ORGANIC CHEMISTRY
TIERS 5 & 6
TIER 5
Predict and explain trends in boiling points of members of a homologous series
Discuss the volatility and solubility in water of compounds containing the functional
groups: compounds up to six carbon atoms with one of the following functional
groups: alcohols, ketones, aldehydes, carboxylic acid, and halides .
Describe using equations the complete and incomplete combustion of alkanes
Describe using equations the reactions of methane and ethane with chlorine and
bromine
Describe using equations the reaction of alkenes with hydrogen and halogens
Describe using equations, the reactions of symmetrical alkenes with hydrogen
halides and water
Distinguish between alkanes and alkenes using bromine water
Describe using equations the complete combustion of alcohol
Describe using equations the oxidation of alcohols
Describe using equations the oxidation of primary and secondary alcohols
Describe using equations the substitution reactions of halogenoalkanes with sodium
hydroxide
TIER 6
Explain the reactions of methane and ethane with chlorine and bromine in terms of
a free radical mechanism
Outline the polymerization of alkenes
Outline the economic importance of the reaction of alkenes
Explain the substitution reactions of halogenoalkanes with sodium hydroxide in
terms of SN1 and SN2 mechanisms
Deduce reaction pathways given the starting materials and the product.
TRENDS IN PHYSICAL
PROPERTIES
Predict and explain trends in boiling points of
members of a homologous series
Discuss the volatility and solubility in water of
compounds containing the functional groups:
compounds up to six carbon atoms with one of the
following functional groups: alcohols, ketones,
aldehydes, carboxylic acid, and halides .
BOILING POINT TRENDS
As the hydrocarbon chain gets larger, the increase in number of
electrons increases the temporary dipoles causing stronger van der
Waals forces. Two features that influence the boiling point of
alkanes are:
the number of electrons surrounding the molecule, which increases
with the alkane's molecular weight
the surface area of the molecule
As a rule of thumb, the boiling point rises 2030C for each
carbon added
A straight-chain alkane will have a boiling point higher than a
branched-chain alkane due to the greater surface area in contact
with a straight chain, thus the greater van der Waals forces,
between adjacent molecules.
INFLUENCE OF FUNCTIONAL GROUPS
ON BOILING POINT TRENDS
Functional groups which are polar will develop dipole-dipole
interactions and thus will have higher boiling points
Functional groups which enable hydrogen bonding between
molecules will have even higher boiling points
The effect of functional groups on boiling points are as follows:
Most volatile
Least volatile
(How easily to change to a gas)
Alkane > Halogenalkane > Aldehyde > Ketone > Alcohol >
Carboxylic acid
Van der Waals
dipole-dipole
hydrogen bonding
Increasing strength of intermolecular forces
Increasing boiling point
BOILING POINT
The boiling points of other
types of organic compounds
are shown on the graph to the
right
IMPORTANCE OF BOILING POINT
TRENDS
For example, fractional
distillation is used in
oil refineries to separate
crude oil into useful
substances (or fractions)
having different
hydrocarbons of different
boiling points. The crude oil
fractions with higher boiling
points:
have more carbon atoms
have higher
molecular weights
are more branched chain
alkanes
are darker in color
are more viscous
are more difficult to ignite
MELTING POINT TRENDS
The melting point of the alkanes follow a similar trend to boiling point and
for the same reason That is, (all other things being equal) the larger the
molecule the higher the melting point.
However, due to the rigidity of solids, they require more energy to break
the intermolecular forces holding the molecules together The more
ordered the molecule the more energy require to over come the
intermolecular forces.
Odd-numbered alkanes have a lower trend in melting points than evennumbered alkanes because even-numbered alkanes pack well in the solid
phase, forming a well-organized structure, which requires more energy to
break apart. The odd-number alkanes pack less well and so the "looser"
organized solid packing structure requires less energy to break apart.
The melting points of branched-chain alkanes can be either higher or lower
than those of the corresponding straight-chain alkanes, again depending
on the ability of the alkane to form more organized structures.
Alkane
Formul
a
Methane CH4
Boiling
point
[C]
Density
Melting
[gcm3
point
] (at 20
[C]
C)
-162
-182
gas
Ethane
C2H6
-89
-183
gas
Propane
C3H8
-42
-188
gas
Butane
C4H10
-138
gas
Pentane
C5H12
36
-130
0.626
(liquid)
Hexane
C6H14
69
-95
0.659
(liquid)
Heptane C7H16
98
-91
0.684
(liquid)
Octane
C8H18
126
-57
0.703
(liquid)
Nonane
C9H20
151
-54
0.718
(liquid)
Decane
C10H22
174
-30
0.730
(liquid)
SOLUBILITY IN WATER
There are two factors to consider when
determining the solubilty of an organic
compound in water:
The length of the hydrocarbon chain
The nature of the functional group
Solubility decreases as the length of the chain increases
Solubility of functional groups depend on their ability
to form hydrogen bonds with water
Lower members of alcohols, aldehydes, ketones,
and carboxylic acids are quite soluble in water
Halogenoalkanes are not soluble in water despite
their polarity b/c they do not form hydrogen bonds
with water
CHEMICAL REACTIVITY
Due to the nature of the strong C-C and C-H non-polar bonds, alkanes
will only react in the presence of a strong source of energy.
Thus alkanes have low reactivity. However, they create highly
exothermic reactions due to the fact that a large amount of energy is
released forming the double bonds in CO2 and the bonds in H2O.
Alkanes burned in the presence of excess oxygen produce CO2 and H2O
by the following reaction:
CxHy +O2 CO2 + H2O
If oxygen supply is limited then the reaction is :
CxHy +O2 CO + H2O
If oxygen supply is extremely limited then the reaction will be:
CxHy +O2 C + H2O
Describe using equations the reactions of
methane and ethane with chlorine and bromine
Step 1: Initiation
Step 2: Propagation
UV
Known as homolytic fission where the
halogen molecule is broken down by UV
light to produce twofree radicals
Step 3: Termination
This chain reaction both use and produce
free radicals and so allow the reaction to
continue.
OVER ALL EQUATION:
OR
These reactions remove the free radicals and
cause them to pair up their electrons
CH4 + Cl2 CH3Cl
+ HCl
EXAMINERS HINT: Be sure to understand that a free
radical has an unpaired electron but no net charge and
an ion carries a charge
Describe using equations, the reactions of symmetrical alkenes
with hydrogen halides and water
&
Describe using equations the reaction of alkenes with hydrogen
and halogens
Distinguish between alkanes and alkenes
BROMINE WATER TEST:
Since alkenes readily undergo addition reactions ,whereas
alkanes will not (they will only undergo substitution reactions in
UV light), brome water is used to distinguish between the two
homologous series.
Bromine water is a reddish-brown liquid that will become colorless
in an alkene but remain a reddish-brown liquid in an alkane.
FLAME TEST:
Alkenes burn with a much dirtier, smokier flame that alkanes due
to the fact that they have a higher C-H ratio. This causes more
unburned carbon to burn in alkenes.
Benzene rings burn even dirtier
Describe using equations the complete
combustion of alcohol
Alcohols react with oxygen to produce carbon dioxide and water
EXAMPLE: Combustion of Ethanol
2C2H5OH + 6O2 4CO2 + 6H2O
Describe using equations the oxidation of
alcohols
&
Describe using equations the oxidation of
The oxidation
of alcohols
involves acidified
potassium
primary
and often
secondary
alcohols
dichromate as the oxidizing agent. The Cr 6+ is reduced to Cr
3+. In the reaction below, the oxidizing agent is represented [O]-
Describe using equations the substitution
reactions of halogenoalkanes with sodium
hydroxide