CHE 176 – ORGANIC CHEMISTRY I

PROF. O O. SONIBARE
OFFICE: F104, CHEMISTRY DEPT.
 LECTURE OUTLINE
 Basic concept of organic chemistry – definition and
importance of organic chemistry, atom and molecular
orbitals including bonding, unique nature of carbon and
hybridization

 Determination of molecular composition and structure of

organic compounds

 Functional group classes of organic compounds and

nomenclature

 Reaction mechanism and Kinetics

 Organic reactions- types and factors affecting them.

DEFINITION OF ORGANIC CHEMISTRY
What is Chemistry?
Chemistry is the branch of physical science that deals with
the study of composition, properties and reactions of
substances.

What is Organic Chemistry?

Branch of chemistry that deals with carbon compounds.
This branch of chemistry is very important because of the
large numbers of organic compounds and their
occurrences and applications.
IMPORTANCE OF ORGANIC CHEMISTRY
Most of the substances we use in our daily life are organic
in nature:
(a) The food types that sustain human body are made up of
organic compounds, e.g. carbohydrates, proteins, fats and oils,
vitamins etc.
(b) the clothes we wear (wool and cotton- cellulose)
(c) the commodities we use (wood- cellulose, plastic- polymer
of hydrocarbons)
(d) the source of primary energy (petroleum, natural gas, coal)
(e) The medicine we take
(f) In agriculture (fertilizers and agrochemicals)
 UNIQUE NATURE OF CARBON
What makes carbon special? Why is a whole field of
organic chemistry dedicated to carbon?
Carbon is very unique due to many reasons:

1. Tetravalent nature: Due to its tetravalent nature,

carbon always form covalent bonds by sharing
electrons with one, two, three or four carbon atoms or
atoms of other elements or group of atoms. Carbon
can form single, double or triple bonds with other
atoms because of its bonding ability.
2. Catenation: The tetra-covalency of carbon atom
allows it to combine easily with other carbon to
form stable chain like structure.

Catenation: Catenation is the ability of an element

to form chains and rings in which its atoms are
bonded to one another i.e. ability to exhibit self–
linkage.
3. Formation of strong C-C covalent bonds: The
single bond formed between the carbon atoms is strong.
This results in the formation of stable compounds.
Carbon atoms also form stable bonds with other atoms
e.g. H, Cl, Br, O etc.

3. Formation of C-C multiple bonds: Due to its small

size, the C-atom can also form multiple bonds. This
gives rise to a variety in the carbon compounds.

4. Hybridisation: Formation of hybrid orbitals allows

carbon to form double and triple bonds.
ATOMS, ATOMIC AND MOLECULAR ORBITALS –
Refer to your CHE 156 Note
 HYBRIDISATION OF ORBITALS IN CARBON

Hybridization simply means mixing

Hybridization of orbitals involves mixing of atomic

orbitals to form new identical orbitals known as
hybrid orbitals.

These hybrid orbitals are subsequently used in

bonding to give more stable compounds.
3 types of Hybridization exist in carbon:

sp3, sp2 and sp

All the three types involve mixing of s and p

orbitals to form new hybrid orbitals.
 sp3 HYBRIDIZATION IN CARBON
Atomic Number of Carbon = 6
Electronic configuration of Carbon in ground state =
1s2 2s2 2p2 [2p1x 2p1y 2pz], thus implying that valency of
carbon should be 2.
However, carbon exhibits a valency of 4 i.e. its tetravalent.
WHY IS THIS SO?
One electron is promoted from the 2s orbital to the vacant 2pz
orbital giving rise to four (4) unpaired electrons viz - the new
electronic configuration of carbon = 1s2 2s1 2p1x 2p1y 2p1z
1s electrons are considered to be core electrons and are not
available for bonding.
Furthermore, there is mixing between the 2s orbital and
the three 2p orbitals to form four (4) new sp3 hybrid
orbitals.
This is sp3 hybridisation i.e.
mixing of one s orbital with 3p orbitals to form
4 sp3 hybrid orbitals.
The sp3 hybrid orbital has the characteristic of both s
and p orbitals.

The 4 sp3 hybrid orbitals are arranged in a tetrahedral

shape i.e. they point towards the corner of a regular
tetrahedron as illustrated below.

109.5o
 H

109.5 o
C

In CH4 , the 4 sp3 hybrid orbitals overlap with 1s

atomic orbital of hydrogen to form 4 equal, covalent
sigma C–H bonds resulting in methane [CH4].

The C–H bond is known as sigma (σ) bond.

The electron pair [..] between the carbon and the
hydrogen (C–H) constitutes a sigma bond which is
a covalent bond i.e. carbon donates one electron
and hydrogen donates one electron to form the
covalent bond between them.

+
C H

sp3 orbital of C 1 s orbital of H C - H bond

The 4 C–H bonds point at an angle of 109.5o to each other
towards the corners of a regular tetrahedron, hence CH 4
has a tetrahedral shape.

109.5 o C

Carbon uses sp3 hybrid orbitals when it combines

with 4 other atoms.
The sp3 hybrid orbital may also overlap with other s or p
orbitals and hybrid orbitals to form different bonds,
e.g. In forming C – C bond, one sp3 hybrid orbital of a C
atom overlaps with sp3 hybrid orbital of another C atom to
form a molecular orbital.

C C

Thus, sp3 hybridised orbitals are used in formation of

alkanes [Saturated hydrocarbons].
Example 1: Formation of Ethane (C2H6):
In the formation of ethane (C2H6), 2sp3 hybridized
orbitals overlap to form the C–C bond in ethane (CH3–
CH3);
while one sp3 hybrid orbital of carbon overlaps with 1s
atomic orbital of hydrogen to form the C-H bond.

Ethane also has a tetrahedral shape.

H H

H C C H

H H
Example 2: In the formation of tetrachloromethane
(CCl4), the sp3 hybrid orbital of C overlap with 4 chlorine
3p orbitals to form the 4 C – Cl bonds.

Cl [17]: 1s2 2s2 2p6 3s2 3p5

3p
Cl

Cl C Cl
C Cl
Cl
Thus, carbon is able to form so many compounds .
 SUMMARY OF sp3 HYBRIDIZATION
sp3 hybridization results in:
(1) Tetrahedral shape
(2) Bond angle of 109.5o
(3) Formation of alkanes [i.e. saturated hydrocabons]
 sp2 HYBRIDIZATION IN CARBON
This involves the mixing of one 2s orbital and
two 2p orbitals to form three sp2 hybrid
orbitals.

All sp2 hybrid orbitals lie in a plane and point

at an angle of 120o to each other thus giving a
TRIGONAL shape.
 E.g. Formation of ethene [C2H4]
C: 1s2 2s1 + 2p 1 2p 1 2pz1
x y

3sp2 hybrid orbitals

1 + [2]2p 3 (+)
2s orbital 2p orbital sp2 hybrid orbital

H H
Covalent (bond
120o C C
Sp2
H H S
Trigonal shape
In forming ethene, the sp2 hybrid orbitals of C
overlap with the 1s atomic orbital of 2 H atoms and
1sp2 hybrid orbital of another carbon atom to form 3
sigma (σ) bonds.

The remaining unhybridised 2pz orbitals on the

carbon atoms overlap to form another bond known
as the pie (π) bond.
bond

CH CH C C

bond
Hence, there are 2 bonds between the 2C atoms of
ethene (a sigma bond and a pie bond). The presence
of the π bond in ethene makes it more reactive than
ethane and accounts for the greater reactivity of
alkenes.

The C=C (double bond) is shorter than the C–C

(single bond) due to the greater closeness from the
overlap of the unhybridized 2pz orbitals.

Note: C=C bond length = 1.34 Å,

C–C bond length = 1.54 Å
 SUMMARY OF sp2 HYBRIDISATION

(1) Trigonal shape [planar molecule]

(2) Bond angle of 120o
(3) Formation of alkenes
 sp HYBRIDISATION IN CARBON
This is the mixing of one 2s orbital and one 2p
orbital to form two sp hybrid orbitals.

For example, in the formation of ethyne, the C

atom uses the 2 sp hybrid orbitals to form 2
sigma bonds [one between C and C; and one
between C and H].
 2px
1 + - (+)
2S 2px
sp hybrid orbital

180o [sp + 1s]

H C C H

[sp + sp

The sp hybrid orbitals point at an angle of 180o to each

other giving a linear shape.
The 2 unhybridized p orbitals on C overlap to
form 2 pie (π) bonds, resulting in 3 bonds
(triple bond) between the 2 C atoms of ethyne
as shown below:
H–C≡C–H
The 3 bonds thus consist of 1σ and 2π bonds.
This makes ethyne more reactive than ethene.
Thus alkynes are more reactive than alkenes The
C≡C bond (Bond length = 1.2 Ao), is also shorter
than the C=C (1.34 Å) bond.
sp hybridization is common to all alkynes.
SUMMARY of sp HYBRIDISATION

(1) Diagonal / linear shape

(2) Bond angle of 180o
(3) Formation of Alkynes
 ELECTRONEGATIVITY OF HYBRIDISED ORBITALS

The greater the s character of a hybrid orbital, the

greater the electronegativity of the orbital relative
to the other unhybridized bonding orbitals.

Electronegativity scale: sp > sp2 > sp3

180o 120o 109.5o

Also, increasing the p character (or decreasing the

s character) of the bond decreases the bond angle
and vice versa.
DETERMINATION OF MOLECULAR COMPOSITION
AND STRUCTURE OF ORGANIC COMPOUNDS

This involves many steps viz;

(1) Isolation and Purification of the compound
(2) Qualitative Analysis of the compound which
involves:
(a) Test for the elements in the compound
(b) Test for the functional Groups
(3) Quantitative Analysis which includes:
(a) Combustion experiments to determine the
amount of each element present in the
compound
(b)Determination of Empirical Formulae
(c)Determination of molecular mass/weight
(d) Determination of molecular formulae
(4) Structure Determination which involves:
(a) Use of the information in 1 to 3 above
(b) Spectroscopic Analysis – IR, UV, NMR,
Mass Spectrometry e.t.c.
(c) Preparation of Derivatives e.g. esters
(d) Degradation reactions
(e) Synthesis.
ISOLATION AND PURIFICATION OF THE COMPOUND

The organic compound could be isolated from different

natural sources: plants, soil, microorganisms etc.
Process of isolation and purification involves extraction
with different solvents (solvents of different polarities)
and various chromatographic techniques e.g. Thin Layer
Chromatography (TLC), Column chromatography (CC),
Paper Chromatography (PC), High Performance or
(Pressure) Liquid Chromatography (HPLC) etc.
 QUALITATIVE ANALYSIS
This involves test for the elements present in the compound
and the different functional groups. Test for C and H is
unnecessary since most organic compounds contain C and H,
(However their presence can be detected (confirmed) by
combustion experiment in which the organic compound is
heated with copper (II) oxide [CuO]. The C is converted to
CO2 and the H to H2O. CO2 turns lime water [Ca(OH)2]
milky while H2O turns anhydrous CuSO4 blue and anhydrous
Cobalt(II)Chloride [CoCl2] pink.
2CHO + 3CuO Δ 2CO2 + H2O + 3Cu
The presence of N, S and Halogens (X) is detected by Sodium
Fusion test known as [LASSAIGNE’S] TEST. In this test, the
organic compound (small portion) is fused (heated strongly) with
small piece of sodium metal in a combustion tube. The products
of the fusion reaction are extracted with water and analyzed
(tested) accordingly. During fusion, the Nitrogen [N] is converted
to sodium cyanide [NaCN], the Sulphur [S] to sodium sulphide
[Na2S] and the Halogens [X] to sodium halide [NaX]
It is important to use a little excess of the sodium metal to
prevent formation of sodium thiocynate [NaCNS] which may
hinder detection of the N and S. In the presence of the excess Na,
any thiocynate formed is converted to NaCN and Na2S i.e.

NaCNS + 2Na Δ NaCN + Na2S

At the end of the reaction, the combustion tube and contents are
added to water, mixed together and filtered. The filtrate is used to
test for the elements.
 TEST FOR NITROGEN
This is the first test to be carried out. To a portion of the
filtrate in a test tube, add freshly prepared Iron (II) sulphate
[FeSO4] solution. Heat, cool and add few drops of Iron (III)
Sulphate solution and dilute H2SO4. A blue or green
colouration with or without precipitate indicates presence of
CN i.e. (N) in the compound.

6NaCN + FeSO4 → Na2SO4 + Na4Fe(CN)6

Na4Fe(CN)6 + 2Fe2(SO4)3 → 6Na2SO4 + Fe4[Fe(CN)6]3
Prussian blue
 TEST FOR SULPHUR
To a portion of the filtrate in a test tube, add dilute HNO3 to
acidify and few drops of lead ethanoate (acetate) solution. A
black precipitate of lead sulphide confirms presence of S.
Na2S + Pb(OCOCH3)2 → PbS + 2CH3COONa

TEST FOR HALOGENS

If N and /or S are (is) present, a small portion of the filtrate is
heated with dil. HNO3 first in a beaker/ flask to about half its
volume. The solution is cooled, then AgNO3 is added.
The purpose of heating with dil. HNO3 is to remove the N/S
present in the compound as HCN and H2S so as not interfere
with the detection of the halide.
NaCN + HNO3 Δ HCN + NaNO3
Na2S + 2HNO3 Δ H2S + 2NaNO3

Otherwise, the cyanide and sulphide can react with AgNO3 to

give insoluble AgCN and Ag2S which will give a false positive
test for the halides.
CN- + S2- + 3Ag+ → AgCN + Ag2S
If N/S is absent in the compound, dilute HNO3 solution and
AgNO3 is added to a portion of the filtrate right away. The
different precipitates produced indicate the presence of the
halogens.

(a) A white precipitate, soluble in excess NH4OH indicates the

presence of chloride [Cl-]
(b) A cream (light yellow) precipitate slightly soluble in excess
NH4OH shows Bromide [Br -].
(c) A yellow precipitate, insoluble in excess NH4OH shows
presence of Iodide [I-].
 TEST FOR FUNCTIONAL GROUP
The various functional groups [viz; alkenes and alkynes,
alcohols, alkanals, alkanones, carboxylic acids, esters, amides,
phenols, amines, nitriles, nitro compounds aromatic
compounds etc can also be tested for (DETAILS LATER).
 QUANTITATIVE ANALYSIS
The goal of quantitative analysis is to know OR determine the
relative amount of the different elements present in the
organic compound i.e. to determine the percentage of each
element present in the compound.
Conventional Method of Determination of the
Percentage Composition of Elements in an Organic
Compound
This is outlined below:
(a) Determination of Quantity of C and H
A known weight of the organic compound is burnt (heated) in
excess oxygen to give CO2 and H2O. The CO2 is absorbed in a
known weight of soda lime (NaOH) or KOH while the H2O is
absorbed in a known weight of magnesium perchlorate
[Mg(ClO4)2] or Calcium chloride [CaCl2]. The weight of CO2
and H2O is obtained by difference or subtraction and the
weights of C and H can be calculated from these:
Wt of Carbon (C) = RAM of carbon × Wt ofCO2
RMM of CO2
i.e. 12 x wt of CO2
44

Wt of Hydrogen (H) = RAM of H2× Wt of H2O

RMM of H2O
i.e. 2 x wt of H2O
18
RAM – Relative Atomic Mass
RMM – Relative Molecular Mass
Determination of Quantity of Oxygen
The percentage of oxygen is always determined as the
difference between 100% and the sum of the percentage
values for all other elements present in the compound i.e.
%O =100% -(Percentage of all other elements).
 CALCULATION OF EMPIRICAL FORMULA
Empirical Formula (E.F.) is the ratio of the number of atoms
of each element present in the compound. It is usually
calculated from the percentage composition of the elements.

WORKED EXAMPLES
Question 1: An organic compound X on quantitative analysis
was found to contain 40.0% carbon and 6.7% hydrogen.
Calculate its empirical formula. [RAM: H = 1, C = 12, O =
16]
Solution: 1st, assume the remaining element is O and calculate its
percentage composition by difference or subtraction: % O = 100 – (40.0
+ 6.7)= 100 – 46.7= 53.3 %
The E.F. can be calculated using a simple table as outlined below:

Element Carbon [C] Hydrogen[H] Oxygen[O]

%Composition OR Weight 40.0 6.7 53.3

No of Moles 40 6.7 53.3
12 1 16

Relative No of Moles 3.33 6.7 3.33

Divide the moles with the 3.33 = 1 6.7 = 2.01 3.33 = 1

3.33 3.33 3.33
lowest
Simplest Mole Ratio 1 2 1

Empirical Formula (E.F.) of compound X = CH2O

DETERMINATION OF MOLECULAR MASS AND
MOLECULAR FORMULA

The molecular formula (M.F.) is the actual number of each

kind of element present in one molecule of the compound.
M.F = (E.F)n where n = whole number.
In order to determine the molecular formula, the molecular
mass (MM) of the compound must be known.
There are many methods of determining the MM. The modern
method of choice is by High Resolution Mass Spectrometry
[HRMS]. This technique gives the exact mass of the
compound.
Once the MF is known, then the structural formula or
structure of the compound can be determined.
Hence for compound X,
If Molecular Mass (MM) = 120, what is the Molecular Formula?
MF = (E.F.)n = MM
MF of cpd. X = (CH2O)n =120

(12+2+16)n =30n = 120,

n=120/30 = 4
MF = (CH2O)4 = C4H8O4

Hence Molecular Formula (MF) of compound X = C4H8O4

Structural formula can then be determined.
Question 2:
6.51mg of an organic compound, B gave on combustion 8.36
mg of H2O and 20.47 mg of CO2. Quantitative analysis
indicated absence of N,S and halogens. Determine the
molecular formula [M.F.] of the compound if the MM is 126.
SOLUTION
1st calculate the weight of each element in the compound and their
percentage composition.
Weight of carbon in sample = 12 × 20.47 = 5.58mg
44
% of Carbon = 5.58 × 100 = 85.7%
6.51
Weight of Hydrogen in sample = 2 × 8.36 = 0.93mg
18
% of H = 0.93 × 100 = 14.3%
6.51
% C + %H = 85.7 + 14.3 = 100%,

hence B is an hydrocarbon, it has no oxygen.

 Empirical Formula(E.F.) Determination
Element C H C H
% 85.7 14.3 5.58 0.93
composition
OR mass
Number of 85.7 = 7.14 14.3 = 14.3 5.58 = 0.47 0.93 = 0.93
moles 12 1 12 1
Relative No 7.14 = 1 14.3 = 2 0.47 = 1 0.93 = 2
of moles 7.14 7.14 0.47 0.47
Simplest 1 2 1 2
Mole Ratio

Therefore, Empirical formula of cpd. B = CH2

MM = 126
MF = (EF)n = MM
MF = (CH2)n = 126
14n = 126
n = 126 = 9, MF = (CH2)9 = C9H18
14
Hence, MF of cpd. B = C9H18
Question 3: Quantitative analysis of a liquid organic compound
D, furnished 48.76% C and 8.07% H. No other element was
found. Calculate it E.F.? If the MM is 74, what is the MF?

SOLUTION
% C + % H = 48.76 + 8.07 = 56.83
Therefore, the compound must contain Oxygen to make
100%
% O = 100 – 56.83 = 43.17
 E.F. Determination

Element C H O
% composition 48.76 8.07 43.17
No of Moles 48.76 8.07 43.17
12 1 16
Since atoms
4.06 8.07 2.70 combine in
whole numbers,
Relative No of 4.06 8.07 2.70
simple mole
2.70 2.70 2.70 ratio is
Moles multiplied by 2.
x2
Simplest Mole Ratio 1.50 2.99 1.0
3.0 5.98 2.0
3.0 6.0 2.0

Empirical Formula of D = C3H6O2

MM = 74
MF = (EF)n = MM
MF = (C3H6O2)n = 74
(36+6+32)n = 74
74n = 74, n=1
MF = (C3H6O2)1= C3H6O2

Hence, MF of cpd. D = E.F. = C3H6O2

Note: If on dividing by the smallest no/or calculating simplest
mole ratio, fractions are obtained as above, multiply the ratios
by small numbers (e.g. 2,3) until a ratio of nearly whole
numbers is obtained. This is because atoms combine in whole
numbers.

Practice questions1.
Compound H has a composition of 78.5% C, 8.4% H and
13.1% N. Determine its Empirical formula. If Molecular Mass
of H = 107, what is the Molecular Formula?
 FUNCTIONAL GROUP CLASSES OF CARBON
COMPOUNDS

A functional group (F.G.) is defined as an atom or group of atoms

responsible for the chemical identity/reactions of a compound.
It’s a term used to identify organic compounds and differentiate
between two or more organic compounds.
The different functional groups constitute different homologous
series.
Homologous series
A homologous series is a series of compounds (or family of
compounds) having the same general formula (i.e. same functional
group) and with its successive members differing by a – CH2 –
unit.
Members of a homologous series have similar methods of
preparation and similar chemical properties.

The simplest homologous series/functional group is the Alkanes

with the general formula: CnH2n+2 [where n ≥ 1]
FUNCTIONAL GROUP CLASSES OF ORGANIC
COMPOUNDS
Serial Homologous Series General Formula Functional Group Molecular Formula of Examples of Nomenclature
No. [F.G.] the 1st Member

1. Alkanes CnH2n+2 [RH] CH4 Methane

Where (n ≥ 1) H3C CH3

2. Alkenes CnH2n ( n ≥ 2) C C C2H4 Ethene

3. Alkynes CnH2n-2 ( n ≥ 2) C C C2H2 Ethyne

4. Arenes ArH e.t.c. C6H6 Benzene

5. Haloalkanes CnH2n+1X CH3X e.g. CH3Cl Halomethane e.g.

(Alkylhalides) R X X Chloromethane

6. Alkanols (Alcohols) CH3OH Methanol

R OH OH

7. Alkoxyalkanes CH3OCH3 Methoxymethane

R O R' O
(Ethers) (Dimethyl ether)
Alkanals O O Methanal
8. R C C
HCHO [CH2O]
(Aldehydes) H H
(Formaldehyde)

9. Alkanones (Ketones) R C O CH3COCH3 Propanone (Acetone)

C O
R'
10. Alkanoic Acid HCOOH Methanoic acid
O O
(Carboxylic Acids)
R C C
(Formic Acid)
OH OH

11. AlkylAmines CH3NH2 Methylamine

R NH2
NH2
(Amines)

12. Alkyl Nitriles CH3CN Methylnitrile (Methyl

(Cyanoalkane or cyanide or
Alkylcyanide) R C N C N
cyanomethane)

Alkyl Alkanoate O O Methyl methanoate

13. C
HCOOCH3
(Esters) R C
OR' OR'

14. Alkanoyl halide (Acid CH3COX e.g. CH3COCl Ethanoyl halide

O O
halide) R C C e.g. Ethanoyl chloride
X
X

Alkanamide (Amide) O
15. O HCONH2 Methanamide
C
R C
NH2
NH2

Alkanoic anhydride O Ethanoic anhydride

16. O
C
(CH3CO)2O
(Acid anhydride) R C
O
O
C
R C
O
O
NOMENCLATURE OF ORGANIC COMPOUNDS
New organic compounds could be named in two different ways:

1. Common Names: These are not based on any logic but given to
reflect the origin, history or properties of the compound e.g.
methane is known as marsh gas, formic acid from ants (formica –
Latin name for ants); vanillin from vanilla; Pejujapo from Jatropha
podagrica, Jatrophone from Jatropha curcas etc.

2. Systematic Names: These are derived from an internationally agreed

logical system based on the structure of the compound. The
systematic nomenclature was first introduced in 1892 (in Geneva,
Switzerland) and is controlled by the International Union of Pure and
Applied Chemistry (IUPAC), hence the Systematic Nomenclature is
also called IUPAC system of nomenclature.
SYSTEMATIC NOMENCLATURE
General Rules for Naming Acyclic Organic Compounds
1. The longest continuous chain of carbon atoms containing the principal
functional group is selected as the parent chain and named accordingly.
The following prefixes are used depending on the number of carbon
atoms :
2. The carbon atoms in the chain are numbered serially from one end to
the other in the order to indicate the position of the
substituents/functional groups on the chain. The numbering is done
such that the substituents/ functional groups have the least numbers
possible.
 6 Hex-
7 Hept-
8 Oct-
9 Non-
10 Dec-
No of Carbon atoms Prefix

11 Undec-
12 Dodec-
13 Tridec-
14 Tetradec-
15 Pentadec-
16 Hexadec-
17 Heptadec-
18 Octadec-
19 Nonadec-
20 Eicos-
[Alkane – eicosane]

Note: Cyclic compounds carry the prefix cyclo – before the

name of the compound e.g cyclobutane.
 X
C C C
C C C C 6 5 4

1 2 3 4 3C C C
4 3 2 1 x C
2 1
(About 3 ways of numbering)

3 1
7
2
5
8 4
6
3. In naming the compound, the number (position) of the substituent
prefix (comes before) the name of the substituent and this prefix the
name of the parent compound.
4. Where there are more than one substituent on the chain, the names of
the substituents are written in alphabetical order i.e. ethyl precedes
methyl, bromo precedes chloro, chloro precedes ethyl etc.

2-bromo-3-chlorohexane

5. Where there are more than one functional group, the higher functional
group is taken as the parent compound while the others are named as
substituents. [i.e. the functional groups are numbered preferentially to
the substituents].
Order of preference ( Priority of Functional Groups)
Alkanes < Arenes < Nitro < Halo < Alkenes < Alkynes <
Ethers < Amine < Alkanols < Alkanones (Ketones) < Alkanals
(Aldehyde) < Alkanonitrile < Amides < Acidhalides < Esters
< Carboxylic acids < Acid anhydride etc.

6. In writing the name, the names of the compounds are written as one
word. Numbers are separated from each other by comas and from
substituent names by hyphen (–) and the substituent names prefix the
name of the parent compound e.g.
 (CH3)2C(Cl)CH(Cl)CH2COOH

Cl
5 2
OH
4 3 1

Cl O
3,4-Dichloro - 4-methylpentanoic acid.
Name/Suffix of the Major Functional Groups
Functional Groups Suffix

Alkanes -ane

Alkenes -ene

Alkynes -yne

Alkanols -ol

Amines -amines

Alkanal -al

Alkanone -one

Alkanoic acid -oic acid

Alkanonitrile -nitrile

Esters -oate

Acid halides -oylhalide

Amides -amide
 EXAMPLES

1. CH3CH2CH(CH3)CH2CH2CH2CH3 2 4 6 7
1 3 5
3 – Methylheptane

1 3
Cl
2. CH2(Cl)CH2CH2CH2(OH) 2 4
HO
4-Chloro-1-butanol or 4-Chlorobutanol

O
3. CH3CH2CH(OH)CH2CH(Cl)COOH 5 3
6 4 2 1
OH

OH Cl
2-Chloro-4-hydroxyhexanoic acid
CH3CH2C(Br2)CH(Cl)CH(C2H5)CHO
4,4-dibromo-3-chloro-2-ethyl-hexanal
1

5 2

4 3
Br
3-Bromocyclopentene

CH3CH(OH)CH(OH)CH2CH2Cl
5-chloro-2,3-pentandiol
 4
1
5
2 63

6
3 5
2
4
1
1,4-cyclohexadiene
OH

5
OH
4 3
Cl 2

1
5-chloro-2,3-pentandiol
 KINETICS AND MECHANISM OF ORGANIC REACTIONS
Chemical kinetics
Chemical kinetics is the study of how fast chemical reactions occur.
The speed of the reaction is measured by the change in
concentration of either the reactants or products with time.
Chemical kinetics also sheds light on the reaction mechanisms
(how the reaction occurs)

Chemical reactions can be classified into three types based on the

speed of the reaction:
Instantaneous reaction: Reactions that occur within a short
period of time (10-13 to 10-16 sec). E.g ionic reactions
AgNO3 + NaCl AgCl + NaNO3
Moderate reactions: Reactios which occur not too fast or slow
(some minutes to some hours). E.g. Hydrolysis of ester

Very slow reaction: Reactions which occur over a long period of

time (some months or years). E.g rusting of iron
4Fe + 3O2 + 6H2O → 4Fe(OH)3

Rate of Chemical Reaction

Rate of chemical reaction is the ratio of change of concentration
(Δc) of either reactant or product with time (Δt).
So, the rate of reactions can be defined as decrease in concentration of
reactant per unit time or increase in concentration of product per unit
time
Factors affecting reaction rate
Temperature: Generally, as temperature increases, so does the reaction rate.
At higher temperature, reaction molecules have more kinetcs energy, move
faster and collide more often with greater energy.

Concentration of reactants: As the concentration of reactants increases, the

rates of collision of the reactant molecules and reaction increase.

Catalyst: Catalyst will speed up reaction rate by lowering the activation

energy

Surface area of solid reactant: Increasing the surface area of a solid reactants
will expose more of its particles to attack. This results in an increase in
chances of collisions and rate of reaction.

Pressure of gaseous reactants or products: Increase in pressure will results in

increase in the number of collosions and thus increase in reaction rate.
Rate laws
- Rate laws are always determined experimentally
- Reaction order is always defined in terms of reactant (not
product) concentrations
- The overall concentration dependence of reaction rate is given
in a rate law
- A general rate law for a reaction will look like
For a reaction:
n AB → A + B
Rate α [AB]
Rate = K [AB]
The order of reaction of the equation R = K [AB] is
known as 1st Order reaction

For a reaction
RX + OH- → ROH + X-
Rate = K [RX][OH]
Order = 2; i.e. this is a 2nd order reaction because
the sum of the powers of the reactant
concentration is equal to two.
REACTION MECHANISM
A balanced equation for a chemical reaction indicates what is reacting
and what is produced , but reveals nothing about how the reaction
actually takes place.

Reaction mechanism is the actual sequence of events by which

reactants are converted to products.

Organic reactions could be one step or multi–step. In actual fact, most

reactions involve many steps.
The rate determining step is the slowest step in the sequence
of steps leading to product formation
The N2O2 in the above equation is known as reaction intermediate. Reaction
intermediates are formed in one step and then consumed in a later step of
the reaction mechanism.

Reaction intermediate: Reaction intermediates are chemical species, often

unstable and short-lived (however sometimes can be isolated), which are not
reactants or products of the overall chemical reaction, but are temporary
products and/or reactants in the mechanism's reaction steps. Reaction
intermediates are often free radicals or ions.

Organic chemical reactions normally involve breaking and forming of bonds:

i.e. [AB + CD → AC + BD]. The bonds could be broken in two different ways
depending on the electronegativity of the atoms involved.

The two methods of bond breaking are referred to as Homolytic and

Heterolytic Fission
HOMOLYTIC FISSION
Homolytic fission takes place between atoms of similar electronegativity. This
is fission in which the electron pair [which constitutes the covalent bond] is
shared equally between the two atoms sharing the bond. Thus, each atom
carries an unpaired electron and is known as a radical.

i.e. A–B = A :B [An electron pair = a covalent bond] e.g. Cl2 = Cl–Cl
A–B → A. + B . [Radicals]

Radical are very reactive species. Homolytic fission is also known as Radical
Fission.

Chemical reactions involving homolytic fission are known as free radical

reactions. Homolytic fission also requires a large amount of energy, thus it
takes place at very high temperature or under UV light.
HETEROLYTIC FISSION
Heterolytic fission takes place between atoms of different electronegativities.
It involves the transfer of the electron pair to the more electronegative atom,
leading to the formation of charged species or ions. Hence, heterolytic fission
is also known as Ionic or Polar Fission.

i.e. C – D → C+ + D-
[D is more electronegative than C]
D- is said to be electron rich while C+ is said to be electron deficient.
e.g H+─Cl- → H+ + Cl-
NUCLEOPHILES AND ELECTROPHILES

Nucleophiles are atoms or group of atoms with a negative (-ve) charge or a

lone pair of electrons. They are always electron rich. They are called
nucleophiles because they are nucleus loving/seeking (i.e they seek the
electron deficient centres). e.g.
:NH3, H2O:, -OH, Halide ions [X-] e.g. Cl-, R3N:, e.g. (CH3N:), ROH, HS-,
RO-, CH3CO2- etc.

Electrophiles: These are atoms or group of atoms which are electron deficient
or positively charged. They are called electrophiles because they are electron
loving (seeking) i.e. they seek electron rich centres.
e.g NO2, H3O+,Br+, FeCl3, RN2+, BF3, CH3C+O, R+
 Types of Organic Reactions
There are 5 main types of organic reactions: Substitution, Addition, Elimination,
Condensation and Rearrangement.

1. SUBSTITUTION OR DISPLACEMENT REACTION

This involves direct displacement of an atom or a group of atoms by another atom
or group of atoms. e.g.,

(i) Chlorination of methane

(ii) Alkylation of benzene.

2. ADDITION REACTION:
This reaction is typical of unsaturated compounds and leads to a decrease in
degree of unsaturation. It involves addition across an unsaturated bond and
gives rise to a less unsaturated or fully saturated product.

In most of these reactions, unsaturated compounds function as a source of

electrons i.e. act as nucleophiles. Consequently, they are susceptible to attack
by electron deficient species i.e. electrophiles.

(3) ELIMINATION REACTION:

This reaction involves the removal of atoms or group of atom from two
adjacent C atoms to form a multiple bond. e.g
(4) CONDENSATION REACTION:
This is the reaction in which two or more compounds react to form another
compound with the elimination of simple substances like water. e.g
5. REARRANGEMENT REACTION
This involves migration of an atom or group of atoms from one site to another
within the same molecule. It could involve migration of functional group from
one point to the other.
FACTORS AFFECTING ORGANIC REACTIONS
An organic reaction can be facilitated or inhibited by certain factors. These
include:

(i) Distribution of electrons around the reaction site

(ii) The nature and/or size of the atoms or group of atoms surrounding the
reaction site.

1. INDUCTIVE EFFECT
This is a permanent polarizing effect in single bonds. The effect is caused
initially by a covalent bond between atoms of different electronegativities.
The effect which is brought about by the unequally sharing of electrons is
transmitted along a chain of sigma bonds.

Cδ+−Xδ−
If the carbon atom attached to polarizing atom or group is itself attached to
other C-atom, the inductive effect is transmitted along the chain, although it
tends to be insignificant beyond the two carbon atom.

When the group (polarizing) attached withdraw electron with respect to

carbon atom, the effect is term NEGATIVE INDUCTIVE EFFFECT (–I).

When the group is electron donating, the effect is called a POSITIVE

INDUCTIVE EFFECT (+I). E.g the alkyl groups have a +I effect.
-I effect:
The -I effect is seen around a more electronegative atom or group, and
electron density is higher there than elsewhere in the molecule. Electron-
withdrawing groups include halogen (X), nitro (−NO2), cyano (−CN), carboxy
(−COOH), ester (−COOR) and aryloxy (−OAr)

+I effect:
The +I effect is observed among the less electronegative atoms of the
molecule by electron-releasing (or electron-donating) groups. The alkyl
groups ® are usually considered electron-releasing (or electron-donating)
groups.

2. MESOMERIC EFFECT
The shift of π electrons in multiple bonds towards the more electronegative
atom is referred to as mesomeric effect. It is similar to inductive effect in
single bonds. it is most common in carbonyl compounds (-C=O) where there is
a shift of π electrons towards oxygen.
The effect can be transmitted along the chain. The difference between the
inductive and mesomeric is that there is no visible shift of electron in inductive but
there is a visible shift of electrons in mesomeric effect.

3. STERIC EFFECT
This is the effect due to the size of the groups surrounding the reaction site of the
molecule. This occurs when certain atoms or group of atom alter or in some cases
completely prevent a reaction from taking place, despite favourable electronic
conditions. This effect is known steric hindrance and particularly effective when the
reaction site is crowded with the large bulky groups.
E.g
(a) CH3COOH + CH3CH2OH CH3COOCH2CH3 + H2O
Note: In (b) above, the –OH is in between the two carbon atom, this makes it
less assesible to the ethanioc acids.This hinders the rate of reaction or
sometimes prevents the reaction from taking place. In (a) above, the –OH
group is at the end, this makes it easy for the CH3COOH to react.
 ISOMERISM
Isomerism is the phenomenon whereby two or more compounds have the
same molecular formula, but different physical and chemical properties.

The compounds which exhibit isomerism are known as isomers. There are
two principal types of isomerism.
1. Structural Isomerism
2. Stereoisomerism.

STRUCTURAL ISOMERISM
These occur when two or more compounds have the same molecular
formulae but different structural formulae. Many types occur, some are;

(a)Nuclear or Chain Isomerism:

This is concerned with the arrangement of carbon atoms in the molecule. i.e.
the structure of the nuclei e.g. C4H10 can be written as butane as butane or 2-
methyl propane i.e (isobutene).
 CH3CHCH3
CH3CH2CH2CH3 CH3
Butane C4H10 2-Methylpropane

(b) Position Isomerism:

This is exhibited by isomers in the same homologous series. They have the
same carbon skeleton but they differ in the position of the functional group.
e.g., C3H8O
(c) Functional Group Isomerism:
This is exhibited by compounds with the same molecular formula but different
functional groups. e.g., C3H6O can either be an alkanal or an alkanone.
(d) Metamerism
Describes the phenomenon whereby different atoms or groups of atoms are
linked to the same functional group. The isomers belong to the same
homologous series and have the same chemical properties but different
structures. E.g, C4H10 can form two types of ethers [ROR].

(e) Tautomerism
This occurs when two or more compounds have the same molecular formula
but different structures due to the migration of an atom from one part of the
molecule to another without leaving the molecule. E.g., ethylacetate E.A.A.

This is known as Keto – enol tautomerism [H atom migrates from C to O].

STEREOISOMERISM
This occurs when two or more compounds have the same molecular and
structural formulae but differ in the spatial arrangement of their atoms i.e. the
arrangement of the atoms in space.

There are two types Viz; Optical and Geometrical.

Optical Isomerism: This occurs when two compounds have the same molecular
formulae and structural formulae but one compound is not super imposable on
the other. Such compounds are termed as Optical Isomers (enantiomers).
Optical isomerism occurs in compounds that has Asymmetric or Chiral carbon
atoms/centres.

A carbon atom is said to be asymmetric/chiral when it has 4 different

substituent. This compound is said to be optically active. Such compounds are
able to affect the position of plane polarized light. Such compounds also occur
in two forms. These are called object and a mirror images. If the compound is
place in the front of a mirror, the mirror image will be different and both will
rotate plane polarized in different directions. e.g., CH3CH(OH)COOH [Lactic acid,
2-Hydroxypropanoic acid].
A solution of one enantiomer rotates the plane of polarisation in
a clockwise direction. This enantiomer is known as the (+) form.

A solution of the other enantiomer rotates the plane of

polarisation in an anti-clockwise direction. This enantiomer is
known as the (-) form.

If the solutions are equally concentrated the amount of rotation

caused by the two isomers is exactly the same - but in opposite
directions.

50/50 mixture of the two enantiomers is known as a racemic

mixture or racemate. It has no effect on plane polarised light.
• Could you get them to align by rotating one of the molecules? The next
diagram shows what happens if you rotate molecule B.
Geometrical isomerism: This occurs when there is no free
rotation around the carbon atoms, either due to the presence of
a multiple bond or the presence of a ring or other steric factors.

There are two types of geometrical Isomer Viz; Cis and Trans
Isomers.

The isomer in which like substituents lie on the same side of the
multiple bonds is called Cis- Isomers. When the substituents lie
on the opposite sides of the multiple bond, it is called Trans-
Isomers.
The trans-isomers are always more stable than the Cis-isomers e.g For
the cis-Butenedioc acid, the melting point is 139oC and for the trans-
Butenedioc acid the melting point is 287oC. The two isomers have
different physical and chemical properties.