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MODULE 1

ELECTROCHEMISTRY
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

LESSON 1.4 Nonstandard Conditions

In real world applications, corrosion, a very common example of redox-
reactions occurs in nature at non-standard conditions. You may have asked “What
must we do to account for the differences that arise when standard conditions are
not present?” This situation has a clear relationship with thermodynamics. The
equation that describes cell potentials in nonstandard conditions is called the Nerst
equation:
𝑅𝑇
E = 𝐸0 − ln 𝑄
𝑛𝐹
where:
Q (in Chemical Equilibrium) – the product of the concentrations of the
products divided by the product of the concentrations of the reactants, each
concentration raised to the power of its stoichiometric coefficients.

In the equation: aA + bB ⇌ cC + dD, Q is written as:

[C]c [D]d
Q=
[A]a [B]b
J
F – Faraday constant, 1 F = 96500
V ∙ mol e−
n – the number of electrons transferred in the redox reaction, mol e - /mole rxn
R = 8.313 J/(mol • K)
Using base – 10 logarithms,
2.303 𝑅𝑇
E = 𝐸0 − log 𝑄
𝑛𝐹
since Q = Keq
2.303 𝑅𝑇
E = 𝐸0 − log 𝐾𝑒𝑞
𝑛𝐹
At room temperature (T = 298K):
2.303 𝑅𝑇
= 0.0591 V
𝐹

Thus the equation becomes

0.0591 𝑉
E = 𝐸0 − log 𝑄
𝑛
or
0.0591 𝑉
E = 𝐸0 − log 𝐾𝑒𝑞
𝑛
Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO
Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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EXAMPLES:
1. One half – cell in a voltaic cell is constructed from a copper wire dipped into
a 4.8 x 10-3 M solution of Cu(NO3)2. The other half – cell consists of a zinc
electrode in a 0.40 M solution of Zn(NO3)2. Calculate the cell potential.
Solution:
i. Assume that the condition is at room temperature, 298K:
0.0591 𝑉
E = 𝐸0 − log 𝐾𝑒𝑞
𝑛
ii.

0.40 M Zn(NO3)2 4.8x10-3 M Cu(NO3)2

anode (oxidation): Zn(s) → Zn+2(aq) + 2e- E0 = + 0.76 V

cathode (reduction): Cu+2(aq) + 2e- → Cu(s) E0 = +0.34 V
Over-all cell reaction: Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s) E0 = +1.10 V
iii. n = 2 mol e- / mole rxn
[Zn+2
(aq) ] [0.40]
iv. Keq = = = 83.33
[Cu+2
(aq) ] [4.8𝑥10−3 ]
v. Substitute values to the working equation:
0.0591 V
E = +1.10 V − log(83.33)
2
E = + 1.04 V

2. Use the Nernst equation to calculate the cell potentials of the following cell at
298 K:
2 Ag+(aq) (0.50 M) + Ni(s) → 2 Ag(s) + Ni2+(aq) (0.20 M)
Solution:

i. anode (oxidation): Ni(s) → Ni+2(aq) + 2e- E0 = + 0.25 V

cathode (redct’n): 2Ag (aq) + 2e → 2Ag(s)
+1 -
E0 = + 0.80 V
Over-all cell Rxn: Ni(s) + 2Ag+1(aq) → Ni+2(aq) + 2Ag(s) E0 = + 1.05 V
ii. n = 2 mol e- / mole rxn
[Ni+2
(aq) ] [0.20]
iii. Keq = = = 0.8
[Ag+1
(aq) ]
2 [0.5]2
iv. Substitute values to the working equation:
0.0591 v
E = +1.05 v − log(0.8) = + 1.0528 V
2
Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO
Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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Practice Task 1.3:

1. Use the Nernst equation to calculate the cell potentials of the following
cells at 298 K:
a. Pb+2/Pb half-cell and a Pt/H+/H2 half-cell if [Pb+2] = 0.10 M, [H+] = 0.050
M,
and PH2 = 1.0 atm?

b. Mg(s) / Mg+2 (0.24 M) // Mg+2 (0.53 M) / Mg(s)

c. Cr(s) / Cr+3 (0.30)//Pb+2(0.40)/Pb

2. One half-cell in a voltaic cell is constructed from a silver wire dipped into
a AgNO3 solution of unknown concentration. The other half-cell consists
of a zinc electrode in a 1.0 M solution of Zn(NO 3)2. A potential of 1.48 V
is measured for this cell. Use this information to calculate the
concentration of Ag+(aq).

LESSON 1.5 Significance of Electromotive Force

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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Electromotive force is used to calculate the amount of electrical energy,

equilibrium constant (K) and standard free-energy change (ΔG0). The K and
ΔG0 are also used to determine the spontaneity of the redox reaction.
ΔG0 K Spontaneity of the reaction Direction of the reaction
Negative >1 Spontaneous reaction Favors forward reaction
0 =1 No net change At equilibrium
Positive <1 Non-spontaneous reaction Favors reverse reaction

1.5.1 Amount of Electrical Energy

The constant flow of electrons generates electrical energy. Electrical energy
is the product of electromotive force expressed in volts and the total electrical charge
in coulombs, which is equal to the number of moles of electrons (n) that pass through
the circuit multiplied to the Faraday’s constant, F .

Electrical energy = nF x E0
= mol e- / mole rxn (C/mol e-) x volts
= coulombs/mole rxn x volts
= joules/ mole rxn
Hence:
J coulomb
1J = 1 C X 1 V 1 F = 96500 = 96500
V ∙ mol e− mol e−
Thus, the amount of electrical energy generated by the reaction:
Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s) with E0 = +1.10 V is
Electrical energy = nF x E0cell
= (2 mol e- /mole rxn)(96500 coulomb/mol e-)(1.10 V)
Electrical energy = 2.12 x 105 C∙ V or 2.12 x 105 Joules/mole rxn

1.5.2 Free – Energy Change (ΔG0)

Electromotive force (E0) and free-energy change at standard-state conditions
are related as can be seen below:
ΔG0 = - nFE0cell
The change in free energy is the maximum amount of useful electrical work
that can be obtained from the reaction. The (-) sign implies that electrical work is
done on the surroundings.
For the reaction written above, free-energy change is:

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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ΔG0 = - nFE0cell
ΔG0 = - (2mol e-/mole rxn)(96500 coulomb/mol e-)(1.10 V)
ΔG0 = - 2.12 x 105 coulomb∙V/mole rxn = - 2.12 x 105 J/mole rxn

1.5.3 Equilibrium Constant (K)

Free-energy change is written as: ΔG0 = - RT ln K
Therefore, it can also be written as: - nFE0cell = - RT ln K
Deriving K:
0
nF Ecell
ln K =
RT
Using R = 8.314 J/K∙mol,
F = 96500 J/V ∙mol e-, and
T = 298 K
n = mol e- /mole
J 0
n (96500 − ) Ecell
ln K = V mol 𝑒
J
(8.314 ) 298 K
K • mole
0
n Ecell
ln K =
0.0257 V
n E0cell
If a = , hence, K = ea
0.0257 V
Again, for the reaction: Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu, equilibrium constant
is:
0
n Ecell
ln K =
0.0257 V

2 (1.10 V)
ln 𝐾 =
0.0257 V

ln K = 85.6

K = 1.50 x 1037

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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Practice Task 1.4:

Calculate the (a) electrical energy, (b) ΔG0, and (c) K of the reaction:
1. Fe+2(aq) / Fe+3(aq) // Ag+(aq) / Ag(s)
2. Zn(s) / Zn+2(aq) // Cr+3(aq) / Cr(s)
3. Fe(s) + Hg+2(aq) ---> Fe+2(aq) + Hg(l)
4. Zn(s) + Ni+2(aq) → Zn+2(aq) + Ni(s)
5. Pb(s) + Sn+2(aq) → Pb+2(aq) + Sn(s)
6. Al(s) / Al+3(aq) // Mg+2(aq) / Mg(s)
7. Ca(s) / Ca+2(aq) // Cr+3(aq) / Cr(s)
8. Mg(s) / Mg+2(aq) // Fe+2(aq) / Fe(s)

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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LESSON 1.6 Applications of Oxidation – Reduction Reactions

1.6.1 Batteries- these include primary cells like dry cells, and secondary cells such
as lead storage battery and Edison storage battery. Primary cells or
irreversible cells cannot be recharged because the electrodes and
electrolytes cannot be restored to the original state by an external potential.
On the other hand, secondary cells can be used repeatedly. The substances
used in the production of electricity through cells are in the reverse direction
during discharge. This recharges the cell. Examples of secondary cells are
lead storage battery, Edison storage battery and nickel-cadmium storage cell.
The Dry Cell
a. Carbon-Zinc dry cell
The Main Components:
1. Zn-anode
2. Carbon rod-cathode
3. Paste of MnO2, NH4Cl, H2O as
the electrolyte
4. Porous paper- separates the
paste from the Zn casing, also
allows for the diffusion of ion.

Figure 1.2: Dry Cell (Voltage output=1.5V)

The reactions involved are:
Anode: Zn(s) → Zn+2(aq) + 2e-
Cathode: 2 NH4+1 (aq) + 2MnO2(s) + 2e- → Mn2O3(s) + 2NH3(aq) + H2O (l)
Over-all Zn(s) + 2NH4+1 (aq) + 2MnO2(s) → Zn+2(aq) + Mn2O3(s) + 2NH3(aq) + H2O (l)
The cathode reaction is complex and a mixture of products is formed.
As NH3 builds up around the carbon rod, it insulates the rod thus
decreasing the power output, but when the cell is allowed to rest, the NH 3
diffuses towards the anode and combines with Zn+2 ions.

b. Alkaline cell also uses Zn and MnO2 but KOH is the electrolyte. The
voltage output is about 1.54 V. It has a longer shelf-life and delivers higher
currents for longer period than Zn-C cell. Alkaline cell is often sold as
cheap watch battery. It is also the battery used in flashlights, MP3
players, and handheld video games.
Anode: Zn + 2 OH- → ZnO + H2O + 2e-
Cathode: 2MnO2 + H2O + 2e-→ Mn2O3 + 2OH-
Zn + 2MnO2 → ZnO + Mn2O3
c. Mercury cell can be made compact so it is used where small size is
important like in pacemakers, hearing aids and electric watches. The
electrolyte is KOH.
Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO
Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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Anode: Zn + 2 OH- → ZnO + H2O + 2e-

Cathode: HgO + H2O + 2e-→ Hg + 2OH-
Zn + HgO → ZnO + Hg
The Hg does not flow since it is mixed with HgO and graphite powder.
The electrolyte is held by an absorbent cotton pad. The emf is 1.3 V.

d. Silver oxide cell is the miniature battery used in wristwatches, calculators

and auto exposure cameras. The silver content increases the cost of the
cell. The emf is about 1.5 V.
Anode: Zn + 2 OH- → Zn(OH)2 + 2e-
Cathode: Ag2O + H2O + 2e-→ 2Ag + 2OH-
Zn + Ag2O + H2O → Zn+2 + 2 OH- + 2Ag or
Zn + Ag2O + H2O → Zn(OH)2 + 2 Ag

The Secondary cells

a. Lead Storage Battery
The lead storage battery functions as a voltaic cell when used as a
source of direct current e.g. to start the engine of a vehicle or to supply
power to the electrical accessories of the vehicle. When the engine is
running, it functions as an electrolytic cell.
The components are (a) Pb spongy as anode (b) PbO 2 and (c) dilute
aqueous solution of H2SO4.
When the cell is discharging the reactions are:
Anode: Pb(s) + SO42- (aq) → PbSO4(s) + 2e-
Cathode: PbO2(s) + 4H+(aq) + SO42- (aq) + 2e- → PbSO4(s) + 2H2O (l)
Over-all Pb(s) + PbO2(s) + 4H+(aq) + 2SO42- (aq) → 2PbSO4(s) + 2H2O (l)

The PbSO4 is insoluble in water and sticks to both electrodes and

causes the discharging of batteries. The electrolyte is also depleted of the
H2SO4 and the concentration decreases, whereby the density also
decreases. The density indicates the state of charge of the battery.
Running an external current recharges the battery, the flow of electrons
and the chemical reactions at each electrode can be reversed.

Anode: PbSO4(s) + 2H2O (l) → PbO2(s) + 4H+(aq) + SO42- (aq) + 2e-

Cathode: PbSO4(s) + 2e- → Pb(s) + SO42- (aq)
Over-all: 2PbSO4(s) + 2H2O (l) → Pb(s) + SO42- (aq) + PbO2(s) + 4H+(aq) + 2SO42- (aq)
The heat produced during the discharging can evaporate some of the
water from the cells. Distilled water should be used to restore the fluid back.
Impurities in water may cause the loss of charge on a battery.
Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO
Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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b. Edison storage battery

The Edison storage battery consists of steel anode plates packed with
iron and cathode plates packed with hydrated NiO 2. The electrolyte is
21% KOH solution with some LiOH. When the cell is delivering current,
the reactions are:
Anode: Fe → Fe2+ + 2e-
Cathode: 2H2O +NiO2 + 2e-→ Ni2+ + 4OH-
Over-all reaction: Fe + 2H2O +NiO2→ Fe2+ + Ni2+ + 4OH- or
Fe + 2H2O +NiO2 → Fe2+ + Ni(OH)2 + 2OH-
The emf of each cell is about 1.47 V. The battery is sealed otherwise
the KOH and the LiOH will form carbonates with atmospheric CO 2. The
Edison storage battery is lighter and more durable than the lead storage
battery, but it is more expensive.

c. Nickel-Cadmium storage cell

The Nickel-Cadmium storage cell is the battery that powers
rechargeable electronic calculators, electric shavers and power rods. The
emf of the cell is about 1.4 V.
Anode: Cd + 2 OH- → Cd(OH)2 + 2e-
Cathode: NiO2 + 2H2O + 2e-→ Ni(OH)2 + 2OH-
Cd + NiO2 + 2H2O → Cd(OH)2 + Ni(OH)2

d. Hydrogen Fuel Cells

In this cell, hydrogen and oxygen gases are bubbled through the two
inert electrodes to form water, heat, and electricity. The anode-cathode
reactions are:
Anode: 2H2(g) + 4OH-(aq) → 4H2O (l) + 4e-
Cathode: O2(g) + 2H2O(l) + 4e- → 4OH- (aq)
Over-all 2H2(g) + O2(g) → 2H2O (l)
1.6.2 Corrosion
Corrosion is the chemical attack on the metal or deterioration of metal
through oxidation by its environment. It is a galvanic process wherein the metal
that corrode acts as the anode.
In the rusting of iron, the following steps occur:
1. Fe + 2H2CO3 → Fe+2 + 2H+ + 2HCO3- + 2e-
2. 4H+ + O2 + 4e- → 2H2O
3. 4Fe+2 + O2 + (4 + 2x) H2O → 2Fe2O3•XH2O + 8H+
LESSON 1.7 Electrolysis

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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Electrolysis is a process that utilizes electrical potential energy to cause a

chemical reaction that does not occur spontaneously. As direct current is passed
through a solution of an electrolyte, the anions move towards the anode, where they
give up their electrons. The electrons move through the metallic conductor and
through the generator of the electric current to the cathode, where the cations are
discharged by taking up these electrons.

1.7.1 Electrode Products

It is not always easy or even possible to predict what products will result when
a direct current is passed through an aqueous solution of an electrolyte. In addition
to the ions from the electrolyte, water molecules and the ions from water (H+ and
OH-) are present. These may also participate in the electrochemical reactions.
Furthermore, the electrode products obtained with concentrated solutions (or molten
state) often differ from those obtained with dilute solutions. In some cases, one or
both of the electrodes may react (the anode in the electroplating of silver is one of
the reactants). To narrow the list of variables, inert electrodes, usually platinum, are
used. The following rules are applied to predict electrode products for a
considerable number of reactants.

At the inert cathode (-), the following occurs,

1. If the metal is below hydrogen activity, electrolysis of aqueous solution of its
salts causes the metal to form at the cathode. For example, if a water
solution of CuCl 2, of AgNO3 or of HgCl2 is electrolyzed, Cu, Ag, or Hg,
respectively will be formed.
2. If a metal is above hydrogen in activity, electrolysis of aqueous solutions of
it usually liberates hydrogen gas at the cathode. For example, if aqueous
NaCl, or KCl, or MgCl2 is electrolyzed, hydrogen will be liberated at the
cathode in each case.

At the inert anode (+), the following occurs,

1. Oxygen is liberated during the electrolysis of most salts with anions
containing oxygen, such as SO4-2 and NO3-. Example:
4 AgNO3 + 2 H2O 4 Ag + O2 + 4 HNO3

2H2O O2 + 4H+ + 4e- (anode)

2. Anions such as Cl -, Br -, and I – (but not F-) are more easily oxidized than
water. Hence, the free halogen is liberated. For example, during electrolysis
of molten or concentrated sodium chloride, chlorine is liberated at the anode.
In case of dilute solution, oxygen as well as chlorine are formed.
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(a) (b)
Anode Rxn: 2Cl- → Cl2 + 2e- A.R: 2H2O → O2 + 4H+ + 4e-
Cathode Rxn: 2Na+ + 2e- → 2Na 2Cl- → Cl2 + 2e-
C.R: 6H+ + 6e- → 3H2
Figure 1.3: Schematic representation of the electrolysis of (a) molten NaCl
and (b) aqueous solution of NaCl.

EXAMPLE
Predict what is liberated at each electrode when each of the following
electrolytes is electrolyzed between inert electrodes.

Electrolytes Cathode Product Anode Product

1. molten AlCl3 Al Cl2

2. dilute solution of AlCl 3 H2 Cl2, O2

3. aqueous solution of Mg(NO3)2 H2 O2

4. aqueous solution of CuSO4 Cu O2

5. concentrated solution of CuCl 2 Cu Cl2

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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Practice Task 1.5:

1. Explain why different products are obtained in the electrolysis of molten

ZnCl2 and in the electrolysis of an aqueous solution of ZnCl 2.

2. What is liberated at each electrode when the following are electrolyzed

between inert electrodes?
a. Aqueous solution of Na3PO4

b. Molten KCl

c. Aqueous solution of AgNO3

d. Concentrated solution of NiSO4

e. Dilute solution of AuCl3

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
SY: 2020 - 2021
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