Shenay Elizabeth

Sagadaven
2
12510295
Experiment 7: Aims and Principles

Aim
To ascertain the concentration of fluoride present in mineral water, drinking water,
toothpaste and mouthwash. This is achieved by using a fluoride ion selective
electrode and the working curve method.

Principles
Potentiometric ion selective electrodes (ISE) are made up of an inner filling solution,
an outer test solution and two reference electrodes as can be seen in figure 1 [1].
The inner filling solution contains a fixed concentration of the analyte while the
outer test solution contains an unknown analyte concentration. These two solutions
are separated by an active membrane [1, 2].

Figure 1: Solid state fluoride electrode [1].

In the fluoride ISE the inner filling solution consists of both 0.1 M NaCl and 0.1 M
NaF while the outer test solution contains the sample fluoride solution [1]. A monocrystal of LaF3 doped with europium ions functions as the active membrane [3]. The
europium ions improve conductivity and aid in ionic charge transport by creating
holes, called anion vacancies, in the crystal lattice [2, 3]. Since the inner filling
solution and outer test solution contain

F- ions at different concentrations, F-

ions from the solution with a higher activity of

F- will move via the anion

vacancies in the membrane into the solution with a lower activity of

causes an excess of

F- [1]. This

to be present on one side of the membrane, which is then

regarded as positive with respect to the other side. As a result a potential difference
which can be measured is generated across the membrane [1, 2]. This measured

potential is dependent on the concentration of

concentrations of

in the solution [1]. For

below 10-5 M, the electrode response is linear and can be

described by a Nernst equation shown below

E = E0 Ej + (RT/ZF) ln a [4].
Where E is the measured electrode potential, E 0 is the reference potential, E j
represents the junction potential, T is the temperature in K, Z represents the charge
and a represents the activity of fluoride ions. Both R and F are constants [4].
At concentrations that are greater than 10% of

F-

present, interfering ions such

as OH- directly affect the measured potential because they bind to the membrane
surface and complex with the

F-

ion, this decreases the concentration of total

free fluoride ions [5]. For this reason a buffer solution must be used [1].
The most commonly used buffer is TISAB (Total Ionic Strength Buffer) [1]. TISAB
maintains a constant ionic strength in the analyte solution and the calibration
standards; it also minimizes interference by controlling the level of OH - [1, 5].
At a pH below 5.0,

protonates to form HF, which interferes with the measured

potential [6]. TISAB has a buffering ability and therefore controls the pH of the
solution so that it does not fall to below 5.0 [1]. TISAB also controls the pH of the
analyte solution so that the concentration of OH - does not become larger than 10%
than that of the fluoride ion present [5].

References
1. Henderson D.E., 2010. A Potentiometric Analysis of Fluoride ion in Toothpaste
[Online].
Available at: http://infohost.nmt.edu/~jaltig/Toothpaste.pdf
[Accessed on 4 April 2015]
2. Lingane J.J., 1968. Lathanum fluoride membrane electrode for potentiometric
determination and titration of fluoride. Analytical chemistry 40(6), pp. 935939.
3. Pillay, L., 2015. CHEM340: Instrumental Analysis Practical Manual, School of
Chemistry and Physics, UKZN Durban, pp 35-36.
4. Kealey D., Haines P.J., 2002. Instant notes on Analytical Chemistry, pp.70-73.
5. Noh J., Coetzee P., 2007. Evaluation of the potentiometric determination of
trace fluoride in natural and drinking water with a fluoride ISE [Online]

Available at: http://www.wrc.org.za/Knowledge%20Hub%20Documents/Water

%20SA%20Journals/Manuscripts/2007/03/WaterSA_2007_03_2084.pdf
[Accessed on 4 April 2015].
6. Khopkar S.M., 1998. Basic concepts of Analytical Chemistry, pp. 393-400.