The le Chatelier's principle can be stated as: When external stress is applied on a system at dynamic equilibrium, the system

shifts the position of equilibrium so as to nullify the effect of stress. Stress can be applied on chemical systems by changing the concentration or pressure or temperature. Therefore the le Chatelier's principle can also be stated as: When a chemical system at dynamic equilibrium is disturbed by changing the concentration of either reactants or products; or by changing the partial pressures of any of gaseous reactants or of gaseous products; or temperature, the position of equilibrium is changed in that direction so as to establish a new equilibrium state i.e., either forward reaction or backward reaction is favored. In Haber process, the ammonia is synthesized by combining pure nitrogen and hydrogen gases in 1:3 ratio in presence of finely powdered iron catalyst and molybdenum promoter at around 450oC and at about 250 atm. of pressure.

The le Chatelier's principle helps in choosing these conditions to improve the yields of ammonia as explained as below. Effect of pressure: In the forward reaction (synthesis of ammonia), the number of moles of gaseous components is decreasing. i.e., ng = (2) - (1+3) = -2 Hence the synthesis of ammonia is favored by increasing the pressure of the system. Industrially, 100 250 atm. of pressure is employed. Effect of temperature: Since the forward reaction is exothermic, the increase in temperature favors the backward reaction i.e., the dissociation of ammonia. That means according to le Chatelier's principle, the synthesis of ammonia is favored at lower temperatures. However the reaction will be too slow at lower temperatures (a kinetic restriction). Hence this reaction is carried out at optimal temperatures i.e., at about 450 - 550 oC to overcome the kinetic barrier. Removal of ammonia: The forward reaction can also be favored by removing ammonia from the system from time to time by liquefying it. Catalyst: To increase the speed of the reaction, finely powdered or porous iron is used as catalyst. Its efficiency can be improved by adding molybdenum or oxides of potassium and aluminium. What will be the effect of addition of inert gas on the equilibrium constant? Effect of addition of inert gas like helium, neon etc has the following effects on the equilibrium constant: There are two cases on which equilibrium depends. These are: (1) Addition of an inert gas at constant volume: When an inert gas is added to the system in equilibrium at constant volume, then the total pressure will increase. But when the concentrations of the products and reactants i.e. ratio of their moles to the volume of the container will not change. Hence, when an inert gas is added to the system in equilibrium at constant volume there will beno effect on the equilibrium. (2) Addition of an inert gas at constant pressure: When an inert gas is added to the system in equilibrium at constant pressure, then the total volume will increase. Hence, the number of moles per unit volume of various reactants and products will decrease. Hence, the equilibrium will shift towards the direction in which there is increase in number of moles of gases. For example: Consider the following reaction in equilibrium: 2 NH3 (g) N2 (g) + 3 H2 (g) The addition of an inert gas at constant pressure to the above reaction will shift the equilibrium towards the forward direction because the number of moles of products is more than thenumber of moles of the reactants.