M.

PRAKASH ACADEMY

IONIC EQUILIBRIUM

IONIC EQUILIBRIUM 1
 IONIC EQUILIBRIUM
ACIDS AND BASES
Chemical substances are classified by Robert Boyle into three types namely acids,
bases and salts.
Robert boyle’s classification explains the characteristic properties of the substances
One of the earlier theories of acids and bases is Arrhenius theory.
Arrhenius theory could explain the acid & base definitions only in aqueous solutions
ARRHENIUS CONCEPT :
An acid is a substance that dissociates to give hydrogen ions when dissolved in
water
eg. HCl , CH 3COOH , H 3 PO4 A base is a
substance that dissociates to give hydroxyl ions when dissolved in water
eg. NaOH , Ca  OH 2
INGOLD CONCEPT :
All electrophiles are acids and nucleophiles are bases .
Hydroniumand HydroxylIons
Hydrogen ion by itself is a bare proton with very smallsize (  10-15m radius) and
intense electric field,binds itself with the water moleculeat one of the two available
lone pairs onit givingn H3O+. This species has been detected in many compounds
(e.g.,H3O+Cl-) in the solid state..In aqueous solution the hydronium ion is further
hydrated to give species like H5O2+,H7O3+and H9O4+. Similarly the hydroxyl ion is
hydrated to give several ionic species like H3O2-,H5O3- and H7O4-etc.
H9 O 4 +

BRONSTED - LOWRY THEORY OF ACIDS & BASES

A substance or a chemical species which can donate proton is known as an acid.ie.
a proton donar is an acid.
A substance or a chemical species which can accept proton is known as a base. ie. a
proton acceptor is a base.
Acid - base reactions are reversible. In the reaction.
HCl  H 2 O  H3 O  Cl

HCl and H3 O are Bronsted - Lowry acids.

IONIC EQUILIBRIUM 2
H2O and Cl are Bronsted - Lowry bases.In the reaction
NH3  H 2 O  NH 4  OH

H2O and NH 4 are Bronsted - Lowry acids.

NH3 and OH  are Bronsted - Lowry Bases.
The transfer of proton from an acid to the base is known as neutralization (or)
protolysis
A pair of acid-base which differ by a single proton is known as a conjugate acid-
base pair.
The removal of a proton from a Bronsted-Lowry Acid gives its conjugate base
Eg: The conjugate base of HCl is Cl
The conjugate base of H2SO4 is HSO 4
The conjugate base of H3O+ is H2O
The conjugate base of H 2PO4 is HPO2 4

The addition of proton to a Bronsted-Lowry base gives its conjugate acid.

Eg: The conjugate acid of NH3 is NH 4
The conjugate acid of PO34 is HPO4-2
The conjugate acid of OH  is H2O
The conjugate acid of H2O is H3O+
The conjugate base of strong acid is a weak base
Eg: HCl is a strong acid so Cl is a weak base.
HNO3 is a strong acid so NO 3 is a weak base.
The conjugate base ofa weak acid is a strong base
Eg: CH3COOH is a weak acid so CH 3COO  is a strong base
The conjugate acid of strong base is a weak acid
Eg: i.OH- is a strong base so H2O is a weak acid
ii. NH3 is a strong base so NH4+ is a weak acid.
The conjugate acid of weak base is a strong acid
Eg: i. C6H5NH2 is a weak base so C6 H 5 NH3 is a strong acid.
ii.C2H5OH is a weak base so C2H5OH2+ is a strong acid.
An acid base reaction contains two conjugate acid - base pairs
Ex: The conjugate acid - base pairs in the reaction
HCl  H 2 O  H3 O  Cl are HCl & Cl and H 3O & H 2 O

IONIC EQUILIBRIUM 3
 An acid which shows a greater tendency to donate protons is a strong acid
An acid which shows a less tendency to donate protons is a weak acid .
A base which shows greater tendency to accept protons is a strong base
A base which shows less tendency to accept protons is a weak base
LEVELLING EFFECT
Water levels all strong acids to the strength of H3O+ ion and all strong bases to
the strength of OH  ions.
Water is not a suitable solvent to determine the relative strengths of acids and
bases.
A solvent having low levelling effect must be used to determine the relative strengths
of acids and bases.
The relative strengths of different acids can be determined in glacial acetic acid
The relative strengths of different bases can be determined in ammonia.
A weak acid will have more levelling effect than water towards different bases.
A weak base will have more levelling effect than water towards different acids.
Generally glacial acetic acid or anhydrous hydrofluoric acid is used as the
differentiating solvent to determine the relative strengths of various acids.
The relative strengths of various acids in glacial acetic acid are
HClO 4  Hl  HBr  H 2SO 4  HCl  HNO 3  H 3PO 4
The order of acidic strength is
HClO4 > H 2 SO4 > HCl > HNO3 > HSO4 > HF > HNO2  CH 3COOH  H 2 CO3  H 2 S  HCN
 NH 4  H 2O  NH 3  OH   H 2  CH 4
Therefore the order of strength of their conjugate bases is
CIO4  HSO4  CI   NO3  H 2O  SO42   F   NO2  CH 3COO   HCO3  HS 
 CN   NH 3  OH   NH 2  O 2   H   CH 3
TYPES OF BRONSTED - LOWRY ACIDS :
n Molecular Acids: HCl, H2SO4, HNO3, HClO4, CH3COOH, HCOOH, H2S, HCN
n Cationic acids: NH4+, H3O+, N2H5+, C6 H 5 NH 3
n Anionic Acids : HSO 4 , H 2 PO 4 , HPO 24 
TYPES OF BRONSTED LOWRY BASES
Molecular Bases: NH3, H2O, C2H5OH, N2H4, C6H5NH2
Cationic Bases: [Al(H2O)5OH]++,[Cu(H2O)3OH]+,
Anionic Bases: HSO4 , NO3 ,Cl ,

IONIC EQUILIBRIUM 4
 Basicity (or) protocity of Bronsted acid is the number of H  ions given by a molecule
/ion
Ex: Basicity of HCl  1
Basicity of H2SO4  2
Basicity of H3 PO3  2
Basicity of H3 PO4  3
Acidity (or) hydroxicity of Bronsted base is the number of OH  ions given by a
molecule / ion
Ex: Acidity of NaOH  1
Acidity of Ca  OH 2  2

Acidity of Al  OH 3  3
Bronsted acid functions as an acid only in the presence of proton acceptor (base)
Ex : HCl functions as an acid in water but not in benzene as it can not accept
protons.
Bronsted base functions as a base only in the presence of proton donor (acid)
The compound which acts as a proton donor as well as proton acceptor is called
amphoteric (or) amphiprotic substance. Ex : H 2O, NH 3 ,....
Bronsted - Lowry theory explains the behaviour of acids and bases in both aqueous
and non aqueous solutions.
DRAWBACKS:
1. Proton donation (or) acceptance happens only in the presence of other substances.
2. Bronsted-Lowry theory could not explain the acidic nature of electron deficient
compounds like AlCl3, BCl3, etc.,
SOLVENTS
On the basis of proton interaction, solvents are of four types
1) Protophilic solvents: Solvents which have greater tendency to accept protons
Ex:- Water, alcohol, liquid Ammonia etc.
2) Protogenic solvents: Solvents which have the tendency to produce protons
Ex:- Water, liquid hydrogen chloride; glacial acetic acid. etc
3) Amphiprotic solvents:- Solvents which act both as protophilic (or) protogenic
Ex:- Water, Ammonia, ethyl alcohol etc
4) Aprotic solvents: Solvents which neither donate nor accept protons
Ex:- Benzene, carbon tetrachloride, carbon disulphide etc.

IONIC EQUILIBRIUM 5
LEWIS THEORY OF ACIDS AND BASES
A substance or a chemical species, that can accept a pair of electrons to from a co-
ordinate covalent bond is known as Lewis acid
A substance or a chemical species that can donate a pair of electrons to form a
dative bond is known as Lewis base.
L ew i s aci d i s an electron pair acceptor.
Lewis base is an electron pair donor.
Lewis acid contains a vacant orbital.
Lewis base contains a lone pair of electrons (or non-bonded pair of electrons)
TYPES OF LEWIS ACIDS
Atoms which contain electron sextet (i.e. 6 electrons) in their valency shell. Eg. O, S,
Se, Te etc.
Molecules in which octet is not complete in the valency shell of central atom.
Eg. BCl3, AlCl3, BF3, BeF2, FeCl3 etc.
Molecules in which central atom can expand its octet using vacant d-orbitals present
in its valency shell. Ex: SiF4 ,SnCl4 ,SF4 , TeF4 , FeCl3 ,........
Molecules having multiple bonds other than carbon-carbon multiple bonds.
Eg. CO2, SO2, SO3, NO2,Cl2O7, P4O10
All simple cations and carbonium ions
 
H+, Ag+, Co3 , C H 3 CH3 C H 2 , Fe3+, Cu2+,Ni2+, Fe2+, Al3+, Na+
In organic chemistry Lewis acids are called ELECTROPHILES. Electrophile means
electron seeking species (or) electron deficient species.
TYPES OF LEWIS BASES :
i) Molecules having one or more lone pairs of electrons on the central atom, available
.. .. .. .. .. .. ..
for the donation to form a dative bond. H2 O, ..
N H3 , R O H, R 2 O, R 2 S, R N H 2 , R OR. ii) All
.. .. .. ..
anions: Cl-, F-, OH-, CN-, SCN-, NH2-
iii) Carbanions : CH 3 , CH3CH 2
iv) Molecules having carbon-carbon multiple bonds or molecules with multiple bonds
CO, NO C2H2, C2H4……etc
In complex compounds all ligands are Lewis bases.
In organic chemistry Lewis bases are called NUCLEOPHILES. Nucleophile means
nucleus seeking species or election rich species.
According to Lewis theory, the formation of co-ordinate covalent bond is known as
Neutralization process. H3 N :  H    H3 N  H  

IONIC EQUILIBRIUM 6
 DRAWBACKS:
1. According to Lewis Theory, neutralization reaction (formation of dative bond)
occurs slowly. But it is a well known fact that the Acid Base neutralization reactions
occur quickly.
2. Acids like HCl, H2SO4 react with bases such as NaOH (or) KOH but do not form
co-ordinate covalent bond. All the acid-base reactions do not involve co-ordinate
bond formation.
3. Lewis theory could not explain the strength of acids and bases.
4. Lewis theory could not explain the catalytic activity of H+ ion.
All Lewis Bases are Bronsted-Lowry bases and similarly all Bronsted-Lowry bases
are Lewis Bases.
All Lewis acids are not Bronsted-Lowry Acids and similarly all Bronsted-Lowry
acids are not Lewis acids.
Pure water is a poor conductor of electricity.
 Pure water ionises to a very small extent .
HARD AND SOFT PRINCIPLE OF ACIDS AND BASES:
Lewis acids and bases are classified as hard and soft acids and bases.
Hardness is defined as the property of retaining valence electrons very strongly.
Thus a hard acid is that in which electron-accepting atom is small has a high
positive charge and has no electron which can be easily polarised (or) removed
Ex: Li+,Na+,Be+2,Mg+2,Al3+,BF3.SO3 etc
A soft acid is that in which the acceptor atom is large, carries a low positive
charge (or) it has electrons in orbitals which are easily polarised (or) distorted
Ex: Pb+2,Cd+2,Pt+2,Hg+2,RO+,RS+, I2 etc
A lewis base which holds its electrons strongly is called hard base
Ex:- OH-,F-,H2O,NH3,CH3-O-CH3 etc
A lewis base in which the position of electrons is easily polarised (or) removed
is called a soft base
Ex:- I-,CO,CH3S-,(CH3)3 Petc
In general hard acids preper to bind hard bases; soft acids preper to bind to soft
bases.
The bonding between hard acids and hard bases is chiefly ionic and between
soft bases and soft acids is mainly covalent.

IONIC EQUILIBRIUM 7
Degree of Ionisation (Dissociation) : The fraction of total number of molecules of
an electrolyte which dissociate in to ions.
No.ofmoleculesdissociated int oions

Tota ln o.ofmoleculesofelectrolyte
%ofdissociation

100
OSTWALD`S DILUTION LAW: Degree of ionisation or dissociation (  ) of weak
electrolytes increases with dilution and law of mass action can be applied to them.
AB  A++B-
c 0 0 (initial conc) c(1-  )c  c  equilibrium conc. ionisation constant
K=c  2

K 1
Therefore  = , 
C C
Concentration of A+ or B- =C  ,  approaches unity at infinite dilution.
DEGREE OF IONISATION
Degree of ionisation (  ) = number of dissociated molecules / Total number of
molecules of electrolyte before dissociation
1 1
(  )  con`c`of solution , (  )  wt of solution
Degree of ionisation of an electrolyte in solution increases with rise in temp.
FACTORS AFFECTING IONISATION OR DISSOIATION:
1. Nature of electrolyte: Stronger the electrolyte, more is the ionisation and vice
versa.
2. Nature of Solvent: Greater the dielectric constnat of solvent, more is the
ionisation
3. Concentration: Lesser the concentration, greater is the ionisation
4. Temperature: The higher the temperature, the more is the ionisation
5. Solvation: Greater the solvation, more is the ionisation
6.Presence of the ions in the solution: Ionisation decreases in presence of
common ions.
ELECTROLYTE: A substance which splits into ions in solution. It can be an acid,
base or a salt
(i) Strong electrolyte: Which dissociates almost completely into ions even in
concentrated solution
Ex: NaOH,KOH,HCl,H2SO4,NaCl,CaCl2
(ii) Weak electrolyte: Which dissociates to a small extent into ions in solution
eg.CH3COOH,NH4OH etc.

IONIC EQUILIBRIUM 8
 COMMON ION EFFECT :-
The suppression of the dissociation of a weak electrolyte by the addition of strong
electrolyte having common ion is called common ion effect.
Ex : - A solution of Sodium Aectate is added to solution of Acetic acid as a result in
the decrease in ionization of acetic acid due to common ion is  CH 3COO 


CH COOH 
 CH COO  H 
3 3

 CH COO  Na
CH COONa 
3 3
common ions
3. According to Lechatlier principle,  H   decreases P H is increases and equilibrium
shifts to left handside.
APPLICATIONS : -
1) It is used in the controlling the H  ion concentration in Buffer solution.
2) The concentration of S 2 in the II Group or OH  in III group of qualitative Analysis
is controlled by HCl and NH 4OH on the basis of common ion effect.
3) Common ion effect is also used in the purification of common salt by passing dry
HCl gas into impure salt solution.
OPPOSITE ION EFFECT :-
TTThe degree of ionisation of weak electrolyte increases when a strong electrolyte
is added so as to form a water molecule in this reaction.
E g : N aO H to H 2S, HCl to NH4OH.
Relative strgths of Acids & Bases :
(i) Compairing dissociation constant :
Relative Strengths of acids :For weak acid K a  C 2 . For two acids with
dissociation constants Ka1 and Ka2 at the same concentration C1
1 Ka1 Strength of acid HA1

2 Ka2 = Strength of acid HA2

Relative Strengths of bases : For weak base K b  C 2 . For two bases with
dissociation constants K b and K b at the same concentration C.
1 2

1 Kb1 Strength of base B1OH

 
2 Kb2 Strengthof base B2OH

IONIC EQUILIBRIUM 9
(ii) Conductivity method :
c
 

1c
For acid A1 ; 1  1

2c
For acid A2 ;  2   
2

At infinite dilution for weak electrolyte 1 = 2

StregthofA1 1 1c k1 x1000 / C k1
    
StregthofA2  2 2c k2 x1000 / C k2
k1 & k2 = specific conductivity.
(iii) Thomson Thermal Method :
In this method, heat of neutralisation of two acids is first determined separately
with NaOH. Let it be 'x' and 'y' calorie. The one gram equivalent of each of the
two acids is mixed and one gram equivalent of NaOH is added. Let the heat
evolved in this case be 'z' calorie. The two acids will neutralise a fraction of the
base proportional to their relative strength.
Suppose n gram equivalent of NaOH is neutralised by acid I and the rest
(1 - n) by acid II.
Total Heat solved, z = nx + (1-n)y = nx + y - ny
or z-y = n(x-y)
or n = (z-y)/(x-y)

StrengthA1 n ( z  y) / ( x  y) ( z  y)
  
StrengthA2 1  n 1  [( z  y ) / ( x  y )] xz
The relative strengths of some of the acids are as follows:
HCIO4 > HBr > HC1 > HNO3 > H2SO4 > H3O+ > H2SO3 >
H2CO3>CH3COOH
HCIO4 > HCl03 > HClO2 > HCIO
HI > HBr > HCl > HF
HClO3 > HBrO3 > HIO3
CCI3COOH > CHCl2COOH > CH2C1COOH > CH3COOH
HCOOH > CH3COOH > C2H5COOH

IONIC EQUILIBRIUM 10
 The relative strengths of some of the bases are as follows:

KOH > NaOH > Ca(OH)2 > NH4OH

(CH3)2NH > CH3NH2 > (CH3)3N > NH3
(C2H5)2NH > C2H5NH2 > NH3 > (C2H5)3N
NaOH>NH3>H20
NH3 > NH2NH2 > NH2OH
NH3 > C5H5N > C6H5NH2
IONIC PRODUCT OF WATER  K W 
The purest form of water also contains a very few H+ or H3O+ and OH ions in it.
This is due to the self ionisation of water.
H 2 O  H   OH 
H 2 O  H 2 O  H 3O   OH 
The product of the concentration of hydrogen ions (or) hydronium ions and hydroxide
ions at any temperature in pure water or in any aqueous solution is known as the
ionic product of water. It is represented by Kw
Kw =[H+][OH-]
Kw = [H3O+][OH-]
P Kw   log K w

The value of Kw depends only on temperature.

As the temperature increases the ionization of water increases and hence Kw value
increases.
At 250C, the value of
(1) Kw is 1.0 x 10-14 moles2/lit2
Kw  1.008 1014 moles 2 / lit 2 at 250 c

(2) Pkw   log K W  14

If temperature increases  H   increases and OH   increases
In pure water or in neutral aqueous solutions
[H+] = [H3O+]= OH  
In aqueous solutions of acids
[H+]> OH  
In aqueous solutions of bases
[H+]< OH  

IONIC EQUILIBRIUM 11
 At 250C, in pure water or in neutral aqueous solutions.
[H+]= OH   = 1 x 10-7 moles/lit
In aqueous solutions of acids
[H+]> 1 x 10-7 M, OH   < 1 x 10-7M

In aqueous solutions of bases

[H+]< 1 x 10-7 M, OH   > 1 x 10-7M
Temperature (°C) Value of Kw
0 0.11 x 10-14

10 0.31 x 10-14

25 1.00 x 10-14

100 7.50 x 10-14

PH SCALE :
The PH scale was introduced by S.P.L Sorenson.
PH Scale is used to express the acidity of only dilute solutions.
The negative logarithm of the hydrogen ion concentration (expressed in moles/lit) of
an aqueous solution is known as the pH of the solution.
i. PH = -log [H+]
1
ii. PH  log  H  
 
H

 H   10
 P
iii.

Just like the PH value,quantities like POH ,P K W ,P Ka ,PK b ,PK In can be defined.
POH = -log [OH-]
P KW =-log Kw
P K a = -log Ka
PKb = -log Kb
For any aqueous solution, the sum of P H and P OH depends on the ionic product of
water.
P H + P OH = P KW

IONIC EQUILIBRIUM 12
At 25o C, for any aqueous solution. PH+POH=14
At 250C,the pH scale lies between 0 to14
For pure water or neutral solution PH= POH =7.
For the aqueous solution of an acid pH value is between 0 to7.
For the aqueous solution of a base pH value is between 7 to14.
For a strong acid pH value is very low.
For a strong base pH value is very high.
If the aqueous solution of an acid is diluted with water its pH value increases. After
dilution, P H =initialP H +log V2 / V1
Where V1 = initial volume of the solution.
V2 = volume of solution after dilution.
If the aqueous solution of a base is diluted, with water its pH value decreases. After
dilution.
PH=initial PH - log V2 / V1
V1 = initial volume of the solution.
V2 = volume of solution after dilution.
Whatever the volume of water added, the pH of acid is always less than 7 and base
is always more than 7
If a very dilute acid is added to a concentrated acid the very dilute acid is treated as
water for the purpose of calculating the pH value of the mixture.
If a very dilute base is added to a concentrated base, the very dilute base is treated as
water for the purpose of calculating the pH value of the mixture.
If the aqueous solution of an acid is diluted by
Ten times, the pH of the solution increases by one unit.
Hundred times, the pH of the solution increases by two units.
Thousand times, the pH of the solution increases by three units.
If the aqueous solution of a base is diluted by ten times, the pH of the solution
decreases by one unit.
Hundred times, the pH of the solution decreases by two units.
Thousand times, the pH of the solution decreases by three units.
For any strong acid.
[H+] = normality of the solution
[H+] = molarity of the acid  basicity of the acid.
For any strong base.
 OH  = normality of the solution.

 OH  = molarity of the base  Acidity of the base

IONIC EQUILIBRIUM 13
If two strong acids are mixed
N1V1  N 2 V2
[H+] = V1  V2
If two strong bases are mixed
N1V1  N 2 V2
OH   =
V1  V2
If excess of strong acid is added to limited quantity of strong base.
N a Va  N b Vb
[H + ] = Va  Vb
If a excess of strong base is added to limited quantity of strong acid
N b Vb  N a Va
OH   =
Va  Vb

PH OF SOME MATERIALS
Material pH Material pH
Saturated solution of NaOH -15 limewater 10.5
Milk of magnasia 10 Gastric juice 1.2
rain water 6.5 Leman juice 2.2
pure water 7.0 Vinegar 2.9
Human saliva 6.4 Soft drinks 3.0
Blood plasma 7.4 Beer 4.5
Tears 7.4 Black coffee 5.0
Egg 7.8 Milk 6.8
Household ammonia 11.9

IONIC EQUILIBRIUM 14
 Chemistry of strong acids & strong bases
PH of exterimely dilute (  106 M ) solution of strong acids &strong bases:
Method-I: (Incorrect method) Let HA  107 M

HA  H   A ,[ H  ]  107  10 7
H 2O  H   OH  ,[ H  ]  10 7  10 7
[ H  ]Total  [ H  ]HA  [ H  ]H2O
[ H  ]Total  2 x10 7 M
 P H   log 2  log107  0.3011  7  6.6989

in this case by adiing HA  107 M to water the conc. of [ H  ] increases , which

makes the reaction to go in the reverse direction, therefore the [ H  ] from water
would become less than 107 M . So, this method gives incorrect result.
Method-II: (Correct method) Let HA  107 M
2H 2O  H 3O   OH 
x x
HCl  H 2 O  H 3O   Cl 
107 107

[ H  ]Total  (107  x) M
Atequi,[ H 3O  ][OH  ]  KW  1014
(10 7  x) x  1014  x 2  107  1014  0
b  b 2  4ac
x 
2a
[OH ]  x  0.618 X 107 M


[ H  ]Total  (0.618 X 107  10 7 ) M

OR,[ H  ]Total  6.18 X 107 M
P H  6.7910

Thus , it is concluded that [ H 3O  ] from water is cosidered only if [ H 3O  ] from

acid is  107 M & if [ H 3O  ] from acid  106 M , [ H 3O  ] from acid is ignored.
P-1: Calculte PH of the following :
a.108 MHCl , ( Ans  PH  6.98)
b.5 x108 MHCl , ( Ans  PH  6.89)
c.5 x108 MHCl , ( Ans  PH  7.00)

IONIC EQUILIBRIUM 15
SOLUTION-C:HCl is so dilute thatits coc. to [ H 3O  ] is negligible as compared whith
the ionization of water.Thus, [ H 3O  ] = 107 M & PH = 7.00.

d .102 MHCl , ( Ans  PH  2)

e.107 MNaOH ,( Ans  PH  7.209)
f .108 MNaOH , ( Ans  PH  7.209)
g.102 MHCl , ( Ans  PH  2)

SOLUTION-G: A negative PH only means that the [ H 3O  ] > 1M. However, in actual
practice, a negative PH is uncommon. Even S.A. (say 100% sulphuric acid)
become partially dissociated at high conc.
according to Sorenson, PH is related to thermodynamic activities rather than
 
[ H 3O  ] . aH   [ H ] fH , where fH  = Activity coefficient.
For dilute solution fH  is near enough to unity..
For conc. solution fH  is less than unity..
 P H   log aH  , i.e. PH of 102 MHCl can not be calculated until fH  is known.
There is no basis for not having negative PH.
h.10 2 MNaOH , ( Ans  PH  12)
i.102 MNaOH , ( Ans  PH  16)
SOLUTION-I: PH >12 only means that the [OH  ] >1 M. So, PH scale become in
between 2 to 16.
j. Calculate the % error in the [ H 3O  ] made by neglecting the ionisation of water
in 106 MNaOH solution.
SOLUTIN-H: (a) Neglecting the ionisation of water:
[OH  ]  10 6 M &[ H 3O  ]  10 8 M  PH  8
(b) Including the ionisation of water :
[OH  ]  ( x  106 ) M &[ H 3O  ]  xM
( x  106 ) x  1014 , x  9.9 x10 9 M
108  9.9 x10 9
 % Error  x100  1%
9.9 x109
NOTE:
log 2  0.3010  0.3, log 3  0.4771  0.48
log 5  0.6990  0.7, log 7  0.8451  0.85
2  1.414, 3  1.372, 5  2.236, 6  2.449
7  2.646, 8  2.828, 10  3.162
IONIC EQUILIBRIUM 16
P-2: Calculte PH of the following :
(a) 100 ml of 0.1 M HCl + 100 ml of 0.2 M H 2 SO4 + 100 ml of 0.1 M HNO3 and
700 ml of H 2O . ( Ans  PH  1.22)
(b) 100 ml of 0.1 M NaOH + 200 ml of 0.1 N Ca (OH )2 + 200 ml of 0.1 M KOH
and 500 ml of H 2O . ( Ans  PH  12.7)
(c) 100 ml of 0.1 M HCl + 300 ml of 0.2 M H 2 SO4 + 100 ml of 0.3 M Ba (OH )2
and 500 ml of H 2O . ( Ans  PH  2.0)
(d) 8g NaOH + 680 ml of 1.00 M HCl + 10 ml of H 2 SO4 (sp.gr = 1.2, 49% by mass)
The total volume of the solution was made to 1 lit with water. ( Ans  PH  0.22)
(e) 37 g of Ca (OH )2 + 360 ml of 1 M HCl + 10 ml of H 2 SO4 (sp.gr = 1.4, 49% by
mass). The total volume of the solution was made to 1 lit with water.
( Ans  PH  13.7)
Calculate the amount of SA & SB using PH:
(1) If
PH  7,[ H  ]  Normalityofacid
 Stregth( gperlit )  NxEquivalentMass
OR
Stregth( gperlit )  MxMolecularMass
(2) If
PH  7,[OH  ]  NormalityofBase
 Stregth( gperlit )  NxEquivalentMass
OR
Stregth( gperlit )  MxMolecularMass

P-1: What amount of H 2 SO4 must be dissolved in 500 ml of solution to have a PH of

2.15? (Ans = 0.1715g/500ml)
P-2: What amount of Ca (OH )2 must be dissolved in 100 ml of solution to have a PH
of 13.85? (Ans = 2.59g/100ml)
Calculate PH & conc. of [ H  ] or [OH  ] . When equal volume of 2 or 3
solutions of known PH are mixed:
(1) Equal volume of two solutions with PH = 2 and 3 are mixed. Find final PH.
Solution:
V1  V2 , PH  2,[ H  ]  102 N
PH  3,[ H  ]  103 N

IONIC EQUILIBRIUM 17
 102  103
[ H  ]Final   1.1X 10 2  0.55 X 10 2  55 X 10 4 N
2
 PH   log 55 X 10 4  1.74  4  2.26
Alternative approximation methos :
When the difference in two PH is one. Take average PH and subtract 0.24 to get
the final exact PH.
23
App.finel PH   2.5
2
Actual final PH  2.5  0.24  2.26 .
(2) Equal volume of two solutions with PH = 3 and 4 are mixed. Find final PH.
(Ans = 3.26)
(3) Equal volume of three solutions with PH = 1,2 and 3 are mixed. Find final PH.
(Ans = 1.44)
(4) Equal volume of three solutions with PH = 2,3 and 4 are mixed. Find final PH.
(Ans = 2.44)
NOTE: (1) When the difference in two PH is one, take the average PH & subtract
0.24 to get exact final PH.
(2) When the difference in three PH is one, take the average PH & subtract 0.56
to get exact final PH.
(3) The two PH values do not differ by one unit, so calculate the PH directly.
Chemistry of weak acids & weak bases

IONISATION OF ACIDS AND BASES AND DEGREE OF IONISATION

Acids which donate protons are generally known as protonic acids. These are
represented as HX
The compounds which contain OH- ions are generally known as bases and represented
by BOH
When acids are dissolved in water, they ionised into H+ and X-
HX  H O
2
 H +X
+ -

When bases are dissolved in water they ionised into B+ and OH-
BOH-  H O2
 B+ OH 
This process in known as ionisation same time referred to as dissociation
The extent of hydrolysis is more for strong acids and strong bases ( 100% ionisation)
The extent of hydrolysis is less for weak acids and weak bases

IONIC EQUILIBRIUM 18
The process of ionisation is an equilibrium process

HX 
H O
 H ++ X- ---------(1)
2


BOH   B++OH--------(2)

H 2O

The dissociation constant of acid

[ H  ][ X  ]
Ka = (based on the equation(1))
[ HX ]
The dissociation constant of base or base ionisation constant
[ B  ][OH  ]
Kb = (based on the equation(2))
[ BOH ]
For any weak acid:

 H+ + X-
HX 

C( 1-  ) C C
C2 2
Ka=
C(1   )
1. Ka  C 2
2.   Ka / C
3.  H    C
 H    Ka  C
4.  
1 1
5. P  2 P  2 log C
H Ka

 = degree of ionization of acid

C = molar concentration of acid
Ka = ionisation constant of acid
For any weak base:

1. K b  C
2

  Kb / C
2.
3. OH  C
 OH   K b  C
4.  
1 1
5. POH  P  log C
K b

2 2
6. P H  14  P OH
IONIC EQUILIBRIUM 19
 = degree of ionisation of base
C = molar concentration of base
Kb = ionisation constant of base
KA - VALUES (THE IONIZATION CONSTANTS OF SOME SELECTED
WEAK ACIDS (AT 298K)
Acid Ionization Constant
Ka
-4
Hydrofluoric Acid (HF) 3.5x 10
-4
Nitrous Acid (HNO2) 4.5 x 10
-4
Formic Acid (HCOOH) 1.8x 10
-5
Niacin (C5H4NCOOH) 1.5 x 10
-
Acetic Acid (CH3COOH) 1.74 x 10
-5
Benzoic Acid (C6H5COOH) 6.5 x 10
-8
Hypochlorous Acid (HCiO) 3.0 x 10
-10
Hydrocyanic Acid (HCN) 4.9 x 10
-10
Phenol (C6H5OH) 1.3 x 10
Kb-Values ( The values of the ionization constant of some weak bases at 298K)
Base Kb
-4
Dimethylamine,(CH3)2NH 5.4 x 10
-5
Triethylamine (C2H5)3N 6.45 x 10
-5
Ammonia, NH3 or NH4OH 1.77x 10
-6
Quinine, ( A plant product) 1.10 x 10
-9
Pyridine, C5H5N 1.77 x 10
-10
Aniline, C6H5NH2 4.27 x 10
-14
Urea, CO(NH2)2 1.3 x 10
RELATION BETWEEN KA AND KB
Ka and Kbrepresent the strength of an acid and a base, respectively. In case of a
conjugate acid-base pair, they are related in a simple manner so that if one is known,
+
the other can be deduced. Considering the example of NH4 and NH3we see

NH 4  H 2Ol   H 3O   aq   NH 3 aq
 
aq

 H 3O    NH 3 
Ka   5.6 1010
 NH 4 

NH 3 aq   H 2Ol   NH 4  aq    OH  
 aq 

IONIC EQUILIBRIUM 20
  NH 4  OH  
Kb   1.8 10 5
 NH 3 
2 H 2Ol   H 3O aq    OH  
 aq 

K w   H 3O   OH    1.0 10 14 M

K a  K b  K w  1.0  10 14 M
This can be extended to make a generalisation. The equilibrium constant for
a net reaction obtained after adding two (or more) reactions equals the product
of the equilibrium constants for individual reactions.
KNET= K1 x K2x........
pK values of the conjugate acid and base are related to each other by the equa
tion
pKa+pKb = pKw = 14 ( at 298K)
PH of mixture of two moderately weak acids:

[ H  ][OCN  ]
HOCN  H   OCN  , K a1 
[ HOCN ]
[ H  ][ HCOO  ]
HCOOH  H   HCOO  , K a2 
[ HCOOH ]
[ H  ]T  [ H  ]ByHOCN  [ H  ]ByHCOOH

A/C to charge balancing:

[ H  ]T  [OCN  ]  [ HCOO  ]
K a1 x[ HOCN ] K a2 x[ HCOOH ]
[ H  ]T  
[ H  ]T [ H  ]T
[ H  ]T2  K a1 x[ HOCN ]  K a2 x[ HCOOH ]
[ H  ]T  K a1 xC1  K a2 xC2

PH of mixture of two moderately weak bases:

[OH  ]T  K b1 xC1  K b2 xC2
PH of mixture of too weak (pka ranging 10 to 14) or solutions are too
dilute:

 [ H  ][ A ]

HA  H  A , K a1 
[ HA]
 [ H  ][ B  ]

HB  H  B , K a2 
[ HB ]
IONIC EQUILIBRIUM 21
 H 2O  H   OH  , KW  [ H  ][OH  ]
[ H  ]T  [ A ]  [ B  ]  [OH  ]
K a1 x[ HA] K a2 x[ HB ] KW
[ H  ]T  
 

[ H ]T [ H ]T [ H  ]T
[ H  ]T2  K a1 x[ HA]  K a2 x[ HB ]  KW
[ H  ]T  K a1 xC1  K a2 xC2  KW

P-1: Determine PH of a solution containing 0.1M AcOH & 0.2 M PhOH. Ka of

AcOH is 2 x 10-5 & Ka of PhOH is 10-10. (PH = 2.85)
P-2: Determine PH of a solution containing 0.1M AcOH & 0.001 M CH2ClCOOH.
Ka of AcOH is 2 x 10-5 & Ka of CH2ClCOOH 1.4 x 10-3.
Hint : Ionisation of water is ignored.
P-3: What volume of 0.1 M HCl solution should be added to a 500 ml of 0.5 M
HCOOH solution in order to prepare an acid solution of PH =1.5. Ka of formic
acid is 2 x 10-4 at 298 K? (Volume = 208 ml)
P-4: A one g sample containing some PhCOOh & other inert impurity was dissolwed
in water & volume made up to 10 ml. PH of the resulting solution was found to
be 2.2. If Ka of PhCOOH is 6 x 10-5 at 298 k. Determine the % purity.
(Mass% = 81.74%)
P-5: In an aq. solution, 0.5 M Trimethylamine is 2.5% ionised.
Determine: (a) OH   ,  Me3 NH   ,  Me3 N  &[ H  ] & PH of solution.
(b) Degree of ionisation if conc. is decreases to 0.01 M?
(a) OH     Me3 NH   = 1.25 x 10-5M,  Me3 N  = 0.4875 M & [ H  ] 8 x 10-13M
PH =12.1 (b)   0.16
P-6: In an experiment, 1.2 g of Mg metal was burnt in air so that a part of metal was
oxidised to MgO & rest in to Mg3 N2 . The residue was dissolved in 100 ml water
& NH 3 produced was not allowed to escape. Assuming, negligible solubility of
Mg (OH ) 2 ,determine the mass % of Mg converted into MgO. PH of the above
solution was 11.35 & Kb of NH 3 = 2 x 10-5.
(Mass % of Mg converted to MgO = 23.8%)

IONIC EQUILIBRIUM 22
IONISATION CONSTANT OF SOME COMMON POLYPROTIC ACIDS
Poly basic acids ionise stepwise as for example ortho phosphoric acid ionises in
three steps andeach step has its own ionisation constant
H3PO 4 H++H2PO 4- I step
H2PO 4- H++HPO 42- II step
HPO 42- H++PO 43- III step
Let k1,k2 and k3 be the ionisation constants of first, second and third steps
respectively, thus
 H    H 2 PO4  
k1=
 H 3 PO4  ;
 H    HPO4 2 
k2=  H PO   ,
 2 4 

 H    PO43 
k3=  HPO 2 
 4 

is general k1>k2>k3.
The overal dissociation constnt (k) is given by the relation
k=k1 x k2 x k3
PH OF POLYPROTIC ACIDS HXA:
If it is a weak acid it will ionize as:
[ H  ]T [ HA ]
H 2 A  H   HA , Ka1       (1)
[ H 2 A]
[ H  ]T [ A2  ]
HA  H   A2  , K a2       (2)
[ HA ]
A/C to material balancing : At eq:
 [ H  ]T  [ A2  ]  [ H 2 A]      (3)
From 1st , 2nd & 3rd


K a2 .[ HA ] [ H  ]T .[ HA ]
[ H ]T  
[ H  ]T K a1
[ H  ]T  x &[ HA ]  C
K a2 .C x.C
x  
x K a1

IONIC EQUILIBRIUM 23
 x 2 .C
x  K a2 .C 
2

K a1
 C 
x 2 1    K a2 .C
 Ka
 1 
 Ka  C 
x2  1   K a2 .C
 Ka 
 1 
K a .K a .C
x 2  1 2 , ( K a1  C  C )
K a1  C
x  K a1 .K a2
Ka1 Ka2
P P
 PH 
2

It is useful when K a & K a are close to each other..

1 2

For most of the cases, K a > K a -----, and in this situation, contribution of higher
1 2

order ionisation to the total [ H ]T could be ignored.



Exa:
  [ H  ][ HCO3 ] 7
H 2CO3  H  HCO , K1  4.2 x10 
3
[ H 2CO3 ]
[ H  ][CO32  ]
HCO3  H   CO32  , K 2  4.8 x10 11 
[ HCO3 ]
If we ignore second ionisation, then

[ H  ]  [ HCO3 ]
[ H  ]2
 K1  & K 2  [CO32  ]
[ H 2CO3 ]
[ H  ]2 [CO32  ]
 K a  K1.K 2   2.016 x1017
[ H 2CO3 ]

This can be applied only if [ H  ] , [CO32 ] & [ H 2CO3 ] are known from indepen
dent sources.

IONIC EQUILIBRIUM 24
P-1: Determine PH of an solution of carbonic acid if molar solubility of
carbondioxide in the given condition is 0.01. K1  4.2 x107 & K 2  4.8 x1011 .
(PH = 4.18)
P-2: Find the conc. of [ H  ] , [ HCO3 ] & [CO32 ] , in a 0.01 M solution of carbonic acid
if the PH of solution is 4.18. Given K1  4.45 x107 & K 2  4.69 x1011 .
( [ H  ]  6.61x105 M ,[ HCO3 ]  6.73 x10 5 M &[CO32 ]  4.78 x10 11 M )
P-3: Ionisation constants of H 2 S are K1  107 & K 2  1014 . If molar solubility of H 2 S
is 0.03 M, determine [ S 2 ] in a saturated solution of H 2 S whose PH = 5.
( [S 2 ] = 3 x1013 M )
P-4: A solution contains 0.1 M H 2 S & 0.3 M HCl. Calculate the conc of [ S 2 ] &
[ HS  ] ions in solution. Given K1  107 & K 2  1.3 x10 13 .

[ HS 
]  3.3 x10 8 M &[ S 2  ]  1.44 x10 20 M 

P-5: The dissociation constants of H 2 S are K1  4 x103 & K 2  1x105 . Calculate

sulphide ion conc. in 0.1 M H 2 S solution. Also report [ H  ] and PH.
[ H 
]  0.018 M  [ HS  ] &[ S 2  ]  10 5 M 
P-6: Acid dissociation constant of phosphoric acid are:
H 3 PO4  H   H 2 PO4 , K1  7.5 x10 5
H 2 PO4  H   HPO42 , K 2  6.2 x10 8
HPO42   H   PO43 , K 3  10 12

If a solution of H 3 PO4 has PH = 3 & [ H 3 PO4 ]  0.1M , determine the conc. of

H 2 PO4 , HPO42  & PO43 in the solution.

[ H 2 PO4 ]  7.5 x10 3 M ,[ HPO42  ]  4.65 x10 7 M &[ PO43 ]  4.65 x10 16 M 

P-7: Calculate the conc. of all species of significant conc. present in 0.1 M H 3 PO4 .
Given K1  7.5 x105 , K 2  6.2 x108 & K 3  3.6 x1013 .

[ H 
]  0.024 M  [ H 2 PO4 ],[ H 3 PO4 ]  0.76 M ,[ HPO42  ]  6.2 x10 8 M &[ PO43  ]  9.3 x10 19 M 

IONIC EQUILIBRIUM 25
Zwitter Ion: Ionic species containing + ve as well as - ve charges in the same
molecule, which we can notseperate. e.g. alpha-amino acid.
H 2 NCH ( R )COOH  H 3 N  CH ( R )COO  (Zwitter Ion)
Amino acids in water always exist as Zwitter Ion.
Isoelectric Point (P. I.): When an acid or base is added to a aq. solution of amino
acid or an amphoteric ion like H 2 PO4 , HPO42  , HCO3 etc. then the conc. of
cations and anions produced are different which can be easily identified by
passing the suitable amount of electricity through the aq. solution of the
compound, then the ion which is in more conc. move towards opposite
electrode till the conc. of cations & anions produced by the compounds
become equal & no migration is observed.
Isoelectric Point (P. I.): The Ph value, when there is no migration of cation or anion is
observed in the presence of electric field is known as Isoelectric Point (P. I.).
In acidic medium: Amino acids exist as cation.


H 2O
H 3 N CH ( R)COOH   H 3O   H 3 N CH ( R)COO 
[ H 3O  ][ H 3 N  CH ( R )COO  ]
K a1       (1)
[ H 3 N CH ( R )COOH ]

 H 3O   H 2 NCH ( R)COO 
H 3 N CH ( R)COO  

H 2O

[ H 3O  ][ H 2 NCH ( R )COO  ]
K a2       (2)
[ H 3 N CH ( R )COO  ]
1x 2
[ H 3O  ]2 [ H 2 NCH ( R)COO  ]
K a1 xK a2 
[ H 3 N CH ( R )COOH ]
AtP.I .  [ H 2 NCH ( R )COO  ]  [ H 3 N  CH ( R )COOH ]
[ H 3O  ]2  K a1 xK a2
 K K
P a1  P a2 
 PH  
 2 

In basic medium: Amino acids exist as anion.


H 2O
H 2 NCH ( R )COO    OH   H 3 N CH ( R )COO 
[OH  ][ H 3 N  CH ( R )COO  ]
K b1       (1)
[ H 2 NCH ( R )COO  ]

IONIC EQUILIBRIUM 26
 
 OH   H 3 N CH ( R )COOH
H 3 N CH ( R)COO  

H2 O

[OH  ][ H 3 N CH ( R )COOH ]

K b2       (2)
[ H 3 N CH ( R )COO  ]
1x 2
[OH  ]2 [ H 3 N  CH ( R )COOH ]
K b1 xK b2 
[ H 2 NCH ( R )COO  ]
AtP.I .  [ H 2 NCH ( R )COO ]  [ H 3 N  CH ( R )COOH ]
[OH  ]2  Kb1 xK b2
 K K
P b1  P b2 
  POH  
 2 

SALT HYDROLYSIS:
The reaction between the cation or anion or both of a salt with water giving
either acidic solution or basic solution or even neutral solution is known as salt
hydrolysis.
M + + H2O  H+ + MOH
A- + H2O  OH- + HA
The reaction between a salt and water is known as salt hydrolysis. The
compounds containing positive and negative ions are known as salts. Their solutions
may be acidic, basic (or) neutral. They are clasified as
SIMPLE SALTS: Formed by neutralisation of an acid and a base. They may
be further classified as
NORMAL SALTS: Salts not containing replceble hydrogen (or) hydroxyl
group
eg. Na2SO4,KNO3,AlPO4, CaCl2
ACIDIC SALTS: Salts containing replaceable hydrogen atoms
Eg:NaHSO4,Na2HPO4,NaHCO3 etc
BASIC SALTS: Salts containing replaceble hydroxyl groups
eg. Zn(OH)Cl,Mg(OH)Cl,Fe(OH)2Cl.
DOUBLE SALTS: Formed by the combination of two simple salts
Eg: FeSO4(NH4)2SO46H2O, K2SO4 Al2(SO4)3 24H2O
COMPLEX SALTS: Salts containing complex ion
eg. K4[Fe(CN)6,[Cu(NH3)4]SO4
MIXED SALTS: Salts containing more than one type of cation (or) anion
eg. CaOCl2,NaKSO4

IONIC EQUILIBRIUM 27
 The hydrolysis reaction is a reversible reaction. The equilibrium constant for the
hydrolysis reaction is known as hydrolysis constant. It is represented by Kh.
The hydrolysis process is a reverse reaction of neutralization.
A ci d + B ase  Salt + Water (neutralisation)
Salt + Water  Acid + Base (hydrolysis)
1. SALTS OF STRONG BASES AND STRONG ACIDS :
NaCl, KNO3, Na2SO4, Kl, CsCl, KCl
This type of salts do not undergo hydrolysis. The aqueous solution of the salt is
neutral. The pH of the aqueous solution of this salt is equal to 7.The aqueous solution
of the salt cannot change the colour of blue litmus to red or red litmus to blue.
2. SALTS OF STRONG ACIDS AND WEAK BASES.
Eg:NH4Cl, ZnSO4, Al(NO3)3, FeSO4, MgCl2, AgNO3, Zn (NO3)2
The cation of the salt undergoes hydrolysis.
M+ + H2O  MOH + H+
MOH   H 
Kh = M  

The aqueous solution of the salt is acidic in nature. The pH of the aqueous solution
of the salt is less than 7.
The aqueous solution of the salt turns blue litmus to red. The hydrolysis constant for
the salt is given by
KW
Kh = K
b

3. SALTS OF WEAK ACIDS AND STRONG BASES

Eg: CH3COONa, KCN, NaClO, K2CO3, Na2S, HCOOK, Na2B4O7 The anion of the
salt undergoes hydrolysis.
A- + H2O  HA + OH
 HA OH  
Kh =  A 

The aqueous solution of the salt is basic in nature. The pH of the aqueous solution
of the salt is more than 7
The aqueous solution of the salt turns red litmus to blue. The hydrolysis constant for
the salt is given by
KW
Kh = K
a

IONIC EQUILIBRIUM 28
4. SALTS OF WEAK ACIDS AND WEAK BASES
Eg. : CH3COONH4 ,(NH4)2CO3Both the cation and anion of the salt undergo
hydrolysis.
(B+ + A-) + H2O  BOH + HA

Kh 
 BOH  HA
 B   A  

The aqueous solution of the salt is

i. Neutral, if Ka of Acid is equal to Kb of base.
ii. Acidic, if Ka of Acid is greater than Kb of the base .
iii. Basic, if Ka of Acid is less than Kb of base
The hydrolysis constant for the salt is given by
Kw
Kh 
K a .K b
DEGREE OF HYDROLYSIS:- It is a defined as the fraction of the total salt
which is hydrolysed at equilibrium
Eg: If 90% of a salt solution is hydrolysed its degree of hydrolysis is 0.90 (or) 90%.
It is generally represented by h.
number of moles of the salt hydrolysed
h = Total number of moles of the salt taken

WA/SB SA/WB WA/WB

h  K hV h  K hV h  Kh

Kh Kh
h h h  Kh
C C
KW KW KW
Kh  Kh  Kh 
Ka Kb K a Kb
KW KW
[H  ]  [H  ]  [ H  ]  Ka h
hC hC

KW K a KW Kb KW K a
[H  ]  [H  ]  [H  ] 
C C Kb

1 Ka 1 1 1 1 Ka 1 Kb
PH  7  P  log C P H  7  P Kb  log C PH  7  P  P
2 2 2 2 2 2

IONIC EQUILIBRIUM 29
P-1: A solution is 100 ppm (w/v) in NaOCl. Determine PH of this solution
if Ka(HOCl) = 3x108 . (PH = 9.33)
P-2: Ca(OCl )2 is usually added to control the PH of swimming pool. Determine
weight of Ca(OCl )2 required to be dissolved in a swimming pool measuring
10m x 5m x 2m to obtain PH = 7.7? Ka(HOCl) = 3x108 . (wt =8.9375 gm)
P-3: A 0.1 M AcOH solution is being titrated against a saturated 0.025 M NaOH
solution. Determine PH at the equivalence point if Ka of AcOH = 2 x105 .
(PH = 8.5)
P-4: Determine PH of 0.05 M aq. solution of NaHCO3 .
Given: K a  4 x107 & K a  5 x1011 for H 2CO3 at 298 K?
1 1
(PH= 8.34)
P-5: A 10 lit. polluted air at a temperature of 298 K & atmospheric pressure was
passed through lime water giving 0.065 g CaCO3 . Determine % by volume of
carbon dioxide in air sample. Also determine PH of lake water that is located on
the polluted site if Henry law constant for carbon dioxide is 3.35 x104 Matm 1 ,
K a1  4 x107 & K a1  5 x1011 . (%VCO2  0.1588%, P H  6.48)
P-6: A 0.01 M solution of H 2CO3 is being titrated with 0.015 M aq. NaOH solution.
Determine PH of the solution at phenolphthalein in end point.
K a1  4 x107 & K a1  5 x1011 . (PH = 9.09)
P-7: A 0.01 M aq. solution of MeNH 2 is titrated by a 0.005 M HCl solution at 298 K.
K b MeNH 2  4 x104 . Determine the PH of the solution at equivalence point.
(PH = 6.5)

IONIC EQUILIBRIUM 30
BUFFER SOLUTIONS :
A solution which reserves its acidity or alkalinity is known as a Buffer Solution.
A solution which resists the changes in its pH value on long standing (or) on dilution
(or) on addition of a small quantity of acid or base is known as a Buffer solution.
The resistence offered by a solution to any change in its pH value is known as its
Buffer action.
The aqueous solution of the salt of a weak acid and weak base will behave as a
Buffer solution. The pH of the solution depends on the salt dissolved in water.
TYPES OF BUFFER SOLUTIONS
1. Acedic buffer: CH3COOH+CH3COONa
2. Basic buffer: NH4OH+NH4Cl
Ex of buffer solutions 1) Phthalic acid+ potassium hydrogen phthalate
2) Citric acid+ sodium citrate 3) Boric acid + borox
4) H2CO3+NaHCO3 (Sodiumhydrogen carbonate)
This system is found in blood and helps in maintaining pH of the blood close to
7.4[pH-value of human blood lies between(7.36-7.42), a change in pH by 0.2
units may cause death]
( 5) NaH2PO4+Na3PO4, 6) NaH2PO4+Na2HPO4
7) Glycerine + HCl, 8) The pH value of gastric juice is maintained between
1.6 to 1.7 due to buffer system
Buffer solutions of desired PH are of two types, namely i) Acid buffer ii) Basic
buffer.
i) Acid buffer:A mixture of weak acid and a salt of same acid with strong base is
known as Acid Buffer.Examples for acid buffers
0.01M-CH3COOH+0.01M-CH3COONa, 0.01M-NaH2PO4+0.01M-H3PO4
0.05M-borax + 0.05M - Tetraboric acid , 0.025M NaHCO3 + 0.025M-Na2CO3
The p of Acid Buffer depends on the P of acid present in the buffer and the
H ka

moles ratio of acid and salt mixed.

The pH of acid - Buffer can be calculated by using Henderson’s equation.

PH  P Ka  log
Salt   H   
Ka  acid 
 acid  ,  Salt 
The pH range in which an acid Buffer works effectively is Pka + 1.
The pH of acid-buffer need not be less than 7.
ii) Basic buffer:A mixture of weak base and a salt of same base with strong acid is
known as Basic buffer.Examples for Basic buffers
0.01M NH4OH  0.01M NH4Cl , 0.01M NH 4 OH  0.01M NH 4 NO3
The pH of basic buffer depends on pKb of base present in the buffer and the moles

IONIC EQUILIBRIUM 31
 ratio of base and salt mixed.
The pOH of basic buffer can be calculated by using Henderson equation.

POH  P Kb  log
Salt  OH   
Kb  Base 
 base ,  Salt 
pH = Pkw-pOH

P H  14  P Kb  log
Salt 
 base
The pOH range in which a basic buffer works effectively is pkb+ 1
The pH of basic buffer need not be more than 7.
Buffer capacity  :The number of moles of acid or base that must be added to one
litre of a buffer solution to change its pH value by one unit is known as the Buffer
capacity of the buffer solution
 No.of moles of acid or base 
added to a litre of solution 
Buffer Capacity      
Change in P H value

A good Buffer will have high buffer capacity.

The Buffer capacity of an acid buffer is very high if its pH value is equal to pka of
Acid present in it.
The Buffer capacity of a basic buffer is very high if its pOH value is equal to the Pkb
of base present in it.
APPLICATIONS
Buffer solutions are used in chemical analysis, industrial synthetic processes and
enzyme catalyzed reactions.
Buffer solutions play an important role in Biochemical reactions.
Buffer solutions are used in water softening process.
The pH of the blood is maintained at 7.4 mainly by the HCO3 / H2CO3 buffer system.
In industries, buffer solutions are used in the alcoholic fermentation (pH 5 to 6.5),
tanning of leather, electroplating manufacture of sugar, paper manufacturing etc
CH3COOH+CH3COONa is used in the removel of phosphate radical during
qualitative analysis of the mixtureNH4Cl+NH4OH is used for theprecipitation of
hydroxides of third group of qualitative analysis.
P-1: How many mole of NaOH can be added to 1 lit of solution of 0.1 M NH 3 & 0.1 M
NH 4Cl without changing POH by more than one unit.PKb of NH 3 = 4.75?
(0.082 mole)

IONIC EQUILIBRIUM 32
P-2: A definite volume of an aq. N/20 AcOH (PKa = 4.74) is titrated with a strong
base. it is found that 75 equal sized drops of NaOH added from a burette effect
the complete neutralization. Find the PH when an acid solution is neutralized to
the extent of 20%, 40%, & 80% respectively.
( At 20%, P H  4.14, At 40%, P H  4.56, At80% & P H  5.70)
P-3: To one lit or decimolar solution of AcOH, how much dry AcONa be added (in
mole) so as to decrease the conc. of [ H  ] to 1/10 th of its previous value?
K a  2 x105 . (0.0142 mole)
P-4: The PH of blood stream is maintained by a proper balance of H 2CO3 &
NaHCO3 conc. what volume of 5 M NaHCO3 solution should be mixed with 10
ml sample of blood which is 2 M in H 2CO3 in order to maintain a PH of 7.4.
Ka of H 2CO3 in blood = 4 x104 ? (V = 40 ml)
SOLUBILITY
The no.of grams of solute is dissolved in 100gm of solvent is known as solubility.
Weight of solute
Solubility=  100
Weight of solvent
Units of solubility are moles/litreSolubility depends on the following factors.
a) Nature of the solute b) Nature of the solvent
c) temperature d) pressure (for gaseous solute)
Lighter salts dissolve more than heavier salts.
Solubility equilibria of sparingly solubily salts:
Solubility of ionic solids in water varies.Ex:CaCl2 is soluble in water and they are
hygroscopic in water and even absorb water vapour from atmosphere.In LiF is little
soluble and they commenly termed as insolubleThe solubility depends on a number
of factors
1) Lattice enthalpy 2) Solvation enthalpy
For a salt to dissolve in a solvent the strong forcesof attraction between its
ions ( Lattice enthalpy) must be over come by the ion - solvent interactionsIn case a
non polar solvent, solvation enthalpy is small and hence not sufficient to over come
lattice enthalpy of the salt .Conscquently the salt does not dissolve in non-polar
solvent.For a salt to be able to dissolve in a particular solvent its solvation enthaply
must be greater then its lattice enthalpy.
Based on solubility, types of salts : -
Category-I Soluble Solubility 0.1M
Category-II Slightly Soluble 0.01M < solubility <0.1M
Category-III Sparingly soluble Solubility < 0.01M
IONIC EQUILIBRIUM 33
a) SOLUBLE SALTS : Which contain more than 1g of solute in 100ml solution.
Eg : - NaCl , KCl , BaCl 2 etc.
b) SPARINGLY SOLUBLE SALTS : - Which contain less than 1g of solute in
100ml solution.
Eg : - AgCl , AgI , BaSO4 , PbSO4 etc.
c) INSOLUBLE SALTS : - Which contain 103 g of solute in 100ml solution.
Based on amount of dissolved solute in solution, solutions are three types
a) SATURATED SOLUTION : - The solution which contain exactly the required
amount of solute for saturation.
1) It is a stable solution.
2) In this solution equilibrium state is established between undissolved solute and
dissolved solute.
3) It gives unsaturated solution on heating and gives super saturated solution on
cooling.
4) A saturated solution of a salt contains
a) Salt in the solid form b) Salt in the dissolved form
5) Saturated solution contains two dynamic equilibria. They are

 dissolved salt
UnDissolved salt 


 Ions of the salt.
Dissolved salt 

So it is represented as
AB 


 AB 
 A  B


 undissolved   Dissolved   Ions 
b) UNSATURATED SOLUTION : - The solution which contains lesser amount solute
that required for saturation.
c) SUPERSATURATED SOLUTION : - The solution which contains more amount
of solute that required for saturation.
SOLUBILITY PRODUCT : -  K SP 
It is the product of the molar concentration of its ions in a saturated solution of
electrolyte. K SP for a salt changes with temperature
Solubility product of a sparingly soluble salt AxBy is given by

Ax B y 
 xA y  yB x

IONIC EQUILIBRIUM 34
  y x  x  y
K  A . B
SP    

Ksp   xs   ys 
x y

If solubility is known K SP can be calculated (or) vice versa.

Examples of KSP
For binary salts like AgCl , AgBr solubility S can be calculated as S  K SP
For ternary salt like PbCl2 , Mg  OH 2 , Ag 2CrO4

K SP K 
1/3

S 3
(or) S   SP 
4  4 

For AB salt K SP  s 2 : AB2 salt K SP  4 S 3 :

AB3 salt K SP = 27S4 : A3 B2 salt K SP  108S 5 ;
Where S=Solubility
Saturated Solution

BaSO4(S)  
 Ba2+(aq)+SO42- (aq)
in water

K = {[Ba2+][SO42-]}/[BaSO4]
KSP= K[BaSO4]=[Ba2+][SO42-]
KSP in the above equation at 298K is1.1 x 10-10
1.1 x 10-10 = (S)(S)=S2 or S = 1.05 x 10-5
consider a salt likezirconium phosphate ofmolecular formula (Zr 4+ )3(PO 4 3-).
Itdissociatesinto 3 zirconium cations ofcharge +4 and 4 phosphate anions of charge
-3. If the molar solubility ofzirconium phosphate is S
[Zr4+]=3S and [PO43-] = 4S
and KSP = (3S)3(4S)4 = 6912(S)7
or S = {KSP/(33 x 44)}1/7 = (KSP/6912)1/7
APPLICATIONS :
1) The concept of solubility product helps the formation of a precipitate.
a) Ionic product  K SP , no ppt is formed (unsaturated solution)
b)Ionic product  K SP , a ppt is formed (super saturated solution)
c) Ionic product  K SP , solution issaturated
2) In predicting the solubility of a sparingly soluble salt.
3) In qualitative analysis, the seperation and identifi cation of various basic radicals into
different groups.
4) In purification of common salts.

IONIC EQUILIBRIUM 35
5) In salting out of soap.
SALTING OUT OF SOAP: From the solution, soap is precipitated by the addition
of concentrated solution of NaCl
RCOONa RCOO-+Na+
soap
NaCl Na++Cl-
Hence, the ionic product [RCOO-][Na+] exceeds the solubility product of soap
and there fore,soap precipitates out from the solution.
IN QUALITATIVE ANALYSIS:- The separation and identification of various
basic rdicals into different groups is based upon solubility product principle
and common ion effect
1) Precipitation of first group radicals:(pb+2,Ag+,Hg+2) The group reagent is
dilute HCl, [Ag+][Cl-] > Ksp for AgCl
2) Precipitation of second group radicals:-(Hg+2,pb+2,Bi+3 ,Cu+2,Cd+2,As+3,Sb+3
and Sn+2)The group reagent is H2S in presence of dilute HCl, [pb=2][S-2]> Ksp
for pbs
3) Precipitation of third group radicals:(Fe+3,Al+3 and Cr+3)The group reagent is
NH4OH in presence of NH4Cl,[Fe+3][OH-]3 >Ksp
4) Precipitation of IV-group radicals:[Co+2,Ni+2,Mn+2 and Zn2+]The group re
agent is H2S in presence of NH4OH,[Co+2][S-2]>Ksp
5) Precipitation of V-group radicals:(Ba+2,Sr+2,Ca+2)The group reagent is Am
monium carbonate in presence of NH4Cl and NH4OH[Ba+2][CO32-]>Ksp
THE SOLUBULITY PRODUCT CONSTANT (KSP) VALUES AT 298K
Name of the salt Formula KSP
Silver Bromide AgBr 5.0 x 10 -13
Silver Carbonate Ag 2CO 3 8.1 x 10-12
Silver Chromate Ag2CrO4 1.1 x 10 -12
Silver Chloride AgCl 1.8 x 10-10
Silver Iodide AgI 8.3 x 10-17
Silver sulphate Ag 2 SO 4 1.4 x 10-5
A.Hydroxide Al(OH)3 1.3x10 -33
B.Chromate BaCrO 4 1.2 x 10-10
B.Fluoride BaF 2 1.0 x 10-6
Barium Sulphate BaSO 4 1.1 x 10-10
Cuprous Iodide CuI 1.1 x 10-12
Lead Bromide PbBr2 4.0 x 10-5
Lead chloride PbCl2 1.6 x 10-5
Lead sulphide PbS 8.0 x 10-28
ThallousIodide TII 6.5 x10-5
Zinc Carbonate ZnCO3 1.4 x10-11

IONIC EQUILIBRIUM 36
 Zinc Hydroxide Zn(OH)2 1.0 x10-15
Zinc Sulphide ZnS 1.6 x 10-24
CALCULATION OF REMAINING CONCENTRATION AFTER
PRECIPITATION:Some times the ion remains after precipittion if it is in
excess remaining concentration can be determined
K sp [ AB]
Ex:- [A+]left =
[ B ]

K sp [ca(OH ) 2 ]
[Ca+2]left =
[OH  ]2

 initial conc  Re maining conc 

% precipitation of ion =  initial conc  100
 
FACTORS AFFECTING SOLUBILITY OR SOLUBILITY PRODUCT:
(1) Common Ion Effect: When a weak electrolyte is dissolved in a strong
electrolyte having one ion common, then solubility of weak electrolyte
decreases.
P-1: Determine molar solubility of AgCl in 0.01 M NaCl solution & also calculate the
factor by which solubility is decreased as compared to solubility in pure water.
K sp ( AgCl )  1.7 x1010 ? ( S  1.3x105 M , 767times )
P-2: Determine molar solubility of PbI 2 in 0.1 M NaOH solution.
K sp ( Mg (OH )2 )  7 x1012 ? (S  7 x10 10 M )
P-3: Determine molar solubility of Mg (OH ) 2 in 0.01 M Pb( NO3 ) 2 solution.
K sp ( PbI 2 )  1.4 x108 ? ( S  5.9 x104 M )
(2) Simultaneous Solubility: If two or more sparingly soluble salts have an ion
common in them.
Example:

AP  A  P 
AQ  A  Q 
[ A ]  S1  S 2
K SP ( AP)  [ A ][ P  ]  ( S1  S2 ) S1
K SP ( AQ )  [ A ][Q  ]  ( S1  S2 ) S2

Note:When Ksp of both the salts are close then add the conc. of common ion
is equal to the ( S1  S2 ) . But when large differance in their Ksp then use solubility
of more soluble salt (i.e. C.I.E.)
IONIC EQUILIBRIUM 37
P-1: Determine simultaneous solubilities of CaSO4 & BaSO4 .
K SP CaSO4  2 x104 & K SP BaSO4  1.9 x10 9 ?
(CaSO4  1.414 x102 M & BaSO4  1.06 x107 M )
P-2: Determine simultaneous solubilities of CaF2 & MgF2 .
K SP CaF2  1.7 x10 10 & K SP MgF2  7.3 x10 9 ?
(CaF2  2.82 x105 M & MgF2  1.213 x103 M )
(3) Selective Precipitation: When two or more metal ions are in a solution then
these can be ppted using a common anion depending on Ksp of salt.
P-1: A solution contains 0.1 M Mg 2 & 0.1 M Sr 2 . The conc. of H 2CO3 is adjusted to
a value of 0.05 M. What range of PH values would permit the separation of
these metal ion as their carbonates. K SP MgCO3  3.5 x108 , K SP SrCO3  9.3 x10 10
& K a H 2CO3  2.4 x10 17 ? (PH = 4.94-5.73)
P-2: For H 2 S K a  107 & K a  10 14 . Asalt solution of H 2 S is 0.1 M in H 2 S and
1 2

contain Mn , Co & Ag  at an original conc. of 0.01 M each. Determine the PH

2 2

range for the selective pption of these metal ions. K SP MnS  2.5 x1010 ,
K SP CoS  4 x1021 & K SP Ag 2 S  6.3x1050 .
( P H  1.8, Ag 2 S will ppt;1.8  P H  6.99, CoS will ppt & P H  6.99, MnS will ppt.)
(4) Solubility & Complex ion EQuilibria: When a complex is formed by metal ion of
an insoluble salt, the solubility is increased as compared to its solubility in pure
water.
Exa-1: AgCl in Ammonia

AgCl( s )  Ag(aq )  Cl(aq )

Ag (aq )  2 NH 3( aq )  [ Ag ( NH 3 ) 2 ]
__________________________________
AgCl( s )  2 NH 3( aq )  [ Ag ( NH 3 ) 2 ]  Cl(aq )
[ Ag ( NH 3 )2 ] [Cl(aq ) ]
 KC 
[ NH 3( aq ) ]2
[ Ag ( NH 3 ) 2 ]
KC   2
x[ Ag(aq ) ][Cl(aq ) ]
[ Ag( aq ) ][ NH 3( aq ) ]
K C  K f xK sp

IONIC EQUILIBRIUM 38
 Exa-2: AgBr in Hypo

AgBr( s )  Ag (aq )  Br(aq )

Ag (aq )  2S 2O3(2 aq )  [ Ag (S 2O3 )2 ]3
__________________________________
AgBr( s )  2 S 2O3(2aq )  [ Ag ( S 2O3 )2 ]3  Br(aq )
[ Ag ( S 2O3 )2 ]3 [ Br(aq ) ]
 KC 
[ S2 O3(2 aq ) ]2
[ Ag (S 2O3 )2 ]3
KC  x[ Ag (aq ) ][ Br(aq ) ]
[ Ag(aq ) ][ S2 O32(aq ) ]2
K C  K f xK sp

P-1: What is molar solubility of AgCl in 1.0 M ammonia at 298K. K SP AgCl  1.7 x1010
& K f  [ Ag ( NH 3 )2 ]  1.7 x107 . (0.049 M)
P-2: How many moles of NaOH be dissolved in 1.0 lit water to dissolve 0.1 mole in
Zn(OH )2 as [ Zn(OH )4 ]4  ? K sp Zn(OH )2  4.5 x1017 & K f [ Zn(OH ) 4 ]4  2.8 x1015 .
(1.09 mole)
P-3: H 2 S is bubbled into 0.2 M NaCN solution,which is 0.2 M in each [ Ag (CN )2 ]
&[Cd (CN )4 ]2  . Determine which sulphide will ppt first? K SP Ag 2 S  1050 ,
 2
K SP CdS  7 x10 28 , K f [ Ag (CN )2 ]  2.5 x10 & K f [Cd (CN )4 ]  10 .
20 17

(CdS will ppted first)

P-4: Determine molar solubility of AgI in 0.01 M KCN solution. K SP AgI  8.5 x1017 ,
K f [ Ag (CN ) 2 ]  5.5 x1018 . ( 4.88 x103 M )
P-5: Determine molar solubility of Ag 2CrO4 in 0.05 M ammonia solution.

K SP Ag 2 CrO4  2 x1012 & K f [ Ag ( NH 3 ) 2 ]  10 . (0.0114 M)
8

(5) Effect of acids & bases on solubility of sparingly soluble salts: The solubility
of a sparingly soluble salt is greatly affected by PH if an acid-base reaction also
occurs as the salt dissolves.
Exa: On adding storng acid to saturated solution of CaF2 equilibrium shift to the
right. i.e. solubility of CaF2 increases.

IONIC EQUILIBRIUM 39
 CaF2  Ca 2   2 F  , K sp  [Ca 2  ][ F  ]2
1 [ HF ]2
2 F   2 H 3O   2 HF  2 H 2O, 
K a2 [ H 3O  ]2 [ F  ]2
____________________________________________
CaF2  2 H 3O   Ca 2  2 HF  2 H 2O,
[Ca 2  ][ HF ]2 [ F  ]2 K sp
KC  x  2  2  K spa
[ H 3O  ]2 [F ] Ka

K spa  Acid solubility product.

Note: The solubility of AgCl is independent of PH , because chloride ion a weak baase,
doesnot accept a proton from acid ( H 3O  ) ,therfore solubility of AgCl doesnot
increase as PH is lowered.
P-1: Determine molar solubility of AgCN in 1.0 M nitric acid solution & determine
factor by which solubility is increased in an acid solution as compared to its
solubility in pure water. K SP AgCN  1.2 x1016 & K a HCN  6.2 x1010 ?
( So lub ility  4.399 x104 M & Factor  40.17 x103 )
P-1: Determine molar solubility of CaF2 in 2.0 M nitric acid solution.
K SP CaF2  5.3 x109 & K a HF  5 x109 ? (0.276 M)
(6) Effect of hydrolysis on solubility: If the salt contains either a conjugate acid of
a weak base or conjugate base of a weak acid or both, its solubility is little more
than the expected vealue due to involvment of these conjugate acid or base in the
hydrolysis equilibrium.
Exa: CaCO3 in water
CaCO3( s )  Ca2 ( aq )  CO3(2aq )

CO3(2aq ) is conjugate base of weak acid HCO3( aq ) it hydrolyses as:

CO3(2aq )  H 2O  HCO3( aq )  OH 
This way solubility of CaCO3 increases.
P-1: Calculate molar solubility of AgCN cosidering hydrolysis of cyanide ion. Also
determine the factor by which solubility is increased due tohydrolsis.
K sp AgCN  2 x1016 , K a HCN  6 x1010 ?
( So lub ility  1.49 x107 & Factor  10.57)

IONIC EQUILIBRIUM 40
P-2: Equal volume of 0.02 M AgCN & 0.02 M nitric acid were mixed. Calculate
conc. of silver ion in the solution. K sp AgCN  2 x1016 , K a HCN  6 x1010 ?
([ Ag  ]  5.77 x105 M )
P-3: Molar solubility of Tl2 S in pure water is 6.3x106 . Assume thar sulphide ion
hydrolyses completely to HS  & further hydrolysis is negligible. Determine
K spTl2 S . K a1 H 2 S  107 & K a2  1014 ? K Tl2 S  1.57 x1021 
sp

IONIC EQUILIBRIUM 41
THEORY OF ACID BASE INDICATER:
OSTWALD`S THEORY:The unionised molecule of the indicator has one colour while
the ionised from has another colour. Hln H++In-
Colour A Colour B
[ H  ][ In  ]
HIn =
[ HIn]
Consider the ionisation of phenolphthalein which in weakly acidic in nature
HPh H++Ph-
coloureless Pink
Addition of a strong base will distrub the equilibrium(OH-+H+ H2O) and
more phenolphthalein will ionise giving pink solution.Addition of a strong acid
will suppress the ionisation of phenophthalein by common ion effect , solution
will be colourlessThe indicator is not suitable for titrating weak base like NH4OH
against strong acid. The OH- ions furnished by weak base are insufficient to shift
the equilibrium and pink colour does not appear just at the end point. Excess of
weak base is required.
ACTION OF METHYL ORANGE: Methyl orange is a weak base and is
ionised as follows:
MeOH Me++OH-
yellow red
addition of a strong acid will disturb the equilibrium
(H++OH- H2O) and more methyl orange will ionised giving red
solutionAddition of a strong base will suppress the ionisation of methyl orange
by common ion effect hence solution will be yellow in colour.The indicator is
not suitable for titrating weak acid like CH3COOH against strong base. The H+
ions furnished by weak acid are not sufficient to shift the equilibrium and red
colour does not appear just at the end point. Excess of weak acid is required
QUINONOID THEORY:In the unionised form the indicator is generally in the
benzenoid form which is less intense in colour and in the ionised form it is in the
Quinonoid form which is more intense in colour.

IONIC EQUILIBRIUM 42
Elements of Titration
The standard solution is the solution of known concentration. An accu
rately measured amount of standard solution is added during titration to the
solution of unknown concentration until the equivalence or endpoint is reached.
The equivalence point is when the reactants are done reacting.The solution of
unknown concentration is otherwise known as the analyte. During titration the
titrant is added to the analyte in order to achieve the equivalence point and deter
mine the concentration of the analyte.
The equivalence point is the ideal point for the completion of titration. In order
to obtain accurate results the equivalence point must be attained precisely and
accurately. The solution of known concentration, or titrant, must be added to the
solution of unknown concentration, or analyte, very slowly in order to obtain a
good result. At the equivalence point the correct amount of standard solution
must be added to fully react with the unknown concentration.
The end point of a titration indicates once the equivalence point has been
reached. It is indicated by some form of indicator which varies depending on
what type of titration being done. For example, if a color indicator is used, the
solution will change color when the titration is at its end point.
The equivalence point  The end point
P range of an indicator: For acidic indicator
H

[ H  ][ In ]
HIn  H   In , K Ind 
[ HIn]
[ In  ]
P H  P In  log
[ HIn]

[ In  ]
The human eye is sensitive to colour differences only when the ratio
[ HIn]
ia greater than 10 or smaller than 0.1.
[ In  ] 1
Thus to see the acidic colour =
[ HIn] 10

 P H  P In  1 OR [ H  ]  10 K In

[ In  ] 10
And to see the basic colour =
[ HIn] 1
1
 P H  P In  1 OR [H  ]  K In
10

IONIC EQUILIBRIUM 43
Therrefore, PH range for colour change is P H  P In  1 i.e. pH range of 2 units.
In the midway between the two colours, one can assume that [ HIn]  [ In  ]
i.e. half equivalence point. So, P H  P K i.e. The P K of indicator should be
In In

close to pH of equivalence point. [ H  ]  K a In

For weak base indicators, at the half equivalence point
POH  P KbIn OR [OH  ]  K bIn
The exact point of the colour change will be at PH when [ HIn]  [ In  ] ,
Thus P H  P K .
In

Hence the indicator selected should be suchfor which P H  P K of the In

solution at equivalence point.

Indicators PH Range In Acid In Base P K In

Cresol red (Acid) 0.2 - 1.8 Red Yellow --

Thymol blue (Acid) 1.2 - 2.8 Red Yellow 1.7
Bromophenol blue 2.8 - 4.6 Yellow Blue 4.1
Methyl orange 2.9 - 4.6 Red Orange 3.7
Congo red 3.0 - 5.0 Blue Red --
Bromocresol green 3.6 - 5.2 Yellow Blue 4.7
Methyl red 4.2 - 6.3 Red Yellow 5.0
Bromocresol purple 5.2 - 6.8 Yellow Purple 6.1
Bromophenol red 5.2 - 7.0 Yellow Red --
Bromothymol blue 6.0 - 7.6 Yellow Blue 7.1
Neutral red 6.8 - 8.0 Red Orange --
Phenol red 6.8 - 8.4 Yellow Red 7.8
Cresol red (Base) 7.2 - 8.8 Yellow Red 8.2
Thymol blue (Base) 8.0 - 9.6 Yellow Blue 8.9
Phenolphthalein 8.3 - 10.0 Colourless Red 9.6
Thymolphthalein 9.3 - 10.5 Colourless Blue 9.3
Alizarin Yellow 10.1 - 12.1 Yellow Orange red --

IONIC EQUILIBRIUM 44
 Mixed Indicators: The sharp colour change over a narrow & selected range of
PH can be achieved by the use of mixture of indicators whose PKIn values are
close togather & the Overlapping colours sre complementry at an intermediate
PH value.
Exam: H 3 PO4  H 2 PO4 : HPh + Naphtholphthalein , 3:1 , PH = 8.9
CO32  HCO3 : Thymol blue + Cresol red , 3 : 1 , PH = 8.3
Universal Indicators: Mixture of several indicators with a wide range of PH .
Exam:Alcoholic solution of HPh + Methyl red + Methyl Yellow + Bromothymol
blue and Thymol blue in NaOH solution is Yellow in colour. This shows the
following colour changes at different PH values.
PH 2 4 6 8 10
Colour Red Orange Yellow Green Blue
Acid-Base titration:
(1) Titration of weak acid v/s strong base:
Case-I: When no titration is carried out. It is a case of weak acid.
1 Ka 1
 P HWA  P  log C
2 2
[ H  ]WA  K a .C

Case-II: When titration is < 100%. The salt is formed & WA is left. So ,It is
a case of acidic buffer.
H AcidicBuffer [ Salt ]
P  P K a  log
[ Acid ]
Case-III: When titration is = 100%. The salt of (WA +SB) is formed.
Which shows salt hydrolysis.
1 Ka 1
 PH  7  P  log C
2 2
Case-IV: When titration is > 100%. WA is completely netralised & excess of
SB is left.
 P OH   log[OH  ]
(2) Titration of strong base v/s weak acid:
Case-I: When no titration is carried out. It is a case of strong base.
 P OH   log[OH  ]
Case-II: When titration is < 100%. The salt is formed & SB is left.
 P OH   log[OH  ]

IONIC EQUILIBRIUM 45
 Case-III: When titration is = 100%. The salt of (WA +SB) is formed.
Which shows salt hydrolysis.
1 Ka 1
 PH  7  P  log C
2 2
Case-IV: When titration is > 100%. .Salt of (WA+SB) is formed & excess of
WA is left i.e. acidic buffer.
H AcidicBuffer [ Salt ]
P  P K a  log
[ Acid ]
(3) Titration of weak base v/s strong acid:
Case-I: When no titration is carried out. It is a case of weak base.
1 Kb 1
 P OHWB  P  log C
2 2
Case-II: When titration is < 100%. The salt is formed & WB is left. So ,It is
a case of basic buffer.
H BasicBuffer [ Salt ]
P  P Kb  log
[ Base]
Case-III: When titration is = 100%. The salt of (WB +SA) is formed.
Which shows salt hydrolysis.
1 1
 P H  7  P Kb  log C
2 2
Case-IV: When titration is > 100%. WB is completely netralised & excess of
SA is left.
 P H   log[ H  ]
(4) Titration of strong acid v/s weak base:
Case-I: When no titration is carried out. It is a case of strong acid.
 P H   log[ H  ]
Case-II: When titration is < 100%. The salt is formed & SA is left.
 P H   log[ H  ]
Case-III: When titration is = 100%. The salt of (SA +WB) is formed.
Which shows salt hydrolysis.
1 1
 P H  7  P Kb  log C
2 2
Case-IV: When titration is > 100%. .Salt of (SA+WB) is formed & excess of
WB is left i.e. basic buffer.
H BasicBuffer [ Salt ]
P  P Kb  log
[ Base]

IONIC EQUILIBRIUM 46
P-1: Calculate the PH of the solutions when the following conditions are provided.
(a) 20 ml of M/10 AcOH solution is titrated with M/10 NaOH solution.
PKa AcOH = 4.76.
(i) No titration is carried out (PH = 2.87)
(ii) When 16 ml of NaOH is added (PH = 5.34)
(iii) When 20 ml of NaOH is added (PH = 10.2)
(iv) When 30 ml of NaOH is added (PH = 12.3)
(b) 20 ml of M/10 NaOH solution is titrated with M/10 AcOH solution.
PKa AcOH = 4.76.
(i) No titration is carried out (PH = 13)
(ii) When 18 ml of AcOH is added (PH = 11.7)
(iii) When 20 ml of AcOH is added (PH = 10.02)
(iv) When 40 ml of AcOH is added (PH = 4.74)
(c) 10 m l of M /10 N H 4OH solution is titrated with M/10 H2SO4 solution.
PKb NH4OH= 4.76.
(i) No titration is carried out (PH = 11.12)
(ii) When 4 ml of H2SO4 is added (PH = 8.64)
(iii) When 5 ml of H2SO4 is added (PH = 5.23)
(iv) When 10 ml of H2SO4 is added (PH = 1.3)
(d) 10 ml of M/10 H2SO4 solution is titrated with M/10 NH4OH solution.
PKb NH4OH= 4.76.
(i) No titration is carried out (PH = 0.7)
(ii) When 10 ml of NH4OH is added (PH = 1.3)
(iii) When 20 ml of NH4OH is added (PH = 5.23)
(iv) When 40 ml of NH4OH is added (PH = 9.24)
P-2: Methyl red Has a Ka = 10-5. The acidic form of indicator is red & and its
conjugate base, In- is yellow. Complete the following table:
PH 3 5 7
[In ]/[HIn]
-
-- -- --
Colour -- -- --
(Ans: (i) [In ]/[HIn] = 10 & Red, (ii) [In-]/[HIn] = 1 & mix of Red
- -2

& Yellow i.e. Orange, (iii) [In-]/[HIn] = 102 & Yellow )

P-3: Calculate the PH at which an acid indicator with Ka = 10-5 changes when the
indicator is 10-3. (PH = 5)
P-4: At what PH will a 10-3 M solution of an indicator with Kb = 10-10 change colour?
(POH = 10 & PH = 4)
P-5: What indicator should be used for the titration of 0.1 M KH2BO3 with 1.10 M
HCl? Ka of H3BO3 = 7.3 x 10-10. (PH =5.22 i.e. Methyl red)

IONIC EQUILIBRIUM 47
P-6: Calculate the PH at which an indicator with PKb = 4 changes colour.
(PH = 10)
P-7: Bromophenol blue is an indicator with a Ka value of 5.84 x 10-5. what is the %
of this indicator in its basic form at a PH = 4.84? (80%)
P-8: Aan acid-base indicator has a Ka of 3.0 x 10 . The acid form of an indicator is
-5

red & the basic form is blue. By how much must the PH change in order to
change the indicator from 75% red to 75% blue. (Change in PH = 0.9452)
Strong acid-strong base titration:

IONIC EQUILIBRIUM 48
Weak acid-strong base titration: 0.1 M acetic acid with 0.1 M NaOH

IONIC EQUILIBRIUM 49
Weak base-strong acid titration: 0.1 M Ammonia with 0.1 M HCl

Weak acid-weak base titration: 0.1 M acetic acid with 0.1 M NH3, Mixed
indicator can be used.

IONIC EQUILIBRIUM 50
 Titration of carbonate ion with a strong acid: In case of Na2CO3 , it can be
titrated in 2 stages according to the equation:
Na2 CO3  HCl  NaHCO3  NaCl    (1)
NaHCO3  HCl  H 2 CO3  NaCl    (2)

P K1  P K 2
At 1 eq. point: P H 
st
= 8.3
2
Here indicator PhTh becomes colourless and can be used to detect the
equvalence point.
The PH at the 2nd eq. point is due to that of H 2CO3 produced in solution.
1 K1 1
PH  P  log C  3.8
2 2
So, indicator can be used is M.O; Congo-red and BPB.

IONIC EQUILIBRIUM 51
Titration of Phosphoric acid with KOH solution:

IONIC EQUILIBRIUM 52