Buffer Solutions

Function
Maintain a constant pH upon addition of small amounts
of either acid or base

Composition
Conjugate acid-base pairs, eg.
- weak acid & its salt (CH3CO2H & CH3CO2-); or
- weak base & its salt (NH3 & NH4+)

Buffer Range
pH range over which the buffer is effective
pH range = pK  1
2

Buffer Calculations
1. Henderson-Hasselbalch Equation
a) Weak acid & its salt (CH3CO2H & CH3CO2-)

[Salt]
pH = pKa + log
[Acid]

b) Weak base & its salt (NH3 & NH4+)

[Salt]
pOH = pKb + log
[Base]
2. Acid/Base Dissociation
Use the acid/base dissociation equilibrium and the ICE
table to solve for the [H3O+]/[OH-].
 Calculation of Buffer pH
Calculate the pH of a buffer composed of 1.062 M acetic
acid and 0.9984 M sodium acetate.
Ka(CH3CO2H) = 1.75 x 10-5

Solution using Henderson-Hasselbalch equation:

This a buffer composed of a weak acid & its salt, .:

pKa = -log Ka = - log(1.75 x 10-5) = 4.757

Using the H-H equation:

[Salt] 0.9984
pH = pKa + log = 4.757 + log = 4.730
[Acid] 1.062

3
Calculation of Buffer pH
Solution using Acid dissociation equation:
CH3CO2H ⇌ H 3 O+ + CH3CO2-
Initial [ ] 1.062 0.9984
Change -x +x +x
Equilib [ ] 1.062 - x +x 0.9984 + x

Using Ka expression to solve for x:

[H3O+] [CH3CO2-] (x)(0.9984 + x)
Ka = =
[CH3CO2H] (1.062 - x)
.: x = 1.86 x 10-5 = [H3O+]
Finally
pH = -log [H3O+] = -log (1.86 x 10-5) = 4.730
4
 Buffer Preparation
Preparation
1. Choose an acid/base whose pK is close to the
desired pH;
2. Choose the concentration of one of the
components then calculate the concentration of
the other component.

Choose a weak acid whose pKa is close to the pH desired,

.: which buffer system would you use to make a buffer of
pH = 7.15?
H3PO4(aq) + H2O(l) ⇌ H2PO4–(aq) + H3O+(aq) Ka,1 = 7.1 x 10-3
H2PO4–(aq) + H2O(l) ⇌ HPO42–(aq) + H3O+(aq) Ka,2 = 6.3 x 10-8
HPO42–(aq) + H2O(l) ⇌ PO43–(aq) + H3O+(aq) Ka,3 = 4.2 x 10-13
5
 Buffer Preparation Calculation
What mass of sodium formate (NaHCO2) must be added
to 1.00 L of a 0.123 M formic acid (HCO2H, pKa = 3.75) to
make a buffer solution for pH = 3.90?

Solution:
This a buffer composed of a weak acid & its salt, .: use
[Salt]
pH = pKa + log
[Acid]
Substituting & rearranging

[Salt]
log = pH - pKa = 3.90 - 3.75 = 0.15
[Acid]

6
 Buffer Preparation Calculation
Solution continued

[Salt]
= antilog (0.15) = 1.4
[Acid]

therefore
[Salt] = 1.4 x [Acid] = 1.4 x 0.123 M = 0.172 M

Calculate the mass of sodium formate:

mass = molarity x volume x molar mass
= 0.172 M x 1.00 L x 68.01 g mol-1
= 11.7 g

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 Addition of Acid or
Base to Buffers
Function - Maintain a constant pH upon addition of
small amounts of either acid or base

Calculate the pH of the formic acid/sodium formate

buffer prepared above, after the addition of 0.0050
moles of (a) HCl, and (b) NaOH. Assume no volume
change

Solution:
1. Addition of a strong acid/base  acid/base
neutralisation reaction;
2. Determine limiting reagent & calculate final
concentrations; and
3. plug values into H-H equation, and solve. 8
9

Addition of Acid or Base to

Buffers
 0

Addition
What is the pH if of Acid
we add ororBase
an acid base? to Buffers

Stoichiometry calculation:
consider acid-base neutralization reaction
and determine its effect on [HX] and [X-]

Equilibrium calculation OR H-H method:

Use Ka or H-H and new concentrations of
[HX] and [X-] to calculate H+
1

Buffer Calculation
Function - Maintain a constant pH upon addition of
small amounts of either acid or base

Calculate the pH of the formic acid/sodium formate

buffer prepared above, after the addition of 0.0050
moles of (a) HCl, and (b) NaOH. Assume no volume
change

Solution:
1. Addition of a strong acid/base  acid/base
neutralisation reaction;
2. Determine limiting reagent & calculate final
concentrations; and
3. plug values into H-H equation, and solve.
2

Buffer Calculation
Solution (a):
i) Acid/base neutralisation reaction:

HCl + NaHCO2 ➔ HCO2H + NaCl(aq)

Acid Base
HCl + NaHCO2 ➔ HCO2H
Initial conc. / M 0.005 0.172 0.123
final conc. / M 0 0.167 0.128

ii) H-H equation:

[Salt] 0.167
pH = pKa + log = 3.75 + log = 3.87
[Acid] 0.128
 Buffer Calculation
Solution (b):
i) Acid/base neutralisation reaction:

HCO2H + NaOH ➔ NaHCO2 + H2O(l)

Acid Base
HCO2H + NaOH ➔ HCO2-
Initial conc. / M 0.123 0.005 0.172
Final conc. / M 0.118 0 0.177

ii) H-H equation:

[Salt] 0.177
pH = pKa + log = 3.75 + log = 3.93
[Acid] 0.118