Determination of the Partial Molar Volume of

Methanol in a Methanol (1)/ Water (2) System

Abagon, Ma. Victoria1, Buendia, Neil Daniel2, Caracas, Corine Jasper3
Department of Chemical Engineering, College of Engineering
University of the Philippines - Diliman
Quezon City, Philippines
1
vicky.abagon@gmail.com | 2ndnbuendia@gmail.com | 3corinecaracas@gmail.com
Abstract To determine the partial molar volume properties of
methanol in a methanol (1) water (2) system, solutions of
different concentrations of methanol were prepared and weighed.
The masses obtained were used to calculate for the actual mole
fractions of methanol and water. Recorded weights and
recalculated mole fractions were used to calculate for partial
molar volume values. The obtained infinite dilution values for
methanol and water at 27C are 36.84 mL/mol and 14.02 mL/mol
and deviated by 2.244% and 1.111% respectively.
Keywords-partial molar volume, methanol, water, infinite
dilution

I.

INTRODUCTION

Partial molar quantities relate changes in extensive

properties of the solution to changes in concentration. [1]
Specifically, the partial property represents the change in the
total property nM of a mixture caused by the addition of
an infinitesimal amount of species i to a definite amount of
solution at constant temperature and pressure. The partial molar
i is given by:
property M

i= ( nM )
M
ni
where

(1)
P ,T ,n j i

is any thermodynamic property.

The molar property of a substance in a pure state at the

same temperature and pressure as the mixture is different from
the partial molar property of the same substance. [2] The
difference comes from the fact that the molecules in a pure
state only interact with its own species while molecules in a
solution tend to interact with other species which may lead to
different interaction potentials. [3]
The partial molar property of a substance can be obtained
from the molar property of the solution and vice-versa. These
relations may be derived from (1) and are given as:

i
M = x i M

(2)

i
nM = ni M

(3)

x i d M i=0

(4)

The first two relations are known as the summability

relations and the third is the Gibbs-Duhem equation.
For a binary solution, a more convenient way of calculating
the partial properties may be employed as compared to using
(1). Using (2) and (3), the solution property may be expressed
as a function of composition at constant temperature and
pressure: [4]

1=M + x2 dM
M
d x1
2=M x 1 dM
M
d x1

(5)
(6)

The partial molar value of pure component 1 at a solution

composed of pure component 2 is the infinite dilution value,
i . This is a property of the component at the mixture
M
should an infinitesimal amount of the said component be
present in the solution.
Experimentally, the partial molar volume two species in a
binary solution may be obtained through the use of a
pycnometer. Two species are mixed at different concentrations.
The molar volumes are then obtained and from these data, the
partial molar volume of methanol and water can be calculated.
In this experiment, the partial molar volumes of water and
ethanol in a binary solution are determined and are compared
with available literature values.
II.

MATERIALS AND METHODS

A. Preparation
The bulb of an alcohol thermometer was wrapped with a
small piece of cotton secured using a rubber band. The cotton
wick was dampened with water and then the thermometer was
swung in a circular motion for about 20 seconds. The
temperature reading was recorded, and the procedure was
conducted for three times.
Room temperature and pressure were recorded prior to
preparing six methanol-water mixtures. To meet the required
mole fraction methanol x as indicated in [5], the amount
of methanol in mL V was determined using the value
given by a modified version of the equation below, rounded
off to the nearest tenth. Respective mole fractions and

amounts are presented in Table 2. Component properties are

shown in Table 1.

x=

V C H OH M W C H
3

V C H

OH

M W CH

OH

V pyc =

OH

(7)

+(50V ) H O M W H
2

B. Experiment Proper
A tap water bath was prepared and the temperature of bath
and the room was taken. The prepared mixtures were placed in
the water bath for around ten minutes so that the samples could
be weighed at the same temperature.
The pycnometer was filled with a mixture from the flask
and then placed to the water bath for around ten minutes before
weighing. Three trials were prepared for each mixture and the
corresponding weights were recorded accordingly.
RESULTS AND DISCUSSION

To illustrate the partial molar volume property of the

methanol (1) / water (2) mixture, a plot of the partial molar
1 , V 2 and total volume V as functions of
volumes V
methanol mole fraction x 1 is generated through a series of
calculations discussed below.
A. Calculating the Molar Volume
Data shown in Table 3 were used to obtain values
necessary to generate the theoretical partial molar volume
versus methanol mole fraction plot.
The respective masses of methanol per mixture were taken
from the difference of the third and second columns of Table
3. Likewise, the masses of water were taken from the
difference of the fourth and third columns. Using the
molecular weights of each component, the number of moles of
methanol and water were determined respectively. From these
values, the mole fractions shown in Table 4 were derived.
To obtain the molar volume V
(mL/mol) of each
mixture, the respective molecular weights and densities were
obtained.

Methanol
0.792

, g/mol

32.04 g
18 g
MW =x 1
+ ( 1x 2 )
mol
mol
the volume of the pycnometer
(9),

( )

V pyc

Wat
1

32.04

18

TABLE 2. VOLUME OF METHANOL PER MIXTURE

Mole Fraction, Methanol
0
0.2
0.4
0.6
0.8
1

and the density of each mixture

Volume, mL M
0
18.0
30.0
38.6
45
50

was given by (10).

mass of the mixture , g

V pyc , mL

(10)

The ratio of the molecular weight and the density gave the
total molar volume of each mixture. Values obtained were
plotted against methanol mole fractions, and the best-fit
second-degree polynomial determined through Microsoft
Excel is shown below.

V =4.3318 x 21 +18.5305 x1 +18.3964

(11)

The derivative of (11) with respect to x 1 is taken, and

the partial molar volumes could then be calculated using (5)
and (6). Figure 1 shows the plot of the total molar volume and
partial molar volumes against the mole fraction of methanol in
each mixture, obtained using the data recorded under
recalculation.
The molar volumes of the mixtures in the third part of the
experiment were determined similarly, however incorporating
the mole fractions previously calculated. The plot of the
values obtained are shown in Fig. 2.
TABLE 3. MOLE FRACTION RECALCULATION DATA

Molecular weights were determined using (8),

(9)

TABLE 1. VOLUME OF METHANOL PER MIXTURE

The flask used to prepare the mixtures were weighed three

times: (1) before the mixture was added (i.e. empty flask); MW
(2)
when the required amount of methanol is transferred to the
flask, and; (3) when the required amount of water was added to
complete the mixture. The mole fraction of methanol in each
mixture was recalculated to determine the actual amount of
methanol present in the prepared mixture.

, g/mL

III.

mH O
H O

(8)

was obtained using

Mixture

Mass of Empty
Volumetric
Flask

Mass of
Volumetric Flask
with Methanol

A
B
C
D
E
F

35.5789
35.5461
38.0129
35.8425
35.2389
35.6973

35.5789
45.5445
63.5980
65.7951
70.2300
74.5653

Mass of
Volumetric Flask
with Methanol &
Water
84.7301
82.5814
82.6329
78.5673
75.9788
74.5653

the methanol-water solution, as observed from the recalculated

mole fractions of methanol in each mixture alone.
TABLE 4. MOLE FRACTIONS
Mixture
A
B
C
D
E
F

mol fraction,
MetOH
0
0.131689442
0.430238695
0.568499517
0.773729167
1

mol fraction, Water

1
0.868310558
0.569761305
0.431500483
0.226270833
0

Partial Volume Properties of methanol (1) / water (2) system

50
40

f(x) = 4.33x^2 + 18.53x + 18.4

R = 1

Molar Volume, mL/mol 30

20
10

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

mol fraction, methanol

Molar Volume
Polynomial (Molar Volume)
Vbar1
Vbar2
Figure 1. Molar volumes obtained from recalculation data plotted against
mole fraction of Methanol

Partial Volume Properties of methanol (1) / water (2) system

50
40
Molar Volume, mL/mol 30
20
10

f(x) = 6.05x^2 + 15.18x + 18.79

R = 1

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

mol fraction, methanol

Molar Volume
P olynomial (Molar Volume)

As the mole fraction of methanol in the solution increases,

the partial molar volume of methanol in the mixture also
increases and the partial molar volume of water in the mixture
decreases, which could be noticed in both graphs. This
illustrates that the total volume of the mixture is also
dependent to the concentration of its components.
The experimental values obtained from the third part of
the experiment were compared to the molar volumes obtained
using recalculation data. Average deviations between these
values are presented in Table 5.
At x 1=0 , or at the pure water solution, a value for the
partial molar volume of methanol was obtained. Likewise, at
x 1=1 , or at the pure water solution, a partial molar
volume value was obtained for water. These are the partial
molar volume values of the respective components at infinite
i , which indicates the limiting values of the
dilution V
partial properties that may be exhibited by the components in
that particular mixture.
Infinite dilution values obtained from recalculation data
were compared to literature data of the partial molar volume at
infinite dilution of the methanol-water system at 27 C.
Respective values and the deviation of these values are shown
in Table 6.
However, all the partial property values obtained are
unique for the system under observation in this experiment.
Methanol and water may behave differently should they be
mixed with other compounds in other solutions.
The difference between the calculated properties could be
attributed to the inconsistent reading given by the analytical
balance. Also, the effects of minute mistakes in solution
preparation, such as material loss from the transfer of fluids
from the volumetric flask to the pycnometer, were not taken
into account and may have caused the differences of the molar
volumes calculated. Differential changes in temperature
throughout the duration of the experiment could also have
affected the density of the mixtures.

Vbar1
Vbar2

TABLE 5. AVERAGE DEVIATIONS BETWEEN EXPERIMENTAL DATA

Property

Figure 2. Molar volumes obtained from experimental data plotted against

mole fractions of Methanol

V
V 1
V 2

B. Analysis of Data
The data obtained shows that methanol and water
molecules interact with each other in the solution, expressed
as partial properties. Therefore, the individual volumes of
methanol and water do not necessarily add up to the volume of

Average %
Deviation
1.7 %
4.9%
1.7%

TABLE 6. INFINITE DILUTION VALUES [2]

Property

From
Recalculation Data

From Literature
Data [x]

%
Deviation


V 1
V 2

36.84 mL/mol

37.687 mL/mol

2.244 %

14.02 mL/mol

14.180 mL/mol

1.111 %

REFERENCES
IV.

CONCLUSION AND RECOMMENDATIONS

From the obtained masses of methanol-water mixtures of

different concentrations, the partial molar volume of methanol
in the solution was obtained. Also, as shown in the recorded
values and calculations, the molar volumes of methanol and
water are not additive. Thus, partial molar properties of a
component in a solution could also be dependent on the other
compounds found in the system.
The infinite dilution values for methanol obtained from the
experiment deviated 2.244% from literature value. The value
obtained for water differed by 1.111%
It is recommended the prepared solutions are enough for
three trials. Partial molar volumes of other compounds could be
determined through the same process indicated in this
experiment, so combinations of other compounds could be
used for further studies.

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http://www2.stetson.edu/~wgrubbs/datadriven/fchen/bartender/partialmol
arvolumechen.html
[2] IIT Bombay. (2013, January 18). Chemical Engineering Thermodynamics
(Web). Retrieved March 25, 2016, from NPTEL Website:
http://nptel.ac.in/courses/103101004/38
[3] DeVoe, H. (n.d.). 9.2 Partial Molar Quantities. Retrieved March 25, 2016,
from UCDAVIS CHEMWiki:
http://chemwiki.ucdavis.edu/Textbook_Maps/Physical_Chemistry_Textbo
ok_Maps/DeVoe's_%22Thermodynamics_and_Chemistry
%22/09%3A_Mixtures/9.2_Partial_Molar_Quantities
[4] Smith, J., Van Ness, H., & Abbott, M. (2005). Introduction to Chemical
Engineering Thermodynamics (7th ed.). New York: McGraw-Hill.
[5] ChE 124 Chemical Engineering Thermodynamics Laboratory Manual,
Quezon City, 2013, pp. 42-45.