Hydrocarbons

Background

The number of known organic compounds totals into the millions. Of these compounds,
the simplest types are those which contain only hydrogen and carbon atoms. These are
known as hydrocarbons. Because of the number and variety of hydrocarbons that can
exist, some means of classification is necessary.
One means of classification depends on the way in which carbon atoms are connected.
Chain aliphatic hydrocarbons are compounds consisting of carbon s linked either in a
single chain or in a branched chain. Cyclic hydrocarbons are aliphatic compounds that
have carbon atoms linked in a closed polygon (also referred to as a ring). For example,
hexane (single) and 2-methylpentane (branched) are chain aliphatic molecules, while
cyclohexane is a cyclic aliphatic compound.

Another means of classification depends on the type of bonding that exists between
carbons. Hydrocarbons which contain only carbon-to-carbon single bonds are called
alkanes. These are also referred to as saturated molecules. Hydrocarbons containing at
least one carbon-to-carbon double bond are called alkenes, and those compounds with at
least one carbon-to-carbon triple bond are called alkynes. These are compounds that are
referred to as unsaturated molecules. Finally, a class of cyclic hydrocarbons that contain a
closed loop (sextet) of electrons are called aromatic.
With so many compounds possible, identification of the bond type is an important
step in establishing the molecular structure. Quick, simple tests on small samples can
establish the physical and chemical properties of the compounds by class.
Some of the observed physical properties of hydrocarbons result from the nonpolar
character of the compounds. In general, hydrocarbons do not mix with polar solvents such
as water or ethyl alcohol. On the other hand, hydrocarbons mix with relatively nonpolar
solvents such as ligroin (a mixture of alkanes), carbon tetrachloride (CC14), or
dichloromethane (CH 2Cl 2 ). Since the density of most hydrocarbons is less than that of
water, they will float. Crude oil and crude oil products (home heating oil and gasoline) are
mixtures of hydrocarbons; these substances, when spilled on water, spread quickly along
the surface because they are insoluble in water.

The chemical reactivity of hydrocarbons is determined by the type of bond in the

compound. Although saturated hydrocarbons (alkanes) will burn (undergo combustion),
they are generally unreactive to most reagents (Alkanes do undergo a substitution
reaction with halogens but require ultraviolet light.) Unsaturated hydrocarbons, alkenes
and alkynes, not only burn, but also react by addition of reagents to the double or triple
bonds. The addition products become saturated, with fragments of the reagent becoming
attached to the carbons of the multiple bond. Aromatic compounds, with a higher carbon-to-
hydrogen ratio than nonaromatic compounds, burn with a sooty flame as a result of
unburned carbon particles being present. These compounds undergo substitution in the
presence of catalysts rather than an addition reaction.

1. Combustion The major component in "natural gas" is the hydrocarbon methane (CH 4).
Other hydrocarbons used for heating or cooking purposes arc propane (C 3 H8 ) and
butane (C 4 H10). The products from combustion are carbon dioxide and water (heat is
evolved, also).

CH4 + 2O 2 → CO2 + 2H2O + Heat

CH3CH2CH3 + 5O2 → 3CO2 + 4H2O + Heat

2. Reaction with bromine: Unsaturated hydrocarbons react rapidly with bromine in a

solution of carbon tetrachloride or cyclohexane. The reaction is the addition of the
elements of bromine to the carbons of the multiple bonds.

The bromine solution is red; the product that has the bromine atoms attached to carbon
is colorless. Thus a reaction has taken place when there is a loss of color from the
bromine solution and a colorless solution remains. Since alkanes have only single C —C
bonds present, no reaction with bromine is observed; the red color of the reagent would
persist when added. Aromatic compounds resist addition reactions because of their
"aromaticity": the possession of a closed loop (sextet) of electrons. These compounds
react with bromine in the presence of a catalyst such as iron filings or aluminum chloride.

C6H5-H + Br2 → C6H5-Br + H B r

Note that a substitution reaction has taken place and the gas HBr is produced.
3. Reaction with concentrated sulfuric acid: Alkenes react with cold concentrated
sulfuric acid by addition. Alkyl sulfonic acids form as products and are soluble in H2SO4.

OSO3H
+ H2SO4 H2O

Saturated hydrocarbons are unreactive (additions are not possible); alkynes react slowly
and require a catalyst (HgSO 4 ); aromatic compounds also are unreactive since addition
reactions are difficult.

4. Reaction with potassium permanganate: Dilute or alkaline solutions of KMnO4 oxidize

unsaturated compounds. Alkanes and aromatic compounds are generally unreactive.
Evidence that a reaction has occurred is observed by the loss of the purple color of
KMnO4 and the formation of the brown precipitate manganese dioxide, MnO2.
Procedure
Objectives
1. To investigate the physical properties, solubility, and density of
some hydrocarbons.
2. To compare the chemical reactivity of an alkane, an alkene, and an
aromatic compound.
3. To use physical and chemical properties to identify an unknown

CAUTION!
Assume the organic compounds are highly flammable. Use only small quantities. Keep
away from open flames. Assume the organic compounds are toxic and can be absorbed
through the skin. Avoid contact; wash if any chemical spills on your person. Handle
concentrated sulfuric acid carefully. Flush with water if any spills on your person. Potassium
permanganate and bromine are toxic; bromine solutions are also corrosive. Although the
solutions are diluted, they may cause burns to the skin. Wear gloves when working with these
chemicals.
Chemicals and Equipment
1. 1% aqueous KMnO4
2. 1% Br2 in cyclohexane
3. Blue litmus paper
4. Concentrated H2SO4
5. Cyclohexene
6. Hexane
7. Aluminum chloride
8. Test tubes
9. Ligroin
10. Toluene
11. Unknowns A, B, and C
12. Watch glasses
13. Ice

General instructions

1. The hydrocarbons hexane, cyclohexene, and toluene (alkane, alkene, and

aromatic) are available in dropper bottles.

2. The reagents 1% Br 2 in cyclohexane, 1% aqueous KMn0 4 , and concentrated

H2 SO4 are available in dropper bottles.
3. Unknowns are in dropper bottles labeled A, B, and C. They may include an
 alkane, an alkene, or an aromatic compound.
4. Test tubes of 100 X 13 mm will be suitable for all the tests. When mixing the
components, grip the test tube between thumb and forefinger; it should be held
firmly enough to keep from slipping but loosely enough so that when the third
and fourth fingers tap it, the contents will be agitated enough to mix.

5. Record all data and observations in the appropriate places on the Data Sheet.
6. Dispose of all organic wastes as directed by the instructor. Do not pour into the sink!

Physical Properties of Hydrocarbons

1. Water solubility of hydrocarbons.
A. Label six test tubes with the name of the substance to be tested. Place into each
test tube 5 drops of the appropriate hydrocarbon: hexane, cyclohexene, toluene,
unknown A, unknown B, unknown C.
B. Add about 5 drops of water dropwise into each test tube. Water is a polar solvent. Is
there any separation of components? Which component is on the bottom; which
component is on the top? Mix the contents as described above.
C. What happens when the contents are allowed to settle? What do you conclude
about the density of the hydrocarbon? Is the hydrocarbon more dense than water or
less dense than water? Record your observations. Save these solutions for
comparison with the next part.
2. Solubility of hydrocarbons in ligroin.
A. Label six test tubes with the name of the substance to be t ested. Pl ace
into each t est tube 5 drops of the appropriate hydrocarbon: hexane,
cyclohexene, toluene, unknown A, unknown B, unknown C.
B. Add about 5 drops of ligroin dropwise into each test tube. Ligroin is a
nonpolar solvent. Is there a separation of components? Is there a bottom layer
and top layer?
C. Mix the contents as described above. Is there any change in the appearance of
the contents before and after mixing? Compare these test tubes to those from
the previous part. Record your observations. Can you make any conclusion about
the density of the hydrocarbons from what you actually see?
Chemical Properties of Hydrocarbons

1. Combustion.

The instructor will demonstrate this test in the fume hood. Place 5 drops of each
hydrocarbon and unknown on separate watch glasses. Carefully ignite each sample
with a match. Observe the flame and color of the smoke for each of the samples.

2. Reaction with bromine.

A. Label six clean, dry test tubes with the name of the substance to be tested.
Place into each test tube 5 drops of the appropriate hydrocarbon: hexane,
cyclohexene, toluene, unknown A, unknown B, unknown C.

B. Carefully add (dropwise and with shaking) 1% Br 2 in cyclohexane. Keep

count of the number of drops needed to have the color persist; do not add
more than 10 drops. Record your observations. To any sample that gives a
negative test after adding 10 drops of bromine solution (i.e., the red color
persists), add 5 more drops of 1% Br 2 solution and a small quantity of
aluminum chloride, the amount on the tip of a micro -spatula; shake the
mixture.

C. Hold, with forceps, a piece of moistened blue litmus paper and lower it into
the test tube until it is just above the surface of the liquid. Be careful and try
not to touch the sides of the test tube or the liquid with the litmus paper.
Record any change in the color of the solution and the litmus paper.

Caution! Use 1% Br2 solution in the hood; wear gloves when using this chemical. Use the
aluminum chloride in the hood: wear gloves when using this chemical. The bottle of aluminum
chloride is kept in a desiccator; quickly take your sample and return the bottle to the desiccator.
Do not leave the bottle open or outside the desiccator for a long time.

3. Reaction with KMnO 4

A. Label six clean, dry test tubes with the name of the substance to be tested.
Place into each test tube 5 drops of the appropriate hydrocarbon: hexane,
cyclohexene, toluene, unknown A, unknown B, unknown C. Carefully add
(dropwise) 1% aqueous KMnO 4 solution; after each drop, shake to mix the
 solutions.

B. Keep count of the number of drops needed to have the color of the
permanganate solution persist; do not add more than 10 drops. Record your
observations.

4. Reaction with concentrated H 2 SO 4

A. Label six clean, dry test tubes with the name of the substance t o be
tested. Place into each test tube 5 drops of the appropriat e
hydrocarbon: hexane, cyclohexene, toluene, unknown A, unknown B,
unknown C.
B. Place all of the test tubes in an ice bath. Wear gloves and carefully add
(with shaking) 3 drops of cold, concentrated sulfuric acid to each test tube.
Note whether heat is evolved by feeling the test tube. Note whether the
solution has become homogeneous or whether a color is produced. (The
evolution of heat or the formation of a homogeneous solution or the
appearance of a color is evidence that a reaction has occurred.) Record your
observations.

5. Unknowns By comparing the observations you made for your unknowns with that
of the known hydrocarbons, you can identify unknowns A, B, and C. Record their
identities on your Data Sheet.
 Name __________________________ Date _________________

Partner ________________________ Section ______________

Data Sheet: Hydrocarbons

Physical properties of hydrocarbons
Solubility: Does the hydrocarbon mix with the solvent, soluble, or not mix with the solvent,
insoluble? Use the observations you make for the solubility tests and determine whether the
hydrocarbons are polar or non-polar substances.
Density: For water, is the density greater than water (sinks) or less than water (floats)? For
ligroin, can you tell anything about the relative densities?

H 2O Ligroin
Hydrocarbon Solubility Density Solubility Density

Hexane

Cyclohexene

Toluene

Unknown A

Unknown B

Unknown C
Chemical properties of hydrocarbons

Bromine KMnO4 H2SO4

Hydrocarbon Combustion Test Test Test

Hexane

Cyclohexene

Toluene

Unknown A

Unknown B

Unknown C

Unknown A is____________________

Unknown B is____________________

Unknown C is____________________
Name __________________________ Section _______________

Date _________________

Pre-lab: Hydrocarbons

1. Give an example of a saturated hydrocarbon and an unsaturated hydrocarbon.

2. Show the structural feature that distinguishes whether a hydrocarbon is an alkane,

alkene, alkyne, aromatic

3. Gasoline and water do not mix. Why?