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NEET CHEMISTRYMedium

Cobalt(III) chloride forms several octahedral complexes with ammonia. A compound among the following that does not give a test for chloride ions with silver nitrate at 25 °C is:

A

CoCl3 . 3NH3

B

CoCl3 . 4NH3

C

CoCl3 . 5NH3

D

CoCl3 . 6NH3

Step-by-Step Solution

According to Werner's coordination theory:

  1. Coordination Number: Cobalt(III) typically has a coordination number (secondary valency) of 6 in these ammine complexes.
  2. Ionisation: Chloride ions present outside the coordination sphere (primary valency only) are ionisable and will precipitate as AgCl with silver nitrate. Chloride ions inside the coordination sphere (secondary valency) are non-ionisable and do not precipitate.
  3. Formulation: We arrange the ligands (NH3NH_3 and ClCl^-) to satisfy the coordination number of 6 inside the square brackets: CoCl36NH3[Co(NH3)6]Cl3CoCl_3 \cdot 6NH_3 \rightarrow [Co(NH_3)_6]Cl_3 (3 ionisable ClCl^-) CoCl35NH3[Co(NH3)5Cl]Cl2CoCl_3 \cdot 5NH_3 \rightarrow [Co(NH_3)_5Cl]Cl_2 (2 ionisable ClCl^-) CoCl34NH3[Co(NH3)4Cl2]ClCoCl_3 \cdot 4NH_3 \rightarrow [Co(NH_3)_4Cl_2]Cl (1 ionisable ClCl^-) CoCl33NH3[Co(NH3)3Cl3]CoCl_3 \cdot 3NH_3 \rightarrow [Co(NH_3)_3Cl_3] (0 ionisable ClCl^-)

Since [Co(NH3)3Cl3][Co(NH_3)_3Cl_3] has no chloride ions outside the coordination sphere, it does not release ClCl^- ions into solution and thus gives no precipitate (test) with silver nitrate .

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