ELECTROCHEMISTRY

PREPARED BY:
GREDA G. BALACUIT
 LEARNING OBJECTIVES
You will be able to:
 Identify main components of an electrochemical cell
 Write shorthand description of electrochemical cell
 Calculate cell voltage using standard reduction
potentials
 Apply Nernst equation to determine free energy
change
 Apply Nernst equation to determine pH
 Calculate amount of material deposited in electrolysis
HISTORY
Electrochemistry started as early as 600BC, there
were several scientist who studied electricity.
In 1780, Italian physician and physicist Luigi Aloisio
Galvani (1737-1798) discovered that muscle and
nerve cells produce electricity. While dissecting a
frog on a table where he had been conducting
experiments with static electricity, Galvani touched
the exposed sciatic nerve with his scalpel, which had
picked up an electric charge. He noticed that the
frog’s leg jumped.
 In 1800 Count Alessandro Giuseppe
Antonio Anastasio Volta (1745 – 1827)
developed the first electric cell, called a
Voltaic Pile.
A voltaic pile consist of alternating
layers of two dissimilar metals, separated
by pieces of cardboard soaked in
a sodium chloride solution.

Volta had built the voltaic pile

to challenge Luigi Galvani’s
claim to have demonstrated
that animals produce
electricity.
• In 1834, Michael Faraday developed
the two laws of electrochemistry:
• The First Law of Electrochemistry
The amount of a substance deposited
on each electrode of an electrolytic
cell is directly proportional to the
amount of electricity passing through
the cell.
• The Second Law of Electrochemistry
The quantities of different elements
deposited by a given amount of
electricity are in the ratio of their
chemical equivalent weights.
DEFINITION OF TERMS
Electrochemistry is a branch of chemistry that deals
with the study of the relationship between electricity
and chemical reaction.
Anode is the electrode where oxidation occurs.
Cathode is the electrode where reduction occurs.
Electrolyte is the electrolytic solution that permits the
movement of electrons.
ELECTRON TRANSFER REACTIONS

Electron transfer reactions are oxidation-

reduction or redox reactions.

Results in the generation of an electric

current (electricity) or be caused by
imposing an electric current.
TERMINOLOGY FOR REDOX
REACTIONS
OXIDATION—loss of electron(s) by a species;
increase in oxidation number.
REDUCTION—gain of electron(s); decrease in
oxidation number; decrease in oxygen.
OXIDIZING AGENT—electron acceptor;
species is reduced.
REDUCING AGENT—electron donor; species
is oxidized.
REDOX AT THE HEART OF THE
MATTER
Zn displaces Cu from CuSO4(aq)
Reaction:
CuSO4 (aq) + Zn Zn SO4 (aq) + Cu
Redox process:
• Zn is the reducing agent
• Cu2+ is the oxidizing agent

Zn(s)  Zn 2 (aq)  2e

Cu 2 (aq)  2e  Cu( s)
YOU CAN’T HAVE ONE… WITHOUT
THE OTHER!
Reduction (gaining electrons) can’t happen without an
oxidation to provide the electrons.
You can’t have 2 oxidations or 2 reductions in the same
equation. Reduction has to occur at the cost of oxidation

LEO the lion says GER!

GER!
 OXIDATION-REDUCTION
REACTIONS
Direct Redox Reaction
Oxidizing and reducing agents in
direct contact.

Cu(s) + 2 Ag+(aq) ---> Cu2+(aq) + 2 Ag(s)

OXIDATION-REDUCTION
REACTIONS
Indirect Redox Reaction
A battery functions by transferring electrons through an
external wire from the reducing agent to the oxidizing
agent.
 ELECTROCHEMICAL CELL
An apparatus that allows a redox reaction to
occur by transferring electrons through an
external connector.
• Voltaic or Galvanic cell relies
on spontaneous process to
generate a potential capable of
performing work – energy out
• Electrolytic cell performs
chemical reactions through
application of a potential –
energy in
 Basic Components
of Voltaic Cells

electrolyte

Anode Cathode
CHEMICAL CHANGE ---> ELECTRIC CURRENT

With time, Cu plates out

onto Zn metal strip, and
Zn strip “disappears.”

Zn is oxidized and is the reducing agent

Zn(s) ---> Zn2+(aq) + 2e-
Cu2+ is reduced and is the oxidizing agent
Cu2+(aq) + 2e- ---> Cu(s)
CHEMICAL CHANGE ---> ELECTRIC CURRENT

To obtain a useful current,

we separate the oxidizing
and reducing agents so
that electron transfer
occurs thru an external
wire.

This is accomplished in a GALVANIC or

VOLTAIC cell.
A group of such cells is called a battery.
 Zn --> Zn2+ + 2e- Cu2+ + 2e- --> Cu

Oxidation Reduction
Anode Cathode
Negative Positive

<--Anions
Cations--> RED CAT

•Electrons travel thru external wire.

Salt bridge allows anions and cations to move between
electrode compartments.
LABELLING THE PARTS
 CELL NOTATION
Anode on left, cathode on right
Electrons flow from left to right
Oxidation on left, reduction on right
Single vertical = electrode/electrolyte boundary
Double vertical = salt bridge

Anode: Cathode:
Zn →Zn2+ Cu2+ + 2e
+ 2e →Cu
VERTICAL │DENOTES
DIFFERENT PHASE
Fe(s)│Fe2+(aq)║Fe3+(aq),Fe2+(aq)│Pt(s)

Cu(s)│Cu2+(aq)║Cl2(g)│Cl-(aq)│C(s)
CELL POTENTIAL, E
- a quantitative measure of the
tendency of reactants to proceed
to products when all are in their
standard states at 25 ˚C.

Standard electrode potential of a half reaction is

defined as its electrode potential when the activities of
the reactants and products are all unity.

For Zn/Cu cell, potential is +1.10 V at 25 ˚C and when

[Zn2+] and [Cu2+] = 1.0 M.
This is the STANDARD CELL POTENTIAL,
CALCULATING CELL VOLTAGE

Balanced half-reactions can be added

together to get overall, balanced
equation.
Zn(s) ---> Zn2+(aq) + 2e-
Cu2+(aq) + 2e- ---> Cu(s)
--------------------------------------------
Cu2+(aq) + Zn(s) ---> Zn2+(aq) + Cu(s)

If we know Eo for each half-reaction, we

could get Eo for net reaction.
 Zn-Cu ELECTROCHEMICAL CELL

+
Anode, Cathode,
negative, positive,
source of sink for
electrons electrons
Zn(s) ---> Zn2+(aq) + 2e- Eo = +0.76 V
Cu2+(aq) + 2e- ---> Cu(s) Eo = +0.34 V
-----------------------------------------------------------------------------
Cu2+(aq) + Zn(s) ---> Zn2+(aq) + Cu(s) Eo = +1.10 V
EO FOR A VOLTAIC CELL

Cd --> Cd2+ + 2e- Fe --> Fe2+ + 2e-

or or
Cd2+ + 2e- --> Cd Fe2+ + 2e- --> Fe

All ingredients are present. Which way does reaction proceed?

CALCULATING CELL POTENTIALS
UNDER STANDARD CONDITIONS

E°cell = E°reduction - E°oxidation

E°cell = E°cathode - E°Anode

When adding E° values for the half-cells, do not

multiply the half-cell E° values, even if you need
to multiply the half-reactions to balance the
equation.
 MORE ABOUT
CALCULATING CELL VOLTAGE
Assume I- ion can reduce water.
2 H2O + 2e- ---> H2 + 2 OH- Cathode
2 I- ---> I2 + 2e- Anode
-------------------------------------------------
2 I- + 2 H2O --> I2 + 2 OH- + H2

Assuming reaction occurs as written,

E˚ = E˚cat+ E˚an= (-0.828 V) - (- +0.535 V) = -1.363 V
Minus E˚ means rxn. occurs in opposite direction
(the connection is backwards)
SAMPLE PROBLEMS

Consider the following redox reactions:

2Fe 3+ + Sn2+ 2Fe 2+ + Sn4+
2H + + Sn (s) H2(g) + Sn2+
Cr(s ) + Ag+ Cr 3+ + Ag(s)

a. Write each net process in terms of two balanced half reations

b. Express each half-reaction as a reduction.
c. Calculate the cell potential
d. Determine if the reaction is spontaneous or not.
THE ROLE OF INERT
ELECTRODES
Not all cells start with elements as the redox
agents
Consider the cell
Fe (s) + 2 Fe3+ (aq) 3Fe2+ (aq)
Fe can be the anode but Fe3+ cannot be the
cathode.
Use the Fe3+ ions in solution as the “cathode”
with an inert metal such as Pt
Anode Catho
de

Oxidati Reduct
on ion
CONNECTIONS: CELL POTENTIAL
AND FREE ENERGY
• The cell in open circuit generates an
electromotive force (emf) or potential
or voltage.
• This is the potential to perform work
• Energy is charge moving under applied
voltage
STANDARD REDUCTION POTENTIAL
We cannot measure the absolute tendency of a
half-reaction, we can only measure it
relative to another half-reaction.
We select as a standard half-reaction the
reduction of H+ to H2 under standard
conditions, which we assign a potential
difference = 0 v.
• Standard hydrogen electrode, SHE
STANDARD CELL
POTENTIALS
The total cell potential is the sum of the
potentials for the two half reactions at each
electrode
Ecell = Ecath + Ean
From the cell voltage we cannot determine the
values of either, we must know one to get the
other
Enter the standard hydrogen electrode (SHE)
All potentials are referenced to the SHE (=0 V)
UNPACKING THE SHE
The SHE consists of a Pt
electrode in contact with H2(g)
at 1 atm in a solution of 1 M
H+(aq).
The voltage of this half-cell is
defined to be 0 V
An experimental cell containing
the SHE half-cell with other half-
cell gives voltages which are
the standard potentials for
those half-cells
Ecell = 0 + Ehalf-cell
ZINC HALF-CELL WITH SHE
Cell measures 0.76 V
Standard potential for Zn(s) = Zn2+(aq) + 2e = 0.76 V
WHERE THERE IS NO SHE
In this cell there is no SHE and the measured voltage
is 1.10 V
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Zn Zn 2 (aq) C u 2 (aq) Cu
STANDARD REDUCTION POTENTIALS

Any half reaction can be written in two ways:

Oxidation:
M = M+ + e (+V)
Reduction:
M+ + e = M (-V)
Listed potentials are standard reduction potentials
APPLYING STANDARD
REDUCTION POTENTIALS
Consider the reaction
Zn(s)  2 Ag  (aq)  Zn 2 (aq)  2 Ag (s)

What is the cell potential?

The half reactions are:

Ag (aq)  e  Ag ( s) Zn(s)  Zn 2 (aq)  2e
E° = 0.80 V – (-0.76 V) = 1.56 V
NOTE: Although there are 2 moles of Ag
reduced for each mole of Zn oxidized, we do
not multiply the potential by 2.
THE NERNST EQUATION
 Solving Problems Using
Nernst Equation
Calculate the potential for the cell

Ag/Ag+ (0.0200M) // Cu2+ (0.0200M)/Cu

Ecell = E red – E ox
 PROBLEM
1. Find the cell potential of a galvanic cell based on the following
reduction half-reactions at 25 °C

Cd2+ + 2 e- → Cd E0 = -0.403 V
Pb2+ + 2 e- → Pb E0 = -0.126 V
where [Cd2+] = 0.020 M and [Pb2+] = 0.200 M.

2. Calculate the potential of the cell and indicate the direction of

the spontaneous cell reaction.
Zn/Zn2+ (0.0955M)//Co2+ (.00678M) / Co
 ELECTROCHEMICAL CELLS
In all electrochemical cells, oxidation occurs at the
anode, reduction occurs at the cathode.
In voltaic cells
• Anode is the source of electrons and has a (−) charge.
• Cathode draws electrons and has a (+) charge.
In electrolytic cells
• Electrons are drawn off the anode, so it must have a
place to release the electrons—the positive terminal of
the battery.
• Electrons are forced toward the anode, so it must have a
source of electrons—the negative terminal of the battery.
Voltaic versus Electrolytic Cells
ELECTROLYSIS
Electrolysis is a method of using a direct
electric current (DC) to drive an otherwise
non-spontaneous chemical reaction.
Electrolysis is commercially highly important
as a stage in the separation of elements from
naturally occurring sources such as ores
using an electrolytic cell
ELECTROLYSIS
Electrolysis is the process of
using electrical energy to
break a compound apart.

Electrolysis is done in an
electrolytic cell.

Electrolytic cells can be used

to separate elements from
their compounds.
 ELECTROLYTIC CELLS
Use an applied voltage to carry out a nonspontaneous
chemical reaction.
Electric current supplied by an external source
Power
Supply

Cathode Anode
e.g. inert Ti e.g. inert Ti

+ -

 Cl- Na+ 

Electrolyte, e.g.
NaCl

• External source must provide a greater potential than that for the spontaneous
reverse reaction
• Electrolysis = process in which electrical energy is used to cause a non-
spontaneous chemical reaction to occur
 Electrolytic Cells
Characteristics …

1. Nonspontaneous redox reaction

2. Produces chemicals from electricity

3. Forces electrolysis to occur

An electrolytic cell is a system of two inert

(nonreactive) electrodes (C or Pt) and an
electrolyte connected to a power supply.

I
Electrolytic Cell
Oxidation always occurs at the anode and reduction at
the cathode
Electrons flow through the wire and go from anode to
cathode
Anions (- ions) migrate to the anode and cations (+ions)
migrate towards the cathode.
The electrode that is connected to the -ve terminal of the
power supply will gain electrons and therefore be the site
of reduction. Oxidation is connected to +ve terminal.
ELECTROLYSIS
In electrolysis we use electrical energy to overcome the
energy barrier of a nonspontaneous reaction,
allowing it to occur.
The reaction that takes place is the opposite of the
spontaneous process.
2 H2(g) + O2(g)  2 H2O(l) spontaneous
2 H2O(l)  2 H2(g) + O2(g) electrolysis
Some applications are
(1) metal extraction from minerals and purification
(2) production of H2 for fuel cells
(3) metal plating.
 Definition of Terms
Polarization denote any (potentially undesirable)
mechanical side-effects that occur at the interface between
electrolyte and electrodes.

Overpotential: voltage actually required to overcome

electrode polarization in electrolytic cells. In aqeous
solutions, it is due to extra voltage required to produce a
gas bubble such as (O2)

Over voltage: the sum of the overpotential on both

electrodes of an electrolytic cell.

Decomposition voltage: refers to the minimum voltage

that is needed for electrolysis to occur
CALCULATION OF
DECOMPOSITION VOLTAGE

E applied = Ecell – IR - OV

Where:
Eapplied = decomposition voltage
Ecell = back emf
IR = cell resistance
OV = over voltage
PROBLEM

The following cell has been used for the determination of

cadmium in the presence of chloride ions.
Ag/AgCl(s),Cl- (0.200M),Cd2+ (0.0050M)/Cd
Calculate the potential that
a) Must be applied to prevent a current from developing in the
cell when 2 electrodes are connected.
b) Must be applied to cause an electrolytic current of 2 mA to
develop. Assume that resistance of the cell is 15.0Ω and no
over voltage.
 PROBLEM
Calculate the initial potential needed foa current of
0.078A in the cell,
Cu/Cu2+ (0.0064M) // Zn2+ (0.00375M)/Zn
I.f the cell resistance is 5.00Ω and overvoltage is
0.5v
 MIXTURES OF IONS

When more than one cation is present, the cation

that is easiest to reduce will be reduced first at
the cathode.
• Least negative or most positive E°red

When more than one anion is present, the anion

that is easiest to oxidize will be oxidized first at
the anode.
• Least negative or most positive E°ox
ELECTROLYSIS OF AQUEOUS SOLUTIONS
Possible cathode reactions
• Reduction of cation to metal
• Reduction of water to H2
• 2 H2O + 2 e−  H2 + 2 OH− E° = −0.83 V at stand. cond.
E° = −0.41 V at pH 7
Possible anode reactions
• Oxidation of anion to element
• Oxidation of H2O to O2
• 2 H2O  O2 + 4 e− + 4H+ E° = −1.23 V at stand. cond.
E° = −0.82 V at pH 7
• Oxidation of electrode
• Particularly Cu
• Graphite doesn’t oxidize
Half-reactions that lead to least negative Ecell will occur.
• Unless overvoltage changes the conditions
 Example 18.9 Predicting the Products of Electrolysis Reactions
Predict the half-reaction occurring at the anode and the cathode for electrolysis for each reaction.
a. a mixture of molten AlBr3 and MgBr2
b. an aqueous solution of LiI

Solution
a. In the electrolysis of a molten salt, the anion is oxidized and the cation is reduced. However, this mixture contains
two cations. Start by writing the possible oxidation and reduction half-reactions that might occur.

Since Br– is the only anion, write the equation for its oxidation, which occurs at the anode.

At the cathode, both the reduction of Al3+ and the reduction of Mg2+ are possible. The one that actually occurs is
the one that occurs most easily. Since the reduction of Al 3+ has a more positive electrode potential in aqueous
solution, this ion is more easily reduced. Therefore, the reduction of Al 3+ occurs at the cathode.
APPLICATION OF
ELECTROLYSIS
ELECTROLYSIS OF WATER
ELECTROLYSIS OF NACL(L)
ELECTROPLATING

In electroplating, the work

piece is the cathode.

Cations are reduced at

cathode and plate to
the surface of the work
piece.

The anode is made of

the plate metal. The
anode oxidizes and
replaces the metal
cations in the solution.
 STOICHIOMETRY OF
ELECTROLYSIS
In an electrolytic cell, the amount of product made is related to the
number of electrons transferred.
• Essentially, the electrons are a reactant.

The number of moles of electrons that flow through the electrolytic

cell depends on the current and length of time.
• 1 amp = 1 coulomb of charge/second
• 1 mole of e− = 96,485 coulombs of charge
• Faraday’s constant
 Stoichiometry of Electrolysis
Gold can be plated out of a solution containing Au3+ according to the half-
reaction: What mass of gold (in grams) is plated by a 25-minute flow of 5.5
Sort
A current?

You are given the half-reaction for the plating of gold, which shows the stoichiometric
relationship between moles of electrons and moles of gold. You are also given the current
and duration. You must find the mass of gold that will be deposited in that time.
Given: 3 mol e– : 1 mol Au
5.5 amps
25 min
Find: g Au

Strategize
You need to find the amount of gold, which is related stoichiometrically to the number of
electrons that have flowed through the cell. Begin with time in minutes and convert to
seconds. Then, since current is a measure of charge per unit time, use the given current and
the time to find the number of coulombs. You can use Faraday’s constant to calculate the
number of moles of electrons and the stoichiometry of the reaction to find the number of
moles of gold. Finally, use the molar mass of gold to convert to mass of gold.
 Example 18.10 Stoichiometry of Electrolysis
Continued

Conceptual Plan

Solve
Follow the conceptual plan to solve the problem, canceling units to arrive at the mass of gold.

Solution

Check
The answer has the correct units (g Au). The magnitude of the answer is reasonable if we consider that 10 amps
of current for 1 hour is the equivalent of about 1/3 mol of electrons (check for yourself), which would produce
1/9 mol (or about 20 g) of gold.
 Stoichiometry of Electrolysis
Silver can be plated out of a solution containing Ag+ according to
the half-reaction:

How much time (in minutes) would it take to plate 12 g of silver

using a current of 3.0 A?