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Determination of Fluoride concentration using Ion Selective Electrode

Name: Shu Yee Lau

Lab partner: Amanda Wang

Due date: 4/12/2018

Lab section: 008

Spring 2018

TA: Peymon Baghernejad


Introduction:

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

According to the U.S Environmental Protection Agency (EPA), the maximum

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

Fluoride content in 7 commercial phosphate fertilizers was determined in a study.

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

would determine the concentration of fluoride using ion selective electrode.3

In this experiment, the concentration of Fluoride in different samples were determined

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

concentration of other dissolved substances in the solution. (See Equation 1)

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

measured species, faraday constant and fluoride activity respectively.


𝑅𝑇
𝐸 = 𝐸 0 + 𝐸𝐽 + 𝑧𝐹 ln 𝑎𝐹− (Equation 2)
The equation can then be defined in terms of the activity of fluoride, while expressing the

concentration of fluoride in as pF. (See Equation 3)4


𝑅𝑇 2.303𝑅𝑇
𝐸 = (𝐸 0 + 𝐸𝐽 + 𝑧𝐹 ln 𝛾𝐹− ) − log 𝑝𝐹 (Equation 3)
𝑧𝐹

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

measuring the voltage of samples using ISE.

Method 1: External calibration curve standard preparation

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

repeated for other 8 standards using series dilution method.

Two mouthwash dilutions were prepared. 5.00 (± 0.01) mL of mouthwash wash

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.

The voltage of 8 standards, stock solution, unknown, mouthwash and mouthwash no

NaCl were measured using ISE.

Method 2: Standard addition method preparation

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

labeled as “SA Unknown”.

Measuring using ISE

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

of 8 standards, stock solution, “unknown wastewater”, “mouthwash”, “mouthwash no NaCl”

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

more times and the measurement of voltage was recorded.


Results

Method 1: External Calibration curve

Fluoride concentration in unknown wastewater and two mouthwash sample can be

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.

Solution Concentration (ppm) Voltage (mV) pF (ppm)

Stock solution 10000 112.4 4

1 5000 130.7 3.69897

2 2500 148.7 3.39794

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

250 y = -54.505x + 332.58


R² = 0.9992
Voltagel (mV)

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

concentration was 2.982 ppm. The calculation was demonstrated as below.

2.95𝑥 + 308.12 = −54.505𝑥 + 332.58


332.58−308.12
𝑥= 54.505−2.95

= 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

inverse log of 1, which was 10 ppm.

[𝐹 − ] = 101

= 10 ppm

Table 2 showed the determined voltage and fluoride concentration of unknown

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

curve. The determined fluoride concentration in unknown wastewater, mouthwash and

mouthwash no NaCl were 4093.5 ppm, 69.7 ppm and 113.9 ppm respectively. Sample

calculation for unknown wastewater solution was shown as below.


135.7−332.58
𝑝𝐹 = −54.505

= 3.612

[𝐹 − ] = 103.612

= 4093.6

Table 2. Voltages and calculated fluoride concentration of unknown wastewater, mouthwash


and mouthwash no NaCl.

Solution Voltage (mV) Log [F-] (ppm) [F-] (ppm)

Unknown Wastewater 135.7 3.6121 4093.6

Mouthwash 232.1 1.8435 69.7

Mouthwash no NaCl 220.5 2.0563 113.9

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

unknown wastewater, mouthwash and mouthwash no NaCl were calculated. Sample

calculation below shown the uncertainty and percent error for fluoride concentration in
unknown waste water. The calculated uncertainty and percent error of fluoride concentration

were shown in Table 3.

𝑠𝑦 1 1 (𝑦−𝑦)2
𝑢𝑥 = √ + 𝑛 + 𝑚2 ∑(𝑥 −𝑥)2
|𝑚| 𝑘
(Equation 4)
𝑖

𝑢[𝐹− ] = 2.3026 × 𝑢log(𝐹− ) × [F−]

= 2.3026 × 0.04 × 4.09 × 103

=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.

Solution [F-] (ppm) 𝒖[𝑭−] %𝒆[𝑭− ] (%)

Unknown wastewater 4093.6 381.60 9.3

Mouthwash 69.7 6.35 6.4

Mouthwash no NaCl 113.9 10.29 10.5

Method 2: Standard Addition


𝐸
Graph of (𝑉𝑜 + 𝑉𝑠 ) × 10𝑆 versus Vs was plotted as shown in figure 2, where S, E, Vo

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

the standard addition curve was 0.99959.


0.020
0.018
0.016
y = 0.0092x + 0.0068
0.014 R² = 0.9959
(Vo+Vs)*10^(E/S)

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)

Figure 2. Standard addition curve of (Vo+Vs)×[10]^(E/S) versus Vs of diluted unknown


solution with reported R2 value of 0.99959.
By using Excel, LINEST Function was calculated and propagation of uncertainty

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.

To determine the concentration of standard solution at 25.00 mL, Equation 5 was

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.

[S] × VS= [V25mL] × [S25mL] (Equation 5)

0.7387 ±(4.0172) 𝑚𝐿×10,000𝑝𝑝𝑚


[S25mL] = 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

standard addition method.


0.7387 ±(4.0172) 𝑚𝐿×10,000𝑝𝑝𝑚
×50 (±0.05)𝑚𝐿
25.00 𝑚𝐿
[X] = = 2954.8 (±4.03%) ppm
5 (±0.02) 𝑚𝐿

Concentration of fluoride and uncertainty obtained from first and second method for

unknown wastewater, mouthwash and mouthwash no NaCl were summarized as shown in

Table 4.

Table 4. Summarization of determined fluoride concentration of unknown wastewater,


mouthwash and mouthwash no NaCl using calibration curve and standard addition method

Solution [F-] from calibration curve [F-] from standard

(ppm) addition (ppm)

Unknown wastewater 4093.6 (±9.3%) 2954.8 (±4.03%)

Mouthwash 69.7(±6.4%) -

Mouthwash no NaCl 113.9(±10.5%) -

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

concentration which did not give linear line.


1) external calibration

-LOD, LOQ – explain importance

- mouthwash – calibration salt or not (Nernst equation, solution with salt - keep ionic

constant, more accurate)

2) Standard addition

- values, calibration curve, accuracy, r^2

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

4) values, calibration curve, accuracy, r^2 of two methods,

-limitation of the experiment : glass give lower value

-uncertainty, range (big range less precise)

- accuracy, trend line, r^2 value

5) compare external calibration and standard addition, which one more accurate, why?

result:

-make sure standard addition curve : positive slope

-linear equation fit, one Nernst equation, one no

- final table of all unknown uncertainty

intro

- talk about how electrode work

-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

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