/home/gencode/cen/s12139/en1213 1 27738 | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | |[.]
BRITISH STANDARD Surface active agents Ð Determination of the total polyethylene glycol content of non-ionic surface active agents (EO adducts) by HPLC/GPC The European Standard EN 12139:1999 has the status of a British Standard ICS 71.100.40 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | BS EN 12139:1999 Confirmed June 2009 BS EN 12139:1999 National foreword This British Standard is the English language version of EN 12139:1999 The UK participation in its preparation was entrusted to Technical Committee CII/34, Methods of test for surface active agents, which has the responsibility to: Ð aid enquirers to understand the text; Ð present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; Ð monitor related international and European developments and promulgate them in the UK A list of organizations represented on this committee can be obtained on request to its secretary 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 ªInternational Standards Correspondence Indexº, or by using the ªFindº facility of the BSI Standards Electronic Catalogue A British Standard does not purport to include all the necessary provisions of a contract Users of British Standards are responsible for their correct application Compliance with a British Standard does not of itself confer immunity from legal obligations Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages to 10, an inside back cover and a back cover This British Standard, having been prepared under the direction of the Sector Committee for Materials and Chemicals, was published under the authority of the Standards Committee and comes into effect on 15 June 1999 BSI 06-1999 ISBN 580 32268 Amendments issued since publication Amd No Date Comments EN 12139 EUROPEAN STANDARD NORME EUROPÊENNE EUROPẰISCHE NORM February 1999 ICS 71.100.40 Descriptors: surfactants, non-ionic surfactants, chemical analysis, determination of content, polyethylene, glycol, condensates, chromatography, high performance liquid chromatography English version Surface active agents Ð Determination of the total polyethylene glycol content of non-ionic surface active agents (EO adducts) by HPLC/GPC Agents de surface Ð DeÂtermination de la teneur totale en polyeÂthyleÁne glycol des agents de surface non ioniques (condensats OE) par CLHP/CPG GrenzflaÈchenaktive Stoffe Ð Bestimmung des Gesamtgehaltes an Polyethylenglycol von nichtionischen grenzflaÈchenaktiven Stoffen (EO-Addukten) mit HPLC/GPC This European Standard was approved by CEN on 25 January 1999 CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration Up-to-date lists and bibliographical references concerning 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 translation under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the 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, Switzerland and United Kingdom CEN European Committee for Standardization Comite EuropeÂen de Normalisation EuropaÈisches Komitee fuÈr Normung Central Secretariat: rue de Stassart 36, B-1050 Brussels 1999 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members Ref No EN 12139:1999 E Page EN 12139:1999 Foreword This European Standard has been prepared by Technical Committee CEN/TC 276, Surface active agents, the Secretariat of 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 August 1999, and conflicting national standards shall be withdrawn at the latest by August 1999 Annexes A, B, C and D are informative According to the CEN/CENELEC Internal 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, Switzerland and the United Kingdom BSI 06-1999 Page EN 12139:1999 Scope Reagents and materials This European Standard specifies a method for the determination of the total polyethylene glycol (PEG) content of aromatic and aliphatic non-ionic surface active agents of the type R2(O2C2H4)p2OH, where p is the mean ethylene oxide (EO) value It applies for concentrations of PEG higher than approximately 0,1 g/100 g of the laboratory sample The method is applicable up to a degree of ethoxylation of at least 25 for products which are soluble in an 80/20 (V/V) mixture of methanol and water Long-chain products with a low degree of ethoxylation, such as tallow alcohol1) EO, are not soluble, and require an amended preliminary treatment During the analysis, unless otherwise stated, use only reagents specified in ISO 6353-2:1983 and ISO 6353-3:1987 if listed there, if not, reagents of recognized analytical grade Normative references This European Standard incorporates by dated or undated reference, provisions from other publications These normative references are cited at the appropriate places 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 referred to applies EN ISO 3696, Water for analytical laboratory use Ð Specification and test methods (ISO 3696:1987) ISO 607:1980, Surface active agents and detergents Ð Methods of sample division ISO 6353-2:1983, Reagents for chemical analysis Ð Part 2: Specifications Ð First series ISO 6353-3:1987, Reagents for chemical analysis Ð Part 3: Specifications Ð Second series Principle Polyethylene glycol is separated from its monoalkyl ethers by a reverse phase chromatography column The use of an additional gel chromatography column (GPC) enables the determination of the molecular mass distribution of the polyethylene glycols in the surface active agent raw material by comparison with PEG calibration PEG standards Small amounts of low carboxylic acids, which are often used in industrial processes to neutralize the ethoxylation catalyst, and which interfere with the determination, are removed together with long-chain alkyl polyglycol ethers by means of a special cartridge method This eliminates potential interference factors and decreases the analysis times 4.1 Methanol, HPLC grade 4.2 Deionized water, filtered, conforming to the requirements of grade in EN ISO 3696 4.3 Polyethylene glycol 800, GPC grade 4.4 Analytical grade anion exchange resin, 100 mesh to 200 mesh, chloride form, total capacity 3,5 milliequivalents/g dry resin 4.5 Reversed phase C18, silica gel, bulk material, particle diameter about 40 mm to 60 mm 4.6 Sodium hydroxide solution, c(NaOH) = mol/l 4.7 Nitric acid, c(HNO3) = mol/l 4.8 Silver nitrate solution, c(AgNO3) = mol/l 4.9 Mobile phase, either a) 80/20 (V/V) mixture of methanol/water for samples of the type alkylphenol (e.g i-nonyl phenol EO) or fatty alcohols (e.g C12/C14 EO) with a low degree of ethoxylation; or b) 75/25 (V/V) mixture of methanol/water for samples of the type of alkylphenol (e.g i-octyl phenol 25 EO) or fatty alcohols (e.g C12/C14 25 EO) with a high degree of ethoxylation Apparatus Ordinary laboratory apparatus and the following 5.1 Isocratic HPLC unit, with refractive index detector and column oven 5.2 Data systems, with reintegration facilities for the chromatograms 5.3 Sample preparation unit, for solid phase extraction, such as a vacuum chamber 5.4 Disposable syringes, 10 ml 5.5 One-mark volumetric flasks, 10 ml and 50 ml 5.6 One-mark pipette, ml 5.7 Piston-type graduated pipette, 10 ml 5.8 Preparative glass chromatography column 5.9 Special cartridge, prepared as follows Convert the ion exchanger (4.4) from chloride to hydroxide form by filling a chromatography column with it and washing it with sodium hydroxide solution (4.6) until no more chloride ions are detected Wash the exchanger with water and remove from the column NOTE The absence of chloride is confirmed when the eluant does not form a precipitate with nitric acid/silver nitrate solution 1) CAS Registry Number 99561-04-3 BSI 06-1999 Page EN 12139:1999 Remove the plunger from a 10 ml disposable syringe (5.4), place some cotton wool in the barrel and press down firmly into the end of the barrel with a rod Add the reversed phase C18 silica gel (4.5) up to the 10 ml mark (4,0 g to 4,5 g) Place some cotton wool above the added reversed phase C18 silica gel, press down firmly with the rod, and set the cartridge on the sample preparation unit (5.3) Apply a vacuum and pour the exchanger suspension into the cartridge until about cm is present (see Figure B.1) Wash the cartridge by filling it three times with ml methanol, then three times with the mobile phase to be used (4.9) Carry out this washing sequence shortly before the sample is added (see clause 6) to prevent the exchanger drying and cracking 5.10 Chromatography columns Prepare two chromatography columns as follows: a) one column, 250 mm long and mm internal diameter, containing reversed phase C18 silica gel, mm; b) one GPC column for aqueous applications, 300 mm long and 7,8 mm internal diameter containing a stationary phase of pore size 120 1024 mm, exclusion limit (PEO) 103 g/mol Convert the GPC column for methanol/water using a gradient from % methanol to 80 % methanol over a period of h Sampling and preparation of the test sample The laboratory sample shall be prepared and stored in accordance with 5.3 of ISO 607 Prepare a sample stock solution by weighing g of the laboratory sample to the nearest 0,1 mg, into a 50 ml volumetric flask (5.5) and making up to the mark with the mobile phase (4.9) Place the solution in an ultrasonic bath until it has dissolved completely Prepare a test sample by placing a 10 ml volumetric flask in the sample preparation unit (5.3) so that the cannula of the special cartridge (5.9) ends in the neck of the flask Using one marked pipette, add ml of the sample stock solution to the special cartridge (5.9) When the sample stock solution has been adsorbed in the cartridge, rinse twice with ml mobile phase (4.9) NOTE These solvent quantities should be used to ensure efficiency of the cartridge Remove the 10 ml volumetric flask from the sample preparation unit and allow it to return to room temperature Fill to the mark with the mobile phase to be used and transfer it to the automatic sampling vessels or use for direct injection Procedure 7.1 Apparatus settings Connect the chromatography columns in series [first: C18 silica gel column (5.10a); second: GPC column (5.10b)] Set the HPLC unit to the following: Detector: Flow rate: Temperature: Injection volume: RI 1,0 ml/min Column 30 8C 100 ml 7.2 Calibration 7.2.1 Preparation of calibration solutions Prepare five calibration solutions using the standard of polyethylene glycol 800 (PEG 800) (4.3) as follows Weigh, to the nearest 0,1 mg, five levels of PEG 800 between 15 mg to 80 mg of the PEG (e.g 15 mg, 25 mg, 40 mg, 60 mg and 80 mg) into separate 50 ml volumetric flasks and fill to the mark with the mobile phase to be used (4.9) Ensure that the solutions are properly dissolved 7.2.2 Calibration curve Analyse each calibration solution, prepared in 7.2.1, at least twice using the chromatographic conditions given in 7.1 Construct a graph of peak area against PEG mass in calibration solutions and draw a calibration curve 7.3 Determination of polyethylene glycol content Carry out at least two analyses on the test sample solution as prepared in clause 6, using the chromatographic conditions given in 7.1 NOTE Evaluation of the chromatograms is carried out automatically with the help of the available data system by means of the external standard method Under some circumstances reintegration can be necessary Analysis times are considerably longer if the sample preparation is not carried out as described in clause Examples of chromatograms are given in annex C Expression of results Use the calibration curve 7.2.2 to obtain the PEG mass corresponding to the area given by the integrator Express the PEG content in percentage by mass as follows: m 100 % PEG = m0 where m0 m is the mass of sample to be analysed (see clause 6) in grams; is the mass of PEG in the sample determined from the calibration curve (see 7.2.1) in grams BSI 06-1999 Page EN 12139:1999 Precision 9.1 Repeatability The repeatability conditions are conditions where mutually independent test results are obtained with the same method on identical test material in the same laboratory by the same operator using the same equipment within short intervals of time The absolute difference between two single test results obtained under repeatability conditions shall not be greater than: Ð 0,12 g/100 g laboratory sample at a level of 0,67 % PEG (see annex A, sample 1); Ð 0,27 g/100 g laboratory sample at a level of 1,19 % PEG (see annex A, sample 2) NOTE In order to take into account the value of the repeatability standard deviation determined from the ring test for low quantities (in sample 1), the result should be calculated as the mean of five determinations to two decimal digits BSI 06-1999 9.2 Reproducibility The reproducibility conditions are conditions where test results are obtained with the same method on identical test material in different laboratories with different operators using different equipment The absolute difference between two single test results obtained under reproducibility conditions shall not be greater than: Ð 0,66 g/100 g laboratory sample at a level of 0,67 % PEG (see annex A, sample 1); Ð 0,45 g/100 g laboratory sample at a level of 1,19 % PEG (see annex A, sample 2) 10 Test report The test report shall include at least the following particulars: a) all information necessary for complete identification of the sample; b) a reference to this European Standard; c) the result; d) details of any operation not specified in this European Standard, and any operation regarded as optional as well as any incidents likely to have affected the results Page EN 12139:1999 Annex A (informative) Ring-test 407-1-92 Table A.2 Ð Sample (alkylphenol-ethoxylate) (Statistical evaluation of 407-7-90 resp.407-2-90) The precision data were determined from a ring test involving eight laboratories and samples with two different polyethylene glycol contents Table A.1 Ð Sample (long-chain alcohol-ethoxylate) Laboratory Mean value m % (m/m) 0,55 0,70 1,24 0,57 0,73 0,48 0,63 Standard deviation s % (m/m) 0,007 0,056 0,076 0,013 0,058 0,012 0,030 Number of collaborative laboratories: Number of laboratories considered for the evaluation: Total number of values (without outliers): Mean value (m): Repeatability standard deviation (sr): Repeatability r (= 2,8 sr): Variation coefficient of repeatability s vr = r 100: m Reproducibility standard deviation (sR): Reproducibility R (= 2,8 sR): Variation coefficient of reproducibility s vR = R 100: m Variation coefficient n % 1,3 8,0 6,1 2,3 7,9 2,5 4,8 29 0,67 % (m/m) 0,044 % (m/m) 0,123 % (m/m) Laboratory Mean value m % (m/m) 1,11 1,11 1,17 1,31 1,03 1,37 1,36 Standard deviation s % (m/m) 0,035 0,147 0,062 0,082 0,056 0,115 0,021 Number of collaborative laboratories: Number of laboratories considered for the evaluation: Total number of values (without outliers): Mean value (m): Repeatability standard deviation (sr): Repeatability r (= 2,8 sr): Variation coefficient of repeatability s vr = r 100: m Reproducibility standard deviation (sR): Reproducibility R (= 2,8 sR): Variation coefficient of reproducibility s vR = R 100: m Variation coefficient n % 3,2 13,2 5,3 6,3 5,4 8,4 1,5 31 1,19 % (m/m) 0,097 % (m/m) 0,271 % (m/m) 8,2 % 0,159 % (m/m) 0,446 % (m/m) 13,4 % 6,6 % 0,235 % (m/m) 0,658 % (m/m) 35,1 % BSI 06-1999 Page EN 12139:1999 Annex B (informative) Structure of the special cartridge Key Anion exchange resin Reversed phase C18 silica gel, bulk material 40 mm to 63 mm 4,0 g to 4,5 g Disposable syringe Cotton wool Figure B.1 Ð Structure of the cartridge BSI 06-1999 Page EN 12139:1999 Annex C (informative) Examples of chromatograms Key Solvent Without cartridge With cartridge Figure C.1 Ð Chromatograms given by long-chain-ethoxylate BSI 06-1999 Page EN 12139:1999 Key Solvent Without cartridge With cartridge Figure C.2 Ð Chromatograms given by alkylphenol-ethoxylate BSI 06-1999 Page 10 EN 12139:1999 Annex D (informative) Bibliography [1] TURNER L.P., MCCULLOUGH D., JACKOWITZ A (Alcolac Inc.) Journal of the American Oil Chemists Society 53 (1976), 691 [2] HENKE H (Enka AG) Tenside Detergents 15 (1978), BSI 06-1999 blank BSI 389 Chiswick High Road London W4 4AL | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | BSI Ð British Standards Institution BSI is the independent national body responsible for preparing British Standards It presents the UK view on standards in Europe and at the international level It is incorporated by Royal Charter Revisions British Standards are updated by amendment or revision Users of British Standards should make sure that they possess the latest amendments or editions It is the constant aim of BSI to improve the quality of our products and services We would be grateful if anyone finding an inaccuracy or ambiguity while using this British Standard would inform the Secretary of the technical committee responsible, the identity of which can be found on the inside front cover Tel: 020 8996 9000 Fax: 020 8996 7400 BSI offers members an individual updating service called PLUS which ensures that subscribers automatically receive the latest editions of standards Buying standards Orders for all BSI, international and foreign standards publications should be addressed to Customer Services Tel: 020 8996 9001 Fax: 020 8996 7001 In response to orders for international standards, it is BSI policy to supply the BSI implementation of those that have been published as British Standards, unless otherwise requested Information on standards BSI provides a wide range of information on national, European and international standards through its Library and its Technical Help to Exporters Service Various BSI electronic information services are also available which give details on all its products and services Contact the Information Centre Tel: 020 8996 7111 Fax: 020 8996 7048 Subscribing members of BSI are kept up to date with standards developments and receive substantial discounts on the purchase price of standards For details of these and other benefits contact Membership Administration Tel: 020 8996 7002 Fax: 020 8996 7001 Copyright Copyright subsists in all BSI publications BSI also holds the copyright, in the UK, of the publications of the international standardization bodies Except as permitted under the Copyright, Designs and Patents Act 1988 no extract may be reproduced, stored in a retrieval system or transmitted in any form or by any means ± electronic, photocopying, recording or otherwise ± without prior written permission from BSI This does not preclude the free use, in the course of implementing the standard, of necessary details such as symbols, and size, type or grade designations If these details are to be used for any other purpose than implementation then the prior written permission of BSI must be obtained If permission is granted, the terms may include royalty payments or a licensing agreement Details and advice can be obtained from the Copyright Manager Tel: 020 8996 7070