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Equilibrium Dynamic equilibrium: the rate of the forward reaction is equal to the rate of the backward reaction.

both forward and backward reactions are still occurring, even it may not be visible. Physical systems: In closed systems, where no particles can escape, particles can be in equilibrium between liquid and gas states, where the rate of evaporation is equal to the rate of condensation. Chemical systems: In reversible reactions, equilibrium is reached when the rate of the forward reaction is equal to the rate of the backward reaction

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Characteristics of the equilibrium position: It is dynamic It is achieved in closed systems (no matter is exchanged with the surroundings) The concentrations of reactants and products remain the same (but not necessarily equal) Equilibrium can be reached from either direction.

Reactants that contain predominantly products are said to lie to the right. Reactants that contain predominantly reactants are said to lie to the left. The equilibrium constant (KC) has a fixed value for a particular reaction at a specific temperature. To find the constant, we need to write the equilibrium constant expression.

Where A is the substance, and a is the coefficient.

This expression can be seen as the ratio of reactants to products. If the constant is high, then the equilibrium lies to the right. If Kc>>1, the reaction is considered to go almost to completion. If the constant is low, then the equilibrium lies to the left. If Kc<<1, the reaction hardly proceeds. Disruption of Equilibrium Le Chataliers principle: a system at equilibrium when subjected to a change will respond in such a way as to minimize the effects of the change.

Changes in concentration: Increasing the concentration of reactants causes an increase in reaction rates. This is a change in favour of the reactants.

The equilibrium will shift to the right, in favour of the products. The concentration of products will increase, and the concentration of reactants will decrease. The value of Kc will remain unchanged. Decreasing the concentration of products will have the same effect, as it reduces the rate of the backward reaction. Changes in pressure: If a change in pressure involves a change in the number of molecules (different number of molecules between reactants and products), the equilibrium will shift. Increase in pressure: The equilibrium will shift in favour of the side with the smaller number of molecules. Decrease in pressure: The equilibrium will shift in favour of the side with the bigger number of molecules. Changes in temperature: Changing the temperature will change the value of KC. The enthalpy changes of the forward and backward reactions are equal and opposite. A decrease in temperature will favour the exothermic reaction. (higher yield from a lower temperature). There will be a decrease in the value of Kc. An increase in temperature will favour the endothermic reaction. There will be an increase in the value of Kc.

Addition of a catalyst: Catalysts do not change the position of equilibrium or the value of KC. Industrial Applications Having a high yield is important in industrial applications. The Haber process: The Haber process is used in the production of ammonia (NH3)

The product, ammonia, is removed as it forms to shift the equilibrium to the left. High pressure is used as the reaction will favour the product side. A low temperature is preferred as the forward reaction is exothermic, but a medium temperature is used to make the reaction faster. A catalyst is added to speed up the reaction. The contact process: The contact process is used in the production of sulfuric acid (H2SO4) High pressure is used Low temperature increases yield, but reduces rate.

Liquid-Vapour Equilibrium In closed systems, where no particles can escape, particles can be in equilibrium between liquid and gas states, where the rate of evaporation is equal to the rate of condensation. Vapour pressure: the particles of vapour above the liquid exert a pressure on the surface of the liquid. The surface area and volume of the liquid do not affect vapour pressure. This is because evaporation and condensation both occur at the surface, hence are equal affected by changes in surface area. Volume changes do affect the equilibrium, but the vapour pressure will remain unchanged. Factors affecting vapour pressure: 1- Temperature: Increasing temperature causes an increase in evaporation, as particles will have sufficient energy to escape the liquid as the average kinetic energy increases. The threshold energy required is known as the escape kinetic energy. Boiling: vapour pressure reaches external pressure. The boiling point depends on pressure. 2- Nature of the substance The forces of attraction between particles must be overcome for evaporation to occur. The stronger the intermolecular forces, the more energy needed for evaporation.

The equilibrium law If the equilibrium concentrations are not know, the following is done: From initial and equilibrium concentrations: If you know the initial and final concentrations of a reactant, the change in concentration can be found. The initial concentration of other reactants will be reduced by the same amount, while the concentration of the products will rise by that amount. The change will be in the same ratio as the coefficients in the balanced equation. From the equilibrium constant: If we know the value of the equilibrium constant, and the values of all the concentrations but one, the equilibrium expression can be rearranged to find the unknown concentration. If only the initial concentrations are known, then algebra is used to find the change in concentration to find the equilibrium concentration. Change in the concentration of reactants= -x Change in he concentration of products: +x Equilibrium concentration of reactants: initial concentration x Equilibrium concentration of products: x To eliminate squared concentrations in the equilibrium expression, take the square root of both sides. If the equilibrium constant is small, the reaction hardly proceeded. In that case, the initial concentration is approximately equal to the equilibrium concentration.

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