Chapter 5: Oxidation & Reduction Reaction

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Oxidation and Reduction Reaction (Redox)

Review yourself for Contents (Self-Study)

➢Oxidation reaction
➢Reduction reaction
➢Oxidizing agent (oxidant)
➢Reducing agent (reductant)
➢Oxidation number (or Oxidation state)

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Balancing redox reactions by ion-electron method
Follow the following steps:
1. Identify which one is reduced or oxidized.
2. Split a redox reaction into two half reactions.
3. Balance each half reaction with respect to atom and electrical charge.
a. Balance the oxidized or reduced atom first.
b. Balance the change in O.N. by adding electrons on required site.
c. Balance the charge by adding OH- ions (in alkaline medium) and H +
(in acidic medium) on required site.
d. Balance H or O atoms by adding H2O on required site.
4. Combine balanced half reactions to form the overall net redox reaction.
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Q. H2O2 + I- = I2 + H2O (Acidic medium)

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Q. C6H5CHO + Cr2O7 2- = C6H5COOH + Cr3+ (Acidic medium)

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Q. ClO- + CrO2 - = CrO4 2- + Cl- (Basic medium)

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Q. P4 + OH- = PH3 + H2PO2 - (Basic medium and Disproportionation reaction )

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Exercise Problems

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Galvanic Cell (also known as a Voltaic cell)
• A device which converts chemical energy into electrical energy as a result of
spontaneous redox reaction. i.e. electrical current is generated by a spontaneous
redox reaction.

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contd…
• Two beakers are connected through a salt bridge and electrodes are connected
by copper wire with an ammeter.
• When a cell is set up, a redox reaction occurs.
•At anode/ left pole/ negative pole (Zinc rod):
Oxidation: Zn → Zn2+ + 2e-
•At cathode/ right pole/ positive pole (copper rod):
Reduction: Cu2+ + 2e- → Cu
• Net redox reaction:
Zn + Cu2+ → Zn2+ + Cu Phase Boundary

• Representation of a Cell

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Salt Bridge
• U shaped tube containing KCl or KNO3 or NH4NO3 solution in agar-
agar gel.
• Establishes electrical contact between two half cells .
• Does not participate chemically in cell reaction.
• Prevents any net charge accumulation in either half cell.
• The excess positive charge (Zn2+) in anode is reduced by NO3- ions
moving out from salt bridge to anode or Zn2+ ions moving into salt
bridge.
• The excess negative ions (SO42-) in cathode is reduced by K+
diffusing out from salt bridge to cathode solution or SO42- ions
moving into salt bridge.
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Common types of electrodes used in Galvanic Cells
• Active metal electrodes
• They are active metals and they are dissolved or formed during
cell reaction. e.g., Zn and Cu electrodes in, Zn / Zn2+ // Cu2+ / Cu ;
Zn + Cu2+ = Zn2+ + Cu
• Inert or sensing electrodes
• They remain unchanged by net cell reaction. e.g., platinum and
graphite (C) electrode Cu / Cu2+ // Fe3+ / Fe2+ , (Pt);
Cu + 2 Fe3+ = Cu2+ + 2 Fe2+
• Gas electrodes
• They also remain unchanged by cell reaction similar to inert
electrode. e.g., standard hydrogen electrode,
(Pt), H2 / 2H+ // Cu2+ / Cu ; H2(g) + Cu2+ = 2H+(aq) + Cu(s)
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 Zn / Zn2+ // Cu2+ / Cu Cu / Cu2+ // Fe3+ / Fe2+ , (Pt) (Pt), H2 / H+ // Cu2+ / Cu

a. A Galvanic cell (Half cell on left using a b. A Galvanic cell (Half cell on left using a c. A Galvanic cell (Half cell on left using a
zinc strip and on right copper rod as platinum strip as inert sensing electrode) hydrogen gas electrode)
active metal electrode)
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contd…
Galvanic cell made up of the zinc and copper half-cells, in which the two
electrodes are connected to the terminals of a voltameter, then at constant
temperature, voltage of the galvanic cell (cell potential) is the function of :
a)The ratio of the concentration of the zinc and cupric ions
• If the temperature is 250C and the concentrations are equal, the voltameter
reads the cell potential of 1.0 Volts
• If Zn++ ion concentration is increased, or the concentration of Cu++ ion
decreased, the voltage decreases and vice-versa
• i.e. the voltage increases as the concentration of reactant increased or cell
voltage decreases as concentration of product increased.
• If we make Galvanic cell of the zinc and silver half-cells, replacing copper half
cell, at same conditions as above, cell potential is 1.56 Volts. Therefore,
b) The voltage of Galvanic cell is the characteristic both of the chemical
substances involved in the cell reaction and of their concentrations. 14
Cell potential (or emf) and standard cell potential (∆Eo)
➢Cell potential is the difference between the electrode potentials of
the electrodes present in two half cells of an electrochemical cell. or net reduction
to proceed from left to right.
➢It is driving force that sends electrons from anode to cathode through the circuit.
➢Standard Cell Potential or emf of a cell (∆Eo) is cell potential of a galvanic measured
at standard conditions of
• 1-M concentrations for all dissolved materials
• 1-atm pressure for all gases and,
• for solids, their most stable form at 250C

For example

❖ Zn + Cu2+ = Zn2+ + Cu ; ∆Eo = 1.1volts

❖Zn + 2Ag+ = Zn2+ + 2Ag ; ∆Eo = 1.56 volts

❖Cu + 2Ag+ = Cu2+ + 2Ag ; ∆Eo = 0.46 volts

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“Standard Cell Potential (∆Eo) is the driving force of the cell reaction”
• Standard Cell Potential (∆Eo) is the quantitative measure of the tendency of
reactants to form products in their standard states. It represents the driving force of
the chemical reaction.
• Illustration: A zinc-copper standard cell (∆Eo = 1.1 v) is connected to the external
variable voltage that opposes the cell voltage and an ammeter that indicates the
direction of the flow of electrons.

(a) (b) 16
)
contd…
There are three distinct cases:
1. External variable voltage < 1.1 v
• The ammeter shows the electron flow from Zn to Cu electrode through external circuit.
Then, the spontaneous cell reaction takes place as:
• Zn + Cu2+ = Zn2+ + Cu
2. External variable voltage = 1.1 v
• No current flows through the ammeter and no net cell reaction occurs.
• The chemical driving force of cell reaction is opposed by equal amount of external
variable voltage.
3. External variable voltage > 1.1 v
• The ammeter shows the electron flow from Cu to Zn electrode.
• Then, the spontaneous cell reaction is reversed and electrolysis occurs.
• Cu + Zn2+ = Cu2+ + Zn
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Electrode Potential (E)
• The potential difference developed at the interface between metal and
electrolyte solution containing its own ions at equilibrium.
• Electrode potential also refers to the ability of an electrode in a cell to get
reduced or oxidized
• Standard electrode potential (Eo):
• 1 M, 25oC (298 K), 1 atm
• Eo = Standard reduction potential
or Standard oxidation potential
• Both have equal numerical value but opposite sign.
• But, IUPAC has recommended the use of standard reduction
potential as standard electrode potential (Eo). Examples,
• Cu2+ + 2e- → Cu ; Eo = + 0.34 v and Zn2+ + 2e- → Zn ; Eo = - 0.76 v
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Single electrode potentials and its measurement
• Determination of emf of a half-cell
• The potential of a single electrode in a half cell.
• It is measured by coupling with standard hydrogen electrode (SHE) as reference
electrode. SHE has zero volt electrode potential .
• Generally, reference electrode. is always used as anode and other single electrode
is cathode. Then, the cell potential produced by cell is the single electrode potential
of that electrode.
• Example, (Pt), H2 / H+ // Zn2+ / Zn during measurement. It gives – 0.76 v cell
potential. So standard electrode potential for Zinc electrode is – 0.76 v.
Zn2+ + 2e- → Zn ; Eo = - 0.76 v
• Example, (Pt) H2 / H+ // Cu2+ / Cu during measurement. It gives + 0.34 v cell
potential. So standard electrode potential for Copper electrode is + 0.34 v.
Cu2+ + 2e- → Cu ; Eo = + 0.34 v

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The zinc electrode (Zn, Zn ) coupled with hydrogen electrode.

SHE can act both as cathode and anode

when joined with another half-cell

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Determination of Standard Cell Potential or emf of a cell (∆Eo)
• ∆Eo = E0cathode - E0anode
• ∆Eo = positive, the reaction is spontaneous/feasible.
• ∆Eo = negative, the reaction is non-spontaneous/not feasible.
Q. Zn2+ + 2e- = Zn ; Eo = - 0.76 v and Cu2+ + 2e- = Cu ; Eo = + 0.34 v
• Calculate the ∆Eo of a cell.
• Write net cell reaction and cell representation .
• Eo = High = Reduction = Cathode and Eo = Low = Oxidation = Anode
• Anode: Zn = Zn2+ + 2e- Eo = + 0.76 v
• Cathode: Cu2+ + 2e- = Cu Eo = + 0.34 v
• Net cell reaction: Zn + Cu2+ = Zn2+ + Cu ∆Eo = 1.1volt
• ∆Eo = E0cathode - E0anode = 0.34 - (- 0.76) = 1.1 volt
• Zn / Zn2+ // Cu2+ / Cu 21
contd..
Q. Pb2+ + 2e- = Pb ;Eo = - 0.13 v and Ag+ + e- = Ag Eo = + 0.8 v

Q. Cu2+ + 2e- = Cu ; Eo = + 0.34 v and Ag+ + e- = Ag; Eo = + 0.8 v

• Answer the following questions

• Write net cell reaction.
• Write cell representation.
• Calculate the ∆Eo of a cell.

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Nernst equation
• Nernst equation is an equation that relates the reduction potential of a reaction
(half-cell or full cell reaction) to the standard electrode potential, temperature,
and activities (often approximated by concentrations) of the chemical species
undergoing reduction and oxidation.
• Consider a reaction, a A + b B = c C + d D;

• Where, ∆E = cell potential, ∆Eo = standard cell potential and n = number of

electrons transferred in the reaction.
• Upon substituting the values of R, F and T at 25°C, the quantity [2.303 RT]/F is
equal to 0.0591.
Q. For a redox reaction, Co + Ni++ = Co++ + Ni ; ∆Eo = 0.03 v, [Ni++ ] = 1M ; [Co++ ] = 0.1 M,
Then, ∆E = ? 0.06 volt
Q. For the above reaction, if [Ni++ ] = 0.01M ; [Co++ ] = 1 M.
Then, ∆E = ? -0.03 volt
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Applications of Nernst equation
1. Cell potential of a reaction remains unaffected by multiplying that reaction by
any positive number.
2Co + 2Ni2+ → 2Co2+ + 2Ni ∆Eo = 0.03 volt

• Here, the form of Nernst equation is consistent with the idea that the voltage
associated with a reaction is unaffected by multiplying that reaction by a positive
number.

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contd..
2. To predict the spontaneity of reaction
• ∆E = +ve, reaction is spontaneous in forward direction
• ∆E = -ve, reaction is spontaneous in backward direction
• The change of electrolyte concentration can change the direction of spontaneity
of a reaction.
a) If the reactant concentration is increased or the product concentration is
decreased , the cell voltage becomes more positive. The reaction is spontaneous
to forward.
• For, Co + Ni++ = Co++ + Ni ; ∆Eo = 0.03 v. If [Ni++ ] = 1M ; [Co++ ] = 0.1 M, Then,

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contd..
b) If the reactant concentration is decreased or the product concentration is
increased, the cell voltage becomes negative. The reaction is spontaneous to
backward.
• For, Co + Ni++ = Co++ + Ni ; ∆Eo = 0.03 v. If [Ni++ ] = 0.01M ; [Co++ ] = 1.0 M,
Then,

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3. Calculation of equilibrium constant (K): Relation between
equilibrium constant, K and standard cell potential, ∆Eo
• Consider a reaction, a A + b B = c C + d D
• At equilibrium, ∆E = 0, Then

• Required equation for the relation between

equilibrium constant (K) and standard cell potential
(∆Eo ).
• If ∆Eo = + ve or ∆Eo > 0, then, K >1 and forward
reaction is spontaneous.
• If ∆Eo = - ve or ∆Eo < 0, then, K < 1 and backward
reaction is spontaneous.

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4. Concentration cell
• The galvanic cell obtained by using same type of electrodes dipped in same type
of electrolytic solution having different concentration. e.g., silver ion
concentration cell.
• More dilute solution = anode ; More concentrated solution = cathode

• At anode: Ag(s) → Ag+ (0.01M) + e –

• At cathode: Ag+ (1M) + e - → Ag(s)
• Net cell reaction:
Ag+ (1M) → Ag+ (0.01M)

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contd..
• The cell reaction is spontaneous until both anode and cathode have
equal concentrations.
• The standard cell voltage (∆Eo ) is zero for concentration cell.
• But, the cell voltage is given by Nernst equation,

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Electrolysis
• 1 faraday = Total charge of one mole of electrons = (1.6 × 10-19) (6.023 ×
1023) = 96,487 coulomb≡ 96,500 coulomb
• Charge (coulomb) = current (ampere) × time (second)
• 1 amp = 1 coul/sec
• 1 mole of e- (1 F charge) can reduce 1 mole Na+ , ½ mole Ca2+ and ⅓ mole
Al3+ .
Na+ + e - = Na
Ca2+ + 2 e - = Ca
Al3+ + 3 e - = Al
• CuSO4 solution is electrolyzed for 7 minutes with 0.6 ampere current.
Charge = 0.6 × (7 × 60) = 252 coul = (252 ÷ 96500) F = 2.61 × 10-3 F
• Cu2+ + 2e- → Cu Here, 1mole e- can reduce half mole of Cu2+
• So, 1.3 × 10-3 mole of copper metal is deposited in the electrolysis.
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Corrosion / Rusting of iron
• The spontaneous destruction of metals due to its interaction with
environment forming a brown scale, called rust.
• Among many theories, electrochemical theory of rusting is the most
convincing one.
• The iron spike with its wet surface when exposed to atmospheric oxygen
undergoes corrosion as follows.

Cathode Anode

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contd..
• Some site of its surface acts as anode where oxidation of Fe to Fe2+ occurs.
Fe(s) → Fe2+ + 2e- ……………………….. (i)
• Iron being good conductor, electrons move towards the next site, cathode where
reduction of dissolved oxygen takes place.
H2O + ½ O2 + 2e- → 2OH- ………………….. (ii)
• In solution, Fe2+ undergo direct oxidation with dissolved oxygen.
2Fe2+ + ½ O2 + H2O → 2 Fe3+ + 2OH- ………………..(iii)
• Finally, Fe3+ and OH- combine to give insoluble solid hydrated iron oxide (rust),
Fe2O3∙3H2O and it gets deposited on the iron surface.
2Fe3+ + 6 OH- → Fe2O3∙3H2O (rust)
• Note: • Cathode and anode part are very close to each other and • Water
containing O2 (electrolyte) helps in the flow of electrons. • These accelerate the
rate of corrosion.
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Prevention of corrosion:
• By coating the metal surface with paints, enamel etc.
• By coating with noble metals like Au, Ag, Cu.
• By using sacrificial anode (by coating with metal like Zn
(galvanization), Sn, Ni ,Cr etc.)

Types of Cell:
• Primary cell: can’t be recharged.
e.g.; Lechlanche dry cell; Mercury cell etc.
• Secondary cell: can be recharged.
Eg; Lead acid cell (lead storage cell); Nickel-cadmium cell;
Alkali metal-sulfur cell etc.
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Fuel cells
• Primary cells in which reactants are continuously supplied to its
electrode from outside as fuel and the energy obtained from the
combustion of fuel is directly converted into electrical energy.

Hydrogen and Oxygen fuel cell

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contd…
• At anode: Oxidation of H2 to water.
H2 + 2OH- → 2H2O + 2e-
• At cathode: Reduction of O2 to OH-.
½ O2 + H2O + 2e- → 2OH-
• Net cell reaction:
H2 + ½ O2 → H2O
• The cell works at high pressure (40 atm).
• For low current demand, it can function at 1 atm and high concentration of KOH. It is
used in spacecraft.
Advantage:
• They are pollution free and more efficient.
Disadvantage:
• Difficulty in finding the suitable fuel-electrode-electrolyte combination.
• Difficulties in handling the gaseous fuels.
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• Q. An electrode chemical cell is constructed of one half-cell in which a platinum
wire dips into a solution containing 1–M Fe3+ and 1–M Fe2+; the other half-cell
consists of thallium metal immersed in 1–M Tl+ solution. Given the following
standard electrode potentials,142 General Physical Chemistry | First Year Tl+ + e–
= Tl, ε0 = –0.34, Fe3+ + e– = Fe2+, ε0 = 0.77, supply the desired information. (a)
Which electrode is negative terminal? (b) Which electrode is cathode? (c) What
is cell voltage? (d) Write the reactions that proceed from left to right as the cell
operates spontaneously. (e) What is the equilibrium constant of the reaction?
(f) How will the voltage of the cell changed by decreasing the concentration of
Tl+ ?
• Thallium electrode acts as a negative terminal
• Platinum electrode dipped in Fe2+ and Fe3+ ion solution will be cathode
• Cell voltage = 1.11 V
• Fe3+ + e– = Fe2+ (Cathode half cell reaction) ε0 = 0.77 Tl = Tl+ + e– , (Anode half cell
reaction) Thus, Fe3+ + Tl = Fe2+ + Tl+ (spontaneous cell reaction)
• K = 6.5 x1018
• From Nernst equation we can say that, decreasing the concentration of Tl+ , the voltage of
the cell increases
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• Q. A Galvanic cell consists of a strip of cobalt metal, Co, dipped into 1-M Co2+
solution, and another half cell in which a piece of platinum dips into 1-M solution
of Cl– . Chlorine gas at 1-atm pressure is bubbled into the solution. Observed cell
voltage is 1.63 volts, and as the cell operates cobalt electrode is negative. Given
only the standard potential for the chlorine-chloride ion half-cell is ½ Cl2 + e– =
Cl– , ε0 = 1.36 volts, supply the desired information. (a) What is the spontaneous
cell reaction? (b) What is the standard potential of the cobalt electrode? (c)
Would the cell voltage increases or decreases if the pressure of chlorine gas
increased? (d) What would the cell voltage be if the concentration Co2+ were
reduced to 0.01 M?
• Spontaneous cell reaction is : Co + Cl2 = Co2+ + 2Cl–
• ε0 Co= –0.27 V
• if the pressure of chlorine gas increased cell voltage increases.
• If the concentration Co2+ were reduced to 0.01 M, using Nernst equation, ∆ε = 1.686 V.
Thus, the cell voltage is increased from its value of standard condition, which was 1.63 V

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