Dlamini Sinegugu Mbali Magnificent

213502471
Practical 7: Aluminium Speciation
Through Complex Titration with
Fluoride-ISE
APCH 332 Environmental Analysis
12 October 2021
Abstract
The aim of the practical was to investigate the speciation of aluminium in natural water and
wastewater using complexometric titrations with a fluorine ion selective electrode, these were
used in conjunction with potentiometry using ISE for detection of the free metal concentration.
The concentration of fluoride in natural water was found to be less than in wastewater, due to
more natural active ions that can complex with the Fluoride ions thereby decreasing its
concentration. This experiment being similar to one previously conducted similarly evaluated
the following aspects: the use of different TISAB solutions (total ion strength adjustment
buffer), minimising electrode drift, electrode care and optimisation, interference correction
procedures, calibration procedures for trace F-, and the determination of the analytical
parameters. The concentration of fluoride in aluminium fluoride, natural water and wastewater
samples were found to be 0,0894, 0,0295, 1.695 x10-4 respectively. Lastly, it can be said that
the objective of this experiment was to evaluate F-ISE for low level F- determination, and how
to apply the method accurately for trace F- determination in natural and wastewater water.
Aim
The aim of this experiment is to determine how the presence of ligands can affect the level of
labile metals in wastewater systems and natural water systems. This experiment was
undertaken by potentiometry using ISE, more specifically Fluoride ion selective electrode (F-
ISE) for detection of labile metal concentration in the water systems.
Introduction
The ion selective electrode (ISE) potentiometric method is an analytical technique that uses
electrical potential to assess the activity of ions in aqueous solution. It's a tool for determining
ions, and it's most typically employed in water[1]. The fluoride ion selective electrode (F-ISE)
was employed in this experiment. A fluoride ion selective electrode is an ion selective electrode
that is sensitive to fluoride ion concentration. The most frequent instrumental technique for
fluoride analysis in water is the fluoride ion selective electrode (F-ISE) potentiometric method.
[2]. The lanthanum fluoride electrode is a fluoride ion selective electrode in which the sensing
element is a lanthanum fluoride (LaF3) crystal membrane doped with europium fluoride
(EuF2). The crystal's inner surface is in touch with the inner reference solution, while the
crystal's outer surface is in contact with the analyte solution [3].
 Figure 1: Fluoride ion selective electrode (F-ISE) [4]
The transmission of the fluorine ions (figure 2) can be measured using the Nernst equation to
determine the concentration of the fluorine in the sample

𝑹𝑻
𝑬 = 𝑬° − 𝒍𝒏𝑸
𝒏𝑭

The pH of the analysis must be kept at between 5 and 5.5 for optimum results. Dependant on
the basicity or acidity of the solution, either HF can form (lower pH) or OH- ions (higher pH)
could be detected by the electrode and affect the analysis. A total ionic strength adjustment
buffer (TISAB) is used to buffer the solution so that the pH of 5 can be maintained throughout
the analysis. In this analysis the aluminium complexes with the free fluorine ions and thus
affects the activity of the fluorine in the sample. This measures the point where all the
aluminium complexes with the fluorine and the thus determine the aluminium content in the
sample.

Figure 2: Movement of fluorine ions in the electrode to create potential difference during
analysis [5].
Potentiometric technique is fundamentally the measure of potential of an electrochemical cell
under static conditions; it’s based on ion selective electrodes. These electrodes respond to
analyte activities rather than concentration. Activities are related to concentrations:
ax= γ [ X]
where ax is the activities, [X] is the concentration and γ is the activity coefficient of X depends
on the ions present in the solution and their total ionic strength
The potential of the cell is the following equation:
ECell =K – 0.0592 /n log aF
where 0.0592 is the Nernst slope.[6]
Adding aluminium solution to buffered fluoride solution is anticipated to decrease the
concentration of fluoride sensed by the F-ISE. Decrease in fluoride concentration is due to the
reaction between Al3+ and F-. When a buffered fluoride titrated with aluminium ion, an Al-F
complex is formed which decreases the free fluoride ion activity and result in a positive slope
as opposed to a negative slope for a direct fluoride curve. [7].

Experimental procedure
Using 0.1 M NaF stock solution the standard concentration of the standard solution was
prepared as follows:
C1V1= C2V2
V1 = C2V2/ C1
= (0.05 M) (100 mL) / 0.1 M
= 50 mL.
Similar calculations were done for all the standard solution and results tabulated
Table 1: Volume of 0.1 M NaF added to each standard

Standard Solution Volume of NaF added

1 0.05 50
2 0.01 10
3 0.005 5
4 0.001 1
5 0.0005 5
6 0.0001 1
7 0.00005 0.5

Therefore, it can be said that to make a concentration of 0.05 M NaF, 50 mL of 0.1 M NaF was
pipette in to 100 mL volumetric flask and made to the mark with the Total ionic strength
adjustment buffer, TISAB solution which was prepared for us beforehand. Several dilutions
were conducted by pipetting the appropriate amount of the stock standard solution, from the
table above, into 100 ml volumetric flasks and dilute to the mark with TISAB buffer. the rest
of the standard solutions were made in a similar way.
For the fluoride calibration curve:
The potential of each standard solution was measured using a pH meter, where the potential
reading was allowed to stabilize for at least 2 minutes before being recorded from the lower to
the higher concentration standards.

For the aluminium-fluoride curve:

10.00 mL of 0.1 M fluoride standard was pipette into a beaker were 10 mL of TISAB buffer
was added and allowed to mix. An initial potential reading is taken before any addition of
aluminium. 2 mL of 0.01 M aluminium standard solution is added into the beaker while stirring
and record the potential of the mixture as we continue to add small increments until the
potential reading reaches a steady state equilibrium.
Results

Table 2: concentrations and potentials of sodium fluoride (NaF) working standards

Standard Concentration (M) Potential (mV) Log (F-)

1 0.00001
2 0.00005 -391.6 -4.30
3 0.0001 -378.1 -4.00
4 0.0005 -412.1 -3.30
5 0.001 -418 -3.00
6 0.005 -456 -2.30
7 0.01 -475 -2.00
8 0.05 -517 -1.30

0
-5 -4,5 -4 -3,5 -3 -2,5 -2 -1,5 -1 -0,5 0
-100

y = -44,418x - 563,58
-200
Potential (mV)

R² = 0,9488

-300

-400

-500

-600
Log [F-]

Figure 3: Calibration curve of the fluorine standards.

Table 3: potentials readings of aluminium fluoride solution with addition of 0.01 M
aluminium solution

Volume of Aluminium Potential reading (mV) DE/DV

solution added (mL)
0 -523 2.0
2 -517 2.0
4 -513 2.0
6 -509 2.5
8 -504 3.0
10 -499 2.0
12 -495 2.5
14 -490 2.5
16 -485 2.5
18 -480 3.0
20 -474 3.5
22 -467 5.0
24 -457 5.0
26 -447 6.5
28 -434 7.0
30 -420 3.5
32 -407 6.5
34 -394 4.8
36 -384.4 4.55
38 -375.3 1.75
40 -371.8 2.8
42 -377.4 1.3
44 -380 0.5
46 -379 1.7
48 -382.4 0.6
50 -383.6 3.65
52 -376.3 1.35
54 -373.6 1.7
56 -370.2 0.2
 0
0 10 20 30 40 50 60

-100

y = 3,1858x - 526,07
-200
Potential (mV)
R² = 0,9342

-300

-400

-500

-600
Volume of Aluminium added(mL)

Figure 4: Aluminium-Fluoride curve.

6 y = -0,0188x + 3,4876
R² = 0,0316
5
DE/DV

0
0 10 20 30 40 50 60
Volume of Aluminium added(mL)

Figure 5: first derivative of AL-F curve

Table 4: Potential readings for aluminium-fluoride in natural water sample (sample 1) upon
addition of standard aluminium solution

Volume of Aluminium Potential reading (mV) DE/DV

solution added (mL)
0 -400 -2.00
2 -404 -0.50
4 -405 4.15
6 -396.7 7.65
8 -381.4 3.00
10 -375.4 2.60
12 -370.2 1.75
14 -366.7 -0.20
16 -367.1 1.85
18 -363.4 0.85
20 -361.7 0.90
22 -359.9 0.25
24 -359.4 0.05
26 -359.3

-340
0 5 10 15 20 25 30
-350
y = 1,9659x - 402
R² = 0,8722
-360
Potential (mV)

-370

-380

-390

-400

-410
Volume of Aluminium added(mL)

Figure 6: Aluminium-Fluoride curve for the in natural water sample.

 10

8
y = -0,0617x + 2,3055
6 R² = 0,0385

4
DE/DV

0
0 5 10 15 20 25 30
-2

-4
Volume of Aluminium added(mL)

Figure 7: First derivative of AL-F curve for natural water sample.

Table 5: Potential readings for aluminium-fluoride in waste sample (sample 2) upon addition
of 0.01 M aluminium solution

Volume of Aluminium Potential reading (mV) DE/DV

solution added (mL)
0 -415 -2.5
2 -410 0.5
4 -409 1.5
6 -406 1.5
8 -403 1.5
10 -400 1.65
12 -396.7 -0.25
14 -397.2 5.1
16 -387 5.1
18 -376.8 3.1
20 -370.6 0.85
22 -368.9 1.3
24 -366.3 0.65
26 -363.5 0.75
28 -363.4 0.05
 -350
0 5 10 15 20 25 30
-360
y = 2,0632x - 417,78
-370 R² = 0,9601
Potential (mV)
-380

-390

-400

-410

-420

-430
Volume of Aluminium added(mL)

Figure 8: Aluminium-Fluoride curve for the wastewater sample.

5
y = 0,0368x + 0,8717
4 R² = 0,029

2
DE/DV

0
0 5 10 15 20 25 30
-1

-2

-3
Volume of Aluminium added(mL)

Figure 9: First derivative of AL-F curve for wastewater sample.

Calculations
For the fluoride concentration in natural water
From table 4 and figure 6, volume of aluminium that brought about a sharp potential change
point is at 4.0 mL.
𝑛(𝑚𝑜𝑙𝑒𝑠) = 𝑀 × 𝑉
Al moles= 0.01M × 4.0×10-3L
=4.0×10-5mol
From the calibration curve obtained in figure 3, 𝒚 = 1,9659𝑥 − 402
𝑦 = −405 𝑚𝑉
-405 mV = 1.9659 - 402
−405+402
x= = -1.53
1.9659
x = Log[F-]= - 1.53
[F-] =0.0295 M
Similar calculations were done for all the sample and results tabulated.
Table 6: Summary table of the respective samples analysed number of moles, potential reading
and respective fluorine concentration and fluorine stoichiometric state.
Sample Mole of Al/mol Potential/mV [F-]/M Al-F complex
-5
Aluminium-Fluoride 8.0×10 - 517 0.0894 AlF3
Natural Water 4.0×10 -5
- 405 0.0295 AlF4-
Wastewater 2.0×10-5 - 410 1.695 ×10-4 AlF2+

Discussion
The aim of this experiment is to determine how the presence of ligands can affect the level of
labile metals in wastewater systems and natural water systems. The calibration curve of
fluoride standards against potential was plotted and the equation of the line was determined
together with the R2 value, the value was found to be 0,9488 which is close to one which meant
a good coloration and that means the results were a bit accurate or close to the literature values
and the good relationship between the values. The calibration curve has a slope of 44.418x mV
per decade concentration of F- which is higher than the known Nernst slope of 517 mV per
decade concentration of F- . The difference in slopes could be due to not allowing potential
reading to stabilize and recording them as they still fluctuating.
The number of moles contained in each sample was calculated using the volume at the sharp
point of the curve and the concentration of Al(NO3)3. The number of moles found for
aluminium fluoride, natural water, and wastewater were 8.0×10-5, 4.0×10-5, and 2.0×10-5,
respectively. The curve point of natural water is discovered to be lower than that of wastewater,
implying that treating natural water is easier and faster than treating wastewater.
The equation of the line was used together with the potential at a sharp point to calculate the
concentration of fluoride in all samples. The concentration of fluoride in aluminium fluoride,
natural water and wastewater samples were found to be 0,0894, 0,0295, 1.695 x10-4
respectively. The concentration of fluoride in natural water was expected to be less than in
wastewater, due to more natural active ions that can complex with the Fluoride ions thus
decreasing its concentration.
 Conclusion
The fluoride ion concentrations were determined in both water samples and aluminium-fluoride
curve. The slopes were positive to indicate the reduction of free fluoride ions for the formation
of complexes. The water systems used were from wastewater systems and natural water
systems these were used in conjunction with potentiometry using ISE for detection of the free
metal concentration. The concentration of fluoride in natural water was found to be less than
in wastewater. Addition of aluminium solution to buffered fluoride solution decreased the
concentration of fluoride due to the reaction between Al3+ and F-.
References
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[3] US Environmental Protection Agency: Fluoride: National primary drinking water

regulations, Proposed Rule. Federal Register 1985; 50:20164- 20175.
[4] “HI4010 - Fluoride Ion Selective Electrode by HANNA Instruments
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