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CHEMISTRY 12

Chapter 11

Cells and Batteries


Solutions for Practice Problems
Student Textbook page 509
1. Problem (a) If the reaction of zinc with copper(II) ions is carried out in a test tube, what is

the oxidizing agent and what is the reducing agent?


(b) In a Daniell cell, what is the oxidizing agent and what is the reducing agent?

Explain your answer. Solution Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) Oxidation: Zn(s) Zn2+(aq) + 2e Reduction: Cu2+(aq) + 2e Cu(s) The half-reactions show that Cu2+ accepts electrons, so Cu2+ is the oxidizing agent. Zn donates electrons, so Zn is the reducing agent. (b) The oxidizing agent is Cu2+ , and the reducing agent is Zn, as in part (a). The net ionic equation and the half-reactions are not affected if the reaction takes place in a cell instead of a test tube.
2. Problem (a) The net ionic equation and the half-reactions are as follows.

Write the oxidation half-reaction, the reduction half-reaction, and the overall cell reaction for each of the following galvanic cells. Identify the anode and the cathode in each case. In part (b), platinum is present as an inert electrode. (a) Sn(s)|Sn2+(aq)||Tl+(aq)|Tl(s) (b) Cd(s)|Cd2+(aq)||H+(aq)|H2(g)|Pt(s) Solution In the shorthand representation, the anode, where oxidation occurs, is on the left. The cathode, where reduction occurs, is on the right. (a) Oxidation half-reaction: Sn(s) Sn2+(aq) + 2e Reduction half-reaction: Tl+(aq) + e Tl(s) The LCM of 1 and 2 is 2. To write the overall cell reaction, multiply the reduction half-reaction by 2, so that equal numbers of electrons are lost and gained. 2Tl+ + 2e 2Tl(s) (aq) Add the half-reactions. Sn(s) Sn2+(aq) + 2e 2Tl+(aq) + 2e 2Tl(s) Sn(s) + 2Tl+(aq) + 2e Sn2+(aq) + 2e + 2Tl(s) Simplify by removing two electrons from both sides. Sn(s) + 2Tl+(aq) Sn2+(aq) + 2Tl(s) (balanced) Anode: Sn Cathode: Tl

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CHEMISTRY 12 (b) Oxidation half-reaction: Cd(s) Cd2+(aq) + 2e

Reduction half-reaction: H+(aq) + e H2(g) (unbalanced) 2H+(aq) + e H2(g) 2H+(aq) + 2e H2(g) (balanced) To write the overall cell reaction, add the half-reactions. Cd(s) Cd2+(aq) + 2e + 2H (aq) + 2e H2(g) Cd(s) + 2H+(aq) + 2e Cd2+(aq) + 2e + H2(g) Simplify by removing two electrons from both sides. Cd(s) + 2H+(aq) Cd2+(aq) + H2(g) (balanced) Anode: Cd Cathode: Pt

3. Problem

A galvanic cell involves the overall reaction of iodide ions with acidied permanganate ions to form manganese(II) ions and iodine. The salt bridge contains potassium nitrate. (a) Write the half-reactions, and the overall cell reaction. (b) Identify the oxidizing agent and the reducing agent. (c) The inert anode and cathode are both made of graphite. Solid iodine forms on one of them. Which one? Solution (a) The potassium nitrate in the salt bridge does not interfere in the reaction, so potassium ions and nitrate ions do not appear in the half-reactions or in the overall cell reaction. The unbalanced net ionic equation is as follows. I + MnO4 Mn2+ + I2 The element iodine is clearly being oxidized, because its oxidation number increases from 1 in I to 0 in I2 . Therefore, there is no need to assign the other oxidation numbers. Write the oxidation half-reaction. I I2 (unbalanced) 2I I2 2I I2 + 2e (balanced) Write the reduction half-reaction. MnO4 Mn2+ (unbalanced) The permanganate ions are acidied, so the reaction occurs in an acidic solution. Add water molecules to balance the oxygen atoms. MnO4 Mn2+ + 4H2O Add hydrogen ions to balance the hydrogen atoms. MnO4 + 8H+ Mn2+ + 4H2O Add electrons to balance the charges. MnO4 + 8H+ + 5e Mn2+ + 4H2O (balanced) The LCM of 2 and 5 is 10. Multiply the oxidation half-reaction by 5, and multiply the reduction half-reaction by 2, so that equal numbers of electrons are lost and gained. Add the half-reactions. 10I 5I2 + 10e + 2MnO4 + 16H + 10e 2Mn2+ + 8H2O 10I + 2MnO4 + 16H+ + 10e 5I2 + 10e + 2Mn2+ + 8H2O Simplify by removing ten electrons from both sides. 10I + 2MnO4 + 16H+ 5I2 + 2Mn2+ + 8H2O (balanced)
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CHEMISTRY 12 (b) From the reduction half-reaction, MnO4 is reduced, so MnO4 is the oxidizing

agent. From the oxidation half-reaction, I is oxidized, so I is the reducing agent. (c) Iodine is formed in the oxidation half-reaction. Oxidation occurs at the anode. Therefore, solid iodine forms on the inert graphite anode.
4. Problem

As you saw earlier, pushing a zinc electrode and a copper electrode into a lemon makes a lemon cell. In the following representation of the cell, C6H8O7 is the formula of citric acid. Explain why the representation does not include a double vertical line. Zn(s) C6H8O7(aq) Cu(s) Solution A double vertical line is used to represent a porous barrier or salt bridge between two half-cells. In a lemon cell, the two half-reactions occur inside the same container (the lemon itself ), not in two half-cells separated by a porous barrier or a salt bridge. This cell has only one electrolyte, and no barrier.

Solutions for Practice Problems


Student Textbook page 521
5. Problem

Write the two half-reactions for the following redox reaction. Subtract the two reduction potentials to nd the standard cell potential for a galvanic cell in which this reaction occurs. Cl2(g) + 2Br(aq) 2Cl(aq) + Br2( ) What Is Required? You need to nd the standard cell potential for the given reaction by subtracting two reduction potentials. What Is Given? You have the balanced net ionic equation and a table of standard reduction potentials. Plan Your Strategy Step 1 Write the oxidation and reduction half-reactions. Step 2 Locate the relevant reduction potentials in a table of standard reduction potentials. Step 3 Subtract the reduction potentials to nd the cell potential, using E cell = E cathode E anode . Act on Your Strategy Step 1 The oxidation and reduction half-reactions are as follows. Oxidation (occurs at the anode): 2Br(aq) Br2( ) + 2e Reduction (occurs at the cathode): Cl2(g) + 2e 2Cl(aq) Step 2 The relevant reduction potentials in the table of standard reduction potentials are: Br2( ) + 2e 2Br(aq) E anode = 1.066 V Cl2(g) + 2e 2Cl(aq) E cathode = 1.358 V Step 3 Calculate the cell potential by subtraction. E cell = E cathode E anode = 1.358 V 1.066 V = 0.292 V
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Check Your Solution The cell potential is positive, as expected for a galvanic cell.
6. Problem

Write the two half-reactions for the following redox reaction. Add the reduction potential and the oxidation potential to nd the standard cell potential for a galvanic cell in which the reaction occurs. 2Cu+(aq) + 2H+(aq) + O2(g) 2Cu2+(aq) + H2O2(aq) What Is Required? You need to nd the standard cell potential for the given reaction by adding a reduction potential and an oxidation potential. What Is Given? You have the balanced net ionic equation and a table of standard reduction potentials. Plan Your Strategy Step 1 Write the oxidation and reduction half-reactions. Step 2 Locate the relevant reduction potentials in a table of standard reduction potentials. Step 3 Change the sign of the reduction potential for the oxidation half-reaction to nd the oxidation potential. Step 4 Add the reduction potential and the oxidation potential, using E cell = E red + E ox . Act on Your Strategy The oxidation and reduction half-reactions are as follows. Oxidation (occurs at the anode): Cu+(aq) Cu2+(aq) + e Reduction (occurs at the cathode): 2H+(aq) + O2(g) + 2e H2O2(aq) Step 2 The relevant reduction potentials in the table of standard reduction potential are: E anode = 0.153 V Cu+(aq) Cu2+(aq) + e + O2(g) + 2H (aq) + 2e H2O2(aq) E cathode = 0.695 V Step 3 The standard electrode potential for the reduction half-reaction is E red = 0.695 V. Changing the sign of the potential for the oxidation half-reaction gives Cu+(aq) E ox = 0.153 V Cu2+(aq) + e Step 4 Calculate the cell potential by addition. E cell = E red + E ox = 0.695 V + (0.153 V) = 0.542 V
Step 1

Check Your Solution The cell potential is positive, as expected for a galvanic cell.
7. Problem

Write the two half-reactions for the following redox reaction. Subtract the two standard reduction potentials to nd the standard cell potential for the reaction. Sn(s) + 2HBr(aq) SnBr2(aq) + H2(g) Solution Step 1 Write the equation in net ionic form to identify the half-reactions. Sn(s) + 2H+(aq) Sn2+(aq) + H2(g) Write the oxidation and reduction half-reactions. Oxidation (occurs at the anode): Sn(s) Sn2+(aq) + 2e Reduction (occurs at the cathode): 2H+(aq) + 2e H2(g)
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Locate the relevant reduction potentials in a table of standard reduction potentials. Sn(s) E anode = 0.138 V Sn2+(aq) + 2e 2H+(aq) + 2e H2(g) E cathode = 0.000 V Step 3 Subtract the standard reduction potentials to calculate the cell potential. E cell = E cathode E anode = 0.000 V (0.138 V) = 0.138 V
Step 2 8. Problem

Write the two half-reactions for the following redox reaction. Add the standard reduction potential and the standard oxidation potential to nd the standard cell potential for the reaction. Cr(s) + 3AgCl(s) CrCl3(aq) + 3Ag(s) Solution Step 1 Write the equation in net ionic form to identify the half-reactions. Cr(s) + 3AgCl(s) Cr3+(aq) + 3Cl(aq) + 3Ag(s) Write the oxidation and reduction half-reactions. Oxidation (occurs at the anode): Cr(s) Cr3+(aq) + 3e Reduction (occurs at the cathode): AgCl(s) + e Cl(aq) + Ag(s) Step 2 Locate the relevant reduction potentials in a table of standard reduction potentials. E anode = 0.744 V Cr(s) Cr3+(aq) + 3e AgCl(s) + e Ag(s) + Cl(aq) E cathode = 0.222 V Step 3 The standard electrode potential for the reduction half-reaction is E red = 0.222 V. Change the sign of the potential for the oxidation half-reaction. Cr3+(aq) + 3e E ox = 0.744 V Cr(s) Step 4 Calculate the cell potential by addition. E cell = E red + E ox = 0.222 V + 0.744 V = 0.966 V

Solutions for Practice Problems


Student Textbook pages 525526
9. Problem

The electrolysis of molten calcium chloride produces calcium and chlorine. Write
(a) the half-reaction that occurs at the anode (b) the half-reaction that occurs at the cathode (c) the chemical equation for the overall reaction

Solution (a) Oxidation occurs at the anode, where chloride ions are oxidized to elemental chlorine. Oxidation half-reaction: Cl Cl2 (unbalanced) 2Cl Cl2 2Cl Cl2 + 2e (balanced) (b) Reduction occurs at the cathode, where calcium ions are reduced to elemental calcium. Reduction half-reaction: Ca2+ Ca (unbalanced) Ca2+ + 2e Ca (balanced)
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(c) Because the reactant and the products are all named in the question, the chemical

equation can be written from the given information. Write the correct formula for each substance. Overall reaction: CaCl2 Ca + Cl2 The chemical equation is already balanced.
10. Problem

For the electrolysis of molten lithium bromide, write (a) the half-reaction that occurs at the negative electrode (b) the half-reaction that occurs at the positive electrode (c) the net ionic equation for the overall cell reaction Solution
(a) In an electrolytic cell, the cathode has a negative polarity. Reduction occurs at the

cathode, where lithium ions are reduced to elemental lithium. Reduction half-reaction: Li+ + e Li (balanced) (b) In an electrolytic cell, the anode has a positive polarity. Oxidation occurs at the anode, where bromide ions are oxidized to elemental bromine. Oxidation half-reaction: Br Br2 (unbalanced) 2Br Br2 2Br Br2 + 2e (balanced) (c) The LCM of 1 and 2 is 2. Multiply the reduction half-reaction by 2, so that equal numbers of electrons are lost and gained. Then add the half-reactions. 2Li+ + 2e 2Li 2Br Br2 + 2e + 2Li + 2e + 2Br 2Li + Br2 + 2e Simplify by removing two electrons from both sides. 2Li+ + 2Br 2Li + Br2 (balanced) Note: Another way to write this net ionic equation is to use the identities of the reactant and the products to write a balanced chemical equation for the overall reaction. The formula of the molten ionic compound can then be written in ionic form. Chemical equation: LiBr Li + Br2 (unbalanced) 2LiBr Li + Br2 2LiBr 2Li + Br2 (balanced) Net ionic equation: 2Li+ + 2Br 2Li + Br2 If the states are included, the net ionic equation is as follows. 2Li+( ) + 2Br( ) 2Li(s) + Br2( )
11. Problem

A galvanic cell produces direct current, which ows in one direction. The mains supply at your home is a source of alternating current, which changes direction every fraction of a second. Explain why the external electrical supply for an electrolytic cell must be a source of direct current, rather than alternating current. Solution If the external electrical supply for an electrolytic cell were a source of alternating current, the direction of the ow of electrons through the external circuit would be reversed every fraction of a second. The chemical reaction taking place in the cell would be reversed each time the current reversed direction. If the external electrical supply is a source of direct current, the electrons ow in one direction, and the chemical reaction proceeds in one direction.

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12. Problem

Suppose a battery is used as the external electrical supply for an electrolytic cell. Explain why the negative terminal of the battery must be connected to the cathode of the cell. Solution Reduction (the gain of electrons) occurs at the cathode of the electrolytic cell, so electrons must be supplied to this electrode through the external circuit. The negative terminal of the battery is the anode. Because oxidation (the loss of electrons) takes place at the anode, electrons ow from the anode of the battery to the cathode of the electrolytic cell.

Solutions for Practice Problems


Student Textbook page 531
13. Problem

Predict the products of the electrolysis of a 1 mol/L solution of sodium chloride. What Is Required? You need to predict the products of the electrolysis of 1 mol/L NaCl(aq) . What Is Given? You are given the concentration of the electrolyte in an aqueous solution. You have a table of standard reduction potentials, and you know the non-standard reduction potentials for water. Plan Your Strategy Step 1 List the four relevant half-reactions and their reduction potentials. Step 2 Predict the products by nding the cell reaction that requires the lowest external voltage. Act on Your Strategy The Na+(aq) and Cl(aq) concentrations are 1 mol/L, so use the standard reduction potentials for the half-reactions that involve these ions. Use the non-standard values for water. E = 1.358 V Cl2(g) + 2e 2Cl(aq) + O2(g) + 4H (aq) + 4e E = 0.815 V 2H2O( ) 2H2O( ) + 2e H2(g) + 2OH(aq) E = 0.414 V Na+(aq) + e E = 2.711 V Na(s) There are two possible oxidation half-reactions at the anode: the oxidation of chloride ions in the electrolyte, or the oxidation of water. 2Cl(aq) Cl2(g) + 2e 2H2O( ) O2(g) + 4H+(aq) + 4e There are two possible reduction half-reactions at the cathode: the reduction of sodium ions in the electrolyte, or the reduction of water. Na+(aq) + e Na(s) 2H2O( ) + 2e H2(g) + 2OH(aq) Step 2 Combine pairs of half-reactions to produce four possible overall reactions. Determine the cell potential for each reaction. Reaction 1: the production of sodium and chlorine 2Na+(aq) + 2Cl(aq) 2Na(s) + Cl2(g) E cell = E cathode E anode = 2.711 V 1.358 V = 4.096 V
Step 1

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Reaction 2: the production of hydrogen and oxygen 2H2O( ) 2H2(g) + O2(g) Ecell = Ecathode Eanode = 0.414 V 0.851 V = 1.229 V Reaction 3: the production of sodium and oxygen 4Na+(aq) + 2H2O( ) 4Na(s) + O2(g) + 4H+(aq) Ecell = E cathode Eanode = 2.711 V 0.815 V = 3.526 V Reaction 4: the production of hydrogen and chlorine 2H2O( ) + 2Cl(aq) H2(g) + 2OH(aq) + Cl2(g) Ecell = Ecathode E anode = 0.414 V 1.358 V = 1.772 V The electrolysis of water requires the lowest external voltage. Therefore, the predicted products of this electrolysis are hydrogen and oxygen. Check Your Solution Use a potential ladder diagram to visualize the cell potentials.
more positive
1.358 0.815

Cl2(g) + 2e

2Cl(aq)

Ecell = 1.772 V
O2(g) + 4H+(aq) + 4e 2H2O(
)

Ecell = 1.229
E (V)

0.414

2H2O( ) + 2e

H2(g) + 2OH(aq)

E cell = 4.069 V

Ecell = 3.526 V

2.711

Na+(aq) + e

Na(s)

The diagram shows that the electrolysis of water requires the lowest external voltage.
14. Problem

Explain why calcium can be produced by the electrolysis of molten calcium chloride, but not by the electrolysis of aqueous calcium chloride. Solution In the electrolysis of molten calcium chloride, there is one possible reduction half-reaction at the cathode. The product formed at the cathode is elemental calcium. Ca2+( ) + 2e Ca(s)

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In the electrolysis of aqueous calcium chloride, there are two possible reduction half-reactions at the cathode. Either calcium ions or water can be reduced. Ca2+(aq) + 2e Ca(s) 2H2O( ) + 2e H2(g) + 2OH(aq) The relevant potentials for the possible reductions at the cathode are: E cathode = 2.868 V Ca(s) Ca2+(aq) + 2e 2H2O( ) + 2e Ecathode = 0.414 V H2(g) + 2OH(aq) The value for the reduction of calcium ions is more negative than the value for the reduction of water. Therefore, the external voltage required for the cell reaction in which calcium is formed at the cathode is greater than for the cell reaction in which hydrogen is formed at the cathode. Hydrogen is formed instead of calcium. Note: You could work through the four possible cell reactions, as in Practice Problem 13, to show that hydrogen and oxygen are the predicted electrolysis products. However, you do not need to consider the product at the anode to explain the observation described in the problem.
15. Problem

One half of a galvanic cell has a nickel electrode in a 1 mol/L nickel(II) chloride solution. The other half-cell has a cadmium electrode in a 1 mol/L cadmium chloride solution. (a) Find the cell potential. (b) Identify the anode and the cathode. (c) Write the oxidation half-reaction, the reduction half-reaction, and the overall cell reaction. Solution E = 0.257 V Ni(s) Ni2+(aq) + 2e 2+ Cd (aq) + 2e E = 0.403 V Cd(s) The cell is galvanic, so the cell potential must be positive. There is one way to subtract the reduction potentials so that the result is positive. E cell = E cathode E anode = 0.257 V (0.403 V) = 0.257 V + 0.403 V = 0.146 V (b) From part (a), cadmium is the anode, and nickel is the cathode. (c) Oxidation (occurs at the anode): Cd(s) Cd2+(aq) + 2e Reduction (occurs at the cathode): Ni2+(aq) + 2e Ni(s) Overall cell reaction: Cd(s) + Ni2+(aq) Cd2+(aq) + Ni(s)
16. Problem (a) The relevant reduction potentials are:

An external voltage is applied to change the galvanic cell in question 15 into an electrolytic cell. Repeat parts (a) to (c) for the electrolytic cell. Solution
(a) The relevant reduction potentials are as in question 15.

E = 0.257 V Ni(s) Ni2+(aq) + 2e Cd2+(aq) + 2e E = 0.403 V Cd(s) The cell is electrolytic, so the cell potential must be negative. There is one way to subtract the reduction potentials so that the result is negative. E cell = E cathode E anode = 0.403 V (0.257 V) = 0.403 V + 0.257 V = 0.146 V
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Note: As shown in Practice Problem 13, the electrolysis of water requires a much greater external voltage than 0.146 V, so the electrolysis of water is not a complication. (b) From part (a), nickel is the anode, and cadmium is the cathode. (c) Oxidation (occurs at the anode): Ni(s) Ni2+(aq) + 2e Reduction (occurs at the cathode): Cd2+(aq) + 2e Cd(s) Overall cell reaction: Ni(s) + Cd2+(aq) Ni2+(aq) + Cd(s)

Solutions for Practice Problems


Student Textbook pages 534535
17. Problem

Look up the standard reduction potentials of the following half-reactions. Predict whether acidied nitrate ions will oxidize manganese(II) ions to manganese(IV) oxide under standard conditions. MnO2(s) + 4H+(aq) + 2e Mn2+(aq) + 2H2O( ) NO3(aq) + 4H+(aq) + 3e NO(g) + 2H2O( ) Solution The standard reduction potentials are as follows: Mn2+(aq) + 2H2O( ) E = 1.224 V MnO2(s) + 4H+(aq) + 2e + NO3 (aq) + 4H (aq) + 3e E = 0.957 V NO(g) + 2H2O( ) The reaction described in the problem involves the oxidation of manganese(II) ions and the reduction of nitrate ions under acidic conditions. The two half-reactions are as follows. Oxidation (occurs at the anode): Mn2+(aq) + 2H2O( ) MnO2(s) + 4H+(aq) + 2e Reduction (occurs at the cathode): NO3(aq) + 4H+(aq) + 3e NO(g) + 2H2O( ) E cell = E cathode E anode = 0.957 V 1.224 V = 0.267 V The standard cell potential is negative, so the reaction is non-spontaneous under standard conditions. Acidied nitrate ions are predicted not to oxidize manganese(II) ions to manganese(IV) oxide under standard conditions.
18. Problem

Predict whether each reaction is spontaneous or non-spontaneous under standard conditions. (a) 2Cr(s) + 3Cl2(g) 2Cr3+(aq) + 6Cl(aq) (b) Zn2+(aq) + Fe(s) Zn(s) + Fe2+(aq) (c) 5Ag(s) + MnO4(aq) + 8H+(aq) 5Ag+(aq) + Mn2+(aq) + 4H2O( ) Solution
(a) The two half-reactions are as follows.

Oxidation (occurs at the anode): Cr(s) Cr3+(aq) + 3e Reduction (occurs at the cathode): Cl2(g) + 2e 2Cl(aq) The relevant standard reduction potentials are: E = 0.744 V Cr(s) Cr3+(aq) + 3e Cl2(g) + 2e E = 1.358 V 2Cl(aq) E cell = E cathode E anode = 1.358 V (0.744 V) = 1.358 V + 0.744 V = 2.102 V The standard cell potential is positive, so the reaction is spontaneous under standard conditions.
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(b) The two half-reactions are as follows.

Oxidation (occurs at the anode): Fe(s) Fe2+(aq) + 2e Reduction (occurs at the cathode): Zn2+(aq) + 2e Zn(s) The relevant standard reduction potentials are: E = 0.447 V Fe(s) Fe2+(aq) + 2e 2+ Zn (aq) + 2e Zn(s) E = 0.762 V E cell = E cathode E anode = 0.762 V (0.447 V) = 0.762 V + 0.447 V = 0.315 V The standard cell potential is negative, so the reaction is non-spontaneous under standard conditions. (c) The two half-reactions are as follows. Oxidation (occurs at the anode): Ag(s) Ag+(aq) + e Reduction (occurs at the cathode): MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O( ) The relevant standard reduction potentials are: E = 0.800 V Ag(s) Ag+(aq) + e MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O( ) E = 1.507 V E cell = E cathode E anode = 1.507 V 0.800 V = 0.707 V The standard cell potential is positive, so the reaction is spontaneous under standard conditions.

19. Problem

Explain why an aqueous copper(I) compound disproportionates to form copper metal and an aqueous copper(II) compound under standard conditions. (You learned about disproportionation in Chapter 10.) Solution The net ionic equation for the reaction is as follows. Cu+(aq) Cu(s) + Cu2+(aq) (unbalanced) 2Cu+(aq) Cu(s) + Cu2+(aq) (balanced) The two half-reactions are as follows. Oxidation (occurs at the anode): Cu+(aq) Cu2+(aq) + e Reduction (occurs at the cathode): Cu+(aq) + e Cu(s) The relevant standard reduction potentials are: E = 0.153 V Cu+(aq) Cu2+(aq) + e + Cu (aq) + e E = 0.521 V Cu(s) E cell = E cathode E anode = 0.521 V 0.153 V = 0.368 V The standard cell potential is positive, so the disproportionation of an aqueous copper(I) compound to form copper metal and an aqueous copper(II) compound is spontaneous under standard conditions.
20. Problem

Predict whether each reaction is spontaneous or non-spontaneous under standard conditions in an acidic solution. (a) H2O2(aq) H2(g) + O2(g) (b) 3H2(g) + Cr2O72(aq) + 8H+(aq) 2Cr3+(aq) + 7H2O( )

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Solution (a) Write the two half-reactions for acidic conditions. Oxidation (occurs at the anode): H2O2(aq) O2(g) (unbalanced) H2O2(aq) O2(g) + 2H+(aq) H2O2(aq) O2(g) + 2H+(aq) + 2e (balanced) Reduction (occurs at the cathode): H+(aq) H2(g) (unbalanced) 2H+(aq) H2(g) 2H+(aq) + 2e H2(g) (balanced) Note: If the reduction half-reaction is unclear to you, remember that adding the two half-reactions must give the equation for the overall reaction. The relevant standard reduction potentials are: E = 0.695 V H2O2(aq) O2(g) + 2H+(aq) + 2e 2H+(aq) + 2e E = 0.000 V H2(g) E cell = E cathode E anode = 0.000 V 0.695 V = 0.695 V The standard cell potential is negative, so the reaction is non-spontaneous under standard conditions in an acidic solution. (b) Write the two half-reactions for acidic conditions. Reduction (occurs at the cathode): Cr2O72(aq) Cr3+(aq) (unbalanced) Cr2O72(aq) 2Cr3+(aq) Cr2O72(aq) 2Cr3+(aq) + 7H2O( ) Cr2O72(aq) + 14H+(aq) 2Cr3+(aq) + 7H2O( ) Cr2O72(aq) + 14H+(aq) + 6e 2Cr3+(aq) + 7H2O( ) (balanced) Oxidation (occurs at the anode): H2(g) H+(aq) (unbalanced) H2(g) 2H+(aq) H2(g) 2H+(aq) + 2e Note: If the oxidation half-reaction is unclear to you, remember that adding the two half-reactions must give the overall reaction. The relevant standard reduction potentials are: E = 1.232 V 2Cr3+(aq) + 7H2O( ) Cr2O72(aq) + 14H+(aq) + 6e + 2H (aq) + 2e E = 0.000 V H2(g) E cell = E cathode E anode = 1.232 V 0.000 V = 1.232 V The standard cell potential is positive, so the reaction is spontaneous under standard conditions in an acidic solution.

Solutions for Practice Problems


Student Textbook page 541
21. Problem

Calculate the mass of zinc plated onto the cathode of an electrolytic cell by a current of 750 mA in 3.25 h. What Is Required? You need to calculate the mass of zinc plated onto the cathode. What Is Given? You know the name of the element plated onto the cathode, the current, and the time.

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Element formed: zinc Current: 750 mA Time: 3.25 h You know that the charge on one mole of electrons is 96 500 C/mol. Plan Your Strategy Step 1 Use the current and the time to nd the quantity of electricity used. Step 2 From the quantity of electricity, nd the amount of electrons that pass through the circuit. Step 3 Use the stoichiometry of the relevant half-reaction to relate the amount of electrons to the amount of zinc plated onto the cathode. Step 4 Use the molar mass of zinc to convert the amount of zinc to a mass. Act on Your Strategy To calculate the quantity of electricity, in coulombs, work in amperes and seconds. 1000 mA = 1 A 1A 750 mA = 750 mA 1000 mA = 0.750 A 3.25 h = 3.25 h 60 min 60 s 1h 1 min = 11700 s or 1.17 104 s Quantity of electricity (in coulombs) = current (in amperes) time (in seconds) Quantity of electricity = 0.750 A 1.17 104 s = 8.78 103 C Step 2 Find the amount of electrons. Amount of electrons = 8.78 103 C 1 mol e 96500 C = 9.10 102 mol e Step 3 The half-reaction for the reduction of zinc ions to elemental zinc is Zn2+ + 2e Zn Amount of zinc formed = 9.10 102 mol e 1 mol Zn 2 mol e 2 = 4.55 10 mol Zn Step 4 Convert the amount of zinc to a mass. 65.39 g Zn Mass of Zn formed = 4.55 102 mol Zn 1 mol Zn = 2.98 g Zn
Step 1

Check Your Solution The answer is expressed in units of mass.


22. Problem

How many minutes does it take to plate 0.925 g of silver onto the cathode of an electrolytic cell using a current of 1.55 A? What Is Required? You need to calculate the time, in minutes, taken to plate the given mass of silver onto the cathode. What Is Given? You know the name of the element plated onto the cathode, the mass of the element formed, and the current. Element formed: silver Mass formed: 0.925 g Current: 1.55 A You know that the charge on one mole of electrons is 96 500 C/mol.
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Plan Your Strategy Step 1 Use the molar mass of silver to convert the mass of silver to an amount. Step 2 Use the stoichiometry of the relevant half-reaction to relate amount of silver to the amount of electrons. Step 3 From the amount of electrons, nd the quantity of electricity that passes through the circuit. Step 4 Use the quantity of electricity and the current to nd the time for which the current ows.
Step 1

1 mol Ag 107.87 g Ag = 8.58 103 mol Ag Step 2 The half-reaction for the reduction of silver ions to elemental silver is Ag+ + e Ag Amount of electrons = 8.58 103 mol Ag 1 mol e 1 mol Ag = 8.58 103 mol e Step 3 Find the quantity of electricity. Quantity of electricity = 8.58 103 mol e 96 500 C 1 mol e = 828 C Step 4 Find the time for which the current ows. Quantity of electricity (in coulombs) = current (in amperes) time (in seconds) quantity of electricity (in coulombs) Time (in seconds) = current (in amperes) 828 C = 1.55 A = 534 s Note: 1 C = 1 A 1 s, or 1 C = 1 As, so the units cancel correctly. Time (in minutes) = 534 s 1 min 60 s = 8.90 min Check Your Solution The answer is expressed in minutes.
23. Problem

Act on Your Strategy Convert the mass of silver to an amount. Amount of silver formed = 0.925 g Ag

The nickel anode in an electrolytic cell decreases in mass by 1.20 g in 35.5 min. The oxidation half-reaction converts nickel atoms to nickel(II) ions. What is the constant current? What Is Required? You need to calculate the constant current required to remove the given mass of nickel from the anode in the given length of time. What Is Given? You know the name of the element that makes up the anode, the mass of the element removed, and the time taken. Element removed: nickel Mass removed: 1.20 g Time: 35.5 min You know that the nickel removed from the anode is converted to Ni2+ ions. You also know that the charge on one mole of electrons is 96 500 C/mol.

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Plan Your Strategy Step 1 Use the molar mass of nickel to convert the mass of nickel to an amount. Step 2 Use the stoichiometry of the relevant half-reaction to relate the amount of nickel to the amount of electrons. Step 3 From the amount of electrons, nd the quantity of electricity that passes through the circuit. Step 4 Use the quantity of electricity and the time to nd the current. Act on Your Strategy Step 1 Convert the mass of nickel to an amount. Amount of nickel removed = 1.20 g Ni 1 mol Ni 58.69 g Ni = 2.04 102 mol Ni Step 2 The half-reaction for the oxidation of nickel to nickel(II) ions is Ni Ni2+ + 2e Amount of electrons = 2.04 102 mol Ni 2 mol e 1 mol Ni = 4.08 102 mol e Step 3 Find the quantity of electricity. Quantity of electricity = 4.08 102 mol e 96 500 C 1 mol e = 3.94 103 C Step 4 Find the current. Quantity of electricity (in coulombs) = current (in amperes) time (in seconds) quantity of electricity (in coulombs) Current (in amperes) = time (in seconds) Time (in seconds) = 35.5 min 60 s 1 min = 2.13 103 s
3 Current (in amperes) = 3.94 10 3 C 2.13 10 s = 1.85A Note: 1 C = 1 As, so the units cancel correctly.

Check Your Solution The answer is expressed in units of current.


24. Problem

The following two half-reactions take place in an electrolytic cell with an iron anode and a chromium cathode. Oxidation: Fe(s) Fe2+(aq) + 2e Reduction: Cr3+(aq) + 3e Cr(s) During the process, the mass of the iron anode decreases by 1.75 g. (a) Find the change in mass of the chromium cathode. (b) Explain why you do not need to know the electric current or the time to complete part (a). Solution
(a) Write the net ionic equation for the reaction to relate the amount of iron that

reacts and the amount of chromium formed. The problem is then a stoichiometry problem. The LCM of 2 and 3 is 6. Multiply the oxidation half-reaction by 3, and multiply the reduction halfreaction by 2, so that equal numbers of electrons are lost and gained. Then, add the half-reactions.

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3Fe(s) + + 6e 3Fe2+(aq) + 6e + 2Cr(s) Simplify by removing six electrons from both sides. 3Fe(s) + 2Cr3+(aq) 3Fe2+(aq) + 2Cr(s) The balanced net ionic equation shows that 2 mol of chromium are formed for every 3 mol of iron that react. Use this ratio to complete the stoichiometry calculation. 52.00 g Cr = 1.09 g Cr 1.75 g Fe 1 mol Fe 2 mol Cr 55.85 g Fe 3 mol Fe 1 mol Cr Because chromium is being plated onto the cathode, the mass of the cathode increases by 1.09 g. (b) Another way to calculate the mass of chromium deposited would be from the quantity of electricity that passes through the cell. The quantity of electricity could be calculated from the current and the time, or from the amount of iron that reacts and the stoichiometry of the oxidation half-reaction. However, because the half-reactions can be combined to give the net ionic equation for the overall reaction, there is no need at any stage of the calculation to know the quantity of electricity that passes.

2Cr3+(aq) 2Cr3+(aq)

3Fe(s) 3Fe2+(aq) + 6e + 6e 2Cr(s)

Solutions for Practice Problems


Student Textbook page 549
25. Problem (a) Use the two half-reactions for the rusting process, and a table of standard

reduction potentials. Determine the standard cell potential for this reaction.
(b) Do you think that your calculated value is the actual cell potential for each of

the small galvanic cells on the surface of a rusting iron object? Explain. Solution Oxidation (at the anode): Fe(s) Fe2+(aq) + 2e Reduction (at the cathode): O2(g) + 2H2O( ) + 4e 4OH(aq) The relevant standard reduction potentials are: E = 0.447 V Fe2+(aq) + 2e Fe(s) O2(g) + 2H2O( ) + 4e E = 0.401 V 4OH(aq) E cell = E cathode E anode = 0.401 V (0.447 V) = 0.848 V (b) No. The calculated value applies to standard conditions. The conditions on the surface are not expected to be standard.
26. Problem (a) The two half-reactions for the rusting process are as follows.

Explain why aluminum provides cathodic protection to an iron object. Solution Aluminum is more easily oxidized than iron. When these two metals are in contact and are exposed to air and water, a galvanic cell results. The aluminum is the sacricial anode in the cell and undergoes oxidation to form aluminum ions. The iron is the cathode in the cell, so iron does not undergo oxidation and does not rust until after all the aluminum has been oxidized.

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27. Problem

In the year 2000, Transport Canada reported that thousands of cars sold in the Atlantic Provinces between 1989 and 1999 had corroded engine cradle mounts. Failure of these mounts can cause the steering shaft to separate from the car. The manufacturer recalled the cars so that repairs could be made, where necessary. The same cars were sold across the country. Why do you think that the corrosion problems showed up in the Atlantic Provinces? Solution Possible reasons include the damp, salty air close to the ocean in the Atlantic Provinces, and the wetter and warmer winters than in some other parts of the country. There is enough snow in the Atlantic Provinces to require the use of large quantities of road salt. Cars are frequently exposed to water and an electrolyte under conditions that are warm enough to permit fairly rapid corrosion.
28. Problem (a) Use the table of standard reduction potentials to determine whether elemental

oxygen, O2(g) , is a better oxidizing agent under acidic conditions or basic conditions. (b) From your answer to part (a), do you think that acid rain promotes or helps prevent the rusting of iron? Solution E = 1.229 V 2H2O( ) O2(g) + 4H+(aq) + 4e O2(g) + 2H+(aq) + 2e E = 0.695 V H2O2(aq) O2(g) + 2H2O( ) + 4e E = 0.401 V 4OH(aq) For the rst two of these half-reactions, the conditions are acidic. For the third half-reaction, the conditions are basic. The rst two half-reactions are higher in the table of standard reduction potentials than the third half-reaction. Better oxidizing agents are found higher in the table of standard reduction potentials. Therefore, elemental oxygen is predicted to be a better oxidizing agent under acidic conditions than under basic conditions. (b) The rst and third of the half-reactions in part (a) are relevant to the rusting process under acidic conditions and basic conditions. Because acid rain would expose iron to oxygen under acidic conditions, it seems that acid rain should promote the rusting of iron.
(a) The relevant standard reduction potential are:

Solutions for Practice Problems


Student Textbook page 551
29. Problem

Calculate E cell for a hydrogen fuel cell. Solution The half-reactions in a hydrogen fuel cell are as follows. Oxidation (at the anode): H2(g) + 2OH(aq) 2H2O( ) + 2e Reduction (at the cathode): O2(g) + 2H2O( ) + 4e 4OH(aq) The relevant standard reduction potentials are: E = 0.828 V H2(g) + 2OH(aq) 2H2O( ) + 2e O2(g) + 2H2O( ) + 4e E = 0.401 V 4OH (aq) E cell = E cathode E anode = 0.401 V (0.828 V) = 1.229 V
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30. Problem

In one type of fuel cell, methane is oxidized by oxygen to form carbon dioxide and water. (a) Write the equation for the overall cell reaction. (b) Write the two half-reactions, assuming acidic conditions.
(a) CH4(g) + O2(g) CO2(g) + H2O( ) (unbalanced)

Solution

Balance by inspection. CH4(g) + O2(g) CO2(g) + 2H2O( ) CH4(g) + 2O2(g) CO2(g) + 2H2O( ) (balanced) (b) Assign oxidation numbers to identify the half-reactions. CH4(g) + 2O2(g) CO2(g) + 2H2O( )
4 +1 0 +4 2 +1 2

The oxidation number of carbon increases, so methane, CH4, is oxidized. The oxidation number of oxygen decreases, so elemental oxygen, O2 , is reduced. Oxidation half-reaction: CH4(g) CO2(g) (unbalanced) Add water molecules to balance the oxygen atoms. CH4(g) + 2H2O( ) CO2(g) Add hydrogen ions to balance the hydrogen atoms. CH4(g) + 2H2O( ) CO2(g) + 8H+(aq) Add electrons to balance the charges. CH4(g) + 2H2O( ) CO2(g) + 8H+(aq) + 8e (balanced) Reduction half-reaction: O2(g) H2O( ) (unbalanced) Add a water molecule to balance the oxygen atoms. O2(g) 2H2O( ) Add hydrogen ions to balance the hydrogen atoms. O2(g) + 4H+(aq) 2H2O( ) Add electrons to balance the charges. O2(g) + 4H+(aq) + 4e 2H2O( ) (balanced) Note that, if the reduction half-reaction is multiplied by 2, the half-reactions are added, and the resulting equation is simplied, then the equation obtained is the overall equation from part (a).
31. Problem

Reactions that occur in fuel cells can be thought of as being ameless combustion reactions. Explain why. Solution The equations for the overall reactions in hydrogen fuel cells and in methane fuel cells are as follows. 2H2(g) + O2(g) 2H2O( ) CH4(g) + 2O2(g) CO2(g) + 2H2O( ) The rst equation is the same as the equation for the combustion reaction in which hydrogen burns in oxygen. The second equation is the same as the equation for the combustion reaction in which methane burns in oxygen. However, for a fuel cell, the equation for the overall reaction is the sum of two half-reactions that occur in aqueous solutions. No ames are involved.
32. Problem

If a hydrogen fuel cell produces an electric current of 0.600 A for 120 min, what mass of hydrogen is consumed by the cell?

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Solution Use Faradays law to solve the problem. The following half-reaction in a hydrogen fuel cell involves the consumption of hydrogen. Oxidation (at the anode): H2(g) + 2OH(aq) 2H2O( ) + 2e Use the current (in amperes) and the time (in seconds) to calculate the quantity of electricity used (in coulombs). Time (in seconds) = 120 min 60 s 1 min = 7.20 103 s Quantity of electricity (in coulombs) = current (in amperes) time (in seconds) = 0.600 A 7.20 103 s = 4.32 103 C Amount of electrons = 4.32 103 C 1 mol e 96 500 C = 4.48 102 mol e Amount of hydrogen consumed = 4.48 102 mol e 1 mol H2 2 mol e = 2.24 102 mol H2 2.02 g H2 Mass of hydrogen consumed = 2.24 102 mol H2 1 mol H2 = 4.52 102 g H2

Solutions for Practice Problems


Student Textbook page 554
33. Problem

Show that the reaction of chlorine gas with water is a disproportionation reaction. Solution In a disproportionation reaction, the same element undergoes both oxidation and reduction. The equation for the reaction is Cl2(g) + H2O( ) HClO(aq) + HCl(aq) Assign oxidation numbers. Cl2(g) + H2O( ) HClO(aq) + HCl(aq)
0 +1 2 +1 +1 2 +1 1

No element except chlorine undergoes a change in its oxidation number. The oxidation number of some chlorine atoms increases from 0 to +1. The oxidation number of other chlorine atoms decreases from 0 to 1. Chlorine is undergoing both oxidation and reduction, so the reaction of chlorine with water is a disproportionation reaction.
34. Problem

Would you predict the products of the chlor-alkali process to be hydrogen and chlorine? Explain. Solution The only method covered so far for predicting the products from the electrolysis of an aqueous solution is to use the standard reduction potentials involving the ions in the electrolyte, and the non-standard reduction potentials for water. If this method is applied to the chlor-alkali process, which involves the electrolysis of sodium chloride solution, the result is as in Practice Problem 13. The predicted products are hydrogen and oxygen, not hydrogen and chlorine.
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However, the sodium chloride solution used in the chlor-alkali process is saturated. Sodium chloride is very soluble in water, so the concentration of sodium ions and chloride ions is far greater than the standard value of 1 mol/L. Moreover, if students use their research skills to nd out the temperature at which a chlor-alkali cell operates, they will nd that the temperature is not the standard value of 25C. The operating temperature is typically around 85C, depending on the design of the cell. Because the conditions in a chlor-alkali cell are not standard, the products of the electrolysis cannot be predicted with any condence by using the method covered so far.
35. Problem

Research and assess the most recent information you can nd on the health and safety aspects of the chlorination of water. Are you in favour of chlorination, or opposed to it? Explain your answer. Solution Chlorination can be effective in killing bacteria in the water supply, and thus in protecting against some water-borne diseases. However, concerns have been expressed that the chlorination of water may result in the formation of organic carcinogens. Because this problem requires the most recent information you can nd, students may well make other arguments for and against chlorination. The Internet may be a more likely source of current information than books. You may wish to have students treat this problem and problem 36 together. Knowledge of the advantages and disadvantages of an alternative process may inuence students views on chlorination.
36. Problem

Some municipalities use ozone gas rather than chlorine to kill bacteria in water. Research the advantages and disadvantages of using ozone in place of chlorine. Solution The use of ozone (ozonation) to purify water is not a recent development. For example, Paris, France, began using this method of water purication early in the twentieth century. There have been claims that ozone is more effective than chlorine at killing viruses in the water supply. However, higher costs may be an argument against ozonation. You may wish to have students treat this problem and problem 35 together. Encourage research methods that lead to the latest information.

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