TSHR 6000 User Manual V1.3 (4)

TN/TS/TX
6000 Series Systems

User Manual v1.3
TSHR International
Strickledeweg 44
3044 EK Rotterdam
The Netherlands
www.tshrinternational.com
TSHR International | 6000 Series Systems - User Manual | v1.3
COPYRIGHT
TSHR International B.V. provides this document to its customers with a product purchase to use in the product operation.
This document is copyright protected and any reproduction of the whole or any part of this document is strictly
prohibited, except with the written authorization of TSHR International B.V.
The contents of this document are subject to change without notice. All technical information in this document is
for reference purposes only. System configurations and specifications in this document supersede all previous
information received by the purchaser.
TSHR International B.V. makes no representations that this document is complete, accurate or error-free and assumes no
responsibility and will not be liable for any errors, omissions, damage or loss that might result from any use of this
document, even if the information in the document is followed properly.
This document is not part of any sales contract between TSHR International B.V. and a purchaser. This document
shall in no way govern or modify any Terms and Conditions of Sale, which Terms and Conditions of Sale shall
govern all conflicting information between the two documents.
Save to the extent permitted by law, the customer hereby undertakes not to alter or modify the whole 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 TSHR International B.V. 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 customer’s 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 TSHR International B.V. or with
which it is incompatible.
The warranty shall not apply to any software which the Customer alters or modifies.
TSHR International B.V. 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 themselves that the
software is so fit.
The photographs/illustrations used in this manual can differ from the actual module and set-up.
2
All photographs, drawings and diagrams are for illustrative purposes only. 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 then TSHR International B.V. would appreciate being informed.
The above notwithstanding TSHR International B.V. can assume no responsibility for any errors in this manual or
their consequences.
For more information, please visit our website at www.tshrinternational.com

Any use of this manual other than intended by the producer is prohibited without the prior written permission
of TSHR International B.V.
© 2016, Copyright reserved by TSHR International B.V. Rotterdam, The Netherlands
3
REGULATORY COMPLIANCE
TSHR International performs complete testing and evaluation of its products to ensure full compliance with applicable
domestic and international regulations. When the system is delivered to you, it meets all pertinent electromagnetic
compatibility (EMC) and safety standards as described below.
EMC Directive 89/336/EEC

EMC compliance has been evaluated by D.A.R.E., Vijzelmolenlaan 7, 3447 GX Woerden, The Netherlands
Low Voltage Safety Compliance

This device complies with Low Voltage Directive 73/23/EEC and harmonized standard EN 61010-1:2001.
Changes that you make to your system may void compliance with one or more of these EMC and safety standards.
Changes to your system include replacing a part or adding components, options, or peripherals not specifically
authorized and qualified by TSHR International To ensure continued compliance with EMC and safety standards,
replacement parts and additional components, options, and peripherals must be ordered from TSHR International or
one of its authorized representatives.
FCC Compliance Statement

This device complies with part 15 of the FCC rules. Operation is subject to the following two Conditions:
(1) this device may not cause harmful interference, and (2) this device must accept any interference received, including
interference that may cause undesired operation.
CAUTION! Read and understand the various precautionary notes, signs, and symbols contained inside this
manual pertaining to the safe use and operation of this product before using the device.
WEEE Compliance
This product is required to comply with the European Union’s Waste Electrical & Electronic Equipment
(WEEE) Directive 2002/96/EC. It is marked with the following symbol:
TSHR International has contracted with one or more recycling or disposal companies in each European Union (EU)
Member State, and these companies should dispose of or recycle this product.
See www.tshrinternational.com for further information on TSHR International’s compliance with these Directives
and the recyclers in your country.
4
Inhoud
CHAPTER 1 GENERAL SAFETY INSTRUCTIONS ........................................................................................................................... 8
1.1 OPERATING MANUAL ............................................................................................................................................................... 9
1.2 INTRODUCTION TO THE 6000-SERIES ................................................................................................................................... 9
1.3 SERVICE AND MAINTENANCE ............................................................................................................................................. 10
1.4 SAFETY MARKS ON THE EQUIPMENT ................................................................................................................................ 11
1.5 SAFETY RULES FOR THE OPERATOR .................................................................................................................................. 12
1.6 OPERATIONAL COMPLIANCE RULES ................................................................................................................................. 13
1.7 WARNING SIGNS! ..................................................................................................................................................................... 14
Chapter 2 CONNECTIONS AND SPECIFICATIONS ......................................................................................................................... 15
2.1 FLOWPATH COULOMETRIC DETECTION ............................................................................................................................. 16
2.2 COULOMETRIC TITRATION DETECTORS............................................................................................................................ 17
2.3 PRINCIPLE OF HALIDE ANALYSIS ........................................................................................................................................ 17
2.4 PRINCIPLE OF SULFUR ANALYSIS ....................................................................................................................................... 20
Chapter 3 6000-SERIES START UP ..................................................................................................................................................... 24
3.1 INTRODUCTION TO THE 6000 SERIES SYSTEMS ............................................................................................................... 25
3.2 OVERVIEW TX6000 .................................................................................................................................................................. 26
TOP VIEW ..................................................................................................................................................................................... 27
BOTTOM VIEW.............................................................................................................................................................................. 1
3.3 TX6000 CONNECTIONS ............................................................................................................................................................. 2
3.4 GLASS PARTS USED WITH COULOMETRIC DETECTION (TX) ............................................................................................ 5
3.5 LIQUIDS SAMPLE INTRODUCTION MODULE ...................................................................................................................... 6
3.6 SOLIDS SAMPLE INTRODUCTION MODULE ........................................................................................................................ 7
3.7 FURNACE ..................................................................................................................................................................................... 8
3.8 TURBO COMBUSTION TUBE .................................................................................................................................................... 9
3.9 CONNECTION FURNACE SCRUBBER (CFS)............................................................................................................................ 9
3.10 OUTLET CONNECTION............................................................................................................................................................ 9
3.11 SULFURIC ACID SCRUBBER ................................................................................................................................................ 10
3.12 TITRATION CELLS ................................................................................................................................................................. 10
CHAPTER 4 TOTAL SULPHUR DETECTION (TS) .......................................................................................................................... 11
4.1 FLOWPATH TOTAL SULFUR DETECTION ............................................................................................................................ 37
4.2 TOTAL SULFUR DETECTION (TS) ........................................................................................................................................... 38
CHAPTER 5 CONNECTIONS AND SPECIFICATIONS TS6000 ...................................................................................................... 40
5.1 TS6000 CONNECTIONS ............................................................................................................................................................ 41
5.2 GLASS PARTS USED WITH UV-F DETECTION .................................................................................................................... 44
5.3 CLAMPS ...................................................................................................................................................................................... 44
5.4 THE PERMAPURE DRYER ....................................................................................................................................................... 45
5.5 THE GLASS FIBER FILTER ...................................................................................................................................................... 47
5.6 THE SULFUR DETECTOR ........................................................................................................................................................ 48
(TS-P-UV-F) ...................................................................................................................................................................................... 48
CHAPTER 6 TOTAL NITROGEN DETECTION (TN) ....................................................................................................................... 49
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6.1 FLOWPATH TOTAL NITROGEN DETECTION ....................................................................................................................... 50
6.2 TOTAL NITROGEN DETECTION (TN) ..................................................................................................................................... 51
CHAPTER 7 CONNECTIONS AND SPECIFICATIONS TN6000 ..................................................................................................... 52
7.1 TN6000 CONNECTIONS ........................................................................................................................................................... 53
7.2 GLASS PARTS USED WITH CHEMILUMINESCENCE DETECTION .................................................................................. 55
7.3 CLAMPS ...................................................................................................................................................................................... 55
7.4 THE PERMAPURE DRYER ....................................................................................................................................................... 56
7.5 THE GLASS FIBER FILTER ...................................................................................................................................................... 58
7.6 THE MOLYBDENE CONVERTER ............................................................................................................................................ 59
7.7 THE NITROGEN DETECTOR (TN-CLD) .................................................................................................................................... 60
7.8 PHOTO MULTIPLIER TUBE (PMT) ......................................................................................................................................... 61
7.9 PRESSURE CONTROL VALVE ................................................................................................................................................ 61
7.10 THE OZONE KILLER .............................................................................................................................................................. 62
CHAPTER 8 HR7000 AUTOSAMPLER .............................................................................................................................................. 63
8.1 HR7000 AUTOSAMPLER .......................................................................................................................................................... 64
8.2 HR7000 CONNECTIONS ........................................................................................................................................................... 66
CHAPTER 9 GLASSWARE MAINTENANCE ................................................................................................................................... 67
9.1 VISIBLE INSPECTION OF GLASSWARE ............................................................................................................................... 68
CHAPTER 10 INSTALLATION GLASSWARE TX6000 ................................................................................................................... 70
10.1 INSTALLATION GLASSWARE TX6000 ............................................................................................................................... 71
10.2 GAS SCRUBBERS AND CONNECTIONS ............................................................................................................................. 72
10.3 TITRATION CELL DETECTOR .............................................................................................................................................. 74
CHAPTER 11 TX6000 START UP ....................................................................................................................................................... 76
11.1 TX6000 START UP.................................................................................................................................................................... 77
11.2 MATERIAL SAFETY DATA SHEETS (MSDS) ......................................................................................................................... 77
11.3 PREPARATION OF REAGENTS ............................................................................................................................................ 78
11.4 PREPARATION OF SAMPLES ............................................................................................................................................... 79
11.5 POWERING UP THE SYSTEM ............................................................................................................................................... 83
11.6 PREPARING THE TITRATION CELL (CHLORIDE) ................................................................................................................. 84
11.7 PREPARING THE TITRATION CELL (SULFUR) ..................................................................................................................... 86
11.8 FILLING THE SCRUBBER ...................................................................................................................................................... 88
11.9 GAS LEAKAGE TEST.............................................................................................................................................................. 90
11.10 TX6000 NORMAL OPERATION ........................................................................................................................................... 91
11.11 TX6000 STANDBY MODE ..................................................................................................................................................... 92
11.12 TX6000 SHUT DOWN ............................................................................................................................................................ 92
CHAPTER 12 TS / TN6000 start up ...................................................................................................................................................... 93
12.1 MATERIAL SAFETY DATA SHEETS (MSDS) ......................................................................................................................... 94
12.2 PREPARING STANDARDS ..................................................................................................................................................... 94
12.3 PERMAPURE CONNECTION ................................................................................................................................................. 95
12.4 MODULE CONNECTION ........................................................................................................................................................ 95
12.5 POWERING THE SYSTEM ..................................................................................................................................................... 96
12.6 STANDARD SOFTWARE SETTINGS ..................................................................................................................................... 96
CHAPTER 13 RUNNING AN ANALYSIS (general) ........................................................................................................................... 97
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13.1 RUNNING AN ANALYSIS (GENERAL) ................................................................................................................................. 98
13.2 6000-SERIES STANDBY MODE ........................................................................................................................................... 103
13.3 6000-SERIES SHUT DOWN................................................................................................................................................... 103
13.4 BASIC SYSTEM SETTINGS .................................................................................................................................................. 104
CHAPTER 14 TROUBLESHOOTING TX6000 ................................................................................................................................. 105
TROUBLESHOOTING TX6000 ...................................................................................................................................................... 105
CHAPTER 15 TROUBLESHOOTING TS6000/TN6000 ................................................................................................................. 111
CHAPTER 16 TECHNICAL SPECIFICATIONS TS6000.................................................................... Error! Bookmark not defined.
CHAPTER 17 TECHNICAL SPECIFICATIONS TN6000 ................................................................... Error! Bookmark not defined.
CHAPTER 18 PRODUCT SPECIFICATIONS TS / TN / TX6000-SERIES ........................................ Error! Bookmark not defined.
CHAPTER 19 CONSUMABLES ........................................................................................................................................................ 123
7
Chapter 1
General safety instructions
8
1.1 OPERATING MANUAL

This operating manual gives instructions detailing the operation of the 6000-series. It does not give detailed
directions for the maintenance or repair of the apparatus.
Before using the 6000-series, carefully read through this operating manual. It is essential that any operator operating
the instrument or who come into direct contact with it must be fully aware of all its associated hazards. 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 warning signs in order to highlight remarks and instructions that require special attention. These
warning signs are listed below. The section “General Safety Instructions” details the warning signs appearing on the
outside and inside of the apparatus. All directions relating to these warning signs 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
contact us.
Please email comments to:
TSHR International BV
Strickledeweg 44
3044 EK Rotterdam, The Netherlands
Phone: 0031 (0)10 2457701. Our telephone service is available from 09:00 to 17:00 (CET).
Email: technicalsupport@tshrinternational.com
1.2 INTRODUCTION TO THE 6000-SERIES

The 6000-series is a Total Nitrogen/Total Sulphur analyser specifically designed for the analysis of gas, LPG and liquid
hydrocarbons produced in the refining of crude oil and natural gas. The 6000-series can be configured as a dedicated
total nitrogen analyser, a dedicated total sulphur analyser or a combined total Nitrogen and total sulphur analyser. The
analyser is compliant with the following regulatory methods:
ASTM D5453, ASTM D4629, ASTM D7183, ASTM D7184, ASTM D6667, ASTM D6069, EN ISO 20846, EN ISO
15486, UOP 936.
The 6000-series operates on the principle of oxidative combustion followed by pulsed UV fluorescence
(sulphur) and reduced pressure chemiluminescence (Nitrogen) detection.
Gases and LPG are introduced into the analyser using the GM 7000 gas/LPG sample introduction module. Liquids
are introduced into the analyser using the HR7000 auto sampler.
The analyser is unique in that it can directly inject liquids of both low and high boiling point samples into the furnace
without the requirement for boat introduction. In order to facilitate this introduction, the viscosity of the sample must
be reduced to a level whereby it can be easily injected via the auto sampler. For light and medium distillates such as
naphtha, formulated gasoline and diesel, no dilution is required and the sample can be directly injected. For heavy
hydrocarbons such as fuel oil (bunker oil), gas oil, crude oil and vacuum gas oil, the sample must be diluted. The
dilution factor depends on the sample viscosity and Nitrogen/sulphur concentration but typically a dilution of 50-
100x is recommended.
The ability to analyse heavy hydrocarbons without the use of boat introduction reduces the analysis time from
typically 10-12 minutes per sample repeat to 2-3 minutes per sample repeat. In addition, there is no requirement to
change the sample introduction module because of the sample type and light and heavy hydrocarbon samples can be
analysed in sequence with the benefit of full automation.
The 6000-series has several main components. These are:
Sample introduction
• Liquids Module (syringe injector) (light distillates, middle distillates)
9
• Solids Module (boat injection) (heavy distillates, solids like coal, catalyst)
• GM 7000 adaptor (gasses and LPGs)
• Horizontal furnace
Gas conditioning
• Membrane dryer
• Mass flow controllers
Detection
• Ozone generator for total Nitrogen detection
• Total Nitrogen detector (NO)
• Total Sulphur detector (SO2)
The 6000-series is controlled by an advanced software suite called Athena®. Athena is designed for use with Microsoft
Windows™ 7, 8, 8.1 and 10 (32 and 64 bit). Athena contains pre-loaded methods which ensure complete regulatory
method compliance. In addition to pre-loaded methods, users can create their own methods or edit existing methods
using intuitive method development tools.
Included with Athena is a module for evaluation of sample and calibration worklists.
1.3 SERVICE AND MAINTENANCE

Maintenance should only be carried out by trained Field Service Engineers trained by TSHR International specialists for
this purpose, with the sole exception of the daily maintenance which may be carried out by the operator. We
recommend annual servicing of the 6000-series be carried out by the supplier’s specialists at least once a year, in order
to ensure optimum performance of the instrument.
10
1.4 SAFETY MARKS ON THE EQUIPMENT

The 6000-series has been designed and manufactured in accordance with the following standard ISO 3864
Safety colours and safety signs.
Before using the 6000-series, carefully read through this operating manual. It is essential that any persons operating
the module or who come into direct contact with it must be fully aware of al its associated hazards. Always carry out
a LMRA (Last Minute Risk Analysis) before starting with the analyser.
We use the following safety colours and signs on the analytical instrument. These are based on the ISO 3864
international standards for safety colours and signs. These signs indicate those locations that require special attention
and/or constitute a danger to personnel or the instrument.
The safety markings may be replaced or supplemented by explanatory texts.
All personnel coming into either direct or indirect contact with the 6000-series should be fully acquainted with these
international safety-markings.
The signs and accompanying texts appearing on or inside the 6000-series are shown below.
CAUTION! HOT AREA!

The furnace can attain temperatures in excess of 1000°C.
CAUTION! HOT AREA!

The outlet reaches a temperature of 300°C.
Allow the outlet to cool before removing.
CAUTION! HIGH VOLTAGE

Do not remove cover! This can only be done by trained Field
Service Engineers, not by the operator.
IMPORTANT!
Any precautions and/or conditions imposed by national laws or company safety
regulations applicable to the space occupied by the 6000-series must be followed.
The management of your organization is responsible for communicating these
precautions and conditions and ensuring compliance. In the event of doubt, consult
your supervisor.
11
1.5 SAFETY RULES FOR THE OPERATOR

The general safety rules applicable to the instrument are given below:
Rules applying to installation
The apparatus must be installed by qualified technicians and factory trained Field Service Engineers in
accordance with the instructions provided by supplier. You should
make the following preparatory arrangements:
• Provide a well ventilated space.

• Avoid installation in a space where the apparatus will be exposed to direct sunlight and where there are large
fluctuations in temperature. Acceptable fluctuation is max. 2°C/H. The satisfactory operation of the equipment is
guaranteed when it is installed in a space with a temperature of between 10 and 30°C and a relative humidity
between 20 and 85%. None condensing.
• Allow 20 cm of free space around the apparatus.
• Provide a flat, stable, horizontal surface measuring at least 80 x 160 cm.
• Provide connections for supplies of Oxygen (O²) and Argon (Ar) /Helium (He), pressure 1-3 Bar,
1/8"swagelok connector.
• Make sure that there is a suitable electrical supply nearby, 230 V, 50/60 Hz, at least 1500 W.
• Always connect the 6000-series directly to a grounded power point with a minimum rating of 10A. In case of
doubt consult an authorized installer.
• Never use adapter plugs, power adaptor.
• Keep wires well clear from the furnace in- and outlet.
• Never connect the 6000-series to other equipment that does not comply to safety class II.
WARNING! Before turning on the 6000-series for the first time, the voltage setting must be checked. The
small plate beneath the power lead should be positioned with the 230V indica- tion in the normal position
(not upside down) and is read from left to right when the operator is facing the back of the instrument. The
115 V indicators will 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 instrument
and re-insert the other way up.
ELECTRICAL HAZARD! Do not open the cabinet when the power cable is connected. Remove the
power cable from the wall socket and disconnect the cable from the instrument completely first. An
incorrectly grounded or ungrounded apparatus may cause electric shock.
WARNING! Wrong connections could lead to malfunction of the instrument or computer.
SPECIAL ATTENTION! After supplying power to the instrument 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.
12
1.6 OPERATIONAL COMPLIANCE RULES

• Always read the manual before starting to use the instrument.
• Refer to the manual in case of doubt about a procedure prior to starting up, running samples or shutting
down.
• Wear protective clothing, masks and spectacles in accordance with the laboratory requirements for
carrying out the measurements (see local PPE HSE regulations).
• Make sure that the apparatus is grounded as specified. Use a grounded power connector.
• 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 sure that the doors of the analyser can be freely opened and closed without obstructions.
• 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 must be operated
by qualified personnel only.
• Never place heavy objects and/or combustible products on the 6000-series.
• Never carry out any maintenance on the 6000-series 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 required.
• Always use authorized TSHR materials and accessories. Unapproved materials and accessories may
cause the malfunction of the instrument or give rise to hazardous situations. Never use materials for a
purpose other than that for which they were originally intended.
• The use of parts, which are not manufactured/approved by us, could result into exclusion of warranty
arrangements.
• In case of a malfunction that could endanger safety, turn off the instrument immediately.
• Never sprinkle the housing with water or other liquids. To clean, wipe with a moist cloth.
• Never close off the ventilation openings and check them regularly to ensure they are free from blockages
such as tissues.
• Never place combustible materials on top of the analyser e.g. tissues, solvents, etc.
13
1.7 WARNING SIGNS!

Read the following warnings before using the 6000-series
SYMBOL CAUTION
ELECTRIC SHOCK!
This instrument uses high voltages that can cause personal injury. Before
servicing, shut down the instrument and disconnect the instrument from line
power. Keep the top cover on while operating the instrument. Do not
remove protective covers from PCBs.
HEAT!
Before servicing the instrument, allow any heated
components to cool.
FIRE!
Use care when operating the system in the presence of
flammable gases.
GENERAL HAZARD!
A hazard is present that is not included in the above categories. Also,
this symbol appears on the instrument to refer the user to instructions in
this manual.
CRUSH HAZARD!
Keep hands clear during operation!
WEAR EYE PROTECTION!

Eye damage could occur from splattered chemicals or flying
particles. Wear safety glasses when handling chemicals or
servicing the instrument.
When the safety of a procedure is questionable, contact your local

Technical Support organization for TSHR International Products!
14
Chapter 2
Connections and specifications
15
2.1 FLOWPATH COULOMETRIC DETECTION
1. A sample is introduced (Liquids or Solids) into the is removed. From there it goes to the sulfuric acid
furnace a boat driver or injection syringe. During scrubber.
the transfer into the furnace the sample is carried 4. The gas flows into the titration cell where the
with an Argon flow. The volatile components are reaction takes place. Silver-ions (Ag+) react with
transported directly into the furnace. halide-ions (X- ).
2. In the furnace the sample is oxidized with a 5. A signal appears on the PC screen and the area
flow of O2. generated by this signal is integrated.
The software (Athena) calculates the actual
3. The gas flow from the furnace is carried
concentration and stores the result.
through a heated connection where the water
1. LIQUIDS
Titration curve
PC
Module
O2 connector
COULOMETER
5 Ar
FURNACE
ZONE II ZONE I
LIQUIDS MODULE
O2 Ar (backside)
CFS
ANALYTE
2
4 3 1
Sample Liquids
LIQUIDS MODULE
SCRUBBER
TITRATION CELL
Titration curve
PC
2. SOLIDS
COULOMETER
5
FURNACE
ZONE II ZONE I
SOLIDS MODULE
CFS ANALYTE
O2
Ar
2
4 3 1
Sample Solids
SCRUBBER Boat driver
TITRATION CELL
16
2.2 COULOMETRIC TITRATION DETECTORS
Two different Titration cells can be used, these are:
The Halogen Titration Cell The Sulphur Titration Cell

Coulometric silver titration of Iodometric analysis of sulphur
halides dioxide at ppm level
2.3 PRINCIPLE OF HALIDE ANALYSIS
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 - 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:
K s = [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 E i-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:
E i-r + Ebias
Ebias is a fixed potential of -315 mV 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.
17
The figure below shows a TX titration curve. Initially 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 below).
Example
titration
curve
The quantity of Ag+ ions which are 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= ∫ I . dt n. f
n. f 0
where:
Q = the quantity of charge in Coulombs

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 (area counts) which has been titrated is shown in ‫ى‬C in the queue manager.
The quantity of halide present in the cell will then be automatically calculated. The
calculations are carried out automatically by the Athena software.
18
AI G
R
C
The Halogen Titration Cell

R
C
The titration cell consists of the parts shown in the AI

picture on the right.
where:
I = Indicator electrode (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.
O = Outlet
G = Gas inlet tube
ACID! The titration cell contains a stabilized electrolyte 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.
Circuit diagram of the Halogen Titration Cell
The figure on the right shows a general and simplified

diagram of the electrical circuit.
Where:
COULOMETER
V = Voltmeter
Amp = Currentmeter/Ampmeter
RΩ = Variable resistance
R = Reference electrode
I = Indicator electrode
A = Anode Amp
C = Cathode RΩ
R I A C
19
The titration cell contains two pairs of electrodes:
Measuring pair:
• Indicator electrode I (silver).

• Reference electrode R (silver/silver chloride).
This electrode is connected to the solution through a bundle of capillary tubes.
Generation pair: R C A/I G
• 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.
2.4 PRINCIPLE OF SULFUR ANALYSIS

E i-ris governed by the concentration of iodine ions (I -) in the3 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 I- changes when sulphur dioxide dissolves in the electrolyte. Sulphur
dioxide reacts with I3- as follows:
SO + I -+ 6 H 0 SO 2- + 3 I- + 4 H O+
2 3 2 4 3
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
I 2 + I- I3-
This process will continue until Ei-r no longer changes, i.e. until the concentration of I 3 has returned- to the value it
had before the addition of SO2. The generator current will then be equal to zero and all the SO2 will have
been converted into sulphate.
20
Here too the difference in potential between anode and cathode is:
E i-r + Ebias ~ 0.5 V
E bias is in this case equal to + 0.145 mV

I A
The quantity of I- converted can be calculated from the charge needed for the C
conversion. Then the quantity of SO2 present in the cell

R
can be determined according to Faraday’s Law. The same
remarks apply here to the titration curve as were made with G
respect to halide analysis.
The Sulphur Titration Cell

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

R = Reference electrode (Pt/I2/I-)
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
R C A/I G
ACID!
The titration cell contains a solution of 0.1% KI, 0.1% NaN3 and 0.5 % acetic acid in de-ionized
water. The NaN3 (sodium azide) is added to prevent possible disturbances to the measurement
caused by nitrous oxides forming in the cell.
TOXIC!
Sodium Azide is extremely toxic. Read the instructions of the chemical safety sheet
carefully and handle accordingly.
21
Circuit diagram of the Sulphur Titration Cell

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

• Reference electrode R (platinum/I2I-). This electro de 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 pair:
• 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. At the anode, I- ions are converted into I2 at the anode.
23
Chapter 3
6000-series start up
24
3.1 INTRODUCTION TO THE 6000 SERIES SYSTEMS
The 6000-series is designed for fast and efficient analysis of total (organic) halogens (X), Sulphur (S) and/or
Nitrogen (N). It supports the use of a number of different modules, which are used for the introduction of
various sample matrices into the furnace.
Analysis of Sulphur (TS) and/or Nitrogen (TN)

To determine both these elements simultaneously, it is necessary to use a “dry” detection technique for the analysis of
sulphur and to combine two detectors in one analyser. We have developed an SO2 - UV fluorescence detector, which is
designed to run simultaneously with the Nitrogen analyser or as a stand-alone unit. This technique uses a
chromatography autosampler (HR7000) which can be used for the incineration of liquid samples in a furnace. The SO 2
and NO produced by combustion are led through both detectors. SO 2 is detected by the principle of fluorescence in
combination with a Photo Multiplier Tube (P.M.T.). NO is detected by the principle of chemiluminescence. Both analysis
techniques require calibration.
Coulometric detection Sulphur (TS) or (organic) halogens (TX)

The 6000-series provides for the use of two different modules (liquids, solids), which can be used for the incineration of
samples in a furnace. The hydrogen halides or the sulphur 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. However it is advised to run a
known standard to ensure the analytical performance.
The 6000 Series Systems

(TS/TN/TX)
The 6000 Series Systems can be

expand with a HR7000 autosampler.
25
3.2 OVERVIEW TX6000
COVER SCRUBBER COMPARTMENT
COVER CELL COMPARTMENT
FRONT VIEW
FURNACE
SAMPLE INTRODUCTION MODULE

(liquids Module)
SULFURIC ACID SCRUBBER
TITRATION CELL (Halogen or Sulphur)
26
TOP VIEW
GAS CONNECTORS TO INTRODUCTION MODULE
COVER FURNACE COMPARTMENT

(removable)
MODULE CONNECTOR
SAMPLE INTRODUCTION MODULE

(solids Module)
27
POWER SWITCH
BOTTOM VIEW
MAIN GAS CONNECTORS
CABLE GROMMETS
COOLING FANS
VIBRATION DAMPERS
COOLING FAN CEL COMPARTMENT
1
3.3 TX6000 CONNECTIONS
Power Connection
A The power cord has to be connected to the 6000-series.
Communication Connection
B The USB cable has to be connected to the 6000-series on the USB-connection. The other
side of this cable has to be connected on the USB-port of the computer. The TX600 has
two Ethernet Ports.
Gas Connections
C Gases must be provided by the customer and need to be
PREFERRED PRESSURE
SETTINGS.
connected to the 6000-series. The gas specifications For Argon/Helium
for Argon/Helium and Oxygen are: advised input pressure is 1-3 bar.
For Oxygen advised input
• Argon/Helium (Ar) (He) 99.998% pressure is 1-3 bar.
• Oxygen (02) 99.6%
• Maximum pressure 3 bar, minimum 1 bar
• Gas connection 1/8” Swagelok
BACK VIEW
230V
US
B
A B INPUT
P-max 3 bar
C ARGON
OXYGE
N2
AR 1-2.5 bar R:10-35 S:21

O 1-2.5 bar
2
MODULE
CONNECTOR
Liquids Module connection
O2
Ar
Gas connection Oxygen to Module
Gas connection Argon to Module
3
Connector
Sulfuric Acid Scrubber
connection
Titration Cell connection
4
3.4 GLASS PARTS USED WITH COULOMETRIC DETECTION (TX)

Glass parts are very important parts of the 6000 Series Systems. Connected to each other, all parts
form the heart of the analyser. Therefore it is very important to connect the parts
carefully with the clamps. Leakage has to be excluded, before an actual analysis can take place. This chapter
describes which glass parts are used in different Module combinations.
The glassware parts are:
1. Syringe
2. Sample introduction module (liquids in
combination with the HR7000 Autosampler)
3. Sample introduction module (liquids)
4. Sample introduction module (solids) 1
5. Furnace tube
6. Connection Furnace Scrubber
2
(CFS)
7. Sulfuric Acid Scrubber
8. Outlet Connection
9. Outlet Connection (ball-joint)
10. Halogen Titration Cell
11. Sulfur Titration Cell
5 4
8
7
9 6
11 10
5
3.5 LIQUIDS SAMPLE INTRODUCTION MODULE

The liquid module is used for analysis of extractable organic halogen (EOX) O2
Module
connector
and extractable organic sulphur (EOS).

Ar
This module permits the injection of solutions of
halogen or sulphur compounds in organic solvents, FURNACE
for example after being extracted. The injected ZONE II ZONE I
sample is then carried by a flow of argon into the O2 Ar
LIQUIDS MODULE
(backside)
furnace and burned in oxygen. ANALYTE
With this module also Total halogen (TXliquid) or Total 2

sulphur (TSliquid) in liquid samples and Total halogen 1 LIQUIDS MODULE
(TXgas) or Total sulphur (TSgas) in gas samples can be Sample Liquids
analysed.
The two liquids modules used are:
The liquid module has two connections in which the
carrier gases are injected.
Argon (red) and Oxygen (blue). 1. Liquids module in combination with the HR7000
Autosampler. (On top the sample is directly injected
in the liquids module by the HR7000 autosampler
which holds the syringe).
2. Universal liquids module. (On the back the sample is

directly injected in the liquids module by the boat
driver which holds the syringe).
1 Sample
injected with
syringe
Sample
injected with
syringe
Ar entrance
O2 entrance
Ar entrance
O2 entrance
6
3.6 SOLIDS SAMPLE INTRODUCTION MODULE
FURNACE
ZONE II ZONE I
SOLIDS MODULE
ANALYTE
O2
Ar
2
1
Sample Solids
Boat driver
Solids module
The solids module is used for the analysis of Total
halogen (TX) or Total sulphur (TS) content in solid
samples. The module is meant for the analysis of halogen
and sulphur 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.
1 2
Ar entrance
O2 entrance
7
3.7 FURNACE
The TX6000 uses a furnace to combust the samples. According to ASTM requirements, the furnace is divided into two
temperature zones. The temperature in each zone can be adjusted individually, up to 1250°C, however operating
temperature is between 800°C/1000°C. The maximum temperature
difference between the zones is approximately 250°C.
ZONE I COMBUSTION TUBE
FURNACE (1000 °C)

ZONE II
TEMPERATURES MODULES
WARNING! The combustion tube, outlet, • Sample introduction module 500 °C
modules, joints, etc. become very hot during • Furnace / Furnace tube 1000 °C
the operation of the 6000-series.
• Connection furnace scrubber 325 °C
Carelessness may result in burns. Avoid contact with bare
hands. Use special protective gloves and/or tools for • Outlet connections 320 °C
“hot tube removal”. The safest way to remove the
combustion tube is to first allow it to cool down to room
temperature.
8
3.8 TURBO COMBUSTION TUBE

This tube is designed for petrochemical/hydrocarbon applications and other highly flammable
samples. It has an extra Oxygen supply at the outlet (the longer outlet leg). This is added to
optimize combustion of organic solvents.
The extra Oxygen in the second part of the furnace tube
along with a spiral configuration is also added to Spiral configuration
improve mixing of the combustion gas.
Turbo O2
3.9 CONNECTION FURNACE SCRUBBER (CFS)

The connection furnace scrubber is connected to the sulfuric acid scrubber and to
the ball-joints of the turbo furnace tube outlet. The CFS ensures that the gases do
not end up in a so-called cold trap which can cause moisture.
3.10 OUTLET CONNECTION

The outlet glass connector is connected to the PermaPure and to the ball-
joints of the turbo furnace tube outlets.
9
3.11 SULFURIC ACID SCRUBBER Glass stopper
The sulfuric acid scrubber is designed with a scrubber buffer which can be
filled with 97-98% sulfuric acid. The sulfuric acid dries the gasses and
removes the possible soot particles.
It has two stopcocks which can be removed. To shut the stopcock of the
scrubber, the red handles must be in horizontal position.
The upper glass stopper prevents the sulfuric acid from splashing.
ACID! Take the necessary PPE precautions to avoid

contact with sulfuric acid. Wear protective gloves,
goggles and acid proof clothing, according safety
procedures on the laboratory. Failure to do so may result in
physical injury.
Stopcock
3.12 TITRATION CELLS

After the gas conditioning, the sample gas is detected in the titration cell. Two different titration cells can be used. These
are: a cell for the coulometric silver titration of halides (Halogen Titration Cell) and a cell for the iodometric analysis of
sulphur dioxide at ppm level (Sulphur Titration Cell).
The titration cells are designed for long term automatic analyses. The signals from the titration cell go directly to the IOC-
board in the computer, where the data is collected and processed.
(See chapter coulometric detection for more information)
The Halogen
The Sulphur Titration Cell
Titration Cell
10
CHAPTER 4
Total Sulphur detection (TS)
4.1 FLOWPATH TOTAL SULFUR DETECTION
1. The sample is introduced into the furnace by 6. The fluorescent light is detected by the Photo
the HR7000 autosampler. Multiplier Tube during the relaxation of the
2. The sample is combusted and oxidized to form
decaying SO2* back to SO2. The PMT signal
SO2.
measured is proportional to the concentration of
3. H2O formed by combustion and present in
sulphur in the gas.
the combustion gases is removed by the
Permapure dryer. 7. The PC processes the PMT signal and
generates a graphical display.
4. Soot and undesired particles
are trapped in the filter assembly.
5. In the reaction chamber from the pulsed Xenon
source, UV light is used to excite the SO2 molecules
present in the gas flow.
ZONE II ZONE I 2
37
4.2 TOTAL SULFUR DETECTION (TS)
The sulphur detector (TS-P-UV-F) detects the presence of SO2 formed during combustion of the sample in the furnace.
During the combustion process, the following reaction occurs:
R-S + O SO + CO + H O
2 2 2 2
Detection is based on the principle that SO2 molecules absorb ultraviolet (UV) light and become excited, then decay to
a lower energy state emitting UV light at specific wavelengths which are separated in wavelength from the incident
wavelength. The process of absorption and fluorescence of an SO 2 molecule is depicted in the Figure below.
Singlet excited states

Triplet excited states
Internal Vibrational
conversion relaxation
Intersystem
crossing
Internal &
external
conversion
Absorption Fluorescence Vibrational Phosphorescence

relaxation
The pulsed UV light is generated by a xenon discharge lamp operating at 10 Hz. The light from the Xe flashlamp is
filtered and shaped such that only light which is sensitive to SO 2 molecules is incident on the sample gas cloud.
After excitation, the excited SO2 molecules decay to a lower energy state and UV light is emitted whose intensity is
proportional to the SO2 concentration. This light is detected by a photomultiplier tube (PMT) oriented perpendicular
to the axis of propagation of the xenon flash lamp light.
The reaction which takes place is: SO2 h

1 →SO2
*
SO*2 →SO2 h2

h1 = primary UV-Light
h2 = Emitted light of decaying SO2
38
A bandpass filter, placed between the sample gas cloud and the photomultiplier tube, ensures that only the fluorescent
radiation is passed to the photomultiplier tube for detection. The emission intensity of the xenon flash lamp is monitored
by a UV photodiode. Through signal processing electronics, fluctuations in the emission intensity of the flash lamp are
compensated for and they do not affect the stability of the instrument. The amount of light detected by the PMT is
proportional to the concentration of sulphur contained in the combusted sample. The exact concentration contained
within a given sample can be determined by calibrating the instrument using samples of known concentration.
The layout of the total sulphur detector is presented in the Figure below.
Mirror Assembly
Condensing Lens
Electronics
PMT
UV Flashlamp Gas entrance Gas exit
Photodetector
Reaction
Chamber
PMT
Excited state
SO2*
SO2 SO2+hv.
UV (8.78Hz)
Ground state Lower energy state
WARNING! UV light from the Xenon flash lamp is harmful for your eyes.
During operation, do not remove the socket and do not look directly into the source.
39
CHAPTER 5
Connections and specifications
TS6000
5.1 TS6000 CONNECTIONS

The TX6000 can be expanded with a Sulphur (UV)
detector. The Titration Cell compartment is replaced
with the Sulphur Module compartment. This section
describes the Sulphur (UV) detector connections.
SULFUR MODULE COMPARTMENT
Power Connection
A The powercord has to be connected to the
Sulfur Module Compartment.
B Connection
230V
C Quick lock 1/4" Loop in upper
B C connector only
D
D Quick lock 1/4"Gas inlet UV-F
detector in lower position.
A
41
Power Connection
E The powercord has to be connected to the 6000-series.
F The USB cable has to be connected to the 6000-series on the USB-connection. The other
two Ethernet Ports.
Gas Connections
G Gases must be provided by the customer and need to be PREFERRED PRESSURE
connected to the 6000-series. The gas specifications SETTINGS.
for Argon/Helium and Oxygen are: For Argon/Helium
advised input pressure is 1-3 bar.
• Argon/Helium (Ar) (He) 99.998% For Oxygen advised input
• Oxygen (02) 99.6% pressure is 1-3 bar.
• Gas connection 1/8" Swagelok
230V
US
B
E F INPUT
P-max 3 bar
G ARGON
OXYGE
N2
AR 1-2.5 bar R:10-35 S:21

O 1-2.5 bar
42
MODULE
CONNECTOR
O2
Ar
43
5.2 GLASS PARTS USED WITH UV-F DETECTION

Glass parts used in combination with the Sulfur or Nitrogen detector.
1. Syringe
2. Universal Sample introduction module (liquids)
3. Sample introduction module (liquids in 1
4. Furnace tube
4 3
2
5.3 CLAMPS
Clamps are a necessary part of the glassware.

Every glass connection must be secured with a clamp. 1
The three types of clamps are:
1. Clamp fork NS 29.2 (Secures the Stopper with the Solids Module).
2. Clamp No.35 (Secures the Liquids or Solids Module with the 2
Combustion Tube).
3. Clamp No.12 (Secures Ball joints of the furnace tube with the CFS. The
Sulfuric Acid Scrubber, Outlet Connections and Titration Cells).
44
5.4 THE PERMAPURE DRYER
Conditioning
The gas flow coming from the furnace travels through a Permapure membrane dryer. The principle of the Nafion
Permapure membrane dryer is diffusion of water from the gas stream via co-polymers with sulfuric acid ligands.
SCHEMATIC EXPLANATION
OFWATER REMOVAL
From vacuum pump
OutletPermapure
To glass fibre filter
Vented gasses
Connected on the outlet pipe of

the combustion tube
Inlet Permapure
Outlet Connection
45
To replace and connect the Permapure dryer, the following steps are necessary.
1. Connect the inlet of the Permapure to the outlet glass connector.
2. Connect the tube from gas outlet coming from the vacuum pump to the outside inlet (for drying).
3. Connect the tube from outlet of the Permapure to the 1/4" bulkhead connection going to the blue
glass fibre filter which is located under the Furnace compartment .
1 2 3
Tube to vacuum pump
Glass fibre filter
Inlet Permapure
Outlet glass connector Outlet Permapure
Outlet Permapure
Tube to glass fiber filter 1/4” bulkhead

connection
NOTE! Replacing the Permapure dryer can be done by the operator.
SPECIAL ATTTENTION!
When installing a new PermaPure dryer, care must be taken not to rotate the end pieces of the PermaPure
about the axis of the 1/4" tubing by more than 10°. Rotation of the end pieces will cause the headers of the
inner Nafion tubing to rotate resulting in permanent damage.
46
5.5 THE GLASS FIBER FILTER

Depending on the use: this filter must be inspected daily/weekly. This
filter must be replaced by a new one if any soot or discoloration is
found. The only suitable filter for 6000-series is made of glass fiber,
part no. 742312010071.
White housing
Replacement Procedure glass fibre filter

The cover for the heated PermaPure compartment should
be removed and the PermaPure and filter removed by
carefully undoing the coupling nuts
at both ends of the PermaPure. The filter can be
removed by unscrewing the blue and white housing in
which it resides. Once unscrewed, the filter holder can Filter
be pulled open to reveal the filter.
NOTE! This procedure can be done by

the operator.
Blue housing
47
5.6 THE SULFUR DETECTOR

(TS-P-UV-F)
1. Chamber inlet
2. PMT
3. Flash lamp TS
4. Coupling
5. Lens Mount Assembly
Gas connections with Sulphur detector
48
CHAPTER 6
Total Nitrogen Detection (TN)
6.1 FLOWPATH TOTAL NITROGEN DETECTION
1. The sample is introduced into the furnace.
2. The sample is oxidized into NO + NO2.
3. The moisture is removed by the PermaPure dryer.
4. Soot and undesired particles are trapped in the filter assembly.
5. In the reaction chamber, the NO is mixed with ozone O3 where an

immediate reaction occurs and NO2 is formed. The emitted light is
detected during the relaxation of the unstable NO2* into NO2 by the
means of a Photo Multiplier Tube.
6. The PC executes the data acquisition.
50
6.2 TOTAL NITROGEN DETECTION (TN)

The Total nitrogen detector detects the presence of NO formed during combustion of the sample in the furnace.
During the combustion process, the following reaction occurs:
R-O + O2 NO + CO 2 + H 2O
The water produced in this reaction is removed by the PermaPure dryer and the NO and CO2 formed pass
through a pressure control valve on their way to the NO engine where the detection takes place. The following
sections describe the function of the detection components.
NO Detector and Ozone Generator

After passing through the pressure control valve, the sample gases enter the NO detector. Inside the NO detector
the sample gas is mixed with ozone (O3) produced from an ozone generator. When NO and O3 molecules
collide, the following reaction takes place:
NO + O NO * + O
3 2 2
2
NO2* NO + hν. NO
O3
Ozone input
The reaction of ozone with NO forms NO2 in
an excited state which then decays by
emitting a chemiluminescent photon. The
number of chemiluminescent photons Reaction PMT
detected is proportional to the concentration Chamber
of nitrogen contained within the combusted
sample.
The exact concentration of nitrogen
contained within a given sample can again
be determined by calibrating the
instrument with samples of known
concentration.
The internal surfaces of the NO detector

are gold coated in order to reflect infra-
red light with the highest efficiency. In Excited state
addition, the PMT is Peltier-cooled as this
enhances the infra-red light detection O3 NO2*
efficiency and reduces detector noise.
NO NO2+hv.
PMT
Ground state Lower energystate
51
CHAPTER 7
Connections and
specifications TN6000
7.1 TN6000 CONNECTIONS
Power Connection
A The powercord has to be connected to the 6000-series.
B The USB cable has to be connected to the 6000-series on the USB-connection. The other
two Ethernet Ports.
Gas Connections
C Gases must be provided by the customer and need to be
PREFERRED PRESSURE
SETTINGS.
connected to the 6000-series. The gas specifications
For Argon/Helium
for Argon/Helium and Oxygen are:
advised input pressure is 1-3 bar.
For Oxygen advised input
• Argon/Helium (Ar) (He) 99.998%
• Oxygen (02) 99.6% pressure is 1-3 bar.
• Gas connection 1/8" Swagelok
230V
US
B
A B INPUT
P-max 3 bar
C ARGON
OXYGE
N2
AR 1-2.5 bar R:10-35 S:21

O 1-2.5 bar
53
MODULE
CONNECTOR
O2
Ar
54
7.2 GLASS PARTS USED WITH CHEMILUMINESCENCE DETECTION
Glass parts used in combination with the Nitrogen detector.
1. Syringe
2. Universal Sample introduction module (liquids) 1
3. Sample introduction module (liquids in
4. Furnace tube
4 3
2
7.3 CLAMPS
Clamps are a necessary part of the glassware.

Every glass connection must be secured with a clamp.
1
The three types of clamps are:
1. Clamp fork NS 29.2 (Secures the Stopper with the Solids Module).
2. Clamp No.35 (Secures the Liquids or Solids Module with the
Combustion Tube).
2
3. Clamp No.12 (Secures Ball joints of the furnace tube with the CFS. The
Sulfuric Acid Scrubber, Outlet Connections and Titration Cells).
55
7.4 THE PERMAPURE DRYER
Conditioning
The gas flow coming from the furnace travels through a PermaPure membrane dryer. The principle of the Nafion
PermaPure membrane dryer is diffusion of water from the gas stream via co-polymers with sulfuric acid ligands.
SCHEMATIC EXPLANATION
OFWATER REMOVAL
From vacuum pump
OutletPermapure
To glass fibre filter
Vented gasses
Connected on the outlet pipe of

the combustion tube
Inlet PermaPure
Outlet Connection
56
To replace and connect the PermaPure dryer, the following steps are necessary.
1. Connect the inlet of the PermaPure to the outlet glass connector.
2. Connect the tube from gas outlet coming from the vacuum pump to the outside inlet (for drying).
3. Connect the tube from outlet of the PermaPure to the 1/4" bulkhead connection going to the blue
glass fibre filter which is located under the Furnace compartment .
1 2 3
Tube to vacuum pump
Glass fiber filter
Inlet Permapure
Outlet glass connector Outlet PermaPure
Outlet Permapure
Tube to glass fiber filter 1/4” bulkhead

connection
NOTE! Replacing the PermaPure dryer can be done by the operator.
SPECIAL ATTTENTION!
When installing a new PermaPure dryer, care must be taken not to rotate the end pieces of the PermaPure
about the axis of the 1/4" tubing by more than 10°. Rotation of the end pieces will cause the headers of the
inner Nafion tubing to rotate resulting in permanent damage.
57
7.5 THE GLASS FIBER FILTER

Depending on the use: this filter must be inspected daily/weekly. This
filter must be replaced by a new one if any soot or discoloration is
found. The only suitable filter for 6000-series is made of glass fibre,
part no. 742312010071.
White housing
Replacement Procedure glass fibre filter

The cover for the heated PermaPure compartment should
be removed and the PermaPure and filter removed by
carefully undoing the coupling nuts
at both ends of the PermaPure. The filter can be
removed by unscrewing the blue and white housing in
which it resides. Once unscrewed, the filter holder can Filter
be pulled open to reveal the filter.
NOTE! This procedure can be done by

the operator.
Blue housing
58
7.6 THE MOLYBDENE CONVERTER

The molybdenum converter is installed behind the particle filter
assembly. The function of the converter is to convert NO2 into NO.
This improves linearity dramatically, especially in the low regimes.
The operational temperature is 320°C and it is controlled by the
software and displayed in the “Analyzer window”.
59
7.7 THE NITROGEN DETECTOR (TN-CLD)
1. PMT housing 6. Analyzer gas input

2. Gold plated, heated reaction chamber 7. Heater connection
3. Capillary location (heated) 8. Photo Multiplier tube connections
4. Gas output 9. PMT cooling block (Peltier driven)
5. Ozone input
➈
➀ ➆
➅
➄ ➂
➃
TO PWT HIGH VOLTAGE

➁
➇
TO INPUT BOARD
60
7.8 PHOTO MULTIPLIER TUBE (PMT)

The basic principles for the PMTs in both the sulphur and Nitrogen detectors are similar. Both PMTs are sensitive to the emitted
light, but at different wavelengths. Smart filter and mirror assemblies filter out undesired wavelengths. The PMT only amplifies
the defined wavelengths. The PMT housing is cooled by a Peltier element in order to reduce dark current. Once the received
light enters the focussed area, a cascade multiplier amplifies the total signal.
Figure: Photomultiplier Tube assembly schematic
Photocathode Dynode Anode
Electrical
Incoming Photon connectors
Focusing
electrode Multiplied Electrons
7.9 PRESSURE CONTROL VALVE

Depending on the point at which the system is in the combustion cycle, the pressure within the system will
vary. When no combustion is taking place then the pressure will be dominated by the Oxygen and Argon flow through
the furnace. During combustion, the sample liquid is transformed into a gas which adds gas to the system. Without
compensation for the changes in flows and pressures during the cycle, the pressure in the TN detector, and subsequent
baseline, would fluctuate. The pressure control valve monitors the total flow in the system and if the flow is below a
factory set level, it will add Oxygen to the sample gas line to bring the sample gas flow up to a constant level. This in
turn keeps the TN detector pressure constant and
provides stable conditions for the entire system. The pressure control valve is situated prior to the detectors in the sample
gas line.
61
7.10 THE OZONE KILLER

The ozone generator will convert a small percentage of the O 2 which passes through it into O3. Some of this O3 will be
consumed in the reaction with NO to form NO2* however not all of the O3 will be destroyed. The O3 which is not
consumed in the reaction must be destroyed since it is harmful to health and will cause corrosion of the pump.
Immediately after the sample gas has passed through the NO detector, it enters an ozone killer. This is a catalytic ozone
killer which transforms the O3 back to O2. The sample gas is pumped from the ozone killer and expelled from the
analyser.
62
CHAPTER 8
HR7000 Autosampler
8.1 HR7000 AUTOSAMPLER

The 6000-series uses the HR7000 autosampler (optional). It has been
designed for sampling and preparing liquid samples in this case to support
the simultaneous analysis of Sulphur(TS) and Nitrogen(TN).
This is an autosampler for liquid samples. The

autosampler is compatible with the 7000 and
6000-series.
It introduces the liquid sample directly in the
liquids module or directly in the solids boat. The
autosampler can use up to six different solvents
for the syringe wash. The tray contents 121
positions.
2
3 5
3
TOP VIEW
4
3
1
3
Closed
Open 3
1. Moving tray: 1 rack, 121-position (2ml vials)

2. Tower: holds the syringe
3. Display
4. Solvent and waste vials: The solvent and waste vials may be located on the left or right side of the
autosampler, depending on how the sampler is configured. Left/Right side configuration is factory set.
5. Injection area: region where an injection can be made.
64
WARNING! Using incorrect syringe/needle or sampler

method can cause:
Using improper vials, caps or septa:
• Recovery issue's.
• • Needle blockages.
Will void the warranty.
• Damages the sampler. • Soot formation due to a higher/wrong injection
Vial gets stuck or flies out (vial flying). speed.
Damages the syringe/needle. • Possible explosion when the sampler injects in a GC
• Creates an unsafe situation. mode (GC-mode: high speed injection).
•
65
8.2 HR7000 CONNECTIONS
A I/O: ON/OFF Power switch
B Power cable socket: low voltage power connection

(external power supply)
C RS232C connector: for remote control

(serial connection, optional)
D RJ45 10/100 auto-sensing connector: for

remote control
(Ethernet connection, standard)
E 5 GC connector:
for other devices
(GC, analyzer....)
66
CHAPTER 9
Glassware maintenance
9.1 VISIBLE INSPECTION OF GLASSWARE
All glassware should be checked at least once a month for scratches, cracks and blockages. After
inspection, a gas leak test should be performed. The frequency of inspection depends strongly on the
sample matrix. Samples containing high concentrations of salts or metals reduce the service life of quartz
and the number of inspections should be increased in this case.
Glassware maintenance
Furnace tube
Soot in the furnace tube is a cause of memory effects. Mineralization can also cause memory effects as the tube
becomes slightly porous. Soot deposited at the end of the furnace tube is relatively easy to remove.
1. Remove the clamp between the furnace tube outlet and the PermaPure dryer.
2. Remove the clamp for the “turbo Oxygen” at the furnace tube outlet.
3. Remove the clamp which connects the sample introduction module to the inlet of the furnace tube and remove
the sample introduction module.
4. Remove the stainless steel fork between the furnace tube and the sample inlet module.
5. Pull back the furnace tube halfway so that outlet tubes are inside the furnace, use the clamp nr. 35 to hold the
combustion tube in position. Set the furnace temperature to 1000°C,
it should be clean in 10 minutes.
The furnace tube can become opaque on the inside and sometimes on the outside. This is
recognized as mineralization of the furnace tube.
WARNING!
PULL BACK THE Removing the soot in the
TUBE HALFWAY combustion tube should
only be carried out by
trained Field Service
Engineers.
SET FURNACE (1000 °C)
Soot
67
Scrubber and Connection Furnace Scrubber (CFS)

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.
ACID! Take the necessary PPE precautions to avoid contact with sulfuric acid.
Wear protective gloves, goggles and acid proof clothing, according safety procedures on the
laboratory. Failure to do so may result in physical injury.
NOTE! This can be done by the operator.

Cleaning procedure:
1. Remove all H2SO4 from the scrubber with a tissue. (image 1)

2. Remove the drip tray from the system.
3. Disconnect the CFS-outlet from the scrubber.
4. Disconnect the CFS.
5. Clean the in-outlets of the CFS with a tissue.
6. Remove the scrubber from the system and remove all “stop cocks”. (image 6)
7. Clean the scrubber with water. (see image 7)
8. Heat the scrubber in an drying oven at 50 °C for approx. 15/30 minutes. (image 8)
9. Re-install the scrubber and the CFS, make sure the heater reaches the set temperature again
(300 °C) and carry out the gas test.
1 7 8
20
50
min 0 90°C
68
Liquids module
During the use of the “liquids module” analysis, the inner part and the injection port can become polluted.
Cleaning procedure:
1. Replace the septum when necessary but at least once every week.
2. Reversing the connected 02 and Ar/He gas flows will burn off this pollution.
3. 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 (500 > 600ºC) accelerates this process.
1
2
REPLACE
SEPTUM!
Universal liquids module
REPLACE
SEPTUM!
Reverse the 02
(blue tube) and
Ar/He (red tube)
HR7000 liquids module

3
pollution
clean
NOTE! Before commencing analysis, make sure the gasses have been reconnected in the correct
order!
69
CHAPTER 10
Installation glassware TX6000
10.1 INSTALLATION GLASSWARE TX6000
This chapter will guide you through the correct installation procedure for the TX7000. Always check if
the surface and table, used for the installation, are strong enough to support the weight of the system.
Keep in mind that chemicals might be spilled, affecting the nature and structure of the support. Acids
like “Sulfuric acid” are substances used in the system.
Check for chemical resistance of the surface before final installation and if necessary take measures.
WARNING!
Before turning the TX7000 on for the first time check the voltage. The selected
voltage should match the “standard” voltage supplied to the laboratory. Unplug the
powercord from the TX7000! E.G: to switch from a 230 V supply. The readable
voltage is the selected voltage! In case of doubt, please contact your local
representative.
ELECTRICAL HAZARD!
Do not open the cabinet when the power cable is connected. Remove the power cable
from the wall socket and disconnect the cable from the instrument completely first.
WARNING!
Wrong connections could lead to malfunction of the instrument or computer.
SPECIAL ATTENTION!
After connecting to the electricity supply the furnaces and heating elements will rise to the
safe stand-by temperatures required by the connected module.
71
10.2 GAS SCRUBBERS AND CONNECTIONS
This chapter describes the installation of the parts used to transport the gas from furnace tube to
detection cell.
Connection furnace scrubber (CFS)

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.
1. Open the the outlet section (blue door) and the scrubber part (white door).
2. Place the CFS in the compartment
3. Connect the tube to the shorter outlet of the furnace tube. (Use clamp no. 12)
4. Set the flow at 20-30 ml/min (use flowmeter which is

connected on the bypass connection of the CFS).
5. Connect the oxygen connector on the bypass connection of the

CFS.
6. Connect the white AMP-connector of the heating jacket of the CFS to

the white connector. Now the outlet temperature
can be adjusted and controlled by the software.
1 2 3
Connect the
4 flowmeter
here! 5 6
25 mL/min
POWER GAS
Digital Flow Meter
72
Sulfuric acid scrubber

To place and connect the scrubber you have to be sure a clean and dry drip tray is placed in the scrubber
compartment. Check that both stopcocks are closed (handle in horizontal position).
Follow the next steps for proper installation.
1. Place the scrubber on the bracket.

2. Connect the inlet of the scrubber to the outlet of the heated CFS (ball-joint), using clamp no. 12.
3. Insert the connector (electrical) into the socket.
Adjust the bypass flow (25 ml/min) and fill the scrubber with sulfuric acid. Use flowmeter.
4. Connect the bypass tubing to the CFS.
1 2 3 CLAMP NO. 12
4 5
Tubing Scrubber / Titration Cell

To place and connect the tubing make sure that a clean and dry drip tray is placed in the cell
compartment. Follow the next steps for the installation of the tubing.
1. Place the tubing through the

hole in the compartments. 1 2
2. Connect the inlet of the splash
bulb to the outlet of the
sulfuric acid scrubber, using
clamp no. 12.
73
10.3 TITRATION CELL DETECTOR
SPECIAL ATTENTION! Before the titration cell is positioned, remove all spilled acetic acid from the
compartment. Check if the drip tray is placed in the detector compartment and the stirrer motor
positioned.
Installation of the Halogen Cell
1. Place the stirring motor on the drip tray.

2. Connect the 5-pole DIN-connector.
3. Place the titration cell over the stirring motor.
4. Connect the outlet of the splash bulb with the gas HALOGEN CELL
inlet tube of the titration cell. clamp 12 (Top view)
5. Connect the leads to the corresponding electrodes.
I (Black) Indicator electrode R

(Red) Reference electrode A C A
(Red) Anode
C (Black) Cathode Gas inlet
Gas outlet/
injection
1 2 3
5 I
74
Installation of the Sulphur Cell
1. Place the stirring motor on the drip tray.

2. Connect the 5-pole DIN-connector.
3. Place the titration cell over the stirring motor.
4. Connect the outlet of the splash bulb with the gas inlet tube of the titration cell.
5. Connect the leads to the corresponding electrodes except the Cathode.

(Red) Reference electrode A
(Red) Anode
Do not connect the cathode yet! SULPHUR CELL

(Top view)
6. Connect as last step the Cathode-electrode connector: R
C (Black) Cathode.
Gas inlet Outlet
1 2 3
4 6 7
75
CHAPTER 11
TX6000 start up
11.1 TX6000 START UP
Next chapter describes the steps how to start up the TX6000 and preparation of the glassware before running an
analysis. The following paragraphs should be read carefully, otherwise the measurement could be worthless.
Please note that the software manual must be read before switching on the TX6000.
NOTE!
Read the Athena software manual before operating the TX7000.
11.2 MATERIAL SAFETY DATA SHEETS (MSDS)
Before operating the TX6000 the operator has to be familiar with the format and understand the contents
of the MSDS.
A Material Safety Data Sheet (MSDS) gives health and safety information on chemical products. All
operators who will be using the material must be aware of its hazards, proper work procedures, and personal
protective equipment requirements.
The TX6000 uses the next solutions:
• Argon (cas 7440-37-1)

• Oxygen (cas 7782-44-7)
• Helium (cas 7440-59-7)
• Xylene (cas 1330-20-7)
• Thiophene (cas 110-02-1)
• Isooctane (cas 26635-64-3)
• Toluene (108-88-3)
• Pyridine (cas 110-86-1)
MSDS datasheets can be downloaded at:

www.tshrinternational.com/MSDS
77
11.3 PREPARATION OF REAGENTS
All necessary solutions needed for a good analysis are described below. For some
specific applications refer to the application notes.
Sulfuric acid solution

The Sulfuric acid scrubber needs a solution of 20mL sulfuric acid (H2SO4). No further solution or dilutions
should be made.
Halide electrolytic solution

Pipette 250 mL of demi water into a liter volumetric flask. Fill up to 1000 mL with 100 % acetic acid, homogenize it, and
degas this electrolyte solution. The degassing can be done by using an ultrasonic bath.
Sulphur 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 coloured 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, homogenize it
and degas this electrolyte.
Nitrate stock solution (AOX)

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.
Nitrate wash solution

Put 50 mL of the nitrate stock solution into a measuring flask and fill to 1000 mL with deionized water.
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 700 mL
deionized water. Dilute to 1000 mL with deionized water. Mix the solution thoroughly.
p-Chlorophenol standard solution (1 mg Cl/L)

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

Pipette 10 mL of the 1 mg/L p-Chlorophenol solution into a 250 mL Erlenmeyer flask and fill to 100 ml. Pipette 5 mL
of the nitrate stock solution into the prepared solution and add 50 mg activated carbon. Mix the solution thoroughly.
Aldrin stock solution (1000 mg Cl/L)

To make a stock solution of aldrin dissolve 428,9 mg of aldrin (C12H8C16) in 200 mL n-hexane. Dilute to 250
mL with n-hexane. Mix the solution thoroughly.
78
Aldrin standard solution (100 mg Cl/L)

Pipette 10 mL 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.
Aldrin test solution (10 mg Cl/L)

Pipette 10 mL 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.
Difenylsulfide stock solution (1000mg S/L)

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

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

Pipette 10 mL of the difenylsulfide standard solution in the measuring flask and fill with ethanol to 100 mL.
Mix the solution thoroughly.
11.4 PREPARATION OF SAMPLES

The sample preparation of the most common measurements (AOX, TOX and EOX) is described in the next paragraphs.
All descriptions are following the known standards.
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 TX6000. 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.
79
AOX SAMPLING
Sampling
Removal of active chlorine
Storage at 4°C.
DOC analysis
< 10mg/L > 10mg/LDilute sample
Determination of an organic chloride
< 1000mg/L > 1000mg/LDilute sample
Choose method
Batch method Column method

100 ml sample
100 ml sample
pH 2-3
pH 2-3
Adsorption onto 2 columns

Add 50 mg activated carbon 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
80
EOX sample preparation EOX

Preparation of extractable organic halogen samples is
essential for analyses performed with the TX6000.
Different kind of samples need different kinds of sample
Soil Water Oil
preparation.
The following diagrams indicate the nature of
samples and their specific preparations.
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 water layer
Add 200mlwater
to 100ml extract
Shake for 10 min
Separate the waterlayer
Dry with sodiumsulfate
Extract and concentrate
EOX analysis
81
EOX WATER SAMPLING

(Acc. NEN 6402)
Sampling
Removal of active chlorine
Store at 4 degrees.C
Pour 1 litre o the sample

into a separating funnel
pH =2
Extract with 100ml petroleum ether
Water layer pH = 9
Separation of organic phase Extract with 100ml petroleum ether
Separation of organic phase
Collect extracts
Dry extracts with sodiumsulphate
Concentrate to 5 ml by evaporation
Add 100ul hexadecane
Concentrate to 1ml
EOX analysis
EOX OIL SAMPLING (Acc.

NEN6600)
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
82
11.5 POWERING UP THE SYSTEM

When the instrument is connected to a computer the TX6000 can be switched on with the
ON/OFF switch on the backside of the instrument.
1. Switch on the computer. Make sure the USB cable is connected with the TX6000.
2. Switch on the TX6000.
3. Check if the introduction module is properly connected and make sure the TX6000 and the
introduction module is connected to the gas cylinders (O2 and Ar).
1 2 3 O
2
A
r
230V
4. Start the TX analyser software by clicking on the software icon and wait 10 seconds.
5. Click system-status.
6. Start-up settings must be:
Settings Stand by Start up
Furnace 1 700 1000
Furnace 2 700 1000
Inlet 100 500
Outlet 100 350
7. The instrument stabilization time can be up to 60 minutes.
83
11.6 PREPARING THE TITRATION CELL (CHLORIDE)
While the system is heating up you can continue with the next steps.
1. Clean the cell thoroughly with demineralized water and/or a tissue paper.
2. Rinse the cell with a small quantity of ammonia in order to remove any excess water and Silver ions.
(Never use organic solvents to clean the cell.)
3. Fill the cell with the correct electrolyte solution up to the level mark
ACID! The titration cell contains a stabilized electrolyte 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.
4. Fill the reference electrode with the electrolyte solution by using a bulb with the fingers to produce a vacuum
for aspiration. Release once the bulb is completely deflated and the reference electrode is filled.
5. Add the reference electrode.
6. Place the teflon stirrer in the titration cell.
7. Place the Electrode container and add the three electrodes and Gas inlet.
8. The inner part of the Cathode must be filled with the electrolyte solution. If the Cathode is clogged with Silver
ions, place it in a cup filled with ammonia to remove the Silver ions deposit.
9. Place the cell on the stirrer motor (Connect the 5-pole DIN-connector first.)

(Red) Anode
C (Black) Cathode
11. Go to Athena software and Set stirrer: 45. See if he stirrer is moving correctly.
12. Set gain: 10. Chloride ions are titrated with silver ions generated at the silver anode.
A peak in the signal can be observed, after automatic calibration the signal will decline to 0mQ.
1 2 3
75%
ACET
IC
ACID
1x rinse 3x rinse LEVEL MARK
84
4 5 6
7 8 9
CATHODE
FILLED WITH
ELECTROLYTE
SOLUTION
ELECTRODE
CONTAINER
10 C A 11
µA 12
0,4
0,35
0,3
0,25
0,2
0,1
0,05
0
85
11.7 PREPARING THE TITRATION CELL (SULFUR)
Make sure the cell (the glass) is clean.
1. Rinse the cell with a small quantity of ammonia in order to remove any excess water.
(Never use organic solvents to clean the cell)
2. Clean the cell thoroughly with demineralized water and/or a tissue paper.
3. Fill the cell with the correct electrolyte solution up to the level mark
4. Fill the reference electrode with the electrolyte solution by using a bulb with the fingers to produce a vacuum
for aspiration. Release once the bulb is completely deflated and the reference electrode is filled.
ACETIC ACID! The titration cell contains a diluted sulfur electrolyte solution.
The concentration of silver ions in solution is maintained at a constant level of about 10 -7 M.
5. Add the reference electrode.

6. Place the eflon stirrer in the titration cell.
7. Place the Electrode container and add the three electrodes and Gas inlet.
8. The inner part of the Cathode must be filled with the electrolyte solution. If the Cathode is clogged with Siver
ions, place it in a cup filled with ammonia to remove the Silver ions deposit.
9. Place the cell on the stirrer motor (Connect the 5-pole DIN-connector first.)

(Red) Anode
Do not connect the cathode yet!
11. Connect as last step the Cathode-electrode connector: C (Black) Cathode.

12. Go to Athena software and Set stirrer: 45. See if he stirrer is moving correctly.
13. Set gain: 10. Chloride ions are titrated with silver ions generated at the silver anode.
A peak in the signal can be observed, after automatic calibration the signal will decline to 0Mq.
1 2 3
SULFUR
ELECTROL
YTE
SOLUTIO
N
1x rinse 3x rinse
LEVEL MARK
86
4 5 6
7 8 9
CATHODE
FILLED WITH
ELECTROLYTE
SOLUTION
10 R I
A
11 C
R
I A
12 µA
0,4
NOTE! I If the signal goes
directly negative, disconnect
13
0,35 the Cathode!
0,3
0,25
0,2
0,1
0,05
0
87
11.8 FILLING THE SCRUBBER
ACID! Take the necessary PPE precautions to avoid contact with sulfuric acid.
Wear protective gloves, goggles and acid proof clothing, according safety procedures
on the laboratory. Failure to do so may result in physical injury.
SPECIAL ATTENTION! Before the scrubber is positioned, remove all spilled acetic acid from the
compartment. Check if the drip tray is placed in the detector compartment.
Fill the scrubber in the following order:
1. Open the scrubber/coulometric cell compartment.

2. Shut both stopcocks of the scrubber, the red handles in horizontal position.
3. Remove the scrubber from the system (remove clamps).
4. Remove the upper glass stopper from the scrubber.
5. Fill the scrubber buffer with 95-98% sulfuric acid.
6. Remove any spilled sulfuric acid.
7. Replace the scrubber within the System.
8. Connect the CFS on the scrubber.
9. Turn on the gas flow for both Ar and O2 to the system and set gas flow by using the software:
Settings flow speed
Argon/Helium 100 ml/min
Oxygen (primairy) 300 ml/min
Oxygen (turbo) 100 ml/min
10. Check that the lower stopcock of the scrubber is shut, before filling the absorber of the scrubber to
the red line by opening the upper stopcock (red handle in vertical position).
11. Close upper stopcock (red handle in horizontal position).
Replace upper glass stopper and the connection from the scrubber to the coulometric cell.
12. Now you can place and connect the tubing Scrubber / Titration Cell!
(see page 73 Tubing Scrubber / Titration Cell)
88
1 2 3a
HORIZONTAL=CLOSED
3b 3c 4
5 6 7
95%
SULFU
3/ RIC
ACID
4
8 9 3 bar(g)
10
O2 Ar
VERTICAL=OPEN
11 12 25ml
HORIZONTAL=CLOSED
HORIZONTAL=CLOSED
89
11.9 GAS LEAKAGE TEST
For reliable and accurate analysis the TX6000 needs to be free of leakage. Therefore a
flow test has to be performed. You can find below the flow-settings:
Measure
Argon = 100 mL/min

Oxygen = 300 mL/min
Tubo = 100 mL/min
Bypass = 25 mL/min
Measure Total Flow = 525 mL/min on the input cell
CAUTION!
The combustion tube, outlet, modules, joints, etc. may become very hot during the operation
of the TX7000. Carelessness may result in burns.
Procedure
1. If there are no bubbles visible, a gas leakage has to be performed. Adjust flows to the “normal” levels.
(setting according current method) in the software.
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.
4. 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.)
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.
7. Following these steps should clearly lead to the “problem” and solution in the flow path.
1 2
NO BUBBLES
90
3 4
USE A
SEPTUM!
500 mL/min
0 mL/min
POWER GAS
POWER GAS
Digital Flow Meter

Digital Flow Meter
NOTE! Don't forget to (re)place the septums in the introduction modules. This is
often the cause of gas leakage!
11.10 TX6000 NORMAL OPERATION

The Athena software controls the operation of the TX6000. 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 Athena software manual.
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 Sulphur analysis method for liquid applications
2. AOX / TOX Absorbable or Total organic halogen analysis method for liquid applications
3. POX Purgeable organic halogen analysis method for liquid applications
4. TX / TS-liquids Total halogen or sulphur analysis method for liquid applications
5. TX / TS-gas Total halogen or sulphur analysis method for gas applications
6. TX / TS solids Total halogen or sulphur analysis method for solid applications
Other methods are custom made by TSHR International or created by customers themselves. The
software manual describes how these methods can be created/changed.
An example of setpoints is given in the basic system settings on page 67.
(For more information see Athena manual.)
91
11.11 TX6000 STANDBY MODE

When no analyses are carried out for a short period of time (a few days) it is recommended to put the TX7000 in
standby mode.
Follow the next steps:

1
1. Disconnect de coulometric cell from the sulfuric acid scrubber.
(Remove the clamp between the splash-bulb and coulometric
cell.
2. Drain the sulfuric acid scrubber into the small beaker.
3. Close header gas supply and close flow meters by setting the
flows at a rate of 0ml/min within the software.
4. Set the following temperatures:
Heating Setpoint
Furnace 1 700 °C
Furnace 2 700 °C 2
Inlet 50 °C
Outlet 25 °C VERTICAL=OPEN
Now the instrument is in standby mode.
11.12 TX6000 SHUT DOWN

If no analysis is required for a prolonged period of time, it is recommended to shut down the TX6000.
1. Close the header gas supply or close the flow meters by turning the black knob clockwise.
2. Shut down the software. Switch off the TX6000 (do not disconnect the power plug in order to keep
cooling fans running).
Now the instrument is now turned off.
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CHAPTER 12
TS / TN6000 start up
SPECIAL ATTENTION! After installation, the 6000-series is ready for operation.

Please note that the software manual should be read before the 6000-series is
switched on.
12.1 MATERIAL SAFETY DATA SHEETS (MSDS)
Before operating the 6000-series the operator has to be familiar with the format and understand the
contents of the MSDS.
A Material Safety Data Sheet (MSDS) gives health and safety information on chemical products.
All operators who will be using the material must be aware of its hazards, proper work procedures, and personal
protective equipment requirements.
The 6000-series uses the next solutions:
• Argon (cas 7440-37-1)

• Oxygen (cas 7782-44-7)
• Helium (cas 7440-59-7)
• Xylene (cas 1330-20-7)
• Thiophene (cas 110-02-1)
• Isooctane (cas 26635-64-3)
• Toluene (108-88-3)
• Pyridine (cas 110-86-1)
MSDS datasheets can be downloaded at: www.tshrinternational.com/MSDS
12.2 PREPARING STANDARDS
6000-series starting up the system

Before starting up the 6000-series several solutions should be prepared. All the necessary solutions, needed for
analysis, are described on the next page.
94
Sulphur Standards
SPECIAL ATTENTION! Advised thiophene in xylene and to order certified standards from Ultra
Scientific. www.ultra-sci.com
A 1000 mg/l mixed TNTS standard is prepared by adding dibenzothiophene (1.437 g) and carbazole (2.986
g) to a 250 ml graduated flask. Pure ACS grade xylene is added to the flask to dissolve the solid. The contents of the
flask are swirled to dissolve any remaining solids before being made up to the calibration line with xylene. A stopper is
applied to the flask which is then thoroughly shaken. A range of standards can then be generated from the 1000 mg/l
standard using a 5 ml, 10 ml and 25 ml pipette together with 100 ml volumetric flask. It is important to thoroughly mix,
by shaking each of the mixtures before diluting further.
250 mg/l 25 ml of 1000 mg/l solution made up to 100 ml with pure xylene 100
mg/l 10 ml of 1000 mg/l solution made up to 100 ml with pure xylene 50
mg/l 10 ml of 100 mg/l solution made up to 100 ml with pure xylene 5 mg/l
10 ml of 50 mg/l solution made up to 100 ml with pure xylene
2.5 mg/l 10 ml of 25 mg/l solution made up to 100 ml with pure xylene 1
mg/l 1 0 ml of 10 mg/l solution made up to 100 ml with pure xylene 0 mg/l
Pure xylene
Nitrogen Standards
SPECIAL ATTENTION! Advised Pyridine in xylene.
Carbazole stock-solution (1000mg N/l)

Dissolve 11.937g of carbazole (C12H9N) in a 1000ml graduated flask containing approximately
800ml acetone and dilute to 1000ml with acetone. Mix the solution thoroughly.
12.3 PERMAPURE CONNECTION

Connect the PermePure to the outlet to the furnace using the outlet glass-connector. Connect all tubing to the PermaPure
as described in the section on the PermaPure in chapter 5.4.
12.4 MODULE CONNECTION

Install the sample introduction module and connect all the tubing. Secure the module to the furnace tube with the
clamp. Attach all gas connections (blue to blue and white to white) and plug in the module
ID-connector.
95
12.5 POWERING THE SYSTEM

When all the steps above are complete and the instrument is connected to a suitable computer, the 6000-series
can be switched on with the ON/OFF switch at the rear of the instrument.
NOTE! The detectors need 30 minutes to reach operational temperatures and optimal
performance conditions.
The UV detector produces a ticking sound after switching on; this is due to the UV flasher lamp and is normal. The TN
detector reaction chamber heats up, PMT cools down as soon as the unit is switched on and produces no sound.
1. Switch on the computer.

2. Start the TS/TN analyser software by clicking on the software icon.
3. Check in the “System status screen” that communication is established between the PC and the 6000-series. If
there is no communication, check that the correct “com port” has been selected and connected. Furnace
temperatures and system parameters can be adjusted and monitored.
At this point the instrument needs time to stabilize.
The software controls the operation of the 6000-series. Methods are described in the Athena software manual. During
normal operation, regular maintenance procedures need to be carried out and these include:
• Visible inspection of glassware (see chapter 9)

• Standard set points
12.6 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 set
up.
96
CHAPTER 13
Running an analysis
(general)
Running an analysis general
13.1 RUNNING AN ANALYSIS (GENERAL)

A brief explanation will be given in the following section on how to start working with the Athena® software
supplied with the analyser. For more details please refer to the manual on the Athena-Thumb- drive or to the
interactive manual built into the Athena help menu. Accessible by hitting the F1 button.
Starting Athena®
Athena is already installed on the computer when supplied with the system and a USB is also included in the shipment.
If no computer was included, Athena can be installed on the computer connected to
the analyser by inserting the Thumbdrive into the USB port. Installation will begin automatically. Please
refer to the installation manual for more details.
Start Athena by clicking the icon on the desktop:

If the system has been installed by a TSHR trained engineer, the correct configuration and
method(s) will already be installed on the computer. If not, please contact your local
representative. After Athena has started a sample queue must be entered.
To do this, open the Queue manager.
98
Next, click the Add button.

The following window will appear:
For analyzing samples, rather than

creating a calibration line, select ‘
Sample’ as Type then enter the
following data in the boxes:
Sample name: The name of the sample to be analysed.

Amount: The quantity of the sample & unit (drop down menu).
Concentration unit: Unit in which the result will be calculated/shown (drop down menu).
Begin sample position: Only used with an autosampler, it denotes the position of the sample
in the autosampler tray. Enter the sample position in this box.
NOTE! If the number of samples entered in the ‘Number of samples’ box is greater than 1
then ‘Begin sample position’ box denotes start position for the first sample in the queue.
Dilution: Use this box to enter the dilution factor if the sample has been diluted prior to
analysis.
NOTE! By double clicking on this box, a dilution calculation wizard is activated. Please
refer to the software manual for more details.
Density: To compensate for density when the density is not 1. E.g. if the sample is dissolved
in toluene then the density for this solution will be 0.85.
This value is used for calculating the analyzed concentration.
Method: Depending on the configuration of the system, one or more methods
are available. Select the correct method from a pull down menu.
NOTE! A method is a sequence of action steps necessary for performing an analysis. Refer to
the software manual for more details.
99
Analyst name: Enter the name of the analyst

Sample Comment: In this box, additional information can be entered.
This information will be stored together with the analysis results.
Number of samples: This is normally 1, however if a number of similar (duplicate) samples
are to be analysed, a value larger can be entered.
NOTE! This will only work when an autosampler is present. Also see Sample start position.
Analysis per sample: In this box, the number of times this sample needs to be analyzed is
entered.
After all parameters have been entered, click the OK button.

The example shown below will generate the following queue:
By clicking the Add button again, the next sample can be added. Repeat this
action until all desired samples have been added to the queue. When finished, click
the analyse button. A similar window will appear:
Make sure ‘Analyse Queue’ is selected (ticked) in order to

analyse the whole queue. This will analyse all un-analysed
samples.
Then click on the OK button and the analysis will

start.
100
Creating a calibration line

Creating a calibration line is similar to analysing samples as described in the previous section. Instead of
selecting ‘sample’ as type, select ‘calibration’. In addition to the normal ‘sample’ information, the names of
the calibration line and the known concentration have to be entered.
If in the ‘calibration line’ box, the option new is selected, a new calibration set will be created. The
following box will be displayed:
A new name, the calibration order, signal and through zero must be entered. For the coulometer
(TX and TS), the order chosen must be ‘Absolute’. In most other cases, a first order (linear fit) is applied.
NOTE! The order can always be changed later in the evaluation.
If the system has more than one detector, the desired signal has to be selected. ‘Through
zero’ is used to force the calibration line through the origin.
An analysis is started in the same way as a sample by clicking the ‘analyse’ button. The
calibration standards are measured and a calibration curve produced.
For more details here please refer to the Athena manual.
101
Performance check in TS/TN mode

Before actual samples are introduced, an overall performance check of the 6000-series must be performed. If these test
results are within the specification set by the factory then samples and calibration procedures may be carried out
without further system proofing.
Before shipment to its final destination, the system undergoes a factory calibration. This instrument specific information
can be found in the Test Report which is sent together with the analyser. The report shows test results and PMT specific
data. The data shows the generated area for a specific standard. This value may be used as an “absolute reference”
for system performance.
By injecting standards at an injection speed of 1μl/s and using the universal “liquids module”,
a comparable result should be obtained at the customer site.
NOTE! The results in terms of area counts strongly depends on the used standards, gas quality
and local contamination levels.
Minimum specifications for a calibration line in the range of 0-50 mg/L, when
certified standards are used:

• Regression r2: 0.995 or better.
• Blank level: 200 or less for Nitrogen. 400 or less for sulphur.
• Baseline level: 10 mV or less.
TN mode test (setting is low range)

A 50mg N/l standard is injected at 0,8μl/s using the flow and temperature settings for the hydrocarbons “liquids
application”. The integrated area generated for a 80μl injection volume should be approximately
80.000 counts. For lower concentrations the area counts strongly depends on the blank levels. The maximum signal
level is approximately 2000 mV. Above this level, the signal may appear flat indicating that the detector is saturated.
If the values above are obtained, the system is functioning correctly and calibration and analysis may be carried out.
Areas lower than ±10% of the values above indicates system problems. In this case, a gas leak test and overall system
check will have to be carried out.
TS-UV mode test (setting is mid-range)

A 50mg S/l standard is injected at 0,8μl/s with flow and temperature settings for the hydrocarbons “liquids
application”. The integrated area generated for a 80μl injection volume should be approximately 160.000 counts. The
maximum signal level is approximately 2000 mV. Above this level, the signal may appear flat indicating that the
maximum level has been reached and the result of the total integration should be ignored.
If the values above are obtained, the system is functioning correctly and calibration and analysis may be carried out.
Areas lower than ±10% of the values above indicate system problems. In this case, a gas test and overall system
check is required.
102
13.2 6000-SERIES STANDBY MODE

If no analysis is required for a short period of time, (several days) it is recommended to put the 6000-series in standby
mode.
Some users however prefer to maintain standard operational parameters, including gas flows.
If the desire is to shut down the vacuum pump only, then shut off the Oxygen supply to the ozonator and switch off the
ozonator.
This will prevent the production of ozone, which could affect the performance of several devices in the 6000-
series. The ozone killer inside the 6000-series only functions properly with the vacuum pump switched on.
WARNING! Whenever the vacuum pump is shut down, shut off the Oxygen supply to the
ozonator. This will prevent the production of ozone, which could affect the performance of
several devices in the 6000-series.

1. Close the main gas supply.
2. Set the following temperatures:
NOTE! If the startup/standby action settings are
set. The instrument can be set to standby by
Heating Setpoint pressing the standby button.
Inlet 100 °C
Furnace 1 700 °C
Furnace 2 700 °C
NOx Converter 100 °C
Ozonator off
Now the instrument is in standby mode.
13.3 6000-SERIES SHUT DOWN

If no analysis is required for a prolonged period of time, it is recommended to shut down the 6000-series.

1. Close the main gas supply.
2. Shut down the software. Set the furnace temperatures at room temperatures and wait till it's below 100°C.
3. Switch off the 6000-series (do not disconnect the power plug in order to keep cooling fans running).
The instrument is now turned off.
103
13.4 BASIC SYSTEM SETTINGS
METHOD FURN 1 FURN INLET OUTLET ARGON/HEL OXYGEN OXYGEN EXT. OXYGEN
NORM/S 2 NORM/S NORM/ TURBO
TD NORM/S TD STD
SORT CELCIUS CELCIUS CELCIUS CELCIUS ML/MIN ML/MIN ML/MIN ML/MIN
TD
EOX/CI 850/700 850/700 550/100 300/100 40/35 50 50 20
EOX/S 1000/700 1000/700 550/100 300/100 40/35 30 30 20
TX/CI 800 1000 500 320 100 300 100 25
TX/S 800 1000 500 320 100 300 100 25
METHOD BYPASS BIAS NEEDLE INJ.

SPEED
NORM/TUR
SORT ML/MIN V MM ML/SEC
BO
TX/CI 25 -315 71 max 1
TX/S 25 145 71 max 1
Tips
1. Take the cell out of the system when you don’t use it for more than a week, remove
the two silver electrodes and leave the rest in the cell.
2. Every day you have to refresh the sulphuric acid in the NOx-scrubber and the scrubber when you get a negative
baseline or whether is an increase in the volume.
3. Unused reference electrodes can be hold in good condition when you store them in demi water.
4. Refresh the cell every day with new stabilized electrolyte 75 %.
104
CHAPTER 14
Troubleshooting tx6000
Troubleshooting TX6000
The TX6000 has been designed to achieve a high level of reliability.

In case of problems or failures, these troubleshooting guidelines will be helpful.
Malfunction Possible cause Action
No cell current. Gain control on zero. Set the gain control at 10.
Cathode or anode disconnected. Re-connect the cathode or anode.
Coulometer cable disconnected Check the wiring and reconnect

from PC or cell. Check by using a dummy cell.
Cell current deviates greatly Electrical connection between cell Fill the titration cell with
from zero or fluctuates. and microcoulometer is broken. electrolyte solution and check
whether electrolyte solution is
present in the side arm of the
titration cell.
Cell current is large and Cl- is leaking from the reference Change the reference electrode.
positive. electrode into the cell. Replace the reference electrode.
Cell current is large and The system is severely Change the electrolyte solution.
negative. contaminated with silver ions.
Cell current is unstable. Irregular stirring, stirrer element out Check the stirrer element and
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 for
electrode has not yet stabilized a period of time or replace with a
e.g. after polishing or renewal. 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.
106
Cell current is unstable. Changing exposure to light of the Make sure that the cell cabinet
cell. 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
Replace the cableset.
No response to Chloride Incorrect bias potential, making Check the potential difference
dosage. 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

Replace the cable set.
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
demineralised water and
electrolyte solution.
The composition of the electrolyte is Replace the solution with new solution
incorrect. with the correct solution.
Incorrect bias potential, causing a Adjust the bias potential until it is

delay in the response of the correct.
indicator electrode. Measure/check the bias using
dummy cell.
Replace the indicator

Indicator electrode is slow.
electrode for example by
switching it with the anode.
107
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

Check the electrolyte
concentration.
High baseline due to high current Sulfuric acid solution is severely Purge the sulfuric acid solution
Cell current is unstable contaminated. 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 TX6000.
Apparatus is contaminated with Clean the titration cell with

organic halogen compounds conc. ammonia, water and
demin. water.
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).
Recalibrate the MFC's.
Check the temperature of the

Halogen adsorption caused by furnace outlet.
insufficient heating of the furnace
outlet.
Dry the splash trap.
Presence of moisture in the
scrubber.
Replace the sulfuric acid in
Too much water in the sulfuric
the scrubber.
acid in the scrubber.
108
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 the Add hexadecane to the extract

injection needle. and raise the injection speed to a
maximum of 0.5 μI per second.
Check the apparatus for the

Gas leaks. presence of 'Teflon' sleeves, etc.
Top up the titration solution.

Too little electrolyte in the
titration cell so that not all
Halogen is absorbed.
Recovery is too high. High blank values for the solvent Check the solvent, if necessary
used for the Liquid analysis. 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 sample heating, e.g. by increasing the
boat. furnace temperature.
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.
109
Irregular or repeating spikes. A defect in the scrubber heating or Increase the temperature to
low temperature setting, (HCI normal levels.
absorption) due to condenses in the
heater section. Contact the TSHR
Technical Support.
Furnace temperature or gas flow is Check the possible causes.

too low (soothing); injection speed is
too high (EOX soothing).
In correct baseline. If the baseline does not behave as Contact the TSHR
outlined above, this may be Technical Support
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.
110
CHAPTER 15
Troubleshooting
TS6000/TN6000
The TS6000 and the TN6000 has been designed to achieve a high level of reliability. In case of
problems or failures, these troubleshooting guidelines will be helpful.
Malfunction Possible Cause Action
The response is too slow. Permapure is blocked. Replace the Permapure.
Recovery is too low or too high. Permapure has melted Replace the Permapure Clean
Soot in the Permapure. it or replace it with a new
Permapure.
Vacuum pump is out of order Contact our Service Department.

(drying of the gasses).
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.
Filter is blocked. Replace or clean the Filter.
Recovery is too low. Furnace temperature is incorrect Check the furnace temperature.
Recovery is too high. High blank values for the Check the solvent and if necessary
solvent used for the liquid clean by distillation. Check the gas
analysis. quality. Make sure that it's according
to the specifications.
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).
112
Malfunction Possible Cause Action
Irregular or repeating spikes. Software error. Contact our Service Department.
Incorrect baseline. If the baseline does not behave as Contact our Service Department.
outlined above, this may be
caused by a number of factors.
Too much noise. Pollution. Clean the glassware.

Check the tubing.
Check the temperature.
Check the environmental air for
high concentrations of NO.
Generally too high baseline. 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 the gas path.

Nitrogen detector.
Defective TS/TN board. Contact our Service Department.
No ticking sound in the Xenon UV lamp is at it's end of Replace the Xenon UV lamp.
TS-detector. lifetime.
113
16. TECHNICAL SPECIFICATIONS TS6000

Parameter 6000 series Type of Analyses Total Nitrogen/
Dimensions 1128 (W) x 372 (H) x 600 (D) mm (extra options: Total Halogens)
44 (W) x 15 (H) x 24 (D) in Detection Principle Pulsed UV-Fluorescence

Furnace Voltage 2 x 24 V, 50/60 Hz (extra options: Coulometrics)
Furnace Power 2 x 300 W PC operating system Windows 7 or higher
Furnace Temperature Sensor 2 x Ni-Cr/Ni Computer Intel Core i3 / AMD Phenom or better
Furnace configuration Dual temperature controlled Software Athena
Furnace Temperature 1250 °C Max Regulatory compliance ASTM, IP, UOP, ISO
FACILITY REQUIRMENTS
Voltage 115/230 V, 50/60 Hz Gasses O2(99,6%) medical grade 2.6
Power 1200W Ar or He (99,998%) technical grade 4.8
Gas connector 1/8” swagelok Gas pressure 2 – 3 Bar (30-45 psi)
Ambient temperature 5 – 35 °C (41 – 95 °F)
Always carry with two persons and

use appropriate lifting equipment. ANALYTICAL SPECIFICATIONS:
Parameter TN LIQUIDS TN Solids
Never connect the TS6000 to other equipment that
does not comply to safety class II. Working ranges 0,03 – 10.000 ppm 0,5 – 10.000 ppm
Detection Limit 30 ppb 30 ppb
Sample Matrix Heavy hydrocarbons,
1128 mm plastics, Solids
Quantity of sample 0,1 – 100 mg
Analysis time 4 – 10 minutes
Relative standard deviation < 5%

600 mm
1128 mm 600 mm
372 mm
372 mm
117
17. TECHNICAL SPECIFICATIONS TN6000
Parameter 6000 series Detection Principle Chemiluminescence (extra
Dimensions 939 (W) x 372 (H) x 600 (D) mm options: Coulometrics and
37 (W) x 15 (H) x 24 (D) in Pulsed UV-Fluorescence)
Furnace Voltage 2 x 24 V, 50/60 Hz PC operating system Windows 7 or higher
Furnace Power 2 x 300 W Computer Intel Core i3 / AMD Phenom or
Furnace Temperature Sensor 2 x Ni-Cr/Ni better
Furnace configuration Dual temperature controlled Software Athena
Furnace Temperature 1250 °C Max Regulatory compliance ASTM, IP, UOP, ISO
Type of Analyses Total Nitrogen (extra options:

Total Halogens/Total Sulphur)
FACILITY REQUIRMENTS
Voltage 115/230 V, 50/60 Hz Gasses O2(99,6%) medical grade 2.6
Power 1200W Ar or He (99,998%) technial grade 4.8
Gas connector 1/8” swagelok Gas pressure 2 – 3 Bar (30-45 psi)
Ambient temperature 5 – 35 °C (41 – 95 °F)
Always carry with two persons and

use appropriate lifting equipment.
Never connect the TN6000 to other equipment that ANALYTICAL SPECIFICATIONS:

does not comply to safety class II.
Parameter TN LIQUIDS TN Solids
Working ranges 0,03 – 5.000 ppm 0,5 – 10.000 ppm
939 mm
Detection Limit 30 ppb 30 ppb
Sample Matrix Heavy hydrocarbons,

plastics, Solids
Quantity of sample 0,1 – 100 mg
600 mm
Analysis time < 10 minutes

Relative standard deviation < 5%
939 mm 600
372 mm
372 mm
119
18. PRODUCT SPECIFICATIONS TS / TN / TX6000-SERIES
Instrument
Properties 6000-series TS6000 TN6000 TX6000
Dimensions (W x D x H) 601 x 580 x 1096 mm 601 x 580 x 1096 mm 601 x 580 x 1096 mm 601 x 580 x 1096 mm
Weight 55 kg 50 kg 50 kg 45 kg
Septum Type 12 mm HT 12 mm HT 12 mm HT 12 mm HT
Operating Temperature 5 - 35°C 5 - 35°C 5 - 35°C 5 - 35°C
Operating Humidity 5% @ 15°C - 60% @ 35°C 5% @ 15°C - 60% @ 35°C 5% @ 15°C - 60% @ 35°C 5% @ 15°C - 60% @ 35°C
6000 Liquids module /

800-1000°C 800-1000°C 800-1000°C 800-1000°C
Furnace Operating Temp.
Software Athena® Athena® Athena® Athena®
Performance 6000-series TS6000 TN6000 TX6000
Injected volume 0-80 μ1 0-80 μ1 0-80 μ1 0-80 μ1
Sample Injection Speed 0,8 μl/s 0,8 μl/s 0,8 μl/s 0,8 μl/s
Min. Sample Analysis time 5 mins 5 mins 5 mins 5 mins
Linearity (R2) 0.995 0.995 0.995 N.A.
Working Range 30 ppb - 10,000 ppm 30 ppb - 10,000 ppm 30 ppb - 10,000 ppm 100 ppb - 10,000 ppm
RSDs Greater of 40 ppb or 2 % Greater of 40 ppb or 2 % Greater of 40 ppb or 2 %
Method Compliance ASTM D4629, ASTM ASTM D7183, ASTM ASTM D4629, ASTM ASTM D4929, ASTM
D6069, ASTM D7184, D5453, ASTM D6667, D6069, ASTM D7184, D5808, ASTM D5194,
ASTM D7183, ASTM ISO 9001 UOP 936, ISO 9001 ASTM D3120, ISO
D5453, ASTM D6667, 9001
UOP 936, ISO 9001
Performance 6000-series TS6000 TN6000 TX6000
Voltage 230 / 115 VAC 230 / 115 VAC 230 / 115 VAC 230 / 115 VAC
Frequency 50/60 Hz 50/60 Hz 50/60 Hz 50/60 Hz
Max. Power Consumption 1250 VA 1250 VA 1250 VA 1250 VA
121
Gases Primary Oxygen 6000-series TS6000 TN6000 TX6000
Minimum Oxygen Grade 2.6 (99.6 %) 2.6 (99.6 %) 2.6 (99.6 %) 2.6 (99.6 %)
Oxygen Consumption 500 - 550 ml/min 400 - 450 ml/min 500 - 550 ml/min 400 - 450 ml/min
Oxygen Input Pressure 2 - 3 bar 2 - 3 bar 2 - 3 bar 2 - 3 bar
Carrier Gas: Choice

of O , Ar or He 6000-series TS6000 TN6000 TX6000
²
Minimum Oxygen Grade 2.6(99.6 %) 2.6(99.6 %) 2.6(99.6 %) 2.6(99.6 %)
Oxygen Consumption 500 - 550 ml/min 400 - 450 ml/min 500 - 550 ml/min 400 - 450 ml/min
Oxygen Input Pressure 2 - 3 bar 2 - 3 bar 2 - 3 bar 2 - 3 bar
Minimum Argon Grade 4.8(99.998 %) 4.8(99.998 %) 4.8(99.998 %) 4.8(99.998 %)
Argon Consumption 0 - 150 ml/min 0 - 150 ml/min 0 - 150 ml/min 0 - 150 ml/min
Argon Input Pressure 2 - 3 bar 2 - 3 bar 2 - 3 bar 2 - 3 bar
Minimum Helium Grade 4.8(99.998 %) 4.8(99.998 %) 4.8(99.998 %) 4.8(99.998 %)
Helium Consumption 150 ml/min 150 ml/min 150 ml/min 150 ml/min
Helium Input Pressure 2 - 3 bar 2 - 3 bar 2 - 3 bar 2 - 3 bar
HR7000
6000-series TS6000 TN6000 TX6000
Autosampler
Dimension (W x H x D) 280 x 570 x 320 mm 280 x 570 x 320 mm 280 x 570 x 320 mm 280 x 570 x 320 mm
Weight 8 kg 8 kg 8 kg 8 kg
Vial Size 2 ml 2 ml 2 ml 2 ml
Number of Positions 121 121 121 121
122
Chapter 19
Consumables
The 6000-series is designed such that instrument maintenance and consumables

replacement is minimized. This ensures a low cost of ownership and maximum
uptime. The following section gives a list consumable parts and a schedule of
routine maintenance.
Refer to Description Qty Part no. Inspect Replace
PGENE0002
1 Syringe 100μL 71mm PS5 GA22, EURO2 1
PGENE0004
2 Needles 71mm PS5 GA22, 3 pieces 1
PANAL0025
3 Septum diameter 12mm, 10 pieces 1
742312010071
4 Particle filters (PTFE) 10pcs. 1
(TN/TS)
PMECH0060
5 Union ¼”x ¼” OD Nylon 1
PMECH0061
6 Connector nylon elbow ¼”x ¼” 1
742312010061
7 Perma pure dryer 1
1. 2. 3. 4.
5. 6. 7.
TECHNICAL SUPPORT
Phone 0031 (0)10 2457701
E-mail technicalsupport@tshrinternational.com
CUSTOMER SERVICE FOR ORDERING INFORMATION

Phone 0031 (0)10 2457701
E-mail sales@tshrinternational.com
TSHR International
Strickledeweg 44
3044 EK
Rotterdam The
Netherlands
www.tshrinternational.com

TSHR 6000 User Manual V1.3 (4)

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TN/TS/TX

6000 Series Systems

• Accident, disaster or event of force majeure

• Customers misuse, fault or negligence by or on the customer’s behalf

• Use of the software in a manner for which it was not designed

content of this manual is protected by copyright.

For more information, please visit our website at www.tshrinternational.com

© 2016, Copyright reserved by TSHR International B.V. Rotterdam, The Netherlands

EMC Directive 89/336/EEC

Low Voltage Safety Compliance

FCC Compliance Statement

1.1 OPERATING MANUAL

Please email comments to:

1.2 INTRODUCTION TO THE 6000-SERIES

1.3 SERVICE AND MAINTENANCE

1.4 SAFETY MARKS ON THE EQUIPMENT

Safety colours and safety signs.

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

CAUTION! HOT AREA!

CAUTION! HOT AREA!

CAUTION! HIGH VOLTAGE

1.5 SAFETY RULES FOR THE OPERATOR

Rules applying to installation

make the following preparatory arrangements:

• Provide a well ventilated space.

WARNING! Wrong connections could lead to malfunction of the instrument or computer.

1.6 OPERATIONAL COMPLIANCE RULES

• Never place heavy objects and/or combustible products on the 6000-series.

1.7 WARNING SIGNS!

WEAR EYE PROTECTION!

When the safety of a procedure is questionable, contact your local

2.2 COULOMETRIC TITRATION DETECTORS

Two different Titration cells can be used, these are:

The Halogen Titration Cell The Sulphur Titration Cell

2.3 PRINCIPLE OF HALIDE ANALYSIS

Ag+ (aq) + Cl - AgCl (s)

K s = [Ag+][CI-] = 1.78 x 10-10

Q = the quantity of charge in Coulombs

The Halogen Titration Cell

The titration cell consists of the parts shown in the AI

I = Indicator electrode (Ag)

The cathode is contained in a glass tube and

Circuit diagram of the Halogen Titration Cell

The figure on the right shows a general and simplified

The titration cell contains two pairs of electrodes:

• Indicator electrode I (silver).

Generation pair: R C A/I G

The coulometer consists of a combination of two circuits:

2.4 PRINCIPLE OF SULFUR ANALYSIS

E i-r + Ebias ~ 0.5 V

E bias is in this case equal to + 0.145 mV

conversion. Then the quantity of SO2 present in the cell

The Sulphur Titration Cell

I = Indicator electrode (Pt spiral wound)

The cathode is contained in a separate compartment

G = Gas inlet tube

Circuit diagram of the Sulphur Titration Cell

The titration cell contains two pairs of electrodes: R I A C

• Indicator electrode I (platinum)

The coulometer consists of a combination of two circuits:

3.1 INTRODUCTION TO THE 6000 SERIES SYSTEMS

Analysis of Sulphur (TS) and/or Nitrogen (TN)

Coulometric detection Sulphur (TS) or (organic) halogens (TX)

The 6000 Series Systems