Chapter 17: Problem 22
How can one construct a galvanic cell from two substances, each having a negative standard reduction potential?
Chapter 17: Problem 22
How can one construct a galvanic cell from two substances, each having a negative standard reduction potential?
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Get started for freeA disproportionation reaction involves a substance that acts as both an oxidizing and a reducing agent, producing higher and lower oxidation states of the same element in the products. Which of the following disproportionation reactions are spontaneous under standard conditions? Calculate \(\Delta G^{\circ}\) and \(K\) at \(25^{\circ} \mathrm{C}\) for those reactions that are spontaneous under standard conditions. a. \(2 \mathrm{Cu}^{+}(a q) \rightarrow \mathrm{Cu}^{2+}(a q)+\mathrm{Cu}(s)\) b. \(3 \mathrm{Fe}^{2+}(a q) \rightarrow 2 \mathrm{Fe}^{3+}(a q)+\mathrm{Fe}(s)\) c. \(\mathrm{HClO}_{2}(a q) \rightarrow \mathrm{ClO}_{3}^{-}(a q)+\mathrm{HClO}(a q) \quad\) (unbalanced) Use the half-reactions: \(\mathrm{ClO}_{3}^{-}+3 \mathrm{H}^{+}+2 \mathrm{e}^{-} \longrightarrow \mathrm{HClO}_{2}+\mathrm{H}_{2} \mathrm{O} \quad \mathscr{E}^{\circ}=1.21 \mathrm{V}\) \(\mathrm{HClO}_{2}+2 \mathrm{H}^{+}+2 \mathrm{e}^{-} \longrightarrow \mathrm{HClO}+\mathrm{H}_{2} \mathrm{O} \quad \mathscr{E}^{\circ}=1.65 \mathrm{V}\)
The overall reaction in the lead storage battery is $$\mathrm{Pb}(s)+\mathrm{PbO}_{2}(s)+2 \mathrm{H}^{+}(a q)+2 \mathrm{HSO}_{4}^{-}(a q) \longrightarrow 2 \mathrm{PbSO}_{4}(s)+2 \mathrm{H}_{2} \mathrm{O}(l) $$ a. For the cell reaction \(\Delta H^{\circ}=-315.9 \mathrm{kJ}\) and \(\Delta S^{\circ}=\) \(263.5 \mathrm{J} / \mathrm{K} .\) Calculate \(\mathscr{E}^{\circ}\) at \(-20 .^{\circ} \mathrm{C} .\) Assume \(\Delta H^{\circ}\) and \(\Delta S^{\circ}\) do not depend on temperature. b. Calculate \(\mathscr{E}\) at \(-20 .^{\circ} \mathrm{C}\) when \(\left[\mathrm{HSO}_{4}^{-}\right]=\left[\mathrm{H}^{+}\right]=4.5 \mathrm{M}\) c. Consider your answer to Exercise \(71 .\) Why does it seem that batteries fail more often on cold days than on warm days?
Consider the standard galvanic cell based on the following half-reactions: $$\begin{array}{c} \mathrm{Cu}^{2+}+2 \mathrm{e}^{-} \longrightarrow \mathrm{Cu} \\ \mathrm{Ag}^{+}+\mathrm{e}^{-} \longrightarrow \mathrm{Ag} \end{array}$$ The electrodes in this cell are \(\mathrm{Ag}(s)\) and \(\mathrm{Cu}(s) .\) Does the cell potential increase, decrease, or remain the same when the following changes occur to the standard cell? a. \(\mathrm{CuSO}_{4}(s)\) is added to the copper half-cell compartment (assume no volume change). b. \(\mathrm{NH}_{3}(a q)\) is added to the copper half-cell compartment. [Hint: \(\left.\mathrm{Cu}^{2+} \text { reacts with } \mathrm{NH}_{3} \text { to form } \mathrm{Cu}\left(\mathrm{NH}_{3}\right)_{4}^{2+}(a q) .\right]\) c. \(\mathrm{NaCl}(s)\) is added to the silver half-cell compartment. [Hint: \(\left.\mathrm{Ag}^{+} \text {reacts with } \mathrm{Cl}^{-} \text {to form } \mathrm{AgCl}(s) .\right]\) d. Water is added to both half-cell compartments until the volume of solution is doubled. e. The silver electrode is replaced with a platinum electrode. $$ \mathrm{Pt}^{2+}+2 \mathrm{e}^{-} \longrightarrow \mathrm{Pt} \quad \mathscr{E}^{\circ}=1.19 \mathrm{V} $$
Balance the following oxidation-reduction reactions that occur in acidic solution using the half-reaction method. a. \(\mathrm{I}^{-}(a q)+\mathrm{ClO}^{-}(a q) \rightarrow \mathrm{I}_{3}^{-}(a q)+\mathrm{Cl}^{-}(a q)\) b. \(\mathrm{As}_{2} \mathrm{O}_{3}(s)+\mathrm{NO}_{3}^{-}(a q) \rightarrow \mathrm{H}_{3} \mathrm{AsO}_{4}(a q)+\mathrm{NO}(g)\) c. \(\mathrm{Br}^{-}(a q)+\mathrm{MnO}_{4}^{-}(a q) \rightarrow \mathrm{Br}_{2}(l)+\mathrm{Mn}^{2+}(a q)\) d. \(\mathrm{CH}_{3} \mathrm{OH}(a q)+\mathrm{Cr}_{2} \mathrm{O}_{7}^{2-}(a q) \rightarrow \mathrm{CH}_{2} \mathrm{O}(a q)+\mathrm{Cr}^{3+}(a q)\)
Which of the following statements concerning corrosion is(are) true? For the false statements, correct them. a. Corrosion is an example of an electrolytic process. b. Corrosion of steel involves the reduction of iron coupled with the oxidation of oxygen. c. Steel rusts more easily in the dry (arid) Southwest states than in the humid Midwest states. d. Salting roads in the winter has the added benefit of hindering the corrosion of steel. e. The key to cathodic protection is to connect via a wire a metal more easily oxidized than iron to the steel surface to be protected.
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