CHM170L Organic Chemistry 1 Laboratory

4th Quarter SY 2016-2017

Determination of Molar Mass of Volatile Liquid

Premarion, Matthew M.1, Rivera, Hazel Anne T.1, Villaflor, Shekinah Mae J.1
1
Student(s), CHM170L /B40, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology

Abstract

This experiment aims to estimate the molar mass of volatile liquids from their vapor densities at a temperature above their
boing points using Dumas Method. This approach is considered as one of the oldest techniques to measure the molar mass
of volatile liquid with the use of the ideal gas law. This experiment proceeds by injecting a small amount of the sample
liquid, namely acetone, ethyl alcohol and ethyl acetate, to a pre-weighed Erlenmeyer flask through a small hole on the cap
made from aluminum foil sealed by fine copper wire. The flask containing the sample is heated through a hot water bath
using a hot plate. After all the liquid has evaporated, the sample is allowed to be cooled at room temperature. The flask is
weighed again where the change on its mass is recorded as the mass of the vapor (m) occupying the fixed volume of the
flask (V) at temperature (T) and at pressure (P). Since air is present in the flask that is displaced by the vapor, a correction
value is added by determining the amount of air present in the empty flask. After calculating the molecular mass of each
sample using the data, a percentage difference of 6.51%, 3.97% and 5.5% were acquired for ethyl alcohol, acetone and
ethyl acetate, respectively.

Keywords: Dumas method, volatile liquid, ideal gas law, vapor pressure, molar mass

Introduction
In the early 19th century, Jean-Baptiste Dumas, a famous
French chemist, created a method for determination of the
molecular weight of a substance. Named after him, the
Dumas Method is considered as one of the pioneer
methods when it comes to identifying the molecular
weight of a substance. This method takes us of the density
of the vapor of the object of interest. Though the
materials used and the process itself has been considered
obsolete, it has been modified in ways such that it can be
used again in the modern times.
A volatile substance is a substance that can perform a
rapid change in its phase turning to gas at a temperature
less than 100oC. By using the Dumas method, the sample
it heated until all of it evaporates. Once it does, the
sample is then cooled where the vapor will escape
through the small orifice made from injecting the
substance through the cap. The vapor which did not
escape, will then condense inside the container, serves as
the amount of vapor that occupied the volume of the
whole container at a certain pressure and temperature.
The mass is then taken and is assumed to behave ideally,
so that it would with accordance to the equation.
Since the experiment requires the molecular mass of the
sample, it will then be modified to comply with the needs,
thus resulting to the equation:
where m is the mass of the vapor, R is the ideal gas
constant, T is the temperature of the vapor at its boiling
temperature, P is the pressure of the atmosphere, and V is
the volume of the container containing the vapor. The
equation above is also known as the combined gas law.
Since it is known that the vaporization is performed under
low pressure and heightened temperature tends to behave
close to being ideal, the proceedings of the experiment is
performed under these conditions.
For this example, the samples used are ethanol, ethyl
acetate and acetone, all of which are known as volatile
substances. Small amounts of the sample are to be
contained in pre-weighed Erlenmeyer flasks which are
then heated until the sample liquid completely vaporized.
Applying the Zeroth law of thermodynamics, the system
is at thermal equilibrium, and thus, the temperature of the
vapor can also be considered as the temperature of the
water.

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Considering that the density of air is smaller than that of

the sample used, the air initially inside the pre-weighed
flask is to be displaced by the vapor, resulting to the loss
of weight of the vapor which can be determined by the
equation stated on the previous part. However, the
pressure used is the vapor pressure of the vapor at the
room temperature as related to the air pressure. Using
Antoines equation, the calculated mass of air can be
added to the mass of the vapor, since the pressure of the
vapor of volatile liquids relate to the room temperature.
The materials used are:
aluminium foil, fine copper wire, pliers, wire
cutter, scissor, glass boiling stones, parafilm,
syringe
The equipment and glassware used are:
analytical balance, 600-mL beakers, 125-mL
Erlenmeyer flasks, hot plate, barometer,
thermometer

Set-up of Apparatus

This equation holds the parameters A, B and C that of

which differ depending on the identity of the substance.
Also, T is the absolute temperature and P vapor is the vapor
pressure. A table can be used as reference for the values
of parameters A, B and C.

The objective of the experiment is to estimate the molar

mass of volatile liquids namely ethanol, ethyl acetate and
acetone from their vapor densities at a temperature above
their boiling points using Dumas method.

Methodology

Preparation
The reagents used are:

o Acetone (CH3COCH3). A colorless,

mobile, flammable liquid with melting
point of 95.4 C and boiling point of
56.53 C; it has a relative density of
0.819 (at 0 C); it is readily soluble in Experimental Procedure
water, ethanol, ether, etc., and itself This experiment makes use of certain materials
serves as an important solvent. that are readily available, all of which are
o Ethanol (C2H6O). Also known as ethyl
necessary in performing the experiment. These
alcohol or grain alcohol, is a flammable,
materials are as follows; aluminum foil that will
colorless chemical compound, one of the
serve as the cap, fine copper wire to serve as the
alcohols that is most often found in
seal of the cap, scissor to cut off the excess foil,
alcoholic beverages; in common
pliers or wire cutter for cutting and twisting the
parlance, it is often referred to simply as
wires, boiling stones which are placed on the hot
alcohol.
water bath, hot plate as the platform for heating,
o Ethyl Acetate (C4H8O2). A volatile
and syringes that will serve as the transferring
colorless liquid with a pleasant fruity
agent.
smell used to manufacture perfumes.
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4th Quarter SY 2016-2017
The experiment proceeds using 125-mL
Erlenmeyer flasks covered by an aluminum foil
tightly held together by some fine copper wire. A
tiny orifice is created by the syringe when the
sample is added and this orifice later serves as a
vent from which the vapor should come out. The
flask is very suitable for the experiment since the
mass is small enough for the analytical balance
and large enough to contain a sufficient mass of
vapor. The flask is weighed with and without the
cover as to determine the volume and vapor mass.
The gathered masses are then considered
collectively as the empty flask.
The aluminum cap is fashioned in such a way that
the improvised cap out of a square aluminum foil
is to be tightly fitted on the mouth of the flask. It
is then sealed by copper wire at the side of the
cap exactly below the flasks rim. (At first failed
attempt, a parafilm was utilized.) The excess
aluminum foil is carefully removed by means of a
cutter or any cutting materials. This is to prevent
the accumulation of condensed water vapor
beneath the foil. The sample is introduced in the
container with the use of the syringe. Injecting
the sample will also cause the production of the
orifice in the cap, as mentioned previously. The
sample must be introduced carefully, at an
amount of 3-4 ml, as to avoid the enlargement of
the orifice which will cause a huge amount of
difference.
The flask containing the sample is then heated by
using a hot water bath, a beaker placed on a hot
plate in this case, until all the sample has
vaporized. The water is brought to a quick boil
and stabilized to a gentle boil for 10 minutes or
until the liquid sample completely vaporizes.
Afterwards, the flask is then set to cool to room
temperature, ensuring that the water around the
surface and the cap edges are removed as the
steam can change the mass of the system. As it
reaches thermal equilibrium, the flask is weighed
again.
Experiment #1 Group No. 6 12th of May 2017
Upon performing this experiment, the flasks are
then filled to the rim with water and weighed,
where the gathered data is to be subtracted from
the mass of the empty flask. The volume of the
flask can then be determined for it is related to
the mass of the water calculated, given the
density of the flask at the room temperature.
Results and Discussion
In the data gathered, it can be observed that the percent
difference varies for each reagent used. A possible
explanation for that is the presence of intermolecular
force on each compound. If a gas behaves ideally, it can
be assumed that the intermolecular force acting on the
compounds will not contribute on the actual pressure of
the gas. When the real behavior is considered, it is
technically wise to use the Van der Waals gas equation as
to which correction factors are present. The correction
factors a and b are for the presence of intermolecular
force and the consideration of the volume of the gas
molecules, respectively.
Analyzing the data, we can see that the magnitude of the
parameters affect the percent different produced. I can be
observed that as these parameters increase, so do the
resulting error. In Table 2 (See Appendices), acetone can
be seen with the second highest parameter a from the
three and yet consists of the highest percent difference
showing that there are other causes of error present. These
causes may be as follows:
the size of the orifice is too big orifice causing
immediate evaporation of the volatile substances
vapor
a high water level which causes the bubbling of
water inside the flask, thus increasing the mass
accumulated or stored condensed water vapor on
the edges of the cap which increases the mass
insufficient or excessive amount of sample used.
contamination of the sample
Though it can be said that the molar mass is constant no
matter how the amount of present sample varies, if the
amount of air that could be displaced is to be considered,
we can say that error could be produced. Since there is
insufficient amount of vapor, some of the air wouldnt be
displaced and just stay inside the flask. The lack of
sample would decrease the actual mass because, what is
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being weighed is not solely a condensed vapor but an
insufficient condensed vapor with air. For a certain
percentage, the air would contribute on the molecular
mass of the weighed sample.
In the gathered data, it can be observed that some of the
molecular mass (MW) are higher than that of the
theoretical value. This shows that the mass from the vapor
or air was also recorded. This can be caused by the water
droplets or vapor stuck at the edges that were
unsuccessfully removed before weighing.
If we assume that the only source of the experimental
error is the assumption that the vapor behaves ideally,
then by using Van der Waals equation, we can calculate
the parameters a and b by using the first and the second
trial as the two-independent linear equation. Taking the
ethanol data as example (See Table 1), it is assumed that
. (see Calculations 1).
Upon comparison with the theoretical values of
coefficient (See Table 2), the values are slightly far. It is
because of the assumption that , given that we are
dealing with very small values, so, great difference
resulted.
Conclusion and Recommendation
Upon performing the experiment, the data was interpreted
and it can be stated that the Dumas method is a reliable
way to determine the molar mass of volatile liquids so
long as the procedures are followed correctly and
avoidable causes of errors be avoided. The said method
allows the liquid to vaporize from which the maximum
amount of vapor at a certain volume of container is
permitted to condense given the temperature and
pressure. Molar mass is determined by the mass of the
vapor condensed and amount of mole that would possibly
be inside the flask that is patterned by parameters
pressure, volume and temperature by ideal gas law.
This method requires the assumption that the vapor
behaves ideally and that the vapor will completely
vaporize under the said conditions.
Experiment #1 Group No. 6 12th of May 2017
Based on the intermolecular forces of attraction (IMFA)
of the samples, it can be considered a trend that a sample
with less molecular weight and IMFA will produce a
greater error.
To avoid a high amount of error, it is essential to obtain
every necessary data, carefully and accurately. Also, the
status of the surroundings must also be taken notice of
such as the temperature of the area where the experiment
is to be performed and the barometric pressure. It is more
accurate, yet not so convenient, to use the real gas law in
calculating the molar mass of the vapor because in this
equation, the two assumption that molecular volume of
the vapor is negligible and the intermolecular force of the
compound does not affect the pressure because repulsive
force is solely present.
Sources of error would be rooted from the deposited
condensed water on the excess foil of the cap, the bubbled
water that went inside the flask, the insufficiency of
injecting sample, the presence of random contaminants
and carelessness on temperature reading. With all that in
mind, it is strongly recommended to fully dry the flasks in
the oven, tighten the copper wire tourniquet multiple
times and use smaller needle to lessen percentage errors.
References
1. Charles E. Smith (Resnick, Robert, and Halliday,
David, Physical Chemistry, 3rd ed., 1997), Lexicon
Universal Encyclopedia, USA, ISBN 0-7172-2025-7,
1999, {Accessed: 05-09-14}
2. Atkins, P., De Paula, J. (2006). Atkins Physical
Chemistry 8th edition. Oxford University Press, New
York. pp. 654, 959
3.http://web.centre.edu/miles/che135/che135labs/Molecul
ar%20Weight%20by%20the%20Dumas%20Method.pdf
4.http://chemlabs.uoregon.edu/Classes/Exton/CH228/Du
mas.pdf
5.http://web.lemoyne.edu/giunta/classicalcs/dumas.html
Appendices
Appendix A. Graphs and Data
Table 1. Data Obtained in Experiment 1
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water
Sample Ethyl Alcohol Moles of vapor 9.240x10^- 9.332x10^- 9.365x10^-3
Trials Trial 1 Trial 2 Trial 3 at T,V and P,n 3 3
Mass of "empty" Estimated 41.775 96.943 38.868
92.193 96.754 90.858
flask molar mass of
Mass of "empty" vapor m/n
93.940 98.897 91.523
flask with vapor Moles of air 1.275x10^-3
1.408x10^- 1.422x10^-
Mass of vapor, displaced by
0.447 0.343 0.438 3 3
m the vapor at Tr
Temperature of 42 Molar mass of 0.0367
42 40 0.0406 0.0410
vapor, T air, calculated
Mass of water 250.18 251.3 250.047 True mass of
Volume of flask vapor that
251.361 252.487 251.228 occupies the
based on water
Moles of vapor flask at the 0.4266 0.955 0.4007
0.01007 0.01011 0.01007 boiling
at T,V and P,n
Estimated molar temperature of
mass of vapor 44.389 33.927 43.496 water
m/n Corrected
Moles of air molar mass of 46.169 92.336 42.787
1.899x10^- 1.898x10^- the vapor
displaced by the 1.732x10^-3
3 3 Corrected
vapor at Tr
Molar mass of molar mass of
0.0547 0.0499 0.0547 60.431
air, calculated the vapor
True mass of (average)
vapor that Molar mass
occupies the (literature 58.08
flask at the 0.5017 0.4929 0.4927 value)
boiling % difference 3.97%
temperature of
water
Corrected molar Sample Ethyl Acetate
mass of the 49.82 48.754 48.928 Trials Trial 1 Trial 2 Trial 3
vapor Mass of
95.774 93.533 90.242
Corrected molar "empty" flask
mass of the 49.167 Mass of
vapor (average) "empty" flask 91.394
96.712 94.621
Molar mass with Al coil
46.069 and Cu wire
(literature value)
% difference 6.506% Mass of vapor,
0.687 0.713 0.826
m
Sample Acetone Temperature of
36 38 38
Trials Trial 1 Trial 2 Trial 3 vapor, T
Mass of Mass of water 249.7569 250.7789 251.6543
89.427 93.919 88.751 Volume of 250. 9363 251.9631 252.8427
"empty" flask
Mass of flask based on
"empty" flask water
90.813 94.833 89.115 Moles of vapor 9.2700 x 9.2481 x 9.2804 x
with Al coil
and Cu wire at T,V and P,n 10^-3 10^-3 10^-3
Mass of vapor, Estimated 74.1100 77.0969 89.0048
0.386 0.914 0.364 molar mass of
m
Temperature of vapor m/n
36 36 34 Moles of air
vapor, T 1.4123 x 1.5667 1.5648 x
Mass of water 248.936 251.417 250.691 displaced by
10^-3 x10^-3 10^-3
Volume of 250.112 252.604 251.875 the vapor at Tr
flask based on Molar mass of
0.0407 0.0451 0.0451
air, calculated
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True mass of Calculations 1. Calculating the parameter a and b for

vapor that ethyl alcohol assuming n3/V2=0.
occupies the
flask at the
0.7321 0.7581 0.8711
boiling
temperature of
water
Corrected
molar mass of 82.110 84.0969 84.0048
the vapor
Corrected
molar mass of
83.4039
the vapor
Equation 1 (1st trial):
(average)
Molar mass
(literature 88.111
value)
% difference 5.5 %

Table 2. Van der Waals Parameters for Sample Used

Percent Equation 2 (2nd trial):

2 2
Compound a (L bar/mol ) b (L/mol) Difference
(%)
Ethyl alcohol 11.721 0.0779 3.9
Acetone 15.010 0.1096 6.5

Ethyl Acetate 19.600 0.1137 5.5

Solving for a and b:
Graph 1. Percentage Error vs. Mass of Vapor Recorded

Appendix B. Sample Computation

Note: Sample computation is from the data obtained in
the 1st trial of ethyl acetate data.

1. Volume of the flask based on water

Table 3. Acetone Data Corrected with Van der Waals

Equation
2. Moles of vapor T, V and P, n
Molecular Percentage Corrected
Behavior
Mass Error Percentage
Ideal Gas
44.15 g/mol 27.26% about
Behavior
1.75%
Real Gas
44.94 g/mol 25.51% decrease
Behavior

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3. Estimated molar mass of vapor

4. Vapor Pressure of the sample related to the pressure f

the air

5. Moles of air

6. Mass of air

7. True mass of vapor

8. Corrected molar mass of vapor

9. Percentage Difference

Appendix C: 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

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atmosphere kg/cm2 1.03325

atmosphere mbar 1012.95
mtorr or micron
atmosphere 7.6 x 105
Hg
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
bar dynes/cm2 1 x 106
bar in. Hg 29.54
bar in. water 401.65
bar kg/cm2 1.02
bar mbar 1000
mtorr or micron
bar 7.5028 x 105
Hg
bar Pa or N/m2 1 x 105
bar psi or lb/in2 14.503861
bar torr or mm Hg 750.2838
torr or mm
bar 1.3328 x 10-3
Hg
torr or mm
dynes/cm2 1.3328 x 103
Hg
torr or mm
kg/cm2 1.3595 x 10-3
Hg
torr or mm
in. Hg 3.937 x 10-2
Hg
torr or mm
in. water 0.5353
Hg
torr or mm
mbar 1.3328
Hg
torr or mm mtorr
1000
Hg or micron Hg
torr or mm
Pa or N/m2 133.28
Hg
torr or mm
psi or lb/in2 1.934 x 10-2
Hg

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