INTRODUCTION

A method in calculating the molar mass of a substance is through the determination of its
density, which was introduced by Jean-Baptiste Dumas. The said method uses a pre-weighed
glass bulb with the unknown substance and then heated to a water bath (while securely sealed)
until it completely vaporized. After that data are collected and calculations needed are done. The
Dumas method is mostly used on volatile liquids because they readily vaporized, and the vapor
form is said to obey the Ideal Gas Law
PV =nRT

[1]

Where P = pressure of the gas in atmospheres

V = volume of the gas in liters
n = number of moles of gas
T = temperature of the gas in Kelvins
R = the ideal gas constant
From this equation the molecular weight of the said liquid is calculated, after the pressure and
temperature are obtain and using any value of ideal gas constant (R). Since the unknown liquid is
being heated excess air and vapors are being pushes out the flask through a pinhole until it is
equal the external atmospheric pressure. The temperature of the boiling water on the water bath
is equal to the temperature of the vaporized liquid in the flask. In weighing the flask, it should be
dried and cooled totally to condense the unknown liquid, to avoid discrepancies in the
calculations. Although today the Dumas method has been modified where in flask are being used
in the experiment instead of using glass bulbs, as what Dumas used in his time.

Figure 1.1 Glass Bulbs

Figure 1.2 Jean-Baptiste Dumas

Many have tried to experiment on the determination of molar mass of substances in order to fill
in any attempt to further experiment on the future. The main quest is to discover the things, may
it be properties, to use in order to be able to be operative in the said experiment.
The Purpose of this experiment 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.
In this experiment the students are predicting that the properties of the unknown liquid
are enough to solve for its molar mass. They are also predicting that the density of the liquid is
useful in the said calculations.
The Dumas method is one of the simplest ways to measure the molecular weight of a
substance. It uses the ideal gas law. In this method we have to confine a sample of gas in a
container of known volume, making sure when we do this that the sample is exactly at
atmospheric pressure. The temperature and the mass of the gas sample have to be measured,
along with the atmospheric pressure. Because liquids are much easier to handle than gases, a
volatile liquid is usually used as the source of the gas. The liquid must have a boiling point
substantially above room temperature and below the boiling point of water in order for this
method to work well. The paragraphs below describe the experimental method generally used by
scientists and the modifications to that method that we will make in our experiment. As you read,
see if you can identify the possible sources of error that our simplified procedure will introduce.
In the classic experiment, a round thin walled glass bulb with a long, thin bent neck is made by a
glassblower and weighed. A small amount of volatile liquid is introduced into the bulb through a
tiny opening at the end of the bulb's neck. The bulb is heated in a boiling water bath to vaporize
the liquid. The volume of vapor formed at 100 C (the approximate temperature of the boiling
water - the exact temperature of the boiling water must be measured experimentally) and
atmospheric pressure is greater than the volume of the bulb. The vapor first pushes all of the air
out of the bulb and then begins to rush out of the opening until the pressure inside the bulb
equals the pressure outside (atmospheric). With careful observation, the vapor can be seen
exiting the bulb. It looks like a jet engine exhaust or a swirling cloud. When all of the liquid is
vaporized and no more vapors is seen leaving the bulb, the bulb contains a sample of vapor at
atmospheric pressure and 100 C with a volume exactly equal to the volume of the bulb. The
opening in the neck of the bulb is quickly sealed with a flame. It is important that the bulb be
sealed at exactly the moment that vapor stops escaping from the bulb. (Sealing before vapor
stops escaping will result too much vapor remains in the bulb. The molecular mass calculated
will be too high. Waiting too long to seal the opening will result in a molecular weight that is too
low. Can you explain why?) The sealed bulb is cooled, dried and carefully reweighed. The
volume of the bulb must now be determined. The vapor inside has condensed, and the space
above the liquid in the bulb is a near vacuum. The sealed tip of the bulb is then cut off with a file
under water in a large container. The water rushes into the bulb, filling it completely. The bulb is

dried on the outside and weighed once again. The volume of the bulb can be determined from the
mass of water it contains. Barometric pressure and room temperature are carefully measured and
recorded. The density of water at room temperature is either measured or obtained from the
chemical literature. The volume (V) of the bulb is calculated from the mass of the water needed
to completely fill the bulb. The mass (g) of vapor is obtained by subtraction. The temperature of
the boiling water bath (T) and atmospheric pressure (P) were measured directly during the
experiment. With this information, the molecular mass of the gas can be calculated using the
ideal gas law. We will make a few simplifications in our experiment. First, we will use an
ordinary Erlenmeyer flask covered with aluminum foil rather than a glass bulb. A tiny hole will
be made in the foil to allow vapor to escape from the flask. We will not seal the flask when vapor
stops escaping from the hole. We will simply remove it from the hot water bath as quickly as
possible. The vapor will condense rapidly. We will measure the volume of the flask by filling it
with water and then measuring the volume of water using a graduated cylinder. The information
needed to determine the molecular mass of the unknown is the same as in the classic Dumas
method: pressure (P), volume,(V) the mass of the vapor,(g), and the temperature (T). Using this
procedure, we should be able to determine the molecular mass of a volatile liquid to within 10%
error.In this experiment, the students will be working with volatile liquids and open flames. The
possibility of fire, and burns, is real. Dispense the liquid unknown from the bottle in the hood,
and cover the flask. Keep it capped when at the vicinity of Bunsen burners. This will keep the
concentration of flammable vapor below the limits of combustion. If a liquid is spilled at a
bench, have those around you extinguish burners until the spill can be cleaned up. Notify your
instructor if there is a spill. Any remaining liquid will drain and safely evaporate. The liquids are
mildly toxic. If you have a spill and large quantities contact your skin, wash well with soap and
water.
Nowadays, thanks to steps forward in technology, the Dumas method is becoming more and
more widespread.
Stringent standards on the composition of food and feed are being applied in ever widening
markets. Precise analysis of these components is now essential to any company wishing to
market
its
products,
particularly
on
an
international
basis.
VELP Scientifica has introduced a new nitrogen analyzer based upon the Dumas nitrogen
determination. Unlike the commonly used Kjeldahl method, Dumas method, also known as
elemental analysis or combustion method, detects the total nitrogen content, not only that which
is contained within proteins.
The Dumas method for nitrogen determination, developed in 1831, is older than the Kjeldahl,
1883, but more convenient in many aspects such as speed, safety, cleanliness, productivity and
cost
per
analysis.
The problem in the past was that it was not easy to reproduce the conditions required by the
Dumas method and for this reason the Kjeldahl technique took the lead, and became considered
as the classical method for nitrogen/protein determination. Nowadays, thanks to steps forward in
technology, the Dumas nitrogen determination is becoming more widespread.
Results obtained with the Dumas nitrogen determination are usually a little bit higher than with
Kjeldahl, since even the heterocyclic compounds and nitrogen compounds (e.g. nitrites and
nitrates) are detected. In the Kjeldahl method, such compounds are converted into the
ammonium
ion
incompletely
or
not
at
all.
The opposite could also happen (rarely), because in this kind of analysis there are lots of

variables that could influence the final result. Indeed, there are many minor variants of the
Kjeldahl method, involving the use of different catalysts, heating times, volumes and distribution
of sulfuric acid and masses of test portion: this shows that the Kjeldahl procedure may be
influenced by experimental errors. Recovery is the same for both the methods ( 99.5%), whilst
the detection limit is lower for Dumas than for Kjeldahl (0.003 mg N absolute vs. 0.1 mg N
absolute).
The determination of the total nitrogen in soy sauce by the Dumas method was studied. Eleven
samples of soy sauce were used and a half gram of each sample was combusted at 870C in an
oxygen atmosphere. The resulting nitrogen oxides (NO x) were reduced to nitrogen by a copper
column at 600C, and nitrogen was detected with a thermal conductivity detector. Analyses of
each sample were repeated 3 times on 2 different days. The samples were also analyzed by the
Kjeldahl method under the optimum digestive condition in order to know the differences
between the methods. The standard lysine solution was analyzed by the Dumas method, and
accurate results were obtained. Two sets of data by the Dumas and the Kjeldahl methods were
tested with a two-sided Welch t-test. There were significant differences in six samples between
the methods (p < 0.05). However, the differences between the methods were within the
repeatability limit, calculated by the Horwitz equation. Also, the correlation between the methods
was 0.9999. The Dumas method had excellent intermediate precision, and was equivalent to, or
more accurate than, the Kjeldahl method under the optimum digestive condition.

REFERENCES:
Gucker, F. T. Jr. and W. B. Meldrum (1942).Physical Chemistry. American Book Company.
Links:
Experiment 8: molecular weight of a volatile
http://intro.chem.okstate.edu/HTML/SEXP8.HTM

liquid.

(n.d.).

Retrieved

from

Molar mass of a volatile liquid by the Dumas method (n.d.). Retrieved from
http://www.webassign.net/userimages/fgdennis@waynecc/lab_molarmassgas_intro.pdf

Determination of molar mass by vapor density (2010). Retrieved from

https://jamyang.wikispaces.com/file/view/lab_3_determination_of_molar_mass_by_vapor_densi
ty_840509.pdf
Bunseki
Kagaku
(March
2007).
Retrieved
from
https://www.researchgate.net/publication/245417859_Application_of_Improved_Dumas_Metho
d_to_the_Determination_of_Total_Nitrogen_in_Soy_Sauce
Dumas
nitrogen
and
total
nitrogen
content
http://www.velp.com/en/service_support/dumas_nitrogen

(n.d.).

retrieved

from