JPS5937465B2 - Electrolyte for coulometric titration by Karl Fischer method - Google Patents
Electrolyte for coulometric titration by Karl Fischer methodInfo
- Publication number
- JPS5937465B2 JPS5937465B2 JP635179A JP635179A JPS5937465B2 JP S5937465 B2 JPS5937465 B2 JP S5937465B2 JP 635179 A JP635179 A JP 635179A JP 635179 A JP635179 A JP 635179A JP S5937465 B2 JPS5937465 B2 JP S5937465B2
- Authority
- JP
- Japan
- Prior art keywords
- iodine
- electrolyte
- karl fischer
- coulometric titration
- chloroform
- 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.)
- Expired
Links
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
【発明の詳細な説明】
本発明はカールフイツシヤー法による電量滴定に使用す
る電解液に係るものであり、特にケトン中の微量水分の
測定に好適な電量滴定用電解液に係るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrolytic solution used for coulometric titration by the Karl Fischer method, and particularly to an electrolytic solution for coulometric titration suitable for measuring trace amounts of water in ketones.
カールフイツシヤー電量滴定法は公知であり、電解液と
しては通常、沃素、二酸化硫黄、ピリジン及びメタノー
ルに水を加えて沃素をイオン化した溶液が用いられてい
る。The Karl Fischer coulometric titration method is well known, and the electrolyte usually uses a solution prepared by adding water to iodine, sulfur dioxide, pyridine, and methanol to ionize iodine.
また、沃素の代りに沃化カリウムや沃化ナトリウムを加
えた硫液も用いられる。これらの溶液は広く各種試料の
水分測定に用いられているが、ケトンは溶液中のメタノ
ールと反応して水を生成するため、これらの溶液を用い
てケトン中の水分を測定することは困難である。A sulfur solution containing potassium iodide or sodium iodide may also be used instead of iodine. These solutions are widely used to measure the water content of various samples, but since ketones react with methanol in the solution to produce water, it is difficult to measure the water content in ketones using these solutions. be.
Ｒ２Ｃ０＋２ＣＨ３ＯＨ→２Ｃ（０ＣＨ３）２＋Ｈ２Ｏ
本発明者は先にケトン中の微量水分の測定に好適な電解
液として、沃素または沃化物、二酸化硫黄、ピリジン、
クロロホルム、第３級ブタノール及びエタノールを含有
してなる電解液を提案した（特願昭５３−１４１８５７
号、特公昭５８一２６１５号公報参照）。本発明者はこ
の電解液について更に検討をすすめた結果、数十〜数百
ｐμｍという極微量の水分を測定する場合にはエタノー
ルが存在しないと水分が過少に測定されるが、水分がこ
れよりも多くなるとエタノールが存在しなくても水分を
正確に測定し得ること及びエタノールが存在しない方が
多数回の反復使用に耐えることを見出し、本発明を完成
した。本発明について詳細に説明すると、本発明に係る
電解液は本質的に沃素または沃化物、二酸化硫黄、ピリ
ジン、クロロホルム及び第３級ブタノールよシなつてい
る。R2C0+2CH3OH→2C(0CH3)2+H2O
The present inventor previously found that iodine or iodide, sulfur dioxide, pyridine,
proposed an electrolytic solution containing chloroform, tertiary butanol and ethanol (Japanese Patent Application No. 141,857/1986).
(Refer to Special Publication No. 58-2615). As a result of further study on this electrolyte, the present inventor found that when measuring extremely small amounts of water of several tens to hundreds of ppm, the amount of water measured is too low in the absence of ethanol. The present invention has been completed based on the discovery that when the amount of water increases, the water content can be accurately measured even in the absence of ethanol, and that the absence of ethanol can withstand repeated use many times. Describing the invention in detail, the electrolyte according to the invention consists essentially of iodine or iodide, sulfur dioxide, pyridine, chloroform and tertiary butanol.
沃化物としては沃化カリウム沃化ナトリウム等が好適で
ある。各成分間の組成比について説明すると、本発明に
係る電解液の大部分を占めるのはピリジン、クロロホル
ム及び第３級ブタノールである。第３級ブタノールとク
ロロホルムとの比率は１／１３〜１／２（重量比）が好
ましい。第３級ブタノールは水酸基を有しているのでカ
ールフイツシヤー試薬と水との反応を進行させることが
でき、しかもケトンと反応して水を生成することがない
。クロロホルムは第３級ブタノール及び反応性成物に対
する溶解力が大きく、カールフイツシヤー試薬と水との
反応を促進する。Potassium iodide, sodium iodide, etc. are suitable as the iodide. To explain the composition ratio between each component, pyridine, chloroform, and tertiary butanol account for the majority of the electrolytic solution according to the present invention. The ratio of tertiary butanol to chloroform is preferably 1/13 to 1/2 (weight ratio). Since tertiary butanol has a hydroxyl group, it can proceed with the reaction between the Karl Fischer reagent and water, and does not react with ketones to produce water. Chloroform has a large dissolving power for tertiary butanol and reactive components, and promotes the reaction between the Karl Fischer reagent and water.
電解液中の第３級ブタノールが少なすぎると反応が進行
し難くなり、逆にクロロホルムが少なすぎると反応に長
時間を要し且つ黄色の沈澱物が生成する。第３級ブタノ
ールとクロロホルムとの特に好適な比率は１／１２〜１
／４（重量比）である。If the amount of tertiary butanol in the electrolyte is too small, the reaction will be difficult to proceed, and if the amount of chloroform is too small, the reaction will take a long time and a yellow precipitate will form. A particularly preferred ratio of tertiary butanol to chloroform is 1/12 to 1.
/4 (weight ratio).
ピリジンは第３級ブタノール及びクロロホルムの合計量
に対して１／７〜１／１４（重量比）の比率で含有され
ているのが好ましい。ピリジンはカールフイツシヤ一試
薬の一成分であＶ１かつ電解液に電気伝導性を付与する
。本発明に係る電解液には上記の第３級ブタノール、ク
ロロホルム及びピリジン鳩外に沃素または沃化物、二酸
化硫黄が含有されている。It is preferable that pyridine is contained in a ratio of 1/7 to 1/14 (weight ratio) with respect to the total amount of tertiary butanol and chloroform. Pyridine is a component of Karl Fischer's reagent and provides V1 and electrical conductivity to the electrolyte. The electrolytic solution according to the present invention contains iodine, iodide, and sulfur dioxide in addition to the above-mentioned tertiary butanol, chloroform, and pyridine.
沃素または沃化物及び二酸化硫黄はそれぞれカールフイ
ツシヤ一試薬の成分である。これらの成分は電解液中に
それぞれ０．７〜２．２％（重量）及び２．２〜４．４
％（重量）存在させるのが適当である。但し沃化物は沃
素に換算した量である。好ましくは沃素または沃化物は
０．９〜１．９％、二酸化硫黄は２．９〜３．７％存在
させる。本発明に係る電解液の組成は上記した通９であ
るが、この電解液には所望により更に他の成分を若干含
有させてもよい。Iodine or iodide and sulfur dioxide are each components of Karl Fischer's reagent. These components are present in the electrolyte at a concentration of 0.7 to 2.2% (by weight) and 2.2 to 4.4%, respectively.
% (by weight) is suitably present. However, the amount of iodide is calculated in terms of iodine. Preferably iodine or iodide is present in an amount of 0.9-1.9% and sulfur dioxide is present in an amount of 2.9-3.7%. Although the composition of the electrolytic solution according to the present invention is as described above, this electrolytic solution may further contain a small amount of other components if desired.
例えば上記の各成分以外に四塩化炭素を少量含有させる
こともできる。本発明に係る電解液を用いる水分定量は
常法に従つて行なわれる。すなわち陽極室に本発明に係
る電解液を入れ、陰極室に適当な陰極液を入れ、通電し
て陽極液中の水分を除去する。次いで陽極液に試料を添
加し、再び通電して試料中の水分を滴定する。この際の
電解電流は２００ｍＡ以下が好ましい。なお、陽極液の
調製に沃素を用いた場合には、使用前に沃素の色が消え
るまで水を添加する．また、陰極液としては例えばメチ
ルゼロ・ソルブ２０〜８０ｍ１１ピリジン２０〜６０ｍ
１１四塩化炭素２０〜６０ｍ１，二酸化硫黄１０〜４０
９の組成のものが適当である。For example, in addition to the above-mentioned components, a small amount of carbon tetrachloride can also be included. Moisture determination using the electrolytic solution according to the present invention is carried out according to a conventional method. That is, the electrolytic solution according to the present invention is placed in the anode chamber, a suitable catholyte is placed in the cathode chamber, and water in the anolyte is removed by applying electricity. Next, a sample is added to the anolyte, and the water in the sample is titrated by applying electricity again. The electrolytic current at this time is preferably 200 mA or less. If iodine is used to prepare the anolyte, add water until the color of the iodine disappears before use. In addition, as a catholyte, for example, Methyl Zero Solv 20-80ml 11 Pyridine 20-60ml
11 carbon tetrachloride 20-60ml, sulfur dioxide 10-40
A composition of No. 9 is suitable.
．本発明に係る電解液を用いるとケトン、特にアセトン
やメチルエチルケトン等の活性なケトン中の微量の水分
を室温で測定することができる。次に実施例によジ本発
明を更に詳細に説明するが、本発明はその要旨をこえな
い限９？下の実施例に限定されるものではない。を混合
し、これに沃素の色が消失するまで水を添加して陽極液
とした。．． By using the electrolytic solution according to the present invention, trace amounts of water in ketones, particularly active ketones such as acetone and methyl ethyl ketone, can be measured at room temperature. Next, the present invention will be explained in more detail with reference to Examples, but the scope of the present invention does not go beyond its gist. It is not limited to the examples below. were mixed, and water was added to this until the color of iodine disappeared to obtain an anolyte.
デイジタル微量水分測定装置（三菱化成工業（株）、Ｍ
ＯＤＥＬ（Ａ一０１）の陽極室に上記の陽極液１００ｍ
１を人れ陰極室に陰極液（メチルセロソルブ３ｍ１１１
ピリジン０．７５ｍ１、二酸化硫黄０．３６ｆ１及び四
塩化炭素１ｍ１の混合液）を入れた。陽極液にアセトン
（純正化学（株）製、試薬特級）を添加し、電解電流１
００ｍＡ、室温で滴定を行なうことを１５〜２０回反復
した（すなわち、同一の陪媒を１５〜２０回反復使用し
た。Digital trace moisture measuring device (Mitsubishi Chemical Industries, Ltd., M
100 m of the above anolyte is placed in the anode chamber of ODEL (A-01).
Place 1 of the catholyte (methyl cellosolve 3ml) into the cathode chamber.
A mixed solution of 0.75 ml of pyridine, 0.36 fl of sulfur dioxide, and 1 ml of carbon tetrachloride was added. Acetone (manufactured by Junsei Kagaku Co., Ltd., special grade reagent) was added to the anolyte, and the electrolytic current was 1.
Titration at 00 mA and room temperature was repeated 15-20 times (i.e. the same solvent was used 15-20 times).
Claims (1)
ホルム及び第３級ブタノールを含有してなりエチルアル
コールを含まないカールフイツシヤー法による電量滴定
用電解液。 ２ 第３級ブタノールとクロロホルムとの重量比が１／
１２〜１／４であり、第３級ブタノール及びクロロホル
ムの合計とピリジンとの重量比が７〜１４である特許請
求の範囲第１項記載の電量滴定用電解液。 ３ 沃素または沃化物の含有量が沃素として０．７〜２
．２％（重量）であり、二酸化硫黄の含有量が２．２〜
４．４％（重量）である特許請求の範囲第１項または第
２項に記載の電量滴定用電解液。[Scope of Claims] 1. An electrolytic solution for coulometric titration by Karl Fischer method, which contains iodine or iodide, sulfur dioxide, pyridine, chloroform and tertiary butanol and does not contain ethyl alcohol. 2 The weight ratio of tertiary butanol and chloroform is 1/
The electrolytic solution for coulometric titration according to claim 1, wherein the weight ratio of the total of tertiary butanol and chloroform to pyridine is 7 to 14. 3 Iodine or iodide content is 0.7 to 2 as iodine
．． 2% (by weight), and the content of sulfur dioxide is 2.2~
The electrolytic solution for coulometric titration according to claim 1 or 2, which has a content of 4.4% (by weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP635179A JPS5937465B2 (en) | 1979-01-23 | 1979-01-23 | Electrolyte for coulometric titration by Karl Fischer method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP635179A JPS5937465B2 (en) | 1979-01-23 | 1979-01-23 | Electrolyte for coulometric titration by Karl Fischer method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5598350A JPS5598350A (en) | 1980-07-26 |
| JPS5937465B2 true JPS5937465B2 (en) | 1984-09-10 |
Family
ID=11635938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP635179A Expired JPS5937465B2 (en) | 1979-01-23 | 1979-01-23 | Electrolyte for coulometric titration by Karl Fischer method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5937465B2 (en) |
-
1979
- 1979-01-23 JP JP635179A patent/JPS5937465B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5598350A (en) | 1980-07-26 |
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