KUMASI POLYTECHNIC

CHEMICAL ENGINEERING DEPARTMENT

CHEMICAL ENGINEERING LAB. II

ORGANIC CHEMISTRY PRACTICALS (CME 208)

REPORT ON IDENTIFICATION OF ALCOHOLS

AND PHENOLS

BY SALIFU MUSAH (CME05061081)

DATE OF EXPERIMENT: 12TH MARCH, 2010

DATE SUBMITTED: 19TH MARCH, 2010

SUPERVISOR: MR. ISAAC FRIMPONG

 INTRODUCTION
Specific groups of atoms in an organic molecule can be used in determining its physical and
chemical properties. These groups are referred to as functional groups. Organic compounds which
contain the functional group –OH (hydroxyl group) are called alcohols.

Alcohols are important commercially and include use as solvents, drugs, and disinfectants.
The most widely use alcohols are methanol or methyl alcohol (CH3OH), ethanol or ethyl alcohol
(CH3CH2OH), and 2-propane or isopropyl alcohol ((CH3)2CHOH).

The general formula of an alcohol is ROH in which the R is an aliphatic hydrocarbon group.
Alcohols may be looked upon as derivatives of water, HOH. One hydrogen of water is substituted
by an alkyl group, R. Like water, alcohols show hydrogen bonding. As the chain of the R group
increases the hydrocarbon character of the compound overshadows the polar character of the OH
group. Consequently, the solubility and boiling point of an alcohol are affected by the length of the
carbon chain and the shape of the molecule. The short chain alcohols are soluble in water, whereas
the longer chain alcohols are insoluble in water. In general a molecule which is more compact (i.e.,
more branched) will be more soluble in water and will have a lower boiling point than the straight
chain isomer.
The hydroxyl group present in all alcohols is a polar functional group. The polarity of this
group allows alcohols to form hydrogen bonds. Small chain alcohols are able to mix with water because
of the hydrogen bonding interactions that will occur between the hydroxyl functional group and the water. If
the R-group of the alcohol becomes too large however, the solubility of the alcohol will decrease.
Although alkyl alcohols have an -OH group, they do not ionize in water, whereas phenols
ionize like acids (donating a proton to water). The -OH group of alkyl alcohols can be positioned on
different carbon atoms of the carbon chain and are classified as primary (1º), secondary (2º), or
tertiary (3º) alcohols depending on whether the -OH group is attached to a carbon with 1, 2 or 3
other carbon atoms attached to it.

CH3
CH3
CH3 C OH
CH3 CH2 OH CH3 CH OH
CH3
ethanol 2-propanol 2-methyl-2-propanol
(primary) (secondary) (tertiary)

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 These different alcohols react differently with Lucas reagent and with Bordwell-Wellman
reagent; hence these reagents can be used for identifying the class of alcohol. The relative acidity of
phenols can be used to characterize this class of alcohols relative to the alkyl alcohols.
Phenols are aromatic alcohols, in which R is an aromatic ring. This experiment will
demonstrate some of the properties of alcohols and phenols.
Phenols are closely related to alcohols because of the presence of the hydroxyl (OH) group.
In phenols, however, the hydroxyl group is directly bonded to an aromatic group, such as benzene.
Phenol compounds often have curious but useful properties. Some are found in preservatives or
medications. The chemistry of phenols is different than that of alcohols. Concentrated solutions of
the compound phenol are quite toxic and can cause severe burns.

OBJECTIVES
1. To observe the solubility of alcohols relative to their chemical structure.
2. To determine the characteristics chemical reactions of alcohols and phenols of an organic
compound.
3. To use chemical characteristics to distinguish primary, secondary and tertiary alcohols and a
colour test will be performed for phenol.

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SOLUBILITY TEST
Some liquids, such as water and alcohol, can dissolve in each other in any proportion.
The solubility of a compound in a given solvent at a given temperature and pressure thus is defined
as the maximum amount of that compound that can be dissolved in the solution. Solubility increases
with the increasing temperature of the solvent for most substances. For some substances, such as
gases or the organic salts of calcium, solubility in a liquid increases with a lowering of temperature.
In general, solutions with molecules that is structurally similar to the molecules of the solvent have
the highest solubility. For example, ethyl alcohol (C2H5OH)
R Hydrogen bonding
and water (HOH) have structurally similar molecules and O

are highly soluble in one another. Alcohols are highly H

.
.
soluble in water because the polar OH groups in water and .
O
alcohols make the two associate through hydrogen bonding H
when they are put together. H

FERRIC CHLORIDE TEST

The ferric chloride test is a traditional colourimetric test for phenols, which uses a 1% iron (III)
chloride solution that has been neutralised with sodium hydroxide until a slight precipitate of FeO
(OH) is formed. The mixture is filtered before use. The organic substance is dissolved in water,
methanol or ethanol, then the neutralised iron (III) chloride solution is added—a transient or
permanent colouration (usually purple, green or blue) indicates the presence of a phenol or enol.

OH OFeCl2
+ FeCl3 + HCl

CHROMIC TEST OR BORDWELL-WELLMAN TEST

The Bordwell-Wellman test solution contains potassium dichromate dissolved in sulphuric acid. It
is an orange-yellow solution. The orange-yellow colour is due to the Cr 2O7 ion. The oxidation
number of chromium is +6. This reagent will oxidize primary and secondary alcohols and, in turn,
becomes reduced. The chromium in dichromate is reduced to chromic ion, Cr 3+. A greenish
coloured solution results. This colour change from orange-yellow to green serves as an indicator for
the presence of a primary or secondary alcohol. A primary alcohol is oxidized first to an aldehyde,
which will be further oxidized to an acid.

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IODOFORM TEST

The iodoform test is a test for compounds that contain either of the following groups:

CH3 CH3

C=O OR H C OH

R R

This includes ethanal and ethanol. If a methyl secondary alcohol is used it will be oxidised to the
methyl ketone before the main part of the process takes place. The compound being tested is reacted
with iodine in sodium hydroxide solution or sodium chlorate (I) and potassium iodate solution. A
bright yellow precipitate of iodoform indicates a positive test. The reaction starts with the
substitution of the hydrogens in the methyl group for iodine atoms. This causes a great withdrawing
of electrons from the C-C bond joining the methyl group to the ketone group, allowing nucleophillic
attack and fission of the bond:

 KMnO4 TEST

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PROCEDURE

APPARATUS AND REAGENTS

Test tubes, Bordwell-Wellman reagent, n-butyl alcohol (1-butanol), secondary-butyl alcohol (2-
propanol), tertiary-butyl alcohol , resorcinol, ferric chloride solution, 6M NaOH, I2-KI reagent,
acetone, KMnO4, 250ml beaker, dropper, water bath and test tube holders.

SOLUBILITY TEST
1. 10 drops of each, 1-butanol, 2-propanol, tertbutyl alcohol and resorcinol were placed in a
clean dry separate test tube.
2. 3ml of distilled water were added to each solution and shaken.
3. The observations were recorded on a reported sheet.

FERRIC CHLORIDE TEST

1. 5 drops of each, 1-butanol, 2-propanol, tertbutyl alcohol and resorcinol were placed into
separate clean dry test tubes.
2. 2 drops of ferric chloride solution was added to each solution.
3. Any colour changes were noted.
4. The observations were recorded.

CHROMIC ACID TEST

1. 3 drops of each, 1-butanol, 2-propanol, tertbutyl alcohol and resorcinol were placed into
separate clean dry test tubes.
2. To each test tube 3 drops of acetone and 3 drops of chromic acid were added and warmed in
a water bath at a temperature of 60ºC for 5 minutes.
3. After heating the colour changes were observed.
4. The results were recorded.

IODOFORM TEST
1. 5 drops of each, 1-butanol, 2-propanol, and tertbutyl alcohol were placed into separate clean
dry test tubes.
2. To each test tube 15 drops of 6M NaOH and drops of I2-KI reagent were added and warmed
in a water bath.
3. After heating the colour changes were observed.
4. The results were recorded.

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KMnO4 TEST
1. 2ml of each, 1-butanol, 2-propanol, and tertbutyl alcohol were placed into separate clean dry
test tubes.
2. To each test tube 2ml of KMnO4 were added and shaken.
3. The colour changes were observed.
4. The results were recorded.

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DATA
Table 2.0 SOLUBILITY TEST
TEST OBSERVATION INFERENCE
10 drops of 1-butanol + 3ml The two were miscible. 1-butanol is soluble in water.
of H2O.
10 drops of 2-propanol + 3ml The two were miscible. 2-propanol is soluble in
of H2O. water.
10 drops of tertbutyl alcohol The two were miscible. Tertbutyl alcohol is soluble
+ 3ml of H2O. in water.
10 drops of 1-butanol + 3ml The two were immiscible. Resorcinol is insoluble in
of H2O. water.

Table 2.1 FERRIC CHLORIDE TEST

TEST OBSERVATION INFERENCE
5 drops of 1-butanol + 2 A light yellow colour was Primary alcohol is present.
drops of ferric chloride. formed.
5 drops of 2-propanol + 2 A yellow colour was formed. Secondary alcohol is present.
drops of ferric chloride.
5 drops of tertbutyl alcohol + A pale yellow colour was Tertiary alcohol is present.
2 drops of ferric chloride. formed.
5 drops of resorcinol + 2 A dark purple colour was Phenol present.
drops of ferric chloride. formed.

Table 2.3 CHROMIC ACID TEST

TEST OBSERVATION INFERENCE
3 drops of 1-butanol + 3 Orange colour changes to 1-butanol is present.
drops of acetone + 3 drops of blue green. Primary alcohol present.

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chromic acid + warming.
3 drops of 2-propanol + 3 Orange colour changes to 2-propanol is present.
drops of acetone + 3 drops of green colour. Secondary alcohol present.
chromic acid + warming.
3 drops of tertbutyl alcohol + No colour change Tertiary alcohol present.
3 drops of acetone + 3 drops
of chromic acid + warming.
3 drops of resorcinol + 3 Formation of brown tarry Phenol present.
drops of acetone + 3 drops of masses.
chromic acid + warming.

Table 2.4 IODOFORM TEST

TEST OBSERVATION INFERENCE
5 drops of 1-butanol + 15 Cloudiness formed. Primary alcohol present.
drops of 6M NaOH + drops
of I2-KI reagent + warming.
5 drops of 2-propanol + 15 Two colour formation. A Secondary alcohol present.
drops of 6M NaOH + drops pale yellow colour below and
of I2-KI reagent + warming. a colourless above.
5 drops of tertbutyl alcohol + Colourless colour formed. Tertiary alcohol present.
15 drops of 6M NaOH +
drops of I2-KI reagent +
warming.

Table 2.5 KMnO4

TEST OBSERVATION INFERENCE
2ml of 1-butanol + 2 drops of Light brown colour with Primary alcohol is present.
KMnO4 + shaking. brown ppt. Formed.
2ml of 2-propanol + 2 drops Pale brown colour formed. Secondary alcohol is present.
of KMnO4 + shaking.
2ml of tertbutyl alcohol + 2 No reaction. Colour Tertiary alcohol present.
drops of KMnO4 + shaking. remained the same.

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Table 2.6 OBSERVATIONS
TEST 1-Butanol 2-Propanol Tertbutyl alcohol Resorcinol
Solubility + + + -
Ferric Chloride - - - +
Chromic acid + + + +
Iodoform _ + -
KMnO4 + + -

RESULTS AND DISCUSSION

FOR 1-BUTANOL
The solubility test gave a result of two miscible clear layers indicating that 1-butanol is
insoluble. The ferric chloride test gave a light yellow colour indicating presence of a primary
alcohol. With the chromic test, there was a colour change from orange to blue-green after
warming indicating the presence of primary alcohol. Primary alcohol turns to an aldehyde and
then to a carboxylic acid.
3CH3CH2OH + 4H2CrO4 + 6H2SO4 → 3CH3CO2H + 2Cr2 (SO4)3 + 13H2O
1º alcohol Orange carboxylic acid blue-green

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 With the iodoform test, cloudiness was formed with a disinfected smell indicating the presence
of a primary alcohol.
The KMnO4 test gave a light brown colour formation with brown precipitate indicating the
oxidation of primary alcohol to an aldehyde. Further oxidation forms an acid.
CH3CH2OH + KMnO4/H+ → CH3CHO + Mn2+ → CH3COOH
Ethanol Ethanoic acid

FOR 2-PROPANOL
The solubility test gave a clear soluble mixture confirming the solubility of the solution. This is
due to the strong intermolecular force of attraction. The ferric chloride test gave a light yellow
colour indicating presence of a primary alcohol.
With the chromic test, there was a colour change from orange to blue-green after warming
indicating secondary alcohols are oxidized to a ketone.

OH O

R CH+ H2CrO4
R → R C + OH
Cr2 (SO4)3 + H2O

(Secondary) (Red-orange) (Ketone) (Blue-green)

Two layers of colour formed, a pale yellow colour below and a colourless colour above indicating no
reaction between the two solutions.

FOR TERTBUTYL ALCOHOL

The two were miscible with the solubility test showing the presence of tertiary alcohol. In the ferric
chloride test, a yellow colour was obtained from the reaction. The chromic acid test gave no colour
change, indicating no reaction between the two solutions

(CH3)3CHOH + H2CrO4 + H2SO4 → NO REACTION

3º alcohol Orange

Iodoform test gave a colourless colour showing presence of a tertiary alcohol. The KMnO4 test
showed there is no reaction with tertiary alcohol. Colour remained purple.

FOR RESORCINOL

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The resorcinol is insoluble in water. In the ferric chloride test, a dark purple colour was formed
showing the presence of phenol. The chromic acid test gave a green colour formation indicating the
presence of a phenol.

SOURCES OF ERROR

1. Not measuring the required volume of solution.

2. Not warming the reagents at the required temperature.
3. Drops of water left beneath the test tubes during cleaning.
4. Used one dropper for two different solutions.

PRE-LAB

1.

Compound Structure 1,2 or 3 Alcohol Molecular Boiling Hazards

weight point

1-butanol CH3-CH2-CH2-CH2-OH Primary alcohol 74g/mol 117ºC Poisonous

2-propanol CH3-C(CH3)-OH Secondary 60g/mol 82.5 ºC Poisonous

alcohol
2-methyl-2-
propanol C(CH3)3-OH Tertiary alcohol 74g/mol 82.5 ºC Poisonous

OH
Resorcinol 94g/mol 276.5 ºC Can cause

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 OH severe skin
burn

2. Alcohols and water have the polar OH groups and it makes them associate free hydrogen
bonding when they are put together. The strange interaction that happens when they are put
together evolves enough hydration energy which overcomes the intermolecular forces of
hydrogen bonding of the alcohols. The hydration energy produced is greater than the
hydrogen bonding in the alcohols thereby causing its dissolution in water.

3. CH3CH (OH) CH2CH3 conc. HCl/ZnCl

2 CH3CH (Cl) CH2CH3 + H20

POST LAB

A.

1. Using the Lucas test, 5 drops 1-hexanol and 2-methyl-2-hexanol is placed in separate clean
dry test tube.
2. 1ml of Lucas reagent is added to both solutions and swirled.
3. After 10 minutes the 2-methyl-2-hexanol reacts slowly and after heating slightly gives a
white layer. The 1-hexanol does not react.

B.

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Chromic acid (acidified dichromate, an oxidizing agent) can also be used to distinguish between
types of alcohols by oxidizing the alcohol. Primary alcohols are oxidized to carboxylic acids;
secondary alcohols are oxidized to ketones; and tertiary alcohols are not oxidized. During the
oxidation, the orange-red color of the chromic acid changes to a blue-green solution. Oxidation
involves the breaking of C-C or C-H bond.

R CH2 OH + H2CrO4 → R C OH + Cr2 (SO4)3 + H2O

(Primary alcohol) (Red-orange) (Carboxylic acid) (Blue-green)

OH O

R CH R + H2CrO4 → R C R + Cr2 (SO4)3 + H2O

(Secondary alcohol) (Red-orange) (ketone) (Blue-green)

OH

R C R + H2CrO4 → No Reaction

R
(Tertiary alcohol)

REFERENCE

Ralph J. Fessenden and John S. Fessenden, Organic Chemistry, 4TH Edition, Page 257-300, Pacific
Grove Inc., California, U.S.A

B.S. Furniss, A.J. Hannaford, P.W.G. Smith and A.K. Tatchell, Practical Organic Chemistry, 5 TH
Edition, Page 517-550, 1989, Singapore

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