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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.
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)
Zn2+ + 2e
Cu2+ + 2e
Cu(s)
H2 Chemistry 9647
H2 Chemistry 9647
Q2.
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
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
+5
H2 Chemistry 9647
Q5.
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?
H2 Chemistry 9647
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.
0.00 V
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
H2 Chemistry 9647
(ii)
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.
H2 Chemistry 9647
Cu(s) cathode
Pt(s) anode
1 mol dm3 Cu2+(aq)
**ALWAYS:
Cathode: reduction
Anode: oxidation
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
Daniel cell:
oxidation
reduction
cell diagram
e.g.
0.76 V
-0.44 V
H2 Chemistry 9647
e.g.
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
Ni(s)
Ni2+(aq)
Consider:
Ni2+ + 2e Ni E = 0.25V
Sn2+ + 2e Sn E = 0.14V
Sn2+(aq)
2+
Therefore,
Ni Ni2+ + 2e
Sn2+ + 2e Sn
Ni + Sn2+ Ni2+ + Sn
e.g.
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
H2 Chemistry 9647
e.g.
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.
H2 Chemistry 9647
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
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)
units: coulombs, C.
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)
10
H2 Chemistry 9647
Factors affecting substance liberated during electrolysis (for electrolytes containing more
than one salt or aqueous salts):
i.
iii. Nature of electrode sometimes the electrodes are deliberately chosen to take part in
the redox reactions
e.g.
(a)
(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) =
11
H2 Chemistry 9647
DISCUSSION QUESTIONS
[ACJC 2006 Prelim Q3]
Q1.
(a)
(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)
(b)
Mo + 3e Mo
MoO2+ + 4H+ + 2e- Mo3+ + 2H2O
MoO42- + 4H+ + 2e- MoO2 + 2H2O
MoO3 + 6H+ + 6e- Mo + 3H2O
MoO42- + 4H2O + 6e- Mo + 8OH-
E/V
-0.20
0.00
-1.40
+0.10
-0.97
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H2 Chemistry 9647
(i)
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)
(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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H2 Chemistry 9647
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)
(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)
(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)
(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)
14
H2 Chemistry 9647
(iii)
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)
(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.
15
H2 Chemistry 9647
(b)
(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.
Q4.
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)
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.
16