Chapter 21

Potentiometry
 Goal of this chapter
• To learn potentiometric measurement methods.
• To learn the structure of reference electrodes.
• To learn the structure and response mechanism
of indicator electrodes.
• To learn the structure and response mechanism
of gas sensing probes.
• To learn the application of potentiometry in
measure reaction constants.
 Electrochemical cells used in
potentiometric method
• Diagram of electrochemical cells used in potentiometric
measurements:
reference electrode I salt bridge I analytical solution I indicator electrode

• Reference electrode:
- an electrode provide a base with which the potential of the indicator
electrode can be compared with.
- its potential must exactly be known.
- constant potential at constant temperature
- potential independents of composition of analyte solutions.

• Indicator electrode:
- potential varies with the analyte concentration in solution.
- the relationship of potential and the concentration of analyte is known.
 Reference electrodes
----Calomel electrode
• Diagram:
Hg I Hg2Cl2 (sat’d), KCl(x M) II

• Half reaction:
Hg2Cl2 + 2e- 2Hg + 2Cl-

• Potential:
- Varies with KCl concentration and
temperature.
- With saturated KCl solution,
E = 0.2444 V at 25 oC.

• A KCl Saturated Calomel electrode is

usually shorted as SCE
 Reference electrodes
----Silver/silver chloride reference electrode
• Diagram:
Ag I AgCl (sat’d), KCl(sat’d) II

• Half reaction:
AgCl + e- Ag(s) + Cl-

• Potential:
E = 0.199 V at 25 oC
 Q Question

• Why don’t we use SHE (standard

hydrogen electrode) as a reference
electrode?
Potential of reference electrodes at
different temperatures
 Use reference electrodes
Which one should be used
–Ag|AgCl or SCE?
• Ag/AgCl ; better for uncontrolled temperature (lower T
coefficient)
• However, Ag reacts with more ions

Precautions in Use:
• Level of liquid inside reference electrode above the
level of analyte solution to minimize contamination.
• Plugging problematic if ion reacts with solution to
make solid (e.g. AgCl in Cl-determination).
 Liquid Junction Potential
- due to the unequal distribution of cations & anions across a
boundary as a result of the differences in rates at which ions
migrate.

Both H+ & Cl- move from H+ smaller and more mobile

high to low concentration relative to Cl-, moves more
(entropy) quickly
Porous
diaphragm

Results in separation of “+” and “-”

charges and creation of potential

Note: Equilibrium condition soon develops

 Liquid Junction Potential

Porous
diaphragm

- junction potential can be as much as 30 mV

- for simple system can calculate if know mobility and
concentration of all ions present
- junction potential can be decreased by using salt bridge
containing concentrated electrolyte
- best if mobility of ions are ~ equal
- 4 M KCl or KNO3
- decrease junction potential to a few mV
Indicator electrodes
Example of metal indicator electrode
 Features of metal indicator electrodes
In general, metal indicator electrodes of “first
kind”:
• Simple
• Not very selective
• Some metals easily oxidized (deaerate solutions)
• Some metals (Zn, Cd) dissolve in acidic solutions.
• Contamination problem.
• Electrodes of the “second kind” -respond to
changes in ion activity through formation of
complex (as seen in example).
 Ion selective membrane electrodes
• 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.
 Ion selective membrane electrodes
Membrane
• Low solubility -solids, semi-solids and polymers
• Some electrical conductivity -often by doping
• Selectivity -part of membrane binds/reacts with analyte.
Two general types -crystalline and non-crystalline
membranes
• Non-crystalline membranes:
- Glass -silicate glasses for H+, Na+
- Liquid -liquid ion exchanger for Ca2+
- Immobilized liquid -liquid/PVC matrix for Ca2+ and NO3-
• Crystalline membranes:
- Single crystal -LaF3 for F-Polycrystalline
- Mixed crystal –AgS for S2-and Ag+
An example of membrane electrodes
---a glass membrane pH electrode
 A glass membrane pH electrode

• The glass membrane has anionic sites:

A glass membrane pH electrode
 A glass membrane pH electrode
----The boundary potential
• Due to the difference in [H+] concentration in the sample
solution and reference solution, different numbers of H+ will
be attached onto the inner/outer surfaces of the glass
membrane. This causes a boundary potential across the
glass membrane.
 A glass membrane pH electrode
• Consider the ion exchanges on each side of the
glass membrane
 A glass membrane pH electrode
• The Nernst equations for the internal and external
membranes:

are constant
A glass membrane pH electrode
• The pH electrode response:
A glass membrane pH electrode
-----The real pH electrode response
 A glass membrane pH electrode
Alkali Error
• H+ not only cation that can bind to glass surface
- H+ generally has the strongest binding
• Get weak binding of Na+, K+, etc
• Most significant when [H+] or aH+ is low (high pH)
- usually pH at around 11-12

At low aH+ (high pH), amount of

Na+ or K+ binding is significant
 increases the “apparent”
amount of bound H+
 Glass electrode for other ions

• Glass electrodes are also available for following ions:

Glass membrane pH electrodes
-----How is the electrode looks like
Work with glass electrodes

1. Be very careful with the glass

membrane bubble (thickness <
100 µm.
2. Keep the electrode soaked in
DI water when not in use.
3. Calibrate the electrode using
standard buffer solution before
use.
4. Rinse the electrode with DI
water between measurements.
A pH electrode at work
 Interference problems in ion
selective electrode potentiometry
 Problems in using glass electrode
for pH measurement
• Applicable limit (acid error and alkaline error).
• Dehydration.
• Variation in junction potential resulted from
difference in the composition of standard
solution and sample solutions
• Nonreproducible junction potentials when
applied to low ionic strength solutions. The
problem is caused by the partial clogging of the
fritted glass plug or porous fiber as salt bridge.
• Watch your standard buffer solution, especially
the solutions made from organic compounds.
 Crystalline membrane electrode
-----Fluoride Electrode
• LaF3 crystal doped with EuF2
• Mechanism similar to pH electrode with potential
developing at two interfaces of the membrane from the
reaction:
LaF3  LaF2+ + F-

Solid Solution
(membrane surface)

The side of the membrane with

the lower aF- becomes positive
relative to the other surface:
Eind = L + 0.0592 pF
 Liquid membrane electrodes
• Based on potential that
develops across two
immiscible liquids with
different affinities for
analyte.
• Porous membrane
used to separate
liquids.
• Selectively bond
certain ions.
– Activities of different
cations
• Calcium dialkyl
phosphate insoluble in
water, but binds Ca2+
strongly
Metal oxide field effect transistor
(MOFET)
• A solid state semiconductor
element.
• When an electrical potential
applied between the gate
and the source, the
electrical conductivity of the
channel is enhanced by a
factor, which is related to
the applied potential.
• What will happen if a
potential due to charged
ions build up on the surface
of gate ?
Ion selective field effect transistor (ISFETS)

• The key for ISFETS sensor is now the ion selective

coating SiO2 insulator layer. If you can design a coating
selectively trap a specific ion, you can design a sensor.
• People in semiconductor industry can help chemists to
fabricate micro sensor arrays.
 Gas sensing probe
Typically based on ISE surrounded by electrolyte solution
- activity of ion measured is affected by dissolved gas
- gas enters interior solution from sample by passing through
a gas permeable membrane
Gas effuses through membrane:
CO2 (aq) -> CO2 (g) -> CO2 (aq)
External membrane internal
Solution pores solution
In internal solution, pH changes:
CO2 (aq) + H2O -> HCO3- + H+
which is detected by ISE probe
Overall reaction:
CO2 (aq) + H2O -> H+ + HCO3-
external internal
solution solution
Eind = c + 0.0592 log [CO2]ext
 Biocatalytic membrane electrodes
• Immobilized enzyme bound to gas permeable
membrane
• Catalytic enzyme reaction produces small
gaseous molecule (H+, NH3, CO2)
• gas sensing probe measures change in gas
concentration in internal solution
– Fast (?)
– Very selective
– Used in vivo
– Expensive
– Only few enzymes immobilized
– Immobilized enzymes change activity
– Limited operating conditions (which is OK for
biochemical application)
• pH
• temperature
• ionic strength
 Biocatalytic Membrane Electrodes
----An example
Urea Enzyme Electrode
Principal:
- In presence of enzyme
urease, urea (NH4)2CO
is hydrolyzed to give
NH3 and H+.
- Monitor amount of NH3
produced using NH3 gas
sensing electrode.

(NH4)2CO + 2H2O + H+  2NH4+ + HCO3-



2NH3 + 2H+
 Applications of potentiometry
---Direct potentiometry
• Direct potentiometry for analyzing/monitoring ions in
aqueous solution: pH, pF, pCa, pCO2.
• Among these, glass electrode pH meter is the most
successful.
• A calibration using standard solutions is usually used in
measurements.
• Potential problems in direct potentiometry include slow
response time, electrode surface contamination, co-
existence ion interference, electrode life-time (when
enzyme is immobilized), long-term stability (base-line
draft), etc.
• Potentiometry measures activity, not concentration. When
seeking concentration, ionic strength match between
calibration standard solution and sample solution is
essential.
• ionic strength match between calibration standard solution
and sample solution can also help reduce junction
potential error in potentiometry.
A typical calibration curve for an ion
selective electrode
Examples of potentiometry applications
Advantages of Ion-selective electrodes
1) When compared to many other analytical techniques,
Ion-Selective Electrodes are relatively inexpensive and
simple to use and have an extremely wide range of
applications and wide concentration range.
2) The most recent plastic-bodied all-solid-state or gel filled
models are very robust and durable and ideal for use in
either field or laboratory environments.
3) Under the most favorable conditions, when measuring
ions in relatively dilute aqueous solutions and where
interfering ions are not a problem, they can be used very
rapidly and easily (e.g. simply dipping in lakes or rivers,
dangling from a bridge or dragging behind a boat).
4) They are particularly useful in applications where only an
order of magnitude concentration is required, or it is only
necessary to know that a particular ion is below a certain
concentration level.
5) They are invaluable for the continuous monitoring of
changes in concentration: e.g. in potentiometric titrations
or monitoring the uptake of nutrients, or the consumption
of reagents.
6) They are particularly useful in biological and medical
applications because they measure the activity of the ion
directly, rather than the concentration.
7) In applications where interfering ions, pH levels, or high
concentrations are a problem, then many manufacturers
can supply a library of specialized experimental methods
and special reagents to overcome many of these
difficulties.
8) With careful use, frequent calibration, and an awareness of
the limitations, they can achieve accuracy and precision
levels of 2 or 3% for some elements and thus compare
favorably with analytical techniques which require far more
complex and expensive instrumentation.
9) ISEs are one of the few techniques which can measure both
positive and negative ions.
10) ISEs can be used in aqueous solutions over a wide
temperature range. Crystal membranes can operate in the
range 0°C to 80°C and plastic membranes from 0°C to 50°C.