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Chemistry 312

Please turn in on your own paper and individually. Problem Set 2 (Due Friday, July 8, 2011)

1. Answer the following questions about the Pourbaix diagram shown below a. Is MnO4– a stronger oxidant at pH 8 or pH 2? Explain your choice. At pH 2, MnO4– has a larger positive potential than it does at pH 8. This matters because stronger oxidants have a higher positive potentials (MnO4– reduces to MnO2). b. Is MnO2(s) easier to reduce at pH 2 or pH 10? How do the half-reactions differ at pH 2 vs. pH 10? Write a balanced equation for each. When MnO2 reduces, it is acting as an oxidant. Following the same reasoning as part a, the stronger oxidant has a higher positive potential; in this case, it is MnO2 at pH 2. At pH 2, MnO2 reduces to Mn2+ (balanced reaction: 4 H+ + 2 e– + MnO2 → Mn2+ + 2 H2O); at pH 10, MnO2 reduces to Mn2O3 (balanced reaction: H2O + 2 e– + 2 MnO2 → Mn2O3 + 2 OH–). c. What reaction occurs across the line labeled “a”? Is this a redox reaction? Give a justification. 3 Mn2O3 + H2O + 2 e– → 2 Mn3O4 + 2 OH– ; this is a redox reaction (a reduction reaction, actually) because one species is gaining electrons. Note that the reverse reaction could also occur; that is, 2 Mn3O4 + 2 OH– → 3 Mn2O3 + H2O + 2 e–. Which one will occur is dependent on the oxidation reaction. d. What reaction occurs across the line labeled “b”? Is this a redox reaction? Give a justification. As seen in part b, 4 H+ + 2 e– + MnO2 → Mn2+ + 2 H2O; this is again a redox reaction (a reduction reaction), and, similarly, Mn2+ + 2 H2O → 4 H+ + 2 e– + MnO2 can also occur, depending on what the oxidation reaction is. e. What reaction occurs across the line labeled “c”? Is this a redox reaction? Give a justification. As seen in part c, H2O + 2 e– + 2 MnO2 → Mn2O3 + 2 OH–; this is again a redox reaction (a reduction reaction), and, similarly, Mn2O3 + 2 OH–→ H2O + 2 e– + 2 MnO2 can

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