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A SCENT

OF
FUTURE

MasterGC
gas chromatograph

Operating manual
rev. 1.0
Edition
MasterGC - Operating manual
Rev. 1.0 (2008)

Warnings
The information contained in this document can be updated by DANI Instruments Spa at any time without
prior warning.
DANI Instruments Spa shall not be held liable for any errors in this manual or improper use of the information
contained in it or of the instrument.
It is advisable for users to carefully read all the information contained in this manual before using the
instrument.

Safety Information
The gas chromatograph MasterGC is in compliance with IEC 1010 (International Electrotechnical
Commission) standards.
The instrument is in compliance with the protection requirements stated by Directives 89/336/EC art.4 10.1
and 10.2, Annex I and III and n.2006/95/EC and 93/68/EC.
The product has been designed and tested in accordance with safety standards for use in closed
environments. If the instrument is used in a manner not indicated by the manufacturer, the protection
devices on the equipment could be damaged. If this occurs, disconnect the unit from the electrical power
supply and make sure it cannot be started up by accident.
The machine should only be serviced by professionally trained personnel. Do not replace parts or make
modifications on the instrument unless authorized too do so.
Always disconnect the power supply cord before lifting the lid.
Users cannot replace the internal fuses.

Safety symbols
The warnings in the manual and on the instrument must be observed both during operating phases and when
servicing the instrument. Failure to observe these rules violates the design and instrument use safety
standards.
DANI Instruments Spa bears no liability for user failure to observe these rules.

Attention!!! Warns of a condition or possible situation which could cause damage or harm the user.

Warning Warns of a condition or possible situation which could damage or destroy the product or
the operator’s work

Indicates a grounded terminal.

Indicates a hot surface.

Attention! Refers to attached documentation.


Table of Contents
Technical Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
MasterGC Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
Oven . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
Display. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2
Injectors and Detectors Compartment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Pneumatic compartments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Electronic compartment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Connection/communication compartment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Master GC User Interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Status Bar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
Desktop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
Tool Bar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
Status page and Ready conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
The Oven . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Oven temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Setting the oven temperature (Rates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Oven fan (General). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Oven Fast Cooling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Conditioning time (General). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Cryogenic system (Cryo) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Installing the columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20


Packed columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Nuts and ferrules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Packed column installation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

Capillary columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Positioning the column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Preparing the column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Nuts and ferrules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Assembling the glass liner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Installation of the column in the Electron Capture Detector . . . . . . . . . . . . . . . . . . . . . 28
Installation of the column in the Photoionization Detector . . . . . . . . . . . . . . . . . . . . . . 28
Installation of the column in the Nitrogen - Phosphorus Detector . . . . . . . . . . . . . . . . . 29

i
Installation of the column in the Thermal Conductivity Detector . . . . . . . . . . . . . . . . . . 29
Installation of the column in the Flame Photometric Detector . . . . . . . . . . . . . . . . . . . . 29
Leak testing the pneumatic circuit. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Conditioning the columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

Introduction systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32


Packed column injector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Pneumatic circuit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Adapter for wide-bore capillary column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Injector temperature (Temp) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Carrier Gas Control (press/flow and column) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

Split/splitless injector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Injector temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Carrier Gas Control (Press/flow and Column) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Injection techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Purge flow rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Gas saving. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Introducing the sample . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

PTV Injector (Programmed Temperature Vaporizer) . . . . . . . . . . . . . . . . . . . . . . . . . 47


Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Injector temperature (Temp) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Carrier Gas Control (Press/Flow and Column) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Introduction techniques (Split). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Purge flow rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Gas saving. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Introducing the sample . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .58
Flame Ionization Detector FID 86/10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Detector temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Regulating the gas flow rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Flame . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

ii
Graphic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

Electron Capture Detector ECD 86/30. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68


Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Sensitivity and selectivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Carrier gas and auxiliary gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Current . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Graphic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Cleaning and conditioning the system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Switching on the detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

Thermal Conductivity Detector TCD 86/40 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80


Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Filaments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Graphic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Switching on . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

Nitrogen-Phosphorous Detector NPD 86/20 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90


Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Sensitivity and selectivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Regulating the gas flow rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Bead. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Detector functioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Graphic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

Flame Photometric Detector FPD 86/72 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100


Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
Gas flow rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
The photomultiplier PMP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104

iii
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Sulphur quenching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Response factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Igniting the flame . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
Graphic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

Micro-Thermal Conductivity Detector mTCD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110


Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Configuration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Carrier and auxiliary gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Filaments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Functioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Graphic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

PhotoIonization Detector PID 86/90 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122


Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Auxiliary gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
Lamp . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Switching on the detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Graphic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129

Valve & Accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130


Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .132
How to create a method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
Method Sequence. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Timed events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136

Status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .140
Instrument condition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Control of analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141

Set up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
Com . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144

iv
Other . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146

Maintenance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .148
Touch screen calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
Counters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

Diagnostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .152
Diagnostic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Alarms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

Master AS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .162
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
Set up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
AS parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
AS Sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Maintenance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

v
Technical Specifications

DIMENSIONS

Size 570x500x590 mm (W x H x D)

ENVIRONMENTAL CONDITIONS

Operating temperature 10–40°C

Operating humidity 0-90%

Line voltage requirements 230V ~ 50 Hz (±10% max) 2800W


115V ~ 60 Hz (±10% max) 2800W

HEATED ZONES

Independent heated zones, not 3 injectors, 3 detectors, 2 auxiliary (max temperature


including oven 450°C)

COLUMN OVEN

Dimensions 280x280x160 mm (W x H x D)

Operating temperature 5°C above ambient to 500°C-50°C to 500°C with liquid


CO2 cryogenic cooling option-100°C to 500°C with liquid
N2 cryogenic cooling option

Temperature resolution 1°C

Thermal accuracy ± 0.1°C

Thermal stability ± 0.1°C

Temperature programming 25 ramps, 26 isotherms, 0.1 to 140°C/min

Typical cool-down rate 300°C to 50°C in 4 min

Isothermal time 0.00 to 999.00 min, 0.01 min resolution

PNEUMATIC CONTROL

Pressure range 0-120 psi

Carrier gas max total flow 1000 mL/min (He)

Pressure/flow programming Constant or programmed flow, constant or programmed


pressure, constant linear velocityFlow programming: 25
ramps/26 cost. flows; pressure programming: 25
ramps/26 isobarsPressure resolution: 0.01 bar

vi
Technical Specifications

Atmospheric pressure and temperature


compensation

INJECTORS

Injectors Packed (PK), split/splitless (SL/IN), programmable


temperature vaporizer (PTV), gas sampling valves

Carrier gas He, N2, H2, Ar, Ar+CH4

Maximum number 3

Maximum number of PTV 2

PACKED

Suitable for Packed (6 mm, 4 mm, 1/8” o.d.) and wide-bore columns
(0.53 mm i.d., adapter included)

Temperature Up to 450°C, 1°C resolution

SPLIT/SPLITLESS (SL/IN)

Suitable for Capillary and wide-bore (0.53 mm i.d.) columns

Temperature Up to 450°C, 1°C resolution

Injection modes Split, splitless

Carrier gas control Digital flow control (DFC)

Split flow and septum purge Included; direct setting of split and purge flow rates and
split ratio

Liner Quartz liner with glass wool

PROGRAMMABLE TEMPERATURE VAPORIZER (PTV)

Suitable for Capillary and wide-bore (0.53 mm i.d.) columns

Temperature 10°C above ambient up to 450°C, 1°C resolution-50°C


to 450°C with liquid CO2 cryogenic cooling option-100°C
to 450°C with liquid N2 cryogenic cooling option

Temperature programming 25 ramps, 26 isotherms

Heating rate 1 - 999°C/min; 1000°C ballistic

Injection modes Split, splitless, solvent split

Carrier gas control Digital flow control (DFC)

Split flow and septum purge Included; direct setting of split and purge flow rates and
split ratio

Liner Quartz liner with glass wool.


Special adsorbent for enrichment technique (with
solvent split injection mode)

DETECTORS

vii
Technical Specifications

Detectors FID flame ionization detector


NPD nitrogen and phosphorous detector
ECD electron capture detector
PID photo ionization detector
TCD thermal conductivity detector
mTCD micro thermal conductivity detector
FPD flame photometric detector

Maximum number of detectors 3

Maximum number of TCD 2

Maximum number of µTCD 1 complete, 1 with a single Master channel working

Output signals Digital and analog outputs (0-1V, 0-10V)

FID (Flame Ionization Detector)

Suitable for Packed, wide-bore and capillary columns

Temperature Up to 450°C, 1°C resolution

Linear dynamic range >106

Minimum Detectable Level <2 pg Carbon/sec

NPD (Nitrogen and Phosphorous Detector)

Suitable for Packed, wide-bore and capillary columns

Temperature Up to 450°C, 1°C resolution

Linear dynamic range > 104

Minimum Detectable Level <0.6 pg nitrogen/sec as azobenzene


<0.1 pg phosphorous/sec as malathion

Selectivity 23000 gN/gC as octadecane


105 gP/gC as octadecane

ECD (Electron Capture Detector)

Suitable for Packed, wide-bore and capillary columns

Temperature Up to 380°C, 1°C resolution

Linear dynamic range >104 lindane

Minimum Detectable Level <0.01 pg/sec lindane


63
Radioactive source 10 mCi Ni

PID (Photo Ionization Detector)

Suitable for Packed, wide-bore and capillary columns

Temperature Up to 250°C, 1°C resolution

Linear dynamic range >105 with naphthalene

Minimum Detectable Level <0.1 pg naphthalene/mL carrier gas

viii
Technical Specifications

Ionization lamp 10.2 eV

TCD (Thermal Conductivity Detector)

Suitable for Packed and wide-bore columns

Temperature Up to 450°C, 1°C resolution

Linear dynamic range >105

Minimum Detectable Level <10 ng hexadecane/mL He (carrier gas)

Configuration Dual filaments (Weathstone bridge)

Filament protection Standard

mTCD (Micro Thermal Conductivity Detector)

Suitable for Wide-bore and capillary columns

Temperature Up to 400°C, 1°C resolution

Cell temperature stability ±1°C

Linear dynamic range >103

Minimum Detectable Level <100 pg butane

Configuration 2 filaments, independent or differential operation;


recommended flow rate 1-10 mL/min

FPD (Flame Photometric Detector)

Suitable for Packed, wide-bore and capillary columns

Temperature Up to 450°C, 1°C resolution

Linear dynamic range S>103


P>104

Minimum Detectable Level <40 pg sulphur/sec as dodecanethiol<0.4 pg


phosphorous/sec as tributylphosphate

Selectivity >106 gS/gC as isooctane


>106 gP/gC as isooctane

Configuration Single or double flame

DATA COMMUNICATION

Remote control Start in; start and ready out (contact relays normally
open)

Communication RS232, LAN, USB

Time events 4 voltage free contacts (contact relays normally open)4


24V outputs

ix
Technical Specifications

TOUCH SCREEN GRAPHIC USER INTERFACE

Display LCD TFT, 5.7”

Resolution 240x320 pixel

Colors 65,536

x
MasterGC Overview

The MasterGC consists of six main components, as shown in figure 1-1:

• oven (1)
• display (2)
• injectors and detectors compartment (3)
• pneumatic compartment (4)
• electronic compartment (5)
• communication compartment (6)

Fig.1 - Master GC system components

Oven
The gas chromatograph oven provides the housing and heating for the analytical columns.
The air circulation and the oven insulation guarantee a homogeneous, stable and accurate heating
of the column and provide very precise analytical performances.

The MasterGC column oven has fast heating and fast cooling capability.
The oven can operate from temperature below ambient, with a cryogenic cooling system, up to
500 °C maximum temperature.

Refer to Chapter “The Column Oven” for details.

1
MasterGC Overview

Display
The high resolution LCD display and its touch screen functionality constitute the MasterGC user
interface.
All functions, including liquid autosampler programming, can be managed by the MasterGC
display.
The display allows to gain access to every parameter by no more than four touches on the touch
screen.

Refer to Chapter “MasterGC User Interface” for details.

Injectors and Detectors Compartment


The injectors and detectors compartment is located on the top of the column oven.

The injectors are installed on the left side, the detectors on the right side. Up to three injectors and
three detectors can be installed contemporarly. The injectors and detectors positions are identified
as A, B and C starting from the front to the back of the instrument.

The following injectors are available on MasterGC:

• packed injector
• split/splitless injector
• programmable temperature vaporizer (PTV) injector

Up to two PTV injectors can be installed in the same time, in positions B and C.

Refer to Chapter “Introduction Systems” for details.

The following detectors are available on MasterGC:

• FID Flame Ionization Detector


• TCD Thermal Conductivity Detector
• mTCD microThermal Conductivity Detector
• ECD Electron Capture Detector
• NPD NitrogenPhospourous Detector
• FPD Flame Photometric Detector

Up to two TCD and/or mTCD can be instralled in the same time.

Refer to Chapter “Detectors” for details.

Pneumatic compartments
The pneumatic compartment contains the gas control circuit for both injectors and detectors.
Besides, an extra position for the control of up to three auxiliary gas lines is available.

All gas control circuits are electronically controlled.

2
MasterGC Overview

Electronic compartment
The electronic compartment on the right side of the instrument contains the main board, the
detector boards and pheripheral control boards. The PTV thermal control is also installed on this
side.

Connection/communication compartment
External electrical/electronic connection are placed on the back of the instrument: the power
supply socket and the main switch are on the lower part.

On the left side, the analog output for the detector signals, the RS232, LAN and USB ports, the
Remote and External Events terminal block are also located.

3
Master GC User Interface

Even if usually coupled with a data system, all Master GC functions, including autosampler
programming, can be managed by the innovative touch screen. The display allows to gain access
to every parameter by no more than four touches on the touch screen.

The display can be divided in three blocks:

• Status Bar
• Desktop
• Tool Bar

fig. 2 - Display

Status Bar
The Status bar is on the bottom of the screen. In this section you can find Menu, Status and Time
Clock.

4
Master GC User Interface

Menu
This section allows to gain access to many functions and to select the submenu (fig. 3). Refer to
each specific chapter for details.

fig. 3 - Menu

Menu and Submenu items are reported in the table below together with the chapter of the manual
where you can find detailed information.

Menu Submenu Reference Chapter

OVEN - Oven

INJECTORS A, B, C Introduction Systems

DETECTORS A, B, C Detectors

AUX - Auxiliary Temps and Gases

TIMED EVENTS - Method

MASTER AS SEQUENCE MasterAS

PARAMETERS MasterAS

MAINTENANCE MasterAS

SET UP MasterAS

TOOLS SET UP Setup

DIAGNOSTIC Diagnostic

MAINTENANCE Maintenance

LOCK/UNLOCK Setup

5
Master GC User Interface

Status
This section is able to show in real time the GC status (see Chapter “Instrument conditions”).
If you press on this bar a window “Status” will appear. This window consists of three pages: GC
status, AS Status and Alarm.
When a component of GC is not in the ready condition (Oven, Injector, Detector, etc.), the red
inscription “Not Ready” will be visualized (fig. 4): pressing on this message, the status page
relative to this parameter will appear (see fig. 5 and “Status page” in this chapter).

fig. 4 - Not Ready fig. 5 - Injector status

When the analysis is running, a blue bar is displayed which describes the progress of the analysis,
the remaining time and the actual oven temperature (fig. 6).

In the page “AS Status” (fig. 7) you can follow all the steps of the automatic liquid sampler
MasterAS (see “Master AS user interface” in the chapter headed “Master AS”) and, in case of a
sample sequence, the number of repetitions, the name of the method in use, the vials and
injector involved in the analysis are also displayed.

fig. 6 - Status during analysis fig. 7 - AS Status

6
Master GC User Interface

In the Alarm page (fig. 8) you can find all the messages concerning problems or advices. To gain
access to this page, press the exclamation mark blinking on the right of the status bar. (see
“Alarm” in the chapter “ Diagnostics”).

fig. 8 - Alarm page

Time Clock and Date


This section allows to read the time and date. If you press here, the window “Time & Date” will
appear. Open the page Time (fig. 9) and enter hours, minutes and seconds in the three boxes to
set the time.
To set the date, open the page “Date” (fig.10) and select month, day and year.

fig. 9 - Clock fig. 10 - Date

7
Master GC User Interface

Desktop
The central portion of the display is the desktop.
Here you can find five buttons that allow to gain access to the corresponding components:
Injector, Detector, Start/Stop, Oven and Lamp.

INJECTORS (see chapter “Introduction systems”)

DETECTORS (see chapter “Detectors”)

OVEN (see chapter “ The column oven”)

LAMP: Pressing this button you can switch on or off the lamp. This
device is equipped with a directional supporting arm and it’s able to
illuminate the oven. (see chapter “MasterGC Overview”).

START/STOP: these two buttons are alternatively displayed on the


desktop. When the instrument is out of an analysis, the START button is
displayed. If an analysis is in progress, the STOP button is available.
(see “Control of analysis” in the chapter “Status”).

8
Master GC User Interface

Tool Bar
The Tool Bar (fig. 11) is positioned on the top of the display and consists of three parts:

• the upper left side, where the name of the current method is shown. If you press on this
inscription, the “Manage Methods” and “Method Sequence” pages will be available. (see
the chapter “Method”)
• the upper right side, where the name of the window opened is displayed.
• the lower rows where seven shortcut keys allow to start an application (Start, Stop, “X”
for window closing) or to jump within the windows corresponding to Oven, Injectors,
Detectors, autosampler from left to right respectively.

fig. 11-Tool bar

Pressing the button “Injector” or “Detectors” more times you can scroll through all
injectors or detectors configured.

START: (See “Control of analysis” in the chapter “Status”).

STOP:(See “Control of analysis” in the chapter “Status”).

OVEN: In order to set all parameters press this shortcut key.


The “Oven” window consists of four pages (see the chapter “ The
column oven”):

• Rates
• General
• Cryo (if installed)
• Status

9
Master GC User Interface

INJECTORS: In order to set all parameters press this shortcut key. The
“Injectors” window consists of five pages (see the chapter headed
“Introduction systems”):

• Temp
• Press/Flow
• Column
• Split
• Status

DETECTORS: In order to set all parameters press this shortcut key.


The pages in the “Detectors” window depend on the installed detector
type. For a FID there are six pages (see the chapter headed
“Detectors”):

• Temp
• Graph
• Flows
• Signal
• Flame
• Status

The last button represents a “X” and allows to close the windows and to
come back to the desktop.

How to enter a value


In order to set a parameter you have to press on the corresponding box and a numeric keypad will
appear (see fig 12 ). Digit the value and press OK.

fig. 12 - Numeric Keypad

10
Master GC User Interface

Status page and Ready conditions


A “Status” page (fig. 13) is available for all the devices (Oven, Injectors, Detectors).
In this page you can control the actual value and the set value for the listed parameters.
Besides, you can find the “Ready conditions- Rdy” function.

When all the parameters checked for the “Ready Conditions”, satisfy the set conditions, the
instrument reaches the Ready status (see “Ready” in the chapter headed “Status”).

The parameters available include all the devices that have a temperature regulation, that is
chromatograph oven, injectors, detectors and auxiliary temperatures, all the pressure and flow
regulations on carrier and detector gases.
In the “Default” method, all Ready conditions are active.

To eliminate a parameter from the ready conditions, press on the corresponding check box and
cancel the check.
To include a parameter in the “Ready conditions”, press on the corresponding check box to display
the check.

The oven temperature can never be excluded from the Ready conditions.

When a parameter, selected for the “Ready condition”, has not reached its setpoint yet, it will be
visualized in red.

fig. 13 - Status page

11
The Oven

Description
The gas chromatograph oven (fig. 14) provides the housing and heating for the analytical
columns.
Access to the oven is through a door on the front of the instrument.
The door is opened by pushing the latch under the GC on the right hand side of the same.
The internal dimensions of the oven are 280x280x160 mm (wxhxd).

The resistance for heating the air and the air circulation fan (1) are located behind the metal grid
(2), on the rear wall. The oven temperature probe is located on the rear wall (3).

fig. 14 - MasterGC oven

On the top of the oven (fig. 15), there are 12 openings: two rows of 3 openings on the left, for
injector terminal fittings(1), and two rows of 3 openings on the right (2), for detector terminal
fittings.
A maximum temperature safety probe for the oven is also in this same area (3).

12
The Oven

fig. 15 - MasterGC oven top

Good heat insulation is guaranteed by thermic insulation material inserted both in the hollow wall
and upper surface spaces as well as in the inner part of the access door.

The back panel can be removed for access to the rear of the oven (fig. 16) where the fan motor is
located.
In the same area, two air locks are located which close two openings:

• the upper opening (1), for emission of hot air


• the lower opening (2) for intake of environmental air

The air locks are operated by a stepper motor which regulates their functioning during the oven
cooling phase.

fig. 16 - MasterGC back

13
The Oven

Oven temperature
The oven operates at both constant temperature (isotherm) and programmed temperature.
The oven temperature ranges from -99°C (by using a cryogenic cooling system) up to 500 °C, with
1°C increments. The temperature rates can be set from 0 to 140°C/min with 0.1°C/min
increments.

Oven Temperature Range

Interval (°C) Increment (°C)

temp from +30 to 500 1

with Liquid CO2 from - 50 to 500 1

with Liquid N2 from - 99 to 500 1

Setting the oven temperature (Rates)


· In order to program the oven temperature, press Menu, select Oven and open the page “Rates”
(fig. 17). Use the numerical keypad to type the initial temperature of the run and press OK, then
insert the length of time, expressed in minutes ( with 0.01 min increment), that you want the oven
to remain at this temperature.
If you want to create a temperature program (up to 25 temperature ramps can be set in a
method), enter a temperature rate, then specify a final temperature and a time, eventually.

The maximum temperature rate for different intervals are shown in the table below. If you enter a

fig. 17 - Oven temp setting

value higher than allowed, both the temperature and rate values will be visualized in red (fig. 18).
In the Alarm page, the message “OVEN RATE TOO HIGH” will be shown.
The maximum value allowed in that interval is automatically suggested when you press on each

14
The Oven

box. Change one of the two values to make the setting acceptable. The alarm will be automatically
recovered.

fig.18 - Oven rate too high

Maximum rates

Interval (°C) Maximum rate (°C/min)

30 - 70 140

71 - 115 95

116 - 175 70

176 - 300 50

301 - 450 35

451 - 500 30

After setting the temperature program, the total analysis time (expressed in minutes) will be
displayed under the table. The value displayed does not include the cooling time unless it is
included in the program through a negative gradient.

Important

The duration of analysis controls to the performance of all time controlled functions.
In fact, if a PVT injector temperature program or a pressure program has a duration time higher
than the analysis time, it will stop at the end of the analysis.
Furthermore, possible programmed time events, with times higher than the analysis time will
return to initial conditions upon termination of said analysis.

15
The Oven

Setting the maximum temperature (General)


This parameter defines the maximum allowable oven temperature setpoint to protect the column
from damage. This limit must be set to the maximum operating temperature recommended by the
producer for that column.

· In order to set the maximum temperature, open the page “General” and insert the value in the
box “Max temp” (fig. 19).

fig. 19 - Oven General page

If the temperature value set is higher than the maximum temperature value, the display will show
an alarm message “OVEN:TEMP SET OVER MAX TEMPERATURE”.
This alarm does not allow GC to get the READY status. The condition of error and consequent
message will be eliminated by modifying either the value in the oven program or the value set for
the maximum oven temperature.
In case of the first isotherm, the set value will be accepted in any case but the oven temperature
will stop at the maximum temperature safety value.

Oven fan (General)


· Open the page “General” (fig. 19) and press the buttons ON or OFF to manually activate or
deactivate the functioning of the oven fan, independently from the oven conditions at the time.
When the oven fan is off, the status OVEN FAN OFF will appear on the Status Bar.

In case of a rapid oven temperature drop, for example caused by the opening the door, the fan and
the oven heating are automatically turned off.

Oven Fast Cooling


The oven project allows to reach high speed cooling (Oven fast cooling). This function and the high
speed separations (Fast GC) allow you to maximize the number of analyses.

16
The Oven

“Oven fast cooling” is always active. In order to disable this function open the page “Other” in the
window “Set up” (See the chapter headed “Set up”) and press the button “OFF

Conditioning time (General)


The conditioning step consists of an additional stabilizing time calculated from the moment when
the instrument reaches the ready condition. The READY message will only show at the end of this
step. The duration of this step can vary from 0 to 999 minutes.

· In order to set the conditioning time, open the page “General” (fig. 19) and insert the value in
the corresponding box.

During this step, the message “CONDITIONING” and the elapsed time will be displayed on the
status bar.

Cryogenic system (Cryo)


The cryogenic cooling system allows to reach temperatures below ambient using a cryogenic liquid
as a coolant (-50°C with liquid Carbon Dioxide and -100°C with liquid Nitrogen).

A DANI service engineer is suggested to install the device and set the configuration. If you need to
change the configuration see the Chapter “Set up”

fig. 20 - Oven cryo page

· In order to control this device open the page “Cryo” (fig. 20). You’ll find the following functions:

• Cryo: this function enables the oven cryogenic cooling. Press “Yes” to activate it.
• Cryo threshold (°C): this parameter defines the temperature at which the
cryogeniccooling is enabled. Set a temperature close to ambient temperature (+30°C) for
regular operation. Set a higher temperature (+45°C) for a faster cooling of the oven.
• Cryo saving: when this function is ON, the cryogenic cooling and the oven fan are
switched off if a run does not start within a specified time (Cryo saving (min) after the
oven ready. This function generates an alarm: “Cryo time out” . It allows to save
cryogenic coolant in case of automation failure.

17
The Oven

• Cryo saving (min): this value ranges from 10 to 120 minutes and represents the time,
calculated from the Ready condition, when the “cryo saving” function occurs.
• Cryo Fault: if the oven temperature doesn’t reach the setpoint within 16 minutes, the
cryogenic cooling will be deactivated. Press ON to activate this function.

Temperature indication - Status


· In order to see the actual oven temperature open the “Status” page (fig. 21). The number on
the right indicates the oven temperature set and that on the left the actual oven temperature
reading as taken by the probe inside the oven.

fig. 21 - Oven status

18
Installing the columns

Installing the columns

Packed columns
Due to their poor flexibility, the packed columns must be installed into the injector and the detector
at the same time.
The injector endof the column must be empty for at least 60 mm to avoid the syringe needle
entering the stationary phase. This space can be filled with glass wool.
The detector end must be empty for at least 40 mm to avoid the stationary phase damaged by the
detector heating.

Nuts and ferrules


Nuts
To install stainless steel or teflon packed columns with 6 or 4 mm external diameter use a 1/4G
brass nut. A 17 mm spanner should be used to tighten the nut.
To install glass packed columns it is advisable to use the specific 1/4G brass nut and tighten it
exclusively by end.

The columns with 1/8 inch external diameter requires the use of an adapter to adapt the 1/4G
thread of the injector and detector end to 1/8 inch thread; the 1/8 inch nut of the column is then
installed on this adapter. An aluminium washer assures the tightness between the adapter and the
injector or detector base body.

Ferrules
The two-piece brass ferrules are mostly used to install the stainless steel packed columns.
Stainless steel ferrules can also be used but the tightness is more difficult to obtain and there is the
risk to damage the column or the threaded end.

To install the glass columns, the graphite ferrules are recommended.


These ferrules provide excellent tightness even at high temperature (up to 400 °C). Furthermore,
they can be removed without damaging the column as they do not adhere to it permanently.
A brass washer must be put into the nut when a graphite ferrule is used.
The glass and Teflon columns can be installed using Viton O-rings keeping in mind that these ring
can not be heated at temperature higher than 200 °C and must be changed quite often.
The Viton O-rings are not recommended for analysis at high sensitivity (for example with ECD) as
they can release interfering substances.
An O-ring 104 with a brass washer is used for 6 mm columns.
An O-ring 104 plus 2 O-ring 2015 are needed for 4 mm column; besides, the lower part of a 4 mm
brass ferrule must be put up side down on the bottom of the nut.
Nuts and ferrules used with packed columns are summarized in the table below.

20
Installing the columns

NUTS

Stainless Steel
columns

6 mm o.d. 4 mm o.d.

Part. no. 2300 095 011


Nut F 1/4G, brass, set of 20 * *
Part. no. 2300 495 001
Nut F 1/8" SW, brass, set of 10
Part. no. 2303 230 040
Adapter F 1/4G-M 1/8SW
Part. no. 2180 095 0081
Washer 6.1x8.0x0.5, Al, set of 20
Part. no. 2300 395 001
Nut F 1/4G hand, brass, set of 10

FERRULES

Stainless Steel
columns
6 mm o.d. 4 mm o.d.

Part. no. 2306 295 004


Ferrule, BF6, brass, set of 20 *
Part. no. 2306 295 003
Ferrule, BF4, brass, set of 20 *
Part. no. 2306 395 001
Ferrule, BF 1/8", brass, set of 10

Packed column installation


Assembling a packed column should be carried out as follow:

• Slide the proper nut onto each end of the column.


• Slide a washer (if required) and a ferrule onto each end of the column.
If the ferrule is conical, this must be slided with the tapered end positioned externally.
• Insert the column into the injector and detector and push the column upwards until it
stops. Partially hand screw the nuts.
• Pull down the column for 1-2 mm and using a spanner, tighten the nut by 1/4 turn
(tighten glass columns only by hand).
• Carry out a leak test on the pneumatic circuit.

21
Installing the columns

Capillary columns
Positioning the column
Capillary columns, because of their flexibility, can be installed between any injector and detector,
independently from their position.

Fused silica capillary columns are usually wrapped on a metal support. The support should be hung
on the hook fitted at the back of the oven. Glass capillary columns or longer and multiple columns
need the appropriate horizontal support (Part. no. 3002 120 000).

When positioning the fused silica capillary column inside the oven, make sure that the terminals
come out of the end of the support without curving excessively or being stretched when connected
to the injector and detector.
Any contact between the column and the wall of the oven must be avoided.

Preparing the column


Fused silica capillary column
Columns in fused silica have an elevated degree of flexibility, thanks to the external covering in
polyimmide.

No particular preparation process is required.


It is, in any case, indispensable that the edges of the column are uniform and free of any particles
originating from the column itself, coming from the stationary phase or ferrule residue.

It is advisable, therefore, to cut one centimeter of column from both ends before inserting the
column, but after having assembled the nuts and ferrules.
In order to do this, first cut into the column with a glass cutter or file at the point in which it should
be cut, then snap off by hand.

Important

While carrying out the aforesaid operation it is advisable to wear protective goggles and gloves to
protect hands and eyes from possible injury caused by fused silica particles.
These precautions should be respected even more rigorously when handling wide bore capillary
columns which are much more rigid.

Glass capillary columns


Glass capillary columns are extremely fragile, therefore, installation requires particular care. For a
correct installation, it is fundamental that the column extremities are perfectly straight.

Nuts and ferrules


Nuts
To install both capillary and wide-bore capillary columns use SS nut F 4M (1). A 7 mm spanner
should be used to tighten the nut.

22
Installing the columns

Ferrules
Two types of ferrules are available for installing capillary columns: graphite ferrules and
vespel-graphite ferrules.

Graphite ferrules have a high degree of seal, are long lasting and can be used at elevated
temperatures (up to 450°C); they are usually recommended for glass capillary columns.
Since they do not adhere permanently to glass, they can be removed without the risk of damage to
the column. They must always be used together with a brass washer (2).
They are available in one size only since they can be adapted to different capillary column
diameters.

Vespel-graphite ferrules are specific for capillary columns. They can be used with temperature of
up to 350°C and are usually re-usable. These ferrules are subject to leakages or cracks if tightened
excessively while cold. They must always be used together with a brass washer (2).
These ferrules are available with through holes of different diameters, adapt for different external
column diameters.

The table below shows the blockages and ferrules to be used according to the type of capillary
column.

NUTS

Fused silica Glass


columns Columns
< 0.25 mm any
0.25 mm i.d. 0.32 mm i.d. 0.56 mm i.d.
i.d. diameter

Part. no. 2300 590 004


Nut F 4M, SS, + washer * * * * *
Part. no. 2180 014 002
Washer 4M, brass, set of 10 * * * * *

FERRULES

Fused silica Glass


columns columns
< 0.25 mm any
0.25 mm i.d. 0.32 mm i.d. 0.56 mm i.d.
i.d. diameter

Part. no. 2180 095 020


Ferrule 3x2x1, graphite, set of 50 * * * * *
Part. no. 2306 095 003
Ferrule 0.76 mm, VGR, set of 10 *
Part. no. 2306 095 002
Ferrule 0.46 mm, VGR, set of 10 *
Part. no. 2306 095 001
Ferrule 0.36 mm, VGR, set of 10 * *

23
Installing the columns

Assembling the glass liner


Split/splitless injector
The split/splitless injector must be used with a specific glass liner (Part.no. 9291.100 003).
It consists of a tube in borosilicate glass of correct dimensions and containing silanized glass wool,
a graphite ferrule in a steel cylinder and a steel friction washer.
The liners supplied by DANI are washed and conditioned at high temperatures.
If a silanized liner is needed, proceed to the cold silanization as explained in the section headed
“Procedure for Silanization of precolumns” in the chapter Introduction System.

The assembling of the liner (fig. 22) is not necessary when using a new instrument, since it is
already inserted in the injector.
In all other cases, assembly of the liner should be carried out as follows:

Caution!

The temperature of the oven, injector and/or detector might be high enough to cause burns.

• Remove the septum holder (1) which contains the introduction septum (2).
• Remove the internal steel ring (3), using the special spanner, which is supplied, on the
side which has two dots.
• With the aid of a pair of pliers, take out the spring (4) from the injector and the
precolumn, if there is one (7).
• Taking care as much as possible to avoid contamination, insert the new precolumn,
complete with ferrule (6) and washer (5), into the injector.
• Using the threaded end of the special spanner, tighten the graphite ferrule on the
precolumn body.

fig. 22 - Assembling the split/splitless liner

24
Installing the columns

The procedure is to screw the spanner onto the threaded part inside the injector. Give the
spanner a quarter turn at a time until a certained resistance is felt.
This operation is only necessary when a new precolumn is being fitted.
• Return the spring into the body of injector.
• Reposition and screw the internal ring, with the special spanner, until it is lined up with
the external edge of the injector.
• Refit the septum holder complete with injection septum.

Warning

Avoid tightening the septum holder more than necessary since this could cause difficulties when
introducing the needle of the syringe.
This can also create septum fragments that can consequently contaminate the precolumn.

PTV injector
A specific liner must be used with the PTV injector.
It differs from the liner used with the split/splitless injector in form and dimension.
It is a borosilicate glass tube in an adequate size which contains silanized glass wool, a graphite
ferrule in a steel cylinder and a steel friction washer.
Special liners for the PTV injector which contain a sorbent material (e.g. Tenax or Carbosieve) are
also available for special applications.
Liners supplied by DANI are washed and conditioned at high temperatures.
If a silanized liner is needed, proceed to the cold silanization as explained in the section headed “
Procedure for Silanization of precolumns”, in the chapter Introduction System.

The assembly of the liner is not necessary when using a new instrument since it is already
inserted in the injector.
In other cases, assembly of the liner should be carried out as follows (fig. 23):

Caution!

The temperature of the oven, injector and/or detector might be high enough to cause burns.

• Remove the septum holder (1) which contains the introduction septum (2).
• Remove the internal steel ring (3), using the special spanner, which is supplied, on the
side which has two dots.
• With the aid of a pair of pliers, take out the spring (4) from inside the injector and the
precolumn, if there is one (7).
• Taking care as much as possible to avoid contamination insert the new precolumn,
complete with ferrule (6) and washer (5), into the injector.
• Using the threaded end of the special spanner, tighten the graphite ferrule on the
precolumn body.
The procedure is to screw the spanner onto the threaded part inside the injector.
Give the spanner a quarter turn at a time until a certained resistance is felt.
This operation is only necessary when a new precolumn is being fitted.
• Return the spring into the body of injector.
• Reposition and screw the internal ring, with the special spanner, until it is lined up with
the external edge of the injector.
• Refit the septum holder complete with injection septum.

25
Installing the columns

fig. 23 - Assembling of the PTV injector liner

Warning

Avoid tightening the septum holder more than necessary since this could cause difficulties when
introducing the needle of the syringe.
This can also create septum fragments which consequently contaminate the precolumn.

Installation of capillary column


The installation procedure for the column is identical for both the split/splitless injector and the
PTV injector.
Identify the correct nut and ferrules for the column to be installed (see section headed Nuts and
Ferrules in this chapter) and carry on the column installation as follows (fig. 24):

Slide a nut (1) onto each end of the column, with the threaded part positioned externally, followed
by a brass washer (2) and a ferrule (3).
If a vespel-graphite ferrule is used, this must be slide with the tapered end positioned externally.
The drawing here below illustrates the correct assembly sequence.

fig. 24 - Nut and ferrule installation

26
Installing the columns

After assembling the seals, 1 cm of column should be cut from each end (see the section Preparing
the column in this chapter).

Installation of the column at the injector


• Check that the glass precolumn and other parts have been correctly inserted inside the
injector (refer to section Assembly of precolumn in this chapter).
• Attach the column cage to the two hooks on the back wall of the gas chromatograph
oven.
• Free the end of the column which is positioned towards the injector in order to avoid any
tension.
• Move the nut along the column until the distance between the end of the column and the
base of the nut measures 23-25 mm, then mark the point with an indelible marker or
liquid corrector (fig. 25).
• Insert the column into the injector and partially hand screw the nut.
• Push the column upwards until the marked point is in line with the base of the nut.

fig- 25 - Positioning the nut at the injector

The column will now be 1-2 mm inside the precolum.


• Using the pitch 7 spanner supplied, the nut should be tightened by 1/4 turn.
Avoid over tightening the nut since it could break the column.

Installation of the column in the Flame Ionization Detector


• Free the end of the column which is positioned towards the detector in order to avoid any
tension.
• Move the nut along the column until the distance between the end of the column and the
base of the nut measures 65-66 mm, then mark the point with an indelible marker or
liquid corrector (fig. 26).
This operation is not necessary if a column with external diameter higher than 0.25 mm
must be installed as it does not pass through the hole of the jet.
• Insert the column into the detector and partially hand screw the nut.

27
Installing the columns

fig. 26 -Positioning the column nut for FID

• Push the column upwards until the marked point is in line with the base of the nut. The
end of the column will now be 1-2 mm below the upper tip of the nozzle.
In the case of a column with the external diameter higher than 0.25 mm, it is possible to
push the column upwards until it stops, tighten the nut by hand and pull the column down
for 1-2 mm.
• Using the pitch 7 spanner supplied, the nut should be tightened by a 1/4 turn.
Avoid over tightening the nut since it could break the column.

Installation of the column in the Electron Capture Detector


• Free the end of the column which is positioned towards the detector in order to avoid any
tension.

• Move the nut along the column until the distance between the end of the column and the
base of the nut measures 55 mm, then mark the point with an indelible marker or liquid
corrector.

• Insert the column into the detector and partially hand screw the nut.

• Push the column upwards until the marked point is in line with the base of the nut.

• Using the pitch 7 spanner supplied, the nut should be tightened by a 1/4 turn.
Avoid over tightening the nut since it could break the column.

Installation of the column in the Photoionization Detector


• Free the end of the column which is positioned towards the detector in order to avoid any
tension.

• Move the nut along the column until the distance between the end of the column and the
base of the nut measures 10 cm, then mark the point with an indelible marker or liquid
corrector.

• Insert the column into the detector and partially hand screw the nut.

28
Installing the columns

• Push the column upwards until the marked point is in line with the base of the nut.

• Using the pitch 7 spanner supplied, the nut should be tightened by a 1/4 turn.
Avoid over tightening the nut since it could break the column.

Installation of the column in the Nitrogen - Phosphorus Detector


• Free the end of the column which is positioned towards the detector in order to avoid any
tension.

• Move the nut along the column until the distance between the end of the column and the
base of the nut measures 10.3 - 10.4 cm, then mark the point with an indelible marker or
liquid corrector.
This operation is not necessary if a column with external diameter higher than 0.25 mm
must be installed as it does not pass through the hole of the jet.

• Push the column upwards until the marked point is in line with the base of the nut. The
end of the column will now be 1-2 mm below the upper tip of the nozzle.
In the case of a column with the external diameter higher than 0.25 mm, it is possible to
push the column upwards until it stops, tighten the nut by hand and pull the column down
for 1-2 mm.

• Using the pitch 7 spanner supplied, the nut should be tightened by a 1/4 turn.
Avoid over tightening the nut since it could break the column.

Installation of the column in the Thermal Conductivity Detector


• Free the end of the column which is positioned towards the detector in order to avoid any
tension.

• Move the nut along the column until the distance between the end of the column and the
base of the nut measures about 40 mm, then mark the point with an indelible marker or
liquid corrector.

• Insert the column into the detector and partially hand screw the nut.

• Push the column upwards until the marked point is in line with the base of the nut.

• Using the pitch 7 spanner supplied, the nut should be tightened by a 1/4 turn.
Avoid over tightening the nut since it could break the column.

• Proceed in the same way to install the column in both the detector channels.

Installation of the column in the Flame Photometric Detector


• Free the end of the column which is positioned towards the detector in order to avoid any
tension.

• Move the nut along the column until the distance between the end of the column and the
base of the nut measures about 14.3 - 14.5 cm, then mark the point with an indelible
marker or liquid corrector.

• Insert the column into the detector and partially hand screw the nut.

29
Installing the columns

• Push the column upwards until the marked point is in line with the base of the nut.
The column will stand out of the nozzle for about 0.8 - 1.0 cm.

• Using the pitch 7 spanner supplied, the nut should be tightened by a 1/4 turn.
Avoid over tightening the nut since it could break the column.

• Proceed in the same way to install the column in both the detector channels.

Leak testing the pneumatic circuit


(to be implemented)

Conditioning the columns


The columns must be conditioned before use.
DANI columns have been pre-conditioned, however, to get excellent performances and to remove
any possible contaminants coming from the liner septum and column handling, we recommend
conditioning again the column. The procedure is even more essential for used columns since they
may also contain residual composites from previous introductions.

The conditioning procedure should be carried out as follows:

• Assemble the column in the chromatograph oven connecting the terminal to the injector
end only and leaving the other end free.
If the column is connected at both ends, the alternative is to remove the detector head
from the base body (except in the case of a ECD detector).
• Switch on the carrier gas and set a flow which is suitable for the type of column.
• Set a temperature program which starts from a relatively low temperature (40 - 60 °C)
and reaches a final temperature 20°C above the operating temperature without
exceeding the maximum allowed for the column, using a gradient of 2-4°C/min.
• Condition the column for 4-6 hours, setting a suitable number of analytical cycles. (When
the operating temperature is the maximum allowed, a longer conditioning time may be
necessary).

30
Introduction systems

Introduction systems

Packed column injector

Description
The packed column injector DANI IN 86/06 is capable to operate with stainless
steel columns with 6 mm, 4 mm or 1/8 inch outer diameter and glass column
with 6 mm outer diameter. It can be used also with wide-bore columns by
means of a special adapter.

The injector (fig. 27) consists of a cylindrical stainless steel body (1) on which a
carrier gas line is inserted (2).
The body is welded to a support (3) which is fixed to the gas chromatograph by two screws.

The injector is closed by an external ring (4) which holds the introduction septum (5). Inside, a steel
cylinder (6) leads the syringe needle directly into the column.

The body is directly heated by an aluminium block (7) which contains the heating resistance and
the temperature probe.
Both glass and stainless steel packed columns are inserted directly into the injector body.
Therefore, the necessity of precolumn or liner is eliminated, dead volume is minimized and the

fig. 27- Packed column injector

32
Introduction systems

compounds are directly injected into the column.


For this reason, the column end at the injector side must be free of stationary phase for at least a 6
cm length and filled with glass wool only.

As the carrier gas flow rates normally used with packed columns are high (about 30 ml/min) and
the injector volume is of a few hundred of microliters, the transfer of the sample is fast enough.

Pneumatic circuit
The pneumatic circuit of the packed column injector, illustrated in figure 28, consists of the carrier
gas line only.
An electronic control module is installed on the carrier gas line to control the flow rate or the
pressure.

When packed or undefined columns are used, the electronic control module is automatically
configured as a flow regulator.
The flow rate is controlled by the Total Flow Regulator “TFR” while an Injector Pressure Sensor
“IPS” measures the actual pressure at the injector.

fig. 28- Packed column injector pneumatic circuit

The flow rate in the packed column varies considerably with the temperature: if the pressure at the
head of the column is constant, the flow rate decreases when the temperature increases.

The flow regulator acts by increasing the pressure at the head of the column when the
temperature increases, thus maintaining the desired flow rate .
In this way, analyses with programmed temperature at constant or programmed flow rate can be
performed .

When wide-bore capillary columns of defined dimensions are used, the electronic control module is
automatically configured as a pressure regulator (fig. 29).
The Injector Pressure Regulator “IPR”, connected at the Injector Pressure Sensor “IPS”, maintains
the needed pressure at the head of the column, to guarantee the desired flow rate.

33
Introduction systems

fig. 29 - Pneumatic circuit with widebore column

Adapter for wide-bore capillary column


The packed column injector may be used with fused silica wide-bore columns (> 0.50 mm i.d.)
using the special adapter supplied with the instrument (Part.no. 0305.047 003). In this
configuration, the carrier gas flow rate must be high enough to guarantee a fast transfer of the
sample into the column.

The adapter (fig. 30) pillary columns.


The adapter must be inserted from the bottom of the injector body and locked with a nut (2) and a
brass ferrule (3).
A glass liner (4) filled with glass wool is inserted inside the body from the upper part after
unscrewing the external screw and taking off the steel cylinder.

fig. 30 - Adapter for wide-bore columns

34
Introduction systems

To install the wide-bore capillary columns on the adapter, follow the same procedure described for
the capillary injectors (refer to Capillary columns in the chapter Installing the columns).

Injector temperature (Temp)


The temperature of the packed injector is normally set at about 50 °C higher than the boiling point
of the solvent used in the sample or equal to the elution temperature of the heavier compound.
Too high temperature can increase the risk of decomposition of the sample or discrimination
effect.

· To set the injector parameters, press the corresponding shortcut key or select Menu, Injector
then A, B or C.

To enter the temperature value, open the page “Temp” and press ON to enable the temperature
control. Pressing on the box, the numeric keypad will appear. Digit the number and press OK to
confirm the setpoint (fig. 31).

fig. 31 - Injector temperature

Carrier Gas Control (press/flow and column)


When a packed/undefined column is selected, the carrier gas of a packed injector can be controlled
in two different modes:

• Constant flow: the column flow is constant during the analysis. The pressure at the head of
the column will increase with the oven temperature to maintain a constant flow.

• Programmed flow rate: in programmed flow mode the column flow rate can be set to change
during the analysis. You can enter up to 25 flow ramps.

When a capillary column is configured, constant pressure and programmed pressure modes are
also available:

• Constant pressure: in this mode the pressure is constant during the analysis. The flow will
change with the oven temperature.

35
Introduction systems

• Programmed pressure: in this mode the inlet pressure can be set to change during the
analysis. You can enter up to 25 pressure ramps

· Open the page “Column”, select the carrier gas and the column type between
packed/undefined or capillary. If you select a capillary column, you have to specify also the
dimensions (fig. 32 and 33).

fig. 32 - Column type fig. 33 - Column dimensions

Open the page “Press/Flow to select the control mode and the pressure or flow rate values (fig.
34).

fig. 34 - Press/flow controlw

36
Introduction systems

Split/splitless injector

Description
The SL/IN 86/2 split/splitless injector can be used with all types of narrow bore
and wide-bore capillary columns.
The injector (fig. 35) consists of a cylindrical steel body (1) on which a carrier
gas line inlet (2)and the split (3) (SPLIT) and septum wash (PURGE) (4) gas
lines outlet are inserted. The body is welded to a support (5) which is fixed to the
gas chromatograph by two screws. A glass precolumn (6) is inserted into the
body: a reinforced graphite seal (7) with a steel washer (8) will guarantee isolation between the
upper and lower parts of the injector body. The upper part contains a spring (9) and an internal
ring (10) through which the carrier gas flows.
The injector is closed by an external ring (11) which holds the introduction septum (12).
The injector is heated directly by an aluminium block (13) which contains the heating resistance
and the temperature probe.

Fig. 35 Split/splitless injector

Pneumatic circuit
The pneumatic circuit of the split/splitless injector consists of three gas lines: the carrier gas inlet
line, the split gas line and the purge line.

An input electronic control module is installed on the carrier gas line of injector. The purge and split
lines are connected at the output electronic control module. A molecular sieve filter “FLT” protects
the split line from contamination.

The input and output electronic control modules are automatically configured depending on the
injection technique utilized.

37
Introduction systems

When the injector is in “split mode”, the input electronic control module works as a flow regulator
(fig. 36).
A total flow rate consisting of the sum of column, split and purge flow rates os regulated by the
Total flow regulator (TFR).

PFR Purge Vent


IPS
Carrier gas Inlet TFR FLT IBPR Split Vent

Detector

Column

fig. 36 - Pneumatic circuit in split mode

The Injector BackPressure Regulator (IBPR), connected to the Injector Pressure Sensor (IPS) ,
maintains the needed pressure at the head of the column to guarantee the desired flow rate into
the column.

The Purge flow rate is controlled by the Purge Flow Regulator (PFR) while The Split flow rate is the
difference between Total flow and Purge flow.

When the injector is in “splitless mode”, the input electronic control module operates as a pressure
regulator (fig. 37).
The Injector Pressure Regulator (IPR), connected to the Injector Pressure Sensor (IPS) , maintains
the needed pressure at the head of the column to guarantee the desired flow rate. The Purge flow
rate is controlled by the Purge Flow Regulator (PFR).

Split flow rate is blocked as the Injector BackPressure Regulator is closed.

fig. 37 - Pneumatic circuit in splitless mode

38
Introduction systems

Injector temperature
In the split/splitless injector, the liquid sample must be volatilized as quickly as possible.
In order to obtain this result, the injector must be 20-30 °C above the maximum oven temperature
set for the analysis.
When the splitless technique is used (see Introduction Techniques, in this chapter), the
permanence time of the sample in the injector is higher than that of the split technique.
It is, therefore, advisable to set the injector temperature at a slightly lower value.

The ideal temperature is the minimum temperature at which complete vaporization of the sample
is obtained (therefore, the maximum area of peaks) without giving signs of thermal degradation of
the compounds.

· To set the injector parameters, press the corresponding shortcut key or select Menu, Injector
then A, B or C.

To enter the temperature value, open the page “Temp” and press “On” to active the temperature
control. If you press on the box a numeric keypad will appear. Digit the number and press OK to
confirm the setpoint. (fig. 38).

fig. 38 Injector temperature

Carrier Gas Control (Press/flow and Column)


The carrier gas of a split/splitless injector can be controlled in five different modes:

• Constant flow: the column flow is constant during the analysis. The pressure at the column
head will automatically increase with the oven temperature to maintain a constant flow.

• Constant pressure: in this mode the pressure is constant during the analysis. The flow will
decrease with the oven temperature.

• Programmed flow rate: in programmed flow mode the column flow rate can be set to change
during the analysis. You can enter up to 25 flow ramps.

39
Introduction systems

• Programmed pressure: in this mode the inlet pressure can be set to change during the
analysis. You can enter up to 25 pressure ramps.

• Linear velocity: in this case Master GC maintains the carrier gas linear velocity constant during
the column temperature program.

· Open the page “Press/Flow” (fig. 39) to select the control mode and insert flow, pressure or
linear velocity values.

fig. 39 - Carrier gas control

The carrier gas control takes into consideration the column specifications. To allow the GC to work
correctly in the selected mode, open the page “Column” and enter the carrier gas type and column
dimensions (fig. 40).

fig. 40 - Column specifications

40
Introduction systems

Injection techniques
The split/splitless injector can operate according to three injection techniques:

• the split injection, for analysing main components


• the splitless injection, for analysing trace components
• the pulsed injection

Split injection
Introduction of a sample with the split technique consists on injecting the sample into a hot
injector.
The generated vapors are divided into two different parts: one part is carried into the column by
the carrier gas and the other is discharged outside through the split line.
The ratio between the quantity of gas entering the column and the quantity discharged is
proportional to the ratio of gas flowing into the column and the flow of gas exiting from the split.
The split ratio is normally referred to the unit of the carrier gas flow rate, that is:

carrier flow rate split flow rate


split ratio = :
carrier flow rate carrier flow rate

where volumetric flow capacities are in ml/min.

For example, if the column flow rate is 2 ml/min and the split flow rate is 100 ml/min, the split ratio
is:

2 ml / min 100 ml / min


split ratio = : = 1 : 50
2 ml / min 2 ml / min

· To operate in split mode open the page “Split” and select “Split” at the voice “Mode”

“Split Flow” and “Split Ratio” values are correlated. If you insert the split flow value, the split ratio is
automatically calculated and vice versa. The split ratio value is the ratio between the split flow and
the column flow. (fig. 41).

fig. 41 - Split mode

41
Introduction systems

Splitless introduction
When using the splitless technique, the sample evaporates completely in the hot injector. When
introduction is carried out the split gas line is closed, and all the sample goes into the column.
At a certain time after introduction, the split gas line is opened. In this way, the excess of solvent is
discharged outside. The solvent peak, which otherwise would be so extended as to cover a large
portion of the initial part of the chromatogram, is significantly reduced in width.

The opening time of the split valve depends on the components, the solvent, the volume of
sample introduced and the flow rate of the carrier gas.
It is usually within a range between 20 seconds and 2 minutes.
The ideal opening time is one which gives the major response for the compounds of interest.
In splitless injection, the absolute split flow rate is not important: set a split flow rate high enough
to purg the injector (40-50 ml/min is a suitable flow rate).

Transfer of the sample into the column is slower when using the splitless injection method
compared to the split method.

Therefore, in order to reduce the subsequent widening of the peaks, the initial column
temperature should be set at a relatively low value (20-30 °C below the solvent boiling point):
under these conditions the solvent recondenses and the components refocuse in a narrow band at
the column head (Solvent effect) to be subsequently eluted in a temperature program.

When the splitless introduction technique is used, it is important to verify the purity of the solvent
used to dilute the sample, since any impurities will reconcentrate at the column head and can
interfere with the peaks under investigation.
It is advisable to carry out the analysis of a blank in order to verify the purity of the solvent.

The technique is more complex but, as the opening and closing action of the valves is
automatically performed, it is perfectly repeatable.

· To operate in splitless mode open the page “Split” and select “Splitless ”at the voice “Mode”.

Set the split flow value used to purge the injector into the box “Split purge”and the time,
calculated from the start of the analysis, at which the split valve will be opened into the box “Split
ON” (fig. 42).

fig. 42- Splitless mode

42
Introduction systems

In the splitless mode, when all setpoints are reached, the split line remains open, the inscription
“Prep” will appear in the “Start” shortcut key and “Stand by” will be displayed in the Status bar.
To perform a manual injection, press “Prep”: the split valve will close and in the Status Bar the
inscription “Ready” will appear.
Insert the syringe into the injector, inject the sample and withdraw the syringe rapidly. Then press
“Start”.
In case of automatic injection, the passage from the “Stand-by” to the “Ready” status will be
automatically performed.

Pulsed injection
When using the pulsed technique, a higher inlet pressure is activated during the injection step for
a preset time.
Increasing the pressure during the injection reduces the expansion volume, temporarly increases
the column flow rate thus improving the transfer of the analytes into the column. This effect is
especially useful in splitless injections where the column flow rate during the sample transfer is
reduced.

· To operate in this mode, it is necessary to set the pressure value at the injection time and the
duration of the pressure pulse.
Open the page “Press/Flow” and press the button “Pulsed inj”. Insert into the boxes the pulsed
pressure value and the time and press ON to activate this mode. (fig. 43).
In case of splitless injection, set the same time as in the “Split On” box.

In the pulsed injection mode, when all setpoints are reached, the carrier gas pressure will remain
at the value set in the method, the inscription “Prep” will appear in the “Start” shortcut key and
“Stand by” will be displayed in the Status bar.
To perform a manual injection, press “Prep”: the pressure at the injector increases at the pulsed

fig. 43 - Pulsed injection

pressure setvalue and in the Status Bar the inscription “Ready” will appear.
Insert the syringe into the injector, inject the sample and withdraw the syringe rapidly. Then press
“Start”. The pressure at the injector remains at the higher value temporarly during the pulsed
pressure period.

43
Introduction systems

In case of automatic injection, the passage from the “Stand-by” to the “Ready” status will be
automatically performed.

Purge flow rate


In a chromatographic system, especially with capillary columns, the introduction septum is an
evident source of contamination. For this reason the split/splitless injector is equipped with a purge
line which provides a constant flow that purges the introduction septum in the internal area of the
injector.
Usually, a 3-6 ml/min purge flow rate is a suitable value.

The purge line is fed by the carrier gas itself.

· To set the flow rate of gas flowing into the purge open the page “Split” and press the button
“Purge”. Insert the value in the corresponding box. (fig. 44).

fig. 44 - Septum purge

Gas saving
The “Gas saving” reduces the carrier gas flow rate from the split vent after the sample has been
transferred into the column until the next injection, thus saving amounts of gases.
Keep a flow rate of at least

· To set the value open the page “Split” and press the button “Gas saving”. Press ON to turn on
the gas saveing flow and in the box “Flow” insert the setpoint value. The split flow rate will be
reduced immediately, the “Stand by” status will be showed on the toolbar and “Prep” will appear
on the Start shortcut key.
In the box “Time” enter the time during the run when the split flow rate is reduced. (fig. 45). In
case of split injection, set a time after the injection time. In case of splitless and/or pulsed
injection, set a time after the splitless or pulsed time.

Pressing “Prep ” will restore the initial split flow rate and “Ready” will be showed on the status bar .

44
Introduction systems

fig. 45 - Gas saving

Introducing the sample


In order to have quantitative and repeatable data with a split/splitless injector, a correct sample
introduction technique must be used to limit the well known discrimination phenomenon. This is
particularly important when the sample contains components in a wide range of concentrations
and which differ in volatility and polarity.

It has been demonstrated that the discrimination phenomenon in the sample is mainly at the
syringe needle level.
When the syringe needle is introduced in the septum, it accumulates heat from the injector, this
resulting in the partial evaporation of the more volatile substances inside the needle itself.

When the syringe plunger is pushed, the solvent and the more volatile substances evaporate more
rapidly than substances with a higher boiling point, subsequently, these tend to remain into the
internal walls of the needle.
Therefore, when the needle is removed from the injector, a fraction of the non volatile components
is also removed.
The result is a discrimination phenomenon caused by the volatility level of each component.

This discrimination effect can be minimized by optimizing the introduction technique regarding
both the operative parameters and correct use of the syringe.
In consideration of this point, it should be noted that the condition of the syringe being used is
fundamental to obtain good results.
Syringes which have imperfections such as deformations or leaks should be discarded.

Use of an automatic sampler will noticeably improve repeatability as opposed to manual


introduction: each step of introduction is identical for each injection.

Different methods of using the syringe have been documented (full needle, cold empty needle, hot
empty needle, solvent plug, air plug).
The Hot needle technique results, for many research workers, as being the technique which
provides the best results.

The Hot needle introduction technique is as follows:

45
Introduction systems

• Take the sample, in direct contact with the plunger, and measure the required quantity.
• Aspirate the all sample into the cylinder of the syringe.
• Introduce the needle into the injector.
• Wait a few seconds (3-5 sec.) until the needle reaches the temperature of the injector.
• Introduce the sample by pushing the plunger as quickly as possible and extract the
syringe within one second.

This method guarantees a minimum of discrimination, even if total elimination is not possible,
more especially with compounds which have very different volatility levels.

In the case of thermolabile compounds, which can degrade in contact with the hot metal surface of
the needle, an alternative is to use the solvent plug technique.

The procedure is the following:

• Clean the syringe by filling and emptying it several times using the solvent, then eliminate
any excess. The needle volume will be filled with solvent.
• Aspirate a significant volume of air.
• Aspirate a more than adequate quantity of sample.
• Regulate the plunger on the level of the required sample volume by measuring the
difference with the air volume then eliminate any excess.
• Aspirate the total volume of liquid (solvent + air + sample) into the cylinder of the
syringe.
• Introduce the syringe into the injector.
• Push the plunger quickly then extract the syringe from the injector.

Example

In order to take 1 ml of sample with a 10 ml syringe: after cleaning the syringe with solvent, bring the
level of the solvent inside the cylinder of the syringe to the 1 ml indication. By doing so the air intake
volume will be 1.0 ml.
Take a more than adequate quantity of the sample then eliminate the excess and measure 1 ml by
bringing the solvent level to the 2 ml indication. Take the entire volume into the syringe and then
inject.

By using this procedure, the volume of solvent corresponding to the volume of the needle (appros.
0.7 ml) will flush the entire sample from both the syringe and the needle.

If the split technique is used, introduction must be rapid and constant. Furthermore, it is advisable
to use a spacer so that the needle penetrates about 20 mm into the injector.

If the splitless technique is used, the carrier gas speed is lower, introduction must be slower but
quite regular.
The whole length of the needle must penetrate (50 mm).

46
Introduction systems

PTV Injector (Programmed Temperature Vaporizer)

Description
The PTV injector (fig. 46) is equivalent to a split/splitless injector which does not
have a constant, but a programmed temperature.
In this case the sample is introduced into the injector at a low temperature.
When the syringe is extracted, the injector is then brought rapidly to a high
temperature.
The temperature can be programmed in a linear manner, that means a
temperature gradient can be set.
The injector is composed of a steel cylinder body (1) where the carrier gas line (2) enters and the
split lines (3) as well as the septum purge gas line (4) exits.

fig. 46 - PTV injector

The body is welded to a support (5) which is fixed to the gas chromatograph by two screws.
A glass precolumn (6) is inserted into the injector body: a reinforced graphite seal (7) with a steel
washer (8) will guarantee insulation between the upper and lower parts of the injector body.
The upper part contains a spring (9) and an internal ring (10) through which the carrier gas flows.
The injector is closed by an external ring (11) which holds the introduction septum (12).
The injector is heated by a heating resistance (13) which is wrapped around the cylinder body
itself.
The temperature probe (14) is positioned near the body.
Cooling is obtained by immission of ambient air through a small fan (15) located on the top of the
instrument.

47
Introduction systems

Pneumatic circuit
The pneumatic circuit of the PTV injector is identical to the split/splitless circuit. Therefore, refer to
the description reported in the paragraph Pneumatic circuit of the split/splitless injector in this
chapter.

Injector temperature (Temp)


In the PTV injector, the liquid sample is introduced maintaining the injector at a temperature lower
than the boiling point of the solvent.
After introduction, the injector is rapidly heated at a temperature high enough to vaporize all the
components of the sample.

· To set the injector parameters, press the corresponding shortcut key or select Menu, Injector
then A, B or C. Press ON to enable the temperature control and use the numeric keypad to to
insert the temperature, time and rate values. Press OK to confirm the setpoint (fig. 47).

fig. 47 - PTV temperature

Carrier Gas Control (Press/Flow and Column)


The carrier gas of a PTV injector can be controlled in five different modes:

• Constant flow: the column flow is constant during the analysis. The pressure at the column
head will automatically increase with the oven temperature to maintain a constant flow.

• Constant pressure: in this mode the pressure is constant during the analysis. The flow will
decrease with the oven temperature.

• Programmed flow rate: in programmed flow mode the column flow rate can be set to change
during the analysis. You can enter up to 25 flow ramps.

• Programmed pressure: in this mode the inlet pressure can be set to change during the
analysis. You can enter up to 25 pressure ramps.

48
Introduction systems

• Linear velocity: in this case Master GC maintains the carrier gas linear velocity constant during
the column temperature program.

· Open the page “Press/Flow” (fig. 48) to select the control mode and insert flow, pressure or
linear velocity values.

fig. 48 - Carrier gas control fig.49 - Column specifications

The carrier gas control takes into consideration the column specifications. To allow the GC to work
correctly in the selected mode, open the page “Column” and enter the carrier gas type and column
dimensions (fig. 49).

Introduction techniques (Split)


In the PTV injector, the liquid sample is introduced maintaining the injector at a temperature lower
than the boiling point of the solvent.
After introduction, the injector is rapidly heated at a temperature high enough to vaporize all the
components of the sample.
The injection may be performed according to four different modes (fig. 50):

• split injection
• splitless injection
• solvent split injection
• pulsed injection

49
Introduction systems

fig. 50 - PTV injection mode

Split injection
In the split technique, the sample vapours are divided into two parts: the minimum part enters the
column, the remaining part is eliminated to the outlet through the split vent.
In the PTV injector, the liquid sample is introduced maintaining the injector at a temperature lower
than the boiling point of the most volatile component.
The ratio between the quantity of gas entering the column and the quantity discharged is
proportional to the ratio of gas flowing into the column and the flow of gas exiting from the split.

The split ratio is normally referred to the unit of the carrier gas flow rate, that is:

carrier flow rate split flow rate


split ratio = :
carrier flow rate carrier flow rate

where volumetric flow capacities are in ml/min.

For example, if the column flow rate is 2 ml/min and the split flow rate is 100 ml/min, the split ratio
is:

2 ml / min 100 ml / min


split ratio = : = 1 : 50
2 ml / min 2 ml / min

As the syringe needle is withdrawn, the injector is rapidly heated. The split line is constantly open
(fig. 51).

The main advantages of the split injection performed with the PTV injector, respect to the
introduction with the split/splitless injector, are the followings:

• The selective evaporation of the sample inside the syringe needle is eliminated. This
phenomenon is considered one of the main sources of discrimination as high boiling
substances vaporize less than the more volatile ones and then remain partially in the
needle.
• Besides, the degradation of thermolabile compounds on the hot surface of the syringe
needle is avoided.
• cold introduction permits precise quantification of the sample amount introduced as well
as an accurate and linear splitting with a minimum discrimination effect. Therefore, it is

50
Introduction systems

the ideal technique for introduction of small quantities in an extremely repeatable and
accurate manner.

fig. 51 - PTV split mode: split and temperature profile

· To operate in split mode open the page “split” and and at the voice “Mode” select “Split”

“Split Flow” and “Split Ratio” values are correlated. If you insert the split flow value, the split ratio is
automatically calculated and vice versa. The split ratio value is the ratio between the split flow and
the column flow (fig.52).

fig. 52 - Split injection

51
Introduction systems

Splitless injection
In splitless injection mode, the liquid sample is introduced into the evaporator with the split line
closed.
After the major quantity of sample has been transferred to the column, the split line is opened and
the excess solvent eliminated.
Therefore, the splitless technique is suitable for highly diluted solution samples.

Unlike in the split/splitless injector, splitless introduction in the PTV is carried out at a low
temperature.
The initial injector temperature must be lower that the solvent boiling point temperature.
A few seconds (2-3 secs) after introduction, the injector is rapidly heated to a temperature at
which the sample evaporates completely.
When enough time has elapsed for the transfer of the sample to the column (30-90 seconds), the
oven temperature programme begins and the split line opens: in this way, any residual solvent is
eliminated (fig. 53).

With splitless introduction, transfer of the sample from the injector to the column is slower that
with split introduction.
In order to reduce the widening of the peaks, the initial column temperature must be set at a
relatively low value (20-25 °C lower than the solvent boiling point): in this way the solvent will
recondense and the components will refocalize on a narrow band at the column head (Solvent
effect), to be consequently eluted in a temperature programme.

fig. 53 - Splitless injector - Split and temperature profile

· To operate in split mode open the page “split” and and at the voice “Mode” select “Splitless.”

Into the box “Split purge” you can set the split flow value and into “Split ON” the time during the
run at which the “Split purge” valve will be opened. (fig. 54).

In the splitless mode, when all setpoints are reached, the split line remains open, the inscription
“Prep” will appear in the “Start” shortcut key and “Stand by” will be displayed in the Status bar.
To perform a manual injection, press “Prep”: the split valve will close and in the Status Bar the
inscription “Ready” will appear.

52
Introduction systems

Insert the syringe into the injector, inject the sample and withdraw the syringe rapidly. Then press
“Start”.
In case of automatic injection, the passage from the “Stand-by” to the “Ready” status will be
automatically performed.

Solvent split injection

fig. 54 - Splitless injection

With this technique, the sample is introduced in the injector maintained at a low temperature with
the split valve open. After most of solvent has been eliminated, the split line closes and the
temperature rapidly increases (fig. 55).

In this way, these effects are obtained:

fig. 55 - Solvent split injection - split and temperature profile

53
Introduction systems

• the elimination of most of the solvent and therefore the possibility to detect also early
eluting peaks.
• the possibility to increase the injection volume and to perform repeated injections to
concentrate a very diluted sample.

The only drawback of this technique is the possibility to analize only compounds with a boiling
point higher than the boiling point of the solvent otherwise they would be partially lost.

To minimize this effect, injection parameters as initial temperature of the injector, split flow rate
and duration of the split phase must be optimized .
To limit the loss of the most volatile substances, the injector temperature must be set at a value as
lower as possible during the split phase.
In some cases, the use of a cryogenic cooling of the injector is necessary.
If the presence of a small amount of solvent is acceptable, the duration of the split phase and the
split flow rate may be reduced, taking advantage of the refocalizing effect of the solvent (Solvent
effect).

Furthermore, the retention capacity of the injector insert can be increased by substituting the glass
wool with an adequate packing material, possibly coated with a stationary phase.

By optimizing the introduction conditions, a sample amount of up to 50-100 ml can be introduced


by this technique.

· To operate in Solvent Split mode open the page “Split” and at the parameter “Mode” select
“Solvent Split.”

Into the box “Split Flow” , set the split flow value, into “Split OFF” the time during the run at which
the “Split ” valve will be closed and in “Split ON the time at which the valve will be opened. (fig.
56).

Pulsed introduction
When using the pulsed technique an higher inlet pressure is activated during the injection step for
a preset time.

fig. 56 - Solvent split injection

54
Introduction systems

Increasing pressure at the injection time helps to control expansion volume and improves transfer
of solutes to the column.

· To operate in this mode, it is necessary to set the inlet pressure at the injection time and the
duration of the pressure pulse.

Open the page “Press/Flow” and press the button “Pulsed inj”. Insert into the boxes the values
and press ON to activate this mode. (fig. 57)

When all setpoints are reached, the inscription “Prep” will appear in the “start” shortcut key and
“Stand by”in the Status bar. Pressing “Start” the pressure will increase up to the set value and in
the Status Bar the inscription “Ready” will appear.

Purge flow rate


As with the split/splitless injector, the PTV injector also has a purge line which provides a constant
flush of the introduction septum inside the injector. The purge line is fed by the same carrier gas as

fig. 57 - Pulsed injection

the injector.

· To set the quantity of gas flowing into the purge open the page “Split” and press the button
“Purge”. Insert the value in the corresponding box. (fig. 58)

Gas saving
The “Gas saving” is a special mode for saving the carrier gas through the reduction of split flow
during the analysis or when the GC isn’t utilized

· To set the value open the page “split” and press the button “Gas saving”. Press ON to turn on
the gas saver flow and in the box “flow” insert the setpoint value.
The split flow rate will be reduced immediately, the “Stand by” status will be showed on the toolbar
and “Prep” will appear on the Start shortcut key.

55
Introduction systems

fig. 58 - Purge flow rate

In the box “Time” enter the time during the run when the split flow rate is reduced. (fig. 59). In
case of split injection, set a time after the injection time. In case of splitless and/or pulsed
injection, set a time after the splitless or pulsed time.

Pressing “Prep ” will restore the initial split flow rate and “Ready” will be showed on the status bar .

Introducing the sample


Introduction of the sample at a low temperature prevents evaporation of the sample inside the
needle of the syringe.
This avoids sample discrimination and allows accurate measurement of the injected volume.
In general, therefore, the use of a syringe is not as critical as with the split/splitless injector.
Since the volume of the evaporation chamber is limited in order to promote thermal exchange, the

fig. 59 - Gas saving

injection of small quantities is advisable in order to avoid over saturating the evaporator.
Higher quantities can be injected with the Solvent split technique (see Solvent split injection, in this
chapter).

56
Introduction systems

When using the Split injection technique, injection must be rapid and continue otherwise double
introduction phenomena can occur. Furthermore, it is advisable to use a spacer so that the needle
penetrates about 20 mm into the injector.

If the splitless technique is used, therefore, the carrier gas speed is lower, introduction must be
slower but quite regular.
The whole length of the needle must penetrate (50 mm).

In case of Solvent split injection, the ideal introduction speed should correspond to the evaporation
speed of the solvent.
Since this is difficult to determine, it is advisable to carry out injection of the sample very slowly (1
ml/sec).
The slower introduction is carried out, the higher the injectable volume will be.

57
Detectors

Detectors

In order to gain access to the “Detector” window, press Menu, Detectors, then A, B or C according
to the detector position.

You can also press the corresponding short cut key on the toolbar.

Flame Ionization Detector FID 86/10

Introduction
In the flame ionization detector (fig. 60), a microflame is produced at the nozzle outlet
when a Hydrogen flow comes into contact with a flow of air.
The nozzle and a coaxial steel tube form the electrodes of a circuit.
A voltage is applied at each end of this circuit.

In normal conditions, the molecules of the pure carrier gas and of the auxiliary gas (if used)
that reach the flame are ionized and produce charges (positive and negative ions and

fig. 60 - Flame Ionization Detector

electrons): these charges, gathered by an electrode, generate a weak and constant current
called base current.
When an organic compound exits from the column and reaches the flame, through a
combustion process, the number of charges produced increases and subsequently the
ionizing current also increases.

58
Detectors

The ionizing current passes through a resistor and generates a signal that is proportional to
the number of charges produced. This signal is adequately amplified and can be
transmitted from the electrometer to a registration system.
The variation of the signal in time, caused by the passage of an organic compound through
the flame, determines registration of a peak.

The flame ionization detector has the characteristic of being highly sensitive to organic
compounds (10 - 100 pg according to the compound).
Sensitivity reaches a maximum with organic compounds containing Hydrogen, whereas it is
lower with organic compounds that have partially or totally oxidized carbon atoms
(carboxyls, carbonyl, alcohols, ...).
Some substances give low response or no response at all, amongst these: H 2O, CO, CO 2,
SO2, CS 2, Formaldehyde, Formic acid, N 2, O 2, NH 3.

The FID detector gives an optimal linearity response, in the order of 10 6 times the minimum
sensitivity.

Description
The FID 86/10 detector can be used with both capillary and packed columns.
It is composed of three main parts:

• the base body


• the detector head
• the control unit

The base body


The base body (fig.61) is composed of a stainless steel cylinder (1) welded to a support (2) and
secured to the gas chromatograph by two screws(3).
The unit is inserted into an aluminium block (4) containing the heating resistor (5) and the
temperature probe (6). Two gas lines are installed on the side of the base body:

• the inferior line (7) for the inflow of Hydrogen and auxiliary gases

• the upper line (8) for the inflow of air.

fig. 61 - FID 86/10 base body

59
Detectors

A nozzle (9), which is electrically grounded, is screwed inside the base body. In the upper part, the
knurled brass ring (10) secures the head to the base body.
The end section of the body, inside the chromatographic oven, has a 1/4G thread (11).
Packed columns can be connected directly to this section with a 1/4G nut (12) and brass ferrules
(13).
If capillary or wide bore capillary columns are used, an adapter (14) to reduce the internal volume
of the base body should be installed: the end section of the adapter has a 4M thread.

The detector head


The detector head (fig. 62) is composed of :

• the electrode collector (1), coaxial to the nozzle

• the connector (2) to link up to the control unit

• the resistor for igniting the flame (3)

• the chimney (4)

The head is secured to the base body by a brass ring assembled on the base body.
An O-ring seal (5) inserted on the lower part of the head provides an adequate seal between the
head and base body.

The signal cable is connected to the connector (2) whereas the power supply cable is inserted onto
the flame ignition resistor connector (3).
Both cables come from the detector control unit.

fig. 62 - FID 86/10 head

The control unit


The control unit (fig. 63) provides electronic control of both the signal coming from the detector
head and the power supply.
The control unit includes an electrometer (1), the detector control board (2) and the resistor power
supply board (3) for igniting the flame.

60
Detectors

On the left side of the main board there is a connector (4) to link the control unit to the main board
of the gas chromatograph.

The signal cable (5), exiting from the electrometer, must be connected to the detector head; the
cable (6) supplies the igniter of the detecctor head.

fig. 63 - FID control unit

Detector temperature
The base body temperature must always be set at a value that is higher than the maximum oven
temperature in order to avoid the condensation of the compounds in the line.
In any case it must be over 100°C in order to avoid water condensation.

Setting the temperature (“Temp” page)


The temperature of the detector can have a value between 40 and 450°C, with increment of 1°C.

fig. 64- FID Temperature

61
Detectors

· In order to set the detector temperature open the page “Temp”, press ON to activate the
temperature control and use the numerical keypad to insert the value in the corresponding box
( fig. 64).

Indication temperature (“Status” page)


· In order to see the detector temperature open the “Status” page. The number on the right
indicates the temperature set for the detecto rand on the left the actual temperature as measured
by the temperature probe (fig. 65).

fig. 65 - FID Status

Regulating the gas flow rates


The sensitivity of the FID detector depends widely on the flow rate of the gases.
More particularly, the maximum ionizing results are obtained by optimizing the ratio between the
sum of carrier gas and auxiliary gas (if used) flow rates and the flow rate of the Hydrogen.

The carrier gas flow rate can vary considerably according to the type of column (packed or
capillary) and the separation.
With packed columns, once the flow rate of the carrier gas is established, the flow rate of the
Hydrogen will have to be optimized in order to obtain maximum response.

With capillary columns, since the flow rate of the carrier gas is reduced, an auxiliary gas flow must
be added. The optimal auxiliary gas is Nitrogen.
Response is higher with a Nitrogen/Hydrogen mixture than with a Helium/Hydrogen mixture.
In both cases, the ratio between the Hydrogen and the inert gas (carrier plus auxiliary) can be
optimized by regulating the auxiliary gas in relation to a constant Hydrogen flow.
In the FID 86/10 detector, for a Hydrogen flow of 38 ml/min, the optimal carrier and auxiliary gas
flow rate is 43 ml/min.

Air, which is the combustion support for the flame, must be available in stoichiometric excess
compared to the Hydrogen: under these conditions any flow variation will not influence the
ionization efficiency of the flame.
It is, therefore, advisable to work with flow rates higher than 300 ml/min.

62
Detectors

Setting the flow rates (“Flows” page)

· By opening the page “Flows” you can set all gas control parameters needed for the functioning
of the detector (fig. 66) .

Press ON to activate the flow controls and, through the drop-down menu, select the auxiliary gas
(Nitrogen or Helium).

fig. 66 FID Gas flow rates

By using the numerical key pad insert the gas flows rate values expressed in ml/min.
Aux and Hydrogen can have a value between 0 and 100 ml/min, with increment of 1 ml/min. The
setpoint of Air can range between 0 and 1000 ml/min, with increment of 1 ml/min.

Warning

Before regulating the Hydrogen flow rate, check that the detector is connected to a column or
protected by a closure in order to avoid the liberal escape of gas inside the gas chromatograph
oven: this can cause an explosion.

Visualizing gas flows (“Status” page)


In order to read the gas flow regulation open the “Status” page. The number on the right indicates
the set value and that on the left the actual value. (fig. 65)

Flame
In the page “Flame” you can find the following parameters (fig. 67):

• Flame threshold (mV): the FID produces a small signal current when lit.
This parameter defines the flame on condition. Master GC uses this value to determine
flame status (ON or OFF; see page “Status”) and controls the automatic re-ignition.
The flame will re-ignite if the signal drops below this value.
This value, expressed in mV, can range between 0 and 1000 mV with increment of 0.01
mV.
• Auto Ignition: press “On” to enable the auto ignition function.

63
Detectors

fig. 67 - FID flame

Auto Ignition
Master GC is able to carryout an auto ignition procedure.

When the detector temperature reaches 200°C, the system starts the auto ignition procedure:

• the auxiliary gas (Aux) turns off and the Hydrogen is adjusted to 60 ml/min.
• the resistor for flame ignition switches on for xx seconds . This process will cause a small
explosion.
When the flame is ignited, the signal level moves from 0 to a positive value.
Ignition can be checked by putting a cold shiny object near the chimney: condensation
will be present.
• the resistor switches off
• the auxiliary gas turns on and the Hydrogen is restored to the set point value
• the flame is checked to be “ON” (see “Status” page)

When the flame is “off”, the alarm “ FID FLAME OUT” will appear: the system will attempt to
re-ignite the flame up to five times at intervals of 1,5 minutes.

If the flame re-ignition fails, after 5 minutes the system turns off all FID gases and the alarm “FID
GAS CLOSED” will be shown.
Press “Clear” to cancel the alarm.

Signal
In order to set all the operative parameters for signal control, open the page “Signal” (fig. 68).

Selecting the RANGE level


The amplitude of the detector dynamic range can be varied to suit the analytic needs by selecting
the RANGE function.
It means that, at different range, the same value of current measured by the detector produces a
different output signal.

64
Detectors

fig. 68 - FID signal

Three range levels (1, 10, 100) are available: for each higher level, the dynamic range of the signal
produced by the detector is increased by a 10 factor compared with the previous level.
This results in a output signal 10 times lower for the same current value.
Set the RANGE function to 1 to get the minimum full scale range, that is the maximum sensitivity.

An example of of the effect of the range on the signal is reported in the table below for both the 0-1
and 0-10 V scale.

Range Current Signal (0 - 1V) Signal (0 - 10V)

1 1 pA 1 mV 10 mV

10 1 pA 0,1 mV 1 mV

100 1 pA 0,01 mV 0,1 mV

Selection of the RANGE level depends on the analytic conditions: select the proper range level to
guarantee that all peaks of interest are within the detector dynamic range, which means that the
corresponding signal does not exceed the scale maximum and that at the same time they are not
too small to be correctly measured.

· Select the range levels through the drop-down menu (fig. 68).

Digital acquisition rate


As a general rule, at least 10-20 data for peak must be acquired to correctly define a peak.
This means that the acquisition rate must be select so that the product of Acquisition rate
(sampling/sec) and the peak width in seconds is between 10-20.

Besides, the response time provided by the electrometer must be adequate to detect fast peaks.
MasterGC provides two levels of response time: one for fast peaks (Min.Half-Peak Width < 0.6 sec)
and one for conventional peaks (Min.Half-Peak Width > 0.6sec). According to the Min. Half-Peak
Width setpoint (< 0.6 sec or > 0.6 sec), the response time will be automatically adjusted.

65
Detectors

Digital acquisition rate (expressed in Hz) can assume the following values: 2.5, 10, 25, 50, 100,
250, 300.
According to the Min.Half-Peak Width set, the optimal acquistion rate is automatically suggested
(fig. 68). You can still select a different one through the drop down menu.

fig. 69 - FID Graph

Graphic
In the page “Graph” the plot of the signal will be visualized. Use the buttons “+” and “-” to change
the time scale (expressed in minutes) and the Voltage scale (expressed in mV).

66
Detectors

Electron Capture Detector ECD 86/30

Introduction
The electron capture detector (fig. 70) functions on the basis that electronegative substances
react with free electrons and form negative ions.

C + e- ® C - + energy

The reduction in the quantity of free electrons is proportional to the concentration of the substance
and its electron affinity, that is, to its aptitude in capturing electrons.
The electrons are produced by ionizing the carrier gas with a radioactive source which produces b
particles.
This means that the flow of carrier gas from the gaschromatographic column, appropriately mixed
with the auxiliary gas, passes into an ionization chamber in which two electrodes are located.
The cathode, particularly, is a source of low energy radiation (63Ni): when the carrier gas exiting
from the column is introduced into the detector chamber, the radiation excites the gas molecules
producing ionization phenomena.
In this manner low energy free electrons and positive ions are formed.
When continuous current is applied to the two electrodes, because of the electrical field, the
charges move towards the electrodes of the opposite sign and generate a constant current in the
detector.
This current, appropriately amplified by an electrometric amplifier, is recorded as a constant base
current.

fig. 70 - Electron Capture Detector

When a certain quantity of substance capable of capturing electrons is introduced into the
ionization cell, it becomes a negative ion and subtracts a certain number of electrons from the
system.
Consequently there is a reduction in the base current: this reduction, being proportional to the
quantity of substance and relative electron affinity, is used for a quantitative calculation of the
substance.

68
The system, as described, in which a constant voltage is applied to each end of the electrodes was
used in the first electron capture detectors which, in spite of a good sensitivity, showed a limited
response dynamic.
In most of the up-to-date devices, which include the DANI ECD 86/30, a variable frequency
impulse voltage is applied in order to maintain the current circulating in the circuit constant even in
presence of electron capturing substances.

Voltage is supplied with low frequency impulse, fo, during the passage of the pure carrier gas.
During the transit of an electron capturing substance, the circuit increases the frequency of the
voltage impulses, fc, in order to maintain the number of electrons in the system constant and
consequently the current in the cell.
The difference between the frequency when an electron capturing substance is present and the
initial frequency of the impulses (fc-fo) is measured: it is proportional to the concentration and to
the electron affinity of the substance under examination and represents the signal exiting from the
detector.

A detector with these characteristics guarantees a higher dynamic of linear response (up to 104).
In fact, the maximum efficiency of electron capture is obtained when the electron capturing
substances interact with “low energy” electrons.
However, because of the effects of the electrical field, the electrons are inevitably subject to an
acceleration which reduces the capture phenomena probabilities.
The supply of very brief impulse voltage limits the acceleration effect in that the electrons which
are not captured are periodically gathered around the electrodes and offers a better capture
efficiency even at higher concentrations.

The DANI ECD 86/30 detector is composed of a single body and the control unit.

The detector body


The detector body (fig. 71) consists of a stainless steel cylinder (1) assembled on a plate (2) which
is secured to the gas chromatograph by two screws (3).
The heating system is enclosed in an aluminium block (4) which contains the heating resistance (5)
and temperature probe (6).
The detector is equipped with an auxiliary gas line (7) which feeds gas just before the entry of the
ionization cell and mixes it with carrier gas.

fig. 71 - ECD body

69
The vent line (8) on the upper part of the body connects the ionization cell with the environment.
The ionization cell is located inside the detector body. It has a coaxial geometry: the collector
electrode (anode) is concentric to the ionization cell itself which consists of a stainless steel
cylinder connected to the ground (cathode).
The electron source consists of a plaque electroplated with 63Ni isotope held on the inside wall of
the cell.
The cell is electrically isolated by high temperature (400°C) resistant dielectric materials.
The anode terminal is connected to the control unit by a connector (10): the polarization voltage
supplied by the control unit reaches the electrode which in turn sends back the charges collected.
The lower part of the detector body ends in a threaded terminal (11) which goes into the
gaschromatographic oven.
The packed columns can be installed directly on the terminal by means of a 1/4G nut (12) and
suitable ferrules (13).
In order to install capillary or wide bore capillary columns a wide bore capillary column adapter
(14) that reduces the volume of the terminal and has a 4M threaded end must be applied.

The control unit


The control unit (fig. 72) provides electronic control of the detector.
The control unit is essentially a board (1) containing an excitation circuit that supplies variable
frequency voltage impulses, an electrometric circuit and a frequency-voltage converter (2).
On the left side of the main board there is a connector (3) for connecting the control unit to the
main board of the gas chromatograph.

fig. 72 - ECD control unit

The control unit is located in the console of the gas chromatograph in one of the four positions
which are, from left to right, A, B, C and D and that correspond to the positions of the detectors.
The electrometer has an external cable with relative connector (4) for charge collection and
transmission of the excitation voltage.

Sensitivity and selectivity


The ECD is one of the most sensitive detectors used in gas chromatography. The detector
response to each single substance depends on the specific affinity of each one to the electrons.
The capacity to capture electrons varies significantly amongst the different substances (in a range

70
of 106) and depends on whether there are, or are not, electrophorus (atoms, groups or structures)
in the molecule.
Higher response is normally obtained from electronegative compounds containing halogens or
nitro groups.
For halogenated compounds, response decreases according to the sequence I> Br> Cl> F.

The table below provides, by way of indication, the relative response factor of several classes of
compounds:

Hydrocarbons 1

Ethers, Esters 10

Aliphatic alcohol, Ketones, Amines, mono-Cl 100


compounds and mono-F substitutes

mono-Br, di-Cl and di-F substitutes 1000

Anhydrides and tri-Cl substitutes 10000

mono I, di-Br, poli-Cl and poli-F substitutes 100000

di-I, tri-Br, poli-Cl and poli-F substitutes 1000000

Among compounds of the same kind, a small difference in the molecular structure can cause a
significant difference in response.
Sensitivity also depends on the position of the electrophorus and their number in the molecule.

o-Dichlorobenzene 42

m-Dichlorobenzene 30

p-Dichlorobenzene 11

-CHCl2 1

Response increases in a synergic manner with the increase in number of substitutions on the same
Carbon atom.

-CH3 , -CH2Cl 1

CH3Cl 2

-CHCl2 22

-CCl3 750 000

CCl4 11 300 000

71
The difference in response between compounds with different halogen/carbon ratio and mainly
the poor or lack of response of hydrocarbons in general make the ECD a detecting system which
other that being a sensitive system is also an extremely selective one.

This means that analyses results provide both quantity and quality information on the compound
of the sample analyzed.
On the other hand, it is precisely for this reason that a correct quantitative calculation always
requires the appropriate use of a calibration system.

Carrier gas and auxiliary gas


In order to produce free electrons, through ionizing radiation, it is essential to have a gas that is
easily ionized inside the cell.
Nitrogen and Argon at 5% Methane* are the most suitable gases and those most commonly used
in the electron capture detector.
They can be used either as carrier gas, more particularly with packed columns, or as an auxiliary
gas, for example with capillary columns, when added to the normally used carrier gas.
In both cases, whether the gas is carrier or auxiliary, it is important that the flow rate of the
Nitrogen or Argon-Methane reaching the detector is of at least 30-40 ml/min. Since the electron
capture detector is sensitive to concentrations, higher gas flow rates only lead to a reduction in the
detector’s sensitivity caused by increased dilution of the sample.

In order to obtain maximum working efficiency from the detector the carrier and auxiliary gases
should be extremely pure and humidity-free.
The presence of impurities, as for example H2O or O2 or any other electron capturing substance,
reduces the detector sensitivity in that any impurities take up some of the available electrons.

It is important to note that any type of leakage will also cause a reduction in sensitivity.
The cause of this is that through the leakage, environmental air sweeps into the detector and
subsequently into the cell. The presence of Oxygen in the air takes up electrons causing a
reduction in sensitivity. For the same reason, when there is a lack of carrier gas or auxiliary gas in
the detector for a certain period of time, Oxygen and humidity from the environment flow into the
lines and detector cell.
When the detector is re-activated it takes several hours to eliminate Oxygen and humidity and
restore optimal working conditions

*Methane, through deactivating molecular collisions, reduces the presence of metastable types of
Argon and reduces the energy of the electrons making them easier to be captured.

When the electron capture detector is in constant use, it is advisable to leave a continuous flow of
gas, even few ml/min, during the periods of inactivity (nights, weekends, etc.) keeping the
detector heating on and the gas chromatographic oven at a low temperature.

Setting the flow rate (“Flows” page)


· Open the page “Flows” (fig. 73) and press ON to activate the control flows: through the
drop-down menu, select the auxiliary gas (Nitrogen or Argon-Methane).
Insert in the box “Aux” the value required. The auxiliary flow can have a value between 0 and 100
ml/min, with increment of 1 ml/min.

72
fig. 73 - ECD Aux gas

Visualizing gas flows (“Status” page)


· In order to read the gas flow regulation open the “status” page. The number on the right
indicates the set value and on the left the actual value (fig. 74).

fig. 74 - ECD status page

Temperature
The response of the electron capture detector is highly influenced by the temperature of the
detector itself.
This is caused by the reaction mechanisms of the electrons with the molecules: some of these
mechanisms are aided by the temperature whereas others are inhibited.
Since different molecules have different reaction mechanisms, temperature effects are not the
same for all compounds. Therefore, it is fundamental that:

73
• the detector temperature remain constant.
• the detector temperature be always indicated particularly when sensitivity data is being
acquired (minimum detectable level) or the response of different compounds is being
compared.

The variation of response can reach three order of magnitude with a temperature difference of
250°C.
By optimizing the operating temperature response selectivity can be increased: by varying the
temperature the response of the particularly interesting compounds can be increased whereas the
response of the remaining compounds is decreased.

Compound Minimum detectable level (ppb)

80°C 227°C 350°C

CCl4 0.01 0.01 0.01

CHCl3 1.0 0.10 0.05

CH2Cl2 1000.0 40.0 8.0

CH2ClCH2Cl 1000.0 20.0 1.0

In any case the temperature of the detector must never fall below boiling point of the heaviest
compound of the sample under analysis and, when packed columns are in use, this is valid also of
the stationary phase.
It should, therefore, be sufficiently high so as to avoid condensation phenomena of heavy
substances inside the cell that could cause a significant reduction in sensitivity.

However, there is a temperature value which, when exceeded, may cause a high loss of
radioactivity: therefore, it is extremely important that the detector never exceed this limit.
It is for this reason that the ECD detector has a maximum temperature setting of 380°C.

Setting the temperature (“Temp” page)


The temperature of the detector can have a value between 40 and 380°C, with increment of 1°C.

· In order to set the detector temperature open the page “temp”, press ON to activate the
temperature control and use the numerical keypad to insert the value in the corresponding box
(fig. 75).

Indication temperature (“status” page)


· In order to see detector temperature open the “status” page. The number on the right indicates
the set oven temperature and on the left the actual oven temperature reading as measured by the
temperature probe (fig. 74).

74
fig. 75 - ECD temperature

Current
· In order to set the detector current open the page “current”, press ON to activate the current
control and use the numerical keypad to insert the value in the corresponding box (fig. 76).

The current value can range between 0 and 10 nA, with increment of 0.001 nA

fig. 76 - ECD Current

Signal
In order to set all the operative parameters for signal control, open the page “Signal” (fig. 77).

75
Digital acquisition rate
As a general rule, at least 10-20 data for peak must be acquired to correctly define a peak.
This means that the acquisition rate must be select so that the product of Acquisition rate
(sampling/sec) and the peak width in seconds is between 10-20.

fig. 77 - ECD Signal

Besides, the response time provided by the electrometer must be adequate to detect fast peaks.
MasterGC provides two levels of response time: one for fast peaks (Min.Half-Peak Width < 0.6 sec)
and one for conventional peaks (Min.Half-Peak Width > 0.6sec). According to the Min. Half-Peak
Width setpoint (< 0.6 sec or > 0.6 sec), the response time will be automatically adjusted.

Digital acquisition rate (expressed in Hz) can assume the following values: 2.5, 10, 25, 50, 100,
250, 300.
According to the Min.Half-Peak Width set, the optimal acquistion rate is automatically suggested
(fig. 77). You can still select a different one through the drop down menu.

Signal zeroing
To zero the outgoing signal from the electrometer open the page “Signal”.
Insert in the box “Signal target” the signal level required and press “Apply”. The level will adjust to
meet the level required.

In the page “Status” you can visualize the signal and the back off (fig. 76))

The back off value, expressed in mV, represents the quantity added algebrically to the signal to
bring the signal level to the value set in the “Signal target” edit box.

Graphic
In the page “Graph” (fig. 78) the plot of the signal will be visualized. Use the buttons “+” and “-” to
change the time scale (expressed in minutes) and the Voltage scale (expressed in mV).

76
fig. 78 - Graphic

Cleaning and conditioning the system


The electron capture detector is highly sensitive, therefore, the presence of impurities in the
system, contrary to other types of detectors, can cause problems.
In addition to the aforementioned pureness of the gas, all the other components of the detector
system require an elevated degree of cleanliness.
In particular, the introduction septa are a source of contamination which cannot be overlooked.

For this reason, it is important to follow the suggestions herebelow:

• use septa that are specifically for use with high sensitivity detectors and that are perfectly
washed and conditioned.
• keep the septa in a scrupulously clean and closed container.
• avoid direct handling of the septa during assembly by using a clean pair of pliers.

The analytic column must also be perfectly conditioned.


It is unadvisable to use columns that have stationary phases with poor stability or that contain a
high quantity of electro affined molecules, especially if the columns are of the packed type.

When turned on, the electron capture detector requires a relatively prolonged space of time (12-24
hours) in which to reach maximum efficiency level even when the columns are conditioned and the
pneumatic system perfectly clean. Conditioning is carried out with the detector at operating
temperature and with the presence of auxiliary gas.
A self cleaning operation is carried out inside the ionizing cell, during this time: environmental
Oxygen and humidity, as well as any condensed substances inside the cell which, by taking up
electrons, reduce the efficiency of the detector, are eliminated through the combined effect of the
temperature and the passage of gas.

The practical effect of conditioning is that of a progressive reduction of the signal exiting from the
detector and, therefore, a progressive lowering of the base line, which indicates a minor presence
of electrocapturing contaminants inside the ionization cell.

77
In usual conditions, the base line is stable and the signal establishes itself on a minimum value: this
value corresponds to the minimum voltage impulse frequency required to maintain the set current
value when the system is clean and when pure gas is present.

Switching on the detector


To turn on the detector, the procedure is as follows:

• The detector conditioning requires a relatively long period of time (12-24 hours).
It is advisable to carry out this procedure from the night before the period of use.
• Start up the flow of auxiliary gas and set at least 15-20 ml/min flow rate value.
• Set the required operating temperature.
• After 12-24 hours, regulate the auxiliary gas (N2 or Argon-Methane) at 30-40 ml/min
flow rate.
If the carrier gas is Nitrogen (or Argon-Methane), regulate the auxiliary gas flow to
obtain a total flow rate of 30-40 ml/min.
• Checking the signal, set increasing current values until the signal rises rapidly.
Allow a few seconds to elapse after each setting before checking the signal or base line
since the setting does not go into effect immediately. The rising signal indicates that the
detector is functional. Wait until the signal settles on a constant value.
The signal will usually settle on a value of about 10 mV .
Sometimes the value will be slightly higher. In this case, the current value can be lowered to
bring the signal to the indicated level.
Higher values indicate that the system is not sufficiently conditioned: detector sensitivity can be
nil or in any case highly reduced. If this happens, the conditioning operation should be
repeated with a higher auxiliary gas flow rate, if necessary.
• Once the detector is conditioned, regulate the auxiliary gas flowrate to the required
setpoint and turn on injector and oven heating.
At this point the signal might rise again: this is due to the elimination of residues from the
injector or the column.
When the column condition is completed, the signal will return to the initial level.
If packed columns are used, the signal will probably settle at a higher value that depends
on the oven temperature, the type of liquid phase in the column and the gas flow rate.
It is evident that the higher the level of the starting signal, the lower the sensitivity of the
detector.
In this case, it is advisable to use operating conditions that minimize this effect on the
column and give a lower signal level (e.g. by decreasing the column temperature).
If in any case, even using capillary columns, the level of the signal remains higher than
the initial one or if it does not settle quickly, this indicates that the system is not clean.
In this case, check the injector (if necessary, change the pre-column) and/or thoroughly
condition the column, disconnecting it at the detector end.

When the conditioning procedure is carried out, the detector is ready for use.
If higher sensitivity is needed, set a higher current value but consider that, by doing so, the base
line noise also increases.
Usually, at maximum sensitivity conditions, the base line noise must not exceed 1% of the full
scale.

78
Detectors

Thermal Conductivity Detector TCD 86/40

Introduction
The thermal conductivity detector is based on the principle that a warm body undergoes a
temperature variation according to the thermal conductivity of the gas which surrounds it. The
temperature variation can be recorded and related to the gas concentration.
In the thermal conductivity detector, four metal filaments, inserted into the internal cavity of a heated
unit, are fed by constant current and, therefore, heated to a certain temperature. The filaments are
made of a metal which has an electrical resistance that varies significantly in relation to temperature
variations.
They are connected amongst themselves, in pairs, according to the Wheatstone bridge circuit (fig. 79).

The gas exiting from the analytical column (analytical channel) flows through one pair of filaments,

fig. 79 - Wheatstone bridge circuit

whereas, pure carrier gas (reference channel) flows through the other pair.
When pure carrier gas flows through both channels, the two pairs of filaments S1, S2, R1 and R2 are at
the same temperature and have the same resistance value; the circuit is balanced and the signal exiting
from the detector is equal to zero.
When the component elutes from the analytical column, the thermal conductivity of the mixture of
carrier gas and component varies causing a corresponding change in the gas temperature.
The results is a variation in the electrical resistance of the filaments of the analytical channel while the gas
and electrical properties in the reference channel remain constant.
Consequently, an unbalance in the Wheatstone bridge occurs which produces an output signal from the
detector: this signal is recorded as a chromatogram.
The thermal conductivity detector is a non-destructive detector and, therefore, can be connected in
series with other detectors.

80
Description
The Thermal Conductivity Detector 86/40 is composed of the following principal parts:

• the main body and heating unit


• the external cover
• the control unit

The main body and heating unit


The main body (fig. 80) consists of a stainless steel block (1) inside of which there are four cells
(2).
Each cell contains a filament in tungsten-rhenium (3), inserted by means of a seal system.
Each filament is connected to two wires (4). All the four filament wires are assembled in a single
cable which connect them to the control unit.
The filaments are connected amongst themselves according to a Wheatstone bridge circuit:
therefore, an analytical channel and a reference channel can be defined.

Each channel is connected at each end to a stainless steel tube with a diameter of 1.6 x 0.8 mm:
the inlet end (5) is connected to the column terminal, the opposite end is in direct contact with the
atmosphere (6).

The heating unit is located at the base of the main body (7).

fig. 80 - TCD 86/40 main body

It contains an electric resistance (8) and a temperature probe (9) both of which are connected to
the gaschromatograph main board by a connector.

The external cover


The main body of the detector and the heating unit (fig. 81) are enclosed in a metal cover (1) lined
with insulating material which protects them from the external environment in order to maintain a
constant temperature.
The heating unit and main body are assembles on a metallic support (2): it has four lateral holes
(3) for securing the detector to the gas chromatograph.

81
The support has two 1/4G threaded ends (4) on which the packed columns can be directly installed
by using 1/4G fitting (5) and the brass ferrules (6).

fig. 81- TCD 86/40 external cover

To operate with wide-bore capillary columns, it is necessary to install an adapter (7) with a lateral
input for the auxiliary gas (8) and a 4M threaded end (9).

Two cables exit from the external cover: the upper cable (10) connects the filaments to the control
unit, the lower one (11) connects the electrical resistance and the temperature probe to the power
supply board of the gaschromatograph.

The control unit


The control unit (fig. 82) power operates the detector.
It consists of an electrometer (1) and the control board of the Wheatstone bridge circuit (2).
On the left side of the main board there is a connector (3) to link the control unit to the main board
of the gas chromatograph.
The wires coming from the detector head are connected to the terminal block (4).

fig. 82 - TCD 86/40 control unit

82
Response
The response given by the thermal conductivity detector is expressed by the following equation:

K I 2
R (l g -l f )
R = f
. . (T f -T b )
F l g

where

K = constant based on the geometry of the cell


I = current of the filaments
Rf = resistance of the filaments
lg = thermal conductivity of the pure carrier gas at temperature Tb
lf = thermal conductivity of the sample
Tf = temperature of the filaments
Tb= temperature of the detector block
F = flow rate of the carrier gas

The factors which influence the detector response are analyzed here below.

Filament current
The term I2 in the above equation indicates that by increasing the value of the current in the
filaments, the response of the detector increases significantly. Moreover, an increase in the
current also corresponds to an increase in the temperature Tf and the resistance R of the
filaments.

The result is that by redoubling the value of the current, a response which is from four to
eight times higher can be obtained.
The entity of the temperature increase of the filaments, and consequently of the response,
depends on the type of carrier gas and the temperature Tb of the detector block.

Therefore, a maximum current value must be respected in relation to the type of carrier gas
used and the detector temperature, otherwise there exists the risk of the overheating and
irremediable deterioration of the filaments.
It is advisable to operate using current values which are slightly lower than the maximum
given values (approx. 80%) in order to ensure higher stability of the base line and guarantee
a prolonged working life of the filaments.

The following table illustrates the maximum recommended current values according to the detector
temperature and the most commonly used carrier gases.

Detector temperature (°C) Carrier gas

He or H2 (mA) N2 or Ar (mA)

Ambient - 100 250 - 270 100 -120

100 - 150 220 - 250 90 - 110

150 - 200 200 - 220 80 - 100

83
Detector temperature (°C) Carrier gas

200 - 250 180 - 200 70 - 90

250 - 300 160 - 180 60 - 80

300 - 400 140 - 160 50 - 70

The current value in the circuit depends on the voltage value which feeds the filaments: it is, in
fact, the power supply voltage which is regulated in order to obtain the required current value.

Carrier and auxiliary gas


The detector response depends on the difference in the thermal conductivity of the pure carrier
gas and the gas containing the component to be detected: the higher the difference, the higher the
response will be for that component.
Thermal conductivity values of several gases are reported in the table below

Gas l (0°C) l (100°C)

Hydrogen 39.60 49.93

Helium 33.80 39.85

Methane 7.20 10.41

Oxygen 5.7 7.43

Nitrogen 5.66 7.18

Argon 3.88 5.09

Carbon Dioxide 3.38 5.06

Helium is the most recommended carrier gas since it has an elevated thermal conductivity value as
well as having the characteristics of chemical inertness and safety in use.
On the contrary, Helium is not the ideal gas for detecting Hydrogen in that the conductivity
difference between the two gases is minimum.
In this case the use of Nitrogen or Argon as carrier gas is more recommendable.
The use of Nitrogen will decrease the response factor in the case of Oxygen and Carbon Dioxide.

It is, therefore, evident that the choice of carrier gas must take into consideration various factors:
the components to be detected and their concentrations, the type of column, the safety conditions,
the purity of the gas available, costs, etc..
Since the detector response is influenced by the type of gas, it is advisable that the carrier and
auxiliary gas be the same.

84
Carrier and auxiliary gas flow rate
The TCD response is function of the concentration and therefore it is inversely proportional to the
total flow rate, that is the sum of carrier and auxiliary gas flow rates: the lower the flow rate, the
higher the response.
It is advisable that the sum of carrier and auxiliary gas flow rates be at least 20-25 ml/min.

Moreover, since the response is influenced by the flow rate it is indispensable that the total flow rate in
both the analytical and reference channels, be constant.
When operating in isothermal conditions, it is not strictly necessary that the flow rates be the same
but they must be constant.
It is, therefore, possible to install a different column or simply a restriction on the reference
channel.
Whereas, in the case of programmed temperature analyses the flow rates must necessarily be
identical because the variation of the flow rate with the temperature must also be identical: it is,
subsequently, indispensable that the columns on both channels be the same.

Temperature
The detector response is directly proportional to the factor (Tf-Tb), that is to the difference of the
temperature of the filaments and the temperature of the detector.
This means that the detector temperature must be set at a minimum value that is sufficient to
maintain the components in a gaseous phase, that is a value slightly higher than the boiling point
of the heaviest gas.
In case of isothermal analyses, the temperature should be equal to, or slightly higher than the
oven temperature; whereas, in the case of programmed temperature analyses, the detector
temperature should be equal or slightly higher than the temperature of the final isotherm.

To conclude, the TCD response can be increased by applying the following methods:

• by increasing the power supply voltage to the filaments


• by decreasing the temperature of the detector
• by optimizing the carrier gas
• by decreasing the gas flow rate to the detector.

Temperature
Setting the temperature (“Temp” page)
The temperature of the detector can have a value between 40 and 450°C, with increment of 1°C.

· In order to set the detector temperature open the page “Temp”, press ON to activate the
temperature control and use the numerical keypad to insert the value in the corresponding box
(fig. 83).

Indication temperature (“Status” page)


· In order to see detector temperature open the “Status” page. The number on the right indicates
the oven temperature setpoint and on the left the actual oven temperature reading as measured
by the temperature probe (fig.84).

85
fig. 83 - TCD temperature fig. 84 - TCD Status

Filaments
In order to control the filaments, open the page “Filaments” (fig. 85) and press ON.

The following parameters will be available:

• Voltage: it represents the power supply voltage on the filaments. This value, expressed in
V, can range between 0 and 20 V , with increment of 0.01 V.
If the pressure on Inj X or Aux X is too low, or an Injector used as safety haven’t been
configured, an alarm “FILAMENT SAFETY” will appear (ref. to table “Red Hand Alarm ” in
the chapter “Diagnostics”
• Polarity: it allows to set the polarity of the signal in order to have a positive signal.

fig. 85 - TCD filaments

• Max Current: this parameter, expressed in mA, represents the maximum current value in
relation to the type of carrier gas and the temperature of the detector. This value can
range between 0 and 300 mA, with increment of 1 mA.
When the Current is over the Max Current parameter, the alarm “TCD Voltage Reduced”

86
will be displayed, and the voltage will be reduced (ref. to table “Red Hand Alarm ” in the
chapter “Diagnostics”
• Filament Safety: through the two drops down you can selected the injector or the gas
auxiliary used as Filament safety.

Signal
In order to set all the operative parameters for signal control, open the page “Signal” (fig. 86).

Selecting the RANGE level


The amplitude of the detector dynamic range can be varied to suit the analytic needs by selecting
the RANGE function.
It means that, at different range, the same value of current measured by the detector produces a
different output signal.

fig. 86 - TCD Signal

Two range levels (1, 10) are available: at the higher level, the dynamic range of the signal
produced by the detector is increased by a 10 factor compared with the previous level.
This results in a output signal 10 times lower for the same current value.
Set the RANGE function to 1 to get the minimum full scale range, that is the maximum sensitivity.

Selection of the RANGE level depends on the analytic conditions: they must be such, as to
guarantee that all peaks of interest are within the detector dynamic range, which means that the
corresponding signal does not exceed the scale maximum and that at the same time they are not
too small to be correctly measured.

· Select the range levels through the drop-down menu.

Digital acquisition rate


As a general rule, at least 10-20 data for peak must be acquired to correctly define a peak.
This means that the acquisition rate must be select so that the product of Acquisition rate
(sampling/sec) and the peak width in seconds is between 10-20.

87
Digital acquisition rate (expressed in Hz) can assume the following values: 2.5, 10, 25, 50, 100,
250, 300.
According to the Min.Half-Peak Width set, the optimal acquistion rate is automatically suggested
(fig. 86). You can still select a different one through the drop down menu.

Signal zeroing
To zero the output signal from the electrometer open the page “Signal”.
Into the box “Signal target”, insert the signal level required and press “Apply”. The signal will
adjust to meet the level required. In the page “Status” you can visualize the signal and the back off
(fig. 84).

The back off value, expressed in mV, represents the quantity added algebrically to the signal to
bring it to the value set in the “Signal target” edit box.

Graphic
In the page “Graph” (fig. 87) the plot of the signal will be visualized. Use the buttons “+” and “-” to
change the value in time scale (expressed in minutes) and the Voltage scale(expressed in mV).

fig. 87 - TCD Graphic

Switching on
In order to switch on the thermal conductivity detector the procedure is as follows:

• Prior to any operation the gas must flow into both channels.
See “Introduction Systems” values to set the required flow rate in the two channels.
• Set the oven temperature and the detector temperature. (See “Oven temperature” in the
chapter“Oven” and “Temperature” in this chapter)
Wait until the temperatures are constant, check that the base line is stable.
• In the parameter MAX CURRENT ,set the maximum current value in relation to the type of
carrier gas and the temperature of the detector (ref. to table in “Current” paragraph and
“Filaments” paragraph of this chapter).

88
• In the parameter VOLTAGE, set the value of power supply voltage on the filaments (
See"Filaments“ paragraph of this chapter).

Since each variation in voltage corresponds to a variation of the current and consequently a
variation in the temperature of the filaments, each time this parameter is modified, a pause is
necessary (30-60 mins) to allow the filaments to stabilize to the new conditions: in stable
conditions the base line must be constant.

Warning

Each time the flow of gas to the detector is suspended, for example when replacing a column, an
introduction septum or on any occasion when the detector comes into contact with environmental
air, power supply to the filaments should be stopped. The presence of air can cause irremediable
oxidation and deterioration of the filaments.

• Check the detector functioning by reading under the parameter CURRENT in the page
“Status”, the value of the current in the circuit.
• Using the function POLARITY set the polarity of the signal in order to have a positive
signal: this setting depends on which of the two channels will be used as analytical and
which as reference channel. (See"Filaments“ paragraph of this chapter

With reference to the above, it is important to observe that if a component, whose thermal
conductivity value is higher than the carrier gas, elutes from the column, the chromatogram will
show a negative peak (for example: Hydrogen with Nitrogen as a carrier gas).

89
Detectors

Nitrogen-Phosphorous Detector NPD 86/20

Introduction
The Nitrogen-Phosphorus detector (fig. 88) is a highly specific and selective detector for the
determination of traces of organic compounds Nitrogen and Phosphorus atoms in presence of
other organic compounds.
It consists of a collector and a jet similar to those of the flame ionization detector; the ion source,
instead, consists of a quartz bead containing a Rubidium salt, supported on a platinum wire and
positioned just over the jet.
During operation, negative ions are produced from catalytic interaction between the alkaline metal
and the compounds containing Nitrogen and Phosphorus.

fig. 88 - Nitrogen- Phosphorus Detector

The mechanism of this reaction is not completely known: the system is very complex and different
phenomena seem to be involved.
The gaseous environment inside the detector consists of a dilute mixture of Hydrogen in Air.
This mixtures is not able to maintain a ionizing flame and so the ionization of hydrocarbons is
negligible.
When the bead is fed with a negative voltage, the Rubidium salt contained generates ions; the
thermal energy produced by this heating forms a very reactive environment in the gaseous layer
surrounding the bead.

When substances containing Nitrogen or Phosphorus reach the reactive zone, they are
decomposed and ionized.
The negative ions formed by this reaction are gathered by a collector and the resulting current is
measured by the electrometer.

Description
The NPD 86/20 detector can be used with both capillary and packed columns.
It is composed of three main parts:

90
• the base body
• the detector head
• the control unit

The base body


The base body (fig. 89) is composed of a stainless steel cylinder (1) welded to a support (2) and
secured to the gas chromatograph by two screws (3).
The unit is inserted into an aluminium block (4) containing the heating resistor (5) and the
temperature probe (6).

fig, 89 - NPD 86/20 base body

Two gas lines are installed on the side of the base body:

• the inferior line (7) for the inlet of Hydrogen and auxiliary gases

• the upper line (8) for the inflow of air.

A nozzle (9), which is electrically grounded, is screwed inside the base body.
In the upper part, the knurled brass ring (10) secures the head to the base body.

The end section of the body, inside the chromatographic oven, has a 1/4G thread (11).
Packed columns can be connected directly to this section with a 1/4G nut (12) and brassThe
detector head.

The detector head


The detector head (fig. 90) is composed of :

• the electrode collector (1), coaxial to the nozzle


• the thermoionic source (2) supported on a platinum wire and fixed to the body by a screw
(3)
• the aluminium flange (4) which closes the inspection holes (5)
• the upper threaded lid (4) and the insulating mantle (7)

91
The head is secured to the base body by a brass ring assembled on the base body.
An O-ring seal (8) inserted on the lower part of the head provides an adequate seal between the
head and the body.
The signal cable is connected to the connector (9) whereas the bead power supply cable is
connected to the connector (10).

fig. 90 - NPD 86/20 head

The control unit


The control unit (fig. 91) provides electronic control of both the signal coming from the detector
head and the power supply.
The control unit includes an electrometer (1), the detector control board (2) and the bead power
supply board (3).

On the left side of the main board there is a connector (4) for linking the control unit to the main
board of the gas chromatograph.

The signal cable (5) exits from the electrometer and the bead power supply cable (6) from the
bead power supply board.

fig. 91 - NPD 86/20 contro unit

92
Sensitivity and selectivity
The NPD detector response towards molecules containing Nitrogen or Phosphorus is different for
different compounds and is difficult to predict.
Some compounds do not give any response to the NPD even if they have Nitrogen or Phosphorus
atoms (e.g. Nitro-glycerine) as it seems necessary a C-N bond to obtain a response.
The inorganic Nitrogen (e.g. N2 and NH3) is not determined as well.

The sensitivity and selectivity of the NPD are strongly affected by the flow rates of the gases and
the temperature of the thermionic source.

Effect of gas flow rates


A minimum change in the Hydrogen flow rate has a significant effect: in fact, the Hydrogen flow
rate affects the quantity of atoms of H in the reactive layer around the bead and in consequence
the detector response.
As the Hydrogen flow rate increases, the signal level and the response increase.
It is better to notice that when the response increases, even the baseline noise increases so that an
actual gain in sensitivity is not always obtained.
A very high flow rate has a negative effect as well as, as it can cause the flame ignition.
This condition brings to a loss in selectivity as the flame detects the presence of Hydrocarbons.
Furthermore, the flame damages the bead and reduces dramatically its working life.

The signal level and the response decrease by increasing the auxiliary gas flow rate.
However, the selectivity to the carbon compounds increases.

In any case, it is useful to observed that the sensitivity and the selectivity are inversely affected by
the gas flow rates so that these must be regulated differently in order to optimize one or the other
aspect.

Voltage to the bead


The voltage supplied to the bead causes its heating.
The ionization mechanism is activated by a threshold value.
By increasing the voltage over this value, the signal level and the response increase: even in this
case, when the signal increases the baseline noise rises too.
Therefore, it is better to evaluate at each condition the actual gain in sensitivity calculated as
signal/noise ratio.
Furthermore, as previously noticed, as the sensitivity increases, the selectivity decreases.

A progressive decrease in the sensitivity of the detector is normal and it is due to the gradual
consumption of the source.
The life expectancy of the bead is not predictable as it depends on the operative conditions: the
higher the power voltage and the Hydrogen quantity, the lower the duration of the bead.

Large quantity of chlorinated solvents and silanizing reagents damage the bead and reduce its
lifetime: therefore, it is advisable to eliminate as far as possible most of the solvent before the
injection.

The NPD detector is very sensitive to the presence of traces of contaminants which comes for
example from washing solutions of glassware or solvents.

93
Some stationary phases containing Nitrogen or Phosphorus (e.g. OV-225, OV-275, FFAP), columns
or glass wool washed with Phosphoric acid are not suggested as they can disturb the system.

Negative peaks can appear and they are caused by a rapid cooling of the bead (mostly due to the
solvent): normally, this problem is eliminated by increasing the bead voltage or the air flow rate.

Temperature
The temperature of the detector must be high enough to avoid condensation phenomena of the
substances in the sample.
Besides, the head temperature must be absolutely constant as it affects the bead temperature and
in consequence the sensitivity of the detector.
The insulating mantle helps to maintain the detector temperature constant.

Setting the temperature (“Temp” page)


The temperature of the detector can have a value between 40 and 450°C, with increment of 1°C.

· In order to set the detector temperature open the page “Temp”, press ON to activate the
temperature control and use the numerical keypad to insert the value in the corresponding box.
(fig. 92).

fig. 92 - NPD Temperature

Indication temperature (“Status” page)


· In order to see detector temperature open the “status” page. The number on the right indicates
the set oven temperature and on the left the actual oven temperature reading as measured by the
temperature probe (fig. 93).

94
fig. 93 - NPD Status

Regulating the gas flow rates


Setting the flow rates (“Flows” page)
· By opening the page “Flows” (fig. 94), you can set all gas control parameters needed for the
functioning of the detectors.

Press ON to activate the control flows and, through the drop-down menu, select the auxiliary gas
type (Nitrogen or Helium).

By using the numerical key pad insert the gas flows rate values expressed in ml/min.
Aux and Hydrogen can have a value between 0 and 100 ml/min, with increment of 1 ml/min. The
Air setpoint can range between 0 and 1000 ml/min, with increment of 1 ml/min.

fig. 94 - NPD Flows

95
Warning

Before regulating the Hydrogen flow rate, check that the detector is connected to a column or
protected by a closure in order to avoid the liberal escape of gas inside the gas chromatograph
oven: this can cause an explosion.

Visualizing gas flows (“Status” page)


In order to read the gas flow regulation open the “status” page. The number on the right indicates
the set value and on the left the actual value (fig. 93).

Bead
In order to set the value of the power voltage of the bead, open the page “Bead” (fig. 95).
Press ON and using the numerical keypad insert the value in the “Bead Voltage” edit box.
This parameter is expressed in V and can range between 0 and 1 V, with increment of 0.001 V.

fig. 95 - NPD Bead

Detector functioning
• Set the detector temperature and wait till it reaches the required value (see
“Temperature” in this chapter)
• Set the carrier gas flow rate to the value required for carrying out the analysis (see the
chapter “Introduction systems”.
• Set the Hydrogen (about 4 ml/min), Air (about 100 ml/min) and auxiliary gas flow rates
(see “Regulating the gas flows rates” in this chapter)
• Select the Bead Voltage (see “Bead” in this chapter)
• Check the baseline at the “Status” page, on the acquisition system or on the page
“Graph” and set a progressive value of current until the signal level will rapidly reach a
positive value.
Wait some seconds between each set as the effect of the current on the signal is slightly
late.
Wait until the signal stabilizes. These are the minimum operating conditions. The bead is

96
incandescent and red.
Usually, a good bead starts working with a voltage between 0.550 and 0.700 V.
• Set a voltage value in order to obtain an output signal of about 10 mV.

Signal
In order to set all the operative parameters for signal control, open the page “Signal” (fig. 96).

Selecting the RANGE level


The amplitude of the detector dynamic range can be varied to suit the analytic needs by selecting
the RANGE function.
It means that, at different range, the same value of current measured by the detector produces a
different output signal.

Three range levels (1, 10, 100) are available: for each higher level, the dynamic range of the signal
produced by the detector is increased by a 10 factor compared with the previous level.
This results in a output signal 10 times lower for the same current value.
Set the RANGE function to 1 to get the minimum full scale range, that is the maximum sensitivity.

Selection of the RANGE level depends on the analytic conditions: select the proper range level to
guarantee that all peaks of interest are within the detector dynamic range, which means that the
corresponding signal does not exceed the scale maximum and that at the same time they are not
too small to be correctly measured.

· Select the range levels through the drop-down menu (fig. 96).

fig. 96 - NPD Range

Digital acquisition rate


As a general rule, at least 10-20 data for peak must be acquired to correctly define a peak.
This means that the acquisition rate must be select so that the product of Acquisition rate
(sampling/sec) and the peak width in seconds is between 10-20.

97
Besides, the response time provided by the electrometer must be adequate to detect fast peaks.
MasterGC provides two levels of response time: one for fast peaks (Min.Half-Peak Width < 0.6 sec)
and one for conventional peaks (Min.Half-Peak Width > 0.6sec). According to the Min. Half-Peak
Width setpoint (< 0.6 sec or > 0.6 sec), the response time will be automatically adjusted.

Digital acquisition rate (expressed in Hz) can assume the following values: 2.5, 10, 25, 50, 100,
250, 300.
According to the Min.Half-Peak Width set, the optimal acquistion rate is automatically suggested
(fig. 96). You can still select a different one through the drop down menu.

Graphic
In the page “Graph” (fig. 97) the plot of the signal will be visualized. Use the buttons “+” and “-”
to change the time scale (expressed in minutes) and the Voltage scale (expressed in mV).

fig. 97 - NPD Graph

98
Detectors

Flame Photometric Detector FPD 86/72

Introduction
The flame photometric detector (fig. 98) provides the selective determination of compounds
containing Sulphur and Phosphorus atoms.
The detector functions on the principle that compounds containing such eteroatoms produce
chemiluminescent species when burned in a Hydrogen enriched flame.

These molecules are produced in a metastable state and when they decay, they emit light of a
specific wavelength.
A photo multiplier measures and amplifies the light emitted.
Sulphur compounds are detected as the S=S molecules that emit light at 394 nm and phosphorous
compounds as the HPO molecules that emit light at 526 nm.

fig. 98 - FPD detector

An optical filter is installed between the flame and the photo multiplier to assure a high selectivity:
the filter has a band at 394 nm for sulphur compounds and at 526 nm for phosphorous
compounds.

When the light enters the photo multiplier, the electronics produce an output signal that is
amplified and can be send to the acquisition system.

Description
The FPD 86/72 detector can be used with both capillary and packed columns.
It is composed of three main parts:

• the base body


• the detector head
• the control unit

100
The base body
The base body (fig. 99) is composed of a stainless steel cylinder (1) welded to a support (2) and
secured to the gas chromatograph by two screws(3).
The unit is inserted into an aluminium block (4) containing the heating resistor (5) and the
temperature probe (6).
Two gas lines are installed on the side of the base body:

• the inferior line (7) for the inflow of Hydrogen and auxiliary gases
• the upper line (8) for the inflow of air.

fig. 99 - FPD 86/72 base body

A nozzle (9) is screwed inside the base body. In the upper part, the knurled brass ring (10) secures
the head to the base body.

The end section of the body, inside the chromatographic oven, has a 1/4G thread (11).
Packed columns can be connected directly to this section with a 1/4G nut (12) and brass ferrules
(13).
If capillary or wide bore capillary columns are used, an adapter (14) to reduce the internal volume
of the base body should be installed: the end section of the adapter has a 4M thread.

The detector head


The detector head (fig. 100) is composed of:

• the combustion chamber (1) containing the upper nozzle coaxial to the nozzle of the base
body, a quartz cylinder blocked by a seal and a coated flange
• the chimney (2)
• the resistor for igniting the flame (3) and its connector
• the inlet for the Air 2 gas line (4)
• the photo multiplier (5)

A cable (6) for the feeding of the auxiliary heating exits from the detector head.
The photo multiplier is secured to the head by two screws (7) that is necessary to unscrew to
approach the filter (8).

101
fig. 100 - FPD 86/72 head

Besides, a thermal filter is installed between the head and the photo multiplier.
The plugs to connect the signal cable (9) and the PMT power supply cable (10) coming from the
control unit, are at the end of the photo multiplier.

The head is secured to the base body by a brass ring assembled on the base body.
An O-ring seal (11) inserted on the lower part of the head provides an adequate seal between the
head and base body.

The control unit


The control unit (fig. 101) provides electronic control of the signal coming from the detector head
and the power supply of the flame resistor and of the photo multiplier.

fig. 101 - FPD 86/72 control unit

The control unit includes an electrometer (1), the detector control board (2) and the boards that
controls the power supply to the flame resistor (3) and to the photo multiplier (4).

102
On the left side of the main board there is a connector (5) to link the control unit to the main board
of the gas chromatograph.

The signal cable (6) exits from the electrometer, the power supply cable for igniting the flame (7)
and the power supply cable for the photo multiplier(8) from the corresponding boards .

Gas flow rates


Sensitivity and selectivity are strongly affected by flame conditions that is by gas flow rates to the
detector. Particularly, the ratio Air/Hydrogen is crucial.
Furthermore, the optimal conditions are different if the Sulphur or the Phosphorus must be
determined.
The Sulphur determination requires a more reducing flame than Phosphorus that is a lower
Air/Hydrogen ratio: the optimal ratio is 0.6 for Sulphur and 0.8 for Phosphorus.

At a constant air flow rate, a Hydrogen flow rate increase increases the response up to a maximum
while the signal noise does not significantly increase; over this value the response decreases.
The selectivity towards hydrocarbons is lower with reduced Hydrogen flow rate.

Furthermore, the total flow rate of all the gases reaching the flame is important as it affects the
flame temperature.
The light intensity emitted by the chemiluminescent species, and the response as a consequence,
increases as the flame temperature decreases.
For this reason, it is advisable to use a gas with a high thermal conductivity as Helium or Hydrogen
as carrier and auxiliary gases instead of Nitrogen.
Using a 120 ml/min air flow rate at least, a total carrier and auxiliary gas flow rate of 20 ml/min is
enough to obtain a good response.

Setting the flow rates (“Flows” page)


· By opening the page “Flows” (fig. 102) you can set all gas control parameters needed for the
functioning of the detectors.

Press ON to activate the control flows and, through the drop-down menu, select the auxiliary gas
(Nitrogen or Helium).

fig. 102 - FPD Flows

103
By using the numerical key pad insert the gas flows rate values expressed in ml/min.
Aux and Air can have a value between 0 and 100 ml/min, with increment of 1 ml/min. The setpoint
of air 2 and Hydrogen can range between 0 and 500 ml/min, with increment of 1 ml/min.

Warning

Before regulating the Hydrogen flow rate, check that the detector is connected to a column or
protected by a closure in order to avoid the liberal escape of gas inside the gas chromatograph
oven: this can cause an explosion.

Visualizing gas flows (“Status” page)


In order to read the gas flow regulation open the “Status” page. The number on the right indicates
the set value and on the left the actual value (fig.103).

fig. 103 - FPD Satus

The photomultiplier PMP


The detector response is strongly affected by the voltage which feeds the photo multiplier.
By increasing the voltage value, the response increases but at the same time the baseline noise
increases too.
The maximum sensitivity, expressed as signal/noise ratio, has been obtained with about 0.600 kV
for Phosphorus and about 0.650 kV for Sulphur determination.

· In order to set the voltage to the photo multiplier open the page “PMP” (fig. 104), press ON to
activate the PMP control and use the numerical keypad to insert the value in the corresponding edit
box.

The Voltage is expressed in kV can have values between 0.500 and 0.900 kV, with increment of
0.001 kV.

104
fig. 104 - FPD Photomultiplier

Temperature
The detector temperature affects its response as it affects the flame temperature.
Furthermore, as the flame is near to the photo multiplier, when the temperature increases the
baseline noise increases too.
Therefore, it is advisable to set the temperature high enough to avoid the condensation
phenomena keeping in mind that the response decreases with higher temperature.

Setting the temperature (“Temp” page)


The temperature of the base body can have a value between 40 and 450°C, with increment of
1°C.

· In order to set the base body temperature open the page “Temp”, press ON to activate the
temperature control and use the numerical keypad to insert the value in the corresponding box
(fig. 105).

fig. 105 - FPD Temperature

105
To set the detector head temperature press “Menu”, select “Aux”, then open the page
“Temperatures” (fig. 106).

Insert the value in the corresponding edit box (see “Auxiliary temps and gases”).

fig. 106 - FPD Aux temperature

Indication temperature (“Status” page)


· In order to see detector temperature open the “Status” page. The number on the right indicates
the set oven temperature and on the left the actual oven temperature reading as measured by the
temperature probe (fig. 103).

Sulphur quenching
An undesired light absorption can occur in the flame when hydrocarbons and sulphur compounds
are analyzed in a mixture.
As a consequence, the response of Sulphur dramatically decreases.
This effect, called “quenching”, is due to the collisions that occur between sulphur species and CO2
molecules in the flame when a hydrocarbon at relatively high concentration coelutes with a sulphur
compound.
It is possible to reduce this negative effect by improving the chromatographic separation or by
using the detector in the double flame mode.
The quenching effect can occur even at high concentration of sulphur compounds (self
quenching).
This phenomenon does not occur with phosphorous compounds.

Response factor
Due to the reactions of sulphur in the flame, the response of the Sulphur is not linear with the
concentration but is proportional to the square of the concentration, that is the square root of the
response is linear with the concentration.
The square root of the response is linear for 3 orders of magnitude.
The response of the Phosphorus is linear to concentration for about 4 orders of magnitude.

106
Igniting the flame
• Set the temperatures of the base body and the head and wait till they reach the required
values. (See “Temperature” in this chapter
• Set the carrier gas flow rate to the value required for carrying out the analysis. (See the
chapter headed “Introduction systems”)
• Set the auxiliary gas flow rate in order to obtain a total flow rate (carrier gas + auxiliary
gas) of 20 ml/min at least.
• Set the Air 1 flow rate (4 ml/min)
• Set the Air 2 and the Hydrogen flow rate at different values depending on the compounds
to be analyzed (sulphur or phosphorous compounds).

Sulphur mode: Air 2 120 ml/min


Hydrogen 200 ml/min
Phosphorus mode: Air 2 160 ml/min
Hydrogen 210 ml/min

Warning

Before regulating the Hydrogen flow rate, check that the detector is connected to a column or
protected by a closure in order to avoid the liberal escape of gas inside the gas chromatograph
oven: this can cause an explosion.

• Before igniting the flame, unscrew the detector cap.


• Open the page “PMP” and press ON to control the photo multiplier (the voltage as default
is 0.5 kV)The flame will ignite. This process will cause a small explosion.
The power voltage feeds the flame resistor for about 10 seconds and successively feeds
the photo multiplier.
• Screw the detector cap immediately after igniting the flame to avoiding the room light
entering the photo multiplier.
• Set the voltage to the photo multiplier.(see “Voltage to the photo multiplier” in this
chapter)
Verify that the signal is positive in the page “Status”.
Ignition can be checked by putting a cold shiny object near the chimney: condensation
will be present.
• Wait until the detector conditions stabilize.
• To operate in the double flame mode (ref. to the paragraph “Quenching of Sulphur”)
proceed in the same way and set the flow rates reported here below:

Air 1 70 ml/min
Air 2 150 ml/min
Hydrogen 160 ml/min

• Optimize the flow rates according to the total gas flow (carrier gas + auxiliary gas).

107
Signal
In order to set all the operative parameters for signal control, open the page “Signal” (fig. 107).

fig. 107 - FPD Signal

Selecting the RANGE level


The amplitude of the detector dynamic range can be varied to suit the analytic needs by selecting
the RANGE function.
It means that, at different range, the same value of current measured by the detector produces a
different output signal.

Three range levels (1, 10, 100) are available: for each higher level, the dynamic range of the signal
produced by the detector is increased by a 10 factor compared with the previous level.
This results in a output signal 10 times lower for the same current value.
Set the RANGE function to 1 to get the minimum full scale range, that is the maximum sensitivity.

Selection of the RANGE level depends on the analytic conditions: select the proper range level to
guarantee that all peaks of interest are within the detector dynamic range, which means that the
corresponding signal does not exceed the scale maximum and that at the same time they are not
too small to be correctly measured.

· Select the range levels through the drop-down menu (fig. 107).

Digital acquisition rate


As a general rule, at least 10-20 data for peak must be acquired to correctly define a peak.
This means that the acquisition rate must be select so that the product of Acquisition rate
(sampling/sec) and the peak width in seconds is between 10-20.

Besides, the response time provided by the electrometer must be adequate to detect fast peaks.
MasterGC provides two levels of response time: one for fast peaks (Min.Half-Peak Width < 0.6 sec)
and one for conventional peaks (Min.Half-Peak Width > 0.6sec). According to the Min. Half-Peak
Width setpoint (< 0.6 sec or > 0.6 sec), the response time will be automatically adjusted.

108
Digital acquisition rate (expressed in Hz) can assume the following values: 2.5, 10, 25, 50, 100,
250, 300.
According to the Min.Half-Peak Width set, the optimal acquistion rate is automatically suggested
(fig. 107). You can still select a different one through the drop down menu.

Graphic
In the page “Graph” (fig. 108) the plot of the signal will be visualized. Use the buttons “+” and “-”
to change the time scale (expressed in minutes) and the Voltage scale (expressed in mV).

fig. 108 - FPD Graph

109
Detectors

Micro-Thermal Conductivity Detector mTCD

Introduction
The principal of operation of the micro-thermal conductivity detector (fig. 109) is based on the
relative change in the thermal conductivity of the gas passing across the detector filament as
components elute from the column. Heat is lost continuously by the filament through the carrier
gas to the cell wall of the detector. A chromatographic signal is produced by measuring the amount
of current required to maintain the temperature of the filament constant when a gas with a
different thermal conductivity cross the filament. This process is non-destructive of the sample and
is concentration- dependent.

fig. 109 - mTCD principle

The detector cell includes two separate filaments. Since changes in conductivity are measured only
by change in current required to keep the filament at a constant temperature, each of the two
filaments can be operated independently without referencing the changes to a match filament with
reference gas. This constant temperature provides longer filament life and safeguards it from the
extremely high temperature and oxidation which can occur with high concentrations of oxidative
or corrosive components.
The two filaments can operate in single or differential mode. The differential signal is provided to
minimize background variables such as column bleed and temperature programming.

Cell volume has been minimized to accommodate capillary column chromatography and optimize
the sensitivity of the detector at low flow rates. Carrier flow rates of 1-10 ml/min are recommended
for best sensitivity.

Each of the two filaments is controlled by a separate control unit which incorporated the
electrometer and the temperature control of the filament.

110
Description
The Micro Thermal Conductivity Detector is composed of the following principal parts:

• the detector cell and heater block


• two control units

The detector cell and heater block


The cell body and the heater block (fig. 110) are assembled into the detector housing and
protected by a housing cover. The housing is mounted on a metallic support secured to the
gaschromatograph by four lateral screws.
The detector housing contains an electric resistance and a temperature probe. Both of them are
connected to the gaschromatograph main board by a cable exiting on the right of the housing. A
cable on the left connects the filaments to the two control units.
The inlet lines installed into the detector are long enough to enter the column oven and permit
column connection. Each line is equipped with a fitting and a special adapter with a 4M threaded
end to directly connect the capillary column.
On the two side, the outlet lines of the two channels are available.

fig. 110 - mTCD - section view

The control units


The two control units are equivalent (fig. 111): they can operate independently to control the two
filaments in the single filament mode or can be linked through a dedicated cable (Part.No.
510.1509004) connected to the connector (1) to operate in the reference mode.

Each control unit consists of a main board (2) and a board for the filament and signal control (3) .
On the left side of the main board there is a connector (4) to link the control unit to the main board
of the gas chromatograph.

Each filament is connected to its control board by two of the four wires of the cable coming from
the detector head to the termonal block (5).

111
fig. 111 - mTCD control unit

Configuration
In the configuration of the mTCD, two definitions for a channel (filament + control unit), “ mTCD”
and “ mTCD ref”, are available.
To operate single filament mode, configure both channels as “mTCD”; to operate in differential
mode, configure one channel “mTCD” and the other one “mTCD ref.”.

· In order to gain access to detector configuration, press “Menu” and select “Set up”. To open the
page “Det” you have to insert the password. (See the paragraph “Lock/Unlock” in the chapter “Set
up”)

Differential mode
In the differential mode, one channel must be configured as “mTCD”, one as “mTCD ref.” and the
control units must be connected trough the proper cable.
The two channels are independent for all the functions except the temperature of the detector cell.
The sample should be injected in the channel named “mTCD”. In the differential operation, the

fig. 112- A-B differential mode fig. 113 - B-C differential mode

112
signal from the main channel is the actual signal produced by that channel while the signal from
the “mTCD ref.” channel is the difference (mTCD Signal - mTCDref. Signal).
It means that, to acquire the differential signal, the signal coming from the “mTCD ref.” control unit
must be connected to the acquisition system.

· Select the “mTCD” and the “mTCD ref.” in the position (A and B) or (B and C) . The filaments
belonging to the same detector cell will be showed joined through a blue line (fig. 112 and 113).

If you have two detector cells, the only configuration admitted is the following (fig. 114):

fig. 114 - Two det. configuration

Single filament mode


In the single filament mode, the two control units are not connected and the signals coming from
the two control units are independent.
While operating in the single filament mode, carrier flow must be maintained to the non selected
filament, but it is not necessary to connect a column nor to apply any filament temperature.
To operate on both filaments, even simultaneously, both channels must be configured as “mTCD”.

fig. 115 - A-B single mode fig. 116 - B-C single mode

113
· Select the two “mTCD” in the position (A and B) or (B and C) . The filaments belonging to the
same detector cell are joined through a grey line (fig. 115 and 116).

If you have two detector cells the only configuration admitted is the following (fig. 117):

fig. 117 - Two det. configuration

Carrier and auxiliary gas


The detector response depends on the difference between the thermal conductivity of the pure
carrier gas and the gas containing the component to be detected: the greater the difference, the
greater the response for that component.
The table below shows the thermal conductivity values of several gases.

Gas l (0°C) l (100°C)

Hydrogen 39.60 49.93

Helium 33.80 39.85

Methane 7.20 10.41

Oxygen 5.7 7.43

Nitrogen 5.66 7.18

Argon 3.88 5.09

Carbon Dioxide 3.38 5.06

Helium is the most recommended carrier gas since it has a high thermal conductivity value as well
as the characteristics of chemical inertness and safety in use. On the contrary, Helium is not the
ideal gas for detecting Hydrogen as the conductivity difference between the two gases is
minimum.

114
In this case the use of Nitrogen or Argon as carrier gas is more recommendable.
On the other hand, the use of Nitrogen will decrease the response factor in the case of Oxygen and
Carbon Dioxide. It is, therefore, evident that the choice of carrier gas must take into consideration
several factors: the components to be detected and their concentrations, the type of column, the
safety conditions, the purity of the gas available, costs, etc..Since detection of low concentration
depends in part on the purity of carrier gas, to achieve the lowest possible detection limit the
highest carrier purity available must be used.

Carrier gas flow rate


The TCD response depends on the concentration: the lower the flow rate through the detecto, the
higher the sensitivity .
The microTCD is designed for the low flow rates typical for capillary columns, and achieves best
sensitivity at rates below 10 ml/min. Since the filaments are maintained at constant temperature,
the detector can operate at extremely low flow rates (less than 0.5 ml/min) without damage to the
filaments.

Temperature
The detector response is directly proportional to the difference between the filament temperature
and detector temperature.
This means that the detector temperature must be set at a value slightly higher than the boiling
point of the highest boiling sample component and the filament temperature high enough to
achieve the desired sensitivity.

Setting the temperature (“Temp” page)


The temperature of the detector can have a value between 40 and 400°C, with increment of 1°C.

· In order to set the detector cell temperature open the page “Temp” (fig. 118) , press ON to
activate the temperature control and use the numerical keypad to insert the value in the
corresponding box.

fig. 118 - mTCD temperature

115
Warning
It is advisable to increase the filament temperature step by step, for example 50, 80, 100 and so on
allowing each time the filaments to stabilize to the new conditions.

Indication temperature (“Status” page)


· In order to see the detector temperature open the “Status” page. The number on the right
indicates thetemperature setpoint and that on the left the actual oven temperature as measured
by the temperature probe (fig. 119).

fig. 119 - mTCD Status

Filaments
Single filament mode
In order to control the filaments open the page “Filaments” (fig. 120) and press ON.

fig. 120 - Main Filament

116
In this way, the following parameters will be activated:

• Main Filament Temp: it represents the Main filament temperature. This value, expressed
in °C, can range between 40 and 400 °C , with increment of 1 °C.
If the pressure on Inj X is too low, or an Injector is selected as safety which is not
configured, an alarm “FILAMENT SAFETY MISSING” will appear (refer to Table “Red Hand
Alarm ” in the chapter headed “Diagnostics”
• Filament Safety: through the drop-down menu, select the injector used as Filament
safety.

Differential mode
In order to control the filaments open the page “Filaments” (fig. 121) and press ON.

fig. 121 - Main and Ref. Filaments

In this way, the following parameters will be activated:

• Main Filament Temp: it represents the Main filament temperature. This value, expressed
in °C, can range between 40 and 400 °C , with increment of 1 °C.
If the pressure on Inj X is too low, or an Injector is selected as safety which is not
configured, an alarm “FILAMENT SAFETY MISSING” will appear (refer to Table “Red Hand
Alarm ” in the chapter headed “Diagnostics”
• Ref. Filament Temp: it represents the Reference filament temperature. This value,
expressed in °C, can range between 40 and 400 °C , with increment of 1 °C.
If the pressure on Inj X is too low, or an Injector is selected as safety which is not
configured, an alarm “FILAMENT SAFETY MISSING” will appear (refer to Table “Red
Hand Alarm ” in the chapter headed “Diagnostics”
• Main Filament Safety: through the drop-down menu, select the injector used as Filament
safety for the main filament.
• Reference Filament Safety: through the drop-down menu, select the injector used as
Filament safety for the reference filament.

117
Functioning
Once the detector has been installed, flow must be established prior to any heating of the detector
or filaments. Columns should be conditioned before connecting them to the detector.
Once conditioned, columns can be connected and flow established across both filaments.

Overall sensitivity increases as the difference between the filament temperature and the detector
temperature increases, but filament life decreases as its temperature increases.
Thus, the block temperature should be set as low as possible, with the ideal being just slightly
above the boiling point of the highest boiling component of the sample.

Allow adequate time for all temperatures to equilibrate as indicated by a stable baseline.
Typical equilibration time for block temperature from cold start-up to 130 °C is approximately one
hour. Detector block temperature changes take much longer to equilibrate than filament
temperature changes do.

Switching on
In order to switch on the micro thermal conductivity detector the procedure is as follows:

• Prior to any operation, the carrier gas must flow into both channels (see the chapter
headed “Introduction systems”)
The flow rates can be measured directly at the two exits, one on the right hand side of the
detector and the other one on the left.
• Set the oven temperature and the detector cell temperature. Wait until the temperatures
are constant. (see “Oven temperature” in the chapter “Oven” and the paragraph
“Temperature” in this chapter).
• Set the desired value of the filament temperature.
Operating in the differential mode, set the same for the other filament.

• When the filament temperatures are stable, proceed to the zeroing of the signal as
follows:

• Set the Main signal at a value slightly over zero (for example 5).
To speed up this procedure, it is advisable to set a higher value and then decrease it step
by step until the lower value is reached (see “Signal” in this chapter).
• Set the Reference signal in the same way. When both the Main and Reference signals are
near zero, the maximum dynamic range is obtained.

• In this condition, to obtain a positive signal the sample should be injected in the Main
channel.

• By injecting the sample in the Reference channel, a negative signal will be produced.

• Besides, the baseline on the Reference should be set to a negative value until a positive
signal is obtained on the acquisition system.

118
Signal
In order to set all the operative parameters for signal control, open the page “Signal”
(fig. 122 and 123).

fig. 122 - Signal - single mode fig. 123 - Signal - diff. mode

Digital acquisition rate


As a general rule, at least 10-20 data for peak must be acquired to correctly define a peak.
This means that the acquisition rate must be select so that the product of Acquisition rate
(sampling/sec) and the peak width in seconds is between 10-20.

Digital acquisition rate (expressed in Hz) can assume the following values: 2.5, 10, 25, 50,
100, 250, 300.
According to the Min.Half-Peak Width set, the optimal acquistion rate is automatically suggested
(fig. 122 and 123). You can still select a different one through the drop down menu.

Signal zeroing
To zero the output signal from the electrometer open the page “Signal” (fig. 122 and 123) .
Into the box “Signal target”, insert the signal level required for the Main and the Reference signal
and press “Apply”. The signal will adjust to meet the level required. In the page “Status” you can
visualize the signal and the back off (fig. 119).

The back off value, expressed in mV, represents the quantity algebrically added to the signal to
bring it to the value set in the “Signal target” edit box.

119
Graphic
In the page “Graph” (fig. 124) the plot of the signal will be visualized. Use the buttons
“+” and “-” to change the value in the time scale (expressed in minutes) and the Voltage
scale (expressed in mV).

fig. 124 - Graph

120
Detectors

PhotoIonization Detector PID 86/90

Introduction
The photoionization detector (fig. 125) basically consists of a UV lamp and an ionization chamber.
UV rays pass through a Magnesium Fluoride window into the ionization chamber.
When the molecules of the compound absorb the radiation, a photo ionization process takes place
according to the following reaction:

fig. 125 - Photoionization Detector

Inside the ionization chamber there are two electrodes to which a voltage is applied.
The electrically charged particles generated by the ionization process flow to the two electrodes
and produce a current.
The current, which is proportional to the charges produced, is subsequently amplified and
measured.
Every compound is characterized by an ionization potential (IP): it represents the minimum energy value
of the radiation needed to ionize the molecules of that single compound.
The PID detector response is conditioned by ionization efficiency and, subsequently, radiation
energy.
A weak response for a particular compound is caused by inefficient ionization which is in turn
caused by insufficient photon energy.
As the lamp gives out photons with a constant energy value, the response of the detector is
conditioned by the ionization potential of each compound and increases as their potential
decreases: only the compounds with an ionization potential which is equal or lower than the
energy value of the photons can be efficiently ionized.
Compounds with higher potential will only be slightly ionized or not ionized at all and, therefore,
will give a weak response or no response at all.

122
There are UV lamps with different radiation energy: the most common are the 9.5, 10.2 and 11.7 eV.
The DANI PID 86/90 is equipped with a 10.2 eV lamp.

Description
The photoionization detector PID 86/90 is composed of :

• the base body


• the detector head
• the control unit

The base body


The base body (fig. 126) is composed of a stainless steel cylinder (1) welded to an aluminium support
(2) secured to the gaschromatograph by two screws (3).
The body is inserted into an aluminium block (4) containing the heating resistance (5) and the
temperature probe (6). The auxiliary gas line (7) is installed on the sides of the base body.
A second line (8), which is usually closed, is available in the case that the base body is used with other
detector systems (e.g. FID, NPD, FDP).
A nozzle (9), which is electrically grounded, is screwed inside the body.
In the upper part, the knurled brass ring (10) secures the head to the base body.
The end section of the body, inside the gaschromatographic oven, has a 1/4 G threaded end (11).
Packed columns can be connected directly to this end with a 1/4G nut (12) and the brass seals (13).
If capillary or wide bore capillary columns are used, an adapter to reduce the internal volume of the
base body should be installed: the adapter has a 4M threaded end.

fig. 126 - PID 86/90 base body

The detector head


The PID 86/90 detector head (fig. 127) has an upper part and a lower part which are screwed
together.

123
The upper part is composed of a nickel plated aluminium cap (1) that holds a UV light (2) held in
place by two brass semicircles (3).
The light gives off radiation with 10.2 eV energy.
The radiation passes through a Magnesium Fluoride window (4) into the ionization chamber.
The power supply cable for the lamp exit from the aluminium cap (5) and has a teflon connector
(6) on the other end.
The lower part is composed of a nickel plated aluminium body (7) covered inside by a teflon
cylinder (8) on which an electrode collector is assembled; it contains a small glass cylinder (10) and
a teflon seal disc (11): the ionization chamber is made up of these parts.
Between the lower and the upper parts there is a steel spring (12).

fig. 127 - PID 86/90 detector head

The body has a connector for link up to the control unit (13) and another for grounding the
detector (14); there is also a vent (15) for expulsion of gases from the ionizing chamber.

The connection between the base body and the head has an O-ring seal (16) positioned on the lower
extremity of the head.

The control unit


The control unit (fig. 128) provides electronic control of the detector.
The control unit includes an electrometer (1), a detector control board (2) and a board for the lamp
power supply (3).
The power supply voltage to the lamp is about 600 V.
The connector (4) for link-up to the gas chromatograph is located on the side of the control unit.

The control unit is located in the console of the gas chromatograph in one of the four positions
which are, from left to right, A, B, C and D and that correspond to the positions of the detectors.

The signal cable (5) exits from the electrometer, the lamp power supply cable (6) and a detector
grounding cable (7) from the corresponding board.

124
fig. 128- PID 86/90 control unit

Temperature
Setting the temperature (“Temp” page)
The temperature of the detector can have a value between 40 and 200°C, with increment of 1°C.

· In order to set the detector temperature open the page “temp”, press ON to activate
the temperature control and use the numerical keypad to insert the value in the
corresponding edit box (fig. 129).

fig. 129 - PID Temperature

Indication temperature (“Status” page)


· In order to see detector temperature open the “status” page. The number on the right
indicates the set oven temperature and on the left the actual oven temperature reading as
measured by the temperature probe. (fig. 130).

125
fig. 130 -PID Status

Auxiliary gas
Setting the flow rate (“Flows” page)
· Press ON to activate the control flows (fig. 131) and, through the drop-down menu, select the
auxiliary gas (Nitrogen or Argon-Methane).

Insert in the edit box “Aux” the value required. The auxiliary flow can have a value between 0
and 100 ml/min, with increment of 1 ml/min.

fig. 131 - PID Aux gas

126
Visualizing gas flow (“Status” page)
· In order to read the gas flow regulation open the “status” page. The number on the right
indicates the set value and on the left the actual value (fig. 130).

Lamp
In the page “Lamp” (fig. 132) you can control the lamp. Press ON to turn on the lamp.
Press OFF to turn it off.

fig. 132 - PID Lamp

Switching on the detector


• Feed the carrier gas and the auxiliary gas (if required). (see the chapter headed
“Introduction systems” and paragraph “Auxiliary gas” in this chapter)
• Set the temperature of the base body at a minimum value that will avoid
condensation of low volatile substances from the sample or from the column
stationary phase.
In most cases 150°C is more than enough.
In any case, the lamp will not withstand temperatures above 200°C.
It must also be considered that the higher the temperature, the lower the life of
the lamp (see “Temperature” in this chapter).
• Turn on the UV lamp (See “Lamp” in this chapter).
• Wait about 30 seconds for the set working conditions to stabilize (Check the signal
in the “Status” page).

127
Signal
In order to set all the operative parameters for signal control, open the page “Signal” (fig. 133).

Selecting the RANGE level


The amplitude of the detector dynamic range can be varied to suit the analytic needs by selecting
the RANGE function.
It means that, at different range, the same value of current measured by the detector produces a
different output signal.

Three range levels (1, 10, 100) are available: for each higher level, the dynamic range of
the signal produced by the detector is increased by a 10 factor compared with the previous
level.
This results in a output signal 10 times lower for the same current value.
Set the RANGE function to 1 to get the minimum full scale range, that is the maximum
sensitivity.

fig. 133 - PID Signal

Selection of the RANGE level depends on the analytic conditions: select the proper range level to
guarantee that all peaks of interest are within the detector dynamic range, which means that the
corresponding signal does not exceed the scale maximum and that at the same time they are not
too small to be correctly measured.

· Select the range levels through the drop-down menu (fig. 133).

Digital acquisition rate


As a general rule, at least 10-20 data for peak must be acquired to correctly define a peak.
This means that the acquisition rate must be select so that the product of Acquisition rate
(sampling/sec) and the peak width in seconds is between 10-20.

Digital acquisition rate (expressed in Hz) can assume the following values: 2.5, 10, 25, 50,
100, 250, 300.

128
According to the Min.Half-Peak Width set, the optimal acquistion rate is automatically suggested
(fig. 133). You can still select a different one through the drop down menu.

Graphic
In the page “Graph” (fig. 134) the plot of the signal will be visualized. Use the buttons “+”
and “-” to change the value in the time scale (expressed in minutes) and the Voltage scale
(expressed in mV).

fig. 134 - PID Graph

129
Valve & Accessories

Valve & Accessories

(to be completed)

130
Method

Method

How to create a method


A method controls the functioning of the instrument during the analytical runs.
To create a method is necessary to specify several parameters:

• Oven temperature program (See the chapter headed "Oven"


• Injector parameters (See the chapter headed "Injection systems")
• Detector parameters (See the chapter headed "Detectors")
• Timed events (See "Timed Events" in this chapter)"
• etc..

It is possible to change some parameters during the analysis. In this case a pop-up "Confirmation"
will appear. Reply "Yes" to the question "Are you sure you want to change this setting during run?"
to modify the selected parameter (fig. 135).

fig. 135 - Confirmation

When a parameter have been modified, an asterisk will be displayed on the right of the method
name (fig. 136).

fig. 136 - Modified Method

132
Method

Pressing on the method name, the" Manage Methods" window will appear.
This window contains two pages: the "Manage Methods" page and "Method Sequence" page.

fig. 137 - Manage Method

In the area of dialog "Active Method" of the "Manage Methods" page (fig. 137), you can find three
options:

to save the modification preserving the same name of the loaded


method. This function is active if:

• the current method has been modified


• The active method is different from the Default method.

to save the parameters entering a new method name.


This key is active when:

• The instrument is not running


• There are no active sequences
• There is still some memory space to save the method

In order to enter a new method name an alphanumeric keypad will


appear. Insert the name and press OK to confirm (fig. 138).

to create a new method starting from the Default method.


This function is active if:

• The instrument is notrunning


• There are no any activesequences
• There is still some memory space to save the method

All saved methods are listed in the frame "Stored Method" (fig. 139).

133
Method

fig. 138 - Keypad fig. 139 - Stored Method

Pressing on the name of method you want to select, four options will be activated.

allows to load a method. This function is active if:

• The instrument is not running

If the current method has been modified and not saved, before loading the selected method, the
pop-up "Save Active Method" will open (fig. 140). Replying "Yes" to the question, the changesto
the current method will be saved, answering "No" they will be lost.

fig. 140 - Save Active Method

allows to copy a memorized method and to save it with a new name .


This key is activated when:

• There are still some memory space to save the method

allows to eliminate a method. This function is active if:

• The instrument is not in running


• There are no active sequences

134
Method

Before deleting a memorized method a pop-up "Delete Method" (fig. 141) will be displayed.
If you are sure you want to eliminate the method, reply "Yes" to the question.

fig. 141 - Delete Method

allows to change the name of the method. The function is available


when:

• The instrument is not running


• There are no active sequences

Method Sequence
This paragraph contains the instructions to program a method sequence.

A sequence is a set of instructions for a range of runs. In this section you can only control the
Master GC and not the Master AS, so no sample will be injected. A method sequence can be useful
to automatize the instrument conditioning or the column cleaning.

In order to program a method sequence open the page "Method Sequence" (fig. 142), select a
method in the list "Stored Methods" and press ADD to insert it in "Method Seq.". You can enter up
to 25 methods and 50 repetitions for each method.

fig. 142 - Method Sequence

135
Method

When you select a method name in "Method Sequence" three functions will be activated:

• UP and DOWN: to modify the progressive order of the methods moving up or down the
selected method.
• REMOVE: to delete a method from the method sequence. If all methods are deleted and
the sequence is active, the message "NO ENTRIES IN METH. SEQUENCE" will appear.

Press ON to active the sequence.

When a sequence is activated and the instrument is not in Ready condition, the inscription
AUTORUN will appear on the Start icon. (See Autorun in the chapther headed "Status and control
of analysis" ).
In this case. the sequence will start automatically when all the ready conditions are reached.

Timed events
This paragraph explains how to automate signal, valve, and external events by programming in a
real-time clock (Clock time events) or during a run (Method Events).

Clock time events

Clock time events happen at certain time on specific days, based on a


real time-clock. (See "Time clock" in the chapter headed "Master GC
user interface".
The following functions can be programmed:

• Load a method
• Start a method
• Start method sequence
• Start AS sequence
• Valve (opening and closing valve)
• External Events (Starting external events for other devices)

· In order to gain access to "Clock Time Events", press "Menu" and select "Timed Events".

Open the page "Cclock time events" and press ON to enable the clock events (fig. 143). Clicking
"Add" the pop-up "Clock Time Event" will appear (fig. 144). Here you can select the event, the
parameter (for example the method name if the instrument must load a method or start a method,
etc..), the execution time and frequency. The Events available are listed in the table below.

Event Parameter

Load Method Method

Start Method Method

Start Method sequence

Start AS sequence

Valve Internal Event "n" ON "n": n. of valves installed (up to 4)

136
Method

Event Parameter

Internal Event "n" OFF "

External Events External event "n" ON "n": n. of external devices installed (up to 4)

External event "n" OFF "

Use the box corresponding to "Execution time" to enter the time you want the event to take place,
based on 24-hour clock.

fig. 143- Events programming fig. 144 - CLock Time Events

The programming event can occur:

• "ONCE": pressing on this box, a calendar will appear. Select day, month and year you
want the event to occur.
• "DAILY": the event will occur every day at the selected time.
• "WEEKLY": choose the day or the days of the week you want the event to happen.

Press OK to confirm the programming of the event.

All events are listed in the page "Clock Time Events". You can store up to 25 events (fig. 144).

When you select an event, the functions "MODIFY" and "DELETE" will be activated.

allows to modify the selected event. Pressing this button the pop up
"Clock Time Event" will appear. Make the changes and click OK to
confirm.

allows to eliminate an event from the list. Pressing this button the
pop-up "Confirmation" will appear. Answer "Yes" to delete the selected
event.

137
Method

Method events
You can program events to happen during a run (for example a valve can open three minutes into
a run). You can include a list of events for each analytical method.

The following events can be programmed:

• Range signal (see Detectors)


• Signal zeroing (see Detectors)
• Polarity change (see Detectors)
• Valve (opening and closing valves. See Valves)
• External Events (events for external devices)
• Aux (see Auxiliary temps and gases)

· In order to gain access to "Method Events" press "Menu" and select "Timed Events".

Open the page "Method Events" (fig. 145) and press ON to enable the events which occur at a
certain point during the analysis.

fig. 145 - Method Events fig. 146 - Method Time Events

Clicking "Add", the pop-up "Method Time Event" will appear (fig. 146). Here you can select
the event, the parameter (for example the detector position if the instrument must carry
out a signal zeroing, etc..). The Events available are listed in the table below.

Event Parameter

Range Change Detector A, B or C 1X

Detector A, B or C 10X

Detector A, B or C 100X

Signal Zeroing Detector A, B or C

138
Method

Event Parameter

Polarity Change Detector A, B or C -

Detector A, B or C +

External Event External event "n" ON "n": number of installed external devices (up to 4)

External event "n" OFF "

Valve Internal event "n" ON "n": number of installed valves (up to 4)

Internal event "n" OFF "

Aux Aux Gas 1, 2 or 3 ON

Aux Gas 1, 2 or 3 OFF

In the box "Executed at" enter the time (expressed in minutes) calculated from the start of the
analysis at which the event occurs. The setting interval allowed for each event is 0 - 999.00
minutes.
Press OK to confirm the event.

All events are listed in the page "Method Events". You can store up to 40 events (fig. 146).

When you select an event the functions "MODIFY" and "DELETE" will be activated.

allows to modify the selected event. Pressing this button the pop up
"Clock Time Event" will appear. Make the changes and click OK to
confirm.

allows to eliminate an event from the list. Pressing this button the
pop-up "Confirmation" will appear (fig. 147). Answer "Yes" to
delete the selected event.

fig. 147 - Confirmation

139
Status

Status

Instrument condition
The status of the instrument is shown on the Status Bar where the operative steps of the GC and
AS (if configured) are reported.

Ready
“Ready” indicates that the oven and all the devices selected as ready conditions (see Ready
conditions) have reached the values initially set for the method. The Status bar will show the
message READY.
The instrument can only accept the START command, whether keyed or remote, when all
conditions under “Ready” are present.

Iso, Rate
When an analysis starts, the status bar continually shows the progress of analysis being carried
out. The display shows the step of the analysis in progress (number of isotherm or temperature
gradient) and time, in minutes and hundredths, which has elapsed since start.

Cooling
At the end of analysis, the oven cooling step is activated and the temperature is brought down to
the value set for the first isotherm. The status bar will show the message COOLING and the time
indication is active also during the cooling step. This means that an evaluation of the complete
analytical cycle can be made, calculated from the start of the analysis to the time when the
instrument reaches the Ready condition and, therefore, is ready for the next analysis.

Waiting
At the end of the cooling step, when the oven temperature reaches the value set for the first
isotherm, the instrument passes to the WAITING step.
During this step, the instrument waits for the oven to adjust, with extreme precision, to the
foreseen value.
The instrument will remain in the “Waiting” condition until the other parameters reach the initial
condition set in the method (See Ready conditions).

Conditioning
The conditioning step consists of an additional stabilizing time, calculated from the moment when
the instrument reaches the initial conditions. During this step, the Status bar will show the
message “CONDITIONING” and the time elapsed.

140
Status

The duration of this step can vary from 0 to 999,00 minutes. To set this value select OVEN and
open the page General (see “Conditioning time” in the chapter headed “Oven”).
The Ready message will only show at the end of this step.

Stand by/Prep run


This condition is only present when “Splitless mode”, “Gas saving” and/or “Pulsed injection”
modes are selected.
In “Stand by” condition, all installed and activated devices are controlled, but their values do not
allow to carry out a correct analysis. During this step, the Status bar will show the message
“STAND BY” and the inscription “PREP RUN” will appear on the Start button.
Pressing “START/Prep run” Master GC will perform the following operation:

• When “Gas saving” function is programmed, PREP RUN ends the gas save mode and
resets the Split flow to the analytical flow. (see “Gas saving” in the chapter headed
“Injection systems”
• In “Splitless” mode, PREP RUN closes the split valve (see “Splitless” in the chapter headed
“Injection systems”
• In “Pulsed injection” mode, PREP RUN initiates the pressure increase (see “Pulsed
injection” in the chapter headed “Injection systems”

The instrument will remain in the “Prep run” condition until these parameters reach the initial
condition set in the method (see Ready conditions).

Autorun
When a sequence is activated and the instrument is not in Ready condition the inscription
AUTORUN will appear on the Start icon (see Method and Sequence in the chapther headed
“Method”).
Pressing this shortkey, the GC passes in AUTORUN condition. In this case when all ready
conditions are reached, the sequence will start automatically

Control of analysis
Start of analysis
The analysis starts by pressing the button “START” positioned in the middle of the desktop or the
shortkey on the tool bar.
The START command determines commencement of all temperatures and pressures programmes.
The programmed time commands of “Method Timed Events” are carried out, according to analysis
time, calculated from the Start time (see Timed Events).
When a sequence of analyses or methods is activated, the Start command determines the start of
the sequence.

The Start command will only be accepted if the instrument is in READY condition.
If the instrument is not in Ready condition and a sequence of analyses or methods is activated the
inscription AUTORUN will appear on the Start icon.
Pressing this shortkey, the GC passes in AUTORUN condition (See Autorun in the chapter headed
“Instrument condition”). In this case, when all ready conditions are reached, the sequence will
start automatically.

141
Status

End of analysis
The analysis will end automatically when the oven temperature program is finished.

However, the analysis can be stopped before completion of the program by pressing the STOP
button in the middle of the desktop or the shortkey on the tool bar.
Interruption of the oven temperature determines the interruption of any other program and the
reinstatement of all initial temperature, flow, pressure or timed event conditions.
Before stopping the analysis, a pop-up will appear. Answering “Yes” at the question “Are you
sure?”, you confirm the stoppage of the analysis (fig. 148).

fig. 148 - End of analysis

If a method sequence is in progress, the STOP command determines the stoppage of the
sequence: the instrument will return to the conditions of the first method of the sequence.
At the next START, the sequence will start from the first repetition of the first level.
If you press STOP when a Master AS is installed and a sample sequence is running, a pop -up will
appear. Selecting “End analysis” the sequence will be stopped, but the analysis in progress will be
completed. Pressing ABORT both analysis and sequence will be interrupted (fig. 149).

fig. 149 - End of sequence

142
Set up

Set up

The Master GC software controls all the parameters of the gas chromatograph: in order to carry
out correctly all the operative functions, the control unit must acquire all the information about the
specific configuration of each instrument. This task is performed at factory or by the DANI
customer service engineer during the instrument installation. Most of the set up parameters are
accesible through a password, and preferably managed by service people, to avoid unintentional
modifications.

Only two pages, "Com" and "Other", are accessible to the final user.

fig. 150 - Set up

· To gain access to "Set up" section, press Menu, Tools, then Set up (fig. 150).

Com
In this page (fig. 151) you can find all the parameters to connect Master GC to Clarity
software.

Activation code
To control Master GC through the Clarity software control driver, a specific code must be
entered in the "Activation code" box.
This code is strictly correlated to each software license and enables the communication ports
to control the instrument through the driver.
This code is reported in the documentation provided with the Clarity software package.

144
Set up

fig. 151 - Communication

Communication pipe
Master GC can communicate to a PC through three communication types: USB, LAN and RS232.
Besides, the analog output is available for all the detector signals.

· Select the communication pipe type through the drop-down menu.

• None: select this, if you use the signal analog output . In this case, connect the signal
cable to an external A/D converter or integrator according to the instruction reported in
the figure below (fig. 152).

A B C

0V 1V 10V 0V 1V 10V 0V 1V 10V

Clarity chn1 Clarity chn2 Clarity chn3

fig. 152 - Analog signal connections

• Serial: to connect the GC serial port 1 or 2 to a PC com port making use of RS232 serial
cable (fig.153). This communication type is suggested only for service (Baud Rate
19200).

145
Set up

fig.153 - RS232 communication fig. 154 - LAN communication

• LAN: use the LAN communication type to connect one or more instruments to a single
computer through a HUB.
A static IP address is required (fig.154). With a default subnet Mask, the first three
numbers must be the same on the GC and PC address. the last number must be different
for each instrument connected to the LAN port.
• USB: The USB communication port is the preferred one to connect one GC to one PC.
Connect the USB cable only after installation of the driver.

Other
In this page you can find four different items:

• Cryo Oven: it allows you to configure the oven cryogenic system between liquid carbon
dioxide (Liquid CO2) or with liquid Nitrogen (Liquid N2) (fig. 155).
The oven temperature range will change accordingly.

fig. 155 - Cryogenic device fig. 156 - Pressure unit

146
Set up

• Pressure Unit: the pressure meausrement unit can be selected (fig. 156).
The meaurement units available are: bar, Psi or KPa. All set values will be automatically
converted.
• Buzzer: select the buzzer ON to have a beep during an error condition.
• Master TD: select this function ON when Master GC is linked up to MasterTD or any other
gas sampling device (headspace sampler, Purge&Trap, ...).

147
Maintenance

Maintenance

The Maintenance window includes four pages to support the instrument maintenance.
Two of them are accessible only through a password, and preferably managed by service people,
to protect from unintentional modifications. The others two are available to the user for a routine
maintanance activity.

fig. 157 - Maintenance

In this chapter you can find information about the pages always accessible without the password.

· To gain access to "Maintenance" section, press Menu, Tools, then Maintenance. The accessible
pages are: "Touch Calib" and "Counters" (fig.157).

Touch screen calibration


In order to make the touch screen suitable to your finger touch, you can calibrate it.

· Open the page "Touch calib" and press the button "Calibrate touch screen".
A series of circles will be displayed. Press at the center of each circle (fig. 158).

At the end of this procedure the message "Congratulation, your touch screen has been calibrated"
will appear.
Press the touch screen again to continue.

148
Maintenance

fig. 158 - Touch screen calibration

Counters
The usage of a gas chromatograph can cause some parts to get dirty or to be consumed.
These parts must be cleaned or changed periodically at a variable frequency, depending on the
number of analyses.
The page "Counters" can help in recording the periodic maintenance, counting the number of
analyses from the last replacement of the parts.

Three columns are available:

• Name: insert the name of the device you want to monitor. Septum, liner and column are
present as default but you can change them; two further boxes are empty to insert others
items.

• Threshold: defines the number of analyses (from 0 to 1000) after which you should clean
or change the part. As soon as the counter reaches this value, an alarm will be produced.

• Counter: shows the actual number of analyses occurred from the last replacement.

fig. 159 - Counters

149
Maintenance

When one counter exceeds its threshold, an alarm will be shown. In the "Alarm page" (fig. 160)
you can read "COUNTER > THRESHOLD". This alarm still allows the instrument to reach the
READY condition.

After replacement of the part, press the button "RESET" to reset the current counter and cancel
the alarm.

fig. 160 - Counter alarm

150
Diagnostics

Diagnostics

Diagnostic
When the instrument is switched on, a Self test is performed to check the correct functioning of the
instrument. During this procedure, all the configured devices are checked one by one. At the end,
the diagnostic page will show all the devices in a list (fig. 161).

fig. 161 - Self test fig. 162 - Self test alarm

[
If the device passes the test, a symbol " " will be showed. If all the devices pass the self test, the
Diagnostic window will close automatically and the desk top will be displayed.

If a device fails the test, an alarm (exclamation mark) will be visualized. In this case, at the end
of the self test, the diagnostic page will remai open. Pressing on the device's name, a pop-up
will appear. Here detailed information about the device and/or the malfunctioning are
reported.

The Diagnostic page can be entered in any moment after the self test.

· To gain access to Diagnostic page press Menu, Tools and then Diagnostic.

The first item in the list is "System". Here you can read the serial number of the instrument and the
firmware version of the Main Board and the other controllers (fig. 163).

152
Diagnostics

fig. 163 - System information

Alarms
When the control unit diagnoses an error condition, an exclamation mark, accompanied by an
acoustical signal (See Buzzer in the chapter "Maintenance"), will blink on the status bar near the
time clock.

This exclamation mark will flash till you click it or the condition which is causing the alarm remains.

Press the icon to display the "Alarms" page (fig. 164). Here, the alarm
message are listed. Press on the row: a pop-up will appear containing
details on the problem and, in most cases, the instructions to solve it .

fig. 164 - Alarms

153
Diagnostics

Errors can be divided in:

• Parameters Error: these troubles spring from incorrect parameters you set. They will be
visualized by an hand near the message.

A red hand indicates an error that could cause serious damages. In this
case the START of analysis is blocked.

A blue hand indicates an error concerning a wrong setpoint. In this case


the START of analysis isn't blocked.

• Hardware Error: it indicates a malfunction of the instrument.

They are visualized by a exclamation mark. Pressing on the text a


pop-up will appear. It contains some details concerning the problem
and, in most cases, the instructions to solve it . The START of analysis
is blocked.

In some cases, when you have solved the trouble, it is necessary to press "CLEAR" under the text
to bring the situation back to normal.

fig. 165 - Alarm details

If the message says shows " HARDWARE ERROR" you are invited to see the diagnostic page for
details. For these problems, it is preferable to refer to the technical assistance (see "Diagnostic" in
this chapter).

154
Diagnostics

BLUE HAND ALARMS

MESSAGE ERROR DESCRIPTION HOW TO SOLVE IT

NO ENTRIES IN Method sequence is NO ENTRIES IN Insert a method in the sequence


METH. SEQUENCE active,but there METHOD SEQUENCE table or deactivate the Method
aren't any methods TABLE Sequence. (See Method)
in the sequence
table

GAS SAVING FLOW In Gas saving mode GAS SAVING FLOW Modify gas saving flow. Gas
< SPLIT FLOW split flow is bigger < SPLIT FLOW saving flow < split flow (See
then gas saving flow Introduction systems)

CRYO THRESH. < The activation CRYO THRESHOLD Modify the cryo threshold. The
OVEN INIT. TEMP temperature of < OVEN INITIAL threshold value must be bigger
cryogenic system is TEMP then the oven initial
lower then the oven temperature. (See Oven)
initial temperature

CRYO THRESH. < The activation CRYO THRESHOLD. Modify the cryo threshold. The
PTV X INIT. TEMP temperature of < PTV X INITIAL threshold value must be bigger
cryogenic system is TEMP then the PTV initial temperature.
lower then thePTV (See )
initial temperature

EVENT(S) LOST(S) One or more clock EVENT(S) LOST(S) Check the parameters in the
time events are lost FOR PARAMETER page Timed events (see
for parameters error ERROR OR GC IN Method)
or GC in run RUN Press CLEAR to delete the alarm

A EVENT WITH An timed event A EVENT WITH Insert a method in Method


SEQUENCE EMPTY correlated with SEQUENCE EMPTY sequence.
Method sequence (See Method)
can't occur because
Method sequence Press CLEAR to delete the alarm
table is empty.

MODIFIED METHOD The current method A MODIFIED Save the method (See Method)
IN SEQUENCE in the active METHOD IS or press START and the method
sequence has been INCLUDED IN THE included in active sequence will
modified. ACTIVE SEQUENCE. be saved.
PRESSING START,
THE METHOD WILL
BE AUTOMATICALLY
SAVED

DET X: ACQ.FREQ. Digital acquisition DET X: DIGITAL Modify the digital acquisition
TOO LOW frequency is too low ACQUISITION frequency or the Min. half peak
for the selected Min FREQUENCY UNDER width.
Half peak-width THE OPTIMAL (See Detectors)

AS: RINSE VOLUME You selected a rinse AS: RINSE VOLUME Modify the rinse volume
OVERFLOW volume bigger the BIGGER THEN See (AS parameters in the
syringe volume SYRINGE VOLUME chapter Master AS)

155
Diagnostics

BLUE HAND ALARMS

AS:SOLVENT You selected a AS: SOLVENT Modify the solvent volume


VOLUME solvent volume VOLUME BIGGER See (AS parameters in the
OVERFLOW bigger the syringe THEN SYRINGE chapter Master AS)
volume VOLUME

AS:INVALID VIAL IN One ore more AS: ONE OR MORE Check the vial type selected and
SEQUENCE selected vials in the VIAL NUMBER modify the selected vials in
sequence don't' exist PRESENT IN THE sequence.
SAMPLER (See Set up and AS sequence in
SEQUENCE ARE the chapter Master AS)
INVALID

FID A FLAME OUT The flame is out FID A FLAME OUT (See Fid in the chapter
Detectors)

AS NEEDS The tray ref and/or AS NEEDS Check in Diagnostic


CALIBRATION the configured CALIBRATION, (Autosampler) which injector or
injectors haven't PLEASE SEE tray ref need to calibrate.
been calibrated DIAGNOSTIC FOR See (How to align Master AS)
MORE DETAILS

COUNTER>THRESH One counter ONE COUNTER (See Counters in the chapter


OLD exceeded its EXCEEDED ITS Maintenance) Reset the counter
threshold. THRESHOLD. RESET for clear the alarm
THE COUNTER TO
CLEAR THE ALARM

UNREACHABLE The oven can't UNREACHABLE See Oven


OVEN RATE reach the rate you OVEN RATE
set

RED HAND ALARMS

MESSAGE ERROR DESCRIPTION HOW TO SOLVE IT

OVEN: TEMP SET the oven OVEN: TEMP SET Insert a correct temperature
OVER MAX TEMP temperature set is OVER MAX TEMP setpoint
superior then the (See the chapter headed Oven)
oven max
temperature

INJ X TOTAL FLOW Total flow is lower INJ X TOTAL FLOW Master GC can't correctly work
< 10 ML/MIN then 10 ml/min < 10 ML/MIN when total flow is lower then 10
ml/min.
Modify the flows. (See
Introduction systems)

156
Diagnostics

RED HAND ALARMS

SPLIT ON TIME < In solvent split SPLIT ON TIME < Set the split ON value superior
SPLIT OFF TIME mode you set the SPLIT OFF TIME then split Off value.
Split on value lower See ( Solvent split mode in the
then split Off value. chapter Introduction systems)

GAS SAVING TIME In Gas saving mode GAS SAVING TIME Set the Split On value superior
< SPLIT ON TIME and Splitless or < SPLIT ON TIME than the Split ON.
Solvent Split, the See ( Introduction systems)
time that you set is
lower then Split On
time

LAST VIAL < INIT you select a first vial LAST VIAL < INIT Insert correctly the values.
VIAL > then last vial VIAL (see AS sequence in the chapter
headed Master AS)

NO ENTRIES IN AS The AS sequence is NO ENTRIES IN AS Insert the line in the table or


SEQ. TABLE active but there SEQUENCE TABLE deactivate the AS sequence.
aren't any entries. see AS sequence in the chapter
headed Master AS)

mTCD REFERENCE A mTCD Ref has mTCD REFERENCE (See Detectors)


FILAMENT been configured FILAMENT
without having a CONFIGURED
microTCD WITHOUT A LINKED
MAIN FILAMENT

AS VOLUMES You set volumes AS VOLUMES (See Set up in the chapter


OVERFLOW larger then the OVERFLOW headed Master AS)
syringe volume

FILAMENT SAFETY Pressure on INJ X PRESSURE ON (See Detectors)


used as safety for INJECTOR X USED
filament is too low AS SAFETY FOR
FILAMENT TOO
LOW

FILAMENT SAFETY Pressure on AUX X PRESSURE ON (See Detectors)


used as safety for INJECTOR X USED
filament is too low AS SAFETY FOR
FILAMENT TOO
LOW

FILAMENT SAFETY An injector used as FILAMENT SAFETY (See Detectors)


safety for filament is NOT SELECTED
not configured

FILAMENT SAFETY Same filament SAME FILAMENT (See Detectors)


safety has been SAFETY SELECTED
selected for more FOR MORE THEN
microTCD FILAMENT

157
Diagnostics

RED HAND ALARMS

FID X GAS CLOSED THE GAS ON FID X (See Detectors). Open the gas
DETECTOR HAS on fid and press Clear in the
BEEN CLOSED "alarm"page to cancel the alarm
BECAUSE FLAME
WAS OUT

CRYO TIMEOUT When cryo saving CRYOGENIC (See Oven)


time has elapsed, COOLING TURNED
cryo system has OFF, CRYO SAVING
turned off. TIME ELAPSED

CRYO FAULT If the oven CRYOGENIC Checking the cryogenic system


temperature doesn't COOLING TURNED (See Oven)
reach the set point OFF, OVEN CAN
by 16 minutes, the NOT REACH
cryogenic system TEMPERATURE SET
will be deactivated POINT

14-158
Diagnostics

HARDWARE ALARMS

MESSAGE ERROR DESCRIPTION HOW TO SOLVE IT

METH. CONFIG. The method has METHOD Modify the method


MISMATCH been saved with a CONFIGURATION (See Method )
GC configuration MISMATCH
different then the
actual

FAULT TEMP When GC is on, a THERMAL Call the technical assistance


SENSOR temperature sensor SHUTDOWN: FAULT
failure is diagnosed TEMPERATURE
SENSOR

OVEN: TEMP OVER Oven temperature is THERMAL Call the technical assistance
MAX TEMP over the safety max SHUTDOWN:OVEN
temperature. TEMPERATURE
OVER SAFETY MAX
TEMP

OVEN The cryogenic THERMAL Call the technical assistance


TEMPERATURE OUT temperature is SHUTDOWN:OVEN
OF RANGE under the minimum. TEMPERATURE OUT
Valve is OF RANGE
malfunctioning

PTV TEMPERATURE The cryogenic THERMAL Call the technical assistance


OUT OF RANGE temperature is SHUTDOWN: PTV
under the minimum. TEMPERATURE OUT
Valve is OF RANGE
malfunctioning

CARRIER GAS Carrier gas pressure CARRIER GAS Check the gas pressure
PRESSURE LOW to Inj X is lower PRESSURE TO INJ X available.
than requested. INLET LOWER THEN (See Introduction systems)
Oven temperature REQUEST
will be forced to Then press "clear" to cancel the
40°C for safety and alarm and restore the
GC in splitless introduction mode and the oven
mode. temperature.

CARRIER GAS Carrier gas pressure CARRIER GAS Check for possible leakage
PRESSURE to Inj X is PRESSURE Then press "clear" to cancel the
DECREASE decreasing. Oven DECREASED alarm and restore the
temperature will be introduction mode and the oven
forced to 40°C for temperature.
safety and GC in
splitless mode.

CRYO FAULT Oven temperature OVEN Call the technical assistance


under the minimum TEMPERATURE
OVEN THE
MINIMUM

HARDWARE ERROR Generic hardware Please see See Diagnostics


error diagnostic page for
details

159
Diagnostics

160
Master AS

Master AS

Introduction
The Master AS Automatic Liquid Sampler is an automatic sampler for the injection of liquid samples
into the Master GC.
It is mounted on the left side wall of the gas chromatograph and can inject into up to three
injectors .

It can operate traditionally using normal syringes for liquids or according to the “Flush & Dry”
technique (optional) using a special modified syringe.

Description
Master AS (fig. 166) includes:

• The moving block (1) consisting of three moving axes X, Y and Z. The vertical axes Z
includes the syringe housing and provide the vertical movement of both the syring and
the plunger.
The block moves along three axes (X,Y and Z) to carry the syringe to the sample vials, to
the solvent and waste vials and to the injector A, B and C.

fig. 166 - MasterAS

• A 160 sample tray for 2 ml vials (standard) or a 65 sample tray for 10 ml vials (optional)
(2). These removable trays are seat in the base of the autosampler and blocked by the
position keys.

162
Master AS

• A Solvent & Waste tray(3) that can contains up to five solvent or Internal standard vials
(10 ml) and up to five waste vials (10 ml). The tray is removable, inserted on the base of
the autosampler and blocked by the position keys.
• The electrical connections are available on the back of the instrument.

Syringe block
The syringe is lodged in an interchangeable support (1) and is held in place by a retainer(2). The
plunger head is set in an adjustable holder(3) and fixed by a blue screw(4). The syringe needle is
inserted in a retractable guide (5) protecting it from possible bends.
A transparent sliding cover protects the block (6) (fig. 167).

fig. 167 - Syringe block

The electrical connections


The electrical connections, available on the back of the instrument (fig. 168) are: the supply
socket (1), the main switch (2), RS232 serial output (3) for the control of the instrument.

fig. 168 - MasterAS connections

163
Master AS

Set up
The "Set up" window consists of two pages, "Vial & Syringe" and "Solv. & Waste", and allows you
to select the syringe volume, the vial dimensions and the position of Solvent, Internal standard and
Waste vials.

· To gain access to this section, press three times on the corresponding short cut key or select
"Menu", "Master AS" then "Set up".

Vial & Syringe


In the "Vial&Syringe" page (fig. 169), the following settings are available:

• Vial: select the vial type through a dropdown menu. (2 ml and 10 ml)
• Syringe: eight different syringes are available through a dropdown menu: 5, 10, 10
Flush&Dry,25, 50, 100, 250 and 500 ml).

fig. 169 - Vial&Syringe

• Syringe Replacement: pressing this button makes the vertical arm of Master AS to move
in a useful position to replacet he syringe (see "How to replace the syringe" in the
paragraph "Maintenance"). Press "Done" after the syringe replacement: the vertical harm
will move to its home position (fig. 170).

fig. 170 - Syringe replacement

164
Master AS

Solvent&Waste
Master AS has five positions, from A to E, for Solvent or Internal Standard vials and five positions,
from A to E, for the Waste Vials. In this page , you can select for each position if it will contain a
Solvent or an Internal Standard (fig. 171). You can also select if you want each Solvent and
Internal Standard wasted in separated vials or in the same vial (fig. 172).

fig. 171 - Solvents fig. 172 - Waste

AS parameters
· To gain access to this section you can press twice on the corresponding short cut key or select
"Menu", "Master AS" then "AS parameters".

Sampling mode (Inj. Mode)


Four sampling modes are available: Sample, Air Plug, Solvent Plug, Internal Standard.
The mode "Sample" is the standard injection mode: it can be combined with one or more other
modes to perform special injection techniques and take analytical advantages.

Sample

The syringe block moves to the sampling point, the needle enters into the vial and the plunger
moves up till measuring the sample volume selected in the method. In this mode, the needle
results full of liquid.

In order to carry out a correct sampling, it is advisble to perform sample rinses and plunger strokes
(see "Sample Handling" in this paragraph).
In this case, before sampling, the syringe takes a selected volume of sample and discharges it into
the waste vial (Sample rinse). This operation is repeated several times according to the number set
in the method. To eliminate the air bubbles inside the syringe, the plunger moves up and down for
the number of times set in the method, keeping the needle dipped into the liquid.

165
Master AS

· To select this injection mode insert the volume, expressed in ml (from 0.1 to 500), in the
"Sample" box.

The sample volume is shown in yellow on the syringe on the right of the display. The remaining
volume, in ul, is displayed on the top of the syringe.

fig. 173 - Sample

If you set a sample volume higher than the capacity of the syringe, an alarm "AS volume overflow"
will be shown in the Alarm" page. The volume in excess is displayed on the top of the syringe.

Air Plug

The syringe block moves to the sampling point, the needle enters into the vial and, after rinses and
strokes (if selected), the plunger moves up till measuring the sample volume selected in the
method.
When the needle is out of the vial, the plunger lifts up to withdraw the volume of air plug set in the
method. By this way, the needle is full of air.

fig. 174 - Air plug

166
Master AS

· To select this injection mode press ON to active the "air plug" function. Insert the air volume,
expressed in ml (from 0.1 to 500), in the "Air plug" box and the sample volume in the "Sample" box
(fig. 174).

On the syringe on the right side of the display, the sample volume is shown in yellow and the air
plug volume in white. The remaining volume, in ul, is displayed on the top of the syringe.

If the total volume is higher than the capacity of the syringe, an alarm" AS volume overflow" will
be shown in the "Alarm" page. The volume in excess is displayed ont the top of the syringe,

Solvent Plug

The syringe block moves to the “Solvent” position and both syringe and plunger move to take the
solvent.
After the syringe is withdrawn from the solvent, the plunger lifts up to take 0.5 ml air which will
separate the solvent from the sample.

Then, both the sample volume set in the method and air volume (if selected) will be taken.
In this way, a solvent plug is created which is separated from the sample by an air plug while a
second air plug fills the needle. During injection, the solvent plug improves the quantitative
transfer of the sample into the injector.
This mode does not allow to make any sample rinse and strokes.

· To select this injection mode press the "Solvent/IS Pos" (fig. 175) to select the position of the
solvent use as plug, then press ON to active the "solvent plug" function. Insert the solvent volume,
expressed in ml (from 0.1 to 500), in the "Solvent plug" box and the sample volume in the
"Sample" box.

fig. 175 - Solvent for solvent plug

On the syringe on theright of the display, the sample volume is shown in yellow, the air plug in
qhite and the solvent plug volume in blue (fig. 176). The remaining syringe volume is displayed on
the top of the syringe.

If the total volume ia higher than the capacity of the syringe, an alarm" AS volume overflow" will be
shown in the "Alarm" page. The volume in excess is displayed on the top of the syringe.

167
Master AS

fig. 176 - Solvent plug

Internal Standard

After the syringe is withdrawn from the Internal Standard, the plunger lifts up to take 0.5 ml air to
separate the IS from the sample.

In order to carry out a correct sampling , it is advisable to set IS rinses and strokes (see "Sample
Handling" in this paragraph).
In this case, before sampling, the syringe takes a selected volume of IS and discharges it into the
waste vial (IS rinse). This operation is repeated several times according to the number set in the
method. To eliminate the air bubbles present inside the syringe, the plunger move up and down
keeping the needle dipped into the liquid.

Then, both the sample volume set in the method and air (if selected) will be taken.
This mode does not allow to make any sample rinse and strokes.

· To select this injection mode press the "Solvent/IS Pos" (fig. 177) to select the position of the
I.S.vial, then press ON to active the "Internal standard" function. Insert the solvent volume,
expressed in ml (from 0.1 to 500), in the "Internal standard" box and the sample volume in the
"Sample" box.

fig.177 - I.S. selection

168
Master AS

On the syringe on the right of the display, the sample volume is shown in yellow and the I.S.
volume in red (fig. 178). The remaining syringe volume is displayed on the top of the syringe.

If the total volume is higher than the capacity of the syringe, an alarm" AS volume overflow" will
be shown in the "Alarm" page. The volume in excess is displayed on the top of the syringe.

fig. 178 - Internal Standard

Sample Handling
Master AS is able to rinse the syringe with the sample or IS (if selected).

In the "Sample Hand" page (fig. 179) the following parameters are available:

• Volume: this is the volume used for the sample rinse or IS rinse (if selected). This value is
expressed in µl and can range from 0.1 to 500 µl. If you set a sample rinse volume or I.S
rinse volume higher then the capacity of the syringe, an alarm" AS volume overflow" will
be shown in the "Alarm" page.
• Number: this value represents the number of repetitions (up to 25) for sample or I.S.
rinse.

fig. 179 - Sample Handling

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Master AS

• Sample Taking Height: It is the needle distance from the bottom of the vial during the
sampling. This value is expressed in millimeters and can range from 0 to 30 mm.
• Plunger strokes: the plunger is able to move up at the speed set in "Plunger speed (ml/s)"
and down at a fixed speed. The strokes are very useful when air bubbles are present
inside the syringe. You can select up to 25 strokes.
• Plunger speed: This is the speed, expressed in µl/sec, at which the plunger moves up. It
can range from 0.1 to 100 µl/sec.
• Viscosity delay: it is the time, expressed in seconds, during which the needle remains
inside the vial before the injection. This function is important when viscose solutions are
sampling.This value can range from 0 to 25 seconds.

Solvent Washing
It is possible to carry out the syringe washing with one or two different solvents at the beginning
and/or at the end of each injection, with the Pre Solvent and the Post Solvent respectively.
To do this, the syringe block lowers on the solvent position, the syringe takes a set volume of
solvent and discharges it into the waste vial. This operation is repeated for the number of washings
with solvent set in the method.

fig. 180 - Solvent washings

The washing volume, expressed in ml, can range from 0.1 to 500 ml. If the washing volume is
higher than the capacity of the syringe, an alarm" AS volume overflow" will be shown in the
"Alarm" page.

The number of washings (up to 25) and the position of the solvent vial to use can be selected
separately for both the " Pre solvent Washing" and the "Post solvent washing" (fig. 180).

Injector
After taking the sample with one of the modes previously described, the syringe block moves to the
injector (A, B or C) selected. The block lowers and the needle enters into the injector at a
selectable speed and a selectable depth.

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Master AS

It is possible to check one or more injectors, if available. In this case, the sample will be injected
first in all the injectors in sequence then for all the repetitions included in the method (es.: sample
1: rep.1-inj.A/rep.1- inj B/rep.1-inj.C, rep.2-inj.A/rep.2-inj.B/rep.2-inj.C, etc..).

The needle can dwell into the injector for a certain time before injecting the sample (Pre Inj delay)
to perform the “Hot Needle” injection technique (see Introduction systems). A dwell time after the
injection (Post inj delay) can be also set in order to get a complete vaporization of the sample (fig.
181).

• Plunger Inj Speed: this is the speed of the plunger during injection: it is expressed in
(ml/s) and can range from 0.1 to 100 ml/sec.
• Injector Needle Depth: It is the needle depth into the injector, expressed in mm, and can
range up to 45 mm.
• Pre Inj Delay/ Post Inj Delay: it is the time, expressed in seconds, during which the needle
remains inside the injector before the plunger lowers and after the injection. It can range
up to 25 seconds.

fig. 181 - Injector

AS Sequence
The"AS Sequence" window (fig. 182) allows to set all parameters concerning the sampling
sequence.

· To gain access to this section, press once on the corresponding short cut key or select "Menu",
"Master AS" then "AS Sequence".

How to create an AS sequence


Press Add to create a new row in the table : then, enter the position of the first and the last vials to
be sampled in the cell "First" and "Last" respectively.
If the number of the first vial is higher than the last vial, the alarm "Last vial < First vial" will be
shown.

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Master AS

fig. 182 - AS Sequence

Specify the number of repetitions for each vial in the cell "Rep". The number of repetions ranges
from 1 to 100. All the repetations for the same vial will be processed before moving to the next.
Clicking on the colum "Method", aall the stored method will be show n. Select the method to be
used for each sequence row.

Up to five different sequence can be stored as Sequence A, B, C, D or E according to the selection


on the dropdown menu (fig. 183).

fig. 183 - AS sequence storing

In order to eliminate a line, click on the row to select it and press "Delete".

Press "ON" to active the sequence.

If the current Method is different from the first AS sequence method a pop up "Load First AS
Sequence Method" will appear (fig. 184).
Replying "Yes" the first AS sequence method will be loaded, selecting "No" the first method will be
loaded after pressing START.

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Master AS

fig. 184 - First AS Sequence Method

How to start an AS sequence


If an AS sequence is active and the GC is READY, press START once and the instrument will carry
out all the operations automatically.

If the instrument is not in Ready condition and a sequence is activated, the inscription AUTORUN
will appear on the Start icon.
Pressing this short cut key, the GC will pass in AUTORUN condition (see "Status and control of
analysis"). The sequence will start automatically as soon as all the ready conditions are reached.

When the run is in progress, the ON/OFF button is disabled. In this case, a pop-up "Sequence
Error" will be shown (fig. 185).

fig. 185 - Sequence Error

How to stop a sequence


In order to stop a sequence, press the icon "Stop" in the toolbar or on the desktop. A pop-up
"Sampler sequence stop" will be shown (fig. 186): the sequence will pause to allow the selection
among four options:

• Resume: the sequence restarts from where it was stopped


• End Analysis: the current analysis ends, then the sequence stops
• Abort: the instrument stops both the analysis and the sequence
• Abort & Wash: this option, active only during sampling, will stop the sequence and wash
the syringe with the solvent selected as "Post Washing Solvent".

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Master AS

fig. 186 - Stop a sequence

AS status
The operating status of the Master AS is shown on the Status Bar by the indication
"SAMPLING".
A detailed description of the AS status is available in the page "AS status" (fig. 187).

In the upper frame "AS Status", all the steps are monitored in real time: Init. Sampling, Pre Solvent
Washing, Internal Standard, Solvent, Sampling, Air plug, Post Solvent Washing and Injection ( see
"Sampling mode" in this chapter).

fig. 187 - AS Status

In the lower frame "AS sequence", the number of set and actual repetitions, the method's name,
the vials and injector involved in the analysis are shown.

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Master AS

Missing vials
Before sampling, the syringe block moves to the position of the current vial and goes down to
check the presence of the vial.
In the AS status page, "Checking Vial" will be displayed.

If the instrument does not check the vial, it moves to the next vial. An alarm "Vials missing " will be
shown. Details on the missing vials are reported in the page "Missing vials" (fig. 188) that you can
open by clicking on the Status bar.

The table "AS Missing vial" consists of four columns and allows you to identifythe missing vials, the
number of repetitions that have not been carried out and the method.

This feature is available only on Master AS equipped with vial presence sensor.

fig. 188 - AS Missing vial fig. 189 - Priority Sequence

Priority Sequence
The "Priority sequence" allows you to setting up a sequence during the analysis. This sequence will
start immediately after the end of the current analysis.

· In order to program the priority sequence press the "Priority Seq" button. A pop- up will appear
(fig. 189).

Insert the first and last vial to be urgently sampled in the corresponding boxes, the number of
repetitions and the method to be used.

Press "On" to activate the Priority sequence control.

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Master AS

Maintenance
To open the "Maintenance" window press Menu, select "Master AS", then "Maintenance" (fig.
190).

Syringe Cleaning
This option allows you to manually wash the syringe.
Select the solvent through the dropdown menu "Position solvent" and insert the number of
washing in the corresponding box.

fig. 190 - AS Maintenance

Pressing "Start", the washing procedure will begin.


During the Syringe cleaning, "SYR. CLEANING" will be reported both in the Status bar and in the
"AS Status" page.
To stop the syringe washing press "Abort"

How to install the syringe


• Open the transparent sliding cover

• Keeping the needle guide completely lifted, insert the syringe into its seat byinserting the
needle through the holes on the seat and on the needle guide.
Keep the syringe with the graduated side frontly.

• Insert the syringe in the interchangeable support and the plunger head into its seat on the
adjustable holder and regulate the heigh by loosing the two front screws, then fix the
plunger head by the blue screw.

• Close the retainer to block the syringe.

• The standard syringe support is suitable for 5 and 10 µl syringes.


For syringe from 25 to 500 a different support is available as an option.

• To remove the syringe support pull it towards you. To install the other support insert the
four pins into the corresponding holes.

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