Prof. O.O.

SORIYAN
LECTURE 2
Electrochemical cell is a device in which an electric current (flow
of electrons) is either produced by a spontaneous chemical
reaction or is used to bring about a non-spontaneous reaction.

Recall in Thermochemistry: A spontaneous reaction is a

reaction that has a natural tendencies to occur on its own
without external influences.

i.e. the free energy of such reaction must be negative

(∆𝑮𝒓𝒙𝒏 = −𝒗𝒆)
A voltaic (galvanic cells) is an electrochemical cell in which a
spontaneous chemical reaction is used to generate an electrical
current.
• Galvanic cell name to honors Luigi, Galvani (1737 – 1798) an
Italian credited with discovery or electricity.
• Voltaic cell - after Aleksandra Volta (1745 – 1829) who
constructed cell of this type -1800.
They take advantage of a spontaneous reaction. e.g. batteries.
 How redox reaction can be use to generate a current, let
consider reaction between Zn(s) and Cu2+(aq)

𝑍𝑛 𝑠 + 𝐶𝑢2+ 𝑎𝑞 → 𝑍𝑛2+ 𝑎𝑞 + 𝐶𝑢(𝑠)

 A key question is: what causes the electrons to flow from the anode to the
cathode?
• The electrons flow from the anode to the cathode because of a difference
in the potential energy of the electrons at the anode compared to the
cathode

• In particular, the potential energy of the electrons is higher at the anode

than at the cathode
The absolute potential of single metal/metal ion system cannot be
measured directly.

• For connivances in working with cell potentials there is a

universal accepted convention for measuring cell potentials.

• We construct a standard hydrogen electrode, which is an

electrode in which gaseous hydrogen at one atmosphere
pressure is in equilibrium with hydrogen ions in solution,
concentration IM at 250C over a platinum surface.
Hence the standard hydrogen potential is the reference potential
against which all half-reaction potentials are assigned.
 𝑐𝑎𝑡ℎ𝑜𝑑𝑒: 2𝐻 + + 2𝑒 → 𝐻2 𝐸 𝑜 = 0.00 𝑉

𝑎𝑛𝑜𝑑𝑒: 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 𝐸 𝑜 = +0.76 𝑉

𝑂𝑣𝑒𝑟𝑎𝑙𝑙: 𝑍𝑛 + 2𝐻 2+ → 𝑍𝑛2+ + 𝐻2
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐻 +→𝐻2 + 𝐸𝑍𝑛→𝑍𝑛2+

= 0.00 V + 0.76 V = +0.76 V

The superscript O indicates that standard states are used
(This will be discussed later).
a. When a half-reaction is reversed, the sign of 𝐸 𝑜 is reversed.
e.g.
𝑐𝑎𝑡ℎ𝑜𝑑𝑒: 𝑍𝑛2+ + 2𝑒 → 𝑍𝑛 𝐸 𝑜 = −0.76 𝑉
𝑎𝑛𝑜𝑑𝑒: 𝐻2 → 𝑍𝑛 + 2𝐻 + + 2𝑒 𝐸 𝑜 = 0.00 𝑉

𝑜 𝑜 𝑜
𝑂𝑣𝑒𝑟𝑎𝑙𝑙: 𝑍𝑛2+ + 𝐻2 → +𝐻2 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑍𝑛→𝑍𝑛 2+ + 𝐸𝐻 + →𝐻
2
= −0.76 𝑉 +0.00 V = −0.76 𝑉

Note: Reaction will spontaneously proceed in the direction

for which the overall cell potential is positive.
b. When a half-reaction is multiplied by an integer,
𝐸 𝑜 remain the same.
 This is because standard reduction is an intensive
properties (it does not depend on how many times
the reaction occurs)
 The potential is not multiplied by the integer required
to balance the cell reaction
𝑐𝑎𝑡ℎ𝑜𝑑𝑒: 2𝐹𝑒 2+ + 2𝑒 → 2𝐹𝑒 3+ 𝐸 𝑜 = 0.77 𝑉
𝑎𝑛𝑜𝑑𝑒: 𝐶𝑢 → 𝐶𝑢2+ + 2𝑒𝐸 𝑜 = 0.34 𝑉
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑎𝑛𝑜𝑑𝑒 + 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒
I. For a gas, the standard state is a pressure of
exactly 1 atm (H2, O2, Cl2 etc)
II. For a substance present in a solution, the
standard state is a concentration of exactly
IM at an applied pressure of 1 atm (e.g. Cu2+,
H+, Cl- etc)
III. For a pure substance in a condensed state
(liquid or solid), the standard state is the pure
liquid or solid. e.g. Cu, Zn, Mg
IV. A temperature of 25oC
 A short hand way of describing the make-up of a
galvanic cell

 anode electrode |anode electrolyte||cathode

electrolyte |cathode electrode

 for in copper – silver cell, it is represented as

 Cu(s)|Cu2+||Ag+|Ag
 Example 5: Calculate 𝑬𝒐 for the following reactions
𝒂 𝑺𝒏 𝒔 + 𝑯− 𝒂𝒒 → 𝑺𝒏𝟐+ 𝒂𝒒 + 𝑯𝟐 (𝒈)
𝒃 𝑨𝒈 𝒔 + 𝑯− 𝒂𝒒 → 𝑨𝒈− 𝒂𝒒 + 𝟏𝟐𝑯𝟐 (𝒈)
will either of the above metals, Sn or Ag, spontaneously dissolve in acid solutions?

Example 6
(a) What is 𝑬𝒐𝒄𝒆𝒍𝒍 for the reaction
𝒁𝒏 𝒔 + 𝑺𝒏𝟒+ 𝒂𝒒 → 𝒁𝒏𝟐+ 𝒂𝒒 + 𝑺𝒏𝟐+ 𝒂𝒒
(b) Will metal Ni reduce
(i) Fe3+ to Fe2+
(ii) Zn2+ to Zn
(c) In which direction can the reaction
𝑺𝒏𝟐+ 𝒂𝒒 + 𝟐𝑭𝒆𝟑+ 𝒂𝒒 → 𝑺𝒏𝟒+ 𝒂𝒒 + 𝟐𝑭𝒆𝟐+ 𝒂𝒒
go spontaneously
Thank You for listening