ACID & BASE

SOLUTIONS : ACID & BASE

EXERCISE # I
1. Deprotonate the compound and check (–I) effect for stability of conjugated base (C.B) (–I)
effect is distance dependent and follow series of (–I) and (+I)
(v)  bond having more (–I)
% S character  (–I) 
   C C > C = > C – C
COO– COO– CH2–COO–
CH2
(vi) COOH COOH CH2–COOH
(–I) (–I) (–I)
(vii) & (viii)  On moving down the group size  stability of C.B 
 On moving left to right EN stability 
(ix) Check order of –I
(x) Sulphonic acid is more acidic (3 equal R.S) carboxylic acid (2 equal R.S)
COOH


2. (a) (b) CH3–CH=CH–O resoanance

NO2
(–R)
O– O–
4.
< (d-orbital resonance)

F Cl
[–NH2 is (+M)]
5. (B) Form aromatic anion after removed of H
6. (B) Is less acidic due to (+R) of OH while in (C) –OH shows but in (D) H-bonding
7. More acidic less pH value
8. Check series of (–I)
III > I > II
Here –NH– is (–I) and distance dependent.
1
10. Acidic 
pKa
Acidic  EWG group
– R  –I

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 ACID & BASE
11. (a) in phenoxide resonance present
(b) (–I)  > = > –
NO2

(c) COOH < COOH < COOH

Br
O– O– O–
NO2 OCH3
(d) (–R) (+R)

NH2

(e) < R–NH2 Basic strongly on  alkyl group (+I) 

12. (i) O-Nitro phenol is less acidic than p-Nitro phenol due to formation of intramolecular H-bonding
 in C two (–R)
 in D three (–R)
(ii)  –NO2 (–R)
 –Cl (–I)
 –CH3 (+H)
(iv)  –CH3 (+H) at O and P position but in meta only (+I) operate.
 But in (a) and (c) +H is same and at artho-position more +I operate than para.
(v)  –Cl is only (–I) and distance dependent
(vi)  Check ortho effect
(vii)  in C artho effect
 in B –NO2 is only (–I)
 in A –NO2 is only (–R)

1 1 1
13. Acidity  –R  –I   
I H R
(i)  –CH3 (+H)
 –NO2 (–R)
 –Cl (–I)
 –NH2 (+R)
(ii) Note: Resonance and hyperconjugation do not work at meta position only inductive
effect will operate
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 ACID & BASE
(iii)  –OMe
 in a +R > –I
 in b Only –I in both case resonance same than check inductive
 in d +R > –I because inductive effect is distance dependent

14. HF + SbF5 H [SbF6]–

Lewis acid Inorganic acid > organic

CH3

15. CH3 C unstable [three (+I)]

CH3

16. B is more acidic due to SIR effect.

19. Important order of acidic strength

OH OH OH
NO2 OCH3 OCH3
(i) R–SO3H > > R–COOH  > H2CO3  >

NO2 NO2 NO2

OH OH
NO2
> > H2O > ROH

Note: CH3–OH > H2O

COOH

HCOOH >

COOH

> R–COOH

O O
(ii) > H2O > R–OH > CCH > H2 > NH2

20. Follow Q. 13 (iii)

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 ACID & BASE
EXERCISE # II
1. For basic strength electron density is more
2  1  3  NH3 R = –CH3

2  3  1  NH3 R = Et
 In gas phase only check electron density.
 Amide are weaken base due to
O
R–C–NH2
(vi) in a N is down atom while O cause (–I)
(vii) in B LP is delocalized and C is 2°
(viii)  –NO2 (–I)
 –CH3 (+I)
 –F (–I)
(ix) Check series of inductive effect

2. (i) sp3N > sp2N > spN (for basicity)

 
NH2 NH2
(ii) C 3 equal R.S C 2 equal R.S
NH2 NH2 CH3 NH2
Amide are weaker base
(iii)  in a Lp is a part of aromaticity (sp2)
 in b Lp is localised (sp2)
 in c Lp is delocalised (sp2)
(iv) Basicity  + R > +H > +I
–NO2 > – CN (–R)

–OMe  –NH2 (R)

Donate easily
(v)  C is least basic due to less solvation effect
 in a –NO2 (–R)
 in b –NO2 (–I)
NH2

(vi) Me Me SIR only (–I) but in a –NO2 is (–R)

NO2
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 ACID & BASE
(viii) Ortho substituted amine are weaker base then other due to less solvation effect d is sp3
while other three are sp2 b & c are less solvated but –CH3 is +H and –NO2 is –R
(ix)  a is weaker base due to less solvation
 in c –CH3 is +H
 in b –CH3 only +I

3. (i) d is strongest base N is sp3 and ‘S’ have less (–I) than ‘O’
(ii) b sp3N
 H
N

(iii) N form equal R.S

H
(iv) (a) have higher electron density

4. (i) Check acidic strength and reverse

(ii) a>b>c>d
H2SO4 is a dibasic aid in HSO4– another OH give H

5. in a less solvation effect

in II –NO2 is only –I and in III –NO2 is –R

6. Check effect resonance an artho & para position.

7. in pyrrole Lp participate in aromaticity

11. HCl is strong acid (because Cl– is stablised than CH3–COOH)

1
12. (b) EN O  N  C EN 
Basicity

13. in ‘C’ Lp repulsion between two nitrogen is very high therefore protonate easily.

14.  in a equl R.S

 in b SiR
 in c Lp is delocalised with highly EN ‘N’

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 ACID & BASE
O
C–O–

Charge  Basic Strength 

15. NO2
CH3 (–I)
(+H)

1 1
16. Acidic strength  Ka   pKb 
pKa Kb
17. (A) Aromatic and 3 resonance
Aromatic and + 3  H
Aromatic

  H
N–H N
.. .. 3 equal R–S
(B) NH2 NH2 N
..
H
(But not in Pyridine)
18. (C)
3 eq PS after protonation > 2 eq. PS > localised > delocalised on 'O'
19. (3)
–O–, N , –NH2
(Ring)

20. (6)
All are more acidic than given str.

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 ACID & BASE
EXERCISE # III
O
R–COO–H 14
HCO3 14 14
1. C CO2+H2O
R–SO3–H
HO OH
unstable carbonic
acid
2. After removed of H2 compound become aromatic but not in case of H1.
3. If H attached with more electronegative atom give metallic test and follow. Follow this order
4. Squaric acid is an aromatic acid and follow following order.
5. In case of –NO2 SIR present but not in case of –CN (linear group)
6. In case of 1st (NO-Resonance bread’t rule) but in IInd resonance is present.

NH2

7. NH2–C–NH2 conjugated acid 3 equal R.S

NH2

NH2–C–NH2 conjugated base

CCl3 have d-orbital resonance


aromatic

1
8. Acidity   Ka
pKa

For question no. 9, 10, 11

Important order of acidic strength follow this order
OH OH OH
NO2 OCH3 OCH3
(i) R–SO3H > > R–COOH  > H2CO3  >

NO2 NO2 NO2

OH OH
NO2
> > H2O > ROH

12. And reaction goes in that direction where weak acid is present.
O O
> H2O > R–OH > CCH > H2 > NH3
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 ACID & BASE
EXERCISE # IV (JEE MAINS)

2. (1) NH3 + N NH4


NH3  NH2  H


O O O
H
(3) HO–S–OH HO–S–O– –
O–S–O– + H
O O O

3. For methylated amine 2° > 1° > 3° > NH3

4.  Ortho substituted acid are more acidic than without Ortho substituted
 in III –NO2 (–R)
 in IV –NO2 (–I)

5. IV having localized lone pair while other having delocalized.

COOH

1
6. Acidic  HCOOH > > R–COOH
pK a

CH2–NH2
7. Benzyl amine

—
8. 
OH O  H
–2 

10. –CF3 strong (–I)

–OMe (–I)
CH3
–CH3 < —C (+I)
CH3

11. For methylated amine

2° > 1° > 3° > NH3

12. Acidity HCCH > H2O > ROH > H2 > NH3 reverse this

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 ACID & BASE
13. Is more acidic due to (–I) of Cl and inductive effect is distance dependent.

14. In B –OCH3 (+R)

In C –NO2 (–I)
In D –NO2 (–R)

15. I and III N having sp3 but in III O cause (–I), IV is aromatic due to Lp (least basic).

17. In gaseous state only inductive effect operate.

18. (I) –Cl (–I)

(II) –CH3 (+H)
(III) –NO2 (–R)
(IV) –OCH3 (+R)

19. N3H hydrazoic acid

20. Follow order of acidic strength

–
OH ONa
NO2 NO2
+ NaHCO3 + H2CO3

Weak acid Strong acid

Reaction not feasible while in other is feasible.

1
21. Basic 
pK b

O
 

22. O–C–O ClO3 ClO2
O
4 identical R.S 3 R.S 2 R.S

23. Make conjugated base and check stability by –I effect :

–NO2 > –CN > –F > –Cl (–I order)

24. sp3N > sp2N . spN

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 ACID & BASE

N
N
sp2 localised H
2
sp delocalised

Lp is a part of aromaticity


25. NC—C—CN

N
26. In aqueous solutions :
2° > 1° > 3° NH3 (for methyl amine)
2 > 3 > 1° > NH3 (for ethyl amine)
27. In (B) –NO2 –R
(C) –NO2 (–I)
(D) –OMe +R
Acidic strength  EWG – R > –I
28. After protonution of b and C nitrogen conjugated acid will form and stabilised by (LP) but in C
LP of N is localised

29. Make conjugated base and check stability of anion :

Here –NO2 (–R), –OCH3 (+R)
–F (–I), –CH3 (+H)
Stability of anion  –R > –I

31. In aqueous solutions :

2° > 1° > 3° > NH3 (for methyl a more)
2° > 3° > 1° > NH3 (for ethyl a more)

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 ACID & BASE
EXERCISE # V (JEE ADVANCED)
1. Formation of equal R.S in benzoic acid.

4. (I) Form 2 equal R.S after protonation (amidine) (IV) is weakleast organic base.

O
C—OH intramolecular hydrogen bonding
O
H
5. 
(more volatile)
 While p-derivative is less volatile due to formation of intermolecular H-bonding.

6. Acidity  Ka

7. IInd having –I of F

O O
8.  > H2O > R–OH > CHCH > H2 > NH3
 R–COOH > –OH attached with –NO2

9. Ans. (B)
 in II –Cl (–I)
 IV –CH3 (+H)

10, 13, & 14.

OH OH
NO2 NO2 NO2
 R–SO3H > > R–COOH  > H2CO3

NO2 NO2
OH OH OH
NO2
> > > H2O > R–OH

NO2
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 ACID & BASE
– 
OH O Na

  > NaOH + H2O

S.A W.A feasible


CH3–CH2–OH + NaOH CH3–CH2–O–Na + H2O
W.A S.A
(Not feasible)

OH ONa

 > NaHCO3 + H2CO3

S.A
W.A
(Not feasible)

COOH COONa

 + NaHCO3 + H2CO3
W.A
S.A
(feasible)
 H2CO3 is highly unstable and liberate CO2 + H2O

O H–O
15. R–C C–R
O–H O
(exist in dimeric form)

16.  IV form 3 equal R.S

 While rest all form 2 equal R.S but in first more salvation than other.

O O
18. (A)  O– (B)  O–
More solvation due to linear arrangement of ( bond)

O O–
..
CH3O C–O– O
.. (Less solvation due to 3D
(Charge  by + M of –OCH3) structure of Alkyl group)

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