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Spring 2018
Fluorine is an element of the halogen group and it is found in human body as Calcium
fluoride. Fluoride can be obtained from fluoridated water and food like asparagus, carrots and
cabbage. Fluoride can help to reduce the incidence of tooth decay and increase bone density.
About 95% of the total Fluoride in the body present in bones and teeth as it is important for
the mineralization of bones and teeth. Dental caries can be prevented by Fluorine as it limits
the solubility of acid that is produced by bacteria. Fluoride is added to tap water as it helps in
reducing cavities in children. Inadequate fluoride intake can lead to increased risk of dental
caries.1
concentration of fluoride allowed in public water systems, also called the Maximum
Contaminant Level (MCL), is set at 4.0 mg/L. The standard is set to reduce the risk of
crippling skeletal fluorosis which is a bone disease that is caused by excessive fluoride
intake. The secondary standard is also recommended by EPA to prevent cosmetic effects or
aesthetic effects. The secondary standard is 2.0 mg/L and is not required for water systems to
comply.2
According to the study, the Fluoride levels were in the range of 0.140 ± 0.006–1.33 ± 0.158
% w/w and the average was 0.851 ± 0.097 % w/w. The Fluoride levels in the phosphate
fertilizers were found out by using ion chromatographic and ion selective electrode methods.
Then, the fraction of Fluoride in feedstock in the fertilizers were determined to be 3-75% by
comparing the [P2O5]/[F] ratio of the seven samples. Taking into account of the annual
consumption of phosphate fertilizers in India, the total Fluoride load in agricultural field was
determined to be 127,650 ± 14,550 MTy−1. While the study focus on analysis of fluoride
content in fertilizers using ion chromatographic and ion selective electrode, our experiment
by using the fluoride ISE. The fluoride ISE is a solid-state electrode that can measure the
voltage that is directly related to the concentration of fluoride in the analyte. A crystal of
lanthanum fluoride doped with 1% of europium fluoride is placed at the bottom of the
electrode. The conductivity of the crystal is increased and migration of fluoride through the
vacancies occurs due to the help of europium in the organic crystal. Migration of fluoride
through the membrane causes a charge separation between concentration inside and outside
of the electrode, producing potential difference. When compared to many other analytical
techniques, ISE are relatively cheap and easy to operate. Moreover, some of the ISEs can be
used to measure wide range of concentration. Fluoride ISE was used in this experiment as it
is does not alter the analyte and it has fast response time. It would not be interfered by most
of the anions other than hydroxide due to the fact that hydroxide ion has similar size as
fluoride ion.4
Ion selective electrodes is used to measure the activity of a free ion in the sample
solution. The activity of an ion is directly proportional to its concentration and the
𝑎𝑖 = 𝛾𝑖 𝐶𝑖 (Equation 1)
The concentration of fluoride in the sample can be found using the electrochemical response
of the fluoride ISE as shown in Equation 2, where 𝐸, 𝐸 0 , 𝐸𝐽 , R T, z, F and 𝑎𝐹− represent the
measured voltage, standard potential, junction potential, gas constant, temperature, charge of
In this report, the concentration of fluoride ion in waste water sample and mouthwash
sample was determined using two methods which were external calibration curve method and
standard addition method with ISE instrument. The result was then compared to . Based on
the findings,
Experimental
The experiment was carried out using two methods, which included external
calibration curve and standard addition method. Both of the methods were conducted by
The first method used in this experimental was by constructing an external calibration
curve. 1 L of 1 M NaCl solution was prepared by adding 58.5390 (±0.0001) g of NaCl salt
into a 1 L reagent bottle and was diluted to the mark using deionized water. In order to
prepare NaF stock solution, 1.0019 (±0.0001) g of NaF powder was added into a 100.00 mL
volumetric flask and was diluted to the mark using NaCl solution.
Nine standards with 5000, 2500, 1000, 100, 10, 1, 0.1 and 0.01 ppm were prepared in
50 mL volumetric flasks by using series dilution method. 25.00 (± 0.03) mL of the NaF stock
solution was pipetted into a 50.00 (± 0.05) mL volumetric flask and was diluted to the mark
using 1M NaCl solution to make 5000 ppm standard. The solution was inverted a few times
to be fully mixed and was transferred to plastic bottle with label. Same procedure was
added into a 50.00 (± 0.05) mL volumetric flask using a pipette and was diluted to mark
using NaCl solution. The solution was transferred to a plastic bottle and was labelled. The
same step was repeated by replacing NaCl with Deionized water to prepare the second
mouthwash sample.
Second method used in the experiment was standard addition. 5.00 (± 0.01) mL of
unknown wastewater was pipetted into a 50.00 (± 0.05) mL volumetric flask and was diluted
to mark using 1M NaCl solution. The solution was transferred to plastic bottle and was
A specialized stirrer was used to stir the solution gently. The plastic beaker was rinsed
with the desired sample and at least 25 mL of the sample was added to the beaker. Voltages
were measured for external calibration curve. For standard addition method, 25.00 (± 0.03)
mL of “SA Unknown” was pipetted into the beaker and the voltage was measured. 200 (±2)
μL of 10,000 ppm standard solution added to the beaker with “SA unknown” using a
micropipette. The addition of 200 (±2) μL of 10,000 ppm standard solution was repeated five
determined by applying the Nernstian equation (See Equation 3). The voltages of eight
calibration standards and stock solution were measured and pF values were calculated by
taking the log of concentration for each solutions. (See Table 1).
Table 1. Recorded concentration, voltage and pF values for stock solution and eight
standards.
3 1000 170.0 3
4 100 225.7 2
5 10 276.1 1
6 1 305.4 0
7 0.1 310.6 -1
8 0.01 299.5 -2
An external calibration curve of voltage (mV) versus log (F-) (ppm) was plotted as
shown in Figure 1. The calibration curve showed the linear part that obeyed the Nernstian
equation and non-Nernstian part with their trendline and R2 value. The reported R2 value for
nonlinear part and linear part of the calibration curve were 0.2822 and 0.9992 respectively.
y = 2.95x + 308.12 350
R² = 0.2822
300
200
150
100
50
0
-3 -2 -1 0 1 2 3 4 5
log (F-) (ppm)
Figure 1. Plot of calibration curve of voltage (mV) versus log (F-) (ppm) showing Nernstian
part and non-Nernstian part with trendline and R2 values of 0.9992 and 0.2822.
From the calibration curve, the limit of detection (LOD) and limit of quantitation
(LOQ) were determined. LOD of log of fluoride concentration was the intersection of the
Non-Nernstian part and Nernstian part. To determine the intersection point, the y values for
two equations of the curve were set to be equal. The LOD of fluoride concentration was
calculated by taking the inverse of the log concentration. The determined LOD of fluoride
= 0.47444 ppm
[𝐹 − ] = 100.47444
= 2.9815 ppm
To determine the LOQ, the lowest concentration in the Nernstian part was
determined. From the calibration curve, the lowest log concentration of Fluoride in linear part
was found to be 1 ppm. The LOQ of Fluoride concentration was calculated by taking the
[𝐹 − ] = 101
= 10 ppm
wastewater, mouthwash and mouthwash no NaCl. The log [F-] for each solutions were
determined by plugging in the voltage into the equation of Nernstian part from the calibration
mouthwash no NaCl were 4093.5 ppm, 69.7 ppm and 113.9 ppm respectively. Sample
= 3.612
[𝐹 − ] = 103.612
= 4093.6
The uncertainty of the calibration curve was calculated by using LINEST Function
with the help of Excel. Equation 4 indicated the propagation of uncertainty of the calibration
curve. From the uncertainty obtained from the LINEST function, the percent errors of
calculation below shown the uncertainty and percent error for fluoride concentration in
unknown waste water. The calculated uncertainty and percent error of fluoride concentration
𝑠𝑦 1 1 (𝑦−𝑦)2
𝑢𝑥 = √ + 𝑛 + 𝑚2 ∑(𝑥 −𝑥)2
|𝑚| 𝑘
(Equation 4)
𝑖
=381.60
381.6×100
%𝑒[𝐹− ] = 4.0 3
9 ×10
= 9.3%
Table 3. Calculated uncertainty for [F-] and percent error (%e[F-]) of unknown wastewater,
mouthwash, mouthwash no NaCl.
and Vs variable represented slope of Nernstian part in calibration curve, voltage, initial
volume of unknown solution and volume of standard solution added respectively. From the
calibration curve in method 1, the determined S value was -54.505. The reported R2 value of
0.012
0.010
0.008
0.006
0.004
0.002
0.000
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Vs (mL)
equation (See Equation 4) was used to determine the volume of standard solution and its
uncertainty. The calculated Vs was 0.7387 mL with uncertainty of 4.0172 using LINEST
function.
used, where [S] stood for the concentration of standard solution, Vs stood for the volume of
standard solution, V25mL stood for 25.00mL and [S25mL] stood for the standard concentration
at 25.00 mL.
Equation 6 was used to calculate the fluoride concentration in the unknown where
[X], Vinitial, [S50mL] and V50mL were the unknown fluoride concentration, initial volume of
unknown solution, fluoride concentration of standard at 50.00 mL, final volume which as
50.00 mL respectively. [S50mL] was replaced with [S25mL] as they had the same value. The
calculated fluoride concentration in unknown solution was 2954.8 (±4.03%) ppm using
Concentration of fluoride and uncertainty obtained from first and second method for
Table 4.
Mouthwash 69.7(±6.4%) -
Discussion
LOD is the lowest concentration of the analyte in the sample that can be reliably
distinguished from zero. Whereas, LOQ is the lowest concentration at which the analyte in
the sample that can be detected with acceptable precision and accuracy. To find the LOD, the
intersection point of Nernstian and Non-Nernstian part of the external calibration curve was
determined. The LOQ was determined by taking the lowest concentration of the Nernstian
part of the curve. LOD and LOQ were estimated From the external calibration curve, the
LOD and LOQ were determined to be 2.982 ppm and 10 ppm respectively. This meant that
the lowest concentration at which the fluoride can be detected was 2.982 ppm while the
lowest concentration of fluoride ion that can be determined precisely and accurately was 10
ppm.
In addition, LOD of ISE had influence on concentration of analyte, and mobility of
primary ion. Lower LOD would lower concentration of analyte existing in samples. Lower
mobility of primary ion made it hard to diffuse outside the membrane and prevent leaking from
inside electrode, which lowered LOD. Figure 1 showed there were two trendlines coming from
linear and Non-Nernstian part of the curve. Non- Nernstian part appeared due to low examined
- mouthwash – calibration salt or not (Nernst equation, solution with salt - keep ionic
2) Standard addition
3) why use plastic bottle, not glass? – fluoride ions on glass (not fluoride dissolving the glass
but van der Waals interaction) – remember citation, note: not hydrofluoric acid
5) compare external calibration and standard addition, which one more accurate, why?
result:
intro
-Nernst equation
1. https://www.nap.edu/read/11537/chapter/35#313
2. https://www.epa.gov/sites/production/files/2015-
10/documents/2011_fluoride_questionsanswers.pdf
3. https://www.sciencedirect.com/science/article/abs/pii/S0022113918300265
4. lab manual