Chemical Engineering

Fundamentals 2A
CEFCHA2
Lecture 8: Multi-Phase Systems II
M Malatji
JOB 4136
[email protected]
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 T, A (e.g. water)
P
A Evaporation
Drying Transfer of liquid
B Q in Humidification to gas phase

C
Gas-Liquid B,C

Systems: Single
Condensable A,
Component T,
P
B
A Qout
Condensation Transfer of gas to
Dehumidification liquid phase
B

C C (e.g. water)

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 Raoult’s Law
A (saturated vapor)

air
Water T = 75 0 C
(liquid) P = 760 m m H g
water p H2O = y H 2 O P

C = water & air, P = liquid &

vapor
F=2+C-P=2 specify 2 of T, P, or yH2O

If a gas at temperature T and pressure P contains a saturated vapor whose mole fraction is yi and if this vapor is the only
species that would condense if the temperature were slightly lowered, the partial pressure of the vapor in the gas equals the
pure-component vapor pressure p*i (T) at the system temperature.

Raoult’s law,
single condensable p i = y i P = p i *(T)
species :
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 Raoult’s Law: Multi-Component Gas-Liquid System
yA , yB
A, B
(liquid)
@T ,P
p A = y A P; p B = y B P

xA , xB

F=2+C-P=2 specify 2 of T, P, yH2O

y A mole fraction of A in a gas phase

Raoult’s Law p A = y A P = x A p A *(T) x A mole fraction of A in a liquid phase
p A *(T) vapor pressure of pure liquid A
Valid
• when xA ==> 1.0 (liquid is almost pure A),
• for the entire range of compositions for mixtures of similar substances, e.g. paraffinic
hydrocarbon off similar molecular weight
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Henry’s Law: Multi-Component Gas-Liquid System

Air,
(less) wa te
NH 3 r
@T ,
P
Air,
NH 3 Water, NH 3

Henry’s pA = y A P =
Law ===> (A =
x A H A (T) NH 3 )
(HA(T) - Henry’s law constant for a specific solvent)

Valid
• when xA ==> 0.0 (dilute solution of A), provided that A does not dissociate, ionize or react in
the liquid phase
• often applied to solutions of non-condensable gases
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 Calculate the pressure and gas phase composition

(mole fractions) in a system containing a liquid

that is 0.3 mole% nitrogen and 99.7 mole% water

Example 1 in equilibrium with nitrogen gas and water vapor

at 80oC. Use appropriate laws (Raoult’s or

Henry’s). Henry’s constant for Nitrogen at 80 ℃

=.

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Example 1: Solution
mol N2 /mol =0.003 mol N2/mol
= 1- mol H2O/mol 0.997 mol H2O/mol Total pressure (P) =+ = 378 + 0.466 = 378.5 atm
80 ℃
Raoult’s Law for water:
Mole fractions in gas phase:
(80 ℃)
Using Vapor Pressure of Water (Table B.3)
vapor pressure of water @ (80 ℃) =

or () mol H2O/mol = 0.001

is Nitrogen’s
Henry’s constant
Using Henry’s Law for Nitrogen:
(80 ℃)
H (80 ℃) = (pg.2-127 Perry’s Handbook)
Raoult’s law can be used for
water and Henry’s law for
nitrogen … WHY ???

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 An equi-molar liquid mixture of Benzene

and Toluene is in equilibrium with its

vapor at 30 0C. What is the pressure and

Example 2
the vapor composition
Since benzene & toluene are structurally similar compound –

use Raoult’s law

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Example 2: Solution

Using Antoine Equation to find for p*

At 30 0C.

pB*= 119 mm Hg , pT*= 36.7

mm hg pB= xBpB*= 0.5 (119)= 59.5 mm Hg

pT= xTpT*= 0.5(36.7)= 18.35 mm Hg

P = pB + pT =77.9 m m H g

vapor composition
yB = pB/ P = 0.764 mol B /mol
yT = pT/P =0.236 mol T /mol

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Gas-Liquid Systems: Single Condensable Component

• A gas in equilibrium with a liquid must be saturated

with the volatile component of that liquid.
(a)the vapor of that species is saturated, or
(b)the vapor of that species is coexisting with the liquid at equilibrium
(which means it must be saturated)

• For a vapor at equilibrium in a gas mixture; pi (= yiP) ≤ p*

• If pi = p* (saturated vapor)
• Any attempt to increase p* by either adding more vapor or increasing
total pressure, would lead to condensation.

• For a given temperature, a vapor (vapor pressure) present in a gas in less

than its saturation amount (saturation pressure) is called superheated
vapor ;
pi = yi P < pi*(T) 10
Gas-Liquid Systems: Single Condensable Component

To achieve condensation in a system containing superheated vapor

Increase the total pressure at constant temperature (isothermal)

constant T
P
Total system pressure,
P
C B
pi = yiP = p*(T) pi =
p* pi<p
For a given pressure, *
the temperature at A
which p* = P is the
boiling point vf , vg
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Gas-Liquid Systems: Single Condensable Component

To achieve condensation in a system containing

superheated vapor

If Decrease
a gas containing a the temperature at constant pressure
T constant
superheated
single vapor
(isobaric) P
constant
is P th
cooled at
Tga A
temperatur
the vapor becomessaturated
at which s
called
is the dew point of
the gas
Tdp B
pi = yiP = pi*(Tdp)

The degrees of superheat

gives the difference
between the Tgas and Tdp vf ,
vg 12
Gas-Liquid Systems: Single Condensable Component

A gas mixture contains 10 mole % water vapor and the balance nitrogen. The gas
is initially at the temperature and pressure of 50 0C and 500 mmHg, respectively.

a. If the gas mixture is put into a cylinder and slowly cooled at constant
pressure, at what temperature would the first drop of liquid form ?
b. If the gas mixture is put into a cylinder and slowly cooled at constant
pressure until the temperature reaches 30oC, what is the percent
condensation of water vapor ?
c. If the gas mixture is put into a cylinder and slowly compressed at constant
temperature, at what pressure would the condensation occurs
d. If the gas mixture is put into cylinder and slowly compressed at constant
temperature until new pressure reaches 1000 mmHg, what is the percentage 13
 Material balances on a condenser.
A stream of air at 100 0C and 5260 mmHg contains 10
% water by volume.

1.Calculate the dew point and degrees of

superheat of the water vapor.
2. Calculate the % of vapor that condenses
and the final composition of the gas
Example 3 phase if the gas is cooled to 80 0C at
constant pressure in equilibrium.
3. Calculate the % condensation and the
final gas phase composition if instead of
being cooled the gas is compressed
isothermally to 8500 mmHg.

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Example 3: Solution
Solution 1

Partial pressure ; pH2O = yH2OP = (0.1)(5260) mmHg = 526 mmHg

Vapor pressure @ 100oC; pH2O* (100oC) = 760 mmHg > pH2O ==> the vapor is superheated

If pH2O = pH2O*(Tdp) = 526 mm Hg

from Table B.3, Tdp = 90oC and the vapor has 100oC - 90oC =

10 o C of superheat

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Example 3: Solution

• Further cooling must lead to condensation.

• Since the products are liquid water in equilibrium with a gas
phase, the water vapor in the gas must remain saturated.
• BDA (bone dry air) is the term used to indicate the water-free
component of an air- water vapor mixture.

Basis: 100 mol feed gas

100 mol
0.1 mol y ( mol H2O/mol)
H
0.9
2O/mol
mol (1-y) (mol BDA/mol)
BDA/mol
T = 100oC, P =5260 T = 80oC, P =5260
mm Hg mm Hg
Q1 mol H2O Saturated with H2O
(liquid)
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Example 3: Solution
Basis: 100 mol feed gas
100 mol
0.1 mol H2O/mol y ( mol H2O/mol)
0.9 mol BDA/mol (1-y) (mol BDA/mol)
T = 100oC, P =5260 T = 80oC, P =5260
mm Hg mm Hg
Saturated with H2O
Q1 mol H2O (liquid)

Problem bookkeeping:
• There are 3 unknowns ==> Q1, Q2 and y,
• Only 2 species are involved - max. 2 independent material
balances. Need a third equation.
• Third relation - Saturation (equilibrium) condition.

Strategy:
•Apply saturation condition at the outlet to get y,
•Use a dry air balance to get Q2, and a total mol or H2O balance
to get Q1
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Example 3: Solution

Saturation condition at outlet: yP = pH2O*(T); y = pH2O*(80)/P

= 355 mmHg/5260mmHg = 0.0675

mol H2O/mol
Balance on Dry Air 100 0.9 mol BDA = Q2(1 - y); (y =
mol 0.0675)
mol
Q2 = 96.5 mol

Total Mole 100 mol = Q1 + Q2; (Q2 = 96. 5

balance mol)
Q1 = 3.5 mol
% H2O condensed
condensatio
n
3.5 mol H2O condensed x
100% = 35% (0.1 x 100) 18

mol H2O fed

Example 3: Solution
Solution 3

Initially, yH2O P < pH2O*(100oC). Saturation occurs when P

is high enough.
= pH2O*(100oC) /yH2O = 760 mmHg/0.1 =
Psaturati
on
7600 mmHg
Any increase in P above Psaturation must lead to condensation.
Products from compression to 8500 mmHg must include a
liquid stream.
Basis: 100 mol Q2 mol
Feed Gas y mol H2O/mol
(1-y) mol BDA/mol
100
0.1 mol 2H T = 100oC, P = 8500
mol
O/mol
0.9 mol mmHg
BDA/mol Q1 mol H2O
5260 mmHg (l)

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Example 3: Solution

Saturation condition
y = pH2O*(100oC)/P = 760 mmHg/
8500 mmHg
= 0.0894 mol
Balance on (100)(0.900) =
H2O/mol Q2(1 - y);
BDA (y = 0.0894) Q2
= 98.8 mol
Total mole
balance 100 = Q + Q ; (Q = 98.8
1 2 2
mol)
% 1.2 mol H O condensed x
Q1 = 1.2 mol 2H2O condensed
condensatio (0.1 x 100) mol H2O = 12 %
100%
n fed

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Relative Saturation (Relative
Humidity)
pi
sr (hr )
= pi*
(T)
Molal saturation (Molal
humidity)

Absolute Saturation (Absolute

humidity)

sa (h ) piMi mass of
=mass of dry
=a p vapor
i
-p dr
y gas

M 21
Gas-Liquid Systems: Single Condensable Component

Percentage Saturation (Percentage Humidity)

is given by:

The relations allow calculations of pi, yi,Tdp, degree of

superheat, and Tbp

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Example 4

The vapor pressure of styrene is 100 mmHg at 82oC and 200 mmHg at 100oC. A gas that
consists of 10 mole % styrene and 90 mole % uncondensables is contained in a tank at
100oC and 1000 mmHg. Calculate the following (a, b, c)
a. The dew point of the gas c. The molal saturation and the percentage
saturation

From given data: @

Molal saturation
𝑝𝑖
𝑠𝑚 ( h 𝑚 ) =
𝑝 −𝑝 𝑖
= ( 100
1000 −100 )
=0.111
𝑚𝑜𝑙 𝑠𝑡𝑦𝑟𝑒𝑛𝑒
𝑚𝑜𝑙 𝑑𝑟𝑦 𝑔𝑎𝑠

b. The relative saturation

Percentage
saturation

( )
𝑃𝑖
𝑠𝑚 𝑃 − 𝑃𝑖 0.111
𝑠𝑝 ( h𝑝 ) = ∗
= ∗
× 100= × 100 = 44 %
𝑠 𝑃 200
𝑚 𝑖 ( )
𝑃 − 𝑃𝑖
∗ 1000 − 200

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