FOUNDATION IN MEDICAL STUDIES (JULY 2013 INTAKE)

CHM1024 LABORATORY REPORT

PRACTICAL 4 : REACTIONS OF ALCOHOLS

NAME : AKMAL ADIB BIN FADZIL

MATRIX ID : CPM0018_2013C

GROUP : A

SEMESTER : TWO

DATE : 4th FEBRUARY 2014

LECTURER : MR. MOHD YUSOFF HUSSAIN

OBJECTIVE

The objective of this experiment is to classify the different types of alcohols.

INTRODUCTION

An alcohol is an organic compound which has a hydroxyl group (-OH) attached to a carbon
atom. This carbon atom should be saturated which means that it is single – bonded to a
hydroxyl functional group and other three atoms. An important class of alcohols are the
aliphatic alcohols which has a general formula of CnH2n+1OH. Aliphatic alcohols can be
considered as a derivative of alkanes with a hydrogen atom replaced by a hydroxyl group.

In the IUPAC system, the name of the alkane chain loses the terminal "e" and replaced with
"ol” such as "methanol" and "ethanol". When necessary, the position of the hydroxyl group is
indicated by a number between the alkane name and the "ol" such as propan-1-ol for
CH3CH2CH2OH and propan-2-ol for CH3CH(OH)CH3. Sometimes, the position number is
written before the IUPAC name: 1-propanol and 2-propanol. If a higher priority group is
present such as an aldehyde, ketone, or carboxylic acid, then it is necessary to use the prefix
"hydroxy". For example: 1-hydroxy-2-propanone (CH3COCH2OH).

Alcohols can be classified into primary (1°), secondary (2°) and tertiary (3°) alcohols
according to the number of alkyl groups bonded to the carbon atom that has the –OH group
attached. In 1° alcohols, the –OH group is bonded to a carbon atom with one or no alkyl
groups attached. Ethanol is an example of a primary alcohol. In 2° alcohols, the –OH group
is bonded to a carbon atom with two alkyl groups attached. For example, 2-propanol is a
secondary alcohol. In 3° alcohols, the –OH group is bonded to a carbon atom with three alkyl
groups attached. For example, 2-methyl-2-propanol is a tertiary alcohol.

Most simple aliphatic alcohols and the lower aromatic alcohols such as phenyl methanol,
C6H5CH2OH are liquids at room temperature while highly branched alcohols and alcohols
with twelve or more carbon atoms are solids. In general, the hydroxyl group makes the
alcohol molecule polar. Those groups can form hydrogen bonds to one another and to other
compounds except in certain large molecules where the hydroxyl is protected by steric
hindrance of adjacent groups. This hydrogen bonding means that alcohols can be used
as protic solvents. Protic solvents are solvents that can dissolve salts. Because of hydrogen
bonding, the boiling points of alcohols are considerably higher than those of alkanes and
chloroalkanes of similar relative molecular mass (RMM). This is because intermolecular
hydrogen bonds exist between the –OH groups in the alcohol molecules. For example:

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 C2H5OH CH3CH2CH3 CH3Cl

ethanol propane chloromethane

RMM : 46 44 50.5

Boiling point : 78°C -42°C -24°C

For isomeric alcohols, straight – chain alcohols have higher boiling point than their branched
– chain alcohols counterpart. The greater the degree of branching in an isomer, the lower its
boiling point. For example:

When it comes to solubility of alcohols, there are two opposing solubility trends in which are:
the tendency of the polar OH to promote solubility in water, and the tendency of the carbon
chain to resist it. Methanol, ethanol, and propanol are miscible in water because the hydroxyl
group wins out over the short carbon chain. Butanol, with a four-carbon chain, is moderately
soluble because of a balance between the two trends. Alcohols of five or more carbons
(pentanol and higher) are effectively insoluble in water because of the hydrocarbon chain's
dominance. All simple alcohols are miscible in organic solvents. Alcohols, like water, can
show either acidic or basic properties at the -OH group. With a pKa of around 16-19, they are
generally slightly weaker acids than water, but they are still able to react with strong bases
such as sodium hydride or reactive metals such as sodium. The salts that result are
called alkoxides, with the general formula RO- M+. The oxygen atom has lone pairs of non-
bonded electrons that render it weakly basic in the presence of strong acids such
as sulphuric acid. As one moves from primary to secondary to tertiary alcohols with the same
backbone, the hydrogen bond strength, the boiling point, and the acidity typically decrease.

For this experiment, three unknown alcohols will be classified into 1°, 2° and 3° alcohols by
conducting several tests to see its results which include the end – product formed, colour of
the end – product and the time taken for the reaction. Besides that, esterification is carried
out to determine the properties of esters by mixing an alcohol with a carboxylic acid.

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APPARATUS AND MATERIALS

1. 0.04 M sodium dichromate, Na2Cr2O7 solution.

2. Alcohol A.

3. Alcohol B.

4. Alcohol C.

5. Ethanol.

6. Concentrated sulphuric acid, H2SO4 solution.

7. Droppers.

8. Glacial acetic acid.

9. Lucas’ reagent.

10. Cold Schiff’s reagent.

11. Distilled water.

12. Rubber stopper.

13. 8 test tubes.

14. Water bath (maintained at 70℃).

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METHOD

A. Lucas’ Test.

1. 1 ml of alcohol A is placed into a test tube.

2. 5 – 10 drops of Lucas’ reagent is added to the test tube.

3. Rubber stopper is inserted onto the test tube. The test tube is then shaken.

4. Any observations and the time taken for the reaction to occur are recorded.

5. Steps 1 – 4 are repeated by replacing alcohol A with alcohol B and C. The test
tube is placed in the water bath (maintained at 70℃) if no change occurs
within 10 minutes.

B. Oxidation.

1. 10 drops of 0.04 M sodium dichromate (VI), Na2Cr2O7 solution is placed into a

test tube.

2. 2 – 3 drops of concentrated sulphuric acid, H2SO4 solution is added into the

test tube in a fume hood.

3. 5 drops of alcohol A is added into the mixture.

4. Any changes in the colour of the mixture are recorded.

5. The mixture is further tested by adding 5 drops of cold Schiff’s reagent and
heated in the water bath (maintained at 70℃) if the colour of the mixture turns
green.

6. Any changes in the colour of the mixture are recorded.

7. Steps 1 – 6 are repeated by replacing alcohol A with alcohol B and C.

C. Esterification.

1. 2 ml of ethanol is placed in a dry test tube.

2. 1 ml of glacial acetic acid and 3 drops of concentrated sulphuric acid, H2SO4

solution are added into the test tube in a fume hood.

3. The mixture is shaken and then warmed in a water bath at 70℃ for 5 – 10
minutes.

4. 3 ml of distilled water is added into the mixture. The vapour released is

smelled and described.

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RESULTS

OBSERVATION
TEST
ALCOHOL A ALCOHOL B ALCOHOL C

The colourless The colourless The colourless

LUCAS’ TEST solution turns cloudy solution turns cloudy solution remains
immediately. after a few minutes. unchanged.

1. Colour of the 1. Colour of the 1. Colour of the

solution remains solution changes solution changes
orange. from orange to from orange to
1. OXIDATION
green. green.
2. SCHIFF’S
2. Colour of the 2. Colour of the
2. Not performed
REAGENT
green solution green solution
because the
TEST
turns magenta turns magenta
colour of the
slowly. immediately.
solution remains
orange.

ESTERIFICATION A pleasant smell is detected from the test tube.

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DISCUSSION

Lucas’ Test.

The Lucas’ reagent used in this experiment is an aqueous solution of strong hydrochloric
acid, HCl and zinc chloride, ZnCl2. The reactants used to react with this reagent must be
water – soluble so that a reaction can take place. An alcohol with more than six carbons is
too large to be dissolved in the reagent while water – soluble alcohol which has low
molecular weight can react with this reagent. This gives further insight of the unknown
alcohols given in which the alcohols can be methanol, ethanol, propanol or butanol of
different classification.

For this experiment, each of the unknown alcohols is treated with Lucas’ reagent. If the
colour of the solution remains unchanged, it is heated in a water bath at 70°C. Positive
indicator of the reaction is the formation of water –insoluble alkyl chloride as cloudiness or a
precipitate. Theoretically, 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.

When alcohol A is used, the colour of the solution changes to cloudy immediately. When
alcohol B is used, the colour of the solution changes to cloudy after a few minutes. When
alcohol C is used, the colour of the solution remains unchanged. The results obtained shows
that alcohol A is a 3° alcohol, alcohol B is a 2° alcohol and alcohol C is a 1° alcohol.

The reaction that occurs in the Lucas test is a nucleophilic substitution. Only alcohols that
can generate stable carbocation intermediates will undergo the reaction. The acid catalyst
activates the OH group of the alcohol by protonating the oxygen atom. The C – OH2+ bond
breaks to generate the carbocation, which in turn reacts with the chloride ion (nucleophile) to
generate an alkyl halide product. A general mechanism for this nucleophilic reaction is as
follows:

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In simpler words, the chemical reaction involves replacing the –OH group of the alcohol with
a chloride ion from HCl to form the insoluble alkyl chloride.

For alcohol A (3° alcohol):

For alcohol B (2° alcohol):

For alcohol C (1° alcohol):

Zinc chloride (ZnCl2) is a catalyst for this reaction, which makes up for the name of test that
is Lucas test. The resultant alkyl chloride is insoluble in water and separates from the Lucas
reagent (ZnCl2 in concentrated HCl), forming a cloudy mixture, an emulsion or a new
“organic” layer to form in the reaction mixture, or sometimes only a colour change will be
observed (red or orange).

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Oxidation.

There are two steps for doing this experiment. The first step is to use sodium dichromate
(VI), Na2Cr2O7 solution acidified with concentrated sulphuric acid, H2SO4 to differentiate
between tertiary and primary/secondary alcohols. If oxidation occurs, the orange solution
containing the dichromate (VI) ions are reduced to a green solution containing chromium (III)
ions. The second step is to use cold Schiff’s reagent to differentiate between primary and
secondary alcohols. If the green colour of the solution turns magenta immediately, it is a
primary alcohol. If it remains green or turns magenta at a slow rate, it is a secondary alcohol.

For the first step, all of the unknown alcohols are added to a mixture of sodium dichromate
(VI), Na2Cr2O7 solution and concentrated sulphuric acid, H2SO4. The result is that alcohol A is
3° alcohol while alcohol B and C is either 2° alcohol or 1° alcohol. The reason is that tertiary
alcohols are not oxidised by the acidified sodium dichromate (VI), Na2Cr2O7 solution as they
do not have a hydrogen atom attached to the carbon. Secondary and primary alcohols can
be oxidised by the acidified sodium dichromate (VI), Na2Cr2O7 solution as the oxidising agent
(acidified Na2Cr2O7 solution) removes a hydrogen from the –OH group and a hydrogen atom
attached to the carbon that has the –OH group.

The general equations for the reactions mentioned above are as follows:

3RCH2OH + Cr2O72- + 8H+ → 3RCHO + 2Cr3- + 7H2O

(1° alcohol) (orange) (aldehyde) (green)

R’ R’

| |

3R – CH – OH + Cr2O72- + 8H+ → 3R – C = O + 2Cr3+ + 7H2O

(2° alcohol) (orange) (ketone) (green)

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Tertiary alcohols do no react with the acidified Na2Cr2O7 solution and thus no equation can
be made. Also note that if the aldehyde formed from the oxidation of 1° alcohol is allowed to
oxidise further, it will produce a carboxylic acid. The diagram of the results obtained is as
follows:

Since the colour produced for both mixture C and B is green, it is not sure which one produce
an aldehyde (1° alcohol) and which one produces a ketone (2° alcohol).

Now that the first step is done, the experiment now proceeds to the second step. The second
step involves adding the green-coloured alcohol C and B from the previous step with cold
Schiff’s reagent. Schiff's reagent is a fuchsin dye decolorized by passing sulfur dioxide
through it. In the presence of even small amounts of an aldehyde, it turns magenta. The
reagent is cooled to prevent ketone from reacting with the reagent to give the same colour.
Theoretically, if the colour of the mixture containing Schiff’s reagent turns magenta, the
alcohol used is a 1° alcohol. This is because 1° alcohols are oxidised by the acidified
Na2Cr2O7 solution to form aldehydes which causes the colour of the solution with cold
Schiff’s reagent to turn magenta. If there is no change in colour of the mixture or only a trace
of pink colour is detected after a while, it is a 2° alcohol as 2° alcohols are oxidised by the
acidified Na2Cr2O7 solution to form ketones. Ketones have no effect on the colour of the
solution with cold Schiff’s reagent.

From the experiment, the colour of the mixture containing alcohol C turns magenta while the
mixture containing alcohol B remains green in colour when added with cold Schiff’s reagent.
Therefore, alcohol C is a 1° alcohol while alcohol B is a 2° alcohol. Alcohol A has been stated
earlier which is a 3° alcohol.

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Esterification.

This experiment is based on the special, classic type of esterification which is the Fischer –
Speier esterification. It involves a reflux between a carboxylic acid with an alcohol in the
presence of an acid catalyst to produce an ester. It is a nucleophilic acyl substitution
reaction. Most carboxylic acids are suitable for the reaction, but the alcohol should generally
be a primary or secondary alkyl. Tertiary alcohols are prone to elimination and phenols are
usually too unreactive to give useful yields. Since esterification is highly reversible, the yield
of the ester can be improved by using Le Chatelier's principle which includes: using the
alcohol in large excess and using a dehydrating agent such as concentrated sulphuric acid to
remove water (one of the end – products). The general equation for this type of esterification
is:

For this experiment, ethanol and glacial acetic acid (ethanoic acid) is mixed in a dry test tube
and added with concentrated sulphuric acid. The mixture is later shaken and heated in a
water bath at 70°C for a few minutes. After that, a few amount of distilled water is added into
the mixture before lightly smelling the vapour released. The smell is a pleasant smell which
seems to be a bubble – gum like smell. The full equation of the reaction is as follows:

CH3CH2OH + CH3COOH → CH3COOCH2CH3 + H2O

The mechanism of reaction between the ethanol and acetic acid is as follows:

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Step 1:
An acid/base reaction. Protonation of the carbonyl makes it
more electrophilic.

Step 2:
The alcohol O functions as the nucleophile attacking the
electrophilic C in the C=O, with the electrons moving towards
the oxonium ion.

Step 3:
An acid/base reaction. Deprotonate the alcoholic oxygen.

Step 4:
An acid/base reaction. Need to make the -OH leave, so convert
it into a good leaving group by protonation.

Step 5:
Use the electrons of an adjacent oxygen to help "push out" the
leaving group, a water molecule.

Step 6:
An acid/base reaction. Deprotonation of the oxonium ion
reveals the carbonyl in the ester product.

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Precaution.

Throughout the experiment, there are several precautions that were taken and noted in the
experiment. One of them is to use concentrated sulphuric acid in a fume hood to avoid
inhalation of the fume released from the acid is dangerous as it is toxic and capable of
damaging the mucous membrane. Besides that, all alcohols must be kept away from any
source of fire throughout the experiment as alcohols are highly flammable. Another one is to
use safety gloves and lab coat to avoid contact with corrosive or irritating substances such as
concentrated sulphuric acid and Lucas’ reagent in case if caution is not fully taken. Wearing
safety gloves also protects the hand from staining of substances that are not easily removed
such as sodium dichromate solution. In addition, all test tubes used in the experiment should
be cleaned and rinsed with distilled water before drying it for use. Last but not least, all
chemical wastes of the experiment need to be disposed thoroughly and carefully.

CONCLUSION

As a conclusion, the unknown alcohols are able to be classified. By conducting the Lucas’
test and oxidation test, the alcohols A, B and C are able to be classified into 1°, 2° and 3°
alcohol. Alcohol A is a 3° alcohol, alcohol B is a 2° alcohol and alcohol C is a 1° alcohol. 1°
alcohol undergoes oxidation but react slowest in halogen substitution reaction. 2° undergoes
oxidation and react with a medium speed under halogen substitution reaction. Tertiary
alcohols never undergo oxidation but react immediately in halogen substitution reaction.
Alcohols react with carboxylic acids to form an ester.

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QUESTIONS

1. Write the full equation for esterification reaction in this experiment.

CH3CH2OH + CH3COOH → CH3COOCH2CH3 + H2O

2. What does the formation of two layers in the Lucas’ test indicate? Explain.

The formation of two layers in the Lucas’ test indicates a positive result of the
experiment. A positive result is the formation of the insoluble alkyl chloride from the
reaction of tertiary/secondary alcohols with Lucas’ reagent. The alkyl halide forms a
layer at the top of the mixture.

3. Give two examples for each type of alcohol and draw the structures.

For the 1° alcohol:

For the 2° alcohol:

For the 3° alcohol:

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REFERENCES

1. CHEMISTRY FOR MATRICULATION SEMESTER 2 FOURTH EDITION, Tan Yin

Toon, Oxford Fajar Sdn. Bhd. 2013.
2. http://www.scribd.com/doc/50151853/exp-3-classification-of-alcohols
3. http://www.chemguide.co.uk/organicprops/alcohols/esterification.html
4. http://www.mhhe.com/physsci/chemistry/carey/student/olc/ch15synthesisesters.html
5. http://www.organicchem.org/oc2web/lab/exp/oxid/lucas.pdf
6. http://swc2.hccs.edu/pahlavan/2425L4.pdf
7. http://chemwiki.ucdavis.edu/Organic_Chemistry/Alcohols/Reactions_of_Alcohols/The
_Oxidation_of_Alcohols
8. http://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/alcohol2.htm

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