JPH04273041A - Electrolytic flow cell using crystal vibrator - Google Patents
Electrolytic flow cell using crystal vibratorInfo
- Publication number
- JPH04273041A JPH04273041A JP5563591A JP5563591A JPH04273041A JP H04273041 A JPH04273041 A JP H04273041A JP 5563591 A JP5563591 A JP 5563591A JP 5563591 A JP5563591 A JP 5563591A JP H04273041 A JPH04273041 A JP H04273041A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- flow cell
- solution
- electrolyte
- working electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 14
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims description 23
- 239000012488 sample solution Substances 0.000 claims description 22
- 238000005259 measurement Methods 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000011002 quantification Methods 0.000 abstract 3
- 239000000470 constituent Substances 0.000 abstract 1
- 230000001850 reproductive effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 61
- 239000000126 substance Substances 0.000 description 28
- 230000010355 oscillation Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical group S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000000232 Lipid Bilayer Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Automatic Analysis And Handling Materials Therefor (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、溶液中に存在する微量
物質を定量的に分析するための装置、特に電気化学的手
段を用いて定量的に分析するための電解定量装置に関す
るものである。[Field of Industrial Application] The present invention relates to an apparatus for quantitatively analyzing trace substances present in a solution, and in particular to an electrolytic quantitative apparatus for quantitatively analyzing trace substances present in a solution. .
【０００２】0002
【従来の技術】水晶発振子は、発振子に物質が付着する
と発振周波数が変化することが見出されて分析の分野に
利用されている。気体中に存在する微量物質が発振子上
に塗布された選択的吸着剤に吸着して、その量に応じて
変化する発振子の発振周波数の変化を測定して微量物質
の吸着量を定量できることは知られている。液体中に溶
解して存在する微量物質についても同様に発振子上に吸
着し得る物質による発振子の発振周波数の変化を測定す
れば微量物質の吸着量を定量できるが、共存する物質に
よる妨害効果等の理由で個々には応用例は有るが、一般
法として確立されるには至っていない。2. Description of the Related Art Crystal oscillators have been used in the field of analysis because it has been discovered that the oscillation frequency changes when a substance adheres to the oscillator. The ability to quantify the amount of adsorbed trace substances by measuring the change in the oscillation frequency of the oscillator, which changes according to the amount of adsorbed trace substances present in the gas, on the selective adsorbent coated on the oscillator. is known. Regarding trace substances dissolved in a liquid, the amount of adsorbed trace substances can be quantified by measuring the change in the oscillation frequency of the oscillator due to the substances that can be adsorbed onto the oscillator, but the interference effect caused by coexisting substances For these reasons, although there are individual application examples, it has not yet been established as a general law.
【０００３】これに対して液体中に溶解して存在する微
量電解質物質を水晶発振子に金をメッキしてそれを作用
極として電解質物質をその上に電着させて、その量を発
振子の発振周波数の変化の測定によって定量して電解質
物質の濃度を定量することは、電解電圧を規定すれば共
存する物質による妨害効果を排除し得るので試みられて
いる。On the other hand, a small amount of electrolyte substance dissolved in a liquid is plated with gold on a crystal oscillator, and the electrolyte substance is electrodeposited on the crystal oscillator using it as a working electrode. Attempts have been made to quantify the concentration of electrolyte substances by measuring changes in the oscillation frequency, since interference effects caused by coexisting substances can be eliminated by specifying the electrolytic voltage.
【０００４】水晶発振子を用いて作成した作用極を一極
とする三極電極系で、微量に溶解している銀を溶液から
作用極に電着させて、溶液中の銀濃度を測定する方法に
ついては、野村等がＡｎａｌｙｔｉｃａ Ｃｈｉｍｉ
ｃａ Ａｃｔａ １３１巻 ９７頁 （１９８
１）に記載している。しかしながら、この従来の装置で
は、試料を含む電解質溶液は、作用極から離れた位置に
ある供給口から流入して、装置中の作用極上をその一方
の端から厚い層の層流として他の端へ流れる形で供給さ
れるため、検知されるべき物質（以下には作用物質とい
う）は作用極上に均一には分布せず、上流の部分では多
く下流では希薄になり、しかも測定条件によってその作
用物質の分布が変化する。また更に、対極が、電解質溶
液が流入する所にも、また作用極にも近接して存在する
ため、対極付近の電解質溶液の組成が測定中絶えず変動
する。かかる状況は測定中の装置を流れる電流値によく
反映され、実際この従来タイプの測定装置を用いての追
試では、電解電流が大きくバラツき、作用極の発振周波
数も不安定で作用極に電着した作用物質の再現性のよい
重量測定ができなかった。電解質試料溶液が少ない場合
、或いは試料の切り換え時の安定化時間を短縮したい等
の場合には、測定セルは小容量のものに設計されるが、
そのことも従来の装置では電解電流の不安定化を助長す
る。[0004] Using a three-electrode electrode system in which a working electrode made using a crystal oscillator serves as one pole, a trace amount of dissolved silver is electrodeposited from the solution onto the working electrode, and the silver concentration in the solution is measured. Regarding the method, Nomura et al.
ca Acta Volume 131 Page 97 (198
It is described in 1). However, in this conventional device, the electrolyte solution containing the sample enters from a supply port located remote from the working electrode and flows over the working electrode in the device from one end of the electrolyte solution to the other end in a thick layer of laminar flow. Since the substance to be detected (hereinafter referred to as the active substance) is not uniformly distributed on the active electrode, it is concentrated in the upstream area and diluted in the downstream area, and its effect varies depending on the measurement conditions. The distribution of substances changes. Furthermore, since the counter electrode is present at the point where the electrolyte solution flows and also in close proximity to the working electrode, the composition of the electrolyte solution near the counter electrode constantly changes during the measurement. This situation is well reflected in the value of the current flowing through the device being measured, and in fact, in a follow-up test using this conventional type of measuring device, the electrolytic current varied greatly, the oscillation frequency of the working electrode was unstable, and the current flowing through the working electrode was unstable. It was not possible to reproducibly measure the weight of the deposited active substance. When the amount of electrolyte sample solution is small, or when it is desired to shorten the stabilization time when switching samples, the measurement cell is designed with a small capacity.
This also contributes to the instability of the electrolytic current in conventional devices.
【０００５】[0005]
【発明が解決しようとする課題】本発明は以下に示す課
題を解決し、電解定量分析に対して、電解電流が安定し
、感度がよくかつ再現性のよい測定を可能にする電解定
量装置用電解フローセルを提供することにある。すなわ
ち、
■ 作用極で作用物質の不均一分布が起こらないこと
。
■ 対極付近で電解質溶液の組成変化が起こらないこ
と。
■ セル容量が大きくならないように工夫して、試料
の切り換え時に測定条件が安定化するのに時間がかから
ないこと。
の諸条件を満足する電解定量装置用電解フローセルを提
供することにある。[Problems to be Solved by the Invention] The present invention solves the following problems, and provides an electrolytic quantitative analysis device for electrolytic quantitative analysis that enables stable electrolytic current, high sensitivity, and highly reproducible measurement. An object of the present invention is to provide an electrolytic flow cell. That is, ■ Non-uniform distribution of the active substance at the working electrode does not occur. ■ No change in the composition of the electrolyte solution occurs near the counter electrode. ■ Take measures to prevent the cell capacity from increasing, so that it does not take long for measurement conditions to stabilize when switching samples. An object of the present invention is to provide an electrolytic flow cell for an electrolytic quantitative device that satisfies the following conditions.
【０００６】本発明はまた、一定の電位をかけた状態で
、水晶発振子上に設けられた膜等の物質に、他の物質が
吸着する挙動の測定、或いは取り込まれる量の定量によ
る膜等の物質の電荷による物性値変化の測定に利用でき
る電解フローセルを提供することにある。The present invention also relates to measuring the adsorption behavior of other substances to a substance such as a film provided on a crystal oscillator while applying a constant potential, or by quantifying the amount absorbed into the film, etc. An object of the present invention is to provide an electrolytic flow cell that can be used to measure changes in physical properties due to charge of a substance.
【０００７】[0007]
【課題を解決するための手段】上記課題は、１）微量成
分を含む電解質試料溶液を、水晶発振子を含んで構成さ
れる作用極と対極とを有する電解フローセルを通して微
量成分を電解定量する電解定量装置において、該電解フ
ローセル内の電解質溶液は一体的であるが、少なくとも
電解質試料溶液の電解定量を行っている間、流動してい
る部分と実質的に静止している部分とがあり、作用極は
流動している部分に接しており、対極は実質的に静止し
ている部分に接していることを特徴とする電解定量装置
用電解フローセルによって達成される。[Means for Solving the Problems] The above-mentioned problems are as follows: 1) An electrolytic method for electrolytically quantifying trace components by passing an electrolyte sample solution containing trace components through an electrolytic flow cell having a working electrode and a counter electrode including a crystal oscillator. In the quantitative apparatus, the electrolyte solution in the electrolytic flow cell is integral, but at least during electrolytic quantitative determination of the electrolyte sample solution, there are flowing parts and substantially stationary parts, and the electrolyte solution does not work. This is achieved by an electrolytic flow cell for an electrolytic metering device, characterized in that the electrode is in contact with a flowing part and the counter electrode is in contact with a substantially stationary part.
【０００８】また、２）測定に当たって測定用電解質試
料溶液を上記１）項に記載の電解フローセルに供給する
場合、電解フローセルに、その水晶発振子を含んで構成
される作用極の面に対して垂直に供給され、電解フロー
セル内の電解質溶液の流動している部分の容積が供給さ
れる電解質溶液の一分間当たりの供給量の１／２．５〜
１／２０倍倍の範囲であることが上記課題の達成のため
に好ましく、更にまた、３）参照電極が上記１）項また
は２）項に記載の電解フローセル中の電解質溶液と直接
電気的に導通状態にある電解質溶液中に存在して、該電
解質溶液に一定の電位をかけていることが電解電流が安
定し、感度がよくかつ再現性のよい測定を可能にする。2) When supplying the electrolyte sample solution for measurement to the electrolytic flow cell described in item 1) above, the electrolytic flow cell is provided with a surface of the working electrode including the crystal oscillator. The volume of the flowing part of the electrolyte solution in the electrolytic flow cell is 1/2.5 to 1/2.5 of the amount of electrolyte solution supplied per minute that is supplied vertically.
In order to achieve the above object, it is preferable that the range is 1/20 times, and 3) the reference electrode is directly electrically connected to the electrolyte solution in the electrolytic flow cell described in 1) or 2) above. Being present in the electrolyte solution in a conductive state and applying a constant potential to the electrolyte solution stabilizes the electrolytic current and enables measurements with good sensitivity and good reproducibility.
【０００９】また、この電解質溶液に一定の電位をかけ
ることによって、電解フローセル用の作用電極としてで
はなく、水晶発振子上に膜等の物質を塗設して、これら
膜等の物質に他の物質が吸着する挙動の測定、或いは取
り込まれる量の定量などの測定に利用できる電解フロー
セルを提供することも可能になる。[0009] Furthermore, by applying a certain potential to this electrolyte solution, a substance such as a membrane is coated on the crystal oscillator rather than as a working electrode for an electrolytic flow cell, and other substances such as the membrane are coated on the crystal oscillator. It is also possible to provide an electrolytic flow cell that can be used to measure the adsorption behavior of a substance or quantify the amount taken up.
【００１０】0010
【作用】本発明の装置が上記効果を発揮する作用を図１
を用いて説明する。ただし、ここで行う説明は本発明を
制限するものではないことは言うまでもない。図１に例
示した電解定量装置用電解フローセル１は本発明の電解
フローセルの一態様を示すものである。[Function] Figure 1 shows how the device of the present invention exhibits the above effects.
Explain using. However, it goes without saying that the description given here does not limit the present invention. The electrolytic flow cell 1 for an electrolytic quantitative device illustrated in FIG. 1 shows one embodiment of the electrolytic flow cell of the present invention.
【００１１】図１において、該電解フローセル１のセル
部２の底部には円形の金メッキした水晶発振子で構成さ
れる作用極８が、その流動する電解質溶液１３と接する
側の面をＯリング３でセル部２の底部のフランジ４に抑
え、その反対面は樹脂板５を介してゴム６でセル本体よ
りの抑え金具（図示せず）を用いて抑えることで液密に
セル部２に取付けられる。後に説明するセルの一部を構
成しているセル中央に穿孔して造られた溶液吹き出し口
７は、作用極８に向かって垂直に設けられ作用極８に接
近するに従って孔径が大きくなって、作用極８の面全体
に液を供給するようにつくられ、要すればその出口には
目皿９が取りつけられる。作用極８の形と、溶液吹き出
し口７の断面の形状は円形であるのが最も自然であるが
他の形、例えば角型であってもよく、任意の形が取り得
る。作用極８の大きさは普通直径が８ｍｍであり、その
とき溶液吹き出し口７の断面の直径は４〜５ｍｍである
ことが好ましい大きさである。作用極８と溶液吹き出し
口７との距離は例えば３ｍｍ程度、好ましくは２ｍｍ程
度と接近しているのが好ましい。In FIG. 1, a working electrode 8 consisting of a circular gold-plated crystal oscillator is located at the bottom of the cell section 2 of the electrolytic flow cell 1, and its surface in contact with the flowing electrolyte solution 13 is connected to an O-ring 3. It is fixed to the cell part 2 in a liquid-tight manner by holding it to the flange 4 at the bottom of the cell part 2, and holding the opposite side to the cell part 2 with a rubber 6 through a resin plate 5 using a holding fitting (not shown) from the cell body. It will be done. A solution outlet 7 formed by drilling in the center of the cell, which forms part of a cell to be described later, is provided perpendicularly toward the working electrode 8, and the hole diameter increases as it approaches the working electrode 8. It is made to supply liquid to the entire surface of the working electrode 8, and if necessary, a perforated plate 9 is attached to the outlet thereof. The most natural shape of the working electrode 8 and the cross-sectional shape of the solution outlet 7 is circular, but other shapes may be used, for example square, or any other shape is possible. The diameter of the working electrode 8 is normally 8 mm, and the cross-sectional diameter of the solution outlet 7 is preferably 4 to 5 mm. The distance between the working electrode 8 and the solution outlet 7 is preferably about 3 mm, preferably about 2 mm.
【００１２】この電解フローセルのセル２は、底部に既
に説明した構造の作用極８、その真上に電解質溶液或い
は電解質試料溶液をセル２に供給する溶液吹き出し口７
があり、作用極８と溶液吹き出し口７との間が作用空間
（２−ｃ）であり、前記溶液吹き出し口７を有する構造
体である円柱状ブロック１１の外周には対極１２がブロ
ックとは絶縁されて巻き付けた構造として配置されてお
り、セル２の外壁を構成するブロックの内側との間が対
極空間（２−ａ）であり、これ等によってセル２が構成
されている。この対極空間（２−ａ）はその幅は３ｍｍ
位、好ましくは２ｍｍである。ここで使用された作用極
８は厚さ０．５ｍｍ、直径１３ｍｍの水晶板に直径８ｍ
ｍの金をメッキしたものであるが、この作用極のサイズ
、形、及びメッキする金属の種類などは特に制限されず
任意のものが使用できる。また、対極１２も通常白金で
作られているが、極を構成する金属の種類、或いは対極
空間（２−ａ）に対極を設置する仕方もこの具体例に制
限されず任意のもの形式のものが使用できる。The cell 2 of this electrolytic flow cell has a working electrode 8 having the structure already explained at the bottom, and a solution outlet 7 directly above the working electrode 8 for supplying an electrolyte solution or an electrolyte sample solution to the cell 2.
There is a working space (2-c) between the working electrode 8 and the solution outlet 7, and a counter electrode 12 is located on the outer periphery of the cylindrical block 11, which is a structure having the solution outlet 7. It is arranged as an insulated and wound structure, and a counter electrode space (2-a) is between it and the inside of the block forming the outer wall of the cell 2, and the cell 2 is constituted by these spaces. The width of this counter electrode space (2-a) is 3 mm.
2 mm, preferably 2 mm. The working electrode 8 used here has a diameter of 8 m on a quartz plate with a thickness of 0.5 mm and a diameter of 13 mm.
Although the working electrode is plated with gold of m, the size, shape, and type of metal to be plated are not particularly limited, and any metal can be used. Further, the counter electrode 12 is also usually made of platinum, but the type of metal composing the electrode or the method of installing the counter electrode in the counter electrode space (2-a) is not limited to this specific example and may be of any type. can be used.
【００１３】ここで、電解質溶液１３或いは電解質試料
溶液について説明すると、電解質溶液１３とは作用物質
を含まないキャリヤー液であり、電解質試料溶液は分析
するべき作用物質を含んだ電解質溶液である。電解質試
料溶液の作用物質を除いた部分は電解質溶液１３と同じ
こともまた異なることもある。流動する電解質溶液１３
はセル部２の側面から溶液通路（２−ｂ）を経て排出さ
れるが，その時対極１２のあるセル部２の一部である対
極空間（２−ａ）の下部を通過する、対極空間（２−ａ
）は上記した通りその幅は３ｍｍ位、好ましくは２ｍｍ
位と狭いのでセル部２の一部である溶液通路（２−ｂ）
を電解質溶液１３が通過する時対極空間（２−ａ）内の
溶液に外乱を与えない。The electrolyte solution 13 or electrolyte sample solution will now be described. The electrolyte solution 13 is a carrier liquid that does not contain an active substance, and the electrolyte sample solution is an electrolyte solution that contains an active substance to be analyzed. The portion of the electrolyte sample solution excluding the active substance may be the same as the electrolyte solution 13 or may be different. Flowing electrolyte solution 13
is discharged from the side surface of the cell part 2 through the solution passage (2-b), but at this time, the counter electrode space (2-a), which is a part of the cell part 2 where the counter electrode 12 is located, passes through the lower part of the counter electrode space (2-a). 2-a
) has a width of about 3 mm, preferably 2 mm, as described above.
The solution passageway (2-b), which is a part of the cell part 2, is very narrow.
When the electrolyte solution 13 passes through, no disturbance is given to the solution in the counter electrode space (2-a).
【００１４】セル２を構成している空間、すなわち作用
空間（２−ｃ）、対極空間（２−ａ）及び溶液通路（２
−ｂ）は空間としては一体的で隔壁を有しない、それで
いて作用空間（２−ｃ）から溶液通路（２−ｂ）へ流れ
る電解質溶液１３或いは電解質試料溶液によって対極空
間（２−ａ）に存在する電解質溶液１３（場合により電
解質試料溶液が存在しても差し支えない）が乱されず、
実質的に静止状態にあることが本発明の特徴である。溶
液通路（２−ｂ）の上面の位置は作用極の上面から６ｍ
ｍ以内（図１ではｘで示される）、対極空間（２−ａ）
の高さｙは５ｍｍ以上１５ｍｍ以内が好ましい寸法であ
る。溶液通路（２−ｂ）を通った電解質溶液１３の一部
は、セル部２とは通常独立して設けられた液溜１４に溶
液通路（２−ｂ）を通って流入する、この液溜１４には
参照電極１５が好ましくは配置される。この参照電極１
５によってフローセル内の電解質溶液１３の電位が一定
に定められる。The spaces constituting the cell 2, namely the working space (2-c), the counter electrode space (2-a), and the solution passage (2-a)
-b) is integral as a space and does not have partition walls, yet exists in the counter electrode space (2-a) by the electrolyte solution 13 or electrolyte sample solution flowing from the working space (2-c) to the solution passage (2-b). The electrolyte solution 13 (in some cases, an electrolyte sample solution may be present) is not disturbed,
It is a feature of the invention that it is substantially stationary. The position of the upper surface of the solution passage (2-b) is 6 m from the upper surface of the working electrode.
Within m (indicated by x in Figure 1), opposite space (2-a)
The height y is preferably 5 mm or more and 15 mm or less. A part of the electrolyte solution 13 that has passed through the solution passageway (2-b) flows into a liquid reservoir 14, which is usually provided independently of the cell section 2, through the solution passageway (2-b). A reference electrode 15 is preferably arranged at 14 . This reference electrode 1
5, the potential of the electrolyte solution 13 in the flow cell is fixed.
【００１５】該電解フローセル１は最初使用する時、溶
液通路（２−ｂ）は閉塞して、試料溶液吹き出し口７か
ら電解質溶液をセル部２に電解質溶液１３を対極室（２
−ａ）を通して流し、対極室（２−ａ）の上部を空気抜
き口キャップ１６において閉塞する。かくして、対極室
（２−ａ）には電解質溶液１３が充満される。次に溶液
通路（２−ｂ）を開ける。そして、電解質溶液１３の供
給を始めて、液の流動が始まっても対極室（２−ａ）の
部分の電解質溶液１３は実質的に動かず、試料溶液は殆
どこの部分に流入してくることがない。作用極近辺の溶
液組成が電気分解や電気化学反応により変化しても、対
極側の組成は殆ど変化することがないので、電解電流が
安定し、感度がよくかつ再現性のよい測定を可能にする
。また、試料電解質溶液１３の流動が始まっても対極室
（２−ａ）の部分の電解質溶液１３は実質的に動かない
ので、実質的にセル部２の容積が小さくなる効果を生じ
試料の切り換え時に測定条件が安定化するのに時間がか
からないことに寄与する。When the electrolytic flow cell 1 is used for the first time, the solution passage (2-b) is closed and the electrolyte solution is supplied from the sample solution outlet 7 to the cell part 2 and the electrolyte solution 13 is supplied to the counter electrode chamber (2-b).
-a), and the upper part of the counter electrode chamber (2-a) is closed with the air vent cap 16. Thus, the counter electrode chamber (2-a) is filled with the electrolyte solution 13. Next, open the solution passage (2-b). Even when the electrolyte solution 13 starts to be supplied and the solution begins to flow, the electrolyte solution 13 in the counter electrode chamber (2-a) does not substantially move, and most of the sample solution does not flow into this part. do not have. Even if the solution composition near the working electrode changes due to electrolysis or electrochemical reactions, the composition on the counter electrode side hardly changes, making it possible to stabilize the electrolytic current and perform measurements with good sensitivity and reproducibility. do. In addition, even if the sample electrolyte solution 13 starts to flow, the electrolyte solution 13 in the counter electrode chamber (2-a) does not substantially move, so that the volume of the cell section 2 is substantially reduced, and the sample is switched. This contributes to the fact that it sometimes takes less time for measurement conditions to stabilize.
【００１６】従って、本発明の装置が、■ 電解室か
ら溶液がセル外へ流出するとき、溶液の流れは対極室の
下部を通るがその流れは対極付近の溶液の状態に影響を
与えない、すなわち、あたかも対極が仕切られた別室に
あるかのように溶液はセル外へ流出する。
■ 作用極への溶液の供給が、上部から垂直に供給さ
れる、とくに好ましくは、溶液供給管の出口の断面の形
状が作用極の形状と同じ、或いは相似していて、溶液は
層流状態で均一に作用極へ供給される。
■ セルの容積は小さく、特に電解室は薄くかつ容積
も小さく作られていて、流入した溶液は効率よく作用極
と接触して、絶えず新鮮な液が供給され、廃液は滞留し
ない。
構造に設計されているため、試料電解質溶液中の微量成
分は作用極に再現性よく均一に電着し、しかも対極付近
の電解室の液組成は殆ど変わらない。このため同じ溶液
を時間を置いて流しても測定中の電流値の再現性が大変
よい。また、上記■〜■の構造に造られた電解定量装置
用電解フローセルでは、溶液の電解質キャリヤー液が同
じであれば、濃度の異なる試料溶液をセル内に注入した
時、図２〜図４に示すように作用極付近の電解質溶液が
試料溶液により迅速に置代わり、電流がすぐに安定して
フローインジェクション法で測定が可能である。Therefore, in the device of the present invention, (1) when the solution flows out of the cell from the electrolytic chamber, the flow of the solution passes through the lower part of the counter electrode chamber, but the flow does not affect the state of the solution near the counter electrode; That is, the solution flows out of the cell as if the counter electrode were in a separate, partitioned room. ■ The solution is supplied to the working electrode vertically from the top, and particularly preferably, the cross-sectional shape of the outlet of the solution supply pipe is the same as or similar to the shape of the working electrode, and the solution is in a laminar flow state. is uniformly supplied to the working electrode. ■ The volume of the cell is small, especially the electrolytic chamber is thin and has a small volume, so that the solution that flows in efficiently contacts the working electrode, so that fresh solution is constantly supplied and waste solution does not accumulate. Because of the structural design, trace components in the sample electrolyte solution are electrodeposited uniformly on the working electrode with good reproducibility, and the liquid composition in the electrolytic chamber near the counter electrode hardly changes. Therefore, the reproducibility of the current value during measurement is very good even if the same solution is passed at different times. In addition, in the electrolytic flow cell for an electrolytic quantitative device constructed with the structure of ■ to ■ above, if the electrolyte carrier liquid of the solution is the same, when sample solutions with different concentrations are injected into the cell, the results shown in Figs. As shown, the electrolyte solution near the working electrode is quickly replaced by the sample solution, and the current stabilizes immediately, allowing measurement using the flow injection method.
【００１７】なお、本発明の電解フローセルは電解電位
をかけないで、単にフローセルとして使用した場合でも
優れた性能を示す。例えば、脂質二分子膜への臭い物質
や苦み物質の取り込み量の測定も試料の交換が簡単に行
える。苦味物質の取り込み量の測定を行うための装置の
システムを示すフローチャートとそれを用いて行った測
定例を図８及び図９に示した。The electrolytic flow cell of the present invention exhibits excellent performance even when used simply as a flow cell without applying an electrolytic potential. For example, samples can be easily exchanged to measure the amount of odorous substances or bitter substances incorporated into lipid bilayer membranes. A flowchart showing a system of an apparatus for measuring the amount of bitter substances taken in and an example of measurement performed using the same are shown in FIGS. 8 and 9.
【００１８】[0018]
【実施例】図５のような電解フローセルを組み込んだ電
解定量装置を用いて、ＥＤＴＡ−Ｆｅの酸化還元電圧電
流曲線及びチオ硫酸銀の電着による電解フローセルの作
用極の発振周波数の変化を測定した。これらの結果から
見ると、この電解フローセルは充分満足できる性能をも
っていることは明らかである。図６はＥＤＴＡ−Ｆｅの
酸化還元電圧電流曲線を示しているが、電圧電流曲線は
再現性がよく測定が安定していることを表している。参
考のために、電圧変化（Ｖ）による電解フローセルの作
用極の発振周波数の変化（Ｈｚ）の関係を示してたが、
当然この場合Ｆｅの電着はないので発振周波数は変化し
ない。図７にはチオ硫酸銀溶液を用いて、銀を電解フロ
ーセルの作用極に電着させた時の作用極の発振周波数の
変化（Ｈｚ）を測定した結果を示す。図７から電解フロ
ーセルに下記表に示したような銀塩濃度の異なる電解質
試料溶液を注入すると、銀塩濃度に応じた作用極の発振
周波数の変化（Ｈｚ）が安定に観測されることがわかる
。[Example] Using an electrolytic quantitative device incorporating an electrolytic flow cell as shown in Fig. 5, we measured the redox voltage-current curve of EDTA-Fe and the change in the oscillation frequency of the working electrode of the electrolytic flow cell due to the electrodeposition of silver thiosulfate. did. From these results, it is clear that this electrolytic flow cell has sufficiently satisfactory performance. FIG. 6 shows the redox voltage-current curve of EDTA-Fe, which indicates that the voltage-current curve has good reproducibility and stable measurement. For reference, the relationship between the change in oscillation frequency (Hz) of the working electrode of the electrolytic flow cell due to voltage change (V) is shown.
Naturally, in this case, since there is no electrodeposition of Fe, the oscillation frequency does not change. FIG. 7 shows the results of measuring the change in oscillation frequency (Hz) of the working electrode when silver was electrodeposited on the working electrode of an electrolytic flow cell using a silver thiosulfate solution. Figure 7 shows that when electrolyte sample solutions with different silver salt concentrations as shown in the table below are injected into the electrolytic flow cell, changes in the oscillation frequency (Hz) of the working electrode depending on the silver salt concentration can be observed stably. .
【００１９】
ＡｇＢ
ｒ濃度 周波数減少量
（グラム／リットル）
（Ｈｚ） サン
プル（１） ０．１０
３００
サンプル（２） ０．２０
６２５
サンプル（３） ０．３０
９５０
サンプル（４） ０．５０
１６５０
なお、ＡｇＢｒ濃度は原溶液を電解質溶液で２０
倍に希釈した溶液の濃度[0019]AgB
r concentration Frequency reduction amount
(grams/liter)
(Hz) Sample (1) 0.10
300
Sample (2) 0.20
625
Sample (3) 0.30
950
Sample (4) 0.50
1650
In addition, the AgBr concentration is 20
Concentration of diluted solution
【００２０】[0020]
【発明の効果】本発明の電解フローセルを有する電解定
量装置を用いることによって、写真処理液中の銀の濃度
を精度及び感度よく定量的に測定できる。本発明の電解
フローセルを有する電解定量装置は銀以外の物質の電解
定量にも利用できる。電位をかけた状態で、物質に他の
物質の吸着や取り込みをする挙動を定量的に評価できる
ので物性的研究に利用できる。Effects of the Invention By using the electrolytic quantitative apparatus having the electrolytic flow cell of the present invention, the concentration of silver in a photographic processing solution can be quantitatively measured with high accuracy and sensitivity. The electrolytic determination apparatus having the electrolytic flow cell of the present invention can also be used for electrolytic determination of substances other than silver. It can be used for physical property research because it can quantitatively evaluate the behavior of adsorption and uptake of other substances by applying an electric potential.
【図１】図１は本発明の電解フローセルの一態様を示す
模式図[Fig. 1] Fig. 1 is a schematic diagram showing one embodiment of the electrolytic flow cell of the present invention.
【図２】図２は大きいセル中の電解質溶液を電解質試料
溶液で置換する態様を示す模式図[Figure 2] Figure 2 is a schematic diagram showing how the electrolyte solution in a large cell is replaced with an electrolyte sample solution.
【図３】図３は小さいセル中の電解質溶液を電解質試料
溶液で置換する態様を示す模式図[Figure 3] Figure 3 is a schematic diagram showing how the electrolyte solution in a small cell is replaced with an electrolyte sample solution.
【図４】図４はセル容量と電解質試料溶液で置換する時
間との関係を示す関係図[Figure 4] Figure 4 is a relationship diagram showing the relationship between cell capacity and replacement time with electrolyte sample solution.
【図５】図５は本発明の電解フローセルを使用した電解
定量装置のシステムを示すフローチャート[Fig. 5] Fig. 5 is a flowchart showing a system of an electrolytic quantitative device using the electrolytic flow cell of the present invention.
【図６】図６
は本発明の電解フローセルを用いて測定したＥＤＴＡ−
Ｆｅの酸化還元電圧電流曲線及び作用極の周波数変化図[Figure 6] Figure 6
is EDTA- measured using the electrolytic flow cell of the present invention.
Redox voltage current curve of Fe and frequency change diagram of working electrode
【図７】図７は本発明の電解フローセルを用いて測定し
たチオ硫酸銀溶液からの銀の電着による作用極の発振周
波数の変化（Ｈｚ）を示す関係図[Figure 7] Figure 7 is a relationship diagram showing the change in oscillation frequency (Hz) of the working electrode due to electrodeposition of silver from a silver thiosulfate solution measured using the electrolytic flow cell of the present invention.
【図８】図８は苦味物質の取り込み量の測定を行うため
の装置のシステムを示すフローチャート[Fig. 8] Fig. 8 is a flowchart showing a system of an apparatus for measuring the amount of uptake of bitter substances.
【図９】図９は
図８の装置を用いて行った苦味物質の取り込み量の測定
の結果を示す関係図[Fig. 9] Fig. 9 is a relational diagram showing the results of measuring the amount of bitter substances taken up using the apparatus shown in Fig. 8.
１ 電解フローセル ２ セル部 （２−ａ） 対極空間 （２−ｂ） 流出経路 （２−ｃ） 作用空間 ３ Ｏリング ４ フランジ ５ 樹脂板 ６ ゴム ７ 溶液吹き出し口 ８ 作用極 ９ 目皿 １１ 円柱状ブロック １２ 対極 １３ 電解質溶液 １４ 液溜 １５ 参照電極 １６ 空気抜き口キャップ ２１ 周波数カウンター ２２ ポテンショスタット ２３ データ処理装置 ２４ 発振器 ２８ 送液ポンプ ２９ 試料注入バルブ ３０ 廃液タンク 1 Electrolytic flow cell 2 Cell part (2-a) Opposite space (2-b) Outflow route (2-c) Action space 3 O-ring 4 Flange 5 Resin plate 6 Rubber 7 Solution outlet 8 Working electrode 9th plate 11 Cylindrical block 12 Opposite 13 Electrolyte solution 14 Liquid reservoir 15 Reference electrode 16 Air vent cap 21 Frequency counter 22 Potentiostat 23 Data processing device 24 Oscillator 28 Liquid pump 29 Sample injection valve 30 Waste liquid tank
Claims (3)
晶発振子を含んで構成される作用極と対極とを有する電
解フローセルを通して微量成分を電解定量する電解定量
装置において、該電解フローセル内の電解質溶液は一体
的であるが、少なくとも電解質試料溶液の電解定量を行
っている間、流動している部分と実質的に静止している
部分とがあり、作用極は流動している部分に接しており
、対極は実質的に静止している部分に接していることを
特徴とする電解定量装置用電解フローセル。1. An electrolytic quantitative device for electrolytically quantifying trace components through an electrolyte flow cell having a working electrode and a counter electrode including a crystal oscillator, in which an electrolyte sample solution containing trace components is passed through an electrolytic flow cell having a working electrode and a counter electrode including a crystal oscillator. Although the solution is integral, at least during electrolytic determination of the electrolyte sample solution, there is a flowing part and a substantially stationary part, and the working electrode is in contact with the flowing part. An electrolytic flow cell for an electrolytic metering device, characterized in that the counter electrode is in contact with a substantially stationary part.
ルに、その水晶発振子を含んで構成される作用極の面に
対して垂直に供給され、電解フローセル内の電解質溶液
の流動している部分の容積が供給される電解質溶液の一
分間当たりの供給量の１／２．５〜１／２０倍の範囲で
あることを特徴とする請求項１記載の電解定量装置用電
解フローセル。2. An electrolyte sample solution for measurement is supplied to the electrolytic flow cell perpendicularly to the surface of the working electrode including the crystal oscillator, and the electrolyte sample solution in the electrolytic flow cell is 2. The electrolytic flow cell for an electrolytic metering device according to claim 1, wherein the volume is in the range of 1/2.5 to 1/20 times the amount of supplied electrolyte solution per minute.
溶液と直接電気的に導通状態にある電解質溶液中に存在
して、該電解質溶液に一定の電位をかけていることを特
徴とする請求項１又は請求項２に記載の電解定量装置用
電解フローセル。3. Claim 1, wherein the reference electrode is present in an electrolyte solution that is in direct electrical continuity with the electrolyte solution in the electrolysis flow cell, and applies a constant potential to the electrolyte solution. Or an electrolytic flow cell for an electrolytic quantitative device according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5563591A JPH04273041A (en) | 1991-02-28 | 1991-02-28 | Electrolytic flow cell using crystal vibrator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5563591A JPH04273041A (en) | 1991-02-28 | 1991-02-28 | Electrolytic flow cell using crystal vibrator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04273041A true JPH04273041A (en) | 1992-09-29 |
Family
ID=13004259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5563591A Pending JPH04273041A (en) | 1991-02-28 | 1991-02-28 | Electrolytic flow cell using crystal vibrator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04273041A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022034782A1 (en) * | 2020-08-12 | 2022-02-17 | 株式会社ファーストスクリーニング | Electrochemical sensor unit |
-
1991
- 1991-02-28 JP JP5563591A patent/JPH04273041A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022034782A1 (en) * | 2020-08-12 | 2022-02-17 | 株式会社ファーストスクリーニング | Electrochemical sensor unit |
| JP2022032926A (en) * | 2020-08-12 | 2022-02-25 | 株式会社ファーストスクリーニング | Electrochemical sensor unit |
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