Electrochemistry Galvanic Cell

Teacher : Doaa Al Mahdawi

Subject : Chem
Aug 21

st

2015

Electrochemistry Galvanic Cell

Introduction: Chemical reactions involving the transfer of
electrons from one reactant to another are called oxidationreduction reactions or redox reactions. In a redox reaction, two halfreactions occur; one reactant gives up electrons (undergoes
oxidation) and another reactant gains electrons (undergoes
reduction).
Terms to Know:
Electrochemistrythe study of the interchange of chemical and
electrical energy
OIL RIG oxidation is loss, reduction is gain (of electrons)
Oxidation the loss of electrons, increase in charge
Reduction the gain of electrons, reduction of charge
Oxidation number the assigned charge on an atom
Oxidizing agent (OA) the species that is reduced and thus
causes oxidation
Reducing agent (RA) the species that is oxidized and thus
causes reduction

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
connected by a salt bridge, or individual half-cells separated by a
porous membrane.

Parts of the voltaic or galvanic cell:

o Anode--the electrode where oxidation occurs. After a period of
time, the anode may appear to
become smaller as it falls into solution.
o Cathode-- the anode where reduction occurs. After a period of
time it may appear larger, due to
ions from solution plating onto it.
o inert electrodesused when a gas is involved OR ion to ion
involved such as Fe3+ being reduced
to Fe2+ rather than Fe0. Made of Pt or graphite.

o Salt bridge -- a device used to maintain electrical neutrality in a

galvanic cell. This may be filled
with agar which contains a neutral salt or it may be replaced with a
porous cup.
o Electron flow -- always from anode to cathode. (through the wire)
o Standard cell notation (line notation) - anode/solution// cathode
solution/ cathode Ex. Zn/Zn2+
(1.0 M) // Cu2+ (1.0 M) / Cu
o Voltmeter - measures the cell potential (emf) . Usually is
measured in volts.

Description :

Schematic of Zn-Cu galvanic cell

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. In essence, 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

Bm+ + me

In general, then, these two metals can react with each other:
m A + n Bm+

n B + m An+

In other words, the metal atoms of one half-cell are able to induce
reduction of the metal cations of the other half-cell; conversely
stated, the metal cations of one half-cell are able to oxidize the
metal atoms of the other half-cell. When metal B has a greater
electronegativity than metal A, then metal B tends to steal
electrons from metal A (that is, metal B tends to oxidize metal A),
thus favoring one direction of the reaction:
m A + n Bm+

n B + m An+

This reaction between the metals can be controlled in a way that

allows for doing useful work:
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 are connected by a salt bridge or a porous plate
in order to conduct the ions (both the metal-A cations from one
solution, and the anions from the other solution), which
balances the charges of the solutions and thereby allows the
reaction between metal A and metal B to continue without
opposition.
By definition:
The anode is the electrode where oxidation (loss of electrons)
takes place; in a galvanic cell, it is the negative electrode, as
when oxidation occurs, electrons are left behind on the
electrode.[ These electrons then migrate to the cathode
(positive electrode). However, in electrolysis, an electric
current stimulates electron flow in the opposite direction. Thus,
the anode is positive, and the statement anode attracts anions
is true (negatively charged ions flow to the anode, while
electrons are expelled through the wire). The metal-A electrode
is the anode.
The cathode is the electrode where reduction (gain of
electrons) takes place; in a galvanic cell, it is the positive
electrode, as less oxidation occurs, fewer ions go into solution,
and less electrons are left on the electrode. Instead, there is a
greater tendency for aqueous ions to be reduced by the

incoming electrons from the anode. However, in electrolysis,

the cathode is the negative terminal, and attracting positive
ions from the solution. In this situation, the statement the
cathode attracts cations is true (positively charged, oxidized
metal ions flow toward cathode as electrons travel through the
wire). The metal-B electrode is the cathode.
Copper readily oxidizes zinc; for the Daniell cell depicted in the
figure, the anode is zinc and the cathode is copper, and the
anions in the solutions are sulfates of the respective metals.
When an electrically conducting device connects the
electrodes, the electrochemical reaction is:
Zn + Cu2+ Zn2++ Cu

Application :
A piece of zinc going into a solution as zinc ions, with each Zn atom
giving up 2 electrons, is an example of an oxidation half-reaction.
Zn(s) Zn2+(aq) + 2e(1)

The oxidation number of Zn(s) is 0 and the oxidation number of the

Zn2+ is +2. Therefore, in this half-reaction, the oxidation number
increases, which is another way of defining an oxidation. In
contrast, the reverse reaction, in which Zn2+ ions gain 2 electrons

to become Zn atoms, is an example of reduction.

Zn2+(aq) + 2e- Zn(s)
(2)
In a reduction there is a decrease (or reduction) in oxidation
number. Chemical equation representing half-reactions must be
both mass and charge balanced. In the half-reactions above, there
is one zinc on both sides of the equation. The charge is balanced
because the 2+ charge on the zinc ion is balanced by two electrons,
2e-, giving zero net charge on both sides.
Another example of reduction is the formation of solid copper from
copper ions in solution.

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

(3)

In this half-reaction the oxidation number of the aqueous copper is

+2, which decreases to 0 for the solid copper, and again charge
and mass are balanced. However, no half-reaction can occur by
itself. A redox reaction results when an oxidation and a reduction
half-reaction are combined to complete a transfer of electrons as in
the following example:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
(4)
The electrons are not shown because they are neither reactants nor
products but have simply been transferred from one species to
another (from Zn to Cu2+ in this case). In this redox reaction, the
Zn(s) is referred to as the reducing agent because it causes the
Cu2+ to be reduced to Cu. The Cu2+ is called the oxidizing agent

because it causes the Zn(s) to be oxidized to Zn2+.

Any half-reaction can be expressed as a reduction as illustrated in
the case where equation (1) can be reversed to equation (2). A
measure of the tendency for a reduction to occur is its reduction
potential, E, measured in units of volts. At standard conditions,
25 C and concentrations of 1.0 M for the aqueous ions, the
measured voltage of the reduction half-reaction is defined as the
standard reduction potential, E. Standard reduction potentials
have been measured for many half-reactions and they are listed in
tables. A short list is also provided at the end of the In-Lab section.
For the reduction half-reactions in equations (2) and (3), the
standard reduction potentials are 0.76 V for zinc and +0.34 V for
copper. The more positive (or less negative) the reduction potential,
the greater is the tendency for the reduction to occur. So Cu 2+ has
a greater tendency to be reduced than Zn2+. Furthermore, Zn has
a greater tendency to be oxidized than Cu. The values of E for the
oxidation half-reactions are opposite in sign to the reduction
potentials: +0.76 V for Zn and 0.34 V for Cu.

A galvanic cell or voltaic cell is a device in which a redox reaction,

such as the one in equation (4), spontaneously occurs and produces
an electric current. In order for the transfer of electrons in a redox
reaction to produce an electric current and be useful, the electrons
are made to pass through an external electrically conducting wire
instead of being directly transferred between the oxidizing and
reducing agents. The design of a galvanic cell (shown in Figure 1 for
the equation (4) reaction) allows this to occur. In a galvanic cell, two
solutions, one containing the ions of the oxidation half-reaction and
the other containing the ions of the reduction half-reaction, are
placed in separated compartments called half-cells. For each halfcell, the metal, which is called an electrode, is placed in the solution
and connected to an external wire. The electrode at which oxidation
occurs is called the anode [Zn in equation (4)] and the electrode at
which reduction occurs is called the cathode [Cu in equation (4)].
The two half-cells are connected by a salt-bridge that allows a
current of ions from one half-cell to the other to complete the
circuit of electron current in the external wires. When the two
electrodes are connected to an electric load (such as a light bulb or
voltmeter) the circuit is completed, the oxidation-reduction reaction
occurs, and electrons move from the anode () to the cathode (+),
producing an electric current.

At standard conditions, indicated by the superscript o, the standard

cell potential, Ecell, is based upon the standard reduction
potentials, as shown in equation (5).
Ecell = Ecathode Eanode (5)

Based on the values for the standard reduction potentials for the
two half-cells in equation (4) [0.76 V for zinc anode and +0.34 V
for copper cathode], the standard cell potential, Ecell, for the
galvanic cell in Figure 1 would be:
Ecell = +0.34 V (0.76 V) = +1.10 V

The positive voltage for Eocell indicates that at standard

conditions the reaction is spontaneous.