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H2 Chemistry 9647

Physical Chemistry (Revision)

Anglo-Chinese Junior College


Department of Chemistry

REDOX & ELECTROCHEMISTRY


(Revision)
Lectured by: Miss Jasmine Zheng

REDOX
A redox reaction consists of two half reactions, reduction and oxidation occurring
simultaneously, i.e. electrons are transferred from the reducing agent to the oxidizing agent.
Hence, in a redox reaction, as one species is oxidised, another species is always reduced.

REDOX REACTION IN TERMS OF ELECTRON TRANSFER


Reduction is defined as the gain of electrons.
Oxidation is defined as the loss of electrons.
Some examples:
Zn(s)

Zn2+ + 2e

Cu2+ + 2e

TIP:
You must be able to
describe and explain redox
processes in terms of
electron transfer and/or of
changes
in
oxidation
number (oxidation state)

Cu(s)

RED = Reducing agent is Electron Donor.

REDOX REACTION IN TERMS OF OXIDATION NUMBER (STATE)


Reduction results in a decrease in the oxidation number (state) of an atom.
Oxidation results in an increase in the oxidation number (state) of an atom.
Oxidation number or state is the charge that an element would have if all the bonds in the
substance were ionic.
Some basic rules:
Uncombined elements are zero.
F is always -1, Group I are +1, Group II +2, oxygen is -2 (except in peroxides), H is +1
(except in metallic hydrides).
Oxidation numbers in a neutral compound add up to zero and in a polyatomic ion they add
up to the charge on that ion.
Some examples:
Zn(s)

Zn2+ + 2e

Cu2+ + 2e

Cu(s)

Oxidation state of Zn increases from 0 to +2.


Oxidation state of Cu decreases from +2 to 0

2015/JC2/Term3/Chem Dept/Physical Chemistry Revision


(Modified from 2011 & 2014 Physical Chemistry Revision (Redox & Electrochemistry)

H2 Chemistry 9647

Physical Chemistry (Revision)

BALANCING REDOX EQUATIONS


Overall redox equations can be obtained by adding half equations. You must check that:
The number of electrons on the left of one half-equation equals the number of electrons on
the right of the other half-equation.
In the overall equation, the total change in oxidation number of the substance being reduced
equals the total change in the substance being oxidized.
Using the Half-Equation Method
General steps to balance a redox reaction (in acidic medium):
1. Identify the two incomplete half-reactions, one for oxidation and the other for reduction.
2. Balance both the half-equations using the following steps:
a. Balance the elements other than H and O
b. Balance oxygen atoms by adding H2O
c. Balance hydrogen atoms by adding H+
d. Balance charges by adding electrons to the side with the greater overall positive
charge.
3. Multiply the balanced half-equations by appropriate integers such that the number of
electrons in both half-equations are equal (electrons gained = electrons lost)
4. Add the resulting half-equations together, and eliminate any common species on both sides
to obtain the overall balanced equation.
Additional steps to balance a redox reaction (in alkaline medium):
5. Use the Steps 1-4 in acidic medium.
6. Add sufficient OH- to both sides of the equation to neutralize any H+ present.
(H+ + OH- H2O)
7. Eliminate electrons and H2O molecules that appear on both sides of the equation.
Using the Half-Equations from the Data Booklet
The overall equation for the oxidation of I- ions by MnO4- ions is obtained from the two half
equations:
MnO4- + 8H+ +5e- Mn2+ + 4H2O
2I- I2 + 2eThe MnO4- half equation has 5 electrons, but the I- equation only 2, so the MnO4- equation has
to be multiplied by 2 and the I- equation by 5, so that both have 10 electrons. They are then
added to give:
2MnO4- + 16H+ +10I- 2Mn2+ + 8H2O + 5I2

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H2 Chemistry 9647

Physical Chemistry (Revision)

Self-Check Assessment (5 minutes)


Q1.

Complete the following half-equations:


(a) Cl- Cl2
(b) Fe3+ Fe2+
(c) MnO4- Mn2+
(d) MnO4- MnO2
(e) C2O42- CO2
(f)
S2O32- S4O62-

Q2.

Combine the following two half-equations:


Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
2I- I2 + 2e-

DISCUSSION QUESTIONS
Q1.

The propellant used in the solid rocket booster of a space shuttle is a mixture of aluminium
and compound X. Compound X contains chlorine in an oxidation state of +7. Which of the
following could be compound X?
A

Q2.

NH4Cl

NH4ClO3

NH4ClO4

Element
Carbon
Nitrogen
Sulphur
Chlorine

Reaction
H2C2O4 H2O + CO + CO2
H2O + 2NO2 HNO3 + HNO2
2FeSO4 Fe2O3 + SO2 + SO3
3ClO- ClO3- + 2Cl-

In an experiment, 25.0 cm3 of a 0.10 mol dm-3 solution metallic salt reacted exactly with
12.5 cm3 of 0.10 mol dm-3 aqueous sodium sulphite. The half equation for the oxidation of
the sulphite ion is shown below.
SO32- (aq) + H2O (l) SO42- (aq) + 2H+ (aq) + 2eIf the original oxidation number of the metal in the salt was 3, what would be the new
oxidation number of the metal?
A

Q4.

N2H5Cl

Disproportionation occurs when an element is both oxidised and reduced in a reaction.


Which named element does not disproportionate in the reaction shown?
A
B
C
D

Q3.

25.0 cm3 of a solution of M2O5 of concentration 0.100 mol dm-3 is reduced by sulphur
dioxide to a lower oxidation state. To reoxidise M to its original oxidation number required
50.0 cm3 of 0.0200 mol dm-3 potassium manganate (VII) solution. To what oxidation
number was M reduced by sulphur dioxide?
A

+2

+3

+4

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+5

H2 Chemistry 9647
Q5.

Physical Chemistry (Revision)

The Winkler method is used to determine the amount of dissolved oxygen in a sample. In
this procedure, oxygen reacts with Mn2+ under alkaline conditions to produce a precipitate
of MnO(OH)2.
2Mn2+ (aq) + O2 (aq) + 4OH (aq) 2MnO(OH)2 (s)
The precipitate is then dissolved in acid and reacted with iodide, forming iodine and Mn2+.
MnO(OH)2 (s) + 2 (aq) + 4H+ (aq) I2 (aq) + Mn2+ (aq) + 3H2O (aq)
Finally, the amount of iodine produced is determined by reaction with thiosulphate.
I2 (aq) + 2 S2O32- (aq) 2I- (aq) + S4O62- (aq)
When a sample of water was analysed using the Winkler method, a total of 0.60 mol of
thiosulphate was used in the reaction. What was the mass of oxygen present in the
original sample?
A

4.8 g

9.6 g

19.2 g

38.4 g

Q6.

A sample of 10.0 cm3 of 0.10 mol dm-3 iron(II) sulfate is titrated against 0.025 mol dm-3
potassium manganate(VII) in the presence of an excess of fluoride ions. It is found that
10.0 cm3 of the manganate(VII) solution is required to reach end-point. What is the
oxidation number of the manganate at the end-point?

Q7.

Sodium thiosulfate is used in the textile industry to remove an excess of chlorine from the
bleaching processes by reducing it to chloride ions:
S2O32- + 4Cl2 + 5H2O 2HSO4- + 8H+ + 8ClIn this reaction, how many moles of electrons are supplied per mole of thiosulphate?

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Physical Chemistry (Revision)

ELECTROCHEMICAL CELL

TIP:
You should be able to define the terms:
(i) standard electrode (redox) potential
(ii) standard cell potential
and describe the standard hydrogen electrode.

Standard electrode potential is defined as the potential difference between a standard


hydrogen electrode and a metal (the electrode) which is immersed in a solution containing
metal ions at 1 moldm-3 concentration at 25 oC and 1 atmospheric pressure.
Standard cell potential is a measure of the tendency of electrons to flow through the external
circuit under standard conditions of 25 oC, 1 atmospheric pressure and 1.00 moldm-3
concentration. It is the maximum potential difference between the electrodes.
Standard hydrogen electrode consists of a platinised electrode in a solution of 1.00 moldm-3
H+ ions (e.g. aqueous HCl)
H2 gas at a pressure of 1 atmospheric pressure is
bubbled over the Pt electrode. On the Pt surface,
equilibrium is set up between the adsorbed layer of H2
(g) and the H+ (aq) ions in solution at 25 oC.
H2 (g)

2H+ (aq) + 2e-

0.00 V

To measure the standard electrode potentials of:


(i)

metals or non-metals in contact with their ions in aqueous solution


e.g. for metals

e.g. for non-metals

TIP:
You should be able to describe methods used to
measure the standard electrode potentials of:
(iii) metals or non-metals in contact with their
ions in aqueous solution
(iv) ions of the same element in different
oxidation states

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H2 Chemistry 9647
(ii)

Physical Chemistry (Revision)

ions of the same element in different oxidation states

Electrochemical cells (Galvanic cells)

To calculate a standard cell potential by combining two standard electrode potentials:


Ecell = Ered (reduction half-cell) - Ered (oxidation half-cell)

TIP:
You should be able to
calculate a standard cell
potential by combining two
standard electrode
potentials

**ALWAYS:
Cathode: reduction
Anode: oxidation
Note:
i) Ered values substituted are as given in the Data Booklet.
ii) Positive Ecell value suggests a thermodynamically feasible reaction. Ecell values give no
information on the reaction rates and apply to standard conditions only.
iii) Electrons flow from the oxidation half-cell to the reduction half-cell in the external circuit.

In this topic, you must:


a) understand the limitations in the use of standard cell potentials to predict the feasibility of a
reaction
b) construct redox equations using the relevant half-equations
c) predict qualitatively how the value of an electrode potential varies with the concentration of the
aqueous ion
d) state the possible advantages of developing other types of cell, e.g. the H2/O2 fuel cell and
improved batteries (as in electric vehicles) in terms of smaller size, lower mass and higher voltage

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Physical Chemistry (Revision)

Electrochemical cell: combination of two half cells to generate/produce electricity (its a


battery!)
e
H2(g) at 1 atm, 25 C

Cu(s) cathode

Pt(s) anode
1 mol dm3 Cu2+(aq)

1 mol dm3 H+(aq)

**ALWAYS:
Cathode: reduction
Anode: oxidation

salt bridge (filter paper soaked in


NaNO3(aq) KNO3(aq))

to determine the direction of electron flow, identify which half-cell loses/gains electrons (look
at the half equation involved)
to determine the polarity of the electrode: "electrons exit from the negative terminal of the
cell and enter into the positive terminal of the cell"
salt bridge - completes the circuit (by allowing charge to move from one half cell to another)
and maintains electrical neutrality (prevents the build up of charges in one half cell)
Anode : H2(g) 2H+(aq) + 2e E (Cu2+|Cu) = +0.34V

Cathode : Cu2+(aq) + 2e- Cu(s)

Daniel cell:
oxidation

reduction

e.g. Pt(s) | H2(g) | H+(aq) || Fe3+(aq), Fe2+(aq) | Pt(s)

cell diagram

(Read from left to right)

H2(g) H+(aq); Fe3+(aq) Fe2+(aq)


H2(g) + 2Fe3+(aq) 2H+(aq) + 2Fe2+(aq)
"|" is used to separate different phases, a comma is used if they are in the same phase
"||" = salt bridge

e.g.

Ecell > 0V energetically feasible;


Ecell < 0V energetically non-feasible
Predict if the following reaction is feasible:
Fe(s) + Zn2+(aq) Fe2+(aq) + Zn(s)
Zn2+(aq) + 2e Zn(s)
Fe2+(aq) + 2e Fe(s)

0.76 V
-0.44 V

Fe(s) + Zn2+(aq) Fe2+(aq) + Zn(s)

Ecell = 0.32 V < 0


energetically non-feasible

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e.g.

Physical Chemistry (Revision)

Which of the following statements are true for a standard cell set up using the half-cells
below?
Ni2+(aq) | Ni(s)
Sn2+(aq) | Sn(s)
1
2
3

E = 0.25 V
E = 0.14 V

Electrons flow in the external circuit from Ni to Sn.


The concentration of Sn2+(aq) will decrease.
Oxidation occurs at the Ni terminal.
V
Sn(s)

Ni(s)

Ni2+(aq)
Consider:
Ni2+ + 2e Ni E = 0.25V
Sn2+ + 2e Sn E = 0.14V

Sn2+(aq)

2+

(more favourable reduction, therefore the Ni /Ni halfcell undergoes oxidation)

Therefore,
Ni Ni2+ + 2e
Sn2+ + 2e Sn
Ni + Sn2+ Ni2+ + Sn
e.g.

Ecell = +0.11 V > 0


energetically feasible

Use the Data Booklet to predict the outcome of mixing acidified potassium
manganate(VII) and aqueous hydrogen peroxide.
MnO4- + 8H+ + 5e- Mn2+ + 4H2O
+1.52V (+7,highest o.s. for Mn-reduction)
+

O2 + 2H + 2e H2O2
+0.68 (H2O2 -oxidation)
_______________________________________________________________
5H2O2 + 2MnO4- + 6H+ 5O2 + 2Mn2+ + 8H2O
Ecell = +0.84 V > 0
energetically feasible

e.g.

Use the Data Booklet to predict the outcome of mixing aqueous tin(II) chloride and
acidified aqueous hydrogen peroxide.
Sn2+ + 2e Sn
Sn4+ + 2e Sn2+
O2 + 2H+ + 2e H2O2
H2O2 + 2H+ + 2e 2H2O
H2O2 + 2H+ + Sn2+ 2H2O + Sn4+

0.14
+0.15
+0.68
+1.77

(reduction)
(oxidation) - most fav ox
(oxidation)
(reduction) - most fav red
Ecell = +1.62 V > 0
energetically feasible

2015/JC2/Term3/Chem Dept/Physical Chemistry Revision


(Modified from 2011 & 2014 Physical Chemistry Revision (Redox & Electrochemistry)

H2 Chemistry 9647
e.g.

Physical Chemistry (Revision)

For the following circuit, will the voltage of the cell increase, decrease, or remain the
same if the concentration of KI is increased.
2Fe3+(aq) + 2I(aq)

2Fe2+(aq) + I2(aq)

If [I] is increased, by Le Chatelier's Principle, the position of equilibrium of half equation (2)
shifts to the left. i.e. more favourable to form I2.
Fe3+(aq) + e Fe2+(aq)
I2(aq) + 2e 2I(aq)

E1
E2

-------- (1)
-------- (2)

Ecell = E1 - E2 Increases.
____________________________________________________________________________
e.g.

Fuel cells are electrochemical cells that were developed as portable energy sources for
the Apollo space program. The overall equation for the reaction occurring in the
methane-oxygen fuel cell is
CH4(g) + 2O2(g) CO2(g) + 2H2O(g)

a) Write the two half-equations for the reaction occurring at the electrodes in the fuel cell.
CH4(g) + 2H2O(g) CO2(g) + 8H+(aq) + 8eO2(g) + 4H+(aq) + 4e- 2H2O(g)
b) At which electrode (positive or negative) does the oxygen react?
Oxygen reacts at the cathode where reduction takes place. In an electrochemical
cell, it is the positive electrode
c) What is the advantage of oxidizing methane in a fuel cell rather than producing energy
by the complete combustion of methane in oxygen?
The combustion of methane results in heat losses to the atmosphere hence is
less efficient than fuel cell. In the fuel cell, there is direct conversion of chemical
to electrical energy.

2015/JC2/Term3/Chem Dept/Physical Chemistry Revision


(Modified from 2011 & 2014 Physical Chemistry Revision (Redox & Electrochemistry)

H2 Chemistry 9647

Physical Chemistry (Revision)

ELECTROLYSIS
The number of Faradays required to discharge one mole of an ion at an electrode equals the
number of charges on the ion. The Faraday is the charge carried by one mole of electrons.
F = Le where L = the Avogadro constant

-19

e = charge on an electron (1.60 x 10


-1
1 F = 96 500 Cmol

TIP:
You should be able to state
the relationship, F = Le,
between
the
Faraday
constant, the Avogadro
constant and the charge on
the electron.

C)

Factors affecting selective discharge during electrolysis:


1) Position in the Redox Series.
Cation with the most positive Ered is discharged first.
Anion with the most negative Ered is discharged first.
2) Relative concentration of ions.
Ions of higher concentration will be selectively discharged
3) Nature of electrodes.
The quantity of charge (Q) passed during electrolysis can be calculated from
Q=Ixt

units: coulombs, C.

where I = current in amperes, A.


t = time in seconds, s

Electrolytic cell:
electrolysis = decomposition of a molten or aqueous compound using electricity

Pt electrode
(anode)

Pt electrode
(cathode)

+
**ALWAYS:
Cathode: reduction
Anode: oxidation

electrolyte

Direction of electron flow: electrons flow out of the negative terminal and into the positive
terminal of the battery
Polarity of the electrode depends on which terminal (+/) of the battery it is connected to
Inert electrodes are used, e.g. Pt, graphite, steel
Electrolyte can be a molten salt or an aqueous solution of a salt (ions are free to move to
conduct electricity)

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Physical Chemistry (Revision)

Factors affecting substance liberated during electrolysis (for electrolytes containing more
than one salt or aqueous salts):
i.

Ered cations/anions with a more positive Ered will be discharged first


Note that for aqueous solutions, water can also be discharged at either electrodes.

2H2O(l) + 2e H2(g) + 2OH(aq)


2H2O(l) 4H+(aq) + O2(g) + 4e
Note that the equations 2H+ + 2e H2 and 2OH 2H+(aq) + O2(g) + 4e are not used as [H+] and [OH] are low
compared to H2O in aqueous solutions.

ii. Relative concentration of ions if a cation/anion is in very high concentration, it may


be discharged in preference to one with a more favourable Ered (if their Ered are close
to each other)
Note that electrolysis of dilute aqueous solutions produces H2 and O2 (electrolysis of water).

iii. Nature of electrode sometimes the electrodes are deliberately chosen to take part in
the redox reactions
e.g.
(a)

A current of 11 A is passed through an aqueous solutions of CrCl3 for 52 min. Calculate


the mass of Cr deposited on the cathode and the volume of Cl2 at stp released at the
anode.
Q = It = 11(52 x 60) = 34320 C
34320
n(e) =
= 0.3556 mol
96500
Cr3+ + 3e Cr
n(Cr) = 1/3(0.3556) = 0.1185
mass(Cr) = 0.1185(52.0) = 6.16 g

(b)

Cl Cl2 + e
n(Cl2) = (0.3556) = 0.1778
V(Cl2) = 0.1778(22.4) = 3.98 dm3

How long would it take to produce 25.0 g of Cr from a solution of CrCl3 by a current of
2.75 A?
25.0
= 0.4808
52.0
Cr3+ + 3e Cr
n(e) = 3 x 0.4808 = 1.442
Q = 1.442 x 96500 = 139200 C
Q
139200
Q = It t =
=
= 50610 s 14.1 h
I
2.75

n(Cr) =

2015/JC2/Term3/Chem Dept/Physical Chemistry Revision


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Physical Chemistry (Revision)

DISCUSSION QUESTIONS
[ACJC 2006 Prelim Q3]

Q1.

(a)

The diagram shows a laboratory illustration of a simple hydrogen-oxygen fuel cell.

(i)

Write the half equation for the reaction occurring at the left hand (oxygen)
electrode when the cell operates and state its polarity.
O2 (g) + 4H+ (aq) + 4e
Polarity of electrode: Positive

(ii)

2H2O (l)

Only a very small current can be drawn from this laboratory cell. Suggest one
way in which it could be modified to enable a larger current to be drawn from
it.
Increase concentrations of ions in reduction half-cell OR Increase in operating
pressure

(iii)

A fuel cell in an orbiting satellite is required to produce a current of 0.010A for


400 days. Calculate the mass of hydrogen that will be needed.
Time taken = 400 x 24 x 60 x 60 = 34560000 seconds
Quantity of electricity = 0.01 x 34560000 = 345600 C
Amount of e- = 345600/96500 = 3.6 mol
H2 (g) 2H+ (aq) + 2eAmount of H2 = 3.6/2
Mass of H2 = (3.6/2) x 2 = 3.60 g

(b)

A major use of molybdenum is as an alloy with iron, ferromolybdenum. Extremely


hard and strong, even at high temperatures, this alloy is used in filament supports,
in heating elements for furnaces and for drill bits. The table below shows five
standard reduction potentials for molybdenum-containing species.
3+

Mo + 3e Mo
MoO2+ + 4H+ + 2e- Mo3+ + 2H2O
MoO42- + 4H+ + 2e- MoO2 + 2H2O
MoO3 + 6H+ + 6e- Mo + 3H2O
MoO42- + 4H2O + 6e- Mo + 8OH-

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E/V
-0.20
0.00
-1.40
+0.10
-0.97

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H2 Chemistry 9647
(i)

Physical Chemistry (Revision)

Using the above data and any other data from the Data Booklet, suggest a
reducing agent that could reduce aqueous molybdate(VI) ion, MoO42-(aq), to
molybdenum(IV) oxide. Calculate the Ecell for the reaction and write a
balanced equation.
Al (s)
Al3+ (aq) + 3e
2+
MoO4 + 4H + 2e
MoO2 + 2H2O

Ered = -1.66V
Ered = -1.40V

2Al (s) + 3MoO42- (aq) + 12H+ (aq) 2Al3+ (aq) + 3 MoO2 (s) + 6H2O (l)
Ecell = -1.40-(-1.66) = +0.26V
Mg (s)
Mg2+ (aq) + 2e
MoO42- + 4H+ + 2e MoO2 + 2H2O

Ered = -2.90V
Ered = -1.40V

Mg (s) + MoO42- (aq) + 4H+ (aq) Mg2+ (aq) + MoO2 + 2H2O (l)
Ecell = -1.40-(-2.90) = +1.50V
Although Ered has to be more negative than -1.40V, Ca(s), Ba(s), K(s), Li(s)
or Na(s) will react with water. Therefore it is not a good answer.
(ii)

An aqueous solution of molybdenum(III) sulphate is electrolysed using inert


electrodes. Give ion-electron equations, with state symbols, for the electrode
reactions at the anode and the cathode.
Anode: 2H2O (l) O2 (g) + 4H+ + 4e
Cathode: Mo3+ (aq) + 3e Mo (s)

(iii)

0.00200 moles of MoO42- (aq) solution was reduced chemically. The reduced
molybdenum species was then re-converted at an electrode of an electrolytic
cell to its original form by passage of 579 C of electricity. Calculate the
oxidation state of the molybdenum in the reduced form.
(Assume that the oxidation state of oxygen remains unchanged throughout
the process.)
96500C = 1 mol of electrons
579C = 6 x10-3 mol of electrons
Let reduced species of molybdenum have an oxidation state of +n
Amount of Mon+ : Amount of electrons lost
2 x 10-3 : 6 x 10-3
1:3
n-(-3) = +6
n = +3

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[ACJC 2006 Prelim Q3]

Q2.

(a)

The electrical current needed to start an automobile engine is provided by a leadacid storage battery. This battery contains aqueous sulfuric acid in contact with two
electrodes. One electrode is metallic lead and the other is solid PbO2. Each
electrode becomes coated with solid PbSO4 as the battery operates.
(i)

Determine the oxidation and reduction half-equations at both electrodes.


anode:
cathode:
OR
anode:
cathode:

(ii)

Pb + SO42-
PbSO4 + 2e
PbO2 + 4H+ + SO42- + 2e PbSO4 + 2H2O
Pb + HSO4-
PbSO4 + H+ + 2e
+
PbO2 + 3H + HSO4 + 2e PbSO4 + 2H2O

Indicate the anode of the lead-acid storage battery and state its polarity.
Pb is the anode and it is the negative electrode.

(iii)

Automobile headlights typically draw 5.9 A of current. The lead-acid storage


battery consumes Pb and PbO2 as it operates.
A typical electrode contains 250 g of PbO2. Assuming that the battery can
supply 5.9 A of current until all the PbO2 has been consumed, how long will it
take for a battery to run down if the lights are left on after the engine is turned
off?
Amount of PbO2 = 250/239 = 1.05 mol
PbO2 + 4H+ + SO42- + 2e PbSO4 + 2H2O
Amount of e = 1.05 x 2 = 2.10 mol
Quantity of charge = 2.10 x 96500 = 202650 C
Time taken = 202650 / 5.9 x60 x60 = 9.5 hrs

(b)

A 1.00 g sample of steel containing manganese was dissolved in nitric acid to give
a solution containing manganese in oxidation state +2. All the manganese present
was then oxidized to manganate(VII) by adding sodium bismuthate, NaBiO3.
After the destruction of any excess bismuthate ion, the resulting purple solution
required 36.00 cm3 of an iron(II) sulfate solution of concentration 0.10 mol dm-3 to
reach an end-point, the iron(II) being oxidized to iron(III).
(i)

What is the oxidation state of bismuth in NaBiO3? +5

(ii)

Given that the bismuthate ion is reduced to Bi3+, write an equation for the
reaction in which it functions as an oxidizing agent. Hence write a balanced
equation for the oxidation of manganese(II) to Mn(VII) by bismuthate ion in
acidic solution.
BiO3- (aq) + 6H+ (aq) + 2e Bi3+ (aq) + 3H2O (l)
Mn2+ 4H2O
MnO4- (aq) + 8H+ (aq) + 5e
2Mn2+ (aq) + 5BiO3- (aq) + 14H+ (aq) 2MnO4- (aq) + 5Bi3+ (aq) + 7H2O (l)

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H2 Chemistry 9647
(iii)

Physical Chemistry (Revision)

Calculate the percentage by mass of manganese in the steel sample. [1 mol


MnO4-(aq) 5 mol Fe2+(aq)]
Amount of Fe2+ = 36.00/1000 x 0.10 = 0.00360 mol
Amount of MnO4- = 0.0036/5 = 0.00072 = Amount of Mn2+
Mass of Mn = 0.00072 x 54.9 = 0.0395 g
% of Mn in steel = 0.0395/1.00 = 3.95%

[ACJC 2005 Prelim Q3]

Q3.

Electrochemical cells are used as portable sources of electricity. When the chemicals get
depleted, the cell becomes flat. Consider the following two examples of electrochemical
cells being used as batteries.
(a)

A heart pacemaker consists of zinc and platinum electrodes implanted into the body
tissues. These electrodes in the oxygen-containing body fluid, with a pH of 7.4,
form a cell in which zinc is oxidised and oxygen is reduced.
(i)

Write the equations for the reactions occurring at the anode and cathode and
hence write a balanced equation for the overall reaction that takes place
when a current flows.
anode: Zn Zn2+ + 2ecathode: O2 + 2H2O + 4e- 4OHoverall: 2Zn + O2 + 2H2O 2Zn(OH)2

(ii)

Calculate the Eocell of this cell.


Eocell = +1.16 V

(iii)

How would the Eocell value change if the pH of the body fluid decreases below
7.4? Briefly explain your answer.
pH falling below 7.4 implies fluid gets more acidic. This allows the position of
equilibrium of the overall reaction to shift right because Zn(OH)2 dissolves.
Therefore, e.m.f. increases.

(iv)

If a current of 4 10-5 A was drawn from the cell, calculate how long a zinc
electrode weighing 5.0 g will last before it needs to be replaced. Correct your
answer to the nearest year. Assume that there are 365 days in a year and
that the cell e.m.f. remains unchanged throughout usage of the cell.
Amount of Zn = 5 65
Complete consumption of Zn requires passage of 2 5 65 mol e-.
Charge passed 2 (5 65) 96500 = 4 10-5 t
t = 12 years.

2015/JC2/Term3/Chem Dept/Physical Chemistry Revision


(Modified from 2011 & 2014 Physical Chemistry Revision (Redox & Electrochemistry)

15

H2 Chemistry 9647
(b)

Physical Chemistry (Revision)

A concentration cell is one that generates voltage due to a concentration difference.


One example is shown below:
Cu(s) | Cu2+(aq) (0.01 mol dm-3) || Cu2+ (1.0 mol dm-3) | Cu(s).
(i)

Calculate the reduction potential of the oxidation half-cell if the Ecell


generated is 0.06 V.
Ecell = Eored(Cu2+/Cu) Ered(Cu2+/Cu)
Ered(Cu2+/Cu) = +0.28 V

(ii)

State how the concentrations of the Cu2+ ions in the two half-cells are related
when the cell becomes flat, i.e. Ecell = 0.00 V.
When Ecell = 0.00 V, electrons don't flow. [Cu2+] in the two half cells are equal.

[ACJC 2005 Prelim Q3]

Q4.

In an electrolytic cell, a current of 0.250 A is passed through a concentrated solution of a


chloride of iron, producing iron metal and chlorine gas.
(a)

Write the equation for the half-reaction taking place at the anode.
2Cl- Cl2 + 2e-

(b)

When the cell operates for 2.00 hours, 0.521 g of iron is deposited at one electrode.
Determine the formula of the chloride of iron in the original solution.
Let formula of Fe ion be Fex+.
Amount of Fe formed = 0.521 56
No. of faradays required = (0.521 56)x
Amount of charge passed = 96500 (0.521 56)x = 1800 C
Therefore, x = 2 &

(c)

Formula of chloride is FeCl2.

Write a balanced equation for the overall reaction that occurs in the cell.
Fe2+ + 2Cl- Fe + Cl2

(d)

What volume of chlorine gas, measured at r.t.p., is produced when the cell operates
as described in part (b)?
Amount of Cl2 evolved = 0.521 56
Vol. of Cl2 at r.t.p. = 0.223 dm3

(e)

Calculate the current that would produce chlorine gas from the solution at a rate of
3.00 g per hour.
Amount of Cl2 liberated = 3 71
Amount of charge required to produce (3 71) mol of chlorine
= 2 96500 (3 71) = I 60 60

I = 2.27 A.

2015/JC2/Term3/Chem Dept/Physical Chemistry Revision


(Modified from 2011 & 2014 Physical Chemistry Revision (Redox & Electrochemistry)

16