1、BSI Standards PublicationBS ISO 17280:2015Surface active agents Determination of 1,4-dioxanresidues in surfactantsobtained from epoxyethane bygas chromatographyBS ISO 17280:2015 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 17280:2015.The UK participation in
2、its preparation was entrusted to TechnicalCommittee CII/34, Methods of test for surface active agents.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are res
3、ponsible for its correctapplication. The British Standards Institution 2015. Published by BSI StandardsLimited 2015ISBN 978 0 580 76267 3ICS 71.100.40Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandard
4、s Policy and Strategy Committee on 30 June 2015.Amendments issued since publicationDate Text affectedBS ISO 17280:2015 ISO 2015Surface active agents Determination of 1,4-dioxan residues in surfactants obtained from epoxyethane by gas chromatographyAgents de surface Dtermination de la teneur en rsidu
5、s de 1,4-dioxane dans les agents tensioactifs obtenus partir dpoxythane par chromatographie en phase gazeuseINTERNATIONAL STANDARDISO17280First edition2015-05-15Reference numberISO 17280:2015(E)BS ISO 17280:2015ISO 17280:2015(E)ii ISO 2015 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2015, Pu
6、blished in SwitzerlandAll rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permi
7、ssion can be requested from either ISO at the address below or ISOs member body in the country of the requester.ISO copyright officeCh. de Blandonnet 8 CP 401CH-1214 Vernier, Geneva, SwitzerlandTel. +41 22 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgBS ISO 17280:2015ISO 17280:2015(E)Fore
8、word iv1 Scope . 12 Normative references 13 Principle 14 Reagents 14.1 1,4-Dioxane, purity 99,5 % minimum. 14.2 4-Methyl-1,3-dioxane, purity 98 % minimum. 14.3 N, N-dimethylformamide (DMF). 14.4 Carrier gas: nitrogen or helium, purity 99,99 % minimum. 25 Apparatus . 25.1 Analytical balance, 0,1 mg r
9、eadability. . 25.2 Gas chromatography system, attached with temperature programmed device and flame ionization detector (FID). . 25.3 Head space sampling unit 25.4 20 ml crimped top glass vials, sealing pliers and sealing clamp suitable for head space unit. . 25.5 Septum and crimped tops, lined with
10、 aluminium or PTFE, for closing the vials. 25.6 Sealing pliers, for the vials. . 25.7 Capillary column, capable of the separation characteristics shown in Figure 2. . 25.8 Volumetric flasks, 50 ml and 100 ml capacity. . 25.9 Gas tight syringes or glass pipettes, 1 ml 0,01 ml capacity. . 26 Preparati
11、on of calibration solutions . 26.1 Calibration solution A . 26.2 Calibration solution B . 37 Procedure. 37.1 Preparation of the test sample 37.2 Standard addition procedure . 37.2.1 Preparation of test sample solutions 37.2.2 Determination 47.2.3 Expression of results 47.3 Relative response factor p
12、rocedure 47.3.1 Determination of relative response factor . 47.3.2 Preparation of test sample solutions 57.3.3 Determination 57.3.4 Expression of results 58 Chromatographic conditions . 59 Evaluation 69.1 General . 69.2 Identification 79.3 Calculation 710 Precision . 710.1 Repeatability limit 710.2
13、Reproducibility limit 711 Test report . 7Annex A (informative) Statistical data from the ring carried out . 8 ISO 2015 All rights reserved iiiContents PageBS ISO 17280:2015ISO 17280:2015(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standard
14、s bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organiz
15、ations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.The procedures used to develop this document and those intended for its fur
16、ther maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directi
17、ves).Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the In
18、troduction and/or on the ISO list of patent declarations received (see www.iso.org/patents).Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement.For an explanation on the meaning of ISO specific terms and expressions related to
19、 conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT), see the following URL: Foreword Supplementary information .The committee responsible for this document is ISO/TC 91, Surface active agents.iv ISO 2015 All rights reserv
20、edBS ISO 17280:2015Surface active agents Determination of 1,4-dioxan residues in surfactants obtained from epoxyethane by gas chromatography1 ScopeThis International Standard provides a method for the determination of 1,4-dioxane residues in surfactants which are synthesized from epoxyethane, such a
21、s alkyl ether sulfates and alcohol ethoxylates.The method is applicable for samples containing 1,4-dioxane more than 5 mg/kg. For samples containing 1,4-dioxane more than 100 mg/kg, the sample solutions should be diluted to appropriate concentration.2 Normative referencesThe following documents, in
22、whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 607, Surface active agents and d
23、etergents Methods of sample divisionISO 3696, Water for analytical laboratory use Specification and test methodsISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement m
24、ethod3 PrincipleThe sample is weighed into a head space vial and a calibration solution is added. The sealed vial is placed in a head space sampling instrument and allowed to reach thermal equilibrium. A portion of the vapour phase is then analysed by temperature programmed GC with flame ionization
25、detection. Either an internal standard or standard addition method of quantification are employed.4 ReagentsDuring the analysis, use only reagents of recognized analytical grade and the water used shall conform to grade 3 in accordance with ISO 3696.4.1 1,4-Dioxane, purity 99,5 % minimum.4.2 4-Methy
26、l-1,3-dioxane, purity 98 % minimum.4.3 N, N-dimethylformamide (DMF).DMF may be substituted with other solvent. Applicability of the solvent should be evaluated by appropriate validation. Possible substitutes are including, but not limited to following: N, N-dimetylacetamide(DMA); Dimethyl sulfoxide
27、(DMSO); Diethyl formamide (DEF);INTERNATIONAL STANDARD ISO 17280:2015(E) ISO 2015 All rights reserved 1BS ISO 17280:2015ISO 17280:2015(E) Formamide.Diluent shall be free from peaks which interfere 1,4-dioxane and 4-methyl-1,3-dioxane.4.4 Carrier gas: nitrogen or helium, purity 99,99 % minimum.5 Appa
28、ratusOrdinary laboratory apparatus and the following.5.1 Analytical balance, 0,1 mg readability.5.2 Gas chromatography system, attached with temperature programmed device and flame ionization detector (FID).5.3 Head space sampling unit5.4 20 ml crimped top glass vials, sealing pliers and sealing cla
29、mp suitable for head space unit.5.5 Septum and crimped tops, lined with aluminium or PTFE, for closing the vials.5.6 Sealing pliers, for the vials.5.7 Capillary column, capable of the separation characteristics shown in Figure 2.NOTE A 30 m 0,32 mm (id) fused silica capillary column (film thickness:
30、 0,25 m) with nitroterephthalic acid modified polyethylene glycol stationary phase is advisable.5.8 Volumetric flasks, 50 ml and 100 ml capacity.5.9 Gas tight syringes or glass pipettes, 1 ml 0,01 ml capacity.6 Preparation of calibration solutions6.1 Calibration solution AAdd approximately 40 ml of
31、DMF (4.3) to a 50 ml volumetric flask. Weigh 0,2 g of 1,4-dioxane (4.1) to record the exact mass to obtain the accurate concentration in each calibration solution I. Make up to volume with DMF and thoroughly homogenize. The solution is A.Prepare each calibration solution I according to Table 1.Table
32、 1 preparation of calibration solutionsCalibration solution I I1I2I3I4I5Volume of the solution A/ml 0,0 0,5 1,0 2,5 5,0Make up to volume with DMF/ml 100 100 100 100 100The approximate concentration of 1,4-dioxanea/(g/ml)0 20 40 100 200aThe accurate concentration of 1,4-dioxane in each calibration so
33、lution I is obtained by the calculation with the mass of 1,4-dioxane.2 ISO 2015 All rights reservedBS ISO 17280:2015ISO 17280:2015(E)6.2 Calibration solution BThe calibration solution B which contains the calibration solution B1and the calibration solution B2is used to relative response factor proce
34、dure.a) Add approximately 40 ml of DMF to a 50 ml volumetric flask, weigh 0,4 g of 4-methyl-1,3-dioxane (4.2) to record the exact mass to obtain the accurate concentration in calibration solution C. Make up to volume with DMF and thoroughly homogenize. The solution is C.b) Add 0,5 ml 0,01 ml of this
35、 solution C and 1,0 ml 0,01 ml of solution A to a 100 ml volumetric flask, make up to volume with DMF and thoroughly homogenize. The solution is B1. The accurate concentration of 4-methyl-1,3-dioxane and 1,4-dioxane in the final solution B1is obtained by the calculation with the mass of 4-methyl-1,3
36、-dioxane and 1,4-dioxane.c) Add 0,5 ml 0,01 ml of this solution C to a 100 ml volumetric flask, make up to volume with DMF and thoroughly homogenize. The solution is B2. The accurate concentration of 4-methyl-1,3-dioxane in the final solution B2is obtained by the calculation with the mass of 4-methy
37、l-1,3-dioxane.7 Procedure7.1 Preparation of the test samplePrepare and store the test sample in accordance with ISO 607.7.2 Standard addition procedure7.2.1 Preparation of test sample solutions7.2.1.1 Add 2 g 0,01 g of test sample (7.1) to each of three separate head space sample vials. For samples
38、where the 1,4-dioxane content is expected to be less than 20 mg/kg, use the procedure described in 7.2.1.2. For samples expected to have a content of 1,4-dioxane from 20 mg/kg to 100 mg/kg, use the procedure described in 7.2.1.3.7.2.1.2 Using the 1ml gas tight syringe or glass pipette (5.9), add the
39、 following to each of the three vials:a) 1 ml 0,01 ml of calibration solution I1(6.1) to the first vial. Seal immediately with septum and crimped top (5.5) and homogenize by shaking vigorously.b) 1 ml 0,01 ml of calibration solution I2(6.1) to the second vial. Seal immediately with septum and crimpe
40、d top (5.5) and homogenize by shaking vigorously. The added amount of 1,4-dioxane relative to the test sample content is approximate 10 mg/kg.c) 1 ml 0,01 ml of Calibration solution I3(6.1) to the third vial. Seal immediately with septum and crimped top (5.5) and homogenize by shaking vigorously. Th
41、e added amount of 1,4-dioxane relative to the test sample content is approximate 20 mg/kg.7.2.1.3 Using the 1 ml gas tight syringe or glass pipette (5.9), add the following to each of the three vials:a) 1 ml 0,01 ml of calibration solution I1(6.1) to the first vial. Seal immediately with septum and
42、crimped top (5.5) and homogenize by shaking vigorously.b) 1 ml 0,01 ml of calibration solution I4(6.1) to the second vial. Seal immediately with septum and crimped top (5.5) and homogenize by shaking vigorously. The added amount of 1,4-dioxane relative to the test sample content is approximate 50 mg
43、/kg.c) 1 ml 0,01 ml of Calibration solution I5(6.1) to the third vial. Seal immediately with septum and crimped top (5.5) and homogenize by shaking vigorously. The added amount of 1,4-dioxane relative to the test sample content is approximate 100 mg/kg. ISO 2015 All rights reserved 3BS ISO 17280:201
44、5ISO 17280:2015(E)7.2.2 DeterminationAnalyse each blend as prepared in 7.2.1 by introducing the sample vial into the head space sampling unit (5.4) and analysing in accordance with the chromatographic conditions given in Clause 8.7.2.3 Expression of resultsConstruct a graph of peak area (y-axis) ver
45、sus content (x-axis) for the1,4-dioxane component. Extrapolate the line to the point where it intercepts the x-axis (see Figure 1). This intersection is the 1,4-dioxane content of the sample, c1, expressed as milligrams per kilogram., ,Figure 1 Example of a peak area versus concentration graph for t
46、he standard addition procedureNOTE When calculating the results in accordance with the standard addition procedure, the relative coefficient r should be above 0,995. Or else, prepare the new solutions and determine again. If necessary, add 12 determination points.7.3 Relative response factor procedu
47、re7.3.1 Determination of relative response factorAdd 2 g 0,01 g of sample to a head space sample vial. Using the 1 mL gas tight syringe or glass pipette (5.9), add 1,0 mL 0,01 mL of calibration solution B16.2, b) to determinate related response factor. Seal immediately with septum and crimped top (5
48、.5) and homogenize thoroughly by shaking vigorously.Note The sample in this procedure is the same matrix as the test sample, which does not contain1,4-dioxane or contains 1,4-dioxane with known concentration, to ensure the consistency of the gas-liquid equilibrium in the sample vial.4 ISO 2015 All r
49、ights reservedBS ISO 17280:2015ISO 17280:2015(E)Calculate the relative response factor k from the following Formula (1):kAcAcsi=21(1)wherek is relative response factor;Asis the area of 1,4-dioxane, in peak area units;Aiis the area of 4-methyl-1,3-dioxane, in peak area units;c1is the 1,4-dioxane content in test sample (7.1), in milligrams per kilogram;c2is the 4-methyl-1,3-dioxane content in the sample (i.e. 20 mg/kg), in milligrams per kilogram.7.3.2 Preparation of test sample solutionsAdd 2 g
