Topic 7: Equilibrium SL Le Chatelier’s Principle 7.2.3 Apply Le Chatelier’s principle to predict qualitative effects of changes of temperature, pressure and concentration on the position of equilibrium and on the value of the equilibrium constant. 7.2.4 State and explain the effect of a catalyst on an equilibrium reaction. 7.2.5 Apply the concepts of kinetics and equilibrium to industrial process Suitable examples include the Haber and Contact processes.

LeChatelier’s Principle When a system at equilibrium is placed under stress, the system will undergo a change in such a way as to relieve that stress.

Le Chatelier Translated: When you take something away from a system at equilibrium, the system shifts in such a way as to replace what you’ve taken away. When you add something to a system at equilibrium, the system shifts in such a way as to use up what you’ve added.

Le Chatelier Example #1 A closed container of ice and water at equilibrium. The temperature is raised. Ice + Energy <-- > Water The equilibrium of the system shifts to the _______ to use up the added energy. right

Le Chatelier Example #2 A closed container of N2O4 and NO2 at equilibrium. NO2 is added to the container. N2O4 (g) + Energy < - - > 2 NO2 (g) The equilibrium of the system shifts to the _______ to use up the added NO2. left

Le Chatelier Example #3 A closed container of water and its vapor at equilibrium. Vapor is removed from the system. water + Energy  vapor The equilibrium of the system shifts to the _______ to replace the vapor. right

Le Chatelier Example #4 A closed container of N2O4 and NO2 at equilibrium. The pressure is increased. N2O4 (g) + Energy < - - > 2 NO2 (g) The equilibrium of the system shifts to the _______ to lower the pressure, because there are fewer moles of gas on that side of the equation. left

Pressure Changes to system If the volume decreases, the concentration increases, and there will be a shift to the side with the less amount of moles. If the volume increases, the concentration decreases, and there will be a shift to the side with the more amount of moles.

Example; If I increase the pressure, where is the shift? (right) If I decrease the pressure, where is the shift? (left) 2SO2 + O2 <--> 2SO3 (3moles) (2moles)

Effect of Concentration If you add more reactant, it shifts to the right increasing the formation of product, using up the reactants. If you add product, it shifts to the left If you remove product, it shifts to the right, increasing the formation of product. If you remove reactant, it shifts to the left

Effect of temperature Energy is treated as a reactant if endothermic equation, and as a product if exothermic equation. If cooling a system, then it shifts so more heat is produced. If heating a system, then it shifts so extra heat is used up.

Example for temp. changes for Endothermic Reaction Heating the below reaction causes the system to shift to the right = more products, because you treat energy like a reactant. 2NaCl +H2SO4 + energy < -- > 2HCl + Na2SO4 Cooling the above reaction causes the system to shift to the left = less reactants, so need to make up more

Effect of temp change on exothermic reactions Heating the below reaction causes the system to shift to the left, to use up the extra heat. 2SO2 + O2 <--> 2SO3 + energy Cooling the above reaction causes the system to shift to the right, to make up for the lost heat.

The effect of a catalyst on equilibrium Adding a catalyst speeds up a reaction by providing an alternative mechanism with a lower activation energy, thus speeding up both the forward and backward reaction rate. It shortens the time needed to attain equilibrium concentrations It has no effect on the position of equilibrium, however equilibrium will be attained more quickly.

Haber Process N2(g) + 3H2(g) < - - > 2NH3(g) ΔH= -92 kJ/mol Mixture’s volume is compressed and passed over a heated iron catalyst. Conditions for his equilibrium is critical. High pressure is favourable due to 4 moles on left and 2 moles on right. Increased pressure causes a shift to the left, favouring product formation. This is expensive to due and most production plants will resist compressing gases in terms of operating costs. Compromise will be met.

Compromise This is an exothermic reaction, so low temperatures would be favourable to produce product. Low temps mean low reaction rates, so we may get a higher yield but it will take a long time to get it. Not good for business. A compromise temp, as well as the use of a catalyst will aid in speeding up the reaction to a more acceptable standard.

Typical conditions Pressure between 20-100 MPa (200-1000 atm) Temperatures around 700 K The reaction is not allowed to reach equilibrium, because reaction rate decreases as we approach equilibrium, and typically only 20% of N2 and H2 is converted. The gases are cooled and NH3 is condensed and removed, leaving unused N2 and H2 available for further production.

Animation of Haber process http://www.absorblearning.com/media/item.action?quick=128# Animation of Haber process

Ammonia’s Uses Manufacture of fertilizers (ammonia salts and urea) Manufacturing nitrogen used in polymers for the fabrication of nylon Used in the production of explosives (TNT, dynamite)

Contact Process Production of sulfuric acid by the oxidation of sulfur. Sulfur is burnt in air to form sulfur dioxide S(s) + O2(g) < - - > SO2(g) Sulfur dioxide is mixed with air and passed over vanadium(V)oxide catalyst to produce sulfur trioxide. 2SO2(g) + O2(g) < - - > 2SO3(g) ΔH= -196 kJ/mol Sulfur trioxide is reacted with water to produce sulfuric acid. SO3(g) + H2O(l)  H2SO4(l)

More money, more SO3… High pressure would favour the formation of SO3 in the 2nd step, however its too expensive. Reactants are compressed to 2 atm to achieve the desired flow rate in the reactor. Pure O2 would drive the equilibrium to the right, however its an unnecessary expense. Low temperatures, because its exothermic, would be best, but it slows the rate too much.

Compromised conditions Temp between 700-800 K (fast initial reaction rate) The use of a finely divided V2O5 catalyst Oxidation is done in converters at lower temperatures (slows reaction rate) Overall conversion is 90% to SO3

Contact process animation http://www.absorblearning.com/media/item.action?quick=12b Contact process animation

Uses of H2SO4 Fertilizers (converting insoluble phosphate rock into soluble phosphates) Polymers Detergents Paints Pigments Petrochemical industry Processing of metals Electrolyte in car batteries

Le Chatelier’s principle is a memory aid, it doesn’t explain why these changes occur. Listen carefully and read over text pages to help you develop further understanding of explanation. http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/lechv17.swf

Haber process notes http://www.chemguide.co.uk/physical/equilibria/haber.html