Sample Exercise 20.

1 Identifying Oxidizing and Reducing Agents

The nickel–cadmium (nicad) battery uses the following redox reaction to generate electricity:

Cd(s) + NiO2(s) + 2H2O(l) → Cd(OH)2(s) + Ni(OH)2(s)

Identify the substances that are oxidized and reduced, and indicate which is the oxidizing agent and which is the
reducing agent.

Solution

Analyze We are given a redox equation and asked to identify the substance oxidized and the substance reduced and to
label the oxidizing agent and the reducing agent.

Plan First, we use the rules outlined earlier (Section 4.4) to assign oxidation states, or numbers, to all the
atoms and determine which elements change oxidation state. Second, we apply the definitions of oxidation and
reduction.

Solve

The oxidation state of Cd increases from 0 to +2, and that of Ni decreases from +4 to +2. Thus, the Cd atom is
oxidized (loses electrons) and is the reducing agent. The oxidation state of Ni decreases as NiO2 is converted into
Ni(OH)2. Thus, NiO2 is reduced (gains electrons) and is the oxidizing agent.

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 Sample Exercise 20.1 Identifying Oxidizing and Reducing Agents
Continued
Comment A common mnemonic for remembering oxidation and reduction is “LEO the lion says GER”: losing
electrons is oxidation; gaining electrons is reduction.

Practice Exercise 1

What is the reducing agent in the following reaction?

2 Br–(aq) + H2O2(aq) + 2 H+(aq) → Br2(aq) + 2 H2O(l)

(a) Br–(aq) (b) H2O2(aq) (c) H+(aq) (d) Br2(aq) (e) Na+(aq)

Practice Exercise 2

Identify the oxidizing and reducing agents in the reaction

2 H2O(l) + Al(s) + MnO4–(aq) → Al(OH)4–(aq) + MnO2(s)

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 Sample Exercise 20.2 Balancing Redox Equations in Acidic Solution
Complete and balance this equation by the method of half-reactions:

Cr2O72–(aq) + Cl–(aq) → Cr3+(aq) + Cl2(g) (acidic solution)

Solution

Analyze We are given an incomplete, unbalanced (skeleton) equation for a redox reaction occurring in acidic solution
and asked to complete and balance it.

Plan We use the half-reaction procedure we just learned.

Solve
Step 1: We divide the equation into two half-reactions:

Cr2O72–(aq) → Cr3+(aq)
Cl–(aq) → Cl2(g)

Step 2: We balance each half-reaction. In the first half-reaction the presence of one Cr2O72– among the reactants
requires two Cr3+ among the products. The seven oxygen atoms in Cr2O72– are balanced by adding seven H2O to the
products. The 14 hydrogen atoms in 7 H2O are then balanced by adding 14 H+ to the reactants:

14 H+(aq) + Cr2O72–(aq) → 2 Cr3+(aq) + 7 H2O(l)

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 Sample Exercise 20.2 Balancing Redox Equations in Acidic Solution
Continued
We then balance the charge by adding electrons to the left side of the equation so that the total charge is the same on
the two sides:

6 e– + 14 H+(aq) + Cr2O72–(aq) → 2 Cr3+(aq) + 7 H2O(l)

We can check this result by looking at the oxidation state changes. Each chromium atom goes from +6 to +3,
gaining three electrons; therefore, the two Cr atoms in Cr2O72– gain six electrons, in agreement with our half-
reaction.

In the second half-reaction, two Cl– are required to balance one Cl2:

2 Cl–(aq) → Cl2(g)

We add two electrons to the right side to attain charge balance:

2 Cl–(aq) → Cl2(g) + 2 e–

This result agrees with the oxidation state changes. Each chlorine atom goes from –1 to 0, losing one electron;
therefore, the two chlorine atoms lose two electrons.

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 Sample Exercise 20.2 Balancing Redox Equations in Acidic Solution
Continued
Step 3: We equalize the number of electrons transferred in the two half-reactions. To do so, we multiply the Cl half-
reaction by 3 so that the number of electrons gained in the Cr half-reaction (6) equals the number lost in the Cl half-
reaction, allowing the electrons to cancel when the half-reactions are added:

6 Cl–(aq) → 3 Cl2(g) + 6 e–

Step 4: The equations are added to give the balanced equation:

14 H+(aq) + Cr2O72–(aq) + 6 Cl– (aq) → 2 Cr3+(aq) + 7 H2O(l) + 3 Cl2(g)

Step 5: There are equal numbers of atoms of each kind on the two sides of the equation (14 H, 2 Cr, 7 O, 6 Cl). In
addition, the charge is the same on the two sides (6+). Thus, the equation is balanced.

Practice Exercise 1

If you complete and balance the following equation in acidic solution

Mn2+(aq) + NaBiO3(s) → Bi3+(aq) + MnO4–(aq) + Na+(aq)

how many water molecules are there in the balanced equation (for the reaction balanced with the smallest whole-
number coefficients)? (a) Four on the reactant side, (b) Three on the product side, (c) One on the reactant side,
(d) Seven on the product side, (e) Two on the product side.

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 Sample Exercise 20.2 Balancing Redox Equations in Acidic Solution
Continued

Practice Exercise 2

Complete and balance the following equation in acidic solution using the method of half-reactions.

Cu(s) + NO3– (aq) → Cu2+(aq) + NO2(g)

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 Sample Exercise 20.3 Balancing Redox Equations in Acidic Solution
Complete and balance this equation for a redox reaction that takes place in basic solution:

CN–(aq) + MnO4–(aq) → CNO– (aq) + MnO2(s) (basic solution)

Solution

Analyze We are given an incomplete equation for a basic redox reaction and asked to balance it.

Plan We go through the first steps of our procedure as if the reaction were occurring in acidic solution. We then add
the appropriate number of OH– to each side of the equation, combining H+ and OH– to form H2O. We complete the
process by simplifying the equation.

Solve
Step 1: We write the
incomplete, unbalanced CN– (aq) → CNO– (aq)
half-reactions: MnO4–(aq) → MnO2(s)
Step 2: We balance each
half-reaction as if it took CN– (aq) + H2O(l) → CNO– (aq) + 2 H+ (aq) + 2 e–
place in acidic solution: 3 e– + 4 H+ (aq) + MnO4– (aq) → MnO2(s) + 2 H2O(l)

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 Sample Exercise 20.3 Balancing Redox Equations in Acidic Solution
Continued

Now we must take into

account that the reaction
occurs in basic solution,
adding OH– to both sides
of both half-reactions to CN– (aq) + H2O(l) + 2 OH– (aq) → CNO– (aq) + 2 H+(aq) + 2 e– + 2 OH– (aq)
neutralize H+: 3 e– + 4 H+ (aq) + MnO4– (aq) + 4 OH– (aq) → MnO2(s) + 2 H2O(l) + 4 OH– (aq)
We “neutralize” H+ and
OH– by forming H2O
when they are on the
same side of either CN– (aq) + H2O(l) + 2 OH– (aq) → CNO– (aq) + 2 H2O(l) + 2 e–
half-reaction: 3 e– + 4 H2O(l) + MnO4–(aq) → MnO2(s) + 2 H2O(l) + 4 OH– (aq)
Next, we cancel water
molecules that appear
as both reactants CN– (aq) + 2 OH– (aq) → CNO– (aq) + H2O(l) + 2 e–
and products: 3 e– + 2 H2O(l) + MnO4– (aq) → MnO2(s) + 4 OH– (aq)
Both half-reactions are now balanced. You can check the atoms and the overall charge.

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 Sample Exercise 20.3 Balancing Redox Equations in Acidic Solution
Continued

Step 3: We multiply the

cyanide half-reaction by 3,
which gives 6 electrons
on the product side, and
multiply the permanganate
half-reaction by 2, which
gives 6 electrons on the 3 CN– (aq) + 6 OH– (aq) → 3 CNO– (aq) + 3 H2O(l) + 6 e–
reactant side: 6 e– + 4 H2O(l) + 2 MnO4– (aq) → 2 MnO2(s) + 8 OH–(aq)
Step 4: We add the two
half-reactions together and
simplify by canceling
species that appear as both
reactants and products: 3 CN– (aq) + H2O(l) + 2 MnO4– (aq) → 3 CNO– (aq) + 2 MnO2(s) + 2 OH– (aq)
Step 5: Check that the
atoms and charges
are balanced.
There are 3 C, 3 N, 2 H, 9 O, 2 Mn, and a charge of 5− on both sides of the equation.

Comment It is important to remember that this procedure does not imply that H+ ions are involved in the chemical
reaction. Recall that in aqueous solutions at 20 °C, Kw = [H+][OH–] = 1.0 × 10–14. Thus, [H+] is very small in this
basic solution. (Section 16.3)

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 Sample Exercise 20.3 Balancing Redox Equations in Acidic Solution
Continued

Practice Exercise 1

If you complete and balance the following oxidation–reduction reaction in basic solution

NO2– (aq) + Al(s) → NH3(aq) + Al(OH)4– (aq)

how many hydroxide ions are there in the balanced equation (for the reaction balanced with the smallest whole-
number coefficients)? (a) One on the reactant side, (b) One on the product side, (c) Four on the reactant side,
(d) Seven on the product side, (e) None.

Practice Exercise 2

Complete and balance the following oxidation–reduction reaction in basic solution:

Cr(OH)3(s) + ClO– (aq) → CrO42– (aq) + Cl2(g)

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 Sample Exercise 20.4 Describing a Voltaic Cell
The oxidation–reduction reaction

Cr2O72– (aq) + 14 H+ (aq) + 6 I– (aq) → 2 Cr3+ (aq) + 3 I2(s) + 7 H2O(l)

is spontaneous. A solution containing K2Cr2O7 and H2SO4 is poured into one beaker, and a solution of KI is poured
into another. A salt bridge is used to join the beakers. A metallic conductor that will not react with either solution
(such as platinum foil) is suspended in each solution, and the two conductors are connected with wires through a
voltmeter or some other device to detect an electric current. The resultant voltaic cell generates an electric current.
Indicate the reaction occurring at the anode, the reaction at the cathode, the direction of electron migration, the
direction of ion migration, and the signs of the electrodes.

Solution

Analyze We are given the equation for a spontaneous reaction that

takes place in a voltaic cell and a description of how the cell is
constructed. We are asked to write the half-reactions occurring at
the anode and at the cathode, as well as the directions of electron
and ion movements and the signs assigned to the electrodes.

Plan Our first step is to divide the chemical equation into half-
reactions so that we can identify the oxidation and the reduction
processes. We then use the definitions of anode and cathode and
the other terminologies summarized in Figure 20.6.

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 Sample Exercise 20.4 Describing a Voltaic Cell
Continued
Solve In one half-reaction, Cr2O72– (aq) is converted into Cr3+(aq). Starting with these ions and then completing and
balancing the half-reaction, we have

Cr2O72– (aq) + 14 H+ (aq) + 6 e– → 2 Cr3+(aq) + 7 H2O(l)

In the other half-reaction, I– (aq) is converted to I2(s):

6 I– (aq) → 3 I2 (s) + 6 e–

Now we can use the summary in Figure 20.6 to help us describe the voltaic cell. The first half-reaction is the
reduction process (electrons on the reactant side of the equation). By definition, the reduction process occurs at the
cathode. The second half-reaction is the oxidation process (electrons on the product side of the equation), which
occurs at the anode.

The I– ions are the source of electrons, and the Cr2O72– ions accept the electrons. Hence, the electrons flow through
the external circuit from the electrode immersed in the KI solution (the anode) to the electrode immersed in the
K2Cr2O7–H2SO4 solution (the cathode). The electrodes themselves do not react in any way; they merely provide a
means of transferring electrons from or to the solutions. The cations move through the solutions toward the cathode,
and the anions move toward the anode. The anode (from which the electrons move) is the negative electrode, and the
cathode (toward which the electrons move) is the positive electrode.

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 Sample Exercise 20.4 Describing a Voltaic Cell
Continued

Practice Exercise 1

The following two half-reactions occur in a voltaic cell:

Ni(s) → Ni2+ (aq) + 2 e– (electrode = Ni)

Cu2+(aq) + 2 e– → Cu(s) (electrode = Cu)

Which one of the following descriptions most accurately describes what is occurring in the half-cell containing the
Cu electrode and Cu2+ (aq) solution?

(a) The electrode is losing mass and cations from the salt bridge are flowing into the half-cell.
(b) The electrode is gaining mass and cations from the salt bridge are flowing into the half-cell.
(c) The electrode is losing mass and anions from the salt bridge are flowing into the half-cell.
(d) The electrode is gaining mass and anions from the salt bridge are flowing into the half-cell.

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 Sample Exercise 20.4 Describing a Voltaic Cell
Continued

Practice Exercise 2

The two half-reactions in a voltaic cell are

Zn(s) → Zn2+ (aq) + 2 e– (electrode = Zn)

ClO3– (aq) + 6 H+ (aq) + 6 e– → Cl– (aq) + 3 H2O(l) (electrode = Pt)

(a) Indicate which reaction occurs at the anode and which at the cathode. (b) Does the zinc electrode gain, lose, or
retain the same mass as the reaction proceeds? (c) Does the platinum electrode gain, lose, or retain the same mass as
the reaction proceeds? (d) Which electrode is positive?

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 Sample Exercise 20.5 Calculating E°red from E°cell
For the Zn–Cu2+ voltaic cell shown in Figure 20.5, we have

Zn(s) + Cu2+(aq, 1 M) → Zn2+ (aq, 1 M) + Cu(s) E°cell = 1.10 V

Given that the standard reduction potential

of Zn2+ to Zn(s) is –0.76 V, calculate
the E°red for the reduction of Cu2+ to Cu:

Cu2+ (aq, 1 M) + 2 e– → Cu(s)

Solution

Analyze We are given E°cell and E°red for Zn2+ and asked to calculate E°red for Cu2+.

Plan In the voltaic cell, Zn is oxidized and is therefore the anode. Thus, the given E°red for Zn2+ is E°red (anode).
Because Cu2+ is reduced, it is in the cathode half-cell. Thus, the unknown reduction potential for Cu 2+ is E°red
(cathode). Knowing E°cell and E°red (anode), we can use Equation 20.8 to solve for E°red (cathode).

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 Sample Exercise 20.5 Calculating E°red from E°cell
Continued
Solve
E°cell = E°red (cathode) – E°red (anode)
1.10 V = E°red (cathode) – (–0.76 V)
E°red (cathode) = 1.10 V – 0.76 V = 0.34 V

Check This standard reduction potential agrees

with the one listed in Table 20.1.

Comment The standard reduction potential for

Cu2+ can be represented as E°Cu2+ = 0.34 V
and that for Zn2+ as E°Zn2+ = –0.76 V. The
subscript identifies the ion that is reduced in
the reduction half-reaction.

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 Sample Exercise 20.5 Calculating E°red from E°cell
Continued

Practice Exercise 1

A voltaic cell based on the reaction 2 Eu2+(aq) + Ni2+(aq) → 2 Eu3+(aq) + Ni(s) generates E°cell = 0.07 V. Given the
standard reduction potential of Ni2+ given in Table 20.1 what is the standard reduction potential for the reaction
Eu3+(aq) + e– → Eu2+(aq)? (a) –0.35 V, (b) 0.35 V, (c) –0.21 V, (d) 0.21 V, (e) 0.07 V.

Practice Exercise 2

The standard cell potential is 1.46 V for a voltaic cell based on the following half-reactions:

In+(aq) → In3+(aq) + 2 e–
Br2(l) + 2 e– → 2 Br– (aq)

Using Table 20.1, calculate E°red for the reduction of In3+ to In+.

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 Sample Exercise 20.6 Calculating E°cell from E°red
Use Table 20.1 to calculate E°cell for the voltaic cell described in Sample Exercise 20.4, which is
based on the reaction

Cr2O72– (aq) + 14 H+ (aq) + 6 I– (aq) → 2 Cr3+ (aq) + 3 I2 (s) + 7 H2O(l)

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 Sample Exercise 20.6 Calculating E°cell from E°red
Continued

Solution

Analyze We are given the equation for a redox reaction and asked to use data in Table 20.1 to calculate
the standard cell potential for the associated voltaic cell.

Plan Our first step is to identify the half-reactions that occur at the cathode and anode, which we did in Sample
Exercise 20.4. Then we use Table 20.1 and Equation 20.8 to calculate the standard cell potential.

Solve The half-reactions are

Cathode: Cr2O72–(aq) + 14 H+ (aq) + 6 e– → 2 Cr3+ (aq) + 7 H2O(l)

Anode: 6 I– (aq) → 3 I2(s) + 6 e–

According to Table 20.1, the standard reduction potential for the reduction of Cr2O72– to Cr3+ is +1.33 V and the
standard reduction potential for the reduction of I2 to I– (the reverse of the oxidation half-reaction) is +0.54 V. We
use these values in Equation 20.8:

E°cell = E°red (cathode) – E°red (anode) = 1.33 V – 0.54 V = 0.79 V

Although we must multiply the iodide half-reaction by 3 to obtain a balanced equation, we do not multiply the E°red
value by 3. As we have noted, the standard reduction potential is an intensive property and so is independent of the
stoichiometric coefficients.

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 Sample Exercise 20.6 Calculating E°cell from E°red
Continued
Check The cell potential, 0.79 V, is a positive number. As noted earlier, a voltaic cell must have a positive potential.

Practice Exercise 1

Using the data in Table 20.1 what value would you calculate for the standard emf (E°cell) for a voltaic cell that
employs the overall cell reaction 2 Ag+(aq) + Ni(s) → 2 Ag(s) + Ni2+(aq)? (a) +0.52 V, (b) –0.52 V, (c) +1.08 V,
(d) –1.08 V, (e) +0.80 V.

Practice Exercise 2

Using data in Table 20.1, calculate the standard emf for a cell that employs the overall cell reaction
2 Al(s) + 3 I2(s) → 2 Al3+(aq) + 6 I–(aq).

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 Sample Exercise 20.7 Determining Half-Reactions at Electrodesand
Calculating Cell Potentials
A voltaic cell is based on the two standard half-reactions

Cd2+(aq) + 2 e– → Cd(s)
Sn2+(aq) + 2 e– → Sn(s)

Use data in Appendix E to determine (a) which half-reaction occurs at the cathode and which occurs at the anode
and (b) the standard cell potential.

Solution

Analyze We have to look up E°red for two half-reactions. We then use these values first to determine the cathode
and the anode and then to calculate the standard cell potential, E°cell.

Plan The cathode will have the reduction with the more positive E°red value, and the anode will have the less
positive E°red. To write the half-reaction at the anode, we reverse the half-reaction written for the reduction, so
that the half-reaction is written as an oxidation.

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 Sample Exercise 20.7 Determining Half-Reactions at Electrodesand
Calculating Cell Potentials
Continued
The anode reaction, therefore, is the loss of electrons by Cd:

Anode: Cd(s) → Cd2+(aq) + 2 e–

(b) The cell potential is given by the difference in the standard reduction potentials at the cathode and anode
(Equation 20.8):

E°cell = E°red (cathode) – E°red (anode) = (–0.136 V) – (–0.403 V) = 0.267 V

Notice that it is unimportant that the E°red values of both half-reactions are negative; the negative values
merely indicate how these reductions compare to the reference reaction, the reduction of H +(aq).

Check The cell potential is positive, as it must be for a voltaic cell.

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 Sample Exercise 20.7 Determining Half-Reactions at Electrodesand
Calculating Cell Potentials
Continued
Practice Exercise 1

Consider three voltaic cells, each similar to the one

shown in Figure 20.5. In each voltaic cell, one half-cell
contains a 1.0 M Fe(NO3)2(aq) solution with an Fe
electrode. The contents of the other half-cells are
as follows:

Cell 1: a 1.0 M CuCl2(aq) solution with a Cu electrode

Cell 2: a 1.0 M NiCl2(aq) solution with a Ni electrode
Cell 3: a 1.0 M ZnCl2(aq) solution with a Zn electrode

In which voltaic cell(s) does iron act as the anode?

(a) Cell 1, (b) Cell 2, (c) Cell 3, (d) Cells 1 and 2, (e) All three cells.

Practice Exercise 2

A voltaic cell is based on a Co2+/Co half-cell and a AgCl/Ag half-cell.

(a) What half-reaction occurs at the anode? (b) What is the standard cell potential?

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 Sample Exercise 20.8 Determining Relative Strengths of
Oxidizing Agents
Using Table 20.1, rank the following ions in the order
of increasing strength as oxidizing agents:
NO3–(aq), Ag+(aq), Cr2O72–.

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 Sample Exercise 20.8 Determining Relative Strengths of
Oxidizing Agents
Continued
Solution

Analyze We are asked to rank the abilities of several ions to act as oxidizing agents.

Plan The more readily an ion is reduced (the more positive its E°red value), the stronger it is as an oxidizing agent.

Solve From Table 20.1, we have

NO3–(aq) + 4 H+(aq) + 3 e– → NO(g) + 2 H2O(l) E°red = +0.96 V

Ag+(aq) + e– → Ag(s) E°red = +0.80 V
Cr2O72–(aq) + 14 H+(aq) + 6 e– → 2 Cr3+(aq) + 7 H2O(l) E°red = +1.33 V

Because the standard reduction potential of Cr2O72– is the most positive, Cr2O72– is the strongest oxidizing agent of
the three. The rank order is Ag+ < NO3– < Cr2O72–.

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 Sample Exercise 20.8 Determining Relative Strengths of
Oxidizing Agents
Continued
Practice Exercise 1

Based on the data in Table 20.1 which of the following species would you expect to be the strongest oxidizing
agent? (a) Cl–(aq), (b) Cl2(g), (c) O2(g), (d) H+(aq), (e) Na+(aq).

Practice Exercise 2

Using Table 20.1, rank the following species from the strongest to the weakest reducing agent: I– (aq), Fe(s), Al(s).

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 Sample Exercise 20.9 Determining Spontaneity
Use Table 20.1 to determine whether the following reactions are spontaneous under standard conditions.

(a) Cu(s) + 2 H+(aq) → Cu2+(aq) + H2(g)

(b) Cl2(g) + 2 I–(aq) → 2 Cl–(aq) + I2(s)

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 Sample Exercise 20.9 Determining Spontaneity
Continued

Solution

Analyze We are given two reactions and must determine whether each is spontaneous.

Plan To determine whether a redox reaction is spontaneous under standard conditions, we first need to write its
reduction and oxidation half-reactions. We can then use the standard reduction potentials and Equation 20.10 to
calculate the standard emf, E°, for the reaction. If a reaction is spontaneous, its standard emf must be a positive
number.

Solve
(a) We first must identify the oxidation and Reduction: 2 H+(aq) + 2 e– → H2(g)
reduction half-reactions that when Oxidation: Cu(s) → Cu2+(aq) + 2 e–
combined give the overall reaction.

We look up standard reduction potentials for E° = E°red (reduction process) – E°red (oxidation
both half-reactions and use them to calculate process)
E° using Equation 20.10: = (0 V) – (0.34 V) = –0.34 V

Because E° is negative, the reaction is not

spontaneous in the direction written. Copper
metal does not react with acids as written in
Equation (a). The reverse reaction, however, Cu2+(aq) + H2(g) → Cu(s) + 2 H+(aq) E° = +0.34 V
is spontaneous and has a positive E° value:

Thus, Cu2+ can be reduced by H2.

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 Sample Exercise 20.9 Determining Spontaneity
Continued
(b) We follow a procedure analogous
to that in (a): Reduction: Cl2(g) + 2 e– → 2 Cl–(aq)
Oxidation: 2 I–(aq) → I2(s) + 2 e–

In this case E° = (1.36 V) – (0.54 V) = +0.82 V

Because the value of E° is positive, this reaction is spontaneous and could be used to build a voltaic cell.

Practice Exercise 1

Which of the following elements is capable of oxidizing Fe2+(aq) ions to Fe3+(aq) ions: chlorine, bromine, iodine?
(a) I2, (b) Cl2, (c) Cl2 and I2, (d) Cl2 and Br2, (e) all three elements.

Practice Exercise 2
Using the standard reduction potentials listed in Appendix E, determine which of the following reactions are
spontaneous under standard conditions:

(a) I2(s) + 5 Cu2+(aq) + 6 H2O(l) → 2 IO3–(aq) + 5 Cu(s) + 12 H+(aq)

(b) Hg2+(aq) + 2 I–(aq) → Hg(l) + I2(s)
(c) H2SO3(aq) + 2 Mn(s) + 4 H+(aq) → S(s) + 2 Mn2+(aq) + 3 H2O(l)

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 Sample Exercise 20.10 Using Standard Reduction Potentials to
Calculate ∆G° and K
(a) Use the standard reduction potentials in Table 20.1
to calculate the standard free-energy change, ∆G°,
and the equilibrium constant, K, at 298 K for
the reaction

4 Ag(s) + O2(g) + 4 H+(aq) → 4 Ag+(aq) + 2 H2O(l)

(b) Suppose the reaction in part (a) is written

2 Ag(s) + O2(g) + 2 H+(aq) → 2 Ag+(aq) + H2O(l)

What are the values of E°, ∆G°, and K when the

reaction is written in this way?

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 Sample Exercise 20.10 Using Standard Reduction Potentials to
Calculate ∆G° and K
Continued
Solution

Analyze We are asked to determine ∆G° and K for a redox reaction, using standard reduction potentials.

Plan We use the data in Table 20.1 and Equation 20.10 to determine E° for the reaction and then use E° in
Equation 20.12 to calculate ∆G°. We can then use either Equation 19.20 or Equation 20.13 to calculate K.

Solve
(a) We first calculate E° by breaking the equation into two half-reactions and obtaining E°red values from
Table 20.1 (or Appendix E):

Reduction: O2(g) + 4 H+(aq) + 4 e– → 2 H2O(l) E°red = +1.23 V

Oxidation: 4 Ag(s) → 4 Ag+(aq) + 4 e– E°red = +0.80 V

Even though the second half-reaction has 4 Ag, we use the E°red value directly from Table 20.1 because emf is
an intensive property.

Using Equation 20.10, we have

E° = (1.23 V) – (0.80 V) = 0.43 V

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 Sample Exercise 20.10 Using Standard Reduction Potentials to
Calculate ∆G° and K
Continued
The half-reactions show the transfer of four electrons. Thus, for this reaction n = 4. We now use Equation 20.12
to calculate ∆G°:

∆G° = –nFE°
= –(4)(96,485 J/V-mol)(+0.43 V)
= –1.7 × 105 J/mol = –170 kJ/mol

Now we need to calculate the equilibrium constant, K, using ∆G° = RT ln K. Because ∆G° is a large
negative number, which means the reaction is thermodynamically very favorable, we expect K to be large.

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 Sample Exercise 20.10 Using Standard Reduction Potentials to
Calculate ∆G° and K
Continued
(b) The overall equation is the same as that in part (a), multiplied by The half-reactions are

Reduction: O2(g) + 2 H+(aq) + 2 e– → H2O(l) E°red = +1.23 V

Oxidation: 2 Ag(s) → 2 Ag+(aq) + 2 e– E°red = +0.80 V

The values of E°red are the same as they were in part (a); they are not changed by multiplying the half-
reactions by 12. Thus, E° has the same value as in part (a): E° = +0.43 V. Notice, though, that the value of n
has changed to n = 2, which is one-half the value in part (a). Thus, ∆G° is half as large as in part (a):

∆G° = –(2)(96,485 J/V-mol)(+0.43 V) = –83 kJ/mol

The value of ∆G° is half that in part (a) because the coefficients in the chemical equation are half those in (a).

Now we can calculate K as before:

–8.3 × 104 J/mol = –(8.314 J/K mol)(298 K) ln K

K = 4 × 1014

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 Sample Exercise 20.10 Using Standard Reduction Potentials to
Calculate ∆G° and K
Continued
Comment E° is an intensive quantity, so multiplying a chemical equation by a certain factor will not affect the
value of E°. Multiplying an equation will change the value of n, however, and hence the value of ∆G°. The
change in free energy, in units of J/mol of reaction as written, is an extensive quantity. The equilibrium constant is
also an extensive quantity.

Practice Exercise 1

For the reaction

3 Ni2+(aq) + 2 Cr(OH)3(s) + 10 OH–(aq) → 3 Ni(s) + 2 CrO42–(aq) + 8 H2O(l)

∆G° = +87 kJ/mol. Given the standard reduction potential of Ni2+(aq) in Table 20.1, what value do you calculate
for the standard reduction potential of the half-reaction

CrO42–(aq) + 4 H2O(l) + 3 e– → Cr(OH)3(s) + 5 OH–(aq)?

(a) –0.43 V (b) –0.28 V (c) 0.02 V (d) –0.13 V (e) –0.15 V

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 Sample Exercise 20.10 Using Standard Reduction Potentials to
Calculate ∆G° and K
Continued
Practice Exercise 2

Consider the reaction 2 Ag+(aq) + H2(g) → 2 Ag(s) + 2 H+(aq). Calculate ∆G°f for the Ag+(aq) ion from the
standard reduction potentials in Table 20.1 and the fact that ∆G°f for H2(g), Ag(s), and H+(aq) are all zero.
Compare your answer with the value given in Appendix C.

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 Sample Exercise 20.11 Cell Potential under Nonstandard Conditions
Calculate the emf at 298 K generated by a voltaic cell in which the reaction is

Cr2O72–(aq) + 14 H+(aq) + 6 I–(aq) → 2 Cr3+(aq) + 3 I2(s) + 7 H2O(l)

when

[Cr2O72–] = 2.0 M, [H+] = 1.0 M, [I–] = 1.0 M, and [Cr3+] = 1.0 × 10–5 M

Solution
Analyze We are given a chemical equation for a voltaic cell and the concentrations of reactants and products under
which it operates. We are asked to calculate the emf of the cell under these nonstandard conditions.
Plan To calculate the emf of a cell under nonstandard conditions, we use the Nernst equation in the form of
Equation 20.18.

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 Sample Exercise 20.11 Cell Potential under Nonstandard Conditions
Continued
Solve We calculate E° for the cell from standard reduction
potentials (Table 20.1 or Appendix E). The standard emf for
this reaction was calculated in Sample Exercise 20.6:
E° = 0.79 V. As that exercise shows, six electrons are
transferred from reducing agent to oxidizing agent, so n = 6.
The reaction quotient, Q, is

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 Sample Exercise 20.11 Cell Potential under Nonstandard Conditions
Continued
Using Equation 20.18, we have

Check This result is qualitatively what we expect: Because the concentration of Cr 2O72– (a reactant) is greater
than 1 M and the concentration of Cr3+ (a product) is less than 1 M, the emf is greater than E°. Because Q is about
10–10, log Q is about –10. Thus, the correction to E° is about 0.06 × 10/6, which is 0.1, in agreement with the more
detailed calculation.

Practice Exercise 1

Consider a voltaic cell whose overall reaction is Pb2+(aq) + Zn(s) → Pb(s) + Zn2+(aq). What is the emf generated by
this voltaic cell when the ion concentrations are [Pb2+] = 1.5 × 10–3 M and [Zn2+] = 0.55 M? (a) 0.71 V, (b) 0.56 V,
(c) 0.49 V, (d) 0.79 V, (e) 0.64 V.

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 Sample Exercise 20.11 Cell Potential under Nonstandard Conditions
Continued
Practice Exercise 2
For the Zn–Cu voltaic cell depicted in Figure 20.5 would the emf increase, decrease, or stay the same, if you increased
the Cu2+(aq) concentration by adding CuSO4 · 5H2O to the cathode compartment?

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 Sample Exercise 20.12 Calculating Concentrations in a Voltaic Cell
If the potential of a Zn–H+ cell (like that
in Figure 20.9) is 0.45 V at 25 °C when
[Zn2+] = 1.0 M and PH2 = 1.0 atm, what
is the pH of the cathode solution?

Solution
Analyze We are given a description of a voltaic cell, its emf, the concentration of Zn2+, and the partial pressure of H2
(both products in the cell reaction). We are asked to calculate the pH of the cathode solution, which we can calculate
from the concentration of H+, a reactant.
Plan We write the equation for the cell reaction and use standard reduction potentials to calculate E° for the reaction.
After determining the value of n from our reaction equation, we solve the Nernst equation, Equation 20.18, for Q. We
use the equation for the cell reaction to write an expression for Q that contains [H+] to determine [H+]. Finally, we use
[H+] to calculate pH.

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 Sample Exercise 20.12 Calculating Concentrations in a Voltaic Cell
Continued
Solve The cell reaction is Zn(s) + 2 H+(aq) → Zn2+(aq) + H2(g)

The standard emf is E° = E°red (reduction) – E°red (oxidation)

= 0 V – (–0.76 V) = +0.76 V

Because each Zn atom loses two electrons, n=2

Using Equation 20.18, we can solve for Q:

Q = 1010.5 = 3 × 1010

Q has the form of the equilibrium constant

for the reaction:

Solving for [H+], we have

Finally, we use [H+] to calculate the pH

of the cathode solution. pH = log [H+] = –log (6 × 10–6) = 5.2

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 Sample Exercise 20.12 Calculating Concentrations in a Voltaic Cell
Continued
Comment A voltaic cell whose cell reaction involves H + can be used to measure [H+] or pH. A pH meter is a specially
designed voltaic cell with a voltmeter calibrated to read pH directly. (Section 16.4)

Practice Exercise 1

Consider a voltaic cell where the anode half-reaction is Zn(s) → Zn2+(aq) + 2 e– and the cathode half-reaction is
Sn2+(aq) + 2e– → Sn(s). What is the concentration of Sn2+ if Zn2+ is 2.5 × 10–3 M and the cell emf is 0.660 V? Use
the reduction potentials in Appendix E that are reported to three significant figures. (a) 3.3 × 10–2 M, (b) 1.9 × 10–4
M, (c) 9.0 × 10–3 M, (d) 6.9 × 10–4 M, (e) 7.6 × 10–3 M.

Practice Exercise 2

What is the pH of the solution in the cathode

half-cell in Figure 20.9 when PH2 = 1.0 atm,
[Zn2+] in the anode half-cell is 0.10 M, and
the cell emf is 0.542 V?

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 Sample Exercise 20.13 Determining pH Using a Concentration Cell
A voltaic cell is constructed with two hydrogen electrodes. Electrode 1 has PH2 = 1.00 atm and an unknown
concentration of H+(aq). Electrode 2 is a standard hydrogen electrode (PH2 = 1.00 atm, [H+] = 1.00 M). At 298 K
the measured cell potential is 0.211 V, and the electrical current is observed to flow from electrode 1 through the
external circuit to electrode 2. Calculate [H+] for the solution at electrode 1. What is the pH of the solution?
Solution

Analyze We are given the potential of a concentration cell and the direction in which the current flows. We also
have the concentrations or partial pressures of all reactants and products except for [H+] in half-cell 1, which is
our unknown.

Plan We can use the Nernst equation to determine Q and then use Q to calculate the unknown concentration. Because
this is a concentration cell, E°cell = 0 V.

Solve Using the Nernst equation, we have

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 Sample Exercise 20.13 Determining pH Using a Concentration Cell
Continued
Because electrons flow from electrode 1 to
electrode 2, electrode 1 is the anode of the
cell and electrode 2 is the cathode. The
electrode reactions are therefore as follows,
with the concentration of H+(aq) in
electrode 1 represented with the unknown x:

Thus,

At electrode 1, therefore, the pH of the

solution is pH = –log[H+] = –log(2.7 × 10–4) = 3.57

Comment The concentration of H+ at electrode 1 is lower than that in electrode 2, which is why electrode 1 is the
anode of the cell: The oxidation of H2 to H+(aq) increases [H+] at electrode 1.

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 Sample Exercise 20.13 Determining pH Using a Concentration Cell
Continued
Practice Exercise 1

A concentration cell constructed from two hydrogen electrodes, both with PH2 = 1.00. One electrode is immersed in
pure H2O and the other in 6.0 M hydrochloric acid. What is the emf generated by the cell and what is the identity of
the electrode that is immersed in hydrochloric acid? (a) –0.23 V, cathode, (b) 0.46 V, anode, (c) 0.023 V, anode,
(d) 0.23 V, cathode, (e) 0.23 V, anode.

Practice Exercise 2

A concentration cell is constructed with two Zn(s)–Zn2+(aq) half-cells. In one half-cell [Zn2+] = 1.35 M, and in the
other [Zn2+] = 3.75 × 10–4 M. (a) Which half-cell is the anode? (b) What is the emf of the cell?

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 Sample Exercise 20.14 Relating Electrical Charge and Quantity
of Electrolysis
Calculate the number of grams of aluminum produced in 1.00 h by the electrolysis of molten AlCl3 if the
electrical current is 10.0 A.

Solution

Analyze We are told that AlCl3 is electrolyzed to form Al and asked to calculate the
number of grams of Al produced in 1.00 h with 10.0 A.

Plan Figure 20.30 provides a roadmap for this problem. Using the current, time, a
balanced half-reaction, and the atomic weight of aluminum we can calculate the mass
of Al produced.

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 Sample Exercise 20.14 Relating Electrical Charge and Quantity
of Electrolysis
Continued
Solve First, we calculate the coulombs
of electrical charge passed into the
electrolytic cell:

Second, we calculate the number

of moles of electrons that pass
into the cell:

Third, we relate number of moles

of electrons to number of moles of
aluminum formed, using the half-
reaction for the reduction of Al3+: Al3+ + 3 e– → Al

Thus, 3 mol of electrons are required

to form 1 mol of Al:

Finally, we convert moles to grams:

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 Sample Exercise 20.14 Relating Electrical Charge and Quantity
of Electrolysis
Continued
Because each step involves
multiplication by a new factor, we
can combine all the steps:

Practice Exercise 1

How much time is needed to deposit 1.0 g of chromium metal from an aqueous solution of CrCl3 using a current
of 1.5 A? (a) 3.8 × 10–2 s, (b) 21 min, (c) 62 min, (d) 139 min, (e) 3.2 × 103 min.

Practice Exercise 2

(a) The half-reaction for formation of magnesium metal upon electrolysis of molten MgCl2 is Mg2+ + 2 e– → Mg.
Calculate the mass of magnesium formed upon passage of a current of 60.0 A for a period of 4.00 × 103 s. (b)
How many seconds would be required to produce 50.0 g of Mg from MgCl2 if the current is 100.0 A?

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 Sample Integrative Exercise Putting Concepts Together
The Ksp at 298 K for iron(II) fluoride is 2.4 × 10–6. (a) Write a half-reaction that gives the likely products of the
two-electron reduction of FeF2(s) in water. (b) Use the Ksp value and the standard reduction potential of Fe2+(aq)
to calculate the standard reduction potential for the half-reaction in part (a). (c) Rationalize the difference
between the reduction potential in part (a) and the reduction potential for Fe2+(aq).

Solution

Analyze We are going to combine what we know about equilibrium constants and electrochemistry to obtain
reduction potentials.

Plan For (a) we need to determine which ion, Fe2+ or F–, is more likely to be reduced by two electrons and complete
the overall reaction FeF2 + 2 e– → ?. For (b) we need to write the chemical equation associated with the Ksp and see
how it relates to E° for the reduction half-reaction in (a). For (c) we need to compare E° from (b) with the value for
the reduction of Fe2+.

Solve
(a) Iron(II) fluoride is an ionic substance that consists of Fe2+ and F– ions. We are asked to predict where two
electrons could be added to FeF2. We cannot envision adding the electrons to the F– ions to form F2–, so it seems
likely that we could reduce the Fe2+ ions to Fe(s). We therefore predict the half-reaction

FeF2(s) + 2 e– → Fe(s) + 2 F– (aq)

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 Sample Integrative Exercise Putting Concepts Together
Continued
(b) The Ksp for FeF2 refers to the following equilibrium: (Section 17.4)

FeF2(s) Fe2+(aq) + 2 F–(aq) Ksp = [Fe2+][F–]2 = 2.4 × 10–6

We were also asked to use the standard reduction potential of Fe2+, whose half-reaction and standard reduction
potentials are listed in Appendix E:

Fe2+(aq) + 2 e– → Fe(s) E = –0.440 V

According to Hess’s law, if we can add chemical equations to get a desired equation, then we can add their associated
thermodynamic state functions, like ∆H or ∆G, to determine the thermodynamic quantity for the desired reaction.
(Section 5.6) So we need to consider whether the three equations we are working with can be combined in a
similar fashion. Notice that if we add the Ksp reaction to the standard reduction half-reaction for Fe2+, we get the half-
reaction we want:

Reaction 3 is still a half-reaction, so we do see the free electrons.

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 Sample Integrative Exercise Putting Concepts Together
Continued
If we knew ∆G° for reactions 1 and 2,
we could add them to get ∆G° for reaction 3.
We can relate ∆G° to E° by ∆G° = –nFE°
(Equation 20.12) and to K by ∆G° = –RT ln K
(Equation 19.20, see also Figure 20.13).
Furthermore, we know that K for reaction 1
is the Ksp of FeF2, and we know E° for
reaction 2. Therefore, we can calculate ∆G°
for reactions 1 and 2:

Reaction 1:

∆G° = –RT ln K = –(8.314 J/K mol)(298 K) ln(2.4 × 10–6) = 3.21 × 104 J/mol

Reaction 2:

∆G° = –nFE° = –(2)(96,485 C/mol)(–0.440 J/C) = 8.49 × 104 J/mol

(Recall that 1 volt is 1 joule per coulomb.)

Then ∆G° for reaction 3, the one we want, is the sum of the ∆G° values for reactions 1 and 2:

3.21 × 104 J/mol + 8.49 × 104 J/mol = 1.17 × 105 J/mol

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 Sample Integrative Exercise Putting Concepts Together
Continued
We can convert this to E° from the relationship ∆G° = –nFE°:

(c) The standard reduction potential for FeF2(–0.606 V) is more negative than that for Fe2+(–0.440 V), telling us that
the reduction of FeF2 is the less favorable process. When FeF2 is reduced, we not only reduce the Fe2+ but also
break up the ionic solid. Because this additional energy must be overcome, the reduction of FeF2 is less favorable
than the reduction of Fe2+.

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