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1. Solvent system
definition of acids and
bases
3RD SEM
BY SOURAV PAUL
(1)Some Facts
 Acid base properties are closely connected with the properties of solvents.
 Solvent system definition applies in all cases where the solvent is capable of
autoionization whetherprotons are involved or not , i.e aprotic as well as
protic solvent .
 Protic Solvent : protic solvent contains ionizable proton. (Eg- H₂O, HF)
 Aprotic Solvent: aprotic solvent not have any ionizable proton. (Eg-
CCl₄,DMF,DMSO,THF)
 According to the solvent system definition -
1. Acid is a substance that can generate the same cation as does the solvent
itself due to autoionization .
2. Similarly, Base can generate the anion part .
(2)Theory of autoionization
 Studies on certain nonaqueous system, reveled that reactions in these solvents may be
explained by assuming auto-ionization of the solvent similar to water :
 Substance furnishing H₃O⁺ ions in water act as acids in aqueous medium
 Substance furnishing NH₃⁺ ion In liquid ammonia behaves as an acid
 Similarly, substance furnishing NH₄⁻ ion in liquid ammonia are similar to those the
compounds giving OH⁻ ion in water.
1. Acids in liquid ammonia –NH₄Cl NH₄NO₃ etc.
2. Bases in liquid ammonia –KNH₂ NaNH₂ etc.
Examples of Autoionization
 Other examples :
Autoionization of SO₂:
Acid in SO₂:
SOCl₂ → SO²⁺ + 2Cl⁻
Base in SO₂:
CaSO₃ → Ca²⁺ + 2SO₃²⁻
Neutralization :
SOCl₂ +CaSO₃ → CaCl₂+2SO₂
Geneal Formula of Autoionization
• AB +AB ⇌ A⁺ + AB₂⁻
• EXCEPTION
COCl₂ ⇌ COCl⁺ + Cl⁻
Acid:
AlCl₃+COCl₂ → COCl⁺ + AlCl₄
Base :
COCl₂ → Ca²⁺ + 2Cl⁻
NEUTRALISATION :
2COCl⁺AlCl₄⁻ + CaCl₂→Ca[AlCl₄]₂ + 2CaCO₂
(3)Strong and weak acid and bases
 Strong acids dissociates completely into ions in water
 HA (g or l) + H₂O (l) → H₃O⁺ (aq) + A⁻ (aq)
 Weak acids dissociates very slightly into ions in water
HA (aq) + H₂O (l) ⇌ H₃O⁺ (aq) + A⁻ (aq)
 acid dissociation constant
Kc = [H₃O⁺] [A⁻] /[H₂O] [HA]
Kc [H₂O] = Ka = [H₃O⁺] [A⁻] / [HA]
strong acid have higher [H₃O⁺] , larger Ka
weak acid have lower [H₃O⁺] , smaller Ka
**similarly we can also calculate Kb, Kb= [B⁺][OH⁻]/[BOH]
(4)Ionic products and nutral points
 For water as a solvent the ionic product is
Kw=[H₃O⁺] ×[OH⁻]
 At 25°C corresponding nutral point is Pᴴ =-log[H⁺]
= - 0.5 log [Kw]
 Ionic product of any solvent AB is
 AB + AB ⇌ A⁺ + AB₂⁻
 K(AB) = [A⁺]×[AB₂⁻]
 The neutral point is P(A) = -0.5 log [Kab] = 0.5 Pᵏᵃ
Ionic products and nutral points of
some non aqueous solvents:
(5)Demerits and Relativity of acidic
and basic character of CH₃COOH
 Behavior of CH₃COOH In H₂O NH₃ and HF:
 In water acetic acid behaves as a weak acid,
 In liquid ammonia acetic acid behaves as a strong acid,
 In HF asetic acid behaves as a base .
 Demerits:
1. It places too much emphasis on Autoionization of solvent,
ignoring other physical and chemical properties of solvents.
2. Acid-base reaction occuring in absence of any solvent
cannot define by it.
Thank You

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Solvent system definition of acids and bases

  • 1. 1. Solvent system definition of acids and bases 3RD SEM BY SOURAV PAUL
  • 2. (1)Some Facts  Acid base properties are closely connected with the properties of solvents.  Solvent system definition applies in all cases where the solvent is capable of autoionization whetherprotons are involved or not , i.e aprotic as well as protic solvent .  Protic Solvent : protic solvent contains ionizable proton. (Eg- H₂O, HF)  Aprotic Solvent: aprotic solvent not have any ionizable proton. (Eg- CCl₄,DMF,DMSO,THF)  According to the solvent system definition - 1. Acid is a substance that can generate the same cation as does the solvent itself due to autoionization . 2. Similarly, Base can generate the anion part .
  • 3. (2)Theory of autoionization  Studies on certain nonaqueous system, reveled that reactions in these solvents may be explained by assuming auto-ionization of the solvent similar to water :  Substance furnishing H₃O⁺ ions in water act as acids in aqueous medium  Substance furnishing NH₃⁺ ion In liquid ammonia behaves as an acid  Similarly, substance furnishing NH₄⁻ ion in liquid ammonia are similar to those the compounds giving OH⁻ ion in water. 1. Acids in liquid ammonia –NH₄Cl NH₄NO₃ etc. 2. Bases in liquid ammonia –KNH₂ NaNH₂ etc.
  • 4. Examples of Autoionization  Other examples : Autoionization of SO₂: Acid in SO₂: SOCl₂ → SO²⁺ + 2Cl⁻ Base in SO₂: CaSO₃ → Ca²⁺ + 2SO₃²⁻ Neutralization : SOCl₂ +CaSO₃ → CaCl₂+2SO₂ Geneal Formula of Autoionization • AB +AB ⇌ A⁺ + AB₂⁻ • EXCEPTION COCl₂ ⇌ COCl⁺ + Cl⁻ Acid: AlCl₃+COCl₂ → COCl⁺ + AlCl₄ Base : COCl₂ → Ca²⁺ + 2Cl⁻ NEUTRALISATION : 2COCl⁺AlCl₄⁻ + CaCl₂→Ca[AlCl₄]₂ + 2CaCO₂
  • 5. (3)Strong and weak acid and bases  Strong acids dissociates completely into ions in water  HA (g or l) + H₂O (l) → H₃O⁺ (aq) + A⁻ (aq)  Weak acids dissociates very slightly into ions in water HA (aq) + H₂O (l) ⇌ H₃O⁺ (aq) + A⁻ (aq)  acid dissociation constant Kc = [H₃O⁺] [A⁻] /[H₂O] [HA] Kc [H₂O] = Ka = [H₃O⁺] [A⁻] / [HA] strong acid have higher [H₃O⁺] , larger Ka weak acid have lower [H₃O⁺] , smaller Ka **similarly we can also calculate Kb, Kb= [B⁺][OH⁻]/[BOH]
  • 6. (4)Ionic products and nutral points  For water as a solvent the ionic product is Kw=[H₃O⁺] ×[OH⁻]  At 25°C corresponding nutral point is Pᴴ =-log[H⁺] = - 0.5 log [Kw]  Ionic product of any solvent AB is  AB + AB ⇌ A⁺ + AB₂⁻  K(AB) = [A⁺]×[AB₂⁻]  The neutral point is P(A) = -0.5 log [Kab] = 0.5 Pᵏᵃ Ionic products and nutral points of some non aqueous solvents:
  • 7. (5)Demerits and Relativity of acidic and basic character of CH₃COOH  Behavior of CH₃COOH In H₂O NH₃ and HF:  In water acetic acid behaves as a weak acid,  In liquid ammonia acetic acid behaves as a strong acid,  In HF asetic acid behaves as a base .  Demerits: 1. It places too much emphasis on Autoionization of solvent, ignoring other physical and chemical properties of solvents. 2. Acid-base reaction occuring in absence of any solvent cannot define by it.