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Transport Mass Transfer

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Henry's law relates the partial pressure of a gas to its concentration in water. It is used to calculate the equilibrium concentration of oxygen in water at different temperatures. The solubility of oxygen decreases with increasing temperature.

Henry's law states that the concentration of a gas dissolved in a liquid is directly proportional to its partial pressure above the liquid. It is used to calculate the equilibrium mole fraction and concentration of oxygen in water exposed to air at a given temperature and pressure.

Raoult's law relates the vapor pressure of a component above a solution to its mole fraction in the solution. Dalton's law relates the partial pressure of a component in a gas mixture to its mole fraction. The combination of Raoult's and Dalton's laws gives the relationship between the mole fraction of a component in the gas phase and liquid phase at equilibrium.

EXAMPLE NO.

2
CP302 Separation Process Principles
The Henrys law constant for oxygen dissolved in water is 4.06 x 10
9
Pa/(mole of
O2 per total mole of solution) at 293 K. Determine (i) the equilibrium mole
fraction of oxygen in water which is exposed to dry air at 1.013 x 10
5
Pa and 293
K, and (ii) the corresponding equilibrium solution concentration of oxygen in
water.

Given
H = 4.06 x 109 Pa/mole of O2 per total mole of solution
T = 293 K

Required
a)
oxygen
x
in water which is exposed to dry air at 1.013 x 105 Pa and 293 K
b) corresponding equilibrium solution concentration of oxygen in water

Solution
Assuming phase equilibrium at the gas-liquid interface, Henrys law is usually written as follows:
A A A
C H p
where pA is the gas-phase partial pressure of component A, CA is the liquid phase concentration of
component A that is in equilibrium with pA, and HA is the Henrys law constant for A in appropriate unit
(which in this case would be pressure / concentration).

The unit of Henrys law constant given in Example 2 is Pa/(mole of O2 per total mole of solution), which is
pressure / mole fraction. Therefore, we need to write Henrys law as follows:

A A A
x H p
where xA is the equilibrium mole fraction of A in the liquid phase.

(a) Equilibrium mole fraction of oxygen in the liquid phase can therefore be calculated using the following
expression :
oxygen
oxygen
oxygen
H
p
x
Since dry air contains 21 mole percent oxygen, partial pressure of oxygen (poxygen) can be calculated as
follows:
Pa 10 13 . 2 ) Pa 10 013 . 1 )( 21 . 0 (
4 5

T oxygen oxygen
P y p
Using the value of Henrys law constant given, we get
solution) /mol O Pa/(mol 10 06 . 4
Pa 10 13 . 2
2
9
4

oxygen
x

solution /mol O mol 10 25 . 5
2
6

oxygen
x


(b) Equilibrium concentration of oxygen in water can be calculated using the following expression:

T oxygen oxygen
C x C
where CT is the total number of moles of solution per unit volume.

Assuming the solution to be very dilute, CT can be calculated as follows:
3
3
3
kmol/m 5.56 5
kg/kmol 18
kg/m 1000
kg/m 1000
T
C

Therefore, we get

3 3 3
3
2
6
gm/m 33 . 9 gm/m 32 292 . 0 mol/m 292 . 0
kmol/m 5.56 5 solution /mol O mol 10 25 . 5



T oxygen oxygen
C x C



oxygen
C mg/l 33 . 9




























EXAMPLE NO. 1
CP302 Separation Process Principles
An exhaust stream from a semiconductor fabrication unit contains 3 mole% acetone and 97
mole% air. In order to eliminate any possible environmental pollution, this acetone-air
stream is to be fed to a mass-transfer column in which the acetone will be stripped by a
countercurrent, falling water stream at 293 K. The tower is to be operated at a total pressure
of 1.013 x 105 Pa. If the combined Raoult-Dalton equilibrium relation may be used to
determine the distribution of acetone between the air and the aqueous phase, determine (i)
the mole fraction of acetone within the aqueous phase which would be in equilibrium with
the 3 mole% acetone gas mixture, and (ii) the mole fraction of acetone in the gas phase
which would be in equilibrium with 20 ppm acetone in the aqueous phase. The vapour
pressure of acetone at 293 K is 5.64 x 104 Pa.

Given
YA = 30%
T = 293 K
PT = 1.013 x 10
5
Pa

Required
a) mole fraction of acetone within the aqueous phase which would be in equilibrium with the 3 mole%
acetone gas mixture
b) the mole fraction of acetone in the gas phase which would be in equilibrium with 20 ppm acetone in the
aqueous phase

Solution
Daltons law gives the partial pressure of a component A in the gas-phase as follows:
P y p
A
phase gas
A


where yA is the mole fraction of A in the gas-phase and P is the total pressure in the gas-phase.

Raoults law gives the partial pressure of component A in the gas-phase as follows:

A A
phase liquid
A
P x p


where xA is the mole fraction of A in the solution and PA is the vapour pressure of pure A.

In a perfectly ideal system, where ideal liquid and ideal vapor are assumed, Raoult's law is combined with
Daltons law to give the following relationship:
A A A
P x P y
which will be used to solve Example 1.

(i) Mole fraction of acetone within the aqueous phase which would be in equilibrium with 3 mole% acetone
gas mixture can be expressed as follows:

Pa 10 64 . 5
Pa) 10 013 . 1 )( 03 . 0 (
4
5



A
A
A
P
P y
x
x
A
0539 . 0

(ii) Mole fraction of acetone in the gas phase which would be in equilibrium with 20 ppm acetone in the
aqueous phase is calculated in two stages. First 20 ppm acetone in the aqueous phase is converted to
mole fraction of acetone in the aqueous phase as follows:


water g 980 , 999 acetone g 20
acetone g 20

phase aqueous in acetone ppm 20

A
x


mol ) 18 / 980 , 999 ( mol ) 58 / 20 (
mol ) 58 / 20 (



6
10 207 . 6



Then the mole fraction of acetone in the gas phase which would be in equilibrium with 20 ppm acetone in
the aqueous phase is expressed as follows:
Pa 10 013 . 1
Pa) 10 64 . 5 )( 10 207 . 6 (
5
4 6




P
P x
y
A A
A

6
10 45 . 3


A
y




























Question No. 1
Interphase Mass Transfer(pdf)
What is the equilibrium concentration (in mg/L) of oxygen in water at 10C, 25C and
40C?

Given
T 1,2,3= 10C, 25C and 40C

Required
Equilibrium concentration of O2 for each temperature

Solution
The mole fraction of oxygen in air is 0.21. The pressure of air will be assumed to be 1.0 atm.
Thus, the partial pressure of oxygen in the air is 0.21 atm.

At 10C:
xOxygen = 0.21 atm/32,700 atm = 6.42 10-6 mol O2/mol H2O

(6.42 10-6 mol O2/mol H2O) (32000 mg O2/mol O2) (mol H2O/18.0 g H2O) (997 g H2O/L)
= 11.4 mg/L

At 25C:
xOxygen = 0.21 atm/43,800 atm = 4.79 10-6 mol O2/mol H2O

(4.79 10-6 mol O2/mol H2O) (32000 mg O2/mol O2) (mol H2O/18.0 g H2O) (997 g H2O/L)
= 8.5 mg/L

At 40C:
xOxygen = 0.21 atm/53,500 atm = 3.93 10-6 mol O2/mol H2O

(3.93 10-6 mol O2/mol H2O) (32000 mg O2/mol O2) (mol H2O/18.0 g H2O) (997 g H2O/L)
= 7.0 mg/L


Oxygen, like the vast majority of gases, is more soluble in water at low temperature than at
elevated temperature.

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