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Acid Base Equilibrium Mr.V
Acid base theories Arrhenius Theory Brönsted – Lowry Theory Lewis acid – base Theory
Acid Base behaviour In this unit when ever we discuss acids and bases we study the behaviour of compounds when dissolved in water The solvent is all the time Water
Arrhenius Theory Acid- any substance that increases the hydronium (H3O+) ion concentration in neutral water.  (or H+ ions for simplicity) Base - any substance that increases the hydroxide (OH-) ion concentration in neutral water. The following pages shows some examples of acids and bases
Strong Acids = Ka is very large Perchloric acid HClO4 Hydroiodic acid HI Hydrobromic acid HBr Sulfuric acid H2SO4 Hydrochloric acid HCl Nitric acid HNO3 Memorise these examples
Weak Acid = Ka is very small at 25oC Sulfurous acid H2SO3 Ka = 1.2 x 10 -2 Hydrogen sulphate ion HSO4- Ka = 1.0 x 10-2 Phosphoric acid H3PO4 Ka = 7.1 x 10-4 Citric acid H3C6H5O7 Ka = 7.1 x 10-4 Nitrous acid HNO2 Ka = 7.1 x 10-4 Hydrofluoric acid HF Ka = 6.8 x 10-4 Formic Acid HCO2H Ka = 1.8 x 10-4
Weak Acids continued at 25oC Acetic acid HC2H3O3 Ka = 1.8 x 10-5 Carbonic acid H2CO3 Ka = 4.5 x 10-7 Hydrogen cyanide HCN Ka = 6.2 x 10-10 Ammonium ion NH4+ Ka = 5.7 x 10-10 Bicarbonate ion HCO3- Ka = 4.7 x 10-11 Water H2O Ka = 1.8 x 10-16
Arrhenius Bases Sodium hydroxide NaOH Ammonium hydroxide NH4OH Calcium hydroxide Ca(OH)2 (Lime water)
Kw and pH Water is weakly dissociated and the equilibrium can be shown like this H2O + H2O = H3O+ + OH H2O = H+ + OH- Kw = [H+][OH-] Kw = 10-14  at 250C for water  H2O = H++ OH- -x         +x      +x Kw = x2 x =                 = 10-7
pH pH = -log[H+] pOH = -log[OH-] For water pH = -log[10-7]         	        = - [-7log 1o]        	        = 7 Similarly pOH = 7 pH + pOH = 14 pOH = 14-pH pH    = 14 - pOH
Brönsted Lowry Theory An acid is a proton donor A base is a proto acceptor An amphoteric substance is one that can act both as an acid and a base. Amphoteric substances are proton acceptors or donors eg. H2O, HCO3-, etc.
Brönsted acids bases examples NH3 + H2O           NH4+      +     OH- base     acid           conjugate      conjugate                                 acid                base  HCl   +   H2O              H3O+    +        Cl-acid       base                conjugate      conjugate                                       acid                base
Ka – Dissociation constant of an acid The equilibrium constant for the dissociation for a weak acid that is an equilibrium mixture Eg. HA  + H2O                     H3O+ + A-
Kb = Dissociation constant of a base NH3(aq) + H2O                     NH4+(aq) + OH-(aq) CO32-(aq) + H2O                    HCO3-(aq) + OH-(aq) B (aq) +   H2O                     BH+(aq) +  OH- (aq)
pKa and pKb These expressions are analogous to the expression for pH. We derived it to express the concentrations in a more convenient way using whole numbers. pKa = -log Ka pKb = -log Kb Smaller value of pKa , stronger the acid Smaller value of pKb , stronger the base.
Ka and Kb for Conjugate acid – base pair For a conjugate acid base pair this is applicable. Ka x Kb = Kw HA                  H+ + A- A- + H2O                  HA  + OH-
Conjugate acid base pairs Ka x Kb
Relationships between Ka, Kb,Kw .
Calculations involving Ka Calculate the value of Ka for a specific acid from the [H+] or pH of a solution for which we also know the initial concentration of the acid Calculate the equilibrium concentrations of H+ and A- from the initial concentration of a specific weak acid and its Ka value
Calculations involving  Kb Calculate the value of Ka for a specific acid from the [OH-] or pOH of a solution for which we also know the initial concentration of the base or from pH as pOH = 14 - pH Calculate the equilibrium concentrations of [H+ ]or [OH-]from the initial concentration of a specific weak base and its Kb value (Or what is almost the same is calculating the pH or pOH from the values of Kb and initial concentration of base)
Hydrolysis of Ions There are many ionic salt’s that make the aqueous solution acidic or basic. The reaction of ionic salts with water is called “Hydrolysis of salts” Hydrolysis can be explained using Brönsted Lowry theory. If the conjugate acid or base is strong then there will be hydrolysis. Weak acids and bases produce strong conjugate bases and acids
Illustration of Hydrolysis A-  is a strong conjugate base  A-(aq)+ H2O      =       HA(aq) + OH- The dissociation constant for the hydrolysis in this case is Kb as one of the products is a base.
Hydrolysis of strong conjugate acid NH4+ + H2O = H3O+ + NH3 NH4+  is a strong conjugate acid therefore undergoes hydrolysis and the solution becomes more acidic or pH is lowered. Other positive metal ions that can undergo hydrolysis is Fe3+, Al3+ etc. ………………
Titration of weak acid Vs base Acetic acid Vs NaOH
Polyprotic acids examples H2SO4 H2CO3 H3PO4
Polyprotic acid For any diprotic acid the value of Ka1 > Ka2 It is easier to pull a H+ from a neutral molecule than an ion Ka1 is usually 104 to 105 times larger than Ka2.  Therefore the contribution of acidity due to the second or third proton is negligible and can be ignored. 
Calculating Ka from pH #1 Formic acid HCHO2 is a monoprotic acid. In a 0.100 M solution of formic acid, the pH is 2.38 at 25oC. Calculate Ka for formic acid at this temperature. Ans: Ka = 1.8x10-4
#1 Determine the [H+] ion concentration from pH Make Ice table sand substitute the concentration of H+ in the table and complete it to get the equilibrium concentration of HA, H+ and A- Use the values to determine the Ka for the acid.
Calculating [H+], pH from Ka for weak acid #2 The concentration of vinegar HC2H3O2 was found to be 0.75 M acetic acid, Calculate the value for the [H+] ion concentration and pH for this acid solution if Ka for acetic acid is 1.8 x 10-5
#2 Create an ice table initial concentration is 0.75 M for acetic acid. Change in concentration is –x,x and x respectively for HA, H+ and A- Since Ka is very small 0.75 –x can be taken as 0.75 and solve for x. X is the concentration of H+ use this value to calculate pH

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Acid Base Equilibrium

  • 2. Acid base theories Arrhenius Theory Brönsted – Lowry Theory Lewis acid – base Theory
  • 3. Acid Base behaviour In this unit when ever we discuss acids and bases we study the behaviour of compounds when dissolved in water The solvent is all the time Water
  • 4. Arrhenius Theory Acid- any substance that increases the hydronium (H3O+) ion concentration in neutral water.  (or H+ ions for simplicity) Base - any substance that increases the hydroxide (OH-) ion concentration in neutral water. The following pages shows some examples of acids and bases
  • 5. Strong Acids = Ka is very large Perchloric acid HClO4 Hydroiodic acid HI Hydrobromic acid HBr Sulfuric acid H2SO4 Hydrochloric acid HCl Nitric acid HNO3 Memorise these examples
  • 6. Weak Acid = Ka is very small at 25oC Sulfurous acid H2SO3 Ka = 1.2 x 10 -2 Hydrogen sulphate ion HSO4- Ka = 1.0 x 10-2 Phosphoric acid H3PO4 Ka = 7.1 x 10-4 Citric acid H3C6H5O7 Ka = 7.1 x 10-4 Nitrous acid HNO2 Ka = 7.1 x 10-4 Hydrofluoric acid HF Ka = 6.8 x 10-4 Formic Acid HCO2H Ka = 1.8 x 10-4
  • 7. Weak Acids continued at 25oC Acetic acid HC2H3O3 Ka = 1.8 x 10-5 Carbonic acid H2CO3 Ka = 4.5 x 10-7 Hydrogen cyanide HCN Ka = 6.2 x 10-10 Ammonium ion NH4+ Ka = 5.7 x 10-10 Bicarbonate ion HCO3- Ka = 4.7 x 10-11 Water H2O Ka = 1.8 x 10-16
  • 8. Arrhenius Bases Sodium hydroxide NaOH Ammonium hydroxide NH4OH Calcium hydroxide Ca(OH)2 (Lime water)
  • 9. Kw and pH Water is weakly dissociated and the equilibrium can be shown like this H2O + H2O = H3O+ + OH H2O = H+ + OH- Kw = [H+][OH-] Kw = 10-14 at 250C for water H2O = H++ OH- -x +x +x Kw = x2 x = = 10-7
  • 10. pH pH = -log[H+] pOH = -log[OH-] For water pH = -log[10-7] = - [-7log 1o] = 7 Similarly pOH = 7 pH + pOH = 14 pOH = 14-pH pH = 14 - pOH
  • 11. Brönsted Lowry Theory An acid is a proton donor A base is a proto acceptor An amphoteric substance is one that can act both as an acid and a base. Amphoteric substances are proton acceptors or donors eg. H2O, HCO3-, etc.
  • 12. Brönsted acids bases examples NH3 + H2O       NH4+     +     OH- base     acid           conjugate   conjugate                                 acid             base HCl + H2O       H3O+    +        Cl-acid    base              conjugate      conjugate                                       acid                base
  • 13. Ka – Dissociation constant of an acid The equilibrium constant for the dissociation for a weak acid that is an equilibrium mixture Eg. HA + H2O H3O+ + A-
  • 14. Kb = Dissociation constant of a base NH3(aq) + H2O NH4+(aq) + OH-(aq) CO32-(aq) + H2O HCO3-(aq) + OH-(aq) B (aq) + H2O BH+(aq) + OH- (aq)
  • 15. pKa and pKb These expressions are analogous to the expression for pH. We derived it to express the concentrations in a more convenient way using whole numbers. pKa = -log Ka pKb = -log Kb Smaller value of pKa , stronger the acid Smaller value of pKb , stronger the base.
  • 16. Ka and Kb for Conjugate acid – base pair For a conjugate acid base pair this is applicable. Ka x Kb = Kw HA H+ + A- A- + H2O HA + OH-
  • 17. Conjugate acid base pairs Ka x Kb
  • 19. Calculations involving Ka Calculate the value of Ka for a specific acid from the [H+] or pH of a solution for which we also know the initial concentration of the acid Calculate the equilibrium concentrations of H+ and A- from the initial concentration of a specific weak acid and its Ka value
  • 20. Calculations involving Kb Calculate the value of Ka for a specific acid from the [OH-] or pOH of a solution for which we also know the initial concentration of the base or from pH as pOH = 14 - pH Calculate the equilibrium concentrations of [H+ ]or [OH-]from the initial concentration of a specific weak base and its Kb value (Or what is almost the same is calculating the pH or pOH from the values of Kb and initial concentration of base)
  • 21. Hydrolysis of Ions There are many ionic salt’s that make the aqueous solution acidic or basic. The reaction of ionic salts with water is called “Hydrolysis of salts” Hydrolysis can be explained using Brönsted Lowry theory. If the conjugate acid or base is strong then there will be hydrolysis. Weak acids and bases produce strong conjugate bases and acids
  • 22. Illustration of Hydrolysis A- is a strong conjugate base A-(aq)+ H2O = HA(aq) + OH- The dissociation constant for the hydrolysis in this case is Kb as one of the products is a base.
  • 23. Hydrolysis of strong conjugate acid NH4+ + H2O = H3O+ + NH3 NH4+ is a strong conjugate acid therefore undergoes hydrolysis and the solution becomes more acidic or pH is lowered. Other positive metal ions that can undergo hydrolysis is Fe3+, Al3+ etc. ………………
  • 24. Titration of weak acid Vs base Acetic acid Vs NaOH
  • 25. Polyprotic acids examples H2SO4 H2CO3 H3PO4
  • 26. Polyprotic acid For any diprotic acid the value of Ka1 > Ka2 It is easier to pull a H+ from a neutral molecule than an ion Ka1 is usually 104 to 105 times larger than Ka2. Therefore the contribution of acidity due to the second or third proton is negligible and can be ignored. 
  • 27. Calculating Ka from pH #1 Formic acid HCHO2 is a monoprotic acid. In a 0.100 M solution of formic acid, the pH is 2.38 at 25oC. Calculate Ka for formic acid at this temperature. Ans: Ka = 1.8x10-4
  • 28. #1 Determine the [H+] ion concentration from pH Make Ice table sand substitute the concentration of H+ in the table and complete it to get the equilibrium concentration of HA, H+ and A- Use the values to determine the Ka for the acid.
  • 29. Calculating [H+], pH from Ka for weak acid #2 The concentration of vinegar HC2H3O2 was found to be 0.75 M acetic acid, Calculate the value for the [H+] ion concentration and pH for this acid solution if Ka for acetic acid is 1.8 x 10-5
  • 30. #2 Create an ice table initial concentration is 0.75 M for acetic acid. Change in concentration is –x,x and x respectively for HA, H+ and A- Since Ka is very small 0.75 –x can be taken as 0.75 and solve for x. X is the concentration of H+ use this value to calculate pH

Editor's Notes

  1. Explain what hydronium ion is.
  2. If HA is a weak acid then A- is a strong conjugate base and it will undergo hydrolysis this will make the solution more basic as OH- ions are produced.