1. Combustion Ion Chromatography
Beyond the horizon – the world of combustion
Dr. Christian Emmenegger
Metrohm International Headquarters

2. Combustion IC Topics Why Combustion IC? – Regulations
Different combustion methods
The Mitsubishi Combustion System
Applications
USP
Combustion Ion Chromatography

3. Regulations Why do we need “halogen-free” products?
Address the fast and global increase of consumer electronics waste
Reduce damage to people and environment
Restriction for the use of hazardous materials mostly in various electronic and electrical equipment:
Europe:
Waste Electrical and Electronic Equipment Directive (WEEE) 2002/96/EC
Restriction of Hazardous Substances Directive (RoHS) 2002/95/EC (polybrominated biphenyls PBB, polybrominated diphenyl ether PBDE, Pb, Hg, Cd, Cr (VI))
PBB and PBDE are flame retardants (AW IN )
Improvement also for staff in production
Plasticizers
RoHS CrVI in coatings AW IN
Combustion Ion Chromatography

4. www.ipc.org www.iec.ch www.jpca.net www.halogenfree.org
Regulations
Halogen-free Definition
JPCA (Japan Printed Circuit Association): JPCA-ES
Br < 900ppm Cl < 900ppm
IEC (International Electrotechnical Commission): IEC
Total halogens < 1500ppm
IPC (Association Connecting Electronic Industries): IEC
Other VIIA group halogens are not included in the definition (F, I)
Combustion Ion Chromatography

5. Regulations Regulations Apple (069-1857-A) Br<900ppm Cl<900ppm
Total halogens<1500ppm
Sony Ericsson 2/ LXE Uen
Samsung Electronics
Combustion Ion Chromatography

6. Regulations Various Test Methods
EPA Method 9056A
Determination of inorganic anions by IC (for drinking water, wastewwater, aques extracts of solids and the bomb combustion samples)
DIN 41727
Determination of Chlorine in different types of Coal (German Norm) with Oven at 1250°C
ASTM D 7359 –08 Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatoghraphy Detection
Combustion Ion Chromatography

7. Regulations Fuel and Petrol Industry
Low sulfur contents reduce air pollutants in the air
Low sulfur contents increase performance of emissions cleaning systemes in automobiles
European Union, Japan… continously reduced sulfur content
DIN EN 228 for automobile max. 10 ppm Sulfur
Continously reduced to presently 10 mg/kg S
Combustion Ion Chromatography

8. Application Fields Which industries are applicable to CIC?
Environmentally relevant oil, plastic waste, acitvated substances: carbon …
Electronic components: printed circuit boards, resins, cables, insulating materials …
Fuels: gasoline, kerosene, crude oil, heating oil, coal, catalysts …
Plastics: polymers such as polyethylene, polypropylene …
Dyestuffs: pigments, paints …
Pharmaceutical products: raw substances, intermediates, finished products
Combustion Ion Chromatography

9. Potentional Customers
Who does not use electronical parts?
Combustion Ion Chromatography

10. Potentional Customers
Who does not use electronical parts?
Combustion Ion Chromatography

11. Sample Combustion Methods
Typical Combustion Setups
Offline:
Schöniger Flask
Wickbold - Apparatus
Parr-Bomb with Na2O2
Oxygen-Bomb
Microwave-induced combustion
Online:
Mitsubishi AQF
Combustion Ion Chromatography

12. Schöniger Flask Combustion by Kurt Schöniger
Closed system to determine halogens and sulfur in organic compounds:
Closed system
Compounds on a filter are burned in a flask filled with oxygen and adsorbed.
Die mikroanalytische Schnellbestimmung von Elementen wie Halogenen und Schwefel in organischen Verbindungen mittels des sogenannten "Schoeniger Kolbens" wurde von Schoeniger 1955, 1956 und 1958 beschrieben.
Zitat:
"Das Prinzip der Methode ist folgendes: Die zu untersuchende Substanz wird in einem Stück aschefreiem Filterpapier in einem mit Sauerstoff gefülltem Erlenmeyerkolben verbrannt, die Verbrennungsprodukte absorbiert und der Gehalt des zu bestimmenden Elementes massanalytisch erfasst. Der ursprünglich verwendete Platindraht zur Befestigung des Filterpapiers wurde, wegen rascher Versprödung, durch ein Platinnetzchen mit einer Drahtstärke von mm ersetzt."
Combustion Ion Chromatography

13. Wickbold Combustion Apparatus
Oxyhydrogen Gas Blowpipe Combustion
Open system mainly for sulfur and chlorine analysis in petroleum products:
Substance is evaporated in oxygen stream
Burned in a cooled quartztube in oxyhydrogengas
Absorption in solution
Oxyhydrogen gas = knallgas
Burning in flame and cooling with Wickbold
Combustion Ion Chromatography

14. Parr-Bomb – Oxygen Bomb
Classical Methodolgy
Closed system for combustion in a sealed, pressure-stable environment:
Parr Bomb: Oxydation e.g. by Na2O2 at elevated temperatures
thermal excitation (slow, hours)
Microwave-induced Combustion (fast, several minutes)
Oxygen bar O2 the sample is ingnited by electrodes
Na2O2 = sodium peroxide
AW UK Calirimetric Bomb by Customer Mervyn Barggott, OSS Group
AW UK Determination of F -, Cl -, PO42- and SO42- combusted oil sample
oxygen bomb
Combustion Ion Chromatography

15. Mitsubishi Combustion System
Complete Prep Station for Ion Chromatography
Open system for fast halogen and sulfur analysis:
Sample is automatically inserted into furnace and incrementally burned in oxygen/argon gas stream
Absorption in H2O2 solution
Combustion Ion Chromatography

16. Which Ions are measured?
Combustion and Absorption Principles
Sulfur and halogen compounds are combusted under Ar/O2 gas and oxidized by H2O2
Sample in combustion gas in absorption solvent
S SO2, SO SO42-
X (F, Cl, Br, I) HX, X X-
N/A for the following compounds:
N NO, NO2 (bad recovery)
P P2O5 (non-volatile)
M (Metal) MO (metal oxides are non-volatile)
Internal standard (e.g. Phosphate, Tartaric Acid, Citric Acid…) is added to the absorption solvent to correct for the absorption volume
Combustion Ion Chromatography

17. Specifications for Samples
Important numbers for Mitsubishi Combustion IC
Solid and Non-Aqueous Liquid Samples
Solid sample mg (typically mg)
Liquid Sample mL (typically mL)
Absorbent Volume
3-10 mL (extendable up to 20 mL)
Furnace Temperature max 1100°C
Combustion Time about 3-7 minutes
Combustion Ion Chromatography

18. Sample Preparation Is sample preparation required?
Inhomogenous, bulky and large samples need sample preparation:
Smaller size by scissors, cutter
Dissolve in solvent
Powdering by grinder, mill
Freeze milling
Combustion Ion Chromatography

19. Flowpath Combustion IC
Common Conditions:
Inlet Temperature: °C
Outlet Temperature: °C
Ar/O2 flow: 200 mL/min
O2 flow: 450 mL/min
WS-100 Ar flow: 150 mL/min
Schematic of the CIC system
Gas Reinheiten minimum:99.98 % Argon
99.7 Oxygen
Combustion Ion Chromatography

20. Burn Process Multistage Combustion Process (gradually)
The combustion process is divided into the following steps for the sample boat:
4. 3rd position
6. Cooling position
End position (oxydation)
7. Home position (Absorption Time)
2. 1st position (preheating)
3. 2nd position
Home Positon (Prepare Sample)
Combustion Ion Chromatography

21. Combustion Program Sample combustion and absorption programs
Combustion must be optimized for each sample for a slow pyrolysis process! Otherwise incomplete combustion!
Combustion Ion Chromatography

22. Time Program Efficient Time Schedule for Combustion and IC
The analysis time schedule is optimized and synchronized:
Remote Signal für IC Start
Cleaning Combustion Ion Chromatography
3 min min min
1st sample
2nd sample
3rd sample
Cleaning Combustion
3 min min
Combustion Ion Chromatography

23. Multiple Combustion Sample Accumulation with multiple combustion
Multiple Combustion time schedule for low concentrations:
Cleaning Combustion Combustion Combustion Ion Chromatography
3 min min min min 15 min
Sample to show multiple injection is Bleifrei 95 (lead-free) aus AW CH
Sulphate and Chloride concentration in absorption solvent correlate well
Combustion Ion Chromatography

24. Combustion Temperatures
Temperatures for ideal combustion
Typical combustion temperatures for following compound types:
Organic /1000 °C
Organic with inorganic /1100 °C
Inorganic /1100 °C
Combustion Ion Chromatography

25. Combustion Improver Protects equipment and increases recovery
Recovery is low when target is inorganic salt or sample matrix has inorganics
Also effective against corrosion of quartz glass
Typical improvers are:
tungsten oxide (effective for alkaline/alkaline earth metal: Na, Ca, …)
copper oxide (halogen analysis in silica compound, glass)
iron oxide (halogen analysis in silica compound, glass)
Cannot prevent corrosion by fluorine
Combustion Ion Chromatography

26. Combustion Improver Effect
Effect of Combustion Improver
Prevent corrosion of quartz glass
CaO + H2O Ca(OH)2 deteriorates tube
CaO + H2O + WO3 CaWO4 + H2O lightens deterioration
Improves e.g. sulfur recovery:
CaSO4 + WO3 Ca WO4 + SO3
Na2SO4 + WO3 Na2WO4 + SO3
Combustion Ion Chromatography

27. Sample Boat Types Several kinds of boats are available Boat for ABC
quartz boat
Boat for ABC
quartz boat: organic sample without residual
ceramic disposable boat: with improver or sample has residue which cannot be cleaned out
Boat for auto sampler
ceramic boat: organic sample without residual.
nickel inner disposable boat: with improver or residue which cannot be cleaned out. Only for halogen (sulfur has low recovery)
Quartz boat can deteriorate by fluorine, alkaline metal, elkaline earth metal. Frequently washing helps to elongate life.
ceramic disposable boat
ceramic boat
nickel inner disposable boat
Combustion Ion Chromatography

28. Pyrolysis Tube Handling and Use
Quartz tube can be deteriorated by fluorine, alkaline and alkaline earth metal. Frequently washing necessary. (deteriorating samples are: sodium sulfonic acid, sodium sulfate, barium sulfate, sodium salt, potassium salt, alakline earth metal. High fluorine)
Alternative: ceramic inner tube
Combustion Ion Chromatography

29. Mitsubishi System Configurations I
Combinations for AQF-100
Basic Units necessary:
GA-100 (gas absorption unit)
AQF-100 (furnace)
WS-100 (water supplier)
Absorption Parts:
Absorption Tube for Low Concentration (10 mL)
Absorption Tube for High Concentration (20 mL, 20 und 5 mL Sampling Loops, Trap Column)
Sample Injectors for combustion:
for liquids: ABC-100 or combo ABC ASC150L
for solids: ABC-100 or ASC-120S
Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis
Combustion Ion Chromatography

30. Mitsubishi System Configurations II
Combinations for AQF-100
Basic Units necessary:
GA (gas absorption unit)
AQF (furnace)
WS-100 (water supplier)
Absorption Parts:
Absorption Tube for Low Concentration (10 mL)
Absorption Tube for High Concentration
(20 mL, 20 und 5 mL Sampling Loops, Trap Column)
Sample Injectors for combustion:
for liquids: ABC-100 or combo ABC ASC150L
for solids: ABC-100 or ASC-120S
Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis
Combustion Ion Chromatography

31. Mitsubishi System Configurations III
Combinations for AQF-100
Basic Units necessary:
GA (gas absorption unit)
AQF (furnace)
WS-100 (water supplier)
Absorption Parts:
Absorption Tube for Low Concentration (10 mL)
Absorption Tube for High Concentration (20 mL, 20 und 5 mL Sampling Loops, Trap Column)
Sample Injectors for combustion:
for liquids: ABC-100 or combo ABC ASC150L
for solids: ABC-100 or ASC-120S
Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis
ASC150L 50 samples
ASC-120S 20 samples
ABC-100
Combustion Ion Chromatography

32. The Metrohm-Mitsubishi Combination
Setup with IC Net
Combination with Compact 761/861
Compact IC 761 need to have an analog output
771 synchronizes the two systems
MagIC Net can be added to such a system (database features) There is a package available for the 771 and MagIC Net ( ).
Part No.
Description
Use
Cable 771 (analog) – 819
Connection of analog and start signals to 771
IC Compact Interface
Receives and records the analog signal of the IC system. Further it receives the contact closure signal of the Mitsubishi instrument and starts the IC instrument.
Combustion Ion Chromatography

33. The Metrohm-Mitsubishi Combination
Setup with MagIC Net
Compact IC pro 881
Scan for a contact closure signal on input line ( *****1** )
Part No.
Description
Use
Remote Box MSB
Connect to MSB port of IC instrument.
Cable 766/788/813/
Connect to the Mitsubishi contact closure output with the open ends and with the 21 pin connector to the Remote box
Combustion Ion Chromatography

34. Applications
Performance check upon installation: S-Benzylthiuroniumsulfate
Check solution S-Benzylthiuroniumsulfate 25mg/25mL Ethanol
Absorbent 30 ppm H2O2, 1 ppm Phosphate
Calibrate IC System
Measure 30 mL check solution
Judgment: within % of theoretical value
% Recovery for Cl and S in AW 953
AW CH
Combustion Ion Chromatography

35. ERM-EC681k Low density Polyethylene pellet
Certified Reference Material
A Supp 5 –150
H2O2 30 ppm, 1 ppm Phosphate
AW CH
Combustion Ion Chromatography

36. Fuel Sulfur in Fuel Available Reference Material by ERM:
Various Fuel Measurements
A Supp 5 –150
50 mL injections
Simultaneous Chloride determination
H2O2 30 ppm, 1 ppm Phosphate
Alternativ mit AW DE Fluoride, Acetate, Formiate and Chloride in Fuel with Matrix Elimination
PO4 1 ppm, H2O2 30 ppm
Sample
Chloride [ppm]
RSD [%]
Sulfur [ppm]
Bleifrei 95 (lead free)
7.9
2.3
10.8
1.0
Diesel
4.5
9.1
1.3
1.1
Migrol Greenlife Biodiesel
5.0
1.2
10.4
Rapeseedmethylester (RME)
4.9
3.1
3.8
1.5
AW CH
Combustion Ion Chromatography

37. Highly viscous oil samples
Determination of Chloride
Crude oil with high content of Sulfur
A Supp 5 –150
100 mL injections
H2O2 300 ppm, 1 ppm Phosphate
50 ppb Cl was the lowest calibration point.
Sample
Chloride [ppm]
RSD [%]
Waxy distillate
36.5
4.3
HCR-Feed
< LOQ
9.1
Migrol Greenlife Biodiesel
5.0
1.2
Rapeseedmethylester (RME)
4.9
3.1
AW CH
Combustion Ion Chromatography

38. Residual solvents Matrix Elimination of H2O2 (no disturbance for F)
Determination of F, Cl,Br, S
A Supp 5 –150
10 or 100 mL injections
H2O2 900 ppm, 20 ppm Phosphate for high concentrated samples
H2O2 90 ppm, 1 ppm Phosphate for low concentrated samples
1P12497E THF/Toluene P760 Diversolvent
A PCC HC, Dosino,
No.
S [%]
Cl [%]
Br [%]
F [%] 1
n.d.
8.16
13.80 2
8.03
13.59 3
8.56
14.58
Avg -
8.25
13.99
RSD %
1.2
3.7
No.
S [ppm]
Cl [ppm]
Br [ppm]
F [ppm] 1
2.4
14.8
20.6
n.d. 2
2.5
14.7
20.7 3
3.3
20.9
Avg
2.7 -
RSD %
0.3
0.6
AW CH
Combustion Ion Chromatography

39. Parameters are adjustable
Adjustable parameters e.g. for lower concentration
Increase amount of sample for combustion
Decrease absorbent volume
Multiple combustion into one absorbent volume
Increase injection loop
Combustion Ion Chromatography

40. USP Advantages by Combustion IC Full Automation with Mitsubishi setup
Reduced analysis time
Fast Sample throughput
Simultaneous determination of sulfur and halogen compounds
Halogens are speciated individually
Analysis of solids and viscous substances!
Analysis within the ppm range
New application fields for IC
Combustion Ion Chromatography

41. Combustion Ion Chromatography
Beyond the horizon – the world of combustion sampling
H2O2 zeigt Störung bei F -> Matrix Elimination