Ion Selective Electrodes

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 Ion Selective Electrode

Electrode
Body

Ion Electrical
Sensitive Connection
Area

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 ION-SELECTIVE ELECTRODES (ISE)
Also known as indicator electrodes

- Respond directly to the analyte

- Used for direct potentiometric measurements

- Selectively binds and measures the activity of one ion

(no redox chemistry)

Examples
pH electrode
Calcium (Ca2+) electrode
Chloride (Cl-) electrode
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ION-SELECTIVE ELECTRODES (ISE)
Advantages
- Exhibit wide response

- Exhibit wide linear range

- Low cost

- Color or turbidity of analyte does not affect

results

- Come in different shapes and sizes

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ION-SELECTIVE ELECTRODES (ISE)
- Made from a perm selective ion-conducting membrane
(ion-exchange material that allows ions of one electrical
sign to pass through)

- Reference electrode is inbuilt

- Internal solution (solution inside electrode) contains ion of

interest with constant activity

- Ion of interest is also mixed with membrane

- Membrane is nonporous and water insoluble

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ION-SELECTIVE ELECTRODES (ISE)
- Responds preferentially to one species in solution

Internal reference
electrode

Internal (filling)
solution

Ion-selective membrane
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ION-SELECTIVE ELECTRODES (ISE)

- Selective (preferential) ion is C+

- Membrane is made of poly(vinyl chloride) (PVC)

- Membrane is impregnated (soaked) with nonpolar liquid

- Membrane contains ligand L (ion-selective ionophore)

- Membrane contains the complex LC+

- Membrane contains hydrophobic anion R- (ion exchanger)

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8
 ION-SELECTIVE ELECTRODES (ISE)
- [C+] inside the electrode ≠ [C+] outside the electrode

- Results in a potential difference across the membrane

RT  [C  ]outer 
E ln   

z i F  [C ]inner 
0.05916  [C  ]outer 
At 25 C, E 
o
log   

zi  [C ] inner 

Log10 = 1
Generally (at 25 oC)
- 10-fold change in activity implies 59/zi mV change in E

- zi is the charge on the selective ion (negative for anions)

zi = +1 for K+,
zi = +2 for Ca2+,
zi = -2 for CO32-
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ION-SELECTIVE ELECTRODES (ISE)
Let ci = molarity of C+

- Activity (ai) rather than molarity is measured by ISEs

- Activity is the effective (active) concentration of analyte

(effective concentration decreases due to ionic interactions)

zi = ionic charge (±)

ai = γici

where γi = activity coefficient (between 0 and 1)

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ION-SELECTIVE ELECTRODES (ISE)
Debye-Hückel Equation

Relates activity coefficients to ionic strength (at 25 oC)

 0.51z i2 μ
log γ 
1  (α μ /305)

α = size of ion in picometers (1 pm = 10-12 m)

µ = ionic strength

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 ION-SELECTIVE ELECTRODES (ISE)
Ionic strength
A measure of the concentration of all ions in solution
with their charges taken into account
1 1
 
μ   c i z i  c i z i2  c i z i2  c i z i2  .........
2 i
2

2
ci = the concentration of the ith species
Ionic strength of electrolytes
1:1 electrolytes (NaCl) µ = molarity
2:1 electrolytes (CaCl2) µ = 3 x molarity
3:1 electrolytes (AlCl3) µ = 6 x molarity
2:2 electrolytes (MgSO4) µ = 4 x molarity
½ {(1)2 +(-1)2} ci = 1 molarity
½ {(+2)2 +(-1)2 + +(-1)2} ci = ½ (4+1+1) molarity = 6/2 = 3 x molarity
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ION-SELECTIVE ELECTRODES (ISE)

- For very dilute solutions ai ≈ ci

- Activity coefficient decreases as ionic strength increases

For zi = 1
- 1 mV change in potential implies 4% change in activity

For zi = 2
- 1 mV change in potential implies 8% change in activity

- This is known as Nernstian behavior

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 ION-SELECTIVE ELECTRODES (ISE)
Selectivity Coefficient (k)

-A measure of the ability of ISE to discriminate(distinguish,

differentiate, separate) against an interfering ion

- It is assumed that ISEs respond only to ion of interest

- In practice, no electrode responds to only one specific ion

- The lower the value of k the more selective is the electrode

- k = 0 for an ideal electrode (implies no interference)

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ION-SELECTIVE ELECTRODES (ISE)

Selectivity Coefficient (k)

For k > 1
- ISE responds better to the interfering ion than to the target ion

For k = 1
- ISE responds similarly to both ions

For k < 1
- ISE responds more selectively to ion of interest

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ION-SELECTIVE ELECTRODES (ISE)
Empirical Calibration Plot
0.05916  [C  ]outer 
At 25 C, E 
o
log   

zi  [C ]inner 
Potential (mV)

Slope = 59/zi mV

zi = charge of ion

Called Nernstian slope

p[C+]

- Used to determine the unknown concentration of analytes

- Departure from linearity is observed at low concentrations 16

ION-SELECTIVE ELECTRODES (ISE)

Three groups of ISEs

- Glass electrodes

- Liquid electrodes

- Solid electrodes

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 GLASS ELECTRODES

- Responsive to univalent cations

- Employs thin ion-selective glass membrane

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 pH GLASS ELECTRODE

- The most widely used

- For pH measurements (selective ion is H+)

- Response is fast, stable, and has broad range

- pH changes by 1 when [H+] changes by a factor of 10

- Potential difference is 0.05196 V when

[H+] changes by a factor of 10

For a change in pH from 3.00 to 6.00 (3.00 units)

Potential difference = 3.00 x 0.05196 V = 0.177
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 pH GLASS ELECTRODE

- Thin glass membrane (bulb) consists of SiO4

- Most common composition is SiO2, Na2O, and CaO

Glass membrane contains

-dilute HCl solution

- inbuilt reference electrode (Ag wire coated with

AgCl) 20
 pH GLASS ELECTRODE
Glass Electrode Response at 25 oC
(potential across membrane with respect to H+)

E  K  β(0.05916)ΔpH
E  K - 0.05916log (a H  )

ΔpH = pH difference between inside and outside of glass bulb

β ≈ 1 (typically ~ 0.98)
(measured by calibrating electrode in solutions of known pH)

K = assymetry potential (system constant, varies with electrodes)

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pH measurements with a Glass electrode
• The glass electrode used to
measure pH is the most common
ion-selective electrode.

• A typical pH combination
electrode, incorporating both
glass and reference electrodes in
one body.

• Glass combination electrode with

a silver-silver chloride reference
electrode.
• The glass electrode is immersed
in a solution of unknown pH so
that the porous plug on the lower
right is below the surface of the
liquid.
• The two silver electrodes measure
the voltage across the glass
membrane. 22
• The potential difference between inner and outer silver-silver chloride electrodes
depends on the chloride concentration in each electrode compartment and on the
potential difference across the glass membrane.

• Because [Cl−] is fixed in each compartment and because [H+] is fixed on the
inside of the glass membrane, the only variable is the pH of analyte solution
outside the glass membrane.

• The voltage of the ideal pH electrode changes by 59.16 mV for every pH-unit
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change of analyte activity at 25°C.
 pH GLASS ELECTRODE
- Equilibrium establishes across the glass membrane with
respect to H+ in inner and outer solutions

- This produces the potential, E

- Linearity between pH and potential

- Calibration plot yields slope = 59 mV/pH units

- Electrode is prevented from drying out by storing in

aqueous solution when not in use
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pH GLASS ELECTRODE

Sources of Error

- Standards used for calibration

- Junction potential
- Equilibration time
- Alkaline (sodium error)
- Temperature
- Strong acids
- Response to H+ (hydration effect)

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 OTHEER GLASS ELECTRODES

Glass Electrodes For Other Cations

K+ -, NH4+-, Na+-selective electrodes

-Mechanism is complex
-Employs aluminosilicate glasses (Na2O, Al2O3, SiO2)
- Minimizes interference from H+ when solution pH > 5

pH Non glass Electrodes

- Quinhydrone electrode (quinone – hydroquinone couple)

- Antimony electrode 26
 LIQUID MEMBRANE ELECTRODES

- Employs water-immiscible substances impregnated in a

polymeric membrane (PVC)

- For direct measurement of polyvalent cations and some anions

- The inner solution is a saturated solution of the target ion

- Hydrophilic complexing agents (e.g. EDTA) are added to inner

solutions to improve detection limits

- Inner wire is Ag/AgCl

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 LIQUID MEMBRANE ELECTRODES
Ion-Exchange Electrodes

- The basis is the ability of phosphate ions to form stable

complexes with calcium ions

- Selective towards calcium

- Employs cation-exchanger that has high affinity for calcium ions

(diester of phosphoric acid)

- Inner solution is a saturated solution of calcium chloride

- Cell potential is given by
0.05916
EK log(a Ca ) 28
2
LIQUID MEMBRANE ELECTRODES

Other Ion-Exchange Electrodes

- Have poor selectivity and are limited to pharmaceutical

formulations

Examples
- IEE for polycationic species (polyarginine, protamine)
- IEE for polyanionic species (DNA)
- IEE for detection of commonly abused drugs
(large organic species)
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LIQUID MEMBRANE ELECTRODES

Neutral Carrier Electrodes

- Employs neutral carriers such as crown ethers and

cyclic polyesters

- Carriers envelope target ions in their pockets

Used for clinical analysis

- detection of blood electrolytes
- Detection of alkali and alkaline earth metal cations

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 LIQUID MEMBRANE ELECTRODES
Neutral Carrier Electrodes

Examples of Carriers
- Monessin (inophore) for sodium
- Macrocyclic thioethers for Hg and Ag
- Valinomycin for potassium ions
- Calixarene derivatives for lead
- 14-crown-4-ether for lithium
Monensin is a polyether antibiotic isolated from Streptomyces cinnamonensis. It
is widely used in ruminant animal feeds.
Monensin A is an ionophore related to the crown ethers with a preference to form
complexes with monovalent cations such as: Li+, Na+, K+, Rb+, Ag+, and Ti+
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LIQUID MEMBRANE ELECTRODES

Anion-Selective Electrodes

- For sensing organic and inorganic anions

Examples of Anions
- Phosphate
- Salicylate
- Thiocyanate
- Carbonate

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 SOLID-STATE ELECTRODES

- Solid membranes that are selective mainly to anions

Solid-state membrane may be

-single crystals

-polycrystalline pellets

or

- mixed crystals

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 SOLID-STATE ELECTRODES
Examples

- Most common is fluoride-ion-selective electrode

(limited pH range of 0-8.5)

(OH- is the only interfering ion due to similar size and charge)

- Iodide electrode (high selectivity over Br- and Cl-)

Chloride electrode (suffers interference from Br- and I-)

Thiocynate (SCN-) and cyanide (CN-) electrodes

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 OTHER ELECTRODES
- Coated-wire electrodes (CWE)

- Solid-state electrodes without inner solutions

- Made up of metallic wire or disk conductor (Cu, Ag, Pt)

- Mechanism is not well understood due to lack of

internal reference

- Usually not reproducible

For detection of
amino acids, cocaine, methadone, sodium
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 APPLICATIONS OF ISEs
- Used as detectors for automated flow analyzers
(flow injection systems)

- High-speed determination of blood electrolytes in hospitals

(H+, K+, Cl-, Ca2+, Na+)

- For measuring soil samples (NO3-, Cl-, Li+, Ca2+, Mg2+)

- Coupling ion chromatography with potentiometric detection

- Micro ISEs as probe tips for SECM (scanning electrochemical

microscopy)

- Column detectors for capillary-zone electrophoresis 36

Thanks

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 Electrochemical
Measuring System
Meter

Reference Sensing
Electrode Electrode

Current Flow

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 Combination Probe

Reference Sensing
Element Element

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NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage
Eo = Reference Constant
T = Temperature
n = Charge on Ion
 = Ionic Strength
C = Concentration
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NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage
Eo = Reference Constant
T = Temperature
n = Charge on Ion
 = Ionic Strength
C = Concentration
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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
T = Temperature
n = Charge on Ion
 = Ionic Strength
C = Concentration
}Meter Reading Also
Affected By All This

What We Want To Know

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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
T = Temperature
n = Charge on Ion
 = Ionic Strength
C = Concentration
} Must Be Accounted
For To Get True
Concentration

What We Want To Know

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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
Must Maintain
T = Temperature Reference Electrode

n = Charge on Ion
 = Ionic Strength
C = Concentration What We Want To Know

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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant Will Be Constant for
Specific Ion,
Whole Number,
T = Temperature 1, 2, 3, etc.
+ or -
n = Charge on Ion
 = Ionic Strength
C = Concentration What We Want To Know

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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
Must Be Controlled By
T = Temperature Making It A Very High
Value
n = Charge on Ion
 = Ionic Strength
C = Concentration What We Want To Know

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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
T = Temperature Add Ions
ISAB
n = Charge on Ion +
OH -

 = Ionic Strength
Na

C = Concentration What We Want To Know

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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
Follow
T = Temperature The
Directions!
n = Charge on Ion
 = Ionic Strength
C = Concentration What We Want To Know

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 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
T = Temperature Must Be
n = Charge on Ion Controlled
 = Ionic Strength
C = Concentration What We Want To Know

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NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage
Eo = Reference Constant
T = Temperature
n = Charge on Ion
 = Ionic Strength
C = Concentration
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NERNST EQUATION
T Log  C
E= Eo + 2.3 n
y = mx + b
T
2.3 n = s = slope

Slope is Direction of “Curve”

When Plotting E vs. C

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