Chemical Engineering

Fundamentals 2A
CEFCHA2
Lecture 11: Multi-Phase Systems II
V Naidoo
JOB 4134
vizellen@uj.ac.za
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 T, A (e.g. water)
P
A Evaporation
Drying Transfer of
B Humidificatio liquid
Q in
n to gas phase
C
Gas-Liquid B,
C
Systems: Single
Condensable A,
Component T,
P
B
A Qout
Condensation Transfer of gas to
Dehumidificatio liquid phase
B
n
C C (e.g. water)

2
 Raoult’s Law
A (saturated vapor)
Water
(liquid air
T = 75 0 C
)
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 pi = y i P =
species : p i *(T)
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Raoult’s Law: Multi-Component Gas-Liquid System

yA ,
A, B yB
(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 p A = y A P = x A p A *(T) x A mole fraction of A in a liquid phase
Law p A *(T) vapor pressure of pure liquid A

Vali • when xA ==> 1.0 (liquid is almost pure A),

d • 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) NH 3 wa ter

@T ,
P
Air, NH 3
Water, NH 3

Henry’s p A = y A P = x A H A (T)
Law ===> (A = 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%

Example 1 nitrogen and 99.7 mole% water in equilibrium with nitrogen

gas and water vapor at 80oC. Use appropriate laws (Raoult’s

or Henry’s)

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Example 1: Solution

Raoult’s law can be used for water and

Henry’s law for nitrogen … WHY ???
y1mol N /mol
2
(1-y1) mol H2O/mol
p
H 2O
= y
H 2O
P = x
H 2O
p*
H 2O  o

80oC. 80 C
p H* 2 O
0.003 mol N2/mol 8 0
C  = 0 .4 7 3 6 b ar ( T ab le atm
o

= 0 .4 7
0.997 mol H2O/mol H O
= 
2
1 - y  P = 0B.9.59 )7 

 0 .4 7 m o lefractio n 
1 2
a tm 3 6 
p
hence

P = 378.5 atm o

p N = y N P = x N HN 80 C
2 2 2 2
y1 mol N2/mol = 0.999
...... pg. 2 -127 (Perry's
(1-y1) mol H2O/mol = 0.001 H N2
80 C  = 12.6x10
o
mole
4 atm
fraction HB)
4 atm
p N2 = y 1P = 0.003 12.6x10 mole fraction = 378 atm

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 An equi-molar liquid mixture of Benzene and

Toluene is in equilibrium with its vapor at 30

Example 2 0 C.What is the pressure and 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)
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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

pi = yiP = p*(T)
C B
pi = p*
For a given pressure, the pi<p*
temperature at which p* = P
is the boiling point A

vf , vg
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Gas-Liquid Systems: Single Condensable Component

To achieve condensation in a system containing superheated vapor

Decrease the temperature at constant pressure (isobaric)

Ifa gas containing a constant P

superheated vapor is cooled at
single T
constant P th temperatur at which
Tgas A
the vapor becomes saturated
called the dew point of the
is
gas
Tdp B
pi = yiP = pi*(Tdp)

The degrees of superheat gives the

difference between the Tgas and Tdp
vf , vg
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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 of water vapor?
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 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 of the air, and degrees of superheat

of the water vapor.
2. Calculate the % of vapor that condenses and the
Example 3 final composition of the gas phase if the gas is
cooled to 80 0C at constant pressure.
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)(5620) 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 H2O/mol y ( mol H2O/mol)
0.9 mol (1-y) (mol BDA/mol)
BDA/mol
T = 100oC, P =5260 mm Hg T = 80oC, P =5260 mm Hg
Saturated with H2O
Q1 mol 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 mm Hg T = 80oC, P =5260 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 = 0.0675)
mol mol

Q2 = 96.5 mol

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

Q1 = 3.5 mol H2O
condensed
% condensation
3.5 mol H2O condensed x 100% =
35% (0.1 x 100) mol H2O fed
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Example 3: Solution
Solution 3

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

enough.
= pH2O*(100oC) /yH2O = 760 mmHg/0.1 = 7600
Psaturation
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 Feed Q2 mol

Gas y mol H2O/mol
(1-y) mol BDA/mol
100 molH2O/mol
0.1 mol T = 100oC, P = 8500 mmHg
0.9 mol
BDA/mol Q1 mol H2O (l)
5260 mmHg

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Example 3: Solution

Saturation condition
y = pH2O*(100oC)/P = 760 mmHg/ 8500 mmHg
= 0.0894 mol H2O/mol

Balance on (100)(0.900) = Q2(1 - y); (y =

BDA 0.0894) Q2 = 98.8
mol
Total mole balance
100 = Q1 + Q2; (Q2 = 98.8 mol)
Q1 = 1.2 mol H2O condensed
% condensation 1.2 mol H2O condensed x 100% = 12
%(0.1 x 100) mol H2O fed

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

Absolute Saturation (Absolute humidity)

sa(h a) = piMi mass of vapor

= mass of dry gas
p - pi dry

M 21
Gas-Liquid Systems: Single Condensable Component

Percentage Saturation (Percentage Humidity) =

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 mm Hg at 82oC and 200 mm Hg at 100oC. A gas that consists of 10 mole %
styrene and 90 mole % uncondensable is contained in a tank at 100oC and 1000 mm Hg. Calculate

a. The dew point of the gas c. The molal saturation and the percentage saturation

pi = yiP = 0.1(1000) =100 mm Molal saturation

Hg T = f(P ) = 82o C sm (hm ) = pi = 100 = 0.111mol styrene

p - pi 1000 -100 mol dry
gas
b. The relative saturation Percentage saturation

sr (h r) =
pi 100 mm Hg  pi 
= x 100% = 50%
p* (T =100o C) 200 mm
i s 
p - p  0.111
Hg sp(h p) = m* =  *  x 100% = 
i
x 100% =
s 200 
m
 i
p  
 p - * 44.4%
 i   1000 - 200 
p
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