POTENTIOMETRY
Potentiometric Analysis
Based on potential
measurement of
electrochemical cells without
any appreciable current
The use of electrodes to
measure voltages from
chemical reactions
Applications of Potentiometric Analysis
Components of a
Potentiometric Cell
1. Reference electrode
2. Salt bridge
3. Analyte
4. Indicator electrode
RE SB A IE
Eref + Ej + Eind
Reference electrode
Half-cell with known potential (Eref)
Left hand electrode (by convention)
Easily assembled
Rugged
Insensitive to analyte concentration
Reversible and obeys Nernst equation
Constant potential
Returns to original potential
Indicator electrode
Generates a potential
(Eind) that depends on
analyte concentration
Selective
Rapid and reproducible
response
Salt bridge
Prevents mixing up of analyte
components
Generates potential (Ej) =
negligible
Reference Electrodes
1. Standard Hydrogen Electrode
2. Calomel Reference Electrode
3. Silver/Silver Chloride
Reference Electrode
SHE
Hydrogen Gas Electrode
Pt (H2 (1 atm), H+ (1M)
Saturated Calomel Electrode
Hg2Cl2(s)+2e-2Hg(l)+2Cl-(aq)
Aka SCE
Easy to prepare
Easy to maintain
0.2444 V at 25C
Dependent on temp
Toxic
SCE
Ag/AgCl Ref. Electrode
Ag AgCl (satd),KCl (satd)
AgCl(s) + e-Ag(s)+Cl-(aq)
E = 0.199 V
Liquid Junction Potential
Liquid junction - interface between
two solutions containing different
electrolytes or different
concentrations of the same
electrolyte
A junction potential occurs at every
liquid junction.
Caused by unequal mobilities of the +
and - ions.
I.
Indicator Electrodes
Metallic IE
A. Electrodes of the First Kind
B. Electrodes of the Second Kind
C. Inert Metallic Electrodes (for Redox Systems)
II. Membrane IE
A.
B.
C.
D.
Glass pH IE
Glass IE for other cations
Liquid Membrane IE
Crystalline-Membrane IE
III. Gas Sensing Probes
METALLIC INDICATOR
ELECTRODES
Electrodes of the First Kind
Pure metal electrode in direct equilibrium with its
cation
Metal is in contact with a solution containing its
cation.
M+n(aq) + ne- M(s)
Disadvantages of First Kind Electrodes
Not very selective
Ag+ interferes with Cu+2
May be pH dependent
Zn and Cd dissolve in acidic solutions
Easily oxidized (deaeration required)
Non-reproducible response
Electrodes of the Second Kind
Respond to anions by forming precipitates or
stable complex
Examples:
1. Ag electrode for Cl- determination
2. Hg electrode for EDTA determination
Inert Metallic (Redox) Electrodes
Inert conductors that respond to redox
systems
Electron source or sink
An inert metal in contact with a solution
containing the soluble oxidized and
reduced forms of the redox half-reaction.
May not be reversible
Examples:
Pt, Au, Pd, C
MEMBRANE
ELECTRODES
Aka p-ion electrodes
Consist of a thin membrane separating 2 solutions of
different ion concentrations
Most common: pH Glass electrode
Glass pH Electrode
Properties of Glass pH electrode
Potential not affected by the presence
of oxidizing or reducing agents
Operates over a wide pH range
Fast response
Functions well in physiological
systems
Very selective
Long lifespan
Theory of the glass membrane potential
For the electrode to become operative, it must be soaked in water.
During this process, the outer surface of the membrane becomes
hydrated.
When it is so, the sodium ions are exchanged for protons in the
solution:
The protons are free to move and exchange with other ions.
Charge is slowly carried
by migration of Na+
across glass membrane
Potential is determined
by external [H+]
Alkaline error
Exhibited at pH > 9
Electrodes respond to
H+ and alkali cations
C,D,E and F:
measured value is <
true value
Electrode also
responds to other
cations
Higher pH at lower
[Na+]
Acid error
Exhibited at pH
< 0.5
pH readings are
higher (curves A
and B)
Saturation effect
with respect to
H+
Selectivity Coefficient
No electrode responds exclusively to one kind of ion.
The glass pH electrode is among the most selective, but it
also responds to high concentration of Na+.
When an electrode used to measure ion A, also
responds to ion X, the selectivity coefficient gives
the relative response of the electrode to the two
different species.
k A, X
response to X
response to A
The smaller the selectivity coefficient, the less interference
by X.
Selectivity Coefficient
Measure of the response of an ISE to other ions
Eb = L + 0.0592 log (a1 + kHBb1)
kHB = 0 means no interference
kHB 1 means there is interference
kHB < 1 means negligible interference
LIQUID MEMBRANE
ELECTRODES
Liquid Membrane Electrodes
Potential develops across the interface between
the analyte solution and a liquid ion exchanger
(that bonds with analyte)
Similar to a pH electrode except that the
membrane is an organic polymer saturated with a
liquid ion exchanger
Used for polyvalent ions as well as some anions
Example:
Calcium dialkyl phosphate insoluble in water, but
binds Ca2+ strongly
0.1 M CaCl2
Responsive to Ca2+
Characteristics of Ca ISE
+2
Relatively high sensitivity
Low LOD
Working pH range: 5.5 11
Relevant in studying physiological processes
A K -selective electrode
+
Sensitive membrane
consists of
valinomycin, an
antibiotic
CRYSTALLINEMEMBRANE
ELECTRODES
Crystalline-Membrane Electrodes
Solid state electrodes
Usually ionic compound
Crushed powder, melted and formed
Sometimes doped to increase
conductivity
Operation similar to glass membrane
Crystalline-Membrane Electrodes
AgX membrane: Determination of X Ag2S membrane: Determination of S-2
LaF3 membrane: Determination of F-
F Selective Electrode
-
A LaF3 is doped with EuF2.
Eu2+ has less charge than the La 3+, so an
anion vacancy occurs for every Eu 2+.
A neighboring F- can jump into the vacancy,
thereby moving the vacancy to another site.
Repetition of this process moves F - through
the lattice.
Fluoride Electrode
GAS SENSING
PROBES
Gas Sensing Probes
A galvanic cell whose potential is related to
the concentration of a gas in solution
Consist of RE, ISE and electrolyte solution
A thin gas-permeable membrane (PTFE)
serves as a barrier between internal and
analyte solutions
Allows small gas molecules to pass and
dissolve into internal solution
O2, NH3/NH4+, and CO2/HCO3-/CO32-
Gas
Sensing
Probe
DIRECT POTENTIOMETRY
A rapid and convenient method of
determining the activity of cations/anions
Potentiometric Measurement
Ionic composition of standards must be
the same as that of analyte to avoid
discrepancies
Swamp sample and standard with inert
electrolyte to keep ionic strength
constant
TISAB (Total Ionic Strength Adjustment
Buffer) = controls ionic strength and pH
of samples and standards in ISE
measurements
Potentiometric Measurement
1. Calibration Method
2. Standard Addition
Method
Special Applications:
Potentiometric pH Measurement
using Glass electrode
One drop of solution
Tooth cavity
Sweat on skin
pH inside a living cell
Flowing liquid stream
Acidity of stomach
Potentiometric Titration
Involves measurement of the potential
of a suitable indicator electrode as a
function of titrant volume
Provides MORE RELIABLE data than
the usual titration method
Useful with colored/turbid solutions
May be automated
More time consuming
Potentiometric Titration Curves
