Electrochemistry

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Chapter 20: 855 - 888

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 1. What is Electrochemistry?

• Electrochemistry deals with the relationships between

electricity and chemical reactions

2. Why is Electrochemistry Important to Engineers?

Provides understanding into:

• how batteries and fuel cells work
• Electroplating
• Corrosion of metals

2
 3. Voltaic Cells
a) What is a Voltaic/Galvinic Cell?
Chemistry: The Central Science,
Brown, LeMay Bursten, 10th ed
• A device in which a
spontaneous redox reaction
occurs with the passage of
electrons through an external
circuit.

Example 1 – Not a Galvanic Cell

• A zinc strip in a beaker
containing a Cu2+ solution
• Reaction is spontaneous
• Cu2+ is reduced to Cu(s)
(blue colour fades;
Cu is deposited on Zn)
• Zn(s) is oxidised to Zn2+
Zn(s) +Cu2+(aq) → Zn2+(aq) + Cu(s)
(Zn dissolves) 3
 Example 2 –Galvanic Cell

Salt bridge

Zn(s) + Cu2+(aq) →
Chemistry: The Central
Science, Brown, LeMay Zn2+(aq) + Cu(s)
Bursten, 10th ed 4
 3. Voltaic Cells

• Anode: electrode at which oxidation occurs. Since negatively

charged e’s are released at the anode, the anode is given a
negative sign. ANOX

• Cathode: electrode at which reduction occurs. Since e’s flow

into the cathode, the cathode is given a positive sign. REDCAT

• Salt bridge: U-shaped tube that contains an electrolyte solution

(eg NaNO3(aq)) in a gel. It is needed to neutralise the inc [Zn2+]
in the anode compartment and the dec [Cu2+] in the cathode
compartment. No current will flow if a salt bridge is not used.
This is because the build of positive charge in the anode
compartment will inhibit further oxidation of Zn(s). The excess
of negative charge in the cathode compartment will inhibit
further reduction of Cu2+. The salt bridge completes the
electrical circuit. 5
 3. Voltaic Cells

• Cell potential or electromotive force (emf): Ecell:

Difference in potential energy per electrical charge between
the two electrodes of a voltaic cell (1V = 1 J/ 1 C)

• The emf of a voltaic cell depends on:

- The reactions that occur at the anode and cathode
- The concentrations of reactants and products
- The temperature

• The reaction will only be spontaneous if the emf of the voltaic

cell is positive.

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 3. Voltaic Cells
θ
b) The Standard Cell Potential / emf (E ) cell

• Standard emf : emf of a cell operated under standard conditions

- 25 ºC
- 1 M concentrations for reactants and products in solution
- 1 atm pressure for gaseous reactants and products
E  E (cathode)  E (anode)
θ
cell
θ
red
θ
red
Note : E   E
θ
red
θ
oxid

• E = standard reduction potential

θ

red

(potential for reduction to occur at an electrode under standard

conditions)

• Values of E are listed in Appendix E

θ

red

• Values were measured relative to the standard hydrogen

electrode which is assigned a standard reduction potential of 0 V.
2H+ (aq, 1 M) + 2e- → H2 (g, 1 atm) E  0 V θ

red

7
 3. Voltaic Cells

b) The Standard Cell Potential / emf

• Emf measures the potential energy per electrical charge →

changing the stoichiometric coefficient in a half reaction does
θ
not affect the value of E .
red

• The more positive the E for a half reaction the more likely it
θ

red

is for the reactant of the ½ reaction to be reduced.

Q. Using the standard reduction potentials calculate the standard

cell potential for the following reaction:

Cr2O72-(aq) + 14H+(aq) + 6I-(aq) → 2Cr3+(aq) + 3I2(s) + 7H2O(l)

• Identify what is being reduced and oxidised.

8
 3. Voltaic Cells

c) The Cell Potential Under Non-Standard Conditions

RT
E E θ
ln Q Nernst Equation
nF
• Eθ = standard cell emf (V)
• n = number of moles of electrons transferred in the reaction (mol
e- )
• F = Faraday’s constant = 96485 J V-1 (mol e-)-1
• Q = reaction quotient – substitute actual reactant and product
concs into equilibrium expression – no units

Q. Calculate the emf of the cell for the following reaction at 25 ºC.
[Cr2O72-] = 2.0 M; [H+] = 1.0 M, [I-] = 1.0 M and [Cr3+] = 1.0 x 10-5 M

Cr2O72-(aq) + 14H+(aq) + 6I-(aq) → 2Cr3+(aq) + 3I2(s) + 7H2O(l)

9
 3. Voltaic Cells

c) The Cell Potential Under Non-Standard Conditions

• If [reactant] increases relative to [products] → emf increases

and cell reaction becomes more spontaneous.

• If [product] increases relative to [reactant] → emf decreases

• As the cell is discharged the emf of a voltaic cell will decrease

since [products] increase and [reactant] decrease.

• When the cell is completely discharged, E = 0 and the cell is

said to be ‘dead’. However the cell reaction has reached
equilibrium. There is no net reaction occurring within the
voltaic cell.

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 3. Voltaic Cells
d) Calculating the Equilibrium Constants for Redox Reactions

• When E = 0, the cell reaction is at equilibrium → Qc = Kc

• Substitute E = 0 into Nernst Equation:

RT
0 E 
θ
ln Kc
nF

nFE
Kc  exp ( )
RT

Q. Calculate the equilibrium constant for the following reaction in

acidic solution at 25 °C.

O2(g) + 4H+(aq) + 4Fe2+(aq) → 4Fe3+(aq) + 2H2O(l)

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 4. Commercial Voltaic Cells

• A battery consists of one or more voltaic cells and serves as a

portable source of electricity.

a) Lead-Storage Battery

• Eg. A 12 V battery used in cars

• Consists of a number of galvanic cells connected in series

• A secondary cell can be recharged from an external power

source after its emf has dropped. Car Battery is recharged by
the generator or alternator of the car

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 4. Commercial Voltaic Cells

b) Zinc-Carbon Dry Cell

• Uses: power flashlights, tape recorders, electronic devices,

etc
• Delivers 1.5 V (single voltaic cell)
• Cannot be recharged (primary cell)

c) Alkaline dry cell

• Uses: power flashlights, tape recorders, etc

• Delivers 1.5 V (eg Duracell)
• More expensive than Zn/C dry cell but delivers more current
and has a longer shelf life
• Cannot be recharged
• Example of miniature alkaline cell for use in cameras,
calculators and watches 13
 5. Electrolysis
a) What is Electrolysis?

• A process in which a non-spontaneous redox reaction is

made to occur by the passage of current under a sufficiently
large external electrical potential.

• ΔE is negative

• Consider the following non-spontaneous reaction of molten

NaCl: 2NaCl(l) → 2Na(l) + Cl2(g)

• Cathode: 2Na+(l) + 2e- → 2Na(l) E   2.71 V

θ
red

• Anode: 2Cl-(l) → Cl2(g) + 2e- E   1.36 V

θ
red

• The reaction can be made to occur by using a battery to

push electrons to Na+(l) and pull electrons from Cl-(l).
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 5. Electrolysis
a) What is Electrolysis?

2NaCl(l) → 2Na(l) + Cl2(g)

Q. What is Eº for the above reaction ?

Q. Draw the cell for the above reaction.

• Note how the anode and cathode are charged in comparison

to a voltaic cell

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 5. Electrolysis
b) Electrolysis of Aqueous Solutions

• You must consider water can be reduced or oxidised

(involved at one or both electrodes)

• Consider an aqueous solution of NaCl.

• Species present: Na+(aq); Cl-(aq) and H2O(l)
• Possible reactions at the cathode:
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E   0.83 V
θ
red

Na+(aq) + e- → Na(s) E   2.71 V

θ
red

• Possible reactions at the anode:

2Cl-(aq) → Cl2(g) + 2e- E  1.36 V
θ
red

2H2O(l) → 4H+(aq) + O2(g) + 4e- E  1.23 V

θ
red

Q. Which reactions would you predict would occur at the

cathode and anode during electrolysis? 16
 5. Electrolysis
b) Electrolysis of Aqueous Solutions

• Actually at higher [NaCl] Cl-(aq) is oxidised to Cl2(g) due to

high overvoltage required for O2 formation. Overvoltage is
necessary because of slow reaction rates at electrodes.

• Overvoltage - larger voltage supplied than predicted from

electrode potentials

• Products depend on concentration and pH

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 5. Electrolysis
c) Calculating Quantities in Electrolysis

• ½ reactions relate the amount of substances reduced or

oxidised in an electrolytic cell to the mols of electrons
needed for electrolysis.

Q = It Moles of
Current (A), ÷F Moles of substance
Charge (C)
Time electrons oxidised or
reduced
Q. Calculate the mass of Al
produced in 1.00 hr by the Grams of
electrolysis of molten AlCl3 if substance
the electrical current is 10.0 A. oxidised or
reduced

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 5. Electrolysis
d) Electrical Work w = -nFE Note: n= moles of e-’s

• Work done by a system on its surroundings is indicated by a

negative sign for w.
• For spontaneous electrochemical processes useful electrical
work can be obtained from the cell (E is positive; therefore w is
– ve )
• For a voltaic cell w is the maximum work obtained from the
cell.

• Work done on a system by its surroundings is indicated by a

positive sign for w.
• For a non-spontaneous process E is –ve therefore w is +ve.
• Ecell is negative for an electrolytic cell. To force the process to
occur an external potential must be applied which is larger than
Ecell. (w = nFEext)
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 5. ELECTROLYSIS
d) Electrical Work

• The unit employed by electric utilities for electrical work is

the kilowatt-hour
 3600 s  1 J/s 
1 kWhr  (1000 W)(1 hr)     3.6 x 10 J
6

 1 hr  1 W 

Q. Calculate the number of kilowatt-hours of electricity required

to produce 1.0 x 103 kg of Al by electrolysis of Al3+ if the
applied emf is 4.50 V.

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 5. Electrolysis
e) Applications of Electrolysis

• Recovery of Mg from dolomite (CaCO3.MgCO3)

• Recovery of Al from bauxite (Al2O3.xH2O)

(Hall – Héroult Process)

• Electroplating: One metal is deposited onto another in order

to improve beauty or resistance to corrosion

• Eg. Silver-plated teaspoons are manufactured by making the

teaspoons the cathode in an electrolytic plating bath. Ag+(aq)
is reduced onto the spoons.
Ag+(aq) + e- → Ag(s)

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 6. Corrosion
• Corrosion reactions are spontaneous redox reactions in which
a metal is attacked by some substance in the environment and
converted to an unwanted compound.

a) Corrosion of Fe

• To rust iron you need oxygen and water

• Presence of salts enhances corrosion (provides electrolyte
necessary to complete electrical circuit)
• Fe(s) can be spontaneously oxidised by O2(g)

• Cathode: O2(g) + 4H+(aq) + 4e– → 2H2O(l) E  1.23 V

θ
red

• Anode: Fe(s) → Fe2+(aq) + 2e– E   0.44 V

θ
red

• Fe2+ is oxidised further to Fe3+ which forms the hydrated

iron(III) oxide (ie. rust)
4Fe2+(aq) + O2(g) + 4H2O(l) + 2xH2O(l) → 2Fe2O3.xH2O(s) + 8H+(aq) 22
 6. Corrosion
b) Cathodic protection

• Iron can be protected from O2 and H2O by covering it with

another metal such as tin or zinc
• Galvanized iron – iron coated with a thin layer of zinc
Fe2+(aq) + 2e- → Fe(s) E   0.44 V
θ
red

Zn2+(aq) + 2e- → Zn(s) E   0.76 V

θ
red

• Zinc is more easily oxidised therefore it will be corroded instead

of iron even if the zinc coating is broken.
• Sacrificial anode → metal that is oxidised while protecting the
cathode
• Fe serves as the cathode and Zn serves as the sacrificial anode

Q. Which of the following metals could provide cathodic protection

to iron?
Al3+/Al, Eº = -1.66 V Cu2+/Cu, Eº = +0.34 V Ni2+/Ni, Eº = - 0.28 V 23