Electrochem Notes

Chemistry Department
CM5106 Inorganic and Electrochemistry
Experiment, Explore, Excel
Lesson 1.1 Oxidation-Reduction Reactions
Silver tarnishes when it comes in contact with sulfur compounds in the air.
Copper gets coated in beautiful green patina as it ages. Metals rust or corrode
in the presence of air and water. Minerals (ionic compounds) found in ore can
be decomposed with the use of electricity to produce pure metals and non-
metals. All of these reactions are examples of oxidation and reduction,
otherwise known as redox reactions. Let’s explore what is happening at the
atomic level in redox reactions.
Oxidation and Reduction
4Al(s) + 3O2(g) → 2Al2O3(s) How are redox

reactions different
from other chemical
This reaction involves a transfer of electrons from Al metal to O2 gas.
reactions?
• Al atoms lose electrons to form Al3+ ions. This can be represented by the
ion-electron equation (also known as half-equation):
Al → Al3+ + 3e-
When a substance (on the left hand side of the arrow) loses electrons, the
substance is said to be oxidized (or it undergoes oxidation).
• Understandably, oxidation cannot take place on its own. Another

substance must accept the electrons lost by Al metal.
O atoms in O2 gain electrons to form O2- ions, represented by
O2 + 4e- → 2O2-
When a substance (on the left hand side of the arrow) gains electrons, the
substance is reduced (or undergoes reduction).
• When oxidation-reduction reactions occur, the number of electrons

transferred must be the same. Hence in the above reaction, 4 mol Al must
react with 3 mol O2 for 12 mol of electrons to be completely transferred.
( Al → Al3+ + 3e- ) x4 … is the oxidation

half-equation
( O2 + 4e- → 2O2- ) x3 … is the reduction
half-equation
4Al + 3O2 → 4Al3+ + 6O2- (or 2Al2O3) … + + is the
overall equation
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After doing this

Which of the following equations represents a redox reaction? question, can you
generalize which type
of reaction is NOT
RedOx?
A 2 Na(s) + 2HCl(aq) 2NaCl(aq) + H2(g)
B NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) Name another
C Na2CO3(s) + 2HCl(aq) 2NaCl(aq) + CO2(g) + H2O(l) reaction type that is
NOT RedOx.
D NaOH(aq) + NH4Cl(s) NaCl(aq) + NH3(g) + H2O(l)
2. Oxidation Numbers (or Oxidation States)
This concept is devised to keep track of the electrons gained by the substance
reduced and the electrons lost by the substance oxidized, especially if the
substances are covalent or are polyatomic ions - such as SO42-, manganate (VII)
ion - MnO4-, dichromate (VI) ion - Cr2O72-.
Each atom in the molecule or charged species is assigned an oxidation number

following these rules:
Oxidation
No Species number Examples
assigned It is the
1. An atom in its elemental The oxidation number of H electronegativity of
form, e.g. Cl2, He, P4 0 in hydrogen gas (H2) is 0. the atom that is the
basis of the
The oxidation number of oxidation number
Mg in magnesium metal is assigned to it in a
0. molecule.
2. Any monoatomic ion, e.g. The oxidation number of Unlike charge, in

charge Na in sodium chloride oxidation
alkali metal ions (Grp 1A) = (NaCl) is +1. numbers, the sign
on ion is written before
+1
number
The oxidation number of Cl
halide ions (Grp 7A) = -1 in sodium chloride (NaCl)
is -1.
O2- and S2- ions (Grp 6A) = -2
3. Hydrogen in a compound
• when bonded to non- +1 The oxidation number of H

metals in H2O or CH4 or HNO3 = +1
• when bonded to metals The oxidation number of H

-1 in NaH or MgH2 = -1
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Oxidation
No Species number Examples
assigned
4. Oxygen in a compound -2 The oxidation number of O
(whether ionic or covalent) in H2O or CO2 or NO = -2
Except in a peroxide -1 The oxidation number of O

compound in H2O2 or BaO2 = -1
5. Fluorine in a compound -1 The oxidation number of F F only has one

in NaF or CF4 = -1 oxidation state, -1
regardless of the
compound it is in.
6. Sum of oxidation numbers of
all atoms in Cl or Br or I may
• a neutral compound 0 The oxidation number of Cr have many
(x) in Cr2O72- is worked out different oxidation
• a polyatomic ion overall as: states.
charge on 2(x) + 7(-2) = -2
ion Oxidation no. of Cr, x = +6
3. Definitions of Oxidation and Reduction
In terms of … Oxidation is… Reduction is…
1. oxygen gain of oxygen loss of oxygen
Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g) Definitions 1 and 2

have limited
usefulness in
CO is oxidized (since CO gains oxygen to become CO2) & reactions involving
Fe2O3 is reduced (since Fe2O3 loses oxygen to become Fe) oxides and
hydrogen.
2. hydrogen loss of hydrogen gain of hydrogen
H2S(g) + Cl2(g) → 2HCl(g) + S(s)
H2S is oxidized (since H2S loses hydrogen to become S) &

Cl2 is reduced (since Cl2 gains hydrogen to become HCl)
3. electrons loss of electrons gain of electrons
Cu(s) + 2AgNO3(aq) → Cu(NO3)2(aq) + 2Ag(s)
Cu is oxidized (since Cu loses 2 electrons to become Cu2+) & The exchange of

electrons is more
easily seen if
Oxidation half-equation: Cu → Cu2+ + 2e- equation is written
as an ionic
AgNO3 is reduced (since Ag+ gains an electron to become Ag) equation.
Reduction half-equation: Ag+ + e- → Ag
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4. oxidation Increase in Decrease in

number oxidation number oxidation number
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)
Mg is oxidized (because the oxidation number of Mg has

increased from 0 in Mg to +2 in MgCl2) &
Oxidation half-equation: Mg → Mg2+ + 2e-
HCl is reduced (because the oxidation number of H has

decreased from +1 in HCl to 0 in H2)
Reduction half-equation: 2H+ + 2e- → H2
A
disproportionation
A special type of redox reaction! reaction is an
Identify the substance oxidized and the substance reduced in the following oxidation-reduction
equation. Justify your choice in terms of oxidation numbers. reaction in which
the same substance
2H2O2(aq) → 2H2O(l) + O2(g) is simultaneously
oxidized and
reduced.
4. Oxidizing agents (OA) and Reducing agents (RA)
• An oxidizing agent causes another species to be oxidized (or to lose In other words, the
electrons). In other words, itself must gain electrons (and is reduced) in the oxidizing agent is
reaction. the substance that is
reduced.
Important examples of common oxidising agents are:
Purple potassium manganate(VII) - KMnO4(aq), which on reaction with What is the

a RA becomes reduced to colourless Mn2+. observed end point
if a titration is
carried out?
e.g. MnO4- + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
MnO4- (purple) is the OA. It is reduced to Mn2+ (colourless) in the reaction. Fe2+ Oxidation number
(pale green) is the RA. It is oxidized to Fe3+ (yellow). refers to the atom;
but the entire
substance is the
Orange potassium dichromate(VI) - K2Cr2O7(aq), which on reaction OA or RA.
e.g. The oxidation
with a RA becomes reduced to green Cr3+.
number of Mn (the
atom) is +7;
e.g. 2Cr2O72- + 3CH3CH2OH + 16H+ → 4Cr3+ + 3CH3CO2H + 11H2O MnO4- (the
substance) is the OA
Cr2O72-is the OA. It turns from orange to green in the reaction. Ethanol is the
RA. It is oxidized to ethanoic acid.
Other oxidizing agents include Cl2 gas or aqueous chlorine - aq Cl2,

hydrogen peroxide - H2O2 and aqueous iron (II) compounds - aq Fe2+.
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• A reducing agent causes another species to be reduced and itself becomes

oxidized in the reaction.
A common laboratory reducing agent is: I2 is non-polar and is

not very soluble in
Colourless aqueous KI which on reaction with an OA becomes water. However, it
oxidized to a brown solution of I2(aq) - with black precipitate of dissolves readily in I-
(aq) to form brown
I2(s). coloured triiodide
ion, I3-.
e.g. Cl2(aq) + 2I-(aq) → 2Cl-(aq) + I2(aq) I2(aq) + I (aq) ⇌ I3-
-
(aq)
What is described as
I2(aq) is actually I3-
(aq)
Hydrogen peroxide(H2O2) can behave as an oxidizing agent and reducing agent.

Study the observations given below and deduce the role of H2O2 in the reaction.
acidified potassium iron (II) sulphate

Reaction of H2O2 with
manganate (VII) solution
Purple solution Light green solution
Observation
decolourised turned yellow
The role of H2O2 in the

reaction (OA or RA)
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DIY Questions
1. Write the oxidation number for the chlorine atom in each of the following chlorine-
containing compounds/ions and draw their Lewis structures.
Cl2 Cl2O ClO4- ClF4-
SrCl2 NaClO Cl2O7 POCl3
ICl NaClO3 ClO2 HClO2
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2. Indicate whether each of the following statements is True or False:
(a) If something is oxidized, it is formally losing electrons.
(b) For the reaction Fe3+ (aq) + Co2+ (aq) Fe2+ (aq) + Co3+ (aq), Fe3+ (aq) is the reducing agent
and Co2+ (aq) is the oxidizing agent.
(c) If there are no changes in the oxidation state of the reactants or products of a particular
reaction, that reaction is not a redox reaction.
(d) If something is reduced, it is formally losing electrons.
(e) A reducing agent gets oxidized as it reacts.
(f) Oxidizing agents can convert CO into CO2.
3. In each of the following balanced oxidation-reduction equations, identify those elements

that undergo changes in oxidation number and indicate the magnitude of the change in
each case.
(a) I2O5(s) + 5CO(g) I2(s) + 5CO2(g)
(b) 2Hg2+(aq) + N2H4(aq) 2Hg(l) + N2(g) + 4H+(aq)
(c) 3H2S(aq) + 2H+(aq) + 2NO3-(aq) 3S(s) + 2NO(g) + 4H2O(l)
(d) Ba2+(aq) + 2OH-(aq) + H2O2(aq) + 2ClO2(aq) Ba(ClO2)2(s) + 2H2O(l) + O2(g)
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4. In the following equation, C17H36 is used as the formula for a typical molecule in fuel oil.
__ NH4NO3(s) + __ C17H36(l) → __ N2(g) + __ CO2(g) + __ H2O(g)
(a) Balance the above equation.
(b) Suggest an explanation why this reaction is explosive.
(c)
i. State the average oxidation state of the nitrogen atom in ammonium nitrate (NH4NO3).
ii. If we consider the ammonium ion (NH4+) and nitrate ion (NO3-) separately, what is the
oxidation number of nitrogen in NH4+ ion and NO3- ion respectively.
iii. Why is the oxidation number of nitrogen atom in part (i) different from part (ii)?
(d) Identify the oxidizing agent and the reducing agent in the above reaction? Explain your
answer.
5. Arrange the following compounds in order of increasing oxidation state for the carbon
atom.
CO , CO2 , H2CO , CH3OH , CH4
Extra Practice Questions

Chemistry (9th edition) by Raymond Chang, Chapter 4.8
Redox Reactions: Page 161 Questions 4.99, 4.116, 4.129, 4.131, 4.135
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Lesson 1.2 Balancing Redox Equations

Redox reactions are usually written as balanced ionic equations to obtain
the mole ratio between the oxidizing and reducing agent.
In balancing ionic equations, check that:
• the number of atoms balance on both sides of the equation

• the total charge on both sides of the equation must also be balanced
Although oxidation and reduction must take place simultaneously, it is often

convenient to consider them separately. The balanced half-equation (or ion-
electron equation) for the oxidation process and reduction process are first
written separately.
In the overall balanced ionic equation, the number of electrons lost in the
oxidation process must equal the number of electrons gained in the reduction
process. There cannot be electrons in the overall final balanced ionic equation.
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Step by Step Guide to writing balanced ionic equations
1. Redox reactions in an acidic medium
E.g. Balance the equation: MnO4-(aq) + Fe2+(aq) → Mn2+(aq) + Fe3+(aq)
Steps Reduction half equation Oxidation half equation

1.
Write the skeletal half MnO4-(aq) → Mn2+(aq) Fe2+(aq) → Fe3+(aq)
equation
2.
• Balance the elements
other than O and H
• Balance the O by adding MnO4-(aq) → Mn2+(aq) + NA

H2O as needed 4H2O(l)
• Balance the H by adding MnO4-(aq) + 8H+(aq)

H+ → Mn2+(aq) + 4H2O(l)
3.
Balance the total charge by MnO4-(aq) + 8H+(aq) + 5e- Fe2+(aq) → Fe3+(aq) + e-
adding electrons → Mn2+(aq) + 4H2O(l)
4.
Multiply each half equation MnO4-(aq) + 8H+(aq) + 5e- [Fe2+(aq) → Fe3+(aq) + e- ] x5
with the appropriate integer → Mn2+(aq) + 4H2O(l)
so that the number of
electrons lost in the oxidation
half equation equals the
number of electrons gained in
the reduction half equation
5.
Add the two half-equations MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) + 4H2O(l)
and simplify by considering 5Fe2+(aq) → 5Fe3+(aq) + 5e-
the net of the species MnO4-(aq) + 8H+(aq) + 5Fe2+(aq)
appearing on both sides of the → Mn2+(aq) + 4H2O(l) + 5Fe3+(aq)
combined equation
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2. Redox reactions in an alkaline medium
In an alkaline medium, half equations are balanced using OH- and H2O but
balancing is difficult because OH- has both hydrogen and oxygen atoms. To
simplify balancing the equation, the half equations are initially balanced as
though it is in an acid medium.
E.g. Balance the equation: MnO4-(aq) + Fe2+(aq) → MnO2(s) + Fe3+(aq)
In an alkaline medium, KMnO4 is not as powerful an oxidizing agent as it is in

the acidic medium. Hence, itself is reduced to MnO2 and not Mn2+.
Steps Reduction half equation Oxidation half equation

1.
Balance as though it is in an MnO4-(aq) + 4H+(aq) + 3e- Fe2+(aq) → Fe3+(aq)
acid medium (Steps 1 – 3 in → MnO2(s) + 2H2O(l)
previous table)
2.
Add the number of OH- MnO4-(aq) + 4H+(aq) + 3e-+ 4OH-
needed to ‘neutralize’ the H+ (aq)
to both sides of the equation. → MnO2(s) + 2H2O(l) -+ 4OH(aq)
NA
H+ neutralizes the OH- to give MnO4-(aq) + 4H2O (aq) + 3e-
H2 O → MnO2(s) + 2H2O(l) + 4OH-(aq)
Write the net number of H2O MnO4-(aq) + 2H2O (aq) + 3e-

remaining → MnO2(s) + 4OH-(aq)
3.
Continue with Steps 4 – 5 in MnO4-(aq) + 2H2O (aq) + 3e- [Fe2+(aq) → Fe3+(aq) + e-] x3
previous table. → MnO2(s) + 4OH-(aq)
MnO4-(aq) + 2H2O (aq) + 3e- → MnO2(s) + 4OH-(aq)

3Fe2+(aq) → 3Fe3+(aq) + 3e-
MnO4-(aq) + 2H2O (aq) + 3Fe2+(aq)
→ MnO2(s) + 4OH-(aq) + 3Fe3+(aq)
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Complete and balance the following disproportionation reactions.
i. MnO42-(aq) → MnO4-(aq) + MnO2(s) in an acid medium
Answer:
3MnO42(aq) + 4H+(aq)→
2MnO4(aq)+MnO2(s)+2H2O(l)
ii. Cl2(aq) → Cl-(aq) + ClO-(aq) in an alkaline medium
Answer:
Cl2(aq) + 2OH-(aq) →
Cl-(aq)+ClO-(aq)+H2O(l)
END OF LESSON CHECKLIST
Are you able to:
explain redox processes in terms of electron transfer and/or of changes in oxidation

number (oxidation state)
recall the common laboratory oxidising and reducing agents and their respective colour
changes
write balanced half equations and the overall equation
write balanced disproportionation equations
Reference
1. Chemistry, The Central Science (Brown), 10th Edition, Chapter 20 Pages 846-855
2. Chemistry (Raymond Chang), 9th Edition, Chapter 19 Pages 820 - 822
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DIY Questions
1. Complete and balance the following redox reactions.
(a) H2O2 + Fe2+ Fe3+ + H2O (in acidic solution)

(b) Cu + HNO3 Cu2+ + NO +H2O (in acidic solution)
(c) CN- + MnO4- CNO- + MnO2 (in basic solution)
(d) S2O32- + I2 I- + S4O62- (in acidic solution)
(e) Mn2+ + H2O2 MnO2 + H2O (in basic solution)
(f) Bi(OH)3 + SnO22- SnO32- + Bi (in basic solution)
(g) Cr2O72- + C2O42- Cr3+ + CO2 (in acidic solution)
(h) ClO3- + Cl- Cl2 + ClO2 (in acidic solution)
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2. The SO2 present in air is mainly responsible for the acid rain phenomenon. Its concentration can
be determined by titrating against standard potassium manganate (VII) solution as follows:
2MnO4-(aq) + 5SO2(g) + 2H2O(l) → 2Mn2+(aq) + 5SO42-(aq) + 4H+(aq)
Calculate the mass of SO2 in a sample of air if 7.37 mL of 0.00800M KMnO4 solution is required
for titration.
3. Ethanedioate ions, C2O42-, are oxidized by acidified aqueous potassium manganate (VII).
2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq) → 2Mn2+(aq) + 10CO2(g) + 8H2O(l)
What volume of 0.020 mol dm-3 potassium manganate (VII) is required to oxidize completely
1.0 x 10-3 mol of the salt KHC2O4.H2C2O4?
4. Sodium thiosulphate is used in the textile industry to remove an excess of chlorine from
bleaching processes by reducing it to chloride ions.
S2O32-(aq) + 4Cl2(aq) + 5H2O(l) → 2HSO4-(aq) + 8H+(aq) + 8Cl-(aq)
In this reaction, how many moles of electrons are supplied per mole of thiosulphate?
5. A 1 cm length of iron wire is dissolved in acid. The solution obtained was titrated with 0.0250 M
K2Cr2O7 solution and 10.50 cm3 of oxidant solution was required to reach the end point.
Calculate the mass of iron in the wire.
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6. Liquid household bleach contains sodium hypochlorite (NaOCl) as its active ingredient. The
manufacturer maintains quality control by performing volumetric analysis on random samples
taken from the end of the production line. In the analytical laboratory a 25.00 mL sample was
diluted to 250.0 mL using distilled water. 20.00 mL aliquots were then pipetted into clean
conical flasks and excess acidified potassium iodide solution was added to each flask to cause
the reaction: ClO- + 2I- + 2H+ → Cl- + I2 + H2O
The free iodine was then titrated with 0.1000 M sodium thiosulfate solution (Na2S2O3), using
starch indicator solution. This indicator gives a dark blue-black colour in the presence of iodine.
The titration reaction is represented by: 2S2O32- + I2 → 2I- + S4O62-
The average titre was 20.42 mL.
(a) What is the oxidation state of Cl in Cl- and ClO-?
(b) Explain whether sodium hypochlorite acts as an oxidant or reductant when it is mixed with
potassium iodide solution.
(c) What colour change is observed at the end point of the titration?
(d) What amount of sodium thiosulfate, in mol, was used in the titration with the free iodine?
(e) What amount of iodine (I2), in mol, was released by the reaction of the sodium
hypochlorite?
(f) Deduce the amount, in mol, of sodium hypochlorite present in each 20.00 mL aliquot of
diluted bleach solution.
(g) What amount of sodium hypochlorite, in mol, was present in the original 25.00 mL sample
of household bleach?
(h) What mass of sodium hypochlorite was present in the original 25.00 mL sample of the
household bleach?
(i) What is the concentration of sodium hypochlorite in g L-1?

Chemistry (9th edition) by Raymond Chang, Chapter 4.8
Redox Reactions: Page 161 Questions 4.99, 4.116, 4.129, 4.131, 4.13
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Challenging Question
Empirical Formula of Argyrodite
The mineral Argyrodite is a stoichiometric compound that contains silver (oxidation state +1),
sulphur (oxidation state -2) and an unknown element Y (oxidation state +4). The ratio between the
masses of silver and Y in Argyrodite is m(Ag) : m(Y) = 11.88 : 1. Y forms a reddish brown lower
sulphide (oxidation state of Y is +2) and a higher white sulphide (oxidation state of Y is +4). The
coloured lower sulphide is the sublimate obtained by heating Argyrodite in a flow of hydrogen. The
residues are Ag2S and H2S. To convert 10.0 g of Argyrodite completely, 0.295 L of hydrogen are
needed at 400 K and 100 kPa.
Determine the molar mass of Y from this information. Give the chemical symbol of Y, and the
empirical formula of Argyrodite.
[IChO Prep]
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Lesson 2.1 Standard Electrode Potentials and Galvanic Cells

1. Electrolytes
An electrolyte is a compound that will conduct electricity when in

an aqueous or molten state. It is able to conduct an electric current
due to the presence of mobile ions which are the charge carriers.
• Strong electrolytes are fully ionized when molten or in an What is a strong

aqueous solution, e.g. ionic compounds and some covalent electrolyte? Weak
compounds such as HCl(aq) and HNO3(aq). electrolyte? Non-
electrolyte?
• Weak electrolytes are partially ionized when in solution, e.g.
weak organic acids (aq CH3COOH) and bases (aq NH3).
• Non-electrolytes do not ionize and do not conduct electricity, e.g.

non-polar organic compounds – hexane(l), benzene(l), CCl4(l) and
sucrose(l).
2. Electrode Potentials
When a strip of metal is placed in a solution of its ions, e.g. Zn rod in aq

ZnSO4 (known as a zinc half-cell), a dynamic equilibrium is established
at the metal surface.
M(s) ⇌ M2+(aq) + 2e- ……….
(a) For metals that are easily oxidized (more reactive metals), e.g. Zn
- the position of equilibrium lies to the right

- there is a net tendency for the Zn metal to dissolve to form Zn2+
Zn(s) ⇌ Zn2+(aq) + 2e-
This results in
- a build-up of electrons on the metal resulting in the Zn electrode
becoming negatively charged
- a high concentration of Zn2+ ions in the solution around the metal
The separation of charge results in a potential difference between

the metal and its solution, known as the electrode potential of the
metal.
(b) For a less reactive metal, such as in a copper half-cell which

consists of a Cu rod dipped in a solution of Cu2+ ions,
- the position of equilibrium lies to the left

- there is a net tendency for the Cu2+ in solution to be reduced
(conc. of Cu2+ decreases)
- electrons are used up and the Cu electrode becomes positively
charged
Cu2+(aq) + 2e- ⇌ Cu(s)
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3. Measurement of the Electrode Potential of a Half-Cell
The measurement of electrode potential of a half-cell requires a

standard electrode as reference electrode.
The reference electrode used is the standard hydrogen electrode (SHE)

which is arbitrarily assigned a value of 0 V.
Platinized Platinum
electrode is used.
Platinum electrode
coated with finely-divided
platinum) to increase the
+
[H (aq)] = 1.0M surface area for a rapid
establishment of
2H+(aq) + 2e- ⇌ H2(g)
equilibrium
Also, the electrode potential value is affected by
i. Temperature
ii. Concentration of ions in the aqueous solution
iii. Partial pressure of the gas - If a gas is involved in the half-cell,
e.g. 2H+(aq) + 2e- ⇌ H2(g)
Thus, the measurement of the electrode potential of a half-cell must be

specified under standard conditions.
The standard electrode potential, Eθ, of any half-cell is defined as the

potential of that half-cell relative to a standard hydrogen half-cell,
under standard conditions:
• at 298 K
• conc. of aq ions = 1.0 M
• partial pressure of gas (if present) = 1 atm
• Pt is the electrode if the half-cell does not include a
metal
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(a) To measure the standard electrode potential of a Zn half-cell,

θ
E Zn 2+ / Zn
1. Set up a Zn half-cell (Zn electrode immersed in a 1.0 M solution of

Zn2+(aq)) connected to a standard hydrogen electrode.
2. The two half-cells are connected by a salt bridge.
o The salt bridge (an inverted U tube) containing a strong

electrolyte solution such as KCl or NH4NO3 solution. The
openings of the U tube are loosely plugged with cotton balls to
prevent the KCl solution from flowing into the containers.
o The electrolytic solution in the salt bridge conducts

electricity through the movement of ions in the bridge but What is the function(s) of
does not allow mixing of the solutions in the 2 half-cells. salt bridge?
o Thus, the salt bridge is for the transfer of ions from the
electrolyte to the half-cells to prevent an accumulation of
charge at each electrode during the operation of the cell and
hence maintain electrical neutrality.
E.g. As Zn is oxidized, there is a build-up of positive ions

(Zn2+) in the solution in the zinc half-cell. The Cl- ions in the
salt bridge migrates towards the Zn half-cell and in this way
reduces the charge gradient in the solution. Similarly as
H+(aq) in the hydrogen half-cell is reduced, the drop in the
concentration of positive ions is prevented as K+ ions in the
salt bridge migrates to the hydrogen electrode.
o Without the salt bridge connecting the two solutions, the

build-up of positive charge in the Zn half-cell (due to
formation of Zn2+ ions) and the negative charge in the
hydrogen half-cell (due to reduction of H+ ions to H2) would
quickly prevent the cell from operating.
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3. Electrons flow externally from the Zn electrode (anode) to the Electrons CANNOT flow
platinum electrode (cathode) through the wire and high in solution only mobile
resistance voltmeter. ions can!!!
The reading on the voltmeter gives the standard electrode potential

for the Zn half-cell since the standard hydrogen electrode has been
assigned the value of 0.0 V.
(b) To measure the standard electrode potential of a Fe3+/Fe2+ half-

θ
cell, E Fe3+ / Fe 2 +
Standard Electrode Potential
The standard electrode potentials of a large number of half-cells are Refer to Lesson Notes
measured under standard conditions relative to the standard hydrogen Pg.vii & viii
electrode and are tabulated.
• By convention, the half equations are written as reduction

processes (hence are also known as standard reduction
potentials)
e.g. I2(s) + 2e- ⇌ 2I-(aq) Eθ = + 0.53 V
• The half-cell reactions are reversible.
• Species on the left-hand side of the equilibrium arrow are

reduced; thus in a redox reaction, act as oxidizing agents.
• Species on the right-hand side of the equilibrium arrow are

oxidized; thus in a redox reaction, act as reducing agents.
20 | S e m e s t e r 2
• When the electrode potentials are written as oxidation half

equations, the electrode potential values take on the opposite
sign.
e.g. 2I-(aq) ⇌ I2(s) + 2e- Eθ = - 0.53 V
To avoid confusion by sometimes writing the electrode potentials as

reduction and sometimes as oxidation potentials, we will always read Eϑ
values as reduction processes.
• Changing the stoichiometric coefficient does not affect the value of

Eθ.
IMPORTANT!!!
e.g. I2(s) + 2e- ⇌ 2I-(aq) Eθ = + 0.53 V
2I2(s) + 4e- ⇌ 4I-(aq) Eθ = + 0.53 V
4. Relationship between Standard Reduction Potential (Eθ ) and

Strength of Oxidizing or Reducing Agent
Compare:
Cu2+(aq) + 2e- ⇌ Cu(s) Eθ = + 0.34 V
Zn2+(aq) + 2e- ⇌ Zn(s) Eθ = - 0.76 V
- The more positive the Eθ value, the more thermodynamically
favorable is the reaction!
- Thus, the more positive the Eθ value, the stronger the left-
hand side species is an oxidizing agent.
- More positive Eϑ value ⇒ Cu2+ is more likely to be reduced than

Zn2+. Thus, Cu2+(aq) is a stronger oxidizing agent than Zn2+(aq).
Reducing agents are on the right hand side of the equilibrium

arrow. The more negative the Eθ value, the stronger the
right-hand side species is a reducing agent.
- Applying the same principle as above, Zn(s) is more likely to be

oxidized than Cu(s).
- Thus, Zn(s) is a stronger reducing agent than Cu(s).
21 | S e m e s t e r 2
θ
5. Standard Cell Potential, E cell of an Electric Cell (or Galvanic Cell
or Voltaic Cell)
When a zinc half-cell is connected to a copper half-cell by an external

circuit, it allows the flow of electrons from the zinc electrode to the copper
electrode. The two half-cells combine to make an electric cell.
At the zinc electrode: At the copper electrode:
- oxidation takes place - reduction takes place

Zn(s) → Zn2+(aq) + 2e- Cu2+(aq) + 2e- → Cu(s)
- is the anode - is the cathode
- is the negative terminal - is the positive terminal
If the bulb is replaced by a high resistance voltmeter, the cell voltage or

electromotive force (emf) measured is the potential difference between
the Zn half-cell and the Cu half-cell.
Given any two half cells are connected together (e.g. Zn2+/Zn and Cu2+/Cu),
how can we predict the spontaneous reaction taking place from the From the two Eθ values,
recall that the more
standard reduction potential values?
positive value indicates
the process in the
Cu2+(aq) + 2e- ⇌ Cu(s) Eθ = + 0.34 V forward direction is more
likely.
Zn2+(aq) + 2e- ⇌ Zn(s) Eθ = - 0.76 V
Thus, when these two
half-cells are connected,
The two processes taking place are the likely process taking
place at the Cu half-cell is
Cu2+(aq) + 2e- → Cu(s) the reduction process:
Cu2+(aq) + 2e- → Cu(s)
Zn(s) → Zn2+(aq) + 2e-
If reduction occurs at the
Overall reaction Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Cu half-cell, then
OXIDATION MUST TAKE
PLACE at the Zn half-cell.
22 | S e m e s t e r 2
REMEMBER THIS!
OARC : Oxidation at Anode; Reduction at Cathode
• The half-cell with the more positive Eθ value is the reduction

half-cell.
• The half-cell with the less positive (or more negative) Eθ value
is the oxidation half-cell.
The zinc electrode in this cell, where oxidation takes place, is the anode. It
is the negative electrode because electrons are produced.
The copper electrode in this cell, where reduction takes place, is the
cathode. It is the positive electrode because electrons are consumed.
θ
The standard cell potential, E cell , is the potential difference between the
two half-cells under standard conditions. It measures the electromotive
force (emf) that causes electrons to flow in a circuit.
θ θ θ
E cell = E red ( reduction process ) − E red (oxidation process ) For the Daniell Cell, the
cell potential:
θ
or E cell = +0.34 - (-0.76)
= +1.10 V
θ θ θ
E cell = E cathode - E anode
NOTE: For a thermodynamically favored reaction, the cell voltage,

θ
E cell is always positive.
23 | S e m e s t e r 2
The Daniell Cell (or any other galvanic cell) can be represented by a
conventional notation called the cell diagram.
It is assumed that the cell is operating under standard conditions (aqueous

solutions are of concentration 1.0 M, 298 K, 1 atm), and by convention, is
written with anode, on the left, to cathode, on the right.
The cell diagram for the Daniell Cell is:
Zn(s) | Zn2+(1M) || Cu2+(1 M) | Cu(s)
| : represents a phase
boundary, e.g. Zn || : denotes a salt bridge
solid to aqueous Zn2+
Write the cell diagram notation for the following voltaic cells:
Fe3+ + e- ⇌ Fe2+ + 0.77 V Cl2 + 2e- ⇌ 2Cl- + 1.36 V

Half- Sn2+ + 2e- ⇌ Sn - 0.14 V MnO4- + 8H+ + 5e- ⇌ Mn2+ + 4H2O +1.52 V
cells
Anode: Anode:
Sn Sn2+ + 2e- 2Cl- Cl2 + 2e-
Cathode: Cathode:
Fe3+ + e- Fe2+ MnO4- + 8H+ + 5e- Mn2+ + 4H2O
Cell
diagram
notation Overall reaction: Overall reaction:
Sn + 2Fe3+ Sn2+ + 2Fe2+ 10Cl- +2MnO4- + 16H+5Cl2 + 2Mn2++8H2O
Cell diagram: Cell diagram:

Sn(s)|Sn2+(aq)||Fe3+(aq),Fe2+(aq)|Pt(s) Pt(s)|Cl-(aq)|Cl2(g)||MnO4-,H+(aq),Mn2+(aq)
|Pt(s)
24 | S e m e s t e r 2
6. Batteries and Fuel Cells
A battery is a self-contained electrochemical power source that contains

one or more voltaic cells. Batteries are based on variety of different redox
reactions. Lead-acid battery, nickel-cadmium battery and lithium-ion
battery are the common examples of rechargeable batteries. The alkaline
dry cells are not rechargeable.
Lead-acid battery Alkaline dry battery

(source: catalog.flatworldknowledge.com)
Fuel cells are voltaic cells that utilize redox reactions in which reactants
(such as H2 in Hydrogen fuel cell) have to be continuously supplied to the
cell to generate voltage.
Hydrogen fuel cell

(source: www.almc.army.mil)
25 | S e m e s t e r 2
DIY Questions
1. Given the following notation for an electrochemical cell:
Pt(s) | H2(g) | H+(aq) || Ag+(aq) | Ag(s)
What is the balanced overall (net) cell reaction?
A. 2H+(aq) + 2Ag+(aq) → H2(g) + 2Ag(s)

B. H2(g) + 2Ag(s) → H+(aq) + 2Ag+(aq)
C. 2H+(aq) + 2Ag(s) → H2(g) + 2Ag+(aq)
D. H2(g) + Ag+(aq) → H+(aq) + Ag(s)
E. H2(g) + 2Ag+(aq) → 2H+(aq) + 2Ag(s)
2. Consider an electrochemical cell constructed from the following half cells, linked by an
external circuit and by a KCl salt bridge.
• an Al(s) electrode in 1.0 M Al(NO3)3 solution

• a Pb(s) electrode in 1.0 M Pb(NO3)2 solution
The balanced overall (net) cell reaction is
A. Pb(s) + Al3+(aq) → Pb2+(aq) + Al(s)

B. 3Pb(s) + 2Al3+(aq) → 3Pb2+(aq) + 2Al(s)
C. 3Pb2+(aq) + 2Al(s) → 3Pb(s) + 2Al3+(aq)
D. Pb2+(aq) + Al(s) → Pb(s) + Al3+(aq)
external circuit and a KCl salt bridge.
• an Al(s) electrode in 0.5 M Al2(SO4)3 solution

• a Pb(s) electrode in 1.0 M Pb(NO3)2 solution
Which electrode is the anode?
A. Al
B. Pb
C. neither
26 | S e m e s t e r 2
external circuit and a KCl salt bridge.
• a Fe electrode in 1.0 M FeCl2 solution

• a Sn electrode in 1.0 M Sn(NO3)2 solution
When the cell is running spontaneously, which choice includes only true statements and no
false ones?
A. The tin electrode loses mass and the tin electrode is the cathode.
B. The tin electrode gains mass and the tin electrode is the cathode.
C. The iron electrode gains mass and the iron electrode is the anode.
D. The iron electrode loses mass and the iron electrode is the cathode.
E. The iron electrode gains mass and the iron electrode is the cathode.
5. Calculate the value of E°cell for the following reaction: [ Eo(Au3+/Au) = + 1.50V ]
2Au(s) + 3Ca2+(aq) → 2Au3+(aq) + 3Ca(s)
A. - 4.37 V
B. - 1.37 V
C. - 11.6 V
D. +1.37 V
E. +4.37 V
6. For the reaction, 2Cr2+ + Cl2(g) → 2Cr3+ + 2Cl-, E°cell is +1.78 V.
Calculate E°cell for the related reaction Cr3+ + Cl- → Cr2+ + ½Cl2(g).
A. +1.78 V
B. +0.89 V
C. - 1.78 V
D. - 0.89 V
E. none of the above
7. The overall reaction 2Co3+(aq) + 2Cl-(aq) → 2Co2+(aq) + Cl2(g) has the standard cell voltage
E°cell= +0.46 V.
Calculate the standard reduction potential for the following the half reaction at 25°C:
Co3+ + e- → Co2+
A. +1.82 V
B. - 0.90 V
C. +0.90 V
D. - 1.82 V
E. - 1.36 V
27 | S e m e s t e r 2
8. Consider an electrochemical cell based on the following cell diagram:
Pt | Pu3+(aq), Pu4+(aq) || Cl2(g) | Cl-(aq) | Pt
Given that the standard cell emf is +0.35 V and that the standard reduction potential of
chlorine is 1.36 V, what is the standard reduction potential E°(Pu4+/Pu3+)?
A. +2.37 V
B. +1.01 V
C. - 1.71 V
D. - 1.01 V
E. +1.71 V
9. Consider the following standard reduction potentials in acid solution:
Which is the weakest oxidizing agent in this list?
A. Al3+(aq)
B. Al(s)
C. I-(aq)
D. I2(s)
E. Sn4+(aq)
10. Consider the following standard reduction potentials in acid solution:
The strongest reducing agent among those shown above is
A. Fe3+
B. Fe2+
C. Br-
D. Al3+
E. Al
28 | S e m e s t e r 2
11. Calculate the standard emf of a cell that uses Ag/ Ag+ and Al/ Al3+ half-cell reactions at 25°C.
Write the cell reaction that occurs under standard-state conditions.
12. A voltaic cell is constructed with the two electrodes connected by an external circuit. One
electrode compartment consists of a silver strip in a solution of AgNO3, and the other has an
iron strip placed in a solution of FeCl2. The two solutions are connected by a KCl(aq) salt
bridge. The overall cell reaction is
Fe(s) + 2Ag+(aq) Fe2+(aq) + 2Ag(s)
(a) What is being oxidized, and what is being reduced?
(b) Write the half-reactions that occur in the two electrode compartments.
(c) Which electrode is the anode, and which is the cathode?
(d) Indicate the signs of the electrodes.
(e) Do electrons flow from the silver to iron electrode or from the iron to the silver
electrode?
(f) In which directions do the K+ cations and Cl- anions migrate in the salt bridge during
discharge?
13. A Leclanché cell consists of a zinc anode and a carbon cathode coated with MnO2 in an acid
paste. During discharge, MnO2 is converted to Mn2O3.
(a) Write the ion-electron equations for the reaction which occurs during discharge (when
the battery is operating) at the anode and cathode respectively.
(b) The voltage of this Leclanché cell is found to be 1.5 V. With reference to the Standard
Reduction Potential values, calculate Eo(MnO2/Mn2O3)
29 | S e m e s t e r 2
14. Direct-methanol fuel cells make use of methanol as the fuel to generate energy. They are
limited in the power they can produce, but can still store high energy content in a small
space. The electrolyte in this fuel cell is a dilute aqueous acid.
(a) Write the ion-electron equations for the reaction which occurs during discharge (when
the battery is operating) at the anode and cathode respectively.
(b) What is the function of the proton exchange membrane?
(c) What is the direction of electron flow in the external circuit?

Chemistry (9th edition) by Raymond Chang, Chapter 19
Galvanic Cells and Standard Emfs: Page 855 Questions 19.11 – 12; 19.61 – 19.66; 19.68
30 | S e m e s t e r 2
Challenging Questions
Electrochemistry: Nicad batteries
1. Sealed type Ni – Cd batteries (“Nicad”) are widely used in portable devices such as cordless
power tools, cellular telephones, camcorders, portable computers, etc. Ni –Cd batteries are cost-
effective and have high cycle lives and excellent low or high temperature performance. They
require no maintenance and can be recharged up to 2000 times. A typical sealed type Ni – Cd cell
consists of the following two half-cells:
Cd(OH)2(s) + 2e− ⇌ Cd(s) + 2OH− Eo1 = − 0.809 V

2NiO(OH)(s) + 2H2O + 2e− ⇌ 2Ni(OH)2(s) + 2OH− Eo2 = −0.490 V
where Eo1 , Eo2 are standard reduction potentials at 25oC.
(a) Which reaction occurs at the cathode? Give the corresponding Nernst equation for the
potential.
(b) Which reaction occurs at the anode? Give the corresponding Nernst equation for the
potential.
(c) Write a balanced equation that shows the reaction that occurs spontaneously as the cell
discharges.
(d) Calculate the electromotive force E of the cell at 25oC.
(e) What is the mass of Cd contained in a cellular telephone Ni – Cd battery of a nominal

capacity of 700 mA h?
[IChO prep question]
31 | S e m e s t e r 2
Electrochemical Energy Conversion
2. Mobility is of vital importance for our modern society. Electric cars are under active
development to ensure our future needs of transportation. One of the major problems for
electrically driven vehicles is the supply of a suitable source of electricity. Batteries have the
drawback that they must be recharged, thus the action radius is limited. The in situ generation of
electricity in fuel cells is an attractive alternative. A fuel cell, or flow battery, is a galvanic cell for
which the reactants are continuously supplied. Fuel cells utilize combustion reactions to produce
electricity. The reactants undergo half-reactions at the electrodes, and the electrons are
transferred through an external circuit. The electrodes are separated by an ionically conducting
liquid or a molten or solid electrolyte. The electrode half-reactions for a hydrogen-oxygen fuel
cell with a concentrated potassium hydroxide electrolyte are:
O2(g) + 2H2O + 4e- → 4OH-(aq) (1)

H2(g) + 2OH-(aq) → 2H2O + 2e- (2)
The fuel-cell reaction, after making electron loss equal to electron gain, is:
2H2(g) + O2(g) → 2H2O (3)
The reaction product is water and the efficiency is about 50-60%.
(a) Which reaction occurs at the cathode?

(b) Which reaction occurs at the anode?
(c) Give the electrode reactions when the electrolyte is phosphoric acid.
The change of the Gibbs energy ΔGo is a measure of the driving force of a reaction. The change of
energy is given by: ΔGo = - n F E where n is the number of electrons transferred in the reaction
and F is the Faraday constant (96487 C).
The standard electrode potential for O2(g) at 25 °C is + 1.23 V.
(d) Calculate the ΔGo of the fuel-cell reaction under acidic conditions.
The production of usable energy by combustion of fuels is an extremely inefficient process. In

The Netherlands natural gas is a highly attractive energy source as it is abundantly available.
Modern electric power plants are able to furnish only 35-40% of the energy theoretically
available from natural gas. The exothermic reaction of natural gas (methane) with oxygen is:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) + energy
Usually, the energy released from this reaction is used indirectly to heat houses or to run
machines. However, in a high-temperature ceramic fuel cell based on a solid oxide-ion
conducting electrolyte, natural gas can be utilized directly, without a catalyst and with a high
efficiency of conversion (75%). The net fuel-cell reaction is:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
(e) Give the reactions at the anode and the cathode.
Another high-temperature fuel cell utilizes molten carbonate as the ionically conducting
electroyte. Hydrogen is used as fuel, oxygen is mixed with CO2.
(f) Give the half-reactions at the anode and cathode, and the net fuel-cell reaction.
[IChO prep]
32 | S e m e s t e r 2
Lesson 2.2 Predicting Spontaneity of a Reaction

θ
Predicting Spontaneity of a Redox Reaction using E cell
θ
E cell are used to predict if a redox reaction is feasible.
θ
• If E cell > 0, the reaction is feasible and spontaneous at
standard conditions
θ
• If E cell < 0, the reaction is not feasible and not spontaneous at
standard conditions
To predict if the reaction, 2Ag+(aq) + Sn2+(aq) → 2Ag(s) + Sn4+(aq) is feasible.
Step 1 Keep in mind that Ag+ and Sn2+ are the reactants. 2Ag+(aq) + Sn2+(aq) →
They must always be on the left hand side of the
equation.
Step 2 Look for the relevant half-equations in the table of Ag+ + e- ⇌ Ag +0.80V
standard reduction potentials.
Sn2+ + 2e- ⇌ Sn -0.14V
Sn4+ + 2e- ⇌ Sn2+ +0.15V
Step 3 There are 2 half-equations involving Sn2+. Which will

Pick the be relevant in this case?
correct
reduction It has to be because if Ag+ is reduced, then for a Ag+ + e- ⇌ Ag +0.80V
potential redox reaction to take place, Sn2+ has to be oxidized. Sn + 2e ⇌ Sn +0.15V
4+ - 2+
If is used, then both Ag+ and Sn2+ will be reduced.
Step 4 θ θ
Calculate E cell E cell = +0.80 - (+0.15)
= +0.65 V > 0
θ θ θ
E cell = E red ( reduction process ) − E red (oxidation process )
Reaction is feasible and
spontaneous
As a general guide, if the standard reduction potential values are

arranged in decreasing order (from positive to negative), then
under standard conditions, any species on the left of a given half-cell
reaction will react spontaneously with a species on the right of any
half-cell reaction located below. This principle is known as the
diagonal rule. BUT please use it for your reasoning and NOT quote it
as though it is an explanation (such as “According to the diagonal
rule, xxx reaction is thus thermodynamically favored”).
33 | S e m e s t e r 2
Notice: The standard reduction potential values are arranged

in decreasing order.
Using the set of values provided above, explain the following observations:
(a) Why does iron (III) iodide not exist? Answer:

Consider the spontaneity
of the two reactions:
EΘ(Fe3+/Fe2+) = +0.77V
and EΘ(I2/I-) = +0.54V
Fe3+ will oxidize I- to I2
and itself become reduced
to Fe2+.
(b) Why does a colorless KI solution turn yellow in the presence of acid? Answer:
Consider the spontaneity
of the two reactions:
EΘ(O2, H+/H2O) = +1.23V
and EΘ(I2/I-) = +0.54V. O2
in the air will oxidize I- to
I2 in the presence of acid
giving a yellow colour.
34 | S e m e s t e r 2
θ
Limitations of the use of E cell in predicting the spontaneity of
reactions
θ
1. E cell is a measure of the feasibility of the reaction but it does not
indicate the rate of the reaction.
e.g.
From the following standard reduction potentials, predict if a
solution of Fe2+(aq) prepared in an acidic solution is stable.
O2(g) + 4H+(aq) + 4e- ⇌ 2H2O(l) Eθ = +1.23 V

Fe3+(aq) + e- ⇌ Fe2+(aq) Eθ = +0.77 V
θ
E cell for the reaction:
4Fe2+(aq) + O2(g) + 4H+(aq) → 4Fe3+(aq) + 2H2O(l)
θ
E cell = +1.23 – (+0.77) = + 0.46 V
θ
E cell > 0 V ⇒ A solution of Fe2+(aq) in an acid solution is unstable
as oxygen gas will oxidize it to Fe3+(aq).
Yet the reaction does not take place. It is likely that the activation
energy for the reaction is high thus though the reaction is
thermodynamically feasible, it is kinetically not feasible.
θ
2. E cell values apply only to solutions at standard conditions. It would
not accurately predict the spontaneity of a reaction carried out at
non-standard conditions.
From the following standard reduction potentials, predict if MnO2

can oxidize HCl(aq) to Cl2(g).
Cl2(g) + 2e- ⇌ 2Cl-(aq) Eθ = + 1.36 V

MnO2(s) + 4H+(aq) + 2e- ⇌ Mn2+(aq) + 2H2O(l) Eθ = + 1.23 V
θ
E cell for the reaction:
MnO2(s) + 4H+(aq) + 2Cl-(aq) → Mn2+(aq) + Cl2(g) + 2H2O(l)
θ
E cell = +1.23 – (+1.36) = - 0.13V
θ
E cell < 0 V ⇒ MnO2 is not able to oxidize 1.0 M HCl(aq) to Cl2(g).
But by using concentrated HCl (i.e. under non-standard conditions),
the reaction is feasible.
35 | S e m e s t e r 2
DIY Questions
1. Which one of the following reactions will occur spontaneously at standard-state conditions
and 25°C?
A. Mg2+ + Ca →Mg + Ca2+

B. Ag + K+ → Ag+ + K
C. 2Al3+ + 3Fe → 2Al + 3Fe2+
D. Cu + 2H+ → Cu2+ + H2
2. Using a table of standard electrode potentials, decide which of the following statements is
completely true.
A. Cu2+ can oxidize H2, and Fe can reduceMn2+.

B. Ni2+ can oxidize Cu2+, and Fe2+ can reduce H+.
C. Fe2+ can oxidize H2, and Fe2+ can reduce Au3+.
D. Br2 can oxidize Ni, and H2 can reduceMn2+.
E. H+ can oxidize Fe, and Ni can reduce Br2.
3. Using a table of standard reduction potentials, determine which of these reactions (if any)
is/are nonspontaneous in the direction indicated at 25°C.
A. 2Fe3+ + 2Cl- → 2Fe2+ + Cl2(g)

B. 2Fe3+ + 2Br- → 2Fe2+ + Br2(l)
C. 2Fe3+ + 2I- → 2Fe2+ + I2(s)
D. 2Fe3+ + 2Cl- → 2Fe2+ + Cl2(g) AND 2Fe3+ + 2Br- → 2Fe2+ + Br2(l)
E. All are spontaneous.
4. Which one of the following reagents is capable of transforming Cu2+(1 M) to Cu(s)?
A. I- (1 M)
B. Ni(s)
C. Al3+(1 M)
D. F- (1 M)
E. Ag(s)
5. Which one of the following reagents is capable of transforming Br- (aq) to Br2(l) under -state
conditions?
A. I-(aq)
B. NO3-(aq)
C. Ag+(aq)
D. Al3+(aq)
E. Co3+(aq)
36 | S e m e s t e r 2
6. Which choice lists all of the following species that can oxidize H2O to O2(g) under standard-
state conditions? (2H2O(l) → O2(g) + 4H+(aq) + 4e-)
MnO4-(aq), Cl2(g), Pb2+(aq), Cl- (aq), Ag+(aq)
A. Cl-(aq) only
B. Cl2(g) only
C. Pb2+(aq) and Ag+(aq)
D. Cl-(aq) andMnO4-(aq)
E. MnO4-(aq) and Cl2(g)
7. Consider the following reaction: 2Fe2+(aq) + Cu2+ → 2Fe3+(aq) + Cu.
When the reaction comes to equilibrium, what is the cell voltage?
A. +0.43 V
B. +1.11 V
C. +0.78 V
D. - 0.43 V
E. 0V
8. Predict whether the following reactions will be spontaneous in acidic solution under
standard conditions:
(a) Oxidation of Sn by I2 in the presence of excess aqueous I2. Can Sn2+ be further oxidized to
Sn4+?
(b) Reduction of Ni2+ by I-
(c) Reduction of Ce4+ to Ce3+by H2O2 [Eo (Ce4+/Ce3+) = +1.61V]
(d) Reduction of Cu2+ by Sn2+
37 | S e m e s t e r 2
9. Which of the following reagents can oxidize H2O to O2(g) under standard-state conditions?
H+(aq), Cl-(aq), Cl2(g), Cu2+(aq), Pb2+(aq), MnO4-(aq) in acid
Support your answer with a calculation.
10. The standard reduction potential for the reduction of Eu3+(aq) to Eu2+(aq) is -0.43V.
Which of the following substances is capable of reducing Eu3+(aq) to Eu2+(aq) under standard
conditions: Al, Co, H2O2, V, Cu, I2? Support your answer with a calculation.

Galvanic Cells and Standard Emfs: Page 855 Questions 19.13 – 18
38 | S e m e s t e r 2
Redox reactions
One important analytical methods for estimation of Cu2+ is iodometric titration. In this reaction Cu2+ is
reduced to Cu+ by I- and the liberated I2 is then titrated with standard Na2S2O3 solution. The redox
reaction is as follows:
2Cu2+ + 4I- → 2CuI(s) + I2(aq)
Electrode potentials of the relevant half-cells are:

Cu2+ + e- = Cu+ E° = 0.153 V
-
I2 + 2e = 2I- E° = 0.535 V
(a) Show, from the electrode potential values, if the reduction of Cu2+ by I- is a spontaneous reaction?
However, in iodometric titrations this reaction does take place. Let us try to understand the anomaly:
(b) CuI has low solubility in water with Ksp ~ 1.1 x 10-12. Calculate the effective E° value for the
equilibrium CuI(s) = Cu+ + I-
(c) Using the result in (b), calculate the effective E° value for the reduction of Cu2+ by I-. What does
this value suggest about the spontaneity of the reaction?
(d) Calculate the equilibrium constant of the reduction reaction in (c).
[IChO prep]
39 | S e m e s t e r 2
θ
Lesson 2.3 E cell , ∆Gθ and Keq
EMF and ∆Gθ at standard conditions
∆G: change in Gibbs Free Energy, a measure of the spontaneity of a process

that occurs at constant temperature and pressure.
In a galvanic cell, as a result of the oxidation and reduction processes

taking place, chemical energy is converted to electrical energy.
Electrical energy is the product of the emf of the cell and the total electrical
charge that passes through the cell, which is determined by the number of
moles of electrons that passes through the circuit. Thus,
θ
∆Gθ = - n F E cell
where
- negative sign indicates that electrical work is done by the system

on the surroundings
- n : number of mol electrons that pass through the circuit ( = no of
mol of electrons exchanged in the overall balanced equation)
- F : Faraday constant = 96500 C / mol e-
⇒ 1 Faraday (F) is the electrical charge contained in 1 mol of
electrons
NOTICE THAT:
θ
When a reaction is spontaneous, E cell positive.
This is consistent with the resulting ∆Gθ < 0 for a spontaneous process.
Recall from CM4106, the relationship between ∆Gθ and equilibrium

constant, K.
∆Gθ = - RT ln K
Combining the above equations give,
θ
- n F E cell = - RT ln K
R = 8.31 J/mol K
T (in K)
θ RT F = 96500 C / mol
E cell = ln K
nF
40 | S e m e s t e r 2
θ
Thus, if any one of the three quantities ∆Gθ , K or E cell is known, the other
two can be calculated.
Ecell under non-standard conditions
θ
• Under non-standard conditions, Ecell ≠ E cell
Qualitatively, by applying Le Chatelier’s principle, any condition that

favors the forward reaction will cause Ecell to be more positive and vice
versa.
E.g.
MnO2(s) + 4H+(aq) + 2Cl-(aq) → Mn2+(aq) + Cl2(g) + 2H2O(l)
θ
Eθ = + 1.36 V
- -
E cell = +1.23 – (+1.36) = -0.13V Cl2 + 2e ⇌ 2Cl
MnO2 + 4H+ + 2e- ⇌ Mn2+ + 2H2O Eθ = +1.23 V
Predict qualitatively the effect on Ecell if the following changes are made.
Change made Effect on Ecell Explanation
1. Concentrated HCl
acid is used
2. More MnO2 solid is

used
41 | S e m e s t e r 2
Nernst Equation is a mathematical relationship between the emf of a

galvanic cell and the concentration of reactants and products in a redox
reaction under non-standard state conditions.
Recall from CM4106, the relationship between ∆Gθ at standard conditions

and ∆G at non-standard conditions.
For a general reaction
θ which has not achieved
∆G = ∆G + RT ln Q equilibrium:
where Q: reaction quotient when system is not at equilibrium aA + bB ⇌ cC + dD
θ
Since ∆Gθ = - n F E cell and ∆G = - n F E cell , the equation becomes [C]c[D]d
Q = --------------------
[A]a[B]b
θ
- n F E cell = - n F E cell + RT ln Q
At equilibrium, Q = k
θ RT
Dividing by –nF gives Nernst Equation: E cell = E cell - ln Q
nF
Concentration Cells
Since electrode potential depends on ion concentration, it is possible to

construct a galvanic cell from two half-cells composed of the same
material but differing in ion concentrations. Such a cell is called a
concentration cell.
For example, two nickel electrodes are put into two aqueous solutions of
nickel sulfate at 1.00 X 10-3 M and 1.00 M. The two solutions are connected
by a salt bridge, and the electrodes are joined by an external wire.
Consider these half-equations:
Half-cell 1: Ni2+(aq, 1.00 X 10-3 M) + 2e- ⇌ Ni(s)

Half-cell 2: Ni2+(aq, 1.00 M) + 2e- ⇌ Ni(s)
The two Ni half-cells do not have the same [Ni2+], thus their electrode
potential, E, will not be of the same value.
42 | S e m e s t e r 2
But, according to Le Chatelier’s Principle, a higher Ni2+ concentration

would favor the forward reduction reaction. Thus half-cell 2 would be the
cathode.
Thus, in this concentration cell,

Anode reaction: Ni(s) Ni2+(aq, 1.00 X 10-3 M ) + 2e- For a redox reaction to
take place, half-cell 1
Cathode reaction: Ni2+(aq, 1.00 M) + 2e- Ni(s) must be where oxidation
takes place and be the
anode.
Overall reaction: Ni2+(aq, 1.00 M) → Ni2+(aq, 1.00 X 10-3 M )
In cell diagram notation, this concentration cell is represented as:
Ni(s) | Ni2+(1.00 X 10-3 M) || Ni2+(1.00 M) | Ni(s)
The emf of the cell is calculated using Nernst Equation,
θ RT
E cell = Ecell − ln Q
nF
Q= [Ni
2+(aq),1.00 X 10-3 M ]
E cell = 0 – [(8.314)(298)]/[(2)(96500)] In (1.00 X 10-3/1.00)
[Ni2+(aq), 1.00M]
= 0.0887V
The emf of concentration cells is usually small and decreases continually

during the operation of the cell as the concentrations in the two
compartments approach each other. When the concentration of ions in the
two compartments is the same, E becomes zero and no further change
occurs.
43 | S e m e s t e r 2
Are you able to:
explain the terms of (i) standard electrode potential (ii) standard cell potential?
describe the standard hydrogen electrode (electrode used, [H+], conditions)?
write balanced equations for the reactions that occur at the anode and cathode of a simple cell?
deduce the direction of electron flow from a simple cell, using standard electrode potentials?
construct balanced overall equations from the relevant half-equations?
write the cell notation for simple cell?
calculate a standard cell potential of a simple cell?
ϑ
predict the spontaneity of a reaction from E cell value?
ϑ
state the relationship between Gibbs free energy, equilibrium constant and E cell ?
predict qualitatively how the value of an electrode potential varies with the concentration of the
aqueous ion?
Reference
1. 1. Chemistry, The Central Science (Brown), 10th Edition, Chapter 20 Pages 855- 876
2. 2. Chemistry (Raymond Chang), 9th Edition, Chapter 19 Pages 818- 838
44 | S e m e s t e r 2
DIY Questions
1. Determine the equilibrium constant (Keq) at 25°C for the reaction
Cl2(g) + 2Br-(aq) ⇌ 2Cl-(aq) + Br2(l)
A. 1.5 × 10-10
B. 6.3 × 109
C. 1.3 × 1041
D. 8.1 × 104
E. 9.8
2. Given the following standard reduction potentials:
Calculate the solubility product of AgCN at 25°C.
A. 4.3 × 10-14
B. 2.3 × 1013
C. 2.0 × 10-14
D. 5.1 × 1013
E. none of these
3. For the electrochemical cell Ni(s) | Ni2+(1 M) || H+(1 M) | H2(1 atm) | Pt(s), which one of the
following changes will cause a decrease in the cell voltage?
A. Increase the pressure of H2 to 2.0 atm .

B. Decrease the mass of the nickel electrode.
C. Lower the pH of the cell electrolyte.
D. Decrease the concentration of Ni2+ ion.
E. none of these
4. Consider an electrochemical cell with the following cell reaction where all reactants and
products are at standard-state conditions: Cu2+(aq) + H2(g) → Cu(s) + 2H+(aq).
Predict the effect on the emf of this cell of adding NaOH solution to the hydrogen half-cell
until the pH equals 7.0.
A. The emf will increase.

B. The emf will decrease.
C. No change in the emf will be observed.
45 | S e m e s t e r 2
5. Calculate the cell emf for the following reaction at 25°C:
Ni(s) + 2Cu2+(0.010 M) → Ni2+(0.0010 M) + 2Cu+(1.0 M)
A. 0.40 V
B. -0.43 V
C. 0.43 V
D. 0.34 V
E. 0.37 V
6. Consider an electrochemical cell based on the spontaneous reaction
2AgCl(s) + Zn(s) → 2Ag(s) + 2Cl- + Zn2+
If the zinc ion concentration is kept constant at 1 M, and the chloride ion concentration is
decreased from 1 M to 0.001 M, the cell voltage should
A. increase by 0.06 V.
B. increase by 0.18 V.
C. decrease by 0.06 V.
D. decrease by 0.18 V.
E. increase by 0.35 V.
7. Consider an electrochemical cell involving the overall reaction
2AgBr(s) + Pb(s) → Pb2+ + 2Ag(s) + 2Br-
Each half-reaction is carried out in a separate compartment. The anion included in the lead
half-cell is NO3-. The cation in the silver half-cell is K+. The two half-cells are connected by a
KNO3 salt bridge. If [Pb2+] = 1.0 M, what concentration of Br- ion will produce a cell emf of
0.25 V at 298 K? [AgBr(s) + e- → Ag + Br-, E° = +0.07 V]
A. 0.02 M
B. 0.14 M
C. 0.38 M
D. 1.0 M
E. 7.0 M
8. The measured voltage of the cell Pt(s) | H2(1.0 atm) | H+(aq) || Ag+(1.0 M) | Ag(s) is 1.02 V at
25°C. Calculate the pH of the solution.
A. 1.86
B. 1.69
C. 3.72
D. 3.89
E. 7.43
46 | S e m e s t e r 2
9. If the measured voltage of the cell Zn(s) | Zn2+(aq) || Ag+(aq) | Ag(s) is 1.37 V when the
concentration of Zn2+ ion is 0.010 M, what is the Ag+ ion concentration?
A. 2.5 M
B. 4.0 × 10-9 M
C. 6.2 × 10-3 M
D. 2.6 × 10-51 M
E. 6.1 × 10-5 M
10. Which one of the following reactions must be carried out in an electrolytic cell rather than in
an electrochemical cell?
A. Zn2+ + Ca → Zn + Ca2+
B. Al3+ + 3Br- → Al + (3/2)Br2
C. 2Al + 3Fe2+ → 2Al3+ + 3Fe
D. H2 + I2(s) → 2H+ + 2I-
11. Calculate Eocell and the equilibrium constant for each of the reactions at 298K:
(a) Fe(s) + Ni2+(aq) Fe2+(aq) + Ni(s)
(b) Co(s) + 2H+(aq) Co2+(aq) + H2(g)
(c) 10Br-(aq) + 2MnO4-(aq) + 16H+(aq) 2Mn2+(aq) + 8H2O(l) + Br2(l)
12. Predict whether the following reaction would proceed spontaneously as written at 298 K:
Co(s) + Fe2+(aq) Co2 (aq) + Fe(s)
Given that [Co2+] = 0.15 M and [Fe2+] = 0.68 M.
47 | S e m e s t e r 2
13. A voltaic cell utilizes the following reaction
4Fe2+(aq) + O2(g) + 4H+(aq) 4Fe3+(aq) + 2H2O(l)
(a) What is the emf of this cell under standard conditions?
(b) What is the emf of this cell when [Fe2+] =1.3M, [Fe3+]= 0.01M, PO2= 0.50 atm, and the pH of
the solution in the cathode compartment is 3.50?
14. Cytochrome, a complicated molecule that we will represent as CyFe2+, reacts with the air we
breathe to supply energy required to synthesize adenosine triphosphate (ATP). The body
uses ATP as an energy source to drive other reactions. At pH 7.0, the following reduction
potentials pertain to this oxidation of CyFe2+.
O2(g) + 4H+(aq) + 4e- → 2H2O(l) Eored = +0.82 V

CyFe3+(aq) + e- → CyFe2+(aq) Eored = +0.22 V
(a) What is ∆G for the oxidation of CyFe2+ by air?
(b) If the synthesis of 1.00 mol of ATP from adenosine diphosphate (ADP) requires a ∆G of
37.7 kJ, how many moles of ATP are synthesized per mol of O2?

Thermodynamic Relationships and the Effect of Concentration on Cell Emf: Page 856 Questions 19.21
– 19.26; 19.29 – 34; 19.67, 19.69 – 19.71; 19.73 – 19.74; 19.82; 19.86
48 | S e m e s t e r 2
For a number of years it was not clear whether mercury (I) ions existed in solution as Hg+ or as Hg22+.
To distinguish between these two possibilities, we could set up the following system:
Hg(l) | solution A || solution B | Hg(l)
Where solution A contained 0.263 g mercury (I) nitrate per litre and solution B contained 2.63 g
mercury (I) nitrate per litre. If the measured emf of such a cell is 0.0289 V at 18 oC., what can you
deduce about the nature of the mercury (I) ions?
49 | S e m e s t e r 2
Lesson 3.1 Electrolysis

In contrast to thermodynamically favored redox reactions, which result in
the conversion of chemical energy into electrical energy, electrolysis is the
process in which electrical energy is used to cause a non-spontaneous
reaction to occur.
Electrolysis
What are the main differences in these two cell diagrams?
What is in the Bulb or voltmeter DC source

external circuit?
Energy conversion? Chemical energy Electrical energy Electrical energy Chemical energy
How do you decide

EΘ values Connection to DC source
the anode/cathode?
What is the polarity Anode Cathode Anode Cathode

of anode/cathode? (-) (+) (+) (-)
1. Factors affecting the substances formed/liberated during

electrolysis
i. state of the electrolyte (molten or aqueous state)

ii. nature of the electrodes
Inert electrodes, e.g. C or Pt – they do not take part in the
electrolysis
iii. position of ion in the electrochemical series (Eθ value)
iv. concentration of ions in the electrolyte
50 | S e m e s t e r 2
2. Electrolysis of a molten electrolyte, e.g. M+A-(l), with inert

electrodes
• Whether the electrode is an anode or cathode depends on

whether it is connected to the positive or negative terminal of a
D.C. electric source.
- If the electrode is connected to the + terminal, it is the anode

- If the electrode is connected to the – terminal, it is the cathode
• Consider the mobile ions present in the electrolyte, M+(l) and A-(l)
- The negative ions (A-) will be attracted to the positive terminal

(anode)
- The positive ions (M+) will be attracted to the negative terminal
(cathode)
• At the respective electrodes, the ions will be discharged (lose their

charge)
At the positive (+) terminal At the negative (-) terminal

(anode) (cathode)
Oxidation takes place Reduction takes place

A- → A + e- M+ + e - → M
E.g. Consider the electrolysis of molten NaCl:

(anode) (cathode)
2Cl- → Cl2 + 2e- Na+ + e- → Na
51 | S e m e s t e r 2
3. Electrolysis of an aqueous electrolyte, e.g. M+A-(aq), with inert

electrodes
• Consider the particles present in the electrolyte, M+(aq), A-(aq)

and H2O(l)
• At the respective electrodes, the ion that is preferentially

discharged depends on its Eθ value.

(anode) (cathode)
Either A- or H2O may be oxidized Either M+ or H2O may be reduced
Comparing their Eθ values, Comparing their Eθ values,
O2 + 4H+ + 4e- ⇌ 2H2O + 1.23 V 2H2O + 2e- ⇌ H2 + 2OH- - 0.83 V

A + e- ⇌ A- xxx V M+ + e- ⇌ M xxx V
the species with the less positive the species with the more positive
(or more negative) Eθ value will (or less negative) Eθ value will be
be preferentially oxidized. preferentially reduced.
E.g. Consider the electrolysis of dilute NaCl:

(anode) (cathode)
Either Cl- or H2O may be oxidized Either M+ or H2O may be reduced
O2 + 4H+ + 4e- ⇌ 2H2O + 1.23 V 2H2O + 2e- ⇌ H2 + 2OH- - 0.83 V

Cl2 + 2e- ⇌ 2Cl- + 1.36 V Na+ + e- ⇌ Na - 2.71 V
The species with the less positive Eθ The species with the less negative Eθ
value will be preferentially oxidized, value will be preferentially reduced,
hence hence
2H2O → O2 + 4H+ + 4e- 2H2O + 2e- → H2 + 2OH-
52 | S e m e s t e r 2
4. Electrolysis of an aqueous concentrated electrolyte, e.g. M+A-(aq),

with inert electrodes
• The particles present in the electrolyte, M+(aq), A-(aq) and H2O(l)

are still the same.
• At the respective electrodes, the ion that is preferentially

discharged depends on its Eθ value and its concentration.
E.g. Consider the electrolysis of brine: concentrated aqueous NaCl.

(anode) (cathode)
Either Cl- or H2O may be oxidized Either M+ or H2O may be reduced
O2 + 4H+ + 4e- ⇌ 2H2O + 1.23 V 2H2O + 2e- ⇌ H2 + 2OH- - 0.83 V

Cl2 + 2e- ⇌ 2Cl- + 1.36 V Na+ + e- ⇌ Na - 2.71 V
H2O has a less positive Eθ value and H2O has a less negative Eθ value and
should be preferentially oxidized. will be preferentially reduced.
However the Eθvalue is only slightly In this case, will the higher Na+
less positive, thus due to the higher concentration causes Na+ to be
Cl- concentration, Cl- becomes preferentially reduced?
preferentially oxidized.
Answer: No. Why?
Observation made at the anode: Observation made at the cathode: What observation is
made of the electrolyte as
A pungent yellowish-green gas that A colourless gas that extinguishes a electrolysis of brine
turns blue litmus red and bleaches it. burning splint with a ‘pop’. proceeds?
Gas is Cl2. Gas is H2.
Answer:
Electrolyte becomes more
2Cl- → Cl2 + 2e- 2H2O + 2e- → H2 + 2OH- alkaline. (Due to the
formation of OH- at the
cathode)
53 | S e m e s t e r 2
5. Electrolysis of an aqueous electrolyte, e.g. M+A-(aq), with active

electrodes (any metal more reactive than Pt)
• Consider the particles present in the electrolyte, M+(aq), A-(aq) and

H2O(l)
• At the cathode, the ion (with the more positive Eθ value) in the
electrolyte is preferentially reduced. Whether the electrode is active
or inert has no effect on the substance liberated.
However, at the anode, when an active electrode is used, there is

another possible oxidation process.
Consider the electrolysis of aqueous copper (II) sulphate with copper

electrodes.

(anode) (cathode)
Either SO42- or H2O or the Cu Either Cu2+ or H2O may be reduced

electrode may be oxidized
O2 + 4H+ + 4e- ⇌ 2H2O + 1.23 V 2H2O + 2e- ⇌ H2 + 2OH- - 0.83 V

S2O82- + 2e- ⇌ SO4 2- + 2.01 V Cu2+ + 2e- ⇌ Cu + 0.34 V
Cu2+ + 2e- ⇌ Cu + 0.34 V
the species with the less positive Eθ Comparing their Eθ values, the
value will be preferentially
species with the more positive Eθ
oxidized.
value will be preferentially
reduced.
Hence, the anode reaction is
Hence, the cathode reaction is
Cu(s) → Cu2+(aq) + 2e-
Cu2+(aq)+ 2e- → Cu(s)
What observation are made as electrolysis proceeds?
At the anode? Copper rod gets thinner (smaller mass).
At the cathode? Copper electrode increases in mass.
Aq CuSO4 electrolyte? No change in concentration.
54 | S e m e s t e r 2
6. Application of Electrolysis
(a) Extraction of aluminium metal from its ore, bauxite
Aluminum metal is a reactive metal, extracted from its ore, bauxite The reason why aqueous
(aluminium oxide) by electrolysis. aluminum oxide is not
used is because it is
insoluble in water. Even if
The electrolyte is molten aluminium oxide (Why can’t aqueous aluminium aluminum oxide is
oxide be used?) Unfortunately, alumina has a high melting point (2040 °C) soluble in water, water
and it is not practical to do electrolysis at such a high temperature. Thus, will be preferentially
alumina is dissolved in cryolite, sodium aluminium fluoride - Na3AlF6, reduced.
which melts about 900 °C.
carbon
anodes
molten purified
aluminum oxide +
cryolite
Molten aluminum collects

at the bottom
Electrolyte: Molten purified aluminum oxide in cryolite
Anode Cathode
Carbon anodes - are Carbon anodes

replaced regularly
Electrode because hot O2
produced reacts with
graphit.
Half-equation 2O2- O2 + 4e Al3+ + 3e Al
Overall reaction:
4Al3+ + O2- 4Al + 3O2
55 | S e m e s t e r 2
(b) Anodising of aluminum
Aluminum oxide forms naturally on the surface of aluminum objects and is

impervious to the corroding agents of air and water thus protecting the
aluminum metal beneath the oxide coating.
The thickness of the Al2O3 layer can be increased by reacting the aluminum
object with oxygen gas produced in electrolysis.
The anode is made of

aluminum.
2Al + 3O2 Al2O3
Electrolyte: Dilute sulfuric acid
Anode Cathode
Electrode object to be anodised graphite
Half-equation 2H2O O2 + 4H+ + 4e 2H+ + 2e H2
56 | S e m e s t e r 2
(c) Purification of (or refining) copper
Copper is extracted as blister copper which is a porous brittle form of

copper, about 98 - 99.5% pure. It contains metal impurities such as iron,
zinc, silver etc.
Electrolyte: aq CuSO4
Anode Cathode
Electrode Impure copper rod Pure copper rod
Half-equation Cu(s) Cu2+ (aq) + 2e Cu2+ (aq) + 2e Cu(s)
The impurities found in blister copper are:
(a) metals more reactive than copper e.g. Fe and Zn
What will happen to these impurities at the anode?
These metals will be preferentially oxidized at the anode and enters

the solution as Mn+.
Why does the presence of Zn2+ or Fe2+ in the electrolyte not affect the
purification process?
At the cathode, these metal ions will not be preferentially discharged

because of their less positive EΘ values.
(b) metals less reactive than copper e.g. Ag and Au
What will happen to these impurities at the anode?
These metals will not be oxidized but they will fall to the bottom as
sludge.
57 | S e m e s t e r 2
(d) Electroplating
Electroplating is the coating of an electrically conductive object with a

layer of metal by electrolysis. The result is a thin, smooth, even coat of
metal on the object.
Electrolyte: The solution contains the metal ion of the plating metal
Anode Cathode
Electrode Plating metal Object to be plated
Half-equation M(s) Mn+(aq) + ne Mn+(aq) + ne M(s)
58 | S e m e s t e r 2
DIY Questions
1. Give the equations of the reactions at the cathode and anode for the following electrolytic
cells.
(a) Dilute NaCl(aq) using graphite electrodes
(b) Concentrated NaCl(aq) using graphite electrodes
(c) CuSO4(aq) using graphite electrodes
(d) CuSO4(aq) using copper electrodes
2. Aqueous sulfuric acid is electrolyzed using a graphite anode and an inert cathode.
(a) Give the equations for the reactions at the electrodes.
(b) If an inert anode is used, find the ratio of the products formed.
59 | S e m e s t e r 2
3. Predict the products obtained from electrolysis of a 1 M AlBr3 solution.
Note that
A. Al and Br2
B. Al and O2
C. H2 and O2
D. H2 and Br2
E. Al and H2
4. When an aqueous solution of AgNO3 is electrolyzed, a gas is observed to form at the anode.
The gas is
A. H2
B. O2
C. NO
D. NO2
5. The half-reaction that occurs at the cathode during electrolysis of an aqueous sodium iodide
solution is
A. Na+ + e- → Na
B. Na → Na+ + e-
C. 2H2O + 2e- → H2 + 2OH-
D. I2 + 2e- → 2I-
E. 2I- → I2 + 2e-
6. The half-reaction that occurs at the cathode during electrolysis of an aqueous CuCl2 solution
is
A. Cu2+ + 2e- → Cu
B. Cu2+ + e- → Cu+
C. 2H2O + 2e- → H2 + 2OH-
D. Cl2 + 2e- → 2Cl-
E. 2Cl- → Cl2 + 2e-
7. The half-reaction occurring at the anode during electrolysis of an aqueous copper(II) iodide
solution is
A. I2 + 2e- → 2I-
B. Cu → Cu2+ + 2e-
C. Cu2+ + 2e- → Cu
D. 2I- → I2 + 2e-
E. 2e- + 2H2O → H2 + 2OH-
60 | S e m e s t e r 2
8. Under standard-state conditions, which of the following half-reactions occurs at the cathode
during the electrolysis of aqueous nickel sulfate at 25°C?
A. 2H2O → O2 + 4H+ + 4e-

B. Ni2+ + 2e- → Ni
C. 2H2O + 2e- → H2 + 2OH-
D. Ni → Ni2+ + 2e-
9. The half-reaction that should occur at the anode during electrolysis of an aqueous potassium
bromide solution is
A. Br2 + 2e- → 2Br-.

B. Na → Na+ + e-.
C. Na+ + e- → Na.
D. 2Br- → Br2 + 2e-.
E. 2H2O → O2 + 4H+ + 4e-.
10. Calculate the minimum voltage required for the electrolysis of 1.0 M NaCl in neutral solution.
2H2O + 2Cl- (1.0 M) → H2(1 atm) + Cl2(1 atm) + 2OH- (1 × 10-7 M)
A. 2.19 V
B. 1.78 V
C. 0.41 V
D. -0.41 V
E. -1.78 V
61 | S e m e s t e r 2
Lesson 3.2 Electrolysis – Quantitative Calculations
Quantitative Aspects of Electrolysis
Faraday’s Laws of Electrolysis
1. The mass of substance formed (or volume of gas liberated) is

proportional to the quantity of electricity, Q, passed through the
electrolytic cell and the molar mass of the substance. It does not
depend on the temperature or concentration of the electrolyte.
2. The quantity of electricity required to discharge 1 mol of an element

depends on the charge on the ion.
• The quantity of electricity, Q, (unit: coulombs, C) is the product of

current, i (unit: ampere, A) and time, t (unit: seconds, s).
Q = i x t
where 1 C is the quantity of electrical charge passed in the circuit in 1

s when the current is 1 A.
• The Faraday constant, F, (unit: C/mol) is the electrical charge carried

by 1 mol of electrons.
F = L x e
where
L: Avogadro’s number = 6.02 x 1023 mol-1
e: charge on 1 electron = 1.60 x 10-19 C
F = (6.02 x 1023) x (1.60 x 10-19) = 96500 C/mol
• Q and F are related by
Q Q
F = 96500 =
n n
where n: no. mol of electrons passed through the circuit
62 | S e m e s t e r 2
A current of 4.50 A is passed through an electrolytic cell containing

a solution of copper (II) sulphate for 1.0 h. Write the half-cell reactions and
calculate the mass (or volume at STP, if the product is a gas) of each
substance formed.
Quantity of charge, Q = ______________________________________
No. of mol of electrons passed = ______________________________________________
Anode (+ terminal) Cathode (- terminal)

Half-equation: Half-equation: H2O is preferentially
oxidized than SO42- at the
anode because of the
highly positive EΘ(S2O82-
/SO42-) values.
No. of mol O2 liberated = No. of mol Cu deposited =
Answer:
Q= 16200 C,
n=0.168 mol e,
0.0420 mol and 0.940
Vol of O2 (at STP) liberated = Mass of Cu formed = dm3 O2 (at STP) of
liberate, 0.0839 mol and
5.33 g of Cu deposited,
Metallic magnesium can be made by the electrolysis of MgCl2.
(a) What mass of magnesium is formed by passing a current of 5.25 A

through molten MgCl2 for 2.5 days.
(b) How many minutes are needed to plate out 10.00 g Mg from molten
MgCl2, using 3.50 A of current?
Answer:
(a) 143g
(b) 378 min
63 | S e m e s t e r 2
Are you able to:
predict the identity of the substance liberated during electrolysis from the state of
electrolyte (molten or aqueous), position in the redox series (electrode potential) and
concentration
explain, in terms of the electrode reactions, the industrial processes of (i) the electrolysis of
brine (ii) the electrolytic purification of copper
state the relationship F = Le, between the Faraday constant, the Avogadro constant and the
charge on the electron
calculate the quantity of charge passed during electrolysis
calculate the mass and/or volume of substance liberated during electrolysis
Reference
1. 1. Chemistry, The Central Science (Brown), 10th Edition, Chapter 20 Pages 877- 888
2. 2. Chemistry (Raymond Chang), 9th Edition, Chapter 19 Pages 839- 854
64 | S e m e s t e r 2
DIY Questions
1. A Cr3+ (aq) solution is electrolyzed, using a current of 7.60 A.
(a) What mass of Cr (s) is plated out after 2.00 days?
(b) What amperage is required to plate out 0.250 mol Cr from Cr3+ solution in a period of
8.00 h?
2. A constant electric current flows for 3.75 h through two electrolytic cells connected in series.
One contains a solution of AgNO3 and the second a solution of CuCl2. During this time, 2.00 g
of silver are deposited in the first cell.
(a) How many grams of copper are deposited in the second cell?
(b) What is the current flowing, in amperes?
3. A quantity of 0.300 g of copper was deposited from a CuSO4 solution by passing a current of
3.00 A through the solution for 304 s. Calculate the value of the faraday constant.
4. Chromium plating is applied by electrolysis to objects suspended in a dichromate solution,

according to the following (unbalanced) half-reaction:
Cr2O72-(aq) + e + H+ aq) Cr s) + H2O l)
How long (in hours) would it take to apply a chromium plating 1.0 x 10-2 mm thick to a car
bumper with a surface area of 0.25 m2 in an electrolytic cell carrying a current of 25.0 A? (The
density of chromium is 7.19 g/cm3.)
65 | S e m e s t e r 2
5. In an electrolysis experiment, a student passes the same quantity of electricity through two
electrolytic cells, one containing a silver salt and the other a gold salt. Over a certain period of
time, she finds that 2.64 g of Ag and 1.61 g of Au are deposited at the cathodes. What is the
oxidation state of gold in the gold salt?
6. An aqueous solution of a platinum salt is electrolyzed at a current of 2.50 A for 2.00 h. As a

result, 9.09 g of metallic Pt are formed at the cathode. Calculate the charge on the Pt ions in
this solution.
7. A 300 mL solution of concentrated NaCl was electrolyzed for 6.00 min. If the pH of the final
solution was 12.24, calculate the average current used.
8. An acidified solution was electrolyzed using copper electrodes. A constant current of 1.18 A
caused the anode to lose 0.584 g after 1.52 x 103 s.
(a) What is the gas produced at the cathode and what is its volume at STP?
(b) Given that the charge of an electron is 1.6022 x 10-19 C, calculate Avogadro’s number.
Assume that copper is oxidized to Cu2+.
66 | S e m e s t e r 2
9. How many coulombs of charge are required to cause reduction of 0.20 mole of Cr3+ to Cr?
A. 0.60 C
B. 3.0 C
C. 2.9 × 104 C
D. 5.8 × 104 C
E. 9.65 × 104 C
10. How many faradays are transferred in an electrolytic cell when a current of 2.0 amperes
flows for 12 hours?
A. 24 F
B. 8.6 × 104 F
C. 0.90 F
D. 6.2 × 10 -3 F
E. 1.1 F
11. A metal object is to be gold-plated by an electrolytic procedure using aqueous AuCl3

electrolyte. Calculate the number of moles of gold deposited in 3.0 min by a constant current
of 10A.
A. 6.2 × 10-3 mol

B. 9.3 × 10-3 mol
C. 1.8 × 10-2 mol
D. 3.5 × 10-5 mol
E. 160 mol
12. A current of 0.80 A was applied to an electrolytic cell containing molten CdCl2 for 2.5 hours.
Calculate the mass of cadmium metal deposited.
A. 3.2 × 10-7 g
B. 1.2 × 10-3 g
C. 4.2 g
D. 8.4 g
E. 16.8 g
13. How many grams of nickel would be electroplated by passing a constant current of 7.2 A
through a solution of NiSO4 for 90.0 min?
A. 0.20 g
B. 0.40 g
C. 12 g
D. 24 g
E. 47 g
67 | S e m e s t e r 2
14. How many minutes would be required to electroplate 25.0 grams of chromium by passing a
constant current of 4.80 amperes through a solution containing CrCl3?
A. 483 min
B. 161 min
C. 322 min
D. 2.01 × 104 min
E. 1.11 × 104 min
15. How many coulombs (C) of electrical charge must pass through an electrolytic cell to reduce
0.44 mol Ca2+ ion to calcium metal?
A. 190,000 C
B. 85,000 C
C. 21,000 C
D. 42,500 C
E. 0.88 C
68 | S e m e s t e r 2

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Chemistry Department

CM5106 Inorganic and Electrochemistry

Experiment, Explore, Excel

Lesson 1.1 Oxidation-Reduction Reactions

Oxidation and Reduction

4Al(s) + 3O2(g) → 2Al2O3(s) How are redox

• Understandably, oxidation cannot take place on its own. Another

O atoms in O2 gain electrons to form O2- ions, represented by

• When oxidation-reduction reactions occur, the number of electrons

( Al → Al3+ + 3e- ) x4 … is the oxidation

After doing this

2. Oxidation Numbers (or Oxidation States)

Each atom in the molecule or charged species is assigned an oxidation number

2. Any monoatomic ion, e.g. The oxidation number of Unlike charge, in

• when bonded to non- +1 The oxidation number of H

• when bonded to metals The oxidation number of H

Except in a peroxide -1 The oxidation number of O

5. Fluorine in a compound -1 The oxidation number of F F only has one

3. Definitions of Oxidation and Reduction

In terms of … Oxidation is… Reduction is…

1. oxygen gain of oxygen loss of oxygen

Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g) Definitions 1 and 2

2. hydrogen loss of hydrogen gain of hydrogen

H2S(g) + Cl2(g) → 2HCl(g) + S(s)

H2S is oxidized (since H2S loses hydrogen to become S) &

3. electrons loss of electrons gain of electrons

Cu(s) + 2AgNO3(aq) → Cu(NO3)2(aq) + 2Ag(s)

Cu is oxidized (since Cu loses 2 electrons to become Cu2+) & The exchange of

Reduction half-equation: Ag+ + e- → Ag

4. oxidation Increase in Decrease in

Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)

Mg is oxidized (because the oxidation number of Mg has

Oxidation half-equation: Mg → Mg2+ + 2e-

HCl is reduced (because the oxidation number of H has

Reduction half-equation: 2H+ + 2e- → H2

4. Oxidizing agents (OA) and Reducing agents (RA)

Important examples of common oxidising agents are:

Purple potassium manganate(VII) - KMnO4(aq), which on reaction with What is the

Other oxidizing agents include Cl2 gas or aqueous chlorine - aq Cl2,

• A reducing agent causes another species to be reduced and itself becomes

A common laboratory reducing agent is: I2 is non-polar and is

Hydrogen peroxide(H2O2) can behave as an oxidizing agent and reducing agent.

acidified potassium iron (II) sulphate

The role of H2O2 in the

Cl2 Cl2O ClO4- ClF4-

SrCl2 NaClO Cl2O7 POCl3

ICl NaClO3 ClO2 HClO2

2. Indicate whether each of the following statements is True or False:

(a) If something is oxidized, it is formally losing electrons.

(d) If something is reduced, it is formally losing electrons.

(e) A reducing agent gets oxidized as it reacts.

(f) Oxidizing agents can convert CO into CO2.

3. In each of the following balanced oxidation-reduction equations, identify those elements

(a) I2O5(s) + 5CO(g) I2(s) + 5CO2(g)

(b) 2Hg2+(aq) + N2H4(aq) 2Hg(l) + N2(g) + 4H+(aq)

(c) 3H2S(aq) + 2H+(aq) + 2NO3-(aq) 3S(s) + 2NO(g) + 4H2O(l)

(d) Ba2+(aq) + 2OH-(aq) + H2O2(aq) + 2ClO2(aq) Ba(ClO2)2(s) + 2H2O(l) + O2(g)

__ NH4NO3(s) + __ C17H36(l) → __ N2(g) + __ CO2(g) + __ H2O(g)

(a) Balance the above equation.

(b) Suggest an explanation why this reaction is explosive.

Extra Practice Questions

Lesson 1.2 Balancing Redox Equations

In balancing ionic equations, check that:

• the number of atoms balance on both sides of the equation

NH4NO3(s) + C17H36(l) → N2(g) + CO2(g) + __ H2O(g)

explain redox processes in terms of electron transfer and/or of changes in oxidation

write balanced half equations and the overall equation

write balanced disproportionation equations