National Standard of the People's Republic of China

GB/T 2912.1-2009
Replace GB/T 2912.1-1998

Textiles – Determination of formaldehyde –

Part 1: Free and hydrolyzed formaldehyde
(water extract method)
(ISO 14184-1:1998, MOD)

Issued on 2009-06-11 Effective on 2010-01-01

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 GB/T 2912.1-2009

Textiles –Determination of formaldehyde – Part 1: free and

hydrolyzed formaldehyde (water extract method)

Warning

The execution of this part of GB/T 2912 is entrusted to those people with practical experience in
regular laboratories. This part of standard does not cover all the possible safety problems. Users shall
have the responsibilities of taking appropriate safety and healthy measures and ensuring the
conditions required in related national regulations.

1 Scope
This standard specifies a method for determining the total amount of free formaldehyde by means of
water extraction or partial hydrolysis method.
This method can be applied to the testing of textile samples in any form. The procedure is intended for
use in the range of free and hydrolysed formaldehyde on the fabric between 20 mg/kg and 3500 mg/kg.
The lower detect limit is 20mg/kg. Below this limit the result is reported as “ not detectable”.

2 Normative References

The following normative documents contain provisions which, through reference in this text, constitute
provisions of this national standard. For dated reference, subsequent amendments to, or revisions of,
any of these publications do not apply. However parties to agreements based on this standard are
encouraged to investigate the possibility of applying the most recent editions of the normative
documents indicated below. For undated references, the latest edition of the normative document
referred to applies
GB 6529 Textiles – Standard atmospheres for conditioning and testing
GB/T 6682 Water for analytical laboratory use. Specification and test methods
GB/T 11415 Laboratory sintered (fritted) filters – Porosity grading. Classification and designation

3 Principle
Formaldehyde is extracted from an accurately weighed textile sample with water at 40°c for a period.
After colorized by acetylacetone, the extraction solution is measured by spectrophotometer at 412nm to
obtain the absorbance. The amount of formaldehyde on sample is then calculated by comparison with
standard formaldehyde working curve. .
4 Reagents
All reagents shall be analytical reagent quality. Water shall be grade 3 water (GB/T 6682-1992).
4.1 Distilled water or Grade 3 water.
As per the requirements of GB/T 6682.
4.2 Acetylacetone reagent (Nash reagent)
Dissolve 150g of ammonium acetate in abut 800ml of water, add 3ml of glacial acetic acid and 2ml of
acetylacetone, transfer into a 1000ml volumetric flask and make up to the mark with water. Store in a
brown bottle.
Note 1 The reagent darkens in color slightly on standing over the first 12 h. For this reason the reagent
should be held 12 h before use. Otherwise, the reagent is useable over a considerable period of time, at
least 6 weeks. Since the sensitivity may change slightly over a long period of time, it is good practice to
run a calibration curve weekly to correct with a standard curve.
4.3 Formaldehyde solution, approximately 37% (m/V, m/m)
4.4 Ethanolic solution of dimedone
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Prepare by dissolving 1 g of dimedone (dimethyl-dihydro resorcinol or 5,5-dimethyl-cyclohexanedione) in
ethanol and by diluting the solution with ethanol to make 100ml. Prepare immediately before use.
5 Apparatus
5.1 Stoppered volumetric flasks, 50ml, 250ml, 500ml and 1000ml.
5.2 Flask, 25o=0ml, with stopper.
5.3 Pipettes, 1ml, 5ml, 10ml, 25ml and 30ml volumetric and 5ml graduated.
Note 2 An automatic pipette system of the same accuracy as manual pipettes may be used.
5.4 Burettes, 10ml and 50ml.
5.5 Photoelectric colorimeter or spectrometer, (wavelength 412nm).
5.6 Test tubes and test tube support.
5.7 Water bath, at (40±2) °c.
5.8 No.2 glass filters (according to GB/T 11415)..
5.9 Balance, accurate to 0.1mg.

6 Preparation of standard solution and calibration

6.1 Preparation

Prepare an approximately 1500mg/l stock solution of formaldehyde by diluting 3.8ml of formaldehyde

solution (4.3) to one liter with water (4.1). Determine the concentration of formaldehyde in the stock
solution by the standard method given in annex A.

Record the accurate concentration of this standardized stock solution. This stock solution will keep for
up to four weeks and is used to prepare standard dilutions.

6.2 Dilution

The equivalent concentration of the formaldehyde in the test specimen, based upon the mass of 1g of
the test specimen and 100ml of water, will be 100 times the accurate concentration of the standard
solutions.

6.2.1 Preparation of the standard-solution (S2)

Dilute 10ml of the titrated standard solution (6.1) with water to 200ml in a volumetric flask (5.1). This
solution contains 75mg/l of formaldehyde.

6.2.2 Preparation of the calibration-solutions

Prepare calibration solutions from the standard solution (S2), by diluting with water in 500ml volumetric
flasks, using a minimum of five solutions from the following:

1ml S2 to 500ml, containing 0.15µg CH2O / ml ≡ 15mg/kg CH2O on the fabric

2ml S2 to 500ml, containing 0.30µg CH2O / ml ≡ 30mg/kg CH2O on the fabric

5ml S2 to 500ml, containing 0.75µg CH2O / ml ≡ 75mg/kg CH2O on the fabric

10ml S2 to 500ml, containing 1.50µg CH2O / ml ≡ 150mg/kg CH2O on the fabric

15ml S2 to 500ml, containing 2.25µg CH2O / ml ≡ 225mg/kg CH2O on the fabric

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20ml S2 to 500ml, containing 3.00µg CH2O / ml ≡ 300mg/kg CH2O on the fabric

30ml S2 to 500ml, containing 4.50µg CH2O / ml ≡ 450mg/kg CH2O on the fabric

40ml S2 to 500ml, containing 6.00µg CH2O / ml ≡ 600mg/kg CH2O on the fabric

Calculate the first order regression curve of the type y =a+bx. This regression curve will be used for all
measurements. If the test specimens contain a higher amount of formaldehyde than 500 mg/kg dilute
the sample solution.

Note 3 This double-dilution is necessary to have the same formaldehyde concentrations in the
calibration solutions as in the test solutions of the fabrics. If the fabric contains 20 mf/kg formaldehyde,
a 1.00g specimen is extracted with 100ml water’ the solution contains 20µg formaldehyde and from
this follows, 1ml of the test solution contains 0.2µg of formaldehyde.

7 Preparation of test specimens

Do not condition the test specimen because the pre-conditioning may cause changes in the
formaldehyde content of the sample. Prior to test store the sample in a container.

Note 4 Storage may be in a polyethylene bad and wrapped in aluminium foil. The reason for the
storage precaution is that formaldehyde may diffuse through the pores of the bag. In addition, catalysts,
or other compounds present in a finished, unwashed fabric may react with the foil if in direct contact.

From the sample, cut two test specimens into small pieces, and weigh approximately 1 g of the pieces
to an accuracy of 10mg. If the formaldehyde content is low, increase the test specimen weight to 2.5g
in order to achieve a sufficient accuracy.

Put each specimen into a 250ml flask with stopper (5.2) and add 100ml of water. Stopper tightly and
place in a water bath at ((40±2)°c for (60±5)min. Then filter the solution into another flask through a
filter (5.8).

In cases of dispute use a conditioned parallel specimen to calculate a correction coefficient to be used
in correcting the mass of the test specimen to be used for the test.

Cut the test specimen from the sample, weigh it immediately and again after conditioning (in
accordance with GB 6529). Use these values to calculate the correction coefficient and use the
coefficient to calculate the conditioned weight of the test specimen used for the sample solution.

8 Procedure

8.1 Take 5ml of the filtered test specimen solution by use of pipette (5.3), put it into a tube (5.6), and
take 5ml of the standard formaldehyde solutions (6.2.2) into further tubes (5.6). Add 5ml of
acetylacetone reagent (4.2) into each tube and shake them.

8.2 Keep the test tubes first in a water bath at (40±2)°c for (30±5)min and then at ambient
temperature for (30±5) min. Taking the solution of 5ml of acetylacetone reagent solutions in 5ml of
water having been treated in the same way as the blank reagent and using a spectrometer, measure
the absorbance in a 10mm absorption cell at a wavelength of 412nm against water.

8.3 If it is anticipated that the fabrics have formaldehyde extraction levels of more than 500mg/kg, or
if the calculated levels from the test using the 5:5 ratio are more than 500mg/kg, dilute the extract to
give absorbance in the range of the calibration curve (the dilution factor shall be taken into account
when calculating the results).
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8.4 In case the color of test specimen solution is too dark, put 5ml of the sample solution in a
separate test tube, add 5ml of water instead and treat in the same way as above. Use water as the
control.

8.5 Make two parallel tests.

CAUTION: Exposure of the developed tallow color to direct sunlight for a period of time will cause
some fading. Therefore the measurement shall be conducted free from any strong sunlight.

8.6 If there is a doubt that the absorption may not be due to formaldehyde but for example to an
extracted coloring agent, carry out a confirmation test, with dimedone (see 8.7)

Note 5 Dimedone reacts with formaldehyde, and thus no color resulting from formaldehyde reaction
will be observed.

8.7 For dimedone confirmation, put 5ml of the sample solution in a test tube (diluted where
necessary), add 1ml of ethanol solution of dimedone (4.4) and shake. Warm the solution in a water
bath at (40±2) °c for (10±1)min, then add 5ml of acetylacetone reagent (4.2), repeat the procedure 8.2.
Determine the absorbance of the solution with water instead of the sample solution. The absorbance
from formaldehyde at 412nm disappears.

9 Calculation and expression of the results

Correct the absorbance of the test specimen as follows:

A = As – Ab – (Ad) ---------------------------------------------------------(1)

Where

A is the corrected absorbance

As is the measured absorbance of the test specimen

Ab is the measured absorbance of the blank reagent

Ad is the measured absorbance of blank specimen (only in case of discoloration or other

contamination)

Determine the amount of the formaldehyde in µg/ml from the calibration curve, using the value of the
corrected absorbance.

Calculate the amount of formaldehyde extracted for each specimen using the following equation (2):

c x 100
F = -------------- ---------------------------------------------------------(2)
m

Where

F is the amount of formaldehyde extracted from specimen, mg/kg

c is the amount of formaldehyde in solution (in mg/l) as read from the calibration graph

m is the mass of test specimen in grams

Calculate the arithmetic mean of 2 values as the test result, and round it to integers.
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If the result is less than 20mg/kg, report as “not detectable”.

10 Test Report

The test report shall contain the following information:

a) Reference to this standard;

b) Sample received date, means in which it was stored prior to test and testing date;

c) Description of the sample tested and how packaged;

d) The mass of the test specimen and, if required, the correction coefficient for the mass;

e) The range of the calibration graph;

f) The amount of formaldehyde extracted from the sample, mg/kg;

g) Any deviation, by agreement or otherwise, from the procedure specified.

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 Annex A
(Normative)
Standardization of formaldehyde stock solution – Sodium sulfite method

A.1 General

The stock solution containing approximately 1500µg/ml of formaldehyde shall be accurately

standardization in order to prepare a precise calibration curve for use in colorimetric analysis.

A.2 Principle

An aliquot of the stock solution is reacted with an excess of sodium sulfite followed by a back-titration
with acid solution in the presence of thymolphthalein as indicator.

A.3 Apparatus

A.3.1 Volumetric pipette, 10ml.

A.3.2 Volumetric pipette, 50 ml.

A.3.3 Burette, 50ml.

A.3.4 Erlenmeyer flask, 150ml.

A.4 Reagents

A.4.1 Sodium sulfite, cNa2SO3 = 1 mol/l, made by dissolving 126g of anhydrous Na2SO3 per liter of
water.

A.4.2 Thymolphthalein, 10g/l in ethanol.

A.4.3 Sulfuric acid. cH2SO4 = 0.01 mol/l

Note This reagent may be purchased in a standardization form or should be standardized using a
standard sodium hydroxide solution.

A.5 Procedure

Pipette 50ml of sodium sulfite (A.4.1) into the Erlenmeyer flask (A.3.4). Add two drops of
thymolphthalein indicator (A.4.2). Add a few drops of sulfuric acid (A.4.3), if necessary until the blue
color disappears.

Pipette 10ml of the stock formaldehyde solution into the flask (the blue color will reappear). Titrate the
solution with sulfuric acid (A.4.3) until the blue color is discharged. Record the volume of sulfuric acid
solution used.

Note 1 The volume of sulfuric acid should be approximately 25ml.

Note 2 A calibration pH meter may be used in place of thymolphthalein indicator, in which case the end
point is reached at pH – 9.5.

Carry out the procedure in dulplicate.

A.6 Calculations
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1ml of 0.01 mol/l sulfuric acid is equal to 0.6mg of formaldehyde.

Calculate the formaldehyde concentration in the stock solution (in µg/ml) from the following equation:

V1 x 0.6 x 1000
C = ---------------------------------------------------------------- ------------------------------------------(A1)
V2

Where:
C – Formaldehyde concentration in the stock solution, µg/ml;
V1 - Volume of sulfuric acid, ml;
V2 - Volume of formaldehyde solution, ml;
0.6 – Mass of formaldehyde equivalent to 1ml 0.01 mol/l of sulfuric acid, mg.

Calculate the average of the results and use the concentration determined by equation (A1) in
preparing the calibration curve for the colorimetric analysis.

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 Annex B
(Informative)
Standardization of formaldehyde stock solution – Iodometric method

B.1 General

The stock solution containing approximately 1500µg/ml of formaldehyde shall be accurately

standardization in order to prepare a precise calibration curve for use in colorimetric analysis.

B.2 Principle

An aliquot of the stock solution is reacted with an excess of iodine solution followed by a back-titration
with acid solution in the presence of starch as indicator.

B.3 Apparatus

B.3.1 Volumetric pipette, 5ml, 10ml, 20ml, 50ml.

B.3.2 Burette, 50ml.

B.3.3 250ml Iodine flask & Erlenmeyer flask with stopper.

B.3.4 Volumetric flask, 500ml, 1L.

B.4 Reagents

B.4.1 Iodine solution [c(I2) = 0.1mol/L]: put 13g of Iodine (I2) and 30g of potassium iodide (KI) into 1L
brown volumetric flask, and dilute with water to the scale, shake and store in dark.

B.4.2 Sodium hydroxide, c(NaOH) = 1mol/L.

B.4.3 Sulfuric acid. c(H2SO4)= 0.5 mol/l

B.4.4 Starch indicator: dissolve 0.5g of soluble starch into 100ml of water, boil for 2 min, prepare
freshly before use.

B.4.5 Sodium thiosulfate [c(Na2S2O3) = 0.1mol/L]: weigh 25g of Na2S2O3⋅5H2O (or 16g anhydrous
Na2S2O3), and pour into in 1L of freshly boiled and cooled water with 0.1g of anhydrous sodium
carbonate added, stir, dissolve and store in brown bottle.

Note Titration method of sodium thiosulfate is given as follows:

Dry potassium dichromate in oven at 120°c -125°c for 1h, cool and then weigh 0.15g to the nearest
0.0001g, put it into a 250ml iodine flask, add 25ml of water, 2g of KI and 20ml of H2SO4 solution (20%),
stir & mix thoroughly and cover with a stopper, keep in dark for 10 min to make sure the sufficient
resolution of iodine. Add 100ml of water and shake thoroughly, titrate the solution with prepared
Na2S2O3 solution [c(Na2S2O3) = 0.1mol/L] until it turns to light yellow color, then add 3ml of 0.5mol
starch solution; continue the titration with Na2S2O3 solution until the color turns from blue to green.

Calculate the concentration of Na2S2O3 as follows:

m x 1000
C1 = ----------------
V x 49.03

Where:
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C1 – Concentration of Na2S2O3, mol;
m – Mass of titrating solution (potassium dichromate), g;
V – Volume of titrate (Na2S2O3), mL;
49.03 – Molar mass of titrating solution (potassium dichromate) [M(1/6K2Cr2O7)], g/mol.

B.5 Procedure

B.5.1 Pipette 10ml of formaldehyde solution (6.1) into the 250ml iodine flask. Accurately add 25ml of
iodine solution (B.4.1) and 10ml of NaOH solution (B.4.2), cover with stopper and keep in dark for 15
min, meanwhile take distilled water as the blank.

B.5.2 Add 15ml of H2SO4 solution (B.4.3), titrate it with Na2S2O3 solution until it is in yellow, add
several drops of starch indicator, and continue the titration until the blue color disappears. Repeat the
above procedures..

B.5.3 Calculation: calculate the formaldehyde concentration in the stock solution from the equation
(B.1):

(VB - Vs)x c1 x 0.015

c= ------------------------------------------ x 106 ------------------------------------------(B.1)
V

Where:
c – Formaldehyde concentration in the stock solution, µg/ml;
VB - Volume of blank Na2S2O3 solution, ml;
V2 - Volume of Na2S2O3 solution, ml;
c1 – Concentration of standard Na2S2O3 solution, mol/L.
0.015 – Mass of formaldehyde equivalent to 1ml of standard Na2S2O3 solution (c = 1.0000 mol/L), g;
V – Volume of formaldehyde solution, ml.

Calculate the average of the results and use the concentration determined by equation (B.1) in
preparing the calibration curve for the colorimetric analysis.

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