CHM 202

COVALENT BOND

It is represented by a dash ( - ) or by dots (electron dot) e.g H2 = H – H or

Wheras electrovalent bond is represented by charges e.g NaCl is not Na – Cl but

The bond b/w H and Cl is covalent so it is represented as: H – Cl better still as:

Lewis Structure: In Lewis structure, bonded electrons are represented by a dash while non-
bonded (lone pair electrons) are represented by dots:

Methanol is thus represented as:

From the above we have 5 bonded and 2 lone pairs electrons in Methanol

Lewis Structure & Partial Charge on some atoms:

NH3

N atom has 7 electrons, 2 in K shell and 5 in L shell. δ covalent bond is made with 3 protons
remaining 2electrons as lone pair on N atom. Lewis structure for NH3 therefore is:

showing 3 δ covalent bonds and a lone pair on N-atom.

1
Assingment:

Draw lewis structures for: (i) Ammonium ion; (ii) Nitromethane (CH3NO2) and (iii) ethane.
How many bonded and non-bonded electrons are present in each indicate charges where
applicable?

Formation of Covalent bond

Covalent bonds are formed by electron sharing in S or P orbitals:

S + S = δ covalent bond

S + P = δ covalent bond

P + P = δ covalent bond ( Orbitals Linearly aligned)

P + P = π covalent bond (Orbitals Laterally aligned)

Polarity In Covalent Bonds:

If the bonded atoms are identical, the compound will be Non-polar or Neutral e.g H – H etc

If the bonded atoms are different in elctronegativity (-veity) values the resultant molecule
will be polar because they will have permanent partial charges. They are compounds with
Dipole

Dipole Moment (µ):

This is the product of the partial charge ‘q’ and the distance ‘d’ between the opposite charges

µ = qd. Dipole moment is expressed in Debye (D), it is a vector quantity

2
Different compounds have different µ depending on the relative (-veity) values of bonded
atoms. The value of q is a function of (-veity) difference b/w bonded atoms. The higher the (-
veity) difference, the higher the value of q hence µ.

Dipole moment of H2O

It has a resultant dipole moment of 1.84

while H – F has a dipole moment of 1.75

Order of (-veity) of some common atoms: F > O > Cl, N > Br > C, H

Dipole moments of some common compounds:

HF = 1.75; NH3 = 1.43; NF3 = 0.24; SO2 = 1.61 and H2O = 1.84.

The µ of H – Cl is lower than that of H – F. Explain?

Intermolecular Forces

These are forces that hold two or more covalent molecules together. They are (i) Induced
dipole (Van de Waals); (ii) Dipole-Dipole and (iii) Hydrogen bonding

(i) Induced dipole (Vander Waals) H−H bonding atoms have same electronegativity

Due to continual movement of the atoms and vibration of the bonds, the bond electron shifts
to one atom than the other at an instant therefore creating an instantaneous dipole. This
instantaneous dipole induces dipole in the surrounding molecule thereby creating a force of
attraction among the molecule. This intermolecular force is weak because it disappears and
reappears. i.e. it is not permanent. It is weaker than Dipole-Dipole force

(ii) Dipole-Dipole ( H−Cl bonding atoms have different electronegativity values)

The bond electrons are permanently towards the more electronegative atom, thereby creating
a permanent dipole force of attraction among the molecules.

(iii) Hydrogen bonding

Hydrogen bond is a form of permanent dipole where hydrogen is bonded to highly
electronegative atoms. This intermolecular force is stronger than dipole-dipole and Van der
waal force of attraction.

3
Application of Intermolecular Forces

(i) Boiling/ Melting Points (Intermolecular Forces between molecules of same compounds):

In Polar Molecules: The higher the µ, the higher the Dipole-Dipole force b/w molecules and
the higher will be the melting / boiling points.

HF has a higher B.pt than HCl, becos F has higher elec-vevity value than Cl

H2O has a higher B.pt than HF though F has higher elec-vevity value than O. This is becos of
H-bonding. As H-bonding increases b.pt increases.

In Non-polar Molecules: The bigger the molecule the higher the electron density and the
Vanderwaal forces hence the higher the b.pt. Order of increasing b.pt of noble gasses:

He (4 K) < Ne (27 K) < Ar (87 K) < Kr (120 K) < Xe (166 K) < Rn (211 K).

(ii) Solubility (Intermolecular Forces between molecules of different compounds):

For a substance to be soluble in another, their molecules must be able to form H-bonding. A
polar substance dissolves in a polar solvent: like dissolves like; non-polar substance dissolves
in non-polar solvent

Polar Protic & Polar Non-Protic (Aprotic) Solvents

A protic solvent is one that has active H-atom in its molecule and is able to form H-bonding
whereas a polar aprotic solvent is one that doesn’t have active H atom and so can’t form H-
bonding.

E.g of Polar Protic solvents include: R-OH, R-SH, H-X etc.

Polar aprotic solvents include:

Dimethylsulphoxide (DMSO,

and Dimethyl formamide (DMF)

4
Ion-Dipole Bonding

Protic solvents can solvate both cations (+ve ions) and anions (-ve ions) i:e able to form ion-
dipole bond whereas aprotic solvents can only solvate cations and not anion.

The Dielectric Constant of a solvent is the ability of the solvent to separate oppositely
charged ion. To dissolve ionic compounds solvent must have high dielectric constant e.g
H2O. However, anions are more available (reactive) in aprotic solvents than in protic solvents
because they are not solvated in aprotic solvents.

5
Resonance in molecules

This is due to the movement of mobile electrons (lone pair or pie electrons) leading to the
formation of two or more Lewis structures, which are identical in their properties : e.g HNO 3

Hybridization in C-compounds: Sp3; Sp2 and Sp

Sp3: e.g (i) CH4

Outer Shell Ground state C: 2S2; 2px1, 2py1, 2pz0

Excited state: 2S1; 2px1, 2py1, 2pz1. Sp3 hybrid orbitals. Because all the 4 Sp3
hybrid orbitals (one S and three p orbitals) are used in forming sigma (δ) covalent bonds with
S-orbital of H-atom, CH4 is referred to as Sp3 hybridised compound with bond angle of
109.5o and tetrahedral geometry.

(ii) C2H4

Excited state C-1: 2S1; 2px1, 2py1, 2pz1

C -2: 2S1; 2px1, 2py1, 2pz1

The single electron in each of 2S1; 2px1, 2py1 in C-1 overlaps (combine) with electron in
each of 2S1; 2px1, 2py1 in C-2 to form Three δ covalent bonds with 120o bond angle and a
trigonal planar geometry. The 2pz1 in each C-atom combine collaterally to form a pie bond.
This is reffered to as Sp2 hybridization because 3 of the Sp hybridized orbitals are involved
in δ covalent bond formation (one S and 2 p orbitals)

(iii) C2H2

The electron in each of the 2S1; 2px1 in C-1 combine with those in each of 2S1; 2px1 in C-2 to
form Two δ covalent bonds aligned 180o to each other resulting in a linear geometry.

6
Assignment:

(a). Determine the hybridisation of each C-atom in the following compounds

(i) CH2CHCH2CH3 & (ii) CH3CH=C=CH2

(b). Determine the total δ covalent bonds in the following C-compounds:

(i) C6H10, (ii) C7H10 (iii) C2H2 and (iii)

*Total δ covalent bonds in C-compounds: = No of C – 1 + Sum of other atoms.

CLEAVAGE OF COVALENT BOND

There are two ways by which covalent bond can be broken:

(i) Homolytic cleavage: It readily takes place in molecules with atoms having
identical electronegativity values. The two electrons involved in bonding are
shared by the two atoms bonded equally resulting in two neutral radicals:

(ii) Heterolytic cleavage: The two bonded electrons on cleavage move to one of the
atoms (more electro-ve atom) resulting in formation of charged entities (a cation,
and an anion)

7
Factors Affecting Availability of Electrons in Organic Reactions

(i) Inductive effect (ii) Mesomeric effect (iii) Resonance effect (iv) Steric effect

Inductive Effect

This is the movement of electrons along sigma covalent bondin a molecule due to the relative
electronegativity of adjacent atom(s). It is designated with letter ‘I’. When an atom or group
of atoms draw electrons away from the centre to which they are attached, it is described as
Negative Inductive Effect designated as – I effect, e,g:

The order of acidity of the above acids increases from acetic acid to trichloroacetic acid due
to the – ve inductive effect of the Cl-atom

If an atom or group of atoms release electrons to the centre atom, it is referred to as Positive
Inductive (+ I) Effect:

The 3o alkyl halide above will undergo heterolytic cleavage fastest due to +I effect of the 3
alkyl groups and the resulting carbocation is stabilised by +I effect of the alkyl groups:

Mesomeric Effect

The effect due to the movement of lone pair electrons in an electronegative atom to the centre
attached: Mesomeric effect is designated by “M”. If electrons are moved away from the

8
centre, this is “-M” effect but if electrons are drawn towards the centre, it is called “+M”
effect.

As seen above the mesomeric effect (+M) of the lone pair electrons in N-atom increases the
single-bond character of carbonyl group, thus the carbonyl group in amides have higher
single-bond character than simple ketone.

Note:

1. N-atom is more elctro-ve than C-atom hence N, draws electron from C by –I effect,
however the +M effect predominates.
2.

The – I effect of Cl-atom predominates over the +M effect, hence carbonyl bond in
ethanoyl chloride has higher double bond character than simple ketone.

Resonance Effect

Resonance effect is movement of pie or lone pair electrons in molecules leading to formation
of 2 or more Lewis structures of the molecule.

(a) b/w 2 or more multiple bonds (b) b/w a charge atom and a multiple bond

Steric Effect

9
This is otherwise called overcrowding effect: when the central atom is attached to
bulky groups, which hinders the approach of incoming reagent.

It is much easier for the Io- carbocation (case a) to react with the incoming anion because
protons are smaller atoms than the 3 alkyl groups surrounding the 3o-carbocation (case b).
Thus we say the reaction is difficult with case b becos of steric hinderance.

Types of Organic Reactions

Various types include:

1. Substitution reaction
2. Elimination reaction
3. Addition reaction
4. Free radical reaction
5. Re- arrangement reaction

1. Substitution Reaction- when an atom/ group of atom is substituted first in a molecule. E.g

CH3OH + HCl CH3Cl + H2O

methanol chloromethane

This reaction can take place by two different mechanism

i. Uni-molecular substitution
ii. Bi- molecular substitution

10
CH3 CH3
H3C C OH + HCl CH3 + H3C C Cl
CH3 CH3
Tertiary alcohol

Electrophile
CH3 CH3
CH3 Nucleophile
+ -
H3C C Cl H3C C Cl
H3C C OH
CH3
CH3 CH3

Carbo cation

Nucleophilic Substitution

This reaction involves generation of a positive center (carbo-cation) for attack by the
nucleophile.

Unimolecular Nucleophilic Substitution: mechanism is initiated by the formation of the

carbo cation (electrophile) by heterolytic cleavage of the substrate. This step involves only
the substrate, reagent is not involved:

Substrate + Reagent Product

Rate Determining Step

RDS
1st step (H3C)3 COH (CH3)C+ + OH-
slow

Cl-
2nd step (CH3)3C+ (CH3)3C Cl
fast

Cl- has equal tendency of attaching to either side of the carbo cation (this forms
enantiomers). If the carbon centre is chiral, it usually produce a Racemate.

11
1. Bi-molecular Substitution

H
H3C C OH + Cl-
H

They do not undergo heterolytic cleavage to form carbon cation. The incoming group will
attach from behind (opposite side) while the leaving group will leave. Both will not be in the
same side.

H
H
Cl -
+ H3C C OH Cl OH Cl CH3 + OH-
H CH3 H

The incoming group attacks the opposite side of the leaving group resulting in Inversion of
configuration.

SN2 involve both substrate and the reagent therefore bulky group surrounding the centre C-
atom doesn’t favour the reaction . In SN2 the carbon centre of the intermediate product is
surrounded by 5 groups. If there are bulky group surrounding the carbon centre the reaction
will be sterically hindered.
In SN2 the incoming group approaches the center C-atom in the opposite side of the
leaving group. This type of reaction is said to be STEREO-SPECIFIC i.e a specific isomer is
obtained. If you start with negative, you will end with positive and vice versa.

2. Elimination Reaction
This means to remove small atoms or group of atoms from a saturated (sp3) molecule to
form an unsaturated molecule (sp2 or sp) product.
e:g

12
alcohol KOH
H3C CH2Cl H2C CH2

substrate product

alcohol KOH is a base acting as a catalyst in the hetereolytic cleavage

Elemination reaction can also take place by two different mechanisms:

E1: Unimolecular elimination and E2: Bimolecular elimination

In E1, the reaction is initiated by heterolytic cleavage in the substrate moleculeto form a
carbocation:

13
Using Sayzeff’s rule helps to determine the main product. It state that In elimination
reaction, after the formation of the carbo- cation, the removal of hydrogen atom takes
place in the adjacent carbon atom containing fewer hydrogen atom.

E1 - Elimination (unimolecular elimination) usually takes place with substrate carrying very
large substituent groups, which can readily undergo heterolytic cleavage to form a carbo
cation which is planar in geometry.

E2- Elimination (bimolecular elimination) is usually favoured with non-bulky substituent.

A primary alkyl halide normally goes with E2.

In E2 the transition state very unstable (5 groups around the olefinic C-atom).

3. Addition Reaction
In addition reaction, small atoms or group of atoms are added to an unsaturated molecule
(sp or sp2) to give a more saturated product. The substrate is SP2 or SP in geometry and the
final product is SP3.
E.g

1. H2C CH2 + H H H3C CH3

SP2 SP3
Reagent here is symmetrical
1 and 2 are Additon reaction

2.
H
H3C C CH2 + HCl H3C C CH3
H
Cl
Non-symmetrical reagent

14
Mechanism of addition reaction

The reaction is called ‘Electrophilic addition’ because it is initiated by electrophilic attack on

the substrate to give a carbocation intermediate:

H2 +
1st step H3C C CH2
H+
H3C C CH2
H
+
H3C C CH3
electrophilic attack H

Using Markownikoff’s rule, which helps us to determine the main product states that when
an unsymmetrical reagent adds to an olefinic (double bond) center, the positive part of
the reagent adds on to the olefinic carbon carrying higher number of hydrogen atom. Thus
the carbocation with correct tick above is the main product.

4. Free Radical Reaction

A radical is generated by homolytic fusion and cleavage of covalent bond.

1st Step (Initiation)

Cl2 Cl Cl 2 Cl

The reaction of alkanes with halogens (like chlorine) under sunlight is an example of a free
radical reaction which goes thus.

2nd Step (Propagation);

CH4 + Cl CH3 + HCl (methyl radical)

CH3 + Cl2 CH3Cl + Cl (monochloro methane)

CH3Cl + Cl CH2Cl + HCl

CH2Cl CH2Cl2 + Cl (Dichloromethane)

+ Cl2

CH2Cl2 + Cl CHCl2 + HCl

CHCl2 + Cl2 CHCl3 + Cl (chloroform or trichloromethane)

CHCl3 + Cl CCl3 + HCl

CCl3 + Cl2 CCl4 + Cl (carbon tetrachloride or tetrachloromethane)

15
The free radical mechanism is always a step-wise reaction. Generation of radicals is the
initiation step. Termination stage can take place either by collision of radicals and end the
reaction.

3rd Step (Termination)

(i) Radical combination

Cl + Cl Cl Cl

CH3 + CH3 H3C CH3

CH2Cl + CH3 H3C CH2Cl

Neutral molecule is formed and free radicals get terminated

(ii). Disproportionation: Alkane and alkene is formed when this process occur. Formation of
neutral molecule with one saturated and the other unsaturated.

2 H3C CH2 CH3CH3 + H2C CH2

Ethane Ethene

2. Re-arrangement reaction: by re-arrangement reaction the migration of an atom group of

atoms for one position in a molecule to another.

R R
+ + +
R CH2 R CH R C
R
increasing order of stability

CH3 CH3 CH3 CH3

+ Cl-
H3C C CH2Cl H3C C CH2 + Cl- H3C C+ CH3 H3C C CH3
H H
Cl

16
Chemistry of Hydrocarbon

Alkanes

Homologous series

Characteristics of Homologous series

As we go down the series, the molecular weight of the member increase down the
group, density, boiling point and melting point also increases.

A member differs from the immediate neighbor by -CH2.

Method of Preparation

1. Alkanes can be obtained from petroleum by the process of cracking or fractional

distillation of higher members.
2. Grignard synthesis: R-MgX alkyl magnesium halide

Dry ether - +
R Cl + Mg R MgCl

Aprotic solvent i.e solvent that does not contain active hydrogen is used in Grignard’s
synthesis. In presence of active H, (e.g water) R-MgCl formed gets hydrolysed:

- + -
R MgCl + H+ OH R H + MgClOH

Alkane

3. Hydrogenation of unsaturated hydrocarbon: If you react alkene in the presence of

hydrogenating catalyst (Pt, Ni or Paladium- Pd)

4. Wurtz reaction: 2 molecules of alkyl halides (identical or different) react in the presence
of metallic sodium to give alkanes. This two molecules may be identical or different.

17
2 CHCl + 2 Na H3C CH3 + 2 NaCl

2 Na
CH3Cl + C2H5Cl H3C C2H5 + 2 NaCl

H2
H3C C CH3 C3H8

5. Reduction of alkyl halide using appropriate reagent such as LiAlH4 (lithium aluminium
tetrahydride)

Reducing agents: NaBH4, Na/NH3, Zn/HCl, LiAlH4

LiAlH4
4 CH3CH2Cl 4CH3CH3 + LiCl + AlCl3

Properties of Alkanes

1. Alkanes are non- polar molecule soluble only in non-polar solvent.

2. Hybridization of alkane is sp3 with tetrahedral geometry.

Chemical Properties in Alkanes

1. Halogenation reaction: Alkanes react with chlorine and bromine in the presence of
sunlight energy to give chloro and bromo derivatives respectively.
2. Combustion reaction: Hydrocarbon or alkanes react in the presence of oxygen to give CO2
and H2O as the only product; If you use excess O2 you are going to have CO2 and H2O.
Sometimes, coke and CO may also be formed depending on the proportion of O2 to
hydrocarbon. In the presence of insufficient O2; coke and CO may be formed.

3. Pyrolysis: it is the same thing as cracking. It is the decomposition of hydrocarbon by

reaction of heat and sometimes in the presence of catalyst.
In Petroleum industry, it is called ‘thermal’ or ‘catalytic cracking’. It usually takes
place at high temperature in the ‘absence of air’. The benefit include:

1. Production of fuel for internal combustion engine

18
2. Production of lower hydrocarbons for the preparation of large number of
chemicals in the petroleum industry.
4. Isomerization: Formation of isomers of organic compounds:

CH3
Al2O3 H2 H H2
CH3CH2CH2CH2CH2CH3 H2CH3C C CH3 + H3C C C C CH3
3000c CH3 CH3
n- hexane
(possess high mp) 2,2- dimethylbutane

Alkyl Halides

An alkyl group have the general formula of CnH2n+1 and it can be represented by R.

Properties of Alkyl Halide

Physical properties

1. They have higher boiling point than corresponding alkene e.g CH3Cl > CH4, because of the
molecular weight. The boiling or melting point of alkyl halides increases with the weight
of halogen.
2. Despite their polarity, they are insoluble in H2O but soluble in organic solvent.
Alkyl halides are denser than water.

Chemical Properties

1. They undergo nucleophilic substitution reaction with reagent that can generate
nucleophile such as

-
a RX + OH R-OH + X-

-
b RX + OEt R-OEt + X-
-
c RX + CN R-CN + X-

- | |
d RX + C CR R C CR + X-
-
e RX + Z R-Z + X-
| |
f RX + R-M R-R + M

19
2. Dehydrogenation- removal of HX to form unsaturated molecule.

alc. KOH
CH3 CH2 H2C CH2 + H X
X

When you have 2 unsymmetrical compound, you will have 2 possible result which leads to the use of
Saytzeff’s rule.

3. Preparation of Grignard reagent: alkyl-halide reacts with magnesium in the presence of

dry ether to give grignard reagent.

Dry ether
R X + Mg R MgX

Preparation of Alkyl halide

1. From Alcohol (ROH): Alcohol react with appropriate halogenation reagent to produce
alkyl halide. There are various halogenation reagent which include:
(i) acid halide (HX);

(ii) Phosphorous trihalide or pentahalide (PCl3 / PCl5)

(iii) Thionyl chloride (SOCl2)

R- OH + HX ------ R – X + H2O

R- OH + SOCl2 ----- R – X + H3PO3

R- OH + PBr3 ----- 3R – Br + H3PO3

R- OH + PBr5 ------ R – Br + HBr + POBr3

2. Halogenation of some hydrocarbon: e.g

CH3 CH3
Cl2 / hv
H3C CH CH3 H3C C CH2Cl

CH3 CH3
2,2-dimethyl propane

20
CH3 CH2Br
Br2 / Reflux

3. Addition of hydrogen halide to alkene (unsaturated compound). Example:

H
H3C C CH2 + HX H3C C CH3
H
X

4. Addition of halogens to alkene or alkyne

H2C CH2 + Cl2 H2C CH2

Cl Cl

Cl Cl
H H Cl2
HC CH + Cl2 H H
Cl Cl
Cl Cl
1,1,2,2- tetrachloroethane

Stereochemistry

Stereo talks about arrangement in space, therefore Stereochemistry means the study of spatial
arrangement of atoms in a molecule. The spatial arrangement of atoms affects the structural
properties of the molecule resulting in different isomers.

Isomerism is a phenomenon whereby a chemical compound have the same molecular

formula but different structural formulae.

21
Chain Isomerism- deals with compounds of same molecular formula but are different in
their own length. E.g

H H H
H H H H
H C C C H
H C C C C H
H C H
H H H H
H
n- Butane (C4H10)
2- methyl propane (C4H10)

Rule for IUPAC Nomenclature

 Determine the longest chain which shall be the parent name.

 Check from the longest chain, points where there are branches.
 Assign numbers to the longest chain and note the points of branches and make use of
the least summation of numbers of the points of branches. E.g

H CH3 H H

H3C C C C C CH3

CH3 CH3 H CH3

2,3,3,5- tetramethylhexane

It will be incorrect to name the above as: 2,4,4,5-tetramethylhexane becos summation of

numbers (15) is higher than 2,3,3,5- which is 13.

 Name the atoms on the point of attachment according to their number.

 When there are 2 or more types of groups attached in a molecule, they are named in
alphabetical order.

2. Positional Isomerism- deals with position of functional group or branch group. E.g

3. Functional group Isomerism- deals with 2 different compounds with same molecular
formula but different functional groups.

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4. Cyclic/Acyclic Isomerism- deals with isomers of unsaturated compounds (double/triple
bond) in which a double bond = a ring structure irrespective of the size of the ring; a triple
bond = 2 double bonds etc. E.g:
H2
C
CH2=CH-CH3
propene (C3H6) H2C CH2
Acyclic structure
Cyclopropane (C3H6)

Stereo-Isomerism

1. Geometrical Isomerism- This is known as cis/trans isomerism. This is as a result of the

double bond in the structure. The double bond confers rigidity on the molecule thereby
restricting free rotation.

Double bond confers rigidity

Identical groups on the opposite side of the double bond =Trans; Identical groups on the side of
the double bond = Cis

Rules in Naming Organic Compounds – Organic Nomenclature

1. Locate the longest chain, this determines the parent name for the compound.
2. Number the longest chain beginning with the end nearest to the substituent group or
number so as to give least summation of numbers.

23
3. Use of the number obtained in 2 above to designate the location of the substituent
groups.
4. When 2 substitute groups are present on the same carbon atom, use the number twice.
5. When two or more chains are of equal length, choose the chain with greater number of
substituent group.

H2 H H H H
H3C C C C C C CH3
CH3 CH2 CH3 CH3
CH2
CH3

2,3,5- trimethyl-4-propyl heptane

6. If the substituent group in a branched alkyl group, note the position of the branching and
write the name of the branch group in bracket and note that the carbon that is directly
attached to the main chain is referred to as carbon number 1 in the substituent group.

Z and E notation
Z means Zusamen; E means entgene

Z and E notation is resolved by: Cahn Ingold- Prelog Rule. It depends on the mass number
(atomic mass) of atoms attached to the alkene (olefinic) center.

If two bulky atoms are on the same side. It is Z- isomer; whereas if two bulky groups are on
opposite side of the double bond it is E-isomer.

Cahn Ingold- Prelog Rule

1. You consider the atoms that are directly attached to the Olefinic center
Br CH3

C C

Br CH3 Cl H
C C
Cl H

24
2. If you cannot distinguish priority based on the 1st set of atoms (1o consideration), then
move to the next set of atoms. H CH3
C C
HO CH2CH3

3. If a substituent group contains unsaturated system, for secondary consideration the

second carbon atom is taking as being connected to 2 or 3 carbon atom of a double or triple
bond.
1.
CH2
H3C HC
C C CH
3
CH C C
H3C CH3

Optical Isomerism
When two or more organic compounds are alike in every aspect, but differ in their action on
plane-polarized light, they are known as ‘Optical Isomers’.

Polarimeter - instrument used to measure the observed rotation of optical isomers.

prism To adjust the rotation

To polarize
(to make travel in one direction)

Any compound that affects the plane polarised light is said to be optically active. If it turns
the plane of polarised light clockwise it is termed Dextro- rotatory compound and
designated as positive (+ve) isomer but if it turns the plane anti-clockwise, it is termed
Levo-rotatory, designated as negative (-ve) isomer. If a compound did not affect the plane of
polarised light, then it is not optically active.

The degree of activity of an optically active compound is measured by its observed rotation
(α) expressed as either + or - in degree. Mathematically observed rotation α is:

Where:

is the specific rotation of the the compound. The specific rotation of a pure organic
compound is a characteristic of the compound. It is expressed as either + or – in degree.

25
C = concentration of the organic compound (g/ml), while l = path length (length of sample
cell in dm); 25 = average room temp and D = Sodium D-line. e.g:

Calculate the observed rotation of an organic compound containing 0.35 g/ml of it a 5.0 cm
cell , if it’s specific rotation is +16o.

α = cxl x

= [ 0.35 x 0.5 x 16 ] o (5.0 cm = 0.5 dm) = + 2.8 o.

Chiral Carbon

For a particular compound to be optically active, it must possess asymmetric center or chiral
center or stereogonic center all of this indicate the presence of chiral carbon atom(s).

A chiral carbon is one that does not possess any element of symmetry, it is attached to four
different atoms or group of atoms. Such C-atom is said to be non symmetrical
(asymmetrical, possesses no element of symmetry)

A and B above are mirror images becos of presence of asymmetric carbon center (a C-atom
connected to 4 different groups), they are none super-impossable mirror images. The none
super impossability of mirror images of a compound is a feature of optically active
compound. C & D possess element of symmetry becos at least 2 of the 4 atoms bonded to
the center C-atom are identical.

Identify chiral C-atom(s) in the following compounds

26
Stereogenic C-atoms & Number of Optical Isomers:

A compound with 1 chiral C-atom will have 2 isomers, which are mirror images; with 2 chiral
C-atoms, 4 isomers will be obtained. The number of optical isomers of a compound with n
chiral C-atoms is given by: 2n
2-hydroxyl-2-methylpentane [CH3CH(OH)CH(CH3)CH2CH3] a molecule with 2 chiral C-atoms
has 4 optical isomers as shown below:

Assignment

1. Draw the structure of glucose

2. How many chiral carbon atom does it have
3. How many optically active isomers does the glucose possess
4. Draw the structures of the isomers

Some important terminologies in Optical Isomerism

(i). Racemic Mixture (Racemate)

This is equimolar amounts of enantiomers i:e a mixiture of equal amount of +ve & -ve
isomers, the resultant optical activity is zero. This implies that a racemate has zero optical
activity i:e it is not optically active. Compounds a & b above are enantiomers therefore a
mixture of equal amounts of a & b will constitute a racemate

(ii) Diastereomers

These are optically active compounds which are not mirror images e.g: compounds a & c; b
& d; a & d; b & c above are diastereomers

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(iii) Meso compounds

These are compounds that contain chiral C-atoms but are not optically active due to internal
compensation, there is presence of element of symmetry within the molecule itself. 2,3-
dihydroxyl butane has 2 chiral centres so should have 4 isomers:

Compounds e & f above are optically active but g is not becos of presence of element of
symmetry (axis and plane of symmetry). Compound g therefore is a meso compound.

Resolution of a Racemate

Enantiomers are alike in every respect except in their action on polarized light. They are
therefore very difficult to separate, hence a racemate is difficult to separate. However, using
chemical means, a racemate can be resolved (separated) by 1st converting it to
diastereomeric mixture which can then be separated using chromatographic method:
Consider an acidic racemate [A(+),(-)]; react the racemic acid with a pure optically active
organic base of known optical activity e.g [B(+)]:

A(+)(-) + B(+) A+B+ + A-B+

Diastereomers can be seperated by

i. Fractional distillation
ii. Distillation
iii. Chromatography

A+B+ A-B+
H+ hydrolysis H+ hydrolysis

A+ + HB+ A- +
+ HB

NOTE: A meso compound cannot be resolved

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Determination of Absolute configuration

Polarimeter- is used to detect if a compound is optically active or not and to check if

positive or negative. However the absolute configuration of an optically active compound
can determined using R/S notation as proposed by Cahn Ingold and Prelog:

R/S Notation By Cahn Ingold Prelog Rule

i. Arrange the 4 groups around the chiral C-atom in order of increasing priority
based on atomic mass
ii. Visualize the molecule with the least priority group directed away from the
viewer
iii. View the remaining groups starting from the highest priority group to the least of
the 3groups
iv. Clockwise movement of view designate R configuration (+ve isomer);
anticlockwise movement of view means S configuration (-ve isomer)
Note

In this exercise, horizontal bonds are assumed pointing out of plane of paper, while
vertical bonds are assumed pointing inside the plane of paper.

R = +ve S= -ve

4
CH3
2 1
ClH2C OH
3
CH2CH3 S- isomer

Imagine horizontal pointing outward and vertical inward

1. Observe the molecule from the opposite end of the least priority.
R- Clockwise
S- Anti-clockwise
4
CH3
1 2
H O C CH2Cl

3 CH CH
2 3

R- isomer

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3 3
CH3 S CH3 CH3 S CH3
R R

H C OH HO C H H C OH HO C H
4 1 4 1
2 2
H C OH HO C H H C OH HO C H
R S R S
CH2OH CH2OH CH2OH CH2OH

1,2,3- trihydroxy butane 1,2,3- trihydroxy butane

Assignment

Assign E or Z configuration

1. 2.
BrH2C CH3C H COOH
C C C C
H3CH2C OH H3CH2C CH2Cl

3. Identify the chiral counter(s) in 1-bromo-1,2- dihydroxylpropane.

4. Determine the absolute configuration of the chiral centers in 3 above.

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