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Overview of Redox Reactions

Oxidation is the loss of electrons and reduction is the


gain of electrons. These processes occur simultaneously.
Oxidation results in an increase in O.N. while reduction
results in a decrease in O.N.

The oxidizing agent takes electrons from the substance


being oxidized. The oxidizing agent is therefore reduced.

The reducing agent takes electrons from the substance


being oxidized. The reducing agent is therefore oxidized.

21-1
Figure 21.1 A summary of redox terminology, as applied to the
reaction of zinc with hydrogen ion.

0 +1 +2 0
Zn(s) + 2H (aq) Zn (aq) + H2(g)
+ 2+

21-2
Half-Reaction Method for
Balancing Redox Reactions
The half-reaction method divides a redox reaction into its
oxidation and reduction half-reactions.
- This reflects their physical separation in electrochemical cells.

This method does not require assigning O.N.s.

The half-reaction method is easier to apply to reactions in


acidic or basic solutions.

21-3
Steps in the Half-Reaction Method
Divide the skeleton reaction into two half-reactions, each
of which contains the oxidized and reduced forms of one
of the species.
Balance the atoms and charges in each half-reaction.
First balance atoms other than O and H, then O, then H.
Charge is balanced by adding electrons (e-) to the left side in
the reduction half-reaction and to the right side in the oxidation
half-reaction.
If necessary, multiply one or both half-reactions by an
integer so that
number of e- gained in reduction = number of e- lost in oxidation
Add the balanced half-reactions, and include states of
matter.

21-4
Balancing Redox Reactions in Acidic Solution

Cr2O72-(aq) + I-(aq) Cr3+(aq) + I2(s)

Step 1: Divide the reaction into half-reactions.


Cr2O72- Cr3+
I- I2
Step 2: Balance the atoms and charges in each half-reaction.
For the Cr2O72-/Cr3+ half-reaction:
Balance atoms other than O and H:
Cr2O72- 2Cr3+
Balance O atoms by adding H2O molecules:

Cr2O72- 2Cr3+ + 7H2O

21-5
Balance H atoms by adding H+ ions:
14H+ + Cr2O72- 2Cr3+ + 7H2O

Balance charges by adding electrons:


6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
This is the reduction half-reaction. Cr2O72- is reduced, and is the
oxidizing agent. The O.N. of Cr decreases from +6 to +3.

For the I-/I2 half-reaction:


Balance atoms other than O and H:
2I- I2
There are no O or H atoms, so we balance charges by adding electrons:
2I- I2 + 2e-
This is the oxidation half-reaction.I- is oxidized, and is the reducing
agent. The O.N. of I increases from -1 to 0.

21-6
Step 3: Multiply each half-reaction, if necessary, by an integer so that
the number of e- lost in the oxidation equals the number of e- gained
in the reduction.
The reduction half-reaction shows that 6e- are gained; the oxidation
half-reaction shows only 2e- being lost and must be multiplied by 3:
3(2I- I2 + 2e-)
6I- 3I2 + 6e-

Step 4: Add the half-reactions, canceling substances that appear on


both sides, and include states of matter. Electrons must always cancel.
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
6I- 3I2 + 6e-
6I-(aq) + 14H+(aq) + Cr2O72-(aq) 3I2(s) + 7H2O(l) + 2Cr3+(aq)

21-7
Balancing Redox Reactions in Basic Solution
An acidic solution contains H+ ions and H2O. We use H+
ions to balance H atoms.
A basic solution contains OH- ions and H2O. To balance
H atoms, we proceed as if in acidic solution, and then
add one OH- ion to both sides of the equation.
For every OH- ion and H+ ion that appear on the same
side of the equation we form an H2O molecule.

Excess H2O molecules are canceled in the final step,


when we cancel electrons and other common species.

21-8
Sample Problem 21.1 Balancing a Redox Reaction in Basic
Solution

PROBLEM: Permanganate ion reacts in basic solution with oxalate


ion to form carbonate ion and solid manganese dioxide.
Balance the skeleton ionic equation for the reaction
between NaMnO4 and Na2C2O4 in basic solution:
MnO4-(aq) + C2O42-(aq) MnO2(s) + CO32-(aq) [basic solution]
PLAN: We follow the numbered steps as described in the text, and
proceed through step 4 as if this reaction occurs in acidic
solution. Then we add the appropriate number of OH- ions
and cancel excess H2O molecules.
SOLUTION:
Step 1: Divide the reaction into half-reactions.
MnO4- MnO2 C2O42- CO32-

21-9
Sample Problem 21.1
Step 2: Balance the atoms and charges in each half-reaction.
Balance atoms other than O and H:
MnO4- MnO2 C2O42- 2CO32-

Balance O atoms by adding H2O molecules:


MnO4- MnO2 + 2H2O 2H2O + C2O42- 2CO32-

Balance H atoms by adding H+ ions:


4H+ + MnO4- MnO2 + 2H2O 2H2O + C2O42- 2CO32- + 4H+

Balance charges by adding electrons:


3e- + 4H+ + MnO4- MnO2 + 2H2O 2H2O + C2O42- 2CO32- + 4H+ + 2e-
[reduction] [oxidation]

21-10
Sample Problem 21.1

Step 3: Multiply each half-reaction, if necessary, by an integer so that


the number of e- lost in the oxidation equals the number of e- gained
in the reduction.
x2 6e- + 8H+ + 2MnO4- 2MnO2 + 4H2O
x3 6H2O + 3C2O42- 6CO32- + 12H+ + 6e-

Step 4: Add the half-reactions, canceling substances that appear on


both sides.
6e- + 8H+ + 2MnO4- 2MnO2 + 4H2O
2 6H2O + 3C2O42- 6CO32- + 412H+ + 6e-
2MnO4- + 2H2O + 3C2O42- 2MnO2 + 6CO32- + 4H+

21-11
Sample Problem 21.1

Basic. Add OH- to both sides of the equation to neutralize H+, and
cancel H2O.

2MnO4- + 2H2O + 3C2O42- + 4OH- 2MnO2 + 6CO32- + [4H+ + 4OH-]


2MnO4- + 2H2O + 3C2O42- + 4OH- 2MnO2 + 6CO32- + 24H2O

Including states of matter gives the final balanced equation:

2MnO4-(aq) + 3C2O42-(aq) + 4OH-(aq) 2MnO2(s) + 6CO32-(aq) + 2H2O(l)

21-12
Electrochemical Cells

A voltaic cell uses a spontaneous redox reaction


(G < 0) to generate electrical energy.
- The system does work on the surroundings.

A electrolytic cell uses electrical energy to drive a


nonspontaneous reaction (G > 0).
- The surroundings do work on the system.

Both types of cell are constructed using two electrodes


placed in an electrolyte solution.
The anode is the electrode at which oxidation occurs.

The cathode is the electrode at which reduction occurs.

21-13
Figure 21.2 General characteristics of (A) voltaic and (B) electrolytic
cells.

21-14
Spontaneous Redox Reactions
A strip of zinc metal in a solution of Cu2+ ions will react
spontaneously:
Cu2+(aq) + 2e- Cu(s) [reduction]
Zn(s) Zn2+(aq) + 2e- [oxidation]
Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)

Zn is oxidized, and loses electrons to Cu2+.

Although e- are being transferred, electrical energy is not


generated because the reacting substances are in the
same container.

21-15
Construction of a Voltaic Cell

Each half-reaction takes place in its own half-cell, so


that the reactions are physically separate.

Each half-cell consists of an electrode in an electrolyte


solution.

The half-cells are connected by the external circuit.


A salt bridge completes the electrical circuit.

21-16
Operation of the Voltaic Cell
Oxidation (loss of e-) occurs at the anode, which is
therefore the source of e-.
Zn(s) Zn2+(aq) + 2e-

Over time, the Zn(s) anode decreases in mass and the


[Zn2+] in the electrolyte solution increases.

Reduction (gain of e-) occurs at the cathode, where the e-


are used up.
Cu2+(aq) + 2e- Cu(s)
Over time, the [Cu2+] in this half-cell decreases and the
mass of the Cu(s) cathode increases.

21-17
Figure 21.4B A voltaic cell based on the zinc-copper reaction.

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Oxidation half-reaction Reduction half-reaction


Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

After several hours, the The Cu cathode gains


Zn anode weighs less as mass over time as Cu2+
Zn is oxidized to Zn2+. ions are reduced to Cu.

21-18
Charges of the Electrodes

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

The anode produces e- by the oxidation of Zn(s). The


anode is the negative electrode in a voltaic cell.

Electrons flow through the external wire from the anode


to the cathode, where they are used to reduce Cu2+ ions.

The cathode is the positive electrode in a voltaic cell.

21-19
The Salt Bridge
The salt bridge completes the electrical circuit and allows
ions to flow through both half-cells.

As Zn is oxidized at the anode, Zn2+ ions are formed and


enter the solution.
Cu2+ ions leave solution to be reduced at the cathode.
The salt bridge maintains electrical neutrality by allowing
excess Zn2+ ions to enter from the anode, and excess
negative ions to enter from the cathode.
A salt bridge contains nonreacting cations and anions, often
K+ and NO3-, dissolved in a gel.

21-20
Flow of Charge in a Voltaic Cell

Electrons flow through the wire from anode to cathode.

Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

Zn2+ SO42-
Cations move through the salt Anions move through the salt
bridge from the anode solution bridge from the cathode solution
to the cathode solution. to the anode solution.

By convention, a voltaic cell is shown with the anode on


the left and the cathode on the right.

21-21
Active and Inactive Electrodes
An active electrode is an active component in its half-
cell and is a reactant or product in the overall reaction.

An inactive electrode provides a surface for the reaction


and completes the circuit. It does not participate actively
in the overall reaction.
- Inactive electrodes are necessary when none of the reaction
components can be used as an electrode.

Inactive electrodes are usually unreactive substances such


as graphite or platinum.

21-22
Figure 21.5 A voltaic cell using inactive electrodes.

Oxidation half-reaction Reduction half-reaction


2I-(aq) I2(s) + 2e- MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l)

Overall (cell) reaction


2MnO4-(aq) + 16H+(aq) + 10I-(aq) 2Mn2+(aq) + 5I2(s) + 8H2O(l)

21-23
Notation for a Voltaic Cell
The components of each half-cell are written in the same
order as in their half-reactions.

The anode components The cathode


are written on the left. components are written
on the right.
Zn(s)Zn2+(aq)Cu2+(aq) Cu(s)

The single line shows a phase The double line shows that the half-
boundary between the cells are physically separated.
components of a half-cell.

If needed, concentrations of dissolved components


are given in parentheses. (If not stated, it is assumed
that they are 1 M.)

21-24
Notation for a Voltaic Cell

graphite I-(aq)I2(s)MnO4-(aq), H+(aq), Mn2+(aq) graphite

The inert electrode is specified.


A comma is used to show components
that are in the same phase.

21-25
Sample Problem 21.2 Describing a Voltaic Cell with Diagram
and Notation

PROBLEM: Draw a diagram, show balanced equations, and write the


notation for a voltaic cell that consists of one half-cell with
a Cr bar in a Cr(NO3)3 solution, another half-cell with an
Ag bar in an AgNO3 solution, and a KNO3 salt bridge.
Measurement indicates that the Cr electrode is negative
relative to the Ag electrode.

PLAN: From the given contents of the half-cells, we write the half-
reactions. To determine which is the anode compartment
(oxidation) and which is the cathode (reduction), we note the
relative electrode charges. Electrons are released into the
anode during oxidation, so it has a negative charge. Since Cr
is negative, it must be the anode, and Ag is the cathode.

21-26
Sample Problem 21.2

SOLUTION:
The half-reactions are:
Ag+(aq) + e- Ag(s) [reduction; cathode]
Cr(s) Cr3+(aq) + 3e- [oxidation; anode]
The balanced overall equation is:
3Ag+ + Cr(s) 3Ag(s) + Cr3+(aq)

The cell notation is given by:


Cr(s)Cr3+(aq)Ag+(aq)Ag(s)

The cell diagram shows the anode on


the left and the cathode on the right.

21-27
Electrical Potential and the Voltaic Cell
When the switch is closed and no reaction is occurring,
each half-cell is in an equilibrium state:
Zn(s) Zn2+(aq) + 2e- (in Zn metal)
Cu(s) Cu2+(aq) + 2e- (in Cu metal)
Zn is a stronger reducing agent than Cu, so the position of
the Zn equilibrium lies farther to the right.
Zn has a higher electrical potential than Cu. When the
switch is closed, e- flow from Zn to Cu to equalize the
difference in electrical potential
The spontaneous reaction occurs as a result of the different
abilities of these metals to give up their electrons.

21-28
Cell Potential

A voltaic cell converts the G of a spontaneous redox


reaction into the kinetic energy of electrons.

The cell potential (Ecell) of a voltaic cell depends on the


difference in electrical potential between the two
electrodes.
Cell potential is also called the voltage of the cell or the
electromotive forces (emf).

Ecell > 0 for a spontaneous process.

21-29
Table 21.1 Voltages of Some Voltaic Cells

Voltaic Cell Voltage (V)


Common alkaline flashlight battery 1.5
Lead-acid car battery (6 cells 12 V) 2.1
Calculator battery (mercury) 1.3
Lithium-ion laptop battery 3.7
Electric eel (~5000 cells in 6-ft eel 0.15
= 750 V)
Nerve of giant squid 0.070
(across cell membrane)

21-30
Figure 21.6 Measuring the standard cell potential of a zinc-
copper cell.

The standard cell potential is designated Ecell and is


measured at a specified temperature with no current
flowing and all components in their standard states.

21-31
Standard Electrode Potentials
The standard electrode potential (Ehalf-cell) is the potential
of a given half-reaction when all components are in their
standard states.

By convention, all standard electrode potentials refer to


the half-reaction written as a reduction.

The standard cell potential depends on the difference


between the abilities of the two electrodes to act as
reducing agents.

Ecell = Ecathode (reduction) - Eanode (oxidation)

21-32
The Standard Hydrogen Electrode
Half-cell potentials are measured relative to a standard
reference half-cell.

The standard hydrogen electrode has a standard


electrode potential defined as zero (Ereference = 0.00 V).

This standard electrode consists of a Pt electrode with H2


gas at 1 atm bubbling through it. The Pt electrode is
immersed in 1 M strong acid.
2H+(aq; 1 M) + 2e- H2(g; 1 atm) Eref = 0.00V

21-33
Figure 21.7 Determining an unknown Ehalf-cell with the standard
reference (hydrogen) electrode.
Oxidation half-reaction
Zn(s) Zn2+(aq) + 2e

Reduction half-reaction
2H3O+(aq) + 2e- H2(g) + 2H2O(l)

Overall (cell) reaction


Zn(s) + 2H3O+(aq) Zn2+(aq) + H2(g) + 2H2O(l)
21-34
Sample Problem 21.3 Calculating an Unknown Ehalf-cell from Ecell

PROBLEM: A voltaic cell houses the reaction between aqueous bromine


and zinc metal:
Br2(aq) + Zn(s) Zn2+(aq) + 2Br-(aq) Ecell = 1.83 V.
Calculate Ebromine, given that EzInc = -0.76 V

PLAN: Ecell is positive, so the reaction is spontaneous as


written. By dividing the reaction into half-reactions, we
see that Br2 is reduced and Zn is oxidized; thus, the zinc
half-cell contains the anode. We can use the equation for
Ecell to calculate Ebromine.

SOLUTION:
Br2(aq) + 2e- 2Br-(aq) [reduction; cathode]
Zn(s) Zn2+(aq) + 2e- [oxidation; anode] Ezinc = -0.76 V

21-35
Sample Problem 21.3

Ecell = Ecathode Eanode

1.83 = Ebromine (-0.76)

1.83 + 0.76 = Ebromine

Ebromine = 1.07 V

21-36
Comparing Ehalf-cell values

Standard electrode potentials refer to the half-reaction as


a reduction.

E values therefore reflect the ability of the reactant to act


as an oxidizing agent.

The more positive the E value, the more readily the


reactant will act as an oxidizing agent.

The more negative the E value, the more readily the


product will act as a reducing agent.

21-37
Table 21.2 Selected Standard Electrode Potentials (298 K)

Half-Reaction E(V)
F2(g) + 2e 2F(aq) +2.87
Cl2(g) + 2e 2Cl(aq) +1.36
MnO2(g) + 4H+(aq) + 2e Mn2+(aq) + 2H2O(l) +1.23
NO3-(aq) + 4H+(aq) + 3e NO(g) + 2H2O(l) +0.96

strength of reducing agent


Ag+(aq) + e Ag(s) +0.80
strength of oxidizing agent

Fe3+(g) + e Fe2+(aq) +0.77


O2(g) + 2H2O(l) + 4e 4OH(aq) +0.40
Cu2+(aq) + 2e Cu(s) +0.34
2H+(aq) + 2e H2(g) 0.00
N2(g) + 5H+(aq) + 4e N2H5+(aq) 0.23
Fe2+(aq) + 2e Fe(s) 0.44
2H2O(l) + 2e H2(g) + 2OH(aq) 0.83
Na+(aq) + e Na(s) 2.71
Li+(aq) + e Li(s) 3.05

21-38
Writing Spontaneous Redox Reactions

Each half-reaction contains both a reducing agent and an


oxidizing agent.
The stronger oxidizing and reducing agents react
spontaneously to form the weaker ones.

A spontaneous redox reaction (Ecell > 0) will occur


between an oxidizing agent and any reducing agent that
lies below it in the emf series (i.e., one that has a less
positive value for E).
The oxidizing agent is the reactant from the half-reaction
with the more positive Ehalf-cell.

21-39
Using half-reactions to write a spontaneous redox reaction:
Sn2+(aq) + 2e- Sn(s) Etin = -0.14 V
Ag+(aq) + e- Ag(s) Esilver = 0.80 V

Step 1: Reverse one of the half-reactions into an oxidation


step so that the difference between the E values will be
positive.
Here the Ag+/Ag half-reaction has the more positive E value, so it
must be the reduction. This half-reaction remains as written.
We reverse the Sn2+/Sn half-reaction, but we do not reverse the sign:
Sn(s) Sn2+(aq) + 2e- Etin = -0.14 V

21-40
Step 2: Multiply the half-reactions if necessary so that the number
of e- lost is equal to the number or e- gained.
2Ag+(aq) + 2e- 2Ag(s) Esilver = 0.80 V

Note that we multiply the equation but not the value for E.

Step 3: Add the reactions together, cancelling common species.


Calculate Ecell = Ecathode - Eanode.

Sn(s) Sn2+(aq) + 2e- Etin = -0.14 V


2Ag+(aq) + 2e- 2Ag(s) Esilver = 0.80 V

Sn(s) + 2Ag+(aq) 2Ag(s) + Sn2+(aq) Ecell = 0.94 V

Ecell = Esilver Etin = 0.80 (-0.14) = 0.94 V

21-41
Sample Problem 21.4 Writing Spontaneous Redox Reactions and
Ranking Oxidizing and Reducing Agents by
Strength
PROBLEM: (a) Combine the following three half-reactions into three
balanced equations for spontaneous reactions (A, B,
and C), and calculate Ecell for each.
(b) Rank the relative strengths of the oxidizing and reducing
agents.
(1) NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l) E = 0.96 V
(2) N2(g) + 5H+(aq) + 4e- N2H5+(aq) E = -0.23 V
(3) MnO2(s) +4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) E = 1.23 V

PLAN: To write the redox equations, we combine the possible


pairs of half-reactions. In each case the half-reaction with
the less positive value for E will be reversed. We make e-
lost equal to e- gained, add the half-reactions and calculate
Ecell. We can then rank the relative strengths of the
oxidizing and reducing agents by comparing E values.
21-42
Sample Problem 21.4
SOLUTION: (a)
For (1) and (2), equation (2) has the smaller, less positive E value:

(1) NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l) E = 0.96 V


(2) N2H5+(aq) N2(g) + 5H+(aq) + 4e- E = -0.23 V

We multiply equation (1) by 4 and equation (2) by 3:


(1) 4NO3-(aq) + 16H+(aq) + 12e- 4NO(g) + 8H2O(l) E = 0.96 V
(2) 3N2H5+(aq) 3N2(g) + 15H+(aq) + 12e- E = -0.23 V

(A) 4NO3-(aq) + 3N2H5+(aq) + H+(aq) 3N2(g) + 4NO(g) + 8H2O(l)

Ecell = 0.96 V (-0.23 V) = 1.19 V

21-43
Sample Problem 21.4

For (1) and (3), equation (1) has the smaller, less positive E value:

(1) NO(g) + 2H2O(l) NO3-(aq) + 4H+(aq) + 3e- E = 0.96 V


(3) MnO2(s) +4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) E = 1.23 V

We multiply equation (1) by 2 and equation (3) by 3:


(1) 2NO(g) + 4H2O(l) 2NO3-(aq) + 8H+(aq) + 6e- E = 0.96 V
(3) 3MnO2(s) +12H+(aq) + 6e- 3Mn2+(aq) + 6H2O(l) E = 1.23 V

(B) 3MnO2(s) + 4H+(aq) + 2NO(g) 2Mn2+(aq) + 2NO3-(aq) + 2H2O(l)

Ecell = 1.23 V (0.96 V) = 0.27 V

21-44
Sample Problem 21.4

For (2) and (3), equation (2) has the smaller, less positive E value:
(2) N2H5+(aq) N2(g) + 5H+(aq) + 4e- E = -0.23 V
(3) MnO2(s) +4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) E = 1.23 V

We multiply equation (3) by 2:


(2) N2H5+(aq) N2(g) + 5H+(aq) + 4e- E = -0.23 V
(3) 2MnO2(s) +8H+(aq) + 4e- 2Mn2+(aq) + 4H2O(l) E = 1.23 V

(C) N2H5+(aq) + 2MnO2(s) + 3H+(aq) N2(g) + 2Mn2+(aq) + 4H2O(l)

Ecell = 1.23 V (-0.23 V) = 1.46 V

21-45
Sample Problem 21.4:

(b) We first rank the oxidizing and reducing agents within each
equation, then we can compare Ecell values.
Equation (A) Oxidizing agents: NO3- > N2
Reducing Agents: N2H5+ > NO
Equation (B) Oxidizing agents: MnO2 > NO3-
Reducing Agents: N2H5+ > NO
Equation (C) Oxidizing agents: MnO2 > N2
Reducing Agents: N2H5+ > Mn2+

Comparing the relative strengths from the Ecell values:


Oxidizing agents: MnO2 > NO3- > N2
Reducing agents: N2H5+ > NO > Mn2+

21-46
The Activity Series of the Metals

Metals that can displace H2 from acid are metals that


are stronger reducing agents than H2.
2H+(aq) + 2e- H2(g) E = 0.00V
Fe(s) Fe2+ + 2e- E = -0.44 V
Fe(s) + 2H+(aq) Fe2+(aq) + H2(g) Ecell = 0.44 V

The lower the metal is in the list of half-cell potentials,


the more positive its Ehalf-cell and the stronger it is as a
reducing agent.
The larger (more positive) the Ehalf-cell of a metal, the
more active a metal it is.

21-47
The Activity Series of the Metals

Metals that cannot displace H2 from acid are metals that


are weaker reducing agents than H2.
2H+(aq) + 2e- H2(g) E = 0.00V
2Ag(s) 2Ag+ + 2e- E = 0.80 V
2Ag(s) + 2H+(aq) 2Ag+(aq) + H2(g) Ecell = -0.80 V

The higher the metal is in the list of half-cell potentials,


the smaller its Ehalf-cell and the weaker it is as a reducing
agent.
The smaller (more negative) the Ehalf-cell of a metal, the
less active a metal it is.

21-48
The Activity Series of the Metals

Metals that can displace H2 from water are metals


whose half-reactions lie below that of H2O:
2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.42 V
2Na(s) 2Na+(aq) + 2e- E = -2.17 V
2Na(s) + 2H2O(l) 2Na+(aq) + H2(g) + 2OH-(aq) Ecell = 2.29 V

21-49
The Activity Series of the Metals

We can also predict whether one metal can displace


another from solution. Any metal that is lower in the list
of electrode potentials (i.e., has a larger E value) will
reduce the ion of a metal higher up the list.
Zn(s) Zn2+(aq) + 2e- E = -0.76V
Fe2+(aq) + 2e- Fe(s) E = -0.44V
Zn (s) + Fe2+(aq) Zn2+(aq) + Fe(s) Ecell = 0.32 V

21-50
Figure 21.8 The reaction of calcium in water.

Oxidation half-reaction Reduction half-reaction


Ca(s) Ca2+(aq) + 2e- 2H2O(l) + 2e- H2(g) + 2OH-(aq)

Overall (cell) reaction


Ca(s) + 2H2O(l) Ca2+(aq) + H2(g) + 2OH-(aq)

21-51
Free Energy and Electrical Work

For a spontaneous redox reaction, G < 0 and Ecell > 0.

n = mol of e- transferred
G = -nFEcell F is the Faraday constant
= 9.65x104 J/Vmol e-

Under standard conditions, G = -nFEcell and

RT ln K or 0.0592 V log K
Ecell = Ecell =
nF n
for T = 298.15 K

21-52
Figure 21.10 The interrelationship of G, Ecell, and K.

G Reaction Parameters at the Standard State

Reaction at standard-
G K Ecell state conditions
<0 >1 >0 spontaneous

G
ll
ce

0 1 0 at equilibrium
E

=-
- nF

>0 <1 <0 nonspontaneous

RT
=

ln
G

Ecell K

RT ln K
Ecell =
nF

21-53
Sample Problem 21.5 Calculating K and G from Ecell

PROBLEM: Lead can displace silver from solution, and silver occurs in
trace amounts in some ores of lead.
Pb(s) + 2Ag+(aq) Pb2+(aq) + 2Ag(s)
As a consequence, silver is a valuable byproduct in the
industrial extraction of lead from its ore. Calculate K and
G at 298.15 K for this reaction.

PLAN: We divide the spontaneous redox reaction into the half-reactions


and use values from Appendix D to calculate Ecell. From this we
can find K and G.
SOLUTION:
Writing the half-reactions with their E values:

(1) Ag+(aq) + e- Ag(s) E = 0.80 V


(2) Pb2+(aq) + 2e- Pb(s) E = -0.13 V

21-54
Sample Problem 21.5

We need to reverse equation (2) and multiply equation (1) by 2:


(1) 2Ag+(aq) + 2e- 2Ag(s) E = 0.80 V
(2) Pb(s) Pb2+(aq) + 2e- E = -0.13 V
2Ag+(aq) + Pb(s) 2Ag(s) + Pb2+(aq) Ecell = 0.80 (-0.13) = 0.93 V

RT ln K 0.0592 V log K = 0.93 V


Ecell = =
nF 2
0.93 V x 2
log K = = 31.42 K = 2.6x1031
0.0592 V

G = -nFEcell = - 2 mol e x 96.5 kJ x 0.93 V


-

mol rxn Vmol e-

= -1.8x102 kJ/mol rxn

21-55
Cell Potential and Concentration

Nernst Equation Ecell = Ecell - RT ln Q


nF

When Q < 1, [reactant] > [product], ln Q < 0, so Ecell > Ecell


When Q = 1, [reactant] = [product], ln Q = 0, so Ecell = Ecell
When Q > 1, [reactant] < [product], ln Q > 0, so Ecell < Ecell

We can simplify the equation as before for T = 298.15 K:

Ecell = Ecell - 0.0592 V log Q


n

21-56
Sample Problem 21.6 Using the Nernst Equation to Calculate Ecell

PROBLEM: In a test of a new reference electrode, a chemist constructs


a voltaic cell consisting of a Zn/Zn2+ half-cell and an H2/H+
half-cell under the following conditions:
[Zn2+] = 0.010 M [H+] = 2.5 M PH2 = 0.30 atm
Calculate Ecell at 298 K.
PLAN: To apply the Nernst equation and determine Ecell, we must
know Ecell and Q. We write the equation for the spontaneous
reaction and calculate Ecell from standard electrode
potentials. We must convert the given pressure to molarity in
order to have consistent units.
SOLUTION:
(1) 2H+(aq) + 2e- H2(g) E = 0.00 V
(2) Zn(s) Zn2+(aq) + 2e- E = -0.76 V
2H+(aq) + Zn(s) H2(g) + Zn2+(aq) Ecell = 0.00 (-0.76) = 0.76 V

21-57
Sample Problem 21.6

Converting pressure to molarity:


n P 0.30 atm
= = = 1.2x10-2 M
V RT 0.0821 atmL x 298.15 K
molK
[H2][Zn2+] = 0.012 x 0.010
Q= = 1.9x10-5
[H+]2 (2.5)2

Solving for Ecell at 25C (298.15 K), with n = 2:

Ecell = Ecell - 0.0592 V log Q


n
0.0592 V
= 1.10 V - log(1.9x10-5) = 0.76 (-0.14 V) = 0.90 V
2

21-58
Figure 21.11A The relation between Ecell and log Q for the zinc-
copper cell.

If the reaction starts with [Zn2+] < [Cu2+] (Q < 1), Ecell is higher than the
standard cell potential.
As the reaction proceeds, [Zn2+] decreases and [Cu2+] increases, so
Ecell drops. Eventually the system reaches equilibrium and the cell can
no longer do work.
21-59
Figure 21.11B The relation between Ecell and log Q for the zinc-
copper cell.

A summary of the changes in Ecell as any voltaic cell operates.

21-60
Concentration Cells

A concentration cell exploits the effect of concentration


changes on cell potential.

The cell has the same half-reaction in both cell


compartments, but with different concentrations of
electrolyte:
Cu(s) Cu2+(aq; 0.10 M) + 2e- [anode; oxidation]
Cu2+(aq; 1.0 M) Cu(s) [cathode; reduction]
Cu2+(aq; 1.0 M) Cu2+(aq; 0.10 M)

As long as the concentrations of the solutions are


different, the cell potential is > 0 and the cell can do work.

21-61
Figure 21.12 A concentration cell based on the Cu/Cu2+ half-reaction.
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Oxidation half-reaction
Cu(s) Cu2+(aq, 0.1 M) + 2e- Ecell > 0 as long as the half-cell
concentrations are different.
Reduction half-reaction
Cu2+(aq, 1.0 M) + 2e- Cu(s) The cell is no longer able to do work
once the concentrations are equal.
Overall (cell) reaction
Cu2+(aq,1.0 M) Cu2+(aq, 0.1 M)

21-62
Sample Problem 21.7 Calculating the Potential of a Concentration
Cell
PROBLEM: A concentration cell consists of two Ag/Ag+ half-cells. In
half-cell A, the electrolyte is 0.0100 M AgNO3; in half-cell
B, it is 4.0x10-4 M AgNO3. What is the cell potential at
298.15 K?

PLAN: The standard half-cell potentials are identical, so Ecell is


zero, and we find Ecell from the Nernst equation. Half-cell A
has a higher [Ag+], so Ag+ ions are reduced and plate out on
electrode A, which is therefore the cathode. In half-cell B, Ag
atoms of the electrode are oxidized and Ag+ ions enter the
solution. Electrode B is thus the anode. As for all voltaic cells,
the cathode is positive and the anode is negative.

21-63
Sample Problem 21.7

SOLUTION: The [Ag+] decreases in half-cell A and increases in half-


cell B, so the spontaneous reaction is:
Ag+(aq; 0.010 M) [half-cell A] Ag+(aq; 4.0x10-4 M) [half-cell B]

0.0592 V log [Ag ]dil


+
Ecell = Ecell -
1 [Ag+]conc
4.0x10-4
= 0.0 V - 0.0592 log = 0.0828 V
0.010

21-64
Figure 21.13 Laboratory measurement of pH.

The operation of a pH meter illustrates an important application of


concentration cells. The glass electrode monitors the [H +] of the
solution relative to its own fixed internal [H+].

An older style of pH meter Modern pH meters use a


includes two electrodes. combination electrode.

21-65
Table 21.3 Some Ions Measured with Ion-Specific Electrodes

Species Detected Typical Sample


NH3/NH4+ Industrial wastewater, seawater
CO2/HCO3- Blood, groundwater
F- Drinking water, urine, soil, industrial
stack gases
Br- Grain, plant tissue
I- Milk, pharmaceuticals
NO3- Soil, fertilizer, drinking water
K+ Blood serum, soil, wine
H+ Laboratory solutions, soil, natural
waters

21-66
Electrochemical Processes in Batteries

A battery consists of self-contained voltaic cells arranged


in series, so their individual voltages are added.
A primary battery cannot be recharged. The battery is
dead when the cell reaction has reached equilibrium.

A secondary battery is rechargeable. Once it has run


down, electrical energy is supplied to reverse the cell
reaction and form more reactant.

21-67
Figure 21.15 Alkaline battery.

Anode (oxidation): Zn(s) + 2OH-(aq) ZnO(s) + H2O(l) + 2e-


Cathode (reduction): MnO2(s) + 2H2O(l) + 2e- Mn(OH)2(s) + 2OH-(aq)
Overall (cell) reaction:
Zn(s) + MnO2(s) + H2O(l) ZnO(s) + Mn(OH)2(s) Ecell = 1.5 V

21-68
Figure 21.16 Silver button battery.

Anode (oxidation): Zn(s) + 2OH-(aq) ZnO(s) + H2O(l) + 2e-


Cathode (reduction): Ag2O(s) + H2O(l) + 2e- 2Ag(s) + 2OH-(aq)
Overall (cell) reaction: Zn(s) + Ag2O(s) ZnO(s) + 2Ag(s)
Ecell = 1.6 V
The mercury battery uses HgO as the oxidizing agent instead of
Ag2O and has cell potential of 1.3 V.

21-69
Figure 21.17 Lithium battery.

The primary lithium battery is widely used


in watches, implanted medical devices,
and remote-control devices.

Anode (oxidation):
3.5Li(s) 3.5Li+ + 3.5e-
Cathode (reduction):
AgV2O5.5 + 3.5Li- + 3.5e- Li3.5V2O5.5
Overall (cell) reaction:
AgV2O5.5 + 3.5Li(s) Li3.5V2O5.5

21-70
The reactions in a lead-acid battery:
The cell generates electrical energy when it discharges as a voltaic cell.
Anode (oxidation): Pb(s) + HSO4-(aq) PbSO4(s) + H+(aq) + 2e-
Cathode (reduction):
PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e- PbSO4(s) + 2H2O(l)
Overall (cell) reaction (discharge):
PbO2(s) + Pb(s) + H2SO4(aq) 2PbSO4(s) + 2H2O(l) Ecell = 2.1 V

Overall (cell) reaction (recharge):


2PbSO4(s) + 2H2O(l) PbO2(s) + Pb(s) + H2SO4(aq)

21-71
Figure 21.19 Nickel-metal hydride battery

Anode (oxidation): MH(s) + OH-(aq) M(s) + H2O(l) + e-


Cathode (reduction): NiO(OH)(s) + H2O(l) + e- Ni(OH)2(s) + OH-(aq)
Overall (cell) reaction:
MH(s) + NiO(OH)(s) M(s) + Ni(OH)2(s) Ecell = 1.4 V

21-72
Figure 21.20 Lithium-ion battery.

Anode (oxidation):
LixC6(s) xLi+ + xe- + C6(s)
Cathode (reduction):
Li1-xMn2O4(s) + xLi+ + xe- LiMn2O4(s)
Overall (cell) reaction:
LixC6(s) + Li1-xMn2O4(s) LiMn2O4(s)
Ecell = 3.7 V

The secondary (rechargeable) lithium-ion battery is used to power laptop


computers, cell phones, and camcorders.

21-73
Figure 21.21 Hydrogen fuel cell.

Anode (oxidation): 2H2(g) 4H+(aq) + 4e-


Cathode (reduction): O2(g) + 4H+(aq) + 4e- 2H2O(g)
Overall (cell) reaction: 2H2(g) + O2(g) 2H2O(g) Ecell = 1.2 V

21-74
Fuel Cells

In a fuel cell, also called a flow cell, reactants enter the


cell and products leave, generating electricity through
controlled combustion.

Reaction rates are lower in fuel cells than in other


batteries, so an electrocatalyst is used to decrease
the activation energy.

21-75
Corrosion: an Environmental Voltaic Cell

Corrosion is the process whereby metals are oxidized to


their oxides and sulfides.

The rusting of iron is a common form of corrosion.


- Rust is not a direct product of the reaction between Fe and
O2, but arises through a complex electrochemical process.
- Rusting requires moisture, and occurs more quickly at low pH, in
ionic solutions, and when the iron is in contact with a less active
metal.

21-76
The Rusting of Iron
The loss of iron:
Fe(s) Fe2+(aq) + 2e- [anodic region; oxidation]
O2(g) + 4H+(aq) + 4e- 2H2O(l) [cathodic region; reduction]
2Fe(s) + O2(g) + 4H+(aq) 2Fe2+(aq) + 2H2O(l) [overall]

The rusting process:


Overall reaction:
2Fe2+(aq) + O2(g) + (2 + n)H2O(l) Fe2O3nH2O(s) + 4H+(aq)

H+ ions are consumed in the first step, so lowering the pH increases the
overall rate of the process. H+ ions act as a catalyst, since they are
regenerated in the second part of the process.

21-77
Figure 21.22 The corrosion of iron.

21-78
Figure 21.23 Enhanced corrosion at sea.

The high ion concentration of seawater enhances the corrosion of


iron in hulls and anchors.

21-79
Figure 21.24 The effect of metal-metal contact on the corrosion
of iron.

Fe in contact with Cu corrodes Fe in contact with Zn does not


faster. corrode. The process is known
as cathodic protection.

21-80
Figure 21.25 The use of sacrificial anodes to prevent iron corrosion.

In cathodic protection, an active metal, such as zinc, magnesium, or


aluminum, acts as the anode and is sacrificed instead of the iron.

21-81
Electrolytic Cells

An electrolytic cell uses electrical energy from an


external source to drive a nonspontaneous redox
reaction.
Cu(s) Cu2+(aq) + 2e- [anode; oxidation]
Sn2+(aq) + 2e- Sn(s) [cathode; reduction]
Cu(s) + Sn2+(aq) Cu2+(aq) + Sn(s) Ecell = -0.48 V and G = 93 kJ

As with a voltaic cell, oxidation occurs at the anode and


reduction takes place at the cathode.
An external source supplies the cathode with electrons,
which is negative, and removes then from the anode,
which is positive. Electrons flow from cathode to anode.

21-82
Figure 21.26 The tin-copper reaction as the basis of a voltaic and
an electrolytic cell.
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Sn(s) Sn2+(aq) + 2e- Cu(s) Cu2+(aq) + 2e-


Cu2+(aq) + 2e- Cu(s) Sn2+(aq) + 2e- Sn(s)

Cu2+(aq) + Sn(s) Cu(s) + Sn2+(aq) Sn2+(aq) + Cu(s) Sn(s) + Cu2+(aq)


voltaic cell electrolytic cell

21-83
Figure 21.27 The processes occurring during the discharge and
recharge of a lead-acid battery.

VOLTAIC (discharge)

Switch

ELECTROLYTIC (recharge)

21-84
Table 21.4 Comparison of Voltaic and Electrolytic Cells

Electrode
Cell Type G Ecell Name Process Sign

Voltaic <0 >0 Anode Oxidation -

Voltaic <0 >0 Cathode Reduction +

Electrolytic >0 <0 Anode Oxidation +

Electrolytic >0 <0 Cathode Reduction -

21-85
Products of Electrolysis

Electrolysis is the splitting (lysing) of a substance by the


input of electrical energy.

During electrolysis of a pure, molten salt, the cation will


be reduced and the anion will be oxidized.
During electrolysis of a mixture of molten salts
- the more easily oxidized species (stronger reducing agent) reacts
at the anode, and
- the more easily reduced species (stronger oxidizing agent) reacts
at the cathode.

21-86
Sample Problem 21.8 Predicting the Electrolysis Products of a
Molten Salt Mixture
PROBLEM: A chemical engineer melts a naturally occurring mixture of
NaBr and MgCl2 and decomposes it in an electrolytic cell.
Predict the substance formed at each electrode, and write
balanced half-reactions and the overall cell reaction.

PLAN: We need to determine which metal and nonmetal will form more
easily at the electrodes. We list the ions as oxidizing or reducing
agents.
If a metal holds its electrons more tightly than another, it has a
higher ionization energy (IE). Its cation will gain electrons more
easily, and it will be the stronger oxidizing agent.
If a nonmetal holds its electrons less tightly than another, it has a
lower electronegativity (EN). Its anion will lose electrons more
easily, and it will be the reducing agent.

21-87
Sample Problem 21.8
SOLUTION:
Possible oxidizing agents: Na+, Mg2+
Possible reducing agents: Br-, Cl-
Mg is to the right of Na in Period 3. IE increases from left to right across
the period, so Mg has the higher IE and gives up its electrons less
easily. The Mg2+ ion has a greater attraction for e- than the Na+ ion.

Mg2+(l) + 2e- Mg(l) [cathode; reduction]

Br is below Cl in Group 7A. EN decreases down the group, so Br


accepts e- less readily than Cl. The Br- ion will lose its e- more easily, so
it is more easily oxidized.
2Br-(l) Br2(g) + 2e- [anode; oxidation]

The overall cell reaction is: Mg2+(l) + 2Br-(l) Mg(l) + Br2(g)

21-88
Figure 21.28 The electrolysis of water.

Overall (cell) reaction


2H2O(l) H2(g) + O2(g)

Oxidation half-reaction Reduction half-reaction


2H2O(l) 4H+(aq) + O2(g) + 4e- 2H2O(l) + 4e- 2H2(g) + 2OH-(aq)

21-89
Electrolysis of Aqueous Salt Solutions
When an aqueous salt solution is electrolyzed
- The strongest oxidizing agent (most positive electrode potential) is
reduced, and
- The strongest reducing agent (most negative electrode potential) is
oxidized.

Overvoltage is the additional voltage needed (above


that predicted by E values) to produce gases at metal
electrodes.

Overvoltage needs to be taken into account when


predicting the products of electrolysis for aqueous
solutions.
Overvoltage is 0.4 0.6 V for H2(g) or O2(g).

21-90
Summary of the Electrolysis of Aqueous Salt Solutions

Cations of less active metals (Au, Ag, Cu, Cr,


Pt, Cd) are reduced to the metal.
Cations of more active metals are not reduced.
H2O is reduced instead.
Anions that are oxidized, because of
overvoltage from O2 formation, include the
halides, except for F-.
Anions that are not oxidized include F- and
common oxoanions. H2O is oxidized instead.

21-91
Sample Problem 21.9 Predicting the Electrolysis Products of
Aqueous Salt Solutions
PROBLEM: What products form at which electrode during electrolysis of
aqueous solution of the following salts?
(a) KBr (b) AgNO3 (c) MgSO4
PLAN: We identify the reacting ions and compare their electrode
potentials with those of water, taking the 0.4 0.6 V overvoltage
into account. The reduction half-reaction with the less negative
E occurs at the cathode, while the oxidation half-reaction with
the less positive E occurs at the anode.
SOLUTION:
(a) KBr K+(aq) + e- K(s) E = -2.93
2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.42V
Despite the overvoltage, which makes E for the reduction of water
between -0.8 and -1.0 V, H2O is still easier to reduce than K+, so
H2(g) forms at the cathode.

21-92
Sample Problem 21.9

2Br-(aq) Br2(l) + 2e- E = 1.07 V


2H2O(l) O2(g) + 4H+(aq) + 4e- E = 0.82 V
The overvoltage makes E for the oxidation of water between 1.2
and 1.4 V. Br- is therefore easier to oxidize than water, so Br2(g)
forms at the anode.
(b) AgNO3 Ag+(aq) + e- Ag(s) E = 0.80 V
2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.42V

As the cation of an inactive metal, Ag+ is a better oxidizing agent


than H2O, so Ag(s) forms at the cathode.

NO3- cannot be oxidized, because N is already in its highest (+5)


oxidation state. Thus O2(g) forms at the anode:
2H2O(l) O2(g) + 4H+(aq) + 4e-

21-93
Sample Problem 21.9

(c) MgSO4 Mg2+(aq) + 2e- Mg(s) E = -2.37 V


2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.42V

Mg2+ is a much weaker oxidizing agent than H2O, so H2(g) forms at


the cathode.
SO42- cannot be oxidized, because S is already in its highest (+6)
oxidation state. Thus O2(g) forms at the anode:
2H2O(l) O2(g) + 4H+(aq) + 4e-

21-94
Stoichiometry of Electrolysis

Faradays law of electrolysis states that the amount of


substance produced at each electrode is directly
proportional to the quantity of charge flowing through
the cell.

The current flowing through the cell is the amount of


charge per unit time. Current is measured in amperes.

Current x time = charge

21-95
Figure 21.29 A summary diagram for the stoichiometry of
electrolysis.

MASS (g)
of substance CURRENT
oxidized or (A)
reduced

M (g/mol) time (s)

AMOUNT (mol)
AMOUNT (mol) CHARGE
of substance
of electrons (C)
oxidized or
transferred
reduced balanced Faraday
half-reaction constant
(C/mol e-)

21-96
Sample Problem 21.10 Applying the Relationship Among Current,
Time, and Amount of Substance
PROBLEM: A technician plates a faucet with 0.86 g of Cr metal by
electrolysis of aqueous Cr2(SO4)3. If 12.5 min is allowed for
the plating, what current is needed?
PLAN: To find the current, we divide charge by time, so we need to find
the charge. We write the half-reaction for Cr3+ reduction to get
the amount (mol) of e- transferred per mole of Cr. We convert
mass of Cr needed to amount (mol) of Cr. We can then use the
Faraday constant to find charge and current.
mass (g) of Cr needed
divide by M
mol of Cr
3 mol e- = 1 mol Cr
mol e- transferred Charge (C) current (A)
1 mol e- = 9.65x104 C divide by time in s
21-97
Sample Problem 21.10

SOLUTION:
Cr3+(aq) + 3e- Cr(s)

0.86 g Cr x 1 mol Cr x 3 mol e- = 0.050 mol e-


52.00 g Cr 1 mol Cr

Charge (C) = 0.050 mol e- x 9.65x10 C = 4.8x103 C


4

1 mol e-

charge (C) 4.8x103 C x 1 min


Current (A) = = = 6.4 C/s = 6.4 A
time (s) 12.5 min 60 s

21-98
Chemical Connections
Figure B21.1 The mitochondrion

Mitochondria are subcellular particles outside the cell nucleus that


control the electron-transport chain, an essential part of energy
production in living organisms.

21-99
Chemical Connections
Figure B21.2 The main energy-yielding steps in the electron-
transport chain (ETC).

21-
Chemical Connections
Figure B21.3 Coupling electron transport to proton transport to
ATP synthesis.

21-