EXPERIMENT 4

Identification of alcohols and phenols

PURPOSE
1. To learn characteristic chemical reactions
of alcohols and phenols.
2. To use these chemical characteristics for
identification of an organic compound.

bond. The H-bonding allows alcohols to dissolve

in water (water has 2 OHs and 2 lone pairs on
the Oxygen). Rule of Thumb: Each OH on the
carbon chain will allow 3 to 4 Carbons to be
dissolved in water.
Aliphatic Alcohols may be classified as
either primary, secondary, or tertiary. Note that
the classification depends on the number of
carbon-containing groups, R (alkyl or aromatic),
attached to the carbon bearing the hydroxyl group.
Examples follow:

BACKGROUND
Specific groups of atoms in an organic
molecule can determine its physical and
OH
OH
OH
chemical properties. These groups are
referred to as functional groups. Organic
R1 C H
R 1 C R3
R1 C H
compounds which contain the functional
H
group OH, the hydroxyl group, are called
R2
R2
alcohols.
Primary
Tertiary
Secondary
Alcohols can be broken into two broad
OH
OH
categories: aliphatic alcohols and aromatic
OH
alcohols. Aliphatic alcohols are where an OH
CH3 C H
CH3 C H
CH3 C CH3
group is attached to a carbon chain that is not
CH3
CH3
H
a benzene ring. Aromatic alcohols have the
OH group attached to a benzene ring. The
(b) 2-propanol (c) 2-methyl-2-propanol
(a) Ethanol
letter R may represent any carbon chain but (Ethyl Alcohol) (Isopropyl alcohol)
(t-butyl alcohol)
the letters Ar specifically represents a
benzene ring or rings are present.
Phenols are the simplest form of an aromatic
Alcohols are important commercially and
alcohol (Ar-OH) bear a close resemblance to
include uses as solvents, drugs, and
regular alcohols since the hydroxyl group is
present. However, since the -OH group is bonded
disinfectants. The most widely used alcohols
directly to a carbon that is part of an aromatic ring,
are methanol or methyl alcohol, CH3OH,
the chemistry is quite different from that of
ethanol or ethyl alcohol, CH3CH2OH, and 2aliphatic alcohols. Phenols are more acidic than
propanol or isopropyl alcohol, (CH3)2CHOH.
alcohols; concentrated solutions of the compound
Methyl alcohol is found in automotive
phenol are quite toxic and can cause severe skin
products such as antifreeze and "dry gas."
burns. Phenol derivatives are found in medicines;
Ethyl alcohol is used as a solvent for drugs
for example, thymol is used to kill fungi and
and chemicals, but is more popularly known
hookworms.
for its effects as an alcoholic beverage.
Isopropyl alcohol, also known as "rubbing
CH3
OH
alcohol," is an antiseptic.
OH
CH
One of the big differences between
alcohols and hydrocarbons is the ability to
CH3
give and receive hydrogen bonds, To give
an H bond there must be an O-H or an N-H
H3C
on the molecule. To receive an H-bond there
Thymol
phenol
must be an O or N with a lone pair of
(2-isopropyl-5-methylphenol)
(carbolic acid)
electrons on those atoms. An H-bond makes
an extra semi-connection between molecules.
When there is an H-bond there is a stronger
attraction (intermolecular force) and therefore
increases the melting and boiling point of the
alcohol relative to a same size hydrocarbon.
Alcohols can both give and receive an H-

Lab 4 Alcohol Identification

PHYSICAL PROPERTIES
IMF forces: The intermolecular forces
present in alcohols are Hydrogen bonding,
Dipolar and LDF. The CO and the OH bonds
in COH are polar. The H attached to the O
can H-bond to the lone pair of another O with
and therefore exert a more attractive force.
Solubility: Alcohols can give one H-bond
and take two H-bonds (there are two lone
pairs of electrons on the O). When mixed with
water, which has two OHs (gives two H
bonds) and two lone pairs (receives two Hbonds). This makes alcohols usually soluble
in water (each OH group on the molecule can
make soluble about 3 carbons)
Melting point/boiling point: When we look
pure compound, each OH group can give and
take an H-bond. This external connection of
one molecule to another makes a stronger
connection and raises the melting and boiling
point of these compounds relative to
hydrocarbons of about the same weight.

Flammability . All alcohols are flammable. The

smaller molecular weight alcohols will burn with a
blue flame. Even in a mixture of water and
alcohol will burn if the percent of alcohol is
greater than 50%
Oxidation and Reduction of alcohols. Alcohols
will undergo oxidation and reduction reactions.
Oxidation is the gaining of new connections to
oxygen or it is losing hydrogen at a single carbon.
Reduction is the losing of oxygen connections or
the gaining of hydrogen at a single carbon. A
quick way to see how many steps of oxidation
that an alcohol can have is to look at the number
of hydrogens at the carbon being oxidized. If the
alcohol carbon has 2 Hs then it can be oxidized
twice. If it has 1 H then it can be oxidized once
and if it does not have any Hs at the alcohol
carbon then it cannot be easily oxidized.
Table 1: Redox terms
Oxidation, [O]

Reduction, [H]

Gain Os or
connections to O

Lose Os or
connections to O

Solubility, The solubility of alcohols in water

is variable. The general rule is that to be very
soluble you need 1 OH group for every 3 to 4
carbons.
Methanol
and
ethanol
are
completely soluble in water but heptanol is
almost insoluble. The reason alcohols are
soluble in water is that alcohols can
hydrogen bond or H-bond.

Lose Hs

Gain Hs

OIL-Oxidation Is
Losing electrons

RIG- Reduction Is
Gaining electrons

Acidity. Aliphatic alcohols are not acidic, the

H in the OH is strongly attached so that pH
paper should show it to be neutral.
Aromatic alcohols (phenols) are acidic and
the H in the OH will come off as an H+ in
water (It will show as an acid with pH paper).
One older name for phenol was carbolic acid
emphasizing the acidic nature of the OH
group. Since phenol is an acid, it will react
with base; thus phenols readily dissolve in
base solutions. In contrast, aliphatic alcohols
do not.

2 alcohol

Oxidation reactions of alcohols

[O]

[O]
aldehyde

1 alcohol

carboxylic acid

[O]

CHEMICAL PROPERTIES
The chemical behavior of the different classes
of alcohols and of phenols can be used as a
means of identification. Quick, simple tests
that can be carried out in test tubes will be
performed.

Lab 4 Alcohol Identification

ketone
[O]
No Reaction

3 alcohol

Reduction reactions (not done today)

[H]
aliphatic
alcohol

alkene

H2O

General information on Redox (oxidationreduction). Oxidation and reduction always

come in pairs. If something gains electrons,
something had to lose them. The symbol [0]
represents a oxidizing reagent that will oxidize
something but itself is reduced. The symbol [H]
represents a reducing agent that will reduce a
molecule (usually by adding Hs) but itself is
oxidized.

CHEMICAL TESTS
Lucas test. This test is used to distinguish
between water-soluble primary, secondary,
and tertiary alcohols. Lucas reagent is a
mixture of zinc chloride, ZnCl2 in concentrated
HCI. Upon addition of this reagent, a tertiary
alcohol reacts rapidly and immediately gives
an insoluble white layer. A secondary alcohol
reacts slowly and, after heating slightly, gives
the white layer within 10 min. A primary
alcohol does not react. Any formation of a
heterogeneous phase or appearance of an
emulsion is a positive test.
primary alcohols & phenols
CH3CH2-OH + HCI + ZnCI2 no reaction

Bordwell Test (Chromic acid test). This test is

able to distinguish primary and secondary
alcohols from tertiary alcohols. Using Bordwells
Reagent (acidified dichromate solution), primary
alcohols are oxidized to carboxylic acids;
secondary alcohols are oxidized to ketones;
tertiary alcohols are not oxidized. (Note that in
those alcohols which are oxidized, the carbon
that has the hydroxyl group loses a hydrogen.) In
the oxidation, the brown-red color of the chromic
acid changes to a blue-green solution. Phenols
are oxidized to nondescript brown tary masses.
(Aldehydes are also oxidized under these
conditions to carboxylic acids, but ketones
remain intact)
primary alcohols
OH
4 H2CrO4
3 CH3 CH2+ brown-red

secondary alcohols
(CH3)2CH-OH + HCI + ZnCI 2
insoluble (10 min. heat)

6 H2SO4

1 alcohol

3 CH3

tertiary alcohols
(CH3)3C-OH + HCI +ZnCI2
insoluble (< 5 min.)

O
C

+ 2 Cr2(SO4)3 +13 H2O

green

OH

carboxylic acid

secondary alcohols
OH

Phenol Test. This test will distinguish

between phenol (an aromatic alcohol) and
the other aliphatic alcohols. Phenols will
displace a chloride ion off the iron leaving an
HCl in solution. The product of substituting
one, two or three phenols will give a violet
(light purple) color.

2 H2CrO4
3 CH3 CH CH3+ brown-red

1 alcohol or
2 alcohol or
3 alcohol

tertiary alcohols

OH
phenol

FeCl3

NO REACTION

orange

stays orange

FeCl3
orange

OFeCl2
violet

3 H2SO4

2 alcohol

3 CH3

O
C

+
CH3

Cr2(SO4)3 + 8 H2O
green

a ketone

OH
CH3 C CH3

H CrO

2
4
+ brown-red
+

H2SO4

CH3
HCl

3 alcohol

NO REACTION
(stays brown-red)

phenols
No reaction
Phenols are not oxidized but may associate with
the chromium and turn dark brown, but they do not
get the blue/green of the positive test .

Lab 4 Alcohol Identification

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For front to back printing

Lab 4 Alcohol Identification

EXPERIMENTAL PROCEDURE
CAUTION! Chromic acid and Lucas reagent
are both very corrosive. Any spill should be
immediately flushed with water. Phenol is
toxic and contact with it can cause burns to
skin: any contact should be thoroughly
washed with large quantities of water. Use
gloves with these reagents. Dispose of
reaction mixtures and excess reagents in
waste containers only as directed by this
handout or your instructor.
You will test the four known alcohols and
one unknown:
1-butanol (a primary alcohol)
2-butanol (a secondary alcohol)
2-methyl-2-propanol (a tertiary alcohol)
Phenol (aq,), sat. See Note
Also an assigned UNKNOWN which is
labeled A,B,C,D
Note: aq = aqueous = dissolved in water
sat. = saturated (solution) = as much dissolved
in water as possible (different than saturated
hydrocarbons (molecule) = only single bonds)

You will Choose one unknown (labeled A, B,

C, or D) which will be one of the known
compounds. As you run a test on the known
alcohols, test the unknown at the same time
for comparison. Note: the phenol will be
provided as an saturated aqueous solution.
Since phenol is not fully soluble in water you
may see a small puddle of phenol on the
bottom. This means that the clear liquid
above is saturated with phenol. Use the
clear liquid for your tests
For efficient time use: find and plug in a HOT
PLATE Put a medium beaker on it filled to
about of tap water and heat to about 60C
for test #5 and #6. This is hot to touch but
not boiling. When hot to touch turn it off.
1. Solubility Test. Into separate test
tubes (100 x 13 mm) labeled 1-butanol, 2butanol, 2-methyl-2-propanol, and unknown,
place 10 drops of each sample; dilute by
mixing with 3 mL of distilled water. Into a
separate test tube, place 2 mL of a prepared
water solution of phenol (do not add water .
Are all the solutions homogeneous? Record
your observations in your data table.

Lab 4 Alcohol Identification

Solubility Observation. The instructor will

have a series of test tubes laid out of alcohols
from C1 to C8 mixed 1:1 with water. Observe
whether the mixture exists as a single layer
(soluble) or as two layers (insoluble). Each one
will be named with a common name, write the
IUPAC name.
2. Flammability In the fume hood place 5
watch glasses and put 5-7 drops of each (four
knowns and 1 unknown). Open the fume hood
barrier to its highest position and light a match
outside the fume hood and bring it to each of
the samples. Look for a flame and if there is a
flame, what color is it. These flames may be
light and hard to see.
Note: do not use gloves during the flame test as
they will melt if caught on fire.
Dispose of any remaining solution down the
sink and glass with soapy water
3. Acidity Test. Test the pH of each of the
aqueous solutions. Do the test by dipping a
clean glass rod into the solutions and then
transferring a drop of liquid to pH paper. Use a
broad pH indicator paper (e.g., pH range 1-12)
and read the value of the pH by comparing the
color to the chart on the dispenser. Record your
observations in your data table.
Dispose of your solutions in the "Organic
Waste" container. Rinse your test tubes in the
sink.
4. Lucas test. Place 5 drops of each sample
into separate clean, dry test tubes (100 x 13
mm), labeled as before. Add 1 mL of Lucas
reagent; mix well by stoppering each test tube
with a cork, tapping the test tube sharply with
your finger for a few seconds to mix; remove
the cork after mixing and allow each test tube to
stand for 5 min. Look carefully for any
cloudiness that may develop during this time
period. If there is no cloudiness after 10 min.,
warm the test tubes that are clear for 15 min. in
a 60C water bath. Record your observations in
your data table.
Dispose of your waste in the "Zinc/Organic
waste" container. Rinse your test tubes with a
small amount of acetone and dispose of the
rinse in the same container

Bordwell Test (Chromic acid test). Place

into separate clean, dry test tubes (small,
100 x 13 mm), labeled as before, 5 drops of
each sample to be tested. To each test tube
add 10 drops of acetone and 2 drops of
Bordwells Reagent (strongly acidified
chromic acid). Place the test tubes in a 60C
water bath for 5 min. Note the color of each
solution. (Remember, the loss of the brownred and the formation of a blue-green color is
a positive test.) Record your observations in
your data table.
Dispose
of
your
waste
in
the
"Chromium/Organic waste"
container.
Rinse your test tubes with a small amount of
acetone and dispose of the rinse in the same
container.
5. Phenol Test . Place into separate
clean, dry test tubes (small, 100 x 13 mm),
labeled as before, 5 drops of each sample
to be tested. To each test tube add 2-3
drops of 1% FeCl3 . Note the color of each
solution. (Remember that iron (III) chloride
is orange-yellow to start with, a positive
result is a change of color to blue/purple)
Dispose of your waste in the "Zinc/Organic
waste" container. Rinse your test tubes with
a small amount of acetone and dispose of
the rinse in the same container

Lab 4 Alcohol Identification

LAB REPORT
Lab Report Cover Sheet
On a separate sheet of paper write the title,
purpose of the experiment, and date that you'll
be performing the experiment.
Show the structures of the four known alcohols
you used in the lab and below each structure
write at least two names for each one.

Data Sheets (During lab

Fill in your data table with observations. Make
note of any changes to the procedures that
occur.
Post lab
Analysis: On a separate sheet of paper (it can
be the backside of the paper with the title) use
your observations to identify whether your
unknown is a primary alcohol, secondary
alcohol, tertiary alcohol, or phenol. Explain how
you determined the identity of your unknown
using the results from your tests: BE SPECIFIC.
Conclusion: Restate the identity of your
unknown, and comment upon the utility of each
of the four tests in your determination and the
validity of including the four "knowns."
Turn in the cover sheet, data sheets, analysis and
conclusion.

Name__________________________

Lab 4 Data sheet: Alcohols and Phenols

Physical Properties
1. Solubility in Water Test
Compound
Observations

Positive Test: one layer

Negative Test: two layers

2. Solubility Observation (these alcohols have no branches)

Compound
Alternate official name
(common name)
(IUPAC)
C1

Methyl alcohol

C2

Ethyl alcohol

C3

n-propyl alcohol

C4

n-butyl alcohol

C5

amyl alcohol

C6

Cyclohexyl alcohol

C7

Heptyl alcohol

C8

Octyl alcohol

3. Flammability
Tests For:
Compound

Observations
(one layer or
two)

Soluble?

Observations

Positive Test: burns

Lab 4 Alcohol Identification

Negative Test: will not ignite

4. Acidity Test
Tests For: Acid present ( aromatic alcohol )
Compound
Observations

aliphatiic alcohols are not acidic

Positive Test: blue pH paper turns pink if acid present

Negative Test: stays blue

Chemical Properties
5. Lucas Test ( Lucas Reagent)
Tests for: tertiary and secondary alcohols
Compound
Observations

Positive Test: turns milky white

6. Chromic Acid Test ( Bordwells Reagent)
Tests for: primary and secondary alcohols
Compound
Observations

Positive Test: turns blue/green

7. Phenol Test ( Iron (III) Chloride Reagent )
Tests for: phenols
Compound
Observations

Positive Test: turns violet (purple)

Lab 4 Alcohol Identification

Fails for: primary and aromatic should fail

Negative Test: stays clear

Fails for: tertiary and aromatic

Negative Test stays orange or turns brown

Fails for: aliphatic alcohols

Negative Test: stays orange/yellow

Questions:
1. Write out methanol showing the lone pairs on the oxygen and two waters each with the Hs
angled out and two lone pairs of electrons on each one. Show methanol H-bonding to one water
and one water H-bonding to the methanol.

2. Would you expect the following molecules to be soluble using the general rule of OHs to carbons

a)

OH
OH
CH3 CH CH2 CH2 CH CH3

b)

CH3 CH CH2 CH3

CH3 CH OH

3. Write out the products from the following oxidations.

a)

CH3
OH
CH3 CH CH2 CH2

[O]

IUPAC Name:

[O]

Class of Compound

Class of Compound

Common Name:

b)

OH
CH3 CH2 CH CH2 CH3

[O]

IUPAC Name:

Class of Compound

c) Why does a) go two steps but b) only goes one step

(use words like primary, secondary, tertiary)

4. Write out a Product from the following reduction [H], (loss of H2O or dehydration).

OH
CH3 CH2 CH2 CH2 CH CH3

acid
heat

5. Is Bordwells Reagent an Oxidizing Reagent or Reducing Reagent?

Lab 4 Alcohol Identification