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Iron, steel and alloy -- Determination of sulfur content -- Methylene blue spectrophotometric method
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Methods for chemical analysis of iron, steel and alloy--The reducing distillation-methylene blue photometric method for the determination of sulfur content
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GB/T 223.67-2008: PDF in English (GBT 223.67-2008) GB/T 223.67-2008
Iron, steel and alloy. Determination of sulfur content. Methylene blue spectrophotometric method
ICS 77.080.01
H11
National Standards of People's Republic of China
GB/T 223.67-2008/ISO 10701..1994
Replacing GB/T 223.67-1989
Steel and alloy - Determination of sulfur content
Methylene blue spectrophotometry
(ISO 10701..1994, IDT)
2008-05-13 released
2008-11-01 implementation
General Administration of Quality Supervision, Inspection and Quarantine of People's Republic of China
China National Standardization Administration released
Foreword
This part of GB/T 223 is equivalent to ISO 10701..1994 "Determination of sulfur content of steel and alloy Methylene blue spectrophotometric
law".
This section is equivalent translation ISO 10701..1994.
For ease of use, this section made the following editorial changes.
a) Replace the word "international standard" with "this part";
b) Use the decimal point "." instead of the decimal point ",";
c) Delete the preface to the International Standard.
This Part Replaces GB/T 223.67-1989 "Methods for chemical analysis of iron, steel and alloy - The reductive distillation - Methylene blue spectrophotometric method for the determination of sulfur
Quantity ", compared with the main changes made to the following.
--- Determination range from 0.001% to 0.030% adjusted to 0.0003% ~ 0.01%;
--- "Use bromine to make sulfur oxidation, and evaporate to drive nitric acid" to "use perchloric acid to smoke and drive away nitric acid";
--- The amount of sample is adjusted from 1.0000g to 0.50g and 1.0g respectively according to the content difference;
--- Distillation and purification devices have been changed.
This part of Appendix A, Appendix B are informative appendix.
This part is proposed by China Iron and Steel Association.
This part of the National Standardization Technical Committee Iron and Steel centralized.
This section mainly drafted by. China Steel Research Technology Corporation.
The main drafters of this section. Yang Guixiang, Teng Xuan.
This part of the standard replaces the previous editions are.
GB 223.2 (three) -1981, GB 223.67-1989.
GB/T 223.67-2008/ISO 10701..1994
Steel and alloy - Determination of sulfur content
Methylene blue spectrophotometry
Warning. Personnel using this section should have practical experience in formal laboratory work. This section does not indicate all possible security issues. Make
It is the user's responsibility to take appropriate safety and health measures and to ensure compliance with the requirements of the relevant state laws and regulations.
1 range
GB/T 223 provisions of this part of the Methylene blue spectrophotometric determination of sulfur content in steel and alloy.
This section applies to steel and alloy mass fraction of 0.0003% ~ 0.01% sulfur content determination. Niobium, Silicon, Tantalum and Titanium to Sulfur
Determination of interference. According to the content of interfering elements, the applicable range and the amount of sample are given in Table 1.
Table 1
Interference elements of the maximum allowable content (mass fraction) /%
Nb Si Ta Ti
The amount of sample
Application (mass fraction) /%
0.5 1.0 0.3 1.0 1.0 0.0003 ~ 0.0010
1.0 2.0 0.6 2.0 0.50 0.0010 ~ 0.010
2 Normative references
The following documents contain provisions which, through reference in this Part of GB/T 223, become the provisions of this section. Any reference to the date of the citation
All subsequent amendments (not including errata content) or revisions do not apply to this section, however, encouraged to be reached under this section
The parties to the agreement study whether the latest versions of these documents are available. For undated references, the latest version applies to this book
section.
ISO 377-2. 1989 Selection and preparation of test specimens for sample and forged steels - Part 2. Samples for determination of chemical composition
ISO 385-1. 1984 Laboratory glassware burets - Part 1. Basic requirements
Laboratory glassware Monoscript pipettes
ISO 1042. 1983 Laboratory glassware single standard line volumetric flask
ISO 3696. 1987 Analysis of laboratory water specifications and test methods
ISO 5725. 1986 Precision of measurement methods - Repeatability and reproducibility of standard measurement methods are determined by interlaboratory tests
3 principle
The sample is dissolved in a mixed acid of hydrochloric acid and nitric acid, evaporated to white smoke with perchloric acid to drive off hydrochloric acid and nitric acid. Dissolved salt with hydrochloric acid to hydrogen
A mixture of iodic acid and hypophosphorous acid was used as a reducing agent, and hydrogen sulfide generated under a stream of nitrogen was distilled and taken up in a zinc acetate solution. Through with N,
N-dimethyl-p-phenylenediamine solution and the ferric solution to produce methine blue. Absorbance was measured at a wavelength of 665 nm.
4 reagent
Unless otherwise stated, use only analytical reagents of very low sulfur content, approved analytical reagents and newly prepared ISO 3696
Level 2 water.
4.1 Hydrochloric acid, p approximately 1.19 g/mL.
4.2 hydrochloric acid, ρ about 1.19g/mL, diluted to 1 +15.
4.3 perchloric acid, ρ about 1.54g/mL.
GB/T 223.67-2008/ISO 10701..1994
4.4 hydrobromic acid, p about 1.48 g/mL.
4.5 hydrochloric acid - nitric acid mixed acid. Mix 1 volume of hydrochloric acid (4.1) with 1 volume of nitric acid (ρ of about 1.40/mL) and prepare beforehand.
4.6 Reducing agent solution..200 mL of hydriodic acid [about 57% (mass fraction)] and 50 mL of hypophosphorous acid [about 50% (mass fraction)] were transferred
Into the purification device (see Figure 1). Flush with nitrogen at a flow rate of 100 mL/min for 10 min to mix the acid and expel the air from the system.
Open the heating mantle, heat to boiling, and then keep slightly boiled for about 120 min at a temperature of about 115 ° C in a stream of nitrogen. After purification (see
10.3), turn off the heating cover. The solution is then cooled and stored in a brown bottle.
Figure 1 reduction solution purification device diagram
4.7 Absorption solution. 5g of zinc acetate dihydrate [(CH3COO) 2Zn · 2H2O] was dissolved in 400mL of water,.200mL of hydrogen peroxide
Sodium solution (30g/L) and 70g of ammonium chloride, then diluted with water to 1000mL, and mix.
4.8 iron solution, 10g/L. Weigh 1.00g sulfur-free pure iron, transferred to a 300mL beaker, add 20mL hydrochloric acid (ρ about
1.19g/mL, diluted to 1 + 1), covered with a watch glass, heated to dissolve, and slightly boiled for about 10min. Then, 2mL of nitric acid was added dropwise (ρ approx
1.40 g/mL) so that the iron is oxidized. Boil to drive nitrogen oxides, cooled to room temperature. Transfer to 100mL single-labeled volumetric flask, diluted with water
To the mark, mix well.
4.9 Ferric chloride solution. 1g of ferric chloride hexahydrate (FeCl3 · 6H2O) was dissolved in about 40mL of water, 10mL of hydrochloric acid was added
(4.1), diluted with water to 100mL, mix well.
GB/T 223.67-2008/ISO 10701..1994
4.10 N, N-dimethyl-p-phenylenediamine solution, hydrochloric acid medium. 0.5 g of N, N-dimethyl-p-phenylenediamine hydrochloride [NH2C6H4N
(CH3) 2 · 2HCl] dissolved in about 100mL water, add 230mL hydrochloric acid (4.1), diluted with water to 500mL, and mix.
4.11 sulfur standard solution
4.11.1 sulfur stock solution, equivalent to 1g sulfur per liter. Weigh pre-dried at 110 ℃ 2h, and cooled to room temperature in a desiccator of potassium sulfate
5.4352g [purity ≥ 99.5% (mass fraction)], dissolved in water, quantitative transferred to 1000mL single-labeled line volumetric flask, diluted to the mark, mixed
uniform. This stock solution 1mL contains 1mg sulfur.
4.11.2 sulfur standard solution A, equivalent to 10mg sulfur per liter. Pipette 10.00mL sulfur stock solution (4.11.1) placed in 1000mL single standard
Line capacity bottle, diluted with water to the mark, mix well. 1 mL of this solution contains 10 μg sulfur.
4.11.3 sulfur standard solution B, equivalent to 1mg sulfur per liter. Pipette 10mL standard solution (4.11.2) placed 100mL single standard line capacity
Bottle, diluted with water to the mark, mix well. Prepared before use. 1 mL of this solution contains 1 μg sulfur.
4.12 nitrogen.
5 device
All glass feelers shall comply with Class A of ISO 385-1, ISO 648 or ISO 1042.
Normal laboratory equipment and the following instruments are used.
5.1 reductive distillation unit in millimeters
Figure 2 reduction distillation unit diagram
Assemble the reductive distillation unit as shown in Fig. 2, all using a close-to-ground glass interface. If this unit is used for the first time, or for a long time no
Use, blank test should be repeated until a stable low blank value.
GB/T 223.67-2008/ISO 10701..1994
5.1.1 decomposition flask, the volume of about 300mL.
5.1.2 reflux condenser, about 150mm.
5.1.3 gas cylinder, the volume of about 150mL.
5.1.4 Absorption bottle, 20mL or 100mL single-labeled volumetric flask.
5.2 spectrophotometer, absorbance can be measured at a wavelength of 665nm.
6 take samples
Take sample according to ISO 377-2 or the appropriate national standard of steel.
7 operating procedures
Warning. Perchloric acid vapor can cause explosions when ammonia, nitrous acid smoke or organic matter are present.
7.1 Sample
According to the estimated sulfur content, weighed sample, accurate to 1mg.
a) Sulfur content (mass fraction) is 0.0003% to 0.0010%, and the amount of sample is about 1.00 g.
b) sulfur content (mass fraction) is 0.0010% ~ 0.010%, the amount of sample is about 0.50g.
7.2 blank test
Follow the same procedure using the same amount of all reagents and perform a blank test parallel to the sample. Recommended. For the sulfur content (mass points
) Is less than 0.001%, the blank value should not exceed 0.7μg of sulfur. For the sulfur content (mass fraction) of 0.001% to 0.010%, the blank
The value should not exceed 1.5 μg of sulfur.
7.3 Determination
7.3.1 Preparation of test solution
7.3.1.1 Place the sample (7.1) in a disintegration flask (5.1.1) and add 15 mL hydrochloric acid-nitric acid mixed acid (4.5). Place at room temperature
After 30 min, heat gently until the dissolution reaction has stopped.
7.3.1.2 Pipette 5.0mL perchloric acid (4.3) and 1.0mL iron solution (4.8), heated to evaporate until white smoke appears. After cooling,
Add 5 mL hydrochloric acid (4.1). (For a possible modification of this step, see 9.) Heat again to smoke on a hot plate at about 300 ° C. Of course
After continued evaporation of perchlorate white smoke to make do.
7.3.1.3 Remove the cooling, add 10mL hydrochloric acid (4.1), heated to dissolve salts, cooled to room temperature.
7.3.2 Reduced distillation
Add 20 mL reducing agent solution (4.6) to the disintegration flask (5.1.1) and allow to stand for 10 min. Add 30mL of water to the scrubbing flask, root
Depending on the sulfur content to be tested, place an appropriate volume of absorbent solution (4.7) in the absorbent container (5.1.4) as follows.
a) The content of sulfur (mass fraction) is less than 0.0010%. Add 10mL absorption solution (4.7) into 20mL absorption bottle.
b) The content of sulfur (mass fraction) is 0.0010% ~ 0.010%, add 50mL absorption solution (4.7) in 100mL absorption
Bottle
Water was introduced into the condenser and connected to a decomposition flask (5.1.1) equipped with a test solution. Nitrogen was passed into the apparatus at a flow rate of 100 mL/min, as shown in the figure
2 shows. The test solution was heated to 114 ℃ ~ 118 ℃ for 30min. This can usually be done by setting the hotplate temperature to 250 ° C (see 10.2)
To be done. The generated gas is carried by the nitrogen carrier gas into the absorption bottle through the scrubber.
7.3.3 color
7.3.3.1 Sulfur content (mass fraction) less than or equal to 0.0010%
Remove 20 mL of the absorbent bottle (5.1.4) and the gas inlet tube from the device. The tube of liquid droplets into the absorption solution, with a trace amount of migration
Dispenser Add 1.0 mL of hydrochloric acid (4.2) from the upper end of the tube to the inner surface of the tube and rinse with 1 mL of water.
Remove the gas inlet tube, gently swirl the 20 mL absorption bottle and place in a thermostat at 25 ° C for 20 min. Then in the absorption bottle
(5.1.4) Add 2.0 mL N, N-dimethyl-p-phenylenediamine solution (4.10) and shake gently. Immediately add 0.4mL ferric chloride solution
(4.9), intense shaking 1min. Dilute to the mark with water and mix well. Place 15min.
GB/T 223.67-2008/ISO 10701..1994
7.3.3.2 sulfur content (mass fraction) of 0.0010% ~ 0.010%
Remove 100 mL of the absorbent bottle (5.1.4) and the gas inlet tube from the device. The tube of liquid droplets into the absorption solution, with a trace amount of migration
Add 1.0 mL of hydrochloric acid (4.2) from the upper end of the tube to the inner surface of the tube and rinse with 1 mL or 2 mL of water.
Remove the gas inlet tube and gently swirl the 100 mL absorption bottle and place in a thermostat at 25 ° C for 20 min. Then in the absorption bottle
(5.1.4) 10.0 mL N, N-dimethyl-p-phenylenediamine solution (4.10) was added and shaken gently. Immediately added 2.0mL ferric chloride solution
(4.9), intense shaking 1min. Dilute to the mark with water and mix well. Place 15min.
7.3.4 Spectrophotometric measurement
After zeroing the spectrophotometer (5.2) with water as reference, a 1 cm dish was used and spectrophotometry was performed at a wavelength of 665 nm.
7.4 Calibration curve establishment
7.4.1 Preparation of calibration solution
1.0mL iron solution (4.8) were placed in six decomposition flask (5.1.1), according to Table 2 were added to the corresponding volume of sulfur standard solution
liquid. Then add 15mL hydrochloric acid - nitric acid mixed acid (4.5), 5.0mL perchloric acid (4.3), heated to smoke. The following press 7.3.1.2
To 7.3.3.
Table 2
Sulfur content (mass fraction) /% Volume of sulfur standard solution A (4.11.2)/mL Volume of sulfur standard solution B (4.11.3)/mL Mass of corresponding sulfur/μg
Less than or equal to 0.0010
0a
1.0
3.0
5.0
7.5
10.0
1.0
3.0
5.0
7.5
10.0
0.0010 ~ 0.010
0a
0.5
1.0
2.0
3.0
5.0
a Zero calibration solution.
7.4.2 Spectrophotometric measurement
Zero calibration solution (see Table 2) as a reference to the spectrophotometer (5.2) zero after the absorption with 1cm dish, at a wavelength of 665nm into
Spectrophotometric determination.
7.4.3 Calibration curve drawing
Draw a calibration curve for absorbance of sulfur concentration, with the sulfur concentration developed for every 20 mL (see 7.3.3.1) or per 100 mL (see 7.3.3.2)
Liquid sulfur content (μg) said.
8 results calculation
8.1 Calculation method
According to the calibration curve (see 7.4.3), the absorbance of the color developing solution as determined in 7.3.4 (see 7.3.3.1 or 7.3.3.2) is converted to the corresponding
Of the mass, expressed as the mass of sulfur (μg).
Sulfur content, expressed in terms of mass fraction (%), is given by equation (1)
106 ×
(1)
GB/T 223.67-2008/ISO 10701..1994
Where.
8.2 Precision
This part of the precision test to 16 sulfur levels, carried out in 11 or 13 laboratories, each laboratory for each level of sulfur content determination
3 times (see note 1 and note 2).
The samples used are shown in Table A of Appendix A. 1.
According to ISO 5725, the results obtained are statistically processed.
Table 3, the data diagram given by Appendix B.
Table 3
Reproducibility limit
R RW
0.0003
0.0005
0.0010
0.0020
0.0050
0.0100
0.00008
0.00011
0.00017
0.00027
0.00047
0.00072
0.00017
0.00023
0.00037
0.00060
0.00111
0.00171
0.00011
0.00014
0.00021
0.00031
0.00051
0.00074
NOTE 1 Two determinations in three determinations are made under the repeatability conditions specified in ISO 5725, that is, by the same investigator, using the same instrument, the same
Test conditions, the same calibration, measured in the shortest possible time.
Note 2. The third determination by the Note 1 Noteworthy staff, using the same instrument, at different times (different days), with a new calibration.
The result, the laboratory reproducibility limit (RW) was calculated.
9 special circumstances
For samples containing selenium, the second paragraph of 7.3.1 "After cooling, add 5mL hydrochloric acid (4.1)" should be changed to "After cooling, add 5mL hydrochloric acid
(4.1) and 5 mL hydrobromic acid (4.4). "
10 Operating Procedure Comments
10.1 Due to the high sensitivity of this method, it is important to eliminate sources of sulfur contamination. In fact, it is possible to provide specialized rooms for such analysis
More effective. If the tester determines that two reagents are blank, the lower one is usually the correct one. When using the new King carefully
When washing the flask, fake sulfur contamination was observed.
It is important that all sample processing should be performed in a rigorous laboratory environment (no soot and any sulfur or sulfur compounds
Of steam or dust).
In order to make the sulfur blank low and constant (eg 狓 = 0.5 μg, σ = 0.15 μg sulfur), care should be taken when choosing the acid, but not required
Purification by distillation.
10.2 From a chemical reaction point of view, the reduction of sulphate to hydrogen sulphide is a difficult reaction. In order to ensure the sulfur recovery, should be strictly controlled
Reaction conditions. The best reduction temperature is 114 ℃ ~ 118 ℃. If the reducing solution is over-diluted by the sample solution, its boiling point is reduced, too
The original reaction rate slowed down slightly. Above 120 ° C, the acidic mixture has hypophosphorous acid decomposition and phosphine formation.
The temperature required for the electric furnace should be set by inserting a pre-blank test of the thermometer in the heating solution.
GB/T 223.67-2008/ISO 10701..1994
10.3 To verify the purification, connect a hydrogen sulfide trap (see Figure 1) containing 10 mL of absorbent (4.7) and continue heating for 30 min.
Remove the collector. According to 7.3.3.1 color, according to the need to use grinding glass stopper. Add 8mL water, dilute to about 20mL. put
Set 15min.
After zeroing the spectrophotometer (5.2) with water as reference, a 1 cm dish was used and spectrophotometry was performed at a wavelength of 665 nm.
Purification is complete when the measured absorbance value is less than 0.055 (corresponding to 1 μg of sulfur).
11 test report
The test report should include the following.
a) Identification of materials, laboratory and analysis date;
b) to comply with the provisions of this section;
c) analysis results and their representation;
d) the anomalies observed in the assay;
e) Actions or optional actions that may have an impact on the analysis but are not covered by this section.
GB/T 223.67-2008/ISO 10701..1994
Appendix A.
(Informative)
Additional information on international cooperation tests
Table 3 shows the international analysis of 12 steel samples and 4 iron samples from 11 or 13 laboratories in 9 countries in 1989 and.1991
The result of the experiment is obtained.
The test results are documented in ISO /T C17/SC1N839, March.1990 and ISO /T C17/SC1N915, February.1992
Reported. Pictorial precision data in Appendix B.
The samples used are shown in Table A 1.
Table A. 1
Sample
Sulfur content (mass fraction) /% precision data
Approved value
measured value
S, 1 S, 2
Reproducibility limit
R RW
1) JSS002-2 (pure iron)
2) JSS003-2 (pure iron)
3) ECRM096-1 (non-alloy steel)
4) JSS244-4 (non-alloy steel)
5) JSS240-8 (non-alloy steel)
6) ECRM480-1 (cast iron)
0.00008
0.0004
0.0009
0.0015
0.0060
0.0086
0.00008
0.00042
0.00084
0.00154
0.00573
0.00817
0.00009
0.00042
0.00084
0.00155
0.00569
0.00819
0.00006
0.00010
0.00017
0.00024
0.00082
0.00107
0.00010
0.00016
0.00032
0.00077
0.00112
0.00203
0.00009
0.00016
0.00023
0.00040
0.00078
0.00095
7) NBS348a (stainless steel)
8) JSS654-10 (stainless steel)
9) JSS611-8 (high speed steel)
10) ECRM191-1 (high silicon steel)
11) ECRM285-1 (high alloy steel)
12) ECRM481-1 (ductile iron)
13) JSS650-9 (stainless steel)
14) ECRM235-1 (high alloy steel)
15) JSS654-7 (stainless steel)
16) NBS339 (selenium-containing stainless steel)
0.0007
0.0007
0.0013
0.0017
0.0024
0.004
0.0053
0.0072
0.0093
0.013a
0.00053
0.00064
0.00133
0.00193
0.00214
0.00324
0.00538
0.00681
0.00912
0.0125
0.00052
0.00062
0.00134
0.00189
0.00211
0.00320
0.00540
0.00680
0.00906
0.0124
0.00011
0.00013
0.00016
0.00041
0.00041
0.00053
0.00062
0.00016
0.00042
0.00125
0.00039
0.00029
0.00053
0.00144
0.00076
0.00169
0.00087
0.00063
0.00158
0.00313
0.00009
0.00010
0.00023
0.00072
0.00028
0.00041
0.00039
0.00033
0.00057
0.00108
S, 1. The average of the measured data on the same day.
S, 2. The average of different days measured data.
a sample amount = 0.25 g.
Note. The following four samples have been omitted from the regression calculations for the following reasons.
Sample 1) (pure iron). sulfur content lower than the lower limit of this method;
Sample 7) (stainless steel). titanium content of 2.1% (mass fraction);
Sample 10) (high silicon steel). silicon content of 3.7% (mass fraction);
Sample 12) (ductile iron). Silicon content 2.3% (mass fraction).
GB/T 223.67-2008/ISO 10701..1994
Appendix B
(Informative)
Precision data illustration
lgR = 0.6756lgS, 1-1.4005
lgRW = 0.5467lgS, 2-2.0368
among them.
S, 1. The average sulfur content obtained on the same day, expressed in terms of mass fraction;
S, 2. The average sulfur content obtained on different days, expressed in terms of mass fraction.
GB/T 223.67-2008/ISO 10701..1994
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Source: Above contents are excerpted from the PDF -- translated/reviewed by: www.chinesestandard.net / Wayne Zheng et al.
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