04 User Manual 3000 Systems V2.0 PDF

User Manual
3000 systems
TN/TS/TX
Version: 2.0.2
User Manual
TN-TS 3000 Rev. 2.0.2
Disclaimer
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or any part of the software incorporated in the Products in any way whatever nor permit the whole or
any part of the software to be combined with or become incorporated in any other programs nor
decompile disassemble or reverse engineer the same nor attempt to do any other such things.
In no event shall [Thermo Fisher Scientific] have any obligation to repair or replace in accordance with
any warranties given with the Product in whole or in part, as the result of
• Accident, disaster or event of force majeure

• Customers misuse, fault or negligence by or on the Customers behalf
• Use of the software in a manner for which it was not designed
• Causes external to the software such as, but not limited to, power failure or electrical power
surges
• Use of the software in combination with equipment or software not supplied by Thermo Fisher
Scientific or with which it is incompatible.
The warranty shall not apply to any software which the Customers alters or modifies.
Thermo Fisher Scientific does not warrant that the software is error-free, will accomplish any particular
result or is fit for any particular purpose of or intended use by the Customer and it is for the Customer
to satisfy yourself that the software is so fit.
The photographs used in this manual can differ from the actual apparatus and set-up’s. All
photographs, drawings and diagrams are for illustrative purposes only.
User Manual 3000 systems V2.0.doc Page 2 of 169

User Manual
TN-TS 3000 Rev. 2.0.2
Copyright
The content of this manual is protected by copyright.
All efforts have been made to ensure the accuracy of the contents of this manual. However should any
errors be detected Thermo Fisher Scientific would greatly appreciate being informed of them
The above notwithstanding Thermo Fisher Scientific can assume no responsibility for any errors in this
manual or their consequences.
For more information, check our website at www.thermo.com
Any use of this manual other than, intended by the producer, is prohibited without the prior written
permission of Thermo Fisher Scientific
© 2000-2007, Copyright reserved by Thermo Fisher Scientific Delft, The Netherlands

User Manual
TN-TS 3000 Rev. 2.0.2
Content
1. GENERAL INFORMATION ....................................................................................... 10

1.1. OPERATING MANUAL ................................................................................................ 10
1.2. PICTOGRAMS ............................................................................................................. 11
1.3. SERVICE AND MAINTENANCE .................................................................................... 12
2. GENERAL SAFETY INSTRUCTIONS ...................................................................... 13
2.1. SAFETY MARKS ON THE EQUIPMENT ......................................................................... 13
2.2. SAFETY RULES FOR THE OPERATOR ........................................................................... 14
2.2.1. Rules applying to installation........................................................................... 14
2.2.2. Do’s and don’ts with the 3000 system.............................................................. 15
3. PRINCIPLE OF THE MEASUREMENT ................................................................... 16
3.1. INTRODUCTION OF THE 3000 SYSTEM (TN-TS) ......................................................... 16
3.2. PRINCIPLE OF THE UV-FLUORESCENCE DETECTION ................................................... 17
3.3. PRINCIPLE OF CHEMILUMINESCENSE DETECTION ....................................................... 19
3.4. GENERAL FLOW-PATH 3000 SYSTEM TN-TS............................................................. 20
3.5. SAMPLE INTRODUCTION ............................................................................................ 21
3.5.1. The "Liquids Module" (solvents, gasses, light hydrocarbons)......................... 21
3.5.2. The "Liquids Module" (model “0019”) ........................................................... 22
3.5.3. The "Solids module" universal ......................................................................... 23
3.5.4. The "TN 3000 Solids module" .......................................................................... 24
The "Liquids Module Water" (Nitrogen according DIN) ............................................... 24
3.5.5. The "TN 3000 Liquids Module" for light hydrocarbons .................................. 25
3.6. FURNACE ................................................................................................................... 25
3.6.1. Standard furnace tube ...................................................................................... 25
3.6.2. Turbo tube ........................................................................................................ 26
3.7. CONDITIONING .......................................................................................................... 27
3.7.1. Drying............................................................................................................... 27
3.7.2. C.F.I.S. (patented) ............................................................................................ 27
3.7.3. Molybdenum converter..................................................................................... 28
3.8. SULFUR DETECTOR .................................................................................................... 28
3.9. PHOTO MULTIPLIER TUBE ......................................................................................... 29
3.10. DETECTOR FOR NITROGEN ........................................................................................ 30
4. INSTALLATION OF THE 3000 SYSTEM................................................................. 31
4.1. INTRODUCTION .......................................................................................................... 31
4.2. 3000 SYSTEM, EXTERNAL CONNECTIONS AND SPECIFICATIONS ................................. 31
4.2.1. Power connections ........................................................................................... 31
4.2.2. Communication connections ............................................................................ 32
4.2.3. Gasses: connections and specifications ........................................................... 33
4.2.4. 3000 system glassware connections................................................................. 34
4.2.5. Sample introduction modules ........................................................................... 34
4.2.5.1. The "Liquids module" .............................................................................. 34
4.2.5.2. The "Solids module" ................................................................................ 34
4.2.5.3. The "Liquids module Water" ................................................................... 35
4.2.6. Furnace tube .................................................................................................... 35
User Manual
TN-TS 3000 Rev. 2.0.2
4.2.7. Outlet connection (TN)..................................................................................... 36

4.3. PERMA PURE .............................................................................................................. 36
4.4. GLASS-FIBER FILTER ................................................................................................. 37
4.5. GAS CONNECTION TN-TS, SEPARATE AND SIMULTANEOUSLY .................................. 37
4.5.1. Separate analyses............................................................................................. 37
4.5.2. Simultaneous analyses ..................................................................................... 37
4.5.3. Connection furnace outlet TS only ................................................................... 38
4.5.4. Mode selection gas flow: separate or simultaneous ........................................ 40
4.6. UV-F DETECTOR MODULE ......................................................................................... 41
4.6.1. Connections and settings on UV-F detector .................................................... 42
5. OPERATING THE 3000 SYSTEM.............................................................................. 44
5.1. 3000 SYSTEM START UP ............................................................................................ 44
5.2. PREPARATION OF SOLUTIONS .................................................................................... 44
5.2.1. Sulfur standards ............................................................................................... 44
5.2.1.1. Dibenzothiophene stock solution (sulfur determination)........................ 44
5.2.1.2. Dibenzothiophene standard solution (100 mg S/L) ................................ 44
5.2.1.3. Dibenzothiophene standard solution (50 mg S/L) .................................. 44
5.2.1.4. Dibenzothiophene test solution (10 mg S/L) .......................................... 45
5.2.1.5. Dibenzothiophene test solution (5 mg S/L) ............................................ 45
5.2.1.6. Dibenzothiophene test solution (1 mg S/L) ............................................ 45
5.2.2. Nitrogen standards (petro)............................................................................... 45
5.2.2.1. Carbazole stock-solution (nitrogen determination).................................. 45
5.2.2.2. Carbazole standard solution ..................................................................... 45
5.2.2.3. Benzonitrile stock-solution ...................................................................... 45
5.2.2.4. Benzonitrile standard solution.................................................................. 45
5.2.3. Nitrogen standards (water) .............................................................................. 46
5.2.3.1. Preparation of the Nitrate stock................................................................ 46
5.2.3.2. Preparation of the Ammonia stock........................................................... 47
5.2.3.3. Preparation of the Ammonia-Nitrate mix stock ....................................... 47
5.2.3.4. Preparation of the Glycine stock .............................................................. 48
5.2.4. Furnace tube and permapure connection ........................................................ 48
5.2.5. Module connection ........................................................................................... 48
5.2.6. Powering the system......................................................................................... 49
5.2.7. Adjust the gas flow (Manual) ........................................................................... 49
5.2.8. Gas leakage test basic 3000 system ................................................................. 51
5.2.9. Gas leakage test UV detection module............................................................. 52
5.3. 3000 SYSTEM NORMAL OPERATION ........................................................................... 53
5.3.1. Visible inspection of glassware........................................................................ 53
5.3.2. Glassware maintenance ................................................................................... 53
5.3.2.1. Furnace tube ............................................................................................. 53
5.3.2.2. SOLIDS glassware ................................................................................... 54
5.3.3. Introduction module ......................................................................................... 54
5.3.3.1. Solids Module .......................................................................................... 54
5.3.3.2. Liquids Module ........................................................................................ 54
5.3.3.3. TN water module...................................................................................... 54
5.3.4. Standard software settings ............................................................................... 54
5.3.5. Running analysis .............................................................................................. 55

User Manual
TN-TS 3000 Rev. 2.0.2
5.3.5.1. Starting ThEuS™...................................................................................... 55

5.3.5.2. Creating a calibration ............................................................................... 58
5.4. QUICK PERFORMANCE CHECK TN/TS MODE .............................................................. 59
5.4.1. TN mode test (setting is low range).................................................................. 59
5.4.2. TS-UV mode test (setting is mid-range) ........................................................... 59
5.5. 3000 SYSTEM STANDBY MODE .................................................................................. 60
5.6. 3000 SYSTEM SHUT DOWN ......................................................................................... 60
6. TN WATER .................................................................................................................... 61
6.1. INTRODUCTION .......................................................................................................... 61
6.2. SPECIFICATIONS ........................................................................................................ 62
6.2.1. Standardized methods ...................................................................................... 62
6.2.2. Test results of the TN-3000 water .................................................................... 62
6.2.3. Summary/conclusion ........................................................................................ 63
6.3. MAINTENANCE OF THE GLASSWARE .......................................................................... 64
6.3.1. Boat and introduction module.......................................................................... 64
6.3.2. Outlining of the boat ........................................................................................ 65
6.3.3. Replacement of the Nickel sample cylinder ..................................................... 65
6.3.4. NeXYZ auto sampler......................................................................................... 66
6.3.5. Furnace tube and outlet ................................................................................... 66
6.3.6. Principle of the furnace outlet tube.................................................................. 68
6.3.7. Cold trap, tubing and filter .............................................................................. 69
6.4. SEVERAL REMARKS AND TIPS .................................................................................... 71
6.5. FREQUENT MAINTENANCE ......................................................................................... 71
6.6. TROUBLE SHOOTING .................................................................................................. 72
6.7. FLOW DIAGRAM TN WATER ...................................................................................... 74
7. EXTERNAL SAMPLERS ............................................................................................. 75
7.1. NEXYZ AUTOSAMPLER ............................................................................................. 75
7.2. ECA1700 AOX COLUMN AUTOSAMPLER ................................................................. 75
7.2.1. Introduction-Description.................................................................................. 75
7.2.2. ECA-TOX method, step by step ........................................................................ 77
7.2.3. Installation ECA1700....................................................................................... 77
7.2.4. ECA1700, Mounting......................................................................................... 78
7.2.5. ECA1700, external connections ....................................................................... 81
7.2.6. ECA1700: System and software settings.......................................................... 82
7.2.7. Software settings ECA1700.............................................................................. 82
7.3. ESA2000 AOX AND SOLIDS AUTO SAMPLER ............................................................ 84
7.3.1. Introduction-Description.................................................................................. 84
7.3.2. ESA-AOX batch method, step by step............................................................... 85
7.3.3. General solids method, step by step ................................................................. 86
7.3.4. Installation of the ESA2000 ............................................................................. 87
7.3.5. ESA2000, Mounting ......................................................................................... 87
7.3.6. ESA2000 hardware alignment procedure ........................................................ 90
7.3.7. ESA2000 external connections......................................................................... 92
7.3.8. ESA2000: System and software settings .......................................................... 93
7.3.9. Software settings ESA2000 .............................................................................. 94
7.3.10. ESA Boat program and related settings........................................................... 96

User Manual
TN-TS 3000 Rev. 2.0.2
8. COULOMETRIC ANALYSIS ON THE 3000 SYSTEM (OPTIONAL).................. 98

8.1. INTRODUCTION 3000 SYSTEM IN HALOGEN/SULFUR MODE .................................... 98
8.2. PRINCIPLE OF THE MEASUREMENTS ........................................................................... 99
8.3. SAMPLE INTRODUCTION ............................................................................................ 99
8.3.1. Manual sampling modules ............................................................................... 99
8.3.1.1. AOX module .......................................................................................... 100
8.3.1.2. POX module ........................................................................................... 100
8.3.1.3. Solids Module ........................................................................................ 100
8.3.1.4. Liquid Module........................................................................................ 101
8.3.2. Auto sampling................................................................................................. 102
8.4. FURNACE ................................................................................................................. 102
8.5. GAS CONDITIONING ................................................................................................. 102
8.6. DETECTOR, COULOMETRIC TITRATION .................................................................... 102
8.6.1. Halide analysis, principle .............................................................................. 103
8.6.1.1. Halide analysis, titration cell.................................................................. 105
8.6.1.2. Halide analysis, circuit diagram............................................................. 106
8.6.2. Sulfur analysis, principle ............................................................................... 107
8.6.2.1. Sulfur analysis, titration cell .................................................................. 108
8.6.2.2. Sulfur analysis, circuit diagram.............................................................. 109
8.7. DATA PROCESSING .................................................................................................. 110
9. INSTALLATION HALOGEN AND SULFUR OPTION (COULOMETRIC)...... 111
9.1.1. Glassware connections................................................................................... 111
9.1.2. Sample introduction module .......................................................................... 111
9.1.2.1. AOX module .......................................................................................... 111
9.1.2.2. POX module ........................................................................................... 112
9.1.2.3. Solids Module ........................................................................................ 112
9.1.2.4. Liquid Module........................................................................................ 112
9.1.3. Furnace tube .................................................................................................. 112
9.1.4. Connection tube furnace scrubber ................................................................. 112
9.1.5. Installation sulfuric acid scrubber ................................................................. 112
9.1.6. Sulfuric acid scrubber connected................................................................... 113
Figure: sulfuric acid scrubber assembly........................................................................ 113
9.1.7. NOx-scrubber.................................................................................................. 113
9.1.8. Detector, titration cell.................................................................................... 114
9.1.9. Cell compartment and cooling ....................................................................... 115
10. OPERATING THE 3000 SYSTEM IN TX/TS MODE ........................................ 116
10.1. 3000 SYSTEM TX/TS MODE STARTING UP........................................................ 116
10.1.1. Preparation of reagents ................................................................................. 116
10.1.1.1. Sulfuric acid solution ............................................................................. 116
10.1.1.2. Halide electrolytic solution .................................................................... 116
10.1.1.3. Sulfur electrolytic solution..................................................................... 116
10.1.2. AOX reagents ................................................................................................. 117
10.1.2.1. Nitrate stock solution ............................................................................. 117
10.1.2.2. Nitrate wash solution.............................................................................. 117
10.1.2.3. p-Chlorophenol stock solution (200 mg Cl/L) ....................................... 117
10.1.2.4. p-Chlorophenol standard solution (1 mg Cl/L) ...................................... 117

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.2.5. p-Chlorophenol test solution (100 μg Cl/L)........................................... 117

10.1.3. POX reagents ................................................................................................. 117
10.1.3.1. Dichloromethane stock solution (1000mg Cl/L).................................... 117
10.1.3.2. Dichloromethane standard solution (100mg Cl/L) ................................ 117
10.1.3.3. Dichloromethane test solution (100 μg Cl/L) ........................................ 117
10.1.4. TX/EOX reagents............................................................................................ 118
10.1.4.1. Aldrin stock solution (1000 mg Cl/L) .................................................... 118
10.1.4.2. Aldrin standard solution (100 mg Cl/L)................................................. 118
10.1.4.3. Aldrin test solution (10 mg Cl/L)........................................................... 118
10.1.5. TS/EOS reagents ............................................................................................ 118
10.1.5.1. Diphenylsulfide stock solution (1000mg S/L) ....................................... 118
10.1.5.2. Diphenylsulfide standard solution (100mg S/L) .................................... 118
10.1.5.3. Diphenylsulfide test solution (10mg S/L) .............................................. 118
10.1.6. Preparation of samples .................................................................................. 119
10.1.6.1. AOX sample preparation........................................................................ 119
10.1.6.2. POX sample preparation ........................................................................ 121
10.1.6.3. TOX sample preparation ........................................................................ 121
10.1.6.4. EOX sample preparation ........................................................................ 122
10.1.7. Adjusting gas flows ........................................................................................ 124
10.1.8. Filling the scrubber........................................................................................ 124
10.1.8.1. Sulfuric acid scrubber ............................................................................ 124
10.1.8.2. NOx-scrubber.......................................................................................... 125
10.1.9. Powering the system....................................................................................... 125
10.1.10. Installing a selected Module ...................................................................... 125
10.1.11. Titration cell (chloride).............................................................................. 126
10.1.12. Titration cell (sulfur).................................................................................. 127
10.1.13. Gas leakage test coulometric configuration .............................................. 128
10.2. 3000 SYSTEM NORMAL OPERATION.................................................................. 130
10.2.1. Visible inspection of glassware...................................................................... 130
10.2.2. Glassware maintenance ................................................................................. 130
10.2.2.1. Scrubber ................................................................................................. 130
10.2.2.2. Furnace tube ........................................................................................... 131
10.2.2.3. Liquids module....................................................................................... 131
10.2.2.4. AOX glassware ...................................................................................... 131
10.2.2.5. POX glassware ....................................................................................... 132
10.2.2.6. Solids glassware ..................................................................................... 132
10.2.3. Introduction module ....................................................................................... 132
10.2.3.1. Solids Module ........................................................................................ 132
10.2.3.2. Liquids Module ...................................................................................... 132
10.2.3.3. AOX Module.......................................................................................... 132
10.2.3.4. POX Module .......................................................................................... 132
10.2.4. Standard setpoints .......................................................................................... 133
10.3. 3000 SYSTEM STANDBY MODE ......................................................................... 133
10.4. 3000 SYSTEM SHUT DOWN................................................................................ 134
11. RUNNING ANALYSIS TX/TS MODE (COULOMETRIC)............................... 135
11.1. MANUAL ANALYSIS IN GENERAL ......................................................................... 135
11.2. MANUAL ANALYSIS USING SPECIFIC MODULES/METHODS.................................... 135

User Manual
TN-TS 3000 Rev. 2.0.2
11.2.1.1. Manual introduction POX ...................................................................... 135

11.2.1.2. Manual introduction AOX ..................................................................... 136
11.2.1.3. Manual introduction Solids, water and heavy hydrocarbons ................. 137
11.2.1.4. Manual injection EOX and “light hydrocarbons”.................................. 138
11.3. AUTOMATIC ANALYSIS IN GENERAL .................................................................... 138
11.4. AUTOMATIC ANALYSIS USING SPECIFIC MODULES/METHODS............................... 139
11.4.1.1. Automatic analysis AOX ....................................................................... 139
11.4.2. Automatic introduction Solids, water and “heavy” hydrocarbons................ 139
11.4.2.1. Automatic injection EOX and “light hydrocarbons” ............................. 139
12. TROUBLESHOOTING NITROGEN-SULFUR UV MODE .............................. 140
13. TROUBLESHOOTING COULOMETRIC OPTION.......................................... 142
14. CONSUMABLES AND SPARE PARTS ............................................................... 146
15. APPENDIX I : SETTINGS .................................................................................... 150
16. APPENDIX II INTERNATIONAL CHEMICAL SAFETY CARDS .............. 151
17. APPENDIX III QUICK REFERENCE START ANALYSIS -STANDBY........ 166
18. APPENDIX IV CONVERSION TABLE: MANUAL ROTAMETERS TO

DIGITAL MASSFLOW METERS .................................................................................... 167
19. APPENDIX V TECHNICAL SPECIFICATIONS .............................................. 168

User Manual
TN-TS 3000 Rev. 2.0.2
1. GENERAL INFORMATION
1.1. Operating Manual
This operating manual has been written with the user of the 3000 system in
mind. For this reason the manual mainly gives instructions detailing
operation of the apparatus and does not give detailed directions for the
maintenance or repair of the apparatus.
The organization making use of the 3000 system must ensure itself that the
operator is qualified to use an instrument of this sort and is capable of
following the recommendations for its use.
The operator should closely follow the instructions contained in this operating
manual in order to ensure the proper operation of the instrument.
This manual makes use of special signs and pictograms in order to highlight
remarks and instructions, which require special attention.
These signs and pictograms are listed in section 1.2 of this chapter.
Chapter 2 – “General Safety Instructions" details the safety pictograms
appearing on the outside of / and inside the apparatus. All directions relating
to these pictograms must be complied with at all times.
Should you encounter problems or have questions, which are not discussed
in this manual, please do not hesitate to get in touch with your Thermo Fisher
Scientific supplier.
Voltaweg 22
2627 BC, Delft
The Netherlands
Tel.: +31 (0)15 2571314

Fax.:+31 (0)15 2572297
EMail: [email protected]
(for technical questions and remarks)
[email protected]
(for questions and remarks about the user’s guide)
Web: http://www.thermo.com

User Manual
TN-TS 3000 Rev. 2.0.2
1.2. Pictograms
The following pictograms are used to highlight the information contained in

the text of this manual.
Special Attention
Text preceded by this sign should be read with special care.
Warning
Instructions preceded by this sign must be complied with

exactly.
Failure to do so may result in damage to the equipment or
physical injury. Furthermore, the measurement procedure may
be disturbed.
Electrical Hazard

exactly. Failure to do so may result in physical injury.
Heat

exactly. Failure to do so may result in physical injury.

User Manual
TN-TS 3000 Rev. 2.0.2
1.3. Service and Maintenance
Maintenance should only be carried out by persons specially trained by

Thermo Fisher Scientific employees for this purpose, with the sole exception
of the routine maintenance. The operator should carry out the latter.
We recommend submitting the 3000 system for technical maintenance by the

suppliers specialists, at least once a year, in order to ensure its continued
precision operation.

User Manual
TN-TS 3000 Rev. 2.0.2
2. GENERAL SAFETY INSTRUCTIONS

The 3000 system has been designed and manufactured in accordance with the
following standard.
- ISO 3864 Safety colors and safety signs.
Before using the 3000 system carefully read through this operating manual. It is
essential that the persons operating the apparatus or who come into direct
contact with it are fully informed of the nature and existence of all possible
hazardous areas in and around the apparatus.
2.1. Safety Marks on the equipment
Thermo Fisher Scientific uses the following safety colors and signs on the
analysis apparatus. These are based on the ISO 3864 international
standards for safety colors and signs. These signs indicate those locations
that require special attention and/or constitute a danger to personnel or the
apparatus.
The safety markings may be replaced or supplemented by explanatory texts.
All personnel coming into either direct or indirect contact with the 3000
system should be fully acquainted with these international safety-markings.
The signs and accompanying texts appearing on or inside the 3000 system
are shown below.
THE FURNACE CAN ATTAIN VERY HIGH

TEMPERATURES
THE OUTLET REACHES A TEMPERATURE OF

300°C.
ALLOW THE OUTLET TO COOL BEFORE
REMOVING.
HIGH VOLTAGE!
DO NOT REMOVE COVER!

User Manual
TN-TS 3000 Rev. 2.0.2
Precautions and/or conditions imposed by national laws or

company safety procedures, applying to the space where
the 3000 system is used must be respected
unconditionally!
Making these instructions known and ensuring compliance
with them is a responsibility for the management of your
organization. In case of doubt, consult your supervisor.
2.2. Safety rules for the operator
The general safety rules applicable to the apparatus are given below.
2.2.1. Rules applying to installation
The apparatus must be installed by duly qualified technicians or in

accordance with the instructions provided by supplier.
Please note the following requirements:
• Provide a well ventilated space;

• Avoid installation in a space where the apparatus is exposed to direct
sunlight and large fluctuations in temperature;
• The satisfactory operation of the equipment is guaranteed when it is
installed in an environment with temperatures between 10 and 30°C
and a relative humidity between 20 and 85%;
• Allow 20 cm of free space around the apparatus;
• provide a firm, smooth and horizontal surface measuring at least 80 x
160 cm
• Provide connections for supplies of oxygen (02) and argon (Ar)
/helium (He), pressure 1-3 Bar, 1/8" connector;
• Make sure that there is a suitable electrical supply nearby, 115/230
V, 50/60 Hz, at least 3600 W;
• Always connect the 3000 system directly to a grounded power point
using a 16 Amp. fused plug. In case of doubt consult an authorized
installer;
• Never use adapter plugs.
• Keep wires well clear from the furnace in- and outlet.
• Never connect the 3000 system to other equipment that does not
comply to safety class II.
Warning
An incorrectly grounded or ungrounded apparatus may

cause electric shock.

User Manual
TN-TS 3000 Rev. 2.0.2
2.2.2. Do’s and don’ts with the 3000 system

• Refer to the manual in case of doubt about a procedure, prior to
start-up, running samples or shut-down.
• Wear protective clothing, masks and spectacles in accordance with
the laboratory requirements for carrying out the measurements.
• Make sure that the apparatus is grounded as specified.
• The apparatus should be set up in such a way that it does not
constitute a danger to the user during the course of the work.
• Make regular checks on the connecting cables and gas piping for
possible damage and leaks.
• The apparatus may only be used for the purpose for which it is
intended and may be operated solely by qualified personnel.
• Never place heavy objects on the 3000 system.
• Never carry out any maintenance on the 3000 system, which is not
described in this manual.
• Never remove any covers, doors or panels, which are fastened into
position by means of screws.
• Keep all the analytical and other compartments provided with
opening flaps shut during the performance of analyses when this is
so required.
• Always use original materials and accessories developed by Thermo
Fisher Scientific. Unapproved materials and accessories may cause
the malfunction of the apparatus or give rise to hazardous situations.
• The use of parts, which are not manufactured/approved by Thermo
Fisher Scientific, could result into exclusion of warranty
arrangements.
• In case of a malfunction that could endanger safety, turn off the
apparatus immediately.
• Never sprinkle the housing with water or other liquids. To clean,
wipe with a moist cloth.
• Never shut the ventilation openings and check them regularly if they
are free from possible tissues and other items that could cause
blockage.
• Never place combustible materials on top of the analyzer. (tissues,
solvents, etc.)

User Manual
TN-TS 3000 Rev. 2.0.2
3. PRINCIPLE OF THE MEASUREMENT
3.1. Introduction of the 3000 system (TN-TS)
For many years, Thermo Fisher Scientific is a high quality producer of

analyzers used for the determination of the sulfur quantity in several kinds of
samples. This reliable technique was and still is, based on coulometric
detection by iodometric-titration.
The use of a coulometric detection is still very reproducible with a low limit of
detection. In practice it becomes more important every year to determine the
amount of sulfur as well as the amount of nitrogen in the same types of
samples. Until this moment, it was only possible to analyze both these
elements on different systems, by performing two analyses. To determine
both these elements simultaneously it is necessary to use a “dry” detection
technique for the analyses of sulfur and combining two detectors in one
analyzer.
Thermo Fisher Scientific has developed a SO2 - UV fluorescence detector,

which is designed to run separately or simultaneously with the Nitrogen
analyzer TN3000 or as a stand-alone unit, attached to any 3000 system.
The 3000 system is designed for fast and efficient analysis of total sulfur (S)
and nitrogen (N2). The 3000 system supports the use of different modules,
which are used for the introduction of various sample matrices into the
furnace. (e.g. ASTM) The SO2 and NO produced by combustion, is led trough
both detectors. SO2 is detected by the principal of fluorescence in
combination with a Photo Multiplier Tube {P.M.T.}. NO is detected by
chemiluminescense. Both analysis techniques are relative and make that
calibration is required. The basic flow-path for the measurement of NO and
SO2 is as follows:
UV-Fluorescence Permapure
detector
Chemiluminescense
detector
Gas outlet

User Manual
TN-TS 3000 Rev. 2.0.2
3.2. Principle of the UV-fluorescence detection

The sample is introduced into the furnace. During the movement towards the
furnace, the sample is flushed with argon or helium. In the furnace, the sulfur
components oxidize with a mixture of Ar/He and pure O2 into SO2. The gas
flow travels through a Perma pure membrane dryer. This device removes the
water from the gas stream. After the water removal, a glass-fiber filter
removes soot and other particles that might occur during uncontrolled
combustion, due to incorrect settings. Next, the conditioned gas flow enters
the sulfur detector. The figure below explains the detection principle of the
P-UV-F.
The following picture explains the principle of the detector.
Gas entrance Gas exit
Fig. 1: principle of the UV-fluorescence detector
Detection is based on the principle that SO2 molecules absorb ultraviolet (UV)
light and become exited, then decay to a lower energy state emitting UV light at
a specific wavelength.
The sample flows into the reaction chamber, where pulsating light (at a rate of
10 Hz) excites the SO2 molecules. The condensing lens focuses the pulsating
UV light into the mirror assembly. The mirror assembly contains eight selective
mirrors that reflect only the wavelengths, which excite SO2 molecules.
As the excited SO2 molecules decay to a lower energy state, an amount of UV

light is emitted that is proportional to the SO2 concentration. The band-pass filter
allows only the wavelengths emitted by the excited SO2 molecules to reach the
Photo Multiplier Tube (PMT). The PMT detects the UV light emission from the
decaying SO2 molecules. The photodetector located at the end of the
fluorescence chamber, continuously monitors the pulsating UV light source and
is connected to a circuit that compensates for fluctuations in the intensity of the
UV light. (AGC controlled)

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TN-TS 3000 Rev. 2.0.2
Singlet excited states Triplet excited states
Internal Vibrational
conversion relaxation
Intersystem
crossing
Internal &
external
conversion
Absorption Fluorescence Vibrational Phosphorescence

relaxation
Fig. 2: Excitation and the relaxation of electrons
The light emission is detected perpendicular on the UV-light by the PMT, to

avoid detection of the primary UV-light. The PMT only detects the emitted
light of the SO2-molecules. The reactions during this detection are:
SO2 + hυ1 → SO*2
SO*2 → SO2 + hυ 2
hυ1 = primary UV-Light

hυ2 = Emitted light of decaying SO2

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In seven steps:
1. The sample is introduced into the furnace.

2. The sample is oxidized into SO2.
3. The moisture is removed in the Perma Pure dryer.
4. Soot and undesired particles are trapped in the filter assembly.
5. In the reaction chamber, UV excites the SO2 molecules present in the
gas flow.
6. The fluorescence light is detected during the relaxation of the decaying
SO2* back to SO2 by the Photo Multiplier Tube, resulting in a voltage
signal, proportional to the sulfur amount.
7. The PC executes the data acquisition and generates a graphic display.
3.3. Principle of chemiluminescense detection

With an introduction module, the sample is brought into the furnace. During the
movement to the furnace the sample is flushed with argon. In the furnace the sample
oxidizes with O2 into nitric oxide (NO). The gas flow will be led through a heated
Perma pure membrane dryer. Here the water is removed from the gas. With a glass-
fiber filter soot and other particles are removed. In the reaction chamber the formed
NO will react with the added Ozone into NO2* (radical). The excited species emit
energy in the form of light when returning to the ground state, according to the
equations:
NO + O3 NO2* + O2
NO2* NO2 + hν
The emitted light is detected by the PMT and the generated area is integrated and
converted into a value representing the amount of nitrogen in the sample.
In seven steps:
1. The sample is introduced into the furnace.

2. The sample is oxidized into NO.
3. The moisture is removed in the Perma Pure.
4. The Thermo Fisher Scientific C.F.I.S. (Controlled Flow Introduction System)
will control both the flow- and pressure difference.
5. In the reaction chamber the gas flow (NO) is mixed with Ozone (O3) where an
immediate reaction occurs and NO2* is formed.
6. The emitted light is detected during the relaxation of the unstable NO2* into
NO2 by the means of a Photo Multiplier Tube.
7. The PC executes the data acquisition.

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TN-TS 3000 Rev. 2.0.2
3.4. General flow-path 3000 system TN-TS
The following figure displays the flow path of the 3000 system.
(Optional extension with a Halogen detection cell requires an exchange of the
permapure dryer for a (heated) glass connection (part number: ECS300009).)
O2 O2
Dryer gas in Ar
Liquid Module
Perma Pure
Dryer gas out
Molybdene Convertor
Vacuum pump
Ozone Killer
Ozone Generator
PMT detector
Temp. Contr.
Capillary

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3.5. Sample introduction

Thermo Fisher Scientific recognizes different types of samples. Therefore
multiple modules are available (water, hydrocarbons/gasses and solids).
The modularity of the 3000 system consists of different introduction modules
using similar connections but supporting different methods for sample
introduction.
When using the introduction modules there are two ways of sample
introduction in the module: manually or with an auto sampler. See chapter 7
The design of the introduction modules is based on current standard
analytical methods for total nitrogen, sulfur and halogens. The modules are
easily interchangeable and after installation controlled by the Thermo Fisher
Scientific software.
Samples are introduced into the system by the use of different introduction
modules. (refer to application info)
1. "Liquids Module" (standard module for light hydrocarbons, gasses)

2. “Liquids module 0019” (enhanced combustion features for low TN-TS)
3. "Solids Module" (universal)
4. “Solids module TN”
5. "Liquids Module Water" (for water samples)
6. “Liquids Module TN” (dedicated TN light hydro carbons)
3.5.1. The "Liquids Module" (solvents, gasses, light hydrocarbons)

This module uses a dual flow feed of gases to the module. The
introduction and combustion of organic solvents, sulfur and halogen
compounds are controlled completely.
Note This module is not suitable for low level nitrogen analysis. Instead
use the Module 0019.
By introducing a sample into the argon/helium stream, it is vaporized at

the appropriate temperature. Conversion into SO2, HCl, HBr, CO2 etc,
takes place. The desired detection compounds are optimally formed
and the risk of incomplete oxidation is minimized.

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Fig. Liquids module hydrocarbons
3.5.2. The "Liquids Module" (model “0019”)

Besides the “liquids module” for light hydrocarbons, a new universal module is
designed to support the simultaneous analysis of Sulfur and Nitrogen. (TN-TS)
Separate analysis of sulfur runs perfectly with the “standard liquids module” for light
hydrocarbons. This module is special designed for low level analysis of nitrogen.
Because no catalyst is present, lower detection levels and less memory effect are
realized. For sulfur analysis, a module without catalyst is a necessity, because of
“catalyst poisoning”. This is a well-known phenomenon.
(sulfur components will attach themselves very easily onto metals for example.)
The only option in running two different elements and still obtaining the best available
result was redesigning the introduction module.
This resulted in the “model 0019”, capable in handling both sulfur and nitrogen,
without compromising any of the two. The actual results are a perfect match with
results obtained from the individual “liquids modules”.
The “liquids module 0019” supports all know ASTM methods in the boiling range
below 400°C
Major advantage is the capability of the temperature controlled inlet zone and
different expansion chambers, which allows full fine-tuning for various application
purposes.

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Fig. Liquids module (model 0019)
3.5.3. The "Solids module" universal

This module uses a dual flow feed of gases to the module. The
introduction and combustion of solids containing various compounds
are in complete control. Both software and boat drive are in control of
the positioning and travel speed of the sample. By introducing the
sample into the argon/helium stream the sample evaporates at the
appropriate temperature (controlled by the boat position) and combusts
when oxygen is added. Conversion into SO2, HCl, HBr, CO2 etc, takes
place. The detection compounds are optimally formed and the risk of
incomplete oxidation is minimized.
Fig. Solids module universal

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3.5.4. The "TN 3000 Solids module"

With this module, a triple flow feed of gas is used. The introduction and combustion
of solids containing nitrogen compounds is in complete control. By introducing a
sample into the argon stream the sample evaporates at the appropriate temperature
(controlled by the boat position) and combusts just in front of the catalyst where
oxygen is added. Now conversion takes place directly over the catalyst. Nitric oxide is
optimally formed and the chance of incomplete oxidation is reduced.
Fig. Solids module TN
The "Liquids Module Water" (Nitrogen according DIN)

This module uses a double flow feed of gases into the module. The
introduction and combustion of water samples containing nitrogen
compounds are in complete control.
By introducing a sample into the argon/helium stream, the sample
vaporizes at high temperature and combusts when oxygen is added.
Conversion into NO takes place. Nitrogen dioxide is optimally formed
and the chance of incomplete oxidation is reduced.
Fig. Water module

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3.5.5. The "TN 3000 Liquids Module" for light hydrocarbons

With this module by using a triple flow feed of gases to the module, the introduction
and combustion of organic solvents, light hydrocarbons and nitrogen compounds are
in complete control. By introducing a sample into the argon stream it is vaporized at
the correct temperature and just before the catalyst, oxygen is added. Now
conversion takes place over the catalyst. Nitric oxide is optimally formed and the
chance of incomplete oxidation is reduced.
Fig. Dedicated TN liquids module
3.6. Furnace
According to ASTM requirements, the furnace is divided into two temperature
zones.
The temperature in each zone can be adjusted individually, up to 1100°C.
Maximum temperature difference between the zones is approximately 500°C.
Two different furnace tubes are available:

A. Standard furnace tube (for water applications and non-
combustibles)
B. Turbo tube (for petrochemical/hydrocarbon applications and
other “highly flammables”)
Both furnace tubes are supporting all available introduction modules.
3.6.1. Standard furnace tube

Actually, this is an empty tube mostly used for water samples where
chance of soot formation is practically excluded.

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3.6.2. Turbo tube

This tube consists of an extra introduction for oxygen at the rear end of
the furnace tube. (the longer leg at the outlet side)
To optimize combustion of organic solvents, extra oxygen is added and
to improve mixing of combustion gas, a spiral is placed into the second
part of the furnace.
fig. Turbo combustion tube

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3.7. Conditioning
3.7.1. Drying
The gas flow coming from the furnace travels through a Perma pure
membrane dryer. The principle of the nafion perma pure membrane
dryer is the diffusion of water out of the gas stream, by co-polymers with
sulfuric acid ligands.
Fig. Schematic explanation of water removal
3.7.2. C.F.I.S. (patented)

Stability of flow and pressure are extremely important for repeatability and precision,
especially for the ultra low ranges.
The “Controlled Flow Introduction System” is implemented to avoid flow differences in
the reaction chambers. A combination of the controlled combustion, flow restrictions,
pressure control and vacuum devices are used for the control. The total
implementation of this process is a patented system by Thermo Fisher Scientific.

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3.7.3. Molybdenum converter

The molybdenum converter is installed behind the particle filter assembly.
The function of the converter is to reduce NO2 into NO. This will improve the linearity
dramatically, especially in the low range. The operational temperature is 320°C and is
controlled by the software and displayed in the “Analyzer window”.
Fig. Molybdenum converter
3.8. Sulfur detector
Fig: assembly UV detector

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TN-TS 3000 Rev. 2.0.2
3.9. Photo Multiplier Tube

The basic principle of the PMT’s in both the Sulfur- and Nitrogen detector are similar.
Both PMT’s are sensitive to the emitted light, but at different wavelengths.
Smart filter and mirror assemblies will filter out undesirables. The PMT only amplifies
the selected wavelength. A graphical representation of the PMT is found below. The
PMT housing is cooled with the use of a peltier element, in order to reduce dark
current.
Fig. Photo Multiplier
Schematic example of PMT

layout. Once the received
light enters the focussed
area, a cascade multiplier
amplifies the total signal.

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3.10. Detector for Nitrogen
5
3 7
4
1
2
1. PMT housing
2. Gold plated, heated reaction chamber
3. Capillary location (heated)
4. Gas output
5. Ozone input
6. Analyses gas input
7. Heater connection
8. Photo Multiplier connections
9. Cooling block PMT (Peltier driven)

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4. INSTALLATION OF THE 3000 SYSTEM
4.1. Introduction
Before running actual samples on the 3000 system an overall check and
installation procedure has to be carried out.
This chapter will guide you through the installation procedure.
4.2. 3000 system, external connections and specifications

All external connections are on the backside of the 3000 system.
1. Power connections
2. Communication connections
3. Gas connections and specifications
In the next paragraphs, all connections are discussed.
4.2.1. Power connections
The power cable has to be connected to the 3000 system. The 3000
system has two additional power-outputs of 150 VA.
Figure: power sockets 3000 system

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TN-TS 3000 Rev. 2.0.2
Warning
Before turning the 3000 system on for the first
time, the voltage setting must be checked. The
small plate beneath the power lead should be
positioned in a way that the 230 V indication is in
the normal position (not upside down) and is read
from left to right when the operator is facing the
back of the apparatus.
The 115 V indication will then be upside down.
Should you need to switch from a 230 V to a 115
Volts supply, pull the plate away from the
instrument so that the prongs of the plug are fully
withdrawn from the apparatus and re-insert the
other way up.
Electrical Hazard
Do not open the cabinet when the power cable is
connected. Remove it from the wall outlet and
disconnect the cable from the analyzer
completely.
Special Attention
After supplying power to the analyzer and starting
the program, the furnaces and heating elements
will rise to the standard temperatures required by
the connected module. (initialization procedure)
When no module is connected, the apparatus will
go into standby mode (i.e. no furnace control).
4.2.2. Communication connections

The RS232-communicationcord (9 pins) is connected to the 3000
system on the serial port connection. The other side of this cable
(9pins) is connected on the COM1-port of the computer.
Figure: com-connector
Warning
Wrong connections could lead to malfunction of
the analyzer or computer.

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4.2.3. Gasses: connections and specifications

Gas, to be provided by the customer, has to be connected to the 3000
system. The gas specifications for Argon/Helium and Oxygen are:
Argon/Helium (Ar) (He) 99.998% (or better*)

Oxygen (02) 99.6% (or better*)
Maximum pressure 2-3 bar*
Gas connection 1/8”
Figure: gas connections, back-side (1/8” Swagelok)
*Notes*
Preferred pressure settings.
For “manual flow meters” advised pressure is 1-3 bar
For “mass flow meters” advised pressure is 1-2 bar
Gas quality/specifications.
For most applications the above mentioned specifications are valid.
For ultra low level Nitrogen analysis, the specifications may differ.
Usually Argon and Helium are of sufficient quality for analysis below
100 ppb.
Specs for Oxygen (ultra low application): 99.998% (or better)
Background information: Oxygen will most likely contain a small amount of nitrogen
as well. This is normal, considering the process for oxygen production. The better the
oxygen, the lower the expected background is. Oxygen is also the larger part of the
total carrier gas used in the 3000 system. During combustion, NOx may be formed
from the oxidation of mainly hydrocarbons in the presence of nitrogen gas. (the
background in the oxygen) This will produce higher areas for blanks and ultra low
standards, affecting the detection capability of the 3000 system. Most interference’s
are covered by the system itself. The gas quality however should be addressed at
the source. Check with your local gas supplier for the details.

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4.2.4. 3000 system glassware connections

Connect the glass parts using the proper clamps. Make sure that the
connecting areas are clean and free of particles.
Check for leakage between connections in order to ensure correct operation.
The glassware parts are:

1. Sample introduction module
2. Furnace tube
3. Outlet connection
In the next paragraphs, all connections will be discussed.
4.2.5. Sample introduction modules
There are a few differences between the introduction modules for the
3000 system. Two of them have to be installed differently. The
introduction modules are easily interchangeable.
Make sure that the furnace tube (when installed) is supported by the
stainless steel fork.
The different introduction modules are:

1. The "Liquids/Gas module"
2. The "Solids module"
3. The “Water module”
4.2.5.1. The "Liquids module"

Slide the Liquids module into the furnace tube. Connect the gas
connectors (O2: blue on blue and Ar: white on white). Place the
clamp tightly on the connected glass parts and install the Liquids
identity-connector. In case of multiple gas connectors, select the
oxygen connector on the left. This one corresponds with the
second flow meter from the right! The right flow meter
corresponds with the oxygen connector on the right!
4.2.5.2. The "Solids module"

Slide the Solids module into the furnace tube. Make sure that the
white Teflon magnet in the boat module is positioned just above
the white Teflon boat driver. The actual movement of the boat is
transferred using magnets, incorporated in the Teflon. Plug-in the
gas connectors (O2: blue on blue Ar: white on white). Place the
clamps tightly on the connected glass parts and install the “Solids
identity-connector”. In case of multiple gas connectors, select the
oxygen connector on the left. This one corresponds with the

User Manual
TN-TS 3000 Rev. 2.0.2
second flow meter from the right! The right flow meter
corresponds with the oxygen connector on the right!
4.2.5.3. The "Liquids module Water"

Introduce the Water module into the furnace tube and make sure
that the solid i.d. connector is in place. Place the clamp over the
glass connectors and check if connecting surfaces are clean.
Insert the gas connectors. (the single O2: blue on blue, using the
left oxygen connector. Ar: white on white and the mixed oxygen
connector into the right one)
Note: A special TN-Water analyzer is also available. For this

analyzer is an additional manual.
4.2.6. Furnace tube

Slide the quartz furnace tube into the furnace compartment with the
narrow end towards the outlet side. Place the stainless steel fork for
correct support in the boat-driver. (module connection side of the tube)
Special Attention
Avoid touching the surface of the furnace tube with your
bare fingers. The traces of grease left by your fingertips will
create hotspots and reduce the service life of the furnace
tube.
The furnace tube and outlet become very hot during the
operation of the 3000 system. Carelessness may result
in burns. Avoid contact with bare hands. Use special
protective gloves and/or tools for “hot tube removal”.
The safest way for removal is allowing the furnace to
cool down completely.

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4.2.7. Outlet connection (TN)

Connect the outlet glass-connector to the Perma-pure first. When using
a turbo furnace tube: connect the outlet glass connector to the shorter
ball-joint (outlet side) and the extra O2 supply connector to the longer
ball-joint . (O2 feed to the rear end of the turbo tube) see figure: gas
connections/permapure below no: 1 and 7
The installation is similar to the perma-pure connection.
Figure: gas connections/permapure
4.3. Perma pure

To place and connect the Perma pure dryer the following steps are
necessary. Refer to figure: gas connections/permapure above.
1. Connect the inlet of the perma pure to the outlet glass-connector.

2. Connect the gas outlet coming from the vacuum pump to the outside inlet
(for drying)
3. Connect the outlet of the Perma pure to the green glass-fiber filter.

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4.4. Glass-fiber filter

Changing a filter requires the special green filter tool, provided with the
accessories. Disconnect the inlet of the filter and remove the opaque side of
the filter-house, using the provided tool. Replace the glass-fiber filter and
reinstall all parts. There are basically two types of glass-fiber filters. One of
them traps SO2 (paper like filter) and is therefore not suitable. Those are
mainly used for TN analysis only. The one suitable for both TN and TS looks
clearly like glass fiber. Check your application to verify if the correct one is
installed.
If a sulfuric acid scrubber is installed, the filter might be polluted by acid. It is

therefore advised to change the filter after 2 days of measurement.
Filters that are moist by acid, can easily cleaned by thoroughly rinsing them
with distilled or de-ionized water. The cleaned filters can dry in the air at
ambient temperature (for example, by placing them on a tissue).
If the filter shows any damage or pollution, replace it with a new one.
4.5. Gas connection TN-TS, separate and simultaneously
4.5.1. Separate analyses

Total Sulfur can be measured in combination with Nitrogen or other Elements.
A tubing loop on the backside of the TN3000 analyzer dictates the flow path of
the gas. With the loop fully connected, the TN only mode is secured. With the
tubing from the UV-F detector connected to the lower connector only, the TS
only mode is enabled. Pictures for the connections are found in chapter 4.5.4
4.5.2. Simultaneous analyses

Simultaneous analyses is obtained by connecting the inlet tubing from the
UV-F detector into the lower quick connector on the back of the TN3000. The
output of the UV-F detector is connected to the upper fast connector at the
back of the TN3000, leading the gas over the Molybdenum converter, (refer
to chapter 3.7.3) before it enters the TN detector. Pictures for the connections
are found in chapter 4.5.4.

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Figure: Molybdenum converter
Note:
If the PC is equipped with 2 interface boards and the proper
software, simultaneous analyses are possible. Data cables
are connected to the “I” sockets of the PC boards.
4.5.3. Connection furnace outlet TS only

The TN detector applies ozone to the analysis gasses. Hence, this type of
detector is characterized as using a destructive detection method. Therefore,
the TS-UV detector always has to be placed in front of the TN detector.
In principle, for gas conditioning the perma pure dryer will suffice. However, in
order to create a more robust system (less sensitive to soot formation), an
additional scrubber filled with concentrated sulfuric acid van be placed after
the perma pure. See figure below:
UV fluorescence detector
Fig.: TS flow path
Note:
Never use a sulfuric acid scrubber in combination with a TN

User Manual
TN-TS 3000 Rev. 2.0.2
detector. Sulfuric acid reacts with NOx resulting in a too low

recovery.
Connection scrubber glass fiber filter (TS3000010)

KS Clamp with screw nr.12
Coupling (PMECH0368)
In-line filter (PANAL0134)
Connector to gasinlet (ECS30010)

KS Clamp with screw nr.12 (PMECH0006)
Sulfuric acid scrubber (ECS300006)
Fig.: Details Scrubber connections
Fig.: Combination perma pure with scrubber

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4.5.4. Mode selection gas flow: separate or simultaneous
Sulfur Mode Only
Loop in upper connector only.
Gas inlet UV-F detector in lower position 3000.
Simultaneous Mode
UV-F output in upper connector. (into Molybdenum

converter and TN detector)
UV-F input in lower connector.
TN Mode Only
Loop in both connectors. (outlet from particle filter

goes into the molybdenum converter)

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4.6. UV-F detector module
Figure: UV detector module

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4.6.1. Connections and settings on UV-F detector
4
1
2
3
6
Figure: Backside UV-F detector
1. On/Off switch, 230-115 Volt selectable.

2. Power socket.
3. Coaxial connection for data transfer to PC board. (“I” socket PC Board)
4. Gas outlet UV-F detector (used for inlet towards TN detector, sometimes
already provided with tubing and fast connector.)
5. Cooling fan exhaust.
6. Range selectors. (0-5, 0-50, 0-500 PPM) Both switches in the “down
position” 0-5 range. Both in the upper position 0-500 range. Both switches
pointing in different directions (preferably bottom switch down and upper
switch up) enables the 0-50 range.
“High range” refers to high sulfur concentration.

“Low range” refers to low sulfur concentration.
Please note that the “Mid range” runs from 25ppb up to approximately 50 ppm!!

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For most applications the mid-range is considered the “ideal working range”
Warning
Before turning the UV detector module on for the
first time, the voltage setting must be checked.
The small plate beneath the power lead should be
positioned in a way that the 230 V indication is in
the normal position (not upside down) and is read
from left to right when the operator is facing the
back of the apparatus.
The 115 V indication will then be upside down.
Should you need to switch from a 230 V to a 115
V supply pull the plate away from the instrument
so that the prongs of the plug are fully withdrawn
from the apparatus and re-insert the other way
up.
Electrical Hazard
Do not open the cabinet before the power cable is

removed.
Special Attention
With power supplied to the UV detector, the
heating elements will rise to the standard
temperature required for optimum performance.

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5. OPERATING THE 3000 SYSTEM
After installation, the 3000 system is ready for operation. The following paragraphs
should be read carefully. Please note that the software manual should be read before
the 3000 system is switched on.
Special Attention
Read the software manual for the 3000 system before operating
the 3000 system.
5.1. 3000 system Start up

Before starting the 3000 system, several standards should be prepared. In
the next paragraphs the following subjects are described:
1. Preparation of standards
2. Furnace tube and permapure connection
3. Module connection
4. Powering the system
5. Adjust gas flow
6. Gas leakage test
5.2. Preparation of solutions

All necessary solutions, needed for good analysis are described below.
5.2.1. Sulfur standards
5.2.1.1. Dibenzothiophene stock solution (sulfur determination)

To make a stock solution of dibenzothiophene dissolve 1436.66 mg of
dibenzothiophene (= diphenylene sulfide; C12H8S) in 200 mL xylene (= 1,2-
dimethylbenzene, 1,2-(CH3)2C6H4; p.a.). Fill with xylene to 250 mL. Mix the
solution thoroughly.
5.2.1.2. Dibenzothiophene standard solution (100 mg S/L)

Pipette 10 mL of the dibenzothiophene stock solution in a 100 mL measuring
flask and with xylene to 100mL. Mix the solution thoroughly.
5.2.1.3. Dibenzothiophene standard solution (50 mg S/L)

Pipette 5 mL of the dibenzothiophene stock solution in a 100 mL measuring
flask and with xylene to 100mL. Mix the solution thoroughly.

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5.2.1.4. Dibenzothiophene test solution (10 mg S/L)

Pipette 10 mL of the dibenzothiophene standard solution in a 100 mL
measuring flask and with xylene to 100 mL. Mix the solution thoroughly.

Pipette 5 mL of the dibenzothiophene standard solution in a 100 mL

Pipette 10 mL of the dibenzothiophene test solution (10 mgS/L) in a 100 mL
5.2.2. Nitrogen standards (petro)
5.2.2.1. Carbazole stock-solution (nitrogen determination)

In a 1000 mL volumetric flask 11.937 g of carbazole has to be dissolved with
approximately 800 mL acetone. Fill the flask with acetone to 1000 mL
after dissolving the carbazole for the preparation of this carbazole stock-
solution with a nitrogen concentration of 1000 mg N/L. Homogenize the
solution.
5.2.2.2. Carbazole standard solution

Pipette 10 mL of the stock-solution into a volumetric flask of 100 mL and fill the
flask to 100 mL with acetone. The homogenized standard solution contains
100 mg N/L.
5.2.2.3. Benzonitrile stock-solution

In a 250 mL volumetric flask 9.20 mg of benzonitrile has to be diluted1 with
approximately 200 mL toluene. Fill the flask with toluene to 250 mL after
dissolving the benzonitrile for the preparation of this benzonitrile stock-solution
with a nitrogen concentration of 5000 mg N/L. Homogenize the solution.
5.2.2.4. Benzonitrile standard solution

Pipette 20 mL of the stock-solution into a volumetric flask of 100 mL and fill the
flask to 100 mL with toluene. The homogenized standard solution contains
1000 mg N/L.

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5.2.3. Nitrogen standards (water)

The Thermo Fisher Scientific TN3000-water analyzer is capable to measure
total Nitrogen in aqueous samples in a range of 0.2 to 100 ppm N. Since the
working principle of this analyzer is based on the combustion of samples in the
presence of oxygen, it is obvious that the conversion of samples into nitric
oxide (NO) is strongly dependent on the type of nitrogen containing molecules.
For example, Ammonia (NH4+) will consume much more oxygen than Nitrate
(NO3-). Hence, these molecules will generate a different yield in case
analyzed simultaneously.
The TN3000-water is guaranteed to keep this Ammonia-Nitrate ratio below
10% deviation according to the NVN-EVN 12260 and DIN 38409 norms, within
the range 0.2 up to 25 ppm.
Preparation of the standards

Standard a TN water is calibrated with a range of Glycine standards. If
Ammonia and/or Nitrate is important, the system can be calibrated with
separate standards or with a mix standard.
If totally different types of samples have to be measured, it is advisable to
calibrate with more representative standards.
In below shown table, the mass that has to be weighed for the most commonly
applied standards.
Nitrate Ammonia Mix Glycine
Conc. N mg KNO3 mg (NH4)2SO4 mg KNO3 and mg (NH4)2SO4 mg C2H5NO2
Name Formula MM Molfr N mg N/L per L per L per L per L
Potassium Nitrate KNO3 101.1 0.138 1 7.22 4.72 3.61 + 2.36 5.36
Ammonium Sulfate (NH4)2SO4 132.13 0.212 2 14.44 9.44 7.22 + 4.72 10.72
Glycine C2H5NO2 75.06 0.187 5 36.11 23.59 18.05 + 11.80 26.81
10 72.21 47.19 36.11 + 23.59 53.61
25 180.54 117.97 90.27 + 58.99 134.04
50 361.07 235.95 180.54 + 117.97 268.07
75 541.61 353.92 270.80 + 176.96 402.11
100 722.14 471.89 361.07 + 235.95 536.14
Stock solution >>> 1000 7221.43 4718.93 3610.71 + 2359.46 5361.43
Nitrate standards are, in general, a very good nutrition source

for microorganisms. Always store the standards in a cool
(approx. 5 °C) and dark place.
5.2.3.1. Preparation of the Nitrate stock

Exactly weigh 7221 mg of anhydrous Potassium Nitrate. Quantitatively transfer
it to a measuring flask of 1000 mL using de-ionized or distilled water.
Exactly fill the flask to 1000 mL. Mix (shake) the solution thoroughly.

User Manual
TN-TS 3000 Rev. 2.0.2
5.2.3.1.1. Preparation of the 100 ppm Nitrate standard

Pipette 10 mL of the Nitrate stock solution into a measuring flask and fill to 100
mL with de-ionized or distilled water. Mix the solution thoroughly.


Pipette 2.5 mL of the Nitrate stock solution into a measuring flask and fill to
100 mL with de-ionized or distilled water. Mix the solution thoroughly.



5.2.3.2. Preparation of the Ammonia stock

Exactly weigh 4718 mg of anhydrous Ammonia Sulfate. Quantitatively transfer
it to a measuring flask of 1000 mL using de-ionized or distilled water.
5.2.3.2.1. Preparation of the x ppm Ammonia standard

Please follow the same procedure as described for the Nitrate standards using
the Ammonia stock solution. (Paragraph: 5.2.3.1.)
5.2.3.3. Preparation of the Ammonia-Nitrate mix stock

Exactly weigh 3610 mg anhydrous Potassium Nitrate and 2359 mg anhydrous
Ammonia Sulfate. Quantitatively transfer both salts to a measuring flask of
1000 mL using de-ionized or distilled water.

User Manual
TN-TS 3000 Rev. 2.0.2
5.2.3.3.1. Preparation of the x ppm Ammonia-Nitrate mix standard

the Ammonia-Nitrate mix stock solution. (Paragraph: 5.2.3.1.)
5.2.3.4. Preparation of the Glycine stock

Exactly weigh 5361 mg Glycine. Quantitatively transfer it to a measuring flask
of 1000 mL using de-ionized or distilled water.
5.2.3.4.1. Preparation of the x ppm Glycine standard

the Glycine stock solution. (Paragraph: 5.2.3.1.)
5.2.4. Furnace tube and permapure connection

Slide the furnace tube into the oven and connect the permapure to the outlet to the
furnace using the outlet glass-connector. Connect all tubing to the permapure as
described in paragraph 4.3
5.2.5. Module connection

Place the introduction module and connect all the tubing. Connect the module with
the clamp to the furnace tube. Install all gas connections (blue at blue and white at
white) and the ID-connector belonging to the module. (refer for detailed info for the
specific modules to 3.5 and 4.2.5

User Manual
TN-TS 3000 Rev. 2.0.2
5.2.6. Powering the system

If all steps above are carried out carefully and the instrument is connected
to a computer, the 3000 system can be switched on with the ON/OFF
switch on the backside of the instrument.
1. Switch on the 3000 system (note that the detectors needs a 30
minute startup before operational temperatures and general
performance conditions are reached. In case of UV start-up a dim
ticking is heard after a few seconds. This is the UV Flasher lamp
and is considered a normal sound. The TN detector heat-up as
soon as the basic unit is switched on, without any particular sound.
2. Switch on the vacuum pump (small switch at the back-side)
3. Switch on the computer
4. Start the TN/TS analyzer software by clicking on the Thermo Fisher
Scientific software icon.
5. Check if communication is established between PC and the 3000
system. This is visually checked in the “System status screen”. If there
is no communication, please check if the correct “com port” is selected
or actually connected. Furnace temperatures and system parameters
can be adjusted and monitored.
6. Check if both the UV module and/or the TN outputs are connected to
the data acquisition board(s) and if a baseline signal appears. The
data cable runs from detector into the “I” socket of the data acquisition
board in the PC. Without the correct settings, the signal of the UV
detector could appear to be noisy.
At this point the instrument needs time to stabilize.
5.2.7. Adjust the gas flow (Manual)
Note: Depending on the configuration, manual or digital gas flow

controllers are installed. In case digital mass flow controllers are
installed, all settings will be automatically done by the ThEuS software.
Below described steps are in that case not necessary.
Before operation, gases have to be supplied with a maximum pressure

of 3 bar. (normal flow meters as seen below)
The supplied gas tubing can be used to hook-up the analyzer.
Open the gas headers on the gas supply line in the following order.
1. Close all flow meters by turning the black knob in the clockwise
direction. (do not over-tighten)
2. Open the gas headers on the gas supply line.
3. Open the flow meters by turning the black knob counter clockwise.

User Manual
TN-TS 3000 Rev. 2.0.2
Figure: Flow meters
E A
The introduction module has to be installed before the five flow meters
are adjusted.
From right to left:
A. Argon/Helium flow meter

B. Oxygen Furnace flow meter
C. Oxygen Extra flow meter
D. Oxygen Bypass flow meter
E. Oxygen Ozone flow meter
The different settings for water, organic -liquids and -solids are given at
Appendix I.
Note: The number of manual flow meters can differ per system
depending on the configuration.

User Manual
TN-TS 3000 Rev. 2.0.2
5.2.8. Gas leakage test basic 3000 system
Procedure 1
For reliable and accurate analysis the 3000 SYSTEM needs to be free of leakage.
Therefore a gas leak test has to be performed.
The next steps explain the gas leak test:
1. Close the flow meters for the oxygen-supply and lower the Argon-flow to
approximately 5 mm.
2. Disconnect the permapure from the particle filter and insert a separate piece of
tubing into it (length about 50 cm and diameter ¼”)
3. Fill a small beaker with water and insert the outer part of the tubing into the water.
4. Observe the flow in the beaker. There still has to be a low flow of bubbles visible.
5. This demonstrates that even at low flow-rates the gas coming from the permapure
dryer, arrives without significant leakage.
Gas leakage test ok > proceed with analysis.
Gas leakage test false > proceed with next steps.
The furnace tube, outlet, modules, joints, etc may become very
hot during the operation of the 3000 SYSTEM. Carelessness may
result in burns.
Procedure 2
1. If there are no bubbles visible, a gas leakage has to be fixed. Adjust flows to the
“normal” levels. (setting according current method)
2. Disconnect the gas stream between furnace output and the “permapure
connection”.
3. Manually obstruct the gas stream on the outlet of the furnace tube (using a
septum) and observe the flow meters. They should drop approximately 5-10 mm
within 10-15 seconds. (do not block the flows longer than that) Removing the
septum from the output should clearly release pressure from the tube. This
indicates that no gas-flow leakage is present in the connectors, Module, Furnace-
tube and other joints. The leakage has to be further down the flow path. (leakage
could be found in the septum of the module, any gas connector, glass joints,
loose clamps, mineralized furnace tube, etc.)
4. Connect the “permapure dryer” again and obstruct the flow, coming from it. The
flow meters should drop approximately 5-10 mm within 10-15 seconds. Removing
the septum from the output should clearly release pressure from the permapure
dryer. This indicates that no gas-flow leakage is present in all connected parts in
User Manual
TN-TS 3000 Rev. 2.0.2
the flow path. The leakage has to be further down the flow path. (leakage could
be found in the gas connector going to the particle filter, the glass joints, due to
dirt on the grind surface, the furnace tube ball-joint, etc.
5. Resolve any other leakage problem found in the flow path and test it.
6. Finally connect a separate piece of tubing to the outlet connection of the particle
filter (see picture chapter 4.5.4 )and run the test from “procedure 1” again.
7. The final check will be the number 3-5 step from procedure 1.
Following these steps should clearly lead to the “problem” and solution in the flow
path.
5.2.9. Gas leakage test UV detection module

For reliable and accurate analysis the 3000 system needs to be free of
leakage. Therefore, a gas leak test has to be performed.
The next steps will guide you trough a gas leak test:
1. Check all connections and glassware for proper installation.

2. Close the oxygen-supply and adjust the Argon/Helium flow to 5 mm.
3. Connect a piece of tubing to the gas outlet of the 3000 system, or
the outlet of the UV module.
4. Put the outlet of the tubing in a glass beaker with water and observe
if small bubbles appear. (if not than a leakage or blockage is most
likely)
5. Reconnect the UV module (if applicable) and set gas flows to
proper levels again.
6. Cleaning glass connections, replacing septa and maintaining all
connectors in proper condition should prevent most of the leakage
problems.

User Manual
TN-TS 3000 Rev. 2.0.2
5.3. 3000 system normal operation

The software controls the operation of the 3000 system. Methods are
described in the 3000 system software manual.
During normal operation, regularly small maintenance has to be carried out.
The next paragraphs will describe the following subjects:
1. Visible inspection of glassware

2. Glassware maintenance
3. Introduction module
4. Standard set points
5.3.1. Visible inspection of glassware

All glassware parts should be checked regularly, once a week, on
scratches, disposals and blocking of the gas path. After the inspection a
gas leak test should be performed. The frequency of inspection
depends strongly on the sample matrix. Samples containing high
concentration of salts or metals could increase the number of
inspections. It is considered normal that the service life of quartz is
reduced because of this.
5.3.2. Glassware maintenance
5.3.2.1. Furnace tube

In the furnace tube soothing is one of the causes of the memory
effect. Mineralization can also cause the same effect (the tube
sometimes becomes slightly porous).
Soot deposited at the end of the furnace tube is relatively easy to
remove.
1. Remove the clamp between the tube and the Perma pure.
(end of the tube)
2. Remove the clamp of the “turbo oxygen”. (end of the tube)
3. Remove the clamp which connects the module to the tube
(front of tube) and remove the module.
4. Remove the latch (stainless steel fork) between the tube
and the module. (front of tube)
5. Set the furnace temperature to 1000 oC and pull back the
tube halfway (it should be clean in 10 minutes).
The tube could become opaque on the inside and sometimes on

the outside. This is recognized as mineralization of the furnace
tube. In some cases, Thermo Fisher Scientific can remedy this.
Please contact the Thermo Fisher Scientific Service Department
or your local representative for more information.

User Manual
TN-TS 3000 Rev. 2.0.2
5.3.2.2. SOLIDS glassware

During solids analysis, the boat and/or frit after many analyses
may cause a memory effect. By introducing samples into the
furnace tube too fast, condensation could appear into the sample
introduction section of the solids glassware. If this happens, a
second peak can occur when the hot boat returns from the
furnace. If this is visible, the glassware must be cleaned in an
oven at approximately 500 oC. Please contact the Thermo Fisher
Scientific Service Department for more information.
The effect may be caused by mineralization of either the boat or
the frit, or both. Replacing them may be the only solution. The
service life of the sample crucible and the boat often depends on
the number of runs, the nature and components in the sample.
5.3.3. Introduction module
5.3.3.1. Solids Module

Replace the septum when necessary but at least every week. If a
new sample boat is used or the boat is dirty, clean this by
introduction into the furnace tube during 4 minutes at 1000 oC.
5.3.3.2. Liquids Module

Replace the septum when necessary, but at least once every
week. (service lifetime when auto sampler is used is usually
longer)
5.3.3.3. TN water module

This is a special module and is supplied with additional hardware.
Please refer to the separate TN-water user manual for details.
5.3.4. Standard software settings

The software controls most of the set points. These parameters are
related to a method. These methods describe all parameters necessary
for running a number of applications.
The software manual describes how these methods are made.
An example of set points is given at Appendix I. For more information
refer to the software manual.

User Manual
TN-TS 3000 Rev. 2.0.2
5.3.5. Running analysis
In this paragraph a brief explanation will be given how to start working with
the ThEuS™ software supplied with the analyzer. For more details please
refer to the manual on the ThEuS™ CD or to the interactive manual build into
the help function of ThEuS™.
5.3.5.1. Starting ThEuS™

ThEuS™ is installed on the computer supplied by the system. Also a CD is
included in the shipment. If no computer was included, please install
ThEuS™ by inserting the CD into de CD-drive of the computer connected to
the analyzer. The installation will start automatically. Please refer to the
installation manual for more details.
Start ThEuS™ by clicking the icon on the desktop:
If the system is installed by an engineer from Thermo, the right
configuration and method(s) are already installed on the computer.
If not, please contact your local Thermo representative.
After ThEuS™ is started a queue of samples must be entered.
To do this, open the Queue manager.
In the following window, click the New Queue button and enter a name for
the Queue that has to be created.

User Manual
TN-TS 3000 Rev. 2.0.2
Next, click the Add button. The following window will appear:
For analyzing samples, not creating a calibration line, select as ‘Type’

sample. Then enter the following data in the boxes:
Sample name The name of the sample to be analyzed
Amount The quantity of the sample + unit (pull down)
Concentration unit Pull down selection: Unit in which the result will be
calculated/shown
Begin sample position If an auto sampler is present, in this box the
position of the sample is entered. Note: If in the
box ‘Number of samples’ a value larger then 1 is
entered, this box will indicate the start position of
first sample in a row.
Dilution If the sample has been diluted in this box the
dilution factor can be entered. Note: By double
clicking on this box a dilution calculation wizard is
activated. Please refer to the software manual for
more details.
Density If for example the sample is dissolved in toluene
the density (e.g. 0.85) for this solution can be
entered. This value is used for calculating the
analyzed concentration.
Method Depending on the configuration of the system, one
or more methods available. Select from this pull
down menu the right method. Note: A method is
sequence of action steps necessary for performing
an analysis. Refer to the software manual for more
details.
Analyst name Enter the name (your name) of the analyst
Sample Comment In this box additional information can be entered.
This information will be stored together with the
analysis results.

User Manual
TN-TS 3000 Rev. 2.0.2
Number of samples Normally 1 is entered. However, if more similar

(duplicate) samples have to be analyzed, a value
larger then 1 can be entered. Note: This will only
work when an auto sampler is present. Also see
Sample start position.
Analysis per sample In this box the number this sample has to be
analyzed has to be entered.
After all parameters have been entered, click the OK button. Above shown
example will generate the following queue:
By clicking the Add button again, the next (set of) sample(s) can be added.
Repeat this action until all desired samples have be added to this queue.
When finished adding samples click the analyze button. A similar window will
appear:
Make sure ‘Analyze Queue’ is selected

(tagged) in order to analyze the whole queue.
Then click the OK button. The analyses will
start. Note: If no auto sampler is present, a
question will pop up asking the user to
inject/insert the sample.

User Manual
TN-TS 3000 Rev. 2.0.2
5.3.5.2. Creating a calibration
Creating a calibration line is similar to analyzing samples as described in the

previous paragraph. Instead of selecting ‘sample’ as type, select ‘calibration’.
In addition to the normal ‘sample’ information, the name of the calibration line
and the known concentration have to be entered.
If in the box ‘calibration line’ the option new is selected, a new calibration set
will be created. In that case a new name is requested:
In this menu, the new name the calibration order, signal and through zero
has to be selected/entered. The order is in case of a coulometer (TX and TS)
Is used, the order should be ‘Absolute’, otherwise in most cases a first order
(linear) is applied. Note: Afterwards the order can always be changed. If the
system has more then one (parallel) detector the desired signal has to be
selected. ‘Through zero’ is used to force the calibration line through the zero
point (0,0).
Similar to analyzing samples, by clicking the ‘analyze’ button, the calibration

standards are measured and calculated into a calibration curve.
For more details please refer to the manual provided with the software.

User Manual
TN-TS 3000 Rev. 2.0.2
5.4. Quick performance check TN/TS mode
Before actual samples are introduced an overall performance of the 3000 system
must be performed. If these test results are within the specification, samples- and
calibration procedures may be carried out, without further system proofing.
Before actual shipment to the final destination of the system a “factory calibration” is
carried out. This information is found in the test report, sent along with the system.
In the report test results and calibration data is found.
The data clearly shows the generated area for a specific standard.
This value may be used as an “absolute reference” for system performance.
By injecting standards with an injection speed of 1µL/s, using the appropriate “liquids
module” manually or with the auto sampler a comparable result should be found.
5.4.1. TN mode test (setting is low range)

A 100 mg N/L standard is injected at 1 µL/s. With flow- and temperature settings
according the “liquids application” for hydrocarbons the integrated area generated for
a 50 µl injection volume should be approximately 100.000 mV.
For 100 µL it should be 200.000 mV.
Maximum signal level is approximately 2100 mV. Above this level the signal may
appear flat-lined, indicating that the maximum level is reached and the result of the
total integration should be ignored.
Double-checking it with a 50 mg N/L standard should give half the area.
If the above mentioned areas are obtained, the system functions correctly and
calibration and analysis may be carried out. Incorrect areas (reduced with10% or
more) are an indicator of malfunction. In this case gas test 5.2.8 and overall system
check will have to be carried out.
5.4.2. TS-UV mode test (setting is mid-range)

A 50 mg S/L standard is injected at 1 µL/s. With flow- and temperature settings
according the “liquids application” for hydrocarbons the integrated area generated for
a 50 µL injection volume should be approximately 100.000 mV.
For 100 µL it should be 200.000 mV.
Maximum signal level is approximately 2100 mV. Above this level the signal may
appear flat-lined, indicating that the maximum level is reached and the result of the
total integration should be ignored.
Double-checking it with a 25 mg S/L standard should give half the area.
If the above mentioned areas are obtained, the system functions correctly and
calibration and analysis may be carried out. Incorrect areas (reduced with10% or
more) are an indicator of malfunction. In this case gas test 5.2.9 and overall system
check will have to be carried out.

User Manual
TN-TS 3000 Rev. 2.0.2
5.5. 3000 system Standby mode
When no analysis are carried out for a short period of time, (one to several
days) it is recommended to put the 3000 system in standby mode.
Some customers however prefer to maintain standard operational

parameters, including gas flows. If the desire is to shut down the vacuum
pump only, than do close the oxygen supply to the ozonator! This will prevent
the production of ozone, which could affect the performance of several
devises in the 3000 system. The ozone killer inside the 3000 system only
functions properly with the vacuum pump switched on!
Warning
Whenever the vacuum pump is shut down, than do close the
oxygen supply to the ozonator! This will prevent the production
of ozone, which could affect the performance of several
devises in the 3000 system.
Follow the next steps:

1. Close header gas supply or close flow meters by turning the black knob
counter clockwise.
2. Set the following temperatures:
Heating Setpoint
Inlet temp 25°C
Furnace 1 700°C
Furnace 2 700°C
Converter 25°C
Now the instrument is in standby mode.
5.6. 3000 system shut down
When no analysis are carried out for a longer period of time it is

recommended to shut the 3000 system down.

clockwise.
2. Shut down the software.
3. Switch off the 3000 system. (do not pull the power plug in order to keep
cooling fans running)
Now the instrument is turned off.

User Manual
TN-TS 3000 Rev. 2.0.2
6. TN Water
6.1. Introduction
This manual is an addition to the TN3000 manual and replaces the paragraphs
in this manual concerning the water configurations.
In contradiction to Total Nitrogen analysis in non-aqueous applications,
additional care of the glassware is essential in order to insure a typical life span.
In addition to this special care, some of the parts will have a relatively short life
span. The main problem with aqueous samples is that often salts are present
(i.e. sea water).
O 2/Ar mixture
Injection into boat

Introduction in furnace
Combustion
Cold trap (drying)
Filter
Water + Salts Detection
Salts will induce, at high temperatures, re-crystallization of quartz resulting in a

very brittle and even porous structure. This problem can be reduced by (very)
slowly injecting the sample into the furnace. However, this is not a practical
solution because of easy blockage of the injection needle and in many cases a
wrong NO3/NH4 ratio. The principle behind this new technique is to introduce
the sample in a fast way, while it is released (evaporated) only then when the
sample is it is in a ‘safe’ environment (e.g. inside the ceramic furnace tube). In
order to do this, the sample is injected into a nickel cylinder filled with quartz
wool and the transported into the furnace using a quartz boat. Please see
paragraph 6.7 for details about the flow diagram.

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TN-TS 3000 Rev. 2.0.2
6.2. Specifications
6.2.1. Standardized methods

In Europe the two most common methods for analysis of Total Nitrogen in
water are: NVN-EVN 12260 and DIN 38409.
A summary of the most significant parameters is given in the table below:

Norm
NVN-EVN 12260 DIN 38409 Remark
Range 0.5 .. 200 > 0.5 mg/L

Injection volume 'Suitable' Not specified
Particles < 0.45 µm Not specified
Calibration points 0, 10, 20, 40, 60, 80, 100 ppm
Linearity Not specified < 0.1%
Recovery Δslope <10%* ± 5% * between 20 ~ 80%
10ppm Glycin min. 95% Not specified of the working range
1-100ppm(NH4)2SO4 min. 95% Not specified
10-50ppm KNO3 97 ~ 105% Not specified
6.2.2. Test results of the TN-3000 water

Although the total range of the TN-3000 is larger than specified in NVN-EVN
12260, it is split into two measurement ranges. Depending on the type of
sample the low range can go up to 100 ppm and the high range up to 2000
ppm. Typically in the low range it will be possible to analyze 1…75 ppm of
Ammonia, Glycin or mix standards/samples. Although it is possible to
measure 0.5 ppm, it is advised to apply a standard addition method when the
expected concentration is below 1 ppm. (Remark: If desired, Thermo Fisher
Scientific can supply a method that automatically adds a standard prior to
analysis.)
The conditions used to obtain the following results are:
Inj. Vol. 175µL Boat program

Add. Water 100µL Pos Speed Delay
Inj. speed 50µL/min (mm) (mm/min) (s)
Ar Flow 300mL/min 90 10 50
O2 Flow 300mL/min 100 1 100
O2 Ozonator 110mL/min 170 2 65
Furnace 1 1000°C 0 2 5
Furnace 2 1000°C
NOx scrubber 320°C

User Manual
TN-TS 3000 Rev. 2.0.2
Calibration 1mg/l ~ 50 mg/l
160000
140000
120000
100000
area (mV/s
NH4
80000 NO3
Glycin
60000
y = -16.064x2 + 3083.6x - 538.37
R2 = 0.9996
40000
y = -1.46x2 + 3050x + 228.86
R2 = 0.9999
20000
y = -15.97x2 + 2728.9x + 922.68
R2 = 0.9996
0
0 10 20 30 40 50 60
conc. (mg/l)
Calibration 1mg/l ~ 25 mg/l
80000
70000
60000
50000
area (mV/s
NH4
40000 NO3
Glycin
30000
y = -17.581x2 + 3122.7x - 647.06
R2 = 0.9999
20000
y = -4.8538x2 + 3136.6x - 4.5776
R2 = 0.9999
10000
y = -25.542x2 + 2981.6x + 131.84
R2 = 0.9998
0
0 5 10 15 20 25 30
conc. (mg/l)
6.2.3. Summary/conclusion
The TN-3000 water system with Nickel boat introduction and cold trap works
good within the in NVN-EVN 12260 and DIN 38409 normalization providing
the total Nitrogen concentration is below 25 ppm and the Ammonia-Nitrate
relation is relevant. If this relation is not relevant, concentrations up to 2000
ppm can be measured.

User Manual
TN-TS 3000 Rev. 2.0.2
Range
Low High
Injection volume 1 ~ 800 1 ~ 800 µL
Typ. Inj. Vol. 200 200 µL
Within NVN/DIN
Ammonia 0.5 ~ 25 - ppm
Nitrate 0.5 ~ 30 - ppm
Extended
Ammonia 0.2 ~ 75 1 ~ 1000 ppm
Nitrate 0.2 ~ 40 1 ~ 750 ppm
Glycin 0.2 ~ 80 1 ~ 1000 ppm
Particles < 250 < 250 µm
6.3. Maintenance of the glassware
6.3.1. Boat and introduction module

If the system is operated normally, the only part on the introduction (AOX)
module that has to be replaced is the septum. Normally this is done approx.
once a month, depending on the number of samples analyzed.
The quartz boat, however, has to be handled as a consumable. Depending

on the number of samples per time period and the salt contents of the
analyzed samples, the life span of a boat can vary from a few weeks to at
least three months. The sample is injected into a Nickel cup filled with quartz
wool. This cup will be quickly oxidized (often turns green) and will become
brittle. After prolonged use, it will happen that sample will leak through onto
the quartz boat resulting in gradual re-crystallization of the quartz. If the
Nickel cups are not replaced in time, the quartz boat will be destroyed
resulting in splinters of quartz, quartz wool, Nickel and salt deposits in the
furnace tube. Do not remove the tube for cleaning, but use the special
scraper tool provided with the system. (Refer to the previous paragraph for
details.)
When the analyzer is not used for a longer period and is put into a
‘hibernation’ state, leave the boat in the cooled (zero) position (e.g. not inside
the furnace). This will increase the life span of the boat significantly. To
ensure a good base line, enter the boat a few times for a few minutes before
starting new analysis.

User Manual
TN-TS 3000 Rev. 2.0.2
Injection opening
Nickel sample cylinder
Main vapor opening

Quartz wool
Magnet
Quartz holder Quartz boat
Quartz wool; for fixation

Quartz holder Magnet
Little edge for locking the position Quartz boat with Nickel sample cylinder
6.3.2. Outlining of the boat

The position of the boat and nickel sample cup can be adjusted by turning
the screw on the end (right side) of the introduction module:
Turning the screw clockwise will move the boat more towards the furnace.
Note: Make sure that the boat drive (magnet) is in its home position.
6.3.3. Replacement of the Nickel sample cylinder

The with quartz wool filled Nickel cylinders are a consumable and can be
ordered at you local distributor. Depending on the type of samples, injection
volume and frequency of analyses, the life span will vary significantly. Please
frequently check the integrity of the cylinder and replace it if necessary.
Warning
Salts of Nickel can be toxic. Handle with care.

User Manual
TN-TS 3000 Rev. 2.0.2
Looking closely to the boat, a little fixation point can be seen. Make sure that
the Nickel sample cylinder is ‘locked’ properly at this point while the injection
opening is pointed up. As shown in the figure above, a little ball of quartz
wool is put into the quartz boot first before inserting the Nickel sample
cylinder. This extra wool is to better fixate the cylinder.
Fixation point
When to replace the Nickel cylinder: During normal use, the cylinder will
remain more or less the same shape. It will, however, become brittle or
porous. Also the color can change to gray and/or green. If the cylinder is
visually damaged (dents or cracks) this might be the result of a bad
alignment of the quartz boat and/or the auto sampler.
6.3.4. NeXYZ auto sampler

Normally, the calibration of the auto sampler is done by a service engineer
from Thermo Fisher Scientific. However, it is advisable to check is the side
outlet of the needle is pointing towards the furnace. In this way, it is ensured
that the sample is distributed evenly through the quartz wool and is
concentrated at the front of the boat. Checking the outlet position of the
needle can best be done when the sampler is running a washing cycle
(waste position).
Depending on the applied method (and syringe size), sample volumes up to
2 mL can be used. However, a typical value is 175 µL.
6.3.5. Furnace tube and outlet

The quartz furnace tube is provided with a ceramic inlay. This inlay protects
the furnace tube from salts. An additional advantage is that the inlay has a
much higher heat capacity resulting in less cooling of the furnace when large
quantities of sample are introduced. A disadvantage is that if the furnace tube
has to be removed from the furnace, this has to be done very slowly (approx.
1 cm/min). If the tube has to be cleaned from e.g. parts of a broken quartz
boat, try to use the scraper tool supplied with the system. The best way to
collect the debris and other deposits is to make a little U-shaped ‘boat’ from a
few layers of Aluminum foil and place this under the inlet of the furnace tube.
With the scraper tool, the fragments can be shoved into the Aluminum foil. If
User Manual
TN-TS 3000 Rev. 2.0.2
some material is stuck between the ceramic inlay and the quartz tube, just
leave it there. This can do no harm to the system. When some quartz
splinters can not be removed with the scraper tool they can also pushed
further into the furnace. Normally this material will not influence the
Scraper tool
measurements.
Is an analyzer is not used for a longer period of time it is common practice to
lower the furnace temperature and reduce the gas flows. In this case, it is
strongly advised not to set the furnace temperature below 750°C. The gas
flows can be reduced to approx. 15 mL/min. If the furnace outlet is
disconnected from the cold trap, the flows can even be set to zero.
The outlet (quartz tube) from the furnace can easily be removed by releasing
the clamp and the wedge nut.
Warning
Please be very careful, the part that is normally inside the
furnace is around 1000°C.
Let it cool to room temperature in a save place (for example on a metal

plate). If cooled sufficiently it can be washed using tap water.
TN filter
None return tube
Furnace outlettube
The none return tube (or recoil tube) is to prevent water from the cold trap
going back to the furnace in case the gas flows totally stop.

User Manual
TN-TS 3000 Rev. 2.0.2
Warning
This recoil tube is an additional safety device to prevent water
going back to the furnace. However, the used must always
disconnect the cold trap prior to setting the gas flows to zero.
The non return tube must be clean, upright and in the correct direction (gas
must flow from the furnace to the cold trap). If the outlet- or recoil tube is dirty
it can be easily cleaned with tap water. Before rebuilding the system, please
dry these parts for example with compressed air.
6.3.6. Principle of the furnace outlet tube

Without this new developed outlet tube mineralization of the end of the quartz
furnace tube (the ‘dead zone’) will occur very fast. To prevent this a zone of
non-turbulent gas is created. See figure. The long inner tube will prevent
large deposits of salts to form by creating a dead volume. Of course the inner
tube itself will eventually be destroyed due to re-crystallization.
Furnace tube Ceramic inlay
Outlet Tube
‘Dead zone’

User Manual
TN-TS 3000 Rev. 2.0.2
6.3.7. Cold trap, tubing and filter

The cold trap is located in the extra module housing. It is designed to trap
water, salts and particles like soot. The trap is filled with water with a low pH.
Filling it, can be done with normal tab water acidified with a few drops of a
strong acid like sulfuric or phosphoric acid. Filling can easily be done through
the small air inlet located on the siphon tube. Optimal level of the liquid in the
cold trap is approx. 80% of the lower chamber. The washing liquid is cooled
to approx. 4°C to ensure a low partial vapor pressure.
Gas outlet
Splash dep ressor and Air inlet/
co oling o f gas/va por Fill input
Siphon tube
Varia ble depth
Gas inlet
Cooled water
(with Salts an d
soot particles)
Excess water outlet
When the system is running fine and the applied method is sufficiently
optimized, the liquid level in the cold trap should be more or less stable and
small amounts of water will be pushed out. This level can be adjusted by
shifting the siphon tube higher or lower (first loosen the red wedge nut). It
can be necessary to adjust the height after some time, depending on the
pollution of the filter (more pollution, higher pressure, higher siphon tube).
Another point that can be adjusted is the gas inlet
However, normally this inlet has to be installed just above the bottom of the
lower chamber. Make sure, no gas bubbles can escape directly to the
overflow siphon. Place a beaker under the overflow tube.

User Manual
TN-TS 3000 Rev. 2.0.2
In case an additional detector is connected (for example a CO2 detector (for

TOC measurements)), the pressure inside the cold trap can become too high
resulting in constantly pushing out all the water. In this case an alternative for
the siphon tube is used. This tube has a little valve. During normal operation,
this valve has to be closed. Depending on the number of samples and the
injected volume, the cold trap will slowl fill up. Please frequently check the
level and when necessary shortly open the valve so, the excess of water is
pushed out. Note: The height of this tube does not have to be adjusted like
the siphon tube.
If the tubing (from the furnace outlet to the cold trap and from the cold trap to
the green filter housing) is polluted or wet, disconnect it and wash it with
ample water. Dry it with compressed air.
Depending on the type of samples, the special paper filter in the green filter
housing can be polluted with salts or other deposits. If so, replace the filter
according to the instructions in de TN3000 manual supplied with the system.
Warning
The deposits on the filter may be toxic.

User Manual
TN-TS 3000 Rev. 2.0.2
6.4. Several remarks and tips

Normally a blank like distilled water will generate a smaller gas volume then a
sample containing nitrogen compounds. This can result in less or even no
squeezing out of water.
When injecting large samples volumes (e.g. > 200 µL), the chance on
delayed cooking inside the furnace increases. When delayed cooking occurs
the following effects can be generated:
Pushing out a lot of liquid from the cold trap
Quick cooling of the furnace tube (with an increase chance on destruction of
the tube or ceramic inlay.
Higher risk of samples getting in direct contact with the quartz components
inside the furnace; resulting in a shorter life span.
To prevent these problems, the boat program should be made slower for the
introduction part. However, this can influence the analytical results.
The squeezing out of liquid from the cold trap can occur at any moment
during the introduction and analysis. However in most cases it can be
observed during the injection of the sample into the boat and during the
return of the boat to its home position.
Warning: The deposits on the filter may be toxic.

Warning: Salts of Nickel can be toxic. Handle with care.
Warning: Sulfuric and phosphoric acid will destroy clothing
and skin.
6.5. Frequent maintenance
Daily:
Check if the boat and Nickel cylinder is still intact and properly outlined. If not,
or in case of any doubt replace it with a new one and clean the furnace tube.
Check the liquid level and temperature (is it cold) of the cold trap. When
necessary add or drain water. If the cold trap should be totally empty, also
add a few drops of a strong acid and check during the first few
measurements if the cold trap is not emptied too fast. If this is the case,
adjust the height of the siphon/overflow tube.
If present, empty the beaker under the overflow tube.
Add extra water if the level is too low (less then half the lower chamber).
Note: Acidification will not be necessary.
Weekly:
Clean the cold trap by rinsing it with ample water. Next, fill it to approx. 1 cm
below the upper chamber with water and a few drops of concentrated acid
like sulfuric or phosphoric acid.

User Manual
TN-TS 3000 Rev. 2.0.2
Check and if necessary replace the filter in the green filter holder next to the
furnace outlet.
Clean the outlet tube and the tubing connected of the furnace.
Check, and if necessary replace the blue septum in the injection port
(Aluminum funnel on top of a red screw).
Keeping the system clean:

We strongly advice to measure blanks (i.e. distilled water) frequently.
Measure these blanks 3 to 5 times first in a new queue. Also measure some
blanks between for example standards and samples. Finally, always
measure at least 5 blanks at the end of a queue.
If the system is not used for more then a week, measure at least 5 blanks
(200~400 µL) prior to setting the system in stand-by mode.
6.6. Trouble shooting

Problem: The cold-trap empties when a sample is introduced
Solutions: Increase the static height of the exit tube on the cold trap
Decrease the speed of the boat for entering and/or exiting the
furnace
Decrease the injection speed of the sample in the boat
Decrease the sample volume
Another possible reason for this problem can be that the sample is not
injected into the boat but into the introduction module. This can be caused by
wrong calibration of the boat and/or needle or when the boat is damaged.
Problem: The boat is not moving anymore, but the boat drive is.
Solutions: Check if the boat is still undamaged. If not, replace it.
If the boat is not damaged, clean the outside of the boat and the
inside of the introduction module with water. Beware that the
quartz wool does not get too wet. Make sure to dry the parts
carefully.
Check for blockage inside the furnace tube. Clean if necessary.
Note: Do not remove the tube from the furnace unless absolutely
necessary. Follow the instructions written above if the tube has to
be removed.

User Manual
TN-TS 3000 Rev. 2.0.2
Problem: Hardly any area is measured or a strange gab in the ‘normal’

peak is seen.
Solution: Most likely the liquid level in the cold trap is too low resulting in
leakage of the analysis gasses. Fill the cold trap and, if
necessary, adjust the siphon tube.

6.7.
User Manual 3000 systems V2.0.doc

Flow diagram TN water
High salt combustion tube

with ceramic inlay
Wash solution
TN-TS 3000
User Manual
Oxygen
Vacuum pump
NO Convertor
Ozone Killer Argon
Ozone Generator
Coldtrap
PMT detector
Temp. Contr.
Capillary
Rev. 2.0.2
Page 74 of 169
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TN-TS 3000 Rev. 2.0.2
7. External samplers
Warning:
Always stop the software (ThEuS or ECS) running before
switching off the sampler. In not doing so, it can happen that
commands are still waiting to be executed while the sampler is
switch on again. This can cause malfunctions like a needle crash.
7.1. NeXYZ autosampler

The NeXYZ auto sampler replaces the ELS3000 and ELS2100 samplers. Please
refer to the User’s Guide of the NeXYZ for installing, maintenance and using
instructions.
7.2. ECA1700 AOX Column autosampler

This paragraph guides the user through installation and operational procedures,
concerning the ECA1700 autosampler. Following these guidelines will explain its
function and possibilities. The described procedures are mainly for the “standard”
AOX/TOX column method. For other purposes or applications, please refer to the
“method sheets” and “application notes”, provided with the unit, whenever applicable.
7.2.1. Introduction-Description
The Thermo Fisher Scientific Column sampler model ECA1700 is designed to
increase the throughput of the TOX/AOX sample load.
In combination with the automatic sample pretreatment units from Thermo Fisher
Scientific, a fully automated configuration ensures unattended and trouble free
analysis.
The autosampler has a 37 position carousel, introducing samples in combination with
the ECA-AOX module. For Q.C. purposes, the ECA system software allows control
standards, samples and reference samples to be measured during one run. The
software handles “multiple point calibration” and the traditional absolute method,
which is commonly used with the coulometric technique. Data acquisition,
recalculation, reintegration, report generation are just a few features within the
software. In short: Both 3000 system and ECA1700 are fully software controlled.

User Manual
TN-TS 3000 Rev. 2.0.2
ECA1700 autosampler

User Manual
TN-TS 3000 Rev. 2.0.2
7.2.2. ECA-TOX method, step by step

Water samples are run over small columns filled with activated carbon. The ECA1700
carries the pretreated columns in a 37-position carousel. The pre-packed columns
placed in the carousel are protected by a cover, which may be purged with Ar or He.
The white unused fast connector, found on the 3000 system may be used for this
purpose. The purge flow is adjusted with the regular flow meter.
After a queue is built/created and the start button is pressed a plunger pushes the
carbon plus ceramic wool from the glass column into the sample boat. The carousel
moves to the home position and the plunger moves downward, closing the stopper
and seal. At this point the module plus furnace tube are gas tight. The boat, which
carries the carbon plus ceramic wool, moves into the high temperature combustion
zone. The content is oxidized completely and a signal appears on the screen.
After combustion, the boat returns to the injection area and a scraper takes out the
remaining ashes. The ashes fall into a collection area, which after a full run is
emptied, using a vacuum device. In the mean while the boat is being cooled to
prepare it for the next sample introduction.
When the curve on the screen reaches the baseline again, the analysis may be
terminated and the curve is automatically integrated. A result appears on the screen
and a printout can be made. In the automatic mode, the next sample is being
introduced.
7.2.3. Installation ECA1700

The installation of the ECA1700 is relatively easy. The ECA1700 must be installed on
top of the 3000 system.
Correct installation procedures and alignments are of great importance. This
paragraph will guide you through the installation procedure of the autosampler.
The ECA-AOX module, necessary for running samples in combination with the
ECA1700, differs in a few details from the standard AOX module.
1) The boat is bigger and has a different shape.

2) There is a scraper in place that cleans the boat from ashes and wool particles as
soon as it returns from the furnace. The remains are collected in a special area,
provided underneath the boats home position.
3) A special tube is connected for vacuum cleaning purposes. Connecting it to a
vacuum cleaner/device, enables the operator to clean the “remains collective
area”. (the size of the area should be sufficient to support a full run, before a
cleaning procedure has to be carried out)
4) An “extended boatdriver” package is supplied or mounted onto the 3000 system
to control and support the special features of this module.

User Manual
TN-TS 3000 Rev. 2.0.2
7.2.4. ECA1700, Mounting

Unpack the ECA1700 carefully and check all the parts according to the checklist.
The Auto sampler size is approximately 330 x 365 x 270 (w x h x d)
The ECA1700 should come with:
• A flat cable for communication with the pc

• A cover with gas connection to exclude “external” influences
• A 37-position carousel
• An integrated ID connector (connects to the 3000 system)
• 2 Mounting brackets for fixation and positioning (or pre-installed)
• An extended boatdriver (in some cases already installed 3000 system)
• Extended Module support (in some cases already installed 3000 system)
• The special ECA-AOX module
• A Column securing-Plunger guide
Check if the mounting brackets are already in place. If not position them as explained
in the picture.
Brackets
Brackets

User Manual
TN-TS 3000 Rev. 2.0.2
Replace the normal boat pusher with the extended one. (mounted on the carriage in
the boatdriver, which could be pre-installed)
Extended items
Standard Boat items
Note that the threads of the ECA bracket are pointing outwards!
(viewed from the furnace tube)
Install the ECA-AOX module, connect the clamp, which joints the furnace tube and
the module and insert the oxygen connector.
Check if the glass parts are aligned in the correct manner. (see picture next page)

User Manual
TN-TS 3000 Rev. 2.0.2
Clamp Furnace tube
ECA fasteners
Rubber sealing
ECA AOX module
Female Module connector
Safety cover plunger

Column securing and
Plunger guide
Fastener ECA
ECA Carousel
Position the ECA1700 sampler over the 3000 system, align it with the module and
lock the sampler, using the supplied fasteners.

User Manual
TN-TS 3000 Rev. 2.0.2
7.2.5. ECA1700, external connections
Power cable 3000 system
PC control cable
All external connections are found at the backside of the ECA1700.

The Power cable coming from the ECA1700 goes into the female module connector
on top of the 3000 system. The PC control cable has to be connected onto the
ECA1700. The other side of the cable goes onto the specially provided parallel port
connection, which (has to be or) is already installed in the external PC. This
connector is attached to the IOC2 board.
The IOC2-board is usually factory installed in the supplied PC.
This board controls the Titration Cell, handles data acquisition and controls the
physical movement of the ECA1700.
Electrical Hazard
Do not open the cabinet before the power cable is removed.
!!Do not temper with safety features of the ECA1700!!

Warning
Wrong connections could lead to malfunction of the analyzer or
computer. Only connect or disconnect cables when power is switched
off!
Warning
Do not temper with- or bypass the safety switch.
Operate the ECA1700 with closed access door only.
Not complying could result in injury.
The column pusher uses excessive force to empty the columns.
Stay away from the pusher during operation and keep the access door
closed!

User Manual
TN-TS 3000 Rev. 2.0.2
7.2.6. ECA1700: System and software settings

Using the ECA1700 in combination with the 3000 system enables the operator to run
unattended analysis. This chapter briefly describes settings and system features for
automated sample throughput.
Basic settings for the 3000 system in the ECA1700 mode are similar to the “normal”
AOX methods.
System flows, temperatures and coulometric settings are the same as for AOX
according the batch and other manual methods.
Differences for ECA configuration are:
• Boat program (number of steps and positioning)

• Additional gas flow (Argon outlet used for sample preservation/stability)
• In some cases, the analysis time
• Optional “2 in 1” analysis
• Measuring screen could start before actual sample introduction (optional)
• Additional installed hardware
7.2.7. Software settings ECA1700

Typical temperatures are 1000°C for both furnace zones, similar to regular TOX/AOX
analysis. Outlet temperature is 300°C
Typical gas flows are:
• O2 50mm (combustion/manual flow meter) = 330 mL/min
• O2 15mm (bypass/manual flow meter) = 45 mL/min
Depending on the specific application the fan will start cooling at maximum capacity
(100%) as soon as the boat returns. The duration of cooling is approximately 4
minutes. Before the next sample gets introduced, the cooling will have to be shut
down or reduced to 10%. Check if this setting is correct in the “Analysis method”
window.
“Normal cooling” is 10% “Forced cooling” is 100%
Beside standard methods, customized method can be made and stored.

• Open a specific analysis method.
• Save it under a different name.
• Modify the necessary items. (boat program, temperatures etc)
• Close the window again.
• Go to the controller window and select the new method.

User Manual
TN-TS 3000 Rev. 2.0.2
Basic boat program, used with current ECA application:
No Name Position Speed Pause

1 Standby 50 mm 15 mm/s 100 s
2 Evaporation 90 mm 5 mm/s 60 s
3 Combustion 175 mm 5 mm/s 180 s
4 Home 0 mm 10 mm/s 240 s
For more details, refer to the electronic manual in ThEuS.
Note: The cooling time must be programmed in step 4. This is the “Home”
position of the boat-program. This step controls the cooling time before the
next sample is introduced.
Not doing so will affect the next result because of too high temperature in the
entrance zone.

User Manual
TN-TS 3000 Rev. 2.0.2
7.3. ESA2000 AOX and Solids auto sampler

This paragraph guides the user through installation and operational procedures,
concerning the ESA2000 auto sampler. Following these guidelines will explain its
function and possibilities. The described procedures are mainly for the “standard”
methods. For other purposes or applications, please refer to the “method sheets” or
“application notes”, provided with the unit, whenever applicable.
Figure: 3000 system with ESA2000
7.3.1. Introduction-Description
The Thermo Fisher Scientific AOX-Solid auto sampler model ESA2000, is designed
to increase the throughput of the sample load. In combination with the 3000 system,
unattended and trouble free analysis are a reality. The auto sampler has a 48
position carousel, introducing the samples in combination with the special sample
cups, made from quartz glass or metal. A laser beam controls the in- and out coming
sample cups, to make sure that there is no pile up in the furnace tube or module. For
Q.C. purposes, the ESA system software allows control standards, samples and
reference samples to be measured during a run. The software handles “multiple point
calibration” as well as the traditional “absolute method”, which is commonly used with
the coulometric technique. Data acquisition, recalculation, reintegration, report
generation are just a few features within the software. In short: Both 3000 system
and ESA2000 are fully software controlled.

User Manual
TN-TS 3000 Rev. 2.0.2
Figure: ESA2000
7.3.2. ESA-AOX batch method, step by step

Water samples are put in a conical flask and approximately 50 mg of activated
carbon is added. The substance shakes for one hour and is filtrated over the Thermo
Fisher Scientific Frit. The Frit is a sample cup, which has a quartz-sintered filter layer,
capable of the separation between the water phase and the activated carbon. The
prepared Quartz Frits are placed on the carousel and protected by a cover, which
may be purged with Ar or He. The white unused fast connector, found on the 3000
system may be used for this purpose. The purge flow is adjusted with the regular flow
meter.
After a queue is listed and the start button is pressed the arm-hand lifts a Frit or
sample-cup from the carousel and puts it into the ESA module on top of the boat.
The grabber-hand has a neoprene sealing ring, which closes the entry of the module,
creating a gas-tight environment.
The boat, which carries the Frit plus carbon, moves into the high temperature
combustion zone. The content is oxidized completely and a signal appears on the
screen.
After combustion, the boat returns to the injection area and the Frit or sample-cup is
taken out and placed onto the carousel again. A laser beam is used to check if the
sample cups placed in the module are taken out as well. An error message will
appear and prompts the operator to take corrective action. (frit detected yes/no)
The laser control will prevent pile-up and malfunction. In the mean while, the boat is
being cooled as soon as the boat starts to retract. The cooling action is necessary to
lower the temperature of the boat and module, prior to the next sample introduction.
As soon as the curve on the screen reaches the baseline again and maximum
analysis time is reached, the analysis may be terminated and the curve is
automatically integrated and stored. The result appears on the screen and a printout
can be made. In the automatic mode, the next sample is being introduced.

User Manual
TN-TS 3000 Rev. 2.0.2
7.3.3. General solids method, step by step

Solid samples, highly viscous samples, high boiling ones, are usually run with the
ESA2000. This will definitely improve repeatability and sample throughput.
Instead of the “Frit” used for the AOX batch method, described in the previous
chapter, a smaller type sample cup is used. The ESA2000 is slightly modified with a
smaller grabber and the “solids module” carries a smaller boat. The sample cups are
placed on the carousel and protected by a cover, which may be purged with Ar or He.
The small flow regulator found on the ESA2000 may be used for this purpose.
An indicator existing of LED’s shows the amount of flow purged over the samples.
The carousel in standard configuration supports the “AOX Frit” only.

For the use of the smaller cups, small inlays are placed for proper positioning.
Next a queue is listed and the start button is pressed the arm-hand lifts a Frit or
sample-cup from the carousel and puts it into the ESA module on top of the boat.
The grabber-hand has a neoprene sealing ring, which closes the entry of the module,
creating a gas-tight environment.
The boat, which carries the sample cup with content, moves into the high
temperature combustion zone. The content is oxidized completely and a signal
appears on the screen.
After combustion, the boat returns to the injection area and the sample-cup is taken
out and placed onto the carousel again. A laser beam is used to check if the sample
cups placed in the module are taken out as well. An error message will appear and
prompts the operator to take corrective action. (cup/crucible detected yes/no)
The laser control will prevent pile-up and malfunction. In the mean while, the boat is
being cooled as soon as the boat starts to retract. The cooling action is necessary to
lower the temperature of the boat and module, prior to the next sample introduction.
As soon as the curve on the screen reaches the baseline again and maximum
analysis time is reached, the analysis may be terminated and the curve is
automatically integrated and stored. The result appears on the screen and a printout
can be made. In the automatic mode, the next sample is being introduced.

User Manual
TN-TS 3000 Rev. 2.0.2
7.3.4. Installation of the ESA2000

The installation of the ESA2000 is relatively easy. The ESA2000 must be installed on
top of the 3000 system, using a special “docking station”.
Correct installation procedures and alignments are of great importance. This
paragraph will guide you through the installation procedure of the autosampler.
The ESA-AOX module, necessary for running samples in combination with the
ESA2000, differs in a few details from the standard AOX module.
1. The boat used is a special ESA-AOX- or Solids-version to support the different

sample cups and “Frits”.
2. The sample entrance in the module does not have a conical joint for stopper
purposes. (the neoprene ring just seals off on the edge of the glass)
3. A “module positioning” package is supplied or mounted onto the 3000 system to
control and support the special features of this module. It enables both positioning
and fixation.
7.3.5. ESA2000, Mounting

Unpack the ESA2000 carefully and check all the parts according to the checklist.
The autosampler should come with the following items:
• A flat-cable for communication

• A carousel cover to exclude “external” influences
• A 48-position carousel
• Mounting brackets for fixation and positioning of the boat module (or pre-
installed)
• Docking-station for ESA positioning (fast removal, positioning)
• The special ESA-AOX module
• Power cord
Mounting brackets
Docking-station
Fastener
Base plate gas and ID

Connector in standard
position
Figure: Front-view Docking-station

User Manual
TN-TS 3000 Rev. 2.0.2
Check if the mounting bracket for the Docking-station is already in place. If not
position it as showed in the picture.
Verify if the base plate including gas connections and ID connector is repositioned in
a way as the picture below.
Base plate re-positioned for

easier ID and gas connector
access. If it is not re-positioned
the ESA2000 will hit the
connectors once placed on top
of the docking station
Figure: Re-positioned base plate for connectors
Mounting bracket ESA
Positioning ESA
Figure: Mounting brackets, positioning

User Manual
TN-TS 3000 Rev. 2.0.2
Spring
Rear- end support
Teflon boat positioning

Fastener
Boat positioner
Figure: right-hand side view 3000 system
The boat positioner is used to adjust the home position of the returning boat.
The exact home position is important for the ESA hand. The hand is adjusted with
both soft- and hardware. The magnet, which controls the movement of the boat, has
some tolerance in the positioning. In order to take away this tolerance, a “mechanical
home” position is created. An adjustable plastic thread is used to dictate the
maximum allowed distance. The boat can not travel beyond this point and all
tolerance is taken out of the motion.
ESA Module
ESA position lock

Boat Magnet
Teflon Boat
positioning
Adjustment screws
ESA position lock
Figure: helicopter view module positioning

User Manual
TN-TS 3000 Rev. 2.0.2
7.3.6. ESA2000 hardware alignment procedure

For correct alignment, please follow this procedure.
1. Check if all brackets, docking station and accessories are correctly

mounted and secured.
2. Install the ESA boat module including the boat, position and align the
module.
3. Secure the module, using the “Plate rear-end support”
4. Check if boat drive is “home” (metal arrow point at zero)
5. Adjust the plastic thread, until the boat is in the exact center of the “module
sample inlet”.
6. Loosen the “ESA position lock Adjustment screws” and carefully place the
ESA2000 on top of the “ESA docking station”
7. Remove the “neoprene sealing ring” from the arm-hand
8. With the power switched off, manually move the arm-hand to the sample
inlet.
9. Lower the hand until the hand is just above the boat (2-3 mm)
10. Observe if the spacing between the sample inlet and the ESA 2000 hand
is equally divided (left and right). If not, move the ESA until the desired
position is reached.
11. Carefully remove the ESA and tighten the “ESA position lock Adjustment
screws”. Reposition the ESA and check if alignment is still ok.
• Verify points 7-11 by the pictures on the next page.

User Manual
TN-TS 3000 Rev. 2.0.2
Neoprene ring present Neoprene ring removed (point 7)
Center hand/arm
Positioned above the inlet (point 8) Lowered completely (points 9+10)
This takes care of the “hardware alignment” for the 3000 system ESA2000
configuration. Besides this procedure a “software calibration” must be carried out.
This procedure is explained in the software part of this chapter.

User Manual
TN-TS 3000 Rev. 2.0.2
7.3.7. ESA2000 external connections
Power cord connector,

On-off switch
Purge gas connection

Flat-cable
connector
ESA2000 rear-view
All external connections are found at the backside of the ESA2000.

The female connector on top of the 3000 system is left empty. The flat-cable has to
be connected at the back of the ESA2000. The other side of the cable goes onto the
specially provided flat-cable connection, which (has to be or) is already installed in
the external PC. This connector is attached to the IOC2 board.
The IOC2-board is usually factory installed in the supplied PC.
This board controls the Titration Cell, handles data acquisition and controls the
physical movement of the ESA2000.
Electrical Hazard
Do not open the cabinet before the power cable is removed.
!!Do not temper with safety features of the ESA2000!!

Warning
Wrong connections could lead to malfunction of the analyzer or
computer. Only connect or disconnect cables when power is switched
off!

User Manual
TN-TS 3000 Rev. 2.0.2
Warning
Do not temper with- or modify the laser settings or adjustment.
Laser light can be a threat to your eyesight.
Even though the intensity is not of a high level, do not look directly into
the beam.
Operate the ESA2000 with supplied cover only.
Not complying could result in injury.
Readjustments should be carried out by trained Thermo Fisher Scientific
technicians only!
7.3.8. ESA2000: System and software settings

Using the ESA2000 in combination with the 3000 system enables the operator to run
unattended analysis. This chapter briefly describes settings and system features for
automated sample throughput.
With the hardware alignment carried out correctly, the next step, “software alignment
must be carried out. This is very important with first time installation or re-calibration,
in case of erratic functioning. The following steps will guide you through the
procedure.
Basic settings for the 3000 system in the ESA2000 mode are similar for the “normal”
AOX methods.
System flows, temperatures and coulometric settings are the same as for AOX,
according the batch and other manual methods.
However, for solid methods refer to application notes or reports, for correct settings.
Features and Differences for the ESA configuration are:
• Boat program (number of steps and positioning depending on application)

• Additional gas flow (Argon outlet used for sample preservation/stability)
• In some cases, the analysis time
• Software calibration protocol.
• Laser control for sampling.
• One special ESA boat module for AOX and one for Solids in general.
• ESA2000 supports the special Thermo Fisher Scientific Frits.
• 2 sizes of sample cups, for different analytical purposes. (1 AOX cups or
Frits for the ESA-AOX module. 2 Solids sample cups for the ESA solids
module.)
• Measuring screen can start before actual sample introduction (optional in
extra window)
• Additional installed hardware

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TN-TS 3000 Rev. 2.0.2
7.3.9. Software settings ESA2000
Special Attention
Before the power is switched on, move the arm into a “neutral position”.
Manually move the arm in the approximate center of the “left-right, up-
down” position.
When the ESA is positioned in the Docking-station the arm should be positioned into
the approximate center of the unit. (check the above “special attention”)
Pressing the “Init” button with the power supplied and data cable connected to the
ESA2000 and a powered 3000 system, should activate the “Arm-hand” and sample
carousel. They both are now moving to their home positions and perform the
initialization procedure. The ESA checks if position 48 is empty. If this is confirmed it
checks if there is no sample cup left in the boat. If one is found, the ESA picks it up
and places it on position 48. The system will produce a message to the screen,
prompting the user to remove it from 48.
Always check if position 48 is empty. This will save analysis time!
For first time operation a calibration procedure has to be carried out, for optimal
performance. Sensors inside the ESA2000 should be positioned correctly.
This is normally carried out in the factory. In case of doubt about the precision of
sensor positioning, contact a Thermo Fisher Scientific representative to correct
and/or assist with this procedure in case of readjustment.
Warning
Do not temper with the laser beam or it’s adjustment!
This must be carried out by a trained Thermo Fisher Scientific
representative.
Direct Sample positioning is also possible. Just key-in a number in the “Sample
Position” window. (1-48) Pressing “Enter” on the keyboard will trigger the action and
moves the carousel to the desired position.
Note: Movement of stepper motors can be “noisy and/or irregular” when data
traffic on the PC gets heavier or initialization is carried out. This should not
affect the sample handling.

User Manual
TN-TS 3000 Rev. 2.0.2
Two parameters should be checked and adjusted for:
1. To check if this procedure is correct, close the bypass gas flow (only for this
specific test) and reduce the oxygen carrier to approximately 10 mm (manual flow
meters) or 25 mL/min for mass flow meters. Observe the Sulfuric acid in the
scrubber and check for bubbles. If there are no bubbles appearing in the acid,
increase the number of steps, to get more pressure on the sealing between the
rubber and the glass wall. If necessary, repeat the procedure until a gas tight
sealing is reached.
Warning
Do not forget to restore the original flow settings! Sulfuric Acid

could be redirected towards the furnace!
2. Another parameter to be checked is the positioning of the sample cup. Check if

the cup is freely placed onto the boat without added pressure from the hand. This
could create damage to the boat or sample cup after repeated action. Closely
observe the sample cup upon positioning onto the carousel. Check if it is freely
positioned without added pressure or a “free-fall” onto the carousel. Correct
positioning is necessary to prevent sample spill out of the cups during positioning
or damage to the hand.
Warning
Prevent the hand from crashing onto the carousel. The alignment or
mechanical features of the stainless steel hand may be lost, because of
mechanical damage.

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7.3.10. ESA Boat program and related settings

A special boat program is needed for the execution of the AOX batch method.
The following settings will have to be checked and if not present, they have to be
programmed. The Standard method is: ESA AOX or ESA solids.
Depending on the specific application the fan will start cooling at maximum capacity
(100%) as soon as the boat returns. The duration of cooling is approximately 4
minutes. Before the next sample gets introduced, the cooling will have to be shut
down or reduced to 10%. Check if this setting is correct in the “Analysis method”
window.
“Normal cooling” is 10% “Forced cooling” is 100%
For some applications a continuous maximum cooling is standardized.

Typical temperatures are 1000°C for both furnace zones, similar to regular TOX/AOX
analysis. Outlet temperature for scrubber heating is 300°C
Typical flows for the applications are:

• O2 50mm (combustion/manual flow meter) = 330 mL/min
• O2 15mm (bypass/manual flow meter) = 45 mL/min
Beside standard methods, customized method can be created and stored.
• Open a specific method.

• Save it under a different name.
• Modify the necessary items. (boat program, temperatures etc)
• Close the window again.
• Go to the controller window and select the new method.
Basic boat program, used with current ESA-AOX batch application:

1 Standby 0 mm 10 mm/s 0s
2 Evaporation 70 mm 5 mm/s 60 s
3 Combustion 180 mm 5 mm/s 180-240 s
4 Home 0 mm 10 mm/s 0s

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Example of a special boat program, used with a specific ESA-solids application:

1 Standby 0 mm 10 mm/s 0s
2 Position1 60 mm 5 mm/s 60 s
6 Home 0 mm 10 mm/s 0s
For more details, refer to the Software manual or the Thermo Fisher Scientific web-
site: www.thermo.com

User Manual
TN-TS 3000 Rev. 2.0.2
8. Coulometric analysis on the 3000 SYSTEM (optional)
8.1. Introduction 3000 SYSTEM in Halogen/Sulfur mode

The 3000 SYSTEM optional, can be upgraded with a “titration package” for the fast
and efficient analysis of organic halogen (X) and sulfur (S) compounds. The 3000
SYSTEM provides for the use of different modules, which can be used for the
incineration of samples in a furnace. The hydrogen halides or the sulfur dioxide in the
incineration products are then coulometrically titrated in an automated microtitration
cell. This coulometric system is based on the KIWA-principle.
(KIWA is the Royal Dutch Waterworks)
The analysis is an absolute measurement, so no calibration is needed. The flowchart
for the measurement is as follows:
Fig. Schematic explanation of coulometric detection

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8.2. Principle of the measurements

With an introduction mechanism using a boat driver or injection syringe, the sample
is introduced into the furnace. During the movement into the furnace the sample is
flushed with argon. The volatile components are transported directly into the furnace.
In the furnace the sample oxidizes with O2. The gas flow is carried through a heated
connection to the scrubber. Here the water is removed from the gas. After the
scrubber, the gas is led to the NOx-scrubber. Then the gas flows into the titration cell,
where the actual reaction takes place. (silver-ions Ag+ react with halide-ions X- ) A
signal appears on the PC screen and the area generated by this signal is integrated.
The program calculates the actual concentration and stores the result.
8.3. Sample introduction

The modularity of the 3000 SYSTEM consists of three different types of titration cells
(halogen, sulfur large volume, sulfur small volume) and four methods of sample
introduction. For most of the applications there are two ways for sample introduction:
manually or with an auto ampler.
8.3.1. Manual sampling modules

In total there are four introduction modules for the 3000 SYSTEM. Each of them has
it own purpose. The design of the introduction modules is based on current standard
analytical methods for organic halogen and sulfur compounds. The introduction
modules are easily interchangeable and after installation fully controlled using the
Thermo Fisher Scientific software.
The four introduction modules are:

1. AOX-module
2. POX-module
3. Solids module (described in chapter 3.5.3 )
4. Liquids module (described in chapter 3.5.2 and 3.5.1 )
The principles of the design of the modules are based on the requirements for the
standard analyses of organic halogen and sulfur compound/content in samples of a
divergent nature and origin. Various fractions of organic halogen (X) and sulfur (S)
compounds are analyzed by these standard analytical methods. The modules can
also be used for non-standard analyses.

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8.3.1.1. AOX module

The AOX module is used for Adsorbable Organic Halogen (AOX). The sample is
adsorbed onto activated charcoal in the preparatory phase. The charcoal bearing the
adsorbed analytical sample is slid into the furnace on a boat and burned in a flow of
oxygen.
With this module also Total Organic Halogen (TOX) can be analyzed.
Warning
Do not use this introduction module for samples containing significant
quantities of (combustible) organic components, like oil, waxes etc.. The
sample is introduced in a flow of pure oxygen. Any combustible
component will ignite prematurely.
8.3.1.2. POX module

The POX module is used for Purgable Organic Halogen (POX). In this module
volatile organic halogen compounds are purged from an aqueous solution by means
of argon gas. The analysis sample is first mixed with oxygen before being blown
directly into the furnace. The POX Module is used in conjunction with the AOX
module.

The solids module is used for analysis of Total halogen (TX) or Total sulfur (TS)
content in solid samples. The module is meant for the analysis of halogen and sulfur
compounds in solid samples and liquids containing large molecular compounds with
boiling temperatures above 450°C. These are carried into the furnace by a flow of
argon and burned in oxygen.

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8.3.1.4. Liquid Module

The liquid module is used for analysis of extractable organic halogen (EOX) and
Extractable organic sulfur (EOS). This module permits the injection of solutions of
halogen or sulfur compounds in organic solvents, for example after being extracted.
The injected sample is then carried by a flow of argon into the furnace and burned in
oxygen.
With this module also Total halogen (TXliquid) or Total sulfur (TSliquid) in liquid samples
and Total halogen (TXgas) or Total sulfur (TSgas) in gas samples can be analyzed.

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8.3.2. Auto sampling

To extend the throughput of the samples Thermo Fisher Scientific has developed a
number of auto samplers for use with the 3000 SYSTEM.
One of them is used for AOX-sampling: ECA1700. This unit automatically dispenses
the carbon into the introduction module. More than 35 (!) samples can be analyzed in
one run. Another one is used for TS/TX Liquid sampling: The ELS3000. More than 70
(!) samples can be analyzed in one run. (refer to chapter 7)
8.4. Furnace
The sample is placed in a boat in a stream of oxygen and/or argon into the furnace.
The furnace is divided into two temperature zones. (according ASTM guidelines)
The temperature in each zone can be individually adjusted to all temperatures up to
1100°C. The sample incineration time in each zone can also be adjusted.
In the furnace the sample is oxidized into gas. In the event of incomplete incineration
soot deposits may be formed. (refer to chapter 13 “trouble shooting”)
8.5. Gas conditioning

The incineration gases leave the furnace via a glass gas exhaust tube or outlet,
through which the sample is led to the scrubber. The outlet is maintained at a high
temperature by means of a heating wire in order to prevent condensation and trap
other “undesired components”. An oxygen bypass is placed in the outlet to prevent a
back flash of sulfuric acid towards the furnace. With a needle valve the amount of
oxygen led through the bypass can be regulated. After this scrubber the gas is led to
the next scrubber, the so-called NOx-scrubber (mainly used for AOX and Cl
analysis).
8.6. Detector, coulometric titration

After the gas conditioning the sample gas will be detected in the titration cell. Three
different titration cells can be used. These are: a cell for the coulometric silver
titration of halides, a cell for the iodometric analysis of sulfur dioxide at p.p.m. level,
and a cell for the iodometric analysis of sulfur dioxide at p.p.b. level. After preparation
and installation, the titration cells are suitable for long series of automatic analyses.
The signals from the titration cell go directly to the IOC-board in the computer, where the
data is collected and processed.

User Manual
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8.6.1. Halide analysis, principle

Ei-r is governed by the concentration of silver ions in solution as stated by Nernst's
Law. A change in the concentration of silver ions will therefore give rise to a change
in Ei-r. The concentration of silver ions changes when halide ions enter the solution.
The halide ions tend to remove silver ions from the solution by the formation of silver
halides, which are notoriously insoluble. This can for example occur by the reaction:
Ag+(aq) + Cl-(aq) --> AgCl(s)
When Ei-r changes, the coulometer passes current (1) through the generator circuit,
thus forming silver ions at the anode. Hydrogen is then formed at the cathode.
The silver ions react with halide ions until these have disappeared or, in other words,
until the concentration of silver ions has returned to the same level as the initial
concentration of roughly 10-7 M.
The solubility product indicates the relationship between the concentrations of silver
ions and halide ions in a saturated solution. For silver chloride this is:
Ks = [Ag+][CI-] = 1.78 x 10-10
As long as Ei-r continues to change current will pass through the generator circuit and
silver ions will be generated. As Ei-r approaches its initial potential the current will fall
off. Once Ei-r has reached its initial value again, i.e. when all the halide ions have
been converted, the generator curve (1) will again be zero.
There is a difference in potential between anode and cathode of:
Ei-r + Ebias
Ebias is a fixed potential of -0.315 V that serves, among other things to compensate
the electrical resistance of the cell. The total of Ei-r + Ebias is equal to about 0.5 V.
Coulometry is a form of titration. The substance to be titrated is converted by means

of an electrical charge. It should therefore be remembered that it is not the
substance itself, which is being titrated but an electrical charge.
The figure below shows an 3000 SYSTEM titration curve. At first the current
increases. The speed with which this takes place depends on the speed with which
the hydrogen halides enter the titration cell, or in other words the way in which the
analysis sample is introduced. After reaching a peak the current strength returns to
zero. (speed of titration depends on gain and Cell condition, see figure next page)

User Manual
TN-TS 3000 Rev. 2.0.2
example titration curve
The quantity of Ag+ ions which is generated by the flow of the current through the cell
and consequently the quantity of deposited halide ions, behave in accordance with
Faraday's Law:
t
1 Q
m= ∫
n. f 0
I . dt =
n. f
where: Q = the quantity of charge in Coulomb passing through the electrode surface in time t.
m= mass of converted substance [mol]
F= Faraday's constant (96487 C/mol)
n= number of electrons involved in the electrode reaction (here n = 1)
t= titration time
I= current (as a function of time)
Integrating the current over time provides the quantity of charge used for titrating the
halide. The quantity of charge, which has been titrated is shown in µC in the right
hand column in the measurement display. The quantity of halide present in the cell
can then be calculated from this figure. The calculations are carried out automatically
by the Thermo Fisher Scientific 3000 SYSTEM software.

User Manual
TN-TS 3000 Rev. 2.0.2
8.6.1.1. Halide analysis, titration cell

The titration cell consists of the parts shown in the picture below.
Where: I = Indicator eIectrode (Ag)

R= Reference electrode (3M KCl saturated with AgCl)
A= Anode (Ag)
C= Cathode (Pt)
The cathode is contained in a glass tube, and is separated from the measurement solution by
means of a frit. The purpose of this frit is to exclude the effect of disruptive reactions around
this electrode.
0= Outlet
G= Gas inlet tube
Acid
The titration cell contains a solution of 75% acetic acid in
water. The concentration of silver ions in solution is
maintained at a constant level of about 10-7 M.

User Manual
TN-TS 3000 Rev. 2.0.2
8.6.1.2. Halide analysis, circuit diagram

The figure below shows a general and simplified diagram of the electrical circuit.
Where: V = Voltmeter
Amp = Ammeter
RΩ = Variable resistance
R = Reference electrode
I = Indicator electrode
A = Anode
C = Cathode
The titration cell contains two pairs of electrodes:

Measuring path:
- Indicator electrode I (silver)
- Reference electrode R (silver/silver chloride). This electrode is connected to the
solution through a bundle of capillary tubes.
Generation path:
- Anode A (silver)
- Cathode C (platinum)
The coulometer consists of a combination of two circuits:

The measuring circuit - Here the difference in potential Er-i, between the indicator and
reference electrodes is measured.
The generator circuit - When there is a change in Er-i, the coulometer passes a
current through the anode/cathode circuit. Ag, ions are
generated at the anode as a result.
Acid
The titration cell contains a solution of 75% acetic acid in
water. The concentration of silver ions in solution is
maintained at a constant level of about 10-7 M.

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8.6.2. Sulfur analysis, principle

Ei-r is governed by the concentration of iodine ions (I3-) in the electrolyte and in the
side leg containing the reference electrode. The concentration of I- in the side leg
containing the reference electrode remains constant. A change in the concentration
of I- in the electrolyte will thus result in a change in Ei-r.
The concentration of I3- changes when sulfur dioxide dissolves in the electrolyte.
Sulfur dioxide reacts with I3- as follows:
SO2 + I3--+ 6 H20 ------ > SO42- + 3 I- + 4 H3O+
When Ei-r changes the coulometer passes current (1) through the generator circuit.
This results in the conversion of I- into I2 at the platinum anode, followed by the
formation of I3- as indicated below:
2 I- -------- > I2 + 2e
I2 + I- --------- > I3-
This process will continue until Ei-r no longer changes, i.e. until the concentration of I3-
has returned to the value it had before the addition of S02. The generator current will
then be equal to zero and all the S02 will have been converted into sulfate.
Here too the difference in potential between anode and cathode of:
Ei-r + Ebias = about 0.5 V
Ebias is in this case equal to + 0.145 V
The quantity of I- converted can be calculated from the charge needed for the
conversion. Then the quantity of S02 present in the cell can be determined according
to Faraday's Law.
The same remarks apply here to the titration curve as were made with respect to
halide analysis.

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8.6.2.1. Sulfur analysis, titration cell

The titration cell consists of the parts shown in the picture below.
Where: I = Indicator electrode (Pt spiral wound)

R= Reference electrode (Pt/l2/l-)
A= Anode (Pt spiral wound)
C= Cathode (Pt)
The cathode is contained in a separate compartment connected to the cell via a
narrow passage.
G= Gas inlet tube
Acid
The titration cell contains a solution of 0.1% KI, 0.1% NaN3 and
0.5 % acetic acid in deionized water.
The NaN3 (sodium azide) is added to prevent possible disturbances to the
measurement caused by nitrous oxides forming in the cell.
Warning
Sodium Azide is extremely toxic. Read the instructions of the

chemical safety sheet carefully and handle accordingly!

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TN-TS 3000 Rev. 2.0.2
8.6.2.2. Sulfur analysis, circuit diagram

The figure below shows a general and simplified diagram of the electrical circuit.
Where: V = Voltmeter
Amp = Ammeter
RΩ = Variable resistance
R = Reference electrode
I = Indicator electrode
A = Anode
C = Cathode
The titration cell contains two pairs of electrodes:

Measuring path:
- Indicator electrode I (platium)
- Reference electrode R (platinum/I2I-). This electrode is connected to the solution
through a bundle of capillary tubes. The actual electrode is a platinum wire. This
is placed in an electrolytic solution containing solid I2.
Generation path:
- Anode A (platinum)
- Cathode C (platinum)
The coulometer consists of a combination of two circuits:

The measuring circuit - Here the difference in potential E, between the indicator and
reference electrodes is measured.
The generator circuit - When there is a change in El-R the coulometer passes a
current through the anode/cathode circuit. I- ion is converted into I2, at the anode as a
result.

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Acid
The titration cell contains a solution of 0.1% KI, 0.1% NaN3 and
0.5 % acetic acid in deionized water.
The NaN3 (sodium azide) is added to prevent possible disturbances to the
measurement caused by nitrous oxides forming in the cell.
8.7. Data processing

The Thermo Fisher Scientific software controls the analyzer and all analysis, using a
separate PC. Several values can be set e.g. furnace temperature. Boat movement and
injection speed can be programmed as well as length of the analysis.
Besides control and programming, the software processes the detector signal and
calculates the concentration. The results and graphics can be printed.
For further information see the Thermo Fisher Scientific software manual for 3000
SYSTEM-systems.

User Manual
TN-TS 3000 Rev. 2.0.2
9. INSTALLATION HALOGEN AND SULFUR OPTION (coulometric)
9.1.1. Glassware connections

Glassware is the most important fact of the Thermo Fisher Scientific analyzers.
Connected to each other all parts form the heart of the analyzer. Therefore it is very
important to connect the parts carefully. Leakage has to be excluded.
The glassware parts are:
1. Sample introduction module

2. Furnace tube
3. Connection tube furnace scrubber
4. Sulfuric acid scrubber
5. Splash trap
6. NOx-scrubber
7. Titration cell
In the next paragraphs all connections will be discussed.
9.1.2. Sample introduction module
In total there are four introduction modules for the 3000 SYSTEM. Each of them has
to be installed differently. The introduction modules are easily interchangeable.
The four introduction modules are:

1. AOX-module
2. POX-module
3. Solids module
4. Liquids module
9.1.2.1. AOX module

The AOX module has to be slide into the furnace tube. Be sure the white Teflon
magnet in the boat module is installed just above the white Teflon boat driver. This is
a magnetic connection. Connect the gas connector (O2: Blue on blue). Place the
clamps in the right position. Place AOX ID-connector.
Warning

User Manual
TN-TS 3000 Rev. 2.0.2
9.1.2.2. POX module

The POX module has to be placed up the boat driver part of the 3000 SYSTEM. The
glass outlet of the module can be connected directly to the furnace tube. Place the
clamps in the right position. If an AOX module is already installed, a special glass
outlet can be used to place on the inlet of the AOX-module.
Connect the gas connectors (O2: Blue on blue, Ar: White on White). Place the clamps
in the right position. Place POX ID-connector.

The solids module has to be slide into the furnace tube. Be sure the white Teflon
magnet in the boat module is installed just above the white Teflon boat driver. This is
a magnetic connection. Connect the gas connectors (O2: Blue on blue, Ar: White on
White). Place the clamps in the right position. Place SOL ID-connector.
9.1.2.4. Liquid Module

The liquid module has to be placed in the boat driver part of the 3000 SYSTEM and
slide into the furnace tube. Connect the gas connector (O2: Blue on blue). Place the
clamps in the right position. Place LIQ ID-connector.
9.1.3. Furnace tube

The quartz furnace tube has to be sliced into the furnace compartment with the
narrow end towards the outlet side.
Special Attention
Avoid touching the surface of the furnace tube with your bare fingers. The
traces of grease left by your fingertips will create hotspots and reduce the
service life of the furnace tube.
9.1.4. Connection tube furnace scrubber

The heated connection tube is the connection between the furnace tube outlet and
the sulfuric acid scrubber. Follow the next steps for installing the tube.
The furnace tube and outlet become very hot during the operation
of the 3000 SYSTEM. Carelessness may result in burns.
9.1.5. Installation sulfuric acid scrubber

To place and connect the scrubber you have to be sure a clean and dry drip tray (F)
is placed in the scrubber department. Check that both stopcocks are closed (handle
in horizontal position). Follow the next steps for proper installation.
1. Remove the Permapure scrubber and install the stainless steel bracket. (A)
2. Suspend the scrubber on the bracket. (B)
3. Place the “connection furnace scrubber”. (C)

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4. Connect the inlet of the scrubber to the outlet of the heated connecting tube (ball-
joint), using clamp no. 12. (D)
5. Insert the connector (electrical) into the socket. (E)
6. Adjust the temperature of the outlet. (typical 300°C)
7. Adjust the gasses and fill the scrubber with sulfuric acid.
9.1.6. Sulfuric acid scrubber connected
D
E
Figure: sulfuric acid scrubber assembly
9.1.7. NOx-scrubber
Sometimes it is necessary to use a NOx-scrubber. Make sure that a clean and dry
drip tray is placed in the “Cell compartment”. The NOx-scrubber is connected directly
onto the gas inlet of the titration cell. Follow the next steps for installing the scrubber:
1. Fill the scrubber with sulfuric acid up to the marker

2. Place the NOx-scrubber.
3. Connect the outlet of the NOx-scrubber onto the gas inlet, using clamp no. 12.
4. Connect the tubing coming from the outlet of the scrubber onto the inlet of the
NOx-scrubber.

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TN-TS 3000 Rev. 2.0.2
9.1.8. Detector, titration cell

To place and connect the titration cell be sure a clean and dry drip tray is placed in
the detector department. See the next picture for the cell configurations.
TOP VIEW
HALOGEN CELL SULFUR CELL
GAS GAS OUTLET GAS OUTLET

INLET / INJECTION INLET
Follow the next steps for installing the titration cell.
1. Place stirring motor

2. Connector 5-pole DIN-connector
3. Fill the titration cell with the appropriate electrolyte up to the marker.
4. Place titration cell on the stirring motor
5. Connect electrode connectors
- I (Black) Indicator electrode
- R (Red) Reference electrode
- A (Red) Anode
6. Set bias for halogen at –0.315 V, for sulfur at +0.145 V
7. Set gain at 10 %
8. Connect the outlet NOx-scrubber with the inlet of the titration cell.
9. Connect at last the electrode connector: C (Black) Cathode
Figure: Scrubber and Cell compartment

User Manual
TN-TS 3000 Rev. 2.0.2
9.1.9. Cell compartment and cooling

The Cell compartment is placed directly besides the “3000 system” on the left-hand
side. The back of the compartment has a big heatsink to release the heat coming
from the “Peltier cooler”. To activate the cooling in the compartment, simply insert the
2 connectors found connected to the back of the unit. One of them is inserted into the
“extra 115-230V outlet” (refer to 4.2.1). The other one is inserted into the connector
specially made for this purpose. The “cooled air” generated by the “Peltier cooler” is
circulated by means of a smaller fan, found on the inside of the compartment. (refer
to the figure below) A green led at the back will start blinking once the preset
temperature is reached. Temperature can be adjusted. In this case contact your local
Thermo Fisher Scientific representative for assistance.
G
A
D
C
Figure: Titration Cell and cooling
1. Insert the connector through the hole of the Titration compartment (5-pole DIN-
connector (A)
2. Place the “Titration Cell” on the stirring motor (B)
3. Connect the inlet coming from the scrubber onto the gasinlet (without NOx
scrubber) (E)
• Drip tray condense water plus additional surplus outlet (C)

• Drip tray electrolyte and/or acid from the NOx scrubber (D)
• Cooling fan for cooled air circulation (F)
• Clamp no. 12 (G)

User Manual
TN-TS 3000 Rev. 2.0.2
10. Operating the 3000 SYSTEM in TX/TS mode
After installation the 3000 SYSTEM is ready for operation. The following paragraphs
should be read carefully, otherwise the measurement is worthless. Please note that
the software manual should be read before switching on the 3000 SYSTEM.
Special Attention
Read the Thermo Fisher Scientific software manual for TOC systems
before operating the 3000 SYSTEM.
10.1. 3000 SYSTEM TX/TS mode Starting up

Before starting up the 3000 SYSTEM several solutions should be prepared. In the
next paragraphs the following subjects will be described:
1. Preparation of reagents
2. Preparation of samples
3. Adjust gas flow
4. Filling the scrubbers
5. Powering the system
6. Gas leakage test
10.1.1. Preparation of reagents

All necessary solutions needed for a good analysis are described below. For some
specific applications refer to the application notes.
10.1.1.1. Sulfuric acid solution

The Sulfuric acid scrubber needs a solution of 95-98% sulfuric acid (H2SO4). No
further solution or dilutions should be made.
Acids
Read the chemical safety sheet before working with sulfuric acid and
follow the safety instructions.
10.1.1.2. Halide electrolytic solution

Pipette 250 mL of demi water into a liter volumetric flask. Fill up to 1000 mL with 100
% acetic acid and homogenize it.
10.1.1.3. Sulfur electrolytic solution

For the preparation of the stock solution add 2.5 g of Potassium iodide and 2.5 g of
Sodium azide into a 250 mL volumetric flask. Solve this in 150 mL demi water. Add
12.5 mL 100 % acetic acid and fill the flask to 250 mL with demineralized water.
Storage of this stock solution should be in a brown colored bottle at room
temperature. Pipette 10 mL of the stock solution into a 100 mL volumetric flask. Fill
the flask to 100 mL with demineralized water and homogenize.

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.2. AOX reagents
10.1.2.1. Nitrate stock solution

To make a stock solution of sodium nitrate dissolve 17 g of sodium nitrate (NaN03) in
800 mL deionized water and add 1,4 mL nitric acid (HNO3, 65%). Dilute to 1000 mL
with deionized water.
10.1.2.2. Nitrate wash solution

Put 50mL of the nitrate stock solution into a measuring flask and fill to 1000 mL with
deionized water.
10.1.2.3. p-Chlorophenol stock solution (200 mg Cl/L)

To prepare a stock solution of p-Chlorophenol dissolve 725,2 mg of p-Chlorophenol
(4-ClC6H4OH) in 700mL deionized water. Dilute to 1000 mL with deionized water. Mix
the solution thoroughly.
10.1.2.4. p-Chlorophenol standard solution (1 mg Cl/L)

Pipette 5mL of the p-Chlorophenol stock solution into a measuring flask and fill to
1000 mL with deionized water. Mix the solution thoroughly.
10.1.2.5. p-Chlorophenol test solution (100 μg Cl/L)

Pipette 10mL of the p-Chlorophenol stock solution into a 250mL erlenmeyer flask and
fill to 100 mL. Pipette 5mL of the nitrate stock solution into the prepared solution and
add 50 mg activated carbon. Mix the solution thoroughly.
10.1.3. POX reagents
10.1.3.1. Dichloromethane stock solution (1000mg Cl/L)

Put 200 mL of ethanol (C2H5OH, 96%) into a measuring flask. Pipette 0,227 mL of
dichloromethane (CH2Cl2) in this measuring flask and fill with ethanol up to 250 mL.
Mix the solution thoroughly.
10.1.3.2. Dichloromethane standard solution (100mg Cl/L)

Put 200 mL of ethanol (C2H5OH, 96%) into a measuring flask. Pipette 25 mL of the
dichloromethane stock solution in the measuring flask and fill with ethanol up to
250 mL. Mix the solution thoroughly.
10.1.3.3. Dichloromethane test solution (100 μg Cl/L)

Put 100 mL deionized water into a POX sample bottle. Inject 100μL of the
dichloromethane standard solution in the POX sample bottle with use a 100 μL gas
tight syringe. Mix the solution thoroughly.

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.4. TX/EOX reagents
10.1.4.1. Aldrin stock solution (1000 mg Cl/L)

To make a stock solution of aldrin dissolve 428,9 mg of aldrin (C12H8C16) in 200mL
n-hexane. Dilute to 250 mL with n-hexane. Mix the solution thoroughly.
10.1.4.2. Aldrin standard solution (100 mg Cl/L)

Pipette 10mL of the aldrin stock solution into a 100 mL measuring flask and fill to 100
mL with a mixture of n-hexane/hexadecane (9/1). Mix the solution thoroughly.
10.1.4.3. Aldrin test solution (10 mg Cl/L)

Pipette 10mL of the aldrin standard solution into a 100 mL measuring flask and fill to
100 mL with a mixture of n-hexane/hexadecane (9/1). Mix the solution thoroughly.
10.1.5. TS/EOS reagents
10.1.5.1. Diphenylsulfide stock solution (1000mg S/L)

To make a stock solution of diphenylsulfide dissolve 1425.7 mg of diphenylsulfide
(C12H10S) in 200mL ethanol (C2H5OH, 96%). Fill up with ethanol to 250 mL. Mix the
solution thoroughly.
10.1.5.2. Diphenylsulfide standard solution (100mg S/L)

Pipette 10 mL of the diphenylsulfide stock solution in the 100 mL measuring flask and
fill with ethanol to 100 mL. Mix the solution thoroughly.
10.1.5.3. Diphenylsulfide test solution (10mg S/L)

Pipette 10 mL of the diphenylsulfide standard solution in the measuring flask and fill
with ethanol to 100 mL. Mix the solution thoroughly.

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.6. Preparation of samples

The sample preparation of the most common measurements (AOX, POX, TOX and
EOX) is described in the next paragraphs. All descriptions are following the known
standards.
10.1.6.1. AOX sample preparation

Preparation of AOX samples follows the known standards:
AOX
DIN ISO SCAN EPA
Preparation of organic halogen sample adsorbed onto activated carbon is essential

for analyses performed with the 3000 SYSTEM. The sample can be prepared either
by the batch or the column method. The following diagram illustrates how the
samples should be prepared, prior to analysis.
Warning

User Manual
TN-TS 3000 Rev. 2.0.2
AOX sampling
Sampling
Removal of active chlorine
Storage at 4°C.
DOC analysis
< 10mg/L > 10mg/L

Dilute sample
Determination of anorganic chloride
< 1000mg/L > 1000mg/L

Dilute sample
Choose method
Batch method Column method
100 ml sample 100 ml sample
pH 2-3 pH 2-3
Add 50 mg activated carbon Adsorption onto 2 columns

flow speed 3 ml/min
Shake for 1 hour Washing by 25 ml nitrate
Quartzfrit filtration Polycarbonaat filter filtration Washing by 25 ml water
Press out columns into two crucibles

Washing in portions by 25 ml nitrate
AOX analysis
Washing by 25 ml water
AOX analysis

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.6.2. POX sample preparation

Care must be taken when taking samples for the POX analyses. It is not allowed to
loose any volatile organic compound. The following diagram illustrates how the
samples should be prepared.
POX sampling
Sample in 1 litre bottle
Add 5 mg sodium sulphite per litre
Seal sample bottle from air
Storage at 4 degr. C
100ml sample in a POX bottle
pH 2-3
POX analysis
10.1.6.3. TOX sample preparation

The TOX analyses is a combination analyses of AOX column and POX. The following
diagram illustrates how the samples should be prepared.
TOX sampling
Sampling
POX method
AOX batchmethod
TOX = POX + AOX

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.6.4. EOX sample preparation

Preparation of extractable organic halogen samples is essential for analyses
performed with the 3000 SYSTEM. Different kinds of samples need different kinds of
sample preparation.
The following diagrams indicate the nature of samples and their specific preparations.
EOX
Soil Water Oil
EOX soil sampling
Sampling
50 g sample
Add 100ml acetone
Shake for 10 min
Add 100ml petroleum ether

or n-hexane
100ml extract in a
separating funnel
Add 200ml water
Shake for 10 min
Separate the waterlayer
Add 200ml water

to 100ml extract
Shake for 10 min
Separate the waterlayer
Dry with sodiumsulfate
Extract and concentrate
EOX analysis

User Manual
TN-TS 3000 Rev. 2.0.2
EOX water sampling (Acc. NEN 6402)
Sampling
Removal of active chlorine
Store at 4 degr. C
Pour 1 litre o the sample

into a separating funnel
pH = 2
Extract with 100 ml

petroleum ether
Water layer pH = 9
Separation of organic phase Extract with 100 ml petroleum ether
Separation of organic phase
Collect extracts
Dry extracts with sodium sulphate
Concentrate to 5 ml by evaporation
Add 100ul hexadecane
Concentrate to 1 ml
EOX analysis
EOX oil sampling (Acc. NEN 6600)
Sampling
Weigh out 2.5 g into a

25ml measuring flask
Fill measuring flask with n-hexaan
Filter the extract with a 0.25 um filter
EOX analysis

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.7. Adjusting gas flows

Before operation gases have to be supplied with a maximum pressure of 3 bar. Open
the gas headers on the gas supply line in the following order.
Close all flow meters by turning the black knob in the clockwise direction. (do not
over- tighten them)
1. Open the gas headers on the gas supply line.
2. Set the oxygen bypass flow meter to 10 mm (35 mL/min) by turning the black
knob counter clockwise. (left flow meter)
The introduction module has to be installed before the next two steps can be
executed.
3. Set the oxygen flow meter to 50 mm (330 mL/min), minimum 40 mm (200
mL/min) (middle flow meter)
4. Set the argon flow meter to 40 mm (200 mL/min), minimum 25 mm (90 mL/min)
(right flow meter)
(Only operating together with the liquids and solids module.)
Note: Instead of manual flow (Rota) meters, digital mass flow controllers can be
installed. In this case, all flow settings will be automatically done by the ThEuS
software.
10.1.8. Filling the scrubber

Before operation the scrubber has to be filled with sulfuric acid.
10.1.8.1. Sulfuric acid scrubber
Special Attention
Make sure that the drip tray is clean and dry and has been placed in
the scrubber compartment.
Place the small beaker under the scrubber.
Fill the scrubber in the following order:
1. Install the selected “sample introduction module” connect it and open the gas
flow.
2. Open the scrubber compartment and position the drip-tray.
3. Shut both stopcocks of the scrubber, the red handles in horizontal position
4. Remove upper glass stopper from the scrubber
5. Fill the scrubber buffer with 95-98 % sulfuric acid
6. Remove any spilled sulfuric acid.
7. Replace upper glass stopper.
8. Check that the lower stopcock of the scrubber is shut. Fill the absorber of the
scrubber to the red line by opening the upper stopcock (red handle in vertical
position) and lift up glass stopper until scrubber is filled.

User Manual
TN-TS 3000 Rev. 2.0.2
9. If the gas is connected take care that a flow is running through the scrubber
immediately after filling.
10. Close upper stopcock (red handle in horizontal position)
11. Close the scrubber compartment.
10.1.8.2. NOx-scrubber
Fill the scrubber in the following order:
1. Open the titration cell compartment and place the drip-tray.
2. Disconnect the outlet of the splash trap with the NOx-scrubber
3. Fill the NOx scrubber with 95-98 % sulfuric acid till the mark on the glass.
4. Remove any spilled sulfuric acid.
5. Reconnect the outlet of the splash bulb to the NOx-scrubber, using clamp no. 12.
6. If the gas is connected take care that a flow is running through the scrubber
immediately after filling.
7. Close the compartment.
10.1.9. Powering the system

If all steps above are carried out carefully and the instrument is connected to a computer
the 3000 SYSTEM can be switched on with the ON/OFF switch on the backside of the
instrument.
1. Switch on the computer
2. Switch on the 3000 SYSTEM.
Now the instrument needs some time to stabilize.
From room temperature up to 1000°C for the furnaces, take approximately 30-45
minutes.
A fresh titration cell will take up to 10-15 minutes to generate a proper baseline.
10.1.10. Installing a selected Module

Place the module on/in the boat driver, located at the right-hand side of the analyzer.
Connect all Argon/Helium and Oxygen inlet tubing, coming from the module (quick
connector) onto the connector socket found on 3000 SYSTEM. Connect the module
with the clamp to the furnace tube and secure it with the screw.

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.11. Titration cell (chloride)

Make sure the cell (the glass) is clean. Any gray deposit should be removed by filling
the cell with ammonia and leaving it for 15 minutes in a ventilated cabinet, then rinse
thoroughly with water. Pre-rinse the cell with a small quantity of electrolyte in order to
remove any excess water. Fill the cell with electrolyte up to a level between the
marks/level lines. (Never use organic solvents to clean the cell.)
Fill the electrode with the halide electrolyte solution and add the four electrodes like
described in paragraph 8.6.1.1. Fill the cell with the correct electrolyte solution, up to
the level mark. Before and during cell replenishing, the gain must be set to zero in
order to prevent heavy pollution of the cell and/or damage to the coulometer
electronics. Once the cell is filled and the electrodes have been inserted, the cell can
be placed onto the stirrer motor.
If the cell replenishment was carried out correctly, with the bias for the halide-
analysis at -315 mV and for the sulfur-analysis at 135-145 mV, a positive signal
should be shown. The current has to have a value between approximately 200 and
600 µA.
Depending on the speed of the cell (condition of the electrodes) and gain level, the
signal should return within 3 to 5 minutes. If upon return, the signal at first drops to
negative and then returns to a positive signal to arrive at a base line between
approximately -0.5 to +1 µA, you may have a case of overshoot due to the excess
gain.
For the halide-cell approximately 5 µL of 0.1 to 0.2 M NaCl has to be injected directly
into the cell before decreasing the gain. While doing this, make sure the needle tip is
fully immersed in the electrolyte in order to obtain a regular signal. This procedure
must be carried out twice. If any overshoot occurs, the gain must be decreased.
After carrying out the procedure of above, the recovery must be tested.
Halide-analysis:
A 2 mM solution of NaCl can be used. Inject 10 µL of the solution. In theory, this
should result in a yield of 1.92 mC, but in practice this value could be exceeded with
approximately 10% due to the contribution of light that enters the cell when the cover
is opened, a statically charge coming from the syringe and operator etc.
If the test results are correct, the cell, coulometer and PC have been tested and are
working properly.
If the subsequent connection of the gases results in insufficient yield or
reproducibility, the cell need not be included in any further trouble-shooting
procedures.

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.12. Titration cell (sulfur)

Make sure the cell (the glass) is clean. Any deposit should be removed by cleaning it
with water and/or a tissue paper. Pre-rinse the cell with a small quantity of the sulfur-
electrolyte in order to remove any excess water. Fill the cell with electrolyte up to a
level between the marks/level lines. (Never use organic solvents to clean the cell.)
Add the four electrodes like described in paragraph 8.6.2.1. Fill the cell with the correct
electrolyte solution, up to the level mark. Before and during cell replenishing, the gain
must be set to zero in order to prevent heavy pollution (incorrect titration) of the cell
and/or damage to the coulometer electronics. Once the cell is filled and the
electrodes have been inserted, the cell is placed onto the stirrer motor. Connect the
sulfur cell to the output of the splash bulb with the gasses turned on. Turn the gain
back on. (level set at 10%) If the cell replenishment was carried out correctly, with the
bias for the sulfur-analysis at 135-145 mV, a positive signal should show. If the signal
goes negative, put the gain to zero again and inject a sample/standard first. This
procedure is carried out, using the “liquids module” and an organic sulfur standard. If
the sample introduction is finished the gain may be turned to the previous level again.
Check if the cell runs “positive” now. Depending on the speed of the cell (condition of
the electrodes) and gain level, the signal should return within 3 to 5 minutes. If upon
return, the signal at first drops to negative and then returns to a positive signal to
arrive at a base line between approximately -0.5 to +1 µA, you may have a case of
overshoot due to the excess gain.
After carrying out the above procedure, the recovery must be tested.
Reproducibility is important at this stage (within 5 %). The yield must be 80 % or

higher.
If the test results are correct, the cell, coulometer and PC have been tested and are
working properly.
If the subsequent connection of the gases results in insufficient yield or
reproducibility, the cell need not be included in any further trouble-shooting
procedures.

User Manual
TN-TS 3000 Rev. 2.0.2
10.1.13. Gas leakage test coulometric configuration
Procedure 1
For reliable and accurate analysis the 3000 SYSTEM needs to be free of leakage.
Therefore a gas leak test has to be performed.
The next steps explain the gas leak test:
1. Close the flow regulator for the oxygen-supply and lower the Argon-flow to
approximately 5 mm.
2. Observe the flow in the Sulfuric Acid of the scrubber. There still has to be a low
flow visible.
3. Shut down the stirrer of the Titration Cell and observe if a similar bubble appears.
This demonstrates that even at low flow-rates the gas arrives into the Cell and at
the same time proves that all other connected items are gas-tight.
Gas leakage test ok > proceed with analysis.
Gas leakage test false > proceed with next steps.
The furnace tube, outlet, modules, joints, etc may become very
hot during the operation of the 3000 SYSTEM. Carelessness may
result in burns.
Procedure 2
1. If there are no bubbles visible, a gas leakage has to be fixed. Adjust flows to the
“normal” levels. (setting according current method)
2. Disconnect the gas stream between furnace output and the “connection furnace
scrubber”.
3. Manually obstruct the gas stream on the outlet (using a septum) and observe the
flow meters. They should drop approximately 5-10 mm within 10-15 seconds.
Removing the septum from the output should clearly release pressure from the
tube. This indicates that no gas-flow leakage is present in the connectors,
Module, Furnace-tube and other joints. The leakage has to be further down the
flow path. (leakage could be found in the septum of the module, any gas
connector, glass joints, loose clamps, mineralized furnace tube, etc.)

User Manual
TN-TS 3000 Rev. 2.0.2
4. Connect the “connection furnace scrubber” and “scrubber” again and obstruct the
flow, coming from the scrubber. The flow meters should drop approximately 5-10
mm within 10-15 seconds. Removing the septum from the output should clearly
release pressure from the scrubber. This indicates that no gas-flow leakage is
present in all connected parts in the flow path. The leakage has to be further
down the flow path. (leakage could be found in the gas connector going to the
scrubber, the glass joints, due to dirt on the grind surface, the furnace tube,
connection furnace scrubber, scrubber-inlet, -outlet etc.
5. Install the splash bulb again including the tubing and repeat the “obstruct”
procedure.
6. The final check will be the number 3 step from procedure 1.
Following these steps should clearly lead to the “problem” and solution in the flow
path.

User Manual
TN-TS 3000 Rev. 2.0.2
10.2. 3000 SYSTEM Normal operation

The software controls the operation of the 3000 SYSTEM. Parameters like
temperature, sample introduction speed, data acquisition, cell stability, etc, are stored
in so called “Method files”. These files are loaded as default- or customer adjustable
methods. Generating or modifying methods is clearly described in the software
manual.
During normal operation small maintenance has to be carried out regularly. The next
paragraphs will describe the following subjects:
1. Visible inspection of glassware

2. Glassware maintenance
3. Introduction module
4. Standard setpoints
10.2.1. Visible inspection of glassware

All glassware parts should be checked regularly, once a week, on scratches,
disposals and blocking of the gas path. After the inspection a gas leak test should be
performed. (refer to 10.1.13 for gas leakage test)
10.2.2. Glassware maintenance
10.2.2.1. Scrubber
If the capillary in the scrubber (final gas inlet into the sulfuric acid) appears black, this
may cause blockage or serious restriction to the flow. In addition, the "soothing" may
cause memory effects to occur. Therefore, a clean scrubber is necessary.
Take the necessary precautions to avoid contact with sulfuric acid.

Ware protective gloves, goggles and clothing, according safety
procedures on the laboratory.
Failure to do so may result in physical injury.
Cleaning procedure:
1. Remove all H2SO4 from the scrubber.
2. Remove the drip tray from the system.
3. Disconnect the connecting plug to the scrubber.
4. Remove the bypass gas connection from the glassware.
5. Remove the scrubber from the system and remove all “stop cocks”.
6. Rinse off as much of the pollution as possible (taking care not to damage the
heater ribbon).
7. Rinse out the scrubber with water.
8. Heat the scrubber in an oven at 500 oC for approx. 30 minutes (leaving the
plastic connection plug to protrude through the oven door!).
9. After re-installation, make sure the heater ribbon reaches the set temperature
again (300°C) and carry out the gas test.

User Manual
TN-TS 3000 Rev. 2.0.2
10.2.2.2. Furnace tube

In the furnace tube also, soot is one of the causes of the memory effect.
Mineralization can also cause the same effect (the tube sometimes becomes slightly
porous).
Soot deposited at the end of the furnace tube is relatively easy to remove.
1. Remove the clamp between the tube and the scrubber.
2. Remove the latch between the tube and the cassette.
3. Set the furnace temperature to 1000 oC and pull back the tube halfway (it will
be clean in 10 minutes).
The tube becomes opaque on the inside and sometimes on the outside. This can be
recognized as mineralization of the tube. The speed of mineralization depends
strongly on the sample matrix and the sample quantity.
In some cases Thermo Fisher Scientific can remedy this. Please contact the Thermo
Fisher Scientific Service/Support Department for more information.
10.2.2.3. Liquids module

During the use of the “liquids module” analysis, the inner tube and the injection port
can become polluted. Reversing the connected 02 and Ar/He gas flows will burn off
this pollution. If required, this can be monitored on the display (base line going up >
pollution, baseline coming down again is clean). A temporary increase of the “liquids
module” temperature accelerates this process.
Note: Before commencing analysis, make sure the gasses have

been reconnected in the correct order!
10.2.2.4. AOX glassware

During AOX analysis, the boat and/or frit often cause a memory effect. By
introducing samples into the furnace tube too fast, moisture can flow back into the
sample introduction section of the AOX glassware (visible as condensation). If this
happens, a second peak can occur when the hot boat returns from the furnace. If
this is visible, the glassware must be cleaned in an oven. Please contact the Thermo
Fisher Scientific Service Department for more information.
The effect may also be caused by mineralization of either the boat or the frit, or both.
Replacing them may be the only solution. The service life of the frit and the boat
often depend on the number of runs, the nature and components of the sample, and
whether or not the equipment is rinsed with demineralized water. Removal of any
nitrate traces increases the service life of the quartz.

User Manual
TN-TS 3000 Rev. 2.0.2
10.2.2.5. POX glassware

The POX module has a bypass gas flow in “standby” and a sample gas flow during
actual analysis.
The gas of the bypass flows directly to the coupling, through the valve and into the
tube.
The sample gas flow travels to the coupling via the valve leading to the long needle,
through the sample bottle, the short needle, the long foam vessel pipe, the short
foam vessel pipe, the valve and into the furnace tube.
Of course, both gas flows must be identical.
Check
1. Set the 02 flow at 10 mm (35 mL/min) and close the bypass.
2. Check gas flow through the scrubber.
3. Insert an empty sample bottle with a septum in good condition (in case of
doubt, use a new one) and insert both needles into the empty sample bottle.
4. Press the analyze button at the control-window and check the gas flow that
should be equal to that of point 2.
If both gas flows are not equal, a leaking septum or the tubing not fitting properly into
the couplings, blocked needles, etc may cause this.
(further info on gas-test, trouble shooting 10.1.13)
10.2.2.6. Solids glassware

The instructions for “liquids module” and AOX apply for solids.
10.2.3. Introduction module

Replace the septum when necessary but at least once every week. If a new sample
boat is used or the boat is dirty, clean this by introduction into furnace tube during 4
minutes at 1000 oC. (or when used for more difficult sample matrices at 1100°C)
10.2.3.2. Liquids Module

Replace the septum when necessary, but at least once every week.
10.2.3.3. AOX Module

If a new boat is used or the boat is dirty, clean this by introduction into the furnace
tube during 4 minutes at 1000 oC. (or when used for more difficult sample matrices at
1100°C)
10.2.3.4. POX Module

Replace the septum after every analysis and check the tubing regularly.

User Manual
TN-TS 3000 Rev. 2.0.2
10.2.4. Standard setpoints

The software controls most of the setpoints. These parameters are related to a
method. These methods describe all parameters necessary for running some
applications.
The following defined methods are as default available in the software:
1. EOX / EOS Extractable organic halogen or organic Sulfur analysis method for
liquid applications
2. AOX / TOX Adsorbable or Total organic halogen analysis method for liquid
applications
3. POX purgable organic halogen analysis method for liquid applications
4. TX / TS-liquids Total halogen or sulfur analysis method for liquid applications
5. TX / TS-gas Total halogen or sulfur analysis method for gas applications
6. TX / TS solids Total halogen or sulfur analysis method for solid applications
Other methods are custom made by Thermo Fisher Scientific or created by customers
themselves. The software manual describes how these methods can be
created/changed.
An example of setpoints is given in “Appendix I : Settings”. For more information see
software manual.
10.3. 3000 SYSTEM Standby mode

When no analyses are carried out for a short period of time (a few days) it is
recommended to put the 3000 SYSTEM in standby mode.
1. Disconnect the gas supply to the NOx-scrubber. (remove the clamp between the
splash-bulb and the NOx-scrubber)
2. Drain the sulfuric acid scrubber into the small beaker.
clockwise. (observe if all acid has left the scrubber before the header is closed)
4. Set the following temperatures:
Heating Setpoint
Furnace 1 700°C
Furnace 2 700°C
Outlet 25°C
Now the instrument is in standby mode.

User Manual
TN-TS 3000 Rev. 2.0.2
10.4. 3000 SYSTEM shut down

When no analysis are carried out for a longer period of time it is recommended to
shut the 3000 SYSTEM down.
1. Disconnect gas supply to the NOx-scrubber. (remove the clamp between the
splash-bulb and the NOx-scrubber)
2. Drain the sulfuric acid scrubber into the small beaker and discard the acid.
3. Remove NOx-scrubber acid.
4. Close header gas supply and close flow meters by turning the black knob
clockwise.
5. Set the gain to zero in the software and/or disconnect the cathode first.
6. Disconnect the coulometer cables from the cell.
7. Empty the cell and remove the electrodes.
8. Close the 3000 SYSTEM software.
9. Switch off the 3000 SYSTEM.
Now the instrument is turned off.

User Manual
TN-TS 3000 Rev. 2.0.2
11. Running analysis TX/TS mode (coulometric)
This chapter gives a brief description of the actual procedure for analysis.
Basically there are two possibilities for running samples: Manually or automatically.
Once the unit is switched on and all setting like temperature, flows etc have reached
their desired levels, the actual analysis may be started.
11.1. Manual analysis in general

An analysis is considered a “manual analysis” when the sample is introduced in a
“one at the time” sequence. This means:
1. check if the baseline run at the expected level

2. introduce the sample in the introduction module
3. press the start button in the software
4. next the sample is introduced by “hand” or by integrated “boat driver” (software
controlled)
5. combustion and titration takes place
6. a graphic appears on the screen
7. wait until the graphic returns to baseline and terminate the analysis or wait until
the maximum time has elapsed
8. the calculated result appears on the screen and the sequence may be repeated
Some system configuration could come without a “boat driver”. This device is
responsible for the actual movement of the sample boat and automatic plunger
pushing for syringe injection (controlled by stepper motor and software).
In case of not having a “boat driver,” the sample boat and plunger from the syringe
are controlled by hand.
11.2. Manual analysis using specific modules/methods
11.2.1.1. Manual introduction POX

The POX module is normally positioned on top of the 3000 SYSTEM system.
The module connector should be inserted into the ID-connector. Closing the software
program (controller window) and starting it again initiates the POX module. The POX
temperature should be visible on the screen. Check all system parameters like gas
flow (see chapter 10.1.13), temperatures, program settings, method selection,
detection cell performance (see chapter 10.1.11) etc.

User Manual
TN-TS 3000 Rev. 2.0.2
The following steps should take you quickly through the procedure and run an actual
sample.
1. Open a new queue list and key-in the necessary parameters (for more details,
refer to the software manual)
2. Open “analysis” in the “controller window” and select the box “methods”. Choose
the appropriate POX analysis method according the application.
3. Open “evaluation” and select the “absolute” calculation method (the calibration
field at this point is not used)
4. Place the sample in the POX module (for sample prep refer to: 10.1.6.2) and
allow the first sample to heat up to approximately 60°C, which usually takes
about 8 minutes. In the mean while the second sample is placed to avoid waiting
time for the next analysis.
5. Lower the injection head of the POX module and observe if both needles have
penetrated the septum sufficiently.
6. Select or add in the queue list the sample to be analyzed and press “analyze”.
Depending on program settings the analysis terminates when sample is
completely purged and the baseline reaches its normal baseline level again.
Manual termination is possible by keying in a lower number of minutes/seconds
analysis time or putting the cursor at the finishing baseline and click on the right
mouse key. This will automatically key in the selected time.
7. The next sample should have reached operational temperature and is ready for
analysis. Select the sample to be analyzed and repeat the steps starting from 5.
11.2.1.2. Manual introduction AOX

The AOX module is positioned in the boat driver and connected onto the furnace
tube of the 3000 SYSTEM system.
The AOX module connector should be inserted into the ID-connector. Closing the
software program (controller window) and starting it again initiates the AOX module
settings. The AOX temperature settings should be visible on the screen. Check all
system parameters like gas flow (see chapter 10.1.13), temperatures, program
settings, method selection, detection cell performance (see chapter 10.1.11) etc.
Warning
sample.
the appropriate AOX analysis method (batch or column) according the application.
(for more details see chapter 10.1.6.1)
User Manual
TN-TS 3000 Rev. 2.0.2
4. Place the prepared carbon-sample in the AOX module.
completely oxidized and the baseline reaches its starting point again. Manual
termination is possible by keying in a lower number of minutes/seconds analysis
time or putting the cursor at the finishing baseline and click on the right mouse
key. This will automatically key in the selected time. Note that a certain “cooling
time” is needed for the sample boat to reach an acceptable temperature again. A
hot boat could oxidize the sample in an early stage, producing erratic numbers.
(typical cooling time is 4 minutes)
6. Now the 3000 SYSTEM is ready for the next analysis. Select the sample to be
analyzed and repeat the mentioned steps starting from 4.
11.2.1.3. Manual introduction Solids, water and heavy hydrocarbons

The Solids module is positioned in the boat driver and connected onto the furnace
tube of the 3000 SYSTEM.
The Solids module connector should be inserted into the ID-connector. Closing the
software program (controller window) and starting it again initiates the Solids module
settings. The Solids temperature settings should be visible on the screen. Check all
system parameters like gas flow (see chapter10.1.13), temperatures, program
settings, method selection, detection cell performance (see chapter10.1.11) etc.
sample.
the appropriate “Solids analysis method” according the application. (for more
details check your application note or check the web: www.thermo.com )
4. Place the sample in the Solids module. (by weight in a sample cup or via syringe
by volume injection in a sample cup)
completely oxidized and the baseline reaches its starting point again. Manual
termination is possible by keying in a lower number of minutes/seconds analysis
time or putting the cursor at the finishing baseline and click on the right mouse
key. This will automatically key in the selected time. Note that a certain “cooling
time” is needed for the sample boat to reach an acceptable temperature again. A
hot boat could oxidize the sample in an early stage, producing erratic numbers.
(typical cooling time is 4 minutes)
6. Now the 3000 SYSTEM is ready for the next analysis. Select the sample to be
analyzed and repeat the mentioned steps starting from 5.

User Manual
TN-TS 3000 Rev. 2.0.2
11.2.1.4. Manual injection EOX and “light hydrocarbons”

The EOX module is positioned in the boat driver and connected onto the furnace
tube of the 3000 SYSTEM.
The EOX module connector should be inserted into the ID-connector. Closing the
software program (controller window) and starting it again initiates the EOX module
settings. The EOX temperature settings should be visible on the screen. Check all
system parameters like gas flow (see chapter10.1.13), temperatures, program
settings, method selection, detection cell performance (see chapter10.1.11) etc.
sample.
the appropriate EOX/TX analysis method according the application. (for more
details see chapter10.1.6.4)
4. Take a 100µL syringe and fill it with the prepared EOX or TX (light hydrocarbon)
sample.
6. Insert the needle through the septum and let the syringe rest on the support. The
plunger pusher in the “boat driver” performs the injection itself. Injection speed
and volume are software controlled and application dependable.
7. The analysis terminates when sample is completely oxidized and the baseline
reaches its starting point again. Manual termination is possible by keying in a
lower number of minutes/seconds analysis time or putting the cursor at the
finishing baseline and click on the right mouse key. This will automatically key in
the selected time. Now the 3000 SYSTEM is ready for the next analysis. Select
the sample to be analyzed and repeat the mentioned steps starting from 4.
11.3. Automatic analysis in general
An analysis is considered “automatic analysis” once samples are unattended

introduced into a “sample introduction module” by means of an “autosampler” and the
sequence runs all samples according the queue list. In order to prepare the 3000
SYSTEM plus autosampler for actual analysis, a few parameters should be checked.
1. check if the baseline runs at the expected level

2. place the samples in the autosampler and built a queue list.
3. press the “analyze” button.
4. next the sample is introduced by the autosampler and/or “boat driver” (software
controlled)
5. combustion and titration takes place
6. a titration curve appears on the screen

User Manual
TN-TS 3000 Rev. 2.0.2
7. the unit waits until the curve has returned to baseline and terminates the analysis
as soon as the maximum time has elapsed or the appropriate baseline level is
reached. (depending on software settings)
8. the calculated result appears on the screen and the sampler starts the next
sample injection/introduction.
11.4. Automatic analysis using specific modules/methods
11.4.1.1. Automatic analysis AOX

The automatic sample handling and introduction for AOX batch method, using the
ESA2000 and AOX/TOX column method, using the ECA1700 are found in chapters:
• 7.2 ECA1700 column sampler

• 7.3 ESA2000 AOX batch method
11.4.2. Automatic introduction Solids, water and “heavy” hydrocarbons

The automatic sample handling and introduction for solids samples or water, waste
water for TX/TS analysis is carried out by the ESA2000 auto sampler. The sampler is
also used for heavy hydrocarbons like waste oil, crude or anything with a high boiling
point or viscosity. The sample is introduced using a sample cup. Simply determine
the weight, key it in the software and place it into ESA2000, which in combination
with the solids module, carries it into the furnace. Detailed information concerning the
ESA2000 is found in chapter:
• 7.3 ESA2000 solids auto sampler
11.4.2.1. Automatic injection EOX and “light hydrocarbons”

Automatic sample introduction for EOX or light hydrocarbons is carried out by the
NeXYZ auto sampler. The sampler is capable to pick up sample volume from a vial
positioned in a sample tray and control the speed of injection into the liquids EOX
module.
Detailed information is found in the User’s Guide of the NeXYZ.

User Manual
TN-TS 3000 Rev. 2.0.2
12. Troubleshooting Nitrogen-Sulfur UV mode
The 3000 system has been designed to achieve a high level of reliability. In case
of problems or failure, these troubleshooting guidelines will be helpful.
Malfunction Possible cause Action

The response is too slow or Perma pure is blocked Replace the perma pure
Recovery is too low or too high Perma pure is melted Replace the perma pure
Soothing in the perma pure Clean it or replace it by a new
perma pure
Vacuum pump is out of order Contact the Thermo Fisher
(drying of the gasses) Scientific Service Department
Gas leakage Check the apparatus
Wrong calibration line Analyze a new calibration set
or choose the right one
Using a wrong size needle Replace the needle
Wrong type of filter installed Replace for proper one
Filter is soothed Replace or clean the Filter
Recovery is too low Furnace temperature is incorrect Check the oven temperature
Recovery is too high High blank values for the solvent Check the solvent, if
used for the Liquid analysis necessary clean by distillation.
Dirty glass fiber filter Replace or clean filter
The injected volume has been Correct for needle content
increased by the contents of the
needle (manual injection)
Heating to a higher temperature Clean the sample boat by
has not adequately cleaned heating, e.g. by increasing the
sample boat. furnace temperature.
Irregular or repeating spikes Software Error Contact the Thermo Fisher
Scientific Service Department
Incorrect communication with Contact the Thermo Fisher
IOC-card Scientific Service Department
Incorrect baseline If the baseline does not behave Contact the Thermo Fisher
as outlined above, this may be Scientific Service Department
caused by a number of factors
Too much noise Pollution Clean new/used glassware
Check the tubing
Check the temperature
Check the environmental air
for high concentrations S
Incorrect communication with Contact the Thermo Fisher


User Manual
TN-TS 3000 Rev. 2.0.2

Generally too high baseline Incorrect communication with Contact the Thermo Fisher
Gas problems Check gas supply and the

sample introduction section
When possible connect the
gas bottles separately, so it is
possible to circumvent the gas
supply network
no signal No gas routing into the UV or Check gas path
Nitrogen detector
Disconnected data cable Check cable back and forth
Defective TS/TN board Check if there is any signal

from the ref. cable
(must be 0-10 V) and contact
the Thermo Fisher Scientific
Service Department

User Manual
TN-TS 3000 Rev. 2.0.2
13. Troubleshooting Coulometric option

No cell current. Gain control on zero. Turn the gain control to 7-15.
Cathode or anode disconnected. Re-connect the cathode or
anode.
Coulometer cable disconnected Check the wiring and
from PC or cell. reconnect.
Cell current deviates greatly from Electrical connection between Fill the titration cell with
zero or fluctuates. cell and microcoulometer is electrolyte solution and check
broken. whether electrolyte solution is
present in the side arm of the
titration cell.
Bad or badly connected Change reference electrode
reference electrode. for a spare one. Check
cables.
Cell current is large and positive. Cl- is leaking from the reference Change the reference
electrode into the cell. electrode.
Cell current is large and The system is severely Change the electrolyte
negative. contaminated with silver ions. solution.
Cell current is unstable. Irregular stirring, stirrer element Check the stirrer element and
out of phase; the cell is not firmly stirrer motor.
located on the stirrer motor.
The silver surface of the indicator Allow the electrode to stabilize
electrode has not yet stabilized for a period of time or replace
e.g. after polishing or renewal. with a stabilized electrode.
Dirty cell. After removing the electrodes,
flush the cell thoroughly with
ammonia, demineralized
water and electrolyte solution.
Droplets of condensation falling Dry the electrode holder and
back into the cell. the electrodes.
Changing exposure to light of the Make sure that the cell

cell. cabinet is properly shut.
Temperature fluctuations in the Prevent excessive heating or

cell. cooling of the cell cabinet.
Draughts, sunlight, etc may
cause heating or cooling.
Small volume of titration solution Top up the titration solution

User Manual
TN-TS 3000 Rev. 2.0.2

No response to Chloride dosage. Incorrect bias potential, making Check the potential difference
the system insensitive to chloride between the indicator
and silver ions. electrode pair. The bias
setting should be –315 mV.
No chloride titrated into the Use a syringe and long needle
solution. to add chloride.
Loose anode or Cathode Reconnect
Disconnected wiring Reconnect
Broken wiring/Electrodes Call service department
Titration time is too long The cell is severely After removing the electrodes,
Contaminated with AgCI. clean the cell with concentrate
ammonia, large amounts of
demineralized water and
electrolyte solution.
The composition of the Replace the solution with new
electrolyte is incorrect. solution with the correct
solution.
Incorrect bias potential, causing Adjust the bias potential until it

a delay in the response of the is correct.
indicator electrode.
Indicator electrode is slow. Replace the indicator
electrode for example by
switching it with the anode.
Titration time is too slow Large volume of titration solution Increase the gain or drain off
some titration solution.
Titration time is too fast Gain level is set too high Reduce the gain
Small volume of titration solution Top up the titration solution
High baseline due to high current Sulfuric acid solution is Purge the sulfuric acid
Cell current is unstable. severely contaminated solution for 15 minutes or
replace it with clean solution.
Contaminated gases (oxygen, Clean the gases, for example
argon) by inserting a gas cleaning
filter between the gas
cylinders and the ECS1200.
Apparatus is contaminated with Clean the titration cell with
organic halogen compounds conc. ammonia, water and
demin. water.

User Manual
TN-TS 3000 Rev. 2.0.2

Long titration time. Gain is set too low. Increase gain level.
Gas flows too low Check the flow setting and the
apparatus for blockages in the
scrubber or titration cell inlet.
Check the apparatus for leaks
(including the septum of the
EOX and POX modules).
Recovery too low Furnace temperature is incorrect Check the oven temperature
Inlet temperature in the liquids Check the inlet temperature
module is incorrect
Organic halogen condensation in Add hexadecane to the
the injection needle extract and raise the injection
speed to a maximum of 0.5 μI
per
second.
Gas leaks Check the apparatus for the
presence of 'Teflon' sleeves,
etc.
Too little electrolyte in the Top up the titration solution
titration cell so that not all
Halogen is absorbed.
Recovery is too high High blank values for the solvent Check the solvent, if
used for the Liquid analysis necessary clean by distillation.
The injected volume has been Correct for needle content
increased by the contents of the
needle
Adsorbed halogen is being Repeat the measurement
released during combustion as a several time or clean the
result of pronounced expansion glasswork by heating.
(AOX)
Heating to a higher temperature Clean the sample boat by
has not adequately cleaned heating, e.g. by increasing the
sample boat. furnace temperature.

User Manual
TN-TS 3000 Rev. 2.0.2

Irregular or repeating spikes Air bubbles in the injection Clean the syringe and check if
syringe (EOX, EOS) there still is enough wash
solution available
Condense in the splash bulb Dry the splash bulb and check
(HCl absorption) the O2 and Ar/He flows
A defect in the scrubber heating Increase the temperature to
or low temperature setting, (HCI normal levels.
absorption) due to condenses in Contact the Thermo Fisher
the heater section Scientific Service Department
Furnace temperature or gas flow Check the possible causes
is too low (soothing); injection
speed is too high (EOX
soothing).
In correct baseline If the baseline does not behave Contact the Thermo Fisher
as outlined above, this may be Scientific Service Department
caused by a number of errors
Too much noise Pollution Clean new/used glassware
Refill the coulometer cell
Check the tubing
Check the temperature
program
Generally too high baseline Cell problems Check whether the baseline
drops to an acceptable level
when the cell is disconnected
from the scrubber
Gas problems Check gas supply and the

sample introduction section
When possible connect the
gas bottles separately, so it is
possible to circumvent the gas
supply network

User Manual
TN-TS 3000 Rev. 2.0.2
14. Consumables and spare parts

The list below gives an overview of consumables and spare parts needed for the
3000 system, samplers and additional system features. This list is updated
September 2004.
SPARE PARTS TS 3000

PGENE0031 Permapure scrubber complete
PGENE0032 Permapure dryer
PANAL0126 Turbo tube model 3000
MODUL0004 Quartz combustion boat Solids
PGENE0002 Syringe 100 µL, 71 mm needle, p.s. 5
PGENE0004 Injection needle Hamilton, 71mm, p.s. 5, 3 pcs
TS3000003 UV scrubber
CONSUMABLES TS 3000
PGENE0052 Glass fiber filters, 10 pcs
PANAL0025 Septum, diam. 12mm, 10 pieces
PINJE0012 Quartz sample boat, solids
PANAL0211* Set of Standards; 0, 1, 5, 10 mg S/L di-n-butyl sulfide in
toluene dibenzothiophene, 1 mg S/L
PANAL0125 Combustion tube universal model 3000
PANAL0174 Ceramic needle, 150 mm
SPARE PARTS TN 3000

PGENE0031 Permapure scrubber complete
PGENE0032 Permapure dryer
TN3000022 Ozone killer
CONSUMABLES TN 3000
PANAL0161 Paper filters 5µm, 10 pcs
PGENE0029 Catalyst Pt on ceramic base, 100 gr
PANAL0167* Ammoniumsulphate, 50 gr
PANAL0168* Potassiumnitrate, 50 gr
SPARE PARTS ORGANIC APPLICATION

PANAL0126 Turbo tube model 3000
MODUL0004 Quartz combustion boat Solids
PGENE0039 Syringe 100 µl, 120 mm needle, p.s. 1
PGENE0038 Injection needle, 120 mm, p.s. 1, 3 pcs

User Manual
TN-TS 3000 Rev. 2.0.2
CONSUMABLES ORGANIC APPLICATION

PANAL0221* Benzonitril in toluene standards:
1, 10, 50 mg N/L
PANAL0220* Benzonitril in iso-octane standards:
100, 200, 500, 1000, 2000, 5000 mg N/L
SPARE PARTS ECS 3000

PANAL0021 Gasinlet
ECS300006 Scrubber ECS 3000
ECS200006 Splash bulb ECS 2000/3000
ECS300009 Connection tube furnace/scrubber 3000
ECS300010 Connector to gasinlet ECS 3000
SPARE PARTS CHLORINE

PANAL0046 Halogens titration cell, capillary
PANAL0047 Electrode container capillary cell
PANAL0049 Generating electrode, Ag, cap. cell
PANAL0050 Measuring electrode, Ag, cap. Cell
PANAL0051 Cathode, Pt, Cap. Cell
PANAL0052 Halogen reference electrode, 3M KCl saturated with AgCl
SPARE PARTS SULPHUR

PANAL0072 Sulphur cell iodometric, 35mL
PANAL0073 Electrode container, 35mL cell
PANAL0074 Generating electrode, Pt, 35mL cell
PANAL0075 Measuring electrode, Pt, 35mL cell
PANAL0076 Sulphur reference electrode, Pt
PANAL0092 Cathode, Pt
PANAL0038 Halogens scrubber
CONSUMABLES TX/TS LIQUIDS

PANAL0095* Standard Aldrin in water, 0 and 5 mg CI/L 10 x 2 mL
PANAL0211* Set of Standards: Di-n-Butyl Sulfide in toluene:
1, 5, 10 mg S/L
CONSUMABLES TX/TS SOLIDS


User Manual
TN-TS 3000 Rev. 2.0.2
CONSUMABLES AOX BATCH

PANAL0094* Standard p-chlorophenol, 200 mg CI/L, 20 mL
PPTRE0047 Quartzfrit, 3 pieces
PPTRE0049 Activated carbon AOX batch 50 gr
PPTRE0058 Activated carbon AOX batch, 10 gr
CONSUMABLES AOX COLUMN

PANAL0094* Standard p-chlorophenol, 200 mg CI/L, 20 mL
PGLAS0032 Quartz samplecup AOX columnmethod
PPTRE0012 Activated carbon AOX column, 50 gr
PPTRE0022 Ejectiontool
CONSUMABLES EOX
PANAL0095* Standard Aldrin in water, 0 and 5 mg CI/L 10 x 2 mL
PANAL0097* Blank to standard aldrin, 5 x 2 mL
CONSUMABLES POX
PINJE0003 POX samplebottle 100 mL complete
PINJE0002 Septum, 24mm, 10 pieces
PANAL0102* Standard DiChloroMethane 10 mg Cl/L; 10 mL
SPARE PARTS ELS 3000

ELS200003 Vial caps, 100 pieces
ELS200016 ELS furnace needle, 1 piece
ELS200042 Vials 2 mL, 100 pcs
ELS300005 Sampler needle ELS 3000
ELS300006 Septa 7.7 mm PTFE, 100 pcs
ELS300003 Washbottle ELS 3000
ELS300004 Screwcap washbottle ELS 3000
ELS300007 Vial 40 mL for washsolution
ELS200015 PEEK fitting kit
ELS200032 ELS furnace needle coupler
Thermo Fisher Scientific does not supply chemical for the

combustion analyzers. Please consult you local Thermo
Fisher Scientific distributor for information.

User Manual
TN-TS 3000 Rev. 2.0.2
SPARE PARTS EGM 1700/II

EGM170007 Expansion vessel coated
EGM170016 Capillary for EGM 1700
EGM170008 Metal sample loop, 100 µL
EGM170014 Metal sample loop, 10 mL
SPARE PARTS ESA 2000 AOX

MODUL0011 Boatguiding tube AOX for ESA/ECS3000
PGLAS0602 Quartz combustion boat AOX for ESA/ECS3000
PPTRE0047 Quartzfrit, 3 pieces
SPARE PARTS TN WATER

TN3000-065 Glass parts Cold trap
TN3000-068 Furnace tube complete
TN3000-063 Furnace tube with ceramic inlay
TN3000-066 Gas outlet tube
TN3000-064 Scraper tool
TN3000-075 None return tube
PMECH-0007 Clamp KS-18
TN3000-061 Boat
TN3000-067 Nickel sample cylinder
TN3000-062 Introduction module complete
ELS2100-12 Funnel for needle
PANAL 0025 Septum 12mm (10 pieces)
MODUL 0006 Stopper for septum
ELS215011 Needle 1/16” 230 mm long (3 pieces)
PMECH-0008 PTFE sleeve NS29.2
PMECH-0009 Clamp (fork) NS29.2
MODUL-0009 Boat guiding tube (‘AOX’)
SPARE PARTS ESA 2000 (For Solids applications)

ESA200029 Sample cups solids ESA 2000
ESA200030 Inlay for ESA200029
The use of parts, which are not manufactured/approved by

Thermo Fisher Scientific, could result into exclusion of
warranty arrangements.

15.
User Manual 3000 systems V2.0.doc

Appendix I : Settings
TN-TS 3000
User Manual
Method Coolforce CoolNOrm Furn. 1 Furn. 2 Inlet Outlet Argon/Hel Oxygen Ext. Oxygen Ozonator Bypass Needle Fast. Fast Injection Injection Measure
. NOrm/std NOrm/std NOrm/std NOrm/std turbo Position Speed Position Speed
sort % % celsius celsius celsius celsius mm mm mm mm mm mm mm mm/sec mm mm/sec sec.
Liq-Petro 10 10 850/700 1000/700 --------- 60/10 65 40 20 40/50 10/15 120 65.0 15 110 0.6 190
Liq-Water 10 10 900/700 900/700 --------- 60/10 50/65 40 20 40/50 05 120 55.0 15 110 1.2 240
Method Coolforce CoolNOrm Furn. 1 Furn. 2 Inlet Outlet Argon/Hel Oxygen Ext. Oxygen Bypass Needle inj. Speed
. NOrm/std NOrm/std NOrm/std NOrm/std turbo NOrm/turbo
sort % % celsius celsius celsius celsius mm mm mm mm mm mm/sec
Sol-Petro 100 100 850/700 1000/700 --------- 60/10 50 30 20 30 ---------- ---------

Sol-Water 100 100 900/700 900/700 --------- 60/10 50 30 20 30 ---------- ---------
Tips: 1) The temperature for the solids method can be higher, but that depends of the sort of sample you want to measure.
2) When you use a 75 mm needle (100 μl) the next value can be used for the injection speed
0.1 mm/sec = 0.167 μl/sec
Page 150 of 169

Rev. 2.0.2
User Manual
TN-TS 3000 Rev. 2.0.2
16. Appendix II International Chemical Safety Cards

TOLUENE ICSC: 0078
CAS # 108-88-3
TOLUENE
RTECS # XS5250000
Methylbenzene
ICSC # 0078
Toluol
UN # 1294
C6H5CH3/C7H8
EC # 601-021-00-3
Molecular mass: 92.1
TYPES OF
ACUTE HAZARDS/ FIRST AID/
HAZARD/ PREVENTION
SYMPTOMS FIRE FIGHTING
EXPOSURE
Highly flammable. no open flames, no sparks, Powder, AFFF, foam, carbon
FIRE and no smoking. dioxide.
Vapour/air mixtures are Closed system, ventilation, In case of fire: keep drums,
explosive. explosion-proof electrical etc., cool by spraying with
equipment and lighting. water.
Prevent build-up of
EXPLOSION electrostatic charges (e.g., by
grounding). Do NOT use
compressed air for filling,
discharging, or handling.
STRICT HYGIENE! AVOID
EXPOSURE EXPOSURE OF
(PREGNANT) WOMEN!
Dizziness. Drowsiness. Ventilation, local exhaust, or Fresh air, rest. Artificial
INHALATION Headache. Nausea. breathing protection. respiration if indicated. Refer
Unconsciousness. for medical attention.
Dry skin. Redness. Protective gloves. Remove contaminated
clothes. Rinse and then wash
SKIN
skin with water and soap.
Refer for medical attention.
Redness. Pain. Safety goggles or face First rinse with plenty of
shield. water for several minutes
EYES (remove contact lenses if
easily possible), then take to
a doctor.
Abdominal pain. Burning Do not eat, drink, or smoke Rinse mouth. Give a slurry of
sensation (further see during work. activated charcoal in water to
INGESTION Inhalation). drink. Do NOT induce
vomiting. Refer for medical
attention.
SPILLAGE DISPOSAL STORAGE PACKAGING & LABELLING
Collect leaking liquid in sealable Fireproof. Separated from strong
containers. Absorb remaining oxidants. F symbol
liquid in sand or inert absorbent Xn symbol
and remove to safe place. Do R: 11-20
NOT wash away into sewer S: (2-)16-25-29-33
(extra personal protection: self- UN Hazard Class: 3
contained breathing apparatus). UN Packing Group: II
SEE IMPORTANT INFORMATION ON BACK
Prepared in the context of co-operation between the International Program on Chemical Safety &
ICSC: 0078 the Commission of the European Communities © IPCS CEC 1993

User Manual
TN-TS 3000 Rev. 2.0.2
International Chemical Safety Cards

TOLUENE ICSC: 0078
PHYSICAL STATE; APPEARANCE:ROUTES OF EXPOSURE:
I COLOURLESS LIQUID , WITH The substance can be absorbed into
CHARACTERISTIC ODOUR. the body by inhalation, through the
M skin and by ingestion.
PHYSICAL DANGERS:
P The vapour is heavier than air and INHALATION RISK:
may travel along the ground; distant A harmful contamination of the air can
O ignition possible. As a result of flow, be reached rather quickly on
agitation, etc., electrostatic charges evaporation of this substance at
R aregenerated. 20°C.
T CHEMICAL DANGERS: EFFECTS OF SHORT-TERM

Reacts violently with strong oxidants EXPOSURE:
A causing fire and explosion hazard. The substance irritates the eyes and
the respiratory tract. Exposure could
N OCCUPATIONAL EXPOSURE cause central nervous system
LIMITS (OELs): depression. Exposure at high levels
T TLV: 50 ppm; 188 mg/m3 (as TWA) may result in cardiac dysrhythmia,
(skin) (ACGIH 1993-1994). unconsciousness and death.
EFFECTS OF LONG-TERM OR
REPEATED EXPOSURE:
D
Repeated or prolonged contact with
skin may cause dermatitis. The
A
substance may have effects on the
central nervous system , resulting in
T
decreased learning ability and
psychological disorders. Animal tests
A show that this substance possibly
causes toxic effects upon human
reproduction.
Boiling point: 111°C Relative density of the vapour/air-
Melting point: -95°C mixture at 20°C (air = 1): 1.06
Relative density (water = 1): 0.87 Flash point: 4°C c.c.°C
PHYSICAL
Solubility in water: SO2ne Auto-ignition temperature: 480°C
PROPERTIES
Vapour pressure, kPa at 20°C: 2.9 Explosive limits, vol% in air: 1.1-7.1
Relative vapour density (air = 1): 3.2 OctaSO2l/water partition coefficient
as log Pow: 2.69
ENVIRONMENTAL
DATA
NOTES
Depending on the degree of exposure, periodic medical examination is indicated.
Transport Emergency Card: TEC (R)-31
NFPA Code: H 2; F 3; R 0;
Neither the CEC or the IPCS nor any person acting on behalf of the CEC or the IPCS is
IMPORTAN responsible for the use which might be made of this information. This card contains the
T LEGAL collective views of the IPCS Peer Review Committee and may not reflect in all cases all the
NOTICE: detailed requirements included in national legislation on the subject. The user should verify
compliance of the cards with the relevant legislation in the country of use.

User Manual
TN-TS 3000 Rev. 2.0.2

ARGON ICSC: 0154
ARGON
(liquefied, cooled)
Ar
Atomic mass: 39.95
CAS # 7440-37-1
RTECS # CF2300000
ICSC # 0154
UN # 1951
TYPES OF
HAZARD/ PREVENTION
EXPOSURE
not combustible. Heating will For cylinders, see notes. In
cause rise in pressure with case of fire in the
FIRE
risk of bursting. surroundings: all
extinguishing agents allowed.
EXPLOSION
EXPOSURE
Asphyxia. Dizziness. Ventilation. Fresh air, rest. Artificial
INHALATION Unconsciousness. respiration if indicated. Refer
for medical attention.
ON CONTACT WITH Cold-insulating gloves. ON FROSTBITE: rinse with
LIQUID: FROSTBITE. Protective clothing. plenty of water, do NOT
SKIN
remove clothes. Refer for
medical attention.
Pain. Blurred vision. Severe Safety goggles, or face First rinse with plenty of
deep burns. shield. water for several minutes
a doctor.
INGESTION
Ventilation. NEVER direct water jet Store outside or in a separate well-
on liquid (extra personal ventilated building. Cool. UN Hazard Class: 2.2
protection: self-contained
breathing apparatus).

Prepared in the context of co-operation between the International
ICSC: 0154 Programme on Chemical Safety & the Commission of the European
Communities © IPCS CEC 1993

User Manual
TN-TS 3000 Rev. 2.0.2

ARGON ICSC: 0154
I PHYSICAL STATE; APPEARANCE:ROUTES OF EXPOSURE:
COLOURLESS, ODOURLESS, The substance is absorbed into the
M LIQUEFIED GAS. body by inhalation.
P PHYSICAL DANGERS: INHALATION RISK:

The gas is heavier than air and may On loss of containment this gas can
O accumulate in low ceiling spaces cause suffocation by lowering the
causing deficiency of oxygen. oxygen content of the air in confined
R areas.
CHEMICAL DANGERS:
T EFFECTS OF SHORT-TERM
EXPOSURE:
A OCCUPATIONAL EXPOSURE The liquid may cause frostbite.
LIMITS (OELs):
N TLV not established. EFFECTS OF LONG-TERM OR
REPEATED EXPOSURE:
T
PHYSICAL Boiling point: -185.9°C Solubility in water, mL/100 mL at

PROPERTIES Melting point: -189.2°C 20°C: 3.4
Relative vapour density (air = 1): 1.66
ENVIRONMENTAL DATA
NOTES
UN number 1006 for argon,
compressed. In case of fire:
keep cylinder cool by
spraying with water. High
concentrations in the air
cause a deficiency of oxygen
with the risk of
unconsciousness or death.
Transport Emergency Card:
TEC (R)-17
IMPORTANT responsible for the use which might be made of this information. This card contains the
LEGAL collective views of the IPCS Peer Review Committee and may not reflect in all cases all the

User Manual
TN-TS 3000 Rev. 2.0.2

OXYGEN ICSC: 0138
OXYGEN
Oxygen, compressed
(cylinder)
O2
CAS # 7782-44-7
RTECS # RS2060000
ICSC # 0138
UN # 1072
EC # 008-001-00-8
TYPES OF
HAZARD/ PREVENTION
EXPOSURE
not combustible but no open flames, no sparks, In case of fire in the
enhances combustion of and no smoking. No contact surroundings: all
other substances. Many with flammable substances. extinguishing agents allowed.
reactions may cause fire or no contact with fuels and
FIRE
explosion. Heating will cause other combustible materials.
rise in pressure with risk of
bursting.
Risk of fire and explosion on In case of fire: keep cylinder

contact with combustible cool by spraying with water.
EXPLOSION
materials such as oils or fats. Combat fire from a sheltered
position.
EXPOSURE
INHALATION
SKIN
Redness. Safety goggles. First rinse with plenty of
water for several minutes
(remove contact lenses if
EYES
a doctor.
INGESTION
Evacuate danger area! Consult an Fireproof. Separated from
expert! Ventilation. combustible and reducing O symbol
substances. Cool. R: 8-34
S: 21
UN Hazard Class: 2.2
Prepared in the context of co-operation between the International
ICSC: 0138 Programme on Chemical Safety & the Commission of the European

User Manual
TN-TS 3000 Rev. 2.0.2

OXYGEN ICSC: 0138
I COMPRESSED GAS. The substance is absorbed into the
body by inhalation and through the
M
PHYSICAL DANGERS: skin.
P
The gas is heavier than air.
O
INHALATION RISK:
R
CHEMICAL DANGERS:
T
The substance is a strong oxidant
A
and reacts violently with combustible EFFECTS OF SHORT-TERM
N
and reducing materials, with risks of EXPOSURE:
T
fire and explosion hazard.
D
OCCUPATIONAL EXPOSURE EFFECTS OF LONG-TERM OR
A
LIMITS (OELs): REPEATED EXPOSURE:
T
TLV not established. Lungs may be affected by inhalation
A
of high concentrations. Symptoms
may be delayed.
Boiling point: -183°C Relative vapour density (air = 1): 1.43

PHYSICAL Melting point: -218.8°C Octanol/water partition coefficient as
PROPERTIES Solubility in water: moderate (3.1 log Pow: 0.65
mL/100 mL at 20°C)
ENVIRONMENTAL
DATA
NOTES
Do NOT use in the vicinity of
a fire or a hot surface, or
during welding. Also consult
ICSC # 0880.
TEC (R)-842
Neither the CEC or the IPCS SO2r any person acting on behalf of the CEC or the IPCS is
IMPORTAN responsible for the use which might be made of this information. This card contains the
T LEGAL collective views of the IPCS Peer Review Committee and may not reflect in all cases all the

User Manual
TN-TS 3000 Rev. 2.0.2

SODIUM AZIDE ICSC: 0950
CAS # 26628-22-8 SODIUM AZIDE
RTECS # VY8050000 Azide
ICSC # 0950 Azium
UN # 1687 NaN3
EC # 011-004-00-7 Molecular mass: 65.02
TYPES OF
HAZARD/ PREVENTION
EXPOSURE
Decomposes on heating. NO contact with acids, heavy Dry sand, special powder.
FIRE
metals.
Risk of fire and explosion on Do NOT expose to friction or In case of fire: keep drums,
contact with acids and many shock. etc., cool by spraying with
EXPLOSION
metals (lead, brass, copper, water.
mercury, silver).
EXPOSURE STRICT HYGIENE!

Cough. Headache. Local exhaust or breathing Fresh air, rest. Artificial
Shortness of breath. protection. respiration if indicated. Refer
Unconsciousness. Nasal for medical attention.
INHALATION
stuffiness. Blurred vision.
Slowing heart beat. Fall in
blood pressure.
MAY BE ABSORBED! Protective gloves. Remove contaminated
SKIN Redness. Blisters. clothes. Rinse skin with
plenty of water or shower.
Redness. Pain. Safety goggles, or eye First rinse with plenty of
protection in combination water for several minutes
EYES with breathing protection. (remove contact lenses if
a doctor.
Abdominal pain. Nausea. Do not eat, drink, or smoke Rinse mouth. Do NOT induce
Sweating (further see during work. vomiting. Give plenty of
INGESTION
Inhalation). water to drink. Rest. Refer for
medical attention.
Evacuate danger area! Consult an expert! Fireproof. Separated from Do not transport with food and
Sweep spilled substance into plastic acids, food and feedstuffs, feedstuffs.
containers; if appropriate, moisten first to metals, especially lead and T+ symbol
prevent dusting. Carefully collect remainder, its compounds. R: 28-32
then remove to safe place (extra personal S: (1/2-)28-45
protection: complete protective clothing UN Hazard Class: 6.1
including self-contained breathing UN Packing Group: II
apparatus).
Prepared in the context of cooperation between the International
Programme on Chemical Safety & the Commission of the European
ICSC: 0950

User Manual
TN-TS 3000 Rev. 2.0.2

SODIUM AZIDE ICSC: 0950
I ODOURLESS COLOURLESS The substance can be absorbed into
HEXAGONAL CRYSTALS. the body by inhalation, through the
M skin and by ingestion.
PHYSICAL DANGERS:
P INHALATION RISK:
Evaporation at 20°C is negligible; a
O CHEMICAL DANGERS: harmful concentration of airborne
May explode on heating above particles can, however, be reached
R melting point, especially on rapid quickly.
heating , causing fire and explosion
T hazard. The solution in water is a EFFECTS OF SHORT-TERM
weak base. Reacts with copper, lead,EXPOSURE:
A silver, mercury and carbon disulfide The substance irritates the eyes, the
to form particularly shock-sensitive skin and the respiratory tract.
N compounds. Reacts with acids, Exposure slightly above OEL could
forming toxic and explosive hydrogen cause effects on the nervous system.
T azide.
OCCUPATIONAL EXPOSURE
LIMITS (OELs):
D TLV (as (ceiling values)): 0.11 ppm
as hydrazoic acid vapour ppm; 0.29
A mg/m3 as sodium azide (ACGIH
1996).
T
Decomposes below melting point at Solubility in water, g/100 mL at 17°C:

PHYSICAL
275°C 41.7
PROPERTIES
Relative density (water = 1): 1.8475 Solubility in water: good (41.7 g/100
mL water at 17°C)
ENVIRONMENTAL
DATA
NOTES
The occupational exposure
limit value should not be
exceeded during any part of
the working exposure. Smite
is a trade name.
TEC (R)-61G12b
LEGAL collective views of the IPCS Peer Review Committee and may not reflect in all cases all the

User Manual
TN-TS 3000 Rev. 2.0.2

SULFURIC ACID ICSC: 0362
CAS # 7664-93-9 SULFURIC ACID
RTECS # WS5600000 Sulfuric acid 100%
ICSC # 0362 Oil of vitriol
UN # 1830 H2SO4
EC # 016-020-00-8 Molecular mass: 98.1
TYPES OF
HAZARD/ PREVENTION
EXPOSURE
Not combustible. Many NO contact with flammable NO water. In case of fire in
reactions may cause fire or substances. NO contact with the surroundings: powder,
FIRE explosion. Gives off irritating combustibles. AFFF, foam, carbon dioxide.
or toxic fumes (or gases) in a
fire.
Risk of fire and explosion on In case of fire: keep drums,
contact with base(s), etc., cool by spraying with
EXPLOSION combustible substances, water but NO direct contact
oxidants, reducing agents or with water.
water.
PREVENT GENERATION IN ALL CASES CONSULT A
EXPOSURE OF MISTS! AVOID ALL DOCTOR!
CONTACT!
Corrosive. Burning Ventilation, local exhaust, or Fresh air, rest. Half-upright
sensation. Cough. Laboured breathing protection. position. Artificial respiration
INHALATION
breathing. if indicated. Refer for medical
attention.
Corrosive. Redness. Serious Protective gloves. Protective Remove contaminated
skin burns. Pain. clothing. clothes. Rinse skin with
SKIN
plenty of water or shower.
Refer for medical attention.
Corrosive. Redness. Pain. Face shield or eye protection First rinse with plenty of
Severe deep burns. in combination with breathing water for several minutes
EYES protection. (remove contact lenses if
a doctor.
Corrosive. Abdominal pain. Do not eat, drink, or smoke Rinse mouth. Do NOT induce
INGESTION Burning sensation. Collapse. during work. vomiting. Refer for medical
attention.
Collect leaking liquid in sealable Separated from combustible and Unbreakable packaging; put
containers. Do NOT absorb in reducing substances, strong breakable packaging into closed
saw-dust or other combustible oxidants, strong bases, other unbreakable container. Do not
absorbents (extra personal materials, food and feedstuffs (see transport with food and feedstuffs.
protection: complete protective Notes). May be stored in stainless C symbol
clothing including self-contained steel containers (see Notes). R: 35
breathing apparatus). S: 2-26-30
UN Hazard Class: 8
UN Packing Group: II
Prepared in the context of cooperation between the International Program on Chemical
ICSC: 0362
Safety & the Commission of the European Communities © IPCS CEC 1993

User Manual
TN-TS 3000 Rev. 2.0.2

SULFURIC ACID ICSC: 0362
COLOURLESS, OILY The substance can be absorbed into
HYGROSCOPIC LIQUID , WITH NO the body by inhalation of its aerosol
ODOUR. and by ingestion.
PHYSICAL DANGERS: INHALATION RISK:

Evaporation at 20°C is negligible; a
I harmful concentration of airborne
M CHEMICAL DANGERS: particles can, however, be reached
P The substance is a strong oxidant quickly on spraying.
O and reacts violently with combustible
R and reducing materials. The EFFECTS OF SHORT-TERM
T substance is a strong acid, it reacts EXPOSURE:
A violently with bases and is corrosive Corrosive. The substance is very
N to most common metals forming a corrosive to the eyes the skin and the
T flammable/explosive gas (hydrogen respiratory tract. Corrosive on
see ICSC # 0001). Reacts violently ingestion. Inhalation of an aerosol of
D with water and organic materials with this substance may cause lung
A evolution of heat (see Notes). Upon oedema (see Notes).
T heating, irritating or toxic fumes (or
A gases) (sulfur oxides) are formed. EFFECTS OF LONG-TERM OR
OCCUPATIONAL EXPOSURE REPEATED EXPOSURE:
LIMITS (OELs): Lungs may be affected by repeated or
TLV: ppm; 1 mg/m3 (as TWA); 3 prolonged exposure to an aerosol of
mg/m3 (as STEL) (ACGIH 1993- this substance. Risk of tooth erosion
1994). upon repeated or prolonged exposure
PDK: 1 mg/m3 (USSR 1988). to an aerosol of this substance.
MAK: ppm; 1 mg/m3; respirable
fraction of aerosol (1991).
PHYSICAL Boiling point (decomposes): 340°C Solubility in water: miscible
PROPERTIES Melting point: 10°C Vapour pressure, kPa at 146°C: 0.13
Relative density (water = 1): 1.8 Relative vapour density (air = 1): 3.4
ENVIRONMENTAL This substance may be hazardous to the environment; special attention
DATA should be given to water organisms.
NOTES
The symptoms of lung oedema often do not become manifest until a few hours have passed and they are
aggravated by physical effort. Rest and medical observation are therefore essential. NEVER pour water
into this substance; when dissolving or diluting always add it slowly to the water. Store in an area having
corrosion resistant concrete floor.
TEC (R)-10B
NFPA Code: H 3; F 0; R 2; W
LEGAL collective views of the IPCS Peer Review Committee and may not reflect in all cases all
NOTICE: the detailed requirements included in national legislation on the subject. The user should
verify compliance of the cards with the relevant legislation in the country of use.

User Manual
TN-TS 3000 Rev. 2.0.2

ALDRIN ICSC: 0774
ALDRIN
CAS # 309-00-2
HHDN
RTECS # IO2100000
1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro,endo,exo-1,4:5.8-
ICSC # 0774
dimethanonaphthalene
UN # 2761
C12H8Cl6
EC # 602-048-00-3
TYPES OF
HAZARD/ PREVENTION
EXPOSURE
Not combustible. Liquid In case of fire in the
formulations containing surroundings: all
FIRE
organic solvents may be extinguishing agents allowed.
flammable.
Explosion hazard will depend
EXPLOSION on the solvent used or on the
characteristics of the dust.
PREVENT DISPERSION OF
DUST! STRICT HYGIENE!
EXPOSURE
AVOID EXPOSURE OF
(PREGNANT) WOMEN!
(see Ingestion). Ventilation (not if powder). Fresh air, rest. Artificial
INHALATION respiration if indicated. Refer
for medical attention.
MAY BE ABSORBED! See Protective gloves. Protective Remove contaminated
SKIN Ingestion. clothing. clothes. Rinse and then wash
skin with water and soap.
Safety goggles or face First rinse with plenty of
shield. water for several minutes
a doctor.
Dizziness. Headache. Do not eat, drink, or smoke Do NOT induce vomiting.
INGESTION Nausea. Vomiting. during work. Rest. Refer for medical
Weakness. Muscle twitching. attention.
Sweep spilled substance into Separated from food and Do not transport with food and
containers. Carefully collect feedstuffs. Cool. Dry. feedstuffs.
remainder, then remove to safe T symbol
place. Do not let this chemical R: 24/25-40-48
enter water courses or sewers S: 22-36/37-44
(extra personal protection: UN Hazard Class: 6.1
complete protective clothing Severe marine pollutant.
including self-contained breathing
apparatus).
Prepared in the context of cooperation between the International
Programme on Chemical Safety & the Commission of the European
ICSC: 0774 Communities © IPCS CEC 1993

User Manual
TN-TS 3000 Rev. 2.0.2

ALDRIN ICSC: 0774
COLOURLESS CRYSTALS. The substance can be absorbed into
the body through the skin and by
PHYSICAL DANGERS: ingestion.
I
M INHALATION RISK:
P CHEMICAL DANGERS: Evaporation at 20°C is negligible; a
O The substance decomposes on harmful concentration of airborne
R heating producing toxic and corrosiveparticles can, however, be reached
T fumes (chlorine fumes, hydrogen quickly on spraying.
A chloride.) Reacts with acids,
N oxidants, active metals, phenols, acidEFFECTS OF SHORT-TERM
T catalysts. Can be corrosive due to EXPOSURE:
the slow evolution of hydrogen The substance may cause effects on
D chloride in storage. the central nervous system , resulting
A in convulsions.
T OCCUPATIONAL EXPOSURE
A LIMITS (OELs): EFFECTS OF LONG-TERM OR
TLV : ppm; 0.25 mg/m3 (as TWA) REPEATED EXPOSURE:
(skin) (ACGIH 1991-1992). The substance accumulates in the
human body. Aldrin may be present in
human placental tissues and blood.
Boiling point at 0.267 kPa: 145°C Solubility in water: none

PHYSICAL Melting point: 104°C Vapour pressure, Pa at 20°C: 0.0086
PROPERTIES Relative density (water = 1): 1.54 Octanol/water partition coefficient as
log Pow: 7.4
Aldrin persists in soils: 50% disappear after 4 to 7 years. This substance

ENVIRONMENTAL may be hazardous to the environment; special attention should be given to
DATA fish and birds. In the food chain important to humans, bioaccumulation
takes place, specifically in aquatic organisms.
NOTES
Other melting points: 40-60°C (technical grade). Technical aldrin is a tan to dark brown waxy solid.
Carrier solvents used in commercial formulations may change physical and toxicological properties. Do
NOT take working clothes home. The recommendations on this Card also apply to ICSC # 0787
(dieldrin). Aldrine, Aldrex, Aldrite, Aldrosol, Drinox, Seedrin, Octalene are trade names.
TEC (R)-61G53b
NFPA Code: H2; F0; R0;
LEGAL collective views of the IPCS Peer Review Committee and may not reflect in all cases all
NOTICE: the detailed requirements included in national legislation on the subject. The user should
verify compliance of the cards with the relevant legislation in the country of use.

User Manual
TN-TS 3000 Rev. 2.0.2

User Manual
TN-TS 3000 Rev. 2.0.2

User Manual
TN-TS 3000 Rev. 2.0.2

User Manual
TN-TS 3000 Rev. 2.0.2
17. Appendix III Quick reference start analysis -standby
Operating procedure
Starting procedure:
1. Start the PC and run the Thermo Fisher Scientific software.
2. If not correct, set the system parameters (temp. etc)
3. Check if glass parts are clean and properly positioned.
4. Connect Argon (white) and Oxygen (blue) connectors of the introduction module.
5. Open Gas supplies with a pre-pressure of approximately 3 bar for Argon and
Oxygen.
6. Adjust all flows on the analyzer by using the flow-regulators.
7. Check all settings in the Software. E.g. smoothing and delay
8. Wait for the signal to stabilize.
9. System is ready for analyses.
Standby procedure:
1. Remove all liquids (e.g. Sulfuric Acid) if applicable.
2. When using an ELS 3000 take furnace needle out of the introduction module
3. Close Argon and Oxygen supplies.
4. Set furnaces at 700 oC.
5. Shut down the software.
6. System is in standby position.

User Manual
TN-TS 3000 Rev. 2.0.2
18. Appendix IV Conversion table: Manual rotameters to digital

massflow meters
Sapphire (red) floater
Display Oxygen Argon Helium
(mm) (mL/min) (mL/min) (mL/min)
0 0.30 0.03 0.69
5 15.0 11.8 13.4
10 37.4 20.8 34.1
15 45.3 37.2 53.0
20 63.7 58.2 72.6
25 97.0 86.3 100
30 134 119 140
35 175 164 192
40 225 197 238
45 294 258 301
50 330 287 364
55 374 359 427
60 400 374 494
65 454 408 579
For example:
10 mm Oxygen is equal to a (mass) flow of 37.4 mL/min
200 mL/min Argon (massflow) is equal to 40-41 mm on the Rotameter scale
45 mm Helium is equal to 301 mL/min

User Manual
TN-TS 3000 Rev. 2.0.2
19. Appendix V Technical specifications
Dimensions (W x H x D) 960 x 400 x 610 mm

Weight 55 kg*
Input Voltage 230/115 V AC

Frequency 50/60 Hz
Fuses 2 x 6.3 A slow at 230 volt nominal
2 x 12 A slow at 115 volt nominal
Power max. 1250 VA
Power/Installation class Class II
Storage temperature 0 – 50 ºC
Operating temperature 10 – 30 ºC
Humidity 20 – 85% (non–condensing)
Safety class Class I**
Furnace 42V; 800W
Connections RS-232; 9 pin sub-D

Service port (RS232 special)
RS-232 to optional sampler
40 pin connector to optional sampler
ID/Introduction module connector: 37 pin sub-D
Power connector
Two aux power outlets; max. 150 VA each
1/8” Gas connector max. 3 bar for O2
1/8” Gas connector max. 3 bar for Ar or He
Max. three quick lock gas connectors ***
*Always carry with two persons and use lift equipment.

** Never connect the 3000 system to other equipment that does not comply to safety class II.
*** Depending on the configuration

User Manual
TN-TS 3000 Rev. 2.0.2
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© 2000-2007, Copyright reserved by Thermo Fisher Scientific Delft, The Netherlands

User Manual 3000 systems V2.0.doc Page 3 of 169

1. GENERAL INFORMATION ....................................................................................... 10

4.2.7. Outlet connection (TN)..................................................................................... 36

User Manual 3000 systems V2.0.doc Page 5 of 169

5.3.5.1. Starting ThEuS™...................................................................................... 55

User Manual 3000 systems V2.0.doc Page 6 of 169

8. COULOMETRIC ANALYSIS ON THE 3000 SYSTEM (OPTIONAL).................. 98

User Manual 3000 systems V2.0.doc Page 7 of 169

10.1.2.5. p-Chlorophenol test solution (100 μg Cl/L)........................................... 117

User Manual 3000 systems V2.0.doc Page 8 of 169

11.2.1.1. Manual introduction POX ...................................................................... 135

13. TROUBLESHOOTING COULOMETRIC OPTION.......................................... 142

14. CONSUMABLES AND SPARE PARTS ............................................................... 146

15. APPENDIX I : SETTINGS .................................................................................... 150

16. APPENDIX II INTERNATIONAL CHEMICAL SAFETY CARDS .............. 151

17. APPENDIX III QUICK REFERENCE START ANALYSIS -STANDBY........ 166

18. APPENDIX IV CONVERSION TABLE: MANUAL ROTAMETERS TO

19. APPENDIX V TECHNICAL SPECIFICATIONS .............................................. 168

User Manual 3000 systems V2.0.doc Page 9 of 169

1.1. Operating Manual

Tel.: +31 (0)15 2571314

User Manual 3000 systems V2.0.doc Page 10 of 169

The following pictograms are used to highlight the information contained in

Text preceded by this sign should be read with special care.

Instructions preceded by this sign must be complied with

Instructions preceded by this sign must be complied with

Instructions preceded by this sign must be complied with

User Manual 3000 systems V2.0.doc Page 11 of 169

1.3. Service and Maintenance

Maintenance should only be carried out by persons specially trained by

We recommend submitting the 3000 system for technical maintenance by the

User Manual 3000 systems V2.0.doc Page 12 of 169

2. GENERAL SAFETY INSTRUCTIONS

- ISO 3864 Safety colors and safety signs.

2.1. Safety Marks on the equipment

The safety markings may be replaced or supplemented by explanatory texts.

THE FURNACE CAN ATTAIN VERY HIGH

THE OUTLET REACHES A TEMPERATURE OF

DO NOT REMOVE COVER!

User Manual 3000 systems V2.0.doc Page 13 of 169

Precautions and/or conditions imposed by national laws or

2.2. Safety rules for the operator

2.2.1. Rules applying to installation

The apparatus must be installed by duly qualified technicians or in

Please note the following requirements:

• Provide a well ventilated space;

An incorrectly grounded or ungrounded apparatus may

User Manual 3000 systems V2.0.doc Page 14 of 169

2.2.2. Do’s and don’ts with the 3000 system

User Manual 3000 systems V2.0.doc Page 15 of 169

3. PRINCIPLE OF THE MEASUREMENT

3.1. Introduction of the 3000 system (TN-TS)

For many years, Thermo Fisher Scientific is a high quality producer of