Buffers

A buffer is a solution that minimizes changes in pH when small amounts of acids or alkalis are added to it.
Acidic Buffers
An acidic buffer is a mixture of a weak acid and its conjugate base. Eg. Ethanoic acid (CH 3COOH) and its
conjugate base, ethanoate (CH3COO-)
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
If H+ ions are added to this buffer, they will react with the ethanoate (the conjugate base) and be removed, so the
pH of the solution will only fall a little.
CH3COO- + H+ ⇌ CH3COOH(aq)
If OH- is added, it will react with the ethanoic acid
CH3COOH + OH- ⇌ CH3COO- + H2O

The Henderson-Hasselbalch equation to determine the pH of an acidic buffer is calculated from the equation:
Ka = [H3O+] [A-]
[HA]
Rearranging [H3O+] = Ka [HA]/[A-]
Determining the -log of each term gives:
pH = pKa + log [A-]/[HA] Henderson-Hasselbalch Equation

Since the salt (ethanoate in this example), which is ionic is completely ionized and the acid (ethanoic acid) only
slightly ionized since it’s a weak acid, we can assume that all the anions come from the salt and put
[A-] = [Salt]
[HA] = [Acid]
Therefore, pH = pKa + log [salt]/[acid]

Example: Three solutions contain ethanoic acid (Ka = 1.80 x 10-5 moldm-3) at a concentration of 0.1moldm-3 and
sodium ethanoate at a concentration of (a) 0.1 moldm -3 (b)0.2 moldm-3 (c) 0.5 moldm-3. Calculate the pH values of
the three solutions.
(a) pH = pKa + log (b) pH = pKa + log (c) pH = pKa + log
[salt]/[acid] [salt]/[acid] [salt]/[acid]
= 4.75 + = 4.75 + = 4.75 +
log(0.10/0.10) log(0.20/0.10) log(0.50/0.10)
= 4.75 + log1.0 = 4.75 + log2.0 = 4.75 + log5.0
= 4.75 + 0 = 4.75 = 4.75 + 0.30 = 5.05 = 4.75 + 0.70 = 5.45
Basic Buffers
A basic buffer is a mixture of a weak base and its conjugate acid. Eg. Ammonia (NH 3) and its conjugate acid,
ammonium (NH4+)
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)
If acid is added, the hydrogen ions combine with the ammonia
NH3 + H+ ⇌ NH4+
If hydroxide ions are added, they combine with the ammonium ions (the conjugate acid)
NH4+ + OH- ⇌ NH3 + H2O
For a basic buffer
pH = pKw – pKb + log [base]/[salt]

Buffers in Biological Systems

The pH of the body is maintained at around 7.4 by three buffer systems.
1.Carbonic acid/hydrogencarbonate buffer in blood
H2CO3 ⇌ H+ + HCO3-
Carbonic acid concentration is controlled by respiration
H2CO3 is in equilibrium with dissolved CO2(aq)
H2CO3 ⇌ CO2(aq) + H2O
An increase in dissolved CO2 stimulates an increase in breathing and excess CO 2 is exhaled by the lungs.
CO2(aq) ⇌ CO2(g)

2. Phosphate Buffer System (dihydrogen phosphate/ hydrogen phosphate)

H2PO4- ⇌ H+ + HPO42-(aq)

3. Amino acids
Amino acids have an acidic -COOH group that acts as the proton donor and a basic amino (-NH 2) group that acts
as a proton acceptor. In solution, amino acids from doubly charged particles known as zwitterions, which act as
buffers.
Eg. Glycine (aminoethanoic acid): NH2CH2COOH→H3N+CH2COO-

If the pH is not maintained, blood would coagulate and enzymes would denature due to breakdown of bonds in
proteins. Acidosis (pH less 7.35) or alkalosis (pH more than 7.45) would also result.

Buffers Practice
1) What is a buffer?
a solution that minimizes changes in pH when small amounts of acids or alkalis are added to it

2) Explain how amino acids (H3N+CHRCOO-) would act as a buffer when excess H+ ions are present in the
blood.
H3N+CHRCOO- + H+ → H3N+CHRCOOH

3) Explain how the phosphate buffer system would reduce the effect of excess OH- in the blood.
H2PO4- + OH- → HPO42-(aq) + H2O

4) Citric acid behaves as a weak monoprotic acid of Ka = 7.24 x 10-4. Calculate the pH of a solution of 0.1M
citric acid and 0.1M sodium citrate. Ans: 3.14

5) Calculate the pH of a buffer solution formed when 40cm 3 of 1M nitrous acid (pKa =3.34) is added to
20cm3 of 1M sodium hydroxide solution.

6) Calculate the pH of a buffer solution made of 500mL of 0.01M CH 3COOH and 750mL of 0.02M
CH3COONa. (Ka = 1.8x 10-5)
7) Calculate the pH of the solution that results from the addition of 0.040 moles of HNO 3 to a buffer made
by combining 0.500 L of 0.380 M HC3H5O2 (Ka = 1.30 x 10¯5) and 0.500 L of 0.380 M NaC3H5O2.
Assume addition of nitric acid has no effect on volume. Ans: 4.7

8) Calculate the pH of a buffer solution made by dissolving 18.5g of propanoic acid (C 2H5COOH) and 12.0g
of sodium propanoate, C2H5COONa in water and then making the volume up to 250cm3. Ka = 1.35 x 10-5
moldm-3. Ans: 4.57
9) You need to produce a buffer solution that has a pH of 5.27. You already have a solution that contains
0.010 mol of acetic acid. How many moles of sodium acetate will you need to add to this solution? The
pKa of acetic acid is 4.75. Ans: 0.033 moles

10) What amount of sodium ethanoate (Mr = 82gmol-1) must be added to 1dm3 of ethanoic acid of
concentration 0.1M and Ka = 2 x 10-5 to produce a buffer solution of pH = 4.7? Ans: 8.2g
11) a) 350mL of 0.4M CH3COOH is mixed with 250mL of 0.5M CH3COONa. Calculate the pH of the system
given Ka = 1.8 x 10-5.

b) If 100ml of 0.5M NaOH is added, what is the pH of the solution?

12) a) Calculate the pOH of an acidic buffer solution made of 200mL of 0.015M HCN and 300mL of 0.012M
NaCN. (Ka = 1.85 x 10-5)

a) If 100 mL of 0.01M NaOH was added, what is the new pH of the buffer solution?
13) a) Calculate the pH of a buffer solution made of 250ml of 0.5M NH 3 and 400mL of 0.25M NH4Cl.
(Kb=1.84 x 10-4).

a) If 100 mL of 0.5M HCl is added to the buffer, what is the pH of the final solution?
 b) If instead of 100mL, 300mL of 0.5M HCl was added, what would be the pH of the final solution?

14) Calculate the pH of a basic buffer solution made of 350mL of 0.05M methylamine (CH 3NH2) and 250mL
of 0.06M CH3NH3+ solution. (Ka of its conjugate acid is 2.4 x 10-6)
15) What is the pH when 25.0 mL of 0.200 M of CH3COOH (pKa = 4.75) has been titrated with 35.0 mL of
0.100 M NaOH? Ans: 5.12

16) A solution containing 50.00 mL of 0.35 M acetic acid CH3COOH (pKa = 4.75) is being titrated with 0.70
M NaOH. Calculate the pH:
a. initially

b. After the addition of 5.00 mL of NaOH

cx

c. After the addition of a total volume of 12.50 mL NaOH

d. After the addition of a total volume of 25.00 mL of NaOH

 e. After the addition of 26.00 mL of NaOH

17) A solution containing 25.00 mL of 0.30 M methylamine CH3NH2 (Kb = 4.4 x 10-4) is being titrated with
0.60 M HCl. Calculate the pH:
a. Initially
 b. After the addition of 2.50 mL of HCl
w

c. After the addition of a total volume of 6.25 mL HCl

d. After the addition of a total volume of 12.5 mL of HCl

e. After the addition of 12.55 mL of HCl