In the Laboratory

edited by
Green Chemistry Mary M. Kirchhoff
ACS Green Chemistry Institute
Washington, DC 20036

A Greener Approach for Measuring Colligative Properties W

Sean M. McCarthy and Scott W. Gordon-Wylie*
Department of Chemistry, University of Vermont, Cook Burlington, VT 05405; *swgordon@uvm.edu

Developing instructional laboratory experiments that
demonstrate key chemical concepts while simultaneously in-
corporating green constraints is not trivial. The results of a
joint effort between faculty, graduate, and undergraduate stu-
dents to develop a new greener laboratory designed to mea-
sure colligative properties are presented. Since colligative
properties depend on the number and not the identity of the
molecules being measured, there is no a priori reason why a
colligative properties experiment cannot be made rigorously
green.
The experiment presented here uses freezing point (fp)
depression data to determine the molar mass, M, of an uni-
dentified compound (1, 2). Normally an aromatic solvent
such as p-dichlorobenzene is used because of a high cryoscopic
constant, convenient freezing point, ease of cleanup, and low
cost. Aromatic solvents readily dissolve aromatic compounds,
so the initial choice of solvent locks in the use of other aro-
matic compounds as unidentified substances, for example,
naphthalene, biphenyl, benzil, p-nitrotoluene, and benzophe-
none. Despite the educational and practical advantages de-
rived from using aromatic substances, aromatic compounds
pose significant environmental and safety hazards, particu-
larly in chlorinated or nitrated form (3). Safety hazards asso-
ciated with aromatics include carcinogenicity (4), noxious
fumes, bioaccumulation of halogenated aromatics, and
ecotoxicity of nitroaromatics (5). A list of aromatic and
nonaromatic compounds, cryoscopic constants, and freezing
points, some of which are commonly used in fp depression
experiments, are provided in Table 1.
Green Aspects
As is apparent from Table 1, relatively few compounds
simultaneously possess convenient freezing points and high
cryoscopic constants at a reasonable cost. The list is even
shorter when green constraints such as toxicity and bioaccum-

Table 1. Cryoscopic Constants, kf, and Freezing Points (fp)

of Some Candidate Compounds for Freezing-Point Depression Experiments
k f/ Cost/
Solvent fp/°C Ref
(°C kg/mol) (U.S.$/kg)a
Water 1.86 0.0 --- 6, 7
Formic acid 2.38 8.3 40.00 6, 7
Acetic acid 3.63 16.7 34.33 6, 7
p-Xylene 4.3 13.3 59.00 6, 7
Stearic acid 4.5 69.0 16.90 6, 7
Benzene 5.07 5.5 28.62 6, 7
Palmitic acid 5.8 64 64.10 this workb
Phenol 6.84 40.9 31.30 6, 7
Nitrobenzene 6.87 5.8 19.00 6, 7
Naphthalene 7.45 80.3 27.80 6, 7
p-Dichlorobenzene 7.57 52.7 15.60 6, 7
Myristic acid 8.5 55.1 27.10 this workb
Lauric acid 13.5 46 19.90 this workb
Bicyclohexane 14.52 3.6 1535.00 6
Cyclohexane 20.8 6.5 31.16 6, 7
Camphor 37.8 178.8 29.20 6, 7
Cyclohexanol 42.2 6.5 17.71 6, 7
a
Values obtained from 2004–2005 Acros Organics catalog, values for liquids were converted to kg
using the density.
b
Approximate kf values based on average kf’s for addition of three different fatty acids over the range
of 0–10 wt. % .

116 Journal of Chemical Education • Vol. 82 No. 1 January 2005 • www.JCE.DivCHED.org

 In the Laboratory

ulation are considered. Fatty acids, however, simultaneously

satisfy all of the above constraints. The physical properties Old Lab Procedure
of fatty acids are right, the cost is low, and two major green
chemical objectives (8) can be reached. First, the waste stream Cl
is nontoxic, which simplifies utilizing the waste stream as a
feedstock for making materials such as soap, biodiesel, or wax.
By utilizing the waste stream instead of throwing it away, we aromatic
petroleum +
unknown
are able to satisfy pedagogical laboratory objectives without
the concomitant generation of waste (see Scheme I and the
experimental section) (9). Second, industrial synthesis of fatty Cl
acids is through the hydrogenation of biomass such as palm
freezing point
oil, cottonseed oil, and other oils from agricultural feedstocks
depression data
(4). Therefore, using fatty acids promotes the use of renew-
able biomass resources as opposed to exhaustible petroleum aromatic or
derived feedstocks. A comparison of the two laboratories from chlorinated
a green perspective is shown in Scheme I. waste

Materials New Greener Lab Procedure

All materials were purchased from Acros Organics and O
used without further purification.
biomass + fatty acid
HO unknown
Hazards 15

Stearic, lauric, myristic, and palmitic acids are nonhaz-

ardous, but prolonged skin contact may cause irritation. If freezing point
depression data
fatty acids are spilled on skin, students should wash affected
areas thoroughly with soap and water. 2-Propanol is flam- useful feedstocks
mable and should be kept away from an ignition source.

Experimental Procedures
In one laboratory period students determine the fp of
three fatty acid samples: pure stearic acid (ca. 9 g) and stearic
acid with first 1 g, then a total of 2 g of an unidentified fatty
acid (lauric, palmitic, or myristic) added. The students ob-
serve the depression in fp relative to the fp of the pure stearic
acid and use the information to determine the molar mass,
M, of their unidentified sample.
Colligative Properties Measurements
A hot water bath (85–90 ⬚C) is used to melt an accu-
rately weighed sample of about 9 g of stearic acid in a test
tube. The test tube containing the molten stearic acid at ap-
proximately 85 ⬚C is removed from the heating bath and
placed in an insulating jacket to cool (see the Supplemental
MaterialW). An alcohol-based thermometer is used to stir and
measure the temperature of the mixture over a period of 8–
10 minutes. Students record temperature data every 30 sec-
onds. After completion of the first cooling trial, the measuring
procedure is repeated 2–3 more times.
Next, an accurately weighed sample of about 1 g of an
unidentified fatty acid is added to the stearic acid and the
measuring procedure repeated. An additional aliquot of about
1 g of the same unidentified fatty acid is added to the mix-
ture and the measuring procedure again repeated. Collected
data are then analyzed (see the Calculations section below
for instructions and equation) to yield the M of the uniden-
tified sample.
SOAP
cleaning
biodiesel wax
products
Scheme 1. Comparison of conventional and green laboratory pro-
cedures for measuring colligative properties.
Utilizing the Waste Stream
The fatty acid mixture is recovered by reheating to
85 ⬚C and pouring the molten mixture into a clean, food-
grade waste container for further use as a feedstock for mak-
ing soap, biodiesel, or wax (see Supplemental MaterialW).
Residual fatty acids remaining in the test tube and on the
thermometer are dissolved with hot 2-propanol and trans-
ferred to a separate container. Cooling of the 2-propanol mix-
ture or removal of the 2-propanol via rotary evaporation
allows an additional crop of fatty acids to be recovered. The
2-propanol can be recycled and reused if desired. Even if the
waste stream from the experiment is not utilized, recycled,
or reused, it is at least benign.

www.JCE.DivCHED.org • Vol. 82 No. 1 January 2005 • Journal of Chemical Education 117

 In the Laboratory

90 25

∆Tf = 4.5 m
85 20
Temp / °C

80 15

Tf
freezing point
75 10

70 5

65 0
0 100 200 300 400 500 600 0 1 2 3 4 5 6

Time / s Molality (m) of Myristic Acid / (mol/kg)

Figure 1. Example of data collected by students using a mixture of
stearic and myristic acids. The squares represent temperature
changes greater than 0.5 ⬚C per 30 seconds and the circles repre-
sent temperature changes by less than 0.5 ⬚C per 30 seconds. The
intersection of the two best-fit lines estimates the fp of the mixture.
Figure 2. Plot of temperature change versus molality of the myristic
acid for addition of myristic acid to stearic acid. The initial slope
of the line yields a kf value that matches the literature value over a
wide range of molalities.

Calculations 2. This is the same number of trials performed by students

in the actual laboratory experiment.
For each trial, a cooling curve is constructed as shown
The accuracy of the M values determined by freezing
in Figure 1. Data are plotted in two separate series. The first
point depression of fatty acid mixtures is directly comparable
series is where the temperature changes by more than 0.5 ⬚C
to M values determined using aromatic hydrocarbon solvents
per 30 seconds and the second series is where the tempera-
with aromatic unidentified samples. Most students can de-
ture changes by less than 0.5 ⬚C per 30 seconds. A best-fit
termine M’s to within about 5–10% using these methods,
line is drawn through each series. The temperature at which
just accurate enough to definitively assign which fatty acid is
the lines intersect is approximately the fp of the mixture.
the unidentified sample. Typical student data demonstrating
Freezing points for each trial are determined, averaged, and
colligative behavior for addition of varying quantities of
used for calculations based on the equation,
myristic acid to stearic acid are shown in Figure 2. Stearic
acid makes a good solvent choice for the experiment because
∆Tf = kf m
it exhibits a linear change in freezing point over a wide con-
centration range of added solute (see the Supplemental
where ∆Tf is the change in fp, kf is the cryoscopic constant
MaterialW).
for stearic acid, 4.5 ⬚C kg兾mole, and m is the molality of the
unidentified sample. The M of the unidentified sample is then
determined for each trial (see Supplemental MaterialW). Conclusion
Using green techniques in a teaching laboratory setting
Results and Discussion
allows pedagogical objectives to be attained without the con-
Experimentally determined M’s for an average of four comitant generation of hazardous wastes. The approach is
independent trials using stearic acid as the solvent and palm- both practical and cost effective. This green lab has been suc-
itic, myristic, or lauric acid as the solute are shown in Table cessfully implemented for about 250 students per semester.

Table 2. Student Obtained M values from ∆Tf Measurements

Unidentified Detd M/ Std Dev Actual M/
Solvent Percent Error
Sample (g/mol) in Detd M (g/mol)
Stearic Acid Lauric Acid 203.13 1.47 200.32 1.4
Stearic Acid Myristic Acid 235.77 6.43 228.37 3.2
Stearic Acid Palmitic Acid 252.79 7.17 256.24 1.3
NOTE: Four trials were performed for each unidentified sample.

118 Journal of Chemical Education • Vol. 82 No. 1 January 2005 • www.JCE.DivCHED.org


Acknowledgments
We would like to thank members of the Spring 2002
and 2003 introductory chemistry classes Denise Pisani,
Rosemarie Candido, Meredith Kocur, Emily King, Colt
Lorson, Patty-Ann Czismesia, Rosalie Wilson, Lisa
Rinaldi, members of the GreenCats student organization,
the ChemCats student organization president Anya
Gushchin, and the chemistry laboratory supervisor John
Sharp for their help in developing and implementing this
laboratory. We would also like to thank the University of
Vermont and VT EPSCoR for their support of this work.
Finally, acknowledgment is made to the donors of the Pe-
troleum Research Fund, administered by the American
Chemical Society, Grant #36567-G3 for partial support
of this research.
W
Supplemental Material
Comprehensive instructor notes, a detailed discussion
of the freezing behavior of various fatty acid mixtures, ex-
amples of typical data obtained, and a detailed description
of the experimental protocols, including student calcula-
www.JCE.DivCHED.org • Vol. 82 No. 1 January 2005
In the Laboratory
tions and quizzes, are all available in this issue of JCE
Online.
Literature Cited
1. Parker, R. C.; Kristol, D. S. J. Chem. Educ. 1974, 71, 492.
2. Beran, J. A. Laboratory Manual for Principles of General Chem-
istry, 5th ed.; John Wiley & Sons, Inc.: New York, 1994.
3. Educating for OSHA Savvy Chemists; Utterback, P. J., Nelson,
D. A., Eds.; American Chemical Society: Washington DC,
1998; ACS Symposium Series Vol. 700.
4. The Merck Index, 13th ed.; O’Neil, M., Ed.; Merck & Com-
pany, Inc.: Whitehouse Station, NJ, 2001.
5. van Loon, W. M. G. M.; Wijnker, F. G.; Verwoerd, M. E.;
Hermens, J. L. M. Anal. Chem. 1996, 68, 2916–2926.
6. Lange’s Handbook of Chemistry; Dean, J. A., Ed.; McGraw-Hill
Inc.: New York, 1979.
7. CRC Handbook of Chemistry and Physics, 76th ed.; Lide, D.
R., Ed.; CRC Press Inc.: New York, 1995.
8. Anastas, P.; Warner, J. Green Chemistry: Theory and Practice;
Oxford University Press: Oxford, 1998.
9. Awang, R.; Ahmad, S.; Ghazali, R. J. Oil Palm Res. 2001, 13,
33–38.
• Journal of Chemical Education 119