Chapter 10 Organic Chemistry

1. Unique properties of carbon

- Able to form multiple bonds (up to 4) with other atoms
- Able to undergo catenation i.e. form long chains and ring structures
- Able to form stronger bonds with other atoms (in contrast to Silicon, the next
member of group IV)
- Unable to expand beyond its octet i.e. forms more kinetically stable compounds
(in contrast to compounds of Silicon)

2. Homologous Series
- Members have the same general formula (i.e. same elements in the same ratio)
- Members have the same functional group; a functional group is a group of atoms
in a compound which gives its members their characteristic chemical properties
- Members differ by -(CH2)- groups
- have similar chemical properties
- show a gradual change (gradation) in physical properties
3. Formulas representing organic compounds
type of formula
empirical formula

description
Shows the simplest whole number ratio of all atoms.

molecular formula

Shows the actual number of the different atoms and

how many of each; no information on how the atoms
are arranged.

structural formula

Shows how atoms are arranged together in the

molecule; a full structural formula (sometimes called a
graphic formula or displayed formula) shows every
atom and bond.

condensed structural
formula

Shows order in which atoms are arranged but which omits

bonds.

example
CH2

C6H14

CH3CH2CH2CH2CH2CH3
or CH3(CH2)4CH3

4. Nomenclature
- When naming an organic compound we want to give a lot of information in its
name which is why the name of an organic compound consists of at least two
parts: one to indicate the number of carbon atoms in the chain and the other the
functional group. Other parts will indicate length and number of branches or if the
compound is cyclic.

Example:

prop ane

this part tells us how many carbons

atoms there are in the molecule;
this part could be:
meth- = means it has 1 carbon atom
eth- = 2 carbon atoms
prop- = 3 carbon atoms
but- = 4 carbon atoms
pent = 5 carbon atoms
hex = 6 carbon atoms
benz- = benzene ring

this part tells us the functional group it

has or which homologous series it
belongs to;
the ending could be:
-ane which means it belongs to the
alkanes (=homologous series)
-ene = alkene
-anol = alcohol
-anal = aldehyde
-anone = ketone
-anoic acid = carboxylic acid.

Naming of halogenoalkanes
-

In the case of the halogenoalkanes, the name begins with the name of the halogen and
not the number of carbon atoms.
The name should also indicate the position and the number of halides if there is more
than two.
For example: chloro, bromo, fluoro, iodo, .. in names such as 2-bromopropane, 1,2dichloroethane.

5. Alkanes
-

Alkanes are a homologous series in which all non-cyclic compounds have the
following general formula: CnH2n + 2
Alkanes only contain carbon carbon single bonds and carbon hydrogen single
bonds, hence they are also known as hydrocarbons.

Structure of alkanes
structure 1
straight-chain: all carbon atoms can be
joined by a continuous line.

structure 2
branched-chains: molecules have side groups and these are
referred to as alkyl groups.

alkyl group

formula

methyl

CH3 -

ethyl

CH3CH2 -

propyl

CH3CH2CH2 -

butyl

CH3CH2CH2CH3 -

C4H10 - butane

2-methylpropane

Naming branched alkanes

A branch is a carbon atom or group of carbon atoms bonded onto a larger carbon chain.
The name of that branch (or side group) should indicate the number of carbon atoms in it and
should end with yl to indicate it is a branch e.g. methyl, ethyl, propyl. You need to identify the
longest chain in the branched compound and any carbon atoms not in it must be part of a branch.
The name of the branched compound should include:
the name of the branch
the number of branches if there is two or more
and, using a number, the position of the branch(es) on the straight chain; the position
should be decided from the end of the longest chain which gives the lowest number(s).
the position of the functional group has priority over alkyl.
Examples: 2-methylpentane, 2,2-dimethylpentane, methylpropan-2-ol, 2,2,4-trimethylpentane

Physical properties of alkanes: melting/boiling points, viscosity, density

Melting points, boiling points, viscosity (resistance to flow) and density increase with
increasing number of carbon atoms
Explanation:
The larger the molecules (the greater the molar mass)
the more sites/surface area there are for intermolecular attraction,
or the greater the number of electrons, the greater the polarisation within the molecule,
or the greater their mass/inertia
and therefore the greater the attraction between the molecules, the more energy is needed to
overcome the intermolecular forces of attraction and cause the alkane to melt or boil; the
greater the viscosity and the greater the density.

Structural isomerism
Structural isomers are compounds with the same molecular formula but the sequence or
arrangement in which the atoms are bonded is different which is why they have a different
structural formula.
Branching has a different effect on the melting point than on the boiling point.
Straight chained alkanes have higher boiling points than branched alkanes of similar
molecular mass as there is more contact/larger surface area between the straight-chained
molecules and therefore more sites for induced polarity and stronger Van der Waals forces;
the higher the number of branches, the lower the boiling points. As branching decreases
surface area, it increases volatility and decreases density.
However, straight chained alkanes generally have lower melting points than branched alkanes
(in particular with symmetrical structures). Branching increases m.p. as branched molecules
can fit more closely together and more energy is needed to separate them; the lattice of a
solid straight chained alkane is like wet spaghetti: molecules can easily slide over each other.

Structural formula
name

pentane

molecular
formula

boiling point
(oC)

C5H12

36

28
2-methylbutane

C5H12

2,2dimethylpropane

C5H12

10

Chemical properties of alkanes

Alkanes are unreactive because:

Large bond enthalpies: the covalent bonds between carbon and hydrogen and carbon and
carbon have large bond enthalpies; this is because both hydrogen and carbon are small
atoms so bonding pairs are attracted strongly by both nuclei.
Low or no difference in electronegativity: due to the very small difference in
electronegativity between carbon and hydrogen the covalent between the two atoms very
low polarity and does therefore not attract other reagents.

The only reactions they easily undergo are combustion and substitution reactions.

(a) Combustion of alkanes

Complete combustion: (in plentiful of oxygen) products are water and carbon dioxide
CxHy + (x + y/4) O2
Examples:

xCO2 + (y/2)H2O

CH 4 + 2O2

CO2 + 2H2O

C3H 8 + 5O2

3CO2 + 4H2O

Incomplete combustion: products are water and carbon monoxide or carbon (=black
smoke) depending on the extent of the lack of oxygen (incomplete oxidation); water is
always produced.
Examples:
CH 4 + 1 O2
CH 4 + O2
C3H 8 + 4O2

CO2 + 2H2O

C + 2H2O
CO2 + 2CO +

4H2O

(b) Free Radical Substitution

Bond fission
When a covalent bond is broken the bonding pair electrons are redistributed between the two
atoms; there are two ways of redistributing these two electrons:
Homolytic fission
* occurs in non-polar bonds or bonds with a very low polarity when bonding
electrons are fairly equally shared in the bond
* each atom gets one of the bonding electrons; each atom has now an unpaired
electron and is therefore unstable and reactive; such a particle with an
unpaired electron is called a free radical
* free radicals have a strong tendency to react and usually have a short
existence; tend to be intermediates in reactions
A B

A
+
B

Heterolytic fission
*
*
*

Both bonding electrons go to one of the atoms forming a negative and positive
ion for example a carbocation and carbanion
occurs in polar bonds
ions are unstable and highly reactive sites
A B

A+
+
B-

During a substitution reaction, a hydrogen atom on the carbon chain is replaced by a halogen
atom. The reaction needs sunlight/UV as UV/sunlight has the corresponding amount of
energy to break the halogen bonds; no reaction will occur in the dark.
Examples of substitution reactions:
UV

CH4 (g)

methane +

Cl2 (g)
chlorine

CH3 Cl (g)

chloromethane

HCl (g)
+

hydrogen chloride

(substitution with chlorine: tetrachloromethane is formed if proportion of chlorine is high

compared to the proportion of methane).

UV

C2H6 (g)
ethane

+
+

Br2 (l)

C2H5 Br (g)

bromine

1-bromoethane +

HBr (g)
hydrogen bromide

Homolytic free radical substitution reaction

The sequence of steps/collisions by which substitution reaction takes place is called the
reaction mechanism. The reaction is an example of a free radical substitution reaction.

step 1:
initiation

The UV light causes homolytic fission of the halogen molecule; each atom
takes one of the electrons in the covalent bond. The two species formed are
not atoms but are called free radicals and each has one electron from the bond.
A free radical is the name given to a species containing an unpaired electron.
They are very reactive, because they have an unpaired electron, and so have a
strong tendency to pair up with an electron from another molecule. A dot is
used to represent the unpaired electron.
Using the example of the reaction between methane and chlorine:

Homolytic fission reaction

Cl - Cl

to form free radicals

Cl

Cl

free radicals

Chain reaction during which the free radicals react with molecules forming
step 2:
propagation more free
radicals and other molecules:
free radical +

molecule

new free radical

new molecule

Free radical knocks an atom off the molecule which itself becomes a free
radical while the radical becomes a molecule.

In the case of the chlorine and methane reaction:

One of the chlorine free radicals reacts with a methane molecule by

substituting itself for a hydrogen atom. A new free radical is formed (or
propagated).

CH4

Cl

CH3

HCl

The CH3 reacts with the Cl2 to form CH3Cl and the free radical Cl:

CH3

step 3:
termination

Cl2

CH3Cl

Cl

Occurs when two free radicals react to form a stable molecule.

In the case of the chlorine and methane reaction:

CH3

Cl

CH3Cl

Cl

Cl

Cl2

CH3

CH3

C2H6

If excess Cl2 is used further substitutions may take place until all the hydrogen atoms are
substituted for:
CH3Cl

Cl2

CH2Cl2

HCl

Followed by
CH2Cl2

Cl2

Cl2

CHCl3

HCl

And then
CHCl3

CCl4

HCl

6. Alkenes

Structure of alkenes
There are 2 types of structures you need to know:
straight chain
branched chains
Physical properties of alkenes
Same trends and explanations as in alkanes; however, boiling points/melting points are
generally a little lower than the boiling points/melting points of the alkanes as the alkenes
have a lower molecular mass.
Chemical properties of alkenes
As they are unsaturated alkenes are reactive. The second bond of the double bond is weaker
than a single carbon-carbon bond as it has a lower enthalpy change less energy needed to
break it.
Alkenes undergo addition reactions; atoms are added to the carbon chain using the double
bond
As they are unsaturated alkenes are reactive. The second bond of the double bond is weaker
than a single carbon-carbon bond and is broken much easier.
It is because of this greater reactivity that alkenes, especially ethene, are important starting
materials in organic synthesis of useful chemicals.
It is important to note that alkenes also easily combust and undergo both complete and
incomplete combustion.
Alkanes undergo addition reaction that means that atoms are added to the molecule at either
side of the double bond so any addition reaction increases the number of atoms in the
molecule. During the addition reaction the double bond is converted to a single bond. The
weaker second bond of the double bond is replaced by a stronger single bond; this increases
the stability of the molecule.

Reactions
The reagents (hydrogen, halogen, water and hydrogen halide molecules) are attracted to the
double bond; the double bond breaks open and is replaced by two single bonds to 2 new
atoms or groups of atoms. One part of the reagent bonds to one carbon atom while the other
part of the reagent bonds onto the second carbon atom of the double bond.

Reaction with bromine (bromination)

Occurs under room conditions (even in the dark); the product is a colourless dihalogenoalkane.
molecular

C2H4 (g)

equation

ethene

+
+

Br2 (l)

C2H4 Br2 (g)

bromine

1,2-dibromoethane

Test for unsaturation

The bromination reaction is useful as it can be used to distinguish between an alkane (no
decolourization of bromine water occurs as it remains yellow/brown) and an alkene (bromine
water which is yellow or brown becomes colourless as 1,2-dibromoethane is a colourless
compound).
Reaction with hydrogen (hydrogenation)
Requires a nickel catalyst and temperature of 180C.
molecular
equation

C2H4 (g)
ethene

H2 (g)
hydrogen

C2H6 (g)
ethane

Reaction with water (=hydration)

(a) Industrial hydration of ethene into ethanol
Reaction in which H and OH are introduced in the molecule: needs a strong concentrated
acid (e.g. H3PO4) as catalyst, 300 C and 70 atm. The reaction is used to make industrial
ethanol.

Example:
molecular

C2H4 (g)

word

ethene

H2O (l)

C2H5OH (l)

water

ethanol

(b) Lab preparation of alkenes into alcohols

Reaction in which H and OH are introduced in the molecule: requires concentrated sulfuric
acid and water at room temperature
Example: equations
molecular

C2H4 (g)

H2SO4 (aq)

C2H5OSO3H (l)

C2H5OSO3H (l) + H2O (l) C2H5OH (l) + H2SO4 (aq)

word

ethene

sulfuric acid

ethyl hydrogensulfate + water

ethyl hydrogensulfate
ethanol + sulfuric acid

Reaction with hydrogen halides

Concentrated aqueous solutions of hydrogen halide at room temperature; product is a
halogenoalkane.

molecular
word

C2H4 (g)
ethene

HCl (l)

C2H5OH (l)

water

ethanol

Economic importance of reactions of alkenes

-

Hydrogenation of vegetable oils in the manufacture of margarine.

Hydration of ethene in the manufacture of industrial ethanol which is used as a
solvent, antiseptic or fuel.
Polymerization in the manufacture of plastics.
Synthesis of drugs.
Synthesis of ethane-1,2-diol which is used as antifreeze.

7. Alcohols
-

Most important alcohol is ethanol which is used as a fuel, solvent, antiseptic, to

make esters.

Primary, secondary and tertiary alcohols

Based on the number of alkyl groups or carbons bonded onto the carbon that carries the OH
group.

primary alcohol

secondary alcohol

tertiary alcohol

Has one alkyl group or 1

carbon atom onto the carbon
which carries the OH group

Has two alkyl groups or 2

carbon atoms onto the carbon
which carries the OH group

Has three alkyl groups or 3

carbon atoms onto the carbon
which carries the OH group

This distinction is important as the product of the same type of reaction e.g. an oxidation will
be different for each type of alcohol. As such the three different types of alcohols can be
considered different homologous series.

Complete combustion of alcohols

Alcohols can be combusted completely (very exothermic reaction) producing carbon dioxide
and water as shown by the symbol equation of the combustion of ethanol.
C2H 5OH + 3O2

2CO2 + 3H2O

Oxidation of alcohols using an oxidising agent

Primary alcohols, such as ethanol, can be oxidised by heating them with an oxidising agent
e.g. potassium dichromate(VI) which needs to be acidified (by adding H2SO4) and which
goes from orange (oxidation state +6) to green (oxidation state +3). The reaction involves the
hydrogen atoms bonded onto the carbon that carries the hydroxyl group.
The oxidation of primary alcohols can yield two different products depending on the
conditions under which it is carried out.
1. Partial oxidation to form an aldehyde, e.g. ethanal from ethanol:
Heating excess alcohol with oxidizing agent; however, to obtain a high yield of the aldehyde
it needs to be distilled (it has a lower boiling point than ethanoic acid) as soon as it is formed
as otherwise it will oxidize further to a carboxylic acid (full oxidation).
Equation for the partial oxidation of ethanol:
full equation:
simpler version:

3C2H5OH + Cr2O72- + 8H+ 3CH3CHO + 2Cr3+ + 7H2O

C2H5OH + [O] CH3CHO + H2O

2. Full oxidation: if an excess of the oxidizing agent is used and the mixture is heated
under reflux, the alcohol oxidises to a carboxylic acid.
Equation for the further oxidation from ethanol to ethanoic acid:
full equation: 3C2H5OH + 2Cr2O72- + 16H+ 3CH3COOH + 4Cr3+ + 11H2O
simpler version:
C2H5OH + 2[O] CH3COOH + H2O

Secondary alcohols can only be oxidized to ketones by heating under reflux with acidified
potassium dichromate(VI). This is because the ketone does not have any hydrogen atom left
on the carbon of the carbonyl group.
Tertiary alcohols cannot be oxidized at all as they have no hydrogen atoms onto the carbon
that carries the hydroxyl group.

8. Halogenoalkanes

Primary, secondary and tertiary halogenoalkanes

-

As with alcohols, the distinction is again based on the number of alkyl groups or
carbons bonded onto the carbon which carries the halogen.

primary
Has one alkyl group or 1
carbon atom onto the carbon
which carries the halogen

secondary
Has two alkyl groups or 2
carbon atoms onto the carbon
which carries the halogen

tertiary
Has three alkyl groups or
3 carbon atoms onto the
carbon which carries the
halogen

SN1 and SN2 mechanisms: SN = nucleophilic subsitution

Halogenoalkanes react with hot dilute sodium hydroxide solution in nucleophilic
substitution reactions of which there are two types. The type of nucleophilic substitution
reaction which is favoured or predominant depends on the structure of the halogenoalkane i.e.
primary, secondary or tertiary.
During a nucleophilic substitution reaction the halogen is substituted by the hydroxide group
to form an alcohol.
In these reactions the hydroxide ion in sodium hydroxide, which is a negative ion, is called
the nucleophile as it seeks a positive nucleus i.e. the carbon atoms that carried the halogen
atom as the bond C-Hal is polar.

There are two different ways in which a nucleophilic substitution reaction can occur: SN1
and the SN2.
SN1
Example: 2-bromo-2-methylpropane with sodium hydroxide to form 2-methyl propan-2-ol
and sodium bromide.

Equation:

(CH3)3 CBr + NaOH (CH3)3 COH + NaBr

Mechanism (multistep):

unimolecular (hence the 1 in SN1 ): rate of reaction depends on 1 molecule only i.e. the
tertiary halogenoalkane;
multistep as it involves 2 steps - involves the formation of an intermediate i.e. carbocation
first order with respect to the halogenoalkane
molecularity of first step is 1
rate = k [halogenoalkane]
steps:
step 1
(slow
step)

Heterolytic fission results in dissociation or spontaneous ionisation of

halogenoalkane resulting in the formation of a carbocation - which is the
intermediate and can be isolated - and a halide ion; this step is the slowest
and therefore the rate determining step.

step 2

Nucleophilic attack of the carbocation formed in step 1.

(fast)

The rate of this multistep mechanism depends on the slowest reaction which is the first step
and therefore the rate of the reaction depends on the concentration of the halogenoalkane.

SN2
Example: 1-bromoethane with sodium hydroxide to form ethanol and sodium bromide.
Equation:

CH3CH2Br + NaOH CH3CH2OH + NaBr

Mechanism (one step) (overall second order):

bimolecular (hence the 2 in SN2 ): as both reactants (halogenoalkane and nucleophile) are
involved in the same single step which is also the rate determining step; overall reaction
is a one step process and involves a transition state/activated complex which produces the
product instead of an intermediate.
rate = k [Halogenoalkane][Incoming nucleophile]
In the single step, a new bond is made at the same time as an old bond is broken:
Bond
broken

as the carbon carrying the halogen is positively charged because of the polar
C-X bond, the carbon is attacked by the OH- on the side of the carbon atom
opposite to the halogen (the halogen atom affects approach by nucleophile);
during this process the carbon-nucleophile bond is formed; the nucleophile
donates its electron pair to the carbon to form the bond.

Bond
made

at the same time, the halogen breaks away from the molecule producing a
negative halogen ion; the energy needed to break the bond comes from the
bond made between the OH- and the carbon atom; the halogen needs to break
away from the molecule which is a very unstable arrangement as there are 5
groups bonded onto the carbon atom; the electron pair of the CX bond is
donated to the halogen.

In summary, the nucleophile donates an electron pair to the carbon that carries the halogen
atom which causes the bonding pair of the halogen to move away; no intermediate is formed
as the transition compound cannot be isolated; a transition state is a dynamic process during
which bonds are broken and made.
Factors which affect the rate of nucleophillic reactions in halogenoalkanes
Factor 1: Identity of the nucleophile
The hydroxide ion is a stronger nucleophile than water because it has a negative charge and
will therefore be attracted more strongly towards the partial positively charged carbon atom
bonded onto the halogen. As a result, the rate of a substitution with hydroxide (or hydrolysis)
is always faster than with water.
You are already familiar with both SN1 and SN2 reaction mechanisms or pathways. In this
section we will focus mainly on factors that affect the rate of both pathways in reactions with
hydroxide ions. This will help us to decide which pathway will be favoured with a certain
combination of reactants.
Factor 2: Nature of the halogenoalkane
The first elementary step in the SN1 pathway involves the formation of a carbocation
intermediate as the halogen leaves the molecule as an anion.
The greater the stability of the carbocation, the lower the activation energy of its formation
and the faster it is formed; the more its formation is favoured, the more SN1 is favoured.
The stability of carbocations depends on the number of alkyl groups on the carbon that
carries the positive charge as the electron-releasing alkyl groups make the carbon atom less
positive (delocalises the positive charge more). As a result, the greater the number of alkyl
groups, the more stable the carbocation.
Therefore, in decreasing stability of the carbocation (most stable first):
tertiary carbocation secondary carbocation primary carbocation
Tertiary carbocations, which are formed from tertiary halogenoalkanes, are more stable/less
reactive as the electron-releasing alkyl groups make the carbon atom less positive (delocalises
the positive charge more).
With primary halogenoalkanes, the formation of a reactive (unstable) primary carbocation has
an activation energy which is higher than the activation energy of the elementary step in
which the halogenoalkane and the nucleophile collide with each other which is why SN2 is
favoured with primary halogenoalkanes.
Another way of explaining favoured pathways is by considering how likely the transition
state in SN2 can be formed. In the transition state of SN2 carbon needs to accommodate five
groups; this is easier in a primary halogenoalkane as the carbon atom has 2 hydrogens on it which

leaves space for a 5th atom or ion. The alkyl groups on the carbon atom in a tertiary
halogenoalkane allow less space for a fifth particle to bond onto the carbon.

Factor 3: mechanism pathway taken by the halogenoalkane

primary halogenoalkanes

secondary
halogenoalkanes

SN2 - slowest

tertiary halogenoalkanes
SN1 - fastest

SN1 or SN2

As SN1 reactions generally occur faster (they are unimolecular), nucleophilic substitutions
involving tertiary halogenoalkanes are usually faster than those involving secondary or
primary halogenoalkanes.

Factor 4: Identity of halogen

As the iodine carbon bond is the weakest bond iodoalkanes tend to react at greater rates
than other haologenoalkanes in both SN1 and SN2.
Relative rates of reaction: fastest/highest rate: I Br Cl F.
9. Other functional groups
functional
group

condensed structural formula of

functional group

amine
(weak bases as
they are
derivatives of
NH3)

-NH2

amide

-CONH2

ester

COOC

nitrile

- CN

Rules for naming compounds with the above functional groups

rules

amines

amides

examples

Take the name the longest alkane chain bonded

onto the NH2
Drop the e
Add amine
If carbon chain is benzene ring: have phenyl as
prefix
Secondary amine: name both alkyl groups but in
alphabetical order
Can also be: name carbon chain and have prefix amino

methanamine,
ethanamine,

Take the name the longest alkane chain onto the

CONH2 including the C of CONH2
Drop the e and add amide
Any other shorter chain becomes an alkyl group
and is named first

methanamide,
ethanamide,
butanamide,
methylpropanamide,

butan-1-amine,
dimethylamine,
methylethanmine,
ethylmethylamine,
2-aminobutane

methylethanamide

esters

nitriles

The carbon chain from the alcohol is named first

and ends with yl; it is the chain bonded onto the
single bonded oxygen
The chain from the acid i.e. the chain bonded with
a double bond onto the oxygen is the anoate part.
Leave space between both parts.
If phenyl is attached to C in COO than benzoate
Take the name the longest alkane chain onto the
CN including the C of CN
Add -nitrile
Other shorter chain becomes an alkyl group and is
named first

methyl methanoate,
ethyl ethanoate, propyl
methanoate,

methanenitrile,
butanenitrile

Reactions involving halogenoalkanes and other nucleophiles

1. Nucleophilic substitution of primary halogenoalkanes with ammonia to form a
primary amine and a hydrogen halide acid.
- Ammonia is a stronger nucleophile than water because nitrogen is less
electronegative than oxygen and donates an electron pair more readily.
- Conditions: warm with excess NH3.

The SN2 mechanism for this reaction is shown below:

transition state
The nucleophile now is a molecule and not a negative ion such as the hydroxide ion. As a
result, after the halogen has left as an ion, the remaining particle has a positive charge and
therefore needs to lose a hydrogen proton to become neutral product.
In the SN2 mechanism this happens in the transition state as shown by the curly arrow
showing the loss of the hydrogen ion; the bonding pair between the nitrogen and the
hydrogen becomes the lone pair on the nitrogen.
In the SN1 mechanism this de-protonation occurs as a step 3 after the nucleophile substitution
has been completed.
2. Nucleophilic substitution of primary halogenoalkanes with potassium cyanide to form
a nitrile and a potassium halide salt.
- Cyanide ions are very strong nucleophiles because of the negative charge. In this
reaction the non-bonding pair donated is from the carbon. The carbon atom also
carries the negative charge of the molecular ion.
- As a result of this substitution reaction the chain length of the halogenoalkane has
been increased by 1 carbon atom.

For example, using 1-bromopropane as a typical primary halogenoalkane:

CH3CH2CH2Br

CN- CH3CH2CH2CN + Br-

The full equation:

CH3CH2CH2Br + KCN CH3CH2CH2CN + KBr
The bromine (or other halogen) in the halogenoalkane is simply replaced by a -CN
group - hence a substitution reaction. In this example, 1-butanenitrile is formed
from 1-bromopropane.
Conditions: reflux with KCN dissolved in ethanol.

Reactions of nitriles
1. Acidic hydrolysis
- Nitriles can undergo hydrolysis with a dilute acid (such as H2SO4) to form
carboxylic acids and the ammonium ion. (It forms ammonia from the hydrolysis
reaction but the ammonia undergoes an acid-base reaction with the acid to form
the ammonium ion)
2. Reduction
- A reduction reaction is the addition of hydrogen. The reduction of nitriles results
in the formation of a primary amine as shown by the equation below showing how
1-butanenitrile is converted into 1-butanamine
- Example: CH3CH2CH2CN + 2H2 CH3CH2CH2CH2NH2

10. Elimination reactions

Elimination of HBr from bromoalkanes
- Bromoalkanes in the presence of nucleophiles can undergo either:
A nucleophilic substitution reaction to form, for instance, an alcohol
Elimination reaction to form an alkene
Whenever a bromoalkane is in the presence of a nucleophile, e.g. OH-, competition between
these two types of reactions occurs. Which type of reaction actually takes place depends on
the conditions like temperature, solvent, structure of the halogenoalkane and the identity of
the nucleophile e.g. if the nucleophile is a strong base or not.
Example:
A hot alcoholic hydroxide ion (e.g. NaOH/KOH dissolved in ethanol) can either substitute
the halogen atom or effect an elimination (remove H+) to produce an alkene.
However, in these conditions, hot alcoholic (condition = heat and alcoholic OH-), the
elimination is favoured. In fact, the OH- reacts with the ethanol to form water and the
ethoxide ion, C2H5O-, which then acts as a base in the reaction with the bromoalkane
(stronger base than OH-).

Mechanism for Elimination Reactions

In each mechanism a base (e.g. C2H5O-, ethoxide ion, from a hot alkanoic solution of NaOH)
abstracts a hydrogen atom from a carbon which is the carbon next to the carbon which
carries the halogen:

Overall equation:

CH3CH2Br

CH2CH2

+ H2O

C2H5ONa + CH3CH2Br

CH2CH2

+ NaBr

NaOH +
or

+ NaBr
+ C2H5OH

E2 :
1 step (similar to SN2); bimolecular; transition state; this involves:
reagent acts as a strong base and abstracts hydrogen (it accepts a hydrogen ion) from
carbon adjacent to the carbon which carries the halogen (instead of attacking
positive carbon); it does this by donating an electron pair to the carbon (Lewis base);
at the same time: the carbon-hydrogen bond breaks and is used to make a double
bond between the two carbons
at the same time: the halogen leaves from the other carbon taking the bonding pair
Rate = k [RHal] [CN-]
Overall second order
Favoured by primary halogenoalkanes

E1 :
2 steps; first step unimolecular; this involves:
1st step: formation of cation/intermediate as halogen leaves (ionisation) and takes bond (at
this point, either a E1 or a SN 1 can occur as there is competition between the two
pathways)
2nd step: reagent acts like a strong Bronsted base as it abstracts hydrogen from a carbon
attached to the carbon to which the halogen was attached; electrons from this carbonhydrogen bond are used to make the double bond.
rate = k [RHal]
overall first order
favoured by tertiary halogenoalkanes: order of reactivity: R3CHal R2CHHal RCH2Hal

11. Condensation Reactions

-

Condensation reactions are reactions between two different reactants that react
together to form a larger molecule with the elimination of a small molecule such as
water.

Reactions between alcohols and carboxylic acids esterification

-

Conditions for esterification: heat and concentrated sulphuric acid.

For example when ethanol and ethanoic acid are heated in the presence of
concentrated sulphuric acid an ester called ethyl ethanoate is formed.
CH3CH2OH + CH3COOH CH3CH2OOCCH3 + H2O

In the above reaction, the hydrogen on the alcohol is eliminated whilst the hydroxide is
eliminated on the acid molecule and both join to form water. It is the carbon-oxygen bond in
the acid molecule that breaks.
Esters have sweet and fruity smells and are used in: perfumes, flavourings in food, solvents,
pain killers and in the production of fibres e.g. polyester
Reactions of amines with carboxylic acids
-

Amines and carboxylic acids react to form amides.

The OH group on the acid is eliminated and forms water with the hydrogen
eliminated from the amine group.

Condensation polymerization
Condensation polymerization requires 2 different monomers with each monomer having two
functional groups so that a new bond can be made between the two monomers. The
monomers can have the same functional groups on them as those used in the examples below
or they can have two different functional groups like in amino acids.
Polymerization involving alcohols and carboxylic acids to form polyesters
Example: ethane-1,2-diol and benzene-1,4-dicarboxylic acid.

Polymerization involving carboxylic acids and amines to form polyamides

Example: polymerization involving 1, 6-diaminohexane and 1, 6-hexanedioic acid.

12. Stereoisomerism
Stereoisomers are compounds with the same molecular formula and same structural formula
but with different arrangements of atoms in space i.e. the order in which atoms are bonded
along the chain is the same but the spatial arrangement around certain (carbon) atoms is
different.
There are two types of stereoisomers: geometric isomerism and optical isomerism. Within
each type of stereoisomers there are only two isomers.
Geometric isomerism (cis-trans isomerism):
This type of isomerism occurs because free rotation of a carbon-carbon bond is prevented
either because it is a double bond or because the carbon-carbon bond is part of a ring
structure.
As a result geometric isomerism happens in:

Non-cyclic alkenes in which there are 2 different atoms (or groups of atoms) on each
carbon atom on either side of the double bond. The bond prevents the C=C from
rotating and changing the position of the atoms on either side. These 2 different atoms on
the one carbon atom can be the same different atoms on the other atom or they can be
different. If both sets of different atoms are all different than we cannot use the terms cis
and trans anymore.

In cycloalkanes when the same atom (other than hydrogen) is found on two carbons in
the ring; no rotation possible without breaking the ring.

Non-cyclic alkenes
Refers to a different arrangement in terms of orientation of atoms or groups attached to a
double bond (free rotation is impossible as there are two regions of overlap within the
bond; above and below the axis between both nuclei; rotation would cause the overlapping
orbitals to separate and therefore break the bond) (a single sigma can rotate as the area of
overlap is between both nucleii).
The two isomeric forms cannot be interconverted without breaking a carbon-carbon bond;
this means that both are chemically different compounds!
Two possible isomers:
cis: two identical groups are on the same side of the double bond;
trans: two identical groups on opposite side of the double bond.
Example 1:

cis-but-2-ene

trans-but-2-ene

melting point
(C)

- 139

- 106

boiling point
(C)

cis-1,2-dichloroethene

trans-1,2-dichloroethene

Example 2:

melting point
(C)

- 80

- 50

boiling point
(C)

60

48

Geometrical isomers have different physical properties and sometimes also, chemical
properties.
Examples:

Physical:
The trans isomers may have lower boiling points than cis-isomers - this is the case
because the trans-isomer is a non-polar molecule whilst the cis-isomer has a dipole
moment so therefore stronger intermolecular forces.
However, trans-isomers tend to have higher melting points as their molecules can fit
more tightly together (more like a mosaic of bricks) than the molecules in the cis-isomers.
As intermolecular forces can only act over a short distance, packing molecules more
closely makes the intermolecular forces more effective needing more energy to melt.
More examples: physical properties of cis/trans isomers of but-2-ene-1,4-dioic acid
(1) The trans form: density = 1.64 g cm-3, solubility in water 0.7g/100 cm3 at 25 o C,
melting point 287 o C,
(2) The cis form: density = 1.59 g cm-3, solubility in water 78.8g/100 cm3 at 25 o C,
melting point 130 o C,
In this example, the trans form has a much higher melting point as a result of
intermolecular hydrogen bonding. However, the cis form, because both COOH groups
are near each other there is intramolecular hydrogen bonding (i.e. between both COOH
groups within the same molecule) and therefore less intermolecular hydrogen bonding.
Intramolecular bonding does not determine any melting and boiling point

Chemical: when cis-but-2-ene-1,4-dioic acid is heated gently, water is eliminated and the
two carbons at either end of the chain are linked to form a cyclic anhydride (contains
O=C-O-C=O) while the trans isomer only sublimes at that temperature.
Explanation of reaction of cis-isomer: because both COOH are on the same side (close
together), they react, eliminating a water molecule and forming a cyclic anhydride. In the
trans isomer, both COOH groups are too far apart for such a reaction to happen.

+ H2O

Cyclo-alkanes
Geometric isomerism also occurs in cyclic alkanes.
Free rotation around a single carbon-carbon bond is also restricted in cyclic alkanes due to
the inflexibility of the ring. Cyclic alkanes have a planar structure which allows cycloalkanes to have other atoms, e.g. halogens, connected on the same side of the plane or one
halogen on one side and one halogen on the other side of the ring.

Geometric isomerism can be recognised by looking for:

a double bond with two different atoms/groups joined to the atoms at either end of the
double bond;
a ring structure with two different atoms or groups of atoms joined to any two carbon
atoms in the ring.

Optical isomerism

Optical isomers (or enantiomers) are two molecules with the same molecular and structural
formulas that are mirror images from each other and that cannot be superimposed. A
substance which has two mirror-image molecules which cannot be superimposed is called
chiral.

You can determine if a substance is chiral by looking for one or more chiral centres in its
molecule.
A chiral centre is an asymmetric carbon atom which is a carbon atom that has four different
atoms of groups of atoms bonded onto it.
These four different groups can be arranged differently in two different ways; each way is
called an enantiomer.
However, some molecules with chiral centres have mirror-images which are super-imposable
and are therefore not chiral or optically active.

Similarities between enantiomers

enantiomers have identical melting and boiling points as the different spatial arrangement
does not affect the strength of intermolecular forces; also because of this solubility is the
same;

have identical chemical energetic stability and identical reaction paths (same activation
energies) which means that when a chiral molecule is formed during a reaction both
enantiomers are formed in equal amounts (=racemic mixture or racemate);

Differences

chemical: they react differently with other chiral molecules; which is why enzymes
(which are chiral) only react with a specific protein (chiral molecules) to catalyse a
reaction;

physical: the chiral centre in each enantiomer rotate the plane of polarised light in the
opposite direction (non-chiral centres do not rotate the light at all!); plane-polarised light is
light that emerges from a polariser and is characterised by the fact that the electric field of
the light oscillates in one plane only e.g. perpendicular to the direction in which the light
travels. Using a polarimeter, which measures the angle of rotation, as shown below, the

degree of rotation can be measured. Both enantiomers will rotate the light over the same
angle but in the opposite direction