WO2010137132A1 - Procédé de mesure d'anions - Google Patents

Procédé de mesure d'anions Download PDF

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Publication number
WO2010137132A1
WO2010137132A1 PCT/JP2009/059683 JP2009059683W WO2010137132A1 WO 2010137132 A1 WO2010137132 A1 WO 2010137132A1 JP 2009059683 W JP2009059683 W JP 2009059683W WO 2010137132 A1 WO2010137132 A1 WO 2010137132A1
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WO
WIPO (PCT)
Prior art keywords
acid
mobile phase
group
organic acid
ion
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Application number
PCT/JP2009/059683
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English (en)
Japanese (ja)
Inventor
幸夫 老川
勝正 坂本
重吉 堀池
博昭 中西
禎宏 早川
喜昭 麻生
淳 家氏
秀三 丸山
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株式会社島津製作所
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Application filed by 株式会社島津製作所 filed Critical 株式会社島津製作所
Priority to JP2011515790A priority Critical patent/JP5408249B2/ja
Priority to PCT/JP2009/059683 priority patent/WO2010137132A1/fr
Publication of WO2010137132A1 publication Critical patent/WO2010137132A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
    • G01N2030/965—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange suppressor columns

Definitions

  • the present invention relates to a method for quantitatively measuring anions, particularly fluoride ions, in a sample solution by ion chromatography.
  • Ion chromatography is an extremely excellent analytical method for analyzing inorganic ions, and has been rapidly spreading in recent years.
  • Ion chromatography is an analytical method that applies liquid chromatography.
  • detection is performed by an electrical conductivity detection method, thereby increasing sensitivity and selectivity. I am trying both.
  • a baseline disturbance (hereinafter referred to as a water dip) occurs in the vicinity of the position at which ppb is to be measured, making it difficult to confirm the peak of the fluoride ion at the ppb level, causing a problem in quantitativeness.
  • the water dip appears as a downward (negative) peak with respect to the baseline as the conductivity of the sample is lower, that is, as the water becomes clearer.
  • the sample solution contains carbonate so that the salt concentration of the sample solution containing fluoride ions is equal to the salt concentration of the eluent of the mobile phase (see Patent Document 1). .
  • the method of adjusting the salt concentration of the fluoride ion-containing sample solution to the salt concentration of the eluent of the mobile phase is often manual adjustment of the salt concentration. Since the concentration of the target fluoride ion may be lowered, another error factor may occur even if the influence of the water dip can be avoided.
  • the present invention is not a method of adding any component for suppressing the influence of water dip to a sample solution, but aims to reduce the influence of water dip by adjusting the solvent constituting the mobile phase. It is.
  • the anion measurement method of the present invention is a method by ion chromatography, and includes the following steps (A) to (E).
  • C introducing the sample solution into the separation column by the mobile phase and separating it into sample component ions;
  • D introducing the eluate from the separation column into a suppressor to convert carbonate in the eluate into carbonic acid; and
  • the pH is 5-6 during the suppressor. Since pKa (acid dissociation constant) of acetic acid is 4.5, it is considered that dissociation is suppressed to some extent.
  • Nafion which has a sulfone group as a functional group, is used as the cation exchange membrane of the suppressor, for example, when the acyl group of acetic acid forms a counter ion by hydrogen bonding with the sulfone group in the water cluster, the Nafion layer though now neutralized, thus fluoride ions F with a large electronegativity - retention of the ion-exchange membrane is increased relative to, delayed elution time of fluoride ions.
  • the sulfone group is neutralized by a counter ion of acetic acid, hydrogen bonds are relaxed, and water dip is considered to be improved.
  • Organic acids added to the mobile phase eluent include acetic acid, propionic acid, citric acid, succinic acid, sodium benzoate, ammonium acetate, sodium hippurate, tartaric acid, malic acid, malonic acid and 18-crown-6 ether.
  • An organic acid selected from the group consisting of the following (hereinafter referred to as “Group A”) is used. When these organic acids belonging to Group A are added to the mobile phase, water dip is reduced.
  • organic acids belonging to Group A in particular, a group consisting of acetic acid, propionic acid, succinic acid, sodium benzoate, ammonium acetate, tartaric acid, malic acid, malonic acid and 18-crown-6 ether (hereinafter “B”)
  • the organic acid (2) improves the retention of fluoride ions by causing interaction between the separation column or suppressor surface and fluoride ions.
  • organic acids belonging to Group A particularly those of citric acid and sodium hippurate group (hereinafter referred to as “C” group) have two or three carbonyl groups (—C ⁇ O).
  • the negative ion (counter ion) associated with the unpaired electron of the oxygen atom shows the effect of ion exclusion (fluoride ion repelled by the influence of the strong negative ion acting as an acid counter), and elution of fluoride ion
  • the effect that the analysis time can be shortened can be obtained.
  • the peak of fluoride ions is closer to the water dip than when these organic acids are not added to the mobile phase, but the water dip itself is reduced by adding these organic acids to the mobile phase.
  • the effect of water dip is less than when these organic acids are not added to the mobile phase.
  • organic acids belonging to Group A particularly, organic acids in the group of citric acid, succinic acid, tartaric acid and 18-crown-6 ether (hereinafter referred to as “D” group) have high detection sensitivity.
  • D group organic acids in the group of citric acid, succinic acid, tartaric acid and 18-crown-6 ether
  • citric acid, succinic acid, and tartaric acid have two or three acyl groups, so there are two or three pKas, and a high pKa (ie, near a weakly acidic suppressor) conductivity meter.
  • the detection sensitivity increases because the release of eluted hydrogen ions increases at the position.
  • 18-crown-6 ether acts as an acid including cations such as potassium ions in the sample, so that the conductivity at the time of detection is increased and the effect of increasing the detection sensitivity is also obtained. .
  • FIG. 1 schematically shows an example of an ion chromatograph to which the present invention is applied.
  • an eluent supply flow path 7 having a liquid feed pump 4 is connected to the separation column 2.
  • the degasser 5 is for removing bubbles in the eluent 6.
  • An injector 8 for injecting a sample is disposed in the eluent supply channel 7.
  • the sample injected into the separation column 2 is separated into respective ions in the separation column 2, and the eluate flow path 9 from the separation column 2 is led to the conductivity meter cell 10, and the eluate passes through the cell 10. Sometimes conductivity is detected.
  • the liquid that has passed through the cell 10 is discharged as waste liquid to the drain.
  • a suppressor 14 is disposed in order to remove carbonate ions that increase the conductivity of the column eluate and enable high-sensitivity measurement.
  • the separation column 2, suppressor 14 and conductivity meter cell 10 are housed in a column oven 26 and the temperature is adjusted so as to reach a constant temperature.
  • a personal computer 28 is connected to the column oven 26 and the conductivity meter cell 10 as a control unit. Yes.
  • the separation column 2 is a column for anion analysis, and is composed of, for example, an anion analysis column (for example, IC-SA2 (polyvinyl alcohol gel quaternary ammonium group) manufactured by Shimadzu Corporation) having an inner diameter of 4 mm and a length of 250 mm. Use things.
  • an anion analysis column for example, IC-SA2 (polyvinyl alcohol gel quaternary ammonium group) manufactured by Shimadzu Corporation) having an inner diameter of 4 mm and a length of 250 mm.
  • the suppressor 14 can be composed of two substrates with an ion exchange membrane 16 sandwiched between them. In that case, flow paths are formed on the opposing surfaces of both substrates so as to oppose each other with the ion exchange membrane 16 interposed therebetween.
  • the inlet of one flow path is connected to a pipe 9 through which the eluate flows from the separation column 2 by a connector, and the eluate flows from the separation column 2 along one surface of the ion exchange membrane 16.
  • the outlet of the flow path is connected to a pipe 18 connected to the conductivity meter cell 10 by a connector.
  • the removal liquid 20 is fed by a liquid feed pump 22 so that the removal liquid 20 flows along the other surface of the ion exchange membrane 16 at the inlet of the other flow path facing the one flow path across the ion exchange membrane 16.
  • a supplied removal liquid channel 24 is connected.
  • the removing liquid 20 regenerates the ionic functional group of the ion exchange membrane 16, and in this example, sulfuric acid is used.
  • the outlet of the flow path along the other surface of the ion exchange membrane 16 is connected to the drain, and the removal liquid 20 that flows along the other surface of the ion exchange membrane 16 is discharged to the drain.
  • the ion exchange membrane 16 is a cation exchange membrane.
  • a functional group for ion exchange may be bonded to a perfluorocarbon polymer. Perfluorocarbon polymers have high chemical resistance.
  • the functional group for ion exchange has an acidic functional group such as a sulfonyl group or a carbonyl group, and the carbonate ion to be exchanged is exchanged with hydrogen ion (H + ).
  • the ion exchange membrane 16 having a sulfonyl group as an acidic functional group is obtained by thinning a copolymer obtained by copolymerization of the following compound A and compound B, followed by saponification treatment. be able to.
  • Compound A): CF 2 CF 2
  • the ion exchange membrane 16 preferably has a thickness of 100 ⁇ m to 300 ⁇ m. With such a thickness, it can have a pressure resistance of 2 MPa or more.
  • carbonate ions which are unnecessary cations are selectively exchanged with hydrogen ions in the ion exchange membrane 16 from the column eluate flowing along one surface of the ion exchange membrane 16 by adsorption and dialysis with the ion exchange membrane 16. Removed. Since the hydrogen ions exchanged with the carbonate ions react with the hydroxide ions in the column eluate and are converted to water, the conductivity of the column eluate is lowered, and detection by the conductivity meter cell 10 of the detector is performed. Noise is reduced. The carbonate ions adsorbed and dialyzed on the ion exchange membrane 16 are exchanged with hydrogen ions in sulfuric acid, which is the removal liquid flowing through the removal liquid flow path 24, and released into the removal liquid.
  • the eluent for analysis in Examples shown in Table 1 as “(1) Acetic acid” is obtained by adding 20 ⁇ L of 1M acetic acid to 100 mL of this stock solution and diluting to 1 L with purified water.
  • organic acid-containing eluents (2) to (11) in Table 1 were prepared using propionic acid, citric acid, or the like instead of acetic acid.
  • FIG. 2 shows ion chromatograms measured using each of the above as a mobile phase.
  • the sample was a solution containing 50 ppb of F ⁇ ions, and 10 ⁇ L was injected from the injector.
  • the column temperature was 25 ° C.
  • the mobile phase flow rate was 1.0 mL / min
  • the suppressor 14 was supplied with 25 mN sulfuric acid as the removal solution 20 at a flow rate of 1.0 mL / min.
  • A does not contain an organic acid, and its baseline is BL1.
  • B is obtained by adding 0.02 mM of acetic acid, and its baseline is BL2.
  • W represents a water dip.
  • the baseline at the position where the peak of F ⁇ ion appears is stabilized by adding acetic acid to the mobile phase.
  • acetic acid slowed the elution time of the F - ion peak and was further away from the water dip position.
  • the elution time under these analysis conditions was 3.363 minutes for the mobile phase to which no organic acid was added, whereas it was 3.788 minutes for the mobile phase to which acetic acid was added.
  • Quantitative results obtained by measuring the same sample 10 times continuously using a mobile phase to which acetic acid has been added under the analysis conditions are shown in Table 2.
  • the concentration was calculated using a calibration curve. That is, calibration curve data based on the concentration and peak area measured using a standard sample was created, and the concentration was calculated by applying the measured chromatogram peak area value to the calibration curve.
  • CV is the rate of change and is the standard deviation / average value.
  • FIG. 3 shows the result of measuring fluoride ions by chromatograph.
  • the sample was a solution containing 500 ppb fluoride ions, and 10 ⁇ L thereof was injected from the injector 8. In this measurement, the column temperature was 30 ° C.
  • the mobile phase flow rate is 1.0 mL / min.
  • 100 mN sulfuric acid was allowed to flow as the removing solution 20 at a flow rate of 0.15 mL / min.
  • FIG. 4 Since the chromatograms in FIG. 3 overlap and are difficult to understand, a representative one is shown in FIG. In FIG. 4, the time axis on the horizontal axis is shown enlarged.
  • the chromatogram of the mobile phase with sodium benzoate added is the B group consisting of acetic acid, propionic acid, succinic acid, sodium benzoate, ammonium acetate, tartaric acid, malic acid, malonic acid and 18-crown-6 ether. It represents an organic acid, and the retention time is longer than that of the comparative example in which no organic acid is added.
  • the chromatogram of FIG. 2 When the chromatogram of FIG. 2 is seen in detail, those using a mobile phase to which an organic acid of group B other than sodium benzoate is added all have a longer retention time than that of the comparative example to which no organic acid is added. ing.
  • the chromatogram of the mobile phase with citric acid added is representative of group C organic acid consisting of citric acid and sodium hippurate, and the retention time is shorter than that of the comparative example without the addition of organic acid. ing.
  • group C organic acid consisting of citric acid and sodium hippurate
  • the chromatogram of the mobile phase with DL tartaric acid added is representative of Group D organic acids consisting of citric acid, succinic acid, tartaric acid and 18-crown-6 ether, and is a comparative example without the addition of organic acid. As compared with, the height of the peak is increased and the detection sensitivity is increased.
  • the chromatogram of FIG. 2 is seen in detail, even when the mobile phase which added the other organic acid which belongs to D group is used, a sensitivity is higher than the thing of the comparative example which does not add an organic acid.
  • Table 1 shows the fluoride ion elution time, the presence or absence of a water dip improvement effect, and the background conductivity measured from the chromatogram results of FIG.
  • the effect of improving the water dip cannot be determined from the portion shown in FIG. 3, but was determined by shifting the display range to the negative region side and comparing the size of the water dip. It was confirmed that even when the mobile phase to which any organic acid was added was used, the size of the water dip was reduced and improved.
  • the measurement result of the background conductivity shows that no increase in the conductivity that hinders the measurement is observed despite the addition of the organic acid.

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Abstract

La présente invention concerne une phase mobile pour chromatographie ionique, obtenue en ajoutant un acide organique comportant un groupe acyle à une solution d'élution contenant un sel de type carbonate. L'acide organique peut être de l'acide acétique, de l'acide propionique, de l'acide citrique, de l'acide succinique, du benzoate de sodium, de l'acétate d'ammonium, de l'hippurate de sodium, de l'acide tartrique, de l'acide malique, de l'acide malonique ou de l'éther 18-couronne-6.
PCT/JP2009/059683 2009-05-27 2009-05-27 Procédé de mesure d'anions WO2010137132A1 (fr)

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JP2011515790A JP5408249B2 (ja) 2009-05-27 2009-05-27 陰イオン測定方法
PCT/JP2009/059683 WO2010137132A1 (fr) 2009-05-27 2009-05-27 Procédé de mesure d'anions

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013024518A1 (fr) * 2011-08-12 2013-02-21 株式会社島津製作所 Procédé d'analyse d'un acide halogéné oxydant
CN103399106A (zh) * 2013-08-08 2013-11-20 四川出入境检验检疫局检验检疫技术中心 同时检测皮革中各种醛分别含量的低压离子色谱法
CN113109496A (zh) * 2021-04-20 2021-07-13 陕西中烟工业有限责任公司 一种卷烟纸中8种阴离子和酸根离子的离子色谱测定方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6234055A (ja) * 1985-08-08 1987-02-14 Mitsubishi Electric Corp 陰イオンクロマトグラフを用いたフツ素イオンの測定方法
JPS62237353A (ja) * 1986-04-09 1987-10-17 Hitachi Ltd 陰イオンクロマトグラフイ−方法
JPH01299457A (ja) * 1988-05-27 1989-12-04 Hitachi Ltd サプレッサ型イオン対クロマトグラフ測定方法及び装置
JP2000065812A (ja) * 1998-08-19 2000-03-03 Showa Denko Kk キレート剤を用いた陰イオン測定方法
JP2000121618A (ja) * 1998-10-14 2000-04-28 Shimadzu Corp 無機陰イオン分析方法
JP2000214146A (ja) * 1999-01-28 2000-08-04 Shimadzu Corp 無機陰イオン分析法
JP2000356630A (ja) * 1999-06-14 2000-12-26 Mitsubishi Electric Engineering Co Ltd ふっ素イオンの測定方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6234055A (ja) * 1985-08-08 1987-02-14 Mitsubishi Electric Corp 陰イオンクロマトグラフを用いたフツ素イオンの測定方法
JPS62237353A (ja) * 1986-04-09 1987-10-17 Hitachi Ltd 陰イオンクロマトグラフイ−方法
JPH01299457A (ja) * 1988-05-27 1989-12-04 Hitachi Ltd サプレッサ型イオン対クロマトグラフ測定方法及び装置
JP2000065812A (ja) * 1998-08-19 2000-03-03 Showa Denko Kk キレート剤を用いた陰イオン測定方法
JP2000121618A (ja) * 1998-10-14 2000-04-28 Shimadzu Corp 無機陰イオン分析方法
JP2000214146A (ja) * 1999-01-28 2000-08-04 Shimadzu Corp 無機陰イオン分析法
JP2000356630A (ja) * 1999-06-14 2000-12-26 Mitsubishi Electric Engineering Co Ltd ふっ素イオンの測定方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013024518A1 (fr) * 2011-08-12 2013-02-21 株式会社島津製作所 Procédé d'analyse d'un acide halogéné oxydant
CN103399106A (zh) * 2013-08-08 2013-11-20 四川出入境检验检疫局检验检疫技术中心 同时检测皮革中各种醛分别含量的低压离子色谱法
CN113109496A (zh) * 2021-04-20 2021-07-13 陕西中烟工业有限责任公司 一种卷烟纸中8种阴离子和酸根离子的离子色谱测定方法

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