JPH01299457A - Method and apparatus for measuring suppressor type ion-pair chromatograph - Google Patents
Method and apparatus for measuring suppressor type ion-pair chromatographInfo
- Publication number
- JPH01299457A JPH01299457A JP63128365A JP12836588A JPH01299457A JP H01299457 A JPH01299457 A JP H01299457A JP 63128365 A JP63128365 A JP 63128365A JP 12836588 A JP12836588 A JP 12836588A JP H01299457 A JPH01299457 A JP H01299457A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- diaphragm
- reagent
- solution
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 64
- 150000002500 ions Chemical class 0.000 claims abstract description 59
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 40
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 35
- 238000005341 cation exchange Methods 0.000 claims abstract description 34
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000007789 gas Substances 0.000 claims description 41
- 239000003480 eluent Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 34
- 239000012528 membrane Substances 0.000 claims description 32
- 238000009792 diffusion process Methods 0.000 claims description 20
- 238000004190 ion pair chromatography Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000000691 measurement method Methods 0.000 claims description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 60
- 238000005259 measurement Methods 0.000 abstract description 6
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- -1 organic group ions Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101100495769 Caenorhabditis elegans che-1 gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は低ＰＨ唄域での測定に好適なサプレッサ型イオ
ン対クロマトグラフ測定方法、測定装置。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a suppressor type ion pair chromatography measurement method and a measurement device suitable for measurement in a low pH range.
並びにそのための溶離液の作成方法及び作成装置に関す
る。The present invention also relates to a method and apparatus for preparing an eluent therefor.
従来のイオン対クロマトグラフ測定方法におい℃は、イ
オン対試薬溶離液としてはテトラブチルアンモニウム等
イオン対試薬の水酸化物溶液が使用されていた。サプレ
ッサ型イオン対クロマトグラフ測定においては分離カラ
ム後にサプレッサか設げられてイオン対試薬の水酸化物
はサプレッサ内での陽イオン交換によりＨ，０に変換さ
れるために溶離液の導電率が低くなり、目面成分を導電
率検出器で検出できるからである。しかし、イオン対試
薬の水酸化物溶液はｐＨが１０以上で、アルカリ性で分
解する試料の分析九は通用できず、またｐＨ７以上の溶
離液では損傷を受けるシリカ糸のカラムは分離カラムと
して使用できない等の問題点があった〇
一方、イオン対クロマトグラフ測定において、イオン対
試薬を含む溶離液のｐＨを下げる方法として、従来は、
ノーマンΦイー・スケリーＣＮｏ？７ｍＡ’ ５ｋｇ
１ｌｙ ） ；逆相液体クロマトグラフィーカラムにお
ける無機および有機基イオンの分＠ （５ｅｐ−ａｒａ
ｔｉｏｎ ｏｆ Ｉｎｏｒｇａｎｉｃ ａｎｃｔ Ｏｒ
ｇａｎｉｃ Ａｎｉｏｎｓ ｏｒｂＲｅｖｅｒｔｅｄ−
ｐｈａｓｅ Ｌｉｑｕｉｄ、 Ｃ’ｈ’ｒｏｙｎａｔｏ
ｇτａｐｈｙ Ｃｏｌｕｍｎｚ’）：アナリテイカル
ケミストリー（ＡｎａｌｙｔＬｃａｌＣｌｔｍｃｚｔｒ
ｙ ｐ ＦＯｌ−５４＋ １９８２ ＃ ７１２〜７１
５ ）に述べられているように、ＥＣｌ、 Ｈ，ＰＯ，
、Ｅ、Ｓｏ、等が用いられていた。しかし、この方法で
はサプレッサ通過後の溶離液の導電率は依然として高い
ために、検出器として導電率検出器を用いることが困難
となる。そのため、上記した方法を用いた場合には検出
器として紫外吸収検出器が使用されることとなる。とこ
ろが、紫外吸収検出器は、紫外債域に吸収をもたない試
料には応答しないため、測定対象イオンが限定されると
いう問題がある。In the conventional ion pair chromatography measurement method, a hydroxide solution of an ion pair reagent such as tetrabutylammonium is used as an ion pair reagent eluent. In suppressor-type ion pair chromatography measurements, a suppressor is installed after the separation column, and the hydroxide in the ion pair reagent is converted to H,0 by cation exchange within the suppressor, resulting in low conductivity of the eluent. This is because the eye surface component can be detected by a conductivity detector. However, the hydroxide solution used as an ion pairing reagent has a pH of 10 or higher, making analysis 9 of samples that decompose under alkaline conditions impossible, and silica thread columns cannot be used as separation columns because they are damaged by eluents with a pH of 7 or higher. On the other hand, in ion pair chromatography measurements, the conventional method of lowering the pH of the eluent containing the ion pair reagent was as follows:
NormanΦE Skelly CNo? 7mA' 5kg
1ly); Part of inorganic and organic group ions in reversed phase liquid chromatography column @ (5ep-ara
tion of Inorganic anct Or
ganic Anions orbReverted-
phase Liquid, C'h'roynato
gτaphy Columnz'): Analytical
Chemistry (AnalytLcalCltmcztr
y p FOl-54+ 1982 # 712-71
5), ECl, H, PO,
, E, So, etc. were used. However, in this method, the conductivity of the eluent after passing through the suppressor is still high, making it difficult to use a conductivity detector as a detector. Therefore, when the above method is used, an ultraviolet absorption detector is used as the detector. However, since ultraviolet absorption detectors do not respond to samples that do not have absorption in the ultraviolet range, there is a problem in that the ions to be measured are limited.
上述した従来の技術は、サプレッサ型のイオン対クロマ
トグラフにおいてイオン対試料を含む溶離液のｐＨをＰ
Ｈ１０以下に下げる方法としては適用不可能なもので
あった。本発明の目的は、低ＰＨ９域で測定可能なサプ
レッサ型イオン対クロマトグラフ測定方法及び装置の提
供及び、サプレッサ型イオン対クロマトグラフ用の溶離
液のｐＨをｐ Ｈ１０以下に下げ、かつ任意のＰＨＶＣ
調整する方法及び装置を提供することにある。The above-mentioned conventional technology is a suppressor type ion pair chromatograph in which the pH of an eluent containing an ion pair sample is adjusted to P.
This method was not applicable to lowering the temperature to H10 or lower. The purpose of the present invention is to provide a method and apparatus for measuring suppressed ion pair chromatography that is capable of measuring in the low pH range of 9, and to lower the pH of the eluent for suppressed ion pair chromatography to below pH 10, and to
An object of the present invention is to provide a method and apparatus for adjusting.
上記目的は、サプレッサ型イオン対りロマトグラフ用溶
離液としてイオン対試薬の炭酸塩溶液又は炭酸水素塩溶
液を用いることにより達成されるイオン対試薬とじ又は
テトラプチルアンモニウムテトラグａビルアンモニウム
、高級アミン、アンモニウムイオン等陰イオンとイオン
対を生成するスヘての陽イオンが使用可能である。The above object is achieved by using a carbonate solution or a bicarbonate solution of an ion pairing reagent as an eluent for suppressor type ion pairing chromatography. Any cation that forms an ion pair with an anion such as ammonium ion can be used.
イオン対試薬の炭酸塩及び炭酸水素塩浴１１１ｆ！液は
、市販のそれら試薬を所定＃度に溶解又は希釈して作成
することができる。Ion pair reagent carbonate and bicarbonate bath 111f! The solution can be prepared by dissolving or diluting commercially available reagents to a predetermined degree.
また、イオン対試薬の炭酸塩及び炭酸水素塩溶離液は、
イオン対試薬の水酸化物溶液にＣ０２ガスを溶解する方
法で作成することＤ）できる。ＣＯ２の溶解は、ＣＯ２
ガスまたはＣＯｌを含むガスをｉａ上記浴液に吹き込む
方法又は上記溶液をガス透過性の拡散膜を介してＣＯ，
ガスと接触させ、ガス拡散膜を通過したＣＯ，ガスを溶
解させる方法などで達成できる。ガス拡散膜としては、
例えばシリコン膜、多孔性のテフロン膜等を使用するこ
とができる。In addition, the carbonate and bicarbonate eluents of ion pairing reagents are
D) Can be created by dissolving CO2 gas in a hydroxide solution of an ion pairing reagent. The dissolution of CO2 is CO2
A method of blowing a gas or a gas containing COl into the bath liquid, or a method of blowing a gas containing CO,
This can be achieved by contacting gas and dissolving CO and gas that have passed through a gas diffusion membrane. As a gas diffusion membrane,
For example, a silicon film, a porous Teflon film, etc. can be used.
同じくイオン対試薬の炭酸塩及び炭酸水素塩溶離液は、
Ｎａ１ｉＣＯｓ等の炭酸水素塩又は炭酸塩溶液なＨ”ｍ
Ｋ、シた陽イオン交換物質中を流すことにより生成され
るＨ、 ＣＯ，水とイオン対試薬の水酸化物溶液を混合
する方法で作成することができる。上記陽イオン交換物
質とし℃は、例えは陽イオン交換膜、陽イオン交換樹脂
等を使用することができる。Similarly, the carbonate and bicarbonate eluents of ion-pairing reagents are
Hydrogen carbonate or carbonate solution H”m such as Na1iCOs
It can be prepared by mixing a hydroxide solution of an ion pairing reagent with H, CO, and water produced by flowing a cation exchange material through a cation exchange material. As the above-mentioned cation exchange material, for example, a cation exchange membrane, a cation exchange resin, etc. can be used.
イオン対試薬の炭酸塩又は炭酸水素塩溶離液のｐＨは、
イオン対試薬の炭酸塩及び炭酸水素塩の混合比を変える
ことにより任意に調整することが可能である。またイオ
ン対試薬の水酸化物溶液に００２を溶解する方法におい
てはＣＱ、ガスの溶解室を変えることによりＰＨを任意
に調整することができる。またイオン対試薬の水酸化物
溶液とＮａＨＣＯ＊溶液等の陽イオン交換により生成さ
れるＨ、Ｃｏ、水との混合により作成する方法において
は、上記両液の混合比又はＨＩＣＯ，濃度を変えること
により任意のＰ ＨＫＷ１４整することができる。The pH of the carbonate or bicarbonate eluent of the ion-pairing reagent is
It can be arbitrarily adjusted by changing the mixing ratio of carbonate and hydrogen carbonate as ion pairing reagents. Furthermore, in the method of dissolving 002 in a hydroxide solution of an ion pairing reagent, the pH can be arbitrarily adjusted by changing the CQ and gas dissolution chambers. In addition, in the method of preparing an ion pairing reagent by mixing a hydroxide solution with H, Co, and water generated by cation exchange such as NaHCO* solution, the mixing ratio of the two solutions or the HICO concentration may be changed. Any PHKW14 can be adjusted by.
イオン対試薬の炭酸塩及び炭酸水素塩溶液より成る溶離
液は従来から使用のイオン対試薬の水酸化物より成る溶
離液に比べてｐＨが低く、かつサプレッサ内での陽イオ
ン交換によりＨ，Ｃｏ、溶液に変換され、サプレッサ通
過後の溶Ｗ＆液の導電率は大幅に低下するため、検出器
として導電率検出器を使用することが可能となる。The eluent consisting of carbonate and bicarbonate solutions of ion-pairing reagents has a lower pH than the eluent of conventionally used ion-pairing reagents of hydroxide, and has a lower pH due to cation exchange within the suppressor. , the conductivity of the solution W & liquid after being converted into a solution and passing through the suppressor is significantly reduced, making it possible to use a conductivity detector as a detector.
イオン対試薬の水酸化物溶液にＣＯ，ガスを溶解させる
ことによりイオン対試薬の炭酸塩又は炭酸水素塩溶離液
を作成する方法においては、蘭単にはＣＯ２ガスまたは
ＣＯｌを一足ｍ！で含むガスをイオン対試薬の水酸化物
溶液に吹き込むことにより作成することができ、ＣＯ，
ガスやＣＯｌを含むガスσ５通気時間や通気速度を変え
ることにより上記作成溶液のｐＨを変えることかできる
。またガス拡散膜を介してイオン対試薬の水酸化物溶液
とＣＯ。In the method of preparing a carbonate or bicarbonate eluent of an ion pairing reagent by dissolving CO2 gas in a hydroxide solution of an ion pairing reagent, one or more m! It can be created by blowing a gas containing CO,
The pH of the prepared solution can be changed by changing the aeration time and aeration rate of the gas σ5 containing gas and COl. Also, the hydroxide solution of the ion pairing reagent and CO through the gas diffusion membrane.
ガスを接触させる方法においては、ガス拡散膜は液体に
比べて分子サイズの小さいガスのみを通すために、ガス
拡散膜を通過したＣＯ□ガスが上記浴液に溶解して炭酸
塩溶液が作成される。同時にガス拡散膜の厚さ、溶液と
の接触面積、接触時間等を変えることにより、上記した
作成溶液のｐＨを任意に調至することができる。In the method of bringing gas into contact, the gas diffusion membrane allows only gases with a smaller molecular size to pass through than the liquid, so the CO□ gas that has passed through the gas diffusion membrane is dissolved in the bath liquid to create a carbonate solution. Ru. At the same time, by changing the thickness of the gas diffusion membrane, the contact area with the solution, the contact time, etc., the pH of the above-described prepared solution can be adjusted as desired.
ＮαＨＣＯ，等の炭酸水素塩又は炭酸塩浴液をＨ＋型に
した陽イオン交換物質中を流すことにより生成されるＨ
、Ｃｏ、水とイオン対試薬の水酸化物浴液な混合する方
法においては、上記ＮａＨｃＯ，等の炭酸水素塩又は炭
酸塩の濃度を一定にすれは一定濃度のＨ，Ｃｏ、水が得
られるので、上記ＮａＨＣＣ）ｓ等の炭酸水素塩又は炭
酸塩溶液の濃度およびイオン対試薬の水酸化物溶液との
混合比を変えること罠より、ＰＨを任意Ｋｉえることが
できる。H generated by flowing a bicarbonate such as NαHCO, or a carbonate bath solution through a cation exchange material in the H+ form.
In the method of mixing ion-pairing reagents such as hydroxide bath liquid with Co, Co, and water, by keeping the concentration of hydrogen carbonate or carbonate such as NaHcO, etc. constant, a constant concentration of H, Co, and water can be obtained. Therefore, by changing the concentration of hydrogen carbonate or carbonate solution such as the above-mentioned NaHCC)s and the mixing ratio of the ion pair reagent with the hydroxide solution, the pH can be adjusted arbitrarily.
以下、−面を参照しながら本発明を詳述する。 Hereinafter, the present invention will be described in detail with reference to the negative side.
第１図は、本発明の一実施例を示す概要図であり、イオ
ン対試薬の炭酸塩又は炭酸水素塩を含む溶離液１は、定
量ポンプ２により定速でインジエクシ賃ンバルプ３から
分離カラム４．陽イオン交換膜サプレッサ５．導電率検
出器８へと送られる。サグレツサ内の陽イオン交換層の
外側へはＨ，５０４溶液７が定量ポンプ６を用いて常時
送入されるため。FIG. 1 is a schematic diagram showing an embodiment of the present invention, in which an eluent 1 containing carbonate or hydrogen carbonate as an ion-pairing reagent is transferred from an injection valve 3 to a separation column 4 at a constant rate using a metering pump 2. ．． Cation exchange membrane suppressor5. It is sent to a conductivity detector 8. This is because the H,504 solution 7 is constantly fed to the outside of the cation exchange layer in the Sagretsusa using the metering pump 6.
上記陽イオン交換膜サプレッサは常にｒ型に再生されて
いる。The above cation exchange membrane suppressor is always regenerated into r-type.
本実施例によれは、サプレッサ５内に送られた上記溶離
液は陽イオン交換によりＨ，Ｃｏ、に変換されるため、
導電率検出器８を用いて測定されるバックグラウンド導
電率が低下するため、インジェクタ１ンバルグ３から注
入される試料成分の溶出による導電率の上昇を導電率検
出器８により扁精度、高感度に検出することができる。According to this embodiment, the eluent sent into the suppressor 5 is converted into H and Co by cation exchange, so that
Since the background conductivity measured using the conductivity detector 8 decreases, the increase in conductivity due to the elution of sample components injected from the injector 1 bulk 3 can be detected with high precision and high sensitivity by the conductivity detector 8. can be detected.
また、上記溶離液は従来から用いられているイオン対試
薬の水酸化物を含む溶離液に比べてＰＨが低く、ＰＨ７
以下にも調整が可能である。従ってアルカリ性で分解し
易い試料の分析に通用することができるｄまた分離カラ
ムとして、従来のイオン対試薬の水酸化物を含む溶離液
を使用した場合はポリマーベース系の分離カラムしか使
用することができなかったが、本実施例によれば、上記
ポリマーベース系の分離カラムはもちろん、アルカリ性
では損傷を受けるために従来から使用できなかったシリ
カベース系の分離カラムをも使用することが可能である
。In addition, the above eluent has a lower pH than the eluent containing the hydroxide of the ion pairing reagent used conventionally, and has a pH of 7.
The following adjustments are also possible. Therefore, it can be used for analysis of samples that are alkaline and easily decomposed.In addition, when using an eluent containing the conventional ion pairing reagent hydroxide, only a polymer-based separation column can be used. However, according to this example, it is possible to use not only the above-mentioned polymer-based separation column but also a silica-based separation column, which could not be used conventionally because it would be damaged by alkalinity. .
第２図は本発明の一実施例を示す図である。定量ポンプ
１０の吸引側はガス拡散膜チューブ１２をへて、イオン
対試薬の水酸化物浴液１３とつながっており、上記溶液
が定速でガス拡散膜チューブ１２内を通過する間に、ガ
ス拡散膜を通過するＣＯ２の溶解によりイオン対試薬の
炭酸塩又は炭酸水素塩溶液が生成される。ＣＯ，ガスは
ＣＯ２ガスポンベ１４より′＃Ｌｔ調整器１５を経て、
定速で連続又は間欠的に外筒１１に供給される。ガス拡
散膜はチューブ状のものの他に、平らな膜を一定間隔で
重ねて使用し。FIG. 2 is a diagram showing an embodiment of the present invention. The suction side of the metering pump 10 is connected to the hydroxide bath solution 13 of the ion pair reagent through the gas diffusion membrane tube 12, and while the solution passes through the gas diffusion membrane tube 12 at a constant speed, the gas The dissolution of CO2 passing through the diffusion membrane produces a carbonate or bicarbonate solution of the ion-pairing reagent. CO, gas passes from the CO2 gas pump 14 through the '#Lt regulator 15.
It is supplied to the outer cylinder 11 continuously or intermittently at a constant speed. In addition to tube-shaped gas diffusion membranes, flat membranes are used stacked at regular intervals.
イオン対試薬の水酸化ｖｌＪ溶液をその間に流すること
も可能である。また本実施例を第１図における実施例に
示したインジエクシ璽ンバルプ５に従続し、連続的に生
成されるイオン対試薬の炭酸塩及び炭酸水素塩浴液をそ
のまま溶離液として分離カラム４に送入することが可能
である。なお、溶離液中にメタノール、アセトニトリル
等の有機溶媒を添加する必要がある場合は、予めイオン
対試薬の水酸化物溶液中に所定濃度で添加しておくこと
或いは定量ポンプ１０とインジエクシ曹ンバルブ５の間
に混合器を設けて他の定量ポンプを用いて一定比率で重
加することが可能である。It is also possible to flow a hydroxylated vlJ solution of the ion-pairing reagent in between. In addition, this example was carried out by following the injection valve 5 shown in the example in FIG. It is possible to send If it is necessary to add an organic solvent such as methanol or acetonitrile to the eluent, add it to the hydroxide solution of the ion pairing reagent at a predetermined concentration in advance, or add it to the hydroxide solution of the ion pairing reagent or It is possible to provide a mixer in between and add in a constant ratio using another metering pump.
く実験例１〉
第２図のガス拡散膜チェープにシリコンチューブを用い
、その中をイオン対試薬の水酸化物溶液として水酸化テ
トラ１チルアンモニウム２ｍＡｆ 浴液を毎分１ｍｌの
流速で流した。シリコンチエ−１の膜厚、長さを変えた
時に生成される溶離液のｐＨは表１に示すとうりであっ
た。Experimental Example 1 A silicone tube was used for the gas diffusion membrane chain shown in FIG. 2, and a 2 mAf bath solution of tetra-1-thylammonium hydroxide was flowed therein at a flow rate of 1 ml per minute as a hydroxide solution of an ion pairing reagent. Table 1 shows the pH of the eluent produced when the film thickness and length of Silicon Che-1 were changed.
ｃ以下余白）
表１
ｗｃｓ図は本発明の一実施例を示す図である。定量ポン
プ１６は流量調節バルブ１７を介してイオン対試薬の水
酸化物溶液１８及び炭酸水素塩浴液１９とつなかってお
り、流量調節バルブ１７で各々の流量を調節することか
できる。２０は陽イオン交換装置で、陽イオン交換膜チ
ェーブ２１の外側に、定量ポンプ２２を用いてＨ，ＳＯ
，を浴液２３を定速で送ることにより陽イオン交換膜チ
ューブは常時Ｈ＋型に再生されχいる。ｒ型の陽イオン
交換膜チューブ２１内を流れる間に炭酸水素塩溶液１９
はＨ，Ｃｏ、水に変換される。生成されたＨ、Ｃｏ、水
とイオン対試薬の水酸化物溶液１８は混合器２４内で均
一に混合される。炭酸水素塩溶液１９としてはＡ’ｃｚ
７１／ＣＯｓ 。(margins below c) Table 1 The wcs diagram is a diagram showing one embodiment of the present invention. The metering pump 16 is connected to a hydroxide solution 18 of an ion pair reagent and a hydrogen carbonate bath liquid 19 via a flow rate control valve 17, and the flow rate of each can be adjusted by the flow rate control valve 17. Reference numeral 20 denotes a cation exchange device, which supplies H, SO to the outside of the cation exchange membrane chamber 21 using a metering pump 22.
, by sending the bath liquid 23 at a constant rate, the cation exchange membrane tube is constantly regenerated into the H+ type. While flowing through the r-type cation exchange membrane tube 21, the bicarbonate solution 19
is converted into H, Co, and water. The generated H, Co, water, and ion pairing reagent hydroxide solution 18 are uniformly mixed in the mixer 24. A'cz as hydrogen carbonate solution 19
71/COs.
ＫＨＣＯ，、ＮＨ４ＨＣＯ，等の炭酸水素塩溶液の他に
Ｎα、Ｃｏ、 、 Ｋ、ＣＯｓ等の炭酸塩浴液も使用で
きる。In addition to bicarbonate solutions such as KHCO, NH4HCO, etc., carbonate bath solutions such as Nα, Co, , K, COs, etc. can also be used.
Ｈ，５０４溶液２３としては、Ｈ！Ｓｏ、の他にＨ’、
ｐｏ４や有機酸など解離度の大きい酸はいずれも使用可
能である。また陽イオン交換装置２０としてはＨ＋型に
再生した陽イオン交換樹脂カラムを使用することも可能
であり、陽イオン交換膜チューブ２１はチューブ状のも
のの他に陽イオン交換族を層状に重ね、その間に炭酸水
素塩溶液を、外側にＥＩＳｏ４溶液を流して使用するこ
とも可能である。As H,504 solution 23, H! In addition to So, H',
Any acid with a high degree of dissociation such as po4 or organic acid can be used. In addition, it is also possible to use a cation exchange resin column regenerated into H+ type as the cation exchange device 20, and the cation exchange membrane tube 21 is a tube-shaped one in addition to a cation exchange group layered in layers. It is also possible to use a bicarbonate solution on the outside and an EISo4 solution on the outside.
本実施例を第１図実施例に示したインジエクシ習ンバル
グ３に接続し、連続的に主成されるイオン対試薬の炭酸
塩及び炭酸水素塩溶液を溶離液としてそのまま分離カラ
ム４に送入することが可能である。なお第２図実施例の
場合と同様の方法で溶離液中に有機溶媒を添加すること
も可能である。This example is connected to the Injiexi Yumbulg 3 shown in the example in Figure 1, and the carbonate and bicarbonate solutions of the ion pairing reagent, which are mainly formed, are continuously fed into the separation column 4 as they are as an eluent. Is possible. Note that it is also possible to add an organic solvent to the eluent in the same manner as in the example shown in FIG.
く芙職例２〉
陽イオン交換膜チューブ５に内径０．２ｍ７７！、長さ
１ｍのポリエチレン系陽イオン交換膜チューブを使用し
、その外側Ｋ Ｏ，０５＃ Ｈ，ＳＯ４溶液を毎分２ｍ
ｌの流速で流した。イオン対試薬の水酸化物溶液１８と
して４輌水酸化テトラブチルアンモニウム溶液、炭酸水
素塩溶液１９としてＮａＥＣＯｓ浴液を使用し、定量ポ
ンプ１６を毎分２ｒｎｌ ／ニルの流速で駆動させた。Kufu job example 2> Cation exchange membrane tube 5 has an inner diameter of 0.2m77! A polyethylene cation exchange membrane tube with a length of 1 m was used, and the outside of the KO, 05# H, SO4 solution was applied at a rate of 2 m/min.
It was flowed at a flow rate of 1. A tetrabutylammonium hydroxide solution was used as the hydroxide solution 18 of the ion pairing reagent, a NaEC0s bath solution was used as the bicarbonate solution 19, and the metering pump 16 was driven at a flow rate of 2 rnl/min.
流速―節パルプ１７を調節して定量ポンプ１６に入る１
８ 、１９の２種の溶液の流速が１：１になるように設
定した。本実嵌装置を用いてＮａＥＣ０３溶液の濃度を
０〜１５店ＶＣ変えたときに生成される溶離液のｐＨは
表２に示すとうりであった。Flow rate - Adjust the node pulp 17 and enter the metering pump 16 1
The flow rate of the two solutions No. 8 and No. 19 was set to be 1:1. Table 2 shows the pH of the eluent produced when the concentration of the NaEC03 solution was varied from 0 to 15 VC using this practical device.
表２
〔発明の効果〕
本発明によれは、サプレッサ型イオン対りロマトグラフ
測足においてＰＨ１０〜ＰＨ５の低ＰＨ鎖酸での測定が
可能となるので、アルカリ性で分解し易い試料の分析が
可能となる。また、分離カラムとして中性以下で使用さ
れるシリカベース系カラムを利用することができ、適用
対象試料が大幅に拡大する。Table 2 [Effects of the Invention] According to the present invention, it is possible to measure with low pH chain acids of PH10 to PH5 in suppressor type ion pair romatograph measurement, so it is possible to analyze samples that are alkaline and easily decomposed. Become. In addition, a silica-based column that is used below neutrality can be used as a separation column, greatly expanding the range of applicable samples.
第１図、第２図、第３図はいずれも本発明の実施例を示
す概要図である。
１・・・イオン対試薬の炭酸水素塩溶液２・・・定量ポ
ンプ
５・・・イ／ジエクシ目ンバルプ
４・・・分離カラム
５・・・陽イオン交換膜サプレッサ
６・・・定量ポンプ
７・・・Ｈ，５０４溶液
８・・・導電率検出器
９・・・記録計
１０・・・定量ポンプ
１１・・・外筒
１２・・・ガス拡散膜チューブ
１５・・・イオン対試楽の水酸化物溶液１４・・・ＣＯ
，ガスボンベ
１５・・・流ｆ調歪器
１６・・・定量ポンプ
１７・・・流を調節パルプ
１８・・・イオン対試薬の水酸化物溶液１９・・・炭酸
水素塩溶液
２０・・・陽イオン交換装置
２１・・・陽イオン交換膜チューブ
２２・・・定量ポンプ
２３・・・Ｈ，ＳＯ４溶液
２４・・・混合器
代理人 升埋士 小 川 膀 男
第１図
？
１ヂオ〕り寸試薬の屓（ぐ２１（素培溶別し侵 ２
、定量ポシプ３つジエクションバル〕゛
４ 分離カラム５服げオシク秒陣莫サプレッサ
６ 定１ボシプ’？ Ｈ２ＳＯ↓溶蔑 ８
導電♀挽出器９ 言己今表計
第２図FIG. 1, FIG. 2, and FIG. 3 are all schematic diagrams showing embodiments of the present invention. 1... Hydrogen carbonate solution of ion pairing reagent 2... Metering pump 5... I/Diexium valve 4... Separation column 5... Cation exchange membrane suppressor 6... Metering pump 7. ... H,504 solution 8 ... Conductivity detector 9 ... Recorder 10 ... Metering pump 11 ... Outer tube 12 ... Gas diffusion membrane tube 15 ... Hydroxylation of ion pair sample Product solution 14...CO
, gas cylinder 15...flow f adjuster 16...metering pump 17...adjust flow Pulp 18...hydroxide solution of ion pairing reagent 19...bicarbonate solution 20...positive Ion exchange device 21... Cation exchange membrane tube 22... Metering pump 23... H, SO4 solution 24... Mixer representative Masuji Ogawa Urinary man Figure 1? 1. Reagent size 21 (prime culture dissolution and invasion)
, three quantitative determination valves゛
4 Separation Column 5 Suppressor
6 fixed 1 bossip'? H2SO↓Disdain 8
Conductive ♀ Extractor 9 Kotoki Now Table Table 2
Claims (1)
に用いることを特徴とするサプレッサ型イオン対クロマ
トグラフ測定方法。 ２、請求項１記載のサプレッサ型イオン対クロマトグラ
フ測定方法において、ガス拡散膜を介してイオン対試薬
の水酸化物浴液とＣＯ＿２ガスを接触させ、ガス拡散膜
を通過するＣＯ＿２をイオン対試薬の水酸化物溶液に溶
解させることにより生成されるイオン対試薬の炭酸塩又
は炭酸水素塩溶液を溶離液に用いることを特徴とするサ
プレッサ型イオン対クロマトグラフ測定方法。 ３、請求項１記載のサプレッサ型イオン対クロマトグラ
フ測定方法において、炭酸水素塩又は炭酸塩溶液をＨ＾
＋型陽イオン交換物質中に流して生成されるＨ＿２ＣＯ
＿３水とイオン対試薬の水酸化物溶液を混合することに
より生成されるイオン対試薬の炭酸塩又は炭酸水素塩溶
液を溶離液に用いることを特徴とするサプレッサ型イオ
ン対クロマトグラフ測定方法。 ４、イオン対試薬の炭酸塩又は炭酸塩溶液を溶離液とし
て用いることを特徴としたサプレッサ型イオン対クロマ
トグラフ測定装置。 ５、請求項４記載のサプレッサ型イオン対クロマトグラ
フ測定装置において、ＣＯ＿２を含むガスを保持する容
器と、その中にあり一方の面が当該気体と接し、かつ他
方の面に接してイオン対試薬の水酸化物溶液を一定流速
で流すことができる構造を持ったガス拡散膜より成る隔
膜を有することを特徴とするサプレッサ型イオン対クロ
マトグラフ測定装置。 ６、請求項４記載のサプレッサ型イオン対クロマトグラ
フ測定装置において、炭酸水素塩又は炭酸塩溶液を炭酸
水に変換するための陽イオン交換装置と、陽イオン交換
装置で生成された炭酸水をイオン対試薬の水酸化物溶液
と混合する混合器とを設けたことを特徴とするサプレッ
サ型イオン対クロマトグラフ測定装置。 ７、ガス拡散膜を介してイオン対試薬の水酸化物溶液と
ＣＯ＿２ガスを接触させ、拡散膜を通過するＣＯ＿２を
該溶液に溶解させることを特徴とするイオン対試薬の炭
酸塩及び炭酸水素塩溶離液の作成方法。 ８、炭酸水素塩又は炭酸塩溶液を、Ｈ＾＋型陽イオン交
換物質中に流して生成される炭酸水をイオン対試薬の水
酸化物溶液と混合することを特徴とするイオン対試薬の
炭酸塩及び炭酸水素塩溶離液の作成方法。 ９、請求項７記載のイオン対試薬の炭酸塩及び炭酸水素
塩溶離液作成方法において、ガス拡散膜の厚さ、拡散膜
の面積、ＣＯ＿２ガスとイオン対試薬の水酸化物溶液の
接触時間を変えて任意のＰＨに調整することを特徴とす
るイオン対試薬の炭酸塩及び炭酸水素塩溶離液の作成方
法。 １０、請求項８記載のイオン対試薬の炭酸塩及び炭酸水
素塩溶離液の作成方法において、Ｈ＾＋型陽イオン交換
物質中を流す炭酸水素塩又は炭酸塩溶液の濃度及び上記
方法で生成された炭酸水とイオン対試薬の水酸化物溶液
との混合比を変えることにより任意のＰＨに調整するこ
とを特徴とするイオン対試薬の炭酸塩及び炭酸水素塩溶
離液の作成方法。 １１、ＣＯ＿２を含むガスを保持する容器と、その中に
あり、一方の面が当該気体と接し、かつ他方の面に接し
てイオン対試薬の水酸化物溶液を一定速度で流すことが
できる構造を持ったガス拡散膜より成る隔膜を有するこ
とを特徴とするイオン対試薬の炭酸塩及び炭酸水素塩溶
離液の作成装置。 １２、炭酸水素塩又は炭酸塩溶液を炭酸水に変換するた
めの陽イオン交換装置と、陽イオン交換装置で生成され
た炭酸水とイオン対試薬の水酸化物溶液とを混合する混
合器より成るイオン対試薬の炭酸塩及び炭酸水素塩溶離
液の作成装置。[Scope of Claims] 1. A suppressor type ion pair chromatography measurement method characterized in that a carbonate or hydrogen carbonate solution of an ion pair reagent is used as an eluent. 2. In the suppressor type ion pair chromatography measurement method according to claim 1, the hydroxide bath liquid of the ion pair reagent and CO_2 gas are brought into contact through a gas diffusion membrane, and the CO_2 passing through the gas diffusion membrane is used as the ion pair reagent. A suppressor-type ion pair chromatography measurement method characterized in that a carbonate or hydrogen carbonate solution of an ion pair reagent produced by dissolving the ion pair reagent in a hydroxide solution is used as an eluent. 3. In the suppressor type ion pair chromatography measurement method according to claim 1, hydrogen carbonate or carbonate solution is
H_2CO generated by flowing into + type cation exchange material
_3 A suppressor-type ion pair chromatography measurement method characterized in that a carbonate or bicarbonate solution of an ion pair reagent produced by mixing water and a hydroxide solution of an ion pair reagent is used as an eluent. 4. A suppressor type ion pair chromatography measuring device characterized in that a carbonate or a carbonate solution of an ion pair reagent is used as an eluent. 5. The suppressor type ion pair chromatography measuring device according to claim 4, comprising: a container holding a gas containing CO_2; 1. A suppressor-type ion pair chromatography measuring device characterized by having a diaphragm made of a gas diffusion membrane having a structure that allows a hydroxide solution to flow at a constant flow rate. 6. The suppressor-type ion pair chromatography measuring device according to claim 4, further comprising a cation exchange device for converting bicarbonate or carbonate solution into carbonated water, and a cation exchange device for converting the carbonated water produced by the cation exchange device into ionized water. 1. A suppressor type ion pair chromatography measuring device characterized by being provided with a mixer for mixing with a hydroxide solution of a counter reagent. 7. Carbonates and hydrogen carbonates of ion pairing reagents, characterized in that the hydroxide solution of the ion pairing reagent is brought into contact with CO_2 gas through a gas diffusion membrane, and the CO_2 passing through the diffusion membrane is dissolved in the solution. How to make the eluent. 8. Carbonic acid as an ion pairing reagent, characterized in that carbonated water produced by flowing a bicarbonate or a carbonate solution through an H^+ type cation exchange material is mixed with a hydroxide solution of an ion pairing reagent. Method for making salt and bicarbonate eluents. 9. In the method for preparing a carbonate and hydrogen carbonate eluent of an ion pairing reagent according to claim 7, the thickness of the gas diffusion membrane, the area of the diffusion membrane, and the contact time of the CO_2 gas and the hydroxide solution of the ion pairing reagent are 1. A method for preparing a carbonate and hydrogen carbonate eluent of an ion pairing reagent, which comprises adjusting the pH to an arbitrary value. 10. In the method for preparing a carbonate and bicarbonate eluent of an ion pairing reagent according to claim 8, the concentration of the bicarbonate or carbonate solution flowing through the H^+ type cation exchange material and the A method for preparing a carbonate and hydrogen carbonate eluent for an ion pairing reagent, which comprises adjusting the pH to a desired value by changing the mixing ratio of carbonated water and a hydroxide solution for an ion pairing reagent. 11. A container that holds a gas containing CO_2, and a structure within the container that is in contact with the gas on one side and that allows a hydroxide solution of an ion pairing reagent to flow at a constant rate in contact with the other side. 1. An apparatus for preparing a carbonate and hydrogen carbonate eluent of an ion pairing reagent, characterized in that it has a diaphragm made of a gas diffusion membrane having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm having a diaphragm. 12. Consists of a cation exchange device for converting bicarbonate or carbonate solution into carbonated water, and a mixer for mixing the carbonated water produced by the cation exchange device and a hydroxide solution of an ion pairing reagent. Device for preparing carbonate and bicarbonate eluents for ion pairing reagents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63128365A JPH01299457A (en) | 1988-05-27 | 1988-05-27 | Method and apparatus for measuring suppressor type ion-pair chromatograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63128365A JPH01299457A (en) | 1988-05-27 | 1988-05-27 | Method and apparatus for measuring suppressor type ion-pair chromatograph |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01299457A true JPH01299457A (en) | 1989-12-04 |
Family
ID=14983021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63128365A Pending JPH01299457A (en) | 1988-05-27 | 1988-05-27 | Method and apparatus for measuring suppressor type ion-pair chromatograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01299457A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010137132A1 (en) * | 2009-05-27 | 2010-12-02 | 株式会社島津製作所 | Method for measurement of anion |
-
1988
- 1988-05-27 JP JP63128365A patent/JPH01299457A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010137132A1 (en) * | 2009-05-27 | 2010-12-02 | 株式会社島津製作所 | Method for measurement of anion |
| JP5408249B2 (en) * | 2009-05-27 | 2014-02-05 | 株式会社島津製作所 | Anion measurement method |
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