Reversible Reactions

These are reactions that can go both forwards and backwards. A + B C + D

At the start, we have a high concentration of A + B but no C + D. As A + B react, their rate of reaction decreases. As C + D are produced, their concentration increases and therefore their rate of reaction increases.

Eventually the rate of the forward reaction equals the rate of the backward reaction and we say the reaction is in dynamic equilibrium. Dynamic moving forwards and backwards at the same rate. Equilibrium concentrations of A,B,C and D appear not to change.

Conditions affecting equilibria Le Chateliers principle: if a reaction in equilibrium is subjected to a change in conditions, the equilibrium shifts to oppose the change. i. Concentration + B C + D

Consider A

In a closed container, this reaction reaches equilibrium and we would have some A, B, C and D in the container. If we increase the concentration of one of the reactants e.g. A, the equilibrium shifts to oppose the change, i.e. it would shift mainly to the right hand side, making more products. If we increase the concentration of one of the reactants, the equilibrium shifts to the right. If we decrease the concentration of one of the reactants, the equilibrium shifts to the left greater proportion of reactants. If we decrease the concentration of the product, the equilibrium shifts to the right. If we increase the concentration of one of the products, the equilibrium shifts to the left.

e.g.

Ethanol + Ethanoic Acid Ethyl Ethanote + Water Increase concentration of ethanol, more ethyl ethanote and water will form. ii. Pressure of gas

If we increase the pressure of a reversible reaction in equilibrium, it will shift to the side where there are fewer moles of gas.

 e.g.

If we decrease the pressure, the equilibrium shifts to the side where there are more moles of gas. N2 (g) + 3H2 (g) 2NH3 (g) 4 moles 2 moles In this example, if we increase the pressure, the equilibrium will shift to the right, where there are fewer moles of gas making more ammonia.

iii. Temperature For exothermic reactions: If we increase the temperature, the reaction moves in a backwards direction, which is endothermic. If we decrease the temperature, the reaction moves in an exothermic direction, i.e. forwards. E.g.

If we increase the temperature, the equilibrium shifts in the endothermic direction i.e. in this case, from right to left (backwards) thus making less ammonia. iv. Catalyst A catalyst does NOT affect the position of equilibrium; it just speeds up the time taken to reach equilibrium.

The Haber process

N2 (g) + 3H2 (g) 2NH3 (g) H = -92kJmol
-1

Raw materials N2 obtained from the air H2 obtained from natural gas Iron catalyst The iron catalust speeds the reaction up, but has no effect on the proportion of ammonia in the equilibrium mixture. If the catalyst wasnt used, the reaction would be so slow that virtually no ammonia would be produced. Conditions 450oC According to le Chateliers principle, the forward reaction (an exothermic change) would be favoured by a low temperature. However, the temperature used is not low. If the temperature was genuinely low, the reaction would be so slow that it would take a very long time to produce much ammonia.

450oC is a compromise temperature, producing a reasonable yield of ammonia reasonably quickly. 200 atm The reaction that produces fewer gaseous molecules is favoured by a high pressure. A high pressure would also produce a fast reaction rate because the molecules are brought closer together. The 200 atmospheres actually used is high, but not very high. This is another compromise. Generating high pressures and building the vessels and the pipes to contain them is very expensive. Pressures much higher than 200 atmospheres cost more to generate than you would get back in the value of extra ammonia produced. Even with the specific conditions of the Haber process, the yield of ammonia is very low. As the reaction mixture leaves the converter, the mixture is cooled, the ammonia condenses (as it has a higher boiling point) and is removed as a liquid. The unreacted N2 and H2 are recycled.

Uses of ammonia To make fertilisers To make explosives To make nitric acid (the Ostwald process)

Manufacture of Sulphuric acid (H 2 SO 4 ) The contact process

Step (1):

Step (2):

450oC Which is a compromise between needing a low temperature for a good yield (as reaction is exothermic), but a high temperature for a fast rate. 200 atm Which is a slightly increased pressure, to increase yield, but no higher as it is expensive. Catalyst Vanadium (V) oxide, V2O5 Step (3):

This reaction is highly exothermic and would produce an uncontrollable mist of sulphuric acid which is highly dangerous. Thus we add the sulphur dioxide to some concentrated sulphuric acid to make oleum.

We then add water to oleum:

Uses of sulphuric acid To manufacture detergents Paints Fertilisers As a dehydrating agent e.g.

Electrolysis
Electrolysis is he splitting up of a compound using electricity. The compound must be ionic and will only conduct when molten or in solution (as only then will the ions move). Migration of ions e.g. Potassium manganate (VII) KmnO4 K+ ions (colourless) and MnO4 ions (purple)

The manganate ions (MnO4) move towards the positive sides which we can see because they are purple and the potassium ions move towards the negative side however, we cannot see them. The ions are attracted to each side.

Product of the electrolysis of aqueous ionic solutions Electrolysis of molten compounds only involves two ions. However, in aqueous solutions we need to consider four ions: the two ions from the compound itself and the ions from the water. H2O Consider the electrolysis of copper (II) chloride: CuCl2 (aq) The solution contains four ions: H
+

+ OH

+
H
+ 2+

OH -

Cu

Cl

Only one positive ion and one negative ion will be discharged at the electrodes. For positive ions, if the metal ion is below hydrogen in the reactivity series, that ion will be discharged. Cu2+ + 2e Cu (at negative electrode) This is reduction (gain of electrons) For the negative, if there are halide ions present, then these are discharged: 2Cl
-

In this case:

Oxidation:

Cl2

2e

Lets consider potassium nitrate solution, KNO3 (aq) Ions present: K

+ +

NO3 OH 2e
-

H 2H
+

In this case, it is the hydrogen ions discharged at the negative electrode: +

-

H2 O2 (gas given up) + 4e

-

As there are no halide ions present, it is he hydroxide ions which are discharged: 4OH 2H2O