ISE

Ion Selective Electrodes

Prepared By
Michigan Department of Environmental Quality
Operator Training and Certification Unit
 Ion Selective Electrode

Electrode
Body

Ion Electrical
Sensitive Connection
Area
 Electrochemical
Measuring System
Meter

Reference Sensing
Electrode Electrode

Current Flow
 Combination Probe

Reference Sensing
Element Element
 Electrochemical
Measuring System
Meter

Reference Sensing
Electrode Electrode

Current Flow
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
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
 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
} Meter Reading
Also Affected
By All This

C = Concentration What We Want To Know

 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
} Must Be
Accounted For
To Get True
Concentration

C = Concentration What We Want To Know

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

 = Ionic Strength
C = Concentration What We Want To Know
 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
T = Temperature Specific Ion,
n = Charge on Ion Whole Number,
1, 2, 3, etc.
 = Ionic Strength + or -

C = Concentration What We Want To Know

 NERNST EQUATION
T Log  C
E= Eo + 2.3 n
E = Measured Voltage What the Meter Tells Us
Eo = Reference Constant
Must Be
T = Temperature Controlled By
n = Charge on Ion Making It A Very

 = Ionic Strength
High Value

C = Concentration What We Want To Know

 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
n = Charge on Ion ISAB

 = Ionic Strength
Na+ OH-

C = Concentration What We Want To Know

 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
n = Charge on Ion Directions!

 = Ionic Strength
C = Concentration What We Want To Know
 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
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
 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
 Effect of Temperature

s is the Direction (Angle) of the Line

Electrode Potential (mv)

100o C
50o C
0o C

Concentration (mg/L)

Temperature Affects the Slope

 Effect of Temperature
Electrode Potential (mv)

O 100o C
50o C
O
O 0o C

Concentration (mg/L)

One Concentration will Result in Different Readings

Dependent on Temperature
 Effect of Temperature
Electrode Potential (mv)

Sample Temperature

X
Calibration Temperature

O O
Concentration (mg/L)
When the Sample Temperature is Different from the
Calibration Temperature, an Incorrect Sample
Concentration will be Obtained
 Effect of Temperature
Electrode Potential (mv)

100o C
50o C
0o C

Isopotential
Point

Concentration (mg/L)
 Effect of Temperature
Electrode Potential (mv)

100o C
50o C
0o C

Isopotential
Point

Concentration (mg/L)

At the Isopotential Point, One Concentration will Result in

the Same Reading Independent of Temperature
 Effect of Temperature
Electrode Potential (mv)

100o C
50o C
0o C

Normal
Range of Analysis
}
Concentration (mg/L)

The Range of Analysis is Far From

the Isopotential Point for Most Samples
 Effect of Temperature
Electrode Potential (mv)

100o C
50o C
0o C

Normal
Range of Analysis
}
Concentration (mg/L)

Temperature Must be Accounted For in All Analyses

 Automatic Temperature Compensation
ATC

Adjusts Slope in Relation to Temperature

Sounds Good!
Does Not Work!
 Automatic Temperature Compensation
ATC

Adjusts Slope in Relation to Temperature

Is Accurate Only When Analysis

is Close to Isopotential Point

Only For pH
Automatic Temperature Compensation

ATC (Except
For
pH)
 Effect of Temperature

Calibrate With
Standards and
Electrode Potential (mv)

Samples At The
SAME Temperature
(Usually Room
Temperature)

Concentration (mg/L)
 Calibration Control
Electrode Potential (mv)

. Standard
Solution

Concentration (mg/L)
The Calibration Control Adjusts the “Curve”
to the Point of Standard Used
 Slope Control
Electrode Potential (mv)

. Standard

Concentration (mg/L)
The Slope Control Rotates the “Curve”
Around the Point Of the First Standard
 Slope Control
Second
Electrode Potential (mv)

. Standard

. Standard

Concentration (mg/L)
The Slope Control Adjust the “Curve”
through the Point of the Second Standard Used
NERNST EQUATION
E1 = E + s Log C1
o

E2 = Eo + s Log C2
If C2 = 10 x C1
Then:

E2 = E o + s Log 10C1
 NERNST EQUATION
E1 = E + s Log C1
o

E2 = Eo + s Log C2
If C2 = 10 x C1
E2 - E1 = s
The Slope of an Electrode
is the millivolt Change that is seen
for a Ten Times Change
in Concentration.
 ISE
Checking Electrode Slope
Carefully Prepare Two Standards
10 X Concentration Difference

Set Meter to Read in millivolts (or Relative mv)

Record mv Reading for Each Standard

Determine Difference = Slope

 ISE
Checking Electrode Slope
T Log  C
E= Eo + 2.3 n
Electrode Potential (mv)

Concentration (mg/L)
 ISE
Checking Electrode Slope
T Log  C
E= Eo + 2.3 n
The Slope Value Determined is Affected By:

Temperature (T)
Charge on the Ion of Interest (n)
Positive or Negative
1, 2, etc.
 ISE
Checking Electrode Slope
T Log  C
E= Eo + 2.3 n
The Slope Value Determined is Affected By:

Temperature (T)
Charge on the Ion of Interest (n)
Quality of the Standards
Efficiency of the Electrode
 ISE
Checking Electrode Slope
The Slope of the Electrode Will Change
{Loss of Efficiency}

The Slope Should be Checked Regularly

to Assure Reliable Results
Most Meters Give Slope When Calibrating
( In mv or %)

Record Slope for QA/QC Daily

(or at least every two weeks)
 ISE
Checking Electrode Slope
Ideal Slope Depends on Ion of interest (n)
Charge on the Ion of Interest (+ or -)
Approximately 59 mv for n=1
or 29 mv for n=2

Check Manufacturer for Acceptable Slope Range

Usually ± 10 % of Ideal
 ISE
Checking Electrode Slope
If Determined Slope is Outside of Acceptable Range
May Be Due To:

Poor Quality of Standards

Improper Probe Maintenance
Faulty Electrode

The Slope Should be Checked Regularly

to Assure Reliable Results
 ISE
Ion Selective Electrodes

Prepared By
Michigan Department of Environmental Quality
Operator Training and Certification Unit