CHM 112 Lab Procedure 3:

ALCOHOLS, ALDEHYDES, AND KETONES

Objectives:
(a) to use different chemical tests to differentiate the alcohol, aldehyde, and ketone
functional groups.
(b) to determine the functional group present in an unknown solution based upon
those chemical tests

Introduction:

There are several tests that may be performed to distinguish among the different
classes of alcohols, aldehydes, and ketones. All these tests exploit differences in the
type and degree of reactivity of each of the functional groups. You will check the
reaction characteristics of five different functional groups (primary alcohols, secondary
alcohols, tertiary alcohols, aldehydes, and ketones), and an unknown, and, based upon
reaction characteristics, determine the functional group of the unknown.

The first step is to identify the structure of each of the functional groups.

• Primary alcohols (1° alcohol) have the group –CH2OH, where the carbon atom
with the alcoholic hydroxyl group has at least two additional hydrogens attached to
that carbon. The alcoholic hydroxyl group is attached to a primary carbon. Think of
a primary alcohol (1°) as one where the carbon with the hydroxyl group is attached
to one R group (R stands for any other organic chain or group).
H
R C OH

• Secondary alcohols (2° alcohol) have the group –CHOH, where the carbon
atom with the alcoholic hydroxyl group has only one additional H atom attached to
it. There are two R groups (R stands for any other organic chain or group), and the
alcoholic hydroxyl group is attached to a secondary carbon. So, a secondary alcohol
(2°) is one where the carbon atom with the hydroxyl group is also attached to two R
groups.

H
R C OH

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• Tertiary alcohols (3° alcohol) have the group –COH, where the carbon atom
with the alcoholic hydroxyl group has no additional H atoms attached to it. There
are three R groups (R stands for any other organic chain or group), and the
alcoholic hydroxyl group is attached to a tertiary carbon. So, a tertiary alcohol (3°)
is one where the carbon atom with the hydroxyl group is also attached to three R
groups.

R C OH

• Aldehydes and Ketones are characterized by a functional group called a

carbonyl group – a carbon atom double-bonded to an oxygen atom.
O

Carbonyl group
The difference between aldehydes and ketones is in the groups attached to the
carbonyl carbon atom. In the case of an aldehyde, there is always at least one H atom
attached to the carbonyl carbon atom. An aldehyde has one R group attached. In the
case of ketones, there are no H atoms attached to the carbonyl carbon. The ketone
has two R groups attached.

O O

C C
H R R R

Aldehyde Ketone

(To keep this straight, you might want to think of the word “aldeHyde.” It has an “H”
in the name and an H atom attached to the carbonyl carbon atom. Ketone is the one
without an “H” in the name and without an H atom in the carbonyl structure.)

Now that the structures have been identified, there are several chemical tests that are
used to distinguish these functional groups.

A. Differences in oxidation: Several different oxidizing agents may be used to

cause the oxidation of molecules. Potassium permanganate (KMnO4) or
potassium dichromate (K2Cr2O7) or even atmospheric oxygen (O2) are oxidizing

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 agents. The symbol [O] is commonly used to mean any oxidizing agent. It’s the
action of the oxidizing agent, not its identity that is important here.

One way to look at oxidation is that oxidation is the reaction that increases the
number of C-O bonds and/or decreases the number of C-H bonds. Therefore,
reduction is the opposite and is a reaction that decreases the number of C-O
bonds and/or increases the number of C-H bonds.

a. A primary alcohol oxidizes readily, first to an aldehyde, then to a carboxylic

acid. These two oxidation steps make sense because the primary alcohol
functional group has two C-H bonds that can be broken.
O
H [O] O
C [O]
R C OH C
R H
R OH
H
Primary alcohol Aldehyde Carboxylic acid

b. A secondary alcohol only has only one C-H bond that can be broken, so it can
only oxidize once, to a ketone.

R O
[O]
R C OH C
R R
H Ketone
Secondary alcohol

c. A tertiary alcohol has no C-H bonds that can be broken, so it is NOT oxidized,
no matter how strong the oxidizing agent may be.

R
[O]
R C OH
NR (no reaction)
R

Tertiary alcohol
d. From this information on alcohols, it is clear that aldehydes will oxidize to
carboxylic acids. An aldehyde has one C-H bond that can be broken. Think
back to what happens to 1° alcohols. The aldehyde produced by the
oxidation of a primary alcohol can be again oxidized to the carboxylic acid,
and therefore, any aldehyde can be oxidized to a carboxylic acid.

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 O
O
C [O]
R H C
R OH

Aldehyde Carboxylic acid

e. Any ketone, just like the product of the oxidation of a 2° alcohol, has no C-H
bonds that can be broken, so ketones cannot be oxidized.

O
[O]
C NR (no reaction)
R R

Ketone

This lab experiment will use a solution of potassium dichromate (K2Cr2O7) as the
oxidizing agent. The starting solution of potassium dichromate is yellow-orange, but if
any oxidation takes place, the solution will turn blue-green. This color change is due to
the Cr+6 ion (orange in K2Cr2O7) being reduced to the Cr+3 ion (blue green).

B. The Lucas test for alcohols: This test distinguishes among the three types of
alcohols (1°, 2°, and 3°), by the speed with which they react. The reaction is a
replacement reaction, where a Cl from HCl (mixed with ZnCl2) replaces the
hydroxyl group on the alcohol. It should be noted that, because aldehydes and
ketones do not have a hydroxyl group to replace with Cl, they would both give a
negative Lucas test.

ZnCl2
C OH + HCl
C Cl

Clear solution Cloudy from the

insoluble chloride

Surprisingly enough, 3° alcohols react very fast with the Lucas reagent (HCl mixed with
ZnCl2), and will turn cloudy almost immediately. Secondary alcohols do react, but more
slowly and must be heated in a water bath in order to react and turn cloudy. Primary
alcohols react so slowly (even in a warm water bath) that NO REACTION is observable.
A yellow or yellow-orange color without any precipitate is a negative result.

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 C. 2,4-Dinitrophenylhydrazine test: This test uses an organic reactant, 2,4-
dinitrophenylhydrazine, to distinguish the carbonyl compounds (aldehydes and
ketones) from the non-carbonyl compounds (the alcohols). The 2,4-
dinitrophenylhydrazine reagent is a translucent yellow solution, but in the
presence of a carbonyl compound, a yellow-colored precipitate will form. In the
presence of an alcohol, the solution will remain translucent yellow, forming no
precipitate.

O2N O2N
O

H2N HN NO2 + C C N HN NO2 + H2O

Carbonyl group
2,4-dinitrophenylhydrazine Cloudy from the
insoluble product

O2N

H2N HN NO2 + C OH No Reaction -- NR

clear solution
2,4-dinitrophenylhydrazine Any alcohol

D. Fehling’s test: This test is very specific for aldehydes; only aldehydes will give
a positive result. Any alcohol or ketone will give a negative result. It is based
upon the ability of the aldehyde group to reduce the Cu+2 ion of Cu(OH)2 (which
is blue) to the Cu+1 ion of Cu2O (which is dark red) in the presence of a base.

O O

+ 2Cu(OH)2 + NaOH + Cu 2O + 3H 2O
C C
R H R O-
Na+

Aldehyde Carboxylate ion

Any other group

(alcohols, ketones) + 2Cu(OH) 2 + NaOH NR -- No reaction

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Here is a summary table of all the reactions:
Reaction Chemical Positive Negative Groups that Groups that
result (seen) result (seen) give positive give
result negative
result
Potassium K2Cr2O7 Orange to Remains 1° and 2° Ketones,
dichromate green, blue or orange alcohols, 3° alcohol
Oxidation blue/green aldehydes
Lucas test ZnCl2 and HCl Clear to Remains clear Secondary Primary
(to distinguish cloudy alcohol- slow alcohol,
alcohols) Tertiary Aldehydes,
alcohol-fast ketones
2,4- 2,4- Form yellow/ No solid Aldehydes, All alcohols
dinitrophenyl- dinitrophenyl- orange solid formed Ketones
hydrazine test hydrazine
(aldeydes,
ketones from
alcohols)
Fehling’s Test Cu(OH)2 Blue to Remains blue Aldehydes Ketones
(aldehydes and OH- something All alcohols
from ketones) else (red,
green yellow)
Experimental Procedure: You will perform each test indicated on 6 solutions (an
aldehyde, a ketone, a primary alcohol, a secondary alcohol, a tertiary alcohol and the
assigned unknown), and fill the results in on the tables provided on the Report Sheet.
Based on the results of the tests with the known solutions and the unknown, you
deduce which functional group (not which compound) is in the unknown. As part of
the report, write a paragraph explaining the reasoning used to identify the functional
group present in the unknown. This paragraph should discuss the tests performed, the
results of each test, and how the results confirmed or ruled out certain functional
groups, allowing identification the functional group in the unknown. There are also four
questions at the end of the report to be answered.

Procedure:
Use clean test tubes for all these tests – wash them out between tests so
that cross-contamination does not occur. DO NOT HEAT STOPPERED
TUBES -- REMOVE STOPPERS BEFORE HEATING!

DO NOT rinse out tubes with acetone! Since acetone is a known solution in
this procedure, rinsing out tubes with acetone will contaminate the tubes
and invalidate results. Wash tubes out with soap and water, using
deionized water as a final rinse. Tubes do not need to be dry for these
procedures.

Except for testing the assigned unknown solution (which you must do
individually), you may work in pairs for this experiment unless directed
otherwise by your instructor.

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 Before starting the procedure, fill a 600-mL beaker slightly less than
halfway with tap water to begin heating for the water baths needed on
two parts of the procedure

Remember the definition of “precipitate”: it isn’t just particulate or

“clumpy” particles; a change in the cloudiness (becoming more cloudy) is
also indicative of a precipitate – the cloudiness represents very fine
particles that do not settle out!

Use the bottle marked “ethanol” as a known primary alcohol solution; use
the bottle marked “95% ethanol” as the solvent in the 2,4-
dinitrophenylhydrazine test (given in the directions for that test).

A. Oxidation by K2Cr2O7: Place 3 mL (about 60 drops) of 5% aqueous K2Cr2O7 in a

50 mL beaker. Carefully add 1 mL (about 20 drops) of concentrated sulfuric acid (if
a precipitate appears at this point, carefully swirl until it dissolves). Slowly (a few
drops at a time with mixing) add 2 mL of the solution to be tested. If the color of
the solution changes to green or blue-green, then oxidation has taken place (the
Cr+6 ion has been reduced to the Cr+3 ion) and the reaction is positive; if no color
change takes place, then the reaction is negative. This procedure must be
performed for each of the 5 known solutions and the unknown, and the results
recorded in your notebook for the Report Sheet. When you have completed
these tests, be sure to place the chromium waste into the proper waste
bottle. Then rinse out beaker with water (tap water is acceptable) and
add this to the waste bottle. Chromium is very toxic, and should NEVER
go down the sink!
B. Lucas test: Place 10 drops of the solution to be tested into a labeled test tube.
Add approximately 30 drops of Lucas reagent. Stopper with a cork and shake
vigorously for a few seconds. Allow mixture to stand at room temperature and
observe how long it takes for any precipitate (cloudiness) to form. If no cloudiness
is observed after 15 minutes, warm the unstoppered test tube in a 60-75 °C water
bath for 15 minutes. Observe the results. Record the results, including the amount
of time taken for the reaction to occur, and temperature at which the reaction
occurred. Sample results might include: immediate cloudiness (immediate
positive reaction), cloudiness after 5 minutes at room temperature (slightly delayed
positive reaction), cloudiness after 3 minutes in 60° C water bath (delayed positive
reaction), no cloudiness after 15 minutes in 60°C water bath (negative reaction). A
yellow or yellow-orange color without any precipitate is a negative result. This
procedure must be performed for each of the 5 known solutions and the unknown,
and the results recorded in your notebook for the Report Sheet.
C. 2,4-dinitrophenylhydrazine test: Place 5 drops of the solution to be tested into
a labeled test tube. Add 10 drops of 95% ethanol (as a solvent) and then add 5
drops of the 2,4 dinitrophenylhydrazine reagent to the tube and mix. Observe the
results. A positive result is the formation of a yellow/orange precipitate. A negative
test result is the absence of a precipitate, and the persistence of the translucent

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 solution. This procedure must be performed for each of the 5 known solutions and
the unknown, and the results recorded in your notebook for the Report Sheet.
When you have completed these tests, be sure to place the 2,4-
dinitrophenylhydrazine waste into the proper waste bottle. Then rinse
out tubes with water (tap water is acceptable) and add this to the waste
bottle. 2,4-dinitrophenylhydrazine is very toxic, and should NEVER go
down the sink!
D. Fehling’s test: Place 15 drops of Fehling’s reagent (Part A) and 15 drops of
Fehling’s reagent (Part B) into a labeled test tube and mix. Add 10 drops of the
solution to be tested; stopper the tube and shake for a few seconds. Remove the
stopper and place the tubes in a boiling water bath for five minutes. Observe the
results. A positive result is the formation of a brick red precipitate. A negative result
is the absence of a precipitate, and the persistence of the blue solution. This
procedure must be performed for each of the 5 known solutions and the unknown,
and the results recorded in your notebook for the Report Sheet.

To figure out your unknown you may construct a table (like this one) in your notebook
to help keep track of results filling by “positive” or “negative” depending upon your
results in lab. If you use a table like this, put it in your notebook and fill in results
there. Don’t fill out this sheet and NOT put this information in your notebook.
Test: Chromate Lucas test: 2,4- Fehling’s test
oxidation dinitrophenyl-
hydrazine
1° alcohol (ethanol)

2° alcohol (2-
propanol)
3° alcohol (2-methyl-
2-propanol)
Aldehyde
(formaldehyde)
Ketone (acetone)

Your unknown:

The pattern of positive and negative results for your unknown should match the
pattern for one of the known solutions to identify the functional group of your
unknown. If no patterns match, an error in testing/reporting was made, either
with one of the known solutions or the unknown solution in one of the tests.
You can determine the error and repeat the erroneous tests. Your instructor can
help you determine which tests to repeat.

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Lab partner(s) ________________________ Notebook points/initials __________

Date ______________________ Name ___________________________

REPORT FOR LAB PROCEDURE 3:

ALCOHOLS, ALDEHYDES, AND KETONES

The unknown assigned to you is number________________

You will be testing six solutions (five with known functional groups and one will be an unknown
functional group) with each of the four tests. Record all experimental data in your notebook;
this report sheet is for your final report only.

Draw structures of these molecules which illustrate the FIVE known functional groups tested
here (draw the structure above the name).

(A) ethanol (1º alcohol) (B) 2-propanol (2º alcohol) (C) 2-methyl-2-propanol (3º alcohol)

(D) formaldehyde (aldehyde) (E) acetone (ketone)

Test #1: Oxidation by K2Cr2O7

Observation of test results Conclusion
(Did the color or odor change? Did the solution become (is test positive
cloudy or clear? How fast did any changes occur?) or negative?)
Solution tested:
ethanol

2-propanol

2-methyl-2-propanol

formaldehyde

acetone

assigned unknown

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Test #2: Lucas test
Observation of test results Conclusion
(Did the color or odor change? Did the solution become (is test positive
cloudy or clear? How fast did any changes occur?) or negative?)
Solution tested:
ethanol

2-propanol

2-methyl-2-propanol

formaldehyde

acetone

assigned unknown

Test #3: 2,4-Dinitrophenylhydrazaine test

Observation of test results Conclusion
(Did the color or odor change? Did the solution (is test
become cloudy or clear? How fast did any changes positive or
occur?) negative?)
Solution tested:
ethanol

2-propanol

2-methyl-2-propanol

formaldehyde

acetone

assigned unknown

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Test #4: Fehling’s test
Observation of test results Conclusion
(Did the color or odor change? Did the solution (is test
become cloudy or clear? How fast did any changes positive or
occur?) negative?)
Solution tested:
ethanol

2-propanol

2-methyl-2-propanol

formaldehyde

acetone

assigned unknown

The functional group of your unknown is:__________________

Write a paragraph explaining how you arrived at the conclusion concerning the functional group
of the unknown. This should include what tests you performed, the results, and how the
results confirmed or ruled out certain functional groups, so that you could conclude the type of
functional group in the unknown.

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Answer the following questions:

1. Is ethanol a primary, secondary, or tertiary alcohol? Write out the structures of

ethanol and also any oxidation products of ethanol. If there is more than one
oxidation product, give the structure of each of the products.

2. Is 2-propanol a primary, secondary, or tertiary alcohol? Write out the structures of

2-propanol and also any oxidation products of 2-propanol. If there is more than
one oxidation product, give the structure of each of the products.

3. Is 2-methyl-2-propanol a primary, secondary, or tertiary alcohol? Write out the

structures of 2-methyl-2-propanol and also any oxidation products of 2-methyl-2-
propanol. If there is more than one oxidation product, give the structure of each
of the products.

4. 2-Propanol is the IUPAC systematic name of this alcohol. It has a common name
by which it is much better known (You’ll see it in the grocery store or pharmacy).
Give that common name.

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