ESTIMATION OF FLUORIDE CONTENT IN DRINKING

WATER USING
ION-SELECTIVE ELECTRODES (ISE)

INTRODUCTION
In recent years, direct potentiometry has become important as an analytical
technique largely because of the development of ion-selective electrodes (ISE).
This type of electrode incorporates a special ion-sensitive membrane which may be
glass, a crystalline inorganic material or an organic ion-exchanger. The membrane
interacts specifically with the ion of choice, in our case fluoride, allowing the
electrical potential of the half-cell to be controlled predominantly by the F-
concentration [1].

Fluoride is a halogen element and it is the most reactive non-metal. Its chemical
behavior and properties are mainly different from other halogens elements.
Fluoride is important anion too and occurs in various environmental, clinical and
food samples. Fluoride is both beneficial oligo element (needed for growth and
bone tissue upholding and teeth) and toxic (for adults the lethal dose is 0.20-0.35 g
F per kg body weight). Fluoride is the most abundant element in nature, and
about 96% of fluoride in the human body is found in bones and teeth. Fluoride is
essential for the normal mineralization of bones and formation of dental enamel
Fluoride is often called as two-edged sword. Higher F concentration in the human
body can be resulted by living in polluted environment and feeding with polluted
food. Higher fluoride intake, above recommended levels (1.5 mg L1), leads to
dental and skeletal fluorosis. Acute fluoride intoxication can have neurological
complications, urinary stone formation and hypocalcemia as consequences on
endemic patients. In recently published papers was described a link between
fluoride intake and cancer [2].

Fluorides come naturally into water by dissolving minerals that contain fluoride,
such as fluoride (CaF2), the most common fluoride mineral, apatite (Ca5(Cl,F,OH)
(PO4)3), cryolite (Na3AlF6). Amphibole minerals, such as hornblende and some
sorts of mica, can contain fluoride that partially replaces hydroxide ion. Rocks rich
in alkali metals have a larger content of fluoride than other volcanic rocks. Fresh
volcanic ash, as well as the ash of the other sediments can contribute to fluoride
content increasing in surface waters. Mixed minerals Na Mg Al (F, OH)6H2O and
Al2(F, OH)6H2O and are rare, but can contribute to the fluoride content
increasing while rinsing with water [3].
Natural water contains less than 0.1 ppm fluoride ions, and in Egyptian waters, it
moves from 0.05 to more than 0.6 ppm. Mineral waters consist, on average, 0.16 to
6.45 ppm. Recommended limited value for fluoride in drinking water by World
Health Organization (WHO) and European Union (EU) is 1.5 ppm (WHO, 1984),
while in our country the standard is 1 ppm [4].

Fluor content in water is expressed through the free fluoride-ion concentration,

whose concentration depends on origin and nature of water. This form is dominant
in many water samples, although other forms of dissolved fluoride can be present.
Fluoride ion has small ion radius, so it shows great tendency to behave as ligand.
Fluoride ion, because of that, forms a great number of different complex ions,
where central ion has a large coordination number (mostly 6). Fluoride forms
stable complexes in water with Al3+, Be2+ and Fe3+ ions, and with boron it forms
mixed fluoride-hydroxy complexes. As Fluoride ion has the same electricity and
almost the same radius as hydroxide ion, these ions can mutually change in mineral
structures.

Fluoride selective electrode

Determination of Fluoride occurs by using one of these different methods: Ion
selective electrode method, Ion chromatograph method, Spectro photometry
method, Spectro fluorimetry method, titrimetric method, Potentiometric method.
The most important electro analytic method for determination of fluoride ion in
water solution is usage of ion selective electrode for fluorides. Fluoride selective
electrode is very sensitive, and temperature range of electrode goes from 0 to 50C.
For potentiometric analysis of fluoride ion, in commercial usage, there are mostly
used electrodes with homogenic membrane made from fluoride lantana (LaF3) [5].

Active phase of fluoride selective electrode makes monocrystalline LaF3 which is

doping by Eu2+ ions, in order to decrease membrane ohm resistance. The great
selectivity of electrode is in the fact that only fluoride ions are included in the
process of diffusion. Commercially available electrodes are made by putting the
electro-active material into the electrode carrier. The electrode carrier is the most
common organic polymer substance (PVC, epoxy resin, polypropylene, Teflon
etc.). The interior of the electrode carrier is filled with Potassium chloride solution
of 1 mol/dm3 concentration and Potassium fluoride solution of 0.01 mol/dm3
concentration, inner referent electrode is Ag/AgCl electrode. The detection limit of
monocrystalline ion selective electrodes depends on the product of solubility of
hardly dissolved compound in test solution. Even if the test solution doesnt
contain fluoride ions, when the fluoride selective electrode plunge into the solution
it will come to LaF3 dissolving, and concentration of La3+ and fluoride ions will
be adequate to values that are countable from the product of LaF3 dissolving. This
means that in the solution there will always be present low, constant, concentration
of fluoride ions, so the applicability of ionomeric for fluoride ion is from 5x10-7
mol/dm3 to 1 mol/dm3 of fluoride [6].

The potential of the ISE is measured against a suitable reference electrode using an
electrometer or pH meter. The electrode potential is related to the logarithm of the
concentration of the measured ion by the Nernst equation.

where n is the ion charge (negative for anions). The factor 2.303 RT/F has a
theoretical value of 59 mV at 25 C. The equation is only valid for very dilute
solutions or for solutions where the ionic strength is constant. Ionic strength is
defined by

where Zi is the charge on an ion and Ci is its concentration. ISEs are available for
measuring more than 20 different cations (e.g., Ag+, Na+, K+, Ca++, Cu++) and
anions (e.g., F-, Cl-, S-2, CN-) [1].

KF

Figure 1: Ion selective electrode of Fluoride

Fluoride selective electrode is very selective to fluoride ions, but at the same time,
in a certain amount, it is selective to hydroxide ion. Adjustment of pH value with
buffer is necessary because fluoride and hydroxide ions have the same electricity
and similar ion radius, so hydroxide ions can interfere in the measurement of the
fluoride selective electrode. In acid solutions, hydrofluoric is formed, to which the
fluoride selective electrode is not sensitive. In that way, with solution pH values
decreasing, the activity of fluoride ion in solution also decreases, so the
measurement will not be reliable. On the other hand, in highly base solutions a thin
layer of La(OH)3 is formed on the surface of the sensor part:

LaF3(s) + 3OH La(OH)3(s) + 3F

In this way, the concentration of fluoride ions in solution increases, that is, with the
increasing of solution pH values, electrode potential of the ion selective electrode
becomes more negative. Accordingly, it can be concluded that pH value of the
solution during the measurement by the fluoride selective electrode must be in the
range 5.00-7.00. Before the measurement with the fluoride selective electrode, all
precautions must be taken to remove all organic uncleanness from the solution,
above all chloroform (CHCl3).

Figure 2: Doped Lanthium Fluoride Electrode- anions move through

Europium vacancies

Determination by the fluoride selective electrode means previous calibration with

the solution with known concentration. During the measurement of concentration
by the fluoride selective electrode, it is advisable, instead of calibration with two
points, to construct calibration diagram, by EMS measurement in 5-6 standard
solutions of different concentrations. This calibration diagram is then used to
determine of fluoride ions concentration in the sample by EMS measurement and
reading from calibration curve. If the fluorides solutions are highly dilute,
concentration of fluoride ions is determined by standard addition method [7].

Figure 3: Calibration curve of Fluoride ions

Material and Methods

Measurements of fluoride ion in bottled mineral water and drinking water
from water-supply system were done on ion meter type PHM240 (Radiometer,
France). Fluoride selective electrode was used as sensor electrode (type ISE25F)
and saturated calomel electrode (SCE) as a reference electrode.

In order to construct a calibration curve, for fluoride ion determination in drinking

water, standard solutions were prepared. First, the standard working solution Ro of
100 mg/dm3 concentration was prepared by dissolving the necessary amount of
sodium fluoride. Before the measurement, sodium fluoride was dried for an hour at
110C. Solutions of 0.1-10 mg/dm3 concentration of fluoride ion were prepared by
diluting the standard working solution (for determination of fluoride in drinking
water and 0.1-5 ppm fluoride ions for determination of fluoride in tea,
respectively). Diluted solutions were prepared in 0.1 mol/dm3 solution of
potassium nitrate, in order to regulate ion intensity [3].

A. Preparation of Fluoride Standard Solutions

1. By serial dilution of the 1000g/mL fluoride standard solution,
prepare 50 mL each of 200, 20 and 2g/mL fluoride standards in 50-
mL volumetric flasks. After thorough mixing, transfer each diluted
standard solution to a labeled plastic reagent bottle
for storage. Calculate the concentration of each diluted standard
using the exact concentration of the stock solution.

B. Calibration Check of Electrode

1. Carefully pipet 25.00 mL of the most dilute fluoride standard into a
50-mL volumetric flask and dilute to the mark with
the TISAB. Stopper the flask and thoroughly mix the solution.
2. Transfer this solution to a 100-mL plastic beaker. Place the beaker
on a stirring plate, add a magnetic stirring bar and begin stirring at a
constant rate.
3. Connect the fluoride ISE to a pH meter and set the meter to the
mV mode. Rinse the electrode with deionized water and blot dry.
4. Lower the electrode into the standard solution. When the reading
is stable record them V value.
5. Repeat steps II.B.1-4 for each of the remaining fluoride standards.
6. Estimate of the slope (S) from the difference in the mV readings
for each factor of ten increase in the fluoride ion concentration. If
your value is outside the expected range, consult with your lab
instructor.

C. Analysis of Unknown
1. Prepare a 500 g/mL fluoride standard by pipetting 5.000 mL of the
1000g/mL fluoride standard solution into a 10-mL volumetric flask
and diluting to the mark with the TISAB.
2. Carefully pipet 50.00 mL of your fluoride unknown, which contains
the TISAB at the same concentration as used for the standard
calibrations, into a 100-mL plastic beaker. Place the beaker on a
stirring plate, add a magnetic stirring bar and begin stirring at a
constant rate.
3. Rinse the ISE with deionized water and blot dry.
 4. Lower the electrode into the unknown solution. When the reading is
stable record the mV value.
5. Pipet 1.000 mL of the 500g/mL F-standard solution into the
unknown solution. When the reading is stable record the mV value.
6. Make three additional 1.000 mL additions of the standard solution
and record the mV reading after each addition as before.
7. When finished, rinse the ISE with deionized water and place it in
the storage container.

Calculations
Calculation of data collected can be performed as the next steps

A. Determination of Calibration Slope

1. Using EXCEL, plot the mV reading for the diluted fluoride standards
versus the log of the actual fluoride ion concentration.
2. Fit the data points with a linear least-squares line and from the
equation for the line obtain the slope (S).

B. Determination of Unknown Concentration by Standard Addition

1. Using the slope determined in the section above, plot 10E/S (V0 +
Vstd) versus C std V std. Remember to include the initial reading
with no added standard.
2. Fit the data points with a linear least-squares line and obtain the
equation for the line.
3. Use the equation for the line to determine the x-intercept and from
this calculate the fluoride ion concentration in the unknown solution.
REFRENCES
onTHAMARAI
M.
-4
1AND
J. poly
sodium
The
obtained
A. (vinyl
tetra
concentration
of
M 1M tostable
with 1x10
VIJAYALAKSHMI
1. A. chloride)
range
detection powder.
limitstime
ofand
potentiometric
within aSELVI
short
Vijayalakshmi1 the Theofof
j.order
signals
period ion
are10selective
4minutes.
Thamarai electrode system,
selvi, Determination of Fluoride Ion
Using an Ion Selective Electrode, 14 May, 2013.

2. Josipa Giljanovi, Ante Prki, Marija Brali, Mia Brkljaa. Determination

of Fluoride Content in Tea Infusion by Using Fluoride Ion-Selective
Electrode, 1 April 2012.

3. M. B. Rajkovi and Ivana D. Novakovi, Determination Of Fluoride Content

In Drinking Water And tea Infusions Using Fluoride Ion Selective Electrode,
Journal of Agricultural Sciences Vol. 52, No 2, 2007 Pages 155-168.

4. World Health Organization (WHO) 2002, Fluorides, World Health

Organization (Environmental Health Criteria 227).

5. Fr ant , M. and Ros s, J.W. Jr. (1966), Science, 154, 1553.

6. Brali , M. Radi , Nj. Br ini , S., Gener a li , E. (2001)): Fluoride

Electrode with LaF3 Membrane and Simple Disjoining Solid-State Internal
Contact, 2001.

7. Ion, I., Ion, A.C., Ba rbu, L. Potentiometric determination of fluoride in

groundwaters, Revue Roumaine de Chimie, 50(5), 2005.