JPS60100049A - Removal of specific ion and specific ion remover using same - Google Patents

Abstract

PURPOSE:To remove a specific ion from a sample by injecting the sample to be measured from an injection needle mounted at the tip of a syringe through a filter unit. CONSTITUTION:After a sample to be measured containing Cl<-> ion is put at the top of a springe 1, a piston 10 is inserted into the syringe 1 and the sample being measured is pressed with a rubber 11. The sample is injected outside passing sequentially through a glass fiber filter 3, an Ag type cation exchange resin 2, a teflon filter 4, a membrane filter 6 and a injection needle 9. While the sample passes through the cation exchange resin 2, Cl<-> ion is removed and Ag<+> is released to generate AgCl in reaction with Cl<-> ion. Thus, Na<+> bonds to the resin and as Na<+> and Cl<-> are consumed, Cl<-> ion vanishes.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing specific ions from a sample injected into an injector such as an ion chromatograph, and a specific ion remover using the method.

When attempting to measure trace amounts of anions contained in samples containing large amounts of chlorine ions, such as foods, biological samples, and seawater using an ion chromatograph, the large beak of chlorine ions interferes with the measurement of specific ions (e.g., Br0). - ions) is difficult to measure. For this reason,
Inject Ag-type cation exchange resin into the sample and use the following formula (1)
The chlorine ions in the sample were removed by causing a reaction like (2) to produce and precipitate poorly soluble silver chloride.

Re5in −Ag + Na + C1+: Re5
in −Na +Ag +cz (1)Resin −
Na +Ag +CL −+ Re5in-Na +
Since the AgCL (2) exchange reaction is determined by the ion selectivity coefficient for the ion exchange resin, in a system where the sample and Ag type ion exchange resin exist together, Na+ and Ag+
exist at a certain ratio. For this reason, the above (
2) The reaction in formula proceeds rapidly to produce AgCt, but
In the above formula (1), the Ct- ion, which is the counter ion of the remaining Na+ ion, remains in the sample in the state of Na+C2-. Therefore, the chloride ion concentration is 1 to 1, such as in foods.
In samples containing 3 ions, the chloride ion concentration was reduced to several ppp.
It is difficult to reduce the concentration to m, and there is a drawback that it is not possible to measure ions (for example, BrO3 ions, etc.) that appear near several ppm of chlorine ions.

The present invention has been made in view of the above drawbacks, and the object thereof is to provide a specific ion removal method for removing from a sample specific ions that interfere with the measurement of ions to be measured, and a specific ion removal method using the same. There is a need to provide utensils.

The features of the present invention are a method for removing specific ions from a sample injected into an injector such as an ion chromatograph, and a specific ion remover using the same, in which a predetermined type of cation exchanger filled in the body of a syringe is used. Specific ions in the sample to be measured are removed by passing the sample to be measured through the resin and injecting the sample to be measured from an injection needle attached to the tip of the syringe via a filter unit. It's what I did.

Hereinafter, the present invention will be explained in detail using figures. 1st
The figure is an explanatory diagram of the configuration of an embodiment of the present invention. In the figure, 1 is a cylindrical disposable syringe, and 2-piece syringe 1
A cation exchange resin of a predetermined type (for example, Ag type) is filled in the body of the resin, 3 is a glass fiber filter that prevents the resin 2 from flowing out, and (3) 4 has a mesh size of, for example, 0.7 to 21 J. A Teflon filter 5 is equipped with a Teflon filter 4.
A filter body of, for example, a Diflon ring is attached to the tip of the syringe 1 so as to prevent the cation exchange resin 2 from flowing out to the other side, 6 is a membrane filter of, for example, 0.22μ, and 7 is a filter body with the filter 6 inside. For example, an MI manufactured by Mllllpore is attached to the tip of the filter body 5.
Disposable filters like LLEX-GS, 8
10 is a hub that has an injection needle 9 such as a 228 gauge needle and is attached to the tip of the disposable filter 7, and 10 is a piston that has a rubber 11 at the tip that has an outer diameter slightly larger than the inner diameter of the syringe 1. be. In addition, the above-mentioned cation exchange resin is, for example, DOW8X 50W-X8, 2
A strongly acidic cation exchange resin of 00 to 400 mesh is made into an Ag type using a silver nitrate aqueous solution, and then sufficiently pressure washed with deionized water to reduce the NO3- ion concentration to 0. The syringe 1 is filled with the syringe whose concentration is 1 ppm or less.

In the embodiment of the present invention having the above configuration, first, a sample to be measured is placed in the space K of the syringe 1 (the part above the glass fiber (4) bar filter 3 in FIG. 1). Next, the piston 10 is inserted into the syringe 1, and the rubber 11 presses the sample to be measured in the space. The sample is passed through the glass fiber filter 3 -> cation exchange measurement While the sample passes through the cation exchange resin 2, the Ct- ions contained therein are removed by the following process. That is, in FIG. 1, the total length of the portion filled with the cation exchange resin 2 is L.
Then, these can be considered to be a collection of a plurality of stages of unit length ΔL. Also, from each of these stages,
Ag'f-on is released by the reaction of formula (1) above.

This Ag+ ion immediately reacts with the Ct- ion in the sample to be measured according to the above equation (2) to generate a sparingly soluble salt AgCt. Because Na+ and Ct- are consumed by such reactions, as the above stages move downward in Figure 1, the amounts of Na+ and Ct- in the sample to be measured gradually decrease compared to the amounts supplied to the upper stages. . Therefore, when the lowest stage is reached, there are no Na+ ions in the sample to be measured. In addition, the Ct- ions, which were trapping the Na+ ions and counter ions, also disappear. In other words, when the sample to be measured is passed from the upstream part of the Ag-type cation exchange resin column, the Na + ion concentration gradually decreases at each stage of the column, and the KC
LC ene also decreases, AgCl is generated and Ct- ions are removed. In this way, the injection needle 9
The sample to be measured that is injected from the sample does not contain Ct- ions.

FIG. 2 is an explanatory diagram of an example of use of the embodiment of the present invention, and in the figure,
For example, 5 mM'Na2B40. /1mM・N
a tank in which an eluent of aHcO3 is stored, 15 a pump for feeding the eluent, 14 an injector, 15 a separation column filled with, for example, an anion exchange resin;
16 is a suppressor, for example, a cation conversion membrane tube; 17 is a detector, for example, a conductivity detector.

Moreover, FIG. 3 is a usage effect explanatory diagram showing the usage effect of the embodiment of the present invention, in which (a) is a chromatogram created without using the embodiment of the present invention, and (b) is a chromatogram created without using the embodiment of the present invention. This is a chromatogram created using an example.

In FIG. 2, the eluent in the tank 12 flows in a flow path of pump 13 → injector 14 → separation column 15 → sublet 16 → detector 17. In this state, first, a kamaboko extract containing a large amount of chloride ions (hereinafter referred to as "experimental solution-1") was injected into a commercially available syringe.
Inject into the injector 14 shown in the figure.

This experimental solution is conveyed to the eluent, reaches the separation column 15, undergoes a predetermined separation, and then is sublet.

For example, the conductivity background is removed by a detector 17, and finally the conductivity is detected by a detector 17.

The detection signal from the detector 17 is guided to a recorder to give a romatogram as shown in FIG. 5(a). In this chromatogram, the chloride ion peak is very large, and B rO3 elutes near this peak.
-Ions etc. cannot be measured. Next, the above experimental solution is introduced into the above-described embodiment of the present invention and injected into the injector 14 shown in FIG. This experimental solution was treated in the same manner as in the case described above.7) As is clear, when the example of the present invention is used, the chloride ions in the sample to be measured are easily removed, and the B rOs eluted near the chloride ion peak. It becomes possible to easily quantify or qualify ions such as -.

According to the embodiment of the present invention as described in detail above, A
Since the configuration is such that the body of the syringe 1 is filled with the G-type cation exchange resin and the sample to be measured is taken into the syringe and injected, it is different from the conventional example in which the Ag-type cation exchange resin is injected into the sample. In contrast, it has the advantage that the removal rate of chlorine ions is extremely high. However, the present invention is not limited to the above-mentioned embodiments, and can be modified in various ways.
It is also possible to easily fill the container with a type cation exchange resin to remove SO;- ions and P07 ions from the sample to be measured. Therefore, according to the present invention, the drawbacks of the conventional examples are solved at once, and a specific ion removal method that removes specific ions that interfere with the measurement of ions to be measured from a sample, and a specific ion removal method using the same are provided. A specific ion remover is realized.

(8)

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of the configuration of an embodiment of the present invention, FIG. 2 is an explanatory diagram of an example of use of the embodiment of the present invention, and FIG. 3 is an explanatory diagram of the effect of use of the embodiment of the present invention. 1...Syringe, 2...Cation exchange resin, 3...
・Glass wool filter, 4...Teflon filter,
5... Filter body, 6... Membrane filter, 7
...Disposable filter, 8...Hub, 9.
...Syringe needle, 10...Piston, 11...Rubber, 1
2... Eluent tank, 15... Pump, 14... Injector, 15... Separation column, 16... Sable,
17...Detector. M3 diagram (a) 0 2 6 5 8 10 12m1n (b)

Claims (5)

[Claims] (1) Pass the sample to be measured through a predetermined type of cation exchange resin filled in the body of the syringe, and inject the sample to be measured from the injection needle attached to the tip of the syringe via a filter unit. Totoyoshi, a specific ion removal method characterized by removing specific ions in the sample to be measured. (2) The specific ion removal method according to claim (1), wherein the predetermined type is an Ag type, and the specific ion is a Ct- ion. (3) The specific ion removal method according to claim (1), wherein the predetermined type is B1 type, and the specific ion is an SO ion. (4) The specific ion removal method according to claim (1), wherein the predetermined type is the Fs type and the specific ion is the Fs type. (5) A syringe whose body is filled with a predetermined type of ion exchange resin, an injection needle attached to the tip of the syringe via a filter unit, and a needle inserted into the syringe and inside the syringe. a piston that presses the sample injected into the space, and injects the sample in the space from the injection needle through the cation exchange resin,
A specific ion remover, characterized in that it removes specific ions in the sample.