Combustion Ion Chromatography Fast and reliable determination of halogens and sulfur using pyrohydrolysis Combustion digestion and ion chromatography combined in one system 02 Combustion Ion Chromatography (CIC) extends the range The principle of ion chromatography to all types of combustible samples. In CIC the samples are first digested under an argon at ­ The focus here is primarily on the simul taneous de ter mimosphere in the oven unit and then burnt with oxygen nation of the various halogens and sulfur in wi dely differand water (Pyrohydrolysis). In the 920 Absorber Module, ing matrices. the resulting gaseous compounds are passed into an absorption solution, which is then transferred inline to a The Metrohm CIC System, including sample preparation, Metrohm ion chromatography system, where it is analyzed. is completely automated. CIC is superior to offline digestion methods with regard to sample throughput on the one hand and precision and correctness of the results on the other. With CIC, unlike with alternative methods, the concentrations of the different halogens can each be de termined separately. Schematic representation of a complete Combustion IC system Configuration with an 930 Compact IC Flex Oven/SeS/PP/Deg, a 920 Absorber Module and a Combustion Module from Analytik Jena equipped with solid autosampler The advantages of CIC at a glance • Extended range of application of IC for all kinds of combustible samples (solid, liquid, 03 gaseous) • Simultaneous determination of sulfur and halogens • Quantification of the concentration for each halogen • Ideal for checking the latest analytical standards with regard to halogen­free products (RoHS, WEEE ...) • High sample throughput, precision, and accuracy • MagIC Net ion chromatography software for control and data management – all information in one sample table or report • Flame sensor ensures optimum combustion time with an universal method • Compliance with FDA and GLP standards • Calibration with just one standard thanks to Metrohm intelligent Partial Loop Injection Technique (MiPT) • Fully automated sample preparation for solid and liquid samples with just one modular sample changer Applications 04 CIC is ideal for routine analysis in a variety of fields, as • environmentally relevant substances neither details about the nature of the sample matrix (oil, plastic waste, glass, activated carbon, ...) need to be known nor complicated method develop­ • electronic components ment is necessary. Not only is CIC recommended for (printed circuit boards, resin, cables, insulation, ...) quality control of raw materials, intermediates and fin­ • fuels ished products, but the method is also suitable for (gasoline, kerosene, crude oil, heating oil, coal, straigthforward and exact monitoring of compliance butane, propane, natural gas, catalysts, ...) with the relevant laws, standards and regulatory require­ • plastics ments in the environmental field (e.g. DIN EN 228, IEC (polymers such as polyethylene, polypropylene, ...) 60502­1, RoHS, WEEE, ...). • coloring agents (pigments, paints, ...) Examples of areas and products where analyses are pos­ • pharmaceutical products sible with CIC: (raw substances, intermediates, finished products, ...) • foods (oils, spices, flavorings and fragrances, ...) 5.5 180 sulfate 5.0 160 1.6 4.5 chloride 140 4.0 120 3.5 0.8 chloride 3.0 100 sulfate 2.5 80 2.0 0.0 60 0 2 4 6 8 10 12 14 Conductivity [µS/cm] Conductivity [µS/cm] Time [min] 1.5 bromide 40 1.0 chloride 0.5 20 0.0 0 0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20 Time [min] Time [min] Determination of halogens and sulfur in certifi ed polyethylene Determination of halogens and sulfur in coal reference material pellets ERM­EC681k: chloride: 102.4%, bromide 95.4%, sulfur NIST 2682b: chloride: 103.4%, sulfur 96.8%. Injection volume 100.3%. Injection volume 20 µL 100 µL Conditions (both analyses): Metrosep A Supp 5 ­ 150/4.0; eluent: 3.2 mmol/L Na CO , 1.0 mmol/L NaHCO , 0.7 mL/min; column 2 3 3 temperature 30 °C; oven temperature 1050 °C; absorption solution: 100 mg/L H O 2 2 Metrohm CIC complies with international norms and standards like for example ... ASTM D7359-14 Standard Test Method for Total Fluo rine, Chlorine and Sul fur in Aromatic Hydro carbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatography Detection (Combustion Ion Chroma to graphy­CIC) UOP991-13 Chloride, Fluoride, and Bromide in Liquid Or ganics by Com bustion Ion Chromato graphy (CIC) ASTM D5987-96 Standard Test Method for Total Fluorine in Coal and Coke by Pyrohydrolytic Ex traction and Ion Selective Electrode or Ion Chromatograph Methods ASTM D7994-17 Standard Test Method for Total Fluorine, Chlorine, and Sulfur in Liquid Petroleum Gas (LPG) by Oxidative Pyrohydrolytic Combustion Followed by Ion Chromatography Detection (Combustion Ion Chromatography­CIC) 05 A flame sensor measures the intensity of light in the Combustion Module and controls the combustion digestion automatically. Combustion digestion controlled automatically Metrohm’s CIC consists of a Combustion Module from plete (no soot formation), and, secondly, there is no need Analytik Jena and an absorption and IC part from for waiting times as a safety buffer. Metrohm. In the Combustion Module the sample digestion can be controlled automatically. The principle is Thanks to the automated control of sample digestion, simple. An optical fiber transfers the light emitted during method development for combustion is not needed. Difcombustion from the pyrolysis oven to an optical sensor. ferent samples as well as different sample quantities can The optical sensor measures the intensity of the light and be subjected to one and the same universal «method». If controls the feed rate of the sample boat into the oven norms have to be followed which define combustion for in proportion to it. Hence the duration of the combustion a specific time at a specific temperature, the sample inlet is optimized so that, firstly, combustion is always cominto the oven can also be programmed manually. CIC automation The MMS 5000 autosampler ensures fully automatic out much effort. The combustion system is unaffected introduction of solid and liquid samples. With the approand can therefore be brought back into operation within priate kit for liquid or solid samples, respectively, this a few minutes. multi­matrix sampler can be converted in minutes with­ CIC automation. Liquid or solid samples – the MMS 5000 autosampler can work with both. Reliable operation under high pressure: LPG/GSS Gas Module and LPG Module 06 The LPG/GSS Gas Module makes it possible to analyze MagIC Net controls the Gas Modules fully automatically. both liquefied gases (LPG) and gaseous samples (GSS) – A special dosing valve that uses Peltier cooling is used for such as natural gas – using Combustion IC. The LPG dosing liquefied gases, which prevents the sample from Module on the other hand allows the analysis of liquebeing released prematurely. Following the sampling profied gases, which however, may be subjected to much cess, the liquefied gas is vaporized in a heated chamber. higher pressures. The Dosing volume for all types of This enables even components that are less easily volatilsamples can be selected freely, something which even ized to be brought into a gaseous state. The sample is allows calibration of a wide concentration range without fully transferred to the combustion system, a process that the need for an additional calibration gas standard. Moreis also supported by a permanent flow of argon rinsing over the separate flow paths for LPG and GSS in the LPG/ gas. This prevents memory effects. GSS Gas Module eliminate any risk of contamination. 2.136.0720 2.136.0740 LPG/GSS Gas Module for LPG Module for analyzing gases in liquefied the analysis of LPG and gaseous states 07 Key parameters for gas analysis using Combustion IC LPG/GSS Gas Module LPG Module Sample cylinder pressure Max. 18 bar (260 psi) Max. 250 bar (3625 psi) Max. 31 bar (450 psi) Determined by sample 0.7–1.7 bar, typically Determined by sample Pressure at sample valve cylinder at 1 bar cylinder Sample volume 1–250 µL in 1 µL steps 1–65 mL in 250 µL steps 1–250 µL in 1 µL steps Temperature of 85 °C – 85 °C decompression chamber CIC at a glance 08 Highly flexible The MMS 5000 sample changer makes the system Straightforward operation highly flexible. The sample changer can be retrofitted to Once the sample table has been created, the Comhandle liquid samples instead of solid ones within two bustion IC system operates entirely automatically. All minutes – meaning that just one sample changer is parameters are controlled by MagIC Net software. The required. Moreover, there is no need to readjust the gas system is automatically switched off after a determinaline when changing bet ween different types of sample, tion series, which saves costs in cases where for example saving valuable time. expensive gases are being used. Straightforward calibration Thanks to the Metrohm intelligent Partial Loop Injection Technique (MiPT), calibration can be performed ra pidly, reliably, and – above all – automatically, using a single multi­ion standard. This saves time and is less prone to error. Reliable 09 CIC is superior to offline digestion methods, not only with respect to sample throughput, but also in terms of Flame sensor technology precision and trueness of the results. Check standards Whether solid or liquid samples are analyzed, or the for calibration and reference materials for the samples amount of sample varies, the flame sensor optimizes the also increase the reliability of CIC. combustion process. This ensures fast, soot­free combustion. No internal standard required MagIC Net documents all liquids that are dosed to the absorption solution. As a result, there is no need for an internal standard in the absorption solution. This prevents any undesirable dilution effects and also any interference between the internal standard and the analytes in the chromatogram. Perfect liquid handling – the 920 Absorber Module 10 In the Metrohm CIC System the Combustion Mo dule and The following items are available for the entire liquid ion chromatograph are linked together by the 920 Ab handling: a 10­port valve, a 6­port injection valve and sorber Module. The 920 Absorber Module ensures that two paten ted Metrohm 800 Dosino Dosing Units. the gaseous compounds of the analytes are brought into solution. The professional liquid handling also includes The 920 Absorber Module can also be used as a semithe input of water for combustion, matrix elimination of online sampler for direct absorption of gas compounds the hydrogen peroxide (oxidizing agent), and rinsing pro­ (NH , HNO , HNO , HCl, SO ) from the air. In this way, for 3 2 3 2 cedures. example, volatile organic acids (hydrochloric acid, sulfuric acid) can be monitored in process flue gases or in the Moreover, a single multi­ion standard may be used for an am bient air at workplaces. automated calibration of the system by means of the Metrohm intelligent Partial Loop Injection Tech nique (MiPT). Because MiPT allows flexible injection vo lumes (4–200 µL), a large concentration range can be cove red. 930 Compact IC Flex 920 Absorber Module Combustion Module Straighforward control with MagIC Net software The complete CIC system is controlled by MagIC Net, the MagIC Net guarantees easy, robust, and reliable hand ling proven software for ion chromatography. MagIC Net of of the system. The user is able at all times to keep an fers great flexibility with regard to configuration, layout overview of all the liquid quantities that are introduced and method programming. Several monitoring and coninto the absorption solution. Consequently, it is possible trol func tions are available to the user. MagIC Net meets to work without an internal standard or other tools. all FDA and GLP requirements and is also available in numerous languages. A modern data management system and a powerful report generator round off the package. Ordering information Metrohm markets the complete system, including installation, service and training − all from the same supplier. Instruments Combustion IC packages 2.930.9010 Metrohm Combustion IC PP. The package includes: 2.930.2560 Compact IC Flex Oven/SeS/PP/Deg 2.850.9010 IC Conductivity Detector 2.920.0010 Absorber Module 2.136.0700 Combustion Module (Oven and ABD) 6.2832.000 MSM Rotor A 6.2842.020 Adapter for Vario for MSM 6.6059.321 MagIC Net 3.2 Compact 6.1006.340 Metrosep A PCC 2 HC/4.0 2.930.9020 Metrohm Combustion IC DR. The package includes: 2.930.2460 Compact IC Flex Oven/SeS/Deg 2.850.9010 IC Conductivity Detector 2.920.0010 Absorber Module 2.136.0700 Combustion Module (Oven and ABD) 6.2832.000 MSM Rotor A 6.2842.020 Adapter for Vario for MSM 6.6059.321 MaglC Net 3.2 Compact 6.1006.340 Metrosep A PCC 2 HC/4.0 2.800.0020 800 Dosino 6.3032.120 Dosing Unit 2 mL 2.136.0700 Combustion Module (Oven and ABD) 2.136.0710 Auto Boat Drive (ABD) 2.136.0720 LPG/GSS Module (including coupling to ABD) 2.136.0730 Combustion Module (Oven and LPG/GSS, including direct coupling 6.7304.030 to oven) 2.136.0740 LPG Module (including coupling to ABD) 2.136.0750 Combustion Oven 6.7304.030 Direct coupling of LPG/GSS Module to oven Sample changers 2.136.0800 Autosampler MMS 5000 (sample rack not included) 6.7302.000 MMS 5000 Kit for solid samples 6.7303.000 MMS 5000 Kit for liquid samples ­9100 Herisau G, CH Columns ohm A 6.01032.420 Metrosep A Supp 17 ­ 150/4.0 6.01032.500 Metrosep A Supp 17 Guard/4.0 witzerland by Metr www.metrohm.com , printed in S SW ­12 Subject to modifications Layout by Ecknauer+Schoch A 8.000.5248EN – 2017