K.A. Cruz, D.L.C. Fernando, R.A.

Soriano, Partial Molar Volume of a Substance, 2014

1

Partial Molar Volume of a Substance
K.A. Cruz, D.L.C. Fernando, R.A. Soriano
Department of Chemical Engineering, College of Engineering, University of the Philippines Diliman
28 January 2014
_________________________________________________________

ABSTRACT
_________________________________________________________________________________

Usage of simple mixing rules for non-ideal solution results to a high error, hence, an understanding of
partial molar properties is of utmost importance to be able to predict what changes occur upon
changing the composition of a solution. The experiment aims to establish a method to determine the
partial molar volume of ethanol and water in a solution with each other by measuring the volume of
mixtures with different composition. An expression of volume as a function of composition is
established to be able to determine its derivative which will be used in partial molar volume
calculations. Experimental values of partial molar volume of ethanol had a maximum deviation of
1.295% while that of water had 3.536%. Measured molar volume of the ethanol-water solution
reached a deviation of 0.982%.

Keywords: partial properties, solution, composition, molecular interaction, summability relation, Gibbs-
Duhem equation
_________________________________________________________



1. Introduction

Some properties of a pure chemical
species change when it is in a solution with
other species. These properties that are
affected by solution composition are called
partial molar properties. The definition of a
partial molar property of species i in a
solution is:

*
()

The symbol

stands for any

property dependent on composition such as
enthalpy and volume. It is a response
function; it represents the change of total
property nM because of the addition of a
differential number of moles of species i, ni,
to a solution at constant pressure and
temperature. As such, partial molar
properties are intensive variables.
Conventions state that M
i
is the molar
property of pure species i and M is the
molar property of the solution
[1][2]
.

If we apply this to volume, addition
of n
i
of species i to a solution with total
property nM at constant temperature and
pressure will result to a total property
change represented by nM and the
corresponding partial molar volume of
species i is

.

The molar property of the solution in
terms of the partial molar properties of all
the species in it are expressed in the
summability relations:

Partial molar properties are
important because they 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]
.

K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

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For a binary system, it is found that
the partial molar volumes and solution
molar volume are:

[]

[]
[D1]

[]

This provides us with a method to
determine the partial molar properties of 2
chemical species when mixed with each
other. This is done by preparing mixtures
with different composition and measuring
the resulting mass of a known volume. An
expression for V as a function of x
i
will be
obtained here and its derivative will provide
the second term of the right hand side of
the equation.

This experiment aims to determine
the partial molar volumes of ethanol and
water in solutions of varying concentrations.
This will be done through the use of a
pycnometer, which consists of a small glass
flask and a glass stopper with a capillary
hole running through the center. Excess
liquid is ejected from the pycnometer
through this capillary hole in order to obtain
the specified solution volume with a very
high accuracy.The experimentally obtained
values for the volume of the solutions will
also be plotted against the ethanol mole
fractions. The generated curve will be
compared to the theoretical one.

2. Material & Methods

The materials for this experiment
were a pycnometer for accurately
measuring 10 mL of the sample solutions, 6
50-mL volumetric flasks to hold the ethanol
solutions, a 10-mL pipette for transferring
the ethanol into the volumetric flasks, a 10-
mL graduated cylinder and a 1-mL pipette
for transferring the solutions into the
pycnometer, 3 1000-mL beakers for the
water baths of the ethanol solutions and the
pycnometer, a 2000-mL beaker for
temporarily holding the waste solutions, a
thermocouple for measuring the
temperature of the tap water baths, ice for
lowering the temperature of the water
baths, an alcohol thermometer for
measuring the wet bulb temperature, a
piece of cloth for drying the pycnometer, a
paper tong for handling the pycnometer, a
stopwatch for measuring time intervals, and
masking tape for making flask labels. The
reagents that were used in this experiment
were distilled water and ethanol. The
apparatus that were used for this
experiment were the analytical balance and
the hot plate.

First, the room temperature and
pressure were recorded. The wet bulb
temperature was also determined. This was
done by wrapping a small piece of cotton
around the bulb of an alcohol thermometer
and securing it in place with a rubber band.
The cotton was dipped in water afterwards
and the thermometer was rapidly, but
cautiously, swung in a circular manner for
30 seconds. The alcohol thermometer
reading was recorded and 2 more trials
were done.

The empty volumetric flasks were
labeled using pieces of masking tape and
were covered. They were weighed using
the analytical balance and their masses
were recorded. The ethanol solutions were
then prepared according to the following
table:

Table 1
Ethanol Mole Fractions
Solution Mole Fraction Ethanol
A 0
B 0.2
C 0.4
D 0.6
E 0.8
F 1

The corresponding ethanol volume for each
solution was calculated through the
following equation:

K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

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Isolating V
ethanol
on one side of the equation
through algebraic manipulation will yield an
expression on the other side in terms of the
desired ethanol mole fraction, the densities
of water and ethanol, and the molar masses
of water and ethanol. The ethanol volumes
for each solution are then obtained:

Table 2
Correct Ethanol Volume for Each Solution
Solution Ethanol Volume
A 0.0000
B 22.4176
C 34.2139
D 41.4916
E 46.4296
F 50.0000

The solutions were all prepared in their
corresponding volumetric flasks. Ethanol
was transferred into the flasks via the 10-
mL pipette and after the correct amount had
been transferred, the flasks were filled to
the mark with distilled water. The flasks
were then covered afterwards and were
weighed once again. The masses were
recorded. The flasks were placed in a 2 tap
water baths afterwards. Using a
thermocouple, the temperature of the baths
was monitored and was kept at room
temperature by the use of a hot plate, when
the temperature had dropped below
26.5
O
C, and ice, when the temperature had
risen above 26.5
O
C. The mole fraction of
ethanol in each flask was recalculated using
the respective masses of ethanol and
water.


Figure 1
The 6 Sample Solutions in the Water Baths

Following this, the empty
pycnometer was washed and dried. It was
weighed thrice with the analytical balance
and the mass for each trial was recorded.
The volumetric flask with solution A was
then removed from the tap water bath and
10 mL of the solution was transferred to the
pycnometer using a graduated cylinder. The
capillary stopper was then slowly inserted
into the pycnometer opening, making sure
that there were no spaces or trapped
bubbles within the capillary space.

For the times when the space wasnt
completely filled with the solution, the
stopper was removed and a small amount
of the solution was placed into the
pycnometer via the 1-mL pipette. The
capillary stopper was then cautiously
replaced back onto the pycnometer. On the
other hand, for times when the solution
overflowed from the top of the capillary
space, a piece of cloth was used to dry the
pycnometer and the stopper, and remove
some of the solution that stayed on the top
of the stopper but outside of the capillary
space as a bead of liquid.

The pycnometer was then placed in
the water bath for five minutes in order for
the solution inside to reach the temperature
of the bath. Afterwards, the pycnometer
was carefully removed from the bath by
handling it by the neck. The pycnometer
was dried with a piece of cloth and was
transferred to the analytical balance through
the use of a paper tong. The mass of the
pycnometer with the solution was recorded.
The solution in the pycnometer was then
placed in the 2000-mL waste beaker. Two
more trials with the pycnometer and
solution A were done to ensure the
consistency of the experimental data. The
pycnometer, graduated cylinder, and the 1-
mL pipette were then cleaned afterwards.

K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

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Figure 2
Pycnometer in the Water Bath

The same procedure was repeated
for solutions B to F. Upon finishing, all the
used glass wares were washed, and the
contents of the waster beaker and the
leftover solutions were disposed in the
designated waste jar.

3. Results & Discussion

The mole fractions of the solutions
were recalculated by solving for the actual
masses of ethanol and water inside the
flasks. The ethanol masses were obtained
by subtracting the mass of the empty flasks
from the recorded masses with the ethanol.
The water masses were obtained similarly:

Table 3
Ethanol and Water Masses in each Solution
Solution Ethanol mass, g

Water mass, g
A 0.0000 49.7933
B 20.3565 25.2183
C 26.9526 16.9129
D 32.7548 9.2531
E 36.5771 3.8803
F 39.1921 0.0000

These values were converted to moles by
dividing the masses in the previous table
with the appropriate molar mass, 46.08
g/mol for ethanol and 18.02 g/mol for water:

Table 4
Moles of Ethanol and Water in each Solution
Solution
Ethanol
moles
Water
moles
Ethanol mole
fraction
A 0.0000 2.7632 0.0000
B 0.4418 1.3995 0.2399
C 0.5849 0.9386 0.3839
D 0.7108 0.5135 0.5806
E 0.7938 0.2153 0.7866
F 0.8505 0.0000 1.0000

Similarly, the masses of the solution
that were placed within the pycnometer
were determined by same procedure that
was employed for table 2:

Table 5
Masses of the Pycnometer Solutions
Solution Trial 1

Trial 2 Trial 3
A 9.9874 10.0005 10.0326
B 9.1903 9.2158 9.2297
C 8.8044 8.8122 8.8363
D 8.4235 8.4368 8.4612
E 8.1118 8.1305 8.1289
F 7.8738 7.8642 7.8823

The average was taken and by dividing
these by the volume of the solution inside
the pycnometer, the densities of the 6
sample solutions were obtained.

Table 6
Densities of the 6 Sample Solutions
Solution Average mass, g Density, g/mL
A 10.0068 1.00068
B 9.2119 0.92119
C 8.8176 0.88176
D 8.4405 0.84405
E 8.1237 0.81237
F 7.8734 0.78734

Since the mass of the sample
solutions are known, as outlined in table 2,
their molar volumes can be calculated as
well. This was done by taking the quotient
of the solution masses and their respective
density, which was then subsequently
divided by the total number of moles in the
parent solution:

Table 7
Molar Volume of the 6 Sample Solutions
Solution Molar volume, mL/mol
A 18.0077
B 26.8700
C 32.6540
D 40.6508
E 49.3520
F 58.5259

Plotting the molar volumes, as the
ordinate, against the mole fraction of
K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

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ethanol, as the abscissa, yields the
following graph:


Figure 3
Solution Molar Volume versus Ethanol Mole
Fraction

Using the equation for best fit curve,
the derivative at the solution mole fractions
can be determined and through equations 1
and 2, the partial molar volumes at those
points can be determined:

Table 8
Partial Molar Volume of Ethanol and Water in
the 6 Sample Solutions
Solution
V

EthanoI
V

Water

A 54.7841 17.9442
B 56.3876 17.7256
C 57.1401 17.3844
D 57.9133 16.6642
E 58.4084 15.5946
F 58.5813 14.1470

Plotting the partial molar volumes of
the two species against the ethanol mole
fraction separately:


Figure 4
Ethanol Partial Molar Volume vs x
Ethanol



Figure 5
Water Partial Molar Volume vs x
Ethanol


Theoretical values were obtained by
digitizing the points in the following figure:













Figure 6
Theoretical Partial Molar Volume versus Ethanol
Mole Fraction
[3]

y = 3.7972x
2
+ 36.84x + 17.944
R = 1
0
10
20
30
40
50
60
70
0 0.5 1
M
o
l
a
r

V
o
l
u
m
e

o
f

S
o
l
u
t
i
o
n

(
m
L
/
m
o
l
)

Ethanol Mole Fraction
52
53
54
55
56
57
58
59
0.0 0.5 1.0
P
a
r
t
i
a
l

M
o
l
a
r

V
o
l
u
m
e

o
f

E
t
h
a
n
o
l

(
m
L
/
m
o
l
)

Ethanol mole fraction
Theoretical
Experimental
14
15
16
17
18
19
0 0.5 1
P
a
r
t
i
a
l

M
o
l
a
r

V
o
l
u
m
e

o
f

W
a
t
e
r

(
m
L
/
m
o
l
)

Ethanol mole fraction
Theoretical
Experimental
K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

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It should be noted that as the mole fraction
of ethanol in the solution increases, the
partial molar volume of ethanol approaches
the molar volume for the pure liquid, which
is approximately 58.700 mL/mol. The same
can be said for water; as the ethanol mole
fraction approaches zero, the molar volume
of the solution approaches the molar
volume of water, which is 18.056 mL/mol at
room temperature. Outside of these two
extremes, the molar volumes of the two
species possess different values. This is a
result of the molecular interactions between
the ethanol and water. Their volumes are
no longer private properties; their volumes
are modified as they exist in a solution
[7]
.

Another quantity that can be
observed from the plots above is the infinite
dilution molar volume of water and ethanol.
These are the values of their partial molar
volume at a very minute concentration. For
water, this is approximately 13.93 mL/mol.
For ethanol, this is approximately 54.31
mL/mol
[6]
.

The theoretical values for the molar
volume of the solution were obtained from
this plot as well by using equation 3.
Superimposing this with the experimental
data:


Figure 7
Solution Molar Volume versus Ethanol Mole
Fraction with Theoretical Data

It can be seen from the plots that the
experimental data is generally in good
agreement with the theoretical values. The
partial molar volume of ethanol consistently
displays positive errors with respect to the
theoretical curve. On the other hand, the
partial molar volume for water was coherent
with the theoretical values. Most of the
experimental data points coincided with the
curve produced from literature values.
Deviations noticeably increased with the
mole fractions and the error peaked at the
5
th
data point. Finally, minute deviations
were only observed with the experimental
and theoretical molar volume of the
solutions. Looking at figure 7, the 6 data
points all fall on the curve that was
generated using equation 3. Quantitatively,
the ethanol and water partial volume, and
solution volume percent errors for each
data point are as follows:

Table 9
Percent Error for each Data Point
Solution V

EthanoI
V

Water
V
A 0.879 0.812 0.461
B 1.295 0.049 0.119
C 1.053 0.353 0.477
D 1.055 1.637 0.734
E 1.000 3.536 0.982
F 1.002 1.532 0.907

Reasons for these deviations are
mainly due to equipment limitations. The
loose, damaged or unfit rubber stoppers of
the volumetrc flasks couldve allowed some
of the alcohol to escape via volatilization.
Some of the stoppers were too loose and
left small gaps along the brim of the flasks.
Damaged ones had small holes in certain
areas.

Difference in the water bath
temperatures and room temperature
couldve also caused the errors for the
density measurement via the pycnometer.
The volume of the solutions were very
sensitive to temperature, such that 10 mL
measured at 26.5
O
C would become
significantly less at a lower temperature and
greater at a higher one. As such, it is
possible to obtain erroneous density values
if the temperature of the room and the tap
water baths were not equal. This could
have been remedied by using a single
y = 3.7972x
2
+ 36.84x + 17.944
R = 1
0
10
20
30
40
50
60
70
0 0.5 1
M
o
l
a
r

V
o
l
u
m
e

o
f

S
o
l
u
t
i
o
n

(
m
L
/
m
o
l
)

Ethanol Mole Fraction
Experimental
Theoretical
K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

7

water bath for all of the flasks and
pycnometer, with a built-in heat source in
order to keep the temperature of the system
constant and close to the room
temperature
[4]
.


Figure 8
Recommended Experimental Set-up
[8]


Furthermore, adhesion of material to
the external and internal surface of the
pycnometer would alter the measured
masses and, as a result, the solution
densities as well. This could take place at
several instances in the procedure, such as
during the removal of the pycnometer from
the water bath for weighing due to improper
handling. Failure to sufficiently clean and
dry the pycnometer before being placed in
the analytical balance would cause positive
errors for the mass of the sample and the
density of the solution, and negative errors
for the volume of the parent solutions. Also,
it is possible for water vapor to condense on
the surface of the pycnometer if the
solutions had a sufficiently low temperature
and if the room had a high humidity, as
indicated by the wet bulb temperature.

After weighing, failure to completely
dry the pycnometer after solution disposal
and cleaning would also consequently
cause the calculated volumes of the parent
solutions to increase, since water will make
the 10-mL sample solutions less dense.
Finally, in line with the previous situation,
this could also take place during the
measurement of the empty pycnometer
mass. This would render the calculated
volumes of the 6 parent solutions incorrect
to some degree.

4. Conclusions & Recommendations

The procedure was able to generate
experimental data for the partial molar
volumes of ethanol and water and the molar
volume of ethanol-water solution at different
ethanol mole fractions that is consistent
with the theoretical values obtained from
literature. Minimum error was observed with
the solution molar volumes, while the
ethanol partial molar volumes exhibited
constant deviations, ranging from 0.879% to
1.295%. The partial molar volumes of water
were in good agreement with the theoretical
values, except for a few data points; the
error range was 0.049% to 3.536%. The
gathered data deviated from the expected
values for a number of reasons.

Procedural mistakes are deduced to
be the primary reason for these deviations.
Improper handling of the pycnometer prior
to weighing, and failure to completely dry
the said glass ware after sample solution
disposals and even during the initial
weighing could all lead to errors in the
calculated volumes of the 6 ethanol-water
solutions. Difficulties were also introduced
by problems with the equipment, such as
the unsuitable covers for the volumetric
flasks. Uncertainties were brought about by
the precision of the instruments, such as
the 10-mL pipette and the thermocouple.

Nevertheless, the procedure proved
to be a decent way of obtaining the partial
molar volumes of water and ethanol at a
specified ethanol mole fraction. Several
modifications can be made to the procedure
in order to obtain more accurate results.

For future endeavors, it is
recommended that a larger container be
made available for the water bath of the
volumetric flasks and the pycnometer. This
will keep the temperature of the flasks and
the pycnometer at a constant value
throughout the experiment and will minimize
any volume contractions and/or expansions
due to differences in the temperature of the
bath and the room. Furthermore, this
negates the necessity of repeatedly
K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

8

removing the flasks and the pycnometer
from the bath for the transferring of the 10-
mL aliquots. Doing so will also decrease the
waiting time between weighing trials since
the temperature of the solutions are kept
nearly constant all throughout.

Furthermore, an additional facet can
be added to the experiment by performing
trials involving electrolytes, such as salt.
This will require modifications to the
equations that were used due to the
increase in solution activity. Pertinent
equations for this is the Debye-Huckle
equation and the like
[5]
. The results will also
be compared with values derived from
theoretical models and literature.

5. References

[1]
Smith, J., et. al. (2004). Introduction to
Chemical Engineering
Thermodynamics, (7th ed.). United
States: McGraw-Hill.

[2]
Chang, R. (2007). Physical Chemistry for
the Biosciences. United States:
McGraw-Hill.

[3]
Atkins, P. & De Paula, J. (2006). Atkins
Physical Chemistry, (8
th
ed.). Great
Britain: Oxford University Press.

[4]
Petek, A., Pecar, D. & Dolecek, V. (2001).
Volumetric Properties of Ethanol-Water
Mixtures Under High Pressure. Acta
Chim. Slov., 48, 317-325.

[5]
ouka, F. & Nezbeda, I. (2009). Partial
Molar Volume of Methanol in Water:
Effect of Polarizability. ResearchGate.
doi:10.1135/cccc2008202.

[6]
Armitage, D., et al. (1978). Partial Molar
Volumes and Maximum Density Effects
in AlcoholWater Mixtures. Nature, 219,
718-720. doi:10.1038/219718a0.

[7]
Sakurai, M. (1988). Partial Molar Volumes
in Aqueous Mixtures of Nonelectrolytes.
II. Isopropyl Alcohol. Journal of Solution
Chemistry, 17(3), 267-275.

[8]
PHYWE. (2014). Pycnometer Water-Bath
Set-up [Image].


6. Appendix

[D1] Derivation of partial molar volumes of
a binary system

The summability relation for volume:

For binary systems, expansion
results to:

If

is a function of x
i
at constant T
and P, from Gibbs/Duhem,

Substituting these to the
summability relation,

(

) (

Sample Calculations

1.) m are in terms of g, ef: empty flask

K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

9

2.) n are in terms of mol

Raw Data Tables

Table 10
Mole Recalculation Data
Solution
Mass (g)
Empty +EthanoI +Water
A 36.1657 36.1657 85.959
B 39.5045 59.861 85.0793
C 36.2671 63.2197 80.1326
D 37.5238 70.2786 79.5317
E 36.7283 73.3054 77.1857
F 36.938 76.1301 76.1301


Table 11
Pcynometer Data
Solution Trial 1, g Trial 2, g Trial 3, g
Empty 15.8457 15.8458 15.8456
A 25.8331 25.8463 25.8782
B 25.036 25.0616 25.0753
C 24.6501 24.658 24.6819
D 24.2692 24.2826 24.3068
E 23.9575 23.9763 23.9745
F 23.7195 23.71 23.7279