Experiment No.

1
Partial Molar Volume and Refractive Index of Solutions

I. INTRODUCTION

A refractometer measures the extent to which light is bent when it moves from air
into a sample and is typically used to determine the index of refraction of a liquid sample. The
refractive index is a unit less number. [1] Measurement of the refractive index depends on the
temperature and wavelength of the light. Determination of the refractive index can provide
information on the purity of a substance, but not its exact composition. [2]

The immersion refractometer is the most precise type of refractometer, which contains a
prism fixed at the end of an optical tube containing an object lens, an engraved scale reticule,
and an eyepiece. This instrument is dipped into a beaker of the liquid clamped in a water bath
for temperature control. The measuring prism acts as the refractive index reference. The
refractive index of the prism has to be higher than that of the medium under measurement, as
otherwise there will be no total internal reflection. In practice, the difference of refractive
indexes has to be relatively high. [3]. Temperature is one of the greatest factors which can
influence the refractive index. Each substance reacts differently and specifically to
temperature. [4]
The objectives of this experiment are (a) to determine the indices of refraction of the
different proportions of liquids in a binary mixture (b) to determine the specific and molecular
refractivity of each proportion of liquids in a binary mixture and their relation with their mole
fraction and (c) to determine the relationship of the partial molar volumes and their
concentration in a binary mixture.

II. METHODOLOGY

In determining the refractive index of toluene and methanol, abbe refractometer was used.
The prism of the refractometer was washed using acetone, distilled water and was dried using
cotton. It was calibrated by placing drops of water in the prism, and taking the reading to correct
adjustment by making the boundary of light and dark fields seen in the eye piece that intersects
the crosshairs. The temperature was also recorded.

The refractive index of pure toluene was determined by putting amount of it in the prism,
and taking the correct adjustment. Same steps were repeated for every solution. The prism is
cleaned before the reading of another solution. The temperature was recorded.
 The amount of methanol required in preparing solutions with 0% to 50% volume
percentages of methanol with 10% increments were calculated. Calculations were repeated to
find the required volume of toluene to make 0% to 50% toluene with 10 % increments.

In determining the density of the solution, the dry empty pycnometer, which was cleaned,
was weighed. Also, the pycnometer was filled with solution together with its cap was weighed.
The difference of the weighed masses is equal to the mass of the solution. The density of the
solution was calculated by taking the ratio of the mass of the solution and volume labeled on the
pycnometer which on our case, was 10 mL.

III. RESULTS AND DISCUSSIONS:

The amount of methanol required for the mixture was calculated using:

x
vol . percent = (100),
x+10

where x is the volume of methanol. 10 mL toluene was mixed with the calculated amount of
methanol for every volume percentages needed ranging from 0 to 50%. Few drops of the mixture
were put in the prism of the abbe refractometer to determine its refractive index. To know the
density of the solution, the dry empty pycnometer was and enough solution was poured on it, and
weighed again. Mass of the solution is calculated by taking the difference of the two weighed
masses. That is,

masssolution = masspycnometer+solution - massempty pycnometer .

The density of the solution was calculated by taking the ratio of the mass and volume of
the pycnometer labeled on it, which is 10 mL.

Table 1. Refractive Indices of Solutions with Different Concentrations of Methanol

Mixture
Refractive
Toluene Methanol Rs Rm Density Xtoluene Xmethanol MWave
Index
100% 0% 1.506 0.3426 31.5672 0.86724 1 0 92.14
90% 10% 1.5 0.4484 35.2263 0.85783 0.774 0.226 78.56
80% 20% 1.462 0.3313 22.6311 0.82986 0.6035 0.3965 68.31
70% 30% 1.472 0.3357 20.2461 0.83419 0.4703 0.5297 60.31
60% 40% 1.485 0.369 19.8817 0.77676 0.3634 0.6366 53.88
50% 50% 1.379 0.2851 13.8587 0.81062 0.2757 0.7243 48.61
Table 1 shows the summary of the data obtained and calculated from the experiment with
different concentrations of methanol present in the solution. It shows that the mole fraction of
methanol decreases as refractive index, density, specific refraction and molecular refraction
decreases.
Table 2. Refractive Indices of Solutions with Different Concentrations of Toluene

Methano Toluene Refractive Rs Rm Density Xmethanol Xtoluene MWave

l Index (g/mL)
100% 0% 1.332 0.078 2.5176 0.79243 1.000 0.00 32.04
6
90% 10% 1.36 0.279 9.6199 0.79096 0.9594 0.0406 34.48
0
80% 20% 1.376 0.301 11.2153 0.76221 0.9131 0.0869 37.26
0
70% 30% 1.391 0.288 11.6796 0.82338 0.8598 0.1402 40.47
6
60% 40% 1.429 0.308 13.6445 0.83506 0.7976 0.2024 44.20
7
50% 50% 1.54 0.361 17.5677 0.8681 0.7243 0.2757 48.61
4

On the other hand, Table 2 shows the summary of the data obtained and calculated from
the experiment with different concentrations of toluene present in the solution. It shows that the
mole fraction of toluene increases as refractive index, density, specific refraction and molecular
refraction increases.

Specific Refractivity vs. Mole Fraction of Methanol

0.50

0.40

0.30
Specific Refractivity (Rs)
0.20

0.10

0.00
0.00 0.20 0.40 0.60 0.80

Mole Fraction of Methanol (Xm)

Figure 1. Specific Refraction vs. Mole fraction of methanol

 Figure 1 shows the relationship between specific refraction and mole fraction of
methanol. The equation of the line is y=- 0.0705 x+ 0.2944 , where x is the mole fraction of
water and y is the specific refractivity. The preciseness of the data is 0.9457. This graph shows
that as mole fraction of water increases, the specific refraction decreases. The graph is a second
order polynomial series of relationship.

Molar Refractivity vs. Mole Fraction of Methanol

40

30

Molar Refractivity (Rm) 20

10

0
0.000.100.200.300.400.500.600.700.80

Mole Fraction of Methanol (Xm)

Figure 2. Molecular Refractivity vs. Mole fraction of water

Figure 2 shows the equation of the line y = -9.621x + 13.12, where x is the mole fraction
of water and y is the molar refraction. R, which is the linearity of the line, is 0.9999. The graph
shows the molar refraction is inversely proportional to mole fraction of water. That is, as the
mole fraction of water increases, the molar refraction decreases.

Based on the figures shown above, the mole fraction of water decreases as the specific refraction
and molecular refraction increases because the value of the refractive index of ethanol is a higher
than water.

Specific refractivity and molecular refractivity, which has been determined in this
experiment, would be more useful in determining the variation of a solution in order to know its
contents by comparing it to the true value.

IV. 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?
2. What are the practical uses of refractive index in chemical engineering? Give some
examples.

There are many practical uses of refractive index in chemical engineering. It measures the
concentration of solute in an aqueous solution and also used to identify a substance or
confirm the purity by measuring the concentration. Knowing the refractive index could
give some information about molecular structure of compounds, determine the sugar
content of solutions and identify the identity of a sample by relating or comparing the
known values to refractive index. It is also used to calculate the focusing power of lenses,
and the dispersive power of prisms.

3. Why is it necessary to the temperature at which the reading from the refractometer is
obtained? Explain your answer.

The temperature has a major effect on the actual reading as can be seen in the formula
below. Generally, the refractive index decreases with increasing temperature. The
medium is less dense, the refraction of the light is usually reduced. Most refractive
indices in the literature are reported at 20 oC or 25 oC. Thus, it is important to record the
temperature at which the refractive index was acquired as well in order to take the
temperature effect into account afterwards.

4. In what practical applications is (a) specific refractivity (b) molecular refractivity

more useful?

Specific refractivity and molecular refractivity, which has been determined in this
experiment, would be more useful in determining the variation of a solution in order to know its
contents by comparing it to the true value.

5. From the results of the mixing volumes, what can you say about the volumes of the
pure components added together theoretically and actually?
6. What is the difference/ similarity between the resulting volume using equation 7 and
the volume by simply adding the measured volume of methanol and toluene.

Conclusions:

In this experiment, the refractive index and the density of water and ethanol solutions were
determined. By knowing the density, the specific and molecular refraction of each solution were
also determined upon calculations. The mole fraction was observed and related to calculated
values and gathered data. As seen in the plotted graph, the refractive index increases as the mole
fraction of ethanol decreases. Moreover, the specific and molecular refraction also increases with
increase in mole fraction of ethanol. Since water has greater refractive index than ethanol, adding
up more of this would increase the refractive index of the solution. The refractive index increases
as density of the mixture increases. The true value of the refractive index of water at 20 o is
1.3330, and the obtained value from our experiment is 1.373 at 28 oC. Meanwhile, the true value
of the refractive index of ethanol at 20o is 1.36, and the obtained value is 1.344 at 28 oC. The
difference in temperature is 8oC. The values obtained are somewhat close to the true values.

References:

1) Davis, Z.; Refractive index definition; 1996-2013

http://www.pcmag.com/encyclopedia/term/50348/refractive-index]

2) Andrew Skipor, Ph.D., Head of Educational Programs; Refractive index in Chemical

Engineering; 2012
http://www.newton.dep.anl.gov/askasci/eng99/eng99387.htm

3) Garland, C. W.; Nibler J. W.; Shoemaker D. P.; Experiments in Physical Chemistry 8th
Edition; McGraw-Hill 2009; pp. 613-617.

http://www2.ups.edu/faculty/hanson/labtechniques/refractometry/intro.htm
http://www.kpatents.com/assets/files/downloads/refractive_index_principle.pdf
http://www.edurite.com/kbase/application-of-refraction-of-light

Appendices:

A. Calculating proportions of toluene and methanol

x
(100)
Vol% = x +10

a.) x =10 mL toluene + 0% methanol

x=0.0 mL methanol
b.) 10 mL toluene + 10% methanol
x
(100 )
10% = x +10

x= 1.11 mL methanol
c.) 10 mL toluene + 20 % methanol
 1.11+ x
(100)
20% = x +10

x=1.1125 mL methanol
d.) 10 mL toluene + 30 % methanol
2.1125 + x
(100)
30% = x +10

x=1.2714 mL methanol
e.) 10 mL toluene + 40 % methanol
3.1125 + x
(100)
40% = x +10

x=1.4833 mL methanol
f.) 10 mL toluene + 50 % methanol
4.1125+ x
(100)
50% = x +10

x=1.78 mL methanol

B. Calculating Density
mass pycnometer with mixturemass empty pycnometer
= volume of pycnometer

mass empty pycnometer = 19.2097 g

volume pycnometer = 10 mL
27.771319.2097 g
10% methanol solution: = 10. mL = 0.857 g/mL

C. Calculating Mole Fraction

For 90% toluene + 10 % methanol :

0.90 x 10 mLx 0.86724 g /mL 0.10 x 10 mLx 0.79243 g /mL

nt = 92.14 g /mol + 32.04 g /mol

nt = 0.09448 + 2.473252x10-3
nt = 0.512 mol
0.495
xtoluene = 0.512 = 0.7740

D. Calculating Mave

E. Calculating the Specific Refraction and Molar Refraction

 1
Rs= [(n2 1) / (n2+ 2)] Rm= Rs (Mave)

where: n= refractive index

= density
Mave = Average Molecular weight
Rs = specific refraction
Rm = molecular refraction
For 90% water + 10 % ethanol:
1
2 2
Rs= [(1.373250 1) / (1.373250 + 2)] 0.826 = 0.276

Rm= 0.276[(0.742x46)+(0.258x18)] = 10.702