Determining the Molar Mass of a Volatile Liquid

Objectives: To use the physical properties of a gas phase sample and the ideal gas law to
determine the molar mass of a volatile liquid

Materials: One 125-mLErlenmeyer flask; one 600-mL beaker; one 25-mL graduated cylinder;
one 50- or 100-mL graduated cylinder; aluminum foil; ring stand with two cast-
iron support rings, clamp, and wire gauze pad; Bunsen burner or hot plate;
analytical balance; thermometer; boiling chips; samples of unknown volatile
liquids

Safety: Most volatile liquids are also flammable. Take appropriate precautions when

S
heating volatile liquids near open flames. Safety goggles should be worn at all

ES
times.

AD T
Waste All recovered or unused samples of volatile liquids should be collected and

PR
Disposal:
HE H
disposed in an appropriate Organic Waste container.
IN RIG
INTRODUCTION
The determination of molar mass represents an important step in the identification of an
TA PY

unknown substance. There are many methods to obtain this vital information that are related to
physical properties (vapor pressure, osmotic pressure), while others rely on chemical behavior,
such as reactions of known stoichiometry. In this lab you will determine the molar mass of an
UN CO

unknown volatile liquid by taking advantage of the properties and behavior of gaseous
substances, and the ideal gas law.

The physical properties of matter in the solid and liquid states (i.e., melting points, boiling
points) are heavily dependent on the intermolecular forces between molecules. Strong attractive
forces, such as dipole-dipole and hydrogen bonding), lead to significant increases in melting
points and boiling points. Likewise, increases in the size of molecules results in increases in
dispersive forces, and a corresponding increase in the observed phase transition temperatures.

By constrast, the behavior of matter in the vapor state is uniformly predictable using the various
FO

gas laws. The volume occupied by gases increases with increasing temperature, decreases with
increasing pressure, and increases as the number of moles of matter increases. The uniformity of
behavior of gases is explained by the postulates of the kinetic molecular theory, which are
summarized here:

1. Molecules in the vapor state are separated by large distances, so interactions between
molecules are negligible.
2. Collisions between molecules in the vapor state are elastic; kinetic energy is
conserved.
 3. The volume occupied by the molecules themselves is negligible compared to the total
volume occupied by the gas.

An important consequence of the kinetic molecular theory is that all gases behave similarly,
regardless of the identity of the substance. Overall, the behavior of gases can be summarized by
the Ideal Gas Law,

PV = nRT (1)

where P = pressure (in atm), V = volume (in L), n = moles of gas, T is the temperature (in
kelvins), and R is the universal gas constant (0.0821 L·atm/mol·K). If the volume occupied by a
gas sample is known at a given temperature and pressure, then the Idea Gas Law can be

S
rearranged to solve for n:

ES
n = PV/RT (2)

AD T
PR
The mass of a vapor sample can be measured as the difference between the mass of an empty
HE H
container and the mass of that same container with the vapor sample. Once the mass is known,
and the number of moles of the vapor sample has been calculated using Equation (1), then the
IN RIG
molar mass of the substance can be calculated:

Mcompound = (masssample) / (nsample) (3)

TA PY

These uniformity of these relationships provides a convenient way to determine the molar mass
of many substances, especially liquids, as long as they are volatile enough to readily enter the
UN CO

vapor state under relatively moderate conditions of temperature and pressure.

Although the Ideal Gas Law works well for most gases under ambient conditions, the
assumptions inherent in the kinetic molecular theory are no longer valid at extreme conditions of
high pressure and low temperature. Under these conditions, molecular collisions are less likely to
be elastic and more likely to be influenced by attractive intermolecular forces between
molecules. The Van der Waals equation, a modification of the Ideal Gas Law, corrects for these
deviations from ideality:

𝑛𝑛 2 𝑎𝑎
�𝑃𝑃 + � (𝑉𝑉 − 𝑛𝑛𝑛𝑛) = 𝑛𝑛𝑛𝑛𝑛𝑛 (4)
𝑉𝑉 2
FO

The P, V, n, R, and T terms are the same as defined previously. The a term corrects for
attractive forces between molecules while the b term corrects for the actual volume occupied by
the gas molecules themselves. Physical data, including Van der Waals constants, for several
volatile organic liquids are included in Table 1.
Table 1. Physical Data for Volatile Organic Liquids.

Compound Formula Molar a b (L/mol) b. p. (ºC)

Mass (L ·atm/mol2)
2

Methanol CH3OH 32.04 9.52 0.0670 65.0

Ethanol CH3CH2OH 46.07 12.02 0.0841 78.5
Propanol CH3CH2CH2OH 60.09 14.92 0.1019 82.4
Acetone CH3COCH3 58.02 13.91 0.0994 56.5
Pentane CH3(CH2)3CH3 72.14 19.01 0.1460 36.0
Hexane CH3(CH2)4CH3 86.17 24.39 0.1735 69.0
Cyclohexane C6H12 84.15 22.81 0.1424 80.7
Water H2O 18.02 5.46 0.0305 100.0

S
ES
AD T
PR
HE H
IN RIG
TA PY
UN CO
FO
Pre-Lab Questions
1. A student performing this experiment records a volume of 175 mL at a barometric pressure
of 755 torr and 93 ºC. Using the Ideal Gas Law, calculate the number of moles of vapor in
the flask under these conditions. Let R = 0.0821 L∙atm/mol∙K, and perform all necessary
conversions before calculating.

S
ES
AD T
2. A student performs this experiment and obtains the data presented in Question 1, but forgets

PR
HE H
to record the temperature of the water bath and uses a temperature of 298 K when calculating
the number of moles. Calculate the value of n he or she would obtain, and the % error that
IN RIG
would result.
TA PY
UN CO

3. List three postulates of the kinetic molecular theory inherent in the ideal gas law.
FO
PROCEDURE
Part A. Determining Volume of Container

1. Obtain a clean, dry 125-mL Erlenmeyer flask, and fill it to the brim with water.

2. Carefully transfer the water from the flask to a 50- or 100-mL graduated cylinder. This
will require multiple transfers and measurements; record all individual volumes
transferred, and sum them to obtain the total volume of the flask.

3. Record the total volume of the 125-mL flask on your Data Sheet.

4. Repeat steps 1–3, and record this total volume on your Data Sheet.

S
5. Calculate and record the average total volume.

ES
Part B. Determining the Mass of a Volatile Liquid Sample.

AD T
PR
6.
HE H
Obtain a 600-mL beaker and add about 300 mL of DI water. Add a few boiling chips to
the beaker.
IN RIG
7. Assemble the ring stand with support rings and clamps, wire gauze pad, 600-mL beaker,
thermometer, and Bunsen burner or hot plate, as illustrated in Figure 1. Start heating the
water in the beaker while completing steps 8–12. Remove from heat if it starts to boil
TA PY

before you reach step 13.

8. Clean and dry the 125-mL 600 mL beaker

UN CO

Erlenmeyer flask from Part A. Dry

the flask either in an oven or by
allowing it to air-dry; do not wipe it
dry with a paper towel, as this may
transfer paper residue to the flask and
affect the total mass.

9. Cover the flask with a small piece of

aluminum foil (about 3-inch square).
Secure the foil with a rubber band.
FO

10. Determine the mass of the dry flask,

foil, and rubber band and record the
mass on your Data Sheet (to the
nearest 0.001 g).

Figure 1. Apparatus for heating volatile

liquid sample
11. Using your 25-mL graduated cylinder, obtain about 20 mL of the unknown volatile liquid
as assigned by your instructor. If more than one unknown is being used, record the ID for
your unknown on your Data Sheet.

12. Carefully remove the rubber band and the foil, and place about 5 mL of your volatile
liquid sample in the flask. Replace the foil over the opening of the flask and secure it with
the rubber band. Poke three or four pin holes in the foil cap, taking care not to tear the
foil.

13. Carefully lower the flask containing the volatile liquid sample into the bath and secure it
with a clamp. Adjust the position of the beaker so that the water level is high on the neck
of the flask but not touching the foil cover, and so that the flask is not in contact with the

S
sides of the beaker.

ES
14. Continue heating the water bath while monitoring the state of the volatile liquid sample.

AD T
You may see vapors escaping though the pin holes while the sample evaporates. When

PR
HE H
the liquid in the flask is no longer visible, continue heating for another three or four
minutes, or until there is no more evidence of vapors escaping from the flask. Record the
IN RIG
temperature of the water bath at this point.

15. Remove the flask from the water bath and allow it to cool to room temperature. Some of
the vapor in the flask may condense at this point, but this will not affect your results. Dry
TA PY

the outside of the flask and obtain the mass of the flask with the sample, foil cap, and
rubber band. Be sure to use the same analytical balance that you used in step 10. Record
this mass on your Data Sheet.
UN CO

16. Perform two additional determinations, repeating steps 12–15 and recording your data for
each determination on the Data Sheet.

17. Record the ambient pressure in the lab from the barometer in the lab.
FO
CALCULATIONS
1. Calculate the mass of the vapor in the flask as the difference between the mass of flask-plus-
sample (recorded in step 15) and the initial mass of the flask with foil cap and rubber band
(recorded in step 10). Record this on the Data Sheet.

2. Using the temperature of the water bath (step 14) the ambient pressure (step 17), and the
volume of the flask (step 2), calculate the moles of vapor in the flask for each trial using the
ideal gas law. Record this on the Data Sheet.

3. From the mass of vapor and the moles of vapor, calculate the molar mass of the vapor and
record it on your Data Sheet for each trial.

S
4. Calculate the average molar mass for your volatile liquid and record it on your Data Sheet.

ES
AD T
PR
HE H
IN RIG
TA PY
UN CO
FO
Data Sheet

ID of Unknown Volatile Liquid: ___________________

Part A. Volume of Flask

Trial 1. Volumes: _______________________________________

Total volume (1) = ______________ (mL)

Trial 2. Volumes: _______________________________________

Total volume (2) = ______________ (mL)

S
ES
Average Volume of flask = ________________ (mL)

AD T
PR
HE H
Part B. Determining the Mass of a Volatile Liquid Sample
IN RIG
Trial 1 Trial 2 Trial 3

Mass of dry flask, foil cap

and rubber band: ______________ ______________ ______________
TA PY

Mass of dry flask + sample,

UN CO

foil cap and rubber band: ______________ ______________ ______________

Temperature of water bath: ______________ ______________ ______________

Barometric pressure: ______________ ______________ ______________

Calculations:
Trial 1 Trial 2 Trial 3
FO

Mass of vapor: ______________ _____________ ______________

Moles of vapor: ______________ ______________ ______________

Molar Mass: ______________ ______________ ______________

Average Molar Mass (g/mol): ________________________

 Post-Lab Questions
1. In this lab, the volume of the flask was determined by direct measurement of the volume of
water it contained, using a graduated cylinder. Can you propose an alternative—and more
precise—method to determine the volume of water contained in the flask?

S
2. A student performing this experiment accidently tore the foil cap, so that extra vapor escaped
from the flask before it was removed from the heat. Describe how this would affect the mass

ES
of vapor and the calculated molar mass.

AD T
PR
HE H
IN RIG
3. A student determines the molar mass of a volatile liquid from the following data using the
TA PY

ideal gas law: V= 138.2 mL, P = 754 torr, T = 371 K, m = 0.330 g. Calculate the molar mass
and identify the volatile liquid from the list in Table 1.
UN CO

4. The Van der Waals equation for a nonideal gas corrects for behavior of gases that do not
conform to the postulates of the kinetic molecular theory. Explain the role of the constant a
in the Van der Waals equation, and how this also explains the observed trend in a values in
FO

Table 1.