CHE553 Chemical Engineering Thermodynamics

3/12/2015

HENRYS LAW
Table 10.1 lists Henrys constant values at 25 oC (298.15K) for a few gases
dissolved in water.
Henrys constant is also an indicator for solubility of a gas in the solvent. The
greater the Henrys constant, the lower is the solubility.

Henrys law states that the partial pressure of the species in the vapor phase is
directly proportional to its liquid-phase mole fraction.
y i P x i Hi

10.4

where Hi is Henrys constant. Values of Hi come from experiment.

Application of Raoults law and Henrys law:
Liquid mixtures that form an ideal solution at low pressure
Use Raoults law for all species
Liquid mixtures that do not form an ideal solution and at low pressure
Use Raoults law for solvent
Use Henrys law for solute
Gases that dissolve in a liquid mixture (e.g. air in water)
Use Henrys law for the dissolved gaseous species

Least soluble
in water
Very soluble
in water

CHE553 Chemical Engineering Thermodynamics

3/12/2015

Example 10.2

Solution:
Given Henrys constant for CO2 in water = 990 bar (i.e CO2 dissolved in
water)
Henrys law is applied to species 1 and Raoults law is applied to species 2 :
y 1 P = x 1 H1
y2P = x2P2sat
F = 2-2+2 = 2, only T is given. Need to specify the mole fraction to solve the
problem. Assume the vapor phase is nearly pure CO 2 (y11) and the liquid
phase is nearly pure H2O (x21). Take x1 = 0.01.
Sum the two equations give
P = x1H1 + x2P2sat
With H1 = 990 bar, x1 = 0.01 and P2sat = 0.01227 bar (Table F.1 at 10 oC or
283.15 K),
P = (0.01)(990) + (0.99)(0.01227) = 9.912 bar
Then by Raoults law, eq. (10.1) written for species 2:

Assuming that carbonated water contains only CO 2(1) and H2O(2), determine
the compositions of the vapor and liquid phases in a sealed can of soda and
the pressure exerted on the can at 10 oC (283.15K). Henrys constant for CO2
in water at 10oC (283.15K) is about 990 bar.

y2

x 2 P2 sat 0.99 0.01227

0.0012
P
9.912

y1 = 1 - y2 = 1 - 0.0012 = 0.9988, and the vapor phase is nearly pure CO 2

as assumed.
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VLE BY MODIFIED RAOULTS LAW

The simplest correlation to predict activity coefficient for binary mixture is as

follow:
ln 1 = Ax22
ln 2 = Ax12
where A is a function of temperature only or simply a constant.
This correlation can only be used in some liquid mixtures which exhibit small
deviation from ideal solution.
Bubblepoint and dewpoint calculation by modifed Raoults law:
Because iyi = 1, eq. (10.5) may be summed over all species to yield

In real life, most solutions are non ideal i.e they do not obey Raoults law. Non
ideal solution deviate from Raoults law.
The non ideality exhibit by these solutions due to dissimilarity in the sizes of
molecules, shapes of the molecules, and inter-molecular interactions between
molecules.
Modified Raoults law accounts for non-ideal solutions, or non-idealities in the
liquid phase:

y i P x i i Pi sat

i 1,2,..., N

P x i i Pi sat

10.5

10.6

where i is activity coefficient.

There are a number of correlations that can be used to predict the value of
activity coefficient e.g. Margules, Van Laar, Non-Random Two Liquid (NRTL),
Wilson, etc.

Because ixi = 1, eq. (10.5) may be summed over all species to yield

y / P
i

sat

10.7

i i

CHE553 Chemical Engineering Thermodynamics

3/12/2015

Example 10.3

Solution:
(a) BUBL P calculation (given T = 318.15K and x1 = 0.25)
1. Calculate P1sat and P2sat using Antoine equation for T = 318.15K

For the system methanol(1)/methyl acetate(2), the following equations provide

a reasonable correlation for the activity coefficients:
ln 1 = Ax22
ln 2 = Ax12
where A = 2.771 - 0.00523T
In addition, the following Antoine equations provide vapor pressures:
ln P1sat 16.59158

3643.31
T 33.424

ln P2 sat 14.25326

ln P1sat 16.59158

3643.31
T 33.424

ln P2 sat 14.25326

2665.54
T 53.424

2. Calculate activity coefficients from the given equation

ln 1 = Ax22
ln 2 = Ax12
where A = 2.771 - 0.00523T

2665.54
T 53.424

3. Calculate P by eq. (10.6)

where T is in kelvins and the vapor pressures are in kPa. Assuming the validity
of eq. (10.5), calculate
(a) P and {yi}, for t/T = 45oC/318.15K and x1 = 0.25
(b) P and {xi}, for t/T = 45oC/318.15K and y1 = 0.60
(c) T and {yi}, for P = 101.33 kPa and x1 = 0.85
(d) T and {xi}, for P = 101.33 kPa and y1 = 0.40
(e) The azeotropic pressure, and the azeotropic composition, for t/T =
45oC/318.15K

P x i i Pi sat x11P1sat x 2 2 P2sat

i

4. Calculate yi by eq. (10.5)

y i x i i Pi sat P

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(c) BUBL T calculation (given P = 101.33 kPa and x1 = 0.85)

Calculate T1sat and T2sat using Antoine equation for P = 101.33 kPa

(b) DEW P calculation (given T = 318.15K and y1 = 0.60)

Values of P1sat, P2sat and A are unchanged from part (a).
Iteration procedure is required to find the liquid phase composition
and to calculate the activity coefficients.
Initial values are provided by Raoults law, for which 1 = 2 = 1.0.
The required steps, with the current value of 1 and 2, are:
1. Calculate P by eq. (10.7), written
1
P
y1 / 1P1sat y 2 / 2 P2 sat
2.

Calculate x1 by eq. (10.5)

yP
x1 1 sat
and
1P1

Evaluate activity coefficients;

ln 1 = Ax22
4. Return to the first step.
Iterate to convergence on a value for P.

Ti sat

x 2 1 x1

3.

ln 2 = Ax12

11

Bi
Ci
Ai ln P

A mole fraction weighted average of these values then provides an initial T:

T = x1T1sat + x2T2sat
An iterative procedure consists of the steps:
1. For the current value of T calculate values for A, 1, 2, P1sat, P2sat, and
= P1sat/P2sat
2. Find a new value for P1sat from eq. (10.6) written:
P
P1sat
x11 x 2 2
3. Find a new value for T from the Antoine equation for species 1
B1
T
C1
A1 ln P1sat
4. Return to the initial step
Iterate to convergence on a value for T.

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CHE553 Chemical Engineering Thermodynamics

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(d) DEW T calculation (given P = 101.33 kPa and y1 = 0.40)

Calculate T1sat and T2sat using Antoine equation for P = 101.33 kPa
Initial value of T:
T = y1T1sat + y2T2sat
Because the liquid phase composition is unknown, the activity coefficients
are initialized as 1 = 2 = 1.
Iterative procedure:
1. Evaluate A, P1sat, P2sat, and = P1sat/P2sat for the current value of T
2. Calculate x1 by eq. (10.5)
x1

3.
4.

y1P

and

(e) First determine whether or not an azeotrope exists at the given

temperature.
This calculation is facilitated by the definition of a quantity called the
relative volatility:
12

x 2 1 x1

10.8

At an azeotrope y1 = x1, y2 = x2, and 12 = 1. By eq. (10.5),

1P1sat
Calculate 1 and 2 from the correlating equation
Find a new value for P1sat from eq. (10.7) written:

y i i Pi sat

xi
P

y y
P1sat P 1 2
1 2

5.

y1 x1
y2 x2

Therefore,

12

Find a new value of T from Antoine equation for species 1

1P1sat
2 P2 sat

10.9

B1
T
C1
A1 ln P1sat

6. Return to the initial step

Iterate to convergence on the value of T.

13

14

The correlating equations for activity coefficients:

ln 1 = Ax22
ln 2 = Ax12
when
x1 = 0, ln 2 = Ax12 = A(0) = 0 2 = exp(0) = 1
x2 = 1, ln 1 = Ax22 = A(1) = A 1 = exp(A)
and
when
x1 = 1, ln 2 = Ax12 = A(1) = A 2 = exp(A)
x2 = 0, ln 1 = Ax22 = A(0) = 0 1 = exp(0) = 1

For the azeotrope, 12 = 1, and eq. (10.9) becomes

Therefore in these limits, eqn. (10.9) becomes

Thus the azeotropic occurs at the value of x1 for which this equation is
satisfied when the activity coefficient ratio has its azeotrope value of 1.4747
(from eq. (A)).

ln 1 ln1.4747 0.388
2

12 x10

P sat exp A
1
P2 sat

1az P2 sat 65.64

1.4747
2 az P1sat 44.51

The difference between the correlating equations for ln 1 and ln 2 provides

the general relation:
ln

P sat
and 12 x11 sat 1
P2 exp A

For T = 318.15 K or 45oC, from part (a)

P1sat = 44.51 kPa
P2sat = 65.64 kPa
A = 1.107
The limiting values of 12 are therefore
(12)x1=0 = 2.052
(12)x1=1 = 0.224
Because the value at one limit is greater than 1, whereas the value at the
other limit is less than 1, an azeotrope does exist. Because 12 is a
continuous function of x1 and must pass through the value of 1 at some
intermediate composition.

1
Ax2 2 Ax12 A x2 x1 x2 x1 A x 2 x1 A 1 x1 x1 A 1 2 x1
2

When ln 1/2 = 0.388, substitute into eq. (B), gives x1az = 0.325. For this
value of x1,
ln 1az = Ax22 1az = exp[(1.107)(1-0.325)2] = 1.657

15

With x1az = y1az, eq. (10.5) becomes

Paz = 1azP1sat = (1.657)(44.51) = 73.76 kPa
x1az = y1az = 0.325

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CHE553 Chemical Engineering Thermodynamics

3/12/2015

REFERENCE
Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction to Chemical
Engineering Thermodynamics. Seventh Edition. Mc Graw-Hill.

PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303

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