Physical Chemistry

Engel
Physical Chemistry
Thomas Engel Philip Reid

Reid
Third Edition

Third Edition
ISBN 978-1-29202-224-6

9 781292 022246
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 Electrochemical Cells, Batteries, and Fuel Cells

8 Determination of Eº and Activity

Coefficients Using an Electrochemical Cell
E⫺0.05916 V log10 m/m⬚

The main problem in determining standard potentials lies in knowing the value of the
activity coefficient g ; for a given solute concentration. The best strategy is to carry out
measurements of the cell potential at low concentrations, where g ; : 1, rather than near
unit activity, where g ; differs appreciably from 1. Consider an electrochemical cell consist-
ing of the Ag+/Ag and standard hydrogen electrode half-cells at 298 K. The cell reaction is
E⬚ Ag+(aq) + 1>2 H2(g) Δ Ag(s) + H+(aq) and Q = (aAg + )-1. Because the activ-
ities of H2(g) and H+(aq) are 1, they do not appear in Q. Assume that the Ag+ arises
from the dissociation of AgNO3. Recall that the activity of an individual ion cannot be
measured directly. It must be calculated from the measured activity a ; and the defini-
tion an; = an++ an-- . In this case, a2; = aAg+ aNO3- and a ; = aAg+ = aNO3-. Similarly,
g ; = gAg+ = gNO3- and mAg+ = mNO3- = m ; = m, and E is given by
m /m° RT RT RT
E = E°Ag+>Ag + ln aAg+ = E°Ag+>Ag + ln(m>m ⴰ ) + ln g ; (41)
F F F
FIGURE 7
The value of E° and the activity coeffi- At low enough concentrations, the Debye–Hückel limiting law is valid and
cient can be measured by plotting the left- log g ; = - 0.5092 2m ; >m ⴰ at 298 K. Using this relation, Equation (41) can be
hand side of Equation (42) against the rewritten in the form
square root of the molality.
E - 0.05916 log10(m>m ⴰ ) = E°Ag+>Ag - 0.05916 * 0.50902(m>m ⴰ )
= E°Ag+>Ag - 0.030112(m>m ⴰ ) (42)
The left-hand side of this equation can be calculated from measurements and plotted as a
function of 2(m>m ⴰ ). The results will resemble the graph shown in Figure 7. An
extrapolation of the line that best fits the data to m = 0 gives E° as the intercept with the
vertical axis. Once E° has been determined, Equation (41) can be used to calculate g ; .
Electrochemical cells provide a powerful method of determining activity coeffi-
cients because cell potentials can be measured more accurately and more easily than
colligative properties such as freezing point depression or boiling point elevation. Note
that although the Debye–Hückel limiting law was used to determine E°, it is not neces-
sary to use the limiting law to calculate activity coefficients once E° is known.

9 Cell Nomenclature and Types

of Electrochemical Cells
It is useful to use an abbreviated notation to describe an electrochemical cell. This nota-
tion includes all species involved in the cell reaction and phase boundaries within the
cell, which are represented by a vertical line. As will be seen later in this section, the
metal electrodes appear at the ends of this notation, the half-cell in which oxidation
occurs is written on the left, and the electrode is called the anode. The half-cell in
which reduction occurs is written on the right, and the electrode is called the cathode.
We briefly discuss an additional small contribution to the cell potential that arises from
the differing diffusion rates of large and small ions in an electrical field. As an electrochem-
ical reaction proceeds, ions that diffuse rapidly across a liquid–liquid junction, such as H+,
will travel farther than ions that diffuse slowly, such as Cl-, in a given time. At steady state,
a dipole layer is built up across this junction, and the rates of ion transfer through this dipole
layer become equal. This kinetic effect will give rise to a small junction potential between
two liquids of different composition or concentration. Such a junction potential is largely
eliminated by a salt bridge. An interface for which the junction potential has been elimi-
nated is indicated by a pair of vertical lines.The separation of different phases that are in
contact and allow electron transfer is shown by a solid vertical line. A single dashed line is
used to indicate a liquid–liquid interface across which charge transfer can occur.

308
 Electrochemical Cells, Batteries, and Fuel Cells

For example, the abbreviated notation for the Daniell cell containing a salt bridge is
Zn(s) ƒ ZnSO4(aq)7CuSO4(aq) ƒ Cu(s) (43)
2+
and a cell made up of the Zn/Zn half-cell and the standard hydrogen electrode is
described by
Zn(s) ƒ ZnSO4(aq) ƒ ƒ H+(aq) ƒ H2(g) ƒ Pt(s) (44)
The overall reaction in this cell is Zn(s) + 2 H+(aq) Δ Zn2+(aq) + H2(g). In gen-
eral, in such a cell the solutions are physically separated by a porous membrane to prevent
mixing of the solutions. In this case, the junction potential has not been eliminated.
The half-cell and overall reactions can be determined from the abbreviated notation
in the following way. An electron is transferred from the electrode at the far left of the
abbreviated notation to the electrode on the far right through the external circuit. The
number of electrons is then adjusted to fit the half-cell reaction. This procedure is
illustrated in Example Problem 7.

EXAMPLE PROBLEM 7

Determine the half-cell reactions and the overall reaction for the cell designated
Ag(s) ƒ AgCl(s) ƒ Cl-(aq, a ; = 0.0010) 7 Fe2 + (aq, a ; = 0.50)
Fe3 + (aq, a ; = 0.10) ƒ Pt(s)

Solution
The anode and cathode reactions are
Ag(s) + Cl-(aq) : AgCl(s) + e-
Fe3+(aq) + e- : Fe2+(aq)
The overall reaction is
Ag(s) + Cl-(aq) + Fe3+(aq) Δ AgCl(s) + Fe2+(aq)
Only after the cell potential is calculated is it clear whether the reaction or the reverse
reaction is spontaneous.

We have already discussed several specific half-cells and next discuss different
types of half-cells. The standard hydrogen electrode involves the equilibrium between a
gas and a dissolved species. A second such electrode is the Cl2>Cl- electrode, for
which the reduction reaction is
Cl2(g) + 2e- : 2 Cl-(aq) E° = + 1.36 V (45)
Another type of half-cell that is frequently encountered involves a metal and a metal
ion in solution. Both half-cells in the Daniell cell fall into this category.
Zn2 + (aq) + 2e- : Zn(s) E° = - 0.76 V (46)
A number of half-cells consist of a metal, an insoluble salt containing the metal, and an
aqueous solution containing the anion of the salt. Two examples of this type of half-cell
are the Ag–AgCl half-cell for which the reduction reaction is
AgCl(s) + e- : Ag(s) + Cl-(aq) E° = + 0.22 V (47)
and the calomel (mercurous chloride) electrode, which is frequently used as a reference
electrode in electrochemical cells:
Hg2 Cl2(s) + 2e- : 2 Hg(l) + 2 Cl-(aq) E° = + 0.27 V (48)
In a further type of half-cell, both species are present in solution, and the electrode is an
inert conductor such as Pt, which allows an electrical connection to be made to the
solution. For example, in the Fe3 + >Fe2+ half-cell, the reduction reaction is
Fe3 + (aq) + e- : Fe2 + (aq) E° = 0.771 V (49)

309
 Electrochemical Cells, Batteries, and Fuel Cells

TABLE 3
The Electrochemical Series

Most Strongly Reducing

10 The Electrochemical Series
(The metal is least easily oxidized.) Tables 1 and Tables 2 (see at the end of the chapter) list the reduction potentials of com-
monly encountered half-cells. The emf of a cell constructed from two of these half-
Gold cells with standard reduction potentials E°1 and E°2 is given by
(most positive reduction potential)
E°cell = E°1 - E°2 (50)
Platinum
Palladium The potential E°cell will be positive and, therefore, ¢G 6 0, if the reduction
Silver
potential for reaction 1 is more positive than that of reaction 2. Therefore, the rela-
tive strength of a species as an oxidizing agent follows the order of the numerical
Rhodium
value of its reduction potential in Table 2. The electrochemical series shown in
Copper Table 3 is obtained if the oxidation of neutral metals to their most common oxida-
Mercury tion state is considered. For example, the entry for gold in Table 3 refers to the
(Hydrogen; zero reduction potential reduction reaction
by convention)
Lead Au3 + (aq) + 3e- : Au(s) E° = 1.498 V
Tin In a redox couple formed from two entries in the list shown in Table 3, the species
Nickel lying higher in the list will be reduced, and the species lying lower in the list will be
Iron
oxidized in the spontaneous reaction. For example, the table predicts that
the spontaneous reaction in the copper–zinc couple is Zn(s) + Cu2+(aq) :
Zinc
Zn2+(aq) + Cu(s) and not the reverse reaction.
Chromium
Vanadium
EXAMPLE PROBLEM 8
Manganese
Magnesium For the reduction of the permanganate ion MnO4- to Mn2+ in an acidic solution,
Sodium E° = +1.51 V . The reduction reactions and standard potentials for Zn2+, Ag+,
and Au+ are given here:
Calcium
Potassium Zn2 + (aq) + 2e- : Zn(s) E° = -0.7618 V
Rubidium
Ag+(aq) + e- : Ag(s) E° = 0.7996 V
Cesium
Lithium Au+(aq) + e- : Au(s) E° = 1.692 V
(most negative reduction potential)
Which of these metals will be oxidized by the MnO4- ion?
Least Strongly Reducing
(The metal is most easily oxidized.) Solution
The cell potentials assuming the reduction of the permanganate ion and oxidation of
the metal are
Zn: 1.51 V + 0.761 V = 2.27 V 7 0
Ag: 1.51 V - 0.7996 V = 0.710 V 7 0
Au: 1.51 V - 1.692 V = -0.18 V 6 0
If E° 7 0, ¢G 6 0. On the basis of the sign of the cell potential, we conclude that
only Zn and Ag will be oxidized by the MnO4- ion.

11 Thermodynamics of Batteries
and Fuel Cells
Batteries and fuel cells are electrochemical cells that are designed to maximize the
ratio of output power to the cell weight or volume. Batteries contain the reactants
needed to support the overall electrochemical reaction, whereas fuel cells are designed
to accept a continuous flow of reactants from the surroundings. Batteries that cannot
be recharged are called primary batteries, whereas rechargeable batteries are called
secondary batteries.

310
 Electrochemical Cells, Batteries, and Fuel Cells

It is useful to compare the relative amount of work that can be produced through an
electrochemical reaction with the work that a heat engine could produce using the same
overall reaction. The maximum electrical work is given by
T¢S
welectrical = - ¢G = - ¢H ¢ 1 - ≤ (51)
¢H
whereas the maximum work available through a reversible heat engine operating
between Th and Tc is

wthermal = qhot e = - ¢H a b
Th - Tc
(52)
Th
where e is the efficiency of a reversible heat engine (see Section 5.2). To compare the
maximum thermal and electrical work, we use the overall reaction for the familiar
lead-acid battery used in cars. For this reaction, ¢GRⴰ = - 376.97 kJ mol-1 ,
¢HRⴰ = - 227.58 kJ mol-1 , and ¢SRⴰ = 501.1 J K-1 mol-1 . Assuming Th = 600. K
and Tc = 300. K and that the battery operates at 300. K, then
welectrical
= 3.31 (53)
wthermal
This calculation shows that much more work can be produced in the electrochemical
reaction than in the thermal reaction. This comparison does not even take into account
that the lead-acid battery can be recharged, whereas the thermal reaction can only be
run once.

12 The Electrochemistry of Commonly Used

Batteries
The lead-acid battery was invented in 1859 and is still widely used in automobiles.
Because the power required to start an automobile engine is on the order of a kilowatt,
the current capacity of such a battery must be on the order of a hundred amperes.
Additionally, such a battery must be capable of 500 to 1500 recharging cycles from a
deep discharge. In recharging batteries, the reaction product in the form of a solid must
be converted back to the reactant, also in the form of a solid. Because the solids in gen-
eral have a different crystal structure and density, the conversion induces mechanical
stress in the anode and cathode, which ultimately leads to a partial disintegration of
these electrodes. This is the main factor that limits the number of charge–discharge
cycles that a battery can tolerate.
The electrodes in the lead-acid battery consist of Pb powder and finely divided PbO
and PbSO4 supported on a Pb frame. The electrodes are supported in a container con-
taining concentrated H2SO4. In use, a battery is discharged. Some batteries, including
the lead-acid battery, can be recharged by applying an external voltage to convert prod-
ucts back to reactants. In that case, the role of anode and cathode are reversed. To avoid
confusion, we write half cell and overall reactions for the discharge mode. In the lead-
acid battery, the cell reactions at the cathode and anode are
PbO2(s) + 4 H+(aq) + SO24 - (aq) + 2e- : PbSO4(s) + 2 H2 O(l)
E° = 1.685 V (54)

Pb(s) + SO24 - (aq) : PbSO4(s) + 2e- E° = - 0.356 V (55)

respectively, and the overall reaction is
PbO2(s) + Pb(s) + 2 H2 SO4(aq) Δ 2 PbSO4(s) + 2 H2 O(l) E° = 2.04 V (56)
The arrows would point in the opposite direction and the sign of the emfs would be
reversed for the charging mode.
Six such cells connected in series are required for a battery that provides a nominal
potential of 12 V. The lead-acid battery is very efficient in that more than 90% of the
electrical charge used to charge the battery is available in the discharge part of the cycle.

311
 Electrochemical Cells, Batteries, and Fuel Cells

FIGURE 8 Smaller
A number of different batteries are classi-
fied with their specific energy density per
800
unit volume and per unit mass.
700

600
Li-ion
500 AA Alkaline

Wh/L
400 Ni-MH
Li-metal
300

200
Ni-Cd
100
Lead-Acid
0 Lighter
0 100 200 300 400 500
Wh/kg

This means that side reactions such as the electrolysis of water play a minimal role in
charging the battery. However, only about 50% of the lead in the battery is converted
between PbO2 and PbSO4. Because Pb has a large atomic mass, this limited convertibil-
ity decreases the power per unit mass figure of merit for the battery. Parasitic side reac-
tions also lead to a self-discharge of the cell without current flowing in the external
circuit. For the lead-acid battery, the capacity is diminished by approximately 0.5% per
day through self-discharge.
As batteries have become more common in portable devices such as cell phones
and laptop computers, energy density is a major criterion in choosing the most suitable
battery chemistry for a specific application. Figure 8 shows a comparison of different
battery types. The lead-acid battery has the lowest specific energy either in terms of
volume or mass. Next we discuss the chemistry of three commonly used rechargeable
batteries: the alkaline, nickel metal hydride, and lithium ion batteries.
The individual elements of the alkaline cell are shown in Figure 9. The anode in this
cell is powdered zinc, and the cathode is in the form of a MnO2 paste mixed with

Positive cover: Can: steel

plated steel

Metalized
Electrolyte: plastic film label
potassium
hydroxide/
water
Anode:
powdered zinc
Cathode:
manganese
Current collector:
dioxide,
brass pin
carbon

Separator: Seal: nylon

non-woven
fabric
Inner cell cover:
steel

Negative cover:
plated steel

FIGURE 9 Metal
washer Metal spur
Schematic diagram of an alkaline cell.

312