JP2003506713A - Sealed salt bridge - Google Patents
Sealed salt bridgeInfo
- Publication number
- JP2003506713A JP2003506713A JP2001515955A JP2001515955A JP2003506713A JP 2003506713 A JP2003506713 A JP 2003506713A JP 2001515955 A JP2001515955 A JP 2001515955A JP 2001515955 A JP2001515955 A JP 2001515955A JP 2003506713 A JP2003506713 A JP 2003506713A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- conduit
- chamber
- salt bridge
- cross
- 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.)
- Withdrawn
Links
- 239000003792 electrolyte Substances 0.000 claims abstract description 75
- 150000002500 ions Chemical class 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000012085 test solution Substances 0.000 claims abstract description 12
- 239000012895 dilution Substances 0.000 claims abstract description 4
- 238000010790 dilution Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000000523 sample Substances 0.000 description 7
- 239000000356 contaminant Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- G01N27/401—Salt-bridge leaks; Liquid junctions
Landscapes
- 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 Analysing Biological Materials (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
(57)【要約】 本発明は、電解質で充填し接続した２つの区間、すなわち遠位端が試験溶液５０または別の塩橋と接触して液絡１６として働き、近位端が電極または第２の液絡１８と接触する電解質室１２に接続された比較的長く狭い電解質導管１４で構成された密封塩橋１０である。電解質室１２は、電解質導管よりかなり広い。導管は、その長さおよび比較的小さい断面のため、試験溶液または別の電解質区画からの異物イオンが、液絡から拡散し、電解質室を汚染する速度を制限する働きをする。電解質室は、その比較的大きい断面寸法およびそれに伴う単位長さ当たりの大きい容積のため、希釈によって、徐々に室に拡散する異物イオンの濃度を制限する働きをする。 SUMMARY OF THE INVENTION The present invention provides two sections filled and connected with an electrolyte, the distal end of which contacts the test solution 50 or another salt bridge to act as a liquid junction 16 and the proximal end of which is an electrode or a second electrode. The sealed salt bridge 10 is composed of a relatively long and narrow electrolyte conduit 14 connected to an electrolyte chamber 12 in contact with a second liquid junction 18. The electrolyte chamber 12 is considerably wider than the electrolyte conduit. Because of its length and relatively small cross-section, the conduit serves to limit the rate at which foreign ions from the test solution or another electrolyte compartment diffuse out of the liquid junction and contaminate the electrolyte chamber. The electrolyte chamber, due to its relatively large cross-sectional dimensions and consequently large volume per unit length, serves to limit, by dilution, the concentration of foreign ions which gradually diffuse into the chamber.
Description
【０００１】
発明の分野
本発明は、電気化学センサに使用する塩橋に関する。塩橋は、電気化学セルの
２つの部分間の電解質接続を維持しながら、それを相互から分離する働きをする
電解質充填区画である。FIELD OF THE INVENTION The present invention relates to salt bridges for use in electrochemical sensors. The salt bridge is an electrolyte-filled compartment that serves to separate the one from the other while maintaining an electrolyte connection between the two parts of the electrochemical cell.
【０００２】
発明の背景
ポテンシオメトリックセルで使用する場合、塩橋は、１次液絡から電極の周囲
または２次液絡へと拡散する異種イオンまたは他の種で徐々に汚染され、電位の
変化を引き起こすことがある。電位変化の開始を遅らせる以前の方法が、米国特
許第４，９５９，１３８号、第５，１４７，５２４号および第５，３４６，６０
６号で見ることができる。BACKGROUND OF THE INVENTION When used in potentiometric cells, salt bridges are gradually contaminated with foreign ions or other species that diffuse from the primary junction to the surroundings of the electrode or to the secondary junction, resulting in a potential difference. May cause change. Previous methods of delaying the onset of potential changes have been described in US Pat. Nos. 4,959,138, 5,147,524 and 5,346,60.
It can be seen in issue 6.
【０００３】
米国特許第４，９５９，１３８号では、内部電解質が本来の位置でゲル化され
て、イオン透過性ポリマーを形成し、イオン透過は、汚染するイオンを吸収する
固体のシリカゲル粒子を組み込むことによって、さらに遅れる。この特許は、電
解質が、本来の位置でイオン透過性ポリマーおよび中性塩懸濁液から生成された
粘度の高いゲルの形態である測定プローブについて説明している。一様に懸濁し
たゲル中の中性塩粒子により、ゲルは混濁した外観を有し、これは懸濁した中性
塩粒子が溶液中に通るにつれて徐々に消え、したがって常に電解質の老化状態を
示す。シリカゲルが追加的に存在することにより、プローブ電位が１０バールを
超える圧力に耐えられるようになる。In US Pat. No. 4,959,138, an internal electrolyte is gelled in situ to form an ion-permeable polymer, the ion-permeation incorporating solid silica gel particles that absorb contaminating ions. By being delayed further. This patent describes a measuring probe in which the electrolyte is in situ in the form of a viscous gel formed from an ion-permeable polymer and a neutral salt suspension. Due to the neutral salt particles in the uniformly suspended gel, the gel has a turbid appearance, which gradually disappears as the suspended neutral salt particles pass through the solution, and thus always lead to an aging state of the electrolyte. Show. The additional presence of silica gel allows the probe potential to withstand pressures above 10 bar.
【０００４】
米国特許第５，１４７，５２４号では、イオン透過性の木栓がイオンの拡散を
妨げ、栓には、さらに、イオンが曲がりくねった路を辿らねばならないような方
法で切欠きを設ける。この特許は、中心の内腔が形成され、栓の第１端付近に空
隙も形成された一体で円筒形の半多孔性栓を含むｐＨセンサについて説明してい
る。ｐＨ電極は、中心の内腔に配置され、試料流体と接触するために栓の第２の
端から外方向に延在し、基準電極が空隙内に配置される。栓は、電解質で飽和し
、基準電極と試料流体との間に電気化学的導通を確立する。試料流体からのイオ
ンが栓を通って移動し、基準電極を汚染することを防止するため、栓の中途まで
複数の切欠きを半径方向に機械加工し、イオン不透過性エポキシで充填する。切
欠きは、栓の軸に対して斜角で配向し、イオン不透過性エポキシで充填すること
が好ましい。切欠きは、栓の軸に対して斜角で配向し、汚染性イオンの有意の比
率を固定して妨げる「デッドエンド」イオントラップを形成し、したがって電極
の寿命を延長することが好ましい。In US Pat. No. 5,147,524, ion-permeable wood plugs prevent the diffusion of ions and the plugs are further notched in such a way that the ions must follow a tortuous path. . This patent describes a pH sensor that includes an integral, cylindrical, semi-porous stopper with a central lumen formed and a void near the first end of the stopper. A pH electrode is positioned in the central lumen, extends outwardly from the second end of the bung to contact the sample fluid, and a reference electrode is positioned in the cavity. The stopper is saturated with electrolyte and establishes an electrochemical connection between the reference electrode and the sample fluid. To prevent ions from the sample fluid from migrating through the stopper and contaminating the reference electrode, the notches are machined radially to the middle of the stopper and filled with an ion impermeable epoxy. The notches are oriented at an oblique angle to the axis of the plug and are preferably filled with ion impermeable epoxy. The notches are preferably oriented at an oblique angle to the axis of the plug, forming a "dead end" ion trap that locks in and prevents a significant proportion of contaminating ions, thus extending the life of the electrode.
【０００５】
米国特許第５，３４６，６０６号は、木製栓を使用する点で米国特許第５，１
４７，５２４号に似ているが、この場合は木から螺旋形を切り出して、イオンに
螺旋路を辿らせる。この特許は、塩橋が電解質で飽和した半透過性材料の一体栓
である電気化学センサについて説明している。栓は、栓の外面から中心の内腔へ
と切削された螺旋を有する。螺旋は、少なくとも１回転し、栓の一方端で、また
はその付近で開始し、栓の他方端で、またはその付近で停止する。不透過性材料
の層を栓に付着させ、それによってイオン不透過性の螺旋形バリアを形成する。US Pat. No. 5,346,606 is US Pat. No. 5,1 in that it uses a wooden plug.
Similar to No. 47,524, but in this case a helix is cut out of a tree, causing the ions to follow a spiral path. This patent describes an electrochemical sensor in which the salt bridge is an integral plug of semi-permeable material saturated with electrolyte. The bung has a helix that is cut from the outer surface of the bung into the central lumen. The spiral makes at least one revolution, starting at or near one end of the stopper and stopping at or near the other end of the stopper. A layer of impermeable material is attached to the stopper, thereby forming an ion-impermeable helical barrier.
【０００６】 これらの参考文献の開示は、参照によって本明細書に組み込まれる。[0006] The disclosures of these references are incorporated herein by reference.
【０００７】
発明の概要
本発明は、電解質で充填された接続された２つの区間、すなわち遠位端が試験
溶液または別の塩橋と接触して液絡として働き、近位端が電極または第２の液絡
と接触する電解質室に接続される（以下で定義しているように）比較的長く狭い
電解質導管で構成された密封塩橋である。電解質室は（以下で定義するように）
電解質導管よりかなり広い。導管は、その長さおよび比較的小さい断面との組合
せのため、試験溶液または別の電解室区画からの異物イオンが、液絡から拡散し
、電解質室を汚染する速度を制限する働きをする。電解質室は、その比較的大き
い断面寸法およびそれに伴う単位長さ当たりの大きい容積のため、希釈によって
、徐々に室に拡散する異物イオンの濃度を制限する働きをする。SUMMARY OF THE INVENTION The present invention provides two connected sections filled with electrolyte, the distal end in contact with a test solution or another salt bridge, which acts as a junction and the proximal end with an electrode or a second A sealed salt bridge composed of a relatively long and narrow electrolyte conduit (as defined below) connected to the electrolyte chamber in contact with the two liquid junctions. The electrolyte chamber is (as defined below)
Significantly wider than the electrolyte conduit. The conduit, due to its length and in combination with its relatively small cross section, serves to limit the rate at which foreign ions from the test solution or another compartment of the electrolytic chamber diffuse out of the junction and contaminate the electrolyte chamber. The electrolyte chamber, due to its relatively large cross-sectional size and the concomitant large volume per unit length, serves to limit the concentration of foreign ions that gradually diffuse into the chamber by dilution.
【０００８】
好ましい実施形態の詳細な説明
以下で説明し、従来技術で示されるように、塩橋は、電気化学セルの２つの部
分を、その間の電解質接続を維持しながら、相互から分離する働きをする、電解
質で充填された区画である。分離されるセルの２つの部分は、電極または他の電
解質区画でよい。Detailed Description of the Preferred Embodiments As described below and shown in the prior art, a salt bridge serves to separate two parts of an electrochemical cell from each other while maintaining an electrolyte connection therebetween. It is a compartment filled with electrolyte. The two parts of the cell that are separated may be electrodes or other electrolyte compartments.
【０００９】
塩橋の１つの目的は、試験溶液またはセルの他の部分からの成分拡散によって
生じ得るセルの一部分の汚染を防止、または遅らせることである。以下で開放塩
橋と呼ぶ一部の塩橋では、汚染防止は、重力で誘発された流れまたは他の加圧手
段によって塩橋電解質を連続的に補充することによって補助され、このような補
充は、汚染物質をシステムから洗い流す働きをする。One purpose of the salt bridge is to prevent or delay fouling of a portion of the cell that may result from component diffusion from the test solution or other portions of the cell. In some salt bridges, referred to below as open salt bridges, pollution control is aided by continuous replenishment of salt bridge electrolytes by gravity-induced flow or other pressure means, and such replenishment is Acts to flush contaminants from the system.
【００１０】
塩橋電解質と、試験溶液またはセル内でそれが接触する他の電解質との大量な
混合は、液体間の接触点を小さいオリフィスまたは多孔性バリアに制限すること
により、防止することができる。以下では、異なる液体間の接触点を、接触点が
小さいオリフィスまたは多孔性バリアであるか、それでなくても、液絡と呼ぶ。Extensive mixing of the salt bridge electrolyte with the test solution or other electrolytes it contacts in the cell can be prevented by limiting the contact point between the liquids to a small orifice or porous barrier. it can. In the following, the contact point between different liquids will be referred to as the liquid junction, whether or not the orifice or porous barrier with the small contact point.
【００１１】
本発明は、開放塩橋ではなく、以下では密封塩橋と呼ぶ。密封塩橋では、汚染
物質の移動は、流れの補充または洗い流しの補助がなくても、汚染物質が拡散し
なければならない電解質を挟むだけで遅延する。汚染物質が拡散によって横断し
なければならない距離が大きいほど、任意の汚染レベルが発生するために必要な
時間が長くなる。The present invention is referred to below as a closed salt bridge, rather than an open salt bridge. In a sealed salt bridge, pollutant migration is delayed by sandwiching the electrolyte through which the pollutant must diffuse, without the aid of flow replenishment or flushing. The greater the distance a contaminant must traverse by diffusion, the longer the time required for any contamination level to occur.
【００１２】
本明細書に添付した図には本願発明の密封塩橋の好的な一実施形態が描かれて
いる。図示のように、密封塩橋１０は電解質３０で充填される。密封塩橋１０は
、さらに、以下の要素を備える。つまり電解質室１２、電解質導管１４、１次液
絡１６および電極または２次液絡１８である。The figures attached to the present specification depict a preferred embodiment of the sealed salt bridge of the present invention. As shown, the sealed salt bridge 10 is filled with an electrolyte 30. The sealed salt bridge 10 further includes the following elements. That is, the electrolyte chamber 12, the electrolyte conduit 14, the primary liquid junction 16 and the electrode or secondary liquid junction 18.
【００１３】
図で示すように、電解質室１２は一方端で電解質導管１４に接続され、これは
１次液絡１６で終了する。１次液絡１６は、密封塩橋１０と試験溶液５０との接
触点である。電解質室１２の反対側の端部には、電極または２次液絡１８が位置
する。As shown, the electrolyte chamber 12 is connected at one end to an electrolyte conduit 14, which terminates in a primary junction 16. The primary junction 16 is a contact point between the sealed salt bridge 10 and the test solution 50. An electrode or secondary liquid junction 18 is located at the opposite end of the electrolyte chamber 12.
【００１４】
本発明では、電位変化の開始は、１次液絡から電解質室への導管の細長い拡散
路によって、および電解質室内にある大量の電解質によって遅延する。汚染物質
が電解質室に到達する速度は、導管の長さおよびその直径の２乗に反比例する。
汚染物質の任意の進入速度では、電解質室中の汚染物質の濃縮速度は、電解質室
の容積に反比例して増加する。In the present invention, the onset of the potential change is delayed by the elongated diffusion path of the conduit from the primary junction to the electrolyte chamber and by the bulk electrolyte present in the electrolyte chamber. The rate at which contaminants reach the electrolyte chamber is inversely proportional to the length of the conduit and the square of its diameter.
For any entry rate of contaminants, the concentration rate of contaminants in the electrolyte chamber increases inversely with the volume of the electrolyte chamber.
【００１５】
したがって、好ましい実施形態では、本発明は、電解質で充填された接続され
た２つの区間、すなわち遠位端が試験溶液または別の塩橋に接触して液絡として
働き、近位端が電極または第２の液絡と接触する電解質室に接続された（電解質
室に対して）比較的長くて細い電解質導管で構成された密封塩橋であって、電界
質室は電解質導管よりかなり広い密封塩橋を対象とする。Therefore, in a preferred embodiment, the invention provides that the two connected sections filled with electrolyte, the distal end, contact the test solution or another salt bridge to act as a junction and the proximal end. Is a sealed salt bridge composed of a relatively long and thin electrolyte conduit (relative to the electrolyte chamber) connected to an electrolyte chamber in contact with an electrode or a second liquid junction, the electrolyte chamber being much larger than the electrolyte conduit. Intended for a wide sealed salt bridge.
【００１６】
特に好ましい実施形態では、電解質導管は、長さが１ｍｍから１００ｃｍ、断
面が１０μｍから２ｍｍで、長さは常に直径の少なくとも５倍ある。In a particularly preferred embodiment, the electrolyte conduit is 1 mm to 100 cm in length, 10 μm to 2 mm in cross section, and the length is always at least 5 times its diameter.
【００１７】
特に好ましい実施形態では、電解質室の断面は導管の断面の５倍から１００倍
であり、その長さは導管の１／２から１／１００である。In a particularly preferred embodiment, the cross section of the electrolyte chamber is 5 to 100 times the cross section of the conduit and its length is 1/2 to 1/100 of the conduit.
【００１８】
概して、本発明の塩橋に使用する電解質は、塩水溶液、非水塩溶液、固体塩、
または塩を含むゲルで構成されたグループから選択することができる。Generally, the electrolytes used in the salt bridges of the present invention include aqueous salt solutions, non-aqueous salt solutions, solid salts,
Alternatively, it can be selected from the group consisting of gels containing salts.
【００１９】
所望に応じて、本発明の塩橋は、例えば導管または室の全部または一部が電解
質に加えて不活性充填剤を含むよう変形することができる。If desired, the salt bridge of the present invention can be modified, for example, so that all or part of the conduit or chamber contains an inert filler in addition to the electrolyte.
【００２０】
所望に応じて、本発明の塩は、このような装置に通常使用される任意の形状お
よび材料を使用して形成することができる。例えば、導管または室に円形、楕円
形、または縦横比が高い、または低い多辺形である断面形状を設けることができ
る。導管または室は、直線、曲線、コイル状、螺旋形、蛇行、または他の形で曲
がりくねってもよい。装置のこれらの部分の形成に使用する材料は、ガラス、セ
ラミック、または他の化学的に不活性で電気的に絶縁性の材料でよい。If desired, the salts of the present invention can be formed using any of the shapes and materials normally used in such devices. For example, the conduit or chamber can be provided with a cross-sectional shape that is circular, elliptical, or high or low aspect ratio polygon. The conduit or chamber may be straight, curved, coiled, helical, serpentine, or otherwise meander. The material used to form these parts of the device may be glass, ceramic, or other chemically inert and electrically insulating material.
【００２１】
導管は、その長さおよび比較的小さい断面積により、試験溶液または別の電解
質区画からの異物イオンが液絡から拡散し、電解質室を汚染する速度を制限する
働きをする。電解質室は、その比較的大きい断面積および単位長さ当たりの汚染
物質の体積が大きいことから、同様に、希釈によって徐々に室に拡散する異物イ
オンの濃度を制限する働きをする。Due to its length and relatively small cross-sectional area, the conduit serves to limit the rate at which foreign ions from the test solution or another electrolyte compartment diffuse out of the junction and contaminate the electrolyte chamber. Due to its relatively large cross-sectional area and the large volume of pollutants per unit length, the electrolyte chamber also serves to limit the concentration of foreign ions that gradually diffuse into the chamber by dilution.
【００２２】
本発明を、本発明の理解に役立つが、その制限としては想定されていない以下
の例に関してさらに実証する。本明細書で報告するパーセンテージは、他に指定
しない限り、重量パーセントである。全ての温度は摂氏で表現される。The present invention will be further demonstrated with respect to the following examples, which are helpful in understanding the present invention, but are not intended to be limiting thereof. The percentages reported herein are weight percentages unless otherwise specified. All temperatures are expressed in degrees Celsius.
【００２３】 密封塩橋：例１ ８つの組合せｐＨ電極を作成した。[0023] Sealed salt bridge: Example 1 Eight combined pH electrodes were made.
【００２４】
電極１〜４は、本発明の大きい電解質室（１２）がなく、狭い電解質導管（１
４）のみがある塩橋を有し、５〜８番は本発明の説明に合致する大きい室を有す
る。The electrodes 1 to 4 do not have the large electrolyte chamber (12) of the present invention, but a narrow electrolyte conduit (1
Only 4) has a salt bridge and numbers 5-8 have large chambers consistent with the description of the invention.
【００２５】
全ての電極で、塩橋電解質（３０）は、４Ｍのヨウ化カリウム、０．００６９
Ｍのヨウ素、０．０１Ｍの硼酸で構成され、水酸化カリウムでｐＨ７．１５に調
節し、次に不活性シックナとして３５ｇ／Ｌのヒュームドシリカ（ＣＡＢ−Ｏ−
ＳＩＬ Ｍ−５、Ｃａｂｏｔ Ｃｏｒｐｏｒａｔｉｏｎ，Ｂｉｌｌｅｒｉｃａ，
ＭＡ）と完全に混合した。For all electrodes, the salt bridge electrolyte (30) was 4M potassium iodide, 0.0069.
Composed of M iodine, 0.01 M boric acid, adjusted to pH 7.15 with potassium hydroxide, and then used as an inert thickener, 35 g / L of fumed silica (CAB-O-
SIL M-5, Cabot Corporation, Billerica,
MA).
【００２６】
電極１〜４では、プラチナのワイヤ電極を、内径１．５ｍｍ、外径２．５ｍｍ
、長さ３００ｍｍで１０回コイル巻きにし、コイル内径１０ｍｍにしたガラス管
から構築した電解質導管（１４）の近位端内に直接密封した。For the electrodes 1 to 4, a platinum wire electrode was used, having an inner diameter of 1.5 mm and an outer diameter of 2.5 mm.
Coiled 10 times with a length of 300 mm and sealed directly into the proximal end of an electrolyte conduit (14) constructed from a glass tube with a coil inner diameter of 10 mm.
【００２７】
電極５〜８では、導管（１４）の近位端を、長さ２０ｍｍで内径１０ｍｍの電
解質室（１２）に接続する。この場合、電解質室はプラチナのワイヤ電極を含ん
でいた。At the electrodes 5-8, the proximal end of the conduit (14) is connected to an electrolyte chamber (12) with a length of 20 mm and an inner diameter of 10 mm. In this case, the electrolyte chamber contained platinum wire electrodes.
【００２８】
全ての電極は、導管の遠位端に多孔性セラミックの栓を有し、３ＭのＫＣｌ電
解質を有する第２の塩橋との液絡（１６）を提供した。第２のセラミック栓が、
３ＭのＫＣｌと試験溶液の間の液絡を提供した。基準半電池を、完全な組合せｐ
Ｈプローブとして、ガラスのｐＨ球半電池と一体作成した。ｐＨ半電池は、プラ
チナのワイヤ内部電極を有し、不活性充填剤以外は内部塩橋と同じ溶液で充填し
た。All electrodes had a porous ceramic plug at the distal end of the conduit and provided a liquid junction (16) with a second salt bridge with 3M KCl electrolyte. The second ceramic plug
Provided a junction between 3M KCl and the test solution. Reference half battery, complete combination p
An H probe was made integrally with a glass pH bulb half cell. The pH half-cell had a platinum wire inner electrode and was filled with the same solution as the inner salt bridge except the inert filler.
【００２９】
新品の場合、全てのプローブはｐＨ７の緩衝液内で約０ｍＶの電位を有した。
ｐＨ球内の溶液のｐＨがほぼ７であり、各半電池の各プラチナ・ワイヤの電位が
ほぼ等しかったからである。つまり、電池が対称で、基準半電池の電位とガラス
膜の電位が相殺されたのである。When new, all probes had a potential of about 0 mV in pH 7 buffer.
This is because the pH of the solution in the pH sphere was approximately 7, and the potential of each platinum wire of each half-cell was approximately the same. In other words, the cell is symmetrical, and the potential of the reference half cell and the potential of the glass film cancel each other out.
【００３０】
表１および表２を参照すると、電極１〜４の電位は、ｐＨ７の緩衝剤中で約４
カ月保存すると、マイナスの方向に平均して−２３ｍＶ近く変化し、同じ条件で
、電極５〜８の変化は１ｍＶ未満であった。電極１〜４の変化は、３ＭのＫＣｌ
溶液が電解質導管の近位端でプラチナワイヤに拡散するせいであった。電極５〜
８では、ＫＣｌの拡散の効果は検出不可能であった。大きい電解質室が入ってく
るＫＣｌを希釈したからである。Referring to Table 1 and Table 2, the potentials of the electrodes 1 to 4 are about 4 in a buffer having a pH of 7.
When stored for a month, the average value changed in the negative direction near -23 mV, and under the same conditions, the change in electrodes 5 to 8 was less than 1 mV. The change of electrodes 1-4 is 3M KCl
This was due to the solution diffusing into the platinum wire at the proximal end of the electrolyte conduit. Electrode 5
In 8, the effect of KCl diffusion was undetectable. This is because the KCl that entered the large electrolyte chamber was diluted.
【表１】 [Table 1]
【表２】 [Table 2]
【００３１】
本発明を、その好ましい実施形態を含めて詳細に説明してきた。しかし、本明
細書の開示を考察すると、当業者なら本発明に関して変形および／または改良を
実行し、それでも請求の範囲に記載されたような本発明の範囲および精神に入っ
ていることが理解される。The invention has been described in detail, including the preferred embodiments thereof. However, it will be understood upon consideration of the disclosure herein that those skilled in the art can make variations and / or modifications with respect to the present invention and still fall within the scope and spirit of the invention as claimed. It
【図１】 本発明の密封塩橋の１つの好ましい実施形態を示す図である。[Figure 1] FIG. 1 shows one preferred embodiment of the sealed salt bridge of the present invention.
───────────────────────────────────────────────────── フロントページの続き (81)指定国 ＥＰ(ＡＴ，ＢＥ，ＣＨ，ＣＹ， ＤＥ，ＤＫ，ＥＳ，ＦＩ，ＦＲ，ＧＢ，ＧＲ，ＩＥ，Ｉ Ｔ，ＬＵ，ＭＣ，ＮＬ，ＰＴ，ＳＥ)，ＯＡ(ＢＦ，ＢＪ ，ＣＦ，ＣＧ，ＣＩ，ＣＭ，ＧＡ，ＧＮ，ＧＷ，ＭＬ， ＭＲ，ＮＥ，ＳＮ，ＴＤ，ＴＧ)，ＡＰ(ＧＨ，ＧＭ，Ｋ Ｅ，ＬＳ，ＭＷ，ＳＤ，ＳＬ，ＳＺ，ＴＺ，ＵＧ，ＺＷ )，ＥＡ(ＡＭ，ＡＺ，ＢＹ，ＫＧ，ＫＺ，ＭＤ，ＲＵ， ＴＪ，ＴＭ)，ＡＥ，ＡＧ，ＡＬ，ＡＭ，ＡＴ，ＡＵ， ＡＺ，ＢＡ，ＢＢ，ＢＧ，ＢＲ，ＢＹ，ＣＡ，ＣＨ，Ｃ Ｎ，ＣＲ，ＣＵ，ＣＺ，ＤＥ，ＤＫ，ＤＭ，ＤＺ，ＥＥ ，ＥＳ，ＦＩ，ＧＢ，ＧＤ，ＧＥ，ＧＨ，ＧＭ，ＨＲ， ＨＵ，ＩＤ，ＩＬ，ＩＮ，ＩＳ，ＪＰ，ＫＥ，ＫＧ，Ｋ Ｐ，ＫＲ，ＫＺ，ＬＣ，ＬＫ，ＬＲ，ＬＳ，ＬＴ，ＬＵ ，ＬＶ，ＭＡ，ＭＤ，ＭＧ，ＭＫ，ＭＮ，ＭＷ，ＭＸ， ＮＯ，ＮＺ，ＰＬ，ＰＴ，ＲＯ，ＲＵ，ＳＤ，ＳＥ，Ｓ Ｇ，ＳＩ，ＳＫ，ＳＬ，ＴＪ，ＴＭ，ＴＲ，ＴＴ，ＴＺ ，ＵＡ，ＵＧ，ＵＺ，ＶＮ，ＹＵ，ＺＡ，ＺＷ (72)発明者 ウエスト，ステイーブン・ジエイ アメリカ合衆国、マサチユーセツツ・ 02045、ハル、ボートリノツト・アベニユ ー・26─────────────────────────────────────────────────── ─── Continued front page (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SL, SZ, TZ, UG, ZW ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, C N, CR, CU, CZ, DE, DK, DM, DZ, EE , ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, K P, KR, KZ, LC, LK, LR, LS, LT, LU , LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, S G, SI, SK, SL, TJ, TM, TR, TT, TZ , UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor West, Stephen Jei United States, Masachi Youth 02045, Hull, Boat Renott Avenir -26
Claims (7)
が試験溶液または別の塩橋と接触して液絡として働き、近位端が電極または第２
の液絡と接触する電解質室に接続された比較的長く狭い電解質導管で構成された
密封塩橋であって、電解質室は電解質導管よりかなり広く、導管の長さは断面直
径の少なくとも５倍あり、 導管は、その長い長さおよび比較的小さい断面のため、試験溶液または別の電
解質区画からの異物イオンが液絡から拡散し電解質室を汚染する速度を制限する
働きをし、 電解質室は、その比較的大きい断面寸法およびそれに伴う単位長さ当たりの大
きい容積のため、希釈によって、徐々に室に拡散する異物イオンの濃度を制限す
る働きをする塩橋。1. An electrolyte-filled, two connected section, the distal end in contact with a test solution or another salt bridge, to act as a junction and the proximal end to an electrode or a second.
A sealed salt bridge consisting of a relatively long and narrow electrolyte conduit connected to an electrolyte chamber in contact with the liquid junction of, the electrolyte chamber being significantly wider than the electrolyte conduit and having a length of at least 5 times the cross-sectional diameter Due to its long length and relatively small cross section, the conduit serves to limit the rate at which foreign ions from the test solution or another electrolyte compartment diffuse out of the junction and contaminate the electrolyte chamber, and the electrolyte chamber is A salt bridge that, due to its relatively large cross-sectional dimensions and the consequent large volume per unit length, serves to limit the concentration of foreign ions that gradually diffuse into the chamber by dilution.
面直径が約１０μｍから約３ｍｍである、請求項１に記載の塩橋。2. The salt bridge of claim 1, wherein the electrolyte conduit has a length of about 1 mm to about 100 cm and a cross-sectional diameter of about 10 μm to about 3 mm.
り、その長さが導管の約１／２から約１／１００である、請求項１に記載の塩橋
。3. The salt of claim 1, wherein the cross section of the electrolyte chamber is about 3 to about 100 times the cross section of the conduit and its length is about 1/2 to about 1/100 of the conduit. bridge.
１に記載の塩橋。4. The salt bridge according to claim 1, wherein the electrolyte is an aqueous solution, a non-aqueous solution, a solid or a gel.
填剤を含む、請求項１に記載の塩橋。5. The salt bridge according to claim 1, wherein all or part of the conduit or chamber contains an inert filler in addition to the electrolyte.
低い多辺形である断面を有する、請求項１に記載の塩橋。6. The salt bridge of claim 1, wherein the conduit or chamber has a cross section that is circular, elliptical, or polygonal with high or low aspect ratio.
他の形で曲がりくねっている、請求項１に記載の塩橋。7. The salt bridge of claim 1, wherein the conduit or chamber is straight, curved, coiled, spiral, meandering, or otherwise meandering.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36824399A | 1999-08-04 | 1999-08-04 | |
| US09/368,243 | 1999-08-04 | ||
| PCT/US2000/012623 WO2001011349A1 (en) | 1999-08-04 | 2000-05-09 | Sealed salt bridge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003506713A true JP2003506713A (en) | 2003-02-18 |
Family
ID=23450449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001515955A Withdrawn JP2003506713A (en) | 1999-08-04 | 2000-05-09 | Sealed salt bridge |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1210591A4 (en) |
| JP (1) | JP2003506713A (en) |
| AU (1) | AU4830400A (en) |
| WO (1) | WO2001011349A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022481A1 (en) * | 2008-08-28 | 2010-03-04 | Stoian Borissov Mitov | Electrochemical method for nickel and cobalt extraction from oxide ores |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2768135A (en) * | 1953-08-04 | 1956-10-23 | Infilco Inc | Electrolytic cell |
| NL110934C (en) * | 1962-09-21 | |||
| DE2333641C2 (en) * | 1973-04-23 | 1983-07-07 | Harco Electronics Ltd., Winnipeg, Manitoba | Method of making an antimony electrode |
| US4282081A (en) * | 1980-07-10 | 1981-08-04 | Graphic Controls Corp. | Double junction reference electrode |
| CH661128A5 (en) * | 1983-09-07 | 1987-06-30 | Proton Ag | MEASURING PROBE FOR POTENTIOMETRIC MEASUREMENT OF ION CONCENTRATIONS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE. |
| WO1988000700A1 (en) * | 1986-07-10 | 1988-01-28 | Terumo Kabushiki Kaisha | Reference electrode |
| DE3818846C1 (en) * | 1988-06-03 | 1988-12-08 | Schott-Geraete Gmbh, 6238 Hofheim, De | |
| JPH02262046A (en) * | 1989-03-31 | 1990-10-24 | Terumo Corp | Apparatus for measuring concentration of bio-substrate |
| US5173166A (en) * | 1990-04-16 | 1992-12-22 | Minitech Co. | Electrochemical gas sensor cells |
| JPH0663557A (en) * | 1991-07-22 | 1994-03-08 | Takao Miyanoo | Method for preventing reddish water by electrolysis using salt bridge |
| US5147524A (en) * | 1991-07-25 | 1992-09-15 | Broadley-James Corporation | pH sensor |
| US5370783A (en) * | 1991-08-01 | 1994-12-06 | Corrpro Companies, Inc. | Electrode |
| US5490916A (en) * | 1993-04-14 | 1996-02-13 | Battelle Memorial Institute | Capillary reference half-cell |
| US5346606A (en) * | 1993-08-16 | 1994-09-13 | Elsag International N.V. | Electrochemical sensor |
| JP3657401B2 (en) * | 1997-08-21 | 2005-06-08 | 大成建設株式会社 | Heavy metal dissociation method from heavy metal contaminated bottom mud using electrolysis |
-
2000
- 2000-05-09 JP JP2001515955A patent/JP2003506713A/en not_active Withdrawn
- 2000-05-09 EP EP00930493A patent/EP1210591A4/en not_active Withdrawn
- 2000-05-09 AU AU48304/00A patent/AU4830400A/en not_active Abandoned
- 2000-05-09 WO PCT/US2000/012623 patent/WO2001011349A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1210591A1 (en) | 2002-06-05 |
| WO2001011349A1 (en) | 2001-02-15 |
| EP1210591A4 (en) | 2003-03-19 |
| AU4830400A (en) | 2001-03-05 |
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