Ionic Equilibrium: Types of K

IONIC EQUILIBRIUM Page # 3
IONIC EQUILIBRIUM
An ionic Equilibrium exists between the unionised electroyte molecules and the ions that result from
ionisation
A + B A+ + B–
 Types of keq

Self ionization Acid dissociation Base dissociation Salt Sparingly
of water constant constant hydrolysis soluble salt
H2O H++OH + –
H A H+ +A– BOH B++ OH– – +
A B +H2O HA+BOH AgCl Ag++Cl–
 Concept of electrolyte

Strong electrolyte Weak electrolyte
A  B–  A   B– AB A+ + B–
a 0 0 a 0 0
0 a a a (1 – ) a a
 100% disssociation ( = 1) <1
 no equilibrium equilibrium
 it is irreversible it is reversible process.
 Self ionization of water
1000 / 18
Concentration of H2O ([H2O]) =  55.5 M
1
Water is very weak electrolyte
H2O H+ + OH–
55.5
55.5 – 10–7 10–7 10–7 (at 25oC)
[H ] [OH– ]
 k eq 
[H2 O]
Constant
 Kw = keq [H2O] = [H+] [OH–]
 Kw = [H+] [OH–], at 25oC, [H+] = [OH–] = 10–7

o –14
Kw (25 C) = 10

Self ionization constant of water
let, Kw1 at temperature T1 , Kw2 at temperature T2
Kw 2 H  1 1 
 log   –  T   Kw 
K w1 2.303 R  T1 T2  ,
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Page # 4 IONIC EQUILIBRIUM
 For calculation of  :
+ –
H2O H + OH
c 0 0
c (1 – ) cc
Kw = c × c
kw
   c = 5 5.56 M    1.8  10 –2 Kw
c
pH (pH scale is given by Sorension)
 potent Hydrogen ion


strength
at 25°C
+
 pH = – log [H ] pH scale
p OH = – log [OH–]
p Kw = – log Kw Neutral
at any temperature :
[H+] = [OH–] O Acidic basic
[H+] [OH–] = Kw 7 14
 – log [H+] – log [OH–] = – log [Kw]
 pH + pOH = p Kw
at 25oC at 80oC
Kw = 10–14 Kw = 10–12
pH + pOH = 14 pH + pOH = 12
25oC 90oC
pH + pOH = 14 pH + pOH = 12
Some concept regarding pH calculation

 Concept 1 :  Concept 2:
5L 1L 3L 2L 5L
pH = 3  pH = ? pH = 3 + pH = 3  pH = ?
 Concept 3:  Concept 4:
2L 8L 10 L 2L 8L 10 L
pH = 3 + H2O = pH = ? pH = 13 + water = pH = ?
Ca lcula te pH (i) Ca lcula te pOH

 Note : 7
pH (ii) pH = 14- pOH
 Concept 5:
pH = 3 + pH = 4 = pH = ?
2 : 1
 Note : The final pH of solution after mixing two solution is in between the previous solution pH.
 Concept 6:  Concept 7:
10 M HCl
–8
V V 2V
pH = 3 + pH = 11  pH = ? pH = ?
 Note :
When [H+] > 10–5  [H+]water neglected
When [H+] < 10–5  [H+]water considered
H2O H+ + OH–
55.56 10–8
55.56 – x 10–8 + x x
 x (10–8 + x) = 10–14  x = .94 × 10–7
 [H+] = 10–8 + .94 × 10–7 = 1.04 × 10–7
 pH = 7 – log (1.04)
 Concept 8:
2
10 M HCl
pH = ?
 Dissociation of weak acid :
H+ A– H+ + A–
c
c (1– ) c c
c 2
Ka  for weak acid < < 1 Ka = c2
1– 

Kw
[H+] = c = c Ka , pH = – log c Ka , for bases [H+] = c  Kb
 Note :
(a) HA1 c Ka 1
||
[H  ]1 Ka 1
HA2 c Ka 2 
 
[H ] 2 Ka 2
 So HA2 is stronger acid than HA1

(b) HA1 c1 Ka 1
[H ]1 c1 ka1
HA2 c2 Ka 2 
[H ]2 c 2 Ka2
 The acidic strength of two weak acid can be compared by Ka value only in the case when their
concentration are same. Otherwise the procedure of case (b) should be followed .

pH of mixture of two acids
 Case (I) (Strong acid + weak acid)
Question : HCl (0.1 M) + CH3COOH (0.2 M)


Ka = 10–5
CH3COOH CH3COO– + H+
t=0 0.2 0 0. 1
t = teq 0.2 – x x 0.1 + x (x is very small)
  
0.2 x 0.1
x  0.1
 pH = – log (0.1) = 1  [CH3COO–] = ?  10 – 5   [CH3 COO– ]  2  10 – 5
0.2
 Case (II-A) (weak acid + weak acid ) (kas are incomparable)
Question : HA1 (0.1 M, Ka 1 = 10–5)
HA2 (0.2 M, Ka 2 = 10–9)
HA1 H+ + A1 – HA2 H+ + A2–

0.1 0 0 0.2 0 0
0.1 – x x+y x 0.2 – y x+y y ( Ka 1 >> Ka 2
       x > > y)
0.1 x x 0.2 x y
x and y are also very less
x. x
10 –5  [H+] = x = 10–3 ,  pH = 3 [A1– ] = [A2–] =
10 –1
 Case (II-B) (weak acid + weak acid ) (kas are comparable)
Question : HA 1
(0.1) Ka 1 = 10–5
HA2 (0.2) Ka 2 = 10–6

HA1 H+ + A1 – HA2 H+ + A2–
0.1 0 0 0.2 0 0
0.1 – x x+y x 0.2 – y x+y y
0.1 x+y x 0.2 x+y y
x (x  y)
 now K a1 
0.1
x (x  y) (x  y) y
 Ka 1  , Ka 2 
c1 c2
 [H  ]  x  y  c 1 Ka1  c 2 Ka 2
 weak polyprotic acids or bases

(H2S, H3PO4, NH2 – NH2, H2CO3)
(a) H2S H+ + HS– Ka 1 HS– H+ + S2– Ka 2

 
(b) NH2 – NH2 + H+ NH2 – NH3+ Kb 1 NH2 – NH3+ + H+ NH3 – NH3 Kb 2
Cases
 Case I : H2S (0.1 M Ka 1 = 10–4 , Ka 2 = 10–9)
 H2S H+ + H S– H S– H+ + S2–
0.1 0 0 x x 0
0.1 – x x+y x–y x–y x+y y
     
0.1 x x x x y
Ka 1 > > Ka 2 x >> y
x2 x y
10 – 4   x 10 –5  10 –9
0.1 x
[H+] = x = [HS–] = x = [S2–] = y =
 Case II : HCl H+ + Cl–

0.2 0 0
0 0.2 0.2
 H2S H+ + HS– H S– H+ + S2–
0.1 0.2 0 x 0.2 + x 0
0.1 – x 0.2 + x + y x x–y 0.2 + x + y y
     
0.1 0.2 x x 0.2 y
[H+] = 0.2  pH = – log (0.2)
 Note : Strong acid controls the pH.

 Now , [H+] = 0.2
 Case III : H3PO4 (0.1 M) Ka 1 = 10–5 , Ka 2 = 10–8 , Ka 3 = 10–11
 H3PO4 H+ + H2PO4– H2PO4– H+ + HPO42–

0.1 0 0 x x
0.1 – x x+y+z x–y x–y x+y y
     
0.1 x x x x y
 HPO42– H+ + PO43–
y y+x
y–z x+y+z z
  
x2
y x z   10 – 5  x  10 – 3  pH = 3
0. 1
 Buffer
 Any solution which resist the change in pH is called Buffer solution.
 Requirement of Buffer
(1) Must have acidic and basic components so that it can consume H+, OH– added to the buffer.
(2) Acidic and basic components should not react with each other.
CH3COOH CH3COO– + H+
acid conjugate base
 
acidic component basic component
do not react with each other.

(3) Buffers can be prepared by following two ways
 Buffer
CH3COOH / CH3COONa NH4OH / NH4Cl

W. A / Canjugate Base W. B / Conjugate acid
 acidic buffer  basic buffer
 0 < pH < 14  0 < pH < 14
 Acidic buffer Basic buffer
Ka c1 c2 Kb c1 c2
CH3COOH CH3COO– + H+ NH4OH NH4+ + OH–
c1 c2 0 c1 c2 0
c1 – x c2 + x x c1 – x c2 + x x
     
c1 c2 x c1 c2 x
in presence of CH3COO– dissociation
c2 .x
of CH3COOH is supressed. Kb 
c1
c1
So x is very small x  Kb
c2
c2 x [salt]
Ka  pOH = pKb + log
c1 [base ]
Ka c 1 c2 [salt]
 x= pH  pK a  log pH  pK a  log
c2 c1 [acid]
 Buffer action
 Acidic Basic
c1 c2 c1 c2
c2 [c 2 ]
pH = pKa + log c pOH = pKb + log [c ]
1 1
 (a) NaOH is added (x M) (a) HCl is added (x M)

– –
CH3COOH + OH CH3COO + H2O NH4OH + H+ NH4+ + H2O
c1 x c2 c1 x c2
c1 – x 0 c2 + x c1 – x 0 c2 + x
c2  x c2  x
pH  pKa  log pOH  pKb  log
c1 – x c1 – x
 (b) HCl is added (x M) (b) NaOH is added (x M)
–
CH3COOH CH3COO + HCl NH4OH NH4+ + OH–
c1 c2 x c1 c2 x
c1 + x c2 – x 0 c1 + x c2 – x 0
c2 – x c2 – x
c1  x c1  x
 How to prepare buffer
Acidic buffer Basic buffer

 (a) CH3COOH / CH3COONa (a) NH4OH / NH4Cl
c1 c2 c1 c2
c2 c2
c1 c1
 (b) CH3COOH + NaOH CH3COONa + H2O (b) NH4OH + HCl NH4Cl + H2O
a x a x 0
a–x 0 x a–x 0 x
x x
a–x a–x
 (c) CH3COONa + HCl CH3COOH + NaCl (b) NH4Cl + NaOH NH4OH + NaCl
a x 0 a x
a–x 0 x a–x 0 x
a–x a–x
x x
 Parameters of buffer
 Buffer range Requirement of good buffer

The range of pH a buffer can work nicely (1) pH = pKa
is called buffer range resist both OH– and H+ in equal amount
salt c2
pH = pKa + log (2) pH = pKa + log c
acid 1
 [salt] 
after buffer action max. ratio   = 10
 [acid ] 
c2 – x
pH = pKa + log c  x  pH = pKa + 1
1
 [salt] 
min. ratio   = 0.1 both will be approximately same when
 [acid ] 
pH = pKa – 1 c1 and c2 are very large
c1 , c2 > > x
c2
pKa – 1 pKa pKa + 1  pH  pK a  log
c1
 Buffer capacity
number of mol of H added/L of solution
 Buffer Capacity 
Change in pH of buffer
 Buffer of polyprotic acid
H2CO3 / NaHCO3
c1 c2
H2CO3 HCO 3– + H+ Ka 1 HCO 3– H+ + CO 23– Ka 2
c1 c2 0 c2 + x x 0
c1 – x c2 + x – y x+y c2 + x – y y+x y
     
c1 c2 x c2 x y
c2 y
pH  pK a1  log pH  pK a 2  log
c1 c2
 Salt Hydrolysis
Acid + Base  Salt + H2O neutralization
Salt + H2O  Acid + Base  reverse of neutralization  Salt hydrolysis
since salt hydrolysis is an endothermic reaction hence on increasing the temperature, the extent
of hydrolysis increases.
 Types of salt
Case I Case II Case III Case IV

W. A + S. B S. A. + W. B. W. A + W. B. S. A. + S. B.
e.g. CH3COONa e.g. NH4Cl e.g. CH3COONH4 e.g. NaCl
Case : (I) Hydrolysis of WA + SB :

+
CH3COONa  CH3COO– + Na  spectator ion
 
Very strong Very weak
Conjugate base Conjugate acid
H – OH
CH3COOH NaOH
CH3COO– + H+ Na+ + OH–

CH3COONa CH3COO– + Na+
–
CH3COO + H2O CH3COOH + OH–
__________________________________________
CH3COONa + H2O CH3COOH + Na+ + OH–
__________________________________________________________________________
Note : (1) Only weaker part of salt undergoes hydrolysis. (2) This solution becomes basic.
Case : (II) S.A. + W.B. (NH4Cl) :
NH4+ + H2O NH4OH + H+, This solution becomes acidic
Case : (III) W.A. + W.B. (CH3COONH4) :
–
CH3COO + H2O CH3COOH + OH–
a x
a–x
NH4+ + H2O NH4OH + H+
a y
a–y
Can be acidic, basic or neutral
 Ka  Kb  acidic Ka  Kb  neutral Ka  Kb  basic
Case : (IV) S. A + S. B (NaCl) :
 No hydrolysis  Solution will be neutral
 Relationship between Ka, Kb, and Kh
Case (I) : W. A. + S.B. (CH3COONa)
CH3COO– + H2O CH3COOH + OH–
[CH3 COOH] [OH– ] [CH3 COOH] [OH– ]  [H ] wK
 Keq  –  Kh  Keq [H2 O]  –   Kh  K
[H2O] [CH3 COO ] [CH3 COO ]  [H ] a
Case (II) : S. A. + W. B. (NH4OH)

+
NH 4
+ H2O NH4OH + H+
[NH4 OH][H ] [NH4 OH][H ]  [OH– ] wK
 Kh    Kh   –  Kh  K
[NH4 ] [NH4 ]  [OH ] b
Case (III) W. A. + W. B. (CH3COO NH4)

CH3COO– + H2O CH3COOH + OH–
+
NH4 + H2O NH4OH + H+
_______________________________________________________
CH3COO– + NH4+ + 2 H2O NH4OH + CH3COOH + H+ + O H–
_______________________________________________________
[NH4 OH] [CH3 COOH] [NH4 OH] [CH3 COOH] [OH– ] [H ] w K
 Kh  –
[CH3 COO ] [NH4 ]   Kh   –   Kh  K . K
[NH4 ] [OH ] –
[CH3 COO ] [H ] a b
 pH calculation
Case (I) : W. A. + S. B. (CH3COONa  c, Ka) , h  degree of hydrolysis.
– –
CH3COO + H2O CH3COOH + OH
c 0 0
c (1 – h) ch ch
(ch) 2 ch 2 Kh
Kh   h<<1 Kh = ch2 h

c (1– h) 1 – h
  c
Kw 1 1
 pOH  [pKw – pKa – log c]  pH  [pKw  pKa  log c]
–
 [OH ]  c  h  c. Kh  c.
Ka 2 2
Case (II) :S. A. + W. B. (NH Cl 4  c, Kb)

+
NH 4
+ H2O NH4OH + H+
c 0 0
c (1 – h) ch ch
ch 2 Kh
 Kh  h<<1  Kh = ch2  h 
1– h c
Kw 1 1 kw
 [H ]  c.h  c  Kh  c   pH  [pKw – pKb – log c]  pOH = p  pk b  log c
 
Kb 2 2
Case (III) W. A. + W. B. (CH3COONH4  Ka, Kb , c)

– +
CH3 COO + NH + H2O 4
NH4OH + CH3COOH
c c
c (1 – h) c (1 – h) ch ch
c 2h 2 h2
 Kh  2 2
  K h = h2 1– h  1  h  Kh
c (1– h) (1 – h)2
Kw
 h - - - - - (1)
Ka Kb
[H ] [CH3 COO – ]  [CH3 COOH]

 CH3COOH CH3COO– + H+  Ka  [CH3 COOH]  [H ]  Ka [CH COO – ]
3
ch Kw
  Ka  (h < < 1)  [H+] = Ka . h  [H ]  Ka . (from 1)
c (1– h) Ka . Kb
Ka 1
 [H ]  Kw .  pH  [pKw  pKa – pKb ]
Kb 2
 If , Ka > Kb  pKa < pKb  acidic, Ka = Kb  neutral, Ka < Kb  basic
 Summary of hydrolysis
Kw 1
1. W. A. + S. B. Kh  K pH 
2
[pK w  pK a  log c]
a
Kw 1
2. W. B. + S. A. Kh  K pH 
2
[pK w – pKb – log c]
b
Kw 1
3. W. A. + W. B. K h  K . K pH 
2
[pK w  pK a – pK b ]
a b
 Hydrolysis of salt of polyprotic acid / base (Na2 CO3)

Kw
 CO 23– + H2O HCO3– + OH– Kh1 (CO3 – – ) 
Ka 2
a
a–x x–y x+y
 
x x
– Kw
 HCO3– + H2O H2CO3 + OH– Kh2 (HCO3 )  K
a1
x–y y x+y
  
x y x
Ka1   Ka 2  Kh1   Kh2  Mainly hydrolysis is governed by CO 23– .
– c  Kw c  Kw Kw x y Kw
[HCO3– ]  [OH– ]  [H2CO 3 ] 
  [OH ]  c  Kh1 
Ka 2 ,   Ka 1 ,   Ka 
x  Ka1
1
 Solubility of sparingly soluble salt
Solubility
AgCl (s)   AgCl (aq.) Ag  (aq)  Cl– (aq)
 In ionic equilibrium all the components of equilibrium should be in same phase.
 In case of solubility equilibrium of sparingly soluble salt equilibrium is a heterogeneous equilibrium.
Example (1) : Solubility of AgCl
AgCl (s) Ag+(aq) + Cl–(aq)
[Ag  ] [Cl – ]
Keq 
[AgCl]
 Ksp = Keq . [AgCl] = [Ag+] [Cl–]
 It is a endothermic reaction on increasing temperature T   solubility 
Ksp2 H 1 1
 log   – 
Ksp1 2.303 R  T1 T2 
Example (2) : Solubility of Ag2 CO3 Ag2 CO3(s) 2 Ag+ + CO 23–
 Ksp  [Ag ]2 [CO 32 – ] ,  In general , if salt is Mx Ny type, Mx Ny x My+ + y Nx–
 Ksp  [M y  ]x [Nx– ]y
let , Q = [My+]x [Nx–]y Q = ionic product
If , Q = Ksp  Equilibrium (Saturated solution) Q > Ksp  PPt (Super saturated)
Q < Ksp  Unsaturated solution.
 Various case in solubility
 Case (1) : Ag2SO4 (S = 10–3 mol/L)
Ag2SO4 2 Ag+ + SO 24 –
S 0 0
0 2S S Ksp = [Ag+]2 [SO4- - ] = (2 S)2 (S) = 4 S3
= 4 × (10–3)3
 Case (2) : S (moL / L)  S (gm / L)

10–3
SAg2SO4 (gm/L) = 10–3 × (108 × 2 + 96)
 Case (3) : Ksp given , Solubility = ?
Ag2 SO4 2 Ag +
+ SO24–
S 0 0
0 2S S
S  3 Ksp
 4 S3 = Ksp  mol/L
4
 Case (4) : 70% of the dissolved salt ionizes .
Ag2SO4 2Ag+ + SO24–
S 0 0
S – 0.7S 2 × 0.7S 0.7S
S  3 K sp
 Ksp = (1.4S)2 (0.7S) 
0.98
 Case (5) : Solubility of Ag2SO4 in 0.1 M AgNO3
AgNO3  Ag+ + NO3–
0.1 0 0
0 0.1 0.1
Ag2SO4 (solid) Ag2 SO4 (aq) 2 Ag+ + SO4–
S 0.1
0 0.1 + 2S S
K sp
 KSp = (0.1 + 2S)2 (S)  Ksp  (0.1)2  S  S 
0.01
 Case (6) : Solubility of Ag2SO4 in 0.1M Na2 SO4
Na2SO4 2 Na+ + SO24–
0.1 0 0
0 0.2 0.1
Ag2SO4 (S) Ag2 SO4 (aq) 2 Ag+ (aq) + SO24– (aq.)
S 0 0.1
0 2S 0.1 + S
K sp
 KSp = (2 S)2 (S + 0.1)   4 S2  0.1  S
0.4
 Case (7) : 100 ml 0.01 M AgNO3 + 400 ml 0.02 M Na2SO4, Ksp (Ag2 SO4) = 4 × 10–9
(a) Will any ppt or not ?
 8 
Q = [Ag+]2 [SO24– ] Q = (1/500)2   = 6.4 × 10–8 Q > Ksp  ppt
 500 
(b) After ppt [Ag+] = ? ; [SO42–] = ?
at equilibrium
4S3 = 4 × 10–9 S = 10–3
Number of moles of (Ag2SO4) = 500 × 10–3 = 0.5 m mole
2 Ag+ + SO24– Ag2SO4
1 8
1 – 2x 8–x x
2
 y   7.5  –9
     Ksp  4  10
y 7.5 0.5  500   500  y =?

Ionic Equilibrium: Types of K

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Ionic Equilibrium: Types of K

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IONIC EQUILIBRIUM Page # 3

 Self ionization of water

 Kw = [H+] [OH–], at 25oC, [H+] = [OH–] = 10–7

pH (pH scale is given by Sorension)

 potent Hydrogen ion

 – log [H+] – log [OH–] = – log [Kw]

Some concept regarding pH calculation

Ca lcula te pH (i) Ca lcula te pOH

 Dissociation of weak acid :

 So HA2 is stronger acid than HA1

 Case (I) (Strong acid + weak acid)

Question : HCl (0.1 M) + CH3COOH (0.2 M)

 Case (II-A) (weak acid + weak acid ) (kas are incomparable)

Question : HA1 (0.1 M, Ka 1 = 10–5)

HA2 (0.2 M, Ka 2 = 10–9)

HA1 H+ + A1 – HA2 H+ + A2–

HA2 (0.2) Ka 2 = 10–6

 weak polyprotic acids or bases

(a) H2S H+ + HS– Ka 1 HS– H+ + S2– Ka 2

 Case I : H2S (0.1 M Ka 1 = 10–4 , Ka 2 = 10–9)

 Case II : HCl H+ + Cl–

 Note : Strong acid controls the pH.

 H3PO4 H+ + H2PO4– H2PO4– H+ + HPO42–

do not react with each other.

CH3COOH / CH3COONa NH4OH / NH4Cl

 (a) NaOH is added (x M) (a) HCl is added (x M)

Acidic buffer Basic buffer

 Buffer range Requirement of good buffer

Case I Case II Case III Case IV

Case : (I) Hydrolysis of WA + SB :

CH3COO– + H+ Na+ + OH–

Case (II) : S. A. + W. B. (NH4OH)

Case (III) W. A. + W. B. (CH3COO NH4)

Case (II) :S. A. + W. B. (NH Cl 4  c, Kb)

Case (III) W. A. + W. B. (CH3COONH4  Ka, Kb , c)

[H ] [CH3 COO – ]  [CH3 COOH]

 Hydrolysis of salt of polyprotic acid / base (Na2 CO3)

 Solubility of sparingly soluble salt

Example (2) : Solubility of Ag2 CO3 Ag2 CO3(s) 2 Ag+ + CO 23–

 Ksp  [Ag ]2 [CO 32 – ] ,  In general , if salt is Mx Ny type, Mx Ny x My+ + y Nx–

 Case (2) : S (moL / L)  S (gm / L)

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