Method of entrapping chlorine dioxide gas, method of determining concentration of chlorine dioxide and entrapping agent for chlorine dioxide

Abstract

A method of entrapping chlorine dioxide gas, including the steps of using an aqueous solution containing an alkaline substance and an iodide and bringing air containing the chlorine dioxide gas into contact with the aqueous solution.

Claims

1. A chlorine dioxide gas entrapping method comprising the steps of using an alkaline aqueous solution containing a strong alkaline substance and an iodide and bringing air containing the chlorine dioxide gas into contact with the aqueous solution, and reacting the strong alkaline substance, the iodide, and the chlorine dioxide gas to produce iodate and/or iodite, chloride, and water, wherein the strong alkaline substance contained in the aqueous solution has a concentration of 0.01 N or more.

2. The chlorine dioxide gas entrapping method according to claim 1, wherein the chlorine dioxide gas contained in the air is present in a concentration ranging from 0.0002 ppm to 5 ppm.

3. The chlorine dioxide gas entrapping method according to claim 1, wherein the iodide contained in the aqueous solution has a concentration of 0.2 g/L or more.

4. A chlorine dioxide gas concentration determining method, the method implementing the chlorine dioxide gas entrapping method according to claim 1, wherein the determining method comprises a step of determining, with using an ion chromatography technique, the concentration of iodate and/or iodite in the aqueous solution contacted with the air containing the chlorine dioxide gas.

5. A chlorine dioxide gas concentration determining method, the method implementing the chlorine dioxide gas entrapping method according to claim 1, wherein the determining method comprises the steps of making acidic the aqueous solution contacted with the air containing the chlorine dioxide gas so as to release iodine and determining the concentration of the iodine by colorimetric method or iodometric titration method.

6. A chlorine dioxide gas entrapping agent used in the chlorine dioxide gas entrapping method according to claim 1, the agent comprising an aqueous solution containing a strong alkaline substance and an iodide.

7. The chlorine dioxide gas entrapping method according to claim 1, wherein the strong alkaline substance is a hydroxide of alkali metal.

8. The chlorine dioxide gas entrapping method according to claim 7, wherein the hydroxide of alkali metal is selected from a group consisting of lithium hydroxide, potassium hydroxide and sodium hydroxide.

9. The chlorine dioxide gas entrapping agent according to claim 6, wherein the strong alkaline substance is a hydroxide of alkali metal.

10. The chlorine dioxide gas entrapping agent according to claim 9, wherein the hydroxide of alkali metal is selected from a group consisting of lithium hydroxide, potassium hydroxide and sodium hydroxide.

Description

EMBODIMENTS

Modes of Embodiment

(1) Next, embodiments of the present disclosure will be explained.

(2) (Chlorine Dioxide Gas Entrapping Agent)

(3) A chlorine dioxide gas entrapping agent relating to the present disclosure comprises an aqueous solution containing an alkaline substance and an iodide.

(4) Some examples of alkaline substance usable include lithium hydroxide, potassium hydroxide, sodium hydroxide and so on, but are not limited thereto. Further, the concentration of the alkaline substance in the aqueous solution is preferably 0.01N or more, more preferably, from 0.1N to 2N.

(5) Some examples of iodide useable include potassium iodide, sodium iodide and so on, but are not limited thereto. Further, the concentration of the iodide in the aqueous solution is preferably 0.2 g/L or more preferably, more preferably, from 2 g/L to 50 g/L.

(6) (Chlorine Dioxide Gas Entrapping Method)

(7) A chlorine dioxide gas entrapping method according to this disclosure comprises a step of bringing air containing chlorine dioxide gas into contact with the above-described chlorine dioxide gas entrapping agent containing an alkaline substance and iodide.

(8) As an example of a method for contacting, there can be cited a method of suctioning air with using a known air pump and feeding the suctioned air to the chlorine dioxide gas entrapping agent for bubbling. For instance, in case the chlorine dioxide gas concentration is determined by the iodometric titration method, for an indoor space having a volume of 50 m.sup.3 or more, the suctioning/bubbling can be effected at a suctioning rate of 0.1 L/min. to 1.0 L/min. for a period of from 2 hours to 200 hours.

(9) The chlorine dioxide gas entrapping method according to this disclosure can make determination for air which contains chlorine dioxide gas in a very low concentration of from 0.0002 ppm to 5 ppm. Needless to say, this method can be used also for air containing chlorine dioxide gas in higher concentrations.

(10) (Chlorine Dioxide Gas Concentration Determining Method)

(11) (1) Ion Chromatography Method

(12) Chlorine dioxide gas entrapped with using the above-described chlorine dioxide gas entrapping agent and the above-described chlorine dioxide gas entrapping method is present in the form of very stable iodate ions and/or iodite ions in the chlorine dioxide gas entrapping agent which comprises an alkaline aqueous solution. Therefore, through direct determination of concentrations of these ions by the known ion chromatography method, a concentration of chlorine dioxide gas in air can be determined. Incidentally, since the ion chromatography method has higher detection sensitivity than the iodometric titration method, determination is possible even for an amount of suctioned air which is about only about 1/10 of that of the case using the iodometric titration method.

(13) (2) Colorimetric Method

(14) Chlorine dioxide gas entrapped with using the above-described chlorine dioxide gas entrapping agent and the above-described chlorine dioxide gas entrapping method is present in the form of very stable iodate ions and/or iodite ions in the chlorine dioxide gas entrapping agent which comprises an alkaline aqueous solution.

(15) When e.g. sulfuric acid from 1N to 18N is added to this chlorine dioxide gas entrapping agent to render this acidic, immediate release of iodine occurs, as shown by the Chemical Formulae (7) and (8) above.

(16) Therefore, it becomes possible to determine iodine concentration by the known colorimetric method using a coloring reagent such as an aqueous starch solution, a DPD reagent and a colorimeter. With this, a concentration of chlorine dioxide gas contained in a low concentration in air can be determined even more easily. Incidentally, since the colorimetric method has higher detection sensitivity than the iodometric titration method, determination is possible even for an amount of suctioned air which is about only about of that of the case using the iodometric titration method.

(17) (3) Iodometric Titration Method

(18) Chlorine dioxide gas entrapped with using the above-described chlorine dioxide gas entrapping agent and the above-described chlorine dioxide gas entrapping method is present in the form of very stable iodate ions and/or iodite ions in the chlorine dioxide gas entrapping agent which comprises an alkaline aqueous solution.

(19) When e.g. sulfuric acid from 1N to 18N is added to this chlorine dioxide gas entrapping agent to render this acidic, immediate release of iodine occurs, as shown by the Chemical Formulae (7) and (8) above.

(20) Therefore, it becomes possible to determine iodine concentration by the known iodometric titration method effecting titration with sodium thiosulfate reference liquid (hypo liquid). With this, a concentration of chlorine dioxide gas contained in a low concentration in air can be determined even more easily.

EXAMPLES

(21) Next, the present disclosure will be explained in greater details by way of Examples thereof. It is understood, however that the present disclosure is not limited to these examples.

Example 1

(22) By a continuous operation with using an electrolysis type chlorine dioxide generating machine (LISPASS S, manufactured by Taiko Pharmaceutical Co., Ltd.), chlorine dioxide gas was generated at a gas flow rate: 300 mL/min and in a generation rate: 5 mg/hr.

(23) A portion of the generated gas was drawn by a corrosion resistant air pump at a rate of 50 mL/min and then diluted with diluting air of 3 L/min. Further, this diluted air was drawn at the rate of 50 mL/min by the corrosion resistant air pump and diluted then with diluting air at a rate of 2.5 L/min, whereby air containing chlorine dioxide in a concentration of 30 ppb approximately was generated continuously.

(24) As chlorine dioxide gas entrapping agents, there were prepared aqueous solutions containing potassium iodide: 50 g/L and potassium hydroxide: 50 g/L, respectively. And, 20 mL of these were introduced respectively into 30 mL impingers.

(25) The two columns of introduced impingers are connected in series and the above-described chlorine dioxide gas was suctioned at a rate of 500 mL/min for 30 hours.

(26) The entrapping agents inside the first and second columns of impingers were put into flasks respectively and then 2 N sulfuric acid was added thereto to render them acidic, and titration was effected with 0.01 mol/L of sodium thiosulfate reference liquid. The titration numbers were 0.55 mL for the first column and 0.00 mL for the second column. The factor of the sodium thiosulfate reference liquid was 1.005 and calculations made showed 29.6 ppb for the first column (incidentally, the theoretical value was 31.9 ppb) and 0 ppb for the second column.

Example 2

(27) The chlorine dioxide gas generated from the chlorine dioxide gas generating device used in Example 1 (flow rate: 2.55 L/min, concentration: about 30 ppb) was mixed with air at 2.5 L/min having an ozone concentration: 50 ppb generated from an ozone generator (Model 1410, manufactured by Dylec Inc., an air purifier Model 1400, Monitor Model 1150) and determination was effected similarly to Example 1.

(28) The chlorine dioxide gas concentration and the ozone concentration of the feed gas were calculated to produce the results: chlorine dioxide gas: 2.55/(2.55+2.5)29.6=14.9 ppb, and ozone: 2.5/(2.55+2.5)50=24.8 ppb.

(29) The titration numbers were found as: 0.30 mL for the first column and 0.00 mL for the second column. The factor of the sodium thiosulfate reference liquid was 1.005 and calculations made showed 16.1 ppb for the first column and 0 ppb for the second column.

Example 3

(30) Like Example 1 above, air containing chlorine dioxide gas in a concentration of 30 ppb approximately was generated continuously. As absorption liquids, there were prepared aqueous solutions containing potassium iodide: 10 g/L and potassium hydroxide: 2 g/L, respectively. And, 20 mL of these were introduced respectively into 30 mL impingers.

(31) The two columns of introduced impingers are connected in series and the above-described chlorine dioxide gas was suctioned at a rate of 500 mL/min for 30 hours. The absorption liquids inside the first and second columns of impingers were put into flasks respectively and then 2 N sulfuric acid was added thereto to render them acidic, and titration was effected with 0.01 mol/L of sodium thiosulfate reference liquid.

(32) The titration numbers were found as: 0.53 mL for the first column and 0.00 mL for the second column. The factor of the sodium thiosulfate reference liquid was 1.005 and calculations made showed 28.5 ppb for the first column and 0 ppb for the second column.

Example 4

(33) Like Example 2 above, air with ozone concentration of 50 ppb was mixed at a rate of 2.5 L/min and determination was made similarly to Example 2.

(34) The feed gas had concentrations of: chlorine dioxide: 14.9 ppb and ozone: 24.8 ppb. As absorption liquids, there were prepared aqueous solutions containing potassium iodide: 10 g/L and potassium hydroxide: 2 g/L, respectively. And, 20 mL of these were introduced respectively into 30 mL impingers.

(35) The two columns of introduced impingers are connected in series and the above-described chlorine dioxide gas was suctioned at a rate of 500 mL/min for 30 hours. The absorption liquids inside the first and second columns of impingers were put into flasks respectively and then 2 N sulfuric acid was added thereto to render them acidic, and titration was effected with 0.01 mol/L of sodium thiosulfate reference liquid.

(36) The titration numbers were found as: 0.28 mL for the first column and 0.00 mL for the second column. The factor of the reference liquid was 1.005 and calculations made showed 14.1 ppb for the first column and 0 ppb for the second column.

Comparison Example 1 (Conventional Method)

(37) Like Example 1 above, air containing chlorine dioxide gas in a concentration of 30 ppb approximately was generated continuously. As absorption liquids, there was prepared aqueous solution containing potassium iodide: 10 g/L, respectively. And, 20 mL of this was introduced respectively into 30 mL impingers.

(38) The two columns of introduced impingers are connected in series and the above-described chlorine dioxide gas was suctioned at a rate of 500 mL/min for 30 hours. The absorption liquids inside the first and second columns of impingers were put into flasks respectively and then 2 N sulfuric acid was added thereto to render them acidic, and titration was effected with 0.01 mol/L of sodium thiosulfate reference liquid.

(39) The titration numbers were found as: 0.42 mL for the first column and 0.07 mL for the second column. The factor of the reference liquid was 1.005 and calculations made showed 22.6 ppb for the first column and 3.8 ppb for the second column. Thus, in comparison with Example 3, the absorption entrapment of chlorine dioxide gas was insufficient and there was a significant minus error in the determined value for the first column.

Comparison Example 2 (Conventional Method, Under Neutral Condition)

(40) Like Example 1 above, air containing chlorine dioxide gas in a concentration of 30 ppb approximately was generated continuously. As absorption liquid, to an aqueous solution of potassium iodide: 10 g/L, potassium dihydrogen phosphate and dipotassium hydrogen phosphate buffer solution were added to adjust pH to 7 to 8 and to 30 mL impingers prepared, 20 mL of the above absorption liquid was introduced.

(41) The two columns of introduced impingers are connected in series and the above-described chlorine dioxide gas was suctioned at a rate of 500 mL/min for 30 hours. The absorption liquids inside the first and second columns of impingers were put into flasks respectively and then 2 N sulfuric acid was added thereto to render them acidic, and titration was effected with 0.01 mol/L of sodium thiosulfate reference liquid.

(42) The titration numbers were found as: 0.43 mL for the first column and 0.06 mL for the second column. The factor of the reference liquid was 1.005 and calculations made showed 23.1 ppb for the first column and 3.2 ppb for the second column. Thus, in comparison with Example 3, the absorption entrapment of chlorine dioxide gas was insufficient and there was a significant minus error in the determined value for the first column.

Comparison Example 3 (Conventional Method)

(43) By the method similar to Example 2, gas containing chlorine dioxide: 14.9 ppb and ozone: 24.8 ppb was fed and as absorption liquid there was prepared aqueous solution containing potassium iodide: 10 g/L and to 30 mL impingers prepared, 20 mL of the respective absorption liquid was introduced.

(44) The titration numbers were found as: 0.34 mL for the first column and 0.04 mL for the second column. The factor of the reference liquid was 1.005 and calculations made showed 18.3 ppb for the first column and 2.2 ppb for the second column. Thus, in comparison with Example 4, there was a significant plus error in the determined value for the first column, due to influence from ozone.

INDUSTRIAL APPLICABILITY

(45) The present disclosure allows accurate determination of a concentration of chlorine dioxide gas contained in a low concentration in air. So, this disclosure can be used advantageously for evaluation or performance confirmation of e.g. deodorant agent releasing chlorine dioxide gas into a room for decomposing odorous component or a medical agent for removing/killing virus or bacteria afloat in a room or for calibration of an instrument for continuously determining a concentration of chlorine dioxide gas with high sensitivity.