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Ion-Selective Electrodes: Ammonium, Calcium, Chloride, and Nitrate Measurements, Slides of Applied Chemistry

Information on the use of ion-selective electrodes (ISEs) for measuring concentrations of Ammonium (NH4+), Calcium (Ca2+), Chloride (Cl-), and Nitrate (NO3-) ions in aqueous solutions. details on the range of ISE electrodes, resolution, interfering ions, electrode slope, approximate calibration voltages, electrode resistance, and reproducibility. It also explains how to maintain and replace the ISE standard calibration solutions, and provides instructions for using ISA solutions to improve accuracy.

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2021/2022

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Ion Selective Electrodes
Ammonium Ion-Selective Electrode (Order Code NavNH4)
Calcium Ion-Selective Electrode (Order Code NavCA)
Chloride Ion-Selective Electrode (Order Code NavCL)
Nitrate Ion-Selective Electrode (Order Code NavNO3)
The Forston Labs Ion-Selective Electrodes can be used to measure the concentration of a specific ion in
aqueous samples. The species available include Nitrate (NO3-), Chloride (Cl-), Calcium (Ca2+), and
Ammonium (NH4+).
Inventory of Items Included with the ISE
One Ion-Selective Electrode (Nitrate, Calcium, Chloride or Ammonium).
One bottle of High Standard solution with MSDS sheet.
One bottle of Low Standard solution with MSDS sheet.
One ISE Soaking Bottle (empty bottle with insertion cap).
Collecting Data with the ISE
Here is the general procedure to follow when using the ISE:
1. The Ion-Selective Electrode (ISE) must be soaked in the High Standard solution (included with the
ISE) for approximately 30 minutes. Note: It is good laboratory practice to condition the electrode in a
standard solution with the same or slightly higher value than the anticipated value of the solution to be
tested. If the anticipated value is unknown or if such a standard is unavailable, use the High
Concentration Standard provided with the electrode. Important: Make sure the ISE is not resting on
the bottom of the container, and that the small white reference contacts are immersed. Make sure no
air bubbles are trapped below the ISE.
2. If the ISE needs to be transported to the field during the soaking process, use the Short-Term ISE
Soaking Bottle. Remove the cap from the bottle and fill it 3/4 full with High Standard. Slide the bottle’s
cap onto the ISE, insert it into the bottle, and tighten. Important: Do not leave the ISE soaking for
more than 24 hours. Long-term storage should be in the Long-Term ISE Storage Bottle.
3. Connect the ISE to the LabNavigator..
4. The software will identify the ISE unless an Electrode Amplifier is used to interface with an electrode
with a BNC type connector. (see Electrode Amplifier Use below for Labnavigator setup for these type
of measurements.)
Labnavigator™ Setup for Use of the Electrode Amplifier (PN NavEamp)
The Electrode Amplifier allows the user to use electrodes using the BNC type connector with the
LabNavigator™. The Electrode Amplifier measurements are displayed in mV potential within the Meter
Screen.
To record the species being measured within the data, go to Table Tab and tap the Title Window. You can
then edit this for species name, run number, etc.
Note: If it is known if whether the species to be measured is monovalent (such as F- or NO3-3) or divalent
(such as Mg2+ or Ca2+), a shortcut for the analysis functions of the LabNavigator App is available:
1. Attach the Electrode Amplifier (EA) to the Electrode and insert the BTA connector on the EA into one of
the analog ports on the LabNavigator™.
2. In the LabNavigator™ App, select Sensors then Sensor Setup.
3. Locate the Drop Down Menu for the port showing the EA.
4. In the Drop Down Menu, select either Nitrate for monovalent ion measurements or Calcium for divalent
ion measurements. Note: Although the display will show labels for Calcium or Nitrate, ALL the
measurements will be in the desired units and correct.
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Download Ion-Selective Electrodes: Ammonium, Calcium, Chloride, and Nitrate Measurements and more Slides Applied Chemistry in PDF only on Docsity!

Ion Selective Electrodes

Ammonium Ion-Selective Electrode (Order Code NavNH4)

Calcium Ion-Selective Electrode (Order Code NavCA)

Chloride Ion-Selective Electrode (Order Code NavCL)

Nitrate Ion-Selective Electrode (Order Code NavNO3)

The Forston Labs Ion-Selective Electrodes can be used to measure the concentration of a specific ion in

aqueous samples. The species available include Nitrate (NO 3

), Chloride (Cl

), Calcium (Ca

2+ ), and

Ammonium (NH 4

).

Inventory of Items Included with the ISE

  • One Ion-Selective Electrode (Nitrate, Calcium, Chloride or Ammonium).
  • One bottle of High Standard solution with MSDS sheet.
  • (^) One bottle of Low Standard solution with MSDS sheet.
  • (^) One ISE Soaking Bottle (empty bottle with insertion cap).

Collecting Data with the ISE

Here is the general procedure to follow when using the ISE:

  1. The Ion-Selective Electrode (ISE) must be soaked in the High Standard solution (included with the

ISE) for approximately 30 minutes. Note: It is good laboratory practice to condition the electrode in a

standard solution with the same or slightly higher value than the anticipated value of the solution to be

tested. If the anticipated value is unknown or if such a standard is unavailable, use the High

Concentration Standard provided with the electrode. Important: Make sure the ISE is not resting on

the bottom of the container, and that the small white reference contacts are immersed. Make sure no

air bubbles are trapped below the ISE.

  1. If the ISE needs to be transported to the field during the soaking process, use the Short-Term ISE

Soaking Bottle. Remove the cap from the bottle and fill it 3/4 full with High Standard. Slide the bottle’s

cap onto the ISE, insert it into the bottle, and tighten. Important: Do not leave the ISE soaking for

more than 24 hours. Long-term storage should be in the Long-Term ISE Storage Bottle.

  1. Connect the ISE to the LabNavigator..
  2. The software will identify the ISE unless an Electrode Amplifier is used to interface with an electrode

with a BNC type connector. (see Electrode Amplifier Use below for Labnavigator setup for these type

of measurements.)

Labnavigator™ Setup for Use of the Electrode Amplifier (PN NavEamp)

The Electrode Amplifier allows the user to use electrodes using the BNC type connector with the

LabNavigator™. The Electrode Amplifier measurements are displayed in mV potential within the Meter

Screen.

To record the species being measured within the data, go to Table Tab and tap the Title Window. You can

then edit this for species name, run number, etc.

Note: If it is known if whether the species to be measured is monovalent (such as F

  • or NO - 3 ) or divalent

(such as Mg

2+ or Ca

2+ ), a shortcut for the analysis functions of the LabNavigator App is available:

  1. Attach the Electrode Amplifier (EA) to the Electrode and insert the BTA connector on the EA into one of

the analog ports on the LabNavigator™.

  1. In the LabNavigator™ App, select Sensors then Sensor Setup.
  2. Locate the Drop Down Menu for the port showing the EA.
  3. In the Drop Down Menu, select either Nitrate for monovalent ion measurements or Calcium for divalent

ion measurements. Note: Although the display will show labels for Calcium or Nitrate, ALL the

measurements will be in the desired units and correct.

  1. Tap the OK button to save the Setup and return to the LabNavigator™ App.

Calibrating the ISE

  1. Choose Calibrate.
  2. High Standard Calibration Point: The ISE should still be soaking in the High

Standard. Enter the concentration value of the High Standard (For example; 100 for

100 mg/L or 1000 for 1000 mg/L).

  1. When the displayed voltage reading for Reading 1 stabilizes (~1 minute), tap enter.
  2. Low Standard Calibration Point: Remove the ISE from the High Standard, rinse well

with distilled water from a wash bottle, and gently blot dry with a paper towel or lab

wipe. Place the electrode into the Low Standard (included with your ISE). Important:

Make sure the ISE is not resting on the bottom of the container, and that the small

white reference contacts are immersed. Make sure no air bubbles are trapped below

the ISE.

  1. Enter the concentration value of the Low Standard (e.g., 1 for 1 mg/L or 10 for

10 mg/L). After 60 seconds, click enter and then done.

Collecting Data

  • After calibrating, rinse off the end of the ISE, and blot it dry with a paper towel or lab wipe.
  • Insert the tip of the ISE into the sample to be tested. Important: Make sure the ISE is not resting on the

bottom of the container, and that the small white reference contacts are immersed. Make sure no air

bubbles are trapped below the ISE. Note: Do not completely submerge the sensor. The handle is not

waterproof.

  • Hold the ISE still for 60 seconds and record the displayed reading.

Storing Your Ion-Selective Electrodes

Proper care and storage of your ISE are important considerations for optimal longevity, especially with the

PVC membrane ISEs (Ammonium, Calcium, and Nitrate).

  • Long-term storage of ISEs (longer than 24 hours) should be done in the Long-Term ISE Storage

Bottle, which is included. The sponge in the bottom of the bottle should be kept moist with distilled

water. When you finish using the ISE, simply rinse it off with distilled water and blot it dry using a paper

towel or lab wipe. Loosen the lid of the bottle and insert the ISE. NOTE: The tip of the ISE should

NOT be touching the sponge. Check to be sure the white ceramic junctions are inside, rather than

outside the bottle or under the grommet. Tighten the lid. This storage system keeps the electrode in a

humid environment, which prevents the reference junctions from completely drying out.

  • Short-term, wet storage (less than 24 hours) can be done by using the Short-Term ISE Soaking Bottle

included with the electrode. Fill the bottle 3/4 full with High Standard. Loosen the cap, insert the

electrode into the bottle, and tighten.

Ammonium ISEs. The membrane is a porous plastic disk, permeable to the ion exchanger, but

impermeable to water. It allows the sensing cell to contact the sample solution and separates the

internal filling solution from the sample. Our PVC membrane electrodes have replaceable membrane

modules.

  • (^) Solid State Membrane: This thin crystal disk, used in our Chloride ISE, is an ionic conductor. It

separates the internal reference solution from the sample solution. The Chloride ISE does not have

replaceable membrane modules.

The voltage developed between the sensing and reference electrodes is a measure of the concentration

of the reactive ion being measured. As the concentration of the ion reacting at the sensing electrode

varies, so does the voltage measured between the two electrodes.

As described in the Nernst equation, ISE response is a linear equation:

E = Eo + m(ln a)

where E is the measured voltage, Eo is the standard potential for the combination of the two half cells, m

is the slope, ln is natural log, and a is the activity of the measured ion species plotted.

Assuming the ionic strength is fairly constant, the Nernst equation may be rewritten to describe the

electrode response to the concentration, C, of the measured ionic species: E = Eo + m

(lnC)

A graph of the natural log of concentration (lnC) vs. potential (V) can be plotted:

The method for determining the concentration of Ca

2+ , NH 4

, NO 3

  • , or Cl - ions using

one of our ISEs is based on the following:

  • (^) The interface reads a voltage that is related to ion concentration.
  • (^) Using the voltage reading and the principle described in Figure 3, the natural log of

concentration of the specific ion can be determined.

  • (^) The ion concentration can be determined from the natural log of concentration.

Maintaining and Replacing the ISE Standard Calibration Solutions

Having accurate standard solutions is essential for performing good calibrations. The two standard

solutions that were included with your ISE can last a long time if you take care not to contaminate them

with a wet or dirty probe. At some point, you will need to replenish your supply of standard solutions.

Forston Labs sells replacement standards in 500 mL bottles. Order codes are

Ammonium Low Standard: NavNH4LST

Ammonium High Standard: NavNH4HST

Calcium Low Standard: NavCALST

Calcium High Standard: NavCAHST

Chloride Low Standard: NavCLLST

Chloride High Standard: NavCLHST

Nitrate Low Standard: NavNO3-LST

Nitrate High Standard: NavNO3HST

Forston Labs sells replacement standards in 500 mL bottles. Please contact Forston Labs for NIST

traceable standards at (800) 301-1259 for availability, or to order immediately go to www.forstonlabs.com.

To prepare your own standard solutions, use the information in Table 1.

Table 1: Replacing ISE Standard SolutionsTable 1: Replacing ISE Standard SolutionsTable 1: Replacing ISE Standard Solutions

Standard Solution Concentration (mg/L or ppm)

Preparation Method using High Quality

Distilled Water

Ammonium (NH 4

)

ISE High Standard

100 mg/L NH 4

as N 0.382 g NH 4 Cl / 1 L solution

Ammonium (NH 4

)

ISE Low Standard

1 mg/L NH 4

as N

Dilute the High Standard by a factor of 100 (from

100 mg/L to 1 mg/L).*

Figure 3

Calcium (Ca

2+ ) ISE

High Standard

1000 mg/L as Ca

2.771 g CaCl 2 / 1 L solution or 3.669 g

CaCl 2 •2H 2 0 / 1 L solution

Calcium (Ca

2+ ) ISE

Low Standard

10 mg/L as Ca

Dilute the High Standard by a factor of 100 (from

1000 mg/L to 10 mg/L).*

Chloride (Cl

  • ) ISE

High Standard

1000 mg/L as Cl 1.648 g NaCl / 1 L solution

Chloride (Cl

  • ) ISE

Low Standard

10 mg/L as Cl

Dilute the High Standard by a factor of 100 (from

1000 mg/L to 10 mg/L).*

Nitrate (NO 3

  • ) ISE

High Standard

100 mg/L NO 3 as N 0.607 g Na NO 3 / 1 L solution

Nitrate (NO 3

  • ) ISE

Low Standard

1 mg/L NO 3 as N

Dilute the High Standard by a factor of 100 (from

100 mg/L to 1 mg/L).*

*Perform two serial dilutions as described below.

a.Combine 100 mL of the High Standard with 900 mL of distilled water. Mix well.

b.Combine 100 mL of the solution made in Step (a) with 900 mL of distilled water. Mix well.

Replacement Membrane Modules (Ammonium, Nitrate, and Calcium only)

The Nitrate, Calcium, and Ammonium ISEs each have a PVC membrane with a limited life expectancy.

They are warranted to be free from defects for a period of nine (9) months from the date of purchase; it is

possible, however, that you may get somewhat longer use than the warranty period. If you start to notice

a reduced response (e.g., distinctly different voltages or voltage ranges during calibration), it is probably

time to replace the membrane module. Important: Do not order membrane modules far in advance of the

time you will be using them; the process of degradation takes place even when they are stored on the

shelf. Note that the Chloride ISE has a solid-state membrane, with a longer membrane life, and does not

need a replacement module.

Using ISA (Ionic Strength Adjuster) Solutions to Improve Accuracy

For optimal results at low concentrations of calcium, chloride, and nitrate ions, a standard method for

making measurements with ion-selective electrodes is to add ionic strength adjuster (ISA) solutions to

each of your standard solutions and samples. Note: Do not use an ISA for low concentrations of

ammonium.

Adding an ISA ensures that the total ion activity in each solution being measured is nearly equal,

regardless of the specific ion concentration. This is especially important when measuring very low

concentrations of specific ions. The ISA contains no ions common to the Ion-Selective Electrode itself.

Note: The additions of ISA to samples or standards described below do not need to have a high level of

accuracy—combining the ISA solution and sample solution counting drops using a disposable Beral pipet

works fine. The following are instructions for using ISA solutions with Forston Labs Ion-Selective

Electrodes.

Calcium ISA: Add the 1.0 M KCl ISA solution (7.46 g KCl / 100 mL solution) to the Ca

2+ standard or to

the solution being measured, in a ratio of 1 part of ISA (by volume) to 50 parts of total solution (e.g., 1

mL of ISA to 50 mL of total solution, or 2 drops of ISA to 5 mL of total solution).

Chloride ISA: Add the 5.0 M NaNO 3 ISA solution (42.50 g NaNO 3 / 100 mL solution) to the Cl

  • standard

or to the solution being measured, in a ratio of 1 part of ISA (by volume) to 50 parts of the total solution

(e.g., 1 mL of ISA to 50 mL of total solution, or 2 drops of ISA to 5 mL of total solution).

Nitrate ISA: Add the 2.0 M (NH 4 ) 2 SO 4 ISA solution (26.42 g (NH 4 ) 2 SO 4 / 100 mL solution) to the NO 3

standard or to the solution being measured, in a ratio of 1 part of ISA (by volume) to 50 parts of total

solution (e.g., 1 mL of ISA to 50 mL of total solution, or 2 drops of ISA to 5 mL of total solution).

Using the Ammonium Ion-Selective Electrode

The Ammonium ISE can be used to determine concentrations of NH 4

ions in aqueous solutions, in units

of mg/L, ppm, or mol/L. Concentrations of aqueous ammonium ions should not be mistaken for

concentration of aqueous ammonia, or NH 3 (aq). The concentrations of these two species, though

different, are often involved in the same equilibrium reaction:

Reaction 1: NH 3 (aq) + H

(aq) ←⎯⎯→ NH 4

(aq)

In a more acidic environment, higher concentrations of H

ions will cause this reaction to shift toward the

It is important to remember that total hardness, taking into account both the Ca and Mg levels, will be

about 1.5 times higher than your calcium hardness value. Water hardness varies considerably in different

parts of the United States, from levels of less than 60 mg/L (total hardness as CaCO 3 ) in Washington,

Oregon, Louisiana, Mississippi, Tennessee, and New England, to levels exceeding 250 mg/L or higher in

Midwestern states (Ohio, Indiana, Illinois, Iowa, Nebraska, South Dakota, and Oklahoma). Water with a

hardness as CaCO 3 level greater than 120 mg/L is considered to be “hard,” while levels exceeding 180

mg/L are referred to as “very hard.”equivalence point occurs first, with the Mg

2+ equivalence point

following; therefore Ca

2+ can be determined as well as total hardness (as Ca

2+ and Mg

2+ ). A plot of ln

[Ca

2+ ] (natural log of calcium ion concentration) vs. volume is used to determine the equivalence point.

The second derivative can be used to calculate the point of maximum inflection at the equivalence point

of the titration.

Using the Chloride Ion-Selective Electrode

Chloride ions are found in freshwater samples as a result of water flowing over salt-containing minerals.

These salts might include either sodium chloride (NaCl) or potassium chloride (KCl). The chloride ion

concentration in seawater is approximately 19,400 mg/L—well below the upper limit of the Chloride ISE of

35,500 mg/L.

When the response of the Chloride ISE begins to slow, the membrane may need polishing. Cut a small

piece (about 1 inch square) from a polishing strip. Wet the end of the electrode and the dull side of the

polishing strip thoroughly with distilled water. Using only moderate pressure, polish the end of the

electrode by gently rubbing in a circular motion. This will remove the inactive layer of the membrane

which impedes measurement. Rinse thoroughly with distilled water and recalibrate in the usual manner.

Sampling Freshwater Samples for Chloride Concentration

For best results, calibrate the Chloride ISE using the 10 mg/L and 1000 mg/L standards.

Measuring Chloride Concentration of Saltwater or Brackish Water

When measuring chloride concentration in seawater or brackish water, calibrate the Chloride ISE using

the 1000 mg/L standard included with your Chloride ISE for one calibration point (or 1.806 parts per

thousand, or ppt). For the second calibration point, prepare a standard that is 20,000 mg/L Cl

  • by adding

32.96 g of solid NaCl to enough distilled water to prepare 1 L of solution:

If you are calibrating in ppt, call this solution 36.13 ppt.

Determining Salinity of Saltwater or Brackish Water

Salinity is the total of all salts dissolved in water, expressed either as mg/L (equal to parts per million,

ppm) or in parts per thousand (ppt). Seawater contains a fairly constant quantity of chloride ions. From

your measurement of chloride ion concentration (in the previous section), salinity can be calculated using

the following formula:

Salinity (mg/L or ppm) = 1.8066 × [Cl

  • concentration, mg/L]

Using this formula, the salinity of saltwater is calculated to be:

Salinity (mg/L or ppm) = 1.8066 × (19400 mg/L) = 35,000 mg/L

The level of salinity of seawater in parts per thousand, or ppt, would be:

Salinity (ppt) = 35000 / 1000 = 35 ppt

Using the Nitrate Ion-Selective Electrode

Nitrate ions, NO 3

  • , may be found in freshwater samples from a variety of sources. Sewage is often the

primary source. Sometimes nitrates are present due to runoff from fertilized fields. Nitrates can also result

from the runoff from cattle feedlots and barnyards. In all of these cases, as plant and animal organisms

die, bacterial action breaks down the protein into ammonia, NH 3. Some ammonia is converted into

ammonium ions, NH 4

. Other bacterial action converts some of the ammonia and ammonium ions into

nitrite ions, NO 2

  • , and then into nitrate ions, NO 3 - .

Units of Nitrate Concentration

Nitrate ion concentration is usually expressed in units of mg/L of NO 3

  • as N, also known as “nitrate-

nitrogen.” This means that the concentration of nitrate is expressed as if the nitrate were only in the form

of nitrogen itself. The standards that are included with your Nitrate ISE have concentrations of 1 and 100

mg/L of NO 3

  • as N. Here is the calculation for making a 100 mg/L NO 3 - as N standard starting with solid

NaNO 3 (as shown in Table 1). Notice that the atomic weight of N, 14.0, is used instead of the atomic

weight of NO 3

  • , 62.0.

Unpolluted waters usually have nitrate-nitrogen (NO 3

  • as N) levels below 1 mg/L. Nitrate-nitrogen levels

above 10 mg/L are considered unsafe for drinking water.

Test results are sometimes published in units of mg/L NO 3

  • instead of NO 3 - as N. To convert 100 mg/L

NO 3

  • as N to mg/L NO 3 - , you would perform this conversion:

Sampling Freshwater Samples for Nitrate Concentration

For best results, calibrate the Nitrate ISE, using the 1 mg/L and 100 mg/L standards.

How can I have my ISE read mV output instead of mg/L?

The amplification equation is: V = 0.00727*mV + 1.

Therefore, the reverse amplification equation, solving for mV, would be: mV = 137.55*V – 0.

Warranty

Forston Labs warrants this product to be free from defects in materials and workmanship for a period of 9

months from the date of shipment to the customer. This warranty does not cover damage to the product

caused by abuse or improper use.

Measure.Analyze.Record

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