Experiment S-5A: Molar Mass of a Volatile Liquid

OBJECTIVE
The molecular weight (molar mass) of a volatile liquid will be determined by measuring what
weight of vapor of the liquid is needed to fill a flask of known volume at a particular temperature and
pressure.

INTRODUCTION
The most common instrument for the determination of molecular weights in modern chemical
research is the mass spectrometer. Such instruments permit very precise determinations of molecular
weight and also give a great deal of structural information about the molecule being analyzed; this is of
great help in the identification of new or unknown compounds. Mass spectrometers, however, are
extremely expensive and take a great deal of time and effort to calibrate and maintain. For this reason,
many of the classical methods of molecular weight determination are still widely applied. In this
experiment, a common modification of the Ideal Gas Law will be used in the determination of the
molecular weight of a liquid which is easily evaporated.
It is often useful to know the molecular mass of a substance. This is one of the properties that
helps characterize the substance. If the substance is a volatile liquid, one common way of determining
its molecular mass involves using the ideal gas law, PV = nRT. Since the liquid is volatile, it can easily
be converted to a gas. While it is in the gas phase, its volume, temperature and pressure are measured.
The ideal gas law will then allow the calculation of the number of moles of the substance present:

PV
n=
RT
where n is the number of moles of gas, P is pressure, V is volume, R is the ideal gas constant, and T is
the temperature on the Kelvin scale. If pressure is given in mmHg, then R = 62.4 mmHg·L/mole·K.
The number of moles of gas is related to the molecular mass, M, by the expression:
grams gas
n=
M
The mass of the gas is found by first cooling the gas so that it condenses back into a liquid, and then
determining the mass of the condensed liquid. The equations above can be combined into one equation
that can be solved directly for molecular mass:
grams gas  RT
M=
PV
In this experiment to determine the molecular mass of a volatile liquid, some of the liquid is placed
into a flask. The flask is closed with aluminum foil that has a small hole in it. The flask is heated in
boiling water. The liquid vaporizes, the vapors fill the flask and excess vapor leaves through the hole.
Since the flask is open to the air, the pressure of the vapor will be the same as the atmospheric
pressure. The gas temperature will be that of the boiling water. The volume of the gas, which is the
volume of the flask, can be easily found. The mass of the gas must also be determined. To do this, the
flask is quickly cooled so that the vapor condenses back into a liquid, and the mass of the flask, foil
and liquid are found using a sensitive balance.
A major assumption is made in this experiment which may affect your results. We assume that
the vapor of the liquid behaves as an ideal gas. Actually, a vapor behaves least like an ideal gas under
conditions near which the vapor would liquefy. The unknown liquids provided in this experiment have
been chosen, however, so that the vapor will approach ideal gas behavior.

SAFETY PRECAUTIONS
 Wear safety glasses.
 Assume that the vapors of your liquid unknown are toxic. Work in a fume hood or other well-
ventilated area.
 The liquid unknowns may be harmful to your skin. Avoid contact and wash immediately if the
liquid is spilled.

EQUIPMENT
 125 mL Erlenmeyer flask  balance
 600 mL beaker  unknown liquid sample
 aluminum foil  digital thermometer
 needle  barometer
 ice

PROCEDURE

1. Prepare a beaker for use as a heating bath for the flask. The beaker (600 mL) must be
large enough for most of the flask to be covered by boiling water when in the beaker.
Add the required quantity of water to the beaker. Set the beaker up on a ring stand over
a hot plate, but do not begin to heat the water bath yet.

2. Prepare a 125 mL Erlenmeyer flask by cleaning the flask and then drying it completely.
The flask must be completely dry, since any water present will vaporize under the
conditions of the experiment and will adversely affect the results. An oven may be
available for heating the flask to dryness, or your instructor may describe another
technique.

3. Cut a square of thick (freezer) aluminum foil to serve as a cover for the flask. Trim the
edges of the foil so that it neatly covers the mouth of the flask but does not extend far
down the neck of the flask.

4. Weigh the dry, empty flask with its foil cover to the nearest 0.0001 gram.

5. Obtain an "unknown" liquid and record its identification number.

6. Add 5 mL of liquid to the flask. Cover the flask with the aluminum foil making sure
that the foil cover is tightly crimped around the rim of the flask. Punch a single small
hole in the foil cover with a needle or pin.

7. Heat the water in the beaker to boiling. When the water in the beaker begins to boil,
adjust the hot plate so that the water remains boiling but does not splash from the
beaker. Record the temperature of the water bath.

8. Immerse the flask containing the unknown liquid in the boiling water so that most of the
 flask is covered with the water of the heating bath. Clamp the neck of the flask to
maintain the flask in the boiling water.

9. Watch the unknown liquid carefully. The liquid will begin to evaporate rapidly, and its
volume will decrease. The amount of liquid placed in the flask is a good deal more than
will be necessary to fill the flask with vapor at the boiling water temperature. Excess
vapor will be observed escaping through the pinhole made in the foil cover of the flask.

10. When it appears that all the unknown liquid has vaporized, and the flask is filled with
vapor, continue to heat for 1-2 more minutes. Then remove the flask from the boiling
water bath; use the clamp on the neck of the flask to protect your hands from the heat.

11. Then cool the flask in an ice bath, dry it off completely and find the mass of the flask,
foil, and condensed liquid.

12. Repeat the determination by adding another 3-4 mL sample of unknown liquid. Reheat
the flask until it is filled with vapor; cool, and reweigh the flask. The mass of the flask
after the second sample of unknown liquid is vaporized should agree with the first
determination within 0.05 grams. If it does not, do a third determination.

13. When two acceptable determinations of the weight of vapor needed to fill the flask have
been obtained, remove the foil cover from the flask and clean it out.

14. Fill the flask to the very rim with tap water, cover with the foil cover, and weigh the
flask, cover, and water to the nearest 0.1 gram. Determine the temperature of the tap
water in the flask. Using the density of water at the temperature of the water in the flask
and the weight of water the flask contains, calculate the exact volume of the flask.

15. If no balance with the capacity to weigh the flask when filled with water is available,
the volume of the flask may be approximated by pouring the water in the flask into a 1
L graduated cylinder and reading the water level in the cylinder.

16. Record the atmospheric pressure in your data table. You can use a PASPORT barometer
connected to the Xplorer GLX or ask the teacher to find it on the Internet.

17. Using the volume of the flask (in liters), the temperature of the boiling water bath (in
Kelvin), and the barometric pressure (in atmospheres), calculate the number of moles of
vapor the flask is capable of containing. R = 0.0821 liter·atm/mole·K.

18. Using the weight of unknown vapor contained in the flask, and the number of moles of
vapor present, calculate the molar mass of the unknown liquid.

DATA/CALCULATIONS (Do not forget UNITS!)

 Trial 1 Trial 2
Unknown Number
Mass of empty flask and cover
Mass of flask/cover/vapor
Mass of Vapor
Temperature of Vapor, ºC
Temperature of vapor, K
Pressure of vapor, mmHg
Pressure of vapor, atm
Mass of flask/cover/water
Mass of water in flask when filled
Temperature of water in flask
Density of water at this temp.
Volume of flask
Moles of vapor in flask
Molar Mass of vapor
Density of vapor in flask

Average molar mass of liquid________________g/mol

QUESTIONS
1. Two methods were described for determining the volume of the flask used for the molecular
weight determination. Which method will give a more precise determination of the volume?
Why?

2. It was important that the flask be completely dry before the unknown liquid was added so that
water present would not vaporize when the flask was heated. A typical single drop of liquid
water has a volume of approximately 0.05 mL. Assuming the density of liquid water is 1.00
gram/mL, how many moles of water is in one drop of liquid, and what volume would this
amount of water occupy when vaporized at 100.C and 1 atm?

3. How can the ideal gas law be used to determine the molecular mass of a liquid?

4. Was the vapor really "ideal?" If not, how would this affect the calculated molecular mass? Be
specific -- for example, too high because. . .

5. Did the entire vapor condense into the liquid? Again, if not, how would this affect the
calculated molecular mass?

6. Why is it not necessary to be precise when the liquid is measured out into the test tube?

Advance Study Assignment: Molar Mass of a Volatile Liquid

1. A student weighs an empty flask and stopper and finds the mass to be 55.441 g. She then adds
about 5 mL of an unknown liquid and heats the flask in a boiling water bath at 100°C. After all the
liquid is vaporized, she removes the flask from the bath, stoppers it, and lets it cool. After it is cool,
she momentarily removes the stopper, then replaces it and weighs the flask and condensed vapor,
obtaining a mass of 56.039 g. The volume of the flask is known to be 215.8 mL. The barometric
pressure in the laboratory that day is 752 mm Hg.

a. What was the pressure of the vapor in the flask in atm?

b. What was the temperature of the vapor in K? the volume of the flask in liters?

c. What was the mass of vapor that was present in the flask?

d. How many moles of vapor are present?

e. What is the mass of one mole of vapor? (Eq. 2.)

2. How would each of the following procedural errors affect the results to be expected in this
experiment? Give your reasoning in each case.

a. All of the liquid was not vaporized when the flask was removed from the water bath.

b. The flask was not dried before the final weighing with the condensed vapor inside.

c. The flask was left open to the atmosphere while it was being cooled, and the stopper was
inserted just before the final weighing.

d. The flask was removed from the bath before the vapor had reached the temperature of the
boiling water. All the liquid had vaporized.