IONIC EQUILIBRIUM Limitations of Arhenius

Limited to
aqueous
Theory
solution
. Types of Lewis Base

Arrhenius Base cannot acids and bases Neutral molecules with at

+
explain
CH3COOH - CH3COO- + H
substance which
weak
electrolytes Any give of- withoutHt and Orions .
least one lone pair
Undissociated dissociated ion in water H2D NH3 R-NH2 R-O-H
Negligibly ionised/dissociated eq is established
k
*
, , ,

( Degree of dissociation (d) < Negatively charged ions

Arrhenius Acid-Base Theory F-CI OH-RO-

Ionic
equilibrium Weak Acid HF CH3COOH HCOOH
G , ,

Arrhenius Acid -
↓
k
Weak Base NH4OH R-NH2 NH3
substance which Ht
give
, .

Any
of Lewis Acid
Equilibrium established between dissociated part and ion in water. Types

↑
Acids -

Ht donors
undissociated Molecules in which neutral atom
part is known as ionic
equilibrium .
Bases -

It acceptors octet
has
incomplete
Acid-Base
conjugate pais
A lC13 BF3
classification of
electrolytes
,

difference of Htion
Electrolytes HCI >
H+ + Cl Pair
having one
D Block cations

-
-

I
which dissociate into component ions
. Acid (SA) conjugate Base (WB)
Fet cut
2

+
CH3COOH > H+ + CH3COO-
CH3COOH CH3C00- H
t
> +
V
-

Acid (WA) Conjugate Base (SB) Bronsted

4 Lowsy theory Molecules in which central atom

strong electrolytes -
>

-
has d-orbitals.
Classification of substances empty

NITESH DEVNANI
Note
100 % jonised/dissociated L siF4
t degree of dissociation < =
1 100 % ionised If Acid is weak then its conjugate CO2 ,
SO2

and vice L
Non-electrolytes strong Acid HCI ,
MBO ,
HI ,
H2SO4
Base is
strong .
versa

Limitations Limitations
which does not dissociated into component ions
. Strong Base NaOH ,
KOH

of Acids and Bases

NH2CONH2(s) H20
, NH2CONHzlag)
Salts NaCl ,
NHyCI ,
CHICOONG cannot explain acidic nature
It fails to
assign strength .

of AlCIs BF3 etC According to this

theory ,
acid-base reaction should be
,
.

accompanied by formation of co-ordinate Bond

.

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 IONIC EQUILIBRIUM which releases

than one Htion

more

E -
which releases

than one OH-ion

move

H2504 H3PO4
"
[OH-] CalOH)2 Al IOHIs
water is weak CH + ] 10 PH T
=

electrolyte
= =

a
very K6 =
[B ] [OH-]
+
Polybasic acids and

kW =
[H ] [OH-]
+ >
- [H + ] < [OH-] Acidic PH < T [BOH]
H3P04 Ka ,
polyacidic bases
Ka =
Ka, X Kaz X Kaz X ....

t
X = T Kaz
K6 KO1 KO2XKb3X
[H + ] [OH-] Neutral
X

product
=

Ionic of water water =

PH
=
T
C
....

Kaz
At 298K kw 10-14 [H + ] < [OH-] Basic PH > T

↓ 1(PK6-log
=

POH
=
,

kep
=
Ka , X Kaz X Kas
of H-X Bond
Polarity :

POH Scale
↑ More the
polarity
Eq constant depends only and
only on
temperature . More is Acidic
Ionisation of weak Base of H-X Bond strength
Effect of T on KW :
Negative logarithm /base 10) of Strength
weaker the Bond the acid
.
↑
↓
TY KW4 :
Dissociation of H2O increases .
Of-ion concentration , stronger
[OH-] H-F < H-CI < H-B0 < H I
POH -109
-

Factors
affecting
=

↑
-

-
weakest
Relation between ka and kb
strongest acidic
strength
PH Scale

H + + At Ka X K6 [H + ] [OH-]
(base 10) ofE
HA
=
+ H20 -

Negative logarithm scale Weak

electrolyte L
Ka =
[H + ] [A] =
K X [H20] KaXKb =
Kw
concentration
hydronium ion Common Ion effect

&
:
[HA] 1) CHICOOH - CH3CO0- + Ht
Valid for
conjugate Acid-Base pair
Ka = CX2 L

+ I
+
[H

(
PKa + PK6 PKW
H <
PH 10910
= - =

1 -
X

strong electrolyte very dilute acid

of
At 298K PKa + PK6 =
14 PH strong

NITESH DEVNANI
"
Total CH + ] < 10
If
+
Ionisation constants of weak acid Nat
=

2) CHICOON = CH3C00- +

Pure water and

pKw pH + POM
( [H + ]
=
=
< + 10 =
C

PH + pOH 14 - 298K
< For weak
electrolyte 10-6
=

if < <,
[H + ]
I
I
C Ka
L
=
>X
=

PKw =
14 1-X = 1 Ka CX2
[Ag"]
=

C
Ksp [Cl ]
Age
=

14
solubility equilibria of which have low
solubility
-

KW =
10
[H ] +
1/ + very
1 KaXC
[Ba ] (504-2)
=
= Ka 2
Ksp BasO4
=
=

kw Pkw
-logio kw ↓T
sparingly soluble salts AGCI AgBo AgI BasOs POSO4
=

C
PH <(PKa log
=
+
< [5-2)
-

Ksp [Ag Ag2S

:

Pka
Ka
-log Ka
=

K6
K6 PKO
log
-
=

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IONIC EQUILIBRIUM
Buffer
Range
of buffer solution
Range over

which it is effective . Buffer solution

dilute solution solution whose does not change

Degree of ionisation (d) is
inversely proportional For
very ,
weak
electrolyte Buffer action
↑
A
pH
addition of small amount of acid
to
square root of conc or
directly proportional start
behaving as
strong electrolyte Action of buffer solution on addition on
Buffer
on dilution of dissociation increase
to
square root of volume , degree of small amount of acid or base
↑
- >
- or base or on dilution is known

* - 7
by which it resist the
change in
PH .
as Buffer solution
.

Ostwald's Dilution law IWA and WB-valid)

AgCl(s) Agt(aq) 4-(ag) solubility
-
- -
- + =

of Buffer solution
KSp [Ag
+
] [CI] Types
L
I
- -
=

Simple Buffer (1 component)

Ksp 52
L I
q S
-

S S =

T salt of weak acid and weak Base

.
e
g.
y (CH3COOH) (NHEOH)
c> 0 x +> 1
I strong electrolyte Components)
Mixed Buffer 12
-

and
Relation between
solubility ksp CH3COONHy < CH3COO- + NHG
+
Buffer Action

Famous
gues 2 Note
: How to
identify acidic Buffer :
↑

Note -

For
precipitation ,

Agcl AgBo AgI More the value of Ksp >

solution
containing weak acid and
IP <
Ksp Ionic product solution weak acid and
Ksp-AgCI
>
AgBo AgI >
More is
solubility &
its salt with Base .
containing
strong
solubility
-

AgCl <
AgBo >
AGI AgI(s) =
Ag(ag) Cilag) + its salt with
strong Base
Less
precipitation e CH3COOH + CHSCOONG
G.

-
.

Ksp [Ag
+
] [CI) equ concentration
Precipitation AgCI
<
AgBo
<
AgI
=

Late
precipitation.
-

CH3COOH + CHSCOONA

NITESH DEVNANI
↑
+
) / CI] conc at time t
IP
[Ag any
=

not defined
Agf-soluble Ksp
Acidic Buffer
>
- solution of weak acid and
strong Base where
Due to communion
>
solubility decreases
( strong Base is
Limiting Reagent
More the common ion < Lesser is
solubility
AgC(s) Aglag) cl'lag) <
Y [Anion of salt] H2O
+

- Acidic Buffer PKa

log
=

PH
+
CH3COOH NaOH 'CHSCOONA +
=
+

HC1 > H+ + d
[Acid] LR
[CI-74 >
-

-XNQ will move in BD common ion effect

·
solubility decreases on
solubility
@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194
.
 IONIC EQUILIBRIUM
of salt of weak acid and weak Base
of salt of Base and weak Acid Hydrolysis
solution
containing weak base and
Hydrolysis strong
:

- Basic Buffer >

-

PK6 [Cation of salt]

PoH +
log
=

CH3COONHy + H2D "CH3COOH + NHGOH

its salt with acid
strong
=

= CH3COOH NaOH
[Base] CH3COON + 120 +

NHyOH +
NHGCI KU = [CH3COOH] [NH4OH]
Kh =
[CH3COOH] [OH-]
[CH3CO0-] [NHG ]
[CH3COO-]

Anionic
hydrolysis Cationic and Anionic hydrolysis
solution weak Base and its
solution of weak base and
strong acid where containing solution becomes basic h2
Kh =

salt with Acid

strong acid is
limiting reagent. strong kn
(l h)2
-

NHaOH +
NH4C
= 1 H 1
=

-
-

NHSOH + HC 'NHGCI + H2O

PH T
+H (PKa +
log
=

Ka > Kb >
PKa < PK6 >
Acidic

h =
KW Ka < K6 >
-

PKa > PKb -Basic

acid and weak Base
Hydrolysis of salt of
strong KaXC
How to
identify Basic Buffer
NH4C H2O =
Ka =
K6 >
Pka =
PK6 >
Neutral
+ HC1 + NH4OH
a

S / -logka log[H ]
+
PKa pH

>
= = -

-
KU =
[NH4OH] [H ] +

L Ka4-PKay [H + ] ↑ =

PH I
[NHst7
A Buffer solution can be
-
L
prepared from Cationic
hydrolysis Salt
hydrolysis
solution becomes acidic
Reverse of neutralisation
Sodium acetate and acetic acid in water
Hydrolysis is always of weak part >
- of salt of

NITESH DEVNANI
Hydrolysis strong acid and
strong base

(
CH3COONG + CHICOOH
kn =
Kw
NACI + H20 =-> HCI + NaOH
Kb L
Sodium chloride and HCI in water
h =

degree of hydrolysis salt

hydrolysis No
hydrolysis
NaCl + HCI Neutralisation
Saltwater - Acid+ Base Neutral solution

T
n =
Acid + Base - Salt Water
Ammonia and NHGCI in water +
At 298K pH
=
7
SA SB WA SB
,
+ +

NH3 + NH4CI WA
SA + WB + WB
pH
=
7
-k (PK6 + logc
Ammonia and Naok in water

NH3 + NaOH

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