Type (I) : Very Short Answer Type Questions : [01 Mark Each]

1. What is a homolytic cleavage? The homolytic fission of C–C bond in ethane produces :

2. What is a carbocation?

I
3. What are free radical reactions?

4. The central carbon atom of a free radical, carbocation and carbanion containing electrons in outermost shell
respectively.

5. Give reason why the following two structures I and II cannot be the major contributors to the real structure of
CH3COOCH3.

6. Identify electrophilic centre in the following :

(i) CH3CH=O (ii) CH3CN

Type (II) : Short Answer Type Questions :

7.

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(iii) CH3I (iv) CH3COOH

[02 Marks Each]

Write resonance structures of CH2=CH–CHO. Indicate relative stability of the contributing structures.

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8. Arrange the following carbocation in increasing order of their stability with reason.

9. Explain why alkyl groups act as electron donors when attached to a -system.

10. Write a stable resonating structure for each of the following compounds :

C
(i) CH2=CH–CH=CH–CN (ii) (iii) (iv)

11. Draw all the hyperconjugating structures of toluene.

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12. Relative stabilities of the following carbocation will be in order.

13. Arrange the following carbocations in increasing order of their stability with reason.
Type (III) : Long Answer Type Questions : [03 Marks Each]

14. Draw the resonance structures for the following compounds. Show the electron shift using curved arrow
notation.
(a) C6H5OH (b) C6H5NO2 (c) CH3CH=CHCHO (d) C6H5–CHO

(e) C6H5– (f) CH3CH=

I
15. What are hybridisation states of each carbon atom in the following compounds ?
CH2=C=O, CH3CH=CH2, CH2=CHCN, C6H6 , (CH3)2CO, HCONH2

16. 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, carbanion and carbocation.

(a) (b)

S
(c)

CH3

|
17. CH3  C C  CH3 The given carbocation rearranges into :
| |
H3 C OH

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Type (IV) : Very Long Answer Type Questions: [05 Marks Each]

18. Draw all the resonating structures of the following compounds :

(a) Benzene (b) Naphthalene
(c) Anthracene (d) Phenanthrene

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PART - I : SUBJECTIVE QUESTIONS
Section (A) : Inductive effect

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A-1. Show the direction of inductive effect in following compounds

(1) (2) (3)

(4) (5) (6)

(7) (8) (9)

(10) (11) (12)

(13) (14) (15)

(16)

(19)

B-1.
(17)

(20)

S I (18)

Section (B) : Resonance Concepts, Conditions, Resonating Structures & Conjugation

Which of the following compounds have delocalized electrons ?
O

M
||
(P) CH2  CHCCH 3 (Q) (R) (S) CH3CH2NHCH = CHCH3

B-2. Number of  electrons in resonance in the following structure is.

C
Section (C) : Stability of Resonating Structures and different species
C-1. In the following sets of resonating structure, label the major and minor contributors towards resonance
hybrid.

(P)

(Q)

(R)

(S)
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C-2. Write the stability order of following resonating structures :
I II I II

(P) (Q)

D-2.
(R)

Section (D) : Mesomeric Effect

D-1.
(i) I, Cl, F, Br (ii) –NH2, –OH,
(S)

S I
Arrange the following groups in the increasing order of +m :

Arrange the following groups in the increasing order of –m :

(i) –NO2, –COOR, –CHO, –CN, –COR (ii) , ,

M
D-3. Classify the following groups as +m, –m, ±m, +I, –I ?
(i) –NO2 (ii) –OH (iii) –ONO
(iv) –NO (v) (vi) –SO3H

D-4. Classify the following groups as +m, –m, ±m, +I, –I ?

(i) –S–R (ii) (iii)

(iv) –Cl (v) –CF3 (vi) –B(OH)3

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D-5. How many groups (attached with benzene ring) show + M effect?

E-2.
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Section (E) : Steric Inhibition of Resonance (SIR Effect)
E-1. Explain the SIR effect.
Compare the SIR effect between orthochloro benzoic acid, orthobromobenzoic acid and orthoiodo benzoic
acid.
Section (F) : Hyperconjugation
F-1. Define hyperconjugation by taking an example of propene.

F-2. In which molecules or ions hyperconjugation effect is observed and write the number of hyperconjugable
hydrogen atoms.

I
(A) C6H5 – CH = CH2 (B) CH3 – CH2 – CH = CH2 (C) CH2 = CH2 (D)

CH3 C 2H5 CH3

|  | |
(E ) (F) CH3 — C — C H2 (G) C 2H5 — C  (H) CH3 — C 
| | |
CH3 C 2H5 CH3

S
(I) (J) (K) (L)

Section (G) : Applications of electronic effects

G-1. The correct decreasing order of electron density in aromatic ring of following compounds is :

O O O
|| || ||
O–C–H C – NH – CH3

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C–H NH – CH3

(I) (II) (III) (IV)

G-2. Correct dipole moment order is

C
(p) (q) (r)

G-3. Identify the relation between given pairs :

G-4.
(a)

(c)

J ,
, (b) ,

(d) CH3–CH=CH–CH3 ,

Find the total number of the position where positive charge can be delocalized by true resonance

. (Excluding the given position)

Section (H) : Concept of Aromaticity
H-1. What is aromaticity ?
H-2. Classify the following as aromatic, antiaromatic and nonaromatic compounds.

(a) (b) (c) (d) (e)

H-3.
(f)

(k)
(g)

(l)

Why cyclooctatetraene is nonplanar.

Section (I) : Carbocations

I-1.
(h)

S
(m)
I
Arrange the following carbocations in decreasing order of their stability :
(I) (II) (III)
(i)

(n)
(j)

(IV)

M
   
(P) CH3—CH2— CH2 CH3 — CH — CH2 CH3 — CH — CH2 CH3 — CH — CH2
| | |
F Br Cl

   
(Q) CH3 – CH2 – C H2 CH3 – C H – CH2 – CH3 (CH3 )3 C C H3

(R)

C
I-2. Write the stability order of following carbocations with proper reason.
I II III IV

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I-3. Which of the following carbocation is more stable and why ?

(I) (II)

I-4. Draw the structures of P and Q.

Section (J) : Carbanions
J-1. Arrange the following in decreasing order of stability.

(a)

I
(b)

J-2. Arrange the following in decreasing order of stability.

..
.. CH3

–
(a) ..
.. CH3

–
1 2 3 4

S
(b)

.. ..
(c) CCl3 CF3
1 2

Section (K) : Carbon free radicals

K-1. Rank the following free radical in increasing order of their stability and give appropriate reasons.

K-2.

CH3 – CH2
I

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Arrange the following free radical in decreasing order of stability :

CH3
IV

C
PART - II : OBJECTIVE QUESTIONS
* Marked Questions may have more than one correct option -

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Section (A) : Inductive effect
A-1. Inductive effect involves :
(A) Delocalisation of  - electrons (B) Partial displacement of  - electrons
(C) Delocalisation of  - electrons (D) Displacement of lone pair electrons.

A-2. Select correct statement about I effect?

(A) I effect transfers electrons from one carbon atom to another.
(B) I effect is the polarisation of  bond electrons.
(C) I effect creates net charge in the molecule.
(D) I effect is distance independent.

A-3. Which of the following group shows +I-effect :

(A) –Br (B) –COOH (C) –OR (D) –COO–

A-4. Which of the following alkyl groups has the maximum +I effect ?
(A) (CH3)2CH– (B) (CH3)3C– (C) CH3CH2– (D) CH3–
A-5. Decreasing –I effect of given groups is :
(i) CN (ii) NO2 (iii) NH2 (iv) F
(A) iii > ii > i > iv (B) ii > iii > iv > i (C) iii > ii > iv > i (D) ii > i > iv > iii

A-6. Which of the following is the strongest -  group :

  

I
(A) – N (CH3)3 (B) – N H3 (C) – S (CH3)2 (D) – F

A-7. In which of the following species, incorrect direction of Inductive effect is shown ?

CH3 O O
-
C – OH C O

(A) (B) (C) (D)

S
CH3
Section (B) : Resonance Concepts, Conditions, Resonating Structures & Conjugation
B-1. The notation for relating two resonating structures is :
(A) (B) (C) (D)

B-2. Resonance is delocalisation of :

(A)  electrons (B)  electrons (C)  electrons (D) None

B-3. Resonance effect involves :

(A) Delocalization of –electrons along a conjugated system.

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(B) Delocalization of lone pair along a conjugated system.
(C) Delocalization of negative charge along a conjugated system.
(D) All are correct.

B-4. During delocalization, which statement is incorrect :

(A) Net charge remains same (B) Number of paired electrons remain same
(C) Number of unpaired electrons remain same (D) Energy of resonating structures always remains same

B-5. Which of the following statements is incorrect ?

(A) The energy of resonance hybrid is always less than that of any resonating structure.

C
(B) The resonance energy is the difference between the enthalpies of formation of the molecule and the
resonating structure having maximum energy.
(C) The resonance structures are hypothetical structure and they do not represent any real molecule.
(D) In delocalized structure of benzene the -charge cloud is spread equally above and below the plane of
molecule.

B-6. Which of the following statement regarding resonance is NOT correct ?

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(A) the different resonating structures of a molecule have fixed arrangement of atomic nuclei.
(B) the different resonating structures differ in the arrangement of electrons.
(C) the hybrid structure has equal contribution from all the resonating structures always.
(D) None of the individual resonating structure explains all characteristics of the molecule.
B-7. Resonance energy is :
(A) The potential energy difference between most stable resonating structure and resonance hybrid
(B) The potential energy difference between the least stable resonating structure and resonance hybrid.
(C) The potential energy difference between the least stable and most stable resonating structure.
(D) None
B-8. Resonance structure of the molecule does not have
(A) higher energy than their hybrid structure.
(B) identical arrangement of atoms.
(C) the same number of paired electrons.
(D) always equal contribution to the resonance hybrid.
B-9. Which of the following species can not show resonance?

(A) (B) (C) (D)

B-10. Resonance is not possible in :

I
(A) (B) (C) CH2=CH–Cl (D)

B-11. Which does not have conjugate system ?

(A) CH2 = CHCl (B) CH2 = CHCHO (C) CH3CH = CH2 (D)

B-12. The compound which is not resonance stabilised

S
(A) CH2=CH–Cl (B) (C) CH2=CH–CH2–Cl (D)

B-13. Which of the following is not acceptable as resonating structure :

(A) (B) (C) (D) None of these

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B-14. Which of the following pair is not pair of resonating structures?

(A) & (B) CH2 = CH – O– & CH2 – CH  O

   
(C) CH2 = CH – O – CH3 & CH2 – CH  O– CH3 (D) CH3 – C  O & CH3 – C  O

B-15. Which of the following structures constitute resonance structures ?

C
(A) & CH3 – O – N = O (B) &

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(C) (CH3)2 CO & (D) CH3 – CH = CH – CH3 & CH3 – CH2 – CH = CH2

B-16. Among the given sets, which represents the resonating structure ?

(A) and (B) and

(C) and (D) and

B-17. In which of the following resonance is not possible?

(A) CH2 = C = CH2 (B) CH2 = C = CH (C) CH2 = C = CH (D) CH2 = C =
Section (C) : Stability of Resonating Structures and different species
C-1. In which of the following first resonating structure is more stable than the second ?

(A)  (B) 

(C) CH2=CH–NH2  (D) 

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C-2. Which one of the following is least stable resonating structure ?

(A) (B)

(C) (D)

S
C-3. Which of the following resonating structure of 1-Methoxy-1,3-butadiene is least stable ?
+ +
(A) CH2 – CH = CH – CH = O – CH3 (B) CH2 = CH – CH – CH = O – CH3
+ +
(C) CH2 – CH – CH = CH – O – CH3 (D) CH2 = CH – CH – CH – OCH3

C-4. Which of the following resonating structure is the least contributing structure ?

(A) (B)

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(C) (D)

C-5. HNCO (isocyanic acid) has following resonating structures :

HN  C  O  

I

C
The order of stablity is :
(A) I > III > II (B) I > II > III (C) II > III > I (D) II > I > III

C-6. The correct stability order of the following resonance structures is :

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(A) (IV) > (I) > (III) > (II) (B) (II) > (IV) > (I) > (III)
(C) (III) > (II) > (IV) > (I) (D) (I) > (IV) > (III) > (II)

C-7. Which of the following is least stable resonating structure ?

(A) (B)

(C) (D)

C-8. Which is the most stable resonating structure ?

(A) (B) (C) (D)

C-9. The correct stability order of given resonating structures is :

I
(A) I > II > III > IV (B) IV > III > II > I (C) I = II = III = IV (D) II = III > I = IV
C-10. Which of the following is incorrect for stability of structures.

O¯ O¯
| | 
(A) CH3  CH  CH  CH2 > CH3  C  CH  CH3 (B) CH2  CH  CH  CH  C H2 >

S
(C) > (D) <

C-11. In which of the following pairs of first species is more stable than second.

(A) , (B) ,

(C) , (D) ,

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Section (D) : Mesomeric Effect
D-1. Which of the following group show +m effect?
(A) –CN (B) –O–NO (C) –CCl3 (D) –CHO
D-2. Which of the following group show –m effect?

(A) –CMe3 (B) (C) (D)

C
D-3. Which of the following group show +m and –I effect ?
(A) (B) (C) –O (D) –OH

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D-4. Which of the following group show +m > –I effect ?

(A) –F (B) (C) (D) –COOH

D-5. Which of the following group show –m and –I effect ?

(A) –NO2 (B) –NH2 (C) –OH (D) –Cl

D-6. Identify which of the following group acts as +m as well as –m ?

(A) –F (B) –NH2 (C) –Cl (D) –OH

D-7. +m and +I both effects are shown by :

(A) (B) (C) (D) – C (CH3)3
D-8. The weakest + m group of the given species is :
(A) – OCH3 (B) – F (C) – I (D) – N (CH3)2
Section (E) : Steric Inhibition of Resonance (SIR Effect)
E-1. Maximum extent of steric inhibition of resonance can be expected in

(A) (B) (C) (D)

I
E-2. Select the correct statement about this compound.

NO2
3

1 5

NO2 NO2
Br

S
(A) All three C–N bond length are same.
(B) C1–N and C3–N bonds length are same but shorter than C5–N bond length.
(C) C1–N and C5–N bonds length are same but longer than C3–N bond length.
(D) C1–N and C3–N bonds length are different but both are longer than C5–N bond length.
E-3. The longest C — N bond length in the given compound is :

F-1.
(A) x

Section (F) : Hyperconjugation

(B) y

In hyperconjugation there is overlap between :

(A) p- and -orbitals (B) 2  - orbitals

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(C) z

(C) d-and--orbtial
(D) w

(D) -and p - orbitals

C
F-2. Which of the following cannot exhibit hyperconjugation -

(A) CH3 C H2 (B) (C) CH3CH = CH2 (D)

F-3. Which of the following alkenes will show maximum number of hyperconjugation forms ?

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(A) CH2 = CH2 (B) CH3–CH=CH2 (C) CH3–CH2–CH=CH2 (D)

F-4. Arrange the stability of following

I II III
(A) I < II < III (B) II < I < III (C) I < III < II (D) II < III < I
F-5. The order of heat of hydrogenation in following compound is :

(I) (II) (III) (IV)

(A) I < II < IV < III (B) III < IV < II < I (C) II < III < I < IV (D) II < IV < I < III
F-6. does not involve :
(A) –p overlap (B) – overlap (C) p–p overlap (D) p–d overlap
F-7. Which one of the following has inductive, mesomeric and hyperconjugation effect ?
(A) CH3Cl (B) CH3–CH=CH2

(C) CH3CH= CH – C – CH3 (D) CH2 = CH – CH = CH2

I
||
O

Section (G) : Applications of electronic effect

G-1. The decreasing order of electron density on the ring is :

G-2.
(A) III > II > I

Correct dipole moment order is

(p)
(B) II > III > I

(q)

S
(C) I > III > II

(r)
(D) III > I > II

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(A) p > q > r (B) r > q > p (C) q > r > p (D) p > r > q

G-3. Arrange following compounds in decreasing order of their dipole moment.

I II III IV
CH3—CH2—NO2 CH3—CH2—NH2 CH3—CH2—F CH3—CH2—CN

(A) IV > III >I > II (B) IV > I > III > II

C
(C) I > III > IV > II (D) I > IV > III > II
G-4. The decreasing order of bond length of C = C bond in the following compounds is:

J
I II III IV
(A) II > I > IV > III (B) III > I > II > IV
(C) IV > II > I > III (D) IV > I > II > III

G-5. Decreasing order of bond length of C = C bond in the following compound?

(A) p > q > r (B) r > q > p

(C) p > r > q (D) q > r > p
G-6. In which of the following C = C bond length is minimum :

(A) (B) C=CH2 (C) CH2 = CH – N (D)

G-7. Which of the following is correct about the following compound

I
(Naphthalene)
(A) All the C-C bond length are same
(B) C1–C2 bond length is shorter than C2–C3 bond length
(C) C1–C2 bond length is greater than C2–C3 bond length
(D) All the C-C bond length are equal to C-C bond length of benzene

S
G-8. The stability order of alkene in following compounds is :

(I) (II) (III) (IV)

(A) I < II < III < IV (B) II < I < III < IV (C) II < III < I < IV (D) II < IV < I < III

G-9. Observe the following statements and choose the correct option.
S1 : Inductive effect is more powerful than mesomeric effect.
S2 : The bond polarity order of bonds a, b, and c in the given molecule (I) is c > a > b

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b CH2–CH=CH2
Ph–CH2 a CH
c CH2–CCH
(I )
S3 : The hybrid structure has always have equal contribution from all the resonating structures.

S4 : shows inductive effect, resonance, hyperconjugation & intramolecular hydrogen bonding.

C
(A) TFTF (B) FTFT (C) FTTF (D) TTFF

Section (H) : Concept of Aromaticity

H-1*. Conditions of aromaticity is/are :

J
(A) Compound must be cyclic
(B) Compound must be planar
(C) Each member of the ring must have p-orbital perpendicular to plane of the ring.
(D) Total number of -electrons must be equal to 4n + 2, where n = 0, 1, 2.....

H-2 . Which out of the following is aromatic hydrocarbon ?

(A) (B) (C) (D)

H-3. Identify the aromatic compound ?

(A) (B) (C) (D)

H-4. Number of  electrons in conjugation for these compounds

, , & will be respectively :

I
(A) 8, 6, 6, 6 (B) 6, 4, 6, 6 (C) 6, 6, 6, 6 (D) 6, 6, 8, 6

H-5. The hybridisation of nitrogen in (pyrrole) is :

S
(A) sp3 (B) sp2 (C) sp (D) Cann't be predicted

Section (I) : Carbocations

I-1. The most unstable carbocation is :
   
(A) CH3 C H2 (B) Cl – CH2 – C H2 (C) C H2 – CHO (D) C H2 – O – CH3

I-2. The most stable carbocation is :

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(A) (B) (C) (D)

I-3. Which of the following is the correct stability order for given carbocations ?


(A) (B) (C) (D)




C
(E)

(A) E > D > B > A > C (B) C > D > B > A > E
(C) C > E > B > A > D (D) A > C > E > D > B
I-4. Write correct stability order of following compounds :

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(1) (2) (3) (4)

(A) 2 > 4 > 3 > 1 (B) 4 > 2 > 3 > 1 (C ) 2 > 3 > 1 > 4 (D) 1 > 2 > 3 > 4

I-5. The stability order of following carbocation is

(i) (ii) (iii) (iv)

(A) i > ii > iv > iii (B) iii > i > ii > iv
(C) iv > ii > iii > i (D) ii > iv > iii > i
I-6. Which of the following shows the correct order of decreasing stability ?

(A) > > > CH3 – C H2


(B) > > > CH3 – C H2

I

(C) > > > CH3 – C H2


(D) > > CH3 – C H2 >

I-7. Which of the following is the rearranged more stable carbocation of the given species ?

S
CH3
| 
CH3 – C – C H  CH3 
|
CH3

CH3 CH3
| | 
(A) CH3 – C – C H – CH3 (B) CH3 – C – C H2 – C H2
|  |
CH3 CH3

M
CH3 CH3 CH3
| | | 
(C) CH3 – C — C H – CH3 (D) CH3 – CH – CH  C H2
 |
CH3

I-8. Which of the following is the rearranged more stable carbocation of the given species ?


CH2 

C


(A) CH2 (B)  CH3 (C) CH3 (D)  CH2

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I-9. The given carbocation rearranges into :

(A) (B)

(C) (D)
Section (J) : Carbanions
J-1. Which of the following is the least stable carbanion ?
(A) HC  C– (B) (C6H5)3C– (C) (CH3)3C– (D) CH3–

J-2. The most stable anion is :

I
(A) (B) (C) (D)

J-3. In which of the following pairs of carbanion the first one is more stable than second.
(A) (B)

S
(C) (D)

J-4. Arrange the following carbanions in decreasing order of stability :

M
I II III IV
(A) III > I > IV > I (B) III > II > I > IV
(C) I > III > II > IV (D) III > I > II > IV

Section (K) : Carbon free radical

K-1. Among the following, the paramagnetic species is :
(A) Free radical (B) Carbonium ion (C) Carbanion (D) All the three

C
K-2. The stability of given free radicals in decreasing order is :
  
(i) CH3– C H2 (ii) CH3– C H –CH3 (iii) (iv) C H3

(A) iii > iv > i > ii (B) i > ii > iii > iv
(C) iii > ii > iv > i (D) iii > ii > i > iv

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K-3. Which of the following is the correct order of stability of free radicals?
(A) benzyl > allyl > 2º > 1º (B) allyl > benzyl > 2º > 1º
(C) allyl > 2º > 1º >benzyl (D) benzyl > 2º > 1º > allyl
K-4. Most stable radical among the following is :

(A) (B) (C) (D)

K-5. Arrange the following radicals in decreasing order of their stability.

(I) (II) (III) (IV)

(A) IV > I > III > II (B) IV > III > II > I
(C) I > II > III > IV (D) IV > III > I > II
 PART - III : ASSERTION / REASONING
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is correct explanation for STATEMENT-1.
(B) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is not correct explanation for STATEMENT-1.
(C) STATEMENT-1 is true, STATEMENT-2 is false.
(D) STATEMENT-1 is false, STATEMENT-2 is true.

I
(E) Both STATEMENTS are false.

1. Statement-1 : Carbon–oxygen bonds are of equal length in acetate ion.

Statement-2 : Bond length decreases with the multiplicity of bond between two atoms.

2.

Statement- : Carbocation (II) is more stable than carbocation (I).

S
Statement-2 : Carbocation (II) has less positive inductive effect of –CD3 group as compared to –CH3 group.

3. Statement-1 :

I and II are resonating structures and III is resonance hybrid.

Statement-2 : The resonance hybrid is the hypothetical structure that is considered to be a ‘blend’ of the

M
real contributing structures.

PART - I : SUBJECTIVE QUESTIONS

C
1. The central carbon-carbon bond in 1, 3-butadiene is shorter than that of n-butane. Why ?

2. Write decreasing order of electron density in aromatic ring in following compounds.

3.

J
Identify the number of compounds in which positive charge will be delocalised ?
4. In how many of the following cases, the negative charge is delocalised?

.. CH3

–
..

5.

6.

S I
Observe the following compound and write the number of hydrogen atom involved in hyperconjugation ?

Write that resonating structure of given carbocation in which all atoms have complete octet.

M
7. Write rearranged carbocation obtained by 1, 2-Methyl shift.

8. Which one of the following cation is most stable. Give reason ?

C
(I) (II) (III) (III)

9. Find the number of carbon atoms including the given structure which can have negative charge in resonating

J
structures. (The structures with charge separation are not acceptable).

10. Arrange the following carbanions in decreasing order of stability :

I II III IV
 PART - II : OBJECTIVE QUESTIONS
Single choice type
1. What is NOT-True for inductive effect but True for Resonance effect (During their functioning)
(Inductive effect) (Resonance effect)
(A) electron pair is delocalised -electron pair delocalized
(B) electron pair is localized -electron pair is localized

I
(C) Bond angle does not change -electron pair is localized
(D) Hybridisation of atoms changes -electron pair is localized

2. The most unlikely representation of resonance structures of p-nitrophenoxide ion is:

(A) (B) (C) (D)

3.

(A)
NH
3

(B)
H
N

H

(C)

S
In which delocalisation of positive charge is possible ?

OH
2

(D)
O

–

M
4. Resonance stabilized cation is :

(A) (B) (C) (D)

5. Which of the following is not the correct resonating structure of C6H5NH2 ?

C
(A) (B) (C) (D)

6. Decreasing order of potential energy of the folowing cations is :

7.

J (I)
(A) II > I > III
(II)
(B) I > II > III

Stability order of the following species ?

(A) > >  (B) > > 

(III)
(C) III > II > I

(C) > > 

(D) II > III > I

(D) > > 

8. Least contributing resonating structure of nitroethene is :

(A) (B) (C) (D)

9. The least and most stable resonating structure respectively are :

I
(1) (2) (3) (4)
(A) 2, 1 (B) 2, 3 (C) 3, 1 (D) 1, 2

10. Which of the following species does not have equally contributing resonating structures ?

(A) (B) CH2=CH–CH=CH2 (C) (D) CH2=CH–CH2

S
11. Which of the following group show +m and +I effect ?

(A) (B) –NH (C) (D) –F

12. The correct order of + m effect of ‘N’ containing functional group on benzene ring, amongst the given compounds
is

13.

14.
(A) I > II > IV > III

same atom.) :
(A) H2C = CH — Cl
(B) II > I > III > IV

(B) CH3 – CH2 – NH2

M
(C) I > II > III > IV (D) IV > III > II > I

In which case the -bond pair and  bond pair of electrons both are attracted in the same direction, (towards

(C) H2C = CH – CH = O (D) H2C = CH – OCH3

Which of the following group has the maximum hyperconjugation effect when attached to bezene ring ?

C
(A) CH3– (B) CH3CH2– (C) (CH3)2CH– (D) (CH3)3C–

15. Hyperconjugation is possible in :

(A) (B)

16.
(C)

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(A) I < III < IV < II
(II)
(B) I < II < III < IV
(D)

Stability of -bond in following alkenes in the increasing order is :

CH3–CH = CH – CH3

(I) (III)
(C) IV < III < II < I
(IV)
(D) II < III < IV < I
17. The correct heat of hydrogenation order of

(A) III > I > II > IV (B) I > III > II > IV

I
(C) II > I > IV > III (D) III > IV > II > I
18. The minimum magnitude of heat of hydrogenation per mole of molecule is of :

(A) (B) (C) (D)

19. The correct order of electron density in aromatic ring of following compounds is :

20.
I
(A) IV > III > II > I
(C) IV > II > I > III
II III

S
(B) I > II > III > IV
(D) IV > II > III > I

The decreasing order of electron density on the ring is :

IV

(A) x > w > y > z

(C) x > z > y > w

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(B) z > y > w > x
(D) y > z > w > x

C
21. The decreasing order of electron density on the ring is :

(I) (II) (III) (IV)

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(A) (II) > (III) > (IV) > (I) (B) (IV) > (I) > (II) > (III)
(C) (IV) > (I) > (III) > (II) (D) (I) > (III) > (IV) > (II)

22. The least polar compound is :

(A) (B) (C) (D)

23. Correct dipole moment order is :

CH2  CH  Cl CH3  CH2  Cl CH2  CH  CN

(p) (q) (r )
(A) r > q > p (B) r > p > q (C) q > r > p (D) p > r > q
24. Which of the following statement is correct ?

I
(A) In the dianion , all the C – C bonds are of same length but C – O bonds are of different length

(B) In the dianion, all C – C bonds are of same length and also all C – O bonds are of same lengths
(C) In the dianion, all C – C bond lengths are not of same length
(D) None of the above
25. The decreasing order of bond length of double bonds is :

26.
(A) c > a > b > d (B) d > c > a > b

S
(C) b > c > a > d

If the given compound is planar. Select the correct statement.

(D) a > b > d > c

M
(A) The boron is sp2 hybridized and the p–orbital contains an unshared pair of electron
(B) The boron is sp2 hybridized and a hybrid orbital contains an unshared pair of electron.
(C) The boron in sp2 hybridized and hybrid orbital is vacant
(D) The boron is sp2 hybridized and the p–orbital is vacant

C
27. Aromatic compounds burn with sooty flame because :
(A) They have a ring structure of carbon atoms. (B) They have a relatively high percentage of hydrogen.
(C) They resist reaction with oxygen of air. (D) They have a relatively high percentage of carbon.

28. In the following carbocations, the stability order is :

29.

30.
3

(A) CH3
J
(A) III > II > IV > I

(A) CH – C H
2

(B) IV > I > II > III

Which of the following is most stable carbocation ?


(B) C H – CH Cl

(B) CH3
2 2

Which of the following is most stable carbocation ?

(C) IV > III > II > I


(C) C H – CH – Cl
2

(C) CH3 –
2
(D) III > IV > II > I


(D) C H – CCl

(D)
2 3
31. The most stable carbocation is :

(A) (B)
+ +

(C) + (D) +

I
32. The most stable carbocation is :

(A) (B) (C) (D)

33. Arrange the following carbanions in decreasing order of stability :

34.
(A) III > II > IV > I
(C) III > I > II > IV

The stability order of the following anions :

S
(B) III > II > I > IV
(D) II > III > I > IV

M
(A) IV > III > II > I (B) I > II > III > IV (C) I > II > IV > III (D) I > III > II > IV

35. Give the stability order of following radicals :

(I) (II) (III) (IV)

(A) III > IV > II > I (B) IV > III > II > I (C) I > II > III > IV (D) IV > II > III > I

C
More than one choice type
36. Which statement is/are true about resonance ?
(A) It decreases the energy of system.
(B) The hybridisation of atoms do not change due to resonance
(C) Resonance hybrid is more stable than any resonating structure.
(D) Resonanting structures can not be isolated at any temperature

J
37. Which of the following statement is incorrect about resonance ?
(A) The most stable structure explains all the characteristics of a species.
(B) All resonating structures remain in equilibrium.
(C) Resonance hybrid has maximum similarity with most stable resonating structure.
(D) Resonance hybrid is real.

38. The correct number of p-electrons have been mentained in :

(A) ; (4) (B) ; (6)

(C) ; (3) (D) ; (6)

39. Which of the hybrid species are correct?

(A) (B)

(C) (D)

I
40. In which of the following pairs of resonating structures first resonating structure is more stable than second?

(A)  (B) 

41.
(C) 

S
(D) 

In which of the following pairs of compounds will second structure have more contribution to resonance
hybrid than first ?

(A)

(C)
&

&

M
(B)

(D)
&

&

42.

43.
(C)

J C
Which of them are correct for magnitude of resonance energy ?

(A) <

<

The correct orders for bond length are :

(A)

(C) (c > c)

(a > a)
(B)

(D)

(B)

(D)
<
<

(b = b)

(d > d)
 PART - III : MATCH THE COLUMN
1. Match the following
Coulmn - I Coulmn - II
(Compounds) (Characteristics)

I
(A) (p) Mesomeric effect / resonance

(B) Ph–CH=CH–CH3 (q) Inductive effect.

(C) (r) Hyperconjugative effect

2.
(D)

Column-I
(Stability order)

S (s) Nonpolar

(t) Polar

Column-II
(Responsible effect)

M
(A) (p) Inductive effect

(B) > (q) Resonance

(C) CH3–CH2– >

C
(r) Hyperconjugation

(D)  > CH3–CH2 (s) Mesomeric effect

J
PART - IV : COMPREHENSION
Comprehension # 1
Identification of +m & –m groups : If the first atom of the group has lone pair or negative charge shows +m
effect. If the group has vacant p-orbital or vacant d-orbital on first atom. Also a multiple bonded group in which
second atom is more electronegative than the first then it shows –m effect.

1. Identify which of the following does not show + m effect.

O O

|| ||
(A) –NH2 (B) –O (C)  NH  C  CH (D)  C  NH  CH
3 3

2. Identify which of the following cannot show – m effect.


(A) –CH = O (B)  P(CH ) (C) –F (D) –B(CH3)2
3 3
3. Decreasing + m-power of given group is :

(I) – NH2 (II) – OH (III) (IV) – NH – CO – CH3

(A) I > III > IV > II (B) III > II > I > IV
(C) III > I > II > IV (D) II > I > IV > III

Comprehension # 2

I
Hydrogenation of unsaturated hydrocarbons is an exothermic reaction. Due to hyperconjugation and resonance
the stability of unsaturated hydrocarbons increases and the increase in stability is more due to resonance.
Compound with same number of -bonds and more stability has lower heat of hydrogenation.
Heat of formation is defined as the energy evolved when a molecule is formed from its atoms. For isomers the
more stable compound has higher heat of formation.
4. The correct heat of hydrogenation order is :
(p) 1, 3-Pentadiene (q) 1, 3-Butadiene
(r) 2, 3-Dimethyl-1, 3-butadiene (s) Propadiene

S
(A) p > q > r > s (B) s > q > p > r
(C) q > s > p > r (D) s > p > q > r
5. The order of heat of formation of the following molecules is :

(A) I > II > III > IV (B) II > III > IV > I (C) IV > II > III > I (D) IV > III > II > I

M
Comprehension # 3
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.

C
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.

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6. Which of the following is the most stable carbanion intermediate ?

(A) (B)

(C) (D)
7. The stability order of following free radicals is :

(A) I > II > III > IV (B) II > III > I > IV
(C) I > III > II > IV (D) III > II > I > IV

I
8. The stability order of following carbocations is

S
(A) I > II > III (B) II > I > III
(C) III > I > II (D) II > III > I

PART - I : IIT-JEE PROBLEMS (LAST 10 YEARS)

* Marked Questions may have more than one correct option.

M
1. Write resonating structure of the compound . [JEE-03(S), 2/60]

2. The correct stability order for the following species is : [JEE-04, 2/60]

C
(A) (II) > (IV) > (I) > (III) (B) (I) > (II) > (III) > (IV)
(C) (II) > (I) > (IV) > (III) (D) (I) > (III) > (II) > (IV)

3. Explain why 7-bromo-1, 3, 5-cycloheptatriene exist as an ion while 5-Bromo-1, 3-cyclopentadiene does not

J
form any ion even in the presence of Ag+ . Explain why ? [JEE 2004, 4/60]

4. Explain the following observations [JEE 2005, 2/84]

but not

5. Which will be the least stable resonating structure : [JEE-05(S), 3/84]


(A) CH2 = CH – – – O – CH3 (B) C H2 – – CH = CH – OCH3


(C) C H2 – CH = CH – CH = – CH3 (D) CH2 = CH – – CH = – CH3
6. Among the following, the least stable resonating structure is : [JEE-07, 3/162]

 O
+
(A) (B) +
N

O


I
 O
+
(C) + N (D)
O


7. Hyperconjugation involves overlap of the following orbitals : [JEE-08, 3/163]

S
(A) – (B) –p (C) p – p (D)  – 

8. The correct stability order of the following resonating structures is : [JEE-09, 3/160]

(A) (I) > (II) > (IV) > (III) (B) (I) > (III) > (II) > (IV)
(C) (II) > (I) > (III) > (IV) (D) (III) > (I) > (IV) > (II)

M
9. In the following carbocation; H/CH3 that is most likely to migrate to the positiviely charged carbon is
[JEE-09, 3/160]

(A) CH3 at C-4 (B) H at C-4 (C) CH3 at C-2 (D) H at C-2

10. The total number of contributing structures showing hyperconjugation (involving C–H bonds) for the following

C
carbocation is [JEE-11, 4/180]

J
11.* Which of the following molecules, in pure form, is (are) unstable at room temperature ? [JEE-12, 4/136]

(A) (B) (C) (D)

12.* The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to
(A)  p (empty) and  * electron delocalisations. [JEE(Advanced)-2013, 4/120]
(B)  * and   electron delocalisations.
(C)  p (filled) and   electron delocalisations.
(D) p (filled)  * and  * electron delocalisations.
 PART - II : AIEEE PROBLEMS (LAST 10 YEARS)

1. In the following benzyl/allyl system R – CH = CH2 and (R is alkyl group)

Then decreasing order of inductive effect is : [AIEEE-2002]

I
(A) (CH3)3 C— > (CH3)2CH— > CH3CH2— (B) CH3CH2— > (CH3)2CH— > (CH3)3C—
(C) (CH3)2CH— > CH3CH2— > (CH3)3C— (D) (CH3)3C— > CH3CH2— > (CH3)2CH—

2. The increasing order of stability of the following free radicals is : [AIEEE-2006, 3/220]
• • • •
(A) (C6H5)3 C < (C6H5)2 C H < (CH3)3 C < (CH3)2 C H
• • • •

S
(B) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (CH3)2 C H
• • • •
(C) (CH3)2 C H < (CH3)3 C < (C6H5)3 C < (C6H5)2 C H
• • • •
(D) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3 C

3. The electrophile, E  attacks the benzene ring to generate the intermediate -complex, which of the following
-complex have lowest energy ? [AIEEE-2008, 3/105]

NO2 NO2 NO2

M
H
H
+ E
(A) (B) + E (C) + (D) +
H
E
H E

4. Arrange the carbanions, (CH3)3 C , C Cl3 , (CH3)2 C H, C6H5 C H2 in order of their decreasing stability :

C
[AIEEE-2009, 4/144]

(A) (CH3)2 CH > CCl3 > C6H5 CH2 > (CH3)3 C (B) CCl3 > C6H5 CH2 > (CH3)2 CH > (CH3)3 C

(C) (CH3)3 C > (CH3)2 CH > C6H5 CH2 > CCCl3 (D) C6H5 CH2 > CCl3 > (CH3)3 C > (CH3)2 CH

J
5. The order of stability of the following carbocations : [JEE(Mains)-2013, 4/120]

; ; is :

(A) III > II > I (B) II > III > I (C) I > II > III (D) III > I > II