Galvanic cell

A Galvanic cell, named after Luigi Galvani, is an electrochemical cell that derives electrical
energy from chemical reactions taking place within the cell. It generally consists of two different
metals connected by a salt bridge, or individual half-cells separated by a porous membrane. It is
sometimes called a "Voltaic cell", after Alessandro Volta, inventor of the voltaic pile, the first
electrical battery. In common usage, the word "battery" has come to include a single Galvanic
cell, but a battery properly consists of multiple cells.[1][2]

Contents
• History
• Description
• Cell voltage
• Notation
• Galvanic corrosion
• Cell types
• External links

History
In 1780, Luigi Galvani discovered that when two different metals (copper and zinc for example)
were connected together and then both touched to different parts of a nerve of a frog leg at the
same time, they made the leg contract.[3] He called this "animal electricity". The voltaic pile
invented by Alessandro Volta in the 1800s is similar to the galvanic cell. These discoveries
paved the way for electrical batteries.
Description
Schematic of Zn-Cu galvanic cell
A Galvanic cell consists of two half-cells. In its simplest form each half-cell consists of a metal
and a solution of a salt of the metal. The salt solution contains a cation of the metal and an anion
to balance the charge on the cation. In essence the half-cell contains the metal in two oxidation
states and the chemical reaction in the half-cell is an oxidation-reduction (redox) reaction,
written symbolically in reduction direction as
Mn+ (oxidised species) +n e- M (reduced species)
In a galvanic cell one metal is able to reduce the cation of the other and, conversely, the other
cation can oxidise the first metal. The two half-cells must be physically separated so that the
solutions do not mix together. A salt bridge or porous plate is used to separate the two solutions.
The number of electron transferred in both directions must be the same, so the two half-cells are
combined to give the whole-cell electrochemical reaction. For two metals A and B
This is not the whole story as anions must also be transferred from one half-cell to the other.
When a metal in one half-cell is oxidised anions must be transferred into that half-cell to balance
the electrical charge of the cation produced. The anions are released from the other half-cell
where a cation is reduced to the metallic state. Thus, the salt bridge or porous membrane serves
both to keep the solutions apart and to allow the flow of anions in the direction opposite opposite
to the flow of electrons in the wire connecting the electrodes.
The voltage of the Galvanic cell is the sum of the voltages of the two half-cells. It is measured by
connecting a voltmeter to the two electrodes. The voltmeter has very high resistance, so the
current flow is effectively negligible. When a device such as an electric motor is attached to the
electrodes a current flows and redox reactions occur in both half-cells. This will continue until
the concentration of the cations that are being reduced goes to zero.
For the Daniell cell, depicted in the figure, the two metals are zinc and copper and the two salts
are sulfates of the respective metal. Zinc is the more reducing metal so when a device is
connected to the electrodes, the electrochemical reaction is
Zn + Cu2+ → Zn2+ + Cu
The zinc electrode is dissolved and copper is deposited the copper electrode. By definition, the
cathode is the electrode where reduction (gain of electrons) takes place, so the copper electrode
is the cathode. The cathode attracts cations, so has a positive charge. In this case copper is the
cathode and zinc the anode.
Galvanic cells are typically used as a source of electrical power. By their nature they produce
direct current. For example, a lead-acid battery contains a number of galvanic cells. The two
electrodes are effectively lead and lead oxide.
The Weston cell was adopted as an International Standard for voltage in 1911. The anode is a
cadmium mercury amalgam, the cathode is made of pure mercury, the electrolyte is a (saturated)
solution of cadmium sulfate and the depolarizer is a paste of mercurous sulfate. When the
electrolyte solution is saturated the voltage of the cell is very reproducible, hence its use as a
standard.
Cell voltage
The standard electrical potential of a cell can be determined by use of a standard potential table
for the two half cells involved. The first step is to identify the two metals reacting in the cell.
Then one looks up the standard electrode potential, E0, in volts, for each of the two half
reactions. The standard potential for the cell is equal to the more positive E0 value minus the
more negative E0 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 SO42− ions to flow freely between the copper and zinc solutions. In order to calculate
the standard potential one looks up copper and zinc's half reactions and finds:
Cu2+ + 2 e− Cu: E0 = +0.34 V
Zn2+ + 2 e− Zn: E0 = −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 as shown
by the fact that 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, 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.[4]
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. This simplifies to
where {Mn+} is the activity of the metal ion in solution. The metal electrode is in its standard
state so by definition has unit activity. In practice concentration is used in place of activity. The
potential of the whole cell is obtained by combining the potentials for the two half-cells, so it
depends on the concentrations of both dissolved metal ions.
The value of 2.303R/F is 0.19845×10-3 V/K, so at 25 °C (298.15 K) the half-cell potential will
change by 0.05918V / n 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 do not obtain and the cell potential
will usually be reduced by various mechanisms, such as the development of overpotentials.[5]
Also, since chemical reactions occur when the cell is producing power, the electrolyte
concentrations change and the cell voltage is reduced. The voltage produced by a galvanic cell is
temperature dependent because standard potentials are temperature-dependent.
Notation
The galvanic cell, as the one shown in the figure, are conventionally described using the
following notation:
Zn(s) | ZnSO4(aq) || CuSO4(aq) | Cu(s)
(anode)----------------------------------(cathode)
An alternate notation for this cell would be:
Zn(s) | Zn+2(aq) || Cu+2(aq) | Cu(s)
Where the following applies:
• (s) denotes solid.
• (aq) means aqueous solution.
• The vertical bar, |, denotes a phase boundary.
• The double vertical bar, ||, denotes a liquid junction for which the junction potential is
near zero, such as a salt bridge.[6]
Galvanic corrosion
Main article: Galvanic corrosion
Galvanic corrosion is a process that degrades metals electrochemically. This corrosion occurs
when two dissimilar metals are placed in contact with each other in the presence of an
electrolyte, such as salt water, forming a galvanic cell. A cell can also be formed if the same
metal is exposed to two different concentrations of electrolyte. The resulting electrochemical
potential then develops an electric current that electrolytically dissolves the less noble material.
Cell types
 • Concentration cell
• Electrolytic cell
• Electrochemical cell
• Lasagna cell
• Lemon battery
External links
• Galvanic (Voltaic) Cells and Electrode Potential. Chemistry 115B, Sonoma.edu.
• Making and testing a simple galvanic cell. Woodrow Wilson Leadership Program in
Chemistry, The Woodrow Wilson National Fellowship Foundation.
• Galvanic Cell An animation.
• Interactive animation of Galvanic Cell. Chemical Education Research Group, Iowa State
University.
• Electrochemical Cells Tutorial Segment. Chemistry 30, Saskatchewan Evergreen
Curriculum.
• Glossary for Galvanic Cells. Spark Notes, by Barnes & Noble. Sparknotes.com.
• Cathodic Protection 101. A basic tutorial on galvanic cells and corrosion prevention.