LEARNING UNIT 7

ELECTROCHEMISTRY

PRESENTED

BY

Dr More/Hadebe
20/10/ 2023
 ELECTROCHEMISTRY
• Electrochemistry deals with the conversion of
chemical energy into electrical energy.

• An electrochemical cell - is a device capable of either

generating electrical energy from chemical reactions
or facilitating chemical reactions through the
introduction of electrical energy.

• An electrochemical cell consists of two half-cells.

• Each half-cell consists of an electrode and an

electrode
 18.2 GALVANIC CELLS
• There are two types of electrochemical cells that is:

✓ Galvanic cells (also called voltaic cells and commonly

known as batteries).

✓ Electrolytic cells

• In a galvanic cell, a spontaneous chemical reaction

generates an electric current (reaction occurs on its
own).
 18.2 GALVANIC CELLS
• In an electrolytic cell an electric current drives a
non-spontaneous reaction. (reaction does not occur
on its own, need outside source)

• The two types are therefore the reverse of each

other.

• In this section we will mostly focus on galvanic cells

and the type of spontaneous redox reaction
required for building a galvanic cell.
 18.2 GALVANIC CELLS
• For example: Let us take a look at the reaction of Zn
metal in an aqueous solution of copper sulfate.
• What you will observe is that the dark colored solids
deposits on the surface of the zinc and the blue color of
Cu2+ ion slowly disappearing from the solution.
 IDENTIFYING REDOX REACTIONS
REDUCING AGENT
• Causes reduction
• Loses one or more electrons
• Undergoes oxidation
• Oxidation number of atom
increases
OXIDIZING AGENT
• Causes oxidation
• Gains one or more electros
• Undergoes reduction
• Oxidation number of atom
decreases
 18.2 GALVANIC CELLS
• Zn (s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
• In this redox reaction, Zn is oxidized to Zn2+ and Cu2+ is
reduced to Cu.
• Oxidation is the loss of electrons (an increase in
oxidation number)
• Reduction is the gain of electrons (a decrease in
oxidation number).
• In a galvanic cells we are looking into the half reaction
method.
• In half reaction method a redox reaction can be broken
down into two parts that is oxidation and reduction.
 GALVANIC CELLS
• Oxidation half reaction: Zn(s) → Zn2+(aq) +2e-
• Reduction half reaction: Cu2+(aq) + 2e- → Cu(s)
• overall reaction: Zn(s) + Cu2+ → Zn2+(aq) + Cu(s)

• Each half reaction is balanced separately and added

to obtain the final reaction

• In this reaction Cu2+ is the oxidizing agent because in

gaining electrons from Zn, it causes the oxidation of
Zn to Zn2+.
• Similarly, Zn is the reducing agent because in losing
electrons to Cu2+ it causes the reduction of Cu2+ to Cu
 GALVANIC CELLS
• If the reaction is carried out as shown in Figure 18.2, electrons are
transferred directly from Zn to Cu2+ and the enthalpy of reaction is
lost to the surroundings as heat.
• If the reaction is carried out using the electrochemical cell depicted
in Fig 18.3, however, some of the chemical energy released by the
reaction is converted to electrical energy which can be used to light
a light bulb or run an electric motor.
• The apparatus shown Figure 18.3 is a type of galvanic cell called
Daniell cell.
• The strips of zinc and copper are called electrodes and are
connected by an electrically conducting wire.
• The two solutions are connected by a salt bridge, a U-shaped tube
that contains a gel permeated with a solution of an inert
electrolyte such as sodium sulfate (Na2SO4).
COMMON COMPONENTS IN GALVANIC
CELLS
• Electrodes:
- conduct electricity between cell and surroundings

• Electrolyte:
- mixture of ions involved in reaction or carrying
charge

• Salt bridge:
- Allows the flow of ions but prevents the mixing of the
different solutions that would allow direct reaction of the
cells reactants.
- completes the electrical circuit
 GALVANIC CELL

Figure 18.3
 ELECTRODES
• There are two types of electrodes that is anode and
cathode.
• Anode: negative (-) electrode
- The electrode at which oxidation occurs is called the
anode (the zinc strip).
• Cathode: positive (+) electrode
- The electrode at which reduction occurs is called the
cathode (the copper strip).
• The anode and cathode half reaction must add to give
the overall cell reaction.
PROPERTIES OF ANODE AND CATHODE

ANODE CATHODE
Is where oxidation occurs Is where reduction occurs
Is where electrons are Is where electrons are
produced consumed
Is what anions migrate Is what cations migrate
toward toward
Has a negative sign Has a positive sign
 WORKED EXAMPLE
❖ Design a galvanic cell that uses the redox reaction.
❖ Fe(s) + 2Fe3+(aq) → 3Fe2+(aq)

❖In this reaction, iron metal is oxidized to iron(II) ions

and iron(III) ions are reduced to iron(II) ions.
❖The half cell reaction:
❖Anode (oxidation): Fe(s) → Fe2+(aq) + 2e-
❖Cathode (reduction) : 2 x [ Fe3+(aq) +e-→ Fe2+(aq)]
❖Overall cell reaction: Fe(s) + 2Fe3+(aq) → 3 Fe2+(aq)
❖ Do worked example 18.3
 18.3 SHORTHAND NOTATION FOR
GALVANIC CELLS
• To describe a galvanic cell it is convenient to use a
shorthand notation to represent the cell.
• For Daniell Cell which use this reaction
• Zn(s) + Cu2+(aq)→ Zn2+ Cu(s)
• This expression can be written as follows
Anode half-cell Cathode half-cell
• Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)
Phase
boundary Salt bridge Phase
boundary
Electrons flow this way
 SHORTHAND NOTATION FOR
GALVANIC CELLS
• The short hand for the anode half cell is always
written on the left of the salt bridge and cathode half
cell on the right.

• NOTE: The reactants in each half-cell are always

written first, follow by the products.

• Electrons move through the external circuit from left

to right (from anode to cathode).

• The shorthand thus suggests the overall cell reaction:

• Zn is oxidized to Zn2+, and Cu2+ is reduced to Cu
 SHORTHAND NOTATION
• shorthand for worked example:
• Fe(s) + 2 Fe3+(aq) → 3 Fe2+(aq)

• Fe(s)/Fe2+(aq)//Fe3+(aq), Fe2+(aq)/Pt(s)

• The shorthand for the cathode half-cell includes both

reactant (Fe3+) and products (Fe2+) as well as the
electrode (Pt).

• The two ions Fe3+ and Fe2+ are separated by a comma

rather than a vertical line called (phase boundary)
because they are in the same phase.
 SHORTHAND
• The notation for a cell involving a gas has an
additional vertical line because an additional phase is
present. Thus, the reaction is

• Cu(s) + Cl2(g) → Cu2+(aq) + 2 Cl- (aq)

• The notation

• Cu(s)/Cu2+(aq)//Cl2(g)/Cl-(aq)/C(s)
✓ Copper is oxidized to Cu2+ at a copper anode and Cl2
gas is reduced to Cl- at an inert graphite (carbon)
cathode.
 WORKED EXAMPLE 18.4
• Given the following shorthand notation
• Pt(s) /Sn2+(aq), Sn4+(aq)//Ag+(aq)/Ag(s)
• Because the anode always appears at the left in the
short hand notation the anode oxidation half
reaction is
• Write a balanced equation for the cell reaction
• Solution:
• Anode: Sn2+ → Sn4+(aq) + 2e-
• Cathode: 2 x [ Ag+(aq) + e- → Ag(s)]
• Overall rn: Sn2+(aq) + 2Ag+ (aq)→ Sn4+ (aq) + 2Ag(s)
• Do Practice 18,7
 18.4 CELL POTENTIAL AND FREE-
ENERGY CHANGES FOR CELL REACTION
 18.4 CELL POTENTIAL AND FREE-
ENERGY CHANGES FOR CELL REACTION

Do worked example 18,5: Calculating a standard free-energy change from a standard cell
potential.
 18.5 STANDARD REDUCTION
POTENTIALS
• The standard potential of any galvanic cell is the sum
of the standard half-cell potentials for oxidation at
the anode and reduction at the cathode.

• E°cell = E°ox + E°red

• Look at table 18.1 for the standard reduction

potentials.

• For example: lets consider a cell in which H2 gas is

oxidized to H+ ions at the anode and Cu2+ ions are
reduced to copper metal at the cathode.
 18.5 STANDARD REDUCTION
POTENTIALS
• Anode (oxidation): H2(g) → 2H+(aq) + 2e- E°ox
• Cathode (reduction): Cu2+(aq) + 2e- → Cu(s) E°ox
• Overall reaction: H2(g) + Cu2+(aq) → 2H+(aq) + Cu(s)

• E°cell = E°ox + E°red

• = 0V + 0.34V
• = 0.34V

• Fig 18.6 A galvanic cell consisting of a Cu2+/ Cu half-cell

and a standard hydrogen electrode (S.H.E)
 18.5 STANDARD REDUCTION
POTENTIALS
• The standard hydrogen electrode (S.H.E.) is used as
reference electrode and is assigned an arbitrary
potential of exactly 0 V. It can serve as either the
cathode or anode in a galvanic cell.

• Because Cu2+/Cu half-reaction is a reduction, the

corresponding half-cell potential, E° = 0.34V, is called
a standard reduction potential.

• Cu2+(aq) + 2e- → Cu(s) E° = 0.34V

 18.5 STANDARD REDUCTION
POTENTIALS
• In a cell in which half reaction occurs in the opposite
direction, the E°cell has the same magnitude but
opposite sign:

• Cu(s) → Cu2+(aq) + 2e- E° = -0.34V

• Whenever the direction of a half reaction is reversed,

the sign of E° must also be reversed.

• Thus, the standard potential for an oxidation half-

reaction is the negative of the standard reduction
potential.
 STANDARD REDUCTION POTENTIALS
• When constructing a table of half cell potentials the
following must be observed.

• The half reactions are written as reductions rather than

as oxidations. This means that oxidizing agents and
electrons are on the left side of each half-reaction and
reducing agents are on the right side.

• The listed half-cell potentials are standard reduction

potentials also known as standard electrode potentials.
 STANDARD REDUCTION POTENTIALS
• The half reactions are listed in order of decreasing
standard reduction potential, meaning a decreasing
tendency to occur in the forward direction and an
increasing tendency to occur in the reverse direction.

• The strongest oxidizing agents are located in the

upper left of the table.

• The strongest reducing agents are found in the lower

right of the table.
TABLE 18.1 STANDARD REDUCTION
POTENTIAL AT 25°C
 PROBLEM

• Calculate E°ox for the following galvanic cell

• Half reaction:
• The E value for oxidation of Zn to Zn2+ is 0.76 and the
standard potential for the Zn2+ /Zn half cell is therefore -
0.76
• Anode (oxi): Zn(s) → Zn2+(aq) +2e- E°= 0.76
• Cathode (red): Cu2+(aq) +2e- → Cu(s) E°= 0.34 V
• Overall rn: Zn(s) + Cu2+(aq)→ Zn2+(aq) + Cu(s) = 1.1V
• Ecell = E°ox + E°red
• = 0.76 + 0.34
• E°Cell = 1.10 V
 PROBLEM 18.11
• The standard potential for the following galvanic cell
is 0.92V.

• Al(s) / Al3+(aq) // Cr3+(aq) / Cr(s)

• Look up the standard reduction potential for the Al3+

/ Al half-cell in Table 18.1, and calculate the standard
reduction potential for the Cr3+ / Cr half-cell
•
 18.6 USING STANDARD REDUCTION
POTENTIALS
• A table of standard reduction potential summarizes
an enormous amount of chemical information in a
very small space.

• It enables us to arrange oxidizing or reducing agents

in order of increasing strength.

• It permits us to predict the spontaneity or non-

spontaneity of thousands of redox reaction
 18.6 USING STANDARD REDUCTION
POTENTIALS
• The standard reduction potentials are useful in
determining the strengths of oxidizing and reducing
agents under standards state conditions.

• Large E°, The strongest oxidizing agents species

undergoes reduction with other species.

• Smaller E°, the strongest reducing agents species

undergoes oxidation with other species.

• Therefore, by calculating the E° values for the cell

reactions it enable us to find whether the reaction is
spontaneous or not.
 USING STANDARD REDUCTION
POTENTIALS
• To illustrate on how to use the tabulated standard
potential E° values for oxidation of Zn(s) by Ag+(aq):

• 2 Ag+(aq) + Zn(s) → 2 Ag(s) + Zn 2+ (aq)

• Note: An oxidizing agent can oxidize any reducing

agent that lies below it in the table but can’t oxidize
a reducing agent that appears above it in the table.

• Tabulate the E values for the reduction and oxidation

half reactions, and if the value of E is positive then
the reaction is spontaneous.
 18.6 USING STANDARD REDUCTION
POTENTIALS
•2 Ag+(aq) + Zn(s) → 2 Ag(s) + Zn 2+ (aq)

• write the half reactions:

Because E° is positive then the oxidation of zinc by

Ag+ is a spontaneous reaction under standard-
state conditions
 Worked example 18.6
• Arrange the following oxidizing agents in order of
increasing strength under standard-state conditions:
Br2(aq), Fe3+(aq) Cr2O72-(aq) - Fe3+ < Br2 < Cr2O72-
• 0.77 1.09 1.36
• Note that the strength of the oxidizing agent
increases on moving up the table

• Arrange the following reducing agents in order of

increasing strength under standard-state conditions:
Al(s), Na(s), Zn(s) – Zn(s) < Al(s) < Na(s)
• 0.76 1.66 2.71
 Problem
• What would be the spontaneity between Cd and Ag?
Calculate E°cell for spon rxn at 25°C and 1M (std cell)

• Given:
• Cd(s ) → Cd2+(aq) + 2e- E° = -0.40 V
• 2[Ag+(aq) + e- → Ag(s)] E° = 0.80 V
• 2Ag+ + Cd(s) → Cd2+(aq) + 2Ag(s) E° = 1.2 V

• Therefore the E° value is positive meaning that the

reaction is spontaneous
 WORKED EXAMPLE 18.7
• Predict from table 18.1 whether Pb2+(aq) can oxidize
Al(s) or Cu(s) under standard-state conditions.
Calculate E° for each reaction at 25°C.

• Note: to predict whether a redox reaction is

spontaneous, an oxidizing agent can oxidize any
reducing agent that lies below it in the table but
can’t oxidize one that lies above it.

• Sum the E values, and if the E value is positive the

reaction is spontaneous. Do Problem 18.14 and
18.15
 CELL POTENTIALS UNDER NONSTANDARD
STATE CONDITIONS: THE NERNST EQUATION
• Cell potential, like free energy changes, depend on
temperature and on the composition of the reaction mixture-
that is on the concentration of solutes and the partial
pressures of the gases.

• This dependency can be derived from the equation:

• ∆G = ∆G° + RT lnQ
• Where ∆G is the free-energy change for a reaction under
nonstandard state conditions

• ∆G° is the free energy change under standard-state conditions

• Q is the reaction quotient

 CELL POTENTIALS UNDER NONSTANDARD
STATE CONDITIONS: THE NERNST EQUATION
• Since ∆G = -nFE and ∆G° = -nFE°, we can rewrite the equation
for ∆G in form
This equation can be
G = G 0 + RTlnQ Written in the form

− nFE = −nFE 0 + RTlnQ

• Dividing by –nF we can obtain the Nernst equation
RT E = E – 2.303RT logQ
E cell = E −
0
lnQ or
nF nF
• Because of an intimate connection between the cell voltage
and pH this Nernst equation can be written this way
(value in volts at 25°C)
0.0592V
E 298K
cell =E −
0
logQ
n
 NERNST EQUATION
• n = number of electrons transferred in balanced eq.

• Q is equilibrium constant for product/reactants.

• In actual galvanic cells, the concentrations and partial

pressures of reactants and products seldom have
standard-state values, and the values changes as the cell
reaction proceeds.

• The Nernst equation is useful because it enables us to

calculate cell potentials under nonstandard-state
conditions.
 WORKED EXAMPLE 18.8
• Consider a galvanic cell that uses the reaction
• Zn(s) + 2H+(aq) → Zn2+(aq) +H2(g)

• Calculate the cell potential at 25°C when [H+] = 1.0,

[Zn2+] = 0.0010 M, and PH2 = 0.10 atm
 PRACTICE 18.16
• Consider a galvanic cell that uses the reaction

• Cu(s) +2Fe3+(aq) Cu2+(aq) + 2Fe2+(aq)

• What is the potential of a cell at 25°C that has the

following ion concentrations?

• [Fe3+] = 1.0 x 10-4 M, [Cu2+] = 0.25 M, [Fe2+] = 0.20 M

 ELETROREFINING AND ELECTROPLATING

• Thus, far we have been focusing on a galvanic cell – in

which a spontaneous reaction produces an electric
current.

• Another kind of electrochemical cell is the electrolytic

cell in which an electric current is used to drive a
nonspontaneous reaction.

• The process of using an electric current to bring about

chemical change is called electrolysis.

• In Electrolysis – a current is forced through a cell to

produce a chemical change for which the cell potential is
negative.
 THE RELATIONSHIP BETWEEN E AND
∆G

• When a reaction has reached equilibrium this means

that we have a dead battery
ELECTROLYSIS OF NaCl
 ELETROREFINING AND ELECTROPLATING

• Electrorefining – is the purification of a metal by

means of electrolysis.

• For example: impure copper obtained from ores is

converted to pure copper in an electrolytic cell that
has electrolytic cell impure copper as the anode and
pure copper is the cathode.
 ELECTROREFINING
• The electrolyte is an aqueous solution of copper sulfate
 ELETROREFINING

• The electrolyte is an aqueous

e-
solution of copper
sulfate. e-

battery
Impure Pure
Copper copper
anode cathode

Cu2+
Zn2+
Fe2+

More easily oxidized impurities

Electrolyte: CuSO4 (Zn, Fe) remain in solution as cations
 ELECTROREFINING
• At the impure Cu anode copper is oxidized along with
more easily oxidized metallic impurities such as zinc and
iron.

• Silver, gold and platinum are less easily oxidized and fall
to the bottom of the cell as anode mud which is
reprocessed to recover the precious metals.

• At the pure Cu cathode, Cu2+ ions are reduced to pure

copper metal, but the less easily reduced metal ions such
as (Zn and Fe2+) remain in the solution
 ELECTROREFINING

• Thus, the net cell reaction simply transfers copper

metal from the impure anode to the pure cathode.

• The copper obtained by this process is 99.95% pure.

• Closely, related to electro-refining is electroplating

 ELECTROPLATING
• Electroplating – is the coating of one metal on the
surface of another using electrolysis.

• For example: Steel motorcycle parts are often plated

with chromium to protect them from corrosion, and
silver-plating is commonly used to make items of fine
table service.

• The object to be plated is carefully cleaned and then

set up as the cathode of an electrolytic cell that
contains a solution of ions of the metal to be
deposited.
 18.14 QUANTITATIVE ASPECTS OF
ELECTROLYSIS
• The amount of substance produced at an electrode by
electrolysis depends on the quantity of charge passed
through the cell (Michael Faraday 1830).

• For example: if you pass 1 mol of electrons through a

Downs cell yields 1 mol (23.0 g) of sodium at the
cathode.

• Similarly, passing 1 mol of electrons in the Hall-Heroult

process produces 1/3 mol (9.0) of aluminum, because 3
mol of electrons are required to reduce 1 mol of Al3+ to
aluminum metal:
• Al3+ + 3e- → Al(l)
 18.14 QUANTITATIVE ASPECTS OF
ELECTROLYSIS
• To find out how many moles of electrons pass through a cell in
a particular experiment, we need to measure the electric
current and the time that the current flows.

• The number of coulombs of charge passed through the cell

equals the product of the current in amperes (coulombs per
second) and the time in seconds:

• Charge (C) = Current (A) x Time (s)

• Because the charge on 1 mol of electrons is 96,500 C, the

number of moles of electrons passed through the cell is

• Moles of e- = Charge (C ) x 1 mol e-

• 96,500 C
 WORKED EXAMPLE 18.12
• A constant current of 30.0 A is passed through and
aqueous solution of NaCl for 1.00 h. How many
grams of NaOH and how many liters of Cl2 gas at STP
are produced.

• Apply 18.30
• A layer of silver is electroplated on a coffee server
using a constant current of 0.100 A. How much time
is required to deposit 3.00 g of silver? (Hint: Work
through the steps in figure 18.20 in reverse order)