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Electronic Effects Applications Jee Main PDF
Electronic Effects Applications Jee Main PDF
1.
Inductive effect :
When a covalent bond is formed between the two atoms of different electronegativity then sigma bond pair
of electrons are shifted towards more electronegative atom as a result dipole is created between two
atoms. Due to this dipole, sigma bonded electrons in the carbon chain becomes polarised. Such
polarisation of bond caused by the polarisation of adjacent bond is referred to as the inductive effect.
Ex.
(v) CH bond is the reference of inductive effect i.e. polarity of CH bond is considered to be negligible.
Inductive effects are of two types :
(i) I effect :
The atom or group which withdraws electron clouds is known asI group and effect is calledI effect.
(ii) +I effect :
The group which releases or donates electron clouds is known as +I group & effect is called +I effect.
> C(CH3)3 > CH(CH3)2 > CH2CH3 > CH3 > T > D > H
CH2
CH2
CH3
2. HOOC
CH2
CH3
3.
4.
5.
6.
7.
8.
9. CH 3
CH
CH
NO2
<
2.
Resonance Effect :
It is a phenomenon in which a particular compound can be written in two or more structures with identical
position of atoms. These lewis structures are called resonating structure or canonical structure or contributing
structures.
Resonating structures
Resonance hybrid
(It is the actual structure)
Or
Or
The resonance structures are hypothetical and individually do not represent any real molecule. But they all
contribute to a real structure which is called resonance hybrid.
The resonance hybrid is more stable than any resonating structure.
The most stable resonating structure contribute maximum to the resonance hybrid and least stable resonating
structure contribute minimum to resonance hybrid.
JEE(MAIN) ELECTRONIC EFFECTS & APPLICATIONS - 2
Resonance energy :
The P.E. difference between the most stable resonating structure and resonance hybrid is called resonance
energy. The stability of molecule is directly proportional to resonance energy.
Types of Conjugation :
1. Conjugation between C = C and C = C (
CH = CH2)
)
CH3 CH = C = CH2
(iii) The no. of paired e are same and no. of unpaired electron are same in two resonating structures.
CH2 = CH CH = CH2
(iv) The octet rule is not violated (for second period element).
CH2 = CH
(v) High energy structures are rejected as resonating structure and their contribution to the resonance hybrid
is negligible.
Opposite charges on adjacent atoms and similar charges on adjacent atoms are cases of high energy.
These are not accepted as resonating structures.
CH2 = CH CH = CH2
O
||
(a) CH3 CH CH C CH3
..
(b) H 2 N CH CH C N
(c) CH3 O CH = CH
(d)
(azide ion)
(e)
N N N
(ii) The resonating structure with more no. of bonds is more stable and structure with complete octet of
each atom is more stable.
(a)
(b)
Note : If the rule of electronegativity and rule of octet are contradictory to each other then priority is given to the
octet rule.
(Stability order = II > I)
HO CH NH2
I
HO CH = NH2
II
(iv) Between two different compounds more conjugated is more stable (provided nature of bonding is same).
CH2=CHCH=CHCH2CH=CH2
CH2=CHCH=CHCH=CH CH3
(v) In two compounds if one is aromatic and another is non aromatic and conjugation is equal in both the
compounds then aromatic compound is more stable (nature of bonding is same)
(Stability order =
II (Aromatic)
(vi) Structure with linear conjugation is more stable than cross conjugation (nature of bonding is same).
Cross conjugation : If two groups are in conjugation with a particular group but not conjugated with each other
then the system is called cross conjugation.
CH2
linear conjugation
Cross conjugation
Note : Equivalent resonance structures make equal contributions to the hybrid and a system described by them
has a large resonance stabilzation.
(Stability order : )
3.
Mesomeric effect :
Mesomeric effect is defined as permanent effect of electron shifting from multiple bond to atom or from
multiple bond to single bond or from lone pair to single bond.
This effect mainly operates in conjugated system of double bond. So that this effect is also known as
conjugate effect and distance independent.
(ii) m effect
(a)
(b)
NO2 > CN > SO2R > CHO > C=O > COCR > COR > COOH > CONH2
||
||
||
O
JEE(MAIN) ELECTRONIC EFFECTS & APPLICATIONS - 5
(a)
(b)
H 2C CH = C = .N:.
H 2C = CH C N:
(c)
4.
Hyperconjugation :
When a sigma CH bond of sp3 hybridised carbon is in conjugation with -bond (p-orbital), half filled p-orbital
or vacant p-orbital, then the bond pair e of sigma CH bond overlap with adjacent p-orbital. This phenomenon
is called hyperconjugation. If may take place in alkene, alkynes, carbocations and carbon free radicals.
Like resonance hyperconjugation is also a stabilising effect but the effect of resonance is more dominating
than hyperconjugation, since in resonance only p-orbital overlap while in hyperconjugation molecular
orbitals overlap with p- molecular orbital.
Structure
+
H3C C CH3
CH3 CH = CH2
CH3
CH3 CH = CH CH3
H3C C CH3
+
CH3 CH2
CH3
H
CH2CH2
Hybrid Structure
CH 2 C H2
H
CH 2 = CH2
H3C
H3C
CH3
HHydrogenat ion
H3C
C = CH CH3
C=C
H3C
C = CH2
H3C
H3C
(ii) Heat of hydrogenation : Greater the number of hydrogen atoms, greater will be stability of
alkene. Thus greater extent of hyperconjugation results lower value of heat of hydrogenation (Hhydrogenation)
CH2 = CH2 > CH3 CH = CH2 > CH3 CH = CH CH3 (Heat of Hydrogenation)
(iii) Bond Length : Bond length is also affected by hyperconjugation
< CH3
(b) CH3
< CH3
>
>
< CH3
(b) CH3
< CH3
>
>
(due to resultant of inductive effect and hyperconjugation)
5.
Electromeric effects :
It is a temporary effect. It is defined as the complete transfer of a shared pair of -electrons to one of the
atoms joined by a multiple bond on the demand of an attacking reagent. The organic compound having a
multiple bond ( double or triple bond) show this effect in the presence of an attacking reagent only. It is
represented by E and the shifting of the electrons is shown by a curved arrow.
There are two types of eletromeric effect.
(i) +E effect : In this effect -electron of the multiple bond transferred to that atom to which the reagent gets
attached.
+
E
CH2 E
CH2 = CH2
(ii) E effect : In this effect the -electron of the multiple bond transferred to that atom to which the attacking
reagent does not get attached.
+
NC
When inductive and electromeric effects operate in opposite directions then the electromeric effect dominates.
JEE(MAIN) ELECTRONIC EFFECTS & APPLICATIONS - 7
6.
Anti Aromatic
compounds (B)
Non-Aromatic
compounds (C)
1. Structure
Cyclic or acyclic
planar,or non planar
sp or sp2 or sp3
3. MOT
Unpaired es in B.M.O.
4. Overlapping
Favourable over
lapping of p orbital
Unfavourable over
lapping of p orbital
Simple overlaping
like alkenes
5. Resonance
energy (R.E.)
Very high
R.E. > 20-25 kcal/mol
Zero
4-8 kcal/mol
like alkenes
Unstable
not-exist at
room temperature
Normal stability
like a conjugated
system
Dimerisation
reaction to attain
stability
Electrophilic addtion
reaction like alkenes
Characteristics
Example
6. Stability
7. Characteristic
Reactions
Electrophilic
substitution Reaction
B.M.O. / Non-bonding
M.O.
Stability of compounds = Aromatic compound > Non-Aromatic compound > Anti-Aromatic compound
Part B : GOC- II
7.
Reaction Intermediates :
A covalent bond can get cleaved either by : (i) Homolytic cleavage or (ii) Heterolytic cleavage
(i) Homolytic bond dissociation : A bond dissociation in which a bond pair electron is equally
distributed to the bonding atoms.
e.g., AB A + B
a homolytic bond dissociation generates radicals.
(ii) Hetrolytic bond dissociation : A bond dissociation in which a bond pair electron is shifted to one
atom only.
e.g., AB A + B
A hetrolytic bond dissociation always generate a cation and an anion.
(A)
Free Radicals :
Homolysis of covalent bond results into free radical intermediates possess the unpaired electrons.
(i)
(ii)
(iii)
(iv)
(v)
(vi)
stability order (C6H5)3 C > (C6H5)2 CH > C6H5 CH2 > CH2 = CH CH2 > 3 > 2 > 1 >
(B)
Carbocation :
A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation. It is a six
electron having electrodeficient, diamagnetic species and rearrangement can be possible if stability increases.
Hybridisation
Example
sp2
, CH3
sp
H2 C =
, HC
(iii) Hyperconjugation
(iv) + I effect
>
>
>
>
>
>
>
>
>
Note : (1) The carbocation is not possible at following bridge head positions I and II
(3) Cyclopropylmethylcarbonium ion is also more stable due to bond overlapping with empty p-orbital.
CH3
1
+
CH2
+
CH2
+
CH2
..
CH3 C O
..
4
OMe
(Stability order : 1 > 3 > 2)
(b)
OMe
OMe
+
(c)
(C)
Carbanion :
A carbon intermediate which contain three bond pair and a negative charge on it, is called carbanion.
Hybridisation : Carbanion carbon is in sp3 hybridised state if it is linked to sp3 hybridised carbon or hydrogen
atom, where as it will be in sp2 hybridised state if it is linked to sp2 hybridised C-atom due to resonance.
Hybridisation
Example
sp3
, CH3
sp2
H2 C =
sp
HC
, CH2 = CH
CH C ..
1
..
CH2
..
..
(b)
CH3
..
..
CH3
(c)
..
(d)
..
CCl3
1
(e)
(D)
..
CF3
2
N2 + : CH2
Types of carbene
(E)
CH2I2 + Zn
: CCl2
: CH2
CH2 = C = O
Singlet
: CH2 + CO
Triplet
Shape
Bent
Hybridisation
sp
Nature of reaction
stereospecific
None
State
Excited state
Ground state
Magnetic
Diamagnetic
Paramagnetic
Nature
Paired electrons
Diradical
Linear
sp
Nitrenes
The nitrogen analog of carbenes are nitrenes. They are very much reactive since in them octet of N is
incomplete.
In nitrenes only one valency of N is satisfied.
(F)
Benzyne
The benzene ring has one extra C C bond in benzyne
Clearly, we can see that the newly formed bond cannot enter in resonance with other orbitals of ring. since
it is in perpendicular plane.
It is also important to note that hybridisation of each carbon involved in 'Benzynic bond' is sp2 since the
overlap between these sp2 hybrid orbitals is not so much effective.
8.
Tautomerism :
Definition :
Tautomerism is a phenomenon by which a single compound exists in two or more readily interconvertible
structures that differ in the relative positions of at least one atomic nucleus, generally hydrogen.
These two isomers remain in dynamic equilibrium, can be isolated and also give different lab test.
Conditions :
1. Usually present in the following functional groups
2. Basic need for its existence is attachment of these groups with the sp3 hybridised C-atom having
atleast one hydrogen atom as
To get tautomer of above structures -hydrogen atom is shifting to more electronegative atom attached
to double bond (i.e. hydrogen atom from 1st atom to 3rd atom) and double bond is developed between
1,2-atom from 2,3-atom. This can be represented as :
H
CC = O
2 3
1
Keto
C = C OH
enol
These two forms (remain in equilibrium) are called tautomers of each other. The interconvertibility of
tautomers is a chemical reaction which involves making and breaking of bonds.
Ex.
O
||
(a) CH3 C CH3
( I)
OH
|
CH2 C CH3
( II)
(c)
(b)
(d)
Decreasing order of enol content for above carbonyl compounds is : 3 > 2 > 1.
(iii) For a carbonyl compound having active methylene group percentage of enol content will be more
because enolic form has intramolecular H-bonding and also it will be stabilised by resonance.
(iv) If active methylene group is more acidic then enol content will be more.
9.
Acidic Strength :
Definitions :
(1) Arrhenius Acid : The compounds which furnish H+ ion in aqueous solution are called Arrhenius acids.
Ex. H2SO4, HNO3, HCl, HClO4 etc.
(2) Bronsted Acids : The species, which are proton (H+ ion) donors, are called Bronsted acids.
Ex. NH4+ , H3O+, etc. All Arrhenius acids are Bronsted acids.
(3) Lewis Acids : The lone pair acceptors are known as lewis acids. They have vacant p or d orbitals.
Ex. BX3, AlX3, ZnX2 etc.
RCOO
(Conjugated base)
(Acid)
RCOO H
Ka
+H
RCOOH
A strong acid is defined as the acid which furnish more number of H+ ion in aqueous solution
So, a stronger acid has higher value of Ka , or it has lower value of pKa.
pKa = log Ka
More stable
ERG R C O
(+m, +I, H.C.)
O
Less stable
(A)
(Ka)
Conjugate base/Anion :
(stability)
(2) Along the group from top to bottom : As size of anion increases, Ka
HF < HCl < HBr < HI
(B)
> ROH > RC CH > Ph3CH > NH3 > RCH=CH2 > RCH2CH3
(C)
Acidity of Phenols :
The phenoxide ion is more stabilised by resonance than the unionised phenol.
Groups which are I, m increases acidic character of phenol because effectively dispersing the negative
charge of phenoxide ion. Alternatively + I and + m groups decreases acid strength.
Ex.
(a)
Ans.
Sol.
Step 1. III will be least acidic as it has no dispersion of negative charge (No delocalisation of negative
charge).
Step 2. since I, m group will increase acid strength, Nitrophenol will be most acidic followed by phenol,
Step 3. Amongst cresol and methoxyphenol, methoxyphenol has +m effect of OCH3 which increases e
density hence decrease acidic strength
Ex.
(b)
Ans.
Sol.
Step 1 : Notice that CH3 have + I effect so all methylphenols (cresols) are less acidic than phenol (I).
Step 2 : Now amongst cresols p- and o- CH3 are increasing the e density due to their hyper conjugation but
ortho isomer has viable + I effect also, which will help in destabilising phenoxide ion therefore o- is least
acidic. Since at meta position only + I works it as least e density amongst the cresol.
JEE(MAIN) ELECTRONIC EFFECTS & APPLICATIONS - 14
Ex.
(c)
Ans.
Sol.
(D)
Cl
Cl
Cl
(c) HCOOH > CH3COOH > CH3 CH2 COOH
COOH
(d)
COOH
COOH
> CH2
CH2 COOH
>
COOH
CH2 COOH
Ex.
Maleic acid :
Fumaric acid :
Now
K1 m > K1 f
Since the conjugate base is stabilised by intramolecular H bonding.
But
K2f > K2m Since in maleate ion, after donation of
two
makes system unstable. In fumarate ion this repulsion is less.
>
(ii) Electron withdrawing group attached to benzene ring will increase the acidic strength while electron
releasing group decreases acidic strength.
(iii) If electron donating group present at para position than it is always less acidic than benzoic acid and also
it is less acidic then meta substituted benzoic acid.
(a)
>
(b)
>
>
>
>
>
(v) On the other hand if e withdrawing group is present at meta position then it is more acidic than benzoic
acid.
(c)
>
>
>
>
Ortho effect :
It is common observation that generally ortho substituted benzoic acids are more acidic as compared to their
isomers and benzoic acids itself. This is called ortho effect (which is combined effect of steric hindrance,
crowding & electronic effect) in benzoic acid. However exceptions are seen.
Ex.
(a)
>
>
>
(b)
>
>
>
COOH
COOH
(c)
>
>
>
NO2
NO2
(d)
>
(e)
>
>
>
>
>
>
OH
(f)
Me
>
Me
NO2
OH
OH
NO2
NO2
(g)
NO2
>
>
O2N
NO2
O2N
NO2
NO2
NO2
(picric acid)
(E)
HY
Strong Acid
NaY
Salt of Strong acid
HX
Weak acid
Remark : A stronger acid displaces the weaker acid from weak acid metal salt. The weaker acid is
released out as a gas or liquid or precipitates out as a solid. The weaker acid cannot displace the
stronger acid from the salt.
(a)
(b)
(c)
(d)
Que.
(b) HC C Na + H2O
ONa
OH
(c)
SO3Na
(d)
COOH
+
NO2
Ans.
10.
Basic strength
(b) Possible
Definitions:
(a) Arrhenius base : Those compound which furinishes OH - ions in aquous solutions are known as
arrhenius base.
e.g. NaOH, KOH, Ca(OH)2 etc.
+
R O R
H
R O R + H+
NH4
NH 3 + H +
e.g.
+
R NH3 + OH Conjugate Acid (C.A.)
[RNH3 ][OH - ]
Kb =
[where Kb = Base dissociation constant].
[RNH2 ]
pKb = logKb
Note : A stronger base always has a weaker conjugate acid and vice versa.
Basic Strength in periodic table:(i) From left to right in a period, Eelectron Negativity of elements increases so, Kb
(ii) From top to bottom in a group, size increases so, Kb
CH 3- is strongest base in periodic table.
(d) - O H > - S H
(e) H2 O > H2 S
(A)
(B)
(E.N. , Kb )
(delocalised lone pair is less basic)
(better resonance due to ve charge on O)
CH2
(d)
<
(Resonance
Stabilisation)
(C)
(localised
ve charge)
N H3 + H N H4
Note : (1) Usually 1 amine is more basic than ammonia but if alkyl part of 1 amine is tertiary butyl then NH3 is
more basic due to steric hindrance caused by bulky nature of tertiary butyl group
RNH2 > NH3
;
(CH3)3 CNH2 < NH3
(2) Basic strength of nitrogeneous compound depends upon the hybridised state of nitrogen
RCH2 CH2 NH2 > R CH2 CH = NH > RCH = CHNH2
>
RCN
sp3 (localised)
sp2 (localised)
sp2 (delocalised)
sp
(3) More electronegative atom will decrease the basic strength
CH3CH2CH2NH2 > CH2=CHCH2NH2 > HCCCH2NH2
(4) Cyclic amines are more basic than acyclic amines of same nature
>
(5) Amidines are more basic in nature because their conjugate acid are more stable due to resonance.
(D)
N:
H
H
A.O. Diagram:
sp hybrid orbital
(localised lone pair)
S.F.:-
NH
(sp2)
S.F.:-
A.O. Diagram:-
NH
Complete delocalisation of e
Lone pair of N in pyrrole is delocalised in the aromaticity so it is very less basic than aniline.
>
>
N
H
H
:NH2
H
NH3
3
N sp (4e )
H
H
Aromatic
Non-aromatic
+
N
H
Aromatic
H2N:
H
+
HNH
G
(conjugate acid)
(i) Ortho-substituted anilines are mostly weaker bases than aniline itself.
(ii) Ortho-substituent causes steric hinderance to solvation in the product (conjugate acid i.e. cation).
(iii) The small groups like NH2 or OH do not experience (SIR) due to small size.
(a) G = (M, ); NO2
NH2
Ex.
NH2
CCl3
NH2
NH2
NH2
CCl3
CCl3
Only () decides the order.
(c) G = ( > + m); Cl
Cl
NH2
NH2
NH2
NH2
Cl
Cl
CH3
NH2
NH2
NH2
NH2
Ortho effect,
CH3
+
( HC
CH3
+I, +HC
more do min ating )
(E)
pKb
Na m e of a m ine
pKb
Methanamine
3.38
N,N-Diethylethanamine
3.25
N-Metheylmethanamine
3.27
Bebzenam ine
9.38
N, N-Dimethylmethanamine
4.22
Phenylmethanamine
4.70
Ethanamine
3..29
N-M ethylaniline
9.30
N-Ethylethanamine
3.00
N,N-Dimethylaniline
8.92
+
R N
R
OH2
OH2
| |
20
H
+|
N
H
R
OH2
Greater is the stability of the substituted ammonium cation, stronger should be the corresponding amine as
a base.
On the basis of above two sequences, we can say that the basic strength of amines is the combined effect
of inductive effect, steric hindrance and solvation.
R2NH > RNH2 > R3N > NH3
(if R = CH3)
......... (1)
R2NH > R3NH > RNH2 > NH3
(if R = C2H5)
..........(2)
(F)
Reaction of Bases :
(1) Nature of aqueous solution : Amines combine with water to form alkyl ammonium hydroxides. This
gives hydroxide ions in solution, thus the aqueous solution of amines is basic in nature.
(a)
R NH3 OH
RNH2 + HOH
[RNH3]+ + OH
1 Amine
(b)
R2NH + HOH
[R2NH2]+ + OH
R 2 NH2OH
2 Amine
The aqueous solution of amines behave like NH4OH and gives the precipitate of ferric hydroxide with ferric
chloride.
(c)
3RNH3OH + FeCl3
Fe(OH)3 + 3RNH3Cl
Brown ppt.
(ii) Aliphatic and aromatic amines form salt because of their basic nature:
(a)
RNH2 + H2O
R N H3 O H
Alkylammoniumhydroxide
(b)
RNH2 + HCI
R N H3 C I
Alkylammoniumchloride
(c)
RNH2 + H2SO4
( R NH3 )2 SO42
(d)
Aniliniumchloride Anilinehydrochloride
Salts of amines are ionic compounds and hence water soluble.
The amine salts react with base to give free amines as
R NH3 CI
+ OH RNH2
H2 O
CI
(Soluble in water)
What is a carbocation?
3.
4.
The central carbon atom of a free radical, carbocation and carbanion containing electrons in outermost shell
respectively.
5.
6.
7.
8.
(IV) (CH3)2CHCOOH
10.
Which has highest percentage of enol content in the solution phase. Write the structure of enol of that
compound.
(a) Acetone
(b) Acetophenone
(c) Acetic acid
(d) Acetyl acetone
11.
12.
(i) CH2=CHCH=CHCN
(ii)
(iii)
(iv)
13.
14.
The basic strength of aliphatic amines in solution is in the order sec. > ter. > primary. While in gaseous
phase the order is ter. > sec. > primary amine. Explain ?
15.
16.
(Q) Ph C Ph
||
O
(S) CH2=CHOH
NH2
NH2
CCl3
NH2
17.
(m)
(p)
CCl3
(Aniline)
(o)
CCl3
18.
(I)
(II)
(III)
(IV)
19.
Arrange the following carbocations in increasing order of their stability with reason.
For the following bond cleavages, use curved-arrows to show the electron flow and classify each as homolysis
or heterolysis. Identify reactive intermediate produced as free radical, carbocation and carbanion.
(a)
(b)
(c)
22.
CH3
|
23.
Cyclohexa -2,5-dien -1-one exists mainly in enol form. Which factor accounts for the stability of its enol form?
(b) Naphthalene
(c) Anthracene
(d) Phenanthrene
A-2.
A-3.
(1)
C OH
(2)
(3)
(4) CH3
CH2
CH3
CH3
A-4.
A-5.
A-6.
A-7.
A-8.
(4) CH3
(iv) Cl
(3) iii > ii > iv > i
II
CH3CH2NO2
(1) IV > III >I > II
CH3CH2Cl
III
CH3CH2Br
(3) I > III > IV > II
IV
CH3CH2
(4) I > II > III > IV
B-2.
B-3.
B-4.
(4) CH2=CHCH2CH=CH2
|
OH
B-5.
B-6.
(2)
(3)
(4)
(4) Benzene
+
(1) CH3 N
(3)
& CH3 O N = O
(2)
&
&
B-7.
B-8.
B-9.
B-10.
(2) 4
(tropylium cation) ?
(3) 5
(4) 7
(3)
(4)
(1)
O
+
(3) CH2CHCH=CHCCH3
O
(2) 2, 3
(1) 1, 4
B-11.
B-12.
(4)
(3) 4, 1
(4) 3, 2
(2)
(3)
(4)
HN C O
I
B-14.
+
CH2 CH = Cl :
C H2 CH = Cl :
: :
CH2 = CH
B-13.
Which of the following resonating structure will contribute minimum to resonance hybrid?
(1) I
(3) III
B-15.
(2) II
(4) All structures contribute equally
(i) C H2 CH=CHNH2
&
CH2=CHCH= NH2
(ii)
&
CH2=CHCH=CHCH=CH2
(iii)
&
(iv) CH2=CHCH=CHCH=CH2
&
CH2=CHCCH=CH2
CH2
(1)
(3)
B-16.
x
x
y
x
y
x
y
x
(2)
(4)
y
y
x
x
y
y
x
y
(1)
(2)
(3)
(4)
(3) electrons
C-3.
(i) O
(1) i > ii > iii > iv
C-4.
(iv) CHO
(4) iv > iii > ii > i
(ii) NH2
(iii) OH
(iv) NHCOCH3
(2)
(3)
(4)
C-5.
In which of the following molecule, the mesomeric effect is not with the benzne nucleus ?
NH
(1)
C-6.
C-7.
(2)
(3)
(4)
Cl
(I)
(II)
CH3
(III)
(IV)
NO2
Rank the following compounds in order of decreasing electron density in the benzene nucleus.
(I) Chlorobenzene
(II) 4-nitrochlorobenzene
(III) 2, 4-dinitrochlorobenzene
(IV) 2, 4, 6-trinitrochlorobenzene
(1) I > II > III > IV
(2) I > III > II > IV
(3) III > I > IV > II
(4) IV > III > II > I
D-2.
D-3.
(1)
D-4.
D-8.
(2) CH3CH=CH2
(3) CH3CH2CH=CH2
(4)
(2)
(3) CH3CH=CH2
(4)
The CC bond length in propene is little shorter (1.49 A ) than the CC bond length (1.54 A ) in ethane.
This is due to
(1) + effect of CH3
D-7.
(4)
D-6.
Which of the following alkenes will show maximum number of hyperconjugation forms ?
(1) CH2=CH2
D-5.
(4) (CH3)3C
I
(1) I < II < III
II
(2) II < I < III
III
(3) I < III < II
E-2.
..
O
..
(1)
E-3.
(4)
(2)
(3)
(4)
(1)
E-5.
(3)
E-4.
(2)
(2)
(3)
(4)
Which of the following molecules have all CC bonds are of equal length?
(1)
E-6.
(1) sp3
E-7.
(2)
(3)
(pyrrole) is :
(2) sp2
(3) sp
In the compound C6H5Z which of the following set of groups is predominatly ortho/para directing ?
(1) Z = NO2, Cl, OH
(2) Z = OMe, CN, NH2
(3) Z = NHCOCH3, Cl, COOH
(4) Z = NHCOCH3, CH3, OH
Part - II (GOC-II)
Section (F) : Carbon free radicals & carbocations :
F-1.
(2) Carbocation
(4) Free radical
F-2.In CH3CH2OH, the bond that undergoes heterolytic cleavage most readily is :
(1) CC
(2) CO
(3) CH
(4) OH
F-3.
F-4.
(i) CH3 C H2
(iii)
(iv) C H3
F-5.
F-6.
(1) CH3 C H2
F-7.
F-9.
(3) (CH3)2 C H
(4) (CH3)3 C
(3)
(4)
(1)
F-8.
(2)
(1)
(2)
(3)
(4)
(R = C2H5)
(1) Allyl carbocation (H2C=CHC H2) is more stable than propyl carbocation.
(2) Ethyl carbocation is more stable than allyl carbocation.
(3) Vinyl carbocation is more stable than ethyl carbocation.
(4) Benzyl carbocation is more stable than cyclopropyl methyl carbocation.
F-11.
<
<
<
<
<
F-12.
F-13.
(ii) CH2=CH C H2
(iii) C6H5 C H2
(1)
F-14.
(i)
(2) C 6H5 C H2
(3)
>
(2)
(3)
>
>
>
> CH3 C H2
>
> CH3 C H2
>
(4)
>
> CH3 C H2
Which of the following intermediates have the complete octet around the carbon atom ?
(1) Carbonium ion
(2) Carbanion
(3) Free radical
(4) Carbene
G-2.
(4) CH3
G-3.
G-4.
G-5.
G-6.
G-7.
O
(2) (ii) > (iii) > (i)
O
(3) (iii) > (ii) > (i)
C CH3
O
(ii)
(iii)
..
(i)
(ii)
(iii)
(iv)
(ii)
(iii)
(iv)
G-8
I
(1) III >
II
I > IV > II
III
II > I > IV
IV
IV
(1)
H-2.
(2)
(3)
(4)
CH3
|
(3) CH3CCH3
|
CHO
(4)
(3) R3CNO2
(4) RCH2NO2
CHO
(2) CH2
(1)
NO2
H-3.
H-4.
H-5.
Molecule
(1) xH
H-6.
H-7.
(2) yH
(3) zH
(i)
(ii)
(iii)
(iv)
(1) C 6H 5 C CH 2 C CH 3
O
(3) CH 3 C CH 2 CH 2 CH 3
(4) CH 3 C CH 2 COOC 2H 5
I-2.
(4) 102
(4) CH3OH
I-3.
(3) C2H6
I-4.
I-5.
I-6.
(4) CH3COOH
(3) CBr3COOH
I-8.
Which of the following option shows the correct order of decreasing acidity :
(1) PhCO2H > PhSO3H > PhCH2OH > PhOH
(2) PhSO3H > PhOH > PhCH2OH > PhCH2OH
(3) PhCO2H > PhOH > PhCH2OH > PhSO3H
(4) PhSO3H > PhCO2H > PhOH > PhCH2OH
I-9.
The correct order of relative acidic strength of phenol, ethtyl alcohol and water is(1) Phenol > Water > Ethyl alcohol
(2) Ethyl alcohol > Water > Phenol
(3) Ethyl alcohol > Phenol > Water
(4) Water > Phenol > Ethyl alcohol
I-10.
I-11.
I-12.
(I)
(II)
(III)
(IV)
In which of the following compounds the hydroxylic proton is the most acidic ?
F
O
I
O
H
O
(1)
(2)
(3)
(4)
H
F
H
Which of the following alcohol is the strongest acid ?
(1) CH3OH
(2) CH3CH2OH
(3) (CH3)2CHCH2OH
O
H
F
I-13.
I-14.
I-15.
I-16.
The reason for higher Ka1 value of oxalic acid () as compared to that of malonic acid () is :
(1) The anion formed after the removal of first Hof oxalic acid () is more stable due to stronger effect of
COOH present at close distance
(2) The anion formed after the removal of first Hof oxalic acid () is less stable due to +effect of COOH
group.
(3) The anion formed on removal of first Hof malonic acid is more stable than that of oxalic acid due to m
effect of other COOH group.
(4) Oxalic acid is more acidic than malonic acid due to its lesser molecular weight.
I-17.
I-18.
(3) cresol
OH
I -19.
(I)
(II)
(III)
(IV)
pka
9.98
7.23
8.40
7.15
Mark True and False statements related to the variation in pKa values given for the compounds mentioned
above ?
S1 : is more acidic than due to effect ofNO2 group.
S2 : due to Hbonding in , it is slightly less acidic than IV.
S3 : due to presences of m effect II & IV are more acidic than that of .
S4 : Mesomeric effect of NO2 group is not operative in case of with respect to OH group.
(1) TTTT
(2) TFTF
(3) FTFT
(4) FFTT
I-20.
(I)
(1) II > I > III > IV
(II)
(III)
(2) III > IV > I > II
(IV)
(3) I > IV > III > II
I-21.
(3)
(2) HC C Na + H2O
ONa
OH
SO3Na
(4)
COOH
+
NO2
J-2.
(3) RNH2
(4) NH3
(3) Ester
J-3.
J-4.
Which of the following shows the correct order of decreasing basicity in gas phase ?
(1) (CH3)3N > (CH3)2NH > CH3NH2 > NH3
(2) (CH3)2NH > (CH3)3N > CH3NH2 > NH3
(3) (CH3)2NH > CH3NH2 > (CH3)3N > NH3
(4) (CH3)2NH > CH3NH2 > NH3 > (CH3)3N
J-5.
Which of the following shows the correct order of decreasing basicity in aqueous medium ?
(1) (CH3)3N > (CH3)2NH > CH3NH2 > NH3
(2) (CH3)2NH > (CH3)3N > CH3NH2 > NH3
(3) (CH3)2NH > CH3NH2 > (CH3)3N > NH3
(4) (CH3)2NH > CH3NH2 > NH3 > (CH3)3N
J-6.
Which of the following shows the correct order of decreasing basicity in aqueous medium ?
(1) (C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3
(2) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
(3) (C2H5)2NH > C2H5NH2 > (C2H5)3N > NH3
(4) (C2H5)2NH > C2H5NH2 > NH3 > (C2H5)3N
J-7.
>
(2)
>
(3)
(4)
J-8.
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
(ii) CH2=CHNH2
(iii) CHCNH2
J-9.
(CH3)2NH
O
||
CH3 C NH2
(II)
(III)
(IV)
(I)
(1) (II) > (I) > (III) > (IV)
J-10.
J-12.
(2)
(3)
(4) CH3NHCH3
(ii) C6H5NHC6H5
(iii)
(iv) CH3CH2NH2
(3)
(4)
J-13.
J-11.
(2) NH
(5)
J-16.
I
(1) II < I < III
J-15.
II
(2) III < I < II
III
(3) III < II < I
(1)
(2)
(3)
(4)
2.
3.
4.
Statement-1 : Heterolytic fission involves the breaking of a covalent bond in such a way that both the
electrons of the shared pair are carried away by one of the atoms.
Statement-2 : Heterolytic fission occurs readily in polar covalent bonds.
5.
Statement-1 : Tertiary carbocations are generally formed more easily than primary carbocations.
Statement-2 : Hyperconjugation as well as inductive effect due to additional alkyl group stabilize tertiary
carbocations.
6.
Statement-1 : Allyl free radical is more stable than simple alkyl free radical.
Statement-2 : The allyl free radical is stabilized by resonance.
7.
8.
10.
11.
Statement-1 : Salicylic acid is much stronger than its m-, p-isomers and benzoic acid itself.
Statement-2 : It is due to steric inhibition to resonance of OH group to COOH.
12.
Statement-1 : Ortho substituted benzoic acids are stronger acid than benzoic acid.
Statement-2 : Ortho substituent tends to prevent coplanarity of COOH with ring. Thus resonance is
diminished which increases acidic strength (ortho effect)
13.
14.
(Q)
(1) PQS
2.
(R)
(S) CH3CH2
(2) PQR
MgBr
(3) PST
(T)
(4) PQT
(2) N H3
(1) N (CH3)3
(3) S (CH3)2
(4) F
3.
Which of the following statement is not true about the resonance contributing structures to a resonance
hybrid ?
(1) Contributing structures contribute to the resonance hybrid in proportion of their energies.
(2) Number of unpaired electrons remain same in the resonating structures.
(3) Contributing structures represent hypothetical molecules having no real existence.
(4) Contributing structures are less stable than the resonance hybrid.
4.
In
(1) 4
5.
(2) 2
(3) 3
(4) None
Which of the following resonance structures does not represent the correct stability order :
CH3
<
CH3 CH2 CH =
CH3
Which of the following series contains atoms/groups having only m (mesomeric) effect ?
(1) COR, OR, COOR
(2) Cl, CHO, NH2
(3) NO2,CN,SO3H
(4) OH,NR2,SR
7.
8.
(1)
9.
(4) CH3
(3)
(4)
Which of the following compounds has inductive, mesomeric and hyperconjugative effect ?
(1) CH3Cl
(2) CH3CH=CH2
(3) CH3 CH CH C CH3
||
O
(4) CH2=CHCH=CH2
10.
Which among the following statements are true with respect to electronic displacement in a covalent bond?
(a) Inductive effect operates through -bond
(b) Resonance effect operates through -bond
(c) Inductive effect operates through -bond
(d) Resonance effect operates through -bond
(e) Hyperconjugation involves CH sigma bond electrons
(1) a and c
(2) b and c
(3) b and d
(4) c, d and e
11.
Carbon-carbon double bond length will be maximum in which of the following compound ?
(1) CH3 CH
CH2
(2) CH3 CH
CH CH3
(3)
12.
13.
CH2
(1)
O
||a
b
(3) CH 3 C
OH
14.
(4) CH2
(b > a)
(b > a)
(2)
(b > a)
(4)
(a = b)
(Naphthalene)
(1) All the C-C bond length are same
(2) C1C2 bond length is shorter than C2C3 bond length
(3) C1C2 bond length is greater than C2C3 bond length
(4) All the C-C bond length are equal to C-C bond length of benzene
15.
The correct order of + m effect of N containing functional group on benzene ring, amongst the given compounds
is :
17.
O
(1) 2
18.
(2) 4
(3) 6
(4) 5
KOH
..
N
|
H
(I)
..
+
N
.. K + H2O
(II)
HCl
+
Cl
H H
(III)
(1) I is nonaromatic
(3) III is antiaromatic
(2) II is nonaromatic
(4) Out of I, II and III only III compound is nonaromatic
20.
21.
CH3H,
CH3CH2H
(CH3)2CHH
1(III)
(2)
2(IV)
3(V)
(3)
(4)
24.
(CH3)3CH,
23.
(1) CH3 CH = CH C H2
()
()
()
(V)
25.
(2)
+
+
(3)
26.
(4)
(2) O N
N=O
NO
+
..
(3) O = N
N=O
..
(4) O N
N=O
27.
(3)
28.
(2)
(4)
(a) CH2 C H
and
CH C
(1)
(2)
(b)
and
CH2 CH C H2
(1)
(2)
(c) CH3 C H CH C H2
and
C H2 CH CH2
(1)
(d)
and
(2)
CH2 CH CH CH
(1)
(1) (a) (2) (b) (1) (c) (2) (d) (1)
(3) (a) (1) (b) (2) (c) (2) (d) (1)
29.
(2)
(2) (a) (2) (b) (2) (c) (1) (d) (2)
(4) (a) (1) (b) (2) (c) (2) (d) (2)
In which of the following pairs of carbocations, the first carbocation is more stable than the second ?
30.
(1)
31.
(2)
(3)
(4)
(2)
(3)
(4)
32.
Which among the following compounds will give maximum enol content in solution :
(1) 3-hexanone
(2) 2, 4-hexanedione
(3) 2, 5-hexanedione
(4) 2, 3-hexanedione
33.
34.
Which of the following substituents will decrease the acidity of phenol (1) NO2
(2) CN
(3) CH3
(4) CHO
(3) BrCH2CH2COOH
(4) CH3CHBrCOOH
(3) Phenol
(4) o-Cresol
35.
36.
37.
38.
39.
(3) F(CH2)2COOH
(4) CH3(CH2)2COOH
40.
41.
42.
(I)
(II)
(III)
Which of the following compounds when dissolved in water, gives a solution with pH less than seven ?
(1) CH3COCH3
(2) C6H5OH
(3) C6H5NH2
(4) C2H5OH
JEE(MAIN) ELECTRONIC EFFECTS & APPLICATIONS - 42
44.
II
III
45.
46.
Which of the following correctly shows the order of decreasing basicity (1) Aniline > o-nitroaniline > p-nitroaniline > m-nitroaniline
(2) Aniline > p-nitroaniline > o-nitroaniline > m-nitroaniline
(3) Aniline > m-nitroaniline > p-nitroaniline > o-nitroaniline
(4) o-Nitroaniline > p-nitroaniline > aniline > m-nitroaniline
47.
48.
(I)
(II)
(III)
(IV)
COCH3
C2H5
49.
The pKa and pKb values of some bases are given below. Which represents the weakest base :
(1) pKb = 9.40
(2) pKa = 11.12
(3) pKa = 3.0
(4) pKb = 3.32
50.
(1)
+ NaHCO3
(2)
+ NaHCO3
(3)
(4)
+ NaHCO3
+ H2O + CO2
+ H2O + CO2
+ H2O + CO2
(2)
52.*
(P)
(Q)
(R)
(S)
Which of the following compounds arranged in their decreasing order of basic strength (Kb) ?
(1)
(2)
PhCH2NH2
PhNHPh
PhNH2
(3)
..
(4)
54.
..
CH2 N CH3 , CH 2 CH N H 2 ,
PART - II : COMPREHENSION
Comprehension # 1
Reaction intermediates : Reaction intermediates are short lived species and are highly reactive. They are
formed by heterolytic and homolytic bond fission. There are various types of reaction intermediates in which
the most important are carbocation, carbanion and free radical.
Carbocation is an organic species in which carbon have positive charge and six electrons in its outermost
shell. The stability of carbocation can be increased by positive inductive effect, hyperconjugation and
delocalisation. If -atom with respect to carbocation has one or more lone pair of electrons then lone pair of
electron strongly stabilises the carbocation due to octet completion.
Species in which carbon have negative charge is called carbanion. Carbanion carries three bond pairs and
one lone pair. The stability of carbanion can be increased by negative inductive effect, negative mesomeric
effect and delocalisation.
Free radical is a species which have seven electrons in its outermost shell. The stability of free radical can
be increased by hyperconjugation and delocalisation.
1.
2.
(1)
(2)
(3)
(4)
Comprehension # 2
The lone pair of amines makes them basic. They react with acids to form acid-base salts. Amines are more
basic than alcohols, ethers and water. When an amine is dissolved in water, an equilibrium is established,
where water acts as an acid and transfer a proton to the amine. The basic strength of an amine can be
measured by basicity constant Kb.
Arylamines are less basic than alkylamines because the lone pair of nitrogen is delocalised with the aromatic
ring and are less available for donation.
Substituted arylamines can be either more basic or less basic than aniline, depending on the substitutent.
ERG substituents, such as CH3, NH2 and OCH3 increases the basicity and EWG substituents, such as
Cl, NO2 and CN decreases basicity. While sp2-hybridized nitrogen atom in pyridine is less basic than the
sp3-hybridized nitrogen in an alkylamine.
4.
5.
6.
(II) NH2NH2
(III) NH3
(IV) H2O
Comprehension # 3
A stronger acid displaces the weaker acid from any metal salt. The weaker acid is released out as a gas or
liquid or precipitates out as a solid. The weaker acid cannot displace the stronger acid from the salt.
7.
(1)
(2)
H3 O + F
(III) HC N + H2O
H3O + CN
(IV) NH3 + H2O
NH4 + HO
According to the above reactions the correct acid strength order is :
(1) H2O > NH3 > HCN > HF > HCl
(2) HF > HCl > HCN > H2O > NH3
(3) HCl > HF > HCN > H2O > NH3
and
(R is alkyl group)
decreasing order of inductive effect is :
(1) (CH3)3 C > (CH3)2CH > CH3CH2
(3) (CH3)2CH > CH3CH2 > (CH3)3C
[AIEEE-2002]
(2) CH3CH2 > (CH3)2CH > (CH3)3C
(4) (CH3)3C > CH3CH2 > (CH3)2CH
2.
In the anion HCOO the two carbon-oxygen bonds are found to be of equal length. What is the reason for it?
(1) electronic orbitals of carbon atom are hybridised
[AIEEE 2003]
(2) the C=O bond is weaker than the CO bond
(3) the anion HCOO has two equivalent resonating structures
(4) the anion is obtained by removal of a proton from the acid molecule.
3.
The correct order of increasing basic nature for the bases NH3, CH3NH2 and (CH3)2NH is :
(1) CH3NH2 < NH3 < (CH3)2NH
(2) (CH3)2NH < NH3 < CH3NH2
(3) NH3 < CH3NH2 < (CH3)2NH
(4) CH3NH2 < (CH3)2NH < NH3
[AIEEE-2003]
4.
[AIEEE 2004]
(1)
5.
6.
(3)
(4)
(iii) p NO2C6H4COOH
(3) iii > ii > iv > i
[AIEEE 2004]
(iv) m NO2C6H4COOH
(4) ii > iv > iii > i
Among the following acid which has the lowest pKa value ?
(1) CH3CH2COOH
7.
(2)
[AIEEE-2005]
(3) HCOOH
(4) CH3COOH
[AIEEE-2005]
(4) Benzylamine
8.
< (CH3)2 H
[AIEEE 2006]
< (C6H5)3
< (CH3)2 H
< (C6H5)2 H
[AIEEE 2006]
Me
10.
11.
12.
(a) CH3CO2H
(b) MeOCH2CO2H
(c) CF3CO2H
(d)
CO2H is
Me
(4) a < d < c < b
[AIEEE 2007]
(4) Aniline
Arrange the carbanions, (CH3)3 C , C Cl3, (CH3)2 C H, C6H5 C H2 in order of their decreasing stability :
[AIEEE-2009, 4/144]
(1) (CH3)2 C H > C Cl3 > C6H5 C H2 > (CH3)3 C
The correct order of increasing basicity of the given conjugate bases (R = CH3) is :
(1) RCO O HC C R N H2
(2) R HC C RCO O N H2
(3) RCO O N H2 HC C R
(4) RCO O HC C N H2 R
[AIEEE-2010, 4/144]
13.
14.
[AIEEE-2011, 4/120]
(4) Phenol
15.
[AIEEE-2011]
(D) p-Nitrophenol
16.
[AIEEE-2011]
is :
[JEE(Mains)-2013]
Which of the following acid has the lowest value of acid dissociation constant :
[JEE-02(S), 3/90]
(A) CH3CHFCOOH
(B) FCH2CH2COOH
(C) BrCH2CH2COOH
(D) CH3CHBrCOOH
2.
3.
[JEE-03(M), 2/60]
4.
[JEE-03(S), 2/60]
(A)
5.
(B)
(C)
[JEE-03(S), 3/84]
(D)
[JEE-04(S), 3/84]
Excess of CH COONa
6.
[JEE-05(S), 3/84]
+ CH3COONa
(C)
7.
(B)
+ CH3COOH
+ CH3COOH
(D)
+ SO3
(A) CH2 = CH
(B) C H2
O CH3
(C) C H2 CH = CH CH =
CH = CH OCH3
(D) CH2 = CH
CH3
NaHCO
8.
[JEE-05(S), 3/84]
CH =
CH3
NaHCO
[JEE-06, 3/184]
Benzenesulphonic acid and para nitrophenol react with NaHCO3 separately. The gases produced are
respectively.
(A) SO2, CO2
(B) SO2, CO
(C) SO2, NO2
(D) CO2, CO2
9.
[JEE-07, 3/162]
(A)
(B)
+
N
(C)
+
N
(D)
10.
11.*
JEE-08, 3/163]
(D)
[JEE-08, 4/163]
12.
[JEE-08, 3/163]
[JEE-09, 3/160]
(A) (I) > (II) > (IV) > (III) (B) (I) > (III) > (II) > (IV) (C) (II) > (I) > (III) > (IV) (D) (III) > (I) > (IV) > (II)
14.
[JEE-09, 3/160]
(A) (III) > (IV) > (II) > (I) (B) (IV) > (III) > (I) > (II) (C) (III) > (II) > (I) > (IV) (D) (II) > (III) > (IV) > (I)
15.
In the following carbocation; H/CH3 that is most likely to migrate to the positiviely charged carbon is
[JEE-09, 3/160]
(B) H at C-4
(D) H at C-2
16.
17.
18.
The total number of contributing structures showing hyperconjugation (involving CH bonds) for the following
carbocation is
[JEE-11, 4/180]
19.
[JEE-10, 3/163]
[JEE-11, 3/180]
[JEE-12,3/136]
(D) aspirin
2.
For an amine RNH2 write the expression for Kb to indicate its base strength.
[CBSE 2000]
3.
[CBSE 2000]
4.
5.
Why is it that phenol is acidic and hexanol is netural towards a solution of NaOH ?
[CBSE-2001, 1999]
6.
Account for chloroacetic acids has lower pKa than acetic acid.
[CBSE-2005]
7.
[CBSE-2006]
8.
[CBSE-2006]
9.
10.
11.
12.
13.
14.
15.
Arrange the following compounds in an increasing order of their property as indicated : [CBSE 2012, 2 M]
(i) Benzoic acid, 3, 4-Dinitrobenzenoic acid, 4-Methoxybenzoic acid (acid strength)
(ii) CH3CH2CH (Br)COOH, CH3CH(Br) CH2COOH, (CH3)2CH COOH (acid strngth)
16.
Arrange the following in the decreasing order of their basic strength in aqueous solutions :
CH3NH2, (CH3)2NH, (CH3)3N and NH3
[CBSE 2012, 1 M]
[CBSE 2008]
[CBSE 2009]
[CBSE 2011, 1 M]