Chapter 2

Introduction to Ionic Equilibria

2.1 Equilibrium constants

- Precipitation Reactions
- Common ion effect and salt effect on solubility
2.2 Effect of acidity on solubility
2.3 Complexation equilibria
- Complex ion and ligands
- Complex formation equilibria with unidentate and multidentate
ligands
- Factors affecting stability of complexes
- Effect of complexation on solubility
2.4 Redox Equilibria
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 2. Introduction
• If a mixture of hydrogen and iodine vapor is heated to a temperature of about
450 OC in a closed vessel, the two elements combine to form hydrogen iodide.

• However, no matter how long the duration of the experiment, some hydrogen
and iodine remain uncombined.

• If pure hydrogen iodide is heated in a closed vessel to a temperature of about

450 OC, the substance decomposes to form hydrogen and iodine.

• But again, no matter how prolonged the heating, some hydrogen iodide
remains unchanged.

• This is an example of a reversible reaction in the gaseous phase.

2
 • It is found that after the elapse of some time interval, al1reversible reactions
reach a state of chemical equilibrium.

• In this state the composition of the equilibrium mixture remains constant,

provided that the temperature (and for some gaseous reactions, the
pressure also) remains constant.

• In the equilibrium state, the two opposing reactions are taking place at the
same rate so that the system is in a state of dynamic equilibrium.

• Le Chatelier-Braun Principle:
• 'If a constraint is applied to a system in equilibrium, the system will
adjust itself so as to nullify the effect of the constraint‘.

(a) Temperature
• The formation of ammonia from nitrogen and hydrogen is a reversible reaction

3
• The forward reaction is accompanied by the evolution of heat (energy), and is said
to be an exothermic reaction

• Thus the reverse reaction absorbs heat and is said to be endothermic.

• If the temperature of an equilibrium mixture of nitrogen, hydrogen and

ammonia is increased, then the reaction which absorbs heat will be favoured, and
so ammonia is decomposed.

(b) Pressure.

• In the preparation of hydrogen iodide, the stoichiometric coefficients of the

molecules on each side of the equation for the reaction are equal.

• Thus there is no change in volume when reaction occurs.

• Changing the pressure of the system affects both the reactant and product equally,
and so the composition of the equilibrium mixture remains unchanged.

4
• In the nitrogen, hydrogen, ammonia equilibrium system, there is a decrease
in volume when ammonia is produced, and hence an increase in pressure
will favor the formation of ammonia.

• Any gaseous equilibrium in which a change in volume takes place will be

affected by a change in pressure.

• For equilibrium in the liquid phase, moderate changes in pressure have

practically no effect on the volume.

(c) Concentration of reagents.

• In the production of HI if hydrogen is added to the equilibrium mixture, it is

found that more hydrogen iodide is present when equilibrium is restored.

• In accordance with the Le Chatelier-Braun Principle, the system has reacted

to remove some of the added hydrogen.

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• THE LAW OF MASS ACTION

• 'The velocity of a chemical reaction is proportional to the product of the

active masses of the reacting substances'.

• 'Active mass' was interpreted as concentration and expressed in moles per

litre.

• For the reversible reaction at constant temperature:

• we write the equilibrium constant, K, in the form

Equilibrium constant:

6
• SOLUBILITY PRODUCT
• The solubility product is the equilibrium constant for the reaction in which a
solid salt dissolves to give its constituent ions in solution.

• Solid is omitted from the equilibrium constant because it is in its standard

state.

• As an example, consider the dissolution of mercury(I) chloride (Hg2Cl 2 , also

called mercurous chloride) in water.

• The reaction is Hg2Cl2 ⇌ Hg22+ + 2Cl−

• for which the solubility product, Ksp , is

Ksp = [Hg22+][Cl−]2 = 1.2 × 10−18

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•

8
• Solubility product

• only apply to slightly soluble ionic compounds.

• shows the interaction between ions in the solution.

• the smaller the value of Ksp, the less soluble the compound in water.

• Example 1: Write the dissociation equation and solubility product expression

for: a) Ca3(PO4)2 b) Ag2S

• Solution

9
• Example 2: The Ksp of silver bromide (AgBr) is 7.7 × 10‒13 , calculate its molar
solubility

• Solution:
• Consider the dissociation of AgBr in water.
AgBr (s) ⇌ Ag+ (aq) + Br‒(aq)
Initial x 0 0
Change −x +x +x
Equilibrium 0 x x

• Where x is the Molar solubility: Ksp = x2 = 7.7 × 10‒13 ; x = 8.5 × 10‒7 M

• Therefore, at equilibrium [Ag+] = [Br‒] = 8.8 × 10‒7, and it is equal to the molar
solubility of AgBr.

• Using the molar solubility we can calculate the solubility in g/L.

10
• Solubility = Molar solubility ×molar mass = 8.8 ×10‒7 mol/L × 188 g/mol =
1.65×10‒4 g/L.

• Example 3: The solubility of calcium sulfate (CaSO4) is found to be 0.67

g/L. Calculate the value of Ksp of calcium sulfate.

• Solution: Molar solubility = Solubility/molar mass

= (0.67 g/L) /(136.2)
= 4.9 ×10‒3 mol/L

• Consider the dissociation of CaSO4 in water.

CaSO4(s) ⇌ Ca 2+ (aq) + SO42‒(aq)
Initial x 0 0
Change −x +x +x
Equilibrium 0 x x
Where x is the Molar solubility: Ksp = x2 = (4.9 × 10‒3 )2= 2.4 × 10‒5

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• Exercise
• The solubility of lead chromate (PbCrO4) is 4.5 ×10−5 g/L. Calculate the
solubility product of this compound.
Factors affecting solubility
A. Common ion effect

• The solubility of an ionic precipitate decreases when a soluble compound

containing one of the ions of the precipitate is added to the solution .

• This behavior is called the common-ion effect.

• Example 4: Consider a saturated solution of calcium sulfate.

• CaSO4(s) ⇌ Ca 2+ (aq) + SO42‒(aq) and Ksp = [Ca 2+ ][SO42−] = 2.4 × 10−5 at

298 K

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• When a solution H2SO4 is added to the saturated CaSO4 solution.

• What is the effect on the equilibrium shift, solubility effect and Ksp value.

• The equilibrium shift to left, CaSO4 will precipitate out

• solubility decrease

• But the Ksp value remains unchanged.

• If a solution that contains Ca2+ ions is added, it will have the same effect.

• Example 5:
• Calculate the solubility of silver chloride (in g/L) in a 8.3 × 10‒3 M silver
nitrate solution.

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• Solution
• The common ion here is Ag+ , which is supplied by both AgCl and AgNO3.

• The presence of the common ion will affect only the solubility of AgCl (in
g/L), but not the Ksp value.

• Step 1: The ionic species in solution are Ag+ ions (from both AgCl and
AgNO3), Cl– ions and the spectator NO3– ions.

• Step 2: Since AgNO3 is a strong electrolyte, it dissociates completely

AgNO3(s) → Ag+ (aq) + NO3– (aq), [AgNO3] = [Ag+ ] = 8.3 × 10‒3 M

• Let s be the molar solubil

AgCl(s) → Ag+ + Cl–
8.3×10‒3 0
+x +x

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 Ksp = [Ag+][ Cl‒] = (8.3 × 10‒3 + x) (x) = 1.6 ×10−10
Assuming x << 8.3 × 10‒3 :
Ksp = (8.3 × 10‒3 ) (x) = 1.6 ×10−10 ,
x = 1.9 × 10‒8 M

Step 4: At equilibrium [Ag+] = 8.3 × 10‒3, [ Cl‒] = 1.9 × 10‒8 M

• Molar solubility of AgCl = 1.9×10−8 M

• Solubility of AgCl = 1.9 × 10‒8 M ×143.4 g/mol

• = 2.7 ×10−6 g/L

• Note: the solubility of AgCl in pure water is 1.9 ×10−3 g/L

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16
17
B. Salt effect (electrolyte effect)

• This is the effect by salts with no common ion and it increases the solubility of
a precipitate.

• The salt effect results from the electrostatic attractive and repulsive forces
between the ions of an electrolyte and the ions involved in an equilibrium.

• These forces cause each ion from the dissociated reactant to be surrounded by a
sheath of solution that contains a slight excess of electrolyte ions of opposite
charge.

• For example, when a BaSO4 precipitate is equilibrated with a NaCl solution,

each dissolved Ba 2+ tends to attract Cl− and repel Na +,

• Therefore a slightly negative ionic atmosphere around the Ba 2+ is created.

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• Similarly, each SO42− is surrounded by a Na+ and tends to be slightly positive.

• The charged layers created by adding NaCl make the Ba2+ appear to be
somewhat less positive and the SO42−somewhat less negative.

• The result of this shielding effect is a decrease in overall attraction between

Ba2+ and SO42− ions and a corresponding increase in the solubility of BaSO4.

• The solubility becomes greater as the number of electrolyte ions in the

solution becomes larger.

• In other words, the effective concentration of Ba2+ and SO42− ions becomes
less as the ionic strength of the medium becomes greater.

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Complex and Formation Constants

• Complexes play important roles in many chemical and biochemical

processes.

• For example, the heme molecule in blood holds iron tightly because the
nitrogen atoms of the heme form strong complexing bonds.

• The iron [as iron(II)] in turn bonds readily with oxygen to transport oxygen
gas from the lungs to elsewhere in the body.

• Carbon monoxide kills because it is a strong complexer and displaces

oxygen;

• CO binds to heme 200 times more strongly than does oxygen, forming
carboxyhemoglobin.

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• Many cations will form complexes in solution with a variety of substances
that have a pair of unshared electrons.

• The metal cation is a Lewis acid (electron pair acceptor), and the
complexer is a Lewis base (electron pair donor).

• The number of molecules of the complexing agent, called the ligand,

combined will depend on the coordination number of the metal cation and
on the number of complexing groups on the ligand molecule.

• Ammonia is a simple complexing agent with one pair of unshared electrons

that will complex copper ion:

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• The copper ion acts as a Lewis acid, and the ammonia is a Lewis base.

• The Cu2+ (hydrated) ion is pale blue in solution, while the ammonia (the
ammine) complex is deep blue.

• Ammonia will also complex with silver ion to form a colorless complex.

• Two ammonia molecules complex with each silver ion in a stepwise

fashion, and we can write an equilibrium constant for each step, called the
formation constant Kf:

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• The overall reaction is the sum of the two steps, and the overall formation
constant is the product of the stepwise formation constants:

• For the formation of a simple 1:1 complex, for example, M + L = ML, the
formation constant is simply Kf = [ML]/[M][L].

• The formation constant is also called the stability constant Ks, or Kstab.

• It is possible to write the equilibria in the opposite direction, as dissociations.

• In this case the concentration terms are inverted in the equilibrium constant
expressions and the formation constants are then called instability constants
Ki, or dissociation constants Kd: Kf = Ks = 1/Kior 1/Kd.
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 • Classification of ligands

• Depending on the number of donor atoms present ligands are classified as:
1. Monodentate (unidentate) ligands: ligands with only one donor atom.
2. Polydentate (multidentate) ligands: ligands with more than one donor atom.
• Bidentate ligand e.g. ethylenediamine ( “en”): oxalate

• Some Common Polydentate Ligands (Chelating Agents)

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Example : A 0.22 M quantity of CuSO4 is added to 1.35 M NH3 solution. Find
the equilibrium concentrations of Cu2+, NH3 and Cu(NH3)42+ . Use Kf = 5 × 1013

Solution
CuSO4 ⟶ Cu2+(aq) + SO42‒(aq)
0.22 M 0.22 M 0.22 M
The addition of CuSO4 to the NH3 solution results in complex ion formation
Cu2+(aq) + 4NH3(aq) ⇌ Cu(NH3)42+(aq)
Kf = 5 × 1013
Since Kf is very large, at equilibrium assume all central ion is converted to
complex product. Hence, Ccomplex = Ccentral atom

so that at equilibrium Ccomplex = 0.22 M

The ligand used in excess (Cligand) = Cinitial given – Cobtained by stoichiometry

= 1.35 – (`4 × 0.22) = 0.47 M

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• Let the equilibrium concentration of Cu2+ be x.

• Exercise: If 2.50 g of CuSO4 are dissolved in 9 × 102 mL of 0.3 M NH3,

what are the concentrations of Cu2+ , NH3 and Cu(NH3)42+ at equilibrium?

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Factors affecting stability of complexes

• Some of the metal-ligand complexes are quite stable.

• The stability of complexes is influenced by a number of factors related to the

ligand and metal ions.

• Some of these are as follows.

The nature of central atom:

• It determines the type of bonding with the ligand donor atom; more the
electrostatic character of the bond, stable the complex.

• Therefore, small ions with high charges lead to stronger complexes.

• When increasing charge/size ratio the stability increase, this means the
nature of central ion refers to:
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a) The greater charge/size ratio the greater will be the stability of the complex.
Example, complex of Fe3+ are more stable than Fe2+.

b) The higher the electronegativity of the central ion the more stable will be
the complex.

The nature of the ligands:

• The nature of bond formed between the ligand and metal ion also influence
the stability.

• More so, the ligands forming chelates impart extra stability.

• For example the complex of nickel with the hexadentate ligand, penten, is
more than 1010 times stronger than the one formed by ammonia.

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Basicity of the ligand:

• The stability of a series of complexes can be correlated to the ability of the

ligand to accept a proton; greater the basicity of the ligand greater the stability
the complex.

• Because the donation of electrons is higher or easier by strong bases than

weak bases.

Number of metal chelate rings:

• The stability of the complex is directly related to the number of chelate rings
formed between the ligand and metal ion.
• The formation of five- or six-membered rings provides the maximum stability

• Greater the number of such rings, greater is the stability.

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 Steric effects:

• The steric effects refer to the sizes of the ligands, their spatial arrangement
and the distances between the coordination sites and also if bulky groups
are present around.

Effect of complexation on solubility

• Consider the dissolution of zinc sulfide in water:

ZnS(s) + H2O(l) ⇌ Zn2+(aq) + HS–(aq) +OH–(aq)

• Upon addition of NaCN, what will happen the solubility of ZnS?

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• Solution

• The CN– ions act as ligands and react with Zn2+ (aq) to form the complex
ion Zn(CN)42–:
Zn2+(aq) + 4 CN–(aq) ⇌ Zn(CN)42–(aq), Kf = 4.2×1019

• To observe the effect, add the above equations and multiply their
equilibrium constants:

• Over all r/n: Koverall = Ksp × Kf = (2 ×10–22 ) × (4.2×1019 ) = 8.4×10–3

• Since Koveral value increase, solubility of ZnS in solution will increase

• Thus, a ligand increases the solubility of a slightly soluble ionic compound

if it forms a complex ion with the cation.

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• Example: Calculate the solubility of AgI in 2.5 M NH3 and Kf of
Ag(NH3)2+ = 1.7×107 and Ksp of AgI = 8.3×10–17

• Solution
• In this example the influence of complexation on solubility will be
identified.

• Step-1: write up of the possible chemical equations

AgI(s) ⇌ Ag+(aq) + I–(aq)

Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq)
• Step-2: write up of the overall reaction and equilibrium constant.

AgI(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + I–(aq)

Koverall = Ksp × Kf = 1.4×10 –9

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• Step-3: setting up equilibrium expression
AgI(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + I–(aq)
Initial 2.5 0 0
Complexation −2x +x +x
Equilibrium 2.5 −2x +x +x

Step-4: determination of equilibrium concentration of each species

at equilibrium
[Ag(NH3)2+] = [I–] = 9.4 × 10−5
Similarly since AgI and I– are in one to one mole ratio, thus
[AgI] = 9.4 × 10−5 M

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• Step-5: conversion of molar solubility to solubility form
Solubility = (9.4 × 10−5 mol/L) × (235 g/mol)
= 2.2 × 10−2 g/L

Redox Equilibria

• In an oxidation–reduction reaction, also known as a redox reaction, electrons

are transferred from one reactant to another.

• As a result of this electron transfer, some of the elements involved in the

reaction undergo a change in oxidation state.

• Those species experiencing an increase in their oxidation state are oxidized,

while those experiencing a decrease in their oxidation state are reduced.

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• For example, in the following redox reaction between Fe3+ and oxalic acid,
H2C2O4, iron is reduced since its oxidation state changes from +3 to +2.

2Fe3+(aq) + H2C2O4(aq) + 2H2O(l) ⇌ 2Fe2+(aq) + 2CO2(g) + 2H3O+(aq)

• Oxalic acid, on the other hand, is oxidized since the oxidation state for
carbon increases from +3 in H2C2O4 to +4 in CO2 .

• Redox reactions, such as that shown in equation, can be divided into

separate half-reactions that individually describe the oxidation and the
reduction processes.

H2C2O4(aq) + 2H2O(l) ⇌ 2CO2(g) + 2H3O+(aq) + 2e

2Fe3+(aq) + 2e ⇌ 2Fe2+(aq)

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• Oxidation is a loss of electron/s and reduction is a gain of electron/s.

• A reducing agent is a species that donates electron/s to another species and

an oxidizing agent is a species that accepts electrons from another species.

Electrochemical Cells

• There are two kinds of electrochemical cells, voltaic (galvanic) and

electrolytic.

• In voltaic cells, a chemical reaction spontaneously occurs to produce

electrical energy. E cell is positive

• The lead storage battery and the ordinary flashlight cell are common
examples of voltaic cells.

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• In electrolytic cells, electrical energy is used to force a nonspontaneous
chemical reaction to occur, that is, to go in the reverse direction it would in
a voltaic cell. E cell is negative

• An example is the electrolysis of water.

• In both types of these cells, the electrode at which oxidation occurs is the
anode, and that at which reduction occurs is the cathode.

• THE CELL POTENTIAL

• Consider the following redox reaction in a voltaic cell:

Fe2+ + Ce4+ ⇌ Fe3+ + Ce3+

• If we mix a solution containing Fe2+ with one containing Ce4+, there is a

certain tendency for the ions to transfer electrons.

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• Assume the Fe2+ and Ce4+ are in separate beakers connected by a salt
bridge, as shown in Figure.

• (A salt bridge allows ion transfer into the solutions and prevents mixing of
the solutions.)

• The salt bridge typically contains a gel containing KCl.

• KCl is the preferred ingredient since K+ and Cl− move at equal speeds.

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• The Fe2+ is being oxidized at the platinum wire (the anode):
Fe2+ → Fe3+ + e− (oxidation half-reaction)

• The released electrons flow through the wire to the other beaker where the
Ce4+ is reduced (at the cathode):
Ce4+ + e− → Ce3+ (reduction half-reaction)

• The electrode at which oxidation occurs is called the anode.

• The electrode at which reduction occurs is called the cathode.

• The net reaction that occurs in the voltaic cell; it is called the cell reaction.

• The platinum wires can be considered electrodes.

39
 Notation for Voltaic Cells

• It is convenient to have a shorthand way of designating particular voltaic

cells.

• The cell, consisting of a zinc metal–zinc ion half-cell and a copper

metal–copper ion half-cell, is written

Zn(s)│Zn2+(aq) ║ Cu2+(aq) │Cu(s)

• In this notation, the anode, or oxidation half-cell, is always written on

the left; the cathode, or reduction half-cell, is written on the right.

• The two electrodes are electrically connected by means of a salt bridge,

denoted by two vertical bars

40
• The shorthand notation for representing the cell with the reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

• Can be written as:

41
• What is the shorthand notation for representing the cell shown below?
1.

2.

42
• Relation between Electrode Potential and Concentration.

• In 1889 Walter Nernst derived a mathematical relationship which enable us

to calculate the half-cell potential, E, from the standard electrode potential,
E°, and the temperature of the cell.

• This relation known as the Nernst equation can be stated as

where E° = standard electrode potential

R = gas constant
T = Kelvin temperature
n = number of electrons transferred in the half-reaction
F = Faraday of electricity
K= equilibrium constant for the half-cell reaction as in equilibrium law

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• Calculation of Half-cell potential

• For an oxidation half-cell reaction when the metal electrode M gives Mn+
ion, M → Mn+ + ne–

• the Nernst equation takes the form

• The concentration of solid metal [M] is equal to zero.

• Therefore, the Nernst equation can be written as

• Substituting the values of R, F and T at 25°C, the quantity 2.303 RT/F

comes to be 0.0591.

• Thus the Nernst equation can be written in its simplified form as

44
• Example . What is the potential of a half-cell consisting of zinc electrode in
0.01M ZnSO4 solution at 25°C, E° =0.763 V.

• The half-cell reaction is Zn ⎯⎯→ Zn2+ + 2e– (oxidation)

• The Nernst equation for the half-cell reaction is

• The number of electrons transferred n = 2 and E° =0.763 V.

• Substituting these values in the Nernst equation, we have

45
 Calculation of Cell potential

• The Nernst equation is applicable to cell potentials as well.

• Thus,

• K is the equilibrium constant of the redox cell reaction.

Example: Calculate the emf of the cell Zn│Zn2+ (0.001M)║Ag + (0.1M)│Ag.

The standard potential of Ag/Ag+ half-cell is +0.80 V and Zn/Zn2+ is – 0.76
V.

• Solution
Step 1. Write the half-cell reactions of the anode and the cathode.

• Then add the anode and cathode half reactions to obtain the cell reaction and
the value of E°cell.
• E° for a reaction is calculated as E°cell = E°cathode – E°anode
46
Step 2. K for the cell reaction

• substitute the given values in the Nernst equation and solving for E°cell, we
have

47
 Calculation of Equilibrium constant for the cell reaction

• The Nernst equation for a cell is

• At equilibrium, the cell reaction is balanced and the potential is zero

• The Nernst equation may, now, be written as

or

• Example: Calculate the equilibrium constant for the reaction between silver
nitrate and metallic zinc.
Solution
Step 1. Write the equation for the reaction 2Ag+ + Zn ⇌ Zn2+ + Ag

48
• Step 2. Substitute values in the Nernst equation at equilibrium

49