Identification of an Unknown: Alcohol, Aldehyde or Ketone?

L. A. Meyer and R. E. Glaser

Introduction

Organic chemists often face the problem of identifying an “unknown” compound.

Sometimes it is a substance obtained from a chemical reaction. In such case, the chemist knows
what starting materials were used (where it came from), and a general structure can be derived,
but confirmation is still necessary. Other times, one might be confronted with a newly isolated
natural product and a complete characterization is essential.
Many tools are available to the modern chemist for compound identification. Recent
developments in chromatographic methods and spectroscopic techniques have made the
characterization a lot easier. Before all these techniques were available, chemists had to rely on
a systematic method of qualitative analysis. A series of classic tests were performed to identify
the structure of an unknown sample. These qualitative tests rely on the detection of the presence
of certain functional groups.
Basic physical properties, like solubility, melting point and boiling point are also useful.
These properties can be compared with published values in reference books such as the
Handbook of Tables for Organic Compound Identification, 3rd Edition (Rappaport, Z., Ed.;
CRC Press: Boca Raton, Fla, 1967). Of course you can only compare if the compound had been
characterized in the past.
There is often the option of converting the unknown solid or liquid into a second
compound that is a solid. This new solid compound is called a derivative of the unknown. The
melting point of these derivatives, also found in reference books, are used in conjunction with
the results obtained from the qualitative chemical and physical tests to reduce the number of
possible identities. When the list of possibilities is limited, as it will be in this experiment, one
should be able to single out and identify the subject without a doubt.
The scope of the investigation for this experiment has been narrowed down to the list of
alcohols, aldehydes and ketones listed in Tables 1 and 2. These compounds are all liquids. Their
boiling point and the melting point of the corresponding derivatives, along with a series of
qualitative tests will be used to identify the unknown assigned to you. No spectroscopic or
chromatographic instrumentation will be used, and you will have to rely on your understanding
of the chemistry of each test. Prepare yourself, so you will know the meaning of each test result.
A set of standards (known samples) will be tested each time along with your unknown.
These standards will show what a positive and a negative result looks like and you will do a
direct comparison with your unknown. In some cases, it will be a good idea to run a “blank”
solvent sample. Solvents can sometimes contain impurities that will conclude in a false positive
result. You will want to make sure that it is your sample reacting and not something else.
As a pre-laboratory assignment, set up a flow chart to guide you through your
investigation. Indicate the possible results for each test and what they suggest. In Tables 3 and
4, fill in what you expect to see for each compound listed. This will help you eliminate possible
suspects as you go along.

1
Test of Physical Properties

Boiling Point Determination

Several boiling point methods are available, using miniscale and microscale techniques.
An example of a miniscale technique uses 0.5 to 1 ml of your liquid in a long narrow Pyrex test
tube equipped with a boiling chip. A thermometer is suspended 2 cm above the liquid level.
Then one heats the sample until a condensation ring is observed, without allowing any vapor to
escape out of the test tube. The thermometer bulb has to be fully immersed in the vapor of the
boiling liquid and the measurement is taken when the vapor and the liquid reach equilibrium. A
boiling point can also be measured using a simple distillation apparatus, as we will do in this
experiment. The amount of solvent needed depends on the size of the apparatus, but it is usually
more than 5 ml. Once you have determined the boiling point, you can eliminated any compound
on the list with a boiling point ±10 °C of the measured value. This range allows some room for
error during the determination and for differences in atmospheric pressure.

Water Solubility Test

The solubility of a compound in water gives you an indication of its polarity and, in the
case of alcohols, aldehydes and ketones, of their size. Alcohols, aldehydes and ketones with low
molecular weight (up to about four carbons) will be more polar and therefore more soluble in
water. The polar fragment that contains the carbonyl or the –OH group will become a smaller
and smaller part of the entire molecule as the alkyl group length increases, and, thus, their
solubility in water will also decrease significantly as the alkyl chain lengthens.

2
Test of Chemical Properties

Preparation of the 2,4-Dinitrophenylhydrazone Derivative

2,4-Dinitrophenylhydrazine reacts with aldehydes and ketones to form brilliant red or

yellow Schiff bases. These bases will precipitate from the reaction mixture and can be
recrystallized. The melting points of these solid derivatives can be used for confirmation of the
identity of your unknown. (see Table 2). Alcohols will not react with 2,4-
dinitrophenylhydrazine (no precipitate will be observed); therefore this test will help you
determine whether your unknown is an alcohol or a carbonyl compound.

R'
H
NHNH2 N
O N R
+
- H2O
O2N NO2 R R' O2N NO2

R = alkyl group or H
R' = alkyl group

Lucas Test

The Lucas test is used to differentiate between primary, secondary and tertiary alcohols.
A solution of zinc chloride in concentrated HCl is used to convert the alcohol to the
corresponding alkyl chloride. The alkyl chloride formed is insoluble and the solution will
become cloudy. This reaction follows a SN1 mechanism. The presence of ZnCl2, a Lewis acid
acting as a catalyst, increases the reactivity of the alcohols towards HCl. Those alcohols leading
to the most stable tertiary carbocation intermediate react the fastest, followed by secondary
alcohols. Primary alcohols will not react.

ZnCl 2
R OH + HCl R Cl + H2O

3° – immediate cloudiness, fast reaction.

2° – cloudiness after 2-5 minutes, slow reaction.
Some 2° alcohols might require some warming up.
1° – solution remains clear, no reaction.

Allylic and benzylic alcohols are exceptions. These alcohols form resonance stabilized
carbocations and this stabilization mechanism increases their reactivity. A primary allylic or
benzylic alcohol will react as would be expected for a 2° alcohol. A major limitation for the
Lucas test is that only water-soluble alcohols can be tested.

3
Chromic Acid Test

The chromic acid test, also known as the Jones test, is based in the chromic acid
oxidation of the alcohols and aldehydes to the corresponding carbonyl compound. Primary
alcohols and aldehydes are oxidized to carboxylic acids. Secondary alcohols are converted to
ketones. Tertiary alcohols and ketones do not react.

1° Alcohol: 3 RCH2OH + 4 H2CrO4 + 12 H+ → 3 RCO2H + 4 Cr+3 + 13 H2O

Aldehyde: RCHO + H2CrO4 + 4 H+ → RCO2H + Cr+3 + 3 H2O

2° Alcohol: 3 RCHOHR’ + 2 H2CrO4 + 6 H+3 → 3 RCOR’ + 2 Cr+3 + 8 H2O

3° Alcohol: R3COH + H2CrO4 → No Reaction

Ketone: R2CO + H2CrO4 → No Reaction

During this test a red-orange Cr(IV) compound is reduced to a blue-green Cr(III)

compound. Sometimes a blue-green precipitate also will be observed. This color change will
serve as verification that a reaction has taken place and that the alcohol or aldehyde has been
oxidized. Aliphatic aldehydes will react within 5 seconds with a precipitate formation within 30
seconds. Aromatic aldehydes will require 30 to 45 seconds. It is important to run a solvent
(acetone) blank for this reaction, which should not turn blue for at least 3 seconds.

Preparation of the 3,5-Dinitrobenzoate Derivative

Alcohols will react with 3,5-dinitrobenzoyl chloride to form the corresponding 3,5-
dinitrobenzoate (3,5-DNB) ester derivatives.

O O

O2N O2N
Cl OR

+ ROH

NO2 NO2

These crystalline derivatives can be easily characterized by their melting points, many of which
can be found in reference books (see Table 1).

4
Iodoform Test

Aldehydes and ketones with α-hydrogens are halogenated in the α-position when treated
with halogens in the presence of base. All three α-hydrogens of the methyl group in methyl
ketones and acetaldehyde are substituted with iodine (brown color) during the iodoform test.
The excess base then reacts with the halogenated intermediate and gives iodoform (HCI3), an
insoluble yellow solid.

O I2, KI O O
H2O, NaOH NaOH

R CH3 -HCI3
R CI3 R O-Na +
Iodoform

Alcohols with a hydroxymethyl group also give a positive test. The alcohol is initially
oxidized by the hypoiodite formed in the basic solution. A methyl ketone intermediate is formed
that subsequently reacts with the excess base.

OH

R CH3

I2, KI
H2O, NaOH

O I2, KI O O
H2O, NaOH NaOH

R CH3 -HCI3
R CI3 R O-Na +
Iodoform

Notice that it is important that the alcohol possesses at least one hydrogen at the hydroxyl-
substituted carbon. Therefore tertiary alcohols will not give a positive test.
If the carbonyl compound or the alcohol is not soluble in water, an alternative procedure
is necessary. The unknown is first dissolved in 1,2-dimethoxyethane (DME). To this solution,
diluted NaOH is added, followed by addition of the iodine solution. The resulting mixture is
diluted with water and precipitation of iodoform indicates a positive test.

5
Purpald® Test

The Purpald® reagent is the heterocyclic compound 4-amino-3-hydrazino-5-mercapto-

1,2,4-triazole developed by Aldrich Chemical Company. It reacts with aldehydes to form a
cyclic derivative and water. The cyclic derivative is then oxidized by exposure to air and forms
an intensely colored (usually purple) product. Although both aldehydes and ketones react with
the reagent to give the initial adduct, only the aldehyde adduct has a C-H bond in the six-
membered ring, which can be oxidized to give the final product.

NH2
O NH2
N
+ HS NH
R H
N N

- water

intensely
colored R R
product H
air ox.

N HN NH
N

N N
HS N HS NH

N N N N

6
 Table 1. Possible Alcohol Unknowns

Alcohol Boiling Point (°C) Melting Point (°C)

3,5-Dinitrobenzoate
Derivative

Methanol 65 108
Ethanol 78 93
2-Propanol 82 123
2-Methyl-2-propanol 83 142
1-Propanol 97 74
2-Propen-1-ol 97 49
2-Butanol 100 76
2-Methyl-2-butanol 102 117
2-Methyl-1-propanol 108 87
3-Pentanol 116 101
1-Butanol 118 64
2,3-Dimethyl-2-butanol 120 111
2-Pentanol 120 62
3,3-Dimethyl-2-butanol 120 107
2-Methyl-2-pentanol 123 72
2-Methyl-1-butanol 130 70
3-Methyl-1-butanol 132 61
3-Hexanol 136 97
1-Pentanol 138 46
Cyclopentanol 141 115
1-Hexanol 158 58
Chyclohexanol 160 113
Furfuryl alcohol 172 81
1-Heptanol 177 47
Tetrahydrofurfuryl alcohol 177 83
1-Octanol 195 61
1-Phenylethanol 204 95
Benzyl alcohol 206 113

(a) Data taken from the Handbook of Tables for Organic Compound Identification,
3rd Edition (Rappaport, Z., Ed.; CRC Press: Boca Raton, Fla, 1967), pp 80-87.

7
 Table 2. Possible Aldehyde and Ketone Unknowns

Aldehyde or Ketone Boiling Point (oC) Melting Point (°C)

2,4-Dinitrophenyl-
hydrazone Derivative

Isobutyraldehyde 64 187
2-Methyl-2-propenal 74 206
Butanal 75 123
2-Methylbutanal 92 120
Pentanal 103 98
3,3-Dimethylbutanal 103 147
2-Butenal 104 190
Hexanal 131 104
2-Methyl-2-pentenal 137 159
Tetrahydrofurfural 142 134
Heptanal 155 109
Furfural 162 212
2-Ethylhexanal 163 114
Benzaldehyde 179 237
4-Tolualdehyde 204 233

2-Butanone 80 116
1-Pentene-3-one 102 129
3-Pentanone 102 156
3,3-Dimethyl-2-butanone 106 125
4-Methyl-2-pentanone 117 95
5-Hexene-2-one 132 108
Cyclopentanone 131 146
4-Heptanone 144 75
3-Heptanone 148 101
2-Methyl-4-heptanone 150 124
Cyclohexanone 156 162
6-Methyl-2-heptanone 171 77

(a) Data taken from the Handbook of Tables for Organic Compound Identification, 3rd Edition
(Rappaport, Z., Ed.; CRC Press: Boca Raton, Fla, 1967), pp. 144-149 and 161-168.

8
Experiment 7

A series of qualitative physical and chemical tests will be performed on an unknown

alcohol, aldehyde or ketone to identify the compound. Solid derivatives will be prepared to
determine their melting points and thereby confirming the structure of the unknown.

Safety: 2,4-Phenylhydrazine is a possible mutagen and may cause skin

sensitization. Handle these reagents with care and avoid skin contact.
Chromium compounds are toxic, and some a carcinogenic. The
solutions used in the Jones test and the Lucas test are highly
corrosive. Dispose of waste from all these tests in the containers
provided. 3,5-Dinitrobenzoyl chloride is lachrymatory and
hydrolyzes in moist air to produce HCl. Pyridine is foul smelling and
toxic, handle in the hood at all times.

Obtain a sample of your unknown and record the identification number. You will have 8
ml to do all your tests and derivative preparation. Use prudent amounts for each test so you
don’t run out!
Place the entire sample in a 25 ml round-bottom flask add a boiling chip, and attach to a
simple distillation apparatus. Determine and record the boiling point by distilling a small
amount of the sample. Combine the distillate and the liquid remaining in the round-bottom flask
for subsequent tests.
Fill a clean test tube with 2 ml of water and add two drops of your unknown. Examine
closely to see if the sample has dissolved completely. Record your observations on water
solubility.
To determine whether you have an alcohol or a carbonyl compound, you will attempt to
prepare the 2,4-dinitrophenylhydrazone derivative. A yellow to red precipitate formation
indicates the presence of an aldehyde or a ketone. Place 5 ml of 2,4-dinitrophenylhydrazine
reagent in a test tube and add about 10 drops of your unknown. Stir with a glass rod vigorously
for 1-2 minutes. If no immediate reaction is observed, stopper the test tube and allow the
solution to stand for 15 more minutes (you can proceed with the chromic acid test or the
iodoform test while you wait). If a precipitate forms, decant the liquid, add 3 ml of fresh cold
water and mix thoroughly with a stirring rod pulverizing the solid (this process is known as
trituration). Decant the aqueous phase and recrystallize the remaining solid from a minimum
amount of hot 95% ethanol. Let the solution sit undisturbed until it has reached room
temperature, then place the test tube in an ice-water bath (prepared in a small beaker) to
maximize the formation of crystals. If no crystals form after cooling, reheat the ethanol solution
and add water dropwise until the first persistent cloudiness is observed. Allow the solution to
cool again as described above. Isolate the crystals using vacuum filtration and rinse them with
cold ethanol. Allow the crystals to dry in the Buchner funnel with suction for 10 minutes.
Determine and record the melting point.
Now you have resolved whether you have an alcohol or a carbonyl compound and you
will have to choose from the remaining classification tests according to your results.
If your unknown alcohol is water-soluble you can perform the Lucas test. Place 1 ml of
the Lucas reagent in a test tube and add 2-3 drops of the alcohol. If the solution remains clear

9
after 30 seconds, warm up the test tube a bit and allow to stand for 5 minutes. Remember 3o
alcohols and 2° allylic alcohols react the fastest, followed by 2° alcohols, which sometimes need
warming up. Primary alcohols do not react. Everyone with an unknown alcohol (water-soluble
or not) should perform the test on the following standards: Ethanol, 2-propanol and 2-methyl-2-
propanol. Record your observations.
For the chromic acid test, place 1 ml of acetone and 2 drops of the chromic acid reagent
in a test tube. Add 2 drops of your alcohol, aldehyde or ketone, and mix. Tertiary alcohols and
ketones will not react, while 1° alcohols, 2° alcohols and aldehydes will turn the red-orange
solution into a blue-green solution. If you have an unknown alcohol try the test on ethanol, 2-
propanol and 2-methyl-2-propanol also. If your unknown is an aldehyde or a ketone, try the test
on 2-butanone, butanal and benzaldehyde. Remember to run an acetone blank too. Record your
observations.
To run the iodoform test for water-soluble compounds, dissolve 2 drops of the compound
in 1 ml of water. Then add 1 ml of 10 % NaOH solution. Finally, add 2 ml of iodine-potassium
iodide solution and mix. A positive test is indicated by the formation of a yellow precipitate.
Test 2-propanol and 2-methyl-2-propanol standards for reference of a positive and a negative
result, respectively. If your sample is not water soluble, dissolve 2 drops of the compound in 1
ml of 1,2-dimethoxyethane. Then add NaOH and iodine solutions as described above. The
mixture is then diluted with 5 ml of water. Record your observations.
For the Purpald test, dissolve 100-200 mg (spatula-tip full) of the Purpald reagent in 2
ml 5% NaOH. Transfer about 0.5 ml of the solution into each of three test tubes. Add 1 drop of
your unknown to one of the test tubes and shake the mixture vigorously. Allow air contact and
record any color change. Test two standards in the remaining test tubes: 2-butanone and
benzaldehyde.
To confirm the structure of your unknown alcohol, prepare the 3,5-dinitrobenzoate
derivative. For a 1 ° and 2 ° alcohol, place 0.5 ml of the alcohol in a test tube and add 200-300 mg
of 3,5-dinitrobenzoyl chloride. Warm up gently in a hot water bath for 5 minutes. Allow the
mixture to cool and add 5 ml of 2 % Na2CO3. Triturate the solid formed with a glass rod, and
continue stirring for ~1 minute to ensure mixing. The ester remains insoluble, but the aqueous
base hydrolyzes any unreacted acid chloride, and removes the resulting 3,5-dinitrobenzoic acid.
Decant the aqueous phase and the crude ester is triturated with 3 ml of cold water. Decant the
aqueous phase again. Recrystallize the remaining solid from a minimum amount of hot 95 %
ethanol. Let the solution sit undisturbed until it has reached room temperature, then place the test
tube in an ice-water bath to maximize the formation of crystals. If no crystals form after cooling,
reheat the ethanol solution and add water dropwise until the first persistent cloudiness is
observed. Allow the solution to cool again as described above. Isolate the crystal using vacuum
filtration and rinse them with cold ethanol. Allow the crystals to dry in the Buchner funnel with
suction. Determine the melting point of the derivative.
Turn in your derivative crystals in a labeled container and return the remaining unknown
to your TA.

10
Post-laboratory Questions

1. What is the identity of your unknown? Outline the logical thought process that led you to this
conclusion.

2. Show chemical equations for the reactions of your unknown in the tests that you performed.
If there is no reaction, then explain why.

3. Describe how you could do simple chemical tests to differentiate between: 2-Methyl-3-
pentanol, 3-methyl-3-pentanol and 3-methyl-2-pentanol.

11
 Table 3. Chart to Record Expected Tests Results on Alcohols

Alcohol BP (°C) Solubility Lucas Chromic Iodoform 3,5-DNB

Test Acid Reaction MP (°C)
Methanol 65 108
Ethanol 78 93
2-Propanol 82 123
2-Methyl-2-propanol 83 142
1-Propanol 97 74
2-Propen-1-ol 97 49
2-Butanol 100 76
2-Methyl-2-butanol 102 117
2-Methyl-1-propanol 108 87
3-Pentanol 116 101
1-Butanol 118 64
2,3-Dimethyl-2-butanol 120 111
2-Pentanol 120 62
3,3-Dimethyl-2-butanol 120 107
2-Methyl-2-pentanol 123 72
2-Methyl-1-butanol 130 70
3-Methyl-1-butanol 132 61
3-Hexanol 136 97
1-Pentanol 138 46
Cyclopentanol 141 115
1-Hexanol 158 58
Chyclohexanol 160 113
Furfuryl alcohol 172 81
1-Heptanol 177 47
Tetrahydrofurfuryl alcohol 177 83
1-Octanol 195 61
1-Phenylethanol 204 95
Benzyl alcohol 206 113

Use the ChemFinder to determine the structures of alcohols with trivial names.

12
 Table 4. Chart to Record Expected Tests Results on Aldehydes and Ketones

Aldehyde or Ketone BP (°C) Solubility 2,4-DNPH Iodoform Chromic Purpald®

MP (°C) Reaction Acid
Isobutyraldehyde 64 187
2-Methyl-2-propenal 74 206
Butanal 75 123
2-Methylbutanal 92 120
Pentanal 103 98
3,3-Dimethylbutanal 103 147
2-Butenal 104 190
Hexanal 131 104
2-Methyl-2-pentenal 137 159
Tetrahydrofurfural 142 134
Heptanal 155 109
Furfural 162 212
2-Ethylhexanal 163 114
Benzaldehyde 179 237
4-Tolualdehyde 204 233

2-Butanone 80 116
1-Pentene-3-one 102 129
3-Pentanone 102 156
3,3-Dimethyl-2-butanone 106 125
4-Methyl-2-pentanone 117 95
5-Hexene-2-one 132 108
Cyclopentanone 131 146
4-Heptanone 144 75
3-Heptanone 148 101
2-Methyl-4-heptanone 150 124
Cyclohexanone 156 162
6-Methyl-2-heptanone 171 77

Use the ChemFinder to determine the structures of carbonyl compounds with trivial names.

13