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Henrys Law Solved Problems

At 25oC and 1 bar, the solubility of ethane in water is 0.33 x 10-4. Given Henry's constant is temperature dependent, the solubility of ethane at 25oC and 35 bar can be calculated using Henry's law and the fugacity coefficient of ethane at different pressures. For methane solubility in methanol at 0oC and 20 bar, the phase equilibrium and Lewis-Randall equations are used along with the second virial coefficients and vapor pressure of methanol. Iteration is done to find values of y1 and y2 such that the sum of mole fractions x1 and x2 is approximately 1, yielding a methane solubility of 0.0186.

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1K views3 pages

Henrys Law Solved Problems

At 25oC and 1 bar, the solubility of ethane in water is 0.33 x 10-4. Given Henry's constant is temperature dependent, the solubility of ethane at 25oC and 35 bar can be calculated using Henry's law and the fugacity coefficient of ethane at different pressures. For methane solubility in methanol at 0oC and 20 bar, the phase equilibrium and Lewis-Randall equations are used along with the second virial coefficients and vapor pressure of methanol. Iteration is done to find values of y1 and y2 such that the sum of mole fractions x1 and x2 is approximately 1, yielding a methane solubility of 0.0186.

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ayush
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© © All Rights Reserved
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Henry's Law: Solved Problems

Example 1: At 25oC and 1 bar pressure, the solubility of ethane in water is x C 2H 6 =

0.33 x 10 -4. Determine the solubility of ethane at 25oC when the pressure is 35 bar, At
25oC, the compressibility factor of ethane is given by the empirical relation
Z = 1 – 7.63 x 10-3 P – 7.22 x 10 -5 P2
where P is the bar. Assume Henry’s constant to be dependent only on temperature. At
25oC the vapour pressure of water is negligible and the gas phase can be assumed to
be pure ethane.

Solution: Let ethane be denoted by (1) and water by (2). The phase equilibrium
equation of ethane is f̂ 1V  x 1H 1 . Since vapor is pure gas, f̂ 1V  x 1H 1 , or, 1P = x1H1,

where 1 is the fugacity coefficient of pure ethane and P is system pressure. The
P
Z 1
fugacity coefficient is given by: ln    dP ..
0
P
P


For ethane: ln 1   7.63 10-3  7.22 10-5 P dP 
0

7.22 105 P 2
ln 1  7.63  103 P 
2
where P is given to be in bar. At 1 bar the fugacity coefficient of ethane is 1 =
0.99236. At 35 bar the value of 1 = 0.7325. Thus fugacity of ethane at 1 bar =
0.99236 and fugacity of ethane at 35 bar = 0.7325 x 35 x= 25.638 bar. Thus at ethane
pressure of 1 bar: x1H1 = 0.99236. Since x1 at 1 bar = 0.33 x 10 -4, therefore H1 =
30071.61 bar. And at ethane pressure of 35 bar: x1H1
25.638
 8.53 x 10 -4
30071.61
Example 2. At 0 oC the solubility of methane (1) in methanol (2) follows Henry’s law;
Henry’s constant is 1022 bar. The vapour pressure of methanol at 0 oC is 0.0401 bar.
The second virial coefficients at 0 oC are B11 = -53.9 cm3/mol, B12 = -166 cm3/mol,
and B22 = -4068 cm3/mol. At 0 oC and 20 bar, what is the solubility of methane in
methanol. The density of methanol at 0 oC is 0.8102 g/cm3 and molecular weight of
methanol is 32.04.

1
Solution: The phase equilibrium equations of the components at high pressure
account for the non-identity of vapour phase
y1 ˆ1 P  x 1 H 1

y2 ˆ2 P  x 2 f 2
there are two equations and two variables (x1 and y1). Note that since methane follows
Henry’s law therefore methanol follows the Lewis-Randall rule. f2 is the fugacity of
the compressed liquid which is calculated using
 V L PP2sat 
f 2  f 2sat exp  2  .
 RT 
where f 2sat is calculated using the virial equation

f 2sat B 22 P2sat
ln  2sat  ln 
P2sat RT

Substituting for f 2sat from the above equation into the previous equation we get

 B P sat   V L PP2sat 
f 2  P2sat exp  22 2  exp  2 
 RT   RT 
Molar volume of methanol is
1
V2L  x 10-6 = 3.95 x 10-5 m3/mol
08102/32.04
P2sat is given to be 0.0401 bar and f 2sat comes out to be 0.0398 bar and f2 comes out to
be 0.0412 bar.

Now let us determine the fugacity coefficients of the species in the vapour mixture
12 = 2(-166) + 53.9 + 4068 = 3789.9 cm3/mol
20 x 10 5
ln ˆ1  53.9  y 22 x 3789.9  x 10 -6
8.314 x 273.15
20 x 10 5
ln ˆ2  4068  y12 x 3789.9  x 10 -6
8.314 x 273.15
The calculation procedure is to assume a value of y1, calculate ˆ1 and ˆ2 and calculate
x1 and x2 from the phase equilibrium equations and see whether x1 + x2= 1, if not then
another value of y1 is assumed. Since x1 is so small let us find the approximate value
of y2 by taking
ˆ1 = 1 and ˆ2 = 1 and x1 = 0 or x2 =1

2
Thus we get
y 2ˆ2 P f 0.0412
x2 =  1 or y2 2  = 2.06 x 10-3
f2 P 20

Let us take y2 = 2.06 x 10-3, therefore y1 = 0.99794


At this value of y1 and y2, we get
ˆ1 = 0.95365 and ˆ2 = 0.7721
Therefore
0.99764x 0.95365x 20
x1 =  0.0186
1022
2.06 x10 3 x 0.7721 x 20
x2 =  0.7721
0.0412
The summation of x1 and x2 does not come to be 1. Now let us take y2 = 2.5 x 10-3
ˆ1 = 0.95366 and ˆ2 = 0.76983
Therefore
x1 = 0.0186
2.5x10 3 x 0.76983 x 20
x2 = = 0.934
0.0412
Let us take y2 = 2.6 x 10 -3
ˆ1 = 0.95366 and ˆ2 = 0.7693
Therefore
x1 = 0.0186
x2 = 0.97096
Let us take y2 = 2.65 x 10-3
ˆ1 = 0.95366 and ˆ2 = 0.76906
Therefore
x1 = 0.0186
x2 = 0.989
x1 + x2 = 1.0079

Since x1 + x2 1 we take y2 = 0.00265 and the solubility of methane in methanol, x1 =


0.0186.

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