Chapter 22, 23, 24 & 25

Electroanalytical Chemistry

Why electroanalytical chemistry?

Electroanalytical methods have certain advantages over other analytical methods.
Electrochemical analysis allows for the determination of different oxidation states of an
element in a solution, not just the total concentration of the element. Electroanalytical
techniques are capable of producing exceptionally low detection limits and an abundance
of characterization information including chemical kinetics information. The other
important advantage of this method is its low cost.
History:
Polarography was first discovered by a czechoslovavian chemist by the name of
Heyrovsky in 1920. He won the Nobel prize for it in 1959. He proposed that the current
recording generated by a oxidation or reduction in a cell as the A.P. is continuously
increased:
Ox + ne Red
Oxygen Probe:
A.P. 650 mV Ag|AgCl
Reactions:
O2 + 2H2O + 4e- 4OH4Ag + 4Cl- 4AgCl + 4eHydrogen Probe:

A.P. +650 mV
Reactions:
H2O2 O2 +2H+ +2e2Ag+ + 2e- 2Ag
The following comprehensive chart below shows the applications of electrochemistry and
its interactions with other branches of science and technology.
Electrochemical Cells
Extremely important classes of oxidation and reduction reactions are used to provide
useful electrical energy in batteries. A simple electrochemical cell can be made from
copper and zinc metals with solutions of their sulfates. In the process of the reaction,
electrons can be transferred from the zinc to the copper through an electrically
conducting path as a useful electric current. An electrochemical cell can be created by
placing metallic electrodes into an electrolyte where a chemical reaction either uses or
generates an electric current. Electrochemical cells that generate an electric current are
called voltaic cells or galvanic cells, and common batteries consist of one or more such
cells. In other electrochemical cells an externally supplied electric current is used to drive
a chemical reaction, which would not occur spontaneously. Such cells are called
electrolytic cells.
Voltaic Cells: A voltaic cell is an electrochemical cell that external electrical
current flow can be created using any two different metals since metals differ in
their tendency to lose electrons. Zinc more readily electrons than copper, so
placing zinc and copper metal in solutions of their salts can cause electrons to
flow through an external wire which leads from the zinc to the copper. The
following is a diagram of a voltaic cell.

As a zinc atom provides the electrons, it becomes a positive ion and goes into
aqueous solution, decreasing the mass of the zinc electrode. On the copper side, the
two electrons received allow it to convert a copper ion from solution into an
uncharged copper atom which deposits on the copper electrode, increasing its mass.
In order for the voltaic cell to continue to produce an external electric current, there
must be a movement of the sulfate ions in solution from the right to the left to
balance the electron flow in the external circuit. The metal ions themselves must be
prevented from moving between the electrodes, so some kind of porous membrane
or other mechanism must provide for the selective movement of the negative ions in
the electrolyte from the right to the left.
Galvanic Cells: A galvanic cell consists of at least two half cells, a reduction cell
and an oxidation cell. Chemical reactions in the two half cells provide the energy
for the galvanic cell operations. The reactions always run spontaneously in the
direction that produced a positive cell potential. The following shows a picture
of an old fashioned galvanic cell:

-the net reaction in a cell is the sum of the two half reactions
-the potential is the measure of the tendency of the cell to
move towards equilibrium
-Galvanic cells react in a way that produces electrical energy
-Electrolytic cells consume energy
-Chemically reversible cell exists when reversing the
direction of current reverses the reaction at the electrodes

The Daniell Cell

This cell is based on the overall reaction

[Cu(OH ) ] + + Zn --> Cu + [Zn(OH ) ] +
2 6

(aq)

2 6

(aq)

and functions by dissolution of Zn from the anode and deposition of Cu at the cathode. It
is therefore very simply represented as
Zn | [Zn(OH ) ] + || [Cu(OH ) ] + | Cu
or just as
Zn | Zn(II) || Cu(II) | Cu
2 6

(aq)

(aq)

2 6

(aq)

(aq)

22A-1. Conduction in a Cell:

-charge is conducted by three distinct processes:
1) in the electrodes and the external conductor, electrons
serve as carriers
2)within the solution the flow of electricity involves the
migration of both the cations and the anions
3)oxidation and reduction occurs at the 2 electrode surfaces
22A-2 Solution Structure- The Double Layer
It is very important to realize that electrochemical measurements involve
heterogeneous systems because an electrode can only donate or accept electrons from a
species that is present in a layer of solution that is immediately adjacent to the electrode.
22A-3 Faradaic and Nonfaradiac Currents
Two types of processes can conduct currents across and electrode solution interface. One
kind involves a direct transfer of electrons via and oxidation reaction at one electrode and
reduction reaction at the other. Processes of this type are called faradaic processes
because they are govern by Faradays Law, which states that the amount of chemical
reaction at an electrode is proportional to the current; the resulting currents are called
faradaic currents.
22A-4 Mass Transfer in Cells with the Passage of Current
- three mechanisms bring about these mass transfer: convection,
migration, and diffusion. Convection involves mechanical motion of
the solution as a result of stirring or the flow of the solution past the
surface of the electrode. Migration is the movement of ions through
the solution brought about by electrostatic attraction between the ions
and the charged electrode. Diffusion is the motion of species brought
about by a concentration gradient.

22A-6 Anodes and Cathodes:

-Cathode- the electrode where reduction occurs in an

electrochemical cell
-Anode- the electrode where oxidation occurs in an
electrochemical cell
-reactions at cathodes
-electrons supplied by external circuit via an inert
electrode (platinum or gold)
-some examples are:
Cu2+ + 2e- <=> Cu(s)
Fe3+ + e- <=> Fe2+
2H+ + 2e- <=> H2(g)
AgCl(s) + e- <=> Ag(s) + Cl-reactions at anodes
-some examples are:
Cu(s) <=>
Cu2+ + 2e2+
3+
Fe <=> Fe + eH2(g) <=> 2H+ + 2eAg(s) + Cl- <=> AgCl(s) + e22A-7 Cells without Liquid Junctions:
-liquid junction - the interface between 2 different
electrolytic solutions
-cell can contain more than one
-a small Junction Potential arises at these interfaces
-sometimes it is possible to prepare cells that share a
common electrolyte to avoid this problem

22A-8 Schematic Representation of Cells:

-anode and information on the solution it is contacting on left
-single vertical line indicates phase boundary where
potential might develop
-two vertical lines indicates liquid junction
-concentration or activity put in parentheses
-example:
Zn/ZnSO4(azn2+ = 1.00)//CuSO4(acu2+ + 1.00)/Cu
Principles of Electrolysis:
When an electric current is forced to pass through an electrolyte or electrolyte solution,
chemical reactions take place both at the anode and at the cathode. The stoichiometry of
these reactions obeys Faraday's laws of electrolysis. However, when several different
reactions are possible at an electrode of an electrolytic cell then the process which
actually does take place will be determined by the potential of the electrode. The
reactions which take place in electrolytic cells are those reactions which require the least
potential difference between the two electrodes.
The reactions which occur at the electrodes during electrolysis will be the oxidation and
the reduction of the solvent unless some solute is more easily oxidized or reduced than is
the solvent. Electrolysis of an aqueous solution of Na2SO4 will produce hydrogen at the
cathode and oxygen at the anode because reduction of H+(aq) is easier than is reduction
of Na+(aq) and oxidation of water is easier than is oxidation of aqueous sulfate ion. The
actual potentials will be close to the standard potentials, and the standard potential of H+
(aq)/H2(g) is less negative than is the standard potential of Na+(aq)/Na, while the standard
potential of O2(g)/H2O is less positive than the standard potential of sulfate oxidation. The
standard potential of sulfate oxidation is so positive that it is meaningless in aqueous
solutions, in which no higher oxidation state than six has been found for sulfur.
Electrolysis of an aqueous solution of copper sulfate will produce copper at the cathode,
because both the Cu2+/Cu+ and Cu+/Cu couples have standard potentials which are
considerably less negative than the standard potential of hydrogen. The electrolysis will

again produce oxygen at the anode, because Cu2+(aq) cannot be further oxidized in
aqueous solution.
Electrolysis of an aqueous solution of NaBr will produce hydrogen at the cathode, as the
aqueous sodium sulfate solution did, because neither Na+(aq) nor Br-(aq) can be reduced
at potentials which are less negative than standard hydrogen. The electrolysis of aqueous
NaBr solutions will produce bromine at the anode because the standard potential of
bromide oxidation is less positive than that of the oxidation of water.
Electrolysis of a solution of aqueous CuBr2 will produce copper at the cathode and
bromine at the anode because these are the least negative possible reduction and the least
positive possible oxidation reactions in that solution. The anode reaction in any
electrolysis will always be the oxidation which occurs at the least positive potential and
the cathode reaction will always be the reduction which occurs at the least negative
potential.
Potentials which are not reversible have values which depend on the current which flows
through them. The difference between the reversible potential of an electrode and its
actual potential when current does flow through it is called overpotential. The
overpotential depends upon the current and other electrode conditions and its
determination is beyond our scope. However, when currents through aqueous electrodes
are small or moderate the overpotentials at those electrodes are generally not more than a
few mV unless the electrode reaction consumes or generates a gas.
Electrode reactions involving gas evolution can have overpotentials as high as a full volt.
Overpotential can lead to different electrode processes in the electrolysis of aqueous
solutions.
Example. An aqueous solution is 1.0 molar in Pb2+ and 1.0 molar in Sn2+, as well as 1.0
molar in H+; the other ions present are electrochemically inert. The reactions which will
occur on electrolysis and the reversible cell potential under standard conditions can be
determined as follows.
The anode reaction will be Sn2+ --> Sn4+ + 2e- at +0.1539 V, since oxidation of water to
produce oxygen could occur only at a much more positive potential. The cathode reaction
at first would appear to be 2H+ + 2e- --> H2(g) at 0.000 V, and on platinum electrodes this
might be observed, but on most metals hydrogen overpotential is at least 0.5 V. With any
significant overpotential the cathode reaction will be Pb2+ + 2e- --> Pb at -0.1266 V,
which will occur in preference to Sn2+ + 2e- --> Sn at -0.1410 V. The usual cell potential
difference will then be DE0 = 0.2805 V, the lead electrode being negative.

Cell Potential Differences From

Electrode Potentials
The standard potential difference across a cell, DE0, is the difference between the two
standard electrode potentials, E0, of the two electrodes in the cell. The actual potential
difference across a cell, DE, is the difference between the two actual electrode potentials,
E, of the two electrodes in the cell, and this will be true whether or not the actual
electrode potentials are standard or even reversible.
Potentials which are not reversible have values which depend on the current which flows
through them. The difference between the reversible potential of an electrode and its
actual potential when current does flow through it is called overpotential. The
overpotential depends upon the current and other electrode conditions and it is generally
beyond our scope. However, when currents through aqueous electrodes are small or
moderate the overpotentials at those electrodes are generally not more than a few mV
unless the electrode reaction consumes or generates a gas. Electrode reactions involving
gases can have overpotentials as high as a full volt. In later sections, we shall see how
overpotential can lead to different electrode processes in the electrolysis of aqueous
solutions.
Concentration Cells
A concentration cell is an electrochemical cell in which the electrode couple at both
electrodes is the same but the concentrations of substances at the two electrodes may
differ. The potential difference across a concentration cell can be calculated using the
Nernst equation. An example of a concentration cell is shown in the Figure below.

Example. A concentration cell is based on the Fe3+/Fe2+ couple whose value of E0 is

+0.769 V. The electrode on the right has a 0.1 molar concentration of Fe3+ and a 0.01
molar concentration of Fe2+. The electrode on the left has a 0.1 molar concentration of
Fe2+ and a 0.01 molar concentration of Fe3+. We can determine which electrode is the
more positive as follows.
The spontaneous reaction in the cell must be to make the concentrations of all species
equal, so on the left the spontaneous reaction is Fe2+ --> Fe3+ + e- while on the right the
spontaneous reaction is Fe3+ + e- --> Fe2+. In the external circuit electrons must then leave
the electrode on the left and flow into the electrode on the right. Since electrons will flow
from a location where they are in surplus, the left, to a place where they are in deficiency,
the right, the electrode on the right must be the more positive.
This qualitative answer matches the quantitative answer obtained from the Nernst
equation. For the electrode on the left,
E = +0.769 - 0.05915 log ([0.1]/[0.01]) = +0.769 - 0.05915 log 10 = +0.7098 V
For the electrode on the right,
E = +0.769 - 0.05915 log ([0.01]/[0.1]) = +0.769 + 0.05915 = +0.8282 V
The potential difference across the cell is 0.1186 V; the electrode on the right is the more
positive.
Equilibrium Constants From Electrode Potentials:
One of the procedures used in quantitative analysis is the reduction of Fe(III) to Fe(II) by
Sn(II); the reaction Sn2+ + 2Fe3+ --> 2Fe2+ + Sn4+ proceeds essentially quantitatively to the
right. This is the direction we would expect it to go in an electrochemical cell made up of
a standard tin and a standard iron half-cell. The tin is being oxidized at the anode and the
iron is being reduced at the cathode. The chemical energy of the cell would be used to do
electrical work in such a system, and the concentrations of Fe(III) and Sn(II) would
decrease as this happened.
Now suppose that the two solutions in the separate half-cells were taken and mixed
together, then the one solution divided into two halves and one half put in each half-cell.
The potential difference between the two electrodes must now be zero since the two halfcells are identical. The energy which could have gone into electrical work has gone into
heat instead. There is now equilibrium between the iron couple which would have been in
one half-cell and the tin couple which would have been in the other half-cell. The
concentrations of the forms of tin and iron present are the equilibrium concentrations and
the potential of each electrode must be the equilibrium potential. In either half-cell, we
could write the half-cell Nernst equation using either couple. So:
E(Sn) = +0.1539 - 0.05915/2 log ([Sn2+]/[Sn4+])
E(Fe) = +0.769 - 0.05915 log ([Fe2+]/[Fe3+])

We want to obtain the value of the equlibrium constant K for the reaction Sn2+ + 2Fe3+ -->
Sn4+ + 2Fe2+, which by definition is
K = a(products)/a(reactants) = [Sn4+][Fe2+]2/[Sn2+][Fe3+]2.
Since at equilibrium there is only one E, that is, E = E(Sn) = E(Fe), we can then write:
0.1539 - 0.05915/2 log ([Sn2+]/[Sn4+]) = 0.769 - 0.05915 log ([Fe2+]/[Fe3+])
It is necessary to have [Fe2+] squared in the resulting equilibrium constant K, so the above
equation is rewritten and then rearranged:
0.1539 - 0.05915/2 log ([Sn2+]/[Sn4+]) = 0.769 - 0.05915/2 log ([Fe2+]2/[Fe3+]2)
0.1539 - 0.769 = 0.05915/2 (log [Sn2+]/[Sn4+] - log [Fe2+]2/[Fe3+]2)
-0.6151 = 0.05915/2 log ([Sn2+][Fe3+]2/[Sn4+][Fe2+])2
0.6151 = 0.05915/2 log ([Sn4+][Fe2+]2/[Sn2+][Fe3+]2)
Then 0.6151 = 0.05915/2 log K, 1.2302 = 0.05915 log K, 20.80 = log K, and K = 6.28 x
10+20. This value is in fact very large as we know it would have to be in order for the
reaction to proceed quantitatively as written.
Potentials in an Electroanalytical Cell:
Electroanalytical chemistry is a group of methods for qualitative and quantitative analysis
based on the behavior of a solution of sample when it is made part of an electrochemical
cell.
In an electrochemical cell, an electric potential is created between two dissimilar metals.
This potential is a measure of the energy per unit charge that is available from the
oxidation/reduction reactions to drive the reaction. It is customary to visualize the cell
reaction in terms of two half-reactions, an oxidation half-reaction and a reduction halfreaction. The cell potential (often called the electromotive force or emf) has a
contribution from the anode which is a measure of its ability to lose electrons - it will be
called its "oxidation potential". The cathode has a contribution based on its ability to gain
electeons, its "reduction potential". The cell potential can then be written:
Ecell = oxidation potential + reduction potential
It is important to understand that the potential of an electrochemical cell is related to the
activities of the reactants and products of the cell reaction and indirectly to their molar
concentrations.
If we could tabulate the oxidation and reduction potentials of all available electrodes,
then we could predict the cell potentials of voltaic cells created from any pair of
electrodes. Actually, tabulating one or the other is sufficient, since the oxidation potential
of a half-reaction is the negative of the reduction potential for the reverse of that reaction.
Two main hurdles must be overcome to establish such a tabulation

1. The electrode potential cannot be determined in isolation, but in a reaction with

some other electrode.
2. The electrode potential depends upon the concentrations of the substances, the
temperature, and the pressure in the case of a gas electrode.
In practice, the first of these hurdles is overcome by measuring the potentials with respect
to a standard hydrogen electrode. It is the nature of electric potential that the zero of
potential is arbitrary; it is the difference in potential which has practical consequence.
Tabulating all electrode potentials with respect to the same standard electrode provides a
practical working framework for a wide range of calculations and predictions. The
standard hydrogen electrode is assigned a potential of zero volts. The second hurdle is
overcome by choosing standard thermodynamic conditions for the measurement of the
potentials. The standard electrode potentials are customarily determined at solute
concentrations of 1 Molar, gas pressures of 1 atmosphere, and a standard temperature
which is usually 25C. The standard cell potential is denoted by a degree sign as a
superscript.
1. Measured against standard hydroden electrode.
2. Concentration 1 Molar

E Cell

3. Pressure 1 atmosphere
4. Temperature 25C

The example below shows some of the extreme values for standard cell potentials.
Cathode (Reduction)
Half-Reaction

Standard Potential
E (volts)

Li+(aq) + e- -> Li(s)

-3.04

K+(aq) + e- -> K(s)

-2.92

Ca2+(aq) + 2e- -> Ca(s)

-2.76

Na+(aq) + e- -> Na(s)

-2.71

Zn2+(aq) + 2e- -> Zn(s)

-0.76

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

0.34

O3(g) + 2H+(aq) + 2e- -> O2(g) + H2O(l)

2.07

F2(g) + 2e -> 2F (aq)

2.87

The values for the table entries are reduction potentials, so lithium at the top of the list
has the most negative number, indicating that it is the strongest reducing agent. The
strongest oxidizing agent is fluorine with the largest positive number for standard
electrode potential.
-we will deal mainly with activities rather than concentration
therefore:

ax = fx [X]
where fx= activity coefficient of solute X and [X] is molar
concentration
-equilibrium constant for a reaction (a + b <=> c + d + e)
K =ac x ad x ae/pb x aa
where a is the activity and p is the pressure in atmospheres
-a pure solid at unity gives this equation:
K = ac x ad/pb
-the second quantity Q:
Q= (ac)i(ad)i/(pb)i
-the change in free energy for the cell reaction:
G= RT ln Q -RT ln K
-cell potential:
G =-nFEcell
where n = # of moles and F = faraday(96,485C/mole of electrons)
Ecell:
Ecell = -RT/nF lnQ + RT/nF ln K
= E0cell - RT/nF ln (ac)i(ad)i/(pb)i
-standard electrode potential:
E0cell = RT/nF ln K
Electrode potentials:
Ecell = E(cathode) - E(anode)
-potentials are measured by difference, they are relative not
absolute
-SHE =Standard hydrogen electrode-1 atm 0volts at all temps.
-NHE = normal hydrogen electrode
-IUPAC says electrode potential refers to reduction 1/2 reactions
-in dilute solutions molar concentration can be used for
computations, rather than activities
-shifts in equilibria cause a shift in cell potential
-to compensate for activity effects and side reactions we can
use (Ef) formal potential instead of standard electrode potential
Calculation of Cell Potential from Electrode Potentials:
Nernst Equation: The cell potential for a voltaic cell under standard conditions can be
calculated from the standard electrode potentials. But real voltaic cells will typically
differ from the standard conditions. The Nernst equation relates the cell potential to its
standard cell potential.
R = gas constant
T = temperature in Kelvins
Q = thermodynamic reaction quotient
F = Faraday's constant
n = number of electrons transferred

The quantity Q, the thermodynamic reaction constant, is like a dynamic version of the
equilibrium constant in which the concentrations and gas pressures are the instantaneous
values in the reaction mixture. For a reaction

the reaction quotient has the form

where [C] is understood to be the molar concentration of product C, or the partial

pressure in atmospheres if it is a gas.
Applied to the Daniell cell where zinc and copper form the electrodes, the reaction is
Zn(s) + Cu2+(aq) <-> Zn2+(aq) + Cu(s)
the form of Q is

since the concentrations of the pure metal solids are assigned the value 1. This implies
that the departure of the cell potential from its standard value of 1.10 volts will be
influenced by the temperature and the ion concentrations.
One implication is that the cell potential will be reduced from
the standard value if the concentration of Zn2+(aq) is greater
than that of Cu2+(aq) at the standard temperature. An excess
concentration of Cu2+(aq) will give a higher voltage. The
graph at right shows the increase in cell voltage with
increasing concentration of the cation. Note that the
horizontal axis is logarithmic, and that the straight line
variation of the voltage represents an logarithmic variation
with Q. Note that the cell potential is equal to the standard
value if the concentrations are equal even if they are not equal
to the standard value of 1M, since the logarithm gives the
value zero.

Consider a concentration of 10-5Molar for Zn2+(aq) and 0.1

Molar for Cu2+(aq) as a test case for temperature dependance.
We can see that the cell potential tends to increase with
temperature, or that a colder cell prodices less voltage - a
commonly observed phenomenon with dry cell batteries. The
variation with temperature is linear with temperature, but
quite small for this cell. The large variations of practical
output voltage with temperature for dry cells does not arise
from the Nernst equation alone.

-calculated potentials are sometimes called thermodynamic

potentials
Ecell = E(cathode) - E(anode)
-negative Ecell indicates non-spontaneity of reaction
-Liquid Junction Potentials can be calculated from the knowledge
of the mobility of the two ions involved, but it is rare that the
system in question is simple enough for this computation
Currents in Electrochemical Cells:
-Ohms law is usually obeyed:
E=IR
where E is the potential difference in volts responsible for the
movement of the ions, I is the current in amps, and R is the
resistance in ohms of the electrolyte to the current
Electrochemical Power Sources:
There are three significant types of power sources which produce electricity by reaction
within electrochemical cells. The two types which use reactants stored within them are
called primary cells and secondary cells. Groups of primary or secondary cells are
called batteries, although the term battery has been extended to include also a single cell
used as a power source. Secondary cells, unlike primary cells, can be driven in reverse or
charged by external electrical power. The third type, fuel cells, employ reactants which
are continuously supplied to the cell; products are also continuously removed. In primary
and secondary cells, the reactants and products are contained within the cell.
Primary Cells
Primary cells are electrochemical cells in which a spontaneous electrochemical reaction
serves as a source of electrical power. A primary cell is not designed to be recharged after
use and must be discarded when its internal supply of reactants is exhausted. Attempts to
recharge sealed primary cells can produce explosions because the cells are not designed
to withstand the pressure of gases generated within the cell by electrolysis. Primary cells
are most useful in providing low-current DC power, particularly when the demand is
intermittent. The oldest practical primary cell is the now-obsolete Daniell cell or wet cell
which was used to power electrical telegraphs at the turn of the century. These cells

consisted of a large glass jar (now called a battery jar) filled with two solutions of
aqueous sulfuric acid. The lower half of the jar was filled with a denser solution of
CuSO4 in the acid, while the upper half was filled with the acid alone. A zinc electrode
was placed in the upper half of the cell and a copper electrode was placed in the lower
half. This cell provided a voltage of about one volt. If the cell was connected constantly
and not agitated, the difference in density between the solutions kept them from mixing
for months. The overall cell reaction is Zn(s) + Cu2+(aq) --> Zn2+(aq) + Cu(s) in the cell:
(-) Zn(s)/Zn2+(aq),H2SO4(aq)//Cu2+(aq),H2SO4(aq)/Cu(s) (+)
The common flashlight cell or dry cell is the acidic Zn/MnO2 cell designed by Leclanche'
in 1887. The structure of this cell is shown in the Figure below.
The zinc casing serves as the anode and is consumed in the anodic electrode reaction
Zn(s) --> Zn2+ + 2e-; the zinc ion dissolves in the moist ZnCl2-NH4Cl electrolyte. A
carbon rod serves as the cathode, but it is chemically inert. The cathodic electrode
reaction which consumes MnO2 is best written as:
[Mn4+ + 2O2-] + H2O + e- --> [Mn3+ + O2- + OH-] + OHwhere the square brackets indicate the species present in the solid phase at the cathode.
The cathode reaction actually occurs within the solid structure; the carbon rod serves only
to transfer electrons from the external circuit.
The dry cell has a potential difference of about 1.25 V; the zinc electrode is negative. It is
a good source of electrical power and the materials of construction are relatively cheap.
The cell voltage during discharge falls off rather badly and the dry cell is not a good
source of power when a constant voltage is needed.
The alkaline manganese cell, or alkaline cell, is a variant of the dry cell in which the
acidic NH4Cl(aq) electrolyte is replaced by a concentrated solution of NaOH. The carbon
electrode is replaced by a steel rod or brass tube. In this battery the anode reaction is Zn +
2OH- --> ZnO(c) + H2O + 2e-, since ZnO is insoluble in the alkaline electrolyte solution.
Alkaline cells cost two to three times as much as their counterpart dry cells because a
more elaborate internal construction is required to prevent leakage of the caustic
electrolyte. They do, however, have almost twice the charge capacity and a higher
available current. The voltage of alkaline manganese cells is the same as the voltage of
dry cells, but under heavy current drain their output voltage decreases less. These
advantages have led to their increasing use in battery-powered electronic equipment.
The mercury cell, also known as the Ruben cell, was developed in 1947. Its reaction on
discharge is Zn(s) + HgO(s) --> ZnO(s) + Hg(l), and it takes place in the cell
(-) Zn(s)/KOH,ZnO(s),H2O/HgO(s),Hg(l) (+)
Mercury cells are much more expensive to manufacture than are dry cells or alkaline
cells. This is due to the high cost of the mercury and mercury (II) oxide they contain.
However, the discharge curve of mercury cells is very flat, which is to say that the
potentials of mercury cells do not drop off significantly as the cell discharges, and the

temperature coefficient of the mercury cells is also less. At 250C the cell voltage is 1.344
V with the zinc electrode negative. The constancy of the mercury cell voltage makes it
useful in sensitive instruments but the high cost prevents its use as a general power
source.
Other types of primary cells, such as the lithium cell, have been developed for special
uses where long life, small size, and very low power are required. Cameras, heart
pacemakers, and electronic wrist watches are powered by these cells.
Secondary Cells
The familiar automobile battery is a group of secondary cells connected in series. A 12volt automobile battery consists of six lead-acid cells in series. Each lead-acid cell is
represented as follows:
(-) Pb(s)/PbSO4(s),H2SO4(aq)//H2SO4(aq),PbO2(s)/Pb(s) (+)
Modern automobile batteries are remarkably rugged in both the physical and electrical
sense. A typical automobile battery rated at 54 ampere-hours can provide currents as high
as 300 A for short periods and a continuous drain of 25 A for over two hours.
The electrode reaction at the negative electrode of a lead-acid cell is PbSO4(s) + 2e- -->
Pb(s) + SO42-(aq), for which E0 = -0.356 V, as measured by Kolthoff in 1931. At the
positive electrode the reaction is PbO2(s) + SO42- + 4H+ + 2e- --> PbSO4(s) + 2H2O, for
which E0 = +1.685 V, as measured by Harned and Hamer, also in 1931. The standard cell
potential difference is then 2.041 V, and the spontaneous direction is for the PbO2 side to
be positive. There is therefore in the external circuit a spontaneous electron flow from the
lead metal side to the lead dioxide side which means that the spontaneous reaction must
be, at the less positive or more negative electrode, Pb --> PbSO4(s), giving electrons. This
is an oxidation process and so this electrode must be the anode. At the more positive
electrode, the spontaneous reaction must be PbO2(s) --> PbSO4(s), taking electrons; this is
a reduction process and so this electrode must be the cathode.
As the battery is being charged, the reaction is forced to proceed in the nonspontaneous
direction Pb(II) --> Pb(IV) + Pb(0) and therefore the amount of PbSO4(s) decreases, the
amount of H2SO4(aq) increases, the amount of PbO2(s) increases, and the amount of lead
metal increases.
Another rechargeable secondary cell, used for hand-held devices such as electric razors,
is the nickel-cadmium cell (NiCd cell or nicad cell). This cell contains an alkaline
electrolyte. The spontaneous reactions on cell discharge at the anode and cathode are to
the right:
2NiOOH(s) + 2H2O <--> 2Ni(OH)2(s) + Cd(OH)2(s)
These reactions take place in the cell
(-) steel/Cd(s),Cd(OH)2(s)/LiOH(aq)/NiOOH(s),Ni(OH)2(s)/steel (+)

The discharge reactions are reversed when the cell is recharged. A fully charged nicad
cell has a potential of about 1.4 V, and the cadmium terminal is negative. Nicad cells are
available in standard flashlight cell sizes and can replace them in many applications.
Nicad cells do lose stored charge (self-discharge) over a period of a few months and so
they are not suitable for very intermittent use.
Fuel Cells
A fuel cell is an electrochemical cell to which reactants are continually supplied and from
which products are continually removed so that there is a continuous production of
electrical power. The best known fuel cell, and the most highly developed, is the
hydrogen/oxygen fuel cell known as the Bacon cell, which is used in the United States
space program. An idealized drawing of this cell is shown in the Figure below.

The spontaneous reactions in this cell are oxidation of hydrogen at the anode and
reduction of oxygen at the cathode:
Pt,H2(g) --> 2H+(aq) + e-; E0 = 0.0000 V
Pt,O2(g) + 4H+(aq) + 4e- --> 2H2O; E0 = +1.2288 V
The overall cell reaction, which yields 1.2288 V under standard conditions, is the
formation of water, O2(g) + 2H2(g) --> 2H2O. Cost is a major problem with this cell; pure
hydrogen, pure oxygen, and platinum are expensive. The platinum electrodes tend to pick
up any trace of impurity in the oxygen or hydrogen and are poisoned by it, so that the cell
efficiency is degraded severely.
Fuel cells have been suggested as future power sources, because they are not as restricted
in efficiency as are power sources based on heat engines. The amount of heat obtainable
and work obtainable from a fuel are roughly the same. However, the conversion of heat
into work with 100% efficiency is not possible; the maximum efficiency possible
depends on the temperature of the input and output heat. Efficiencies of 30 - 40% are
commonly found in practice. The theoretical advantage in avoiding the heat step is about
a factor of three, a considerable advantage if electrical power rather than heat is desired.
Example. Suppose we used methanol as a fuel in a fuel cell and in a heat engine. The net
reaction in either case would be 2CH3OH(l) + 3O2(g) --> 2CO2(g) + 4H2O(g)
DG0 = 2(-394.359) + 4(-228.572) - 2(-166.36) - 3(0) = -1370.29 kJ

A total of -685.14 kJ/mole methanol of work are possible. The heat which could be
obtained is -638.49 kJ/mole methanol:
DH0 = 2(-393.509) + 4(-241.818) - 2(-238.66) - 3(0) = -1276.97 kJ
Practical fuel cells using the oxidation of methane (natural gas) operate at 800oC to
1000oC with a molten carbonate salt serving as the electrolyte. Long-term operation of
these cells is compromised by impurities in natural gas which react irreversibly with the
molten carbonate electrolyte. For example, sulfur-containing impurities such as H2S are
oxidized to sulfate ion which accumulates in the cell electrolyte.
Effect of current on cell potential:
-can result in
1) reduced potential of galvanic cell
2) increased potential needed to develop current in an
electrolytic cell:
-this is due to ohmic resistance and polarization effects such
as: charge transfer over-voltage, crystallization over-voltage
-to account for an ohmic potential, or IR drop:
Ecell = E(cathode) - E(anode) IR
Polarization:
Polarization has occurred if the relationship Eapp = Ec Ea IR does not hold true.
Cells that exhibit a nonlinear increase of current with potential are polarized. Complete
polarization has occurred when I is independent of potential no matter how much more
negative one makes the Eapp, I wont change. Metallic surfaces can be polarized by the
application of an external voltage or by the spontaneous production of a voltage away
from equilibrium. This deviation from equilibrium potential is called polarization. The
magnitude of polarization is usually described as an overvoltage (h) that is a measure of
polarization with respect to the equilibrium potential (E ) of an electrode.
eq

This polarization is said to be either anodic, when the anodic processes on the electrode
are accelerated by changing the specimen potential in the positive (noble) direction or
cathodic when the cathodic processes are accelerated by moving the potential in the
negative (active) direction. There are three distinct types of polarization in any
electrochemical cell, the total polarization across an electrochemical cell being the
summation of the individual elements:
E - E = h = h +h +iR
app

eq

total

act

conc

Concentration Polarization- When the mass transfer limits

the rate of the reaction and therefor the current. Concentration polarization occurs
when the concentration at the surface is not the same as that in the bulk, get less
current than predicted. Stirring will decrease concentration polarization. As the

voltage becomes much more negative all the reagent is reduced as soon as it reaches
the surface, therefore the surface concentration of the reagent is zero.
Reaction Polarization- When the rate of formation of the
intermediate limits the current
When a physical process limits the reaction it is said to be
adsorption, desorption, crystallization etc. polarization
Charge Transfer Polarization- When rate of electron transfer
from electrode to oxidized species or reduced species to
electrode limits the current. An overvoltage is required to observe the reaction.
When the degree of polarization is measured by the overvoltage n
n = E - Eeq
where E is electrode potential and Eeq is thermodynamic or
equilibrium potential and E<Eeq
It is necessary that the reactant be brought to the surface
of the solution from the bulk at a rate of:
I = dQ/dt = nFdc/dt
where dQ/dt is the rate of flow of the electrons in the
electrode, n is the # of electrons in the 1/2 reaction, and
F is the faraday
The rate of concentration change is:
dc/dt = AJ
where A=surface area of electrode(m2) and J= the
concentration flux in mol/s.m2
I = nFAJ
Ecell = E(cathode) - E(anode) - IR + n(cathode) + n(anode)
The rate of diffusion:
dc/dt = k(c -c0)
where k=proportionality constant, c=reactant concentration,
and c0=equilibrium concentration.
Summary:
To summarize, concentration polarization is observed when diffusion, migration and
convection are insufficient to transport the reactant to or from an electrode surface at a
rate demanded by the theoretical current.

The following diagram summarizes the procedures for the voltammetric analysis of
various types of water.

The above diagram illustrates the importance of derivative polarogram in clarifying a

regular polarogram recording.

Some very important types of Polarography are shown below:

LCEC:

The illustration below depicts the comparison of the detection ranges of a number of
different techniques including Polarometry.

The following table shows the application of the Electrochemical Stripping Analysis:

WHAT IS POTENTIOMETRY?

Introduction
Potentiometry is the field of electroanalytical chemistry in which potential is measured
under the conditions of no current flow. The measured potential may then be used to
determine the analytical quantity of interest, generally the concentration of some
component of the analyte solution. The potential that develops in the electrochemical cell

is the result of the free energy change that would occur if the chemical phenomena were
to proceed until the equilibrium condition has been satisfied.

Grxn = -nFErxn

This concept is typically introduced in quantitative analysis courses in relation to

electrochemical cells that contain an anode and a cathode. For these electrochemical
cells, the potential difference between the cathode electrode potential and the anode
electrode potential is the potential of the electrochemical cell.

Ecell = Ecathode Eanode

If the reaction is conducted under standard state conditions, this equation allows the
calculation of the standard cell potential. When the reaction conditions are not standard
state, however, one must utilize the Nernst equation to determine the cell potential.

Ecell = E RT/nF(ln(Keq)
o

Physical phenomena which do not involve explicit redox reactions, but whose initial
conditions have a non-zero free energy, also will generate a potential. An example of this
would be ion concentration gradients across a semi-permeable membrane. This can also
be a potentiometric phenomena, and is the basis of measurements that use ion-selective
electrodes.

Emem = (constant) RT/ziF(ln(ai)

WHAT IS COULOMETRY?
Introduction
Coulometry is an analytical method for measuring an unknown concentration of an
analyte in solution by completely converting the analyte from one oxidation state to
another. Coulometry is an absolute measurement similar to gravimetry or titration and
requires no chemical standards or calibration. It is therefore valuable for making absolute
concentration determinations of standards.
Coulometry uses a constant current source to deliver a measured amount of charge. One
mole of electrons is equal to 96,485 coulombs of charge, and is called a faraday.

Schematic of a coulometric cell

Coulometry encompasses a group of analytical methods that involve measuring
the quantity of electricity needed to convert the analyte quantitatively to a different
oxidation state.
Coulometric Methods- rather that relying on electrode weight gain, an analysis can be
conducted based on electrical usage. Resistance, voltage, current and time can all be
measured with great accuracy. A precipitate is not required so a larger number of
reactions can be used. Smaller quantities can be measured. These methods are often as
accurate as gravimetric or volumetric procedures, they are usually faster and more
convenient than the former.

Coulometric Titration
Due to concentration polarization it is very difficult to completely oxidize or reduce a
chemical species at an electrode. Coulometry is therefore usually done with an
intermediate reagent that quantitatively reacts with the analyte. The intermediate reagent
is electrochemically generated from an excess of a precursor so that concentration
polarization does not occur. An example is the electrochemical oxidation of I- (the
precursor) to I2 (the intermediate reagent). I2 can then be used to chemically oxidize
organic species such as ascorbic acid.
The point at which all of the analyte has been converted to the new oxidation state is
called the endpoint and is determined by some type of indicator that is also present in the
solution. For the coulometric titration of ascorbic acid, starch is used as the indicator. At
the endpoint, I2 remains in solution and binds with the starch to form a dark purple
complex.
The analyte concentration is calculated from the reaction stoichiometry and the amount of
charge that was required to produce enough reagent to react with all of the analyte.

WHAT IS VOLTAMMETRY?
Voltammetry refers to the measurementof current that results from the application of
potential. Unlike potentiometry measurements, which employ only two electrodes,
voltammetric measurements utilize a three electrode electrochemical cell. The use of the
three electrodes (working, auxillary, and reference) along with the potentiostat instrument

allow accurate application of potential functions and the measurement of the resultant
current. The different voltammetric techniques that are used are distinguished from each
other primarily by the potential function that is applied to the working electrode to drive
the reaction, and by the material used as the working electrode.

What is Cyclic Voltammetry (CV)?

Cyclic voltammetry (CV) is an electrolytic method that uses microelectrodes and an
unstirred solution so that the measured current is limited by analyte diffusion at the
electrode surface. The electrode potential is ramped linearly to a more negative potential,
and then ramped in reverse back to the starting voltage. The forward scan produces a
current peak for any analytes that can be reduced through the range of the potential scan.
The current will increase as the potential reaches the reduction potential of the analyte,
but then falls off as the concentration of the analyte is depleted close to the electrode
surface. As the applied potential is reversed, it will reach a potential that will reoxidize
the product formed in the first reduction reaction, and produce a current of reverse
polarity from the forward scan. This oxidation peak will usually have a similar shape to
the reduction peak. The peak current, ip, is described by the Randles-Sevcik equation:
ip = (2.69x105) n3/2 A C D1/2 v1/2
where n is the number of moles of electrons transferred in the reaction, A is the area of
the electrode, C is the analyte concentration (in moles/cm3), D is the diffusion coefficient,
and v is the scan rate of the applied potential.
The potential difference between the reduction and oxidation peaks is theoretically 59
mV for a reversible reaction. In practice, the difference is typically 70-100 mV. Larger
differences, or nonsymmetric reduction and oxidation peaks are an indication of a
nonreversible reaction. These parameters of cyclic voltammograms make CV most
suitable for characterization and mechanistic studies of redox reactions at electrodes.

What is Polarography?
Introduction
Polarography is an voltammetric measurement whose response is determined by
combined diffusion/convection mass transport. Polarography is a specific type of
measurement that falls into the general category of linear-sweep voltammetry where
the electrode potential is altered in a linear fashion from the initial potential to the final
potential. As a linear sweep method controlled by convection/diffusion mass transport,
the current vs. potential response of a polarographic experiment has the typical
Picture
sigmoidal shape. What makes polarography different from other linear sweep
of a
voltammetry measurements is that polarography makes use of the dropping mercury
DME
electrode (DME). Close-up of the DME.
A plot of the current vs. potential in a polarography experiment shows the current
oscillations corresponding to the drops of Hg falling from the capillary. If one

connected the maximum current of each drop, a sigmoidal shape would result. The
limiting current (the plateau on the sigmoid), called the diffusion current because
diffusion is the principal contribution to the flux of electroactive material at this point
of the Hg drop life, is related to analyte concentration by the Ilkovic equation:
id = 708nD1/2m2/3t1/6c
Where D is the diffusion coefficient of the analyte in the medium (cm2/s), n is the
number of electrons transferred per mole of analyte, m is the mass flow rate of Hg
through the capillary (mg/sec), and t is the drop lifetime is seconds, and c is analyte
concentration in mol/cm3.
There are a number of limitations to the polarography experiment for quantitative
analytical measurements. Because the current is continuously measured during the
growth of the Hg drop, there is a substantial contribution from capacitive current. As the
Hg flows from the capillary end, there is initially a large increase in the surface area. As a
consequence, the initial current is dominated by capacitive effects as charging of the
rapidly increasing interface occurs. Toward the end of the drop life, there is little change
in the surface area which diminishes the contribution of capacitance changes to the total
current. At the same time, any redox process which occurs will result in faradaic current
that decays approximately as the square root of time (due to the increasing dimensions of
the Nernst diffusion layer). The exponential decay of the capacitive current is much more
rapid than the decay of the faradaic current; hence, the faradaic current is proportionally
larger at the end of the drop life. Unfortunately, this process is complicated by the
continuously changing potential that is applied to the working electrode (the Hg drop)
throughout the experiment. Because the potential is changing during the drop lifetime
(assuming typical experimental parameters of a 2mV/sec scan rate and a 4 sec drop time,
the potential can change by 8 mV from the beginning to the end of the drop), the charging
of the interface (capacitive current) has a continuous contribution to the total current,
even at the end of the drop when the surface area is not rapidly changing. As such, the
typical signal to noise of a polarographic experiment allows detection limits of only
approximately 10-5 or 10-6 M. Better discrimination against the capacitive current can be
obtained using the pulse polarographic techniques.
Qualitative information can also be determined from the half-wave potential of the
polarogram (the current vs. potential plot in a polarographic experiment). The value of
the half-wave potential is related to the standard potential for the redox reaction being
studied.
References:
http://www.anachem.umu.se/jumpstation.htm
http://userwww.service.emory.edu/~kmurray/mslist.html
http://www.anachem.umu.se/jumpstation.htm
http://www.acs.org
http://www.chemcenter/org
http://www.sciencemag.org
http://www.scimedia.com
http://www.kerouac.pharm.uky.edu/asrg/wave/wavehp.html
http://en.wikipedia.org/wiki/Image:Galvan.png