pH of Buffer Solutions

Kimia Dasar
Jurusan Fisika dan Biologi
Sri Kadarwati, Ph.D.
 What is a buffer solution?

A buffer solution is an aqueous solution consisting

of a mixture of a weak acid and its conjugate base,
or vice versa.
Its pH changes very little when a small amount of
strong acid or base is added to it.
Buffer solutions are used as a means of keeping pH
at a nearly constant value in a wide variety of
chemical applications.
 An example of buffer solution
In nature, there are many systems that use buffering for pH regulation. For example,
the bicarbonate buffering system is used to regulate the pH of blood.

The bicarbonate buffer system is an acid-base homeostatic mechanism

involving the balance of carbonic acid (H2CO3), bicarbonate ion (HCO3−),
and carbon dioxide (CO2) in order to maintain pH in the blood and duodenu,
among other tissues, to support proper metabolic function.

Catalyzed by carbonic anhydrase, carbon dioxide (CO2) reacts with water (H2O)
to form carbonic acid (H2CO3), which in turn rapidly dissociates to form
a bicarbonate ion (HCO3−) and a hydrogen ion (H+) as shown in the following
reaction
The pH is balanced by the presence of both a weak acid (for example, H2CO3) and
its conjugate base (for example, HCO3−) so that any excess acid or base
introduced to the system is neutralized.

Failure of this system to function properly results in acid-base imbalance,

such as acidemia (pH<7.35) and alkalemia (pH>7.45) in the blood.
 An example of buffer solution

If the pH value of a solution rises or falls too much, the effectiveness of an enzyme
decreases in a process, known as denaturation, which is usually irreversible. 
The majority of biological samples that are used in research are kept in a buffer
solution, often phosphate buffered saline (PBS) at pH 7.4.

In industry, buffering agents are used in fermentation processes and in setting

the correct conditions for dyes used in colouring fabrics.
They are also used in chemical analysis and calibration of pH meters.
 Principles of buffering
Buffer solutions resist pH change because of an equilibrium between the weak acid HA and its conjugate base
A−
HA ⇌ H+ + A−

When some strong acid is added to an equilibrium mixture of the weak acid and its conjugate base,
hydrogen ions (H+) are added, and the equilibrium is shifted to the left, in accordance with Le Châtelier's
principle. Because of this, the hydrogen ion concentration increases by less than the amount expected for the
quantity of strong acid added.

Similarly, if strong alkali is added to the mixture, the hydrogen ion concentration decreases by less than the
amount expected for the quantity of alkali added.

The pH changes relatively slowly in the buffer region, pH = pKa ± 1, where [HA] = [A−].
The hydrogen ion concentration decreases by less than the amount expected because
most of the added hydroxide ion is consumed in the reaction
OH− + HA → H2O + A−
and only a little is consumed in the neutralization reaction.
Some buffering agents

Universal buffer mixtures

N-Cyclohexyl-2-
aminoethanesulfonic
acid
 CALCULATING pH of buffers
Suppose we have:

Henderson-Hasselbalch Eq.
 Problem example -1
 a. A solution was prepared by dissolving 0.02 moles of acetic acid (HAc; pKa
= 4.8) in water to give 1 L of solution. What is the pH?
• Ka = 1.6 x 10-5
• pH = -log [H+]
b. To this solution was then added 0.008 moles of concentrated sodium
hydroxide (NaOH). What is the new pH? (In this problem, you may
ignore changes in volume due to the addition of NaOH).
o HAc + NaOH  NaAc + H2 O
o HAc + OH- ⇆ Ac- + H2O
0.02 mol 0.008 mol
0.008 mol 0.008 mol 0.008 mol 0.008 mol
0.012 mol 0 0.008 mol 0.008 mol
c. An additional 0.002 moles of NaOH is then added. What is the
pH?
The same reaction takes place:
HAc + OH- ⇆ Ac- + H2 O
0.012 mol 0.002 mol 0.008 mol 0.008 mol
0.002 mol 0.002 mol 0.002 mol 0.002 mol
0.010 mol 0 0.01 mol 0.01 mol
 What is next?

An additional 0.01 moles of NaOH is then added. What is the pH?

Sisa asam HAc dari soal b adalah 0.010 mol.

Jika ditambah basa sebanyak 0.010 mol maka semua HAc akan
bereaksi dengan basa NaOH  next discussion: hydrolysed salts
Hydrolysis of salts
Week 9
Sri Kadarwati, Ph.D.
What is a “salt”

o Composed of the negative ion of an acid and the positive ion of a base.
o One of the products of a Neutralization Reaction
o Acid + Base  Salt + Water  DOUBLE DISPLACEMENT
REACTION
HCl + Mg(OH)2  MgCl2 + H2O
Examples: KCl, NaCl, MgSO4 , Na3PO4

When dissolved in water, salts produce ions.

KCl (s)  K+(aq) + Cl-(aq)
The ions could REACT with water*  HYDROLYSIS
*term and condition applied: the ions must come from weak acids and/or weak
 Hydrolysis of salts
Hydrolysis only occur for the ions must come from weak acids and/or weak
bases
 COMMON RULE

Remember the production of H+ or OH- during the

hydrolysis of the ions coming from the weak acids/bases
Calculating the pH of salt solutions
1. Hydrolysis of Acidic Salts (from weak bases)

 
2. Hydrolysis of Basic
Salts (from weak acids)
 
3. Hydrolysis of Salts of
weak acids and weak
bases
A salt formed between a weak acid and a weak base can be neutral,
acidic, or basic depending on the relative strengths of the acid and base.

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 Example problems
1. Calculate the pH of a solution which is 0.010 M in NaOCN. The
Ka of HOCN is 3.5 x 10-4 .
 NaOCN  Na+ + OCN-
0.01 M 0.01 M 0.01 M

OCN- + H2O ⇆ HOCN + OH-

2. Calculate the pH of a solution which is 0.10 M in NH4Cl. The Kb
for NH3 is 1.8 x 10-5

 NH Cl  NH +
+ Cl -
4 4
0.1 M 0.1 M 0.1 M

NH4+ + H2O ⇆ NH4OH + H+

 3. If 100.0 mL of a solution is originally 0.10 M CH3COOH and one
adds exactly enough solid NaOH to neutralize this solution, what
would be the resultant pH of the solution? The Ka for CH3COOH is
1.8 x 10-5.
 CH COOH + NaOH  CH COONa + H2O
3 3
10 mmol 10 mmol initial
10 mmol 10 mmol 10 mmol reaction
0 0 10 mmol equilibrium
CH3COONa  CH3COO- + Na+
10 mmol 10 mmol 10 mmol (Remember: Vsolution = 200 mL; M = 0.05 M)

CH3COO- + H2O ⇆ CH3COOH + OH-

4. Calculate the pH of a solution which is 0.10 M in HOCN and 0.30
M in NaOCN. The Ka of HOCN is 3.5 x 10-4.
Pre- and post-laboratory activity
• Flow chart & pre-test
https://forms.gle/KWrbZtqPNhcTQsdX9
• Report
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