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Acidic & Basic Nature

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Factors affecting acidic nature or basic nature of compounds;
A. Inductive Effect
1
⟹+I effect ∝ Basic Nature ∝
Acidic Nature

⟹ +I effect ∝ number of carbon atom

⟹ +I effect ∝ branching in carbon chain
⟹ +I effect order : - 1o< 2o< 3o
1
⟹ –I effect ∝ Acidic Nature ∝
Basic Nature

⟹ – I effect ∝ Electronegativity
1
⟹Both + I & – I effect ∝
Distance
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1. CH3–OH > C2H5–OH

2. CH3–CH2–COOH > CH3–CH2–CH2–COOH
3. CH3–NH2> CH3–CH2–NH2

5. H2O > ROH

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C. Stability of anion formed:

Fast
Acid H+ + Anion (If anion is comparatively stable)
Slow
Acid H+ + Anion (If anion is comparatively unstable)
Stability anion depends on resonance

6. C6H5OH > ROH As benzene ring shows – I effect & R group shows + I effect or
after the removal of H+ ion phenoxide ion (C6H5O–) formed is stables by resonance
while alkoxide ion (RO–) does not shows resonance & thus unstable.
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7. RCOOH > ROH As after the removal of H+ ion carboxylate ion (RCOO–) formed is
stables by resonance while alkoxide ion (RO–) does not shows resonance & thus
unstable.
8. In case of benzoic acid after donation of H+ ion benzoate ion formed is comparatively
more stable as –ive charge is present on more electronegative O – atom in most of the
resonating structures while in case of phenoxide ion –ive charge is present on less
electronegative C – atom in most of the resonating structures thus the stability of
benzoate ion is more & thus acidic nature is more.
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D. (i) +R or +M effect or O, P - directing groups or activating groups:
a) These groups in which atoms directly attached to ring contains lone pair of electron
b) + R or +M effect groups: -Cl, -Br, -I, -NH2, -NR2, -OH, -OR, -SH, -
OCH3……etc
c) These groups also shows +I effect (except if O / N / halogen is directly attached to
ring it shows -I effect)
d) In aromatic compounds these groups increases electron density at ortho & para
position
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e) ∴ during the electrophilic substitution reactions incoming electrophile will get attached
at ortho & para position thus these groups are also known as O, P - directing groups
f) (Note: All hydrocarbons -CH3 group is also O, P -directing group but it due to hyper
conjugation not due to R - effect)
g) As electron density is increased on the ring ∴ electrophile will get attracted towards the
ring & reaction becomes fast thus they are also known as activating groups
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(ii) -R or -M effect or m - directing groups or deactivating groups:
a) These groups decrease the electron density. These groups contains multiple bond
O
||
b) -M effect groups: - NO 2 ,-C  N , - C -,-CHO ,-COOH ,-SO 3 H

c) These groups also shows -I effect (no exception)

d) In aromatic compounds these groups decreases electron density at ortho & para
position (Note: these groups does not have any effect at meta position)
e) ∴ during the electrophilic substitution reactions incoming electrophile will get
attached at meta position thus these groups are also known as m- directing groups
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f) As electron density is decreased on the ring ∴ electrophile will get repelled away
from the ring & reaction becomes slow thus they are also known as deactivating
groups
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Note: (i) Both +R &-R effect does not act at m - position & both (+R &-R) does not
depend on position
(ii) R effect is more powerful than I effect
(iii) Electron-withdrawing group (EWG) (-R effect showing groups) increases the acid
strength.
(iv) Electron-donating group (EDG) (+R effect showing groups) decreases the acid
strength.
(v) Due to intra molecular H – bonding acidic nature decreases as removal of H+ ion
decreases.
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9. In a, b, c presence of NO2 group (as it is electron withdrawal group) acidic nature is
more
In a & b group shows -I &-R effect thus acidic nature is more than that of C which
has only -I effect not -R effect
In a & b -R is same as it does not depend on distance but in b acidic nature should
be more than a as it shows it shows more -I effect but actually acidic nature of a is
more because in b Intramolecular H -bonding decreases the acidic nature
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10. Greater the number of electron withdrawing groups at 0- and p-positions, more acidic is
the phenol. Thus, the acidity of nitrophenols w.r.t. phenol decreases in the order
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11. In b, c, d presence of CH3 group (as it is electron donating group) acidic nature is less
In c & d group shows +I & +R effect thus acidic nature is less than that of b which has
only +I effect not +R effect
In c & d +R is same as it does not depend on distance but in c acidic nature should be
more than d as it shows it shows less +I effect
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12. Meta-methoxyphenol (a) or a meta-aminophenol (b)cannot show +R effect but can
exert only -I effect from this position.
∴m-methoxy phenol and m-amino phenols are more acidic than phenol due to -I effect of
-OCR3 and –NH2 groups.
As the –I effect of - OCH3 group is more than that of NH2 group, ∴m methoxy phenol
is a stronger acid than m amino phenol.
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13. -OH group shows -I as well as +R effect
a i.e. resorcinol does not show +R effect but only show -I effect only ∴ have more acidic
nature
In b i.e. hydroquinone& c i.e. catechol +R is same ∴ acidic nature depends only on-I
effect&-I effect of b is more than that of c ∴ Acidic nature must be a > b > c
In catechol, the two OH groups forms intra molecular H-bonding (chelation) ∴ acidic
nature is less.
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14. Halogens have both +R & –I effect but –I effect predominates over the +R effect ∴
Halophenols are more acidic then phenols (Except p – fluoro phenols, In case p-fluoro
phenol, because of almost identical sizes of 2p-orbitals of C and F, +R effect and –I
effect of F almost balance each other and hence it is almost as acidic as phenol itself.)
as–I effect depends on the distance thus acidic nature follows the order o –
Halophenols > m – Halophenols > p – Halophenols.
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15. Amongst o-halophenols, o-fluorophenol is the weakest acid due to strong
intramolecular H- bonding. The acidity of other halophenols decreases as the –I effect of
the halogen decreases. Thus, the acidity of all the o- halophenols decreases in the order:
O – Chloro phenol > o – Bromo phenol > o-Iodo phenol > o-Fluoro phenol
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Example. 1: Arrange the following compounds in increasing order of their acid strength:
(i) Propan-1-ol, 2, 4, 6-trinitrophenol, 4-nitrophenol, 3- nitrophenol, 3, 5-dinitrophenol,
phenol,4-methylphenol (p- cresol), 4-methoxyphenol[NCERT]
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(ii) F—CH2—COOH or Cl—CH2—COOH [AI 13, 14][NCERT]
(iii) CH3COOH or FCH2COOH [NCERT]
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[NCERT]

(v) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH

[AI 08, 09, 12] [NCERT]
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(vi) FCH2CH2CH2COOH or CH3-CHF-CH2COOH[NCERT]
(vii) (CH3)2CHCOOH, CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH [DB 08] [AI 09, 12]
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Example. 2: Explain why: (i) Ortho and para-nitrophenols are more acidic than phenol. Draw
the resonance structures of the corresponding phenoxide ions. [NCERT]
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(ii) Give two reactions that show the acidic nature of phenol. Compare its acidity with that of
ethanol.[NCERT]
(iii) ortho-nitrophenol more acidic than ortho-methoxyphenol? [NCERT]
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(iv) Ethanoic acid is a weaker acid than benzoic acid. [AI 08]
(v) Chloroacetic acid is more acidic than acetic acid. [SP 13]
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(vi) 4-nitrobenzoic acid is more acidic than 4-methoxy benzoic acid. [SP 13]
(vii) Phenol is more acidic than ethanol. [DB 08] [SP 09]
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(viii) Phenoxide ion has more resonating structures than carboxylate ion, but carboxylic acid is
more acidic than phenol. [DB 13][AI 13, 14][NCERT]
(ix) Monochloroethanoic acid (CH2ClCOOH) has a higher pKavalue than dichloroethanoic acid
(CHCl2COOH). [DB 08]
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(x) pKa value of chloroacetic acid is lower than pKa value of acetic acid [SP 11]
(xi) p-Nitro benzoic acid has higher Ka value than benzoic acid. [SP 11]
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10.
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11.
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12.
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13.
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 Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230

5. Assertion (A): o-nitrophenol is a weaker acid than p -nitrophenol.

Reason (R) : Intramolecular hydrogen bonding makes ortho isomer weaker than para isomer.
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6.
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Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
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 Simplified Chemistry (Simple Approach for difficult Concepts) Contact Sharma Sir 9826259230
BASIC NATURE OF AMINES
Factors affecting basic nature of compound

1. +I effect ∝ Basic Nature

2. +R effect ∝ Basic Nature
1
3. Sterric Hindrance ∝
Basic Nature
4. Kb ∝ basic nature
1
5. PKb ∝ (As PKb = –log Kb)
basic nature

1
6. Ortho effect ∝
Basic Nature
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1. Aliphatic amines (All the three classes) > Ammonia (NH3).

Alkyl groups are electron donating groups, thus the electron density on the nitrogen atom
increases and ∴ they can donate the lone pair of electrons more easily then ammonia.
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2. Aliphatic amines (All the three classes) > Ammonia (NH3) > Aniline (C6H5NH2)

NH3, & R group , shows +I effect while Benzene shows – I effect

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3. Basicity of Methyl amine in aqueous medium: Me = CH3 group

H Me Me
Me N N H
H Me Me N

1o Methyl Amines 2o Methyl Amines Me

3o Methyl Amines

Basic Nature ∝ +I effect ∴ 3o > 2o > 1o.

1
Basic Nature ∝ ∴ 1o > 2o > 3o.
Sterric Hindrance
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H
H H O
Fast H+ H Hydration Energy
H
Me N Me N+ H O
H H Maximum
H H O
H
H
Me Me H O
H+ H
N H N+
H
Me Me H O
H

Me
Me
Slow H+ H Hydration Energy
Me N Me N+ H O
H Minimum
Me
Me
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 Methyl amines are Bronsted base i.e. they can able to gain H+ ions
 Basic nature ∝ Tendency to gain H+ ions ∝ Speed of reaction
 Speed of reaction ∝ Stability of product
 But all protonated amines are charged species thus unstable
 They can be stabilized by dissolving them in water
 When 1o amine is dissolved in water it forms 3 H–bonds thus Hydration energy given out
is maximum
 When 3o amine is dissolved in water it forms 1 H–bond thus Hydration energy given out
is minimum
 Thus in 1o amines reaction is fast & in 3o amines reaction is slow
Basic nature according to Bronsted concept 1o > 2o > 3o
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These three effect are apposite to each other ∴ combined effect of these three & Pkb value
(CH3)2NH = 3.27 < CH3NH2 = 3.38 < (CH3)3N = 4.22
Correct order of basic nature is: (SPT)
(CH3)2NH > CH3NH2 > (CH3)3N > NH3 > C6H5NH2
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4. Basicity of Ethyl amine in aqueous medium: Et = C2H5 group

H Et Et
Et N N H
H Et Et N

1o Ethyl Amines 2o Ethyl Amines Et

3o Ethyl Amines

Basic Nature ∝ +I effect ∴ 3o > 2o > 1o.

1
Basic Nature ∝ ∴ 1o > 2o > 3o.
Sterric Hindrance
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H
H H O
Fast H+ H Hydration Energy
H
Et N Et N+ H O
H H Maximum
H H O
H
H
Et Et H O
H+ H
N H N+
H
Et Et H O
H

Et
Et
Slow H+ H Hydration Energy
Et N Et N+ H O
H Minimum
Et
Et
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 Ethyl amines are Bronsted base i.e. they can able to gain H+ ions
 Basic nature ∝ Tendency to gain H+ ions ∝ Speed of reaction
 Speed of reaction ∝ Stability of product
 But all protonated amines are charged species thus unstable
 They can be stabilized by dissolving them in water
 When 1o amine is dissolved in water it forms 3 H–bonds thus Hydration energy given out
is maximum
 When 3o amine is dissolved in water it forms 1 H–bond thus Hydration energy given out
is minimum
 Thus in 1o amines reaction is fast & in 3o amines reaction is slow
Basic nature according to Bronsted concept 1o > 2o > 3o
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If alkyl group is bigger than CH3 group, i.e., ethyl, propyl etc. there will be some steric
hindrance to H - bonding.
As a result, stability due to + I effect predominates over stability due to H - bonding and
hence 3° amines become more basic than 1o amines,
∴ combined effect of these three & Pkb
(CH3CH2)2NH = 3.00 < (CH3CH2)3 N = 3.25 < CH3CH2NH2 = 3.29
Correct order of basic nature is
(CH3CH2)2NH > (CH3CH2)3 N > CH3CH2NH2 > NH3 > C6H5NH2
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5. Basicity of amine in non aqueous medium:

H R R
R N N H
H R R N

1o Amines 2o Amines R

3o Amines

Basic Nature ∝ +I effect ∴ 3o > 2o > 1o.

1
Basic Nature ∝ ∴ 1o > 2o > 3o.
Sterric Hindrance

Actual Order 3o > 2o > 1o

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6. Basicity of aromatic amine (Toluidine’s):

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

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7. Basic nature of Nitro anilines:

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

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8. Basic nature of Chloro anilines:

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

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Q. 1. Explain Why
(i) O-Toludine is more basic than aniline. [SP 13]
(ii) pKb for aniline > methylamine. [DB 08][AI 08, 11][F 13][NCERT]
(iii) alkylamine more basic than ammonia? [DB 09, 11][F 10, 11]
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(iv) (CH3)2NH is more basic than (CH3)3N in an aqueous solution. [AI 14]
(v) Amines are more basic than comparable alcohols. [NCERT]
(vi) why are aliphatic amines are basics then aromatic amine? [NCERT]
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Q. 2. Arrange following compounds in order of basic strengths in aqueous solutions:
(i) NH3, CH3NH2, (CH3)2NH, (CH3)3N [AI 09] [DB 12, 13][SP 09][NCERT]
(ii) C6H5NH2, C6H5N(CH3)2, (C6H5)2NH and CH3NH2 [DB 10, 14][AI 11][NCERT]
(iii) C2H5NH2, (C2H5)2NH, (C2H5)3N, CH3NH2 [AI 08] [NCERT]
(iv) C6H5NH2, C2H5NH2, (C2H5)2NH, NH3 [NCERT]
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(v) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH [NCERT]
(vi) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2 [NCERT]
(vii) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2. [NCERT]
(viii) CH3NH2 & C6H5NH2 [F 14]
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(ix) CH3NH2 & NH3 [F 14]
(x) p–CH3–C6H5–NH2 & C6H5NH2 [F 14]
(xi) C6H5NH2, C6H5N(CH3)2, (C2H5)2NH & CH3NH2[AI 10] [NCERT]
(xii) Aniline, p-nitroanilins and p-toluidine [NCERT]
(xiii) C6H5NH2, C6H5NHCH3, C6H5CH2NH2 [NCERT]
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Q. 3. Arrange the following compounds in an increasing order of basic strengths in their
gaseous phase:
(i) NH3, RNH2, R2NH, R3N [F 09]
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3. [NCERT]
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Q. 4. Arrange following in order of pKb values
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2. [NCERT]
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