JP3175022B2 - pH measuring device and its calibration method - Google Patents
pH measuring device and its calibration methodInfo
- Publication number
- JP3175022B2 JP3175022B2 JP03867592A JP3867592A JP3175022B2 JP 3175022 B2 JP3175022 B2 JP 3175022B2 JP 03867592 A JP03867592 A JP 03867592A JP 3867592 A JP3867592 A JP 3867592A JP 3175022 B2 JP3175022 B2 JP 3175022B2
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- JP
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- Prior art keywords
- electrode
- solution
- metal oxide
- metal
- terminal
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は溶液のｐＨを測定するｐ
Ｈ測定装置及び該装置を校正する方法に関するものであ
る。The present invention relates to a method for measuring the pH of a solution.
The present invention relates to an H measuring device and a method for calibrating the device.
【０００２】[0002]
【従来の技術】周知のように、溶液のｐＨ測定には水素
イオン選択性の感応膜を有するｐＨ電極が使用され、そ
の代表的なものにガラスをｐＨ感応膜とするガラス電極
がある。また、高温溶液等の特殊な溶液や特殊な用途に
おいては、白金等の金属や酸化チタン等の金属酸化物を
ｐＨ感応膜とするｐＨ電極が使用されている。実際に溶
液のｐＨを測定する場合には、上記のｐＨ電極を作用電
極とし、この作用電極を甘汞電極や銀−塩化銀電極等の
比較電極と共に測定すべき溶液（被測定溶液）に浸漬
し、両電極間の電位差から被測定溶液のｐＨ値が求めら
れる。2. Description of the Related Art As is well known, a pH electrode having a hydrogen ion selective sensitive membrane is used for measuring the pH of a solution, and a typical example thereof is a glass electrode using glass as a pH sensitive membrane. For special solutions such as a high-temperature solution or a special use, a pH electrode using a metal such as platinum or a metal oxide such as titanium oxide as a pH-sensitive film is used. When actually measuring the pH of the solution, the above-mentioned pH electrode is used as a working electrode, and this working electrode is immersed in a solution to be measured (solution to be measured) together with a reference electrode such as a calomel electrode or a silver-silver chloride electrode. Then, the pH value of the solution to be measured is determined from the potential difference between the two electrodes.
【０００３】ところで、被測定溶液のｐＨの測定には、
直接電位差測定方法が広く用いられており、ｐＨの測定
に先立ち、ｐＨ電極を通常、ｐＨ６．８６とｐＨ４．０
１又はｐＨ９．１８の２つの標準液に浸漬し、２点校正
（場合によっては３点校正）を行なってから被測定溶液
のｐＨを測定する。By the way, in measuring the pH of a solution to be measured,
Direct potentiometric methods are widely used, and prior to measuring the pH, the pH electrode is usually measured at pH 6.86 and pH 4.0.
The sample is immersed in two standard solutions of 1 or pH 9.18, subjected to two-point calibration (in some cases, three-point calibration), and then measuring the pH of the solution to be measured.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記校
正操作は甚だ煩雑で、面倒であり、かつ時間がかかると
いう欠点があった。However, the above-mentioned calibration operation has the drawback that it is extremely complicated, troublesome, and time-consuming.
【０００５】一方、上述の金属や金属酸化物をｐＨ感応
膜として用いたｐＨ電極は安定性の点で問題があり、例
えば金属酸化物のｐＨ電極は濃度１０-1〜１０0 Ｍのア
スコルビン酸、フェロシアン、フェリシアンといった共
存物質の影響を受けると電極電位がしばしば変動するこ
とがある。このように電極電位が変動すると、不斉電位
が大きくなるから、ｐＨ測定装置（ｐＨ計）での校正が
できなくなる。このため、電極電位が変動したｐＨ電極
を元の電位状態に復帰させる必要があり、従来はｐＨ一
定（例えばｐＨ６．８６）の標準液に元の電位状態に復
帰するまで浸漬していた。On the other hand, the pH electrode using the above-mentioned metals or metal oxides as pH sensitive film has a problem in terms of stability, for example pH electrode of the metal oxide concentration 10 -1 to 10 0 M ascorbic acid The electrode potential often fluctuates under the influence of a coexisting substance such as ferrocyanide, ferrocyan and ferricyan. When the electrode potential fluctuates in this way, the asymmetry potential increases, so that calibration using a pH measuring device (pH meter) cannot be performed. For this reason, it is necessary to return the pH electrode whose electrode potential has fluctuated to the original potential state. Conventionally, the pH electrode has been immersed in a standard solution having a constant pH (eg, pH 6.86) until the original potential state is restored.
【０００６】しかしながら、ｐＨ電極が元の電位状態に
復帰するまでに通常は最短で１０時間を必要とし、１日
（２４時間）〜２日（４８時間）かかるものも多数あっ
た。従って、その間はｐＨ電極が使用できないので、極
めて効率が悪いという欠点があり、また、影響の受け方
によっては全く復帰しないこともあり、その場合には不
良品として廃棄せざるを得ないという欠点もあった。However, it usually takes a minimum of 10 hours for the pH electrode to return to the original potential state, and in many cases it takes one day (24 hours) to two days (48 hours). Therefore, since the pH electrode cannot be used during that time, there is a disadvantage that the efficiency is extremely low, and there is also a disadvantage that it may not return at all depending on how it is affected, in which case it must be discarded as a defective product. there were.
【０００７】従って、本発明の１つの目的は、金属や金
属酸化物をｐＨ感応膜とするｐＨ電極の電極電位を短時
間で簡単に安定化することができ、しかも校正操作が容
易になるｐＨ測定装置を提供することである。Therefore, one object of the present invention is to provide a pH electrode that uses a metal or metal oxide as a pH-sensitive film, thereby stabilizing the electrode potential of a pH electrode in a short time, and furthermore, a pH operation that facilitates a calibration operation. It is to provide a measuring device.
【０００８】本発明の他の目的は、金属や金属酸化物を
ｐＨ感応膜とするｐＨ電極を簡単かつ正確に、しかも短
時間で校正することができるｐＨ測定装置の校正方法を
提供することである。Another object of the present invention is to provide a method for calibrating a pH measuring apparatus capable of calibrating a pH electrode using a metal or metal oxide as a pH-sensitive film simply, accurately, and in a short time. is there.
【０００９】[0009]
【課題を解決するための手段】上記目的は本発明に係る
ｐＨ測定装置及びその校正方法によって達成される。要
約すれば、本発明は、金属酸化物又は金属をｐＨ感応膜
とするｐＨ電極と、該ｐＨ電極のｐＨ感応膜と同じ金属
酸化物又は金属を内極として使用する比較電極と、前記
ｐＨ電極が接続されるｐＨ端子及び前記比較電極が接続
される比較端子を備え、これら電極によって検出された
電位からｐＨ値を計測し、そのｐＨ値を指示する測定・
指示部とを具備するｐＨ測定装置において、前記ｐＨ電
極及び比較電極を収納する収納部を有し、該収納部内に
前記比較電極の内部液と同一のｐＨ一定の溶液を入れて
収納した両電極を該溶液に浸漬し、かつこれら電極を互
いに電気的に短絡させて前記ｐＨ電極の電極電位を安定
化させる手段を設けたことを特徴とするｐＨ測定装置、
並びに、金属酸化物又は金属をｐＨ感応膜とするｐＨ電
極と、該ｐＨ電極のｐＨ感応膜と同じ金属酸化物又は金
属を内極として使用する比較電極とを、互いに電気的に
短絡させた状態で、前記比較電極の内部液と同一のｐＨ
一定の溶液中に浸漬し、装置本体のｐＨ端子と比較端子
とを短絡させてｐＨ表示値を前記比較電極の内部液のｐ
Ｈ値に合わせることを特徴とするｐＨ測定装置の校正方
法である。The above objects can be attained by a pH measuring apparatus and a calibration method according to the present invention. In summary, the present invention provides a pH electrode using a metal oxide or metal as a pH-sensitive film, a comparative electrode using the same metal oxide or metal as the pH-sensitive film of the pH electrode as an inner electrode, Is provided with a pH terminal and a comparison terminal to which the comparison electrode is connected. The pH value is measured from a potential detected by these electrodes.
A pH measuring device having an indicator and a storage unit for storing the pH electrode and the comparison electrode, and both electrodes containing a solution having the same pH as the internal liquid of the comparison electrode and stored in the storage unit. A pH measuring device characterized by having a means for stabilizing the electrode potential of the pH electrode by immersing the electrode in the solution and electrically short-circuiting the electrodes to each other.
A state in which a pH electrode using a metal oxide or metal as a pH-sensitive film and a comparative electrode using the same metal oxide or metal as the pH-sensitive film of the pH electrode as an inner electrode are electrically short-circuited to each other. At the same pH as the internal liquid of the reference electrode.
It is immersed in a certain solution, and the pH terminal of the device body and the comparison terminal are short-circuited, and the pH display value is set to p of the internal solution of the comparison electrode.
This is a method for calibrating a pH measuring device, which is characterized by adjusting to an H value.
【００１０】[0010]
【実施例】以下、本発明の実施例について添付図面を参
照して詳細に説明する。Embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
【００１１】図１は本発明によるｐＨ測定装置の一実施
例を示す概略構成図であり、ｐＨ電極３０及び比較電極
１０が装置本体に付属するアダプタ１内に収納されてい
る状態を示す。このアダプタ１はその内部に比較電極１
０の内部液１３と同一のｐＨ一定の溶液１５が注入され
ており、また、ｐＨ電極３０のリード線３１及び比較電
極１０のリード線２３の先端にそれぞれ取り付けられた
電極プラグ（図示せず）が差し込めるｐＨ端子（入力ジ
ャック）２及び比較端子（入力ジャック）３を備えてい
る。これら端子間にはオン・オフスイッチ４が接続され
ており、スイッチ４をオンにすると、ｐＨ電極３０と比
較電極１０とが短絡できるように構成されている。FIG. 1 is a schematic diagram showing an embodiment of a pH measuring apparatus according to the present invention, in which a pH electrode 30 and a reference electrode 10 are housed in an adapter 1 attached to a main body of the apparatus. This adapter 1 has a reference electrode 1 inside.
An electrode plug (not shown) into which a solution 15 having the same constant pH as the internal solution 13 of the pH electrode 30 is injected, and which is attached to the leading ends of the lead wire 31 of the pH electrode 30 and the lead wire 23 of the comparative electrode 10, respectively. A pH terminal (input jack) 2 and a comparison terminal (input jack) 3 into which the plug can be inserted. An on / off switch 4 is connected between these terminals. When the switch 4 is turned on, the pH electrode 30 and the reference electrode 10 can be short-circuited.
【００１２】本実施例のｐＨ電極３０のｐＨ感応膜及び
比較電極１１の内極にはそれぞれ酸化イリジウムよりな
る金属酸化物が使用されている。本発明者達は金属酸化
物について種々の研究を行なった結果、化学的に安定で
フッ化水素酸を含む酸に侵されない、しかも膜抵抗値の
低い酸化イリジウムがｐＨに感応する事実を確認し、こ
の酸化イリジウム膜をｐＨ感応膜とするｐＨ電極及び酸
化イリジウム膜を内極とする比較電極を製造した。次
に、これら電極について説明する。A metal oxide made of iridium oxide is used for each of the pH-sensitive film of the pH electrode 30 of the present embodiment and the inner electrode of the reference electrode 11. As a result of various studies on metal oxides, the present inventors have confirmed that iridium oxide, which is chemically stable, is not attacked by acids including hydrofluoric acid, and has a low film resistance, is sensitive to pH. A pH electrode using the iridium oxide film as a pH-sensitive film and a comparative electrode using the iridium oxide film as an inner electrode were manufactured. Next, these electrodes will be described.
【００１３】上記比較電極１０は内筒１１及び外筒１２
にそれぞれジャンクション１１ａ及び１２ａを有するダ
ブルジャンクション形のものが使用され、内筒１１内の
内部液１３中に浸漬された内極１４に酸化イリジウムが
使用されている。この内極１４は、図２に拡大して示す
ように、所定の形状及び寸法の導電性の電極支持体２１
と、この支持体２１の１つの面に、例えばスパッタリン
グによって製膜された酸化イリジウム膜２２とから構成
され、電極支持体２１が内筒１１内に同軸的に配置され
た支持管体１６の底面に形成された透孔中に液密状態に
取り付けられることによって、酸化イリジウム膜２２は
内筒１１内の内部液１３中に完全に浸漬した状態で支持
されている。The comparison electrode 10 comprises an inner cylinder 11 and an outer cylinder 12
A double-junction type having junctions 11a and 12a is used, and iridium oxide is used for an inner electrode 14 immersed in an internal liquid 13 in an inner cylinder 11. As shown in an enlarged manner in FIG. 2, the inner pole 14 is made of a conductive electrode support 21 having a predetermined shape and dimensions.
And an iridium oxide film 22 formed on one surface of the support 21 by, for example, sputtering, and the bottom surface of the support tube 16 in which the electrode support 21 is coaxially arranged in the inner cylinder 11. The iridium oxide film 22 is supported in a state of being completely immersed in the internal liquid 13 in the inner cylinder 11 by being attached in a liquid-tight state in the through-hole formed in the inner cylinder 11.
【００１４】電極支持体２１は酸化イリジウム膜２２の
支持体として機能するもので、アルミニウム、白金、タ
ンタル、チタン、イリジウムなど導電性を有するもので
あればどんな金属でも良いが、本実施例では細長い板状
体のタンタルの金属板が使用され、酸化イリジウム膜２
２が被着された以外の全表面は絶縁膜２４で電気的に絶
縁されている。また、電極支持体２１の内部液１３と接
触しない上端部にはリード線２３が電気的に接続され、
このリード線２３は支持管体１６内を通り、その先端に
取り付けられた電極プラグがアダプタ１の比較端子３に
差し込まれている。なお、溶液のｐＨを測定するときに
は、図示しない装置本体の測定処理回路の比較端子（入
力ジャック）に接続される。The electrode support 21 functions as a support for the iridium oxide film 22, and may be made of any conductive material such as aluminum, platinum, tantalum, titanium, and iridium. A plate-shaped tantalum metal plate is used, and an iridium oxide film 2 is used.
The entire surface other than the surface where 2 is applied is electrically insulated by the insulating film 24. Further, a lead wire 23 is electrically connected to an upper end portion of the electrode support 21 which does not contact the internal liquid 13,
The lead wire 23 passes through the inside of the support tube 16, and an electrode plug attached to the tip thereof is inserted into the comparison terminal 3 of the adapter 1. When measuring the pH of the solution, it is connected to a comparison terminal (input jack) of a measurement processing circuit (not shown) of the apparatus main body.
【００１５】なお、図２では酸化イリジウム膜２２と電
極支持体２１との間に絶縁膜２４が存在しないが、電極
支持体２１には初めにその全面に絶縁膜２４が被着され
ており、酸化イリジウム膜２２を、例えばスパッタリン
グ被着することによってその間にある絶縁膜が除去さ
れ、酸化イリジウム膜２２は電極支持体２１と電気的に
強固に接続される。従って、酸化イリジウム膜を形成す
る部分の絶縁膜を予め電極支持体２１から除去しておく
必要はない。In FIG. 2, there is no insulating film 24 between the iridium oxide film 22 and the electrode support 21, but the electrode support 21 is first covered with the insulating film 24 over its entire surface. The iridium oxide film 22 is, for example, deposited by sputtering to remove the insulating film therebetween, and the iridium oxide film 22 is electrically and strongly connected to the electrode support 21. Therefore, it is not necessary to remove the insulating film at the portion where the iridium oxide film is to be formed from the electrode support 21 in advance.
【００１６】また、電極支持体２１として、例えばサフ
ァイヤ、ガラス、セラミックスなどの無機材料やポリ塩
化ビニル（ＰＶＣ）、フッ素樹脂などのプラスチック材
料よりなる絶縁物の板状体を使用してもよい。この場合
には酸化イリジウム膜２２の上部を支持管体１６内に配
置し、リード線２３を酸化イリジウム膜２２の上端部に
接続することになる。一方、絶縁膜２４としては、五酸
化タンタル(Ta2O5) 、アルミナ(Al2O3) 、二酸化ケイ素
(SiO2)、窒化ケイ素(Si3N4) などの絶縁性の酸化物、窒
化物とフッ素樹脂などのプラスチック材料が使用でき
る。絶縁膜２４は自然酸化膜を利用しても良いし、スパ
ッタリング、ＣＶＤなどの真空薄膜製造技術、加熱酸
化、金属アルコキシドを材料としたディップコーティン
グ法などの製造方法を使用して形成しても良い。なお、
電極支持体２１の形状や寸法は任意に選択できるもので
あり、例えば、棒状体、円筒及び角筒状体等の種々の形
状の支持体が使用できる。また、金属酸化物としては、
酸化イリジウムの他に、例えば酸化パラジウム、酸化チ
タンなどの金属酸化物が使用できる。勿論、比較電極１
０の内極１４は任意の構成のものが使用できる。The electrode support 21 may be an insulating plate made of an inorganic material such as sapphire, glass, or ceramics, or a plastic material such as polyvinyl chloride (PVC) or fluororesin. In this case, the upper part of the iridium oxide film 22 is disposed in the support tube 16, and the lead wire 23 is connected to the upper end of the iridium oxide film 22. On the other hand, as the insulating film 24, tantalum pentoxide (Ta 2 O 5 ), alumina (Al 2 O 3 ), silicon dioxide
Insulating oxides such as (SiO 2 ) and silicon nitride (Si 3 N 4 ), and plastic materials such as nitride and fluororesin can be used. The insulating film 24 may use a natural oxide film, or may be formed using a manufacturing method such as a vacuum thin film manufacturing technique such as sputtering or CVD, a thermal oxidation, or a dip coating method using a metal alkoxide as a material. . In addition,
The shape and dimensions of the electrode support 21 can be arbitrarily selected. For example, various shapes of supports such as a rod, a cylinder, and a rectangular tube can be used. Also, as the metal oxide,
In addition to iridium oxide, for example, metal oxides such as palladium oxide and titanium oxide can be used. Of course, reference electrode 1
The inner pole 14 of 0 may be of any configuration.
【００１７】上記酸化イリジウムのｐＨ電極３０は、図
３に拡大して示すように、所定の形状及び寸法の導電性
の電極支持体３２と、この支持体３２の１つの面に、例
えばスパッタリングによって製膜された酸化イリジウム
膜よりなるｐＨ感応膜３３とを含み、このｐＨ感応膜３
３を支持する電極支持体３２が、例えばガラスの支持管
３４の底面に固着されることによって、ｐＨ感応膜３３
は支持管３４に支持される。本実施例では、電極支持体
３２として直径２ｍｍ、厚さ０．２ｍｍの白金の円板を
使用し、この白金円板に白金のリード線３１を接続し、
このリード線３１をｐＨ電極３０のガラスの支持管３４
の端面に形成されたリード線挿通孔に挿通して白金円板
のリード線３１が接続された面をガラス支持管３４の端
面に接触させ、加熱して白金円板をガラス支持管３４の
端面に融着させた。このときリード線挿通孔は閉塞さ
れ、リード線３１はガラス支持管３４の端面に封止され
た。次に、酸洗浄により十分に表面の酸化被膜を除去し
た後、白金円板の表面の中心部に直径１ｍｍの円形の感
応膜形成部を残して、残りの部分をマスキングし、これ
をスパッタリング装置の成膜室に入れて、酸化性雰囲気
下でＩｒターゲットを電圧０．８ＫＶにて１００分間ス
パッタリングして酸化イリジウム膜を形成し、次いで、
この成膜された酸化イリジウム膜をマスキングし、アル
カリ性の溶液中に２４時間浸漬して酸化イリジウム膜部
分を除く白金円板の全露出面に酸化膜（絶縁膜）３５を
形成した。リード線３１はガラス支持管３４内を通り、
その先端に取り付けられた電極プラグがアダプタ１のｐ
Ｈ端子３に差し込まれている。なお、溶液のｐＨを測定
するときには、図示しない装置本体の測定処理回路のｐ
Ｈ端子（入力ジャック）に接続される。As shown in the enlarged view of FIG. 3, the iridium oxide pH electrode 30 has a conductive electrode support 32 having a predetermined shape and dimensions, and is provided on one surface of the support 32 by, for example, sputtering. A pH-sensitive film 33 made of a formed iridium oxide film.
3 is fixed to the bottom surface of a support tube 34 made of, for example, glass to form a pH-sensitive film 33.
Is supported by the support tube 34. In this embodiment, a platinum disk having a diameter of 2 mm and a thickness of 0.2 mm is used as the electrode support 32, and a platinum lead wire 31 is connected to the platinum disk.
The lead wire 31 is connected to a glass support tube 34 of the pH electrode 30.
The platinum disc is connected to the end face of the glass support tube 34 by being inserted into the lead wire insertion hole formed on the end face of the glass support tube 34, and heated to bring the platinum disc into the end face of the glass support tube 34. Was fused. At this time, the lead wire insertion hole was closed, and the lead wire 31 was sealed on the end face of the glass support tube 34. Next, after the oxide film on the surface is sufficiently removed by acid cleaning, a circular sensitive film forming portion having a diameter of 1 mm is left at the center of the surface of the platinum disk, and the remaining portion is masked. , An Ir target was sputtered under a oxidizing atmosphere at a voltage of 0.8 KV for 100 minutes to form an iridium oxide film.
The formed iridium oxide film was masked and immersed in an alkaline solution for 24 hours to form an oxide film (insulating film) 35 on the entire exposed surface of the platinum disk except for the iridium oxide film portion. The lead wire 31 passes through a glass support tube 34,
The electrode plug attached to the tip is
Connected to H terminal 3. Note that when measuring the pH of the solution, p
Connected to H terminal (input jack).
【００１８】また、他の例においては、電極支持体３２
として厚さ０．５ｍｍ、直径４ｍｍのタンタルの円板を
使用し、このタンタル円板の全面に自然酸化により形成
された五酸化タンタルの被膜を絶縁膜３５とし、この絶
縁被膜を有するタンタル円板上にマスキング材を用いて
直径３ｍｍの酸化イリジウム膜をスパッタリングにより
被着し、厚さ約１０００ÅのｐＨ感応膜３３を形成し
た。In another example, the electrode support 32
A tantalum disk having a thickness of 0.5 mm and a diameter of 4 mm is used, and a tantalum pentoxide film formed by natural oxidation on the entire surface of the tantalum disk is used as an insulating film 35, and a tantalum disk having this insulating film is used. An iridium oxide film having a diameter of 3 mm was applied thereon by sputtering using a masking material to form a pH-sensitive film 33 having a thickness of about 1000 °.
【００１９】なお、図３では酸化イリジウムのｐＨ感応
膜３３と白金円板の電極支持体３２との間に絶縁膜３５
が存在しないが、電極支持体３２には初めにその全面に
絶縁膜３５が被着されており、酸化イリジウムの金属酸
化物膜を、例えばスパッタリング被着することによって
その間にある絶縁膜が除去され、金属酸化物膜は電極支
持体３２と電気的に強固に接続される。従って、金属酸
化物膜を形成する部分の絶縁膜を予め電極支持体３２か
ら除去しておく必要はない。In FIG. 3, an insulating film 35 is provided between the pH-sensitive film 33 of iridium oxide and the electrode support 32 of a platinum disk.
However, an insulating film 35 is first applied to the entire surface of the electrode support 32, and the insulating film therebetween is removed by applying a metal oxide film of iridium oxide, for example, by sputtering. The metal oxide film is electrically and strongly connected to the electrode support 32. Therefore, it is not necessary to remove the portion of the insulating film where the metal oxide film is to be formed from the electrode support 32 in advance.
【００２０】上記導電性の電極支持体３２は金属酸化物
膜のｐＨ感応膜３３の支持体として機能するもので、ア
ルミニウム、白金、タンタル、チタン、イリジウムなど
導電性を有するものであればどんな金属でも良い。ま
た、絶縁膜３５としては、五酸化タンタル(Ta2O5) 、ア
ルミナ(Al2O3) 、二酸化ケイ素(SiO2)、窒化ケイ素(Si3
N4) などの絶縁性の酸化物、窒化物とフッ素樹脂などの
プラスチック材料が使用できる。絶縁膜３５は自然酸化
膜を利用しても良いし、スパッタリング、ＣＶＤなどの
真空薄膜製造技術、加熱酸化、金属アルコキシドを材料
としたディップコーティング法などの製造方法を使用し
て形成しても良い。さらに、金属酸化物膜としては、酸
化イリジウム、酸化パラジウム、酸化チタンなどの金属
酸化物が使用でき、スパッタリング、ＣＶＤなどの真空
薄膜製造技術によって電極支持体３２上に製膜される。
勿論、上記ｐＨ電極の構成、使用材料、製造方法等は単
なる例示であり、必要に応じて種々に変形、変更可能で
ある。The conductive electrode support 32 functions as a support for the pH-sensitive film 33 of a metal oxide film, and can be made of any conductive material such as aluminum, platinum, tantalum, titanium, and iridium. But it is good. As the insulating film 35, tantalum pentoxide (Ta 2 O 5 ), alumina (Al 2 O 3 ), silicon dioxide (SiO 2 ), silicon nitride (Si 3
Plastic materials such as insulating oxides such as N 4 ), nitrides and fluororesins can be used. The insulating film 35 may use a natural oxide film, or may be formed using a manufacturing method such as a vacuum thin film manufacturing technique such as sputtering or CVD, heat oxidation, or a dip coating method using a metal alkoxide as a material. . Further, as the metal oxide film, a metal oxide such as iridium oxide, palladium oxide, or titanium oxide can be used, and is formed on the electrode support 32 by a vacuum thin film manufacturing technique such as sputtering or CVD.
Of course, the configuration, materials used, manufacturing method, and the like of the pH electrode are merely examples, and various modifications and changes can be made as needed.
【００２１】このように、比較電極１０の内極１４にも
ｐＨ電極３０のｐＨ感応膜３３と同じ金属酸化物、本実
施例では酸化イリジウム、が使用されているときには、
比較電極１０の内筒１１内に注入されている内部液１３
と同一のｐＨ一定の溶液１５をアダプタ１内に注入して
おき、ｐＨ電極３０と比較電極１０を浸漬しておく。こ
の場合、アダプタ１のスイッチ４はオンにし（スイッチ
４は常時オンにしておき、必要なときにオフにすると好
便である）、両電極３０及び１０を互いに電気的に短絡
しておく。本発明者達の実験によれば、ｐＨ６．８６の
標準液である中性リン酸塩溶液での電極電位が３２０ｍ
Ｖである酸化イリジウムのｐＨ電極３０と２４７ｍＶの
比較電極１０とを、この比較電極１０の内筒１１内の内
部液１３と同一のｐＨ一定の溶液１５中に浸漬し、１時
間放置した。その後、このｐＨ電極３０を上記ｐＨ６．
８６の中性リン酸塩溶液に浸漬してその電極電位を測定
したところ、比較電極１０と同じ２４７ｍＶであった。
このように、ｐＨ電極３０と比較電極１０とを互いに電
気的に短絡し、比較電極１０の内筒１１内の内部液１３
と同一のｐＨ一定の溶液１５（内部液１３としてｐＨ
６．８６の中性リン酸塩溶液を用いても良い）に１時間
浸漬させると、大幅に変動した酸化イリジウムのｐＨ電
極３０の電極電位が１時間という短時間で比較電極１０
の電極電位とほぼ同じになり、ほぼ元の電位状態に復帰
し、安定化されることが分かった。また、１ｐＨ当りの
傾きも理論値と一致した。このように大幅に変動した酸
化イリジウムのｐＨ電極の電位が短時間でほぼ元の状態
に復帰し、安定化するのは、酸化イリジウムが半導体金
属酸化物であるため、相互に電気的に短絡することで電
流が流れ、平衡状態になる作用が生ずるものと考えられ
る。Thus, when the same metal oxide as the pH-sensitive film 33 of the pH electrode 30, in this embodiment, iridium oxide, is also used for the inner electrode 14 of the reference electrode 10,
Internal liquid 13 injected into inner cylinder 11 of reference electrode 10
A solution 15 having the same constant pH as above is injected into the adapter 1, and the pH electrode 30 and the reference electrode 10 are immersed. In this case, the switch 4 of the adapter 1 is turned on (it is convenient to keep the switch 4 on all the time, and it is convenient to turn it off when necessary), and the electrodes 30 and 10 are electrically short-circuited to each other. According to the experiments of the present inventors, the electrode potential in a neutral phosphate solution, which is a standard solution of pH 6.86, was 320 m
The pH electrode 30 of iridium oxide V and the comparative electrode 10 of 247 mV were immersed in a solution 15 having the same pH as the internal liquid 13 in the inner cylinder 11 of the comparative electrode 10 and left for 1 hour. Thereafter, the pH electrode 30 is set to the pH 6.
86 was immersed in a neutral phosphate solution, and the electrode potential was measured.
In this way, the pH electrode 30 and the comparison electrode 10 are electrically short-circuited to each other, and the internal liquid 13 in the inner cylinder 11 of the comparison electrode 10 is
A solution 15 having the same pH as that of
6.86 neutral phosphate solution may be used), the electrode potential of the pH electrode 30 of iridium oxide, which fluctuates greatly, changes in a short time of 1 hour,
It turned out to be almost the same as the electrode potential, and returned to almost the original potential state and stabilized. Also, the slope per pH was in agreement with the theoretical value. The reason that the potential of the pH electrode of iridium oxide that fluctuates greatly in this manner returns to almost the original state in a short time and stabilizes is that iridium oxide is a semiconductor metal oxide, so that it is electrically short-circuited with each other. It is considered that the current flows, and the effect of the equilibrium state occurs.
【００２２】次に、上記構成の本実施例のｐＨ測定装置
の動作について説明する。Next, the operation of the pH measuring apparatus of the present embodiment having the above configuration will be described.
【００２３】まず、溶液のｐＨを測定するときには、装
置本体の測定処理回路のｐＨ端子及び比較端子を短絡
し、メータ（アナログ又はディジタル）の表示値を比較
電極１０の内部液１３のｐＨ値に合わせる。なお、通常
はｐＨ電極３０及び比較電極１０のリード線３１及び２
３の電極プラグを装置本体の測定処理回路のｐＨ端子及
び比較端子からはずすと、これら端子は自動的に短絡さ
れるようになっているので、別個の短絡手段は設けなく
ても良い。これによって２点校正のうちの１点目の校正
が電気的校正で行なえることになる。即ち、１点目の校
正を行なう必要がなくなる。First, when measuring the pH of the solution, the pH terminal and the comparison terminal of the measurement processing circuit of the apparatus main body are short-circuited, and the display value of the meter (analog or digital) is changed to the pH value of the internal liquid 13 of the comparison electrode 10. Match. The lead wires 31 and 2 of the pH electrode 30 and the comparative electrode 10 are usually
When the electrode plug of No. 3 is removed from the pH terminal and the comparison terminal of the measurement processing circuit of the apparatus main body, these terminals are automatically short-circuited, so that it is not necessary to provide a separate short-circuit means. Thus, the first calibration of the two calibrations can be performed by electrical calibration. That is, it is not necessary to perform the first calibration.
【００２４】例えば、比較電極１０の内部液１３がｐＨ
６．８６の溶液である場合には、同一のｐＨ６．８６の
溶液をアダプタ１内に注入し、測定が終了した後、ｐＨ
電極３０と比較電極１０をアダプタ１内に収納し、それ
らの電極プラグをアダプタ１のｐＨ端子２及び比較端子
３に差し込み、スイッチ４をオンにして両電極を短絡し
ておく。これによって、ｐＨ電極３０はその電極電位が
すぐに元の状態に復帰し、安定化される。一方、装置本
体のｐＨ端子と比較端子を短絡し（上述したように、ｐ
Ｈ電極３０及び比較電極１０の電極プラグを装置本体の
ｐＨ端子及び比較端子からはずすと、これら端子は自動
的に短絡されるので、実際には短絡されている）、メー
タの表示値をｐＨ６．８６に合わせる。これによって、
ｐＨ測定時に両電極３０、１０を校正液に浸漬し、装置
本体の測定処理回路に接続して校正操作をする必要なし
に、１点目の校正が完了したことになる。For example, the internal liquid 13 of the comparison electrode 10
In the case of a 6.86 solution, the same pH 6.86 solution is injected into the adapter 1, and after the measurement is completed,
The electrode 30 and the comparison electrode 10 are housed in the adapter 1 and their electrode plugs are inserted into the pH terminal 2 and the comparison terminal 3 of the adapter 1, and the switch 4 is turned on to short-circuit both electrodes. As a result, the electrode potential of the pH electrode 30 immediately returns to its original state, and is stabilized. On the other hand, the pH terminal of the device body and the comparison terminal were short-circuited (as described above, p
When the electrode plugs of the H electrode 30 and the comparison electrode 10 are removed from the pH terminal and the comparison terminal of the apparatus main body, these terminals are automatically short-circuited, so that they are actually short-circuited). Adjust to 86. by this,
At the time of pH measurement, both electrodes 30, 10 are immersed in the calibration solution, and the first point calibration is completed without the need to connect to the measurement processing circuit of the apparatus main body and perform the calibration operation.
【００２５】次に、２点目の校正は両電極プラグを装置
本体の端子に差し込み、例えばｐＨ４．０１の溶液など
で通常のように校正すれば良い。電極プラグの抜き差し
が面倒であれば、装置本体のｐＨ端子と比較端子を短絡
するスイッチを設け、校正時にこのスイッチをオンにす
れば良い。この場合には、アダプタ１にｐＨ端子２、比
較端子３、スイッチ４を設けなくても良い。ただし、ア
ダプタ１は装置本体から取り外し可能に構成されている
ので、上述したように、アダプタ１にｐＨ端子２、比較
端子３、スイッチ４を設けておけば、アダプタ１だけで
使用していないｐＨ電極の電極電位を安定化でき、好便
である。Next, the second calibration may be performed by inserting both electrode plugs into the terminals of the apparatus body and performing calibration as usual with a solution of pH 4.01, for example. If it is troublesome to insert and remove the electrode plug, a switch for short-circuiting the pH terminal and the comparison terminal of the apparatus main body may be provided, and this switch may be turned on during calibration. In this case, the adapter 1 does not need to be provided with the pH terminal 2, the comparison terminal 3, and the switch 4. However, since the adapter 1 is configured to be detachable from the apparatus main body, as described above, if the adapter 1 is provided with the pH terminal 2, the comparison terminal 3, and the switch 4, the pH not used only by the adapter 1 is used. The electrode potential of the electrode can be stabilized, which is convenient.
【００２６】このように、本実施例によれば、１点目の
校正が不要になるから、直ちに２点目の校正操作が行な
え、校正操作が簡単化され、短時間で行なえるという利
点がある。特に、精度をさほど必要とせず、１点校正だ
けで十分な場合には、２点目の校正をする必要がないの
で、実質的に校正操作が不必要になるし、また、校正液
が比較電極１０の内部液１３だけで済むという利点があ
る。さらに、ｐＨ電極の電極電位が酸化剤、還元剤など
により大幅に変動した場合でも、従来は校正不能であっ
たが、本実施例によれば、ｐＨ電極の電位が短時間で復
帰し、安定化されるため、常時校正が可能になるという
利点もある。As described above, according to this embodiment, since the first point calibration is not required, the second point calibration operation can be performed immediately, and the calibration operation is simplified, and the advantage is that the calibration operation can be performed in a short time. is there. In particular, when accuracy is not so much required and only one-point calibration is sufficient, there is no need to perform the second point calibration, so the calibration operation is substantially unnecessary, and the calibration solution can be compared. There is an advantage that only the internal liquid 13 of the electrode 10 is required. Furthermore, even if the electrode potential of the pH electrode fluctuates greatly due to an oxidizing agent, a reducing agent, etc., it has been impossible to calibrate conventionally, but according to the present embodiment, the potential of the pH electrode is restored in a short time, Therefore, there is also an advantage that calibration can be always performed.
【００２７】図４は本発明の第２の実施例を示す概略構
成図であり、本発明をフローシステムに適用した場合を
示す。上記構成のｐＨ電極３０及び比較電極１０はフロ
ー系４０中に配置されており、これら電極３０、１０は
リード線３１、２３を通じて装置本体の測定処理回路４
１のｐＨ端子４２及び比較端子４３に接続されている。
これら端子４２、４３間にはスイッチ４４が接続されて
おり、選択的にこれら端子間を短絡できるようになって
いる。また、フロー系４０には校正液４５及び比較電極
１０の内部液１３と同一のｐＨ一定の溶液４６のいずれ
か一方がポンプ４７により選択的にフローできるように
構成されている。FIG. 4 is a schematic diagram showing a second embodiment of the present invention, in which the present invention is applied to a flow system. The pH electrode 30 and the comparative electrode 10 having the above configuration are arranged in a flow system 40, and these electrodes 30, 10 are connected to the measurement processing circuit 4 of the apparatus main body through the lead wires 31, 23.
1 pH terminal 42 and comparison terminal 43.
A switch 44 is connected between these terminals 42 and 43 so that these terminals can be selectively short-circuited. Further, the flow system 40 is configured so that either one of the calibration solution 45 and the solution 46 having the same pH as the internal solution 13 of the comparison electrode 10 can be selectively flown by the pump 47.
【００２８】上記構成において、被測定溶液のｐＨを測
定する場合には、スイッチ４４がオフにされ、フロー系
４０に被測定溶液が流入され、ｐＨ電極３０及び比較電
極１０を通じて測定処理回路４１に検出電位が供給さ
れ、被測定溶液のｐＨが測定される。一方、校正時には
スイッチ４４がオンにされてｐＨ電極３０と比較電極１
０が短絡され、同時にポンプ４７により比較電極１０の
内部液１３と同一の溶液４６がフロー系４０に供給され
る。必要ならば、測定処理回路４１のメータを内部液１
３のｐＨ値に合わせる。これによって、被測定溶液など
で変動したｐＨ電極３０の電極電位はすぐに元の状態に
復帰し、安定化されるから、次の測定を行なうことがで
きるようになる。In the above configuration, when measuring the pH of the solution to be measured, the switch 44 is turned off, the solution to be measured flows into the flow system 40, and the measurement processing circuit 41 passes through the pH electrode 30 and the comparison electrode 10. The detection potential is supplied, and the pH of the solution to be measured is measured. On the other hand, during calibration, the switch 44 is turned on, and the pH electrode 30 and the reference electrode 1 are turned on.
0 is short-circuited, and at the same time, the same solution 46 as the internal solution 13 of the comparison electrode 10 is supplied to the flow system 40 by the pump 47. If necessary, set the meter of the measurement processing circuit 41 to the internal liquid 1
Adjust to a pH value of 3. As a result, the electrode potential of the pH electrode 30 fluctuated by the solution to be measured or the like is immediately returned to the original state and stabilized, so that the next measurement can be performed.
【００２９】また、測定が連続的でなく、間欠的に行な
われる場合には、フロー系４０に内部液１３と同一の溶
液４６を供給しておき、スイッチ４４をオンにしてｐＨ
電極３０と比較電極１０を短絡しておく。そして測定処
理回路４１のメータを内部液１３のｐＨ値に合わせる。
このようにするとｐＨ電極３０は常時は安定化状態にあ
るから、測定時にフロー系４０に被測定溶液を供給すれ
ば、直ちに測定が行なえることになる。When the measurement is performed intermittently instead of continuously, the same solution 46 as the internal solution 13 is supplied to the flow system 40, and the switch 44 is turned on to adjust the pH.
The electrode 30 and the comparative electrode 10 are short-circuited. Then, the meter of the measurement processing circuit 41 is adjusted to the pH value of the internal liquid 13.
In this case, since the pH electrode 30 is always in a stable state, if the solution to be measured is supplied to the flow system 40 during measurement, the measurement can be performed immediately.
【００３０】本実施例においても上記第１の実施例と同
様の作用効果が得られることは明白であるので、その説
明を省略する。It is apparent that the same operation and effect as those of the first embodiment can be obtained in this embodiment, so that the description thereof will be omitted.
【００３１】図５は本発明をｐＨコントロールシステム
に適用した本発明の第３の実施例を示す概略構成図であ
る。本実施例は、ｐＨを制御すべきサンプル５１のｐＨ
値が既知であり、比較電極１０の内部液１３としてこの
ｐＨ既知のサンプル５１を使用し、このサンプル５１に
例えばｐＨ制御用ノズル５２によって試薬を添加した
り、或は電解などでｐＨ値を制御する場合である。この
場合には、１点目の校正は従来通りｐＨ一定の標準液で
行ない、２点目の校正は、図５（Ａ）に示すように、サ
ンプル５１のｐＨを制御する前にスイッチ４４をオンに
してサンプル５１中に浸漬したｐＨ電極３０と比較電極
１０を短絡し、サンプル５１のｐＨ値を校正値として測
定処理回路４１のメータを合わせる。これによって２点
目の校正が終了するから、測定時には、図５（Ｂ）に示
すように、スイッチ４４をオフにし、例えばｐＨ制御用
ノズル５２を通じて試薬を添加することによってｐＨ値
が制御されたサンプル５１′のｐＨ値を、校正の終了し
たｐＨ電極３０及び比較電極１０により検出して測定処
理回路４１で測定すれば良い。FIG. 5 is a schematic diagram showing a third embodiment of the present invention in which the present invention is applied to a pH control system. In this embodiment, the pH of the sample 51 whose pH is to be controlled is
A sample 51 whose pH is known and whose pH is known is used as the internal liquid 13 of the reference electrode 10, and a reagent is added to the sample 51 by, for example, a pH control nozzle 52, or the pH value is controlled by electrolysis or the like. This is the case. In this case, the first calibration is performed with a standard solution having a constant pH as in the past, and the second calibration is performed by turning the switch 44 before controlling the pH of the sample 51 as shown in FIG. When turned on, the pH electrode 30 immersed in the sample 51 and the comparative electrode 10 are short-circuited, and the meter of the measurement processing circuit 41 is adjusted using the pH value of the sample 51 as a calibration value. As a result, the calibration of the second point is completed. At the time of measurement, as shown in FIG. 5B, the switch 44 is turned off, and the pH value is controlled by, for example, adding a reagent through the pH control nozzle 52. The pH value of the sample 51 ′ may be detected by the pH electrode 30 and the reference electrode 10 that have been calibrated, and may be measured by the measurement processing circuit 41.
【００３２】本実施例においても、精度をさほど必要と
しない場合には、１点目の校正は省略できるので、校正
液が１種類で済み、しかも校正操作が非常に簡単になる
という利点がある。Also in this embodiment, when the accuracy is not so much required, the first point calibration can be omitted, so that there is an advantage that only one kind of calibration liquid is required and the calibration operation becomes very simple. .
【００３３】図６は本発明の第４の実施例を示す概略構
成図であり、本実施例は、ｐＨを制御すべきサンプル５
１のｐＨ値が既知であり、比較電極１０の内部液１３と
してこのｐＨ既知のサンプル５１を使用し、比較電極１
０及びｐＨ電極３０が液絡部５３を介して配置され、ｐ
Ｈ電極３０に供給されるサンプル５１のｐＨ値がｐＨコ
ントロール部５４によって制御されるように構成された
ｐＨコントロールシステムに適用した場合である。この
場合には、１点目の校正を通常のように行なった後、図
６（Ａ）に示すように、スイッチ４４をオンして比較電
極１０とｐＨ電極３０を短絡し、２点目の校正を行な
う。勿論、比較電極１０にはｐＨ既知のサンプル５１が
供給される。次に、測定時には、図６（Ｂ）に示すよう
に、スイッチ４４をオフにし、ｐＨコントロール部５４
によってｐＨ値が制御されたサンプル５１′をｐＨ電極
３０に供給し、液絡部５３を介して検出された電位を測
定処理回路４１に送り、制御されたサンプル５１′のｐ
Ｈ値を測定すれば良い。FIG. 6 is a schematic diagram showing the configuration of a fourth embodiment of the present invention.
The pH value of the reference electrode 1 is known, and this sample 51 with a known pH is used as the internal liquid 13 of the reference electrode 10.
0 and pH electrodes 30 are arranged via a liquid junction 53, and p
This is a case where the present invention is applied to a pH control system configured so that the pH value of a sample 51 supplied to the H electrode 30 is controlled by a pH control unit 54. In this case, after the first calibration is performed as usual, the switch 44 is turned on to short-circuit the comparison electrode 10 and the pH electrode 30 as shown in FIG. Perform calibration. Of course, the reference electrode 10 is supplied with a sample 51 whose pH is known. Next, at the time of measurement, as shown in FIG. 6B, the switch 44 is turned off and the pH control unit 54 is turned off.
The sample 51 ′ whose pH value has been controlled is supplied to the pH electrode 30, the potential detected via the liquid junction 53 is sent to the measurement processing circuit 41, and the p of the controlled sample 51 ′ is adjusted.
The H value may be measured.
【００３４】本実施例においても、上記実施例と同様の
作用効果が得られることは明白であるので、その説明を
省略する。In this embodiment, it is apparent that the same operation and effect as those of the above embodiment can be obtained, and the description thereof will be omitted.
【００３５】上記各実施例では金属酸化物として酸化イ
リジウムを使用したが、類似する性質の他の金属酸化物
の場合にも上記実施例と同様の作用効果が期待できる。
また、金、銀、白金などの金属をｐＨ感応膜とするｐＨ
電極に対しても上述した本発明は適用でき、同様の作用
効果が期待できる。In each of the above embodiments, iridium oxide is used as the metal oxide. However, the same operation and effect as in the above embodiments can be expected in the case of other metal oxides having similar properties.
In addition, a metal such as gold, silver, or platinum is used as a pH-sensitive film.
The present invention described above can be applied to an electrode, and the same operation and effect can be expected.
【００３６】[0036]
【発明の効果】以上の説明で明白なように、本発明によ
れば、電極電位の変動した金属酸化物又は金属をｐＨ感
応膜とするｐＨ電極と、このｐＨ電極のｐＨ感応膜と同
じ金属酸化物又は金属を内極とした比較電極とを互いに
電気的に短絡させた状態で、比較電極の内部液と同じｐ
Ｈ一定の溶液に浸漬するようにしたので、ｐＨ電極の変
動した電極電位を、たとえ大幅に変動していても、短時
間でほぼ元の電位状態に復帰させ、安定化させることが
できる。従って、メータを比較電極の内部液のｐＨ値に
合わせることによって１点目の校正が不要になるから、
直ちに２点目の校正操作が行なえ、校正操作が簡単化さ
れ、短時間で行なえる。特に、精度をさほど必要とせ
ず、１点校正だけで十分な場合には、２点目の校正をす
る必要がないので、実質的に校正操作が不必要になる
し、また、校正液が内部液１種類だけで済む。さらに、
ｐＨ電極の電極電位が酸化剤、還元剤などにより大幅に
変動した場合でも、その電極電位が短時間で復帰し、安
定化されるため、常時校正が可能になる等の多くの顕著
な効果がある。As is apparent from the above description, according to the present invention, a pH electrode using a metal oxide or a metal whose electrode potential fluctuates as a pH-sensitive film, the same metal as the pH-sensitive film of the pH electrode, In a state in which the reference electrode having an oxide or metal as the inner electrode is electrically short-circuited to each other, the same p as the internal liquid of the reference electrode is used.
Since the electrode is immersed in a solution having a constant H, the fluctuating electrode potential of the pH electrode can be returned to the original potential state in a short time, even if it fluctuates greatly, and can be stabilized. Therefore, adjusting the meter to the pH value of the internal liquid of the reference electrode eliminates the need for the first calibration.
The second calibration operation can be performed immediately, the calibration operation is simplified, and the calibration can be performed in a short time. In particular, when the accuracy is not so much required and only one-point calibration is sufficient, there is no need to perform the second point calibration, which substantially eliminates the need for the calibration operation. Only one type of liquid is required. further,
Even when the electrode potential of the pH electrode fluctuates significantly due to an oxidizing agent, a reducing agent, etc., the electrode potential recovers in a short time and is stabilized, so that many remarkable effects such as constant calibration can be achieved. is there.
【図１】本発明によるｐＨ測定装置の第１の実施例を示
す概略構成図である。FIG. 1 is a schematic configuration diagram showing a first embodiment of a pH measuring device according to the present invention.
【図２】図１のｐＨ測定装置で使用された比較電極の一
例を拡大して示す概略構成図である。FIG. 2 is a schematic configuration diagram showing, on an enlarged scale, an example of a comparative electrode used in the pH measuring device of FIG.
【図３】図１のｐＨ測定装置で使用されたｐＨ電極の一
例を拡大して示す概略構成図である。FIG. 3 is a schematic configuration diagram showing, on an enlarged scale, an example of a pH electrode used in the pH measurement device of FIG.
【図４】本発明によるｐＨ測定装置の第２の実施例を示
す概略構成図である。FIG. 4 is a schematic configuration diagram showing a pH measuring apparatus according to a second embodiment of the present invention.
【図５】本発明によるｐＨ測定装置の第３の実施例を示
す概略構成図である。FIG. 5 is a schematic configuration diagram showing a third embodiment of the pH measuring device according to the present invention.
【図６】本発明によるｐＨ測定装置の第４の実施例を示
す概略構成図である。FIG. 6 is a schematic configuration diagram showing a fourth embodiment of the pH measuring device according to the present invention.
１ アダプタ ２ ｐＨ端子 ３ 比較端子 ４ スイッチ １０ 比較電極 １３ 比較電極の内部液 １４ 比較電極の内極 １５ 比較電極の内部液と同一のｐＨ一定
の溶液 ２１ 電極支持体 ２２ 酸化イリジウム膜 ２３ リード線 ３０ ｐＨ電極 ３１ リード線 ３２ 電極支持体 ３３ 酸化イリジウムのｐＨ感応膜 ４０ フロー系 ４１ 測定処理回路 ４２ ｐＨ端子 ４３ 比較端子 ４４ スイッチ ４６ 比較電極の内部液と同一のｐＨ一定
の溶液 ５１ ｐＨ値が既知のサンプル ５１′ ｐＨ値が制御されたサンプル ５２ ｐＨ制御用ノズル ５３ 液絡部 ５４ ｐＨコントロール部DESCRIPTION OF SYMBOLS 1 Adapter 2 pH terminal 3 Comparative terminal 4 Switch 10 Comparative electrode 13 Internal liquid of comparative electrode 14 Inner electrode of comparative electrode 15 Solution with constant pH same as internal liquid of comparative electrode 21 Electrode support 22 Iridium oxide film 23 Lead wire 30 pH electrode 31 Lead wire 32 Electrode support 33 pH sensitive film of iridium oxide 40 Flow system 41 Measurement processing circuit 42 pH terminal 43 Comparison terminal 44 Switch 46 The same constant solution as the internal solution of the comparison electrode 51 The pH value is known Sample 51 'Sample whose pH value is controlled 52 Nozzle for pH control 53 Liquid junction 54 pH control
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金野 裕子 埼玉県狭山市大字北入曽613番地 東亜 電波工業株式会社 狭山工場内 (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 27/416 G01N 27/26 381 G01N 27/30 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuko Konno 613 Kitairiso, Sayama-shi, Saitama Toa Denpa Kogyo Co., Ltd. Sayama Plant (58) Field surveyed (Int. Cl. 7 , DB name) G01N 27 / 416 G01N 27/26 381 G01N 27/30
Claims (6)
ｐＨ電極と、該ｐＨ電極のｐＨ感応膜と同じ金属酸化物
又は金属を内極として使用する比較電極と、前記ｐＨ電
極が接続されるｐＨ端子及び前記比較電極が接続される
比較端子を備え、これら電極によって検出された電位か
らｐＨ値を計測し、そのｐＨ値を指示する測定・指示部
とを具備するｐＨ測定装置において、前記ｐＨ電極及び
比較電極を収納する収納部を有し、該収納部内に前記比
較電極の内部液と同一のｐＨ一定の溶液を入れて収納し
た両電極を該溶液に浸漬し、かつこれら電極を互いに電
気的に短絡させて前記ｐＨ電極の電極電位を安定化させ
る手段を設けたことを特徴とするｐＨ測定装置。1. A pH electrode comprising a metal oxide or a metal as a pH-sensitive film, a reference electrode using the same metal oxide or metal as the pH-sensitive film of the pH electrode as an inner electrode, and the pH electrode connected to the pH electrode. A pH terminal having a pH terminal and a comparison terminal to which the comparison electrode is connected, measuring a pH value from a potential detected by these electrodes, and a measurement / instruction unit for indicating the pH value. A storage portion for storing the pH electrode and the reference electrode is provided, and a solution having the same pH as the internal solution of the comparison electrode is placed in the storage portion, and both the stored electrodes are immersed in the solution, and the electrodes are mutually put together. A pH measuring device, comprising means for stabilizing the electrode potential of the pH electrode by electrically short-circuiting.
Ｓｎ、Ｒｈ、Ｔａ、Ｏｓ、Ｒｕ、Ｗ、Ｔｉから選ばれた
金属の酸化物であることを特徴とする請求項１のｐＨ測
定装置。2. The method according to claim 1, wherein the metal oxide is Ir, Pd, Pt,
The pH measurement device according to claim 1, wherein the pH measurement device is an oxide of a metal selected from Sn, Rh, Ta, Os, Ru, W, and Ti.
ことを特徴とする請求項１のｐＨ測定装置。3. The pH measuring device according to claim 1, wherein said metal oxide is iridium oxide.
ｐＨ電極と、該ｐＨ電極のｐＨ感応膜と同じ金属酸化物
又は金属を内極として使用する比較電極とを、互いに電
気的に短絡させた状態で、前記比較電極の内部液と同一
のｐＨ一定の溶液中に浸漬し、装置本体のｐＨ端子と比
較端子とを短絡させてｐＨ表示値を前記比較電極の内部
液のｐＨ値に合わせることを特徴とするｐＨ測定装置の
校正方法。4. An electrical short circuit between a pH electrode using a metal oxide or metal as a pH sensitive film and a reference electrode using the same metal oxide or metal as the pH sensitive film of the pH electrode as an inner electrode. In this state, the electrode is immersed in a solution having the same pH as the internal liquid of the reference electrode, and the pH terminal of the apparatus body and the comparison terminal are short-circuited to change the pH display value to the pH value of the internal liquid of the reference electrode. A method for calibrating a pH measuring device, characterized by matching.
Ｓｎ、Ｒｈ、Ｔａ、Ｏｓ、Ｒｕ、Ｗ、Ｔｉから選ばれた
金属の酸化物であることを特徴とする請求項４の校正方
法。5. The method according to claim 1, wherein the metal oxide is Ir, Pd, Pt,
The calibration method according to claim 4, wherein the metal oxide is a metal oxide selected from the group consisting of Sn, Rh, Ta, Os, Ru, W, and Ti.
ことを特徴とする請求項４の校正方法。6. The calibration method according to claim 4, wherein said metal oxide is iridium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03867592A JP3175022B2 (en) | 1992-01-29 | 1992-01-29 | pH measuring device and its calibration method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03867592A JP3175022B2 (en) | 1992-01-29 | 1992-01-29 | pH measuring device and its calibration method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05203616A JPH05203616A (en) | 1993-08-10 |
| JP3175022B2 true JP3175022B2 (en) | 2001-06-11 |
Family
ID=12531854
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|---|---|---|---|
| JP03867592A Expired - Fee Related JP3175022B2 (en) | 1992-01-29 | 1992-01-29 | pH measuring device and its calibration method |
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| JP4824489B2 (en) * | 2006-07-03 | 2011-11-30 | 株式会社堀場製作所 | Reference electrode, ion concentration measuring device using the reference electrode, reference electrode internal solution, method for adjusting pH of reference electrode internal solution, and salt bridge |
| JP4936536B2 (en) * | 2006-07-13 | 2012-05-23 | 国立大学法人富山大学 | Quantitative and qualitative analysis methods |
| US9128045B2 (en) | 2007-04-12 | 2015-09-08 | Mocon, Inc. | Electrochemical sensor with zero calibration feature and method of calibrating |
| CN114689669A (en) * | 2012-03-26 | 2022-07-01 | 株式会社堀场制作所 | Comparative electrode and electrochemical measuring device |
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1992
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| Publication number | Publication date |
|---|---|
| JPH05203616A (en) | 1993-08-10 |
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