exp12.

qxd 11/15/13 10:40 AM Page 173

Experiment 12
Molar Mass of a
Courtesy of VWR International, LLC

Volatile Liquid

The mercury barometer accurately measures atmospheric pressure in mmHg

(or torr).

• To measure the physical properties of pressure, volume, and temperature for a Objectives
gaseous substance
• To determine the molar mass (molecular weight) of a volatile liquid

The following techniques are used in the Experimental Procedure: Techniques

Chemists in academia, research, and industry synthesize new compounds daily. To Introduction
identify a new compound, a chemist must determine its properties; physical properties
such as melting point, color, density, and elemental composition are all routinely mea-
sured. The molar mass of the compound, also one of the most fundamental properties,
is often an early determination.
A number of analytical methods can be used to measure the molar mass of a
compound; the choice of the analysis depends on the properties of the compound. For
example, the molar masses of large molecules, such as proteins, natural drugs, and
enzymes found in biochemical systems, are often determined with an osmometer. For Osmometer: an instrument that
smaller molecules, a measurement of the melting point change of a solvent (Experi- measures changes in osmotic
pressure of the solvent in which a
ment 14) in which the molecule is soluble can be used. Recent developments in mass substance, the solute, is soluble
spectrometry have expanded its use to include not only molar mass measurements but
also the structures of high molar mass compounds in the biochemical fields. Mass spectrometry: an instrumental
method for identifying a gaseous ion
For volatile liquids, molecular substances with low boiling points and relatively according to its mass and charge
low molar masses, the Dumas method (John Dumas, 1800–1884) of analysis can pro-
Volatile: readily vaporizable
vide a fairly accurate determination of molar mass. In this analytical procedure, the liq-
uid is vaporized into a fixed-volume vessel at a measured temperature and barometric
pressure. From the data and the use of the ideal gas law equation (assuming ideal gas
behavior), the number of moles of vaporized liquid, nvapor, is calculated:
P(atm) V(L)
nvapor = PV = (12.1)
RT (0.08206 L •atm/mol • K) T(K)
In this equation, R is the universal gas constant, P is the barometric pressure in R = 0.08206 L • atm/mol • K
atmospheres, V is the volume in liters of the vessel into which the liquid is vaporized,
and T is the temperature in kelvins of the vapor.

Experiment 12 173
exp12.qxd 11/15/13 10:40 AM Page 174

The mass of the vapor, mvapor, is determined from the mass difference between the
empty vessel and the vapor-filled vessel.
mvapor = mflask + vapor – mflask (12.2)
The molar mass of the compound, Mcompound, is then calculated from the acquired
data:
mvapor
Mcompound = n (12.3)
vapor

Gases and liquids with relatively large intermolecular forces and large molecular
volumes do not behave according to the ideal gas law equation; in fact, some com-
pounds that we normally consider as liquids, such as H2O, deviate significantly from
ideal gas behavior in the vapor state. Under these conditions, van der Waals’ equation, a
modification of the ideal gas law equation, can be used to correct for the intermolecular
forces and molecular volumes in determining the moles of gas present in the system:

冢 冣
2
P + n 2a (V – nb) = nRT (12.4)
V
In this equation, P, V, T, R, and n have the same meanings as in Equation 12.1; a is
an experimental value that is representative of the intermolecular forces of the vapor, and
b is an experimental value that is representative of the volume (or size) of the molecules.
If a more accurate determination of the moles of vapor, nvapor, in the flask is
required, van der Waals’ equation can be used instead of the ideal gas law equation.
Values of a and b for a number of low-boiling-point liquids are listed in Table 12.1.
Others may be found in your textbook or on the Internet.

Table 12.1 Van der Waals’ Constants for Some Low-Boiling-Point Compounds

a b
Name ( )
L2•atm
mol 2
(L/mol) Boiling Point (ºC)

Methanol 9.523 0.06702 65.0

Ethanol 12.02 0.08407 78.5
Acetone 13.91 0.0994 56.5
Propanol 14.92 0.1019 82.4
Hexane 24.39 0.1735 69.0
Cyclohexane 22.81 0.1424 80.7
Pentane 19.01 0.1460 36.0
Water 5.46 0.0305 100.0

Experimental Procedure Overview: A boiling water bath of measured temperature is used to vapor-
Procedure ize an unknown liquid in a flask. The volume of the flask is measured by filling the flask
with water. As the flask is open to the atmosphere, you will record a barometric pressure.
You are to complete three trials in determining the molar mass of your low-
boiling-point liquid. Initially, obtain 15 to 20 mL of liquid from your instructor.
The same apparatus is used for each trial.
Be aware of the number of significant figures when recording data.

A. Preparing the Sample

Prepare a boiling water bath for Part A.3.
1. Prepare the flask for the sample. Clean a 125-mL Erlenmeyer flask and dry it either
in a drying oven or by allowing it to air-dry. Do not wipe it dry or heat it over a direct
flame. Cover the dry flask with a small piece of aluminum foil (Figure 12.1) and
Data Analysis, A secure it with a rubber band. Determine the mass (±0.001 g) of the dry flask,
aluminum foil, and rubber band.

174 Molar Mass of a Volatile Liquid

exp12.qxd 11/15/13 10:40 AM Page 175

Jo A. Beran
Ken Karp

Figure 12.1 Preparation of a flask for the placement of Figure 12.2 Apparatus for determining the molar mass
the volatile liquid of a volatile liquid

2. Place the sample in the flask. Record the number of the unknown liquid on the
Report Sheet. Transfer about 5 mL of the unknown liquid into the flask; again
cover the flask with the aluminum foil and secure the foil with a rubber band. You
do not need to conduct a mass measurement. With a pin, pierce the aluminum foil
several times.
3. Prepare a boiling water bath. Half-fill a 400-mL beaker with water. Add one or
two boiling chips to the water. The heat source may be a hot plate or a Bunsen Boiling chip: a piece of porous
flame—consult with your instructor. Secure a thermometer (digital or glass) to ceramic that releases air when heated
(the bubbles formed prevent water
measure the temperature of the water bath. from becoming superheated)

1. Place the flask/sample in the bath. Lower the flask/sample into the bath and B. Vaporize the Sample
secure it with a utility clamp. Be certain that neither the flask nor the clamp
touches the beaker wall. Adjust the water level high on the neck of the flask
(Figure 12.2).1 Before proceeding, have your instructor approve your apparatus.
2. Heat the sample to the temperature of boiling water. Gently heat the water until
it reaches a gentle boil. (Caution: Most unknowns are flammable; use a
hot plate or moderate flame for heating.) When the liquid in the flask and/or the
vapors escaping from the holes in the aluminum foil are no longer visible, con-
tinue heating for another 5 minutes. Read and record the temperature of the boil-
ing water.

1
You may choose to wrap the upper portion of the flask and beaker with aluminum foil; this will
maintain the upper portion of the flask not in the boiling water bath at nearly the same temperature
as the boiling water.

Experiment 12 175
exp12.qxd 11/15/13 10:40 AM Page 176

3. Measure the mass of the flask/sample. Remove the flask and allow it to cool to
room temperature. Sometimes the remaining vapor in the flask condenses; that’s
okay. Dry the outside of the flask and determine the mass (±0.001 g, use the same
balance!) of the flask, aluminum foil, rubber band, and the remaining vapor.
Record the mass on the Report Sheet.
4. Do it again and again. Repeat the experiment for Trials 2 and 3. You only need
to transfer another 5 mL of liquid to the flask (i.e., begin with Part A.2) and repeat
Parts B.1–B.3.

Disposal: Dispose of the leftover unknown liquid in the Waste Organics

container.

C. Determine the Volume
and Pressure of the Vapor
Data Analysis, A
1. Measure the volume of the flask. Fill the empty 125-mL Erlenmeyer flask to the
brim with water. Measure the volume (±0.1 mL) of the flask by transferring the
water to a 50- or 100-mL graduated cylinder. Record the total volume.
2. Record the pressure of the vapor in the flask. Find the barometer in the labora-
tory. Read and record the atmospheric pressure in atmospheres, using all certain dig-
its (from the labeled calibration marks on the barometer) plus one uncertain digit
(the last digit which is the best estimate between the calibration marks); that is,
to the correct number of significant figures.

D. Calculations
Data Analysis, C and D
1. Molar mass from data. Calculate the molar mass of your unknown for each of
the three trials.
2. Determine the standard deviation and the relative standard deviation
(%RSD). Refer to Data Analysis, C and D and calculate the standard deviation and
the %RSD for the molar mass of your unknown from your three trials.

The Next Step A number of techniques can be used to determine the molar mass of a volatile liquid;
the most common (if the instrument is available) is mass spectrometry. Describe how
your sample’s molar mass would be determined using mass spectrometry. Search the
Internet for other procedures that can be used to measure the molar mass of volatile
substances.

NOTES AND CALCULATIONS

176 Molar Mass of a Volatile Liquid

exp12.qxd 11/15/13 10:40 AM Page 177

Experiment 12 Prelaboratory Assignment

Molar Mass of a Volatile Liquid
Date __________ Lab Sec. ______ Name ____________________________________________ Desk No. __________

1. a. How is the pressure of the vaporized liquid determined in this experiment?

b. How is the volume of the vaporized liquid determined in this experiment?

c. How is the temperature of the vaporized liquid determined in this experiment?

d. How is the mass of the vaporized liquid determined in this experiment?

2. The ideal gas law equation (equation 12.1) is an equation used for analyzing ideal gases. According to the kinetic mol-
ecular theory that defines an ideal gas, no ideal gases exist in nature, only real gases. Van der Waals’ equation is an
attempt to make corrections to real gases that do not exhibit ideal behavior. Describe the type of gaseous molecules
that are most susceptible to nonideal behavior.

Experiment 12 177
exp12.qxd 11/15/13 10:40 AM Page 178

3. a. The following data were recorded in determining the molar mass of a volatile liquid following the Experimental
Procedure of this experiment. Complete the table for analysis. (See Report Sheet.) Record calculated values with
the correct number of significant figures.

A. Preparing the Sample Calculation Zone

1. Mass of dry flask, foil, and rubber band (g) ____________
74.722
Part D.1
B. Vaporize the Sample
2. Temperature of boiling water (°C) ____________
98.7
3. Mass of dry flask, foil, rubber band,
and vapor (g) ____________
74.921
C. Determine the volume and Pressure
of the Vapor Part D.2
1. Volume of 125 mL flask (L) ____________
0.152
2. Atmospheric pressure (torr, atm) ____________
752, 0.989
D. Calculations
1. Moles of vapor, nvapor (mol)
Equation 12.1.
Show calculation. ____________ Part D.3
2. Mass of vapor, mvapor (g)
Show calculation. ____________
3. Molar mass of vapor (g/mol)
Show calculation. ____________

3. b. For Trials 2 and 3, the molar mass of the vapor was determined to be 46.5g/mol and 43.1 g/mol respectively.
a. What is the average molar mass of the vapor? Data Analysis, B.

b. What are the standard deviation and the relative standard deviation (%RSD) for the molar mass of the vapor?
Data Analysis, C and D.

4. a. If the atmospheric pressure of the flask is assumed to be 760 torr in question 3, what is the reported molar mass of
the vapor?

b. What is the percent error caused by the error in the recording of the pressure of the vapor?
M
% error = difference 100
Mactual

178 Molar Mass of a Volatile Liquid

exp12.qxd 11/15/13 10:40 AM Page 179

Experiment 12 Report Sheet

Molar Mass of a Volatile Liquid
Date __________ Lab Sec. ______ Name ____________________________________________ Desk No. __________

A. Preparing the Sample

Unknown number _____________________________ Trial 1 Trial 2 Trial 3

1. Mass of dry flask, foil, and rubber band (g) _____________________________

B. Vaporize the Sample

1. Instructor’s approval of apparatus _____________________________

2. Temperature of boiling water (ºC, K) ______,_________ ______,_________ ______,_________

3. Mass of dry flask, foil, rubber band, and vapor (g) _______________ _______________ _______________

C. Determine the Volume and Pressure of the Vapor

1. Volume of 125-mL flask (L)

_____ + _____ + _____ = total volume _____________________________

2. Atmospheric pressure (torr, atm) ____________,__________________

D. Calculations

1. Moles of vapor, nvapor (mol) _______________ _______________ _______________

2. Mass of vapor, mvapor (g) _______________ _______________ _______________

3. Molar mass of compound (g/mol) _______________ _______________ _______________

4. Average molar mass (g/mol) _____________________________ Data Analysis, B

5. Standard deviation of molar mass _____________________________ Data Analysis, C

6. Relative standard deviation of molar mass (%RSD) _____________________________ Data Analysis, D

Show the calculation for the standard deviation and the relative standard deviation (as %RSD) of the molar mass of the
unknown. Data Analysis, C and D.

Experiment 12 179
exp12.qxd 11/15/13 10:40 AM Page 180

(Optional) Ask your instructor for the name of your unknown liquid. Using van der Waals’ equation and the values of a
and b for your compound, repeat the calculation for the moles of vapor, nvapor (show for Trial 1 below), to determine a more
accurate molar mass of the compound.

E. Calculations (van der Waals’ equation)

Unknown number ______a = ______, b = ______ Trial 1* Trial 2 Trial 3

1. Moles of vapor, nvapor (mol) _______________ _______________ _______________

2. Mass of vapor, mvapor (g) _______________ _______________ _______________

3. Molar mass of compound (g/mol) _______________ _______________ _______________

4. Average molar mass (g/mol) _____________________________

*Calculation of nvapor from van der Waals’ equation for Trial 1. Show work here.

Laboratory Questions
Circle the questions that have been assigned.
1. Part A.1. The mass of the flask (before the sample in placed into the flask) is measured when the outside of the flask is
wet. However, in Part B.3, the outside of the flask is dried before its mass is measured.
a. Will the mass of vapor in the flask be reported as too high or too low, or will it be unaffected? Explain.
b. Will the molar mass of vapor in the flask be reported as too high or too low, or will it be unaffected? Explain.
2. Part A.1. From the time the mass of the flask is first measured in Part A.1 until the time it is finally measured in Part
B.3, it is handled a number of times with oily fingers. Does this lack of proper technique result in the molar mass of
the vapor in the flask being reported as too high or too low or as unaffected? Explain.
3. Part A.2. The aluminum foil is pierced several times with large pencil-size holes instead of pin-size.
a. How will this oversight in the procedure affect the mass of vapor measured in Part B.3, too low, too high, or
unaffected? Explain.
b. Will the reported molar mass of the liquid be reported too low, too high, or unaffected? Explain.
4. Part B.2. The flask is completely filled with vapor only when it is removed from the hot water bath in Part B.3.
However, when the flask cools, some of the vapor condenses in the flask. As a result of this observation, will the
reported molar mass of the liquid be too high, too low, or unaffected? Explain.
5. Part B.2. Suppose the thermometer is miscalibrated to read 0.3°C higher than actual. Does this error in calibration
result in the molar mass of the vapor in the flask being reported as too high, too low, or as unaffected? Explain.
6. Part C.1. If the volume of the flask is assumed to be 125 mL instead of the measured volume, would the calculated
molar mass of the unknown liquid be too high, too low, or unaffected by this experimental error? Explain.
7. Part C.2. The pressure reading from the barometer is recorded higher than it actually is. How does this affect the
reported molar mass of the liquid: too high, too low, or unaffected? Explain.

180 Molar Mass of a Volatile Liquid