Electrochemistry

2.4 Oxidation Numbers

Oxidation numbers are fictitious charges that can be

assigned to the elements in a compound. They are
useful in describing redox reactions and also in
chemical nomenclature.
 Rules for assigning oxidation numbers
The sum of the oxidation numbers of the elements in
a molecule or ion must conserve the overall charge.
Uncombined elements are 0
Alkali metals are +1
Alkaline earths are +2
Fluorine is -1
Other halogens -1, +ve in cmpds with O
Hydrogen +1, except in metal hydrides -1
Oxygen -2, except in oxyfluorides and peroxides
Note that the oxidation number is not necessarily the same as the
true charge on an atom.
+1 +7 -2 +1 +6 -2
KMnO4 H2SO4

+5 -2 +6 -2
N 2O 5 SO42-

+1 -2 +3 -1
H 2S ClF3
 10.1 Balancing Oxidation-Reduction
Reactions
(see O+N problems 10.1-10.4)
Oxidation/reduction reactions involve a change of
oxidation state of some of the species.

eg. Burning of Mg in air is oxidation reaction

Mg(s) + O2(g) → 2MgO(s) Mg oxidized;O2 is
reduced

REDOX reactions can be written down as the sum

of two half reactions each of which will involve
electrons.
Example: Copper dissolving in AgNO3 solution
The overall process appears to be:
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
But notice that the copper and silver are reacting in
different regions of the solution.
The copper half reaction must be:
Cu(s) → Cu2+(aq) + 2e– Oxidation
The silver half reaction must be:
Ag+(aq) + e– → Ag(s) Reduction

Remember - Oxidation Is Loss of electrons; Reduction Is

Gain of electrons - OILRIG
No net electrons produced or consumed. So we need to
double the silver reaction:
2Ag+(aq) + 2e– → 2Ag(s)
Cu(s) → Cu2+(aq) + 2e-
______________________________
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
The "oxidant" or oxidizing agent = the reactant which
causes the other reactant to be oxidized. The oxidant is
itself reduced. Oxidant Gains Electrons and is Reduced
OGER - in this case Ag+
The "reductant" or reducing agent = the reactant which
causes the other reactant to be reduced. The reductant is
itself oxidized. Reductant Loses Electrons and is
Oxidized RLEO - in this case Cu
Example: Zn dissolving in acidic dichromate solution
Zn → Zn2+ + 2e- ; Cr2O72- (orange) → Cr3+ (green)
Steps for balancing the Cr half reaction:
(i) balance Cr Cr2O72– → 2Cr3+
(ii) add water to balance oxygen :
Cr2O72– → 2Cr3+ + 7H2O
(iii) add H3O+ to balance hydrogen (ensuring O balance)
Cr2O72– + 14 H3O+ → 2Cr3+ + 21H2O
(iv) balance charges:
Cr2O72– + 14 H3O+ + 6e- → 2Cr3+ + 21H2O
Add the half reactions to balance electrons :
3Zn + Cr2O72- + 14H3O+ → 2Cr3+ + 21H2O + 3Zn2+
Example - Chromium III hydroxide reacts with sodium
hypochlorite in basic solution

Cr(OH)3 → CrO42- ; ClO - → Cl-

Balance as for acidic solutions

Cr(OH)3 + 6H2O → CrO42- + 5H3O+ + 3e-

Add OH- to both sides of equation to ‘remove H3O+’

Cr(OH)3+ 6H2O + 5OH-→ CrO42- + 5H3O+ + 5OH-+ 3e-

H3O+ and OH- form water; balance water

Cr(OH)3 + 5OH-→ CrO42- + 4H2O + 3e- Eq.1
 Repeat for other 1/2 equation.

ClO- + H2O + 2e- → Cl- + 2OH- Eq. 2

Add both half equations taking care to balance for electrons.

3  Eq. 2 + 2  Eq. 1 :

(Cr(OH)3 + 5OH-→ CrO42- + 4H2O + 3e- Eq.1)

2Cr(OH)3 + 3ClO - + 4OH- → 2CrO42- + 3Cl - + 5H2O

10.2 Electrochemical Cells and Cell
Reactions
Lithium Iodide
Consider the
Lithium Iodide Iodine (on
polymer
Battery: support)
the overall reaction
is 2Li + I2 → 2LiI
Although the cell is
Lithium
very light it is
energy dense. electron flow
This cell is often written as:
Li | LiI | I2(polymer)
The vertical bars signify a boundary between phases.
In the laboratory this cell could be studied in the
form: electron flow

Lithium salt bridge (lithium iodide in

gelled propylene carbonate)

Platinum electrode

Iodine in solution
in propylene
Li+ Li+ carbonate

I– I–
We would then denote the cell as
Li | Li+ || I2 | I- | Pt
where the double bars indicate the salt bridge.

The reduction reaction is usually put on the right of

the diagram-reduction occurs at the cathode (+).

Oxidation occurs at the anode (-).

The individual half cell reactions are written in
standard form as reductions:
Li+ + e– → Li and
I2 + 2e– → 2I-

The overall cell reaction is then taken to be:

Half reaction(right) - Half reaction(left)

Make sure the electrons cancel ( Li reaction  two).

Cell Voltage
Vcell = Vright - Vleft
The overall cell voltage should be measured under
conditions in which no current is drawn. Then the half cell
reactions are in equilibrium (each with its own solution).
We denote the cell voltage in this special case as:
Ecell = Vcell (i=0)
If the cell current is not zero then a cell reaction occurs
either in the spontaneous direction (a galvanic cell), or in
the reverse direction (an electrolytic cell).

The measured cell voltage for the LiI cell is 3.5 V.

How do we split this between the two half cells?
Half-Cell Voltages (10.3)
We assign our zero of voltage as the standard
hydrogen electrode, i.e.
Pt | H2(P=100kPa) | H+(a=1).
Standard electrode potentials, E0, can then be found for
each half cell reaction from measurements on cells.
from tables of standard reduction potentials ( O&N Appendix E):
E0(Li+/Li) = -3.0 V
E0(I2/I–) = 0.53 V
Hence: Ecell = E0(cathode) - E0(anode)
= 0.53 V - (-3.0 V) = 3.53 V
Warning: Don't try to multiply these voltages by the number of moles
of electrons in the reaction.
Faradays Laws (10.2) (Quantitative relationship between
amounts of substance reacting and the total electric charge
that passes)
Say we have passage of 1 mol of electrons in the circuit.
The charge passed is 6.023  1023  1.60  10-19 C
So there are 96485 Coulomb per mol of e–
This quantity is given the symbol
F "Faraday's constant"
The charge in coulombs passed in external circuit is
Q (C) = I(A)  t(s)
So the number of moles of electrons generated or
consumed at the electrodes is: - It
mol e =
F
Problem:
If 0.10 A passes for 30s, how many moles of Li
have oxidized in the battery to supply this current?

Solution:
0.10A   s
mol of electrons = = 3.1  10 -5 mol
96485 C mol-1
Now, since 1 mol e– = 1 mol Li
The number of mol Li used is 3.1  10-5
The corresponding mass of Li is
3.1  10-5 mol  6.94 g mol-1= 0.22 mg(Li)

Ignore material on G in section 10.3 !!!

10.5 Concentration Effects

Tabulated E0 values are measured and

quoted for conditions when the activities of
all ions = 1.

What happens if activities of ions  1?

The Nernst equation relates E to activities:
RT
0
E = E – ln[ Qcell reaction ]
nF
R = 8.314 JKmol-1
T is the temperature in Kelvin
n = number of electrons
F = 96485 C mol-1
The cell reaction can be for a complete cell, or a half cell.

If dealing with half-cells, the Qcell should be set up by

writing each half-reaction as a reduction.

For a complete cell, write the equation for the overall

spontaneous process, and set up Qcell from this.
Example 1:
In the lithium iodide cell,
[Li+] = 10-4 M,
[I2] = 0.01 M,
[I-] = 10-5 M

Calculate the half cell and overall cell voltages

under these conditions.
 First we work out the two half cell potentials using the
Nernst Equation:
(i) for the lithium half cell: Li+ + e- → Li; Eo = (Li +/Li) = -3.0 V

RT
0 a Li 1
E = E – ln[Q cell reaction] and Q = =
nF a +
Li [ ]
Li +

(8.314 JK -1mol-1) (298 K)  1 

E = -3V - ln -4
1 (96485 Cmol ) -1 10 

= -3.0 V - (0.24 V)
= -3.24 V
joule
(note: 1 = 1 volt )
coulomb
(ii) for the iodide half cell: I2 + 2 e– → 2I- ;E0(I2/I–) = 0.53 V

2
Q =
a I2–
=
[I]
-

aI2 [ I2]
8.314 JK - 1mol - 1 298 K (10 - 5 )2 
E = 0.53 - - 1 ln -2 
2 (96485 Cmol )  10 

= 0.53 V + 0.237 V
= 0.77 V
Hence the overall cell voltage is:
Ecell = Ecathode- Eanode
= 0.77 V - (-3.24 V)
= 4.01 V
 We see that the cell voltage is higher than for
standard concentrations.
Because both products are at low concentrations the
cell reacts to produce more products.
As the cell reacts ("discharges")
products build up and reactants run down
cell potential drops.
Suggestion: try re-calculating the cell potential for [Li+] =
1M, [I2] = 10-5 M, [I-] = 10-2 M.

Most useful batteries have solid reactants and products

such that the activities stay approximately = 1 as the
cell discharges.
Example 2

The Daniel cell is

Zn + Cu2+ Cu + Zn2+
Zn|Zn2+||Cu2+|Cu

The E0(cell) under standard conditions (a =1) is

E0(cell) = 0.34 - (-0.76) = 1.1 V

Calculate E(cell) for the Daniel cell when

[Zn2+] = 10-5 mol dm-3
[Cu2+] = 1.0 mol dm-3
Solution:

a Cu a Zn2+
Q cell = = 10 - 5
a Zn a
Cu2+

8.314 JK - 1mol- 1 298 K -5 )

E = 1.10 - ln(10
2 (96485 Cmol - 1)

= 1.10 - (- 0.148 )

= 1.25V
 In the above examples the result we determine for
E(cell) does not depend on the way we write down
the cell reaction.
For example in the LiI cell, we could write
2Li + I2 → 2Li+ + 2I-
 Li+ 2 I- 2 
0 RT  [ ][ ] 
for which E = E - ln
2F  Li 2 I 1 
[ ] [ ]
 2 
or alternatively:
Li + 0.5I2 → Li+ + I-
 Li+ 1 I- 1 
0 RT  [ ][ ] 
E = E - ln
F  Li 1 I 0.5 

[ ] [ ] 2 

The two expressions evaluate to identical results!!

Lead-acid storage batteries 12 volts, 6 cells in series
Anodes :lead plates. Cathodes: PbO2 coated on lead.
Gaston Plante 1859
 Anode reaction:
Pb(s) + SO42–(aq) → PbSO4 (s) + 2e-
Cathode reaction:
PbO2(s)+SO42-(aq)+4H3O+(aq)+2e- → PbSO4 (s) + 6H2O(l)
The electrolyte density drops and pH increases in the discharge
reaction:
Pb(s)+PbO2(s)+2SO42-(aq)+4H3O+ (aq)
→PbSO4(s)+6H2O(l)
NB. From standard reduction potentials:
E0(PbO2/PbSO4) = +1.685 V
E0(PbSO4/Pb) = -0.356 V V= RHS - LHS = 2.041V

Charging reaction goes in reverse !

Equilibrium Constants and E0 values

If a cell runs down to the point where E = 0

equilibrium is reached and hence Q = K.

Using the Nernst equation:

0 RT
E = E – ln[Q cell reaction ]
nF
so 0 RT
E = ln(K)
nF
This gives us a way to work out the equilibrium
constant K
Example: Discharge reaction of a lead-acid battery

Electrochemical data (given):

E0(PbO2/PbSO4) = +1.685 V
E0(PbSO4/Pb) = -0.356 V

so E0(cell) = 2.041 V

=> ln K = 159

=> K = 1.1 × 1069

10.4 Oxidizing and Reducing Agents:
Oxidation/reduction reactions can take place in
solution as well as on electrodes:
Electrons are transferred directly from one reactant
to the other:
e.g. Fe2+/Cr2O72–
E0(Fe3+/Fe2+) = 0.77V
E0(Cr2O72–/Cr3+) = 1.33V
Fe2+ → Fe3+ + e–
Cr2O72– + 14H3O+ + 6e– → 2Cr3+ + 21H2O
Erxn = 1.33 - 0.77 = 0.56V
Practical example:
Ethanol + dichromate + silver nitrate in
"breathalyzers" Captain R.F. Burkenstein -
Indiana State Police 1954.

CH3CH2OH(aq)+5H2O→CH3COOH(aq)+4H3O+(aq)+4e-

Cr2O72–(aq) + 14H3O+ (aq) + 6e– → 2Cr3+ (aq) + 21H2O

2Cr2O72–(aq) + CH3CH2OH (aq) + 16H3O+

(red)
Ag NO3 catalyst

2Cr3+ + CH3COOH(aq) + 11H2O

 10.6 Batteries and Fuel Cells
Cells that deliver energy are called "galvanic cells"
and are of two types: primary and secondary.
Primary:
e.g. the "Leclanche Cell" - "zinc-carbon cell"
electrolyte is moist paste of NH4Cl and ZnCl2
Zn → Zn2+ + 2e–
2MnO2 + 2NH4+ + 2e– → Mn2O3 + 2NH3 + H2O
Zinc anode shell, and a central carbon cathode.
This reaction involves dissolved species whose
concentrations will change during discharge.
 e.g. alkaline dry cells:
Zn + 2OH– → Zn(OH)2 + 2e–
2MnO2 + H2O + 2e– → Mn2O3 + 2OH–
Here all participants are solids no drop-off in voltage.

Secondary:
The electrodes in these batteries can be regenerated
after discharging by applying an external voltage
larger than their original voltage.
Ni-Cad batteries
Pb-acid car batteries

During the charging cycle the electrode reactions run in

the reverse direction to those in the discharge cycle.
Fuel cell:
A battery with continuous replacement of reactants
e.g. the hydrogen oxygen fuel cell:
H2 + 2OH– → 2H2O + 2e–
E0(H2/H2O) = -0.828V

›O2 + H2O + 2e– → 2OH–

E0(O2/OH–) = -0.401V

H2 + ›O2 → H2O
E0(cell) = 1.229V

Transforms chemical energy to electrical energy.

10.7 Corrosion and Its Prevention
Consider corrosion as a short circuited cell.
Some regions act as anodes, oxidizing the metal:
Fe → Fe2+ + 2e–
Other regions act as cathodes, at which reduction of
oxygen occurs:
O2 + 4H3O+ + 4e– → 6H2O
The process needs oxygen => these regions are
usually those most exposed.
Reactions also require the presence of a solution =
salt water, rain water and acid rain.
Sacrificial Anodes
Connect the metal object to a metal of more
negative standard reduction potential
: this oxidizes and makes the object the cathode:
e.g.
Fe2+ + 2e– → Fe
E0 = – 0.41V
Mg2+ + 2e– → Mg
E0 = –2.39V
or zinc
Zn2+ + 2e– → Zn
E0 = – 0.76V
 "galvanized iron"
 Now to get our coins
from the Atocha

Original problem was oxidation of Ag to Ag+

2Ag(s) + H2S(aq) → Ag2S(s) + H2 (g)

We need to reduce the Ag+ to Ag.
Ag2S(s) + 2e- → Ag(s) + S2- (aq)
 Power supply

Na+ OH-
H2 O
Ag2S coated coin

Ag2S(s) + 2e- → Ag(s) + S2-

2H2O(l) + 2e- → H2 (g) + 2OH- (aq)

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The process of electrolysis results in coins that

retain the original features and can be sold for many
times the value of silver bullion of the same mass.

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