NSSCAS Chemistry

Theme 4
Organic Chemistry
Theme 4 consists of SEVEN topics
4.1 Foundations of organic chemistry
4.2 Hydrocarbons
4.3 Halogen derivatives
4.4 Hydroxyl compounds
4.5 Isomerism: structural and
stereoisomerism
4.6 Carbonyl compounds
4.7 Carboxylic acids and derivatives
4.1 Foundations of organic chemistry

4.1.1 Organic chemistry terminology

4.1.2 Shapes of organic molecules

4.1.3 Infra-red spectroscopy

 Topic 4.2 Hydrocarbons

4.2.1 Alkanes
4.2.2 Alkenes
4.2.3 Hydrocarbons as fuels
 4.1.1 Organic chemistry terminology
• interpret and use the following terminology associated with
organic reactions:
 functional group
 homolytic fission and heterolytic fission
 free radical, initiation, propagation, termination
 nucleophile, electrophile
 addition, substitution, elimination, hydrolysis, condensation
 oxidation and reduction
• recall and use systematic nomenclature to name alkanes, alkenes,
halogenoalkanes, alcohols, aldehydes, ketones, carboxylic acids,
esters and amines, with chain length up to six carbon atoms,
including:
– numbering the carbon atoms in a direction to give the lowest prefix
possible e.g. 1-chlorobutane (not 4-chlorobutane)
– the use of the prefixes mono-, di-, tri-, tetra-, penta-, hexa-.
(in equations for organic redox reactions, the symbols [O] and [H] are
acceptable for oxidising and reducing agents)
 What is organic chemistry?

• Organic chemistry is a branch of chemistry

that studies the structure, properties and
reactions of organic compounds which contain
carbon in covalent bonding (excluding simple
compounds such as: CO, ,,).
 Formulae used in organic chemistry
• There are several formulae in which organic
compounds / molecules can be presented as:

– General formula
– Structural formula
– Displayed formula
– Skeletal formula
– Condensed formula
 General formula
• The general formula is an algebraic formula that
can be applied to chemicals in the same family of
compounds.
• The following are the general formulae for
alkanes, alkenes and alcohols as examples:
– Alkanes -
– Alkenes -
– Alcohols - OH
 Structural formula
• The structural formula shows the order of the
arrangement of atoms joined together in an
organic compound without showing all the bonds.
• Only double (=) and triple () bonds are shown
• These formulae are usually written in one line.
• Examples:
– Ethane:
– Ethene: =
– Ethanoic acid: COOH
- 2-methylbutane: CH()
 Displayed
formula

• Displayed formula shows all the atoms, all the

bonds(single ; double = and triple ) present in the
molecule and the order of the atoms joined together.
• A displayed formula also shows the orientation of the
atoms and bond angles.
 Skeletal formula

• The skeletal formula shows only the functional groups. The carbon and
hydrogen atoms are simplified and hidden.
• In a skeletal formula:
– there is a carbon atom at each junction and at the end of the bond, there is no
carbon atom at a place occupied by another functional group.
– there is enough hydrogen atoms bonded to each carbon so that each carbon has
four bonds only.
 Homologous series
• A homologous series is a group (family) of compounds which
have the same functional group and general formula.
• A functional group is the reactive group attached to the
compound’s chain that defines the physical and chemical
properties of the compounds in a specific homologous series.
homologous series prefix / suffix example

alkanes -ane butane CH3CH2CH2CH3

alkanes (branched) alkyl- methylpropane CH3CH(CH3)CH3

cycloalkanes cyclo- - ane cyclopenthane C5H10

alkenes -ene propene CH3CH=CH2

halogenoalkanes fluoro-/ chloro- / bromo- / bromoethane CH3CH2Br

iodo- - alkane
alcohols -ol ethanol CH3CH2OH

aldehydes -al propanal CH3CH2CHO

ketones -one propanone CH3COCH3

carboxylic acids -oic acid butanoic acid CH3CH2CH2COOH

esters alkyl- -anoate methyl ethanoate CH3COOCH3

amines -amine propan-1-amine, CH3(CH2)2NH2

 Names of organic compounds
• Organic compounds are named systematically according to the
IUPAC (International Union of Pure and Applied Chemistry)
nomenclature.
• Nomenclature is a system of names used in a particular subject.
• There are some basic rules you need to be familiar with to be
able to name organic compounds with a chain length of up to six
carbons.
• The rules will be emphasised each time when we look at a
particular homologous series (alkanes, alkenes,
halogenoalkanes, alcohols, aldehydes, ketones, carboxylic
acids, esters and amines).
 Basic rules for naming organic compounds
1. Find the length of the stem by counting the
longest continuous (consecutive) chain of carbons
and decide the prefix. The stem name is based on
the number of carbon atoms.
1 2 3 4 5 6
number
of carbon
atoms

stem meth- eth- prop- but- pent- hex-

name
 Basic rules for naming organic compounds conti…
2. Look for the functional group (containing oxygen) and decide on the suffix
(ending). The functional group on the molecule normally tells you the ending of
the name (suffix). Other functional groups and substituents (not containing
oxygen) are indicated by prefixes (e.g. alkyl groups and halogens). of which the
position of each is shown by its locant (carbon number on the main chain).
3. Number the carbon chain so that the functional group sits on the lowest
possible number carbon.
4. Make a note of the carbon number the functional group is attached to. Place
this number before the suffix. For example, butan-1-ol.
5. Any side chains and less important functional groups are written as prefixes in
alphabetical order.
6. If there is more than 1 identical functional group or side chain, put di- (2), tri-
(3) or tetra- (4).
7. Consecutive numbers are separated by a comma and a number and a letter/
word is separated by a hyphen (e.g. 2,2-dichloropentane) which is generally taken
as locant-prefix-parent-locant-suffix.
 Basic rules for naming organic compounds
8. If the compound contains double or triple bonds between carbon
atoms, it must be indicated using infixes.

infixes meaning

-an- All single bonds C-C

-ene- One double bond C=C

-yn- One triple bond CC

-dien- Two C=C double bonds

-trien- Three C=C double bonds

 Naming compounds with one or more functional groups

1. Identify the longest chain of unbranched carbon atoms for

the stem name.
2. Identify any functional groups and alkyl side chains. Give
the appropriate prefix or suffix.
3. Provide any locant on the longest unbranched chain.
4. If the compound has more than one functional group, use
the one with the highest priority (principal group) as the
suffix and the others indicated as the prefix substituents. The
order from highest to lowest priority according to the IUPAC
rules of a comprehensive system of priority is alkene, alkyne,
halogenoalkane, carboxylic acids, esters, aldehydes, ketones,
alcohols, amines.
 Naming compounds with one or more functional
groups
6. The functional group with the highest oxidation state
gets the higher ranking, that is, a functional group with
more bonds to oxygen will outrank one with fewer bonds.
7. There are certain functional groups that never get a
suffix, they will always be prefixes and get the suffix of the
hydrocarbon. (-ane, -ene, or –yne)
8. One such group are the halides (bromo, chloro, fluoro,
iodo). If more than one halide is present, they are named in
alphabetical order.
9. When carbon-carbon multiple bonds are present with
other functional groups they are ranked lower than the
amines.
 organic chemistry terminology
• You should be able to interpret and use the
following terminology.
– functional group
– homolytic and heterolytic fission
– free radical, initiation, propagation and
termination
– nucleophile and electrophile
– addition, substitution, elimination, hydrolysis,
condensation
– oxidation and reduction
 functional groups
• A functional group is defined as an atom or
group of atoms within a molecule.
• It determines the characteristic chemical
properties of the compound which contains
that specific functional group.
Examples
Alkanes C-C and C-H single bond , hydrocarbon
Alkenes C=C double bond functional group
Carboxylic acids –COOH functional group
 functional groups
homologous Functional group
series
alkanes C-C single bonds AND C-H single bonds
alkenes C=C AND C-H single bonds
halogenoalkanes C-C single bonds AND C-hal
alcohols C-OH
aldehydes

ketones
carboxylic acids H
esters R
amines
 Bond fission
• Bond fission is the breaking of a covalent bond.
• The electron pair in the bond can be distributed
in two ways depending on the type of bond
fission.
• There are two types of fission.
– homolytic fission (homolysis)
– heterolytic fission (heterolysis)
 homolylitic fission

• In homolytic fission, a covalent bond breaks in such a way

that each of the bonded atoms gets one of the shared
electrons.
• The species produced during homolytic fission are called free
radicals.
• Free radicals – are species produced when a bond breaks
homolytically. All free radicals have an unpaired electrons
(represented by dots on the diagram) and they are highly
reactive.
examples of homolytic fission
 heterolytic fission

• In heterolytic fission, a covalent bond breaks in

such a way that one of the bonded atoms gets
both of the shared electrons, and form ions.
• In a heterolytic fission the more electronegative
atom takes both the electrons in the covalent
bond.
examples of heterolytic fission
 Free radical chain reactions: initiation,
propagation and termination
Homolytic fission involves a series of steps known as
initiation, propagation and termination.
• Initiation step- involves breaking the bond using input
energy ( UV-light), this is called a photochemical
reaction and it results in the formation of free radicals.
• Propagation step-involves free radicals attacking the
reactant molecules, generating more free radicals.
( only stops when radicals stops with each other.
• Termination step –when two free radicals reacts
together, forming a molecule and no other free
radicals generated.
initiation, propagation and termination
 nucleophile
• A nucleophile is a species which contains a lone
pair of electrons and is attracted to regions of
positive charge or electron-deficient sites.
• Nucleophiles are often negatively-charged or carry
a partial negative charge.
• Some examples of nucleophiles are:
– ,
– ,
– ,
– ,

–O
 electrophile
• An electrophile is an electron-deficient species
which can accept electrons and is attracted to
regions of negative charge or electron-rich sites.
• Electrophiles are often positively-charged or
carry a partial positive charge.
• Some examples of electrophiles are:
–,
 Activity
1. Write an equation to show the heterolytic
fission of the C-Cl bond in chloromethane.
Include a curly arrow in your answer. (2)
Which of the following species H2 , H+ , OH-
is likely to act as:
i. Nucleophile
ii. Electrophile
iii. Free radical when exposed to UV light
 Some common organic reactions

• Most organic reactions happen at the functional group, while the

rest of the molecule does not react. The different functional groups
have characteristic reactions. These types of organic reactions are:
– free-radical substitution
– electrophilic addition
– electrophilic substitution
– nucleophilic addition
– nucleophilic substitution
– redox (oxidation and reduction)
– Hydrolysis
• These reaction types are introduced now as concepts and we will
look at a few examples, however they will be explained in more
details under the specific sections where they are applied in detail.
 addition, substitution and elimination
• An addition reaction is a reaction in which one
molecule combines with another to form a larger
molecule with no other products.
C2H4 + Br2 C2H4Br2
• A substitution reaction is a chemical reaction during
which one functional group or atom in a chemical
compound is replaced by another functional group.
CH4 + Cl2 CH3Cl + HCl
• Elimination reaction is any of a class of organic
chemical reaction in which a pair of atoms or groups
of atoms are removed from a molecule.
C2H5OH C2H4 + H2O
 hydrolysis and condensation
• Hydrolysis is a breakdown of a molecule by
water / is a reaction in which water is added and
usually it involves breaking large molecules.
C2H5Br + H2O C2H5OH + HBr

• Sometimes acids or alkalis are added to catalyze

the hydrolysis.
C2H5Br + NaOH C2H5OH + NaBr
• Condensation is a reaction in which a small
molecule like water, HCl, HBr, etc is given out
in a reaction in which two molecules
combine.
 oxidation and reduction
• Oxidation in organic reactions is the addition of
oxygen atoms to a molecule and/ a removal of
hydrogen atoms from a molecule.
1. C2H5OH +[O] CH3CHO + H2O

2. CH4 + O2 CO2 + H2O

• Reduction in organic reactions is the removal of
oxygen atoms from a molecule and /or the
addition of hydrogen atoms to a molecule.
1. CH3CHO + 2[H] CH3CH2OH

2.
 4.1.2 Shapes of organic molecules

• describe and explain the shape of, and bond

angles in, the ethane and ethene molecules in
terms of electron pair repulsion theory
(including relative length of bonds between
carbon atoms) (see section 1.3.2)
• predict the shapes of, and bond angles in
other related molecules
 VSEPR theory
• VSEPR theory is an improved and extension of
Lewis model but predicts the shapes of
polyatomic molecules.
 SN –Steric Number
• Steric number (SN) = No. of attached atom +
No. of lone pairs
 shape of ethane
• It has a Trigonal planar shape with a bond
angle of approximately 121.7° and 116.6°
 shape of ethane
• It has a tetrahedral shape with a bond angle
of approximately 109.5°
 4.1.3 Infra-red spectroscopy
• analyse an infra-red spectrum of a simple
molecule to identify functional groups (see
Data Booklet for the functional groups
required)
 Infrared spectroscopy in everyday life

• In everyday life, infrared spectroscopy is used in breathalysers

to identify the –OH functional groups that is indicative of
alcohol.
• The level of absorption that is observed on the spectrum is
related to the concentration of alcohol in the blood.
• It uses the principle that infrared light is
absorbed when shined on alcohol.
• The infrared light passes through a chamber
where it will interact with the alcohol and
cause the light density to decrease.
• The decrease in light intensity is proportional
to the alcohol present in the captured breath.
 Analysing infra-red spectroscopy
• A beam of infrared radiation is passed through the sample. This
beam will have a frequency in the infrared region of the
electromagnetic spectrum.
• Molecules of our samples will absorb some of these frequencies.
• The beam that passes through is analysed.
• We can plot a graph of % transmittance against frequency / wave
numbers per centimetre.
• The wave numbers per centimetres are found in the Data
Booklet.
• The peaks on the IR spectrum show the absorbed functional
group.
• The appearance of the peak can be strong s or weak w and very
broad and sharp.
Infrared region in the electromagnetic
spectrum
Data Booklet infor..
I. R. spectra
 4.2.1 Alkanes
• interpret and use the general, structural, displayed and skeletal formulae of the
alkanes
• recall and use systematic nomenclature to name alkanes, with chain length up to
six carbon atoms, e.g. 2,2-dimethyl hexane
• deduce the molecular formula of alkanes, given its structural, displayed or skeletal
formula
• explain the general unreactivity of alkanes, including towards polar reagents
• describe the chemistry of alkanes as exemplified by the following reactions of
ethane:
– combustion
– substitution by chlorine and by bromine
• describe the mechanism of free-radical reactions with particular reference to the
initiation (homolytic fission), propagation and termination reactions, including the
substitution of methyl groups by halogens
• explain the use of crude oil as a source of both aliphatic and aromatic
hydrocarbons
• explain that cracking can be used to obtain more useful alkanes and alkenes of
lower Mr from larger hydrocarbon molecules
 What is a hydrocarbon?
• Is a compound containing carbon and hydrogen
atoms only.
• Examples of hydrocarbons are:
– alkanes,
– alkenes,
– alkynes
– arenes
 alkanes
• Alkanes are saturated hydrocarbons, the carbon
atoms are joined to each other via single
covalent bond only.
• They form the homologous series with a
general formula .
• You should be able to interpret and use the
general, structural, displayed and skeletal
formulae of alkanes.
 Examples of alkanes
name molecular structural formula state melting boiling density / g
formula point / point /

methane gas 182 164 0.424

ethane gas 183 88 0.546
propane gas 190 42 0.582
butane gas 138 0.5 0.579

pentane liquid 130 36 0.626

hexane liquid 95 69 0.657

heptane liquid 90 98 0.684

octane liquid 57 126 0.703

nonane liquid 51 151 0.718

decade liquid 30 174 0.730

eicosane solid 37 344 0.785

 Formulae of alkanes (molecular, structural,
displayed and skeletal formulae)
• General formula=CnH2n+2
• Molecular formula = C5H12 (pentane)
• Structural / displayed formula

• Skeletal formula
NB: Naming alkanes and deduce their
molecular formulae from given formulae
Naming unbranched alkanes
 TIPS: Naming branched alkanes
• Identify the longest unbroken carbon chain and name it.
This chain is called the parent chain.
• Identify all of the substituents (groups appending from the
parent chain) and name them.
• Number the carbons of the parent chain from the end that
gives the substituents the lowest numbers. Indicate the
positions of the substituents.
• If the same substituent occurs more than once, the location
of each point on which the substituent occurs is given. In
addition, the number of times the substituent group occurs
is indicated by a prefix (di, tri, tetra, etc.).
• Assemble the name, by listing the substituents in
alphabetical order.
 Naming branched alkanes
•
Practice - Naming branched alkanes
Practice - Naming branched alkanes
 Physical properties of alkanes
• Alkanes are non-polar, thus they are soluble in
non-polar solvents like .
• They are, in general, insoluble and less dense
than water.
• The boiling point of straight-chain alkanes
increases with the size of molecule. This is
because the number of electrons in each
molecule increases, resulting in the increased
strength of van der Waals'. Thus more energy is
required to break these forces.
 Physical properties of alkanes …
• For a branched alkane, it is more volatile and its boiling
point is lower than its counterpart with the same number
of carbon atoms. This is because they are more spherical
and have a lower surface area. Thus less temporary
dipoles can be set up and the van der Waals' forces are
weaker, less energy is required to overcome it.
• The density of liquid alkanes increases slightly. The mass
of each succeeding molecule increases but due to the
increased strength of van der Waals' forces, the
molecules are more closer together. This results in higher
ratio of mass/volume.
 Cycloalkanes
• Cycloalkanes are alkanes that are joined up as a
ring.
• The smallest possible cycloalkane is
cyclopropane.
• Cycloalkanes have two hydrogen less than the
corresponding straight-chain alkanes.
• Cycloalkanes have the general formula
• The general formula is the same for
cycloalkanes and alkenes, however,
cycloalkanes (like straight chain alkanes) only
consists of single bonds
Examples of cycloalkanes
 Reactions of alkanes
• Alkanes are saturated and generally unreactive
because they are non-polar, hence they are
unattractive towards nucleophiles and
electrophiles.
• Alkanes will only react with non-polar reagents
in the presence of heat or ultraviolet light.
• You are required to describe the chemistry of
alkanes as exemplified by:
– Combustion
– Substitution by chlorine and bromine (free radical
reactions)
 Complete combustion of alkanes
• Alkanes undergo complete combustion under
excess oxygen gas to give carbon dioxide and water.
• For example: (g) + 2 (g) → (g) + 2O(g) ΔH° = 890 kJ
mol⁻¹
• In general, + (x + ) x + () O
• Larger alkanes are more difficult to ignite. This is
because alkanes only burn in the gaseous state and
larger alkanes have stronger van der Waals' forces
that hold them together. Therefore more energy is
required to vaporise it.
Incomplete combustion of alkanes
• When the supply of oxygen is limited, alkanes
undergo incomplete combustion. The possible
products are carbon monoxide, carbon and
water.
• For example:
2C (g) + 3 (g) → 2CO (g) + 4O (g)
or (g) + (g) → C(s) + 2 O(g)
 Halogenation
• Alkanes undergo halogenation via free-radical
substitution to give a range of products.
• In free-radical substitution, hydrogen atoms in the
molecule are gradually substituted by halogen atoms.
– Reagent: Chlorine gas, or bromine gas,
– Condition: The presence of ultraviolet (UV) light or sunlight
– Product : Halogenoalkanes (alkanes with halogens)
• Free-radical substitution proceeds via a chain
reaction. During a chain reaction, for every reactive
species you start off with, a new one is generated at
the end, and this keeps the process going.
 Halogenation – free radical substitution
• Free-radical substitution proceeds via a chain
reaction. During a chain reaction, for every reactive
species you start off with, a new one is generated at
the end, and this keeps the process going.
• When methane reacts with chlorine in sunlight, the
greenish-yellow colour fades and steamy acidic
fumes of hydrogen chloride can be observed.
• Reaction: + Cl + HCl
• However, this is a chain reaction and does not end here.
More hydrogen atoms will be substituted as long as
there are sufficient chlorine atoms.
free radical substitution of hydrogen by
chlorine
 Substitution reaction
• Substitution by chlorine

• Substitution by bromine
 Halogenation – free radical substitution - Step 1: initiation

• The reaction is initiated by the homolytic fission

of chlorine molecule in the presence of UV light,
forming chlorine free radicals.
• ClCl
• The represents free radicals and the reaction
takes place in the presence of UV light.
 Halogenation – free radical substitution -
Step 2: propagation

• During propagation step The free radicals then

attack the methane molecules, leading to a
chain reaction.
• + + HCl
• + Cl +
• Cl + + HCl
• + +
 Halogenation – free radical substitution -
Step 3: Termination
• Termination step The reaction ends with the
free radicals joining up with each other.
• +
• + Cl
• +
• + Cl
• +
• + ClCl
Free-radical mechanism
Free-radical mechanism
 The mechanism of free - radical
substitution – formation of

• To produce mainly tetrachloromethane (), an

excess of chlorine gas is used so that all the four
hydrogen atoms in eventually get substituted.
• Bromine gas reacts in a similar manner but the
reaction is slower because the electronegativity
of bromine is lower than that of chlorine.
 Crude oil (petroleum)
• Crude oil is formed under the earth’s crust through
a process called fossilisation.
• When the remains of the once living organism are
subjected to high pressure and temperature they
are converted into crude oil and some other
fossils fuels like coal.
• Crude oil (petroleum) is mainly a mixture of
naturally occurring hydrocarbons - aliphatic and
aromatic compounds.
• The major use of alkanes is to make fuels (natural
gas, petrol, diesel,kerosine, etc).
aliphatic and aromatic hydrocarbons
• Aliphatic - are straight chain hydrocarbons
consisting of a single, double or triple bond.
Examples: alkanes, alkenes and alkynes.
• Aromatic – also called arenes, they are cyclic
in nature, consisting of alternating single and
double bonds.
• Example: benzene ring.
aliphatic and aromatic hydrocarbons
 Cracking
• Crude oil often contains a greater quantity of heavier
fractions than lighter fractions.
• Lighter fractions are more useful and therefore more in
demand.
• The large hydrocarbon molecules in the heavier fractions
can be broken down into smaller, more useful molecules.
This is called cracking.
• Cracking is a reaction in which larger saturated
hydrocarbon molecules are broken down into smaller,
more useful hydrocarbon molecules, some of which are
unsaturated: the original starting hydrocarbons are
alkanes.
• The products of cracking include alkanes and alkenes
Cracking …
• Long-chain hydrocarbon molecules can be
broken down into smaller, more useful
molecules using a catalyst.
• This is called catalytic cracking and is an
example of a thermal decomposition reaction.
• Catalytic cracking requires: high temperatures
and a catalyst
• During cracking, the long molecules break
apart, forming smaller alkanes and alkenes.
• Alkenes are reactive molecules that are used
to make plastics and other chemicals.
 End of topic activity
• Mr Sovi should give us more activities and
tests