Electrochemistry

By: Fatima Al Zahra Amin

Table of contents
02
01 Quantitative
Electrolysis Electrolysis

03 04
Electrode Combining
Potentials Half-Cells

05 06
Using More about
E⦵ values Electrolysis
Electrolysis
revisited
• In a redox reactions,
electrons may be gain or
lost
• The species that loses
electrons is oxidised; it is
the reducing agent.
• The species that gains
electrons is reduced; it is
the oxidising agent.
01
Electrolysi
s
Fundamentals
• Electrolysis is the decomposition of a
compound into its elements by an
electric current. It is often used to
extract metals that are high in the
reactivity series.

In this electrolysis cell:

• The electrolyte is the compound that
is decomposed. It can be a molted
ionic compound or a concentration
aqueous solution of ions.
• The electrode are rods, made from
carbon (graphite) or metal, which
conduct electricity to and from the
electrolyte.
• The anode is the positive electrode.
• The cathode is the negative
Redox Reactions in
Electrolysis
• Ions that are attracted to the cathode
and are positively charged are called
cations
• Ions that are attracted to the anode
and are negatively charged are called
anions
• Reduction is taking place at the
cathode.
• Oxidation is taking place at the
anode.
• In the electrolysis of molten KCl,
Potassium ions are reduced
• Chlorine eyes are oxidised
• The electron lost at the anode
Reactivity series of Metals
Police Most
Potassium (K)
• The more reactive
Reactiv
Sargent Sodium e
substance keeps
(Na) itself in the ionic
Lee Lithium
form
(Li)
Charlie Calcium Decreasin • The reactive metal
(Ca) g is the one that
M Reactivity/ remains in solution
Magnesium (Mg) Power of
A displacem
during electrolysis
Aluminum (Al) ent Like between
C Carbon decreases Hydrogen and
(C)
Z Zinc
Sodium, Hydrogen
(Zn) would be given off
I Iron Least at the electrode
(Fe) Reactiv • Reactive metal
N Nickel e
 Question

Cu(s) - 2e-  Cu2+ (aq)

Cu2+ (aq) + 2e-  Cu (s)

02
Quantitative
Electrolysis
The mass of a substance
deposited during electrolysis
Faraday
It is a unit used to define the The mass of a substance produced during
quantity of electricity. electrolysis is proportional to:
One Faraday is the quantity of • The time over which a constant electric
electric charge carried by 1 mole current passes
of electrons or 1 mole of singly • The strength of the electric current
charged ions. Its value is 96500 • The quantity of electricity which passes
C/mol. through the electrolyte
Avogadro Constant So, the formula used to calculate the charge is
Q=Ixt
It is denoted with the letter L. Where Q is the charge in Coulombs (C), I is the
It is the number of specified particles in 1 mole. current in Amperes (A), and t is the time in
The relationship between Faraday (F) and L is: seconds (s).
F = Le
Where e is the charge on an electron and is fixed as 1.6 x 10-19.
Examples
Situation Equation: Conclusion
During the electrolysis Ag+ (aq) + e-  One Faraday of
of silver nitrate Ag (s) electricity (96500) is
solution, silver is 1 mol 1 mol required to deposit 1
deposited at the 1 mol mole of silver.
cathode.

Situation Equation Conclusion

During the electrolysis Cu2+ (aq) + 2e-  Since there are 2
of copper (II) sulfate Cu (s) moles of electrons to
solution, copper is 1 mol 2 mol produce 1 mole of
deposited at the 1 mol copper, it requires two
cathode. Faradays of Electricity.
2 x 96500 C = 193 000
C
Question

Moles = mass/Mr

= 225/63.5

=+
Cu2+ (aq) 3.54
2e-  Cu (s)
= 2 x 3.54 = 7.08 mol

Q = It = 20 x (10x60x60) =7.2 x
105 C
1 : 96500
x : 7.2 x 105
x = 7.46 mol
03
Electrode
Potentials
 Introduction
• A redox equilibrium exists between two
chemically related species that in different
oxidation states.
It is established when the rate of electron
gain equals the rate of electron loss.
• In the reaction of aqueous solution of
copper ions and copper rod dipped in it:
Cu2+ (aq) + 2e- ⇌ Cu (s)
• The two opposing reactions taking place
during this are:
Cu (s)  Cu2+ (aq) + 2e-
Cu2+ (aq) + 2e-  Cu (s)
• The metal atoms from the rod are entering
the solution as metal ions, leaving electrons
on the surface of the rod.
• While the ions in solution gain the electrons
 Electrode
Potential
• Denoted as E
• Measure in Volts (V)
• It is the difference in potential
between the metal / metal ion
system and another system
• The voltage is produced when, for
example:
• Zinc is placed in a solution
containing zinc ions
• A small amount of zinc atoms on the
surface of the metal are converted to
zinc ions, which go into solution
• This leaves an excess of electrons on
the surface of the zinc
• The solution now has excess zinc
ions
• Some ions near the zinc are
attracted to the its surface
• An electrical double layer is formed
and the build up of charge causes an
electric potential (voltage)
 Standard Hydrogen Electrode
• Used as reference electrode to
determine standard electrode
potential
• Standard conditions are:
1. 101 kPa pressure
2. Concentration of 1 mol/dm3
• The platinum wire is used to make
electrical contact of hydrogen gas
with its ions. It is inert so it doesn’t
take place in the reaction.
• The half-equation for the hydrogen
electrode is written as:
2H+ (aq) + 2e- ⇌ H2 (g)
• The value of E⦵ for this cell is 0 V,
which is why we use this as the
reference electrode
Electrode Potential and
redox reactions
• For unreactive metals such as copper, • The more positive (or less negative)
redox equilibrium lies to the right the value of the electrode potential,
Cu2+ (aq) + 2e- ⇌ Cu (s)
Copper ions are therefore relatively
the easier it is to reduce the ions
easy to reduce • Ag+ (aq) + e- ⇌ Ag (s) voltage
• For reactive metals such as vanadium, = +0.80 V
the equilibrium lies to the left • So the metal on the right is
V2+ (aq) + 2e- ⇌ V (s) unreactive and a poor reducing
Vanadium ions are therefore relatively agent
difficult to reduce • The more negative (or less positive)
• Electrode potential values give us an
indication how easy it is to reduce a
the electrode potential, the more
substance. difficult it is to reduce the ions
• By convention, the electrode potential • Zn2+ (aq) + 2e- ⇌ Zn (s) voltage
refers to the reduction reaction, so the = -0.76 V
electrons appear on the left side of the • So the metal on the right is reactive
04
Combining
Half-Cells
 Half-Cells
• Half cell is one half of an
electrochemical cell which either
donates electrons to or receives
electrons from an external circuit
when connected to another half-
cell.
• Like placing a pure copper rod in a
solution of copper ions.
• The conditions for a half-cell are:
1. Ions should have a 1 mol/dm3
concentration
2. 298 K Temperature
3. The rod must be pure form of the
metal
Combining Half-Cells
• A salt bridge is used to complete
the electrical circuit to allow
movement of ions between the two
half-cells
• It does not allow the movement of
electrons
• It is made from a strip of filter
paper soaked in saturated solution
of potassium nitrate
• The voltages for the half-cells
shown:
Cu2+ (aq) + 2e- ⇌ Cu (s) voltage =
+0.34 V
 Standard
Half-Cell Electrode
equations Potential
• Fe3+ (aq) + e- ⇌ Fe2+ (aq) • Standard Electrode Potential (E⦵)
is the voltage produced when a
• Cl2 (g) + 2e- ⇌ 2Cl- (aq)
standard half-cell (ion concentration
• MnO4- (aq) + 8H+ (aq) + 5e+ ⇌ Mn2+ (aq) 1.00 mol/dm3 at 298 K) is connected
+ 4H2O (l) to a standard hydrogen electrode
The charge of manganese in MnO4- is under standard conditions.
• Standard conditions are:
+7 1. Concentration of 1.00 mol/dm3
• The oxidised species is always written 2. Temperature of 298 K
on the left hand side 3. Gases at pressure of 1 atmosphere
• The reduced species is always on the (101 kPa)
right hand side 4. The value of the electrode
potential of the half-cell is measure
relative to the standard hydrogen
Measuring Standard
Electrode Potential
● There are three main type of half-
cells of which hydrogen electrode
potentials can be calculated:
1. Metal/metal ion half-cell
2. Non-metal/non-metal ion half-
cell
3. Ion/ion half cell
● In non-metal half cells, Platinum
foil or wire is used as an electrode
to make electrical contact
because it is inert​
Metal / Metal ions
The voltage of the cell is
+0.34 V
The voltage of Copper is
+0.34 V.
It means that it is easier to
reduce than Hydrogen ions,
so it is the positive electrode.
Copper ions will gain
electrons from the Hydrogen
The voltage of the cell is -
0.76 V
The voltage of Zinc is –
0.76 V.
It means that it is difficult
to reduce than Hydrogen
ions, so it is the negative
elctrode.
Hydrogen ions will gain
electrons from the Zinc
The voltage of the cell is
-0.44 V​
The voltage of Iron is –
0.44 V.​
It means that it is difficult
to reduce than Hydrogen
ions, so it is the negative
electrode.​
Hydrogen ions will gain
electrons from the Iron
half-cell while it loses to
The voltage of the cell is -
0.91 V
The voltage of Chromium is
–0.91 V.
It means that it is difficult to
reduce than Hydrogen ions,
so it is the negaive
electrode.
Hydrogen ions will gain
electrons from
The voltage of the cell is
+0.80 V​
The voltage of Silver is
+0.80 V.​
It means that it is easier
to reduce than
Hydrogen ions, so it is
the positive electrode.​
Silver ions will gain
electrons from the
Hydrogen half-cell while
Question
Non-Metal / Non-Metal ions
The voltage of the cell is
+1.36 V
The voltage of Chlorine is
+1.36 V.
It means that it is easier to
reduce than Hydrogen ions,
so it is the positive
electrode.
Chlorine ions will gain
The voltage of the cell is
+0.51 V​
The voltage of
Platinum is +0.51 V.​
It means that it is easier
to reduce than
Hydrogen ions, so it is
the positive electrode.​
Platinum ions will gain
electrons from the
Hydrogen half-cell while
it loses to Platinum.​
Ion / Ion of same element in
different oxidation states
The voltage of the cell is
+0.77 V
The voltage of Iron ions is
+0.77. V.
It means that they easier to
reduce than Hydrogen ions,
so they are the postive
elctrode.
Iron ions will gain electrons
The voltage of the cell is
+1.52 V​
The voltage of the Manganese
ions and Hydrogen ions is
+1.52 V.​
It means that they are easier
to reduce than Hydrogen ions,
so they are the positive
electrode.​
Manganese ions will gain
electrons from the Hydrogen
half-cell while it loses to them.​
H+ ions are included in the
Question
05
Using E
⦵

values
 Predicting
Cell Direction of
Voltages electron flow
• Standard cell potential is the • Remember that the
difference in standard electrode more positive the E⦵
potential between two specified value, the easier it
half cells is to reduce the
• The equations for the half-cells metal and vice
shown are: versa
Ag+ (aq) + e- ⇌ Ag (s) E⦵ = • In the half cell
+0.80 V shown, Silver is
Zn2+ (aq) + 2e- ⇌ Zn (s) E⦵ = - easier to reduce and
0.76 V Zinc is not
• To find Ecell value of the cell we • So, Zinc will lose
subtract the less positive value electrons to Silver
from the more positive value • The electrons move
• Ecell = +0.80 - (-0.76) through the wires in
= +1.56 V the external circuit
• In a half cell / half cell set up, the • The more positive
pole attracts the
Using E⦵ values to predict if a
reaction will occur
• Cu2+ (aq) + 2e- ⇌ Cu (s) E⦵ = +0.34
• The more positive
V
the E⦵, the greater Zn2+ (aq) + 2e- ⇌ Zn (s) E⦵ = -0.76
the tendency for a V
half-equation to • Copper has a greater tendency to gain
electrons so the reaction proceeds in the
proceed in the forward direction as it is
forward direction and • While Zinc has a greater tendency to lose
vice versa electron so the reaction proceeds in the
• The more positive backward direction:
Zn (s)  Zn2+ (aq) + 2e-
the value of E⦵, the • We can combine these half-equations:
easier it is to reduce Zn (s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s)
the species on the • This is the reaction that takes place in the
electrochemical cell but also the one that
left side of the half- takes place when zinc metal is placed in a
Question

1.47 – (-0.13) = 1.6 V

Pb + PbO2 + 4H+  Pb2+ + 2H2O + Pb2+

In the first equation on the right side, Pb has a tendency to lose electrons since E ⦵ is negative,
so:
Pb  Pb2+ + 2e-
The second reaction proceeds as it is:
PbO2 + 4H+ + 2e-  Pb2+ + 2H2O
Combining them:
Pb + PbO2 + 4H+ + 2e-  Pb2+ + 2H2O + Pb2+ + 2e-
 E⦵ values and oxidising and
reducing agents
As the E⦵ becomes more
negative:
• The species on the left
become weaker oxidising
agent.
• They accept electrons less
readily.
• The species on the right
become stronger reducing
agent.
• They release electrons more
readily.
• Copper does not reduce Zinc
Oxidisin
g
Ability
Decreas
es
How E⦵ varies with concentration
• If we change the concentration or temperature
of a half-cell, the electrode potential also
changes
• We use the symbol E for the electrode potential
Examples
under these non-standard conditions

• • Fe3+ + e- ⇌ Fe2+ E⦵ = +0.77 V

Zn2+ (aq) + 2e- ⇌ Zn (s) E⦵
• If the concentration of Fe3+ ions is
= -0.76 V
• If the concentration of zinc ions greater than 1.00 mol/dm3 (keeping
is greater than 1.00 mol/dm3, [Fe2+] as 1], the value of E becomes
the value of E becomes less more positive / less negative and vice
negative / more positive and the versa
• If the concentration of Fe2+ is greater
equilibrium shifts to the right
• If the concentration of zinc ions than 1.00 mol/dm3 (keeping [Fe3+] as 1],
is less than 1.00 mol/dm3, the the value of E becomes less positive /
values of E becomes more more negative and vice versa
• If both ion concentration is increase,
Question

No change (because H2O does not

change)

Less positive
Whether a given reaction will occur
under non-standard conditions
• If the difference between E⦵ of the two half-reactions involved
is greater than 0.3 V, then the reaction predicted by values is
highly likely to occur
• If the values differ less than 0.30 V, non-standard conditions
may result in unexpected outcomes
Examples
• ½ Cl2 (g) + e- Fe3+ ⇌ Cl- (aq) E⦵ = +1.36 V
Fe3+ (aq) + e- ⇌ Fe2+ (aq) E⦵ = +0.77 V
• The difference between them is 0.59 V so the reaction will occur

• ½ Cl (g) + e- ⇌ Cl- (aq) E⦵ =

+1.36 V
MnO4- (aq) + 8H+ (aq) + 5e+ ⇌ Mn2+ (aq) + 4H2O (l) E⦵ =
 Feasibility
predictions based
on E⦵ don’t always
work!
● It only tells us if a reaction
will occur, not if it will
proceed quickly
● It only tells us that the
reaction is possible and
that the reverse will not
occur
The Nernst Equation
• Cu (s) + 2Ag+ (aq) ⇌ Cu2+ (aq) + 2Ag(s)
E⦵ = +0.46 V
• Where:
E is the electrode potential under non-
standard conditions
• E⦵ is the standard electrode potential
• R is the gas constant, 8.31, in J/k/mol
• T is the kelvin temperature
• z is the number of electrons transferred in
the reaction
• F is the value of the Faraday constant in
C/mol
• ln is the natural logarithm
• We can simplify this
ln x = 2.303 log10 x
• The effect of temperature and concentration on R, T, and F are constant
the value of Ecell can be deduced using the And the concentration of the metal does not
Nernst equation which is for a given metal / change
metal ion electrode
Question

E = 1.82 + (8.31)(298)/(1)(96500) ln
[0.02]/[2]
E = 1.702
1.702
06
More about
Electrolysis
Electrolysis of Molten Electrolytes
Compound
Cathode Product Anode Product
Electrolysed

Aluminium Oxide Aluminium Oxygen

Magnesium Bromide Magnesium Bromine

Sodium Chloride Sodium Chlorine

Zinc Iodide Zinc Iodine

Electrolysis of aqueous solutions
• Discharged means when ions are changed into atoms or molecules.

Electrode Potential Solution Concentration

• In an aqueous solution, the cation which • Only the discharge of ions is
has a more positive E⦵ is reduced at the effected by concentration
cathode • When concentrated sodium
• For example between Sodium ions and
Hydrogen ions, Hydrogen gas is given
chloride is electrolysed, chloride
off at electrode ions discharged at the anode
• For anions, the ease of discharge of ions rather than hydroxide ions
follows the order because they have a greater
• For example, between hydroxide ions concentration
and nitrate ions, the former is oxidised • In a dilute solution of sodium
at the anode chloride, oxygen is given off at the
anode rather than chlorine
Question

Zinc

Chlorine Hydrogen

Oxygen Hydrogen
Definitions
Standard Electrode
Reduction Faraday Electrolysis Electrolyte
Potential, E⦵

Gain of The quantity of The voltage produced The A molten ionic

electrons electric charge when a standard half- decomposition of compound or
(in coulombs) cell (ion conc. 1 an ionic an aqueous
carried by 1 mole mol/dm3 at 298 K) is compound when solution of ions
Oxidation
of electrons or 1 connected to a molten or in that is
mole of singly standard H2 electrode aqueous solution decomposed
Loss of charged ions under standard by an electric during
electrons conditions. current electrolysis

Electrode Potential, E Standard Cell Potential

The voltage measured for a half-cell compared The difference in standard electrode potential
with another half-cell between two specified half-cells
 Thanks!
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