On the basis of following observations arrange the following compounds in increasing order of mol of AgCI precipitated per mol of the compound with excess of $AgNO_3$
|
|
Formula |
Secondary valences |
Solution conductivity |
|
(A) |
$PdCl_2.4NH_3$ |
4 |
1:2 electrolyte |
|
(B) |
$NiCl_4.2K$ |
4 |
2:1 electrolyte |
|
(C) |
$CoCl_3.4NH_3$ |
6 |
1:1 electrolyte |
|
(D) |
$CrCl_3.6H_2O$ |
6 |
1:3 electrolyte |
Choose the correct answer from the options given below:
Answer & explanation
Correct answer: option 2
The correct answer is Option (2) → (B), (C), (A), (D)
Only ionisable (outer sphere) $\text{Cl}^-$ ions react with $\text{AgNO}_3$ to form $\text{AgCl}$.
Electrolyte type reveals number of free chloride ions.
Step 1: Key Concept
$\text{AgNO}_3$ forms $\text{AgCl}$ only with free (ionisable) $\text{Cl}^-$ ions
$\text{Cl}^-$ inside coordination sphere $\rightarrow$ does NOT precipitate
$\text{Cl}^-$ outside coordination sphere $\rightarrow$ gives $\text{AgCl}$
So we must find:
How many $\text{Cl}^-$ are outside the coordination sphere?
Electrolyte type helps us determine this.
Step 2: Interpret Electrolyte Type
|
Electrolyte type |
Meaning after dissociation |
|
$1:1$ |
gives 1 anion outside |
|
$1:2$ |
gives 2 anions outside |
|
$1:3$ |
gives 3 anions outside |
|
$2:1$ |
gives least free $\text{Cl}^-$ (since $\text{Cl}^-$ mostly coordinated) |
Number of anions formed $=$ number of free $\text{Cl}^-$ ions
Step 3: Analyse Each Compound
(B) $\text{NiCl}_2 \cdot 2\text{KH}_2\text{O} \rightarrow \text{2:1 electrolyte}$
Dissociation produces more cations than anions
This implies very few $\text{Cl}^-$ are free
So $\rightarrow$ minimum $\text{AgCl}$ formed
(C) $\text{CoCl}_3 \cdot 4\text{NH}_3 \rightarrow \text{1:1 electrolyte}$
Dissociates into:
$1 \text{ complex ion} + 1 \text{ Cl}^-$
So:
$1 \text{ free Cl}^- \rightarrow \text{forms 1 mol AgCl}$
(A) $\text{PdCl}_2 \cdot 4\text{NH}_3 \rightarrow 1:2$ electrolyte
Dissociates into:
$1 \text{ complex ion} + 2 \text{ Cl}^-$
So:
$2 \text{ free Cl}^- \rightarrow \text{forms 2 mol AgCl}$
(D) $\text{CrCl}_3 \cdot 6\text{H}_2\text{O} \rightarrow 1:3$ electrolyte
Dissociates into:
$1 \text{ complex ion} + 3 \text{ Cl}^-$
So:
$3 \text{ free Cl}^- \rightarrow \text{forms 3 mol AgCl}$
$\rightarrow \text{Maximum AgCl formed}$
Step 4: Arrange in Increasing Order
$\text{AgCl}$ formed:
$(B) < (C) < (A) < (D)$