Department of Pure and Applied Chemistry

College of Arts and Sciences

Visayas State University
CHEM 151- PHYSICAL CHEMISTRY I
Name: Ryan Dave C. Sugano
Course & Yr.: BS Chemistry- IV
30, 2015
Group No.:

Date Performed: July 8, 2015

Date Submitted: July
Rating:

Experiment No. 1
Determination of Molecular Weight by Dumas Method
I.

INTRODUCTION

The Dumas method for molecular weight determination, was first

developed by Jean-Baptiste Andre' Dumas exploiting the ideal gas law in
order to determine the molecular weight of a compound that can be
vaporized (without significant decomposition).
The ideal gas law serves as the basis for the Dumas Method for the
determination of molecular weight. According to the ideal gas law,
PV =nRT
where P, V, n, R and T are the pressure in atm, the volume in liters, the
moles of gas, the gas constant (equal to 0.08206 L-atm/(K mole) and the
absolute temperature, respectively. Letting n = mass/(MW) where m is the
mass of gas grams and MW is its molecular weight, the ideal gas law gives,
mRT
MM=
PV
In this method, a liquid is placed in a container with a very small hole.
The liquid is then heated in a constant temperature bath, such as a boiling
water bath, until all the liquid vaporizes. Excess vapor escapes via the hole in
the container; the remainder is sufficient to occupy entirely the containers
volume at the temperature of the bath and at the pressure of the adjoining
atmosphere. The figure below shows set- up for the Dumas method.

Figure 1. Experimental Set- up for Dumas Molecular Weight

Determination
The experiment aims is to determine the molecular weight of a
compound that is a volatile liquid. By vaporizing a measured amount of the
sample, and determining the pressure, volume, and temperature of the
sample, the approximate molecular weight may be determined by presuming
ideal gas behavior.
II.

RESULTS AND DISCUSSION

The Dumas method uses the ideal gas law to determine the molar
mass of a compound which is a liquid that has a boiling point between room
temperature and 100 C. The Dumas method was carried out using 5 mL of
volatile liquid in an Erlenmeyer flask in the fumehood. The volume of the
flask was obtained by completely filling the container with water and
converting the mass of the water to volume by density (~1g/mL). The
determination was done in triplicate to assure reproducibility of results.
Table 1. Data obtained from Dumas Method Experimentation

Trial 1
Mass of Erlenmeyer flask (g)
Mass of flask with water (g)
Volume of the flask (L)
Mass of flask with foil (g)
Temperature (K)
Mass of flask with condensate and
foil (g)

120.2
402.1
0.2819
120.8
358.15
121.2

Trial 2
116.3
397.3
0.2808
116.6
359.15
116.9

Trial 3
113.4
397
0.2836
114
357.15
114.4

The molar mass calculations for the three trials conducted was
obtained using MM= mRT/PV. Table 3 shows the data obtained molar masses
for the liquid sample.
Table 2. Molar Mass Results of Liquid Sample (Methanol, MM= 32 g/mol)
using Dumas Method

Trial 1

Trial 2

Trial 3

mass of liquid (g)

Temperature (K)

0.40
358.15

0.30
359.15

0.40
357.15

Pressure (atm)
Volume (L)
Molar Mass of Sample
(g/mol)
Percentage Error (%)

1
0.2819
41.722
76

1
0.2808
31.502
37

1
0.2836
41.356
86

30.38%

1.56%

29.24%

Mean
0.37
358.1
5
1.00
0.28
38.19
19.36
%

The molar masses obtained for three trials is represented by the mean
value 38.19 g/ mol, which has 19.36 % error from the actual molar mass of
the liquid.
The sample liquid was methanol, CH3OH, with molecular weight 32.04
g/mol, 64.5 C, and vapor pressure of 12.3 kPa @ 20 C. Such properties of
the liquid used may contribute to the deviations for the molar mass
determination and that deviations for different gases is also at different
extent due to difference in properties.
The major cause of error in the method is the 2 assumptions of the
Dumas method where The compound vapor behaves ideally at high
temperature and either the volume of the vessel does not vary significantly
between room and the working temperature, or the volume of the vessel
may be accurately determined at the working temperature. Such 2
assumptions caused the largest deviations in the determination since the
temperature is not high enough in order to neglect the volume and pressure
corrections caused by the volumes and intermolecular attractions of the gas
molecules. This error may cause the molar mass to be obtained to be larger
than the actual and may account for the large molar masses obtained in
Trials 1 and 3.
The Dumas method depends on a number of things. The liquid, for
example, must be volatile enough to vaporize at a high temperature. But too
much volatile liquids would cause a significant amount of loss due to
evaporation 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

the forces that allow condensation. Generally speaking, the larger these are,
the greater the error in the determination.
The "empty" container is really filled with an amount of air determined
by the volume, temperature and pressure in the container. This air has mass
and contributes to the overall mass of the container assembly.
The volume of the flask at higher temperature was greater than that at
room temperature because of expansion of the glass. (The expansion of the
glass is 1.4 105 deg C1. That is, the volume of the flask increases by
approximately 1.4 103 percent per degree rise in temperature. This is
also a source of error in the experiment.
At the end of the experiment, some of the liquid vaporizes, depending
on its vapor pressure at room temperature. The presence of this vapor forces
out some of the air through the orifice since the internal pressure will be
equalized with the room pressure. The number of gas particles remains
constant if the temperature and pressure remain constant. Thus when the
container is weighed again there is air missing that needs to be counted in
the final mass when the mass of the condensed liquid is determine by
difference. This results in an apparent mass of liquid that is too small, which
in turn makes the formula weight too small which may be accounted for the
small molar mass obtained for Trial 2.
The Dumas Method was one of the first techniques available for the
measurement of the molecular weights of compounds and was a major step
towards being able to determine the chemical formulas of these compounds.
Currently, the Molecular Weight of many compounds can be measured with a
high degree of accuracy using Mass Spectrometry.
III.

CONCLUSION

The molar mass of a volatile liquid was carried out using Dumas
Molecular Weight Determination Method carried out in three replicates. The
molar mass obtained for the liquid is 38.19 g/mol which has a 19.36% error
from the actual molar mass, 32 g/mol, of the liquid usedmethanol.
The Dumas method is an easy set- up for the determination molecular
weight of a liquid but is restricted to some situations such that the liquid
must be volatile and its boiling point must not exceed 100 C otherwise, a
sand or oil bath should be used.
Also, the Dumas method has a number of loopholes which causes
errors in the determinations such as the glass expansion, intermolecular
forces of the gas, the density of water, and the air present upon getting the
mass.
The Dumas method, however gives a major step in molar mass
determination techniques and is still widely used for its simplicity.
IV.

REFERENCES

Catalyst - The Prentice-Hall Custom Laboratory Program for Chem 53 at

the University of Pennsylvania Department of Chemistry, Pearson
Custom Publishing, 2005, pages 57-65.
http://www.roanestate.edu/faculty/chemistry/chemistryslideshows/Dum
as/Dumas.pdf
http://web.centre.edu/miles/che135/che135labs/Molecular%20Weight
%20by%20the%20Dumas%20Method.pdf
http://www.chemtopics.com/aplab/mmvliq.pdf
http://www.sas.upenn.edu/~kennethp/chemlab1.pdf
http://infohost.nmt.edu/~jaltig/VolatileLiquid.pdf
http://homepage.smc.edu/gallogly_ethan/files/dumas%20bulb
%20report.pdf
http://chemistry.bd.psu.edu/jircitano/FW05.pdf