1、STD-BSI BS EN 12974-ENGL 2000 = Lb24665 OB3529 BRITISH STANDARD Surface active agents - Determination of the 1,4=dioxane content in alkyl-e thoxy-sulfate products by GLChead space procedure The European Standard EN 129741999 has the status of a British Standard ICs 71.100.40 NO COPYING WITHOUT BSI P
2、ERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW T7b BS EN 12974:2000 STD-BSI ES EN 12974-ENGL 2000 1ib2qbb9 0835297 702 M BS EN 12974:2000 This British Standard, having been prepared under the direction of the Sector Committee for Materiais and Chemicals, was published under the authority of the Stan
3、dards Committee and comes into effect on 15 March 2000 National foreword This British Standard is the official English language version of EN 129741999. The UK participation in its preparation was entrusted to Technical Committee CII/34, Methods of test for surface active agents, which has the respo
4、nsibility to: - aid enquirers to understand the text; - present to the responsible European committee any enquiries on the - monitor related international and European developments and promulgate interpretation, or proposals for change, and keep the UK interests informed them in the UK A list of org
5、anizations represented on this committee can be obtained on request to its secrem. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “Intemational Standards
6、 Correspondence Index“, or by using the A British Standard does not purport to include all the necessary provisions of a conhct. Users of British standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. fac
7、ility of the BSI Standards Electronic Catalogue. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 12, an inside back cover, and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued. A
8、mendments issued since publication I ISBN O 580 35774 O STD.BS1 BS EN 12974-ENGL 2000 H 1624bb9 0835298 849 m EUROPEAN STANDARD NORME EUROPEENNE EUROPISCHE NORM EN 12974 December 1999 ICs 71.100.40 English version Surface active agents - Determination of the 1,4-dioxane content in alkyl-ethoxy-sulfa
9、te products by GLClhead space procedure Agents de surface - Dtermination de la teneur en 1,4- dioxane dans les alkylsulfates thoxyles par CGUEspace de tte Grenzfichenaktive Stoffe - Bestimmung des Gehaltes von 1,4-Dioxan in Alkylethoxysulfatprodukten durch ein GLCIHead-Space-Verfa hren This European
10、 Standard was approved by CEN on 27 October 1999. CEN members are bound to comply with the CENICENELEC Internal Regulations which stipulate the conditions for giving this Europmn Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concer
11、ning such national standards may be obtained on application to the Central Secretariat or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by traslation under the responsibility of a CEN member into its own la
12、nguage and notified to the Central Secretariat has the same status as he official versions. CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden,
13、 Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION EUROPISCHES KOMITEE FR NORMUNG COMIT EUROPEN DE NORMALISATION Central Secretariat: rue de Stassart. 36 8-1050 Brussels Q 1999 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Member
14、s. Ref. No. EN 12974:1999 E Page 2 EN 12974: 1999 Contents Foreword . 3 I Scope 4 2 Normative references . - . 4 3 Principle _ 4 4 Reagents 4 5 Apparatus - 4 6 Calibration - . 5 7 Sampling . - 6 8 Procedure . 7 9 Evaluation of chromatograms . 8 10 Expression of results 8 11 Precision 9 12 Test rep0
15、rt .- 9 Annex A (informative) Statistical data from the ring test carried out in 1996 12 OBSI 03-2000 STD-BSI BS EN 12974-ENGL 2000 1b24bb9 0835300 227 Page 3 EN 12974: 1999 Foreword This European Standard has been prepared by Technical Committee CENTTC 276, Surface active agents, the Secretariat of
16、 which is held by AFNOR This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by June 2000, and conflicting national standards shall be withdrawn at the latest by June 2000. According to the CENCENELEC Int
17、ernal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerlan
18、d and the United Kingdom. Annex A is informative. OBSI 03-2000 STDoBSI BS EN 12974-ENGL 2000 = Lb21ibb9 0835301 Lb3 = Page 4 EN 12974: 1999 1 Scope This European Standard specifies a gas-liquid chromatography GLClhead space method for the determination of the 1,4-dioxane content in alkyl-ethoxy-sulf
19、ate products. The method is applicable to samples containing 1,4-dioxane in the range from 5 mg/kg to 100 mglkg. 2 Normative references This European Standard incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate place
20、s in the text and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated in it by amendment or revision. For undated references the latest edition of the publication referr
21、ed to applies. EN IS0 3696, Water for analytical laboratory use - Specification and test methods (IS0 36963987). IS0 607, Surface active agents and detergents - Methods of sample division. 3 Principle The sample is weighed into a head space vial and a calibration solution/solvent is added. The seale
22、d vial is placed in a head space sampling instrument and allowed to reach thermal equilibrium. A portion of the vapour phase is then analyzed by temperature programmed GLC. Flame ionization detection and either an internal standard or standard addition method of quantification are employed. 4 Reagen
23、ts During the analysis, use only reagents of recognized analytical grade and the water used shall conform to grade 3 in accordance with EN IS0 3696. 4.1 1,4dioxane, purity 98 g/100 g minimum (density 1,03 g/ml at 20 OC). 4.2 4-methyl-l,3dioxane, purity 98 g/1 O0 g minimum (density 0,98 g/ml at 20 OC
24、). 4.3 N,Ndimethylacetamide (DMA). The suitability of this reagent shall be confirmed by analyzing a 1 ml aliquot portion in accordance with clause 8. It shall be free from peaks which interfere with 1,6dioxane and 4-methyl-I ,3- dioxane. NOTE HPLC grade DMA is suitable. 4.4 Carrier gas, nitrogen or
25、 helium. 5 Apparatus Ordinary laboratory apparatus and the following. 5.1 Chromatograph, with the items specified in 5.2 to 5.5. 5.2 Capillary column, capable of the separation characteristics shown in Figure 1 NOTE methyl silicone stationary phase is advisable. A 50 m x 0,53 mm ID fused silica capi
26、llary column (film thickness: 5,O vm) with 5 % phenyl silicone and 95 % OBSI 03-2000 STDeBSI BS EN LZ974-ENGL 2000 Lb24bb7 0835302 OTT Page 5 EN 12974: 1 999 5.3 Flame ionization detector. 5.4 apparatus. 5.5 5.6 Head space sampling unit, complete with 20 ml crimped top glass vials, suitable for head
27、 space GLC Septum and crimped tops, lined with aluminium or PTFE, for closing the vials. Sealing pliers, for the vials. 5.7 Electronic integrator. 5.8 Volumetric flasks, 50 ml and 100 ml capacity. 5.9 Gas tight syringes, 1 ml i 0,001 ml capacity. 5.10 Analytical balance, accurate to 0,l mg. 6 Calibr
28、ation 6.1 Preparation of calibration solutions 6.1 .I Calibration solution A Add approximately 40 ml of DMA (4.3) to a 50 ml volumetric flask (5.8). Weigh 400 mg f 1 mg 4-methyl-I ,3- dioxane (4.2). Make up to volume with DMA and thoroughly homogenize. Quantitatively dilute OS ml of this solution to
29、 100 ml with DMA. The final solution A contains 40 pg/ml4-methyl-l,3-dioxane. 6.1.2 Calibration solution B Add approximately 40 ml of DMA (4.3) to a 50 ml volumetric flask (5.8). Weigh 200 mg f 1 mg of 1,4-dioxane (4.1) and 400 mg f 1 mg of 4-methyl-l,3-dioxane (4.2). Make up to volume with DMA and
30、thoroughly homogenize. Quantitatively dilute 0,5 ml of this solution to 1 O0 ml with DMA. The final solution B contains 20 pglml of 1,4-dioxane and 40 pg/ml of 4-methyl-l,3-dioxane. 6.1.3 Calibration solution C Add approximately 40 ml of DMA (4.3) to a 50 ml volumetric flask (5.8). Weigh 400 mg f 1
31、mg of 1,4-dioxane (4.1) and 400 mg I 1 mg of 4-methyl-l,3-dioxane (4.2). Make up to volume with DMA and thoroughly homogenize. Quantitatively dilute 0,5 ml of this solution to 1 O0 ml with DMA. The final solution C contains 40 pglml of 1,4-dioxane and 40 pglml of 4-methyl-l,3-dioxane. 6.1.4 Calibrat
32、ion solution D Add approximately 40 ml of DMA (4.3) to a 50 ml volumetric flask (5.8). Weigh 1 O00 mg f 1 mg of 1,4-dioxane (4.1) and 400 mg f 1 mg of 4-methyl-l,3-dioxane (4.2). Make up to volume with DMA and thoroughly homogenize. Quantitatively dilute 0,5 ml of this solution to 100 ml with DMA. T
33、he final solution D contains 1 O0 pglml of 1,4-dioxane and 40 pg/ml of 4-methyl-l,3-dioxane. 6.1.5 Calibration solution E Add approximately 40 ml of DMA (4.3) to a 50 ml volumetric flask (5.8). Weigh 2 O00 mg f 1 mg of 1,4-dioxane (4.1) and 400 mg f 1 mg of 4-methyl-l,3-dioxane (4.2). Make up to vol
34、ume with DMA and thoroughly homogenize. Quantitatively dilute 0,5 ml of this solution to 100 ml with DMA. The final solution E contains 200 pg/ml of 1 ,4-dioxane and 40 pglml of 4-methyl-l,3-dioxane. OBSI 03-2000 STD-BSI BS EN 12974-ENGL 2000 m LbS4bL 0635303 T3b m Page 6 EN 12974: 1999 7 Sampling 7
35、.1 Preparation of the test sample Prepare and store the test sample in accordance with IS0 607. 7.2 Preparation of test sample solutions 7.2.1 internai standard procedure For test samples of known response factor and internal standard calibration factor as determined in 8.2, use the following proced
36、ure. Add 2 g f 0,Ol g of test sample (7.1) to a head space sample vial. Using the I ml gas tight syringe (5.9), add 1 ml i 0,Ol ml of calibration solution A (6.1.1). Seal immediately with septum and crimped top (5.5) and homogenize thoroughly by shaking vigorously. 7.2.2 Standard addition procedure
37、7.2.2.1 Add 2 g 10,Ol g of test sample (7.1) to each of three separate head space sample vials. For samples where the 1,4-dioxane content is expected to be less than 20 mg/kg, use the procedure described in 7.2.2.2. For samples expected to have a content of 1,4-dioxane from 20 mg/kg to 1 O0 mg/kg, u
38、se the procedure described in 7.2.2.3. 7.2.2.2 Using the 1 ml gas tight syringe (5.9), add the following to each of the three vials a) 1 ml f 0,Ol ml of calibration solution A (6.1.1) to the first vial. Seal immediately with septum and crimp top (5.5) and homogenize by shaking vigorously. b) 1 ml f
39、0,Ol ml of calibration solution B (6.1.2) to the second vial. Seal immediately with septum and crimped top (5.5) and homogenize thoroughly by shaking vigorously. This solution contains 10 mglkg of added 1,4-dioxane. c) 1 ml i 0,Ol ml of calibration solution C (6.1.3) to the third vial. Seal immediat
40、ely with septum and crimped top (5.5) and homogenize thoroughly by shaking vigorously. This solution contains 20 mg/kg of added 1,4-dioxane. 7.2.2.3 Using the 1 ml gas tight syringe (5.9), add the following to each of the three vials: a) 1 ml i: 0,Ol ml of calibration solution A (6.1 .I) to the firs
41、t vial. Seal immediately with septum and crimped top (5.5) and homogenize thoroughly by shaking vigorously. b) 1 mi f 0,Ol ml of calibration solution D (6.1.4) to the second vial. Seal immediately with septum and crimped top (5.5) and homogenize thoroughly by shaking vigorously. This solution contai
42、ns 50 mg/kg of added 1 ,4-dioxane. c) 1 ml f 0,Ol ml of calibration solution E (6.1.5) to the third vial. Seal immediately with septum and crimped top (5.5) and homogenize thoroughly by shaking vigorously. This solution contains 1 O0 mg/kg of added 1 ,Cdioxane. OBSI 03-2000 STD.BS1 BS EN 12974-ENGL
43、2000 lb24bb9 Ud35304 972 Page 7 EN 12974: 1999 8 Procedure 8.1 Chromatographic conditions The choice of chromatographic conditions depends on the apparatus in use and can be varied from those given below, provided that suitable separation of the compounds of interest is maintained. The following con
44、ditions have been found to be suitable for the column recommended in NOTE in 5.2: a) injection temperature 200 OC; b) column settings as follows: 1) initial temperature 60 OC held for 3 min; 2) initial program rate of 4 OClrnin to an intermediate temperature of 80 OC; 3) a final program rate of 30 O
45、C/min to a final temperature of 300 OC; and 4) maintain the final temperature for 5 min. c) carrier gas flow rate of 10 mllmin; and d) detector temperature 325 OC. The head space sampling conditions shall be optimized in accordance with the instrument suppliers recommendations. The test sample bath
46、temperature shall be 70 OC and the equilibrium time shall be 30 min. 8.2 Relative response factor Determine the 1 ,4-dioxane content of the test sample using the standard addition procedure according to 8.3.2. Calculate the result in milligrams per kilogram as specified in 10.2. Calculate the relati
47、ve response factor, Fd, from the following equation: Ai C, Fd=- Ad Ci where Ai is the area 4-methyl-I ,3-dioxane, in peak area units; Ad is the area 1,4-dioxane, in peak area units; cd is the content of ,4-dioxane in the sample, in milligrams per kilogram; Ci is the content of 4-methyl-I ,3-dioxane
48、in the sample, .e. 20 mg/kg. 8.3 Determination 8.3.1 Internal standard procedure Prepare a sample blend as specified in 7.2.1. Introduce the sample vial into the head space sampling unit (5.4) and analyze in accordance with the chromatographic conditions given in 8.1. A typical chromatogram is shown
49、 in Figure 1 OBSI 03-2000 Page 8 EN 12974: 1999 8.3.2 Standard addition procedure Prepare sample blends as specified in 7.2.2. Analyze each blend individually by introducing the sample vial into the head space sampling unit (5.4) and analyzing in accordance with the chromatographic conditions given in 8.1. A typical chromatogram is shown in Figure 1. 9 Evaluation of chromatograms Identify the components of the test sample by reference to Figure 1 Determine the area of the 1,4-dioxane peak and, if appropriate, the 4-rnethyl-l,3-dioxane peak using the dat
