REDOX EQUILIBRIA

 INTRODUCTION
 OXIDATION NUMBERS
 BALANCING OF REDOX EQUATIONS
 REDOX POTENTIALS AND THEIR MEASUREMENTS
 ELECTROCHEMICAL CELLS
 REDOX EQUILIBRIA IN OTHER SYSTEMS
 THE STANDARD HYDROGEN ELECTRODE (S.H.E)
 CELL DIAGRAMS, ELECTROCHEMICAL SERIES AND IT’S
IMPORTANCE
 FACTORS AFFECTING ELECTRODE POTENTIAL
 CORROSION AND METHOD OF PREVENTION
 MECHANISM OF RUSTING
 DISADVANTAGESOF RUSTING/CORROSION
 PREVENTION

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REDOX EQUILIBRIA
• Introduction
• 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 + Cu
(s)
2+(aq) Zn + Cu 2+(aq) (s)

RA OA
 A disproportionation reaction is one in which a single species is
beingC l oxidized
+ H O
2 (g)
and reduced simultaneously,
2 (l ) HCl + HOCl (aq ) (aq )

e.g
0 -1 +1
C l 2 ( g ) + O H - ( aq ) C l - ( aq ) + C l O - ( aq ) + H 2O (l)

 An oxidant (oxidising agent) is an electron acceptor, e.g. Cu , while a 2+

reductant 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 2
OXIDATION NUMBERS

 The oxidation number of an element is the number of electrons

it has lost ,gained or shared as a result of chemical bonding.
 Oxidation involves an increase in oxidation number while
reduction involves a decrease in oxidation number.
Rules for Assigning Oxidation Numbers
 The oxidation number of an element in its uncombined state is
zero. e.g. Cl2(g), Na, Ca, Al,
 In an ion, the algebraic sum of the oxidation numbers equals to
the charge on the ion.
 In neutral molecules, the algebraic sum of the oxidation
numbers is zero.

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 Rules for Assigning Oxidation Numbers
 In any substance, the more electronegative atom has the negative
oxidation number, and
 the less electronegative atom has the positive oxidation number.
c
 The oxidation number of hydrogen in all its compounds, except
metal hydrides like NaH,
MgH2 is +1.
 The oxidation number of oxygen in all its compounds is -2, except
in peroxides where its oxidation number is -1 and in OF2 where the
oxidation state is +2.
 Fluorine which is the most electronegative element has an ox
dation number of -1 in its compounds.
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Balancing of Redox Equations
Steps involved in balancing redox equations
 Assign oxidation numbers to each atom to identify the atom
which is oxidized and that which is reduced.
 Split the skeletal equation into two half equations. Note the
species containing the element that increases in oxidation
number and write the oxidation half-equation.
 Similarly note the species containing the element that
decreases in oxidation number and write the reduction half-
equation.

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Balancing of Redox Equations continues
 Balance the number of electrons in the oxidation and reduction
half equations.
 Balance the charge on both sides of the equation by adding H"
to one side of the equation (in acid medium) or OH to one side
of the equation (in alkaline medium).
 Balance the number of oxygen and hydrogen atoms by adding
water on the appropriate side of the equation.

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 Example
Balance the following redox reaction in acidic medium
a) Cr₂O₇²⁻+ S₂O₃²⁻ ↔ Cr3+ + S₄O₆²⁻
• 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)

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Redox potentials and their measurements

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. 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+).

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Redox potentials and their measurements continues

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 Redox potentials and their measurements
continues
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.

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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).

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Electrochemical Cells continues
 The spontaneous redox reaction at the electrodes causes electrons
to flow in the external circuit from the anode (-) to the cathode (+)
Definitions
 The anode is the oxidation electrode (half-cell), i.e.
Zn(s) ↔ Zn2+(aq) + 2e-
 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.
 For example saturated KCl or KNO3 is required through which
cations (+) move to cathode and anions (-) to the anode.
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 Electrochemical Cells continues
 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 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)
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 Electrochemical Cells continues
 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.
 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; and
• Temperature of the system.

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 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.

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ELECTRODE/REDOX POTENTIALS(E) AND STANDARD ELECTRODE
POTENTIALS (𝑬Ɵ)
 Absolute electrode potentials for single electrodes are not
measurable 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).
 Ecell = ERHS - ELHS
 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.
 Ecell = Ecathode - Eanode
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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
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.

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The Standard Hydrogen Electrode (S.H.E)

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The Standard Hydrogen Electrode (S.H.E)

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

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Definitions


 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.
 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.
 For EƟ, [Mn+(aq)] = 1.0M at 298K.
 OR the standard electrode potential of a standard half cell is the
potential of that half cell relative to the standard hydrogen half cell,
under standard conditions.

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 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
c) Predict the effect of change in concentration on cell e.m.f.

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• INTRODUCTION
• State Le Chatelier’s principle.
• Write a chemical equation for the reaction in the Daniel cell.
• What is the effect of increasing the concentration of Cu2+ ions on the
equilibrium position in the reaction in (b) above?
CELL DIAGRAMS
• A cell diagram is a conventional method of representing cells
and the e.m.f. they produce.

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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 23
• 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)
• Pt(s) /2I-(aq), I2(aq) ⁞ Cu2+(aq)/Cu(s)

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• 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:
• 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

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• 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
• 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.

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• 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-

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• 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.

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PREDICTING THE FEASIBLITY OF A REACTION
• Generally, reactions with an overall positive cell e.m.f (i.e. EƟcel
l > 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+↔ Cu(s), EƟ = +0.34v
• Zn(s) ↔ Zn²⁺(aq) + 2e-, EƟ = -0.76v
• Zn(s) + Cu ↔ Zn²⁺(aq) + Cu(s)
• EƟcell = EƟRed - EƟox
• = EƟRHS - EƟLHS
• = 0.34 –(-0.76) = +1.10v 29
• 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- ↔ (aq), EƟ = +0.77v
• But 4Fe3+(aq) + 4e ↔ 4Fe2+(aq), EƟ = +0.77v and not 4(+0.77v)
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• 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

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

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- 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.
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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)

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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 35
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