Mass & Energy Balance

HCMUT-CheEng

CHAPTER 6
MULTIPHASE SYSTEMS

Reference: Chapter 6 of R.M. Felder & W. Rousseau, Elementary Principles of Chemical Processes, 3rd
ed. 2005 (Wiley).
INSTRUCTIONAL OBJECTIVE
After completing this chapter, you should be able to do the following:
Sketch a phase diagram (P versus T) for a single species and label the region (solid, liquid, vapour,
gas).
Explain the difference between a vapour and a gas.
Use the phase diagram to define
a) the vapour pressure at a specified temperature
b) the boiling point at a specified pressure
c) the normal boiling point
d) the melting point at a specified pressure
e) the sublimation point at a specified pressure
f) and the triple point
SINGLE-COMPONENT SYSTEM
Phase Diagram of a pure substance: Plot of pressure versus temperature that shows condition at which a
substance exists as a solid, liquid or gas.
EXAMPLE

Boundaries between single-phase regions represent P,T values for coexistence of two phases in
equilibrium

All phase transitions take place at boundaries at const T or P until changes are complete

If T and P correspond to a point on the Vapour-Liquid equilibrium:

Chapter 6

P vapour pressure of substance at T

T boiling point temperature of substance at P

If P=1 atm, then T Normal boiling point

Summer 2014

Page 1 of 13

Mass & Energy Balance

HCMUT-CheEng

If (T,P) falls on the Vapour-Solid equilibrium:

o

P vapour pressure of substance at T

T sublimation point at P

If (T,P) falls on the Liquid-Solid equilibrium:

o

T melting point or freezing point at P

(T,P) condition where S, L and G can all coexist is triple point of the substance

at T>TC (critical temperature) a substance can exist as a gas (non-condensable)

Data for normal boiling point and melting point temperatures are available in Felder & Rousseau
(Table B1) and in Perry's handbook (pp. 3-6 to 3-44)

Vapour Pressure
Pressure corresponding to the boiling point temperature of a liquid
Frequently needed in process analysis involving liquid-vapour system
Vapour pressure data available in Felder & Rousseau (Tables B3, pages 638-639 for water) and in
Perry's handbook (pp. 3-45 to 3-73) for others.
Vapour pressure can also be predicted using known equations.
i.

Clausius-Clapeyron Equation

plot of ln (P*) vs (1/T) is linear with slope = -

With known

/R and intercept = C

, known value of P* at any T can be used to predict P* at another T.

EXAMPLE 1 - Calculate vapour pressure of pure substance

For benzene, the following data are available:
T1 = 7.6oC, P1* = 40 mm Hg
T2 = 15.4oC, P2* = 60 mm Hg
Predict vapour pressure at 42.2oC by means of the Clausius-Clapeyron equation
Solution:

Chapter 6

Summer 2014

Page 2 of 13

Mass & Energy Balance

HCMUT-CheEng

for T = 42.2oC

P* = 211 mm Hg

ii.

Antoine Equation

P* in mm Hg, T in oC
Values of A, B and C are tabulated for various substances in Felder & Rousseau (Table B.4,
Appendix B)

EXAMPLE 2 - Calculate vapour pressure of benzene at 42.2oC using Antoine equation.

From Table B.4 (page 640) Felder & Rousseau, find for C6H6:

Chapter 6

Summer 2014

Page 3 of 13

Mass & Energy Balance

HCMUT-CheEng

A = 6.89272; B = 1203.531; C = 219.888

P* = 200 mmHg

MULTICOMPONENT SYSTEMS
Degrees of Freedom (DF)
Number of intensive variables that can be independently specified for a system at equilibrium
Gibbs Phase Rule
DF = 2 + C - P
C:
number of chemical species
P:
number of phases present at equilibrium
Note:
C-r).

If r independent reactions occur and proceed to equilibrium, value of C must be reduced by r (i.e.,

EXAMPLE - Phase Rule

Pure liquid water: DF = 2 + 1 1 = 2

2 intensive variables must be specified, eg. T and P

Mixture of ice and liquid water: DF = 2 + 1 2 = 1

only 1 intensive variable can be specified, eg. T or P. If P is fixed then T is uniquely determined as the
freezing (or melting) point

Liquid ethanol in equilibrium with ethanol vapour and carbon dioxide: DF = 2 + 2 2 = 2

2 intensive variables must be specified, eg. T and P, or T and 1 composition (of CO2 or ethanol
vapour)

A gaseous mixture of H2, Br2 and HBr, given the following reaction has proceeded to equilibrium:
H2 + Br2 2 HBr
DF = 2 + (3-1) 1 = 3
3 variables must be specified, eg. T, P and concentration of 1 component

Gas-Liquid System with 1 Condensable Component

Systems containing several components but only one is capable of existing as a liquid at process
condition are common.
Examples: evaporation, drying, humidification, condensation, etc

When any gas comes in contact with a liquid, the gas will acquire molecules from the liquid. The
liquid is said to vaporize. This proceeds until equilibrium is reached, where:

Chapter 6

Summer 2014

Page 4 of 13

Mass & Energy Balance

HCMUT-CheEng

The gas is saturated with the particular vapour of the liquid at the given T

The partial pressure of the vapour in the gas is equal to the vapour pressure of the liquid at
the system T
The gas mixture is at its dew point (temperature where the vapour just starts to condense
when cooled at a constant P)

Gibbs phase rule applies at equilibrium: DF = 2 + C 2 = C

eg. Water and air: DF = 2, specify T and P to define condition at L-V equilibrium

If a gas at (T, P) contains saturated vapour whose mol fraction is yA and if this vapour is the only
species that would condense if temperature is lowered, then

EXAMPLE 3
Air and liquid water are contact in a humidification chamber at 75oC and 760 mmHg. Calculate the molar
composition of the gas phase at equilibrium.
Solution:
At equilibrium: from Table B.3 (page 639) or Table B.5 (page 643)
at T= 75oC, P* = 289.1 mm Hg = 0.386 bar

Pwater

vap

= vapour pressure of water at 75oC = 289 mm Hg

ywater vap = Pwater vap / P = 289 / 760 = 0.380

yAir = 1 - ywater vap = 0.620
Important points to remember:
A gas in equilibrium with a liquid must be saturated with the vapour of the liquid at the system
temperature
Chapter 6

Summer 2014

Page 5 of 13

Mass & Energy Balance

HCMUT-CheEng

The partial pressure of a vapour at equilibrium in a gas mixture containing a single condensable
component cannot exceed the vapour pressure of that component at the system T
A vapour present in a gas in less than its saturation amount is referred to as superheated vapour. For
such vapour:
If a gas containing a single superheated vapour is cooled at const P, the temperature at which the
vapour becomes saturated is called the dew point of the gas, ie

Degree of superheat = T - TDew

EXAMPLE 4 - System with single condensable component

A stream of air at 100oC and 5260 mm Hg contains 10% vol water.
1.

what is dew point of the air and degree of superheat of the water vapour?

2.

if the gas is cooled to 80oC at constant pressure, what would be the percentage of the vapour
that condenses and the final gas composition?

Solution:
1)

partial pressure of water vapour:

Pwater = ywater P = 0.1 x 5260 = 526 mm Hg
At 100oC, P*water= 760 mmHg > Pwater water vapour is superheated
for P = 526 mm Hg
Tables B.4, Td = 90oC

dew point of gas = 90oC

2)

degree of superheat = 100 90 = 10oC

gas is cooled from 100oC to 80oC at 5260 mm Hg

Chapter 6

Summer 2014

Page 6 of 13

Mass & Energy Balance

HCMUT-CheEng

At 80oC, from Table B.3, P*water= 355.1 mmHg

ywater = 355.1/5260 = 0.067

yAir = 1 - 0.067 = 0.933

Basis: 100 mol wet air

Mass balance on dry air: (100) (0.9) = (0.933) n2 n2 = 96.56 mol.
Overall mass balance: 100 = 96.46 n1
n1 = 3.54 mol: amount of water condensed
% water vapour condensed =

Chapter 6

Summer 2014

Page 7 of 13

Mass & Energy Balance

HCMUT-CheEng

Relative Saturation (Relative Humidity)

pi = pVap :
pi* (T) =p*vap:

partial pressure of the vapour in the gas mixture

partial pressure of the vapour if the gas is saturated at the given T of the mixture

EXAMPLE A relative humidity of 40% signifies that the partial pressure of water vapour equal 4/10 of the
vapour pressure of water at the system temperature.
Molal saturation (Molal Humidity)

Absolute Saturation (Absolute Humidity)

where Mi is the molecular weight of the vapour and Mdry is the average molecular weight of the dry (vapourfree) gas.

Percentage Saturation (Percentage Humidity)

EXERCISE
Humid air at 75oC, 1.1 bar, and 30% relative humidity is fed into a process unit at a rate of 1000 m3/h.
Determine (1) the molar flow rates of water, dry air, and oxygen entering the process unit, (2) the molal
humidity, absolute humidity, and percentage humidity of air, and (3) the dew point.
Solution:
(To be covered in lecture)

Chapter 6

Summer 2014

Page 8 of 13

Mass & Energy Balance

HCMUT-CheEng

MULTICOMPONENT GAS-LIQUID SYSTEM

In 2-phase (liquid-vapour) equilibrium, a component in one phase is in equilibrium with the same
component in the other phase. The specific equilibrium relationship depends on T, P and
compositions.
Example: A vapour-liquid mixture of benzene and toluene.
C = 2; P = 2
B, T (vapour phase)
y B , yT

B, T (liquid phase)
x B , xT

At equilibrium
Gibbs phase rule DF = 2 + C P = 2
need to specify 2 variables :
- T and P, or
- T and 1 concentration, or
- P and 1 concentration, or
- 2 concentrations
Raoult's Law
PA = yAP = xAP*A (T)
yA:
xA:
P*A :
P:

mol fraction of A in vapour

mol fraction of A in liquid in equilibrium with the vapour
vapour pressure of A at T
total pressure

Valid for concentrated solutions where xA ~ 1

Valid for ideal mixtures and solutions at all concentrations
yA = (P*A/P) xA = KA xA
K A:
equilibrium constant

Chapter 6

Summer 2014

Page 9 of 13

Mass & Energy Balance

HCMUT-CheEng

EXAMPLE 5 - Raoults law

An equimolar liquid mixture of benzene and toluene is in equilibrium with its vapour at 30oC. What is the
system pressure and composition of the vapour?
Solution:
Use Antoine equation to calculate vapour pressures at 30oC.
From Table B.4 of Felder & Rousseau (page 640-641), find C6H6 (Benzene) and C7H8 (Toluene):

C6H6 (Benzene):
C7H8 (Toluene):

A = 6.89272; B = 1203.531; C = 219.888

A = 6.95805; B = 1346.773; C = 219.693

P*B = 146.7 mm Hg

Chapter 6

Summer 2014

Page 10 of 13

Mass & Energy Balance

HCMUT-CheEng

C7H8: P*T = 36.7 mm Hg

Use Raoult's law to calculate partial pressures:
C6H6: PB = yB P= xB P*B = 0.5 x146.7 = 73.35 mm Hg
C7H8: PT = yT P= xT P*T = 0.5 x36.7 = 18.33 mm Hg
Total pressure:
P = PB + PT =73.35 + 18.33 = 91.69 mm Hg
Composition of vapour:
C6H6: yB= PB/P = 73.35 / 91.69 = 0.800 (80.0%mol)
C7H8: yT= PT/P = 18.33 / 91.69 = 0.200 (20.0%mol)

Henry's Law
PA = yAP = xAHA(T)
yA:
xA:
HA :
P:

mol fraction of A in gas

mol fraction of A in liquid in equilibrium with the gas
Henrys law constant
total pressure

Valid for dilute liquid solutions where xA ~ 0

Valid for mixtures of non condensable gases

Data for HA for several gases in water can be found in Perrys Handbook

Chapter 6

Summer 2014

Page 11 of 13

Mass & Energy Balance

HCMUT-CheEng

VAPOUR-LIQUID EQUILIBRIUM CALCULATIONS

Ideal Binary Mixtures
Constant Pressure

Liquid mixture at a (Ta) with composition (xA, xB) is continuously heated:

at b (Tb): Liquid starts to vaporise

Tb: Bubble-point temperature of liquid at given pressure
yAb: mol fraction of A in vapour

at c (Tc): Liquid and vapour in equilibrium

xAc: mol fraction of A in liquid
yAc: mol fraction of A in vapour

at d (Td): Vaporisation is complete

Td: Dew-point temperature of vapour at given pressure
yAd (=xA): mol fraction of A in vapour

at e (Te): Mixture is vapour with composition

yAe = xA; yBe = xB

Bubble-Point Calculation
Determine the temperature at which a liquid mixture starts to boil at a fixed total pressure
Given liquid mixture with composition (xA, xB)
At Tb, first vapour is formed in equilibrium with the liquid
Raoults law applies:

or

Trial and error procedure to find Tb that satisfies the above equation

Chapter 6

Summer 2014

Page 12 of 13

Mass & Energy Balance

HCMUT-CheEng

Dew-Point Calculation
Determine the temperature at which a vapour mixture starts to condense at a fixed total pressure
Given vapour mixture with composition (yA, yB)
At Td, first liquid is formed in equilibrium with the vapour
Raoults law applies:

or

Trial and error procedure to find Td that satisfies the above equation

EXAMPLE 6 - Bubble-point calculation

Find the temperature at which a liquid mixture containing 40 mol% benzene and 60 mol% toluene starts to
boil at 1 atmosphere.
Solution:
Find the temperature Tb that satisfies the equation:

where:
P = 1 atm = 760 mm Hg
xA = 0.4 (benzene)
xB = 0.6 (toluene)
Use Antoine equation to calculate vapour pressures of A and B at different assumed values of Tb.

From Table B.4 (Felder & Rousseau), find

Benzene :
A = 6.89272; B = 1203.531; C = 219.888
Toluene :
A = 6.95805; B = 1346.773; C = 219.693
T (oC)
80
100
94.25
95.09
95.15

P*A (mm Hg)

757.620
1350.109
1152.133
1179.559
1181.386

P*B (mm Hg)

292.211
556.3432
465.7848
478.2256
479.0552

f (Tbp)
- 0.371
0.1498
- 0.02589
- 0.00163
- 1.7E-05

Tnew (oC)
100
94.25
95.09
95.15
95.15

Solution Tb = 95.1oC: Bubble-point temperature

At this temperature:
C6H6: PA = xA P*A = (0.4) x ( 1181.386) = 472.5 mm Hg
C7H8: PB = xB P*B = (0.6) x ( 479.055) = 287.5 mm Hg
Total pressure = PA + PB = 472.5 + 287.5 = 760 mm Hg
Composition of vapour: C6H6: yA= PA/P = (472.5) / (760) = 0.622 (62.2 mol%)
C7H8: yB= PB/P = (287.5) / (760) = 0.378 (37.8 mol%)

Chapter 6

Summer 2014

Page 13 of 13