In general, when equilibrium is disturbed by the addition/removal of any reactant/ products, Le Chatelier’s principle predicts that:
The concentration stress of an added reactant/product is relieved by net reaction in the direction that consumes the added substance.
The concentration stress of a removed reactant/product is relieved by net reaction in the direction that replenishes the removed substance.
or in other words,
“When the concentration of any of the reactants or products in a reaction at equilibrium is changed, the composition of the equilibrium mixture changes so as to minimize the effect of concentration changes”.
Let us take the reaction, H2(g) + I2(g) ⇔ 2HI(g)
If H2 is added to the reaction mixture at equilibrium, then the equilibrium of the reaction is disturbed. In order to restore it, the reaction proceeds in a direction wherein H2 is consumed, i.e., more of H2 and I2 react to form HI and finally the equilibrium shifts in right (forward) direction (Figure). This is in accordance with the Le Chatelier’s principle which implies that in case of addition of a reactant/product, a new equilibrium will be set up in which the concentration of the reactant/product should be less than what it was after the addition but more than what it was in the original mixture.
The same point can be explained in terms of the reaction quotient, Qc
Qc = [HI]2/ [H2][I2]
Addition of hydrogen at equilibrium results in value of Qc being less than Kc . Thus, in order to attain equilibrium again reaction moves in the forward direction.
Similarly, we can say that removal of a product also boosts the forward reaction and increases the concentration of the products and this has great commercial application in cases of reactions, where the product is a gas or a volatile substance.
In case of manufacture of ammonia, ammonia is liquified and removed from the reaction mixture so that reaction keeps moving in forward direction.
Similarly, in the large scale production of CaO (used as important building material) from CaCO3, constant removal of CO2 from the kiln drives the reaction to completion.
It should be remembered that continuous removal of a product maintains Qc at a value less than Kc and reaction continues to move in the forward direction.
Effect of Concentration – an Experiment
This can be demonstrated by the following reaction:
Fe3+(aq) + SCN-(aq) ⇔ [Fe(SCN)]2+(aq)
Yellow colorless deep red
KC = [[Fe(SCN)]2+(aq)]/[ Fe3+(aq)][ SCN-(aq)]
A reddish colour appears on adding two drops of 0.002 M potassium thiocynate solution to 1 mL of 0.2 M iron(III) nitrate solution due to the formation of [Fe(SCN)]2+. The intensity of the red colour becomes constant on attaining equilibrium.
This equilibrium can be shifted in either forward or reverse directions depending on our choice of adding a reactant or a product. The equilibrium can be shifted in the opposite direction by adding reagents that remove Fe3+ or SCN– ions.
For example, oxalic acid (H2C2O4), reacts with Fe3+ ions to form the stable complex ion [Fe(C2O4)3]3–, thus decreasing the concentration of free Fe3+(aq).
In accordance with the Le Chatelier’s principle, the concentration stress of removed Fe3+ is relieved by dissociation of [Fe(SCN)]2+ to replenish the Fe3+ ions. Because the concentration of [Fe(SCN)]2+ decreases, the intensity of red colour decreases.
Addition of aq. HgCl2 also decreases red colour because Hg2+ reacts with SCN– ions to form stable complex ion [Hg(SCN)4]2–. Removal of free SCN– (aq) shifts the equilibrium in equation from right to left to replenish SCN– ions.
Addition of potassium thiocyanate on the other hand increases the colour intensity of the solution as it shift the equilibrium to right.