20.

2 Voltaic Cells

• Voltaic cells use spontaneous oxidation-reduction

reactions to convert chemical energy into electrical
energy.

Spontaneous redox: doesn’t need external help to start

the reaction

• Also called galvanic cells

• The most common application is in batteries

Types of voltaic cells:

-Batteries ( dry/wet cells)
-fuel cells

• The Zn/Cu electrochemical cell is an example of

wet cell (voltaic cell)

Wet cell: has a liquid electrolyte

• Electrons given up at the anode pass along the external
connecting wire to the cathode.

• The movement of electrons through the wire must be

balanced by the movement of ions in the solution

* Thus, sulfate ions in the CuSO4 solution can move through the
barrier into the ZnSO4 solution.

• In a voltaic cell, electrons spontaneously ow from

anode to cathode.

• In a Daniell cell, the copper strip gains mass as copper

ions become copper atoms. The zinc strip loses mass as
the zinc atoms become zinc ions

• Electrons interact with copper ions in the solution

• To complete the circuit, both positive and negative ions

move through the aqueous solutions via the salt bridge.
 I Dry Cells

• Common sources of electrical energy

• Are voltaic cells

Types of dry cells:

-Zinc-carbon battery
-Alkaline battery
-Mercury battery

• They di er in the substances being oxidized

and reduced

Zinc-Carbon Dry Cells

• Batteries such as those used in ashlights

• Zinc container is lled with a moist paste of MnO2,

carbon black (in the notes H2O), NH4Cl, and ZnCl2
• When the external circuit is closed, zinc atoms
are oxidized at the negative electrode (anode)

• Electrons move across the circuit and reenter

the cell through the carbon rod (cathode)

• MnO2 is reduced in the presence of H2O

Anode: Zinc container Zn (s) —> Zn^2+ (aq) + 2e^-

Cathode: Carbon rod

2MnO2 (s) + H2O (l) + 2e^- —> Mn2O3 (s) + 2OH^- (aq) [book]
Mn^4+ + 2e^- —> Mn^3+ [notes]

* Although the carbon rod is the cathode, MnO2 is

being reduced

Electrolyte: MnO2, ZnCl2, NH4Cl, carbon black/H2O

 Alkaline Batteries

• Batteries found in a television remote or other

small electronic devices

• Don’t have a carbon rod cathode which allows

them to be smaller

• This cell uses a paste of Zn metal and potassium

hydroxide instead of a solid metal anode

Anode: Zinc and KOH [book + revision]

Zn (s) + 2OH^- (aq) —> Zn(OH)2 (s) + 2e^-

Cathode: MnO2 [book] MnO2, graphite [notes]

2MnO2 (s) + H2O (l) + 2e^- —> Mn2O3 (s) + 2OH^- (aq) [book]
Mn^4+ + 2e^- —> Mn^3+ [notes]

Electrolyte: KOH [book]

• Called alkaline because KOH is the base
[not really sure]

Mercury Batteries

• Tiny batteries found in hearing aids, calculators,

and camera ashes

• It is important that mercury batteries be recycled

and not just discarded, because mercury is a
poisonous substance

Anode: Zinc and KOH [book + revision]

Zn (s) + 2OH^- (aq) —> Zn(OH)2 (s) + 2e^-

Cathode: HgO and carbon

HgO (s) + H2O (l) + 2e^- —> Hg (l) + 2OH^- (aq) [book]
Hg^2+ + 2e^- —> Hg [notes]

Electrolyte: not included

 I Fuel Cells

• A voltaic cell in which the reactants are being

continuously supplied and the products are
being continuously removed

• Unlike a battery, a fuel cell could, in principle,

work forever, changing chemical energy into
electrical energy

• Fuel cells are e cient, cheap, a renewable

source, need no recharge, and no pollutants.

• Fuel cells exhaust water, not CO2 (greenhouse

gas) or CO (poisonous gas) as internal combustion
engines do

• Used in space programs such as in shuttles

Anode: H2 [notes + revision]
Porous graphite [book]
2H2 (g) + 4OH^- (aq) —> 4H2O (l) + 4e^- [book]
2H2 —> 2H^+ + 4e^- [notes]

Cathode: O2 [notes + revision]

Porous graphite [book]
O2 (g) + 2H2O (l) + 4e^- —> 4OH^- (aq) [book]
O2 + 4e^- —> 2O2^2- [notes]

Net reaction: 2H2 + O2 —> 2H2O

• The reactions in a fuel cell take place at carbon

electrodes that contain metal catalysts.

• The water formed is removed as a gas

 I Corrosion

• Corrosion is an electrochemical process that has

a large economic impact

• Approximately 20% of all the iron and steel produced

is used to repair or replace corroded structures

• One of the metals most commonly a ected by

corrosion is iron

Anode: Fe
Fe (s) —> Fe^2+ (aq) + 2e^-

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

Rust (hydrated iron III oxide ) net reaction:

4Fe(s) + 3O2(g) + xH2O(l) —> 2Fe2O3 * xH2O(s)
• When the iron is exposed to water and oxygen at
the anodic site is oxidized to Fe^2+ ions

• The electrons released from the anodic site travel

along the metal (like a wire) to the cathodic site,
where oxygen is reduced

• The Fe^2+ ions travel along the moisture toward the

cathodic site.

• At the cathode, the Fe^2+ ions are further oxidized

to Fe^3+ ions and form rust (hydrated iron oxide)
Fe2O3 * H2O
• The amount of hydration of the iron oxide
(coe cient x) varies and a ects the color of the rust

• The anode and cathode reactions occur at di erent

regions of the metal surface.

• The electric circuit is completed by electron ow

through the metal itself, which acts like the wire in
an electrochemical cell.

• The water on the surface of the metal serves as the

salt bridge

• For corrosion to occur, water and oxygen must be

present with the iron

• The cathodic reaction happens where the O2

concentration is high

• The anodic reaction happens where the O2

concentration is low (such as a pit in the metal)
 I Prevention

1- Paint the metal to protect it

2- Coat the steel with zinc (galvanizing)

• Zinc is more easily oxidized than iron, so it will react
before the iron oxidized.

3- Coating steel with a metal (cathodic protection)

• The metal being oxidized in called sacri cial anode

• The Alaskan oil pipeline, is an example of steel that

is cathodically protected. Instead of coating, zinc is
connected to the pipe by a wire.

• The zinc will oxidize before the iron in the steel

does, so as the zinc corrodes, it gives electrons to
the cathode (steel) to protect it.

• After the zinc reacts, it needs to be replaced.

 I Electric Potential
• In a voltaic cell, the oxidizing agent at the cathode
pulls the electrons through the wire away from the
reducing agent at the anode.

Electric potential (voltage): the “pull” or driving force

on the electrons; measured in volts (V)

• Volts is the same as potential energy per unit charge

Current: the movement of the electrons; measured in

amperes, or amp (A)

• Electric potential is similar to gravitational potential

• Electrons ow from higher electrical potential to

lower electrical potential
• In a voltaic cell, there are two electrodes (Zn and Cu).
These two metals each have di erent tendencies for
accepting electrons

Reduction potential: the tendency for the half-reaction

of either copper or zinc to occur as a reduction half-
reaction in an electrochemical cell

Electrode potential: the di erence in potential between

an electrode and its solution

• When the two half-cells are connected and the

reaction begins, a di erence in potential is observed
between the electrodes.

• The potential di erence (voltage) is proportional to

the energy required to move a certain electric charge
between the electrodes
• A voltmeter connected across the Zn Cu voltaic
cell measures a potential di erence of about 1.10 V
when the solution concentrations of Zn^2+ and
Cu^2+ ions are each 1 M

• The potential di erence across the complete voltaic

cell is easily measured and equals the sum of the
electrode potentials for the two half-reactions

• Individual electrode potential cannot be measured

directly, because there can be no transfer of electrons
unless both the anode and the cathode are connected
to form a complete circuit.

• A relative value for the potential of a half-reaction can

be determined by connecting it to a standard half-cell
as a reference.

Standard hydrogen electrode (SHE): is the standard

reference electrode for measuring electrode potentials
• It consists of a platinum electrode dipped into a
1.00 M acid solution surrounded by hydrogen gas at
1 atm pressure and 25°C

• Other electrodes are ranked according to their ability

to reduce hydrogen in the SHE

Anodic reaction: H2 (g) i 2H^+ (aq) + 2e^-

Anodic reaction: 2H^+ (aq)

i + 2e^- i H2 (g)

• An arbitrary potential of 0.00 V is assigned to both

of these half-reactions

Standard electrode potential (E^0): is the potential of a

half-cell under standard conditions measured relative
to the standard hydrogen electrode

• Electrode potentials are expressed as potentials for

reduction, which provide a reliable indication of the
tendency of a substance to be reduced
• Oxidizing agents have positive E^0 values.

• Half-reactions with negative reduction potentials

prefer oxidation over reduction.

• Reducing agents have negative E^0 values,

indicating that the metal or other electrode is more
willing to give up electrons than hydrogen

• When a half-reaction is written as an oxidation

reaction, the sign of its electrode potential is reversed

• Standard electrode potentials can be used to predict

if a redox reaction will occur spontaneously

• A spontaneous reaction will have a positive value for

E^0 cell.

E^0 cell = E^0 cathode - E^0 anode

• The half-reaction that has the more negative
standard reduction potential will be the anode and
vice versa