Öğr Gör Sedef Günday Özcan

ELECTROCHEMISTRY
 Electrochemistry is the branch of chemistry that deals
with relationships between electricity and chemical
reactions.

• The reactions where electrons are transferred between

reactants are called “oxidation-reduction”, or “redox”
reactions.
Oxidation-Reduction Reactions

• Loss of electrons is oxidation.

• Gain of electrons is reduction.
• One cannot occur without the other.
• The reactions are often called redox reactions.
Oxidation-Reduction Reactions
Rules to Assign Oxidation Numbers
• Elements in their elemental form have an
oxidation number of zero.
Fe, Au (oxidation number=0)

• The oxidation number of a monatomic ion

is the same as its charge.
Cl- (oxidation number= -1)
Fe2+ (oxidation number= +2)
Rules to Assign Oxidation Numbers
• Nonmetals tend to have negative oxidation
numbers, although some are positive in
certain compounds or ions.
– Oxygen (O2-) has an oxidation number of −2.
– Hydrogen is +1 when bonded to a nonmetal (HCl).
– Fluorine always has an oxidation number of −1.
– The other halogens have an oxidation number of −1
when they are negative; they can have positive
oxidation numbers, most notably in oxyanions (ClO4-)
Rules to Assign Oxidation Numbers
• The sum of the oxidation numbers in a neutral
compound is zero.
H2O, oxidation number is 0
• The sum of the oxidation numbers in a polyatomic
ion is the charge on the ion ClO4- , oxidation
number is -1.

!! NOTE: The oxidation number increases in an

oxidation process & the oxidation number
decreases in a reduction process.
EXAMPLE 1:
Fe2O3 (s) + 3 CO (g) → 2 Fe (l) + 3 CO2 (g)
O: -2 O: -2 Fe: 0 O: -2
Fe: +3 C: +2 C: +4

Reduced Oxidized

Oxidation Oxidation
Number Number
Decreases Increases
3→0 2→4
It is not a redox reaction!!

H2PO4- (aq) + OH- (aq) → HPO42- (aq) + 3 H2O (l)

O: -2 O: -2 O: -2 O: -2
H: +1 H: +1 H: +1 H: +1
P: +5 P: +5
 Oxidation and Reduction
In redox reactions,
ions oxidize an
element.
In this reaction,
silver ions oxidize
copper metal:

Oxidation
Cu(s) + 2 Ag+(aq) → Cu2+(aq) + 2 Ag(s)
Number 0 +1 +2 0
oxidation
reduction
 Oxidation and Reduction

• A species is oxidized when it loses electrons.

• Zinc loses two electrons, forming the Zn2+ ion.
• A species is reduced when it gains electrons.
• H+ gains an electron, forming H2.
• An oxidizing agent causes something else to be oxidized
(H+); a reducing agent causes something else to be
reduced (Zn).
 Half-Reactions
• The oxidation and reduction are written and
balanced separately.
• We can use them to balance a redox reaction.

Oxidation: Zn(s) → Zn2+(aq) + 2e-

Reduction: 2 H+(aq) + 2e- → H2(g)

Overall: Zn(s) + 2 H+(aq) → Zn2+(aq) + H2(g)

 VOLTAIC CELLS
• In spontaneous redox
reactions, electrons are
transferred, and energy is
released.
• That energy can do work if
the electrons flow through
an external device.
• This is a voltaic cell.
VOLTAIC CELLS
 A strip of metal, M, is called an electrode.
 An electrode immersed in a solution containing ions
of the same metal, Mn+, is called a half-cell.

Two kinds of interactions are possible between metal atoms on an

electrode and metal ions in solution:

 A metal ion, Mn+ from the solution may collide with the electrode,
gain n electrons from it and be converted to a metal atom M. The
ion is reduced.
 A metal atom M on the surface may lose n electrons to the
electrode and enter the solution as the ion Mn+. The metal atom is
oxidized.
VOLTAIC CELLS
Equilibrium is quickly established between the metal and the
solution, which can be represented as;
M(s) Mn+(aq) + ne
In order for the redox reaction to do work;
• the half-reactions need to be separated, and
• the electrons need to be able to flow from one half-reaction
to the other.
VOLTAIC CELLS
 VOLTAIC CELLS
• Voltaic cells consist of
– Anode (where oxidation occurs): Zn(s) → Zn2+(aq) + 2e−
– Cathode (where reduction occurs): Cu2+(aq) + 2e− → Cu(s)
– Salt bridge (used to complete the electrical circuit):
cations move towards cathode; anions move towards
anode.
 The two solid metals are the electrodes [cathode, (+), and
anode, (–).]
 If oxidation takes place, the electrode is called anode. If
reduction takes place the electrode is called the cathode.
 When electrons flow, charges aren’t balanced. So, a salt
bridge, usually a U-shaped tube that contains a salt solution, is
used to keep the charges balanced.
 VOLTAIC CELLS
• In the cell, electrons leave the
anode and flow through the
wire to the cathode.
• Cations are formed in the
anode compartment.
• As the electrons reach the
cathode, cations in solution are
attracted to the cathode half
cell.
• The cations gain electrons and
are deposited as metal on the
cathode.
 Electromotive Force (emf) or Cell Voltage
 The flow of electrons from anode
to cathode (from high to low
potential energy) is spontaneous.

 Potential difference (Cell Voltage):

Difference in electrical potentials
of two electrodes.
 The potential difference is
measured in volt.
Volts=Joules/Coulomb
 Cell voltage is also called cell
potential or electromotive force
(emf) and represented by Ecell.
CELL DIAGRAM AND TERMINOLOGY
Anode Cathode
Zn(s)|Zn2+(aq) || Cu2+(aq)|Cu(s) Ecell=1.103V
Half-cell(oxidation) salt bridge Half-cell(reduction) Cell voltage

Oxidation: Zn(s) → Zn2+(aq) + 2e-

Reduction: Cu2+(aq) + 2e- → Cu(s)

Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

CELL DIAGRAM AND TERMINOLOGY
 The anode, the electrode at which oxidation occurs, is placed
at the left side of the diagram.
 The cathode, the electrode at which reduction occurs, is
placed at the right side of the diagram.
 A boundary between different phases (e.g. an electrode and a
solution) is represented by a single-vertical line (|).
 The boundary between half-cell compartments, commonly a
salt bridge, is represented by a double vertical line (||).
Species in aqueous solution are placed on either side of the
double vertical line. Different species within the same solution
are separated from each other by a comma.
 EXAMPLE 2:
Aluminum (Al) metal displaces zinc (Zn2+) ion from aqueous solution.
a. Write oxidation and reduction half-reactions and the overall equation for
this redox reaction.
b. Write a cell diagram for a voltaic cell in which this reaction occurs.
Standard Electrode Potentials
A standard electrode potential, E0 measures tendency for a
reduction process to occur at an electrode.

Potentials of individual electrodes cannot be measured

precisely. Instead, the electrode potential results can be
achieved by choosing a particular half-cell that is assigned an
electrode potential zero.

Other half-cells can then be compared to this reference.

 SHE (Standard Hydrogen Electrode)
 The commonly accepted reference is the standard hydrogen
electrode (SHE).
 The H2 gas at a pressure of 1 bar is bubbled over an inert metal such
as platinum electrode immersed in 1M aqueous acid (H+) at 25°C.
 A voltage of exactly 0 V (E°=0 V) is assigned to this half cell
2H+ (1M) + 2e- H2 (g, 1 bar) E0=0 volt (V)

The diagram for this half-cell is:

Pt|H2(g, 1bar)|H+ (1M)

 Standard Reduction Potentials
• Reduction potentials for
many electrodes have
been measured and
tabulated.
• The values are
compared to the
reduction of hydrogen as
a standard.
!!!!! The more positive the value of
E°red, the greater the tendency
for reduction under standard
conditions.
 SHE AND COPPER CATHODE

Anode: H2 (g) → 2H+ (aq) + 2e-

Cathode: Cu2+ (aq) + 2e- → Cu (s)
Overall reaction: H2 (g) + Cu2+ (aq)→ 2H+ (aq) + Cu (s)
 SHE AND ZINC ANODE

Zinc is oxidized. Since the Eºcell is + 0.76 V, that means the Eºred for [Zn2+(aq) + 2e− Zn(s)]
would be –0.76 V.
Standard Cell Potentials, E 0
cell
The cell potential at standard conditions can be
found through this equation:

° = Ered
Ecell ° (cathode) – Ered° (anode)
 Cell Potentials
• For the anode in this cell, E°red = –0.76 V
• For the cathode, E°red = +0.34 V
• So, for the cell, E°cell = E°red (cathode) – E°red (anode)
= +0.34 V – (–0.76 V) = +1.10 V
 EXAMPLE 3:
A new battery system currently under study for possible use in electric vehicles is the
zinc-chlorine battery. The overall reaction producing electricity in this cell is

Zn(s) + Cl2 (g) → ZnCl2 (aq) What is the Eocell of this voltaic cell?
 Ecell as a function of Concentrations (Nernst
Equation)
Ecell= E°cell – 0.0592 V
Ecell= E°cell - x log Q
n

Ecell > 0 SPONTANEOUS reaction

Ecell < 0 NONSPONTANEOUS reaction

• Notice that the Nernst equation implies that a cell could be created that has
the same substance at both electrodes, called a concentration cell.
• For such a cell, E°cell , would be 0, but Q would not.
• Therefore, as long as the concentrations are different, E will not be 0.
 EXAMPLE 4:
What is the value of Ecell for the voltaic cell diagrammed as
follows?
Pt|Fe2+(0.10 M) , Fe3+(0.20 M) || Ag+(1.0 M) |Ag(s) Ecell= ?
EXAMPLE 5:
Write the half-reactions and calculate the cell potential for the following
system predict whether the reaction would proceed spontaneously.
Cu (s) | Cu2+(0.024 M) || Ag+(0.0048 M) |Ag (s) Ecell= ?
 CORROSION
Corrosion is the decomposition of metals by an
electrochemical process.

For corrosion to happen, a difference in electrical

potential must exist between the different areas of the
substance.

 Rust on iron
 Tarnish on silver

 Corrosion is an example of an undesirable redox reaction

of metals.
 A metal is attacked by a substance in the environment and
converted to an unwanted compound.
 CORROSION
Consider the corrosion (rusting) of iron:
Since Eºred(O2) > Eºred(Fe2+), iron can be
oxidized by O2.
Cathode: O2(g)+4H+(aq) +4e−2H2O(l)
Eºred = +1.23 V
Anode: Fe(s)  Fe2+(aq)+ 2e−
Eºred = −0.44 V
One region of the iron acts
The reaction products at the anode and as the cathode and another
the cathode combine to form red iron region acts as the anode

oxide (rust)

4Fe2+(aq)+O2(g)+4H2O(l)+xH2O(l)2Fe2O3 xH2O(s) +8H+(aq)

 DRY CORROSION
Dry corrosion or oxidation occurs when oxygen in the air reacts
with metal without the presence of a liquid.

 It is very sensitive to temperature.

(corrosion rate increases with the increase of T)

 The differences in the rate of dry corrosion vary from

metal to metal because of the mechanisms involved.

 Oxygen should be able to contact with the metal surface.

2 M + nO2 → M 2On (metal oxide)

 STAINLESS STEEL
Stainless steel has chromium added to it, which
forms a very protective oxide layer that prevents
further corrosion.

 Alloying metallic elements increase corrosion

resistance, hardness, or strength.
 The commonly used metals as alloying elements in
stainless steel include nickel, molybdenum and
manganese.
 Since stainless steel resists corrosion, maintains
its strength at high temperatures, and it is widely
used in items such as automotive, propulsion
shaft for high speed craft.
 WET CORROSION
ELECTROLYTE

The corrosion process consists of an anodic and a cathodic reaction.

In the anodic reaction (oxidation) the metal is dissolved and

transferred to the solution as ions M2+.

The cathodic reaction in the example is reduction of oxygen

CORROSION IN MARINE ENVIRONMENT

The characteristic corrosion types which are seen in marine

environment are

 crack (crevice) corrosion

 pitting corrosion
 stress corrosion
 biological corrosion

Besides, stainless steel connection components could cause a

galvanic corrosion and cavitations corrosion could occur on
screw of a ship.
 PITTING CORROSION

A bronze prop shaft and rudder showing

pitting corrosion
 STRESS CORROSION

A hanger with large stress corrosion cracks

Stress corrosion of a copper

tube
 GALVANIC CORROSION
Galvanic corrosion is an electrochemical process in which
one metal corrodes preferentially to another when both
metals are in electrical contact, in the presence of
an electrolyte.
 PREVENTION OF CORROSION
Cathodic protection (CP) is a technique used to control the
corrosion of a metal surface by making it the cathode of an
electrochemical cell.

The principle of cathodic protection is;

to create a potential gradient opposing the flow of

electrons from the surface to be protected.

The simplest method to apply CP is by connecting the metal to

be protected with another more easily corroded “sacrificial
metal" to act as the anode of the electrochemical cell.
PREVENTING THE CORROSİON OF IRON
The standard reduction potentials indicate that Zinc is
easier to oxidize than iron.
• Zinc can be used as “sacrificial anode” and is slowly
destroyed as a result of the oxidation process. Iron acts
as the cathode..
• Zn, Mg and Al are used as a sacrificial anode…
PREVENTING THE CORROSİON OF IRON
Other than Cathodic Protection:
1. Corrosion can be prevented by coating the iron
with paint or another metal (such as Cu, Sn) to
keep it away from O2 and water.
3. Coating iron with a layer of zinc, “galvanized
iron”, can protect the iron from corrosion even
after the surface coat is broken.
Zn2+(aq) + 2e−  Zn(s) Eºred = − 0.76 V
Fe2+(aq) + 2e−  Fe(s) Eºred = − 0.44 V
EXAMPLE