ARAVINTHAN A/L RAMAN

S59879

Ts. ChM. Dr. Nabilah Ismail

1
10 JUNE 2021
ASSIGNMENT 1

CHLORATE ION STANDARD SOLUTION ESTABLISHED BY MULTIPATH TITRATION

TECHNIQUES.

The aim of this study was to analytes chlorate of interest, particularly in terms
of water quality assessment. Several organisations, including the World Health
Organization and the American Public Health Association, have weighed in on the
issue. The documentation to investigate chlorate levels in water as a result of due to
its toxicity, not only for humans but also for other living organisms.

Analytical devices such as ionselective electrodes, spectrophotometers, flow

injection analyzers, and chromatography are used to test chlorate ions. These
instruments require a chlorate standard solution to quantify; however, there has never
been a chlorate ion standard solution described by a metrologically valid process.

Chlorate ions were measured using multipath gravimetric titration procedures

linked to the International System of Units in this investigation (SI). Titrimetry is one
of the most well-known and exact methods for measuring major and minor
constituents, and it outperforms other instrumental approaches in the following two
areas.

The sample preparations are three CRMs (NMIJ CRM 3002-a potassium
dichromate, NMIJ CRM 3008-a sodium chloride, and NMIJ CRM 3006-a potassium
iodate) and the coulometric titrations used to determine them were previously
described (NMIJ CRM 3002-a potassium dichromate, NMIJ CRM 3008-a sodium
chloride, and NMIJ CRM 3006-a potassium iodate). Unless otherwise noted, analytical
reagent grade compounds were utilised.characteristics and interaction type use
mechanisms of ion exchange, surface adsorption, partition, and size exclusion. There
are two main ways to interpret a chromatogram determination of the peak height of
a chromatographic peak as measured from the baseline and determination of the peak
area. Hence, HPLC used for trace analysis, preparation of pure compound and,
separation and analysis of non-volatile or thermally unstable compounds.

For back titration, a potassium dichromate solution of approximately 10 mmol

kg1 was made gravimetrically by dissolving in water.

2
 By dissolving iron(II) sulphate heptahydrate in roughly 2 mol L1 sulfuric acid,
a 300 mmol kg1 iron(II) sulphate heptahydrate was obtained. Gravimetric titration
with the standard potassium dichromate on heating was used to quantify the
concentration of the iron(II) sulphate solution. The end point was chosen as the
inflection point determined using third order polynomial approximation. Back titration
with the standardised excess iron(II) sulphate solution and the standard potassium
dichromate solution on heating was used to quantify sodium chlorate. The final point
was chosen in the same way as the beginning point.

The sample techniques used for the end-point detection of their titrations are back
titration. Back titration is a titration in which a known excess of standard reagent is
introduced to the solution and the excess is titrated instead of the original sample.
When the endpoint of the reverse titration is easier to recognise than the endpoint of
the regular titration, such as in precipitation reactions, a back titration is
advantageous. When the interaction between the analyte and the titrant is very slow,
or when the analyte is in a non-soluble solid, back titrations are also effective.

Back titration works as follows (with an example): 1: An unknown concentration

substance or solution (4 gramme of tainted chalk, CaCO3) is made to react with an
intermediate reactant solution of known volume and concentration (200 ml, 0.5N HCl).
The reaction has progressed beyond the point of equality.

Here are the technique back titration in the journal:

Path A (back titration with dichromate ions and iron(II) ions); A type HM-30R
potentiometer (pH meter) with a Pt–Ag/AgCl combination electrode.

In line with the certificate, standard potassium dichromate (NMIJ CRM 3002-a) was
dried at 150 °C for 1 hour and stored in a desiccator with silica gel. The oxidants'
certified value represented as potassium dichromate was 99.974 percent 0.011
percent (coverage factor k = 2, which gives a level of confidence of about 95 percent).

Path B (precipitation titration between chloride ionsand silver ions); a type HM-30R
potentiometer (pH meter) with a silver working electrode and a mercury-sulfate
reference electrode.

3
In line with the certificate, standard sodium chloride (NMIJ CRM 3008-a) was dried at
600 °C for 2 hours and stored in a desiccator with silica gel. For argentometry, the
verified purity represented as sodium chloride was 100.001 percent 0.045 percent (k
= 2).

Path C (titration between thiosulfate ions and triiodide ions, the titration curves of
which were drawn by constant-voltage biamperometry a type 7651 DC current source
and a type 7562 digital multimeter of Yokogawa Electric Corporation, Tokyo, Japan,
equipped with a dual‑platinum electrode.

In line with the certificate, standard potassium iodate (NMIJ CRM 3006-a) was dried
at 130 °C for 2 hours and stored in a desiccator with silica gel. The oxidants have a
verified value of The results of three sodium chlorate test are summarised here.

Various titrations are displayed. Sodium chloride was used.Finally, a weighted mean
was used to characterise the data. Values for weighing,and final weighting values,
were calculated using the following formulas: 99.973 percent 0.018 percent (k = 2)
when expressed as potassium iodate.

The iodine liberation time affects sodium chlorate tests. Panel (b) is an expanded
version of panel (a) with a different background with data correction.

4
According to data the figure shows assays for sodium chlorate in pathways A, B, and
C. Each bar represents the enlarged level of uncertainty (k = 2).

According to data the figure shows The reaction pathways A and B were used to assess
the stability of sodium chlorate in solids.

5
The figure shows The reaction route A was used to test the stability of sodium
chlorate in solution. Symbol O and a solid regression line saved at 8°C; symbol▲
and a dotted regression line saved at room temperature; symbol △ and another
dotted regression line corrected by mass changes for symbols▲.

where xi is each value.

Finally, the assay (mass fraction) of sodium chlorate calculated was 99.829% ±
0.029% (k = 2).

The reaction pathways A and B in the figure above were used to test the stability of
sodium chlorate in solids. According to the residual errors from the F test, the
difference between the data deviation and the slope of the regression line with
storage time was statistically insignificant. The standard uncertainty of the stability
was derived from the standard uncertainty of the slope as a consequence of this
test. The standard uncertainty of the slope per day was 0.0000411 percent; thus,
the standard uncertainty for one year's long-term stability was 0.015 percent.

In conclusion, Multipath titrations based on different reactions eliminated

unknown biases and gave further reliable results. The results through the reaction
paths (a) and (b) were in good agreement, though these reactions were totally
different. The mass fraction of sodium chlorate by using a weighted mean calculated
from the results of three titrations was 99.829%.

6
Reference:

ASAKAI, T.,(2018). CHLORATE ION STANDARD SOLUTION ESTABLISHED BY MULTIPATH

TITRATION TECHNIQUES. Microchemical Journal,(142),9-16 retrieved from:

www.elsevier.com/locate/microc

7
 Microchemical Journal 142 (2018) 9–16

Contents lists available at ScienceDirect

Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Chlorate ion standard solution established by multipath titration techniques T

Toshiaki Asakai
National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: Analyses of chlorate ion are essential in evaluating water quality; however, there is no standard solution of
Chlorate ion standard solution chlorate ion characterized by a metrologically valid procedure. This paper describes the measurement proce-
Water quality dures and assays of chlorate ions with the linkage to the International System of Units (SI) by multipath
Certified reference material gravimetric titration techniques. Three different titration techniques were employed to assay chlorate ions:
Oxidation-reduction titration
oxidimetric-reductometric back titration with an iron(II) solution standardized with standard potassium di-
Precipitation titration
Ion chromatography
chromate, precipitation titration with a silver nitrate solution standardized with standard sodium chloride, and
oxidimetric-reductometric titration with a thiosulfate solution standardized with standard potassium iodate. The
results obtained through three different reactions were in good agreement with each other within their un-
certainties. A certified reference material of chlorate ions with the linkage to the SI was first established by
evaluating the storage stability of the solution and estimating measurement uncertainties. The assay (mass
fraction) of sodium chlorate was characterized by using a weighted mean of the results of three methods;
99.829% ± 0.029% (the value following ± gives a level of confidence of approximately 95%, coverage factor
k = 2). Providing with the standard solution through Japan Calibration Service System (JCSS) under Japanese
Measurement Act widely allows all analysts to obtain their reliable analytical results.

1. Introduction obtain repeatabilities below 0.5% relative.

Chlorate is one of the analytes of interest, especially from the
viewpoint of evaluating water quality. Several institutions such as the
World Health Organization and the American Public Health Association
have issued documents to examine chlorate contents in water [1, 2] due
to its toxicity for not only human being but also other living organisms
[3–5]. The Ministry of Health, Labour and Welfare has posed chlorate
measurements in Japanese Water Supply Act [6].
Chlorate ions are measured by analytical instruments such as ion-
selective electrodes [7], spectrophotometers [8, 9], flow injection
analyzers [10–13] and chromatography [14–19]. These instruments
require a standard solution of chlorate to quantify; however, no stan-
dard solution of chlorate ion characterized by a metrologically valid
procedure has existed [20, 21].
In the present study, chlorate ions were assayed by multipath
gravimetric titration techniques with the linkage to the International
System of Units (SI). Titrimetry is one of the most classic and precise
methods for measurements of both major and minor constituents, and is
highly superior in terms of the following two points in comparison to
other instrumental methods: measurements of major constituents and
its repeatability. Titrimetry is applicable to determine major con-
stituents up to 100%, and has a higher repeatability below 0.01% re-
lative. It is difficult using instrumental analyses mentioned above to
The all assays for chlorate ions given in the present paper were
traceable to the SI (mass, time and ampere) because the roots of them
reached to coulometric assays which yield the amount of substances on
an absolute basis based on Faraday's laws of electrolysis [22]. Gravi-
metric titrations performed in the present study were based on the
following reactions (Fig. 1):
NaClO3 + 6FeSO4 + 3H2 SO4 → NaCl + 3Fe2 (SO4 )3 + 3H2 O (A.1)
6FeSO4 + K2Cr2O7 + 7H2 SO4 → 3Fe2 (SO4 )3 + Cr2 (SO4 )3 + 7H2 O
+ K2SO4 (A.2)
Chlorate ions were assayed by oxidimetric-reductometric titration
based on standard potassium dichromate traceable to the SI which was
determined by oxidimetric-reductometric coulometric titration with
electrogenerated iron(II) [23, 24]. Excess iron(II) which was standar-
dized with potassium dichromate was added to chlorate, and then the
excess iron(II) was back-titrated with potassium dichromate.
NaClO3 + 3Na2SO3 + 6HNO3 → NaCl + 3H2 SO4 + 6NaNO3 (B.1)
NaCl + AgNO3 → AgCl + NaNO3 (B.2)
Chlorate ions were assayed by argentometric titration based on
standard sodium chloride traceable to the SI which was determined by

E-mail address: t-asakai@aist.go.jp.

https://doi.org/10.1016/j.microc.2018.06.015
Received 4 January 2018; Received in revised form 9 June 2018; Accepted 9 June 2018
Available online 14 June 2018
0026-265X/ © 2018 Elsevier B.V. All rights reserved.
T. Asakai
Fig. 1. Experimental design for the assay of chlorate ions through three different titration techniques.
argentometric coulometric titration with electrogenerated silver(I)
[25]. The decomposition reaction of chlorate ions by sodium sulfite
could be proceeded according to the reaction (B.1) [26–29]. Chloride
ions generated through the decomposition of chlorate ions by excess
sodium sulfite were titrated with a silver nitrate solution which was
standardized with sodium chloride in precipitation reaction.
NaClO3 + 6KI + 6HCl → 3I2 + NaCl + 6KCl + 3H2 O (C.1)
2Na2S2 O3 + I2 → 2NaI + Na2S4 O6 (C.2)
KIO3 + 5KI + 3H2 SO4 → 3I2 + 3K2SO4 + 3H2 O (C.3)
Chlorate ions were assayed by oxidimetric-reductometric titration
based on standard potassium iodate traceable to the SI. Iodine (triio-
dide) liberated by chlorate ions in an acidic potassium iodide solution is
titrated with a sodium thiosulfate solution [30, 31]. This sodium thio-
sulfate solution was standardized with potassium iodate which was
determined based on the oxidimetric-reductometric coulometric titra-
tion and was traceable to the SI [32].
Chlorate ions were assayed by metrologically valid multipath ti-
tration techniques with the linkage to the SI. Multipath titrations based
on different reactions eliminated unknown biases and gave further su-
perior results than those based on a conventional single titration
method. The reactions of oxidation of iron(II) and iodide ions are
known in volumetric analysis; however, the present study has several
advantages and new information: first establishment of a certified re-
ference material (CRM) of chlorate ions by multipath titration techni-
ques eliminated unknown biases, a reliable back titration between
chlorate ions and iron(II) with examining appropriate titration condi-
tions, an application of precipitation titration for chlorate ions through
10
Microchemical Journal 142 (2018) 9–16
the decomposition of them with sodium sulfite, an examination of io-
dine liberation reactions by chlorate ions with iodide ions and acids,
and stability data of sodium chlorate and chlorate ion solutions.
Titrimetry traceable to the SI on an absolute basis could give the sta-
bility as new information because the examinations for stability need an
absolute method not a relative one. Estimating related uncertainties, a
CRM of chlorate ions was first established with the linkage to the SI on
an absolute basis. This CRM has provided through Japan Calibration
Service System (JCSS) under Japanese Measurement Act [33], in which
it widely allows all analysts to obtain reliable CRMs in solution form
and their reliable analytical results.
2. Material and methods
Sodium chlorate was of analytical reagent grade, Wako first grade,
obtained from Wako Pure Chemical Industries, Ltd., Osaka, Japan.
Three CRMs and the coulometric titrations for their determinations
were previously described (NMIJ CRM 3002-a potassium dichromate
[23, 24], NMIJ CRM 3008-a sodium chloride [25] and NMIJ CRM 3006-
a potassium iodate [32]). Analytical reagent grade chemicals were used
unless otherwise stated.
Gravimetric titrations were performed with a plastic syringe with a
polyetheretherketone (PEEK) or PFA needle. Solid materials were
weighed with resolution of 1 μg by a type XP26 balance. Solution-form
samples were weighed with resolution of 10 μg by a type XP205 bal-
ance. The balances used were of Mettler Toledo, Tokyo, Japan.
Buoyancy corrections were always applied.
Chlorate ion solutions were kept in a high density, narrow-neck
polyethylene bottle with inner lid (100 mL) purchased from Sanplatec
T. Asakai
Corp., Osaka, Japan.
Instruments used for the end-point detection of their titrations were
as follows:
a type HM-30R potentiometer (pH meter) with a Pt–Ag/AgCl com-
bination electrode of DKK-TOA Corporation, Tokyo, Japan for path
A (back titration with dichromate ions and iron(II) ions);
a type HM-30R potentiometer (pH meter) with a silver working
electrode and a mercury-sulfate reference electrode of DKK-TOA
Corporation for path B (precipitation titration between chloride ions
and silver ions);
a type 7651 DC current source and a type 7562 digital multimeter of
Yokogawa Electric Corporation, Tokyo, Japan, equipped with a
dual‑platinum electrode for path C (titration between thiosulfate
ions and triiodide ions, the titration curves of which were drawn by
constant-voltage biamperometry [32]).
2.1. Back titration with dichromate ions and iron(II) ions − path A
Standard potassium dichromate (NMIJ CRM 3002-a) was dried at
150 °C for 1 h, and kept in a desiccator with silica gel in accordance
with the certificate. The certified value of the oxidants expressed as
potassium dichromate was 99.974% ± 0.011% (coverage factor k = 2,
which gives a level of confidence of approximately 95%).
An approximately 10 mmol kg−1 potassium dichromate solution
was gravimetrically prepared by dissolving in water for back titration.
An approximately 300 mmol kg−1 iron(II) sulfate heptahydrate was
prepared by dissolving in ca. 2 mol L−1 sulfuric acid. The concentration
of the iron(II) sulfate solution was determined by gravimetric titration
with the standard potassium dichromate on heating. The inflection
point calculated by third order polynomial approximation was decided
as the end point.
Sodium chlorate was determined by back titration with the stan-
dardized excess iron(II) sulfate solution and the standard potassium
dichromate solution on heating. The end point was determined in the
same manner as that mentioned above.
2.2. Titration between chloride ions and silver ions after decomposition of
chlorate ions − path B
Standard sodium chloride (NMIJ CRM 3008-a) was dried at 600 °C
for 2 h, and kept in a desiccator with silica gel in accordance with the
certificate. The certified value of the purity expressed as sodium
chloride for argentometry was 100.001% ± 0.045% (k = 2).
An approximately 300 mmol kg−1 silver nitrate solution was pre-
pared by dissolving in water. The concentration of the silver nitrate
solution was determined by gravimetric titration with the standard
sodium chloride. The inflection point calculated by third order poly-
nomial approximation was decided as the end point.
Sodium chlorate was determined by gravimetric titration with the
standardized silver nitrate solution after the decomposition of chlorate
ions with sodium sulfite. The end point was determined in the same
manner as that mentioned above.
2.3. Titration between thiosulfate ions and triiodide ions through iodine
liberation reaction − path C
Standard potassium iodate (NMIJ CRM 3006-a) was dried at 130 °C
for 2 h, and kept in a desiccator with silica gel in accordance with the
certificate. The certified value of the oxidants expressed as potassium
iodate was 99.973% ± 0.018% (k = 2).
An approximately 300 mmol kg−1 sodium thiosulfate solution was
prepared by dissolving in water. The concentration of the sodium
thiosulfate solution was determined by gravimetric titration with the
standard potassium iodate through the iodine liberation reaction by
adding potassium iodide and acids. The end point was decided at
11
Microchemical Journal 142 (2018) 9–16
substantially zero ampere of the indicator current.
Sodium chlorate was determined by gravimetric titration with the
standardized sodium thiosulfate solution through the iodine liberation
reaction with potassium iodide and acids. The end point was de-
termined in the same manner as that mentioned above.
3. Results and discussion
3.1. Back titration with dichromate ions and iron(II) ions − path A
Sodium chlorate was assayed through path A: excess iron(II) sulfate
was added and then gravimetrically back-titrated with a standard so-
lution of potassium dichromate. The iron(II) sulfate solution was pre-
liminarily standardized by gravimetric titration with standard po-
tassium dichromate.
3.1.1. Examination of back titration with dichromate ions and iron(II) ions
Approximately 0.14 g of the standard potassium dichromate was
placed in a 50 mL beaker, dissolved in 20 mL of 2 mol L−1 sulfuric acid,
and then titrated with an iron(II) sulfate solution on heating around
70 °C. The relative standard deviation (RSD) of the concentration of the
iron(II) sulfate solution obtained was 0.0126% (n = 7, n is the number
of measurements under a repeating condition); the relative standard
deviation of the mean was 0.00476% (n = 7).
Approximately 0.08 g of sodium chlorate was placed in a 50 mL
beaker, and was added the standardized excess iron(II) sulfate solution
(ca. 0.5% excess). The solution was heated around 70 °C for 10 min, and
then the excess iron(II) sulfate was titrated with the standard potassium
dichromate solution on heating. The dependency of the assay of sodium
chlorate on heating duration is given in Fig. 2. This examination
showed no dependency of the assays of sodium chlorate on the heating
duration; therefore, the condition of heating for 10 min was adopted for
the back titration because no heating procedure gave larger repeat-
ability. The RSD of the assay of sodium chlorate obtained was 0.0341%
(n = 5); the RSD of the mean was 0.0152% (n = 5).
3.1.2. Uncertainty of back titration of sodium chlorate with dichromate ions
and iron(II) ions
Measurement uncertainties of sodium chlorate by back titration
with dichromate ions and iron(II) ions are given in Table 1. The ex-
panded uncertainty of potassium dichromate was 0.011% (k = 2). Re-
peatabilities of titration between dichromate ions and iron(II) ions, and
back titration of sodium chlorate were the RSDs of the mean of each
titration. The uncertainties of weighing of solid materials were calcu-
lated from the linearity (6 μg) and the sensitivity (0.022 mg, expanded
Fig. 2. Dependency of sodium chlorate assays on heating duration in the back
titration of sodium chlorate with dichromate ions and iron(II) ions.
T. Asakai Microchemical Journal 142 (2018) 9–16

Table 1
Uncertainty budget for sodium chlorate assay by back titration with dichromate
ions and iron(II) ions.
Uncertainty source Relative standard uncertainty, %

Uncertainty of standard potassium 0.005 5

dichromate
Repeatability of titration between 0.004 76
dichromate ions and iron(II) ions
Repeatability of back titration of sodium 0.015 2
chlorate
Weighing of potassium dichromate 0.002 47
Weighing of sodium chlorate 0.004 33
Weighing of an iron(II) ion solution Negligible
Weighing of a dichromate ion solution Negligible
Preparation of a standard potassium Negligible
dichromate solution
Molar mass of potassium dichromate Included in the certified value of
standard potassium dichromate
Molar mass of sodium chlorate Negligible
Buoyancy correction Negligible
Fig. 3. Dependency of sodium chlorate assays on time with acetate buffer and
Combined standard uncertainty 0.017 6
Expanded uncertainty (coverage factor 0.035 heating (X) without buffer nor heating (O) in the titration of chloride ions
k = 2) generated through the decomposition of chlorate ions with a silver nitrate so-
lution.

uncertainty of a standard weight (20 g) used for calibration) of the titration was carried out with acetate buffer (2 mL of 410 g sodium
balance. The uncertainties of weighing of solution-form materials and acetate per 1 L) after heating at 80 °C. This titration was performed with
gravimetric preparation of a standard potassium dichromate solution the intention to accelerate the decomposition reaction by heating, and
were negligible because the related uncertainties were very small in to make a mild condition (ca. pH 4) for the precipitation titration by
comparison to the weighing operations: weighing masses of the solu- adding the buffer. There were no dependencies on the reaction time and
tions were 6 g or 12 g, the linearity of the balance (0.1 mg) and the the condition of the solution; therefore, the assay of sodium chlorate
sensitivity (0.05 mg for 100 g). The uncertainty of the molar mass of through this reaction was calculated from the all results illustrated in
potassium dichromate was included in its certified value. Other un- Fig. 3. The RSD of the assay of sodium chlorate obtained was 0.0509%
certainty sources, molar mass of sodium chlorate and buoyancy cor- (n = 24); the RSD of the mean was 0.0104% (n = 24).
rection were also small compared to other dominant sources. Conse-
quently, the assay (mass fraction) of sodium chlorate was
99.821% ± 0.035% (k = 2). 3.2.2. Uncertainty of titration of sodium chlorate with silver ions after
decomposition of chlorate ions
3.2. Titration between chloride ions and silver ions after decomposition of Measurement uncertainties of sodium chlorate by titration with
chlorate ions − path B silver ions after decomposition of chlorate ions are given in Table 2. The
expanded uncertainty of sodium chloride was 0.045% (k = 2). Re-
Sodium chlorate was assayed through path B: chloride ions gener- peatabilities of titrations between chloride ions and silver ions were the
ated through the decomposition of chlorate ions by excess sodium RSDs of the mean of each titration. The uncertainties of weighing and
sulfite were titrated with a silver nitrate solution. The silver nitrate other related sources were estimated in the same manner as those of the
solution was preliminarily standardized by gravimetric titration with oxidimetric-reductometric titration (vide supra). Consequently, the
standard sodium chloride. assay (mass fraction) of sodium chlorate was 99.837% ± 0.050%
(k = 2).
3.2.1. Examination of decomposition of chlorate ions by gravimetric
titration with silver ions
Approximately 0.17 g of the standard sodium chloride was placed in
a 100 mL beaker, dissolved in 50 mL of water, and then titrated with a Table 2
silver nitrate solution. The RSD of the concentration of the silver nitrate Uncertainty budget for sodium chlorate assay by titration with silver ions after
solution obtained was 0.00290% (n = 4); the RSD of the mean was decomposition of chlorate ions.
0.00145% (n = 4). Uncertainty source Relative standard uncertainty, %
Approximately 0.5 g of sodium chlorate was placed in a 100 mL
beaker, and was added ca. 20 mL of ca. 1.2 mol L−1 sodium sulfite (ca. Uncertainty of standard sodium chloride 0.022 5
Repeatability of titration between 0.001 45
150 g per 1 L), which was the excess amount of reductants.
chloride ions and silver ions
Approximately 7 mol L−1 nitric acid (nitric acid/water = 1/1 in vo- Repeatability of titration of sodium 0.010 4
lume) was added to accelerate the decomposition reaction. The acidity chlorate (chloride ions)
of the solution was monitored with dropping the nitric acid solution: pH Weighing of sodium chloride 0.002 04
Weighing of sodium chlorate 0.000 70
values of the solution were ca. pH 7 with 1 mL of the nitric acid solu-
Weighing of a silver ion solution Negligible
tion, ca. pH 6 with 2 mL, and less than pH 1 with 3 mL. After dropping Molar mass of sodium chloride Included in the certified value of
3 mL of the nitric acid solution, the decomposition reaction violently standard sodium chloride
proceeded with generating gas and self-heating. Fig. 3 illustrates the Molar mass of sodium chlorate Negligible
dependency of sodium chlorate assays on time under two different ti- Buoyancy correction Negligible
Combined standard uncertainty 0.024 9
tration conditions. Sodium chlorate was titrated with the standardized
Expanded uncertainty (coverage factor 0.050
silver nitrate solution after starting the decomposition followed by di- k = 2)
luting with water up to 50 mL without buffer nor heating. The other

12
T. Asakai
3.3. Titration between thiosulfate ions and triiodide ions through iodine
liberation reaction − path C
Sodium chlorate was assayed through path C: iodine (triiodide)
liberated by chlorate ions in an acidic potassium iodide solution was
titrated with a sodium thiosulfate solution. The sodium thiosulfate so-
lution was preliminarily standardized by gravimetric titration with
standard potassium iodate through iodine liberation reaction. This re-
action path was challenging to apply to assay chlorate ions due to the
lower reactivity of chlorate ions with iodide ions.
3.3.1. Examination of iodine liberation by constant-voltage biamperometry
Constant-voltage biamperometry was utilized to roughly investigate
the iodine liberation profile. Constant-voltage biamperometry is a
method of monitoring the current between twin electrodes, typically
twin platinum electrodes, where a constant voltage is applied. The
current flows in the presence of both iodide ions and triiodide ions
through the reaction [3I− ↔ I3− + 2e−] on each surface. The current
was proportional to the amount of liberated iodine for up to 1 g of
potassium iodide in 100 mL water when using a dual Pt-chip electrode
which had small surfaces because this electrochemical reaction is dif-
fusion-controlled [32]. The conditions of the examination were as fol-
lows: a dual Pt-chip electrode (each 0.5 mm ϕ × 0.5 mm long), a con-
stant-voltage of 500 mV, and stirring at 900 rpm (revolutions per
minute).
Fig. 4 shows profiles of iodine liberation monitored by constant-
voltage biamperometry. Approximately 0.1 g of sodium chlorate was
placed in a beaker, and was dissolved in ca. 50 mL of ca. 6 mol L−1 or
ca. 3 mol L−1 hydrochloric acid. After adding 3 g to 7 g of potassium
iodide, the currents were monitored. Approximately 0.1 g of sodium
chlorate potentially oxidizes 0.006 mol of iodide ions (ca. 0.9 g of po-
tassium iodide) and consequently liberates ca. 0.8 g iodine. Under the
condition using 3 mol L−1 hydrochloric acid, the indicator currents
gradually increased; the iodine liberation reaction was apparently very
slow. Using 6 mol L−1 hydrochloric acid, the reaction proceeded with
Fig. 4. Profiles of iodine liberation by oxidizing iodide ions with sodium
chlorate. The iodine liberation process was monitored by constant-voltage
biamperometry for 0.1 g of sodium chlorate using a dual Pt-chip electrode
(applied constant voltage 500 mV), stirring at 900 rpm. The indicator currents
were recorded after adding different amounts of potassium iodide (3 g, 5 g and
7 g) into a sodium chlorate solution. The currents are proportional to the
amount of liberated iodine. The samples were dissolved in: (a) 50 mL of
6 mol L−1 hydrochloric acid, (b) 50 mL of 3 mol L−1 hydrochloric acid.
13
Microchemical Journal 142 (2018) 9–16
higher reaction rate. Smaller amounts of potassium iodide (e.g., 3 g) led
to the deposition of solid iodine and larger vaporization of iodine from
the solution. Solutions in any conditions had an odor, which might be
chloride compounds', at the initial stage of reaction. When using
9 mol L−1 or 4.5 mol L−1 sulfuric acid instead of hydrochloric acid,
there were similar problems occurred such as significant vaporization
of iodine. Use of potassium chlorate instead of sodium chlorate showed
the similar phenomena.
Chlorate ions required highly acidic conditions to oxidize iodide
ions in comparison with those of iodate ions [32], periodate ions [34],
bromate ions [35], dichromate ions [36], and cerium ions [37]. Judging
from these examinations, the following condition of the iodine libera-
tion was adopted: use of 50 mL of 6 mol L−1 hydrochloric acid, 5 g of
potassium iodide, and more than 10 min liberation time.
3.3.2. Examination of iodine liberation by gravimetric titration with
thiosulfate ions
Approximately 0.15 g of the standard potassium iodate was placed
in a 100 mL beaker, dissolved in 40 mL of water, and then titrated with
a sodium thiosulfate solution. The RSD of the concentration of the so-
dium thiosulfate solution obtained was 0.00506% (n = 3); the RSD of
the mean was 0.00292% (n = 3).
Approximately 0.09 g of sodium chlorate was placed in a 100 mL
beaker, and was dissolved in ca. 50 mL of 6 mol L−1 hydrochloric acid,
and added 5 g of potassium iodide. The liberated iodine was titrated
with the standardized sodium thiosulfate solution. Fig. 5 illustrates the
dependency of sodium chlorate assays on the iodine liberation time. It
was natural that shorter iodine liberation time led smaller assays of
sodium chlorate since iodine was not completely liberated stoichio-
metrically corresponding to that of sodium chlorate given in Fig. 5 (a);
the complete iodine liberation required more than 20 min. There was
no dependency of the sodium chlorate assays on the iodine liberation
time over 20 min from the enlarged Fig. 5 (b).
Iodide ions are easily oxidized in an acidic medium caused by air
oxygen and light [32]. In order to evaluate the amount of the influence,
method blanks were examined under the same condition without so-
dium chlorate. The bias caused by oxidation of iodide ions was very
large and significant due to the higher acidic conditions compared with
that for other compounds such as potassium iodate, the impact of the
background increase on the sodium chlorate assays was ca. 0.01% per
minute. Corrected data were plotted in Fig. 5 (b).
There was no dependency of the sodium chlorate assays on the io-
dine liberation time over 20 min; therefore, these all data were used for
the calculation. The RSD of the assay of sodium chlorate obtained was
0.157% (n = 8); the RSD of the mean was 0.0554% (n = 8).
3.3.3. Uncertainty of titration of sodium chlorate with thiosulfate ions
through iodine liberation reaction
Measurement uncertainties of sodium chlorate by titration with
thiosulfate ions through iodine liberation reaction are given in Table 3.
The expanded uncertainty of potassium iodate was 0.018% (k = 2). The
uncertainty for the correction caused by oxidation of iodide was con-
servatively estimated by assuming a rectangular distribution with its
half range of the amount of the correction. The other uncertainties were
estimated in the same manner as those of the other titrations (vide
supra). Consequently, the assay (mass fraction) of sodium chlorate was
100.01% ± 0.27% (k = 2).
3.4. Establishment of sodium chlorate assay with a metrological traceability
to the SI by multipath titration techniques
The summary of the assays of sodium chlorate measured by three
different titrations is shown in Fig. 6 and Table 4. Sodium chlorate was
finally characterized by using a weighted mean [38]. Weighting values,
w′i, and final weighting values, wi, were obtained using:
T. Asakai Microchemical Journal 142 (2018) 9–16

Fig. 6. Sodium chlorate assays through the paths A, B and C. Each bar indicates
the expanded uncertainty (k = 2).

Table 4
Characterization of sodium chlorate using a weighted mean.
Path Mean Combined standard Weighting (w′i) Final
(xi), % uncertainty (ui), % weighting (wi)

Path A 99.821 0.018 3238.07 0.660171

Path B 99.837 0.025 1609.92 0.328226
Path C 100.01 0.13 56.9118 0.0116031
Weighted 99.829 0.014 – –
mean

Fig. 5. Dependency of sodium chlorate assays on the iodine liberation time.

Panel (b) is the enlarged view of panel (a) and displayed with background
correction data.

Table 3
Uncertainty budget for sodium chlorate assay by titration with thiosulfate ions
through iodine liberation reaction.
Uncertainty source Relative standard uncertainty, %

Uncertainty of standard potassium iodate 0.009 0

Repeatability of titration between 0.002 92
potassium iodate and sodium
thiosulfate
Repeatability of titration of sodium 0.055 4 Fig. 7. Stability of sodium chlorate in solid evaluated using the reaction paths A
chlorate (iodide ions) or B.
Weighing of potassium iodate 0.002 31
Weighing of sodium chlorate 0.003 85
Correction caused by oxidation of iodide 0.120 1
w′ =
ions ui2 (D.1)
Weighing of a thiosulfate ion solution Negligible
Molar mass of potassium iodate Included in the certified value of
standard potassium iodate
w′
w=
Molar mass of sodium chlorate Negligible ∑ w′i (D.2)
Buoyancy correction Negligible
Combined standard uncertainty 0.133 where ui is a combined standard uncertainty for each titration. The
Expanded uncertainty (coverage factor 0.27 mean, x-bar, and the associated standard uncertainty, u(x-bar), were
k = 2)
calculated from:

x = ∑ wi xi (D.3)

u (x ) = ∑ wi2 ui2 (D.4)

14
T. Asakai
Fig. 8. Stability of sodium chlorate in solution evaluated using the reaction
path A. Concentration of chlorate ions plotted symbol O and a solid regression
line stored at 8 °C; symbol ▲ and a dotted regression line stored at room
temperature; symbol △ and another dotted regression line corrected by mass
changes for symbols ▲.
where xi is each value.
Finally, the assay (mass fraction) of sodium chlorate calculated was
99.829% ± 0.029% (k = 2).
3.5. Stability of sodium chlorate and chlorate ion solutions
Stability of sodium chlorate in solid was evaluated using the reac-
tion paths A or B (Fig. 7). The difference between the deviation of the
data and the slope of the regression line with the storage time was
statistically insignificant judging from the residual errors by F test. As a
result of this test, the standard uncertainty of the stability was esti-
mated from the standard uncertainty of the slope. The standard un-
certainty of the slope per day was 0.0000411%; therefore, the standard
uncertainty for the long-term stability was 0.015% for one year.
Stability of sodium chlorate in solution was evaluated by direct ti-
tration for the solution form through the reaction path A; oxidation-
reduction reaction with iron(II) ions. Approximately 10 L of sodium
chlorate solution (ca. 1000 mg kg−1) was prepared by dissolving in
water, and afterward each solution was subdivided into 81 high den-
sity, narrow-neck polyethylene bottles with inner lid (100 mL) pur-
chased from Sanplatec Corp., Osaka, Japan. The divided 81 bottles were
in homogeneous within the measurement repeatability checked by
oxidimetric-reductometric titration for the bottles No. 1, No. 40 and No.
81. These solutions were stored at room temperature in a laboratory for
the odd-numbered bottles, and around 8 °C in a refrigerator for the
even-numbered bottles in order of the bottling. Fig. 8 illustrates the
long-term stability of the solutions. The chlorate ion solutions stored in
a refrigerator were stable. In comparison, the concentration of chlorate
ion solutions stored in a laboratory linearly increased. The reason of the
increase was very simple, just vaporization of water. The mass of the
100 mL of polyethylene bottles decreased ca. 0.1% a year in a labora-
tory and ca. 0.01% a year in a refrigerator. Data corrected by using each
mass change showed its good stability. Judging from the results, chlo-
rate ions were stable and could not be decomposed.
4. Conclusions
Multipath titration techniques were performed to assay sodium
chlorate and its solution with the linkage to the SI. Utilized titration
techniques were (a) oxidimetric-reductometric back titration with di-
chromate ions and iron(II) ions, (b) precipitation titration with silver
ions of chlorate ions generated from the decomposition of chlorate ions
15
Microchemical Journal 142 (2018) 9–16
with sodium sulfite, and (c) iodometric titration with thiosulfate ions
for chlorate ions through iodine liberation reaction. The results through
the reaction paths (a) and (b) were in good agreement, though these
reactions were totally different. Though the repeatability of the reaction
path (c) was larger in comparison, it was confirmed that this reaction
path was available in practical. Multipath titrations based on different
reactions eliminated unknown biases and gave further reliable results.
Uncertainties of sodium chlorate assays were estimated by evaluating
the storage stability and estimating measurement uncertainties. The
assay (mass fraction) of sodium chlorate by using a weighted mean
calculated from the results of three titrations was 99.829% ± 0.029%
(k = 2). Standard sodium chlorate characterized by a metrologically
valid procedure was established. Japan Calibration Service System
(JCSS) under Japanese Measurement Act is a national measurement
standards provision scheme. Chlorate standard solutions have been
provided under JCSS via calibration laboratories. The supply of chlo-
rate standard solutions in solution-form widely allows all analysts to
obtain their reliable instrument analyses.
References
[1] World Health Organization, Guidelines for Drinking-Water Quality, 4th ed., WHO
Press, Geneva, 2011.
[2] American Public Health Association, American Water Works Association, Water
Environment Federation, Standard Methods for the Examination of Water and
Wastewater, 20th ed., American Public Health Association, Washington, D.C., 1999.
[3] M. Asami, N. Yoshida, K. Kosaka, K. Ohno, Y. Matsui, Contribution of tap water to
chlorate and perchlorate intake: a market basket study, Sci. Total Environ.
463−464 (2013) 199−208.
[4] D.J. van Wijk, S.G.M. Kroon, I.C.M. Garttener-Arends, Toxicity of chlorate and
chlorite to selected species of algae, bacteria, and fungi, Ecotoxicol. Environ. Saf. 40
(1998) 206−211.
[5] R.C. Anderson, S.A. Buckley, L.F. Kubena, L.H. Stanker, R.B. Harvey, D.J. Nisbet,
Bactericidal effect of sodium chlorate on Escherichia coli O157:H7 and Salmonella
typhimurium DT104 in rumen contents in vitro, J. Food Prot. 63 (2000)
1038−1042.
[6] Ministry of Health, Labour and Welfare, Water Quality Standard in Japanese Water
Supply Act, Ministry of Health, Labour and Welfare, Tokyo, 2003.
[7] K. Hiiro, G.J. Moody, J.D.R. Thomas, A chlorate ion-selective electrode based on a
poly(vinyl chloride)-matrix membrane, Talanta 22 (1975) 918−919.
[8] T. Chen, Spectrophotometric determination of microquantities of chlorate, chlorite,
hypochlorite, and chloride in perchlorate, Anal. Chem. 39 (1967) 804−813.
[9] S.G. Hosseini, S.M. Pourmortazavia, Kh. Gholivand, Spectrophotometric determi-
nation of chlorate ions in drinking water, Desalination 245 (2009) 298−305.
[10] K.G. Miller, G.E. Pacey, G. Gordon, Automated iodometric method for determina-
tion of trace chlorate ion using flow injection analysis, Anal. Chem. 57 (1985)
734−737.
[11] D.G. Themelis, D.W. Wood, G. Gordon, Determination of low concentrations of
chlorite and chlorate ions by using a flow-injection system, Anal. Chim. Acta 225
(1989) 437−441.
[12] O. Tue-Ngeun, J. Jakmunee, K. Grudpan, A novel stopped flow in-
jection−amperometric procedure for the determination of chlorate, Talanta 68
(2005) 459−464.
[13] T. Chuesaard, T. Wonganan, T. Wongchanapiboon, S. Liawruangrath, Reversed flow
injection spectrophotometric determination of chlorate, Talanta 79 (2009)
1181−1187.
[14] B. Nowack, U. Gunten, Determination of chlorate at low μg/l levels by ion-chro-
matography with postcolumn reaction, J. Chrom. A 849 (1999) 209−215.
[15] R. Michalski, Inorganic oxyhalide by-products in drinking water and ion chroma-
tographic determination methods, Pol. J. Environ. Stud. 14 (2005) 257–268.
[16] B. Zhu, Z. Zhong, J. Yao, Ion chromatographic determination of trace iodate,
chlorite, chlorate, bromide, bromate and nitrite in drinking water using suppressed
conductivity detection and visible detection, J. Chrom. A 1118 (2006) 106−110.
[17] B. Rao, P.B. Hatzinger, J.K. Boulke, N.C. Sturchio, B.J. Andraski, F.D. Eckardt,
W.A. Jackson, Natural chlorate in the environment: application of a new IC-ESI/
MS/MS method with a Cl18O3− internal standard, Environ. Sci. Technol. 44 (2010)
8429−8434.
[18] A.N. Pisarenko, B.D. Stanford, O. Quiñones, G.E. Pacey, G. Gordon, S.A. Snyder,
Rapid analysis of perchlorate, chlorate and bromate ions in concentrated sodium
hypochlorite solutions, Anal. Chim. Acta 659 (2010) 216−223.
[19] N. Wang, R.Q. Wang, Y. Zhu, A novel ion chromatography cycling-column-
switching system for the determination of low-level chlorate and nitrite in high salt
matrices, J. Hazard. Mater. 235−236 (2012) 123−127.
[20] The International Database for Certified Reference Materials, (COMAR) provided by
the Federal Institute for Materials Research and Testing (BAM), http://www.comar.
bam.de/, (2018) , Accessed date: 4 January 2018.
[21] National Institute of Standards and Technology (NIST), Standard reference mate-
rials (SRMs), https://www.nist.gov/srm/, (2018) , Accessed date: 4 January 2018.
[22] W. Richter, Primary methods of measurement in chemical analysis, Accred. Qual.
T. Asakai
Assur. 2 (1997) 354–359.
[23] T. Asakai, Y. Kakihara, Y. Kozuka, S. Hossaka, M. Murayamaa, T. Tanaka,
Evaluation of certified reference materials for oxidation-reduction titration by
precise coulometric titration and volumetric analysis, Anal. Chim. Acta 567 (2006)
269−276.
[24] T. Asakai, A. Hioki, Comparison of three electrochemical end-point detection
methods to assay potassium dichromate by coulometric titration, Accred. Qual.
Assur. 17 (2012) 45−52.
[25] T. Asakai, H. Hara, M. Murayama, T. Tanaka, Influence of AgCl precipitates on the
precipitation titration of sodium chloride by constant-current coulometry, Anal. Sci.
22 (2006) 1121−1124.
[26] A.C. Nixon, K.B. Krauskoff, The rate of reaction between chlorate and sulfur dioxide
in acid solution, J. Am. Chem. Soc. 54 (1932) 4606−4608.
[27] J. Halperin, H. Taube, The Transfer of Oxygen Atoms in Oxidation-Reduction
Reactions. III. The Reaction of Halogenates with Sulfite in Aqueous Solution, 74
(1952), pp. 375–380.
[28] E.H. Gleason, G. Mino, W.M. Thomas, Kinetics of the chlorate-sulfite reaction, J.
Phys. Chem. 61 (1957) 447−450.
[29] L. Szirovicza, The kinetics of the chlorate-bisulfite and chlorate-sulfite bisulfite
reaction systems, React. Kinet. Catal. Lett. 96 (2009) 311−317.
[30] L.C. Adam, G. Gordon, Direct and sequential potentiometric determination of
16
Microchemical Journal 142 (2018) 9–16
hypochlorite, chlorite, and chlorate ions when hypochlorite ion is present in large
excess, Anal. Chem. 67 (1995) 535−540.
[31] L.S. Villata, D.O. Mártire, A.L. Capparelli, The catalytic effect of MoV on the oxi-
dation of iodide by chlorate, J. Mol. Catal. A Chem. 123 (1997) 85−90.
[32] T. Asakai, A. Hioki, Investigation of iodine liberation process in redox titration of
potassium iodate with sodium thiosulfate, Anal. Chim. Acta 689 (2011) 34–38.
[33] M. Kubota, K. Kato, A. Hioki, H. Iijima, Y. Matsumoto, Development and supply
system of reference materials based on the measurement law in Japan, Accred.
Qual. Assur. 2 (1997) 130−136.
[34] T. Asakai, A. Hioki, SI traceable assay of periodate compounds, Accred. Qual. Assur.
19 (2014) 105−109.
[35] T. Asakai, A. Hioki, Potassium bromate assay by primary methods through iodine
liberation reaction, Anal. Methods 5 (2013) 6240–6245.
[36] T. Asakai, A. Hioki, Reliability in standardization of sodium thiosulfate with po-
tassium dichromate, Microchem. J. 123 (2015) 9−14.
[37] T. Asakai, A. Hioki, Precise coulometric titration of cerium(IV) as an oxidising agent
with electrogenerated iron(II) and reliability in cerium(IV) standardisation with
sodium thiosulfate, Anal. Methods 4 (2012) 3478–3483.
[38] ISO Guide 35, Reference Materials−General and Statistical Principles for
Certification, ISO, Geneva, 2006.