A2 – Physical Chemistry: Electrochemistry

L6– Applying Electrochemistry

Objectives:
•To understand that electrochemical cells can be used as a commercial source of
electrical energy, and that cells can be non-rechargable (irreversible), rechargable or fuel
cells
•To be able to use given electrode data to deduce the reactions occurring in non-
rechargeable and rechargeable cells and to deduce the e.m.f. of a cell
•To explain how some cells can be recharged
•To explain how a hydrogen fuel cell works
•Understand the electrode reactions of a hydrogen-oxygen fuel cell and appreciate that a
fuel cell does not need to be electrically recharged
•Evaluate the benefits and risks associated with uses these cells.

Specification:
3.1.11 A-level Electrode potential
and electrochemical cells
Commercial cells
Batteries are based on the principles of electrochemical cells.
You will need to apply the principles of electrochemical cells but
you will not be expected to learn the details of the construction
of the cells described below

Batteries and cells:

A battery is 2 or more cells connected in series.
Commercial cells
3 main types of commercial electrochemical cells:

1. Primary cells: non-rechargeable and thrown away after they run

down. The chemicals are used up over time (one or more), the
cell is flat and the emf is 0V. Single use only

2. Secondary cells: can be recharged after they run down.

3. Fuel cells: produces electricity from gaseous or liquid fuels.

1. Primary Cells (Non-rechargeable cells)
Daniell Cell (1836)
• Zn dipped in aqueous ZnSO4 in a porous pot.

• The pot itself is surrounded by aqueous CuSO4 in a copper can.

Zn acts as the anode. e- are lost and the Zn is oxidised.

Zn(s) → Zn2+(aq) + 2e-

Cu acts as the cathode. e- are gained and Cu2+ ions are reduced:

Cu2+(aq) +2e- → Cu(s)

It works on the principle of electrons being transferred from a more reactive
metal to a less reactive one
Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Ecell = 1.1V
1. Primary Cells (Non-rechargeable cells)

•The vol
tage can
differenc be worke
e in elect d out by t
•Not ver r ode pote he
y portabl ntials
electrolyt e b ecause of
es. the liquid
•Most m
odern cel
•Electrol ls are “dr
yte is pre y cells”
gel, which se nt as a da
does not mp paste
turned up spill if the or
side down c ell is
.
Disadvantages in red and advantages in
green
1. Primary Cells (Non-rechargeable cells) - Zinc-Carbon Cell
Cheap • Standard cell
Short shelf life - as the cell discharges zinc is used • Use door bells
up (oxidation). Zinc wall becomes thin + eventually • For small current intermittently
causes the contents to leak out
The ammonium chloride electrolyte is acidic and
can be corrosive – remove batteries from An alternative is to use the zinc
equipment chloride (electrolyte) cell – they are
Zinc canister (negative electrode) with ammonium better at supplying high currents
chloride paste and water – the electrolyte. Carbon and are marketed as extra life-0.80 V
rod centre (positive electrode) with a mixture of batteries for radios, torches and
manganese (IV) oxide and powdered carbon. +0.70 V
shavers. (see EQ 1 booklet LJW)
Zinc : Zn2+ + 2 e- ⇌ Zn
Carbon rod: 2NH4 + (aq) + 2e- ⇌ 2NH3(g) + H2(g)
Produce a p.d. approx 1.5V, which gradually
reduces to approx 0.8V when run down.
Overall discharge: Zn(s) + 2NH4+(aq) → 2NH3 + Zn2+(aq) + H2 (g)
The hydrogen gas is oxidised to water by the
manganese (IV) oxide preventing a build up of
pressure. Whilst ammonia dissolves in the water of
the paste
-0.80 V [Zn(NH3)2]2+(aq) + 2e- ↔ Zn(s) + 2NH3(aq)
+0.70 V 2MnO2 (s) + 2H+ (aq) + 2e- ↔ Mn2O3(s)+ H2O (l)
Overall: Zn(s) + 2MnO2 (s) 2NH4+(aq) → [Zn(NH3)2]2+(aq) + Mn2O3(s)+ H2O (l)
1. Primary Cells (Non-rechargeable cells) Alkaline Dry Cells
• Longer life
•Produce the same p.d. as zinc-carbon cells but
they last longer (1.6V)
•Electrolyte = KOH rather than ammonium
chloride or zinc chloride.
•Closed in a steel container to prevent leakage
•Personal stereos (16 x longer)
•More expensive

Anode: Powdered zinc alloy (greater SA allows

battery to supply high currents) mixed with KOH.
Cathode: Mixture of KOH, powdered
manganese(IV) oxide and graphite.
At anode: Zn is oxidised from 0 to +2. hydroxide
ions react with Zn ions.
At Cathode: Manganese is reduced from +4 to Porous separator = allow ions
+3 to pass through it

76 V ZnO (s) +H2O (l) + 2 e- ↔ Zn (s) + 2OH- (aq)

.84 V 2MnO2 (s) + H2O + 2e- ↔ Mn2O3(s) + 2OH-
Overall: Zn (s) + 2MnO2 (s) + → ZnO (s) + Mn2O3(s)
2. Rechargeable (secondary) cells

• In non-rechargeable (primary) cells, the chemicals are

used up so the voltage drops.
• In rechargeable (secondary) cells the reactions are
reversible – they are reversed by applying an external
current that is greater than the voltage of the cell to
drive the electrons in the opposite direction.
• It is important that the products from the forward
reaction stick to the electrodes and are not dispersed
into the electrolyte.
 2. Rechargeable (secondary) cells - Lead-acid batteries
•6 cells in series – each producing 2V, giving a
total voltage of 12V.
•Each cell consists of 2 plates dipped into a
solution of sulfuric acid.
•Electrolyte = approx 6M H2SO4

When charged:
Anode: spongy lead rod made of lead alloy.
Cathode: lead(IV) oxide in a similar grid
Grid provides a large SA for electrode reactions
to happen and improve the efficiency of the
battery.
Anode: when the battery discharges • Used in sealed car
Pb (s) + SO4 (aq) ↔ PbSO4 (s) + 2 e
2- -
batteries
Cathode: When battery discharges:
PbO2 (s) + 4H+ (aq) + SO42- (aq) + 2 e- ↔ PbSO4(s) + 2 H2O(l)
Overall : PbO2 + Pb + 2H+ + 2HSO4–  2PbSO4 + 2H2O emf 2.04
These reactions are reversed as the battery is charged up and electrons flow in
the reverse direction, driven by the car’s generator
Charging: 2PbSO4 + 2H2O  PbO2 + Pb + 2H+ + 2HSO4–
.68 V PbO2 (s) + 4H+ (aq) + SO42- (aq) + 2 e- ↔ PbSO4(s) + 2 H2O(l)
- 2-
 Lead-Acid Battery – for environmental
advantages and disadvantages see further down
• Advantages:
– Batteries of all shapes and sizes, available in
– Maintenance-free products and mass-produced
– Best value for power and energy per kilowatt-hour
– Have the longest life cycle and a large environmental advantage
– Ninety-seven percent of the lead is recycled and reused in new
batteries

• Disadvantages:
– Lead is heavier compared to alternative elements

5
Portable batteries
• There are now rechargeable batteries that come in all shapes
and sizes
2. Rechargeable (secondary) cells - Nickel/Cadmium (Nicads)
Most common cell in everyday use.
P.d. Of 1.4V (slightly less than pd of zinc-
carbon cells and alkaline dry cells.
Recharged 500x
Anode: Cadmium
Cathode from nickel(III) hydroxide
Electrolyte: KOH
Anode reactions:
Cd(OH)2 (s) + 2 e- ↔ Cd (s) + 2 OH- (aq)

-0.88
Cathode reactions:
NiO(OH) + H2O + e- ↔ Ni(OH)2 + OH-
+0.52
Overall: 2NiO(OH) + 2 H2O + Cd  2Ni(OH)2 + Cd(OH)2
Emf = +1.40 V
The reaction goes from left to right on discharge (electrons flowing from Cd to Ni)
and right to left on charging
+0.52 V Ni(OH)3 + 2 H2O + 2 e- ↔ Ni(OH)2 + 2 OH-
-0.88 V Cd(OH)2 (s) + 2 e- ↔ Cd (s) + 2 OH- (aq)
Nickel-Cadmium Battery -for environmental
advantages and disadvantages see further down
• Advantages:
– Operate in a range of temperatures
– Tolerates abuse well and performs well after long periods
of storage

• Disadvantages:
– It is three to five times more expensive than lead-acid
– Its materials are toxic and the recycling infrastructure for
larger nickel-cadmium batteries is very limited

7
Lithium ion cell ;- On charging the electrons are forced through
the external circuit from + to – electrodes and at
Used in Laptops, mobile phones and the
power
same tools
time Li ions move through the
electrolyte towards the positive electrode to
maintain the balance of charge
 2. Rechargeable (secondary) cells – Li-ion batteries
•Used in portable devices: Laptops and mobile phones.
•Light as they use Li (less dense metal) instead of heavier metals.
•More complex than other secondary cells – they include a computer
chip to control charging and discharging.
•Electrolyte is a solid polymer (rather than (l)) so it cannot leak
•Charge can be topped up at any time – doesn’t have to be fully
discharged to recharge.
•Much higher p.d., 3.7V
Anode: graphite (carbon)
Cathode: lithium cobalt oxide (LiCoO2)
These are arranged in layers with a sandwich of solid electrolyte in
between
• Rechargeable
Anode:
Charging: Li+ + e- ↔ Li • Most common
Cathode: rechargeable cell
Charging: Li+ (aq) + CoO2 (s) + e- ↔ Li+(CoO2 )- (s)
In use: CoO2 + Li  LiCoO2
Charging: LiCoO2  CoO2 + Li Emf = +3.60 V

0.60 V Li+ (aq) + LiCoO2 (s) + e- ↔ Li2CoO2 (s)

3.00 V Li+ + e- ↔ Li (Actually Li+ (aq) + 6C (s) + e- ↔ LiC (s) )
Lithium- ion battery for environmental advantages and
disadvantages see further down
3. Fuel Cells - The hydrogen-oxygen fuel cell
• Transform the chemical energy in a fuel such as hydrogen or methanol
directly into electrical energy.
• Fuel is oxidised by oxygen from air using electrochemical reactions in
the fuel cell.

• 2 flat electrodes, each coated on 1 side with Pt catalyst.

• A PROTON EXCHANGE MEMBRANE sandwiched between the 2
electrodes.
• Air flows to the cathode.
• Any un-reacted hydrogen is re-circulated – no need for recharge
• Water vapour - reaction product – is pushed out by the stream of air
• Used for spacecraft – used as drinking water by the astronauts

• There are two types of hydrogen fuel cell: Alkaline and acidic
Alkaline hydrogen fuel cell

3. Oxygen gas
enters
1. Hydrogen gas flows
to the anode (-) O2(g) + 2H2O(l) + 4e- 
4OH-(aq)
2H2(g) + 4OH-(aq) 
4. This accepts
4H2O(l) +4e- electrons from the
2.This releases other electrode
electrons that flow and releases OH-
through the circuit ions which travel
to the other through the semi
electrode permeable
membrane to that
electrode

5. Overall
2H2 (g)+ O2(g)  2H2O(l) emf = 1.23V
NB: no nitrogen oxides are produced as this takes place at a low temp (these form if hydrogen burn directly)
Alkaline hydrogen fuel cell
To increase the
current the heat
generated by the cell
is used to raise the

temperature
and pressure .

The electrodes are

also impregnated with
the catalysts
Pt and Pd .

This may appear to be ‘green’ energy but only if the hydrogen is

made by the electrolysis of water using electricity

generated without the use of fossil fuels.

Other fuels
• The fuel doesn’t have to be hydrogen either
• Similar reactions can take place with hydrogen rich fuels i.e.
methanol and ethanol
• Which can also reduce the oxygen and form water

• See Q 1(e) booklet

Acidic hydrogen fuel cell

Acidic electrolyte (down the centre)

3. Oxygen gas
enters
1. Hydrogen gas
flows to the anode O2 (g) + 4H+ (aq) + 4 e-
↔ 2H2O (l)
2 H+ (aq) + 2 e- ↔ H2 (g)
4. Oxygen is
2.This releases reduced to water
electrons that flow
vapour. It reacts
through the circuit
to the other
with the H+ ions
electrode that pass through
the proton
The H+ ions pass exchange
through the membrane to the
proton exchange cathode.
membrane to the
5. Overall
cathode
2H2 (g)+ O2(g)  2H2O(l) emf = 1.23V
NB: no nitrogen oxides are produced as this takes place at a low temp (these form if hydrogen burn directly)
There are two types: Alkaline and acidic hydrogen fuel cells

hydrogen fuel cell (alkaline) hydrogen fuel cell (acidic)

Negative H2 + 2OH– ⟶ 2H2O + 2e– H2 ⟶ 2H+ + 2e–

electrode
(anode) E° = –0.83 V E° = +0.00 V

Positive O2 + 2H2O + 4e– ⟶ 4OH– O2 + 4H+ + 4e– ⟶ 2H2O

electrode
(cathode) E° = +0.40 V E° = +1.23 V

Overall
2H2 + O2 ⟶ 2H2O 2H2 + O2 ⟶ 2H2O
equation

Cell emf +1.23 V +1.23 V

Fuel Cells- Benefits and Risks and the ‘green energy’ claims

Benefits Risks

To replace fossil fuels Storage/Transport

Fuel prices are high Lifetime

(savings possible)
Production Costs
Constant output
Toxic Chemicals used in
production
If the Hydrogen comes from fossil fuels then there is no ‘green energy’
claim possible. If however we source H2 from electrolysis of water based
on solar/hydro/wind resources then we can claim this.
 OVERALL Benefits & risks of using cells

Benefits Risks

Using cells  portable source of electrical energy  waste issues

Using non-
 cheap  waste issues
rechargeable cells

 less waste (no landfill problems)

 some waste issues (at end of useful life)
 Does not leak
Using re-  Waste gases (CO2 released) – electricity
chargeable cells  Metal compounds are reused/supplies
from recharging may come from
are not depleted
powerstations
 Less mining/less energy to extract
 only waste product is water (less waste)  need constant supply of fuels

Using hydrogen  do not need re-charging  hydrogen is flammable & explosive

fuel cells  very efficient  hydrogen usually made using fossil fuels
 Useful energy created  high cost of fuel cells
For Lead batteries voltage reduces steadily with time so power is
lost steadily.

For Fuel cells and Li cells voltage is maintained with time so power is
constant until cell suddenly losses all power..