► Le Chatelier principle
, Ways of shifting the chemical equilibrium
Chemical Equilibrium
□ It is a fact that many reactions do not go to completion, but proceed to a certain
point and then apparently stop. Then we say tha,t it has reached the equilibrium.
For example:
H2 + 12 ~ 2HI
3Fe + 4H 20 ~ Fe 30 4 + 4H 2
□ Effect of insolubility or volatility:
, A reaction often appears to go to completion instead of going to a state of
equilibrium.
For example:
BaCl 2 + H2 SO4 ~ BaSO 4 t + 2 HCI (Sulfate determination)
NaCl + H2S0 4 ~ NaHS0 4 + HCI t (Lab. method of HCI preparation)
CaCO3 ~ Cao + CO2
(closed vessel???) or (current of air???)
-
Chemical Equilibrium
□ Le Chatelier principle:
If one of the conditions of a system in equilibrium be altered, the system will adjust
itself in such a direction as partially to neutralise the change in condition.
U For example the well known Haber process of ammonia preparation from N1 and H2
N2 + 3H 2 ~ 2NH 3 + 22,000 cal
(i) Effect of temperature on equilibrium:
If the temperature is increased what will happen ????
(ii) Effect of pressure on equilibrium:
If the pressure is increased what will happen ????
(iii) Effect of altering concentration on equilibrium:
NaCl + H2 S04 ~ NaHS0 4 + HCI
(iv) Effect of adding a substance to a system in equilibrium:
PCl 5 ~ PCl 3 + Cl 2
Che n1 i ca I Eq u i I i b r i u tn
r Solubility product
► Solubility
□ Solubility Product:
, All solids, even if they are insoluble, are soluble to some extent. For example, AgCI
and BaSO 4 is considered to be very insoluble. But in contact with water they
dissolve slightly, and establish the following equilibria:
AgCl(s) ~ Ag• (aq) + Cl· (aq) -----------(1)
BaSO 4 (s) += Ba 2• (aq) + sO 4 • 2 (aq) ----------(2)
The equilibrium that exists for reaction (1) can be expressed as:
K = [Ag• (aq)] (Cl· (aq)] / [AgCI (s)]
K,p= [Ag+ {aq)) (cl· (aq))
Ksp is called solubility product or solubility product constant
It is a constant at a particular temperature. In almost all text books or hand books
dealing with qualitative and quantitative analysis the solubility product values are
available. In a similar way for a complex salt such as Ca 3 (P0 4 }z we can write
Ca 3 (P0 4 )z ~ 3Ca 2 .. + 2P0 4 •3
_ _ _ _Ksa = [Ca 2•p X (P04·3 )2
- - ~ - - - - - - - -
D Solubility
BaSO4 (s) ~ Ba 2+ (aq) + SO 4•2 (aq)
If S represents the solubility of BaSO4, then
S =[Ba 2• ] =[SO4•2 ]
Ksp =S x S =lx10-10
Therefore, S = lx10-5 = Solubility of BaSO4
Similarly for Caf 2
Caf 2 ~ Ca 2+ + 2f·
Ksp = [Ca 2• ] x [F·)2
If S is the solubility of CaF 2, then So it can be said that calcium
fluoride is 20 times more
[Ca 2• ] =S; [f·] =2S soluble than barium sulfate
Ksp = (S) X (25) 2 = 4S3 =3 x 10·11
S = 1.96 X 10-4 = 19.§ X 10·5
□ Understanding of phenomenon of precipitation
1. In an unsaturated solution:
For a species AB
[A•] [B·] < K,p
,. If undissolved AB is present, it will dissolve until [A+] [B·] = K,p
2. In a supersaturated solution:
For a species AB
[A+] [B·] > K,p
,. Nothing will happen until some crystals of AB are introduced in to the solution or
some internal forces allow formation of crystal nuclei
► Then precipitation will occur until the situation becomes
[A+] [B·] = Ksp
• ,
