1、BRITISH STANDARD BS EN 14667:2005 Surface active agents Determination of low boiling solvents in liquid formulations Gas chromatographic method The European Standard EN 14667:2005 has the status of a British Standard ICS 71.100.40 BS EN 14667:2005 This British Standard was published under the author
2、ity of the Standards Policy and Strategy Committee on 11 July 2005 BSI 11 July 2005 ISBN 0 580 46361 3 National foreword This British Standard is the official English language version of EN 14667:2005. The UK participation in its preparation was entrusted to Technical Committee CII/34, Methods of te
3、st for surface active agents, which has the responsibility to: 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
4、 the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. Users are responsib
5、le for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the U
6、K interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 9 and a back cover. The BSI copyright notice displayed in this document indicates
7、when the document was last issued. Amendments issued since publication Amd. No. Date CommentsEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 14667 June 2005 ICS 71.100.40 English version Surface active agents - Determination of low boiling solvents in liquid formulations - Gas chromatographic m
8、ethod Agents de surface - Dtermination des solvants faible point dbullition dans les formulations liquides - Mthode par chromatographie en phase gazeuse Grenzflchenaktive Stoffe - Bestimmung des Gehaltes an leichtsiedenden Lsemitteln in flssigen Formulierungen - Gaschromatographisches Verfahren This
9、 European Standard was approved by CEN on 19 May 2005. 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
10、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
11、 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, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxe
12、mbourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels 2005 CEN All rights of
13、exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 14667:2005: EEN 14667:2005 (E) 2 Contents Page Foreword 3 1 Scope .4 2 Normative references .4 3 Terms and definitions.4 4 Principle.4 5 Reagents4 6 Apparatus 4 7 Sampling and preparation of the sample
14、 5 8 Procedure 5 9 Calculation and expression of results.6 10 Precision6 11 Test report .7 Annex A (informative) Typical gas chromatogram.8 Annex B (informative) Results of inter-laboratory test 9EN 14667:2005 (E) 3 Foreword This European Standard (EN 14667:2005) has been prepared by Technical Commi
15、ttee 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 December 2005, and conflicting national standards shall be withd
16、rawn at the latest by December 2005. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary
17、, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 14667:2005 (E) 4 1 Scope This European Standard specifies a method for the determination of the content of low boiling solvent
18、s, e.g. methanol, ethanol propan-1-ol and propan-2-ol in liquid detergents. Typically only one solvent is present in these kinds of samples. The method is applicable to liquid detergents containing low boiling solvents in the range from 0,5 % to 10 % by weight. 2 Normative references The following r
19、eferenced documents are indispensable for the application of this document. 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 detergents Methods of sample
20、division. 3 Terms and definitions For the purposes of this European Standard, the following terms and definitions apply. low boiling solvent alcohol with a boiling point below 100 C NOTE For example ethanol, propan-1-ol and propan-2-ol. 4 Principle The liquid detergent is dissolved in butan-1-ol, wh
21、ich is a water miscible solvent with higher boiling point than the solvents to be determined. The content of low boiling solvents is determined with gas chromatography. 5 Reagents During the analysis, unless otherwise specified, use only reagents of recognized analytical grade that have been checked
22、 in advance as to not interfere with the analytical results. 5.1 Ethanol, purity 99,5 % (m/m) 5.2 Propan-1-ol, purity 99,5 % (m/m). 5.3 Propan-2-ol, purity 99,5 % (m/m). 5.4 Butan-1-ol, purity 99,5 % (m/m). 5.5 Carrier gas, nitrogen or helium for gas chromatography. 5.6 Auxiliary gases, for gas chro
23、matography. 6 Apparatus Normal laboratory apparatus and the following: EN 14667:2005 (E) 5 6.1 Gas chromatograph, suitable for work with a fused silica capillary column and equipped with a split injector and a flame ionization detector (FID). 6.2 Capillary column, capable of the separation character
24、istics shown in Figure A.1. NOTE A 30 m x 0,53 mm ID, fused silica capillary column (film thickness 0,25 m) with 5 % phenyl-, 95 % methyl polysiloxane stationary phase is advisable. 6.3 Electronic integrator 6.4 Ultrasonic bath 6.5 Membrane filter, 0,45 m pore size. 7 Sampling and preparation of the
25、 sample The laboratory sample shall be taken and stored in accordance with ISO 607. 8 Procedure 8.1 Calibration Weigh to the nearest 0,1 mg approximately 40 mg of each solvent standard (5.1, 5.2 and respectively 5.3) each into a 10 ml volumetric flask and make up to volume with butan-1-ol (5.4) (cal
26、ibration solutions A1, B1 and respectively C1). Weigh to the nearest 0,1 mg approximately 20 mg of each solvent standard (5.1, 5.2 and respectively 5.3) each into a 10 ml volumetric flask and make up to volume with butan-1-ol (5.4) (calibration solutions A2, B2 and respectively C2). Pipette 1ml of e
27、ach calibration solution A1, B1 respectively C1 each into a 5 ml volumetric flask and make up to volume with butan-1-ol (5.4) (calibration solutions A3, B3 and respectively C3). Calculate the concentration of each standard solution in milligrams per 10 ml. Pipette 1ml of each calibration solution A2
28、, B2 respectively C2 each into a 5 ml volumetric flask and make up to volume with butan-1-ol (5.4) (calibration solution A4, B4 respectively C4). Calculate the concentration of each standard solution in milligrams per 10 ml. Transfer each solution into an autosampler vial and inject 1 l of each into
29、 the gas chromatograph. At least the quality of separation shown in Figure A.1 shall be achieved. NOTE Manual injection is also suitable. Record the peak areas and calculate the calibration curve for each solvent, using linear regression (least square) and without forced origin. 8.2 Determination We
30、igh to the nearest 0,1 mg approximately 400 mg of the liquid detergent into a 10 ml volumetric flask and make up to volume with butan-1-ol (5.4). Treat the solution in an ultrasonic bath (6.4) if necessary and filter through a membrane filter (6.5) if undissolved particles remain in the solution. Fi
31、ll an autosampler vial with the sample solution and inject 1 l into the gas chromatograph. At least the quality of separation shown in Figure A.1 shall be achieved. NOTE 1 Manual injection is also suitable. EN 14667:2005 (E) 6 Record the peak areas of the peaks of interest. Peak assignment is made b
32、y comparison of the retention times of the sample peaks with the retention times of the reference peaks. NOTE 2 In cases where peak assignment is not clear, the solvent of interest should be added to the sample solution and then the gas chromatography should be repeated. 9 Calculation and expression
33、 of results The content of the low boiling solvent i, w i , expressed in grams per 100 g is calculated according to the following equation: m a b A w i i i i 100 = (1) where A iis the peak area of the low boiling solvent i in the sample in counts; b iis the axis intercept of the calibration curve of
34、 the solvent i in counts; a iis the slope of the calibration curve of solvent i in counts/milligrams per10 ml; m is the mass of the sample, in milligrams. 10 Precision 10.1 Repeatability limit The absolute difference between two independent single test results, obtained using the same method on iden
35、tical test material in the same laboratory by the same operator and using the same equipment within a short interval of time will not exceed the repeatability limit, r, in more than 5 % of cases. Precision data are given in Annex B. 10.2 Reproducibility limit The absolute difference between two inde
36、pendent single test results, obtained using the same method on identical test material in different laboratories by different operators using different equipment will not exceed the reproducibility limit, R, in more than 5 % of cases. Precision data are given in Annex B. EN 14667:2005 (E) 7 11 Test
37、report The test report shall include the following information: a) all information necessary for the complete identification of the sample; b) method used (a reference to this document); c) test results; d) details of any operations not specified in this document or in the European standards to whic
38、h reference is made, and any operations regarded as optional, as well as any incidents likely to have affected the results. EN 14667:2005 (E) 8 Annex A (informative) Typical gas chromatogram Key 1 Methanol 4 Time, in minutes 2 Ethanol 5 Response, in millivolts 3 Propan-2-ol Figure A.1 Typical gas ch
39、romatogram The following GC conditions have been found to be suitable: Column Head-pressure: 115 kPa; Split ratio: 1:50; Injection temperature: 200 C; Temperature programme: 30 C for 4 min, then to 120 C at 10 C/min, then to 280 C at 40 C/min Detector temperature: 280 C; Injection volume : 1 l. EN 1
40、4667:2005 (E) 9 Annex B (informative) Results of inter-laboratory test The inter-laboratory test was carried out in 2002 by CESIO/AISE WG “Surfactant Analysis“. Test sample 1 was a commercial softener formulation. Test sample 2 was a commercial dish washing liquid. The analyses were done using eithe
41、r automatic or manual injection into the gas chromatograph. The results of the inter-laboratory test were evaluated in accordance with ISO 5725-2. Table B1 Results of inter-laboratory test Designation Propan-2-ol determination Ethanol determination (sample 1) (sample 2) Number of laboratories partic
42、ipating 12 12 Number of laboratories not eliminated 10 10 Number of individual test results of all laboratories 36 36 Mean value, m, in g/100 g 1,17 3,09 Repeatability standard deviation, s r, in g/100 g 0,025 0,074 Repeatability limit, r (s r 2,8), in g/100 g 0,07 0,21 Variation coefficient of repe
43、atabilityin % 2,16 2,40 Reproducibility standard deviation, s R, in g/100 g 0,091 0,132 Reproducibility limit, R (s R 2,8), in g/100 g 0,25 0,37 Variation coefficient of reproducibility, in % 7,75 4,27 NOTE Two laboratories were eliminated, because they did not follow the calibration procedure as it
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