Accred Qual Assur (2010) 15:391399 DOI 10.

1007/s00769-010-0646-0

GENERAL PAPER

Investigation on drying conditions and assays of amidosulfuric acid and sodium carbonate by acidimetric coulometric titration and gravimetric titration
Toshiaki Asakai Akiharu Hioki

Received: 7 December 2009 / Accepted: 1 February 2010 / Published online: 4 March 2010 Springer-Verlag 2010

Abstract Amidosulfuric acid and sodium carbonate as standards for acidbase titrimetry were assayed by coulometric titration and gravimetric titration. Amidosulfuric acid was directly assayed by coulometric titration with electrogenerated hydroxide ions, and sodium carbonate was assayed by gravimetric back-titration. For sodium carbonate, excess amount of sulfuric acid, whose concentration was determined by coulometric titration, was added to sodium carbonate, and then gravimetrically back-titrated using a sodium hydroxide solution whose concentration was determined by gravimetric titration using the sulfuric acid. The accuracy of the coulometric titration for amidosulfuric acid and sulfuric acid was evaluated by examining the current efciency of pulse electrolysis, the amount of the electrolysis current used, and the time spent for a titration. In addition, the drying conditions for high purity primary standards have a signicant effect on the titration results due to changes in the acidbase assay. The suitable drying conditions for amidosulfuric acid and sodium carbonate were evaluated by mass-change measurements, coulometric titration and gravimetric titration. The measurement uncertainties were estimated from the uncertainties on the titration processes. Finally, the assays of amidosulfuric acid and sodium carbonate were 99.986% 0.010% (k = 2) after drying at 50 C for 2 h, and 99.970% 0.016% (k = 2) after drying at 280 C for 4 h, respectively. In addition, the international consistency was conrmed by measuring certied reference materials (CRMs) available from different

National Metrology Institutes, and the compatibility of values among CRMs was experimentally ascertained. Keywords Coulometric titration Gravimetric titration Certied reference material Acidbase titration High purity amidosulfuric acid High purity sodium carbonate

Introduction Amidosulfuric acid and sodium carbonate are very important materials in acidbase titrimetry [1] and were recommended as primary standards by the Analytical Methods Committee [24]. Amidosulfuric acid is a strong acid and is used for determination of the concentration of a base such as sodium hydroxide. Sodium carbonate is a weak base and is used for determination of the concentration of an acid such as sulfuric acid and hydrochloric acid [15]. Both materials are very useful in acidbase titration; however, there are some instabilities in drying processes. The evaluation of the drying processes for high purity primary standards is required because the drying conditions have a signicant effect on the titration results due to changes in the acidbase assay [hereinafter, assay means effective purity (mass fraction) or assay of the amount content recalculated to mass fraction in acidbase titrimetry and apparent assay means apparent effective purity (mass fraction) or determined value of the amount content recalculated to mass fraction in acidbase titrimetry under the experimental condition used]. A few reports on the determination for amidosulfuric acid by coulometric titration have been published [69]. Studies for amidosulfuric acid are of interest in Japan because it is a central material as an acid standard [5].

T. Asakai (&) A. 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 e-mail: t-asakai@aist.go.jp

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Potassium hydrogen phthalate is generally used as an acid standard as well as a raw material for a pH buffer solution and a standard for a total organic carbon (TOC) analysis [10]; however, potassium hydrogen phthalate, a weak acid, is signicantly inuenced by atmospheric carbon dioxide near the end point, and the acidbase titration curve is not steep. One of the authors reported an accurate coulometric measurement procedure for amidosulfuric acid [11], and also investigated the optimum drying conditions by some methods such as thermogravimetry/mass spectrometry and Karl Fischer titration [12]. We have followed up the instability on heat by coulometric titration and measuring the mass of amidosulfuric acid dried at different temperatures in the present report. The change in the mass of amidosulfuric acid placed under a humid condition was also presented. In addition, the effect of the intermediate compartments (to avoid the diffusion of samples from the working-electrode chamber to the counter-electrode one) of the coulometric titration cell (vide infra) was examined by changing the sample size, the electrolysis current, and the delay time after introducing the samples. Finally, we estimated the combined standard uncertainty to certify an acid standard. There are some reports concerning the sodium carbonate assay utilizing coulometric titration. Taylor et al. [13] assayed sodium carbonate dried at 350400 C for several hours by coulometric titration with electrogenerated hydrogen ion. They used sodium sulfate as a supporting electrolyte instead of potassium chloride to avoid having chlorides oxidized on an anodic electrode. Carbon dioxide generating through the neutralization process between sodium carbonate and hydrogen ions was removed near the end point by spending sufcient time. The sodium carbonate assay was 99.911% 0.007% (mass fraction experimental SD; hereinafter, the same expression means that the values before and after indicate mass fraction and the experimental standard deviation, respectively), though the investigations of drying conditions and the estimation of uncertainty sources were insufcient. Yoshimori and Hikawa [14] reported that the assay of sodium carbonate dried at 600 C for 50 min was 99.991% 0.044% (mass fraction experimental SD) with electrogenerated hydrogen ions using 1 mol L-1 sodium sulfate as a supporting electrolyte solution. The rst acid-dissociation point (near pH 8) was adopted as the end point since the pH change near the second one was less sensitive. Yoshimori et al. [15] also mentioned that sodium carbonate contained some water content: about 0.005% after drying at 200 C for 1 h and below 0.001% after drying at 600 C for 1 h, where it was cooled at a desiccator with magnesium perchlorate. Pratt achieved the repeatability of 0.0028% (experimental relative standard deviation) utilizing automated constant-current coulometric

acidimetry [16]. One of the authors of the present paper investigated the suitable drying condition for sodium carbonate by thermogravimetry/mass spectrometry, gravimetric titration, mass-change measurement, and pH measurement [17]. The assays of sodium carbonate dried at different temperatures were measured by gravimetric titration using a hydrochloric acid titrant. The results were relative values because the concentration of hydrochloric acid was not absolutely determined for the measurements. The results revealed that a capability as a base increased according to the decomposition process (2NaHCO3 ? Na2CO3 ? Na2O or 2NaOH); thus, the increase of the assay accords with the decrease of mass. The report also indicated that sodium hydrogen carbonate as an impurity changed into sodium carbonate by heating and that the adsorbed water was detached at the temperature lower than 200 C. In addition, the decomposition of sodium carbonate occurred over about 400 C. In the present paper, we assayed sodium carbonate by a two-step titration to obtain more accurate results on an absolute basis: determination of the acid concentration of sulfuric acid by coulometric titration, and a gravimetric back-titration after excessively adding the sulfuric acid to sodium carbonate, using a sodium hydroxide solution whose concentration was gravimetrically determined based on the concentration of the sulfuric acid. Using this method, carbon dioxide generating in the neutralization process was completely removed by boiling the solution, and the assay linked to the International System of Units was obtained. We also measured changes in the sodium carbonate assays after drying at 230350 C for 224 h, and of the material placed under humid conditions. In addition, short-term stabilities of sulfuric acid and sodium hydroxide solutions were also discussed to estimate the uncertainty of the sodium carbonate assay.

Experimental Reagents Analytical reagent grade chemicals were used unless otherwise stated. Amidosulfuric acid was obtained from Wako Pure Chemical Industries, Ltd., Osaka, Japan. The following physical constants were used for the material: molar mass 97.0937 g mol-1 [18], density 2.15 g cm-3 [19], the Faraday constant 96485.3399 C mol-1 [20]. The certied reference material (CRM) of amidosulfuric acid (No. A0108604) obtained from Slovak Institute of Metrology (SMU, Slovakia) was used for clarifying the linkage among CRMs. The certied value of the SMU CRM is 99.983% 0.013% (k = 2); hereinafter, the similar expression means that the values before and after indicate

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the mass fraction and the expanded uncertainty expressed with the coverage factor following k = , respectively, and the material was used in accordance with the certicate except for the sample size (the minimum sample size is 0.5 g on the certicate). For sodium carbonate, its source material was obtained from Wako Pure Chemical Industries, Ltd., and was the product of GFS Chemicals, Inc., Ohio, USA. The following physical constants were used for the material: molar mass 105.9884 g mol-1 [18], density 2.54 g cm-3 [19], the Faraday constant 96485.3399 C mol-1 [20]. The material was compared with two CRMs: NIST SRM 351a from National Institute of Standards and Technology (NIST, USA) and SMU 298/99 from SMU. The certied value and the drying condition of NIST SRM 351a were 99.970% 0.014% (k = 2.08) and 275280 C for 4 h, respectively. For SMU 298/99, they were 99.904% 0.014% (k = 2) and 275 10 C for 2 h. The accuracy of the temperature in the drying oven used was conrmed by a calibrated thermometer. Apparatus We newly developed a highly automated coulometry system shown in Fig. 1. The coulometric titration cell was equipped with a working electrode (a platinum mesh 45 mm wide 9 120 mm long with a platinum rod 1.5 mm / 9 150 mm long), a counter electrode (a silver plate 50 mm wide 9 160 mm long 9 1 mm thick), a GST5721C combination glass electrode (DKK-TOA Corporation, Tokyo, Japan), a PFA sheet to avoid the splash of the supporting electrolyte placed above the working electrode, and inlet and outlet tubes for argon gas purging. Measurements of pH were carried out with a pH meter (type HM-30R, DKK-TOA Corporation). The unit to apply current was comprised a constant-current source (type 6243,

ADC Corporation, Tokyo, Japan), a custom-built switching timer (Taiyo Corporation, Tokyo, Japan), standard resistors (type 2792A, 10 and 100 X, Yokogawa Electric Corporation, Tokyo, Japan), a voltmeter (type 6581, ADC Corporation), and a universal counter (type TC110, Yokogawa Electric Corporation). The resistor used was appropriately chosen for different applied currents. The value of the applied current was determined on the basis of Ohms law using the voltmeter connected in parallel with the standard resistor, and the applied time was measured with the universal counter based on 10 kHz reference frequency. All devices were controlled and logged using a software written in National Instruments Corporation LabVIEW ver. 8.5. Log analyses were performed using a software written in Microsoft Excel Visual Basic for Application. Automatically controlled instruments improved the repeatability of the titration results. The balances used were an XP26 and an XP205 (Mettler-Toledo, Tokyo, Japan) and appropriate one was chosen for a different size of mass. General procedure of coulometric titration for amidosulfuric acid Coulometric titration was performed according to an usual acidimetric coulometric procedure [8, 11]. The supporting electrolyte solution was 1 mol L-1 KCl. The salt bridge was 3% agar gel containing 1 mol L-1 KCl. Solid samples were directly introduced to the coulometric titration cell using a polyethylene cup (ca. 16 mm / 9 ca. 8 mm deep) weighed with resolution of 1 lg. Solution samples were introduced to the cell using a plastic syringe with a PEEK needle weighed with resolution of 10 lg. Buoyancy correction was always applied for each sample. A large constant current (e.g. 100 mA) was used to electrolyze most of a sample and small constant-current pulses (e.g. 5 mA 9 2 s) were used to

Fig. 1 Circuit diagram of the automated coulometric titration system

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draw a titration curve near an end point. As the equivalence point the inection point was adopted and was estimated using third-order polynomial approximation near the point. General procedure of coulometric titration and gravimetric titration for sodium carbonate The determination of sodium carbonate has three steps: determination of the concentration of sulfuric acid by coulometric titration, determination of the concentration of sodium hydroxide solution by gravimetric titration with the sulfuric acid, and back-titration of sodium carbonate using the sulfuric acid and the sodium hydroxide solution. The acidimetric coulometric titration of a sulfuric acid was carried out in the same manner as the determination of amidosulfuric acid in a solution form. For the gravimetric titration of a sodium hydroxide solution, approximately 2 g of the sulfuric acid solution was titrated with a sodium hydroxide solution using a weighed plastic syringe with a PFA needle or a PEEK one, when argon gas was own above the surface of the solution. For the determination of sodium carbonate by gravimetric back-titration, approximately 0.4 g of sodium carbonate was weighed with resolution of 1 lg and was placed in a 200 mL tall beaker. The beaker was put on an electronic pan balance, and then the 0.10.3% excess amount of the sulfuric acid was carefully added to the sodium carbonate using the pan balance only as a guide to the addition. The solution was boiled to eliminate generated carbon dioxide. It was cooled to about 40 C on a water bath, and then it was back-titrated with the sodium hydroxide solution under argon gas. The end points in both gravimetric titrations were xed at pH 7, the inection point of a titration curve for strong acidstrong base, and were determined by a pH meter with a combination glass electrode.

Figure 2 shows the changes in the masses of amidosulfuric acid with crushing and without crushing at different drying temperatures. Amidosulfuric acid signicantly gained in mass over 100 C, and the rate of increase in mass of crushed amidosulfuric acid was larger than without crushing. The Analytical Methods Committee mentioned the thermal stability of amidosulfuric acid [2, 4]: it was concluded that amidosulfuric acid decomposes rapidly at temperatures above 136 C and that this decomposition proceeds slowly at lower temperatures. Further, amidosulfuric acid decomposes at 100 C with the surrounding moist air and changes into ammonium hydrogen sulfate by hydrolysis [2, 4]. Therefore, the committee recommended that the suitable drying condition was in a vacuum desiccator with an appropriate desiccant. The drying condition using a vacuum desiccator is adopted in the Japanese Industrial Standard K 8005 [21]. One of the authors [8] and Notley [22] also mentioned the instability of an amidosulfuric acid solution by hydrolysis. The results in Fig. 2 supported the decomposition of amidosulfuric acid over 100 C, and indicated that the decomposition rate signicantly depended on the surface area. Concerning the investigation of the mass changes by drying amidosulfuric acid without crushing on different drying durations, its mass increased about 0.003% after drying at 80 C for 47 h and decreased about 0.001% after drying at 50 C for 43 h. Thus, there were no signicant changes in the mass at 50 C and 80 C; however, there was slight indication of decomposition at 80 C. The coulometric titration for amidosulfuric acid (ca. 0.2 g) dried by several different treatments was carried out to clarify the instability more accurately. Consequently, there were no signicant changes within 99.97099.985% of the assays treated as follows: no drying without crushing, 50 C for 2 h without crushing, 50 C for 24 h without crushing, 80 C for 24 h without crushing, and no drying

Results and discussion Examination of drying conditions for amidosulfuric acid by weighing Changes in the mass of amidosulfuric acid by weighing before and after drying were examined to investigate the instability. Approximately 35 g of amidosulfuric acid placed in a platinum dish was weighed with resolution of 10 lg. It was dried and then kept at room temperature for 30 min in a desiccator with silica gel. The platinum dish with amidosulfuric acid was always weighed compared with an empty platinum dish of the same size in order to minimize the inuence of the uctuation of the weighing condition.

Fig. 2 Changes in the masses of amidosulfuric acid with crushing or without crushing by drying at 50140 C for 1 h

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after crushing. One of the authors reported that there was a slight indication of decomposition dried at 80 C for 24 h with crushing [12]. The amidosulfuric acid assay seems to depend on the way of crushing. Crushing thoroughly leads to an increase in its surface area and acceleration of decomposition at high temperature. In addition, crushing generates heat and thermally decomposes amidosulfuric acid. Therefore, we adopted 50 C for 2 h without crushing as a pretreatment in the present study. Concerning hygroscopicity, changes in the mass of amidosulfuric acid placed under a humid condition and its mass recovery by drying were measured in the following procedure: approximately 5 g of amidosulfuric acid was placed in a desiccator with a beaker containing water, and change in mass was monitored for 5 days. Consequently, it gained in mass 0.0010.002% for 2 h, 0.0040.006% for 9 h, 0.10.25% for 26 h, and 1.53.5% for 5 days. After adsorbing moisture, the amidosulfuric acid gaining 1.5% was placed in a desiccator with silica gel for 23 h, and the other amidosulfuric acid gaining 3.5% was placed at an ordinal laboratory atmosphere (ca. 23 C and humidity of ca. 40%) for 23 h; then the masses were monitored. The masses under both conditions gradually decreased; nally, they almost recovered the original masses and were little changed by drying again at 50 C for 1 h or 2 h. It was concluded that high purity amidosulfuric acid was not hygroscopic under an ordinal laboratory condition; neither higher drying temperature nor longer drying time was necessary. Determination of pulse efciency in acidimetric coulometric titration Applying a constant-current pulse to the cell and measuring a pH value were repeated and a titration curve was drawn near an end point. Generally speaking, multiple short electrolyses tend to result in a low current efciency due to non-Faradaic current and in an inaccurate of apparent current efciency due to the performance of the switching timer. Dependencies of apparent assay on the number of constant-current pulses were investigated to estimate both the pulse efciency and the switching performance of the custom-build switching timer. After electrolyzing the most part of 0.2 g of amidosulfuric acid, its apparent assay was measured using the different number of constant-current pulses (number of pulses 14304, one pulse 5 mA 9 2 s). The linear regression curve of the dependency of the apparent assay on the number of pulses was y = 0.0000238x ? 99.9816 [x the number of pulses, y the apparent assay (mass fraction), %]: one pulse increased the apparent assay of 0.2 g of amidosulfuric acid by 0.0000238%. The standard uncertainty of the slope in the linear regression was 0.0000243% (mass fraction) per one

pulse (ca. 101% relative of the slope itself). The number of pulses used in one titration for the real assay was 15 at most; therefore, the standard uncertainty of the assay resulting from the pulse efciency was less than 0.0004% in the case of 0.2 g sample. Using an extremely small sample size, it would be necessary to combine the uncertainty caused by the pulse efciency or to correct the apparent assay of amidosulfuric acid. Diffusion loss of amidosulfuric acid from workingelectrode chamber Two intermediate compartments (each compartment: ca. 22 mm / 9 16 mm long) separated by three porosity glass lters were placed between the working-electrode chamber and the counter-electrode one to avoid any loss of amidosulfuric acid as a result of diffusion from the working-electrode one. Lindberg [23] reported theoretical diffusion processes. One of the authors reported sample diffusion losses of an antimony(III) solution and an arsenic(III) one using a cell without any intermediate compartment [24]. Because the amount of diffusion strongly depended on the cell, the efciency of the intermediate compartments was experimentally investigated by the following procedure. Approximately 0.2 g of amidosulfuric acid dried at 50 C for 2 h was assayed with 30 mA, 50 mA or 100 mA electrolysis current. The dependency of the apparent assay on the electrolysis current is shown in Fig. 3. There was a slight dependency on the electrolysis current (or electrolysis time). The lower electrolysis current needs the longer electrolysis time which could lead larger amidosulfuric acid loss (or lower apparent assay). Figure 4 illustrates the dependency of the apparent assay on the delay time before starting the electrolysis after introducing the sample (ca. 0.2 g) with 100 mA electrolysis

Fig. 3 Dependency of the apparent assay of amidosulfuric acid (ca. 0.2 g) on the electrolysis current

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Coulometric titration for sulfuric acid and gravimetric titration for sodium hydroxide For the evaluation of the acidimetric coulometric titration procedure, dependencies of the concentration of sulfuric acid (approximately 200 mmol kg-1) measured by coulometric titration on both the solution mass and the electrolysis current were examined: about 16 g of sulfuric acid was electrolyzed with 30 mA, 50 mA or 100 mA. There was neither signicant dependency on the sample size nor the electrolysis current; therefore, there was neither signicant diffusion loss of the sample solution nor lowering of the current efciency. Consequently, we adopted the experimental conditionabout 3 g of the sample solution of sulfuric acid and 100 mA of the electrolysis current. To carry out the two-step titration for sodium carbonate, it was necessary to evaluate the short-term stabilities of sulfuric acid and sodium hydroxide solutions. Concerning the stability of the sulfuric acid, a 200 mmol kg-1 solution was stored in a 1 L high-density polyethylene bottle at room temperature for 26 days, and then the acid concentration of the solution was measured by coulometric titration; consequently, the concentration was 0.009% higher than the initial concentration. The mass of the 1 L bottle decreased by approximately 0.006% during 26 days; hence, it is obvious that increasing the concentration was basically caused by the evaporation of water. It was necessary to evaluate the concentration of sulfuric acid before and after the back-titration of sodium carbonate to correct the concentration change of the sulfuric acid. Concerning the stability of the sodium hydroxide solution as a titrant (approximately 50 mmol kg-1), its concentration was measured two times before and after back-titrating sodium carbonate; the difference of the results was within 0.03%. Although the uncertainty of correcting the concentration change of the titrant was combined to the uncertainty of the sodium carbonate assay, the contribution was very small. In the titration of sodium carbonate, only 0.10.3% excess amount of sulfuric acid was added to sodium carbonate and was back-titrated using the titrant. Therefore, the concentration change of the titrant during a day substantially did not affect the sodium carbonate assay. Drying condition for sodium carbonate The result of coulometric titration for the SMU CRM was 99.983% 0.003% (mass fraction experimental SD) from 5 measurements, and in good agreement with the certied value 99.983% 0.013% (k = 2) within the uncertainty. This result means that the international consistency between CRMs produced by different laboratories was conrmed. Figure 5 shows the dependency of the sodium carbonate assay on the drying temperatures and the drying durations. Figure 6 shows the dependency of the sodium carbonate assay on the temperatures of drying for 4 h. There were signicant differences among the assays at the different drying temperatures and the different drying time. As

Fig. 4 Dependency of the apparent assay of amidosulfuric acid (ca. 0.2 g) on the delay time before starting the electrolysis after introducing the sample with 100 mA electrolysis current

current; this dependency strongly indicates the diffusion loss of the sample. It took about 33 min to electrolyze 0.2 g of amidosulfuric acid with 100 mA, and about 110 min with 30 mA; the dependency of the apparent assay on the delay time (Fig. 4) and that on the electrolysis current (or electrolysis time) (Fig. 3) were very consistent. This investigation claried the effect of the diffusion loss. The strict estimation of the amount of diffusion is complicated because the diffusion process is affected by the cross-section area of the intermediate compartments, the porosities of glass lters, etc. We also determined the amidosulfuric acid in a solution form (ca. 0.3 mol kg-1) to minimize the sample diffusion loss effect. Approximately 15 g of the solution (below 0.15 g in solid) was electrolyzed with 100 or 30 mA. The results of smaller mass of the solution electrolyzed with 100 or 30 mA were in the range of 99.97599.995% and not different from those of 0.2 g of solid amidosulfuric acid (see Figs. 3, 4); in addition, there was no signicant dependency of the apparent assay on the mass of sample solution. Finally, we adopted the experimental condition 0.2 g of the sample mass in solid and 100 mA electrolysis current, since the results of amidosulfuric acid in solid were not different from those in solution under the condition where the sample diffusion loss was minimized. Conrmation of international consistency for amidosulfuric acid

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Fig. 5 Dependency of the sodium carbonate assay on the drying temperature and drying duration

Fig. 6 Dependency of the sodium carbonate assay on the drying temperature for 4 h

previously reported by one of the authors, the dependencies were caused by the following decomposition process, 2NaHCO3 ? Na2CO3 ? Na2O (or 2NaOH) [17]. The assay increases due to the decomposition since it makes the mass smaller in spite of the unchanged ability as a base. In the previous report, one of the authors compared the concentrations as a base of sodium carbonate under different drying conditions by a direct titration using hydrochloric acid [17]. The concentrations were not absolutely determined, and the repeatabilities were poor due to the carbon dioxide generating through the neutralization reaction; consequently, the dependencies of the sodium carbonate assay on the drying temperature and the drying duration were obscure. In the present study, the coulometric titration and the precise back-titration made the dependency denitely clear. Finally, we adopted 280 C for 4 h as a drying condition because sodium carbonate can be dried stably at around 280 C, and the drying duration of 4 h is expected to be convenient in a daily experiment. For that purpose, the

detailed dependencies on the drying temperature and the drying time were examined around 280 C for 4 h. We estimated that the standard uncertainty caused by the drying time, 4 1 h, was 0.00327% (the relative standard deviation among three values) and that the standard uncertainty caused by the drying temperature, 280 C 10 C, was 0.00559% (the relative standard deviation of the rectangular distribution between the assay at 270 C and that at 280 C). To conrm the effectiveness of the drying condition, 280 C 10 C for 4 h, a hygroscopicity test for sodium carbonate was carried out in a similar manner previously described for amidosulfuric acid. Approximately 3 g of sodium carbonate in a platinum dish was placed in a desiccator with a beaker containing water for 4 h, and changes in the mass of sodium carbonate were monitored. And then, both a dish with moisture-adsorbing sodium carbonate and a dish with moisture-unadsorbing one were dried at 280 C for 4 h together, and those were assayed by the back-titration. Sodium carbonate under the humid condition gained the masses of 0.635% for 2 h and of 1.071% for 4 h. After drying the sodium carbonate with moisture at 280 C for 4 h, the mass decreased 1.800% compared with that before drying, and 0.729% compared with the initial mass. The other fresh sodium carbonate lost the mass of 0.735% after drying at 280 C for 4 h; hence, the total decrease in mass was almost the same between the sodium carbonate containing moisture and the fresh one. The assays after drying of the moisture-adsorbing sodium carbonate and the moisture-unadsorbing one were 99.965% 0.0018% (mass fraction experimental SD) from 4 measurements and 99.964% 0.0046% (mass fraction experimental SD) from 4 measurements, respectively. There were no signicant differences; therefore, it was concluded that the drying condition, 280 C for 4 h, was enough to dry sodium carbonate stored under an ordinal laboratory condition. Conrmation of international consistency for sodium carbonate The combination method of the acidimetric coulometric titration and the gravimetric back-titration was validated using CRMs of sodium carbonate available from SMU and NIST. The results of back-titration for the SMU CRM [the certied value 99.904% 0.014% (k = 2)] and the NIST SRM [the certied value 99.970% 0.014% (k = 2.08)] of sodium carbonate were 99.890% 0.003% (mass fraction experimental SD) from 2 measurements, and 99.969% 0.004% (mass fraction experimental SD) from 5 measurements, respectively. Each result was in good agreement with the certied value within the uncertainty, and the international consistency of the method in the present study was ascertained.

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398 Table 1 Uncertainty budget for amidosulfuric acid by coulometric titration Uncertainty source Repeatability and homogeneity Faraday constant Standard resistor Timer Switch performance Voltmeter Weighing of amidosulfuric acid Molar mass of amidosulfuric acid Combined standard uncertainty (relative, %) Relative standard uncertainty (%) 0.0038 0.0000025 0.00022 0.00005 0.000030 0.00015 0.0017 0.0030 0.0052

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Uncertainty estimation The uncertainty budgets for amidosulfuric acid and sodium carbonate are shown in Tables 1 and 2, respectively. Concerning amidosulfuric acid, the uncertainties were derived from repeatability of titration, the Faraday constant, calibrations of the resistor, of the reference frequency and of the voltmeter, switching speed, sample weighing (sensitivity and linearity of each balance), and molar mass of amidosulfuric acid: the expanded uncertainty with a coverage factor 2 was 0.010%. On the other hand, concerning sodium carbonate, the uncertainties were calculated from the gravimetric titration in addition to the coulometric titration: the expanded uncertainty with a coverage factor 2 was 0.016%. The nal results for amidosulfuric acid and sodium carbonate were 99.986% 0.010% (k = 2) after drying at 50 C for 2 h, and 99.970% 0.016% (k = 2) after drying at 280 C for 4 h, respectively. Thus, acidbase standards with values linking to the SI were developed.

Table 2 Uncertainty budget for sodium carbonate by coulometric titration and gravimetric back-titration Uncertainty source (1) Sulfuric acid Repeatability Faraday constant Standard resistor Electrolysis time 1 (reference frequency) Electrolysis time 2 (switch performance) Voltmeter Weighing of sulfuric acid Combined standard uncertainty for sulfuric acid (relative, %) (2) Sodium hydroxide Repeatability Weighing of sulfuric acid Weighing of sodium hydroxide Combined standard uncertainty for sodium hydroxide (relative, %) (3) Sodium carbonate Repeatability and homogeneity Weighing of sodium carbonate Weighing of sulfuric acid Weighing of sodium hydroxide Concentration of sulfuric acid [the combined standard uncertainty of (1)] Concentration of sodium hydroxide (1/100 contribution) [the combined standard uncertainty of (2)] Molar mass of sodium carbonate Drying temperature (280 10 C) Drying time (4 1 h) Combined standard uncertainty for sodium carbonate (relative, %) 0.0040 0.00087 0.00039 0.00058 0.0024 0.00012 0.011 0.0058 0.00058 0.012 0.00072 0.0000025 0.00022 0.00005 0.000060 0.00015 0.0023 0.0024 Relative standard uncertainty (%)

Conclusions Acidbase standards, amidosulfuric acid and sodium carbonate, were assayed by coulometric titration and gravimetric titration. For the coulometric titration, the uncertainty and the accuracy were evaluated by examining the dependencies of the assay (or concentration) on the electrolysis current, the sample size used, and the efciency of the intermediate compartments. Drying conditions were also examined by mass measurements, coulometric titration and gravimetric back-titration. National Metrology Institute of Japan (NMIJ) has started providing amidosulfuric acid (NMIJ CRM 3004-a) and sodium carbonate (NMIJ CRM 3005-a) as CRMs based on the methods in the present paper. These CRMs have high accuracy, traceability to the SI, and were validated with CRMs from other national metrology institutes. Field laboratories and researchers can obtain them directly, and reagent manufacturers can use them for preparing secondary reference materials. Highly reliable CRMs are now available and will signicantly contribute to obtain accurate analytical data. References
1. Kolthoff IM, Stenger VA (1947) Volumetric analysis, volume ii titration methods: acidbase, precipitation, and complex-formation reactions, second revised edition. Interscience Publications Inc., New York 2. Analytical methods Committee (1967) Analyst 92:587592 3. Analytical Methods Committee (1965) Analyst 90:251255 4. Analytical Methods Committee (1969) Pure Appl Chem 19:445 455

0.00066 0.0056 0.0033 0.0081

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