ACCREDITATION ISO17025 Calibration level

1. ACCREDITATION ISO17025Calibration level Quality in Calibration Mixtures P.Boermans Maastricht February 2002 www.praxair.com Praxair and the Flowing Airstream design are trademarks or registered trademarks of Praxair Technology, Inc in the United States and/or other countries Other trademarks used herein are trademarks of their respective owners

2. Application of Calibration Mixtures • Crucial role in the Calibration of Lab- and Proces analytical Equipment used in: • Chemical - Petrochemical Industries • Refineries • Natural Gas Processors • Environmental applications: • Stack Emission • Ambient Air control • Personal protection • Workplace and Safety Monitoring

3. Application of Calibration Mixtures • High versatility of requirements in these applications: • Multicomponents in different hydrocarbon matrices for QC of raw material (propylene,ethylene,…..) • Process control of cracker fractions • LEL mixtures for explosimeters • Multi-emission (NO-CO-CO2-SO2 in N2) • Volatile Organics • Benzene, HCl, HF, HCN, NH3, ……..

4. Quality of Calibration Mixtures • Enduser expects despite this versatility in components and concentrations: • Reliable (low) uncertainty in certification • Consistent quality • (Long term) Stability • Traceability of the certification result……for his specific application

5. Quality of Calibration Mixtures • Quality fullfillment in function of this versatility in needs : • Quality systems under ISO 9000 / QS 9000 • Specific acceptance protocols between producer <--> enduser • ISO17025 accreditation at calibration level ….. Driven by

6. Quality of Calibration Mixtures • Legislation • Capabilities of (inter)national Metrology Institutes or Labs (NMI, LNE, NPL, NIST,…) • Quality Systems at endusers (ISO 9000, ISO17025 Testing level,…..)

7. Calibration Mixtures: Quality under ISO 9000 • Typical for the Chemical and Petrochemical Industries: • Large variety in compositions • Concentration ranges from low ppm to high % • Critical Processes like f.e.: • Monitoring of Product Quality • Monitoring of Proces Safety • Explosion risk control

8. Preparation of Calibration Mixtures:CertifiedStandard • Filling on basis of weight,volume(@21°C,1 atm) or partial pressure • Specific filling manifolds for:- Hydrocarbons,CO,CO2,H2,... - Inerts - Nox, HCl, SO2, H2S, NH3, HF COCl2 - Liquids • Calibrated weights,volumes and manometers • ISO 9002 follow up system of measuring tools - calibrationfrequency and uncertainty level

9. Certified Standard:Certification method • Reference Standards • Volumetrical (ISO 6144) • Gravimetrical (ISO 6142 NBN T97-101 VDI 3490) • External Standards (NMI - NIST -, …….) • Calibration method • Comparison method (ISO 6143) • Certificate of Analysis • Conform ISO 6141

10. Certified Standard:Certification method • ISO 6143 • dCx/Cx < Ö(dCe/Ce)2+(dYe/Ye)2+(dYx/Yx)2dCx/Cx rel.error on [Cx] in the sample dCe/Ce rel.error on [Ce] in reference material dYe(x)/Ye(x) rel.error outputsignal sample & reference • dYe(x) = Sy x t / Ön Sy standard deviation analytical result tStudent-Fisher for 2σ probability n number of analytical results

11. Traceability: Certified Standard External Standard Mass ISO 6142 Primary Standard Preparation of Calibration Mixtures (W V P) Internal Management Reference Standards Stock of Primary Standards Analytical validation External Reference Standards ISO 6143 Other Certified Reference Standards ISO 6144 ISO 6141 Certification ISO 6145 25/2/99/mb

12. Calibration Mixtures:Quality under Acceptance Protocol • Example: Synthetic Natural Gas • Low uncertainties required • Determination of composition for Wobbe index calculation of the Natural gas stream • Traceability to an accredited level (EN45000 / ISO 17025 calibration level) • NMI • EffecTech

13. High Accuracy Gravimetric Standard:Gravimetrical Preparation • Analytical balance (100 kg capacity - 10 mg sensitivity) • Identification and follow up of all uncertainties in the filling process • Uncertainty calculation accordong Guideline EAL-R2 • Filling Procedures according ISO 6142

14. Operational Weights OIML Class 2 Resolution 105 - 107 Checkups: Linearity Reproductibility Sensitivity Quality Components with known impurities Validation (analytical) Error sources Buoyancy P,T,humidity Molar mass Cylinder expansion Effects on fill lines Stability Chemical stability of the components Cylinder choice High Accuracy Gravimetric Standard: Preparation Method: ISO 6142

15. High Accuracy Gravimetric Standard: Traceability Aspects • Traceability (ISO,OIML,BIPM) is the characteristic of a measuring result to be related to an unbroken chain of national and international standards,each with their respective uncertainties • Direct relation to mass • Calibrated reference weights (BKO - NMI) • Controlled conditions of P and T (climatisation) • Operational procedures (ISO 9002) and follow up of measuring tools • Filling- and control procedures according ISO 6142 • Error calculation (EAL-R2) • Analytical Validation Protocol with traceability to recognised Metrological level (NMI, Effectech / NPL)

16. High Accuracy Gravimetric Standard: Certification method Considering all error sources , their uncertainties and the acceptance criteria of the Analytical Protocol [MOL]A = MRA / AN Mf [MOL]A Molar fraction of component A MRA Number of mol A (real purity) AN Mf Total number of mol of all components incluve their impurities

17. Traceability: Gravimetric Standard ISO 6142 Quality Control pure products Certified Standard Calculation and iteration of filling weights External Standard Mass Internal and/or external Reference Standard Filling on Voland (ISO 6142) Analytical Quality Control (ISO 6143) Validation Protocol Example for Synthetic Natural Gas Certification Error calculation (ISO 6141en ISO 6142) 16/10/00 Rev 1

18. Calibration Mixtures:Quality under EN 45000 (Calibration level) • Accreditation: What is it ?? • Protection of consumers by certification of products and manufacturing under certified qualitysystems,checked and audited by accreditation bodies • Accreditation bodies are under the umbrella of EA (European Accreditation) and can demonstrate that they operate an accreditation system compatible with EN 45003 or ISO/IEC Guide 58 • EA members signed multilateral agreements (see Publication reference EA-01/08)

19. Accreditation Equivalencies: Example for Benelux - France - Germany

20. Calibration Mixtures:Quality under EN 45000 (Calibration level) • Environmental Monitoring Applications • Labs operating under EN 45000 Testing level • Basis for uniformity in analytical results • Highest quality and traceability level (“End product”)EXTERNAL AUDIT HIGH ACCURACY ANALYTICAL GRAVIMETRIC VALIDATION PROCES PROCES METROLOGICALTRACEABILITY

21. Accreditation ISO17025 in Oevel by the BKO • Project approved mid 1999 • Dossier sent to BKO March 2000 • Preaudit November 2000 • Corrective measures + adaption dossier • Final audit July 2001 • Final corrections • Approved September 2001 • Official signature of Ministery end October 2001 • Official Certificate end November 2001 • First scope extention in 2003 • Major re-audit in Q4 2004 • Second scope extention planned for Q4 2005

22. Accreditation Scope

23. Thanks for your attention ! Questions ???