CHM170L Physical Chemistry 1 Laboratory

4th Quarter SY 2009-2010

Determination of Molar Mass of a Volatile Liquid by Vapor-Density Method

Nieva, Aileen D.1, Arceo, Mary Anne V., Cuales, Jelline C., Kim, Sung Min, Ngan, Emil Joseph T., Rivera, Jainie Lynne
B.2
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology; 2Student (s), CHM170L/A41, School of Chemical Engineering,
Chemistry and Biotechnology, Mapua Institute of Technology
1

ABSTRACT
In this experiment, the objective is to estimate the molar mass of volatile liquids from their vapor densities at a
temperature above their boiling points using the Dumas method. In the Dumas method a volatile liquid is heated to
a known temperature (above its boiling point) and allowed to escape from a container through a tiny orifice. Once
the liquid has vaporized, the container is cooled to room temperature. Volatile substances are usually composed of
non-polar molecules. Among five reagents available, three can be used namely acetone, ethyl acetate and ethyl
alcohol. After introducing the sample with syringe in the flask, it should be boiled at least 10 minutes until the liquid
is evaporated. The flask should be removed for cooling down and should be reweighed again. There are many
factors which can be considered for the percentage errors. One of which is the intermolecular forces of each
compound. Ethyl alcohol for example has the ability to form hydrogen bonds due to the presence of lone pairs of
electrons in the oxygen atom behaving non-ideally. The molecular volume and the intermolecular forces are some
of the variables which create deviations from the ideal behavior. Therefore conclude, among the three samples
given, the ethyl acetate has the one with the highest value for molar mass of the vapor which is 95.634 percent for
trial 1 and 96.677 percent for trial 2.

INTRODUCTION
One of the properties that helps characterize a substance is
its molar mass. Chemical and physical methods for
determining atomic and molecular formula weights or molar
masses have been important historically as a way of
analyzing and categorizing new materials. The modern
laboratory is generally equipped with instrumentation which
makes many of these methods obsolete. However the
principles upon which the older methods were based are
not insignificant and many form the foundation for the
prediction of physical and chemical properties and
behaviors of substances.

volume which would contain a gram-atomic weight of a

gaseous element or compound under fixed conditions, what
we know today as the molar volume. At STP this volume is
22.4 L for an ideal gas.

Volatile substances are usually composed of nonpolar

molecules. The classic Dumas method for determining the
formula weight of a volatile liquid is a case in point. The
Dumas method is one of the simplest ways to measure the
molecular weight of a substance. Avogadro proposed as
early as the mid-1800's that equal volumes of gases
measured under identical conditions would contain equal
numbers of gas particles. With an established relative
atomic mass scale it was possible to describe a constant

Massing a sample of gas is relatively simple. These two

pieces of information are the minimum required
for
a
molar
mass
determination.

Experiment 01 Group No. 4 08 June 2010

An understanding of the various gas laws allows for an

application of this useful information to liquids and solids
which are appreciably volatile, i.e., possess relatively high
vapor pressures. As long as the temperature and pressure
are known, a measured volume of gas can be converted to
moles
since:
PV =nRT
n= PV/RT

In the Dumas method a volatile liquid is heated to a known

temperature (above its boiling point) and allowed to escape
from a container through a tiny orifice. Once the liquid has
vaporized, the container is cooled to room temperature.

1 of 5

CHM170L Physical Chemistry 1 Laboratory

4th Quarter SY 2009-2010

Gradually the vapor which remained in the container at the

higher temperature condenses to a liquid and is then
massed. If the volume of the container is known along with
the high temperature, the room pressure can be used
(because the system is open to the atmosphere through the
orifice) to calculate moles. From there a molar mass can be
determined.

Analytical balance, 600-mL beaker, 125-mL Erlenmeyer

flasks, Bunsen burner, wire gauze, thermometer
Set-up of Apparatus

aluminum foil

This method depends on a lot of things going right. One

assumption is that while the liquid is volatile enough to
vaporize at the elevated temperature, it is not so volatile
that a significant amount will be lost to evaporation through
the orifice as the container cools. The vapor is also
assumed to behave ideally at the temperature and pressure
at which it occupies the container. The amount of error
implicit in this approximation varies from compound to
compound and is tied to the variables which create
deviations from ideal behavior: molecular volume and
intermolecular forces.

Erlenmeyer flask
Beaker
Wire gauze
Bunsen burner

Experimental Procedure
Generally speaking, the larger these are, the greater the
error in the determination. The situation is further
complicated by the interaction of these two factors. For
example, a small molecule may have significant
intermolecular forces (hydrogen bonding perhaps) but a
large molecule may have comparatively weak forces (like
dispersion forces). Combinations run between these
extreme examples making predictions of error from
this source difficult.

METHODOLOGY
EXPERIMENTAL METHOD
Materials

Aluminium foil, fine copper wire, razor blades, pliers or wire

cutter, boiling stones, syringe

Reagents

acentonitrile, ethanol, ethyl acetate, isopropyl acetate, 2propanol

Equipment and Glassware

Experiment 01 Group No. 4 08 June 2010

A clean, dry 125 mL Erlenmeyer flask serves as a

suitable container. Its mass is small enough for the
analytical balance and large enough to contain a
sufficient mass of vapor.
The mass of the flask on the balance is required
for the volume determination. When full of water, it
will be too heavy for analytical balance.
A cap may be fashioned for the flask from a
square of aluminium foil and secured with fine
copper wire twisted tightly around the neck just
below the rim. Excess foil should be removed as it
provides a place for condensed water.
The sample is introduced with syringe. The needle
is used to make a tiny hole in the foil cap and 3-4
mL of the liquid is injected.
Enlarging the hole with an unsteady hand will
introduce serious errors into the determination.
The flask should be immersed in a 600 mL beaker
of water. The water level should be high enough to
cover most of the flask but not so high as to allow
water to enter through the hole in the foil.
The water bath should be brought quickly to a boil
but then the heat should be reduced to achieve a
gentle boil for about 10 minutes or until all the

2 of 5

CHM170L Physical Chemistry 1 Laboratory

4th Quarter SY 2009-2010

liquid is evaporated.
The flask is removed from the water and allowed
to cool down. Water must be removed completely
from the outside of the flask. When the flask has
returned to room temperature and is completely
dry on the outside, it should be reweighed.
Additional trials may be done simply by adding
more liquid through the same hole.
Repeat the procedure described above.
After the final trial, the cap assembly is removed
and the flask is rinsed thoroughly and then filled
almost completely with room-temperature water.
Repeat the entire procedure stated above using
other samples.

RESULTS AND DISCUSSION

In this experiment, the determination of the molar masses
of volatile liquids namely acetone, ethyl acetate and ethyl
alcohol. The determination of molar mass in Dumas
method experiment uses the ideal gas law: knowing the
pressure, volume, and temperature of a gas sample
allows us to know the number of moles and knowing the
mass that corresponds to that number of moles allows
computation of the molar mass.
Regarding to the percentage difference of each sample, it
obtain 17.21%, 9.13% and 6.93% respectively. There are
many factors which can be accounted for these
percentage errors. One of which is the intermolecular
forces of each compound. Ethyl alcohol for instance has
the ability to form hydrogen bonds due to the presence of
lone pairs of electrons in the oxygen atom behaving nonideally. Knowing that an intermolecular forces for gases,
deviates from behaving ideally at conditions with high
pressures and low temperatures. The molecular volume
and the intermolecular forces are some of the variables
which create deviations from the ideal behavior. And
generally speaking, the larger and stronger these are, the
greater the error in the determination.
Increasing the amount of the liquid sample injected in the
flask doesnt matter for when all the liquid vaporizes it will
contain constant maximum amount of vapor and the excess
exits through the tiny orifice, this happens at equilibrium

Experiment 01 Group No. 4 08 June 2010

Sample 1
Sample
name
Mass
of
vapor, m
Moles
of
vapor at T,
V and P, n
Estimated
molar mass
of
vapor,
m/n
Moles of air
displaced
by
the
vapor at TR
Molar mass
of
air,
calculated
Mass
air
displaced
by
the
vaporized
liquid
True mass
of
vapor
that
occupied
the flask at
the boiling
temperature
of water
Corrected
molar mass
of the vapor
(average)
Molar mass
(literature
value)
%
difference

Acetone

Sample 2
Ethyl Acetate

Sample 3
Ethyl Alcohol

Trial 1

Trial 2

Trial 1

Trial 2

Trial 1

Trial 2

0.647

0.319

0.553

0.453

0.354

0.32

5.1297
x 10-3

5.0296
x 10-3

4.9265
x 10-3

4.8573
x 10-3

4.9145
x 10-3

4.9427 x
10-3

126.127

63.42

112.25

93.26

72.0317

64.7419

5.835 x
10-4

5.7385
x 10-4

5.8027
x 10-4

5.754 x
10-4

5.788 x
10-4

5.7886 x
10-4

28.84

28.84

28.84

28.84

28.84

28.84

0.01682

0.01654

0.0167

0.01659

0.01669

0.016694

0.66392

0.33354

0.5697

0.46969

0.37061

0.336694

68.069

96.1555

49.2736

58.078

88.104

46.08

17.21%

9.13%

6.93%

Table 1. Determination of Molar Mass of a Volatile

Liquid by Vapor-Density Method
when the pressure inside equals the pressure outside. This
is evident in the close quantitative relation of the data have
gathered (especially that for ethyl alcohol) for the mass of
the vapor.
Another important point to be considered is that the flask
used before the liquid is added or before the liquid is
formed contains a fixed amount of air. This air has mass
and contributes to the overall mass of the flask. The volatile
liquid sample when boils, it exerts a vapor pressure in
which when the liquid was placed in the vessel, some of the
air is pushed out of the flask because of the vapor pressure
exerted by the liquid. Therefore, when the container is

3 of 5

CHM170L Physical Chemistry 1 Laboratory

4th Quarter SY 2009-2010

massed again, there is air that is missing and this should be

considered in the final mass if the final mass of the air is to
be determined by difference. This is visible with the results
showing that the calculated molar mass of the vapor for the
three samples are all less than their literature value. Adding
the missing mass of air at room temperature and pressure
brings closer to the true value.
The experiment is susceptible; thus the following measures
are to be taken into consideration in order to lessen and to
avoid possible sources of error:
Improper cutting of the aluminum foil which
serves as the cap. Excess foil should be
removed for it may serve as a hiding place for
water vapor while boiling and thus may add
up to the total weight of the flask plus the
condensed vapor.
Improper injecting of the syringe in the foil
which may create a bigger hole and thus
cause the volatile liquid to rapidly escape from
the flask.
Incompletely remove the water from the outside of the flask
after allowing it to cool down. Condensed water under the
edges of the cap can change the mass of the container
significantly.
CONCLUSION AND RECOMMENDATION
Through the experiment, it is concluded that among the
three samples given, the ethyl acetate has the one with the
highest value for molar mass of the vapor which is 95.634
percent . Probably, one of the main reasons for this is that
among the three, ethyl acetate has the largest molar mass.
Second to the highest is the acetone that has 72.4256
percent and lastly is the ethanol which has found to have
52.4278 percent.
With these result, it is found to have a 16.21 percent error
for acetone, 9.13 percent error for ethyl acetate and 6.93
percent error for ethanol. Probable reason for this is
perhaps human error. It is the way on how it is the sample
injected in the Erlenmeyer flask because some of it after
injected left a little bit big hole in the aluminum foil. It is
strongly recommended to use smaller needle to lessen
percentage errors.

Experiment 01 Group No. 4 08 June 2010

REFERENCES
1. Experimental Studies for General Chemistry,
Malcolm F. Nicol, Arlene A. Russell, Eleanor D.
Siebert
2. Advanced Chemistry with Vernier & Laboratory
Experiments for Advanced Placement Chemistry,
Sally Ann Vonderbrink, Ph. D.
3. Laboratory Manual for Chemistry, Lawrence
Epstein
4. Physical Chemistry Laboratory Manual, Part 1
(2006), Alvin R. Caparanga, John Ysrael G.
Baluyut and Allan N. Soriano
5. Elementary Principles of Chemical Processes, 3rd
ed., Felder, R.M. and Rousseau, R.W. 2000.
6. Chemistry Principles and Reactions, 4th ed.,
Masterton, W. and Hurley, C. 2001
APPENDICES

Appendix 1: Useful Mathematical Methods

General strategies
If the vapor in the flask is assumed to be an ideal gas,
equation (1) can be used to determine its molecular weight.
In equation (1): MW =mRT/(PV)
The temperature of the vapor is that of the boiling water
bath.
The pressure of the vapor is that of the atmosphere.
The volume of the vapor is that of the flask and glass tube.
The mass of the vapor is determined by removing the flask
from the waterbath, allowing it to cool, weighing the flask

4 of 5

CHM170L Physical Chemistry 1 Laboratory

4th Quarter SY 2009-2010

and condensed liquid, and subtracting the mass of the

empty flask.
Pressure Unit Conversion Constants
Conversion Factors
To convert Into
Multiply by
atmosphere bar
1.01295
atmosphere dynes/cm2
1.01295 x 106
atmosphere in. Hg
29.9213
atmosphere in. water
406.86
2
atmosphere kg/cm
1.03325
atmosphere mbar
1012.95
atmosphere mtorr or micron Hg 7.6 x 105
atmosphere Pa or N/m2
1.01295 x 105
atmosphere PSI or lb/in2
14.696
atmosphere torr or mm Hg
760
bar
atmosphere
0.9872
2
bar
dynes/cm
1 x 106
bar
in. Hg
29.54
bar
in. water
401.65
bar
kg/cm2
1.02
bar
mbar
1000
bar
mtorr or micron Hg 7.5028 x 105
bar
Pa or N/m2
1 x 105
2
bar
psi or lb/in
14.503861
bar
torr or mm Hg
750.2838
torr or mm Hg
bar
1.3328 x 10-3
torr or mm Hg
dynes/cm2
1.3328 x 103
2
torr or mm Hg
kg/cm
1.3595 x 10-3
torr or mm Hg
in. Hg
3.937 x 10-2
torr or mm Hg
in. water
0.5353
torr or mm Hg
mbar
1.3328
torr or mm Hg
mtorr or micron Hg 1000
torr or mm Hg
Pa or N/m2
133.28
2
torr or mm Hg
psi or lb/in
1.934 x 10-2

Appendix 2: Miscellaneous Useful Information

Experiment 01 Group No. 4 08 June 2010

Gases and liquids with relatively large

intermolecular forces and large molecular volume do not
calculate according to the ideal gas laws equation; in fact
some compounds that we normally consider as liquids
deviate significally from ideal gas behaviour at
temperatures at or slightly above their boiling points. Under
these conditions, van der Waals equation, a modification of
the ideal gas law equation, can be used to correct for the
intermolecular forces and molecular volumes in determining
the moles of gas present in the system:
(P + n2a / V2)(V- nb) = nRT
In this equation, P,V,T,R, and n have the same meanings

a, is an a experimental value that is representative of the

intermolecular forces of the vapour, and b is an
experimental value that is representative of the
volume of the molecules.
If a more accurate determination of the moles of vapour,
nvapor, in the flask is required, van der Waals
equation can be used instead of the ideal gas law
equation. Some values of a and b for a number of
low boiling point liquids are listed in table.
van der Waal's Constants for Real Gases
The van der Waal's equation of state for a real
gas is:
(P + n2a / V2)(V- nb) = nRT
To convert 'a' into atm L2/mol2 multiply by 0.986
atm/bar
To convert 'a' into kPa L2/mol2 multiply by 100.0
kPa/bar

Molecular
Formula

Name

C2H5OH

Ethanol

12.56

0.08710

C3H6O

Acetone

16.02

0.1124

C4H8O2

Ethyl
acetate

20.57

0.1401

5 of 5