Electrochemistry: is reserved for the study of the processes that

convert chemical energy to electrical energy

Electrochemical Cells Electrochemical Cells are of two basic types:

Galvanic Cells a spontaneous chemical reaction generates an electric current
G = Electrolytic Cells an electric current drives a nonspontaneous reaction
G = +

For electrochemical reactions, a redox reaction can be separated in two,

oxidation which occurs at the anode and reduction that occurs at the cathode.

Review of Terms:
Oxidationreduction (redox) reaction involves a transfer
of electrons from the reducing agent to the oxidizing agent
Oxidation loss of electrons
Reduction gain of electrons
Reducing agent electron donor
Oxidizing agent electron acceptor

Reactions
Examples of Redox Reactions:
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s);
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Cu(s) + 2AgNO3(aq) CuNO3(aq) + 2Ag(s);
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)

A Galvanic Cell

In Galvanic Cell:
Oxidation occurs at the anode.
Reduction occurs at the cathode.
Salt bridge or porous disk allows ions to flow without
extensive mixing of the solutions.
Salt bridge contains a strong electrolyte as KCl

Cell Potential
A galvanic cell consists of an oxidizing agent (in cathode half-cell)
and a reducing agent (in anode half-cell).
Electrons flows through a wire from the anode half-cell to the cathode
half-cell.
The driving force that allows electrons to flow is called the
electromotive force (emf) or the cell potential (Ecell).
The unit of electrical potential is volt (V).

Standard Reduction Potentials

Values of E in standard table of half-cell potentials
are for reduction half-cell reactions
1 M, 1 atm, 25C

When a half-reaction is multiplied by an integer, the

value of E remains the same.
A galvanic cell runs spontaneously in the direction
that gives a positive value for Ecell

Example: Fe3+(aq) + Cu(s) Cu2+(aq) + Fe2+(aq)

Half-Reactions:
Fe3+ + e Fe2+
Cu2+ + 2e Cu

E = 0.77 V
E = 0.34 V

To balance the cell reaction and calculate the cell

potential, we must reverse reaction 2.
Cu Cu2+ + 2e

E = 0.34 V

Each Cu atom produces two electrons but each Fe3+

ion accepts only one electron, therefore reaction 1
must be multiplied by 2.
2Fe3+ + 2e 2Fe2+

E = 0.77 V

Standard Cell Potential

2Fe3+ + 2e 2Fe2+ ; E = 0.77 V (cathode)
Cu Cu2+ + 2e ; E = 0.34 V (anode)
Balanced Cell Reaction:
Cu + 2Fe3+ Cu2+ + 2Fe2+

Cell Potential: E
Ecell
Ecell

= E(cathode) E(anode)
= 0.77 V 0.34 V = 0.43 V

Cell Notations for Galvanic Cells

Used to describe electrochemical cells.
Anode components are listed on the left.
Cathode components are listed on the right.
Separated by double vertical lines.
The concentration of aqueous solutions should be
specified in the notation when known.
Example: Mg(s)|Mg2+(aq)||Al3+(aq)|Al(s)
Mg Mg2+ + 2e

(anode)

Al3+ + 3e Al (cathode)

Designation of Anode and Cathode

Write balanced net ionic equation for the spontaneous cell reaction.
The oxidizing agent (one with the more positive or less negative
reduction potential E) will be the cathode and the other will be the
anode.
Oxidation occurs in anode half-cell and reduction in cathode half-cell.
Anode is negative(-) and cathode is positive(+).