B.Sc. Sem. I, Chemistry P.II, 1.

Structure and Bonding SCSCO

Chapter –I
Structure and Bonding

Importance of Organic Chemistry: Organic Chemistry is defined as the study of carbon

compounds. Organic Chemistry is a separate discipline due to rapid increasing
compounds each year (Approx.5 million) and several thousand new compounds are
synthesized each year. In case of Inorganic Chemistry there are approximately 10,000
known Inorganic compounds. Secondly the unique physical and chemical property shown
by organic compounds which make organic chemistry separate branch more practical and
useful. Third is unique character of atom that is catenation property of carbon atom which
is responsible for the variety and large number of organic compounds. Thus no field of
science is as closely related with our daily activities as is organic chemistry. The food we
eat is mainly organic in nature. The changes which this food undergoes in our bodies are
organic chemical reactions metabolism, growth and maintain of our bodily functions
involves organic chemistry. The cloth we wear, the dyes that color them, the soaps and
starch used to launder them, the leather in our shoes, as well as the dye and shoe polish
are products of organic industry.

Many of the appointments in our motor cars, their fuels and lubricants and the fuel which
power our industrial plants are all organic in nature. The tremendous importance of
organic compounds in everyday life is given as,
Food: proteins, fats, carbohydrates etc.
Clothing: cotton, silk, wool, nylon, rayon, Dacron etc.
Shelter: wood, paints, varnishes etc.
Power and transportation: natural gas, petroleum products, coal etc.
Medicines and drugs: penicillin G, streptomycin, LSD etc.
Insecticides: Treflan, 2,4-D etc.
Hormones and steroids ,vitamins and enzymes, antiseptics and anesthetics, pigments and

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 1
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

dyes ,paper and inks Photographic film and developers, perfumes and flavors, plastics,
rubber and resins, explosives, soaps and detergents etc.
The course of civilization has been greatly affected by the advances in medicine; much of
the advance has been due to the introduction of such organic compounds as antiseptics,
anesthetics and antibiotics. Disease has been checked, the death rate reduced and the life
expectancy of mankind doubled within the last half century.
Introduction of Structure and bonding: At the heart of Organic Chemistry are
fundamental concepts of molecular structure and reactivity of carbon containing
compounds. The properties and reactions of organic compounds can be understood on the
basis of their structure. Structural theory plays an essentially central role in the study of
organic molecules. Chemists can use the theory of structure and bonding to explain the
physical and chemical properties of materials of widely varying composition e.g. salt
crystals, metals and polymer plastics and many more organic molecules...
Chemical bonding theory (covalent, ionic and metallic) explains how atoms are held
together in these different types of structure. The bonding and structure of substances
determine their properties .There are various elements which hold the greatest interest in
bonding with carbon to form various useful organic compounds.

Localized Chemical Bonding: Localized chemical bonding may be defined

as bonding in which the electrons are shared by two and only two nuclei. In this type of
bonding electrons that are restricted to a particular region. Localized electrons are not in
resonance. For example, covalent bond between two hydrogen atoms of H 2 molecule.
There is greatest possibility of finding electros in the region between the two nuclei.
Concentration of negatively charged electrons between the two positive nuclei that holds
the nuclei together. Since spins of the two electrons is antiparallel, this produces less
repulsion between two electrons, tending to concentrate them in the antinuclear region.
The net result is that the electron density for paired electrons is greatest between the two
nuclei. Due to localization of electron pair in a chemical bond gives rise the properties of
bond lengths, dipole moment, force constants etc.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 2
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

CH3 NH2 CH3 CH CH2

Localized electrons
Localized electrons

Delocalized chemical bond: A bond pair that moves between two different pairs of atoms is
considered delocalized. You can identify delocalized bonds by checking the electron locations in
two different resonance forms; if the pair changes location and form, it is delocalized.
Delocalization happens when electric charge is spread over more than one atom. The
term delocalization is general and can have slightly different meanings in different fields. In
organic chemistry, this refers to resonance in conjugated systems and aromatic compounds.

In the delocalized chemical bonding the electrons neither belongs to a single atom nor are
confines to a bond between two atoms, but are shared by three or more atoms.

It is process of bond formation involving delocalizes electrons. Delocalization is characteristics

of pi electrons, where the pi electrons change its position in between different sub orbital.
(Changes location).
Why delocalization occurs?
1) Delocalization is characteristics of pi bond.
2) It occurs due to presence of odd double and triple bond which is characteristics of
hybridization.
3) Delocalization involves sp2, sp3 and other complex hybridization.
4) Delocalization is carried out by forming delocalized bond to maintain the stability of the
molecule.
5) Delocalized bonding (resonance) exists for molecules that differ only in the allocation of
single and double bonds to the same kind of atoms.

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O -
CH3C
O - The Difference between Delocalized and Localized Electrons

Delocalized electrons can affect the reactivity of a compound for example Relative reactivity
toward HBr..

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CH3 CH3 CH3

CH2 C > CH2 C > CH2 C
OCH3 CH3 CH2OCH3
Other examples are,
1) Benzene: Benzene, a common organic solvent, is the simplest example of an aromatic
compound. ... Benzene is also a cyclic molecule in which all of the ring atoms are sp2-hybridized
that allows the π electrons to be delocalized in molecular orbital that extend all the way around
the ring, above and below the plane of the ring.

2) In Phenol:

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 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

3) In Amines and Nitro compounds:

4) In acetic acid:

5) In para nitro phenol:

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Charge transfer complexes (CT complex) or electron-donor-acceptor complex:

When two or more reactant combines with each other results in single product generally called
as addition reaction and product contains all the mass of two or more reactants, such product is
also called as addition compound.

1) In this type of complexes, one molecule acts as donor (D) and thus donates an unshared
pair of electrons or has pair of electrons in second orbit of double bond or aromatic
system.
2) Another molecule capable of accepting electron acts as acceptor (A).
When the two molecules combine due to attractive forces, a bond results between donor
and accepter molecule such an interaction is called as electron doner-accpter or Charge
transfer interaction and formed complex is known as electron donor-accepter (EDA) or
Charge transfer (CT) complex.
3) Speed of EDA formation: The formation of EDA complexes facilitated (fast formation)
by presence of electron withdrawing group(s) present on accepter molecule and electron
withdrawing group on donor molecule.
4) The distance between donor and acceptor is about 3-3.5 A0, which is larger than the
normal covalent bond length.
5) CTC shows dipole moment which indicates the charge separation in ground state of EDA
complex.
6) Examples are, A) toluene forms CTC with HCl at -78oC.Here pi electrons of pi electron
cloud (acts as donor) are responsible for formation of complex.

CH3 CH3

-780C
HCl HCl

Charge transfer complex.

B) Aromatic hydrocarbons also forms CTC complex with halogens and silver cations. for
example 2,4,6 trinitro phenol (Picric acid) forms CTC with silver cations.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 7
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

OH OH

NO2 NO2 NO2 NO2

Ag+ Ag+

NO2 NO2

2,4,6 tribromo phenol (Picric Acid) Charge transfer complex.

C) Benzene in the presence of Lewis acid like FeBr 3 reacts with Br2 to form bromobenzene.
Mechanism shows there is formation of EDA complex.

FeBr3 Br-Br--------FeBr3

Ferric bromide
Benzene (Lewis acid) Charge transfer complex.

D) Picric acid (A) forms stable colored crystalline CTC complex called as picrates, generally
with aromatic hydrocarbons (D) like Naphthalene and Anthracene. Bonding is possible
because as donor and accepter molecules lie in same plane/parallel plane.

OH OH

O2N NO2 O2N NO2

Warm

NO2 NO2

Benzene 2,4,6 trinitrophenol (Picric acid) Charge transfer complex.

(Donar) (Accepter)

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 8
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

Resonance effect or Mesomeric effect/Conjugative effect: Properties of a compound cannot

explain by a single Lewis structure. Two or more structure assigned to the compound which
differs in the arrangement of electrons of a pi bond or lone pair of electrons but none of them
represents true (Real) structure of a molecule. These hypothetical structures are called as
resonating or canonical structures. Phenomenon is known as resonance and effect is called as
resonance or mesomeric or conjugative effect. It is permanent effect.
Example 1)

Structure 2) cannonical structures of acetate anion.

Above the canonical structures are not real structures of acetate anion, its true structure is not
adequately represented by any single structure. Hence real structure represented by non
conventional Lewis structure that is resonance hybrid.

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 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

Example 2)

Example 3)

The polarity developed between atoms of a conjugated system by the electron transfer or
pi–bond electron transfer is known as the Mesomeric effect. In simple terms, we can describe
mesomeric effect occurs when π electrons move away from or towards a substituent group in a
conjugated orbital system. There are two types of mesomeric effects..
+M effect (Positive mesomeric effect) When the electrons or the pi electrons are transferred
from a particular group towards conjugate system, thus increasing the electron density of the
conjugated system then such a phenomenon is known as (+M) effect or positive mesomeric
effect. Example 1)

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 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

Example 2)

-M Effect (Negative mesomeric effect):

When the pi-bond electrons are transferred from the conjugate system to a particular group thus
the electron density of the conjugate system is decreased, then this phenomenon is known as
negative mesomeric (–M) effect.
1) Examples

Resonance effect or Mesomeric effect is permanent effect and they affect the physical as well as
chemical property of the compound. Resonance refers to delocalization of electrons in a given
system. Mesomeric effect is the electron donating or withdrawing nature of a substituent due
to resonance.

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Resonance hybrid structure is more stable than other canonical structures. It is denoted by double
headed arrow.

Conjugative effect is observed in Conjugated system which is a system of connected p orbital

with delocalized electrons in a molecule, which in general lowers the overall energy of the
molecule and increases stability. It is conventionally represented as having alternating single and
multiple bonds.

The difference in energy between the actual molecule and the canonical form of the lowest
energy is called as resonance energy.

Hyper conjugation effect: There are certain organic compounds which are stabilized due to
conjugation involving sigma electrons. This type of extended conjugation involving sigma
bond orbital (electrons of sigma bond), generally of C-H or C-X bond (X= halogens) is called
as hyper conjugation. Hyper conjugation effect is a permanent effect.
In propene molecule

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1) Structure II, III and IV are resonating structures, there is n covalent bond between carbon
and hydrogen atoms.
2) These structures possesses less number of covalent bonds than the main uncharged
structure -I .
3) Hence this type of hyper conjugation is also called as no bond resonance and resonating
structures are called as hyper conjugative structures.
4) Due to this effect ionic character of C-H sigma bond and partial delocalization of its
electrons increases.
5) Hyper conjugation decreases the bond length.
6) More the resonating structures more is the stability to the molecule.
7) For example Propene (3 hyper conjugative structures) is more stable than ethane (no hyper
conjugative structure).
Examples are 1)

H3C H3C H3C H3C H

CH3 H H H H

H3C H3C H H H

CH3 CH3 CH3 H H

1,1,2,2,tetramethyl ethene 1,1,2 tetramethyl ethene 1,2 dimethyl ethene 1-Methyl ethene Ethene
12 hyperconjugative 9 hyperconjugative 6 hypercojugative 3 hyperconjugatve No
structures structures structures structures hyperconjuga
tive structure

2) In Toluene stability can be explained by following hyper conjugative structures.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 13
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Inductive effects: Covalent bond between two atoms differs in their

electronegativities.Thu electrons are shifted towards more electronegative atoms, as a
result δ+ and δ-
Permanent displacement of electrons in a sigma bond due to presence of
electronegative atom or group and formation of partial polar molecule is called as
inductive effect denoted by ‘I’ and represented by arrowhead pointing towards
more electronegative atom.
For example in methyl bromide, due to inductive effect of Br atom, CH 3Br in ground state
becomes a partial polar molecule. Hence CH 3will bear δ+ charge and Br shows δ- charge.
CH3 Br
δ+ δ-
1) It is permanent effect and always transmitted along a chain of carbon atoms.
2) It decreases as the distance from the electronegative atom increases.Generally
inductive effect diminishes beyond carbon atom number four.
For example, in 1-bromo pentane,
CH3-CH2-CH2-CH2-CH2-Br

δδδδ+ δδδ+ δδ+ δ+

3) There are two types of Inductive effects
A) +Inductive effect (+I): Electron releasing (repelling) groups like -CH3,-C2H5,
- (CH3)2-CH,-OCH3 etc. are said to exhibit +I effect.
B) – Inductive effect (-I): Electron attracting (withdrawing) groups like –NO2, halogens,
-CHO, ˃C=O, SO3H,-CN, RCOOR etc. are said to exhibit -I effect.
Example
CH3

H3C C Br

CH3

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In the above example both effect observed one is +I, due to electron donating nature of –
CH3 group and second one is due to presence of –Br atom produces –I effect on central
carbon atom.
Applications of Inductive effect:
1) Effect of bond length: Inductive effect produces ionic character in the bond. The bond
length of covalent bond decreases with increase in inductive effect due to presence of
more electronegative atom or group.
Example 1) H3C-I 2) H3C-Br 3) H3C-Cl 4) H3C-F
Bond length 2.14 A0 1.94 A0 1.78 A0 1.38 A0
2) Dipole moment: Dipole moment increases with increase in inductive effect.
Example 1) H3C-I 2) H3C-Br 3) H3C-Cl
Dipole moment 1.64 D 1.79 D 1.83 D
3) Strength of Carboxylic acids:
Case I) when electronegative substituent particularly attached to the alpha ‘α’ carbon
atom of carboxylic acid (-I effect).
For example 1) Monochloroacetic acid is 100 times more acidic than acetic acid.
Explanation: H3C-COOH H3C-COO- + H+
Cl-H2C-COOH Cl-H2C-COO- + H+
Chloro acetic acid Chloro acetate anion
Due to(-) inductive effect of electronegative chlorine atom, electrons on oxygen atom
of chloro acetate anion are more delocalized resulting in more stability of mono
chloro acetate anion.
But in case of acetic acid, due to (+I) effect of –CH3 group, electrons on oxygen of
acetate anion are less delocalized resulting in less stability of acetate anion and hence
less acidic than mono chloro acetic acid.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 15
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For example 2) Tri chloro acetic acid is 7000 times more acidic than acetic acid.
Explanation: The greater number chlorine (Three Chlorine) atoms produces most
stable trichloro acetate ion, due to electrons on oxygen atom of tri chloro acetate anion
are more stabilized which results more stability for tri chloro acetate anion.

Case II) 2, 2 –dimethyl propanoic acid is less acidic than methanoic acid OR
Methanoic acid is more acidic than 2,2-dimethyl propanoic acid.

Explanation: The presence of greater number of alkyl groups on alpha ‘α’ carbon
atom of carboxylic acid (+I effect).Due to +I effect destabilize the corresponding
carboxylate anion resulting less ionization of carboxylic acid in the solution.
For example: Increasing order of acidity of alkyl substituted acetic acid can be
represented as,
CH3 H H
H3C CH3 H3C CH3 H
C COOH HCOOH
C COOH C COOH C COOH

H H
CH3 H

2,2-dimethyl propanoic 2-methyl propionic Proponic acid Ethanoic acid/ Methanoic acid/
acid acid Acetic acid Formic acid

Less acidic More acidic

Example 3) Acidity of Fluroacetic acid is greater than iodoacetic acid.

F-CH2-COOH Cl-CH2-COOH Br-CH2-COOH I-CH2-COOH

PKa 2.66 2.86 2.86 2.66

Explanation Fluroacetic acid is more acidic than chloroacetic acid, which is more acidic
than bromoacetic acid….In these halo acids, the halogen can stabilize the conjugate anion

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 16
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

via inductive delocalization. In an inductive effect, electronegative atom can draw

electron density toward them and stabilizes to anion.

Hydrogen Bonding: As hydrogen atom possess 1s orbital with one electron thus
expected to form only one covalent bond but it has been found to possess special ability
to form a link between two electronegative atoms.

One link is in the form of polar covalent bond with one electronegative atom and
another link is in the form of electrostatic attraction with another electronegative atom
(represented in the form of dotted line).
In a polar covalent bond between hydrogen atom and highly electronegative atom,
due to uneven sharing of electros, partial positive charge (δ+) develops on hydrogen
atom which electro statically attracts negative end of a group of the same or other
molecules forming a weak bond.
This type of weak bond formed due to dipole-dipole attraction is called a hydrogen
bond and is usually represented by dotted line.
As Hydrogen bond is being as electrostatic in character, it is weaker (Bond energy3-10
Kcal/mole) than a covalent bond (Bond energy 50-100 Kcal/mole).
Generally hydrogen bond is formed with more electronegative atoms like oxygen,
Nitrogen, Sulphur and Fluorine There are two types of Hydrogen bonding..
A) Intermolecular hydrogen bonding:(within different molecules) When hydrogen
bonding is observed in different molecule which exists in alcohols, carboxylic
acids, amines, HF and other compounds also.
For example In O-H group of alcohols, due to difference between
electronegativity of oxygen and hydrogen atoms, O-H bond becomes polar
covalent bond developing partial negative charge on oxygen and partial positive
charge on hydrogen (O-H). This partial positively charged H atom attracts –ve
oxygen atom of another alcohol molecule forming a hydrogen bond. This type of
electrostatic attraction between O-H group of alcohol; molecules continues
resulting in the formation of intermolecular hydrogen bonding.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 17
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1) An extra energy is required to break the intermolecular hydrogen bond. This

type of bonding increases the melting and boiling point of organic
molecules.
2) A substance is said to be soluble in water, if it is capable of forming hydrogen
bonding with water.
3) Alcohols (O-H) are capable of forming intermolecular hydrogen bonding with
water.
4) Alkanes, alkenes and alkynes due to less electronegativity difference
between carbon and hydrogen atom, do not possess partial polar groups and
hence do not form intermolecular hydrogen bonding with water molecules.
5) Hence alcohols are more soluble in water than hydrocarbons.
6) Intermolecular hydrogen bonding increases water solubility of the organic
compound.

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B) Intramolecular hydrogen bonding:(within same molecules)

It occurs within two atoms of the same molecule. This type of hydrogen bonding is
also called as chelation.
1) It is only possible when two groups are present at ortho positions in the same
molecule.
2) This type of hydrogen bonding restricts the possibility of intermolecular
hydrogen bonding and thus prevents molecular association which would have
risen melting and boiling points. Thus due to this Intramolecular hydrogen
bonding there is decrease in melting and boiling point.
3) For example, the m.pt of o-nitrophenol is 44oC, while m.pt. of p-nitrophenol is
114oC.
4) Intramolecular hydrogen bonding decreases solubility of organic compounds in
water due to chelation which prevents hydrogen bonding between the water and
the compound.
5) Examples are,

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Steric effect: The influence of inductive, conjugative or hyper conjugation effects on the
electron availability within the molecule may be modified or nullified by the operation of Steric
factor.
Steric effect is an influence on a reaction's course or rate determined by the fact that all of the
atoms within a molecule occupy space or due to the size of atoms or groups. Thus certain
collision paths are either disfavored or favored.

1) This effect operates via preventing the effective delocalization of pi-electrons in a

molecule or impending (incoming) the approach of a reagent to the reacting centre by
bulky groups.
2) Example 1) Why 2,6-dimethyl N,N-dimethyl aniline is more basic than N,N-
dimethyl aniline ?
Explanation: A) In this case both molecule possess lone pair of electron on nitrogen
atom .In N,N dimethyl aniline lone pair of electrons on N-atom gets delocalized over
benzene ring due to coplanarity between Pz orbital of N-atom containing lone pair of
electrons and Pz- orbitals of benzene ring. Hence lone pair of electrons on N-atom of
N,N dimethyl aniline is not readily available for basicity of this compound.
B) In 2,6-dimethyl N,N dimethyl aniline,due to presence of two bulky –CH3
groups at 2 and 6 positions (at ortho position with respect to (CH 3)2N group), as
a result of Steric hindrance, Pz orbital of N atom containing lone pair of
electrons and Pz orbital’s of benzene ring are prevented from becoming
parallel to each other and sidewise overlapping is inhibited.
C) As co planarity for effective delocalization is disturbed, lone pair of
electrons on N atom of this compound does not get delocalized over the
benzene and remains available on N atom to increase its basic strength.
D) Hence 2,6-dimethyl N,N dimethyl aniline is more basic than N,N dimethyl
aniline. It is shown by presenting structure of both molecules….

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 20
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

H3C
.. CH3
H3C ..
N
CH3 H3C
N
CH3
N

. effective
delocalisation

. .
etc..
. .
N,N-dimethyl aniline
.
Effective delocalization in N,N- dimethyl aniline

H3C ..
N
CH3 Steric hinderance

H3C CH3

No coplanarity,hence ,no effective delocalisation in

2,6-dimethyl N,N-dimethyl aniline.

2,6-dimethyl-N,N-dimethylaniline

Example 2) Esterification of aromatic acids:

Why 2,2-dimethyl propanoic acid and 2,6-dimethyl benzoic acid are not readily
esterifies?
This Esterification is not undergoes readily because –COOH group in both compounds is
sterically hindered by the adjacent two bulky methyl groups. But 2,6- dimethyl phenyl
acetic acid is readily esterifies because –COOH group is beyond Steric hindrance range
of –CH3 substitutes due to the presence of –CH2 group in between them.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 21
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

c e
eran
d
h in CH2-COOH
ric
S te
COOH

H3C CH3 H3C CH3

H3C CH3
C COOH

n ce
CH3 dra
hin
ric
Ste
2,2-dimethyl propanoic acid 2,6-dimehyl phenyl acetic acid (No
2,6-dimethyl benzoic acid
steric hindrance hence readily
(Not readily esterified) esterified)

Example 3) Nucleophilic substitution reaction with cyanide:

Example 4) ) Nucleophilic substitution reaction with KOH:

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 22
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

Department of Chemistry
Question Bank
Class: B.Sc. Semester –I
Name of Paper: Organic Chemistry (Paper –II) CHE-102
Title of Chapter: Structure and Bonding

Questions
1. What is resonance? What are main conditions of resonance/write resonating structure
of acetate anion?
2. Explain hyper conjugation? How will you explain the more stability f 2,3-dmethyl-2-
butane than 2-butane b hyper conjugative effect?
3. What is inductive effect? Explain with suitable examples, the effect of inductive effect
on strength of carboxylic acids?
4. What is Hydrogen bond? Explain different types of hydrogen bonding and their effect
on M.Pt. and B.Pt. of organic compounds?
5. Write a note on charge transfer complexes?
6. Why propene is more stable than ethane?
7. Why monochloroacetic acid is stronger acid than acetic acid?
8. Explain the Following
A) The presence of greater number of alkyl groups at alpha carbon atom of a
carboxylic acid decreases the acidity of a carboxylic acid?
B) 2,6- Dimethyl –N,N-dimethyl aniline is more basic than N,N-dimethyl aniline even
though nitrogen atoms of both compounds possess lone pair of electrons.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 23
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

C) 2,6-dimethyl benzoic acid is difficult but 2,6-dimethyl phenyl acetic acid can be easily
esterifies?
D) Alcohols are water soluble while higher alkanes are water insoluble?
E) M.P.of o-nitrophenol is 440C while M.P.of p-nitrophenol is 114 0C?
F) Picric acid can form picrate with benzene as addition compound?
G) Why trichloroacetic acid is 7000 times stronger acid than monochloroacetic acid?
9) Write short notes on followings:
A) Steric effect
B) Charge transfer complexes
C) Effect of Inductive effect on strength of carboxylic acids
D)Hyperconjugation
E) Intermolecular and Intramolecular hydrogen bonding
F) Localized and delocalized chemical bonding
G) Effect of steric hinderence on reactivity of compounds

Multiple choice Questions

1. Which of the following corresponds to an observed phenomenon that when atoms that are
forced to come close together and occupy the same space the energy of the system is overall
increased?
A. Electronic effect
B. Steric effect
C. Resonance effect
D. Delocalization effect
2. Why won't the following reaction take place as shown?

A) The two reactants are too sterically hindered i.e. there's too much steric strain with each
reactant
B) The Grignard reagent isn't reactive enough
C) The ketone needs to be activated more

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 24
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

D) D)There's no catalyst present

3. All bonds in benzene are equal due to…..

A) Tautomerrism
B) Inductive effect
C) Resonance effect
D) Isomerism
4. Inductive effect is ______.
A) Temporary
B) Permanent
C) Always temporary but permanent in specific condition
D) None of these.
5. Which one of the following orders is correct regarding the -I effect of substituent’s?
A) NR2 ˂OR˃ F
B) NR2 ˃OR˃ F
C) NR2 ˂OR˂ F
D) NR2˃ OR˂ F
6. Polarization of sigma bond caused by polarization of adjacent sigma bond is..

A) Mesomeric effect
B) Resonance effect
C) Inductive effect
D) none of these.
7. Which of the following occurs due to electronegativity difference?
A) Mesomeric effect
B) Resonance effect
C) Inductive effect
D) None of these
8.Choose correct decreasing order of -I effect..
A) NO3 ˃F˃ OCH3˃ C6H5
B) NO3 ˃ OCH3˃ F ˃ C6H5
C) NO3 ˃F˃ C6H5˃ OCH3

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 25
 B.Sc. Sem. I, Chemistry P.II, 1.Structure and Bonding SCSCO

D) NO3 ˃ C6H5 ˃ F˃ OCH3

9. State whether the following statements or True or False? Explain your choice.

i) Inductive effect is the ability of an atom or a group of atoms to cause polarization of electron
density along the covalent bond so that the atom of higher electronegativity becomes electron
deficient.

Ans: False. Inductive effect is the ability of an atom or a group of atoms to cause polarization of
electron density along the covalent bond, but the atom of higher electronegativity acquires
slightly higher electron density and becomes ö-.

ii) The –OH group cannot exhibit Inductive effect.

Ans: False. –OH group can exhibit mesomeric effect through donation of the lone pair when it is
bonded to a sp2 carbon, at the same time the oxygen through its higher electronegativity can
show Inductive effect. But the mesomeric effect when it is prevalent is predominating.

iii) Inductive effect can be responsible for the dipole moment in a molecule.

Ans: True. Dipole moment is charge times the distance separating the charge, Inductive effect
causes charge separation hence will have dipole moment. There are however examples of
molecules which have charge separation in a bond but the molecule has net zero dipole moment
due to symmetry induced cancellation.

iv) All alkyl groups exhibit –I effect.

Ans: False. All alkyl groups exhibit +I effect. An alkyl group pushes electron density away from
itself towards the carbon to which it is attached.

10. Select incorrect statement(s):

A) Electron-withdrawing inductive effect to the carbonyl group in —COOH group weakens the
O — H bond and favors ionization of a carboxylic acid compared with an alcohol
B) Inductive effect of the chlorine destabilizes the acid and stabilizes the conjugate base
C) Aniline is a weaker base than ammonia
D) Phenol is a weaker acid than water.
11.The + I effect is shown by
A) –CH3
B) -OH
C) -F
D) -C6H5

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 26
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12. The - I effect is shown by

A) –COOH
B) –CH3
C) - CH3CH2
D) –CHR2
13. The boiling point of water is exceptionally high because
A) there is a covalent bond between H and O
B) water molecule is linear
C) water molecules associate due to hydrogen bonding
D) water molecules are not linear.
14. Which one of the following elements is least likely to participate in a hydrogen bond?
A) O
B) F
C) S
D) N
15. Which one of the following represents the weakest interaction between two species?
A) Hydrogen bond
B) Disulfide bond
C) Ionic bond
D) Dispersion force
16. Which of the following compounds has the highest boiling point?
A) Methane CH4
B) Ethane C2H6
C) Ethanol CH3CH2OH
D) Dimethyl ether H3C-O-CH3
17. True or false:
A hydrogen bond forms a stronger chemical bond than a covalent bond.
18. In a water molecule, which atom(s) has/have a partial negative charge?
A) Oxygen
B) Hydrogen
C) None of the atoms

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 27
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D) All of the atoms

19. Hydrogen bonding occurs in molecules when ___________________.
A) Hydrogen atom forms a covalent bond with another atom.
B) Hydrogen atom in a molecule forms a bond with any atom.
C) Hydrogen atoms form an ionic bond with another atom on an adjacent molecule.
D) Hydrogen atom bonded to F, O or N is attracted to an electron pair on a F, O or N atom on an
adjacent molecule.
20. Which of the following is correct for formation of hydrogen bond…
A)-O-H-O-H-X
B) -O-H-----O-X
C) -O-H-----H-O-X
D) -O-H-----C-O-X
21.Which of the following statement is true? The number of intermolecular hydrogen bonds
between water molecules will be…
A) Maximum in ice and minimum in water vapor
B) Maximum in liquid water and minimum in water vapor
C) Minimum in liquid water and maximum in water vapor
D) Same in ice, liquid water and water vapor
22.Non polar molecules are insoluble in water. This is because….
A) Non polar molecules are uncharged
B) Non polar molecules cannot be ionized
C) Non polar molecules unable to form water-solute interaction
D)Hydrogen bonding is not possible with non polar molecules.

Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 28
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Dr. Suryawanshi Venkat S.-Dept. of Chemistry, Shri Chhatrapati Shivaji College, Omerga, (M.S.) 29