Determination of Halogens and

Sulphur in Complex Matrices

Daniel Hemmler1, S. Kaufmann2, Christian Emmenegger3, Dirk Schmitz3, and
Alfred Steinbach3, 1Aalen University, Aalen, Germany, 2Analytik Jena AG, Jena, Germany,
3Metrohm International Headquarters, Herisau, Switzerland.

This article presents a method that combines combustion digestion and ion
chromatography into a single analysis (combustion ion chromatography
[CIC]) making it possible to detect halogens and sulphur in complex matrices.
The method is suitable for use in a wide range of application areas.
There are a number of different methods CIC Method Principles
available to determine fuorine, chlorine, Combustion: Combustion takes place
bromine, iodine, and sulphur in fammable in the presence of steam, which ensures
substances. The majority of these are based that the gaseous halogen and sulphur
on independent analysis steps, beginning compounds (HX, X 2, SOx) are quantitatively
with sample digestion using high-temperature collected by the absorption solution. Adding
combustion followed by halogen and sulphur hydrogen peroxide to the absorption
analysis. As an alternative, combustion digestion solution (for example, 90 mg/L) ensures that
coupled with ion chromatography (CIC) all sulphur compounds are present in the
combines sample digestion and analysis in one form of sulphate, which is necessary for ion
step. CIC can be performed on a wide range of chromatographic detection. However, when
sample types regardless of whether solid, liquid, hydrogen peroxide is added as an oxidizing
or gas. The only condition is that the sample agent it can result in various interference
has to be fammable. In addition to the halogen peaks that overlay the fuoride peak. With
and sulphur analysis processes discussed in this in-line matrix elimination, these interferences
article, which are used in the plastics, power disappear and the fuoride peak can be
generation, petroleum, and fuel industries, evaluated again (Figure 1).
CIC is also suitable for samples from the An optical sensor in the pyrolysis oven
Photo Credit: Martin Diebel/Getty Images

pharmaceutical, environmental, and food sector.
It is for these advantages that many international
standards refer to CIC when determining the
presence of halogens and sulphur in complex
matrices (Table 1).
indicates the progression of the combustion
and regulates the feed of the sample boat.
This ensures complete combustion by
similarly reducing the sample’s oven
dwell time.

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Figure 1: Effect of 90 mg/L hydrogen peroxide in the absorption solution. Red: once with
in-line matrix elimination; Black: once without.

0.97
0.96
0.95
0.94
DOWNLOAD
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LCGC E-Book Educational
Conductivity (µS/cm)

0.91 Series: Advances in

0.90 Ion Chromatography
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0.88 This exclusive e-book assembles the top experts in
ion chromatography from across the world to provide
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0.84 KEY TOPICS INCLUDE:
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0 1 2 3 4 5 6 7 8
» Advances in detection for IC
Time (min) » Best practices in
sample preparation
» Tools for simulation and
optimization of IC separations
Table 1: A selection of international standards that recommend combustion ion chromatography
as a means of determining the halogen and sulphur content in fammable samples. » High-speed and high-
resolution methods
Combustion IC in international standards » Perspectives from Hamish
Small, the inventor of ion
Standard test method for total fluorine, chlorine and sulphur in aromatic chromatography, on the
hydrocarbons and their mixtures by oxidative pyrohydrolytic development of the technique
ASTM D 7359-08
combustion followed by ion chromatography detection (combustion ion
chromatography-CIC). A format for everyone –
This e-book is available for
Chloride, fluoride, and bromide in liquid organics by combustion ion the iPad or for a standard
UOP 991-11
chromatography (CIC). computer web browser

Standard test method for total fluorine in coal and coke by pyrohydrolytic SPONSORED BY
ASTM D 5987-96
extraction.

Screening of total bromine in electric and electronic products by combustion

DIN EN 62321-3-2
ion chromatography.

DIN 51727 Testing of solid fuels — Determination of chlorine content.

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 The Column www.chromatographyonline.com Steinbach et al.

Figure 2: Determination of halogens and sulphur in polymer standard ERM–EC680k. Column: and fuel samples as well as latex and vinyl
Metrosep A Supp 5 - 150/4.0, eluent: 3.2 mmol/L sodium carbonate, 1 mmol/L sodium gloves.
hydrogen carbonate, 0.7 mL/min, column temperature: 30 °C.
Plastic Samples: The combustion of organic
0.7 materials containing halogen and sulphur
6.5
produces toxic gases that are harmful to

Chloride
6.0
humans and materials. To guarantee that
5.5
5.0
plastics are halogen- and sulphur-free, a quick
and reliable analysis is required. A certifed

Sulphate
4.5
Conductivity (µS/cm)

4.0 polymer standard, ERM–EC680k (Institute

3.5 for Reference Materials and Measurements,
3.0 Geel, Belgium), is used to check the precision
Bromide

2.5
and accuracy of CIC. It is a low-density
2.0
polyethylene granulate containing known
Fluoride

1.5
quantities of chlorine, bromine, and sulphur.
1.0
0.5
Figure 2 illustrates the analysis of halogen and
0.0 sulphur content of the reference standard by
0 2 4 6 8 10 12 14 16 18 20
CIC. The recovery rates, ranging between 99%
Time (min)
and 102.4% (Table 2), demonstrate that the
plastic has quantitatively combusted and that
Table 2: Certifed chlorine, bromine, and sulphur content of the polymer standard
the combustion gases have been completely
ERM–EC680k determined using combustion ion chromatography.
collected by the absorption solution.
ERM-EC680ka Certified Combusion ICb
Liquid Fuels: Burning fuels that contain
content (mg/kg) Content (mg/kg) RSD (%) Recovery (%)
sulphur produces sulphur dioxide that is
Chlorine 102.2 + 3.0 104.7 1.3 102.4
harmful to the environment. In addition,
Bromine 96.0 + 4.0 97.1 1.8 101.2
high sulphur content deactivates catalysts
Sulphur 76.0 + 4.0 75.2 3.6 99.0 in combustion engines and affects both the
a
Certified polyethylene standard from the Institute of Reference Materials, Geel, Belgium storage stability and ignition behaviour of fuels.
b
Mean of three determinations
The halogen content also plays an important
Instrumentation: The combustion unit is Application Areas role, as chloride in particular accelerates
from Analytica Jena, while the liquid handling The application areas described in this corrosion in the refnery process and in engines.
and IC are from Metrohm. The software used article illustrate the precision and accuracy The quality requirements for gasoline are
was MagIC Net from Metrohm. of CIC. The samples analyzed were plastic defned in DIN EN 228 and DIN 51626-1.

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Figure 3: Determination of sulphur and halogen content in gasoline. Column: Metrosep A

Supp 5 - 150/4.0, eluent: 3.2 mmol/L sodium carbonate, 1 mmol/L sodium hydrogen
E-Book Educational Series
carbonate, 0.7 mL/min, column temperature: 30 °C. Advances in GC-MS
Analysis of Pesticides

Sulphate
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Conductivity (µS/cm)

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Fluoride

Chloride

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Time (min)

Solid Fuels: It is also possible to analyze
Table 3: Determination of sulphur content in
gasoline. halogens and sulphur in solid fuels such
Contenta(mg/kg) RSD (%)
as wood pellets and brown or black coal
(Figure 4). In the case of the analyzed
Fluorine 0.78 0.46
coal sample, the results demonstrated
Chlorine 0.75 0.34
similar precision to those for the liquid
Sulphur 9.88 0.42
fuel. Recovery rates in the coal sample
a
Mean of three determinations
were 96.8% for sulphur and 103.4% for
The sulphur content must not exceed a limit chlorine. Representative and, therefore,
value of 10 mg/kg. Figure 3 shows that in homogeneous samples are a prerequisite
the gasoline sample under investigation, the for reproducible results. In the case of solid
sulphur content was just below this limit value samples, however, these are something of
at 9.88 mg/kg. an exception, which is why any irregularities
A format for ARTICLES INCLUDE DISCUSSIONS OF:
everyone – How to improve detection limits and reduce matrix interferences
This new e-book is to extend the range of pesticides that can be analyzed with GC
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The benefits of using an accurate-mass database
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A comparison of qualitative and quantitative results obtained
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An evaluation and comparison of three dSPE sorbent combinations,
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Shimadzu_TheColumn_02.2013.qxd 16.01.2013 11:06 Uhr Seite 1

Figure 4: Determination of halogen and sulphur in a coal sample. Column: Metrosep

A Supp 5 - 150/4.0, eluent: 3.2 mmol/L sodium carbonate, 1 mmol/L sodium hydrogen
carbonate, 0.7 mL/min, column temperature: 30 °C.

180
Sulphate

160 1.6

140

120
Conductivity (µS/cm)

0.8
Chloride

100

80
0.0
0 2 4 6 8 10 12 14
60 Time (min)

40

Chloride
20

0
0 2 4 6 8 10 12 14 16 18 20
Time (min)

Table 4: Determination of chlorine and hands. Only materials with low amounts
sulphur in solid fuels. of halogen and sulphur may be used in
Contenta RSD the water-steam cycle of power plants and
(mg/kg) (%)
the primary circuit of pressurized water
Chlorine 17 5.5
reactors, so that no corrosive halogenides
Sulphur 1439 1.5
or sulphates can get into these systems.
a
Mean of three determinations
Halogen and sulphur content is therefore
must be taken into consideration when a key consideration when selecting
selecting samples. appropriate materials for use in clean room
Gloves in Clean Room Environments: environments. In this case, vinyl gloves
Gloves are used in clean room are the better choice because of their
environments to hold back the ionic significantly lower halogen and sulphur
contamination found in perspiration from content (Figure 5 and Table 5).

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Figure 5: Determination of chloride and sulphate in latex gloves. Column: Metrosep A Supp as halogenides and sulphate during the She studied environmental chemistry at the
5 - 150/4.0, eluent: 3.2 mmol/L sodium carbonate, 1 mmol/L sodium hydrogen carbonate, subsequent ion chromatography process. Friedrich-Schiller-University in Jena, Germany,
0.7 mL/min, column temperature: 30 °C. By measuring the light intensity, a sensor where she also obtained her diploma. Before
90 tracks the progress of the combustion joining Analytik Jena AG in 2010, she worked

Sulphate
digestion and ensures that the samples as scientifc assistant at Saarland University,
80
combust fully. Complex samples no longer Germany, where she earned her Ph.D. in
70 require method development because the analytical chemistry.
60
optimum parameters for combustion digestion Christian Emmenegger is a product
Conductivity (µS/cm)

are selected according to the type and manager ion chromatography in the
50
quantity of the sample. Competence Center Ion Chromatography at
40 Metrohm International Headquarters. After his
References diploma in chemistry, he obtained his Ph.D.
30
1. A. Wagner, B. Raue, H.-J. Brauch, E. Worch, and T. in analytical environmental chemistry at the
Chloride

20 Lange, J. Chromat. A 1295, 82–89 (2013). Swiss Federal Institute of Technology in Zürich,
10
2. M. Laeubli, C. Emmenegger, and B. Bogenschütz, Switzerland.
Ion chromatographic determination of halogens Dirk Schmitz is a project manager in the Ion
0
0 2 4 6 8 10 12 14 16 18 20 and sulphur in solids using combustion as inline Chromatography Development of Metrohm
Time (min) sample preparation, 7th Conference on Ion International Headquarters. Dirk studied
Analysis, Berlin, Germany, 2013 (downloadable chemical engineering at the Fachhochschule
Table 5: Chlorine and sulphur content in latex and vinyl gloves. from metrohm.com/com/Applications/, search for Aachen in Germany.
8.000.6091). Alfred Steinbach is a scientifc technical
Latex Vinyl
writer and editor in the Marketing Department
Contenta (ppm) 638.8 35.9
Chlorine Daniel Hemmler is an MSc student at Aalen at the Metrohm International Headquarters.
RSD (%) 4.4 3.3
University, Germany. His major felds of study He obtained his MSc in nuclear chemistry
Contenta (ppm) 7263.6 363.2
Sulphur are analytical and bioanalytical chemistry. from the University of Cologne, Germany,
RSD (%) 4.7 2.4
a
Mean of three determinations
Within his studies, he did an internship in the and his Ph.D. in environmental and analytical
R&D Department of Ion Chromatography at biogeochemistry from the University of
Summary they are in liquid, solid, or gaseous form. Metrohm International Headquarters, based in Hamburg, Germany.
The CIC technique presented here provides Following combustion digestion of the Herisau, Switzerland.
a fully automated method of determining samples, the combustion products containing Sophia Kaufmann is an R&D assistant in E-mail: ast@metrohm.com
individual halogens and sulphur in a multitude halogens and sulphur are collected in an the Analytical Instrumentation Department of Website: www.metrohm.com
of organic matrices — regardless of whether oxidizing absorption solution and determined Analytik Jena AG in Langewiesen, Germany.

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