Inductive Effect

The inductive effect is a permanent state of polarization. The electron density in a  bond

between two unlike atoms is not uniform. The electron density is more dense toward the
more electronegative of the two atoms.
The inductive effect is a distance-dependent phenomenon:

The atom  above acquires a slightly negative charge  and the carbon atom a slightly positive
charge  which means the bond is polarized:

If the electronegative atom  is connected to a chain of carbon atoms, then the positive
charge is relayed to the other carbon atoms. , with its positive  charge, exerts a pull on the
electrons of , but the pull is weaker than it is between  on . The effect rapidly dies out and is
usually not significant after the  carbon atom, or at most the 

The inductive effect is permanent, but relatively weak, and can be easily overshadowed by
the electronic effects discussed later.

There are two categories of inductive effects: the electron-withdrawing (-I effect) and

the electron-releasing (+I effect). The latter is also called the electron-donating effect. In
the image above,  is electron-withdrawing and  is electron-donating.

These relative inductive effects are measured with reference to hydrogen:

 
-I effect:

The -I effect is seen around a more electronegative atom or group, and electron density is
higher there than elsewhere in the molecule. Electron-withdrawing groups include halogen,
nitro  cyano  carboxy  ester  and aryloxy 

 
+I effect:

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

Resonance
Sometimes, there are several correct Lewis structures for a given molecule. Ozone  is one
example. The compound is a chain of three oxygen atoms, and minimizing the charges
while giving each atom an octet of electrons requires that the central oxygen atom form a
single bond with one terminal oxygen and a double bond with the other terminal oxygen.
When drawing the Lewis structure, the choice of placement for the double bond is arbitrary,
and either choice is equally correct. The multiple correct ways of drawing the Lewis
structure are called the resonance forms.

Based on the resonance forms, a beginning chemistry student might wonder if ozone has
bonds of two different lengths, since single bonds are generally longer than double bonds.
However, the ozone molecule is perfectly symmetrical, with bonds that are the same length.
None of the resonance forms represent the true structure of the molecule. Rather, the
negative charge of the electrons that would form a double bond are delocalized, or
distributed evenly across the three oxygen atoms. The true structure is a composite, with
bonds shorter than what would be expected for single bonds, but longer than the expected
double bonds.

The resonance hybrid for ozone is

found by identifying the multiple resonance structures for the molecule.
Thus for  the two structures (I and II) shown above constitute the canonical structures or
resonance structures and their hybrid (i.e. the III structure) represents the structure of  more
accurately. Resonance is represented by a double-headed arrow between the resonance
structures, as illustrated above.

(1)

(2)
The resonance hybrid is more stable than its canonical forms, i.e. the actual compound
(hybrid) is at a lower energy state than its canonical forms. Resonance stability increases
with increased number of resonance structures.

The difference in the experimental and calculated energies is the amount of energy by
which the compound is stable. This difference is known as resonance energy or
delocalization energy.

All resonance structures are not equivalent. The following rules help determine whether or
not a resonance structure will contribute significantly to the hybrid structure.

Rules of Resonance

Rule 1: The most significant resonance contributor has the greatest number of full octets (or
if applicable, expanded octets).

Rule 2: The most significant resonance contributor has the fewest atoms with formal
charges.

Rule 3: If formal charges cannot be avoided, the most significant resonance contributor has
the negative formal charges on the most electronegative atoms, and the positive formal
charges on the least electronegative atoms.

Rule 4: The most significant resonance contributor has the greatest number of covalent
bonds.

Rule 5: If a pi bond is present, the most significant resonance contributor has this pi bond
between atoms of the same row of the periodic table (usually carbon pi bonded to boron,
carbon, nitrogen, oxygen, or fluorine).

Rule 6: Aromatic resonance contributors are more significant than resonance contributors
that are not aromatic.
Mesomeric Effect
The permanent polarization of a group conjugated with a  bond or a set of alternate  bonds
is transmitted through the  electrons of the system, resulting in a different distribution of
electrons in the unsaturated chain. This kind of electron distribution in unsaturated
compounds conjugated with electron-releasing or withdrawing groups or atoms is
called mesomeric effect.
As shown above, a polarity is induced in compounds due to transfer of electrons
through bonds. This effect is a consequence of resonance and is seen in compounds that
contain a double bond that is separated from another double bond or a lone pair of
electrons by a single bond.
Electromeric Effect
The electromeric effect is an intramolecular movement of electrons from a pi bond to
another atom in the molecule due to attack by a reagent. It is temporary and reversible.
There are two distinct types of electromeric effects:

(i) Positive Electromeric Effect (+E effect): In this effect the -electrons of the multiple
bond are transferred to that atom to which the reagent gets attached. For example:

(ii) Negative Electromeric Effect (-E effect): In this effect the -electrons of the multiple
bomd are transferred to that atom to which the attacking reagents do not get attached. For
example:

Hyperconjugation
Hyperconjugation helps explain the stability of alkyl radicals. It involves the delocalization
of -electrons belonging to the C-H bond of the alkyl group attaching to an atom with an
unshared orbital. The more the hyperconjugative hydrogen, the more is the stability.
SS

STARIC EFFECT

Steric effect is the influence of the spatial configuration of reacting substances upon the rate,
nature, and extent of reaction. The sizes and shapes of atoms and molecules, the electrical
charge distribution, and the geometry of bond angles influence the courses of chemical
reactions

here spatial configuration means the arrangement of molecules in a 3 dimensional space. it

looks something like this-
Think of a molecule like an elevator in regard to steric effects. If a bunch of people are too
close together, everybody is really unhappy, just like when atoms are close to each other in a
molecule. They need their personal space (electron cloud) to be free of other people. If you
put way too many people onto the elevator, it’ll break.

Molecules with large steric effects typically only exist for an extremely short period of time
as intermediates, but smaller steric effects are more associated with reactivity.

Same is the case with molecules.

when they are bonded this gives rise to electronic repulsions between them.
so when a external attacking reageant is introduced it becomes difficult for the regeant to
attack the active site of molecule.

In the above example you may see that its not possible for a bigger nucleophile OH- to
attack at central atom and give SN2 reaction. because of the presence of bulky groups OH-
RADICAL IS REPELLED.

2 .EXAMPLE-

IN THIS FIRST diagram is more sterically hindered because of presence of bulky -CH3
GROUPS than the second molecule