1、BSI Standards PublicationBS ISO 17293-1:2014Surface active agents Determination of chloroaceticacid (chloroacetate) insurfactantsPart 1: HPLC methodBS ISO 17293-1:2014 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 17293-1:2014.The UK participation in its prep
2、aration 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 responsible
3、 for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 76268 0ICS 71.100.40Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy
4、 and Strategy Committee on 31 March 2014.Amendments issued since publicationDate Text affectedBS ISO 17293-1:2014 ISO 2014Surface active agents Determination of chloroacetic acid (chloroacetate) in surfactants Part 1: HPLC methodAgents de surface Dtermination de lacide chloroactique (chloroactate) d
5、ans les agents tensioactifs Partie 1: Mthode CLHPINTERNATIONAL STANDARDISO17293-1First edition2014-04-01Reference numberISO 17293-1:2014(E)BS ISO 17293-1:2014ISO 17293-1:2014(E)ii ISO 2014 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2014All rights reserved. Unless otherwise specified, no par
6、t 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. Permission can be requested from either ISO at the address below or ISOs member bo
7、dy in the country of the requester.ISO copyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandBS ISO 17293-1:2014ISO 17293-1:2014(E) ISO 2014 All rights reserved iiiContents PageForeword iv1 Scope . 12
8、 Normative references 13 Principle 14 Reagents 14.1 General . 15 Apparatus . 26 Procedures 26.1 HPLC conditions . 26.2 Calibration 36.3 Sampling and analysis 37 Results and calculation 37.1 General . 37.2 The content of monochloroacetic acid . 47.3 The content of dichloroacetic acid . 48 Precision .
9、 48.1 Repeatability limit 48.2 Reproducibility limit 49 Test report . 4Annex A (informative) Preliminary treatment of betaine sample . 6Annex B (informative) Typical chromatogram 8BS ISO 17293-1:2014ISO 17293-1:2014(E)ForewordISO (the International Organization for Standardization) is a worldwide fe
10、deration of national standards 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 com
11、mittee. International organizations, 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 a
12、nd those intended for its further 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, Pa
13、rt 2 (see www.iso.org/directives). 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
14、the document will be in the Introduction 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 t
15、erms and expressions related to 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 informationThe committee responsible for this document is ISO/TC 91, Surface active agents
16、.ISO 17293 consists of the following parts, under the general title Surface active agents Determination of chloroacetic acid (chloroacetate) in surfactants: Part 1: HPLC method Part 2: Ionic chromatographic methodiv ISO 2014 All rights reservedBS ISO 17293-1:2014INTERNATIONAL STANDARD ISO 17293-1:20
17、14(E)Surface active agents Determination of chloroacetic acid (chloroacetate) in surfactants Part 1: HPLC method1 ScopeThis part of ISO 17293 specifies a method for the determination of monochloroacetic acid (monochloroacetate) and dichloroacetic acid (dichloroacetate) in surfactants by HPLC method.
18、The method applies for anionic surfactants such as alkyl (phenyl) ethoxylated carboxylate (AEC) or amphoteric surfactants such as alkyl imidazoline carboxylate, alkyl dimethyl betaine, and fatty acetyl propyl dimethyl betaine.The limit of detection (LOD) is 0,3 g/ml for monochloroacetic acid and 0,2
19、 g/ml for dichloroacetic acid; the limit of quantification (LOQ) is 1,0 g/ml for monochloroacetic acid and 0,75 g/ml for dichloroacetic acid (using a standard solution).The LOD, at 5 g of sample weight, is 6 mg/kg for monochloroacetic acid and 4 mg/kg for dichloroacetic acid; and the LOQ is 20 mg/kg
20、 for monochloroacetic acid and 15 mg/kg for dichloroacetic acid.2 Normative referencesThe following documents, in 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
21、 latest edition of the referenced document (including any amendments) applies.ISO 607, Surface active agents and detergents Methods of sample divisionISO 3696, Water for analytical laboratory use Specification and test methodsISO 5725-2, Accuracy (trueness and precision) of measurement methods and r
22、esults Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method3 PrincipleThe sample is dissolved in the mobile phase in order to analyse by high performance liquid chromatography (HPLC). After injection, it flows through a C8-bonded silicone g
23、el column. The monochloroacetic acid (monochloroacetate) and dichloroacetic acid (dichloroacetate) are separated in the column and detected by an UV detector.The contents of monochloroacetic acid and dichloroacetic acid in the sample are achieved by external calibration method.4 Reagents4.1 GeneralD
24、uring the analysis, use only reagents of recognized analytical grade and the water used shall conform to grade 1 in accordance with ISO 3696, unless otherwise specified. ISO 2014 All rights reserved 1BS ISO 17293-1:2014ISO 17293-1:2014(E)4.2 Monochloroacetic acid (ClCH2COOH), purity 99 % (w/w).4.3 D
25、ichloroacetic acid (Cl2CHCOOH), purity 99 % (w/w).4.4 Acetonitrile (CH3CN) HPLC grade, filtered before use with filter unit (5.7).4.5 Phosphoric acid (H3PO4).4.6 Hydrochloric acid (HCl).4.7 Hydrochloric acid solution, 1:1 (V/V).Add to about 10 ml of hydrochloric acid (4.6) and 10 ml of water in port
26、ions. Mix well.5 ApparatusUse usual laboratory apparatus and, in particular, the following.5.1 HPLC instrument, equipped with pump and a high-resolution UV detector or photodiode array detector, with the noise and the drift of baseline at 254 nm 2 105AU/s (blank cell) and at 254 nm 1 103AU/h (blank
27、cell, after stabilizing for 60 min), respectively.5.2 HPLC column: C8-bonded phase silicone gel (particle size 5 m), 250 mm 4,6 mm (ID), pH range from 1 to 8, or equivalent.5.3 Filter syringe, of capacity 2 ml or 5 ml.5.4 Injection syringe, of capacity 25 l.5.5 Analytical balance, accurate to 0,1 mg
28、.5.6 Ultrasonic device, for the degassing of reagents.5.7 Filters with suitable porosity (0,2 m or 0,45 m), for the filtration of reagents and sample.5.8 Vacuum pump.5.9 pH meter, for pH measurement.5.10 Volumetric flasks, of capacity 50 ml and 100 ml.5.11 Glass beakers, of capacity 50 ml and 100 ml
29、.6 Procedures6.1 HPLC conditionsThe choice of HPLC 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 conditions have been found to be suitable for the HPLC column recommende
30、d in 5.2.6.1.1 Mobile phase: Add 100 ml of acetonitrile (4.4) in 900 ml of water, then pipette 2,0 ml of phosphoric acid (4.5) and mix well. Before using, the mobile phase should be degassed with an ultrasonic device (5.6).6.1.2 Flow rate: 1,0 ml/min.6.1.3 Detecting wavelength: 214 nm.6.1.4 Column t
31、emperature: room temperature.2 ISO 2014 All rights reservedBS ISO 17293-1:2014ISO 17293-1:2014(E)6.1.5 Injection volume: 20 l.Based on the above conditions, a typical chromatogram is shown in Figure B.1 in Annex B.6.2 Calibrationa) Weigh 0,1 g of monochloroacetic acid (4.2) and 0,1 g of dichloroacet
32、ic acid (4.3), accurate to 0,1 mg, in a 50 ml beaker, add approximately 20 ml of mobile phase (6.1.1) to it, and then stir to thoroughly dissolve. Transfer quantitatively to a 100 ml volumetric flask, make up to the mark with mobile phase, and completely homogenize.Store this solution in a refrigera
33、tor at (4 2) C and renew it every 7 d.Quantitatively dilute 0,1ml, 0,5 ml, 1,0 ml, 1,5 ml, and 2,5 ml of this solution to 100 ml with mobile phase (6.1.1), respectively. These standards shall be freshly prepared before analysis.b) Filter (5.7) the diluted solutions and inject 20 l to the HLPC for an
34、alysis. The analysis shall be done at least twice in accordance with the chromatographic conditions given in 6.1. The obtained linear correlation coefficient (R) shall be 0,999 or above.6.3 Sampling and analysisPrepare and store the test sample in accordance with ISO 607.Add approximately 5 g of tes
35、t sample, accurate to 0,1 mg, in 30 ml of mobile phase (6.1.1), and stir until the sample is dissolved completely. Measure the pH with a pH meter (5.9). Adjust the pH to the same as that of the mobile phase with HCl solution (4.7). Quantitatively dilute the sample to 100 ml with mobile phase (6.1.1)
36、. Filter (5.7) it and inject 20 l of the diluted solution for analysis on the chromatographic conditions given in 6.1.NOTE If interference to the peak of monochloroacetic acid or dichloroacetic acid in the betaine chromatogram was found during the test of the betaine sample, prepare the sample solut
37、ion in accordance with the method in Annex A, using a cation-exchange column to remove the interference. After preliminary treatment, this solution shall be filtered (5.7) and injected 20 l for analysis on the chromatographic conditions given in 6.1.7 Results and calculation7.1 GeneralDetermine the
38、monochloroacetic acid and dichloroacetic acid contents in the test sample using the procedure according to 6.3. Calculate the results in milligrams per kilogram (mg/kg) according to Formula (1) and Formula (2). ISO 2014 All rights reserved 3BS ISO 17293-1:2014ISO 17293-1:2014(E)7.2 The content of mo
39、nochloroacetic acidThe content of monochloroacetic acid in the test sample is calculated using Formula (1):XAVm1mg kg/()=(1)whereX1is the content of monochloroacetic acid, in mg/kg;A is the calculated concentration of monochloroacetic acid in the test sample solution, in g/ml;V is the volume of the
40、test sample, in ml;m is the mass of the test sample, in g.7.3 The content of dichloroacetic acidThe content of dichloroacetic acid in the test sample is calculated using Formula (2):XBVm2mg kg/()=(2)whereX2is the content of dichloroacetic acid, in mg/kg;B is the calculated concentration of dichloroa
41、cetic acid in the test sample solution, in g/ml.8 Precision8.1 Repeatability limitThe absolute difference between two independent single test results, obtained using the same method on identical test materials in the same laboratory by the same operator using the same equipment within a short interv
42、al of time, shall not exceed the repeatability limit (r) in more than 5 % of cases.According to ISO 5725-2, r can be expected to be 10 % for contents greater than or equal to 50 mg/kg, and 15 % for contents less than 50 mg/kg.8.2 Reproducibility limitThe absolute difference between two single test r
43、esults, obtained using the same method on identical test materials in different laboratories by different operators using different equipment, shall not exceed the reproducibility limit (R) in more than 5 % of cases. R can be expected to be 40 %.9 Test reportThe test report shall contain at least th
44、e following information:a) the test method used, with reference to this part of ISO 17293 (i.e. ISO 17293-1);b) all information necessary for the complete identification of the test compound;4 ISO 2014 All rights reservedBS ISO 17293-1:2014ISO 17293-1:2014(E)c) all the data (e.g. in tabular form) ob
45、tained and the calibration curve;d) all operating details not specified in this part of ISO 17293, or regarded as optional, together with details of any incidents which might have influenced the test result(s). ISO 2014 All rights reserved 5BS ISO 17293-1:2014ISO 17293-1:2014(E)Annex A (informative)
46、 Preliminary treatment of betaine sampleA.1 ReagentsDuring the analysis, use only reagents of recognized analytical grade, and the water used shall conform to grade 3 in accordance with ISO 3696, unless otherwise specified.A.1.1 Cation exchanger (KAT), strongly acidic, 50 to 100 mesh.A.1.2 Hydrochlo
47、ric acid, 4 mol/l solution.Add 700 ml of hydrochloric acid to 1 400 ml of water; mix well.A.1.3 Acetonitrile (CH3CN): HPLC grade.A.1.4 Acetonitrile solution, 10% (V/V).Add 30 ml of acetonitrile (A.1.3) to 270 ml of water; mix well.A.2 ApparatusA.2.1 Volumetric flask, of capacity 100 ml.A.2.2 Glass b
48、eakers, of capacity 200 ml and 3 000 ml.A.2.3 Glass exchange column with tap, for resin preparation: inner tube 50 mm to 60 mm in diameter and 550 mm to 600 mm in height.A.2.4 Glass exchange column with tap, for sample analysis: inner tube 15 mm in diameter and 400 mm in height.A.3 ProcedureA.3.1 Pr
49、eparation of cation-exchange resinPlace 600 ml of cation-exchange resin (A.1.1) in a 3 000 ml beaker (A.2.2) and cover by adding 2 000 ml of hydrochloric acid (A.1.2). Allow to stand for at least 2 h, with occasional stirring. Decant the acid and transfer the resin into the preparation column (A.2.3) by means of deionized water.The column should contain a glass-wool plug. Wash the column with water until the eluate is free of chloride.A.3.2 Cation-exchange columnPlace 60 ml of cation-exchange resi
