UNIVERSITI TUNKU ABDUL RAHMAN

FACULTY OF SCIENCE

BACHELOR OF SCIENCE (HONS) BIOCHEMISTRY

YEAR 1 TRIMESTER 3

UDEC 1164 ORGANIC CHEMISTRY

Name

Sri Sangliswaran s/o Subramaniam

ID

1203776

Experiment Title
Partners

Date of Submission

Title: Properties of Alcohols

Experiment 4:

Properties of Alcohols

Nurul Maswin bt Anaqi Suen

Tan Chai Yuin
Beh Wan Chin
25.2.2015 (week7)

Objectives :

To study the properties of alcohol

To determine the reactivity of alcohol
To determine the nature of given alcohols by using several chemical tests.

Introduction :
Simple hydrocarbon chains or rings that contain a hydroxyl group (-OH) bonded to a
carbon atom are called alcohols. The following are several such compounds:

Methanol

Ethanol

propan-2-ol

2-methylpropan-2-ol

An alcohol is any organic compound in which the hydroxyl functional group (-O H) is bound to
a hydrocarbon chain. The suffix -ol appears in the IUPAC chemical name of all substances where
the hydroxyl group is the functional group with the highest priority; in substances where a higher
priority group is present the prefix hydroxy- will appear. The general formula for alcohol is
CnH2n+1OH.
As shown above if the carbon atom is bonded to three hydrogen atoms in addition to the
OH, the alcohol is methanol. If the carbon bonded to the OH is bonded to one alkyl group and
two hydrogen atom, the alcohol is primary alcohol (1 o). If the carbon that is bonded to the OH
is bonded to two alkyl group and one hydrogen atom, the alcohol is a secondary (2 o) alcohol. If
the carbon that is bonded to the OH is bonded to three alkyl group, the alcohol is a tertiary (3 o)
alcohol. All of these alcohols share some characteristics but other characteristics are different
owing to their different structures.

Physical Properties
The larger an alcohol the higher the boiling point, usually. Small alcohols are water soluble
because the hydroxyl groups can hydrogen bond with water molecules. But as the size of the
alkyl group increases the solubility in water decreases. This is the result of the alkyl group
disrupting hydrogen bonding among the water molecules. If the disruption becomes large enough
the water molecules, in effect, expel the alcohol molecules to reestablish hydrogen bonding.

Chemical Properties

The chemical test taken into consideration are those that assist in the identification of the classes
of alcohols.
1. Lucas Test
This test is used to distinguish among primary, secondary and tertiary water-soluble alcohols.
Lucas reagent is a mixture of concentrated hydrochloric acid and zinc nchloride. Zinc chloride is
a Lewis acid, which when added to hydrochloric acid makes it even more acidic. Water soluble
tertiary alcohols react with Lucas reagent almost immediately to form an alkyl chloride which is
insoluble in the aqueous solution. The formation of a second liquid phase in the test tube almost
as soon as the alcohol initially dissolves is indicative of a tertiary alcohol. A secondary alcohol
reacts slowly to form a chloride and, after heating a little, gives a second phase, usually within
ten minutes. Primary alcohols and methanol do not react under these conditions.

2. Chromic Acid Test

Primary alcohols are oxidized to carboxylic acids by chromic acid. The Cr+6 ions in the chromic
acid, which is red-brown, is reduced to Cr +3 ions, which is green. Secondary alcohols are
oxidized to ketones by chromic acid. The chromium reduction is the same here as for the primary
alcohols. Tertiary alcohols are not oxidized by chromic acid. Thus, this reaction can distinguish
between primary and secondary alcohols, on the one hand, and tertiary alcohols, on the other.

3. Reaction with Metallic Sodium

Alcohols, like water, are weak acids. The hydroxyl group can act as a proton donor to form an
alkoxide ion. Alkoxide ions dissolved in alcohol, like hydroxide ions in water, are strong bases
which can be prepared by the reaction of an alcohol with sodium metal. This reaction produces
hydrogen gas.
2 R-OH + 2 Na ---------> 2 R-O-Na+ + H2

Glassware :

Test tubes, 5mL measuring cylinder

Materials :

Ethanol (C2H5OH), isopropyl alcohol (C3H7OH), t-butyl alcohol (C4H9OH), Lucas

reagent (mixture of concentrated hydrochloric acid and zinc chloride), chromic
acid (H2CrO4), sodium metal.

Procedures:

A. Solubility of Alcohols
1. In three separate test tubes, about 1 mL of ethanol, isopropyl alcohol and t-butyl alcohol
was added into each test tubes.
2. About 2 mL of water was added to each tube, mixed and observed.
3. The experiment was repeated with two unknown liquids.
4. The observation was recorded.

B. Lucas Test
1. Approximately 1 mL portions of ethanol, isopropyl alcohol and t-butyl alcohol was added
in separate dry test tubes together with 6mL of Lucas reagent at room temperature.
2. The tubes was corked and shake. The time taken for the solution to turn cloudy or to form
layered solution was noted.
3. The solutions that does not turn cloudy was heated in a hot water bath for few minutes
and the observation was recorded.
4. The experiment was repeated with two unknown liquids.

C. Chromic Test
1. About 1mL of chromic acid was added into test tubes containing 2ml portions of ethanol,
isopropyl alcohol and t-butyl alcohol each.
2. Observation on the colour change was recorded .
3. The experiment was repeated with two unknown liquids provided.

D. Reaction with metallic sodium

1. In three separate dry test tubes, about 2mL of ethanol, isopropyl alcohol and t-butyl
alcohol was added, then a small piece of sodium metal was inserted into the tubes.
2. Any visible changes in the solution was recorded.
3. The different rate of gas evolution was compared and the alcohols was arranged in
increasing order of acidity.
4. The experiment was repeated with two unknown liquids provided.

Hydrocarbons

Ethanol

Isopropyl
alcohol

t-butyl alcohol

Unknown A

Unknown B

 Completely
soluble in
Solubility in
water
water
No visible
changes
Lucas Test

Completely
soluble in
water

Soluble in water Soluble in water Soluble in

water

Colourless
Immediate
Colourless
Immediate
solution turns
change to
solution turns
change to
cloudy upon
cloudy solution
cloudy upon
cloudy
heating in hot
from colourless
heating in hot
solution from
water bath
upon addition
water bath
colourless
of reagent
upon
addition of
reagent
Reddish-brown No visible
Reddish-brown No visible
solution turns
changes
solution turns
changes
to green
to green
colour
colour
solution with
solution with
black
black
precipitate
precipitate

Reddishbrown
solution
turns to
Chromic acid
blackishTest
green
solution
with black
precipitate
Vigorous
Moderate
Slow and calm Moderate
Slow and calm
reaction
reaction with
reaction with
reaction with
reaction with
with sodium
sodium metal
sodium metal.
sodium metal
sodium
metal.
metal.
Bubbles are
Bubbles are
Bubbles are
Reaction with
Bubbles are
sodium metal Bubbles are
released
released in
released
released
slowly.
little amount
slowly.
released in
readily
little amount
Results:

Discussion:

The general formula of an alcohol is R-OH in which the R is an aliphatic hydrocarbon

group. Alcohols may be looked upon as derivatives of water, H-OH. 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 or highly branched will be more soluble in water and will
have a lower boiling point than the straight chain isomer. Although alkyl alcohols have an -OH
group, they do not ionize in water. The -OH group of alkyl alcohols can be positioned on
different carbon atoms of the carbon chain and are classified as primary (1), secondary (2), or
tertiary (3) alcohols depending on whether the -OH group is attached to a carbon with 1, 2 or 3
other carbon atoms attached to it. [1][2]
In this experiment, the properties of alcohols were studies by treating the selected alcohol
of different natures to be tested with several testing reagents. The alcohols used were ethanol as
the primary alcohol, isopropyl alcohol as the secondary alcohol, and t-butyl alcohol as the
tertiary alcohol. Besides that, two unknown liquids were given to be tested and the nature of the
liquid was quest to be found.
Firstly, the solubility of the alcohols in water was tested. It was observed that all the
alcohols was reasonably soluble in water as no layer of mixtures was found in any of the test
tubes. This proves that all the alcohols are of simple compounds as the complex compound
would be insoluble in water due to the long hydrocarbon chain.

t-butyl
alcohol

Ethanol
Isopropyl
alcohol

Unknown

Unknown A

Hydrocarbon

Reaction equation

Ethanol

CH2H5OH(l) + H2O(l) C2H5O-(aq) + H+(aq)

Isopropyl alcohol C3H7OH(l) +H2O(l) C3H7O-(aq) + H+(aq)

t-Butyl alcohol

C4H9OH(l) + H2O (l) C4H9O-(aq) + H+(aq)

Observation
Soluble in water
Soluble in water
Soluble in water

Unknown A
Soluble in water
Unknown B
Soluble in water
Secondly, Lucas test was carried out on all the alcohols provided. This test is used to
distinguish among primary, secondary, and tertiary water soluble alcohols. Lucas reagent is a
mixture of concentrated hydrochloric acid and zinc chloride. Zinc chloride is a Lewis acid, which
when added to hydrochloric acid makes it even more acidic. Water soluble tertiary alcohols react

with Lucas reagent almost immediately to form an alkyl chloride which is insoluble in the
aqueous solution. The formation of a second liquid phase in the test tube almost as soon as the
alcohol initially dissolves is indicative of a tertiary alcohol. A secondary alcohol reacts slowly to
form a chloride and, after heating a little, gives a second phase, usually within 10 minutes.
Primary alcohols and methanol do not react under these conditions. In the case of tertiary
alcohols the chloride is usually attached to the carbon that held the hydroxyl group. In the case of
secondary alcohols, it is often the case that the chlorine is attached to the carbon that held the
hydroxyl, but rearrangements are possible.[2]
When the alcohols are tested with Lucas reagent, the t-butyl alcohol and Unknown B
liquids reacts at instance by forming a cloudy solution. This proves that both the solution are of
tertiary alcohol. On the other hand, isopropyl alcohol and Unknown A liquid forms a cloudy
solution only when introduced to heat, this prominently shows that the solutions are of the
secondary alcohols. Ethanol unlikely to form any interaction with the Lucas reagent and proved
to be primary alcohol.
Isopropyl
alcohol

Ethanol
t-butyl
alcohol

Unknown

Isopropyl
alcohol

Unknown

Unknown A

Addition of Lucas reagent: Before

Addition of Lucas reagent: After

Thirdly, the alcohols were tested with chromic acid. Generally, primary alcohols are
oxidized to carboxylic acids by chromic acid. The Cr +6 ions in the chromic acid, which is redbrown, is reduced to Cr+3 ions, which is green in colour. Secondary alcohols are oxidized to
ketones by chromic acid. The chromium reduction is the same here as for the primary alcohols.

Tertiary alcohols are not oxidized by chromic acid. Thus this reaction can distinguish between
primary and secondary alcohols on one hand and tertiary alcohols on the other.[2]

When the samples was tested with Chromic acid, ethanol, isopropyl alcohol and
Unknown A shows a positive results where the orange colour of the chromic acid was changed
to greenish blue-black solution with precipitate for ethanol and green solution with black
precipitate for isopropyl alcohol and Unknown A alcohol. This shows that oxidation reaction
occurs and the alcohols are of primary and secondary alcohols. For t-butyl alcohol and
Unknown B alcohol, there are no visible change to the orange colour of the chromic acid, this
indicated that there are no oxidation reaction took place and that the alcohols are of tertiary
alcohols.
t-butyl
alcohol

Ethanol

t-butyl
alcohol
Isopropyl
alcohol

Unknown

Isopropyl
alcohol

Unknown
Unknown A

Unknown A

Finally, the alcohols was tested with sodium metal. Chemically, alcohols are only slightly
weaker acids than water, with a K a value of approximately 1 10 16. The reaction of primary
alcohol, which in this experiments is ethanol with sodium metal, a base, produces sodium
ethoxide and hydrogen gas.[3]

This reaction is identical to the reaction of sodium metal with water.

However, the this reaction occurs faster because of the increased acidity of water
(K a value of 1 10 15). The acidity of alcohols decreases while going from primary to
secondary to tertiary. This decrease in acidity is due to two factors that is an increase of electron
density on the oxygen atom of the more highlysubstituted alcohol, and steric hindrance due to
the alkyl groups, which inhibit the dissolving property of the resulting alkoxide ion. Both of
these situations increase the activation energy for proton removal.[3]
The basicity of alkoxide ions increases while going from primary to tertiary. This increase in
basicity occurs because the conjugate base of a weak acid is strong. The weaker the acid, the
stronger the conjugate base[3]
In this experiment, it is observed that ethanol produce a vigorous reaction and release of
bubbles when introduced to sodium metal. The isopropyl alcohol and Unknown A alcohol
produce a moderately fast eaction with sodium metal and bubbles release. In contrast, t-butyl
alcohol and Unknown B alcohol show very slow and calm reaction towards sodium metal and
bubbles release. This shows, that the reactivity decreases from primary alcohol; ethanol, to
secondary alcohol; isopropyl alcohol and Unknown A and lastly tertiary alcohol; t-butyl alcohol
and Unknown B
Several precautionary steps was taken while conducting the experiment. Following
standard lab requirements, all students was ensured wearing lab coats, hand gloves and safety
goggles. When handling the Lucas reagent, extra caution was taken as it is highly toxic and
corrosive. The Lucas reagent was ensured to be handled in a fume chamber as the hydrochloric
acid vapour is highly toxic to respiratory system. When handling the chromic acid, high
precaution was taken to not to introduce any sodium to the acid as it produce a reaction with
incandescence.

References :
1. Alcohol. (1997). In Compendium of Chemical Terminology, (The Gold Book) (2nd ed.).
Online corrected version - (2006).

2. Properties of alcohol and phenol. (n.d.). Retrieved February 17, 2015, from
http://employees.oneonta.edu/knauerbr/chem226/226expts/226_expt08_pro.pdf
3. (n.d.). Retrieved November 1, 2014, from
http://www.cliffsnotes.com/sciences/chemistry/organic-chemistry-ii/alcoholsand-ethers/reactions-of-alcohols