About Batteries

A battery consists of one or more electrochemical cells. Each cell contains two
metal electrodes and at least one electrolyte solution (a solution containing ions
that can conduct electricity). The battery operates through electrochemical
reactions called oxidation and reduction. These reactions involve the exchange of
electrons between chemical species. If a chemical species loses one or more
electrons, this is called oxidation. The opposite process, the gain of electrons, is
called reduction.

Oxidation occurs at the Anode.

Reduction occurs at the Cathode.

If the reactive components of an electrochemical cell are placed in contact with
each other, they will react by direct transfer of electrons (an oxidation -
reduction reaction) and there is no way to harness this energy to do electrical
work. Most of the energy of the reaction is released as heat.

In most batteries, there are different materials at the two electrodes, such that
they want to react - with one material being oxidized and the other being
reduced. In the cell below, Zinc is used for the electrode on the left (the Anode)
in contact with a solution of Zinc (II) ions, possibly a solution of Zinc
Nitrate. Copper is used for the electrode on the right (the Cathode) in contact
with a solution containing Copper (II) ions, perhaps Cupric Nitrate. By keeping
the materials separated, the electrons being produced by the oxidation at the
Anode could be used to do electrical work as they are transferred to the Cathode
where they will be consumed by the reduction process.
However, the oxidation process either produces positive ions or removes negative
ions from the solution at the anode (or it may change one ion to a more positive
one), and the reduction process either removes positive ions or produces negative
ions in the solution at the cathode. This produces electrically charged solutions,
and very quickly stops the process before a measurable number of electrons are
transferred.

There must be a path for the ions to move between the two solutions in order for
electrons to flow continuously through the wire. This produces an "ion current"
within the battery with cations (positively - charged ions) moving from anode to
cathode, and anions (negatively - charged ions) moving from the cathode toward
the anode.

This path may be provided by having the two solutions in contact with each
other, but this allows diffusion of all of the ions and "runs down" the battery
pretty quickly. This diffusion can be slowed down by separating the solutions
with a membrane or a porous plug. All of these can lead to a "liquid junction
potential" due to differing rates of movement by the cations and anions. A "salt
bridge" can be used to separate the two solutions with a third concentrated
solution of well - matched cations and anions, completely eliminating the "liquid
junction potential". In a few cases, it is possible to design a battery so that both
electrodes can be placed in the same container with only one solution.

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The voltage of a cell may depend on many factors: the electrode materials, the
components and concentrations of the solutions, the type of liquid junction, the
temperature, and the pressure. The voltage also depends on the electrical
current being drawn from the cell. The voltage (E) and the current (I) are
related to the resistance (R) through Ohm's Law:
E = IR
The current is directly related to the rate at which electrons are pumped through
the wire and any resistances in the circuit. As the resistance is lowered to zero (a
short-circuit), the current increases and the voltage of the cell decreases to zero.
As the resistance is increased, the current decreases, and the voltage increases
toward a limiting value. In Chemistry, we are primarily interested in this
limiting value, the maximum voltage that the electrochemical cell can
deliver. This maximum voltage or electrochemical potential is a measure of the
maximum electrical work that can be obtained from the chemical reaction
occurring within the cell, and this can be related to the Gibbs' Free Energy
Change associated with the chemical reaction.

In the cell above, electrons are produced by metallic lead being oxidized to lead
(II) ions, and they are removed by copper (II) ions being reduced to metallic
copper. Even with the ions moving across the boundary between the solutions,
there is an increase in the concentration of lead ions on the left and a decrease in
copper ions on the right. This causes the voltage of the battery to decrease, and
eventually the voltage will decrease to zero. Some batteries are designed to be re-
chargeable by forcing electrons to flow backwards through the cell, reversing the
chemical reaction.

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Calculating the Maximum Voltage of a Cell

The Nernst Equation describes the effects of concentrations on the maximum
voltage that the chemical reaction can produce by relating the voltage to the
Standard Electrochemical Potential (E°). This Standard Electrochemical
Potential represents the maximum voltage the reaction can produce with all of
the components in their standard states or at unit activity.

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Calculating E° for a Reaction

In a cell shown above,

there is a chemical reaction occurring in the half-cell on the left, which involves
an oxidation associated with the metal electrode, which is called the anode. If
this electrode is a piece of Zinc, the oxidation is conversion of metallic zinc to zinc
ions in solution:
Zn(s) Zn2+(aq) + 2 e- (oxidation)

On the right side of this cell a reduction is occurring, associated with the metal
electrode, which is called the cathode. If this electrode is a piece of copper, the
reduction is conversion of copper (II) ions in solution into metallic copper:

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

Each of these half-cell reactions has a Standard Electrochemical

Potential. Irrespective of whether the half-cell reaction is a reduction or an
oxidation, the Standard Electrochemical Potentials are tabulated for a
reduction. Here's an abbreviated table:
The Cu/Cu2+ half-cell reaction (a reduction in this case) has Eredo = 0.339 V, and
the Zn/Zn2+ half-cell reaction (an oxidation in this case) has Eoxo = - 0.763
V. For the combined reaction,

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) .

Note that the number of electrons on the left and right hand sides of this
equation must cancel out in combining the half-cell reactions. The Standard
Electrochemical Potential for the Reaction (Erxo) is calculated by subtracting the
value for the oxidation (Eoxo ) from the value for the reduction (Eredo):

Erxo = Eredo - Eoxo = 0.339 - (-.763) = 1.102 V .

Note that the combination of half-cell potentials to obtain Erxo is not affected at
all by the numbers of electrons in the half-cell reactions.

A positive value for this result indicates that the reaction will occur as written (if
it is allowed to occur at all) as opposed to the reverse reaction. For the reverse
reaction,

Zn2+(aq) + Cu(s) Zn(s) + Cu2+(aq)

the value of the Standard Electrochemical Potential is negative , Erxo = - 1.102 V ,

because the oxidation and reduction half-cells have been reversed.

The Nernst Equation and Effects of Concentrations on the Voltage

The effect of concentration on the voltage (E) is described by the Nernst

Equation:

E = E° - (RT/NF) ln (Q) or E = E° - 2.303(RT/NF) log (Q)

in which R is the Gas Constant (8.314 J/mol-K), T is the Absolute Temperature
(K), F is the Faraday Constant (F = 96,485 C/mol), and N is the number of moles
of electrons transferred per mole of reaction (equivalents/mol). N represents the
number of electrons that are cancelled out in combining the half-cell reactions to
obtain the net reaction. Voltages are often calculated for cells near room
temperature (T = 298.15 K), and the Nernst Equation takes the form:

E = E° - (0.0257/N) ln (Q) or E = E° - (0.059/N) log (Q)

The Reaction Quotient Q is written exactly as the Equilibrium Constant for

the reaction would be written, but Q can be applied to a reaction whether it is at
equilibrium or not. For a Generalized Reaction:

a A(s) + b B(g) + c C(aq) d D(aq) + e E(g) + f F(liq) ,

The value of Q may be approximated:

Q = [D]d PEe / PBb [C]d .

(This approximation is best at low concentrations of the ions and low pressures
of any reacting gases.)

For the reaction above:

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) N=2 Erxo = 1.102 V ,

the approximate voltage is calculated as:

E(V) = 1.102 - (0.0257/2) ln ( [Zn2+(aq)] / [Cu2+(aq)] )

or
E(V) = 1.102 - (0.059/2) log ( [Zn2+(aq)] / [Cu2+(aq)] ) .

These equations show that the voltage of this cell decreases with increasing
concentration of zinc ion, and increases with increasing concentration of copper
(II) ion. This agrees with LeChatelier's Principle, such that increasing the
concentration of zinc ion "pushes" the reaction to the left, and increasing the
concentration of copper (II) ion "pushes" the reaction to the right.

The value of Erxo for a reaction may be estimated experimentally by constructing

the cell with the concentrations of all ions at unity (1.00 mol/L) and any gases at
unit pressure (1.00 bar), and measuring the voltage E(V) of the cell. Under these
conditions,
E(V) ~ Erxo .

For some reactions (none of the concentrations of ions in the expression for Q are
raised to a power other than 1) the approximation becomes even better if all of
the relevant ions are at the same (very low) concentration.

Measuring the Voltage of a Battery

Chemists use calculations with the Nernst Equation to determine the

theoretical voltage of an electrochemical cell. In doing so, they define one
electrode as the anode and the other as the cathode. They also make assumptions
regarding the reactions which will occur at those electrodes. The ultimate test of
these assumptions is measurement of the voltage. The voltage that is observed
depends on the reactions which are actually occurring, and the algebraic sign of
the reading depends on how the leads of the voltmeter are connected to the
electrodes.
Batteries have well-marked positive (+, cathode) and negative (-, anode)
electrodes, but electrochemical cells which are constructed in the laboratory do
not. When the positive lead of the voltmeter is connected to the positive pole of
the battery, a positive voltage will be observed. This means that the electrons
that are released by the oxidation at the anode are travelling through the
voltmeter to the cathode, where they are consumed in the reduction that occurs
there. Therefore, when a voltmeter is connected to an electrochemical cell, a
positive voltage indicates that the positive lead is connected to the cathode and
the negative lead is connected to the anode.
Electrochemical Cells
This is an interactive simulation of electrochemical cells, involving various metal
electrodes. The electrode is immersed in a solution of its nitrate salt. Various cells
may be constructed and the expected voltage of a cell is displayed. Calculations are
based on the Nernst Equation using reasonable approximations for activity
coefficients and the assumption of zero junction potential across the sodium nitrate
salt bridge. Cells may be constructed in order to solve problems presented at several
levels, using measured voltages and an abbreviated Table of Standard Reduction
Potentials, included in the program.

Level:
(0) The student may construct cells with various electrodes (including the
Pt/Hydrogen electrode) and concentrations, and the voltages of these cells may be
measured.

(1) A cell is presented, and the student is asked to calculate the cell's standard
potential (Eo).

(2) There is a fictitious metal/salt pair, Whodatium (Wd)/Whodatium (II)

Nitrate. The user is asked to determine the standard reduction potential (Eo) for this
pair.

(3) The student is asked to design a cell which will produce a specified standard
potential (Eo).

(4) A cell is presented (with concentrations), and the student is asked to calculate the
expected voltage (E) of the cell.

(5) The electrode menu contains five fictitious metals: Fonium (Fo), Imagium (Im),
Mysterium (My), Oddmium (Od), and Whodatium (Wd). These metals have
different properties in each problem. The user is asked to determine the activity series
for these metals. In the activity series, the most active metal has the most negative
reduction potential and the least active metal has the most positive reduction potential.

(6) The user must determine the mean ionic activity coefficient of Whodatium (II)
Nitrate in a 1.00 M solution. (Physical Chemistry Level)

Answers to the problems are checked by the program.

Purpose

The purpose of this simulations lab is to build a set of galvanic (voltaic) cells and
measure their cell potentials. These values will then be compared to the
accepted values.

Level 0: Construct a Cell

The purpose of this experiment is to build a set of voltaic cells and measure the potential
difference (voltage) produced by them. These values will then be compared to the accepted
values for these reactions.
2. Calculate the emf of a cell, given a table of standard reduction potentials.

3. Draw a particle diagram representing the dynamic events occurring at each electrode and in
the salt-bridge.
Footnotes

References

Given a diagram of a simple electrochemical cell involving two metal electrodes and
the corresponding solution of the metal ions identify: the site of oxidation reduction,
the anode, the cathode, movement of electrons, migration of ions, the chemical
equation representing the cell reaction.

The purpose of this experiment is to build a set of voltaic cells and measure the potential
difference (voltage) produced by them. These values will then be compared to the accepted
values for these reactions.