Analytica Chimica Acta 689 (2011) 34–38

Contents lists available at ScienceDirect

Analytica Chimica Acta

journal homepage: www.elsevier.com/locate/aca

Investigation of iodine liberation process in redox titration of potassium iodate

with sodium thiosulfate
Toshiaki Asakai ∗ , Akiharu Hioki
National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 3-9, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563,
Japan

a r t i c l e i n f o a b s t r a c t

Article history: Potassium iodate is often used as a reference material to standardize a sodium thiosulfate solution which
Received 15 November 2010 is a familiar titrant for redox titrations. In the standardization, iodine (triiodide) liberated by potassium
Received in revised form 12 January 2011 iodate in an acidic potassium iodide solution is titrated with a sodium thiosulfate solution. The iodine
Accepted 12 January 2011
liberation process is significantly affected by the amount of acid, that of potassium iodide added, the
Available online 19 January 2011
waiting time for the liberation, and light; therefore, the process plays a key role for the accuracy of
the titration results. Constant-voltage biamperometry with a modified dual platinum-chip electrode
Keywords:
was utilized to monitor the amount of liberated iodine under several liberation conditions. Coulometric
Coulometric titration
Oxidation–reduction titration
titration was utilized to determine the concentration of a sodium thiosulfate solution on an absolute basis.
Iodine liberation Potassium iodate was assayed by gravimetric titration with the sodium thiosulfate solution under several
Certified reference material iodine liberation conditions. The liberation process was discussed from the changes in the apparent assay
Sodium thiosulfate of potassium iodate. The information of the appropriate titration procedure obtained in the present study
Potassium iodate is useful for any analysts utilizing potassium iodate to standardize a thiosulfate solution.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction Germany according to the International Database for Certified Ref-

Sodium thiosulfate (Na2 S2 O3 ) is widely used in titrimetric anal-
ysis and is often used as a central material for iodometry [reduction
of iodine (I2 )] [1–4]. In general, the concentration of Na2 S2 O3 in
a redox titration is determined based on the assay of potassium
iodate (KIO3 ) or potassium dichromate (K2 Cr2 O7 ) according to the
following reactions [reactions (1)–(3)] [1–4].
KIO3 + 5KI + 3H2 SO4 → 3K2 SO4 + 3H2 O + 3I2
K2 Cr2 O7 + 6KI + 7H2 SO4 → Cr2 (SO4 )3 + 4K2 SO4 + 7H2 O + 3I2
2Na2 S2 O3 + I2 → 2NaI + Na2 S4 O6
In the reaction (1) or (2), the I2 (triiodide, I3 −)
liberated by
KIO3 or K2 Cr2 O7 in an acidic potassium iodide (KI) solution can
be titrated with a Na2 S2 O3 solution to determine the concen-
tration of the Na2 S2 O3 solution. In literature, the availability of
KIO3 for the titration was discussed and it was recommended
as a primary standard [1,5]; however, there are only two certi-
fied reference materials (CRMs) of high purity KIO3 in Japan and
∗ Corresponding author. Tel.: +81 29 861 6881; fax: +81 29 861 6890.
E-mail address: t-asakai@aist.go.jp (T. Asakai).
erence Materials (COMAR) as of September 2010 [6–8], few reports
on the KIO3 assay [9–12] and on the Na2 S2 O3 assay by coulo-
metric titration [10–14]. In those past reports [10–12], KIO3 was
assayed with Na2 S2 O3 whose concentration was determined by
coulometric titration with electrogenerated I2 ; that is reverse to
a usual redox volumetric titration in which KIO3 as a reference
material is used to standardize Na2 S2 O3 . The accuracy of the coulo-
metric titration for Na2 S2 O3 was discussed in the reports and the
(1) repeatability for the assay of KIO3 was sufficient; however, the
iodine liberation processes were insufficiently investigated. Ma did
not mention the validity of the adopted weak acidic condition for
(2) the liberation in his paper [10]. One of the authors and Tanaka
et al. [11,12] adopted the condition similar to the Japanese Indus-
(3) trial Standard (JIS) [3,15]. Various conditions for the liberation of
I2 have been used as shown in Table 1 [1–3,10–12,15]. The lib-
eration of I2 is significantly affected by the amount of acid, that
of KI added, the waiting time for liberation and light; therefore,
the liberation process is essential to the accuracy of the titration
results.
In the present study, we utilized constant-voltage biamper-
ometry (a dead stop method) [16] to monitor the amount of I2
generation under several liberation conditions and to examine the
sufficient conditions for I2 generation. This method was often used
for an electrical end-point determination in the reactions involv-
ing I2 [10–13,16–20]. To investigate the I2 liberation process more
accurately, we assayed KIO3 under several liberation conditions

0003-2670/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2011.01.021
 T. Asakai, A. Hioki / Analytica Chimica Acta 689 (2011) 34–38 35

Table 1
Conditions for the liberation of iodine.

Reference KIO3 Water to dissolve KI Acid I2 liberation time

−1
[1] 0.12–0.17 g 25 mL 2g 10 mL of 1 mol L HCl 0 min
[2] 0.14 g 50 mL 3g 1 mL of H2 SO4 3 min
[3] 0.4–0.5 g 100 mL 5g 5 mL of 9 mol L−1 H2 SO4 5 min
[3] 0.09–0.11 g as an aliquot of a 100 mL 2g 2 mL of 9 mol L−1 H2 SO4 5 min
KIO3 concentrated solution
[3] 0.0075–0.01 g as an aliquot of a 100 mL 1g 2 mL of 9 mol L−1 H2 SO4 5 min
KIO3 concentrated solution
[10] 0.15 g 90 mL of 0.5 mol L−1 CH3 COOH– 2g 15 min
CH3 COONa (pH 4.5)
−1
[11] 0.15 g 150 mL 2g 5 mL of 3 mol L H2 SO4 10 min
[12] 0.15 g 25 mL 2g 5 mL of 3 mol L−1 H2 SO4 5 min
[15] 0.14–0.16 g 100 mL 2.00 g ± 0.05 g 5 mL of 3 mol L−1 H2 SO4 10 min

based on the procedure which was used for the assay of KIO3 in 3. Results and discussion
the past reports [10–12]. The liberation processes are clearly dis-
cussed with high accuracy from the changes in the apparent assay 3.1. Determination of Na2 S2 O3 by coulometric titration and
of KIO3 . uncertainty estimation

2. Experimental The major uncertainty sources for Na2 S2 O3 by coulomet-

2.1. Reagents, apparatus and procedure of constant-voltage
biamperometry
High purity KIO3 was obtained from Wako Pure Chemical Indus-
tries, Ltd., Osaka, Japan. Analytical reagent grade KI and H2 SO4 were
used for I2 liberation.
A DC current source (type 7651, Yokogawa Electric Corpora-
tion, Tokyo, Japan) and a digital multimeter (type 7562, Yokogawa
Electric Corporation) with a modified dual platinum-chip electrode
(each platinum chip: 0.5 mm  × 0.5 mm long, placed 2 cm apart)
were used for constant-voltage biamperometry. Constant voltage
was applied between the platinum pair, and the current was moni-
tored. Using the method, the amounts of liberated I2 under several
conditions were measured.
2.2. Reagents, apparatus and procedure of coulometric titration
and gravimetric titration
The KIO3 here was the same as that in the constant-
voltage biamperometry (vide supra). The following constants
were used for the material: molar mass 214.001 g mol−1 [21]
and density 3.89 g cm−3 [22]. The Faraday constant used was
96 485.339 9 C mol−1 [23]. Buoyancy corrections were always
applied.
The instruments used for coulometric titration were the same
as those described previously [24]. The coulometric titration of
Na2 S2 O3 and the gravimetric titration of KIO3 with Na2 S2 O3 were
also presented in detail in the previous report [11]. Reagents and
electrodes used for the coulometric titration are briefly described
here. The salt bridge was 3% (mass fraction) agar gel contain-
ing 3% (mass fraction) sodium sulfate. The catholyte consisted
of 42.6 g L−1 disodium hydrogen phosphate and 27.2 g L−1 potas-
sium dihydrogen phosphate, and the anolyte consisted of the
catholyte containing 16 g L−1 KI. The electrodes used were a plat-
inum plate (40 mm wide × 25 mm long, supporting rod: 1.5 mm
 × 150 mm long) as a working electrode and a platinum wire
(1.5 mm  × 300 mm long) as a counter electrode. A weighed plas-
tic syringe with a PEEK (polyetheretherketone) needle was used
for gravimetric titration and also for solution-sample introduction
to the coulometric titration cell. The end-point determination used
in both coulometric titration and gravimetric one was constant-
voltage biamperometry (applied voltage: 150 mV) using a dual
platinum-plate electrode (each 5 mm × 5 mm, type M-512, Kyoto
Electronics Manufacturing Co., Ltd., Kyoto, Japan).
ric titration are the current efficiency and the diffusion loss of
Na2 S2 O3 from the working-electrode chamber to the counter-
electrode one. Marinenko et al. investigated the current efficiency
of I2 electrogeneration in a phosphate buffer containing KI
[18]. We adopted the conditions under which the 100% cur-
rent efficiency was substantially achieved according to them.
To examine the current efficiency and the sample diffusion
loss using our own coulometric titration system, we measured
ca. 200 mmol kg−1 Na2 S2 O3 with different applied electroly-
sis currents (50 mA and 100 mA) and different sample masses
(3 g, 6 g and 9 g). The measured concentrations of the Na2 S2 O3
solution (ca. 6 g) electrolyzed with 50 mA and 100 mA were
195.737 mmol kg−1 (RSD 0.005%, n = 3) and 195.743 mmol kg−1
(RSD 0.005%, n = 3), respectively (‘RSD’ means ‘relative stan-
dard deviation’, and ‘n’ is number of measurements under
a repeating condition). In addition, the results for different
amounts of the Na2 S2 O3 solution electrolyzed with 100 mA were
195.739 mmol kg−1 (ca. 3 g, RSD 0.004%, n = 4), 195.741 mmol kg−1
(ca. 6 g, RSD 0.005%, n = 4) and 195.739 mmol kg−1 (ca. 9 g, RSD
0.002%, n = 4). There were no significant dependencies of the con-
centration on the electrolysis current and the mass of sample
solution; therefore, we concluded that the assays had no significant
biases.
Applying short pulses of a constant current (typically 10 mA,
1 s) and measuring an indicator current were repeated to draw a
titration curve near the end point. The measured concentrations
of Na2 S2 O3 under applying different number of the short constant
current (4–304 times) were in good agreement with each other
within the repeatability (RSD 0.002%, n = 15; the difference between
maximum and minimum values was 0.01%). This fact confirmed
that there was no influence of non-Faradaic current and that the
current efficiency of the short pulses of constant current was sub-
stantially 100%.
The contributions to the combined standard uncertainty of
the Na2 S2 O3 solution (ca. 6 g of ca. 200 mmol kg−1 ) were as
follows (the number in each parenthesis indicates the rela-
tive standard uncertainty): repeatability (0.0014%, RSD of the
mean, n = 7), Faraday constant (0.000 002 5%), standard resistor
(0.000 22%), timer (0.000 05%), switching performance (0.000 12%),
voltmeter (0.000 15%) and weighing (sensitivity and linear-
ity: 0.000 96%, and other possible bias: 0.000 84%). Finally, the
combined standard uncertainty was 0.0019% relative and the
expanded uncertainty with a coverage factor k = 2 was 0.004% rel-
ative.
36 T. Asakai, A. Hioki / Analytica Chimica Acta 689 (2011) 34–38
Fig. 1. Linearity of constant-voltage biamperometric detection. : a dual Pt-chip
electrode (each 0.5 mm  × 0.5 mm long); 100 mL of water, 5 g of KI, 2 mL of 9 mol L−1
H2 SO4 , constant-voltage 500 mV, stirring at 900 rpm. : a dual Pt-plate electrode
(each 5 mm × 5 mm); the same condition as for the dual Pt-chip electrode.
3.2. Linearity of constant-voltage biamperometry detection
In constant-voltage biamperometry, a constant voltage is
applied between twin platinum plates of the electrode and the cur-
rent change is measured. The current under a sufficiently small
voltage (e.g., 150 mV, where water is not electrolyzed) is nearly
zero in the presence of K+ , I− , and IO3 − in the absence of I3 − . But
the current easily flows in the presence of both I- and I3 - through
the reaction 3I− ↔ I3 − + 2e− on each platinum surface. Constant-
voltage biamperometry is a sensitive method for the detection of I2 ;
however, the current under a high concentration of I2 could be not
proportional to the amount of liberated I2 because the electrochem-
ical reaction 3I− ↔ I3 − + 2e− is diffusion-controlled. Therefore, we
used a small platinum–chip pair and obtained wider linearity
instead of higher sensitivity.
The linearity between the amount of I2 and the current was
examined by adding I2 as a solid to a KI solution as shown in Fig. 1.
While the linearity using a dual platinum-plate electrode (each
5 mm × 5 mm) was poor, a wide linearity of the indicator current
was obtained using a small dual platinum–chip pair (each 0.5 mm
 × 0.5 mm long). To improve the linearity, relatively higher volt-
age (500 mV) and higher stirring rotation rate [900 rpm] were used.
The current had good proportionality to the amount of liberated I2
up to ca. 0.8 g at least. Therefore, the chip pair made it possible to
monitor the amount of generated I2 corresponding to 0.15 g of KIO3
through the reaction (1).
3.3. Examination of I2 liberation by constant-voltage
biamperometry
In the reaction (1), 0.15 g of KIO3 require a minimum of ca. 0.58 g
of KI and ca. 0.23 mL of 9 mol L−1 H2 SO4 , and liberate ca. 0.53 g of I2 .
Fig. 2 shows changes in the indicator current by constant-voltage
biamperometry after acid addition; the indicator current is pro-
portional to the amount of I2 liberation. Under the condition using
1 mL of 9 mol L−1 H2 SO4 and 1 g of KI, the lack of I− in the solu-
tion led to the deposition of solid I2 on the electrodes and in the
solution, and the indicator current drastically decreased after the
Fig. 2. I2 liberation process monitored by constant-voltage biamperometry for
0.15 g of KIO3 using a dual Pt-chip electrode (applied constant-voltage 500 mV), stir-
ring at 900 rpm. (a) 100 mL of water, 1 g, 2 g, 3 g, 4 g and 5 g of KI, 1 mL of 9 mol L−1
H2 SO4 , (b) 100 mL of water, 3 g of KI, 0.15 mL, 0.25 mL, 0.5 mL, 1 mL, 2 mL and 3 mL
of 9 mol L−1 H2 SO4 .
initial increase. Using 1 mL of 9 mol L−1 H2 SO4 and 2 g of KI, the cur-
rent gradually decreased with the waiting time; from this fact, it
was inferred that the generated I2 evaporated because the concen-
tration of I− was not enough to keep all I2 in the solution. Brown
color was observed on the lid over the beaker after several runs.
These conditions were apparently inappropriate; however, those
could be appropriate because I− is resupplied through the reaction
(3) between Na2 S2 O3 and I2 . Regarding the amount of 9 mol L−1
H2 SO4 , the liberation of I2 was not complete under the condition
using 0.15 mL of 9 mol L−1 H2 SO4 because the volume of 9 mol L−1
H2 SO4 was theoretically short [reaction (1)] for 0.15 g of KIO3 . There
were apparently no problems under the other conditions in Fig. 2.
The indicator current instantaneously rose (within 1–2 s) using
sufficient amounts of 9 mol L−1 H2 SO4 and KI. Judging from Fig. 2,
the titration was expected to completely proceed using both more
than 3 g of KI with 1 mL of 9 mol L−1 H2 SO4 and 3 g of KI with more
than 0.25 mL of 9 mol L−1 H2 SO4 . In addition, it was recommended
to immediately titrate after I2 generation to minimize both the
vaporization of I2 and the influence of light.
3.4. Background caused by oxidation of iodide ions
End-point determinations in both coulometric titration and
gravimetric one were done by constant-voltage biamperometry,
whose instrument was the same as that used in the investiga-
tion of I2 liberation except for the dual platinum-plate electrode
(each 5 mm × 5 mm) and the voltage of 150 mV. The electrode
showed higher sensitivity than the modified dual platinum–chip
electrode. In gravimetric titration, the indicator current proportion-
ally decreased with the titration proceeding near the end point and
the current was kept at zero amperes after the end point. The end
point was the intersection between the linear regression curve of
indicator currents vs. the amounts of Na2 S2 O3 used and the baseline
(0 ␮A).
Using the constant-voltage biamperometry to detect I2 , the
influence of air oxidation of iodide ions was examined under sev-
eral conditions and its contribution to the uncertainty of the KIO3
assay was estimated. Fig. 3 illustrates changes in background cur-
rents resulting from air oxidation of iodide ions. The changes in the
 T. Asakai, A. Hioki / Analytica Chimica Acta 689 (2011) 34–38 37

Fig. 3. Increase of background current after acid addition 100 mL of water, 1–5 mL
of 9 mol L−1 H2 SO4 , 3 g of KI, without KIO3 . The currents were substantially at zero
amperes using 1 mL of 9 mol L−1 H2 SO4 under both conditions of bright and dark.
indicator currents were monitored under the conditions of some
different 9 mol L−1 H2 SO4 concentrations with ca. 3 g of KI in both
the presence and the absence of room light. The current exponen-
tially increased in all cases in a bright room and proportionally
increased in a dark room. The larger amount of 9 mol L−1 H2 SO4
used, the larger increasing rate of the current under each condition
of bright and dark. The currents were below 0.06 ␮A using 1 mL of
9 mol L−1 H2 SO4 at 5 min under both conditions of bright and dark.
The current 0.6 ␮A corresponds to 0.005% of 0.15 g of KIO3 under
the adopted measurement condition. The titration was practically
completed in 2 min after I2 generation; therefore, the background
current did not cause any error. The larger background current was
caused by the larger amount of KI used. To be concluded, the most
appropriate way was to finish a titration within a couple of minutes
in a dark room using smaller amounts of KI and 9 mol L−1 H2 SO4 if
the amounts are enough to completely generate I2 from KIO3 .
Fig. 4. Dependency of the apparent KIO3 assay on the I2 liberation time (100 mL of
water, 0.15 g of KIO3 , 3 g of KI and 1 mL of 9 mol L−1 H2 SO4 ). The assay was based on
the concentration of Na2 S2 O3 standardized by coulometric titration. For the equa-
tions in the Figure, x indicates the liberation time (min) and y indicates the apparent
purity (mass fraction, %). Each data point under the same condition was measured
on independent runs to obtain the repeatability. : stoppered beaker during the
liberation, : unstoppered beaker during the liberation.
KI. There is no contradiction between the results of Figs. 2 and 5.
Fig. 2 apparently indicates that using 1–2 g of KI was not enough to
completely generate I2 ; however, the results shown in Fig. 5 were
relatively close to 99.97%. The unexpected good results were caused
probably because iodide ions were sufficiently resupplied by the
reaction between Na2 S2 O3 and I2 generated by KIO3 [reaction (3)].
In the case using 1–2 g of KI, the apparent assays of KIO3 titrated at
5 min after starting I2 generation were lower than those (Fig. 5) of
KIO3 titrated immediately; probably this fact was caused by loss of

3.5. Examination of I2 liberation by coulometric titration and

gravimetric titration

Gravimetric titration was performed to assay KIO3 in a dark

room using a Na2 S2 O3 solution standardized by coulometric titra-
tion. The dependencies of the apparent KIO3 assay on the liberation
time of I2 are shown in Fig. 4, where 100 mL of water, 0.15 g
of KIO3 , 3 g of KI, 1 mL of 9 mol L−1 H2 SO4 and a 200 mL tall
beaker were used. The apparent assay of KIO3 with an unstop-
pered beaker proportionally decreased during the I2 liberation due
to the volatilization of generated I2 . Shorter times taken for the I2
liberation and for the titration with a Na2 S2 O3 solution were better.
The dependencies of the apparent assay of KIO3 on the amounts
of 9 mol L−1 H2 SO4 and KI used are shown in Fig. 5, where the gravi-
metric titrations were carried out immediately after I2 liberation
starting. The apparent assays of KIO3 were in the 99.96–99.97%
(mass fraction) range using 0.25–5 mL of 9 mol L−1 H2 SO4 and 3 g
of KI. The apparent assay using 0.15 mL of 9 mol L−1 H2 SO4 and 3 g
of KI was, however, about 66%. It agreed with the observation in
Fig. 2 and was natural because 0.15 mL of 9 mol L−1 H2 SO4 was Fig. 5. Dependency of the apparent KIO3 assay on the amount of KI and 9 mol L−1
H2 SO4 used. Each data point under the same condition was measured on indepen-
stoichiometrically short in the reaction (1) for 0.15 g of KIO3 . The
dent runs to obtain the repeatability. : dependency on the amount of 9 mol L−1
apparent assays of KIO3 were in the 99.96–99.97% range using 1 mL H2 SO4 with 3 g of KI, ×: dependency on the amount of KI with 1 mL of 9 mol L−1
of 9 mol L−1 H2 SO4 and 3–5 g of KI, but were lower using 1–2 g of H2 SO4 .
38 T. Asakai, A. Hioki / Analytica Chimica Acta 689 (2011) 34–38
slowly generated I2 from the solution. In conclusion, the liberation
of I2 from 0.15 g of KIO3 dissolved in 100 mL of water should be
carried out using up to 5 mL more than 0.5 mL of 9 mol L−1 H2 SO4
at least and 3 g of KI. The 0.25 mL aliquot of 9 mol L−1 H2 SO4 prac-
tically raised no problem but the condition is not recommended
because the theoretical amount required is 0.23 mL. The titration
of KIO3 with a Na2 S2 O3 solution should be done immediately after
I2 liberation to avoid the influence of light and the volatilization of
I2 and air-oxidation of I− .
The uncertainty for the KIO3 assay can be calculated from the
uncertainties of the repeatability, the weighings of both KIO3 and a
Na2 S2 O3 solution, the determination of the Na2 S2 O3 concentration,
the molar mass of KIO3 and the possible bias caused by I2 liber-
ation. The approximate figures of relative standard uncertainties
are as follows: repeatability 0.005% (RSD based on the 20 measure-
ments from 10 different bottles, 2 measurements in each bottle),
the both weighings 0.003%, the concentration of Na2 S2 O3 0.004%
and the molar mass of KIO3 0.001%. An estimation of the bias caused
by I2 liberation was especially important. Fig. 4 indicates that the
amount of I2 loss with an unstoppered beaker was 0.0174% relative
a minute. Most of the liberated I2 was titrated within 30 s, and a
whole titration was completed in 2 min; therefore, the bias for I2
loss fell much smaller than half of 0.0174%. On the other hand, the
influence of light was negligible since the increase of background
caused by light was less than 0.0005% in 2 min (Section 3.4 and
Fig. 3).
3.6. Drying conditions for KIO3
A change in the mass of KIO3 (ca. 3 g) by weighing before and
after drying was examined to investigate the instablity of the mate-
rial. The change in each mass under drying at 50 ◦ C, 130 ◦ C and
180 ◦ C for 6 h was within 0.003%. A change in the mass of KIO3 (ca.
3 g) placed under a humid condition for 6 h was examined to inves-
tigate the hygroscopicity. The observed change was within 0.001%.
In addition, there was no dependency of the assays of KIO3 on the
drying temperatures from room temperature to 180 ◦ C, judging
from the results of the gravimetric titration with Na2 S2 O3 stan-
dardized with coulometric titration. Therefore, it was concluded
that KIO3 was very stable and did not have hygroscopicity.
3.7. Consideration for procedures in Japanese Industrial Standard
The methods to prepare three different concentrations
of Na2 S2 O3 (ca. 10 mmol kg−1 , ca. 100 mmol kg−1 and ca.
500 mmol kg−1 ), which are standardized with KIO3 (Table 1), are
defined in JIS K 8001 [3]. We assayed KIO3 by gravimetric titration
with a Na2 S2 O3 solution whose concentration was determined by
coulometric titration under the appropriate condition described
above. The JIS method using the KIO3 as a standard was vali-
dated by comparing the concentration of Na2 S2 O3 by the method
with that directly determined by coulometric titration. Conse-
quently, the results indicated that the concentration of Na2 S2 O3
(ca. 10 mmol kg−1 ) by the JIS method under room light was ca. 1.7%
lower than the concentration determined by coulometric titration.
This difference resulted from the I2 liberation by the light dur-
ing the titration of the JIS method. On the other hand, regarding
the Na2 S2 O3 solution (ca. 10 mmol kg−1 ), the modified JIS method
under the appropriate condition of immidiate titration after I2 gen-
eration in a dark room gave no significant difference from the
coulometric titration (within ±0.04% relative). The results for the
other two concentrations by the modified JIS method under the
condition of no delay after I2 generation in a dark room were consis-
tent with that determined by coulometric titration within ±0.02%
relative, and the concentrations by the JIS method were within
±0.1% relative.
4. Conclusions
Coulometric titration and gravimetric titration were performed
to investigate the I2 liberation process in the redox titration of KIO3
with a Na2 S2 O3 solution. Constant-voltage biamperometry with a
modified dual platinum–chip electrode was used to detect a wide-
range concentration of liberated I2 under several concentrations
of KI and H2 SO4 , and the appropriate liberation conditions were
found. The I2 liberation process was evaluated more accurately
from changes in the apparent assay of KIO3 by gravimetric titraion
with a Na2 S2 O3 solution standardized by coulometric titration on
an absolute basis. In the most appropriate procedure, KIO3 (0.15 g)
was dissolved into 100 mL of water, then more than 3 g of KI and
0.5 mL of 9 mol L−1 H2 SO4 were added, and immediately the solu-
tion was titrated with a Na2 S2 O3 solution. No waiting time for the I2
liberation was necessary and a room light influence was negligible
under quick operation. In addition, the JIS method was evaluated by
comparing the concentrations of a Na2 S2 O3 solution determined by
the JIS method with that by coulometric titration. The information
of the appropriate titration procedure obtained in the present study
is useful for any analysts utilizing KIO3 to standardize a Na2 S2 O3
solution.
References
[1] I.M. Kolthoff, R. Belcher, Volumetric Analysis Volume III Titration methods:
Oxidation–Reduction Reactions, Interscience Publications Inc., New York, 1957.
[2] American Chemical Society, ACS—Specifications Reagent Chemicals, 9th ed.,
Oxford University Press, New York, 2000.
[3] JIS K 8001, General rule for test methods of reagents, Japanese Industrial Stan-
dards Committee, Tokyo, 2009 (in Japanese).
[4] T. Asakai, M. Murayama, Accred. Qual. Assur. 13 (2008) 351–360.
[5] V.A. Stenger, Anal. Chem. 23 (1951) 1540–1543.
[6] The International Database for Certified Reference Materials (COMAR) provided
by the Federal Institute for Materials Research and Testing (BAM).
[7] R. Pradel, T. Steiger, H. Klich, Accred. Qual. Assur. 8 (2003) 317–318.
[8] R. Pradel, T. Steiger, Accred. Qual. Assur. 12 (2007) 265–268.
[9] T. Asakai, Y. Kakihara, Y. Kozuka, S. Hossaka, M. Murayama, T. Tanaka, Anal.
Chim. Acta 567 (2006) 269–276.
[10] L. Ma, Accred. Qual. Assur. 7 (2002) 163–167.
[11] T. Asakai, M. Murayama, T. Tanaka, Talanta 73 (2007) 346–351.
[12] T. Tanaka, H. Hayashi, Y. Komiya, H. Nabekawa, H. Hayashi, Bunseki Kagaku 56
(2007) 327–332 (in Japanese).
[13] K. Rowley, E.H. Swift, Anal. Chem. 26 (1954) 373–375.
[14] T.R. Markova, Y.I. Tur’yan, Sov. Electrochem. 22 (1986) 505.
[15] JIS K 8005, Reference Materials for Volumetric Analysis, Japanese Industrial
Standards Committee, Tokyo, 2006 (in Japanese).
[16] C.W. Foulk, A.T. Bawden, J. Amer. Chem. Soc. 48 (1926) 2045–2051.
[17] J.J. Lingane, A.J. Bard, Anal. Chim. Acta 16 (1957) 271–273.
[18] G. Marinenko, J.K. Taylor, Anal. Chem. 39 (1967) 1568–1571.
[19] A. Hioki, M. Kubota, A. Kawase, Analyst 117 (1992) 997–1001.
[20] W.J. Ramsey, P.S. Farrington, E.H. Swift, Anal. Chem. 22 (1950) 332–335.
[21] IUPAC, Pure Appl. Chem. 78 (2006) 2051–2066.
[22] D.R. Lide, CRC Handbook of Chemistry and Physics 2005–2006, 86th ed., CRC
Press, Boca Raton, 2005.
[23] P.J. Mohr, B.N. Taylor, D.B. Newell, Rev. Mod. Phys. 80 (2008) 633–730.
[24] T. Asakai, A. Hioki, Accred. Qual. Assur. 15 (2010) 391–399.