JPS63138260A - Method and device for analyzing organic acid - Google Patents
Method and device for analyzing organic acidInfo
- Publication number
- JPS63138260A JPS63138260A JP28489786A JP28489786A JPS63138260A JP S63138260 A JPS63138260 A JP S63138260A JP 28489786 A JP28489786 A JP 28489786A JP 28489786 A JP28489786 A JP 28489786A JP S63138260 A JPS63138260 A JP S63138260A
- Authority
- JP
- Japan
- Prior art keywords
- mobile phase
- organic acid
- organic
- perchloric acid
- acid
- 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
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title abstract description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- -1 organic acid anion Chemical class 0.000 claims abstract description 5
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 3
- 238000001032 ion-exclusion chromatography Methods 0.000 claims description 18
- 150000004010 onium ions Chemical class 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000010494 dissociation reaction Methods 0.000 abstract description 7
- 230000005593 dissociations Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 235000005985 organic acids Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical compound [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
この発明は有機酸分析法およびその装置に関する。さら
に詳しくはイオン排除クロマトグラフィ法を用いた高速
液体クロマトグラフィにより有機酸を分析する方法およ
び装置に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to an organic acid analysis method and an apparatus therefor. More specifically, the present invention relates to a method and apparatus for analyzing organic acids by high performance liquid chromatography using ion exclusion chromatography.
（ロ）従来の技術
有機酸の分析は高速液体クロマトグラフィを利用したイ
オン排除クロマトグラフィにより行われている。このイ
オン排除クロマトグラフィは負に帯電した固定相と過塩
素酸、硫酸等の移動相を用い、分析対象の有機酸を該有
機酸陰イオンと上記固定相との静電気斥力の強さに基づ
いて分離する方法である。そしてこのような方法により
分離される有機酸は、吸光光度計、示差屈折計または電
気伝導度検出器により検出されている。(b) Prior art Analysis of organic acids is carried out by ion exclusion chromatography using high performance liquid chromatography. This ion exclusion chromatography uses a negatively charged stationary phase and a mobile phase such as perchloric acid or sulfuric acid, and separates the organic acid to be analyzed based on the strength of the electrostatic repulsion between the organic acid anion and the stationary phase. This is the way to do it. Organic acids separated by such a method are detected using an absorption photometer, a differential refractometer, or an electrical conductivity detector.
（ハ）発明が解決しようとする問題点
しかしながら上記イオン排除クロマトグラフィにおいて
吸光光度計または示差屈折計により検出する場合、検出
上の感度および選択性が悪く十分な分析ができない。そ
こでイオン排除クロマトグラフィにさらにボストカラム
誘導体化法を用いて可視部での吸光度を測定する方法が
考えられているが、選択性の向上は認められるものの感
度の点で問題を残している。一方電気伝導度検出器はイ
オンの検出に有用なものであるが、上記イオン排除クロ
マトグラフィによる有機酸の分析に用いた場合、用いる
前記移動相のｐ）（が２〜３と低くバックグラウンドの
伝導度が大きく、しかも有機酸の解離が抑制されている
ため（移動相に比べて有機酸は弱酸であるため）感度が
不十分である。(c) Problems to be Solved by the Invention However, when detecting with an absorptiometer or a differential refractometer in the above ion exclusion chromatography, the detection sensitivity and selectivity are poor, and sufficient analysis cannot be performed. Therefore, a method of measuring absorbance in the visible region using Bost column derivatization method in addition to ion exclusion chromatography has been considered, but although the selectivity has been improved, problems remain in terms of sensitivity. On the other hand, electrical conductivity detectors are useful for detecting ions, but when used for the analysis of organic acids using ion exclusion chromatography, the mobile phase used has a low p) of 2 to 3, resulting in low background conductivity. Since the sensitivity is large and the dissociation of the organic acid is suppressed (because the organic acid is a weak acid compared to the mobile phase), the sensitivity is insufficient.
この発明はかかる状況に鑑み為されたものであり、こと
に電気伝導度検出器を用いたイオン排除クロマトグラフ
ィ法により、感度を向上させた有機酸分析法およびその
装置を提供しようとするものである。The present invention has been made in view of the above circumstances, and specifically aims to provide an organic acid analysis method and apparatus thereof with improved sensitivity using an ion exclusion chromatography method using an electrical conductivity detector. .
（ニ）問題点を解決するための手段
かくしてこの発明によれば、有機酸を含有する試料を、
過塩素酸水溶液を移動相としたイオン排除クロマトグラ
フィに付して分離し、該クロマトグラフィからの分離溶
出液に、過塩素酸と難溶性塩を形成しうる有機オニウム
イオンを含有する塩基性水性溶液を添加混合して該混合
液のｐ）１を５〜９に調節した後、該混合液中の有機酸
陰イオンを電気伝導度に基づいて検出することを特徴と
する有機酸分析法が提供される。(d) Means for solving the problem Thus, according to the present invention, a sample containing an organic acid is
Separation is performed by ion exclusion chromatography using an aqueous perchloric acid solution as a mobile phase, and the separated eluate from the chromatography contains a basic aqueous solution containing organic onium ions that can form poorly soluble salts with perchloric acid. An organic acid analysis method is provided, which comprises adding and mixing to adjust p)1 of the mixed solution to 5 to 9, and then detecting organic acid anions in the mixed solution based on electrical conductivity. Ru.
この発明の方法は、イオン排除クロマトグラフィにおい
て、移動相として用いる過塩素酸をボストカラム誘導体
化法を利用して難溶性塩に変換してバックグラウンドを
減少させるとともに、該移動相のｐＨを調節して有機酸
の解離度の上昇を図ることを特徴とする。The method of the present invention reduces background by converting perchloric acid used as a mobile phase into a poorly soluble salt using the Bost column derivatization method in ion exclusion chromatography, and adjusts the pH of the mobile phase. It is characterized by increasing the degree of dissociation of organic acids.
上記難溶性塩に変換しうる試薬としては、過塩素酸を中
和する塩基性のものでかつ１価の、イオン半径の大きい
有機オニウムイオンを含有する水性溶液が適している。As the reagent that can be converted into the above-mentioned sparingly soluble salt, an aqueous solution containing a basic monovalent organic onium ion with a large ionic radius that neutralizes perchloric acid is suitable.
上記有機オニウムイオンとしては、トリアルキル−、テ
トラアルキル−、トリアリル−またはテトラアリルオニ
ウムイオンが適しており、これらの有機オーラムイオン
は有機オニウム化合物とし゛て供給される。この有機オ
ニウム化合物としてはアンモニウム、ホスホニウム、ア
ルソニウム等からなる化合物が挙げられるが、これらに
限定されない。上記有機オニウム化合物は水酸化物の形
で用いられる。この中で水酸化テトラブチルアンモニウ
ムが容易に入手できる点で好ましい。Suitable organic onium ions are trialkyl, tetraalkyl, triallyl or tetraaryl onium ions, and these organic aurum ions are supplied as organic onium compounds. Examples of the organic onium compound include, but are not limited to, compounds consisting of ammonium, phosphonium, arsonium, and the like. The above organic onium compounds are used in the form of hydroxide. Among these, tetrabutylammonium hydroxide is preferred because it is easily available.
上記有機オニウム化合物は、水または水と混和しうる有
機溶媒からなる水性溶媒により溶解され、水性溶液に調
製される。この場合数本性溶液の液性は、該水性溶液を
添加混合した移動相のｐＨが５〜９となりうる範囲の塩
基性に調製される。The organic onium compound is dissolved in an aqueous solvent consisting of water or an organic solvent miscible with water to prepare an aqueous solution. In this case, the liquid property of the aqueous solution is adjusted to be basic so that the pH of the mobile phase to which the aqueous solution is added and mixed becomes 5 to 9.
上記有機オニウムイオンを含有する塩基性水性溶液は、
イオン排除クロマトグラフ用カラムから分離・溶出され
た有機酸含有移動相に供給される。The basic aqueous solution containing the organic onium ion is
It is supplied to the organic acid-containing mobile phase separated and eluted from the ion exclusion chromatography column.
上記有機オニウムイオンを含有する塩基性水性溶液が供
給されることにより、移動相のｐＨが増加しこれにつれ
て該移動相中に分離・溶出された有機酸の解離度か上昇
し、生成する有機酸陰イオンの電気伝導度に基づいて有
機酸が検出されること従ってこの発明は、過塩素酸水溶
液を移動相とした移動相供給部から試料導入口、イオン
排除クロマトグラフ用カラム、混合コイルを経て電気伝
導度検出器へ延設される分析流路と、過塩素酸と難溶性
塩を形成しうる有機オニウムイオンを含有する塩基性水
性溶液を上記カラムと混合コイルのとの間に導入しうる
反応試薬供給流路とから構成されてなる有機酸分析装置
をも供給するものである。By supplying the basic aqueous solution containing organic onium ions, the pH of the mobile phase increases, and the degree of dissociation of the organic acid separated and eluted into the mobile phase increases accordingly, resulting in an organic acid being generated. Organic acids are detected based on the electrical conductivity of anions. Therefore, in this invention, a mobile phase supply section using an aqueous perchloric acid solution as a mobile phase is passed through a sample inlet, an ion exclusion chromatography column, and a mixing coil. An analytical channel extending to an electrical conductivity detector and a basic aqueous solution containing organic onium ions capable of forming a poorly soluble salt with perchloric acid may be introduced between the column and the mixing coil. The present invention also supplies an organic acid analyzer comprising a reaction reagent supply channel.
（ホ）作用
この発明によれば、過塩素酸からなる移動相に −より
移送される有機酸は、該移動相中でその解離が押さえら
れてイオン排除クロマトグラフ用カラムを通過する間に
夾雑イオン種と分離され、該カラム通過後この分離され
た有機酸を含有する移動相に、有機オニウムイオンを含
有する塩基性水性溶液が導入されると、移動相の過塩素
酸は中和されて有機オニウムイオンと難溶性のイオン対
を形成して該移動相に由来するイオンが消失する一方、
移動相のｏＨが増加して跡移動相中に保拮される有機酸
の解離が促されて、該有機酸に由来するイオンが増加す
る。(E) Effect According to the present invention, the organic acid transferred to the mobile phase consisting of perchloric acid is suppressed from dissociation in the mobile phase and is contaminated while passing through the column for ion exclusion chromatography. When a basic aqueous solution containing organic onium ions is introduced into the mobile phase containing the separated organic acid after it has been separated from the ionic species and passed through the column, the perchloric acid in the mobile phase is neutralized. While ions originating from the mobile phase disappear by forming poorly soluble ion pairs with organic onium ions,
As the oH of the mobile phase increases, the dissociation of the organic acid retained in the residual mobile phase is promoted, and the number of ions derived from the organic acid increases.
以下実施例によりこの発明の詳細な説明するが、これに
よりこの発明は限定されるものではない。The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereby.
（へ）実施例
第１図はこの発明の有機酸分析装置の一例の構成説明図
である。図において有機酸分析装置（１）は、移動相貯
留槽（２）から送液ポンプ（３）、試料導入口（４）、
イオン排除クロマトグラフ用カラム（５）、混合コイル
（６）をこの順に経て電気伝導度検出器（７）へ延設さ
れる分析流路（ａ）と、反応試薬貯留槽（８）から送液
ポンプ（９）を経て上記分析流路（ａ）のイオン排除ク
ロマトグラフ用カラム（５）と混合コイル（６）との間
の管路に管路接続される反応試薬供給流路（ｂ）とから
構成されている。なお、（１０）はカラム恒温槽、（１
１）は記録部、（１２）はドレインへ延設される排出用
管路である。(f) Example FIG. 1 is an explanatory diagram of the configuration of an example of an organic acid analyzer of the present invention. In the figure, an organic acid analyzer (1) includes a mobile phase storage tank (2), a liquid sending pump (3), a sample inlet (4),
An analysis flow path (a) extending in this order to an electrical conductivity detector (7) through an ion exclusion chromatography column (5) and a mixing coil (6), and a liquid feed from a reaction reagent storage tank (8). a reaction reagent supply channel (b) connected via a pump (9) to a channel between the ion exclusion chromatography column (5) and the mixing coil (6) in the analysis channel (a); It consists of In addition, (10) is a column constant temperature bath, (1
1) is a recording section, and (12) is a discharge pipe extending to a drain.
上記のごとく構成された装置（１）において、移動相と
して１ｍＭ過塩素酸（ＨＣＩＯ，）水溶液、反応試薬と
して１ｍＭ水酸化テトラブチルアンモニウム水溶液をそ
れぞれ用い、下記の条件にて有機酸である酢酸（ｃ）の
検出を行ったところ第２図に示す結果を得た。In the apparatus (1) configured as described above, a 1mM aqueous solution of perchloric acid (HCIO) was used as a mobile phase, and a 1mM aqueous solution of tetrabutylammonium hydroxide was used as a reaction reagent, under the following conditions. When the detection of c) was carried out, the results shown in FIG. 2 were obtained.
イオン排除クロマトグラフ用カラム
Ｓ ｈｉｍ−ｐａｃｋ Ｓ ＣＲ−１０１Ｈ（７，９
ｍｍ１．ｄ、 Ｘ ２５０ｍｍＬ ）カラム温度
５０ ’Ｃ移動相流ＭＬ
Ｏ，５ｍ１２／ｍｉｎ反応試薬流量 ０
．５ｍ１２／ｗｉｎ試薬混合後の移動相９口： ７
また、比較として反応試薬を供給しない（カラム溶出液
を中和しない）従来例の装置で同様に行った結果を第３
図に示す。Ion exclusion chromatography column S him-pack S CR-101H (7,9
mm1. d, X 250 mmL) Column temperature
50'C mobile phase flow ML
O, 5m12/min Reaction reagent flow rate 0
．． 5m12/win 9 ports of mobile phase after mixing reagents: 7 Also, for comparison, the results of a similar experiment using a conventional device that does not supply reaction reagents (does not neutralize column eluate) are shown in the third column.
As shown in the figure.
以上の結果から、この装置によれば有機酸である酢酸（
ｃ）を感度良好に検出することができる。From the above results, this device shows that acetic acid, an organic acid (
c) can be detected with good sensitivity.
（ト）発明の効果
この発明によれば、移動相の液性をｐＨ５〜つとして検
出するため、有機酸がイオンに解離し感度の向上が図れ
る。また移動相の過塩素酸の中和が、該過塩素酸と難溶
性のイオン対を形成して行われるため、移動相に由来す
るバックグラウンドの伝導度が低下し、ノイズレベルを
低くできる。(G) Effects of the Invention According to the present invention, since the liquid property of the mobile phase is detected at a pH of 5 to 5, the organic acid is dissociated into ions and the sensitivity can be improved. Furthermore, since the perchloric acid in the mobile phase is neutralized by forming a poorly soluble ion pair with the perchloric acid, the background conductivity originating from the mobile phase is reduced and the noise level can be lowered.
第１図はこの発明の有機酸分析装置の一例の構成説明図
、第２図は第１図の装置による酢酸の検出状態を示すグ
ラフ図、第３図は従来例の装置による第２図相当図であ
る。
（２）・・・・・・移動相貯留槽、
（３）、（９）・・・・・・送液ポンプ、 （４）・・
・・・・試料導入口、（５）・・・・・・イオン排除ク
ロマトグラフ用カラム、（６）・・・・・・混合コイル
、
（７）・・・・・・電気伝導度検出器、（８）・・・・
・・反応試薬貯留槽、（１０）・・・・・・カラム恒温
槽、（１１）・・・・・・記録部、 （１２）・
・・・・・排出用管路、（ａ）・・・・・・分析流路、
（ｂ）・・・・・・反応試薬供給流路、第１図Fig. 1 is an explanatory diagram of the configuration of an example of the organic acid analyzer of the present invention, Fig. 2 is a graph showing the detection status of acetic acid by the apparatus of Fig. 1, and Fig. 3 is equivalent to Fig. 2 by the conventional apparatus. It is a diagram. (2)...Mobile phase storage tank, (3), (9)...Liquid pump, (4)...
...Sample introduction port, (5) ...Ion exclusion chromatography column, (6) ...Mixing coil, (7) ...Electric conductivity detector , (8)...
... Reaction reagent storage tank, (10) ... Column thermostat, (11) ... Recording section, (12) ...
...Discharge pipe, (a) ... Analysis flow path, (b) ... Reaction reagent supply flow path, Fig. 1
Claims (1)
としたイオン排除クロマトグラフィに付して分離し、該
クロマトグラフィからの分離溶出液に、過塩素酸と難溶
性塩を形成しうる有機オニウムイオンを含有する塩基性
水性溶液を添加混合して該混合液のｐＨを５〜９に調節
した後、該混合液中の有機酸陰イオンを電気伝導度に基
づいて検出することを特徴とする有機酸分析法。 ２、過塩素酸水溶液を移動相とした移動相供給部から試
料導入口、イオン排除クロマトグラフ用カラム、混合コ
イルを経て電気伝導度検出器へ延設される分析流路と、
過塩素酸と難溶性塩を形成しうる有機オニウムイオンを
含有する塩基性水性溶液を上記カラムと混合コイルのと
の間に導入しうる反応試薬供給流路とから構成されてな
る有機酸分析装置。[Claims] 1. A sample containing an organic acid is separated by ion exclusion chromatography using an aqueous perchloric acid solution as a mobile phase, and the separated eluate from the chromatography contains a sample that is sparingly soluble in perchloric acid. After adjusting the pH of the mixture to 5 to 9 by adding and mixing a basic aqueous solution containing organic onium ions capable of forming a salt, organic acid anions in the mixture are adjusted based on electrical conductivity. An organic acid analysis method characterized by detection. 2. An analysis channel extending from a mobile phase supply section using an aqueous perchloric acid solution as a mobile phase to an electrical conductivity detector via a sample inlet, an ion exclusion chromatography column, and a mixing coil;
An organic acid analyzer comprising a reaction reagent supply channel capable of introducing a basic aqueous solution containing organic onium ions capable of forming a poorly soluble salt with perchloric acid between the column and a mixing coil. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28489786A JPS63138260A (en) | 1986-11-28 | 1986-11-28 | Method and device for analyzing organic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28489786A JPS63138260A (en) | 1986-11-28 | 1986-11-28 | Method and device for analyzing organic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63138260A true JPS63138260A (en) | 1988-06-10 |
Family
ID=17684459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28489786A Pending JPS63138260A (en) | 1986-11-28 | 1986-11-28 | Method and device for analyzing organic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63138260A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103543236A (en) * | 2013-10-12 | 2014-01-29 | 福建省农业科学院农业工程技术研究所 | Method for determining organic acid content of fermented wine by ion-exclusion chromatography |
| CN105758982A (en) * | 2016-02-25 | 2016-07-13 | 杭州飞山浩科技有限公司 | Device and method for measuring nitrite ions in milk powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5719443B2 (en) * | 1977-08-01 | 1982-04-22 |
-
1986
- 1986-11-28 JP JP28489786A patent/JPS63138260A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5719443B2 (en) * | 1977-08-01 | 1982-04-22 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103543236A (en) * | 2013-10-12 | 2014-01-29 | 福建省农业科学院农业工程技术研究所 | Method for determining organic acid content of fermented wine by ion-exclusion chromatography |
| CN103543236B (en) * | 2013-10-12 | 2014-12-10 | 福建省农业科学院农业工程技术研究所 | Method for determining organic acid content of fermented wine by ion-exclusion chromatography |
| CN105758982A (en) * | 2016-02-25 | 2016-07-13 | 杭州飞山浩科技有限公司 | Device and method for measuring nitrite ions in milk powder |
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