Oxidation and reduction – Redox - Chapter 6

Why are redox reactions important?

1. In industry?
- The production of aluminum, magnesium, chlorine, bleach
- The rechargeable lithium ion battery LiC6 + CoIVO2  LiCoIIIO2 + 6C

2. In the environment and nature?

- Aerobic (surface water) and anaerobic (bogs, lake bottoms) water
- “Cold combustion” of sugars in cells
- Oxygen evolution in photosynthesis:
- (MnIV )3(MnV) + 2H2O  (MnIII)3(MnIV) + O2 + 4H+

3. At home?
- Bleaching hair (peroxide), clothes (bleach)
- Rusting and tarnishing of metal surfaces
- Oxidation of wine, apples 1
 Oxidation and reduction – Redox - Chapter 6

Topics to understand:
1. Half cells and electrochemical potentials
2. Effects of pH (acidic vs basic), ligands, disproportionation
3. Diagrams presenting electrochemical potential data: Latimer and
Frost diagrams

Prior knowledge: balancing redox reactions under acidic and basic

conditions

The corrosion of iron in sea water:

2Fe + O2 + 2H2O  2FeII(OH)2 Fe0 (reductant)  FeII + 2e-
O02 (oxidant) + 4e- + 2H2O 4O-IIH
4FeII(OH)2 + O2  2FeIII2O3 + 4H2O FeII (reductant)  FeIII + e-
rust O02 (oxidant) + 4e-  2O2- 2
 Electrochemical cells
Galvanic cell: - chemical energy into electrical energy
- half cells are linked so that e- flow spontaneously
- ammeter indicates flow of current through wire
Cell notation for cell with active electrodes (reduction on the right):
e.g. - Cu | Cu2+ | | Ag+ | Ag +

Electrons move
Anode: through the wire
oxidation Cathode:
of CuCu2+ Change Reduction
(Cu dissolves) of phase of Ag+ + e- Ag (Ag added to cathode)
Half cell: (The NO3- of Ag+(NO3-) is not written)
Cu Cu2+ + 2e-

Salt bridge, NaNO3(aq)

Cu is a stronger reductant than Ag.
NO3- moves from Ag+ to Cu2+ solution
Ag+ is a stronger oxidant than Cu2+.
Na+ moves from Cu2+ to Ag+ solution
e-
0.46 V +
- e-

Cu | Cu2+ || Ag+ | Ag
Cu | Cu2+ || Ag+ | Ag
 Cell conventions
The A, B, C of Electrochemistry

Anode Bridge Cathode

(an oxidation always occurs (reduction always
at the anode) occurs on the right)
reduction-Cathode
red cat

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 Electrochemical potential

Electrochemical potential difference Ecell between

electrodes of a cell is measured at zero e- flow
(reversible conditions) with a potentiometer.
This is usually similar to the cell voltage measured
with a voltmeter.
At standard states of substances (1 M, 1 bar, 25 °C)
it is called Ecell.
e.g. for:

Zn | Zn2+ | | Cu2+ | Cu
Ecell = 1.10 V
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DGº and Eºcell

ΔG° = – n F E°cell
F = 96,485 C mol−1
n = no. of moles of electrons transferred in reaction
ΔG° = Gibbs Free Energy change (Joule)
E°cell = standard cell potential (Volt)

Standard State Conditions:

• unit activity for each component in the cell
( for dilute solutions activity ≈ concentration (mol L−1) )
• pressure of any gaseous component is 1 bar ( = 100 kPa )
( recall that 1 atm = 101.325 kPa = 1.01325 bar )
• a solid component is in its standard state
• temperature = 298 K ( 25 °C )

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Definition of the Faraday (F) and Ampere (A)

F = Total amount of electrical charge on 1 mole of electrons

= (1.60218 x 10−19 Coulomb e−1)(6.02217 x 1023 e mol−1)
= 96,485 C mol−1

1 Volt = 1 Joule Coulomb−1 or 1 Joule = (1 C)(1 V)

1 Ampere = 1 Coulomb per second (C s−1)

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 DGº, Keq and Eºcell

ΔG° = –RT lnKeq R = 8.314

lnKeq = n F Eºcell
RT

Cell Reaction is Thermodynamically

favourable if:

• Eºcell > 0 (positive)

• ΔGº < 0 (negative)
• Keq > 1

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Eº is proportional to ln(K) or log(K)

Eº = RT(InKeq)/n F = 2.30 RT(log Keq)/n F

logK
34
17
0
-17
-34

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Standard Hydrogen Electrode (SHE)

Consists of a Platinum electrode over which

H2 gas at 1 bar pressure is bubbled while the
electrode is immersed in a solution that is
1.00 M hydronium ion at 25 ºC (298 K)

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 Galvanic cell to determine the
electrochemical potential E°(Zn2+/Zn)

(1 bar)

(1.0 M) (1.0 M)

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A galvanic cell for measuring the Zn2+/Zn half-cell potential
Spontaneous current
flow from negative to
positive producing:
Zn + 2H+  Zn2+ + H2
The spontaneous
reaction (Ecell positive)
is Zn oxidation. But
Eº(Zn2+/Zn) is for a
reduction. Therefore
Eº(Zn2+/Zn) must be
negative.

Anode (Zn electrode): Cathode (Pt electrode):

negative terminal positive terminal

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 The Zn2+/Zn half-cell potential
Anode (Zn electrode): Cathode (Pt electrode):
negative terminal positive terminal

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 Half cell voltages of Galvanic cells
- 0.00 V assigned arbitrarily to standard or normal hydrogen electrode (SHE, NHE) :
H3O+(1 M) | H2(1 atm) | Pt
-measure difference in cell voltages (or energies- see below)
-
0.00 V ?V
Pt | H2(1 atm.) | H3O+(1 M) | | Cu2+(1 M) | Cu
Ecell = 0.34 V = E(cathode) - E(anode) = 0.34 – 0.00
E(cathode) = E(Cu2+ /Cu) = 0.34 V

Zn | Zn2+ (1 M) | | H3O+(1 M) | H2(1 atm) | Pt

Ecell = 0.76 V = E(cath.) - E(an.) = 0.00 – (-0.76)
E(an.) = E(Zn2+ /Zn) = -0.76 V

Zn | Zn2+ (1 M) | | Cu2+(1 M) | Cu
Ecell = E (cath.) - E (an.) = 0.34 - (-0.76) = +1.10 V
for the reaction Zn + Cu2+  Cu + Zn2+
 E and Ecell
Positive E: Favorable reduction, unfavorable oxidation vs H+/H2

Cu2+ +2e-  Cu(s)

0.34 V

2 H3O+ +2e-  H2(g) + 2H2O

0.00 V Ecell 1.10 V

E (V)

Zn2+ +2e-  Zn(s)

-0.76 V

Unfavorable reduction, favorable oxidation

- strong oxidants at top left, reductants at bottom right

 Table of E

E always refers to reduction reaction vs SHE

- strong oxidants at top left, reductants at bottom right
Stronger oxidant - note the effect of pH on E

F2(g) + 2 e-  2 F- E 2.87 V
MnO4- + 4H3O+ + 3 e-  MnO2(s) + 6H2O 1.68 V
Fe3+ +e-  Fe2+ (1 M acid e.g. HNO3) 0.77 V
I2 +2e-  2I- 0.54 V
Cu2+ +2e-  Cu(s) 0.34 V
Fe2+ +2e-  Fe(s) -0.41 V
Fe(OH)3 +e-  Fe(OH)2(s) + OH- (1 M base) -0.56 V
Zn2+ +2e-  Zn(s) -0.76 V
Li+ +e-  Li(s) -3.04 V
Some standard reduction potentials

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 Periodic trends of electronegativity C and E
- note relationship between E and electronegativity of the elements
- H2 in middle of electronegativity scale (good choice for reference)
- metals are usually reductants (loss of an electron to H+ is favorable)
- coinage metals (Cu, Ag, Au) are the weakest reductants (their cations are oxidants)
- nonmetals are oxidants (addition of an electron from H2 is favorable)

Reference Oxidant
E 0 E positive
C 2.2 C big

Strong reductant
E negative
C small

Electronegativity Weak reductant

 Periodic trends: main group
Weak oxidant  Strong reductant (Eº negative) Strong oxidant (Eº positive) 
Weak reductant
Li+ + e- h Li -3.05 V
Rb+ + e- h Rb -2.92 V
Be2+ + 2e- h Be -1.70 V
Ca2+ + 2e- h Ca -2.76 V
CO + 2H+ + 2e- h C + H2O -0.21 V
Sn2+ + 2e- h Sn -0.14 V
Pb2+ + 2e- h Pb -0.13 V
2H+ + 2e- h H2 0.0 V
½ O2 + 2H+ + 2e- h H2O +1.23 V
½ S8 + 2H+ + 2e- h H2S(aq) +0.14 V
½ Se8 + 2H+ + 2e- h H2Se(aq) -0.40 V
F2 + 2H+ + 2e- h HF +3.06 V
Cl2 + 2e- h 2Cl- +1.36 V
I2 + 2e- h 2I- +0.54 V
 Periodic trends: transition metals
the transition metal series inserts between Ca and Ga and continues the trend:

Ca2+ + 2e-  Ca -2.8 V

Sc3+ + 3e-  Sc -2.1 V
Ti2+ + 2e-  Ti -1.63 V
V2+ + 2e-  V -1.19 V
Cr3+ + 3e-  Cr -0.74 V
Mn2+ + 2e-  Mn -1.18 V (Mn2+ with d5 configuration is extra stable)
Fe2+ + 2e-  Fe -0.44 V
Co2+ + 2e-  Co -0.28V
Ni2+ + 2e-  Ni -0.25 V Pt2+ + 2e-  Pt 1.2 V
Cu2+ + 2e-  Cu 0.34 V Ag+ + e-Ag 0.80 V Au+ + e-Au 1.68 V
Zn2+ + 2e-  Zn -0.76 V (Zn2+ with d10 configuration is stable)
Ga3+ + 3e-  Ga -0.53 V
Proton exchange membrane fuel cell

Anode: hydrogen oxidation

H2  2e- + 2H+

Cathode: oxygen reduction

O2 + 4H+ + 4e-  2H2O

Eºcell = Eº(O2/H2O) = 1.23 V

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 The hydrogen economy
Wind
Solar
Hydro
Geothermal
Biomass

Transportation
H2

Nuclear

Natural gas
Distributed generation
with CO2 sequestration
Rechargeable Li ion battery – Section 24.5 page 743

Oxidant Co4+

CoO2 + Li+ + e- h LiCoO2 1 V

Ecell 4 V
LiC6 h Li+ + C6 + e- - 3 V
Reductant Li

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 Latimer diagram for an element
- summarizes a large amount of Eº data for an element starting on the left from the
highest oxidation number
- For example here is the Latimer diagram for chlorine in acidic pH 0 solutions (H+, e-,
H2O omitted):

- This diagram summarizes redox couples (balance charge, H, and O with e-, H+, H2O) including:

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 Latimer diagram for chlorine in pH 14 (basic) solution

- This diagram summarizes redox couples (balance with e-, OH-, H2O) including:

- Other Eº for non-adjacent species can be calculated, but not by adding Eº values, but
instead free energies. E.g. for Eº(ClO4-/ClO2):

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 Latimer diagram for oxygen in pH 0 (acidic) solution

- H2O2 (hydrogen peroxide) with oxidation number -1 at oxygen is unstable with

respect to disproportionation. This can be seen in the Latimer diagram when the
Eº to the right is more positive than the Eº to the left of the species with the
oxidation number of interest.

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Exercises for this part from the textbook

6.2, 6.10, 6.12, 6.14, 6.17

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