Analytical Chemistry Laboratory 2

Direct Potentiometric Titration of Fluoride Ion

Mr. *****

Department of Chemical Engineering and Chemistry, Mapua Institute of Technology

In this experiment, the concentration of fluoride in drinking water will be determined by

a potentiometric method.. The activity of fluoride in solution can be determined with a solid-state
fluoride selective electrode. Four standard solutions were measured for its potentials, and a
straight line was obtained. An unknown sample, in this case, sample # 3 (6 mL) was analyzed
from the potential reading of 82.1 mV. The concentration of the fluoride was therefore computed
using linear regression and the result was 2.07 ppm.

Objective
The main objective of the
experiment is to determine the concentration
of Fluoride ion in a sample drinking water.
Discussion
Overview
To measure a potential, we create a
voltaic cell with the indicator and reference
electrodes. We measure the voltage of the
cell, giving a reading of the indicator
electrode potential relative to the reference
electrode. We can relate this to the analyte
activity or concentration using the Nernst
equation.
The standard fluoride solution and
the total ionic strength adjustment buffer
(TISAB) can be purchased readily from
commercial sources.
Fluoride is a "general protoplasmic
poison." When present as a soluble salt, it is
readily absorbed from the alimentary tract.
A 2% solution of sodium fluoride kills
mucosal cells, and its ingestion leads to a
severe hemorrhagic gastroenteritis; in part
this corrosiveness is due to a toxic action on
mucosal capillaries and is seen even after
parenteral administration. The systemic
actions of fluoride are presumably related to
the inhibition of one or more enzymes
controlling cellular glycolysis and to the
binding or precipitation of calcium as CaF2.
Methodology
50 mL portions of water were
transferred to 100 mL volumetric flasks, and
were diluted to the mark with TISAB
solution.
A 5 ppm F- solution was prepared
by diluting 5 mL of the 100 ppm standard to
100 mL in a volumetric flask. Aliquots of
2.50-, 5.0-, 10.0-, 25.0-mL of the 5 ppm
solution were transferred to 100 mL
volumetric flasks as well as 6 mL of the
sample, 25 mL of TISAB solution were
added, and diluted to the mark. (These
solutions corresponded to 0.5, 1.0, 2.5, and
5.0 ppm F-, respectively, in the sample.)
After thorough rinsing and drying
with paper tissue, the electrodes were
immersed in the 0.5 ppm standard. It was
stirred mechanically for 3 min; the potential
was then recorded. It was repeated similarly
with the remaining standards and the
sample.

Instrumentation
The apparatus for this experiment
consists of a solid state fluoride electrode, a
saturated calomel electrode, and a pH meter.
pH measurements with an electrode
involve the measurement of potentials. The
pH meter acts like a voltage measuring
device designed for use with high-resistance
electrodes.
The commonly used reference
electrode is the saturated calomel electrode.
It is designed to make measurements with
high-resistance electrodes.
Interpretation
The potential data obtained from the
pH meter readings is shown below with its
corresponding concentration.
Potential (mV) Concentration (ppm)
113.4 0.5
100.9 1
84 2 References
82.1 x
60.5 5 1. Christian, G.D., Analytical Chemistry, 6th
A linear graph is derived when
concentration is in logarithmic form.
120
100
80
potential
60
40
20
0
-0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
log [concentration]
In the presence of the total ionic
strength adjustment buffer, a plot of
potential vs. log [conc.] should be linear. To
determine the amount of fluoride in a
solution of unknown concentration, we must
first calibrate the electrode by measuring the
potential for a series of fluoride standard
solutions. The unknown concentration, x,
was found to be 2.07 ppm from the graph.
The effect of all the common
interferences and activity effects can be
overcome by addition of a total ionic
strength adjustment buffer (TISAB) to the
standard and sample solutions.
Sources of error include fluoride ion
activity changes due to the ionic strength of
solution, temperature, which can affect the
measured potential through the Nernst
equation which governs the electrode
potential response and through the several
equilibria that fluoride may have with
species present in solution, and substances
that complex fluoride in solution.
Conclusion
Potentiometric methods relate the
potential generated at an indicator electrode
to the concentration of an analyte in
solution. The unknown concentration of the
drinking water was obtained from the
graphical visual from the experimental data.
It was found out to be 2.07 ppm by using the
method of linear regression for accuracy.
edition, New Jersey, John Wiley, 2004.
2. Skoog, D. A., and Leary, J. J., Principles
of Instrumental Analysis, 4th edition,
Saunders, New York 1992.

3. Harris, D.C., Quantitative Chemical

Analysis, 3rd edition, Freeman, New York,
1991.