CHM170L Physical Chemistry 1 Laboratory

4nd Quarter SY 2015-2016

Determination of Molar Mass of Volatile Liquid by a Vapor-Density Method

1Badiola,Ma. Denisse W., 1Brillas, Catherine Jill D., 1Celocia, Shaira L., 1Combalicer, Mark Eugene A., 1Tolentino,
Aika Cecille I.

1School of Chemical Engineering and Chemistry, B.S. Chemical Engineering, Mapua Institute of Technology

ABSTRACT
Molar mass of volatile liquids from their vapor densities at a temperature above their boiling points using
Dumas method was intended in this experiment. The simplest way of measuring the molecular weight of a
substance using the ideal gas law is by Dumas method. The temperature and the mass of the gas sample
are measured, along with the atmospheric pressure. A volatile liquid is usually used as the source of the
gas since liquids are much easier to handle than gases. The liquid must have a boiling point substantially
above room temperature and below the boiling point of water. Ethyl acetate, ethyl alcohol and acetone
were the three volatile reagents exploited. The main step in determining the molecular mass is to inject
small amount of volatile liquid into the foil covered flask through a tiny opening and to heat in a boiling
water bath to vaporize the liquid. When all of the liquid is vaporized and no more vapor is seen leaving the
bulb, the bulb contains a sample of vapor at atmospheric pressure and 100 ºC with a volume exactly equal
to the volume of the bulb. Pressure (P), volume (V), temperature (T) and mass of the vapor (g) were the
data needed to obtain the molecular mass of the given volatile liquids. After the calculations, the
gathered percentage difference for ethyl acetate, acetone and ethyl alcohol are
12.21%, 80.06% and 8.22% respectively.

Keywords: Dumas method, molar mass, volatile liquids

INTRODUCTION

Dumas method determines the molar mass of volatile The molar mass of an ideal gas can be calculated if the
organic substances that are liquids at room temperature mass, temperature, pressure and volume are known.
and has a boiling point between room temperature
and100°C [1]. It uses the ideal gas law to determine the Two major assumptions are used in this method. The first
molar mass of a compound [2]. one is that the compound vapor behaves ideally. The
second one is that either the volume of the vessel does not
(1) vary significantly between room and the working
temperature, or the volume of the vessel may be accurately
determined at the working temperature [3].
Where P is the pressure in atm, L is the volume in liters, n
is the moles of gas, R is the gas constant which is equal to
In this method, a small volume of the liquid sample whose
0.08206 and T is the absolute temperature. Letting molar mass is to be determined is placed in a flask of
, where m is the mass of the gas in grams and M is known mass and volume. The flask has a small opening to
the molar mass, the ideal gas law gives: the atmosphere. Heating the flask with the liquid sample in
a boiling water bath causes the liquid to vaporize. The
resulting vapor fills the flask, driving air out through the
(2) hole. Excess vapor escapes until the pressure of the vapor
inside the flask equals that of the atmosphere outside. The

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flask now contains pure vapor at atmospheric pressure. The Each flasks were then injected by four millimeters acetone,
small hole reduces the diffusion of air into the flask [4]. ethyl acetate, and absolute ethanol with a syringe. The
holes were made to be small to limit the possibility of error.
If the vapor in the flask is assumed to be an ideal, equation
(2) can be used to determine its molar mass. The
temperature of the vapor is that of the boiling water bath.
The pressure of the vapor is that of the atmosphere. The
volume of the vapor is that of the flask and glass tube. The
mass of the vapor is determined by removing the flask from
the water bath, allowing it to cool, weighing the flask and
condensed liquid, and subtracting the mass of the empty
flask [4].

The main focus of this experiment was to estimate the

molar mass of volatile liquids (ethyl alcohol, ethyl acetate
and acetone) from their vapor densities at a temperature
above their boiling points using the dumas method.
Figure 2. Getting samples with syringe.

Then, three 400 ml beakers were half filled with distilled

MATERIALS AND METHODS water that served as hot water bath of the three samples.
The beaker were heated and the flasks were then
For this experiment, three 125 ml Erlenmeyer flasks were immersed in it. The water was boiled until the liquid
weighed in analytical balance first and recorded. Then, samples in the flasks were vaporized. The flasks were then
cooled to room temperature, weighed again and recorded.
these three flasks were covered with foil and sealed by
The recorded mass were served as the mass of condensed
copper wire. Copper wire must be sealed the flask tightly, if
vapor. After weighed, the aluminum foil was removed and
not, this may cause error throughout the experiment. The the flasks were filled with water, weighed and recorded.
excess aluminum foil were removed with a pair of scissors
so as to prevent the vapor from the boiling process to
escape. The covered flasks were then weighed again and
recorded.

Figure 3. Flasks immersed into their respective beakers.

Same procedure applied for the second trial.

Figure 1. Erlenmeyer flasks sealing with copper wire.

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RESULTS and DISCUSSIONS The molar mass of each substance, which was intended to
be determined, relies directly upon the mass of vapour
The experiment focuses on the volatile samples: ethyl measure. The missing mass of the air which has escaped is
acetate, ethyl alcohol and acetone. The vapor densities at a result of displacement by the volatilization of the liquids
the temperature above the samples’ boiling point were used were accounted for by determining the vapour pressure of
to determine their molar masses. The Dumas method was the liquid at the prevailing room temperature from the
also used to determine the molar mass of a compound Antoine equation, then using it in the perfect gas law
which is a liquid that has a boiling point between room formula to obtain the number of moles of vapour. Since the
temperature and 100 °C [1]. moles of vapour that volatilized at this partial pressure is the
same as the moles that has escaped, it was used to
Before the experiment, all constants are maintained. The determine the mass of air that has not been considered
barometric pressure 756 mmHg with the room temperature when computing for the final value of the molar mass. After
of 32 ◦C. The density of water is 0.996 g/cm³. the two trials performed with ethyl acetate there was a
minimal percent difference which implies that the
Table 1. (Determination of Molar Mass of Ethyl Acetate) experimental values were precise with the literature value.

Sample Name: ETHYL ACETATE Table 2. (Determination of Molar Mass of Ethyl Alcohol)
Trial 1 Trial 2
Mass of empty flask 66.68 79.34 Sample Name: ETHYL ALCOHOL
Mass of empty flask + foil 67.31 79.99 Trial 1 Trial 2
and wire Mass of empty flask 93.57 96.43
Mass of Vapor, m 0.503 0.392 Mass of empty flask + foil 94.27 97.28
Temp of Vapor, T 99 98 and wire
Mass of flask filled with 214.40 224.60 Mass of Vapor, m 0.523 0.538
water Temp of Vapor, T 92 90
Mass of water 147.73 145.25 Mass of flask filled with 247.46 250.79
Volume of flask based on 148.32 145.83 water
water V, Mass of water 153.89 154.36
Moles of Vapor at T,V,P 0.00483 0.00476 Volume of flask based on 154.51 154.97
Estimated molar of Vapor, 104.14 82.35 water V,
m/n Moles of Vapor at T,V,P 0.00511 0.00551
Moles of air displaced by 0.00483 0.00102 Estimated molar of Vapor, 102.35 104.47
Vapor m/n
Molar mass of air 28.84 28.84 Moles of air displaced by 0.00704 0.00706
calculated Vapor
Mass of air displaced by 0.0299 0.2942 Molar mass of air 28.84 28.84
the vaporized liquid calculated
True mass of vapor that 0.533 0.421 Mass of air displaced by 0.0203 0.0203
occupied the flask at the vaporized liquid
boiling temp of water True mass of vapor that 0.5433 0.5583
Corrected molar mass of 110.35 88.53 occupied the flask at boiling
Vapor temp of water
Corrected molar mass of 99.44 Corrected molar mass of 106.32 108.41
the average Vapor Vapor
Molar mass (literature 88 Corrected molar mass of 107.37
value) the average Vapor
% difference 12.21% Molar mass (literature 46
value)
% difference 80.06%

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In table 2, there was a large percent error between the Table 3. (Determination of Molar Mass of Acetone)
experimental value and molar literature values which
denotes that there were errors that occurred. The test was
performed in an open system, which was subjected to Sample Name: ACETONE
various conditions that may potentially affect the final Trial 1 Trial 2
results. The structures or natures of the substances under Mass of empty flask 98.22 91.14
consideration are also factors to consider. The substances Mass of empty flask + foil 98.83 91.92
and wire
were organic compounds with conservable hydrogen
Mass of Vapor, m 0.205 0.192
attractive forces due to the presences of an electronegative
Temp of Vapor, T 86 84
element, oxygen and a net dipole due to a functional group,
Mass of flask filled with 251.42 229.94
which are ester, ketone and alcohol groups respectively. water
These effects were not considered when using an ideal Mass of water 153.20 138.80
equation of state such as the perfect gas law when Volume of flask based on 153.81 139.80
correlating the values of pressure, volume, temperature, water V,
and to the moles of gas [5]. Under the perfect gas law, the Moles of Vapor at T,V,P 0.00519 0.00475
gases were also considered to have zero volume, for the Estimated molar of Vapor, 39.5 40.42
gases under consideration, which are actually liquids under m/n
room temperature and molecules with attractive hydrogen Moles of air displaced by 0.00519 0.00475
bonding, the perfect gas law is a poor approximation. Vapor
Considering the manner by which the experiment was Molar mass of air calculated 28.84 28.84
performed, there are various factors which largely affect the Mass of air displaced by the 0.0709 0.0646
result such as the weighing with an analytical valance, size vaporized liquid
of the orifice, and length of time of vaporization. The length True mass of vapor that 0.2759 0.2566
of time of vaporization, if not completed or extended until occupied the flask at boiling
equilibrium has achieved, will result to the mass of vapour temp of water
Corrected molar mass of 53.16 53.68
higher than it should. The more expected result would be
Vapor
that the molar mass computed would be lesser than the
Corrected molar mass of the 53.42
literature value. This is due to the fact that high molecular average Vapor
weight gases such as the volatile liquids used in the test Molar mass (literature value) 58
tend to have low kinetic energies, which are exactly the % difference 8.22%
factor that aids their escape though, the orifice. With lower
kinetic energies, the chance of each gas molecule to
escape is lower. Additionally, related to the above- The last part of the experiment gave the best result among
mentioned case is when the correction factor of considering the others because of an acceptable percent difference. A
the mass of air that escaped is not valuable if air has not value of molar mass within the accepted value could most
been actually displaced. likely mean that time of vaporization was sufficient. This
also means that when taking the flask out of the hot plate is
not prematurely done because it gave good result and a
steady state was also achieved.in the immediate
condensation of vapours that would have escaped if steady
state was allowed to be achieved.

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CONCLUSIONS AND RECOMMENDATIONS APPENDIX

Using Dumas method, the molar masses of volatile liquids Sample computation of Trial 1 Ethyl Acetate
were estimated based from their densities at a temperature
above their boiling point. This method depends on a lot of Mass of vapor = mass of vapor + flask – mass of empty
factors going right. One assumption is that while the liquid flask with foil and wire
is volatile enough to vaporize at the elevated temperature, it =67.809-67.306
is not volatile enough, so that a significant amount will be =0.503 g
lost to evaporation as the container cools down. Three
liquids were given: ethanol, ethyl acetate and acetone and
Mass of water = mass of flask filled with water – mass of
all the measurements were different with each other
however, at the end of the experiment we can see that their empty flask
molar masses were identical with each other. This is = 214.40-66.675
probably because their chemical properties were almost the =147.725 g
same with each other. The excess of the foil, orifice created
by the syringe and execution of the procedure were the Volume of flask based = mass of water / density of water
possible sources of errors. The flask should be dry so no on water, V
water or moisture will affect the point of volatilization and
average molar mass of the sample will be obtained with =
less error. The weight of condensate will be affected by the
presence of moisture. Excess foil would allow accumulation = 148.32 mL
of water vapour from the hot water bath at the side of the
Erlenmeyer flask which would affect the weight of the
sample together with the covered Erlenmeyer flask. Moles of Vapor =

REFERENCES =

[1] Darrell Ebbing; Steven D. Gammon (12 January = 0.00483 mol

2007). General Chemistry: Media Enhanced Edition.
Cengage Learning. pp. 192–. ISBN 0-618-73879-7.
Estimated molar mass of vapor =
[2] Dumas Method. Retrieve May 24, 2015 from
http://www.roanestate.edu/faculty/chemistry/chemistryslides
hows/Dumas/dumas.pdf =

[3] Grider, Douglas J.; Tobiason, Joseph D.; = 104. 14 g/mol

Tobiason, Fred L. (1988). "Molecular weight determination
by an improved temperature monitored vapor density
method". Journal of Chemical Education 65 (7): 641. Moles of air displaced by the vapor =
Bibcode:1988JChEd..65..641G. doi:10.1021/ed065p641.

[4] Molecular Weight of Volatile Compound.

Retrieve May 24, 2015 from
http://wwwchem.csustan.edu/chem1102/molwt.htm =

[5] Caparanga, A. R., Baluyot, J. Y., Soriano, A.N.

(2206). Physical Chemistry Laboratory Manual Part 1 = 0.00104 mol

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* =

= 133.3229 mmHg

Mass of the air calculated = 28(0.79) + 32(0.21)

= 28.84 g/mol

Mass of air displaced = molar mass of air * moles of air

= 28.84 g/mol * 0.0014 mol
= 0.02999 g

True mass of vapor = mass air displaced + mass of vapor

= 0.02999g + 0.503 g
= 0.5330 g

Corrected Molar Mass =

= 110.53 g/mol

Corrected Molar Mass of the vapor =

(Average of the mass Vapor) =

= 99.44 g/mol

% difference =

= 12.21 %

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