MODULE 111: ENERGY- APPLICATIONS AND USES.

TOPIC 8. REDOX EQUILIBRIA

TOPIC OBJECTIVES
At the end of the topic, the learners should be able to:
a) Explain: Oxidation, Reduction, Oxidation-reduction, Oxidation numbers and disproportionation
b) Give examples of oxidation-reduction reactions, oxidizing and reducing agents
c) Explain oxidation-reduction reactions in terms of oxidation numbers
d) Redox potentials and their measurements – The Daniel cell, use of e.m.f values to compare
relative tendencies of metal-metal half cells to release electrons.
e) Describe the standard hydrogen half-cell and different types of half-cells
f) Cell diagrams and their uses
g) Corrosion and its prevention

COMPETENCIES:
- Memorize definitions
- Write and balance redox equations in aqueous and acidic media
- Draw the Daniel cell and write cell diagrams
- Calculate cell e.m.fs
- define corrosion and state some methods of prevention
- State some applications of redox reactions.

DIDACTIC RESOURCES:
Salt bridge, filter paper, platinum wire, porous pot, AgNO3, KNO3/KCl, Na2S2O3.5H2O, iodine,
acids and bases, CuSO4, KMnO4, distilled water, millivoltmeter (v.v), chart of ECS and some
common lab. Equipment.

REFERENCES:
- Chemistry Teaching syllabus (LSS and USS)
- Complete Advanced Level Chemistry by Ngulle Emmanuel, p. 208-228,4th edition.

- Advanced Chemistry by Michael Clugston and Rosalind Flemming, p.212-236, Oxford.

Bangsi Bernard/ Redox Equilibria 1

 LESSON TITLE: 8.1- REVIEW OF REDOX REACTIONS
LESSON OBJECTIVES
At the end of the lesson, the students should be able to:
a) Distinguish between a Redox reaction and a disproportionation reaction, using examples.
b) Distinguish between an oxidant and a reductant
c) Recall rules for assigning oxidation numbers
d) Use oxidation numbers to balance redox equations.

I PRESENTATION
a) REDOX AND DISPROPORTIONATION REACTIONS
 A Redox reaction is one in which a chemical species is oxidized and the other is reduced at the
same time, e.g.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
RA OA
OOA
 A disproportionation reaction is one in which a single species is being oxidized and reduced
simultaneously, e.g.
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
0 -1 +1

Cl2(g) + OH-(aq) Cl-(aq) + ClO-(aq) + H2O(l)

An oxidant (oxidising agent) is an electron acceptor, e.g. Cu2+, while a reductant is an electron
donor, e.g. Zn in the above reaction.
Hence, a redox reaction is simply the transfer of electrons from a reductant to an oxidant at the
same time
BALANCING OF REDOX EQUATIONS
EXAMPLES:
Balance the following redox reactions
a) Cr2O72- + S2O32- Cr3+ + S4O62-
b) MnO4- + C2O42- Mn2+ + H2O + CO2(g)
SOLUTIONS

Bangsi Bernard/ Redox Equilibria 2

a) Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O(l)

2S2O32-(aq) S4O62-(aq) + 2e- X3

Cr2O72-(aq) + 14H+(aq) + 6S2O32-(aq) 2Cr3+(aq) + S4O62-(aq) +7H2O(l)

b) MnO4-(aq) + 8H+(aq) +5e- Mn2+(aq) + 4H2O(l) X2

C2O42-(aq) 2CO2(g) + 2e- X5

2MnO4-(aq) + 18H+(aq) + 5C2O42-(aq) 10CO2(g) + 2Mn2+(aq) + 8H2O(l)

EXERCISES

Determine the oxidation numbers of the following elements:

a) Cr in K2Cr2O7 b) Cl in ClO4- c) Mn in MnO4- d) S in H2SO4

SOLUTION

a) Let the oxidation number of Cr be x

2x + 2(1) + 7(-2) = 0 2x + 2 – 14 = 0 x = +6

b) x + 4(-2) = -1 x = +7

c) x + 4(-2) = -1 x = +7

d) 2(1) + x + 4(-2) = 0 x = +6

EXERCISE

Questions 9, P.16, Tutorial workbook, 5th edition by Njinoh.

SOLUTION TO EXERCISE

a) i) Standard solution -One whose concentration or molarity is known accurately

ii) Redox reaction–One in which one species is oxidized and the other is reduced simultaneously

b) MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) +5Fe3+(aq) + 4H2O(l)

i) KMnO(aq) is both a reactant and an indicator, pale pink at the end-point

ii) To catalyze the action of KMnO4(aq) and to prevent the oxidation of Fe2+ to Fe3+

iii) A. From the balanced equation:

Mp.Vp
= 1/5
MFe.VFe

Bangsi Bernard/ Redox Equilibria 3

 5Mp.Vp 5(0.02)(26.5)
=> MFe = = = 0.106moldm-3
VFe 25
B. 25cm3 of Fe2+ 26.5cm3 KMnO4(aq)
250(26.5)
: - 250cm3 of Fe2+ x= = 265cm3
25
C. Moles, n = MV
250
= 0.106 1000 = 0.265moles
9.80
D. n = m/Mr Mr = m/n = = 369.81g/mole
0.0265
E. Mr = 369.81 = 2(14+4) + 56 + 2(32+64) +18n
369.81-288
n= = 4.55 ≈ 5
18
ASSIGNMENT
Question 2, page 10, Tutorial workbook by Njinoh, 5th edition.

LESSON TOPIC: 8.2 – REDOX POTENTIALS AND THEIR MEASUREMENTS

LESSON OBJECTIVES
At the end of the lesson, the students should be able to:
a) Describe metal-metal ion electrodes
b) Draw the Daniel cell and describe how it functions
c) State the factors that affect the electromotive force (e.m.f) of a cell
d) Define standard electrode potential
e) Draw the standard hydrogen half-cell and describe how it is used to measure electrode potentials.
I INTRODUCTION
a) What is i) an electrolyte?, ii) an electrolytic cell?
b) Define the following terms i) Anode ii) Cathode, as used in electrolysis.
II PRESENTATION
3.2.1 REDOX POTENTIALS AND THEIR MEASUREMENTS
1) METAL-METAL-ION ELECTRODE (OR HALF-CELL)
When a metal rod/wire is immersed in an aqueous solution of its own ions, either of the following
situations may occur:
a) Metal atoms from the surface of the rod ( or wire) go into solution as metal ions, i.e.
Bangsi Bernard/ Redox Equilibria 4
M(s) Mn+(aq) + ne- (oxidation)
e.g. Zn(s) Zn2+(aq) + 2e-
The electrons released accumulate on the surface of the metal rod giving it a net negative charge
while the solution around the rod becomes positively charged. Hence, a potential difference (p.d)
is established between the negatively charged rod (M) and the positively charged solution of the
metal ions (Mn+).

b) Metal ions in solution gain electrons from the metal rod to be deposited as metal atoms
i.e. Mn+(aq) + ne- M(s) (Reduction)
e.g. Cu2+(aq) + 2e- Cu(s)
The metal rod becomes positively charged and the solution negatively charged.
The metal rod dipping into a solution of its own ions is called an electrode because electrons may
enter or leave the solution through it. The potential difference or electrode potential is a measure
of the tendency of a metal to go into solution. The electrode potential of a metal may be positive
or negative depending on its chemical reactivity (i.e. position on the ECS). A more reactive metal
will have a negative p.d (E) while a less reactive one will have a positive p.d.
2- ELECTROCHEMICAL CELLS: - THE DANIEL CELL
Two electrodes or half cells combine to give an electrochemical cell called a GALVANIC or
VOLTAIC CELL which can produce electric current. An example of a voltaic cell is the Daniel
cell which consists of the Zn and Cu half cells that are short-circuited (i.e. connected).

Bangsi Bernard/ Redox Equilibria 5

The spontaneous redox reaction at the electrodes causes electrons to flow in the external circuit
from the anode (-) to the cathode (+)
DEFINITIONS
a) The anode is the oxidation electrode (half-cell), i.e.
Zn(s) Zn2+(aq) + 2e-
b) The cathode is the reduction electrode, i.e.
Cu2+(aq) + 2e- Cu(s)
To complete the electric circuit, a conducting medium called a salt bridge or porous partition
(Made by filling a u-tube with an inert electrolyte, e.g. saturated KCl or KNO3 is required
through which cations (+) move to cathode and anions (-) to the anode.
The flow of electrons from the anode to the cathode implies a potential or voltage difference
between the two electrodes called the ELECTROMOTIVE FORCE or E.M.F (E). The e.m.f
of a cell is a measure of the tendency of electrons to flow through the external circuit or the
relative tendency of the metals to go into solution. The e.m.f can be measured using a valve
voltmeter (v.v) or a potentiometer. But a valve voltmeter is preferable because it has a high
internal resistance (r), thus ensures that no current is wasted in the external wire (i.e. I = 0) so
that the cell registers its maximum e.m.f (p.d).
However, connecting the two half cells directly using a wire, electrons flow from the anode (Zn)
to the cathode (Cu) thus favouring the forward reaction in the following equilibrium:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Consequently, the Zn metal decreases in size and the concentration of Zn2+ ions increases while
the Cu metal increases in size as Cu2+ ions are discharged from the solution.

Bangsi Bernard/ Redox Equilibria 6

A high value of electromotive force means that one metal gets into solution much easier than the
other, and a low value implies that the tendencies are almost the same. The e.m.f of a cell
depends on:
 the nature of the electrodes
 Concentration of ions in the electrolytes
 Temperature of the system.
3-REDOX EQUILIBRIA IN OTHER SYSTEMS
-Non-metal ions- non-metal ions electrodes
Redox equilibria extend to other systems involving oxidized and reduced forms such as:
2Br-(aq) Br2(l) + 2e-
Fe2+(aq) Fe3+(aq) + e-
MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + H2O(l)
Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + H2O(l)
Each form could constitute a half-cell or electrode which will be connected via a neutral electrode
(e.g. platinum wire) to another electrode to form a voltaic cell.
4- ELECTRODE/REDOX POTENTIALS(E) AND STANDARD ELECTRODE
POTENTIALS (𝑬Ɵ )
Absolute electrode potentials for single electrodes are not measurable (because an e.m.f can be
measured only for a complete circuit with two electrodes), only differences in potentials are
measurable. The electrode/redox potential or e.m.f (E) of each electrode system can be obtained
by connecting that electrode to a standard/reference electrode, i.e.one with a known standard
potential (EƟ) to form a complete cell, and then measuring the e.m.f of the cell (Ecell). For a cell
with a standard electrode on the L.H.S.
Ecell = ERHS - ELHS
= Eelectrode - Eelectrode
with unknown with known p.d
p.d
If Ecell > 0 or positive, the electrons flow from left (anode) to right (cathode) in the external
circuit and current flows conventionally in the opposite direction. i.e.
Ecell = Ecathode - Eanode
a) THE STANDARD HYDROGEN ELECTRODE (S.H.E)
The hydrogen electrode is chosen as the standard/reference electrode and assigned a redox
potential value EƟ = 0.00v. It consists of H2 gas at 1atm pressure bubbled over a platinum wire

Bangsi Bernard/ Redox Equilibria 7

coated with finely divided platinum black, immersed in a 1.0M solution of HCl acid at 298K or
250C.
The finely divided Pt black provides a good surface for the dissociation of H2 and the
establishment of the equilibrium: H2(g) 2H+(aq) + 2e-

Or H2(g) +H2O(l) 2H3O+(aq) + 2e-

 Pt acts as a catalyst and as an electrical conductor to the external circuit.

DISADVANTAGES OF THE S.H.E

 It is cumbersome and difficult to use

 Easily poisoned by impurities

A more preferable standard electrode is the calomel which comprise Hg(l) chloride:

Hg2Cl2(s) +2e- 2Hg(l) + 2Cl-(aq)

EƟ = +0.244v at 298K

DEFINITIONS:

i) The electrode/redox potential (E) of a system is the e.m.f of a cell comprising the S.H.E as the
L.H.S electrode and that system as the R.H.S, i.e.

For E, [Mn+(aq)] ≠ 1.0M.

ii) The standard electrode/redox potential (EƟ) of an electrode is the e.m.f of a cell comprising the
S.H.E as the L.H.S and the electrode/metal dipping into a molar (1.0M) solution of its ions at 298K
as the RHS electrode. i.e.

Bangsi Bernard/ Redox Equilibria 8

For EƟ, [Mn+(aq)] = 1.0M at 298K.

OR the standard electrode potential of an electrode is the e.m.f of a cell comprising the electrode
dipping into a molar solution of its ions at 298k and 1atm relative to the standard hydrogen
electrode.

MEASUREMENT OF E/ EƟ OF AN ELECTRODE USING THE S.H.E

To measure the E/ EƟ of an electrode connect it to a S.H.E as follows:

For E: [Mn+(aq)] ≠ 1.0M

 For EƟ: [Mn+(aq)] = 1.0M at 298K.

III. EVALUATION:
a) State the differences between an electrochemical cell and an electrolytic cell.
b) Under what conditions does an electrode potential (E) becomes standard ( Eθ )?
c) Define standard electrode potential.
e) State the function of i) salt bridge, ii) valve voltmeter in an electrochemical cell.

LESSON 8.3- CELL DIAGRAMS, ELECTROCHEMICAL SERIES (ECS) AND

IT’S IMPORTANCE.
LESSON OBJECTIVES:
At the end of the lesson, the learners should be able to:
a) Write cell diagrams
b) Calculate cell e.m.fs from cell diagrams

Bangsi Bernard/ Redox Equilibria 9

 c) Predict the effect of change in concentration on cell e.m.f.
I. INTRODUCTION
a) State Le Chatelier’s principle.
b) Write a chemical equation for the reaction in the Daniel cell.
c) What is the effect of increasing the concentration of Cu2+ ions on the
equilibrium position in the reaction in (b) above?
II. PRESENTATION.
8.3.1- CELL DIAGRAMS
A cell diagram is a conventional method of representing cells and the e.m.f. they produce.
IUPAC RULES FOR WRITING CELL DIAGRAMS
a) For each electrode, the solid is separated from its aqueous ions by a vertical stroke, e.g.
Zn(s)/Zn2+(aq), Cu(s)/Cu2+(aq), etc.
b) The two half-cell diagrams are separated by a double vertical stroke or a vertical dotted line,
representing a salt bridge or porous partition or any other conducting devise to ensure electrical
contact between the two half-cells. i.e. // or ⁞ = salt bridge.
c) The oxidizing part of an electrode is placed nearer the salt bridge than its reduced form, e.g.
i) Zn(s)/Zn2+(aq) // Cu2+(aq)/Cu(s), EƟ = +1.10v
ii) Cu(s)/Cu2+(aq) ⁞ Zn2+(aq)/Zn(s), EƟ = -1.10v
d) The half-cell undergoing oxidation (anode) is placed on the left and the one undergoing
reduction (cathode) on the right of the salt bridge
e) The sign (+ve or –ve) of the cell e.m.f (EƟcell) is the polarity of the RHS electrode, e.g. in c(i)
above Cu is the positive electrode and Zn is the negative
f) Half-cell diagrams can also be represented with their corresponding electrode potentials, e.g.
Zn(s)/Zn2+(aq), EƟ = -0.76v
Cu(s)/Cu2+(aq), EƟ = -0.34v
Pt(s)/H2(g), 2H+(aq), EƟ = 0.00v
g) If the redox equation is between aqueous forms, e.g. ions needing the intervention of a neutral
electrode, the reduced form of it is placed nearer the neutral electrode and the oxidized part
nearer the salt bridge, and the two forms separated by a comma, e.g.
Pt(s)/Fe2+(aq), Fe3+(aq); Pt(s)/2I(aq), I2(aq)
Pt(s)/2I-(aq), I2(aq)// Fe3+(aq), Fe2+(aq)/ Pt(s)

Bangsi Bernard/ Redox Equilibria 10

Pt(s) /2I-(aq), I2(aq) ⁞ Cu2+(aq)/Cu(s)
h) If the oxidized or reduced form has more than one chemical species (i.e.ions, molecules, etc.)
which take part in the cell reaction, these ions and molecules must be included in the oxidized or
reduced form, and square brackets used to group the oxidized and reduced forms together.
For the equilibria:
i) Mno4-(aq) + 8H+(aq) 5e- Mn2+(aq) +4H2O(l)
[Mno4-(aq) + 8H+(aq)], [Mn2+(aq) +4H2O(l)]/ Pt(s), EƟ = +1.51v
ii) Cr2O72- (aq) + 14H+ (aq) + 6e- 2Cr3+(aq) + 7H2O(l)
[Cr2O72- (aq) + 14H+ (aq)], [2Cr3+(aq) + 7H2O(l)]/ Pt(s), EƟ = +1.33v
iii) 2H+(aq) +2e- H2(g)
Pt(s)/ H2(g), 2H+(aq), EƟ = 0.00v
8.4- SOME STANDARD ELECTRODE/REDOX POTENTIAL (EƟ) –
ELECTROCHEMICAL SERIES (ECS)
Conventionally, standard electrode potentials are always written as standard reduction potentials
and each electrode process is written as a reduction, i.e.
Oxidant + ne- reductant
N.B. See table 10.1, page 217-218, Advanced Level Chemistry by Ngulle Emmanuel.

HALF-CELL EƟ/V at 298K

Li+(aq)/Li(s) -3.04
K+(aq)/K(s) -2.92
Ba2+(aq)/Ba(s) -2.90
2+
Mg (aq)/Mg(s) -2.37
3+
Al (aq)/Al(s) -1.66
Increasing oxidizing power
Increasing reducing power

Zn2+(aq)/Zn(s)
(Electron acceptor)

-0.76
(Electron donor)

Fe2+(aq)/Fe(s) -0.44
2+
Pb (aq)/Pb(s) -0.13
+
2H (aq), H2(g)/Pt(s) 0.00
Cu2+(aq)/Cu(s) +0.34
I2(aq), 2I-(aq)/Pt(s) +0.54
Fe3+(aq), F2+(aq)/Pt(s) +0.77

Bangsi Bernard/ Redox Equilibria 11

 Ag(aq)+/Ag(s) +0.88
Br2(l), 2Br-/Pt(s) +1.07
Cl2(g), 2Cl-(aq)/Pt(s) +1.36
F2(g), 2F-(aq)/Pt(s) +2.87

Each of these values is the e.m.f of a complete cell obtained by connecting the S.H.E on the left
and the other half-cell to the right, the EƟ is read from the valve voltmeter.

8.4.1 USES OF STANDARD ELECTRODE POTENTIALS (EƟ)

a) TO SHOW THE RELATIVE OXIDISING POWER OF DIFFERENCE SPECIES

The order of EƟs is similar to the order of ECS, with the most reactive metal having the highest
negative value of the EƟ and the most reactive non-metal having the highest positive value. The
more negative the EƟ the easier the oxidation process

M(s) Mn+(aq) + ne-

Hence, species with more negative EƟs are strong reductants (electron donors) and those with more
positive EƟ are strong oxidants (electron acceptors). Examples:

[MnO4-(aq) + 8H+(aq)], [Mn2+(aq) +4H2O(l)]/Pt(s), EƟ = +1.5v

Cl2(g) + 2Cl-(aq)/Pt(s), EƟ = +1.36v

EƟ MnO4-/Mn2+ > EƟCl2/2Cl-

: - MnO4-(aq) is a strong oxidant than Cl2.

b) PREDICTING THE FEASIBLITY OF A REACTION

Generally, reactions with an overall positive cell e.m.f (i.e. EƟcell > 0) are energetically feasible
while those with EƟcell < 0 or negative are not feasible. Hence, the criterion for a spontaneous cell
reaction is that the standard cell e.m.f (EƟcell) should be positive. Examples:

Cu2+(aq) + 2e- Cu(s), EƟ = +0.34v

Zn(s) Zn2+(aq) + 2e-, EƟ = -0.76v

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

EƟcell = EƟRed - EƟox

= EƟRHS - EƟLHS

= 0.34 –(-0.76) = +1.10v

Bangsi Bernard/ Redox Equilibria 12

Therefore, the reaction is feasible in the forward direction, but the reverse reaction with an EƟcell
= -1.10v is not feasible.

However, EƟ values give no information about the rate of a reaction or its kinetic feasibility.

c) TO CALCULATE THE E.M.F OF CELLS (EƟcell)

First, the cell diagram is written, then apply

EƟcell = EƟRed - EƟox

= EƟcathode - EƟanode

N.B. It doesn’t matter how many electrons are transferred because standard cell e.m.f refers to the
probability of a reaction occurring and not to the quantity of material involved. Examples

Fe3+(aq) + e- Fe2+(aq), EƟ = +0.77v

But 4Fe3+(aq) + 4e- 4Fe2+(aq), EƟ = +0.77v and not 4(+0.77v)

EXERCISES

1. Given the half-cells below:

Mg2+(aq) / Mg(s), EƟ = -2.37v

Ag+(aq) / Ag(s), EƟ = +0.80v

a) Write the cell diagram

b) Calculate the cell e.m.f

c) State the polarity of the RHS electrode

d) With the aid of an equation, describe the chemical reaction that will occur when the voltaic cell
in (a) is short-circuited.

SOLUTIONS

a) Mg(s) / Mg2+(aq) // 2Ag+(aq)/2Ag(s)

b) EƟcell = EƟRHS - EƟLHS

= +0.80 – (-2.37) = +3.17v

c) Sign of EƟcell is positive i.e. polarity of the RHS electrode is positive (and that of the LHS
electrode is negative)

d) LHS (anode): Mg(s) Mg2+(aq) + 2e-

Bangsi Bernard/ Redox Equilibria 13

 RHS (cathode): 2Ag+(aq) + 2e- 2Ag(s)

: - Mg(s) + 2Ag+(aq) Mg2+(aq) + 2Ag(s)

Hence, electrons flow from the anode to the cathode through the external wire,

2. Given the following half-cells:

S4O62-(aq), 2S2O32-(aq) / Pt(s), EƟ = +0.11v

I2(aq), 2I-(aq) / Pt(s), EƟ = +0.54v

a) Predict what will happen and state your observation(s) when standard solutions of iodine and
sodium thiosulphate are mixed

b) Write a balanced chemical equation of the reaction

c) Write the cell diagram

d) Calculate the EƟcell

SOLUTION

a) Anodic reaction: 2S2O32-(aq) will be oxidized to S4O62-(aq) i.e.

2S2O32-(aq) S4O62-(aq) + 2e-

Cathodic reaction: I2 is reduced to 2I- i.e.

I2(aq) + 2e- 2I-(aq)

Observation: Reddish-brown colour of I2(aq) is discharged

b) 2S2O32-(aq) + I2(aq) S4O62-(aq) + 2I-(aq)

Thiosulphate ion Tetrathionate ion

c) Pt(s) / 2S2O32-(aq), S4O62-(aq) ⁞ I2(aq), 2I-(aq) / Pt(s)

d) EƟcell = EƟcathode - EƟanode

= 0.54 – 0.11 = +0.43v

III-EVALUATION

a) What is a cell diagram?

b) Write a cell diagram for the Daniel cell reaction.
c) Consider the half-cell, Fe3+(aq) +e- ⇌ Fe2+(aq) , Eθ =+0.78v.State four conditions under
which the standard emf of the electrode can be obtained.

Bangsi Bernard/ Redox Equilibria 14

ASSIGNMENT

Structural: nos 1, 2, p. 148-149, nos 6, 7, 8, 9, 10, p. 152-157, Tutorial wkbk,Njinoh.

8.5- FACTORS AFFECTING ELECTRODE POTENTIALS

1. CONCENTRATION OF IONS
When ion concentration is different from 1.0M, the cell e.m.f (Ecell) may be greater or smaller than
the standard cell e.m.f (EƟcell). Generally, the effect of changes in concentration can be predicted
by Le Chatelier’s principle.
For metal-metal ion electrodes, their electrode potentials become more positive as the
concentration of the metal ion increases.
For the reactions:
a) Cu2+(aq) + 2e- Cu(s), EƟ = +0.34v
An increase in [Cu2+(aq)] shifts the equilibrium position to the right thus increasing the EƟ
b) Fe3+(aq) e- Fe2+(aq), EƟ = +0.77v
The EƟ increases as the [Fe3+(aq)) increases

THE NERNST EQUATION

The equation relates the electrode potential (E) of a half-cell at a concentration of [Mn+(aq)] to its
standard electrode potentials (EƟ) as follows:
RT [oxidized species]
E = EƟ + ln [Reduced species]
nF
Where R = Molar gas constant = 8.314KJmol-1
H = absolute temperature in kelvin = 298k
n = number of electrons transferred between the oxidized and reduced species
F = Faraday constant (96,500C)
At 25oC or 298k,
RF 8.314(298)
= = 0.026
T 96500

0.026 [ox ]
E = EƟ + RF ln
T n [Red]
But lnx = 2.303logx
[ox]
E = EƟ + 0.059 log10 , (0.059 ≈ 0.06)
n [Red]

Bangsi Bernard/ Redox Equilibria 15

E.g. Fe3+(aq) e- Fe2+(aq), EƟ = +0.77v
n=1
[Fe3+(aq)]
E = EƟ + 0.06log
[Fe2+(aq)]
= 0.77 + 0.06log [Fe3+(aq)]
[Fe2+(aq)]

Hence, an increase in [Fe3+(aq)] increases the electrode potential (E).

The e.m.f of a cell depends on the concentration of its component ions. Examples:

The overall reaction for the Daniel cell is

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Ecell = EƟRHS - EƟLHS

= EƟCu2+/ Cu + 0.06
log[Cu2+(aq)] –( EƟZn2+/Zn + 06 log[Zn] )
2
2

0.06 [Cu2+(aq) ]
= EƟcell + log
2 [Zn2+(aq) ]
Generally, for a cell reaction,

Ecell = EƟcell + 0.06 log [reactants]

2 [products]
EXAMPLES

1. MnO4-(aq) + 8H+(aq) +5Fe2+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)

0.06 - 2+ 5 + 8
Ecell = EƟcell + log [MnO4 ][Fe ] [H ]
5 [Mn2+][Fe3+]5

2. I2(aq) + 2S2O32-(aq) 2I-(aq) + S4O62-(aq)

0.06
Ecell = EƟcell + log [I2(aq)][2S2O3
2-(aq) ]2

2 [I-(aq)]2 [S4O62-]
Therefore, an increase in the concentration of reactants will increase the cell e.m.f and vice versa.

2. ACCIDITY OF MEDIUM (pH)

For redox reactions that require acidic media, the more acidic a medium, the higher the redox
potential and vice versa

3. TEMPERATURE OF THE MEDIUM

Bangsi Bernard/ Redox Equilibria 16

The cell e.m.f increases with increase in temperature provided the ionic concentration remains
constant.

8.6 - CORROSION AND METHODS OF PREVENTION

DEFINITION: Corrosion is the deterioration (or wearing away) of a substance/metal through

chemical reaction

 An example of corrosion is rusting of iron

 Conditions for rusting: air (oxygen) and water (or moisture)
 Other factors that accelerate rusting:
- Impurities in the metal,
- Presence of dissolved oxygen and other gases such as CO2, SO2, SO3, etc
- Presence of electrolytes in solution in contact with the metal.

MECHANISM OF RUSTING

Rusting is an electrochemical process where one part of a metal (e.g iron) is acting as the cathode
and the other as the anode.

Anodic reaction: Fe(s) Fe2+(aq) + 2e-

Cathodic reaction: O2(aq) + 2H2O(l) + 4e- 4OH-(aq)

The Fe2+ in solution combine with the OH- ions forming Fe(OH)2(s) precipitate which is then
oxidized by oxygen to hydrated iron (III) oxide (rust) thus:

2Fe(OH)2(s) + ½O2(aq) + H2O(l) Fe2O3.XH2O(s)

Rust (brown)

DISADVANTAGES OF RUSTING/CORROSION

Damages buildings, bridges, ships, cars, kitchen utensils, statues, etc.

PREVENTION OF RUSTING

1. Sacrificial protection of iron by Zinc or magnesium - a block of Zn or Mg is connected to iron

to act as the anode, undergoing corrosion while iron remains intact. i.e.

Zn(s) Zn2+(aq) + 2e-

2. Galvanization with Zinc / Cathodic protection where Zn is made the anode and iron the cathode
in an electrochemical cell.
3. Alloying iron with non-corrosive metals such as Ni, Mn, Cr, etc.
4. Painting of the metal surface

ASSIGNMENT

Bangsi Bernard/ Redox Equilibria 17

MCQs: type 1, nos 1-30, p. 139-141

2, nos 52-75, p. 144

3, nos 76-85, p.148

4, nos 94-103, p.147, Tutorial workbook by Njinoh, 5th edition.

Bangsi Bernard/ Redox Equilibria 18