Chemistry 5

Chapter-5
Reactions in Aqueous Solutions

Part-3

2 October 2002
 Important Applications of
Redox Reactions: Fuel Cells
How is electrical power generated??
ƒ The combustion of fossil fuels is one of
the most common methods used to
generate electrical power. In this process,
the heat of combustion is converted to
steam that drives a turbine which drives a
generator.
• typical efficiency: 30-35%; best: ~ 40%
• automobile efficiency: ~20%

ƒ An alternative approach that has the

potential to achieve close to 100 %
efficiency involves the use of fuel cells.
• In a fuel cell, the reactants are used to produce
electrical power directly through coupled oxidation
and reduction ½-reactions.
• What are some limitations (i.e., why not more
widely used)?
- cost/MW is high (but decreasing)
- most efficient fuel sources can be dangerous
 Hydrogen/Oxygen Fuel Cell
ƒ Overall reaction:
2H2 + O2 Æ 2 H2O
OS’s:
ƒ Half-reactions:
• oxidation (anode): 2( H2 Æ 2H+ + 2e- )
• reduction (cathode): O2 + 4H+ + 4e- Æ 2H2O

anode, (-) (+), cathode

H2 Æ H 3O +
Å O2
electrolyte

H2O

Key Points:
• run continuously at high efficiency
• product is benign
 Fuel Cells: Other Directions
ƒ Potential limitations of hydrogen-oxygen
fuel cell?
• need better, cheaper electrodes
• safety/fuel storage

ƒ Other possible fuels?

Scientific American July 1999
Nature 414, 345-352 (2001)

Hydrocarbons:
• replace H2 more safely stored hydrocarbon gas,
such as methane; continue to oxidize with O2
• overall reaction: 2O2 + CH4 Æ CO2 + 2H2O
• ½-reactions
oxidation: CH4 + 4O2- Æ CO2 + 2H2O
reduction: 2( O2 + 4e- Æ 2O2- )

Alcohols:
• advantages of handling/replacing
liquid fuel
• operate at lower temperatures
• potential for consumer electronics,
including portable computers, cell
phones, etc.
 Disproportionation Reactions
ƒ In redox reactions, there is always a reactant
that is oxidized and a reactant that is
reduced.
A + B Æ A + B
+ -

ƒ However, it is possible for one reactant to

both be oxidized and reduced– in these
cases, the reaction is called a
disproportionation reaction.

If B = A, then: A + A Æ A+ + A-
or 2A Æ A+ + A-

ƒ Example: Sodium Thiosulfate

Demonstration– observations?
• solid precipitate
• smell
• Overall disproportionation reaction:
S2O32-(aq) + 2H+(aq) Æ S(s) + SO2(g) + H2O
S-OS’s: +2 0 +4
 Oxidizing & Reducing Agents
ƒ In redox reactions, there is always a reactant that is
oxidized and a reactant that is reduced.
A + B Æ A+ + B-
ƒ The reactants that accept and give up electrons are
called oxidizing and reducing agents, respectively.
• Oxidzing Agent or Oxidant:
- contains element whose OS decreases in redox reaction
- gains electron(s)
• Reducing Agent or Reductant:
- contains element whose OS increases in redox reaction
- loses electron(s)

ƒ Strengths of oxidants & reductants, e.g.:

• metals: Cu, Na, Zn
- Stronger reductant: Na > Zn > Cu
- Periodic trends

• KMnO4 vs. MnO2

- Demonstration– observations?
- MnO4- is stronger oxidant!
- use oxidation states as guide
Determining Reaction Stoichiometry
ƒ How does one determine solution concentration
(and do we care)?
• for example, want to know concentration of
alcohol in large wine cask….
• could do so by reacting known volume with
known concentration solution.
ƒ Titration
• what is it?
- Addition of a standard solution that undergoes a reaction of
known stoichiometry with a solution of unknown concentration
• equivalence point
- The point at which stoichiometric quantity of standard solution
has been added to the unknown solution.

• indicators
- Dyes that exhibit dramatic color change at equivalence point.
The chosen dye should be specific to the titration reaction; that
is the type of acid-base or redox reaction.

phenolphthalein: A = colorless; B = pink

 Acid-Base Titration
ƒ If you are given an unknown concentration solution
of acid or base how can the concentration be
determined and thus pH?
• overall reaction:

• observations:

• determination of unknown concentration:

 Redox Titrations
ƒ The concept of titration can be used generally for
determination of the concentration of unknowns in
solution.
ƒ For example, oxidation-reduction reactions
represent another general class where titrations are
useful.
• Determination of Fe in ore:
- prepare Fe2+ solution of know volume
- tritrate with standard KMnO4 solution
- endpoint?

• Breathalyzer Test
3C2H5OH + 2Cr2O72- + 16H+ Æ 3CH3COOH + 4Cr3+ + 11H2O
orange-red green

Standard?
Unknown?