Tag: ionization constants of weak acids and weak bases

$HA,  \alpha =\sqrt{\displaystyle\frac{10^{-5}}{0.1}}=0.01$ 
(A) On adding $HCl, \left [ HA \right ]=\frac{0.1}{2},\left [ HCl \right ]=\displaystyle\frac{10^{-3}}{2}$
$HCl \rightarrow H^{+}+Cl^{-}$
$HA \rightleftharpoons H^{+}  +A^{-}$
$\displaystyle\frac{0.1}{2}\left ( 1- \alpha  \right )\left (\displaystyle\frac{10^{-3}}{2}+\displaystyle\frac{0.1 \alpha }{2}  \right ) \displaystyle\frac{0.1 \alpha }{2} $
$\Rightarrow 10^{-5}=\displaystyle\frac{\displaystyle\frac{0.1\alpha }{2} \times \left (\displaystyle\frac{10^{-3}}{2}+\displaystyle\frac{0.1 \alpha }{2}  \right ) }{\displaystyle\frac{0.1}{2}\left ( 1-\alpha  \right )}$
Neglecting $\alpha $
$10^{-5}=\alpha \times \left ( \displaystyle\frac{10^{-3}}{2}+\displaystyle\frac{0.1\alpha  }{2} \right )$
$\Rightarrow 0.1 \alpha ^{2}+10^{-3} \alpha -2\times 10^{-5}=0$
$\Rightarrow  \alpha ^{2}+10^{-2}\alpha -2\times 10^{-4}=0$
$\Rightarrow \alpha =\displaystyle\frac{-10^{-2}+\sqrt{10^{-4}+8\times 10^{-4}}}{2}=\displaystyle\frac{2\times 10^{-2}}
{2}=2$
Which is similiar to initial.
(B) In case of two weak acids
$\left [\mathrm H^{+}  \right ]=\sqrt{10^{-5}\times \frac{0.1}{2}+2\times 10^{-6}\times \displaystyle\frac{0.5}{2}}$
$=\sqrt{\displaystyle\frac{10^{-6}}{2}+\displaystyle\frac{10^{-6}}{2}}=10^{-3}$
$\alpha =\displaystyle\frac{10^{-5}}{10^{-3}}=10^{-2}$
which is same as earlier
(C) $HNO _{3}\rightarrow H^{+}+NO _{3}^{-}$
$\displaystyle\frac{0.1}{2}       \displaystyle\frac{0.1M}{2}$
$HA \rightleftharpoons H^{+}   +  A^{-}$
$\displaystyle\frac{0.1M}{2}\left ( 1-\alpha  \right )  \displaystyle\frac{0.1}{2}+\displaystyle\frac{0.1}{2}\alpha                
\displaystyle\frac{0.1}{2}\alpha$
$\Rightarrow 10^{-5}=\displaystyle\frac{\frac{0.1\alpha }{2}\times \displaystyle\frac{0.1 }{2} \left (1+\alpha  \right )  }{\displaystyle\frac{0.1}{2}\left (1-\alpha  \right )}$
Neglecting $\alpha $ due to common ion effect.
$\Rightarrow 10^{-5}=\displaystyle\frac{0.1 \alpha }{2}$
$\Rightarrow \alpha =2\times 10^{-4}$
Hence, it decreases from $0.01  to  2\times 10^{-4}$.

The common ion effect describes the changes that occur with the introduction of ions to a solution containing that same ion.
The role that the common ion effect in solutions is mostly visible in the decrease of solubility of solids. Through the addition of common ions, the solubility of a compound generally decreases due to a shift in equilibrium.
$BaCl _2\rightarrow Ba^{2+} + 2Cl^{-}$
$HCl \rightarrow H^{+} + Cl^{-}$
As $Cl^{-} $ is the common ion so, the $ Ba^{2+}$and $ 2Cl^{-}$ combines ( associate ) to give the undissociated $BaCl _2$. 
Hence , there is increase in concentration of undissociated $BaCl _2$.

$Ag^+ + Cl^- \rightarrow AgCl$
$NaCl \rightarrow Na^+ + Cl^-$
As $Cl^- $ is the common ion in both the solution ( i.e. $NaCl $ and $AgCl$ ) , hence $AgCl$ being weaker electrolyte is precipitated or solubility of the silver chloride would decrease.
Common ion Effect : The common ion effect is responsible for the reduction in the solubility of an ionic precipitate when a soluble compound containing one of the ions of the precipitate is added to the solution in equilibrium with the precipitate. It states that if the concentration of any one of the ions is increased, then, according to Le Chatelier's principle, some of the ions in excess should be removed from solution, by combining with the oppositely charged ions. Some of the salt will be precipitated until the ion product is equal to the solubility product. In short, the common ion effect is the suppression of the degree of dissociation of a weak electrolyte containing a common ion

The correct answer is $(A)$.

While the NH4OH is weak base it does not ionises completely. Thus due to presence of common ion NH4+ in NH4Cl, it supresses the ionisation of weak base NH4OH in order to decrease the OH-concentration so that higher group cations will not get precipitated. 

$\text{On reacting with NaOH(aq) the Mg+2 gives precipitation reaction.}$