Chemistry for Grade 12

HARAR SENIOR SECONDARY

SCHOOL,
HARAR

CHEMISTRY FOR GRADE 12

CHAPTER: - 2
ELECTROCHEMISTRY

Prepared By:- SOLOMON KASSA

Academic Year:- 2016/2023

 Chemistry for Grade 12

CHAPTER:- 4
ELECTROCHEMISTRY

ELECTROCHEMISTRY
Electrochemistry is the area of chemistry dealing with the interconversion of electrical energy
and chemical energy. There are many applications of this in everyday life. Batteries, control of
corrosion, metallurgy and electrolysis are just a few examples of the applications of
electrochemistry. This handout will look at the basic principles of electrochemistry and show
some of its applications.

Electrochemistry always involves an oxidation-reduction process. Recall that oxidation involves

the loss of electrons by a substance (i.e, oxidation number increases and the number of electrons
decreases) and that reduction involves the gain of electrons by a substance. ( i.e, oxidation
number decreases and the number of electrons increases). You can’t have one process without
the other. The substance that is reduced is the oxidizing agent. This makes sense, because how
you define an oxidizing agent – a compound that is able to oxidize another substance by
removing electrons from that substance. Since the oxidizing agent is gaining the electrons that
it pulls off the substance it is oxidizing, the oxidizing agent becomes reduced during the process.
Similarly, the substance that is oxidized is the reducing agent. A reducing agent is a compound
that will reduce another substance by giving away its own electrons to the substance it is
reducing. Thus, since the reducing agent is losing those electrons, it becomes oxidized during
the process. It is important to be able to determine the oxidation states of the compounds
involved in an electrochemical process so as to identify which substance is oxidized and which
substance is reduced.

In general, metals tend to make good reducing agents because they can only be oxidized.
The reducing ability of the metal is given by the activity series. The more active metal is able to
reduce the less active metal cation. This activity series is:

Li>K>Ca>Na>Mg>Al>Zn>Cr>Fe>Ni>Sn>Pb>H2>Cu>Hg>Ag>Pt>Au
most active least active
So for example, magnesium metal is able to reduce copper(II) ions in solution to form
magnesium ions and copper metal: Mg(s) + Cu2+(aq) → Mg2+(aq) + Cu(s)
 Chemistry for Grade 12

ELECTROLYSIS OF AQUEOUS SOLUTIONS

►This circuit consists of a current source, an electrolyte, a wire, a light bulb, and two graphite rods
called electrodes.
►The brightness of the bulb increases with current strength, which increases with the number of ions
in the solution.
►The ability of different solutes to provide ions can be compared by comparing the brightness of the
light bulb at the same concentration.
 Chemistry for Grade 12
►Note that metallic conduction is a physical process, but electrolytic conduction causes chemical
changes to occur on the surface of the electrodes.

PREFERENTIAL DISCHARGE
The preferential discharge of ions is affected by:
1) the nature of the electrodes,
2) the positions of the ions in the electrochemical series and
3) the concentration of the ions in the electrolyte.

1. Nature of the electrodes

Inert electrodes:- do not take part in the chemical reaction.
do not affect the product of electrolysis, like graphite or platinum
Reactive or Active Electrodes:- such electrodes participate (take part) in the chemical reaction.
-can affect the product of electrolysis. like copper,

2. The position of the ions in the electrochemical series

The reactivity series or activity series is an empirical series of metals, in order of "Reactivity" from
highest to lowest. The reactivity series is sometimes quoted in the reverse order of standard electrode
potentials:
Li > K> Sr > Ca > Na > Mg> Al > Zn> Cr > Fe > Cd >
Co > Ni > Sn > Pb > H> Cu > Ag > Hg > Pt > Au
►Standard electrode potentials offer a quantitative measure of the power of a reducing agent, rather
than the qualitative considerations of other reactivity series. However, they are only valid for standard
conditions.
In particular, they only apply to reactions in aqueous solution.
►The order of reactivity, as shown by the vigor of the reaction with water or the speed at which the
metal surface tarnishing in air, appears to be:potassium > sodium > lithium > alkaline earth metals
►The ease of discharge of some common cations and anions.
►Cations:- The ease of discharge increase downward
Li+ < K+ < Na+ < Mg2+ < Al3+ < Mn2+ < Zn2+ < Cr3+ <
Fe2+ < Cd2+ < Pb2+ < Fe3+ < H+ < Cu2+ < Ag+ < Au3+
►Anions:- The ease of discharge increase downward
F– < SO42– < NO3– < CO32– < Cl– < Br– < l– < OH– < S2–
The ions that are lower in the electrochemical series get discharged in preference to those above
them.
►In general, if two or more positive ions migrate to the cathode, the ion lower in the series is
discharged preferentially. Similarly, if two or more negative ions migrate to the anode, the ion
lower in the series is discharged preferentially.

3. Concentration of the ions in the electrolyte

If an electrolyte contains a higher concentration of ions that are higher in the electrochemical
series than of those that are lower, then the higher ions get discharged in preference to the
lower ones.

ELECTROLYSIS OF SOME SELECTED AQUEOUS SOLUTIONS

1. Electrolysis of Molten NaCl

►Ions are:- Na+ ion (move towards the cathode) and Cl– ion (move towards the anode).
Cathode (reduction) : 2Na+ + 2e– ® 2Na( s)
Anode (oxidation) : 2Cl– ® Cl2(g) + 2e–
 Chemistry for Grade 12
Overall reaction : 2Na+ + 2Cl–  2 Na( s) + Cl2(g)
►Results in the formation of chlorine (Cl2) gas at anode and sodium (Na) metal at cathode.

2. Electrolysis of dilute NaCl solution

►Ions are:- Na+ & H+ ions (move towards the cathode) and Cl– & OH– ions (move towards the
anode).
Cathode (reduction) : [ 2H+(aq) + 2e–  H2(g) ] × 2
Anode (oxidation) : 4OH (aq)  2H2O(l) + O2(g) + 4e–
–

Overall reaction : 2H2O(l)  2H2(g) + O2(g)

► results in the decomposition of water to oxygen and hydrogen gases.

3. Electrolysis of brine solution (conc. NaCl solution)

►Ions are:- Na+ & H+ ions (move towards the cathode) and Cl– & OH– ions (move towards the
anode).
Cathode (reduction) : 2H+(aq) + 2e–  H2(g)
Anode (oxidation) : 2Cl–(aq)  Cl2 (g) + 2e–
Overall reaction : 2H+(aq) + 2Cl–(aq)  H2(g) + Cl2(g)
►The solution becomes Basic, b/c the solution yields NaOH.

4. Electrolysis of dilute H2SO4 solution

►Ions are:- H+ ions (move towards the cathode) and SO4–2 & OH– ions (move towards the
anode).
Cathode (reduction) : [ 2H+(aq) + 2e–  H2(g) ] × 2
Anode (oxidation) : 4OH–(aq)  2H2O(l) + O2(g) + 4e–
Overall reaction : 2H2O(l)  2H2(g) + O2(g)
► results in the decomposition of water to oxygen and hydrogen gases.

5. Electrolysis of Copper (II) Sulphate, Using Inert Electrodes

►Ions are:- Cu2+ & H+ ions migrate towards the cathode, and SO4 2– & OH– ions migrate
towards the anode.
Anode (oxidation) : 4OH–(aq)  2H2O(l) + O2(g) + 4e–
Cathode (reduction) : [Cu2+(aq) + 2e–  Cu(s)] × 2
Overall reaction : 2Cu 2+(aq) + 4OH–(aq)  2Cu(s) + 2H2O(l) + O2(g)
►The solution becomes Acidic, due to the formation of H2SO4.
►Oxygen gas is liberated at the anode and copper metal is deposited at the cathode.

6. Electrolysis of Copper (II) Sulphate, Using Copper (Active) Electrodes

►Ions are:- Cu2+ & H+ ions migrate towards the cathode, and SO4 2– & OH– ions migrate
towards the anode.
Anode (oxidation) : Cu (s)  Cu2+(aq) + 2e–
Cathode (reduction) : Cu2+(aq) + 2e–  Cu(s)
Overall reaction : Cu 2+(aq) + Cu (s)  Cu(s) + Cu 2+(aq)
►The copper electrode at the anode dissolves and copper metal will be deposited at the cathode
 Chemistry for Grade 12

VOLTAIC (GALVANIC) CELLS

A common application of electrochemistry is the galvanic cell, commonly known as a battery. A
galvanic cell has the capability of producing a voltage and was invented by Luigi Galvani and
Alessandro Volta. A schematic of such a cell is shown below:

The schematic shows how a zinc anode connected by a salt bridge to a copper cathode will
convert chemical energy to electrical energy and allow the light bulb to light up. Lets look at
the electrochemistry involved. For any electrochemical cell, oxidation always occurs at the
anode and reduction always occurs at the cathode. An easy way to remember this is to keep the
vowels together and the consonants together (oxidation at the anode; reduction at the cathode).
Also, when drawing a galvanic cell, most people use the convention where the anode is on the
left and the cathode is on the right. Use the mnemonic:ABC to remember
(Anode/Bridge/Cathode).

1. What is salt bridge? Give examples of such electrolytes that are used as salt bridge?
2. What are the purposes (uses) of salt bridge? (List at least three)

CELL NOTATION:- is a shorthand representation of a Galvanic cell.

anode | anode electrolyte (M) || cathode electrolyte (M) | cathode

The cell notation for the above cell would be: Zn(s) | Zn2+(aq), 1M || Cu2+(aq), 1M | Cu(s)
 Chemistry for Grade 12
One begins at the solid zinc anode. A single vertical line ( | ) indicates a phase change from solid
zinc anode to aqueous zinc sulfate solution in the anode compartment. The double vertical line(
|| ) indicates the salt bridge connecting the anode compartment to the cathode compartment.
Next, one describes the copper(II) sulfate solution in the cathode compartment. Once again, a
single vertical line indicates a phase change from aqueous copper(II) solution in the cathode
compartment to the solid copper cathode.

Electrode polarity Electrolytic cell Galvanic cell

Anode Positive Negative
Cathode Negative Positive

STANDARD REDUCTION POTENTIALS

The cell potential is the difference between two electrode potentials, one associated with the
cathode and the other associated with the anode.
 The energy released by a spontaneous redox reaction can be used to perform
electrical work
 Voltaic or galvanic cells are devices in which electron transfer occurs via an
external circuit
 If a strip of zinc is placed in a solution of CuSO4 , Cu is deposited on the Zn and
the Zn dissolves and is converted to Zn+2
 Zn is spontaneously oxidized and Cu is spontaneously reduced
 This voltaic cell consists of :
o An oxidation half reaction of Zn(s)Zn+2 + 2e
 Oxidation takes place at the anode
o A reduction half reaction : Cu+2 + 2e  Cu(s)
 Reduction takes place at the cathode
 A salt bridge ( used to complete the circuit)
o Cations move from anode to cathode
o Anions move from cathode to anode
 2 solid metal strips which are the anode and cathode
 We expect the Zn strip to lose mass and the copper strip to gain mass
 Electrons flow from anode to cathode
o The anode is negative , the cathode is positive
o Electrons can not move through the solution. They are carried through an
external wire
o Anions and cations move through the salt bridge
A Molecular View

 At the anode electrons are products ► Oxidation occurs at the

anode
 At the cathode electrons are reactants ► Reduction occurs at the
cathode
Cell EMF
 The flow of electrons from anode to cathode is spontaneous
 Chemistry for Grade 12
 Electrons flow from anode to cathode because the cathode has a lower electrical
potential
 Potential difference is measured in volts
 One volt is the potential difference required to impart one joule of energy to a charge of
one coulomb
 1 volt = 1 J/C
 Electromotive force is the force required to push electrons through the external circuit
 Cell potential is the EMF of the cell = Ecell
 Ecell  0 for a spontaneous reaction
 For 1M solutions or 1 atm for gases at 25 C, the standard emf is called E0 cell
Standard Reduction Potential
 The emf of a cell can be calculated from standard reduction potentials.
o Ecell = Ered(Cathode) – Ered (Anode)
 We use the reaction: 2H+(aq,1M) + 2e H2(gas,1 atm) Ecell = 0 V. This is the standard
hydrogen electrode (SHE)
 Consider the half reaction:
o Zn(s)  Zn+2 + 2e
o We can measure this reaction relative to SHE. In this case, SHE is the cathode. It
consists of a Pt electrode in a solution of 1M H+ .
o H2 is bubbled through the solution.
 Ecell = Ered (cathode) – Ered (anode)
0.76V = 0V – Ered (anode) , so anode= -0.76V

 Standard reduction potentials must be written as reduction reactions:

Zn+2 + 2 e Zn(s) Ered = - 0.76 V
► Since E is negative we conclude that the reduction of Zn+2 in the presence of SHE is not
spontaneous. However the oxidation of Zn(s) with SHE is spontaneous
 The standard reduction potential is an intensive property. Therefore changing the
stochiometric coefficients does not change E
2 Zn+2 + 4 e  2 Zn(s) E = --0.76 V
 If Ered is greater than zero the reaction is spontaneous relative to SHE
 The more positive the value of Ered , the greater the driving force for reduction

Oxidizing and Reducing Agents

 The table of standard reduction potentials can be used to determine the relative strength
of reducing (and oxidizing) agents
o The more positive Ered , the stronger the oxidizing agent
o The more negative Ered , the stronger the reducing agent
o we can predict F2 will oxidize H2 or Li(s)
o We can predict Ni+2 will oxidize Al(s)

Spontaneity of Redox Reactions

 For any electrochemical process : Ecell = Ered(reduction process) – Ered(oxidation process).

 If positive, the reaction is spontaneous
 Consider the reaction of nickel solid and silver ion:
 Chemistry for Grade 12
Ni(s) + 2Ag+  Ni+2 + Ag(s)

The standard potential is: Ecell = Ered (Ag+ / Ag) – Ered ( Ni+2/ Ni)

= 0.8V – (-0.28V) = +1.08 V (This reaction is spontaneous & the forward rxn is
favored)

An E˚ > 0 means the cell will be spontaneous (produce a voltage). An E˚ < 0 means the cell must
be supplied that voltage from an external power supply in order for the cell reaction to run in
the direction it is written. If anything, that cell would want to run in the reverse direction.
Often these nonspontaneous cells are called electrolytic cells.

Exercise-1:
1. For each of the following galvanic cell, write the anode and cathode half-cell reactions, the
overall cell reaction, and calculate the standard cell potential. Use the standard reduction half-
cell potentials
(a) Zn|Zn2+(aq, 1 M)||Fe3+,Fe2+(aq, 1 M)|Pt;
(b) Zn|Zn2+(aq, 1 M)||Br2,Br-(aq, 1 M)|Pt;
2. Write the cell notation and calculate the standard cell potential for galvanic cells in which the
following reactions occur:
(a) Pb(s) + 2 Fe3+(aq)  Pb2+(aq) + 2Fe2+(aq)
(b) 2Li(s) + I3-(aq)  2Li+(aq) + 3I-(aq)

ELECTROMOTIVE FORCE (EMF)

►It is the driving force that allows the electrons to overcome resistance from localised atoms
and move
around the circuit.
►The electromotive force in a Galvanic cell comes from the redox reaction that pushes
electrons from
the anode to a cathode through the external circuit. ►Electrons on the negative electrode
repel each
other and have more potential energy than electrons on the positive electrode.
►Energy that overcomes resistance appears as heat or as light emitted by a glowing filament.
► Electrical work is used for starting cars, running watches, radios, and computers etc.
►Electrical work (W) is the product of the emf of the cell and the total charge that passes
through the
cell:
W=Q×E where Q is the charge and E is electrical potential.
The total charge is determined by, Q = nF 1 F = 96,500 C/mol e– = 96, 500 J/V. mol e–
Wmax = Wele = – nFEcell
►The change in free energy (ΔG) represents the maximum amount of useful work that can be
obtained
from a reaction. ΔG = Wmax = – nFEcell
ΔG = – nFEcell
►Both n and F are positive quantities, and ΔG is negative for a spontaneous process, so Ecell
must be
positive.
►A positive Ecell value corresponds to a negative ΔG value, which is the condition for
spontaneity.
For standard state conditions,
ΔG° = – nFE°cell and ΔG° = – RT ln K
 Chemistry for Grade 12
If we substitute -- nFE°cell = -- RT ln K
E°cell = RT ln K
nF
When T = 298 K, the equation can be simplified by substituting for R and F.

E°cell = (8.134J/mol K) (298 K) lnK = 0.0257 V ln K

n (96,500J/V mol) n

Therefore, E°cell = 0.0592V log K.

n
Equations ΔG° = – RT ln K, ΔGo = – nFE°cell E°cell = – ΔG° .
nF
Relationship among ΔGo, K and E°cell
ΔGo K Eocell Reaction under standard state conditions
Negative >1 Positive Favours the formation of products.
Zero =1 Zero Reactants and products are equally favoured.
Positive <1 Negative Favours the formation of reactants.

EMF and Free Energy Change

 We can show that : G = -nFEcell , where G is the change in free energy, n is the
number of moles of electrons transferred , F is Faradays constant and E is the emf of the
cell.
 1F = 96,500 Coulomb/mol= 96,500 J/ V-mol
 Since n and F are positive, if G is negative, then Ecell must be positive and the reaction
will be spontaneous

Effect of Concentration on Cell EMF

 A voltaic cell is functional until Ecell = 0. At this point equilibrium is reached

o The cell is dead
o This point, E cell = 0, is determined by the concentrations of the species involved in
the Redox reaction
 Nernst Equation
o The dependence of cell EMF on concentration can be derived from the
dependence of free energy change on concentration
G = G0 + RT ln Q where Q is the reaction quotient

substituting G = -nFEcell we get -nFEcell = -nFE0cell +RTlnQ

Solving for E cell gives the Nernst equation:

Ecell = E0cell – RT/nF (lnQ) which is customarily written in base 10 so:

Ecell = E0cell – 2.303RT/nF (log Q) at T= 298 K the equation becomes:

Ecell = E0cell - 0.0592V/n (log Q) for Zn(s) + Cu+2 Zn+2 + Cu(s) we get the following:

Ecell = 1.10V - 0.0592V/2 log [Zn+2] / [Cu+2] in this case n=2 since 2 electrons are being
transferred. Remember solids = 1 in an equilibrium expression.

Concentration Cells
 Chemistry for Grade 12

A cell whose EMF is generated solely by a difference in concentration

Consider a cell with 2 Ni(s) electrodes but a difference in the concentration of Ni+2 . One
cell has [Ni+2] = 1M and the other [Ni+2] = 0.001M
 The standard cell potential is obviously zero. However, the cell is operating under
nonstandard conditions
 The driving force is the difference in concentration
 Using the Nernst equation we calculate a EMF of + 0.0888V
Cell EMF and Chemical Equilibrium

 A system is at equilibrium when G = 0

 From the Nernst equation : log Keq = nE0cell
0.0592
 Thus if we know the cell EMF we can calculate the equilibrium constant

DEPENDENCE OF CELL POTENTIAL ON CONCENTRATION

The quantitative relationship between electrolyte concentration and cell potential is given by
the
following
Nernst Equation: Ecell = Eocell - (RT/nF) lnQ;
Ecell is cell potential under non-standard conditions, while Eocell is cell potential under standard
conditions, R = 8.314 J/(mol.K), F = 96,485 C/mol, is the Faraday’s constant; Q is the reaction
quotient, such that, for the reaction:
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s), Q = [Zn2+]/[Cu2+].
RT (8 . 314 J/mol. K )(298 K )
At 25 C, F = 96,500 C/mol
o
= 0.0257 J/C = 0.0257 V
The expression for the Nernst equation becomes,
(0 . 0257 V)
Ecell = Eocell - n lnQ ;
(0 . 0591 V )
Ecell = E cell - o n logQ
For example, the non-standard cell potential for
Zn|Zn2+(aq, 0.010 M)||Cu2+(aq, 1.0 M)|Cu can be calculated as follows:

Ecell = (EoCu2+|Cu + EoZn|Zn2+) - (0.0591 V) log([Zn2+]/[Cu2+]);

n
(0 . 0591 V)
= (0.34 V + 0.76 V) - n log(0.010 M/1.0 M)
= 1.10 V + 0.060 V = 1.16 V

For the voltaic cell, Cu|Cu2+(aq)||Ag+(aq)|Ag, the Nernst equation is expressed as:
Ecell = (EoAg+|Ag + EoCu|Cu2+) - (0.0591 V/2) log ([Cu2+]/[Ag+]2)

If [Ag+] = 0.010 M, [Cu2+] = 1.0 M, and Eocell = 0.80 V – 0.34 V = 0.46 V,

 Chemistry for Grade 12
(0 . 0591 V )
Ecell = 0.46 V – 2 log{1.0/(0.010)2}
(0 . 0591 V)
= 0.46 V – 2 (4.0) = 0.46 V – 0.12 V = 0.34 V
The cell potential calculated from Nernst equation is the maximum potential at the instant the
cell circuit is connected. As the cell discharges and current flows, the electrolyte concentrations
will change, Q increases and Ecell deceases.

The cell reaction will occur spontaneously until it reaches equilibrium, at which point Q = K
(the equilibrium constant) and
Ecell = Eocell - (RT/nF) ln(K) = 0 ;
ln(K) = nFEocell/RT; K = exp(nFEocell/RT)
Note also that at equilibrium, G = Go – RT ln(K) = 0 (no current flows through the circuit)

Exercise-3:
1. Write an overall net ionic equation and calculate the cell potential at 25 oC for:
Zn|Zn2+(aq, 0.0050 M)||Cu2+(aq,1.0 M)|Cu
2. Write an overall net ionic equation and calculate the cell potential at 25 oC for:
Cu|Cu2+(aq, 0.0050 M)||Ag+(aq, 0.50 M)|Ag
3. The standard cell potential (Eocell) for the following galvanic cell is 1.10 V
Zn|Zn2+(aq, 1M)||Cu2+(aq, 1M)|Cu
What is the K value for the reaction: Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s) ?


Concentration Cells
A concentration cell is an electrochemical cell in which both half-cells are of the same type,
but with different electrolyte concentrations. The following cell notations are examples of
concentration cells:
Cu|Cu2+(aq, 0.0010 M)||Cu2+(aq, 1.0 M)|Cu
Ag|Ag+(aq, 0.0010 M) ||Ag+(aq, 0.10 M)|Ag
In concentration cells, the half-cell with the lower electrolyte concentration serves as an anode
half-cell and one with the higher electrolyte concentration is the cathode half-cell. At the anode
half-cell, oxidation reaction occurs to increase the electrolyte concentration and at the cathode
half-cell, a reduction reaction occurs to decrease its electrolyte concentration. Oxidation-
reduction reaction will continue until the electrolyte concentrations in both half-cells become
equal.

At anode half-cell: Cu(s)  Cu2+(aq) + 2e-; (in 0.0010 M Cu2+)

At cathode half-cell: Cu2+(aq) + 2e-  Cu(s); (in 0.50 M Cu2+)

BATTERIES
Batteries are galvanic cells or a group of galvanic cells connected in series, where the total battery
potential is equal to the sum of the potentials of the individual cells. There are three types of batteries
– primary batteries, secondary batteries, and the fuel cell. Primary batteries are not re-chargeable,
where as secondary batteries are re-chargeable. Fuel cell will last as long as there is an ample supply
of fuel to provide the energy.
 Chemistry for Grade 12
Dry Cells:- The normal (acidic) dry batteries, alkaline batteries, and the mercury batteries are
example of primary batteries.
1. LeClanchè cells The “acidic” dry battery consists of Zinc casing as container, anode and as the
reducing agent; graphite rod as (inert) cathode; aqueous NH 4Cl paste as electrolyte, and MnO2
powder as the oxidizing agent.

Zn|Zn2+,NH4+,NH3(aq)||Mn2O3,MnO2|C(s)

Anode reaction: Zn(s)  Zn2+(aq) + 2e-;

Cathodic reaction: 2MnO2(s) + 2NH4+(aq) + 2e-  Mn2O3(s) + 2NH3(aq) + H2O(l)

Net reaction: Zn(s) + 2MnO2(s) + 2NH4+(aq)  Zn2+(aq) + Mn2O3(s) + 2NH3(aq) + H2O(l)
► The reverse reaction is prevented by the formation of [Zn(NH3)4]2+ ions.
► A new dry cell battery has a potential of about 1.5 V regardless of the size, but the amount of
energy that a battery can deliver depends on its size. For example, a D-size battery can deliver more
current (greater amperes) than an AAA-size battery. Normal dry batteries use aqueous NH 4Cl paste as
electrolyte and are referred to as acidic batteries due to the following ionization: NH 4+(aq) 
NH3(aq) + H+(aq)

2. Alkaline batteries also use zinc (as the reducing agent) and MnO2 (as oxidizing agent), but aqueous
paste containing KOH, instead of NH4Cl, is used as the electrolyte. The anode and cathode reactions
are as follows:
At anode: Zn(s) + 2OH-(aq)  ZnO(s) + H2O(l) + 2e-;
At cathode: 2MnO2(s) + H2O(l) + 2e-  Mn2O3(s) + 2OH-(aq);

Net reaction: Zn(s) + 2MnO2(s)  ZnO(s) + Mn2O3(s)
Since all reactants involved are in the solid form, alkaline batteries can deliver a fairly constant
voltage until the limiting reactant is completely used up. They also last longer because zinc metal
corrodes more slowly under basic conditions.

3. mercury batteries Batteries used in calculators and watches are mercury batteries. The following
reactions occur at the anode and cathode sections of the cell:
Anode reaction: Zn(s) + 2OH-(aq)  ZnO(s) + H2O + 2e-;
Cathode reaction: HgO(s) + H2O + 2e-  Hg(l) + 2OH-(aq)
Net cell reaction: Zn(s) + HgO(s)  ZnO(s) + Hg(l)

4. Lead Storage Batteries

These are batteries used in all types of automobiles. The lead storage batteries contain sulfuric
acid as electrolyte. Each cell contains a number of grids of lead alloy. One set of alternating grids is
packed with lead metal and the other with lead(IV) oxide, PbO 2. Each set of grids, which are the
electrodes, are connected in a parallel arrangement, which enables the cell to deliver more current -
the amount of current delivered depends on the surface area of the electrode. Each cell in a lead
storage battery produces a potential of about 2.01 V. A standard 12-V battery used in most cars
contains six cells connected in series.
Spontaneous Reactions that occur in the lead storage battery are:
Anode reaction: Pb(s) + HSO4-(aq)  PbSO4(s) + H+(aq) + 2e-
Cathode reaction: PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e-  PbSO4(s) + 2H2O(m)

 Chemistry for Grade 12
Net reaction: Pb(s) + PbO2(s) + 2H+(aq) + 2HSO4-(aq)  2PbSO4(s) + 2H2O(l) 
discharging
The greatest advantage of lead storage batteries is that they are re-chargeable. When you start the
engine the discharge reaction occurs, but while the car is being driven, the battery obtains energy
from the motor through the alternator and the following re-charging reaction occurs:
2PbSO4(s) + 2H2O(l)  Pb(s) + PbO2(s) + 2H+(aq) + 2HSO4-(aq)  re-charging
Lead storage batteries also have a longer lifetime and can deliver a relatively large amount of current
and electrical energy within a short time. The major disadvantages are: (1) they are very heavy and
bulky - non-portable; (2) lead is a toxic metal and the disposal creates environmental problems; (3)
the battery must be kept upright and H2SO4 is very corrosive.

5. Lithium batteries: these are batteries used in cameras and computers.

Anode reaction: 2 Li(s)  Li+(aq) + 2e-;
Cathode reaction: I3-(aq) + 2e-  3I-(aq)
Net cell reaction: 2Li(s) + I3-(aq)  2Li+(aq) + 3I-(aq)
6, Nickel-Cadmium batteries are rechargeable batteries used in cordless phones. They contain
cadmium as the anode and hydrated nickel oxide as the cathode. The electrolyte is made up of
aqueous KOH paste.
Anode reaction: Cd(s) + 2OH-(aq)  Cd(OH)2(s) + 2e-;
Cathode reaction: 2NiO(OH)(s) + 2H2O(l) + 2e-  2Ni(OH)2(s) + 2OH-(aq);
Net cell reaction: Cd(s) + 2NiO(OH)(s) + 2H2O(l)  Cd(OH)2(aq) + 2Ni(OH)2(aq);

7, Fuel Cells:
A fuel cell is a galvanic cell that uses hydrogen (as fuel), which reacts with oxygen, and a large
amount of energy from the reaction is available to produce electricity. The fuel is supplied
continuously from an external tank. The hydrogen-oxygen fuel cells are used in the space shuttle
modules.
Anode reaction: 2H2(g) + 4OH-(aq)  4H2O(l) + 4e-;
Cathode reaction: 2H2O(l) + O2(g) + 4e-  4OH-(aq)
Net cell reaction: 2H2(g) + O2(g)  2H2O(l) + Energy

CORROSION CONTROL
Corrosion is a spontaneous oxidation of metals by atmospheric oxygen – a process that has
great economic impact. Consider the rusting process of a steel pipe. The process is accelerated by the
presence of water droplets on the metal surface. At the edge of the droplet, the part of iron exposed to
the air acts as the cathode for the electrochemical reaction. At the center of the droplet, the metal acts
as anode and get oxidized (corroded).

O2 OH- Fe2+ OH- O2

Cathode Anode Cathode

At the edge of the droplet, molecular oxygen is reduced to OH-:

O2(g) + 2H2O(l) + 4e-  4OH-(aq)
 Chemistry for Grade 12
and at the center of the droplet, metallic iron is oxidized to Fe2+:
2Fe(s)  2Fe2+(aq) + 4e-
Inside the droplets, Fe2+ combines with OH- to form iron(II) hydroxide, Fe(OH)2, which is then
further oxidized to iron(III) oxide, Fe2O3.H2O.
Fe2+(aq) + 2OH-(aq)  Fe(OH)2(s)
4Fe(OH)2(s) + O2(g)  2Fe2O3.H2O(s) + 2H2O
"rust"
Corrosion prevention can be done by passive method, such as by painting the metal surface, thus
prevents contact of the metal surface with oxygen and moisture. The active method of corrosion
prevention involves electrochemical process, which is the method employed in the control of
corrosion of underground steel pipes and tanks. If the pipe is wrapped or tied with a metal that is
more electropositive than iron, such as magnesium, aluminum, or zinc, then in electrochemical
reactions these metals will act as the anodes and the iron (pipe) as the cathode, while the wet soil acts
as the electrolyte. The sacrificial metals will be oxidized before the pipe.

For example, if magnesium is used as sacrificial anode, the following reactions will occur:
2Mg(s)  2Mg2+(aq) + 4e-; (at anode)
and, O2(g) + 2H2O(l) + 4 e-  4OH-(aq) (at cathode)
Net reaction: 2Mg(s) + O2(g) + 2H2O  2Mg(OH)2(s);
This method of corrosion prevention using active metals such as magnesium as sacrificial anode is
called a cathodic protection, because as a cathode the pipe will not oxidized.

Electrochemistry Worksheet
1. Assign oxidation numbers to each atom in the following:
a. P4O6 b. BiO3 − c. N2H4 d. Mg(BrO4)2 e. MnSO4 f. Mn(SO4)2
2. For each of the reactions below identify the oxidizing agent and the reducing agent.
A. 2 KCl + MnO2 + H2SO4 → K2SO4 + MnSO4 + Cl2 + H2O
B. SiCl4 + 2 Mg(s) → 2 MgCl2 + Si
3. Use the half-reaction method to balanceeach of the following oxidation-reduction reactions.
Identify the oxidizing agent and the reducing agent.
+ 2+
A. Cu(s) + Ag (aq) → Ag(s) + Cu
B. Al(s) + I2(s) → AlI3 (s)
3+ 2+
C. Pb(s) + Fe (aq) → Pb (aq) + Fe(s)

4.Balance each of the following oxidation-reduction reactions. Identify the oxidizing agent and the
reducing agent.
2− − − 2−
A. S2O3 + OCl → Cl + S4O6 (in acid )
−
B. CH3OH + MnO4 → HCOO + MnO2 (in base )
C. NO3 − + Zn → NH4+ + Zn2+ (in acid)
D. Br2 → Br + BrO3
− −
(in base)

5. Write the cell notation for the voltaic cell that incorporates the following redox reaction.
Mg(s) + Sn2+(aq) → Mg2+(aq) + Sn(s)
 Chemistry for Grade 12
2+ 2+
6. Drawa voltaic cell that is constructed with a Mn/Mn electrode and a Cd/Cd electrode. Use the
emf table in the textbook to determine which electrode will be the cathode and which will be the
anode. Your drawing should include all of the following components:
2+ 2+
a. Label the location of each substance (Mn, Mn , Cd, and Cd )
b. Label the cathode and the anode
c. Label the direction of electron flow
d. Label which electrode is positively charged and which is negatively charged.
e. Include a salt bridge with NaNO3. Label the direction that each ion flows
f. Write the cell notation for this voltaic cell.
g. Calculate the cell potential of this cell.

7. Given the following half-reactions and half-cell potentials, write the balanced overall
electrochemical reaction that would occur and calculate the cell potential of a voltaic cell
incorporating these two half reactions.
O2(g) + 2 H2O(l) + 4 e− ––→ 4 OH−(aq) E° = +0.40 V
Cr3+ (aq) + 3 e− ––––→ Cr(s) E° = −0.74 V
8. Balance the following skeleton reaction, calculate E°cell, and determine whether the reaction
would be spontaneous as written. You will need to use the emf table in the textbook.
Cr3+(aq) + Cu(s) → Cr(s) + Cu2+(aq)
2+ − 3+
9.Answer the question below regarding the reaction, Cl2(g) + Fe (aq) –––→ Cl (aq) + Fe (aq).
a. Balance the reaction using the half-reaction method.
b. calculate the E°cell and determine whether this reaction would occur in a voltaic cell or an
electrolytic cell.
c. Use E°cell to calculate Kc for this reaction at 25 °C.
d. Use E°cell to calculate ΔG° for this reaction
2+ +
10.Answer the question below regarding the reaction, Pb (aq) + Ag(s) →Pb(s) + Ag (aq).
a. Balance the reaction using the half-reaction method.
b. calculate the E°cell and determine whether this reaction would occur in a voltaic cell or an
electrolytic cell.
c. Use E°cell to calculate Kc for this reaction at 25 °C.
d. Use E°cell to calculate ΔG° for this reaction
11. Calculate the cell potential for a voltaic cell with Pt/Pt2+ and Ag/Ag+ half-cells and the initial
concentrations
[Pt2+] = 0.90 M and [Ag+] = 0.20 M.

Pt2+ (aq) + 2 e− → Pt(s) E° = +1.20 V

Ag+ (aq) + e− → Ag(s) E° = +0.80

Prepared by Solomon Kassa