IONIC EQUILIBRIUM

According to strength ionic conductors are Acids, Bases and Salts:

of 2 types: Arrhenius concept:
1. Strong electrolyte: Those ionic Arrhenius Acid: Substance which gives H+ ion
conductors which are completely ionized in on dissolving in water (H+ donor)
aqueous solution are called as strong Ex. HNO3, HClO4, HCl, HI, HBr, H2SO4, H3PO4
electrolyte. etc. Ex:
Ex. Na+Cl–, K+Cl–, etc. H3BO3 is not Arrhenius acid.
(a) Strong acid: H2SO4, HCl, HNO3, Acid Conjugate Base Conjugate
Arrhenius base: Any substance which base acid
HClO4, H2SO5, HBr, HI. releases OH (hydroxyl) ion in water (OH ion
(b) Strong base: KOH, NaOH, Ba(OH)2 donor). HCl Cl NH3 NH4
CsOH, RbOH First group elements (except Li.) form strong
(c) All Salts: NaCl, CuSO4……… base H2SO4 HSO4 H2O H3O+
2. Weak electrolytes: Those electrolytes Bronsted-Lowery concept: (conjugate acid HSO4 SO24 RNH2 RNH3
which are partially ionized in aqueous – base concept) (Protonic concept)
solution are called as weak electrolytes. Acid: substances which donate H+ are H2O OH
For weak electrolytes the value of  is less Bronsted Lowery acids (H+ donor)
than one. LEWIS CONCEPT (electronic concept):
Base: substances which accept H+ are
Ex. Bronsted Lowery bases (H+ acceptor) An acid is a molecule/ion which can accept an
(a) Weak acid: HCN, CH3COOH, HCOOH, electron pair with the formation of a coordinate
Conjugate acid–base pairs: bond.
H2CO3, H3PO3, H3PO3, H3PO2, B(OH)3
In a typical acid base reaction Acid  e– pair acceptor
(b) Weak base: NH4OH, Cu(OH)2,
Zn(OH)2, Fe(OH)3, Al(OH)3 HX + B  X– + HB+

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Ex.
Electron deficient molecules : BF3, AlCl3
Cations + 2+
: H , Fe , Na +
Molecules with vacant orbitals : SF4, PF3
A base is any molecule/ion which has a lone
pair of electrons which can be donated.
Base  (One electron pair donor)
Ex. Molecules with lone pairs
: NH3’ PH3, H2O, CH3OH
Anions : OH, H–, –NH2
IONIC PRODUCT OF WATER
According to Arrhenius concept
H2O  H+ + OH
so, ionic product of water,
Kw = [H+][OH–]= 10–14 at 25 (exp.)
Dissociation of water is endothermic, so
increasing temperature Kw increases.
Kw increases with increase in temperature.
Now pH = –log[H+] = 7 and pOH = –log[OH] =
7 for water at 25 C (experimental)
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IONIC EQUILIBRIUM
So, pKa = pKa = pKb = – log (1.8 10–16)
pH  7  pOH  neutral = 16 – log 1.8 = 15.74

pH  7 or pOH  7  acidic  at 25 C ACIDITY AND pH SCALE :
pH  7 or pOH  7  Basic  Acidic strength means the tendency of an acid
Ionic product of water is always a constant to give H3O+ or H+ ions in water.
whatever has been dissolved in water since its So greater then tendency to give H+, more will
an equilibrium constant so will be dependent be the acidic strength of the substance.
only on temperature. Basic strength means the tendency of a base
Degree of dissociation of water: to give OH ions in water.
H2O  H+ + OH So greater the tendency to given OH ions, more
will be basic strength of the substance.
no. of moles disociated
 = The concentration of H+ ions is written in a
Total no.of moles initially taken
simplified from introduced by Sorenson known
10 7 as pH scale.
  18  10 10 or 1.8×10–7%[at 25 C] pH is defined as negative logarithm of
55.55
activity of H+ ions.
Absolute dissociation constant of water:
 pH = – log a H+ (where aH+ is the activity of
H2O  H+ + OH H+ ions)
H  OH  107  107 Activity of H+ ions is the concentration of free
Ka  Kb   H+ ions or H3O+ ions in a dilute solution.
H2O 55.55
=1.8×10–16
 IONIC EQUILIBRIUM
The pH scale was marked from 0 to 14 with So [H+] = normality of strong acid + H+ Ka 1
central point at 7 at 25 C taking water as ions coming from water in presence of [H+] = C = C  K a  C So pH =
solvent. this strong acid C 2
(pKa – logC)
If the temperature and the solvent are changed, (b) pH of a weak acid (monoprotic)
the pH range of the scale will also change. For Solution: on increasing the dilution  C  =   and
example [H+]   pH
 Weak acid does not dissociated 100 %
0 - 14 at 25 C (Kw = 10–14) therefore we have to calculate the (c) pH of a mixture of weak acid
percentage dissociation using Ka (monoprotic) and a strong acid
Neutral point, pH = 7
dissociation constant of the acid. solution:
–13
0 - 13 at 80 C (Kw = 10 )  We have to use Ostwald’s Dilution law  Weak acid and Strong acid both will
Neutral point, pH = 6.5 (as have been derived earlier) contribute H+ ion.
pH can also be negative or > 14 HA  H+ + A–  For the first approximation we can
neglect the H+ ions coming from the
pH Calculation of different Types of t=0 C 0 0 weak acid solution and calculate the
solutions:
teq C(1 – ) C C pH of the solution from the
(a) Strong acid solution: concentration of the strong acid only.
H   A   C 2
(i) If concentration is greater than 10–6 M. Ka    To calculate exact pH, we have to take
+
In this case H ions coming from water HA  1  the effect of presence of strong acid on
the dissociation equilibrium of the
can be neglected, so [H+] = normality If  << 1  (1 – )  1  Ka  C2 weak acid.
of strong acid solution.
 If the total [H+] from the acid is more
(ii) If concentration is less than 10–6 M In Ka
  (is valid if  < 0.1 or 10%) than 10–6 M, then contribution from the
this case H+ ions coming from water C water can be neglected,
cannot be neglected.  if not then we have to take [H+] from the
water also.
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 IONIC EQUILIBRIUM
Relative strength of weak acids and base: C2 2  C11  C2 2 Diprotic acid the one, which is capable of
K a2  giving 2 protons per molecule in water. Let
For two acids of equimolar concentrations. C2 1   2 
us taken a weak diprotic acid (H2A) in water
Strength of acid (I) K a1 (Since 1, 2 both are small in comparison whose concentration is c M.

Strength of acid (II) K a2 to unity) In an aqueous solution, following equilibria
K a1 = (C11 + C22)1 ; exist.
(d) pH of a mixture of t wo weak acid (bot h
If
monoprotic) solution: K a2 = (C11 + C22)2
1= degree of ionization of H2A in presence
 Both acids will dissociate partially.
K a1 1 of HA–
 Let the acid are HA1 & HA2 and their
  Ka1 = first ionisation constant of H2A
final concentrations are C1 & C2 K a2 2
respectively, then 2= degree of ionization of HA– in presence
[H+] = C11 + C22 of H2A
HA1  H+ + A1
C1K a1 C2 K a2 Ka1 = second ionisation constant of H2A
t=0 C1 0 0 = 
C1K a1  C2 K a2 C1K a1  C2 K a2 I step
At eq. C1(1 – 1) C11 + C22 C1 1
H2A + H2O  HA– + H3O+
C11  C11  C2  2   [H ]  C1K a1  C2 K a2
K a1  at eq. c(1 – 1) c1(1 – 2) (c1 + c1 2)
C1 1  1  If the dissociation constant of one of the
acid is very much greater than that of the H3 O  HA  
HA2  H+ + A 2 second acid then then contribution from the K  H O   H A 
eq 1 2  K a1
C2 0 0 second acid can be neglected. 2

C2 (1 – 2) C22 + C11 C22

(e) pH of a solution of a polyprotic weak  c1  c1 2  [c1 1   2 ]
acid:  K a1 
c 1  1 

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 IONIC EQUILIBRIUM

c1 1   2   1 1   2   Finally, for calculation of pH Salts are the ionic compounds formed when its
 …(i)  + –6
If the total [H3O ] < 10 M, the contribution positive part (Cation) come from a base and its
1  1 negative part (Anion) come from an acid.
of H3O+ from water should be added.
II step  If the total [H3O+] > 10–6 M, then [H3O+] Classification of salts:
HA– + H2O  A2– + H3O+ contribution from water can be ignored. (1) Simple salts
 Using this [H3O+], pH of the solution can be (2) Normal salt:
at eq. c1 (1 – 2) c12 (c1 + c1 2) calculated. (i) Acid salts (ii) Basic salts
Approximation: (3) Double salts
H3 O    A 2 
(Keq)2 [H2O]=   K a2 For diprotic acids, Ka2 << Ka1 and 2 would
(4) Complex salts
HA   (5) Mixed salts
be even smaller than 1
TYPES OF SALT HYDROLYSIS:
c1  c1 2  [c1 1   2 ]  1 – 2  1 and 1 + 2  1
(1) Hydrolysis of strong acid – weak base
Ka2 = K a2  Thus, equation (i) can be reduced to
c 1   2  [SA – WB] type salt–
C1  1 Ex. CaSO4, NH4Cl, (NH4)2SO4, Ca(NO3)2,
c1 1   2    2 K a1 
1  1 ZnCl2’ CuCl2’ CaCl2
= …(ii)
1  2 NH4Cl + H2O  NH4OH + HCl
This is expression similar to the expression
Knowing the values of Ka1, Ka2 and c, the for a weak monoprotic acid. NH4+ + Cl– + H2O  NH4OH + H+ Cl–
values of 1 and 2 can be calculated using Hence, for a diprotic acid (or a polyprotic
equations (i) and NH4  H2O  NH4 OH  H
acid) the [H3O+] can be calculated from its
(ii) After getting the values of 1 and 2, [H3O+] first equilibrium constant expression alone Summary:
can be calculated as provided Ka2 << Ka1
Kw Kh Kw
[H3O+]T = c1 + c1 + c12 SALTS (1) K h  (2) h 
Kb C Kb  C

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 IONIC EQUILIBRIUM

Kw  C K w  Ka (4) Hydrolysis of [SA – SB] type salt

(3) [H ]  Ch  (4) [H ] 
Kb C Ex. NaCl, BaCl2, Na2SO4, KClO4 etc.
(5) pH = –log [H+] (i) Hydrolysis of salt of [SA – SB] is not
(4) pH   log[H ] possible
1 1 (ii) Solution is neutral in nature (pH = pOH = 7)
1 1 pH  7  pK a  logC
pH  7  pK b  logC 2 2 (iii) pH of the solution is 7
2 2
(3) Hydrolysis of (WA – WB) type salt: BUFFER SOLUTIONS
(2) Hydrolysis of [WA – SB] type salt
Ex. NH4CN, CaCO3, (NH4)2CO3, ZnHPO3 A solution that resists change in pH value upon
Ex. KCN, NaCN, K2CO3, BaCO3, K3PO4 Summary: addition of small amount of strong acid or base
NaCN + H2O  NaOH + HCN (less than 1 %) or when solution is diluted is
Kw called buffer solution.
+ – + –
(1) K h 
Na + CN + H2O  Na + OH + HCN K a  Kb The capacity of a solution to resist alteration in
CN  H2 O  HCN  OH
  its pH value of is known as buffer capacity and
Kw
(2) h  K h  the mechanism of buffer solution is called
Summary: Ka  Kb buffer action.
Kw Types of buffer solutions
(1) K h  Kw  Ka
Ka (3) H    K a .h (A) Simple buffer solution
Kb
(B) Mixed buffer solution
Kh Kw
(2) h   (4) pH = – log [H+] SIMPLE BUFFER SOLUTION
C Ka  C
1 1 A Salt of weak acid and weak base in water e.g.
pH = 7 + pk a  pK b
Kw  C 2 2 CH3COONH4, HCOONH4, AgCN, NH4CN.
(3) [OH ]  Ch 
Ka

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 IONIC EQUILIBRIUM
Buffer action of simple buffer solution The best known example is a mixture of Solubility product (Ksp) is a type of equilibrium
NH4OH and NH4Cl. constant, so will be dependent only on
1 1 temperature for a particular salt.
pH  7  pk a  pk b Condition for maximum buffer action:
2 2
Simple solubility
MIXED BUFFER SOLUTIONS
NH4 OH : [NH4Cl]
Let the slat is AxBy, in solution in water, let the
(a) Acidic buffer solution: 1 1 solubility in H2O = ‘s’ M, then
 A   1 AxBy  xAy+ + yB–x
pH  pK a  log pOH = pKb + log
HA  1 – xs ys
pOH = pKb and pH = 14 – pKb
Salt   Ksp = (xs) (ys) = xx, yy. (s)x+y
x y
pH  pK a  log Solubility (s) and Solubility Product (ksp):
 Acid Condition of precipitation
This is generally used for sparingly soluble For precipitation ionic product [IP] should be
(b) Basic buffer solution: salts. We will be dealing with the solubilities in greater than solubility product ksp.
A basic buffer solution consists of a mixture the following type of solution.
of a weak base and its salt with strong acid.

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