Name: Nerissa Rajkumar

Student Number: 219003070

Date of Practical: 24 March 2021

AIM:

The aim of the experiment was to determine the content of fluoride in different dental
products such as toothpaste, mouthwash, mineral water and tap water using the solid-state
fluoride electrode and TISAB to match the standard solutions and samples in terms of activity
coefficient of the analyte.

ABSTRACT:

The aim of the experiment was to find the fluoride content in toothpaste, mouth wash,
mineral water and tap water using Ion selective electrode (ISE). TISAB was added to adjust
the pH ionic strength. The standards containing different Fluoride concentrations and samples
were prepared and their potential difference were measured. The standards of 0.1, 0.5, 1.0,
2.5, 5.0 and 10 ppm were prepared and calibration graph was obtained with a correlation
coefficient of 0.9167. The graph of potential difference vs log [f-] of the standards was
plotted and the equation of the line which was found to be y = -38.164x-342. This was used
to calculate the fluoride concentrations in samples using their mean measured potential
difference in the place of y. Using the calibration curve the concentrations of tap water,
mineral water and mouthwash were respectively calculated to be 0.2244, 0.3992 and 249.43
ppm. The obtained results showed that mouthwash had the highest fluoride content. Mineral
water is healthier than tap water, it had the permitted amount of fluoride in it. The solid-state
was a suitable technique, it inorganic crystal salt.
PRINCIPLES:

Potentiometry is a method used in electroanalytical chemistry, normally to quantify the

concentration of a solute in a solution. Ion Selective Electrode (ISE) is the analytical method
used to quantify the concentration of ions available in aqueous solutions. ISE is also known
as a membrane electrode which is a main component of all potentiometric ion sensors used, it
responds selectively to ions in the availability of dissimilar interrupting ions from the sample
1
.

In this experiment, a solid-state fluoride electrode will be used to analyse sample solutions
based on an inorganic salt. The electrode is accomplished for the detection of fluoride ions
(F-) in aqueous solutions and is appropriate to be used in field and laboratory analysis. As ion
selective electrode responds to activity, the standard solutions and samples must be contested
in expression of activity coefficient of the analyte ion. In order to achieve this, it requires that
the ionic strength of these solutions is uniform 2.

Ion selective electrodes (ISEs) provide a relatively easy and inexpensive way to measure
certain ion concentrations. The fluoride ISE is especially sensitive and has a temperature
range of 0 to 80°C. The electrode is made from a crystal of LaF3 that has been doped with
EuF2 to increase its conductivity. At 25°C, the cell potential of the fluoride ISE is expressed
in terms of the fluoride activity.

In practice, the ionic strength of the solution is kept constant by adding a constant amount of
a solution with a high ionic strength, called a total ionic strength adjusting buffer (TISAB), to
all standards and samples. The activity coefficient is then constant. The TISAB also contains
the complexing agent trans-1,2-cyclohexylenedinitrilotetraacetic acid (CDTA) which forms
complexes with ions such as Al3+ that would otherwise bind F- and interfere with the
potentiometric measurements 3,4.
 Figure 1: an ion selective electrode

Source: https://www.scigiene.com/analytical-
instruments/ise%20ion%20selective%20electrode%20meters.htm

Figure 2: Rational design of all-solid-state ion-selective electrodes and reference

electrodes

Source: https://www.sciencedirect.com/science/article/abs/pii/S0165993615301230
INTRODUCTION:

Fluoride is a halogen found in group 17 of the periodic table. It has high reactivity and
therefore naturally does not occur in the elemental state. It accounts for about 0.3 g/kg of the
Earth’s crust and exists in the form of fluorides in a number of minerals, of which fluorspar,
cryolite and Fluorapatite are the most common and has the -1 oxidation state 5.

Fluoride is a natural occurring element or mineral which is abundant in nature and it is a

halogen with an oxidation state of -1. Fluoride is natural occurring in water and mostly used
in tooth paste and mouth wash or most dental products. Fluoride plays a major role in cavity
reduction and prevention of tooth decay, this is done through absorption of floured by the
enamel (hard surface of the tooth, it is the most mineralized part of the tooth) thus helping the
enamel to be restore back through restoring of calcium and phosphorus compound which
later on strengthens the teeth thus preventing the dissolution 6. The following reaction shows
the reaction between enamel of the tooth and fluoride.

Ca10(PO4)6(OH)2 + 2F-→ Ca10(PO4)6F2 + 2OH-. (1)

The amount of fluoride in water samples, mouth wash and toothpaste were determined using
ion selective method (fluoride electrode), this method converts the activity of the electrode
into electric potential that can be easily read by the voltmeter 7. The electrode basically
measures the free ions of fluoride that are present in a solution. The ion selective electrode
consists of the thin membrane which is very selective and it transports the ions understudy of
which in this case were fluoride ions, this is done so through diffusion where it transports
them from high concentration to a lower concentration thus generating the potential
difference which is then read of by the voltmeter. In this experiment Total Ionic Strength
Adjustment Buffer (TISAB) was added so as to adjust the analyst activity and the pH of the
solution 8.

There are four types of ion selective electrode whose construction and mode of operation
differ considerably. These are 9:

1. Glass body electrode

2. Solid state (crystalline membrane)

3. Liquid ion exchange (polymer membrane)

4. Gas sensing type

1.Glass body electrodes

The most common ISE is the glass-bodied pH combination electrode. The sodium (Na+)
combination has a similar construction which houses a glass bulb that is sensitive to sodium
ions in solution.

2. Solid state ion selective electrode

The electrode potential of standard and sample solutions is measured across a solid, polished
crystalline membrane. The crystalline material is prepared from a single compound or a
homogeneous mixture of compounds (for example, the fluoride ISE has a Lanthanum
Fluoride crystal).

3. Polymer membrane ion selective electrode

These electrodes use a replaceable membrane cap which has a solid, polymeric membrane
containing a selective ion exchanger. The electrode potential of solutions is measured by their
effect on the ion exchange material. Due to the complex properties of the ion exchangers,
they are subject to more interferences than other ion selective electrodes.

4. Gas sensing type

Electrodes, including the ammonia ISE, use a gas sensing mode of operation. In the case of
ammonia, a caustic solution is added to the sample solution to liberate ammonia. The gas
permeates through a membrane and changes the pH of the filling solution. The change in pH
is proportional to the ammonia concentration. This gives a quantitative measurement of the
ammonia in the sample solution.
Figure 3: glass body electrode Figure 4: solid state ion selective
electrode

Source: Source:
https://hanna.co.za/e-
https://www.vernier.com/product/c
shop/electrodes-probes/ph-orp-
electrodes/1900/hi1190t- hloride-ion-selective-electrode/
combination-glass-body-ph-
electrode-6-bar-max-pressure-and-
t-type-connection

Figure 5: polymer membrane ion Figure 6: gas sensing type

selective electrode

Source: Source:

http://shop.hannasingapore.com
/shopping-items/electrodes-and-
probes/ion-selective-
electrodes/847/hi4104-calcium-
ise-polymer-membrane-
combination
https://hanna.co.za/e-
shop/electrodes-probes/ise-
electrodes-probes/849/hi4105-
carbon-dioxide-combination-ion-
selective-electrode-ise-gas-sensing
 Figure 7: Construction of the sensing portion on the 4 main types of Ion-selective/gas
sensing electrodes

Source: https://www.mt.com/dam/MT-
NA/pHCareCenter/Ion_Selective_Measurement_APN.pdf

Fluoride is beneficial to teeth because it helps to:

 rebuild (remineralize) weakened tooth enamel

 slow down the loss of minerals from tooth enamel

 reverse early signs of tooth decay

 prevent the growth of harmful oral bacteria

When bacteria in your mouth break down sugar and carbs, they produce acids that eat away
at the minerals in your tooth enamel. This loss of minerals is called demineralization.
Weakened tooth enamel leaves your teeth vulnerable to bacteria that cause cavities.

Fluoride helps to remineralize your tooth enamel, which can prevent cavities and reverse
early signs of tooth decay 10.

Fluoride has an essential role in avoidance of dental decay and crumbling of a tooth or bones
when insufficient. However, immoderate subjection to fluoride can lead to various
disadvantageous effects, ranging from mild dental fluorosis to crippling skeleton fluorosis. In
spite of the fact that fluoride’s primary benefits are resulted by its tropical contact with teeth,
sufficient use of fluoride is important for dental health, mostly in children. Since water is
main drinking fluoride source for human, the fluoride content in drinking water must be taken
into consideration. The fluoride concentration in drinking water must be 0.5 – 1.5 mg/L, this
has been approved by the World Health Organisation 11.

The mechanism by which fluoride controls caries (Permanently damaged areas in teeth that
develop into tiny holes) has been clearly elucidated in the last decades of the last century
12
. Fluoride available in the ionic form in the oral cavity is able to counterbalance the mineral
losses caused by acid production in the biofilm, by inducing the precipitation of the less
soluble mineral phase fluorapatite in the tooth structure. Perhaps the great effect of fluoride to
control caries is based on the concentration needed for it to exert its effect: when fluoride is
present at concentrations as low as 1 µM (approximately 0.02 ppm F), the oral fluids (saliva,
plaque fluid) are supersaturated with respect to the mineral phase fluorapatite. Thus, even
when available at very low concentrations in the mouth, fluoride can induce the precipitation
of minerals on teeth. This effect, occurring every day, results in delayed mineral loss and
prolongs the time needed for caries lesions to be clinically observed – or even maintains the
mineral loss at subclinical stages for the whole life of an individual 13.

Total ionic strength adjustment buffers (TISAB) are buffer solutions that increase the ionic
strength of a solution to a relatively high level. This is important for potentiometric
measurements, including ion-selective electrodes, because they measure the activity of the
analyte rather than its concentration. TISAB is very commonly applied to fluoride ion
analysis such as in fluoride ion-selective electrodes. Each constituent of TISAB plays an
important role in controlling the ionic strength and pH of the analyte solution 14.

The usual concentration of fluoride in toothpaste ranges from 1000 to 1500 parts per million
(ppm) 15.
EXPERIMENTAL:

Calculations of 1000 ppm F- solution preparation:

1000 ppm = 1000 mg L-1

Molar mass of NaF = 41.99 g mol-1

Molar mass of F = 19.00 g mol-1

Mass = 19.00 g mol-1 / 41.99 g mol-1

= 0.4525

= 1g / 0.4525

Therefore mass = 2.210g F in NaF

The Total Ionic Strength Adjustment Buffer solution was already prepared in the lab for
analysis. A 1000 ppm of standard fluoride solution was prepared by measuring 2.210 g of F
in NaF sample and transferred to a 1L plastic bottle and diluted to the mark with deionised
water. The calculations of F in NaF measured are shown above.

Two 25ml aliquots of tap water and bottled mineral water samples were prepared using 50 ml
volumetric flasks and diluted to the mark with TISAB. Mouthwash sample was prepared also
by pipetting 5 ml of mouthwash solution and mixed with 30 ml of deionised water; followed
by 50 ml of TISAB and made up to 100 ml with deionised water.

A 50 ppm of stock solution was prepared by diluting 5 ml of 1000 ppm fluoride solution to
100 ml with deionised water. The calculations are shown below:
Calculation of stock solution preparation:

C1V1 = C2V2

1000 ppm x V1 = 50 ppm x 10 mL

V1 = 5.00 mL

From the 50 ppm stock solution prepared, standards 0, 0.1, 0.5, 1.0, 2.5, 5.0 and 10.0 ppm F-
were prepared with the addition of volumes shown on the table below. For each standard, 50
ml of TISAB was added and diluted to the mark of 100 ml volumetric flasks with deionised
water.

Calculation of 50 ppm F standard solutions:

C1V1 = C2V2

50 ppm V1 = 0 ppm x 100 mL

V1 = 0.00 ml

Table 1: concentrations and volumes of standards

Standard: Concentration (ppm): Volume (ml):

1 0 0.0
2 0.1 0.2
3 0.5 1.0
4 1.0 2.0
5 2.5 5.0
6 5.0 10.0
7 10.0 20.0
After all preparations, the solid state fluoride electrode was used to measure the potential
difference in mV. The electrode was firstly rinsed and dried, immersed into the sample or
standard to be analysed and then the readings were taken after 3 minutes of stirring.

RESULTS:

Table 2: the measured potential differences at 22℃ of the fluoride standards

Standard: Concentration Potential (mV): Log[F-]:

(ppm):
1 0 -308.7 undefined
2 0.1 -311.2 -1
3 0.5 -323.7 -0.301
4 1.0 -334.3 0.0
5 2.5 -356.1 0.398
6 5.0 -376.9 0.699
7 10.0 -397.8 1

Figure 8: potential vs log [F-] for the standards

 Table 3: the potential difference measured for fluoride in different samples

Sample: Potential (mV): Mean potential (mV):

mouthwash -384.7 -383.8

-382.9
Mineral water -316.4 -315.3

-314.1
Tap water -306.9 -305.7

-304.5

Calculations:

Mouth wash 1

The equation of the straight line: y = -38.164x-342

y = -384.7

Therefore -384.7 = -38.164x - 342

[F-] =101.119 = 13.15ppm

Dilution factor = 20

F content in mouth wash 20 x 13.15 = 262.96 ppm

262.96/1000 =0.2630 mgmL-1

The true value of F in mouthwash is 225 ppm

262.96−225
% Error = 225
x 100 = 16.87%
Mouth wash 2

The equation of the straight line: y = -38.164x-342

y = -382.9

Therefore -382.9 = -38.164x - 342

[F-] =101.072 = 11.79ppm

Dilution factor = 20

F content in mouth wash 20 x 11.79 = 235.90 ppm

235.90/1000 =0.2359 mgmL-1

The true value of F in mouthwash is 225 ppm

235.90−225
% Error = x 100 = 4.84%
225

Mineral Water 1

The equation of the straight line: y= -38.164x-342

y = -316.4

Therefore -316.4 = -38.164x -342

[F-] = 10-0.6708= 0.2134 ppm

Dilution factor is 2

[F-] = 2 x 0.2134 =0.4268 ppm

Mineral Water 2

The equation of the straight line: y= -38.164x-342

y = -314.1

Therefore -314.1 = -38.164x -342

[F-] = 10-0.7311= 0.1858 ppm

Dilution factor is 2

[F-] = 2 x 0.1858 =0.3715 ppm

Since it is stated on the mineral water container that the fluoride content is less than 1 ppm
the experimental value falls within the range.

Tap Water 1

The equation of the straight line: y = -38.164x-342

y = -306.9

Therefore -306.9 = -38.164x-342

[F-] = 10-0.9197= 0.1203 ppm

Dilution factor is 2

[F-] in tap water= 2x 0.1203 =0.2406 ppm

Tap Water 2

The equation of the straight line: y = -38.164x-342

y = -304.5
Therefore -304.5 = -38.164x-342

[F-] = 10-0.9826= 0.1041 ppm

Dilution factor is 2

[F-] in tap water= 2x 0.1041 =0.2081 ppm

Table 4: true Values of the Concentration of Fluoride in dental products and in water

Sample: True value (ppm):

Tap water 0.18 to 0.2
Mineral water <1
Mouthwash 225

Statistics:

T-test

Calculation for mouth wash mean concentration is 249.43, SD=19.13

T table for 95% CI and 1 df is 12.71

249.43−225
tcalc =
19.13
x √2

= 1.806

T cal.< Ttable therefore there is no significance difference between experimental and true
value.
 Table 5: summarised stat calculations

Samples: Mean±SD(ppm): %RSD T-calculated:

Mouthwash 249.43±19.13 7.669 1.806
Mineral water 0.3992±0.03910 9.795 <21.73
Tap water 0.2244±0.02298 10.241 2.732-1.502

DISCUSSION:

The experiment was conducted under room temperature of 22.0 0C .The standards containing
the Total Ionic Strength Adjustment Buffer which was used to overcome the effect of the
variable ionic strength of the solutions were prepared and the graph of their potential
difference against log [F] was plotted this relationship is best described by the Nernst
equation, the equation of the line is y = -38.164x-342 with R2 = 0.9167, the linear correlation
is close to one this indicates the directly proportional response between the standards
concentrations and potential difference hence high accuracy and precision in the results
obtained.

The obtained equation of the line was then used to calculate the concentrations of the
samples. For the mouth wash the mean and standard deviation were calculated to be

249.43±19.13 and the RSD is 7.669% which indicates the variation in the results obtained.

The T test was performed and the calculated T=1.806 was less than the table T, this indicates
that there is no significantly difference in the results obtained from the true value hence there
is high accuracy. The mean % error for this analysis is 10.86% which can be systematic or
random or both.

For mineral water the calculated mean and standard deviation are 0.3992±0.03910 and RSD=
9.795% this means the results were quite precise and the T cal=21.73 is higher than T table =
12.71 this indicated low accuracy in the results hence this means the sample was wrongly
prepared and this type of error is called random error.
For tap water the calculated mean and standard deviation were calculated to be
0.2244±0.02298 and the RSD is 10.241%, this is slightly high thus there is low precision in
the results. The T calculated range is 2.732-1.502 this is less than the T table hence there is
no significantly difference in the true and experimental value which indicates high accuracy
in the results.

The mouthwash had the highest concentration, considering toothpaste being left out of this
experiment.

Fluoride in both mouthwash and toothpaste is added to prevent tooth decay hence it is
required in large amounts but for toothpaste it cannot be too high because it will cause
damages in teeth and gums.

Mineral water is healthier than tap water, according to the World Health Organisation the
concentration of fluoride in water should not exceed 0,7 ppm the calculated concentration is
0,2244 ppm. The %RSD were calculated and it showed a good precision for all the samples.
TISAB was used in the experiment to maintain the pH constant and adjust the ionic strength.
Ion selective electrode should be held with care when it is being used because it can be easily
damaged, it should always be in a wet solution. It is responsive un-complexed ion. ISE
responds to ion activity rather than concentration and it is suitable technique to use for it uses
organic salt crystals.

CONCLUSION:

The aim of the experiment was to determine the content of fluoride in different dental
products such as toothpaste, mouthwash, mineral water and tap water using the solid-state
fluoride electrode and TISAB to match the standard solutions and samples in terms of activity
coefficient of the analyte. The aim was successfully achieved and the concentrations were
obtained. It was observed that mouth wash had the highest fluoride content. Mineral water is
healthier than tap water. TISAB was used to enhance the function of the electrode, the solid-
state was a suitable technique as it uses inorganic salt crystal.
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[3] Quantitative Chemical analysis, 6th Ed., Daniel C. Harris, W. H. Freeman and Company,
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[4] David L. Zellmer, ‘Fluoride Ion Selective Electrode Experiment – Direct Potentiometry
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[10] Healthline. 2021. What Is Fluoride? Uses, Benefits, Side Effects, and Safety. [online]
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[15] Walsh, Tanya, et al. “Fluoride Toothpastes of Different Concentrations for Preventing
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NOTE: as instructed by our lecturer, toothpaste has been left out of my experiment and
report.