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• 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
Acids and Bases
••
[
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
4
Acids and Bases
Eg : CO2, SO2, SO3, NO2, N2O5, Cl2O7, P2O5
δ+ δ− ••
O = C = O + OH → O = C − O − or HCO3−
OH
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
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
6
Acids and Bases
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
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
9
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 ⎦
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
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
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
CH3COO– + H2O CH3COOH + OH–
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
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
⎯
+y x 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
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