JPH08304334A - Ozone water concentration measuring device - Google Patents

Abstract

PURPOSE: To provide an ozone water concentration measuring device in which the more precise ozone concentration can be continuously detected with a simple structure of crude electrode type both in running water and still water with a short response time. CONSTITUTION: This device is formed of a detecting electrode 30 and a reference electrode 40 dipped a solution to be measured, and a measuring part 50 for measuring the electromotive force between the detecting electrode 30 and the reference electrode 40. Either one or the both of the detecting electrode 30 consisting of nickel-chromium alloy (Xi-Cr alloy) or nickel-chromium alloy having a slight palladium (Pd) added thereto and the reference electrode 40 consisting of silver (Ag) or silver chloride (Ag/AgCl) are linearly reciprocated in the direction never changing the space with the partner electrode by a driving device 20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ozone water concentration measuring device for measuring the ozone concentration of ozone water (water in which ozone is dissolved). More specifically, the present invention relates to a detection electrode and a reference electrode immersed in a liquid to be measured. The present invention relates to a so-called bare electrode type ozone water concentration measuring device, which is constituted by a measuring unit that measures an electromotive force between the detection electrode and the reference electrode.

[0002]

2. Description of the Related Art Conventionally, an ultraviolet absorption method and a titration method have been widely used as the most reliable methods for measuring the ozone concentration of ozone water, but recently, the mechanism is simple and responsive. An electrode-type ozone water concentration measuring device capable of quick and continuous measurement has been attracting attention as a device that can be easily measured.

As the electrode type ozone water concentration measuring device, there are proposed a diaphragm type in which ozone water and a pair of electrodes are partitioned by an ozone permeable membrane, and a bare electrode type in which the electrodes are directly immersed in ozone water. . And, in the above diaphragm type, a container whose tip opening is closed by an ozone permeable membrane is filled with an electrolytic solution, and the detection electrode and the reference electrode are housed in this electrolytic solution, and the tip of the container is inserted into ozone water. The ozone concentration is detected by reading the effect of ozone passing through the ozone permeable membrane, which becomes a diaphragm, on the electrolytic solution in the container as a change in electrical signal.

In the bare electrode type, when a pair of electrodes are made of a combination of certain specific different metals and the paired electrodes are inserted and dipped in ozone water, the ozone concentration between the electrodes is matched. That is, gold (Au) is used for one detection electrode and copper (Cu) is used for the other comparison electrode (referred to as the Grisheim method). It is known that electromotive force due to ozone can be obtained.

The mechanism of generating the above electromotive force is considered to be a kind of so-called galvanic cell in which a pair of electrodes having different ionization tendencies are separated from each other and immersed in a solution to generate electromotive force. Ionization columns arranged in order of magnitude of tendency are shown in "Table 1" below.

[0006]

[Table 1]

[0007] In the above "Table 1", it is the principle of the galvanic cell that electromotive force is generated between the two metals when a pair of electrodes are made of different metals and immersed in a solution. Many studies have been conducted in the past that have an efficient electromotive force in an ozone solution, that is, ozone water, and a tendency that the electromotive force in an electrolytic solution such as chlorine (Cl) is small (called an ozone selective electromotive force). The one that has been studied by the researchers and has been continuously put into practical use is a combination using copper (Cu) for one electrode and gold (Au) for the other electrode. In this case, the gold (A
It is known that (u) serves as a cathode and (Cu) serves as an anode for the copper of the reference electrode, and electromotive force is approximately proportional to the ozone concentration.

A specific example of the conventional bare electrode type ozone water concentration measuring apparatus has a structure as shown in FIGS. 15 to 18, and the conventional example shown in FIG. The electrode 30 and the reference electrode 40 have a predetermined space and
The container 90 is provided with an inlet 91 of the liquid to be measured at one end and an outlet 92 at the other end of the container 90.
1 to the arrow Y1 by a solution to be measured supply device (not shown) or the like.
The container 90 is filled with the liquid as shown by (4) and filled in the container 90, and then is discharged from the outlet 92 as shown by an arrow Y2.

Then, the detection electrode 30 and the comparison electrode 40
Is a dissimilar metal as described above, and by immersing the detection electrode 30 and the comparison electrode 40 in ozone water, an electromotive force proportional to the ozone concentration of ozone water is measured.
I read it as 0.

However, it is empirically known that the above-mentioned electromotive force usually has a phenomenon of being attenuated in a relatively short time in still water. One of the reasons why electromotive force cannot be obtained continuously is that the electrode deteriorates due to ozone, and in particular, conventionally used copper (Cu) is immediately oxidized when it comes into contact with ozone.

Another cause that the electromotive force due to ozone does not continue is caused when the electromotive force due to ozone is different from the electromotive force of a normal galvanic battery and ions are eluted from a metal having a large ionization tendency. It is described that the electric double layer prevents ozone water from coming into contact with the electrode surface.

Therefore, in the conventional example shown in FIG. 15, ozone water, which is a new liquid to be measured, is constantly passed through the container 90 so that the ozone electromotive force is continuously maintained. This is called "running water bare electrode system", and most of the conventional examples adopt this system. This "Fig. 1
5 ”When the liquid to be measured was passed through the ozone water concentration measuring device of the conventional example while gradually increasing the flow rate, the electromotive force due to ozone was gradually increased up to a certain flow rate, as shown in FIG. When the flow velocity was above a predetermined level, the ozone electromotive force was almost stable, and when the flow velocity was further increased, the ozone electromotive force tended to decrease and became unstable.

The measuring unit 50 is composed of an ammeter, a voltmeter, etc., and measures the ozone electromotive force to know the ozone concentration of the liquid to be measured. When the electrolyte is dissolved, it also constitutes a normal galvanic cell, so the electromotive force due to the ozone is also affected by the dissolved amount, so the electromotive force is not the electromotive force due to ozone. Absolutely, the absolute ozone concentration cannot be measured only by the electromotive force, and usually the water (liquid) before ozone is dissolved is used as a standard solution to detect the ozone concentration.

In addition, in contrast to the above-mentioned running water electrode system, "Fig.
7 ”The conventional example is a part of which is proposed so that the measurement liquid can be measured with a fixed amount taken out in a container 93 for sampling. This method forces the measurement liquid to flow through. Instead, the plate-shaped detection electrode 30 is normally attached to the arrow Y3.
It is rotated in the direction or the like and used as a stirring blade so that the electromotive force due to ozone is continuous for the time required for detection. The rest of the configuration is almost the same as the flowing water electrode system, and this system will be referred to as "static water stirring bare electrode system".

Further, the conventional example shown in FIG. 18 is a cylindrical container 90.
The reference electrode 40 made of copper (Cu) is provided on the inner peripheral surface of a, and the detection electrode 30 made of gold (Au) is provided at the center of the cylindrical container 90a. It passes through between the reference electrode 30 and the reference electrode 40 and flows out from the outlet 92. The cylindrical container 90a is provided with a stirring blade 70 having a rotating shaft at the central axis portion thereof, and abrasive particles 7 such as quartz beads are contained in the liquid to be measured.
1, 71, 71 ... Are thrown in.

That is, since the surface of the copper (Cu) used for the reference electrode 40 is oxidized and denatured by ozone water, the stirring blade 70 is provided and in the measured liquid stirred by the stirring blade 70. The abrasive particles 71, 71,
By adding 71 ..., The surface of the reference electrode 40 is constantly polished and measured (this method is referred to as “bare electrode polishing method”).
Say ) It is done like this.

[0017]

However, the conventional flowing water bare electrode method has a problem in that reliability and reproducibility cannot be obtained unless the flow velocity of the liquid to be measured is adjusted to a predetermined speed within a narrow range in practice. In addition, the presently proposed ozone water concentration measuring device of this kind of flowing water naked electrode method uses a flow rate of about 1 to 2 liters / minute, and in consideration of stability and averaging of measured values, Since a practical measurement requires several tens of seconds or more, a large amount of liquid to be measured is required for accurate measurement, and there is a problem that continuous measurement is practically difficult. .

That is, in the flowing water bare electrode method, if the flow velocity of the liquid to be measured is too slow, the electrode surface cannot be sufficiently purged, so that the electromotive force is not proportional to the ozone concentration and the measured value appears to be low, thus ensuring reproducibility. It will not be possible. Therefore, in order to ensure reproducibility, there is no choice but to set the flow velocity of the liquid to be measured to be high, but when the flow velocity exceeds a certain constant value, the reliability of the measured value is rapidly increased as shown in "Fig. 16". It has a phenomenon of being lost, and when the cause was investigated, it was found that it was caused by the next cause.

First, when the flow velocity of the liquid to be measured is high, a complicated eddy current is generated in the fluid that collides with the detection electrode 30 or the comparison electrode 40 at a high speed, and this vortex flow is locally measured. This makes the flow-through amount of the liquid non-uniform and reduces the reliability of the measurement results. Actually, this phenomenon appeared as a phenomenon in which the measured value always fluctuates greatly.

Next, when the liquid to be measured collides with the detection electrode 30 or the comparison electrode 40 at a high speed, dissolved ozone (partially mixed with other gas such as oxygen) is deposited as fine bubbles. However, the ozone concentration of the liquid to be measured is lowered, and bubbles such as ozone gas are usually poor electrical conductors, so that the electromotive force cannot be accurately detected by the measuring unit 50.

Further, the still water bare electrode system of FIG. 17 has a problem that the reliability is generally lower than that of the running water electrode system. When a trial manufacture and a test were conducted to pursue the cause of this low reliability, firstly, when this kind of detection electrode 30 is rotated, a detection signal from the detection electrode 30 is extracted from the rotating portion by a contact signal extraction mechanism such as a brush. It was actually difficult to take out the minute electromotive force. The brush contact part is made of a highly conductive material such as precious metal, and the signal output part is equipped with a smoothing circuit and a noise removing circuit.However, the electromotive force is extremely low at a few millivolts, so it is not very useful. It wasn't effective.

Further, as a result of the experiment, it was found that when the ozone water as the liquid to be measured is agitated, a swirl flow is generated or bubbles such as ozone gas are generated in the same manner as described above, and there are problems similar to those of the running water electrode system. .

Further, in the electrode polishing method of FIG. 18, not only stirring but also polishing particles 71, 7 for polishing the reference electrode 40.
Since 1,71 ... rotate at high speed, the generation of eddy currents and the precipitation of dissolved ozone are unavoidable, and there is also the problem that copper (Cu) polishing debris and the like are mixed into ozone water. Have

Therefore, the present invention has been made in view of the above problems, and provides an ozone water concentration measuring device having a simple structure and capable of continuously detecting a more accurate ozone concentration with a short response time in running water or still water. This is the purpose.

[0025]

In order to solve the above-mentioned problems, in order to solve the above-mentioned problems, the structure of the present invention, which has the above-mentioned claims as its gist, has been made in accordance with the above object. In the ozone water concentration measuring device comprising 40 and a measuring unit 50 for measuring an electromotive force between the detecting electrode 30 and the comparing electrode 40, the detecting electrode 30 and the comparing electrode 4
The technical means is characterized in that either or both of 0 and 0 are linearly reciprocated in a direction in which the gap between the drive device 20 and the opposite electrode is not changed.

Further, in the invention of "claim 2", the detection electrode 30 and the reference electrode 40 immersed in the liquid to be measured, and the measuring unit 5 for measuring the electromotive force between the detection electrode 30 and the reference electrode 40 are measured.
In the ozone water concentration measuring device configured with 0, the detection electrode 30 and the reference electrode 40 immersed in the liquid to be measured, and the measurement unit 50 for measuring the electromotive force between the detection electrode 30 and the reference electrode 40 are used. In the constituent ozone water concentration measuring device,
Either or both of the detection electrode 30 and the comparison electrode 40 are linearly reciprocated in a direction in which the gap between the detection electrode 30 and the comparison electrode 40 is not changed by the drive device 20, and the detection electrode 30 is provided opposite to the detection electrode 30. The detection electrode 30 is made of a material different from that of the detection electrode 30. The calibration electrode 61 is made of a metal whose ozone electromotive force is small enough to be ignored even if ozone water is present between the detection electrode 30 and the detection electrode 30. And reference electrode 40
Between the calibration electrode 61 and the detection electrode 30, there is provided a calibration voltage application device 60 for applying a voltage of the opposite polarity corresponding to the galvanic cell electromotive force, or the calibration electrode 6
1 is a technical means characterized in that a galvanic cell electromotive force of a reverse polarity corresponding to the galvanic cell electromotive force generated between the detection electrode 30 and the comparison electrode 40 is generated.

Further, in the invention of "claim 3", the detection electrode 30 and the reference electrode 40 immersed in the liquid to be measured, and the measuring section 50 for measuring the electromotive force between the detection electrode 30 and the reference electrode 40 are measured. In the ozone water concentration measuring device constituted by the above, the detection electrode 30 is linearly reciprocated by the driving device 20, and the reference electrode 40 is located at the same radial distance from the axis of the detection electrode 30 in the linear movement direction. Cylindrical body 40a, cylindrical wire mesh body 40b, metal coil body 40c, a plurality of electrode bodies 4
0d, 40d, 40d, etc. are fixed to constitute the technical means.

Further, in the invention of "claim 4", the detection electrode 30 and the reference electrode 40 immersed in the liquid to be measured, and the measuring unit 50 for measuring the electromotive force between the detection electrode 30 and the reference electrode 40 are measured. In the ozone water concentration measuring device configured by the above, the detection electrode 30 is composed of a coil 30c, the upper end of which is fixed to the densitometer main body 10, and at least one pitch of the coil is larger than the fixed part of the detection electrode 30. The drive shaft 2 that linearly reciprocates in the up and down direction protruding from the densitometer main body 10 at a position separated from the above
3, the reference electrode 40 is a metal cylinder 40a located at the same radial distance from the axis of the detection electrode 30 in the movement direction,
A technical means characterized in that any one of the cylindrical wire netting body 40b, the metal coil body 40c, and the plurality of electrode bodies 40d, 40d, 40d ... Is fixed.

Further, in the invention of "Claim 5", the detection electrode 30 and the reference electrode 40 immersed in the liquid to be measured, and the measuring unit 50 for measuring the electromotive force between the detection electrode 30 and the reference electrode 40 are measured. In the ozone water concentration measuring device configured by the above, the detection electrode 30 has a large-diameter coil portion 31 into which the densitometer main body 10 is fitted, and the detection electrode 30 is separated from the large-diameter coil portion 31 by at least one pitch of the coil. Main part of the densitometer 1
Drive shaft 23 protruding from 0 and reciprocating in the vertical direction
And the large-diameter coil portion 3
1 and the small-diameter coil portion 32 and the intermediate portion are constituted by a metal coil body 30c which is a free-diameter coil portion 33 that does not come into contact with the drive shaft 23. The large-diameter coil portion 31 is attached to the densitometer body 10 and the small-diameter coil portion 32 is attached It is fixedly attached to the drive shaft 23, and
The reference electrode 40 is composed of a metal coil body 40c that is coaxial with the detection electrode 30 and surrounds the outside of the detection electrode 30, and the upper end portion of the reference electrode 40 should not contact the densitometer body 10 electrically with the detection electrode 30. It is a technical measure characterized by being fixed.

The invention of "Claim 6" is "Claim 1".
The detection electrode 30 according to claim 5 is composed of a nickel-chromium alloy (Ni-Cr alloy) or a nickel-chromium alloy to which some palladium (Pd) is added, and the comparison electrode 40 is silver. (Ag) or silver chloride (Ag / AgCl).

The invention of "Claim 7" is "Claim 1".
The drive device 20 according to claim 5 has a motor 21, a crown gear 22 rotated by a motor drive shaft 21a of the motor 21, and a gear mounted on a horizontal shaft 25 and meshed with the crown gear 22. 24
And an eccentric disc 26 attached to this horizontal shaft 25
The eccentric disc body 2 is fixed to the horizontal shaft 25 and rotates together with the eccentric disc body 26a.
6a and a driven body 26b including the eccentric disc body 26a.
The drive shaft 23 is integrally suspended from the driven body 26b, and the drive shaft 23 is freely inserted into the vertical hole 10a provided in the densitometer body 10 to move only in the vertical direction. It is possible to take technical means characterized in that the drive shaft 23 and the detection electrode 30 connected to the drive shaft 23 are linearly reciprocated in the vertical direction by the motor 21.

The invention of "Claim 8" is "Claim 1".
The drive device 20 according to claim 5 is composed of an electromagnetic vibrator 20a.
The drive shaft 23 and the detection electrode 30 connected to this drive shaft 23 are connected to the vibrator 23a of 0a, and the detection electrode 30 is linearly reciprocated. is there.

The invention of "Claim 9" is "Claim 1".
The drive device 20 according to claim 5 is composed of an electromagnetic vibrator 20a driven by a trapezoidal wave AC power source, and the vibrator 23a of the electromagnetic vibrator 20a is connected to the drive shaft 23 and the drive shaft 23. The technical means is provided by connecting the detection electrodes 30 so that the detection electrodes 30 reciprocate in a straight line.

[0034]

Therefore, in the ozone water concentration measuring apparatus of the present invention, when the detection electrode 30 and the reference electrode 40 are immersed in the liquid to be measured,
Between the detection electrode 30 and the comparison electrode 40, an electromotive force due to ozone that is approximately proportional to the ozone concentration of the liquid to be measured (in the present embodiment, the detection electrode 30 is provided with a nickel-chromium alloy (Ni.C)).
(r alloy), or nickel-chromium alloy to which a small amount of palladium (Pd) is added, and silver (Ag) or silver chloride (Ag / AgCl) is used for the reference electrode 40. The reference electrode 40 serves as a cathode, which has a polarity opposite to that of the conventional example. Is generated, and the electromotive force due to this ozone is detected by the measuring unit 50, and the ozone concentration of the liquid to be measured can be measured as in the conventional case.

Since either or both of the detection electrode 30 and the comparison electrode 40 are linearly reciprocated in the direction in which the gap between the detection electrode 30 and the comparison electrode 40 is not changed by the driving device 20, the moving detection is performed. The electrode 30 or the comparison electrode 40 constantly comes into contact with a new liquid to be measured, prevents the formation of an electric double layer, and exerts the action of continuing the electromotive force for a time suitable for reading by the measurement unit 50. Since the distance to the electrode 40 is not changed, a stable output signal can be obtained.

Further, the detection electrode 30 or the detection electrode 30
Since either or both of the reference electrode 40 and the reference electrode 40 are not rotated but are linearly reciprocated in the direction in which the gap between the reference electrode and the counterpart electrode is not changed by the drive device 20, the measured liquid and the detection electrode 30 or the reference electrode The frequency of contact with 40 improves,
There is little agitation of the liquid to be measured, and the external force applied to the liquid to be measured is smaller than that of high-speed running water or agitation.
It has the effect of suppressing the precipitation of dissolved ozone and the like as bubbles to a minimum.

In addition, according to the result of the experiment, by increasing the speed of the linear reciprocating motion, the electromotive force of the dissolved ozone is measured in a short response time.

Furthermore, since the signal can be taken out from the linear reciprocating motion without using the contact signal taking-out part such as the rotating part and the brush, it is possible to accurately read a weak signal. Is.

Further, since either or both of the detection electrode 30 and the comparison electrode 40 are linearly reciprocated in the driving device 20 in a direction parallel to the other electrode, it exhibits an action that can be measured in running water or still water. is there.

Further, the invention of "claim 2" is the calibration electrode 6
1 is provided, the normal galvanic cell electromotive force between the detection electrode 30 and the calibration electrode 61 is read to detect the detection electrode 30.
Between the reference electrode 40 and the reference electrode 40, a voltage for canceling the galvanic electromotive force is applied, or the calibration electrode 61 has a reverse polarity corresponding to the galvanic cell electromotive force generated between the detection electrode 30 and the reference electrode 40. The galvanic cell electromotive force is generated so that the measurement error due to the electrolyte dissolved in the solution to be measured can be calibrated.

Further, the invention of "Claim 3" is the comparison electrode 4
0 is located at the same radial distance from the axis of the detection electrode 30 in the movement direction, the metal cylindrical body 40a, the cylindrical wire mesh body 40b, the metal coil body 40c, the plurality of electrode bodies 40d, 40d, 40d.
Since it is configured by any of the above, a uniform electric field due to electromotive force can be obtained between the detection electrode 30 and the comparison electrode 40 in substantially all directions centering on the detection electrode 30, and a stable detection signal with little fluctuation can be obtained. Exhibits the effect of being. The reference electrode 40
Are located at the same radial distance from the axis of the detection electrode 30 in the direction of movement, the metal cylindrical body 40a, the cylindrical wire mesh body 40b, the metal coil body 40c, the plurality of electrode bodies 40d, 40d, 40d.
By configuring with either of the
A new liquid to be measured can be freely passed through the inside of the detection electrode 3
It has the effect of being filled between 0 and the reference electrode 40.

Further, in the invention of "Claim 4", the detection electrode 30 is constituted by the coil 30c, and the upper end portion thereof is fixed to the densitometer main body 10, and the detection electrode 30 has at least a coil portion at which the detection electrode 30 is fixed. Since the portions separated by one pitch or more are fixedly attached to the drive shaft 23 protruding linearly from the densitometer body 10 and reciprocating linearly, the lower free end of the coil 30c can reciprocate linearly. The upper part of the detection electrode 30 is fixed, and by connecting and fixing a conducting wire to this fixed portion, the function of easily extracting a signal with less noise is exhibited.

The invention according to claim 5 is the detection electrode 3
The upper end portion of 0 is a large-diameter coil portion 31 into which the densitometer main body 10 is fitted, and a portion apart from this large-diameter coil portion 31 by one pitch or more is a straight line in the vertical direction protruding from the densitometer main body 10. The coil 30c includes a small-diameter coil portion 32 into which the reciprocating drive shaft 23 is fitted, and the large-diameter coil portion 31, the small-diameter coil portion 32, and the intermediate portion are free-diameter coil portions 33 that do not contact the drive shaft 23. Since the large-diameter coil portion 31 is fixedly attached to the densitometer body 10 and the small-diameter coil portion 32 is fixedly attached to the drive shaft 23, the large-diameter coil portion 31 which is a fixed portion and the small-diameter coil portion which is a free end side. Since the free-diameter coil portion 33, which does not contact the drive shaft 23, is interposed between the free-diameter coil portion 33 and the lower part of the drawing, the free-end side linear reciprocating motion is facilitated by expansion and contraction of the free-diameter coil portion 33, and Free end side is straight Its movement amount be backward movement is one that exhibits an effect that does not affect the large-diameter coil part 31 is absorbed by expansion and contraction of the free diameter coil section 33.

The reference electrode 40 is composed of a coil 40c which is coaxial with the detection electrode 30 and surrounds the outside of the detection electrode 30, and the upper end portion of the coil 40c is provided on the densitometer body 10.
Since the liquid to be measured is fixed so as not to make electrical contact with, the liquid to be measured can move in both the parallel direction and the vertical direction with respect to the detection electrode 30, and even if the detection electrode 30 is linearly reciprocated at a considerably high speed, a vortex flow is generated. It has low generation of ozone and precipitation of ozone, and exhibits high-performance measuring ability. The details of this action will be described later.

The invention according to claim 6 is the detection electrode 3
0 is composed of a nickel-chromium alloy (Ni-Cr alloy) or a nickel-chromium alloy to which some palladium (Pd) is added, and the reference electrode 40 is silver (Ag) or silver chloride (Ag / AgCl). ), When the detection electrode 30 and the comparison electrode 40, which are different metals, are immersed in the liquid to be measured, an electromotive force proportional to the ozone concentration is generated between them and the ozone concentration can be detected. Met.

The combination of the materials of the detection electrode 30 and the reference electrode 40 was selected through various trials and errors, and it was experimentally found that this combination has an effect of obtaining an electromotive force comparable to that of the conventional example. The result was confirmed.
It was easily found that nickel (Ni), which has a relatively low ionization tendency, has a favorable ozone-selective electromotive force with respect to silver (Ag), which has a lower ionization tendency.
Similar to copper (Cu), nickel (Ni) had an oxide film formed on its surface by ozone. Therefore, chromium (Cr) and nickel (Ni), which have somewhat higher ozone resistance,
When an alloy was prepared and tested, it was confirmed that it has ozone selective electromotive force required for ozone water concentration measurement and ozone resistance.

It should be noted that in the prior art, a material having a small ionization tendency is used on the detection electrode 30 side, whereas a material having a larger ionization tendency than the reference electrode 40 is used as the electrode material of the detection electrode 30 in the present invention. There is. Although this difference only reverses the direction of the electromotive force and does not directly affect the measurement, it is intentionally configured in this manner in connection with the rehabilitation electrode 61 described later (details will be described later).

That is, the detection electrode 30 is made of nickel.
By comprising a chromium alloy (Ni / Cr alloy) or a nickel / chromium alloy to which a small amount of palladium (Pd) is added, it has corrosion resistance and exhibits an effect of not deteriorating even in ozone water. As shown in "Table 1", nickel and chromium both have a greater ionization tendency than conventional gold, but by using an alloy, corrosion resistance is improved although it does not reach that of gold. nickel·
Chromium alloy forms an oxide film on the surface when it is oxidized by ozone and immobilizes it, resulting in an extremely stable composition, and even if this oxide film is formed, the electromotive force due to ozone is not significantly reduced. Was presented.

Further, since the reference electrode 40 is made of silver (Ag) or silver chloride (Ag / AgCl), it is oxidized by ozone water (silver is a conventional copper (Cu) as shown in "Table 1"). Although it has a smaller ionization tendency, it is unavoidable that it is oxidized by ozone.) However, as with the detection electrode 30, an oxidation layer is formed on the surface by the oxidation with ozone, and it becomes an immobilization layer. After the layer is formed, it maintains a stable state thereafter and does not denature, and
Even if an oxide film was formed, in the case of silver (Ag), the electromotive force did not decrease. Further, chlorine (Cl) treatment is known as an immobilization of silver (Ag) instead of oxidation, and the reference electrode 40 is composed of silver chloride (Ag / AgCl) (the surface of Ag / AgCl is expressed as silver chloride). (AgCl)
Means to ), An equivalent electromotive force was obtained.

The invention according to claim 7 is the drive device 2.
Since the motor 21 is used for 0 and the linear reciprocating motion of the drive shaft 23 is changed by the crown gear 22 to the eccentric disc 26, either or both of the detection electrode 30 and the comparison electrode 40 can be reliably driven with a simple configuration. Exhibits the effect of.

The invention according to claim 8 is the drive device 2
Since the electromagnetic vibrator 20a is used for No. 0, it has the effect of enabling long-term continuous operation.

Further, in the invention of "Claim 9", since the electromagnetic vibrator 20a is operated by the trapezoidal wave AC power source, the drive of either or both of the detection electrode 30 and the comparison electrode 40 is performed at the top dead center. And is driven near the bottom dead center and is driven quickly at the middle point of the ascending and descending, and even if the driving amount speed is increased, the ratio of stirring the liquid to be measured is reduced.

[0053]

Embodiments of the present invention will be described below with reference to the accompanying drawings. In the figure, 30 is a detection electrode immersed in the liquid to be measured, 40 is a reference electrode which is also immersed in the liquid to be measured, and the detection electrode 30 and the reference electrode 40 are made of conventionally known materials as described above. Good.

The detection electrode 30 and the reference electrode 40 are made of different metals, and as a result of the experiment, one of the detection electrode 30 and the reference electrode 40 is gold (Au), platinum (Pt), nickel (Ni), One of chromium (Cr), the other is silver (A
g), copper (Cu), lead (Pb), especially lead dioxide (Pb)
Each respective combination of O ₂ ) was effective in obtaining the electromotive force by ozone.

Further, 50 is a detection electrode 30 and a comparison electrode 40.
And a voltmeter 50a (in this embodiment, a voltmeter 50a).
Are using. ) Is used to display the electromotive force between the detection electrode 30 and the comparison electrode 40 on the display unit 50b. If necessary, the measurement unit 50 may include a necessary circuit such as an amplifier circuit. It may be the same as the conventional one.

A densitometer main body 10 is composed of a container for accommodating necessary equipment in the densitometer main body 10. In the embodiment shown in FIG. 1, it has a pencil shape. It is not particularly limited.

The necessary equipment to be housed in the densitometer body 10 will be described later in sequence. The drive device 20 including the motor 20a, the ammeter or voltmeter 50a, and the display unit 5 will be described.
0b including the measurement unit 50, the batteries B1 and B2, the drive unit 20, and the ammeter or the voltmeter 50a (the built-in amplifier circuit) of the power supply opening / closing switches S1 and S2. Needless to say, it may be provided outside the densitometer body 10 in some cases.

In the present invention, either or both of the detection electrode 30 and the comparison electrode 40 are connected to the drive unit 20.
The linear reciprocating motion is performed in a direction that does not change the gap between the other electrode.

In all of the illustrated embodiments of the present invention including "FIG. 1", the reference electrode 40 is fixed to the densitometer main body 10 and only the detection electrode 30 is linearly reciprocated. In the embodiment shown in FIG. The reference electrode 40 is composed of a coil 40c, the upper part of which is omitted in FIG.
It is fixed and fixed to 0 and can be suspended from the densitometer main body 10. The detection electrode 30 is located at the central axis portion of the comparison electrode 40 and linearly reciprocates in the axial direction, that is, in the direction that does not change the distance from the comparison electrode 40. In the embodiment shown in FIG. 1, the detection electrode 30 has a linear shape. In addition, according to the result of the experiment, it is most suitable to drive the comparison electrode 40. When only the comparison electrode 40 side is driven, "Fig. 15" is almost the same as the conventional example and the electromotive force is "Fig. 15".
It was a little lower than the example. In addition, when driving both the detection electrode 30 and the comparison electrode 40, no clear difference was observed between when driving only the detection electrode 30.

The reference electrode 40 may have a linear shape similar to the detection electrode 30 (similar to the conventional example of FIG. 15) instead of the coil 40c. In this case, the detection electrode 30 is used.
The reference electrode 40 and the reference electrode 40 are installed in parallel with each other, and if either or both of the detection electrode 30 and the reference electrode 40 are linearly reciprocated in the longitudinal direction, they can be driven without changing the distance between them. It is a thing.

In order to reciprocate the detection electrode 30 in a straight line,
In the example shown in FIG. 1, the densitometer body 10 accommodates a drive device 20 composed of a motor 21, and a drive shaft 23 that linearly reciprocates by the drive device 20 extends below the densitometer body 10. A detection electrode 30 is connected and fixed to 23.

That is, the drive unit 20 includes a motor 21
A crown gear 22 rotated by a drive shaft 21a of the motor 21; and a gear 24 fixed to a rotatably supported horizontal shaft 25 and meshing with the crown gear 22.
And convert the vertical axis rotation of the drive shaft 21a of the motor 21 (direction of arrow Y7 in FIG. 1) into the horizontal axis rotation of the horizontal shaft 25 (direction of arrow Y8 in FIG. 1). The eccentric disc 26 is attached to 25, and the horizontal shaft 2
The rotation of 5 is converted into a vertical movement (direction of arrow Y9 in FIG. 1).

The eccentric disc 26 is, as shown most clearly in FIG. 2, an eccentric disc main body 26a fixed to the horizontal shaft 25 and rotating together with the horizontal shaft 25, and a ring shape enclosing the eccentric disc main body 26a. It is composed of a driven body 26b. The drive shaft 23 is integrally suspended from the ring-shaped driven body 26b.
Reference numeral 3 is loosely inserted in a vertical hole 10a provided in the densitometer main body 10 so as to be movable only in the ascending / descending direction of FIG.

Therefore, the eccentric disc body 26a rotates about the horizontal shaft 25 in the direction of the arrow Y4 in FIG. 2 by the rotation of the horizontal shaft 25. Since the large point P is located at the upper rotational position, the driven body 26b to the drive shaft 23 (including the detection electrode 30 connected to the drive shaft 23) are at the highest position, and when the eccentric disc body 26a makes a half rotation, The point P portion is lowered to the lowest position, the driven body 26b to the drive shaft 23 are lowered, and when the point P portion is further rotated a half turn, the step of returning the driven body 26b to the drive shaft 23 to the original highest position is repeated. It is a thing.

3 shows another embodiment in which the detection electrode 30 reciprocates by electromagnetic force. Instead of the motor 201 as the driving device 20, the electromagnetic coil 27 and the electromagnetic coil 27 are loosely inserted. The electromagnetic vibrator 20a configured with the permanent magnet column 28 is used.

That is, the drive shaft 23 is attached to the electromagnetic coil 27, the permanent magnet column 28 is loosely inserted in the hollow portion of the electromagnetic coil 27, and the energization direction from the input end V0 to the electromagnetic coil 27 is controlled (not shown). Controlled by a circuit or by connecting an AC power source to the input end, the electromagnetic coil 27 to the drive shaft 23 are vertically moved in the same figure.
In FIG. 3, 29 is a magnetic body forming an electromagnetic circuit,
Reference numeral 23a indicates a connecting arm.

The electromagnetic vibrator 20a is not limited to the embodiment shown in FIG. 3, but various conventionally known methods can be adopted. However, as shown in the example shown in FIG.
Is preferable because the vibration stroke can be set to a desired size. In this example, a vibration stroke of 3 mm and a vibration frequency of 60 times / second were used.

A control circuit (not shown) for controlling the energization of the electromagnetic coil 27 outputs a trapezoidal current as shown in FIG. 4, and the trapezoidal current is input to the input end of the electromagnetic vibrator 20a. If input is made, the ascending / descending speed is slow in the vicinity of the top dead center and the bottom dead center when the detection electrode 30 is ascended / descended, and the ascending / descending speed becomes fast in the middle of the ascending / descending result. In other words, it is desirable that the ascending / descending speed can be substantially increased without applying a large external force to the liquid to be measured. In addition, "Figure 4"
Shows the voltage on the vertical axis and the time on the horizontal axis.

Further, the electromagnetic vibrator 20 of the example shown in FIG.
In the case of a, since it is usually impossible to drive with a small battery B1 such as a dry cell, it is of course possible to use a commercial power source. In this case, if a transformer, a rectifying circuit, etc. can be housed in the densitometer main body 10, A plug cord (not shown) that connects to the commercial power outlet from the densitometer main body 10 may be extended. If there is no space to store these devices, the necessary devices are separately prepared and connected as a power circuit. Just do it.

Unlike the illustrated example, when both the detection electrode 30 and the comparison electrode 40 are linearly reciprocated by the drive unit 20 or the electromagnetic vibrator 20a, a pair of drive units 20 as described above are used, or It suffices that one driving device 20 drives the detection electrode 30 and the comparison electrode 40 together via a link mechanism or the like. It was assumed that it is desirable to drive the detection electrode 30 and the comparison electrode 40 in opposite directions, but the experimental results show that it is more effective to synchronize them and move together in the same direction. It was

As described above, the detection electrode 30 and the reference electrode 40 may be made of the material used in the conventionally known device of this type, as described above. However, in the present embodiment, the detection electrode 30 is made of nickel.・ Chromium alloy (Ni ・ Cr alloy) or nickel ・ chromium alloy with some palladium (Pd)
Is used as the reference electrode 40, and silver (Ag) is used as the reference electrode 40.
Alternatively, silver chloride (Ag / AgCl) is used.

A nickel-chromium alloy or a nickel-chromium alloy with some palladium added was used for the detection electrode 30, and silver (Ag) or silver chloride (Ag / AgCl) was used for the reference electrode 40. This is because, as a result of experiments, it was found that this combination of the various electrode material combinations obtained the most effective ozone-selective electromotive force and had ozone resistance.
The nickel-chromium alloy is used for the conventional copper (C
Nickel (Ni) has a greater ionization tendency than u), but because it forms an alloy with chromium (Cr), the corrosion resistance is improved. Furthermore, this nickel-chromium alloy (Ni-C)
(r alloy), once the surface is oxidized by ozone, exhibits corrosion resistance that is incomparable to that of copper (Cu) that has been conventionally used for ozone water, and the selectivity of ozone Electricity was comparable to that using gold. It should be noted that the reason for adding palladium is that it is desirable to add a small amount of palladium to give stability in the nickel-chromium alloy. Therefore, the technique of using palladium as the stabilizer for the nickel-chromium alloy is conventionally known. .

As a result of various experiments, silver (Ag) or silver chloride (Ag / AgCl) was used for the reference electrode 40. As a result of various experiments, silver (Ag) has a larger ionization tendency than conventional gold (Au). Nevertheless, compared with conventional gold (Au), nickel-chromium alloy (Ni-Cr alloy) or nickel-chromium alloy with some palladium (Pd) added is used as the counterpart electrode for a long time. It was found that a stable ozone concentration can be detected. When the cause was investigated, when silver (Ag) was used for the reference electrode 40, the surface was immediately oxidized by ozone, but When an oxide film is formed on the steel, it becomes immobile, and thereafter the oxidation by ozone does not proceed, and the electromotive force by ozone does not decrease.

Therefore, when chlorine (Cl) treatment (the surface is silver chloride) is used for passivation of silver (Ag), the same result is obtained, and the silver reference electrode 40 is used.
Was previously contacted with chlorine to form a layer of silver chloride (AgCl) as a passivation film on its surface, and stable use was possible for a long period of time.

In the present application, silver chloride (Ag / AgCl)
The term means not silver chloride (AgCl) having a uniform whole, but silver chloride (AgCl) obtained by reacting only the surface of silver (Ag) with chlorine (Cl) as described above.

Although it was of course examined that gold (Au) having a smaller ionization tendency was used for the reference electrode 40 instead of silver (Ag) or silver chloride (Ag / AgCl), a nickel-chromium alloy (Ni .Cr alloy) or nickel-chromium alloy with some palladium (Pd) added, silver (Ag) or silver chloride (A
g / AgCl) had higher ozone selectivity. Moreover, this silver (Ag) or silver chloride (Ag / Ag
By using Cl) as the reference electrode 40, it is possible to prepare a calibration electrode 61 described later made of gold (Au) having a smaller ionization tendency.

In addition to the above configuration, the invention of "Claim 2" does not change the gap between one or both of the detection electrode 30 and the comparison electrode 40 by the drive device 20 and the opposite electrode. Direction, and is made of a material different from that of the detection electrode 30 in opposition to the detection electrode 30, and even if ozone water is present between the detection electrode 30 and ozone, A calibration electrode 61 made of a metal whose electromotive force is small enough to be ignored is provided, and a reverse electrode corresponding to a galvanic cell electromotive force generated between the calibration electrode 61 and the detection electrode 30 is provided between the detection electrode 30 and the reference electrode 40. A calibration voltage applying device 60 for applying a voltage of a pole is provided, or a galvanic cell electromotive force of a reverse polarity corresponding to a galvanic cell electromotive force generated between the detection electrode 30 and the reference electrode 40 is generated by the calibration electrode 61. It is none in the jar.

As the calibration electrode 61, a nickel-chromium alloy (Ni-Cr alloy) or a nickel-chromium alloy to which a small amount of palladium (Pd) is added, that is, different from the detection electrode 30, and further copper (Cu) is used. ), Lead dioxide (PbO ₂ ), silver (Ag), that is, a metal whose ozone electromotive force is so small that it can be ignored,
In this example, gold (Au) was used.

When gold (Au) is used for the calibration electrode 61,
A nickel-chromium alloy (Ni-Cr alloy) or a nickel-chromium alloy to which a small amount of palladium (Pd) is added for the detection electrode 30, and a silver (A
g) or silver chloride (Ag / AgCl), almost no electromotive force due to ozone is obtained, and this electromotive force is a so-called galvanic electromotive force which is proportional to the concentration of the electrolytic substance dissolved in the liquid to be measured. .

An example of providing the calibration electrode 61 in a pair is as shown in FIG. 6, and a small-diameter main body portion 10c or a small-diameter main body portion 10c which will be described later so that the coil-shaped detection electrode 30 and the coil-shaped calibration electrode 61 do not come into contact with each other. The drive shaft 23 or both the small-diameter main body portion 10c and the drive shaft 23 are fixedly attached.

As shown in FIG. 7, the calibration voltage applying device 60 has a battery 63, a variable resistor 62, and a third voltmeter 50a between the detection electrode 30 and the comparison electrode 40.
3 is connected in series, and the second voltmeter 50a2 is attached between the detection electrode 30 and the calibration electrode 61 via the changeover switch S3.
3 is adapted to be able to switch between the first voltmeter 50a1 connected to the detection electrode 30 and the comparison electrode 40. A desired voltage can be applied to the detection electrode 30 and the comparison electrode 40 by adjusting the variable resistor 62. And before measuring the concentration of ozone water,
The electromotive force between the detection electrode 30 and the calibration electrode 61 is measured by the second voltmeter 50a2. That is, the switch S3 of "FIG. 7" is connected to the side of the second voltmeter 50a2 opposite to the one shown in the figure, and the detection electrode 30, the comparison electrode 40, and the calibration electrode 61 are immersed in the liquid to be measured, and the second voltage is applied. Record the total detected value of 50a2.

The above-mentioned electromotive force is generated when an electrolyte such as chlorine is dissolved in the liquid to be measured, and it is almost recognized that it is not due to ozone. Therefore, it is necessary to grasp its value in advance and remove it. Therefore, when the above value is obtained, a voltage having a value that cancels this electromotive force is applied between the detection electrode 30 and the comparison electrode 40 by the calibration voltage applying device 60.

That is, the third voltmeter 5 is connected by the variable resistance.
When a voltage of the same magnitude as the detected value recorded above is applied between the detection electrode 30 and the comparison electrode 40 by the calibration voltage applying device 60 while observing 0a3, the voltage is dissolved in the liquid to be measured. The effect of electrolytes other than ozone can be eliminated.

In the present embodiment in which gold (Au) is used for the calibration electrode 61, the calibration voltage applying device 60 is used as a result of the experiment.
Was optional. That is, when the solution to be measured is an electrolytic solution, the calibration electrode 61 serves as an anode and the detection electrode 30 serves as a cathode, and the detection electrode 30 serves as a cathode and the comparison electrode 40 serves as an anode between the detection electrode 30 and the comparison electrode 40. , The current flowing between the calibration electrode 61 and the detection electrode 30 and the current flowing between the detection electrode 30 and the comparison electrode 40 have substantially the same magnitude and opposite directions, and therefore, as shown in FIG. If a method is adopted, that is, if both output terminals of the detection electrode 30 and the calibration electrode 61 are electrically connected, it can be considered that the correction is automatically performed without using the battery 63. It turned out to be a thing. The symbol R in FIGS. 7 and 8 indicates the shunt resistance.

The invention according to claim 3 is the detection electrode 3
0 is configured to be linearly reciprocated by the driving device 20, and the comparison electrode 40 is positioned at the same radial distance from the axis of the detection electrode 30 in the movement direction. The cylinder 40a, the cylindrical wire netting 40b, the coil 40c, and the plurality of electrode bodies 40d. , 40d, 40d ...
・ It consists of either.

In this kind of ozone water concentration measuring device, since the electromotive force to be measured is very small, the detection electrode 30 and the comparison electrode 40 are
Has a need to increase its surface area and detect a small electromotive force. Therefore, as described above, even if the detection electrode 30 and the comparison electrode 40 are arranged in parallel with each other in a straight line, the measurement is not impossible. Even if the signal is amplified, the fluctuation amount tends to increase. It is known that this phenomenon can be suppressed by increasing the surface area of the detection electrode 30 and the comparison electrode 40, but the effect is not so recognized in the conventional device, and the surface area of the electrode is increased. Even the phenomenon in which the fluctuation of the detected value became larger due to this was observed.

That is, when the surface areas of the detection electrode 30 and the comparison electrode 40 are increased, a relatively large electromotive force can be obtained, but in the relationship of the contact moving parts of the liquid under measurement and the detection electrode 30 or the comparison electrode 40. The contact area becomes wider, and the frictional portion at the contact portion between the liquid to be measured and the detection electrode 30 or the comparison electrode 40 increases, and as a result, an eddy current is likely to be generated, and this eddy current causes a variation in the measured value. It turned out that

Therefore, when a structure in which the influence of the vortex flow is small even if the electrode area is enlarged is pursued, it is firstly found from the results of experiments that it is effective to increase the surface area on the comparison electrode 40 side. That is, the vortex flow generated near the surface of the detection electrode 30 interferes with the contact of the new measured liquid with the detection electrode 30, but the vortex flow near the comparison electrode 40 far from the detection electrode 30 is less affected. It was not received.

Therefore, when the surface area on the comparison electrode 40 side was set large, the electromotive force increased.
Forming 0 as a cylinder 40a as shown in FIG. 9 located at the same radial distance from the axis of the detection electrode 30 in the direction of movement makes it possible to effectively utilize the entire inner peripheral surface of the reference electrode 40, and thus the most electromotive force. Was large and stable.

However, when the above-mentioned cylinder 40a is used as the reference electrode 40, it is used in still water and the arrow Y5 is shown in FIG.
Although there was no problem in using this cylinder 40a in running water in the axial flow, the running water flowing in the cylinder 40a indicated by arrow Y6 in FIG.
0a is difficult to flow into, and the liquid flow that wraps around the upper and lower open ends of the cylinder 40a and flows into the cylinder 40a becomes a vortex flow. This vortex flow reaches the vicinity of the surface of the detection electrode 30. It was accompanied.

Therefore, as shown in FIG. 10, the cylinder 40
a is vertically divided into sub-pieces, and each electrode body 40d,
40d, 40d, ... Are respectively located at the same radial distance from the axis of the detection electrode 30 in the movement direction. However, the above problems can be almost solved, and the axial flow indicated by the arrow Y5 and the arrow Y6. There was almost no problem in use in the flow in the direction orthogonal to the axial direction indicated by.

However, the comparative electrode 40 of the above-mentioned "FIG. 10" example
Also, since a vortex is generated when the liquid flow in the direction of the arrow Y6 flows inward from the gap between the electrode bodies 40d, 40d, "Fig.
In the "1" example, the cylindrical wire netting 40b was adopted in order to provide a large number of passage spaces for the liquid flow, but the vortex flow did not reach the central detection electrode 30 site, and the measured value was stable with little fluctuation.

In the reference electrode 40 of the above-mentioned "FIG. 11", too, if the flow velocity in the direction orthogonal to the axis (direction of arrow Y6) is too high, the eddy current may reach the detection electrode 30. Use "Fig. 1""Fig.5""Fig.6"
The coil 40c shown in FIG. 12 was used. Although this coil 40c has a relatively large total surface area depending on the pitch of the spiral, and a vortex is generated on the downstream side after passing through the constituent line portion of the coil 40c, the distance between adjacent vortices is wide, so As in the case of the cylindrical wire netting 40b, the fine eddy currents influence each other and never reach the detection electrode 30 without being damped.

In the above-mentioned "FIG. 10" example, the cylinder 40a is vertically divided into a plurality of sub-pieces, and the respective electrode bodies 40d, 40 are divided.
d, 40d, ..., However, each of the electrode bodies 40d may be changed to a plurality of vertical bars instead of the illustrated arc-shaped plate.

The metal cylindrical body 40a, the cylindrical wire mesh 40b, the metal coil body 40c, and the plurality of electrode bodies 40d, 4 located at the same radial distance from the axis of the detection electrode 30 in the movement direction.
Reference electrode 4 composed of either 0d, 40d ...
0 has its upper end connected or fixed to the densitometer body 10 directly or via a connecting arm (not shown), or the densitometer body 1
It is connected to the drive unit 20 housed in 0.

Next, in addition to the above-mentioned structure, the invention of "Claim 4" comprises the detection electrode 30 with a coil 30c, the upper end of which is fixed to the densitometer main body 10, and the detection electrode 30 is fixed. The drive shaft 23 protruding from the densitometer main body 10 and reciprocating linearly in a vertical direction is fixed to a portion at least one pitch away from the coil.

FIG. 5 shows the detection electrode 30 in the coil 3
In an example configured with 0c, the upper end of the detection electrode 30 is a large-diameter coil portion 31 into which the densitometer main body 10 is fitted, and a portion distant from the large-diameter coil portion 31 by at least one pitch is a densitometer. A small-diameter coil portion 32 into which a drive shaft 23 protruding from the main body 10 and linearly reciprocating in the vertical direction is inserted, and the large-diameter coil portion 31, the small-diameter coil portion 32, and an intermediate portion do not come into contact with the drive shaft 23. The coil 30c is formed as 33, and the large-diameter coil portion 31 is fixed to the densitometer body 10 and the small-diameter coil portion 32 is fixed to the drive shaft 23.

The above-mentioned coil 30c is attached to the densitometer main body 10 at the lower part of the large-diameter main body 10b.
0c are continuously provided, and a concave groove 10d is spirally provided on the outer periphery of the small-diameter main body portion 10c. The large-diameter coil portion 31 at the upper end of the coil 30c is screwed and fixed to the concave groove 10d.

A concave groove 10e is also provided in the outer periphery of the drive shaft 23 in a spiral shape, and a small-diameter coil portion 32 separated from the coil of the coil 30c by one pitch or more is screwed into the concave groove 10e. Since the drive shaft 23 protrudes from the small-diameter main body portion 10c and is usually configured to have a smaller diameter than the small-diameter main body portion 10c, the drive shaft 23 at an intermediate portion between the large-diameter coil portion 31 and the small-diameter coil portion 32 of the coil 30c. The free-diameter coil portion 33 that does not come into contact with is configured so that the upper portion has a larger diameter in order, and can be screwed together with the concave grooves 10d and 10e having different diameters.

As described above, the free-diameter coil portion 33 allows the lower end free end of the coil 30c to easily move, and prevents the movement from affecting the large-diameter coil portion 31 on the fixed side. Therefore, a minute electric signal can be directly taken out without a sliding portion.

Incidentally, the densitometer main body 10 of the coil 30c
The fastening to the drive shaft 23 and the drive shaft 23 may be performed by using appropriate means such as fitting, fastening, and fixing in place of, or in addition to, screwing into the concave grooves 10d and 10e.

In the invention of "Claim 4", the reference electrode 40 has the metal cylindrical body 40a, the cylindrical wire netting 40b, and the metal cylindrical body 40a located at the same radial distance from the axis of the detection electrode 30 in the movement direction.
Metal coil body 40c, multiple electrode bodies 40d, 40d, 4
"Claim 2" is configured by any of 0d ...
It is the same as the invention of.

Further, in the invention of "Claim 5", the detecting electrode 30 and the reference electrode 40 immersed in the liquid to be measured, and the measuring section 50 for measuring the electromotive force between the detecting electrode 30 and the reference electrode 40 are measured. In the ozone water concentration measuring device configured by the above, the detection electrode 30 has a large-diameter coil portion 31 into which the densitometer main body 10 is fitted, and the detection electrode 30 is separated from the large-diameter coil portion 31 by at least one pitch of the coil. Main part of the densitometer 1
Drive shaft 23 protruding from 0 and reciprocating in the vertical direction
And the large-diameter coil portion 3
1 and the small-diameter coil portion 32 and the intermediate portion are constituted by a coil 30c which is a free-diameter coil portion 33 that does not contact the drive shaft 23, the large-diameter coil portion 31 is used for the densitometer body 10, and the small-diameter coil portion 32 is used for the drive shaft. It is the same as the invention of "Claim 4" that it is fixedly attached to 23.

Further, in the invention of this section, the reference electrode 40 is constituted by a coil 40c which is coaxial with the detection electrode 30 and surrounds the outside of the detection electrode 30, and the upper end of the coil 40c.
The detection electrode 30 is fixedly attached so that it does not make electrical contact with the detection electrode 30.

The reason why the comparison electrode 40 is limited to the coil 40c in the present invention is that the eddy current does not affect the detection electrode 30 even at a relatively high flow velocity. In order to fix the coil 40c to the densitometer main body 10 so as not to make electrical contact with the detection electrode 30, in the example of FIG. 5, a spiral shape is formed on the outer peripheral surface of the large-diameter main body 10b of the densitometer main body 10. Although the groove 10f is provided in the above and the upper portion of the coil 40c is screwed into the groove 10f, it may be fixed by other appropriate means as described above.

Further, in the invention of "Claim 6", the detection electrode 30 according to "Claim 1" to "Claim 5" is made of nickel-chromium alloy (Ni-Cr alloy) or nickel-chromium alloy. Of palladium (Pd), and the reference electrode 40 is made of silver (Ag) or silver chloride (Ag / AgCl).

The detection electrode 30 is a nickel-chromium alloy (N
i.Cr alloy) or nickel-chromium alloy (Ni.
The reason why the reference electrode 40 is made of silver (Ag) or silver chloride (Ag / AgCl) is the same as the previous period, but the palladium is nickel. It is conventionally known that it functions as a stabilizer for an alloy of chrome and chromium. When the detection electrode 30 and the comparison electrode 40 are immersed in ozone water, silver has a smaller ionization tendency, so that the comparison electrode 40 serves as a cathode and the detection electrode 30 serves as an anode. When an oxide film is formed on the surface of the reference electrode 40 by ozone water, it becomes immobile and is less likely to be denatured thereafter, so that stable electromotive force can be permanently detected thereafter.

Since the inventions of "Claim 7" to "Claim 9" have already been described as one mode of the embodiment,
The description is omitted here.

[0109]

As described above, according to the present invention, since the liquid to be measured is moved on the electrode side without moving, a stable and highly reliable ozone concentration with little eddy current and gas precipitation is obtained. It is possible to provide an ozone water concentration measuring device which can measure the above-mentioned characteristics and which has a high responsiveness due to the high speed movement of the electrode.

As a concrete effect, test measurement values are shown in FIG. This testing device uses nickel
Chromium alloy (Ni / Cr alloy) or nickel / chromium alloy with some palladium (Pd) added,
Silver (Ag) or silver chloride (Ag / AgC) is used as the reference electrode 40.
Using the example of "FIG. 5" using 1), the detection electrode 30 was moved up and down 60 times per second with a stroke of 3 mm.
Then, 100 KΩ and 10 KΩ were prepared for the shunt resistance R, and the voltmeter 50 a was used for the measurement unit 50. As a result, the value of B in the figure using a shunt resistance R of 10 KΩ is smaller than the value of A in the figure using a shunt resistance R of 100 KΩ, but the linearity is good, and the ozone water concentration is sufficient for practical use. It was possible to provide a measuring device.

Further, "FIG. 14" shows that when the two-dot chain line makes the liquid to be measured stationary, the one-dot chain line shows the liquid to be measured at 2 cm / cm2.
In the case of seconds, the broken line represents the measured liquid of 5 cm / sec, the solid line represents the case of the present invention, and the measured liquid holds the ozone concentration of 12 ppm, and the same device (shunt resistance 10 KΩ) as described above is used. The results are compared with time.
As a result, as is clear from the figure, the present invention was able to provide an ozone water concentration measuring device that hardly changes with time.

Further, since the present invention is constituted by linearly reciprocating the electrode, the signal can be taken out from the linear reciprocating motion without using a contact signal taking-out part such as a rotating part and a brush. It is possible to provide an ozone water concentration measuring device capable of accurately reading a signal.

The invention of "Claim 2" is the calibration electrode 6
Since No. 1 is provided, it is possible to provide an ozone water concentration measuring device capable of appropriately calibrating the measurement error due to the electrolyte dissolved in the liquid to be measured.

Further, the invention of "claim 4" is the comparison electrode 4
0 is located at the same radial distance from the axis of the detection electrode 30 in the movement direction, the metal cylindrical body 40a, the cylindrical wire mesh body 40b, the metal coil body 40c, the plurality of electrode bodies 40d, 40d, 40d.
Since it is configured by any of the above, a uniform electric field due to electromotive force can be obtained between the detection electrode 30 and the comparison electrode 40 in substantially all directions centering on the detection electrode 30, and a stable detection signal with little fluctuation can be obtained. The ozone water concentration measuring device can be provided.

Further, in the inventions of "Claim 4" and "Claim 5", the detection electrode 30 is constituted by the coil 30c, and the upper end of the detection electrode 30 is fixed to the densitometer main body 10 and the detection electrode 30 is stopped. A part that is at least one pitch apart from the coiled part,
Drive shaft 2 that linearly reciprocates protruding from the densitometer body 10
Since the lower end of the coil 30c can be linearly reciprocated, the detection electrode 30 is fixed to the detection electrode 30.
The upper part of is fixed, and by connecting and fixing a conducting wire to this fixing part, it is possible to provide an ozone water concentration measuring device which can easily take out a signal with less noise.

Further, the invention of "claim 5" is the detection electrode 3
The upper end portion of 0 is a large-diameter coil portion 31 into which the densitometer main body 10 is fitted, and a portion apart from this large-diameter coil portion 31 by one pitch or more is a straight line in the vertical direction protruding from the densitometer main body 10. A metal coil body 30c is used which is a small-diameter coil portion 32 in which the reciprocating drive shaft 23 is fitted, and the large-diameter coil portion 31, the small-diameter coil portion 32, and an intermediate portion are free-diameter coil portions 33 that do not contact the drive shaft 23. The large-diameter coil portion 31 is provided in the densitometer main body 10, and the small-diameter coil portion 3 is provided.
Since 2 is fixedly attached to the drive shaft 23, the ozone water concentration measuring device in which the movement of the detection electrode 30 is easy and reliable can be provided.

Further, the reference electrode 40 is a metal coil body 40 coaxial with the detection electrode 30 and surrounding the detection electrode 30.
c, and the upper end of the sample is fixed to the densitometer body 10 so as not to make electrical contact with the detection electrode 30, so that the liquid to be measured can be placed either parallel to or perpendicular to the detection electrode 30. It is also possible to provide an ozone water concentration measuring device having a high performance and capable of generating a vortex and less ozone deposition even if the detection electrode 30 is linearly reciprocated relatively quickly.

Further, the invention of "claim 6" is the detection electrode 3
0 is composed of a nickel-chromium alloy (Ni-Cr alloy) or a nickel-chromium alloy to which some palladium (Pd) is added, and the reference electrode 40 is silver (Ag) or silver chloride (Ag / AgCl). Since the reference electrode 40 is made immobile, the reference electrode 40 can provide an ozone water concentration measuring device capable of stable measurement for a long period of time.

Further, the invention of "Claim 7" is the drive unit 2
Since the motor 21 is used for 0 and the linear reciprocating motion of the drive shaft 23 is changed by the crown gear 22 to the eccentric disc 26, either or both of the detection electrode 30 and the comparison electrode 40 can be reliably driven with a simple configuration. It is possible to provide a compact and simple ozone water concentration measuring device that can be used as a portable device.

The invention according to claim 8 is the drive device 2
Since the electromagnetic vibrator 20a is used for 0, continuous operation is possible for a long period of time, and an ozone water concentration measuring device suitable for continuous measurement in an ozone water utilization system can be provided.

Further, in the invention of "Claim 9", since the electromagnetic vibrator 20a is operated by the trapezoidal wave AC power source, the driving of either or both of the detection electrode 30 and the comparison electrode 40 is performed at the top dead center. It is driven near the bottom dead center and fast at the middle point between the two, and even if the driving amount speed is increased, the ratio of stirring the liquid to be measured is reduced, and a higher performance ozone water concentration measuring device can be provided. .

[Brief description of drawings]

FIG. 1 is a perspective view of an essential part showing an embodiment of an ozone water concentration measuring device of the present invention.

FIG. 2 is a vertical cross-sectional view of a drive unit of a detection electrode used in the present invention.

FIG. 3 is a vertical cross-sectional view of another embodiment of the drive unit of the detection electrode used in the present invention.

FIG. 4 is a graph showing a power supply current to the “FIG. 3” driving unit.

FIG. 5 is a front view of a main part showing another embodiment of the ozone water concentration measuring device of the present invention.

FIG. 6 is a front view of a main part showing still another embodiment of the ozone water concentration measuring device of the present invention.

FIG. 7 is a wiring diagram of a calibration electrode used in the present invention.

FIG. 8 is another wiring diagram of the calibration electrode used in the present invention.

FIG. 9 is a perspective view of a reference electrode used in the present invention.

FIG. 10 is a perspective view of another embodiment of the reference electrode used in the present invention.

FIG. 11 is a perspective view of yet another embodiment of a reference electrode used in the present invention.

FIG. 12 is a perspective view of yet another embodiment of a reference electrode used in the present invention.

FIG. 13 is an actual measurement data graph in the device of the present invention.

FIG. 14 is a graph of measurement data over time in the case where the flow velocity of the liquid to be measured is changed and the device of the present invention.

FIG. 15 is a vertical sectional view of a conventional example.

FIG. 16 is a graph showing fluctuations in measured values obtained by changing the flow velocity of the liquid to be measured in the “FIG. 13” conventional example.

FIG. 17 is a front view of another conventional example.

FIG. 18 is a vertical sectional view of still another conventional example.

[Explanation of symbols]

 10 densitometer main body 20 drive device 20a electromagnetic vibrator 21 motor 21a motor drive shaft 22 crown gear 23a oscillator 23a 24 gear 25 horizontal shaft 26 eccentric disc 26a eccentric disc body 26b driven body 23 drive shaft 30 detection electrode 30c coil 31 large diameter coil Part 32 Small-diameter coil part 33 Free-diameter coil part 40 Reference electrode 40a Metal cylinder 40b Cylindrical wire mesh body 40c Metal coil body 40d Electrode body 50 Measuring part 60 Calibration voltage application device 61 Calibration electrode

Claims (9)

[Claims] 1. A detection electrode (30) immersed in a liquid to be measured.
And a comparison electrode (40), and a measuring unit (50) for measuring an electromotive force between the detection electrode (30) and the comparison electrode (40). ) And the reference electrode (40), or both of them, are linearly reciprocated in a direction in which the gap between the drive device (20) and the opposite electrode is not changed. measuring device. 2. A detection electrode (30) immersed in a liquid to be measured.
And a comparison electrode (40), and a measuring unit (50) for measuring an electromotive force between the detection electrode (30) and the comparison electrode (40). ) And the reference electrode (40) or both of them are linearly reciprocated in a direction in which the gap between the drive device (20) and the opposite electrode is not changed. Further, the detection electrode (30) And is made of a material different from that of the detection electrode (30).
0) is provided with a calibration electrode (61) made of a metal whose ozone electromotive force is small enough to be ignored even if ozone water is present, and between the detection electrode (30) and the comparison electrode (40),
A calibration voltage applying device (60) for applying a reverse polarity voltage corresponding to a galvanic cell electromotive force generated between the calibration electrode (61) and the detection electrode (30) is provided, or the calibration electrode (61) is detected. An ozone water concentration measuring device characterized in that a galvanic cell electromotive force of a reverse polarity corresponding to a galvanic cell electromotive force generated between an electrode (30) and a comparison electrode (40) is produced. 3. A detection electrode (30) immersed in a liquid to be measured.
And a comparison electrode (40), and a measuring unit (50) for measuring an electromotive force between the detection electrode (30) and the comparison electrode (40). ) Is made to reciprocate linearly by the driving device (20), and the reference electrode (40) is located at the same radial distance from the axis of the detection electrode (30) in the linear movement direction.
a), cylindrical wire mesh body (40b), metal coil body (40)
c), a plurality of electrode bodies (40d, 40d, 40d ...)
An ozone water concentration measuring device characterized in that any one of the above is fixed. 4. A detection electrode (30) immersed in a liquid to be measured.
And a comparison electrode (40), and a measuring unit (50) for measuring an electromotive force between the detection electrode (30) and the comparison electrode (40). ) Is composed of a coil (30c), the upper end of which is fixed to the densitometer main body (10), and a portion at least one pitch away from the fixed part of the detection electrode (30) is separated from the densitometer. The reference electrode (40) is fixed to a drive shaft (23) protruding from the main body (10) and linearly reciprocating in the vertical direction, and the comparison electrode (40) is located at the same radial distance from the axis of the detection electrode (30) in the movement direction. Cylinder (40a),
An ozone water concentration measuring device characterized in that any one of a cylindrical wire mesh body (40b), a metal coil body (40c), and a plurality of electrode bodies (40d, 40d, 40d ...) Is fixed. 5. A detection electrode (30) immersed in a liquid to be measured.
And a comparison electrode (40), and a measuring unit (50) for measuring an electromotive force between the detection electrode (30) and the comparison electrode (40). ) The densitometer body (1
0) is inserted into the large-diameter coil portion (31), and a linear reciprocating motion in a vertical direction protruding from the densitometer main body (10) at a portion at least one pitch away from the large-diameter coil portion (31) The small diameter coil portion (32) into which the drive shaft (23) is inserted, and the large diameter coil portion (31), the small diameter coil portion (32) and the intermediate portion do not come into contact with the drive shaft (23). 33) Metal coil body (30)
c), the large diameter coil portion (31) is fixedly attached to the densitometer body (10), and the small diameter coil portion (32) is fixedly attached to the drive shaft (23), and the comparison electrode (40) is also provided. Is a metal coil body (4) which is coaxial with the detection electrode (30) and surrounds the outside of the detection electrode (30).
0c), the upper end of which is attached to the densitometer body (10) so as not to make electrical contact with the detection electrode (30). 6. The detection electrode (30) is composed of a nickel-chromium alloy (Ni-Cr alloy) or a nickel-chromium alloy to which some palladium (Pd) is added, and the comparison electrode (40). Is composed of silver (Ag) or silver chloride (Ag / AgCl), and the ozone water concentration measuring device according to any one of claims 1 to 5. 7. The drive device (20) comprises a motor (2).
1) and a motor drive shaft (21a) of this motor (21)
The crown gear (22) rotating by the gear, the gear (24) attached to the horizontal shaft (25) and meshing with the crown gear (22), and the eccentric disc (26) attached to the horizontal shaft (25). The eccentric disc body (2) is fixed to the horizontal shaft (25) and rotates together with the eccentric disc body (26a).
6a) and a driven body (26b) including the eccentric disc body (26a), and a drive shaft (23) is integrally suspended from the driven body (26b). (23) is a vertical hole (1
0a) so that it can move only in the vertical direction,
The drive shaft (23) and the detection electrode (30) connected to the drive shaft (23) are linearly reciprocated in the vertical direction by the motor (21).
To the ozone water concentration measuring device according to claim 5. 8. The drive device (20) is composed of an electromagnetic vibrator (20a), and the electromagnetic vibrator (2).
0a) vibrator (23a) is connected to a drive shaft (23) and a detection electrode (30) connected to the drive shaft (23),
The ozone water concentration measuring device according to any one of claims 1 to 5, characterized in that the detection electrode (30) reciprocates linearly. 9. The drive device (20) is composed of an electromagnetic vibrator (20a) driven by a trapezoidal wave AC power source, and a vibrator (23) of the electromagnetic vibrator (20a).
The drive shaft (23) and the detection electrode (30) connected to this drive shaft (23) are connected to a), and this detection electrode (30) is connected.
The apparatus for measuring ozone water concentration according to any one of claims 1 to 5, characterized in that it reciprocates linearly.