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?? 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%

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
Overall reaction:
OS’s: 2H2 + O2 2 H2O

Half-reactions:
• oxidation (anode): • reduction (cathode):
anode, (-)

2H+ + 2e- ) 2( H2 O2 + 4H+ + 4e2H2O
(+), cathode

H2

H 3O + electrolyte

O2

H2O Key Points: • run continuously at high efficiency • product is benign

Fuel Cells: Other Directions
Potential limitations of hydrogen-oxygen fuel cell?
• need better, cheaper electrodes • safety/fuel storage

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 CO2 + 2H2O • ½-reactions oxidation: CH4 + 4O2reduction: 2( O2 + 4eCO2 + 2H2O 2O2- )

Alcohols:
• advantages of handling/replacing liquid fuel • operate at lower temperatures • potential for consumer electronics, including portable computers, cell phones, etc.

Disproportionation Reactions
In redox reactions, there is always a reactant that is oxidized and a reactant that is reduced. + A + B A + B

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: or A + A A+ + A2A A+ + A-

Example: Sodium Thiosulfate
Demonstration– observations? • solid precipitate • smell • Overall disproportionation reaction: S2O32-(aq) + 2H+(aq) S(s) + SO2(g) + H2O S-OS’s: +2 0 +4

Oxidizing & Reducing Agents
In redox reactions, there is always a reactant that is oxidized and a reactant that is reduced. A + B A+ + BThe 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)

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
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. Titration • what is it?
- Addition of a standard solution that undergoes a reaction of known stoichiometry with a solution of unknown concentration - The point at which stoichiometric quantity of standard solution has been added to the unknown solution. - 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.

• equivalence point

• indicators

phenolphthalein: A = colorless;

B = pink

Acid-Base Titration
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
The concept of titration can be used generally for determination of the concentration of unknowns in solution. 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+ orange-red Standard? Unknown? 3CH3COOH + 4Cr3+ + 11H2O green

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