Redox Equilibria

Electron
Electrochemical cells flow
This type of cell can be called a Voltaic cell or Galvanic cell.
Salt bridge
Voltaic cells convert energy from spontaneous, exothermic
chemical processes to electrical energy. copper
electrode
•A cell has two half–cells. Zinc
electrode
•The two half cells have to be connected with a salt
bridge.
1M
•Simple half cells will consist of a metal (acts an 1M zinc copper
electrode) and a solution of a compound containing sulphate sulphate
that metal (eg Cu and CuSO4). solution solution
•These two half cells will produce a small voltage if
connected into a circuit. (i.e. become a Battery or
cell).

Why does a voltage form?

In the cell pictured above
When connected together the zinc half-cell has more of a tendency
to oxidise to the Zn2+ ion and release electrons than the copper
half-cell. (Zn Zn2+ + 2e-)
More electrons will therefore build up on the zinc electrode than the
copper electrode.
A potential difference is created between the two electrodes.
The zinc strip is the negative terminal and the copper strip is the
positive terminal.

This potential difference is measured with a high resistance

voltmeter, and is given the symbol E. The E for the above cell is E=
+1.1V.

Electron flow

e- e-

e- e-
-ve
+ve
NO3-

Na+ Na+

NO3-

2e- 2e-

Zn NO3-
Zn2+ Cu
Cu2+

Zn(s)  Zn2+(aq) + 2 e- Cu2+(aq) + 2e-  Cu(s)

Oxidation occurs at the anode (negative electrode) reduction occurs at the cathode (positive electrode)

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 Why use a High resistance voltmeter?
The voltmeter needs to be of very high resistance to stop the current from flowing in the circuit. In this state it is
possible to measure the maximum possible potential difference (E).
The reactions will not be occurring because the very high resistance voltmeter stops the current from flowing.

Salt Bridge
The salt bridge is used to connect up the circuit. The free moving ions conduct the charge.

A salt bridge is usually made from a piece of filter paper (or material) soaked in a salt solution, usually
Potassium Nitrate.

The salt should be unreactive with the electrodes and electrode solutions.. E.g. potassium chloride would not
be suitable for copper systems as Chloride ions can form complexes with copper ions.

A wire is not used because the metal wire would set up its own electrode system with the solutions.

What happens if current is allowed to flow?

If the voltmeter is removed and replaced with a bulb or if the circuit is short circuited, a current flows. The
reactions will then occur separately at each electrode. The voltage will fall to zero as the reactants are used up.

The most positive electrode will always undergo reduction.

Cu2+ (aq) + 2e-  Cu(s) (positive as electrons are used up)

The most negative electrode will always undergo oxidation.

Zn(s)  Zn2+ (aq) + 2e- (negative as electrons are given off)

Terminology: Cathode and Anode

In electrochemical (galvanic cells) the cathode and anode have the opposite signs to what they have in
electrolysis cells. The key point to remember is that in both galvanic and electrolytic cells reduction always
occurs at cathode and oxidation always occurs at anode

Process that occurs at Sign of electrode in Sign of electrode in

electrode electrolysis cells voltaic cells
cathode reduction Negative Positive
anode oxidation Positive Negative

Systems that do not include metals.

If a system does not include a metal that can act as an electrode, then a platinum electrode must be used.
A platinum electrode is used because it is unreactive and can conduct electricity.

Pt electrode
Salt bridge
copper KNO3 (aq)
electrode

1M
copper
sulfate
solution

1M FeSO4 and 0.5 M Fe2(SO4)3

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Cell Diagrams
• The solid vertical line represents the boundary
Electrochemical cells can be represented by a cell diagram:
between phases e.g. solid (electrode) and
solution (electrolyte)
Zn(s) | Zn2+ (aq) | | Cu2+ (aq) | Cu (s) E= +1.1V
•The double line represents the salt bridge
between the two half cells
Most oxidised form is put next to the double line
•the voltage produced is indicated
•the more positive half cell is written on the right
if possible (but this is not essential)

Systems that do not include metals.

If a system does not include a metal that can act as an electrode, then a platinum electrode must be used
and included in the cell diagram.

e.g. for Fe2+ (aq)  Fe3+ (aq) + e- there is no If the system contains several species
solid conducting surface, a Pt electrode must be e.g. MnO4- + 8H+ + 5e- Mn2+ + 4H2O
used. then in the cell diagram the balancing numbers, H+
ions and H2O can be left out.
The cell diagram is drawn as:
| | Fe3+ (aq), Fe2+ (aq) |Pt | |MnO4- , Mn2+ |Pt
or if on left hand side
Still with more oxidised form near double line Pt | Mn2+ , MnO4- | |
A comma separates the oxidised from the reduced
species.

If a half equation has several physical states then the solid vertical
line should be used between each different state boundary.
4e- + 2H2O (l) +O2 (g) 4OH- (aq) | | O2 | H2O, OH- | Pt

Cl2 (g) + 2e-  2Cl- (aq) | | Cl2 | Cl- | Pt

As the phase line also separates the oxidised and

reduced terms a comma is not necessary here.

Measuring the electrode potential of a cell

• It is not possible to measure the absolute potential of a half electrode on its own. It is only
possible to measure the potential difference between two electrodes.
• To measure it, it has to be connected to another half-cell of known potential, and the
potential difference between the two half-cells measured.
• by convention we can assign a relative potential to each electrode by linking it to a reference
electrode (hydrogen electrode), which is given a potential of zero Volts

Standard Cell potential is the potential of a cell composed of two electrodes under standard conditions

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The Standard Hydrogen Electrode

The potential of all electrodes are measured by comparing

their potential to that of the standard hydrogen electrode. Metal
Salt bridge
electrode
H2 gas at KNO3 (aq)
e.g. Fe
The standard hydrogen electrode (SHE) is assigned the 100kPa
potential of 0 volts.

Pt electrode
The hydrogen electrode equilibrium is:
H2 (g) 2H+ (aq) + 2e-
1M HCl
In a cell diagram the hydrogen electrode is
represented by: Pt |H2 (g) | H+ (aq)
Solution containing metal
ions (e.g. Fe2+) at 1 mol
Components of a standard hydrogen electrode. dm-3 concentration
To make the electrode a standard reference electrode
some conditions apply: Because the equilibrium does not include a
1. Hydrogen gas at pressure of 100kPa conducting metal surface a platinum wire is used
2. Solution containing the hydrogen ion at 1 M which is coated in finely divided platinum. (The
(solution is usually 1M HCl) platinum black acts as a catalyst, because it is
3. Temperature at 298K porous and can absorb the hydrogen gas.)

Secondary standards
Standard conditions are needed because
The Standard Hydrogen Electrode is difficult to use, so often a
the position of the redox equilibrium will
different standard is used which is easier to use.
change with conditions.
These other standards are themselves calibrated against the SHE.
For example, in the equilibrium:
This is known as using a secondary standard - i.e. a standard
Mn+(aq) + n e- M(s)
electrode that has been calibrated against the primary standard.
The common ones are:
An increase in the concentration of Mn+
silver / silver chloride E = +0.22 V
would move the equilibrium to the right,
calomel electrode E = +0.27 V
so making the potential more positive.

Standard Electrode Potentials E

The standard conditions are :
When an electrode system is connected to the •All ion solutions at 1M
hydrogen electrode system, and standard conditions •temperature 298K
apply the potential difference measured is called the •gases at 100kPa pressure
standard electrode potential, •No current flowing

Salt bridge
Standard electrode potentials are found in KNO3 (aq)
data books and are quoted as H2 gas at
100kPa
Li+(aq) | Li (s) E= -3.03V Pt electrode
more oxidised form on left

They may also be quoted as half Pt electrode

equations
Li+ (aq) + e- Li (s) E= -3.03V
but again the more oxidised form is on 1M HCl
the left

1M FeSO4 and
Pt|H2|H+||Fe3+,Fe2+|Pt 0.5 M Fe2(SO4)3

Note: in the electrode system containing two solutions it is

necessary to use a platinum electrode and both ion solutions
must be of a 1M concentration so [Fe2+] = 1M and [Fe3+] = 1M .

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Calculating the EMF of a cell
In order to calculate the Ecell, we must use ‘standard
Mg(s) | Mg2+ (aq) | | Cu2+ (aq) | Cu (s) E= +1.1V electrode potentials’ for the half cells.

use the equation Ecell= Erhs - Elhs Each half cell has a standard
electrode potential value
For the cell diagram above Mg2+ (aq)| Mg(s) E= -2.37V
Ecell = 0.34 - -2.37 Cu2+ (aq) | Cu (s) E = +0.34V
= + 2.71 V

Using electrode potentials

The most useful application of electrode potentials is to show

the direction of spontaneous change for redox reactions

The easiest way to use electrode potentials is as follows:

For any two half equations The more negative half cell will
always oxidise (go backwards)
If we want to work out the Ecell
Mg2+ (aq) + 2e- ⇌ Mg(s) E= -2.37V that corresponds to this
Cu2+ (aq) + 2e- ⇌ Cu (s) E = +0.34V spontaneous change then use
The reaction would be Ecell = Ered – Eox
The more positive half cell will always Mg + Cu2+  Cu + Mg 2+ A spontaneous change will
reduce (go forwards) always have a positive Ecell

The most negative electrode will oxidise and go from right to left
Zn2+(aq) + 2e- ⇌ Zn(s) E= - 0.76V
The half equation is therefore Zn(s)  Zn2+ (aq) +2e-
Fe2+(aq) + 2e- ⇌ Fe(s) E= -0.44V
Electrons are given off (lost) and travel to positive electrode

To get the full equation of the reaction add the

The more positive electrode will reduce and go from left to
two half reactions together, cancelling out the
right Fe2+ (aq) +2e-  Fe(s)
electrons.
Electrons arrive at this electrode and are absorbed (gained)
Zn + Fe2+  Fe + Zn2+

Using series of standard electrode potentials

Most strong reducing
oxidation agents found here

As more +ve As more -ve

Li+ + e- ⇌ Li -3.03V
increasing increasing
Mn2+ + 2e- ⇌ Mn -1.19V
tendency for tendency for
species on left to species on right
reduce, and act to oxidise, and
2H+ + 2e- ⇌ H2 0V
as oxidising act as reducing
agents agents
Ag+ + e- ⇌ Ag +0.8V
F2 + 2e- ⇌ 2F- +2.87

Most strong oxidising reduction If we want to work out the Ecell from two
agents found here standard electrode potentials then use
Ecell = Ered – Eox

The most powerful reducing agents will be found at the most negative end of the series
on the right (ie the one with the lower oxidation number)
The most powerful oxidising agents will be found at the most positive end of the series on
the left (ie the one with the higher oxidation number)

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Example 1

Use electrode data to explain why fluorine reacts with water.

Write an equation for the reaction that occurs.
oxidise
O2(g) + 4H+(aq) + 4e– ⇌ 2H2O(I) Eo+1.23V
First apply idea that more positive Eo will reduce (go forward)
F2(g) + 2e– ⇌ 2F–(aq) Eo +2.87V
and more negative Eo will oxidise (go backwards)
reduce
Explanation to write
As Eo F2/F- > Eo O2/H2O, and Ecell is a positive work out Ecell and quote it as part of your
value of +1.64V, F2 will oxidise H2O to O2 answer
Ecell = Ered - Eox = 2.87-1.23 =1.64V

Equation Remember to cancel out electrons in full equation

2F2(g) + 2H2O(I) → 4F–(aq) + O2(g) + 4H+(aq)

Example 2
Cl2(aq) + 2e– ⇌ 2Cl–(aq) Eo+1.36V
Use data from the table to explain why chlorine
2HOCl(aq) + 2H (aq) + 2e ⇌ Cl2(aq) + 2H2O(I) Eo+1.64V
+ –
should undergo a redox reaction with water. Write
H2O2(aq) + 2H+(aq) + 2e– ⇌ 2H2O(I) Eo +1.77V
an equation for this reaction.
O2(g) + 4H (aq) + 4e ⇌ 2H2O(I)
+ – Eo +1.23V
reduce
First select relevant half equations by considering the Eo
values and applying the idea that more positive Eo will reduce Cl2(aq) + 2e– ⇌ 2Cl– (aq) Eo+1.36V
(go forward) and more negative Eo will oxidise (go backwards) O2(g) + 4H (aq) + 4e ⇌ 2H2O(I) Eo +1.23V
+ –

oxidise
Explanation to write
Equation
As Eo Cl2/Cl- > Eo O2/H2O, and Ecell is a positive
value of +0.13V, Cl2 will oxidise H2O to O2 2Cl2(g) + 2H2O(I) → 4Cl–(aq) + O2(g) + 4H+(aq)

Example 3

Suggest what reactions occur, if any, when hydrogen gas Fe3+ (aq) + e– ⇌ Fe2+ (aq) Eo +0.77V
is bubbled into a solution containing a mixture of iron(II) 2H+(aq) + 2e– ⇌ H2(g) Eo 0.00V
and iron(III) ions. Explain your answer. Fe2+ (aq) + 2e– ⇌ Fe(s) Eo–0.44V
reduce
First select relevant half equations by considering the Eo
values and applying the idea that more positive Eo will reduce Fe3+ (aq) + e– → Fe2+ (aq) Eo +0.77V
(go forward) and more negative Eo will oxidise (go backwards) 2H+(aq) + 2e– → H2(g) Eo 0.00V

Explanation to write oxidise

Fe3+ will be reduced to Fe2+ by H2 oxidising to H+
Equation
because Eo Fe3+ /Fe2+ > Eo H+/H2 and Ecell is a
positive value of +0.77V 2Fe3+ (aq) + H2(g) → 2Fe2+ (aq) + 2H+(aq)

Example 4
Use the half-equations to explain in terms of oxidation states what
happens to hydrogen peroxide when it is reduced.
reduce
Explanation to write H2O2(aq) + 2H+(aq) + 2e– ⇌ 2H2O(I) Eo+1.77V
O2(g) + 2H+(aq) + 2e– ⇌ H2O2(aq) Eo +0.68V
As Eo H2O2/H2O > Eo O2/H2O2 and Ecell is a positive
value of +1.09V , H2O2 disproportionates from -1 oxidise
oxidation state to 0 in O2 and -2 in H2O Equation
2H2O2(aq) → O2 + 2H2O(I)

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 Ecell and equilibrium constants can all be used to predict if a reaction might occur.

Reaction ‘does Reactants equal amounts Products predominate Reaction goes to

not go’ predominate in an of products and in an equilibrium completion
equilibrium reactants

Kc < 10-10 Kc  0.1 Kc = 1 Kc 10 Kc > 1010

E < -0.6 E -0.1 V E =0 E +0.1 V E>0.6 V

Ecell is directly proportional to the total entropy change and to lnK (where K is equilibrium
constant)for a reaction
A positive Ecell will lead to a positive total entropy change

Effect of Conditions on Cell e.m.f

The effects of changing conditions on cell e.m.f can be E.m.f. is a measure of how far from equilibrium the cell
made by applying le chateliers principle. reaction lies. The more positive the e.m.f the more
likely the reaction is to occur.
If current is allowed to flow, the cell reaction will occur
and the emf will fall to zero as the reaction proceeds and
the reactant concentrations drop.
Zn2+(aq) + 2e- ⇌ Zn(s) E= - 0.76V
Effect of concentration on cell e.m.f Fe2+(aq) + 2e- ⇌ Fe(s) E= -0.44V

Looking at cell reaction is a straight forward application of Zn + Fe2+  Fe + Zn2+ E= +0.32

le chatelier. So increasing concentration of ‘reactants’
Increasing the concentration of Fe2+ and decreasing
would increase EMF and decreasing them would cause
the concentration of Zn2+ would cause Ecell to
EMF to decrease
increase
Effect of temperature on cell e.m.f
Most Ecells are exothermic in the spontaneous direction so applying Le chatelier to a temperature rise to these would
result in a decrease in Ecell

If the Ecell positive it indicates a reaction might occur. There is still a possibility, however, that the reaction will not occur
or will occur so slowly that effectively it doesn’t happen.
If the reaction has a high activation energy the reaction will not occur.

Nernst equation
The Nernst equation enables the electrode
potential for a system with non- standard E = E⦵ + (0.059/z) log [oxidised species]
concentrations to be calculated. [reduced species]

Z = the number of electrons transferred in the reaction equation

Example Example
Consider the half cell with the equilibrium Ag++ e- ⇌ Ag Consider the half cell with the equilibrium Fe3++ e- ⇌ Fe2+
Calculate the Ecell for the half cell when [Ag+] = 0.33 mol dm–3 Calculate the Ecell for the half cell when [Fe2+] = 0.43 mol dm–3
was used instead of the standard Ag+ solution. and [Fe3+] = 1.20 mol dm–3 were used instead of the standard
solutions.
E = E⦵ + (0.059/z) log [oxidised species]
[reduced species] E = E⦵ + (0.059/z) log [oxidised species]
z=1 as one e- in half equation [reduced species]
The reduced species is given a value of 1 as it is a
solid (silver) E = 0.77+ (0.059) log [1.20]
[0.43]
E = 0.80+ (0.059) log [0.33] =0.86 V
=0.77 V

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Uses of Cells
Electrochemical cells are used as a commercial source of electrical energy in every piece of portable electrical
equipment from torches to mobile phones. The chemical reactions that take place in the cells produce electricity.
The cells can be non-rechargeable (irreversible), rechargeable and fuel cells.
Primary: non rechargeable cells
Primary cells are non-rechargeable ones. These are the ones which have to be thrown away when they become flat.
Cells are non-rechargeable when the reactions that occur with in them are non-reversible.

Dry Cell
The dry cell is the standard 1.5V cell used in toys, remote controls etc.
There are several variations on the chemical reactions inside them but the negative
electrode tends to be zinc metal and the positive electrode contains manganese (IV)
oxide +
carbon rod
layer of
The outer container of the dry cell is a zinc can (This is powdered
the negative electrode). This contains a layer of NH4Cl carbon &
with ZnCl2 aqueous paste. This is separated by a MnO2
porous separator from a mixture of powdered carbon
& manganese (IV) oxide (MnO2), which is packed porous
around a carbon rod (this is the positive pole). separator

The porous separator allows the passage of ions Zinc Moist paste of
through so charge is conducted within the cell. casing NH4Cl with ZnCl2
The carbon rod is the electrode conducting
surface. -
Example standard electrode potentials for reactions in cell
Zn2+(aq) + 2e- ⇌ Zn(s) E = - 0.76 V
2MnO2(s) + 2NH4+(aq) +2 e- ⇌ Mn2O3(s) + 2NH3(aq) + H2O(l) E = 0.75 V

The more negative half equation will oxidise so the two reactions are

Anode: negative Zn(s)  Zn2+(aq) + 2e- oxidation

Cathode: positive 2MnO2(s) + 2NH4+(aq) + 2 e-  Mn2O3(s) + 2NH3(aq) + H2O(l) reduction
Overall reaction
2MnO2 + 2NH4++ Zn → Mn2O3 + 2NH3 + H2O + Zn2+ Ecell =+1.51V

The zinc electrode acts as a container for the cell and is protected from external damage. During the reaction
the outer zinc casing will be used up. A cell often leaks after being used for a long time because the zinc case
has become weakened due to being used up

Alkaline Dry Cell

This is a variation of the dry cell. The alkaline conditions in
these long life cells prevent the acid attack on the zinc casing. layer of
+
Notice the position of the manganese oxide and zinc are powdered
reversed in this cell. The outer casing of this cell is usually steel graphite & Paste of Zinc and
MnO2 KOH around the
Anode: negative Zn(s) + 2 OH- (aq)  Zn(OH)2(s) + 2e- anode

Cathode: positive MnO2(s) + H2O(l) + e- → MnO(OH)(s) + OH-(aq) porous

separator
overall reaction
brass rod filled
Zn(s) + 2 MnO2(s) + 2 H2O(l) → 2 MnO(OH)(s) + Zn(OH)2(s) with KOH
insulator
The cell produces a voltage of around 1.5V -
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Example primary
Lithium –manganese dioxide cell is a type of non rechargeable cell.
These are small cells used in many portable consumer electronic devices

The cell uses metallic lithium as MnO2

anode and manganese dioxide +
as the cathode. A salt of lithium porous
dissolved in an organic solvent separator
is the electrolyte -
Lithium

standard electrode potentials for reactions in cell

Li+aq +e- ⇌ Li (s) E = - 3.04 V More negative half equation will oxidise
Li+aq + MnO2 (s) +e- ⇌ LiMnO2(s) E = - 0.13 V (Mn will reduce changing oxidation state from +4 to +3)

Anode: negative Li (s)  Li+aq +e- oxidation

Cathode: positive Li+aq + MnO2 (s) +e-  LiMnO2(s) reduction

Overall reaction Li + MnO2 → LiMnO2 Ecell = E red- Eox = -0.13 - - 3.04 = 2.91 V

Conventional cell Li (s)| Li+aq | | Li+aq | MnO2 (s) , LiMnO2(s) | Pt (s)

diagram Ecell =+2.91V

Example secondary rechargeable cells

Lead acid Cell
The lead acid rechargeable battery made from several of these cells in series is
used commonly as batteries in cars.
The anode has a spongy lead covering on a lead-antinomy grid. The cathode is
lead(IV) oxide on a similar lead-antinomy grid. The electrolyte is sulfuric acid

standard electrode potentials for reactions in cell

PbSO4 + 2e- ⇌ Pb + SO42- E= -0.356V
PbO2 + SO42- + 4H+ + 2e- ⇌ PbSO4 + 2H2O E= +1.685 V

spongy lead
Anode: negative Pb + SO42-  PbSO4 + 2e- covering on a
lead grid PbO2 on a
Cathode: positive PbO2 + SO42- + 4H+ + 2e-  PbSO4 + 2H2O lead grid
Overall reaction PbO2 +Pb + SO42- + 4H+  2 PbSO4 + 2H2O
Ecell= +2.04V
During discharge

The forward reaction occurs on discharge giving out charge. Charging causes
the reaction to reverse

Overall reaction 2 PbSO4 + 2H2O  PbO2 +Pb + SO42- + 4H+

During recharging

Reversible cells only work if the product stays attached to the electrode and does not disperse
PbSO4 is insoluble and does not disperse

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Example secondary Nickel–cadmium cells are used to power electrical equipment such as drills and shavers.
They are rechargeable cells.
This cell has an anode made from cadmium and a cathode made from NiO(OH)
The electrolyte is potassium hydroxide

The standard potential electrode reactions are shown below.

NiO(OH) + H2O + e- ⇌ Ni(OH)2 + OH– E = +0.52 V (Ni will reduce changing oxidation state from 3 to 2)
Cd(OH)2 + 2e- ⇌ Cd + 2OH– E = –0.88 V (Cd will oxidise changing oxidation state from 0 to 2)

Overall reaction discharge 2NiO(OH) + Cd + 2H2O  2Ni(OH)2 + Cd(OH)2 E= +1.40V

Ecell = E red- Eox = +0.52 - - 0.88 = + 1.40 V
The overall reaction would be reversed in the recharging state
2Ni(OH)2 + Cd(OH)2  2NiO(OH) + Cd + 2H2O

Example secondary Lithium ion cells are used to power cameras and mobile phones.
Li+ + CoO2 + e- ⇌ Li+[CoO2] - E=+0.6V (Co will reduce changing oxidation state from 4 to 3
Li+ + e- ⇌ Li E=-3.0V
The reagents in the cell are absorbed onto
Overall discharge Li + CoO2  LiCoO2 E=3.6V powdered graphite that acts as a support
reaction medium. The support medium allows the ions
Conventional cell to react in the absence of a solvent such as
Li | Li+ || Li+ , CoO2 | LiCoO2 | Pt water. The electrolyte is a lithium compound
diagram
dissolved in an organic solvent

The overall reaction would be reversed

Water would not be good as a solvent as it
in the recharging state
would react with the lithium metal.

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 Fuel cell
A fuel cell uses the energy from the reaction of a fuel with oxygen to create a voltage

Hydrogen Fuel cell (potassium hydroxide electrolyte)

Fuel cells oxidise a fuel to produce an electric current. They will

maintain a constant voltage over time as they are continuously fed
with fresh O2 and H2 so maintaining constant concentration of H2 O2
reactants. This differs from ordinary cells where the voltage drops over from from air
time as the reactant concentrations drop. Fuels cells operate fuel
continuously as long as the reactants are supplied

standard electrode potentials for reactions in hydrogen fuel

cell in alkaline conditions H2O
+heat
4e- + 4H2O ⇌ 2H2 +4OH- E=-0.83V
4e- + 2H2O +O2 ⇌ 4OH- E=+0.4V

Anode: negative 2H2 +4OH-  4e- + 4H2O

Using standard conditions: The rate is too slow to
Cathode: positive 4e- + 2H2O +O2 ⇌ 4OH- produce an appreciable current.

Overall reaction 2H2 + O2  2H2O E=1.23V Higher temperatures are therefore used to increase rate
but the reaction is exothermic so by applying le chatelier
would mean the emf falls.
A higher pressure can help counteract this

2e- + 2H+ ⇌ H2 E=0V In acidic conditions these are the

electrode potentials. The Ecell is the
4e- + 4H+ +O ⇌ 2H2O E=1.23V
2 same as alkaline conditions as the
Overall 2H2 + O2  2H2O E=1.23V overall equation is the same

Advantages of Fuel cells over conventional petrol or Limitations of hydrogen fuel cells
diesel-powered vehicles (i) expensive
(i) less pollution and less CO2. (Pure hydrogen emits (ii) storing and transporting hydrogen, in terms of safety,
only water whilst hydrogen-rich fuels produce only feasibility of a pressurised liquid and a limited life cycle of a
small amounts of air pollutants and CO2). solid ‘adsorber’ or ‘absorber’
(ii) greater efficiency; (iii) limited lifetime (requiring regular replacement and
disposal) and high production costs,
(iv) use of toxic chemicals in their production

Hydrogen is readily available by the electrolysis of Hydrogen can be stored in fuel cells
water, but this is expensive. To be a green fuel the (i) as a liquid under pressure,
electricity needed would need to be produced from (ii) adsorbed on the surface of a solid material,
renewable resources (iii) absorbed within a solid material;

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Ethanol fuel cells

Ethanol fuel cells have also been developed. Compared to

Equation that occurs at oxygen electrode
hydrogen fuel cells they have certain advantages including.
4e- + 4H+ +O2  2H2O E=1.23V
Ethanol can be made from renewable sources in a carbon
neutral way Equation that occurs at ethanol electrode
Raw materials to produce ethanol by fermentation are C2H5OH + 3H2O → 2CO2 + 12H+ + 12e-
abundant
Ethanol is less explosive and easier to store than hydrogen. Overall equation
New petrol stations would not be required as ethanol is a C2H5OH + 3O2 → 2CO2 + 3H2O
liquid fuel.

Breathalysers

The earliest breathalysers used the colour change that

occurs when dichromate(VI) ions react with ethanol to
measure the amount of alcohol. They could measure the
extent to which dichromate turns green

Fuel cells measure the current from an ethanol fuel cell.

More alcohol means larger current measured. Fuel cell
breathalysers are portable
Many countries will use evidence from
Infrared breath analysers can determine the amounts both fuel cells and infrared breath
of alcohol from an infrared spectrum. More alcohol means analysers for evidence for prosecution,
greater absorbance. The infrared breathalysers do not because additional evidence is more
use the OH absorption to detect the amount of alcohol on reliable.
the breath because Water in the breath also has an OH
bond.

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