Salazar, Nicole Anne U.

Date Performed: March 4, 2019

Section: P-ChE321-L Group No. 8 Date Submitted: March 25, 2019

Experiment No. 1
Partial Molar Volume and Refractive Index of Solutions

Introduction

Refractive Index

Refractive index is a value calculated from the ratio of the speed of light in a vacuum to
that in a second medium of greater density [1]. The refractive index of a material is directly
proportional to the extent to which a light beam is deflected or refracted upon entering or leaving
the material. To some extent, the refractive index of a medium is dependent to the frequency of
light passing through. When a heterogenous light beam contains more than one frequency that
enters or leaves the medium, the wavelength experiences a slightly different degree of refraction.
The measure of refractive index can determine the concentration of a solute in a solvent in most
solutions [2].

Partial Molar Volume

The partial molar volume of a substance in a mixture is the change in volume per mole of
the substance added to the mixture. The partial molar volume is dependent on the composition of
the mixture. The composition is responsible for the changing environments of the molecules in
the mixture. The slope of the plot of the total volume as the amount of substance is changed with
all other variables is the partial molar volume. Measurement of the dependence of the volume of
a solution upon its composition is a common method of measuring the partial molar volume [3].
 The relation between partial molar volume and refractive index is that one can calculate
the partial molar volume when the refractive index of a mixture with known composition is
measured, the molar volume may be estimated and from that the partial molar volume can be
calculated [4].

The objectives of this experiment were to determine the indices of refraction of the
different proportions of liquids in a binary mixture, to determine the specific and molecular
refractivities of each proportion of liquids in a binary mixture and their relation with their mole
fraction and lastly is to determine the relationship of the partial molar volumes and their
concentration in a binary mixture.

Methodology
The prisms of the refractometer were cleaned by placing a drop of acetone and wiping it
gently with a cotton and was rinsed with a few drops of water and then gently wiped with a
cotton. The lower prism was saturated with distilled water, closed and the thermometer is set in
its socket. The refractometer was situated in order to make sure that light passes through the
lower prism. The hand wheel and compensator dial were adjusted to make sure that the
demarcation line between light and dark fields seen through the eyepiece is distinct. Three
readings were done using the fresh water drops. Lastly, the water on the prism was absorbed by a
cotton and the refractometer is ready for the experiment to carry on.

The dry empty pycnometer was weighed for an easier reading of the succeeding
measurements. The pycnometer was filled to the brim with liquid sample, pure toluene was the
first liquid sample used, the pycnometer was covered and although some of the liquid spilled it
was better for it that way to remove any bubbles present. Excess liquid was wiped and the
covered pycnometer was weighed.

The volume of methanol required for the mixtures with the volume percentages ranging
from 10%-50% with 10% increments, using the pure 10 mL toluene, was calculated beforehand.
The refractive index of the mixtures was determined the same way the refractive index of the
fresh water sample was determined. The same procedure was the repeated with the use of pure
methanol, and 10%-40% toluene.
Results and Discussion

The mass of the pure toluene was obtained by weighing the empty pycnometer, and the
pycnometer was filled to the brim with pure toluene and the resulting weight of the pycnometer
with the pure toluene was subtracted to the weight of the empty pycnometer which turned out to
be 8.3759 g. The pycnometer’s volume is 10 mL and the density of the solution was calculated
using the obtained mass of pure toluene and volume of the pycnometer. The partial molar
volumes were obtained using the formula:

𝑀𝑊
PMV = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (Equation 1)

The molecular weight (MW) is the molecular weight of either pure toluene or pure
methanol. The same calculations through out the varying solutions were applied.

Specific Volume vs. Weight Percent Methanol

1.3
Specific Volume, cm3/g

1.28

1.26
y = 0.0009x + 1.1914
1.24
R² = 0.9754
1.22

1.2

1.18
0% 2000% 4000% 6000% 8000% 10000% 12000%
Weight Percent

Fig. 1: Plot of Specific Volume vs the Weight Percent of Methanol for each Solution

As shown in figure 1, the R squared value of the graph is close to the value of 1 which
indicates that the regression prediction fits almost perfectly with the data.
 Partial Molar Volume vs. Mole Fraction
(Methanol)
41.5
Partial Molar Volume, cm3/mol 41
y = 6.0207x2 - 4.2841x + 39.362
40.5
40
39.5
39
38.5
38
0 0.2 0.4 0.6 0.8 1 1.2
Mole Fraction

Fig. 2: Plot of Partial Molar Volume vs. the Mole Fraction of Methanol

Partial Molar Volume vs. Mole Fraction

(Toluene)
120
Partial Molar Volume, cm3/mol

118
116
114
y = 10.434x2 - 17.874x + 117.78
112
110
108
0 0.2 0.4 0.6 0.8 1 1.2
Mole Fraction

Fig. 3: Plot of Partial Molar Volume vs the Mole Fraction of Methanol

Figure 2 and 3 shows the plot of partial molar volume of methanol and toluene together
with their mole fractions. As shown in Figure 2, the partial molar volume of methanol is
proportional to its mole fraction, as the mole fraction increases the partial molar volume of
methanol also increases. While for toluene, as the mole fraction increases its partial molar
volume decreases.
 Using the known partial molar volume, mole fraction, average molecular weight obtained
and the mass of the solution, the total volume of the solution can be calculated using the
equation:

V = nAVA + nBVB (Equation 2)

Rs vs. Mole Fraction

0.4
0.35
0.3
0.25
y = -0.0948x + 0.3704
Rs

0.2
0.15
R² = 0.8444

0.1
0.05
0
0 0.2 0.4 0.6 0.8 1 1.2
Mole Fraction

Fig. 4: Plot of Specific Refractivity (Rs) vs of the Mole Fraction of Methanol

Rm vs. Mole Fraction

40
35
30
25
Rm

20
15 y = -24.527x + 35.719
10 R² = 0.9295
5
0
0 0.2 0.4 0.6 0.8 1 1.2
Mole Fraction

Fig. 5: Plot of Molecular Refractivity (Rm) vs. the Mole Fraction of Methanol
 Figure 4 and 5 showed good linearity, being their linearity values were close to the value
of 1. Both the specific and molar refractivities are both decreasing as the mole fraction of
methanol was increasing. Thus, specifying that the specific and molecular refractivities are both
inversely proposrtional to the mole fraction of methanol.

Answers to Questions
1. What do the refraction graphs (a) and (b) indicate? Give an interpretation of the graphs.
What are the practical uses of these graphs?
- Figures 4 and 5 indicates that as the mole fraction of methanol is increasing the
molecular and specific refractivites of the solution are inversely proportional to the
mole fractions. The graphs can be used in solutions or products because there is a
change on the effects of the medium at different proportions where light is bent.

2. What are the practical uses of the refractive index in chemical engineering? Give some
examples.
- Applications of using the refractive index is for identifying a particular substance,
confirmation of its purity, or measure its concentration. For example, the refractive
index can determine the sugar content in a sugar solution.

3. Why is it necessary to note the temperature at which the reading from the refractometer is
obtained? Explain your answer.
- It is because most substance’s refractive index depends on the temperature. When the
temperature increases the refractive index decreases. Which is why it is necessary to
record the temperature as well as it is important to maintain it at constant temperature
as much as possible.

4. In what practical application is (a) specific refractivity (b) molecular refractivity useful?
- Molecular refractivity can be useful in the radio refractive index that is referred to a
zero value altitude or sea level that is effective in removing the systematic altitude
density of air [5].
 5. From the results of the mixing volumes, what can you say about the volumes of the pure
components added together theoretically and actually?
- The increase in volume of a pure component depends on the molecules surrounding
it.
6. What is the difference/similarity between the resulting volume using equation 7 and the
volume by simply adding the measured volume of the methanol and toluene?
- The equation is dependent on the mole fraction and the average molecular weight of
the solution, whereas when the volumes are simply measured these factors are not
considered and it would result to a wrong calculation.
7. Why is partial molar volume important?
- It is important because it denotes the degree of non-ideality of a system.

Conclusions

The relationship between the partial molar volume and the mole fraction is dependent on
the liquids in a binary mixture. The partial molar volume methanol is directly proportional to its
mole fraction, while the partial molar volume of toluene is inversely proportional to its mole
fraction.

The refractive index is affected by the mole fraction. In the experiment, it can be
concluded from the data and calculations obtained that toluene, compared to methanol, is more
capable of refracting light.

References
[1] Retrieved on March 24, 2019 from https://www.microscopyu.com/microscopy-
basics/refractive-index-index-of-refraction
[2] Retrieved on March 24, 2019 from
http://www.kpatents.com/assets/files/downloads/refractive_index_principle.pdf
[3] Retrieved on March 24, 2019 from
http://www.everyscience.com/Chemistry/Physical/Mixtures/a.1265.php
[4] Retrieved on March 24, 2019 from
https://pubs.acs.org/doi/abs/10.1021/ed079p865?journalCode=jceda8
[5] Retrieved on March 24, 2019 from
https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/JZ064i010p01439?fbclid=IwAR1bUaia
LjH0Nzxcp43C4_ZYMGo-bYBUXaM5pBT-K0hZ6g_SX5eys9qikNQ