QUALITATIVE TESTS FOR IDENTIFICATION OF CARBON-CARBON

UNSATURATION AND ALCOHOL FUNCTIONS (Rev’d 12/12/2004)

In this experiment we will examine two reagents (bromine in carbon tetrachloride and
aqueous potassium permanganate) which are widely used for qualitative identification of
carbon-carbon unsaturation and three reagents (chromic acid, hydrochloric acid, and
hydrochloric-zinc chloride) which are widely used for qualitative identification of alcohols.

Please handle these reagents with care and avoid contact with skin. Bromine causes
chemical burns, permanganate causes stubborn to remove stains, and chromic acid and
Lucas reagent are very strongly acidic solutions.

Reagents for Detection of Unsaturation

Bromine in Carbon Tetrachloride

This reagent is commonly used to identify the presence of olefinic or acetylenic functions.
The red bromine color of this reagent is discharged when the unsaturated function reacts
with the bromine. This reagent should be used in conjunction with the aqueous
permanganate reagent to avoid erroneous conclusions. Erroneous results with the bromine
reagent may occur for two reasons. Firstly, not all olefinic or acetylenic compounds take
up bromine. When electron withdrawing groups are attached to the unsaturated carbon
atoms the uptake of bromine is considerably slowed and in extreme cases completely
stopped.

C 6H5CH CH2 + Br2 fast

C 6H5CHBrCH 2Br

slow
C 6H5CH CHCO 2H + Br2 C 6H5CHBrCHBrCO 2H

Secondly, some other functionalities discharge the bromine color but with the evolution of
hydrogen bromide. That is to say, they undergo bromine substitution instead of bromine
addition. Compounds which undergo substitution extremely rapidly are phenols, enols,
and anilines. Thus a positive test for unsaturation is one that discharges the bromine color
without the evolution of hydrogen bromide.

Procedure: Add 1 drop of the liquid (or the tip of a microspatula of a solid plus 3 drops of
ethanol) to a small test tube and then add a 5% (0.3 M) solution of bromine in carbon
tetrachloride drop by drop (with agitation) until the bromine color remains. Run this test
on (1) cyclohexene, (2) cyclohexane, (3) ethanol, and (4) cinnamic acid and record your
observations. For the cinnamic acid, let the test tube sit and check it periodically during
the remainder of the lab period to see how long it takes for the bromine color to disappear.
Aqueous Potassium Permanganate

The purple permanganate color of this reagent is discharged by olefinic and acetylenic
functions. This is known as the Baeyer test for unsaturation. In cold (room temperature or
below) dilute aqueous solutions the main products from the reaction of an olefin with
permanganate are the corresponding vicinal diol and manganese dioxide (brown solid).
Acetylenes produce the corresponding diones. If heated these initial products undergo
further oxidation, leading eventually to carbon chain cleavage with the formation of
carboxylic acids. This test is very general and gives positive tests with those unsaturated
compounds that do not decolorize bromine in carbon tetrachloride.

RCH CHR + KMnO4 + 2 H2O RCH CHR + MnO2 + 2 KOH

OH OH

RCH CHR further

2 RCO 2H
oxidation
OH OH

Two cautions are in order when using the Baeyer test. Firstly, aldehydes give positive tests
because they are readily oxidized to carboxylic acids by permanganate. Secondly, although
pure alcohols do not react within 5 minutes, they often contain trace impurities that are
easily oxidized and give a slight reaction. Likewise alkanes often contain trace amounts of
olefins as impurities and may give a slight reaction. For these reasons decolorization of a
drop or two of the reagent should not be accepted as a positive test.

Procedure: Add 4 drops of the liquid (or the tip of a microspatula of a solid) to be tested
to 1 mL (~20 drops) of ethanol in a small test tube. Then add a 1% potassium
permanganate solution drop by drop with shaking until a dark precipitate forms or the
purple color of the permanganate persists. Run this test on the same compounds used in
the bromine test above and record your observations. If decolorization doesn't occur in ~1
minute, allow the mixture to stand for 5 minutes with occasional shaking.

Perform both the above tests with the two unknowns and report your observations and
conclusions.

Reagents for Detection and Classification of Alcohols

Chromic Acid

This reagent provides a rapid method for the detection of alcohol functions and also allows
for distinguishing primary and secondary alcohols from tertiary alcohols. When a solution
of the alcohol in acetone is treated with several drops of the chromic acid solution, the
orange-red color of the chromic acid is disappeared and a green to blue opaque suspension
of chromium(III) sulfate is formed. Primary and secondary alcohols react within 2 seconds
but tertiary alcohols do not. Tertiary alcohols will eventually react when allowed to stand
for longer periods of time in the strongly acidic solution. Aldehydes give a positive test,
but olefins, acetylenes, amines, ethers, and ketones give negative tests within 2 seconds.

RCH 2OH + H2CrO4 + H2SO 4 RCO 2H + Cr2(SO 4) 3 + H2O

R2CHOH + H2CrO4 + H2SO 4 R2CO + Cr2(SO 4) 3 + H2O

Procedure: Add 1 drop of the liquid to be tested to 1 mL of reagent grade acetone in a

small test tube. Then add 1 drop of the chromic acid reagent and note the result within 2
seconds. A positive test is for the orange color of the chromic acid to be replaced by a
green to blue opaque suspension. Run this test on (1) 1-butanol, (2) 2-butanol, and
(3) 1,1-dimethylethanol (t-butanol) and record your observations.

Hydrochloric Acid-Zinc Chloride (Lucas Reagent)

Only tertiary alcohols and alcohols that can form carbocations of equal stability to tertiary
carbocations react with concentrated hydrochloric acid to produce alkyl chlorides.
However, alcohols are more reactive towards Lucas reagent than with concentrated
hydrochloric acid. The zinc chloride is a potent Lewis acid and forms such a strong Lewis
acid-base complex with the hydroxyl group that it becomes a better leaving group than
even water. Thus Lucas reagent allows for distinguishing primary, secondary, and tertiary
alcohols from one another. Primary alcohols are essentially inert towards Lucas reagent at
ordinary temperatures, but secondary and tertiary alcohols are converted into their alkyl
chlorides at easily discernible different rates by Lucas reagent. Because a positive test
depends upon the appearance of the alkyl chloride as a second liquid phase, the test is
clearly limited to alcohols that are soluble in the reagent. This usually limits the test to
monofunctional alcohols with less than 6 carbons and to certain polyfunctional alcohols
such as glycols. Tertiary alcohols give positive tests in less than 1 minute, whereas
secondary alcohols begin to show milky emulsions within 5 minutes with a distinct layer
visible in about 10 minutes.

H
HCl H2O
R 3COH R 3C O H R3C + Cl R3CCl

Cl

H
ZnCl 2 HOZnCl
R 2CHOH Cl R 2CH O ZnCl R 2CHCl

H
ZnCl 2 HOZnCl
R 3COH R 3C O ZnCl R 3C + Cl R3CCl

Cl

Procedure: To 3 drops of the alcohol in a small test tube add 1 mL of Lucas reagent
which has been warmed to ~25 oC. Using a gloved finger, stopper the tube and shake. Allow
the mixture to stand and note the time required for the formation of the alkyl chloride,
which appears as a milky emulsion or a second layer. Run this test on (1) 1-butanol, (2) 2-
butanol, (3) 1,1-dimethylethanol (t-butanol) and record your observations. Repeat this
procedure using concentrated hydrochloric acid in place of the Lucas reagent and record
your observations.

Perform the tests for detection and classification of alcohols with the two unknowns given
by your TA and report your observations and conclusions. Record the unknown code in
your lab notebook.

Lab Notebook Preparation

Prior to lab, prepare tables similar to the example provided for each of the five tests that are
to be performed during the lab period. These will serve for all of your data and observation
entries. Conclusions should also be entered directly into the tables and turned in by the end
of the lab period you complete the experiment in. Some points, which are normally
assigned to the postlab exercise, have been redistributed to these conclusions. The
experiment’s Postlab Exercise is due one week following the completion of the
experiment.

NOTE: Some of the reactions can (or should be) observed immediately; others should be
observed over a period of time.

WASTE DISPOSAL INFORMATION

1. Detection of Unsaturation Tests

a. Br2 in CCl4 TEST: Discard ALL test solutions in Halogenated Waste Container.
b. KMnO4 (aq) TEST: Discard ALL test solutions in NON-halogenated Waste Container.

2. DETECTION & CLASSIFICATION OF ALCOHOLS

Use sink for disposal (with plenty of running water).
Name:_______________________________Section:________ Date:___________

POSTLAB EXERCISES FOR: QUALITATIVE TESTS FOR IDENTIFICATION OF CARBON-

CARBON UNSATURATION AND ALCOHOL FUNCTIONS (Rev’d 12/12/2004)

Due in lab one week following the scheduled experiment. Please answer questions
on this form.

SUMMARY (21pts)
The summary is in the form of conclusions for each of the tests performed and
(should be) included in your notebook.
1. Conclusions for the unsaturation tests (3pts/test = 12pts).
2. Conclusions for the alcohol tests (3pts/test = 9pts).

QUESTIONS (9pts)
Based upon the background information provided on the above qualitative tests and
your observations answer the following two questions on this form.

1. (3pts) A compound that is known to be one of the three shown below gives a negative
bromine test, but a positive permanganate test. Which is the correct structure?

OH CH3CH2 H HO2C H
C C C C
CH3CH2CH2C(CH 3) 2
H CH2CH3 H CO2H

A B C

2. (6pts) An alcohol gives a positive Lucas test, but does not react with concentrated
hydrochloric acid. Would you expect this alcohol to give a positive or negative
chromic acid test? Explain.