1

ELECTROCHEMISTRY
Chapter 3
 2
Electrochemistry
Electron transfer reactions are oxidation-reduction or redox

reactions.

Electrochemical processes are oxidation-reduction reactions

in which:

the energy released by a spontaneous reaction is

converted to electricity or

electrical energy is used to cause a nonspontaneous

reaction to occur
 3

Electrochemistry

Branch of Chemistry that deals with interconversion

of electrical and chemical energy.

Importance

Use of electricity in everyday life

Interconversion of energy

Study of electrochemical processes

 4
An electrochemical cell is a system consisting of electrodes

that dip into an electrolyte in which a chemical reaction either

uses or generates an electric current.

A voltaic, or galvanic cell is an electrochemical cell in which a

spontaneous reaction generates an electric current.

An electrolytic cell is an electrochemical cell in which an

electric current drives an otherwise nonspontaneous reaction.

 5
Terminology for Redox
Reactions
OXIDATION
OXIDATIONloss
lossof
ofelectron(s)
electron(s) by
byaaspecies;
species;increase
increase
in
inoxidation
oxidationnumber;
number; increase
increasein
in oxygen.
oxygen.
REDUCTION
REDUCTIONgain
gainofof electron(s);
electron(s); decrease
decreasein
in
oxidation
oxidationnumber;
number; decrease
decreasein inoxygen;
oxygen;increase
increasein
in
hydrogen.
hydrogen.
OXIDIZING
OXIDIZINGAGENT
AGENTelectron
electronacceptor;
acceptor;species
speciesis
is
reduced.
reduced.
REDUCING
REDUCINGAGENT
AGENTelectron
electrondonor;
donor;species
speciesis
is
oxidized.
oxidized.
 6

OXIDATION-REDUCTION
REACTIONS
Direct Redox Reaction

Oxidizing and reducing agents

in direct contact.

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

(aq) + 2 Ag(s)
 7

Electrochemical Cells
An apparatus that allows a redox reaction to occur by

transferring electrons through an external connector.

Product favored reaction ---> voltaic or galvanic cell

----> electric current

Reactant favored reaction ---> electrolytic cell --->

electric current used to cause chemical change.

 Basic Concepts 8

of Electrochemical Cells
wire
wire
electrons
electrons
Zn
Zn salt
salt
bridge
bridge
Cu
Cu

Zn2+ 2+
Zn2+ ions
ions Cu
Cu2+ ions
ions

Anode Cathode
 9
CHEMICAL CHANGE --->
ELECTRIC CURRENT
Zn
Zn metal
metal
With
With time,
time, Cu
Cu plates
plates out
out
onto
onto Zn
Zn metal
metal strip,
strip, and
and
Zn
Zn strip
strip disappears.
disappears.
Cu2+
Cu 2+ ions
ions

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)
 10
CHEMICAL CHANGE --->
ELECTRIC CURRENT
To obtain a useful wire
wire
electrons
electrons
current, we separate the
Zn
Zn
salt
salt
bridge Cu
Cu
oxidizing and reducing bridge

agents so that electron

transfer occurs thru an Zn
Zn2+ions
2+
ions Cu
Cu2+ions
2+
ions
external wire.

This is accomplished in a GALVANIC or

VOLTAIC cell. http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/galvan5.swf
A group of such cells is called a battery.
 11
Voltaic Cells
consists of two half-cells connected electrically.

Each half-cell is a portion of the electrochemical cell in

which a half-reaction takes place.

A simple half-cell can be made from a metal strip

dipped into a solution of its metal ion.

E.g. zinc-zinc ion half cell consists of a zinc strip dipped

into a solution of a zinc salt.

 12
Another simple half-cell consists of a copper strip

dipped into a solution of a copper salt.

In a voltaic cell, two half-cells are connected in

such a way that electrons flow from one

metal electrode to the other through an

external circuit.
 13
Atomic view of voltaic cell.
 14
Voltaic Cells
As long as there is an external circuit, electrons can flow

through it from one electrode to the other.

Because zinc has a greater tendency to lose

electrons than copper, zinc atoms in the zinc electrode

lose electrons to form zinc ions.

The electrons flow through the external circuit to the

copper electrode where copper ions gain the electrons to

become copper metal.

 Voltaic Cells
15

The two half-cells must also be connected internally

to allow ions to flow between them.

Without this internal connection, too much positive

charge builds up in the zinc half-cell (and too much

negative charge in the copper half-cell) causing the

reaction to stop.
Two electrodes are connected by an
16

external circuit.
 17
Voltmeter
e e
Zinc Copper
anode Cl K + cathode
Salt
bridge
SO 2 Cotton Cu2+
4
Zn 2+ plugs SO 2
4
ZnSO4 CuSO4 2e
2+
solution solution Cu2+
Zn
Cu

Zn is oxidized to Cu2+ is reduced

Zn2+ at anode. to Cu at cathode.
Zn(s) Zn2+ (aq) + 2 e 2e + Cu2+ (aq) Cu(s)
Net reaction
Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)
 18

Voltaic Cells
A salt bridge is a tube of an electrolyte in a gel that is

connected to the two half-cells of a voltaic cell.

The salt bridge allows the flow of ions but prevents the

mixing of the different solutions that would allow

direct reaction of the cell reactants.

 19

Terms Used for Voltaic Cells

 20

Voltaic Cells
The two half-cell reactions, as noted earlier, are:
2
Zn(s ) Zn (aq ) 2e (oxidation half-reaction)
2
Cu (aq ) 2e Cu(s ) (reduction half-reaction)

The first reaction, in which electrons are lost, is the

oxidation half-reaction.

The second reaction, in which electrons are gained, is

the reduction half-reaction.

 21

Voltaic Cells
The sum of the two half-reactions

2 2
Zn(s ) Cu (aq ) Zn (aq ) Cu(s )
is the net reaction that occurs in the voltaic cell; it is called
the cell reaction

Note that electrons are given up at the anode and thus flow
from it to the cathode where reduction occurs.
 22

Voltaic Cells

The anode in a voltaic cell has a negative sign

because electrons flow from it.

The cathode in a voltaic cell has a positive sign

 23
Notation for Voltaic Cells
The cell consisting of the zinc-zinc ion half-cell and

the copper-copper ion half-cell, is written

2 2
Zn(s ) | Zn (aq ) || Cu (aq ) | Cu(s )
salt bridge
anode cathode
The two electrodes are connected by a salt bridge, denoted
by two vertical bars.

Cell terminals are at the extreme ends in the cell notation.

A single vertical bar indicates a phase boundary, such as

between a solid terminal and the electrode solution.
 24

Line Notation
solid Aqueous Aqueous solid

Anode on the left Cathode on the right

Single line different phases.

Double line porous disk or salt bridge.

If all the substances on one side are aqueous, a

platinum electrode is indicated.

 25
Notation for Voltaic Cells
When the half-reaction involves a gas, an inert material
such as platinum serves as a terminal and an
electrode surface on which the reaction occurs.

Figure below shows a hydrogen electrode; hydrogen

bubbles over a platinum plate immersed in an acidic
solution.

The cathode half-reaction is

2H (aq ) 2e H 2 (g )
26
 27
Notation for Voltaic Cells
The notation for the hydrogen electrode, written
as a cathode, is

H (aq ) | H 2 (g ) | Pt
To write such an electrode as an anode, you
simply reverse the notation.

Pt | H 2 (g ) | H (aq )
To fully specify a voltaic cell, it is necessary to give the
concentrations of solutions and the pressure of gases.

2
Zn(s ) | Zn (1.0 M ) || H (aq ) | H 2 (1.0 atm ) | Pt
 28

A Problem To Consider

Give the overall cell reaction for the voltaic cell

2
Cd(s ) | Cd (1.0 M ) || H (aq ) | H 2 (1.0 atm ) | Pt
The half-cell reactions are
2
Cd(s ) Cd (aq ) 2e

2H (aq ) 2e H 2 ( g )
2
Cd(s ) 2H (aq ) Cd (aq ) H 2 ( g )
 29
Electromotive Force
An electric charge moves from a point of high electrical

potential to one of lower electrical potential.

The work expended in moving the electrical

charge through a conductor depends on the
amount of charge and the potential difference.
 30
Electromotive Force
Potential difference is the difference in electric potential

between two points.

Units: volts.
The volt, V, is the SI unit of potential difference equivalent
to 1 joule of energy per coulomb of charge.

1 volt 1 J
C
 31
Electromotive Force
The Faraday constant, F, is the magnitude of charge
on one mole of electrons; it equals 96,500 coulombs
(9.65 x 104 C).

work done by a voltaic cell In moving 1 mol of electrons

through a circuit is the product of the Faraday constant (F)
times the potential difference between the electrodes.

work(J) F(coulombs ) volts(J/coulomb )

work done by the system
 32
Electromotive Force
In the normal operation of a voltaic cell, the potential

difference (voltage) across the electrodes is less than

than the maximum possible voltage of the cell.

The actual flow of electrons reduces the electrical

pressure.

Thus, a cell voltage has its maximum value when no

current flows.
 33
Electromotive Force
The maximum potential difference between the

electrodes of a voltaic cell is referred to as the

electromotive force (emf) of the cell, or Ecell.

It can be measured by an electronic digital voltmeter

which draws negligible current.

 34
Electromotive Force
Expression for the maximum work attainable by

a voltaic cell:

Let n be the number of (mol) electrons transferred

in the overall cell reaction.

The maximum work for molar amounts of

reactants is

wmax nFE cell

 35

A Problem To Consider
The emf of the electrochemical cell below is 0.650 V.

Calculate the maximum electrical work of this cell

when 0.500 g H2 is consumed.

2
Hg 2 (aq ) H 2 (g ) 2Hg(l ) 2H (aq )
The half-reactions are
2
Hg 2 (aq ) 2e 2Hg(l )

H 2 (g ) 2H (aq ) 2e
 36
A Problem To Consider
2
Hg 2 (aq ) H 2 (g ) 2Hg(l ) 2H (aq )
n = 2, and maximum work for the reaction is written as

wmax nFE cell

4
wmax 2 (9.65 10 C) (0.650 V )
wmax 1.25 105 J
For 0.500 g H2, the maximum work is

1 mol H 2 1.25 105 J

0.500 g H 2 3.09 104 J
2.02 g H 2 1 mol H 2
 37
Cell emf
A cell emf is a measure of the driving force of cell reaction.

The reaction at the anode has a definite oxidation

potential, while the reaction at the cathode has a definite

reduction potential.

Thus, the overall cell emf is a combination of these two

potentials.

Ecell = oxidation potential + reduction potential

 38
Cell emf

A reduction potential is a measure of the

tendency to gain electrons in the reduction half-

reaction.

The oxidation potential for an oxidation half-

reaction is the negative of the reduction

potential for the reverse reaction.

 39
Cell emf

By convention, the Table of Standard Electrode

Potentials are tabulated as reduction potentials.

Consider the zinc-copper cell described earlier.

Zn(s ) | Zn 2 (aq ) || Cu 2 (aq ) | Cu(s )

The two half-reactions are

Zn(s ) Zn 2 (aq ) 2e
Cu 2 (aq ) 2e Cu(s )
40
 41
Cell emf

The zinc half-reaction is an oxidation.

If you write EZn for the reduction potential of zinc,

then EZn is the oxidation potential of zinc.

Zn 2 (aq ) 2e Zn(s ) (EZn)

Zn(s ) Zn 2 (aq ) 2e -(EZn)
The copper half-reaction is a reduction..
Write ECu for the electrode potential.

Cu 2 (aq ) 2e Cu(s ) (ECu)

 42
Cell emf
For this cell, emf is the sum of the reduction potential for the

copper half-cell and oxidation potential for the zinc half-cell.

Ecell ECu ( E Zn ) Ecell ECu E Zn

So, cell emf is difference between two electrode potentials.

In general, Ecell is obtained by subtracting the anode

potential from the cathode potential.

Ecell Ecathode Eanode

 43
Standard Electrode Potentials (Ecell)
Standard emf is the emf of a cell operating under standard

conditions of conc. (1 M), pressure (1 atm), & temp. (25C).

By convention, the reference chosen for comparing

electrode potentials is standard hydrogen electrode.

0 0
E0cell= Ecathode - Eanode

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

[Zn2+] and [Cu2+] = 1.0 M, this is the STANDARD CELL

POTENTIAL, Eocell
Strengths of Oxidizing and Reducing44
Agents
Standard electrode potentials are useful in determining

the strengths of oxidizing and reducing agents under

standard-state conditions.

Consequently, the strongest oxidizing agents in a table

of standard electrode potentials are the oxidized

species corresponding to the half-reactions with the

largest (most positive) Eo values. (For example F2(g))

 45

Reduction potential
More negative E

more easily electron is added

More easily reduced

Better oxidizing agent

More positive E

more easily electron is lost

More easily oxidized

Better reducing agent

Strengths of Oxidizing and Reducing46
Agents

Consequently, the strongest reducing agents in a

table of standard electrode potentials are the

reduced species corresponding to the half-

reactions with the smallest (most negative) Eo

values. (for example, Li(s))

 47

Calculating Cell Voltage

Balanced half-reactions can be added
together to get overall, balanced
equation.
Zn(s)
Zn(s) ---> Zn2+(aq)
---> Zn 2+
(aq) ++ 2e-2e-
Cu
Cu2+(aq)
2+
(aq) ++ 2e-
2e- --->
---> Cu(s)
Cu(s)
--------------------------------------------
--------------------------------------------
Cu
Cu (aq) + Zn(s) ---> Zn2+(aq)
2+(aq) + Zn(s) ---> Zn2+
2+
(aq) ++ Cu(s)
Cu(s)

If we know Eo for each half-reaction, we

could get Eo for net reaction.
 48

Calculating Cell Voltage

Note that the emf of the cell equals the standard

electrode potential of the cathode minus the standard

electrode potential of the anode.

o o o
Ecell Ecathode Eanode
 49
TABLE OF STANDARD
REDUCTION POTENTIALS
oxidizing
ability of ion Eo (V)

Cu2+ + 2e- Cu +0.34

2 H+ + 2e- H2 0.00

Zn2+ + 2e- Zn -0.76

To determine an oxidation
from a reduction table, just
reducing ability
take the opposite sign of the
of element
reduction!
 50
Zn/Cu Electrochemical Cell
wire
wire
electrons
electrons +
Zn
Zn
salt
salt
bridge
bridge
Cu
Cu
Anode, Cathode,
negative, positive,
source of sink for
Zn2+ 2+
electrons Zn2+ions
ions Cu
Cu2+ions
ions 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
51
 Eo for a Voltaic Cell
52

Volts
Volts

Cd
Cd Salt
Salt Bridge
Bridge Fe
Fe

2+ 2+
Cd2+
Cd Fe2+
Fe

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

or or
Cd2+ + 2e- --> Cd Fe2+ + 2e- --> Fe
All ingredients are present. Which way does
reaction proceed?
 53
Eo for a Voltaic Cell
Volts
Volts

Cd
Cd Salt
SaltBridge
Bridge Fe
Fe

Cd 2+ Fe 2+
Cd2+ Fe2+

From the table, we can see

Fe is a better reducing agent than Cd

Cd2+ is a better oxidizing agent than Fe2+

 More About 54

Calculating Cell Voltage

Assume I- ion can reduce water.
22 H O + 2e- --->
H22O + 2e- ---> H22 + 2 OHH + 2 OH --
Cathode
Cathode
22 II-- --->
---> II22 ++ 2e-
2e- Anode
Anode
-------------------------------------------------
-------------------------------------------------
22 II-- ++ 22 H
H22O --> II22 ++ 22 OH
O --> OH- ++ H
-
H22
Assuming reaction occurs as written,
E = Ecat+ Ean= (-0.828 V) - (- +0.535 V) = -1.363 V
Minus E means rxn. occurs in opposite direction
(the connection is backwards or you are
recharging the battery)
 55

Tips
E0 is for the reaction as written

The more positive E0 the greater the tendency for

the substance to be reduced

The half-cell reactions are reversible

The sign of E0 changes when the reaction is

reversed

Changing the stoichiometric coefficients of a half-

cell reaction does not change the value of E0
 56
A Problem To Consider
Calculate the standard emf for the following voltaic cell at 25C

using standard electrode potentials. What is the overall reaction?

Al(s ) | Al 3 (aq ) || Fe 2 (aq ) | Fe(s )

The reduction half-reactions and standard
potentials are
Al 3 (aq ) 3e Al(s ); Eo 1.66 V
Fe 2 (aq ) 2e Fe(s ); Eo 0.41 V
 57
A Problem To Consider
Reverse the first half-reaction & its half-cell potential to obtain

Al(s ) Al 3 (aq ) 3e ; Eo 1.66 V

Fe 2 (aq ) 2e Fe(s ); Eo 0.41 V

To obtain overall reaction we must balance the electrons.

2 Al(s ) 2 Al 3 (aq ) 6e ; Eo 1.66 V

3Fe 2 (aq ) 6e 3Fe(s ); Eo 0.41 V
 58
A Problem To Consider

Now add the reactions to get overall cell reaction and cell emf.

2 Al(s ) 2 Al 3 (aq ) 6e ; Eo 1.66 V

3Fe 2 (aq ) 6e 3Fe(s ); Eo 0.41 V
2 Al(s ) 3Fe 2 (aq ) 2 Al 3 (aq ) 3Fe(s ); Eo 1.25 V
 Equilibrium Constants from
59

emfs
For a voltaic cell, work = -nFEo, so when reactants are in
their standard state

o o
G nFE

Combining the previous equation, Go = -nFEocell, with the

equation Go = -RTlnK, we get

o
nFE cell RT ln K
 60

Spontaneity of Redox Reactions

 61

Relationships between Ecell, G

and K
 62

A Problem To Consider

The standard emf for the following cell is 1.10 V.

Zn(s ) | Zn 2 (aq ) || Cu 2 (aq ) | Cu(s )

Zn(s ) Cu 2 (aq ) Zn 2 (aq ) Cu(s )

Calculate the equilibrium constant Kc for the reaction

log K 37.2
37
K c 2 10
 Dependence of emf on Concentration 63

The free energy change, G, is related to the standard free

energy change,G, by the following equation.

o
G G RT ln Q
If we substitute G = -nFEcell and Go = -nFEocell into this
equation, we get
o
nFE cell nFE cell RT ln Q
The result rearranges to give the Nernst equation, an

equation relating the cell emf to its standard emf and

the reaction quotient.

 64

Substituting values for R and F at 25 oC, we get

Ecell Eocell
2.303RT
log Q Ecell Eocell
0.0592
log Q
nF n

The Nernst equation illustrates why cell emf decreases as

the cell reaction proceeds.

As reactant concentrations decrease and product

concentrations increase, Q increases, thus increasing

log Q which in turn decreases the cell emf.

 65
A Problem To Consider
What is the emf of the following voltaic cell at 25C?
Zn(s ) | Zn 2 (1 105 M ) || Cu 2 (0.100M ) | Cu(s )

The standard emf of the cell is 1.10 V.

Answer: The cell emf is 1.22 V.

 66

Electrolysis
Electrolysis- is the process in which electrical

energy is used to cause a nonspontaneous

chemical reaction to occur.

Electrolytic Cell- an apparatus for carrying out

electrolysis.
 67
Stoichiometry of Electrolysis
The quantity of electric charge passing through a
circuit in a given amount of time is given by

Electric charge(coul) = electric current (coul/sec) time lapse(sec)

 68

Faradays law
Relationship between the quantity of current (charge)

passed through a system, and the quantity of (electro)

chemical change that occurs due to the passage of the

current

Faradays First Law

The amount of chemical change is proportional to the

amount of current passed

 69

Faradays First law

Mathematical statement m = M I t /n F

m - mass of substance

M - molecular weight of the substance

I - current passed (A)

t - time for which the current is passed (s)

n - number of electrons transferred

F - Faraday constant (96475 C / eqv)

 70

Faradays Second law

 71
A Problem To Consider
When an aqueous solution of potassium iodide is
electrolyzed using platinum electrodes, the half-
reactions are
2I (aq ) I 2 (aq ) 2e
2H 2O(l ) 2e H 2 (g ) 2OH (aq )

How many grams of iodine are produced when a current of

8.52 mA flows through the cell for 10.0 min?

Answer: 6.73 X 10-3 grams

 72
Calculate the mass of copper which can be deposited
by the passage of 12.0 A for 25.0 min through a
solution of copper(II) sulfate.

How long would it take to plate 5.00 g Fe from an

aqueous solution of Fe(NO3)3 at a current of 2.00 A?
 73

A
Leclanche
dry cell
Anode (-)
Zn ---> Zn2+ + 2e-
Cathode (+)
2 NH4+ + 2e- --->
2 NH3 + H2

Return to slide 89
 Dry Cell or LeClanche Cell 74

Dry Cells
Invented in the 1860s the common dry cell or LeClanche

cell, has become a familiar household item.

An active zinc anode in the form of a can house a mixture

of MnO2 and an acidic electrolytic paste, consisting of

NH4Cl, ZnCl2, H2O and starch powdered graphite

improves conductivity.
The inactive cathode is a graphite rod.
 75
Anode (oxidation)
Zn(s) Zn2+(aq) + 2e-
Cathode (reduction). The cathodic half-reaction is complex.
MnO2(s) is reduced to Mn2O3(s) through a series of steps that
may involve the presence of Mn2+ and an acid-base reaction
between NH4+ and OH- :

2MnO2 (s) + 2NH4+(aq) + 2e- Mn2O3(s) + 2NH3(aq) + H2O (l)

The ammonia, some of which may be gaseous, forms a
complex ion with Zn2+, which crystallize in contact Cl- ion:

Zn2+(aq) + 2NH3 (aq) + 2Cl-(aq) Zn(NH3)2Cl2(s)

Overall Cell reaction:

2MnO2 (s) + 2NH4Cl(aq) + Zn(s) Zn(NH3)2Cl2(s) + H2O (l) +
Mn2O3(s) Ecell = 1.5 V
 Dry Cell or LeClanche Cell 76

Uses: common household items, such as portable radios,

toys, flashlights,

Advantage; Inexpensive, safe, available in many sizes

Disadvantages: At high current drain, NH3(g) builds up

causing drop in voltage, short shelf life because zinc anode

reacts with the acidic NH4+ ions.

 Dry Cell or LeClanche Cell 77

Acid version: Zinc inner case that acts as the anode and a
carbon rod in contact with a moist paste of solid MnO2 , solid
NH4Cl, and carbon that acts as the cathode. As battery wear
down, Conc. of Zn+2 and NH3 (aq) increases thereby decreasing
the voltage.
Half reactions: ECell = 1.5 V
Anode: Zn(s) Zn+2(aq) + 2e-

Cathode: 2NH4+(aq)+MnO2(s) + 2e- Mn2O3(s) +2NH3(aq)+H2O(l)

Advantage:
Inexpensive, safe, many sizes

Disadvantage:
High current drain, NH3(g) build up, short shelf life
 Alkaline Battery 78

An improved dry cell with similar half-reactions, but electrolyte is

a basic KOH paste, which eliminates the buildup of gases and
maintains the Zn electrode.

Anode (oxidation)
Zn(s) + 2OH- (aq) ZnO(s) + H2O (l) + 2e-
Cathode (reduction).
2MnO2 (s) + 2H2O (l) + 2e- Mn(OH)2(s) + 2OH-(aq)
Overall Cell reaction:
2MnO2 (s) + H2O (l) + Zn(s) ZnO(s) + Mn(OH)2(s) Ecell = 1.5 V
Uses: Same as for dry cell.
Advantages: No voltage drop and longer shell life than dry
cell because of alkaline electrolyte; sale ,amu sizes.
Disadvantages; More expensive than common dry cell.
 Alkaline Battery 79

Leclanche Battery: Alkaline Version

Solid NH4Cl is replaced with KOH or NaOH. This makes cell

last longer mainly because the zinc anode corrodes less
rapidly under basic conditions versus acidic conditions.
Half reactions: ECell = 1.5 V

Anode: Zn(s) + 2OH-(aq) g ZnO(s) + H2O(l) + 2e-

Cathode: MnO2 (s) + H2O(l) + 2e- g MnO3 (s) + 2OH-(aq)

Nernst equation: E = E - [(0.592/n)log Q], Q is constant

Advantage:
No voltage drop, longer shelf life.
Disadvantage:
More expensive
 80
A small alkaline dry cell.
Mercury and Silver batteries are similar.
Like alkaline dry cell, both these batteries use zinc in a basic
medium as the anode. The solid reactants are each
compressed with KOH, and moist paper acts as a salt bridge.
Anode: Zn is reducing agent under basic conditions
Cathode: HgO + H2O + 2e- ---> Hg + 2 OH-
 81
Lead-Acid Battery.

A typical 12-V lead-acid battery has six cells connected in

series, each of which delivers about 2 V.

Each cell contains two lead grids packed with the electrode

material: the anode is spongy Pb, and the cathode is

powered PbO2.

Grids are immersed in an electrolyte solution of 4.5 M H2SO4.

When the cell discharges, it generates electrical energy as a

voltaic cell.
 82

Lead Storage Battery

Half reactions: ECell = 2.0 V
Anode: Pb(s)+SO42PbSO4(s)+2e E=0.356
Cathode (Hg): PbO2(s)+SO42+4H++2e
PbSO4(s)+2H2O E=1.685V
Net:PbO2(s)+Pb(s)+2H2SO4PbSO4(s)+2H2O ECell =
2.0 V
Note that both half-reaction produce Pb2+ ion, one

through oxidation of Pb, the other through reduction

of PbO2. At both electrodes, the Pb2+ react with SO42-

 83

A lead
storage
battery.
 Nickel-Cadmium Battery 84

Battery for the Technological Age

Rechargeable, lightweight ni-cad are used for variety of

cordless appliances. Main advantage is that the oxidizing
and reducing agent can be regenerated easily when
recharged. These produce constant potential.

Half reactions: ECell = 1.4 V

Anode: Cd(s) + 2OH-(aq) Cd(OH)2 (s) + 2e-

Cathode:

2NiO(OH) (s) + 2H2O(l) + 2e- 2Ni(OH)2 (s) + 2 OH-(aq)

Ni-Cad Battery
85
86
Fuel Cells 87
Fuel Cells 88
 Fuel Cells; Batteries 89

Fuel Cell also an electrochemical device for converting

chemical energy into electricity.

In contrast to storage battery, fuel cell does not need to

involve a reversible reaction since the reactant are supplied to

cell as needed from an external source. This technology used

in Gemini, Apollo and Space Shuttle program.

Half reactions: ECell = 0.9 V

Anode: 2H2 (g) + 4OH-(aq) 4H2O(l) + 4e-

Cathode: O2 (g) + 2H2O(l) + 4e- 4OH-(aq)

 H2 as a Fuel
90

Cars can use electricity generated by H2/O2 fuel cells.

H2 carried in tanks or generated from hydrocarbons

Figure 20.15: A hydrogen-oxygen fuel91
cell.
 Fuel Cells; Batteries 92

Advantage:

Clean, portable and product is water. Efficient (75%) contrast to

20-25% car, 35-40% from coal electrical plant

Disadvantage:

Cannot store electrical energy, needs continuous flow of

reactant, Electrodes are short lived and expensive.

 Corrosion 93

Not all spontaneous redox reaction are beneficial.

Rusting - spontaneous oxidation.
Most structural metals have reduction potentials that are less
positive than O2 .
Fe Fe+2 +2e- E=
0.44 V
O2 + 2H2O + 4e- 4OH- E= 0.40 V

Fe+2 + O2 + H2O Fe2O3 + H+

Reactions happens in two places.
Rust: Fe2O3 X H2O
Anode: Fe(s) Fe+2 + 2e- E = 0.44 V
Cathode: O2 (g) + 4H+ + 4e- 2H2O (l) E = 1.23
 94

Salt speeds up process by increasing

conductivity
Water
Fe2+ Rust

e-
Iron Dissolves- O2 + 2H2O +4e- 4OH-
Fe Fe+2

Fe2+ + O2 + 2H2O Fe2O3 + 8 H+

 Conditions for Corrosion 95

Iron will oxidize in acidic medium

SO2 H2SO4 H+ + HSO4+
Anions improve conductivity for oxidation.
Cl- from seawater or NaCl (snow melting) enhances rusting
Conditions for Prevention:
Iron will not rust in dry air; moisture must be present
Iron will not rust in air-free water; oxygen must be present
Iron rusts most rapidly in ionic solution & low pH (high H+)
The loss of iron and deposit of rust occur at different place
on object
Iron rust faster in contact with a less active metal (Cu)
Iron rust slower in contact with a more active metal (Zn)
 Iron Corrosion; Chemistry 96
Most common & economically destructive form of corrosion

is the rusting of iron. Rust is not a direct product of the

reaction between iron and oxygen but arises through

complex electrochemical process.

The loss of iron and the depositing of rust often occur at

different places on the same object.

Iron Corrosion; Chemistry 97
 Corrosion Prevention 98

Coating to keep out air and water.

Galvanizing - Putting on a zinc coat

Has a lower reduction potential, so it is more easily

oxidized.

Alloying with metals that form oxide coats.

Cathodic Protection - Attaching large pieces of an

active metal like magnesium that get oxidized

instead.
 99

Balancing Equations
for Redox Reactions
Some redox reactions have equations that must be balanced by
special techniques.

MnO4- + 5 Fe2+ + 8 H+
---> Mn2+ + 5 Fe3+ + 4 H2O
Mn = +7 Fe = +2
Mn = +2 Fe = +3
 100

Balancing Equations
Consider the
reduction of Ag+
ions with copper
metal.

Cu + Ag+ --give--> Cu2+ + Ag

 101

Balancing Equations
Step 1: Divide the reaction into half-reactions, one
for oxidation and the other for reduction.
Ox Cu ---> Cu2+
Red Ag+ ---> Ag
Step 2: Balance each element for mass. Already
done in this case.
Step 3: Balance each half-reaction for charge by
adding electrons.
Ox Cu ---> Cu2+ + 2e-
Red Ag+ + e- ---> Ag
 102

Balancing Equations
Step 4: Multiply each half-reaction by a factor so
that the reducing agent supplies as many electrons
as the oxidizing agent requires.
Reducing agent Cu ---> Cu2+ + 2e-
Oxidizing agent 2 Ag+ + 2 e- ---> 2 Ag
Step 5: Add half-reactions to give the overall
equation.
Cu + 2 Ag+ ---> Cu2+ + 2Ag
The equation is now balanced for both
charge and mass.
 103

Balancing Equations
Balance the following in acid solution
VO2+ + Zn ---> VO2+ + Zn2+
Step 1: Write the half-reactions
Ox Zn ---> Zn2+
Red VO2+ ---> VO2+
Step 2: Balance each half-reaction for mass.
Ox Zn ---> Zn2+
Red
2 H+ + VO2+ ---> VO2+ + H2O
Add H2O on O-deficient side and add H+
on other side for H-balance.
 104

Balancing Equations
Step 3: Balance half-reactions for charge.
Ox Zn ---> Zn2+ + 2e-
Red e- + 2 H+ + VO2+ ---> VO2+ + H2O
Step 4: Multiply by an appropriate factor.
Ox Zn ---> Zn2+ + 2e-
Red 2e-
+ 4 H+ + 2 VO2+
---> 2 VO2+ + 2 H2O
Step 5: Add balanced half-reactions
Zn + 4 H+ + 2 VO2+
---> Zn2+ + 2 VO2+ + 2 H2O
 105

Tips on Balancing Equations

Never add O2, O atoms, or
O2- to balance oxygen.
Never add H2 or H atoms to
balance hydrogen.
Be sure to write the correct
charges on all the ions.
Check your work at the end
to make sure mass and
charge are balanced.
PRACTICE!