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Wayne M. Saslow
Department of Physics, Texas A&M University, College Station, Texas 77843-4242
I. INTRODUCTION
Voltaic cells convert chemical energy to electrical energy.
Therefore, a complete discussion of voltaic cells must discuss both chemistry and physics. However, introductory
chemistry textbooks typically discuss the chemical energies
associated with voltaic cells, but not their operation in electrical circuits; and introductory physics textbooks typically
discuss the use of voltaic cells in electrical circuits, but not
their chemical energies.
From a pedagogical viewpoint, this omission on the part
of physics texts misses at least two opportunities. First, without invoking chemistry one cannot explain many well-known
properties of voltaic cells, such as the size dependence of
their energy storage, as opposed to the size independence of
their emf. ~Voltaic cells can move electric charge; historically, this led to the terminology electromotive force, or
emf.! An operational definition of the emf of a voltaic cell, to
be justified in Sec. XI, is the open circuit voltage, as measured by a high-impedance voltmeter.
Second, without invoking chemical reactions localized at
the electrodeelectrolyte interfaces, one cannot correctly describe the voltage changes on going around a circuit containing a voltaic cell. In many texts, figures of voltage profiles
around a circuit show a linear rise in voltage within the cell,
and the internal resistance issomewhat mysteriously
placed outside the cell. However, as is well known to electrochemists, there are two steplike voltage jumps, one at each
electrodeelectrolyte interface, and the internal resistance is
associated with the electrolyte between the electrodes.13
The chemical reactions at the electrodeelectrolyte interfaces provide the source of emf, or the seat of emf, as it
has been known historically. The location of the seat of emf
was the subject of dispute at the end of the 18th and the
beginning of the 19th century.
Note that a typical automobile battery consists of six 2 V
cells in series, to raise the emf to 12 V. Each of the 2 V cells
consists of a number of voltaic cells in parallel, to raise the
current-carrying capacity. Moreover, a 12 V battery for electronics use consists of eight 1.5 V voltaic cells in series; each
cell alone could be used to power an electronic watch. The
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574
Fig. 1. Schematic of the Daniell cell during discharge. Zn21 goes into solution off the Zn electrode, and Cu21 comes out of solution onto the Cu
electrode. The electrolytes are H2O with ZnSO4 and CuSO4, which then
dissociate. See text for discussion of how mixing is avoided.
To establish the nature of the chemical reactions responsible for the emf of this cell, Heller modifies the Daniell cell.
Hellers cell consists of a sandwich of a flat plate of zinc, a
sheet of blotter paper ~Z!, a second sheet of blotter paper ~C!,
and finally a flat plate of copper. However, both blotter C,
touching the Cu electrode, and blotter Z, touching the Zn
electrode, are moistened by ZnSO4 solution. When a circuit
containing this cell is closed, no significant current flows.
However, if a few drops of CuSO4 solution are placed on the
Cu side of blotter C, then current will flow, temporarily, an
indication that Cu21 ions in the electrolyte are flowing to the
Cu electrode. On preparing the cell by first applying, for a
short time, a reverse emf ~to drive Cu21 ions from the Cu
into blotter C!, current will also flow, for a time proportional
to the charging time, when the reverse emf is removed and
the circuit is closed.5
These two experiments provide clear evidence that the
chemical energy driving the reaction is due to the competition between Zn on the Zn electrode going into the electrolyte as Zn21, and Cu on the Zn electrode going into the
electrolyte as Cu21. The Zn wins, causing Cu21 from the
CuSO4 electrolyte to plate onto the Cu electrode. Without
Cu21 ions in the electrolyte, there would be no electroplating, and no emf. As discussed in Secs. VII and VIII, the emf
is a measure of the energy release per unit charge ~more
precisely, the Gibbs free energy release per unit charge! that
is transferred from one electrode to the electrolyte and then
to the second electrode.
If CuSO4 solution actually were directly in contact with
the Zn electrode, in the absence of current flow the Zn electrode would blacken due to poisoning by Cu plating onto
it.5 This is because the Zn tends to go into the CuSO4 solution, driving Cu21 out of solution at the Zn electrode. As
already indicated, Daniell cells perform this separation by
employing a porous cup. Specifically, a porous cup containing a ZnSO4 solution is placed in a larger container of
CuSO4 solution; then a piece of Zn is placed within the
ZnSO4 solution, and a piece of Cu is placed within the
CuSO4 solution. A poor mans version of the Daniell cell
would employ a thick blotter Z moistened with ZnSO4
solutionthick enough to impede diffusion of Cu21 ions to
the Zn electrodeand a blotter C moistened with CuSO4
solution.5
III. SEAT OF EMF OF VOLTAIC CELLS
Although we have already discussed the location of the
seat of emf in the Introduction, the answer bears repeating, in
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Fig. 2. The chemical reactions at the Pb and PbO2 interfaces. Both reactions
produce PbSO4, with consumption of the ions constituting H2SO4 and production of H2O.
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~3! The more the ionic fuel on the electrodes and in the
electrolyte, the larger the energy storage by a voltaic
cell. This explains why large D cells last longer than
small AAA cells.
~4! The chemical reactions driving voltaic cells provide a
characteristic electromotive force, or emf ~energy per
unit charge transported around the circuit!. Hence cells
with the same chemical reactions ~e.g., AAA cells and D
cells! have the same emfs.
~5! The greater the electrode area, the greater the current a
voltaic cell can provide. This explains why larger D cells
provide more current than smaller AAA cells.
The first four of these items follow from our discussion of
energetics in Sec. VII. The fifth is implied by our discussion
of resistance in Sec. XI.
Physics coursesand physicistsgain credibility with
students by explaining such well-known facts about batteries, which typically are not discussed elsewhere. Moreover, a
student armed with the knowledge that chemical reactions
drive a voltaic cell might be able to recognize that someone
claiming to have a voltaic cell of 30 V is either lying, ignorant that his cell is really a battery of voltaic cells in
series, or is destined to receive the Nobel Prize in Chemistry
~or Physics! for discovering a new form of chemical bonding. Because the typical chemical bonding energy per electron is on the order of an eV, the typical voltaic cell has an
emf on the order of a volt. The maximum voltaic cell emf to
date is found in cells using Li, with emfs as large as 4.5 V.
The finite amount of energy stored in voltaic cells and
batteries of them ~in series and/or in parallel! can be seen in
the fact that they are rated in terms of the finite amount of
charge they can send around a circuit. This charge is measured in terms of amp-hours ~1 amp-hour equals 3600 C!. A
good car battery might be rated at 100 amp-hours, or 360 000
C. By way of comparison, note that a mole of electrons is
about 96 500 C ~a unit known as the faraday!.
V. ELECTRODES AND ELECTROLYTE IN MORE
DETAILSOME TERMINOLOGY
The reader may find it helpful to be reminded or informed
~as the case may be! of certain chemical and electrochemical
terminology. This material is not really necessary for the
sections that follow.
A. Half-cells
Electrochemists refer to each electrode and its associated
electrolyte as a half-cell. 13,6,7 Electrochemists distinguish between two types of electrolyte. Supporting, or
spectator, electrolyte consists of nonreactant ionswhich
can affect the electric field and can carry current in the bulk
of the cell, although they do not react at the electrodes. Nonsupporting electrolyte consists of the reactant ions.
B. Standard hydrogen electrode SHE
It has become conventional to determine the emf of each
half-cell relative to a standard electrode consisting of H2 gas
bubbled over platinum in water of pH7 ~the concentration of
H1 is 1027 moles per liter!. At atmospheric pressure and
temperature T525 C, this is known as the standard hydrogen electrode, or SHE. The H2 gas serves as the reacting part
of the electrode, and the chemically unaffected platinum
serves as the part of the electrode that provides a source or
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~1!
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Fig. 3. ~a! Detailed view of a voltaic cell and ~b! schematic view of a voltaic
cell.
When the electrodes are the same, they pump with equal
strengths in opposite directions, so there is no net emf. Since
there is an emf associated with each electrode, the net emf E
is their difference,
E5E21[E2 2E1 52 ~ E1 2E2 ! [2E12 .
~2!
~3!
Cu2112e 2 Cu.
~4!
Note that the Zn21 changes its environment, going from the
solid electrode to the electrolyte solution; hence the energy
~properly, free energy! involved here is not merely the energy to remove the electrons, which would involve only the
work function. By Voltas relationship, Eq. ~2!, the emf associated with this is 0.7622~20.345!51.107 V. The Zn is
the negative electrode, so it would be the shorter electrode on
typical circuit diagrams, the Cu being the longer electrode. In
Fig. 3~b!, the Cu would be on the left, and the Zn would be
on the right.
At each electrode, the reaction stops when the emf for the
electrode reaction is cancelled by the voltage change brought
about by the charge separation.
Wayne M. Saslow
577
~5!
where N 1,i is one of the ions associated with the reaction, and
E 1,i is the total energy release at electrode 1, from all reactants, when a single ion of type i spontaneously reacts. Because the chemical balance requires specific integer relations
between the numbers of ions, it does not matter which ion is
chosen. Further, because of Faradays law of electrolysis, the
number of ions stored on electrode 1 is proportional to the
electric charge Q 1 that electrode 1 can provide to the external circuit. Hence we can rewrite ~5! by introducing the energy per charge E1 associated with the faradaic chemical reaction at electrode 1, and the charge Q 1 that can be driven
from the electrode to the circuit by that reaction:
E 1 5E1 Q 1 .
~6!
Similarly,
E 2 5E2 Q 2 .
~7!
d E5 d E 1 1 d E 2 5 ~ E2 2E1 ! d Q 2 .
~8!
d E cell5Ed Q cell ,
E5E2 2E1 .
~10!
1 Q2
.
2 C
~11!
When the cell and the capacitor are connected, the cell
will discharge, and the capacitor will charge. If the cell has
(0)
an initial charge Q (0)
50, then by
cell , and the capacitor Q
(0)
charge conservation Q cell5Q cell2Q after the capacitor has
received a charge Q. In equilibrium, the total energy will be
a minimum. By ~10! and ~11! we thus have
05
d
d
Q2
0!
E~ Q ~cell
2Q ! 1
~ E cell1E cap! 5
dQ
dQ
2C
5 2E1
~9!
Q
.
C
~12!
From ~12! we thus deduce that the voltage drop across the
capacitor, when there is no more charge flow, is
DV5
Q
5E.
C
~13!
Q2
2C
0!
0!
2CE2 1 21 CE2 5E ~cell
2 21 CE2 .
5E ~cell
~14!
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Fig. 6. Ion density profile for lead-acid cell: ~a! fast discharge and ~b!
relaxation after fast discharge.
Fig. 5. An open circuit containing a voltaic cell and the voltage profile
around the circuit.
The chemically inclined reader will note that we have considered the equilibrium condition for a system in a real environment, at a given temperature T and pressure P. In that
case, thermodynamic theory tells us to minimize the total
energy of the system ~voltaic cell, capacitor, and environment!. This is equivalent to minimizing the Gibbs free energy for the voltaic cell and capacitor alone. ~Since the capacitor is taken to have no volume or entropy, the Gibbs free
energy and the energy are the same for it.! Hence E really
should be interpreted as the change in Gibbs free energy per
unit charge.13 One of Hellers experiments makes this point
clearly.5
IX. VOLTAIC CELLS ON OPEN CIRCUIT
It is well known that, for a parallel plate capacitor, the
larger the plate separation, the smaller the capacitance C.
Hence, if the two electrodes of an isolated voltaic cell are
thought of as the opposite plates of a capacitor, that capacitor
has a very small C. Similarly, a voltaic cell that is part of a
circuit with an open switch may be thought of as connected
to a capacitor of very small C. Small amounts of charge
~equal and opposite! go to the two sides of the switch, producing a voltage difference. By ~13! this corresponds to
DV5E, so that for a voltaic cell on open circuit, the terminal
voltage is the same as the emf. Hence, measuring the open
circuit voltage of the cell with a voltmeter ~as indicated in
the introduction! yields the emf. In Fig. 5 we show an open
circuit and the corresponding voltage for it as we go around
the circuit. To be specific, we have taken E2 51.4 V and E1
520.6 V ~so E52.0 V!; there is a voltage gain at each electrode. For later purposes, when we consider current flow, we
will take the internal resistance to have the value r50.1 V,
and the external resistance to have the value R50.4 V. Note
the jumps in voltage that occur at each of the electrodes, and
the change in voltage across the switch.
To produce DV 1 at electrode #1, charges 6Q (1)
electrode must
build up on the electrode and electrolyte sides of the interface. Treating that interface as a parallel plate capacitor of
plate separation d 1 and dielectric of dielectric constant k, we
have
DV 1 5E 1 d 1 ,
E 15
1!
Q ~electrode
A 1 ke 0
~15!
~16!
tance per unit area. It is a nontrivial matter to actually determine d 1 , known as the thickness of the dipole layer. Electrochemists also call this the electric double layer. In
practice, the capacitance per unit area is measured, and d 1 is
deduced. Since automobile batteries have plate areas of
about 5 m2, their capacitance is on the order of 12 F. This
large battery capacitance smoothes out voltage changes in
automobile electrical systems.
Each electrode of the voltaic cell possesses a dipole moment
~17!
p5Q electroded.
s5
ne 2 t
,
m
~18!
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Fig. 7. Ion density profile for lead-acid cell: ~a! fast charge and ~b! relaxation after fast charge.
Fig. 8. Ion density profile for lead-acid cell: slow discharge leads to a
steadily decreasing, nearly uniform density.
t5
w2
,
D
~19!
580
~20!
Fig. 9. A closed circuit containing a voltaic cell and the voltage profile
around the circuit.
Positive DV 2 tends to drive current to the right. A measurement of DV 2 for I50 would yield E2 , and if I depends
linearly on DV 2 , a measurement of the slope of I vs DV 2
would yield r 2 . As for ordinary resistors, the electrode resistance varies inversely with area. This explains point 5 in Sec.
IV.
For electrode #1, positive emf drives current to the right,
so we take
present model, the largest current that a voltaic cell can provide. It cannot provide this current for very long, because the
ions in the vicinity of the electrodes will be rapidly depleted,
leading to an increase in r. The present discussion, with fixed
r, is valid only for discharges that are either so slow, or last
such a short time, that such depletion does not occur.
I5
I52
E1 2DV 1
.
r1
~21!
B. Voltaic cell in series with a resistor
DV 1 5E1
~ no current flow! .
~22!
DV electrolyte
.
r electrolyte
~23!
E2DV
,
r
r5r electrolyte1r 1 1r 2 ,
~24!
E
r1R
~25!
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Fig. 10. ~a! A single ZnCu voltaic cell and ~b! Voltas Pile, using ZnCu
cells, showing the extra, unnecessary metallic plates at the leads.
A. Galvani
In 1786 Galvani began a series of electrophysiology experiments on freshly prepared frog specimens: spinal cord B
connected to crural nerve C connected to leg muscle D. Connected to spinal cord B was grounded wire A, and leg muscle
D rested on metal frame E. Thus ABCDE were all connected
in order, but there was no circuit. The leg muscle would go
into convulsions when there was a nearby electrical discharge, either from an electrical device within his laboratory,
or from atmospheric discharge in the outdoors. ~The current
causing the convulsions is now known to be due to electrostatic induction.19!
On rare but noticeable occasions, the leg muscle would
convulse without apparent source of discharge. Finally,
wearied by such fruitless waiting, I began to scrape and press
the hook @A# fastened to the backbone @spinal cord B# against
the iron railing @E, touching the leg muscle D#...I then noticed frequent contractions, none of which depended on
variations in the weather. 18 That is, Galvani had connected
A to E, producing the circuit ABCDEA.
In this way, Galvani discovered that two dissimilar metals
~A and E! must be placed in a circuit with the frog specimen
~B,C,D! in order to cause the leg muscle to convulse, although he did not fully appreciate the significance of the
metals. He made the assumption of a very fine nervous
fluid that during the phenomenon flowed into the muscles
from the nerves, similar to the electric current in the Leyden
flask @a two-plate capacitor#. 18 Thus, his source of animal
electricity ~distinct from ordinary electricity! was the nervous system, which through the nerves ~assumed to be insulated on their outer surface! could bring animal electricity to
the inner part of the muscle, leaving the exterior of the
muscle oppositely charged.19 Spasms would occur when the
nerves and the muscle exterior were connected; here is
where, to Galvani, the role of the metalsas conductors of
electricityentered.
Galvanis explanation was incorrect, but he had made a
great discovery, which he published in 1791. Galvani is one
of the founders of the field of electrophysiology.19,20
B. Volta
The physicist Voltaalready known for his discovery of
methane and for electrical studies that included the invention
of the electrophorus and the relation between charge and
voltage for capacitorsbegan to study Galvanis effect. He
realized that the frogs legs were serving as extremely sensitive detectors of electricity, rather than as sources of electricity. By 1792 Volta had established that the two metals
~dry conductors! were necessary, but that the frogs leg
was not. By using more conventional ~but sensitive! detectors of electricity, he found that the frogs leg could be replaced by what he called a moist conductor ~i.e., an electrolyte, like salt water!. Volta went on to discover the
electrochemical series, which enabled him to determine that
an effective 1.55 V battery ~still in use today! can be made
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from silver ~Ag! and zinc ~Zn! electrodes. He also made the
observation that placing intermediate metals in the circuit
~e.g., between the silver and the zinc! had no effect on the
current produced.
In 1800, Volta invented what came to be known as the
voltaic pile: a battery of voltaic cells connected in series,
which made the effects that he had been studying much more
intense. See Fig. 10. One of his early piles had 32 ZnAg
voltaic cells in series, with about 50 V across the terminals
of the pile, a powerful battery indeed. Almost immediately,
more chemically inclined scientists utilized the voltaic pile to
decompose water, collecting hydrogen at one electrode and
oxygen at the other. Thus was born the subject of electrochemistry.
Utilizing his considerable experimental skill, in 1797
Volta also discovered another effect related to voltaic cells
the contact potential between two dissimilar metals, which
causes a transfer of electric charge. The contact potential,
unlike the chemical emf, involves only electrons. It is a measure of the work function of a metal. ~Recall that the work
function is the minimum energy to remove an electron from
a metal. It is related to the minimum energy to remove an
electron from an isolated atom of that metal.!
Although Volta was aware that oxidation occurs at the
silver electrode, he focused only on the electric current aspect of his cells, considering the associated flow of chemicals to be a mere side effect, of no fundamental significance.
His view was that the contact potential at the metalmetal
interface was the power source that drove the electric current
in his cells, and that the electrolyte served only to bring the
other ends of the metals to the same electrical potential. In
other words, to Volta the voltaic cell was a perpetual motion
machine. As he writes explicitly on March 20, 1780:18
[The apparatus either] works without stopping, or its
charge is again automatically restored after each sparking. In other words it has an inexhaustible charge...[The
pile] consists of a plate of silver in contact with one of
zinc, and is connected with the next pair through a sufficient layer of moisture, which should better be salt water
than plain...
Volta performed his work some 50 years before conservation of energy was an established principle. He was wrong
about the location of the seat of emf, but his reputation,
justly deserved on the basis of his many contributions to the
science of electricity, kept the scientific community from seriously challenging his viewpoint for many years. Even after
Faradays work on electrolysis ~chemists refer to Faradays
law as the law of electrolysis! established that the electrical
and chemical effects are inextricable, many prominent scientists continued to accept the contact potential as the energy
source for the voltaic cell.
Wayne M. Saslow
582
Applied Chemistry! where voltaic cells are drawn so that positive emf
corresponds to rightward current flow. Physicists employ a convention
where the larger electrode is used to indicate the direction of current flow.
This notation is more flexible, because it permits voltaic cells to be given
any orientation, as is needed for real circuits.
5
P. Heller ~unpublished!.
6
I. N. Levine, Physical Chemistry, 4th ed. ~McGrawHill, New York,
1995!. See Chap. 14.
7
R. A. Alberty and R. J. Silbey, Physical Chemistry, 2nd ed. ~Wiley, New
York, 1997!. See Chap. 7.
8
For a theoretical estimate, see H. Reiss and A. Heller, The Absolute
Potential of the Standard Hydrogen ElectrodeA New Estimate, J.
Phys. Chem. 89, 42074213 ~1985!. For a measurement, see W. N.
Hansen and G. J. Hansen, Absolute Half-Cell PotentialA Simple Direct Measurement, Phys. Rev. A 36, 13961402 ~1987!. For a survey,
see S. Trasatti, The Absolute Electrode PotentialThe End of the
Story, Electrochim. Acta 35, 269271 ~1990!.
9
M. Faraday, reprinted in W. F. Magie, A Source Book in Physics ~Harvard
U.P., Cambridge, MA, 1963!. See pp. 492495. Magie cites the original
material as M. Faraday, Philosophical Transactions of 1834, p. 77, and M.
Faraday, Experimental Researches in Electricity, Vol. I, p. 195.
10
L. P. Williams, Michael Faraday ~Basic Books, New York, 1965!. See p.
242.
11
J. C. Maxwell, A Treatise on Electricity and Magnetism ~Clarendon, Oxford, 1891! ~reprinted by Dover, New York, 1954!. See Sec. 237.
12
L. Pauling, General Chemistry, 3rd ed. ~Freeman, San Francisco, 1970!
~reprinted by Dover, New York, 1988!.
13
Chemists normally write the Gibbs free energy change DG, for the cell, of
emf E, in terms of the faraday F ~96 500 coulombs! and the number n of
faradays that pass through the cell under discharge. Thus DG52EnF.
14
W. M. Saslow, What Happens When You Leave the Car Lights on Overnight: Violation of Local Electroneutrality in Slow, Steady Discharge of a
Lead-Acid Cell, Phys. Rev. Lett. 76, 48494852 ~1996!.
15
O. Blackwood, General Physics ~Wiley, New York, 1943!. See figure on
p. 456.
16
E. M. Purcell, Electricity and Magnetism ~McGrawHill, New York,
1965!. See the two figures on p. 137. Note that these figures do not appear
in the second edition.
17
W. Scott, The Physics of Electricity and Magnetism, 2nd ed. ~Wiley, New
York, 1966!. See Fig. 5.5a ~p. 211! and Fig. 5.5b ~p. 212!.
18
The authors primary resource on the early history of the voltaic cell is W.
Ostwald, Electrochemistry: History and Theory ~Veit & Co., Leipzig,
1896!. The Smithsonian Institution and the National Science Foundation
had this remarkable two-volume work translated into English, and published by the Amerind Publishing Company, New Delhi ~1980!.
19
H. Hoff, Galvani and the Pre-Galvanian Electrophysiologists, Annals
of Science 1, 157172 ~1936!.
20
J. F. Fulton and H. Cushing, A Bibliographical Study of Galvani and
Aldini Writings on Animal Electricity, Annals of Science 1, 239268
~1936!.
21
W. L. Bragg, Electricity ~Macmillan, New York, 1936!. See p. 50.
DO THE PROBLEMS
I have done my best to simplify this subject as much as possible ~but no further!, as will your
instructor. But finally it is up to you to wrestle with the ideas and struggle for total mastery of the
subject. Others cannot do the struggling for you, any more than they can teach you to swim if you
wont enter the water. Here is the most important rule: do as many problems as you can!
R. Shankar, Basic Training in MathematicsA Fitness Program for Science Students ~Plenum Press, New York, 1995!, p.
xi.
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Wayne M. Saslow
583