IAL Chemistry Ms.

Pabasari Goonetilleke
Unit 5
Redox Equilibria

Standard electrode potentials and thermodynamic feasibility

• Consider the following two equilibria

• The equilibrium of the first reaction lies further to the ……………………………….than that of the hydrogen
electrode the equilibrium of the second reaction lies further to the ………………………………………

• If the two equilibrium are linked by combining the two half cells to make an electrochemical cell, then
electrons will flow from the …………………………………….electrode to the ………………………………….electrode
therefore the equilibrium will disturbed.

• The following reactions will take place in each half step

…………………………………………………………………..

…………………………………………………………………..

• Electrons flow from the half-cell with …………………… negative Eθ value to the half cell with …………………..
negative (more positive) Eθ value
1. Is this reaction thermodynamically feasible?/ Will Zinc displace Copper?

• ……………………………………………………………..
…………………………………………………………..…
………………………………………………………..……
• ……………………………………………………………..
…………………………………………………………..…
………………………………………………………..……
• ……………………………………………………………..

2. Is this reaction thermodynamically feasible?/ Will Magnesium displace Copper?

• ……………………………………………………………..
…………………………………………………………..…
………………………………………………………..……
• ……………………………………………………………..
…………………………………………………………..…
………………………………………………………..……
• ……………………………………………………………..

3. Is the following reaction thermodynamically feasible?

Zn (s) + Fe 2+ (aq) → Zn 2+ (aq) + Fe (s)

• ……………………………………………………………………………………….………………………………………………………..
…………………………………………………………..……………………………………..………………………………………..……
• …………………………………………………………………………………………………………………………………………….…..
…………………………………………………………..…………………….………………………………………………………..……
• …………………………………………………………………………………………………………………………………………….…..
…………………………………………………………..…………………….………………………………………………………..……
4. Does Zinc react with dilute acid?

• ……………………………………………………………………………………….………………………………………………………..
…………………………………………………………..……………………………………..………………………………………..……
• …………………………………………………………………………………………………………………………………………….…..
…………………………………………………………..…………………….………………………………………………………..……
• …………………………………………………………………………………………………………………………………………….…..
…………………………………………………………..…………………….………………………………………………………..……

5. Does copper react with dilute acid?

• ……………………………………………………………………………………….………………………………………………………..
…………………………………………………………..……………………………………..………………………………………..……
• …………………………………………………………………………………………………………………………………………….…..
…………………………………………………………..…………………….………………………………………………………..……
• …………………………………………………………………………………………………………………………………………….…..
…………………………………………………………..…………………….………………………………………………………..……
Alternative Method - Calculating Eθcell

Example 1:

Will Zinc displace Copper?

It is necessary to write the two half equations as they occur in the proposed reaction changing the sign of the standard
electrode potential as necessary

…………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

Example 2:

Will copper react with dilute sulfuric acid?

Proposed reaction:

Writing the standard electrode potential as necessary

…………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

The drawback of this method is that there is no emf produced in reactions taking place inside a test tube. However,
the results produced are the same.
Reaction between Manganese (IV) oxide and hydrochloric acid

Consider,

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

Disproportionation reactions

Copper(I) iodide when reacting with sulphuric acid will disproportionate to Cu2+ and Cu metal

Consider,

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………
Summary

▪ ………………………………………………………………………………………………………………………………………….…………………………………..
▪ ………………………………………………………………………………………………………………………………………………………………………………
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▪ ………………………………………………………………………………………………………………………………………….…………………………………..
▪ ………………………………………………………………………………………………………………………………………………………………………………
▪ ………………………………………………………………………………………………………………………………………….…………………………………..
▪ ………………………………………………………………………………………………………………………………………………………………………………

Questions

Q1

Q2

Q3

Q 4 :Use the half-equations to explain in terms of oxidation states what happens to hydrogen peroxide when it is
reduced.
Total entropy and Eθcell

n- …………………………………………………………………….

F- …………………………………………………………………….

T- …………………………………………………………………….

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………………………………………………

………………………………………………………………………………………………………………………………………….…………………………………..

………………………………………………………………………………………………………………………………………………………………………………

Consider the following cell,

………………………………………………………………………………………..

The two half- cell reactions taking place are,

………………………………………………………………………………………..

The overall reaction is,

………………………………………………………………………………………..

In the following cell diagram;

………………………………………………………………………………………..

Half- cell reactions written left to right will not occur since E cell is negative. The reaction will occur from right to left

………………………………………………………………………………………..

The overall reaction is,

………………………………………………………………………………………..

………………………………………………………………………………………..………………………………………………………………………………………..
Equilibrium constant and Eθcell

Equilibrium constant and Eθcell are related by

………………………………………………………………………………………..………………………………………………………………………………………..

………………………………………………………………………………………..………………………………………………………………………………………..

Fuel cell

A fuel cell uses the energy from the reaction of a fuel with oxygen to create a voltage

Hydrogen- oxygen Fuel cell (potassium hydroxide electrolyte)

Both metal electrodes are coated with platinum which catalyzes the reactions.

Two reactions taking place are;

………………………………………………………………………………………..………………………………

………………………………………………………………………………………..………………………………
The H+ ions pass through the proton exchange membrane which allows them to enter the compartment containing
the positive electrode where they react with oxygen

The overall cell reaction is

………………………………………………………………………………………..

The hydrogen – oxygen fuel cell that has an alkaline electrolyte has the following reactions

………………………………………………………………………………………..

………………………………………………………………………………………..

………………………………………………………………………………………..

Using standard conditions: The rate is too slow to produce an appreciable current.

Higher temperatures are therefore used to increase rate, but the reaction is exothermic so by applying le chatelier
would mean the emf falls.

A higher pressure can help counteract this

Fuel cells will maintain a constant voltage over time as they are continuously fed with fresh O2 and H2 so maintaining
constant concentration of reactants. This differs from ordinary cells where the voltage drops over time as the reactant
concentrations drop

Advantages of Fuel cells over conventional petrol or diesel-powered vehicles

(i) Offer an alternative to the direct use of fossil fuel

(ii) Less pollution and less CO2. (Pure hydrogen emits only water whilst hydrogen-rich fuels produce only
small amounts of air pollutants and CO2).
(iii) They are lighter and have greater efficiency

Limitations of hydrogen fuel cells

(i) Hydrogen explodes when ignited so, should be careful when transporting.
(ii) Expensive
(iii) Storing and transporting hydrogen, in terms of safety, feasibility of a pressurised liquid and a limited life
cycle of a solid ‘adsorber’ or ‘absorber’
(iv) Limited lifetime (requiring regular replacement and disposal) and high production costs
(v) Use of toxic chemicals in their production

Hydrogen is readily available by the electrolysis of water, but this is expensive. To be a green fuel the electricity
needed would need to be produced from renewable resources

Hydrogen can be stored in fuel cells

(i) as a liquid under pressure,

(ii) adsorbed on the surface of a solid material,
(iii) absorbed within a solid material
Ethanol fuel cells

Ethanol fuel cells have also been developed. Compared to hydrogen fuel cells they have certain advantages including.

Ethanol can be made from renewable sources in a carbon neutral way

Raw materials to produce ethanol by fermentation are abundant Ethanol is less explosive and easier to store than
hydrogen.

New petrol stations would not be required as ethanol is a liquid fuel.