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 ION SELECTIVE ELECTRODES
HISTORY
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Middle of the 60’s

First ISE for fluoride

Na+ K+ Ag+ Ca2+ NH+4 Cu2+ Pb2+

F- Cl- Br- I- CN- S2- NO3-

Until the 60’s the only ISE is in fact the pH electrode with a glass sensitive to
protons.

The fluoride electrode appeared in the middle 60’s. Since then a number of ISE
have been developed for cations and anions.

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 ION SELECTIVE ELECTRODES
WHERE?
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Environment

Food industry and agriculture

Medecine, pharmaceutical ,
cosmetics

Power plants

Ion measurements can be implemented in a number of applications :

for instance nitrate in waster water and brackish water,

Chloride and fluoride in mineral waters, potassium in fruit juices, chloride in beer,

Chloride in infusion solutions, in soap and shampoo

Chloride traces (high sensitivity chloride electrode) for boiler water ( corrosion
protection)

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ION SELECTIVE ELECTRODES
APPLICATIONS
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Fluoride water, plants, minerals, drugs

Calcium water, milk, cheese, beer, wine, serum, blood

Nitrates ground, surface and drinking waters

plants, soils, foodstuff

Copper plating bathes

complex. titration of copper, nickel, cadmium

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 ION SELECTIVE ELECTRODES
WHY?
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Economical

Time saving

Instrumentation simple

Automation (sample changer)

The measuring chain is very economical compared to other analytical techniques

like ion chromatography , AA or ICP...

The setup for measurements is fast : programmation of instrument, calibration of

electrode and measurements depending on response and stabilization time of the
electrode ( depends on electrode type , sample matrix, concentration level and
required level of accuracy). The most time consuming part is the preparation of
standard solutions, electrolyte and if necessary preparation of sample (wet
mineralization etc.)

The measuring chain consists of an ionmeter (originally a high accuracy

millivoltmeter), an ISE , a reference electrode, an ISB (ion strength buffer) and
standard solutions for electrode calibrations.

For routine analysis, a sample changer can be connected to the ionmeter.

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 ION SELECTIVE ELECTRODES
WHY?
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Wide dynamic range from 100 to 10-7 M

Measurement not disturbed by colour

or turbidity, no interference from solid
particles

According to the type of electrode and to sample matrix , the detection limit is at
10-6M for most models (high sensitivity chloride electrode) or even at 10-7 M like
the fluoride electrode.

To the contrary of colorimetric or spectrophotometric techniques for elemental

analysis, the measurement is undisturbed by colour , turbidity or particle in
suspension in the sample.

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 ION SELECTIVE ELECTRODES
LIMITATIONS
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Free ions only

Interferences from other ions

present in the sample

When ions are bound, it is necessary to free them before hand by an adequate
handling such as for instance wet mineralisation

Other ions present in the sample may interfere with the measurement : either they
also respond to the same electrode like for instance iodide, bromide to the chloride
electrode or they will bind or precipitate the ion to be measured, like silver ions
with chloride ions. The selectivity degree of the electrode is expressed by the
selectivity constant K and the activity of the interfering ion.

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 ION SELECTIVE ELECTRODES
THEORY
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Based on Nernst equation modified by:

Sensitivity factor Selectivity factor

E=E 0+
RT
*
S
nF 100
log (ax + Σkxia n ni )

The response of ISE is nearly Nerstian.

R/F can be replaced by 0.198 called Nernst factor.

The factor 0.198T/n will be ideally 59 mV for a monovalent ion, this represents
100% sensitivity. The Nernst equation can be modified by the sensitivity of the
electrode S/100%.

Second the selectivity of an electrode is never 100%, other ion may interfere and the
degree of selectivity to the ion to be measured x versus the interfering ion x1 is
expressed by the selectivity constant Kxi. The selectivity factor has to be included
for all interfering ions.
When Kxi = 2.10-2 for instance it means that the electrode is 50 times more sensitive
to x than to 1 (1/2 . 1/10-2 ).

When the value of Kxi is higher than one for a given ion it means that the electrode
is more sensitive to the interfering ion than to the ion to be measured.

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ION SELECTIVE ELECTRODES
THEORY
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Parameters of the equation

E= electrode potential
E0 = standard electrode potential (temperature dependant)
T= absolute temperature
F= Faraday’s constant
R= gas constant
n= valence of ion x
ax= activity of ion x
S/100% = sensitivity of electrode
Kxi = selectivity constant of primary ion x to interfering ion i

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 ION SELECTIVE ELECTRODES
WHAT IS NEEDED?
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Ionmeter
ISE (with filling solution)

Temperature sensor, reference electrode

Standard (addition) solution

Ion Strength Adjuster (ISA)

Ionmeter
ISE with filling solution if it is a ion exchange type electrode
Reference electrode preferably with double bridge of type REF251 of with salt
bridge extension
Temperature sensor : like for pH the electrode behaviour is Nernstian and therefore
temperature has to be taken into account
Standard solution or addition solution (known concentration) to calibrate the
electrode
Ionic strength is an important parameter in ion mesurements,it expresses the
concentration of all ions present in the solution both as concerns molarity and
charge.
Ion Strength Adjuster (also called “electrolyte”) is needed in order to give the
sample and the standard solutions a high and constant ionic strength. It does not
interfere on the measurement but compensatse for the difference between activity
and concentration. A Total Ion Strength Adjuster Buffer (TISAB) like for the
fluoride electrode allows at the same time to adjust the pH range.

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 ION SELECTIVE ELECTRODES
TYPICAL PROPERTIES
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Concentration range

pH range

Response time

Life time

The detection limit is different according to type of ion. This is determined by the
solubility constant of the crystal (or crystal powder ) used for the sensing
membrane. The less soluble the membrane, the lower the detection limit. Let us take
the example of chloride : at some point the Chlorides coming from the membrane
will be measured , this is the background noise or detection limit of the electrode.
The concentration range is an essential spec of the electrode

For some electrodes the pH range is essential as hydroxide ions or protons can
interfere : for instance OH- interfere on the fluoride crystal and H+ on the
measurement of sodium, as the sodium ion selective electrode is based on a
modified pH glass. The pH range is given in the specs of the electrode.

The response time of the electrode depends on its nature and design, and on the
concentration of the ion to be measured. At high concentration the response will be
faster than at low concentrations. An approximate response time is given in the
users manuals.

The life time depends on the working principle of the electrode and on its use: for
instance the Ag(CN)-2 building up when working with cyanide electrode is very
soluble and therefore the life time of the electrode is limited. Organic ion exchange
membrane electrodes also have a shorter life time than solid electrodes.

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 ION SELECTIVE ELECTRODES
TYPICAL PROPERTIES
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Membrane resistance (high)

Sensitivity deviation from the 100% (59 mV/decade)

Check point : potential for a 10-2 M standard solution

The membrane resistance is normally high and therefore the electrode is connected
to the high impedance input of the meter.

The sensitivity is a priority criterion. The check point is only an approximate

indication valid only in the same conditions strictly as the ones of the checking
bulletin , in particular using a difference reference electrode may radically modify
its value. The check point is an absolute value, whereas the sensitivity is a relative
one.

Both the sensitivity and the check point can drift with time, therefore regular
calibration is necessary.

The checking bulletin of a new electrode is always enclosed in the package

showing the value of the sensitivity and the check point.

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 ION SELECTIVE ELECTRODES
CHECKING BULLETIN
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sensitivity

Check point

All ISE of Radiometer Analytical are supplied with their checking bulletin showing
the calibration curve and the respective potential values for each of the standard
used.
The procedure used is a measurement in the electrolyte first, after stabilization a
100 µL addition of a concentrated standard solution is made in the electrolyte so as
to obtain the lowest concentration i.e. mostly 10 - 6 M, then successive additions ,
eventually of more concentrated solutions, are made in the same beaker so as to
cover the range of concentration of the electrode.

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 ION SELECTIVE ELECTRODES
VARIOUS TYPES
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Glass

Solid state

Organic membrane (ion exchange)

Single or combined

Glass electrode is the sodium (glass is of pH type modified) with a strong

interference from Potassium

Solid state: chloride, fluoride, silver/sulfide, lead, copper, bromide, iodide, cyanide

Ion exchange membrane : potassium, nitrate, ammonium, calcium

Combined : fluoride

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 ION SELECTIVE ELECTRODES
H+ and Na+
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Hydrated layer around the glass membrane

Surface acts as a cation exchanger

H+ (pH ) electrode unique Na+ electrode modified pH glass

14 decades of concentration Strong interference from H+

Short response time

The hydrated layer is very narrow (order of 10-6 cm), it forms spontaneously when
electrode is left in a solution.

For H+, the sodium or lithium ions in the glass membrane are exchanged with the
protons.

The sodium electrode is just a modified pH glass. It is still very sensitive to H+ ions,
but this is overcome by adjusting the pH to alkaline values.

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 ION SELECTIVE ELECTRODES
H+ and Na+
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Inner reference element Ag/AgCl wire

Inner solution

Ion sensitive glass membrane

The glass for the sodium electrode is modified compared to the glass used for pH.

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 ION SELECTIVE ELECTRODES
SOLID STATE
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Cl-
AgCl
FF- -
Ag+/S--
LaF3
LaF3 Ag2S

Solid state
Electrodes
CN
CN,-,II-
- - Pb ++
Pb++
AgI
AgI PbS
PbS

Br-
Br- Cu ++
Cu++
AgBr
AgBr Cu
Cu1.8 Se
1.8Se

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ION SELECTIVE ELECTRODES
SOLID STATE
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Ionically conducting membrane made of one or

more inorganic salts

Monocrystal (LaF3) or polycrystal (Ag2S)

Inorganic salt solubility determines detection

limit

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 ION SELECTIVE ELECTRODES
SOLID STATE
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F- electrode CN- electrode

LaF3 monocrystal AgI polycrystal

F- CN- Ag+
F-
TISAB pH adjuster and Ag(CN)2- soluble, limited life
decomplexer of AlF6 and MgF4 in high CN- concentrations

The working principle of the ISE is different according to reaction type.

On the most common fluoride electrode the equilibrium (charge carrier) is F-
according to the reaction :

LaF3 ⇔ La 3+ + 3 F-

TISAB : total ion strength adjuster buffer. 3 Functions: adjusts the pH, decomplex
the bound F- ions and adjust the ion strength so as to make sure that measurements
in samples can be referred to calibration conditions.

For the cyanide electrode for instance the equilibrium is based on the CN-
exchanged with Ag+ (from the AgI polycrystal) following the reaction :

AgI + 2CN- ⇔ Ag(CN)-2 + I -

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ION SELECTIVE ELECTRODES
SOLID CONTACT
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Cyanide, iodide, copper

Black epoxy tube

Conductive rod

Conductive pads

Sensing polycrystal

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ION SELECTIVE ELECTRODES
LIQUID CONTACT
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Chloride, Bromide, Fluoride

Silver, Lead

Black epoxy tube

Conductive wire

Filling solution
Insulating material

Sensing element

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 ION SELECTIVE ELECTRODES
ORGANIC ION EXCHANGER
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Ammonium, Potassium, Calcium, nitrate

Potassium valinomycin antibiotics

Calcium organic calcium phosphate

Nitrate organic ammonium nitrate

Ammonium antibiotic

The ion exchange element is incorporated in a PVC membrane.

The potassium and ammonium ion exchanger have structure with a cavity where the
size of the respective ion fits perfectly.

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ION SELECTIVE ELECTRODES
ORGANIC ION EXCHANGER
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Ammonium, Potassium, Calcium, nitrate

Ion exchanger dissolves in water

Life time shorter than crystaline electrodes

Membrane tube is removable

Spare membranes are supplied

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 ION SELECTIVE ELECTRODES
COMBINED FLUORIDE ELECTRODE

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Filling aperture for external reference

AgAg/Cl wire external reference

KCl 3M AgCl solution for ext. ref.

AgAg/Cl wire internal reference
Internal filling solution ( not refillable)

Porous junction of external reference

LaF3 Monocrystal

The ion exchange element is incorporated in a PVC membrane.

The potassium and ammonium ion exchanger have structure with a cavity where the
size of the respective ion fits perfectly.

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 ION SELECTIVE ELECTRODES
REFERENCE ELECTRODE
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Constant potential

No interference with ion in solution, no Hg/HgCl2 or

Ag/AgCl with:

Sodium K+ of KCl interferes

Chloride Cl- of KCl contributes to measurement

salt bridge or double junction reference electrode

filled with relevant ISA

Calomel electrode is very stable but goes only up to 70°C and shows hysteresis
when temperature changes, in turn the Ag/AgCl electrode goes up to 100°C fast
response to temperature variations, but slightly more instable and sensitive to light.

However in some cases, elements from the 2 electrodes may interfere on the
measurement : for instance for sodium measurement the potassium from the KCl
filling solution will act as an interfering ion, and when measuring chloride, the
chloride from the KCl will increase the result and bring an error.

Therefore reference electrode with double junction of type REF251 or the use of a
removable salt bridge is preferred. The advantage of using a salt bridge is that when
measuring different ions, it is easier to fill it with the relevant electrolyte. However
in order to avoid contaminations, it is recommended to use one dedicated salt bridge
or double junction reference for each different ion.

The solution filled in the second junction of in the salt bridge is the electrolyte (Ion
Strenght Adjuster) in order to minimize the junction potential.

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ION SELECTIVE ELECTRODES
MEASURING METHODS
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Direct potentiometry (calibration curve)

Standard addition

Standard subtraction

Analate addition

Analate subtraction

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ION SELECTIVE ELECTRODES
SELECTION OF THE METHOD
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Sample matrix

Concentration level

Accuracy requested

Time

Convenience

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 ION SELECTIVE ELECTRODES
PROCEDURE
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Use of 2 or more standards

Bracketing procedure

Use of Ionic Strength Adjuster

pH adjuster and/or decomplexing agent

Temperature identical in standards and samples.

The sample and standard solutions must be similar in composition in order to avoid
matrix effects. This is the reason why ISA is added to both standard solutions and
sample.

The TISAB used for the fluoride measurements is alltogether an ISA ( NaCl), pH
adjuster between 5 and 6 and a decomplexing agent DCTA which builds complexes
with Aluminium, iron and magnesium to release fluoride ions.

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 ION SELECTIVE ELECTRODES
DIRECT POTENTIOMETRY
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E = E 0 + S 25T / T 25 log(C + Bl )
E = measured potential
E0 = standard electrode potential (mV determined by calibration)
S25 = sensitivity at 25°C (mV/pC)
T = calibration temperature
T25 = 298.16 K
C = concentration of standard
Bl= blank detection limit of electrode

Csmp = C meas - Bl

The concentration of the sample is the total concentration measured less the value of
the Blank, this is specially significant for very low concentrations ( non linear part
of the electrode response range).

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 ION SELECTIVE ELECTRODES
CALIBRATION CURVE
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E (mV)
E¡
90 Standard potential
60
C1
E1
dC/Std
ST
30 Deviation from
C2 -0
fitted curve
E2
for each point
-30

-90

-120

-150

Bl
Blank = experimental
-180 detection limit of the
electrode
log[C] -210
10-7 10-6 10-5 10-4 10-3 10-2 10-1 1

The blank is determined during the calibration. It represents the detection limit of
the electrode.

It is the intersection of the extrapolated linear response part and horizontal part of
the electrode. It allows to have results in the non linear response area of the
electrode which have the same accuracy as in the linear part.

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 ION SELECTIVE ELECTRODES
ACCURACY OF DIRECT POTENTIOMETRY

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Typically ± 2-4% for monovalent ions, ±4-8 % for divalent ions

Accuracy of the meter

Precision of the electrode

Accuracy on sensitivity (standard solutions)

Accuracy on temperature control

Sample pretreatment (all ions free or not)

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 ION SELECTIVE ELECTRODES
STANDARD ADDITION PRINCIPLE
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ISE = F-
Sample = F-
Standard addition = F-

Sample Addition 1 Addition 2…9

In the standard addition method, the potential of the sample is measured first, then
several additions of identical volume of a concentrated standard solution are added
and each time the potential of sample + addition recorded.

The addition volume must be small with regard to the sample volume so that the
total ionic strength remains constant, the degree of complexation of the specific ion
remains constant, the liquid junction potential of the reference electrode remains
constant.

The electrode sensitivity is determined by 2or more additions. If only one addition
is made, the slope/sensitivity of the electrode must be known.

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ION SELECTIVE ELECTRODES
STANDARD ADDITION WHEN?
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If sample matrix difficult to reproduce for standards

Best accuracy if total amount of ion added is 0.5 to 2

total amount of ions in sample

Valid only in linear response range

Potential variation due to addition :

10-30 mV for a monovalent ion

5-15 mV for a divalent ion

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 ION SELECTIVE ELECTRODES
STANDARD SUBTRACTION PRINCIPLE
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ISE = I-
Sample = I-
Standard addition = Ag+-

Sample Addition 1 Addition 2…9

The potential measurement is taken first in the sample. A reagent which combines
with the specific ion is added ( here silver to iodide), i.e. the concentration of the
specification in the sample will decrease at each subtraction.

Calculation of sample concentration is same as for addition with a negative sign.

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 ION SELECTIVE ELECTRODES
STANDARD SUBTRACTION WHEN?
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When standard of the ion is instable (I- or S 2- )

Addition volume and concentration adjusted

so as not to react with all the amount of ion in the sample

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 ION SELECTIVE ELECTRODES
STANDARD ADDITION/SUBTRACTION
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± CstdVstd
Csmp =
(Vsmp + Vstd )10( E1− E ) / S − Vsmp
For one addition/subtraction
Csmp sample concentration
Cstd standard concentration
Vsmp sample volume
Vstd standard volume
E potential before 1st addition/subtraction
E1 potential after addition/subtraction
S sensitivity

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 ION SELECTIVE ELECTRODES
ANALATE ADDITION PRINCIPLE
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ISE = F-
Standard = F-
Analate (sample) = F-

Sample Analate add. 1 Analate add. 2…9

First a potential measurement is taken in the standard solution.

The, sample aliquots (same volume, small volumes) are added to the standard and
potential taken after each measurements

The sample concentration is calculated after the procedure has been completed.

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ION SELECTIVE ELECTRODES
ANALATE ADDITION WHEN?
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High ion concentration in sample, avoids dilution errors

When sample volume available is small

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 ION SELECTIVE ELECTRODES
ANALATE SUBTRACTION PRINCIPLE
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ISE = Pb2+
Complexing Standard = Pb(NO3)2
Analate (sample) = SO42-

Sample Analate add. 1 Analate add. 2…9

First a potential measurement is taken in the standard solution, which is in this case
a complexing reagent of known concentration like lead nitrate (in solution) , the
electrode is selective to lead.

Additions of the sample (here sulfate) are made. The reaction is the formation of
lead sulphate which precipitates, i.e. the lead detected by the electrode is decreasing
(difference between the solubility product of lead nitrate and lead sulphate). This is
a way to measure the sulphate in a sample by direct potentiometry with a lead
electrode, as no sulphate electrode is available.

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 ION SELECTIVE ELECTRODES
ANALATE SUBTRACTION WHEN?
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Indirect method, no ISE for the ion to determine

High concentration in samples, avoids dilution

CARE : the sample aliquots have to be well adjusted

to avoid reacting with all reagent upon first addition.

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 ION SELECTIVE ELECTRODES
ANALATE ADDITION/SUBTRACTION
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± Cstd (Vstd + Vsmp )10 ( E1− E ) / S − CstdVstd

Csmp =
Vsmp

For one addition/subtraction

Csmp sample concentration
Cstd standard concentration
Vsmp sample volume
Vstd standard volume
E potential before 1st addition/subtraction
E1 potential after addition/subtraction
S sensitivity

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 ION SELECTIVE ELECTRODES
BENEFITS OF ADDITIONS/ANALATES
42

When matrix is difficult to reproduce

From 2 addition or analates: S calculated automatically:

No need to calibrate
Permanent check of electrode response

Avoids dilution errors

No temperature variation between measurements:

volumes added are very small.

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 ION SELECTIVE ELECTRODES
LIMITS OF ADDITIONS/ANALATES
43

Only in electrode linear response range

Time consuming : procedure repeated at each measurement

Ion concentration in sample must be approx. known

to adjust volume and concentration s of additions/analates

Total volume added must be kept small

to keep ionic strength/pH constant.

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