The Analytica Societas Journals

Determination of pH of Shampoo and Fluoride Content of Toothpaste, Mouthwash, and Tap Water.
2
Malolot, Ryan Dave*, 2Barbaza, Marjette, 2Dela Paz, Xech Rafael, 1De Castro-Cruz Kathlia**,

1
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology;
2
Student (s), CHM115L/A12, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology

ARTICLE INFO

Article History:
Volume No.: 2
Issue No.: 1
ABSTRACT
Date of Submission: 17 August 2017 Potentiometry is a method of analysis used in order to measure the pH by using a glass
Date of Acceptance: 17 August 2017 membrane electrode or it can also be used in measuring the potential of a sample with
respect to its concentration. In this experiment, the pH of hair shampoos, shampoo-
Keywords: conditioner, and conditioner was determined using a pH meter and the fluoride
Potentiometry concentration of toothpastes and mouthwash was also determined using an ion
selective potentiometer. The fluoride content was determined by using the potentials
Calibration Curve
measured from potentiometer, generating a standard calibration curve. The researchers
Standard Addition. had conducted two methods in determining the concentration of fluoride which are the
calibration curve method or direct potentiometry and the standard addition method.
Electrode The pH observed among the samples showed that the shampoo are acidic in its
concentrated but the pH increases when it becomes diluted.
Electrode

Introduction is highly sensitive to measure pH or potential. The glass should

Potentiometry branch of electrochemistry concerned with the
relationship between the potential of an electrochemical cell
and the concentration of the contents of the cell. [1]. These
electrical potential is a useful property to observe the ionic
activities on a sample. Such chemical properties that can be
determined in potentiometry are pH and the concentration of a
specific ion. Through this experiment, the researchers attempt
to determine the pH of various hair shampoos using the
potentiometer and the fluoride concentration of known fluoride
products such as the toothpaste and mouthwash.
The assembly of the instrument for potentiometry which is the
primarily composed of a set of indicator and reference
electrode. These electrodes is bounded by a glass surface which
not be touched roughly because of its sensitivity and should be
washed every time of usage. The reference electrodes are ions
inside the potentiometer which interacts indicator electrode that
touches the analyte and interacts accordingly. [2]
For data analysis in Potentiometry, the data gathered are
efficiently analyzed through linear regression statistics which
can be generated by two methods namely the calibration curve
method and the standard addition method.
Calibration curve method is commonly practiced for
determining the concentration of a substance in an unknown
sample by comparing the unknown to a set of standards in
which they have known concentrations. It is highly
recommended for a large scale analysis of same samples.

Meanwhile, standard addition method is a type of quantitative
analysis that requires a set of prepared standards in which they
are directly added to aliquots of the sample in different
volumes. [3]. It is recommended for small scale analysis of
samples and when the analyte in the sample is consist of
complicated matrix. The addition of different volumes from the
sample aliquots should have an organized increment and should
be diluted at equal volume marks.
The objectives for this experiment are to be familiarized with
the potentiometric methods of analysis by determining the pH
and potential of various samples and compare the results
through their statistics. The samples to be used are hair
shampoos, shampoo with conditioner, and a conditioner for pH
determination while for ion selective Potentiometry, the
samples used were toothpastes, mouthwash, and tap water.
Experimental Section
The reagents used were Buffer solutions of pH 4 and 7, TISAB
(total ionic strength adjustment buffer) solution, 0.1 M F stock
standard solution.
The apparatus used were the pH meter, fluoride ion selective
electrode, beakers (25ml, 100ml, and 150ml) pipets (5ml,
10ml), volumetric flasks (100ml, 500ml).
The pH meter was used for the determination of the pH of
shampoo, shampoo with conditioner, and a conditioner while
fluoride ion selective electrode was used for the measurement
of potentials.
The brands of shampoo, conditioner, shampoo- conditioner,
toothpaste and mouthwash were tabulated below. The tap water
source was also included
Table 1: Brands used for Experiment 1.
Required Data
Shampoo Rejoice
Black Beauty
Head and shoulders (green)
Pantene (violet)
Dove
Pregroe
Conditioner Rejoice
Black Beauty
Head and shoulders (green)
Pantene (pink)
Dove
Pregroe
Page |2
Shampoo-Conditioner Rejoice
Black Beauty
Gard (pink)
Palmolive (green)
Palmolive (pink)
Toothpaste Close-up
Hapee
Colgate(green)
Mouthwash Colgate Plax
Astringosol
Listerine
Tap Water Mapua University, N405
The procedure for this experiment can be divided into two parts.
The first part is for the determination of pH on shampoo
samples while the second part is for the fluoride ion
concentration determination on toothpastes, mouthwash and tap
water.
For the determination of pH, the pH meter should be calibrated
first by adjusting the reading of the pH meter with buffer
solutions of known pH. As the pH meter already read the exact
pH of the buffer solutions, the samples are ready to be analyzed.
Each of the shampoo, shampoo with conditioner, and
conditioner samples were transferred to a beaker with an
amount possible to be read. The pH determination is done on
concentrated and diluted form of the sample. The first reading
of the pH meter are the concentrated samples and after that, the
samples were diluted to 45 mL to make a dilution ratio of 1:10.
It is recommended to calibrate the pH if the reading becomes
vague or imprecise.
After the researchers performed the pH determination with
three trials each sample, the data gathered would be analyzed
by determining the mean and its uncertainty.
For the fluoride ion determination, the samples should be
prepared first using the TISAB solution. Toothpaste samples
were weighed at about 0.20 grams and added with 50 mL of
TISAB solution in order to ionize completely the fluoride on
the samples. It was then heated and stirred at which it would be
diluted to a 100 mL volumetric flask.
On the mouthwash samples, about 25 mL of the sample was
mixed with 50 mL of TISAB solution and then it was diluted to
a 100 mL volumetric flask. Same procedure goes through with
the tap water samples. Figure 1 (on supporting information)
shows the prepared samples in the volumetric flask in which
they are ready for potentiometric measurement.
 Page |3

Tap water samples were also prepared by the same procedure. Head and shoulders(green)- 6.89± 0.13146 7.68± 0.04969
As for the standard sample preparation, 5.00 ppm fluoride stock Shampoo
solution was prepared by a series of dilution and aliquot it at an Head and shoulders(green)- 4.99± 0.07724 4.37± 0.02484
incremental volume. The aliquots were added with 50 mL of Conditioner
TISAB solution and dilute also to a 100 mL volumetric flask. Gard(pink)- Shampoo- 5.28 ± 0.04757 5.32 ± 0.08364
The concentration of the standards prepared should be 0.25, 0.5, Conditioner
1.0, and 2.5 ppm respectively. Pantene(violet)- Shampoo 6.22± 0.07027 6.00 ± 0.0203
Pantene(pink)- Conditioner 4.19± 0.35512 3.44 ± 0.08725
All of the samples are ready for the calibration curve method. Palmolive(green)- 5.04 ± 0.05914 4.94 ± 0.06085
Calibration curve method involves the plotting of the potentials Shampoo-Conditioner
measured versus the logarithm m of the concentration of the Dove- Shampoo 5.73 ± 0.10829 6.12 ± 0.07724
standards. Dove- Conditioner 4.41 ± 0.13758 5.6 ± 0.41694
Palmolive(pink)- Shampoo- 5.15 ± 0.05367 5.56 ± 0.15712
For the preparation of samples on the standard addition method,
Conditioner
5 mL of the prepared samples should be transferred to another
Pregroe- Shampoo 5.38± 0.0476 5.6± 0.43
volumetric flask and each of the standards should be added to
Pregroe- Conditioner 4.48 ± .2404 3.62 ± 0.1259
each of the samples making another series of dilution with
additional 50 mL of TISAB solution. *data with confidence level at 95%.

Table 2: Solution prepared for Standard Addition Method. It was observed that most of the diluted shampoo, conditioner
Solution Composition and shampoo-conditioner has higher pH than concentrated.
1 50 mL TISAB + 5 mL sample Water acts as a base when mixed in shampoo, conditioner and
+ 0 mL standard shampoo-conditioner.
2 050 mL TISAB + 5 mL sample
+ 10 mL standard Table 4: Fluoride content of Toothpaste, Mouthwash and
3 50 mL TISAB + 5 mL sample Tap Water using Calibration Curve.
+ 20 mL standard Brand- type Fluoride content (ppm)
4 50 mL TISAB + 5 mL sample Close-up- Toothpaste 177059104.4 ± 3.59
+ 30 mL standard Astringosol- Mouthwash 24044 ± 15290.7
M.U.- Tap Water (G2) 0.4956 ± .25
Measure the potential of each solution. Plot the Response ((Vo Hapee- Toothpaste 32497.3± 29.3878
+ Vstd)10⌃((E2-E1)/S))) vs (CV)std. and determine the Listerine- Mouthwash 0.0163± 0.003314
concentration of fluoride in the sample M.U.- Tap Water (G3) 1.0604± 43.2
Colgate (green)- toothpaste 1.46x10^5 ± 7.6213x10^-5
Colgate Plax- mouthwash 7.458x10^5 ± 3.3697x10^-5
Results and Discussion M.U.- Tap Water (G1) 16633990200± 1.97593x10^12
*only the 1st three set of data was computed by The Analytica Societas,
The students were able to meet the objectives of the experiment. others were collected from other groups
The findings were the following;
The calibration curve method is also known as direct
Table 3: pH of Shampoo, Conditioner and Shampoo- potentiometry in the procedure because the prepared samples
Conditioner. have their potentials measured directly without further
Brand- type pH conc. pH diluted modification unlike the standard addition method. The
Rejoice-Shampoo 5.562± 0.249 6.063± 0.121 calibration curve generated by the researchers are shown on
Rejoice -Conditioner 4.4 ± 0.105 4.574± 0.106 figure 2 (on supporting information).
Rejoice- Shampoo- 5.4433± 0.068 5.6878± 0.207
Conditioner The calibration curve method is commonly used for small scale
Black Beauty- Shampoo 5.97± 0.06085 6.31± 0.07172 of samples for content identification and in this case fluoride
Black Beauty- Conditioner 4.54± 0.05555 4.74± 0.08240 ions were detected. The plotting of the graph of calibration
Black Beauty- Shampoo- 5.37± 0.11110 5.65 ± 0.05555 curve are based on the potential of the standards versus the
Conditioner logarithm of the standard concentration. The slope and intercept
of the curve generated was used to calculate the fluoride content
 Page |4

of the samples. Calculations are further elaborated on the Conclusion

sample computation section
The experiment shows that potentiometry is an effective
Table 4: Fluoride content of Toothpaste, Mouthwash and method in the determination of pH and Fluoride concentration
Tap Water using Standard Addition Method. of various samples.
Brand- type Fluoride content (ppm)
Close-up- Toothpaste 38.203 ± 0.0011 The pH of various hair shampoos were identified using a
Astringosol- Mouthwash 2.436 ± 1.043 calibrated pH meter and among the samples of hair shampoos.
M.U.- Tap Water 2.331 ± 1.421 As observed from the data gathered, pH rises when the samples
Hapee- Toothpaste 0.7491± 4.3143 was diluted. The researchers learned that upon dilution of these
Listerine- Mouthwash 5.5517± 5.401 samples, the pH increases because water acts as a base
M.U.- Tap Water (G3) 13.77 ± 5.281
Colgate (green)- toothpaste 38.203 ± 1.1x10^-3 On the fluoride concentration determination, the researchers
Colgate Plax- mouthwash 408.155 ± 1.95x^-4 had shown the use of calibration curve method and standard
M.U.- Tap Water (G3) 11.288 ± 2.756x10^-3 addition method. The values obtained from the standard
*only the 1st three set of data was computed by The Analytica calibration method is different from the data obtained from
Societas, others were collected from other groups standard addition method. It shows that the identification of
fluoride concentration is still limited for these types of analysis.
The fluoride determination using standard addition method Both of these methods are highly dependent on the set of
involves the use of the calibration curve generated on the first standard solutions prepared. To generate the calibration curve,
method used. It means that this method is highly dependent on the set of standards should be accurately prepared to obtain a
the calibration curve generated in order to calculate for the result on the samples that are feasible.
concentration of the fluoride ion on the samples
References
The potentials gathered from the standard addition were used
for plotting the graph of standard addition on each sample. It 1] Harvey, D. (2013). Potentiometric Methods. Retrieved from
was used in calculating the response of the potentiometer (y- UC Davis ChemWiki:
axis of the graph) on each of the sample following the formula http://chemwiki.ucdavis.edu/Analytical_Chemistry/Analytical
𝐸2−𝐸1 _Chemistry_2.0/11_Electrochemical_Methods/11B%3A_Pote
( )
((𝑉𝑜 + 𝑉𝑠𝑡𝑑)10 𝑆 ntiometric_Methods

Where Vo is the initial volume, Vstd is the volume of the 2] Skoog, D. (2007). Principles of Instrumental Analysis 6th
standard added on the sample, E2 is the potential of the sample Edition. Toronto: Thomson Higher Education.
with standard, E1 is the potential of the sample without standard
(at 0 mL composition), and S is the slope of the calibration 3] Skoog, D. (2014). Fundamentals of Analytical Chemistry.
curve. Meanwhile for the x-axis of the graph of standard California: Cengage Learning.
addition, the milligrams of standard was calculated by
multiplying the concentration of the standard to the volume of
the standard added on the sample.

Furthermore, after generating the graph or line. The equation of

the line was used to determine the concentration of the fluoride.
Setting y=0 from the equation, the x value is to be solved and
to be divided by the initial volume of the sample which is 5 mL
in this case. The resulting value is the concentration of the
fluoride present on the sample.
 Page |5

Supporting Information
SAM Tap water
500
Standard Calibration Curve

(Vo + Vstd) x 10((E2-E1)/S)

400
135.0 y = 3.5156x - 163.87
300 R² = 0.9511
125.0
Measured potential, E

115.0 200
105.0 100
95.0
y = -17.257x + 122.35 0
85.0 R² = 0.9542 0 50 100 150 200
75.0
(CV)std
65.0
55.0
45.0 Figure 2: Standard Addition method for Tap water
-0.70 -0.20 0.30 0.80
log [F]
Sample Computation

Figure 1: Std. Calibration Curve 1. Mean pH and Uncertainty

For Rejoice Shampoo,

SAM Toothpaste Mean (conc.)
150 5.54+5.65+5.45
(Vo + Vstd) x 10((E2-E1)/S)

y = 0.9986x - 35.286 𝑥̅ = 3
= 5.5467
100 R² = 0.9714
Standard Deviation
50 ∑𝑛 (𝑥𝑖 − 𝑥̅ )2
𝑆𝐷 = √ 𝑖=1
𝑛−1
0
0 50 100 150 200 (5.54 − 5.5467)2 − (5.65 − 5.5467)2 − (5.45 − 5.5467
= √
(CV)std 3−1
SD = 0.1002
Figure 2: Standard Addition method for Close-Up toothpaste
Uncertainty

𝜇 at 95% Confidence Interval

SAM Mouthwash
𝑡(𝑆𝐷)
100 𝜇 = 𝑥̅ ±
√𝑛
(Vo + Vstd) x 10((E2-E1)/S)

80
y = 0.5373x - 3.7262 (4.3)(0.1002)
60 R² = 0.9774 𝜇 = 5.5467 ±
√3
40
𝜇 = 5.5467 ± 0.249
20
0
0 50 100 150 200
-20
(CV)std 2. Calibration Curve Method

Figure 3: Standard Addition method for Astringosol For x-axis,

𝑥 = log[𝐹 − ]
mouthwash
Where [F-] = 0.25, 0.5, 1.0, and 2.5 ppm

𝑥 = log(0.25) = −0.60206
 Page |6

For y-axis,
Mean potential at 0.25 ppm Set y=0, x= 35.335
47.6 𝑚𝑉+48.9 𝑚𝑉+49.5 𝑚𝑉
𝑥̅ = = 48.66 35.335
3 [𝐹 − ] = | | = 38.203 𝑝𝑝m
0.93

3. Fluoride Concentration by Calibration Curve Method

𝐸
10𝑚
[𝐹− ] = 𝑏
10𝑚
where E= potentials of each trial on the sample, m= slope,
and b= y-intercept

Trial 1 Close Up Toothpaste,

24 𝑚𝑉
10−17.257
[𝐹− ] = 6122.35
= 177059104𝑝𝑝𝑚
10−17.257

4. Standard Addition Method

For x-axis,
𝑥 = 𝐶𝑠𝑡𝑑 𝑉𝑠𝑡𝑑

where Cstd= 5.0 ppm

Vstd= 5 mL, 10 mL, 20 mL, and 30 mL

𝑥 = (5 𝑝𝑝𝑚)(5 𝑚𝐿) = 25 𝑚𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑

For y-axis,

𝐸2−𝐸1
( )
y= ((𝑉𝑜 + 𝑉𝑠𝑡𝑑)10 𝑆

where V0 = 55 mL (from 50 mL TISAB and 5 mL

sample), Vstd = 5 mL, 10 mL, 20 mL, and 30 mL, S= -
7.037 (from slope of calibration curve), E 1= mean
potential of sample at 0 mL std, E2= mean potential of
sample at 5,10,20, and 30 mL std

For Close Up Toothpaste,

At 25 mg standard,
38.6−39.37
𝑦 = (55 + 5)(10) −17.257 = 66.49 *This is the 1st submission. resubmission is still processing

5. Fluoride Concentration by Standard Addition

For Close Up Toothpaste,

Equation of the Graph:

𝑦 = = 0.9986𝑥 − 35.286