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Sonny
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Chemistry
Equilibrium & Reaction Conditions
Position of the equilibrium
- Theposition of the equilibriumrefers to the relative amounts of products and reactants in an equilibrium mixture
- When the position of equilibrium shifts to theleft, it means the concentration ofreactantsincreases
- When the position of equilibrium shifts to theright, it means the concentration ofproductsincreases
Le Chatelier’s principle
- Le Chatelier’s principlesays that if a change is made to a system in dynamic equilibrium, the position of the equilibrium moves to counteract this change
- The principle is used to predict changes to the position of equilibrium when there are changes in temperature, pressure or concentration
Effects of concentration
How the equilibrium shifts with concentration changes
Worked example
Changes in equilibrium position
Using the reaction below:
CH3COOH (I) + C2H5OH (I)⇌ CH3COOC2H5(I) + H2O (I)
Explain what happens to the position of equilibrium when:
1. MoreCH3COOC2H5is added
2. Some C2H5OH is removed
Using the reaction below:
Ce4+(aq) + Fe2+(aq)⇌Ce3+(aq)+ Fe3+(aq)
Explain what happens to the position of equilibrium when
3. Water is added to the equilibrium mixture
Answer 1:
- The position of the equilibrium moves to the left and more ethanoic acid and ethanol are formed
- The reaction moves in this direction to oppose the effect of added ethyl ethanoate, so the ethyl ethanoate decreases in concentration
Answer 2:
- The position of the equilibrium moves to the left and more ethanoic acid and ethanol are formed
- The reaction moves in this direction to oppose the removal of ethanol so more ethanol (and ethanoic acid) is formed from ethyl ethanoate and water
Answer 3:
- There is no effect as the water dilutes all the ions equally so there is no change in the ratio of reactants to products
Effects of pressure
- Changes in pressure only affect reactions where the reactants or products are gases
How the equilibrium shifts with pressure changes
Worked example
Changes in pressure
Predict the effect of increasing the pressure on the following reactions:
1. N2O4(g)⇌2NO2(g)
2. CaCO3(s)⇌CaO (s) + CO2(g)
Predict the effect of decreasing the pressure on the following reaction:
3. 2NO2(g)⇌2NO (g) + O2(g)
Answer 1:
- The equilibrium shifts to the left as there are fewer gas molecules on the left
- This causes a decrease in pressure
Answer 2:
- The equilibrium shifts to the left as there are no gas molecules on the left but there is CO2on the right
- This causes a decrease in pressure
Answer 3:
- The equilibrium shifts to the right as there is a greater number of gas molecules on the right
- This causes an increase in pressure
Effects of temperature
How the equilibrium shifts with temperature changes
Worked example
Changes in temperature
Using the reaction below:
H2(g) + CO2(g)⇌ H2O (g) + CO (g) ΔH = +41.2 kJ mol-1
1. Predict the effect of increasing the temperature on this reaction
Using the reaction below:
Ag2CO3(s)⇌ Ag2O (s) + CO2(g)
2. Increasing the temperature increases the amount of CO2(g) at constant pressure. Is this reaction exothermic or endothermic?
Explain your answer
Answer 1:
- The reaction will absorb the excess energy and since the forward reaction is endothermic, the equilibrium will shift to the right
Answer 2:
- The reaction will absorb the excess energy and since this causes a shift of the equilibrium towards the right (as more CO2(g) is formed) this means that the reaction is endothermic
Equilibrium & Catalysts
Effects of catalysts
- A catalyst is a substance that increases the rate of a chemical reaction (they increase the rate of theforwardandreversereactionequally)
- Catalysts only cause a reaction to reach equilibriumfaster
- Catalysts therefore haveno effecton theposition of the equilibriumonce this is reached
Investigating changes to the equilibrium position with concentration
- The equilibrium between aqueous chromate ions, CrO42-, and dichromate ions, Cr2O72- is sensitive to changes in acid concentration
- Solutions of chromate and dichromate ions have different colours so it is easy to see any shift in the equilibrium position
- By adding dilute sulfuric acid, we can increase the concentration of H+(aq) in the solution
- This increases the rate of the forward reaction causing the equilibrium position to shift to minimise the change in H+(aq) concentration
- This decreases the concentration of the added reactant, H+(aq)
- Equilibrium shifts to the right, making more products
- Solution turns orange due to the formation of more Cr2O72-(aq)
- By adding aqueous sodium hydroxide, we can decrease the concentration of H+(aq) in the solution
- The added OH-(aq) ions react with H+(aq) ions forming water
- H+(aq) + OH-(aq) → H2O (l)
- This decreases the rate of the forward reaction causing the equilibrium position to shift to minimise the change in H+(aq) concentration
- This decreases the concentration of reactant that has been removed, H+(aq)
- Equilibrium shifts to the left, making more H+(aq) reactant
- Solution turns yellow due to the formation of more CrO42-(aq)
Investigating changes in equilibrium position with temperature
- Cobalt chloride, CoCl2, dissolves in water to form a pink solution
- The dissolving process produces an equilibrium between two different coloured cobalt complexes
[Co(H2O)6]2+ (aq) + 4Cl- (aq) ⇌ [CoCl4]2- (aq) + 6H2O (l)
- The forward reaction in this process is endothermic and the backward reaction is exothermic
- By heating up the solution we can increase the amount of heat energy in the system
- This causes the equilibrium to shift to minimise the change
- Equilibrium shifts to the right favouring the endothermic reaction (ΔH is positive)
- This allows the system to take heat energy in and minimise the increase in temperature
- The solution turns blue as more CoCl42-(aq) is formed
- This causes the equilibrium to shift to minimise the change
- Cooling down the solution removes the heat energy from the system
- This again causes the equilibrium to shift to minimise the change
- Equilibrium shifts to the left favouring the exothermic reaction (ΔH is negative)
- This allows the system to release heat energy and minimise the decrease in temperature
- The solution turns pink as more Co(H2O)62+(aq) is formed
- This again causes the equilibrium to shift to minimise the change
Operational Conditions
- Equilibrium reactions are involved in some stages of large-scale production of certain chemicals
- An understanding of equilibrium and Le Chatelier’s principle is therefore very important in the chemical industry
Haber process
- The Haber process involves the synthesis of ammonia according to:
N2(g) + 3H2(g) ⇌ 2NH3(g)ΔHr= -92 kJ mol-1
- Le Chatelier’s principle is used to get the best yield of ammonia
Maximising the ammonia yield
Pressure
- An increase inpressurewill result in the equilibrium shifting in the direction of the fewest molecules of gas formed to reduce the pressure
- In this case, the equilibrium shifts towards the right so the yield of ammonia increases
- An increase in pressure will cause the particles to be closer together and therefore increasing the number of successful collisions leading to an increased reaction rate
- Very high pressures are expensive to produce therefore acompromise pressureof 200 atm is chosen
Temperature
- To get the maximum yield of ammonia the position of equilibrium should be shifted as far as possible to the right as possible
- Since the Haber process is an exothermic reaction, according to Le Chatelier’s principle the equilibrium will shift to the right if the temperature is lowered
- A decrease intemperaturewill decrease the energy of the surroundings so the reaction will go in the direction in which energy is released to counteract this
- Since the reaction is exothermic, the equilibrium shifts to the right
- However,at a low temperature the gases won’t have enough kinetic energy to collide and react and therefore equilibrium would not be reached thereforecompromise temperatureof 400-450oC is used in the Haber process
- A heat exchangerwarms the incoming gas mixture to give molecules morekinetic energysuch that the gas moleculescollide more frequentlyincreasing the likelihood of a reaction
Catalysts
- In the absence of a catalyst the reaction is so slow that hardly anything happens in a reasonable time!
- Adding an iron catalyst speeds up the rate of reaction
Contact process
- The Contact process involves the synthesis of sulfuric acid according to:
2SO2(g) + O2(g) ⇌ 2SO3(g)ΔHr= -197 kJ mol-1
- Le Chatelier’s principle is used to get the best yield of sulfuric acid
Maximising the sulfuric acid yield
Pressure
- An increase inpressurewill result in the equilibrium shifting in the direction of the fewest molecules of gas formed to reduce the pressure
- In this case, the equilibrium shifts towards the right so the yield of sulfuric acid increases
- In practice, the reaction is carried out at only 1 atm
- This is becauseKpfor this reaction is already very high meaning that the position of the equilibrium is already far over to the right
- Higher pressures than 1 atm will be unnecessary and expensive
Temperature
- The same principle applies to increasing the temperature in the Contact process as in the Haber process
- Acompromise temperatureof 450oC is used
Catalysts
- The Contact process uses vanadium(V) oxide as a catalyst to increase the rate of reaction
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