A2 CHEMISTRY

SAHAN SATHARASINGHE

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Electrochemistry encompasses chemical and physical processes that involve the transfer
of charge. Some examples are electroplating, iron oxidation (rusting), solar-energy
conversion, energy storage (batteries), photosynthesis, and respiration.
Reduction and oxidation
Redox reactions involve oxidation and reduction occurring simultaneously.
Rules for assigning oxidation number:
1 Oxidation number for an un-combined element is 0.
2 The sum of the Oxidation numbers in a compound is equal to the overall charge.
3 Group 1 compounds are +1 & group 2 are +2.
4 F is always -1 in a compound. And Cl is usually -1 except when its with O or F.
5 H is +1 (except metal hydrides) and O is -2 (except Peroxides).
Redox is any reaction which involves one species being oxidised (loss of electrons)and
another being reduced (gain in electrons).
Half Equationsare used to show which species is oxidised and which is reduced.
changes in oxidation number to reaction stoichiometry
The number of electrons transferred in a reaction must always be the same on each side
so by using half equations you can split it up, eg the reaction between chloride ions and
chromium (III) ions:
Cl-(aq) Cl2(g) + 2e-x3 to make the electrons balance
Cr3+(aq) + 3e- Cr(s)x2 to make the electrons balance
So this gives the overall equation:
2Cr3+(aq) + 6Cl-(aq) 2Cr(s) + 3Cl2(g)

Oxidation is the loss of electrons

Reduction is the gain of electrons

As stated previously, these two reactions cannot occur in isolation.

The two equations are added to provide the reaction equation:

In terms of oxidation number:

For the oxidation: there has been an increase of +2
For the reduction: there has been an increase of -2
Displacement reactions
Displacement reactions occur if for example you place a more reactive metal in a solution
containing ions of a less reactive metal.For example:

If we now compare this with the following reaction:

We see that metals can be both oxidised and reduced, we write:

Metals in solutions of their ions

If a piece of metal is placed into a solution of its own ions, two occurrences may appear.
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Metal atoms may leave the solid and become metal ions in solution:
Oxidation

In this case the electrons that are released stay on the surface of the solid, which causes
it to gain a negative charge.
Or, metal ions in solution may become metal atoms on the surface of the solid.
Reduction

In this case, electrons are attracted into the solution.

Electrolysis
The electrolysis cell

The process of decomposing a compound using electricity is called electrolysis.

2H2O(l) 2H2(g) + O2(g)
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Electrolysis is a most important industrial process with a wide application. However, the
largest application is that of the manufacture of chlorine and sodium hydroxide from
concentrated aqueous sodium chloride in the Chlor-alkali industry.
The cell consists of two conducting rods called electrodes, dipped into a compound in a
molten state or in solution, that is able to conduct electricity called the electrolyte.
Electrolysis only works with direct current (the charge flows in only one direction). Direct
current causes one electrode to take on a positive charge called the anode. The second
electrode takes on a negative charge called the cathode.
Note: Anions (negative ions) are attracted to the anode. Cations (positive ions) are
attracted to the cathode.
An example of electrolysis:
If we place molten sodium chloride into the electrolysis cell and allow current to flow, the
following reactions occur at the electrodes:
At the cathode: Reduction
Na+(l) + e- Na(l)
At the anode: Oxidation
2Cl-(l) Cl2(g) + 2eThese two half equations give the overall reaction:
2Na+(l) + 2Cl-(l) Na(l) + Cl2(g)
A redox reaction has occured.
Predicting products in electrolysis
In the example above, of molten sodium chloride, there was one cation Na + and one
anion Cl-. Therefore, the products were easily calculated.
However, if a compound is in an aqueous solution, then we have two more ions to deal
with, OH- and H+.
So how do we decide with ions will appear at the electrodes and which remain in
solution?
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In the case of the cathode, we must decide which of the two cations, H + or Na+ is reduced
most easily back to their atoms. Hydrogen ions are most easily reduced so the following
cathode reaction occurs:
2H+(aq) + 2e- H2(g)
In the case of the anode, we must decide which of the two anions, OH - or Cl- will be most
easily oxidised back to atoms. Chloride ions are most easily oxidised, hence the following
anode reaction:
2Cl-(aq) Cl2 + 2eThis leaves Na+

(aq)

and OH-(aq) in solution i.e. sodium hydroxide.

We can refer to the electrochemical series, redox series or reactivity series for this
information.

Calculating mass of products in electrolysis

In 1832, Michael Faraday deduced that:
The quantity of electricity passed is proportional to the amount of substance
discharged at the electrode.

Quantity of electricity (charge) = current x time

The units used are, coulombs for charge, amps for current and seconds for time.

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Note 1: One mole of electrons has a charge of 96500C. This quantity of charge is called
the Faraday constant,F. Thus, the Faraday constant is related to Avagadro's
constant, L, and the charge on the electron, e.

F=Lxe
Note 2: The number of moles of electrons required to discharge 1 mole of ions is equal to
the charge on the ion.
For example, ions with a double charge, such as Cu 2+ - it will take two moles of electrons
to deposit one mole of copper.
Chlor-alkali industry

This industry involves the production of chlorine and the alkali sodium hydroxide from the
electrolysis of concentrated aqueous sodium chloride (brine).
The electrolysis cell used for this reaction is called the diaphram cell.
As previously stated, four ions are present Na +, Cl-, OH-, H+.
At the cathode:
2H+(aq) + 2e- H2(g)
At the anode:
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2Cl-(aq) Cl2(g) + 2eThe ions remaining in solution are OH- and Na+.
In the diaphragm cell, a porous asbestos partition, is placed between the electrodes to
prevent the sodium hydroxide making contact with the chlorine (sodium hydroxide tends
to concentrate near the cathode).
Purified brine solution is fed into the anode side and the level kept above that of the
cathode. This allows the sodium chloride solution to seep into the cathode compartment
and also prevents OH- ions migrating to the anode.

Standard hydrogen electrode

How do we find the potential of any half-cell individually? The answer is that we use
a standard hydrogen electrode (s.h.e) and give it a potential of zero.
Therefore, when it is connected to another half-cell, the electromagnetic
field (e.m.f) between the s.h.e and the second half-cell is equal to the potential of the
second half-cell.
The diagram below outlines the main characteristics and conditions required to establish
the s.h.e:
The reaction that takes place is:
2H+(aq) + 2e- 2H2 (g)
Standard Electrode Potential

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Definition - We can place redox systems in order of their oxidising/reducing ability if we

measure their electrode potential against the standard hydrogen electrode, which has a
potential of 0.00V.
Note: Standard conditions must be adhered to, so for example if using copper rods they
must be immersed into a solution of 1 mol dm-3 copper ions.
By convention, we define the e.m.f of an electrochemical cell as follows:

E = E

right-hand half-cell

- E left-hand half-cell

The s.h.e is always placed on the left-hand side.

The standard electrode potential of a metal is the potantial acquired when the metal is
immersed in a 1 mol dm-3solution of its ions at a temperature of 25oC.
It has the symbol E and the units V.

The electrochemical series

As stated previously, we can tabulate the order of oxidising/reducing ability of a system,
this we call the electrochemical series.
The most positive E value is at the top, i.e. the greatest oxidising agent. The most
negative value E at the bottom i.e. the greatest reducing agent.

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Eo (298K)/V

Reactio
n
F2(g)

+2
e-

&ruldhar;

2F-(aq)

+2.8
7

Co3+(aq)

+ e-

&ruldhar;

Co2+(aq)

+1.8
2

Pb4+(aq)

+2
e-

&ruldhar;

Pb2+(aq)

+1.6
9

Mn3+(aq)

+ e-

&ruldhar;

Mn2+(aq)

+1.5
1

Au3+(aq)

+3
e-

&ruldhar;

Au(s)

+1.4
2

Cl2(aq)

+2
e-

&ruldhar;

2Cl-(aq)

+1.3
6

Br2(aq)

+2
e-

&ruldhar;

2Br-(aq)

+1.0
7

NO3-(aq)
+ 2H+

+ e-

&ruldhar;

NO2(aq)
+ H2O(I)

+0.8
1

Ag+(aq)

+ e-

&ruldhar;

Ag(s)

+0.8
0

Fe3+(aq)

+ e-

&ruldhar;

Fe2+(aq)

+0.7
7

I2(aq)

+2
e-

&ruldhar;

2I-(aq)

+0.5
4

Cu+(aq)

+ e-

&ruldhar;

Cu(s)

+0.5
2

02(g) +
2H2O(l)

+4
e-

&ruldhar;

4OH-(aq)

+0.4
0

Cu2+(aq)

+2
e-

&ruldhar;

Cu(s)

+0.3
4

(aq)

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S042-(aq)
+ 4H+

+2
e-

&ruldhar;

SO2(aq)
+
2H20(l)

+0.1
7

Cu2+(aq)

+ e-

&ruldhar;

Cu+(aq)

+0.1
5

Sn4+(aq)

+2
e-

&ruldhar;

Sn2+(aq)

+0.1
5

Fe3+(aq)

+3
e-

&ruldhar;

Fe(s)

+0.0
4

2H+(aq)

+2
e-

&ruldhar;

H2(g)

0.00

Pb2+(aq)

+2
e-

&ruldhar;

Pb(s)

-0.13

Sn2+(aq)

+2
e-

&ruldhar;

Sn(s)

-0.14

Ni2+(aq)

+2
e-

&ruldhar;

Ni(s)

-0.26

Co2+(aq)

+2
e-

&ruldhar;

Co(s)

-0.28

Cr3+(aq)

+ e-

&ruldhar;

Cr2+(aq)

-0.41

Fe2+(aq)

+2
e-

&ruldhar;

Fe(s)

-0.44

Cr3+(aq)

+3
e-

&ruldhar;

Cr(s)

-0.74

Zn2+(aq)

+2
e-

&ruldhar;

Zn(s)

-0.76

Cr2+(aq)

+2
e-

&ruldhar;

Cr(s)

-0.90

Al3+(aq)

3e-

&ruldhar;

Al(s)

-1.67

Mg2+(aq)

+2

&ruldhar;

Mg(s)

-2.37

(aq)

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eNa+(aq)

+ e-

&ruldhar;

Na(s)

-2.71

Ca2+(aq)

+2
e-

&ruldhar;

Ca(s)

-2.84

K+(aq)

+ e-

&ruldhar;

K(s)

-2.93

Li+(aq)

+ e-

&ruldhar;

Li(s)

-3.04

Note: These reactions are in equilibrium, they can go either way.

To calculate the standard cell potential, from the standard electrode potentials we do the
following:

Ecell = E

right hand half-cell

- E

left-hand half cell

The left-hand half cell is conventionally the oxidising half-cell

e.g. E cell = E Cu2+/Cu - E Zn2+/Zn
= +0.34 - (-0.76) V
= +1.1V

Cell statements
This is the shorthand way of representing an electrochemical cell.
For example:
Daniell cell:

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The continuous vertical line represents the phase boundary. The broken vertical line
represents the salt bridge.
Making predictions with reactions
We can predict the likelihood of a reaction if two systems in the electrochemical series
are linked by cells. Remember, the system which is lower in the series will lose electrons,
and the one higher in the series will gain electrons.
For example:

Cell reaction:

understanding of why the predictions may not be borne out in practice due to
kinetic effects and nonstandard conditions
Limitations of Ecell:
- Ecell doesnt account for kinetic stability. For example if a reaction has very high
activation energy, it may be feasible but occur at an unobservable, slow rate.
- Actual conditions may be different to the standard conditions.
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- Electrode potentials apply only to aqueous equilibria so it cant be used for lots of
reactions.

Carry out and evaluate the results of an experiment involving the use of
standard electrode potentials to predict the feasibility of a reaction, eg
interchange of the oxidation states of vanadium or manganese
Oxidation states of Vanadium:
Manganese:

Oxidation states of

Species

Oxidatio
n no.

Colour

Species

Oxidatio
n no.

Colour

V2+

+2

Purple

Mn2+

+2

Pale Pink

V3+

+3

Green

MnO2

+4

Black

VO2+

+4

Blue

MnO4-

+7

Purple

VO2+

+5

Yellow

understanding of the procedures of the redox titrations below (1 and 2) and

carry out a redox titration with one:
1 - Potassiummanganate(VII), eg the estimation of iron in iron tablets
MnO4-(aq) is purple and Fe2+(aq) is colourless (But when concentrated, MnO 4-(aq) is pale pink
and Fe2+(aq) is pale green). At the end point, the solution will turn pale pink by itself. So this
is a self-indicating reaction.

2 - Sodium thiosulfate and iodine, eg estimation of percentage of copper in an alloy

Throughout the titration, I2 slowly turns from Brown to colourless I-. To clearly see the
change, starch is added near the end when the solution is pale yellow (otherwise Iodine is
adsorbed onto it and reduces accuracy) and will turn from blue-black to colourless.
A third example: Potassium manganate (VII) with ethanedioic acid
This reaction is an example of autocatalysis. The reaction is catalysed by manganese (II)
ions. So at the start there are none so it goes slow and needs heating. But then once a
few have been produced, they will begin to catalyse it and the reaction goes faster and
faster. (This is shown in the graph).
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the uncertainty of
and their implications for the validity of the final results

measurements

Level of accuracy in a burette is 0.05 cm 3

When working out percentage of uncertainty in the reading, it has to be multiplied by two
since you read the burette once at the start and once at the end of the titration:
% uncertainty in a burette

0.05
100
Volume Measured

Uncertainty in the readings can make the results less reliable.

Electrochemical Cells

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The Daniell cell

An electrochemical cell converts chemical energy into electrical energy using a redox
reaction.
Since, metals can be oxidised or reduced depending upon their chemical environment,
then such an arrangement as shown below may be set-up.
The Daniell cell, specifically, uses Zn (s)/Zn2+(aq) and Cu(s)/Cu2+(aq) reactions. Note that the
two rods in the diagram are called electrodes.
The zinc rod is the negative electrode and the copper rod the positive electrode.
Each metal in contact with a solution of its ions is called a half-cell. Half-cells are often
represented by half-cell equations, which show the electrode processes:
At the negative electrode: Oxidation
Zn(s) Zn2+(aq) + 2eAt the positive electrode: Reduction:
Cu2+(aq) + 2e- Cu(s)
So the overall reaction equation is:

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Remember this is a REDOX reaction.
Note in the diagram:
The electrons flow in a clockwise direction, from the zinc rod to the copper.
The salt bridge, completes the circuit by allowing the passage of ions from the copper
sulphate solution to the zinc sulphate solution. This salt bridge is usually a strip of filter
paper soaked in saturated potassium sulphate.
Electrochemical cells can be made, as long as you pair up two half-cells of different
potential so that an electrical current can be produced.

Hydrogen Fuel cell:

used in space exploration, in electric cars
Electrons are released at the hydrogen electrode
and are used at the oxygen electrode. The P.D. set
up pushes the electrons into an external circuit.
LHS: 2H2(g) 4H+(aq) + 4eRHS: O2(g) + 4H+(aq) + 4e- 2H2O(l)
Overall: 2H2(g) + O2(g) 2H2O(l)

Advantages:
- Hydrogen can come from the hydrolysis of water using a clean (non-fossil) energy
source.
- Hydrogen fuel cells dont produce CO 2 or nitrous oxides.

Disadvantages:
- Hydrogen is difficult to store.
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Methanol Fuel Cell:

This uses a similar principle to the H fuel
cell.
Overall: CH3OH(g) +

3
2 O2(g) CO2(g) +

2H2O(l)
Note: This occurs between
(BPT of CH3OH is 65C).

90 -120C

Advantages:
- Ethanol/methanol can be obtained from biomass.
- It is easier to store than Hydrogen.

Disadvantages:
- Methanol is flammable and poisonous.
- It is less efficient than the hydrogen fuel cell since its proton membrane works less well.

Both of these processes are renewable unlike the extraction of fossil fuels.

principles of modern breathalysers based on an ethanol fuel cell and compare

this to methods based on the use of IR and to the reduction of chromium
compounds.
Dichromate (VI) breath analyser:
Any ethanol in the breath would be oxidised to ethanoic acid reducing orange Potassium
dichromate(VI) to green Chromium(III). The colour change is detected by a meter which
displays the amount of alcohol present.
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Fuel cell breathalyser:
Exhaled air goes in and any alcohol is oxidised by a piece of platinum to ethanoic acid,
H+& e-. The Platinum electrodes are connected to an external ammeter; the more current
generated, the more alcohol is present.
IR spectroscopy and breath analysis:
IR radiation is passed through the sample and certain wavelengths are absorbed. The
more ethanol present in the sample, the greater the absorption peak will be. This gives
the most reliable results of the three.
Issues:
- Breath analysers must be calibrated regularly to be accurate.
- It is assumed the breath comes from deep within the lungs, but alcohol may have come
from mouth/throat etc. This means operators are trained to wait for at least 15-20 mins
before taking another reading.

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