21.
6 Buffer Solutions
Starter:
3. As water is always slightly ionised, we can write the following equilibrium for water;
H2O(l) ⇌ H+(aq) + OH–(aq) ΔH = +ive
As only a very small amount of the water is ionised, we define a new equilibrium constant for this equilibrium
called the ionic product of water, Kw;
Kw = [H+(aq)] [OH–(aq)]
Like any other equilibrium constant, the value of Kw depends on the temperature of the equilibrium.
(a) Predict what effect increasing the temperature will have on the pH of pure water. (1 mark)
(b) Calculate the pH of pure water (to 2 dp) at each of the temperatures below;
(i) 10 C, Kw = 0.29 × 10–14 mol2 dm–6
(ii) 25 C, Kw = 1.01 × 10–14 mol2 dm–6
(iii) 40 C, Kw = 2.92 × 10–14 mol2 dm–6 (3 marks)
(c)Complete the paragraph below;
As the temperature decreases, water becomes (more acidic / less acidic / remains neutral).
Explain your answer (2 marks)
21.6 Buffer Solutions
Starter:
3. As water is always slightly ionised, we can write the following equilibrium for water;
H2O(l) ⇌ H+(aq) + OH–(aq) ΔH = +ive
Kw = [H+(aq)] [OH–(aq)]
Like any other equilibrium constant, the value of Kw depends on the temperature of the equilibrium.
(a) Predict what effect increasing the temperature will have on the pH of pure water. (1 mark)
(b) Calculate the pH of pure water (to 2 dp) at each of the temperatures below;
(i) 10 C, Kw = 0.29 × 10–14 mol2 dm–6
(ii) 25 C, Kw = 1.01 × 10–14 mol2 dm–6
(iii) 40 C, Kw = 2.92 × 10–14 mol2 dm–6 (3 marks)
(c)Complete the paragraph below;
As the temperature decreases, water becomes (more acidic / less acidic / remains neutral).
Explain your answer (2 marks)
21.6 Buffer Solutions
Learning Objectives
• Define a buffer
• Explain how buffers work
• Calculate the pH of an acidic buffer solution
• Describe applications of buffer solutions
Key words: acid, base, titration, buffer, conjugate
base/acid, salt, equilibrium, neutralisation
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1.
–
Buffer solutions 1.
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pH
• Many biological systems (and industrial processes) can only occur at
correct pH (small margin)
• A Buffer solution is one which resists changes in pH when small
quantities of an acid or an alkali are added to it.
• Buffers enable pH to be regulated
pH 7.35-7.45
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Buffer Solutions
Buffer solutions are systems that minimise pH changes on the
addition of small amounts of an acid or base.
They are composed of weak acids and their conjugate bases:
HA ⇌ H+ + A-
HA and A- act as two independent reservoirs that are capable
of reacting with added alkalis or acids, respectively:
• The buffer is most effective when [HA] = [A-].
• The buffer is no longer effective when one of the
components is completely used up.
The pH of a buffer does vary slightly when reacting with any
added species, so shouldn’t be considered totally constant.
Le Chatelier
• If a dynamic equilibrium is disturbed by
changing the conditions, the position of
equilibrium moves to counteract the
change
Eg A + 2B C + D
Add more of anything or change the conditions
(temperature, pressure) equilibrium will change to
get back to where it was 6
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How Buffers Work
As buffers have two independent reservoirs, a reaction with
one will cause a shift in the equilibrium to negate the change:
Adding acid
HA ⇌ H+ + A-
Adding alkali
Addition of Acid: Addition of alkali:
1. [H+] increases 5. [OH-] increases
2. Conjugate base (A-) reacts 6. H+ reacts (H+ + OH- → H2O)
3. Equilibrium shifts left 7. Equilibrium shifts right
4. [H+] removed 8. HA dissociates restoring [H+]
Forming Buffers
There are three ways to form buffers:
1. Adding solutions of a weak acid and its conjugate salt. (pH<7)
• As the dissociation of weak acids is very low, the concentration of the acid
can assume to remain the same.
• As salts are ionic they completely dissociate in solution so provide a
concentration for the conjugate base.
eg ethanoic acid & sodium ethanoate
2. Adding solutions of a weak base and one of its salts (pH>7)
eg ammonia solution & ammonium chloride
3. Partial neutralisation of a weak acid.
• Add an alkali, e.g. NaOH(aq) to excess weak acid.
• This will neutralise some of the acid to form the conjugate base and
leaving some acid left over.
Weak acid and It’s Conjugate salt
e.g.Ethanoic acid & Sodium Ethanoate
• Ethanoic acid is a weak acid so...
• Equilibrium almost entirely to left
sodium ethanoate (a salt) is fully ionised
CH3COONa (aq) CH3COO- (aq) + Na+ (aq)
Concentration of ethanoate ion from CH3COONa far outweighs that
from dissociation of weak acid – equilibrium of acid is pushed 9
further to the left
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Ethanoic acid
& Sodium Ethanoate
• Ethanoic acid weak so equilibrium over to Left
• Adding Ethanoate pushes further over to Left
The solution will therefore contain these important things:
•lots of un-ionised ethanoic acid;
•lots of ethanoate ions from the sodium ethanoate;
•enough hydrogen ions to make the solution acidic.
•If H+ ions are added – they will combine with the ethanoate ions and so the pH
will hardly change.
•If OH- ions are added - they will react with the ethanoic acid to make
ethanoate ions and water.
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Partial neutralisation of a weak acid
e.g. Ethanoic acid and NaOH
• The same acid buffer is formed if sodium
hydroxide is added
Add NaOH – sodium ethanoate is formed
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H 2O (l)
Concentration of ethanoate ion from CH3COONa far
outweighs that from dissociation of weak acid –
equilibrium of acid is pushed further to the left
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If acid is added the equilibrium will move to the left to
reduce the concentration of H+ ions by reacting with
the CH3COO-
CH3COOH (aq) CH3COO- (aq) + H+ (aq)
If alkali is added the OH- will react with the H+ ions
and so the equilibrium will move to the right to
replace H+
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Weak Base and one of it’s Salts
Ammonia Solution & Ammonium Chloride
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
• Ammonia is a weak base so equilibrium over to Left
Ammonium chloride ionises fully in solution
NH4Cl (aq) NH4+ (aq) + Cl- (aq)
Concentration of ammonium ion from NH4Cl far outweighs that from
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dissociation of weak base – equilibrium of base is pushed further to
the left
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Weak Base and one of it’s Salts
Ammonia Solution & Ammonium Chloride
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
• Weak base so not much ionisation (Equilibrium over to
left)
NH4Cl (aq) NH4+ (aq) + Cl- (aq)
This solution contains:
Lots of unreacted ammonia
Lots of ammonium ions (mainly from ammonium chloride)
Enough hydroxide ions to make the solution alkaline. 14
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If acid is added the equilibrium will move to the left to
reduce the concentration of H+ ions and more
ammonium ions are made.
• NH4+ (aq) NH3 (aq) + H+ (aq)
If alkali is added the OH- will react with the
ammonium ions to make ammonia and water and so
the equilibrium will move to the right to replace H+
• NH4+ (aq) + OH- (aq) NH3 (aq) + H2O (l)
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Only small changes in pH
• If large amounts of alkali or acid are added this changes the pH
measurably.
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And now
The maths!
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For the reaction
• HA (aq) H+ (aq) + A- (aq)
• What is Ka ?
Ka = [H+] [A-] [H+] ≠ [A-]
[HA]
Nearly all the A- is from the salt
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Create a Different Equation
• HA (aq) H+ (aq) + A- (aq)
Acid is hardly dissociated so [HA] = concentration at start
Ka = [H+] [A-] = [H+] [salt at start]
[HA] [acid at start]
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EXAMPLE 1: Methanoic acid &
Potassium methanoate
• Methanoic acid (0.5 moldm-3)is a weak acid so
hardly dissociated...
• HCOOH (aq) HCOO- (aq) + H + (aq)
Potassium methanoate (2.5 moldm-3) is fully
ionised
HCOOK (aq) HCOO- (aq) + K+ (aq)
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Ka = 1.6 x 10 -4
moldm -3
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EXAMPLE 1: Methanoic acid &
ThesePotassium methanoate
Now almost all from
2 no longer equal
methanoate
concentrations
[H+] [HCOO-]
• Ka =
[HCOOH] Acid hardly ionised
[H+] [methanoate at start]
[acid at start]
pH = -log [H+]
1.6 x 10-4 = [H+] 2.5 = 4.5
0.5
[H+] = 1.6 x 10-4 x 0.5 = 3.2 x 10-5 mol dm-3 22
2.5
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EXAMPLE 2
Buffers & pH
The pH of a buffer depends on the weak acid that is used and
the concentration of each component in the buffer.
Buffers are most effective when [HA]=[A-] as pH = pKa.
The operating pH of a buffer will be ±1 pKa.
• e.g. pKa = 2.50, then operating pH = 1.50–3.50
RECAP: To calculate pH of a buffer the expression for Ka is
rearranged:
Ka = so [H+] = Ka x
Calculating pH of a buffer differs from a weak acid as weak
acids assume [H+]=[A-] but buffers have A- added so [H+]≠[A-].
1. Practice Q
• Calculate the pH of a buffer solution
of 0.500 mol dm-3 propanoic acid and
1.00 mol dm-3 sodium propanoate
Ka propanoic acid = 1.35 x 10-5 mol dm-3
Ka = [H+] [C2H5COO-]
Could they have used a buffer
[C2H5COOH] solution?
1.35 x 10-5 = [H+] x 1.00
0.500
[H+] = 1.35 x 10-5 x 0 .500 = 6.8 x 10-6 mol dm-3
25
pH = 5.17
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Example 3: Calculating pH of a Buffer Solution
What is the pH of a buffer formed when 75 cm3 of 0.15
mol dm-3 of a weak acid and 50 cm-3 of a 0.25 mol dm-3
solution of its salt are mixed?
• Ka = 2.51 x10-6 mol dm-3
1. Determine new concentrations:
• Acid = 75 cm3 ÷ 125 cm3 = 0.6 x 0.15 mol dm-3 = 0.09 mol dm-3
• Salt = 50 cm3 ÷ 125 cm3 = 0.4 x 0.25 mol dm-3 = 0.08 mol dm-3
2. Calculate [H+]:
• [H+] = Ka x = 2.51 x10-6 mol dm-3 x = 2.82 x10-6 mol dm-3
3. Calculate pH:
• pH = -log[H+] = -log[2.82x10-6] = 5.55
Example 4: Calculating pH of a Buffer Solution
What is the pH of a buffer formed by adding 50 cm3 of 0.10
mol dm-3 of NaOH to 50 cm3 of 0.25 mol dm-3 ethanoic acid
(CH3COOH)?
• Ka = 1.7 x10-5 mol dm-3
1. Determine moles of reactants:
• Acid = 0.25 mol dm-3 x 0.05 dm3 = 0.0125 mol
• Alkali = 0.10 mol dm-3 x 0.05 dm3 = 5 x10-3 mol = mol of salt
2. Calculate moles of acid remaining:
• 0.0125 mol – 5 x10-3 mol = 0.01245 mol of acid
3. Calculate acid and salt concentration in new volume:
• Acid = 0.1245 mol ÷ 0.1 dm3 = 0.1245 mol dm-3
• Salt = 5 x10-3 mol ÷ 0.1 dm3 = 0.05 mol dm-3
Example 4: Calculating pH of a Buffer Solution cont….
What is the pH of a buffer formed by adding 50 cm3 of 0.10
mol dm-3 of NaOH to 50 cm3 of 0.25 mol dm-3 ethanoic acid
(CH3COOH)?
• Ka = 1.7 x10-5 mol dm-3
4. Calculate [H+]:
• [H+] = Ka x = 1.7 x10-5 x = 4.233 x10-5 mol dm-3
5. Calculate pH
• pH = -log[H+] = -log[4.233x10-5] = 4.37
EXAMPLE 5
Henderson-Hasselbach Equation
• This puts all the calculation steps into one equation
pHbuffer = pKa – log [acid]
[salt]
What if [salt] = [acid] ?
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Half – Equivalence point
ff er
Bu Half-equivalence point
zone When half the acid has been
neutralised......
Amount of salt = amount of acid
formed remaining
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and pH = pKa
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Salt solutions
• Solutions of some salts are not neutral
The taste (bad or otherwise) because of the
flavouring – sodium ethanoate (acetate)
Also used in
as a buffer in petroleum production, a
retardant in plastic production and is an
intermediate in the production of dyes,
pigments, soaps and pharmaceuticals
Read more:
32
http://www.livestrong.com/article/261886-foo
ds-containing-sodium-acetate/#ixzz2QYcbBrqK
A2 3.9 Acid-Base Equilibria 18/08/2022
SALTS OF......
• Strong acid & strong base.... eg NaCl
Complete ionisation of salt – water slightly
dissociated but neither Na + nor Cl- react with
water pH = 7
H2O H+ + OH –
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SALTS OF......
• Strong acid & weak base....eg NH4Cl
• Complete ionisation of salt – water slightly dissociated so
acidic NH4+ reacts with water
NH4 + + H2O NH3 + H2O + H+
[ H+ ] > [ OH- ] so pH < 7
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SALTS OF......
• Weak acid & strong base....eg CH3COONa
• Complete ionisation of salt – water slightly dissociated basic
CH3COO- reacts with water
CH3COO - + H2O CH3COOH + OH -
[ H+ ] < [ OH- ] so pH > 7
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SALTS OF......
• Strong acid & strong base.... eg NaCl
Complete ionisation of salt – water slightly
dissociated but neither Na + nor Cl- react with
water pH = 7
Strong acid & weak base....eg NH4Cl
Complete ionisation of salt – water slightly dissociated
so acidic NH4+ reacts with water pH < 7
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Buffers: Video Support
