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CLASSIFICATION OF ELECTRODES.

Conventional electrodes as half cells for electroanalytical techniques involve


redox reactions (electrodes of zeroth, 1st, 2nd and 3rd kinds) as follows:

Class 0: Inert metals used in oxidation-reduction electrolytic cells. Ideal inert


materials exchange electrons reversibly with the electrolyte components and are not
subject to oxidation or corrosion themselves, i.e., ideally polarizable electrodes.
Example: Gas electrode ( Hydrogen electrode)
Class 1: Reversible metal/metal ion (ion exchanging metals bathed in electrolytes
containing their own ions), for example Ag/Ag+.
Class 2: Reversible metal/metal ion with saturated salt of the metal ion and
excess anion X- , for example Ag/AgX/X-.
Class 3: Reversible metal/metal salt or soluble complex/second metal salt or
complex and excess second cation, for example Pb/Pboxalate/Caoxalate/Ca2+ or
Hg/HgEDTA2-/CaEDTA2-/Ca2+.

GAS ELECTRODE. CLASS 0


It consists of gas bubbling over an inert metal wire or foil immersed in a solution
containing ions of the gas.
Standard hydrogen electrode is the primary reference electrode, whose electrode
potential at all temperature is taken as zero arbitrarily.

CONSTRUCTION.
Representation: Pt,H2(g)/ H+

The electrode reaction is reversible as it can undergo either oxidation or reduction


depending on the other half cell.
If the concentration of the H+ ions is 1M, pressure of H2 is 1atm at 298K it is called as
standard hydrogen electrode (SHE).

APPLICATIONS.
To determine electrode potential of other unknown electrodes.
To determine the pH of a solution.

E=Eo- 2.303 RT/nF log [H2]1/2/[H+]


= 0 -0.0591 log 1/[H+]
= -0.0591pH.
pH = E(cell)/ 0.0592
Cell Scheme: Pt,H2,H+(x)// SHE

LIMITATIONS.
Construction and working is difficult.
Pt is susceptible for poisoning.
Cannot be used in the presence of oxidizing agents.

CLASS 1 ELECTRODES
Reversible metal/metal ion

First class of electrodes are limited to the following metals: Ag,


Bi, Cd, Cu, Hg, Pb, Sn, Tl, and Z:

The slow kinetics of electron transfer at the metalsolution


Interface the formation of metal oxides on the electrodes
surface
Interfering reactions-electrodes

If we place a copper electrode in a solution containing


Cu2+, the electrodes potential due to the reaction
is determined by the activity of Cu2+

If copper is the indicator electrode in a potentiometric electrochemical cell


that also includes a saturated calomel reference electrode

then we can use the cell potential to determine an unknown activity of Cu2+ in
the indicator electrodes half-cell

An indicator electrode in which a metal is in contact with a


solution containing its ion is called an electrode of the first
kind. In general, if a metal, M, is in a solution of Mn+, the cell
potential is

where K is a constant that includes the standard-state potential


for the Mn+/M redox couple, the potential of the reference
electrode, and the junction potential.

CLASS 2. METAL METAL SALT ION


ELECTRODE.
These electrodes consist of a metal and a sparingly soluble salt
of the same metal dipping in a solution of a soluble salt having
the same anion.
Eg: Calomel electrode.
Ag/AgCl electrode.

CONSTRUCTION.

Representation: Hg; Hg2Cl2 / KCl


It can act as anode or cathode depending on the nature of the

other electrode.
As anode: 2Hg + 2Cl- Hg2Cl2 + 2e-

As Cathode: Hg2Cl2 + 2e- 2Hg + 2 Cl-

The Nernst equation for this reaction is


aHg is the activity for the mercury cation (the activity for a liquid of 1 Molar is
1). This activity can be found from the solubility product of the reaction
By replacing the activity in the Nernst equation
with the value in the solubility equation, we get

The only variable in this equation is the activity (or concentration) of the
chloride anion. But since the inner solution is saturated with potassium chloride,
this activity is fixed by the solubility of potassium chloride.

Its electrode potential depends on the concentration of KCl.


Conc. of Cl-

Electrode potential

0.1M

0.3335 V

1.0 M

0.2810 V

Saturated

0.2422 V

APPLICATIONS.
Since the electrode potential is a constant it can be used as a
secondary reference electrode.

To determine electrode potential of other unknown electrodes.


To determine the pH of a solution.
Pt,H2/H+(X) // KCl,Hg2Cl2,Hg

pH = E(cell) 0.2422/ 0.0592

ION SELECTIVE ELECTRODE.


In 1901 Fritz Haber discovered that there is a change in potential across
a glass membrane when its two sides are in solutions of different
acidity. The existence of this membrane potential led to the development of
a whole new class of indicator electrodes called ion-selective electrodes
(ISEs). In addition to the glass pH electrode, ion-selective electrodes are
available for a wide range of ions.

It is sensitive to a specific ion present in an electrolyte.


The potential of this depends upon the activity of this ion in the
electrolyte.
Magnitude of potential of this electrode is an indicator of the
activity of the specific ion in the electrolyte.

*This type of electrode is also called indicator electrode.

Typical pH glass electrode

1.a sensing part of electrode, a bulb


made from a specific glass
2.internal electrode, usually silver
chloride electrode or calomel
3.internal solution, usually a
pH=7 buffered solution of
0.1 mol/L KCl for pH electrodes or
0.1 mol/L MeCl for pMe electrodes
4.when using the silver chloride
electrode, a small amount of AgCl
can precipitate inside the glass
electrode
5.reference electrode, usually the
same type as 2
6.reference internal solution, usually
0.1 mol/L KCl
7.junction with studied solution,
usually made from ceramics or
capillary with asbestos or quartz
fiber.
8.body of electrode, made from nonconductive glass or plastics.

The potential of an electrode of the first kind responds to the activity of


Mn+.We also can use this electrode to determine the activity of
another species if it is in equilibrium with Mn+. For example, the
potential of a Ag electrode in a solution of Ag+ is

If we saturate the indicator electrodes half-cell with AgI

the solubility reaction determines the concentration of Ag+; thus

The potential of the silver electrode is a function of the activity of I. If we


incorporate this electrode into a potentiometric electrochemical cell with a saturated
calomel electrode
the cell potential is

where K is a constant that includes the standard-state potential for the Ag+/Ag redox
couple, the solubility product for AgI, the reference electrodes potential, and the junction
potential

ELECTRODE POTENTIAL OF GLASS ELECTRODE.


The overall potential of the glass electrode has

The boundary potential Eb,

Internal reference electrode potential Eref.

three components:

Asymetric potential Easy.- due to the difference in response of the


inner and outer surface of the glass bulb to changes in [H+].
Eg = Eb + Eref. + Easy.

Eb = E1 E2
= RT/nF ln C1 RT/nF ln C2
= L + RT/nF ln C1
Eb depends upon [H+]
Eg = Eb + EAg/AgCl + Easy.
= L + RT/nF ln C1 + EAg/AgCl + Easy.
= Eog + RT/nF ln C1
= Eog + 0.0592 log [H+]
Eg = Eog 0.0592 pH.

Advantages:

1. It can be used without interference in solutions


containing strong oxidants, strong reductants, proteins,
viscos fluids and gases as the glass is chemically robust.
2. It can be used for solutions having pH values 2 to 10.
With some special glass (by incorporation of Al2O3 or
B2O3) measurements can be extended to pH values up to
12.
3. It is immune to poisoning and is simple to operate
4. The equilibrium is reached quickly & the response is rapid

5.

It can be used for very small quantities of the


solutions. Small electrodes can be used for pH
measurement in one drop of solution in a tooth
cavity or in the sweat of the skin (micro
determinations using microelectrodes)

6. If recently calibrated, the glass electrode gives an


accurate response.
7. The glass electrode is much more convenient to handle
than the inconvenient hydrogen gas electrode.

Disadvantages:

The bulb of this electrode is very fragile and has to be used with
great care.
The alkaline error arises when a glass electrode is employed to
easure the pH of solutions having pH values in the 12 range or
greater. In the presence of alkali ions, the glass surface becomes
responsive to both hydrogen and alkali ions. Low pH values arise
as a consequence and thus the glass pH electrode gives erroneous
results in highly alkaline solutions.

The acid error results in highly acidic solutions (pH less than
zero)Measured pH values are high.
Dehydration of the working surface may cause erratic electrode
performance. It is crucial that the pH electrode be sufficiently
hydrated before being used. When not in use, the electrode should be stored in an
aqueous solution because once it is dehydrated, several hours are required to rehydrate it fully.

As the glass membrane has a very high electrical resistance (50


to 500 m), the ordinary potentiometer cannot be used for
measurement of the potential of the glass electrode.
Standardization has to be carried out frequently because
asymmetry potential changes gradually with time. Because of an
asymmetry potential, not all glass electrodes in a particular
assembly have the same value of EoG . For this reason, it is best to
determine EoG for each electrode before use.
The commercial version is moderately expensive

APPLICATIONS.
Determination of pH:
Cell: SCE Test solution / GE

E cell = Eg Ecal.
E cell = Eog 0.0592 pH 0.2422
pH = Eog -Ecell Ecal. / 0.0592

PROBLEMS
The cell SCE (0.1M) HCl AgCl(s) /Ag
gave emf of 0.24 V and 0.26 V with buffer having pH
value 2.8 and unknown pH value respectively. Calculate the
pH value of unknown buffer solution. Given ESCE= 0.2422 V

PROBLEMS
The cell SCE (0.1M) HCl AgCl(s) /Ag
gave emf of 0.24 V and 0.26 V with buffer having pH
value 2.8 and unknown pH value respectively. Calculate the
pH value of unknown buffer solution. Given ESCE= 0.2422 V
Eog= 0.0592pH +Ecell + Ecal.
= 0.0592x2.8 +0.24 + 0.2422
=0.648 V
pH = Eog -Ecell Ecal. / 0.0592

= 0.648 -0.26-0.2422/0.0592
= 2.46

MEMBRANE ELECTRODES
If metals are the only useful materials for constructing indicator electrodes, then
there would be few useful applications of potentiometry.
Change in potential across a glass
membrane when its two sides are in
solutions of different acidity
In addition to the glass pH electrode,
ion-selective electrodes are available
for a wide range of ions.
It also is possible to construct a
membrane electrode for a neutral
analyte by using a chemical
reaction to generate an ion that can
be monitored with an ion-selective
electrode. The development of new
membrane electrodes continues to be
an active area of research.

MEMBRANE POTENTIALS
The short hand notation for this cell is

where the ion-selective membrane is shown by the vertical slash separating the
two solutions containing analytethe sample solution and the ionselective
electrodes internal solution.
The electrochemical cell includes two reference electrodes: one immersed in the
ion-selective electrodes internal solution and one in the sample. The cell
potential, therefore, is

where Emem is the potential across the membrane.


Because the junction potential and the potential of the two reference
electrodes are constant, any change in Ecell is a result of a change in the
membranes potential.
The analytes interaction with the membrane generates a membrane potential if
there is a difference in its activity on the membranes two sides.

Current is carried through the membrane by the movement of either the


analyte or an ion already present in the membranes matrix. The
membrane potential is given by the following Nernst-like equation

where (aA)samp is the analytes concentration in the sample, (aA)int is the


concentration of analyte in the ion-selective electrodes internal solution, and z
(OR n) is the analytes charge. Ideally, Emem is zero when (aA)int = (aA)samp. The term
Easym, which is an asymmetry potential, accounts for the fact that Emem is usually not
zero under these conditions.
Substituting equation into previous equation, assuming a temperature of 25 C, and
rearranging gives

A general equation and applies to


all types of ion-selective electrodes.
where K is a constant that includes the potentials of the two reference electrodes,
the junction potentials, the asymmetry potential, and the analyte's activity in
the internal solution.

GAS-SENSING ELECTRODES
Membrane electrodes responding to the
concentration of a dissolved gas.

The basic design of a gas-sensing


electrode is shown, consisting of a thin
membrane that separates the sample
from an inner solution containing an
ion-selective electrode.
The membrane is permeable to the
gaseous analyte, but impermeable to
nonvolatile components in the samples
matrix.
The gaseous analyte passes through the membrane where
it reacts with the inner solution, producing a species whose
concentration is monitored by the ion-selective electrode.

For example, in a CO2 electrode, CO2 diffuses across the


membrane where it reacts in the inner solution to produce
H3O+.
The change in the activity of H3O+ in the inner solution is monitored with a pH
electrode. To find the relationship between the activity of H3O+ in the inner solution
and the activity CO2 in the inner solution:

where Ka is the equilibrium constant. If the activity of HCO3 in the internal solution
is sufficiently large, then its activity is not affected by the small amount of CO2 that
passes through the membrane.

where K is a constant that includes the constant for the pH electrode, the
equilibrium constant and the activity of HCO3 in the inner solution

Properties of some gas-sensing electrodes


The composition of the inner solution changes with use, and both the inner
solution and the membrane must be replaced periodically

POTENTIOMETRIC BIOSENSORS
The approach for developing gas-sensing electrodes can be modified to create
potentiometric electrodes that respond to a biochemically important species.
The most common class of potentiometric
biosensors are
Enzyme Electrodes
Antibodies Electrodes
Bacterial Electrodes
Tissues Electrodes
Hormone receptors Electrodes
One example of an enzyme electrode is the urea
electrode, which is based on the catalytic
hydrolysis of urea by urease

CONCENTRATION CELLS.
Two electrodes of the same metal are in contact with solutions of different concentrations.
Emf arises due to the difference in concentrations.

Cell Representation:
M/ Mn+[C1] Mn+/M[C2]

CONSTRUCTION.

At anode: Zn Zn2+(C1) + 2eAt cathode: Zn2+(C2) + 2e- Zn


Ecell = EC-EA

= E0 + (2.303RT/ nF)logC2[E0+(2.303RT/nF)logC1]
Ecell = (0.0592/n) log C2/C1
Ecell is positive only if C2 > C1

Anode - electrode with lower electrolyte concentration.

Cathode electrode with higher electrolyte concentration.


Higher the ratio [C2/C1] higher is the emf.

Emf becomes zero when [C1] = [C2].

PROBLEMS
Zn/ZnSO4(0.001M)||ZnSO4(x)/Zn is 0.09V at 25C. Find the concentration
of the unknown solution.

Ecell = 0.0592/n log C2/C1


0.09 =(0.0592/2) log ( x / 0.001)
x =1.097M

2. Calculate the valency of mercurous ions


with the help of the following cell.
Hg/ Mercurous

|| Mercurous

nitrate (0.001N)

/Hg

nitrate (0.01N) when the emf observed at 18 C is 0.029 V

Ecell=(2.303 RT/nF) log C2/C1

Ecell=(2.303 RT/nF) log C2/C1


0.029 = 2.303RT/n) log (0.01/0.001)
0.029 =0.057 x 1/ n
n = 0.057/0.029 = 2
Valency of mercurous ions is 2, Hg2 2+

2. Calculate the valency of mercurous ions


with the help of the following cell.
Hg/ Mercurous

|| Mercurous

nitrate (0.001N)

/Hg

nitrate (0.01N) when the emf observed at 18 C is 0.029 V

Ecell=(2.303 RT/nF) log C2/C1

MORE EXAMPLES
Determine E for the concentration cell whose net reaction is Cu2+ (0.035 m)
(0.0077 m).

Cu2+

Determine the ratio of molarities necessary to have E equal to 0.050 V for a concentration cell
composed of (a) Fe2+ ions; (b) Fe3+ ions; (c) Co2+ ions. (d) Compare your answers and explain
the differences or similarities.

PLEASE CHECK E-LEARNING


Electrochemistry assignment. I, Answer 4 questions in details and submit
by 17 March)

Quiz. On Friday, 18 March