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Given reduction potentials:

Chemistry

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e(i)

Cr2O72−>I2>Fe2+>Ca2+\text{Cr}_2\text{O}_7^{2-} > \text{I}_2 > \text{Fe}^{2+} > \text{Ca}^{2+}

e(iii)

Ca(s)∣Ca2+(aq)∣∣Fe2+(aq)∣Fe(s)\text{Ca}(s) | \text{Ca}^{2+}(aq) || \text{Fe}^{2+}(aq) | \text{Fe}(s)

+2.43 V+2.43 \text{ V}

Here are the solutions to the electrochemistry problems:

e)

i) To arrange the species in order of decreasing oxidizing strength, we compare their standard reduction potentials (E∘E^\circ). A higher (more positive) E∘E^\circ indicates a stronger oxidizing agent.

Given reduction potentials:

  • Cr2O72−(aq)+14H+(aq)+6e−→2Cr3+(aq)+7H2O(l)\text{Cr}_2\text{O}_7^{2-}(aq) + 14\text{H}^+(aq) + 6e^- \to 2\text{Cr}^{3+}(aq) + 7\text{H}_2\text{O}(l) E∘=+1.33 VE^\circ = +1.33 \text{ V}
  • I2(aq)+2e−→2I−(aq)\text{I}_2(aq) + 2e^- \to 2\text{I}^-(aq) E∘=+0.54 VE^\circ = +0.54 \text{ V}
  • Fe2+(aq)+2e−→Fe(s)\text{Fe}^{2+}(aq) + 2e^- \to \text{Fe}(s) E∘=−0.44 VE^\circ = -0.44 \text{ V}
  • Ca2+(aq)+2e−→Ca(s)\text{Ca}^{2+}(aq) + 2e^- \to \text{Ca}(s) E∘=−2.87 VE^\circ = -2.87 \text{ V}

Arranging the species (Cr2O72−\text{Cr}_2\text{O}_7^{2-}, I2\text{I}_2, Fe2+\text{Fe}^{2+}, Ca2+\text{Ca}^{2+}) in decreasing order of oxidizing strength:
Cr2O72−>I2>Fe2+>Ca2+\boxed{\text{Cr}_2\text{O}_7^{2-} > \text{I}_2 > \text{Fe}^{2+} > \text{Ca}^{2+}}

ii) When granules of calcium are added to a solution of potassium dichromate, a redox reaction will occur. Calcium metal (Ca\text{Ca}) is a strong reducing agent (has a very negative reduction potential, meaning it is easily oxidized), while dichromate ions (Cr2O72−\text{Cr}_2\text{O}_7^{2-}) are strong oxidizing agents (have a very positive reduction potential, meaning they are easily reduced).

The relevant half-reactions are:
Oxidation: Ca(s)→Ca2+(aq)+2e−\text{Ca}(s) \to \text{Ca}^{2+}(aq) + 2e^- (Eoxidation∘=+2.87 VE^\circ_{\text{oxidation}} = +2.87 \text{ V})
Reduction: Cr2O72−(aq)+14H+(aq)+6e−→2Cr3+(aq)+7H2O(l)\text{Cr}_2\text{O}_7^{2-}(aq) + 14\text{H}^+(aq) + 6e^- \to 2\text{Cr}^{3+}(aq) + 7\text{H}_2\text{O}(l) (Ereduction∘=+1.33 VE^\circ_{\text{reduction}} = +1.33 \text{ V})

Since the overall cell potential would be positive (2.87 V+1.33 V=4.20 V2.87 \text{ V} + 1.33 \text{ V} = 4.20 \text{ V}), the reaction is spontaneous.

Observations:

  • The calcium granules will disappear/dissolve as they are oxidized to Ca2+\text{Ca}^{2+} ions.
  • The orange solution of potassium dichromate will turn green as the Cr2O72−\text{Cr}_2\text{O}_7^{2-} ions (orange) are reduced to Cr3+\text{Cr}^{3+} ions (green).

iii) When the calcium and iron half-cells are coupled:
Calcium half-cell: Ca2+(aq)+2e−→Ca(s)\text{Ca}^{2+}(aq) + 2e^- \to \text{Ca}(s), E∘=−2.87 VE^\circ = -2.87 \text{ V}
Iron half-cell: Fe2+(aq)+2e−→Fe(s)\text{Fe}^{2+}(aq) + 2e^- \to \text{Fe}(s), E∘=−0.44 VE^\circ = -0.44 \text{ V}

The half-cell with the more negative reduction potential will undergo oxidation (anode), and the half-cell with the more positive reduction potential will undergo reduction (cathode).
Since −2.87 V<−0.44 V-2.87 \text{ V} < -0.44 \text{ V}:

  • Calcium will be oxidized (anode): Ca(s)→Ca2+(aq)+2e−\text{Ca}(s) \to \text{Ca}^{2+}(aq) + 2e^-
  • Iron(II) ions will be reduced (cathode): Fe2+(aq)+2e−→Fe(s)\text{Fe}^{2+}(aq) + 2e^- \to \text{Fe}(s)

Cell diagram:
The cell diagram represents the anode on the left and the cathode on the right, separated by a salt bridge (∣∣||).

Ca(s)∣Ca2+(aq)∣∣Fe2+(aq)∣Fe(s)\boxed{\text{Ca}(s) | \text{Ca}^{2+}(aq) || \text{Fe}^{2+}(aq) | \text{Fe}(s)}

Calculation of the EMF of the cell (Ecell∘E^\circ_{\text{cell}}):

Ecell∘=Ecathode∘−Eanode∘E^\circ_{\text{cell}} = E^\circ_{\text{cathode}} - E^\circ_{\text{anode}} Ecell∘=E∘(Fe2+/Fe)−E∘(Ca2+/Ca)E^\circ_{\text{cell}} = E^\circ(\text{Fe}^{2+}/\text{Fe}) - E^\circ(\text{Ca}^{2+}/\text{Ca}) Ecell∘=(−0.44 V)−(−2.87 V)E^\circ_{\text{cell}} = (-0.44 \text{ V}) - (-2.87 \text{ V}) Ecell∘=−0.44 V+2.87 VE^\circ_{\text{cell}} = -0.44 \text{ V} + 2.87 \text{ V} Ecell∘=+2.43 VE^\circ_{\text{cell}} = \boxed{+2.43 \text{ V}}
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