degree of freedom
c
: Number of chemical species

: Number of phases in a system at equilibrium
Example 6.2-1: The Gibbs Phase
Rule
Determine the degree of freedom for each of the
following systems at equilibrium. Specify a feasible
set of independent variables for each system.

1. Pure liquid water.

2. A mixture of liquid, solid, and vapor water.

3. A vapor-liquid mixture of acetone and

methyl ethyl ketone.
 6.3 GAS-LIQUID SYSTEMS: ONE
CONDENSIBLE COMPONENT

w w w

w w
DF 2 2 2 2
w w
w
w
w
w
w w

Dry Air at T=75oC and 760 mm Hg Dry Air at T=75oC and 760 mm Hg
In contact with liquid water
Eventually equilibrium is established between the two phases.
Separation processes involving single condensable components

are: evaporation, drying, humidification, condensation, and

dehumidification.
Separation Processes:
Evaporation:
Liquid water
Liquid water
Evaporator Water vapor

Transfe
Drying: r of
Dried solids Liquid
Wet solids into
Dryer Water vapor Gas
phase
Humidification:
Dry air
Humidified air
Liquid water Humidifier
Separation Processes:

condensation and dehumidification:

Transfer
of
compone
Liquid water nt from
Wet air Condenser
Gas to
or Air of less water
Dehumidifier Liquid
phase
Raoults Law, Single Condensable
Species
w w w

w w

w w
w w
w
w w w

If a gas at temperature T and pressure P contains vapor whose mole

fraction is yi (mol vapor/ mol total gas), and if this vapor is the only
species that would condense if the temperature were slightly lowered,
then the partial pressure of the vapor in the gas equals the pure-
component vapor pressure at the system temperature:
pi yi P pi* T
Raoults Law, Single Condensable Species:
 Example 6.3-1 Composition of a
saturated Gas-Vapor System

Air and liquid water are contained at

equilibrium in a closed chamber at 75 oC
and 760 mm Hg, calculate the molar
composition of the gas phase.
Table B.3 in Appendix B: Vapor Pressure of
Water
Remarks on Equilibrium Concept:
A gas in equilibrium with a liquid must be saturated with the
volatile components of that liquid.
The partial pressure of a vapor at equilibrium in a gas
mixture containing a single component cant exceed the
vapor pressure of the pi pure
pi* T component at the system
temperature. If , the vapor is saturated; any
attempt to increase either by adding more vapor to the gas
phase or by increasing the total pressure of the system at
constant temperature, will lead to condensation.
A vapor present in a gas in less than its saturation amount is
referred to as a superheated vapor. For such a vapor,
pi yi P pi* T

Achieving the condensation required changing the system

conditions till equilibrium is maintained, then either the
pressure is increased at constant temperature or the
temperature is lowered at constant pressure.
Remarks on Equilibrium Concept:

If a gas containing a single superheated vapor is cooled at

constant pressure, the temperature at which the vapor
becomes saturated is referred to as the dew point of the
gas:
pi yi P pi* Tdp

Degree of superheat of a gas is the deference between the

temperature of the gas and the dew point.
Equilibrium Concept:

A w
A w A w w w
A A A
w w
A A A w
A w A w w A A
A A w w
A A A
w w w w A w

w w w w w w w w w w w w w w w
w w w w w w w w w w w w w w
w w w w
w w w w w w w w w w w
w
w w w w w w
w w
w w w w w w w w w w w w w w
w w

Beginning of contact Air with Air saturated with vapor

between the Phases superheated vapor
pH 2O 0.0 mm Hg pH 2O y H 2O P pH* 2O T p H 2O y H 2O P p H* 2O T
Example 6.3-2 Material Balances
Around a Condenser
A steam of air at 100oC and 5260 mm Hg contains 10.0% water by

volume.

1. Calculate the dew point and degrees of superheat of the air.

2. Calculate the percentage of the vapor that condenses and the

final composition of the gas phase if the air is cooled to 80oC at

constant pressure.

3. Calculate the percentage condensation and the final gas-phase

composition if, Instead of being cooled, the air is compressed

isothermally to 8500 mm Hg.

4. Suppose the process of part 2 is run, the product gas is analyzed,

and the mole fraction of water differs considerably from the

Table B.3 in Appendix B: Vapor Pressure of
Water
Terminologies in Humidification:

Relative Saturation (Relative Humidity):

pi
sr hr 100%
pi* T
Molal Saturation (Molal Humidity)
pi moles of vapor
sm hm
P pi moles of vapor free ( dry ) gas
Absolute Saturation (Absolute Humidity):
pi M i mass of vapor
sa ha
P pi M dry mass of dry gas
Percentage Saturation (Percentage Humidity):

sr hr
sm

pi P pi
*
sm
100%
pi* P p 100%
*
i
Example 6.3-3:

Humid air at 75oC, 1.1 bar, and 30% relative

humidity is fed into a process until at a rate of 1000
m3/h. Determine:

1. The molar flowrate of water, dry air, and

oxygen entering the process unit.

2. The molal humidity, absolute humidity, and

percentage humidity of the air.

3. The dew point.

6.4 MULTICOMPONENT GAS-LIQUID
SYSTEMS

w w A w w
w w C A
A w
w w w A
A w C
w w A A w
A w w A
w w A
A w C
w w w A w C
A
w w A w

w w w w w
C w w w w
w w w w w C w w
w w w w C
w w w w
w w C w
w w w w
w
w w w w w C w w w C

Already discussed in 6.3 Will be discussed in 6.4

(Pure Liquid) (Liquid Mixtures)
pi yi P pi* T pi yi P xi pi* T
Remarks in Raoults Law:
General Raoults law for multicomponent mixtures is:

pi yi P xi pi* T
If the liquid mixture is a diluted one, i.e. , Raoults law can be
xi 0.0
reduced to:

Henerys Law: pi yi P xi H i T

H i Henerys
T constant of i in a specific solvent
If the liquid phase is a pure one, Raoults law can be reduced into:

pi yi P pi* T
Example 6.4-2: Raoults and Henerys Law

Use either Raoults law or Henrys law to solve the following problems:

1. A gas containing 1.0 mol% ethane is in contact with water at 20 oC and 20.0 atm.
Estimate the mole fraction of the disolved ethane.

2. An equimolar liquid mixture of benzene (B) and toluene (T) is in equilibrium

with its vapor at 30oC. What is the system pressure and the composition of the
vapor.
Newton Method:
It is used to find zero(s) of nonlinear equation(s) starting from (an) initial guess(es).

The problem is: find the value(s) of x making f x equals to zero starting from x
n 1

xn 1
Any function can be expanded by Taylors series into:
1
f xn 1 f xn xn 1 xn f xn xn 1 xn 2 f xn ..........
2

f xn 1
Eventually, the value of should reach to zero.
the correction formula for the guess is obtained after cancelling the higher order
terms as:
xn 1 xn f xn / f xn
Newton Method Procedure:

1. Start with an initial guess x

o

2. Evaluate the values of the function f x and the first derivative

f x

3. Calculate the new updated value of x using:

x1 xo f xo / f xo

4. Check the value of the function at the new value x1

5. If the value is within a certain tolerance, stop

6. If not, keep on iterating.

Example on Newton Method:

Example: Find the value of 5 ?

Answer: we need to solve: f x x 2 5 0
Lets start with 2.5 as an initial guess. Then, the update formula can be
expressed as:

xn 1 xn
x 5
2
n
2 xn
x f(x) f(x)
xo 2.5 1.25 5.00
x1 2.25 0.0625 4.500
x2 2.23611111 0.0001929012 4.4722222222
1
x3 2.2360679 0.00000018
779
5
I will stop here as the value of the function is small
enough to accept the value of x. The value of from
the calculator is 2.2360679775.
6.4c Vapor-Liquid Equilibrium Calculations for Ideal
Solutions

It is very important to know conditions at which condensation or

evaporation occurs.
Bubble-point temperature is the temperature at which the first bubble is
formed at constant pressure. Liquid phase composition is given.

x p T P
n
*
i i bp
i 1
Dew-point temperature is the temperature at which the first droplet of
liquid is formed at a given pressure. Gas phase composition is given.

n
yi P
p T 1 *

Dew-point pressure is the pressure at which condensation occurs at

i 1 i dp

constant temperature
Example 6.4-3 Bubble- and Dew-Point Calculations

1. Calculate the temperature and composition of a vapor in equilibrium with a liquid that is
40.0 mole% benzene-60 mole% toluene at 1 atm. It the calculated temperature a bubble-
point or dew-point temperature?

2. Calculate the temperature and composition of a liquid in equilibrium with a gas mixture
containing 10.0 mole% benzene., 10.0 mole% toluene, and the balance nitrogen (which may
be considered noncondensable) at 1.0 atm. Is the calculated temperture a bubble-point or
dew-point temperature?

3. A gas mixture consisting of 15.0 mole% benzene, 10.0 mole% toluene, and 75.0 mole %
nitrogen is compressed isothermally at 80oC until condensation occurs. At what pressure
will condensation begin? What will be the composition of the initial condensate?
Problem 4.74