Presented To: Miss Fatima Ijaz Presented By : Muhammad Talha Wasim Muhammad Ahmad Majad Khan Ashfaq Ahmed

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Irreversible Reaction:
The reaction in which product of the reaction do not react to reform the original reactants, under same set of condition are called irreversible reaction. E.g. 2kClO3 (S) 2KCl (S) + 3O2 (g) The irreversible reactions proceeds in one direction only. In such reactions chemical equilibrium is not established. These reactions are denoted by a single full headed arrow ( ).

Reversible Reaction:
The reaction in which product of the reaction react to reform the original reactants, under same set of condition are called irreversible reaction. E.g. CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l) Reversible reaction proceeds in both direction i.e. forward as well as backward direction. In such reaction chemicals equilibrium is usually established. These reaction are denoted by two half headed arrow(
).

STATE OF EQUILIBRIUM: A state of chemical reversible reaction at which rate of forward reaction becomes equal to the rate of reverse reaction at the condition of T,P etc is called chemical equilibrium state and mixture of reactants and products obtained at this state is called chemical equilibrium mixture. The chemical reaction does not stop at this state but continuous to take place in both direction at equal rate. Therefore chemical equilibrium state is not a static state but is a dynamic state. But the concentration of reactants and products becomes constant at equilibrium under given conditions of T and P. Once an equilibrium has been establish it will last forever if undisturbed.

Example: Let us take an example for the illustration of chemical equilibrium.

Let the initial concentration of A and B be equal. As time goes on, concentration of A and B decrease at first quite rapidly but later slowly. Eventually the concentration of A and B level off and become constant. The graph is plotted between time and concentration for reactants and products. The initial concentration of C and D are formed. Their concentration increase rapidly then level off. At the time of equilibrium, the concentration becomes constant. This is how the chemical equilibrium is attained

Homogenous Chemical Equilibrium: An equilibrium in which all the substances are in the same phase is called homogenous equilibrium. e.g. PCl5 (g) PCl3 (g) + Cl2 (g) CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l) Heterogeneous Chemical Equilibrium : An equilibrium in which all the substances are in the different phases is called homogenous equilibrium. e.g. 3Fe (s) +4 H2O (g) Fe3O4 (s) + 4 H2 (g) C (s) + H2O (g) CO(g) + H2

Statement: The rate at which the reaction proceeds is directly proportional to the product of the active masses of the reactants. Now consider a general reaction in which A and B are the reactants and C and D are the product. The reaction is represented by the following chemical reaction. The a,b,c,d are the moles . Rate of forward reaction (Rf ) = kf [A]. [B] Rate of backward reaction (Rr) = kr [C]. [D] When equilibrium is achieved (Rf ) = (Rr)

This equation is known as equilibrium constant expression for a general reversible reaction. The subscript c indicates the molar concentration of substances of equilibrium state. In gaseous equilibrium their concentration are measured in term of partial pressure and in gaseous equilibrium constant are measured in term of partial pressure.

Where

As long as the number of moles of product and reactants, which are in the gaseous state are equal, the value of Kc and Kp remains the same. Other wise the following relation ship between Kc and Kp can be derived by using Daltons law of partial pressure. Kp = Kc (RT)n
n = (moles of gaseous product) (moles of gaseous reactant)

The value of equilibrium constant is specific and remains constant at a particular temperature. The value of equilibrium constant (kc) can be used to predict Direction of reaction Extent of reaction Effect of various factor on equilibrium constant and equilibrium position. Direction of reaction: we know that kc = The direction of a chemical reaction at any particular time can be predicted by mean of [Product]/[Reactants] ratio, calculated before the reaction attains equilibrium. The value leads to the three possibilities. The ratio is less than kc. Its mean more product is required to attain the equilibrium. The reaction moves to forward direction. The ratio is greater than kc . Its mean the reverse reaction will occur to attain the equilibrium. When the ratio is equal to kc . Then the reaction is at equilibrium.

Extent of reaction: The magnitude of the equilibrium constant allows us to predict the extent of the reaction. Very large K (e.g. 1010) mostly products. It means the reactants are almost completely into the products. Its mean that the reactants are highly unstable and reactive whereas products are highly stable and unreactive. Very small K (e.g. 1010) mostly reactants. It means the reactants are not converted into the products. Its mean that the reactants are highly stable and unreactive whereas products are highly unstable and reactive When K is around 1, a significant amount of reactant and product present in the equilibrium mixture. It means neither the reactants or product is too reactive or un reactive. The Effect Of Condition On Equilibrium Position: Equilibrium constant and equilibrium position are the two different entities. Kc is the equilibrium constant and has a constant value at particular temperature. The ratio or product to reactant is described as position of equilibrium and it can be changed if the external conditions e.g. temperature, pressure and concentration are altered. If Kc is large the position of equilibrium lies on the right and if it is small, the position lies on the left for the reversible reaction. We have to discuss an important principle in this respect i.e. Le-Chateliers principle.

Le-Chateliers Principle:

Consider the reaction BiCl3 + H20 Kc =

BiOCl + 2HCl

In this reaction BiCl3 reacts with water to give a white insoluble compound Bi0Cl. Aqueous solution of BiCl3 is cloudy, because of hydrolysis and formation of BiOCl . If small amount of HCl is added to this solution, it will disturb the equilibrium and force the system to move in such a way so that effect of addition of HCl is minimized. The reaction move in the backward direction to restore the equilibrium again. However if the water is added in the above reaction the system moves in the forward direction and the solution again become cloudy. The shifting of reaction to forward and backward direction by disturbing the concentration is according to Le-Chatlier principle. So in general the addition of a substance among the reactants and removal of the substance among the product at equilibrium stage disturb the equilibrium and reaction move in forward direction or vice versa. Removing one of the product formed increases the yield of a reversible reaction.

Effect Of Change In Volume Or Pressure:

For a given reaction 2SO2 (g) + O2 (g) 2SO3 (g) a moles b moles 0 moles t=0 (a-2x) moles (b-x) moles 2x moles t = teq The equilibrium constant expression for this reaction is Kc = This gas phases reaction proceeds with the decrease in the number of moles and hence decrease in volume at equilibrium stage. When the reaction approaches the equilibrium stages, the volume of equilibrium mixture is less than the volume of reaction taken initially. If one decreased the volume further at equilibrium stage, the reaction is disturbed. It will move to the forward direction to minimize the effect of disturbance. The reverse is happen when volume is increased or pressure is decreased at equilibrium stage.

The quantitative effect can be inferred from the previous reaction. 2SO2 (g) + O2 (g) 2SO3 (g) a moles b moles 0 moles t=0 (a-2x) moles (b-x) moles 2x moles t = teq Where V is the volume, a and b are the moles of SO2 and O2 present initially and x are the number of moles of oxygen which has reacted at equilibrium. According to the above equation, when volume is increased x has to be decreased to keep the Kc constant . The decrease of x means the reaction is pushed to backward direction. From the amount of the increase in volume, we calculate the amount of x which has to be decreased. If the factor of volume is present in nominator then the reactant have greater moles than product. So volume and moles have inverse relation. When volume is present in denominator then volume and moles have direct relation. Kc =

If we consider heat as a component of equilibrium mixture, a rise in temperature adds heat to the system and a drop in temperature removes heat from the system. According to the principle a temperature favors the endothermic reactions and temperature decreases favors the exothermic reactions. Considers a reaction in gaseous state CO + H20 CO2 + H2 H = -41.84 KJ/mol In this reaction if we take out heat and keep the system at this new lower temperature, the system will re adjust itself, so as to compensate the loss of heat energy. Thus more reactants molecules will react to form products molecules, therefore liberating heat because reaction is exothermic in the forward direction. Its mean decreasing temperature will shift the equilibrium to the right direction.

In most of the reaction equilibrium is not achieved in an suitable time. So an appropriate catalyst is added. A catalyst does not affect the equilibrium position of the reaction. It increases the rate of both forward and backward reaction and this reduce the time to attain the state of equilibrium.