JPH03216545A - Flow through type electrode apparatus - Google Patents
Flow through type electrode apparatusInfo
- Publication number
- JPH03216545A JPH03216545A JP2012079A JP1207990A JPH03216545A JP H03216545 A JPH03216545 A JP H03216545A JP 2012079 A JP2012079 A JP 2012079A JP 1207990 A JP1207990 A JP 1207990A JP H03216545 A JPH03216545 A JP H03216545A
- Authority
- JP
- Japan
- Prior art keywords
- comparison liquid
- water
- reverse osmosis
- osmosis membrane
- comparison
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 24
- 238000005259 measurement Methods 0.000 claims abstract description 16
- 238000012360 testing method Methods 0.000 claims description 32
- 238000004891 communication Methods 0.000 abstract description 6
- 238000011109 contamination Methods 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 5
- 239000011521 glass Substances 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
- 238000001139 pH measurement Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、測定セル内に電極を組み込んだフロースルー
型電極装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flow-through electrode device incorporating an electrode within a measuring cell.
フロースルー型電極装置は各種のイオン濃度分析計等に
利用され、プラスチック等からなる測定セル内に形成し
た検水流路内に作用電極と比較電極の両方を配置した構
造になっている。Flow-through electrode devices are used in various ion concentration analyzers and have a structure in which both a working electrode and a reference electrode are placed in a test water channel formed in a measuring cell made of plastic or the like.
比較電極は内部に比較液と内極を備え、多孔質セラミッ
クス等からなる液絡部を介して検水と接するようになっ
ている。作用電極は比較電極と対をなして使用される測
定用電極を意味し、例えば１）Ｈ７ＷＪ定に用いるガラ
ス電極や電解質溶液の濃度分析に用いる各種のイオン電
極等がある。The reference electrode has a reference liquid and an inner electrode inside, and is brought into contact with the sample water through a liquid junction made of porous ceramics or the like. The working electrode refers to a measuring electrode used in pair with a reference electrode, and includes, for example, 1) a glass electrode used in H7WJ determination and various ion electrodes used in concentration analysis of electrolyte solutions.
しかし、従来のフロースルー型電極装置においては、比
較電極の液絡部から検水中に拡散する比較液の量が比較
的多く、例えばｐＨの連続測定ではＭＣＩに換算して１
日約０．３ｇに達する。この消耗分を補なうために、比
較電極内部に頻繁に比較液を補充する必要があるなど、
保守が面倒であった。However, in conventional flow-through electrode devices, the amount of reference liquid that diffuses into the sample water from the liquid junction of the reference electrode is relatively large.
It reaches about 0.3g per day. In order to compensate for this consumption, it is necessary to frequently replenish the reference liquid inside the reference electrode.
Maintenance was troublesome.
又、比較電極の液絡部から検水中に浸出する比較液によ
る汚染を無くすため検水流路の上流に作用電極を及び下
流に比較電極を配置し、検水が最初に作用電極の感応部
に接した後比較電極を通って排出されるように構成した
フロースルー型電極装置も知られている。しかし、この
構成により作用電極感応部の汚染が多少抑えられたとし
ても、前記した比較液の大量消費と、その補充を要する
点については何等解決されていなかった。In addition, in order to eliminate contamination due to the comparison liquid leaking into the test water from the liquid junction of the reference electrode, the working electrode is placed upstream of the test water flow path, and the reference electrode is placed downstream, so that the test water first reaches the sensitive part of the working electrode. A flow-through type electrode device is also known, which is configured to be discharged through a reference electrode after contacting the electrode. However, even if this configuration suppresses contamination of the working electrode sensitive part to some extent, it does not solve the above-mentioned problem of large consumption of the comparison liquid and the need for its replenishment.
しかも、上記の如く構成したフロースルー型電極装置で
あっても、純水のようにｐＨ緩衝性が全くなく極めて電
導度が低い、例えば０．１μｓ／ｃｍ未満程度の検水の
ｐＨ測定では、流動電位の変動により安定な測定が出来
なかった。その一例として、電導度が０．０６５μ３７
ｃｍの純水のｐＨを流量を変えながら測定した結果を第
４図に示したが、検水の流量が増すにつれｐＨ指示値の
変動が次第に大きくなることが判る。Moreover, even with the flow-through type electrode device configured as described above, it is difficult to measure the pH of sample water, which has no pH buffering properties and extremely low conductivity, such as less than 0.1 μs/cm, like pure water. Stable measurements were not possible due to fluctuations in streaming potential. As an example, the conductivity is 0.065μ37
Figure 4 shows the results of measuring the pH of pure water of cm while changing the flow rate, and it can be seen that as the flow rate of the test water increases, the fluctuation in the pH indication value gradually increases.
本発明はかかる従来の事情に鑑み、従来よりも比較液の
検水中への拡散が少なく、従って保守が簡単であると共
に、流動電位の変動を抑え寸検水流量に拘らず安定な測
定が可能な、フロースルー型電極装置を提供することを
目的とする。In view of such conventional circumstances, the present invention allows for less diffusion of the comparison liquid into the test water than in the past, which simplifies maintenance, suppresses fluctuations in streaming potential, and enables stable measurement regardless of the flow rate of the test water. The present invention aims to provide a flow-through type electrode device.
上記の目的を達成するため、本発明のフロースルー型電
極装置では、測定セルと、測定セル内に形成された検水
流路部及び比較液貯溜部と、比較液貯溜部内に比較液に
浸漬して取付けた比較電極と、比較液貯溜部内の比較液
と検水流路部を流れる検水とを区画するように比較液貯
溜部と検水流路部の間に設けた逆浸透膜とを備えたこと
を特徴とする。In order to achieve the above object, the flow-through type electrode device of the present invention includes a measurement cell, a test water flow path portion and a comparison liquid storage portion formed in the measurement cell, and a comparison liquid storage portion immersed in the comparison liquid. and a reverse osmosis membrane provided between the comparison liquid reservoir and the test water flow path so as to separate the comparison liquid in the reference liquid storage and the test water flowing through the test water flow path. It is characterized by
本発明のフロースルー型電極装置で検水と比較液とを隔
てているのは逆浸透膜であるから、ＫＯ！溶液などから
なる比較液は逆浸透膜を通って検水中に拡散し難く１従
って比較液の拡散による消耗を従来の半分以下に抑え、
又作用電極の汚染を著し〈低減させることが出来る。In the flow-through electrode device of the present invention, it is the reverse osmosis membrane that separates the sample water from the comparison solution, so KO! The comparison liquid, such as a solution, is difficult to diffuse into the test water through the reverse osmosis membrane.1 Therefore, the consumption of the comparison liquid due to diffusion is reduced to less than half of that of conventional methods.
In addition, contamination of the working electrode can be significantly reduced.
しかも、検水流路部に設けた作用電極の感応部に対して
、逆浸透膜を検水の流れ方向の下流又はほぼ同位置に設
ければ、検水中に僅かに拡散する比較液によって作用電
極の感応部が汚染されることが殆ど無くなる。Moreover, if a reverse osmosis membrane is installed downstream of or at approximately the same position in the flow direction of the sample water with respect to the sensitive part of the working electrode provided in the sample water flow path, the reference liquid slightly diffused in the sample water can be applied to the working electrode. The sensitive part of the sensor is almost never contaminated.
更に、本発明のフロースルー型電極装置では、検水と比
較液を区画する逆浸透膜が比較電極の液絡部の役割を果
たしている。この逆浸透膜は上記の如く比較液を殆ど拡
散させないので作用電極の感応部に２０闘程度まで接近
させて設置することが可能となる。その結果、流動電位
の変動を抑制することができ、従来は流動電位の影響が
大きかった純水のｐＨ測定においても、検水流量に拘ら
ず常に安定した測定が可能となる。Furthermore, in the flow-through type electrode device of the present invention, the reverse osmosis membrane that partitions the test water and the comparison liquid plays the role of a liquid junction of the comparison electrode. As mentioned above, this reverse osmosis membrane hardly diffuses the comparison liquid, so it can be installed as close as 20 mm to the sensitive part of the working electrode. As a result, fluctuations in the streaming potential can be suppressed, and stable measurement is always possible regardless of the sample water flow rate, even in the pH measurement of pure water, where the influence of the streaming potential was conventionally large.
本発明の一具体例であるフロースルー型のｐＨ測定装置
を第１図及び第２図により説明する。A flow-through type pH measuring device which is a specific example of the present invention will be explained with reference to FIGS. 1 and 2.
アクリル樹脂等のプラスチックからなるフロースルー型
の測定セル１には、検水流路部２と比較液貯溜部３が別
々に測定セル１の上面から下方向に穿設してある。検水
流路部２の下端には検水人口４が及び上端側には検水出
口５が夫々設けてあり、検水流路部２内にはガラス電極
６が感応部を下にして着脱可能に取付けられている。又
、比較液貯溜部３にはＫＣｌ溶液からなる比較液７が満
たしてあり、この比較液７に浸漬して通常、の比較電極
８が着脱可能に取付けられている。A flow-through type measurement cell 1 made of plastic such as acrylic resin has a test water channel section 2 and a comparison liquid storage section 3 separately drilled downward from the top surface of the measurement cell 1 . A water test volume 4 is provided at the lower end of the water test flow path section 2, and a test water outlet 5 is provided at the upper end side, and a glass electrode 6 is installed and detached within the test water flow path section 2 with the sensitive part facing down. installed. Further, the comparison liquid reservoir 3 is filled with a comparison liquid 7 made of a KCl solution, and a normal comparison electrode 8 is detachably attached to the electrode 8 immersed in the comparison liquid 7.
測定セルｌ内の検水流路部２と比較液貯溜部３との間に
は、両者間を連通ずる連通孔９がガラス電極６の感応部
より検水１１の流れの下流に形成され、この連通孔９を
閉鎖するように設けた逆浸透膜１０が検水流路部２の検
水１１と比較液貯溜部３の比較液７とを区画している。A communication hole 9 is formed between the test water flow path section 2 and the comparison liquid storage section 3 in the measurement cell 1, downstream of the flow of the test water 11 from the sensitive section of the glass electrode 6, which communicates between the two. A reverse osmosis membrane 10 provided to close the communication hole 9 separates the test water 11 in the test water channel section 2 from the comparison liquid 7 in the comparison liquid storage section 3 .
即ち、ホルダ一部１２の円筒状に形成した一端に逆浸透
膜１０を当て、その上からホルダー外筒１３をホルダ一
部１２に嵌合又は螺合することにより逆浸透膜１０を扶
持する。ホルダ一部１２は測定セル１の側面に連通孔９
と中心を一致させて形成した孔に挿入され、袋ナット１
４で測定セル１に螺合することにより固定され、ホルダ
一部１２の円筒状一端にホルダー外筒１３で保持された
逆浸透膜１０が連通孔９に嵌め込まれる。又、ホルダ一
部１２の円筒状部分には上下方向に貫通孔１６が形成し
てあり、比較電極８と逆浸透膜１０が比較液７で連通ず
るようになっている。That is, the reverse osmosis membrane 10 is supported by applying the reverse osmosis membrane 10 to one cylindrical end of the holder part 12 and fitting or screwing the holder outer cylinder 13 onto the holder part 12 from above. The holder part 12 has a communication hole 9 on the side of the measurement cell 1.
The cap nut 1 is inserted into the hole formed by aligning the center with the cap nut 1.
4, the reverse osmosis membrane 10 is fixed by screwing onto the measurement cell 1 and held by the holder outer cylinder 13 at one cylindrical end of the holder part 12, and is fitted into the communication hole 9. Further, a through hole 16 is formed in the cylindrical portion of the holder part 12 in the vertical direction, so that the comparison electrode 8 and the reverse osmosis membrane 10 communicate with each other through the comparison liquid 7.
逆浸透膜１０はボリアミド系、酢酸セルロース系などの
通常の逆浸透膜で良い。又、逆浸透膜１０の大きさ及び
取付位置や取付手段は上記の例に限宇されず、例えば検
水流路部２と比較液貯溜部３をほぼ一室に形成し、両者
を逆浸透膜で区画しても良いが、出来るだけ小面積の逆
浸透膜を着脱可能に取付けることが好ましい。The reverse osmosis membrane 10 may be a normal reverse osmosis membrane such as a polyamide-based or cellulose acetate-based membrane. Further, the size, mounting position, and mounting means of the reverse osmosis membrane 10 are not limited to the above example. For example, the test water flow path section 2 and the comparison liquid storage section 3 may be formed in approximately one chamber, and both may be connected to the reverse osmosis membrane. However, it is preferable to removably attach a reverse osmosis membrane with as small an area as possible.
更に、浸透圧により検水１１から比較液貯溜部３へ浸透
した水によって比較液貯溜部３の液量が増加してくるが
、一Ｆ側にドレイン１５を設けることにより、増加した
液はドレイン１５からオーノくフローするようになって
いる。Furthermore, the amount of liquid in the comparison liquid storage part 3 increases due to water permeating from the test water 11 to the comparison liquid storage part 3 due to osmotic pressure, but by providing a drain 15 on the 1F side, the increased liquid is drained. From 15 onwards, it starts to flow smoothly.
−ｈ記装置を用いて、電導度が０． ０６５μｓ／ｃｍ
の純水のｐ｝ｌを流量を変えながら連続測定したところ
、第３図に示す如く流量に拘らず安宇したｐＨ指示値が
得られた。この結果は、同じ純水のｐＨを従来の装置で
測定した第４図に比べて遥かに優れていることが判る。- Using the device described in h, the electrical conductivity is 0. 065μs/cm
When the p}l of pure water was continuously measured while changing the flow rate, a stable pH indication value was obtained regardless of the flow rate, as shown in Fig. 3. It can be seen that this result is far superior to that shown in FIG. 4, where the pH of the same pure water was measured using a conventional device.
又、上記本実施例の装置では、有効表面積２８間２の逆
浸透＠１０を用いた時、ｐＨの連続測定における比較液
の消耗がＫＣｌに換算して１日約０．１ｇであり、従来
の装置における１日約０．３ｇの半分以下であった。In addition, in the device of this embodiment, when using reverse osmosis @10 with an effective surface area of 28.2, the consumption of the comparison solution in continuous pH measurement is about 0.1 g per day in terms of KCl, which is compared to conventional methods. This amount was less than half of the approximately 0.3 g per day in the device.
本発明によれば、比較液と検水を逆浸透膜で液絡させて
いるので、比較液の検水中への拡散が極めて少なく又拡
散した比較液による作用電極感応部の汚染が少なくなる
ので、比較液の補充や作用電極の洗浄等の保守管理が従
来よりも遥かに簡単になる。特に、逆浸透膜を検水流路
部に設けた作用電極の感応部に対して検水の流れ方向の
下流又はほぼ同位置に設ければ、作用電極感応部の汚染
を殆ど無くすことが出来る。According to the present invention, since the comparison liquid and the test water are connected to each other by a reverse osmosis membrane, the diffusion of the comparison liquid into the test water is extremely small, and the contamination of the working electrode sensitive part by the diffused comparison liquid is reduced. , maintenance management such as replenishment of the reference liquid and cleaning of the working electrode becomes much easier than in the past. In particular, if the reverse osmosis membrane is provided downstream in the flow direction of the test water or at approximately the same position as the sensitive part of the working electrode provided in the test water flow path, contamination of the working electrode sensitive part can be almost eliminated.
又、比較液の検水中への拡散が極めて少ないので、液絡
部たる逆浸透膜と作用電極感応部を従来よりも接近させ
、流動電位の変動を抑えて安定な測定を行なうことが可
能であり、特に流動電位の影響により従来は安定した測
定が困難であった純水の−ｐＨ測定においても、検水流
量に拘らず安定な測定を行なうことが出来る。In addition, because the diffusion of the comparison liquid into the sample water is extremely small, the reverse osmosis membrane, which is the liquid junction, and the working electrode sensitive area can be brought closer together than before, making it possible to suppress fluctuations in the streaming potential and perform stable measurements. In particular, even in the -pH measurement of pure water, which has conventionally been difficult to measure stably due to the influence of streaming potential, stable measurement can be performed regardless of the sample water flow rate.
第１図は本発明のフロースルー型電極装置の一具体例を
示す一部切欠正面図であり、第２図は同装置の比較電極
側から見た一部切欠側面図である。
第３図は第１図の装置を用い流量を変えて測定した純水
のｐＨ指示値のグラフであり、第４図は従来の装置を用
いて同様に測定した純水のｐＨ指示値のグラフである。FIG. 1 is a partially cutaway front view showing a specific example of a flow-through type electrode device of the present invention, and FIG. 2 is a partially cutaway side view of the same device as seen from the reference electrode side. Figure 3 is a graph of the pH indication value of pure water measured using the apparatus shown in Figure 1 at different flow rates, and Figure 4 is a graph of the pH indication value of pure water measured in the same manner using the conventional apparatus. It is.
Claims (1)
及び比較液貯溜部と、比較液貯溜部内に比較液に浸漬し
て取付けた比較電極と、比較液貯溜部内の比較液と検水
流路部を流れる検水とを区画するように比較液貯溜部と
検水流路部の間に設けた逆浸透膜とを備えたフロースル
ー型電極装置。(1) A measurement cell, a test water flow path formed in the measurement cell, a comparison liquid storage part, a comparison electrode attached to the comparison liquid storage part by immersing it in the comparison liquid, and a comparison liquid in the comparison liquid storage part. A flow-through type electrode device comprising a reverse osmosis membrane provided between a comparison liquid reservoir and a test water flow path so as to separate the test water flowing through the test water flow path.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012079A JP2952501B2 (en) | 1990-01-22 | 1990-01-22 | Flow-through type electrode device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012079A JP2952501B2 (en) | 1990-01-22 | 1990-01-22 | Flow-through type electrode device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03216545A true JPH03216545A (en) | 1991-09-24 |
| JP2952501B2 JP2952501B2 (en) | 1999-09-27 |
Family
ID=11795580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012079A Expired - Fee Related JP2952501B2 (en) | 1990-01-22 | 1990-01-22 | Flow-through type electrode device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2952501B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007057459A (en) * | 2005-08-26 | 2007-03-08 | Kyushu Univ | Chemical sensory sensor chip |
-
1990
- 1990-01-22 JP JP2012079A patent/JP2952501B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007057459A (en) * | 2005-08-26 | 2007-03-08 | Kyushu Univ | Chemical sensory sensor chip |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2952501B2 (en) | 1999-09-27 |
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