Lab 5: Determination of Fluoride in Commercial Products and Water with an Ion Selective

Electrode
Greta Becker, Austin Kuchenbecker, Michael Witkowski
20 November 2018
Abstract:
The purpose of this experiment was to determine the concentration of fluoride (F- ) in a
variety of samples including water, toothpaste, mouthwash, and an unknown sample. The electric
potential , in mV, of each sample was measured using an ion selective electrode, and the F-
concentration in each sample was found by generating a calibration curve using standards of
known sodium fluoride concentrations. The unknown sample was found to have a fluoride
concentration of 0.00067 +/- 0.00005 M, the tap water concentrations for the house, water
fountain, and science hall were 0.9 +/- 0.1 ppm, 0.7 +/- 0.1 ppm, and 1.1 +/- 0.3 ppm,
respectively. The mouthwash and toothpaste mass/volume percents were 0.011 +/- 0.002% and
0.14 +/- 0.04%, respectively. The findings for the mouthwash matches the value 0.01% that was
given on the manufacturer's bottle label, and the findings for toothpaste also matches the value
0.14% that was on the manufacturer's tube label.

Introduction:
The purpose of this experiment is to construct a calibration curve with a set of standards
of known fluoride concentrations using an ion selective electrode. This curve is used in order to
calculate the amount of fluoride in water, mouthwash, toothpaste, and in an unknown solution.
Fluoride, which is present in most drinking water, can have a positive impact on human
health (Farwell, 2006). This is most evident in its effect on teeth. When bacteria in the mouth
metabolize sugars, the pH in the in saliva is reduced which promotes tooth decay (Kanduti,
2016). Fluoride can adsorb to the crystal surface of the tooth and prevent tooth demineralization.
When pH levels rise, the fluoride can absorb into the enamel which allows the tooth to become
more resistant to decay in the future. However, excess fluoride can lead to adverse effects on
human health, including dental fluorosis, which changes the appearance of tooth enamel, or even
skeletal fluorosis, a debilitating bone disease (Farwell, 2006). Due to the helpful, but also
harmful roles of this chemical, it is essential to have an accurate and precise way to measure
fluoride levels especially in dental products and drinking water.
One way to measure the fluoride concentration of a sample is with an ion selective
electrode. Unlike a normal metal electrode, ion selective electrodes do not utilize redox
reactions. They are made of an internal and external reference electrode which are separated by a
membrane. This membrane can be made of glass, a liquid-infused organic polymer, or, in the
case of the fluoride ion selective electrode, a doped inorganic polymer. Because the electric
potential of both reference electrodes remains constant, the overall potential generated is only
dependant on the junction potential formed across the membrane. Fluoride ions travel from an
area of high concentration in the analyte to an area of lower concentration in the membrane and
settle in lattice vacancies in the doped inorganic crystal. The potential difference across the
membrane is measured in mV by the reference electrodes (Harris, 2006).

The potential difference formed at the ion selective membrane can be related to the
concentration of the fluoride ion based on the Nernst Equation:
 2.303𝑅𝑇
E=E°+ 𝑙𝑜𝑔 [𝑀− ]
𝑛𝐹

By plotting the potential difference (mV) vs the log[F-] for a series of standards with known
fluoride ion concentrations, a linear trendline can be generated. The validity of this line can be
2.303𝑅𝑇
assessed by comparing the slope to the theoretical slope of which gives a value of 59.16.
𝑛𝐹
If this data can be represented by the Nernst equal model, the equation of this line can be used to
solve for the fluoride concentration of a variety of samples including tap water, drinking fountain
water, toothpaste, mouthwash, and even an unknown solution.

Methods:
A 0.02629 M NaF solution and a 100 mL 10% total ionic strength adjustment buffer
(TISAB) solution were prepared in 100 mL volumetric flasks. Six standard solutions were also
made with concentrations of 5.2586x10-6, 5.2586x10-5, 2.6931x10-4, 5.3862x10-4, and 1.052x10-
3
, respectively in 100 mL volumetric flasks. The XL25 pH/Ion meter, the Ag/AgCl reference
electrode, and the fluoride ion selective electrode were placed in each standard solution in order
to measure the potential in mV. A calibration curve was generated by plotting Potential (mV) vs
Log[F-] using Microsoft Excel.
A 10% fluoride unknown solution was made by combining 10 mL of the unknown, 10
mL of TISAB solution and bringing up to volume with deionized water in a 100 mL volumetric
flask. This process was repeated twice and the voltage of each sample was measured.
The fluoride concentration, in Colgate Total Whitening toothpaste was analyzed by
measuring 0.2005 g, 0.2004 g, and 0.2000 g of toothpaste in three separate beakers with 10 mL
of TISAB solution and 40 mL of deionized water. The beakers were placed on a hot plate and
boiled for 5 min. The solutions were then transferred to 100 mL volumetric flasks and brought
up to volume with deionized water. After the solutions were cool, the voltage of each sample was
measured.
A mouthwash solution was prepared by pipetting 10 mL of the Crest Pro-Health
Complete mouthwash and 10 mL of TISAB solution into a 100 mL volumetric flask. The flasks
were brought up to volume with deionized water. Two more samples were prepared and the
voltage was measured.
Three types of water were collected; three samples from the tap in the science hall
analytical lab, three samples from the science hall water fountain, and three samples from the tap
at a house. The voltages were measured for the 9 samples.
Utilizing the equation generated from the calibration plot, the fluoride concentration for
the unknown, the mouthwash, the toothpaste, and the water samples, in each of the three trials,
was calculated. The average, standard deviation, relative standard deviation, and 95% confidence
interval were found using Microsoft Excel.
Results:

Molarity of Fluoride Standard Sample Calculation:

𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 1
𝐶1 𝑉1 = 𝐶2 𝑉2
(0.0269𝑀)(0.0100𝐿) = (𝐶2 )(0.100𝐿)
𝐶2 = 2.630x10-3 𝑀
𝑙𝑜𝑔(2.630x10-3 𝑀)=2.58 𝑀

Six standards with known fluoride concentrations were prepared, and the molarity of
each standard was calculated by multiplying the stock fluoride solution concentration of 0.02629
M by the initial fluoride solution volume and dividing by the final volume of 0.1 L. The
potential, in mV, was measured using the ion selective electrode. A calibration plot was
generated by plotting Potential (mV) vs. -log[F-]. A linear trendline was fit to the data and an
equation and R2 value were generated.

Table 1: Determination of Fluoride in an Unknown Solution

Potential (mV) [F-] (M)

Trial 1 259 mV 6.13x10-4

Trial 2 257 mV 6.64x10-4

Trial 3 255 mV 7.20x10-4

Average [F-] (M) 0.00067

Standard Deviation (M) 0.00005

Relative Standard Deviation (%) 8

95% Confidence Interval (M) 0.0001

Molarity of Fluoride in Unknown Sample Calculation:

𝑈𝑛𝑘𝑛𝑜𝑤𝑛 𝑇𝑟𝑖𝑎𝑙 1 259 𝑚𝑉
𝒚 = 𝟓𝟓. 𝟓𝟓𝟓𝒙 + 𝟓𝟓. 𝟓𝟓𝟓
259 = 56.95𝑥 + 19.072
− log[𝐹 − ] = 4.21
10−4.21 = 6.13 × 10−5 𝐹 − 𝑀 × 10 (𝑑𝑖𝑙𝑢𝑡𝑖𝑜𝑛 𝑓𝑎𝑐𝑡𝑜𝑟) = 6.13 × 10−4 𝐹 − 𝑀

Using the equation generated from the calibration plot, the potential reading for the
unknown solution was substituted for y and the equation was solved for x, which gave the
concentration of F-. This concentration was multiplied by a factor of 10 because 10 mL of the
unknown solution was diluted with water and TISAB buffer to a final volume of 100 mL.
 Table 2: Determination of Fluoride in Home Tap Water

Potential (mV) [F-] (M) [F-](ppm)

Trial 1 265 mV 4.81x10-5 0.913

Trial 2 268 mV 4.26x10-5 0.809

Trial 3 267 mV 4.43x10-5 0.842

Average [F-] (M) 0.9

Standard Deviation (M) 0.05

Relative Standard 6
Deviation (%)

95% Confidence 0.1

Interval (M)

Table 3: Determination of Fluoride in Water from Science Hall Water Fountain

Potential (mV) [F-] (M) [F-](ppm)

Trial 1 274 mV 3.34x10-5 0.635

Trial 2 271 mV 3.77x10-5 0.717

Trial 3 273 mV 3.48x10-5 0.661

Average [F-] (M) 0.7

Standard Deviation (M) 0.04

Relative Standard 6
Deviation (%)

95% Confidence 0.1

Interval (M)

Table 4: Determination of Fluoride in Science Hall Tap Water

Potential (mV) [F-] (M) [F-](ppm)

 Trial 1 263 mV 5.21x10-5 0.990

Trial 2 260 mV 5.88x10-5 1.12

Trial 3 258 mV 6.38x10-5 1.21

Average [F-] (M) 1.1

Standard Deviation (M) 0.1

Relative Standard 10
Deviation (%)

95% Confidence 0.3

Interval (M)

Fluoride in Water Sample Calculation:

𝐻𝑜𝑚𝑒 𝑇𝑎𝑝 𝑇𝑟𝑖𝑎𝑙 1 265 𝑚𝑉

𝒚 = 𝟓𝟓. 𝟓𝟓𝟓𝒙 + 𝟓𝟓. 𝟓𝟓𝟓
265 = 56.95𝑥 + 19.072
−𝑙𝑜𝑔[𝐹 − ] = 4.32
18.9984 𝑔 𝐹 − 1000 𝑚𝑔 𝑚𝑔
10−4.32 = 4.81 × 10−5 𝐹 − 𝑀 × × = 0.913 = 0.913 𝑝𝑝𝑚
1 𝑚𝑜𝑙 𝐹 − 1𝑔 𝐿

From the calibration plot equation, the potential reading for the unknown solution was
substituted for y and the equation was solved for x, which gave the concentration of F-. This
concentration was multiplied by the molar mass in order to find grams of F- per liter, and then
multiplied by a factor of 1000 in order to solve for parts per million (ppm).

Table 5: Determination of Fluoride in Mouthwash

Potential [F-] (M) Mass of F- (g) Mouthwash F-

(mV) Volume (mL) Mass/Volume
Percent (%)

Trial 1 263 mV 6.39x10-4 0.001215 10 0.0122

 Trial 2 260 mV 5.90x10-4 0.001120 10 0.0112

Trial 3 258 mV 5.66x10-4 0.001075 10 0.0108

Average [F-] 0.011

(M)

Standard 0.0007
Deviation
(M)

Relative 6
Standard
Deviation
(%)

95% 0.002
Confidence
Interval (M)

Fluoride in Mouthwash Sample Calculation:

𝑀𝑜𝑢𝑡ℎ𝑤𝑎𝑠ℎ 𝑇𝑟𝑖𝑎𝑙 1 201 𝑚𝑉

𝒚 = 𝟓𝟓. 𝟓𝟓𝟓𝒙 + 𝟓𝟓. 𝟓𝟓𝟓
201 = 56.95𝑥 + 19.072
−𝑙𝑜𝑔[𝐹 − ] = 3.19
18.9984 𝑔 𝐹 − 1𝐿
10−3.19 = 6.39 × 10−4 𝐹 − 𝑀 × × × 100 𝑚𝐿 = 0.001215 𝑔 𝐹 −
1 𝑚𝑜𝑙 𝐹 − 1000 𝑚𝐿
0.001215 𝑔 𝐹 −
× 100 = 0.0122%
10 𝑚𝐿 𝑚𝑜𝑢𝑡ℎ𝑤𝑎𝑠ℎ

Based on the calibration plot equation, the potential reading for the unknown solution
was plugged in for y and the equation was solved for x, which gave the concentration of F-. This
concentration was multiplied by the molar mass of F- and then divided by 1000 mL in order to
solve for g per mL of F-. Because the mouthwash was diluted to 100 mL, this mass was
multiplied by 100 mL in order to solve for the mass of F-. This mass was divided by the volume
of the mouthwash and multiplied by a factor of 100 in order to solve for a mass/volume percent.
 Table 6: Determination of Fluoride in Toothpaste

Potential [F-] (M) Mass of F- Mass of Toothpaste F-

(mV) (g) toothpaste Volume Mass/Volum
(g) (mL) e Percent
(%)

Trial 1 246 mV 1.04x10-4 1.97x10-4 0.2005 0.155 0.127

Trial 2 240 mV 1.32x10-4 2.51x10-4 0.2004 0.155 0.162

Trial 3 245 mV 1.08x10-4 2.05x10-4 0.2000 0.155 0.132

Average [F-] 0.14

(M)

Standard 0.02
Deviation
(M)

Relative 11
Standard
Deviation
(%)

95% 0.04
Confidence
Interval (M)

Fluoride in Toothpaste Sample Calculation:

𝑇𝑜𝑜𝑡ℎ𝑝𝑎𝑠𝑡𝑒 𝑇𝑟𝑖𝑎𝑙 1 246 𝑚𝑉

𝒀 = 𝟓𝟓. 𝟓𝟓𝟓𝒙 + 𝟓𝟓. 𝟓𝟓𝟓
246 = 56.95𝑥 + 19.072
−𝑙𝑜𝑔[𝐹 − ] = 3.99
18.9984 𝑔 𝐹 − 1𝐿
10−3.99 = 1.04 × 10−4 𝐹 − 𝑀 × × × 100𝑚𝐿 = 1.97 × 10−4 𝑔 𝐹 −
1 𝑚𝑜𝑙 𝐹 − 1000 𝑚𝐿
1 𝑚𝐿 𝐹 −
0.2004 𝑔 × = 0.155𝑚𝐿 𝑡𝑜𝑜𝑡ℎ𝑝𝑎𝑠𝑡𝑒
1.29 𝑔 𝐹 −
1.97 × 10−4 𝑔 𝐹 −
× 100 = 0.1267%
0.155 𝑚𝐿 𝑡𝑜𝑜𝑡ℎ𝑝𝑎𝑠𝑡𝑒

Again, using the calibration plot, the potential reading for the unknown solution was
plugged in for y and the equation was solved for x, which gave the concentration of F-. This
concentration was multiplied by the molar mass of F- and then divided by 1000 mL in order to
solve for g per mL of F-. Because the toothpaste was diluted to 100 mL, this mass was
multiplied by 100 mL in order to solve for the mass of F- in the toothpaste. The volume of the
toothpaste was found by multiplying the initial mass of the toothpaste by 1.29 g/mL, the density
of toothpaste. This mass of F- in the toothpaste was divided by the volume of the toothpaste and
multiplied by a factor of 100 in order to solve for a mass/volume percent.

Discussion:

The purpose of this experiment was to measure the fluoride concentration in a variety of
samples using an ion selective electrode. The fluoride ion concentration for each lab sample was
determined from the a calibration curve generated from standard solutions of a known
concentration and used to confirm the concentrations listed by the manufacturer. According to
the United States Public Health Service, the current recommendation for fluoride in drinking
water is 0.7 ppm (PHS, 2015). The drinking water the home tap water had a fluoride
concentration of 0.9 +/- 0.1 ppm, the science hall water fountain 0.7 +/- 0.1 ppm, and the
science hall tap water 1.1 +/- 0.3 ppm. These levels are all within acceptable HHS range, which
extends from 0.7-1.2 ppm. The mouthwash was determined to be 0.011 +/- 0.002% mass by
volume, with the manufacturer reporting 0.01% active ingredient. The toothpaste was found to
have 0.14 +/- 0.04 % mass by volume, with the manufacturer reporting 0.14%. The confirmation
of these fluoride concentrations between the experimental results and the manufacturer’s listings
provides support that ion selective electrodes are accurate instruments and would be useful to
measure fluoride concentration for commercial products.
The ion selective electrode used is highly sensitive to the fluorine ion. This experimental
setup allows for an easy measurement and provides a large linear response range. This was seen
in this experiment as a variety of concentrations were used to serve as standards and generate a
calibration curve with an R2 value of 0.9924, indicating that the data was linearly fit.
Furthermore, the slope of this calibration curve was 56.952 which was fairly close to the
2.303𝑅𝑅
theoretical slope of which gives a value of 59.16. The experiment also involves a short
𝑅𝑅
response time and is nondestructive which would allow us to do further testing on these sample
in the future, if necessary.
However, these electrodes are associated with some experimental issues as well. Firstly,
they have poor precision. The voltage readings would not easily stabilize, and although the
fluoride concentrations were accurate in comparison to the manufacturer's label, the uncertainties
associated with the measurements were large. Another major drawback of the ISE is that it
cannot detect complex ions containing the ion, meaning that non-active fluoride ingredients or
additives in the samples can interfere with the determination of isolated fluoride ion if the
additives can serve as a ligand or chelating agent.
Another drawback of ISEs is that they can be sensitive to other ions present in solution.
In order to overcome this, a different ion selective electrode could be utilized to determine
which, if any, additional ions may have been present in any of the samples. In addition to this,
more standard measurements could be taken in order to allow for more interpolation along the
calibration curve, improving accuracy. Furthermore, additional testing of water from more than
one tap in each building, as well as from more than one sample of the same products could work
well to eliminate the possibility of an erroneous initial sample.
Conclusion:

The purpose of this experiment was to determine the fluoride concentration of different
samples by measuring the voltage, using an ion selective electrode for fluoride. Knowing the
concentration of fluoride in a solution is important because if the concentration is too low, it will
not be as effective in dental products for rebuilding teeth but if too high, the fluoride will have
the opposite effect on a tooth and cause it to deteriorate. In order to find how much fluoride is in
a solution, an ion selective electrode for fluoride is used to create a fluoride calibration curve.
The voltage can then be obtained from the electrode and the concentration of fluoride can be
found using the graph. The fluoride sample was found to have a concentration of 0.00067 +/-
0.00005 M, the tap water concentrations for the house, water fountain, and science hall were 0.9
+/- 0.1 ppm, 0.7 +/- 0.1 ppm, and 1.1 +/- 0.3 ppm, respectively. The mouthwash and toothpaste
mass/volume percents were 0.011 +/- 0.002 % and 0.14 +/- 0.04 %, respectively. The values for
the mouthwash and toothpaste were consistent to those found on the product at 0.01% and
0.14%, respectively.

References:

Harris, D.C. Quantitative Chemical Analysis, 8th edition, W. H. Freeman and Co., New York;
2006.

Farwell, J.; Bailey, K.; Chilton, J.; Dahi, E.; Fewtrell, L.; Magara, Y. World Health
Organization 2006.

Kanduti, D.; Sterbenk, P.; Artnik, A. Materia Socio Medica 2016, 28(2), 133–137.

Public Health Reports 2015, 130(4), 318–331.