Chemistry 1B Lab Manual 13-14 Page | 8

Experiment 1: Observational Skills in Synthetic Chemistry

Background and Experimental Objective

Visual observation continues to be a highly important tool in the study of chemical
reactions; in this experiment you will use your observational skills to investigate
the reactivities of alkyl halides, hydrocarbons and carbonyl containing compounds.

Part 1: Investigation of the Reactivities of Alkyl Halides

Alkyl halides undergo nucleophilic substitution reactions. A typical example of this
is the reaction of 2-chloro-2-methylpropane with water, as shown below in Figure
1.

Scheme 1: Reaction of 2-chloro-2-methylpropane with water.

In this reaction the nucleophilic reagent is water and the overall result is hydrolysis
of the alkyl halide to form an alcohol. A general mechanism for such reactions is
shown in Scheme 2.




The rate determining step in these reactions is the formation of the carbocation
intermediate. This experiment will allow you to investigate what effect changing
the alkyl group, R, and the halogen, X, will have on the rate of reaction. Although
you will be using a silver ion catalyst in this experiment, the rate determining step
is still the formation of the carbocation intermediate as shown in Scheme 3. So,
the rate at which the silver halide is precipitated is a measure of the rate of
formation of the carbocation.

H
2
O + CH
3
C
CH
3
CH
3
Cl CH
3
C
CH
3
CH
3
OH + HCl
R X X
-
+ R
+
H 2 O
c a r boc a t i on
R ' O H
R O R '
R O H
a l ke n e
Scheme 2: The formation and further reactions of carbocations
Chemistry 1B Lab Manual 13-14 Page | 9


Scheme 3: Silver catalysed substitution reactions.

Part 2: Investigation of the Reactivities of Hydrocarbons

Different kinds of hydrocarbons, e.g. alkanes, alkenes and aromatics, may be
distinguished from each other by their reactivity.

Reacts with
Electrophiles?
Undergoes
Friedel-Crafts
Acylation?
Alkane
Alkene
Aromatic
Table 1: Differentiation of the reactivity of hydrocarbons

You will investigate four hydrocarbons, using the tests shown in the table, to
identify which is an alkane, alkene, aromatic or polyaromatic compound.

Part 3: Investigating the Reactivities of Carbonyl- Containing Compounds

The carbonyl group plays an important role in a wide range of organic and
biochemical reactions. The carbonyl group in aldehydes and ketones is fairly
reactive so these are often used as intermediates in the synthesis of more complex
molecules.

You will investigate five liquids and use the tests shown in the table below to
identify if the liquid contains an aldehyde, ketone, ester or amide functional group.

Aldehyde Ketone Ester Amide
Bradys Test
Iodoform Test (if HCOCH
3
) (if RCOCH
3
)
Fehlings Test
Tollens Test
Alkaline Hydrolysis
Table 2: Differentiation of the reactivity of carbonyl compounds




RX
slow
AgX + R
+
fast
Products
Chemistry 1B Lab Manual 13-14 Page | 10

Experimental Procedure

Part 1: Investigation of the Reactivities of Alkyl Halides

1.1 Primary, Secondary and Tertiary Alkyl Halides
Collect 3 test tubes from your cabinet and the following alkyl halides
from the experiment trolley: 1-chlorobutane, 2-chlorobutane and 2-
chloro-2-methylpropane.

Label the test tubes 1, 2 and 3 using a marker pen. Then place two
drops of 1-chlorobutane into test tube 1, two drops of 2-chlorobutane
into test tube 2 and two drops of 2-chloro-2-methylpropane into test
tube 3. Next add 2 cm
3
of 0.05% silver nitrate in ethanol solution into
each tube, and then swirl each test tube to ensure the solutions mix
thoroughly. Using a stopwatch record how long it takes for a
precipitate to form in each test tube, and record this time on your report
sheet. If after 30 minutes no precipitate has formed, place the test
tube(s) into a beaker containing hot water and monitor precipitate
formation for a further 20 minutes.

1.2 Variation of Leaving Group

Collect 3 test tubes from your cabinet and the following alkyl halides
from the experiment trolley: 2-chlorobutane, 2-bromobutane and 2-
iodobutane.

Label the test tubes 4, 5 and 6 using a marker pen. Then place two
drops of 2-chlorobutane into test tube 4, two drops of 2-bromobutane
into test tube 5 and two drops of 2-iodobutane into test tube 6. Next
add 2 cm
3
of 0.05% silver nitrate in ethanol solution into each tube
then swirl each test tube to ensure the solutions mix thoroughly. Using
a stopwatch record how long it takes for a precipitate to form in each
test tube, and record this time on your report sheet. If after 30 minutes
no precipitate has formed, place the test tube(s) into a beaker containing
hot water and monitor precipitate formation for a further 20 minutes.






Work in pairs for this experiment

Alkyl halides
are suspected
carcinogens
and silver salts
are toxic- wear
gloves

Alkyl halides
are suspected
carcinogens
and silver salts
are toxic- wear
gloves
Chemistry 1B Lab Manual 13-14 Page | 11

1.3 Variation of Alkyl Group
Collect 3 test tubes from your cabinet and the following alkyl halides
from the experiment trolley: 1-bromobutane, 3-bromo-1-propene and
bromobenzene.

Label the test tubes 7, 8 and 9 using a marker pen. Then place two
drops of 1-bromobutane into test tube 7, two drops of 3-bromo-1-
propene into test tube 8 and two drops of bromobenzene into test tube
9. Next add 2 cm
3
of 0.05% silver nitrate in ethanol solution into each
tube then swirl each test tube to ensure the solutions mix thoroughly.
Using a stopwatch record how long it takes for a precipitate to form in
each test tube, and record this time on your report sheet. If after 30
minutes no precipitate has formed, place the test tube(s) into a beaker
containing hot water and monitor precipitate formation for a further 20
minutes.

Part 2: Investigation of the Reactivities of Hydrocarbons

Collect hydrocarbons H1, H2, H3 and H4 from the experiment trolley. Then carry
out the following tests on them all to identify which is an alkane, which is an
alkene and which is aromatic. Make sure you record all observations on the table
on your report sheet. The bottles labelled H1 to H4 contain one or another of the
following compounds shown in the table below: you will use these tests to work
out which is which!




Test 2.1 Bromine Test for Alkene Presence

Weigh out 1-2 mg of each unknown hydrocarbon and transfer them into
four test tubes (each test tube should only contain 1 unknown!). Add
0.5 cm
3
of dichloromethane to each test tube and then add two drops of
3% bromine solution and record the results on your report sheet (a
positive result from this test is that the bromine is decolourised).






n-hexane cyclohexene methylbenzene phenanthrene

Alkyl halides
are suspect
carcinogens
and silver salts
are toxic- wear
gloves

Treat all organic
compounds as
toxic. Bromine
and aluminium
chloride are
toxic- wear
gloves
Chemistry 1B Lab Manual 13-14 Page | 12

Test 2.2 Friedel-Crafts Test for Aromatic Systems

Weigh out 5-10 mg of each unknown hydrocarbon and transfer them into four test
tubes (each test tube should only contain 1 unknown!). Add 0.5 cm
3

dichloromethane to each test tube. Then collect a micro test tube and add some
anhydrous aluminium chloride to it, to cover the bottom of the tube. Do not add
any more than this!

Next, carefully heat this solid using a heating block to sublime the
material. Allow this tube to cool to room temperature and then add 4
drops of H1 to the micro test tube. Then prepare more sublimed
anhydrous aluminium chloride and repeat the test using unknowns H2,
H3 and H4. Record the colour of the solution formed on your report
sheet.

A positive result for this test is the formation of a coloured precipitate. Benzene
gives an orange or red colour, whereas polycyclic aromatics give purple colours.

Part 3: Investigation of the Reactivities of Carbonyl- Containing Compounds

Collect unknown carbonyl compounds C1 to C5 from the experiment trolley and
carry out the following tests on each of them. The bottles labelled C1 to C5 contain
one or another of the following carbonyl compounds shown in the table below;
you will use these tests to work out which is which!

Test 3.1 Bradys Test for Carbonyl Functionality

Collect a test tube and then add 1 cm
3
of Bradys reagent into it. Then
add two drops of the unknown to the test tube. Carry out this test for
each of the unknowns C1 to C5.

A positive result for this test is the formation of a yellow or red
precipitate.

Ethanal Propan-2-one Pentan-3-one Formamide Ethyl ethanoate

Aluminium
chloride is
Corrosive- wear
gloves

Treat all organic
compounds as
toxic - wear
gloves
Chemistry 1B Lab Manual 13-14 Page | 13


A scheme for this test is shown below:


Scheme 4: Brady's Test

Test 3.2 The Iodoform Test for Aldehydes and Ketones

Collect a boiling tube and then add 1 cm
3
of iodine solution to it. Next, add five
drops of the unknown to the test tube. Then add 2 M sodium hydroxide until the
colour of the iodine disappears and gently heat the solution for 2-3 minutes using
a heating block. Carry out this test for each of the unknowns C1 to C5.

A yellow precipitate will form if an aldehyde or ketone containing is
present.

Test 3.3 Fehlings Test for Aldehyde Functionality

Collect a boiling tube and then add 2 cm
3
of Fehlings A and 2 cm
3
of
Fehlings B solution to it. Next, add five drops of the unknown to the
test tube and gently boil the solution for 2-3 minutes using a heating
block. Carry out this test for each of the unknowns C1 to C5.

A positive result for this test is the formation of a red precipitate.

A general scheme for this test is show below:


Scheme 5: Fehling's test

R
C O
R'
R, R' = H, alkyl or aryl
+ H
2
NNH NO
2
O
2
N
NNH NO
2
O
2
N
C
OH
R
R'
H
-H
2
O
NNH NO
2
O
2
N
C
R'
R
C
CH
3
O

Treat all organic
compounds as
toxic - wear
gloves
Chemistry 1B Lab Manual 13-14 Page | 14

Test 3.4 Tollens test for Aldehydes

Collect a test tube and add 1 cm
3
of 0.1 M silver nitrate solution and 2-3 drops of 2
M sodium hydroxide solution. This will result in the formation of a silver oxide
precipitate. Add dilute ammonia until this precipitate dissolves. Then add 2-3
drops of the unknown carbonyl compound. Next, place the test tube in a warm
water bath for 5 minutes. Record any observations on your report sheet.

A positive result for this test is the formation of a silver mirror effect in the test
tube.

A general scheme for Tollens test is shown below:-


Scheme 6: Tollen's Test


Test 3.5 Alkaline Hydrolysis Test for differentiation of an Amide and Ester

Collect a test tube and add 5 drops of the unknown carbonyl compound
to it. Then add 2 cm
3
of 2 M sodium hydroxide to the test tube. Leave
this solution to react for 2-3 minutes, and then hold a piece of
moistened red litmus pH paper above the test tube, and record the
colour of it on your report sheet.

A positive result in this test is that the pH test paper turns blue, as this
shows ammonia has been produced, showing that an amide was
present. An ester would also be hydrolysed by the sodium hydroxide, but
the red litmus pH paper would remain red, as no ammonia will be
produced.


Now complete the report sheet.

This report sheet must be submitted at your next lab session
to your demonstrator for marking and feedback.


Treat all organic
compounds as
toxic - wear
gloves