Experiment 16

Alcohols and Phenols

Goals:
1.
To learn some common properties of alcohols and phenols.
2. To distinguish phenols from the three types of alcohols by chemical tests.
Concepts:
Alcohols are organic compounds containing an -OH functional group bonded
to a carbon atom. There are three classes (types) of alcohols: primary,
secondary, and tertiary as shown below.
Primary alcohol: RCH2-OH , the R, an alkyl group, and the OH are attached
to a primary carbon atom, a carbon bonded to one other carbon atom
(highlighted).
R

OH
C

H3C
H

primary carbon

OH
C
H

Secondary alcohol: R2CH-OH , the 2 R alkyl groups, and the -OH are
attached to a secondary carbon atom, a carbon attached to two other carbon
atoms from the 2 R(CH3-),
R

H3C
H3C

OH
R
R

secondary carbon

OH
C
H

C
H

Tertiary alcohol: R3C-OH, the 3 R alkyl groups, and the OH are attached to
a tertiary carbon atom (highlighted), a carbon attached to three other carbon
atoms from the 3 R (CH3-)
R

H3C
H3C

OH
R
R

tertiary carbon

OH
C
CH3

C
R

The International Union of Pure and Applied Chemistry (IUPAC) method of

nomenclature for alcohols use the ending ol. Change the e ending of an
alkane to ol (i.e. methane to ol
methanol ethane to ol
ethanol).

Physical Properties of Alcohols:

1. Alcohols are colorless at room temperature.
2. Alcohols form hydrogen bonds with water.
H

O
R

3. Alcohols form intermolecular hydrogen bonds (with itself).

This causes alcohols to have higher boiling points than
hydrocarbon of similar molecular mass.
R

O
R

4. Alcohols with 5 or less carbon atoms are soluble in water.

Chemical Properties of Alcohols:
1. Oxidation of alcohols by strong oxidants such as K2Cr2O7 in H2SO4 is
possible, but differs depending on the degree of alcohol. Examples a, b, and c
below show how a primary, secondary, and tertiary alcohol respectively
respond to treatment of oxidants. If a reaction has occurred using K2Cr2O7 in
H2SO4, there is a color change from orange to green.
+

RCH2 OH

a)

primary
alcohol

+6

K2Cr2O7

C
R

orange

C
R

Cr+3
green/blue

aldehyde

Further oxidation of

carboxylic acid

C
R

OH
O

CH3CH2OH
a primary alcohol

Cr+3

Cr +6
orange

green/blue

C
H3C

an aldehyde
further
oxidation
O
C
H3C

OH

a carboxylic acid

R2CHOH

b)

secondary
alcohol

+6

K2Cr 2O7

C
R

orange

Cr+3

+
R

green/blue

ketone

OH
H3C C CH3

Cr+3

Cr +6
orange

a secondary
alcohol

green/blue

C
H3C

CH3

a ketone

NO
further
oxidation

c) Tertiary alcohol: R3COH + K2Cr2O7 NO OXIDATION

OH
H3C C CH3
CH3

a tertiary
alcohol

Cr +6

No reaction (still orange)

orange

2. Lucas Test: This test is for low molecular weight alcohols and it distinguishes
the rates of reaction of alcohols with the Lucas reagent (HCl and ZnCl2).
Positive indicator of the reaction is the formation of a water insoluble alkyl
chloride as cloudiness or a precipitate. The formation of an alkyl chloride
with tertiary alcohol is very rapid, followed by the secondary alcohol that may
take from 5 to 20 minutes to form visible cloudiness. Primary alcohols do not
react with Lucas reagent or it may show very little result in a very long time.
3o alcohol: R3COH + HCl (ZnCl2) R3Cl (alkyl chloride) + H2O Very Fast
(insoluble/cloudiness)
CH3
H3C C OH

HCl

CH3

ZnCl2

H3C C Cl

CH3

CH3

3o alcohol

alkyl chloride
(insoluble-cloudiness)

+ H 2O

2o alcohol: R2CHOH + HCl (ZnCl2) R2CHCl (alkyl; chloride) + H2O Slow

(insoluble/cloudiness)
CH3
H3C C OH

HCl

CH3

ZnCl2

+ H 2O

H3C C Cl

slow

2 alcohol

alkyl chloride
(insoluble-cloudiness)

1o alcohol: RCH2OH + HCl (ZnCl2) No reaction/very very slow

H
H3C C OH

HCl

ZnCl2

no reaction (no cloudiness)

H
o

1 alcohol

Phenols:
Phenolic compounds have a benzene ring with the OH group attached to the
benzene ring carbon atom. The simplest compound is phenol (C6H5OH) or
OH

. Phenols are considered very weak acids. They have different

physical and chemical properties from alcohols. They neither undergo oxidation
nor react with the Lucas reagent.
However, phenols react with FeCl3 to form a para-phenol-Fe complex (which has
a purple color).
OH

OH

Fe

+3

para phenol complex

(purple)

(orange)
Fe

Materials:
6 medium size test tubes, ethanol (ethyl alcohol), 2-propanol (isopropyl alcohol),
tertiary butyl alcohol, (2-methyl-2-propanol), phenol, cyclohexanol, 2% K2Cr2O7
in H2SO4 (oxidant), HCl ZnCl2 (Lucas reagent), 20 % phenol, 1% FeCl3, pH
paper, stirring rod, and an unknown
Wear safety goggles and dispose of chemicals in proper containers.
Procedures:

Do all parts of this experiment in the fume hood.

1.

Solubility in Water:
Place 20 drops of each alcohol, phenol, and an unknown in 6 separate test
tubes in a test tube rack, labeling each test tube. Add 2 mL of distilled water
to each test tube. If the substance is soluble (miscible) in water, there will be
no separate layers. If it is insoluble (immiscible), a cloudy mixture or layers
will form. Record your observation in the table below.

2.

Acidity:
To each test tube in step 1, dip a stirring rod and touch it to the pH paper.
Compare the color of the paper with the chart on the container to check the pH
of the solution. Wash and dry the stirring rod before dipping it to the next test
tube. Record your observations in the table below.

3.

Oxidation of alcohols:
Clean 5 test tubes with soap and water and dry the test tube with a paper
towel. Label each test tube and place them on a test tube rack. Place 5 drops
of the alcohols, phenol, and an unknown in each test tube. Add 3 drops of the
oxidant (K2Cr2O7-H2SO4) to each test tube. Observe if there is a change in
color from orange to green/blue for the alcohols. Remember that only the
primary and secondary alcohols undergo oxidation. The positive indicator is a
change from orange to green/blue in 1-2 minutes. Color change to any other
color but green/blue is a negative reaction. Record your observations.

4.

Ferric Chloride Test for Phenolic compounds:

Clean 5 test tubes with soap and water and dry the test tube with a paper
towel. Label each test tube and place them on a test tube rack. Place 5 drops
of the alcohols, phenol, and an unknown in each test tube. Add 3 drops of 1%
FeCl3 to each test tube. The positive indicator is the purple color of the
phenol-Fe complex. Any color other than purple is negative.
Observation Sheet for Procedures 1-4
Name of
substance
phenol

Solubility
in water

Acidity

Color
change
(orange to
green/blue)

n/a

ethanol
2-propanol
cyclohexanol
t-butyl alcohol

Reaction product
(aldehyde, ketone,
Fe-complex)

Type
of
alcohol

Your unknown

5. Lucas Reagent Test:

Measure 2 mL of the Lucas reagent into five labeled test tubes on a test tube
rack. Add 5 drops of each of the following to each test tube: ethyl alcohol, 2propanol, cyclohexanol, t-butyl alcohol, and deionized water as a control.
Mix reagents well using a stirring rod. Wash and dry your stirring rod after
each use. Observe and record formation of an insoluble product (cloudiness),
the positive indicator that a reaction has taken place at different times.
Alcohols

Type of
alcohols
(1o, 2 o, 3 o )

1
minute
(cloudy)

3
minutes
(cloudy)

5
minutes
(cloudy)

10
minutes
(cloudy)

15
minutes
(cloudy)

Ethanol
2-propanol
Cyclohexanol
t-butyl alcohol
(2-methyl-2propanol)
your unknown
water

Use the results of the tests for alcohol and phenol to identify your unknown. Give
reasons why you believe your unknown is _______. Justify your answer.

Questions:
1.

Since all alcohols form hydrogen bond with water, does this mean
all alcohols are soluble (miscible) in water? Why?

2. Write the structure for each of the following alcohol, identify what
type of alcohol (its degree), and write the reaction product with an
oxidant, K2Cr2O7-H2SO4. If no reaction occurs, write NR.
2
a) 2-pentanol

b) 1-methyl-cyclopentanol
c) 1-hexanol
d) 2-methyl-2-butanol
e)
3.

methylphenol

Write the structure for each of the following alcohols, identify what type
of alcohol (its degree), and write the reaction product with the Lucas
reagent. If no reaction, write NR.
4
a) 2-pentanol
b) 1-methyl-cyclopentanol
c) 1-hexanol
d) 2-methyl-2-butanol
e) methylphenol

4.

If you add K2Cr2O7 in H2SO4 to a test tube with an unknown alcohol in it,
and the solution stays orange, what can you conclude about the alcohol?