KR101453286B1 - Verification Methods of Reference Electrode and Glass Electrode - Google Patents

Verification Methods of Reference Electrode and Glass Electrode Download PDF

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KR101453286B1
KR101453286B1 KR1020140056240A KR20140056240A KR101453286B1 KR 101453286 B1 KR101453286 B1 KR 101453286B1 KR 1020140056240 A KR1020140056240 A KR 1020140056240A KR 20140056240 A KR20140056240 A KR 20140056240A KR 101453286 B1 KR101453286 B1 KR 101453286B1
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electrode
water quality
sensor
potential difference
measurement
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길주형
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길주형
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    • 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
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • 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
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301—Reference electrodes
    • 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
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
    • 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
    • G01N27/416—Systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water

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Abstract

The present invention relates to a reference electrode for verifying abnormality of each electrode of a water quality sensor for measuring a hydrogen ion concentration of water used in various fields and a method of verifying the measurement electrode. More particularly, A reference electrode and a reference electrode are formed on the second terminal of the potential difference measuring device, and a reference electrode and a reference electrode are separately formed in the second terminal of the potential difference measuring device, The reference electrode of the water quality measurement sensor comprising the composite electrode provided with the electrodes separated from each other is connected to the first electrode and the reference electrode of the water quality measurement sensor is immersed in the first sample after the verification electrode and the water quality measurement sensor are stabilized, It is verified whether or not the reference value of the reference electrode is abnormal by confirming that the indication value of the measuring apparatus is included in the range of -40 mV ± 5 mV, A test electrode of a water quality measuring sensor comprising a half electrode or a composite electrode to be verified is connected to the second terminal of the potential difference measuring apparatus and the test electrode is washed and immersed in the second sample together with the water quality measuring sensor After confirming that the measured value of the probe electrode and the water quality sensor is stabilized, verifying whether the indication value of the potential difference measuring apparatus included in the range of + 130 mV ± 10 mV includes the abnormality of the measuring electrode; It is possible to grasp the impurities which interfere with the hydrogen ion potential and the ions which influence the abnormality in the measured value, so that it is possible to perform on-site diagnosis, thereby improving the ability to cope with the field.

Description

[0001] The present invention relates to a method of verifying a reference electrode and a measurement electrode,

The present invention relates to a method of verifying a reference electrode and a measuring electrode, and more particularly, to a method of verifying a reference electrode and a measuring electrode, And to a method of verifying a reference electrode and a measuring electrode that can easily identify an impurity characteristic that affects the determination of an anomaly and a hydrogen ion concentration.

Generally, the hydrogen ion concentration (pH) refers to the measurement of the acidity or basicity of an aqueous solution. The acidity and basicity of the aqueous solution are determined by the relative number of H + and OH- ions present. The acid solution has a large number of relative H + ions and the basic solution has a large number of OH- ions. The acid dissociates to generate H + ions or react with water to form H + ions. On the other hand, the base dissociates to form OH - ions or react with water to produce OH - ions.

The following are the various industrial fields that require measurement of pH (pH).

(1) Fibers, Dyeing Sector: In the textile industry, the measurement of pH is very important in the process of determining how fibers respond to something like sweat.

(2) Paper and pulp fields: pH is controlled in the process of decomposition and bleaching in the paper making process, and the durability and dyeing speed of the paper also depend on the pH.

(3) Chemistry: pH control of samples is considered very important to optimize reaction conditions and prevent unwanted side reactions.

(4) Metals and minerals refining: It is necessary to adjust the pH when extracting specific metals from ores or mixed metals.

(5) Electrical and electrochemical fields: pH control is important in determining the quality of products by plating or etching the metal surface or adjusting the pH in the battery manufacturing process.

(6) Electric power, natural gas: Boiler water used in large boiler operation such as thermal power plant is important as a check area to prevent pipe corrosion.

(7) Pharmaceuticals and cosmetics: In the pharmaceutical and cosmetic industries, it is important to measure the pH to check the chemical half of the production process.

(8) Field of Aquaculture: The pH balance of seawater has a great influence on the marine biota and measurement of water quality in the farm is very important.

(9) Food and brewing fields: There are many processes involved in the production of foods and beverages such as bread, liquor, beer, soy sauce, miso, cheese, and dairy products.

(10) Agriculture, livestock: The pH measurement of soil and water is very important for increasing productivity and controlling growth of crops.

(11) Sewage Sector: Control of pH is needed to optimize bacterial activity in the sludge as well as at each treatment and discharge after treatment at the sewage treatment plant.

(12) Medical field: In the medical field, the pH of the reagent is measured as well as the pH of the blood, stomach fluid and urine for the purpose of research, experimentation and therapy.

(13) Environmental pollution field: The measurement of pH is very important when the effluent needs to be treated to meet the standards applicable to effluent effluent at each factory.

(14) Printing field: This is because it greatly affects the degree of drying of the ink, the contrast of the color, and the color sharpness in printing such as photographs.

(15) Other areas: Scientific criminal investigation by police Science provides useful information for determining the time of death of a victim.

A method for verifying the abnormality of a conventional hydrogen ion concentration (pH) electrode is to measure a pH meter by combining a hydrogen ion concentration (pH) electrode and amplify (amplify) a minute electromotive force generated in the glass electrode. (Operation unit) to the pH value and display it by Digital or Analogue (instruction unit).

And, the buffer solution (buffer solution) is a reference solution made to maintain a constant pH for a small amount of contaminants. Although the pH value of the buffer solution is said based on 25 ° C, the actual pH value varies depending on the temperature.

As a result, the pH measurement is highly sensitive and should not be a simple process but a careful calibration and storage and solution of various parameters.

In particular, the pH measurement in the field is very difficult and different pH electrodes should be used for each application. Also, it is necessary to calibrate the pH meter regularly. In this case, the pH meter and the pH electrode are connected to each other to calibrate or verify the pH electrode.

However, this is very wrong and the pH electrode and pH meter are separate issues in pH measurement. All pH meters have instrumental errors and can not be regarded as perfect instruments in the manufacturing process. Therefore, it is very urgent to have an accurate, simple, and easy method for verifying the abnormality, lifetime, and verifying of the measurement electrode and the reference electrode of the pH electrode.

1. Registration number 20-0438336 (Water quality sensor management device)

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the problems of the prior art as described above, and it is an object of the present invention to provide a water quality sensor for measuring hydrogen ion concentration of water and to determine whether a reliable measurement value can be obtained And a method of verifying the reference electrode and the measurement electrode.

Another object of the present invention is to separately measure the reference electrode and the measurement electrode of the water quality measurement sensor and to separately determine whether each electrode is abnormal so as to check whether the error or abnormality of the meter or the pH value is normal regardless of the solution .

Another object of the present invention is to make it possible to detect the impurities which interfere with the hydrogen ion potential and the ions which influence the abnormality in the measured value by using the proved water quality measuring sensor, thereby enabling the field diagnosis.

In order to accomplish the above object, the present invention provides a method of measuring a potential difference, comprising the steps of: connecting a first electrode of a potential difference measurement apparatus to a first electrode of a potential measurement apparatus, A reference electrode of a water quality measuring sensor including a reference electrode and a measuring electrode formed separately from each other or a composite electrode having a reference electrode and a measuring electrode separated from each other is connected to the reference electrode and the water quality measuring sensor is connected to a buffer solution, Solution. Then, after the measurement values of the verification electrode and the water quality measurement sensor are stabilized, it is verified that the indication value of the potential difference measurement device included in the range of -40 mV ± 5 mV is verified as the abnormality of the reference electrode After the verification of the reference electrode, a half-electrode or a composite electrode to be verified is applied to the second terminal of the potential difference measuring device The test electrode is washed and then immersed in a second sample formed with a buffer solution of 4.00 pH or 4.01 pH together with a water quality measurement sensor. Then, the measurement value of the verification electrode and the water quality measurement sensor are stabilized And verifying whether or not an abnormality of the measuring electrode is confirmed by confirming that the indication value of the measuring device for potential difference displayed after the measurement is included in the range of + 130 mV ± 10 mV.

As described above, according to the present invention, it is possible to judge whether a reliable measurement value can be obtained by judging whether the measuring electrode is normally operating or not, which is the standard of the water quality sensor for measuring the hydrogen ion concentration of water.

In addition, it is possible to separately judge the abnormality of each electrode by separately measuring the reference electrode and the measurement electrode of the water quality sensor, and it is possible to check whether the error or abnormality of the meter or pH value is normal regardless of the solution. It is effective to judge a high water quality measurement sensor.

In addition, by using the proven water quality measurement sensor, it is possible to identify impurities that interfere with the hydrogen ion potential and ions that affect the measured value, thereby improving on-site capability by enabling field diagnosis .

FIG. 1 is a schematic diagram for a reference electrode verification of a half-electrode according to the present invention.
FIG. 2 is a configuration diagram for a measurement electrode verification of a half-electrode according to the present invention,
FIG. 3 is a schematic view for a reference electrode verification of a composite electrode according to the present invention;
FIG. 4 is a schematic diagram for a reference electrode verification of a composite electrode according to the present invention. FIG.
5 and 6 are cross-sectional views illustrating a silver-standard electrode and a gamma electrode of a verification electrode according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG.

As shown in FIGS. 1 to 4, the method for verifying the reference electrode and the measuring electrode of the present invention includes a potentiometric measurement device 10 for measuring a measurement value, a measurement device 10 connected to the potentiometric measurement device 10, A water quality measurement sensor 30 formed with a reference electrode 31 connected to the potential difference measurement device 10 and a measurement electrode 32; The first and second samples 40 and 50 for generating a potential difference in the sensor 30 are configured for the verification method.

The verification method may include a continuous method of verifying the measurement electrode 32 after the verification of the first reference electrode 31 according to a method of verifying the water quality measurement sensor 30, A single method, and a single method in which only the third measuring electrode 32 is independently verified.

First, constitutional features for the verification method will be described as follows.

1. A continuous method for verifying a measurement electrode (32) after verification of a reference electrode (31) comprises:

First, the first terminal 11 of the potential difference measuring apparatus 10 is constituted by connecting a verification electrode 20 which generates only a potential difference to a measurement object sample and indicates an absolute value of measurement as '0'.

The reference electrode 31 and the measuring electrode 32 are separately formed in the second terminal 12 of the potential difference measuring apparatus 10 and the reference electrode 31 and the measuring electrode 32 And the reference electrode 31 of the water quality measuring sensor 30, which is composed of the separated composite electrode 30b.

The verification electrode 20 and the water quality measurement sensor 30 are immersed in the first sample 40 and then measured by the potential difference measuring device 30 after the measurement values of the verification electrode 20 and the water quality measurement sensor 30 are stabilized 10) is included in the range of -40 mV ± 5 mV to verify the abnormality of the reference electrode (31).

After the verification of the reference electrode 31, the second terminal 12 of the potential difference measuring apparatus 10 is connected to the measuring electrode 30 of the water quality measuring sensor 30, which is composed of the half-electrode 30a or the composite electrode 30b to be verified. (32).

After the probe 20 is cleaned and immersed in the second sample 50 together with the water quality measurement sensor 30, the measured values of the probe 20 and the water quality measurement sensor 30 are stabilized and displayed It is configured to check whether the indication of the potential difference measuring apparatus 10 is included in the range of + 130 mV ± 10 mV to verify the abnormality of the measuring electrode 32.

2. A reference electrode only verification method for verifying the reference electrode 31 singly;

First, the first terminal 11 of the potential difference measuring apparatus 10 is constituted by connecting a verification electrode 20 which generates only a potential difference to a measurement object sample and indicates an absolute value of measurement as '0'.

The reference electrode 31 and the measuring electrode 32 are separately formed in the second terminal 12 of the potential difference measuring apparatus 10 and the reference electrode 31 and the measuring electrode 32 And the reference electrode 31 of the water quality measuring sensor 30, which is composed of the separated composite electrode 30b.

The verification electrode 20 and the water quality measurement sensor 30 are immersed in the first sample 40 and then measured by the potential difference measuring device 30 after the measurement values of the verification electrode 20 and the water quality measurement sensor 30 are stabilized 10) is included in the range of -40 mV ± 5 mV to verify the abnormality of the reference electrode (31).

3. A measurement electrode-only verification method for verifying the measurement electrode (32) alone;

The second terminal 12 of the potential difference measuring apparatus 10 is constructed by connecting the measuring electrode 32 of the water quality measuring sensor 30 including the half electrode 30a or the composite electrode 30b to be inspected .

After the probe 20 is cleaned and immersed in the second sample 50 together with the water quality measurement sensor 30, the measured values of the probe 20 and the water quality measurement sensor 30 are stabilized and displayed It is configured to check whether the indication of the potential difference measuring apparatus 10 is included in the range of + 130 mV ± 10 mV to verify the abnormality of the measuring electrode 32.

In general, the potential difference measuring apparatus 10 is a device for measuring a standard precision electric potential in a continuous method as described above or a stand-alone method of verifying only the reference electrode 31 or the measuring electrode 32, The first and second terminals 11 and 12 for connecting the terminals connected to the display unit 32 are formed and a display window 13 for displaying measured values is formed.

The verification electrode 20 generates a potential difference for measurement after being settled in the water quality measurement sensor 30 and the first and second samples 40 and 50. The verification electrode 20 is not affected by temperature or concentration, Quot; 0 ".

5 and 6, the verifying electrode 20 includes a gamma electrode 21 and a silver-standard electrode 22 as follows.

1. The gamma electrode 21 has Hg, Hg 2 Cl 2 , and Hg 2 Cl 2 in an inner tube 21 b having a mercury layer 21 a formed thereunder. A platinum wire 21d is immersed in the inner mixture liquid 21c filled with KCL and the inner tube 21b is filled with a KCL solution or a KCL crystal and a glass body 21f having a liquid- 21e.

2. The silver electrode 22d is immersed in an internal liquid 22c filled with a KCl and AgCl mixed solution into the sensor body 22b having the sensing part 22a formed at the lower part thereof And a silver-standard electrode 22 to be installed.

The sensor body 22b of the silver-standard electrode 22 is formed with an injection port 22e for filling the internal liquid 22c to communicate with the internal space of the sensor body 22b, And a cap 22f that can be opened and closed is fastened.

At this time, cables 21d 'and 22d' are connected to the platinum wire 21d and the Ag wire 22d, respectively, and the cables 21d 'and 22d' (11).

The reference electrode 31 is contained in the half electrode 30a and the composite electrode 30b of the water quality measurement sensor 30 through a porous film 31b formed in the reference glass body 31a, (Ag / Agcl reference junction: 31d), which is immersed in a gel (gal) or a solution of the internal replenishment solution (3 mol to 3.5 mol of KCl saturated solution: 31c).

The measurement electrode 32 in the half electrode 30a and the composite electrode 30b of the water quality measurement sensor 30 is disposed inside a measurement glass body 32a having a hemispherical glass diaphragm 32a ' Ag / Agcl wire 32c is immersed in the internal electrolyte solution (0.1 mol to 0.5 mol of HCl: 32b).

The measuring glass body 32a of the composite electrode 30b is inserted into the reference glass body 31a while being separated from each other and the measurement glass body 31a of the composite electrode 30b is inserted into the reference glass body 31a. A temperature sensor 31b 'for checking the temperature of the substrate W is formed.

In addition, the cable 31d 'and the cable 32c' are connected to the internal conductor (Ag / Agcl reference junction 31d) and the Ag / Agcl wire 32c of the water quality sensor 30, respectively, And the cable 31d 'and the cable 32c' to the second terminal 12, respectively.

In addition, the first sample 40 may be composed of a buffer solution or a water-soluble solution, and the buffer solution may be composed of 1 pH to 14.00 pH or 4.01 pH buffer solution.

On the other hand, it is preferable that the second sample 50 is composed of 4.00 pH or 4.01 pH buffer solution.

The operation and effect of the present invention constructed as described above will be described below.

First, the method of verifying the water quality measurement sensor 30 includes a continuous method for verifying the measurement electrode 32 after verification of the reference electrode 31, a stand-alone method for verifying only the reference electrode 31 alone, ) Can be categorized into a single method in which only a single verification is performed. In the present invention, a continuous verification method will be described as an example.

A preparation process for verifying the reference electrode 31 and the measurement electrode 32 will be described below with reference to the water quality measurement sensor 30 including the half electrode 30a and the composite electrode 30b.

1. The potential difference measuring apparatus 10 always puts the switch in the OFF state while not measuring the electromotive force.

The hydrogen ion concentration is obtained by subtracting the difference between the standard pH solution and the reference electrode 31 and the measurement electrode 32 of the water quality measurement sensor 30 in the first and second samples 40 and 50 to obtain the Nernst formula , The potential difference measuring apparatus 10 is practically used as a device for measuring the difference between two potentials.

2. The method of managing the water quality measuring sensor 30 to be verified must be cleaned before and after use. A preferable washing method is to use a water quality measuring sensor 30, which supports the beaker below the water quality sensor 30, (30) is washed down, and the water droplets that are attached are absorbed by gently pulling soft paper. At this time, take care not to hit or scratch the glass of the water quality sensor 30, and if it is finished, immerse it in water or an appropriate buffer solution.

Particularly, even if the water quality measuring sensor 30 is a new product or used, the water quality measuring sensor 30 which has been dried and stored is immersed in the buffer solution for about 2 hours or more overnight to be used after being stabilized.

The water quality measuring sensor 30 is immersed in a phosphate buffer solution having pH, when it is intended to be used for measuring the hydrogen ion concentration below pH 9. For use only in alkaline solutions, immerse in boric acid solution. Sensitive alkaline solution (pH> 10) will damage the glass membrane and efforts should be made to shorten the immersion time.

If the hydrogen ion concentration measurement result exceeds 11 pH, rinse with 0.1 M HCl as soon as the measurement is completed, and immerse in water or a suitable buffer solution. When using in a solvent (including chromium sulfuric acid) having a dehydrating ability other than water, it is preferable to avoid time-consuming and immerse in water to stabilize after use.

3. The sensing electrode 20 is immersed in water, and when the temperature is suddenly changed, the electrode potential gradually changes due to a change in the concentration of KCl.

4. Since the body of the verification electrode 20 and the water quality measurement sensor 30 are formed of a thin glass film and are susceptible to breakage, the verification electrode 20 and the water quality sensor 30 are firmly fixed to the bracket 200 do.

Then, the first terminal 11 of the potential difference measuring apparatus 10 is connected to a verifying electrode 20 which generates a potential difference only in the sample to be measured and indicates an absolute value of measurement as '0'.

The reference electrode 31 and the measuring electrode 32 are formed on the second terminal 12 of the potential difference measuring apparatus 10 and the reference electrode 31 and the measuring electrode 32, The reference electrode 31 of the water quality measurement sensor 30 including the composite electrode 30b provided in a separated state is connected.

When the verification electrode 20 is connected to the first terminal 11 of the potential difference measurement apparatus 10 and the connection of the reference electrode 31 of the water quality measurement sensor 30 is completed to the second terminal 12, The verification electrode 20 and the water quality measurement sensor 30 are immersed in the first sample 40 placed in a container such as a beaker.

Then, after the measured value of the verification electrode 20 and the water quality measurement sensor 30 is stabilized after the potential difference measurement apparatus 10 is turned on, the indicated value of the potential difference measurement apparatus 10 displayed is -40 mV ± 5 mV It is possible to verify whether the reference electrode 31 is abnormal or not.

After the verification of the reference electrode 31, the second terminal 12 of the potential difference measurement apparatus 10 is connected to the measurement electrode 30 of the water quality measurement sensor 30, which is composed of the half-electrode 30a and the composite electrode 30b to be verified. (32).

Thereafter, the inspection electrode 20 is cleaned and then immersed in the second sample 50 together with the water quality measurement sensor 30.

Next, after confirming that the measured values of the verifying electrode 20 and the water quality measuring sensor 30 are stabilized, it is checked whether the indicated value of the potential difference measuring apparatus 10 is included in the range of + 130 mV ± 10 mV, There is a characteristic that it can be verified whether or not it exists.

In this case, the stabilization of the measurement value means that when the verification electrode 20 and the water quality measurement sensor 30 are immersed in the first and second samples 40 and 50, the measured values are constantly changed, Which indicates a correct measurement value when indicating a value to be measured.

That is, the KCl solution of the verification electrode 20 maintains the concentration of Ag + ions reproducibly so that the potential difference between the probe electrode 20 and the water quality sensor 30, which has a reproducible potential difference on the Ag / AgCl surface, The hydrogen ion concentration (pH) value can be known.

One example of conditions for determining the normal range of the reference electrode 31 and the measurement electrode 32 of the water quality measurement sensor 30 using the above verification method is that the temperature of the first and second samples 40, The reference value measured by the reference electrode solution 50 in the standard buffer solution 4 pH is approximately 178 mV, the measurement value of the reference electrode 31 is -40 mV, and the measurement value of the measurement electrode 32 is +138 mV.

Here, when the first and second samples 40 and 50 are 4.01 pH, the measured value of the composite electrode water quality sensor 30 is 178 mV because the temperature compensation value per pH is 59.16 mV (7pH-4pH) × 59.16mV = 177.48mV in the 4.01 standard buffer solution, the result obtained by adding the reference electrode 31 and the measuring electrode 32 regardless of the sign is obtained. When 170mV is displayed, it is judged as normal.

In the measurement of the hydrogen ion concentration, the probe electrode 20 and the water quality sensor 30 are immersed in the first and second samples 40 and 50 to generate a potential difference in proportion to the pH value, ) Maintains a constant potential irrespective of the temperature, and the potential difference between the water quality sensor 30 and the verifying electrode 20 indicates a signal proportional to the pH value, and most The pH sensor theoretically has a response slope of -59.16 mV / pH (25 ° C) to be 0 mV at pH 7.0.

In addition, the reason why the temperature measurement is necessary in the measurement of the hydrogen ion concentration is that the millivolt signal generated between the water quality sensor 30 and the verification electrode 20 is affected by the temperature. However, it has an isopotential point indicating a constant potential regardless of the temperature change. The equipotential point is often designed at pH 7.0 to 0 mV. When the equipotential point is used, the temperature sensor 30b 'is constructed so as to be able to compensate at a reference temperature (25 ° C) even if the temperature is measured at a certain temperature.

That is, in the conventional method of verifying the water quality measurement sensor, the water quality measurement sensor such as the complex sensor connected to the meter is immersed in the buffer solution and the abnormality is determined by measuring the measured value of the water quality measurement sensor displayed on the meter. When the solution is 4 pH, if there is no abnormality in the reference electrode and the measuring electrode, it is normal that the value of about 170 mV should be displayed on the meter. If the value exceeds the error range, it is difficult to judge which of the reference electrode and the measuring electrode is abnormal The present invention is characterized in that the reference electrode 31 and the measuring electrode 32 are separately verified and the abnormality can be easily judged by measuring the measured value of each electrode.

In addition, the existing water quality measuring sensor verification method is a water quality measuring sensor connected to the meter, and when measuring the buffer solution for measurement, if an error value slightly over the error range is displayed, the meter is adjusted to set the measurement value of the water quality measuring sensor There is a problem in that it is impossible to judge whether there is an abnormality even in the presence of an abnormality to the electrode of the water quality sensor, and there is a problem that the meter is temporarily set to the display value. On the other hand, There is a characteristic that it is possible to clearly determine whether or not the function of the water quality measuring sensor 30 is abnormal for each electrode by using the potential difference measuring device 10. [

In addition, the verification method of existing water quality measurement sensors is different from each company that manufactures the buffer solution, and when it is measured by using normal water quality measurement sensor, the manufacturer of buffer solution used for measurement, There is a problem in that the measured value is varied. In order to calibrate it, there is a problem that the meter is adjusted so that the display value is adjusted through the calibration operation each time of measurement, By establishing a measurement criterion by judging the abnormality with respect to the measurement value measured by the reference electrode 31 or the measurement electrode 32 by using the verification electrode 20 irrespective of the buffer solution used for the measurement, There is a feature that the abnormality of the electrode can be accurately diagnosed without the necessity.

Thus, in the case where there is no abnormality in the meter and the water quality sensor 30 in the field using the water quality measurement sensor 30, the present invention can easily determine whether or not the presence of a sulfur compound that interferes with the hydrogen ion potential and the presence of OH - ions And the characteristic of the measurement solution can be easily and accurately judged.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limited to the embodiments set forth herein. Various changes and modifications may be made by those skilled in the art.

10: potential difference measuring device 11: first terminal
12: second terminal 13: display window
20: Verification electrode 21:
21a: mercury layer 21b: inner tube
21c: inner mixture liquid 21d: platinum wire
21d ': cable 21f:
21e: glass body 22: silver-standard electrode
22a: sensing part 22b: sensor body
22c: internal solution 22d: Ag wire
22d ': Cable 30: Water quality measurement sensor
30a: half electrode 30b: composite electrode
31: reference electrode 31a: reference glass body
31b: Porous membrane 31c: Inner replenisher
31d: internal conductor 31d ': cable
32: measuring electrode 32a: measuring glass body
32a ': glass diaphragm 32b: internal electrolyte
32c: Ag / Agcl wire 31c ': Cable
40: first sample 50: second sample

Claims (9)

The first terminal 11 of the potential difference measuring apparatus 10 is connected to a verifying electrode 20 which generates only a potential difference in the sample to be measured and indicates an absolute value of measurement as '0'
The reference electrode 31 and the measuring electrode 32 are separately formed in the second terminal 12 of the potential difference measuring apparatus 10 and the reference electrode 31 and the measuring electrode 32 are separated from each other. The reference electrode 31 of the water quality measurement sensor 30,
The verification electrode 20 and the water quality measurement sensor 30 are immersed in a first sample formed of either a buffer solution or an aqueous solution and then measured values of the verification electrode 20 and the water quality measurement sensor 30 are stabilized and displayed It is confirmed whether or not the reference value of the reference electrode 31 is abnormal by confirming that the indication value of the potential difference measuring apparatus 10 included in the range of -40 mV ± 5 mV is included,
After the verification of the reference electrode 31, the measurement electrode 32 of the water quality measurement sensor 30 is connected to the second terminal 12 of the potential difference measurement device 10,
After the cleaning of the probe electrode 20, it is immersed in a second sample formed with a buffer solution of 4.00 pH or 4.01 pH with the water quality sensor 30, and then the measured value of the probe electrode 20 and the water quality sensor 30 And verifying whether or not an abnormality of the measuring electrode (32) is confirmed by checking whether the indication of the potential difference measuring apparatus (10) displayed after stabilization is included in the range of + 130 mV ± 10 mV. The method as claimed in claim 1, wherein the verification electrode (20) is formed of Hg, Hg 2 Cl 2 , A platinum wire 21d is immersed in the inner mixture liquid 21c filled with KCL and the inner tube 21b is filled with a KCL solution or a KCL crystal and a glass body 21f having a liquid- 21b, 21c, 21c, 21e, respectively,
A silver-standard electrode 22 in which an Ag wire 22d is deposited on an inner liquid 22c filled with a mixed solution of KCl and AgCl into a sensor body 22b having a sensing part 22a at a lower part thereof Wherein the reference electrode and the measuring electrode are electrically connected to each other. delete The first terminal 11 of the potential difference measuring apparatus 10 is connected to a verifying electrode 20 which generates only a potential difference in the sample to be measured and indicates an absolute value of measurement as '0'
The reference electrode 31 and the measuring electrode 32 are separately formed in the second terminal 12 of the potential difference measuring apparatus 10 and the reference electrode 31 and the measuring electrode 32 are separated from each other. The reference electrode 31 of the water quality measurement sensor 30,
The verification electrode 20 and the water quality measurement sensor 30 are immersed in a first sample formed of either a buffer solution or an aqueous solution and then measured values of the verification electrode 20 and the water quality measurement sensor 30 are stabilized and displayed And verifying whether or not an abnormality of the reference electrode (31) is confirmed by confirming that the instruction value of the potential difference measuring apparatus (10) included in the range of -40 mV ± 5 mV is included. The method of claim 4, wherein the inner tube (21b) the validation electrode 20 is formed of a mercury layer (21a) to the lower Hg, Hg 2 Cl 2, A platinum wire 21d is immersed in the inner mixture liquid 21c filled with KCL and the inner tube 21b is filled with a KCL solution or a KCL crystal and a glass body 21f having a liquid- 21b, 21c, 21c, 21e, respectively,
A silver-standard electrode 22 in which an Ag wire 22d is deposited on an inner liquid 22c filled with a mixed solution of KCl and AgCl into a sensor body 22b having a sensing part 22a at a lower part thereof Wherein the reference electrode and the measuring electrode are electrically connected to each other. delete The first terminal 11 of the potential difference measuring apparatus 10 is connected to a verifying electrode 20 which generates only a potential difference in the sample to be measured and indicates an absolute value of measurement as '0'
The measurement electrode 32 of the water quality measurement sensor 30, which is a half electrode or a composite electrode to be verified, is connected to the second terminal 12 of the potential difference measurement apparatus 10,
After the cleaning of the probe electrode 20, it is immersed in a second sample formed with a buffer solution of 4.00 pH or 4.01 pH with the water quality sensor 30, and then the measured value of the probe electrode 20 and the water quality sensor 30 And verifying whether or not an abnormality of the measuring electrode (32) is confirmed by checking whether the indication of the potential difference measuring apparatus (10) displayed after stabilization is included in the range of + 130 mV ± 10 mV. The method of claim 7, wherein the inner tube (21b) the validation electrode 20 is formed of a mercury layer (21a) to the lower Hg, Hg 2 Cl 2, A platinum wire 21d is immersed in the inner mixture liquid 21c filled with KCL and the inner tube 21b is filled with a KCL solution or a KCL crystal and a glass body 21f having a liquid- 21b, 21c, 21c, 21e, respectively,
A silver-standard electrode 22 in which an Ag wire 22d is deposited on an inner liquid 22c filled with a mixed solution of KCl and AgCl into a sensor body 22b having a sensing part 22a at a lower part thereof Wherein the reference electrode and the measuring electrode are electrically connected to each other. delete
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101618042B1 (en) 2015-10-08 2016-05-04 길주형 Water quality measurement sensor
KR20160057140A (en) * 2014-11-13 2016-05-23 대한민국(농촌진흥청장) APPARATUS FOR MEASURING pH IN SOIL
CN106501136A (en) * 2016-11-23 2017-03-15 西南大学 A kind of Acquisition Circuit system of compound ion electrode electromotive force and acquisition method
WO2018062639A1 (en) * 2016-09-28 2018-04-05 한국전력공사 Water ph measurement device and water ph measurement method using same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009070778A (en) * 2007-09-18 2009-04-02 Toyota Motor Corp State detection device of secondary battery
JP2010145380A (en) * 2008-12-22 2010-07-01 Dkk Toa Corp Method for inspecting electrode of oxidation-reduction potential measuring apparatus, and standard solution for inspecting electrode of oxidation-reduction potential measuring apparatus
JP4625390B2 (en) * 2004-10-04 2011-02-02 メトラー−トレド アクチェンゲゼルシャフト Reference electrode for potentiometric measurement and method for monitoring the reference electrode

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4625390B2 (en) * 2004-10-04 2011-02-02 メトラー−トレド アクチェンゲゼルシャフト Reference electrode for potentiometric measurement and method for monitoring the reference electrode
JP2009070778A (en) * 2007-09-18 2009-04-02 Toyota Motor Corp State detection device of secondary battery
JP2010145380A (en) * 2008-12-22 2010-07-01 Dkk Toa Corp Method for inspecting electrode of oxidation-reduction potential measuring apparatus, and standard solution for inspecting electrode of oxidation-reduction potential measuring apparatus

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
pH Electrode Test Procedure, BROADLEY JAMES CORPORATION, [online], 2011.01.17. 최종수정(http://archive.org/web 기준), 인터넷 : http://www.broadleyjames.com/PDFs/130.pdf *
pH Electrode Test Procedure, BROADLEY JAMES CORPORATION, [online], 2011.01.17. 최종수정(http://archive.org/web 기준), 인터넷 : http://www.broadleyjames.com/PDFs/130.pdf*

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160057140A (en) * 2014-11-13 2016-05-23 대한민국(농촌진흥청장) APPARATUS FOR MEASURING pH IN SOIL
KR101651919B1 (en) * 2014-11-13 2016-08-30 대한민국 APPARATUS FOR MEASURING pH IN SOIL
KR101618042B1 (en) 2015-10-08 2016-05-04 길주형 Water quality measurement sensor
WO2018062639A1 (en) * 2016-09-28 2018-04-05 한국전력공사 Water ph measurement device and water ph measurement method using same
CN106501136A (en) * 2016-11-23 2017-03-15 西南大学 A kind of Acquisition Circuit system of compound ion electrode electromotive force and acquisition method
CN106501136B (en) * 2016-11-23 2023-10-03 西南大学 Acquisition circuit system and acquisition method for composite ion electrode electromotive force

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