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net

ICS 71.100.01; 87.060.10

G 55

National Standard of the People’s Republic of China

GB/T 24101-2018
Replaces GB/T 24101-2009

Limit and determination of

4-aminoazobenzene in dye products
染料产品中 4-氨基偶氮苯的限量及测定

(English Translation)

Issue date: 2018-12-28 Implementation date: 2019-11-01

Issued by the State Administration for Market Regulation
the Standardization Administration of the People's Republic
of China

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Contents

Foreword ............................................................................................................................ i
1 Scope .......................................................................................................................... 1
2 Normative references .................................................................................................. 1
3 Requirements .............................................................................................................. 1
4 Test methods ............................................................................................................... 1
5 Test report ................................................................................................................... 9
Annex A (Normative) Structure information of 4-aminoazobenzene ............................. 10
Annex B (Informative) Standard chromatogram of 4-aminoazobenzene ...................... 11

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Foreword

ChinaStandards.net is in charge of this English translation. In case of any doubt about

the English translation, the Chinese original shall be considered authoritative.

This standard is developed in accordance with the rules given in GB/T 1.1-2009.

This standard replaces GB/T 24101-2009 Limit and determination of 4-aminoazobenzene

in dye products. In addition to editorial changes, the following main technical changes
have been made with respect to GB/T 24101-2009:

——High-performance liquid chromatography for the determination of

4-aminoazobenzene is added (see 4.2).

This standard was proposed by China Petroleum and Chemical Industry Association.

This standard is under the jurisdiction of Technical Committee on Dyestuff of

Standardization Administration of China (SAC/TC 134).

The previous edition of this standard is as follows:

——GB/T 24101-2009.

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Limit and determination of 4-aminoazobenzene

in dye products

Warning: The personnel using this standard shall have practical experience in
laboratory work. This standard does not address all of the safety problems. The
users are under the obligation to adopt proper safety and health measures and
shall ensure conformance with the requirements specified in national relevant
regulations.

1 Scope

This standard specifies the limit requirements and determination methods for
4-aminoazobenzene (see Annex A) in dye products.

It applies to the limit and determination of 4-aminoazobenzene in commercial dyes, dye

products, dye intermediates and textile dyeing auxiliaries.

2 Normative references

The following referenced documents are indispensable for the application of this
document. For dated references, only the edition cited applies. For undated references,
the latest edition of the referenced document (including any amendments) applies.

GB/T 6682-2008 Water for analytical laboratory use - Specification and test methods
(ISO 3696:1987, MOD)
GB/T 8170-2008 Rules of rounding off for numerical values & expression and judgment
of limiting values

3 Requirements

The content of 4-aminoazobenzene (see Annex A) in dye products shall be less than or
equal to 150mg/kg, in which the limit of 4-aminoazobenzene in liquid dye and pigment
printing paste shall be converted according to its solid content.

4 Test methods

4.1 Gas chromatography-mass spectrometry (arbitration method)

4.1.1 Principle

The dye sample is subjected to reductive pyrolysis with sodium hydrosulfite in weakly
alkaline medium, and the azo bond of 4-aminoazobenzene is kept non-breaking by

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controlling the pyrolysis temperature and the pyrolysis time; 4-aminoazobenzene in the
pyrolysis solution is extracted with a solvent; after concentration, it is tested by gas
chromatograph-mass spectrometer and quantified by characteristic ion external standard
method.

4.1.2 Determination methods

4.1.2.1 General

Unless otherwise specified, only recognized analytical reagent and Grade 3 water
(specified in GB/T 6682-2008) shall be used in analysis. Judgment of the inspection result
shall be carried out according to the rounding-off value comparison method specified in
GB/T 8170-2008, 4.3.3.

4.1.2.2 Reagents and solutions

4.1.2.2.1 Sodium chloride

4.1.2.2.2 Sodium hydroxide solution: 20g/L.

4.1.2.2.3 Acetone.

4.1.2.2.4 Sodium hydrosulfite (rongalite).

4.1.2.2.5 Anhydrous sodium sulfite.

4.1.2.2.6 Anhydrous sodium sulfate.

4.1.2.2.7 Anhydrous ether: it shall be purified when being used as it is easy to produce
peroxide after long time storage. Take 500mL of ether, add 100mL of ferrous sulfate
solution (50g/L aqueous solution), shake well and then discard the water layer, re-distill it
in an all-glass device, and collect fractions of 33.5°C to 34.5°C.

4.1.2.2.8 Ethyl acetate.

4.1.2.2.9 Methanol: chromatographically pure.

4.1.2.2.10 4-aminoazobenzene standard: content (mass fraction) ≥ 98%.

4.1.2.2.11 Standard stock solution: weigh proper amount of 4-aminoazobenzene

standard, dissolve it with methanol and prepare into standard stock solution of about
1.0mg/mL. Properly seal the standard stock solution and store it in a refrigerator at 0℃
~4℃. It is valid for 6 months.

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4.1.2.2.12 Standard working solution: dilute the standard stock solution with methanol
and prepare it into the standard working solution of proper concentration. Properly seal
the standard working solution and store it in a refrigerator at 0℃~4℃. It is valid for 1
month.

4.1.2.3 Apparatuses

4.1.2.3.1 Gas chromatograph-mass spectrometer (GC-MS).

4.1.2.3.2 Chromatographic column: capillary column with 50% of

phenyl-methylpolysilicone stationary phase, 30m×0.25mm×0.25μm or the equivalent.

4.1.2.3.3 Microinjector or automatic sample injector: 10μL.

4.1.2.3.4 Extractor: made of hard glass, tubular, with ground mouth and bottle
stopper,50mL.

4.1.2.3.5 Ground centrifugal tube with stopper: 10mL or 25mL.

4.1.2.3.6 Centrifuge: 4 000r/min.

4.1.2.4 Sample pretreatment

Accurately weigh 0.1g of sample (1mL of liquid sample) to the nearest 0.000 1g, add 7g of
sodium chloride to the extractor, then add 9mL of sodium hydroxide solution and make
them fully infiltrate and dissolve (if the sample is difficult to be dissolved, add 5mL of
acetone), shake well and add 0.2g of rongalite to fully oscillate and dissolve. Put it into
40±2℃ water bath for thermal insulation for 30min, shake the extractor intermittently to
make the sample pyrolyzed, then take it out and cool to room temperature. Extract for
three times with anhydrous ether, 10mL per time, (if it is difficult to layer and separate
during extraction, transfer the solution to a ground centrifugal tube with stopper for
centrifugation), collect the extract into a 50mL beaker, add about 0.5mL of ethyl acetate,
and about 0.5g of anhydrous sodium sulfite (antioxidant) and anhydrous sodium sulfate
(desiccant) to heat under infrared light so as to make the ether solution gently and evenly
boiling. When the remaining solution is slightly less than 1mL, transfer it into a graduated
small sample bottle, make up to 1.0mL with ethyl acetate. Determine the recovery rate
after the standard samples is treated under the same conditions.

4.1.2.5 Gas chromatography-mass spectrometry analysis conditions

As the test result depends on the used apparatus, it is impossible to give general
parameters for the chromatographic analysis. The following parameters (see Table 1)
have been proved appropriate to the test.

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Table 1 Gas chromatography-mass spectrometry analysis conditions

Control parameter Operation condition

Carrier gas Helium (99.999%)

Carrier gas flow/(mL/min) 1.0

Injection port temperature/℃ 300

Ion source temperature/℃ 230

Transfer line temperature/℃ 280

Injection mode Splitless injection

Ionization method EI

Injection volume/μL 1.0

Keep at an initial temperature of 80℃ for 2min; rise to 150℃ at 5℃

Column temperature programming /min, keep for 0min and then rise to 260℃ at 8℃/min, keep for
0min, finally rise to 280℃ at 30℃/min and keep for 10min.

4.1.2.6 Determination

According to the content of the substance to be tested in the specimen, select standard
working solution with similar concentration for the determination. Respectively take
specimen solution and standard working solution for determination according to the above
chromatographic analysis conditions, and quantify by an external standard method. See
Figure B.1 in Annex B for gas chromatography-mass spectrometry total ion chromatogram
of 4-aminoazobenzene standard sample.

4.1.2.7 Result calculation

The 4-aminoazobenzene content which is represented by mass fraction ω1 and

expressed in mg/kg is calculated according to equation (1):

AcV
w1 
A8 m
(1)

where,

A——the peak area of 4-aminoazobenzene target ion in specimen solution;

c——the corresponding concentration of 4-aminoazobenzene in standard solution,

μg/mL;

V——the final constant volume of specimen solution, mL;

A8——the peak area of 4-aminoazobenzene in standard solution;

m——the mass of specimen, g.

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Round the calculation result to one decimal place.

4.1.2.8 Permissible deviation

The absolute value of the difference between the two parallel determination results of
4-aminoazobenzene content shall be no more than 20% of the arithmetic mean, and the
arithmetic mean thereof is taken as the determination result.

4.1.2.9 Lower determination limit

The lower limit of gas chromatography-mass spectrometry in this standard is 1.0mg/kg.

4.1.2.10 Recovery rate

Adopt standard addition technique; add 1.0mL of standard working solution to 0.1g of the
dye product which is free of 4-aminoazobenzene as determined by this method, operate
according to the gas chromatography-mass spectrometry given in 4.1, and the measured
recovery rate of various 4-aminoazobenzenes shall be between 80% and 120%.

4.1.2.11 Precision

The absolute difference between the results of two mutually independent tests performed
by the same operator for the same object, with the same equipment and test method and
in the same laboratory during a short time shall not be greater than 20% the arithmetic
mean.

4.2 High-performance liquid chromatography

4.2.1 Principle

The dye sample is subjected to reductive pyrolysis with sodium hydrosulfite in weakly
alkaline medium, and the azo bond of 4-aminoazobenzene is kept non-breaking by
controlling the pyrolysis temperature and the pyrolysis time; 4-aminoazobenzene in the
specimen is extracted with anhydrous ether; the extract is determined by
high-performance liquid chromatography-ultraviolet detector and quantified by external
standard method.

4.2.2 Determination method

4.2.2.1 General

Unless otherwise specified, only recognized analytical reagent and Grade 3 water
(specified in GB/T 6682-2008) shall be used in analysis. Judgment of the inspection result

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