Inductive effect and resonance

Exercise -1

PART A: (Subjective)

1.. Write the direction of Inductive-effect in following compounds.

CH = CH,

(III) ~

C",CH

~,/COONa

(II) T

OH

2. In which of the following cases I effect has incorrect representation.

COOe

(5)6~

OCH,

C",N:

(2)V

(3)U

o

COOH (IV) jJ(.

NaO

(4) CH3 - CH2 -+- MgBr

3, Arrange the following groups in increasing order of magnitude for -I effect

- S03H, - SR , - flR, - S02R

o

n III IV

Write the decreasing order of dipolemoment for following compounds:

(I) CH3-CH2-CN (II) HC",C-CI (lll) CH2=CH-C1

4.

5, Write the decreasing order of dipole moment and boiling point for following compounds:

(I) CH3F (II) CH3-CI (III) CH3-Br (IV) CH3-1

6. Arrange decreasing order of dipolemoment for following compounds:

(y)

CH3-CH2-N02 CH3-CH2COOH

CH3-CH2-NH2 CH3-CH2-OH

II!

IV

Ell

CH3-CH2-N(CH3)3 CH3-CH2-C=N

CH3-CH2-C1 CH3-CHz-NH2

7. Arrange the following in decreasing order of their solubility in water:

CH,'-.... /CH,

/c=c'-....

H H

I

CH" /H

/C=C,

H CH,

Ii

CH" ,/H

/c=c"

H Br

III

Write the resonating structures of following compounds

(I) Benzene (II) Naphthalene (III) Anthracene

9. Identify the more stable form in the following resonance structures.

NH2 NH
I I \9
(i) NH2 - C - NH2 and NH2-C = NH2
e
(1 ) (2)
0
a 6
(iii) a and
e
(1 ) (2) (IV) Phenanthrene

o 0 0 00

.. ii 0 II II I

(II) CH -C-CH-C-CH3 and CH3-C-CH=C-CH3

(1)

(2)

0° 0°

I .. I ..

(iv) CH3 - C - OH and CH3 - C = OH

e .. e

(1) (2)

10. Write the stability order of following resonating structures:
I II I II
e 0 I'DOCH3 OCH3
a
(P) 6 ~'" 6 (Q) QNH ( ) ~~H

N e 2 2
e 0
a
¢ en I'D
(R) (--;> (8) Cl< ) ~
( Ci ~~I
.«/I'-j~ /N, e
o 0 o 0
PART: B (SeQ) 11. The inductive effect.

(A) decreases with increases of distance

(8) its extent increases with increases of distance

(C) Indicates the transfer of 11: electrons from less electronegative atom to more electronegative atom in a molecule.

(D) Show the transfer of lone pair of electrons

12. Inductive effect involves:

(A) Oelocalisation of (J - electrons (C) Oelocalisation of IT - electron

(8) Displacement of (J - electrons (0) Displacement of n - electron

13. Choose correct statement

(A) I effect transfers e - from one carbon atom to another (8) I effect operates in both (J / 1I bond

(C) 1 effect creates net charge in molecule (0) I effect is distance dependent

14. VVhich of them shows incorrect representation of Inductive effect.

o

II G

(C10.f+O

(0) CH3 -E- IT +-CH2 +- CH3 o

15. What is the % s character in hybridisation of carbon when it exerts strongest -I effect

(A) 25% (8) 50% (C) 75% (0) 100%

16. Which of the following is not involved in resonance

(A) 11: bonds (8) positive charge (vacant orbital)

(C) negative charge (lone pair) (0) Sigma bond

17.

In which of the following resonance is possible (A) CH2 = CH - CH2 - CHO

(C) CH3COCH3

(8) CH2 := CH - CH = 0

(0) CH2 = CH - CH2 - CH = CH2

18. Which of the following compounds have delocalised electrons?

NH~

I

(810

(0) CH2 = CH - CH2 - CH = CH2

t 9. Which of the following species are conjugated?

..

:SH

(8)6

(0) All of these

~O. Which of the following pairs of structures is not a pair of resonating structures?

(A) (fj Ell ..

H-C=NH; H-C=NH

(C) CH3 - C = CH - C - CH3

be ~

(D) 0 ; CJ"

Ei)

!1. Which of the following is not a permissible resonating form:

e

CH3 - C - CH - C - CH3

II II

o 0

+ .. ~

(A) CH2 - ~ - Q:

CH3

+ ~

(8) CH = N -0: 2 I ..

CH3

(C) CH2 = ~ = o.

I

CH3

!'! +

(0) CH2- N = 0:

I ..

CH3

!2. Which of the following pairs of structures do not represent resonating structures?

o II

(A) CH3 - C - CH3

(8) 00; D-.d'

EBOH OH

II I

(C) CH3 -C-CH3 ; CH3 -C-CH3 EEl

!3. Which of the following resonating structure is the minor contributor to the real structure

o

II CH,-C-OCH,

I

0- I

CH,- £ - OCH,

II

0-

I +

~ CH,-C=OCH,

(A) I

(8) II

(C) III

III

(0) All structure are equally stable

!4. HNCO is isocyanic acid exists as following resonating structures

e $ $ e

H-N=C=O ~ H-N-C=O ~ H-N=C-O

II III

The correct order of stablity is :

(A) I > III > II

(8) I > II > III

(C) II> III > I

(0) II > I > III

!5. Which will be the least stable resonating structure:

E9 0

(A) CH, = CH - CH - CH - NH,

o E9

(C) CH, - CH = CH - CH = NH,

o E9

(8) CH, - CH - CH = CH - NH,

o E9

(0) CH, = CH - CH - CH = NH,

27.

28.

26.

Which of the following example has both the resonating structure contributing equal to the resonance hybrid

$ $

(A) CH3-C-CH =CH-CH3 ~ CH3-C=CH-CH-CH3

I I

C~ C~

(8) CH3-C-NH2 ~

8

..• -: ••

..

, ,

e 0

(0) CH2 = CH - CH = 0 ~ CH2 - CH = CH - a

Least contributing structure in nitroethene is

+..-;:::::0 + +..-;:::::0

(A) CH,=CH-N( (8) CH,-CH-N(

0- 0-

Which will be the least stable resonating structure:

0=Et> 1° .r=«: 1°

(A) N'-..00 (8) ~ N'd-~

+ +0°

(C) CH,-CH-N( 0-

29. Which of the following resonating structures of 1-methoxy-1 ,3-butadiene is least stable:

e Ell e Ell

(A) CH2 - CH = CH - CH = 0 - CH3 (8) CH2 = CH - CH - CH = 0 - CH3

e Ell EEl e

(C) CH2 - CH - CH = CH - 0 - CH3 (D) CH2 = CH - CH - CH - OCH3

30. The pair (s) of groups both of which have overall electron withdrawing effect when attached to a phenyl ring

(A) -CI, -N02 (8) -N02, OH (C) -CI, -OH (D) -CN, -NH2

PART: C (MCQ)

31. Which of the following statement (s) is (are) correct for the inductive effect?

(A) It is a permanent effect (8) It transmits through sigma electrons

(C) It is represented by () (D) !t is represented by - >

32.

During resonance, which is/are correct (A) Net charge remains same

(C) Number of unpaired electron remain same

(8) Number of paired electron remain same

(D) Energy of resonating structures always remains same

33. Which of the following statements is/are correct?

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

(8) The resonance energy is the difference between the enthalpies of formation of the molecule and the resonating structure having maximum energy

(C) Kekule's structures have larger contribution than Dewar'S structure in the hybrid structure of benzene (D) In delocalized structure of benzene the n-charge cloud is spread equally above and below the plane of molecule

Which of the following is / are resonating structures of diazomethane

;,.--N + - - +

(A) CH,"'-._II (8) CH2 = N = N (C) CH2 - N == N

N

34.

(D) all of these

35. Which of the following pairs represent resonating structure.

(A) 6 and 6 (B)CH,CH=CHCHCH=CH,andCH,CHCH=CHCH=CH,

+

(0)0

+

and

+

EXERCISE # 1

1.

~CH3 (1)4J-COOH

_t. vCOONa $CH = CH2

(II) ./" t (III) 0

OH

C=CH

eOCH (IV) P

NaO

2. Cases 1, 4, 5, 7 incorrect representation of I effect

3. increasing order of magnitude for -I effect is" < "' < IV < I

4. decreasing order of dipolemomentfor given compounds I > IV > III > II

5. ).t = CH3-CI > CH3F > CH3-Br > CH3-1 B.P. = CH3-1 > CH3-Br > CH3-CI > CH3F

6. decreasing order of dipolemoment for following compounds

(x) : III > I > IV> II (y) : I > III > II > IV

7. IV> Iii > I > II

01 O~

8. (I);:.... ~ .0

Benzene has two

~ (II)~

Naphthalene has three

Anthracene has four

(IVlCr:O ~ o:o~ ~ ~ cy ~ ~
.,---:; .,---:; ;:.....,---:; ;:....:::-.. »: ;:....
I I I I) . ".
~ ~ ~ <» I,.:::;
Phenanthrene has five resonating structures
~'L (i) -? 2 (ii) -? 2 (iii) -? 1 (iv) -? 2
10. (P) I> II ; (Q) II> I ; (R) I> II; (S) II> I
11. A 12. B 13. 0 '14. D 15. S 16. D 17. 8
18. B 19. 0 20, B 21. C 22. A 23. B 24. A
25. A 26. C 27. C 28. C 29. D 30. A 31. ABD
32. ABC 33, ACO 34.····· BC 35. SO · .'. .'. . '.' ... ' . . . . ..... : -.' .'."-:-~::. '.' ... .. :.<:' - '-.-: -: _,< --' .

85<~-~ ··'::O:;:-::1iifo:·,···,··';::,~.o:--_- __ -~-"----'-,;,:,"·_~':r.:-_:~-,.;.;.~'-~J~-"=<'-:-.e-JO~,(';~~~:;:-:.$":.;::r;~~-,_:;.'s·:,·.'fv_:~x:.-;.l·ff-,W~cJ-,:-.;~="':"~_"""'-_':"_~K<-"O-~--"';"_";:;-:;-j"~·f.-..,""","':P:.~~;;h''');\.~·:'''::;'-'';;''-<:-.i;ff;;f.%i;;~0_; ... ?,-,':;f_-.:~>_-;_:.,_: __ :)fr""':7~'·!':>·',,:-i·::':';··:·"··7 .. -~~·:-,:~.:,.:..;>::.::_~~·~:''t'?:~:--~~~~~~>~:-' __ 9

PART: A (Subjective)

1. Give the number of hydrogens involved in hyperconjugation in the following compounds '?

CH3 CH

I I 3

CH3- C~ /CH - CH3

C=C

/ "

CH - CH CH - CH,

3 I I

CH CH3

3

IV

CH3 CH3

I I

CH3- CH - CH = CH - C - CH3 I

VII CH3

~

CH3 - CH - CH - CH3 , i

CH3

X

CH3 I

CH3- CH CH _ CH

" / 2 3

C=C

CH( "Ch3

II

VIII

@ CH3 XI

CH3

I 9 CH -C-CH

3 I 2

CH3

XII

CH, !

CH3-- CH c~'.'

" " 11,.--

,y" t.

G=C

/ '''CH C""

CH -CH - il3

J .f,. I

CH;

I

Ph --

6

XIII

III

VI

- He :c; eH ~.- -

(1) CH3 -,.- CH,

IX

2. Write the number of hyperconjugable hydrogen atoms of following species:

6)

(b) CH3-CH-CH2-CH3

3. Arrang the stability order for following compounds:

(I) CH2=CH2 (II) CH3-C=CHz (III)
I
CH3
(IV) CH3-CH=CH2 01) CD3-CH=CHz
4. Write the stability order of alkene by hyperconjugation : (I)

(iii)

(II)

(IV)

S. Write the stability order of following carbocatlons
I II III IV
~ (3 0 c5
(P) 6
($
CH3,'-. $ CH3 Ph
63 I I
(0) CH3-CH-C,Hs /C-CH3 Ph--C-C H Ph-C-C2Hs
CH, ($ 2 b e . foi!owing compound contains three C=C bond arrange in stability order:

CH, CH, I b I a

C=y-C=r-H

CH3 CH3

H

H

if c Write the correct heat of hydrogenation order:

~,~~/' <,

I

~)1'v)l..........

III

IV

13" Among the following compounds, the decreasing order of reactivity towards electrophilic substitution is:

CH, OCH, CF,
~~ 0 ~. 6
I II
~)J ;J LJ
II III IV Observe the following compound and report the values of P, Q, Rand S.

P ,:; Number of geometrical isomers

Q ::;: "lumber of optically active compounds

R = Number of hyperconjugable hydrogen atoms

S::;;: If the statement that the )C ::: C( double bond length is shorter than "):C = c( length of ethene is then S=:;O (zero), if false then S :: 1.

'\I\frite the correct reactivity order of following compounds towards nitration in aromatic ring

o II

CH C-O-CH

@' ,

(I)

(II)

nIl)

o

!I

~C-O-C,H'

(IV)

PART: B (seQ)

11. The no-bond resonance is known as :.

(A) mesomerism (8) conjugation (C) hyperconjugation (0) metamerism

12. In hyperconjugation there is overlap between :

(A) p- and n-orbitals (8) 2 1t - orbitals (C) d-end-n-orbnal (D) a -and n- orbitals

13. Hyperconjugation involves

(A) delocalisation of a-electrons into an adjacent p-bond

(8) delocalisation of p-electrons into an adjacent double bond (C) delocalisation of 1t-electrons into an adjacent double bond (0) All are true

14. Hyperconjugation phenomenon is possible in CH3

I

(A) CH - C - CH = CH_ 3 I <

CH3

(C) C6H5 - CH = CH2

15.

Stability of following alkenes in the increasing order is

CHaCH = CH - CH3 CH3 - C = C - CH3 CH3 - ~ = CH2

I I CH

CH3 CH3 3

(I) (II) (Iii)

(A) I < III < IV < II

(8) I < II < III < IV

(C) IV < III < II < !

16.

Which of the following carbocations is most stable CH2CH3

I

(8) CH3 CH2 - C$

I CH2CH3

CH, E9

(C) )CH

CH3

CH3 - C == CH - CH3 I

CH3

(IV)

(0) II < III < IV <: I

17. The C - C bond length in propene is little shorter 149 pm than the C - C bond length 154 pm in ethane. This is due two

(A) + I effect of CHa group (8) mesomeric effect

(C) electromeric effect (D) hyper conjugation

18. Alkyl group are 0, p- directing because of

(A) Inductive effect (8) electromeric effect (C) hyperconjugation (C) All the three

19, Which one of the following has all the effects, namely inductive, mesomeric and hyper- conjugative?

(8) CH3 - CH = CH2

(C) CH3CH = CH- C- CH3

~

20.

,

Correct arrangement of the following Acids in correct K, order is

@ ,

H3N - CH2 - eOOH NC - CH2 - COOH

(I) (II)

H3C - CH2 - COOH (III)

(A) I > II > III > IV

(8) II > I > III > IV

(C) I > III > II > IV

(D) CH2 = CH - CH = CH2

e

ooe,,, CH2 - eOCH

(IV)

(D) IV > HI > II > I

21. The electron density at benzene ring in the following compounds follows the order:
COOEt OCOEt 6' 6COCH,
© ©
I II m IV
(A) IV > III > II > I (8) I > II > III > IV (C) IV > II >- I > III (D) IV > u > III > I 22. Select the option that incorrectly defines the order of electron density in benzene ring.
OH CI @
(A) @ > @ > @ :>
NH2 NO CN NO,
(8) @ > @ > @ > @
eN CH3 OH
(C) @ < @ < @ < @
NH2 0 OH OCH3
0
(D) @ > © > © > © 23. The correct order of increasing C-O bond length of CO, CO~- I CO2 is

(A) C032- < CO2 < CO (8) CO2 < C032- < CO (C) CO < CO/- < CO2 (0) CO < CO2 < CO/-

~4. Which of the following molecule has longest C = C bond length?

(A) CH2 = C = CH2 (8) CH3 - CH :: CH2

250 The decreasing order of bond length of C = C bond in the following compounds is:

0 H,C)) 0 0
H3C
I II III IV
(A) n :> I > IV > III (8) III :> I > II :> IV (C) IV > IT :> I > III (0) IV :> I :> II :> III 2~t Give the stability order of the foiiowing compounds.

6'

H Y (I)

~t

(HI) Y

(A) I > II > HI > KV

(8) IV > I > II > III

(C) IV > I > III > II

(D) ]V > II > I > III

27. Match List - I with List - II and select the correct answer using the codes given below.

List - I (Stability) List -II (Reason)

CH3 EJj CH3 EB
(I) "'C/ > CH3 (A) Inductive effect
6
/"CH3
(II) H c-ce e (B) Resonance
3 ......... < CH
CH 3
3
CH3
/" EB
(III) H3C - CEB > H C _ CH2 (C) Hyperconjugation and resonance
'CH 3
3
. 6tH:
ctH,
(IV) > CH, (D) Hyperconjugation and inductive
~
Codes:
(A) I-B, 11- C, III-D, IV-A (B) I-C, II-A, 111- D, IV-B
(C) I-D, 11- C, III-A, IV-B (D) I-C, 11- D, 111- B, IV-A 28. The reactvity order of benzene ring for the given compound is (benzene ring with highest 1t electron density will be most reactive)

~

CH3

Y

z

~

CI

w

(A) Y > z > w > x

(B) z > Y > x > w

(C) z > y > w > x

(D) z > w > y> x

29. Choose the correct statement about this compound.

~5

N~N02

Br

(A) All three C - N bond are of same length

(B) C1 - Nand C3 - N bonds are of same length but shorter than C5 - N bond (C) C1 - Nand C5 - N bonds are of same length but longer than C3 - N bond

(D) C1 - Nand C3 - N bonds are of different length but both are longer than C5 - N bond

The least stable resonating strucutre is

(A)eo~EB

30.

(B)O~ EB

(D)r,/"VV

PART: C (MCQ)

31.

Hyperconjugation can explains the stability of the following:

(A) carbonium ions (8) carbanions (C) free radicals

(0) carbenes

~n, Which of the following represent the resonating structure of 0-0 .

(8) 0-0 (C)~ (D)0-0

Which of the following is true for stability between the two structures.

CH,

(B)CH2 := CH-CH:= CH--CH; > CH,-~~CH = CH,

CH3

I (-!:) e

(C) CH2 :::: C - CHz > CH3 - eH :::: CH - CH2

o

'@- e II e

(0) 0 < CH3 - C - 0

34, Which of the statement is/are correct about foliowing resonating structures

(A) I and Il structure have equal contribution towards the resonance hybrid (8) III structure is most contributing to the resonance hybrid

(C) The stability order is I :::: II > III

(0) The resonance hybrid is more stable than I, " & III

3~, Choose the correct statementis) :

Always ail canonical forms do not contribute equally to the resonance hybrid, (8) In ethanamine and ethenarnine nitrogen is Sp3 hybridised.

(C) Ail 'C-O' bond length in carbonate dianion are equal.

(D) CH2=C=O does not exhibit resonance because it is not a conjugated system.

EXERCISE # 2
1. (I) 12 (II) 9 (III) 6 (IV) 4 (V) 3
(VI) 2 (VII) 1 (VIII) 6 (IX) 3 (X) 4
(XI) 0 (XII) 0 (XIII) 4 (XIV) 6
2. (a) 3, (b) 5, (c) 9, (d) 5 3. III>II>IV>V>I
4. I > III > II > IV 5. (P) III > II > I > IV ; (Q) IV> III > II > I
6. b>a>c 7. I < II < IV < III
8. III > I > II > IV
P Q R S 1
9. 2 4 7 1

H
~I
C-H h
I
H
H H It has two geometrical isomers at double bond (acyclic)

It has four optically active compounds having configurations.

R, E R, Z S, E S, Z

It has 7 hyperconjugable hydrogen atoms. (shown in figure). It has a conjugated diane so its double bond character at C = C will be less, so it will be longer than that of ethene.

10. IV> II > I > III
The electron releasing effect of the following groups follows the order:
0 0
II II COOC2HS
- 0 - C - 0 - C2HS > 0- C-C2HS > CH2COOCH3 >
(+ m > - I) (+ m > - I) (+ I only) (- m, -I)
11. C 12. 0 13. A 14. 0 15. A 16. A 110 D
18. C 19. C 20. A 21. 0 22. 0 23. 0 240 0
25. B 26. C 27. B 28. C 29. C 30. C 310 AC
32. ABeD 33. BO 34. ABO 35. AC -

Acids

PART: A (Subjective)

'1. Write the acidic strength order of following compounds:

I II III

(M) HCOOH CH3COOH FCH2COOH

(N) HC:=CH C2H4 C2H6

(0) H20 HC=CH C6HsOH

(P) CH3-CH -eOOH I

F

(0) CH2 -COOH I

N02

CH2-C00H I

F

CHz-COOH I

Sr

2. Write the correct order of ease of deprotonation of labelled H-atoms.

4 1 Hooc:qS03H

::::.... I 2

0zN. C:; CH

o

CH3

3. Write the correct acid strength order of labelled H-atoms.

H-{0o

CH~)~ __

HO OH

(x) (y)

Write the correct order of acid strength for following compounds.

I IT ITI

(P)

eOOH COOH GOOH
~ ~ ~
N02 S03H OH
COOH @H OH
@ @
GOOH eOOH GOOH
@ p-'("<,,..,CI ©rCH,
I (-., ff
1\.""/)
~'"
GOOH eOOH eOOH
~' ©rF ©rCI
$~.' (0)

(R)

(S)

IV BrCH2COOH

CH30H CH3-C-OH

~

GH3- GH -GOOH I

Sr

GH2-COOH

tN

IV GOOH

~

NH2

eOOH

©rOMe

OH

5. (z) aooc

HO

eOOH (x) OH

eOOH (y)

Write the correct acidic strength order of acidic hydrogen x, y and z.

6. Write the Ka1 values in decreasing order of following acids.

H" /COOH HaC" /COOH H" /COOH HaC" /COOH
C C C C
II II II II
C /C" C /C"
H2N/ "H HaC COOH H/ "NH HOOC CHa
2
(W) (X) (Y) (Z) 7. Write the correct order of acidic strength for following compounds
I II III
eOOH COOH COOH
&CI &F 6
(P)
.Q .Q
OH OH OH
&CI &F 6
(0)
.Q
COOH COOH COOH
(R) ¢ ¢ 6
CI F 8. Write tile correct order of acidic strength for following compounds.
F COOH F F
Fx$rCOOH (§rCOOH 6 F-:W-©-COOH
M=F F
IT F F
F III IV
T
OH OH OH
N;&NO' 0 ¢ OH
O,N&NO
I ~ 2
NO .Q
2
(II) ,
(I) N02 (IV)
(III) Write acidic strength order:

~NO'

NO,

(I)

10. Identify the feasible reactions

9.

~H

NO,

(II)

eOOH eOONa
(I)@ + NaHC03 ~ @ + Hp + CO2
o $
NH2 NHNa
(II)@ + NaHC03 ~ @ + Hp + CO2
OH ONa
(III) @ + NaHCO, ~ @ + Hp + CO2 (IV) ~ONa . + .~OH N02

COONa

+~

PART: B (SeQ)

Amongst the following compounds select the strongest acid / correct acidic strength order I correct option.

11.

(A) CH3CHCOOH

~O

2

(8) CH3 - yH - COOH

I

CI

(D) CH3THeOOH C=N

12.

(8) H3Nffi - (CHZ)2 - eOOH (D) CH3 - (CH2)2 - COOH

(A) HOOC - (CH)2 - COOH (C) F - (CH2)2 - COOH

o

II r;:::.yO - C - CH3

(A) ~COOH

13.

~COOH (0) ~CH3

@teOOH

(C) C - 0 -- CH

II 3

o (o-Methoxycarbonyl benzoic acid)

(o-Toluic acid)

(Aspirin)

(Oil of winter green)

14.

©COOH

(I)

CH3CH2COOH (III)

CHz == CHCH2COOH (II)

15.

o

II

c (j(' "OH

02~

I

(A) I > II > II j

16.

eOOH

m@

(A) II > I > III > IV > V (C) II > III > I > V > IV

17.

COOH

6

(II

(I)

o II

. C-OH

CH'~

II

(8) II > I > III

eOOH

(ll)~

N02

eOOH

(!Il) ~

OH

(C) I > !II > II

eOOH

(1v)~

NH2

(8) II > I > III > V > IV (0) I > II > III > V > IV

eOOH

erNO,.

(D) III > I -u

(V) l$J

OH

(V)

(A) I < II < III -c IV < V (8) IV < I < iii < II < V (C) III < II < I < IV < V (0) V < IV < III < II < I

18.

(A) IV> I > II > III

19.

eOOH (~/OH (I)LSJ

(A) III > IV > I > II

20.

eOOH

I

N02~N02

(I) 0

(A) (Ill) > (I) > (IV) > (II)

eOOH

ONO

2

(II)

(III)

(8) II > IV> III > I

eOCH O~OH (II) L9J

(8) II > I > III > IV

(IV)

(e) I > IV> II > III

eOOH

I

(III)~H'

(C) II > III > I > IV

~o,

(III) Y

NOz

(S) (I) > IIID > (II) > (IV)

(IV)

(0) IV> II > I > III

eOOH

(1V)0J

OH

(D) II > I > > IV > III

(IV)

Phenol
Mark the strongest acid in following questions
OH OH OH
21" (A)¢ ¢ ¢
(8) (C)
NOz CI CH3
OH
OH OH ¢
22. (A)aF (8)A
(C)
~F F I/N02

(A) M

O,N

24.

OH

(A) 0

02~N02 C

ill

N

25. The Correct order of acidic strength is -

OH

(D)¢

NHz

OH (o)A

U

?H (O)~I

~ NO

2

NO,

OH

(0) 0

02N~N02 CHO

LMe Me~Me rb Me-,&Me ~ r&

~ ~ ~ ~ Me~Me Me~Me

N~ N~ N~

I II III IV V VI

(A) III> IV> VI> V> II> I (C) III> IV> V > VI > I > II

(8) Ill> IV> VI> V> I> II (O) IV> III> VI> V> I> II

26. Amongest the following compound strongest acid is

~OH (A) LSJ

OH (C) rC3I ~

27. The correct order of acid strength of therollowing compound is -

(I) CH3 -C-CH3 "

o

(A) III> II> I

(II) CH3 -C-C-CH3 " II

o 0

(8) HI> I> II

(III) CH3 -C-CH2 -C-CH3

II II

o 0

(C) II> I> III

(0) I > II > III

28. The decreasing order of acid strength indicated by the following sequence of reaction is

~

@-C-H

@

NaNH,

(A) NH3 > Ph3CH > C2H2 > Hp

(e) HC == CH > Hp > Ph3CH > NH3

(8) Hp > HC == CH > Ph3CH > NH3 (0) Ph3eH > HC == CH > Hp > NH3

29. ln the following arrange the H (numbered) for their ease of displacement during acid base reaction.

(2) OH (3)HO~

-...;::: ~

d /3 ~'H

<s-: (1)

(A) 1 > 2> 3

NaNH2 (liquid NH3) 2 equivalent

(8) 3 > 2 > 1

30. The correct pKa order of the foliowing acids is

H-OgO-H o (P) "0

(A) P > Q > R

PART: C (MeQ)

(8) P > R > Q

In which pair first is stronger acid than second. (A) Adipic acid, succinic acid

(C) Phthalic acid, terepthafic acid

32. Which of the following is/are correct for Ka order

31,

COOH 1.cH3

(A)@(

eOOH

/' > 12J

>

COOH

©l>

CH,

~ r::"

fB) ( 0 ;-CH2 - eOOH > \ 0 )--COOH

.. 'L_;. ,_I

COOH HO I OH (0) l§:(

>

(C) 3 > 1 > 2

(0) 2 > 3 > 1

HO):=:(OH o (R) 0

(C) R > Q > P (0) R > P > Q

(8) Fumaric acid, maleic acid (D) Salicylic acid, 0 - toluic acid

eOOH I

@

i CH3

> CH3 - coon > ~-OH SO,H

> ~OH

CH~CH3 N02

eOOH

~OH

>LSJ

33. Which of them is arranged correctly for decreasing Ka order

(A) CH4, NH3, H20, HF (8) CH3 - OH, CH3 - NH2, CH3 - F, CH3 - CH3

(C) HI, HBr, ncr. HF (0) PhOH, Hp, C2HpH CH3-C=CH

34. Select the correct option

(A) Carbonic acid is weaker acid than acetic acid.

(8) The boiiing points of acids are higher than corresponding alcohols. (C) Chloroacetic acid is stronger acid than acetic acid.

(D) Phenol is more acidic than ethanol.

350 In which of the following first is more acidic than second.

OH

A

UOH

A'

fD)Y

N02

OH

A

(8) MeYMe

N02 OH

9

OH

OH MehMe

y

N02

OH

(A)¢

CH3 OH

(C) 9

OH

OH

(rCH3

I

,

,; . , '

If

.'

. ,

..... " . '. " ' ~

EXERCISE # 3

1.

(M) (0) (0)

III > IV > I > II; (N) IV> III > I > II; (P) I> IV> II > III

IV> I > II > III I > IV> III > II

2. 1 > 4> 2 > 3

Acidic strength order is, -·S03H > -COOH > -C=CH > -CH3

3. x> y > z

4.

(P)

II > I > Iii > IV, (0)

Ii > I > III > IV, (R)

II > Iii > IV> I, (S)

! > IV> III > II

5. x> z > y

O''-H

. 'S

/0 C

g

6. X> Z > y > W

7. (P) I > II > III, (0) I > II > III , (R) I > II > III

8. M = I > IV > II > III, N = IV > III > I > II

9. I> II

10.

(I) and (IV)
The stronger acids displace the weaker acids from the salts of weaker acids.
A 12. B 13. C 14. A 15. C 16. A 17. A
D 19. B 20. B 21. A 22. A 23. C 24. C
B 26. B 27. A 28. B 29. B 3O. C 31. CD
AC 33. BCD 34. ABCD 35. AD 11.

18.

25.

32.

PART: A (Subjetive)

10 Write the basic' strength order of the following amines :

I II III

(P) (CH3)31\J (0) (CH3)2NH (R) (C2H5)2NH

(CH3)2NH CH3NH2 (CH3CH2)3N

CH3NH2 (CH3)3N (C2H5NH2

2, At what position the base shows faster reaction in the compound.

o

'0~::

3V5'

4

:t Write the increasing pkb values for following compounds:

e e e e

CH3, NH2, OH' F

4.

H

I

(PiN • i'" '"

£"'//""1'.1

o ~~~o

~

(q)

Write the correct basicity order of atoms p,q and r is :

(Gaseous phase) (H20 as solvent) (H20 as solvent)

5. What is the effect of substitution of electron releasing and electron withdrawing groups on the basic strength of aniline.

0.

'X'

Hel (2eq.)

Identify the X.

70 Mark the more basic atom

F\

I \

(iii) N~ ,.....N - .. H

1 '/ 2

8. Which nitrogen is more basic

(c) Arrange the following compounds or anions in order of decreasing basicity

0 0
II "
(i)~- .0:)- CX)-
# C/
11 (Y) (Z)
o (x)
(ii) H2O H2N- HO-
(X) (Y) (Z)
(iii) HO- H2N- N03-
(X) (Y) (Z)
9. Write the decreasing orderof basic strength -
0 0 OJ 0
N
N N ~
I ~
H
(I) (II) (III) (IV)
10. Write the correct basic strength order:
0 0
~NH" /CH3 II
?i ~ /CH, H2Nl§(~
NH o CH3
0
I II m
PART: B (SeQ) 11.

Choose Correct option I order of Basic strength in the following question:

(I) R4N+ OH- (II) R3N (III) R2NH (IV) RNH2

(A) (1) > (III) > (IV) > (II) (B) (IV) > (III) > (J) > (II)

(if R '" Me)

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

(D) (II) > (IV) > (1) > (III)

Correct option for order of basic strength in the following questions (Q. No. 12 to 15)

0 6' Q'
"':
12. I //
I ~
~ CH3 N02
II III
(A) II > I > III (8) I > II > III (C) III > II > I (0) II > IIi > I 13.

°

II

~ C-CH,

: ~

"

(A) I > II > III

(8) III > I > II

14, (llOON"

o (lIl~N' o

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

15.

Q-NH2 (I)

(A) III > I > II

(II) (III)

(8) III > I > II

(C) III > II > I

(1IIl©r:;J' o

(8) (IV) > (I) > (II) > (III) (0) (I) > (III) > (IV) > (II)

(C) 1 > II > III

Choose the strongest base among the following:

i6. (A) -CH2 - CH2 - NH2 (8) -CH2 - CH = CH2 (C) -CH2 - C == N

18.

19.

e (Al@

(A)

Q

N

22,

NH2 (Al6

(C) CaHs - C - NH2 "

o

(C) m-N02 - C6H4NH2

s

(C)( )

N I H

(0) II > I > III

(IVl~O

(0)11>1>111

e (DlO

{O)Q I

H

The decreasing order of relative basic strengths of following compoundsrenlons is :

23. OH-, NHz-' H - C =: C-, CH3 - CH2-

24.

25.

26.

(A) CH3 - CHz<- > NH2~ > H - C == C- > OH(C) OH- :> NHz- > H - C == C- > CH3 - CH2-

(8) H - C =: C-> CH;,- CH.:- > NH2- > OH'\0) NH - > H -- C c= C-~ > OH-' :> CH - CH -

2 3 2

(A) (I) > (II) > (IIi) > (IV) (8) (III) :> (IV) > (II) :> (I) (C) (I) > (Ii) :> (IV) :> (ill) (D) (II) > (IV) :> (III) :> (I)

o

(III)

I c-,

,

:NH2

(iV)(J

N I H

(A) (iV) > (I) :> (1) :> (ill) (C) (II) > (I) :> (IV) > (III)

(B) (I) > (II) :> (Ill) > (IV) (0) (II) > (I) :> (III) > (IV)

(I) CHpNa (IT) CH3NHNa

(A) (N) > (II) > (I) > (III)

(C) (IV) :> (II) > (HI) :> (I)

(HI) CH3COONa (IV) CH3Na

(8) (III) > (I) > (IV) > (II)

(0) (II) > (J) > (III) > (IV)

27. (-~\ T) 0 C)
'N/ " .. N
'~N I
I I CH3
H H H
I II III IV
(A) I > H! > IV:> iI (8) II! > II > IV :> f (C) IV> III > II > I (0) II! > IV> I > II 28.

(A) I > Il > IV > HI ca) II > rv » I > III (C) IV > n > I > III (0) IV > II > HI > I
NH'\,_ /NH, NH" /NH, NH~ /NH, NH" /NH2
C C I" C
.....
@ I ~ I
29. (I) (II) ©J (III) (IV) (9J
! \
""~)
I
NH, NO, G!
(A) (II) > (!V) :> (I) :> (II!) (8) (III) > (I) :> (IV) > (II) (C) (III) > (IV) > (I) :> (II) (D) (11) :> (!) :> (1\1) > (iii) 30.,

The correct basic strength order is

<::;> (21 8 888

(A) GH3--CH2 :> r~H" :> CH2=CH :> CH=C :> HO > F

83 8 8 A 8

(8) NH2 :> CH3--CHz :> CH2=CH :> CH""C :> F> HO

8 8 A P - A e

(C) CHr-CHz:> CI-l2""C;H:> r::.iHz :> CH==C :> HO:> F

8 G 8 \::;> G 8

(0) F :> HO :> CH'=OC :> CHz"'CH > NH2 :> CH3--CH2

PART: C (MCQ)

31. In which of the following pairs the first one is the stronger base than second.

(A) CH3COOe• HCOOe (8) HOe, NH~

(C) CHz ::;: C~: • H - C '" ~: (D) CH3NH2• CHpH

32, Which of them are arranged in decreasing order of basic strengths (~) :

NH, Me;¢iMe ~ Me*Me
(A) ~
Me Me
NO, NOf NO,
(8) PhCH2NH2 PhNHPh PhNH2
N(CH3)' ~~(CH3)'
I © ©
(C)©
N N
.. ..
(D) CH2 = N- CH3 • CH2=CH-NH2• CH, - C - NHo
"II •
0
~3o Find the correct option/so :NMe,

(III) 6

:NH,

MedMe

'9'

(IV) ,

~

34.

(A) II is most basic compound

(8) In II lone pair of nitrogen is less involved in resonance (C) The extent of resonance in I, III is same

(D) IV is most basic due to + I effect of two methyl groups.

Choose the correct option/s for basic strength order: (A) NH3 > CH3 - NHz > Ph - NH2

(C) P-toluidine > N. N-dimethyl-p-toluidine > Aniline.

35. Which of the following reactions are feasible.

N (A)F'~h.

~N'

"H

NH2

(8) N~cF + @ ---->

(C) ~jJ + [Ij ----* U~ +0
N ll. h ~N'
H/e"H 1\1 v Ie
I I
H H CH2 II ffi

., CH3-C·-NH3 --~

-

EXERCiSE # 4

1. 2.

(P) 4

I> II:> III;

(Q)

I> II> III;

(R)

I > II > III

e e e e CH3 < NH2 < OH < F

r> p > q

ERG increase the basic strength because they tend to stabilise the cation formed by protonation, on the other hand, EWG decrease the basic strength they tend to destabilise the protonated amine.

'9 NH3

~G

l8J (ERG)

$

1: G'

~WG)

(G stabilises the cation)

(G' destabilises the cation)

H CH3 CH3 (b)

"'" I 1~

(a)--~:tl~

~ ~ (C)

IX vi

\ ) 0 - C - NH - CH

II 3

o

i"

(i) 1

(ii) 2

(iii) 1

s, (8) X ; (b) X (c) (i) Z > Y > X, (ii) Y > Z > X, (iii) Y:> X > Z

g, I :> II > III > IV

10t III> n> I

The basicity order wi!! be inversaly proportional to resonance stability of lone pair.

11. A 12. A 13. a 14. D 15. A 16. A 17. D
13. D rs, D 20. D 21. C 22. A 23. A 24. A
zs. D 26. A 27. A 28. A 29. D 30. C 31. ACD
32. AS 33. AS 34. SD 35. CD Car6anion·.~tTautomerism

'Exercise

-

Part A: Subjective

10 Which of the foHowing will show tautomerism.

(a) Butanal (b) Butanone

(c) Cyclohexanone

(d) Ph-C-Ph II

o

(f)~ /CH3 yCH3

o

(h) HO-CH=CH-OH

2. Write one tautomers of each of the following compounds

o

II

(ii) CH3 - C - CH,

(i) CH3 - CH = NH

(iv) CH3 - C·- CH2 -C - CH3

II II

o 0

P Q R S

3. If CH3 - C - CH2 - C - CH2 - CH3 is mixed with NaOH solution. Acid base reaction occurs and HOe

II II

o 0

snatches H$ from organic molecule. Which carbon will loose H+ most easily and why?

4. In monocarbonyl compounds amount of the enol form present at equilibrium is very small. Explain.

S. Pentane-Z, 4-dione exists 76% in its enol form, Explain.

Part B: SeQ
Arrange the following carbanions in decreasing order of stability: (Q. No.6 to 8)
6. a e eCHz-Q eCH,
CHz - CH, CH2 - C(CH,},
I II III IV
(A) III > IV > I > II (8) III > IV > II > I (C) III > I > IV > II (D) IV > III > I > II
9CHz- CHO e e e
7. CH r: C - CH - C - CH H-C-CH-C-H OHC-C-CHO
a. II II 3 II II I
0 0 0 0 CHO
I II III IV
(A) IV > III > I > II (8) IV > II > III > I (C) IV > III > II > I (D) III > IV > II > I
e e e
e ~ ~ ~
a, ©
CH, NOz OCH,
I n III IV
(A) III > I > IV > I (B) In > II > I > IV (C) I > III > II > IV (D) III > I > II > IV 9. Which of the following intermediate have the complete octet around the carbon atom:

(A) Carbonium ion (S) Carbanion (C) Free radical (0) Carbene

10.

Tautomerism (A) (CH3)2NH

be exhibited by :

(8) (CH3)3CNO

_III Rt:lc::::nn~nr-Q

12. Which of the following pairs are tautomers ?

('YCHCI2 (A) ~\

OH

(8) HO-CH2-CH:= CH2 OH ~./~

(C) ~ "T

..-;:P ..-;:P

OH

~

V-yJV

o

(0) CH~ - C -- C - CH-

._ II Ii ~

o 0

CH-C=C-CHo

3 I I ,)

H~ OH

13. Which among the following compounds will give maximum enol content in solution:

o 0 0 0

II II II II

(A) C6HS - C - CH2 - C - CH3 (B) CH3 - C - CH2 - C - CH,

o

I'

(C) CH3 - 6 - CH2 - CH2 - CH3

14. Which of the following has highest % enol content in the liquid?

(A) O'~ -C-C-CH3 , - II"

o 0

15. Which among the foiiowing compounds will give maximum enol content in solution'

(A) 3-hexanone

(8) 2,4 - hexanedione (0) 2,5 - hexanedione (0) 2,3 - hexanedione

16.

OH

HO*OH

The most stable keto isomer of the following compound I is :

HO ~ OH

OH

o ohOH (8) HO¥OH OH

o HOyllyOH

(C) o~Ao OH

o OHhOH

(D)HO~OH o

Part C: MeQ

17. In which set first is more stable than second

e e (A) CF3 CCI3

e e

(C)OO

1 ~t Which among the following compounds will show tautomerism:

(A) 2, 2 -Dimethyl propanal (8) 2, 2 -Dimethyl-1-nitropropane

(C) Acetyl acetone (D) 8enzophenone

19. Which of them are tautomers :

o

t

. CH -C::: N - OH

, 3 I

CH3

CHO

(8)

CH-OH

II

C-OH

I CH2-0H

20. Which one of the following molecules contains deuterium after reaction with NaOD in Dp ?

o

(A) Oa

(8) CH -C-H 3 II

o

(C) o-~ C - C(CH )

_ II 33

o

HO

(0) bQ

OH

21. Which of the following compound will racemize on keeping in aquous solution.

Et Me

I I

(C) Me - C - C - C - Ph

l II I

n 0 Et

: ~

(8) CH - C - CH = CH - C - CH,

3 I II v

Ph 0

--

EXERCISE # 5

1. (a), (b), (c), (e), (g) and (h)

2.

(i) CH2 = CH - NH2

/0 (iii) CH3 - C = N~

I OH

CH3

(iv) CH3 - C - CH == C - CH3

II I

o OH

3. Q will loses W easily because anionic charge of Q is delocalized with two > C = 0 group.

4. Due to greater stability of keto form in monocarbonyl compound. ketoform is more stable due to greater strength of the carbon-oxygen 7t bond compared to the carbon carbon 11: bond.

S. The greater stability of the enol form of p-dicarbony! compounds can be attributed to stability gained through resonance stablization of the conjugated double bond through hydrogen bonding.

Resonance stabilization as the enol form

A

BC

12. 19.

A

B

S. 15.

D B

9. 16.

B

10. 17.

D BC

11. 18.

c

6.

A

7. 14.

C

13.

C

ACD

20.

ABO 21.

AS

CarbocatiiJrls & Free .R~tlibals

Exercise-6

Part A : Subjective

Arrange the following intermediate in increasing order of their stability:

E& (i)CH3~H2~~~CH2

ffi

(II) CH2 - CH -CH2 .

~

"1- Among the following carbocation which carbocation is more stable and why?

$ $

O~CH2 ~. I ~ CH2

o V

(A) (8)

3. V\fhich of the following pairs will rearrange from A ~ B and explain. Why?

A B

(l)

(1)~

K

~

OH

X

(2) r---f- 011

Rank the following intermediates in increasing order of their stability and give appropriate reasons.

5.

/j., 6 c-:
U
(I) (II) (III)
(I) 1,2-Me shift (P)
.. '>«:>
\__/ ffi
(I!lJ.JJ. :80rl.9_ ~
(Q)
shift (IV)

Draw the structure of P and Q.

B:SCQ

The most stable cerbocatlon amongst the foflowin9 is : (Q. No.6 to 10)

iW. (A) eM;) -CHz -CH2 (8) CH3 -CH-CHz -CH3

i.

CYCH' C]XCH, arCH, e
QJCH,
(A) (8) (C) (0)
(A)O-~H2 ED (C) (CH3CH2)3CED (0) O-CH2-~H2
(8) (CH3CH2)2CH 8.

9.

CH3 CH3

10. (A) CH3-O-CH2--Q- CH2 -~H-c!H2 (8) CH3-O-CH2--Q-CH2 -~-CH3

11. The most unstable carbocation is

12. The number of electrons present in the valence shell of carbon of carbocation bearing positive charge.

(A) 8 (8) 6 (C) 7 (0) 4

13.

The most unstable carbocation is
Ell Ell Ell
(A) CH3 (8) CH3CH2 (C) HC2
Nonplanar cation is -
ED e ED
fA) NH4 (8) CH3 (C)CH3CO
The stability order of following carbocation is
@ G) G)
OJ 0 @
I II III
(A) I > II > IV > III (8) III > I > II > IV (C) IV > II > III > I 14.

15.

16. Following carbocation changes to more stable carbocation :

o-

(A)O~H,

11. In the following reaction, most stable intermediate is:

CH3 I

CH3- C-CH = CH2 + HBr ~

tH3

IV

(0) II > IV > III > I

CH3 Ell I

18. The following carbocation rearranges to CH3 - C- C - CH3

I I H3C OH

CH3

I e

(A) CI;3 - C - C - CH3

I I CH30H

OHCH3 I I

(8) CH3 -C -CH -CH3

I E9

CH3

CH3 I

(C) CH3 -CH-CH-CH3

I I CH20H

Ell

(D) none of above

';1'.

'" N!liC'r-lE&

~:\.D" The following carbocation rearranges to ~

H3C CH3

2et Arrange the following radicals in their decreasing order of stability.

(A) IV > I > III > II

(8) IV > III > II > I

(C) I > II > III > IV

(D) IV > III > I > II

22.

Most stable radical is
• (Bl6 (elO (DJ6
(A) 0
In which case first is more stable than second
(A)O' 0 (8)0' 0- (C)~ 0 (0) Ph3C (CH3)3C 23. Arrange the radicals in their decreasing order of stability.

(1) CH;-Q

(II) O-CH-Q (III) 0-6-0 (IV) 0

6

(A) III > II > IV > I Part C: Mea

24. Which of the following statement is true?

(A) The structure of carbocation is trigonal planar like that of 8F 3

ffi ffi

(8) CH3 - CH - CD3 is more stable than CH3 - CH - CH3

ffi e

(C) 1'\ is more stable as compared to D·

(D) Heterolytic fission leads to the formation of charged or ionic species, one having a positive charge and other a negative charge.

(8) III > IV > II > I

(C) III > II > I > IV

(D) II> HI> IV > I

25. Which of the following statement is not correct

(A) Free radical are very less reactive as compared to corresponding cations/anions (8) Free radicals are diamagnatic.

(C) Free radicals are generally formed either in presence of UV/ visible light or in presence of rv"",.,v",!,~", (D) Free radicals are generally electrically neutral

26. In which of the following option 1st is more stable than lind

e

(A) 0,

e

o

ffi $

(C) CH3 - 0 - CH - CH3, CH - C - CH - CH

3 I 3

CH3

OMe

(D)~

, - -~'

EXERCISE # 6

____________________________ """""=~.'''''~~'I'ffi!llo~==_~~

1. (I) > (III) > (IV) > (II)

2. (8) is more stable CEil due to extented 1t bonding conjugation

3. 1 & 3 will rearrange to A ~ 8 because in tst pair due to - CH3 shift 2° carbc<>:ltion converted ink! 3':; Carbocation . In 2nd pair A is more stable C(Jl . In 3rd pair B is more stable due to cyclopropyl group.

4. Stability order: - IV > III > II > I

IV is most stable being 3° and resonance stabilized but III is 2° and resonance ~tabjlta:Ki,

a<CX
5. (P) =: ; (Q)
6. C 7. A 8. e 9. C 10. D 11. C 12. 8
13. C 14. A 15. D 16. B 17. C 18. A 1~ D
, "',
20. 8 21. C 22. B 23. C 24. ACD 25. AS 4~1o 1.

[JEE-2009, 3 Marks]

The correct stability order of the following resonating structures is :

+ - + - - +

H2C=N=N H2C-N=N H2C-N=.o.N

(I) (II) (iii)

(A) (I) > (II) > (IV) > (III) (8) (I) > (III) > (II) :> (IV) (C) (II)

2.

The correct acidity order of the following is :

OH OH COOH
6 ¢ I
),
~ ""
Ii ".
Ii I
~.
_-;.r
CI
(I) (II) (II!) (D) (Iii) > (I) > (IV) > (II) [JEE-2009,3 Marks]

(A) (III) > (IV) > (II) > (I) (8) (IV) > (III) > (I) > (l!) (C) (HI) :> > (I) > (IV) (D) (II) > (IIi» (IV) > (I)

3. In the following carbocation; H/CH3 that is most like!y to migrate to the positiviely charged carbon is

H H

1 12 + 14 5

HoC-C-C-C-CH,

c I 31 I " [JEE-2009, 3 Marks]

HO H CH3

(A) CH3 at C-4

(8) Hat C-4

(D) H at C-2

4. Hyperconjugation involves overlap of the following orbitals [JEE-2008,3 Marks]

(A) o-cr (8) a-p (e) p ~ p (0) T( - 'IT

5. The correct statements(s) concerning the structures E,F and G is (are) [JEE-2008, 4 Marks]

H~~J=<~:3

(F)

(A) E,F, and G are resonance structures (C) F and G are geometrical isomers

(8) E,F and E, G ere tautomers

(0) F and G are diastereorners

6.

The correct stability order for the foilowing species is

~oA

(I)

3 j

/'''0/'\,

(III)

(II)

[JEE-2008,3 Marks]

(IV)

(A) (II) > (IV) > (I) > (IIi) (8) (I) > (tt) > (Ii!) > (IV) (C) (II) > (I) >

> (!II) (0) (I) > (III) > (II) > (IV) [JEE-2007 ,3 Marks]

7.

Among the following, the least stable resonance structure is :

12.

8.

o

II r,::yS-OH

~~

[JEE-2006 ,3 Marks]

~ NaHCO,

N02

A mixture of benzenesulphonic acid and paranitrophenol react with NaHC03 separately. The gases produced are respectively.

(A) S02' CO2 (8) S02' CO (C) S02' NOz (0) CO2, CO2

9.

$'H Excess of CH,COONa

CH3

The products will be :

(A) H3C-@- S03Na + CH3COONa

(C) H3C-@- S03H+ CH3COOH

(8) H3C-@- S03Na+ CH3COOH (0) H3C-@ + S03

[JEE-2005(s),3 Marks]

10.

[JEE~~W05(s) ,3 Marks]

Which will be the least stable resonating structure:

e 0

(A) CHz = CH - CH - CH - ° - CH3

o e

(8) CH2- CH - CH = CH - OCH3

o $

(0) CHz = CH - CH - CH = 0 - CH3

[JEE~2004(s) ,3 Marks]

11.

e e

(C) CH2 - CH = CH - CH = ° - CH3

What is the acidity order of x, y & z ?

NH (Y) NH(Z)

YVV'

COOH (X)

(8) x > z > y

(0) z > y > x [JEE(main),,2003, 2 iVi;';!rks]

(A) x > Y > z

(C) Y > z > x

Match the Ka values:

'-
Compounds K,
(a) Benzoic acid (i) 3.3 x 10-'
(b) O,N -o-COOH (ii) 6.3 x 10-0
(c) CI-Q-COOH (iii) 30.6 x 10-5
(d) H,CO-D-COOH (iv) 6.4 x 10-'
(e) H,C-Q-COOH (v) 4.2 x 10-' Write resonating structure of the compound H3C~CH2' OH

14. Which of the following represent the given mode of hybridisation Sp2 - Sp2 - sp - sp from left to right.

[JEE(main)-2003,4 Marks]

CH,

(A) H2C = CH - C == N (8) HC == C - C == CH (C) H2C = C = C :: CH2 (0) ~

, H,N

13.

[JEE(main)-2003,2 Marks]

2 moles NaNH,

A , The product A will be -

[JEE-2003(s) ,3 Marks]

OH

-ooc OH -OOC OH HOOC 0- HOOCO_P0H
(A) fj , (8) ~ (C) fj , ~ ..? (D) fj _' \ ~
O,N O,N ...., "''c- O,N "" O,N'q' '~-
~ C ....
H 'R
0- 0 0- 0-
I
H 16. There is a solution of p-hydroxy benzoic acid and p-amino benzoic acid, Discuss one method by which we can separate them and also write down the confirmatory test of the functional groups present

[JEE-2003{s) ,3 Marks]

'1'7. Which of the following acids has the lowest value of acid dissociation constant: [JEE-2002(s) ,3 Marks]

(A) CH3CHFCOOH (8) FCH2CH2COOH (C) 8rCH2CH2COOH (0) CH3CHBrCOOH

18.

Write the basicity order of the following:

(I)

(II)

(III)

[JEE-2001{s) ,1 Marks] o

II

CH3 -C--NH2

(IV)

(A) (II) > (I) > (III) > (IV) (8) (I) > (III) > (II) > (IV) (C) (III) > (I) > (II) > (IV) (0) (i) > (ll) >- (In) >

19. 20,

CH2= CH- is more basic than He = C-. Explain.

The most unlikely representation of resonance structures of

,3

0+/0- 'N

)l....__ (8) ~ .. )

<, H o

o 0 ~N~

('11

(e)y

0'-

21. A solution of (+ }-2-Ch!oro-2-phe!1y!eth~nif) In toluene racemises slowly in the presence of small amount of

SbCI5, due to the formation of [JEE-1999 ,:3 i'tihuil:$]

(A) carbanion (8) caroene (C) free-radical (D) carbocaton

22. The central carbon-carbon bond in 1, 3-butadiene is shorter than that of n-butane. Why ? [,;EE4~S]

23.

Among the (A) HC=CH

compounds, the strongest is :

(8) C(lHS (C) C)'16

(D)CHPH

r----------------------------------

25.

Tautomerism is exhibited by (A) O-CH = CH - OH

(8) O~O

(C) yo

°

[JEE -981 [JEE-98}

(D)Qo

°

24.

Dimethylamine is stronger base than trimethylamine. Explain.

26.

Write the order of basic strength.

o

I H

o

N

()

N I H

o

N

I H

(I) Piperidine

(II) Pyridine

(Ill) Morpholine

(IV) Pyrrole

(A) (IV) > (I) > (III) > (IV) (8) (Ill) > (I) > (IV) > (II) (C) (II)!> (I) > (Ill) > (IV) (0) (I) > (III) > (II) > (IV)

27. _ Although phenoxide ion has more number of resonating structures than benzoate ion, beznoic acid is a

stronger acid than phenol. Why? [JEE-97]

LEVEL-JEE

1. 7.

12.

8 2. A 3. 0 4. 8 5. 8,C,D 6. 0
A 8. D 9. B 10. A 11. A
e
eH~CH2
(a) - (ii) ; (b) - (iii) ; (c) - (iv) ; (d) - (i) ; (e) - (v) 13. 3 . ':::::
I
(BOH
A 15. A 14.

16. For the separation of p-hydroxy benzoic acid and p;-aminobenzoic acid with a solution, the solution is treated with HC!. Therefore p-aminobenzoic acid is remained in solution as form of ammonium salt while phydroxy benzoic acid is not soluble (non soluble, so it separated easily).

Soluble form in aqueous solution

Insoluble form

Test: (1)

OH

~

eOOH

~

Neutral FeCI3

Violet blue ppt.

Test: (2)

NaN02/HCI

p-Naphthol/KOH

Red Orange dye.

eOOH

17.

c

18.

B

19. Carbon has higher percentage of's' character in HC=:C-.

23.

27.

20. 22.

C

21.

D

1, 3-Butadiene shows the property of resonance.

E!l e

CH2 = CH - CH = CH2 ( ) CH2 - CH = CH - CH2

So bond between second & third C-atoms show partial double bond character. Hence bond length is shorter than C - C bond in n-butane.

D

24.

Due to steric hinderance.

25 .

A,C,D

26.

o

. ·e

(0:.. :0:

~, ~

"V~V

IV

V

In resonting structure of phenoxide negative charge is present on C-atom (which is less electronegative) while in benzoate ion, negative charge is present on more electronegative 0 atom. Hence in ionic structure, if negative charge is present on more electronegative atoms, therefore, it is more stable in comparison to that ion which have negative charge on less electronegative atoms.

.. 1"'"\_

Resonating structures of benzoate ion

II

1. Arrange the carbanions, (CH3)3 C, CCI3, (CH3)2 CH, CsHs CH2 in order oftheir decreasing stability:

[AIEEE~2(l()91

(A) (CH3)2 CH > CCI3> C6HS CH2 > (CH3)3 C (8) CCCi3> CsHs CH2 > (CH3)2 CH > (CH)3 C

- - --

(C) (CH3)3 C > (CH3)2 CH > C6HS CH2 > CCCI3 (D) CaHs CH2 > CCI3> (CH3)3 C > (CH3)2 CH

2. A liquid was mixed with ethanol and a drop of concentrated H2S04 was added. Acompound with a fruity smell

was formed. The liquid was: [AIEEE~20091

(A) HCHO (8) CH3COCH3 (C) CH3COOH (D) CHpH

3.

Which one of the following is the strongest base in aqueous solution?

(A) Trimethylamine (8) Aniline (C) Dimethylamine

IAIEEfE~20u)"J (D) Methylamine

4. The increasing order of stability of the following free radicals is [AIEEE~2006] (A)(CsH5)3 C < (CSHS)2 C H < (CH3)3 C < (CH3)2 CH (8) (CSH5)2 CH < (CeHS)3 C < (CH)3 C < (CH3)2 CH

(C) (CH3)2 C H < (CH3)3 C < (C6Hs)3 C < (CSH5)2 C H (D) (CH3)2 C H < (CH3)3 C < (CeHS)2 C H < (CSHS)3 C

5.

The correct order of increasing acid strength of th'e compounds

Among the following acid which has the lowest pKa value?

(A) CH3CH2COOH (8) (CH3)2CH - COOH (C) HCOOH

Amongst the following the most basic compound is

(A) p-nitroaniline (8) acetanilide (C) aniline

(a)CH3C02H

(A) d < a < c < b

(b) MeOCH2C02H (8) d < a < b < c

(c)CF3C02H

(C) a < d < c < b

Me

(d) >-CO,H Me

(D) b < d < a < c

[AiEEE~2005]

6.

7.

8.

consider the acidity of the carboxylic acids:

(i) PhCOOH (ii) o-N02CsH4COOH

Which of the following order is correct

(A) i > ii > iii> iv (8) ii > iv > iii> i

[AIEEE-2005] (D) benzylamine

[AIEEE-2004]

Oii) P-N02C5H4COOH (iv) m-N02CsH4COOH

(C) ii :;. iv > i > iii (D) ii > iii> iv > i

9. The correct order of increasing basic nature for the bases NH3• CH3NH2 and (CH)2NH is: [AIEEE-2003]

(A) CH3NH2 < NH3 < (CH)2NH (8) (CH3)}~H < NH3 < CH3NH2

(C) NH3 < CH3NH2 < (CH)2NH (D) CH3NH2 < (CH3)2NH < NH3

10. In the following benzyl/allyl system !~!EEE-201l2J

R-CH = CH2 or

Q-R

(8) CH3CH2- -» (CH3)2CH'-~' (CH3)3G(D) (CH3)2C~-~ CH3CH2--)

(R is alkyl group)

decreasing order of inductive effect is : (A) (CH3)3 C--» (CH3)2CH- -) CH3CH2- (C) (CH3)2CH- -) CH3CH2- -) (CH3)3C-

1. 8.

c

3. 10.

C A

8 D

2. 9.

c

4.

D

D

B

c

5.

6.

· ..... . .. -

Miscellaneo.u.S<,-Clu::esii:ooBank

PartA: sec

1. Polarization of electrons in acrolein may be written

3- 1)+

(A) CH2 =CH-CH=O

1)- 1)+

(8) C H2 == CH - C H = 0

8- B-

(C) C H2 = CH - C H == 0

2. Which does not contain conjugate system?

(A) CH2 = CHCI

(8) CH2 :: CHCHO

(0)0

3. Which of the following structures are resonance strucures

(D)CH -CH=CH-CH &CH -CH -CH=CH

, 3 3 3 2 2

4. Which of the following is the major contributor to the real structure of CH3COOCH3

81.. $ I=> e

(A) CH3 - « - Q - CH, (8) CH3 - 9 = Q - CH3 (C) CH3 - Y - Q - CH3 (D) CH3 - 9 = Q - CH3

·b· -0' :Q$ :Q@

'G' 'e'

5. Most acidic hydrogen is present in :

(Bl~

6. Which of the foltowinq is most acidic?

SOH

(Bl@

7. in the foliowing compounds
OH OH
OH ¢ OH ¢
I ~
~~ ©-NO,
,OJ
~
CH3 N02
(1) (III) (IV)
(II) the order of is :

(Ai III > IV > I :> II

(8) I> IV > HI > Il

(C) II > I > III > IV

(D) N > HI:> I:> n

Et Arrange the following compounds in decreasing order of their acidic strength.

eOOH eOOH eOOH eOOH

OCH, (rCI (yNO' (y0CH,

(I) (Ii) (III) (IV)

(A) (I) :> (II) :> > (IV) (8) (II) > (I) > (IV) > (lll) (C) (III) > (IV) > (II) > (I}

W!~!,;;h of the foilowing is most acidic.

(II!) > (ll) > (I) > (IV)

eOOH eOOH eOOH
I I
~;/'~ () A CO()r1
(0)0
y (8) ~ ! (C)YI
(A) r
N02 OH GH3
OH OH OH OH
J I (C)61/;H,
(8)0- (D) r_(~
(A) ()_
::,__ F " 'OH ~
0 0 ;
(A) (c5>-~-- NH2 r;:::\, I' (C)~NH2 (D)ONH2
(8) \, 0 _rc- NH2
- 0 (A) III < II < ,

GOOH

~

Lv)

'-.""_.". .....

(A) n « J <:}}}

In the following

(A) Ill > TV:> ~.

II

COOH

~~I .o

<, '-.:::/ ....

! CH3

n I,

(U)

(8) III <: i < II

(B)} <:)J <'; m

(C) II < Ii! -c I

(0) I < !II <: II

(C) II;; ill

OH

(Ii)

(1\-')

(el IT

IV>IU>I>U

16.

o NH

II Ii

(c) H2N - C - NH2 and NH2,- c.

(I)

(A) (a) - (I), (b)-- (11), (c)·- 0) (C) (a) - (II), (b) - (I), (c) ,-- (II)

Which is the most basic among (a) (C2HShN and f)

(I) (i!)

pails of

(I). (c) .,- (I) -_. OJ), OJ)'_ (11), {c) -- (II)

17> Strongest base among the follO'vVing compounds is :

18. Steric inhibition of resonance can be expected in

(A)~~-r<

"

)-. ,',

!_.f \\ ."

(8) ~. ')-!~

,=J

/

Most stable carbocation among the

. , CH3 .~ J

(A) ~ (B) / V' "1"/

19.

20. Which one of the following is most stable?

example is,

(C)

21. Which allylic carbocation is most stable carbocation ?

EEl (A) CH3 -CH = CH-CH2

EEl

(C) CH3 - CH = CH - C- CH3

I

CH3

(0)

EP (0) (~, I

,-,.N3

EEl

-CH = CH-CH-CH3

(D) AI! have same stability

22. Arrange the following free radical in decreasing order of

(A) III > II > I > IV

u

(8) IV> I > II > II!

In the following carbocations, the

23.

(A) III > II > IV> I

--

i ...... l•

vn3

(II)

(8) IV> I > II > III

(C) IV:> III > II

order is:

(I iI)

.II

(C) IV> III > II > I

I"i,_1

(D) iii> iV> II:> I

(10\ :"1-'

,._,_, 'I

::::::./ 'J",

(!\/)

(0) III > IV> II :> I

r

24. 'Arrange the following carbocations in decreasing order of stability:

26.

27.

CH3 -CH-CH3 (I)

(A) (II) > (I) > (III)

+

CH3 -CH-O-CH3 (II)

(B) (I) > (II) > (III)

25.

+

CH3 -CH-CO-CH3 (III)

(C) (III) > (II) > (I) (0) (II) > (III) > (I)

Arrange the following carbanions in decreasing order of stability:

e e e

CH2- CI CH2- CN CH2- N02

(I) (II) (ill)

(A) III > II > IV > I (B) III > II > I > IV (C) III > I > II > IV (0) II > III > I > IV

The most stable carbocation amongst the following is :

Ell (A) CH3-CH2

E9

(A) CH3CH2

(A)~ (B)~

~ CH,

CH,

E9 (A) P - 02N - CSH4 - CH2

E!3

(C) P - CI- C6H4 - CH2

30. The following carbocation rearranges to

28.

29.

CH3 CH3

I Ell I

CH2 = C- C-CH-CH-CH3 I I

CH3CH3

CH3 CH3

I I

(A) CH2 = C - CH - CH - CH - CH3

I I

CH3CH2 EB

CH, CH,

I I EB

(C) CH2 = C - C - CH - C - CH,

I I I

CH,CH, H

E9 Et>

(C) CH3 - C = NH (0) CH2 = CH

LCH3 (C)~

E& H,CCH

(0) ©

CH3 CH3

I I

(B) CH = C - C - CH - C - CH

2 2 EB 3

I I

CH3CH3

CH3 CH3 EEl I I

(0) CH2 = C - C - CH - CH - CH3

I I

CH3CH3

31. A Binary mixture of aromatic compound A & B, A is soluble in NaHC03 but B remain as residue. Residue undergo sublimation on heating identify A & B respectively

(

COOH OH COOH

(A) ~ @@ (B) ~ @@J0H

Br Br

COOH

(C)~

Br

.. ,,---

(O)c§:@

brisk effervesence is obtained its residue give

(8) ReOOH and Ri'l02

~~ '~' ... '

(D) ReaOH and R - C -- R

II u

o

OMs .<&J., (C) r, II

~~-~~/'

some acidic or basic impurities

- C;·· Ii

(..,)

(8)

(D)AII

arenium ion is

r- ", \

(C) t~ j-NH, ~-\.

'E

isomeric with I, II & III as

ID)(~ N+'·

~ ~-t=' d,

'E

___ -~--'_c

~j, '3

H r··~· I

-r v ('. ~/""'.'\ ;""'-

l! ~) r=~'" V ~ N - 0

~~

CH,

(8) Metamers, tautomer, identical

(D) Functional. tautorners & oeometncat

HI

38. Observe the following statement and choose the correct option. (True/False) 51 : 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 ~ CH2-CH=CH2

Ph-CH2~CH;::...._ _

c CH2-C=CH

(1)

S3 : The hybrid structure has always equal contribution from all the resonating structures 0 NH,

S4: H00 shows inductive effect, resonance, hyper conjugation & intra molecular hydrogen

VCH3

bonding.

(A) TFTF (8) FTFT (C) FTIF (D) 1TFF

Part B: MeQ

39. Number of n- electrons in butadienyl anion (C4H4)2- is

(A) 2 (8)4 (C)6

(D)8

40. Keto-enol tautomerism is observed in :

o II

(A) CoHo - C - H

o

II

(C) C6HS - C - CH(CH3)2

41.

Which of the following will show tautomerism.

N-OH

(A)Q

°

42. Which of the following is correct relation between given pairs

~ ~e

(A) yC"",- ,yC"",- ----f Resonating structure

CH2 ~H2

$

(6) 0 6 ~ Resonating structure

e

~ Geometrical isomers

('YC

(D)X

I ~.v~~(OH

,.,:/1 "".A~,

---» Tautorner

43. The tautornerc =2 ·s sre

(A) Me2C = NO'- 3-: 1.'e::~:,,~;·..j=O

(D)

and

-

Write up-I

Oelocalisation of electrons take place in alternate single and multiple bonds involving carbon atoms. Oelocalisation may also occur in a conjugated system involving carbon atom and atom other than the carbon. There are also examples in which 11: orbital and p orbital (vacant or half- filled or filled) overlap. Thus delocalisation are of the following types;

(i) delocalisation by 11:, 11: overlap

(ii) delocalisation by 11:, P overlap

Oelocalisation makes system stable. more is the number of resonating structures more is the stability of the system.

In which of the following compounds delocalisation is not possible;

(A) 1, 4-pentadiene (8) 1,3-butadiene (C) 1,3,5-hexatriene

44.

45. Which of the following anion is most stable due to the delocalisation ?

o

~II e

(A) \:::!_;'C-O

e

°AN02

(8) V

e

o=c-o

A

(C) I~ 11

~NO

• 2

(0) benzene

e

0(S0

(0) Y N02

46. Which one of the following carbocation is most stable by resonance effect

EB CH,

(B)@

. - ...

Write up-II If bulky groups are attached at conjugated system at adjacent atoms then resonance greatly decrease. The phenomenon is describe as steric inhibition to resonance (SIR). SIR affects many physical & chemica! properties of compounds like bond length, acidic strength, basic strength, reactivity.

47. The acid strength order is
COOH
eOOH eOOH ¢l eOOH
I'(rI OcI JAI
"",I
I
I I
(a) (b) (c) (d)
(A) a > b > c> d (8) a > c > b > d (e) a > b> d > c (0) b > a > d > c (1 ) (A) 3, 1

(2) (8) 3, 2

49. The correct acidic strength order is

o

L~"

lSJ eH3

(X)

(A) X > Z > W > Y

---

OH ~/CH' e

(Y) "

o

(8) Z > X > Y > W

(3) (4)
(e) 1, 2 (0) 1,4
OH OH
$ $
e el
-f' 'eH
o 3 (W)
(Z)
(e) W > Z> X > Y (0) X > Z > Y> W

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