Talanta 73 (2007) 346351

Precise coulometric titration of sodium thiosulfate and development of potassium iodate as a redox standard
Toshiaki Asakai a, , Mariko Murayama a , Tatsuhiko Tanaka b
a b

National Institute of Technology and Evaluation, 2-49-10, Nishihara, Shibuya-ku, Tokyo 151-0066, Japan Faculty of Engineering, Tokyo University of Science, 13, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan Received 14 February 2007; received in revised form 23 March 2007; accepted 23 March 2007 Available online 1 April 2007

Abstract In this paper, we determine the effective purity of potassium iodate as a redox standard with a certied value linked to the international system of units (SI units). Concentration measurement of sodium thiosulfate solution was performed by precise coulometric titration with electrogenerated iodine, and an assay of potassium iodate was carried out by gravimetric titration based on the reductometric factor of sodium thiosulfate assigned by coulometry. The accuracy of the coulometric titration method was evaluated by examining the current efciency of iodine electrogeneration, stability of sodium thiosulfate solutions and dependence on the amount of sodium thiosulfate solution used. The measurement procedure for gravimetric titration of potassium iodate with sodium thiosulfate was validated based on determination of a reference material of known purity (potassium dichromate determined by coulometry with electrogenerated ferrous ions) using the same gravimetric method. Solutions of 0.2 and 0.5 mol/L sodium thiosulfate were stable over 17 days without stabilizer. Investigation of the dependency of titration results on the amount of sodium thiosulfate solution used showed no signicant effects, no evidence of diffusion of the sample, and no effect of contamination appearing during the experiment. Precise coulometric titration of sodium thiosulfate achieved a relative standard deviation of less than 0.005% under repeating conditions (six measurements). For gravimetric titration, the results obtained for the effective purity of potassium dichromate were sufciently close to its certied value to allow conrmation of the validity of the gravimetric titration was conrmed. The relative standard deviation of gravimetric titration for potassium iodate was less than 0.011% (nine measurements), and a redox standard with a certied value linked to SI units was developed. 2007 Elsevier B.V. All rights reserved.
Keywords: Constant-current coulometry; Stoichiometric standards; Sodium thiosulfate; Potassium dichromate; Potassium iodate; Certied reference material

1. Introduction High reliability in reference materials has been rapidly increasing in importance owing to recent advances in R&D and industrial activities requiring highly reliable analytical data. Furthermore, it is essential that there is access to accurate and global reference materials that have traceability to the international system of units (SI units) or are in compliance with ISO guides, because mutual recognition and laboratory accreditation based on the International Organization for Standardization/International Electrotechnical Commission (ISO/IEC) 17025 quality system are becoming increasingly

Corresponding author. Tel.: +81 3 3481 1921; fax: +81 3 3481 2900. E-mail address: asakai-toshiaki@nite.go.jp (T. Asakai).

common, with the aim of eliminating technical barriers to international trade. Titrimetric analysis is one of the most fundamental and precise methods for determination of a constituent based on the effective purity of reference materials for stoichiometric analysis. It is used in neutralization, redox, chelatometric, and precipitation titration processes. In Japan, eleven materials are listed as standard materials for volumetric or other analysis in the Japanese Industrial Standard (JIS K 8005) [1], and are referred to in more than 300 Japanese industrial standards, and other standards such as the Japanese Pharmacopoeia. Of these, potassium dichromate (K2 Cr2 O7 ) and potassium iodate (KIO3 ) are particularly important in stoichiometric analysis by redox reaction. K2 Cr2 O7 is extremely stable and easily puried, can be used for direct titration of ions such as S2 O3 2 or Fe2+ , and is recommended as a primary standard in various countries [24]. Reports

0039-9140/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.talanta.2007.03.052

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on coulometric titration of K2 Cr2 O7 [510] and an investigation of drying conditions [10,11] are available, and a comparison of the certied values of reference materials obtained from different laboratories in different countries has been carried out in order to validate reliability [12]. Another useful material is KIO3 , which is used for direct titration with S2 O3 2 , Fe2+ , I , etc. It is also recommended as a primary standard [24]. Iodimetry and coulometric iodimetry with electrogenerated iodine are sensitive and useful methods for standardization of redox standards [2,4,13]. Determination of arsenious oxide and antimony were studied by coulometric iodimetry, and electrical end-point determination for iodimetry was investigated [1418]; however, there are few reports of accurate determination of purity of KIO3 . Tuthill et al. reported an assay of KIO3 by comparison with arsenic trioxide, and achieved a precision of 0.04% at a 95% condence level [19]. The discussion of uncertainty, SI unit traceability and method validation, which has been gaining importance in recent years, is interesting. Ma [20] reported the determination of KIO3 using sodium thiosulfate (Na2 S2 O3 ) assigned by coulometry with electrogenerated iodine. Excess Na2 S2 O3 including KIO3 was back-titrated in the coulometric cell with a buffer solution (pH = 4.5); however, in terms of method validation, in such areas as dependency on sample mass, solution stability, current density and comparison among materials, this investigation was insufcient. This paper describes an accurate measurement procedure for KIO3 using a Na2 S2 O3 solution whose effective concentration is determined by coulometry. For validation of the coulometric method, we determined the uctuation in pH value in the coulometric cell during the experiment, the current efciency of iodine electrogeneration, the stability of Na2 S2 O3 solutions, and dependence on the amount of the sample solution used. In addition, the gravimetric titration procedure between Na2 S2 O3 and KIO3 was validated by conducting measurements using K2 Cr2 O7 of known purity, determined by coulometry. 2. Experimental 2.1. Apparatus (coulometric titration) The automated coulometric system comprised a coulometric titration cell, electrolysis unit, indicating unit, and PC/AT-based controlling system (written in LabVIEW ), which is illustrated in Fig. 1. The electrolysis unit comprised a 6181C Model2400 constant current source (Keithley Instruments Inc., OH, USA), a custom-built timer and switching circuit (Taiyo Corp., Tokyo, Japan), Type-1794 standard resistors (10 and 100 : Yokogawa Electric Corporation, Tokyo, Japan), and a Type1281 voltmeter (Wavetek Ltd., CA, USA). The resistors used were chosen to be appropriate for different applied currents. The value of the applied current was calculated using a voltmeter and standard resistors connected in series based on Ohms law. The working electrode was platinum foil (25 mm 40 mm) and the cathode was a coiled platinum wire (1.2 120 mm). The indicating unit, which was used as an end-point detector, comprised a Type-7651 voltage source (Yokogawa), a Type-7562

Fig. 1. Schematic diagram of the automated coulometric system.

ampere meter (Yokogawa), and a Type-512 PtPt indicating electrode (two plates 5 mm 5 mm: Kyoto Electronics Manufacturing Co., Ltd., Kyoto, Japan). The end-point was detected by a dead-stop method with an applied voltage of 150 mV between two Pt plates. The same end-point determination method was used for gravimetric titration of K2 Cr2 O7 /Na2 S2 O3 and KIO3 /Na2 S2 O3 . 2.2. Chemicals Analytical reagent-grade chemicals were used unless otherwise stated. The salt bridge in the coulometric cell consisted of 100 mL of 33 g/L sodium sulfate containing 3% agar gel, and was prepared in advance. The composition of the catholyte was 0.05 mol/L potassium dihydrogen phosphate and 0.05 mol/L disodium hydrogen phosphate. The anolyte consisted of 0.05 mol/L potassium dihydrogen phosphate, 0.05 mol/L disodium hydrogen phosphate and 0.1 mol/L potassium iodide (pH about 6.8). K2 Cr2 O7 (used for gravimetric method validation) and KIO3 (for determination) were obtained from Yanagishima Pharmaceutical Co., Ltd. (Tokyo, Japan), and were compliant with JIS K 8005 (Table 1); the former was the same material used in previous research [12]. The drying conditions used were in accordance with the instructions in JIS K 8005; K2 Cr2 O7 was crushed, dried at 150 C for 1 h, and cooled in a desiccator with anhydrous magnesium perchlorate for 1 h. KIO3 was crushed, dried at 130 C for 2 h, and cooled in a desiccator with anhydrous magnesium perchlorate for 1 h. The molar mass and density of K2 Cr2 O7 were 294.1846 g/mol (K: 39.0983(1), Cr: 51.9961(6), O: 15.9994(3)) and 2.676 g/cm3 ; those of KIO3 were 214.00097 g/mol (K: 39.0983(1), I: 126.90447(3), O: 15.9994(3)) and 3.89 g/cm3 [21]. The density of the Na2 S2 O3 solution was measured, and buoyancy corrections were applied for each sample and solution.

348 Table 1 Specications of K2 Cr2 O7 and KIO3 in JIS K 8005 K2 ,Cr2 O7 Assay Insoluble matter Chloride (Cl) Sulfate (SO4 ) Sodium (Na) Calcium (Ca) Iron (Fe) pH (50 g/L at 25 C) Chloride and bromide (as Cl) Iodide (I) Nitrate (NO3 ) Cupper (Cu) Lead (Pb) Ammonium (NH4 ) 99.98% K2 Cr2 O7 2.0 g in 30 ml of water 5 ppm 0.003% 0.01% 0.002% 2 ppm

T. Asakai et al. / Talanta 73 (2007) 346351

KIO3 99.95% KIO3 1.0 g in 20 ml of water 0.001% 0.005% 1 ppm 5.08.0 0.001% 2 ppm 5 ppm 1 ppm 1 ppm 5 ppm

2.3. Procedure (pH conditions and current efciency) Na2 S2 O3 is smoothly oxidized by I2 between pH 5 and pH 9 (reaction (1)) [2,4,22]: 2Na2 S2 O3 + I2 2NaI + Na2 S4 O6 (1)

porting electrolyte. In the main titration, 39 g of 0.2 mol/L Na2 S2 O3 solution, which was weighed with a resolution of 10 g using a GastightTM syringe with a needle made of peak and to which a buoyancy correction was applied, was titrated using a large constant current (100 mA) to about 30 mC before the end-point. The redox assay was calculated from experimental electric charge, the sample mass, and the Faraday constant (96485.3383(83) C/mol) [23]. The determination of the effective purity of KIO3 has two steps: determination of the reductometric factor of Na2 S2 O3 by coulometry, and gravimetric titration of Na2 S2 O3 and KIO3 . Therefore, it was necessary to carry out short-term stability testing of the Na2 S2 O3 solution. Samples (500 mL) of 0.1, 0.2 and 0.5 mol/L Na2 S2 O3 were stored without any stabilizer in a high-density polyethylene bottle purged with Ar gas at room temperature (approximately 22 C) for 17 days, and the reductometric factors of solutions, 5 g of 0.1 mol/L, 2.5 g of 0.2 mol/L and 1 g of 0.5 mol/L, were measured by coulometry. 2.5. Procedure (gravimetric titration) The titrations of K2 Cr2 O7 with Na2 S2 O3 and KIO3 with Na2 S2 O3 are based on the following reactions (reactions (2), (3), and (4)): K2 Cr 2 O7 + 6KI + 7H2 SO4 Cr 2 (SO4 )3 + 4K2 SO4 + 7H2 O + 3I2 KIO3 + 5KI + 3H2 SO4 3K2 SO4 + 3H2 O + 3I2 2Na2 S2 O3 + I2 2NaI + Na2 S4 O6 (2) (3) (4)

Rowley et al. examined coulometric titration of Na2 S2 O3 with electrolytically generated iodine at various pH values [22]. Conditions at pH values higher than 9 and lower than 5 lead to prominently large titration biases. I2 is easily hydrolyzed above pH 9, and air oxidation of I and production of sulfurous acid are observed below pH 5. To determine the changes in pH level in the coulometric titration cell under all experimental conditions, pH was measured after addition of 025 mL of ca. 0.1, 0.2 and 0.5 mol/L Na2 S2 O3 , and 016 g of KI to 100 mL of the catholyte in advance of the coulometric titration. Marinenko et al. reported that the current efciency for electrogeneration of I2 from a Pt anode was approximately 100% [15]. However, it was important to investigate the current efciency of the coulometric titration using our own Pt electrode and coulometric cell. The curve of generating current versus potential was drawn using a Type HABF-5001 potentiostat/galvanostat (Hokuto Denko Corporation, Tokyo, Japan) for 100 mL of the catholyte containing 03.2 g of KI. The potential was measured for the Pt generating electrode versus an Ag/AgCl reference electrode, linked with a Luggin capillary, and saturated KCl solution. 2.4. Procedure (coulometric titration) Approximately 150 mL of the anolyte and 100 mL of the catholyte were placed in the coulometric titration cell, and dissolved air was removed by bubbling Ar gas (>99.999% purity) through for 30 min in advance. During the experiment, the anode compartment was purged with Ar gas. The end-point was detected by a dead-stop method with an applied voltage of 150 mV between two Pt plates. Pre-titration was carried out using small constant-current pulses (2 mA 6 s) to about 40 mC after the end-point in order to eliminate impurities in the sup-

Prior to the titration, the time dependence of the I2 generation after addition of H2 SO4 to K2 Cr2 O7 in reaction (2) and KIO3 in reaction (3) with KI was investigated. Approximately 0.2 g of K2 Cr2 O7 , dried in accordance with JIS K 8005, was placed in a 300 mL beaker, to which 150 mL of deaerated water was added. KI (14 g) and 3.2 mol/L H2 SO4 (5 mL, conc. H2 SO4 :water = 1:5) were added, and the indicating current was monitored, using the same end-point determination system as that of the coulometric titration. For KIO3 , approximately 0.15 g of KIO3 and KI (0.53 g) were used. In the determination of K2 Cr2 O7 using Na2 S2 O3 , about 0.2 g of dried K2 Cr2 O7 was dissolved in 150 mL water, and 3 g KI and 5 mL of 3.2 mol/L H2 SO4 were added. The titration beaker was covered and placed in a cool dark space for 10 min, after which K2 Cr2 O7 was gravimetrically titrated with ca. 0.2 mol/L Na2 S2 O3 using a 25 mL GastightTM syringe with a needle made of peak. The end-point was determined in a similar manner to that of coulometric titration, using a dead-stop method with an applied voltage of 150 mV between two Pt plates, but the titration curve was reversed. Blanks were estimated using the same indicator. The assay of KIO3 using Na2 S2 O3 was carried out in a similar manner to the determination of K2 Cr2 O7 , except for the amounts used: approximately 0.15 g of KIO3 and 2 g of KI.

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Fig. 2. Changes in pH value obtained by adding 025 mL of ca. 0.1 mol/L ( ), 0.2 mol/L ( ) and 0.5 mol/L ( ) Na2 S2 O3 .

Fig. 5. Dependence of coulometric titration results on short-term storage time: ca. 0.1 mol/L ( ), 0.2 mol/L ( ) and 0.5 mol/L ( ) Na2 S2 O3 solutions.

Fig. 3. Changes in pH value obtained by adding 016 g of KI.

3. Results and discussion 3.1. pH conditions and current efciency

sured with respect to an Ag/AgCl reference electrode linked to the generating electrode via a Luggin capillary and saturated KCl solution. The current efciency for coulometric titration with electrogenerated I2 can be calculated from the ratio of the electric currents in the electrolyte with and without KI [15,16,24]. The estimated current efciency was approximately 100% using a phosphate buffer containing 1.23.2 g of KI; therefore, in the experiment, we used phosphate buffer with about 1.6 g of KI as a supporting electrolyte in order to take into account electrolyte dilution due to sample addition. 3.2. Determination of Na2 S2 O3 by coulometry

Changes in pH due to addition of 025 mL of ca. 0.1, 0.2 and 0.5 mol/L Na2 S2 O3 , and 016 g of KI to 100 mL of the catholyte are shown in Figs. 2 and 3, respectively. The pH values remained between 6 and 7 under all experimental conditions. In addition, after addition of 25 mL of ca. 0.1, 0.2 and 0.5 mol/L Na2 S2 O3 , the pH values of the solutions containing Na2 S2 O3 completely oxidized by I2 were 6.686, 6.640, and 6.550, respectively; hence, reaction (1) proceeds smoothly using this electrolyte in the coulometric titration cell. Fig. 4 shows the relationship between current and electrode potential for catholyte solutions containing 0, 0.4, 0.8, 1.2, 1.6, 2.4 and 3.2 g of KI. The dependence of the Pt anode (25 mm 40 mm) potential on the electrolysis current was mea-

The end-point using a dead-stop detection method was estimated by extrapolation of the plot of linear indicator current versus amount of electrolysis to the intercept (0.00 A) after the end-point. The results of short-term stability testing are shown in Fig. 5. Na2 S2 O3 solutions of 0.2 and 0.5 mol/L were stable for 17 days except for an initial couple of days. In comparison with these, the 0.1 mol/L Na2 S2 O3 solution was relatively unstable. Na2 S2 O3 slowly decomposes in solution with O2 and CO2 according to the following reactions: Na2 S2 O3 + H2 CO3 H2 S2 O3 + Na2 CO3 H2 S2 O3 H2 SO3 + S or Na2 S2 O3 Na2 SO3 + S 2Na2 SO3 + O2 2Na2 S2 O4 (7) (8) (5) (6)

Fig. 4. Relationship between current and electrode potential. Catholyte containing 0 g KI ( ), 0.2 g KI ( ) and 0.4 g3.2 g KI (thin line).

The reductometric factor of the solution containing decomposed Na2 S2 O3 rises because 1 mol SO3 2 reacts with 1 mol I2 in a redox reaction. To prevent decomposition of Na2 S2 O3 , Cu, which acts as a catalyst for air oxidation, is precipitated as CuCO3 by adding Na2 CO3 as a stabilizer. Some manufacturers in Japan produce a Na2 S2 O3 solution for titrimetry containing 0.50.8% of 3-methyl-1-butanol as a stabilizer instead of

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Fig. 6. Dependence of titration results on amount of Na2 S2 O3 solution used.

Na2 CO3 . Small rises in the reductometric factors of the Na2 S2 O3 solutions within 23 days after preparation are expected as a result of the initial decomposition of Na2 S2 O3 caused by dissolved air. The relative instability of the 0.1 mol/L Na2 S2 O3 solution may be due to the presence of a larger amount of air in the upper space of the bottle, because the amount of the solution removed for sampling was greater than for the other solutions. It was concluded that for 0.2 and 0.5 mol/L solutions, coulometric titration and gravimetric titration must be carried out within 17 days at the least estimate, but not within the rst 2 days. The dependence of the coulometric results on the amount of Na2 S2 O3 used is shown in Fig. 6. This investigation conrmed that there was no loss of Na2 S2 O3 as a result of diffusion into the counter-electrode chamber and no other external causes due to an increase in electrolysis time. Changes in the titration parameter did not have any signicant effect on the titration results; therefore, we adopted 9 g as the most suitable amount of Na2 S2 O3 in order to minimize the uncertainties due to sample weighing and end-point determination. Finally, 0.2 mol/L Na2 S2 O3 was assayed by coulometric titration for certication of KIO3 and determination of K2 Cr2 O7 for method validation. We used a 0.2 mol/L solution of Na2 S2 O3 because the gravimetric titration volume was sufciently large to minimize the uncertainties of titrant weighing and endpoint determination. The uncertainties of the measurements for Na2 S2 O3 are shown in Table 2 [25]. The combined expanded uncertainty for determination of Na2 S2 O3 was 0.0077%, calculated based on the uncertainties of the equipment (resistor, timer, voltmeter and linearity of balance), fundamental constants (Faraday constant) and other chemical determinations (repeatability,
Table 2 Uncertainty of coulometric analysis of Na2 S2 O3 Uncertainty source Repeatability End-point (1) End-point (2) Faraday constant Resistor Timer Voltmeter Mass of Na2 S2 O3 Dependence on the amount of Na2 S2 O3 Combined expanded uncertainty

Fig. 7. Time dependence of I2 generation on I concentration.

end-point determination and dependence on the amount of the samples). 3.3. Certication of KIO3 and determination of K2 Cr2 O7 by gravimetric titration Fig. 7 shows the time dependence of the I2 generation in solutions containing 14 g of KI after the starting reaction (2) and 0.53 g of KI after the starting reaction (3), obtained by monitoring the indicator current based on a dead-stop method. The indicator current is not directly proportional to the concentration of I2 , and it has an upper limit; however, it is relative data regarding the rate and amount of I2 generation. For K2 Cr2 O7 , it was concluded that a time of 7 min was not enough for complete generation of I2 , and while there were no differences among the 24 g of KI, the results for 1 g of KI were lacking. For determination of K2 Cr2 O7 with Na2 S2 O3 , 3 g of KI and 10 min generation time were adopted as experimental conditions. In reaction (3), there were no differences among the 23 g of KI, however, 0.51 g of KI were not enough for generation of I2 because lacking of I in the solution led to the deposition of solid I2 . For determination of KIO3 with Na2 S2 O3 , 2 g of KI and 10 min generation time were adopted to maintain consistency with JIS K 8005 [1] and previous research [12]. The results of titration between K2 Cr2 O7 and coulometrically determined Na2 S2 O3 are shown in Fig. 8, and uncertainty esti-

Relative expanded uncertainty (%, k = 2), n = number of measurements 0.00400, n = 6 0.00144 0.00239 0.0000172 0.00035 0.00121 0.0013 0.00534 0.00203 0.00772

Note 198.293 mmol/kg Regarding collinear approximation Incomplete rinsing 96485.3383(83) C/mol 10 and 10010 ppm + 3 ms 25 mV10 V Linearity, sample 9 g

T. Asakai et al. / Talanta 73 (2007) 346351 Table 3 Sources of uncertainty in the determination of K2 Cr2 O7 and KIO3 with Na2 S2 O3 by gravimetric titration Uncertainty source Relative expanded uncertainty (%, k = 2), n = number of measurements K2 Cr2 O7 Value of Na2 S2 O3 Repeatability End-point Weighing K2 Cr2 O7 or KIO3 Weighing Na2 S2 O3 Molar mass of K2 Cr2 O7 or KIO3 Blank Combined expanded uncertainty 0.0111, n = 5 0.0106, n = 9 0.0112 0.00707 0.00229 0.000953 0.00163 0.0205 KIO3 0.0077, n = 6 0.0072, n = 9 0.00857 0.00943 0.00229 0.000489 0.000674 0.0167

351

ple mass, current efciency of I2 electrogeneration and stability of Na2 S2 O3 solutions. For the gravimetric titration method, validity was ascertained using K2 Cr2 O7 of known purity. The results presented for Na2 S2 O3 , K2 Cr2 O7 and KIO3 were established with high accuracy, SI unit traceability, and uncertainty. References
[1] Japanese Industrial Standard (JIS), K 8005, Reference Materials for Volumetric Analysis, Japanese Standards Association, 2006. [2] I.M. Kolthoff, R. Belcher, Volumetric Analysis, vol. 3, Titration Methods: Oxidation-reduction Reactions, Interscience Publishers, Inc., New York, 1957, pp. 169243 and 449473. [3] V.A. Stenger, Anal. Chem. 23 (1951) 1540. [4] I.M. Kolthoff, E.B. Sandell, E.J. Meehan, S. Bruckenstein, Quantitative Chemical Analysis, The Macmillan Company Collier-Macmillan Limited, London, 1969 (Chapter 44). [5] J. Knoeck, H. Diehl, Talanta 16 (1969) 181. [6] G. Marinenko, J.K. Taylor, J. Res. NBS (Phys. Chem.) 67A (1963) 453. [7] K.W. Pratt, Anal. Chim. Acta 289 (1994) 125. [8] M. Mariassy, L. Vyskocil, A. Mathiasova, Accredit. Qual. Assur. 5 (2000) 437. [9] C.E. Champion, G. Marinenko, J.K. Taylor, W.E. Schmidt, Anal. Chem. 42 (1970) 1210. [10] T. Yoshimori, Talanta 22 (1975) 827. [11] T. Yoshimori, N. Sakaguchi, Talanta 22 (1975) 233. [12] T. Asakai, Y. Kakihara, Y. Kozuka, S. Hossaka, M. Murayama, T. Tanaka, Anal. Chim. Acta 567 (2006) 269. [13] S. Popoff, J.L. Whitman, J. Am. Chem. Soc. 47 (1925) 2259. [14] J.J. Lingane, A.J. Bard, Anal. Chim. Acta 16 (1957) 271. [15] G. Marinenko, J.K. Taylor, Anal. Chem. 39 (1967) 1568. [16] A. Hioki, M. Kubota, A. Kawase, Analyst 117 (1992) 997. [17] W.J. Ramsey, P.S. Farrington, E.H. Swift, Anal. Chem. 22 (1950) 332. [18] C.W. Foulk, A.T. Bawden, J. Am. Chem. Soc. 48 (1926) 2045. [19] S.M. Tuthill, R.S. Sprague, W.C. Stoecker, Anal. Chem. 36 (1964) 1994. [20] L. Ma, Accredit. Qual. Assur. 7 (2002) 163. [21] Atomic Weights of the Elements 2001 (IUPAC technical report), Pure Appl. Chem. 75 (2003) 1107. [22] K. Rowley, E.H. Swift, Anal. Chem. 26 (1954) 373. [23] P.J. Mohr, B.N. Taylor, Rev. Mod. Phys. 77 (2005) 1. [24] G. Marinenko, J.K. Taylor, J. Res. NBS (Phys. Chem.) 67A (1963) 402. [25] BIPM, IEC, IFCC, ISO, IUPAC, IUPAP and OIML, Guide to the expression of uncertainty in measurement, rst ed., Geneva, 1995.

Fig. 8. Results of determination for K2 Cr2 O7 and KIO3 . (*) See reference [12].

mates are shown in Table 3. The titration trial was carried out one day after the coulometric determination. The uncertainties were derived from the following: repeatability of titration, end-point determination (uctuation of collinear approximation), sample weighing (linearity of balance), molar mass of K2 Cr2 O7 , and blank (correction, uctuation in blank); the combined expanded uncertainty was 0.021% (k = 2). The effective purity of K2 Cr2 O7 was 99.984% 0.006% (k = 2), which was directly determined by coulometry with electrogenerated ferrous ions [12]. The assay of K2 Cr2 O7 by gravimetric titration based on the reductometric factor of Na2 S2 O3 determined by coulometry was 99.990% 0.021% (k = 2); these results were sufciently close to the certied value to conrm the validity of gravimetric titration between K2 Cr2 O7 and Na2 S2 O3 and the coulometric titration of Na2 S2 O3 . The results and uncertainty estimations on KIO3 are shown in Fig. 8 and Table 3, respectively. The assay of KIO3 was 99.972% 0.017% (k = 2) determined in a similar manner to K2 Cr2 O7 , and KIO3 was developed as a redox standard with a certied value linked to SI units. 4. Conclusions Redox reference materials were studied by coulometric and gravimetric titration. The accuracy of the coulometric method was investigated by examining the areas of dependency on sam-