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I.

Abstract
This experiment focuses on the determination of molar mass of a volatile liquid by vapour density
method. This particularly revolves around the estimation of the molar mass of volatile liquid from
their vapour densities at a temperature above their boiling points using Dumas Method, which is a
classical technique still used in the laboratories despite the new technological instrumentations. With
the values of pressure, temperature, and density on hand, the data regarding the relative masses of the
flask and water were utilized to get the unknown molar masses. After considering some sources of
errors which are naturally occurring in the execution of the Dumas method for molar mass
determination, the group was able to get the value of 90.33 g/mol for the average molar mass. Thus,
with the data gathered and the results interpreted, it is therefore concluded by the end of the
experiment that the closest match to it was that of Ethyl Acetate, also known as ethyl ethanoate,
commonly abbreviated EtOAc or EA.

II. Introduction
The chemical and physical methods for determining molecular and atomic formula weights or
molar masses as a way of categorizing and analysing new materials have been observed through time.
Many of these methods have been out of date because the modern laboratory is generally equipped
with instrumentation. However, the principles used in the older methods are still considered
significant and many form the basis for the prediction of chemical and physical behaviours and
properties of substances.
The Dumas method is a classic technique for determining the formula weight of a volatile liquid.
The concept of equal volumes of gases measured under identical conditions would contain equal
numbers of gas particles was proposed by Avogadro. It was possible to describe a constant volume
which would contain a gram-atomic weight of a gaseous element or compound under fixed conditions
with an established relative atomic mass scale, known today as the molar volume.
An application of this useful information to liquids and solids which are appreciably volatile is
allowed by understanding the concept of the different gas laws.. As long as the temperature and
pressure are known, a measured volume of gas can be converted to moles since: n = PV/RT. Since
massing a sample of gas is relatively simple, these two pieces of information are the minimum
required for a molar mass determination.
A volatile liquid is heated to a known temperature, usually above its boiling point, and allowed to
escape from a container through a tiny orifice in the Dumas method. The container is cooled to room
temperature once the liquid has vaporized. The vapour which gradually remained in the container at
the higher temperature condenses to a liquid and is then massed. The room pressure can be used
because the system is open to the atmosphere through the orifice to calculate moles if the volume of
the container is known along with the high temperature and from there a molar mass can be
determined.
This method depends on a lot of things to consider. One assumption is that the liquid is not so
volatile that a significant amount will be lost to evaporation through the orifice as the container cools
while it is volatile enough to vaporize at the elevated temperature. At the temperature and pressure at
which it occupies the container, the vapour is also assumed to behave ideally. 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. Generally
speaking, the larger these are, the greater the error in the determination, which means both share a
direct relationship. The situation is further complicated by the interaction of these two factors.
There is another problem with the basic method which is more easily addressed. There is a fixed
amount of air determined by the volume, temperature and pressure in the container when the container
is "empty", or the instant before the liquid is added or the vapour forms. This air has mass and
contributes to the overall mass of the container assembly, but when the liquid is present it vaporizes to
some extent determined by its vapor pressure at room temperature. If the temperature and pressure
remain constant, the presence of this vapour forces out some of the air through the orifice since the
internal pressure is equalized with the room pressure and the number of gas particles remains
constant. Thus there is air missing that should be counted in the final mass if the mass of the
condensed liquid is to be determined by difference when the container is massed again.
This condition results in an apparent mass of liquid that is too small which in turn makes the
molar mass calculation too small. The moles of air forced out by the vapour are equal to the moles of
vapour that forms. This is determined by the vapour pressure of the liquid at room temperature. If this
value is known, the moles of vapour that are present in the flask above the residual condensed liquid
can be calculated as:
n
vapour
= (P
vapour
x V
container
)/RT
Avogadro's Law tells us that these moles of vapour 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. All of this
depends, of course, on knowing the vapour pressure of the liquid, P
vapour
.

III. Methodology

List of Chemicals and apparatus
2-propanol
Ethanol
Ethyl acetate

Analytical balance
600-ml beaker
125-ml Erlenmeyer flasks
Bunsen burner
Wire gauze
Thermometer/barometer
Here is a photo of the Dumas set-up that we used upon
performing the experiment. An Erlenmeyer flask was immersed
in a 600-ml beaker. A thermometer was used to measure the
temperature as the unknown sample was vaporized. Several
reminders had to be taken down throughout the experiment. A
foil cap must be used. The hole in it must only be tiny, enlarging
the hole could give an error into the determination. The water
should be high enough not to enter through the hole.





1. A clean and dry Erlenmeyer flask with a foil cap was weighed in an analytical balance; this was
weighed as the empty flask.
2. 4 ml of an unknown sample was injected through the foil making a tiny hole.
3. This flask was then immersed in a 600-ml beaker of water which was then quickly boiled.
4. A gentle boil had to be achieved until all the liquid was evaporated.
5. Boiling point of water at room pressure and the pressure itself was recorded.
6. After allowing the flask to dry and to cool down, the mass was also then recorded.
7. The same flask was used for water. It was filled with water almost completely with room
temperature. This temperature was recorded.
8. This flask filled with water was then weighed in an analytical balance and mass was then
recorded.
9. The volume of the flask was determined using this measurement, the first measurement and the
density of the water at room temperature.

IV. Results and Discussion

Barometric pressure, P:
752.5 mmHg or
0.990 atm

Room Temperature, T
R
:
33
o
C or
306.15K
Density of water at T
R
: 995.948 Kg/m
3



Sample Name Ethyl Acetate

Table 1.1: Determination of Estimated Molar Mass of the Unknown Sample
Trial 1 Trial 2 Trial 3
Mass of empty flask, g 94.687 89.242 89.245
Mass of empty flask with Al foil and Cu wire, g 96.131 90.388 90.527
Mass of "empty" flask with Al foil, Cu wire, and sample
96.618 90.809 90.968
Mass of vapor (m), g 0.487 0.421 0.441
Temperature of vapor (T
B
), K

368.15 366.16 368.15
Mass of flask filled with water, g 255.607 249.557 250.086
Mass of water, g 160.92 160.315 160.841
Volume of Flask based on water (V), L 0.162 0.161 0.161
Moles of vapor at T,V and P,n 0.0053062 0.0053022 0.0052734
Estimated molar mass of vapor, g/mol
91.7794 79.4010 83.6273

Table 1.2: Determination of the True Mass of Vapor that Occupied the Flask at Boiling Temperature
Trial 1 Trial 2 Trial 3
Moles of air displaced by the vapor at T
R
0.00092778 0.00110878 0.00092205
Molar mass of air, g/mol 28.97 28.97 28.97
Mass air displaced by the vaporized liquid at T
R ,
g 0.02688 0.03212 0.02671
True mass of vapor that occupied the flask at the boiling
temperature of water, g
0.5139 0.4531 0.4677

Table 1.3: Determination of Corrected Molar Mass of the Unknown Sample
Trial 1 Trial 2 Trial 3
Corrected Molar mass of the vapor,g/mol
96.84 85.46 88.69
Corrected Molar mass of the vapor (Average),g/mol
90.33
Molar mass (literature Value), g/mol 88.11
% difference 9.45 3.05 0.66
average % difference 2.49

In this experiment, the group utilized the Dumas method in obtaining the identity of an
unknown sample using the calculated molar mass. The first part involved injecting about 3-4 mL of
sample leaving a tiny hole on top. This was then heated and brought to boil until all the liquid
evaporated. The air was swept out of the container. What was important at that point is to be be able
to judge the point at which the flask is just filled with sample vapor. This vapor was then cooled to
room temperature, 306K and was weighed. This consitutes the mass of the vapor. Using the
atmospheric pressure indicated in the barometer, 0.990 atm; the temperature at which the sample
boiled, 366.15K, and the volume of the flask, 0.161L, moles of the sample vapor,n, was calculated
using the gas equation:
n
vapor
= PV/RT
boiling
With the mass of the vapor and the number of its moles, estimated molecular weight had been
computed, however this was way far from the literature value,and lower than expected. To correct
this, the group had to account for the moles of the sample that remained as vapor at room temperature
during the weighing. This is equal to the moles of air the sample vapor displaced. To determine the
number of moles of this, a corrected value of P was used 131.531895 mmHg or 0.1731 atm. The
temperature used was room temperature which was 306.15K, and the same equation was used:
n
displaced
= P
corrected
V/RT
room.
Using the molar mass of air, 28.97 g/mol, the mass of air displaced was obtained. This was
added to the mass of the sample vapor obtained previously. The combined mass was then divided to
the moles of sample vapor to obtain the correct molar mass.

The average molar mass obtained was 90.33 g/mol. The closest match to it was that of Ethyl
Acetate, also known as ethyl ethanoate, commonly abbreviated EtOAc or EA. Its formula is CH
3
-
COO-CH
2
-CH
3.
This colorless liquid has a characteristic sweet smell (similar to pear drops) and is
used in glues, nail polish removers, decaffeinating tea and coffee, and cigarettes.
Dumas method depends on several things which had to be done correctly.The group had to
make sure that prior to removing from hot water bath, the flask must no longer contain liquid sample.
This means that all the sample had turned to vapor. The copper wire used to seal the foil must be
neatly done and no room for water to hide or else, it could have also affected the weight of the vapor
obtained. The hole must be tiny to avoid significant loss of of sample vapor. While the group carried
out the experiment delicately, there was still an average of 2.49 % difference from the literature value
of 88.11 g/mol. This can be accounted for the non-ideal behavior of sample vapor: volume of the
molecules itself and intermolecular forces which were factors to consider for container that small. In
the Physical Chemistry book of Peter Atkins, it was mentioned that the excluded volume can actually
be computed by V
3
or 8 Vmolecule .

Another source of error could be the presence of water vapor in the flask which may had come
from the water bath. Water vapor contributes to the mass of the sample vapor which would have made
the result deviate from the true value.

V. Sample Calculations


Moles of vapor (n) =


P = (752.5mmHg) (


) = 0.990 atm
T = 366.15K
V

= 0.161 L
R = 0.0821


Moles of vapor (n) =
()()
() ()
= 5.3022 x 10
-3
mol
Estimated molar mass of vapor
MM =


mVapor = 0.421 g ; nVapor = 5.3022 x 10
-3
=



MM = 79.40 g/mol
Moles of air displaced by the vapor at T
R

n
displaced
=


P = 131.531805 mmHg x


= 0.1731 atm
V = 0.161L
T
R
= 306.15 K
n
displaced
=
()()
()()
= 1.1088 x 10
-3

moles
Molar mass of air = 28.97 g/mol
n
displaced
= 1.088 x 10
-3
mol x 28.97 g/mol = 0.03212 g
True mass of vapor
m
true mass
= 0.421 g + 0.032 g = 0.453 g
Corrected MM
vapor

MM
corrected
=

( )
= 85.44 g/mol

VI. Summary and Conclusion
The experiment enabled us to attain more knowledge regarding the molar masses of volatile
liquid compounds or mixtures which were determined using the Dumas method. Also, we learned to
be extra careful in handling the sample because it can be lost through evaporation, spilling, etc. This
could lead to a less accurate data calculated because of the wrong measurements obtained. The
estimated molar mass of vapor was also calculated, and used to compute for the corrected molar mass
of the vapor, which was compared to the theoretical molar mass of vapor. Overall, an accurate result
was obtained, which led to an average percent difference of 2.49%. The main formula for this
experiment was PV = nRT, which is the ideal gas equation. The limitation of the experiment is that
only volatile liquids were used.

VII. References

Experimental Studies for General Chemistry, Malcolm F. Nicol, Arlene A. Russell, Eleanor D. Siebert
(1973)
Laboratory Manual for Chemistry, Lawrence Epstein (1986)