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ACIDITY & BASICITY Page # 3

Acidity & Basicity

HA H + A
Acid Conjugate base

Note : More stable the conjugate base (i.e., A ), more will be the forward reaction which results more
acidic nature of HA.

Ex.1 Compare the acidic strength of the following acids.

(a) C – C – C – COOH (b) C = C – C – COOH (c) C ≡ C – C – COOH
Sol. The acid whose conjugate base is most stable will be more acidic.
After forming conjugate base from the above acids.

(a) C – C – C – COO– (b) C = C – C – COO– (c) C ≡ C – C – COO–

sp3 sp2 sp
It is clear that sp hybridised carbon being most electronegative will decrease e– density from O most
effectively making the conjugate base most stable.
c>b>a (acidic strength)

Ex.2 Which is more acidic between the two

(a) CHF3 (b) CHCl3
Sol. CHF3 > CHCl3
If we consider the –I effect of F and Cl But this effect will not be considered here
After the removal of proton

F Cl
(a) – C F (b) –
C Cl
F Cl
(vacant d-orbital available where C will coordinate its electron) (pπ – dπ bonding)
⇒ a < b (acidic strength)

Ex.3 Compare the acidic strength of the following

(a) CHF3 (b) CHCl3
(c) CHBr3 (pπ – dπ bonding in Br is not as much as effective as in Cl due to large size of Br)
Sol. CHCl3 > CHBr3 > CHF3

Ex.4 Compare the acidic strength of the following

(a) CH (CN)3 (b) CH (NO2)3 (c) CHCl3
Sol. After removing H +

C≡N
–
C
C ≡ N (Resonance) In its resonating structure, –ve charge will be on N)
C ≡N

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Page # 4 ACIDITY & BASICITY

N=O
–
C
N=O (Resonance) (– In its resonating structure –ve charge will reside on O
O N=O
O
⇒ more effective Resonance

Cl
–
C
Cl (pπ – dπ)
Cl
b>a>c

* –ve charge on O is more

stable than –ve charge on N as O is more electronegative than N.
* Pπ – dπ Resonance < Actual Resonance

Ex.5 Compare the acidic strength of the following

(a) CH ≡ CH (b) CH2 = CH2 (c) CH3 – CH3

–
CH ≡ C > CH2 = CH > CH3 – CH2
Sol.
sp sp2 sp3
(Stability of the conjugate base)
⇒ a > b > c (acidic strength)

Ex.6 Compare the acidic strength of the following :

(a) CH3 – CH2 – CH2 – COOH
(b) CH3 – CH2 – CH – COOH
|
Cl
(c) CH3 – CH2 – CH – COOH
|
F
(d) CH3 – CH2 – CH – COOH
|
NO2
Sol. d>c>b>a

Ex.7 Compare the acidic strength of the following :

(a) H2O (b) H2S (c) H2Se (d) H2Te
Sol. Conjugate base is in an stability order

OH < HS < HS e < H2 Te

⇒ H2O < H2S < H2Se < H2Te (acidic strength)

394 - Rajeev Gandhi Nagar Kota, Ph. No. 0744-2209671, 93141-87482, 93527-21564
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ACIDITY & BASICITY Page # 5

Ex.8 Compare the acidic strength of the following compound

CH3 CH2Cl CH2F

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

Sol. After forming conjugate base of the above

CHCl CHF
CH2
–

pπ – dπ bonding due C – I effect of F

–ve charge is not vacant d-orbital of Cl decrease e– density
in resonance from C making the
(most stable) carbanion stable

c>d>b>a

Ex.9 Compare the reactivity of the following compounds with 1 mole of AgNO3

CH2Cl
Cl CH2Cl CHCl2

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

CH3

Sol. After removing Cl–

+
+ CH2

(+ve charge is not on resonance

∴ least stable)

+
CH – Cl

(most stable as L.P. of Cl will be coordinated to +ve charge completing the octet of each atom and
making the corbocation most stable)

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Page # 6 ACIDITY & BASICITY

+
CH2

(By hyper conjugation)

CH3

extent of +ve charge decreases stability increases

Ex.10 Compare the acidic strength

CH3
CH3 CH3 CH3

NO2
(a) (b) (c) (d)
NO2
NO2

Sol. After making conjugate base

–
CH2
CH2
CH2 CH2
NO2
(–I, –M)
NO2 NO2
(–I)
(–I, –M)

c>b>a>d

BASIC STRENGTH
+
A H
A+ – H
Basic strength directly depends on the availibility of lone pair for H+

Ex.11 Compare the basic strength of following

(a) NH3
(b) PH3
(c) AsH3 Basic strength
Sol.
(d) SbH3
(e) BiH3

Ex.12 Compare the basic strength of the following

(a) C H3 (b) N H2 (c) O H (d) F

394 - Rajeev Gandhi Nagar Kota, Ph. No. 0744-2209671, 93141-87482, 93527-21564
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ACIDITY & BASICITY Page # 7

Sol. C H3 , N H2 , O H , F
CH4 < NH3 < H2O < HF
(acidic strength)
– –
CH3 > NH2 > OH > F
(Basic strength)
* Strong Acids have weak conjugate base.
– –
CH3 > NH2 > OH > F
(Nucleophilicity)
* For the same period
less electronegativity, more nucleophilicity as more electronegative element has less tendencey to
give its electron pair.

Ex.13 Which is more basic O H or HS ?

Sol. OH > HS
–
Which is more basic NH3 or NH
2
forming conjugate acid
+
NH 4 > NH 3 (acidity)
–
∴ NH < NH (Basicity)
3 2

COMPARISON
COMPARISON OF BASICITY OF AMMONIA AND ALKYL AMINES :

Ex.14 Compare the basic strength of the following NH3, CH3NH2, (CH3)2NH, (CH3)3N
Factors which affect the basicity of Amines
(1) steric effects
(2) Inductive effect
(3) solvation effect.
• The base whose conjugate acid is more stable will be more acidic
forming conjugate acid of the given base
+ + + +
N H4 , CH3 NH3 , (CH3 )2 NH2 , (CH3 )3 N H
Stability order of conjugate acid
+ + + +
(CH3 )3 NH > (CH3 )2 NH2 > CH3 N H3 > N H4
(due to +I effect)
Therefore basic strength
(CH3)3N > (CH3)2NH > CH3NH2 > NH3
(vapor phase or gaseous is phase or in Non polar solvent)
In Aqueous solution or in polar solvent
(CH3)2NH > CH3NH2 > (CH3)3N > NH3

394 - Rajeev Gandhi Nagar Kota, Ph. No. 0744-2209671, 93141-87482, 93527-21564
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Page # 8 ACIDITY & BASICITY

• In aqueous solution, the conjugate acids form H-bonds (intermolecular) with water molecules and
stabilise them selves conjugat acid of 1° amine which has largest no. of H-atoms form maximum H-
bond with water and is most stable. Consequently 1° amine is most basic.

• Due to steric effect 1° amine is considered more basic as compared to 3° amine as lone pair is hindered
by three alkyl group and less available for H+.
Considering the combined effect of the three (Inductive, solvation and steric effect) we can conclude
that
2° > 1° > 3° > NH3

• Aromatic amines are least basic as their lone pair is in conjugation and less avaibable for protonation.

Ex.15 Compare the basic strength of the following

N NH2 H
|
(no Resonance as
N
ring will break if we
draw the resonating
(a) (b) (c)
structure)
(Resonance)
(most basic)
(if L.P. will be participate in Resonance, then molecule becomes aromatic)
∴ Hence L.P. will have a greater tendency to take part in Resonance and will be less available for H+
∴ This compound will be least basic.

Ex.16 Compare the basic strength of the following

sp
Common for all
(a) CH ≡ C – CH2 – NH2
(b) CH2 = CH – CH2 – NH2
sp2
(c) CH2 – CH2 – CH2 – NH2

sp3

Sol. sp hybridised carbon being most electronegative will attract e– density from nitrogen and will make it
less available for H+. Hence basicity decreases.
c>b>a

Ex.17 Compare the basic strength

H
|
N H
|
N
(a) O (b)
(–I of O at attracts e– density
from N making it less basic)
a<b

394 - Rajeev Gandhi Nagar Kota, Ph. No. 0744-2209671, 93141-87482, 93527-21564
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ACIDITY & BASICITY Page # 9

Ex.18 Compare the basicity of the following compounds

••
(a) CH3 – CH2 – CH = CH – N H (b) CH 3 – CH 2 – CH 2 – CH 2 – NH 2
2

sp3
(c) CH2 = CH – CH2 – CH2 – NH2 (d) CH ≡ C – CH2 – CH2 – NH2

sp2 sp
Sol. In part (a) the lone pair of nitrogen in Resonance therefore will be less available for H+ making it least
basic among all followed by sp, sp2, sp3 hybridised carbon atoms.
b>c>d>a

Ex.19 Compare the basicity of the numbered nitrogen atoms.

(As L.P. in
Resonance)
H sp2 sp2
|
N N
H–N 1 2 3 as L.P. is not in Resonance
(or in conjugation)
sp3 N

Sol. The planerity of ring will be destroyed if L.P. will take part in Resonance.
Basicity order of Nitrogen follows the order
N(sp3) > N(sp2) > N(sp)

1 > 3> 2

sp2 sp2

(In this sp2, l.p. is in Resonance

with ring hence will be less
available for H+ therefore it will
be least basic)

Ex.20 Compare the basic strength of the following

NH2
NH2
NH2

(a) (b) (c)

NO2 NO2

Sol. In part (a) NO2 is at p-position Hence will attract e– density by both –M and –I
In part (b) NO2 is at m-position hence will attract e– density by –I only
There is no such effect in part (c)
⇒ Availibity of L.P. on nitrogen in part (a) is minimum followed by b and then c.
c>b>a

Ortho effect :
The ortho substituted aniline are less basic than aniline and ortho substituted benzoic acids are more
acidic than benzoic acid.

394 - Rajeev Gandhi Nagar Kota, Ph. No. 0744-2209671, 93141-87482, 93527-21564
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Page # 10 ACIDITY & BASICITY

• Ortho effect is valid only for benzoic acid and aniline.

NH2 NH2 NH2 NH2
NO2 CH3
e.g. < Also <

Ex.21 Compare the basic strength of the following :

NH2
NH2
NH2
NH2
CH3

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

CH3 CH3
(+I) (+I)
(+I, Hyperconjugation)
Sol. a>b>d>c

* Due to ortho effect d > c

if c is less basic than d then it will be certainly less basic than b as b is more basic than d.

Ex.22 Compare the basic strength of the following :

NH2
NH2
NH2 NH2

NO2
(a) (b) (c) (d)

NO2 NO2

Sol. Do your selves

S.I.P → Steric inhibition of Protonation (ortho effect)

+
NH2 NH3
G G
H+

after protonation, repulsion increases therefore ortho substituted aniline is less basic than aniline

S.I.R → Steric inhibition of resonance

NH2
NH3 CH3

CH3 NO2
(a) CH3 (b)
NO2

(Shows –I as well as – M this

(Shows only –I effect) means delocalisation of e– is more)

394 - Rajeev Gandhi Nagar Kota, Ph. No. 0744-2209671, 93141-87482, 93527-21564
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