a

as external insulation) extracted at temperatures substantially

below the boiling point of the solvent-as much as 15 cooler
for hexane (bp 68.7 C). This represents an advantage for
the microscale apparatus, since the extraction temperature can
be accurately set very close to the boiling point of the solvent
chosen.

Microscale (4-mL)
Macroscale (1000-mL)

Conclusions

50.0
30

40

50

60

70

Time / min

00

figure 3. The microscale extractor remains at a constant temperature

near the boiling point of the solvent throughout the extraction. The
macroscale Soxhlet (with moderate insulation) extracts at a significantly cooler temperature and exhibits a periodic fluctuation in
temperature coinciding with the rise and fall of the solvent level.

very near the boiling point of the solvent, whereas without

extensive insulation, the sample temperature of extraction of
the Soxhlet fluctuates with the rising and falling of the solvent
level. The 1000-mL Soxhlet (with a layer of aluminum foil

The microscale continuous hot solvent extractor compares extremely well with traditional Soxhlet extractors while
reducing the solvent waste produced in a 300-mL extraction
by 99%. The extractor can be made by an amateur glassblower and has promise for use in the microscale lab as a
teaching tool for extractions as well as introducing representative sampling.
Acknowledgment
Special tanks to the Geneva, IL, Laboratory of Waste
Management, Inc. for the use of a variety of Soxhlet extractors
for comparison.
Literature Cited
1. Williamson, K. W. Macroscale andMicroscale Organic Experiments,
2nd ed.; D. C. Heath: Lexington, MA, 1994.

Qualitative Analysis in the Beginning Organic Laboratory

James H. Cooley and Richard Vaughan Williams*

Department of Chemistry, University of Idaho, Moscow, ID, 83844-2343; *williams@neon.chem.uidaho.edu

Simple questions from students are frequently provocative

enough to make us rethink our teaching methods. Such was
a question that came from a student during the beginning
part of an organic course. It was, "How do you know all these
things?" Many of the textbooks of 25 years ago presented
more of the methods by which the subject is studied (1).
Organic chemistry, as it is presented in textbooks today, is a
collection of facts originating from conclusions reached by
interpretation of data collected in some laboratory at some
time. Except for the description and interpretation of spectra,
description of other data obtained in the laboratory is not
found. This approach adds to the students' perception that
organic chemistry is an abstract subject. As an example, most
organic texts start with a description of bonding and move on
to discuss molecular structure. The structures are presented
as factual information to be remembered-and for all too
many students, just memorized.
A New Approach

We have developed an approach to teaching the organic

laboratory course (2) which emphasizes the collection and
i nterpretation of data in order to solve a problem. This approach
provides a more balanced introduction to organic chemistry
and an answer to the question posed by our student. One
topic which we include in our laboratory course, and which is
very popular with our students, is qualitative organic analysis.

The debate over whether to include classical methods of

qualitative analysis in the laboratory course has been relatively
quiescent in this journal recently. However, two papers on
this topic appeared a few years ago (3, 4). The first claimed
that with the advent of a computer library of organic compounds attached to an IR instrument, students always got the
unknown correct and learned very little from the experience
(3). The second defended classical qualitative analysis as a good
way to learn organic chemistry (4). Our own, admittedly
li mited, poll suggests that at least a third of professors feel that
because of spectroscopy, classical "qual" is no longer needed.
In "qual" the student is exposed to many of the reactions
discussed in the lecture course. For most students this is a
very positive experience, which reinforces their understanding
of organic chemistry. All these reactions give highly visual
and pleasing results such as a color change or formation of a
precipitate. Reactions covered in a lecture text, such as the
reaction of potassium permanganate with an alkene or 2,4dinitrophenylhydrazine with an aldehyde or ketone, are
reviewed and performed in the laboratory. The standard
textbook presentation tends to treat each functional group
i n isolation. In qual, the very different reactivities of the various functional groups are compared. This comparison of the
reactivity of different functional groups strengthens the
student's understanding of the subject. The shift in emphasis
away from synthesis experiments, where the objective is to

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1117

I n the Laboratory
obtain a product, to using reactions to deduce information
about an unknown is usually a welcome change. Data such
as boiling points and melting points, as well as spectra, must
be determined carefully in order for the student to justify
reaching a conclusion about the structure of the unknown.
When formation of a derivative is required, students must
adapt a general procedure to a specific compound. They
frequently learn a great deal from such an experience. For
example, when a derivative is required, we find that students
gain a greater understanding of recrystallization and the
relationship of purity to melting point. Finally, introduction
of a very systematic and logical approach to determining
structure is something students like. We consider qual to be
an invaluable part of our organic chemistry course.
In classical qualitative analysis, as presented in Shriner,
Fuson, Curtin, and Morrill (5) or Cheronis, Entrikin, and
Hodnett (6), the student is directed to identify the unknown
from tables that list possible compounds. The tables are
organized to collect together compounds with a particular
functional group and to index these compounds in order of
i ncreasing boiling point for liquids or increasing melting point
for solids. To use these tables, the student must determine
the functional group that is present in the unknown and the
unknown's boiling or melting point.
Since it is crucial that the boiling point or melting point
be determined correctly, we advise students to repeat the
determination of these properties until they are certain that
the results can be reproduced. In an earlier experiment we
i ntroduce IR spectroscopy as the best method for identifyi ng a functional group; in these experiments we introduce
solubility and classification tests as a means of identifying
functional groups. We ask students to classify unknowns by
using solubility and classification tests before recording any
spectra. Students welcome the verification of results that
comes from using both methods.

Method

The First Experiment

We elected to introduce this systematic approach to

qualitative analysis, but to limit the number of classes of
compounds and to use only three experiments. In the first
experiment the unknowns are limited to alkanes, alkenes,
alkyl halides, primary and secondary alcohols, and ethers. The
procedure followed by our students is summarized in Flow
Chart I. For tables, we refer students to the CRC Handbook
of Tables for Organic Compound Identification (7). Solubility
tests introduced at this point are in water, ether, and concentrated sulfuric acid. Water and ether serve to introduce
the technique used in determining solubilities and help to
distinguish a low-molecular-weight alcohol or ether from the
rest. Concentrated sulfuric acid distinguishes an alkane or
alkyl halide (which are insoluble) from an alkene, alcohol,
or ether (which are soluble). Classification tests include, for
the alkyl halide, the Beilstein test, formation of a precipitate
with ethanolrc silver nitrate or with sodium iodide in acetone;
for the alkene-, - the Baeyer test with aqueous potassium permanganate and decolorization of bromine in methylene
chloride; and for the alcohol (primary or secondary) oxidation
with chromic acid. Because good classification tests specific
for the alkane or ether are not known, the presence of these
functional groups must be deduced from the solubility test
in sulfuric acid, negative results on other classification tests,
and eventually from IR and NMR spectra. The data students
collect allow them to use the tables to select a few possibilities.
While we recommend that proton and carbon NMR and IR
spectra be used to confirm the identity of the unknown after
its identification from "wet tests", students are required to
decide for themselves exactly what data to collect. Grading
is based not only on the right answer but also on the written
discussion the student makes by careful interpretation of the data

now,,-narr i
For Alkane, Alkene, Alkyl Halide, Alcohol, and Ether

"Only primary and secondary alcohols are used as unknowns (tertiary alcohols are, of course, not oxidized by chromic acid).
1 11 8

Journal of Chemical Education

Vol. 76 No. 8 August 1999

JChemEd.chem.wisc.edu

that have been collected. A major aim of these experiments,

emphasized in the grading scale, is that the student gain and
display understanding.
The Second Experiment

In a second experiment the classes of compounds introduced are aldehyde, amine, carboxylic acid, ester, ketone, and
phenol. The procedure followed is summarized in Flow Charts

II and III. In this experiment solubility tests in water, 5%

hydrochloric acid, 5% sodium hydroxide, and 5% sodium
bicarbonate are introduced. To decide between weak and
strong acids and bases, the student is directed to test water
solutions with litmus or pH paper. These tests introduce the
solubility behavior of acidic and basic compounds, and most
students are able to use them to decide among the various
functional groups without too much difficulty. Classification
tests introduced in this experiment include a 2,4dinitrophenylhydrazine test for an aldehyde or
ketone, a Tollens test foran aldehyde, formation
of CO 2 bubbles in the solubility test with sodium
bicarbonate for a carboxylic acid, Hinsberg and
nitrous acid tests for an amine, ferric chloride and
bromine water tests for a phenol, and hydroxylamine, followed by ferric chloride, for an ester.
As in the previous experiment, students use both
the solubility and classification tests and boiling
or melting point to identify the unknown.' As
before, following identification with "wet tests",
the student is encouraged to confirm the identification with IR and NMR spectra.
The Third Experiment

For Acid, Aldehyde, Amine, Ester, Ketone, and Phenol

In a third experiment, the student is given

an unknown belonging to one of the 11 classes
of compounds introduced in the first two experiments. We ask the student not only to identify
this unknown, but also to select, prepare, and purify by crystallization a solid derivative of it. The
melting point of the derivative is determined and
compared with that listed in the tables.
Discussion and Conclusions

Flow Chart III

For Water-Insoluble Acid, Aldehyde, Amine, Ester, Ketone, and Phenol

Confirmatory tests for amines (Hinsberg and nitrous acid tests also distinguish between primary, secondary, and tertiary amines), esters (saponification and ferric
hydroxamic acid tests), and phenols (ferric chloride and bromine water tests) may
also be run.
JChemEd.chem.wisc.edu

The qual experiments are a big departure

from earlier laboratory experiences. The student
is to develop a plan for "solving" the unknown
by deciding what tests to run and how much data
to collect to present a convincing argument to
the instructor in support of their structural assignment. We find that students need time to
reach an understanding of the experiment in addition to enough time to complete the assigned
tasks. We inform the students in the first period
how many unknowns of each type they must
i dentify in the scheduled time (up to seven threehour laboratory periods). We allow them to work
at their own pace and encourage them to identify additional bonus compounds. At every step
there is sufficient time to carry out confirmatory
positive tests on authentic samples (provided) of
each class of compounds. We strongly encourage students to carry out these additional positive tests, as it is, of course, imperative that they
should know what to look for in a positive test.
In addition, we frequently adopt the following
approach. Tests like the evolution of a gas when
an aqueous solution of sodium bicarbonate and acetic acid are mixed are easily interpreted. However, the same test with a high-molecular-weight
carboxylic acid is much more difficult to inter-

Vol. 76 No. 8 August 1999

Journal of Chemical Education

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I n the Laboratory
pret, and students invariably ask the instructor for help. At
this point, the importance of side-by-side comparison is demonstrated for the entire class. Thereby, even students who not
have a particular class of unknown and are not motivated to
explore all tests with authentic samples are exposed to the
widest possible variety of positive tests. This series of experiments is a confidence builder for our students. They feel that
they have enough time to complete the tasks assigned and
that they are learning something useful from each test.
In informal surveys conducted over a period of several
years upon completion of the courses, the majority of students
state, without being prompted, that they thoroughly enjoyed
the qual and learned a great deal from it. Many consider it
to have been one of their best educational experiences. For
the past four years, one of us has taught a second-semester
organic lab designed to meet the needs of our chemical
engineering majors. This lab meets only once per week for
three hours rather than the two three-hour lab meetings per week
for our regular chemistry major sequence second-semester
l ab. The first half of this lab is devoted to qual as described
above. Many of the students in this lab resent that they are
required to take "so much organic chemistry" and are not
kindly disposed toward a three-hour lab with only one hour
of credit. We frequently notice a considerable change in these
students as the lab progresses. They become very involved
in the "detective work" of qual and express, with some surprise,
that they are really enjoying the lab and learning things that
they consider valuable. They are subsequently much more
receptive to the remaining half of the course. Usually at least
one student per semester from these labs decides to change
to a double major of chemical engineering and chemistry or

even to become a chemistry major, often citing the lab as

the turning point in this decision. Similarly, many students
i n these labs have gone on to participate in undergraduate
research with one of the authors. Again they cite their very
positive experience in the lab course, and particularly qual,
as their reason for choosing to engage in research. In many
laboratory experiments, students race through procedures,
submit a result to the instructor, and finish without a chance
to reflect on what has been done. We feel that the necessity
of understanding these experiments has caused the very favorable comments from our students.
Note

1. A reviewer suggested that more classical experiments (e.g., the

i odoform test and ceric ammonium nitrate oxidation of alcohols) be
i ncorporated. While this is perfectly feasible, we have deliberately simplified the classical qual scheme to make the concepts more accessible
and meaningful to the students. Certainly, at the discretion of the individual instructor, other "wet tests" could be added or substituted.

Literature Cited

1. Noller, C. R. Chemistry of Organic Compounds, 3rd ed.; Saunders:

Philadelphia, 1965; Chapter 4.
2. Cooley, J. H. J. Chem. Educ. 1991, 67, 503.
3. Zubrick, J. W. J. Chem. Educ. 1992, 69, 387.
4. Ziegler, H. E. J. Chem. Educ. 1993, 70, 230.
5. Shriner, R. L.; Fuson, R. C.; Curtin, D. Y.; Morrill, T C. Systematic
Identification of Organic Compounds, 6th ed.; Wiley: New York, 1979.

6. Cheronis, N. D.; Entrikin, J. B.; Hodnett, E. M.

Semimicro Quali-

tative Analysis, 3rd ed.; Wiley: New York, 1965.

7. CRC Handbook of Tables for Organic Compound Identification;
Rappoport, Z., Compiler; CRC: Boca Raton, FL, 1967.

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