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

Soriano, Partial Molar Volume of a Substance, 2014

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 pressure will result to a total property

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:
change represented by ΔnM and the
corresponding partial molar volume of
species i is Ḿ i .
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:

∂ ( nM ) M =∑ x i Ḿ i
Ḿ i=
[ ∂ ni ] P , T , nj
i

The symbol Ḿ i 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 Mi 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 Δni of species i to a solution with total
property nM at constant temperature and
ni
nM =∑ ni Ḿ i , xi =
i n
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].

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 K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014
For a binary system, it is found that
the partial molar volumes and solution
molar volume are:
dV dV
V́ 1=V + x 2 =V + ( 1−x 1 ) [1 ]
dx 1 dx 1
dV
V́ 2=V −x 1 [2 ]
dx 1
[D1]
V =x 1 V́ 1+ x 2 V́ 2 [ 3 ]
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 xi 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
Solutio
Mole Fraction Ethanol
n
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:
nethanol
x ethanol=
nethanol + nwater
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 K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014
ρethanol
V ethanol
M ethanol
¿
ρ ethanol
V ethanol + ( 50−V ethanol ) water
M ethanol
Isolating Vethanol 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
Solutio
Ethanol Volume
n completely filled with the solution, the
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 of the bath. Afterwards, the pycnometer
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 26.5OC,
and ice, when the temperature had risen
above 26.5OC. 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
ρ Following this, the empty
M water 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 wasn’t
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
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.
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 K.A. Cruz, D.L.C. Fernando, R.A. Soriano, Partial Molar Volume of a Substance, 2014

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
Figure 2 D 8.4235 8.4368 8.4612
Pycnometer in the Water Bath E 8.1118 8.1305 8.1289
F 7.8738 7.8642 7.8823
The same procedure was repeated
for solutions B to F. Upon finishing, all the The average was taken and by dividing
used glass wares were washed, and the these by the volume of the solution inside
contents of the waster beaker and the the pycnometer, the densities of the 6
leftover solutions were disposed in the sample solutions were obtained.
designated waste jar.
Table 6
3. Results & Discussion Densities of the 6 Sample Solutions
Solution Average mass, g Density, g/mL
The mole fractions of the solutions A 10.0068 1.00068
were recalculated by solving for the actual B 9.2119 0.92119
masses of ethanol and water inside the C 8.8176 0.88176
flasks. The ethanol masses were obtained D 8.4405 0.84405
by subtracting the mass of the empty flasks E 8.1237 0.81237
from the recorded masses with the ethanol. F 7.8734 0.78734
The water masses were obtained similarly:
Since the mass of the sample
Table 3 solutions are known, as outlined in table 2,
Ethanol and Water Masses in each Solution their molar volumes can be calculated as
Solution Ethanol mass, g Water mass, g well. This was done by taking the quotient
A 0.0000 49.7933 of the solution masses and their respective
B 20.3565 25.2183 density, which was then subsequently
C 26.9526 16.9129 divided by the total number of moles in the
D 32.7548 9.2531 parent solution:
E 36.5771 3.8803
F 39.1921 0.0000 Table 7
Molar Volume of the 6 Sample Solutions
These values were converted to moles by Solution Molar volume, mL/mol
dividing the masses in the previous table A 18.0077
with the appropriate molar mass, 46.08 B 26.8700
g/mol for ethanol and 18.02 g/mol for water: C 32.6540
D 40.6508
Table 4 E 49.3520
Moles of Ethanol and Water in each Solution F 58.5259
Ethanol Water Ethanol mole
Solution
moles moles fraction Plotting the molar volumes, as the
A 0.0000 2.7632 0.0000 ordinate, against the mole fraction of
B 0.4418 1.3995 0.2399
C 0.5849 0.9386 0.3839

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

ethanol, as the abscissa, yields the 59

Partial Molar Volume of Ethanol (mL/mol)

following graph:
58
70 57
Molar Volume of Solution (mL/mol)

60 56
f(x) = 3.8 x² + 36.84 x + 17.94
50 R² = 1 55
Theoretical
40 54
Experimental
30 53
20 52
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
10
Ethanol mole fraction
0
Figure 4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Ethanol Partial Molar Volume vs xEthanol
Ethanol Mole Fraction
Figure 3 19
Partial Molar Volume of Water (mL/mol)
Solution Molar Volume versus Ethanol Mole
Fraction
18
Using the equation for best fit curve,
the derivative at the solution mole fractions 17
can be determined and through equations 1
and 2, the partial molar volumes at those
points can be determined: 16

Theoretical
Table 8 15
Partial Molar Volume of Ethanol and Water in Experimental
the 6 Sample Solutions
Solution 14
V́Ethanol V́Water
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
A 54.7841 17.9442 Ethanol mole fraction
B 56.3876 17.7256
C 57.1401 17.3844 Figure 5
D 57.9133 16.6642 Water Partial Molar Volume vs xEthanol
E 58.4084 15.5946
F 58.5813 14.1470 Theoretical values were obtained by
digitizing the points in the following figure:
Plotting the partial molar volumes of
the two species against the ethanol mole
fraction separately:

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

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

It can be seen from the plots that the

It should be noted that as the mole fraction experimental data is generally in good
of ethanol in the solution increases, the agreement with the theoretical values. The
partial molar volume of ethanol approaches partial molar volume of ethanol consistently
the molar volume for the pure liquid, which displays positive errors with respect to the
is approximately 58.700 mL/mol. The same theoretical curve. On the other hand, the
can be said for water; as the ethanol mole partial molar volume for water was coherent
fraction approaches zero, the molar volume with the theoretical values. Most of the
of the solution approaches the molar experimental data points coincided with the
volume of water, which is 18.056 mL/mol at curve produced from literature values.
room temperature. Outside of these two Deviations noticeably increased with the
extremes, the molar volumes of the two mole fractions and the error peaked at the
species possess different values. This is a 5th data point. Finally, minute deviations
result of the molecular interactions between were only observed with the experimental
the ethanol and water. Their volumes are and theoretical molar volume of the
no longer private properties; their volumes solutions. Looking at figure 7, the 6 data
are modified as they exist in a solution[7]. points all fall on the curve that was
generated using equation 3. Quantitatively,
Another quantity that can be the ethanol and water partial volume, and
observed from the plots above is the infinite solution volume percent errors for each
dilution molar volume of water and ethanol. data point are as follows:
These are the values of their partial molar
volume at a very minute concentration. For Table 9
water, this is approximately 13.93 mL/mol. Percent Error for each Data Point
For ethanol, this is approximately 54.31 Solution V́Ethanol V́Water V
mL/mol[6]. A 0.879 0.812 0.461
B 1.295 0.049 0.119
The theoretical values for the molar C 1.053 0.353 0.477
volume of the solution were obtained from D 1.055 1.637 0.734
this plot as well by using equation 3. E 1.000 3.536 0.982
Superimposing this with the experimental F 1.002 1.532 0.907
data:
Reasons for these deviations are
f(x) =70
0 mainly due to equipment limitations. The
R² = 0 loose, damaged or unfit rubber stoppers of
the volumetric flasks could’ve allowed some
Molar Volume of Solution (mL/mol)

60
of the alcohol to escape via volatilization.
50 Some of the stoppers were too loose and
left small gaps along the brim of the flasks.
40 Damaged ones had small holes in certain
areas.
30
Difference in the water bath
20
temperatures and room temperature
Experimental
10 Polynomial could’ve also caused the errors for the
(Experimental) density measurement via the pycnometer.
0 The volume of the solutions were very
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 sensitive to temperature, such that 10 mL
Ethanol Mole Fraction measured at 26.5OC would become
significantly less at a lower temperature and
Figure 7
greater at a higher one. As such, it is
Solution Molar Volume versus Ethanol Mole
Fraction with Theoretical Data 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

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

removing the flasks and the pycnometer

from the bath for the transferring of the 10- 6. Appendix
mL aliquots. Doing so will also decrease the
waiting time between weighing trials since [D1] Derivation of partial molar volumes of
the temperature of the solutions are kept a binary system
nearly constant all throughout.
The summability relation for volume:
Furthermore, an additional facet can
be added to the experiment by performing V =∑ xi V́ i
trials involving electrolytes, such as salt. i
This will require modifications to the
equations that were used due to the For binary systems, expansion
increase in solution activity. Pertinent results to:
equations for this is the Debye-Huckle
equation and the like[5]. The results will also V =x 1 V́ 1+ x 2 V́ 2
be compared with values derived from dV =d x 1 V́ 1+ x 1 d V́ 1 + d x 2 V́ 2 + x 2 d V́ 2
theoretical models and literature.

5. References If V́ i is a function of xi at constant T

and P, from Gibbs/Duhem,
[1]
Smith, J., et. al. (2004). Introduction to
Chemical Engineering x 1 d V́ 1 + x 2 d V́ 2=0
Thermodynamics, (7th ed.). United dV =d x 1 V́ 1+ d x 2 V́ 2
States: McGraw-Hill.
[2]
Chang, R. (2007). Physical Chemistry for x 1+ x2=1, d x2 =−d x1
the Biosciences. United States:
McGraw-Hill. dV =d x 1 V́ 1−d x1 V́ 2
dV
=V́ 1−V́ 2
[3]
Atkins, P. & De Paula, J. (2006). Atkins’ d x1
Physical Chemistry, (8th ed.). Great dV dV
Britain: Oxford University Press. V́ 1=V́ 2 + , V́ 2=V́ 1 −
d x1 d x1
[4]
Petek, A., Pecar, D. & Dolecek, V. (2001).
Substituting these to the
Volumetric Properties of Ethanol-Water
summability relation,
Mixtures Under High Pressure. Acta
Chim. Slov., 48, 317-325.
dV
[5]
Moučka, F. & Nezbeda, I. (2009). Partial (
V = ( 1−x 2 ) V́ 1 + x 2 V́ 1−
d x1 )
Molar Volume of Methanol in Water: dV
Effect of Polarizability. ResearchGate. V =V́ 1−x 2
d x1
doi:10.1135/cccc2008202.
dV dV
V́ 1=V + x 2 =V + ( 1−x 1 )
[6]
Armitage, D., et al. (1978). Partial Molar d x1 d x1
Volumes and Maximum Density Effects
in Alcohol–Water Mixtures. Nature, 219, dV
718-720. doi:10.1038/219718a0. (
V =x 1 V́ 2 +
d x1 )
+ ( 1−x1 ) V́ 2

[7]
Sakurai, M. (1988). Partial Molar Volumes dV
V =V́ 2+ x 1
in Aqueous Mixtures of Nonelectrolytes. d x1
II. Isopropyl Alcohol. Journal of Solution dV
V́ 2=V −x 1
Chemistry, 17(3), 267-275. d x1
[8]
PHYWE. (2014). Pycnometer Water-Bath Sample Calculations
Set-up [Image].

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

1.) m are in terms of g, ef: empty flask Table 11

Pcynometer Data
m ef +etOH =59.8610 ± 0.0001, mef =39.5045 ± 0.0001 Solution Trial 1, g Trial 2, g Trial 3, g
Empty 15.8457 15.8458 15.8456
A 25.8331 25.8463 25.8782
m etOH =m ef +etOH −mef
~ B 25.036 25.0616 25.0753
metOH =~m ef +etOH −~
m ef , Δ metOH = Δ mef +etOH + Δ mef C 24.6501 24.658 24.6819
~
m etOH =59.8610−39.5045 , Δm etOH =0.0001+ 0.0001 D 24.2692 24.2826 24.3068
~
metOH =20.3565 , Δm etOH =0.0002 E 23.9575 23.9763 23.9745
F 23.7195 23.71 23.7279
metOH =20 . 3565± 0 . 0002

2.) n are in terms of mol

n etOH =0.793774 ± 4 ×10−6 , nw =0.215332 ±11 × 10−6

netOH
x etOH =
netOH +nw
m 4 =7.5136 ±0.0004
~
n
x etOH = ~ etOH~ ,
~
netOH + n w
Δ n etOH ΔnetOH + Δ n w
Δ x etOH =~ (
x etOH ~
netOH
+ ~
netOH + ~
nw )
~ 0.793774
x4 N = ,
0.793774 +0.215332
4 ×10−6 4 ×10−6 +11× 10−6
~
Δ x4 N =x4N ( +
0.793774 0.793774 +0.215332 )
~
x 4 N =0.786610 , Δ x 4 N =0.000016

Raw Data Tables

Table 10
Mole Recalculation Data
Mass (g)
Solution
Empty +Ethanol +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