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Solutions question

2015 · Shift 1 · Q4
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Solutions question

2015 · Shift 1 · Q4

JEE AdvancedChemistrySolutionsNumerical+4 / −1
If the freezing point of a 0.01 molal aqueous solution of a cobalt (III) chloride-ammonia complex(which behaves as a strong electrolyte) is – 0.0558oC, the number of chloride(s) in the coordination sphere of the complex is [Kf of water = 1.86 K kg mol–1 ]
Numerical answer
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Correct answer: 1

  1. Use depression in freezing point formula

For a strong electrolyte: ΔTf=iKfm\Delta T_f = i K_f mΔTf​=iKf​m where:

  • ΔTf=0.0558 ∘C\Delta T_f = 0.0558\,^\circ\mathrm{C}ΔTf​=0.0558∘C
  • Kf=1.86 K kg mol−1K_f = 1.86\,\mathrm{K\,kg\,mol^{-1}}Kf​=1.86Kkgmol−1
  • m=0.01 molalm = 0.01\,\mathrm{molal}m=0.01molal

So, i=ΔTfKfm=0.05581.86×0.01i = \frac{\Delta T_f}{K_f m} = \frac{0.0558}{1.86 \times 0.01}i=Kf​mΔTf​​=1.86×0.010.0558​

i=0.05580.0186=3i = \frac{0.0558}{0.0186} = 3i=0.01860.0558​=3

Thus, the van't Hoff factor is: i=3i=3i=3

  1. Interpret i=3i = 3i=3

Since the complex behaves as a strong electrolyte, it dissociates completely into ions.

Let the complex be of the type: [Co(NH3)xCly]Cl3−y[\mathrm{Co}(\mathrm{NH}_3)_x\mathrm{Cl}_y]\mathrm{Cl}_{3-y}[Co(NH3​)x​Cly​]Cl3−y​

Here:

  • yyy chloride ions are inside the coordination sphere.
  • (3−y)(3-y)(3−y) chloride ions are outside the coordination sphere and dissociate as counter ions.

On dissociation: [Co(NH3)xCly]Cl3−y→[Co(NH3)xCly](3−y)++(3−y)Cl−[\mathrm{Co}(\mathrm{NH}_3)_x\mathrm{Cl}_y]\mathrm{Cl}_{3-y} \rightarrow [\mathrm{Co}(\mathrm{NH}_3)_x\mathrm{Cl}_y]^{(3-y)+} + (3-y)\mathrm{Cl}^-[Co(NH3​)x​Cly​]Cl3−y​→[Co(NH3​)x​Cly​](3−y)++(3−y)Cl−

So total number of ions formed is: 1+(3−y)=4−y1 + (3-y) = 4-y1+(3−y)=4−y

Since for complete dissociation, number of ions equals van't Hoff factor: 4−y=34-y = 34−y=3

Therefore, y=1y=1y=1

  1. Conclusion

The number of chloride ions in the coordination sphere is: 1\boxed{1}1​

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