EXERCISE # I

1. Which of the following is false order of- I effect?

 
(A) –F > –Cl > –Br > –I (B) – NH3  – NH3  –NO2

(C) –F > –OH > –NH2 (D) > C  > CH > –H

2. What is the correct order of inductive effect?

(A) –O– > –CH3 > –CMe3 (B) –CO2- > –O– > CHMe2
-
(C) –O > –CH2Me > –D > –H (D) None

3. Which of the following groups have + I effect:

(A) (B) (C) (D) –CH = CH2

4. Which of the following groups have - I effect :

(A) –OH (B) – C– OH (C) –CH3 (D) –OCH3
||
O

5. How many of the following groups have+ I effect :


(a) –OH (b) –O (c) –NH2 (d) – N H
(e) –COOH (f) –COO (g) –Me (h) –OMe

(i) –F (j) – N H3

6. Which of the following statements is (are) true about resonance.

(a) Resonance is an intramolecular process.
(b) Resonance involves delocalization of both  and  electrons.
(c) Resonance involves delocalization of  electrons only.
(d) Resonance decreases potential energy of an acyclic molecule.
(e) Resonance has no effect on the potential energy of a molecule.
(f) Resonance is the only way to increase molecular stability.
(g) Resonance is not the only way to increase molecular stability.
(h) Any resonating molecule is always more stable than any non resonating molecule.
(i) The canonical structure explains all features of a molecule.
(j) The resonance hybrid explains all features of a molecule.
(k) Resonating structures are real and resonance hybrid is imaginary.
(l) Resonance hybrid is real and resonating structures are imaginary.
(m) Resonance hybrid is always more stable than all canonical structures.

47
7. Which of the following statement is incorrect?
(A) Resonating structure are real & have real existence
(B) Equivalent contributing structures make resonance hybrid very stable.
(C) Contributing structures are hypothetical having no real existence
(D) Contributing structures are less stable than the resonance hybrid.

8. Which of the following is most stable?

(A) Conjugated alkadiene (CH2 = CH–CH = CH2)
(B) Isolated alkadiene (CH2 = CH–CH2–CH = CH2)
(C) Cumulated alkadiene (CH2 = C = CH2)
(D) All are equally stable

9. Consider structural formulas A, Band C:

   
H 2C– N  N H2 C N N H2C– N  N
(A) (B) (C)
(a) Are A, B and C isomers, or are they resonance forms?
(b) Which structures have a negatively charged carbon?
(c) Which structures have a positively charged carbon?
(d) Which structures have a positively charged nitrogen?
(e) Which structures have a negatively charged nitrogen?
(f) What is the net charge on each structure?
(g) Which is a more stable structure, A or B? Why?
(h) Which is a more stable structure, B or C? Why?

l0. A canonical structure will be more stable if

(A) it involves cyclic delocalization of (4n + 2)-electrons than if it involves acyclic
delocalization of (4n + 2)  - electrons.
(B) it involves cyclic delocalization (4n-electrons than if it involves acyclic delocalization of
(4n) 7-electrons.
(C) +ve charge is on more electronegative atom than if +ve charge is on less electronegative
atom provided atoms are in the same period.
(D) –ve charge is on more electronegative atom than if –ve charge is on less electronegative
atom provided atoms are in the same period.
48
 11. Which one of the following pair of structures does not represent the phenomenon of resonance?
O O–
||  |
(A) H2C  CH – C– H; C H 2 – CH – C – H
 
(B) CH3 CH
 – CHCl;CH2 – CH CH – Cl
O O–
|| |
(C) (CH3 )2 CH – C– O – ;(CH3 )2 CH – C  O
O O–
|| |
(D) (CH3 )2 CH 2 – C– CH3 ;CH3 – CH
 C CH3

12. In which of the following, lone-pair indicated is involved in resonance:

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


(f) CH2 CH
(e) CH2  CH – CH2   – CH NH

13. In which of the following lone-pair indicated is not involved in resonance :

 
(a) CH2  CH – NH– CH3 (b)
 CH2 CH
 – CH O



(c) CH2 CH
  – O– CH CH2 CH2 CH – C  N
(d)


CH2
(e) (f)
O O

14. Which of the following groups cannot participate in resonance with other suitable group:

(a) –COOH (b) –COOCH3 (c) –COCl (d) – N H3

(e) – CH2

15. Identify electron donating groups in resonance among the following :

(a) –CONH2 (b) –NO2 (c) –OCOCH3 (d) –COOCH3
(e) –CHO (f) –NHCOCH3

16. Identify electron withdrawing groups in resonance among the following :

(a) –COOH (b) –CONHCH3 (c) –COCl (d) –CN

(e) –O–CH= CH2 (f)

49
17. Which of the following groups can either donate or witl).draw a pair of electrons in resonance
depending upon situation :
(a) –NO2 (b) –NO (c) –CH=CH2 (d) –CHO
(e) –NH2 (f) –N = NH

18. Draw the resonance forms to show the delocalization of charges in the following ions
O O
||  || 
(a) CH3 – C– CH2 (b) H – C– CH  CH– CH2 (c) (d)

(e) (f) (g) (h)

 
(i) CH
3 – CH CH
 – CH CH – CH – CH3 (j) CH
3 – CH CH
 – CH CH – CH2

19. Identify less stable canonical structure in each of the following pairs:
 
(a) CH2 – O – CH3 
CH2  O– CH3 (b)

(c) (d)

(e)

20. Identify more stable canonical structure in each of the following pairs :

(a) (b)

(c) (d)

 
(e) CH
2 – CO CH – O 
CH2 CH
  – CH O (f)

50
21. Which of the following group can participate in resonance With other suitable group:
— 
(a) –OH (b) –CH2 – CH2 (c) –CH2 – CH2 (d)


(e) (f) –BH2 (g) – PPh3

22. Arrange the following resonating structure according to their contribution towards resonance
hybrid?
        
(a) CH2 N N (b) CH2 – N  N (c) CH 2 – N  N (d) CH2 – N  N


(A) a > d > c > b (B) b > a > c > d (C) a > c > b > d (D) d > a > b > c

23. In each of the following pairs of resonating structure which resonating structure is more stable:
 —
 


(a) CH3 – CH – C  N   CH3 – CH   C N – 
 
 

(b)

(c)

24. Formic acid is considered as a hybrid of the four structures

Which of the following order is correct for the stability of four contributing structures?
(A) I > II > III > IV (B) I > II > IV > III (C) I > III > II > IV (D) I > IV > III > II

25. In the given pair of compounds select the one in each pair having lesser resonance energy :

(a) (b)

(c) (d)

51
26. Resonance energy of resonance hybrid of a molecule will be more if:
(a) canonical structures are equivalent than if canonical structures are non-equivalent
(b) molecule is aromatic than if molecule is not aromatic.

27. In the given pair of compounds select the one in each pair having higher resonance energy :

(i) (ii) CH2 = CH – O – CH = CH2 and CH2 = CH – NH – CH = CH2

 
(iii) CH2 CH
  – NHand HN CN – NH (iv) CH2 = CH – F and CH2 = CH – Br


(v) and CH2  CH – CH2 (vi)

(vii) (viii)

(ix) CH2 = CH – OH and CH2 = CH – CH = CH – OH

(x) (xi) CH3COOH and CH3COONa


(xii) CH2  CH – O and CH2 = CH – OH (xiii)

(xiv) (xv) and CH2=CH – CH=CH – CH=CH2

28. In the given pair of compounds select the one in each pair having lesser resonance energy :

(a) CO32– and HCOO– (b) and CH2 = CH – CH2–


(c) and CH2 = CH – CH – CH2 (d) and CH2 = CH – CH2

(e)

29. In which of the following pairs first one is having more resonance energy than the second one –

(A) (B)

(C) (D) None of these

52
30. In which of the following molecules  - electron density in ring is minimum:

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

31. In which of the following molecules  -electron density in ring is maximum:

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

32. Arrange following compounds in decreasing order of reactivity of ring towards attack of
electron deficient species –

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

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

33. In which of the following molecule all the effect namely inductive, mesomeric &
hyperconjugation operate:

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

34. Which one of the following molecules has all the effect, namely inductive, mesomeric and
hyperconjugative?
(A) CH3Cl (B) CH3–CH = CH2
(C) CH3 – CH  CH – C– CH3 (D) CH2 = CH – CH = CH2
||
O

35. Select the correct statement.

(i) Delocalisation of -electron is hyperconjugation.
(ii) Delocalisation of -electron is resonance.
(iii) Permanent partial displacement of -electron is inductive effect.
(A) i & iii (B) ii & iii (C) i & ii (D) i, ii, iii

53
36. Which of the following compound is correctly matched with number of hyperconjugating
structures (involving C–H bond) :

(A) (3) (B) (9) (C) (8) (D) CH3–CC–CH3 (5)

37.

These are three canonical structures.of naphthalene. Examine them and find correct statement
among the following :
(A) All C–C bonds are of same length (B) C1–C2 bond is shorter than C2–C3 bond.
(C) Cl–C2 bond is longer than C2–C3 bond (D) None

38. Which of the following has longest C–O bond:

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

39.

Among these compounds, the correct order of C–N bond lengths is :

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

40. Cl–C2 bond is shortest in

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

41. Which of the following molecule has longest C=C bond length?

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

|
CH3

54
42. Which of the following molecule has shortest C=C bond length ?

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

|
CH3

43. C–C and C=C bond lengths are unequal in:

(A) Benzene (B) 1,3-buta-di-ene (C) 1,3-cyclohexa-di-ene (D)

44. Among the following molecules, the correct order of C–C bond length is (C6H6 is benzene)
(A) C2H6 > C2H4 > C6H6 > C2H2 (B) C2H6 > C6H6 > C2H4 > C2H2
(C) C6H4 > C2H6 > C2H2 > C6H6 (D) C2H6 > C2H4 > C2H2 > C6H6

45. CH3O–CH= CH–NO2 I

CH2 =CH–NO2 II
CH2 = CH–Cl III
CH2 = CH2 IV
Which of the following is the correct order of C–C bond lengths among these compounds:
(A) I > II > III > IV (B) IV > III > II > I (C) I > III > II > IV (D) II > III > I > IV

46. Which of the following is (are) the correct order of bond lengths:
(A) C–C > C = C > C  C > C  N
(C) C = C > C = N > C = O
(B) C = N > C = O > C = C
(D) C–C > C = C > C  C > C–H

47. In which of the following pairs, indicated bond having less bond dissociation energy:

(a) (b) CH3 – C  CHand HC  CH

 
(c)

(d) (e)

(f)

55
48. In which of the following pairs, indicated bond is of greater strength:
(a) CH3 – CH2 – Br andCH3 – CH2 – Cl
 
(b) CH3 – CH  CH – Br and CH3 – CH– CH3
 |
Br

(c) and CH3 – CH2 – Cl



(d) CH2 CH
 – CH CH2 and CH2  CH2 – CH2 – CH3
 

(e) CH2 CH
 – CH CH2 and CH2  CH – NO2
 

(f)

49.

the correct order of bond dissociation energy (provided bond undergoes homolytic cleavage):
(A) C2–H > C3– H > C4–H > C1–H (B) C2–H > C3–H > C1–H > C4
(C) C1–H > C4–H > C2–H > C3–H (D) C1–H > C4–H > C3–H > C2 – H

50. Compare the C–N bond-length in the .following species:

(A) (B) (C)

51. In which case, C–O bond length is shorter for Ist compound:

(A) (B)

(C) (D)

56
 EXERCISE # II
1. In each set of species select the aromatic species.

(i)

(ii)

(iii)

(iv)

(e)

2. Which of the given compound is aromatic, antiaromatic or nonaromatic.

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

(e) (f) (g)

57
3.

Compare carbon-carbon bond rotation across I, II, III.

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

4. Which of the given compunds has minimum rotation energy barrier across indicated carbon-
carbon bond.

Compare carbon-carbon bond rotation across I, II, III.

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

5 Which species is not aromatic?

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

6 Which of the following are non-aromatic

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

7. Write down the structure of the following molecule and comment on aromaticity?
(a) B3H3O3
(b) C3N3(NH2)3
(c) Trimer of isocyanic acid (HN = C = O)3

8. Select the least stable one :

(A) CH3 – CH2 (B) CH3 – CH2 – CH2

(C) (D)

58
9. Write stability in decreasing order of following intermediates:
CH3
  |
(i) (a) CH3 – CH2 (b) CH3 – CH – CH3 (c) CH3 – C
|
CH3

(ii)

(iii)

(iv)
  
(v) (a) CF3 – CH2 (b) CCl3 – CH2 (c) CBr3 – CH2

(vi)
  
(vii) (a) HC  C (b) CH2  CH (c) CH3 – CH2
(viii) (a) C6H5+ (b) p–NO2(C6H4)+ (c) p-CH3–(C6H4)+ ( d) p–Cl–C6H4+

(ix) (a) (b) (c)

(x) (a) (b) (c)

(xi) (a) (b) (c)

59
(xii) (a) (b) (c) (d)

Me Ph 

(xiii) (a) Me–C+ (b) Ph–C+ (c) Me – CH2 (d)
Me Ph
+
+
(xiv) (a) (b)

+
(c) (d)

(e) +
+
+ CH2
CH2 +
(xv) (a) (b) (c)

+ + +
(xvi) (a) (b) (c)

10. Consider the following statements:

 
(I) CH3OCH2 is more stable than CH3 CH2
 
(II) Me2 CH is more stable than CH3CH2 CH2
 
(III) CH2  CH –CH 2 is more stable than CH3CH2 CH2
 
(VI) CH2  CH is more stable than CH3 CH2
Of these statements:
(A) I and II are correct (B) III and IV are correct
(C) I, II and III are correct (D) II, III and IV are correct

60
11. In each of the following pairs of ions which ion is more stable:
 
(a) (I) C6H5 – CH2 and (II) CH2  CH – CH2
 
(b) (I) CH3 – CH2 and (II) CH2  CH
 
CH2 CH2
(c) (I) and (II)

CH3–CH–CH3 CH3–N–CH3
(d) (I) and
CH3–C–CH3 CH3–C–CH3
 

12. Find out correct stability order in the following carbocations-




(I) (II) (III) (IV)


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

13. Which of the following carbonium ion is most stable ?

(A) Ph3C+ (B) (CH3)3C+ (C) (CH3)2 CH+ (D) CH2=CH–CH2+

14. Consider the following carbocations

 
(a) CH3O CH2 (b) CH2

 
(c) CH3 CH2 (d) CH3 – CH2

The relative stabilities of these carbocations are such that :-

(A) d < b < c < a (B) b < d < c < a (C) d < b < a < c (D) b < d < a < c

   
CH2 CH2 CH3 CH2

15.

OH NH3 CH3 CH3–C–CH3

CH3
Correct order of carbocation stability is :
(A) 2 > 1 > 4 > 3 (B) 1 > 2 > 4 > 3 (C) 3 > 4 > 2 > 1 (D) 2 > 1 > 3 > 4

61
16. Arrange the following carbocation in the increasing order of stability :
  
CH2 CH2 CH2

CH3
CH2–CH CH–CH3
CH3 NO2 CH3 NO2
(I) (II) (III)
(A) I < II < III (B) II < III < II (C) III < II < I (D) III < I < II

17. Rank the following sets of iritermediates in increasing order of their stability.
CH2 CH2

(i) (a) (b)

F NO2
CH2 CH2 CH2 CH2

(ii) (a) (b) (c) (d)

N
Cl O O CN
 
(iii) (a) CH2–CH (b) CH2 – CH3
O
O O O
(iv) (a) (b) (c)
  
– –
CH2 CH2– CH2

(v) (a) (b) (c)

Cl NO2

  
(vi) (a) (b) (c)

CH2 CH2–CH2

(vii) (a) (b) (c)

62
(viii) (a) (b) (c)

(ix) (a) (b)

 
(x) (a) CH2  CH (b) CH2  CH – CH2 (c) CH2 (d) CH3

18. Most stable carbanion is :-

(A) HCC (B) C6H5 (C) (CH3)3C–CH2 (D) (CH3)2C=CH

19. Most stable carbanion is :

 
CH2 CH2


(A) CH3 (B) CH2  CH – CH2 (C) (D)

NO2

20. Identify the most stable anion.

   
(A) (B) (C) (C)
O
O
21. Correct order of stability :
CH3
  
(A) > H3 C CH3 > CH2–OCH3 > CH3


(B) > >

   
CH2–CH2 CH2 CH2 CH2

(C) > > >

NO2 Br CH3
CH3   
(D) CH2=CH–C  CH
2 CH – CH2  CH3  CH2  CH
2 CH
CH3
63
22. Rank the following sets of intermediates in increasing order of their stability giving appropriate
reasons for your choice.
+ + +
+ O O O
(a)
+
O O O
O O O O
– – – –
(b) CH2–C–CH3 , CH2–C–H , CH2–C–NH2 , CH2–C–OCH3

23. Select the correct order of stability of carbon free radicals :

  
I. Ph – CH2 II. Ph – CH– CH2 – CH3

III. Ph – CH– CH  CH2 IV. Ph–C–CH=CH2
CH3
(A) IV > Ill > I > II (B) IV > III> II > I (C) I > II > III > IV (D) I> III > II > IV

24. CH2=CH–CH=CH–CH3 is more stable than CH3–CH=C=CH–CH3 because

(I) (II)
(A) there is resonance in I but not in II (B) there is tautomerism in I but not in II
(C) there is hyperconjugation in I but not in II (D) II has more cononical structures than I

25. Choose the more stable alkene in each of the following pairs. Explain your reasoning.
(a) 1-Methylcyclohexene or 3-methylcyclohexene
(b) Isopropenylcyclopentane or allylcyclopentane

(c) or

26. Match each alkene with the appropriate heat of combustion:

Heats of combustion (kJ/mol) : 5293 ; 4658; 4650; 4638; 4632
(a) 1-Heptene (b) 2,4-Dimethyl-l-pentene
(c) 2,4-Dimethyl-2-pentene (d) 4,4-Dimethyl-2-pentene
(e) 2,4,4-Trimethyl-2-pentene

27. Stability of:

CH3
(I) CH3–CH=CH–CH3 (II) CH3–C=C–CH3
CH3
(II) CH3–C=CH2 (IV) CH3–C=CH–CH3
CH3 CH3
in the increasing order is :
(A) I < III < IV < II (B) I < II < III < IV (C) I < IV < III < I (D) II < III < IV < I

64
28. Which of the following C–H bonds participate in hyperconjugation?

(A) I and II (B) I and IV (C) I and III (D) Ill and IV

29. Rank the following alkenes in decreasing order of heat of combustion values:

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

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

30. Write decreasing order of heat of hydrogenation :

(i) (a) (b)

(c) (d)

(ii) (a) (b)

(c) (d)

(e)

CH3 CH3
(iii) (a) (b)
CH3 CH3
O O
(iv) (a) (b)

CH3 H CH3 CH3

(v) (a) C=C (b) C=C
H CH3 H H
CH3 CH3
(vi) (a) CH2=CH–CH (b) CH2=C
CH3 CH2–CH3
65
31. Write increasing order of heat of hydrogenation :

(i) (a) (b)

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

(iii) (a) (b) (c)

(iv) (a) (b) (c) (HOH per benzene ring)

32. Give decreasing order of heat of combustion (HOC):

(i) (a) (b) (c)

(ii) (a) (b) (c) (d)

(iii) (a) (b)

(iv) (a) (b) (c)

33. Among the following pairs identify the one which gives higher heat' of hydrogenation :

(a) and (b) and

(c) CH3–CH = CH–CH3 and CH3–CH2–CH= CH2

CH2 CH3
(d) and
CH3 CH3

34. Arrange the following compounds in order of:

(I) Stability (II) Heat of hydrogenation

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

35. If Heat of hydrogenation of 1-butene is 30 Kcal/mol then heat of hydrogenation of 1, 3-

butadiene is ?
(A) 30 (B) 60 (C) 57 (D) 25

66
 NMe2 NH2 SO3H NO2 Br

36.
A B C D E
Steric inhibition of resonance takes place :
(A) In A,B only (B) In A, B, C, E (C) C only (D) In A only

37. Consider the following two structures and choose the correct statements –

O– +
O –O
+
O
N N

(I) (II)
(A) carbon-nitrogen bond length structure I is greater than that in structure II
(B) carbon-nitrogen bond length in structure I is less than in structure II
(C) carbon-nitorogen bond length in both structure is same
(D) It cannot be compared

38. Which of the following statements would be true about this compound:
NO2
5

1 3
NO2 NO2
Br
(A) All three C–N bonds are of same length.
(B) Cl–N and C3–N bonds are of same length but shorter than C5–N bond.
(C) Cl–N and C3–N bonds are of same length but longer than C5–N bond.
(D) Cl–N and C3–N bonds are of different length but both are longer than C5–N bond

67
39. Arrange given compounds in decreasing order of dipole moment:
CH3 CH3 CH3
Cl
(i) (a) (b) (c)
Cl
Cl
NO2 NO2 NO2
Cl
(ii) (a) (b) (c)
Cl
Cl
NMe2 NMe2

(iii) (a) (b)

40. Why a cation like is not possible.

68
 EXERCISE # III
1. Cyclopentadienyl anion is much more stable than allyl anion because :
(A) Cyclic anion is more stable than acyclic anion
(B) Delocalised anion is more stable than localised anion
(C) Cyclopentadienyl anion is aromatic in nature
(D) None of these
2. Select correct statement regarding given compounds :
CH3OCH3 C2H5OH
I II
(A) Boiling point of II is higher than I
(B) Boiling point of II is lower than I
(C) Compound I forms intramolecular H-bonding
(D) Compound II forms intermolecular H-bonding
I II III IV
3. In the compound, CH3–CH=CH–CN, the most electronegative carbon is :
(A) I (B) II (C) III (D) IV
 
CH2 CH2

4.

CH3 CD3
(I) (II)
Carbocation (I) is more stable than carbocation (II), because :
(A) –CD3 has more + I effect than –CH3 (B)–CH3 has more + I effect than –CD3
(C) –CH3 has more + H effect than –CD3 (D)–CD3 has more + H effect than –CH3
5. Select correct statement :
(A) Carbon-oxygen bonds are of equal length in acetate ion
(B) Resonating structures of acetate ion are equivalent
(C) Carbon-oxygen bonds are of unequal length in formate ion
(D) Resonating structures of formate ion are equivalent
6. Match the column I with column II.
Column-I Column-I
(Group attached with benzene ring) (Effect shown by the group)
(A) –NO2 (P) –R effect
(B) –O– (Q) +R effect
(C) –O–CH3 (R) +I effect
(D) –CN (S) –I effect

69
7. Column- I Column- I
(Groups attached to phenyl ring) (Effect shown)

(A) –N0 (P) +M
(B) –CH3 (Q) –M
O
(C) –NH–C (R) +H
CH3
(D) –C–OCH3 (S) –I
O

8. Match the column :

Column-I Column-II
(A) Group donate e– inductively but does not (P) –OH
donate/withdraw by resonance
(B) Group withdraw e– inductively but does not (Q) –NO2
donate/withdraw by resonance
(C) Group withdraw e– inductively & donate (R) –CH2–CH3
-
e by resonance

(D) Group withdraw e– inductively & withdraw (S) – NH3
e- by resonance
(T) –NH2

9. Match the column I with column II.

Column-I Column-II

(A) (P) Aromatic

(B) (Q) Non-aromatic

(C) + (R) Anti-aromatic



(D) (S) Cyclic structure

70
10. Statement-I : –C–OEt
a –C–O–C–
b bond length a < b
O O O
Because
Statement-II: More is the double bond character less is the bond length.
(A) Statement-I is true, statement-II is true and statement-II is correct explanation for statement-I.
(B) Statement-I is true, statement-II is true and statement-II is NOT the correct explanation for
statement-I.
(C) Statement-I is true, statement-II is false.
(D) Statement-I is false, statement-II is true.
   
11. Statement-I: Me3 C is more stable than Me2 CH and Me2 CH is more stable than the MeCH2 .
Because
Statement-II: Greater the number of hyperconjugative structures, more is the stability of carbocation.
(A) Statement-I is true, statement-II is true and statement-II is correct explanation for statement-I .
(B) Statement-I is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-I.
(C) Statement-I is true, statement-II is false.
(D) Statement-I is false, statement-II is true.
12. Statement-I : The potential energy barrier for rotation about C=C bond in 2-butene is much
higher than that in ethylene.
Because
Statement-II : Hyperconjugation effect decreases the double bond character.
(A) Statement-I is true, statement-II is true and statement-II is correct explanation for
statement-I.
(B) Statement-I is true, statement-II is true and statement-II is NOT the correct explanation for
statement-I
(C) Statement-I is true, statement-II is false
(D) Statement-I is false, statement-II is true.
Paragraph for Question 13 to 15
The intramolecular delocalisation of n and non-bonding electrons without any change in the
position of atoms is called resonance. Delocalisation may occur in conjugated system involving
carbon atom and atom other than carbon. Delocalisation makes system stable. More is the
number of resonating structures, more is the stability of the system. A resonating structure is
less stable when a higher electronegative atom has positive charge and when identical charges
are present on adjacent atoms.
13. The decreasing order of stability of the following resonating structures
 —   
CH2 CH – Cl
 

  CH2 – CH
   Cl 

 CH2 – CH 
  Cl –

  is:
(I) (II) (III)
(A) I > II > III (B) II > III > I (C) III > II > I (D) I > III > II

71
  
14. If A is PhCH2 and B is CH2  CH – CH2 , the greater number of resonating structure is of-
(A) A (B) B (C) both A and B (D) None of these

15. Which of the following pairs represent resonance?

 
(A) CH2 = CHOH ; CH3CHO (B) CH2 – CHO ;H2C  CH– O
+
O OH OH OH
(C) CH3–C–CH3 ; CH3–C=CH2 (D) CH3–C–CH3 ; CH3–C–CH3

Paragraph for Question 16 to 18

Carbocation is a specie with-positively charged carbon atom having six electrons irrthe valence
shell after sharing. Carbocations are formed in the heterolysis of a bond and are planar species.
Stability of carbocation is determined by inductive effect, hyperconjugation and resonance
effect Greater the number of contributing structures, more is the stability of a Carbocation.
Electron releasing groups (+I effect) increases the stability of a carbocation whereas the
electron withdrawing groups (–1 effect) have an opposite effect.

16. Which of the following is most stable carbocation?

   +
(A) CH3 (B) CH3 – CH– CH3 (C) CH3 – CH2 (D) CH3–C–CH3

CH3

17. The most stable carbocation among the following :

NO2

(A) (B)  (C)  (D) 

18. In which of the following cases, the carbocation (I) is less stable than the carbocation (II)?
+ +
 
CH2 CH2
(A) C6H5 – CH2 (I),CH2  CH – CH2 (II) (B) (I) , (II)

  + 
(C) CH2  CH(I), CH3 – CH2 (II) (D) H3C–CH2(I), CH2–CH2 (II)

CH3

72
19. Examine the structures I and II for nitromethane and choose the statement correctly:
–
+ O +2 O
CH3–N – CH3–N –
O O
(I) (II)
(A) Structure II is unlikely representation because electrons have shifted to oxygen
(B) Structure II is unlikely representation because nitrogen has sextet of electrons
(C) Structure II is acceptable and important
(D) None of these

20. Examine the following two structures for pyrrole and choose the correct statement given below
+

N N–
H H
(I) (II)
(A) II is not an acceptable resonating structure because carbonium ions is less stable than
nitride ion
(B) II is not an acceptable resonating structure because there is charge separation
(C) II is not an acceptable resonating structure because nitrogen has ten valance electrons
(D) II is an acceptable resonating structure

21. Delocalization of electrons increases molecular stability because :

(A) Potential energy of the molecule decreases (B) Electron-electron repulsion decreases
(C) Both (A) and (B) (D) Electron-electron repulsion increases

22. The most stable and the least stable carbocation among

  
(I) (II) CH2  CH– CH2 (III) C6H5 – CH2 (IV) CH3 – CH– CH3

are respectively :
(A) II, I (B) III, IV (C) I, II (D) I, IV

23. Most stable carbocation is formed by the heterolysis of:

(A) (CH3)3CBr (B) (C6H5)3CBr (C) (C6H5)2CHBr (D) C6H5CH2Br

73
24. Total number of aromatic compounds
HO O

(a) (b) (c) (d) 

N
HO O H H
O

(e) (f)

25. Identify total number of compounds which are unstable at room temperature ?
O

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

H
B
(v) (vi) (vii)

74
 EXERCISE # IV (JEE-MAINS)
1. In the following benzyl/allyl system [AIEEE-2002]
R–CH=CH2 or R
(R is alkyl group)
decreasing order ofinductive effect is-
(1) (CH3)3C– > (CH3)2CH– > CH3CH2– (2) CH3–CH2– > (CH3)2CH– > (CH3)C–
(3) (CH3)2CH– > CH3CH2– > (CH3)3CH– (4) None of these

2. In the anion HCOO- the two carbon-oxygen bonds are found to be of equal length. What is the
reason for it- [AIEEE-2003]
(1) Electronic orbits of carbon atoms are hybridised
(2) The C=O bond is weaker than the C–O bond
(3) The anion HCOO– has two resonating structure
(4) The anion is obtained by removal of a proton form the acid molecule

3. Which one of the following does not have sp2 hybridised carbon [AIEEE-2004]
(1) Acetamide (2) Acetic acid (3) Acetonitrile (4) Acetone

4. Due to the presence of an unpaired electron, free radicals are - [AIEEE-2005]

(1) Chemically inactive (2) Chemically reactive
(3) Cations (4) Anions

5. The increasing order of stability of the following free radicals is [AIEEE-2006]

   
(1) (C6H5 )3 C  (C6H5 )2 CH  (CH3 )3 C  (CH3 )2 CH
   
(2) (C6H5 )2 CH  (C6H5 )3 C  (CH3 )3 C  (CH3 )2 CH
   
(3) (CH3 )2 CH  (CH3 )3 C  (C6H5 )3 C  (C6H5 )2 CH
   
(4) (CH3 )2 CH  (CH3 )3 C  (C6H5 )3 CH  (C6H5 )3 C
— — — —
6. Arrange the carbanions, (CH3 )3 C,CCl3 ,(CH3 )2 CH,C6H5 CH2 in order of their decreasing
stability [AIEEE-2009]
— — — —
(1) CCl3  C6H5 CH2  (CH3 )2 CH  (CH2 )3 C
— — — —
(2) (CH3 )3 C  (CH3 )2 CH  C6H5 CH2  CCl3
— — —
(3) C6H5 CH2  CCl3  (CH3 )3 C  (CH3 )2 CH
— — — —
(4) (CH3 )2 CH  CCl3  C6H5 CH2  (CH3 )3 C

75
7. The non aromatic compound among the following"is :- [AIEEE-2011]

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

S 

8. ortho-Nitrophenol is less soluble in water than ir-and m- Nitrophenols because : [AIEEE-2012]

(1) Melting point of o-Nitrophenol is lower than those of m- and p–isomers
(2) o- Nitrophenol is more volatile in steam than those of m- and p–isomers
(3) o-Nitrophenol shows lntramolecular H–bonding
(4) o-Nitrophenol shows Intermolecular H–bonding

9. Which of the following compounds are antiaromatic :- [AIEEE-2012(0nline)]

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

O 

(V) (VI)

(l) (III) and (VI) (2) (II) and (V) (3) (I) and (V) (4) (V) and (VI)

10. Among the following the molecule with the lowest dipole moment is :- [AIEEE-2012(0nline)]
(1) CHCl3 (2) CH2Cl2 (3) CCl4 (4) CH3Cl

11. The order of stability of the following carbocations [JEE-MAIN-2013]


CH2

 
CH2=CH–CH2; CH3–CH2–CH2 ; is :
I II
III
(l) III > II > I (2) II > III > I (3) I > II > III (4) III > I > II

12. For which of the following molecule significant μ  0 (JEE-MAIN-2014]

Cl CN OH SH

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

Cl CN OH SH
(1) Only (3) (2) (3) and (4) (3) Only (1) (4) (1) and (2)

13. Which of the following molecules is least resonance stabilized ? [JEE-MAIN-2017]

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

O N O
76
14. Which of the following compounds is not aromatic ? [JEE MAIN-2019]

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

N N
H

15. Which compound(s) out of the following is/are not aromatic ? [JEE MAIN-2019]

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

77
 EXERCISE # V (JEE-ADVANCED)
l. Which one of the following has the smallest heat of hydrogenation per mole of H2? [IIT-93]
(A) 1–Butene (B) trans–2-Butene
(C) cis–2–Butene (D) I, 3–Butadiene

2. Most stable carbonium ion is [IIT-95]

 
(A) p – NO2 – C6H4 – CH2 (B) C6H5 CH2
 
(C) p – Cl – C6H4 – CH2 (D) p – CH3O – C6H4 – CH2

3. Arrange the following compounds in order of increasing dipole moment : [IIT-96]

toluene (I) m-dichloroobenzerie (II)
o-dichlorobenzene (III) p-dichlorobenzene (IV)
(A) I < IV < II < III (B) IV < I < II < III (C) IV < I < III < II (D) IV < II < I < Ill

4. The most unlikely representation ofresonance structure of p-nitrophenoxide ion is - [IIT-99]

       
O–N=O O–N–O O=N=O O–N=O

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



O O O O
5. An aromatic molecule will not [IIT-99]
(A) have 4n  electrons (B) have (4n + 2) electrons
(C) be planar (D) be cyclic

6. Statement-I: p-Hydroxybenzoic acid has a lower boiling point that o-hydroxybenzoic acid.
Because
Statement-II: o-Hydroxybenzoic acid has intramolecular hydrogen bonding. [IIT-2003]
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for
Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-IT is True.

7. Among the following, the molecule with the highest dipole moment is [IIT-2003]
(A) CH3Cl (B) CH2Cl2 (C) CHCl3 (D) CCl4

78
8. Give resonating structures of following compound. [IIT-2003]

OH

9 Which of the following is least stable : [IIT-2005]

   
(A) CH3 – C CH
  – CH– HC CH2 (B) CH
 3 –O CH
 – HC HC – CH2
   
(C) CH3 – O– CH– CH– HC  CH2 (D) CH3 – O– CH– CH– CH  CH2

10 Among the following, the least stable resonance structure is - [IIT-2007]


  O   O   O  O
 N  N  N  N
(A) O (B) O (C) O (D) O
   

11 The correct stability order for the following species is : [IIT-2008]

  
O O 

(I) (II) (III (IV

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

12 The correct stability order of the following resonance structures is [IIT-2009]

 —  — —  — 
(I) H2C N N (B) H2 C– N  N (C) H2 C– N  N (D) H2 C– N  N
(A) (I) > (II) > (IV) > (III) (B) (I) > (III) > (II) > (IV)
(C) (II) > (I) > (III) > (IV) (D) (III) > (I) > (IV) > (II)

13 The total number of contributing structures showing hyperconjugation (involving C-H bonds)
for the following carbocation is. [IIT-2011]
H3C  CH2CH3

14 Which of the following molecules, in pure from, is (are) unstable at room temperature?
[IIT-2012]
O O

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

79
Q.15 The hyperconjugative stbilities of tert-butyl cation and 2-butene, respectively, are due to
(A) p (empty) and  electron delocalisations [IIT-2013]
(B)  and  electron delocalisations
(C) p (filled) and  electron delocalisations
(D) p (filled)  and  electron delocalisations

Q.16 The total number of lone-pairs of electrons in melamine is [IIT-2013]

Q.17 The number of resonance structures for N is : [IIT-2015]

OH
NaOH
N

Q.18 Among the following the number of aromatic compound(s) is [JEE ADV. 2017]
 

  

80
 ANSWER KEY
EXERCISE # I
l. (D) 2. (C) 3. (B) 4. (A,B,D) 5. 4(b,d,f,g)
6. (a), (c), (d), (g), (j), (l), (m) 7. (A) 8. (A)
9. (a) Resonance forms, (b) A, (c) C, (d) A & B, (e) B & C, (f) 0, (g) B, (h) B
10. A,D 11. (D) 12. b,d,e 13. b,d,e 14. (d) 15. c,f
16. a,b,c,d,f 17. b,c,f 19. a-I, b-II, c-II, d-II, e-1
20. a-I,b-I,c-I,d-I,e-II,f-II 21. a,e,f,g 22. (A) 23. (a) II; (b) II; (c) II
24. (A) 25. a-II, b-II, c-II, d-II 26. a&b
27. (i)-I, (ii)-II, (iii)-II, (iv)-I, (v)-I, (vi)-II , (vii)-I, (viii)-II, (ix)-II, (x)-II, (xi)-II ,(xii)-I, (xiii)-I,
(xiv)-I, (xv)-I
28. a-II, b-I, c-I, d-II, e-I 29. (B) 30. (D) 31. (B) 32. (C)
33. (C) 34. (C) 35. (D) 36. (A,B,C)
37. (B) 38. (B) 39. (C) 40. (D) 41. (D) 42. (A)
43. (B,C,D) 44. (B) 45. (A) 46. (A,C,D)
47. a-I ,b-I, c-II, d-I, e-I, f-I 48. a-II ,b-I, c-I, d-I, e-II, f-II
49. (D) 50. C>B>A 51. (A)

EXERCISE # II
1. (i) a, b ; (ii) a, c ; (iii) b, c, d ; (iv) a, b, c, d, e, f
2. Aromatica, b, d, e, g; Non-aromaticc, f 3. (C) 4. (C) 5. (B)
6. (A)
H NH2 OH
B C C
O O N N N N
7. (a) (b) (c)
H–B B–H NH2–C C–NH2 HO–C C–OH
O N N
8. (D)
9. (i) c > b > a (ii) c > b > a (iii) b > c >a (iv) d > c > b > a (v) c > b > a
(vi) b > c > a (vii) c > b >a (viii) c > a > d > b (ix) b > c > a (x) c > a > b
(xi) c > a > b (xii) a > b > c > d (xiii) b > a > c > d (xiv) d > e > b > a > c
(xv) a > c > b (xvi) b > c > a

81
10. (C) 11. (a) I; (b) I; (c) II; (d) II; 12. (C) 13. (A) 14. (A)
15. (D) 16. (B)
17. (i) a < b (ii) d < a < c < b (iii) b < a (iv) c < b < a (v) c < a < b (vi) a < c < b
(vii) c < b < a (viii) c < b < a (ix) b < a (x) a < c < b < d 18. (A)
19. (D) 20. (B) 21. (D) 22. (a) IV < I < II < III < V (b) III < IV < I < II
23. (B) 24. (A) 25. (a)-I ; (b)-I ; (c)-II
26. (a) 4658 ; (b) 4638 (c) 4632 ; (d) 4650; (e) 5293 27. (A) 28. (B) 29. (D)
30. (i) d > c > b > a ; (ii) e > c > d > b > a; (iii) b > a (iv) a > b (v) b > a ; (vi) a > b
31. (i) a < b ; (ii) e < d < c < b < a ; (iii) a < c < b ; (iv) a > b > c
32. (i) c > b > a ; (ii) a > b > c > d ; (iii) a > b ; (iv) c > b > a
33. a-I; b-I; c-II, d-I 34. Stability order: d > c > b > a ; HOH order: a > b > c > d
35. (C) 36. (D) 37. (B) 38. (C)
39. (i) c > b > a (ii) a > b > c (iii) a > b

EXERCISE # III
1. (C) 2. (A,D) 3. (D) 4. (C) 5. (A,B,D)
6. (A)P,S ; (B)Q,R ; (C)Q,S ; (D)P,S
7. (A)P,Q,S ; (B) R ; (C)P,S ; (D)Q,S
8. (A)R ; (B)S ; (C)P, T ; (D)Q 9. (A)Q,S; (B)-P,S; (C)P,S; (D)R,S
10. (D) 11. (A) 12. (D) 13. (A) l 4. (A) 15. (B) 16. (D)
17. (C) 18. (C) 19. (B) 20. (C) 21. (C) 22. (D) 23. (B)
24. (4) 25. (4)

EXERCISE # IV (JEE-MAINS)

1. (1) 2. (3) 3. (3) 4. (2) 5. (4) 6. (1) 7. (1)

8. (3) 9. (4) 10. (3) 11. (4) l2. (2) 13. (4) 14. (1)
15. (2)

EXERCISE # V (JEE-ADVANCED)
1. (D) 2. (D) 3. (B) 4. (C) 5. (A) 6. (D) 7. (A)
9. (D) 10. (A) l 1. (D) l 2. (B) 13. (6) 14. (B,C) 15. (A)
16. (6) 17. (9) 18. (5)

82
 SOLUTIONS : ELECTRONIC DISPLACEMENT EFFECTS
EXERCISE # I
Note : Check series of –I.
1. Ans. (D)
2. Ans. (C)
3. Ans. (B)

+ – +
4. (A) C–C–C–C–OH (B) C–C–C–C–O–H
E.N. – I
more O – – I
+I
(C) C–C–CH3 (D) –O–CH3
E.N. – I

5. + I effect group
— 
– O, – NH, – COO , – Me `

6. True statement about resonance

(c) Resonance involves delocalization of  electrons only.
C=C–C=C–C=O
(d) Resonance decreases potential energy of an acyclic molecule.
(Due to resonance stability of molecular  in acyclic mol so potential energy)  (mol
cyclic A.B.)
(g) Resonance is not the only way to increase molecular stability.
(+I, H·C also increases stability) (Aromaticity)

(j) The resonance hybrid explains all features of a molecule.

(l) Resonance hybrid is real and resonating structures are imaginary.

(m) Resonance hybrid is always more stable than all canonical structures.

7. Incorrect statement-
Resonating structure are real & have real existence
(Resonating structure is a hypothetical structure which is imaginary)

8. (A) Conjugated alkadiene (CH2 = CH–CH = CH2) (resonance)

83
10. Canonical structure will more stable if
(A) It involves cyclic delocalization of (4n + 2) -electrons than if it involves acyclic
delocalization of (4n + 2) -electrons.

4n + 2 = 6e–

Non aromatic

O O–
|| |
11. CH3 – CH2 – C– CH3 
 CH3 – CH
 C CH3
Its not a resonance phenomena tautomeris-
For resonance 3 parallel P orbital is necessary.

12. (a) (b) N (d)

N H N
l. p localised l. p delocalised l. p delocalised
When l. p is adjacent position of two parallel P-orbital, then l. p is delocalized.


13. CH2 CH
(b)   – CH O (d)
CH2 CH – C  N


(e)
O
l. p localised


14. – NH3
 –I
NH3 NH3


(not possible)
N can't form
S bond
So not involved in resonance only inductive effect.

84
 O O
C–NH2 EWG C–NH–CH3 EWG
15. (a) (b)

O O O

C–Cl EWG O–C–CH3 ERG NH–C–CH3 ERG

(c)

O O O
C–OH C–NH–CH3 C–Cl CN
16. (a) (b) (c) (d)

N EWG
(f)

 

17. (b) – N  O CH2 – N = O EWG CH2 – N = O ERG

+ 
(c) –CH = CH2 CH3 – CH2 – CH = CH2 ERG CH3 – CH – CH = CH2 EWG

N = NH N = NH


(f) – N  NH ERG EWG

85
 –
O O

18. (a) CH3 – C – CH2 CH3 – C = CH2
–
O O O
 
(b) H – C – CH = CH = CH2 H – C – CH – CH = CH2 H – C = CH – CH = CH2

 
(c) CH2 CH2  CH2 CH2 CH2



(d)
 


 
(e) O O  O O O



(f)  NH N–H NH



(g)  
(h)

O O O

O O O

(i) CH3 – CH = CH – CH = CH – CH – CH3


CH3 – CH = CH – CH – CH = CH – CH3


CH3 – CH – CH = CH – CH = CH – CH3

(j) CH3 – CH = CH – CH = CH – CH2


CH3 – CH = CH – CH – CH = CH2


CH3 – CH – CH = CH – CH = CH2

86
  
19. (a) CH2 – O – CH3 
CH2  O– CH3
Incomplete octet Complete octet
(less stable) (more stable)

(b)

Two benzene structure One benzene ring

(more stable) (less stable)
-
O O
(c) C C –
H CH2 H CH2
Negative charge on more Negative charge on less
E.N. atom is more stable E.N. atom is less stable
– 
O NH O NH
(d) C C
H H H H
Negative charge on Negative charge on
more E.N. atom 'O' less E.N. atom 'N'

(e)
   
CH2 CH2
Aromatic ring


O O
20. (a) H—C C 
OH H O—H
Neutral charged
more stable

(b) O O

Aromatic negative Non-aromatic negative
charge on 'O' charge on 'C'
more stable less stable


(c)
N N

Aromatic
more stable

87
 (d)
 

 
CH2 CH2
Aromatic Anti Aroamtic
more stable
 
(e) CH
2 – CH CH – O 
CH2 CH
  – CH O
'Charged structure' 'Neutral'
(f) More EN contain –ve charge and less EN contain +ve charge.

  H.C
OH CH2–CH2 CH2–CH2 CH2
H.C H.C
21. (a) (b) (c) (d)

 Vacant d
CH=CH BH2 Ph–P–Ph

(e) (f) (g)

resen

       
22. (a) CH2 = N = N (b) CH2 – N = N (c) CH2 – N = N (d) CH2 – N  N
Complete Negative charged Positive charged Negative charged
octet on 'C' atom on 'C' on 'C' complete octet
(a > d > c > b)


23. (a) CH3 = CH – C  N CH3 – CH = C = N
Negative charge charge on 'N' (more stable)
on 'C'

O O O O

(b) CH3 – C – CH – C – CH3 CH3 – C = CH – C – CH3
Negative charge on 'C' Negative charge on 'O'
(cross conjugation) extended conjugation
(more stable)
NH2 NH2

(c) CH3 – CH2 – C – NH2 CH3 – CH2 – C = NH2

Incomplete octet Complete octet
(more stable)

88
24.

Neutral positive charge on 'C'

(less stable)
(i > ii > iii > iv)

25. (a) >

O OH
Aromatic compound Extended
(more stable) conjugation

(b) > 
CH2

Aromatic compound Resonance

(c) >
NO2
N
O
Aromatic compound Resonance

(d) >
N O
H
Aromatic

 

N O O
+ +
Positive charge on 'N' Positive charge on 'O'
(more stable) (less stable)

27. (i) >

N N
6 e–/6 atom –
H 6 e /5 atom
Aromatic Aromatic
6 membered 5 membered

89
(ii) CH2 = CH – O – CH = CH2

CH2 = CH – NH – CH = CH2
LP donation tendency N > O
    
(iii) CH2 = CH – NH CH2 – CH = NH < HN = CH – NH HN = CH – NH
Negative charge on 'C' Negative charge on 'N'
(iv) CH2 = CH – F > CH2 = CH – Br
2P 2P 2P 4P
So, electron donatives is for
CH2
(v) > CH2 = CH – CH2
Extended conjugation
(Aromatic ring)
OH
(vi) <
1 Aromatic ring 2 Aromatic ring
 benzene

(vii) >
Benzene Benzene 1 Benzene
36 kal 36 kal
O O
(viii) <
Cross conjugation Extended conjugation

(ix) CH2 = CH – OH < CH2 = CH – CH = CH – OH

less conjugated sys long conjugation

(x) <
Cross Extended conjugation
O O

(xi) CH3 – C – OH < CH3 – C – O Na
equal R.S

 
O O

CH3 – C = O – H CH3 – C = O Na
Resonance

90
 
(xii) CH2 = CH – O < CH2 = CH – OH
charged neutral
–
COO O–
(xiii) >

Equal R.S

(xiv) >
36 kal 36 kal naphthalene
Two individual 62 kcl
benzene ring

(xv) > CH2 = CH – CH = CH – CH = CH2

Aromatic Resonance


O O

28. (a) CO32– > H–C–O H–C=O
2 equal structure

O O
 C   C
O O O O
3 equal R.S


O
 C 
O O


(b)  < CH2 = CH – CH2 (c) < CH2 = CH – CH = CH2
A. Aromatic Resonance A. Aromatic Resonance

O–H

(d)  > CH2 = CH – CH2 (e) <
Aromatic Resonance

91
29. (A) <
Resonance Aromatic
compound


(B)  >
Resonance A. Aromatic
(C) N < NH2
H
Cross conjugation Extended resonance

NO2
–M
30. Low e– density in the ring
NO2
–M


O
31. + M, + I

CH3 CH3 H

CH3 CH–CH3 CH3–C–CH3 H–C–CH3

32. (i) (ii) (iii) (iv)

3H 1H 0H 2H
H.C H.C
more e– density

+I O –M
33. C–CH3

CH3
H.C

34. CH3 – CH = CH – C – CH3

H.C O +I
Mesomeric

92
35. (i), (ii), (iii)

CH3
CH3 CH3

N
36. (A) C (B) (C) CH3
H H CH3 8  11
9  11

1 1 1
2 2 2

3 3 3
37. 3 R.S of Napthalene 4 4 4

2-1 bond two time double but one time single

O
38. extended conjugated C–O bond length

NH2 NH2 NH3

39. (i) (ii) (iii) (iv) CH2 = NH pure = bond

C–H
O
(iii > ii > i > iv)
More resonance
More = bond character

2 
1 CCH CCH
40.


Resonance

41. Longest bond length CH3 – C = CH2

CH3
6  11

42. CH2 = C = CH2 (pure double bond)

93
43. (A) Benzene (close conjugated)

Two equal R.S all C–C bonds are equal

 
(B) 1, 3-buta.di-ene C = C – C = C C – C = C – C not same length

(C) C–C & C=C are not same length

1 1
2 2
(D) all C–C & C=C are same length
3 3
4 4
Aromatic compound

44. CH3 – CH3 > > CH2 = CH2 > CH  CH

1.39 A 1.39 A

O O
45. CH3 – O – CH = CH – N CH2 = CH – N
+M O O
–M
(I) more resonance (II)
 
CH2 = CH – Cl CH2 – CH = Cl CH2 = CH2 pure double bond

(III)

46. (A,C,D)

47. (a) CH2 = CH2

2 –bond Pure = bond
4H
H.C
Bond angle with  H
(b) CH3 – C  CH CH  CH
 
(c) CH2 = CH CH = CH2 < CH2 = CH CH = CH2
C C
CH2 CH2

94
 O O O O

(d) C C (e) C C
NH2 NH2 CH3 NH2 Cl Cl CH3 Cl
3.R.S cross 2.R.S
O O

(f) C C
NH2 NH2 H NH2

48. Bond S
 
(a) CH3 – CH2 – Br   CH – CH – Cl
  3 2  
 
In group top to bottom C–X bond length  so bond strength 
(b)
CH3 – CH = CH – Br > CH3 – CH – CH
Double bond character Br
O
(c) CH3 – C – Cl > CH3 – CH2 – Cl
d.b.c
(d) CH2 = CH – CH = CH2 > CH2 = CH – CH2 – CH3

d.b.c H.C
Due to resonance
CH2 = CH – CH = CH2 < CH2 = CH – NO2


(e)    O
CH2 – CH = CH – CH2 CH2 – CH = N
O
less stable more stable
Due negative charge on 'C'

CH3
(f) <
C2H3 C2H3
9H 6H H.C

95
49. * Remove hydrogen and make radical
1
* Stability 
Bonddissociation energy
1>4>3>2

NH2 NH2 NH2

50. (A) (B) (C) C>B>A

O
more stable so more d.b.c

51. Due to SIR in A Ist compound not participate in resonance.

96
 EXERCISE # II

1. (a)  4n + 2 = 10 e– Aromatic n=2

All pheripheri e– count

(b) Total = 6e–

S


(ii) 

6e– 10e–

  
(iii) 6e –
2e– 6e–
N
H

(iv) 10e– Aromatic

H
Si B
H
6e– 6e– Aromatic 6e– Aromatic

B
H–N N–H
(c) Inorganic benzene 6e– Aromatic
H–B B–H
N
H

(f) 10e– Aromatic

N
H

97
2. (a) N 6e– Aromatic Isoxazolc (b) N S 6e– Aromatic
O

H
sp3

(c) Non-Aromatic pyran (d) Aromatic pyryliun ion 6e–
O O

(e) 6e– Aromatic (f) N SP3 Non-Aromatic

O H

NH2

N
–
(g) N O 6e Aromatic cystosine
H

3. (i) (ii) (iii) Not break due to A. N

 
(iv)  Aromatic most stable (v) Aromatic large size ring

 ii > i > iii

4. (i) Anti Aromatic so not break (ii) Anti Aromatic not break

(iii) Aromatic so minimum rotation energy barrier is required

98
5. 
Tub-shab
non-Aromatic non-planar
system

+
6. N
H sp3
H

7. (a) B3H3O3 (Boroxine)

NH2
B
O O
Aromatic
H–B B–H
O
(b) C3N3(NH2)3 (Melamine) (Trimer of cynamide)
N  sp3

N
NH2–C C–NH2
Aromatic
N N
C
NH2
(c) Trimer of isocyanic acid (HN = C = O)3
OH

C
N N
Aromatic
HO–C C–OH
N
 
8. (A) CH3 – CH2 (B) CH3 – CH2 – CH2
3H 2H H.C
H.C
CH3 CH3
 
(C) CH–CH2 (D) CH3 CH–CH2
CH3 CH3
1H 0H

99
 CH3
 
9. (i) (C) CH3 – C > CH3 – CH – CH3 > CH3 – CH2

CH3
9H 6H 3H


 
(ii) > >

7H 3H 1H


(iii) 


1H 7H 3H
bca

(iv) Angle strain  S-charactic on ring positive charge is unstable at most E.N. ring
   

> > >

  
(v) (a) CF3  CH2 (b) CCl3  CH2 (c) CBr3  CH2
–I –I –I
– I order – F > – Cl > Br
cba

(vi) (a)  (b) (c)

 

1H +I 2H +I 2H

bca + I effect it distance dependent
  
(vii) (a) HC  C (b) CH2  CH (c) CH3 – CH2
sp sp2 sp3 H.C
cba
   

(viii) (a) (b) (c) (d)

NO2 CH3 Cl
–I +I –I
ca db
100
   
CH2 CH2 CH2

(ix) (a) (b) (c)

N OMe b>c>a
O O
– M, – I + M, – I

  
CH2 CH2 CH2
OH
(x) (a) (b) (c)
OH
+M, –I –I
OH +M, –I
In a and b +H is same but CH3 having more +I in C
ca b

  
CH2 CH2 CH2
CH3
(xi) (a) (b) (c)
CH3
CH3 +I H.C, +I
H.C, +I
ca b

   
CH2 CH2 CH2 CH2

(xii) (a) (b) (c) (d)

CH3 CH2–CH3 CHMe2 CMe3.

H.C = 3  H 2H 1H O
a bcd

Me Ph 

(xiii) (a) Me–C+ (b) Ph–C+ (c) Me – CH2 3  H (d)
Me Ph Highly unstable
9H Resonance
101
(xiv)  In case of d and e resonace is present but in d having more  H.
 Check other by  H
deba c

 
CH2 CH2


(xv) (a) (b) 1H (c) 4H

-resonance

  

(xvi) (a) (b) (c)

Anti Aromatic Aromatic Resonance
highly unstable
bca

   
10. (i) CH3 – O – CH2 > CH3 – CH2 (ii) Me – CH > CH3 – CH2 – CH2
+M H.C Me 2H
6H
   
(iii) CH2 = CH – CH2 > CH3 – CH2 – CH2 (iv) CH2 = CH < CH3 – CH2
Resonance 2H H.C sp2 3H

   
11. (a) (I) CH2 > (II) CH2 = CH – CH2 (b) CH3 – CH2  CH2 
CH

more resonance Resonance

 
CH2 CH2
CH3–CH–CH3 CH3–N–CH3
(c) < (d) (I) <
CH3–C–CH3 CH3–C–CH3
 
H.C Resonance 6H 6  H + (+M of N)




12. (I) (II) (III) (IV)


6H Bridge head 1H 2H

Highly unstable
i  iv  iii  ii

102
13. (carbocation)

CH3 CH3

(A) C (B) CH3–C (C) CH (D) CH2 = CH – CH2
CH3 CH3 Resonance
9H 6H
Resonance

ADBC



14. k(a) CH3O CH2 (b) CH2

+M Resonance

 
(c) CH3 CH2 (d) CH3 – CH2
3H
H.C
a cbd

   
CH2 CH2 CH3 CH2

15.

OH NH2 CH3 C–C–C

C
+M, –I +M, –I H.C O  H, +I
Donation tendency of N > O
ii  i  iii  iv

  
CH2 CH2 CH2

16.
H2–CH CHMe2
CH3 NO2 NO2
H.C –M SIR not in resonance
i  iii  ii

103
  
CH2 CH2

17. (i) (a) < (b)

F NO2
–I –M

   
CH2 CH2 CH2 CH2

(ii) (a) (b) (c) (d)

Cl NO2 CN
–I –M, –I –M, –I
b>c>a>d

 
(iii) (a) CH2 – CH > (b) CH2 – CH3
O +I
Resonance

O O O +I +I
+I
(iv) (a) (b) (c)
 

more resonance Resonance, +I
+I, , stability of anion.
a bc

 

CH2 CH2 CH2

(v) (a) (b) (c)

Cl NO2
–I –M
ba c

 


(vi) (a) (b) (c)

Ant. A Aromatic
Resonance
bca

104
 CH2 CH2–CH2

(vii) (a) (b) (c)

Resonance +I Highly unstable
a bc

–I
–I
(viii) (a) (b) (c) –I
Resonance +I Less stable
a bc

(ix) (a) (b)  having more –I

Resonance –I
ab

–I Resonance

(x) (a) CH2 = CH (b) CH2 = CH – CH2 (c) CH2 (d) CH3
sp2 Resonance +I +I
dbca

18. HCC (negative charge is more stable on sp hybridised 'C')


CH2

19. –M, –I group  stability of carbon ion

NO2
–M, –I


20. Aromatic

O
CH3
21. CH2=CH–C > CH2=CH–CH2 > CH3–CH2 > CH2=CH
CH3
Reso + 6  H Resonance 3H

105
   
O O  O
22. (a) +M +M > > > >

O O O
+M +M –I Bridge head
Extended 'C' sp2

O O O O
   
(b) CH2–C–H > CH2–C–CH3 > CH2–C–OH > CH2–C–NCH3
+I +M +M

23. (iv) Ph–C–CH=CH2 i &iv

CH3

24. CH2=CH–CH=CH–CH3 > CH3–CH=C=CH–CH3

Resonance
C
C–C CH3

25. (a) > (b) >

7H 3H

(c) <

2H 4H

26. (a) 1-Heptene (b) 2,4-Dimethyl-l-pentene

CH3 CH3
C=C–C–C–C
C=C–C–C–C–C–C 1 2 3 4 5

7.C, 2  H 7.C, 5  H

(c) 2,4-Dimethyl-2-pentene (d) 4,4-Dimethyl-2-pentene

C C C

C–C=C–C–C C–C=C–C–C
7.C, 7  H C
7.C, 3  H

106
 (e) 2,4,4-Trimethyl-2-pentene
C C
HOC  number of 'C'
C–C=C–C–C 8.C 1

C Stability
ea dbc

CH3
27. CH3–C=C–CH3 > CH3–C=CH–CH3 > CH3–C=CH2 > CH3–CH=C
CH3 CH3 CH3 CH3

28. i &iv

29. > > >

Isobuten 2° anion
1° anion

30. Ans. (D > C > B > A)

(i) (a) (b)

8H 9H
Reso + H.C H.C

(c) (d)

4H 2H

(ii) (a) (b)

Reso + H.C 8H H.C

(c) (d)

5H 6H
107
(iii) (a) <

O O
(iv) (a) > Resonance more stable

CH3 H CH3 CH3

(v) (a) C=C < C=C
H CH3 H H
more stable Ci>

CH3 CH3
(vi) CH2=CH–CH > CH2=C
CH3 CH2–CH3
1H more stable 5  H

31. HOH
a bcde
(i) < (ii)
See  H
stable due to
resonance

(iii) (a) (b) (c)

less more stable

bca

(iv) (a) (b) (c) (HOH per benzene ring)

36 Ka R.E 63 Ka R.E K

cba

1
32. H.O.C.  number of 'C' atom 
stable &1

(i) (a) (b) (c)

6.C 7.C 8.C

cba

108
(ii) (a) (b) (c) (d)

(iii) (a) (b) more stable

(iv) (a) > >

33. (a) > (b) >

Resonance stability 3 = bond

(c) CH3–CH = CH–CH3 < CH3–CH2–CH= CH2
6H 2H

(d) >

3H 10  H

34. (a) (b) (c) (d)

stability order resonance extend resonance Benzene aromatic

ring
d  c  b  a H.O.C order a bcd

35. (57)
1-butene C=C–C–C 30 kcal
C=C–C=C 1,3-butation resonance
If two '=' bond mol in resonance than Holt = 2 × 30 = 60 kal
But due to resonance holt is slightly less than 60 kcal

Show
NMe2 sir NH2 SO3H NO2 Br

36.

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

109
 – –
O +
O O O SIR
+
N N NCr

37. (i) (ii)

resonance not is resonance
(B) C–N (1) < C–N (2)

N=O
5

38. O 1 3
N N=O
less resonance
O Br
When the l.P of Br participates in resonance long conjugation C–S–N and short with C–3 &
Cl–N & C–3–N so bond length of C–1–N & C–3–N are of same length and longer than C.S–N

ssp3
CH3 CH3 CH3
sp 2
Cl
39. (i) (a) (b) (c) r0
Cl
Cl
Direction of dipoles   
a bc (dipole moment angle  dipole moment )

NO2 NO2 NO2

Cl
(ii) (a) (b) (c)
Cl
Cl
Angle  dipole moment  a  b  c
NMe2 NMe2
3
Sp Sp3
(iii) (a) (b) a>b

40. Due to, bridge bound carbon can never be sp2 by brad's rule no real structure possible.

110
 EXERCISE # III


1. > R – CH2
Aromatic

2. (i) CH3 – O–

CH3 (ii) CH3–CH2–OH

NO–H–bonding Due to H–bonding intermolecular

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

3. CH3
– CH CH– C  N
sp (more electronegative)

 
CH2 CH2

4.

CH3 CD3
H.C H.C
Strength of C–D/H bond
C–D>C–H
–CH3 has more +H effect than –CD3

O O– O–
5. Acetate ion CH3 – C – O– CH3 – C = O– CH3 – C – O
equal R.S R.H
O O– O–
Formate ion H – C – O– H–C=O H – C – O
R.H C–O equal

NO2 O

6. (A) –M/–R, –I (B) +M, +I

O–CH3 CCH3

(C) +M, –I (D) –M, –I

111
 N=O N=O

7. (A) –N = O +M/–I –M/–I

P, Q, S
CH3H.C,+I

(B) –CH3 (R)

O
NH–C–CH3
O

(C) –NH – C – CH3 +M/–I

P, S

CH3 H.C

8. (A)  R +I

NH3 N can't form 5 bond

(B)  S

O–H OH NH2 NH2

(C)  P,T –I –I

(D)  Q

9. (A) Q, S (B) P, S

(C) P, S (D) R, S

4e–

10. – C – O – Et –C–O–C–
O O O
only one side here l.P involved in
resonance fast both side in resonance
a > b (bond length)

112
   
11. CH3 – C – CH3 > C – C > C–C
CH3 C
9H 6H 3

12. 2-butene H3C – C = C – CH3 6H

ethylene CH2 = CH2 less = bond character
pure '=' bond
Hyperconjugation effect , the '=' bond character

 —   
13. CH
 2 CH – Cl 

  CH2 – 
  CH Cl

 CH2 – 
  CH Cl 
–


'Neutral' completeoctet incompleteoctel

(I) (II) (III)

I  II  III

 
CH2 CH2 CH2 CH2 CH2
 
14. (A)


S  R.S
 
(B) CH2 = CH – CH2 CH2 = CH – CH2
A>B


O O

15. CH2 – CH – H CH2 = CH


16. CH3 – C – CH3 9H
CH3 H.C


17.
7H

113
  
18. CH2 = CH < CH3 – CH2
+ve charge 3  H H.C
on '=' bond

+ O +2 O–
19. (I) CH3–N – (II) CH3–N –
O O


20. 10 e– on 'N' not value
N N
H H
(I) (II)

21. Delocalization of electrons  molecular stability CO2 pot energy 



22. (I) Aromatic most stable compound 6e–


(IV) CH3 – CH– CH3
H.C least stable


23. (C6H5) C–Br 
heterolysis
 C

3 ring resonanc with C

O
HO O
24. (a) (b) (c) Azulene (f)

10e– HO O

114
 EXERCISE # IV (JEE-MAINS)
CH3 C
1. CH3 — C — > C — C — > CH3 — CH2 —
CH3
3° 2° 1°
+I effect order

O O–
–
2. H—C—O H—C=O
–1/2
O
–1/2
R.H H — C — O two equal R.S.

3. (i) Acetamide (ii) Acetic acid (iii) Acetonitrile

O O
CH3—C—NH2 CH3—C—OH CH3—C  CN
sp2 sp2 sp3 sp
O
(iv) Acetene CH3—C—CH3

4. CH3 (reactive)

  
5. (C6H5 )3 C  (C6H5 )2 CH  (CH3 )C
Resonance

  
 CH — CH3 CH2
6. CH3 — C — CH3 Cl — C — Cl
CH3 Cl CH3
Vacant-d- +I
+I
+I effect  orbital
resonance
Stability of anion
(equal R.S)
  
CCC 3  C6H5 CH2  (CH3 )2 CH  (CH3 )3 C

7. Non-Aromatic

sp3

115
8. Ortho-nitrophenol p-nitrophenol
OH
OH OH
H-bonding
NO2

NO2 NO2
Less acidic due to intramolecular H-bonding

9.

4e 4e
A.A A.A

H H Cl

10. (i) Cl—C—Cl (ii) H—C—Cl (iii) Cl—C—Cl
 
Cl Cl Cl
 = 0 most symmetrical

CH2
 
11. (I) CH2 = CH – CH2 (II) CH3 – CH2 – CH2 Resonance
resononc H.C.
III > I > II
N
C H H
C O O
=0
12. (1) =0 (2) (3)

C
C O O
N H H
=0 0
H H
S S

(4) 0
=0
S S—H
H
13. Non-Aromatic
116
 EXERCISE # V (JEE-ADVANCED)
1. HOH per mole of H2
CH3 C C
(A) C=C–C–C (B) C=C (C) C=C
cis
CH3 Trans
(d) C=C–C=C
C = C resonance stabilized
1
 HOH 
stability

ACBD


CH2

2.  stability


 O–CH3 + M, – I
 

CH3
Cl Cl
Cl
3. (i) (ii) (iii)
9-bond resonance (3  H) Cl

Cl

(iv) =0   D.M. 

Cl

iii  ii  i  iv

4. Because nitrogen can't form five bond.

5. 4ne–

117
6. P-hydroxybenzoic acid O- hydroxybenzoic acid
O
C–OH COOH
OH
(Inter molecular H-bond) (Intra molecular H-bonding)

OH
B.P order inter > intra H-bond

7. (A) CH3Cl (B) CH2Cl2 (C) CHCl3

H H H
H – C – Cl H – C – Cl Cl – C – Cl
H Cl Cl


8.

OH O
H

  
9. CH3 – O–

CH– CH– CH  CH 2

Lp and C repulsion.

10. Adjacent positive like charges unstable

  O
(A)  N
O
+ve and +ve repulsion.

+I 
 
11. (I) O (II) (III) O (IV) 
6  H +M 5H 3  H +M 2H

+M and 2CH3 +I effect

I  III  II  IV

118
         
12. (I) CH 2C N N (B) CH 2 – N  N (C) C H 2– N  N (D) CH2 – N  N
complete octet Incomplete octel complete octet
–ve charge on 'N'
+ve charge on 'C' (For maximum stability)

CH3 
CH2CH3
H
H.C = 6 (6  H)
13.

O


14. Anti aromatic Anti aromatic

H
O–(f)
 H
15. (i) H—C—C
H
H
Vacant P

H ()
O–(f)
H
(ii) H—C—C—C
H
H

NH2 N NH2
16. Melamine N N
NH2

119
17. 9 R.S
OH O
NaOH
+ H2 O


O O O


(1) (2) (3)
O O

 
(6) (4)
 
O O

(7) (5)
 
O O

(8) (9)

18. tub-shape (non-planar) non-aromatic


 4e– 4n = 4 n = 1 Anti-aromatic

sp3

 Aromatic  Non-Aromatic

 

 6e– Aromatic  4e– Anti Aromatic

 6e– Aromatic  Aromatic compound

6e–

 Aromatic

14e–

120