JPS62218849A - Reference sample for calibration of electrode for measuring ion - Google Patents

Abstract

PURPOSE:To simplify the preservation, carrying and use of a calibration refer ence liquid, by gelatinizing calibration reference liquid by a gelatinizing agent to house it into a cylindrical container in such a manner as to be allowed to be easily withdrawn. CONSTITUTION:When using a bar-like gelatinization reference liquid 1 arranged by adding gliserine to a reference liquid for calibration such as KCl as gel evaporation preventing agent and gelatinizing the mixture by agar, a cap 11 is removed and, for example, with a knob 6 fixed, an outer cylinder 7 is turned. Here, with the rotation of a spiral groove 9, a retaining projection 3 moves along a slit 5 to eject the gelatinization reference liquid 1 out of the outer cylinder 7 as shown by the chain line, so that a response section of an electrode for measuring ion to be calibrated comes into contact with the surface thereof. When being preserved and carried, the gelatinization reference liquid 1 is housed entirely into an inner cylinder 4 as shown by the solid line. Thus, the gelatinization reference liquid 1 is protected by the cap 11 and the contents 4 to make the preservation and the carrying thereof simple while enabling a simplified use at the calibration.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a standard sample for calibration of a -glass electrode, an ion electrode such as Na, ni, d, etc., a reference electrode, and other electrodes for measuring ions.

[Conventional technology]

When calibrating pH gas electrodes, ion electrodes such as Ha, Ni, D, and other ion measurement electrodes, conventionally, for example, a powdered calibration standard sample was dissolved in pure water such as distilled water during calibration. A calibration standard solution is prepared, and an ion measurement electrode is inserted into this standard solution.

In addition, in the ion measurement electrode, it was proposed in the 4th year of the Tokugawa Shogunate to gel the internal liquid with a gelling agent such as agar or gelatin.
It is disclosed in Japanese Patent Application Laid-open No. 7-45317 and Japanese Patent Application Laid-Open No. 47-7749.

[Problem that the invention seeks to solve]

When calibrating an ion measurement electrode, the conventional calibration standard solution in which a powdered calibration standard sample is dissolved in pure water has a problem in that it requires time and effort to prepare pure water and dissolve the sample therein. In addition, there is a problem in that the prepared standard solutions are often inconvenient to store and carry.

As a means to facilitate the storage and carrying of calibration standard solutions, the above-mentioned Japanese Patent Publication No. 47-45317 or Japanese Unexamined Patent Publication No. 47-7
It is conceivable to gel the standard solution like the gelled internal solution disclosed in Japanese Patent No. 749. However, the internal liquids disclosed in both of the above publications are simply gelatinized internal liquids using a gelling agent.

If it is left in the air at room temperature, it dries out, which poses many packaging and storage problems, making it almost impossible to use as a standard sample for calibration that can be stored or carried.

The present invention solves the above-mentioned problems, and aims to obtain a standard sample for calibrating an ion measurement electrode that is easy to use during calibration and can be stored and carried.

[Means for solving problems]

The calibration standard sample of the present invention uses a gel such as glycerin or ethylene glycol, which is water-soluble, has a lower b-p than water, and has a low vapor pressure at room temperature, as a calibration standard solution. The present invention is characterized in that an evaporation inhibitor is added, this calibration standard solution is gelled with a gelling agent, and this gelled standard solution is shaped into a rod and is housed in a cylindrical container so that it can be put in and taken out.

[Effect]

Since the calibration standard sample of the present invention is gelled and housed in a container, it can be stored or carried as is. Calibration of the ion measurement electrode is performed by taking one end of the gelled standard solution out of the cylindrical container and bringing the surface of the gelled standard solution into contact with the liquid junction of the ion measurement electrode, a responsive glass membrane, or the like.

Since gel evaporation prevention agents are added to the gelling standard solution, even if it is left in the air at room temperature for a long period of time, the surface will not dry and will always remain wet, so during calibration. It is only necessary to take out a portion of the gelling standard solution from the container.
And it can be used for a long time. When renewing the surface of the gelled standard solution, cut off the edge of the gelled standard solution along the mouth of the container.

〔Example〕

A first embodiment of the standard sample for calibration of the present invention will be described with reference to FIG.

In the figure, reference numeral 1 denotes a rod-shaped gelling standard solution, which is constructed by adding glycerin as a gel evaporation inhibitor to a Kd standard calibration solution and gelling it with agar. Reference numeral 2 denotes a container-shaped moving body into which one end of a gelled standard solution is inserted and fixed. Reference numeral 3 denotes a locking protrusion protruding from the outer surface of the peripheral wall of the movable body 2.

Reference numeral 4 denotes an inner cylinder into which the gelled standard solution 1 is slidably inserted together with the movable body 2, and the locking protrusion 3 is slidably inserted into a slit 5 provided in the axial direction of the inner cylinder 4. It has been inserted. 6 is a cylindrical knob fixed to the bottom end of the inner cylinder 4, 7 is an outer cylinder, and a spiral groove 9 is formed on the inner circumferential surface of a locking pipe 8 inserted and fixed inside the outer cylinder. .

The inner cylinder 4 is rotatably inserted into the locking pipe 8, and the tip of the locking protrusion 3 is inserted into the spiral groove 9. One end of the outer cylinder 7 is supported together with the locking pipe 8 by the knob 6, and the locking pipe 8
At the other end, a locking protrusion 10 provided on the outer periphery of the tip of the inner cylinder 4
is locked and attached to the inner cylinder 4 in a manner that cannot be separated. 11 is a cap.

When using this gelling standard solution 1, remove the camp 11 and, for example, fix the knob 6 and turn the outer cylinder 7. Then, the rotation of the spiral groove 9 causes the locking protrusion 3 to move along the slit 5. Since the gelled standard solution 1 is moved to the outside of the outer cylinder 7 as shown by the chain line, the response part of the ion measurement electrode to be calibrated is brought into contact with the surface of the gelled standard solution 1.

When storing or carrying, the entire gelled standard solution 1 is accommodated in the inner tube 4 as shown by the solid line as described above. Therefore, since the gelled standard solution 1 is protected by the cap 11, inner tube 4, etc., it can be easily stored and carried.

In addition to the above-mentioned glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and derivatives thereof can also be used as the gel evaporation inhibitor.

As the gelling agent, gelatin or any other substance capable of gelling the standard solution and the gel evaporation inhibitor can be used, and a super absorbent resin can also be used in combination.

The blending amounts of the standard solution, gel evaporation inhibitor, and gelling agent are as follows:
It is sufficient to select an amount that can gel the standard solution and the gel evaporation inhibitor, prevents the gel from evaporating, and maintains the surface of the gelled standard solution wet in air at room temperature.

An example of the above-mentioned blending amount is as follows when a Kd aqueous solution is used as the standard solution.

Ethylene glycol agar 3.3
ocz water tlfi 40cc 1 g
20cc25cc
Ig 5cc glycerin
Agar Kd aqueous solution 40cc
1 g (0,1M) 20cc35
cc 1 g 2
Each formulation example of 5 cc or more gelled to a hardness suitable for handling, and was left in air at room temperature for a long period of time.
The surface remained wet.

3.3 The amount of gel evaporation inhibitor such as glycerin relative to the standard solution such as MKcj aqueous solution should be 50 VOL% or more, even if the gelled standard solution is left in the air at room temperature for a long period of time. Suitable for preventing dryness.

In the above formulation example, a Kd aqueous solution was shown as the standard solution, but
Any other standard solution can be used.

2 and 3 show a second embodiment of the calibration standard sample of the present invention.

In the figure, reference numeral 21 represents a gelling standard solution in the form of a rod, which is the same as in the first embodiment. Reference numeral 22 denotes a moving body, to which an end of the gelled standard solution 21 is fixed. 2
3 is a cylindrical body, inside which a gelling standard solution 21 and a moving body 22 are placed.
is slidably inserted, and a protrusion 24 provided on the inner surface of the cylindrical body 23 in the axial direction engages with a groove 25 provided on the moving body 22.

Reference numeral 26 designates a knob, and a screw shaft 27 fixedly and protrudingly provided on this knob is passed through the bottom wall of the cylinder body 23, and a locking protrusion 28 provided on the screw shaft 27 allows the screw shaft 27 to be rotated and separated. The screw shaft 27 is attached to the cylinder body 23 and the screw shaft 27 is attached to the moving body 22.
is screwed into the screw hole 29 of the gelatinized standard solution 2.
It is inserted within 1. 30 is a cap.

In this embodiment, for example, the cylinder 23 is fixed and the knob 2
6, the gelled standard solution 21 comes out of the cylindrical body 23 together with the movable body 22 and enters the cylindrical body 23 due to the rotation of the screw shaft 27.

〔Effect of the invention〕

The calibration standard sample of the present invention is made by gelling the calibration standard solution with a gelling agent and storing it in a cylindrical container so that it can be put in and taken out, so its bulk can be reduced and it can be easily stored and carried. can. To calibrate the ion measurement electrode, simply bring its response part into contact with the surface of the gelled standard solution (
Easy to use.

In addition, a gel evaporation inhibitor is added to the gelled standard solution to prevent it from drying out and keep the surface constantly wet, allowing for highly accurate calibration and eliminating the need to seal the container. Because of this, it is possible to use a cylindrical container with any configuration, and the configuration can be simplified. Further, since the gelled standard solution is stored in a rod-like shape in a cylindrical container so that it can be taken out and put in, it is easy to use it repeatedly.

[Brief explanation of drawings]

FIG. 1 is a sectional front view showing a first embodiment of the present invention, FIG. 2 is a sectional front view showing a second embodiment, and FIG. 3 is a sectional plan view thereof. 1.21...gelling standard solution, 7...outer cylinder, 23...
・Cylinder body. Applicant Horiba Ltd. Agent Patent Attorney Hideo Fujimoto Figure 1 Figure 2 Figure 3 Voluntary Procedure Amendment June 18, 1988 Patent Application No. 63565 2, Title of Invention Ion Measurement Standard sample for calibration of electrodes for ion measurement 3, Relationship with the case of the person making the amendment Patent applicant 4, Agent 5, Full text correction statement of date of amendment order 1, Title of invention Standard sample for calibration of electrodes for ion measurement 2, Claims: The standard solution for calibration is water-soluble and has a -.p lower than that of water.
- Add a gel evaporation inhibitor such as glycerin or ethylene glycol, which has a high p value and a low vapor pressure at room temperature, gel this calibration standard solution with a gelling agent, and make this gelled standard solution into a rod shape and cylindrical. A standard sample for calibrating an electrode for ion measurement, characterized in that it is housed in a removable container. 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a standard sample for calibration of a glass electrode, an ion electrode such as Na, K%d, a reference electrode, and other ion measurement electrodes. [Prior Art] When calibrating ion electrodes such as pl+glass electrodes, Na, Ksd, and other ion measurement electrodes, conventionally, for example,
During calibration, a powdered calibration standard sample is dissolved in pure water such as distilled water to prepare a calibration standard solution, and an ion measurement electrode is inserted into this standard solution. In addition, in the ion measurement electrode, it was proposed in the 4th year of the Tokugawa Shogunate to gel the internal liquid with a gelling agent such as agar or gelatin.
It is disclosed in Japanese Patent Application Laid-open No. 7-45317 and Japanese Patent Application Laid-Open No. 47-7749. [Problems to be Solved by the Invention] When calibrating electrodes for ion measurement, the conventional calibration standard solution in which a powdered calibration standard sample is dissolved in pure water requires the labor and time of preparing pure water and adding the sample to it. There is a problem that requires time and effort to dissolve. In addition, there is a problem in that the prepared standard solutions are often inconvenient to store and carry. As a means to facilitate the storage and carrying of calibration standard solutions, the above-mentioned Japanese Patent Publication No. 47-45317 or Japanese Unexamined Patent Publication No. 47-7
It is conceivable to gel the standard solution like the gelled internal solution disclosed in Japanese Patent No. 749. However, the internal liquids disclosed in both of the above-mentioned publications are simply gelatinized internal liquids using a gelling agent, and if left in the air at room temperature, they will dry out, resulting in many problems with packaging and storage. occurs, making it almost impossible to use as a standard sample for calibration that can be stored or carried. The present invention solves the above-mentioned problems, and aims to obtain a standard sample for calibrating an ion measurement electrode that is easy to use during calibration and can be stored and carried. [Means for solving the problem] The calibration standard sample of the present invention has a calibration standard solution that is water-soluble, has a lower p (melting point) and higher b-p (boiling point) than water, A gel evaporation inhibitor such as glycerin or ethylene glycol, which has a low vapor pressure at room temperature, is added, this calibration standard solution is gelled with a gelling agent, and this gelled standard solution is shaped into a rod and placed in a cylindrical container. It is characterized by being housed so that it can be taken in and taken out. [Function] Since the calibration standard sample of the present invention is gelled and housed in a container, it can be stored or carried as is. Calibration of the ion measurement electrode is performed by taking one end of the gelled standard solution out of the cylindrical container and bringing the surface of the gelled standard solution into contact with the liquid junction of the ion measurement electrode, a responsive glass membrane, or the like. Since gel evaporation prevention agents are added to the gelling standard solution, even if it is left in the air at room temperature for a long period of time, the surface will not dry and will always remain wet, so during calibration. It is only necessary to take out a portion of the gelling standard solution from the container.
And it can be used for a long time. When renewing the surface of the gelled standard solution, cut off the edge of the gelled standard solution along the mouth of the container. (Example) A first example of the standard sample for calibration of the present invention will be described with reference to FIG. In the figure, reference numeral 1 denotes a rod-shaped gelling standard solution, which is constructed by adding glycerin as a gel evaporation inhibitor to a calibration standard solution such as Kd, and gelling it with agar. Reference numeral 2 denotes a container-shaped moving body into which one end of a gelled standard solution is inserted and fixed. Reference numeral 3 denotes a locking protrusion protruding from the outer surface of the peripheral wall of the movable body 2. Reference numeral 4 denotes an inner cylinder into which the gelled standard solution 1 is slidably inserted together with the movable body 2, and the locking protrusion 3 is slidably inserted into a slit 5 provided in the axial direction of the inner cylinder 4. It has been inserted. 6 is a cylindrical knob fixed to the bottom end of the inner cylinder 4, 7 is an outer cylinder, and a spiral groove 9 is formed on the inner circumferential surface of a locking pipe 8 inserted and fixed inside the outer cylinder. . The inner cylinder 4 is rotatably inserted into the locking pipe 8, and the tip of the locking protrusion 3 is inserted into the spiral groove 9. One end of the outer cylinder 7 is supported together with the locking pipe 8 by the knob 6, and the locking pipe 8
At the other end, a locking protrusion 10 provided on the outer periphery of the tip of the inner cylinder 4
is locked and attached to the inner cylinder 4 in a manner that cannot be separated. 11 is a cap. When using the gelled standard solution 1, remove the cap 11 and, for example, fix the knob 6 and turn the outer cylinder 7. Then, due to the rotation of the spiral groove 9, the locking protrusion 3 moves along the slit 5, causing the gelled standard solution 1 to protrude to the outside of the outer cylinder 7 as shown by the chain line, so that the calibration is applied to its surface. The response part of the ion measurement electrode is brought into contact with the ion measurement electrode. When storing or carrying, add gelation standard solution 1 as described above.
The entire body is accommodated in the inner cylinder 4 as shown by the solid line. Therefore, since the gelled standard solution 1 is protected by the cap 11, inner tube 4, etc., it can be easily stored and carried. In addition to the above-mentioned glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and derivatives thereof can also be used as the gel evaporation inhibitor. As the gelling agent, gelatin or any other substance capable of gelling the standard solution and the gel evaporation inhibitor can be used, and a super absorbent resin can also be used in combination. The blending amounts of the standard solution, gel evaporation inhibitor, and gelling agent are as follows:
What is necessary is to select an amount that can gel the standard solution and the gel evaporation inhibitor, prevents the evaporation of the gel, and maintains the surface of the gelled standard solution wet in air at room temperature. An example of the above-mentioned blending amount is as follows when a WcJ aqueous solution is used as the standard solution. Ethylene glycol agar 3.3
MKd aqueous solution 40cc 1 g
20cc25cc
Ig 5cc glycerin
Agar Kd aqueous solution 40cc
l g (0,1M) 20cc35
cc 1 g 2
5cc40cc 20g
Each formulation example of 20 cc or more gelled to a hardness suitable for handling, and the surface remained wet even when left in air at room temperature for a long period of time. 3.3 The amount of gel evaporation inhibitor such as glycerin relative to the standard solution such as MKd aqueous solution should be 50 VOL% or more, even if the gelled standard solution 1 is left in the air at room temperature for a long period of time. Suitable for preventing dryness. In the above formulation example, a Kd aqueous solution was shown as the standard solution, but
Any other standard solution can be used. 2 and 3 show a second embodiment of the calibration standard sample of the present invention. In the figure, reference numeral 21 represents a gelling standard solution in the form of a rod, which is the same as in the first embodiment. Reference numeral 22 denotes a moving body, to which an end of the gelled standard solution 21 is fixed. 2
3 is a cylindrical body, inside which a gelling standard solution 21 and a moving body 22 are placed.
is slidably inserted, and a protrusion 24 provided on the inner surface of the cylindrical body 23 in the axial direction engages with a groove 25 provided on the moving body 22. Reference numeral 26 designates a knob, and a screw shaft 27 fixedly and protrudingly provided on this knob is passed through the bottom wall of the cylinder body 23, and a locking protrusion 28 provided on the screw shaft 27 allows the screw shaft 27 to be rotated and separated. The screw shaft 27 is attached to the cylinder body 23 and the screw shaft 27 is attached to the moving body 22.
While being screwed into the through hole 29, the gelling standard solution 2
It is inserted within 1. 30 is a cap. In this embodiment, for example, the cylinder 23 is fixed and the knob 2
6, the gelled standard solution 21 comes out of the cylindrical body 23 together with the movable body 22 and enters the cylindrical body 23 due to the rotation of the screw shaft 27. [Effects of the Invention] The calibration standard sample of the present invention gels the calibration standard solution with a gelling agent and stores it in a cylindrical container so that it can be put in and taken out, so its bulk can be reduced and it can be stored easily. or mobile phone. The ion measurement electrode is easily calibrated by simply bringing its response part into contact with the surface of the gelled standard solution. In addition, a gel evaporation inhibitor is added to the gelled standard solution to prevent it from drying out and keep the surface constantly wet, allowing for highly accurate calibration and eliminating the need to seal the container. Because of this, it is possible to use a cylindrical container with any configuration, and the configuration can be simplified. Further, since the gelled standard solution is stored in a rod-like shape in a cylindrical container so that it can be taken out and put in, it is easy to use it repeatedly. 4. Brief Description of the Drawings FIG. 1 is a sectional front view showing a first embodiment of the present invention, FIG. 2 is a sectional front view showing a second embodiment, and FIG. 3 is a sectional plan view thereof. 1.21...gelling standard solution, 7...outer cylinder, 23...
・Cylinder body. Applicant: HORIBA, Ltd. Agent: Hideo Fujimoto, Patent Attorney Figure 1 1...Gelification standard solution 7...Outer tube 21...Gelification standard solution 23...Cylinder body 2Figure 3 figure

Claims (1)

[Claims] The calibration standard solution is water-soluble and has a lower m/p than water.
・Add a gel evaporation inhibitor such as glycerin or ethylene glycol, which has a high p value and low vapor pressure at room temperature, gel this calibration standard solution with a gelling agent, and make this gelled standard solution into a rod shape and transfer it to a cylinder. A standard sample for calibrating an electrode for ion measurement, characterized in that it is housed in a removable container.