Justine Camille Castillo

3ChE-A
Group No. 1

Date Performed: February 5, 2016

Date Submitted: May 31, 2016
Experiment No. 1

Partial Molar Volume and Refractive Index of Solutions

Introduction
Some properties of pure chemical substances change when mixed together with another
substance. These are known as the partial molar properties. These properties are dependent to the
composition of the mixtures; therefore, partial molar properties are known to be intensive
variables. These properties are important because they can show the significance of the degree of
non-ideality of a system. When the components of a solution are mixed, their individual
properties are modified to some degree due to their molecular interactions. This implies that
substances in a solution cannot remain truly unaffected despite being in the presence of another
material [1]. One of these properties is the partial molar volume, which is the easiest to visualize
among the others. For an instance, 1 mol of H 2O is added to a huge volume of pure water at
room temperature. The volume increases by 18cm3 and therefore we could say that 18cm3/mol is
the partial molar volume of water. However, if we add the same amount of H2O to a huge volume
of ethanol, the total volume will only increase by 14cm 3 and therefore its partial molar volume is
14cm3/mol. The reason for this difference in volume is that the increase in volume depends on
the identity of the molecules that surround the given amount of water. Partial molar volume is
denoted by the equation

( nV )

V A=

A p ,T ,n '

Where VA is the partial molar volume of substance A, nA is the amount of A, and n is the amount
of all other substances which are indicated as constant [2].
For binary mixtures, it is found that the total volume, V, of a solution is
V =n A V A +n B V B
Refractometry is also involved in the experiment. It is a technique that measures how
light is refracted when it passes through a given substance. The amount by which the light is
refracted determines the refractive index, . It is the ratio of the velocity of light in a vacuum to
the velocity of light in the medium being measured. This can be used to identify an unknown
liquid compound, or it can be used to determine whether the liquid compound being measured is
pure or not [3].
The experiment aims to determine the indices of refraction, the specific and molecular
refractivities of the different proportions of liquids in a binary mixture and their relation with
their mole fraction. It also aims to determine the relationship of the partial molar volume and
their concentration in binary mixture.

Methodology
The materials needed for the experiment were Abbe refractometer for the reading of the
refractive index, a 24.628cm3 pycnometer, four 25mL Erlenmeyer flasks which held the two
reagents needed: toluene and methanol, one for the mixing of the reagents and one for the
acetone, which was used in cleaning the prisms of the refractometer together with the cotton,
analytical balance for the determination of mass of the pycnometer and the solution, two
calibrated pipettes to transfer the measured volumes of the liquid reagents and cork stoppers
which fit the Erlenmeyer flask since the reagents were highly volatile.

The prism of the Abbe refractometer was first cleaned by placing a drop of acetone on it
and was gently wiped with cotton. It was rinsed using few drops of distilled water and then
gently wiped with cotton. The lower prism was then saturated with distilled water and the
settings of the refractometer were modified by adjusting the hand wheels and the compensator
dial. This was followed the reading of the refractive indices of pure toluene and pure methanol.
The pycnometer was weighed together with its lid and thermometer and was recorded.
The liquid samples were then placed in the pycnometer separately. The excess samples on the
surface of the pycnometer were wiped out with tissue and their weighs were determined and
recorded afterwards. Using the masses obtained and the volume indicated on pycnometer, the
densities of the samples were determined.
Same procedures were used for the determination of the refractive indices and density of
the solutions prepared with different volume percentages. The amount of methanol and toluene
to be used in the preparation of the solutions with different volume percentages were computed
using the equation
0.10=

amount
24.628

Results and Discussion

The mass of the first solution shown on Table 1 (see Appendix) was obtained by
subtracting the weighed mass of the dry and empty pycnometer, which was 32.80g, from the
mass of pycnometer with the solution. Using the mass of the solution obtained and the volume
indicated on the pycnometer, which was 24.628cm3, the density of this solution was calculated
which was shown below:

mass
volume

21.16 g
g
=0.859185 3
3
24.628 c m
cm
The Partial Molar Volumes (PMV) of toluene and methanol as shown on Table 2 (see

Appendix) were calculated using the formula:

PMV =

MW
solution

Where MW is the molecular weight of toluene (92.14g/mol) or methanol (32.04g/mol).

g
mol
c m3
PMV methanol=
=32.2912
g
mol
0.859185 3
cm
32.04

Same calculations were applied to the rest of the solutions.

41.0
f(x) = 3.5x + 36.97
R = 0.95

40.0

39.0

Partial Molar Volume (cm3/mol)

38.0

37.0

36.0

35.0
0

0.2

0.4

0.6

0.8

1.2

1.2

Mole Fraction

Figure 1 Plot of Partial Molar Volume vs. Mole fraction (Methanol)

118.0
116.0

f(x) = - 9.94x + 116.33

R = 0.94

114.0
112.0
Partial Molar Volume (cm3/mol)

110.0
108.0
106.0
104.0
102.0
0

0.2

0.4

0.6
Mole Fraction

0.8

Figure 2 Plot of Partial Molar Volume vs. Mole Fraction (Toluene)

As shown on Figures 1 and 2, the partial molar volume of ethanol increases together with
its mole fraction, meanwhile, the partial molar volume of toluene decreases as its mole fraction
increases. The linearity of both graphs was close to 1, which shows that partial molar volume of
ethanol is directly proportional with its mole fraction while the partial molar volume of toluene is
inversely proportional with its mole fraction.
Using the partial molar volume, mole fraction, average molecular weight obtained on
Table 2 and the mass of the solution on Table 1, the total volume of the solution could be
computed using
V =n A V A +n B V B
x
( A V A + nB V B)
mass of solution

average MW
V =

V=

( ( 0.4 )( 38.0831 ))+(0.6)(109.5185)=24.628 cm

( 20.72
68.1 )

The calculated total volume was 24.628cm3 is equal to the measured volume of the pycnometer
which was 24.628cm3 as well.
Specific and molecular refractivities from Table 3 (see Appendix) were also calculated
using the formulas:

[ ]

21 1
Rs= 2
+2

Rs=

1.502 1
1
=0.253557
2
1.502 +2 0.859185

Rm=Rs (MW ave )

Rm=0.253557 ( 92.14 )=23.36274

These

refractivities

were

plotted

against

methanols

mole

fractions

as

shown:

0.27
f(x) = - 0.1x + 0.26
R = 0.96

0.25
0.23

Specific Refraction (Rs)

0.21
0.19
0.17
0.15
0

0.2

0.4

0.6
Mole Fraction

Figure 3 Rs vs. Plot of Mole Fraction of Methanol

0.8

1.2

25
f(x) = - 18.79x + 23.21
R = 0.99

20

15
Molecular Refraction (Rm)
10

0
0

0.2

0.4

0.6

0.8

1.2

Mole Fraction

Figure 4 Plot of Rm vs. Mole Fraction of Methanol

The linearities of Figures 3 and 4 were 0.9567 and 0.9923, respectively. Both were close to 1
which show good linearity. It was shown that the specific and molecular refractivies were both
decreasing as the mole fraction of methanol was increasing, thus, the specific and molecular
refractivities of solutions are both inversely proportional with mole fraction.

Answers to Questions
1.

What do refraction graphs Rs vs. mole fraction of methanol and Rm vs. mole fraction of
methanol indicate? What are the practical uses of these graphs?
It can be seen from Figures 3 and 4 that as the mole fraction of methanol increases,
the specific and molecular refractivities of the solution both decreases because the refractive

index of pure toluene, which is 1.496, is greater than that of pure methanol, which is 1.328.
These 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 [4].
2. What are the practical uses of refractive index in chemical engineering? Give as many
examples as you can.
Refractive index has a large application in chemical engineering. It is widely used in
identifying a substance, confirming its purity, measuring a substances concentration.
Generally, it is used to measure the concentration of solute in an aqueous solution. It can be
used to determine the sugar content, which is a process known as Brix degree. It is also
applied for estimation of thermophysical properties of hydrocarbons and petroleum mixtures
[5].
3. Why it is necessary to note the temperature at which the reading from the refractometer is
obtained? Explain your answer.
In most substances, the refractive index usually decreases when the temperature
increases [5]. Therefore, it is necessary to take note of the temperature and maintain it in a
constant value as much as possible since the reading of the refractive index would be affected
if this was not done.
4. In what practical applications is (a) specific refractivity (b) molecular refractivity more
useful?
Specific and molecular refractivity would be more useful when determining the
concentration and composition of each substance in a binary mixture.
5. From the results of mixing volumes, what can you say about the volumes of pure components
added together theoretically and actually?
Mixing the volumes of pure components seems like an ordinary addition; when you
add 1mL of pure component A to a 1mL of pure component B, their total volume would

result to 2mL of A-B solution. However, in reality, the increase in volume of a pure
component depends on the molecules surrounding it.
6. What difference/similarity between the resulting

volume

using

the

equation

V =n A V A +n B V B
and the volume by simply adding the measured volume of methanol and toluene?
There is a difference in the resulting volume using the equation and by simply
adding the measured volume of methanol and toluene. The equation depends on the mole
fraction and the average molecular weight of the solution. However, when we simply add the
measured volumes of methanol and toluene, these factors were not considered, thus, resulting
to wrong calculations.
7. Why is Partial Molar Volume important?
Partial molar volume is important because it can denote the degree of non-ideality of a
system. In a solution, the constituents are intimately mixed. Due to molecular interactions
between the species in the solution, their individual properties are modified to some degree.
This implies that substances in a solution cannot have private properties, or ones that remain
truly unaffected despite being in the presence of another material [1].

Conclusions
The concept of partial molar volume was seen in the experiment. After the procedures
were executed, it can be inferred that the relationship of the partial molar volume and mole
fraction depends on the liquids in a binary mixture. In the experiment, it can be seen that the
partial molar volume of methanol is directly proportional to its mole fraction; on the other hand,
the partial molar volume of toluene is inversely proportional to its mole fraction. As the mole

fraction of the substance increases, its partial molar volume gets closer to its pure liquid molar
volume.
Mole fraction of a substance affects its refractive index. In the experiment, the specific
and molecular indices of the solutions are inversely proportional to the mole fraction of
methanol; however, it is directly proportional to that of toluene. It can be concluded from the
data obtained that toluene is more capable of refracting light compared to methanol.
For future endeavors, it is recommended that the prisms of the refractometer must be
cleaned well after each reading of the solutions and to maintain a constant temperature reading to
have more accurate readings of the refractive indices.

Appendix
Table 1 Densities and Refractive Indices Obtained
%Methanol
Mass of Pycnometer
Mass of
(by volume)
with the Solution (g) Solution (g)
0
53.96
21.16
10
53.84
21.04
20
53.8
21
30
53.66
20.86
40
53.52
20.72
50
53.48
20.68
60
52.81
20.01

Density
(g/cm3)
0.859185
0.854312
0.852688
0.847003
0.841319
0.839695
0.812490

Refractive
Index ()
1.502
1.498
1.489
1.477
1.457
1.447
1.389

70
80
90
100

52.69
52.58
52.48
52.32

19.89
19.78
19.68
19.52

0.807617
0.803151
0.799090
0.792594

Table 2 Partial Molar Volumes of Toluene and Methanol

%Methano
l
X of methanol X of toluene PMV of methanol
0
0
1
37.2912
10
0.1
0.9
37.5039
20
0.2
0.8
37.5753
30
0.3
0.7
37.8275
40
0.4
0.6
38.0831
50
0.5
0.5
38.1567
60
0.6
0.4
39.4343
70
0.7
0.3
39.6723
80
0.8
0.2
39.8929
90
0.9
0.1
40.0956
100
1
0
40.4242

1.38
1.368
1.356
1.34

PMV of toluene
107.2412
107.8528
108.0583
108.7835
109.5185
109.7304
113.4045
114.0887
114.7232
115.3061
116.2512

Ave. MW
92.14
86.13
80.12
74.11
68.1
62.09
56.08
50.07
44.06
38.05
32.04

Table 3 Specific and Molecular Refractivities of Methanol

Density
Refractive
X of
Ave.
3
%Methanol (g/cm )
Index ()
methanol
MW
Rs
Rm
0
0.859185
1.502
0
92.14
0.253557
23.36274
10
0.854312
1.498
0.1
86.13
0.250416
21.56836
20
0.852688
1.489
0.2
80.12
0.246098
19.71736
30
0.847003
1.477
0.3
74.11
0.239329
17.73664
40
0.841319
1.457
0.4
68.1
0.229131
15.60385
50
0.839695
1.447
0.5
62.09
0.224355
13.93019
60
0.812490
1.389
0.6
56.08
0.192161
10.77641
70
0.807617
1.38
0.7
50.07
0.187073
9.366762
80
0.803151
1.368
0.8
44.06
0.180782
7.965268
90
0.799090
1.356
0.9
38.05
0.174595
6.643358
100
0.792594
1.34
1
32.04
0.166136
5.323013

References
[1] Smith, J., et. al. (2004). Introduction to Chemical Engineering Thermodynamics, (7th ed.).
United States: McGraw-Hill.
[2] Atkins, P. & De Paula, J. (2014). Atkins Physical Chemistry, (10th ed.). Oxford, UK: Oxford
University Press.

[3] Chem 211 - Refractometry. (n.d.). Retrieved April 9, 2016, from

http://academics.wellesley.edu/Chemistry/chem211lab/Orgo_Lab_Manual/Appendix/Instru
ments/Refractometry/refractometry.html
[4] Caddarao, P. S. (n.d.). Experiment 2: Refractive Index. Retrieved April 15, 2016, from
http://documents.mx/documents/x2g2aw.html
[5] Koohyar F (2013) Refractive Index and Its Applications. J Thermodyn Catal 4:e117.
doi:10.4172/2157-7544.1000e117