ELECTROCHEMISTRY

&
REDOX POTENTIAL

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 OUTLINE
1. Basic Electrochemical Terminology

2. Applications of Redox Reactions

3. Galvanic Cells – Redox Potentials & Electrochemistry

4. Spontaneity of Reactions

5. Corrosion Science

6. Corrosion Prevention

7. Electrolysis

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 Electrochemical Terminology
Electrochemistry
• the study of chemical processes that cause electrons to move.

Electrochemical Cells

Eelctrodes
Anode

Cathode

Salt Bridge

Cell Potential, Ecell

Volts

Potentiometer:

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 Step by Step Galvanic Cell
1. Y2+ leaves Y(s) at the anode
2. e- produced at anode move to
cathode causing apotential
difference measured by
voltmeter
3. e- arrives at the cathode
combining with X2+ to form
X(s)
4. Cl- from the salt bridge move
toward the another half-cells to
counter the charge build up by
Y2+
5. K+ from slat bridge a travels
toward the cathode half-cell
A typical Electrochemical Cell (Galvanic)

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 Anode: Zn→ 𝑍𝑛2+ + 2𝑒 −
Cathode: 𝐶𝑢2+ + 2𝑒 −+ → 𝐶𝑢𝑠
Cell rxn: Zn + 𝐶𝑢2+ → 𝑍𝑛2+ + 𝐶𝑢𝑠

Daniell cell having zinc and copper dipped in the the solutions
of their respective salts
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Standard Hydrogen Potential

Standard Reduction Potential

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Cell Potentials
o oxidation of Zn(s) into Zn2+ and the reduction of Cu2+ to Cu(s) occur
spontaneously.
o i.e., the redox reaction between Zn and Cu2+ is spontaneous.
o due to the difference in potential energy between the two substances
o the difference in potential energy between the anode and cathode dictates the
direction of electronic movement
o e- move from areas of higher potential energy to areas of lower potential energy
o In this case, the anode has a higher potential energy; electrons therefore move
from anode to cathode.
o The potential difference between the two electrodes is measured in units of volts.
o One volt (V) is the potential difference necessary to generate a charge of 1
coulomb (C) from 1 joule (J) of energy
o For voltaic cell, this potential difference is called the cell potential (emf, though
not really a force), denoted Ecell
o For a spontaneous reaction, Ecell is +ve
o ΔG (Gibbs free energy; determine spontaneity) is -ve
o Thus, when ΔG is negative the reaction is spontaneous, ΔG=−nFEcell
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Cell Potentials
o Cell potential is different for each voltaic cell
o depends on the concentrations of specific reactants and products as well as
temperature of the reaction.
o For standard cell potential, temperature of the reaction is assumed to be 25o C
the concentration of the reactants and products is 1 M, and reaction occurs at 1
atm pressure.
o The standard cell potential is denoted Eocell, and can be written as oxidation
potential + reduction potential. For voltaic cells:
𝐸 𝑜 𝑐𝑒𝑙𝑙 = 𝐸 𝑜 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 𝑜 𝑎𝑛𝑜𝑑𝑒
Note that to use Equation the cell potentials must be in reduction form.

o Since standard potentials are given in the form of reduction potential for each half-reaction
o To calculate the standard cell potential Eocell, the substances being oxidized must be
identified;
o then the standard reduction potential of the oxidation reaction is subtracted from the
standard reduction potential of the reducing reaction

𝐸 𝑜 𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛) − 𝐸 𝑜 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛)

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Example 1:
What is the cell potential for the following reaction?
Zn(s)+Cu2+(aq)→Zn2+(aq)+Cu(s)
Solution
Zn(s) is being oxidized, and Cu(s) is being reduced. The potentials for the two half reaction are
given in the reduction form:
Oxidation half reaction: Zn(s)→Zn2+(aq)+2e− Eo= -0.763V
Reduction half reaction: Cu2+(aq)+2e−→Cu(s) Eo= +0.342V
The cell potentials indicate which reaction takes place at the anode and which at the cathode.
The cathode has a more positive potential energy, and thus:
• Cu(s)Cu(s) is the cathode
• Zn(s)Zn(s) is the anode.
To calculate Eocell, subtract the Eo of the oxidized half reaction from the Eocell of the reduction
half reaction, e.i.
𝐸 𝑜 cell= 𝐸 𝑜 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 𝑜 𝑎𝑛𝑜𝑑𝑒
Net reaction: Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
Thus:
Eocell = Eocathode − Eoanode=0.340V− (−0.763V) = +1.103V = +1.103
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 Table 1: Standard Electrode Potentials

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Example 2:
Calculate the cell potential in the following redox reaction under standard conditions:
Fe3+(aq)+V2+(aq)→Fe2+(aq)+V3+(aq)
Solution
Consult the table 1 of standard reduction potentials for each half reaction:
Fe3+(aq) + e− → Fe2+ (aq) Eo = 0.771V
V2+(aq)→V3+(aq)+e−with Eo =− 0.255V
The cell potential is:
Eocell = Eocathode − Eoanode = 0.771V−(−0.255V) = 1.026V

Exercise
Calculate Eocell for the following redox reaction under standard conditions:
2Al(s) + 3Sn2+(aq) → 2Al3+(aq) + 3Sn(s)

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Voltage is an Intensive Property
o Standard reduction potential is an intensive property
o changing the stoichiometric coefficient in a half reaction does not affect the
value of the standard potential.
o For example,
Oxidation:{Al(s) → Al3+(aq) +3e-} x 2 is still Eo= -1.676
Reduction:{Sn2+(aq) +2e- → Sn(s)} x 3 is still Eo= -0.137
o if the stoichiometric coefficient is multiplied by 2, the standard potential
does not change:

Predicting Feasibility of Reaction

o The feasibility of a redox reaction can be predicted with the help of the electrochemical
series.
o The net emf of the reaction, 𝐸𝑐𝑒𝑙𝑙, can be calculated from the expression
𝑜 0 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
In general, if
𝑜
𝐸𝑐𝑒𝑙𝑙 = +𝑣𝑒, the reaction is feasible
𝑜
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𝐸𝑐𝑒𝑙𝑙 = − 𝑣𝑒, the reaction is not feasible 13
Example 3: Predict whether the following reaction is feasible or not.
2𝐴𝑔 𝑠 + 𝑍𝑛2+ 𝑎𝑞 → + 𝑍𝑛(s)
Solution
The cell half reactions are
Anode: 2𝐴𝑔 𝑠 → 2𝐴𝑔+ 𝑎𝑞 + 2𝑒 − 𝐸 𝑜 = 0.80𝑉
Cathode: 𝑍𝑛2+ 𝑎𝑞 + 2𝑒 − 𝐸 𝑜 = −0.763𝑉
𝑜 0 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜
𝐸𝑐𝑒𝑙𝑙 = − 0.763 − 0.80 𝑉 = −1.563 V
𝑜
Since 𝐸𝑐𝑒𝑙𝑙 is -ve, the given reaction is not feasible
Example 4: Determine the feasibility of the reaction
2Al(s) + 2𝑆𝑛4+ 𝑎𝑞 → 2𝐴𝑙 3+ 𝑎𝑞 + 3𝑆𝑛2+ (𝑎𝑞)
Solution
Anode: 2Al(s) → 2𝐴𝑙 3+ 𝑎𝑞 + 6𝑒 − 𝐸 𝑜 = −1.66𝑉
Cathode 3𝑆𝑛4+ + 6𝑒 − → 3𝑆𝑛2+ 𝐸 𝑜 = +0.15𝑉
𝑜 0 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜
𝐸𝑐𝑒𝑙𝑙 = 0.15 – 1.66𝑉 = 1.81V
𝑜
Since 𝐸𝑐𝑒𝑙𝑙 is positive, the reaction is feasible
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The Nernst Equation
• the potential of a single electrode/half-cell reaction varies with the concentration of ions in
the cell
• mathematical relationship which enable us to calculate the half-cell potential, E from the
standard electrode potential 𝐸 𝑜 & the temperature of the cell → Nernst equation
2.303𝑅𝑇
E = 𝐸𝑜 − log 𝐾 (1)
𝑛𝐹
𝐸 𝑜 = standard electrode potential; R = gas constant, T = Kelvin temperature;
n=number of electrons transferred in the half reaction; F = Faraday of electricity;
K = equilibrium constant for the half-cell reaction as in equilibrium law
o For a half-cell reaction when the metal electrode gives 𝑀𝑛+ + 𝑛𝑒 −
2.303𝑅𝑇 [𝑀𝑛+ ]
E= 𝐸𝑜 − log (2)
𝑛𝐹 [𝑀]

o concentration of solid metal, [M] = 0

o Therefore, the Nernst equation can be written as
2.303𝑅𝑇
E = 𝐸𝑜 − log[𝑀 𝑛+ ] (3)
𝑛𝐹
o Substituting the values of R, F and T at 25 ℃ , the quantity 2.303RT/ = 0.0591.
o thus
0.0591
o E = 𝐸𝑜 − log[𝑀 𝑛+ ]
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Corrosion
o Oxidation of metal into oxide

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Prevention of Corrosion

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 Electrolytic Cells (Electrolysis)
o Application of an external voltage to drive a nonspontaneous reaction
o The applied voltage forces electrons through the circuit in the reverse direction,
converting a galvanic cell to an electrolytic cell
Table 1: Comparison of Galvanic and Electrolytic Cells
Property Galvanic Cell Electrolytic Cell

ΔG <0 >0

Ecell >0 <0

Electrode Process

Anode oxidation oxidation

Cathode reduction reduction

Sign of Electrode

Anode − +

Cathode + −
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 Electrolysis…
o At sufficiently high temperatures, ionic solids melt to form liquids that conduct
electricity extremely well due to the high concentrations of ions.
o If two inert electrodes are inserted into molten NaCl, for example, and an
electrical potential is applied, Cl− is oxidized at the anode, and Na+ is reduced at
the cathode
o The overall reaction is as follows:
2NaCl(l) → 2Na(l) + Cl2(g) (4)
o This is the reverse of the formation of NaCl from its elements
o The product of the reduction reaction is liquid sodium because the melting point
of sodium metal is 97.8°C,
o well below that of NaCl (801°C).
o ≈ 20,000 tons of sodium metal are produced commercially in the US each year
by the electrolysis of molten NaCl in a Downs cell (Figure 2).
o In this specialized cell, CaCl2 (melting point = 772°C) is first added to the NaCl
to lower the melting point of the mixture to about 600°C, thereby lowering
operating costs

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 Figure 2: A Downs Cell for the Electrolysis of Molten NaCl. The electrolysis of a
molten mixture of NaCl and CaCl2 results in the formation of elemental sodium and
chlorine gas
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o The Hall–Heroult process used to produce aluminum commercially,
o molten mixture of about 5% aluminum oxide (Al2O3; melting point = 2054°C) and 95%
cryolite (Na3AlF6; melting point = 1012°C) is electrolyzed at about 1000°C
o producing molten aluminum at the cathode and CO2 gas at the carbon anode
o The overall reaction is as follows:
2Al2O3(l) + 3C(s) ⟶ 4Al(l) + 3CO2(g) (5)
o Oxide ions react with oxidized carbon at the anode, producing CO2(g)
o In general, any metal that does not react readily with water to produce hydrogen can be
produced by the electrolytic reduction of an aqueous solution that contains the metal
o p-block metals and most of the transition metals are in this category
o metals in high oxidation states, which form oxoanions, cannot be reduced to the metal by
simple electrolysis.
o Active metals, such as aluminum and those of groups 1 and 2, react so readily with water
that they can be prepared only by the electrolysis of molten salts
o Similarly, any nonmetallic element that does not readily oxidize water to O2 can be
prepared by the electrolytic oxidation of an aqueous solution that contains an appropriate
anion
o In practice, among the nonmetals, only F2 cannot be prepared using this method
o Oxoanions of nonmetals in their highest oxidation states, such as NO3−, SO42−, PO43−, are
usually difficult to reduce electrochemically and usually behave like spectator ions that
remain
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Quantitative Considerations
o The knowledge of stoichiometry of an electrolysis reaction, the amount of current
passed, and the length of time, can be calculate the amount of material consumed or
produced in a reaction
o Similarly, we can use stoichiometry to determine the combination of current and time
needed to produce a given amount of material
o The quantity of material that is oxidized or reduced at an electrode during an
electrochemical reaction is determined by the stoichiometry of the reaction and the
amount of charge that is transferred.
o For instance, in the following reaction
Ag+(aq )+ e- −→ Ag(s)
o 1 mol of electrons reduces 1 mol of Ag+ to Ag metal.
o In contrast, in the reaction
Cu2+(aq) + 2e- −→ Cu(s)
o 1 mol of electrons reduces only 0.5 mol of Cu2+ to Cu metal
o Recall that the charge on 1 mol of electrons is 1 faraday (1 F = 96,485 C)
o Therefore, we can calculate the number of moles of electrons transferred when a known
current is passed through a cell for a given period of time.
o The total charge (Q in coulombs) transferred is the product of the current, I ( in A) and
the time, t (in s):
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 Faraday Laws of Electrolysis
Faraday’s first law of Electrolysis
o the amount of substance liberated/deposited at a particular electrode is directly proportional
to the quantity of electricity passed in the solution.
mα Q
m α It
m is the mass of product of electrolysis when current I(A) passed for t (s)
Faraday’s second law of Electrolysis
o when the quantity of electricity is passed through the
solution of different electrolyte connected in series,
the mass of the substances liberated/deposited at the
electrodes are directly proportional to their chemical
equivalent.
Worked Examples 1

Calculate the mass of lead deposited at the cathode during electrolysis when a current of 1.50
A flows through molten lead(II) bromide for 20.0 min. ([Pb = 207; 1 F = 96 500 C mol–1)
Soln:
Step 1: Write the half-equation for the reaction
Pb2+ + 2e → Pb
Step 2: Find the number of coulombs required to deposit 1 mole of product at the electrode
2 moles of electrons are required per mole of Pb formed
2F = 2 × 96 500 = 193 000 C mol–1
Step 3: Calculate the charge transferred during the electrolysis.
Q=I×t = 1.50 × 20 × 60 = 1800 C
Step 4: Calculate the mass by simple proportion using the relative atomic mass.
193 000 C deposits 1 mole Pb, which is 207 g Pb

207 1800
so 1800 C deposits = × = 1.93 𝑔 of Pb
19300 1
Worked Examples 2
Calculate the mass of aluminium deposited at the cathode during electrolysis when a current of
4.50 A flows through molten Aluminium(III) bromide for 1.0 hour. (Al = 27; F = 96 500 C mol–1)
Soln:
Step 1: Write the half-equation for the reaction.
Al3+ + 3e → Al
Step 2: Find the number of coulombs required to deposit 1 mole of product at the electrode.
3 moles of electrons are required per mole of Pb formed
3F = 3 × 96 500 = 289 500 C mol–1
Step 3: Calculate the charge transferred during the electrolysis.
Q=I×t = 4.50 × 60 × 60 = 16, 200 C
Step 4: Calculate the mass by simple proportion using the relative atomic mass.
289 500 C deposits 1 mole Al, which is 27 g Al

27 16200
so 16,200 C deposits = × = 1.511 𝑔 of Al
289500 1
Exercises
1. 1.5g of silver was deposited at the cathode when 5.0A of current flows through a solution
Of silver nitrate. Calculate the time taken for the experiment (Ag = 108; F = 96 500 C mol–1)

2. Calculate the mass of silver deposited at the cathode during electrolysis when a current of
1.80 A flows through an aqueous solution of silver nitrate for 45.0 min (Ag = 108; F = 96 500 C
mol–1)

3. Calculate the volume of hydrogen produced at r.t.p. when a concentrated aqueous solution of
sulfuric acid is electrolysed for 15.0 min using a current of 1.40 A. (F = 96 500 Cmol–1; 1 mole
of gas occupies 24 dm3 at stp).

4. Calculate the volume of oxygen produced at r.t.p. when a concentrated aqueous solution of
sodium sulfate is electrolysed for 55.0 min using a current of 0.70 A. (F = 96 500 C mol–1; 1
mole of gas occupies 24.0 dm3 at stp).
Electroplating
o a layer of a second metal is deposited
on the metal electrode that acts as the
cathode during electrolysis
o Electroplating is used to enhance the
appearance of metal objects and
protect them from corrosion
o Examples of electroplating include
the chromium layer found on many
bathroom fixtures
o or (in earlier days) on the bumpers
and hubcaps of cars, as well as the Electroplating uses an electrolytic cell in which
thin layer of precious metal that coats the object to be plated, such as a fork, is
silver-plated dinnerware or jewelry. immersed in a solution of the metal to be
deposited
o In all cases, the basic concept is the
same

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Worked Examples 2
A silver-plated spoon typically contains about 2.00 g of Ag. If 12.0 h are required to achieve
the desired thickness of the Ag coating, what is the average current per spoon that must flow
during the electroplating process, assuming an efficiency of 100%?
Soln:
Given: mass of metal, time, and efficiency and to determine current require
We must first determine the number of moles of Ag corresponding to 2.00 g of Ag:
2.00
𝑀𝑜𝑙𝑒𝑠 𝐴𝑔 = = 1.85 × 10−2 𝑚𝑜𝑙 𝐴𝑔
107.868 𝑔/𝑚𝑜𝑙
Ag+(aq) + e− → Ag(s),
So 1 mol of electrons produces 1 mol of
Using the definition of the faraday,
coulombs = (1.85 × 10−2mol e−)(96,485 C/mol e−) = 1.78 × 103 C / mole
The current in amperes needed to deliver this amount of charge in 12.0 h is therefore
1.78 × 103 𝐶
𝑎𝑚𝑝𝑒𝑟𝑒𝑠 =
12 × 60 × 60
10−2 𝐶
= 4.12 × = 4.12 × 10−2 𝐴
𝑠
Because
1/13/2025the electroplating process is usually much less than 100% efficient (typical values
29 are
closer to 30%), the actual current necessary is greater than 0.1 A.