ELECTROCHEMISTRY

LESSON NOTES – FOR ADVANCE LEVEL

NEW

2012
….. with more questions for revision

Prepared by: Makame Kh. H. Sancho

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December, 2012.
M KH. H. SANCHO Lessons notes for Advanced level

ELECTROCHEMISTRY
OBJECTIVES OF THE TOPIC:

After studying this topic, you will be able to:

♠ differentiate oxidation and reduction reactions.
♠ balance oxidation and reduction half reactions.
♠ explain the effects of electricity on electrolytes (Faraday’s Laws of electrolysis)
♠ explain corrosion as a redox reaction
♠ compare the mechanism of iron corrosion protection by zinc and tin.
♠ explain standard electrode potentials
♠ explain the effect of varying electrolyte concentration on the emf of a cell.
♠ determine the emf of a cell by using the Nernst equation.
♠ Calculate equilibrium constants for redox reactions
♠ describe the electrical conductivity of solutions of electrolytes
Proudly prepared by: M Kh. H. Sancho, Dark-room – Zanzibar

INTRODUCTION:
Electrochemistry: Is a branch of chemistry that deals with interchange of electrical energy and
chemical energy.
This is a branch of chemistry that studies chemical reactions which take place in a
solution at the interface of an electron conductor (a metal or a semiconductor and an
ionic conductor (the electrolyte), and which involve electron transfer between the
electrode and the electrolyte or species in solution.

If a chemical reaction is driven by an external applied voltage as in electrolysis, or if a

voltage is created by a chemical reaction as in battery, it is an electrochemical reaction.
Electrochemical reactions occur as a result of transference of electrons from one
species to the other. Electrochemical reactions are redox reactions.
Redox reactions: Are the one where oxidation and reduction take place simultaneously.
The process like rusting of iron articles, fading of the colour of the clothes, burning of
the combustible substances such as cooking gas, wood, coal, etc, fall in the category of
redox reactions. A large number of industrial processes like, electroplating, extraction
of metals like aluminium and sodium, bleaching of wood pulp, manufacture of caustic
soda etc, are also based upon the redox reactions.

** Half component of redox reaction is called half reaction.

** In the overall redox reaction, no free electrons are generated.
Example: 2Na 2Na+ + 2ē (Oxidation – half reaction)
Cl2 + 2ē 2Cl- (Reduction – half reaction)
+ -
2Na + Cl2 2Na + 2Cl (Overall reaction)

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 M KH. H. SANCHO Lessons notes for Advanced level
OXIDATION – REDUCTION (REDOX) REACTION
Oxidation: Is the process of
- is of loosing of electrons or
- increasing of oxidation number or
- adding oxygen to a substance or
- Removing of hydrogen from a substance.
- 2Mg(s) + O2(g) 2MgO(s)
- C6H12O6(s) + 6O2(g) 6CO2(g) + 6H2O(l)
- Zn Zn+2 + 2ē

Reduction: Is the process of

- gaining electrons to a substance or
- decreasing of oxidation number or
- adding hydrogen to a substance or
- Removal of oxygen from a substance
- CuO(s) + H2(g) Cu(s) + H2O(g)
- Fe2O3(s) + 3CO(g) 2Fe(l) + 3CO2(g)
2+
- Cu + 2 ē Cu

** In the latter reaction, the CO has been oxidized and Fe2O3 reduced.
Note: ** Oxidation and reduction always occur together.

Reducing agent (Reductant): Is the one that cause the reduction process to occur. Or; Is the
chemical that removes the oxygen from an oxide i.e. carbon, carbon monoxide
or sometimes hydrogen. In most cases reductant is negative ions or metals.
A species which undergo oxidation, itself is reductant.

Oxidizing agent (Oxidant): Is a substance which accepts electrons. Or; Is the substance which
brought about oxidation to take place. Is the species which undergo gain of
electrons. In most cases, oxidant is non-metal or positive ions.
A species which undergo reduction, itself is oxidant.

Accordingly the following definitions were proposed to explain the process of

oxidation and reduction.
Oxidation: It is a process of addition of hydrogen or any electronegative radical or removal of
hydrogen or any electropositive radical.
Reduction: Is the process of addition of hydrogen or any electropositive radical or removal of
oxygen or any electronegative radical.

Oxidation

PbO + C Pb + CO

Reduction

Here, oxygen is being removed from lead oxide (PbO) and is being added to carbon (C).
Thus, PbO is reduced while C is oxidized.

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 M KH. H. SANCHO Lessons notes for Advanced level
Example 1: In the reactions given below, identify the species undergoing oxidation and
reduction:
(i) H2S(g) + Cl2(g) 2HCl(g) + S(g)
(ii) 3Fe3O4(s) + 8Al(s) 9Fe(s) + 4Al2O3(s)
(iii) 2Na(s) + H2(g) 2NaH(s)
Solution:
(i) H2S is oxidized because either we consider the addition of more
electronegative element chlorine to hydrogen or we may say that from it the
electropositive element hydrogen has been removed. Chlorine is reduced due to
addition of hydrogen to it.
(ii) Aluminium is oxidized because oxygen is added to it. Fe3O4 is reduced because
from it oxygen has been removed.
(iii) On the basis of concept of electronegativity only we may infer that sodium is
oxidized and hydrogen is reduced.

Example 2: Identify the oxidant and reductant in the following reactions:

(i) Zn(s) + ½ O2(g) ZnO(s)
+
(ii) Zn(s) + 2H (aq) Zn2+(aq) + H2O
(iii) I2(g) + H2S(g) 2HI(g) + S(s)
Solution:
(i) Zinc loses electrons and hence is reductant while oxygen is oxidant.
(ii) Zinc is reductant while hydrogen is oxidant.
(iii) Sulphur is reductant while iodine is oxidant.

Example 3: Justify that the reaction, 2Na(s) + H2(s) 2NaH(s) is a redox change.
Solution:
Since in the above reaction the compound formed is an ionic compound which may
also be represented as Na+H-(s), this suggests that one half reactions in this process is:
2Na(s) 2Na+ + 2ē …. Oxidation half
-
H2(g) + 2ē 2H ….. Reduction half

Every redox reaction can be split up into two half reactions, one representing loss of
electrons i.e., oxidation half reaction while the other representing gain of electrons, i.e.,
reduction half reaction.

OXIDATION NUMBER (OXIDATION STATE)

Oxidation number (O.N) of the element: Is defined as the residual charge which its atom has
or appears to have when all other atoms from the molecule are assumed to be
removed as ions by counting the shared electrons with more electronegative atom.

** For example, in hydrogen chloride molecule (HCl), chlorine is more electronegative

than hydrogen. Therefore, the shared pair is counted towards chlorine atom.
** As a result of this, chlorine gets one extra electron and acquires a unit negative
charge. Hence, oxidation number of chlorine is – 1. On the other hand, hydrogen
atom without electron has a unit positive charge. Hence, the oxidation number of
hydrogen in hydrogen chloride is +1.

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 M KH. H. SANCHO Lessons notes for Advanced level
Rules for assigning oxidation number to an atom.
The oxidation number of various elements in their compounds can be calculated by applying
following rules. These rules have been formulated on the basis of the assumption that
electrons in a covalent bond belong entirely to the more electronegative atom.

1. The oxidation number of the element in the free or elementary state is always zero
irrespective of its allotropic form.
For example, O.N of Na = 0, O.N of Cl2 = 0, O.N of P4 = 0, O.N of S8 = 0
2. In accordance with principle of conservation of charge, the algebraic sum of the oxidation
numbers of all the atoms in molecule is zero.
For example, O.N of Na2CO3 = 0, O.N of KMnO4 = 0
3. In case of polyatomic ion the sum of oxidation numbers of all of its atoms is equal to the
charge on the ion.
For example, O.N of Cr2O7-2 = - 2, O.N of NO3- = - 1, O.N of CO32- = - 2
4. *The oxidation number of fluorine is always – 1 in all its compounds.
5. *Hydrogen is assigned oxidation number + 1 in all its compounds except in metal hydrides.
In metal hydrides like NaH, CaH2, LiH, etc, the oxidation number of hydrogen is – 1.
6. Oxygen is assigned oxidation number – 2 in most of its compounds, however, in peroxides
like H2O2, BaO2, Na2O2, etc its oxidation number is – 1.
7. In binary compounds of metal and non-metal, the metal atom has positive oxidation number
while the non-metal atom has negative oxidation number.
For example, O.N. of K in KI is +1 but O.N. of I is – 1.
8. In binary compounds of non-metal, the more electronegative atom has negative oxidation
number, but less electronegative atom has positive oxidation number.
For example, O.N. of Cl in ClF3 is positive (+3) while that in ICl is negative (- 1).

Brief summary of rules

Oxidation number of:
 Free elements = 0
 Fluorine = -1
 Simple ions = Charge on them
 Oxygen = - 2 ; peroxides (- 1); F2O (+2); F2O2 (+1)
 Hydrogen = +1 ; metal hydrides (- 1)
 Sum of O.N. of atoms in molecules = 0
 Sum of O.N. of atoms in polyatomic ions = Charge on them

Example 1: Consider the elements: Ar, Cs, O, F.

(a) Identify the element that exhibits only –ve oxidation state.
(b) Identify the element that exhibits only +ve oxidation state.
(c) Identify the element that exhibit both +ve and –ve oxidation state.
(d) Identify the element which neither exhibits negative nor does +ve oxidation state.
Solution:
(a) F can exhibit – ve oxidation state as it is highly electronegative element.
(b) Cs is highly electropositive element and exhibits +ve oxidation state.
(c) O can show both – ve as well as +ve oxidation state.
(d) Ar is a noble gas with stable electronic configuration and hence neither exhibits
– ve nor +ve oxidation state.

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 M KH. H. SANCHO Lessons notes for Advanced level
Example 2: Calculate the oxidation number of underlined elements in the following species:
(i) Cr2O7- 2 (ii) S2O3- 2 (iii) HNO3 (iv) K2MnO4 (v) NH4+

Solution:
(i) Cr in Cr2O72 - :
Let oxidation number of Cr = x
O.N. of each O atom = - 2
Sum of O.N. of all atoms = 2x + 7(- 2) = 2x – 14
Sum of O.N. must be equal to the charge on the ion.
Thus, 2x – 14 = - 2
x = +6

(ii) S in S2O32- :
Let O.N. of S be x
O.N. of each O atom = - 2
Sum of O.N. of each atoms = 2x + 3(- 2) = 2x – 6
Sum must be equal to the charge, ie., - 2
2x – 6 = - 2
x=+2

(iii) N in HNO3 :
Let O.N. of N be x
O.N. of each O atom = - 2
O.N. of each H atom = + 1
Sum of O.N. of various atoms = x + 1 + 3(- 2) = x + 1 – 6 = x – 5
In molecule, sum be equal to zero
... x – 5 = 0 or x = + 5

(iv) Mn in K2MnO4 :
Let O.N.of Mn be x
O.N. of each O atom = - 2
O.N. of each K atom = + 1
Sum of O.N. of all atoms = 2 + x + 4(- 2) = x – 6
Sum must be equal to zero
... x – 6 = 0 or x = + 6

(v) N in NH4+
Let O.N.of N be x
O.N. of each H atom = +1
Sum of O.N. of all atoms = x + 4(+ 1) = x + 4
Sum must be equal to the charge i.e., +1
... x + 4 = 0 or x = + 4
NOTE:
** Fractional oxidation number appears because the average oxidation state has been taken.
** The knowledge of bonding and individual molecular structure is also important aspect and
has to be considered for calculating the oxidation number of the elements.

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 M KH. H. SANCHO Lessons notes for Advanced level
TYPES OF REDOX REACTIONS
1. Combination reactions: Some important examples of this category are:
C(s) + O2(g) CO2(g)
Mg(s) + N2(g) Mg3N2(s)

2. Decomposition reactions: Some examples of this class of reactions are:

2H2O(l) 2H2(g) + O2(g)
NaH(s) 2Na(s) + H2(g)
2KClO3(s) 2KCl(s) + 3O2(g)

3. Displacement reactions: In a displacement reaction, an ion (or atom) in a compound is

replaced by an ion (or atom) of another element. A general displacement reaction is
denoted as;
X + YZ XZ + Y
Some examples of this type of reaction are:
CuSO4(aq) + Zn(s) Cu(s) + ZnSO4(aq)
Cr2O3(s) + 2Al(s) Al2O3(s) + 2Cr(s)
2Na(s) + 2H2O(l) 2NaOH(aq) + 2H2(g)
2Fe(s) + 3H2O(l) Fe2O3(s) + 3H2O(g)
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
2H2O(l) + 2F2(g) 4HF(aq) + O2(g)
Cl2(g) + 2KI(aq) 2KCl(aq) + I2(s)

4. Disproportionation reactions: A special type of redox reactions.

In a disproportionation reaction an element in one oxidation state is
simultaneously oxidized and reduced.
One reacting substance in a disproportionation reaction always contains an
element that has at least three oxidation states.

NOTE: Among halogens fluorine does not show disproportionation tendency.

** The decomposition of hydrogen peroxide is a familiar example of the reaction, where oxygen
element experiences disproportionation.
+1 -1 +1 -2 0
2H2O2(aq) 2H2O(l) + O2(g)
Here the oxygen of peroxide which is present in – 1 state is converted to zero state in O2
and decreases to – 2 in H2O.

** Phosphorous, sulphur and chlorine are known to undergo disproportionation in the alkaline
medium. The disproportionation reactions are:
P4(s) + 3OH- (aq) + 3H2O(l) PH3(g) + 3H2PO2–(aq)
–
S8(s) + 12OH (aq) 4S2–(aq) + S2O32 – (aq) + 6H2O(l)
Cl2(g) + 2OH-(aq) ClO -(aq) + Cl –(aq) + H2O(l)

Others:
3Ga+ Ga3+ + 2Ga
3In+ In3+ + 2In
2Cu+ Cu2+ + Cu

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 M KH. H. SANCHO Lessons notes for Advanced level
BALANCING OF REDOX REACTIONS
During redox reactions there is a change in oxidation number of the elements due to the
transference of electrons. The number of electrons lost during oxidation is equal to number of
electrons gained during reduction.

The various steps involved in the balancing of redox equations are:

1. Indicate the oxidation number of each atom involved in the reaction. Identify the elements
which undergo a change in the oxidation number.
2. Divide the skeleton redox equation into two half reactions; oxidation half and reduction
half. In each half reaction balance the atoms which undergo a change in the O.N.
3. Add an electron to whichever side is necessary in order to make up for the difference in
O.N in each half reaction.
4. Balance oxygen atoms by addition of proper number of H2O molecules to the side which is
falling short of O atoms in each half reaction.
5. This step is meant for ionic equations only. It involves the balancing of H atoms in each half
reaction.
(i) For acidic medium: Add proper number of H+ ions to the side falling short of H atoms.
(ii) For basic medium: Add proper number of H2O molecules to the side falling short of H
atoms and equal number of OH – ions to the other side.
6. Equalize the number of electrons lost and gained by multiplying the half reactions with
suitable integer and add them to get the final equation.
The application of various steps described above has been illustrated as follows by balancing the
redox equation representing the reaction between iodine and nitric acid.
HNO3 + I2 HIO3 + NO2 + H2O.
Thus, only nitrogen
Step 1: Indication of oxidation numbers of each atom.
+1 +5 -2 0 +1 +5 -2 +4 -2 +1 -2 and iodine undergo
H N O3 + I 2 H I O3 + N O2 + H2 O changes in O.N.
Step 2: Division into two half reactions and balancing the atoms undergoing change in O.N.
0 +5
I2 2HIO3 (oxidation half reaction)
+5 +4
HNO3 NO2 (reduction half reaction)
Step 3: Addition of electrons to make up the difference in O.N.
0 +5
I2 2HIO3 + 10ē (Each I atom loses 5ē therefore, 2 I atoms would lose 10ē)
+5 +4
HNO3 + ē NO2 (Each N atom gains 1 electron)
Step 4: Balancing of O by adding proper number of H2O molecules to the side falling short of O
atoms.
I2 + 6H2O 2HIO3 + 10ē
HNO3 + ē NO2 + H2O
Step 5: Not required because the equation is not ionic.
Step 6: To equalize the electrons multiply reduction half by 10 and add the two.
I2 + 6H2O 2HIO3 + 10ē
[HNO3 + ē NO2 + H2O] x 10

I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O

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 M KH. H. SANCHO Lessons notes for Advanced level
Example 2: Balance the following redox equations by half reaction method:
(i) Cr2O7 2- + Fe2+ Cr3+ + Fe3+ + H2O (in acidic medium)
– – 2-
(ii) Cr(OH)3 + IO3 I + CrO4 (in basic medium)

+6 -2 +1 -2
2- 2+ 3+ 3+
(i) Cr2O7 + Fe Cr + Fe + H2 O
Thus, Cr and Fe change their oxidation number

Cr2O7 2- 2Cr3+ (Reduction half)

Fe2+ Fe3+ (Oxidation half)

Cr2O7 2- + 6ē 2Cr3+
Fe2+ Fe3+ + ē

Cr2O7 2- + 6ē 2Cr3+ + 7H2O

Fe2+ Fe3+ + ē

Cr2O7 2- + 6ē + 14H+ 2Cr3+ + 7H2O

Fe2+ Fe3+ + ē

Cr2O7 2- + 6ē + 14H+ 2Cr3+ + 7H2O

[ Fe2+ Fe3+ + ē] x 6

6Fe2+ + Cr2O7 2- + 14H+ 2Cr3+ + 6Fe3+ + 7H2O

(ii) +3 -2 +1 +5 -2 +6 -2
Cr(OH)3 + IO3 – I– + CrO4 2-
Thus, Cr and I undergo change in oxidation number

Cr(OH)3 CrO42- (Oxidation half)

IO3 – I– (Reduction half)

Cr(OH)3 CrO42- + 3ē
IO3 – + 6ē I–

Cr(OH)3 + H2O CrO42- + 3ē

IO3 – + 6ē I – + 3H2O

Cr(OH)3 + H2O + 5OH – CrO42- + 3ē + 5H2O

IO3 – + 6ē + 6H2O I – + 3H2O + 6OH –

[Cr(OH)3 + H2O + 5OH – CrO42- + 3ē + 5H2O] x 2

IO3 – + 6ē + 6H2O I – + 3H2O + 6OH –

2Cr(OH)3 + 4OH – + IO3 – 2CrO4 2- + 5H2O + I –

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 M KH. H. SANCHO Lessons notes for Advanced level
Neutral medium
The same procedure as used on acid medium is applied, for example on balancing using
electron ion method to complete combustion of propane.
Unbalanced reaction: C3H8 + O2 → CO2 + H2O

Reduction: 4 H+ + O2 + 4 e– 2 H2O
Oxidation: 6 H2O + C3H8 3 CO2 + 20 e– + 20 H+

As in acid and basic medium, electrons which were used to compensate oxidation
changes are multiplied to opposite half reactions, thus solving the equation.
20 H+ + 5 O2 + 20 e– 10 H2O
6 H2O + C3H8 3 CO2 + 20 e– + 20 H+

Equation balanced:
C3H8 + 5 O2 3 CO2 + 4 H2O

Question 1: Write the skeleton equations for the following chemical reactions and balance them
by oxidation number method.
(i) Chloride ions reduce manganese dioxide to manganese (II) ions in acidic
medium and get oxidized itself to chlorine gas.
(ii) Nitrate ions in acidic medium oxidize magnesium to Mg 2+ ions but itself
gets reduced to nitrogen (I) oxide.
(iii) Zinc reacts with conc. Nitric acid to produce zinc nitrate, nitrogen dioxide
and water.
(iv) Permanganate ion oxidizes oxalate ions in acidic in acidic medium to
carbon dioxide and get reduced itself to Mn2+ ions.
(v) Zinc reacts with nitric acid to form zinc (II) ions, ammonium ions and
water.
Question 2: The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+,
and H+ ions. Write a balanced ionic equation for the reaction.
Question 3: Balance the following redox reactions by ion-electron method:
(a) MnO4 – + I – MnO2 + I2 (in basic medium)
(b) MnO4 – + SO2 Mn2+ + HSO4 – (in acidic medium)
(c) H2O2 + Fe2+ Fe3+ + H2O (in acidic medium)
(d) Cl2O7 + H2O2 ClO2 – + O2 (in basic medium)
(e) S2 – + NO3 – NO + S (in acidic medium)
(f) Cr3+ + Na2O2 CrO4 – + Na+ (in basic medium)
(g) MnO4 – + C2H2O4 Mn2+ + CO2 + H2O (in acidic medium)
(h) N2H4 + ClO3 – NO + Cl – (in basic medium)
Question 4: Which of the following are redox reactions?
(i) Zn + 2HCl ZnCl2 + H2
(ii) Al(OH)3 + 3HCl AlCl3 + 3H2O
+
(iii) Disproportionation of Cu ions in aqueous solution.
(iv) Ag+(aq) + I –(aq) AgI(s)
Question 5: Hydrogen peroxide reacts with ozone to produce water and dioxygen gas. Write the
balanced equation and indicate oxidizing and reducing agent.

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 M KH. H. SANCHO Lessons notes for Advanced level
SOME IMPORTANT OXIDIZING AGENTS AND REDUCING AGENTS
Some important oxidizing agents and reducing agents along with their corresponding
reduction/oxidation half reactions are summarized below:

(A). OXIDIZING AGENTS:

1. Potassium permanganate (KMnO4). KMnO4 is a powerful oxidizing agent. It can act
oxidant in acidic, neutral as well as in alkaline medium giving different reduction products.
Acidic medium: MnO – + 8H+ + 5ē Mn2+ + 4H2O
–
Neutral medium: MnO4 + 2H2O + 3ē MnO2 + 4OH –
Alkaline medium: MnO4 – + ē MnO4 2 –
2. Potassium dichromate (K2Cr2O7). It is powerful oxidizing agent. It acts as oxidizing agent
in acidic medium and gets reduced to Cr3+
Cr2O7 2 – + 14H+ + 6ē 2Cr3+ + 7H2O
3. Halogens. Halogens are very good oxidizing agents. They get reduced to halide ions.
X2 + 2ē 2X –
4. Potassium iodate (KIO3). It acts as oxidizing agent in acidic medium and gets oxidized to I–
ions
IO3 – + 6H+ + 6ē I– + 3H2O
5. Nitric acid (HNO3). Both concentrated and dilute HNO3 can act as oxidizing agents.
However, their reducing products are different.
Conc. HNO3: NO3 – + 2H+ + ē NO2 + H2 O
Dil. HNO3: NO3 – + 4H+ + 3ē NO + 2H2O
6. Manganese dioxide (MnO2). MnO2 gets reduced to Mn2+ ions in acidic medium
MnO2 + 4H+ + 2ē Mn2+ + 2H2O

(B). REDUCING AGENTS:

1. Ferrous sulphate (FeSO4.7H2O). It act as reducing agents in acidic medium, and iron
increases its oxidation number from +2 to +3.
Fe2+ Fe3+ + ē
2. Stannous chloride or tin (II) chloride (SnCl2). Sn increases its O.N. from +2 to +4
Sn2+ Sn4+ + ē
3. Hydrogen sulphide (H2S). H2S gets oxidized to sulphur
S2 – S + 2ē
4. Sulphur dioxide (SO2). In aqueous solutions SO2 exists as H2SO3, which gets oxidized to
SO4 2 – ions.
SO32 – + H2O SO42 – + 2H+ + 2ē
5. Oxalic acid, (H2C2O4). Oxalic acid gets oxidized to carbon dioxide. The O.N.of carbon
increases from +3 to +4.
C2O42 – 2CO2 + 2ē

Others:
(i) Hydrogen peroxide (H2O2). In H2O2, the oxidation number of O is – 1, it can increase its
O.N. to zero and get oxidized. Similarly, it can decrease its O.N. to – 2 and get reduced.
H2O2 2H+ + O2 + 2ē (Reducing agent)
+
H2O2 + 2H + 2ē 2H2O (Oxidizing agent)

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 M KH. H. SANCHO Lessons notes for Advanced level
INDIRECT REDOX REACTIONS AND ELECTROCHEMICAL CELLS
The redox reactions in which oxidation and reduction take place in different vessels are called
indirect redox reactions.

In such reactions, the transference of electrons between reducing agent and oxidizing
agent takes place indirectly through the conducting wires. These reactions involve the
conversion of the chemical energy into electrical energy. The arrangement for carrying out
the indirect redox reaction is referred to as electrochemical cell.

Electrochemical cell: Is a device in which chemical energy is converted into electrical energy.
These are also called galvanic cells or voltaic cells.

** An arrangement involving contact between the oxidized and reduced form of the substance
such as Zn/Zn2+ or Cu/Cu2+ at the interface is called redox couple. The two metals act as
electrodes and are connected by a conducting wire through a galvanometer. The two
solutions are joined by the inverted U–tube known as salt bridge.
Salt bridge: Is an electrolyte which joins the half cell of two electrodes without disturbing their
potentials. The U–tube is filled with aqueous solution of some electrolyte such as
KCl, KNO3, or NH4Cl.
Functions of Salts Bridge, in electrochemical cell, a salt bridge serves two important functions:
(i) It allows the flow of current by completing the circuit.
(ii) It maintains electrically neutrality.
Thus, the salt bridge helps to prevent the accumulation of charges and maintains
the flow of current.
** The electrode at which oxidation takes place is called anode (constitute – ve terminal) and
that at which reduction takes place is called cathode (constitute +ve terminal of the cell).
** By convection, the direction of flow of current is from +ve terminal to – ve terminal which is
opposite to the flow of electrons.
** A galvanic cell whose electrodes are zinc and copper submerged in zinc sulfate and copper
sulfate, respectively, is known as a Daniel cell.

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 M KH. H. SANCHO Lessons notes for Advanced level
HALF CELLS AND HALF CELL REACTION
Oxidation and reduction in electrochemical cell take place in different vessels. These two parts
of the electrochemical cell are called half cells and reactions taking place in them are called half
cell reactions.

For example, the half cell reactions in zinc-copper sulphate cell are:
Zn(s) Zn2+(aq) + 2ē (Oxidation half cell reaction)
Cu2+(aq) + 2ē Cu (Reduction half cell reaction)
The overall reaction taking place may be represented as:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Representation of galvanic cell

The half cell is constituted by a redox couple which is represented M/M n+ or M n+/M, where M
represent the symbol of the element, and M n+ represents its cation in electrolyte. The slash (/)
represent interface between two phases (may be solid/liquid or liquid/gas). The concentration of
electrolyte may also be mentioned in brackets.

** Let us consider copper electrode in contact with cupric ions with concentration equal to 1.0M.
- It can be represented as Cu2+(1.0M)/Cu, if it constitutes reduction half cell.
- It can be represented as Cu/Cu2+(1.0M), if it constitutes oxidation half cell.
- The two half cells are separated by the two vertical lines (//)which indicate salt bridge.

Example1: Zn-CuSO4 cell may be represented as:

Zn/Zn2+(1.0M) // Cu2+ (1.0M)/Cu

Question 1: In galvanic cell Cu/Cu2+//Ag+/Ag, what is the net cell reaction and which electrode
acts as – ve terminal.
Question 2: Represent the cell in which the net cell reaction is:
Fe + Sn2+ Fe2+ + Sn
Question 3: What is the direction of flow of electrons and convectional current in the cell,
Zn/Zn2+ // Ag+/Ag

ELECTRODE POTENTIAL
Electrode potential: Is the electrical potential difference in volts set up between the metal and
its solution.
The potential difference at equilibrium depends upon:
* The nature of metal and its ion.
* Concentration of ions in the solution
* Temperature
According to the present convections the half reactions are always written as reduction half
reactions and their potentials are represented by reduction potentials.
Reduction potential (Ered), (tendency to gain electrons) and oxidation potential, (Eoxi) (tendency
to lose electrons) of an electrode are numerically equal but have opposite signs.
Standard electrode potential: Is the reduction potential of electrode when the concentration of
the ions in the solution is 1molL – 1 and temperature is 298K.

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 M KH. H. SANCHO Lessons notes for Advanced level
Standard hydrogen electrode (SHE): Its electrode potential is arbitrarily taken to be zero. It is
taken as a common reference electrode potential, hence, the electrode potential of
various electrodes are measured relative to it.

** SHE consists of a platinum wire sealed into a glass tube and carrying a platinum foil at one
end. The platinum foil is coated with finely divided platinum. This electrode is placed in
beaker containing an aqueous solution of some acid having concentration nearly one molar
HCl solution. Hydrogen gas at 1 atm pressure is continuously bubbled through the solution
at a temperature of 298K. The oxidation or reduction in the SHE takes place at platinum
foil.

** When SHE acts as anode, oxidation will take place at it as H2(g) 2H+(aq) + 2ē
in such a case it is represented as Pt, ½ H2/H+ (1M).
** When SHE acts as cathode, reduction will take place at it as 2H+(aq) + 2ē H2(g)
in this case it is represented as H+ (1M)/ ½ H2, Pt. Pt here, is an inert electrode.

** The electrode potentials of other electrodes are determined by coupling them with SHE. The
electrode potential of an electrode determined relative to the standard hydrogen electrode
under standard conditions is called standard electrode potential. The standard conditions
are 1M concentration of ions in the solution, 298K temperature and 1 atm pressure.
** What is the role of platinum foil in the SHE? -- Platinum foil has a large surface area. It
provides a channel for inflow and out flow of electrons in the cell.

Measurement of standard electrode potentials

In order to determine the standard electrode potential of an electrode, the electrode in standard
conditions is connected to normal hydrogen electrode to constitute a cell.

If the electrode forms the negative terminal of the cell, it is allotted (fixed) negative electrode
potential and vise verse.

The potential difference between the electrodes is determined with help of voltmeter (or
potentiometer). At the same time, the direction of flow of current is also observed which gives
the idea of direction of flow of electrons.

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 M KH. H. SANCHO Lessons notes for Advanced level
Measurement of Eθ using the S.H.E

Temperature,
25oC (298K)
High resistance
voltmeter
Hydrogen gas
1 atmosphere Salt bridge
Zinc electrode
Standard Hydrogen
electrode

Catalytic 1 mol dm – 3 1 mol dm – 3

Platinum H+ (aq) ions Zn2+ (aq) ions
surface
The conditions are important, because the electrode potential is affected by both concentration
of the solutions and the temperature.

In the case of the zinc half cell it has an electrode potential of - 0.76 V. This means that
compared to the standard hydrogen electrode, it forms the relatively negative electrode (it
provides electrons) by the process:
Zn(s) Zn2+(aq) + 2e
While the standard hydrogen elctrode is relatively more positive and undergoes the reduction
reaction
2H+(aq) + 2e H2(g)
And the overall reaction for the zinc-standard hydrogen electrode cell:
Zn|Zn2+(aq)||H+(aq)|Pt|H2(g):
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

REDOX SERIES:
Is a list of redox potentials for the atoms or molecules as measured against standard hydrogen
electrode. Or,

* The arrangement of various elements in order of increasing values of standard reduction

potentials is called electrochemical series or activity series.

** Standard electrode potentials are usually tabulated as reduction potentials. However, the
reactions are reversible and the role of a particular electrode in a cell depends on the relative
oxidation/reduction potential of both electrodes.

** The oxidation potential for a particular electrode is just the negative of the reduction
potential. A standard cell potential can be determined by looking up the standard electrode
potentials for both electrodes (sometimes called half cell potentials).
** The one that is smaller electrode potential will be the anode and will undergo oxidation
(more reactive). The electrode having higher reduction potential acts as cathode.

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 M KH. H. SANCHO Lessons notes for Advanced level

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 M KH. H. SANCHO Lessons notes for Advanced level
APPLICATIONS OF THE ELECTROCHEMICAL SERIES
Some of the important applications of the electrochemical series are:
1. Calculation of the standard EMF of the cell
2. Determination of equilibrium constant of redox reaction.
3. Determination of pH of the cell.
4. Determination of solubility product.
5. Predicting the feasibility of redox reactions.
6. Comparison of the reactivities of metals.

CALCULATION OF THE STANDARD EMF OF THE CELL

The EMF of a cell can be calculated from the half-cell potentials of the two cells (anode and
cathode) by using the following formula

E°cell = E°red(cathode) – E°red(anode)

= E°red(cathode) + E°oxi(anode)
Since, in representation of a cell cathode is written on right hand side and anode on left hand
side, therefore, EMF of a cell is also sometimes written as:
E°cell = ERight - ELeft = ER - EL

Example 1: Calculate the EMF of the given cell, also write the overall cell rection.
Zn/Zn2+ (1M) // Ag+(1M)/Ag.
Standard electrode potential for Zn2+/Zn is – 0.76volts and for Ag+/Ag is 0.80volts.

It is clear from cell, that silver electrode acts as a cathode and zinc electrode acts as
anode:
2Ag+ + 2ē 2Ag Eo = 0.80 V
Zn2+ + 2ē Zn Eo = - 0.76V

EMF = Eocathode - Eoanode

= 0.80 – (- 0.76) = 1.56V

The overall cell reaction is:

2Ag+(aq) + Zn(s) 2Ag(s) + Zn2+(aq)

Example 2: Calculate the EMF of the cell in which the following reaction takes place.
Zn(s) + Ni2+(aq) Zn2+(aq) + Ni(s)
o 2+ o 2+
Given that E Zn /Zn = - 0.76V, E Ni /Ni = - 0.25V

The above reaction can be split into two half reactions as given below:
Zn(s) Zn2+(aq) + 2ē … Oxidation
2+
Ni (aq) + 2ē Ni(s) … Reduction
Since at Zinc electrode oxidation takes place so it acts as anode and at Nickel
electrode reduction takes place so it acts as cathode.
EMF = Eocathode - Eoanode
= EoNi2+/Ni - EoZn2+/Zn
= - 0.25 - (- 0.76) = 0.51V

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 M KH. H. SANCHO Lessons notes for Advanced level
A CELL OF GREATEST OR SMALLEST EMF
Sometimes you may given a several electrodes and their respective electrodes potential and
asked to choose two electrodes and then, construct the cell that yield a greatest or smallest EMF.

A cell of greatest EMF

To construct a cell that will give maximum EMF, choose two electrodes of largest reactivity
differences. That is, construct a cell from most and least reactive.

A cell of smallest EMF

To construct such as cell that may yield smallest EMF, choose two electrodes of smallest
reactivity differences.

Example: Study the electrodes given below;

A3+ + 3ē A Eθ = + 1.72V
B2+ + 2ē B Eθ = - 1.78V
2+ θ
C + 2ē C E = - 3.56V
D+ + ē D Eθ = - 0.72V
3+ θ
E + 3ē E E = + 2.99V
F2+ + 2ē F Eθ = + 0.34V
(a) Choose two electrodes and construct a cell that will yield,
(i) the greatest EMF (ii) the smallest EMF
(b) Which electrode is
(i) the strongest oxidizing agent (ii) the strongest reducing agent

(a) (i) A cell of greatest EMF (more negative and more positive electrodes)
... More negative value is C and more positive value is E
C/C2+ // E3+/E
Eθcell = ER.H.S - EL.H.S
= 2.99 - (- 3.56)
= 6.55 V

(a) (ii) A cell of smallest EMF (small –ve value and +ve value electrodes)
... Less negative value is D and less positive value is F
D/D + // F2+/F
Eθcell = ER.H.S - EL.H.S
= 0.34 - (- 0.72)
= 1.06 V

(b) (i) The strongest oxidizing agent is E, since it causes the more oxidation to take
place on C.
The more positive half cell will contain the oxidizing agent.

(ii) The strongest reducing agent is C, since it causes the more reduction to take
place on E.
The more negative half cell will contain the reducing agent.

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 M KH. H. SANCHO Lessons notes for Advanced level
DEPENDENCE OF ELECTRODE POTENTIAL ON
CONCENTRATION AND TEMPERATURE
In electrochemical series the electrode potential of various electrodes are given in standard state.
However, the galvanic cells are generally operated under conditions different from the standard
state conditions.

The relationship between electrode potential and concentration of the substances involved in the
half cell reaction is given by Nernst equation. The general half reaction for an electrode may be
written as:
Mn+ + nē M

The Nernst equation for the above half reaction can be written as:

Or,

Where, R = 8.314JK – 1 mol – 1

T = Temperature in Kelvin scale
F = 96500 coulombs
n = Number of moles of electrons transferred
[M] and [Mn+] refer to the molar concentrations of element and its cation respectively.

Substituting the values of R, F, and T (298K) in equation above we get,

( ... [M] = 1)

This is, Nernst equation

for Electrode potential
only.

** In calculating cell potential, the Nernst equation is applicable as well. The Nernst equation
for a particular cell reaction can be written as:

Substituting the values of R, F, and T (298K) in equation above we get,

Nernst equation for Cell

potential of a reaction

Where, K is the equilibrium constant for a redox reaction. For simplicity, the equation can be
expressed as,

Or

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 M KH. H. SANCHO Lessons notes for Advanced level
Example 1: Determine the EMF of the following cell;
(a) Al/Al3+ (0.01M) // Zn2+/Zn (1.0M) ;
EθAl3+/Al = - 1.66V, EθZn/Zn2+ = - 0.76V
(b) Pb/Pb2+ (0.01M) // Br – / ½ Br2 (0.02M)
Eθ Pb2+/Pb = - 0.13V , Eθ ½ Br2/Br - = +1.07V

(a) Ecell = EθZn - EθAl

The Aluminium electrode is not under standard conditions; hence, the Nernst
equation for electrode potential is applied as follow:

In case of Al: [Al3+] = 0.01M, n = 3 (electrons transferred) and Eθ = - 1.66V

EAl = - 1.66 + (0.0591/3) x log(0.01)
= - 1.66 + (- 0.04)
= - 1.70V
... Ecell = EθZn - EθAl = - 0.76 - ( - 1.70)
= 0.94V

Alternatively,

Al Al3+ + 3ē x2 (Oxidation half reaction)

Zn2+ + 2ē Zn x3 (Reduction half reaction)

2Al + 3Zn2+ 2Al3+ + Zn (Net reaction)

Then, ; n = 6 and E θcell = - 0.76 – (-1.66) = 0.90V

From, Nernst equation for cell potential we get,

E = 0.90 - (- 0.04)
= 0.94V

(b) Cell potential for Lead (Pb) half – cell; n = 2, Eθ Pb = - 0.13V, [Pb2+] = 0.01M
EPb = - 0.13 + (0.0591/2) x log (0.01)
= - 0.19V
Cell potential for Bromine (Br) half – cell; n = - 1 , Eθ = 1.07V, [Br – ] = 0.02M
EBr = 1.07 + {0.0591/(- 1)} x log (0.02)
= 1.17V

... Ecell = EBr - EPb = 1.17 - (- 0.19)

= 1.36V

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 M KH. H. SANCHO Lessons notes for Advanced level
Alternatively,
Pb Pb2+ + 2ē x 1 (oxidation half reaction)
½ Br2 + ē Br – x 2 (Reduction half reaction)
Pb + Br2 2Br – + Pb2+ (Net redox reaction)

... Eθcell = EθBr - EθPb

= 1.07 - (- 0.13) = 1.20V

[oxidized form] = [Pb2+] = 0.01M

[Reduced form] = [Br – ] = 0.02M and n=2

K = [Pb2+] [Br – ] 2 = {0.01 x (0.02)2} = 4 x 10 – 6 M3

Ecell = 1.20 - (0.0591/2) x log (4 x 10 – 6)

= 1.20 + 0.16
= 1.36V

Example 2: What is the potential of a half – cell consisting of zinc electrode in 0.01M ZnSO4
solution at 25oC, Eθ = - 0.76V.

Number of electrons transferred by Zinc = 2, and [Zn2+] = 0.01M

The electrode potential is given by:

E = - 0.76 + (0.0591/2) x log (0.01)

= - 0.76 + (- 0.0591)
= - 0.76 - 0.06 = - 0.82V

Example 3: Calculate the EMF of a Daniel cell at 35oC using a 2.0M ZnSO4 solution and a
0.5M CuSO4 solution.

T = 35oC = 308 K, [Zn2+] = 2.0M and [Cu2+] = 0.5M

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) (Net reaction) (n = 2)

whereas,

Substitute values of R (8.314Jmol-1K-1), T (308K), F (96500C), K = 4, and n = 2

Eθcell = EθCu - EθZn = 0.34 - (- 0.76) = 1.10V

E = 1.10 - 0.0184 = 1.10 - 0.02 = 1.08V

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 M KH. H. SANCHO Lessons notes for Advanced level
A CONCENTRATION CELL
Concentration cell: is an electrochemical cell where the two electrodes are the same material,
the electrolytes on the two half-cells involving the same ions, but the electrolyte
concentration differs between the two half-cells. Or
Concentration cells: These are galvanic cells which consist of electrode of same element but
concentrations of electrolyte in cathodic and anodic half cells are different.

** The potential difference across the two electrodes is developed because of the difference in
the concentrations of electrolytes. The electrode in which concentration of electrolyte is
larger acts as cathode whereas the electrode in which concentration of electrolyte is less
acts as anode. That is, Reduction will take place in the cell's compartment where
concentration is higher and oxidation will occur on the more dilute side.

The cell's EMF of concentration cell is calculated through Nernst equation as follows: Consider
the cell;
M/Mn+ (C1 (Diluted)) || Mn+ (C2 (Concentrated)) /M

** The value of E° in this kind of cell is zero, as electrodes and ions are the same in both half-
cells. For the concentration cell to exhibit positive EMF, C2 > C1.

Example 1: The following cell notation describes the cell mentioned above:
Cu(s) | Cu2+ (0.05 M) || Cu2+ (2.0 M) | Cu(s)

Oxidation: Cu(s) Cu2+ (0.05 M) + 2ē (Diluted)

Reduction: Cu2+ (2.0 M) + 2ē Cu(s) (Concentrated)
Overall reaction: Cu2+ (2.0 M) Cu2+ (0.05 M)
The cell's emf is calculated through Nernst equation as follows:

EMF = 0.047V

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 M KH. H. SANCHO Lessons notes for Advanced level
DETERMINATION OF EQUILIBRIUM CONSTANT OF REDOX REACTION

** A cell is said to be at equilibrium if the rate at which anode dissolves equal to the rate at
which cathode dissolve.
** At equilibrium, there is no flow of electron to the external circuit and EMF of the cell
becomes zero. By using EMF equal to zero and applying Nernst equation, equilibrium
constant can be calculated.
0.05 1
Eo log
n
0.05 1
Eo log
n
0.05 1
Eo log
n
n Eo cell
log
0.05 1

16. n Eo cell
10
Example 1: Oxidation of Fe2+ by aqueous acidified Cr2O7 2 – proceeds according to the equation,
6Fe2+ + Cr2O7 2 – + 14H+ 6Fe3+ + 2Cr3+ + 7H2O
Calculate (i) EMF of the cell
(ii) Numerical value of K
Given that, Fe3+ + ē Fe2+ + 0.77V
2– +
Cr2O7 + 14H + 6ē 2Cr3+ + 7H2O + 1.33V

(i) Ecell = Ecathode - Eanode

= 1.33 - 0.77
= 0.56V

Fe3+ + ē Fe2+ x6
2–
Cr2O7 + 14H+ + 6ē 2Cr3+ + 7H2O x 1

6Fe2+ + Cr2O7 2 – + 14H+ 6Fe3+ + 2Cr3+ + 7H2O

16. n Eo cell
(ii) From, 10 ; n = 6, Eocell = 0.56V
1016. x 6 x 0.56
K = 6.08 x 1056

Question 1: Calculate the equilibrium constant of the cell Zn/Zn2+ // Ag+/Ag

Question 2: The reduction potentials of Cu2+/Cu and Ag+/Ag electrodes are 0.34V and 0.80V
respectively. For what concentration of Ag+ ions, the EMF of the cell at 25oC is
zero? Given the concentration of Cu2+ ions is 0.01M.

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 M KH. H. SANCHO Lessons notes for Advanced level
DETERMINATION OF pH OF CELL
** pH of a cell is determined when one of the electrode is hydrogen and platinum of unknown
concentration and another of known concentration
** A voltammeter must be provided for measuring EMF of the cell. It is also connected to the
external circuit across the two electrodes to record the EMF of the cell.

Example 1: The EMF of a cell corresponding to the reaction;

Zn(s) + 2H+(aq) Zn2+(0.01M) + H2(g) is 0.28V.
Calculate the pH of solution of hydrogen electrode. (Ans: 9.12)

According to the equation above and Nernst equation of redox reaction. EMF is
given by:
0.05 1 n2+ ]
EMF Eθ log + 2 n 2, n2+ ] 0.01M
n H ]
0.05 1
0.2 0. 6 log 1 x 10 2 log H+ ]2
2
0.05 1 0.05 1
0.2 0. 6 x 2 x( 2 log H+
2 2

0.05 1 log H+ 0. 1 1 0.2

0.53 1
pH log H+
0.05 1

Example 2: Calculate the pH of the following cell Pt/ ½ H2/H+ // Ag+/Ag.

If Ag+/Ag Eo = 0.80V, and Ecell 1.22V

H2 2H+ + 2ē
(Oxidation half reaction)
2Ag+ + 2ē Ag (Reduction half reaction)
H2 + 2Ag+ (aq) 2H+(aq) + 2Ag (Net reaction)

Since, EoAg = 0.8V, at standard conditions (25oC and [Ag+] = 1M) and n = 2
Eocell = EoAg - EoH = 0.80 - 0.00 = 0.80V
Hence,
0.05 1 H+ ] 2
EMF Eo log
n g+ ] 2
0
0.05 1
1.22 0. ( log H+ ]2 log g+ ]2 )
2
1.22 0. 0
log H+
0.05 1

pH = 7.1

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 M KH. H. SANCHO Lessons notes for Advanced level
DETERMINATION OF SOLUBILITY PRODUCT

Solubility: Is the maximum amount of solute which can be released into solution as ions at a
given temperature.
Solubility product (Ksp): Is the product of the concentrations of ions raised to the power of
their stoichiometric coefficient of sparingly soluble electrolyte in a standard solution
at a five temperature.

** NOTE:
More details concerning with solubility products are obtained in its reliant topic.

** The solids having solubility less than 0.01M are termed as sparingly soluble solids. The salts
such as barium sulphate, silver chloride, silver chromate, etc. belong to this category of salts.
** Ksp is constant at a given temperature.

Consider, AB(s) aA+ (aq) + bB – (aq)

... Ksp = [A+] a [B – ] b

Example 1: The standard electrode potential for Cu/Cu2+ is 0.34V. Calculate the reduction
potential of pH = 14 for the above couple. (Ksp (Cu(OH)2 = 10 – 19 ))

Cu(OH)2 Cu2+(aq) + 2OH – (aq)

Ksp = [Cu2+] [OH – ] 2

From,
pH +
pOH = 14
14 +
pOH = 14
... pOH = 0
pOH = - log[OH- ] = 10 o = 1M

Recall,
Ksp = [Cu2+] [OH – ] 2
10 – 19 = [Cu2+] (1)2
[Cu2+] = 10 – 19 M

The reduction potential is obtained from Nernst equation,

0.05 1
EReduction Eθ + log Cu2+
n

Substitute, EθCu = 0.34V, n = 2 and [Cu2+] = 10 – 19 M

0.05 1 1
0.34 + log 10
2

Example 2: Find the solubility product of a saturated solution of AgCrO 4 in water at 25oC. If the
EMF of the cell Ag/Ag+ is 0.164 V at 25oC.

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 M KH. H. SANCHO Lessons notes for Advanced level
AgCrO4 Ag+ (aq) + CrO4 – (aq)
+
Ksp = [Ag ] [CrO4]
But, [Ag+] = [CrO4]
Hence, Ksp = [Ag+] 2
From Nernst equation,

0.05 1
EMF Eθ + log g+
n

Substitute, EθAg = 0.80 V , n = 1 and EMF of cell = 0.164 V

0.164 0. 0 + 0.05 1 log g+
0.164 0. 0
log g+
0.05 1

log [Ag+] = - 10. 76

[Ag+] = 10 – 10.76 = 1.7 x 10 – 11
+ 2
Recall, Ksp = [Ag ]
= (1.7 x 10 – 11 ) 2
= 3.02 x 10 – 22 mol2dm – 6
. . The solubility product is 3.02 x 10 – 22 mol2dm – 6
.

COMPARISON OF THE REACTIVITIES OF METALS

** The metals which occupy higher position in electrochemical series have lower reduction
potentials. This indicates that ions of such metals will not be reduced to metals easily. On the
contrary, such metals would be easily oxidized to their ions by loosing electrons. Therefore,
from the position of the metal in the electrochemical series, it is possible to predict the
relative reactivities of metals.
** The metal having smaller reduction potential can displace metals having larger reduction
potential from the solutions of their salts. In other words, the metals occupying higher
position in the series (are more reactive) can displace the metals lying below it from the
solutions of their salts.
For example, zinc lies above copper in the series and hence, it can displace copper from
copper sulphate solution. Copper cannot displace zinc from zinc sulphate solution because
lies below zinc in the series and hence, it is less reactive.

Example 1: Colour of the KI solution containing starch turns blue when Cl2 water is added.
Explain.

Chlorine is placed below iodine in electrochemical series having higher E θred and
thus undergoes reduction whereas I – undergoes oxidation.
2I – I2 + 2ē
Cl2 + 2ē 2Cl –

Cl2 + 2I – I2 + 2Cl –
The I2 so formed gets absorbed in starch to give blue colour.

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 M KH. H. SANCHO Lessons notes for Advanced level
PREDICTING THE FEASIBILITY OF REDOX REACTIONS
** With the help of electrochemical series we can predict whether a given reaction will take
place or not. From the given equation, the substance undergoing oxidation and reduction
are identified.
** When two electrodes combine to form a cell, the value of E for the cell must be positive
(i.e., E > 0), if the cell reaction is to happen spontaneously, and if EMF comes out to be
negative, the given redox will not take place.

NOTE: ** The electrode potential of a half reaction which undergoes oxidation must be
reversed.
** Multiplication of any constant number (integer) will not affect the value of electrode
potential.
(Since the number of electron lost must be equal to the number of electron gained,
the half reaction must be multiplied by integers).

Example 1: Predict whether the following redox reaction is feasible or not under standard
conditions:
(i) Sn +2 (aq) + Cu(s) Sn(s) + Cu +2 (aq)
(ii) Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s)
+
(iii) Cu(s) + 2H (aq) H2(g) + Cu2+(aq)
–
(iv) Cl2(g) + 2F (aq) F2(g) + 2Cl – (aq)
Given that; Eθ Sn2+/Sn = - 0.14V , Eθ Cu2+/Cu = 0.34V
E Zn /Zn = - 0.76V , Eθ Ag+/Ag = 0.80V
θ 2+

Eθ H+/ ½ H2 = 0.00V , Eθ ½ F2/F – = 2.85V

Eθ ½ Cl2/Cl – = 1.36V

The above reactions can be split into two half reactions as given below:
(i) Cu(s) Cu2+(aq) + 2ē …..Oxidation Eθ = - 0.34V
2+
Sn (aq) + 2ē Sn(s) ….. Reduction E θ = - 0.14V

Sn+2(aq) + Cu(s) Sn(s) + Cu +2 (aq) ….. Net reaction Eθ = - 0.48V

Since the value of EMF comes out to be negative, the given reaction is not feasible

(ii) Zn(s) Zn2+(aq) + 2ē Eθoxi = 0.76V

2Ag+(aq) + 2ē 2Ag(s) Eθred = 0.80V

Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s) Ecell = 1.56V

The reaction is feasible (spontaneous), since, EMF comes out to be positive

(iii) Cu(s) Cu2+(aq) + 2ē Eθoxi = - 0.34V

2H+(aq) + 2ē H2(g) Eθred = 0.00V

Cu(s) + 2H+(aq) H2(g) + Cu2+(aq) Ecell = - 0.34V

Since the value of EMF comes out to be negative, the given reaction is not feasible

(iv) Cl2(g) + 2F – (aq) F2(g) + 2Cl – (aq) Ecell = 1.36 – 2.85 = - 1.49V
The reaction is not spontaneous, E = -1.49V

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 M KH. H. SANCHO Lessons notes for Advanced level
Example 2: Given; Zn2+ + 2ē n Eθ = - 0.76V
Ni2+
+ 2ē Ni E θ = - 0.25V
Ag +
+ ē g E θ = 0.80V
Predict whether a spontaneous reaction will occur or not, when,
(i) a piece of silver wire is dipped in a ZnSO4 solution.
(ii) a piece of zinc metal is dipped in a NiSO4 solution.

(i) 2Ag + ZnSO4 Ag2SO4 + Zn

2Ag + Zn2+ 2Ag+ + Zn
2Ag 2Ag+ + 2ē Eθoxi = - 0.80V
Zn2+ + 2ē n E θred = -0.76V

2Ag + Zn2+ 2Ag+ + Zn Eθcell = - 1.56V

The reaction will not occur, this means that silver cannot replace zinc from ZnSO4
solution.

(ii) Zn + NiSO4 ZnSO4 + Ni

Zn + Ni2+ Zn2+
+ Ni
Zn Zn2+ + 2ē Eθoxi = 0.76V
Ni2+ + 2ē Ni E θred = - 0.25V

Zn + Ni2+ Zn2+ + Ni Eθcell = 0.51V

The reaction will occur, this means that zinc can replace nickel from NiSO4
solution.

Question 1: Given the following:

Cu2+(aq) + 2ē Cu(s) E θ = 0.34V
Ag+(aq) + 2ē g(s) E θ = 0.80V
(i) Which of the following is thermodynamically feasible, the reduction of silver ion
(Ag+) by copper or reduction of copper ion (Cu2+) by silver? Give reason(s) for
your answer.
(ii) Write the redox equation for the thermodynamically feasible reaction.
(iii) Write the cell notation for the thermodynamically feasible reaction.
(iv) Determine the standard cell EMF.

Question 2: Explain why 1M AgNO3 solution cannot be stored in a copper vessel but 1M CuSO4
can be stored in a silver vessel.

Question 3: Check the feasibility of the following redox reactions with the help of
electrochemical series:
Ni(s) + 2Ag+ (aq) Ni2+ (aq) + 2Ag(s)
θ 2+ θ +
[E Ni /Ni = - 0.25V , E Ag /Ag = + 0.80V ]

Question 4: Chlorine gas is passed through a bromide solution. Explain the feasibility of the
reaction on the basis of given electrochemical data:
Eθ Cl/Cl – = + 1.36V ; Eθ Br/Br – = + 1.07V

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 M KH. H. SANCHO Lessons notes for Advanced level
CORROSION AND ITS PROTECTION

Corrosion is the term applied to steel rust caused by an electrochemical process. Most people
are likely familiar with the corrosion of iron, in the form of reddish rust. Other examples include
the black tarnish on silver, and red or green corrosion that may appear on copper and its alloys,
such as brass.

Corrosion: Is the process by which metals are oxidized in the atmosphere. Example of corrosion
is rusting of iron.

** Rusting is a slow chemical reaction which will only take place under favourable conditions.
Water and air (oxygen) are necessary for rusting to occur.

IRON CORROSION
** Is an electrochemical reaction, steel has non – uniform surface because of chemical
composition is not homogeneous.
** For iron rust to occur the metal has to be in contact with oxygen and water, although
chemical reactions for this process are relatively complex and not all of them are completely
understood.

** It is believed the causes are the following: Electron transferring (reduction-oxidation), one
area on the surface of the metal acts as the anode, which is where the oxidation (corrosion)
occurs.
At the anode (anodic region), the metal gives up electrons,
Fe(s) Fe2+(aq) + 2ē

** These electrons that are releases transferred from iron, reducing oxygen in the atmosphere
into water on the cathode (cathodic region).
O2(g) + 4 H+(aq) + 4ē 2 H2O(l)

**Global reaction for the process:

2 Fe(s) + O2(g) + 4 H+(aq) 2 Fe2+(aq) + 2 H2O(l)
+
Iron corrosion takes place on acid medium; H ions come from reaction between carbon
dioxide in the atmosphere and water, forming carbonic acid.

** The Fe2+ ion formed in anodic region travel to the cathodic region through the moisture on the
surface of steel and on the way they oxidized to iron (iii), (Fe3+) by oxygen.
The Fe3+ ion hydrolyse to form rust.

Fe2+ ions oxides, following this equation:

4 Fe2+(aq) + O2(g) + (4+2x)H2O(l) 2 Fe2O3·xH2O + 8 H+(aq)

** Iron(III) oxide hydrated is known as rust. The concentration of water associated with iron
oxide varies, thus chemical representation is presented as Fe2O3·xH2O. The electric circuit
works as passage of electrons and ions occurs, thus if an electrolyte is present it will
facilitate oxidation, this explains why rusting is quicker on salt water.

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 M KH. H. SANCHO Lessons notes for Advanced level
METHODS OF PREVENTING CORROSION
The following methods can be used for preventation of corrosion
1. Sacrificial anodes: A method commonly used to protect a structural metal is to attach a metal
which is more anodic than the metal to be protected. This forces the structural metal
to be cathodic, thus safe corrosion.
It is called "sacrificial" because the anode dissolves and has to be replaced
periodically.
2. Oiling and greasing: This involves coating iron with oil/grease.
3. Painting: This is the coating of items with special pigment paint. Items that are made of iron
are usually painted to make them last longer.
4. Use of silica gel: Is a chemical containing silicon found in sand and rocks. Silica gel is a
substance in the form of grains and absorbs moisture. Some fragile instruments such
as cameras have iron and steel parts. These cannot be protected by painting, oiling,
galvanizing or even tin plating. Silica gel absorbs any moisture that may cause
rusting.
5. Electroplating: Iron is coated with another metal like zinc, tin, or chromium for protection of
its surface from rust. But these materials have not equally efficient.
(i) Galvanization: This is process of coating iron or steel with zinc.
Compare the position of these metals in electrochemical series
EθZn2+/Zn = - 0.76V
EθFe2+/Fe = - 0.44V
EθSn2+/Sn = - 0.14V

Zinc (Zn) Iron (Fe)

Zinc is more reactive than iron, when exposed can easily undergo oxidation.
Zn Zn2+ + 2ē
2+ –
Zn + 2OH Zn(OH)2
Zn(OH)2 formed is very stable and cannot undergo further oxidation.
This is used to prevent rust.

NOTE: Galvanization cannot be used for food cane it dissolves in acid and form zinc
compounds which is very poisonous.
Zn2+ + Cl – ZnCl2
Question 1: Why do you think the zinc on galvanized iron is sometimes called sacrificial anode?
Question 2: Explain why blocks of magnesium can be attached to the hulls of ships or attached
to iron pipes with the aim of preventing rusting.

(ii) Tin plating: This is coating of iron with tin. Iron is more reactive than tin compound,
therefore, iron go into solution and ionized and react with OH – ion to form
Fe(OH)2 which oxidized by O2 forming Fe(OH)3 which is rust.

Tin (Sn) Iron (Fe)

NOTE: Tin cans are actually made of steel, but the inside of the can is coated with a thin layer
of tin. This makes them suitable for canning foods, although encourage rust when is
screeched and exposed to the atmosphere.

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 M KH. H. SANCHO Lessons notes for Advanced level
ELECTROLYSIS
The production of chemical, changes by passing an electric current through a solution or molten
salt (the electrolyte), resulting in the migration of ions to the electrodes; positive ions (cations) to
the negative electrode (cathode) and negative ions (anions) to the positive electrode (anode).

Electrolysis: Is the decomposition of an electrolyte by passing an electric current through it.

The word “lysis” means to dissolve or break apart.
Electrolysis requires an external source of electrical energy to induce a chemical
reaction, and this process takes place in a compartment called an electrolytic cell.
Electrolytes: Are substances which when in solution or molten, conduct an electric current and
decomposed by it.
** Electrolytes are described as ‘strong’ or ‘weak’ according to whether their aqueous
solutions are good or poor conductors.
** Electrolyte consists of ions (the charged particle), but all atoms are neutral.
An anion: Is a negatively charged ion that moves to the anode
A cation: Is a positively charged ion that moves to the cathode.
Electrodes: Are two poles/plates of carbon or metal at which the current enters or leaves an
electrolyte.
** Cathode: Is the negative electrode at which electrons enters an electrolyte (i.e.,
electrons leave external circuit).
** Anode: Is the positive electrode at which electrons leaves an electrolyte (i.e.,
electrons enter the external circuit). This is electrode, which is attached to
the positive terminal of the battery.
** If electrodes take no part, they are described as inert electrodes. If inert electrodes
are used the overall reaction usually (but not always) consists of decomposition of
electrolyte only. Platinum and Carbon (graphite) usually behave as inert electrode,
although platinum is attacked by liberated chlorine and graphite by liberated
oxygen.

Selective discharge (preferential) discharge of ions during electrolysis

At electrodes, some of the ions gain or lose electrons. This has the effects of discharging the ions.
Only one type of ions is discharged at each electrode. If two or more different ions with similar
charges (such as Na+ and H+ or OH – and SO4 2 –) are present at electrodes, they will compete
for discharge.

The discharge depends on:

1. Position of ion on electrochemical series (ease of discharge of ion). An arrangement of
metal ions in order of which they can be reduced is referred as electrochemical series. It is a
list of metals with most active at the top (they are not readily discharged because their ions are
very stable in solution) and the least active at the bottom. If all other factors are constant, any
ion will be discharged from solution in preference to those above it.
2. Nature of electrode. This factor may sometimes influence the choice of ion for discharge. The
mass of anode decreases, while the cathode never dissolved regardless of the material used.
3. Concentration of competing ions. Increasing concentration of ions tends to promote its
discharge at the electrodes. For example, in HCl acid, containing OH – (from water) and Cl – ),
the conc. of Cl – is discharge in preference to OH – , however, OH – being below in
electrochemical series.

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 M KH. H. SANCHO Lessons notes for Advanced level
FARADAY’S LAWS OF ELECTROLYSIS
The process of electrolysis of a substance is governed by the two laws of Michael Faraday,
known as Faraday’s laws of electrolysis (named after him).
Expressed in modern terms they declare that the amount (expressed in moles) of an
element liberated during electrolysis depends upon:
(a) The time of passing the steady current.
(b) The magnitude of the steady current passed
(c) The charge on the ion of the current.

FARADAY’S FIRST LAW OF ELECTROLYSIS

It states that “The mass of the substance librated or deposited on an electrode during electrolysis
is directly proportional to the quantity of electric charge passed through the
electrolyte”.
i.e., M α Q M ZQ
Z is electrochemical equivalent, given as:
r
F
Since, M = ZQ but Q = It, then,
A I
M
F
Whereas; I = current in ampere (A), Q = Quantity of electricity
Ar = Relative atomic mass, t = time in seconds
V = Valency, M = Mass of substance
F Faraday’s constant ( 6500 Coulomb/mole)

Electrochemical equivalent (ECE) may be defined as “the mass of the substance deposited by
passing a current of one Ampere for one second (i.e., by passing Coulomb of
electricity)”. Its unit is gram per coulomb (g/C).

NOTE: 1 Faraday = 96500 Coulomb = 1 mole of particles

Number of mole of electron transferred = valency
Thus one mole of V3+ corresponds to three equivalents of this species, and will
require three faradays of charge to deposit it as metallic vanadium.

FARADAY’S SECOND LAW OF ELECTROLYSIS

It states that “When same quantity of electricity is passed through different electrolytes, the
amount of different substances deposited at the electrodes is directly proportional
to their equivalent weights.”
i.e., M1 α E1 and M2 α E2, hence, M1 = QE1 and M2 = QE2
M E
M E
Where, M1 and M2 are respective masses of substances produced on the electrodes.
E1 and E2 are the chemical equivalent of two substances respectively.
Chemical equivalent: Is the relative atomic mass of the substance divided by the number of
electrons required to oxidize or reduce each unit of the substance.
R. .M r
Chemical equivalent
alency

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 M KH. H. SANCHO Lessons notes for Advanced level
Example 1: The same quantity of electricity is used to liberate iodine (at anode) and a metal X
(at cathode). The mass of X liberated is 0.617g and the iodine is completely
reduced by 46.3cm3 of 0.124 molar Na2S2O3 solution. Calculate the chemical
equivalent mass of X.

Mass of X liberated = 0.617g ( I = 127 )

Number moles of Na2S2O3 = MV = (46.3/1000) x 0.124 = 5.741 x 10 – 3 moles.
R.T.C, Chemical equivalent mass of X = ?

From Equation,
2S2O3 2 – + I2 S 2 O6 2 – + 2I –
2moles 1mole
5.741 x 10 – 3 moles (5.741 x 10 – 3 /2) = 2.871 x 10 – 3 moles

Mass of iodine = Moles x Molar mass

= 2.871x 10 – 3 x 254
= 0.729 g

MI = 0.729g ; Mx = 0.617 g ; EI = Ar/V = 254/2 = 127 ; Ex = ?

Then, from Faraday’s second law,

MX EI 0.61 x 12
EX
MI 0. 2

Example 2: By passing a current of 0.65A for 35min through water, copper and silver
coulometer the following masses of elements were liberated: 0.0143g of
hydrogen, 0.114g of oxygen, 0.449g of copper, and 1.542g of silver.
Show that these results agree with faraday’s second law.
(H = 1.008, O = 16.0, Cu = 63.5, Ag = 107.9)

The ratios of masses of H : O : Cu : Ag = 0.0143 : 0.114 : 0.449 : 1.542

= 1 : 7.97 : 31.40 : 107.8
The ratios of the equivalent masses obtained from the relative atomic masses
= 1.008 : 8.0 : 31.75 : 109.9
Hence, within the limits of experimental working, the experimental results agree
with Faraday’s second law.

Question 1: 0.406g of a metal X was deposited from a solution by a current of 1A flowing for
965second. The metal formed a volatile chloride of relative vapour density of 114.
Calculate the relative atomic mass of the metal. (Ans: 121.8)
Question 2: When does the electrolysis of CuSO4 solution using copper electrodes stop?
Question 3: What does the amount of element liberated in electrolysis depend upon?

“We came here to be philosophers and I hope you will always remember that
whenever a result happens especially, if it be new, you should say, “what are the
causes? Why does it occur?” and you will in the course of time to find out
reason.” (Michael Faraday).

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 M KH. H. SANCHO Lessons notes for Advanced level
CONDUCTIVITY

O M’S LAW: It states that,

“The current passing through the solid conductor is directly to the potential
difference between electrodes, provided that all physical factors are kept
constant.”
i.e., Potential difference, α Current, I
V = IR
Resistance (R) : It is the property of a substance by which it obstructs the flow of current
through it. Its SI unit is ohm (Ω).
In a uniform conductor, resistance of the material is directly proportional to its
length and also inversely proportional to its area.
l l
R α R
A

Here, l/A is fixed for a conductor, called cell constant and

ρ (Rho), the constant of proportionality is called the Resistivity or specific resistance.

Hence, Resistance = Resistivity × cell constant.

If, in a uniform conductor, l = 1m, A = 1m2 , then R ρ

Thus, Resistivity of a uniform conductor is equal to its resistance when its length is 1 m and its
cross-sectional area is 1m2.

Therefore, the conduction of current through an electrolyte also obeys ohm’s law.
(i) The reciprocal of resistance is called conductance. Its unit is per ohm (Ω - 1 or Siemens, S).
1
i.e., Conductance,
R

(ii) The reciprocal of resistivity is called conductivity or specific conductance.

Its unit is Ω - 1 m – 1 or S m – 1 .
1 l
i.e., Conductivity,
ρ R

Conductivity, K = Conductance, G x cell constant, l/A

Conductivity, K: Is defined as a conductance of a solution which rest between two parallel
electrodes of 1m apart and each having a cross-section area of 1m2.

Question 1: A column of electrolyte 3.00cm long and of cross – section 2.00cm3 has a resistance
of 15.00Ω. Calculate (a) the resistivity and (b) the conductivity of the electrolyte.
Question 2: The resistance of a cell containing 0.01moldm – 3 Cl solutions is 12.5Ω. The
conductivity of KCl at this concentration is 0.1413 Sm – 1. What is the cell constant?
Question 3: The resistance of a conductance cell containing 0.010moldm – 3 KCl solution at
25oC is 4 . 5Ω. If the same cell contains sodium nitrate solution of concentration
0.020moldm – 3, the resistance is 254Ω. The conductivity of the Cl solution is
0.012 Ω - 1 m – 1. Calculate (a) cell constant (b) the conductivity of sodium nitrate
solution.

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 M KH. H. SANCHO Lessons notes for Advanced level
MOLAR CONDUCTI ITY (Λ)
Molar conductivity of solution: Is electrolytic conductivity per concentration of electrolyte in
mole per metre cube. It is denoted by Λ (lambda).
electrolytic conductivity, k
Molar conductivity, Λ
concentration, C

Λ
C in mol/m3

Unit of molar conductivity, Ω - 1 m2 mol – 1 or Sm2 mol – 1

Equivalent conductance: Is the conductivity of the electrolyte which contains 1g equivalent

when the electrodes of cross-section area of 1m2 are kept 1m apart in conducting cell.
The molar conductivity of a solute depends on its concentration. When values of
molar conductivity, Λ are plotted against the volume of solution containing 1mole of
solute, that is the dilution, the graphs obtained for different electrolytes fall into two
categories. These are shown in figure below;
M a c nduc ivi y, Λ

Dilution
Strong electrolytes (Curve A): Are those which are completely ionized in solution. They give
graph of shape , quickly rising to maximum. The maximum value of Λ is called the
molar conductivity at infinite dilution, as further dilution has no effect on its value. It
is represented as Λ∞ or Λo. Molar conductivity decreases slightly with concentration.
Weak electrolyte (Curve B): Are those which are incompletely ionized, give graph similar in
shape to B. The molar conductivity cannot reach maximum with dilution. The value
of Λ increases as the solution becomes more and more dilute.

The conductivity of all electrolytes increases with temperature. However, the

conductivity slightly varies with the pressure due to change in viscosity of the medium.
This alters the speed and hence the conductivity of ions. The viscosity of dilute solution
decreases with increasing the pressure

FACTORS AFFECTING MOLAR CONDUCTIVITY:

1. Nature of electrolyte i.e. strong or weak.
2. Temperature
3. Concentration of electrolytes in solution.

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 M KH. H. SANCHO Lessons notes for Advanced level
KOHL – RAUSC ’S LAW OF IONIC MOBILITY
It states that, “The molar conductivity at infinite dilution for a given salt can be expressed as the
sum of contributions from the ions of the electrolyte.”

lternatively, “molar conductivity of an electrolyte at infinite dilution Λ∞ is the sum of the ionic
conductivities of the cations and the anions each multiplied by the number of ions present in one
formula unit of the electrolyte.”
i.e., for compound AxBy
Λ∞ xΛ∞( y+) + yΛ∞(Bx – )

For example, CaCl2 Ca2+ + 2Cl –

Λ∞ 1 x Λ∞Ca2+ + 2 x Λ∞Cl –
Λ∞Ca2+ + 2Λ∞Cl –

APPLICATION OF KOHL - RAUC ’S LAW:

(i) For determination of Λ∞ of weak electrolytes,
For example,
(ii) For determining degree of dissociation (α) of an electrolyte at a given dilution,
(iii) For calculation of dissociation constant (Kc) of a weak electrolyte at concentration, C of
solution,
(iv) For determination of the solubility of a sparingly soluble salt:

MOLAR CONDUCTIVITIES AND THE DEGREE OF DISSOCIATION

Degree of dissociation: Is the fraction of an electrolyte in the solution which has changed into
ions.
The fraction α of the solute which is ionized gradually increases with dilution. If
measurements could be extended to even more dilute solutions, α would approach a
value of 1, and Λ would level off at a maximum value, Λ∞.

Molar conductivity (Λ) is proportional to the degree of dissociation (α) of an

electrolyte if Λ∞ is molar conductivity of dilution.
Therefore, Λ α (α)
Λ kα ………… (i)
lso, Λ∞ α (α)
Λ∞ kα but in this case α 1
Λ∞ k …………… (ii)

Divide equation (i) by (ii)

Λ kα
Λ∞ k

Therefore,
Λ
α
Λ

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 M KH. H. SANCHO Lessons notes for Advanced level
For weak electrolyte,
HA H+ + A–
Initial C 0 0
At equilibrium C(1 – α) Cα Cα
H+ ]
cid dissociation constant, a
H ]
C2 α2
a
C(1 α)
If 1–α ~ 1
Then, Ka Cα 2

Ostwald’s dilution law

a
α
C

Example 1: Calculate molar conductivity of a 0.05M NaOH solution, if at 25 oC conductivity of

the solution is 1.57 x 10 – 3 Ω - 1 m – 1.

Given, K = 1.57 x 10 – 3 Ω - 1m – 1 C 0.05M Λ ?

1.5 x 10 x 10 3
3
Λ
C 0.05
= 3.14 x10 – 4 Ω- 1 m2 mol – 1

Example 2: Calculate the molar conductivity at infinite dilution at 25 oC of ethanoic acid, given
that the molar conductivities at infinite dilution of HCl acid, NaCl and CH3COONa
are 4.26 x 10 – 2 , 1.26 x 10 – 2 , and 9.1 x 10 – 3Ω- 1m2 mol – 1 respectively.

According to Kohl – rausch’s law,

Λ∞(CH3COOH) Λ∞(CH3COO – ) + Λ∞(H+)

HCl H+ + Cl –
NaCl Na+ + Cl –
CH3COONa CH3COO – + Na+

Thus, Λ∞(CH3COOH) Λ∞(HCl) + Λ∞(CH3COO –) - Λ∞(NaCl)

= 4.26 x 10 – 2 + 9.1 x 10 – 3 - 1.26 x 10 – 2
= 0.0391
= 3.91 x 10 – 2 Ω- 1 m2 mol – 1

The End of the topic

Proudly prepared by: M Kh. H. Sancho.
Dec, 2012 – Feb, 2013

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 M KH. H. SANCHO Lessons notes for Advanced level

CONCEPTUAL QUESTIONS
FOR ACSEE AND OTHER COMPETITIVE EXAMINATIONS

SECTION A:

PROBLEMS ON REDOX REACTIONS:

Question 1: What mass of K2Cr2O7 is required to produce 5.0L of CO2 at 75oC and 1.07atm
pressure from excess of oxalic acid in the presence of dilute H 2SO4? (Ans: 9.173g)
Question 2: 2.55g of iron wire was dissolved in excess of dilute H2SO4 and the volume was
made up to 100ml, 20ml of this solution required 30ml of 0.05M solution of
K2Cr2O7 in acidic medium. Calculate the percentage purity of iron. (Ans: 98.8%)
Question 3: 10ml of a solution of potassium dichromate is allowed to react with saturated
solution of potassium iodide. The iodine liberated quantitatively consumed 32ml of
M/50 solution of sodium thiosulphate. What is concentration of potassium
dichromate solution in gL – 1. (Ans: 3.136gL – 1)
Question 4: A cell is prepared by dipping copper rod in 1M copper sulphate solution and zinc
rod 1M zinc sulphate solution. The standard reduction potentials of copper and zinc
are 0.34V and – 0.76V respectively.
(i) What will be the cell reaction?
(ii) What will be the standard electromotive force (EMF) of the cell?
(iii) How will the cell be presented?
Question 5: (i) Comment on the statement “It is not possible to determine the absolute value of
single electrode potential”.
(ii) When zinc rod is dipped in a copper sulphate solution, the blue colour of copper
sulphate is slowly discharged. Explain the phenomenon.
(iii) Chlorine gas is passed through a bromide solution. Explain the feasibility of the
reaction on the basis of given data: ECl/Cl – = +1.36V ; EBr/Br – = +1.07V
(iv) Why will Ag not react with dil. H2SO4 whereas zinc reacts?
Question 6: (a) A layer of CuO on copper vessel can be easily cleaned by dilute HCl but oxide
layer of aluminium on the aluminium vessel cannot be cleaned by HCl. Give
reason.
(b) An iron nail accidentally fell into a 1M solution of silver nitrate placed in glass
vessel. What observations will be made?
Question 7: Write correctly balanced half reactions and the overall equations for the following:
(i) Fe(OH)2 + H2O2 Fe(OH)3 + H2O (in basic medium)
(ii) MnO4 – + H2C2O4 Mn2+ + CO2 (in acidic medium)
(iii) PbO2 + Cl – ClO – + Pb(OH)3 – (in basic medium)
(iv) MnO4 – + Br – Mn2+ + Br2 (in acidic medium)
Question 8: Starting with the correctly balanced half reactions write the overall ionic reaction
for the following changes:
(i) Chloride ion is oxidized to Cl2 by MnO4 – in acid solution.
(ii) Nitrous acid (HNO2) reduces MnO4 – in acid solution.
(iii) Nitrous acid (HNO2) oxidizes I – to I2 in acid solution.
(iv) Chromite ion (CrO3 – ) is oxidized by H2O2 in strongly basic solution.

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 M KH. H. SANCHO Lessons notes for Advanced level
PROBLEMS ON CONDUCTIVITY:
Question 1: At 25oC a solution of 0.1M acetic acid is 1.3% ionized. If the molar conductivity at
infinite dilution for acetic acid is 3.97 x 10 – 2 mol – 1Ω- 1 m2. Calculate
(i) Molar conductivity at 25oC.
(ii) Conductivity at 25oC. (Ans: K = 5.161 x 10 – 2 Ω -1m – 1)
Question 2: After making allowance for the conductivity of water, the conductivity of a
saturated of silver chloride at 25oC = 1.5 x 10 – 4 Ω- 1 m – 1. If Λ∞(Ag+) = 6.2 x 10 – 3
and Λ∞(Cl – ) = 7.6 x 10 – 3 Ω- 1m2 mol – 1, what is the solubility of silver chloride in
moldm – 3. (Ans: 1.09 x 10 – 5 moldm – 3)
Question 3: 0.005M HF solutions have a conductivity of 92 Ω-1 m – 1 at 25oC. At the same
temperature, molar conductivities at infinite dilution of NaF, NaOH, and H 2O are
493, 360 and 162 mol – 1Ω- 1 m2 respectively. Calculate
(i) dissociation constant of HF solution
(ii) pOH (Ans: pOH = 10.5)
Question 4: How many grams of acetic acid must be dissolved in 1.0 litre of water in order to
prepare a solution of molar conductivity 759 Ω-1cm2 mol – 1 and electrolytic
conductivity 17.5 Ω- 1 cm – 1. (Ans: 1386g)
–3
Question 5: An electrolytic solution of concentration 3.00 x 10 M has a resistance of 45.0Ω in
a cell with cell constant of 2.20 m – 1. Calculate the molar conductivity of the
electrolyte.
Question 6: Experiment shows that, for strong electrolytes, a graph of Λ against
Concentration (i.e. C, ) is a straight line, provided the concentration is not too
large. This provides a way of determining Λ∞. Plot this type of graph using the
following results for sodium hydroxide solutions:
C(NaOH) moldm – 3 0.01 0.04 0.09 0.16 0.25 0.36
Λ Scm2 mol – 1 238 230 224 217 210 202
(i) What is the dilution when C = 0?
(ii) Use your graph to estimate the value of Λ∞ for sodium hydroxide.
Question 7: Calculate the degree of dissociation of ethanoic acid of concentration 1.00x 10 – 3M.
The conductivity of the solution is 4.85 x 10 – 3 Ω - 1 m – 1 and the values of Λ∞ for
ethanoic acid 3.91 x 10 – 2 Ω - 1 m2mol – 1.

PROBLEMS ON ELECTROLYSIS:
Question 1: A metal of relative atomic mass 27 is deposited by electrolysis. If 0.176g of the
metal is deposited on the cathode when 0.15A flows for 3 ½ hours, what is the
charge on the cations of this metal? (Ans: +3)
Question 2: How long would it take a current of 1.20A to put uniform layer of copper 0.10mm
thick on both sides of a brass rectangular plate 10cm by 0.15m?
(e.c.e of Cu = 0.00033g/C, density of Cu = 8.9g/cm3) (Ans: 6.7 x 104sec)
Question 3: An element X has a relative atomic mass of 88. When a current of 0.5A was passed
through fused chloride of X for 32minutes and 10seconds, 0.44g of X was deposited
at the cathode.
(i) Calculate the number of Faradays needed to liberate one mole of X.
(ii) Write the formula of the ion
(iii) Write the formula of the hydroxide of X.
Question 4: 0.2 Faraday of electricity was passed through a solution of copper sulphate.
Calculate mass of copper deposited.

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 M KH. H. SANCHO Lessons notes for Advanced level

PAST PAPERS - QUESTIONS

NECTA - ACSEE

SECTION B:
1. (a) (i) With the aid of a well labeled diagram, describe how Daniel cell is used to supply
electricity.
(ii) Write equations for the reactions taking place at the electrodes and the overall
equation at (a)(i).
(b) (i) Calculate the e.m.f. of the cell operating under standard conditions given that:
Eθ/V
Cu2+/Cu(s) + 0.34
2+
Zn /Zn(s) - 0.76
Ag+/Ag(s) + 0.799
(ii) Explain how the e.m.f. of the cell would be affected by increasing either [Cu 2+] or
[Zn2+].
(iii) If the Zn2+/Zn(s) electrode system was replaced by Ag+/Ag(s) electrode system,
what would be the e.m.f. of the cell?
(NECTA: Qn.2 ; 1986 p1, Qn.3 ; 1995 p1, Qn.1; 2004 p2 and Qn.3 ; 2012 p2)
2. (a) (i) Define oxidation and reduction in terms of current flow.
(ii) Write the oxidation state of sulphur and carbon in the following radicals, S4O62 –
and C2O42 – .
(b) Balance the following reactions which take place in acidic solutions.
(i) ClO – (aq) + I – (aq) I2(aq) + Cl – (aq)
(ii) Cr2O72 – (aq) + I – (aq) Cr3+(aq) + I2 (aq)
2–
(iii) S2O3 (aq) + I2(aq) I – (aq) + S4O62 – (aq)
(c) A standard solution made by dissolving 1.015g of potassium dichromate (VI) is made
up to 250cm3. A 25cm3 portion is added to an excess of potassium iodide and dilute
sulphuric acid. The iodine liberated required 19.20cm3 of sodium thiosulphate. The
reaction equation between thiosulphate and iodine is given by:
S2O32 – (aq) + I2(aq) I – (aq) + S4O62 – (aq)
Find the concentration of the thiosulphate solution in moles per litre.
(NECTA: Qn.4; 2008 p2)
3. (a) With the aid of chemical equation(s), briefly describe the process of rusting of iron.
(b) Given the standard electrode potential t 25oC as;
Metal E θ, V
2+
Zn / Zn - 0.76
2+
Fe / Fe - 0.44
Sn2+ / Sn - 0.14
(i) Predict which coating protects iron more effectively even when coating has been
broken to expose the iron.
(ii) Which of the two metals, Zinc or Tin, is normally used to protect the inside of food
cans and why?
(NECTA: Qn.3 ; 1990 p1)

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 M KH. H. SANCHO Lessons notes for Advanced level

ACKNOWLEDGEMENT
FROM AUTHOR

MR. SANCHO

All praise is for almighty Allah for his blessing, giving strength in all ways, through him
everything is possible. Also, I delightedly extend my heartfelt gratitude to all who are in one way
or another contributed towards the accomplishment of this pamphlet. I say thank you to you all.

This pamphlet of electrochemistry prepared for A-level students and has been written according
to the new syllabus issued by Ministry of education and vocational training of the United
Republic of Tanzania. The more difficult portions of the subject matter and in a few cases more
advanced material have been printed in italic or bolded form so as to possess thoughtfulness to
the readers. In addition, special attempt has been made to keep the language and presentation
simple and free from confusion as possible and there are numbers of examples and questions that
provide wide range of concept to the students and it may also enhance and stimulate teachers in
their teaching activities as a reference but I do not wish to prescribe an order in which teachers
take classes through their chemistry syllabus, I have had to order mine.

Moreover, my innermost thanks should go to the team hand of Dark-room, Zanzibar, for the
excellent work they did in processing this pamphlet. Intentionally, I congratulate all authors of
the text books and other literatures that helped enrich this work. Their contribution in the
production of this pamphlet is very useful. I am also thank you for taking your time to pass
through my work.

Before closing, I wish to place on record my most sincere personal thanks to my wife MARISA
and our dearest daughter SHUFAA M. SANCHO (LAFINGA) for their constant support and for
bearing my partial absence during the preparation of this pamphlet.

I hope you will find that this pamphlet builds on the strengths and serves students even better.
Any errors arising from this pamphlet are the sole responsibility of the author.

Makame Kh. H. Sancho

0773542465 / 0714789590.
Dark – Room,
Zanzibar – Tanzania.
December, 2012 – Feb. 2013

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