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
2006, Prentice Hall, Inc.

Electrochemistry

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
oxidation reactions.
Electrons are
transferred.

When an atom is
losing electrons its
O.N. increases. It is
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
Electrochemistry
agent is reduced.

Balancing OxidationReduction 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) +2e2Fe3+(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 OHe. 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

MnO4 + C2O42-

+2

+4

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) + 2e3. 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) + 10eElectrochemistry

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 oxidationreduction 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 reactionfrom
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:
Ecell
(cathode) Ered
(anode)
= Ered
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,

Ered
= 0.76 V
For the reduction,

Ered
= +0.34 V

Electrochemistry

Cell Potentials
Ecell
= Ered
(cathode) Ered
(anode)
= +0.34 V (0.76 V)
= +1.10 V

Electrochemistry

 Since Ered = -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
Ered.
Therefore,
2Zn2+(aq) + 4e- 2Zn(s), Ered = -0.76 V.
Reactions with Ered > 0 are spontaneous reductions
relative to the SHE.
Electrochemistry

 Reactions with Ered < 0 are spontaneous oxidations

relative to the SHE.
The larger the difference between Ered values, the larger
Ecell.
In a voltaic (galvanic) cell (spontaneous) Ered(cathode) is
more positive than Ered(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) Ered(cathode) is
more positive than Ered(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 potentials
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-

2Fe3+(aq) + Cu(s) ----> Cu2+(aq) + 2Fe2+(aq)

Eo = - 0.34 V

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 Ecell, the
direction of electron flow, direction of ion
migration through salt bridge, and identify
the anode and cathode:
1. Cr3+ + Cl2 (g) Cr2O72- + Cl2. 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 Ecell 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 Ecell 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.
For such a cell, Ecell
would be 0, but Q would not.
Therefore, as long as the concentrations
are different, E will not be 0.

Electrochemistry

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, lea

Electrochemistry
dioxide cathode, and an electrolyte of 38% sulfuric

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

Common dry cell and its components.

Electrochemistry

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) + 4eElectrochemistry

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 measu

a change in potential when [H+] varies. Used toElectrochemistry
measure

Corrosion
Corrosion of Iron
Since Ered(Fe2+) < Ered(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), Ered = -0.76 V
Fe2+(aq) + 2e- Fe(s), Ered = -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), Ered = -2.37 V
Fe2+(aq) + 2e- Fe(s), Ered = -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