Topic 12: Acid-base Equilibria
Buffer Solutions
Lesson Objectives:
18. Know what is meant by the term ‘buffer solution’
19. understand the action of a buffer solution
20. be able to calculate the pH of a buffer solution given appropriate data
21. be able to calculate the concentrations of solutions required to prepare a
buffer solution of a given pH
24. understand the roles of carbonic acid molecules and hydrogencarbonate ions
in controlling the pH of blood
What is a buffer solution?
So they are used to make the pH of a solution
remain almost unchanged when small amounts of
acid or base are added.
“A buffer solution resists changes in
pH when small amounts of acid or
base are added.”
Buffer solutions are made by:
- Mixing equimolar solutions of a weak acid with its conjugate base
- Mixing equimolar solutions of a weak base with its conjugate acid
e.g.
Ethanoic acid is weak, so the position of equilibrium lies to the left:
CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)
Sodium ethanoate (conjugate base) fully dissociates:
NaCH3COO (aq) → Na+ (aq) + CH3COO– (aq)
So the buffer solution contains equimolar amounts of a weak acid and
its conjugate base.
CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq) q)
NaCH3COO (aq) → Na+ (aq) + CH3COO– (aq)
Weak acid and conjugate base buffer The mixture will almost entirely be
made up of the:
CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)
- undissociated CH3COOH molecules
NaCH3COO (aq) → Na+ (aq) + CH3COO– (aq) - CH3COO− ions from the salt
When a small amount of acid is added to the buffer:
The H+ ions will combine with the CH3COO– ions to form CH3COOH:
CH3COO– (aq) + H+ (aq) ⇌ CH3COOH (aq)
When a small amount of base is added to the buffer:
The OH– ions will combine with the undissociated ethanoic acid molecules:
CH3COOH (aq) + OH– (aq) → CH3COO– (aq) + H2O (l)
An alternative approach to making an acidic buffer solution is to take a weak
acid and add half as many moles of a strong base
E.g.
1.0 mol of ethanoic acid reacted with 0.5 mol of sodium hydroxide
This gives a mixture containing 0.5 mol of ethanoic acid and 0.5 mol of sodium
ethanoate.
This solution is a buffer because it contains equal amounts of a weak acid and
its conjugate base.
A weak acid-conjugate base buffer solution will have a
pH less than 7, which is calculated as follows…
Calculating the pH of buffer solutions
A buffer solution was made by mixing equal volumes of 1.00 mol dm-3 ethanoic
acid and 1.00 mol dm-3 sodium ethanoate at 298K. Ka = 1.74 x 10-5 mol dm-3 .
We assume that the extent of dissociation of the weak acid is negligible so the
concentration of CH3COOH is 1.00 mol dm-3.
We assume that the dissolving of the sodium ethanoate is complete so the
concentration of CH3COO– is 1.00 mol dm-3.
Since we are mixing the two solutions together, the volume will double
∴ the concentration of each solution will be halved…
Calculating the pH of buffer solutions
A buffer solution was made by mixing equal volumes of 1.00 mol dm-3 ethanoic
acid and 1.00 mol dm-3 sodium ethanoate at 298K. Ka = 1.74 x 10-5 mol dm-3 .
As the concentration has halved due to mixing the solutions, we can express
them as follows:
To calculate the pH we use Ka to find [H+]:
[CH3COOH] = 0.500 mol dm-3
Ka = [CH3COO ] [H ]
– + rearranged
[CH3COO– ] = 0.500 mol dm-3
[CH3COOH] [H+] = Ka x [CH3COOH]
[CH3COO– ]
pH = -log(1.74 x 10-5) [H+] = 1.74 x 10-5 x 0.500
= 1.74 x 10-5 mol dm-3
= 4.76 0.500
Weak base and conjugate acid buffer The mixture will almost entirely be
made up of the:
NH3 (aq) + H2O ⇌ NH4+ (aq) + OH- (aq)
- unprotonated NH3 molecules
NH4Cl (aq) → NH4+ (aq) + Cl– (aq) - NH4+ ions from the salt
When a small amount of acid is added to the buffer:
The H+ ions will combine with the NH3 molecules to form NH4+:
NH3 (aq) + H+ (aq) ⇌ NH4+ (aq)
A weak base-conjugate
When a small amount of base is added to the buffer: acid buffer solution will
The OH– ions will take a proton from the NH4+ ions: have a pH greater than 7
NH4+ (aq) + OH– (aq) → NH3 (aq) + H2O (l)
Checking our understanding…
Carbonic acid is a weak acid with the formula H2CO3.
What other reactant would be needed to make a buffer solution with a pH < 7?
State the relative quantities of each species used.
H2CO3 (aq) ⇌ HCO3– (aq) + H+ (aq)
(equal molar ratios)
NaHCO3 (aq) → Na+ (aq) + HCO3– (aq)
or
H2CO3
NaOH (half as many moles as the acid)
Making a buffer solution with a specific pH…
How can we produce a buffer solution with a pH of 5.00 at 298K using
ethanoic acid (Ka = 1.74x10-5 mol dm-3)?
The [H+] needed will be 10-5.00 = 1.00 x 10-5 mol dm-3
Ka = [CH3COO– ] [H+] Rearranged [H+] = Ka x [CH3COOH]
[CH3COOH] [CH3COO–]
Inputting the values gives us the concentration ratio needed:
[CH3COOH] [CH3COOH]
1.00 x 10-5 = 1.74x10-5 x = 0.575
[CH3COO–] [CH3COO–]
So we combine equal volumes of 0.575 mol dm-3 of acid and 1.00 mol dm-3 salt
So we combine equal volumes of 0.575 mol dm-3 of acid and 1.00 mol dm-3 salt
[CH3COOH]
= 0.575 0.575 / 2 1.00 / 2
[CH3COO–] = 0.2875 mol dm-3 = 0.500 mol dm-3
Putting in the numbers gives the
Remember that we are combining two same ratio:
[0.2875]
solutions of equal volume, so their = 0.575
concentrations will be halved upon [0.500]
mixing…
When concentrations are fixed we have to calculate the ratio of volumes...
In what proportions would 0.100 mol dm-3 solutions of ammonia and
ammonium chloride need to be mixed to produce a buffer solution of pH 9.80?
Ka = 5.62 x 10-10 mol dm-3
Ka = [NH3] [H+] Rearranged [NH3] 5.62 x 10-10
= 5.62 x 10-10 mol dm-3 =
[NH4+] [NH4+] [H+]
[H+] = 10-9.80 = 1.58 x 10-10 mol dm-3
[NH3] 5.62 x 10-10
Inputting the values gives us the volume ratio: = = 3.56
[NH4+] 1.58 x 10-10
So we mix equal concentrations in the ratio 3.56 NH3 : 1.00 NH4+ dm3
When the volume of the weak acid and conjugate base (or vice versa for bases) are in
equimolar amounts, pH = pKa
We saw this relationship at the half-equivalence
point for titration curves…
Since we know the following relationship: [H+] = Ka x [CH3COOH]
[CH3COO–]
Equal amounts of the weak acid and conjugate base will result in them
cancelling out….
So [H+] = Ka and therefore ‘– log’ of both sides gives:
pH = pKa
pH = pKa at equimolar amounts of weak acid and conjugate base.
Controlling the pH of blood
The pH of blood and cells are controlled by buffers.
One such example is a carbonic acid-hydrogen carbonate buffer mixture.
H2CO3 (aq) HCO3– (aq)
Interestingly, there is usually 20x more HCO3– in blood because normal
metabolism tends to produce more acids than bases.
Controlling the pH of food
Microorganisms tend to thrive in pH values around 6.6-7.5.
This leads to greater multiplication and faster spoiling.
So buffers are used to ensure that the pH remains above or below these values.
Citric acid-sodium citrate buffers are a
common example used in jams…
