Energy Changes in reversible reactions

Reversible reactions are exothermic (give out heat) in one direction and endothermic (take in heat) in the other. The same amount (Joules) of heat energy is given out in one direction and taken in in the other direction. When the forward and the backward reaction are happening at the same time, an equilibrium can be set up. At equilibrium there will be both products and reactants present in a mixture the concentrations of each will not be changing even though reactions are constantly taking place. The rate of the forward reaction will be the same as the rate of the backwards reaction. (Just like the runner on the treadmill the runner and the belt are moving at the same speed but in opposite dircetions, so the runner is staying in the same place) To get an equilibrium, none of the reactants or products must escape you need a closed system.

How much is there at equilibrium ? The amounts of the products and the reactants at equilibrium depends on the conditions (e.g. temperature, pressure). Changing the conditions will change the amounts of reactants and products present in the mixture - a new equilibrium gets set up. We call this changing the position of equilibrium. - if changing the conditions causes the position of equilibrium to move in the forward direction (to the right) we get more products, less reactants in the equilibrium mixture - if changing the conditions causes the position of equilibrium to move in the backwards direction (to the left) we get less products, more reactants in the equilibrium mixture

N2

3H2

2NH3

position of equilibrium towards the right more ammonia and less nitrogen and hydrogen at equilibrium

N2

3H2

2NH3

position of equilibrium towards the left less ammonia and more nitrogen and hydrogen at equilibrium

Check your understanding : True or False ?

All chemical reactions are reversible. The mass can change if a solid product is formed in a closed system. Equilibrium can only happen in closed systems. In a reversible reaction, reactants can form products and products can form reactants. A symbol shows that an equilibrium has been set up. Once at equilibrium no more products are formed. Once at equilibrium, the forward and backward reactions stop.

[Answers at the end]

Controlling the position of equilibrium - making more product

Whenever we change the conditions, the position of the equilibrium will shift to try and oppose the change. (This is called LeChateliers Principle). To know the effect of changing temperature on the position of equilibrium, we need to know which direction is exothermic and which direction is endothermic:

The effect of increasing the pressure is to move the position of equilibrium to whichever side of the equation has fewer moles of gas (look at the numbers in front for the gaseous products and reactants) thus reducing the effect of the pressure increase:

Case Study: The Haber Process .

Use: industrial manufacture of ammonia Equation:

N2 + 3 H2 nitrogen + hydrogen

2 NH3 ammonia

Raw materials: - nitrogen (N2) which is obtained from the air (by fractional distillation of air) - hydrogen (H2) which is mainly obtained from natural gas and steam (CH4(g) + H2O(g) CO(g) + 3 H2(g)) Conditions in the ammonia reactor: iron catalyst; moderate temperature of about 450C; high pressure of about 200 atmospheres

Uses of ammonia: Ammonia is a very important substance, used in huge quantities for manufacturing other chemicals: dyes medicines fertilisers explosives

How the Haber process works:

By removing the ammonia and recycling the unreacted gases: - Reactants are used efficiently, not wasted - Energy used to make reactants is not wasted - a reasonable yield of ammonia is made as quickly as possible

Why do we use a temperature of 450C for the Haber process ? Heat energy is given out when ammonia is formed the forward reaction is exothermic

N2 + 3H2 2NH3
Should we do the reaction at a high or low temperature to shift the position of equilibrium to make more NH3 ? If we do the reaction at a low temperature then we should get more ammonia in the reaction mixture at equilibrium. BUT the rate of reaction is too slow at low temperatures. We therefore use a moderate temperature as a compromise in order to make ammonia quickly enough to be economical. We also use a catalyst to speed up the reaction (rather than using more heat), so the process is more energy efficient. Why use a pressure of about 200 atmospheres ? 4 molecules of gas (N2 and 3 H2) turn into 2 molecules of ammonia gas when ammonia is formed: N2 + 3H2 2NH3 What should we do to the pressure to get more ammonia in the equilibrium mixture ? If we carry out the reaction at high pressure then we will get more ammonia in the reaction mixture at equilibrium. BUT high pressures take a lot of energy to create, and require greater safety precautions to prevent leaks or explosions. We therefore use a moderately high pressure as a compromise.

Answers : True or False ?

All chemical reactions are reversible. FALSE FALSE

The mass can change if a solid product is formed in a closed system. Equilibrium can only happen in closed systems. TRUE

In a reversible reaction, reactants can form products and products can form reactants. TRUE A symbol shows that an equilibrium has been set up. FALSE (see note 1) Once at equilibrium no more products are formed. FALSE (see note 2) Once at equilibrium, the forward and backward reactions stop. FALSE

Note 1: The symbol indicates a reversible reaction, not that an equilibrium has been established. Note 2: Products are being formed continually, its just that they are being used up (turned back into reactants) at the same rate, so the amount of products present is not changing.