CN117310046A - Method for determining citrate content in special paper by headspace gas chromatography - Google Patents
Method for determining citrate content in special paper by headspace gas chromatography Download PDFInfo
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000003988 headspace gas chromatography Methods 0.000 title claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 20
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 20
- 238000004817 gas chromatography Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 235000019504 cigarettes Nutrition 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 abstract description 21
- 239000001509 sodium citrate Substances 0.000 abstract description 21
- 239000007788 liquid Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 5
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 polytetrafluoroethylene silicon Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000037230 mobility Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
- G01N30/02—Column chromatography
-
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/66—Thermal conductivity detectors
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention relates to the technical field of special paper citrate detection, in particular to a method for accurately measuring the sodium citrate content in special paper by using a headspace gas chromatography. The invention provides a method for determining the citrate content in special paper by using headspace gas chromatography, which is characterized by comprising the following steps: (1) sample preparation: placing potassium permanganate solution into a headspace bottle, sealing the headspace bottle, injecting acidified special paper leaching solution into the headspace bottle, and shaking uniformly; (2) sample detection: placing the headspace bottle in the step (1) into a headspace sample injector, and detecting a GC signal value of carbon dioxide in the headspace bottle by adopting a gas chromatography after balancing for a period of time; (3) citrate content calculation: and calculating the citrate content in the specialty paper according to the established linear relation between the citrate concentration and the GC signal value of the carbon dioxide. The invention can rapidly and accurately measure the citrate content, and is suitable for detecting large-scale industrial samples.
Description
Technical Field
The invention relates to the technical field of special paper citrate detection, in particular to a method for accurately measuring the sodium citrate content in special paper by using a headspace gas chromatography.
Background
The special paper is paper with special functions provided by adding various auxiliary agents into the paper, and is widely applied to the fields of medical treatment, batteries, tobacco, food packaging, automobile electronics and the like. The cigarette paper is used as special paper, and the proper addition of the combustion improver can not only enhance the ash coagulation capacity of the cigarette paper to ensure that the cigarette paper has good ash holding capacity, but also adjust the combustion speed of the cigarette to improve the quality of the cigarette. Most importantly, the combustion improver can eliminate peculiar smell and pungency of cigarettes and reduce the content of CO. The combustion improver can bring a lot of benefits, but the content of the combustion improver still needs to be controlled, otherwise, the combustion speed of cigarette paper is not matched with tobacco shreds, and the smoking quality is affected. The most commonly used combustion improver of the cigarette paper at present is citrate, so that the rapid detection of the content of the citrate in the cigarette paper has important significance.
Currently, common detection methods for citrate are redox titration, ion chromatography (Ion Chromatography, IC), inductively coupled plasma mass spectrometry (Inductively Coupled Plasma Mass Spectrometer, ICP-MS), atomic absorption spectrometry (AtomicAbsorption Spectrometry, AAS), and the like. The redox titration method is to perform a color reaction by titrating potassium permanganate, and judge the consumption of the potassium permanganate so as to judge the content of sodium citrate. IC is a high-efficiency chromatographic method, which separates substances according to different mobilities of the substances on an ion exchange column, and further automatically detects the substances, and is widely used for anion and cation analysis, and ICP-MS is a method for enabling a solution to be detected to be atomized and then to be dissociated by high-energy plasma of argon atoms and then to be detected by a mass spectrometer. Although the two methods have small artificial subjective factors in the operation process, the sample pretreatment needs continuous extraction, which is time-consuming and has residual influence on the measurement result. In addition, the principle of AAS is that the gaseous ground state atoms of the element to be measured in the vapor absorb the characteristic radiation of the element to be measured emitted from the light source, and the content of the element to be measured in the sample is obtained from the degree of attenuation of the radiation. It is one of the most commonly used analysis techniques, but the method is generally used for detecting metal elements, the concentration of citrate can only be estimated through Na+ concentration, and the process is relatively complex. The patent application publication No. CN116008353A provides a rapid detection method for the citrate content in cigarette paper, which adopts a conductivity meter to detect the citrate content, the detection is rapid, however, the conductivity meter can only provide a measurement result of the total conductivity of the solution, and different ion types cannot be distinguished. Therefore, the method cannot accurately measure the specific content of the citrate, only gives the total ion content, and the detection result is inaccurate.
Disclosure of Invention
The invention aims to solve the problems, and aims to provide a method for determining the citrate content in special paper by using headspace gas chromatography, which is simple to operate, rapid in detection and high in accuracy.
The invention provides a method for determining the citrate content in specialty paper by using headspace gas chromatography, which is based on the following reaction principle:
according to the invention, the GC signal value of carbon dioxide in the gas phase of the headspace bottle is determined by adopting a headspace gas chromatography, and the citrate content in the specialty paper is calculated by a standard curve.
The invention provides a method for determining the citrate content in special paper by using headspace gas chromatography, which is characterized by comprising the following steps:
(1) Sample preparation: placing potassium permanganate solution into a headspace bottle, sealing the headspace bottle, injecting acidified special paper leaching solution into the headspace bottle, and shaking uniformly;
(2) Sample detection: placing the headspace bottle in the step (1) into a headspace sample injector, and detecting a GC signal value of carbon dioxide in the headspace bottle by adopting a gas chromatography after balancing for a period of time;
(3) Citrate content calculation: and calculating the citrate content in the specialty paper according to the established linear relation between the citrate concentration and the GC signal value of the carbon dioxide.
According to the method, the content of the citrate in the special paper is measured by using a headspace gas chromatography, and the sample preparation step of the method is simple and does not need complex pretreatment steps. On the other hand, the headspace gas chromatography avoids the influence of other complex components brought into the sample when the sample is directly taken from liquid or solid, and the headspace gas chromatography can realize the rapid and accurate analysis of micro-and ultra-micro-carbon dioxide, thereby rapidly and accurately measuring the citrate content, and being suitable for the detection of large-batch industrial samples.
In some embodiments of the present invention, the sample injection amount of the specialty paper leaching solution in the step (1) is 0.1-0.5 mL.
The method screens the sample injection amount of the special paper leaching liquid, ensures that the GC signal value and the sample injection amount of the special paper leaching liquid have good linear relation, ensures the sensitivity of detection and ensures the accuracy of detection, because the sample injection amount can directly influence the signal intensity of the detector, and the stronger the sample injection amount is, the higher the sensitivity is, and the sensitivity of detection is further influenced, but the oversaturation of the detector can be caused by the overlarge sample injection amount, so that the signal distortion is caused, and the detection accuracy is reduced.
In some embodiments of the present invention, the sample injection amount of the potassium permanganate solution in the step (1) is 1-2 mL.
In some embodiments of the invention, the molar concentration of the potassium permanganate solution in step (1) is 0.1 to 0.3mol/L.
The method is further matched with the sample injection amount of the special paper leaching solution, the sample injection amount and the concentration of the potassium permanganate solution are screened and controlled, and the citrate in the special paper leaching solution can be ensured to react with the permanganate completely, so that the measurement accuracy is improved.
In some embodiments of the present invention, the equilibrium temperature of the headspace sampler in step (2) is 60-80 ℃.
In some embodiments of the invention, the balance time of the headspace sampler in step (2) is at least 20min.
The higher the equilibrium temperature is, the faster the reaction reaches equilibrium, but in order to prevent the water peak from being too high, so that the headspace bottle leaks gas, and the measurement result is influenced, the invention controls the proper equilibrium temperature and enough equilibrium time through screening so as to improve the accuracy and speed of detection.
In some embodiments of the present invention, the carrier gas used in the gas chromatography in the step (2) is nitrogen or helium.
According to the invention, nitrogen or helium is used as carrier gas, helium and nitrogen are inert gases, and are stable at normal temperature, so that chemical reaction with a sample is not easy to occur, an analysis result is not interfered, and the two gases have higher diffusion rate in a chromatographic column, can rapidly transfer a sample separator, and provide a better separation effect.
In some embodiments of the invention, the thermal conductivity detector used in the gas chromatography in step (2) is a thermal conductivity detector.
The thermal conductivity detector has high responsiveness and high sensitivity to most gases and a plurality of volatile liquids, can detect the target compound with low concentration, is relatively stable and insensitive to environmental temperature change, so the invention adopts the thermal conductivity detector for analysis.
In some embodiments of the invention, the specialty paper comprises cigarette paper, citrate preservative paper, citrate filter paper, citrate coated paper.
In some embodiments of the present invention, the preparation step of the acidified specialty paper leaching solution in step (1) includes: adding special paper into distilled water, placing on an oscillator, rotating and oscillating for a period of time, adding dilute sulfuric acid until no bubbles are generated, adding dilute sulfuric acid for acidification, and wherein the pH value of the acidified special paper leaching solution is=3-5.
Because the citrate and the potassium permanganate can generate carbon dioxide gas under the acidic condition, the special paper leaching liquid needs to be acidified, so that the citrate in the special paper leaching liquid can be fully reacted with the potassium permanganate, and the detection accuracy is improved.
By implementing the technical scheme, the invention has the following beneficial effects:
according to the method, the content of the citrate in the special paper is measured by using a headspace gas chromatography, and the sample preparation step of the method is simple and does not need complex pretreatment steps.
According to the method, the potassium permanganate is utilized to react with the citrate in the special paper to generate the carbon dioxide, the content of the citrate in the special paper is measured by measuring the content of the carbon dioxide, and the content of the carbon dioxide can be accurately measured by a gas chromatography.
The invention adopts the headspace gas chromatography to measure, which not only avoids the influence of other complex components brought into the sample when the sample is directly taken from liquid or solid, but also can realize the rapid and accurate analysis of micro-and ultra-micro carbon dioxide, thereby rapidly and accurately measuring the citrate content, being beneficial to improving the analysis efficiency and reducing the influence of manual operation, and being suitable for the detection of large-batch industrial samples.
Drawings
FIG. 1 is a schematic diagram of the procedure for determining the citrate content of specialty paper based on headspace gas chromatography in example 1 of this invention;
FIG. 2 is a graph showing the relationship between the sodium citrate content and the GC signal value in example 1 of the present invention;
FIG. 3 is a chromatogram of the headspace gas chromatography based citrate content determination in example 2 of the present invention;
FIG. 4 is a graph showing the effect of sample injection amount on GC signal value in example 4 of the present invention;
FIG. 5 is a graph of equilibrium time versus equilibrium temperature versus GC signal values for example 6 of the invention.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purpose and the effect of the present invention easy to understand, the present invention is specifically described below with reference to the embodiments and the drawings.
Example 1: study of the linear relationship between citrate concentration and GC Signal value of carbon dioxide
This example investigated the linear relationship of citrate concentration to GC signal value of carbon dioxide, comprising the steps of:
(1) Preparing a potassium permanganate solution: 1.58g of potassium permanganate solid powder is dissolved in 100ml of water to prepare 0.1mol/L potassium permanganate solution;
(2) Preparing a dilute sulfuric acid solution: adding 20ml of sulfuric acid (w/% =95-98%) into 80ml of distilled water to prepare a dilute sulfuric acid solution with volume fraction of 20%;
(3) Preparing a sodium citrate standard stock solution: dissolving 0.05g sodium citrate in 100ml distilled water to obtain 1.94X10 g sodium citrate -3 Standard stock of sodium citrate at mol/L;
(4) Preparing sodium citrate solutions with different concentrations: 1ml, 2ml, 4ml, 6ml and 8ml of standard stock solution of sodium citrate are respectively taken in a 10ml volumetric flask by a pipette, and distilled water is used for fixing the volume to scale marks to obtain different dilution concentrations (0.19 multiplied by 10) -3 、0.39×10 -3 、0.77×10 -3 、1.16×10 -3 、1.55×10 -3 、1.94×10 -3 mol/L) sodium citrate standard solution;
(5) Measurement of sodium citrate solutions of different concentrations: respectively placing 5mL of sodium citrate solution with different concentrations in 6 beakers, respectively adding dilute sulfuric acid for a plurality of times until no bubbles are generated, then adding dilute sulfuric acid to adjust the pH value of the solution to be 4, filtering supernatant to a reagent bottle to obtain acidified sodium citrate solution with different concentrations, respectively adding 1mL of potassium permanganate solution into 6 headspace bottles, pressing an aluminum cover provided with a polytetrafluoroethylene silicon rubber sealing gasket to seal the headspace bottles, then respectively injecting 0.5mL of acidified sodium citrate solution with different concentrations into the headspace bottles by using a syringe, and shaking uniformly to ensure that the sodium citrate solution and potassium permanganate completely react under an acidic condition; the headspace bottle is put into a headspace sampler, the operation schematic diagram is shown in fig. 1, and the conditions of the headspace sampler are as follows: the balance time is 20min, the balance temperature is 80 ℃, and the shaking grade is intense shaking. The temperature of the quantitative ring is 90 ℃ and the temperature of the transmission line is 100 ℃. The pressurizing pressure is 0.73bar, the carrier gas pressure is 0.68bar, the carrier gas balance time in the headspace sample bottle is 0.2min, the pipeline inflation time is 0.2min, the pipeline balance time is 0.2min, and the quantitative ring volume is 3.0mL. The volume of each headspace sample vial was 20.0mL. The signal value of carbon dioxide was recorded by gas chromatography detection, and a standard curve was obtained as shown in fig. 2. Gas chromatography operating conditions: the carrier gas is nitrogen, the flow rate is 2mL/min, the chromatographic column flow rate is 15.06mL/min, the sample inlet temperature is 250 ℃, the column box temperature is 95 ℃, and the DB-5 capillary column (30 m multiplied by 0.32mm multiplied by 0.25 mu m). The detection time is 3min, the split ratio of the split is 0.1:1, and the Thermal Conductivity Detector (TCD) is used for detecting the thermal conductivity. As can be seen from the standard curve, the CO detected by HS-GC, as shown in FIG. 2 2 Has a good linear relationship with the concentration of sodium citrate. Thus, the linear relationship between the two can be used for measuring CO in the headspace bottle by headspace gas chromatography 2 To determine the sodium citrate content of the cigarette paper.
Example 2: determination of citrate content in specialty paper
In this example, 5 sets of repeated experiments were performed on 3 different cigarette paper samples, and the citrate content was detected as follows:
(1) Sample preparation: adding 2g of cigarette paper into 100ml of distilled water, oscillating for 90min on an oscillator at a rotating speed of 130r/min, adding a small amount of dilute sulfuric acid prepared in the embodiment 1 for many times until bubbles are not generated, adding a certain amount of dilute sulfuric acid, adjusting the pH=4 of the cigarette paper leaching solution, and filtering the supernatant to a reagent bottle for later use; taking 1mL of the potassium permanganate solution prepared in the example 1 into a headspace bottle by using a pipetting gun, pressing an aluminum cover with a polytetrafluoroethylene silicon rubber sealing gasket to seal the headspace bottle, then injecting 0.5mL of cigarette paper leaching liquid into the headspace bottle by using a syringe, and shaking uniformly to enable the cigarette paper leaching liquid to completely react with the potassium permanganate under an acidic condition;
(2) Sample detection: putting the headspace bottle in the step (1) into a headspace sampler, wherein the headspace sampler is under the following conditions: the balance time is 20min, the balance temperature is 80 ℃, and the shaking grade is intense shaking. The temperature of the quantitative ring is 90 ℃ and the temperature of the transmission line is 100 ℃. The pressurizing pressure is 0.73bar, the carrier gas pressure is 0.68bar, the carrier gas balance time in the headspace sample bottle is 0.2min, the pipeline inflation time is 0.2min, the pipeline balance time is 0.2min, and the quantitative ring volume is 3.0ml. The volume of each headspace sample vial was 20.0ml. The signal value of carbon dioxide was recorded by gas chromatography detection. Gas chromatography operating conditions: the carrier gas is nitrogen, the flow rate is 2mL/min, the chromatographic column flow rate is 15.06mL/min, the sample inlet temperature is 250 ℃, the column box temperature is 95 ℃, and the DB-5 capillary column (30 m multiplied by 0.32mm multiplied by 0.25 mu m). The detection time is 3min, the split ratio of the split is 0.1:1, and the Thermal Conductivity Detector (TCD) is used for detecting the thermal conductivity. As a result of measurement, as shown in FIG. 3, it can be seen from the graph that when N is used 2 When used as carrier gas, the gas chromatograph can detect O 2 、CO 2 And H 2 O, it can be seen from the following figures that under the current gas chromatography conditions, their peaks are well separated.
(3) Citrate content calculation: according to the established linear relation between the citrate concentration and the GC signal value of the carbon dioxide, the citrate content in the cigarette paper is calculated, and the experimental result is shown in table 1.
Table 1 results of citric acid content measurements in cigarette paper
As shown in Table 1, the relative deviation of the experiment is less than 3%, which indicates that the method has good measurement accuracy and can be used for detecting the sodium citrate content in special paper.
Example 3: accuracy test of method
To verify the accuracy of the method, 5 samples of the selected examples were subjected to a standard recovery test, and 0.39X10 samples were added to each of the 5 samples -3 mol/L、0.77×10 -3 mol/L、1.16×10 -3 mol/L、1.55×10 -3 mol/L、1.94×10 -3 The concentration of the standard solution is defined as a, the concentration of the standard solution is calculated by using the GC signal value of the carbon dioxide measured by the method, the concentration of sodium citrate in a sample measured when the standard solution is subtracted from the concentration of the standard solution is defined as b, and the ratio of a to b is the standard recovery rate. The labeled recovery can assess the accuracy of the analytical method to the target analyte in the actual sample. If the recovery rate is close to 100%, the method is accurate and reliable.
TABLE 2 test results of recovery rate by addition of standard
The results in Table 2 show that the labeled recovery rate of sodium citrate is 91% -102%, which indicates that the method has good accuracy.
Example 4: screening of sample injection amount of special paper leaching liquid
According to the experimental method in example 2, the sample injection amount of the specialty paper leaching solution in step (1) was further selected, and experiments were performed with sample injection amounts of 0.1ml, 0.2ml, 0.3ml, 0.4ml, 0.5ml, 0.6ml, 0.7ml and 0.8ml of the specialty paper leaching solution, respectively, as shown in fig. 4.
As can be seen from fig. 4, when the sample injection amount of the specialty paper lixivium is 0.1 to 0.5mL, the linear relation between the sample injection amount of the specialty paper lixivium and the signal value of carbon dioxide is good, but when the sample injection amount is more than 0.5mL, the linear relation starts to be poor, and meanwhile, the sample injection amount is too large to cause oversaturation of the detector, so that the signal distortion is caused, and the detection accuracy is reduced, so that the sample injection amount of the specialty paper lixivium is limited to be 0.1 to 0.5mL in the invention.
Example 5: balance time and balance temperature screening of headspace sampler
According to the experimental method in example 2, the balance time and the balance temperature of the headspace sampler in step (2) are further screened, and experiments are performed at the balance temperature of 60 ℃, 70 ℃ and 80 ℃ respectively, and the experimental results are shown in fig. 5.
As can be seen from FIG. 5, the higher the equilibrium temperature, the faster the reaction reaches equilibrium, and the longer the reaction reaches equilibrium at 60℃and 70℃respectively, 40min and 60min, and the reaction reaches equilibrium at 20min at 80 ℃. Meanwhile, in order to prevent the air leakage of the headspace bottle caused by too high water peak, the temperature is not too high. Therefore, the invention sets the balance temperature to be 60-80 ℃ and the balance time to be at least 20min.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. A method for determining the citrate content of specialty paper by headspace gas chromatography, comprising the steps of:
(1) Sample preparation: placing potassium permanganate solution into a headspace bottle, sealing the headspace bottle, injecting acidified special paper leaching solution into the headspace bottle, and shaking uniformly;
(2) Sample detection: placing the headspace bottle in the step (1) into a headspace sample injector, and detecting a GC signal value of carbon dioxide in the headspace bottle by adopting a gas chromatography after balancing for a period of time;
(3) Citrate content calculation: and calculating the citrate content in the specialty paper according to the established linear relation between the citrate concentration and the GC signal value of the carbon dioxide.
2. The method for determining the citrate content of the specialty paper by headspace gas chromatography according to claim 1, wherein the sample injection amount of the specialty paper leaching solution in step (1) is 0.1-0.5 ml.
3. The method for determining the citrate content in the specialty paper by using the headspace gas chromatography according to claim 2, wherein the sample injection amount of the potassium permanganate solution in the step (1) is 1-2 ml.
4. The method for determining the citrate content in the specialty paper by headspace gas chromatography according to claim 3, wherein the molar concentration of the potassium permanganate solution in step (1) is 0.1-0.3 mol/L.
5. The method for determining the citrate content in the specialty paper by headspace gas chromatography according to claim 1, wherein the equilibrium temperature of the headspace sampler in step (2) is 60-80 ℃.
6. The method for determining the citrate content of specialty paper by headspace gas chromatography as recited in claim 5, wherein the balance time of said headspace injector in step (2) is at least 20min.
7. The method for determining the citrate content of the specialty paper by headspace gas chromatography according to claim 1, wherein the carrier gas used in said gas chromatography in step (2) is nitrogen or helium.
8. The method for determining the citrate content of specialty paper by headspace gas chromatography as recited in claim 7, wherein said gas chromatography in step (2) employs a thermal conductivity detector.
9. The method for determining the citrate content of specialty paper by headspace gas chromatography as recited in claim 8, wherein said specialty paper comprises any of cigarette paper, citrate preservative paper, citrate filter paper, citrate coated paper.
10. The method for determining the citrate content of specialty paper by headspace gas chromatography as recited in claim 4, wherein said step of preparing said acidified specialty paper leachate of step (1) comprises: adding special paper into distilled water, placing on an oscillator, rotating and oscillating for a period of time, adding dilute sulfuric acid until bubbles are not generated, adding dilute sulfuric acid for acidification, and wherein the pH value of the acidified special paper leaching solution is 3-5.
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