Wesley Viola (Daniel Bowen, Jingcheng Huang)

Performed, Due, Submitted: 10/8/14, 10/22/14, 10/22/14

Experiment #3 - Binary Liquid Phase Diagram
Abstract:
In this lab, ten mixtures of varying ethanol and heptane compositions were
brought to their boiling points and the produced distillates and residues were
collected. Using an Abbe refractometer, the indices of refraction of the samples
were measured and compared to a calibration curve that related index of refraction
and mixture composition. A phase diagram of the molar fraction of heptane in the
residue and distillate of different mixtures versus the mixtures boiling points was
then plotted. From lines of best fit of this plot, the minimum boiling azeotrope was
determined.
The minimum boiling azeotrope for the mixture was found to be .346407
while the true value is .32. The approximately 6 percent error of the experimental
value indicates that this lab was a successs.
Introduction:
In ideal mixtures of liquids with different volatilities, the partial pressure of
each component can be calculated by Raoults Law:

where XA is the molar fraction of A in the mixture and

is the vapor pressure of a

pure solution of A. Ideal mixtures in this situation are defined as mixtures in which
the different components experience no intermolecular interactions among each
other. For each component, the deviation from ideal behavior can be expressed as
the activity coefficient:

where YA is the molar fraction of A in the vapor above the mixture and P is the total
pressure. Since intermolecular interactions govern the activity coefficient, this
expression can be interpreted as a measure of these interactions. If in a mixture of A
and B, A experienced a significant attractive force with B, then it makes sense that A
would become less volatile than expected and it would make up less of the total
vapor pressure compared with the ideal model. In this case the numerator of the
fraction in the above expression would be less than the denominator and yield an
activity coefficient that is less than one. When the mixture behaves ideally, the
partial pressure of A is as expected (as defined by Raoults Law) and so the
numerator is equivalent to the denominator and

is equal to one. Following the

same logic, repulsive forces would cause

to be greater than one.

The existence of azeotropes, ratios of components in mixtures that exhibit
boiling points above or below either of the boiling points of the components, can be
explained by deviations from Raoults Law. A mixture can have a minimum boiling
azeotrope, for example, if the components experience repulsive forces, raising each
others volatility and giving the mixture an extra low boiling point.
In this lab, ten mixtures of varying ethanol and heptane compositions were
boiled and the compositions of the produced distillates and residues were
determined using a calibration curve of mixture composition versus index of
refraction. A phase diagram was created for the mixtures and the azeotrope was
found. Activity coefficients of ethanol and heptane were also found using known
vapor pressures of each.
Experimental Methods:
The procedure as described in the lab handout Experiment 5 Binary Liquid Phase
Diagram was followed with a few exceptions.
A
The ethanol and heptane volumes
were reduced by 30%. The data obtained during the lab was also substituted for
more accurate data collected by another group.
Results:
Table 1. Masses of components and indices of refraction for samples. Boiling
temperature of each sample is also included
Sample M Empty M EtOH (g)
M
Heptane
(g)
Undistilled
Index
Distillate
Index
Residue
Index
Boiling
Temp
E X X X 1.3620 X X X
M1 47.3212 68.1029 71.3762 1.3640 1.3670 1.3630 76
M2 47.3023 64.4065 71.8475 1.3680 1.3640 1.3680 72.1
M3 46.8403 57.2117 68.9096 1.3730 1.3725 1.3720 71
M4 47.6171 57.7158 70.5712 1.3755 1.3755 1.3745 70.55
M5 47.0786 54.2203 68.5903 1.3780 1.3750 1.3775 71.3
M6 47.4146 52.9048 69.7972 1.3805 1.3750 1.3760 71.8
M7 46.792 50.7517 67.8521 1.3820 1.3750 1.3735 71.4
M8 47.1978 50.3451 70.6094 1.3850 1.3750 1.3835 73.2
M9 49.6984 51.3391 72.1714 1.3870 1.3755 1.3870 75.1
M10 48.4141 49.4392 70.3495 1.3870 1.3760 1.3860 79
H X X X 1.3870 X X X

Figure 1. Vapor pressures of heptane and ethanol at varying temperatures.
B










y = 0.179x
2
- 14.214x + 419.7
y = 0.4683x
2
- 43.518x + 1286.4
0
200
400
600
800
1000
1200
1400
1600
0 50 100
V
a
p
o
r

P
r
e
s
s
u
r
e

Degrees C
Heptane Vapor
Pressure
Ethanol Vapor
Pressure
Poly. (Heptane
Vapor Pressure)
Poly. (Ethanol
Vapor Pressure)
Conclusion:
Figure 2. Calibration curve of refractive index of mixture versus mole fraction of
ethanol in mixture.

Table 2. Data plotted in Figure 2. The refractive index and molar ethanol fraction of
the different mixtures.
Refractive index Molar fraction of ethanol
1.3620 1
1.3640 0.93247938
1.3680 0.833336216
1.3730 0.658537262
1.3755 0.630830802
1.3780 0.519477142
1.3805 0.414168511
1.3820 0.334969433
1.3850 0.252527774
1.3870 0.146259877
1.3870 0.096362442
1.3870 0



y = -671.72x
2
+ 1811.2x - 1219.8
0
0.2
0.4
0.6
0.8
1
1.2
1.3600 1.3650 1.3700 1.3750 1.3800 1.3850 1.3900
M
o
l
e

F
r
a
c
t
i
o
n

o
f

E
t
h
a
n
o
l

Refractive Index
Figure 3. Plot of mole fraction of heptane versus boiling point of mixture.

Minimum boiling azeotrope found at heptane mole fraction = .346407
Table 4. Data plotted in Figure 3. Distillate and residue compositions for different
mixtures.

Distillate Composition Residue Composition

Mole fraction heptane Mole fraction heptane Boiling Temp
E 0 0 78.3
M1 0.12537508 0.03499268 76
M2 0.05557312 0.15132928 72.1
M3 0.28474825 0.26858048 71
M4 0.38880793 0.35277793 70.55
M5 0.370625 0.46489825 71.3
M6 0.370625 0.40732672 71.8
M7 0.370625 0.31809137 71.4
M8 0.370625 0.72541177 73.2
M9 0.38880793 0.89971268 75.1
M10 0.40732672 0.84823312 79
H 1 1 98.4

y = 57.626x
2
- 46.451x + 78.806
y = 50.377x
2
- 28.375x + 76.562
0
20
40
60
80
100
120
0 0.2 0.4 0.6 0.8 1 1.2
B
o
i
l
i
n
g

t
m
p
e
r
a
t
u
r
e

o
f

m
i
x
t
u
r
e

Mole fraction heptane

Residue
Composition
Distillate
Composition
Poly. (Residue
Composition)
Poly. (Distillate
Composition)
Figure 4. Activity coefficients of heptane and ethanol in residues of varying heptane
compositions.

Table 4. Data plotted in Figure 4. Activity coefficients of residue components
heptane and ethanol.

Activity coefficient of residue compositions

Heptane Ethanol
E N/A 1
M1 7.293619233 1.007143606
M2 0.857741764 1.450271536
M3 2.57555597 1.333520063
M4 2.720965454 1.311868888
M5 1.9160105 1.5841945
M6 2.148096168 1.401136201
M7 2.790298996 1.238022096
M8 1.147583997 2.855007526
M9 0.907795109 7.024032824
M10 0.881680459 3.848749633
H 1 N/A

This labs calculations began with the making of calibration curve relating index
of refraction of a mixture with its molar composition. Knowing the masses of ethanol
and heptane in each mixture, the molar compositions of the mixtures could be
0
1
2
3
4
5
6
7
8
0 0.5 1 1.5
A
c
t
i
v
i
t
y

c
o
e
f
f
i
c
i
e
n
t

Molar fraction of heptane
Heptane
Ethanol
Poly. (Heptane)
Poly. (Ethanol)
determined. The molar fractions of ethanol were then plotted against the measured
indices of refraction of the mixtures and a second order polynomial was fit to the data
1
.
Using this calibration curve, the compositions of the distillates and residues
could be determined simply by plugging each samples recorded index of refraction into
the best-fit polynomial
2
. The heptane compositions of the distillates and residues were
then plotted against the boiling points of the mixtures. Lines of best fit (polynomials)
were found for each phase (shown in Figure 3). The azeotrope of a phase diagram is
either the maximum or minimum sum of the phase curves. Therefore, the polynomials
were added and the minimum of this summed function was found. This minimum
boiling azeotrope was determined to exist when heptane made up a mole
fraction .346407 in the ethanol/heptane mixture
3
.
Finally, the activity coefficients were found for the ethanol and heptane in the
residues using the determined compositions and the literature values of vapor
pressures of pure heptane and pure ethanol shown in Figure 1
4
. These activity
coefficients were plotted against molar composition of heptane.
The true minimum boiling azeotrope for the heptane/ethanol mixture can be
found in literature to be at the heptane molar fraction of .32
5/C
. This value differs from
the calculated value by only about 6%, suggesting that the experimental method is valid.
The main sources of error for this lab are likely human error. Preparing the
many samples involved volume measurements that likely accumulated error. The
refractometer readings were also subjective and, since the tool was difficult to read, it is
likely that the values obtained with it have substantial error. Other sources of error
might include some unintended evaporation of samples at temperatures other than the
boiling point, possibly occurring at stages such as when the samples were pipetted onto
the refractometer. This evaporation at another temperature would change the
composition of the sample and contribute to error in the phase diagram.
The plot of the activity coefficients showed that, as the azeotrope ratio was
reached around molar fraction of heptane = .34, the activity coefficients of heptane and
ethanol appear to be at about 3 and 1 respectively. Together, these activity coefficients
are quite high relative to any other point which makes sense because at the azeotropic
point. These high activity coefficients represent strong repulsive interactions between
the ethanol and heptane. These forces cause higher than ideal volatilities for each
component and thus an extra low boiling point for the mixture.
Looking at the Figure 4, it is difficult to judge the data trends with certainty since
there are some significant outliers to the fitted curves, especially the heptane curve.
Judging by the polynomial fits, the activity of heptane decreases as the azeotrope is
reach while the activity of ethanol increases. However, weighting the outliers more, the
curves might also be seen as third order polynomials. In this interpretation, the
azeotropic point is represented by the local maximum and local minimum of the two
curves. It would be worthwhile to analyze more samples in this mixture composition
range to get better detail in the graph. Doing so would allow one to more confidently
identify trends.
Overall, the experiment seems to be a success and the calculated values prove to
be legitimate.

References:
A. Course Document Experiment 5 Binary Liquid Phase Diagram, Course
Website on Trunk
B. The Vapour Pressures of Pure Substances, T. Boublk, V. Fried, E. Hla, Elsevier,
New York, NY, 1973
C. http://eweb.chemeng.ed.ac.uk/chem_eng/azeotrope_bank.html