Solubility and Reactivity of Alkanes, Alkenes

and Aromatic Compounds Course Notes

Hydrocarbons: Alkanes, Alkenes, Alkynes and Aromatic
Hydrocarbons are organic molecules made up of only carbon and hydrogen. If the
hydrocarbon has only single bonds between the carbon atoms , it is said to be an
alkane. If there is a double bond between two carbon atoms, then the molecule is said
to be an alkene. When there is a triple bond between two carbon atoms, that molecule
is called an alkyne.
Benzene is a special case because there are three alternating double bonds within the
six carbon ring, presenting chemical and physical properties that are not possessed by
either alkanes or alkenes. Hydrocarbons with a benzene like ring within them are said
to be aromatic hydrocarbons

London Dispersion Intermolecular Force

The forces that hold molecules together in a liquid, solid and solution phases are very
weak. They are generally called London dispersion forces.
The electrons in the orbitals of a molecule are free to move around. If you could
compare a "snapshot" of the molecule at an instant in time, you would see that there
would be slightly different charge distributions caused by the different positions of the
electrons in the orbitals. The amount of difference is based on the polarizability of the
molecule, which is a measure of how well electrons can move around in their orbitals.
In general, the polarizability increases as the size of the orbital increases; since the
electrons are further out from the nucleus they are less strongly bound and can move
about the molecule more easily.
When two molecules come together, these variations in charge can create a situation
where one end of a molecule might be slightly negative and the other end of that
molecule could be slightly positive. This would result in a slight attraction of the two
molecules (until the charges moved around again) but is responsible for the attractive
London dispersion forces all molecules have.
These London dispersion forces are weak, the weakest of all the intermolecular forces.
Their strength increases with increasing size and polarizability of the molecule.

Hydrocarbon Solubility
The rule to use when determining hydrocarbon solubility is: Like dissolves like.
This means that polar compounds (water, alcohols, and carboxylic acids) dissolve
other polar compounds. Water can be broken down into H - OH, thus it has the -OH
group which identifies alcohol and carboxylic acids. Nonpolar compounds dissolve
other nonpolar compounds but tend not to dissolve polar compounds.
When you test for solubility you are looking for either a homogeneous solution or a
heterogenous solution. Homogeneous solutions have no layers evident indicating the
hydrocarbon being tested is soluble. These hydrocarbons are miscible. Heterogenous
solutions have layers evident indicating the hydrocarbons are insoluble. These
hydrocarbons are immiscible.

Hydrophobic - Hydrophilic
When you are trying to evaluate the solubility properties of alcohols and carboxylic
acids, it becomes necessary to consider the relative sizes of the hydrocarbon and
water-like portions of the molecule. The hydrocarbon portion is said to
be hydrophobic (water hating) because it will not hydrogen bond with water but
does tend to dissolve in hydrocarbon liquids. The water-like alcohol and carboxylic
acid groups hydrogen bond with water and are said to be hydrophilic (water-loving).
If the ratio of the size of the hydrophilic portion to the hydrophobic portion is small,
the hydrophilic portion is too small to carry the molecule into solution with water. If
the ratio is large, it can carry the molecule into solution.
The solubility of alcohols and carboxylic acids in water is made smaller when the
hydrophobic portion of the molecule is made larger.
When determining the solubility of a molecule there is one final rule.
The solubility of hydrogen bonding molecules is improved if either the positive
charge on the hydrogen is made larger or the negative charge on the
electronegative atom (oxygen or nitrogen) is increased.

Unsaturation and Alkanes and Alkenes

Alkanes are considered saturated because they have only single C-C bonds and cannot
add a hydrogen. Alkenes are unsaturated because they are capable of adding a
hydrogen when the C=C double bond is broken.

Bromine Test for Hydrocarbon Reactivity

The bromine test is used to determine if the colorless organic compound contains any
double C=C bonds (the alkene functional group). Bromine does not react with an
alkane because the alkane contains only single C-C bonds which cannot add the
bromine. Alkanes merely dilute the red-brown bromine color to an orange or yellow
color in the absence of a strong catalyst.
Due to their C=C double bonds which can be broken, alkenes react readily with
bromine to produce saturated dibromoalkanes. When an alkene is reacted with
bromine, the red-brown color of the bromine is immediately lost due to the reaction of
the bromine.

Alkane + bromine (No strong light or heat) results in diluted solution colored
orange or yellow indicating no reaction.
Alkane + bromine (heat or strong light acting as a catalyst) results in the brown
red color of bromine slowly disappearing.
Alkene + bromine results in the red brown color of bromine rapidly or
immediately disappearing giving a colorless solution
Aromatic hydrocarbon + bromine (no heat or light acting as a catalyst) results in
no reaction and the red brown color of bromine is diluted to orange or yellow.

Aromatic hydrocarbons are too stable to react without a catalyst so they act like
alkanes.

Red brown color of bromine

Bromine Test (left) No reaction, saturated, (right) Reaction, unsaturated

If an alkene is present, the bond breaks and bromine is added in two places.

Cholesterol

Cholesterol has only one -OH group which is polar. This single alcohol functional
group does not make it polar enough to dissolve in water or blood (made up of mostly
water). Since cholesterol is not polar enough to dissolve in water it will dissolve in
nonpolar solvents. Cholesterol when tested with the bromine test will react, losing the
red-brown color of bromine and turning colorless. This is due to the one double ()
bond. This double bond can break allowing bromine to be added, indicating an alkene
is present and cholesterol is unsaturated allowing the red brown color of bromine to
slowly disappear.

Red brown color of bromine slowly disappears = unsaturated.

Red brown color of bromine dilutes to yellow or orange = saturated.

Bromine test for Unsaturation

Again bromine is used to determine whether an alkane, alkene, or aromatic
hydrocarbon is present. If the substance is an alkene it will react with the bromine,
indicating the compound is unsaturated. When the red-brown color of bromine
disappears it indicates the substance is unsaturated and a reaction has occurred.

ALKANES contain only (single C-C) bonds and cannot add any Br so red
brown color of bromine dilutes to yellow or orange = saturated.
ALKENES contains a bond making it possible to add Br so the red brown
color of bromine disappears rapidly or immediately = unsaturated.
AROMATIC HYDROCARBONS are extremely stable and will not react without
a catalyst = saturated.
When the red-brown color of bromine is diluted to yellow or orange (no reaction), the
substance is saturated.

Red-brown color of bromine is diluted to yellow or orange (no reaction), the

substance is SATURATED.
Red brown color of bromine disappears (reaction), the substance is
UNSATURATED.
Digital Video from DVAction of the Bromine Test for Alkenes

Baeyer Test for Unsaturation

The Baeyer reagent is a cold dilute aqueous solution of potassium permanganate
which is a deep purple color. Potassium permanganate does not react with alkanes
because they are saturated (single bonds which are all taken). When it is added to

alkanes the purple color does not change. However, when it is added to an alkene, the
purple color slowly disappears and a brown MnO2 precipitate forms. The appearance
of the brown precipitate indicates a positive test for unsaturation. The Baeyer test
for unsaturation is used when the color of the organic compound may interfere with
the result of the Bromine Test for Unsaturation.

Purple color dilutes to light purple = SATURATED.

Purple color disappears and brown ppt forms = UNSATURATED.

The purple color of KMnO4

Baeyer Test for Unsaturation (left) purple diluted to light purple: saturated, (right)
purple disappears, brown preciptate forms: unsaturated.