CONSTRUCTION.
Representation: Pt,H2(g)/ H+
APPLICATIONS.
To determine electrode potential of other unknown electrodes.
To determine the pH of a solution.
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
then we can use the cell potential to determine an unknown activity of Cu2+ in
the indicator electrodes half-cell
CONSTRUCTION.
other electrode.
As anode: 2Hg + 2Cl- Hg2Cl2 + 2e-
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.
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.
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
three components:
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:
5.
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.
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
GAS-SENSING ELECTRODES
Membrane electrodes responding to the
concentration of a dissolved gas.
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
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.
= E0 + (2.303RT/ nF)logC2[E0+(2.303RT/nF)logC1]
Ecell = (0.0592/n) log C2/C1
Ecell is positive only if C2 > C1
PROBLEMS
Zn/ZnSO4(0.001M)||ZnSO4(x)/Zn is 0.09V at 25C. Find the concentration
of the unknown solution.
|| Mercurous
nitrate (0.001N)
/Hg
|| Mercurous
nitrate (0.001N)
/Hg
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.