Experiment 6

ANALYSIS OF HYDROCARBONS
Hydrocarbons are the simplest of all organic compounds because they are composed only of two
elements, carbon and hydrogen. They may be saturated or unsaturated. The saturated hydrocarbons or
alkanes are organic compounds in which carbon is bonded to four other atoms by single bonds.
Unsaturated hydrocarbons include alkenes, alkynes and the aromatics.
Alkanes have no functional groups, hence they are not abundant in the human body. However, most
compounds in human cells contain parts consisting solely of carbon and hydrogen that behave very much like
hydrocarbons. Understanding the physical and chemical properties of hydrocarbons will help understand the
properties of more complex biomolecules.
Hydrocarbons also play a crucial role in the industry as primary sources of energy and as important
sources of raw materials for the manufacture of plastics, synthetic fibers, drugs and other compounds used
daily.

Reactions of important functional groups include:

a. tests for unsaturation
b. test for 1-alkynes or the silver acetylide test/Tollens test
c. tests for aromaticity

A. Tests for Unsaturation

1. Bromine test
- Alkenes and alkynes form a colorless 1,2 dibromo addition product with red colored bromine. However,
aromatic compounds and conjugated systems do not react with bromine.
2. Baeyer's test
- Unsaturated hydrocarbons undergo oxidation by strong oxidizing agents like KMnO4 (Baeyer's reagent)
at room temperature. Olefins are oxidized to a colorless diol while the purple colored KM04 is reduced
to a brown precipitate of manganese dioxide.

B. Test for 1-Alkynes / Silver Acetylide test

- Acetylides are formed when alkynes containing acidic hydrogens react with metal ions to form a solid
product which explodes when dry.

C. Test for Aromaticity

1. Le Rosen test
- Aromatic hydrocarbons react with formaldehyde in the presence of an acid to form benzophenone, a
purple colored product.

2. Nitration test
- Aromatic compounds can undergo nitration with concentrated nitric acid in the presence of
concentrated sulfuric acid to produce nitro compounds which are usually yellow.

3. Ignition test
- Aromatic hydrocarbons burn with sooty flame because of an incomplete combustion that causes the
formation of unburned carbon.
 Experiment 6
ANALYSIS OF HYDROCARBONS
4. Oxidation with Alkaline Potassium Permanganate
- Aromatic hydrocarbons are resistant to oxidation except when an alkyl side chain is present. Strong
oxidizing agents like alkaline KMnO4 can oxidize the side chain producing benzoic acid. The purple
permanganate in turn, is reduced to a brown precipitate of MnO2.
APPARATUS
- Burner, platform balance, iron stand, pneumatic trough, 400 mL beaker, combustion tube, delivery tube,
corks/rubber stoppers, clamp, droppers, test tubes, thermometer, watch glass, match

REAGENTS
- Calcium carbide, CaC2, 5% Br2 in dichloromethane, hexane, cyclohexene, toluene, alkaline KM04,
Tollen's reagent, Le Rosen reagent (10% solution of formaldehyde in conc. H204 ), styrene, conc. HNO,
conc.H2SO4

SAFETY PRECAUTION
1. Both concentrated H2SO4 and HNO are very corrosive. Do not allow them to come in contact with your
skin. In case of contact, wash any affected area thoroughly with cold water and apply 5% sodium
bicarbonate solution.
2. Solutions of KM04 and AgNO: can cause unsightly stains on your hands for several days. Wear rubber
gloves. If you get them on your skin, wash the affected area thoroughly with warm water.
3. Bromine is a hazardous chemical. It causes severe burns to every area of contact. All operations
involving the transfer of bromine should be performed in a hood. In case of skin contact, wash the
affected area with warm water and soak in 0.6M Na2S203 solution.
4. Cyclohexene is extremely flammable: keep away from open flames.

Preparation of Acetylene
Acetylene may be prepared in the laboratory by the action of water on calcium carbide. Acetylene forms
explosive mixtures with air and care should be exercised to keep the gas generator away from all flames.
Acetylene has an unpleasant smell, always keeping the end of the rubber tubing under water to prevent the
gas from diffusing into the air.

PROCEDURE
1. Place a spatula of CaC2 in an ignition tube and gradually add 3 mL of water. Cover and connect the
delivery tube as shown in the following figure.
2. Collect at least five test tubes of the gas per group by water displacement and cover the tubes with
corks/rubber stoppers.
 Experiment 6
ANALYSIS OF HYDROCARBONS
A. Tests for Unsaturation
Wear gloves and protective glasses.
1. Bromine test
a. In a test tube containing acetylene gas, place 5 drops of 5% bromine in dichloromethane. Note the
color change produced and compare with a control tube containing the bromine reagent only.
b. Repeat the same test using 5 drops of the following test compounds in separate test tubes: hexane,
cyclohexene, toluene.
2. Baeyer's test
a. To another test tube containing acetylene, add 5 drops of alkaline KMnO4. What do you observe?
b. Perform the same test by using 5 drops of the following test compounds in separate test tubes: hexane,
cyclohexene, toluene.

3. Test for 1- Alkynes/ Silver Acetylide test

a. Into a test tube containing acetylene gas, add 10 drops of the freshly prepared Tollen's reagent.
b. Stopper and shake the tube. Note the color of the precipitate formed.
c. Repeat step 3a using 5 drops each of hexane, cyclohexene and toluene in three different test tubes.

4. Ignition Test
a. Hold a test tube containing acetylene gas at arm's length with a test tube holder
b. Into the test tube containing acetylene gas, introduce a lighted splinter.
c. Observe the flame and the inside of the test tube.

B. Tests for Aromaticity

1. Le Rosen test
a. Place 10 drops of Le Rosen reagent in a test tube.
b. Add 5 drops of toluene on the side of the test tube. Note the color change.

2. Nitration test
a. Prepare the nitrating mixture by carefully mixing 10 drops of conc. HaSO. and 10 drops of conc. HNO in
a test tube placed in a beaker containing cold water.
b. Add 10 drops of toluene dropwise to the nitrating mixture. Shake the test tube to ensure complete
mixing. (Keep the mouth of the tube away from anyone.)
c. If no apparent reaction is observed within one minute, place the test tube in a water bath (-50°C) for 15
minutes.
d. Slowly pour the mixture into a beaker containing 10 mL of water. Observe the color of the compound
formed.

3. Ignition test
a. Place 5 drops of toluene in a watch glass and ignite with a match.
b. Observe the color of the flame.

4. Oxidation with Alkaline Potassium Permanganate

a. Place 2 to 3 drops of toluene in a test tube.
b. Add 5 drops of alkaline KMn04.
c. Warm the tube for 1 minute and observe any change in color.
 Experiment 6
ANALYSIS OF HYDROCARBONS
CLEANING UP
1. Any solution in which the color of bromine is visible can be decolorized by the dropwise addition of
cyclohexene. Discard the resulting mixture in the container for halogenated liquids.
2. Filter all solutions to remove the manganese dioxide produced in the Baeyer's test. Discard the filter
paper together with the precipitate in the chemical container for solid wastes. Flush all filtrates down the
drain.
3. Destroy solid silver acetylide salt by treatment with hydrochloric acid. Put the resulting silver chloride in
the container for solid waste, and then flush the filtrate down the drain.