Chemical Equilibrium

*Dynamic Equilibrium-It is the state of reversible reaction when 1)rate of forward reaction is
equal to the rate of backward reaction 2)The reactant and the products are in constant
proportion.

*The factors which effect Equilibrium Position: 1)Temperature 2)Concentration 3)Pressure

*The factors which do not affect the Equilibrium Position: 1)Catalyst 2)Surface Area

Le Chatelier’s Principle: The principle states that the reaction reaches Dynamic Equilibrium
state and in this state if any of the factors (temperature,concentration,pressure) involved is
altered then the reaction proceeds in opposite direction in order to restore its dynamic
equilibrium state.

*Temperatre: How temperature affects the equilibrium position depends on the nature of the
reaction. i.e. For exothermic, the high temperature favors backward reaction. For endothermic,
high temperature favors forward reaction. If H=0 temperature has no effect./ For an
exothermic reaction, increase in temperature favors the reactants. For endothermic reactions
increase in temperature favors the products. Thus from le-Chateliers principle, if the
temperature is increased, the equilibrium position shifts so as to reduce the temperature.

*Pressure: Pressure can affect the equilibrium position of these reaction in which gases are
involved. If the molar ratio of the gaseous reactant to product are the same, then no effect. If
different, then high pressure will favor the direction where number of moles are less./ In
gaseous equilibria, the effect of pressure is the same as the effect of concentration. An increase
of pressure, or decrease, allows the equilibrium to adjust itself so that the equilibrium constant
remains the same.

*Concentration: When the concentration of the reactants is changed, the the forward rate
increases to produce more products and thus increase in concentration; and vice versa. Thus
the concentrations arrange themselves so that the equilibrium constant remains unaltered.

*Catalyst don’t have any effect on the equilibrium position.

Example

1)

*High temperature will favor backward reaction, since backward reaction is endothermic by
shifting to the left it uses up the surplus energy to restore is dynamic equilibrium state.
*High pressure will favor forward reaction due to the molar reaction.

*Increase in concentration of any of the reactants in the example will shift the reaction forward.
Increase in the concentration of product will favor backward reation.

Example

2)

*A temperature below forward reaction as it is exothermic but the rate will not be cost effective, where
as a temperature greater than 500 C would increase the rate but reduce the yield as backward reaction
is favoured. A temperature of 450 C is a compromise between rate and yield to make the process
economical.

*Since the molar ratio of reactants to product is 2, high pressure would have favored the forward
reaction but only a moderate pressure of 20atm to make the process economical (high pressure is
expensive)

*Catalyst has no role in equilibrium position it only increases the rate.

Example

3)

*On increasing the temperature the vessel will turn brown as forward reaction is favored and on
decreasing it will turn more yellow.

*On increasing the pressure the mixture turns yellow as backward reaction is favored as the molar ratio
is 1:2.

*Microscopic and Macroscopic: Some equilibrium reactions have macroscopic properties along with
microscopic ones. Macroscopic means observable properties (like color change) and microscopic are the
ones that cannot be observed and can only be determined experimentally (like change in volume,
pressure, concentration).

Example

4)

Q: What will be seen if to this mixture, 1) excess acid is added 2) excess alkaline is added?
Ans: 1) If excess acid is added, the equilibrium position will shift to the right.

2) If excess alkaline is added, the equilibrium position will shift to the left.

Example:

5)

*Initially when limited Cl is poured through a brown liquid is formed. At this time if chlorine supply is
cut off then nothing happens as this reaction is irreversible.

*If the ICl is allowed to react with excess Cl the a yellow solid ICl is produced. At this point if Cl supply
is cutoff, then the mixture gradually turns from yellow to brown (equilibrium position shifts to the left).