Some standard content:
HG 3310--1999
This standard is revised from the chemical industry standard HG3310-1987 "O-phenylenediamine". The main technical differences between this standard and HG3310-1987 are: the melting point index and its determination method are cancelled. The original "superior grade" and "first grade" are changed to "superior grade, first grade". A chapter "referenced standards" is added.
In the test method chapter, identification tests are added. At the same time, the gas chromatography method in this standard is different from the original standard in terms of chromatographic column, internal standard and solvent, and the main content and impurity content can be measured simultaneously in one injection (different from the method of separate determination in the original standard); peak area is used instead of peak height for calculation. The thin layer diazo method is retained, but the washing and filtration process is removed, and the method summary is supplemented, clarifying that the rounding value comparison method is used for the limit value processing.
"Foreword", "Scope", "Technical requirements" are changed to "Requirements", and "Packaging, marking, storage and transportation" are changed to "Marking, labeling, packaging, storage and transportation".
This standard replaces HG3310-1987 from the date of implementation. This standard was proposed by the Technical Supervision Department of the former Ministry of Chemical Industry of the People's Republic of China. This standard is under the technical jurisdiction of Shenyang Chemical Research Institute of the Ministry of Chemical Industry. The drafting units of this standard are Nanjing Chemical Plant and Shanghai Pesticide Plant of the Ministry of Chemical Industry. The main drafter of this standard is Qian Yingchun.
This standard was first issued as a professional standard in 1987, and was adjusted to a mandatory chemical industry standard in 1997, and was renumbered. 359
Chemical Industry Standard of the People's Republic of China
o-Phenylenediamine
o-PhenylenediamineOther names, structural formulas and basic physicochemical parameters of o-Phenylenediamine are as follows: ISO common name: o-PhenylenediamineTrade name: o-Phenylenediamine
Chemical name: 1.2-diazobenzene
Structural formula:
Experimental formula: C.HgNz
Relative molecular mass: 108.14 (according to the 1993 international relative atomic mass)Melting point: 103~104℃
Boiling point: 256~258℃
Solubility: easily soluble in ethanol, ether and chloroform, slightly soluble in waterStability: the color will darken in air and light, sealed and stored away from light for 1 circle
HG 3310--1999
HG3310~1987
This standard specifies the requirements, test methods, inspection rules, and marking, labeling, packaging, storage and transportation of o-phenylenediamine. This standard applies to o-phenylenediamine obtained by ammoniation reduction of o-nitrochlorobenzene and o-phenylenediamine obtained by further refining.
2 Cited Standards
The provisions contained in the following standards constitute the provisions of this standard through reference in this standard. When this standard is published, the versions shown are valid. All standards will be revised, and the parties using this standard should explore the possibility of using the latest versions of the following standards. GB190—1990 Dangerous Goods Packaging Markingbzxz.net
GB/T601-1988 Preparation of Standard Push Solution for Chemical Reagent Titration Analysis (Volumetric Analysis) GB/T603-1988 Preparation of Preparations and Products Used in Chemical Reagent Test Methods GB/T1250-1989 Methods for Expressing and Determining Limit Values GB/T4946-1985 Terminology for Gas Chromatography
GB/T6678--1986 General Rules for Sampling of Chemical Products GB/T66791986 General Rules for Sampling of Solid Chemical Products 3 Requirements
3.1 Appearance: Superior products are white to purple-grey solids, and medium and qualified products are light brown to brown crystals. 3.2 O-phenylenediamine should meet the requirements of Table 1.
Approved by the State Administration of Petroleum and Chemical Industry on June 16, 1999 360
Implemented on June 1, 2000
Content of o-phenylenediamine
o-chloroaniline
o-nitroaniline
Test method
4.1 Identification test
HG 3310—1999
Table 1 Control item index of o-phenylenediamine
Superior product
First-class product
Qualified product
a) Gas chromatography: This identification test can be carried out simultaneously with the determination of o-phenylenediamine. Under the same chromatographic operating conditions, the relative difference between the retention time of a chromatographic peak of the sample solution and the retention time of the chromatographic peak of o-phenylenediamine of the standard solution should be within 1.5%. b) Infrared spectroscopy: There should be no obvious difference between the infrared spectra of the sample and the standard sample in the wave number range of 4000~~400cm-1 (see Figure 1).
Figure 1 Infrared spectrum of o-phenylenediamine standard sample
4.2 Determination of test results
The test results shall be determined in accordance with the rounded value comparison method specified in GB/T1250, and the final expression of the results shall be consistent with the required index value.
4.3 Determination of o-phenylenediamine content and impurity content 4.3.1 Determination of o-phenylenediamine content by thin layer-diazo method 4.3.1.1 Method summary
Dissolve the o-phenylenediamine sample in ethyl acetate, then spot it on a plate covered with GF 254 silica gel, develop it with a mixture of petroleum ether and ethyl acetate, scrape the main spot and dissolve it in hydrochloric acid, and then perform diazo titration. Reaction principle:
+2HCI+NaNO,
NaNO +HCI ----HNO2 +NaCl
+NaC1+2H,0
2HNO2+2KI+2HCl-2NO+2KCI+2HzO+124.3.1.2 Instruments and equipment
Ultraviolet lamp: wavelength 254nm.
Chromatography cylinder.
Flat glass: 180mm×150mm.
Pipette: 0.5mL, calibrated by spotting method. Acid burette: 10 mL.
4.3.1.3 Reagents and solutions
Hydrochloric acid solution: 1+4.
HG 3310--1999
Sodium nitrite standard titration solution: c(NaNO2)=0.02mol/L, prepared according to 3.9 and 4.22 of GB/T601-1988. Potassium iodide starch test paper: prepared according to 4.2.3 of GB/T603-1988. Potassium bromide solution: 200g/L.
Petroleum ether: boiling range 90～120℃.
Ethyl acetate.
Silica gel GF254: chemically pure, for thin layer chromatography. 4.3.1.4 Preparation of developing agent
When the developing temperature is 10-25℃, the volume ratio of petroleum ether and ethyl acetate is 1:4; when the developing temperature is greater than 25℃, the volume ratio of petroleum ether and ethyl acetate is 1:2. 4.3.1.5 Preparation of silica gel plate
Weigh 10g silica gel in a mortar, add 25mL water, grind carefully until it is homogeneous and paste-like, immediately pour it on a clean chromatography glass plate, gently shake the glass plate to make the silica gel evenly distributed on the plate without bubbles, place the plate in a horizontal position, solidify under an infrared lamp or in the air, put it in a 130℃ oven for activation for 40min, take it out after cooling slightly, store it in a desiccator filled with color-changing silica gel for cooling and standby use. 4.3.1.6 Preparation of sample solution
Accurately weigh 1.1g (accurate to 0.0002g) of o-phenylenediamine sample, put it in a 25mL volumetric flask, dissolve it with ethyl acetate and dilute it to the scale, shake it.
4.3.1.7 Operation steps
a) Thin layer separation
Take an activated thin layer plate, use a 0.5mL pipette to accurately transfer 0.5mL of the sample solution, and spot it in a straight line 2.5cm away from the bottom edge of the thin layer plate (the two ends of the spotting line are 1.5cm). After the sample is spotted, rinse the tip of the pipette with ethyl acetate, and the washing liquid is evenly spotted on the spotting line. After air drying to remove the solvent, stand it upright in a chromatography cylinder containing an appropriate amount of developing agent for development (the thin layer plate is immersed in the developing agent for about 1cm). When the solvent front rises to about 13cm from the spotting line, take out the plate, wait for the solvent to evaporate to dryness, place the plate under ultraviolet light for 2min, use a needle tip to draw the purple-red spectrum band of o-phenylenediamine, use a scraper to scrape the o-phenylenediamine spectrum band into a 200mL beaker, wipe the unscratched silica gel on the glass plate with a cotton ball moistened with ethyl acetate, put it in the beaker together, and then add 40mL of hydrochloric acid solution to the beaker to dissolve it. b) Diazo titration
Add 10mL of potassium bromide solution to the above beaker, place it in an ice bath and cool it to 0-5℃, insert the tip of the burette into the solution, add about 95% of the total required amount of sodium nitrite standard solution at one time under constant stirring, then remove the burette from the liquid surface, rinse the tip of the burette with a small amount of water, and continue to titrate until the solution makes the potassium iodide starch test paper turn slightly blue and remain unfaded for 1 minute. This is the end point. At the same time, perform a blank test under the same conditions.
c) Calculation
The o-phenylenediamine content (X,) expressed as mass percentage is calculated according to formula (1): X, = (Vi- Vo)c× 0. 108 1
Wherein: c——actual concentration of sodium nitrite standard titration solution, mol/L; V. volume of sodium nitrite standard titration solution consumed by the sample, mL; V. —Volume of sodium nitrite standard titration solution consumed in blank test, mLm
Mass of o-phenylenediamine sample, g;
0.1081--Mass of o-phenylenediamine in grams equivalent to 1.00mL of sodium nitrite standard titration solution [c(NaNO,)=0.0200mol/L].
4.3.1.8 Allowable difference
Take the arithmetic mean as the determination result. The difference between the results of two parallel determinations should not exceed 1.0%. 362
HG 3310—1999
4.3.2 Determination of o-phenylenediamine content and its impurities by gas chromatography (arbitration method) 4.3.2.1 Determination of o-phenylenediamine content and its impurities in superior products 4.3.2.1.1 Summary of the method
The sample is dissolved in chloroform, and a glass column with 7% OV-225/101 white support as filler and a hydrogen flame ionization detector are used to calibrate the o-phenylenediamine and its impurities in the sample by gas chromatography, and the area is normalized to a certain amount. 4.3.2.1.2 Reagents and solutions
Chloroform.
O-phenylenediamine standard: The corresponding impurity peak should not be detected under the determination conditions. o-chloroaniline standard: known content, greater than or equal to 99.0%. o-nitroaniline standard: known content, greater than or equal to 99.0%. Stationary phase: OV-225.
Carrier: 101 white carrier (149~177μm), pre-treated by alkali washing or coating. 4.3.2.1.3 Instruments and equipment
Gas chromatograph: with hydrogen flame ionization detector. Chromatographic data processor.
Chromatographic column: 2.0m×3.2mm(id) glass column. Column filling: 0V-225 coated on 101 white carrier (149~177um). Stationary liquid: (stationary liquid + carrier) = 7:100 (mass ratio). 4.3.2.1.4 Preparation of chromatographic columns
a) Coating of stationary liquid
Alkali washing: Prepare 50mL of 50g/L potassium hydroxide methanol solution in a 200mL beaker, slowly pour 10g of carrier into the beaker to completely soak the carrier, soak for about 2h, then wash with distilled water until neutral, rinse twice with anhydrous ethanol, place in a 100℃ oven to dry, and set aside.
Alkali coating: Weigh 0.1g potassium hydroxide into a 250mL beaker, add an appropriate amount (slightly larger than the volume of the added carrier) of methanol to dissolve it, slowly pour 10g of carrier into the beaker to completely soak the carrier, soak for 15min, heat under an infrared lamp, gently tap and rotate the beaker to make the coating even, after the solvent evaporates, dry the beaker in a 100℃ oven for 30min, and set aside. Accurately weigh 0.70g of OV-225 stationary liquid into a 250mL beaker, add an appropriate amount (slightly larger than the volume of the added carrier) of chloroform to completely dissolve it, pour it into the alkali-washed or alkali-coated carrier, shake it gently to mix it evenly and evaporate the solvent. Then dry the beaker in an oven at 110℃ for 1h, take it out and cool it to room temperature in a desiccator. b) Filling of chromatographic column
Connect a small funnel to the outlet of the washed and dried chromatographic column, fill the prepared filler into the column in batches, and tap the column wall continuously until it is filled to 1.5cm from the column outlet. Move the funnel to the inlet of the chromatographic column, plug a small ball of silanized glass wool at the outlet, connect it to the vacuum pump through a rubber tube, turn on the vacuum pump, continue to slowly add the filler, and tap the column wall continuously to make it evenly and tightly filled. After filling, also plug a small ball of glass wool at the inlet end and press it appropriately to prevent the column filler from moving. c) Aging of the chromatographic column
Connect the inlet end of the chromatographic column to the vaporization chamber, and do not connect the outlet end to the detector for the time being. Pass the carrier gas (Nz) at a flow rate of 20 mL/min, and heat it to 200℃ in stages. At this temperature, age it for at least 24 hours. 4.3.2.1.5 Gas chromatography operating conditions
Temperature (℃): column chamber 180; vaporization chamber 250; detector chamber 250. Gas flow rate (mL/min): carrier gas (N2) 40; hydrogen 50; air 500. Injection volume: 1 μL.
Retention time (min): o-phenylenediamine 5.4; o-chloroaniline 2.2; o-nitroaniline 15; p-nitrofluorinated benzene 3.4. The gas chromatogram of the superior grade of o-phenylenediamine is shown in Figure 2, and the gas chromatogram of the first-class and qualified products is shown in Figure 3. 363
HG 3310—1999
1 Solvent; 2-o-chloroaniline, 3-o-phenylenediamine Figure 2 Gas chromatogram of the superior grade of o-phenylenediamine 2
1 Solvent; 2-o-fluoroaniline; 3-nitrochlorobenzene; 4-o-phenylenediamine, 5-o-nitroaniline Figure 3 Gas chromatogram of the first-class and qualified o-phenylenediamine 3
The above operating parameters are typical. According to the characteristics of different instruments, the given operating parameters can be appropriately adjusted to obtain the best effect. Start the machine every day, wait for the operating conditions to stabilize, first inject 2~3 injections of o-phenylenediamine saturated solution, and then inject the sample for analysis. 4.3.2.1.6 Determination steps
1) Determination of correction factor
a) Preparation of calibration stock solution
According to Table 2, weigh various reagents (accurate to 0.0002g) into a brown volumetric flask, dissolve and dilute to the mark with chloroform. Store in a refrigerator, and its shelf life is one month. Table 2 Preparation of calibration stock solution
Reagent name
Mass g
Dilution volume, mL
b) Preparation of calibration mixed solution
o-Chloroaniline
o-Nitroaniline
o-Phenylenediamine
According to Table 3, use a pipette to draw the calibration stock solution into 5 10mL brown volumetric flasks, and then dilute to the mark with chloroform. Store in a refrigerator and recalibrate once a week. Table 3
Preparation of calibration mixed solution
Standard number
Stock solution number
Volume after dilution
Standard number
c) Determination of correction factor
HG 3310—1999
Table 3 (end)
Stock solution number
Volume after dilution
Select a mixed standard sample with the same content as the sample. Under the above operating conditions, after the instrument baseline is stable, draw 1μL of the mixed standard sample for injection.
The correction factor (f) of each component is calculated according to formula (2): m
Where: fi—correction factor of component i, g/mm2; m;—mass of component i, g;
A; peak area of component i, mm2.
2) Preparation of sample solution
Weigh 0.20g (accurate to 0.0002g) of o-phenylenediamine sample into a 10mL brown volumetric flask, dissolve it with chloroform and dilute to the scale, shake it thoroughly.
3) Determination
Under the above operating conditions, after the instrument baseline is stable, continuously inject several needles of sample solution, injecting 1μuL. Use a data processor or formula (3) to calculate the mass percentage content (X,) of each component: X.
Where: X,—the content of component i, %;
f.—the correction factor of component i, g/mm2; A, the peak area of component i, mm2.
4.3.2.1.7 Allowable difference
Take the arithmetic mean as the determination result. The difference between two parallel determination results should not exceed 0.5%. 4.3.2.2 Determination of o-phenylenediamine content and impurities in first-class and qualified products 4.3.2.2.1 Method Summary
The chromatographic conditions are the same as those for superior products. The quantitative method is the internal standard method, and the internal standard is p-nitrofluorobenzene. 4.3.2.2.2 Reagents and solutions
Same as 4.3.2.1.2.
p-Nitrochlorobenzene: It should not contain impurities that interfere with the analysis. 4.3.2.2.3 Instruments and equipment
Same as 4.3.2.1.3.
4.3.2.2.4 Gas chromatography operating conditions
Same as 4.3.2.1.5.
4.3.2.2.5 Determination steps
1) Preparation of calibration stock solution
According to the requirements of Table 4, accurately weigh various reagents (accurate to 0.0002) into a brown volumetric flask, dissolve and dilute to the scale with chloroform, and store in a refrigerator. The shelf life is one month. 365
Reagent name
Mass, g
Dilution volume, mL
o-Chloroaniline
2) Preparation of calibration mixed solution
HG 3310 1999
Table 4 Preparation of calibration stock solution
o-Nitroaniline
o-Phenylenediamine
p-Nitrochlorobenzene
According to Table 5, use a pipette to pipette the calibration stock solution into 5 10mL brown volumetric flasks, and then dilute them to the scale with chloroform respectively. Store in a refrigerator and recalibrate once a week. Table 5 Preparation of calibration mixed solution
Standard sample number
3) Determination of sample
a) Preparation of internal standard solution
Stock solution number
Volume after dilution
Accurately weigh 2.0 g (accurate to 0.0002 g) of p-nitrofluorobenzene in a 50 mL brown volumetric flask, dissolve and dilute to scale with chloroform.
b) Preparation of sample solution
Accurately weigh 0.20 g (accurate to 0.0002 g) of o-phenylenediamine sample in a 10 mL brown volumetric flask, use a pipette to accurately transfer 5 mL of internal standard solution, dissolve and dilute to scale with chloroform. c) Determination
Select a mixed standard sample with the same content as the sample. Under the above operating conditions, after the baseline is stable, continuously inject several injections of standard solution, calculate the repeatability of the relative response value of each injection, and when the relative response value of two adjacent injections changes less than 1.5%, perform the determination in the order of standard solution, sample solution, sample solution, and standard solution. d) Calculation
Average the ratio of the peak area of each component in o-phenylenediamine to the internal standard in the two injections of sample solution and the two injections of standard solution before and after the sample.
The content of each component in o-phenylenediamine expressed as mass percentage (X,) is calculated according to formula (4): remip
mass percentage of component, %;
where X,
the average value of the peak area ratio of the component to the internal standard in the standard solution; the average value of the peak area ratio of the component to the internal standard in the sample solution; the mass of component i in a standard sample, name;
m—mass of the sample, g;
P,—mass percentage of component i in the standard sample, %4.3.2.2.6 Allowable difference
(4)
HG3310—1999
Take the arithmetic mean of each as the determination result. The difference between the two parallel determination results should not be greater than 1.5% for o-phenylenediamine, 0.1% for o-chloroaniline, and 0.05% for o-nitroaniline. 5 Inspection rules
5.1 Products with uniform quality are considered as one batch.
5.2 According to the provisions of GB/T6678 and GB/T6679, samples shall be collected from 100% of the packaging containers of each batch of products. The samples in the packaging containers shall be taken out with a stainless steel probe, and the total amount of samples shall not be less than 250g. 5.3 Mix the samples evenly and put them into two clean and dry brown ground-mouth bottles. Label the bottles with the following: manufacturer name, product name, batch number and sampling date. One bottle shall be inspected by the inspection department and the other bottle shall be sealed and kept for three months for future reference. 5.4 If any index does not meet the requirements of this standard in the inspection results, samples shall be collected from twice the amount of packaging containers for re-inspection. Even if only one index does not meet the requirements of this standard in the re-inspection results, the entire batch of products shall be unqualified. 6 Marking, labeling, packaging, transportation
6.1 Marking
The packaging of o-phenylenediamine shall be firmly marked. The contents include: manufacturer name, factory address, product name, trademark, net content, production date, batch number, grade, and the "toxic substance" sign shall be marked in accordance with the provisions of GB190. 6.2 Label
The label shall indicate the product name, net content, grade, batch, production date and manufacturer name. 6.3 Packaging
O-phenylenediamine is packed in an iron barrel lined with a polyethylene bag, and the net content of each barrel shall not exceed 140kg. Other forms of packaging can also be used according to user requirements.
6.4 Storage and Transportation
The package should be stored in a ventilated and dry warehouse. The container should be sealed, never exposed to sunlight, and should not be mixed with flammable materials. It should be kept away from fire and heat sources to avoid contact with skin, eyes and inhalation. 3673. Mix the samples evenly and put them into two clean and dry brown ground-mouth bottles. Label the bottles with the following information: manufacturer name, product name, batch number and sampling date. One bottle will be inspected by the inspection department and the other bottle will be sealed and kept for three months for future reference. 5.4. If one of the indicators does not meet the requirements of this standard, the sample should be taken from the packaging container with twice the amount for re-inspection. Even if only one indicator does not meet the requirements of this standard, the whole batch of products will be unqualified. 6. Marking, labeling, packaging, and transportation
6.1. Marking
The packaging of o-phenylenediamine should be firmly marked. The contents include: manufacturer name, address, product name, trademark, net content, production date, batch number, grade, and the "drug-containing" mark in accordance with the provisions of GB190. 6.2. Labeling
The label should indicate the product name, net content, grade, batch, production date and manufacturer name. 6.3 Packaging
O-phenylenediamine is packed in iron barrels lined with polyethylene bags, and the net content of each barrel shall not exceed 140kg. Other forms of packaging may also be used according to user requirements.
6.4 Storage and Transportation
The packaged products should be stored in a ventilated and dry warehouse. The container should be sealed and not exposed to sunlight. It should not be mixed with flammable materials and should be kept away from fire and heat sources to avoid contact with skin and eyes and inhalation. 3673. Mix the samples evenly and put them into two clean and dry brown ground-mouth bottles. Label the bottles with the following information: manufacturer name, product name, batch number and sampling date. One bottle will be inspected by the inspection department and the other bottle will be sealed and kept for three months for future reference. 5.4. If one of the indicators does not meet the requirements of this standard, the sample should be taken from the packaging container with twice the amount for re-inspection. Even if only one indicator does not meet the requirements of this standard, the whole batch of products will be unqualified. 6. Marking, labeling, packaging, and transportation
6.1. Marking
The packaging of o-phenylenediamine should be firmly marked. The contents include: manufacturer name, address, product name, trademark, net content, production date, batch number, grade, and the "drug-containing" mark in accordance with the provisions of GB190. 6.2. Labeling
The label should indicate the product name, net content, grade, batch, production date and manufacturer name. 6.3 Packaging
O-phenylenediamine is packed in iron barrels lined with polyethylene bags, and the net content of each barrel shall not exceed 140kg. Other forms of packaging may also be used according to user requirements.
6.4 Storage and Transportation
The packaged products should be stored in a ventilated and dry warehouse. The container should be sealed and not exposed to sunlight. It should not be mixed with flammable materials and should be kept away from fire and heat sources to avoid contact with skin and eyes and inhalation. 367
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