06.acids and Bases 93-116

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6. ACIDS AND BASES

Synopsis:
• Based on apparent properties, Robert Boyle classified the substance into acids and bases.
Acids Bases
1. Sour to taste Bitter to taste
2. Turn blue litmus to red Turn red litmus to blue
3. Neutralise bases Neutralise acids
4. Liberate H2 gas on reaction with metals They are soapy to touch
5. Aqueous solutions are good conductors Aqueous solutions are good conductors
6. They decompose metal carbonates and
bicarbo-nates to liberate CO2
• According to Lavoiser all acids must contain oxygen. But dray proved that all acids must contain
Hydrogen but not oxygen.
Eg: HCl, HBr, HI, HF etc,.
• The chemical behaviour of acids and bases is explained by following three theories.
1) Arrhenius theory
2) Bransted - lowery theory
3) Hewis theory
• Bronsted – Lowery theory of Acids and bases:
This is also called protonic theory .
Acid : which donates proton
Eg: HCl, H2SO4, HNO3 etc.
Base : which accepts proton
Eg: NH3, PH3, N2H4, R – NH2 etc.
• Bronsted acid could be a neutral molecule , anion, cation.
Neutral molecule → HCl, HNO3, H2SO4 etc.
Cations → H 3 O + , NH +4
Anions → HSO 4− , HCO 3− , H 2 PO 4− , H(PO 4 ) , H 2 (PO 3 ) Bronsted base could be neutral, cation or
2− −
anion
Neutral → NH3 , PH3, N2H4 etc.
anions → CN−, Br−, I−, OH− etc.
Cations → [Al(H2O)5OH)]2+, [Fe(H2O)5OH]2+
• Neutralisation :
It involves transfer of proton from acid to base and formation of conjugate acid – base pair.
1) HCl+ H2O Cl − + H 3 O +
A1 B2 B1 A2
2) NH 3 + H 2 O → NH ⊕
4 + OH −
B1 A2 A1 B2
−
3) NH 3 + HCl → NH +4 + Cl
B1 A2 A1 B2
• Amphoteric or Amphiprotic substance : The act as both acids and base because they donate proton and
accept proton.
Eg : H2O
1
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Acids and Bases
• Conjugate acid – base pairs :

The acid base pair which differs by a proton is called conjugated acid base pair.
Acid − H⊕ = conjugate base
Base + H⊕ = conjugate acid
Eg : Acid Base
HCl Cl−
H2SO4 HSO −4
HSO −4 SO 24−
H2S HS−
C2H2 CH ≡ C−
CH4 CH3−
[Al(H2 O)6 ]3+ [Al(H2 O)5 OH]2+
[Fe(H2O)6 ]3+ [Fe(H2O)5 OH]2 +
H2 H−
H e−
• In any conjugate acid base pair, if the acid is stronger , the base is weak and if base is stronger , the
acid is weak.
Eg:
1. HCl is strong acid, Cl− is weak conjugate base.
2. CH3COOH is weak acid CH3COO−is strong base
3. NH3 is weak base, NH+4 strong acid
4. HClO4 is strongest acid, ClO −4 weak base
• List of conjugate acid base pairs in a particular order of strength.
Acid Base
[Decreases acidic strength]
1. HClO4 ClO −4
2. HI I−
−
3. HBr Br
4. H2SO4 HSO −4
−
5. HCl Cl
6. HNO3 NO 3−
7. H3O+ H2O
8. HSO −4 SO 24 −
9. H3PO4 H 2 PO −4
−
10. HF F
−
11. CH3COOH CH3COO
12. H2CO3 HCO 3−
−
13. HCN CN
14. NH+4 NH3
−
15. H2O OH
2
Acids and Bases

16. NH3 NH 2−
−
17. OH O2−
18. CH4 CH3−
• Strength of bronsted acids and bronsted bases will depend on the ability to donate or to accept proton.
• Strong acids : which have more ability to donate protons.
Eg: HClO4, HCl, H2SO4
• Weak acids : which have less tendency to donate proton.
Eg: HF, CH3COOH, H2CO3, HCN
• Among Hydracids HCN is the weakest acid
• Strong bases : which have greater tendency to accept protons
Eg: OH−, CH3COO−, CH 3− etc.
• Weak bases → which have less tendency to accept the proton.
−
Eg: Cl−, ClO −4 , Br−, I , NH3…..etc.
• Levelling effect : The strength of stronger acids like HClO4, H2SO4, HCl, HNO3 will become equal to
the strength of H3O+ ion in presence of H2O. This is called levelling effect
HClO4 ≈ H2SO4 ≈ HCl ≈ HNO3 = H3O+
• Similarly the strength of stronger bases like NaOH, KOH, CsOH will become equal to the strength of
OH− ion in presence of H2O
NaOH ≈ KOH ≈ CsOH = OH−
• This levelling effect of acids is due to greater proton accepting tendency of H2O and instantly conversion
into H3O+ therefore the real strength cannot be determined.
• The acids like HClO4, H2SO4 etc. cannot be determined in a levelling solvent like H2O.
• Therefore the strongest acid that can exist in water is H3O+ and the strongest base that can exist is
OH− ion.
• In a solvent like glacial acetic acid, the real strength of acids can be determined because of poor
tendency to accept protons. Therefore acetic acid is differentiating solvent and the strongest acid that
can exist in acetic acid solvent is HClO4.
• In acetic acid, HClO4 > H2SO4 > HCl > HNO3
• Types of solvents: Based on proton donating or proton accepting tendency, solvents are classified into
4 types by bronsted lowery solvents.
1) Protophilic solvents : which accept proton
Eg : H2O, NH3 , ether , C2H5OH etc.
Protophilic solvents will increase acidic strength and decrease the basic strength.
2) Photogenic solvents : which donate H+
protogenic solvents will decrease the acidic strength and increase the basic strength.
3) Amphiprotic solvents : which donates and accept proton
Eg : H2O, C2H5OH
4) Aprotic solvents: which neither donates nor accepts proton.
Eg : CCl4, CHCl3, C6H6, Acetone
Merits of Bronsted – Lowery theory :
1) It could explain acid base behaviour in non – aqueous solvents also .
Eg: liquid SO2, liquid NH3
2) It could explain the basic nature of substances like NH3.
3) It could explain the acidic nature of HCl gas.
3
Acids and Bases

4) It is more generalized than Arrhenius theory.
• Limitations of Bronsted – Lowery theory :
1) This theory explains behaviour of acids only when there is a base (or) It explains behaviour of base
only when there is a acid. (Acid base pairs must be present)
2) It fails to explain the acidic nature of electron deficient compound like BF3, AlCl3 etc.
• Lewis theory of acids – bases :
Acid : which accepts electron pair.
• All electrophiles are Lewis acids
• Lewis acid must contain suitable vacant orbitals.
Eg: BF3, BCl3, AlCl3, H+, Ag+ etc.
Base : which donates e− pair.
• All nucleophiles are Lewis bases
• Lewis base must contain 1 or more lone pairs of electrons.
•• ••• ••
Eg: NH3 , PH3 , R − NH2 ,
•• •• ••
NH2 − NH2 ,OH−, Cl−, H2 O
••
Neutralisation: It involves formation of coordinate covalent bond by the transfer of e− pair form base to
acid.
••
H3 N + BF3 → [H3 N → BF3]
••
H2 O + H⊕ → [H2O − H]+ or H3 O ⊕
••
••••
H3 N + H⊕ → [H3N − H]+ or NH⊕
4
Cl − + AlCl3 → [Cl − AlCl3 ] or AlC l −4

−
• Types of Lewis acids :

1) All simple cations :
Eg : H+, Ag+, Li+, Cu2+, Co3+, Al3+ etc.
••
[
Ag+ + 2NH3 → Ag(NH3 )2 + ]
2) Electron deficient molecules :
Eg: BF3, BCl3, BBr3, BI3, AlCl3, GaCl3 etc.
BF3 < BCl3 < BBr3 < BI3
••
BF3 + F − → [F3B − F]− or BF4−
• 3) Molecules which can extend octet configuration:
Eg: SiF4 , SiCl4, SnCl4, SF4, SFCl4, TeCl4 etc.
2−
⎡F F ⎤
⎢ ⎥
⎢ | ⎥
SiF4 + 2 F− → ⎢F − S − F⎥ or SiF62 −
⎢ ⎥
⎢ | ⎥
⎢⎣ F F⎥⎦
• 4) Molecules with multiple bonds in between atoms of different electronegativities
Acids and Bases

Eg : CO2, SO2, SO3, NO2, N2O5, Cl2O7, P2O5
δ+ δ− ••
O = C = O + OH → O = C − O − or HCO3−
OH
• 5) Molecules in which the central atom with sextet configuration

Eg : S, O, Se……..
O
•• ||
•• O + •• SO 3 → O ← S − O
2− −
•• |
O−
••
•• S + •• SO3 → S 2O3
2− 2−
••
• Types of Lewis bases :

All simple anions :
Eg : Cl−, P− , Br −, OH−, CN− etc.
SiCl4 + 2Cl− → SiCl26 −
• Molecules with lone pairs :
•• •• •• •• •• ••
Eg : N H3 , P H3 , N2 H4 , R − N H2 , R − O H, H2 O ,
•• ••
•• ••
R − O− R, R 2 S etc.
•• ••
••
N H3 + H+ → [H3N → H]+ or NH+4
• Molecular multiple bonds in between similar atoms:
Eg: CH2 = CH2 , CH≡ CH, pyridine , : NO, : CO
+
⎡H 2 C − CH 2 ⎤
CH2 = CH2 + Ag → ⎢ + ⎥
⎢ Ag ⎥
⎣ ⎦
• Draw backs of Lewis theory :
1) It will not consider popular acids like HClO4, HNO3, H2SO4 as they do not form co-ordinate covalent
bond.
2) It fails to explain the catalytic activity of H+.
3) Lewis acid base neutralisation is very slow as it involves formation of co-ordinate covalent bond but
actually neutralisation reactions are very fast.
4) It fails to explain strength of acids and bases.
5) It fails to explain the simple neutralisation reactions where H+ is involved.
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++X-
2 H O
When bases are dissolved in water they ionised into B+ and OH-
BOH- ⎯⎯⎯
H 2O
→ B+
This process in known as ionisation same time referred to as dissociation
5
Acids and Bases

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
The process of ionisation is an equilibrium process
⎯⎯⎯
HX ←⎯⎯
2
→ H ++ X- ---------(1)
⎯
H O
⎯⎯⎯
BOH ←⎯⎯
2
→ B++OH--------(2)
⎯
H O
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- α)C α C α
C 2α 2
Ka=
C (1 − α )
1. Ka = Cα 2
2. α = Ka / C
3. ⎡⎣ H + ⎤⎦ = Cα
4. ⎡⎣ H + ⎤⎦ = Ka × C
1 Ka 1
5. P = P − log C
H
2 2
α = degree of ionization of acid
C = molar concentration of acid
Ka = ionisation constant of acid
For any weak base:
1. K b = Cα 2
2. α = Kb / C
3. OH = Cα
⎡ OH ⎤⎦
4. ⎣
= Kb × C
1 Kb 1
5. P
OH
=
P − log C
2 2
6. P = 14 − P
H OH
α = degree of ionisation of base

C = molar concentration of base
Kb = ionisation constant of base
Acids and Bases
• Comparison of acid – base theories :

1) All Arrhenius acids are bronsted lowery acids but all bronsted lowery bases are not Arrhenius bases.
Eg: HCl(aq) → It is Arrhenius acid as it gives H+ and bronsted lowery acid as it donates proton.
NH3 → It is bronsted lowery base because it accepts proton but it is not Arrhenius base as it will
not give OH−.
• 2) All bronsted lowery bases are Lewis base but Lewis acids need not be bronsted lowery acids.
••
Eg: N H3 → It is Bronsted lowery base because it accepts proton and it is Lewis base because it
donates e- pair.
BF3→ It is Lewis acid as it accepts electron pair but it is not bronsted lowery acid as it will not
donate proton.
• Ionic product of water :
Pure water is weak electrolyte that is just one molecule out of 556 millions of water molecules will
ionise.
• Ionisation of water :
H2O H+ + OH− (or)
2H2O H3O + + OH−
By applying law of mass action to the above ionisation reaction.
[H + ] [OH − ] [H 3 O + ] [OH − ]
K= (or)
[H 2 O] [H 2 O] 2
since the molar concentration of [H2O] is practically a constant and therefore
K or Kω = [H+] [OH−]
Kω → ionic product of water.
• Kω is defined as the product of molar concentration of H+ and OH– ions.
• At 250C, Kω = 1 × 10-14 mol2 / lit2.
• “with an increase in temperature the value of kω increase as the extent of ionisation of water increases”
• At a given temperature the value of Kω remains constant for any given dilute aqueous solution. i.e.
neutral (or) acidic (or) basic.
In pure water (or) neutral aqueous solution.
[H+] =[OH–] = 10–7 mol/lit
[H+] = 10–7 mol/lit
[OH–] = 10–7 mol / lit
Kω = 1 x 10–14 mol/ lit
In acidic solution :
[H+] > [OH–]
[H+] > 10–7
[OH–] < 10–7
Kω = 10–14
In basic solution
[OH–] > 10–7
[H+] < 10–7
Kω = 10–14
• At 900C the concentration of H3O+ ions is 10–6 mole/ lit in pure water. The value of Kw is
7
Acids and Bases

Pure H2O → [H3O ] = [OH ]
+ –
1 x 10–6 = 1 x 10–6
∴ Kw = 1 x 10–12 mol2 / lit2
• pH of solutions:
It was introduced by Sorensen to calculate lower concentrations of H+ ion.
• pH is –ve logarithm of H+ ion concentration.
pH is logarithmic reciprocal of H+ ion concentration.
PH is the negative power rised on ten in order to express H+ ion concentration.
pH = – log[H+]
1
pH = log +
[H ]
[H+] = 10–pH
Even OH– ion concentration can be expressed on pH scale.
pOH = – log(OH–)
[OH–] = 10 −P
OH
For any dilute solution; [H+] [OH–]= 10–14 mol2/ litre2

H OH
PK w = p + p = 14
• Other similar expressions:
p OH = − log[OH − ]
Similarly
pk a = − log k a
pk b = − log k b
pk ω = − log k ω
pk = − log k
p M = − log[M + ] M+ → metal ion concentration
pH scale 1 ⎯⎯ ⎯→ 7 ⎯⎯
acids
⎯
⎯→ 14
bases
neutral
• The maximum concentration of H+ ion that could be expressed on pH scale is 0.1 M. When [H+] = 0.1; pH
= 1. If [H+] = more than 0.1 pH is less than 1
[no provision for less than 1 on scale]
• The maximum concentration of OH– ion that could be expressed on pH scale is 1M. When [OH–] =1M;
pOH = 0; pH = 14 if [OH–] = more than 1M; pOH < 0 and pH > 14 [no provision for more than 14 on pH
scale]
• PH scale is applicable for dilute solutions.
• With increase in the concentration of [H+], pH value decreases, pOH value increases.
• With increase in the [OH–] the pH value increases, and pOH value decreases.
• With increase in temperature pH value decreases. At higher temperature, the extent of ionisation
increases and H+ ion concentration increases. There fore pH value decreases.
Similarly OH– ion concentration also increases and pOH decreases and thus the entire pH scale
contracts.
• If [H+] ion concentration is increased by 10n times pH value decreases by n units.
• If [H+] ion concentration is decreased by 10n times pH value increases by n units.
• If acid solution is diluted by 10n times, pH value increases by n units.
8
Acids and Bases

• n H
If basic solution is diluted by 10 times, p value decreases by n units.
• PH of weak acids and weak bases :
Ionisation of weak acid(HA) :
HA H+ + A–
C00
C – Cα Cα Cα
Cα.Cα α 2C
Ka C − Cα (1 − α ) = α C (∵ α is very less)
= 2
=
Ka = α2C; α2 = Ka / C
Ka ⎛1 ⎞
α= = K a .V = ⎜ = v ⎟
C ⎝ c ⎠
Ostwald’s law of dilution explains the variation of degree of ionisation with concentration. The degree of
ionisation is inversely proportional to its square root of its concentration (or) directly proportional to
square root of its dilution.
[H+] = Cα
ka
[H+] = C ; [H+] = K a .C
C
log [H+] = log K a .C
1 1
log[H+] = log K a + log C
2 2
• Ostwald’s law of dilution is applicable for weak electrolytes (weak acid and weak base) it is not
applicable to strong electrolytes because they completely ionise at moderate concentration.
• The behaviour of strong electrolytes is explained by Debye – Huckel’s theory.
1 1
– log [H+] = – log k a − log C
2 2
1 1
pH = pk a − log C
2 2
• Ionisation of weak bases (MOH) :
MOH M+ + OH–
C 00
(C – Cα) Cα Cα
Cα x Cα
Kb =
C − Cα
α 2C
Kb = ( ∵ α is very less)
(1 − α )
Kb
K b = α 2C ; α2 =
C
Kb ⎛1 ⎞
α= ⇒ α = K b. v ⎜ = v ⎟
C ⎝c ⎠
Kb
[OH − ] = Cα = C
C
[OH − ] = K b .C
1 1
− log[OH] − = − log K b − log C
2 2
Acids and Bases

1 1
p OH = p K b − log C
2 2
pH = K w − pOH
1 Kb 1
pH = k w − p + log C
2 2
For weak acids :
[H + ] = Cα ; [H + ] = K a. C
Κa
α=
C
For weak bases :
[OH − ] = Cα ; [OH − ] = K b .C
Kb
α=
C
For strong acids ; [H+] = N of acid
For weak acids ; [H+] < N of acid
For strong bases; [OH–] = N of base
For weak bases; [OH–] < N of base
• Buffers : The solutions which maintain constant pH value on addition of acid or base.
• Resisting change in pH value on adding acid or base to a buffer is called Buffer action.
• Buffers posses reserve acidity and reserve alkality. Reserve acidity will nullify the effect of added base
and reserve basicity will nullify the effect of added acid.
• Blood buffer is H2CO3 + NaHCO3.
Types of buffers:
1) Acid buffers: It is the mixture of weak acid and it’s salt of strong base.
CH3COOH + CH3COONa
H2CO3 + NaHCO3
Tetra boric acid + Borax → [pH > 7]
H3PO4 + NaH2PO4
The pH of acid buffers is usually less than 7 but not always.
2) Basic buffers: It is mixture of weak base and its salt of strong acid.
NH4 OH + NH4Cl
Glycine + Glycine hydro chloride
3) Normal salt of weak acid and its acidic salt
Na2CO3 + NaH CO3
Na3PO4 + Na2HPO4
4) Salt of weak acid and weak base
Eg : CH3COONH4 ; HCOONH4
5) Ampholytes Amino acids proteins :
Which of the following can act as buffer
• Action of Acid buffers:
Eg : CH3COOH + CH3COONa
Acetic acid mostly remains as unionised and sodium acetate is almost completely ionised. Therefore the
components present in the above buffer are
10
Acids and Bases

– +
(CH3COOH+CH3COO + Na )
If little strong acid (H+) is added to the above buffer, the added strong acid will convert into weak acid.
Thus the effect is nullified.
CH3COO– + H+ → CH3COOH
If little strong base (OH–) is added to buffer, the added strong base is converted into water (H2O). Thus
the effect of added base is nullified.
CH3COOH + H– → CH3COO– + H2O
Thus acid buffer can resist change in pH on addition of little amount of acid or little amount of base.
In the above buffer the reserve acidity is due to CH3COOH and reserve basisity is due to CH3COO–.
• Action of Basic buffer :
Eg : NH4OH + NH4Cl
NH4OH ionizes to very small extent and NH4Cl being a salt ionizes completely. Therefore the
components present in the above buffer are [NH4OH + NH+4 + Cl–]
The reserve acidity of the above buffer is due to NH+4 and reserve bascity is due to NH4OH.
• If strong acid [H+] is added to buffer, it is converted into H2O
H+ + NH4OH → NH+4 + H2O
• If strong base [OH–] is added to buffer, it will convert into weak base
NH+4 + OH– → NH4OH
Thus an acid buffer or a basic buffer can maintain constant pH value by adding acid as well as base.
• PH of Buffers : [Henderson’s equation]
Deriving pH expression for Acid buffer :
HA H+ + A–
(weak acid)
[H + ][ A − ]
Ka =
[HA ]
K a [HA ]
[H+ ] =
[A − ]
⎡ Acid ⎤
[A − ] = K a ⎢ ⎥
⎣ Salt ⎦
[∵ most of the A– concentration comes from salt ]
By applying – log on both sides.
⎡ Acid ⎤
− log[H + ] = − log K a − log⎢ ⎥
⎣ salt ⎦
⎡ Acid ⎤
p H = p K a − log⎢ ⎥
⎣ salt ⎦
⎡ salt ⎤
p H = p K a + log⎢ ⎥
⎣ acid ⎦
• Deriving pH expression for basic buffer :
BOH B+ + OH–
(weak base)
[B + ] [OH − ]
Kb =
[BOH]
11
Acids and Bases

− [BOH]
[OH ] = K b
[B + ]
⎡ base ⎤
[OH − ] = K b ⎢ ⎥
⎣ salt ⎦
[∵ most of the B+ concentration come from salt]

By applying – log on both sides
⎡ base ⎤
− log[OH] − = − log K b − log⎢ ⎥
⎣ salt ⎦
⎡ base ⎤
pOH = pK b − log⎢ ⎥
⎣ salt ⎦
⎡ salt ⎤
pOH = pK b + log⎢ ⎥
⎣ base ⎦
pH = 14 − pOH
⎡ salt ⎤
pH = pK ω − pK b − log⎢ ⎥
⎣ base ⎦
⎡ salt ⎤ ⎫
p H = p K a + log⎢ ⎥ ⎪
⎣ acid ⎦ ⎪
⎬ [Henderson' s equation]
⎡ salt ⎤ ⎪
p OH = p K b + log⎢ ⎥
⎣ base ⎦ ⎭⎪
• Buffer capacity :
It is the capacity of a buffer to resist change in pH by adding acid or base.
• A good buffer shows only a slight change in pH on addition of acid or base.

• Buffer capacity is defined as the number of moles of acid or base added per litre of buffer to cause the
change in its pH by one unit
(or)
Buffer capacity is the ratio of number of moles of acid or base added per litre of buffer to the change in
pH
Buffer capacity =
no.of mole of acid or base added per litre of buffer
change in p H
• pH range of buffer :
It is the range of pH values where a buffer can effectively resist the change in pH on adding acid or base.
• For an acid buffer the pH range.
pH = pK a ± 1
For example PK a of CH3COOH + CH3COONa buffer is 4.5. Therefore it functions effectively between pH
values 3.5 and 5.5.
• The pH range of basic buffer.
pOH = pK b ± 1
• Buffer capacity will maximum if pH=pKa:[salt] =[acid]
Buffer capacity will be more if the components are taken in higher concentrations.
• Any buffer has a definite pH values. The pH of buffer does not change on long standing.
• The pH of buffer does not change on dilution.
12
Acids and Bases

Applications of buffers :
1) Buffers are used in various chemical industries
2) Buffers are used in various enzyme catalyses reaction.
3) used in softening of hard water.
4) used in various research programmes.
5) used in chemical analysis. [precipitation of radicals]
• Salt of Hydrolysis :
neutralisation
Acid + base salt + H2O
salt hydrolysis
Salt hydrolysis is endothermic because t is reverse of neutralisation.

• The reaction of the salt with water to produce acid or base or both is called salt hydrolysis.
• Salt hydrolysis is of three types.
1) Cationic hydrolysis : Cation of the salt reacts with water to produce H+ ions.
Eg: NH4Cl, NH4NO3, [NH4]2SO4 , AlCl3 etc.
In these salts cation is stronger because it is the conjugate of weak base therefore they undergo
cationic hydrolysis.
Eg: NH4+ Cl − : NH+4 + H2O NH4OH + H+
2) Anionic Hydrolysis : Anion of the salt reacts with water to produce OH–.
Eg: CH3COONa, HCOOK, Na2CO3, etc.
In these salts anion is stronger as it is the conjugate of weak acid.
Eg: CH3COONa+ :
CH3COO– + H2O CH3COOH + OH–
3) Cationic and Anionic hydrolysis : Both cation and anion of the salt react with water to produce H+
and OH– ions. Therefore the solution is neutral.
Eg: CH3COONH4, HCOONH4, Al(CH3COO)3
In these salts both cation and anion are stronger because they are the conjugates of weak base and
weak acid respectively.
Eg: CH3COO NH +4 :
CH3OO– + H2O CH3COOH + OH–
NH +4 + H2O NH4OH + H+
there are four types of salts depending on the nature of acid and base involved in the titrations.
• Salt of strong acid and weak base :
Eg: NH4Cl, NH4NO3, (NH4)2SO4, AlCl3 , MgCl2, Al2(SO4)3 etc,…
• These salts undergo cationic hydrolysis to produce H+ ions.
• Their aqueous solution is acidic and pH is less than 7.
• Their aqueous solution will turn blue litmus to red and they can be used for titrating against bases.
Eg: NH4+Cl−
Hydrolysis : NH+4 +H2O NH4OH + H+
[NH4OH] [H+ ]
K=
[NH4+ ] [H2O]
[NH 4 OH] [H + ]
K.[H 2 O] =
[NH +4 ]
13
Acids and Bases

+
[NH4OH][H ]
Kh =
[NH+4 ]
Ionisation of
NH4OH : NH4OH NH+4 +OH–
[NH +4 ][OH − ]
Kb =
[NH 4 OH]
Ion product of water = kω = [H+] [OH–]
K w [H+ ] [OH− ] [NH4OH]
=
Kb [NH+4 ] [OH− ]
Kw
Kh =
Kb
The degree of hydrolysis of the salt is inversely proportional to the square root of its molar
concentration.
Kb Kw
α= ⇒
C K b .C
[H+] = Cα
Kw
[H+] = C
K b .C
K w .C
[H+] =
Kb
Appling – log on both sides
1 1 1
− log[H + ] = − log K w − log C + log K b
2 2 2
1 Kw 1 K b 1
p = p − p − log C
H
2 2 2
• Salt of weak acid and strong base :

Eg: CH3COONa, HCOOK, Na2CO3, NaHCO3, Na3PO4, Na2HPO4, KCN etc.
Anionic hydrolysis : CH3COONa
[CH3COOH] [OH− ]
K=
[CH3OO− ] [H2O]
[CH3COOH] [OH− ]
K[H2O] =
[CH3COO− ]
[CH3COOH] [OH− ]
Kh =
[CH3COO− ]
Ionisation of CH3COOH :
CH3COOH CH3COO– + H+
[CH3COO− ] [H+ ]
Ka =
[CH3COOH]
ionic product of water : Kw = [H+] [OH–]
Kw [H + ] [OH − ] [CH 3 COOH]
=
Ka [CH 3 COO − ] [H + ]
14
Acids and Bases

K
Kh = w
Ka
The degree o hydrolysis of these salts is also inversely proportional to the square root of its
concentration.
kh kw
α= ⇒
C k a .C
[OH ] = C
− Kw
K a .C
⇒
K w .C
Ka
applying – log on both sides
1 1 1
− log[OH − ] = − log K w + log K a − log C
2 2 2
1 1 1
pOH = pK w − pK a − log C
2 2 2
• aqueous solution of these salts are basic they undergo anionic hydrolysis because the anion of the salt
is stronger as it is the conjugate of weak acid.
[OH–] is produced and solution is basic.
• Salt of weak acid and weak base :
Eg: CH3COONH4, HCOONH4, NH4CN, Al(CH3COO)3 etc…
• The aqueous solution of these salts is all most neutral and pH is all most equal to 7.
• The nature of the salt solution actually depends on Ka and Kb values of acid and base.
i) If Ka = Kb, solution is exactly neutral.
Eg: CH3COONH4
Ka of CH3COOH = Kb of NH4OH
ii) If Ka > Kb, solution is acidic
Eg: HCOONH4
Ka of HCOOH > Kb of NH4OH
iii) If Ka < Kb, solution is basic
Eg: Mg(CN)2
Kb of Mg(CN)2 > Ka of HCN
• These salts will undergo both cationic and anionic hydrolysis to produce both H+ and OH– ions.
Eg: CH3COONH4
NH+4 + H2O NH4 OH + H+
[CH 3 COOH] [NH 4 OH] [H + ] [OH − ]
K=
[CH 3 COO − ] [NH 4+ ] [H 2 O] 2
[CH 3 COOH] [NH 4 OH] [H + ] [OH − ]
K[H 2 O] 2 =
[CH 3 COO − ] [NH +4 ]
[CH 3 COOH] [NH 4 OH] [H + ] [OH − ]
Kh =
[CH 3 COO − ] [NH +4 ]
The [H+] = [OH–] they get cancelled mutually
[CH 3 COOH] [NH 4 OH]

Kh =
[CH 3 COO − ] [NH +4 ]
15
Acids and Bases

+ –
ionic product of water Kw = [H ] [OH ]
[CH 3 COO − ] [H + ]
Ka =
[CH 3 COOH]
[NH 4+ ] [OH − ]
Kb =
[NH 4 OH]
Kw [H + ][OH − ] [CH 3 COOH][NH 4 OH]
=
K a .k b [CH 3 COO − ] [H + ] [NH 4+ ] [OH − ]
Kω [CH3 COOH] [NH 4 OH]
=
K a .k b [CH3 COO − ] [NH +4 ]
Kw
Kb =
K a .K b
• The degree of hydrolysis [α] is independent of concentration of the salt because both cation and anion
of the salt are stronger as they are conjugate of weak base and weak acid respectively.
Kw
α= Kh ⇒
K a .K b
Kw K w .K a
[H + ] = K a .α ⇒ K a ⇒
K a .K b Kb
apply - log on both sides
1 1 1
− log[H + ] = − log K a − log K a + log K b
2 2 2
1 1 1
pH = pK w + pK a − pK b
2 2 2
[OH − ] = Kb α
.
kw k w × kb
= Kb =
k a .k b ka
apply – log on both sides
1 1 1 1 1 1
− log[OH − ] = − log k w − log k b + log k a p OH = p kw + p k b − p k a
2 2 2 2 2 2
• Salt of strong acid and strong base :
Eg: NaCl, KNO3, Na2SO4, BaCl2, NaClO4, Ba(NO3)2, Sr.(NO3)2 etc.
• These salts do not undergo hydrolysis because both anion and cation are weak as they are conjugates
of strong acid and strong base respectively.
• Therefore their aqueous solutions are exactly neutral and pH is exactly.
• 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 is given by
⎯⎯
Ax By ←⎯→ xA+ y + yB − x
⎯
x y
+y
∴K = ⎡ A ⎤ . ⎡ B− x ⎤
SP ⎢⎣ ⎥⎦ ⎢⎣ ⎦⎥
Ksp = [ xs ] [ ys ]
x y
16
Acids and Bases

• If solubility is known K SP can be calculated (or) vice versa.
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 is saturated
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.
5) In salting out of soap.
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
1/3
K SP ⎛K ⎞
S= 3 (or) S = ⎜ SP ⎟
4 ⎝ 4 ⎠
For 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
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
According to Lechatlier principle ⎡⎣ H ⎤⎦ , decreases P is increases and equilibrium shifts to left hand
+ H
3.
side.
APPLICATIONS : -
+
1) It is used in the controlling the H ion concentration in Buffer solution.
2− −
2) The concentration of S 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
17

06.acids and Bases 93-116

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6. ACIDS AND BASES

Acids and Bases

• Conjugate acid – base pairs :

Acids and Bases

Acids and Bases

Cl − + AlCl3 → [Cl − AlCl3 ] or AlC l −4

• Types of Lewis acids :

Acids and Bases

• 5) Molecules in which the central atom with sextet configuration

• Types of Lewis bases :

IONISATION OF ACIDS AND BASES AND DEGREE OF IONISATION

Acids and Bases

The dissociation constant of acid

α = degree of ionisation of base

Acids and Bases

• Comparison of acid – base theories :

Acids and Bases

For any dilute solution; [H+] [OH–]= 10–14 mol2/ litre2

Acids and Bases

Acids and Bases

Acids and Bases

Acids and Bases

[∵ most of the B+ concentration come from salt]

• A good buffer shows only a slight change in pH on addition of acid or base.

Acids and Bases

Salt hydrolysis is endothermic because t is reverse of neutralisation.

Acids and Bases

• Salt of weak acid and strong base :

Acids and Bases

[CH 3 COOH] [NH 4 OH]

Acids and Bases

Acids and Bases

COMMON ION EFFECT :-

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