Chemistry 1B

SCHM3512
Lesson 9_
Electrochemistry
Prof. O. T. Johnson
(Department of Mining and Metallurgical Engineering,
University of Namibia)
 Chemistry, The Central Science, 10th edition
Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

Chapter 20
Electrochemistry

John D. Bookstaver
St. Charles Community College
St. Peters, MO Electrochemistry
© 2006, Prentice Hall, Inc.
Electrochemical Reactions

In electrochemical reactions, electrons

are transferred from one species to
another.
Metals tend to lose electrons and are
oxidized, non metals tend to gain
electrons and are reduced.

Electrochemistry
LEO GER
Losing
Electrons is
Oxidation.

Gaining
Electrons is
Reduction
Electrochemistry
 OIL RIG

• Oxidation
• Is
• Loss.

• Reduction
• Is
Gain.
Electrochemistry
 REDOX REACTIONS
• Are reduction – • When an atom is
oxidation reactions. losing electrons its
• Electrons are O.N. increases. It is
transferred. being oxidized.

• When an atom gains

electrons its O.N.
decreases. It is being
reduced
Electrochemistry
Oxidation Numbers

In order to keep
track of what loses
electrons and what
gains them, we
assign oxidation
numbers.

Electrochemistry
 Assigning Oxidation Numbers
1. Elements in their elemental form have an ON= 0.
2. The oxidation number of a monatomic ion is its
charge.
3. Nonmetals tend to have negative oxidation
numbers, although some are positive in certain
compounds or ions.
➢ Oxygen has an oxidation number of −2,
except in the peroxide ion in which it has an
oxidation number of −1.
➢ Hydrogen is +1 except in metal hydrides when
is −1 .
➢ Fluorine always has an oxidation number of −1.
Electrochemistry
Assigning Oxidation Numbers
➢ The other halogens have an oxidation
number of −1 when they are negative;
they can have positive oxidation
numbers, however, most notably in
oxyanions
4. The sum of the oxidation numbers in a
polyatomic ion is the charge on the
ion.
5. The sum of the oxidation numbers in a
neutral compound is 0.

Electrochemistry
 Oxidation and Reduction

• A species is oxidized when it loses electrons.

➢ Here, zinc loses two electrons to go from neutral
zinc metal to the Zn2+ ion.

Electrochemistry
 Oxidation and Reduction

• A species is reduced when it gains electrons.

➢ Here, each of the H+ gains an electron and they
combine to form H2.

Electrochemistry
 Oxidation and Reduction

• What is reduced is the oxidizing agent.

➢ H+ oxidizes Zn by taking electrons from it.
• What is oxidized is the reducing agent.
➢ Zn reduces H+ by giving it electrons.
Electrochemistry
 Oxidation-Reduction
Reactions
• Zn added to HCl yields the spontaneous reaction
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g).
• The oxidation number of Zn has increased from 0 to 2+.
• The oxidation number of H has reduced from 1+ to 0.
• Zn is oxidized to Zn2+ while H+ is reduced to H2.
• H+ causes Zn to be oxidized and is the oxidizing agent.
• Zn causes H+ to be reduced and is the reducing agent.
• Note that the reducing agent is oxidized and the oxidizing
agent is reduced. Electrochemistry
 Balancing Oxidation-
Reduction Reactions
• Law of conservation of mass: the amount of each element
present at the beginning of the reaction must be present at
the end.
• Conservation of charge: electrons are not lost in a
chemical reaction.
Half Reactions
• Half-reactions are a convenient way of separating
oxidation and reduction reactions.
Electrochemistry
 Half Reactions
• The half-reactions for
Sn2+(aq) + 2Fe3+(aq) → Sn4+(aq) + 2Fe2+(aq)
are
Sn2+(aq) → Sn4+(aq) +2e-
2Fe3+(aq) + 2e- → 2Fe2+(aq)
• Oxidation: electrons are products.
• Reduction: electrons are reactants.
Loss of Gain of
Electrons is Electrons is
Oxidation Reduction Electrochemistry
 Balancing Equations by the Method of
Half Reactions
• Consider the titration of an acidic solution of Na2C2O4
(sodium oxalate, colorless) with KMnO4 (deep purple).
• MnO4- is reduced to Mn2+ (pale pink) while the C2O42- is
oxidized to CO2.
• The equivalence point is given by the presence of a pale
pink color.
• If more KMnO4 is added, the solution turns purple due to
the excess KMnO4.

Electrochemistry
What is the balanced chemical equation?
1. Write down the two half reactions.
2. Balance each half reaction:
a. First with elements other than H and O.
b. Then balance O by adding water.
c. Then balance H by adding H+.
d. If it is in basic solution, remove H+ by adding OH-
e. Finish by balancing charge by adding electrons.
3. Multiply each half reaction to make the number of electrons
equal.
4. Add the reactions and simplify.
5. Check!

Electrochemistry
 Half-Reaction Method

Consider the reaction between MnO4− and C2O42− :

MnO4−(aq) + C2O42−(aq) ⎯⎯→ Mn2+(aq) + CO2(aq)

Electrochemistry
 Balancing Equations by the Method of
Half Reactions
• Consider the titration of an acidic solution of Na2C2O4
(sodium oxalate, colorless) with KMnO4 (deep purple).
• MnO4- is reduced to Mn2+ (pale pink) while the C2O42- is
oxidized to CO2.
• The equivalence point is given by the presence of a pale
pink color.
• If more KMnO4 is added, the solution turns purple due to
the excess KMnO4.

Electrochemistry
 Half-Reaction Method

First, we assign oxidation numbers.

+7 +3 +2 +4

MnO4− + C2O42- ⎯⎯→ Mn2+ + CO2

Since the manganese goes from +7 to +2, it is reduced.
Since the carbon goes from +3 to +4, it is oxidized.
Electrochemistry
For KMnO4 + Na2C2O4:

• The two incomplete half reactions are

MnO4-(aq) → Mn2+(aq)
C2O42-(aq) → 2CO2(g)
2. Adding water and H+ yields
8H+ + MnO4-(aq) → Mn2+(aq) + 4H2O
• There is a charge of 7+ on the left and 2+ on the right.
Therefore, 5 electrons need to be added to the left:
5e- + 8H+ + MnO4-(aq) → Mn2+(aq) + 4H2O

Electrochemistry
• In the oxalate reaction, there is a 2- charge on the left
and a 0 charge on the right, so we need to add two
electrons:
C2O42-(aq) → 2CO2(g) + 2e-
3. To balance the 5 electrons for permanganate and 2
electrons for oxalate, we need 10 electrons for both.
Multiplying gives:
10e- + 16H+ + 2MnO4-(aq) → 2Mn2+(aq) + 8H2O
5C2O42-(aq) → 10CO2(g) + 10e-

Electrochemistry
4. Adding gives:
16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq) → 2Mn2+(aq) +
8H2O(l) + 10CO2(g)
5. Which is balanced!

Electrochemistry
 Balancing in Basic Solution

• If a reaction occurs in basic solution, one

can balance it as if it occurred in acid.
• Once the equation is balanced, add OH−
to each side to “neutralize” the H+ in the
equation and create water in its place.
• If this produces water on both sides, you
might have to subtract water from each
side.
Electrochemistry
Examples – Balance the following oxidation-
reduction reactions:
1. Cr (s) + NO3- (aq)  Cr3+ (aq) + NO (g) (acidic)

2. Al (s) + MnO4- (aq)  Al3+ (aq) + Mn2+ (aq)

(acidic)

3. PO33- (aq) + Mn4- (aq)  PO43- (aq) + MnO2 (s)

(basic)

4. H2CO (aq) + Ag(NH3)2+ (aq)  HCO3- (aq) + Ag

(s) + NH3 (aq) (basic)

Electrochemistry
 Section 20-3 20-4

• Voltaic Cells – Spontaneous reactions

• ELECTRODES – POLARITIES
• SALT BRIDGE
• DRIVING FORCE- EMF
• STANDARD REDUCTION POTENTIALS
• HW Q 23, 25, 31, 33 (a, b ) , 35

Electrochemistry
Voltaic Cells

In spontaneous
oxidation-reduction
(redox) reactions,
electrons are
transferred and
energy is released.

Electrochemistry
 Voltaic Cells

• We can use that

energy to do work if
we make the
electrons flow
through an external
device.
• We call such a
setup a voltaic cell.

Electrochemistry
Voltaic Cells

• A typical cell looks

like this.
• The oxidation
occurs at the anode.
• The reduction
occurs at the
cathode.

Electrochemistry
Voltaic Cells

Once even one

electron flows from
the anode to the
cathode, the
charges in each
beaker would not be
balanced and the
flow of electrons
would stop.
Electrochemistry
Voltaic Cells
• Therefore, we use a
salt bridge, usually a
U-shaped tube that
contains a salt
solution, to keep the
charges balanced.
➢ Cations move toward
the cathode.
➢ Anions move toward
the anode.
Electrochemistry
 Voltaic Cells
• In the cell, then,
electrons leave the
anode and flow
through the wire to
the cathode.
• As the electrons
leave the anode, the
cations formed
dissolve into the
solution in the
anode compartment.
Electrochemistry
 Voltaic Cells
• As the electrons
reach the cathode,
cations in the
cathode are
attracted to the now
negative cathode.
• The electrons are
taken by the cation,
and the neutral
metal is deposited
on the cathode.
Electrochemistry
Electromotive Force (emf)
• Water only
spontaneously flows
one way in a
waterfall.
• Likewise, electrons
only spontaneously
flow one way in a
redox reaction—from
higher to lower
potential energy.
Electrochemistry
 Electromotive Force (emf)

• The potential difference between the

anode and cathode in a cell is called the
electromotive force (emf).
• It is also called the cell potential, and is
designated Ecell.

Electrochemistry
 Cell Potential
Cell potential is measured in volts (V).
One volt is the potential difference required
to impart 1J of energy to a charge of 1
coulomb. (1 electron has a charge of 1.6 x
10-19 Coulombs). The potential difference
between the 2 electrode provides the
driving force that pushes the electron
through the external circuit.

Electrochemistry
Cell Potential or Electromotive
Force (emf)
• The “pull” or driving force on the
electrons.
• ELECTROMOTIVE FORCE EMF
• CAUSES THE ELECTRON MOTION!

J
1V=1
C
Electrochemistry
Standard Reduction Potentials

Reduction
potentials for
many
electrodes
have been
measured and
tabulated.

Electrochemistry
Standard Hydrogen Electrode
• Their values are referenced to a standard
hydrogen electrode (SHE).
• By definition, the reduction potential for
hydrogen is 0 V:
2 H+ (aq, 1M) + 2 e− ⎯⎯→ H2 (g, 1 atm)

Electrochemistry
 Standard Cell Potentials

The cell potential at standard conditions

can be found through this equation:

 (cathode) − Ered
 = Ered
Ecell  (anode)

Because cell potential is based on

the potential energy per unit of
charge, it is an intensive property. Electrochemistry
For the reaction to be SPONTANEOUS
E has to be positive

Electrochemistry
Cell Potentials
• For the oxidation in this cell,
 = −0.76 V
Ered

• For the reduction,

 = +0.34 V
Ered

Electrochemistry
 Cell Potentials

 = Ered
Ecell  (cathode) − Ered
 (anode)
= +0.34 V − (−0.76 V)
= +1.10 V

Electrochemistry
• Since Ered = -0.76 V we conclude that the reduction of
Zn2+ in the presence of the SHE is not spontaneous.
• The oxidation of Zn with the SHE is spontaneous.
• Changing the stoichiometric coefficient does not affect
Ered.
• Therefore,
2Zn2+(aq) + 4e- → 2Zn(s), Ered = -0.76 V.
• Reactions with Ered > 0 are spontaneous reductions
relative to the SHE.

Electrochemistry
• Reactions with Ered < 0 are spontaneous oxidations
relative to the SHE.
• The larger the difference between Ered values, the larger
Ecell.
• In a voltaic (galvanic) cell (spontaneous) Ered(cathode) is
more positive than Ered(anode).
• Recall

Ecell = Ered (cathode) + Eox (anode)

Electrochemistry
 PNEUMONICS

• LEO GER
• OIL RIG
• RED CAT
• AND ALWAYS THE SOURCE OF
ELECTRONS IS THE NEGATIVE
ELECTRODE!!!

Electrochemistry
 Spontaneity of Redox
Reactions
• In a voltaic (galvanic) cell (spontaneous) Ered(cathode) is
more positive than Ered(anode) since
Ecell = Ered (cathode) + Eox (anode) Or
Ecell = Ered (cathode) − Ered (anode)
• More generally, for any electrochemical process
Ecell = Ered (reduction process) + Eox (oxidation process)
• A positive E indicates a spontaneous process (galvanic
cell).
• A negative E indicates a nonspontaneous process.
Electrochemistry
 Cell Potential Calculations
• To Calculate cell potential using
Standard Reduction Potentials:
• 1. One reaction and its cell potential’s
sign must be reversed--it must be
chosen such that the overall cell
potential is positive.
• 2. The half-reactions must often be
multiplied by an integer to balance
electrons--this is not done for the cell
potentials. Electrochemistry
 Cell Potential Calculations
Continued
• Fe3+(aq) + Cu(s) ----> Cu2+(aq) + Fe2+(aq)
• Fe3+(aq) + e- ----> Fe2+(aq) Eo = 0.77 V
• Cu2+(aq) + 2 e- ----> Cu(s) Eo = 0.34 V
• Reaction # 2 must be reversed.

Electrochemistry
 Cell Potential Calculations
Continued
• 2 (Fe3+(aq) + e- ----> Fe2+(aq)) Eo = 0.77 V
• Cu(s) ----> Cu2+(aq) + 2 e- Eo = - 0.34 V
• 2Fe3+(aq) + Cu(s) ----> Cu2+(aq) + 2Fe2+(aq)

• Eo = 0.43 V

Electrochemistry
 Oxidizing and Reducing Agents

The greater the

difference between
the two, the greater
the voltage of the cell.
REMEMBER TO
REVERSE THE SIGN
OF THE SPECIE
THAT GETS
OXIDIZED (THE ONE
BELOW!!!!!)
Electrochemistry
• Section 4.5 – 4.6
• Free energy and redox rx
• Cell EMF under nonstandard conditions
• Nerst Equation- Concentration cells
• Redox Applications - Batteries and fuel
cells – Corrosion prevention
• HW 47, 51 a, 59, 63
Electrochemistry
Oxidizing and Reducing Agents
• The strongest
oxidizers have the
most positive
reduction potentials.
• O.A. PULL electrons
• The strongest
reducers have the
most negative
reduction potentials.
• R.A. PUSH their
electrons
Electrochemistry
Examples – Sketch the cells containing the
following reactions. Include E°cell, the
direction of electron flow, direction of ion
migration through salt bridge, and identify
the anode and cathode:
1. Cr3+ + Cl2 (g)  Cr2O72- + Cl-
2. Cu2+ + Mg (s)  Mg2+ + Cu (s)
3. IO3- + Fe2+  Fe3+ + I2
4. Zn (s) + Ag+  Zn2+ + Ag

Electrochemistry
 Free Energy
G for a redox reaction can be found by
using the equation

G = −nFE

where n is the number of moles of

electrons transferred, and F is a
constant, the Faraday.
1 F = 96,485 C/mol = 96,485 J/V-mol
Electrochemistry
Free Energy and Cell Potential

Under standard conditions

 G = −nFE
• n = number of moles of electrons
• F = Faraday = 96,485 coulombs per
mole of electrons = 96,485 J/Vmol
• E=V
Electrochemistry
Find the free energy for the reaction of
Zn + Cu2+ ---> Zn2+ + Cu

Electrochemistry
 Effect of Concentration
on Cell EMF
The Nernst Equation
• A voltaic cell is functional until E = 0 at which point
equilibrium has been reached.
• The point at which E = 0 is determined by the
concentrations of the species involved in the redox
reaction.
• The Nernst equation relates emf to concentration using
G = G + RT ln Q
and noting that
− nFE = −nFE  + RT ln Q Electrochemistry
 The Nernst Equation
• This rearranges to give the Nernst equation:
RT
E = E − ln Q
nF
• The Nernst equation can be simplified by collecting all
the constants together using a temperature of 298 K:
0.0592
E = E − log Q
n
• (Note that change from natural logarithm to base-10 log.)
• Remember that n is number of moles of electrons.
Electrochemistry
 Cell EMF and Chemical Equilibrium
• A system is at equilibrium when G = 0.
• From the Nernst equation, at equilibrium and 298 K (E =
0 V and Q = Keq):

0.0592
0 = E − log K eq
n
nE 
log K eq =
0.0592 Electrochemistry
Examples
1. Calculate E°cell for the following reaction:
Zn (s) + Cu2+  Zn2+ + Cu (s)
2. Calculate Ecell if [Zn2+] = 1.88 M and [Cu2+] =
0.020 M

3. Calculate E°cell for the following reaction:

IO3- (aq) + Fe2+ (aq)  Fe3+ (aq) + I2 (aq)

4. Calculate Ecell if [IO3-] = 0.20 M, [Fe2+] = 0.65

M, [Fe3+] = 1.0 M, and [I2] = 0.75 M
Electrochemistry
 Concentration Cells

• Notice that the Nernst equation implies that a cell

could be created that has the same substance at
both electrodes.
 would be 0, but Q would not.
• For such a cell, Ecell
• Therefore, as long as the concentrations
Electrochemistry
are different, E will not be 0.
 Concentration Cells
• We can use the Nernst equation to generate a cell that has
an emf based solely on difference in concentration.
• One compartment will consist of a concentrated solution,
while the other has a dilute solution.
• Example: 1.00 M Ni2+(aq) and 1.00 10-3 M Ni2+(aq).
• The cell tends to equalize the concentrations of Ni2+(aq)
in each compartment.
• The concentrated solution has to reduce the amount of
Ni2+(aq) (to Ni(s)), so must be the cathode. Electrochemistry
Concentration Cells

Electrochemistry
 PROBLEM

• Use the Nernst equation to

determine the (emf) at 25oC of
the cell.
Zn(s)│Zn2+(0.00100M
║Cu2+(10.0M)│Cu(s).
• The standard emf of this cell is
1.10 V. Electrochemistry
 Applications of
Oxidation-Reduction
Reactions

Electrochemistry
 Batteries

•A battery is a galvanic cell or,

more commonly, a group of
galvanic cells connected in
series.

Electrochemistry
Batteries

Electrochemistry
17_370

+
–
H2SO4
electrolyte
solution

Anode (lead
grid filled with
spongy lead) Cathode (lead
grid filled with
spongy PbO2)

A lead storage battery consists of a lead anode, lead

dioxide cathode, and an electrolyte of 38% sulfuric acid.
Electrochemistry
 Lead Storage Battery
• Anode reaction:
Pb(s) +H2SO4(aq) ---> PbSO4(aq) + 2H+(aq) + 2e-
• Cathode reaction:
PbO2(s)+H2SO4(aq)+ 2e-+2H+(aq)-
>PbSO4(aq)+2H2O(l)
• Overall reaction:
Pb(s)+ PbO2(s) + 2H2SO4(aq)-->PbSO4(aq)+ 2H2O (l)
Electrochemistry
17_371

Anode
(zinc inner case)

Cathode
(graphite rod)

Paste of MnO2,
NH4CL, and
carbon

Electrochemistry
Common dry cell and its components.
 Alkaline Battery
• Anode: Zn cap:
Zn(s) → Zn2+(aq) + 2e-
• Cathode: MnO2, NH4Cl and C paste:
2NH4+(aq) + 2MnO2(s) + 2e- → Mn2O3(s) + 2NH3(aq) +
2H2O(l)
• The graphite rod in the center is an inert cathode.
• For an alkaline battery, NH4Cl is replaced with KOH.

Electrochemistry
• Anode: Zn powder mixed in a gel:
Zn(s) → Zn2+(aq) + 2e-
• Cathode: reduction of MnO2.

Electrochemistry
Electrochemistry
 Fuel Cells
• Direct production of electricity from fuels occurs in a
fuel cell.
• On Apollo moon flights, the H2-O2 fuel cell was the
primary source of electricity.
• Cathode: reduction of oxygen:
2H2O(l) + O2(g) + 4e- → 4OH-(aq)
• Anode:
2H2(g) + 4OH-(aq) → 4H2O(l) + 4e-
Electrochemistry
17_372

Insulation
Cathode (steel)
Anode (zinc container)

Solution of HgO (oxidizing

agent) in a basic medium (KOH
and Zn(OH)2)

Mercury battery used in calculators. Electrochemistry

 Fuel Cells

• ... galvanic cells for which the

reactants are continuously supplied.
• 2H2(g) + O2(g) → 2H2O(l)

• anode: 2H2 + 4OH− → 4H2O + 4e−

• cathode: 4e− + O2 + 2H2O → 4OH−

Electrochemistry
Hydrogen Fuel Cells

Electrochemistry
 17_369

Reference solution of
dilute hydrochloric acid

Silver wire coated with

silver chloride

Thin-walled membrane

Ion selective electrodes are glass electrodes that measures

a change in potential when [H+] varies. Used to measure pH.
Electrochemistry
 Corrosion
Corrosion of Iron
• Since Ered(Fe2+) < Ered(O2) iron can be oxidized by
oxygen.
• Cathode: O2(g) + 4H+(aq) + 4e- → 2H2O(l).
• Anode: Fe(s) → Fe2+(aq) + 2e-.
• Dissolved oxygen in water usually causes the oxidation
of iron.
• Fe2+ initially formed can be further oxidized to Fe3+
which forms rust, Fe2O3.xH2O(s).
Electrochemistry
• Oxidation occurs at the site with the greatest
concentration of O2.
Preventing Corrosion of Iron
• Corrosion can be prevented by coating the iron with paint
or another metal.
• Galvanized iron is coated with a thin layer of zinc.

Electrochemistry
Electrochemistry
• Zinc protects the iron since Zn is the anode and Fe the
cathode:
Zn2+(aq) +2e- → Zn(s), Ered = -0.76 V
Fe2+(aq) + 2e- → Fe(s), Ered = -0.44 V
• With the above standard reduction potentials, Zn is easier
to oxidize than Fe.

Electrochemistry
Electrochemistry
 Preventing Corrosion of Iron
• To protect underground pipelines, a sacrificial anode is
added.
• The water pipe is turned into the cathode and an active
metal is used as the anode.
• Often, Mg is used as the sacrificial anode:
Mg2+(aq) +2e- → Mg(s), Ered = -2.37 V
Fe2+(aq) + 2e- → Fe(s), Ered = -0.44 V

Electrochemistry
Electrochemistry
 Corrosion
•Some metals, such as copper, gold,
silver and platinum, are relatively difficult
to oxidize. These are often called noble
metals.
•About 1/5 of all iron and steel produced
each year is used to replace rusted
metal.

Electrochemistry
 Self-protecting Metals
• Some metals such as aluminum,
copper, and silver form a protective
coating that keeps them from
corroding further.
• The protective coating for iron and
steel flakes away opening new
layers of metal to corrosion.
Electrochemistry
 Prevention of Corrosion
• Coating--painting or applying oil to
keep out oxygen and moisture.
• Galvanizing--dipping a metal in a more
active metal -- galvanized steel bucket.
• Alloying -- mixing metals with iron to
prevent corrosion -- stainless steel.
• Cathodic protection -- attaching a more
active metal. Serves as sacrificial
metal--used to protect ships, gas lines,
and gas tanks.
Electrochemistry
 Redox Titrations

• Same as any other titration.

• the permanganate ion is used often because
it is its own indicator. MnO4- is purple, Mn+2
is colorless. When reaction solution remains
clear, MnO4- is gone.
• Chromate ion is also useful, but color change,
orangish yellow to green, is harder to detect.

Electrochemistry
 Example
• The iron content of iron ore can be
determined by titration with standard
KMnO4 solution. The iron ore is dissolved
in excess HCl, and the iron reduced to
Fe+2 ions. This solution is then titrated
with KMnO4 solution, producing Fe+3 and
Mn+2 ions in acidic solution. If it requires
41.95 mL of 0.205 M KMnO4 to titrate a
solution made with 10.613 g of iron ore,
what percent of the ore was iron?
Electrochemistry