I.

Abstract

This report contains all the necessary information, results and conclusions that the group
have gathered during the experiment which is the determination of molar mass of a volatile liquid by
vapour-density method or Dumas method. During the experiment the students are asked to
estimate the molar mass of volatile liquid from their vapour densities at a temperature above their
boiling points using Dumas method and also master the ideal gas equation which is PV=nRT.

II. Introduction

In the early 19th century, Jean-Baptiste Dumas, a distinguished French chemist, created a
relatively simple method for determination of the molecular weight of a substance. With this
method, molecular weight is calculated by measuring the mass of a known volume of a vaporized
liquid. Because the concept of the mole had not been developed in Dumas era, he computed
relative molecular weights based on relative gas densities. Though Dumas got mixed results based
on erroneous assumptions concerning elements in the gas phase, he is credited with establishing
values for the molecular weights of thirty elements. One of the early methods for the determination
of the molar mass of volatile substances was through the measurement of the density of the vapor
of the substance. The method is reliable and convenient and is still employed in some situations.

In the modern version of the Dumas procedure, an Erlenmeyer flask is used rather than the
glass bulb of Dumas day. The temperature, pressure and volume of the vapour are determined and
the molar mass is found utilizing the Ideal Gas Law.

A volatile liquid is one that easily can be converted to a gaseous state. The gas that forms
from the vaporization of a volatile liquid is called a vapor. A vapor is assumed to act as an ideal gas. If
the volatile liquid is unknown, utilizing the Ideal Gas Law can determine the molar mass of the
volatile liquid using the Dumas method. The Dumas method is also referred to as the vapor density
method. With the Dumas method, the molar mass of the volatile liquid is determined by measuring
the mass of the vaporized liquid and the volume occupied by the vapor. When heated, the vaporized
liquid forces the air and excess vapors in the flask out through a pinhole until the vapor pressure
inside the flask equals the external atmospheric pressure. Then, the volume occupied by the vapor is
measured. The mass of volatile liquid is determined from the mass of the condensed liquid in the
flask. The temperature of the gas will be the temperature of the boiling water bath. In this
experiment, the boiling point of each volatile liquid is below the boiling point of water. The pressure
will be the same as the room pressure.

The Ideal Gas Law expresses the relationship between the number of moles of a particular
substance in a gaseous state and the volume, temperature, and pressure of that gas (Equation 1).
Hence, the Ideal Gas Law can be used to determine the molar mass of a volatile liquid from the
density of the vapor. The number of moles can be expressed as the mass of the substance (m)
divided by the molar mass of the substance (M) (Equation 2). Molar mass is defined in terms of the
mass in grams of a substance per mole of that substance, g/mol.

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Equation 1 (Ideal Gas Law): PV = nRT

where R is the ideal gas constant, which is equal to 0.0821( L atm)/(mol K).

Equation 2: n =m / M

If Equation 2 is substituted into Equation 1, it yields the following result:

Equation 3: PV = mRT / M

Solving for the molar mass of the substance yields the following equation:

Equation 4: M = mRT / PV = dRT / P

Equation 4 shows the relationship between density and molar mass. Density equals mass divided by
volume. Hence, if the vapor density can be determined at a given temperature and pressure, then
the molar mass can be calculated.

III. Methodology

Materials used:

Analytical Balance 600-ml beaker 125-ml Erlenmeyer flasks

Hot Plate Thermometer Barometer
Iron Stand Iron clamp boiling chips
Distilled water 50-ml graduated cylinder Aluminum foil
Copper wire syringe

Methodology

1. A completely cleaned and dried 125-ml Erlenmeyer flask was used.

2. The empty flask was weighed in the Analytical Balance.
3. After weighing the mouth of the flask was covered with aluminum foil and a copper wire
was twisted tightly around the neck just below the rim.
4. Excess foil was removed so that water does not condense under the foil.
5. The flask with copper and foil was reweighed again and the assembly was carefully
prepared.
6. A 3-4 ml of unknown sample was injected carefully into the flask with a syringe in order
not to cause large hole causing errors.
7. The flask was immersed in a 600-ml beaker with few boiling stones. The water should be
high enough to cover most of the flask.
8. The water bath was boiled immediately but the heat was reduced to achieve gentle boil
until all of the liquid in the flask was evaporated.
9. The boiling point of water at room pressure, the pressure itself and the temperature of
the vapor were recorded.
10. The flask was removed from the water bath and allowed to cool. The water was
removed completely form the outside of the flask especially under the cap edges as the
steam from boiling water can condense under the edges and change the mass of the
container significantly.

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 11. The mass of the flask was weighed again after cooling at room temperature.
12. After weighing, the flask was filled completely with water at room temperature and then
the mass was recorded.
13. Two trials were made using the same procedures.
14. The last measurement, together with the first one and the density of water at room
temperature, allows the volume of the flask to be determined.

IV. Results and Discussion

One of the properties that helps characterize a substance is its molar mass. If the substance
in question is a volatile liquid, a common method to determine its molar mass is to vaporize it and
apply the ideal gas law, PV = nRT to the data collected. Because the liquid is volatile, it can easily be
converted to a vapor. Volatile substances are usually composed of nonpolar molecules. As a result
the molecules have primarily London dispersion forces and very little thermal energy is required to
overcome these attractive forces since the molecules are relatively small. Therefore, the liquid
vaporizes easily and quickly at temperatures less than 100C. While the substance is in the vapor
phase, you can measure its volume, pressure, and temperature. You can then use the ideal gas law
to calculate the number of moles of the substance. Finally, you can use the number of moles of the
gas to calculate molar mass.

Table 1.1: Constants at room pressure and temperature

Barometric Pressure, P Room Temperature @ TR Density of water @ TR

752 mm Hg 33 C = 306.15 K 0.994711 g/mL

Table 1.2: Determination of molar mass of a volatile liquid by vapor-density method

Trial 1 Trial 2 Trial 3

Mass of empty flask (g) 96.983 g 93.630 g 96.992 g
Mass of empty flask with Al foil and 97.837 g 93.948 g 97.838 g
Cu wire (g)
Mass of flask with vapour (g) 98.305 g 94.383 g 98.326 g
Mass of vapor (g) 0.468 g 0.435 g 0.488 g
Temperature of vapor (C) 94 C 95 C 97 C
Mass of flask filled with water (g) 254.504 g 252.160 g 254.515 g
Mass of water (g) 157.521 g 158.53 g 157.523 g
Volume of flask based on water (mL) 158.36 g 158.53 g 157.523 g
Moles of vapour at T,V and P, n (mol) 6.24x10-3 mol 6.28x10-3 mol 6.24x10-3 mol
Estimated molar mass of vapor (g/mol) 75.02 g/mol 69.29 g/mol 78.23 g/mol
Moles of air displaced by the vapor at 1.09x10-3 mol 1.097x10-3 mol 1.09x10-3 mol
TR (mol)
Molar mass of air (g/mol) 28.97 g/mol 28.97 g/mol 28.97 g/mol
Mass of air displaced by the vaporized 0.0316 g 0.0318 g 0.0316 g
liquid at TR (g)
True mass of vapour that occupied the 0.4996 g 0.4668 g 0.5196 g
flask at the boiling temperature of
water (g)
Corrected molar mass of the vapor 80.06 g/mol 74.33 g/mol 83.27 g/mol
(g/mol)

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 Corrected molar mass of the vapor 79.22 g/mol
(average) (g/mol)
Molar mass (literature value) (g/mol) 88.105 g/mol
% Difference 9.13 % 15.63 % 5.49 %
% Difference (average) 10.08 %

At first, the room pressure, room temperature

and the density of the water at room temperature were
determined which will be used for the calculations all
throughout the computations. The figure at the right is a
sample set-up of the experiment. After all of the
required data were gathered and finished all of the
calculations, we come up with the result of an average
molar mass of 79.22 g/mol which is quite far from the
theoretical value which is 88.105 g/mol. The reasons
why the result is quite far are explained further below.
The identity of the unknown sample that is given to us is
ethyl acetate (88.1 g/mol, vp298 = 82 mmHg, bp = 76.5
C) has a characteristic fruity odor and a pleasant taste
when diluted. It is somewhat soluble in water and
mostly soluble in common organic solvents. It is used in
artificial fruit essences and as a solvent for lacquers and
varnishes including fingernail polish. Prolonged
breathing of vapors may cause liver and kidney damage. Figure 1: Sample set-up

In essence, the experiment consists of creating a container with a reproducible volume and a
pinhole orifice from which the volatile liquid will be vaporized at the boiling point of water and room
pressure. When the unknown liquid in the flask has evaporated, the vapor pressure at room
temperature has led to the displacement of some air. Since that air was in the flask at the outset, it
should be weighed too, so the resulting mass will be too low. The determination of the point, when
no liquid is present, is difficult. Stopping too soon will result in large positive errors in the mass;
stopping too late will result in small negative errors in the mass due to diffusion. After cooling, the
mass of the container is greater by the amount of liquid that remains, representing the amount of
vapour which filled the volume at the boiling point of water and room pressure. A mass correction
must also be made for the air displaced by the vapor. This results in an apparent mass of liquid that
is too small which in turn makes the molar mass calculation too small.

The vapor is 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 behaviour which are
molecular volume and intermolecular forces. 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 like hydrogen
bonding 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. Non ideal behaviour of vapor affects the results of the experiment simply because gases in
nature are difficult to handle, some of it may evaporate and escape the flask which will cause a large

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error, so it is important select a compound which is a gas at high temperature and pressure while
liquid at room temperature.

The moles of air forced out by the vapor are equal to the moles of vapor that forms. This is
determined by the vapor pressure of the liquid at room temperature. If this value is known, the
moles of vapor that are present in the flask above the residual condensed liquid can be calculated.
The vaporized liquid is able to force the air in the flask along with the some of the vaporized liquid
into the environment because the presence of the vapor in the flask creates a pressure inside the
flask that is greater than the external atmospheric pressure. This causes the air and excess vapor to
be expelled until the pressure inside the flask equals the atmospheric pressure. Avogadro's Law tells
us that these moles of vapor must equal the moles of air displaced since the conditions are the same
for both. These "missing" moles of air can be converted to grams using the weighted average molar
mass of air and added into the final mass of the assembly.

Errors in mass determination are very important. Since the experiment requires at lot of
mass measurements, fingerprints can cause errors. An uncertainty of 0.01 g will cause a big change
in the molar mass. Other possible sources of errors are, the compound may have impurities, the
liquid was not completely vaporized, there was an error in measuring the volume of the flask, all the
liquid was not allowed to condense, some of the vapors escaped through the pinhole.

V. Sample Calculation

First Trial:

() = , ,

() = 98.305 97.837

() = 0.468

() =

= 254.504 96.983

= 157.521

() =

= 157.521 0.994791

= 158.36

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, () =

1
{(752.5 ) (760 )} (0.15836 )
=

(0.0821 ) (33 + 273.15 )

= 6.24103

(/) =

= 75.02 /

() =

1
{(131.53 ) (760 )} (0.15836 )
=

(0.0821 ) (33 + 273.15 )

= 1.09103

=

= 1.09103 28.97

= 0.0316

()
=
+ .

/ = 0.468 + 0.0316

/ = 0.4996

/
( )=

0.4996
/ =
6.24103

/ = 80.06

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 | |
% = 100%

|88.105 80.06|
% = 100%
88.105
% = 9.13%

The Solution above shows the results and computations for the determination of molar mass
and identity of an unknown sample for trial 1. Same way of computation and formulas were used for
the other two trials.

VI. Summary and Conclusion

The scope of this experiment has helped us gain knowledge about how the molar masses of
volatile liquid compounds or mixtures were determined during the early times using the Dumas
method. We also had great time learning and at the same time had fun during the experiment
because in modern laboratory, modern equipments and techniques were used, but the principles
are still applied which is an advantage for us because of this experiment, and we experienced the
older technique. The experiment is limited only for volatile liquid with the use of vapor-density
method or Dumas method. As long as all of the data required for computation were gathered, the
computation will follow with the use of the main formula which is the ideal gas equation: PV=nRT,
the computation itself is simple as shown in the sample computation part, after computation the
results showed that the average molar mass that we had in the three trials was: 79.22 g/mol; the
theoretical molar mass of our unknown liquid is 88.105 g/mol which is ethyl acetate that gives us
10.08 percent difference.

VII. References

Atkins, P. & de Paula, J. (2010). Physical chemistry (9th ed.). New York, USA: Oxford
University Press.

Atkins, P. & de Paula, J. (2006). Physical chemistry (8th ed.). New York, USA: Oxford
University Press.

Skoog, D. A., West, D. M., Holler, F. J., & Crouch, S. R. (2014). Fundamentals of analytical
chemistry (9th ed.). California, USA: Brooks/Cole, Cengage Learning.

http://www.chemtopics.com/aplab/mmvliq.pdf

http://suhiapchem.weebly.com/uploads/5/9/6/5/5965534/lab_3-_determination_of_molar
_mass_by_vapor_density_840509.pdf

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