Professional Documents
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Gas Chromatography
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
abcit
What is
Gas Chromatography?
A Separation Science
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What is analyzed with a Gas Chromatograph?
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Chromatography
A Separation Technique
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Gas Chromatography, Basic Steps
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Chromatography Gives
= + + +
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The Chromatographic Process
Column
Tubing
Sample
Stationary Phase
(Liquid Phase)
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Column Chromatography
Liquid Phase
Carrier Phase
Time 2
Liquid Phase
Carrier Phase
Time 3
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Chromatographic Results
Plot of Component
Concentration
High Concentration
Component Bands
Low Concentration
Component Molecule
Concentration
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Component Peaks
Peak Areas are Determined By
Components and Concentration
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Gases and
Gas Controls
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Gas Supplies and Control
Carrier Gas
( Helium TANK PRESSURE REGULATOR
( Nitrogen Inlet
Outlet Gauge
( Hydrogen Gauge
Gas
Shutoff Inlet
Combustion Gases
Pressure Control
( Hydrogen
Outlet Fitting or H2 Snubber
( Air
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Typical Carrier Gases
N2, Ar/Methane
Ar/Methane ECD Electron Capture
He MS Mass Spectrometer
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Combustion Gases
FID
GAS GAS
CONTROL CONTROL
H
Y Detector
D A
R Dry Compressed
O
G or I
E 99.995 % Pure Zero Grade R
N
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Line Filters
Use filter/drier for all gases
Add O2 filter for carrier gas
• ECD and capillary columns (esp. Carbowax)
Carbowax)
Use indicating O2 trap in
series with filter
Change traps according to
maintenance schedule
Replace internal AutoSystem
or Clarus charcoal trap for ECD
Indicating filter
Gas Gas
in Heated Filter
Indicating packing out
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Pressure Regulators
Tank regulator
Two stages of regulation are required:
•Retention Time reproducibility
•Stable detector performance
GC gas control
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Pressure Regulator (Flow Rate)
Inlet Pressure A
G
A
S
Flow
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Flow Controller (Flow Rate)
Constant Back
Pressure Pressure
G
A
S
Flow
Controller
Constant
Pressure Variable Back Pressure
due to Restriction More Restriction
G
A
S
Flow
Controller Same mL/min
mL/min Flow
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Instrument Flow Control Panel
Manual Pneumatics
Programmable
Pneumatic Control (PPC)
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FID Typical Gas Flows
(Pressure Regulator/Needle Valve)
FID
Needle *
Dual Valve
Hyd. Stage
Regulator 40 - 45 mL / min
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Gas Leaks
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Locating Gas Leaks
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Leak Checking
All fittings must be
checked for leaks
Shutoff gas
Leaks are bi-
bi-directional: at cylinder
gas can leak out and air
can diffuse into the gas
stream
Pressure drop technique is
the easiest and preferred
method to check for leaks: Pressure
holds - no
• Cap off all outlets leaks
• Pressurize system and
close cylinder valve
• Watch for pressure
drop on cylinder tank
Pressure
(10 min period) drops – leak
downstream
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Locating Leaks
Electronic gas detectors are
the preferred equipment for
locating leaks
Observe all manufacturer’s
precautions
An acceptable alternative is
a 50:50 solution of
isopropanol and water
Never use soap solutions to
check for leaks on GC gas
lines – fittings and tubing
become contaminated
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Leak Testing Can Cause
Contamination
Leak -Tec
Detects Leaks
Safe-
Safe-Sure-
Sure-Fast
250 mL
PYREX
Long Lasting
Non-
Non-Flammable
Non-
Non-Explosive
50:50 Mixture
4 FL OZ. (112 mL)
mL) Alcohol/Water
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Flow Measurement
10 10 10 10
Start Stop
Calibration
Marks
Bubble Time Time
at 0 at 10
Gas In 0 0 0 0
Soap
Bubble
Squeeze Bulb
Step 1 Step 2 Step 3 Step 4
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Cylinder Safety Precautions
Always properly secure gas cylinders in
place
Always have cylinders transported by a
licensed supplier
Always consult the gas safety data sheet
provided by the supplier
Always use a safety snubber on
hydrogen cylinders
Never move a cylinder without the valve
cover in place
Never place a cylinder in a high traffic
area
Do not allow gas cylinder pressure to
drop below 200 psig
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Typical Problems with Gases and
Pneumatics
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Injectors
Packed, Capillary,
Programmable Split/Splitless,
Programmable On-Column
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Packed Column
Injector
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Packed Column Injector
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Injection Port Temperature Profile
260
240
220
Degrees Celcius
200
180
160
140
120
100
80
0.25 1 3 5 7 9 11
cm
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Packed Column Injector
Wide Bore Adapter Accessory
Standard Packed Off-
Off-Column On-
On-Column
Column Position Position
p Low flow element
(1 to 20 ml/min)
p 1/16 inch adapter fitting Hourglass
Silanized
(0.46 i.d.
i.d. needle required) Glass Wool
2. Holds non-
non-volatiles and septum
debris
p Must cut column end square Adapter Adapter
Adapter
1 5/8-
5/8-inches Fitting Fitting Fitting
530 Micron 530 Micron 530 Micron
Wide-
Wide-Bore Wide-
Wide-Bore Wide-
Wide-Bore
Column Column Column
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Split/Splitless
Injector
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AutoSystem (XL)
or Clarus Gas Chromatograph
Split/Splitless Injector
Septum
Purge Carrier gas in Split
Split Vent Point
Liner
Capillary Column
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph
Ground
p Liner Portion
Ground
Portion
• 6 mm O.D. / 4 mm I.D. O-Rings O-Rings
• 6 mm O.D. / 2 mm I.D. Quartz Wool Quartz Wool
Loosely Packed Loosely Packed
p Packing
Quartz Wool
• Silanized Glass wool Tightly Packed
recommended Dimple Dimple
• Top portion loosely
packed
• Bottom portion tightly 4-mm i.d.
i.d. 2-mm i.d.
i.d. 4-mm i.d.
i.d.
Wide-
Wide-Bore Liner Narrow-
Narrow-Bore Liner Wide-
Wide-Bore Liner
packed (P/N N612-
N612-1001) (P/N N612-
N612-1002) (P/N N612-
N612-1001)
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph
Split/Splitless Injector
p Autosampler compatible and matched
p Single “O” ring seal
p Mechanically defined septum purge path
p Fixed septum purge restrictor
p 1/4 inch removable end fitting (N6100157)
p 1/16 inch reverse ferrule column connection
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph
Split/Splitless Injector
Conventional Pneumatic control
p Pressure regulated
p Digital display of column head pressure
p Needle valve for split flow
p Solenoid valve for split vent
p Fixed septum purge
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Split Injection
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Split/Splitless Injector
Effect Of Injection Speed on Area
Split Mode (fast) Split Mode (norm)
2000
1800
1600
Absolute Area (10^3)
1400
1200
1000
800
600
400
200
0
C11
C14
C17
C24
C28
C32
C36
Carbon Number C40
C44
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Splitless Injection
Mode of Operation
p Splitless mode uses narrow bore liner (2 mm i.d.)
i.d.)
p Trace analysis of high boiling compounds in solvents
p Vent opened 30-30-90 seconds after injection removes bulk of the
solvent tail, but leaves most of the sample condensed at the
head of the column
p Advantages:
Advantages:
• Good for trace analysis (less than 100 ppm)
ppm)
• Good for high boiling point compounds
• Easily automated using timed events
p Considerations:
• Limited to trace analysis
• Requires low oven temperature (below solvent) and then oven
temperature programming
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Programmed
Split/Splitless Injector
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AutoSystem (XL)
or Clarus Gas Chromatograph
Programmed Split/Splitless Injector
Septum
purge Carrier gas in
Split vent
Cooling fins
Cooling fan
Liner
Capillary column
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph
Programmed Split/Splitless Injector
p Conventional pneumatics
• Pressure regulated with screen readout and ready interlock
p Pneumatic Pressure Control
• Carrier gas controlled from instrument keypad or TotalChrom
p Operating modes:
• Oven Programming
• Inlet Programming (initial, rate, final)
• Solvent Purge
p “O” ring seal
• Silicone, Viton (250oC)
• Kalrez, (450oC)
Kalrez, graphite (450
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph
Programmed Split/Splitless Injector
p Cooling fan standard
p Compatible with 0.1 - 0.53 um columns
p Split/Splitless capability with septum purge
p 1 & 2 mm ID and On-Column glass liners shipped as
standard
p Autosampler compatible
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Sampling Valve
Sample Gas
GSV
Carrier Gas
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Gas Sampling Valve Operation
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Special Modes
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Oven
Rapid Heating and Cooling for High Productivity
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AutoSystem XL Gas Chromatograph
Oven
( Dual packed or capillary
columns
( Mixed packed or capillary
columns
( Rapid heating and cooling
( 0.1 to 45oC/min.
( Can be used with:
( LN2(-100oC) or CO2(-60oC)
( Operating range:
-100 to 450°
450°C
( Oven volume:
11 Liters (23 x 23 x 20 cm)
( Oven fan automatically shuts off
at 40oC when the oven door is
open
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem
Oven-Column Connections
1/8in Nut
& Ferrule
Column
0.10 – 0.32 i. d. Column
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Column Connections
Good Cut
Poor Cuts
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Column Connections
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Column Conditioning
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Checking Column Flow
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Detectors
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Effluent Splitting
Two Detectors
Interface
Carrier
Column Detector
Gas
1
Controls
Detector
2
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Gas Chromatography Detectors
Destructive
p Flame Ionization Detector (FID)
p Nitrogen Phosphorus Detector (NPD)
p Flame Photometric Detector (FPD)
Non-Destructive
p Electron Capture Detector (ECD)
p Thermal Conductivity Detector (TCD)
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Flame Ionization
Detector
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The Flame Ionization Detector (FID)
Hydrogen in
Jet
Assembly
Column
connection
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The Autoignite FID
Igniter
p Requires PPC gas Amplifier
control option Connection
method Extension
Detector
Fitting
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GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Ionization Detector
Manual and PPC
p Conventional pneumatics
• On/off needle valve for air
• On/off pressure regulator for hydrogen
p Programmed Pneumatic Control
• Control of hydrogen and air from
instrument keypad
p Sealed collector for easy gas measurements
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Flame Ionization Detector
Application Areas
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Flame Ionization Detector
Mode of Operation
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Flame Ionization Detector
Characteristics
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FID Gas Flows and Measurement
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FID Maintenance
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Nitrogen Phosphorus
Detector
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Nitrogen Phosphorus Detector
Collector
Bead power connection
Bead
Air in
Hydrogen in
Column connection
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Nitrogen Phosphorus Detector
Mode of Operation
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Nitrogen Phosphorus Detector
Application Areas
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Nitrogen Phosphorus Detector
Characteristics
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Flame Photometric
Detector
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Flame Photometric Detector
Optical
Filter Window Filter
Assembly Assembly
Cap
O-Ring
Glass Liner
Flame Jet
O-Ring Air In
Hydrogen In
Photomultiplier
Tube Assembly Column
Connection
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Flame Photometric Detector
Mode of Operation
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Flame Photometric Detector
Mode of Operation
p Sulfur
• Flame emits blue light when S2 species burn
• Narrow band filter for S2 wavelength
• Maximum transmittance is at 394 nm and has a
(concentration)2 response
p Phosphorus
• Flame emits yellow light when HPO species burn
• Narrow band filter for HPO wavelength
• Maximum transmittance is at 526 nm and has a linear
response
p Tin
• Flame emits pink light when Sn species burn
• Narrow band filter for Sn wavelength
• Maximum transmittance is at 610 nm and has linear
response
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Flame Photometric Detector
Application Areas
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Flame Photometric Detector
Characteristics
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Electron Capture
Detector
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Electron Capture Detector
Collector
(Anode)
63Nickel foil
(Source)
Make-up gas in
Column connection
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ECD Regulations
Handle Carefully
RADIOACTIVE
Contents_____________
No of Curies__________
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Electron Capture Detector
Mode of Operation
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ECD Makeup Flow and Measurement
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Electron Capture Detector
Application Areas
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Electron Capture Detector
Characteristics
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Electron Capture Detector
90
% Sensitivity
80
70
60
50
0
10
20
30
40
Makeup Flow 50
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ECD Maintenance
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Thermal Conductivity
Detector
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Thermal Conductivity Detector
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TCD Bridge Current Settings
Current
Setting He/H2 N2 Ar
(mA)
4 160 100 XX XX
3 120 300 XX XX
2 80 350 110 XX
1 40 350 350 350
0 Off Off Off Off
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Thermal Conductivity Detector
Mode of Operation
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Thermal Conductivity Detector
Application Areas
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Thermal Conductivity Detector
Manual and PPC
p Conventional pneumatics
• Standard flow controller and line for
reference channel
p Programmed Pneumatic Control
• Reference channel controlled from
instrument keypad
p Can be used with 0.53 and 0.32 mm columns
without make-up.
p Series connection optional
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