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8.1. Introduction
A redox reaction involves both oxidation and reduction
Oxidation is the loss of electrons
Reduction is the gain of electrons
(Remember OILRIG)
Redox reactions can be divided up into two half equations, one showing the reducing
agent and the other the oxidising agent.
A reducing agent is a species that loses electrons easily, becoming
oxidised in the process.
An oxidising agent is a species which gains electrons easily, becoming
reduced in the process
These half equations show how many electrons the reducing agent loses and how
many the oxidising agent loses. The change in oxidation number of the species is
directly related to the number of electrons transferred. Water and hydrogen ions also
often appear in half equations to balance any hydrogen or oxygen atoms.
e.g. the oxidation of hydrogen peroxide by dichromate(VI) ions,
Cr2O72- + 8H+ + 3H2O2 2Cr3+ + 7H2O + 3O2
(+6)(-2)
(+1) (+1)(-1)
(+3)
(+1)(-2) (0)
Each Cr in Cr2O72- gains 3 electrons to form Cr3+ - it is the oxidizing agent and
becomes reduced
2+
3+
Cr2O7 + 14H + 6e 2Cr + 7H2O
Each O in H2O2 loses 1 electron to form O2 - it is the reducing agent and
becomes oxidized
+
H2O2 O2 + 2H + 2e
In this chapter, the system of electrode potentials will be introduced. At a basic level,
electrode potentials are measurements which show the relative strengths of oxidizing
agents and reducing agents.
8.2. Electrode potentials and the electrochemical series
At GCSE level, test-tube displacement reactions are used to demonstrate that some
metals are more reactive than others. By comparing the results of such experiments, a
reactivity series can be drawn up.
So zinc must be
more reactive
than copper
zinc
metal
copper(II)
sulphate
solution
copper
metal
ppte.
- 68 -
zinc(II)
sulphate
solution
The displacement reaction between zinc and copper(II) sulphate is actually a redox
reaction, as shown by the changes in oxidation number:
CuSO4(aq) + Zn(s) Cu(s) + ZnSO4(aq)
(+2)
(0)
(0)
(+2)
In simple terms, the Cu2+ ions have gained two electrons and been reduced whilst the
zinc atoms have lost two electrons and been oxidised. The zinc is therefore a more
powerful reducing agent than copper.
At A-level, the reactivity series is called the electrochemical series as it is listed more
o
Na+ + e-
E = -2.92 V
o
Na
E = -2.71 V
Zn2+ + 2e-
Zn
E = -0.76 V
Fe2+ + 2e-
Fe
E = -0.44 V
2H+ + 2e-
H2
E = 0.00 V
Cu2+ + 2e-
Cu
E = +0.34 V
I2 + 2e-
o
o
o
o
2I-
Br2 + 2e-
E = +0.54 V
o
2Br-
E = +1.09 V
Mn2+ + 4H2O
E = +1.51 V
o
E = +1.33 V
E = +1.36 V
o
2F-
E = +2.87 V
The most powerful reducing agent in the list is potassium metal - the species which
loses electrons most effectively. As the very first equation has the most negative
electrode potential, it goes backwards most readily and potassium loses electrons.
The most powerful oxidizing agent is fluorine. The final equation has the most
positive electrode potential, goes forwards most readily and fluorine gains electrons.
The hydrogen equation has been given an electrode potential value of 0.00 volts by
chemists so that it acts as the standard.
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a negative E
reaction
reaction
values. Again,
reaction
e.g.1 for the reaction between manganate(VII) ions and iodide ions,
(1) MnO4- + 8H+ + 5e(2) 2I-
Mn2+ + 4H2O
E = +1.51 V
o
I2 + 2e-
E = -0.54 V
reaction
reaction
e.g.2 for the reaction between manganate(VII) ions and fluoride ions,
(3) MnO4- + 8H+ + 5e(4) 2F-
Mn2+ + 4H2O
E = +1.51 V
o
F2 + 2e-
E = -2.87 V
reaction
reaction
A positive value for E reaction shows that a reaction is feasible, not that it definitely will
happen. There are 2 main reasons why reactions that are feasible do not actually
occur in reality:
o
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b) E predictions are only valid for reactions mixed under standard conditions.
Real reactions are rarely mixed at 25C, 1 atm and 1 moldm-3.
Methods for answering exam questions
o
There are two general methods for answering exam questions on E predictions. The
second method is much faster than the first, but it is best to be able to master both.
Method 1 calculating E
reaction
To see if a reaction is feasible or not, the half equations are combined and E reaction
calculated as before. However, before this can be done, one of the half-equations
must be reversed and the sign of its electrode potential changed. To decide which
half-equation to reverse, look closely at the reactants in the question these must
both appear on the left of the final overall equation.
e.g.1. Will zinc reduce copper(II) ions to copper metal?
o
Zn
E = -0.76 V
Cu
E = +0.34 V
As zinc and copper(II) ions are the reactants, equation (1) must be flipped
[zinc is on the right in equation (1)].
Zn + Cu2+ Zn2+ + Cu
So,
and E
reaction
2Br-
E = +1.09 V
2Cl-
E = +1.36 V
reaction
A simple comparison of the E values of two half equations will show which will
proceed forwards (the most positive) and which will go backwards (the most
negative). Again, a close inspection of the reagents in the question will then show
whether or not reaction will occur.
e.g.1. Will manganate(VII) ions oxidize chloride ions to chlorine?
(1) MnO4- + 8H+ + 5e(2) Cl2 + 2e-
Mn2+ + 4H2O
E = +1.51 V
o
2Cl-
E = +1.36 V
- 71 -
Equation (1) will go forwards as its E is more positive, and (2) will go backwards.
So MnO4- will oxidise Cl- as E
MnO4-/Mn2+
Cl2/Cl-
Zn
E = -0.76 V
Mg
E = -2.37 V
Equation (1) will go forwards as its E is more positive, and (2) will go backwards.
So Zn will NOT reduce Mg2+ as E
Zn2+/Zn
Mg2+/Mg
There are always four possible ways to express the answer using this method (E
o
A/B
more positive than E C/D or E C/D less positive than E A/B etc.). Care must be taken to
avoid silly errors. The advantage of this method lies in the fact that it allows a large
range of reactants to be compared quickly. Many A-level questions rely on this skill.
e.g.3 Which metal ions can be reduced by zinc metal?
o
K+ + e -
E = -2.92 V
Na+ + e-
Na
E = -2.71 V
Zn2+ + 2e-
Zn
E = -0.76 V
Fe2+ + 2e-
Fe
E = -0.44 V
Ni2+ + 2e-
Ni
E = -0.25 V
Cu2+ + 2e-
Cu
E = +0.34 V
o
o
o
Ag+ + e- Ag
E = +0.80 V
The zinc equation must go backwards and be more negative than the other half
equation if reaction is to occur.
So Zn will reduce Fe2+, Ni2+, Cu2+ and Ag+ because E
more negative than E
Fe2+/Fe
,E
,E
Ni2+/Ni
Cu2+/Cu
and E
Zn2+/Zn
Ag+/Ag
is
.
8.4. Disproportionation
Just as electrode potentials can be used to predict the feasibility of normal redox
reactions, they can also reveal the possibility of a species undergoing
disproportionation.
Disproportionation is the simultaneous oxidation and
reduction of a single species
A species must be able to undergo oxidation and reduction and will therefore appear
on the left in one half equation and on the right in another. Reversing one of these
and adding it to another then gives a disproportionation equation the overall sign of
o
Cu+
E = +0.15 V
o
Cu
E = +0.52 V
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ezinc metal
zinc(II) sulphate
solution
i.e. Zn2+(aq)
copper metal
salt
bridge
copper(II) sulphate
solution
i.e. Cu2+(aq)
The salt-bridge is used to complete the circuit without using a metal wire metals
are good reducing agents and would set up more competing redox reactions. A salt
bridge can be made by dipping a filter paper in an aqueous solution of potassium
nitrate and allows ions to flow between half cells.
The reaction driving the cell is the same as that above in the test-tube reaction but
electrical energy is produced instead of heat.
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
(0)
(+2)
(+2)
(0)
In this circuit, electrons travel from left to right because the zinc has lost electrons
and the copper(II) ions have gained them.
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As electrons flow through the wire away from the zinc, the metal dissolves, the
copper electrode grows fatter and the blue colour of the copper(II) ion fades. When
either reagent runs out, the cell becomes flat.
8.6. Electromotive force (emf) and electode potentials
Consider the cell produced if the zinc above is replaced with magnesium. As
magnesium is more reactive (i.e. a better reducing agent) than zinc, it pushes electrons
around the circuit much more strongly. If a voltmeter is added in place of the bulb, it
will measure the electromotive force (emf) of the cell.
high resistance voltmeter
V
magnesium
metal
copper metal
copper(II) sulphate
solution
i.e. Cu2+(aq)
magnesium
sulphate solution
i.e. Mg2+(aq)
As electrode potentials are used to show the strength of oxidizing agents and reducing
agents, they can be used to predict the emf of any cell. Electrode potentials are
actually measured using cells; this is why they have units of volts.
The half equations for the cell above are:
o
Cu
E = +0.34 V
Mg
E = -2.37 V
reaction
and E
cell
Again, electrons flow away from the mort reactive metal (magnesium) until all of it
dissolves or all of the copper(II) ions have reacted. If the voltmeter is replaced with
an electrical supply with a voltage higher than 2.71v, electrons can be pushed back to
the magnesium and the cell is re-charged. During this process, the reverse reaction
occurs.
8.7. Measuring electrode potentials
As a circuit is required to measure a potential difference, single electrode potentials
cannot be measured. Instead, chemists have chosen a standard electrode against
which all other electrodes are then compared. The standard hydrogen electrode has
- 74 -
been given an electrode potential of 0.0v and is included in circuits to measure other
electrode potentials.
o
Cu
voltmeter
V
copper metal
H2(g)
1atm
platinum
metal
copper(II) sulphate
solution 1 moldm-3
i.e. Cu2+(aq)
H+(aq)
1 moldm-3
The Cu2+/Cu
electrode
(half cell)
The Standard
Hydrogen
Electrode
2H+ + 2e-
H2
E = 0.00v
E =?
As the electrode potential of hydrogen has been given a value of 0.0v, the voltmeter
o
reading gives E for the copper(II)/copper half equation, in this case, +0.34v.
The whole apparatus can be placed in a temperature controlled waterbath at 25C
for more accurate results.
o
2ClV
H2(g)
1atm
Cl2(g) 1 atm
platinum
metal
platinum
metal
H+(aq)
1 moldm-3
(e.g. HCl)
Cl-(aq) 1 moldm-3
(e.g. NaCl)
- 75 -
The voltmeter reading again gives the E value for Cl2/Cl-. The platinum electrode
must be in contact with both chlorine and chloride ions dissolved in water. A
temperature controlled waterbath increases the accuracy of results.
o
Mn2+ + 4H2O
H2(g)
1atm
platinum
metal
H+(aq)
1 moldm-3
(e.g. HCl)
platinum
metal
MnO4-(aq)
+
Mn2+(aq)
+
H+(aq)
all at
1 moldm-3
Notice than in the half-cell under test, the platinum electrode must be in contact with
both reactants (MnO4-, H+) and products (Mn2+). The voltmeter reading again gives
the electrode potential for the MnO4-/Mn2+ system.
Mn2+ + 4H2O
(colourless)
As can be seen from the half equation, mandanate(VII) ions only work in the presence
of acid for this reason, dilute sulphuric acid must be added to any reducing agent
before titration commences.
As the titration proceeds, the
purple colour of the manganate
disappears until the end-point
is reached.
KMnO4 solution
in burette
2+
Calculation:
moles of MnO4- used = 28.2 x 0.05 = 1.41 x 10-3
1000
2+
moles Fe = 5 x 1.41 x 10-3 = 7.05 x 10-3 in 25 cm3
= 0.0705 in 250 cm3
2+
mass Fe = mass Fe = moles x rmm
= 0.0705 x 56 = 3.948g
so % Fe in the steel = 3.948 x 100 = 98.8%
4.0
Standardisation of manganate(VII) solutions
Manganate(VII) ions are such strong oxidizing agents that they will react with dust in
the air. This means that manganate(VII) solutions go off and their concentration
must be checked before super-accurate analyses. This is done via titration of a known
mass of sodium ethandioate (Na2C2O4). The ethandioate ions are oxidized to carbon
dioxide:
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 8H2O + 10CO2
A typical standardization calculation:
A 5.0g mass of sodium ethandioate was dissolved in water and made up to 250cm3.
When a 25cm3 sample was titrated with manganate(VII) solution, a volume of
16.8cm3 was needed for reaction.
Moles Na2C2O4 used = mass = 5.0 = 0.03731 in 250cm3
rmm 134
= 3.731 x 10-3 in 25cm3
-3
moles MnO4 = 3.731 x 10 x 2 = 0.01492
5
conc. MnO4 = moles x 1000 = 0.01492 x 1000 = 0.0888 moldm-3
volume
16.8
8.9.2. Analysing oxidizing agents with potassium iodide and sodium thiosulphate
In these analyses, the oxidizing agent is first treated with a large excess of potassium
iodide (KI) solution. The iodide ions are oxidized to iodine and the reaction mixture
turns brown. The amount of iodine is then found by titration with sodium
thiosulphate solution (Na2S2O3):
2S2O32- + I2
brown
S4O62- + 2Icolourless
Na2S2O3 solution
in burette
oxidising agent (e.g. Cu2+)
and
excess KI produces I2
Note: The thiosulphate ion can actually be oxidized in two different ways depending
on the strength of the oxidizing agent. This is shown by the following half equations:
2SO42- + 10H+ + 8eS4O62- + 2eo
As E
I2/I-
S2O32- + 5H2O
2S2O32-
E = +0.57 V
o
E = +0.09 V
is only +0.54 V, iodine will only react to form S4O62-. Stronger oxidizing
o
agents like chlorine (E Cl2/Cl- = 1.36 V) makes both S4O62- and SO42- simultaneously in
different reactions and can therefore not be analysed by titration with thiosulphate.
- 79 -
OH-
water with
dissolved O2
O2
2. oxygen
reduced
iron
metal
1. At areas of weakness, iron(II) ions dissolve, leaving behind electrons in the metal:
Fe Fe2+ + 2e-
(oxidation)
2. Electrons travel through the metal to another point on the surface where oxygen is
reduced to hydroxide ions:
O2 + 2H2O + 4e- 4OH(reduction)
3. The iron(II) hydroxide now present in the water is further oxidized to rust
2Fe(OH)2 + O2 Fe2O3 + 2H2O
As more and more rust forms it flakes away from the surface, exposing fresh metal
and so deep pitting eventually results where the iron(II) ions dissolve.
Rust prevention
There are two general methods used to prevent iron from rusting:
a) Coverage of the iron surface
If water and oxygen are not in contact with the metal then no rusting can occur.
Painting, oiling and tinning all work in this way. As tin is unreactive, it does not
readily corrode.
o
Fe2+ + 2e-
Fe
E = -0.44 V
Sn2+ + 2e-
Sn
E = -0.14 V
b) Sacrificial protection
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Mg2+ + 2e-
Mg
E = -2.37 V
Zn2+ + 2e-
Zn
E = -0.76 V
Fe2+ + 2e-
Fe
E = -0.44 V
o
o
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