LITERATURE REVIEW In 1884, as noted by G.

Austin (1984) the French Chemist Henri Le Chatelier suggested that equilibrium systems tend to compensate for the effects of perturbing influences. When a system at equilibrium is disturbed, the equilibrium position will shift in the direction which tends to minimise, or counteract, the effect of the disturbance. For a reversible chemical reaction, Chatelieris principle has several important implications. Firstly if the concentration of a reactant is increased, the equilibrium position shifts to use up the added reactants by producing more products. Secondly, M.Morgan(2002) for gaseous reactions, gas pressure is related to the number of gas particles in the system, more gas particles means more gas pressure. Consider a reaction which is accompanied by decrease in number of moles for ammonia synthesis. By increasing the pressure on this equilibrium system will result in the equilibrium position shifting to reduce the pressure, that is, to the side that has the least number of gas particles. Furthermore, according to Z.Kowalczyk and J.Sentek (1996.) the amount of ammonia formed in a single gas pass is much too small to be of interest for the economic production of ammonia. Therefore, the gases were recycled over the catalyst after separating the ammonia formed by condensation. The gas lost by conversion was compensated with a fresh gas input and the mixture was recycled under pressure. This process became the basis for the technical manufacture of ammonia. Since then, the same principle has found widespread application for numerous high-pressure reactions in the organic chemistry sector. Habers recycle idea changed the previously static conception of process engineering in favour of a more dynamic approach. For the first time, reaction kinetics as well as the thermodynamics of the system was being considered. In addition to chemical equilibrium, they recognized that reaction rate was a determining factor in this problem. Instead of simple reaction yield, J.Sentek (1996) concentrated on space-time yield, that is, the amount of ammonia obtained per unit volume of the catalyst per unit time. In this manner it became apparent that the real problem was to find a suitable catalyst so that the maximum amount of product is obtained with minimum volume of the catalyst in the shortest time possible, that is, space time yield needs to be maximized.

REFERENCES G.Austin(1984) Shreves Chemical Process Industries, 5th ed, McGraw-Hill International Editions, New York. M.Morgan(2002) The Story of Fritz Haber, University of Oklahoma Press, 67(2) (May): 209-216. Mott, Frank L. and Sylvia F. Moore (1996) Applied Catalyst : Haber Process, 41(2) (May): 355-365.

BACKGROUND OF STUDY During the last century, the populations of Europe and America rose very rapidly. More food and more crops were needed to feed more and more people. So farmers began to use nitrogen compounds as fertilisers. The main source of nitrogen compounds for fertilisers was sodium nitrate from Chile. By 1900 supplies of this were running out. Another supply of nitrogen had to be found or many people would starve. The obvious source of nitrogen was the air (about 78% of the air is nitrogen). Unfortunately, nitrogen is not very reactive. This made it difficult to convert it into ammonium salts and nitrates for use as fertilisers. A German chemist called Fritz Haber solved the problem. In 1904, Haber began studying the reaction between nitrogen and hydrogen. By 1908 he had found the conditions needed to make ammonia (NH3). Eventually, the Haber process became the most important method of manufacturing ammonia. The Haber process, also known as the Haber-Bosch Process. Haber discovered the conditions for the formation of ammonia, and Bosch discovered the work of high-pressure on chemical reactions (developed into industrial process). Both were awarded the Nobel Prize. It only requires 1% of the world's energy to make 500 million tons of artificial fertilizer per year, which, in turn, helps feed 40% of the world's population. THE PROCESS The Haber process takes nitrogen gas from air and combines it with molecular hydrogen gas to form ammonia gas. This is an exothermic reaction, meaning it releases energy so that the sum of the enthalpies of N2 and H2 (the reactants) is greater than the enthalpy of NH3 (the products). N2(g) + 3H2(g) 2NH3(g) which is a reversible reaction: 2NH3(g) N2(g) + 3H2(g) H=+ 92.4 kJ mol-1 H=-92.4 kJ

Here's a visual to help convey the process:

The raw materials for the Haber process are Natural gas, air and water. From the flow chart above, in the first stage, Natural gas (which is mostly methane) is reacted with steam to produce carbon dioxide and hydrogen. To speed up the reaction, a catalyst is used. A high temperature and a high pressure also speed up the reaction. In the second stage, some of the hydrogen from the first stage is burnt in air. The oxygen in the air reacts with the hydrogen to make steam. The reason for this second stage is to remove the oxygen from the air to leave nitrogen behind. It also makes a lot of the heat needed in the Haber process. In the third stage, hydrogen from the first stage is mixed with nitrogen from the second stage. The two gases are put under high temperature and high pressure. Usually 400C and 150300 atmospheres of pressure are used. Iron is also added as a catalyst. Some of the gases are converted to ammonia. The ammonia is cooled to turn it into a liquid. The liquid ammonia is then run off from the gases. The unconverted gases are then recycled to have another chance of reacting. In predicting how to obtain the highest yield from this reaction we must refer to Le Chatlier's Principle. This states that for an equilibrium reaction the equilibrium will work in the opposite direction to the conditions forced upon it. The conditions most pertinent to the above reaction are temperature and pressure. The pressure exerted by any gas or mixture of gasses in an enclosed space is directly proportional to the number of atoms or molecules of gas regardless of their size or molecular mass. Reference to the above reaction shows that, as the reaction moves to the right the number of molecules and hence the pressure decreases. Therefore the reaction moving to the right (i.e. towards the product required) is favoured by an increase in pressure.

With regard to temperature, the reaction moving to the right is exothermic i.e. it gives off energy (in the form of heat). Therefore reference to Le Chatlier's Principle shows that the reaction to the right is favoured by low temperatures.However, when Haber placed the reactants together under these conditions it was shown that the rate of reaction was so slow as to render the process unfeasible as an industrial process. This is because of unusually high activation energy. At extremely high temperature the nitrogen molecule will dissociate and so, as the temperature approaches this point the rate at which the reaction to the right occurs and therefore the speed with which equilibrium is reached increases rapidly. Unfortunately experimentation showed that, as temperature approached the point at which the speed of the reaction was sufficient to produce a viable reaction the amount of ammonia produced was so low that the reaction was still unfeasible on as an industrial process.

The Future of the Haber Process. In 1998 the Haber Process accounted for 29% of the atmospheric nitrogen fixed in the form of nitrates used by vegetation world-wide. If this reliance on artificial fertiliser is continued and the world population increases as expected (with the attendant increase in the number of crops being grown) then by the year 2050 160,000,000 tons of nitrogen will need to be manufactured per annum requiring the burning of 270,000,000 tons of coal or its equivalent to feed this energy - hungry process with all of the attendant environmental problems. Further to this the use of chemical fertilisers also affects the global nitrogen cycle, pollutes groundwater and increases the level of atmospheric nitrogen dioxide - a potent "greenhouse" gas. As a result of this work is now underway to both try to solve the problem of the high energy consumption of the Haber Process and to reduce our reliance on chemical fertilisers. The Unit of Nitrogen Fixation at Sussex University has now identified the reaction with the metal molybdenum within the enzyme nitrogenase which allows bacteria to fix atmospheric nitrogen at soil temperatures. This has enabled research to commence on low energy methods of producing ammonia. The current method of production of nitrates via the production of ammonia in the Haber Process has been identified as being destructive to the environment despite its beneficial effects in helping to feed the world population. As a result funding is now being allocated to finding alternatives to this process. Though both of the above projects are far from complete they do demonstrate a commitment to making the Haber Process redundant and it is fairly certain that even if these avenues of research prove to be unsuccessful others will be explored until an alternative is found. it therefore seems that the days of one of the most widespread industrial processes in the world are now numbered.