Chapter 17 Additional Aspects of Aqueous Equilibria
Tuesday, 15 April 2025 12:47
THE COMMON ION EFFECT
Consider a 0.10 M solution of acetic acid in water, at equilibrium.
CH3COOH(aq) ⇌CH3COO-(aq) + H+(aq)
Add CH3COONa (sodium acetate)
i.e., Na+ (aq) and CH3COO-(aq) ions.
According to Le Chatelier’s principle in which way is the equilibrium expected to shift?
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
There is an increase in [CH3COO-].
Therefore, equilibrium shifts to the left according to Le Chatelier’s principle.
H3O+ ions are used up and [H3O+] decreases.
The pH increases (less acidic).
The common ion is CH3COO- as it is in both acetic acid and sodium acetate.
Note: Na+ ions are spectator ions.
Acetic acid (CH3COOH) is a weak acid and ionises incompletely.
Sodium acetate (CH3COONa) is a strong electrolyte and dissociates completely.
They share a common ion CH3COO-.
The shift to the left due to the addition of CH3COONa solution means that the added
acetate ions cause the acetic acid to ionise less than it normally would.
Whenever a weak electrolyte and a strong electrolyte, in solution together, contain a
common ion, the weak electrolyte ionises less than it would if it were alone in solution.
This observation is called the common ion effect.
It has important applications in buffer solutions.
Exercise
In a solution containing 1.0 M HF
(Ka = 7.2 x 10-4) and 1.0 M NaF, calculate :
a)the [H+].
b)the percentage dissociation of HF.
Buffer Solutions
These are solutions that contain a weak conjugate acid -base pair.
These solutions can resist drastic changes in pH when small amounts of acid or base are
added. Therefore, pH is kept nearly constant.
For proteins and enzymes to function properly the pH must be kept constant.
A buffer needs large concentrations of a weak acid and its conjugate base.
For the best efficiency of the buffer, they should be in similar amounts.
Buffer capacity: The amount of acid or base that a buffer can neutralise before an
appreciable pH change occurs.
The greater the amount of the conjugate acid-base pair, the greater is the buffer
capacity.
How does a buffer work?
Consider the acetate buffer:
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
• Add a strong acid (e.g. HCℓ)
• [H+] increases. Equilibrium shifts to the left .
• Both CH3COO- + H+ are used up.
• pH remains nearly constant.
• The solution will act as a buffer when acid is added as long as enough CH3COO-
ions are present.
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
• Add a strong base (eg. NaOH)
• The OH- ions from the added base will react with the H+ ions of the acid.
• H++ OH-→H2O
• [H+] decreases. Equilibrium shifts to the right .
• Some CH3COOH dissociates and more H+ ions are formed.
• The pH is kept nearly constant.
• The solution will act as a buffer provided enough CH3COOH is present.
• Acetic acid by itself cannot act as a buffer. Additional acetate ions (conjugate base
of acetic acid) must be added.
Blood Buffers
•Bicarbonate buffers
H2CO3/HCO3-
•Phosphate buffers
HPO42- /H2PO4-
•Protein buffers
haemoglobin/oxyhaemoglobin
Example : Uncontrolled diabetes/ketosis
Uncontrolled diabetes results in acidosis where the plasma becomes more acidic (pH
drops).
This affects the following equilibrium:
HCO3-(aq) + H+(aq) ⇌ H2CO3(aq) ⇌ H2O(ℓ) + CO2(g)
base conjugate acid
► As pH drops (more H+ ions), more H2CO3 is produced (shift to the right).
► H2CO3 decomposes into H2O and CO2.
► Excess CO2 stimulates the brain, so the patient breathes faster (to remove CO2
from the blood).
► As the level of CO2 in the blood drops, breathing returns to normal.
Summary
A buffer solution – a solution that has the ability to resist pH changes.
A buffer solution must contain a weak acid and its conjugate base or a weak base and
its conjugate acid.
A buffer system contain large concentrations of conjugate acid and base and they are
almost equal.
Eg: 1 M CH3COOH/ 1 M CH3COO-√
not 0.1 M CH3COOH/ 0.1 M CH3COO-
Buffer capacity
The greater the concentration of the conjugate acid
and base , the greater the buffering capacity.
Problems
2 types of problems
[Link] out the pH of a given buffer.
[Link] a buffer of a certain pH.
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By choosing appropriate components and adjusting their relative concentrations, one
can buffer a solution to almost any pH.
The previous example with a 1.0 L solution of
3.0 mol. acetic acid and 2.0 mol. sodium acetate can be solved using the Henderson -
Hasselbach Equation:
pH = -log (1.8 x 10-5) + log (2.0 mol/1.0 L)
(3.0 mol/1.0 L)
= 4.54
• What would the possible buffer system be?
• Unless there is an extra source of HCOO- ions, we cannot claim to
have a buffer.
• One needs more conjugate base in the form of a salt.
• Adding 1.2 M HCOONa (sodium formate ) to the formic acid would
create a buffer system.
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• What would the possible buffer system be?
• Unless there is an extra source of HCOO- ions, we cannot claim to
have a buffer.
• One needs more conjugate base in the form of a salt.
• Adding 1.2 M HCOONa (sodium formate ) to the formic acid would
create a buffer system.
Solubility Equilibria
→ Up to now we have dealt with homogeneous acid/base equilibria (all species in the same phase).
→ We will now consider the equilibria involved in dissolution or precipitation of ionic compounds. The compounds are usually slightly soluble.
→ Before, we considered various solubility rules when we considered the solubility of common salts, in order to predict whether a substance was going to be soluble in
water or whether a precipitate would form.
→ Now considering solubility equilibria we can make quantitative predictions about the amount of a given compounds that will or will not dissolve.
The Solubility Product (Ksp)
→ Consider the following equilibrium:
→ CaF2(s) ⇌ Ca2+(aq) + 2F-(aq)
→ Since the equilibrium describes the dissolution of a solid, we call the equilibrium constant the solubility product or Ksp.
→ Ksp = [Ca2+][F-]2
→ Ksp is the product of the molar concentrations of the ions involved in the equilibrium, each raised to the power of its coefficient in the equilibrium reaction.
→ Molar concentrations of the ions are in mol L-1.
→ For slightly soluble salts it is more usual to describe their solubility using Ksp.
Solubility
→ The quantity of a substance that dissolves to form a saturated solution.
→ Often expressed as g.L-1 or mol.L-1
→ Ksp is an equilibrium constant of the equilibrium between an ionic solid and its saturated solution.
→ Ksp has only one value for a given solute at any specific temperature.
→ There are limitations to solubility products because
➢we assume that ionic compounds fully dissociate when they dissolve, and this is not always true.
➢Also, we tend to ignore other equilibria that may occur simultaneously in solution e.g. acid-base equilibria
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➢Also, we tend to ignore other equilibria that may occur simultaneously in solution e.g. acid-base equilibria
Factors Affecting Solubility
The solubility of a substance is affected by:
Temperature
Presence of common ions *
pH of the solution **
Presence of complexing agents
* The common ion effect
In general, the solubility of a slightly soluble salt decreases in the presence of a common ion.
** pH of a solution
The solubility of slightly soluble salts containing basic anions increases as [H+] increases i.e. As pH is lowered.
Precipitation and Solubility Product
→ Given the concentration of substances in a reaction mixture, will a precipitate form?
→ We need to compare the ion product (Q) and the Ksp values.
→ Ion product Q = [ ]x[ ]y
→ where the concentrations are the initial concentrations not the equilibrium concentrations like in Ksp.
→ The ion product expression has the form of the Ksp expression − each concentration is raised to the power of the number of ions in the ionic formula.
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Precipitation and Solubility Product
→ Given the concentration of substances in a reaction mixture, will a precipitate form?
→ We need to compare the ion product (Q) and the Ksp values.
→ Ion product Q = [ ]x[ ]y
→ where the concentrations are the initial concentrations not the equilibrium concentrations like in Ksp.
→ The ion product expression has the form of the Ksp expression − each concentration is raised to the power of the number of ions in the ionic formula.
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