CHAPTER 3

VLE IN A BINARY
MIXTURE
HENRYS LAW
Raoults law:
y i P x i Pi sat

What if one component is at supercritical state

(T > Tc)?

Raoults law is not appropriate for a species

whose Tc < T.
 sat sat
xwater Pwater Pwater
ywater
P P
xwater 1

y air P
xair sat ??
Pair
Henry's law is applied for
pressures low enough that the vapor
phase may be assumed an ideal gas.
a species present as a very dilute solute
in the liquid phase.
The amount of dissolved gas is
proportional to its partial pressure in the
gas phase.

The proportionality factor is called the

Henrys law constant.
Henrys constants are needed in:

Atmospheric chemistry

Environmental research
Two fundamental types of Henrys constants:
1. Henry solubility constant (A/G)
2. Henry volatility constant (G/A)
where A and G are the equilibrium compo-
sition (at infinite dilution) of the aqueous
phase and the gas phase, respectively.
A/G
The Henry solubility constant is defined
as:
cp ca
H (3.4)
p
where ca is the concentration of a species in
the aqueous phase, and p is the partial
pressure of that species in the gas phase
under equilibrium conditions.
The SI unit for
Hcp : mol m3 Pa1 or M atm1
M : M (1 M = 1 mol dm3)
p : atm (1 atm = 101 325 Pa)

Data for Henrys solubility constants can be

found in Sander (2015).
(Sander, L., Atmos. Chem. Phys., 15, 4399
4981, 2015)
The dimensionless Henry solubility
constant is defined as:

cc ca
H (3.4)
cg

where ca and cg are aqueous and gaseous

concentration of a species.
For an ideal gas, the conversion is:

Hcc = Hcp RT (3.5)

Sometimes, this dimensionless constant is

called the waterair partitioning
coefcient KWA.
Henry solubility dened via aqueous-
phase mixing ratio (Hxp):

xp x
H Pa-1 (3.6)
p

where x is the molar mixing ratio in the

aqueous phase.
G/A
The Henry volatility constant is defined
as:

pc p 1
K H cp (3.7)
ca H

The SI unit for KHpc is Pa m3 mol1

..
The Henry volatility dened via
aqueous-phase mixing ratio (KHpx):

px p 1
K H xp (3.7)
x H

The SI unit for KHpx is Pa.

Another way to define Henry's volatility
constant is that the partial pressure of
the species in the vapor phase is directly
proportional to its liquid-phase mole
fraction.

yi P = xi Hi (3.8)

where Hi is Henrys constant (in bar)

Example 3.7
Assuming that carbonated water contains
only CO2 and H2O, determine the
composition of the vapor and liquid phases
in a sealed can of soda and the pressure
exerted on the can at 10C. Henrys
volatility constant for CO2 in water at 10C
is about 990 bar.
Solution
For CO2 : y1 P = x1 H1
For H2O : y2 P = x2 P2sat
P = x1 H1 + x2 P2sat

From Steam Table, at 10C:

P2sat = 0.01227 bar
Assume: x1 = 0.01
 P = x1 H1 + x2 P2sat
= (0.01) (990) + (0.99) (0.01227)
= 9.912 bar
With y1 1:
P 9.912
x1 0.01
H1 990
which confirm the original assumption.
By Raoults Law, y2 can be calculated:

x2P2sat 0.990.01227
y2 0.0012
P 9.912

y1 1 y2 1 0.0012 0.9988

The vapor phase is nearly pure CO2 as

assumed.
THANK YOU