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Galvanic cell
A galvanic cell or voltaic cell, named
after Luigi Galvani or Alessandro Volta,
respectively, is an electrochemical cell that
derives electrical energy from spontaneous
redox reactions taking place within the cell.
It generally consists of two different metals
immersed in an electrolyte, or of individual
half-cells with different metals and their
ions in solution connected by a salt bridge or
separated by a porous membrane.

Volta was the inventor of the voltaic pile, the

first electrical battery. In common usage, Galvanic cell with no cation flow
the word "battery" has come to include a
single galvanic cell, but a battery properly
consists of multiple cells.[1]

Contents
History
Basic description
Electrochemical thermodynamics of galvanic cell reactions
Half reactions and conventions
Cell voltage
Galvanic corrosion
Cell types
See also
References
External links

History
In 1780, Luigi Galvani discovered that when two different metals (e.g., copper and zinc) are in contact and then both
are touched at the same time to two different parts of a muscle of a frog leg, to close the circuit, the frog's leg
contracts.[2] He called this "animal electricity". The frog's leg, as well as being a detector of electrical current, was also
the electrolyte (to use the language of modern chemistry).

A year after Galvani published his work (1790), Alessandro Volta showed that the frog was not necessary, using
instead a force-based detector and brine-soaked paper (as electrolyte). (Earlier Volta had established the law of
capacitance C = Q
V
with force-based detectors). In 1799 Volta invented the voltaic pile, which is a pile of galvanic cells
each consisting of a metal disk, an electrolyte layer, and a disk of a different metal. He built it entirely out of non-
biological material to challenge Galvani's (and the later experimenter Leopoldo Nobili)'s animal electricity theory in
favor of his own metal-metal contact electricity theory.[3] Carlo Matteucci in his turn constructed a battery entirely out

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of biological material in answer to Volta.[4] Volta's contact electricity view characterized each electrode with a number
that we would now call the work function of the electrode. This view ignored the chemical reactions at the electrode-
electrolyte interfaces, which include H2 formation on the more noble metal in Volta's pile.

Although Volta did not understand the operation of the battery or the galvanic cell, these discoveries paved the way for
electrical batteries; Volta's cell was named an IEEE Milestone in 1999.[5]

Some forty years later, Faraday (see Faraday's laws of electrolysis) showed that the galvanic cell -- now often called a
voltaic cell -- was chemical in nature. Faraday introduced new terminology to the language of chemistry: electrode
(cathode and anode), electrolyte, and ion (cation and anion). Thus Galvani incorrectly thought the source of electricity
(or source of emf, or seat of emf) was in the animal, Volta incorrectly thought it was in the physical properties of the
isolated electrodes, but Faraday correctly identified the source of emf as the chemical reactions at the two electrode-
electrolyte interfaces. The authoritative work on the intellectual history of the voltaic cell remains that by Ostwald.[6]

It was suggested by Wilhelm König in 1940 that the object known as the Baghdad battery might represent galvanic cell
technology from ancient Parthia. Replicas filled with citric acid or grape juice have been shown to produce a voltage.
However, it is far from certain that this was its purpose—other scholars have pointed out that it is very similar to
vessels known to have been used for storing parchment scrolls.[7]

Basic description
In its simplest form, a half-cell consists of a solid
metal (called an electrode) that is submerged in a
solution; the solution contains cations (+) of the
electrode metal and anions (−) to balance the charge
of the cations. The full cell consists of two half-cells,
usually connected by a semi-permeable membrane
or by a salt bridge that prevents the ions of the more
noble metal from plating out at the other electrode.

A specific example is the Daniell cell (see figure),

with a zinc (Zn) half-cell containing a solution of
ZnSO4 (zinc sulfate) and a copper (Cu) half-cell
containing a solution of CuSO4 (copper sulfate). A
salt bridge is used here to complete the electric
circuit.

If an external electrical conductor connects the

Schematic of Zn-Cu galvanic cell
copper and zinc electrodes, zinc from the zinc
electrode dissolves into the solution as Zn2+ ions
(oxidation), releasing electrons that enter the external conductor. To compensate for the increased zinc ion
concentration, via the salt bridge zinc ions leave and anions enter the zinc half-cell. In the copper half-cell, the copper
ions plate onto the copper electrode (reduction), taking up electrons that leave the external conductor. Since the Cu2+
ions (cations) plate onto the copper electrode, the latter is called the cathode. Correspondingly the zinc electrode is the
anode. The electrochemical reaction is:

Zn + Cu2+ → Zn2+ + Cu

In addition, electrons flow through the external conductor, which is the primary application of the galvanic cell.

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As discussed under #Cell voltage, the emf of the cell is the difference of the half-cell potentials, a measure of the
relative ease of dissolution of the two electrodes into the electrolyte. The emf depends on both the electrodes and on
the electrolyte, an indication that the emf is chemical in nature.

Electrochemical thermodynamics of galvanic cell

reactions
The electrochemical processes in a galvanic cell occur because reactants of high free energy (e.g. metallic Zn and
hydrated Cu2+ in the Daniell cell) are converted to lower-energy products (metallic Cu and hydrated Zn2+ in this
example). The difference in the lattice cohesive energies [8] of the electrode metals is sometimes the dominant
energetic driver of the reaction, specifically in the Daniell cell.[9] Metallic Zn, Cd, Li, and Na, which are not stabilized
by d-orbital bonding, have higher cohesive energies (i.e. they are more weakly bonded) than all transition metals,
including Cu, and are therefore useful as high-energy anode metals.[9]

The difference between the metals' ionization energies in water [9] is the other energetic contribution that can drive
the reaction in a galvanic cell; it is not important in the Daniell cell because the energies of hydrated Cu2+ and Zn2+
ions happen to be similar.[9] Both atom transfer, e.g. of zinc from the metal electrode into the solution, and electron
transfer, from metal atoms or to metal ions, play important roles in a galvanic cell. Concentration cells, whose
electrodes and ions are made of the same metal and which are driven by an entropy increase and free-energy decrease
as ion concentrations equalize, show that the electronegativity difference of the metals is not the driving force of
electrochemical processes.

Galvanic cells and batteries are typically used as a source of electrical power. The energy derives from a high-cohesive-
energy metal dissolving while to a lower-energy metal is deposited, and/or from high-energy metal ions plating out
while lower-energy ions go into solution.

Quantitatively, the electrical energy produced by a galvanic cell is approximately equal to the standard free-energy
difference of the reactants and products, denoted as ΔrGo. In the Daniell cell, most of the electrical energy of ΔrGo =
-213 kJ/mol can be attributed to the -207 kJ/mol difference between Zn and Cu lattice cohesive energies.[9]

Half reactions and conventions

A half-cell contains a metal in two oxidation states. Inside an isolated half-cell, there is an oxidation-reduction (redox)
reaction that is in chemical equilibrium, a condition written symbolically as follows (here, "M" represents a metal
cation, an atom that has a charge imbalance due to the loss of "n" electrons):

Mn+ (oxidized species) + ne− ⇌ M (reduced species)

A galvanic cell consists of two half-cells, such that the electrode of one half-cell is composed of metal A, and the
electrode of the other half-cell is composed of metal B; the redox reactions for the two separate half-cells are thus:

An+ + ne− ⇌ A
Bm+ + me− ⇌ B

The overall balanced reaction is

m A + n Bm+ ⇌ n B + m An+

In other words, the metal atoms of one half-cell are oxidized while the metal cations of the other half-cell are reduced.
By separating the metals in two half-cells, their reaction can be controlled in a way that forces transfer of electrons
through the external circuit where they can do useful work.

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The electrodes are connected with a metal wire in order to conduct the electrons that participate in the reaction.

In one half-cell, dissolved metal-B cations combine with the free electrons that are available
at the interface between the solution and the metal-B electrode; these cations are thereby
neutralized, causing them to precipitate from solution as deposits on the metal-B electrode, a
process known as plating.
This reduction reaction causes the free electrons throughout the metal-B electrode, the wire,
and the metal-A electrode to be pulled into the metal-B electrode. Consequently, electrons
are wrestled away from some of the atoms of the metal-A electrode, as though the metal-B
cations were reacting directly with them; those metal-A atoms become cations that dissolve
into the surrounding solution.
As this reaction continues, the half-cell with the metal-A electrode develops a positively
charged solution (because the metal-A cations dissolve into it), while the other half-cell
develops a negatively charged solution (because the metal-B cations precipitate out of it,
leaving behind the anions); unabated, this imbalance in charge would stop the reaction. The
solutions of the half-cells are connected by a salt bridge or a porous plate that allows ions to
pass from one solution to the other, which balances the charges of the solutions and allows
the reaction to continue.

By definition:

The anode is the electrode where oxidation (loss of electrons) takes place (metal-A electrode); in a galvanic cell, it
is the negative electrode, because when oxidation occurs, electrons are left behind on the electrode.[10] These
electrons then flow through the external circuit to the cathode (positive electrode) (while in electrolysis, an electric
current drives electron flow in the opposite direction and the anode is the positive electrode).
The cathode is the electrode where reduction (gain of electrons) takes place (metal-B electrode); in a galvanic
cell, it is the positive electrode, as ions get reduced by taking up electrons from the electrode and plate out (while
in electrolysis, the cathode is the negative terminal and attracts positive ions from the solution). In both cases, the
statement 'the cathode attracts cations' is true.
Galvanic cells, by their nature, produce direct current. The Weston cell has an anode composed of cadmium mercury
amalgam, and a cathode composed of pure mercury. The electrolyte is a (saturated) solution of cadmium sulfate. The
depolarizer is a paste of mercurous sulfate. When the electrolyte solution is saturated, the voltage of the cell is very
reproducible; hence, in 1911, it was adopted as an international standard for voltage.

A battery is a set of galvanic cells that are connected together to form a single source of voltage. For instance, a typical
12V lead–acid battery has six galvanic cells connected in series with the anodes composed of lead and cathodes
composed of lead dioxide, both immersed in sulfuric acid. Large battery rooms, for instance in a telephone exchange
providing central office power to user's telephones, may have cells connected in both series and parallel.

Cell voltage
The voltage (electromotive force Eo) produced by a galvanic cell can be estimated from the standard Gibbs free energy
change in the electrochemical reaction according to

where νe is the number of electrons transferred in the balanced half reactions, and F is Faraday's constant. However, it
can be determined more conveniently by the use of a standard potential table for the two half cells involved. The first
step is to identify the two metals and their ions reacting in the cell. Then one looks up the standard electrode potential,
Eo, in volts, for each of the two half reactions. The standard potential of the cell is equal to the more positive Eo value
minus the more negative Eo value.

For example, in the figure above the solutions are CuSO4 and ZnSO4. Each solution has a corresponding metal strip in
it, and a salt bridge or porous disk connecting the two solutions and allowing SO2−
4 ions to flow freely between the
copper and zinc solutions. To calculate the standard potential one looks up copper and zinc's half reactions and finds:

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−
Cu2+ + 2 e ⇌ Cu Eo = +0.34 V
−
Zn2+ + 2 e ⇌ Zn Eo = −0.76 V

Thus the overall reaction is:

Cu2+ + Zn ⇌ Cu + Zn2+

The standard potential for the reaction is then +0.34 V − (−0.76 V) = 1.10 V. The polarity of the cell is determined as
follows. Zinc metal is more strongly reducing than copper metal because the standard (reduction) potential for zinc is
more negative than that of copper. Thus, zinc metal will lose electrons to copper ions and develop a positive electrical
charge. The equilibrium constant, K, for the cell is given by

where F is the Faraday constant, R is the gas constant and T is the temperature in kelvins. For the Daniell cell K is
approximately equal to 1.5 × 1037. Thus, at equilibrium, a few electrons are transferred, enough to cause the electrodes
to be charged.[11]

Actual half-cell potentials must be calculated by using the Nernst equation as the solutes are unlikely to be in their
standard states,

where Q is the reaction quotient. When the charges of the ions in the reaction are equal, this simplifies to

where {Mn+} is the activity of the metal ion in solution. In practice concentration in mol/L is used in place of activity.
The metal electrode is in its standard state so by definition has unit activity. The potential of the whole cell is obtained
as the difference between the potentials for the two half-cells, so it depends on the concentrations of both dissolved
metal ions. If the concentrations are the same, and the Nernst equation is not needed under the
conditions assumed here.

R
The value of 2.303 F is 1.9845 × 10−4 V/K, so at 25 °C (298.15 K) the half-cell potential will change by only 0.05918 V/
νe if the concentration of a metal ion is increased or decreased by a factor of 10.

These calculations are based on the assumption that all chemical reactions are in equilibrium. When a current flows in
the circuit, equilibrium conditions are not achieved and the cell voltage will usually be reduced by various
mechanisms, such as the development of overpotentials.[12] Also, since chemical reactions occur when the cell is
producing power, the electrolyte concentrations change and the cell voltage is reduced. A consequence of the
temperature dependency of standard potentials is that the voltage produced by a galvanic cell is also temperature
dependent.

Galvanic corrosion

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Galvanic corrosion is a process that degrades metals electrochemically. This corrosion occurs when two dissimilar
metals are in contact with each other in the presence of an electrolyte, such as salt water, forming a galvanic cell with
H2 formation on the more noble metal. The resulting electrochemical potential then develops an electric current that
electrolytically dissolves the less noble material. A concentration cell can be formed if the same metal is exposed to two
different concentrations of electrolyte.

Cell types
Concentration cell
Electrolytic cell
Electrochemical cell
Lemon battery
Thermogalvanic cell

See also
Bioelectrochemical reactor
Biological cell voltage
Bio-nano generator
Cell notation
Desulfation
Electrochemical engineering
Electrode potential
Electrohydrogenesis
Electrosynthesis
Enzymatic biofuel cell
Galvanic series
Isotope electrochemistry
List of battery types
Sacrificial anode

References
1. "battery" (def. 4b) (http://www.merriam-webster.com/dictionary/battery), Merriam-Webster Online Dictionary
(2008). Retrieved 6 August 2008.
2. Keithley, Joseph F (1999). Daniell Cell. John Wiley and Sons. pp. 49–51. ISBN 978-0-7803-1193-0.
3. Kipnis, Nahum (2003) "Changing a theory: the case of Volta's contact electricity" (http://ppp.unipv.it/Collana/Page
s/Libri/Saggi/Nuova%20Voltiana5_PDF/p__143-162.pdf), Nuova Voltiana, Vol. 5. Università degli studi di Pavia,
2003 ISBN 88-203-3273-6. pp. 144–146
4. Clarke, Edwin; Jacyna, L. S. (1992) Nineteenth-Century Origins of Neuroscientific Concepts (https://books.google.
com/books?id=38Sjkp-JlPcC&pg=PA198), University of California Press. ISBN 0-520-07879-9. p. 199
5. "Milestones:Volta's Electrical Battery Invention, 1799" (http://www.ieeeghn.org/wiki/index.php/Milestones:Volta%2
7s_Electrical_Battery_Invention,_1799). IEEE Global History Network. IEEE. Retrieved 26 July 2011.
6. Ostwald, Wilhelm (1980). Electrochemistry: History and Theory.
7. Haughton, Brian (2007) Hidden History: Lost Civilizations, Secret Knowledge, and Ancient Mysteries. Career
Press. ISBN 1564148971. pp. 129–132
8. Ashcroft, N. W.; Mermin (1976). Solid State Physics. N. D. Brooks/Cole, Belmont, CA.
9. Schmidt-Rohr, K. (2018). "How Batteries Store and Release Energy: Explaining Basic Electrochemistry" "J.
Chem. Educ." 95: 1801-1810 https://dx.doi.org/10.1021/acs.jchemed.8b00479
10. "An introduction to redox equilibria" (http://www.chemguide.co.uk/physical/redoxeqia/introduction.html#top).
Chemguide. Retrieved 20 July 2014.

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11. Atkins, P; de Paula (2006). Physical Chemistry. J. (8th. ed.). Oxford University Press. ISBN 978-0-19-870072-2.
Chapter 7, sections on "Equilibrium electrochemistry"
12. Atkins, P; de Paula (2006). Physical Chemistry. J. (8th. ed.). Oxford University Press. ISBN 978-0-19-870072-2.
Section 25.12 "Working Galvanic cells"

External links
How to build a galvanic cell battery (http://www.miniscience.com/link/Airbattery.htm) from MiniScience.com
Galvanic Cell (http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/galvan5.swf), an animation
Interactive animation of Galvanic Cell (http://www.chem.iastate.edu/group/Greenbowe/sections/projectfolder/flashf
iles/electroChem/voltaicCell20.html). Chemical Education Research Group, Iowa State University.
Electron transfer reactions and redox potentials in GALVANIc cells - what happens to the ions at the phase
boundary (NERNST, FARADAY) (https://av.tib.eu/media/34660?pag=1) (Video by SciFox on * TIB AV-Portal (http
s://av.tib.eu/))

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