CHG 2317

Introduction to Chemical
Process Analysis
Chapter 6
Multiphase Systems

Contents
 Terminology
 Phase diagram
 Vapor pressure estimation
 Gibbs phase rule
 V-L system
 Ideal solution
 V-L equilibrium calculations
 Solubility of solids in liquids
 L-L equilibrium
 Adsorption
 Example

2
 Phase Diagram
a. Triple point
b. Critical point (Tc, Pc): Tc is the highest temperature that a
liquid can exist and Pc is the liquid pressure under Tc

H2O Critical point

218

Liquid
P (atm)
Gas
Solid
Vapour
0.006
Triple point

273.15 647 T (K) 3

Phase diagram: a graph showing T and P at which L,

S, and V phases of a substance can exist
Propane

(Tc, Pc)

4
 Propane tank example:

When valve is closed and T is fixed,

Vapour/Liquid reach a dynamic
equilibrium  phase equilibrium;

The equilibrium vapour phase

pressure = saturated vapour
pressure under the given T;

Open the valve for BBQ  vapour is

being burned at a vapour phase
pressure < vapour pressure  liquid
propane replenishes it via
evaporation;
A: Triple point;
B: Pc, Tc;
AB: V-L equilibrium; EvaporationCondensation;

AD: L-S equilibrium; MeltingFreezing;

AC: V-S equilibrium; SublimationCrystallization; 5

Phase Diagram
 Tb: Under fixed P, heating liquid until it bubbles, the T is
called the boiling point of the substance under that P; if the
P is 1.0 atm, we call it normal Tb
 Tm@given P
 Tsub@given P Phase Diagram of Water

How could you

cook a potato at
the crest of
Mount
Himalaya?
(potato must go to
100oC)
6
Phase Diagram
Tb: T at which vapour bubbles form in liquid (Pvap = Phead space),
Example: Heating of a kettle of water

If P2 = 760 mmHg, Tb = 100oC;

If P2 = 5 mmHg, Tb ≈ 0oC;

If P2 = 1064 mmHg, Tb = 109oC

On Himalaya, altitude = 8848 m

P = 0.3 atm, and Tb = 40oC

No potato can be cooked!

7
Phase Diagram of Water

Vapour Pressure Estimation

1. Why do we need vapour pressure?
2. Volatility, principle of distillation ˆ
dp * H
Clapeyron equation (empirical):  v
3.
dT 
ˆ V
TVg
ˆ
l 
4. Clausius-Clapeyron equation (vapour ideal gas, H
independent of T):

d ln p * 
 Hˆ v  P  Hˆ v
ln T 1  
1 1
  
d 1 / T  R or  PT 2  R  T2 T1 

5. Vapour Pressure Plots

 Reference-substance plot (P* vs. T)
 Cox chart (ln P* vs. T)
 Antoine equation: B
log10 p*  A 
T C
8
 Cox Chart

Vapour Pressure Example

The vapour pressure of benzene is measured at two temperatures, with the

following results: T1 = 7.6oC, p1 = 40 mmHg; T2 = 15.4oC, p2 = 60 mmHg.
Calculate the latent heat of vapourization and vapour pressure at 10oC using
the Cox chart.
Solution:
The slope of the line through the two data points on a plot of ln p vs 1/T is:
from B-C equation: d(ln p*)/d(1/T) = -H/R
 -H/R = {ln p*2 - ln p*1}/{1/T2 - 1/T1} = {ln (p*2/p*1) T1 T2}/{T1 - T2}
Plug in the numbers,
-H/R = {280.8 x 288.6 x ln(60/40)}/{280.8 - 288.6}
= -4213 K  H = 4213 K x 8.314 J/[mol.K] = 35,030 J/mol
(Note: The true value is 31,000 J/mol)

From the Cox chart, at a temperature of 10oC (i.e., 50F),

p*= 0.9 lbf/in2 = 0.9/14.7 x 760 mmHg = 46.5 mmHg
10
 The Gibbs Phase Rule

1. System variables:
 Extensive variables: Volume, mass
 Intensive variables: P,T, for each phase: xi, (i=1,2,…c), 

2. Gibbs Phase Rule

 System: Closed system with c components in  phases at
equilibrium, r independent reactions proceeding
 # of intensive system variables: (c-1)  +2 (i.e., P & T)
 # of equations in the system: (-1)c + r

 DOF = [(c-1)  +2 ] – [(-1)c + r] = 2 + C -  - r

11

Phase Rule cont…

 Comparison with DOF analysis in mass balances
 Similarity in definition of DOF
 Difference in system in question & type of variables
 Example:
 H2O pure liquid:

DF = 2 + c - P
 =2
1 1
 We must therefore specify two variables (T and P) to
completely define the system.
 A mixture of water in the form of ice, vapour and liquid
at equilibrium:
Triple point
DF = 2 + c - P
 =0
1 3

12
Gas-Liquid System – single condensable
component

1. Saturation, saturated

Evaporation (the Air +Vapour Condensation

process) (the process)
Drying (solid)
Dehumidification
Humidification (air) (of air)
Water
Chemical species A
= water
2. 2 components, 2 phases, at equilibrium, DOF = 2 + 2 – 2 = 2,
2 of the three variables P,T, and yA are needed to specify the
system
13

Gas-Liquid System – single condensable

component
Observations:
1. At equilibrium, gas phase
saturated with the volatile
component and partial
pressure of vapour equal to the
pure-component vapour
pressure under the condition
(P,T):
Air +Vapour
Pi = yiP = p*(T) special case of
Raoult’s Law
2. Superheated vapour (after
dried up,…)
Water
3. Dew point (from Superheated
steam,…)
4. Degrees of superheat
14
Multi-component Gas-Liquid System
Equilibrium Curve (closed system w/ A, B, C, …)
1. A portion of substance A migrates from the
liquid phase to the gas phase until equilibrium
is reached.
2. If a small additional quantity of A is added to
the liquid phase, a new balance is reached. By yA, yB, yC
measuring the concentration of A in the two
phases for each balance reached, an
equilibrium curve is thus obtained.
3. Raoult’s law (ideal liquid phase)
xA, xB, xC
pA = yAP = xAP*A(T)

pA – partial pressure of A in the gas

1
xA – molar fraction of A in the liquid

yA
P*A(T) – saturated vapour pressure of pure A
yA – molar fraction of A in the gas phase
P – total gas pressure
4. True for systems with similar components or
when xA is close to 1
xA 15

Henry’s Law
 Henry’s law (dilute solutions, xA
close to 0)
pA = yAP = xAHA(T)
pA - partial pressure of A in
the gas phase
xA - concentration of A in the
liquid phase
H(T) - Henry’s law constant

Henry’s law (dilute

solutions, i.e., the slope
near the origin is straight)

16
Ideal solution vs non-ideal solution
(Azeotropic point)

V-L equilibrium of water ethanol mixtures

If aqueous Ethanol solution were
ideal solution
100

95

90

85

80

75
0 0.2 0.4 0.6 0.8 1

17

Vapour-Liquid Equilibrium Calculations for

Ideal Solutions
Why do we need V-L
equilibrium calculations?

1. Heating of liquid water

2. Heating of mixtures with Dew point curve
components A,B,C
3. Bubble point temp (Tbp)
Dew point temp (Tdp)
Bubble point pressure
(Pbp) Boiling point
Dew point pressure (Pdp) curve
4. How to determine them
on phase diagram?

18
• Pure water is placed in a leakproof evacuated cylinder fitted
with a movable piston,
• Heat can be added to or withdrawn from the cylinder, to adjust
the temperature

19

V-L Equilibrium for Ideal Solutions: Bubble

Point Calculation
Consider a V-L equilibrium with 3 components:
P, xi (i = A, B, C) known, calculate bubble point temperature.
Assume vapour phase as ideal gas and liquid phase as
ideal solution, based on Raoult’s law:

pi = xip*i(Tbp)…….. (i = A, B, C)

Total pressure P = xAp*A(Tbp) + xBp*B(Tbp) + xCp*C(Tbp) yA, yB, yC

Tbp can be determined by trial and error method using
p*i(Tbp) relationships such as Antoine equation, charts,
or tables, xA, xB, xC
yi can be calculated using yi = pi/P

Bubble-Point Pressure can also be determined using the

total pressure expression, given T; yi can then be
calculated using yi = pi/Pbp = xip*i(T)/Pbp

20
 V-L Equilibrium for Ideal Solutions: Dew
Point Calculation
For the same system:

Gas phase contains condensable components A, B, and C

and non-condensable component G at a fixed pressure. If
the mixture is cooled to its dew point temperature, it will be
in equilibrium with the first liquid that forms. P, yi (i = A, B,
C) known
yA, yB, yC
Applying Raoult’s law to liquid phase,

xi = yiP/p*i(Tdp)……(i = A, B, C, but G excluded) (1) xA, xB, xC

xA + xB + xC = 1 (only condensables enter liquid) (2)

Equations 1 & 2 can be used to calculate Tdp using a trial

and error method.

If the system T is known, 1 & 2 can also be used to calculate

the dew point pressure. 21

Calculation of Dew-Point Pressure:

Consider an ideal gas mixture with n components, of which k are

condensable. When the gas starts to be in equilibrium with its condensate
(first drop of liquid formed), after compressing to its dew-point pressure (i.e.,
Pdp) at a constant T, (after rearranging eqn. 6.4-7) we get,

1
Pdp  k
i  1,2,..., k
yi
i 1
*
p i (T )

Example: gas mixture containing 15 mol% benzene, 10 mol% toluene,

75 mol% nitrogen is compressed isothermally (i.e., T constant) at 80oC
until condensation occurs. At what pressure will condensation begin?

22
 Calculation of Dew-Point Pressure:

Known quantities are, yb = 0.15; yt = 0.1; yn = 0.75, T = 80oC;

To calculate: Pdp
Solution: Based on equation in last slide or 6.4-8 in text, we have

1
Pdp  (6.4.8)
yb yt

pb* (80 oC ) pt* (80 oC )

From Table B.4,

for benzene the Antoine constants are A = 6.89272; B = 1203.531; C = 219.888
for toluene the Antoine constants are A = 6.95805; B = 1346.773; C = 219.693

B 1203.531
A 6.89272 
pb*  10 T C
 10 80  219.888
 757.7 mmHg Plug in the numbers into
B 1346.773
equation (6.4.8), we get
A 6.95805 
pt*  10 T C
 10 80  219.693
 291.2 mmHg
Pdp = 1847 mmHg 23

Solid-Liquid Solutions
 Solubility and saturation
 The solubility of a solid is the maximum amount of
that substance that can be dissolved in a specific
amount of liquid at equilibrium.
 A solution containing a maximum amount of a
component dissolved at equilibrium is said to be a
saturated solution of that component.
 A solution at equilibrium with a dissolved solid
must be saturated, else more solids can dissolve.
Thus, if we know the T and P of a stream at
equilibrium, we can know its composition.

24
 Solid-Liquid Solutions
 Solubility of solids and hydrated salts
The solubility of a solid in a liquid depends on P
and T. Certain solids (e.g., Na2SO4, MgSO4)
can form hydrated salts (e.g.,
Na2SO410H2O), which changes the solubility
of the solid.

25

Solid-Liquid Solutions

NaCl: special case; Others: trend for most of chemicals

26
 Solid-Liquid Solutions
 Colligative solution properties (e.g., freezing point
depression, boiling point elevation, vapor pressure
lowering, and osmotic pressure.) depend on the
concentration of the solute. Compared to pure solvents,
solid-solvent solution have higher boiling points but lower
melting points (i.e., salty water).

27

Gas-Liquid Solutions
 The solubility of gas in liquid solvents usually decrease
with temperature (i.e., dissolved oxygen in water, think
about air stripping)

 The solubility of solid in liquid solvents usually increase

with temperature (with Table salt as exception); think
about why heat a solvent to speed up solution of a solute

28
 Liquid-liquid equilibrium
 The liquid-liquid extraction principle is simple: a solute is
recovered by a solvent with which it has great affinity.
 Solvent: insoluble or weakly soluble in the solution to be
extracted.
 Liquid-liquid extraction steps:
 Intimate mixing of solvent with solution containing solute to be
extracted;
 Separation of the mixture into two immiscible liquid phases;
 May be followed by a separation of the solute from the solvent
and solvent recovery for re-use in additional extraction steps.

29

Liquid-liquid equilibrium

 Miscibility and distribution coefficients

 The equilibrium relation may be given by the
distribution coefficient which is a ratio of
mass fractions of solute in each phase at
equilibrium. Data for several ternary systems
are found in Perry’s Chemical Engineering
Handbook.

30
 Liquid-liquid equilibrium
Triangular phase
diagram: LLE to
extract Acetone
from Aqueous
solution to MIBK

Useful for partially

miscible solvents

Organic phase

Aqueous phase

31

Adsorption on Solid Surfaces

 One or more components of a gas or liquid
are adsorbed on the surface of a solid and a
separation is thereby achieved.
 The adsorbent is typically present as small
particles in a fixed bed.
 Equilibrium relations for adsorbents at a
specific temperature (i.e., adsorption
isotherms) are very similar to other
equilibrium data.

32
 Adsorption on Solid Surfaces

33

6.28：On a hot summer day the temperature is 35°C, barometric pressure

is 103 kPa, and the relative humidity is 90%. An air conditioner draws in
outside air, cools it to 20°C, and delivers it at a rate of 12,500 L/h.
Calculate the rate of moisture condensation (kg/h) and the volumetric flow
rate of the air drawn from the outside.

34
 Examples, Problem 6:59

Solution:
From problem description, the process flowchart is prepared below,
Where the molar flowrate of nitrogen is kept constant at 10 Litre (80oC & 3 atm) per minute, and
the system temperature and pressure are 80 oC and 3 atm respectively.

Let assume the initial amount of liquid mixture is nL0=2mol, since liquid components vaporize and
go out of the system with nitrogen, the system is an open one but not at steady state. Therefore, the
mole fractions of the liquid and vapor mixtures as well as the molar flowrate of the vapor phase all
changes with time.

35

6:59 Continued…

Assuming the vapor phase is ideal gas, we get:

Benzene and Toluene saturated vapor pressure at 80oC:

a)
at time t=0, xB = 0.5, xT = 0.5. Based on Raoult’s law, below, we can get yB and yT .
PB = P*yB =xB*pB(80oC) and PT = P*yT =xT*pT(80oC)

b)

c) 36
Examples, Problem 6:80

Solution

37