JPH037266B2 - - Google Patents
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- Publication number
- JPH037266B2 JPH037266B2 JP57177274A JP17727482A JPH037266B2 JP H037266 B2 JPH037266 B2 JP H037266B2 JP 57177274 A JP57177274 A JP 57177274A JP 17727482 A JP17727482 A JP 17727482A JP H037266 B2 JPH037266 B2 JP H037266B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- sample liquid
- hole
- predetermined
- sample
- 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 - Lifetime
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【発明の詳細な説明】
本発明は、所定の流量で連続的に供給されるサ
ンプル液のPHを測定するPH測定装置に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a PH measuring device that measures the PH of a sample liquid that is continuously supplied at a predetermined flow rate.
第１図は、このようなPH測定装置の従来例の要
部構成説明図であり、図中、１，２は上記サンプ
ル液３を装置内の所定槽に連続的に供給する導入
口および導出口、４は感応部等の所定部分が上記
サンプル液中に浸漬されてなるガラス電極、５は
先端に設けられた例えばセラミツクでなる液絡部
６が上記所定槽と連通する奥まつた場所に設けら
れた穴部７内に収容されてなる比較電極、８は穴
部７内の液体と上記サンプル液３との境界面であ
る。第１図において、上記サンプル液３は太線矢
印で示す如く、導入口１から導入され上記装置内
所定槽を充たしたのち溢流となつて導出口２から
排出される。また、上記液絡部６から上記穴部７
へ例えばKClでなる内部液が約0.3〜3.0ml／day
の割合で浸透して流出され、上記ガラス電極４と
比較電極５によつて上記サンプル液のPHが測定さ
れるようになつている。更に、上記内部液は上記
穴部７内を充たしてのち、サンプル液が流れる上
記所定槽内に流れ込み、該サンプル液と共に上述
のようにして導出口２から排出されるようにな
る。 FIG. 1 is an explanatory diagram of the main part configuration of a conventional example of such a PH measuring device. In the figure, 1 and 2 are an inlet and an inlet for continuously supplying the sample liquid 3 to a predetermined tank in the device. An outlet 4 is a glass electrode with a predetermined part such as a sensitive part immersed in the sample liquid, and 5 is a recessed place where a liquid junction part 6 made of ceramic, for example, provided at the tip communicates with the predetermined tank. A comparison electrode 8 accommodated in the provided hole 7 is the interface between the liquid in the hole 7 and the sample liquid 3. In FIG. 1, the sample liquid 3 is introduced from the inlet 1 as indicated by the thick arrow, fills a predetermined tank in the apparatus, and then is discharged from the outlet 2 as an overflow. Also, from the liquid junction 6 to the hole 7
For example, the internal liquid consisting of KCl is about 0.3 to 3.0 ml/day.
The pH of the sample liquid is measured by the glass electrode 4 and the comparison electrode 5. Further, after the internal liquid fills the hole 7, it flows into the predetermined tank through which the sample liquid flows, and is discharged from the outlet 2 together with the sample liquid as described above.
然し乍ら、上記従来例においては、サンプル液
が流れる上記所定槽と内部液が充たされる上記穴
部７の境界面８でサンプル液と内部液が接触する
ため、該境界面８で乱流が生じ流動電位が発生し
易いという欠点があつた。第２図は、上記従来例
においてサンプル液に低電導度である純水をもち
い、該流量を変化させながらサンプル液のPHを測
定した結果を示すPH測定図であり、上述の流動電
位が大きなハンチングとなつて明らかに表われて
いる。しかも、該ハンチング現象は、測定時間の
経過とともに増大する傾向を示し、PH測定上早急
な解決が強く望まれていた。 However, in the above-mentioned conventional example, since the sample liquid and the internal liquid come into contact at the boundary surface 8 between the predetermined tank through which the sample liquid flows and the hole section 7 filled with the internal liquid, turbulent flow occurs at the boundary surface 8, causing a flow. The drawback was that potential was easily generated. Figure 2 is a PH measurement diagram showing the results of measuring the PH of the sample liquid while changing the flow rate using pure water with low conductivity as the sample liquid in the conventional example. This clearly appears as hunting. Furthermore, the hunting phenomenon tends to increase with the passage of measurement time, and an immediate solution for pH measurement has been strongly desired.
本発明は、かかる状況に鑑みてなされたもので
あり、その目的は、上記欠点が除去され上述のよ
うなハンチング現象が極力生じないようなPH測定
装置を提供することにある。 The present invention has been made in view of this situation, and its purpose is to provide a PH measuring device that eliminates the above-mentioned drawbacks and prevents the above-mentioned hunting phenomenon as much as possible.
本発明の特徴は、所定の流量で連続的に供給さ
れるサンプル液のPHを測定するPH測定装置におい
て、上記サンプル液の流速の影響を受けない所定
の穴部内に比較電極の液絡部を収容すると共に、
該穴部の側壁所定部分に開口した小穴を設け該小
穴から上記穴部内の液体を導いて排出するように
構成したことにある。 A feature of the present invention is that in a PH measurement device that measures the PH of a sample liquid that is continuously supplied at a predetermined flow rate, a liquid junction portion of a reference electrode is placed in a predetermined hole portion that is not affected by the flow rate of the sample liquid. Along with accommodating
A small hole is provided in a predetermined portion of the side wall of the hole, and the liquid in the hole is guided and discharged through the small hole.
以下、本発明について図を用いて詳細に説明す
る。第３図は本発明実施例の要部構成説明図であ
り、図中、第１図と同一記号は同一意味をもたせ
て使用しここでの重複説明は省略する。また、９
はガラス電極４の感応部との距離が大きく保たれ
た液絡部１０を有する全長の長い比較電極、１１
はガラス電極４および比較電極９の夫々所定部分
を収納してなるボデイ、１２は所定の流量で連続
的に供給されるサンプル液３が流れる装置内所定
槽と連通され且つ奥行きが深く形成されてなる穴
部、１３は穴部１２の側壁所定部分に開口した第
１の小穴１４および該小穴１４と連通しサンプル
液導出口２に開口する第２の小穴１５を有すると
共に保守時に装置から取りはずして内部の清掃等
が可能な様に（例えばＯ−リングａ等を介し装置
にネジ結合で着設されると共に第１小穴１４と対
向する位置に盲栓ｂ等が設けられている）構成さ
れてなる内部液排出管である。第３図において、
上記サンプル液３は太線矢印で示す如く、導入口
１から導入され上記装置内所定槽を充たしたのち
溢流となつて導出口から排出される。また、例え
ばKClでなる内部液は、第３図の細線矢印で示す
如く、比較電極９内に供給された液絡部１０から
浸透して上記穴部１２へ流出し、その後、第１お
よび第２の小穴１４，１５を経てサンプル液と共
に導出口２から排出される。ところで、ガラス電
極４と液絡部１０の距離は、ガラス電極４→穴部
１６→液絡部１０からなる第１経路l1よりもガラ
ス電極４→装置内所定槽→第２小穴１５→第１小
穴１４→液絡部１０からなる第２経路l2の方が長
い。また、第１経路l1はサンプル液で殆んど覆わ
れているが、第２経路l2はサンプル液で覆われて
いる部分が少ない。従つて、ガラス電極４と液絡
部１０との間の電気抵抗は、上記サンプル液の電
導液が小さいことと相まち、上記第１経路l1より
も上記第２経路l2の方が極めて小さくなる。因み
に、第１および第２経路l1，l2における上記電気
抵抗を夫々R1，R2とし、該経路l1，l2において生
ずる波動電位を夫々VN1，VN2とすると、第５図
に示す等価回路と下式(1)が成立する。 Hereinafter, the present invention will be explained in detail using figures. FIG. 3 is an explanatory diagram of the main part configuration of an embodiment of the present invention. In the figure, the same symbols as in FIG. 1 are used with the same meanings, and redundant explanation will be omitted here. Also, 9
11 is a comparative electrode having a long overall length and having a liquid junction part 10 that is kept at a large distance from the sensitive part of the glass electrode 4;
12 is a body that houses predetermined portions of the glass electrode 4 and the comparison electrode 9, and 12 is formed to be deep and communicate with a predetermined tank in the device through which the sample liquid 3 is continuously supplied at a predetermined flow rate. The hole section 13 has a first small hole 14 opened in a predetermined part of the side wall of the hole section 12, and a second small hole 15 that communicates with the small hole 14 and opens to the sample liquid outlet 2, and can be removed from the apparatus during maintenance. It is configured so that the inside can be cleaned (for example, it is screwed onto the device via an O-ring a, etc., and a blind plug b, etc. is provided at a position facing the first small hole 14). This is an internal liquid discharge pipe. In Figure 3,
The sample liquid 3 is introduced from the inlet 1 as indicated by the thick arrow, fills a predetermined tank in the apparatus, and then becomes an overflow and is discharged from the outlet. Further, as shown by the thin arrow in FIG. 3, the internal liquid made of, for example, KCl permeates through the liquid junction 10 supplied into the reference electrode 9 and flows out into the hole 12, and then flows into the first and second holes 12. It is discharged from the outlet 2 together with the sample liquid through the small holes 14 and 15 of 2. By the way, the distance between the glass electrode 4 and the liquid junction 10 is longer than the first path l1 consisting of the glass electrode 4 → hole 16 → liquid junction 10. The second path l2 consisting of the first small hole 14 and the liquid junction 10 is longer. Furthermore, the first route l1 is mostly covered with the sample liquid, but the second route l2 is covered with a small portion of the sample liquid. Therefore, the electrical resistance between the glass electrode 4 and the liquid junction 10 is significantly higher in the second route l2 than in the first route l1, due to the fact that the conductive liquid in the sample liquid is small . becomes smaller. Incidentally, if the electrical resistances in the first and second paths l 1 and l 2 are respectively R 1 and R 2 and the wave potentials generated in the paths l 1 and l 2 are respectively V N1 and V N2 , then FIG. The equivalent circuit shown in and the following equation (1) hold true.
VN＝R1／R1＋R2xVN2＋R2／R1＋R2xVN1
＝R1／R2／R1／R2＋１xVN2＋１／R1／R2＋１xVN1 (1)
但し、VN：ガラス電極４と比較電極９に加え
られる流動電位
上記第(1)式において、R2≫R1であるからVN≒
VN1となる。また、ガラス上記内部液は、上記穴
部１２内において第１小穴１４の位置と対応する
境界面１６で上記サンプル液と接触し、該境界面
１６が穴部１２の内部に存することから、上記サ
ンプル液の流れの影響を受けない。従つて、上記
(1)式でVN1≒０が成立して結局VN≒０となる。よ
つて、第３図の上記装置内所定槽におけるサンプ
ル液３の流速が変化しても、流動電位は殆んど生
じない。尚、第１小穴１４や第２小穴１５等に目
詰りが生じたりして故障がおきたときは、上記サ
ンプル液３の流れを止めたのち、内部液排出管１
３を装置から取りはずして点検・修理が行なわれ
る。V N = R 1 /R 1 +R 2 xV N2 +R 2 /R 1 +R 2 xV N1 = R 1 /R 2 /R 1 /R 2 +1xV N2 +1/R 1 /R 2 +1xV N1 (1) However, V N : Flowing potential applied to the glass electrode 4 and the comparison electrode 9 In the above equation (1), since R 2 ≫ R 1 , V N ≒
V N1 . Further, the internal liquid of the glass comes into contact with the sample liquid at the boundary surface 16 corresponding to the position of the first small hole 14 within the hole section 12, and since the boundary surface 16 exists inside the hole section 12, the above-mentioned Not affected by sample liquid flow. Therefore, the above
In equation (1), V N1 ≒0 holds true, and V N ≒0 after all. Therefore, even if the flow rate of the sample liquid 3 in the predetermined tank in the apparatus shown in FIG. 3 changes, almost no streaming potential is generated. If a malfunction occurs due to clogging of the first small hole 14, second small hole 15, etc., stop the flow of the sample liquid 3, and then open the internal liquid discharge pipe 1.
3 is removed from the device for inspection and repair.
第４図は、上述の本発明実施例を用いて第２図
の場合と同一条件で上記サンプル液３のPHを測定
した結果を示すPH測定図であり、第２図と比較す
れば明らかなように前記ハンチングが消失してい
る。 FIG. 4 is a PH measurement diagram showing the results of measuring the PH of the sample liquid 3 using the above-described embodiment of the present invention under the same conditions as in FIG. The hunting has disappeared.
以上、詳しく説明したような本発明の実施例に
よれば、液絡部１０から浸透して流出した内部液
がサンプル液３の流速変化を受けない場所で該サ
ンプル液と接触するような構成であるため、前記
従来例のような流動電位に基ずくハンチングが生
じないという利点がある。また、上記内部液排出
管１３を装置から容易に着脱できるような構成で
あるため、目詰り等の故障が生じた場合も点検修
理が迅速かつ容易にできるという利点もある。 According to the embodiment of the present invention as described in detail above, the internal liquid that has permeated and flowed out from the liquid junction 10 is configured to come into contact with the sample liquid 3 at a location where the flow velocity of the sample liquid 3 is not affected. Therefore, there is an advantage that hunting based on the flowing potential does not occur as in the conventional example. Further, since the internal liquid discharge pipe 13 is configured to be easily attached and detached from the apparatus, there is an advantage that even if a failure such as clogging occurs, inspection and repair can be performed quickly and easily.
第１図は従来のPH測定装置の要部構成説明図、
第２図は従来例を用いたときのPH測定図、第３図
は本発明実施例の要部構成説明図、第４図は本発
明実施例を用いたときのPH測定図、第５図は第３
図の等価回路図である。
１，２……サンプル液導出入口、３……サンプ
ル液、４……ガラス電極、５，９……比較電極、
６，１０……液絡部、７，１２……穴部、８，１
６……境界面、１３……内部液排出管、１４，１
５……小穴。
Figure 1 is an explanatory diagram of the main part configuration of a conventional PH measuring device.
Fig. 2 is a PH measurement diagram when using the conventional example, Fig. 3 is an explanatory diagram of the main part configuration of the embodiment of the present invention, Fig. 4 is a PH measurement diagram when using the embodiment of the present invention, and Fig. 5 is the third
FIG. 2 is an equivalent circuit diagram of FIG. 1, 2... Sample liquid inlet/outlet, 3... Sample liquid, 4... Glass electrode, 5, 9... Reference electrode,
6,10...liquid junction, 7,12...hole, 8,1
6...Boundary surface, 13...Internal liquid discharge pipe, 14,1
5...Small hole.
Claims (1)
のPHを測定するPH測定装置において、前記サンプ
ル液が導入され溢流となつて排出されると共に該
サンプル液にガラス電極が浸漬されてなる所定形
状の槽と、該槽と連通され内部所定部分に比較電
極の液絡部が収容されるように奥行き深く形成さ
れてなる穴部と、該穴部の側壁所定部分に開口し
た第１の小穴を有し該小穴から導入される前記穴
部内の液体を前記サンプル排出液と合流させて排
出する内部液排出管とを具備し、前記穴部内の所
定部分で前記液絡部から浸透流出する内部液と前
記サンプル液が接触するように構成したことを特
徴とするPH測定装置。 ２ 前記内部液排出管は、装置へ着脱自在に構成
されてなる特許請求範囲第１項記載のPH測定装
置。[Scope of Claims] 1. In a PH measuring device that measures the pH of a sample liquid that is continuously supplied at a predetermined flow rate, the sample liquid is introduced and discharged as an overflow, and a glass electrode is connected to the sample liquid. a tank having a predetermined shape in which is immersed, a hole communicating with the tank and formed deep so that the liquid junction of the reference electrode is accommodated in a predetermined part of the inside, and a predetermined part of the side wall of the hole. an internal liquid discharge pipe that has an open first small hole and discharges the liquid introduced from the small hole by merging with the sample discharge liquid, and the liquid junction is formed at a predetermined portion in the hole. 1. A PH measurement device characterized in that the sample liquid is configured so that the internal liquid that permeates and flows out from the part comes into contact with the sample liquid. 2. The PH measuring device according to claim 1, wherein the internal liquid discharge pipe is configured to be detachable from the device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57177274A JPS5965756A (en) | 1982-10-08 | 1982-10-08 | Ph measuring apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57177274A JPS5965756A (en) | 1982-10-08 | 1982-10-08 | Ph measuring apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5965756A JPS5965756A (en) | 1984-04-14 |
| JPH037266B2 true JPH037266B2 (en) | 1991-02-01 |
Family
ID=16028181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57177274A Granted JPS5965756A (en) | 1982-10-08 | 1982-10-08 | Ph measuring apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5965756A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8021529B2 (en) | 2005-04-20 | 2011-09-20 | Thermo Orion, Inc. | Ion measurement/calibration cell |
| JP6337448B2 (en) * | 2013-11-20 | 2018-06-06 | 東亜ディーケーケー株式会社 | Flow-type electrode device |
-
1982
- 1982-10-08 JP JP57177274A patent/JPS5965756A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5965756A (en) | 1984-04-14 |
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