JP4742727B2 - Indicator electrode used for redox potential measurement - Google Patents

Description

The present invention relates to an indicator electrode used for electrochemical measurement of a liquid, such as an indicator electrode of an oxidation-reduction potential measuring device, particularly for measurement of an oxidation-reduction potential.

であり、酸化還元電位Ｅは次のネルンストの式で示される。
Ｅ＝Ｅｏ＋ｎＦ−ＲＴ １ｎ ［Ｒｅｄ］ ［Ｏｘ］
ここに、Ｅｏ：標準酸化還元電位（［Ｏｘ］＝［Ｒｅｄ］）のときのＥで、系に固有の値）
Ｒ：ガス定数 Ｔ：絶対温度 Ｆ：ファラデー定数
ｎ：反応に関与する電子数
［］：濃度（活量）An electrochemical reduction device that measures the potential and current generated at the interface between the indicator electrode and the solution using a conductive substance as an indicator electrode is, for example, an oxidation-reduction potential measurement device. The oxidation-reduction potential measuring device is equipped with an indicator electrode and a reference electrode of a conductive substance such as metal, and the solution is brought into contact with the indicator electrode to measure the concentration of the electrolyte in the solution and the ion concentration ratio of the oxidant / reductant. To do. That is, when an electrode such as platinum that is not affected by this solution is immersed in a solution containing an oxidant and a reductant, the electrode reaches an equilibrium with a potential with respect to the solution. This potential is called a redox potential.
If the oxidant is Ox and the reductant is Red, the redox reaction is

The oxidation-reduction potential E is expressed by the following Nernst equation.
E = Eo + nF-RT 1n [Red] [Ox]
Here, Eo: E when standard oxidation-reduction potential ([Ox] = [Red]), a value specific to the system)
R: Gas constant T: Absolute temperature F: Faraday constant n: Number of electrons involved in the reaction []: Concentration (activity)

However, the conventional indicator electrode may have a large difference in measured values. For example, when the concentration of the redox substance in the solution is low, or when the properties of the solution are too pure, the redox potential E becomes indefinite, and the stability of the potential measurement is lowered. That is, the measured value when the same solution is measured a plurality of times under substantially the same time under the same conditions is not only constant but also the difference is large. Various liquids such as plant water and industrial water for water quality inspection are the objects of measurement. However, depending on the type of solution, there is a problem that the measurement is stable and accurate.
JP-A-11-118756

An object of the present invention is to solve is to overcome this drawback, regardless of the type of solution, such as oxidation-reduction potential measuring device capable of accurate measurement of a stable potential, used in oxidation-reduction potential measurement The present invention relates to an indicator electrode. In particular, the present invention provides an indicator electrode capable of measuring an accurate and stable potential not only for a solution having a high concentration of redox material but also for a solution having a low concentration of redox material or a pure solution.

The present invention takes the following means to solve the above problems. That is, in the indicator electrode made of a metal conductive material used for measuring the oxidation-reduction potential generated at the interface with the liquid, the indicator electrode is subjected to polishing treatment on the outer peripheral surface including the tip portion, and the surface roughness characteristics are the center according to JIS B0601-1994. The linear arithmetic average roughness Ra (μm) is 0.50 or less, and the outer peripheral surface of the round bar including the rounded tip as a whole is integrated with the tip and has low buffering force such as biological fluid. It is exposed so as to be able to come into contact with the liquid, and a hollow hollow portion is formed in the longitudinal direction.

In addition, in the indicator electrode of the metal conductive material used for measuring the oxidation-reduction potential generated at the interface with the liquid, the indicator electrode is subjected to polishing treatment on the outer peripheral surface including the tip portion, and the surface roughness characteristics are set to the maximum height according to JIS B0601-1994. Ry (μm) is 1.70 or less, and a round bar-shaped outer peripheral surface including a rounded tip formed integrally with the tip is in contact with a liquid with a low buffering force such as a biological fluid. It is exposed as possible, and a hollow hollow part is formed in the longitudinal direction.

In addition, in the indicator electrode of the metal conductive material used for measuring the oxidation-reduction potential generated at the interface with the liquid, the indicator electrode is subjected to polishing treatment on the outer peripheral surface including the tip portion, and the surface roughness characteristics are ten points according to JIS B0601-1994. An average roughness Rz (μm) of 1.00 or less, and a round bar-shaped outer peripheral surface including a rounded tip formed integrally with the tip is seamless, and has a low buffering force such as biological fluid. Are exposed so as to be in contact with each other, and a hollow portion is formed in the longitudinal direction.

According to the indicator electrode of the present invention whose surface roughness is below the standard, not only a solution having a high redox substance concentration but also a solution having a low redox substance concentration or a solution whose properties are too pure has a stable potential. Measurement is possible. Therefore, it is possible to measure an accurate and stable potential not only for a solution having a high concentration of redox substances such as drainage but a high buffering capacity, but also for a biological fluid such as saliva or a solution having a low buffering capacity such as pure water.

The best mode for carrying out the invention of the indicator electrode according to the present invention will be described. One electrochemical measuring device that uses a conductive substance as an indicator electrode and measures the potential and current generated at the interface between the indicator electrode and the solution is a redox potential measuring device that measures the redox potential of the solution. Hereinafter, the oxidation-reduction potential measuring device will be described as an example. As shown in the conceptual diagram of FIG. 1, the oxidation-reduction potential measuring device 1 includes an indicator electrode 2 and a reference electrode 3. The indicator electrode 2 and the reference electrode 3 are immersed in a solution 5, and a solution 5 is placed on the surface of the indicator electrode 2. Then, the electro-oxidation reduction potential generated at the interface between the indicator electrode 2 and the solution 5 is measured. The indicator electrode 2 is made of a conductive material such as a metal that is not affected by the solution. Inert metals such as platinum and gold are often used, but are not limited thereto. The reference electrode 3 is made of a metal such as a silver-silver chloride electrode. An oxidation-reduction potential measuring apparatus having such a configuration is known.

When a conventional indicator electrode is observed closely, it can be seen that there are innumerable small irregularities on the surface of the indicator electrode. There are various irregularities such as small irregularities of the material before processing and scratches generated during the manufacturing process. These irregularities include those that can be seen with the naked eye, those that are difficult to see, and those that are not visible. As a result of various experiments and researches, the present inventor has found that the micro-level surface roughness characteristics of the indicator electrode are related to the stability and accuracy of the potential measurement. In particular, when the concentration of the redox material in the solution is low or the properties of the solution are too pure, it has been confirmed that the surface roughness characteristics of the indicator electrode affect the stability of the potential measurement. That is, when the surface roughness of the solution that contacts the indicator electrode surface exceeds a certain standard and becomes excessive, the measured value is not constant, that is, the potential measurement becomes unstable. However, when the roughness of the surface of the indicator electrode is below a certain standard and the surface roughness is not excessive, the potential measurement is stable. One reason is that excessive roughness on the surface of the indicator electrode generates a local battery, which inhibits stable potential measurement.

In the indicator electrode according to the present invention, the roughness of the surface of the indicator electrode is adjusted. That is, the surface roughness of the indicator electrode is set to a certain standard or less, and the surface roughness characteristics are regulated. The surface roughness of the indicator electrode is based on the centerline arithmetic average roughness Ra, the maximum height Ry, and the ten-point average roughness Rz of JIS B0601-1994. The standard of the surface roughness is that the center line arithmetic average roughness Ra (μm) is 0.50, the maximum height Ry (μm) is 1.70, and the ten-point average roughness Rz (μm) is 1.00. It is. One of the surface roughnesses may be less than the standard. By making the surface roughness of the indicator electrode below this reference, the potential measurement is stabilized. Further preferable criteria for the surface roughness are a center line arithmetic average roughness Ra (μm) of 0.40, a maximum height Ry (μm) of 1.50, and a ten-point average roughness Rz (μm) of 0.90. is there. Similarly, it is only necessary that one of the surface roughnesses of the indicator electrode is below the reference. By making the surface roughness of the indicator electrode below this reference, the potential measurement is further stabilized. Accurate and stable potential measurement is possible not only for solutions having a high concentration of redox substances and therefore having a high buffer capacity, but also for solutions having a low buffer capacity.

The definitions of the center line arithmetic average roughness Ra, the maximum height Ry, and the ten-point average roughness Rz (JIS B0601-1994) of the surface roughness are as follows. The centerline arithmetic average roughness Ra is a value obtained by extracting a reference length from the roughness curve in the direction of the average line, and summing and averaging the absolute values of deviations from the average line of the extracted portion to the measurement curve. The maximum height Ry is the sum of the height from the average line of the extracted portion to the highest peak and the depth to the lowest valley bottom from the roughness curve in the direction of the average line. The ten-point average roughness Rz is extracted from the roughness curve by the reference length in the direction of the average line, and the average value of the absolute values of the altitudes of the peaks from the average line of the extracted part to the fifth highest peak, It is the sum of the absolute values of the altitudes of the bottoms of the valleys from the lowest bottom to the fifth.

The surface roughness of the indicator electrode such as platinum or gold is adjusted by precise polishing. In order to make the indicator electrode have a surface roughness equal to or less than the above-mentioned standard by mechanical precision polishing, a known polishing method such as lapping or polishing can be selected, but the polishing method and apparatus are not limited. For example, loose abrasive particles of 1 μm to several tens of μm are mixed with a lubricant to form a powder material, and this powder agent is supplied to a rotating surface plate and an indicator electrode (metal piece) is pressed to wrap by relative movement of these three members Processing. Further, if polishing is performed using a fine abrasive of 1 μm or less, predetermined polishing is easy. It can also be polished with a polishing cloth.

The indicator electrode may have any shape such as a flat plate shape, a square rod shape (not shown). The indicator electrode 2 shown in FIGS. 14 and 15 has a round bar shape integrally formed without a joint with the rounded tip portion 10, and the outer peripheral surface including the tip portion 10 is polished. Polishing of the base end portion 11 of the indicator electrode is optional. Since the indicator electrode 2 is formed integrally with the distal end portion 10 without a joint, and is round bar-like and the entire outer peripheral surface is a curved surface, the outer peripheral surface can be uniformly and precisely polished. Further, the indicator electrode 2 shown in FIG. 15 has a hollow portion 12 formed in the longitudinal direction. The hollow portion 12 can reduce the cost of expensive materials such as platinum and gold. The solution contacts the indicator electrode 2, that is, the outer peripheral surface of the polished indicator electrode 2. However, since the solution does not contact the hollow portion 12, it is not necessary to polish the inner peripheral surface of the hollow portion 12.

Here, the polishing of the indicator electrode disclosed by the prior art (Japanese Patent Publication No. 11-118756) will be described. Sure, it is shown that the surface of the indicator electrode is polished in the publication, but it may cause a film such as an oxide film on the indicator electrode surface when the number of times of contact with the solution increases, such as repeated potential measurement. Therefore, it is only polishing for removing such a film and returning the surface of the indicator electrode to its original state. There is no awareness of the adjustment of the surface roughness characteristic of the indicator electrode and precise polishing. In the present invention, the surface roughness of the indicator electrode is adjusted at a micro level by precision polishing, and the surface roughness is set below a certain standard. As a result, stable potential measurement is possible for the first time, and the technical significance is different from that of the prior art even in the case of polishing.

If the solution remains on the surface of the indicator electrode after measuring the potential of the solution, the stability of the subsequent potential measurement of the solution may be hindered. This is because the remaining solution may contaminate the next solution. When the buffer capacity of the remaining solution is high, or when the buffer capacity of the solution to be measured next is low, the contamination is particularly likely to occur. Therefore, it is preferable to measure the potential of the next solution after the measurement by washing the indicator electrode and sufficiently removing the attached residual solution. In the present invention, since the surface roughness of the indicator electrode is below a certain standard and the surface roughness is not excessive, the residual solution adhering to the indicator electrode surface is reliably removed by washing. Therefore, the potential measurement instability due to the residual solution on the surface does not occur. Further, purified water (pure water) is sufficient for removing the residual solution, and it is not necessary to use a cleaning chemical. When measuring the potential of a solution having a high buffering capacity such as drainage, the potential measurement is usually not unstable because the influence of contamination by the remaining solution is relatively small.

Electrochemical measurement of a solution can be stably performed by various measuring devices such as an oxidation-reduction potential measuring device using an indicator electrode whose surface roughness is set to the standard or less. Stable potential measurement is possible not only for a solution having a high buffer capacity but also for a solution having a low buffer capacity. Solutions with low buffering capacity include saliva, blood, biological fluids including urine, drinking water, purified water (pure water) and the like.

Examples according to the present invention will be described below together with comparative examples. In the examples and comparative examples, the indicator electrode is in the shape of a round bar with a platinum tip rounded. There is no hollow part inside (see FIG. 14). It is 40 mm long and 2 mm in diameter. The indicator electrodes (4) to (9) were subjected to precise polishing treatment by lapping on the surface. That is, lapping was performed using a powder material in which free abrasive grains of about 1 μm to several tens of μm were mixed with a lubricant, and further lapping was performed with a fine abrasive of μm or less. A commercially available polishing machine was used for lapping. Note that some indicator electrodes with particularly small surface roughness were finished with an abrasive cloth. As the polishing cloth for finishing, “Pearl Cloth” (manufactured by Pearl Research Institute) was used. The surface roughness of the indicator electrodes (1) to (9) is different, and the surface roughness is determined based on the center line arithmetic average roughness Ra (μm), the maximum height Ry (μm), and the ten-point average roughness Rz (μm). (Both measured according to JIS B0601-1994). Of the comparative examples (indicating electrodes (1) to (3)) that are not the subject of the present invention, the indicating electrode (1) is unpolished and the indicating electrodes (2) and (3) are not sufficiently polished. The reference electrode is a silver-silver chloride electrode.

The sample solution was (A) human saliva, (B) purified water (pure water), (C) KCl (1 mol), (D) Fe (CN) ₆ ^co- / Fe (CN) ₆ ^4- system standard solution There are four types. Sample solutions (A) and (B) are solutions with low buffer capacity, and sample solutions (C) and (D) are solutions with high buffer capacity. The sample solution was brought into contact with the surfaces of the indicator electrode (1) to indicator electrode (9), and the oxidation-reduction potential (unit: mV) was measured. Three measurements were taken for the same sample solution. Currently, many manufacturers manufacture and sell oxidation-reduction potential measuring devices. The indicator electrodes (1) to (9) were replaced with commercially available oxidation-reduction measuring devices, and the oxidation-reduction potential of the sample solution was measured.

According to Table 1 and the graphs of FIGS. 2 to 13, when the sample solution (C) (D) having a high buffer capacity is observed, it is determined by the indicator electrodes (4) to (9) of the example that is the object of the present invention. The measured values and the measured values by the indicator electrodes (1) to (3) of the comparative example which is not the subject of the present invention are almost the same, and both are basically the same. That is, in the case of a solution having a high buffering capacity, it is shown that stable potential measurement is possible regardless of the surface roughness of the indicator electrode, that is, the presence or absence of polishing treatment and the degree of polishing. Looking at the sample solutions (A) and (B) having a low buffering capacity, there are considerable variations in the measured values of the indicator electrodes (1) to (3) that are not the subject of the present invention. Moreover, the difference between the measured values is quite large, and it is difficult to measure a stable potential. This is consistent with the pointed out as a drawback of the conventional indicator electrode.

In the indicator electrodes (4) to (9) of the embodiment, the measurement of the potential with respect to all the sample solutions is stable. That is, any one of Ra, Ry, and Rz is based on the center line arithmetic average roughness Ra (μm) 0.50, the maximum height Ry (μm) 1.70, and the ten-point average roughness Rz (μm) 1.00. The indicator electrodes (4) to (9), one of which is below the reference, all have stable potential measurements. More preferably, the center line arithmetic average roughness Ra (μm) is 0.40, the maximum height Ry (μm) is 1.50, and the ten-point average roughness Rz (μm) is 0.90, and Ra, Ry, Rz Any one of the indicator electrodes (5) to (9) below this reference is more stable in potential measurement. In contrast, the indicator electrodes (1) to (3) of the reference example are unstable in measuring the potential with respect to the sample solution having a low buffer capacity. Thus, the measurement of the potential by the indicator electrode of the present invention is effective even for a solution having a low buffer capacity, and it is possible to measure the potential accurately and stably.

The graphs of FIGS. 2 to 5 show the measurement results of the potentials of the sample solutions (A), (B), (C), and (D) using indicator electrodes having different center line arithmetic average roughness Ra (the unit of potential on the vertical axis is mV). The unit of surface roughness on the horizontal axis is μm). According to this, the indicator electrode polished with the center line arithmetic average roughness Ra (μm) of 0.50 or less has stable potential measurements for four types of sample solutions. Further, the indicator electrode having Ra (μm) of 0.40 or less has a more stable potential measurement. On the other hand, the poorly polished indicator electrode having a center line arithmetic average roughness Ra (μm) exceeding 0.50 is stable in measuring the potential with respect to the sample solution (C) (D), but the sample solution (A) The potential measurement for (B) is unstable. In the graphs of FIGS. 2 to 13, small white circles (◯) are measured values by the indicator electrode that is the object of the present invention, small black circles (●) are measured values by the indicator electrode that is not the subject of the present invention, and are poorly polished. A small double circle (◎) represents a value measured by a conventional indicator electrode (commercial indicator electrode).

The graphs of FIGS. 6 to 9 show the measurement results of the potentials of the sample solutions (A), (B), (C), and (D) using the indicator electrodes having different maximum heights Ry. According to this, the measurement of the potential with respect to four types of sample solutions is stable for the indicator electrode whose maximum height Ry (μm) is polished to 1.70 or less. The indicator electrode having Ry (μm) of 1.50 or less is further stable in potential measurement. On the other hand, an insufficiently polished indicator electrode having a maximum height Ry (μm) exceeding 1.70 is stable in measuring the potential with respect to the sample solutions (C) and (D), but with respect to the sample solutions (A) and (B). Potential measurement is unstable.

The graphs of FIGS. 10 to 13 show the measurement results of the potentials of the sample solutions (A), (B), (C), and (D) using indicator electrodes having different ten-point average roughness Rz. According to this, the measurement of the potential with respect to the four types of sample solutions is stable for the indicator electrode whose 10-point average roughness Rz (μm) is polished to 1.00 or less. In addition, the indicator electrode having a 10-point average roughness Rz (μm) of 0.90 or less has a more stable potential measurement. On the other hand, an insufficiently polished indicator electrode having a ten-point average roughness Rz (μm) exceeding 1.00 is stable in measuring the potential with respect to the sample solution (C) (D), but the sample solution (A) (B ) Is unstable.

In the conventional oxidation-reduction potential measuring device, for example, when the measurement range is −1500 mV to +1500 mV, −1999 mV to +1999 mV, an allowable range of 0.2 to 0.5% is set for the measurement accuracy of reproduction. Accordingly, in this case, measurement errors in the range from a minimum of 60 mV to a maximum of 150 mV are allowed in the former, and in the range from a minimum of 79 mV to a maximum of 199 mV in the latter. In the case of the indicator electrode according to the present invention, as shown in Table 1 and graph, the maximum measurement accuracy of reproduction was 15 mV or less even in saliva having a low buffering capacity. More preferably, the reproducible measurement accuracy is 5 mV or less at maximum. Similar results were obtained for the indicator electrode having the hollow portion 12 (see FIG. 15).

As described above, the indicator electrode according to the present invention improves the measurement accuracy even for a solution having a low buffer capacity, and enables accurate and stable potential measurement. Therefore, for example, by measuring the saliva of the living body, the state of the oxidant and the reductant in the body can be confirmed, which can contribute to maintenance of health management and can be widely used in industry.

It is a conceptual block diagram of the conventional oxidation-reduction potential measuring device. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in centerline arithmetic mean roughness Ra. The sample solution is human saliva. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in centerline arithmetic mean roughness Ra. The sample solution is purified water. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in centerline arithmetic mean roughness Ra. The sample solution is KCl (1 mol). It is a graph which shows the measurement result by the indicator electrode from which surface ancestry differs in centerline arithmetic mean roughness Ra. The sample solution is Fe (CN) ₆ ³⁻ / Fe (CN) ₆ ⁴ -based standard solution. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in maximum height Ry. The sample solution is human saliva. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in maximum height Ry. The sample solution is purified water. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in maximum height Ry. The sample solution is KCl (1 mol). It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in maximum height Ry. The sample solution is Fe (CN) ₆ ³⁻ / Fe (CN) ₆ ⁴ -based standard solution. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in ten-point average roughness Rz. The sample solution is human saliva. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in ten-point average roughness Rz. The sample solution is purified water. It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in ten-point average roughness Rz. The sample solution is KCl (1 mol). It is a graph which shows the measurement result by the indicator electrode from which surface roughness differs in ten-point average roughness Rz. The sample solution is an Ee (CN) ₆ ³⁻ / Fe (CN) ₆ ⁴ system standard solution. It is an enlarged front view of an indicator electrode. It is an expanded sectional view of another indicator electrode.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Oxidation reduction potential measuring apparatus 2 Indicator electrode 3 Reference electrode 5 Sample solution 6 Electrometer 7 Indicator electrode side lead wire 9 Reference electrode side lead wire 10 Tip end portion of indicator electrode 11 Base end portion 12 of indicator electrode Hollow portion

Claims (4)

In the indicator electrode of the metal conductive material used for measuring the oxidation-reduction potential generated at the interface with the liquid, the outer peripheral surface including the tip is subjected to polishing treatment, and the surface roughness characteristics are calculated as the centerline arithmetic average roughness Ra according to JIS B0601-1994. (Μm) is 0.50 or less, and the outer peripheral surface of the round bar that includes the rounded tip as a whole is seamlessly connected to the tip so that it can come into contact with a liquid with low buffering force such as biological fluid. An indicator electrode that is exposed and has a hollow portion formed in the longitudinal direction. In the indicator electrode of the metal conductive material used for measuring the oxidation-reduction potential generated at the interface with the liquid, the outer peripheral surface including the tip is subjected to polishing treatment, and the surface roughness characteristics are the maximum height Ry (μm) according to JIS B0601-1994. 1.It is 1.70 or less, and the outer peripheral surface of the round bar shape including the tip portion rounded as a whole formed seamlessly with the tip portion is exposed so as to be in contact with a low buffering force liquid such as a biological fluid, An indicator electrode in which a hollow portion of the bore is formed in the longitudinal direction. In the indicator electrode of the metal conductive material used for measurement of the oxidation-reduction potential generated at the interface with the liquid, the outer peripheral surface including the tip is subjected to polishing treatment, and the surface roughness characteristics are expressed in ten-point average roughness Rz (according to JIS B0601-1994) μm) is 1.00 or less, and the outer peripheral surface of the round bar that includes the rounded tip as a whole is seamlessly connected to the tip, and is exposed so that it can come into contact with a liquid with low buffering force such as biological fluid. An indicator electrode in which a hollow portion of the bore is formed in the longitudinal direction. The indicator electrode according to claim 1, 2 or 3, wherein a hollow portion of the bore is formed in the indicator electrode in the longitudinal direction.

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