INTRODUCTION

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: Primary alcohols are those alcohols where the carbon atom of the hydroxyl
group(OH) is attached to only one single alkyl group. RCH2OH the ‘R’, an alkyl group, and
the –OH are attached to a primary carbon atom, a carbon bonded to one other carbon atom.
Some of the examples of these primary alcohols include methanol, propanol, ethanol, etc.

Example of Primary alcohol

Secondary alcohol: R2CHOH, 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-)

Example of Secondary alcohol

Tertiary alcohol: Tertiary alcohols are those which feature hydroxyl group attached to the
carbon atom which is connected to 3- alkyl groups. The physical properties of these alcohols
mainly depend on their structure. The presence of this -OH group allows the alcohols in the
formation of hydrogen bonds with their neighbouring atoms. The bonds formed are weak,
and this bond makes the boiling points of alcohols higher than its alkanes. The examples of
tertiary alcohols include-

Example of Tertiary alcohol

For physical properties, the size of alcohol determines its boiling point. Usually, the larger
the size of the alcohol, the higher the boiling point. This is because the bigger the size of the
molecules, the stronger the Van der Waals force between the alcohol molecules. So, more
heat energy is needed to be absorbed in order to break down the intermolecular force between
each alcohol molecules. Hence, the boiling point of the alcohols increases with the size of the
alcohols. The solubility of the alcohol is depending on the size of molecules. Small alcohols
are water soluble because the hydroxyl group can form hydrogen bond with water molecules.
But, as the size of the alkyl group increases, the solubility of alcohol in water decreases as the
hydrophobic property of alcohol increases. For example, if the carbon molecules in alcohol
more than six per molecule, the particular alcohol definitely are not soluble in water. This is
the result of the alkyl group disrupting the hydrogen bond among the water molecules. If the
disruption becomes larger enough, the water molecules will repel the alcohol molecules
effectively to re-establish hydrogen bonding. Due to their different classes, the alcohols may
give out different chemical properties when they react with the same compounds. Based on
their chemical properties, we are able to differentiate among the classes of alcohols.
Generally, Lucas test and chromic acid test is the two common tests that we always use to
distinguish and categorize the classes of alcohols.

Lucas test

Water soluble alcohols are always tested by using the Lucas reagent to differentiate among
the primary, secondary, and tertiary alcohols. This test depends on the appearance of an alkyl
chloride as an insoluble second layer. Lucas reagent is the mixture of zinc chloride and
hydrochloric acid. Zinc chloride is a Lewis acid which is added with hydrochloric acid to
make its property becomes more acidic. The tertiary alcohol (water soluble) reacts with Lucas
reagent almost immediately to form an alkyl chloride which is insoluble in the aqueous
solution. The formation of a second layer liquid phase in the test tube almost as soon as the
alcohol initially dissolves is indicative of a tertiary alcohol. The secondary alcohol reacts
slowly with Lucas reagent, and it gives a second phase after heating for 10 minutes whereas
the primary alcohol and methanol do not react with Lucas reagent under normal condition.
The chemical equation is as shown below (if the reaction takes place)

ZnCl2
R-OH + HCl R-Cl + H2O

Chromic acid test

Chromic acid is a strong oxidizing agent which uses to oxidize the alcohols. This test is based
on the reduction of chromium (VI) ions to chromium (III) ion. When chromic acid reacts with
alcohols, the change in colour of the solution from red-brown to green is a positive test.
Primary alcohols are oxidized to carboxylic acid by chromic acid. The Cr6+ in the chromic
acid which is red-brown is reduced to green Cr3+; secondary alcohols are oxidized to ketones
by the reagent with the same colour change. Tertiary alcohols are not oxidized at all by the
chromic acid. Hence, this reaction can be used to distinguish tertiary alcohols form primary
and secondary alcohols. For tertiary alcohols, the alcohols would not be oxidized by the
reagent. Hence, this test is used to distinguish the tertiary alcohols from primary and
secondary alcohols.

Reaction with sodium metal

The acidic properties of alcohol can be shown by adding the sodium metal into alcohol. The
alcohols are weak acids when they react with sodium metal. The hydroxyl group can act as a
proton donor to form an alkoxide ion. Alkoxide ions dissolved in alcohol are strong bases
which can be prepared by the reaction of an alcohol with sodium metal. Hydrogen gas is
released by the reaction.

2 R-OH + 2 Na 2 R-O- Na+ + H2

The hydrogen gas can be collected and tested by using a burning wooden splinter. A pop
sound will be produced.
ABSTRACT

The objective of the experiment (Properties of Alcohols: Structure, Reactions and

Identification of Alcohols) are to examine molecular models and observe some physical and
chemical properties of selected alcohols. Besides that, the objective of this experiment is to
relate the observed properties to the molecular structure and identify an unknown alcohol.

In experiment A (solubility of alcohol), three separate dry test tubes, ethanol,

isopropyl alcohol and t-butyl alcohol are added into each test tube. Water is added to each
tubes, the contents are mixed and observed. The results are recorded in a table. The above
procedures are repeated with two unknown liquids and observations are being made

In experiment B (Lucas Test), Ethanol, isopropyl alcohol and t-butyl alcohol are
added into separate dry test tubes and Lucas reagent is added at room temperature. The tubes
are closed with a cork, the tubes are shaken and the length of time it takes for the mixture to
become cloudy or separate two layers. The results are recorded. The above procedures are
repeated with the two unknown liquids and observations are being made.

In experiment C (Chromic Acid Test), ethanol, isopropyl alcohol and t-butyl alcohol
are added into separate dry test tubes. A small piece of sodium metal is added and any
reactions occur are noted. The step 1 and step 2 are repeated with two unknown liquids and
any observations are made.

From the experiment, it is found that Lucas test is used to distinguish among the
primary, secondary, and tertiary alcohols. For Lucas test, the formation of two layers
(aqueous layer and cloudy layer) is known as a positive test. The second layer (cloudy layer)
formed is alkyl chloride which is insoluble in the aqueous solution because all the alkyl
halides molecules are insoluble in the water. The alkyl chloride produced from the reaction is
not water soluble and causes cloudiness (emulsion) to form in the aqueous solution. When
ethanol is added with Lucas reagent, the yellowish solution is still remains the same before
and after heating. This is because primary alcohol does not react with Lucas reagent. Besides,
isopropyl alcohol does not react with Lucas reagent before heating but it does turns to cloudy
solution after heating for 10 minutes. The reason is the reaction between Lucas reagent and
secondary alcohol is slow. For tertiary alcohol (t-butyl alcohol), the reaction of alcohol with
Lucas reagent is very fast which can be known as an instant reaction. The reaction that takes
place on the Lucas test is a SN1 nucleophilic substitution. The alcohols with the properties of
generating a stable carbocation intermediates will undergo the particular reaction. The OH
group of the alcohol attracts the H in hydrochloric acid to form oxonium ion and leave the
group (form water). The carbocation intermediate is formed and tends to react with Cl-
(nucleophile) to produce the alkyl halide product. The purpose of chromic acid test used in
this experiment is to distinguish the primary and secondary alcohols from the alcohols group.
In the reaction between alcohols and chromic acid, the chromic acid is being reduced which
the chromium (VI) ions, Cr6+ reduced to become chromium (III) ion, Cr3+. The positive test
for chromic acid is represented by the change in colour from orange to green-blue. In the test
tube with ethanol, the colourless alcohol is turned to green solution because the chromium
(IV) ions, Cr6+ are being reduced by ethanol. In the test tube containing isopropyl alcohol,
two layers of colour are formed. The upper layer is green whereas the lower layer is black.
This is shows that the isopropyl reacted with the chromic acid due to the secondary alcohol is
readily to be oxidized. The black layer actually is the dark blue colour, it is hard to
differentiate because the light is not enough in the laboratory. The t-butyl alcohol would not
have oxidized by the chromic acid since the tertiary alcohol is a highly oxidized alcohol. This
is shown by the formation of reddish brown precipitate. Hydrogen ions will be attracted to
one of the oxygen atom in the chromic acid that is double bonded to chromium. The lone pair
electrons from hydroxyl group of alcohols will then attack the chromium ion and form a
chromate intermediate. The hydrogen on the hydroxyl group of alcohols will then leave as
hydrogen ion and combine with the oxygen atom that is previously attacked by a hydrogen
ion. A water molecule will come and attack α-hydrogen on the alcohol and produce
hydronium ion, forming C=O double bond. A water molecule will leave the chromate
intermediate and the carbonyl product is formed. Since the oxidation of alcohol requires at
least one hydrogen atom to be presence on α-carbon, thus tertiary alcohol cannot be oxidized
because it does not have the α-hydrogen. This explains why t-butyl alcohol does not change
the color of the chromic acid which is red brown to green. The precipitate formed at the
beginning may be because of the formation of chromium trioxide precipitate.