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Chapter 24: Problem 44

Write half-equations and an overall equation to represent the oxidation of tetraammineplatinum(II) ion to trans-tetraamminedichloroplatinum(IV) ion by \(\mathrm{Cl}_{2}\) Then make sketches of the two complex ions.

Short Answer

Expert verified
The half-reactions are:\( \mathrm{[Pt(NH_{3})_{4}]^{2+}} \rightarrow \mathrm{[Pt(NH_{3})_{4}]^{4+}} + 2e^{-} \) and \( \mathrm{Cl_{2}} + 2e^{-} \rightarrow 2\mathrm{Cl^{-}} \).The overall redox reaction after balancing is: \( \mathrm{[Pt(NH_{3})_{4}]^{2+}} + \mathrm{Cl_{2}} \rightarrow \mathrm{[Pt(NH_{3})_{4}Cl_{2}]^{2+}}\).The complex ions' sketches show Pt as the center atom surrounded by the respective ligands.

Step by step solution

01

Determine and write down the half-reactions

The two half reactions would look like this:1. \( \mathrm{[Pt(NH_{3})_{4}]^{2+}} \rightarrow \mathrm{[Pt(NH_{3})_{4}]^{4+}} + 2e^{-} \) -- This is the oxidation half-reaction where Platinum ion is losing electrons.2. \( \mathrm{Cl_{2}} + 2e^{-} \rightarrow 2\mathrm{Cl^{-}} \) -- This is the reduction half-reaction where Chlorine is gaining electrons.
02

Write down the overall redox reaction

Combine the two half reactions to form the overall redox reaction. Don’t forget to balance the electrons.The overall reaction after balancing would look like:\( \mathrm{[Pt(NH_{3})_{4}]^{2+}} + \mathrm{Cl_{2}} \rightarrow \mathrm{[Pt(NH_{3})_{4}Cl_{2}]^{2+}}\)
03

Sketch the two complex ions

First, sketch the tetraammineplatinum(II) ion which is a square planar complex. The Pt(II) ion is at the center and is surrounded by 4 NH3 groups at corners. In the sketch, show Pt in the center with all 4 NH3 groups attached. Then, sketch the trans-tetraamminedichloroplatinum(IV) ion which is also a square planar complex. The Pt(IV) ion is in the center surrounded by 4 ligands - 2 NH3 groups and 2 Cl- ions. Cl- ions are trans, that is, opposite to each other.

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Most popular questions from this chapter

Predict: (a) whether the square-planar complex ion \(\left[\mathrm{Cu}(\mathrm{py})_{4}\right]^{2+}\) is diamagnetic or paramagnetic (b) whether octahedral \(\left[\mathrm{Mn}(\mathrm{CN})_{6}\right]^{3-}\) or tetrahedral \(\left[\mathrm{FeCl}_{4}\right]^{-}\) has the greater number of unpaired electrons.

Predict: (a) which of the complex ions, \(\left[\mathrm{MoCl}_{6}\right]^{3-}\) and \(\left[\mathrm{Co}(\mathrm{en})_{3}\right]^{3+},\) is diamagnetic and which is paramagnetic; (b) the number of unpaired electrons expected for the tetrahedral complex ion \(\left[\mathrm{CoCl}_{4}\right]^{2-}\).

Explain the following observations in terms of complex-ion formation. (a) \(\mathrm{CoCl}_{3}\) is unstable in aqueous solution, being reduced to \(\mathrm{CoCl}_{2}\) and liberating \(\mathrm{O}_{2}(\mathrm{g}) .\) Yet, \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{6}\right] \mathrm{Cl}_{3}\) can be easily maintained in aqueous solution. (b) AgI is insoluble in water and in dilute \(\mathrm{NH}_{3}(\mathrm{aq})\) but AgI will dissolve in an aqueous solution of sodium thiosulfate.

The most soluble of the following solids in \(\mathrm{NH}_{3}(\mathrm{aq})\) is (a) \(\mathrm{Ca}(\mathrm{OH})_{2} ;\) (b) \(\mathrm{Cu}(\mathrm{OH})_{2} ;\) (c) \(\mathrm{BaSO}_{4} ;\) (d) \(\mathrm{MgCO}_{3}\) (e) \(\overline{\mathrm{Fe}_{2} \mathrm{O}_{3}}\).

We have seen that complex formation can stabilize oxidation states. An important illustration of this fact is the oxidation of water in acidic solutions by \(\mathrm{Co}^{3+}(\) aq) but not by \(\left[\mathrm{Co}(\mathrm{en})_{3}\right]^{3+} .\) Use the following data. \(\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+}+\mathrm{e}^{-} \longrightarrow\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}\) $$ E^{\circ}=1.82 \mathrm{V} $$ \(\left[\operatorname{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}+3 \mathrm{en} \longrightarrow\left[\mathrm{Co}(\mathrm{en})_{3}\right]^{2+}+6 \mathrm{H}_{2} \mathrm{O}(1)\) $$ \log \beta_{3}=12.18 $$ \(\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+}+3 \mathrm{en} \longrightarrow\left[\mathrm{Co}(\mathrm{en})_{3}\right]^{3+}+6 \mathrm{H}_{2} \mathrm{O}(1)\) $$ \log \beta_{3}=47.30 $$ Calculate \(E^{\circ}\) for the reaction $$ \left[\mathrm{Co}(\mathrm{en})_{3}\right]^{3+}+\mathrm{e}^{-} \longrightarrow\left[\mathrm{Co}(\mathrm{en})_{3}\right]^{2+} $$ Show that \(\left[\mathrm{Co}(\mathrm{en})_{3}\right]^{3+}\) is stable in water but \(\mathrm{Co}^{3+}(\mathrm{aq})\) is not.
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