JPH05240846A - Cation measuring method - Google Patents
Cation measuring methodInfo
- Publication number
- JPH05240846A JPH05240846A JP4310292A JP4310292A JPH05240846A JP H05240846 A JPH05240846 A JP H05240846A JP 4310292 A JP4310292 A JP 4310292A JP 4310292 A JP4310292 A JP 4310292A JP H05240846 A JPH05240846 A JP H05240846A
- Authority
- JP
- Japan
- Prior art keywords
- cation
- cations
- sample
- column
- organic solvent
- 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
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、イオンクロマトグラフ
ィなどを用いて試料に含まれている陽イオンを測定する
陽イオンの測定方法に係わり、特に、水溶性の有機溶媒
に含まれている陽イオンを簡便かつ高精度に測定する方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cation measuring method for measuring cations contained in a sample by using ion chromatography or the like, and particularly to cations contained in a water-soluble organic solvent. The present invention relates to a simple and highly accurate method for measuring.
【０００２】[0002]
【従来の技術】周知のように、イオンクロマトグラフィ
は簡便な陽イオンの測定方法である。しかし、イオンク
ロマトグラフィの主たる適用分野は、水溶液中の陽イオ
ンを測定することであり、有機溶媒中の陽イオンの測定
をイオンクロマトグラフィで行う場合、次のような前処
理が必要となる。As is well known, ion chromatography is a simple method for measuring cations. However, the main field of application of ion chromatography is to measure cations in an aqueous solution, and when measuring cations in an organic solvent by ion chromatography, the following pretreatment is required.
【０００３】即ち、有機溶媒が非水溶性有機溶媒の場合
には、分液ロートなどで非水溶性有機溶媒の中に含まれ
ている陽イオンを水の中へ排出することが必要であり、
有機溶媒が水溶性有機溶媒の場合には、適宜希釈するこ
とが必要である。このような前処理は、大量の有機溶媒
が注入されると分離カラムやサプレッサの性能が低下す
る危険性があるため、有機溶媒を分離カラムやサプレッ
サにできるだけ入れないようにするために行われる。That is, when the organic solvent is a non-water-soluble organic solvent, it is necessary to discharge the cations contained in the non-water-soluble organic solvent into water with a separating funnel or the like.
When the organic solvent is a water-soluble organic solvent, it is necessary to appropriately dilute it. Such pretreatment is performed to prevent the organic solvent from entering the separation column or the suppressor as much as possible, because the performance of the separation column or the suppressor may be deteriorated when a large amount of the organic solvent is injected.
【０００４】[0004]
【発明が解決しようとする問題点】然しながら、上述の
ような前処理は陽イオンの分析操作上、注入される陽イ
オンの絶対濃度が低くなってしまう上、イオンクロマト
グラフィでの分析とは別に試料毎に前処理を行わなけれ
ばならないという欠点があった。特に、注入される陽イ
オンの絶対濃度が低くなると、有機溶媒中の微量陽イオ
ンを分析するうえで重大な支障が生じていた。このた
め、近時、分離カラムやサプレッサを改善することによ
り、上述のような希釈操作を行うことなく試料を注入す
る方法も試みられていた。しかし、この方法は全ての有
機溶媒に適用できるわけではなかった。However, in the pretreatment as described above, the absolute concentration of the injected cations is lowered due to the cation analysis operation, and the sample is separated from the sample by the ion chromatography analysis. There was a drawback that pretreatment had to be performed every time. In particular, when the absolute concentration of the injected cations becomes low, there has been a serious problem in analyzing trace cations in the organic solvent. Therefore, recently, a method of injecting a sample without performing the above-described dilution operation has been attempted by improving a separation column and a suppressor. However, this method was not applicable to all organic solvents.
【０００５】また、薬品の高純度化が進展するに伴い、
有機溶媒とりわけ水溶性有機溶媒に含まれている微量の
陽イオンを測定することが重要視されてきており、該陽
イオンを簡便かつ高精度に測定する陽イオンの測定方法
の実現が強く望まれていた。本発明は、かかる状況など
に鑑み上述のような従来例の欠点を解消せんとして成さ
れたものであり、水溶性有機溶媒に含まれている陽イオ
ンを簡便かつ高精度に測定する陽イオンの測定方法を提
供することを目的とする。Further, as the purification of chemicals progresses,
It has been emphasized to measure a small amount of cations contained in an organic solvent, especially a water-soluble organic solvent, and it is strongly desired to realize a cation measurement method that can easily and accurately measure the cations. Was there. The present invention has been made in view of the above circumstances in order to solve the drawbacks of the conventional examples as described above, and a cation for easily and accurately measuring a cation contained in a water-soluble organic solvent. The purpose is to provide a measuring method.
【０００６】[0006]
【問題点を解決するための手段】本発明は、陽イオンの
測定方法において、水溶性有機溶媒などでなる試料を一
定量採取する試料導入部と該試料中の陽イオンをクロマ
トグラフィックに分離する分離カラム部との間に、陽イ
オン交換樹脂を充填した陽イオン捕捉用カラムを設置
し、該陽イオン捕捉用カラムで前記試料中の陽イオンを
捕捉し、その後、前記陽イオン捕捉用カラムに洗浄用純
水を流して前記陽イオン捕捉用カラムに含まれている水
溶性有機溶媒を洗い出し、その後、溶離液で前記陽イオ
ン捕捉用カラムに捕捉されている陽イオンを前記分離カ
ラム部に搬入することによって前記課題を解決したもの
である。According to the present invention, in a method for measuring cations, a sample introducing part for collecting a fixed amount of a sample made of a water-soluble organic solvent and the cations in the sample are chromatographically separated. A cation trapping column filled with a cation exchange resin is installed between the separation column section, the cations in the sample are trapped by the cation trapping column, and then the cation trapping column is used. Pure water for washing is flowed to wash out the water-soluble organic solvent contained in the cation trapping column, and then the cations trapped in the cation trapping column with an eluent are carried into the separation column section. By doing so, the above problem is solved.
【０００７】[0007]
【作用】本発明は次のように作用する。即ち、試料導入
部と分離カラム部との間に陽イオン交換樹脂を充填した
陽イオン捕捉用カラムを設置して試料中の陽イオンを捕
捉したのち、洗浄用純水を流して水溶性有機溶媒を洗い
出し、その後、溶離液で陽イオン捕捉用カラムに捕捉さ
れている陽イオンを分離カラム部に導くようになってい
る。このため、希釈操作などを行うことなく水溶性有機
溶媒１０００％の試料を注入しても、分離カラムやサプ
レッサに水溶性有機溶媒を入れることなく、該水溶性有
機溶媒中の陽イオンを簡便かつ高精度に測定できる。The present invention operates as follows. That is, a cation trapping column filled with a cation exchange resin is installed between the sample introduction part and the separation column part to trap cations in the sample, and then pure water for washing is flowed to dissolve the water-soluble organic solvent. Are washed out, and then the cations trapped in the cation trapping column with the eluent are guided to the separation column section. Therefore, even if a sample of 1000% water-soluble organic solvent is injected without performing a diluting operation or the like, the cation in the water-soluble organic solvent can be simply and easily introduced without inserting the water-soluble organic solvent into the separation column or suppressor. Can measure with high accuracy.
【０００８】[0008]
【実施例】以下、本発明の実施例について図を用いて詳
細に説明する。図１は本発明実施例を説明するための図
であり、図中、１は溶離液を貯留する溶離液槽、２は純
水を貯留する純水槽、３は溶離液を送液する溶離液送液
ポンプ、４は純水を送液する純水送液ポンプ、５は第１
〜第６の接続口５ａ〜５ｆと計量管５ｇを有する試料採
取弁、５ｈは試料を注入するためのシリンジ、６は第１
〜第６の接続口６ａ〜６ｆを有する第１切換弁、７は第
１〜第６の接続口７ａ〜７ｆを有する第２切換弁、８は
搬入された試料に含まれている陽イオンを捕捉する陽イ
オン捕捉用カラム、９は搬送される純水に含まれている
陽イオン性不純物を捕捉して除去する不純物除去カラ
ム、１０は搬入される試料に含まれている陽イオンをク
ロマトグラフィックに分離する分離カラム、１１は例え
ば導電率計でなる検出器である。Embodiments of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a diagram for explaining an embodiment of the present invention, in which 1 is an eluent tank for storing an eluent, 2 is a pure water tank for storing pure water, and 3 is an eluent for sending the eluent. Liquid delivery pump, 4 is a pure water delivery pump for delivering pure water, and 5 is a first
~ Sample collection valve having sixth connection ports 5a to 5f and measuring pipe 5g, 5h is a syringe for injecting a sample, and 6 is a first
~ First switching valve having sixth connection ports 6a to 6f, 7 is a second switching valve having first to sixth connection ports 7a to 7f, and 8 is a cation contained in the loaded sample. A cation trapping column for trapping, 9 is an impurity removal column for trapping and removing cationic impurities contained in the pure water to be conveyed, and 10 is a chromatograph of cations contained in the sample to be carried in. The separation column 11 is a detector composed of, for example, a conductivity meter.
【０００９】図２は上記試料採取弁５，第１切換弁６，
及び第２切換弁７の動作を説明するためのタイムチャー
トであり、区間Ａは試料注入、区間Ｂは捕捉・洗浄、区
間Ｃは分離・測定、区間Ｄは溶離液の追出をそれぞれ示
している。FIG. 2 shows the sampling valve 5, the first switching valve 6,
3A and 3B are time charts for explaining the operation of the second switching valve 7. Section A shows sample injection, section B shows trapping / washing, section C shows separation / measurement, and section D shows ejection of eluent. There is.
【００１０】以下、図１，図２を用いて本発明実施例の
動作について説明する。最初、図２の区間Ａで示すよう
に、試料採取弁がオンで、第１切換弁と第２切換弁がオ
フとなっている。このため、図１の試料採取弁５は内部
流路が破線接続状態となっており、第１切換弁６と第２
切換弁７の内部流路は各々実線接続状態となっている。The operation of the embodiment of the present invention will be described below with reference to FIGS. First, as shown in section A of FIG. 2, the sampling valve is on and the first switching valve and the second switching valve are off. For this reason, in the sample collection valve 5 of FIG. 1, the internal flow path is in a broken line connection state, and the first switching valve 6 and the second switching valve 6 are connected.
The internal flow paths of the switching valve 7 are in a state of being connected by solid lines.
【００１１】また、溶離液送液ポンプ３が駆動すると、
溶離液槽１内の溶離液が、溶離液送液ポンプ３→第１切
換弁６の第１，第２接続口６ａ，６ｂ→第２切換弁７の
第５，第６接続口７ｅ，７ｆ→分離カラム１０→検出器
１１の流路を流れる。同様にして、純水送液ポンプ４が
駆動すると、純水槽２内の純水が、純水送液ポンプ４→
第１切換弁６の第３，第４接続口６ｃ，６ｄ→試料採取
弁５の第１，第６接続口５ａ，５ｆ→陽イオン捕捉用カ
ラム８→第２切換弁７の第１，第２接続口７ａ，７ｂの
流路を流れる。When the eluent liquid feed pump 3 is driven,
The eluent in the eluent tank 1 is the eluent feed pump 3 → the first and second connection ports 6a, 6b of the first switching valve 6 → the fifth and sixth connection ports 7e, 7f of the second switching valve 7. → Separation column 10 → Flows through the flow path of the detector 11. Similarly, when the pure water feed pump 4 is driven, the pure water in the pure water tank 2 becomes pure water feed pump 4 →
Third and fourth connection ports 6c, 6d of the first switching valve 6 → first and sixth connection ports 5a, 5f of the sampling valve 5 → column 8 for capturing cations → first and first of the second switching valve 7 2 Flows through the flow paths of the connection ports 7a and 7b.
【００１２】この状態で、シリンジ５ｈから試料採取弁
５の第３接続口５ｃへ試料を注入し、該試料を計量管５
ｇに満たす。その後、図２の区間Ｂで示すように試料採
取弁をオフにすると、図１の試料採取弁５はその内部流
路が実線接続状態となる。このため、計量管５内の試料
は純水に搬送され、該試料中の陽イオンが陽イオン捕捉
用カラム８で捕捉されると共に、該カラム８に捕捉され
ない成分（例えば、水溶性有機溶媒や陰イオン）が第２
切換弁７の第１，第２接続口７ａ，７ｂを通って廃棄さ
れる。このようにして、試料中の水溶性有機溶媒が洗い
流される。In this state, the sample is injected from the syringe 5h into the third connection port 5c of the sample collection valve 5, and the sample is fed into the measuring pipe 5
to g. After that, when the sampling valve is turned off as shown in the section B of FIG. 2, the internal channel of the sampling valve 5 of FIG. 1 is in the solid line connection state. Therefore, the sample in the measuring pipe 5 is transported to pure water, and the cations in the sample are captured by the cation capturing column 8 and the components not captured by the column 8 (for example, water-soluble organic solvent and Anion) is second
It is discarded through the first and second connection ports 7a and 7b of the switching valve 7. In this way, the water-soluble organic solvent in the sample is washed away.
【００１３】次に、図２の区間Ｃで示すように、試料採
取弁、第１切換弁、及び第２切換弁を全てオンにする
と、これらの弁の各内部流路は全てが破線接続状態とな
る。このため、純水槽２内の純水が、純水送液ポンプ４
→不純物除去カラム９→第１切換弁６の第３，第２接続
口６ｃ，６ｂ→第２切換弁７の第５，第４接続口７ｅ，
７ｄの流路を流れる。また、溶離液槽１内の溶離液が、
溶離液送液ポンプ３→第１切換弁６の第１，第６接続口
６ａ，６ｆ→第１切換弁６の第５，第４接続口６ｅ，６
ｄ→試料採取弁５の第１，第６接続口５ａ，５ｆ→陽イ
オン捕捉用カラム８→第２切換弁７の第１，第６接続口
７ａ，７ｆ→分離カラム１０→検出器１１の流路を流れ
る。Next, as shown in the section C of FIG. 2, when the sampling valve, the first switching valve, and the second switching valve are all turned on, all the internal flow paths of these valves are connected in broken lines. Becomes Therefore, the pure water in the pure water tank 2 is transferred to the pure water feed pump 4
→ Impurity removal column 9 → Third and second connection ports 6c and 6b of the first switching valve 6 → Fifth and fourth connection ports 7e of the second switching valve 7
It flows through the channel of 7d. In addition, the eluent in the eluent tank 1 is
Eluent delivery pump 3 → first and sixth connection ports 6a and 6f of the first switching valve 6 → fifth and fourth connection ports 6e and 6 of the first switching valve 6
d → first and sixth connection ports 5a and 5f of the sampling valve 5 → column 8 for cation trapping → first and sixth connection ports 7a and 7f of the second switching valve 7 → separation column 10 → detector 11 Flow through the flow path.
【００１４】従って、陽イオン捕捉用カラム８に捕捉さ
れていた陽イオンは、溶離液に搬送されて分離カラム１
０に至り、ここでクロマトグラフィックに分離される。
また、分離カラム１０の溶出液は検出器１１に導かれて
例えば導電率が検出され、該検出信号が図示しない演算
器などに導かれて陽イオン濃度などが算出される。Therefore, the cations trapped in the cation trapping column 8 are conveyed to the eluent and separated into the separation column 1.
It reaches 0, where it is chromatographically separated.
Further, the eluate of the separation column 10 is guided to the detector 11 to detect, for example, conductivity, and the detection signal is guided to a calculator (not shown) or the like to calculate the cation concentration and the like.
【００１５】このようにして陽イオンの測定が終了した
ら、図２の区間Ｄで示すように試料採取弁がオンのまま
で第１切換弁と第２切換弁がオフにされ、陽イオン捕捉
用カラムに残っている溶離液が純水で洗い出される。こ
れは、図１の陽イオン捕捉用カラム８に溶離液が残って
いると、計量管５ｇ内の試料を陽イオン捕捉用カラム８
に搬入した時、該試料中の陽イオンの一部が残留してい
る溶離液によって陽イオン捕捉用カラム８から溶出する
ため、このような現象が生ずるのを回避するため行われ
るものである。When the measurement of cations is completed in this way, the first switching valve and the second switching valve are turned off while the sampling valve remains on, as shown in the section D of FIG. The eluent remaining on the column is washed out with pure water. This is because if the eluent remains in the cation trapping column 8 of FIG.
This is done in order to avoid the occurrence of such a phenomenon, since the cations in the sample are eluted from the cation trapping column 8 by the eluent in which some of the cations in the sample remain.
【００１６】尚、本発明は上述の実施例に限定されるこ
となく種々の変形が可能であり、例えば検出器１１とし
て紫外線吸収検出器などを使用してもよい。また、いわ
ゆるサプレスト型イオンクロマトグラフィーに本発明を
適用してもよい。The present invention is not limited to the above-described embodiment, but can be variously modified. For example, an ultraviolet absorption detector or the like may be used as the detector 11. The present invention may also be applied to so-called suppressed ion chromatography.
【００１７】[0017]
【発明の効果】以上詳しく説明したような本発明によれ
ば、希釈操作などを行うことなく水溶性有機溶媒１００
％の試料を注入しても、分離カラムやサプレッサに水溶
性有機溶媒を入れることなく、該水溶性有機溶媒中の陽
イオンを簡便かつ高精度に測定できるという利点があ
る。従って、本発明によれば、水溶性有機溶媒に含まれ
ている陽イオンを簡便かつ高精度に測定できる陽イオン
の測定方法が実現する。According to the present invention as described in detail above, the water-soluble organic solvent 100 can be used without performing a diluting operation.
% Of the sample, there is an advantage that the cation in the water-soluble organic solvent can be easily and accurately measured without putting the water-soluble organic solvent in the separation column or the suppressor. Therefore, according to the present invention, a cation measuring method capable of simply and highly accurately measuring the cation contained in the water-soluble organic solvent is realized.
【図１】本発明実施例の構成説明図である。FIG. 1 is a structural explanatory view of an embodiment of the present invention.
【図２】本発明実施例に関するタイムチャートである。FIG. 2 is a time chart regarding an example of the present invention.
１ 溶離液槽 ２ 純水槽 ３，４ 送液ポンプ ５ 試料採取弁 ５ｈ シリンジ ６，７ 切換弁 ８ 陽イオン捕捉用カラム ９ 不純物除去カラム １０ 分離カラム １１ 検出器 1 Eluent tank 2 Pure water tank 3,4 Liquid feed pump 5 Sampling valve 5h Syringe 6,7 Switching valve 8 Cation capture column 9 Impurity removal column 10 Separation column 11 Detector
Claims (1)
取する試料導入部と該試料中の陽イオンをクロマトグラ
フィックに分離する分離カラム部との間に、陽イオン交
換樹脂を充填した陽イオン捕捉用カラムを設置し、該陽
イオン捕捉用カラムで前記試料中の陽イオンを捕捉し、
その後、前記陽イオン捕捉用カラムに洗浄用純水を流し
て前記陽イオン捕捉用カラムに含まれている前記水溶性
有機溶媒を洗い出し、その後、溶離液で前記陽イオン捕
捉用カラムに捕捉されている陽イオンを前記分離カラム
部に搬入することを特徴とする陽イオンの測定方法。1. A cation-exchange resin-filled cation between a sample introduction part for collecting a fixed amount of a sample made of a water-soluble organic solvent and a separation column part for chromatographically separating cations in the sample. An ion capturing column is installed, and the cations in the sample are captured by the cation capturing column,
Then, pure water for washing is flowed through the cation trapping column to wash out the water-soluble organic solvent contained in the cation trapping column, and then the eluent is trapped in the cation trapping column. The method for measuring cations is characterized in that existing cations are carried into the separation column section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4310292A JPH05240846A (en) | 1992-02-28 | 1992-02-28 | Cation measuring method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4310292A JPH05240846A (en) | 1992-02-28 | 1992-02-28 | Cation measuring method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05240846A true JPH05240846A (en) | 1993-09-21 |
Family
ID=12654473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4310292A Pending JPH05240846A (en) | 1992-02-28 | 1992-02-28 | Cation measuring method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05240846A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101359944B1 (en) * | 2012-10-05 | 2014-02-24 | 주식회사 위드텍 | Eluent automatic manufacturing device for chromatography and eluent automatic manufacturing method |
-
1992
- 1992-02-28 JP JP4310292A patent/JPH05240846A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101359944B1 (en) * | 2012-10-05 | 2014-02-24 | 주식회사 위드텍 | Eluent automatic manufacturing device for chromatography and eluent automatic manufacturing method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10794874B2 (en) | Sample injection device | |
| JP4457135B2 (en) | Liquid chromatograph analyzer and sample introduction device | |
| US20120262178A1 (en) | Apparatus And Method For Coupled LC-NMR Analysis | |
| JP4887199B2 (en) | Liquid chromatography | |
| US7555937B2 (en) | Sample injection device, sample injection method, and liquid chromatograph | |
| US20070062876A1 (en) | IC system including sample pretreatment and using a single pump | |
| JPS60219554A (en) | Method and apparatus for measuring minor component in major component | |
| CN105510483A (en) | System for full-automated and online detection of perfluoro and polyfluoro compounds in serum | |
| EP1843153B1 (en) | Sample injector, sample injecting method and liquid chromatography device | |
| JP3865119B2 (en) | Mobile phase gradient apparatus and high-performance liquid chromatograph using the same | |
| JP4946647B2 (en) | Sample pretreatment device and liquid chromatograph device | |
| JP6260719B2 (en) | Liquid chromatograph | |
| JP2950697B2 (en) | Direct connection method and apparatus for high performance liquid chromatograph / mass spectrometer | |
| EP3816622A1 (en) | Interface system and corresponding method | |
| JPH05240846A (en) | Cation measuring method | |
| JPH11125624A (en) | Liquid chromatograph | |
| JPH05240845A (en) | Anion measuring method | |
| CN104502498B (en) | With online aerosol sample pretreating device and detection method associated with chromatography of ions | |
| JP2002098678A (en) | Sample introduction device as well as liquid chromatographic apparatus and sample introduction method using it | |
| JP2905824B2 (en) | Ion species analysis method and apparatus | |
| GB2519395A (en) | Chromatographic interface | |
| JPH01116444A (en) | Anion analyzer | |
| JPH09257779A (en) | Method and apparatus for analyzing very small amount of anion | |
| JPH0552825A (en) | Analyzing method for trace ion species of ion | |
| JPH0587789A (en) | Measuring method of positive ions |