Potentiometry
Chapter 21
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• Potentiometric methods of analysis are based on measuring the potential of
electrochemical cells without drawing appreciable current.
• Ion concentrations are measured directly from the potential of ion-selective
membrane electrodes.
• Relatively free from interferences and provide a rapid, convenient, and
nondestructive means for quantitatively determining numerous important
anions and cations.
• Equipment:
• Reference electrode
• Indicator electrode
• Potential measuring device
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General Principles
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Reference electrode
• Known half-cell
• Insensitive to solution under examination
• Reversible and obeys Nernst equation
• Accurate and constant potential
• Returns to original potential
• INPE
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Calomel electrode
• Hg in contact with Hg(I) chloride
E(sat,KCl) = +0.244 V
• E depends on the chloride concentration
• The crystal structure of calomel, Hg Cl , which has a limited solubility in water Notice the Hg
2 2
—Hg bond in the structure.
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Silver/Silver Chloride Reference Electrodes
E(sat,KCl) = +0.199 V AgAgCl(sat’d), KCl(sat’d)i
Advantage: They can be used at temperatures
greater than 60°C, while calomel electrodes cannot
mercury(I) ions react with fewer sample components
than do silver ions (which can react with proteins.
-plugging of the junction between the electrode and
the analyte solution.
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Liquid Junction
• When two electrolyte solutions of different composition are in contact with one another, there is a potential
difference across the interface.
• Unequal distribution of cations and anions across the boundary due to differences in the rates at which
these species diffuse.
• Both hydrogen ions and chloride ions tend to diffuse across this boundary from the
more concentrated to the more dilute solution, that is, left to right.
-Hydrogen ions are substantially more mobile than chloride ions
a separation of charge results
1-Two identical electrolytes with different concentration
2-Two different electrolytes
Salt Bridgh
Saturated KCl
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Indicatore Electrodes
• Responds rapidly, selectively and reproducibly to changes in the concentration of
an analyte ion
Types
1-Metalic
2-Membrane
3-Ion selective Field Effective Transistor
Metallic Indicator Electrodes
1-First Kind
2-Second Kind
3-Inert Redox Kind
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Electrodes of the First Kind
• A pure metal electrode that is in direct equilibrium with its cation in the solution
First kind are not widely used for potentiometric determinations for several reasons:
-are not very selective
-many metal electrodes, such as zinc and cadmium dissolve in the presence of acids
-Iron, chromium, cobalt, and nickel, do not provide reproducible potentials
-Metals are so easily oxidized
Ag, Hg, Cu, Zn, Cd,Bi, Tl, Pb
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Electrodes of the Second Kind
• Metals response to the activities of anions that form sparingly soluble precipitates
or stable complexes with such cations.
Note that the sign of the log term for an electrode of this type is opposite that for an
electrode of the first kind
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Inert Metallic Electrodes for Redox Systems
• Several relatively inert conductors respond to redox systems.
Platinum, gold, palladium, and carbon
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Membrane Indicator Electrodes
• Glass Membrane Electrode
Determining pH has involved measurement of the potential that appears across a thin
glass membrane that separates two solutions with different hydrogen ion concentrations.
p-ion electrodes because the data obtained from them are usually presented as p-
functions, such as pH, pCa.
Glass Electrode for Measuring pH
• 1-A thin pH-sensitive glass membrane sealed onto one end of a heavy-walled glass or plastic tube
• 2-Inner solution:A small volume of dilute hydrochloric acid saturated with silver chloride or buffer
containing chloride ion.
• 3-Internal reference electrode (Ag/AgCl): A silver wire in this solution forms a silver/silver chloride
reference electrode
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• Cell: The cell consists of a glass indicator electrode and a saturated calomel reference
electrode immersed in the solution of unknown pH.
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External reference electrode: SCE
Internal reference lectrode: Ag/AgCl
Glass membrane sensitive to pH
Concentration of protons inside the membrane is constant. The concentration outside the membrane is
determined by the activity of hydrogen ions in the analyte solution.
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The Composition and Structure of Glass Membranes
• Corning 015 glass: 22% Na2O, 6% CaO, and 72% SiO2 (up to a pH=9)
• An three-dimensional network of groups in which each silicon atom is bonded to four
oxygen atoms and each oxygen atom is shared by two silicon atoms.
• Within the empty spaces inside this structure are enough cations to balance the negative
charge of the silicate groups. Singly charged cations, such as sodium and lithium, can move
around in the lattice and are responsible for electrical conductionwithin the membrane.
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• The two surfaces of a glass membrane must be hydrated by soaking it in water.
• The hydration of a pH-sensitive glass membrane involves an ion-exchange reaction
between singly charged cations in the interstices of the glass lattice and hydrogen
ions from the solution.
• There is an exception to this situation in highly alkaline media, where the hydrogen
ion concentration is extremely small and the sodium ion concentration is large.
Under this condition, a significant fraction of the sites are occupied by sodium ions.
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Membrane Potentials
• Four Potential
-Internal reference electrode, EAg,AgCl
- External reference electrode, ESCE
-Junction potential, Ej
-boundary potential, Eb (which varies with the pH of the analyte solution)
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Boundary Potential
• Boundary potential is determined by potentials, E1 and E2, which appear at two
surfaces of glass membrane. (subscript 1 refers to external interface, 2 refers to
internal interface)
• When positions of the two equilibria differ, surface where the greater dissociation
has occurred is negative with respect to other face
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Asymmetry Potential
• When identical solutions and reference electrodes are placed on the two sides of a
glass membrane, the boundary potential should in principle be zero. we find a
small asymmetry potential that changes gradually with time.
• Differences in strain on the two surfaces of the membrane created during
manufacture, mechanical abrasion on the outer surface during use, and chemical
etching of the outer surface.
• Elimination: calibration against one or more standard analyte solutions.
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Alkaline Error
• In basic solutions, glass electrodes respond to the concentration of both
hydrogen ion and alkali metal ions.
where a1 and b1 represent the activities of H1 and B1 in
solution and ar1 and br1 are the activities of these ions on
the glass surface
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Describing Selectivity
• Selectivity Coefficient
Selectivity coefficients range from zero (no interference) to values greater than unity. Thus, if an
electrode for ion A responds 20 times more strongly to ion B than to ion A, kH,B has a value of
20. If the response of the electrode to ion C is 0.001 of its response to A (a much more desirable
situation), kH,B is 0.001.
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Acid Error
• Positive Error
• Acid error are not well understood
• Saturation effect that occurs when all the surface sites on the glass are
occupied with H+ ions.
• Under these conditions, the electrode no longer responds to further increases
in the H + concentration, and the pH readings are too high.
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Glass Electrodes for Other Cations
• Alkaline error is negligible below about pH 12
• Al2O3 or B2O3
• Na+, K+, NH4+, Rb+, Cs+, Li+, and Ag+
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Liquid-Membrane Electrodes
• The potential of liquid-membrane electrodes develops across the
interface between the solution containing the analyte and a liquid-ion
exchanger that selectively bonds with the analyte ion
liquid-membrane electrode for calcium
• Conducting membrane that selectively binds calcium ions (an ion
exchanger (calcium dialkyl phosphate) is dissolved in an immiscible
organic liquid that is forced by gravity into the pores of a hydrophobic
porous disk)
• Internal solution containing a fixed concentration of calcium chloride
• Internal reference electrode (Ag/AgCl)
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• DL=0.5 mM
• pH in the range between 5.5 and 11
• At lower pH levels becomes sensitive to pH as well as to pCa.
Potassium Ion Selective Electrode
• valinomycin
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Crystalline-Membrane Electrodes
A membrane with cationic sites might be expected to respond selectively
toward anions chloride, bromide, and iodide ions.
polycrystalline Ag2S sulfide ion
silver ions are sufficiently mobile to conduct electricity
• Mixtures of PbS, CdS, and CuS with Ag2S Pb2+, Cd2+, Cu2+
• A single crystal of lanthanum fluoride that has been doped with
europium(II) fluoride to improve its conductivity F-
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Ion-Sensitive Field Effect Transistors (ISFETs)
• Field effect transistor, or the metal oxide field effect transist (MOSFET),is a tiny
solid-state semiconductor device
• Two islands of n-type semiconductors are formed on the surface of the p-type
substrate, and the surface is then covered by insulating SiO2.
• Deposition of metallic conductors that are used to connect the MOSFET to
external circuits
• When an electrical potential is applied between the gate and the source, the
electrical conductivity of the channel is enhanced by a factor that is related to the
size of the applied potential
• Variation in the concentration of the ions of interest provides the variable
• gate voltage to control the conductivity of the channel
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Gas-Sensing Probes
• A tube containing a reference electrode, a specific ion electrode, and an
electrolyte solution
• A thin, replaceable, gas-permeable membrane
Membrane Composition
• Highly porous hydrophobic polymer
• (thickness 0.1 mm)
Mechanism of Response
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Instruments for Measuring Cell Potential
• In order to measure potentials of such highresistance circuits accurately, it is
necessary that the voltmeter have an electrical resistance that is several
orders of magnitude greater than the resistance of the cell being measured.
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Direct Potentiometry
• A rapid and convenient method for determining the activity of a
variety of cations and anions.
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The Electrode-Calibration Method
Constant K is made up of several constants, the junction potential, cannot
be measured directly or calculated from theory without assumptions.
K is determined by measuring Ecell for one or more standard solutions of
known pX or pA.
Assumption is then made that K is unchanged
Inherent Error in the Electrode-Calibration
Procedure
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Activity versus Concentration
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An obvious way to convert potentiometric measurements from activity
to concentration is to make use of an empirical calibration curve.
A total ionic strength adjustment
buffer (TISAB) is used to control the
ionic strength and the pH of samples
and standards, in ion-selective electrode
measurements.
Both samples and standards are diluted with a solution that contains sodium chloride, an
acetate buffer, and a citrate buffer; the diluent is sufficiently concentrated so that the samples
and standards have essentially identical ionic strengths.
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The Standard Addition Method
The standard addition method (see Section 8D-3) involves determining the potential of the
electrode system before and after a measured volume of a standard has been added to a known
volume of the analyte solution.
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Potentiometric Titrations
Potential of a suitable indicator electrode as a function of titrant volume
A rapid change in potential near the equivalence point, potentiometric titrations
are not dependent on measuring absolute values of Ecell
end point
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Neutralization Titrations
Determining Dissociation Constants
Half-titration point
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Potentiometric Determination of Equilibrium Constants
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