Combustion

Ion Chromatography

Fast and reliable determination of halogens and sulfur

using pyrohydrolysis
 Combustion digestion and ion chromatography
combined in one system
Combustion Ion Chromatography (CIC) extends the range The principle
02 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 simul­taneous de­­ter­­mi­ mosphere in the oven unit and then burnt with oxygen
nation of the various halogens and sulfur in wi­­dely differ­ and 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 diges­
tion 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,
gaseous)
03
• Simultaneous determination of sulfur and halogens
• Quantification of the concentration for each halogen
• Ideal for checking the latest analytical standards with regard to halogen-free 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
04 Applications
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
chloride

1.6

4.5
140
4.0
Conductivity [µS/cm]

Conductivity [µS/cm]

120
3.5 0.8
sulfate

chloride

3.0 100

2.5 80
0.0
2.0
bromide

0 2 4 6 8 10 12 14
60 Time [min]

1.5
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 certified 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 Na2CO3, 1.0 mmol/L NaHCO3, 0.7 mL/min; column
temperature 30 °C; oven temperature 1050 °C; absorption solution: 100 mg/L H2O2

Metrohm CIC complies with international norms and standards like for example ...
ASTM D7359-14 Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and
Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatography
Detection (Combustion Ion Chromatography­CIC)
UOP991-13 Chloride, Fluoride, and Bromide in Liquid Organics by Combustion Ion Chromatography (CIC)
ASTM D5987-96 Standard Test Method for Total Fluorine in Coal and Coke by Pyrohydrolytic Extraction 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 diges­
tion 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. Dif­
combustion 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 com­ into 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 appro­ and can therefore be brought back into operation within
priate kit for liquid or solid samples, respectively, this a few minutes.
multi-matrix 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

both liquefied gases (LPG) and gaseous samples (GSS) –
MagIC Net controls the Gas Modules fully automatically.
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 lique­ being released prematurely. Following the sampling pro­
fied 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 volatil­
samples 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. More­ is 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 Com­ handle 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 determina­ line when changing bet­ween 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 ra­­pidly,
reliably, and – above all – automatically, using a single
multi-ion standard. This saves time and is less prone to
error.
Reliable
CIC is superior to offline digestion methods, not only
09
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, soot-free com­
bustion.

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 pre­
vents 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 Mo­­dule and

ion chromatograph are linked together by the 920 Ab­­
The following items are available for the entire liquid
handling: a 10-port valve, a 6-port injection valve and
sorber Module. The 920 Absorber Module ensures that two paten­ted 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 semi-
the input of water for combustion, matrix elimination of online sampler for direct absorption of gas compounds
the hydrogen peroxide (oxidizing agent), and rinsing pro­ (NH3, HNO2, HNO3, HCl, SO2) from the air. In this way, for
­cedures. example, volatile organic acids (hydrochloric acid, sulfuric
acid) can be monitored in process flue gases or in the
Moreover, a single multi-ion standard may be used for an am­­bient air at workplaces.
automated calibration of the system by means of the
Metrohm intelligent Partial Loop Injection Tech­nique
(MiPT). Because MiPT allows flexible injection vo­­lumes
(4–200 µL), a large concentration range can be cove­­red.

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 hand­ling
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 con­ into the absorption solution. Consequently, it is possible
trol func­­tions 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)
Layout by Ecknauer+Schoch ASW, printed in Switzerland by Metrohm AG, CH-9100 Herisau

6.7302.000 MMS 5000 Kit for solid samples

6.7303.000 MMS 5000 Kit for liquid samples

Columns
6.01032.420 Metrosep A Supp 17 - 150/4.0
6.01032.500 Metrosep A Supp 17 Guard/4.0

www.metrohm.com
8.000.5248EN – 2017-12
Subject to modifications