JPH0412262A - Reference electrode used in nonaqueous solvent - Google Patents
Reference electrode used in nonaqueous solventInfo
- Publication number
- JPH0412262A JPH0412262A JP11446690A JP11446690A JPH0412262A JP H0412262 A JPH0412262 A JP H0412262A JP 11446690 A JP11446690 A JP 11446690A JP 11446690 A JP11446690 A JP 11446690A JP H0412262 A JPH0412262 A JP H0412262A
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- internal
- isopropyl alcohol
- solvent
- reference electrode
- 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
- 239000002904 solvent Substances 0.000 title claims abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000003125 aqueous solvent Substances 0.000 claims description 13
- 230000000052 comparative effect Effects 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005259 measurement Methods 0.000 abstract description 8
- 238000004448 titration Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract 4
- 238000012423 maintenance Methods 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004401 flow injection analysis Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013470 LiC1 Inorganic materials 0.000 description 1
- 229910011687 LiCu Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、非水溶液のイオン濃度を測定する場合に使用
される比較電極に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a reference electrode used when measuring the ion concentration of a non-aqueous solution.
（従来の技術）
溶液のイオン濃度を測定する場合に使用される比較電極
は、例えは、特公昭５５−１６２６２号公報に開示され
たものか知られている。(Prior Art) A reference electrode used in measuring the ion concentration of a solution is known, for example, as disclosed in Japanese Patent Publication No. 16262/1983.
この比較電極は、支持管の一部に液絡部を設けるととも
に、支持管内に内部電極が配置され、かつ支持管内に内
部液として飽和塩化カリウム（Ｋ（Ｊ２）水溶液が注入
されたものである。This reference electrode includes a liquid junction provided in a part of the support tube, an internal electrode placed inside the support tube, and a saturated potassium chloride (K(J2) aqueous solution) injected as an internal liquid into the support tube. .
（発明が解決しようとする課題）
前記従来の比較電極は、水溶液または非水溶液中に挿入
して、その溶液のイオン濃度を測定するために使用され
るものである。(Problems to be Solved by the Invention) The conventional reference electrode is inserted into an aqueous solution or a non-aqueous solution and used to measure the ion concentration of the solution.
そして、前記水溶液のイオン濃度を測定する場合の使用
に対しては支障はほぼ生じない。There is almost no problem when using the method to measure the ion concentration of the aqueous solution.
しかし、例えは、ＪＩＳ Ｋ−２５０１（石油製品中和
価試験）て規定された電位差滴定法で使用する溶媒は、
１〜ルエン：イソプロビルアルコール：水（５０：４９
．５：０．５）である。したがって、この測定に前記比
較電極を使用すると、前記溶媒に対する内部液のＫＣＩ
、の溶解度か小さいため、このＫＯ２の析出で液絡部が
詰まって、内部液のスムースな流出が妨けられたり、ま
たは前記内部液の溶媒である水が液絡部から支持管外に
出て、前記１へルエン：イソプロピルアルコール：水か
らなる溶媒の見かけのｐＨ値を大きく変化さぜるなどす
る。このため、ノイズやドリフｌ〜ががなり大きくなっ
て、正確な滴定を妨ける問題が発生する。However, for example, the solvent used in the potentiometric titration method specified in JIS K-2501 (petroleum product neutralization value test) is
1 ~ Luene: Isoprobyl alcohol: Water (50:49
．． 5:0.5). Therefore, when the reference electrode is used for this measurement, the KCI of the internal solution with respect to the solvent is
Because the solubility of KO2 is low, the liquid junction may be clogged by the precipitation of KO2, preventing the internal liquid from flowing out smoothly, or water, which is the solvent for the internal liquid, may leak out from the liquid junction to the outside of the support tube. Then, the apparent pH value of the solvent consisting of toluene: isopropyl alcohol: water is greatly changed. For this reason, noise and drift l~ increase and become large, causing a problem that prevents accurate titration.
これをフローインジェクション（ＦＩＡ）電位差滴定に
適用すると、ｐＨ測定用フローセルの容積が小さいから
、前記内部液の溶媒である水の流出などの影響は一層大
きくなるものである。When this is applied to flow injection (FIA) potentiometric titration, since the volume of the flow cell for pH measurement is small, the influence of outflow of water, which is the solvent of the internal liquid, becomes even greater.
また、液絡部から支持管外に流出したＫＣＪ、や水がフ
ローセル内部に溜まるので、それらを適宜に取除くこと
が必要になる問題もある。Furthermore, since KCJ and water flowing out of the support tube from the liquid junction accumulate inside the flow cell, there is also the problem that it is necessary to remove them appropriately.
本発明は上記のような課題を解決するものてあって、非
水溶媒中で電解質が析出して液絡部が詰まったり、また
は内部液の溶媒が前記非水溶媒の見かけのｐＨ値を変化
させるおそれか少ない非水溶媒中で使用する比較電極を
うろことを目的とするものである。The present invention is intended to solve the above-mentioned problems, and the electrolyte may precipitate in a non-aqueous solvent, clogging the liquid junction, or the solvent in the internal solution may change the apparent pH value of the non-aqueous solvent. The purpose is to use a reference electrode to be used in a non-aqueous solvent where there is little risk of damage.
（課題を解決するための手段）
本発明の非水溶媒中で使用する比較電極は、液絡部を設
けた支持管内に内部電極が配置され、支持管内に電解質
を溶解した内部液が注入された比較電極において、前記
内部液の溶媒としてイソプロピルアルコールが、電解質
としてイソプロピルアルコールに溶解するものが、それ
ぞれ使用されたことを特徴とするものである。(Means for Solving the Problems) In the reference electrode used in a non-aqueous solvent of the present invention, an internal electrode is arranged in a support tube provided with a liquid junction, and an internal solution containing an electrolyte dissolved in the support tube is injected. The comparative electrode is characterized in that isopropyl alcohol is used as the solvent of the internal solution, and an electrolyte that is dissolved in isopropyl alcohol is used as the electrolyte.
前記内部液の溶媒としては、イソプロピルアルコールの
みを使用、またはイソプロピルアルコールに少量の水、
トルエンなどを添加するなど任意である。そして、前記
電解質としては、その溶媒であるイソプロピルアルコー
ルに溶解する、例えば、ＬｉＣ，９、Ｂｔ４ ＮＣ，ｐ
などを使用する。As the solvent for the internal solution, only isopropyl alcohol is used, or isopropyl alcohol with a small amount of water,
It is optional to add toluene or the like. The electrolyte includes, for example, LiC,9, Bt4 NC,p, which is dissolved in isopropyl alcohol, which is the solvent.
etc.
（作用）
前記本発明の非水溶媒中て使用する比較電極は、それを
サンプルとしての非水溶媒中で使用すると、その内部液
が液絡部から前記溶媒中に流出するが、前記内部液の溶
媒がイソプロピルアルコールであるから、前記非水溶媒
の見かけのｐＨ値を変化させることが少ない。そして、
前記イソプロピルアルコールに溶解する電解質としての
、例えは、Ｌｉｃｊ２．Ｅｔ４ＮＣｊ２などは非プロト
ン性溶媒（＋−ルエン）中においても溶解度か比較的大
きく、液絡部から非水溶媒中に流出したときに結晶する
ことは少ないから、液絡部に結晶した電解質か詰まるこ
とによる内部液のスムーズな流出を妨Ｃすることがほぼ
なくなる。(Function) When the reference electrode of the present invention is used in a non-aqueous solvent as a sample, its internal liquid flows out from the liquid junction into the solvent. Since the solvent is isopropyl alcohol, the apparent pH value of the non-aqueous solvent is hardly changed. and,
As the electrolyte dissolved in the isopropyl alcohol, for example, Licj2. Et4NCj2 etc. have a relatively high solubility even in an aprotic solvent (+- toluene), and are unlikely to crystallize when flowing out from the liquid junction into a non-aqueous solvent, so crystallized electrolyte may clog the liquid junction. Therefore, there is almost no interference with the smooth outflow of the internal liquid.
（実施例）
本発明の非水溶媒中で使用する比較電極の第１実施例を
第１図について説明する。(Example) A first example of a comparative electrode used in a non-aqueous solvent according to the present invention will be described with reference to FIG.
第１図において、１は外部支持管で、その先端にセラミ
ックからなる液絡部２が設けられている。In FIG. 1, reference numeral 1 denotes an external support tube, and a liquid junction 2 made of ceramic is provided at the tip thereof.
３は外部支持管１に注入された内部液としての外管液で
、これは１．５ｍｏｌ／ｊ２のＬｉＣｊ２を溶解したイ
ソプロピルアルコール、水（９：１）の溶液で構成され
ている。４は外部支持管１内に挿入された内部支持管で
、その端部にセラミックからなる液絡部５が設けられて
いる。６は内部支持管３内に配置された内部電極、７は
内部支持管３に注入された内管液で、これは３．３３ｍ
ｑｌ／１のＬｉＣｕ水溶液て構成されている。８は外部
支持管１に対する外管液３の補充口、９は内部支持管３
に対する内管′ａ、７の補充口、１０は上記構成からな
るタプルジャンクション型の比較電極である。Reference numeral 3 denotes an outer tube liquid as an internal liquid injected into the outer support tube 1, which is composed of a solution of isopropyl alcohol and water (9:1) in which 1.5 mol/j2 of LiCj2 is dissolved. Reference numeral 4 denotes an internal support tube inserted into the external support tube 1, and a liquid junction 5 made of ceramic is provided at the end thereof. 6 is an internal electrode placed in the internal support tube 3, and 7 is the internal tube liquid injected into the internal support tube 3, which is 3.33 m long.
It is composed of a LiCu aqueous solution of ql/1. Reference numeral 8 indicates a replenishment port for the outer tube liquid 3 to the outer support tube 1, and 9 indicates an inner support tube 3.
The inner tube 'a, the replenishment port 7, and 10 are tuple junction type reference electrodes having the above structure.
１１はフローインジェクション（ＦＩＡ）電位差滴定の
フローセルで、上下に傾斜させた液通路１２が設けられ
るとともに、この液通路１２に連通して挿入孔１３．１
４が形成さ′ｉｔて、挿入孔１３にｐＨ電極１５が挿入
され、挿入孔１４に前記外部支持管１の先端部が挿入さ
れている。Reference numeral 11 denotes a flow cell for flow injection (FIA) potentiometric titration, which is provided with a liquid passage 12 that is inclined up and down, and an insertion hole 13.1 that communicates with this liquid passage 12.
4 is formed, the pH electrode 15 is inserted into the insertion hole 13, and the tip of the external support tube 1 is inserted into the insertion hole 14.
そして、前記液通路１２の低位側から高位側にトルエン
：イソプロピルアルコール：水（５０：４９．５：０．
５）からなるキャリヤー液を流動させて滴定を行った。Then, from the lower side to the higher side of the liquid passage 12, toluene:isopropyl alcohol:water (50:49.5:0.
Titration was carried out by flowing the carrier liquid consisting of 5).
その結果、外部支持管１の液絡部２に対する外管液３の
ＬｉＣｊ２結晶の詰まりかなくて、外管液３が液絡部２
から継続してスムーズに流出するから、前記従来例の比
較電極に比して、ノイズやドリフトが大中に低下して、
正常に見かけのｐＨを測定することができな。また、外
部支持管１の液絡部２から流出した外管液３のＬ ｉ
Ｃｊ２か結晶して、フローセル１１の液通路ｌｉ！８１
２に溜まることもなかった。As a result, the liquid junction 2 of the external support tube 1 is not clogged with LiCj2 crystals in the outer tube liquid 3, and the outer tube liquid 3 is not clogged with the liquid junction 2.
Since the electrode continues to flow smoothly from the previous example, noise and drift are greatly reduced compared to the conventional reference electrode.
Unable to measure apparent pH correctly. In addition, Li of the outer tube liquid 3 flowing out from the liquid junction 2 of the outer support tube 1
Cj2 crystallizes and the liquid passage li of the flow cell 11! 81
It never got to 2.
なお、前記液絡部２を外部支持管１の先端に股りている
が、液絡部２は外部支持管１の周壁部に設りるなと任意
である。これは内部支持管４の液絡部５についても同様
である。Note that although the liquid junction 2 is provided at the tip of the external support tube 1, it is optional that the liquid junction 2 is not provided on the peripheral wall of the external support tube 1. This also applies to the liquid junction portion 5 of the internal support tube 4.
第２図は第２実施例を示すものである。FIG. 2 shows a second embodiment.
第２図において、１ａは支持管で、その端部にセラミッ
クからなる液絡部２ａが設けられている。３ａは支持管
１ａに注入された内部液て、これは１，５ｍｏｌ／４の
Ｉ−ｊＣｆ！を溶解したイソプロピルアルコール：水（
９：１）の溶液て構成されている。In FIG. 2, 1a is a support tube, and a liquid junction 2a made of ceramic is provided at the end of the support tube. 3a is the internal liquid injected into the support tube 1a, which is 1.5 mol/4 I-jCf! isopropyl alcohol dissolved in water (
9:1) solution.
６ａは内部電極である。１０ａは上記の構成からなるシ
ングルジャンクション型の比較電極である。6a is an internal electrode. Reference numeral 10a is a single junction type comparison electrode having the above-described configuration.
この比較電極１０ａを、石油中和価電位差測定に使用し
た結果、液絡部２ａに結晶した電解質ＬｉＣ１が詰まっ
て内部液の流出が困鉗、または不能などになること、及
び測定セル内に液絡部２ａから流出した内部液３ａのＬ
ｉＣＪ２が結晶して溜まるようなこともなく、精度よく
測定することができた。As a result of using this reference electrode 10a for petroleum neutralization potential difference measurement, it was found that the liquid junction 2a was clogged with crystallized electrolyte LiC1, making it difficult or impossible for the internal liquid to flow out, and that the liquid in the measuring cell L of internal liquid 3a flowing out from junction 2a
There was no crystallization and accumulation of iCJ2, and accurate measurements were possible.
（発明の効果）
本発明の非水溶媒中で使用する比較電極は、上記のよう
に、その内部液の溶媒としてイソプロピルアルコールを
使用し、電解質としてイソプロピルアルコール
して、前記電解質は、非プロ１〜ン性溶媒に対する溶解
度が比較的大きい。(Effects of the Invention) As described above, the reference electrode used in a non-aqueous solvent of the present invention uses isopropyl alcohol as a solvent for its internal solution, and isopropyl alcohol as an electrolyte. It has relatively high solubility in aqueous solvents.
したがって、この比較電極を井水溶媒中で使用しても、
液絡部から支持管外に流出する内部液の電解質が結晶し
て液絡部を詰まらせることは少なく、液絡部から内部液
を継続してスムーズに流出させることが可能である。し
かも、液絡部から流出する内部液の溶媒としてのイソプ
ロピルアルコールは、前記非水溶媒の見かけのＰＨ値に
対する影響が小さい。このため、本発明の比較電極は、
非水溶媒中て１吏用しても電位再現性・安定性、保守性
が向上し、精度よく測定をすることかできる。Therefore, even if this reference electrode is used in well water solvent,
The electrolyte of the internal liquid flowing out of the support tube from the liquid junction is less likely to crystallize and clog the liquid junction, and the internal liquid can continue to flow smoothly from the liquid junction. Moreover, isopropyl alcohol as a solvent for the internal liquid flowing out from the liquid junction has little influence on the apparent pH value of the non-aqueous solvent. Therefore, the reference electrode of the present invention is
Even after one use in a nonaqueous solvent, potential reproducibility, stability, and maintainability are improved, and accurate measurements can be made.
図面は本発明の実施例を示し、第１図は第１実施例の断
面図、第２図は第２実施例の断面図である。
１：外部支持管、２：液絡部、３：外管液、６：内部電
極、１ａ：支持管、２ａ：液絡部、３ａ：内部液、６ａ
＋内部電極。The drawings show embodiments of the present invention, with FIG. 1 being a sectional view of the first embodiment, and FIG. 2 being a sectional view of the second embodiment. 1: External support tube, 2: Liquid junction, 3: Outer tube liquid, 6: Internal electrode, 1a: Support tube, 2a: Liquid junction, 3a: Internal liquid, 6a
+ Internal electrode.
Claims (1)
内に電解質を溶解した内部液が注入された比較電極にお
いて、前記内部液の溶媒としてイソプロピルアルコール
が、電解質としてイソプロピルアルコールに溶解するも
のが、それぞれ使用されたことを特徴とする非水溶媒中
で使用する比較電極。A comparison electrode in which an internal electrode is placed in a support tube provided with a liquid junction, and an internal solution in which an electrolyte is dissolved is injected into the support tube, in which isopropyl alcohol is dissolved as a solvent for the internal solution and isopropyl alcohol is dissolved in isopropyl alcohol as an electrolyte. A comparative electrode for use in a non-aqueous solvent, characterized in that each of these electrodes is used in a non-aqueous solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11446690A JPH0412262A (en) | 1990-04-28 | 1990-04-28 | Reference electrode used in nonaqueous solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11446690A JPH0412262A (en) | 1990-04-28 | 1990-04-28 | Reference electrode used in nonaqueous solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0412262A true JPH0412262A (en) | 1992-01-16 |
Family
ID=14638441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11446690A Pending JPH0412262A (en) | 1990-04-28 | 1990-04-28 | Reference electrode used in nonaqueous solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0412262A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998041856A1 (en) * | 1997-03-14 | 1998-09-24 | Shiseido Company, Ltd. | Liquid chromatography electrochemical detector, liquid chromatograph, and analyzing method using the chromatograph |
| CN104297313A (en) * | 2014-11-06 | 2015-01-21 | 河北科技大学 | Preparation method of all-solid-state sliver/silver chloride reference electrode for nonaqueous solution |
-
1990
- 1990-04-28 JP JP11446690A patent/JPH0412262A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998041856A1 (en) * | 1997-03-14 | 1998-09-24 | Shiseido Company, Ltd. | Liquid chromatography electrochemical detector, liquid chromatograph, and analyzing method using the chromatograph |
| CN104297313A (en) * | 2014-11-06 | 2015-01-21 | 河北科技大学 | Preparation method of all-solid-state sliver/silver chloride reference electrode for nonaqueous solution |
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| Holmes et al. | Thermal Electroanalysis. Effect of Nonelectroactive Ions | |
| JPS54137395A (en) | Analyzer |