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COVENANT UNIVERSITY CANAANLAND, OTA

OMEGA SEMESTER 2007/2008 SESSION


COURSE TITLE:

GENERAL ORGANIC CHEMISTRY

COURSE CODE:

CHM 121

LECTURER:

AJANI O.O.

Topics under This Section are:


(1)Hybridization.
(2)Formation of sp3, sp2, sp orbitals in carbon.
(3)Homologous series.
(4)Functional groups.
(5)Isomerisim.
Objectives: At the end of this section of the course, students are expected to
know the following:

What is hybridization?
Hybridization in carbon atom systems
Homologous series: introduction and characteristics.
Various classes of functional groups.
General and selective tests for some functional groups.
Some carboxylic acid derivatives.
Isomerism - both structural and stereoisomerism.
Ordinary and plane polarized light.

Hybridization: can be defined as the blending of two or more atomic


orbitals of different energy to obtain a hybrid orbital of equivalent energy
level. This depends on the concept of overlapping of atomic orbital and
mathematical summing of their wave functions towards a specific direction.
Every overlap of atomic orbitals results in bond formation which could be
either sigma () or pi () bond. However, the type of bond formed depends
on the nature of the overlap e.g. axial overlap results in sigma () bond while
lateral (side-to-side) overlap results in pi () bond formation. This is why
sigma () bond is stronger than pi () bond.
Hybridization helps us to know the molecular geometry of the compounds,
their bond angles, the nature of electron pair [i.e. number of Bond Pair (BP),
Lone Pair (LP)]. When all the electron pairs surrounding the central atom are
1

bond pair (BP), the compound shows the normal shape peculiar to its
hybridization pattern. However, when there is lone pair (LP), there will be
slight distortion to give it another shape because the lone pair (LP) tends to
re-orientate itself in order to minimize repulsion. The order of the repulsive
power is: LP-LP > LP-BP > BP-BP. This is established by Valence Shell Electron
Pair Repulsion Theory (VSEPAR).
Determination of Hybridization Pattern
Write out the ground state (GS) valence electronic configuration of
central atom.
Promote the excited state (ES) in such a way to accommodate
electrons from surrounding groups or atoms.
Pair each electron from the surrounding atoms with each half-filled
suborbital level of the central atom to have fully filled configuration at
each suborbital level.
Write out the valence suborbital level at this stage as the hybrid
orbital.
You can then predict the shape, bond angle and some other factors as
shown in the table below:
Total
Electron
Pair

No of
No of
Bond Pair Lone Pair
(BP)
(LP)

Geometrical
Distribution
or Shape

Ideal
Bond
Angle

Typical
Example

Hybri
d
orbita
l
sp

Linear

180O

BeCl2

3
3

3
2

0
1

sp2
sp2

Trig. Planar
Trig. Planar

120O
120O

BF3
SiO2

4
4
4

4
3
2

0
1
2

sp3
sp3
sp3

Tetrahedral
Trig.
Pyramid
Angular/Ben
t

109.5o
107 o
104.5 o

CH4
NH3
H2O

5
5
5
5

5
4
3
2

0
1
2
3

sp3d
sp3d
sp3d
sp3d

90o, 120o
90o, 120o
120o
180o

PCl5
SF4
ClF3
XeF2

6
6

6
5

0
1

sp3d2
sp3d2

Trig.
Bipyramid
Trig.
Pyramid
Trig. Planar
Linear
Octahedral
Sq. pyramid

90o
90o

SF6
BrF5

sp3d2

90o

Sq. planar

XeF4

Example: What is the hybridization pattern or the hybrid orbital of Sulphur


tetrafluoride (SF4) and use it to predict the shape and bond angle of the
compound.

Solution:
(i)

Central atom is Sulphur (16S) with G.S. electronic configuration of


1s2 2s2 2p6 3s2 3p4
3P4

3S2

G.S. valence electronic configuration


(ii)

Ex. State valence electronic conf.

3d1

3P4

3S2

(iii)

Each of the up spin half filled sub-orbital accepts each of the 4down
3S2

3P4

3d1

spin electron from fluorine

(iv)

Hybrid. Pattern of SF4 = sp3d (with 4BP + 1LP = 5TP).

(v)

Shape is Trig. Pyramid with bond angle of 90o and 120o


F
F
F

Hybridization in Carbon

Considering the carbon context, hybridization is the blending or mixing of s


and p orbitals in the valence shell to produce equivalent orbital known as
Hybrid orbitals. There are three main types of hybridization in carbon: They
are sp3, sp2 and sp. The hybrid orbitals are named after the atomic orbitals
from which they were constructed or formed e.g.
2s + 2p3

Four of sp3 hybrid orbitals.

2s + 2p2

Three of sp2 hybrid orbitals.

2s + 2p

Two of sp hybrid orbitals.

Sp3 Hybridization in Carbon


2s orbital mixed with three 2p (i.e. 2px, 2py and 2pz) orbitals to form four sp3
hybrid orbitals of equivalent energy which are tetrahedrally arranged (to
minimize repulsion) with the bond angle (B.A.) of 109.5o. Carbon will be sp3hybridized when it is directly bonded to four atoms in a neutral molecule e.g.

C
X

Energy Level Diagram

PX

PY

Energy

PZ
after blending

G.S. Valence of Carbon


2s2 2p2

SP3

SP3

SP3

SP3

sp3 hybrid state of Carbon

E.S. Valence of Carbon

Orbital Blending Diagram

A Typical sp3 Hybridization in Methane (CH4)


Each of the half-filled four sp3 hybrid orbital can use bigger side of its lode to
overlap with each 1s orbital of hydrogen to form 4 bonds in methane.

3-D Structure

Orbital picture

Sp2 Hybridization in Carbon


2S orbital mixed with two of its 2p (i.e. 2px, 2py) orbitals to obtain three sp2
hybrid orbitals of equivalent energy which are all in the same plane with
trigonal planar arrangement having bond angle of 120o. Here, the third 2p
orbital (i.e. 2pz) is unhybridized. Carbon will be sp2-hybridized if it is directly
bonded to three atoms in a neutral molecule e.g.

Energy Level Diagram


PZ
PX

unhybridize

PY

PZ
after blending

G.S. Valence of Carbon


2s2 2p2

SP2

SP2

SP2

sp2 hybrid state of Carbon

E.S. Valence of Carbon

Orbital Blending Diagram:

Sp Hybridization in Carbon
5

The carbon 2s orbital combines with one of its 2p orbital (i.e. 2px) to
generate two sp hybrid orbitals of equivalent energy which are linear in
shape with bond angle of 180o. The remaining two 2p (i.e. 2py, 2pz) are
unhybridized. This sp hybrid orbital has 50% s and 50%p character. Carbon
will be sp-hybridized when it is directly linked to two atoms in a neutral
molecule e.g.
Energy Level Diagram

PX

PZ
PY
Unhybridized
PY

PZ
after blending

G.S. Valence of Carbon


2s2 2p2

SP

SP

sp hybrid state of Carbon

E.S. Valence of Carbon

Orbital Blending Diagram:

Formation of Sigma () and Pi () Bonds


Having seen the hybridization patterns (sp3, sp2 and sp) of a single carbon, it
is of great interest to know that this carbon can overlap with another carbon
to form either sigma () or pi () bond. The hybrid orbital of adjacent carbon
atoms can overlap with one another or with atomic orbital of other elements
such as sulphur, phosphorus, oxygen, nitrogen etc to form covalent bond
which could either be () or () bond.
Sigma bond can be formed by any of the following three overlaps:
(i) Overlap of two hybrid orbitals: These include sp3-sp3, sp2-sp2, sp-sp,
sp3-sp2, sp3-sp, sp2-sp. For instance, the kind of overlap seen in
carbon-carbon bond of ethane is sp3-sp3

Orbital Picture

3D-Structure

(ii) Overlap of a hybrid orbital and s orbital e.g. sp3-s, sp2-s, sp-s. This is
seen in carbon-hydrogen bone of methane and other alkanes.

C
H

1s
(iii)

Orbital Picture

3D-Structure

Overlap of a hybrid orbital and p orbital that is linearly aligned e.g.


sp3-p, sp2-p, sp-p. For example sp3-p is seen in overlap of carbon
with p-block elements such as chlorine.

Cl

Orbital Picture

Cl

3D-Structure

Pi bond: can only be formed when two adjacent carbons are unhybridized.
It is a covalent bond formed as a result of lateral overlap of two unhybridized
p-orbitals on adjacent carbon atoms.

Pi-bond
Sp3-sp3 Overlap in Ethane (C2H6)

Two sp3 hybridized carbon atoms formed carbon-carbon sigma bond in


ethane as shown below both in orbital picture and 3D-stucture.
H

H
H

3D-Structure

Orbital Picture

In summary ethane contains 1 of C-C + 6 of C-H = 7 bonds in all.

Sp2-sp2 Overlap in Ethene (C2H4)


When two sp2 hybridized carbon atoms link up, they form a double bond
(C=C) which is made up of 1 and 1-bonds. The -bond is formed as a
result of overlap of the hybridized orbital sp2-sp2 while -bond is formed as a
result of lateral overlap of unhybridized 2pz orbital of one carbon with that of
the other as seen in ethene. In summary ethane has 1 of C-C + 4 of C-H +
1bond of C-C = 5 + 1 bonds.

Pi bond
120o
C

The electrons in the -bond are called electrons while those in the -bond
are called electrons. Since -bond is weaker than -bond, the bond energy
of C=C is less than twice the bond energy of C-C.
Rotation about C=C is restricted unlike that involve in C-C which is free. The
bond length is 1.34 (shorter because of higher electron density).
Sp-sp Overlap in Ethyne (C2H2)

Overlap of sp-sp hybrid orbital of two carbon atoms gives rise to a triple bond
(C C), which has 1 +2-bonds. The 2-bonds are product of lateral overlap
of two unhybridized p orbitals (i.e. 2py, 2pz) of one sp carbon with that of
other as seen in ethyne (C2H2). The whole of ethyne in summary, has 3 + 2
bonds.
Pi-bond
H

sigma

C
sigma

180o
H

sigma
3D-Structure

Orbital Picture
Pi-bond

Rotation about C C is the most difficult. The bond energy of a C C is also


less than thrice the bond energy of C-C, it has the shortest bond length of
1.20 because of its highest electron density.

Example 2: Assuming the normal bond angle at sp3, sp2 and sp hybridized
carbon atom, draw the graphical formula of each of the following compounds
in 3-Dimensional representation.
(i) CH3CH2 C CCH=CH2 (Hex-1-en-3-yne)
(ii) H2C=C(CH3)CH=CH2 (2-Methylbuta-1,3-diene or isoprene)
(iii)

CH3CH=CHCH2 C CH (Hex-4-en-1-yne)

(iv)

CH3CH=CHCH3 (Both cis- and trans-but-2-ene)

(v) CH3 C CCH=CH C CH (Hept-3-en-1,5-diyne).

Solution2: To solve this problem, you need 3 things.


Identification of the type of hybridization for each carbon.
Draw the graphical formula showing the bond angles and shape
(geometry).

Put each bond angle at appropriate carbon center.


(i)

H3C
sp3
H

CH

CH2

sp3

sp

sp

sp2

sp2

H
a

a
H

CH2

C
a
H

C
e

a = b = 109.5o

c = d = 180o
e = f = 120o

C
f
H

Questions for Practice.


1. Draw the orbital pictures of all the compounds (i) to (v) in the example
2 above.
2. What are the two types of covalent bonds; hence, which of the two is
stronger and why?
3. Using the common hybridization pattern, what is the hybrid orbital of
BF3 and state why it is being referred to as a Lewis acid.
4. Each of CH4 and NH3 has a total of 4 electron pairs surrounding the
central atom. However, CH4 is tetrahedral while NH3 is trigonal
pyramid. How can you account for this using hybridization pattern?
5. Give two examples of compounds in each , in which the following
overlaps occur:
(i)

Sp3-sp3 overlap

(iv) sp2-p overlap

(ii)

Sp3-sp2

(v) sp3-d overlap

(iii)

Sp-p overlap

(vi) sp-s overlap

Note: in each case, show the resulting bond of such overlap.

Homologous Series and Functional Groups


Compounds that are member of the same family (i.e. compounds having the
same functional groups) but differ from their neighbours in their molecular
formula by a constant unit CH2- are called members of a homologous series.
10

For example, alkane is a family of saturated hydrocarbon with its first four
members being methane (CH4), ethane (C2H6), propane (C3H8) and butane
(C4H10). Each of these hydrocarbons differs from its neighbor by a constant of
CH2- despite the fact that they are all alkanes; so, they are members of the
same homologous series.

Characteristics of a Homologous Series


(1). All members can be represented by a general formula e.g. the general
formula of alkane is CnH2n+2
When n = 1, we have CH4 which is methane
When n = 2, we have C2H6 which is ethane
When n = 3, we have C3H8 which is propane
When n = 4, we have C4H10 which is butane.
The prefix alk- is determined by the number of carbon atom present
while the
suffix -ane implies the presence of saturation, e.g. C1(meth-), C2(eth-),
C3(prop-),
C4(but-), C5(pent-), C6(hex-), C7(hept-), C8(oct-), C9(non-), C10(dec-)
.
and C20(eico-).
(2). Each member differs from the next by a constant of CH2-, e.g.
C4H10 C3H8 = C3H8 C2H6 = C2H6 CH4 = -CH2(3). Members can be prepared by the same method. For instance, alkanes
can be prepared by the action of sodium alkanoate on NaOH. For the
preparation of methane (CH4), sodium ethanoate (CH3COONa) is used while
for the preparation of ethane C2H6, sodium propanoate (CH3CH2COONa) is the
most appropriate precursor. However, the rate of reaction will be different.
The bulkier the alkyl substituent the lower the rate of reaction. Some
reaction will not even proceed without the presence of a catalyst.
CH3COONa + NaOH
CH3CH2COONa + NaOH

CH4 + Na2CO3
C2H6 + Na2CO3

11

(4). Members of the same homologous series have similar chemical


properties e.g. all alkanes undergo combustion reaction to give CO2 and H2O
irrespective of their state of matter.
CH4(g) + 2O2
C7H16(l) + 11O2
C17H36(s) + 26O2

CO2 + 2H2O
7CO2 + 8H2O
17CO2 + 18H2O

(5). Physical properties of the members vary with change in the molecular
weight.
C1 C4 are gases at room temperature.
C5 C14 are liquid at room temperature.
C15 are above are solid at room temperature.

1. Write out the structural formular of methanoic acid (formic acid),


ethanioc acid (acetic acid) and propanoic acid (propionic acid) showing
all the necessary bonds. Hence, or otherwise In not more than three
sentences, how can you establish that they are members of the same
family?.
2. Nonadecane (C19H40) is a solid hydrocarbon with the properties of a
wax; write out a balanced chemical equation for the complete
combustion of this alkane in air. How can you test for each of the
products of this reaction?
3. Write a balanced chemical equation for the reaction of sodium
pentanoate with sodium hydroxide under acid catalyzed medium. What
is the relevance of the product of this reaction?.
4. Decane used up x moles of oxygen in a complete combustion to
produce y moles of carbon dioxide and z moles of water. Using a
balanced chemical equation, determine the value of x, y and z. Hence,
solve these equations:
(i)

2x2 + 3y2 + z2 5xyz.

(iii) 4x2 + (2y)2 2(xy + yz)

(ii)

3x + 3y 3z + xyz

(iv) x + y - 21zo

12

Functional Group: can be defined as an active part of a compound or


molecule that takes part in chemical reaction. It depicts the family of an
organic compound and at the same time determines its properties.
Functional group is responsible for the type of reaction a compound
undergoes under a prescribed set of condition. All chemical reactions in the
whole world are just conversion of functional groups from one form to the
other.
Reaction Mechanism: is the pathway or route that explains how the
structure of the reactants is transformed to that of products.
S/N IUPAC(Trivial)
Name

Suffix

General
Form.

Functional
Group

Typical
Example

Alkane

-ane

CnH2n+2

-C- paraffin

Methane

Alkene

-ene

CnH2n

C=C

Ethene

Alkyne

-yne

CnH2n-2

CC

Propyne

Alkoxy alkane

-ether R-O-R

-O- (ether)

Diethylether

Alkanol (Alcohol)

-ol

R-OH

-OH
(hydroxyl)

Ethanol (1o)

Alkanal (aldehyde)

-al

R-CHO

C=O
(carbony of
aldehyde)

ethanal

Alkanone (ketone)

-one

R-CO-R

C=O
(carbonyl of
ketone)

Propanone
(acetone)

Akanoic acid
(carboxylic acid)

-oic
acid

R-COOH

-COOH
(carboxylic)

Ethanoic acid
CH3COOH

Amine

amin
e

R-NH2

-NH2 (amino)
1o, 2o or 3o

Ethanamine
CH3CH2NH2

Test for Alkane, Alkene and Alkyne


13

Alkene and alkyne will undergo a positive reaction and decolourize the
following reagents because of the presence of unsaturation whereas alkane
will not react with them.
Acidified potassium permanganate ( KMnO4/ H+).
Alkaline potassium permanganate ( KMnO4/ HO-).
Acidified potassium heptaoxochromate vi (K2Cr2O7/ H+).
Bromine water in carbon tetrachloride (Br2/H2O IN CCl4).
Hydrogen gas in finely divided Nickel catalyst (H2/Ni at 200oC).
However, to distinguish between alkene and alkyne, ammoniacal silver
nitrate or ammoniacal cupper oxide is employed. While alkene remains
unreactive in ammoniacal solution, terminal alkyne will react positively with
such solution.
CH2=CH2 + Br2/H2O

HO-CH2-CH2-Br

CH2=CH2 + KMnO4/ HO-

HO-CH2-CH2-OH

Test for Carbonyl Group


There are two kinds of carbonyl; they are (i) carbonyl of aldehyde and (ii)
carbonyl of ketone.
Carbonyl of aldehyde is found at the terminal end of a chain while that of
ketone is inserted between two carbon atoms.
(i)

(ii)
R

O
C

H
Aldehyde

ketone

R'

So, in aldehyde, one hydrogen is attached to the carbonyl carbon while in


ketone the H had been replaced with carbon.
(a).DNP Test (General Test for Carbonyl)
Due to the close relationship exhibited by the two, they both react positively
with 2,4-dinitrophenyl hydrazine (2,4-DNP) to give colored crystalline solid
called 2,4-dinitrophenyl hydrazone .

14

R
R'

C O+

H
NH2 N

NO2

R'

O2 N
2,4-dinitrophenylhydrazine

H
N

NO2

+ H2O

O2N
corresponding hydrazone

when R' = H, we have Aldehyde


when R' = carbon, we have ketone

Since, both aldehye and ketone have the same reaction with 2,4-DNP how
then can we distinguish between the two? This can be achieved by using
either Fehling or Tollens test; since aldehyde react positively with the two
reagents (Fehling and Tollens reagents) while ketone will not. Otherwise, you
can react ketone with semicarbazide (NH2NHCONH2) to obtain a coloured
precipitate of semicarbazone while aldehyde will not react with
semicarbazide.
(b).Fehling Solution Test
Add few drops of alkanal (aldehyde) to the blue coloured fehling solution and
warm; the mixture will turn to brick red precipitate whereas with alkanone
(ketone) the blue colour remains (i.e. no reaction).
This change is as a result of reduction of Cu+2 to Cu+1
RCHO + Cu+2

RCOONa + Cu+1

NaOH/H2O/warm

Blue

brick red

This is also what happens in test for glucose because it is a reducing sugar.
Glucose will give a positive reaction with fehling solution while fructose will
not. Fehling solution is a mixture of fehling A (CuSO4) and Fehling B (NaOH
and Rochelle salt).

(c).Tollens Test
This is otherwise called silver mirror test. Warming a mixture of aldehyde and
ammoniacal silver nitrate (Tollens reagent) gives a deposit of shining silver
metal on the wall of the test-tube whereas with carbonyl of ketone, there is
no reaction.
RCHO + Ag(NH3)2+

RCOO- + Ag

15

Tollens reagent (AgNO3/NH3) is good for the synthesis of ,-unsaturated


acid from ,-unsaturated aldehydes because it does not attack the double
bond (C=C) in the process.
Ag(NH3)2+

R-CH=CH-CHO
,-unsaturated aldehyde

R-CH=CH-COOH

,-unsaturated acid

Test for Phenol


Add few drops of freshly prepared iron III chloride (FeCl3) to the phenol and
shake lightly; observation of an intense colouration confirms the presence of
phenolic OH. This test is very good for the confirmation of the polyphenolic
groups (anthocyanin) in natural product.
Test for -OH of Alcohol
There are three types of alcohols. These are the primary (1o), the secondary
(2o) and the tertiary (3o) alcohols. All these alcohols give steamy or dense
white fume when treated with PCl5 or PCl3 or thionyl chloride at room
temperature.
ROH + PCl5

RCl + POCl3 + HCl

However to distinguish between 1o, 2o and 3o alcohol, Lucas reagent is being


used. Add few drops of Lucas reagent to the alcohol; with 1o alcohol, there is
formation of a clear liquid; with 2o, the liquid separates into two layers after
5minutes while with 3o alcohol, the separation into two layers happens
immediately.
Lucas reagent is prepared by dissolving 0.5 mole of ZnCl2 in 0.5 mole of
concentrated HCl followed by cooling at room temperature.
Test for Carboxylic Acid (-COOH)
When few drops of saturated sodium bicarbonate (NaHCO3) is added to any
carboxylic acid group, there is an effervescence of a gas (CO2) which turns
lime water milky. However, the milkiness disappears when the gas is
liberated in excess.
RCOOH + NaHCO3

RCOONa + H2O + CO2

16

Preparation of Carboxylic Acid Derivatives


Carboxylic acid derivatives are the compounds in which the OH of carboxyl
functional group has been replaced by another element or group.
O
R

OH

Y = halogen; acid halide


Y = NH2; amide
Y = OR'; ester
Y = OCOR'; acid anhydride

1. Acid Halide: This is obtained when the OH of COOH is being replaced


with a halogen (e.g. Y = F, Cl, Br, I). Acid chloride is much more
reactive than the carboxylic acid from which it is being obtained. It can
be prepared by treating carboxylic acid with either thionyl chloride
(SOCl2) or PCl5.

COCl

COOH
+

PCl5

benzoic
acid

(ii) CH3COOH + PCl5


HCl(g)

POCl3

HCl

benzoyl
chloride

CH3COCl + POCl3(l) +

(iii) CH3COOH + SOCl2

CH3COCl + SO2(g)

+ HCl(g)

2. Amide: This is obtained when the OH of COOH is being replaced with


an amino group (e.g. Y = NH2). This is a derivative of carboxylic acid
that is formed by the reaction of ammonia or amine with acid halide or
carboxylic acid.
CH3COOH + NH3
CH3COCl + NaNH2

CH3CONH2 + H2O
CH3CONH2 + NaCl

17

Ethanoyl chloride

ethanamide

3. Acid Anhydride: This is obtained when the OH of COOH is being


replaced with an alkoxylcarbonyl group (e.g. Y = OCOCH3). This is a
derivative of carboxylic acid that is formed by distillation of two
molecules of the acid in the presence of a suitable dehydrating agent
such as P4O10. The driving force for the reaction is the elimination of a
stable molecule of water.
P4O10

2CH3COOH

(CH3CO)2O

O
CH3

CH3

P4O10
-H2O

CH3

C
O

CH3

C
O

4. Ester: This is obtained when the OH of COOH is being replaced with


an alkoxy group (e.g. Y = OR). Ester can be obtained by the reaction of
the acid with alcohol in the presence of a mineral acid. However, if the
acid chloride is used the reaction takes place at low temperature (0-5oC
) and need no catalyst. This forward reaction is called esterification
(alkanoation) while the backward reaction is called hydrolysis.
CH3COOH + CH3CH2OH

H+

CH3COOCH2CH3 + H2O
Ethyl ethanoate

CH3COCl + CH3CH2OH

0-5oC

CH3COOCH2CH3 + HCl

Questions for Practice


1. An unlabelled bottle on the shelf is suspected to contain either
propanal, propanone or propanoic acid. Describe the chemical test(s)
to establish which of the three is actually in the bottle.
2. Name four classes of carboxylic acid derivatives with two examples of
each. Then, explain how each of those compounds can be obtained
from the corresponding carboxylic acid.

18

3. The compound Y below is the structure of the ampicillin which is a -

lactam antibiotic used in the treatment of infections. Circle and write


the name of the functional group(s) present in Y. Hence, explain briefly
how to test for those identified functional group(s).
H O
C

NH
N

NH2

CH3
CH3

CO2H

4. With the aid of equation only, how can you synthesize 3-methyl-2pentenoic acid from 3-methyl-2-pentenal .

Isomerism
In 1823, transformation of ammonium cyanate (inorganic compound) to urea
(organic compound) was first observed by Wohler who was a student of J.J.
Berzelius in Germany. Then, Berzelius was interested in a case in which two
clearly different materials had the same elemental composition and he
invested the term isomerism to describe it.
NH4OCN
ammonium cyanate
(CH4ON2)

NH2CONH2
urea
(CH4ON2)

Isomerism: is said to occur when two or more compounds have the same
molecular formula but different physical properties and/or chemical
properties. The compounds that exhibit this behavior are called Isomers.
There are two main types of isomerism: (i) structural (ii) stereoisomerism.

19

ISOMERISM

STRUCTURAL

POSITION

STREREOISOMERISM

FUNCTIONAL
GROUP

CHAIN

GEOMETRICAL

OPTICAL

1. Structural Isomerism: This occurs when two or more compounds have


the same molecular formula but different structure (i.e. arranging atoms in
different ways). It is subdivided into three namely: positional, functional
group and chain isomerism.
(i). Positional Isomerism: This occurs within a particular homologous
series that involves changing of the position of some substituents. This type
of isomerism has the same chemical properties but different physical
properties.
e.g.
(i)

butan-1-ol

OH

OH

(C4H10O)

butan-2-ol (C4H10O)

(ii)
H

OCH3

H
OCH3

1-methoxybutane (C5H12O)

2-methoxybutane

(C5H12O)

(ii). Functional Group Isomerism: This occurs when two or more isomers
have the same molecular formula but different functional groups, e.g. alcohol
and ether.

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CH3CH2OH

and

ethanol (-OH)

both have Mol. Form. C2H6O

CH3OCH3

dimethylether (-O-)

Presence of polar OH with formation of Hydrogen bonding makes alcohol to


have high boiling point while low boiling point and high volatility in ether is
as a result of the presence of weak force of attraction. Another example of
the functional group isomers are alkanal (aldehyde) and alkanone (ketone).
CH3CH2CHO

and

propanal

CH3COCH3

propanone(acetone)
O

F.G.

both have Mol. Form. C3H6O


O

F.G.

CH3

(ii). Chain Isomerism: This occurs when two or more isomers have their
chains differently arranged. It occurs within the same homologous series.
There is an occurrence of straight and branched chain isomers. However, the
straight chain isomers have higher boiling point and lower volatility than the
branched chain counterparts despite they have the same molecular formula
e.g.

(i)
H

n-pentane (C5H12)

CH3

H
CH3 H

2-methylbutane (C5H12)

H
H

H C
H

CH3

CH3

2,2-dimethylpropane (C5H12)

2. Stereoisomerism: This occurs when two or more compounds have the


same molecular formula but different arrangement in space. This is
established by using the three dimensional structure of sp3, sp2 and sp
hybridization of carbon atoms. It is subdivided into two namely: geometrical
and optical isomerism.
(i). Geometrical Isomerism: This exists in compounds where free rotation
is not possible either because of C=C or presence of ring in cyclic
compounds. For this to occur C=C must be symmetrically positioned. It is
exhibited inform of cis- and trans-isomers. The two atoms attached to a sp2
carbon must not be the same in order to have cis-trans isomerism, e.g.
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CH3

C
CH3

H3C

transbut-2-ene
(opp. side of plane)

C
H

H3C

C
D

no geometrical isomerism

cis-but-2-ene
(same side of plane)

Another example of the compound that exhibits geometrical isomerism is


1,2-dichloroethene. ClCH=CHCl.
H

Cl

Cl

trans-1,2-dichloroethene
(opp. side of plane)

C
H

Cl

C
Cl

cis-1,2-dichloroethene
(same side of plane)

(ii). Optical Isomerism: This occurs when a compound is able to rotate a


plane polarized light. When a plane polarized light is made to pass through
the solution of an optically active compound, the plane of polarization rotates
to the right or clockwisely to give a dextrorotatory, (+) compound. If the
rotation is to the left or anticlockwise in nature, it gives lavorotatory
compound which is indicated with the symbol (-) as the prefix. For any
isomer to be optically active, it must possess an asymmetric carbon atom
(i.e. carbon with a stereogenic or chiral center). Sp3 carbon atom is said to
have a chiral center if it is surrounded by four different atoms or groups. If a
compound has a chiral carbon center but it is not superimposable on its
mirror image, it is called an enantiomer while the phenomenon is known as
enantiomerism. Enantiomeric pairs have the same physical properties,
except for the direction of rotation of plane polarized light, e.g. 1chloropropan-1-ol and 2-hydroxypropanoic acid (lactic acid) have one chiral
carbon center each, so, they are optically active and their enantiomeric pair
will be the mirror image that is not super imposable on the starting isomer.

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(i)

C2H5

OH

C2H5

HO

Cl

Cl

This is one enantiomeric pair of 1-chloropropan-1-ol

(ii)
COOH

COOH

C
H

C
OH

CH3

HO
CH3

This is one enntiomeric pair of 2-hydroxypropanoic acid(Lactic acid)

Other examples of optical isomers are:


(iii) chloroiodomethane sulfonic acid (ICHCl.SO3H)
(iv) 2-bromobutane (CH3CH2CHBr.CH3)

Ordinary and Plane Polarized Light


Ordinary Light: can be defined as electromagnetic radiation vibrating at right
angle to the direction of its propagation (transverse wave motion) in an
infinite numbers of plane. When ordinary light passes through polarizer, its
light vibrates only in one plane and become polarized. When this plane
polarized light is made to pass through solution of some compounds, the
plane of polarization is either rotated to the right or left.

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