EN 13268:2001

Surface active agents - Determination of ethylene oxide and propylene oxide groups in ethylene oxide and propylene oxide adducts

This European Standard specifies a method for the qualitative and quantitative determination of ethylene oxide and propylene oxide groups in ethylene oxide (EO) and propylene oxide (PO) adducts, polyethers and polyglycol esters.
NOTE   If a suitable calibration is performed, methoxy groups can also be determined.

Grenzflächenaktive Stoffe - Bestimmung von Ethylenoxid- und Propylenoxid-Gruppen in Ethylenoxid- und Propylenoxid-Addukten

Diese Europäische Norm legt ein Verfahren für den Nachweis und die Bestimmung von Ethylenoxid- und Propylenoxidgruppen in Ethylenoxid (EO)- und Propylenoxid (PO)-Addukten, Polyethern und Polyglycolestern fest.
ANMERKUNG   Bei geeigneter Kalibrierung können auch Methoxygruppen bestimmt werden.

Agents de surface - Détermination de la teneur en oxyde d'éthylène et en oxyde de propylène dans les condensats à base d'oxyde d'éthylène et d'oxyde de propylène

1 Domaine d'application
La présente norme européenne spécifie une méthode de détermination qualitative et quantitative des groupements d'oxyde d'éthylène et d'oxyde de propylène dans les condensats à base d'oxyde d'éthylène (OE) et d'oxyde propylène (OP), les polyéthers et les esters polyglycoliques.
NOTE   Lorsque l'étalonnage est approprié, les groupements méthoxy peuvent également être déterminés.

Povšinsko aktivne snovi - Določevanje etilen oksidnih in propilen oksidnih skupin v etilen oksidnih in propilen oksidnih kondenzatih

General Information

• Status: Published
• Publication Date: 03-Apr-2001
• Withdrawal Date: 30-Oct-2001
• ICS: 71.100.40 - Surface active agents
• Technical Committee: CEN/TC 276 - Surface active agents
• Drafting Committee: CEN/TC 276/WG 1 - Methods of analysis
• Current Stage: 9092 - Decision on results of review/2YR ENQ - revise - Review Enquiry
• Start Date: 10-Nov-2006
• Completion Date: 10-Nov-2006
• Ref Project: SIST EN 13268:2002 - Surface active agents - Determination of ethylene oxide and propylene oxide groups in ethylene oxide and propylene oxide adducts

Relations

• Corrected By: EN 13268:2001/AC:2002 - Surface active agents - Determination of ethylene oxide and propylene oxide groups in ethylene oxide and propylene oxide adducts
• Effective Date: 22-Dec-2008

Overview

EN 13268:2001 - Surface active agents - Determination of ethylene oxide and propylene oxide groups in ethylene oxide and propylene oxide adducts - is a CEN method for the qualitative and quantitative analysis of EO (ethylene oxide) and PO (propylene oxide) groups in EO/PO adducts, polyethers and polyglycol esters. The procedure converts EO/PO groups into alkyl iodides by hydroiodic cleavage, extracts them into nonane and quantifies them by gas chromatography (GC) using an internal standard.

Keywords: EN 13268:2001, surface active agents, ethylene oxide, propylene oxide, EO/PO adducts, gas chromatography, hydroiodic cleavage.

Key topics and technical requirements

• Scope: Determines content of EO and PO groups; methoxy groups can be determined if suitable calibration is performed.
• Principle: Hydroiodic acid reacts with ethoxy and propoxy groups to form ethyl iodide (stoichiometric) and propyl iodide (partial yield). Alkyl iodides are extracted into nonane and analyzed by GC.
• Reagents & materials: HI (approx. 6.7 %), adipic acid, nonane (GC grade), toluene internal standard, pure ethyl/isopropyl/propyl iodide for calibration.
• Sample preparation: ~50 mg sample, add adipic acid, HI and internal standard in a pressure-resistant digestion vial; heat at 150 ± 5 °C (or 130 °C if shaken) for the prescribed time, then cool and separate phases.
• Chromatography: GC with on-column injector and FID or TCD; specified capillary column type and temperature program are provided (alternative instrument/conditions allowed if comparable separation achieved).
• Calibration & calculation: Use internal standard method to compute relative response factors from pure alkyl iodides. Apply equations in the standard to convert measured alkyl iodide mass to EO/PO percent; a correction factor (1.33) accounts for incomplete transformation of PO groups.
• Precision: Repeatability and reproducibility are reported from ring tests (examples in Annex A). For instance, EO repeatability limits for example samples ranged up to ~11% (absolute) for some matrices, and reproducibility up to ~13% - reporting depends on sample type and matrix.

Applications and users

• Practical applications:
  • Quality control of nonionic surfactants, EO/PO adducts, polyethers and polyglycol esters.
  • Verification of degree of ethoxylation/propoxylation in raw materials and finished formulations.
  • Regulatory compliance and material specification testing in chemical and detergent manufacturing.
• Who uses it:
  • Analytical chemists in surfactant and specialty chemical labs.
  • QC/QA teams in detergents, personal care, and polymer industries.
  • Test laboratories providing certified analysis of EO/PO content.

Related standards

• EN ISO 3696 (water for analytical use)
• ISO 607 (sample division for surfactants/detergents)
• ISO 5725-2 (precision - repeatability and reproducibility)

EN 13268:2001 provides a standardized GC-based method to reliably quantify EO and PO group content in surface-active materials, supporting consistent quality control and comparative testing across laboratories.

Standards Content (Sample)

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Grenzflächenaktive Stoffe - Bestimmung von Ethylenoxid- und Propylenoxid-Gruppen in Ethylenoxid- und Propylenoxid-AdduktenAgents de surface - Détermination de la teneur en oxyde d'éthylene et en oxyde de propylene dans les condensats a base d'oxyde d'éthylene et d'oxyde de propyleneSurface active agents - Determination of ethylene oxide and propylene oxide groups in ethylene oxide and propylene oxide adducts71.100.40Površinsko aktivna sredstvaSurface active agentsICS:Ta slovenski standard je istoveten z:EN 13268:2001SIST EN 13268:2002en01-januar-2002SIST EN 13268:2002SLOVENSKI
STANDARD
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 13268April 2001ICS 71.100.40English versionSurface active agents - Determination of ethylene oxide andpropylene oxide groups in ethylene oxide and propylene oxideadductsAgents de surface - Détermination de la teneur en oxyded'éthylène et en oxyde de propylène dans les condensats àbase d'oxyde d'éthylène et d'oxyde de propylèneGrenzflächenaktive Stoffe - Bestimmung von Ethylenoxid-und Propylenoxid-Gruppen in Ethylenoxid- undPropylenoxid-AdduktenThis European Standard was approved by CEN on 19 January 2001.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Management Centre or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Management Centre has the same status as the officialversions.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.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2001 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 13268:2001 ESIST EN 13268:2002

Page 2EN 13268:2001ContentsPageForeword.3Introduction.41Scope.52Normative references.53Principle.54Reagents.55Apparatus.66Sampling and preparation of the test sample.67Procedure.78Expression of results.89Precision.910Test report.10Annex A (informative)
Ring test results (CESIO/AISE Ring test 408-1-92).11Bibliography.15SIST EN 13268:2002

Page 3EN 13268:2001ForewordThis European Standard has been prepared by Technical Committee CEN/TC 276 "Surface active agents", thesecretariat 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 orby endorsement, at the latest by October 2001, and conflicting national standards shall be withdrawn at the latestby October 2001.Annex A is informative.According to the CEN/CENELEC Internal Regulations, the national standards organizations of the followingcountries 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.SIST EN 13268:2002

Page 4EN 13268:2001IntroductionUnder the specified reaction conditions, ethylene oxide groups convert stoichiometrically into ethyl iodide.However, the conversion of propylene oxide groups to isopropyl iodide is not stoichiometric.SIST EN 13268:2002

Page 5EN 13268:20011 ScopeThis European Standard specifies a method for the qualitative and quantitative determination of ethylene oxide andpropylene oxide groups in ethylene oxide (EO) and propylene oxide (PO) adducts, polyethers and polyglycolesters.NOTEIf a suitable calibration is performed, methoxy groups can also be determined.2 Normative referencesThis European Standard incorporates by dated or undated reference, provisions from other publications. Thesenormative references are cited at the appropriate places in the text and the publications are listed hereafter. Fordated references, subsequent amendments to or revisions of any of these publications apply to this EuropeanStandard only when incorporated in it by amendment or revision. For undated references the latest edition of thepublication referred to applies (including amendments).EN ISO 3696, Water for analytical laboratory use – Specification and test methods (ISO 3696:1987). ISO 607, Surface active agents and detergents – Methods of sample divisionISO 5725-2, Accuracy (trueness and precision) of measurement methods and results – Part 2 : Basic method forthe determination of repeatability and reproducibility of a standard measurement method.3 PrincipleHydroiodic acid and nonane are added to the sample to be analysed and the mixture is heated in a closed vesselfor 1 h at 150 °C. Upon conversion, ethylene oxide groups form stoichiometric amounts of ethyl iodide, andpropylene oxide groups form (74 % to 77 % (m/m)) of propyl iodide (mainly the iso-form, less frequently the n-form).These compounds are extracted by the nonane present and thus removed from the reaction medium.Under the specified digestion conditions, ethyl iodide is formed from all compounds containing ethoxy groups(ethers and esters) and ethylene glycol derivatives; and isopropyl iodide is formed from all compounds containingisopropoxy groups, propylene glycol and glycerol derivatives.The alkyl iodides are determined directly from the nonane solution by means of gas chromatography using tolueneas internal standard.Substances that contain isobutyl groups give isobutyl iodide when cleavage takes place. Isobutyl iodide cannot beexactly separated from the internal standard, toluene, in the chromatogram.4 ReagentsDuring the analysis, use only reagents of recognized analytical grade and water complying with grade 3 as definedin EN ISO 3696.4.1Hydroiodic acid, HI, w(HI)
6,7 %.4.2Adipic acid, C8H6O4, w(C8H6O4)
98 %.4.3Toluene, C7H8, w(C7H8)
99 %.4.4Nonane, C9H20, wC9H20)
99 %, GC quality.SIST EN 13268:2002

Page 6EN 13268:20014.5Ethyl iodide, C2H5I, w(C2H5I)
99 %, GC quality.4.6Propyl iodide, C3H7I, w(C3H7I)
98 %.4.7Isopropyl iodide, C3H7I, w(C3H7I)
98 %.4.8Internal standard solution. Fill a 1000 ml volumetric flask with about 200 ml nonane (4.4). Addapproximately 2 g of toluene (4.3), weighed to nearest 0,01 g. Fill the flask up to the mark with nonane.4.92-phenoxyethanol, C8H10O2, w(C8H10O2)
98 %.4.101,2-propanediol, C3H8O2, w(C3H8O2)
99 %.5 ApparatusOrdinary laboratory apparatus and the following:5.1Metal heating block, thermostatically controlled, to fit the pressure resistant digestion vial (5.2), capable ofmaintaining a temperature of (150 ± 5) °C, or drying cupboard, capable of maintaining a temperature of(150 ± 5) °C.5.2Pressure resistant
digestion vial for hydroiodic cleavage, for example as shown in Figure 1, with a screwtop lined with a rubber septum onto which a protective polytetrafluorethylene foil is glued.5.3Syringes, with capacities of 1 µl and 50 µl.5.4Gas chromatograph, equipped with on-column injector and flame ionization detector (FID) or thermalconductivity
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