Potentiometry
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principles of potentiometry

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Potentiometry

POTENTIOMETRY


Potentiometric analysis

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

Applications of Potentiometric Analysis


Components of a potentiometric cell

Components of a Potentiometric Cell

  • Reference electrode

  • Salt bridge

  • Analyte

  • Indicator electrode

RE SB A IE

– Eref + Ej + Eind


Reference electrode

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

Indicator electrode

  • Generates a potential (Eind) that depends on analyte concentration

  • Selective

  • Rapid and reproducible response


Salt bridge

Salt bridge

  • Prevents mixing up of analyte components

  • Generates potential (Ej) = negligible


Reference electrodes

Reference Electrodes

  • Standard Hydrogen Electrode

  • Calomel Reference Electrode

  • Silver/Silver Chloride Reference Electrode


Potentiometry

SHE

  • Hydrogen Gas Electrode

  • Pt (H2 (1 atm), H+ (1M)


Saturated calomel electrode

Saturated Calomel Electrode

Hg2Cl2(s)+2e-2Hg(l)+2Cl-(aq)

  • Aka SCE

  • Easy to prepare

  • Easy to maintain

  • 0.2444 V at 25C

  • Dependent on temp

  • Toxic


Potentiometry

SCE


Ag agcl ref electrode

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 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.


Indicator electrodes

Indicator Electrodes

  • Metallic IE

    • Electrodes of the First Kind

    • Electrodes of the Second Kind

    • Inert Metallic Electrodes (for Redox Systems)

  • Membrane IE

    • Glass pH IE

    • Glass IE for other cations

    • Liquid Membrane IE

    • Crystalline-Membrane IE

  • Gas Sensing Probes


Metallic indicator electrodes

METALLIC INDICATOR ELECTRODES


Electrodes of the first kind

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

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

Electrodes of the Second Kind

  • Respond to anions by forming precipitates or stable complex

  • Examples:

    • Ag electrode for Cl- determination

    • Hg electrode for EDTA determination


Inert metallic redox electrodes

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

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

Glass pH Electrode


Properties of 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


Potentiometry

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

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

Acid error

  • Exhibited at pH < 0.5

  • pH readings are higher (curves A and B)

    • Saturation effect with respect to H+


Selectivity coefficient

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.

    • The smaller the selectivity coefficient, the less interference by X.


Selectivity coefficient1

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


Liquid membrane electrodes1

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


Potentiometry

0.1 M CaCl2

Responsive to Ca2+


Characteristics of ca 2 ise

Characteristics of Ca+2 ISE

  • Relatively high sensitivity

  • Low LOD

  • Working pH range: 5.5 – 11

  • Relevant in studying physiological processes


A k selective electrode

A K+-selective electrode

  • Sensitive membrane consists of valinomycin, an antibiotic


Crystalline membrane electrodes

CRYSTALLINE-MEMBRANE ELECTRODES


Crystalline membrane electrodes1

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 electrodes2

Crystalline-Membrane Electrodes

  • AgX membrane: Determination of X-

  • Ag2S membrane: Determination of S-2

  • LaF3 membrane: Determination of F-


F selective electrode

F- Selective Electrode

  • A LaF3 is doped with EuF2.

  • Eu2+ has less charge than the La3+, so an anion vacancy occurs for every Eu2+.

  • 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

Fluoride Electrode


Gas sensing probes

GAS SENSING PROBES


Gas sensing probes1

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

Gas Sensing Probe


Direct potentiometry

DIRECT POTENTIOMETRY

  • A rapid and convenient method of determining the activity of cations/anions


Potentiometric measurement

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 measurement1

Potentiometric Measurement

Calibration Method

Standard Addition Method


Special applications potentiometric ph measurement using glass electrode

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

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

Potentiometric Titration Curves


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