SAMPLE CALCULATIONS AND RESULTS
At the first step of the calculations, densities of water and acetone should be determined
from the measured weights and volumes:
msample − mempty flask
ρwater =
Volume
161.92 g −142.6 g
¿
20 ml
g
¿ 0.966
ml
157.61 g −142.6 g
ρacetone =
20 ml
g
¿ 0.750
ml
After this step, there should be a calibration made between density and acetone molar
fraction values. The density and the mole fraction of the first sample (75ml acetone – 5ml water)
will be handled only. The rest will be tabulated according to the calculation shown below. The
molecular weight of water and acetone is 18.015 g/mol and 58.08 g/mol respectively:
g
macetone=0.750 ×75 ml
ml
¿ 56.25 g
56.25 g
mole of acetone=
g
58.08
mol
¿ 0.968 moles
g
m water =0.966 × 5 ml=4.83 g
ml
4.83 g
moles of water = =0.268 moles
g
18.015
mol
Finally, the mole fraction of acetone and the density of the solution can be determined:
0.968 moles
x acetone= =0.783
( 0.968+0.268)moles
206.26 g − 142.6 g g
ρ solution= =0.806
79.0 ml ml
The same procedure is applied to all solution samples and the values are tabulated in the table
below:
Table 5.1 Molar fraction of acetone vs density of the mixture.
Mole Fraction of Acetone Density of Solution
0 0.966
0.194 0.911
0.419 0.859
0.628 0.823
0.783 0.806
1.00 0.750
This data is plotted to a graph to obtain a linear relationship. The graph is shown below:
Density vs Acetone Mole Fraction
1.2
1
f(x) = − 0.206067452472096 x + 0.956360984861175
0.8 R² = 0.987318686824889
Density (g/ml)
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2
Mole Fraction of Acetone (mol/mol)
Figure 5.1 Density vs acetone mole fraction graph
Since this relation is obtained by the equation y = -0.2061x + 0.9564, liquid mole fraction
of acetone (and water) can be determined from the densities of the solutions. For 550 mbar
recording, the calculation is carried out as follows:
167.77 g − 142.6 g g
ρ solution= =0.9254
27.2 ml ml
0.9254 − 0.9564
mole fraction of acetone= =0.1504
− 0.2061
mole fraction of water=1− 0.1504=0.8496
Same steps are applied to all recorded pressures and the results are shown in the table
below:
Table 5.2 Density and liquid mole fraction of acetone values for each pressure data
Density
Pressure (mbar) Mole Fraction (Acetone) Mole Fraction (Water)
g/ml)
550 0.9254 0.1504 0.8496
450 0.9304 0.1262 0.8738
350 0.9303 0.1266 0.8734
250 0.8952 0.2969 0.7031
After finding the liquid mole fractions, saturation pressure of both water and acetone will be
calculated at 55 °C with the Antoine coefficients[?]:
sat 2756.22
ln Pacetone =14.3145 − =4.577
55 ℃ +228.060
sat
Pacetone =972.22 mbar
sat 3885.70
ln Pwater =16.3872 − =2.761
55℃ +230.170
sat
Pwater =158.16 mbar
By using the samples from the distillation flasks, vapor mole fraction of both water and
acetone can also be determined. One example (550 mbar) is shown below:
163.39 g −142.6 g g
ρ solution= =0.77
27 ml ml
Same relation between density and liquid molar fraction can be used for vapor mole
fraction:
0.7700 − 0.9564
y acetone = =0.9044
−0.2061
y water =1 −0.9044=0.0956
Same operation is applied to all recordings for each pressure data and the results are
tabulated below:
Table 5.3 Vapor molar fractions of water and acetone in different pressures.
Pressure Density
Mole Fraction (Acetone) Mole Fraction (Water)
(mbar) g/ml)
550 0.77 0.9044 0.0956
450 0.7703 0.9030 0.0970
350 0.7838 0.8375 0.1625
250 0.7869 0.8224 0.1776
To proceed to calculations, a relation between P (550mbar) and x values will be
established by using the modified Raoult’s Law and activity coefficient equations x 1, y1, γ 1and
P1sat represents the mole fractions, activity coefficient and saturation pressure of acetone
respectively:
P y1
γ 1= sat
P1 x1
P y2
γ 2= sat
P2 x2
P y1 2
ln sat
=x 2 [ A 12+2 ( A 21 − A12 ) x 1]
P x1
1
P y2 2
ln sat
=x 1 [ A 21+ 2 ( A 12 − A21 ) x 2]
P x2
2
P y1
=exp (x 2 [ A 12+2 ( A21 − A 12 ) x 1 ] )
2
sat
P 1 x1
P y2
=exp (x 1 [ A 21+2 ( A12 − A 21 ) x2 ] )
2
sat
P 2 x2
P y 1=P1 x 1 × exp ( x 2 [ A 12+2 ( A 21 − A12 ) x 1 ])
sat 2
2 x 2 × exp (x 1 [ A 21 + 2 ( A 12 − A 21 ) x 2 ])
P y 2=Psat 2
P ( y 1 + y 2 )=P1sat x 1 × exp ( x 22 [ A 12+ 2 ( A 21 − A12 ) x 1 ] )+ P2sat x 2 × exp ( x 21 [ A21 +2 ( A 12 − A 21) x 2 ] )
P=P1sat x 1 × exp ( x 22 [ A12 +2 ( A 21 − A 12) x 1 ] )+ P sat
2 x 2 ×exp ( x 1 [ A 21 +2 ( A12 − A 21 ) x 2 ] )
2
When these relations are solved by Excel solver, A12 and A21 values are determined to be
2.04 and 1.546 respectively.
These margules parameters are used for obtaining a relation between composition and
pressure values. This relation is plotted on a graph as shown below:
Composition vs Pressure
1200
liquid molar
fractions
1000
vapor molar
800 fractions
Pressure (mbar)
600 Experimental
liquid mole
fractions
400
Experimental
200 vapor mole
fractions
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Composition
Figure 5.2 Composition vs Pressure graph and experimental composition values
