Vapour-Liquid Equilibria 1

(KIL 1002 Chemical Process Principles 1)

Dr. Faidzul Hakim Adnan

faidzulhakim.adnan@um.edu.my

DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITI MALAYA
Learning outcomes
At the end of this class, you should be able to

explain vapour-liquid equilibrium involving one condensable

component

apply this phenomenon to mass balance

2
3
Vapour-Liquid phase equilibrium
Consider a bottle of water: At equilibrium, compositions
will not change with time
What is in
What if a smaller volume of
this space?
water is used?
Air
Water vapour More water will evaporate
to fill the space
Less air will dissolve in the
smaller volume of water
What about
here?
The final compositions in
Water each phase remain unchanged
Dissolved air

4
Effects of temperature
If we put the bottle under Temperature strongly
the sun? affects physical equilibrium

Generally, as T ↑
vapour pressure ↑
What happens to
the moisture content? solubility of a gas ↓
the pressure?

What about the

dissolved air?

5
6
The idea of “saturation”
At phase equilibrium, each phase contains the MAXIMUM -

amount of every species, so that the excess has to be in

-

another phase.
Seen another way,
Saturated with water vapour, the
-
phases in equilibrium
excess water stays as liquid must exist together,
otherwise the “excess”
species in a phase has
nowhere to go!
Saturated with dissolved air, the
-

excess air stays in the gas phase

7
 Vocabulary for saturation
Saturated vapour pressure =
-
Relative humidity (RH) =
-

the maximum partial pressure Pk

of a species at equilibrium RH = × 100%
-

*
Pk
ene
-

saurate Pk = partial pressure of species-k

It indicates whether the gas phase
↓
can take more of the volatile
O
P* k
saturated vapour pressure of species, e.g.
species-k
RH = 60% ⇒ not yet saturated, more
Time liquid can evaporate

Liquid just Equilibrium

00-
RH = 100% ⇒ saturated, no more
liquid can evaporate
introduced achieved -

8
continued …
Dew point = Bubble point =
temperature at which the temperature at which the first
->
vapour will start to condense bubble forms in the liquid (boils!)

T1 oC T2 oC T3 oC T4 oC
Cooling First drop Heating First
Vapour of liquid Liquid bubble

Pk < P*k (T1) Pk = P*k (T2) P*R (T3) < PR P*R (T4) = PR

T2 = dew point T4 = bubble point

RH < 100% RH = 100%

9
 Finding saturated vapour pressure
P*H2O
Use the pure liquid, e.g. Exponential
distilled water: 1 atm rise!

Fix T
Wait for boiling (why?)
PI Take P as P*(T) T
Repeat with other T 100oC

Results of experiments for

water are widely available,
TI Water only e.g. steam tables (the most
Rigid container accurate)

10
P* for other species
For other species, the Cox Where available, the Antoine#
chart is the classical way: equation is preferred:
autoine
X
ln (P ) or log 10 (P * ) = A −
P* (log scale) * B
T+C

One line for

Watch out for
each species
base of the logarithm
units of P* and T
range of validity

T (not linear, not log, see textbook) #French name, pronounced as “on tuan”

11
 Example 1
A boiler generates saturated P*H2O = (10 + 1.01325) bara
steam at 10 barg. What is ≈ 11 bara
-

the expected temperature of &73.3

the steam? From the steam table:
P*(bara) T(oC) T(k)
-
P = 10 barg = P*H2O
10.02 180.0 453

Feed water Saturated 12.54 190.0 463

Boiler steam
T(°C)
Water in equilibrium N

a
with its vapour only
so
Scope: **.02
-80 -

Mio.or ee
43Ir
n -
10.02

12
X 184°
=
Example 2
method:cool down.
it

In a vapour, component X
is the only condensable Px PxCT.
= < T)

species. the
method:compress
subtle
such that
What are the 2 ways to vapour

Px (T).
Px
induce condensation of X? =

Or

Clearly
ToC PX < P*X(T) ↓ y xp P
=

(T)
x

At
X+
etc. How to equate
both sides?

13
Impact on DoF analysis
Phase equilibrium fixes the Every phase equilibrium
allowable compositions of
species across phases
C
condition, e.g. yi = P*i /P is
one additional condition to
be satisfied.
I want P = 1 atm,
T = 38oC and
Possible? []
yA = 0.45
Thus counted as
an equation

yA
Phase equilibrium tends to
reduce the DoF of the
Liquid A
problem.

14
 Example 3
A wet gas stream is cooled analysis:
Dot
in a condenser to remove Y1)
Nr= (W and
some moisture. Find the 2

flow rate of the condensed Ne=2 (water

sequilibr
water.
bot: o

Feed Vapour
atphase equilibrium:
F = 1 kmol/s V = ? kmol/s

Moee
yF = E
0.33 mol H2O/mol y1 = ? mol H2O/mol Y.
=

Water 10 oC ↳1.5ban
W kmol/s 150 kPa
xH2O = ? mol H2O/mol
=
1227
8.2x167
=

55
15
45/w0 0.45
=
continue...
mB/ overall:

F w
=
V
+

MB/ water:
the refore:
Y .F xH,jw y,V
= +

W 1 0.68
=
-

YFF (1) (F-V) y, V

+
-
=

W 0.32
=

e
0.61
=

16
 Extension of Example 3
that lowest temp is

If the feed stream pressure

-

is 160 kPa, and it must not the dew point of

have liquid water, what is this stream

its lowest temperature? -atthe dew point,

PH2 PA*
=

P = 160 kPa PH2 = 0.22 (160kPa)

yF = 0.33 mol H2O/mol
T > ? oC 52.8 kRG
=

from the
stream table

T 82.6°
=

17
 Example 4 P*(720)) 0.34 bar
=

Given

Water is sprayed into a stream analysis:

Dot
of dry air to saturate it with
water vapour. Heat is supplied Nr= 3 Cha, kw
and y)

to keep the humid air at 72oC.

What is the required mass flow
rate of the water?
nW kmol/h

I
Water Humid air
Dry air
40 m3/h nA + nW kmol/h
Humidifier
1.2 atm abs, 80oC 1.1 atm abs, 72oC
nA kmol/h mol / mol
y H2O
Basis: as given above 1 − y Air

18
 continued …
ideal behaviour
assume
gas m3
4
UA b x15pax
-

8.314 (273.15 80)

+

molk

=ba ) e5 75 70 75 72
-

v
-

= =

- >

-8 n -

38.578-31.188

balance on air:
mole

Fing*sto
I
a
(nw) +(1 y) (ra nw)
-

n
+
=

0 -

(y) nF 0.6766x 3
=

nw= 261015
-

n 34.143
=

nw= (85) (1.657 0.24bawr

=

nw 0.73 knol/n
= 19
Example 5
One kilogram of acetone is Antoine equation:
kept in a closed container at
40oC. log 10 (P * bar )
1312.253
= 4.42448 −
The 200 mL space above the (T K ) - 32.445
liquid is filled with its vapour
and nitrogen, to a pressure of (valid for 259.16 – 507.60 K)
350 kPa.

What fraction of all acetone is

in the vapour phase?

20
Solution
Sketch, with A = acetone

21
continued …

22
Extension of Example 5 …
How big should the vapour
space be for 99% of the
acetone to exist in the vapour
form?

23
Summary
For vapour-liquid equilibrium involving 1 condensable
species A:

Saturated with A,
P i.e. P = P * T
A A ( ) Vocabularies
T saturated vapour
Phases yA pressure
relative humidity
co-exist Reduces DoF
dew point
Liquid A by dictating bubble point
PA* (T )
yA =
P

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