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Question: In the dissociation of \(N{H_4}OH\), if excess of \(N{H_4}Cl\) is added before adding \(N{H_4}OH\), ...

In the dissociation of NH4OHN{H_4}OH, if excess of NH4ClN{H_4}Cl is added before adding NH4OHN{H_4}OH, the concentration of:
(A) NH4+NH_4^ + ions increases and OHO{H^ - } ions decreases
(B) Both NH4+NH_4^ + ions and OHO{H^ - } ions increases
(C) NH4+NH_4^ + ions decreases and OHO{H^ - } ions increases
(D) Both NH4+NH_4^ + ions and OHO{H^ - } ions decreases

Explanation

Solution

NH4OHN{H_4}OH is a weak base and does not dissociate completely, while the NH4ClN{H_4}Cl is a strong electrolyte and undergoes complete dissociation. Since both of them have NH4+NH_4^ + ion in common, the common ion effect takes place thus suppressing the dissociation of NH4OHN{H_4}OH.

Complete step by step answer:
-First of all we will see how dissociation of NH4OHN{H_4}OH occurs. It dissociates into NH4+NH_4^ + and OHO{H^ - } ions as shown below:
NH4OHNH4++OHN{H_4}OH \rightleftharpoons NH_4^ + + O{H^ - }

According to the law of mass action the above equation at equilibrium can be expressed by the equation:
K=[NH4+][OH][NH4OH]K = \dfrac{{\left[ {NH_4^ + } \right]\left[ {O{H^ - }} \right]}}{{\left[ {N{H_4}OH} \right]}}
We should keep in mind that NH4OHN{H_4}OH is a weak base and so it does not undergo complete ionisation.

-The NH4ClN{H_4}Cl acts as a strong electrolyte and thus undergoes complete ionisation. It’s ionisation reaction would be:
NH4ClNH4++ClN{H_4}Cl \rightleftharpoons NH_4^ + + C{l^ - }
-In the above two ionisation reactions we can see that the ion NH4+NH_4^ + is common in both. Hence this leads to the common ion effect. The common ion effect is the decrease in the solubility of some ionic precipitate due to the addition of a soluble compound into the solution which has an ion in common with the precipitate. This occurs in accordance with Le Chatelier’s principle for the equilibrium reaction of the ionic association or dissociation.
Hence according to the common ion effect the addition of excess of NH4ClN{H_4}Cl before adding NH4OHN{H_4}OH leads to increased concentration of NH4+NH_4^ + ions and hence the dissociation of NH4OHN{H_4}OH gets suppressed in accordance with the Le Chatelier’s principle. Hence this leads to decreased concentration of OHO{H^ - } ions.
So, the correct answer is “Option A”.

Note: We should know that if a small amount of HCl is added to this solution,H+{H^ + } ions of HCl get neutralized by the OHO{H^ - } ions already present and thus more of NH4OHN{H_4}OH molecules will get ionized to compensate the loss of OHO{H^ - } ions. Thus pH practically remains constant.