Journal of Analytical Sciences, Methods and Instrumentation, 2020, 10, 97-103

https://www.scirp.org/journal/jasmi
ISSN Online: 2164-2753
ISSN Print: 2164-2745

Determination of Fluoride in Various Samples

Using a Fluoride Selective Electrode

Kamal Shaiyad Miya, Vinay Kumar Jha*

Central Department of Chemistry, Tribhuvan University, Kathmandu, Nepal

How to cite this paper: Miya, K.S. and Jha, Abstract

V.K. (2020) Determination of Fluoride in
Various Samples Using a Fluoride Selective
Electrode. Journal of Analytical Sciences, Me-
thods and Instrumentation, 10, 97-103.
https://doi.org/10.4236/jasmi.2020.104007
Received: October 15, 2020
Accepted: December 20, 2020
Published: December 23, 2020
Copyright © 2020 by author(s) and
Scientific Research Publishing Inc.
This work is licensed under the Creative
Commons Attribution International
License (CC BY 4.0).
http://creativecommons.org/licenses/by/4.0/
Open Access
Fluoride is widespread in the environment, water, air, vegetation and Earth’s
crust which can entre ground and surface water by natural process. Fluoride
in minute quantities is essential component for human health and help in nor-
mal mineralization of bone and formation of dental enamel. The determina-
tion of fluoride in some species was performed by using fluoride ion-selective
electrode by direct measurement and standard addition method. The concen-
tration of fluoride ion was determined in drinking water (from different place
at Kathmandu), toothpaste, various brand of tea and coffees. The range of
fluoride concentration in water sample was 0.16 to 0.39 mg/l, tea and coffee
samples were 0.011 to 0.084 mg/l and its value of toothpaste was 0.026 to 0.75
mg/l. The concentration of fluoride ion obtain from different sample was
compared with the legitimate value given by the world health organization.
Keywords
Fluoride, TISAB, Water, Tea, Coffee, Toothpaste, Fluoride Ion Selective
Electrode, Dental Carries

1. Introduction
Fluoride ion is the ionic form of fluorine which is mostly found in various sam-
ple and play Vitol role for human health and environment, but consumption or
presence of large amount of fluoride harmful for health and environment [1].
The higher concentration of fluoride is toxic. The optimal range of fluoride is
0.05 - 0.07 mg per kg body weight has been considered. Fluoride ion is mostly
formed as the by-product in certain process and entre in the human body by
means of food chain (water, juices, tea, and coffee), toothpaste and pollution
(air, water). The main source of fluoride in toothpaste, water is sodium fluoride,

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K. S. Miya, V. K. Jha

stannous fluoride and sodium monofluorophosphate [2]. It has indispensable

role in prevention of dental caries [3]. However, the beneficial effect of reduced
dental caries is balanced by an increased prevalence of dental fluorosis [4]. Flu-
orosis is defined as an abnormal condition caused by excessive intake of fluoride
as from fluoridated drinking water, characterized chiefly by mottling of the teeth.
Fluorosis appears as marking of the enamel surface of the teeth (enamel de-
fects). Mostly fluorosis appears barely visible white flecks on the tooth surface;
with the more sever cosmetically unacceptable form being rather uncommon.
Dental fluorosis occurs during tooth development, especially between the ages of
6 month to 5 years. The British Fluoridation Society considers fluorosis as a cos-
metic rather than a health problem [5].
Several determination technique of fluoride in various sample such as direct
measurement, standard addition, titration method and anion-chromatography,
Ion-Selective electrode etc. are use in this present work. Ion-Selective method is
selected for the determination of Fluoride ion in various samples.
Health Hazards of fluoride
Fluoride is an important element for all tissues in the body. Appropriate fluo-
ride consumption is beneficial to bone and tooth integrating and it has impor-
tant positive impact on oral health and overall health. However, high level of fluo-
ride has been associate with various adverse effects in living being. The permiss-
ible does to human being, according to WHO, is 1.5 mgL−1 as a safe limit of fluo-
ride in drinking water.
High levels of fluoride in childhood were associated with a reduction in IQ.
The author noted that this research is not applicable to the safety of artificial
water fluoridation because the adverse effect on IQ were found with fluoride lev-
el that were much higher than typically found in artificially fluoridated water.
Consumption of fluoride at level beyond those used in fluoridated water for a
long period of time causes skeletal fluorosis. In some areas, particularly the
Asian subcontinent especially India, Pakistan and Bangladesh skeletal fluorosis
is endemic. It is known to cause irritable bowel symptoms and joint pain. Early
stages are not clinically obvious and may be misdiagnosed as rheumatoid arthri-
tis or anklosingspondylitis [6].
Fluoride causes nephrotoxicity in kidney due to toxic level of serum fluoride,
commonly due to release of fluoride from fluoride containing drugs, such as me-
thoxyflurane. Fluoride induced nephrotoxicity is dependent on the serum fluo-
ride level, typically serum fluoride level exceeding 50 micromoles per liter (about
1 ppm) to cause clinically significant renal dysfunction [7] [8]. The only gener-
ally accepted adverse effect of fluoride at level used for water fluoridation is
dental fluorosis, which can alter the appearance of children’s teeth during tooth
development; this is mostly mild and usually only on aesthetic concern. As a
Compared to unfluoridated water, fluoridation to 1 mg/L is estimated to cause
fluorosis in one of every 6 people (range 4 - 21), and to cause fluorosis of aes-
thetic concern in every 22 people [9].

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 K. S. Miya, V. K. Jha

2. Experimental
2.1. Determination of Fluoride in Drinking Water and Bottled
Water Sample
A combination fluoride electrode was used to determine the fluoride content in
drinking water and bottled water. The solution which contained 25 ml of the sam-
ple and 25 ml of TISAB solution were mixed with a magnetic stirrer for 3 minute.
The electrode potential of the solution is measured by using fluoride selective
electrode. The potential of the sample solution were directly compared with those
of fluoride standard solution.
Then 1 mL of the 0.1 M fluoride standard solution was added in to the text
solution and placed in magnetic stirrer. Then new electrode potential was meas-
ured. Similarly this process was carried out up to 5 mL. The mean concentration
of fluoride was determined.

2.2. Determination of Fluoride Content in Toothpaste

For the determination of fluoride in toothpaste, 1 g of the sample was weighted
in to the 100 mL beaker. After 25 mL of TISAB solution was added to the sam-
ple, the mixture was boiled thoroughly for 2 min. The suspension was completed
to 50 mL with distilled water and placed in magnetic stirrer.
The electrode potential of the solution is measured by using fluoride selective
electrode. The potential of the sample solution were directly compared with those
of fluoride standard solution.
1 mL of the 0.1 M fluoride standard solution was added in to the text solution
and placed in magnetic stirrer. Then new electrode potential was measured. Si-
milarly this process was carried out up to 5 mL. The mean concentration of fluo-
ride was determined.

2.3. Determination of Fluoride in Tea and Coffee Sample

1 gm of dried tea sample was placed in to a beaker. Then 100 mL of boiling de-ioni-
zed water was poured in to the beaker and 25 mL of the tea liquor was taken after the
5 minute. Then 25 ml of TISAB solution was added and placed in magnetic stirrer.
The electrode potential of the solution is measured by using fluoride selective
electrode. The potential of the sample solution were directly compared with those
of fluoride standard solution.
1 mL of the 0.1 M fluoride standard solution was added in to the text solution
and placed in magnetic stirrer. Then new electrode potential was measured. Si-
milarly this process was carried out up to 5 mL. The mean concentration of fluo-
ride was determined.

3. Results and Discussion

3.1. Results of Fluoride Analysis
3.1.1. Fluoride Concentration of Water and Bottled Water at Kathmandu
The fluoride level was determined in drinking water samples collected from cite

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K. S. Miya, V. K. Jha

at Kathmandu by direct measurement and standard addition method. A total of

4 different water samples are collected. In the drinking water from all the sample
location, the fluoride content was less than 0.40 mg/L. As can be seen from table,
the highest fluoride level was observed in tap water about 0.399 mg/L. The natu-
ral concentration of fluoride in ground water depend on such factor as the geo-
logical, chemical and physical characteristic of the water supplying area, the
consistency of soil, porosity of rocks, the pH and temperature. The complexing
action of other element and depth of wells. The result obtain indicate that the
fluoride level of the drinking water and bottled water are generally low regarding
drinking water standards. This lack of fluoride content in the drinking water
which are one of the main source of fluoride nutrition for human, may causes
health problem for human health especially teeth and bone structure.
Fluoride concentration of water and bottled water at Kathmandu Valley as
shown in Table 1.

3.1.2. Fluoride Concentration in Toothpaste

The fluoride content of 7 different brands of toothpaste was analyzed by direct
measurement and standard addition method. Toothpaste is an ideal form of ad-
ministration of F as it is routinely used by a very large part of the world’s popu-
lation. For better comparison of divergent formulation as well as for sound in-
terpretation and comparison of data from different laboratories, a potentiome-
tric method for F determination in toothpaste is required.
The total fluoride determination was made on sample by fluoride selective
electrode. Analysis shows that all fluoride in toothpaste were in the form of NaF,
SnF2, Na2PO3F. Seven brand of toothpaste were analyzed for their fluoride con-
tent by this method.
This toothpaste can be classified in to 4 group’s non-fluoridated, fluoridated,
sodium fluoride, sodium monoflorophosphate and fluoridated with stannous flu-
oride but there is no independent indication of their quantitative composition.
One of these samples was non-fluoridated. In all probability, concentration is
naturally occurring fluoride impurity level in the component of the toothpaste.
Out of these other toothpaste were identified on their packaging as containing
fluoride added as sodium fluoride and sodium monoflorophosphate. All this group
had a fluoride concentration between 0.026 to 0.75 mg/g.
Fluoride concentration in toothpaste as shown in Table 2.

3.1.3. Fluoride Concentration in Tea and Coffee

The concentration of fluoride ion in 5 different sample of tea and 2 sample of
coffee were analyzed. All samples of tea and coffee were purchased from local
market at Kathmandu. The analyzed tea and coffee are commonly used by local
people. Tea and coffee infusion were prepared on a customary way of tea and
coffee preparation. Fluoride levels were determined in liquors taken at 5 min of
infusion. Table 3 shows the release of fluoride in tea and coffee were 0.0110 to
0.07792 mg/g and 0.083 to 0.084 mg/g respectively.

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 K. S. Miya, V. K. Jha

Table 1. Fluoride concentration of water and bottled water at Kathmandu.

Sample Concentration of Fluoride(mg/L) Concentration of Fluoride (mg/L)

(Water) by direct Measurement by standard addition method

W1 0.39 0.37

W2 0.28 0.26

W3 0.18 0.17

W4 0.16 0.14

Table 2. Fluoride concentration in toothpaste.

Sample Concentration of Fluoride (mg/L) Concentration of Fluoride (mg/L)

(Toothpaste) by direct Measurement by standard addition method

T1 0.75 0.73

T2 0.65 0.64

T3 0.35 0.32

T4 0.16 0.15

T5 0.14 0.13

T6 0.05 0.05

T7 0.02 0.03

Table 3. Fluoride concentration in tea and coffee sample.

Sample Concentration of Fluoride (mg/L) Concentration of Fluoride (mg/L)

(Coffee & Tea) by direct Measurement by standard addition method

C1 0.084 0.083

C2 0.083 0.083

TE1 0.077 0.076

TE2 0.074 0.072

TE3 0.024 0.025

TE4 0.016 0.015

TE5 0.011 0.010

Fluoride concentration in tea and coffee sample as shown in Table 3.

4. Conclusions
Measuring performed potentiometrically using a fluoride selective electrode is
simple and inexpensive. The fluoride selective electrode has gained prominence
over the traditional chemical and colorimetric method due to its sensitivity, spe-
cificity, speed of use and ability to response to a wide range of concentration. A

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K. S. Miya, V. K. Jha

possible matrix effect can be easily eliminated by the addition of TISAB. Traces
of fluoride can be determined directly in the liquid media studied (no laborious
and time consuming operation of sample preparation such as analytic enrichment
are required).
According to WHO, the optimum fluoride intake for human ranges from 2 to
4 mg per days. The total daily intake of fluoride that may causes fluorosis in
adults in over 13.0 to 14.5 mg per days. We can see from the results, if daily tea
consumption is too high and intake of fluoride from another source is excluded,
tooth fluorosis due to the uptake excessive of fluoride may result.

Acknowledgements
The authors are thankful to the Central Department of Chemistry, Tribhuvan
University, for providing laboratory facilities.

Conflicts of Interest
The authors declare no conflicts of interest regarding the publication of this pa-
per.

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https://doi.org/10.1016/S0003-2670(02)01481-2
[2] Konieczka, P., Zygmunt, B. and Namiesnik, J. (2000) Effect of Fluoride Content in
Drinking Water in Tricity on Its Concentration in Urine of Pre-School Children.
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https://doi.org/10.1080/02772240009358874
[3] Fung, K.F., Zhang, Z.Q., Wong, J.W.C. and Wong, M.H. (1999) Fluoride Contents
in Tea and Soil from Tea Plantations and the Release of Fluoride into Tea Liquor
during Infusion. Environmental Pollution, 104, 197-205.
https://doi.org/10.1016/S0269-7491(98)00187-0
[4] Tokaliogly, S., Kartal, S. and Shain, U. (2004) Determination of Fluoride in Various
Samples and Some Infusions Using a Fluoride Selective Electrode. Turkish Journal
of Chemistry, 28, 203.
[5] Borremans, M., Van Loco, J., Meerssche, P.V.D., Meurier, J., Vrindts, E. and Goeyens,
L. (2007) Analysis of Fluoride in Toothpastes on the Belgian Market. International
Journal of Cosmetic Science, 30, 145.
https://doi.org/10.1111/j.1468-2494.2008.00425.x
[6] Gupta, R., Kumar, A.N., Bandhu, S., Gupta, S. and Scand, J. (2007) Skeletal Fluoro-
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154-155. https://doi.org/10.1080/03009740600759845
[7] Cousins, M.J., Skowronski, G. and Plummer, J.L. (1983) Anaesthesia and the Kid-
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https://doi.org/10.1177/0310057X8301100402
[8] Cousins, M.J., Greenstein, L.R., Hitt, B.A. and Mazze, R.I. (1976) Metabolism and
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sis, 21, 384-389. https://doi.org/10.1016/j.jfda.2013.08.006

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124

Volume 46, Number 3, September 2013

Research Report

Determination of fluoride content in toothpaste using

spectrophotometry

Susanti Pudji Hastuti, Devinta Lestari and Yohanes Martono

Department of Chemistry
Faculty of Science and Mathematics Satya Wacana Christian University
Salatiga - Indonesia

abstract
Background: Intake excessive fluoride in children’s teeth are generally marked with white and brown patches. Excessive fluoride
of more than 4.0 mg/L can cause a person suffering from poisoning, fragility of the bones (osteoporosis), liver and kidney damage.
Knowledge about the spectrophotometry for determination method of fluoride content in commercially available toothpaste is very
few. Purpose: The purposes of study were to examine the suitable method for fluoride extraction and to determine out the accuracy,
precision, linearity, and stability of the measurement method of fluoride content in toothpaste. Methods: The suitable F extraction
method was determined by the comparison among 3 methods of extraction; e.g. the dried samples were immersed in (1) distilled water,
(2) 96% HCl, and (3) 96% HNO3; and the validation methods of measurement were the maximum wavelength, standart curve, accuracy
test, precision test, and stability test. Results: Result showed that the fluoride extraction by using the concentrated HNO3 was found to
have the highest levels of fluoride, followed by hydrochloric acid dissolution (HCl) and distilled water, while the method of validation
showed that SPADNS revealed the acceptable accuracy. Precision has the RSD ≤ 2.00%. Furthermore the stability test result showed
that the measurement of fluoride less than 2 hours was still reliable. Conclusion: The study suggested that the best result of fluoride
extraction from toothpaste could be gained by using concentrate HNO3, and the spectrophotometer (UV-Vis Mini Shimadzu U-1240)
and SPADNS have the acceptable accuracy.

Key words: Spectrophotometry, fluoride content, toothpaste

abstrak
Latar Belakang: Pemasukan fluoride yang berlebihan pada gigi anak ditandai dengan bercak putih dan coklat. Fluoride lebih
dari 4.0 mg / L dapat menyebabkan seseorang menderita keracunan , kerapuhan tulang (osteoporosis), kerusakan hati dan ginjal.
Pengetahuan tentang spektrofotometri untuk metode penentuan kadar fluoride dalam pasta gigi yang tersedia secara komersial sangat
sedikit . Tujuan: Penelitian ini bertujuan meneliti metode yang tepat untuk mengektrak kandungan fluoride dan mengukur akurasi,
presisi, linearitas dan stabilitas pengukuran kandungan fluoride pada pasta gigi. Metode: Metode ekstrak yang tepat ditentukan
dengan membandingkan 3 metode, yaitu dengan perendamam sampel kering dalam (1) air destilasi, (2) HCl 96%, dan (3) HNO3
96%; dan validasi metode yang memperhitungkan panjang gelombang, kurva standar, tes akurasi, presisi, dan stabilitas. Hasil:
Hasil menunjukkan bahwa metode ekstrasi fluoride pada pasta gigi dengan menggunakan metode HNO3 didapatkan level fluoride
tertinggi, diikuti dengan metode HCl dan air destilasi. Hasil validasi metoda menunjukkan bahwa penggunaan SPADNS akurasinya
dapat diterima. Presisi mempunyai RSD ≤2,00%. Pada tes stabilitas didapatkan hasil bahwa pengukuran kadar fluorida dalam waktu
Hastuti, et al.,: Determination of fluoride content in toothpaste using spectrophotometry 125

tidak lebih dari 2 jam masih dapat dilakukan. Simpulan: Penelitian ini menunjukkan bahwa hasil terbaik ekstraksi fluoride dari pasta
gigi dapat diperoleh dengan menggunakan HNO3, dan spectrophotometer (UV-Vis Mini Shimadzu U-1240) dan SPADNS memiliki
pengukuran yang akurat.

Kata kunci: Metode spektrofotometrik, kandungan fluorida, pasta gigi

Correspondence: Susanti Pudji Hastuti, c/o: Departemen Kimia, Fakultas Matematika dan Ilmu Pengetahuan Alam, Universitas Kristen
Satya Wacana. Jl. Diponegoro 52-60 Salatiga 50711, Indonesia. E-mail: susanti012@yahoo.com

introduction three levels of precision, i.e. repeatability, between the

The use of toothpaste is a part of tooth brushing which is
needed for healthy teeth. Toothpaste makes the teeth cleaner
and reduce oral microorganism.1 Fluoride in toothpaste is
one of the substances that needed for healthy teeth. The
mechanisms of fluoride in dental caries prevention are;
reducing the enamel solubility caused by acid, lowering the
enamel surface permeability and inhibiting the fermentation
of carbohydrates by microorganisms of the oral cavity.2
The needs of fluoride is between 0.7 to 0.9 mg/L (parts
per million).3 Therefore, despite the growing controversy,
the provision of fluoride in toothpaste should not be
exaggerated. This is due to the excess fluoride (fluorosis)
can cause cells die and the teeth become brittle.
The degree of dental fluorosis depends on the amount
of fluoride exposure up to age of 8 to10 years old.
The fact that an adult shows no signs of dental
fluorosis does not mean that his or her fluoride
intake is within the safety limit. 4 Excessive fluoride
in children’s teeth are generally marked with white and
brown patches. Excessive fluoride of more than 4.0 mg/L
can cause a person suffering from poisoning, the fragility
of the bones (osteoporosis), liver and kidney damage.3-7
To ensure accuracy of fluoride content measurement
in toothpaste, the validation of method need to be done.
Validation of the method according to United States
Pharmacopeia (USP) in Martono8 is aimed to determine
that the analysis method is accurate, specific, reproducible,
and hold in the range of analytes to be analyzed. Some
parameters according to the USP are accuracy, precision,
linearity, and stability.
Accuracy is the closeness between the measured values,
which acceptable to the convention, the true value, or
value of referrals. Accuracy is measured as the amount of
analyte recovered in a measurement by performing spiking
on a sample. Accuracy can be obtained by comparing the
results of measurements with standard reference materials.
International Conference on Harmonisation (ICH)
recommends the collection of data from nine times the assay
with 3 different concentrations (e.g. 3 concentrations with
3 times replication). Data are reported as percent recovery
(% recovery).
Precision is a measurement of repeatability analysis
method, and is usually expressed as relative standard
deviation of statistically different samples. There are
precision (intermediate precision), and reproducibility.
The precision are include: Standard Deviation, Relative
Standard Deviation (RSD) or Coefficient of Variation
(CV), and the range of beliefs. Data for precision test is
often collected as part of other studies related to precision,
linearity or accuracy. Usually 6 to 15 replications are done
for a single sample of each concentration. In testing, the
value of RSD is 1-2% for the active compounds in large
quantities, while for compounds with a little amount, RSD
ranged between 1-5%.8-10
Linearity is the ability to obtain test result which is
proportional to the concentration of analyte in a given
range. Linearity is measurement of how well the calibration
curve method connects between the response (y) with
concentration (x). Linearity can be measured by performing
a single measurement at different concentrations. The data
obtained is processed by the method of least squares, and
then determined the value of the slope (slope), intercept,
and correlation coefficient (r).10
To obtain the reproducible and reliable test results, the
sample, reagents and raw materials used should be stable at
a certain time. The stability of all solutions and reagents is
very important, either in relation to temperature or in respect
of time. If the solution is not stable at room temperature,
the temperature should be decreased 2-8°C to increase the
stability of samples and standards.
The purposes of study were to examine the suitable
method for the fluoride extraction and to determine the
accuracy, precision, linierity, and stability of the method
concerning to the measurement of fluoride content in
toothpaste.
materials and methods
Determination of maximum wavelength was done by
mixing 5 mL of distilled water with 1 mL of SPADNS
reagent, then performed using a scanning spectrophotometer
(UV-VIS Mini Shimadzu U-1240). Measurements were
taken at region of 350-700 nm wavelength. Ten series
of fluoride standard solutions levels are: 0.2 mg/L; 0.4
mg/L; 0.6 mg/L; 0.8 mg/L; 1 mg/L; 1.2 mg/L; 1.4 mg/L;
1.6 mg/L; 1.8 mg/L and 2 mg/L respectively (each made​​
in a volume of 10 ml) was prepared for configuration of
standard curve. From each level taken 5 mL of solution
126 Dent. J. (Maj. Ked. Gigi), Volume 46, Number 3, September 2013: 124–129

was then added 1mL of reagent SPADNS into each test
tube, stirred until homogeneous and then incubated for 5
min at room temperature. The absorbance of each solution
was measured with a spectrophotometer (UV-VIS Mini
Shimadzu U-1240) at a wavelength of 550 nm (maximum
wavelength after scanning).8,10
Accuracy and precision was obtained with standard
solutions of fluoride levels of 0.4 mg/L, 1 mg/L and 1.8 mg/
L respectively which is made from a standard solution of
fluoride of 2 mg/L. From each level taken 5 mL of solution
was then added 1 mL of reagent SPADNS into each test
tube, stirred until homogeneous and then incubated for 5
min at room temperature. The absorbance of each solution
was measured with a spectrophotometer (Shimadzu UV-
VIS Mini U-1240) at a wavelength of 550 nm (maximum
wavelength after scanning). Assay performed nine times,
including three kinds of levels, each of 3 replications.8,10
Stability of reagent SPADNS was done by comparing
volume of reagent at 0.5 mL and 1 mL within 5 mL of
standard fluoride solution in three different levels of
0.4 mg/L, 1 mg/L, and 1.8 mg/L respectively and then
measured with a spectrophotometer (UV-VIS Mini
Shimadzu U-1240) at a wavelength of 550 nm. SPADNS
reagent stability is determined by mixing 5 ml of distilled
water with 1 mL of reagent SPADNS. Determination
of wavelength and absorbance of the mixture was done
by using a spectrophotometer (UV-VIS Mini Shimadzu
U-1240). Measurements were made every 5 minutes in
a span of 120 minutes and on the wavelength region of
350-700 nm.11
Six adults toothpastes and 3 children toothpastes which
commercially available, were dried in order to make
comparison between the method used in the comparison
of Fluoride extraction by putting the samples in an oven
at ±105o C temperature until constant mass was obtained
while cooling in the desicator. Furthermore as a first step,
the optimization method performed by a comparison of
three methods of sample dissolution.12
There were three methods used, in method 1: the dried
samples (1 g) was immersed in 50 mL of distilled water
for 24 hours in a porcelain dish. The mixture was filtered
and put in a 100 mL volumetric flask, then add distilled
water until the calibration line (tera-line fulfillment to be
done by washing the residue). Prior to the measurement of
fluoride levels, first centrifuge solution at a speed of 3000
rpm for 10 minutes.
Method 2: the dried samples (1 g) was included in a
porcelain dish and immersed in 5 mL of concentrated HCl
(96%) for 24 hours in the fumehood. After that, heated ±
2 hours at a temperature of 50ºC using a hot plate in the
fumehood. Once heated, add another 5 mL of concentrated
HCl and heating was continued until no white gas formed.
The solution was then cooled, then filtered and put in a
100 mL volumetric flask, then add distilled water until the
calibration line.
Method 3: the dried samples (1 g) was included in a
porcelain dish and immersed in 5 mL of concentrated HNO3
(96%) for 24 hours in the fumehood. After that, heated ±
2 hours at a temperature of 50ºC using a hot plate in the
fumehood. Once heated, add another 5 mL of concentrated
HNO3 and a few drops of H2O2. Heating is continued until
no more gas to form nitrogen oxides and the resulting brown
solution nodes. The solution was cooled, then filtered and
the filtrate was added in 100 ml flask, then add distilled
water until the calibration line.

Table 1. The comparative analysis of fluoride method

Fluoride level (mg/L)

Method 1 Method 2 Method 3
Sample code
1 2 3 1 2 3 1 2 3
X 0.85 0.853 0.85 0.803 0.80 0.80 0.91 0.913 0.91
Y 0.713 0.71 0.716 0.807 0.807 0.81 0.857 0.85 0.85
Z 0.81 0.81 0.813 0.87 0.87 0.87 0.907 0.903 0.893

Table 2. The accuracy of fluoride standard solution based on the measurement of absorbance at λ 550 nm

Concentration of fluoride A550 (x 100) Average A550 Measurable levels Average of

Recovery (%)
standard solution (mg/L) I II III of fluoride (mg/L) recovery (%)
0.4 181.9 181.9 181.9 181.9 0.4286 107.15 99.84
1.0 181.2 181.2 181.2 181.2 0.8286 82.86
1.8 179.2 179.2 179.2 179.2 1.9714 109.52
Hastuti, et al.,: Determination of fluoride content in toothpaste using spectrophotometry 127

Table 3. Repeatability of fluoride standard solution based on the measurement of absorbance at λ 550 nm

standard levels of fluoride (mg/L) repeatation A550 (x 100) measurable levels of fluoride (mg/L)
1 181.9 0.4286
0.4 2 181.9 0.4286
3 181.9 0.4286
average 181.9 0.4286
SD 0 0
RSD (%) 0 0
1 181.2 0.8286
1 2 181.2 0.8286
3 181.2 0.8286
average 181.2 0.8286
SD 0 0
RSD (%) 0 0
1 179.2 1.9714
1.8 2 179.2 1.9714
3 179.2 1.9714
average 179.2 1.9714
SD 0 0
RSD (%) 0 0

Table 4. Stability of SPADNS reagent

t (minutes) λ (nm) absorbance t (minutes) λ (nm) absorbance

0 549 1.843 65 548 1.830
5 549 1.834 70 549 1.827
10 547 1.837 75 549 1.827
15 548 1.840 80 548 1.836
20 551 1.839 85 550 1.832
25 549 1.842 90 550 1.839
30 548 1.832 95 548 1.828
35 548 1.831 100 550 1.830
40 550 1.836 105 548 1.836
45 549 1.832 110 549 1.833
50 550 1.836 115 548 1.834
55 547 1.825 120 550 1.837
60 548 1.838

results disccusion

The comparison of three extraction methods of samples
could be seen in Table 1. Accuracy was expressed as percent
recovery of analyte added.13 (Table 2). Precision was
determined by measuring the spread of individual results
from the average, if the procedure was applied repeatedly in
samples which were taken from a homogeneous mixture.13
(Table 3). The stability of the volume of reagents was very
important thing (Table 4).
All three methods of sample extraction were compared,
and the result showed extraction by using concentrated
HNO3 was found to have the highest levels of fluoride,
followed by hydrochloric acid dissolution (HCl) and
distilled water. This result is supported by Oyewale12 which
states that the use of HNO3 extraction gave the optimum
extraction for all inorganic parameters or components of
all different toothpastes.
DISCCUSION
All three methods of sample extraction were compared,
128 and J.
Dent. the(Maj.
result Ked.
showed extraction
Gigi), Volume 46, Number 3, September 2013: 124–129
by using concentrated HNO3 was found to have the highest levels of fluoride, followed by
12
hydrochloric The component
acid dissolution of toothpastes
(HCl) arewater.
and distilled combined of calcium
This result To examine
is supported by Oyewale the accuracy of the developed methods
carbonate and phosphates, which have low solubility in from the experiments, standard addition method was
which states that the use of HNO3 extraction gave the optimum extraction for all inorganic
water. Acidic condition is often required to release some carried out, then the percentage recovery was calcutated.16
parameters or componentsinto
of components of allwater
different toothpastes.
soluble form. This may partly Accuracy can be determined by the assay minimum of
account for the acidic nature of some of the toothpaste
The component of toothpastes are combined of calcium carbonate and phosphates, 9 times,which covering a certain range e.g. 3 different levels,
samples. Furthermore Oyewale12 stated that the fluoride each of 3 replications. The average percent recovery were
have low solubility in water. Acidic condition is often required to release some of components
content is all essentially available even in aqueous medium in the range of 98-102% 10 as seen in Table 2. The study
into water
since soluble
it isform.
oftenThisincorporated
may partly account for the acidicas
in toothpastes nature of some ofshowed
sodium the toothpaste
that the spectrophotometer instrument (UV-VIS
salts, which are generally
12 soluble in water. Based on
samples. Furthermore Oyewale stated that the fluoride content is all essentially available even Mini Shimadzu U-1240) and methods developed SPADNS
this experiment, the F extraction from toothpaste can be have acceptable accuracy.8,14
in aqueous medium using
determined since itconcentrated
is often incorporated
HNO3. in toothpastes as sodium salts, The whichtest are precision was conducted on three kinds
generally soluble in water. Based on this experiment, the F extraction from toothpaste can be levels with 3 repetitions for each target
An important point related to validation method is of different
selection of the maximum wavelength which in turn will compound. The low Relative Standard Deviation (RSD)
determined using concentrated HNO3.
be used for the manufacture of standard curves. The results values indicates precision of the method. In majority, the
An important
showed thatpoint
therelated to validation
wavelength of method
maximum is selection of the maximum
absorption wavelength were below 2%, indicating high degree of
determinations
17
which in turn will be used for the manufacture of standard curves. The results showed that the(repeatability) between experimental values.
was at a wavelength of 550 nm. Validation method was agreement
done using reagents SPADNS and an instrument of Determination of repeatability can be done with a minimum
wavelength of maximum absorption
spectrophotometer (UV-VIS was atMini
a wavelength
Shimadzu of 550 nm. Validationofmethod
U-1240). 6 times wasdetermination levels of 100%, or 9 times in
done using
SPADNS reagents reagent
SPADNS and is aanmixture
instrumentof of spectrophotometer
solution SPADNS (UV-VIS Mini Shimadzu
the range of levels with 3 different levels, each repeated
[Sodium 2 - (Para-sulfophenylazo) -1, 8-dihydroxy-3,
U-1240). SPADNS reagent is a mixture of solution SPADNS [Sodium 2 - (Para-sulfophenylazo) 6- a number of 3 times. According to Ermer and Miller 10
naphtalene disulfonate] with a solution of zirconyl chloride it may be accepted if the repeatability RSD ≤ 2.00% of
-1, 8-dihydroxy-3,
octahydrate, 6-naphtalene
ZrOCl2.8H disulfonate]
O, in with conditions.
acidic a solution of13,14
zirconyl chloridetheoctahydrate,
test. The repeatability of fluoride standard solution
2
Determination
ZrOCl2.8H2O, in acidic conditions. of fluoride
13,14 was done by using based on the measurement of absorbance at λ 550 nm, the
spectrophotometry method and it based on metal three standard levels of fluoride (mg/L) and measurable
Determination of fluoride was done by using spectrophotometry method and it based on
displacement from a colored complex or the formation levels of fluoride (mg/L) gave the RSD of 0%. This shows
metal displacement
of a mixed-ligandfrom a colored
complex,complex or the formation of a mixed-ligand
Zr(IV)-F-SPADNS. Fluoride complex,
that the Zr(IV)-
repeatability with RSD ≤ 2.00% of the test is
17
addition will bleach SPADNS-Zirconyl chloride
F-SPADNS. Fluoride addition will bleach SPADNS-Zirconyl chloride and degrade the red and acceptable.
degrade the red colored complex. The degree of bleaching The stability of all solutions and reagents is very
coloredwas
complex. The degreewith
determined of bleaching was determined with and
a spectrophotometer, a spectrophotometer,
the and the
important, whether in relation to temperature or in respect of
8
concentration of fluoride ions was assessed by comparison
concentration of fluoride ions was assessed by comparison with standard solutions. The color time. Comparison the stability of SPADNS reagent volume
with standard solutions. The color loss was measured based on absorbance at λ 550 nm showed that the absorbance
loss was measured at wavelength on maximum absorbtion of mixed-ligand complex.14 The
at wavelength on maximum absorbtion of mixed-ligand was stable, when the volume reached SPADNS reagent was
reaction is as follows
complex. 14 :
The reaction is as follows : added to the standard solution of 1 mL. In contrast the use of
0.5 mL of reagent gave absorbance measurement results of
H+ an unstable (fluctuating). The possibility of this result was
Zr-SPADNS + 6F SPADNS + ZrF 6 + nH2O
- 2-
because the amount of SPADNS reagent still not enough
(red) (colorless)
to indicate the amount of fluoride (levels) contained in the
6
standard solution. Therefore, the determination of fluoride
This is consistent with the theory SPADNS method that
the use of wavelength will be in the region of 550-580 nm levels in this study was carried out by applying the ratio of
wavelength. In addition, the use of 550 nm wavelength on a the volume of the sample with a SPADNS reagent by 5:1 (v:
spectrophotometer supported by theory which stated that the v). The results showed that up to 120 minutes, a mixture of
red light located on the complementary wavelength region sample and SPADNS reagent continued to show stable and
14
of 490-560 nm. The red color observed (as seen by the unaffected by environmental factors, especially from the air.
eye) is the color of the reagent SPADNS. As an indication This is according to US Environmental Protection Agency
19
of the content of fluoride, the red color of the reagent (USEPA) which also states that during 2 hours of color
SPADNS will be degraded, and if the higher fluoride formed from the sample and SPADNS reagent will remain
content, the red color will fade (degradation increases) so stable. This means that measuring the levels of fluoride in
15
that the smaller absorbance. The results of absorbance the range of no more than 2 hours is still reliable.
measurements of fluoride standard solution at various levels The study suggested that the best result of fluoride
in the manufacturing of standard curves. The results of the extraction from toothpaste could be gained by using
linear regression relationship is created from “y = bx + a”, concentrate HNO3, and the validation test results showed
where “y” is the response (absorbance), “b” is the slope and that the spectrophotometer (UV-Vis Mini Shimadzu
“a” is the intercept. Equation of the regression line (content U-1240) and SPADNS have the acceptable accuracy.
vs absorbance) and then “y = - 1.75 x + 182.6” with r = Precision has RSD ≤ 2.00%. The stability test results
1. Standard curve was made to give a perfect correlation revealed that the measurement of fluoride in the range of
coefficient (r = 1). less than 2 hours is still reliable.
Hastuti, et al.,: Determination of fluoride content in toothpaste using spectrophotometry
references
1. Andriewongso. Pasta gigi. (on line) http://www.andriewongso.
com/awartikel-1984-Tahukah_Anda-Pasta_Gigi. 2008. Accessed
March 20, 2009.
2. Arnold W, Dorow A, Langenhorst S, Gintner Z, Bánóczy J, Gaengler
P. Effect of fluoride toothpastes on enamel demineralization. BMC
Oral Health 2006; 6: 8.
3. Meenakshi, Maheshwari RC. Fluoride in drinking water and its
removal. J Hazard Mater 2006; 137(1): 456-63.
4. Oxford Instruments Molecular Biotools Limited. Determination of
fluoride content in toothpaste. USA: http://www.oxford-instruments.
com/OxfordInstruments/media/industrial-analysis/magnetic-
resonance-pdfs/Determination-of-Fluoride-Content-in-Toothpaste.
pdf 2008. p. 1-2.
5. Darmawan L. Cara cepat membuat gigi sehat dan cantik dengan
dental cosmetics. Jakarta: Gramedia Pustaka Utama; 2007. p.144.
6. Moghaddam AA, Fijani E. Distribution of fluoride in groundwater
of Maku area, northwest of Iran. Environmental Geology 2008;
56(2): 281-7.
7. Msonda KWM, Masamba WRL, Fabiano E. A study of fluoride
groundwater occurrence in Nathenje, Lilongwe, Malawi. Physics
and Chemistry of the Earth 2007; 32: 1178-84.
8. Martono Y. Validasi metoda kromatografi cair kinerja tinggi isokratik
untuk penetapan kadar asam galat, kafein dan epigalokatekin galat
pada berbagai produk teh celup. Thesis. Yogyakarta: Program Studi
Ilmu Farmasi, Fakultas Farmasi Universitas Gadjah Mada; 2009.
9. Gujarathi SC, Shah AR, Jagdale SC, Datar PA, Choudari VP,
Bhanudas SK. Spectrophotometric simultaneous determination
of Aspirin and Ticlopidine in combined tablet dosage form by
first order derivative spectroscopy, AUC and ratio derivative
spectrophotometric methods. Int J Pharm Sci Review and Research
2010; 3(1): 115-9.
129
10. Ermer J, Miller JH. Method validation in pharmaceutical analysis.
A guide to best practice. Weinheim: WILEY-VCH Verlag GmBH
& Co.KgaA; 2005. p. 4-22.
11. Gandjar IG, Rohman A. Kimia farmasi analisis. Yogyakarta: Pustaka
Pelajar; 2007.
12. Oyewale AO. Estimation of the essential inorganic consituents of
commercial toothpaste. Scientific & Industrial Research 2005; 64:
101-7.
13. Harmita. Petunjuk pelaksanaan validasi metoda dan cara
perhitungannya. Majalah Ilmu Kefarmasian 2004; 1(3): 117-35.
14. Battaleb-Looie S, Moore F. A study of fluoride groundwater
occurrence in Posht-e-Kooh-e-Dashtestan, South of Iran. World
Applied Sci J 2010; 8(11): 1317-21.
15. HACH Company. 2006. Fluoride for water and seawater SPADNS,
SPADNS 2 and ion-selective electrode methods. (on line) http://www.
hach.com/fmmimghach?/CODE%3AEX_FLUORIDE15801/1.
Accessed September 15, 2013.
16. Sharma MC, Sharma S. Validated simultaneous spectrophotometric
estimation of Paroxetine HCl bulk and tablet dosage form using ferric
chloride. J Opteoelectronics and Biomedical Materials 2010; 2(4):
185-9.
17. Garcia PL, Santoro MIRM, Singh AK, Kedor-Hackmann ERM.
Determination of optimum wavelength and derivative order in
spectrophotometry for quantitation of Hydroquinone in creams.
Brazilian J Pharm Sci 2007; 43: 397- 404.
18. Sharma R, Pervez S. Study of dental fluorosis in subjects related
to a phosphatic fertlizer plant environment in Chhattisgarh State.
Scientific & Industrial Research 2004; 63: 985-88.
19. US Environmental Protection Agency. Method 13A - Determination
of total fluoride emissions from stationary sources. SPADNS
ZIRCONIUM LAKE METHOD. (on line) http://www.epa.gov/ttn/
emc/promgate/m-13a. Accessed September 16,2013.
 View Article Online / Journal Homepage / Table of Contents for this issue

404 SHORT PAPERS [Artalyst, Vol. 88

SHORT PAPERS
Determination of Fluoride by Complexometric Titration
BY M. A. LEONARD
Published on 01 January 1963. Downloaded by Brown University on 26/09/2013 08:30:41.

(Boots Pure Drug Co. Ltd., Analytical Development Group, Standards Department, Station Street, Nottingham)

THEdirect titration of fluoride ions in aqueous solution with solutions of metal salts, such as thorium
nitrate, suffers from lack of stoicheiometry and from adsorption of the indicator on the gelatinous
precipitate. Precipitation of fluoride with excess of such reagents as calcium chloride or cerous
nitrate, with titration of the excess of metal ion in the filtrate, frequently gives rise to precipitates
of an intractable gelatinous nature or of dubious composition.
Lead chlorofluoride can, however, be precipitated quantitatively from a suitable solution in
a coarse crystalline form of definite composition over a wide range of conditions. Also, in con-
junction with this, lead ions are easily and accurately titrated with ethylenediaminetetra-acetic
acid (EDTA).
In the proposed method fluoride is precipitated, in the presence of chloride and ethanol, with
standard 0-05 M lead nitrate, a reagent now available in bulk in many routine laboratories.
Laszlovsky first introduced the general principle mentioned above, but titrated the lead
content of the precipitate. Titration of the excess of precipitant in the filtrate is usually a simpler
and more rapid procedure and only becomes impracticable when a great excess of precipitant
is needed.
VfeSkil and co-workers1 precipitated fluoride with 150-ml portions of a saturated solution of
lead chloride. This did not appear to be a particularly suitable standard reagent for routine
use. Their titration of lead in the filtrate with EDTA, with xylenol orange as indicator, is similar
to the proposed method.
Sakharova and Shishkina2precipitated lead chlorofluoride from dilute acetic acid with standard
lead acetate solution; I regard the presence of acetate ions as detrimental to such a precipitation
(see Table I). They continued by titrating lead ions in the filtrate with EDTA a t pH 10 t o 11
and used tartrate as secondary complexing agent and Solochrome black T as indicator.

METHOD
PROCEDURE-
Dissolve 5 to 45 mg of dry AnalaR or “Extra Pure” sodium fluoride in 20 ml of water, and
add 8.0 ml of 0.2 M sodium chloride and 13 ml of 95 per cent. ethanol. Heat almost to boiling,
and add from a burette 25.00 ml of standard 0-05 M lead nitrate, dropwise a t first, then more rapidly
as the precipitate becomes established. Swirl the solution constantly. Maintain the mixture
just a t the boiling-point for 1 minute to coagulate the precipitate, cool to room temperature,
filter, and wash the residue with four 15-ml portions of 20 per cent. v/v ethanol in aqueous 0-02M
sodium chloride. Titrate the filtrate and washings with standard 0 . 0 5 ~EDTA with xylenol
orange as indicator and solid hexamine t o bring the pH to approximately 6.
1 ml of 04X00 M lead nitrate = 2.10 mg of sodium fluoride.

RESULTS
AND DISCUSSION

Sixteen concurrent determinations carried out on 30- to 45-mg samples of pure sodium fluoride
gave a mean recovery of 100.0 per cent. with a standard deviation of 0.19 per cent.
In the absence of fluoride, lead chloride does not precipitate unless the alcohol content exceeds
43 per cent. v/v. This does not rule out possible co-precipitation, though the relation between
recovery and volume of solution a t the precipitation stage indicates that there is little cancelling
of errors due to co-precipitation and precipitate solubility. Some results showing the variation
in recovery of 42 mg of sodium fluoride with the volume at precipitation, the concentrations of
ethanol and sodium chloride being maintained a t the levels indicated under “Method,” were-
Total volume, ml .. .. 100 200 250
Recovery, yo .. .. .. 100.0 100.0 99.7
 May, 19633 SHORT PAPERS View Article Online
405
The choice of wash liquid is important as lead chlorofluoride is appreciably soluble in cold
water. A 20 per cent. v/v solution of ethanol was reasonably effective, but addition of sodium
chloride to 0.02 M introduced a common-ion effect that completely overcame this difficulty.
The concentration of ethanol present a t the precipitation stage is not critical, but for the best
results it should lie between 10 and 20 per cent., as indicated by the results shown below-
Concentration of ethanol, yo . . 0 10.0 14.3 18.6 28-6 51-5
Recovery, % . . .. .. 98.7 99.6 100.0 100.0 100.6 101.6
Published on 01 January 1963. Downloaded by Brown University on 26/09/2013 08:30:41.

The quality of the precipitate is inversely proportional to the concentration of ethanol. Ethanol
may be replaced by acetone or methanol.
The ratio of chloride t o fluoride (tested up to 4 to 1) is not critical once the 1 to 1 ratio has
been exceeded. In the absence of chloride, lead fluoride precipitates to give 87 per cent. recovery
based on lead fluoride. This recovery rises to 99.3 per cent. when the ratio of [Cl-) to [F-] reaches
1.1 to 1.
The excess of lead nitrate is not critical provided that the weight of chloride present is kept
constant. If 25 ml of 0.05 M lead nitrate are taken for a final volume of approximately 70 ml,
as in the method, then good recoveries can be obtained on sample weights of sodium fluoride
from 4 to 46 mg.
For a total volume a t precipitation of 7 0 ml, the temperature a t filtration is not critical and
may rise t o as high as 50" C with negligible loss in recovery. However, a t greater volumes this
influence becomes more important, and temperatures should not exceed 25" C.
The pH of the fluoride solution before precipitation may be from a t least 4.5 to 10.1, as
indicated by the results shown below (pH was adjusted with dilute nitric acid or sodium hydroxide
solution)-
pH . . .. 2.48 2.96 3.91 4.50 6-13 6-95 7.90 9-14 10.1 11.0
Recovery, yo 80.4 86.4 95.8 99.5 99.6 99.7 99.8 100.0 100.0 101.1
At low pH precipitation is slow and incomplete, but large crystals are formed. Co-precipitation
of basic lead salts does not cause interference until pH 11 is reached.
In the absence of alcohol and additional acid or alkali-
pH before precipitation = 6.5
pH after precipitation = 4.0
(pH of 0.05 M lead nitrate = 4.3)
Thus if no buffering component is present the pH of the mixture after precipitation appears to
be fixed by the acid nature of the lead nitrate. If buffering ions are present in similar concen-
tration to the lead nitrate, the results shown above for the variation in recovery with pH would
no longer be valid.
The possible introduction of a buffer at pH 4 to 6 cannot be recommended, since this must
contain a weak acid radicle that will complex to a greater or lesser extent with lead. This statement
is amply borne out for acetate. Different volumes of an acetic acid - sodium acetate solution
0.50 M in acetate and of pH 5.0 were introduced into the method and the recoveries noted (see
Table I); the concentration of chloride was kept constant.

TABLEI
INFLUENCE
OF ACETATE

Volume of 0.5 M Ratio [CH3C00-1

acetate added, [Pb2+] Recovery,
ml %
2.0 0.8 98.7
5.0 2.0 96.9
10.0 4.0 93.0

The stability constant for the equilibrium-

+
Pb2+ 2CH3COO- = Pb(CH3COO),
has a value3 of log K = 4.2, which would well explain this interference from acetate.
From the foregoing considerations it is evident that an unknown fluoride solution, which
may contain buffering components, should be brought to a pH of 5 to 6 by addition of dilute
nitric acid or sodium hydroxide only.
 View Article Online
406 SHORT PAPERS [Analyst, Vol. S8
Interference in the method is caused by ions that precipitate or complex lead or fluoride;
, ~ . g .sulphate
, and phosphate can be titrated almost quantitatively as fluoride.
The method mas applied to solutions resulting from oxygen flask combustion of fluorinated
.organic compounds, but carbonate ions seriously interfered, and the time involved in removing them
rendered the method no more rapid than some conventional colorimetric procedures.

REFERENCES
Published on 01 January 1963. Downloaded by Brown University on 26/09/2013 08:30:41.

1. VieSfAl, J., Havi?, J., BrandStetr, J., and liotrlf, S., Chem. Listy, 1957, 51, 16i7; Anal. Absfv.,
1958, 5, 2199.
2. Sakharova, Ya. G., and Shishkina, N. I., Zavod. Lab., 1959, 25, 1442; Anal. Abstv., 1960, 7, 3239.
3. “Stability Constants of Metal-Ion Complexes, with Solubility Products of Inorganic Substances,”
Part 1, Special Publication No. 6, The Chemical Society, London.
Received October 24th, 1962