ELECTROCHEMISTRY

Prepared by:
Tr. Stephen Omondi Oketch
0711410583/0714839279
©Edited 2023
 KCSE MAPPING ON ELECTROCHEMISTRY
FROM 1995-2022 CHEMISTRY PAPER 2
YEAR QUESTION YEAR QUESTION YEAR QUESTION
1995 WAS NOT TESTED 2008 6 2020 4
1996 2 2009 3 2021 7
1997 1 2010 1 2022 3
1999 2 2011 2 2023 ?
2000 1 2012 5
2001 3 2013 4
2002 4 2015 4
2003 2 2016 4
2004 7 2017 2
2005
2006
3
1
2018
2019
3
6
85.52%
tested
 ELECTROCHEMISTRY
 It is a branch of physical chemistry which deals with interconversion of chemical
energy to electrical energy or electrical energy to chemical energy.
 It can also be defined as the study of electron movement in an oxidation or reduction
reaction at a polarized electrode surface.
 Electrochemistry therefore deals mainly with:
i) Reduction and oxidation
ii) Electrochemical (voltaic) cell
iii) Electrolysis (electrolytic) cell

Redox reactions
The term redox is an abbreviation of reduction and oxidation. The first three letters are
taken from the word reduction and the other two from the word oxidation respectively, to
form redox. Redox reactions therefore involve oxidation and reduction.
6. In ions containing more than one element, the overall charge is equal to the sum
of the oxidation numbers of the constituent elements.

Compound NH4+ OH- SO42-

Oxidation number -3+4(+1)=+1 -2+(+1)= -1 +6+4(-2)= -2

Note: When the oxidation number of an element in a compound or

ion is not known, it is calculated from those of others by using rule 5
and 6 respectively.
worked example
Determine the oxidation number of;
(a) Nitrogen, NO2

=> x + (-2 x2)= -1

x = -1 – (-4) = + 3
 Electrochemical Cell
 An electrochemical cell is a device that can generate electrical energy from the chemical
reactions occurring in it, or use the electrical energy supplied to it to facilitate chemical
reactions in it.

The Tendency of Metals to Form Ions

 When a metal rod is dipped in an aqueous, solution of its ions, some of its surface atoms lose
electrons and go into solution as ions. The lost electrons remain on the metal surface as
illustrated.
 When a metal rod/plate is put in a solution of its own salt, some of the metal ionizes and
dissolve into the solution i.e.
Metal atoms solution Metal ions in solution
M(s) M+ (aq) + e- (Monovalent metal)
M(s) M2+ (aq) + 2e- (divalent metal)
M(s) M3+ (aq) + 3e- (trivalent metal)
The ions move into the solution leaving electrons on the surface of the metal rod/plate.
 The metal rod becomes therefore negatively charged while its own solution
positively charged. As the positive charges of the solution increase, some of them
recombine with the electrons to form back the metal atoms.
M+ (aq) + e- M(s) (Monovalent metal)
M2+ (aq) + 2e- M(s) (divalent metal)
M3+ (aq) + 3e- M(s) (trivalent metal)
 When a metal rod is put in a solution of its own salt, it forms a half-cell. The tendency
of metals to ionize differ from one metal to the other. The difference can be measured
by connecting two half cells to form an electrochemical cell.
 The half cell can be represented as: metal | metal ion. The vertical line represents
the phase boundary where a potential difference develops. For example, a zinc
half-cell is represented as;
Zn(s) | Zn2+ (aq)
 The concentration of electrons on the metal rod is measured by a quantity called the
electrode potential.
 Things to note when drawing an electrochemical or voltaic cell:
i. The half-cell of the more receive metal is placed on the left hand side.
ii. The electrons move from anode to cathode and the movement is showed by
an arrow. This is because the oxidation always take place at the anode and
the reduction at the cathode.
iii. The two half-cells are connected with a salt bridge. The salt bridge can be a
U-tube filled with electrolyte e.g.KNO3 , NaNO3 or a filter paper soaked in
the electrolyte.
iv. The two electrodes that is anode and cathode are connected using a copper
wire.
v. Each electrode is dipped in 1M of its solution.
 Below is an example of zinc-copper metal electrochemical cell:
 When a copper-copper ions half-cell, Cu(s) | Cu2+ (aq) is connected to a zinc-zinc ions
half-cell, Zn(s) | Zn2+(aq), the following observations are made:
i. The zinc rod in the zinc-zinc ions half-cell wears out.
ii. The intensity of the blue colour of copper(II) sulphate solution decreases
and red-brown deposits appear on the copper rod in the copper-copper ions
half-cell.
iii. A voltage of 1.10V is registered by the voltmeter as a measure of the
electromotive force (e.m.f) of the cell. Practically the voltage reading is
lowered because the connecting wires have some resistance to be
overcome.
 In the left-hand side beaker (anode), the zinc rod dissolves by
losing two electrons to form zinc ions, Zn2+(aq).
Zn (s) Zn2+(aq) + 2e-
 The electrons then flow through the external wire to the right-hand side beaker
(Cathode). The copper(II) ions, Cu2+(aq), take these electrons and copper metal
is deposited.

Cu2+(aq) + 2e- Cu(s)

 The overall reaction is as follows:
Zn (s) + Cu2+(aq) Zn2+(aq) + Cu(s)
 The overall reaction is an oxidation-reduction reaction. Oxidation always
occurs at the anode and reduction always occurs at the cathode The Zn(s)|
Zn2+(aq) half-cell is therefore the anode, and the Cu2+(aq) |Cu(s) half-cell is the
cathode.
 For the negative half cell (anode) the Cl- from salt bridge neutralize the
increased positive (Zn2+) ion, while for the positive half cell (cathode) the K+
from salt bridge increase the decreased positive(Cu2+) ion.
 The purpose of the salt bridge therefore is to:
i. complete the circuit by making contact between the two solutions
ii. Maintains balance of charges in electrolytes by providing ions to replace
those ions that are used up or those that are formed.
 The ionic equation and the e.m.f. of the electrochemical cell can be summed up
in what is called a cell notation. A cell diagram is a shorthand for writing
down the cell formed by connecting two half-cells.
Zn(s) | Zn2+ (aq) | | Cu2+ (aq) | Cu (s) E = + 1.10 V
Note:
 | – A single vertical line represents a change in state or a phase between the
metals and their ions
 || – A double vertical line indicates the salt bridge connecting the half-cells.
 Within a half- cell, the reactants are written before the products e.g. zinc metal
(reactant) dissolves to form zinc ions (product), in the other half-cell, copper(II)
ions, Cu2+, (reactant) gain, electrons to form copper metal, Cu(s), (product).
 By convention, the more electropositive electrode (one that does not ionise
easily) is put on the right-hand side.
The e.m.f. of the cell is given by:
E cell = E (right-hand side electrode) – E (left-hand side electrode)
E cell = E RHS – E LHS.
 Standard Electrode Potentials
 The standard electrode potential is denoted by Eθ .
 The standard electrode potential is obtained if the hydrogen half cell is used as
reference and is therefore referred to as the standard hydrogen half cell. Being the
reference electrode, it is assigned an electrode potential 0.00 V.
standard conditions for measuring electrode potential
i. Temperature of 25°C.
ii. All solutions have a concentration of 1 mole per litre (1 M).
iii. Pressure of 1 atmosphere.
 Platinised platinum electrode is used as the electrode when the half-cell does not include a
metal, e.g., H2(g) | H+(aq).

Functions of the platinized platinum electrode

i. It acts as an inert metal connection to the H | H+(aq) system.
ii. It provides a surface area on which dissociation of hydrogen molecules can take
place.
iii. It serves as an electrical conductor to the external circuit.
 The standard electrode potential consist of inert platinum electrode immersed
in 1M solution of (sulphuric(VI) acid) hydrogen ions. H+. Hydrogen gas is
bubbled on the platinum electrode which is dipped in a solution containing 1 M
hydrogen ions.
H2 (g) H+ (aq) + e-
 The standard hydrogen half-cell is presented as:

Pt(s), H2(g) | H+(aq).

 standard electrode potential, E for this reference half-cell which is
zero can be represented as:
½ H2(g) H+(aq) + e– E = 0.00 V
 The emf of the unknown half-cell, E° , can then be calculated from
the expression
Emeasured = ER – EL
If the standard half-cell acts as anode, the equation becomes.
ER = Emeasured (EL = 0)
On the other hand, if standard half-cell is cathode, the
equation takes the form
EL = -Emeasured (ER = 0)
For example, it is desired to determine the emf of the zinc electrode, Zn | Zn2+. It is
connected with the standard hydrogen electrode as shown in figure. The complete
electrochemical cell may be represented as :
Eθ cell= Eθ R – Eθ L
= 0.00V-0.76V
= -0.76V
The overall ionic equation is:
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) Eθ = – 0.76 V
Cell notation,
Zn(s)| Zn2+(aq) || H+ (aq) | H2 (g), Pt(s) Eθ = –0.76V
 Similarly, the emf of the copper electrode, Cu2+ | Cu can be determined by pairing it with
the Standard hydrogen electrode when the electrochemical cell can be represented as :
Pt(s) H2 (g) | H+ (aq) || Cu2+(aq) | Cu(s) Eθ = +0.34V
Measuring the standard electrode potential
for Cu(s) | Cu2+ (aq) half cell

1 M Cu2+
Eθ cell= Eθ R – Eθ L
= 0.34V – 0.00V
=+0.34V
Overall equation;
H2(g) + Cu2+(aq) 2H+(aq) + Cu(s) Eθ = +0.34 V
 The standard electrode potential difference is the potential difference for a cell
comprising a particular element in contact with one molar solution of its ions and the
standard hydrogen electrode.
 Standard electrode potentials are sometimes referred to as standard reduction potential
because they relate to the reduction reactions.
Standard electrode potential
Uses of Standard Electrode Potentials
 Standard electrode potentials are used in:
(i) Comparing the oxidising and reducing powers of substances.
(ii) Determining the e.m.f. of a cell.
(iii) Predicting whether or not a reaction will take place.

Comparing Oxidising and Reducing Power

 Lithium with Eθ = – 3.04 V has the highest tendency to lose electrons and
therefore it is the strongest reducing agent. The more negative the Eθ value
the greater the reducing power. Lithium has the least tendency to accept
electrons hence it is the weakest oxidising agent.
 Fluorine with Eθ of + 2.87 V has the highest tendency to accept electrons
and therefore the strongest oxidising agent. The more positive the Eθ
value, the greater the oxidising power. Conversely, fluorine is the weakest
reducing agent since it has the least tendency to lose electrons.
 Predicting Feasibility of Reaction.
 The feasibility of a redox reaction can be predicted with the help of the electrochemical
series.
 The net emf of the reaction, Ecell, can be calculated from the expression

Eθ cell= Eθ R (Cathode) – Eθ L (anode)

Eθ cell= + ve, the reaction is feasible
Eθ cell= -ve, the reaction is not feasible
Solved problem 1.
Predict whether the reaction 2Ag(s) + Zn2+ (aq) ⎯⎯→ Ag+ (aq) + Zn(s) is feasible or not
hence write the cell notation for the reaction given the cell half reactions as:
2Ag+(aq) + 2e– 2Ag(s) Eθ = +0.80V
Zn2+ (aq) + 2e– Zn(s) Eθ = -0.76 V
Solution
Anode: 2Ag(s) 2Ag+(aq) + 2e– Eθ = +0.80V
Cathode: Zn2+ (aq) + 2e– Zn(s) Eθ = -0.76 V

Eθ cell= Eθ Cathode – Eθ anode

= – 0.763 V – 0.80
= – 1.563
Since Eθ cell is negative, the given reaction is not feasible.
Cell notation:
Ag(s)| Ag+(s) || Zn2+ (aq) | Zn(s) Eθ = –1.56V
 Solved problem 2
The reduction potentials of Mg(s) | Mg2+(aq) and Zn(s) | Zn2+(aq) half-cells are:
Mg2+(aq) + 2e– Mg(s) Eθ = – 2.37V
Zn2+(aq) + 2e– Zn(s) Eθ= – 0.76 V
Using the electrode potentials, answer the following questions.
(i) Write an ionic equation for a cell made by combining the two half cells.
(ii) Calculate the e.m.f. of the cell formed in part (i).
(iii) Write the cell notation for the cell.

Solution:

(i) Since the electrode potential of magnesium is more negative, magnesium is the
stronger reducing agent. Zinc undergoes reduction while magnesium is oxidised.
The sign of the Eθ value of Mg changes from negative to positive.
 Anode: Mg(s) Mg2+(aq) + 2e– Eθ = – 2.37V
Cathode: Zn2+(aq) + 2e– Zn(s) Eθ= – 0.76 V
Eθ cell= Eθ R (Cathode) – Eθ L (anode)
= -0.76V-(-2.37V)
=-0.76+2.37
=+1.61
Mg(s) + Zn2+(aq) Mg2+(aq) + Zn(s) Eθ= +1.61V

(iii) Mg(s) | Mg2+(aq) | | Zn2+ (aq) | Zn (s) Eθ cell = + 1.61V

 Solved problem 3
Calculate the e.m.f. for the electrochemical cell represented below: Al(s) | Al3+ (aq)
| | Zn2+ (aq) | Zn(s).
Give that:
Al3+ (aq) + 3e– Al(s) E° = – 1.66 V
Zn2+(aq) + 2e– Zn (s) E° = –0.76 V
Solution
Note: to combine the two half equations, the number of electrons should be equal.
To do this, multiply the first equation by 2 and the second by 3.
2Al(s) 2Al3+ (aq) + 6e– E° = – 1.66 V
3Zn2+(aq) + 6e– 3Zn (s) E° = –0.76 V

Eθ cell= Eθ R (Cathode) – Eθ L (anode)

= -0.76V-(-1.66V)
=-0.76+1.66v
=+0.90V
2Al(s) + 3Zn2+(aq) 2Al3+ (aq) + 3Zn (s) E° = +0.90V
 Solved problem 4
Use the cell representation below to answer the question that follows
Cu(s) | Cu2+ (aq) | | Ag+ (aq) | | Ag(s) Eθ cell = + 0.46 V
Given that the E value for Ag+(aq) | Ag(s) is + 0.80 V, calculate the Eθ value for
Cu(s) | Cu2+(aq).

Solution
Eθ cell = Eθ R (Cathode) – Eθ L (anode)
+0.46V =+0.80V - Eθ L (anode)
=-+0.80V – 0.4
Eθ L (anode) =+0.34V
Solved problem 5
Use the standard electrode potentials for elements A, B, C, D and E given below to
answer the questions that follow. The letters do not represent actual symbols of
elements.

(i) What is the Eθ value of the strongest oxidising agent? Explain.

+ 1.36 most positive
(ii) Which two of the above elements would produce the largest e.m.f or potential
difference in an electrochemical cell Explain.
 A and E, the elements with the most positive Eθ and the most negative Eθ
.
(iii) What would be the initial potential difference of the cell chosen in(ii) above?

Eθ cell = Eθ R (Cathode) – Eθ L (anode)

=+1.36V –(-2.37V)
= +1.36V +2.37V
=+3.73V

(vi) Write the cell representation for the electrochemical cell formed.

A(s) | A2+(aq) | | E2(g) | E–(aq), Pt (s) Eθ = +3.73 V

Note: Pt presents platinum electrode, any gas half cell MUST be
attached to the platinum electrode.
 When the half cells given are having positive and negative Eθ then:
1. Positive Eθ is a an oxidizing agent positive means addition. The oxidizing
agent undergoes reduction hence makes the Cathode electrode and is placed on
the right hand side of the electrochemical cell.
2. Negative Eθ is a reducing agent, negative meaning substraction. The reducing
agent undergoes oxidation hence makes the anode electrode and placed at the
left-hand side.
 If given half cells are both have positive Eθ then;
1. The one with the most positive is the strongest oxidizing agent hence have
higher tendency of accepting electron (s) therefore, it undergoes reduction
hence make the cathode and placed on the right-hand side.
2. The one with the least positive have high tendency of losing electrons hence
oxidized therefore, makes the anode and placed on the left-hand side.
 When both half-cell have negative Eθ then the one with the highest negative Eθ is
the strongest reducing agent therefore, undergoes oxidation hence make the anode
electrode thus placed on the left-hand side. The one with the least negative Eθ
undergoes reduction therefore, make the cathode electrode and placed on the right-
hand side.