CN115436558A - Method for measuring content of chlorine-series oxides by ion chromatography - Google Patents
Method for measuring content of chlorine-series oxides by ion chromatography Download PDFInfo
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- CN115436558A CN115436558A CN202210926964.3A CN202210926964A CN115436558A CN 115436558 A CN115436558 A CN 115436558A CN 202210926964 A CN202210926964 A CN 202210926964A CN 115436558 A CN115436558 A CN 115436558A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004255 ion exchange chromatography Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 104
- 239000000523 sample Substances 0.000 claims description 86
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 70
- 229910001919 chlorite Inorganic materials 0.000 claims description 61
- 229910052619 chlorite group Inorganic materials 0.000 claims description 61
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 59
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 49
- 239000000460 chlorine Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 35
- 239000004155 Chlorine dioxide Substances 0.000 claims description 35
- 229910052801 chlorine Inorganic materials 0.000 claims description 35
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 35
- 239000012488 sample solution Substances 0.000 claims description 30
- 150000001450 anions Chemical class 0.000 claims description 16
- 238000004458 analytical method Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000012417 linear regression Methods 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 239000012086 standard solution Substances 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 8
- 125000001309 chloro group Chemical class Cl* 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000872 buffer Substances 0.000 description 11
- 238000009776 industrial production Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 description 3
- 229940005993 chlorite ion Drugs 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical class Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910001902 chlorine oxide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
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Abstract
The invention discloses a method for measuring the content of chlorine-series oxides by ion chromatography, which comprises the following steps: (1) processing a sample to be detected; (2) setting chromatographic conditions; (3) preparing a standard curve solution; (4) drawing a standard curve; and (5) measuring the sample. The method has the advantages of low detection limit, high accuracy, simple steps and low cost, can meet the requirement of quickly and accurately measuring the content of the chlorine series oxides, and has industrial application value and development prospect.
Description
Technical Field
The invention belongs to the field of chemical analysis, and particularly relates to a method for measuring the content of chlorine oxides by using ion chromatography.
Background
The chlorine-based oxides having mainly Cl 2 O、ClO 2 、ClO 3 、Cl 2 O 3 、Cl 2 O 4 、Cl 2 O 5 、Cl 2 O 6 、Cl 2 O 7 、Cl 2 O 8 And the like, and most of them are strongly oxidizing substances. Wherein chlorine dioxide (ClO) 2 ) As typical representatives of the chlorine-based oxides, compounds having the formula (I) and (II) Cl 2 Similar toxicity can cause erosion of the respiratory organs and eyes of the human body, and if the concentration of the gas is high, the gas can invade the central nerve of the human body, and the death of the human body can be seriously caused. Current state regulation of ClO in air 2 The concentration should not exceed 0.3mg/m 3 . The existing chlorine dioxide content measuring method is used for measuring Cl produced in industry 2 Middle ClO 2 In the case of content, cl is determined due to the lower content of chlorine dioxide in the sample 2 High content of and Cl 2 Chemical nature and ClO 2 Similarly, the interference with the measurement is large, resulting in inaccurate measurement data.
For example, CN101556264A discloses a method for measuring chlorine dioxide content, which comprises the first four steps of a five-step iodometry method, wherein in the first step and the third step, a phosphate buffer solution is added until the pH value of a test solution is 7; the adding amount of potassium iodide solution is 15-20ml; in the second step and the fourth step, 2.5mol/L hydrochloric acid solution is added until the pH value is 2, so that the addition of the phosphoric acid buffer solution is ensured to meet the requirement that the pH value is nearly neutral, enough potassium iodide solution is also ensured to fully react, and the pH value of the obtained solution is adjusted to 2 after the A value and the C value are additionally measured, thereby eliminating the influence of the pH value of the solution on each component. The method has the disadvantages of poor reproducibility and accuracy and complicated operation when measuring the low-concentration chlorine-series oxide.
Also, for example, CN104995132A discloses a method for capturing chlorine dioxide gas, a method for measuring the concentration of chlorine dioxide gas, and a capturing agent, in which chlorine dioxide gas is reacted with iodide in an iodine solution to release iodine, and the iodine is analyzed by an iodine titration method, a colorimetric method, or the like, to measure the concentration of chlorine dioxide gas. The disadvantage is that the method is only suitable for measuring the concentration of chlorine dioxide gas with low concentration in the air.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the method for measuring the content of the chlorine-containing oxide by using the ion chromatography, which has the advantages of low detection limit, high accuracy, simple steps and low cost.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for measuring the content of chlorine-containing oxides by ion chromatography comprises the following steps:
(1) Treating a sample to be tested: weighing a sample to be detected, adding the sample to be detected into an alkali absorption solution for reaction, adjusting the pH value of a reaction solution to be 8.0-9.0 after the reaction is finished, and transferring a certain volume of the reaction solution to dilute and fix the volume to obtain a sample solution for later use;
(2) Setting chromatographic conditions: adopting a Metrosep A Supp 5-250/4.0 anion analysis column, a Metrosep ASupp5Guard/4.0 protection column and a Metrohm Suppressor Module anion Suppressor; the temperature of the column box is 25 ℃; the leacheate is Na 2 CO 3 And NaHCO 3 The mixed solution of (1); the flow rate of the leaching solution is 0.2-2.0mL/min; the sample injection volume is 10 mu L;
(3) Preparing a standard curve solution: mixing the prepared chlorite (ClO) 2 -/chlorate (ClO) 3 -) respectively diluting the standard solutions and fixing the volume to obtain a series of standard curve solutions;
(4) Drawing a standard curve: drawing a standard curve by taking the concentration of the solution of the standard curve as a vertical coordinate and taking a peak area as a horizontal coordinate;
(5) And (3) determining a sample: measuring the sample solution and the blank control solution according to the operating conditions of the standard curve, qualitatively determining the retention time, quantitatively determining the peak area of the measured sample, calculating the concentration of chlorite/chlorate in the sample by a linear regression equation, and calculating the content x (%) of chlorine dioxide in the sample according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 -reading the chlorite/chlorate concentration in milligrams per liter (mg/L) of the blank from the instrument;
c 1 -chlorite/chlorate concentration in milligrams per liter (mg/L) of the sample solution read from the instrument;
m-mass of the chlorine sample weighed in grams (g);
v-volume of reaction removed in milliliters (mL).
As a preferred embodiment of the invention, the weighed sample to be measured has a mass of 2.0-20.0g.
As a preferred embodiment of the present invention, the volume of the reaction solution to be removed is 20ml.
As a preferred embodiment of the present invention, the alkali absorption solution is at least one selected from a potassium hydroxide solution, a sodium carbonate solution, and a sodium bicarbonate solution.
As a preferred embodiment of the invention, the concentration of the alkali absorption solution is 0.2-2.0mol/L.
In the invention, the sample to be detected is a chlorine sample containing chlorine dioxide in industrial production, and because the content of chlorine dioxide in the chlorine in the industrial production is lower, chlorite (ClO) in the solution is selected by properly adjusting the dilution times of the solution with a standard curve 2 -/chlorate (ClO) 3 -) concentration 0-1000mg/L can better meet the requirement of analyzing chlorine dioxide in liquid chlorine. Therefore, as a preferred embodiment of the present invention, the concentration of the standard curve solution is 0 to 1000mg/L.
As a preferred embodiment of the present invention, na is mentioned 2 CO 3 And NaHCO 3 In the mixed solution of (3), na 2 CO 3 The concentration of (A) is 3.5mmol/L, naHCO 3 The concentration of (B) was 1.0mmol/L.
In the present invention, since ClO is used 2 Is not in an ionic state in solution and is not suitable for direct analysis by ion chromatography, and the invention adopts alkali liquor and ClO firstly 2 Obtaining chlorite and chlorate by reaction of the following formula (by hydrogen and oxygen)Sodium sulfide as an example):
2ClO 2 +2NaOH＝NaClO 2 +NaClO 3 +H 2 O
the reaction is quantitative and can therefore be determined by measuring the chlorite radical (ClO) 2 – ) Chlorate radical (ClO) 3 – ) Indirectly determining the amount of change of ClO 2 And (4) content.
The method for measuring the content of the chlorine-containing oxide by using the ion chromatography has the advantages of low detection limit, high accuracy, simple steps, lower cost and the like, can meet the requirement of quickly and accurately measuring the content of the chlorine-containing oxide, has industrial application value and development prospect, and is particularly suitable for measuring Cl produced in industry 2 Middle ClO 2 The content of (a).
Compared with the prior art, the invention has the following advantages:
1. the method has low detection limit and high accuracy, the detection limit of the method is low (0.2 mg/L), and the sensitivity is high; the linear range is wide (0-1000 mg/L); the relative error is small (less than 2.6), and the result is reliable. The method is suitable for measuring chlorine oxides, especially Cl in industrial production 2 Middle ClO 2 The content of (a).
2. The method has the advantages of simple process, high efficiency, simple treatment steps, convenient operation, obvious simplification of the detection process and improvement of the detection efficiency.
3. Simple and quick, low cost, and the invention adopts ion chromatograph to detect the reaction product of chlorite (ClO) 2 -/chlorate (ClO) 3 -) to indirectly determine ClO 2 The content of (2) can realize the rapid determination of the sample to be detected.
4. Safe and environment-friendly, and adopts alkali liquor and ClO 2 Chlorite and chlorate are obtained through reaction, the detection process is safer and more environment-friendly, and the damage to instruments is less.
Drawings
FIG. 1 is an ion chromatogram of a sample to be tested according to example 1 of the present invention;
FIG. 2 is a standard curve chart of example 1 of the present invention;
FIG. 3 is a standard curve chart of example 2 of the present invention;
FIG. 4 is a standard graph of example 3 of the present invention;
FIG. 5 is a standard curve chart of example 4 of the present invention;
FIG. 6 is a standard graph of example 5 of the present invention;
FIG. 7 is a standard curve chart of example 6 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description will be made with reference to specific examples, but the present invention is not limited to the examples.
Example 1
(1) A sample treatment step: weighing 2.0g to 250mL of chlorine gas sample containing chlorine dioxide in industrial production, accurately weighing the chlorine gas sample to 0.1g, slowly introducing the weighed sample into a reaction flask filled with 0.2mol/L sodium hydroxide solution from the buffer flask, reacting for 15min under stirring, then adjusting the pH =8 with sulfuric acid solution, transferring reaction liquid into a volumetric flask with the volume of 20mL to 100mL, diluting the reaction liquid to a scale with deionized water, and uniformly mixing to obtain sample solution for later use.
(2) Setting chromatographic conditions: metrosep A Supp 5-250/4.0 anion analysis column (4 mm. Times.250 mm) and Metrosep A Supp5Guard/4.0 Guard column; temperature of the column box: 25 ℃; leacheate Na 2 CO 3 (3.5mmol/L)+NaHCO 3 (1.0 mmol/L); a Metrohm supressor Module anion Suppressor; the flow rate of the leaching solution is 0.2mL/min; the injection volume is 10. Mu.L.
(3) Preparing a standard curve solution:
0mL, 2.0mL, 5.0mL, 10.0mL and 20.0mL of the prepared 1000mg/L chlorite standard solution are respectively transferred into a 100mL volumetric flask, the volume is determined by deionized water, and the solutions are uniformly mixed to prepare 0mg/L, 20.0mg/L, 50.0mg/L, 100.0mg/L and 200.0mg/L series standard curve solutions.
(4) Drawing a standard curve:
and (3) analyzing the standard curve solution under the chromatographic conditions, and drawing a standard curve by taking the concentration of the standard curve solution as a vertical coordinate and the peak area as a horizontal coordinate, wherein the obtained standard curve is shown in figure 2.
(5) Determination of sample solution: determining sample solution and blank control solution according to standard curve operating condition, determining qualitative by retention time, determining peak area of sample, and calculating chlorite ion (ClO) in sample by linear regression equation 2 ) The concentration of (a), the chlorine dioxide content x (%) in the sample is calculated according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 read-out of chlorite (ClO) from the instrument blank 2 -) concentration in milligrams per liter (mg/L);
c 1 reading of chlorite (ClO) from the sample solution 2 -) concentration in milligrams per liter (mg/L);
m-mass of the chlorine sample weighed in grams (g);
v-volume of reaction removed in step (1) in milliliters (mL).
Example 2
(1) A sample treatment step: weighing 5.0g of chlorine sample containing chlorine dioxide in industrial production, accurately measuring the chlorine sample to 0.1g, slowly introducing the chlorine sample into a 250mL buffer conical flask at a constant speed, slowly introducing the weighed sample into a reaction flask filled with 0.5mol/L sodium hydroxide solution from the buffer conical flask, reacting for 18min under stirring, adjusting the pH =8.5 by using sulfuric acid solution, transferring 20mL to 100mL of volumetric flask of reaction solution, diluting the reaction solution to a scale by using deionized water, and uniformly mixing to obtain sample solution for later use.
(2) Setting chromatographic conditions: metrosep A Supp 5-250/4.0 anion analysis column (4 mm. Times.250 mm) and Metrosep A Supp5Guard/4.0 Guard column; temperature of the column box: 25 ℃; leacheate Na 2 CO 3 (3.5mmol/L)+NaHCO 3 (1.0 mmol/L); metrohm supressor Module anion Suppressor; eluent flow rate 0.5mL/min; the injection volume is 10. Mu.L.
(3) Preparing a standard curve solution:
respectively transferring 20.0mL, 30.0mL, 40.0mL, 50.0mL and 60.0mL volumetric flasks from the prepared 1000mg/L chlorite standard solution, fixing the volume by deionized water, uniformly mixing, and preparing into 200.0mg/L, 300.0mg/L, 400.0mg/L, 500.0mg/L and 600mg/L series standard curve solutions.
(4) Drawing a standard curve:
the standard curve solution was analyzed under the above chromatographic conditions, and a standard curve was plotted with the concentration of the standard curve solution as ordinate and the peak area as abscissa, and the obtained standard curve was shown in fig. 3.
(5) Determination of sample solution: determining sample solution and blank control solution according to standard curve operating condition, determining qualitative by retention time, determining peak area of sample, and calculating chlorite ion (ClO) in sample by linear regression equation 2 ) The concentration of (a), the chlorine dioxide content x (%) in the sample is calculated according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 read-out of chlorite (ClO) from the instrument blank 2 -) concentration in milligrams per liter (mg/L);
c 1 reading of chlorite (ClO) from the sample solution 2 -) concentration in milligrams per liter (mg/L);
m represents the mass of the weighed chlorine sample in grams (g);
v-volume of reaction removed in step (1) in milliliters (mL).
Example 3
(1) A sample treatment step: weighing 10.0g of chlorine gas sample containing chlorine dioxide in industrial production, accurately measuring the chlorine gas sample to 0.1g, slowly introducing the chlorine gas sample into a 250mL buffer conical flask at a constant speed, slowly introducing the weighed sample into a reaction flask containing 0.8mol/L sodium hydroxide solution from the buffer conical flask, reacting for 20min under stirring, then adjusting the pH =8.5 by using sulfuric acid solution, transferring 20mL to 100mL of reaction solution in a volumetric flask, diluting the reaction solution to a scale by using deionized water, and uniformly mixing to obtain sample solution for later use.
(2) Setting chromatographic conditions: metrosep A Supp 5-250/4.0 anion analysis column (4 mm. Times.250 mm) and Metrosep A Supp5Guard/4.0 Guard column; temperature of the column box: 25 ℃; leacheate Na 2 CO 3 (3.5mmol/L)+NaHCO 3 (1.0 mmol/L); a Metrohm supressor Module anion Suppressor; the flow rate of the leaching solution is 0.8mL/min; the injection volume is 10. Mu.L.
(3) Preparing a standard curve solution:
60.0mL, 70.0mL, 80.0mL, 90.0mL and 100.0mL of the prepared 1000mg/L chlorite standard solution are respectively transferred into a 100mL volumetric flask, the volume is determined by deionized water, and the solutions are mixed uniformly to prepare 600.0mg/L, 700.0mg/L, 800.0mg/L, 900.0mg/L and 1000mg/L series standard curve solutions.
(4) Drawing a standard curve:
the standard curve solution was analyzed under the above chromatographic conditions, and a standard curve was plotted with the concentration of the standard curve solution as ordinate and the peak area as abscissa, and the obtained standard curve was shown in fig. 4.
(5) Determination of sample solution: determining sample solution and blank control solution according to standard curve operating conditions, determining qualitative retention time, determining peak area of the sample, and calculating chlorite ion (ClO) in the sample by linear regression equation 2 ) The concentration of (b), the content x (%) of chlorine dioxide in the sample is calculated according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 read-out of chlorite (ClO) from the instrument blank 2 -) concentration in milligrams per liter (mg/L);
c 1 chlorite (ClO) in the sample solution read from the instrument 2 -) concentration in milligrams per liter (mg/L);
m-mass of the chlorine sample weighed in grams (g);
v-volume of reaction solution removed in step (1) in milliliters (mL).
Example 4
(1) A sample treatment step: weighing 15.0g of chlorine sample containing chlorine dioxide in industrial production, accurately measuring the chlorine sample to 0.1g, slowly introducing the chlorine sample into a 250mL buffer conical flask at a constant speed, slowly introducing the weighed sample into a reaction flask containing 1.0mol/L sodium hydroxide solution from the buffer conical flask, reacting for 25min under stirring, adjusting the pH =9.0 by using sulfuric acid solution, transferring 20mL to 100mL of volumetric flask of reaction solution, diluting the reaction solution to a scale by using deionized water, and uniformly mixing to obtain sample solution for later use.
(2) Setting chromatographic conditions: metrosep A Supp 5-250/4.0 anion analysis column (4 mm. Times.250 mm) and Metrosep A Supp5Guard/4.0 Guard column; temperature of the column box: 25 ℃; leacheate Na 2 CO 3 (3.5mmol/L)+NaHCO 3 (1.0 mmol/L); a Metrohm supressor Module anion Suppressor; the flow rate of the leaching solution is 1.0mL/min; the injection volume is 10. Mu.L.
(3) Preparing a standard curve solution:
0mL, 2.0mL, 5.0mL, 10.0mL and 20.0mL of the prepared 1000mg/L chlorate standard solution are respectively transferred into a 100mL volumetric flask, the volume is determined by deionized water, and the solutions are uniformly mixed to prepare 0mg/L, 20.0mg/L, 50.0mg/L, 100.0mg/L and 200.0mg/L series standard curve solutions.
(4) Drawing a standard curve:
the standard curve solution was analyzed under the above chromatographic conditions, and a standard curve was plotted with the concentration of the standard curve solution as ordinate and the peak area as abscissa, and the obtained standard curve was shown in fig. 5.
(5) Determination of sample solution: the sample solution and the blank control solution were measured according to the operating conditions of the standard curve, characterized by retention time,determining the peak area of the sample, and calculating chlorate (ClO) in the sample by a linear regression equation 3 ) The concentration of (b), the content x (%) of chlorine dioxide in the sample is calculated according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 read-out of chlorate (ClO) from instrumental blank control solution 3 -) concentration in milligrams per liter (mg/L);
c 1 chlorate (ClO) in the sample solution read off from the instrument 3 -) concentration in milligrams per liter (mg/L);
m-mass of the chlorine sample weighed in grams (g);
v-volume of reaction solution removed in step (1) in milliliters (mL).
Example 5
(1) A sample treatment step: weighing 18.0g of chlorine sample containing chlorine dioxide in industrial production, accurately measuring the chlorine sample to 0.1g, slowly introducing the chlorine sample into a 250mL buffer conical flask at a constant speed, slowly introducing the weighed sample into a reaction flask containing 1.5mol/L sodium hydroxide solution from the buffer conical flask, reacting for 26min under stirring, adjusting the pH =9.0 by using sulfuric acid solution, transferring 20mL to 100mL of volumetric flask of reaction solution, diluting the reaction solution to a scale by using deionized water, and uniformly mixing to obtain sample solution for later use.
(2) Setting chromatographic conditions: metrosep A Supp 5-250/4.0 anion analysis column (4 mm. Times.250 mm) and Metrosep A Supp5Guard/4.0 Guard column; temperature of the column box: 25 ℃; leacheate Na 2 CO 3 (3.5mmol/L)+NaHCO 3 (1.0 mmol/L); a Metrohm supressor Module anion Suppressor; the flow rate of the leaching solution is 1.5mL/min; the injection volume is 10. Mu.L.
(3) Preparing a standard curve solution:
respectively transferring 20.0mL, 30.0mL, 40.0mL, 50.0mL and 60.0mL of the prepared 1000mg/L chlorate standard solution into a 100mL volumetric flask, fixing the volume by using deionized water, uniformly mixing, and preparing into 200.0mg/L, 300.0mg/L, 400.0mg/L, 500.0mg/L and 600mg/L series standard curve solutions.
(4) Drawing a standard curve:
the standard curve solution was analyzed under the above chromatographic conditions, and a standard curve was plotted with the concentration of the standard curve solution as ordinate and the peak area as abscissa, and the obtained standard curve was shown in fig. 6.
(5) Determination of sample solution: determining sample solution and blank control solution according to standard curve operating condition, determining qualitative by retention time, determining peak area of sample, and calculating chlorate (ClO) in sample by linear regression equation 3 ) The concentration of (a), the chlorine dioxide content x (%) in the sample is calculated according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 chlorate (ClO) in a blank control solution read from the instrument 3 -) concentration in milligrams per liter (mg/L);
c 1 chlorate (ClO) in the sample solution read off from the instrument 3 -) concentration in milligrams per liter (mg/L);
m-mass of the chlorine sample weighed in grams (g);
v-volume of reaction solution removed in step (1) in milliliters (mL).
Example 6
(1) A sample treatment step: weighing 20.0g of chlorine sample containing chlorine dioxide in industrial production, accurately measuring the chlorine sample to 0.1g, slowly introducing the chlorine sample into a 250mL buffer conical flask at a constant speed, slowly introducing the weighed sample into a reaction flask containing 2.0mol/L sodium hydroxide solution from the buffer conical flask, reacting for 30min under stirring, adjusting the pH =9.0 by using sulfuric acid solution, transferring 20mL to 100mL of volumetric flask of reaction solution, diluting the reaction solution to a scale by using deionized water, and uniformly mixing to obtain sample solution for later use.
(2) Chromatographic condition setting: metrosep A Supp 5-250/4.0 anion analysis column (4 mm. Times.250 mm) and Metrosep A Supp5Guard/4.0 Guard column; temperature of the column box: 25 ℃; leacheate Na 2 CO 3 (3.5mmol/L)+NaHCO 3 (1.0 mmol/L); metrohm supressor Module anion Suppressor; the flow rate of the leaching solution is 2.0mL/min; the injection volume is 10. Mu.L.
(3) Preparing a standard curve solution:
60.0mL, 70.0mL, 80.0mL, 90.0mL and 100.0mL of the prepared 1000mg/L chlorate standard solution are respectively transferred into a 100mL volumetric flask, the volume is determined by deionized water, and the solutions are uniformly mixed to prepare 600.0mg/L, 700.0mg/L, 800.0mg/L, 900.0mg/L and 1000mg/L series standard curve solutions.
(4) Drawing a standard curve:
and (3) analyzing the standard curve solution under the chromatographic conditions, and drawing a standard curve by taking the concentration of the standard curve solution as a vertical coordinate and the peak area as a horizontal coordinate, wherein the obtained standard curve is shown in fig. 7.
(5) Determination of sample solution: determining sample solution and blank control solution according to standard curve operating conditions, determining qualitative retention time, determining peak area of the sample, and calculating chlorate (ClO) in the sample by linear regression equation 3 ) The concentration of (a), the chlorine dioxide content x (%) in the sample is calculated according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 read-out of chlorate (ClO) from instrumental blank control solution 3 -) concentration in milligrams per liter (mg/L);
c 1 chlorate (ClO) in the sample solution read from the instrument 3 -) concentration in milligrams per liter (mg/L);
m represents the mass of the weighed chlorine sample in grams (g);
v-volume of reaction removed in step (1) in milliliters (mL).
Measurement results
The data of examples 1 to 6 are shown in Table 1, and it is understood from Table 1 that the measurement of chlorine dioxide content by ion chromatography according to the present invention gives a good linear relationship.
TABLE 1 EXAMPLES 1-6 measurement data
Claims (7)
1. A method for measuring the content of chlorine-containing oxides by using ion chromatography is characterized by comprising the following steps:
(1) Treating a sample to be detected: weighing a sample to be detected, adding the sample to be detected into an alkali absorption solution for reaction, adjusting the pH value of a reaction solution to be 8.0-9.0 after the reaction is finished, and transferring a certain volume of the reaction solution to dilute and fix the volume to obtain a sample solution for later use;
(2) Setting chromatographic conditions: adopting a Metrosep A Supp 5-250/4.0 anion analysis column, a Metrosep A Supp5Guard/4.0 protection column and a Metrohm Suppressor Module anion Suppressor; the temperature of the column box is 25 ℃; the leacheate is Na 2 CO 3 And NaHCO 3 The mixed solution of (1); the flow rate of the leaching solution is 0.2-2.0mL/min; the sample injection volume is 10 mu L;
(3) Preparing a standard curve solution: respectively diluting the prepared chlorite/chlorate standard solution to a constant volume to obtain a series of standard curve solutions;
(4) Drawing a standard curve: drawing a standard curve by taking the concentration of the solution of the standard curve as a vertical coordinate and taking a peak area as a horizontal coordinate;
(5) And (3) determining a sample: determining the sample solution and the blank control solution according to the operating conditions of the standard curve, performing qualitative determination by using retention time, determining the peak area of the determined sample quantitatively, calculating the concentration of chlorite/chlorate in the sample by using a linear regression equation, and calculating the content x (%) of chlorine dioxide in the sample according to the formula (a):
in the formula:
x-mass fraction of chlorine dioxide in the sample, expressed as%;
c 0 -reading the chlorite/chlorate concentration in milligrams per liter (mg/L) of the blank from the instrument;
c 1 -reading the chlorite/chlorate concentration in milligrams per liter (mg/L) of the sample solution from the instrument;
m represents the mass of the weighed chlorine sample in grams (g);
v-volume of reaction removed in milliliters (mL).
2. The method for measuring the content of chlorine-containing oxides by ion chromatography as claimed in claim 1, wherein the weighed sample has a mass of 2.0 to 20.0g.
3. The method for measuring a chlorine-containing oxide content by ion chromatography as claimed in claim 1, wherein the volume of the reaction solution to be removed is 20ml.
4. The method for measuring the content of chlorine-based oxides by ion chromatography as claimed in claim 1, wherein said alkali absorption solution is at least one selected from the group consisting of potassium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution.
5. The method for measuring the content of chlorine-based oxides by ion chromatography as claimed in claim 1, wherein the concentration of said alkali absorbent is 0.2 to 2.0mol/L.
6. The method for measuring the content of chlorine-based oxides by ion chromatography as claimed in claim 1, wherein the concentration of said standard curve solution is 0 to 1000mg/L.
7. The method for measuring the content of chlorine-containing oxides by ion chromatography as claimed in claim 1, wherein said Na is 2 CO 3 And NaHCO 3 In the mixed solution of (3), na 2 CO 3 The concentration of (A) is 3.5mmol/L, naHCO 3 The concentration of (B) was 1.0mmol/L.
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