Reversible reactions Until now we have assumed that once a chemical reaction has started it will continue until all of the available reactants have been used up. Many reactions do behave in this way but others do not. If a mixture of H 2 (g) and I 2 (g) is placed in a sealed container of fixed volume some HI(g) molecules are formed by the reaction! H 2 (g) " I 2 (g) 2HI(g) Initially the reaction is very fast as the concentration of the two reactants is high but as the reaction proceeds their concentration and the rate of reaction decreases. #onversely the chance of two HI molecules colliding and decomposing is very small initially because their concentration is so small but as the HI concentration increases so does the rate of the reverse reaction! H 2 (g) " I 2 (g) 2HI(g) $ventually the rates of the forward and reverse reactions become e%ual and no other net change occurs to the concentrations of any of the species present. It is called !namic equilibrium because although no visible change is observed the reaction is still proceeing but at t"e same rate in bot" irections. $%uilibrium is possible because the reaction is reversible and the container is sealed so that no elements of the system can enter or leave & eg no particles and no heat. 'he s!stem is close. 'he characteristics of a system in e%uilibrium are! 'he system is closed. (oth forward and reverse reactions are occurring simultaneously and their rates are e%ual. (oth reactants and products are present together but )*' necessarily in e%ual amounts 'here is no observable change in colour pressure temperature and the ratio of reactants to products. TASIS Chemistry Exercises# Equilibrium reactions +. ,hich of the following processes are examples of dynamic e%uilibrium. a. -i%uid and gaseous mercury in a sealed thermometer at a given temperature. ./) b. ,ater running into a la0e at the same rate at which it is leaving. ./) c. 1 saturated solution of 2b#l 2 in a bea0er at a constant temperature. ./) d. 1 sealed bottle of soft3drin0. ./) e. 1 pencil contained in a sealed 4ar. ./) S!stems at equilibrium 1 system stays at e%uilibrium unless is it sub4ected to a change from outside. $e %"atelier&s 'rinciple states that (a s!stem at equilibrium sub)ecte to ne* conitions *ill a)ust itsel+ to reuce t"e e++ect o+ t"e ne* conitions in orer to restore equilibrium&. In other words the reaction will read4ust itself so that it opposes and minimi5es the effect of the new conditions. 'his applies to any system in e%uilibrium ,ppl!ing $e %"atalier&s 'rinciple to s!stems in equilibrium 1. %"ange in concentration If the concentration of a chemical on one side of the e%uation is lowered for some reason the reaction shifts in the direction that replaces that which is lost. If the concentration of one side is increased then that side will react %uic0ly to get rid of the excess and restore e%uilibrium conditions. -. %"ange in temperature 1 change in temperature will affect the e%uilibrium. 1 reversible reaction is exothermic in one direction and endothermic in the other. If the temperature is raised ie the heat of the system is increased the e%uilibrium shifts so more endothermic reactions occur and so the temperature decreases again. 'he excess heat is absorbed. If the temperature is lowered the e%uilibrium shifts so the more exothermic reactions occur and more energy is released to increase the temperature. 3. %"ange in pressure If the reaction involves gaseous particles with different numbers of molecules on each sides and a pressure change occurs the e%uilibrium shifts so that e%uilibrium pressure is restored. If the pressure is increased on a gaseous e%uilibrium it must somehow create less pressure to reduce the effect and does this by ma0ing a smaller number of gas particles by shifting toward the side with less gas particles. TASIS Chemistry If the pressure is decreased then the e%uilibrium needs to ma0e more gas particles in order to bring the pressure bac0 up again and shifts toward the side with more gas particles. .. ,ing a catal!st 'he addition of a catalyst oes not c"ange the concentrations of reactants or products. It does speed up the reaction rate in bot" forward and reverse directions and allows the system to reach e%uilibrium more rapidly but neither reaction is favoured and thus no more/less of either reactants/products is used/formed. )* #H1)6$ I) $7UI-I(8IUM. T"e /aber 'rocess 0 ,n example o+ an equilibrium s!stem 'he Haber process is the process by which ammonia is made from nitrogen and hydrogen. It is an important industrial process for changing nitrogen into a form that is useful for plants to absorb as a source of nitrogen. 'he reaction follows the e%uation below! ) 2 " 9H 2 2)H 9 H : 3;2 0< mol 3+ 'he reaction is exothermic in the forward direction and endothermic in the reverse direction. 1ccording to -e #hatelier=s principle an increase in temperature should move the e%uilibrium to the left to produce less ammonia because this will use up the added heat. -owering the temperature will produce a greater yield of ammonia but it will also decrease the rate of the overall reaction. 1ccording to -e #hatelier=s principle an increase in pressure should move the e%uilibrium to the right to produce more ammonia. However disadvantages to increasing pressure are! (i) increased cost because of the thic0ness of the walls of the plant needed to contain the reaction. (ii) increased pressure means increased temperature and its disadvantages. High pressure is expensive to maintain and at low temperature the e%uilibrium is slow to reach e%uilibrium so a compromise has to be reached. 'he conditions at which the Haber process usually operates are as follows! 2ressure of 2>> atm. 'emperature from 9?> to @A> #. 6round Iron catalyst. (to increase the rate at the lower temperature) 'he e%uilibrium mixture is cooled to li%uefy the ammonia and remove it. Becreasing the concentration of a product causes the e%uilibrium to shift to ma0e more. Unused nitrogen and hydrogen is continuously recycled bac0 into the system. Increasing the concentration of the reactants causes the e%uilibrium to shift to ma0e more products. TASIS Chemistry