Chapter 20

Copper corrodes to cuprous oxide, \(\mathrm{Cu}_{2} \mathrm{O},\) or cupric oxide, CuO, depending on environmental conditions. (a) What is the oxidation state of copper in cuprous oxide? (b) What is the oxidation state of copper in cupric oxide? (c) Copper peroxide is another oxidation product of elemental copper. Suggest a formula for copper peroxide based on its name. (d) Copper(III) oxide is another unusual oxidation product of elemental copper. Suggest a chemical formula for copper(III) oxide.

(a) What is electrolysis? (b) Are electrolysis reactions thermodynamically spontaneous? (c) What process occurs at the anode in the electrolysis of molten NaCl? (d) Why is sodium metal not obtained when an aqueous solution of NaCl undergoes electrolysis?

(a) What is an electrolytic cell? (b) The negative terminal of a voltage source is connected to an electrode of an electrolytic cell. Is the electrode the anode or the cathode of the cell? Explain. (c) The electrolysis of water is often done with a small amount of sulfuric acid added to the water. What is the role of the sulfuric acid? (d) Why are active metals such as Al obtained by electrolysis using molten salts rather than aqueous solutions?

Metallic magnesium can be made by the electrolysis of molten \(\mathrm{MgCl}_{2}\). (a) What mass of \(\mathrm{Mg}\) is formed by passing a current of 4.55 A through molten \(\mathrm{MgCl}_{2}\), for 4.50 days? (b) How many minutes are needed to plate out \(25.00 \mathrm{~g} \mathrm{Mg}\) from molten \(\mathrm{MgCl}_{2}\) using \(3.50 \mathrm{~A}\) of current?

Elemental calcium is produced by the electrolysis of molten \(\mathrm{CaCl}_{2}\). (a) What mass of calcium can be produced by this process if a current of \(7.5 \times 10^{3} \mathrm{~A}\) is applied for \(48 \mathrm{~h}\) ? Assume that the electrolytic cell is \(68 \%\) efficient. (b) What is the minimum voltage needed to cause the electrolysis?

Metallic gold is collected from below the anode when a mixture of copper and gold metals is refined by electrolysis. Explain this behavior.

A disproportionation reaction is an oxidation-reduction reaction in which the same substance is oxidized and reduced. Complete and balance the following disproportionation reactions: (a) \(\mathrm{Fe}^{2+}(a q) \longrightarrow \mathrm{Fe}(s)+\mathrm{Fe}^{3+}(a q)\) (b) \(\mathrm{Br}_{2}(l) \longrightarrow \mathrm{Br}^{-}(a q)+\mathrm{BrO}_{3}^{-}(a q)\) (acidic solution) (c) \(\mathrm{Cr}^{3+}(a q) \longrightarrow \mathrm{Cr}_{2} \mathrm{O}_{7}^{2-}(a q)+\mathrm{Cr}(s)\) (acidic solution) (d) \(\mathrm{NO}(g) \longrightarrow \mathrm{N}_{2}(g)+\mathrm{NO}_{3}^{-}(a q)\) (acidic solution)

Gold exists in two common positive oxidation states, +1 and +3 . The standard reduction potentials for these oxidation states are $$ \begin{array}{l} \mathrm{Au}^{+}(a q)+\mathrm{e}^{-} \quad \longrightarrow \mathrm{Au}(s) \quad E_{\mathrm{red}}^{\circ}=+1.69 \mathrm{~V} \\ \mathrm{Au}^{3+}(a q)+3 \mathrm{e}^{-} \longrightarrow \mathrm{Au}(s) \quad E_{\mathrm{red}}^{\circ}=+1.50 \mathrm{~V} \end{array} $$ (a) Can you use these data to explain why gold does not tarnish in the air? (b) Suggest several substances that should be strong enough oxidizing agents to oxidize gold metal. (c) Miners obtain gold by soaking gold-containing ores in an aqueous solution of sodium cyanide. A very soluble complex ion of gold forms in the aqueous solution because of the redox reaction $$ \begin{aligned} 4 \mathrm{Au}(s)+8 \mathrm{NaCN}(a q) &+2 \mathrm{H}_{2} \mathrm{O}(l)+\mathrm{O}_{2}(g) \\ & \longrightarrow 4 \mathrm{Na}\left[\mathrm{Au}(\mathrm{CN})_{2}\right](a q)+4 \mathrm{NaOH}(a q) \end{aligned} $$ What is being oxidized, and what is being reduced in this reaction? (d) Gold miners then react the basic aqueous product solution from part (c) with \(\mathrm{Zn}\) dust to get gold metal. Write a balanced redox reaction for this process. What is being oxidized, and what is being reduced?

(a) Write the reactions for the discharge and charge of a nickel-cadmium (nicad) rechargeable hattery. (b) Given the following reduction potentials, calculate the standard emf of the cell: $$ \begin{array}{r} \mathrm{Cd}(\mathrm{OH})_{2}(s)+2 \mathrm{e}^{-} \longrightarrow \mathrm{Cd}(s)+2 \mathrm{OH}^{-}(a q) \\ \qquad \begin{aligned} E_{\mathrm{red}}^{\circ} &=-0.76 \mathrm{~V} \end{aligned} \\ \mathrm{NiO}(\mathrm{OH})(s)+\mathrm{H}_{2} \mathrm{O}(l)+\mathrm{e}^{-} \longrightarrow \mathrm{Ni}(\mathrm{OH})_{2}(s)+\mathrm{OH}^{-}(a q) \\ E_{\mathrm{red}}^{\circ}=+0.49 \mathrm{~V} \end{array} $$ (c) A typical nicad voltaic cell generates an emf of \(+1.30 \mathrm{~V}\). Why is there a difference between this value and the one you calculated in part (b)? (d) Calculate the equilibrium constant for the overall nicad reaction based on this typical emf value.

The capacity of batteries such as a lithium-ion battery is expressed in units of milliamp-hours (mAh). A typical battery of this type yields a nominal capacity of \(2000 \mathrm{mAh}\). (a) What quantity of interest to the consumer is being expressed by the units of \(\mathrm{mAh}\) ? (b) The starting voltage of a fresh lithium-ion battery is \(3.60 \mathrm{~V}\). The voltage decreases during discharge and is \(3.20 \mathrm{~V}\) when the battery has delivered its rated capacity. If we assume that the voltage declines linearly as current is withdrawn, estimate the total maximum electrical work the battery could perform during discharge.

Disulfides are compounds that have \(\mathrm{S}-\mathrm{S}\) bonds, like peroxides have \(\mathrm{O}-\mathrm{O}\) bonds. Thiols are organic compounds that have the general formula \(\mathrm{R}-\mathrm{SH},\) where \(\mathrm{R}\) is a generic hydrocarbon. The \(\mathrm{SH}^{-}\) ion is the sulfur counterpart of hydroxide, \(\mathrm{OH}^{-}\). Two thiols can react to make a disulfide, \(\mathrm{R}-\mathrm{S}-\mathrm{S}-\mathrm{R} .\) (a) What is the oxidation state of sulfur in a thiol? (b) What is the oxidation state of sulfur in a disulfide? (c) If you react two thiols to make a disulfide, are you oxidizing or reducing the thiols? (d) If you wanted to convert a disulfide to two thiols, should you add a reducing agent or oxidizing agent to the solution? (e) Suggest what happens to the H's in the thiols when they form disulfides.

Magnesium is obtained by electrolysis of molten \(\mathrm{MgCl}_{2}\). (a) Why is an aqueous solution of \(\mathrm{MgCl}_{2}\) not used in the electrolysis? (b) Several cells are connected in parallel by very large copper bars that convey current to the cells. Assuming that the cells are \(96 \%\) efficient in producing the desired products in electrolysis, what mass of \(\mathrm{Mg}\) is formed by passing a current of 97,000 A for a period of 24 h?

Aqueous solutions of ammonia \(\left(\mathrm{NH}_{3}\right)\) and bleach (active ingredient \(\mathrm{NaOCl}\) ) are sold as cleaning fluids, but bottles of both of them warn: "Never mix ammonia and bleach, as toxic gases may be produced." One of the toxic gases that can be produced is chloroamine, \(\mathrm{NH}_{2} \mathrm{Cl}\). (a) What is the oxidation number of chlorine in bleach? (b) What is the oxidation number of chlorine in chloramine? (c) Is Cl oxidized, reduced, or neither, upon the conversion of bleach to chloramine? (d) Another toxic gas that can be produced is nitrogen trichloride, \(\mathrm{NCl}_{3}\). What is the oxidation number of \(\mathrm{N}\) in nitrogen trichloride? (e) Is N oxidized, reduced, or neither, upon the conversion of ammonia to nitrogen trichloride?

Cytochrome, a complicated molecule that we will represent as \(\mathrm{CyFe}^{2+}\), reacts with the air we breathe to supply energy required to synthesize adenosine triphosphate (ATP). The body uses ATP as an energy source to drive other reactions (Section 19.7). At \(\mathrm{pH} 7.0\) the following reduction potentials pertain to this oxidation of \(\mathrm{CyFe}^{2+}\) : $$ \begin{aligned} \mathrm{O}_{2}(g)+4 \mathrm{H}^{+}(a q)+4 \mathrm{e}^{-} & \longrightarrow 2 \mathrm{H}_{2} \mathrm{O}(l) & E_{\mathrm{red}}^{\circ} &=+0.82 \mathrm{~V} \\\ \mathrm{CyFe}^{3+}(a q)+\mathrm{e}^{-} & \longrightarrow \mathrm{CyFe}^{2+}(a q) & E_{\mathrm{red}}^{\circ} &=+0.22 \mathrm{~V} \end{aligned} $$ (a) What is \(\Delta G\) for the oxidation of \(\mathrm{CyFe}^{2+}\) by air? \((\mathbf{b})\) If the synthesis of \(1.00 \mathrm{~mol}\) of ATP from adenosine diphosphate (ADP) requires a \(\Delta G\) of \(37.7 \mathrm{~kJ},\) how many moles of ATP are synthesized per mole of \(\mathrm{O}_{2} ?\)