An ELECTROCHEMICAL CELL consists of two half-cells joined by a wire and solutions by a salt bridge.

It is an
apparatus for generating electricity through the use of a spontaneous redox reaction
3 Types of Electrode/Half-Cell
1. INERT
 An electrode that serves only as a source or sink for electrons without playing a chemical role in
the electrode reaction. Noble metals, mercury, and carbon are typically used as inert
electrodes.
2. MEMBRANE (Glass)
 A membrane electrode with a thin glass membrane (usually in the form of a bulb at the end of a
glass tubing) sensing element. It is most often used as a pH electrode, but some glass
compositions can also be sensitive to the concentration of other cations (e.g., sodium).
3. METALLIC
 Certain metals, such as silver, mercury, copper, and lead that is in contact with a solution of
their ions.
 A strip of metal, M, partially immersed in a solution containing ions of the same metal, Mn+ may
undergo two types of reaction: ELECTRODEPOSITION or ELECTRODISSOLUTION.
Electrodeposition:
A metal ion Mn+ from solution gains electron producing the metal atom M.
Reduction took place, or the ion is reduced
Electrodissolution:
 A metal atom M may lose electron and enter the solution as the ion Mn+.
Oxidation took place, or the metal atom oxidized.
 By definition, the electrode which the oxidation occurs is called the anode and the electrode which
reduction occurs is called the cathode (An Ox Ate a Red Cat)
 The salt bridge is a conducting medium through which the cation and anion can move from one
electrode compartment to the other. It completes the external circuit. It is usually a solution of inert
electrolytes such as KCl and NH4NO3.
ELECTRODE POTENTIAL & CELL POTENTIAL
 Electrode Potential is the measure of the electric charge density on an electrode at which a redox
equilibrium has been established in half reaction.
 Cell Potential/ Electromotive Force (E) is the difference in electrical potential between the anode and
the cathode.
- depends on the nature of the electrode and ions, concentration and temperature.
CELL DIAGRAM is the conventional notation for representing electrochemical cells.
- a single vertical line represents a phase boundary. The double vertical line denotes the salt
bridge.
- The anode is written first (left side) then the cathode.
Zn(s)/ Zn2+ (0.5 M)//Cu2+ (0.5 M)/Cu(s)
Exercise: Write the cell diagram for an electrochemical cell consisting of an Al electrode placed in a 1M
Al(NO3)3 solution and an Ag electrode placed in a 1 M AgNO3 solution.
E° = standard electrode potential
= is based on the tendency for a reduction process to occur at the electrode
POINTS REGARDING THE E° TABLE
1. E° value apply to the half cell reaction as read in the forward reaction
2. the more positive the E°, the greater the tendency to be reduced
3. the half cell reaction are reversible
4. E° value is intrinsic

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

OXIDIZING & REDUCING AGENTS
• Species on the left side of the half reactions can act as oxidizing agents, and those on the right side
can serve as reducing agents.
• As E° becomes more positive, the oxidizing strength of the species on the left increases. And as it
becomes more negative, the reducing strength of the species on the right increases

SPONTANIEITY OF REDOX REACTIONS

Galvanic cells: reactions proceed spontaneously  (+) E°
Electrolytic cells: non-spontaneous reaction occur  (-) E°

GIBB’S FREE ENERGY & SPONTANEITY

∆G° = -nFE°cell
∆G°: a measure of the spontaneity of a process that occur at constant temperature and pressure at
standard state

n: a positive number without units that represents the number of electrons transferred in the reaction.

F: Faraday’s constant
1 F = 96,500 C/mol = 96,500 J/V-mol

a) Calculate ∆G° for the following reaction:

4Ag(s) + O2(g) + 4H+(aq)  4Ag+(aq) + 2H2O(l)
b) Suppose the reaction in (a) were written as 2Ag(s) + ½ O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l) what will be
the value of E° and ∆G°?