You are on page 1of 93

Fundamental

Gas Chromatography

1
GC Fundamentals Rev B 5/23/2006 PerkinElmer
abcit

What is
Gas Chromatography?
A Separation Science

2
GC Fundamentals Rev B 5/23/2006 PerkinElmer
What is analyzed with a Gas Chromatograph?

Air, Water, Wastewater


Pesticides, Herbicides
Cosmetics, Hand Lotions, Soaps
Crude Oil, Gasoline, Jet Fuel, Natural Gas, Crude Oil
Pharmaceuticals
Inks, Dyes (Food Packaging)
Flavors, Fragrances
Food Products (Cheese, Chocolate, etc.)
Beverages (Beer, O.J., Soda, Whisky, Vodka,Wine)
Rubber and Plastics
Fabrics Gas Chromatography is used to test or analyze
Blood thousands of products and materials everyday.

3
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Chromatography
A Separation Technique

Physical Separation of Components


Gases - Liquids - Solids
Organic and Inorganic

4
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Chromatography, Basic Steps

Vaporization of the sample. Injector


Transfer of sample onto the column. Carrier Gas
Separation of sample. Column
Detection of Ions. Detector
Collection of Results. TotalChrom
Evaluation of Data. Analyst

5
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Chromatography Gives

Identity and Quantity

= + + +

Sample Component A Component B Component C

6
GC Fundamentals Rev B 5/23/2006 PerkinElmer
The Chromatographic Process

Column
Tubing

Mobile Phase Carrier Gas

Sample
Stationary Phase
(Liquid Phase)

7
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Column Chromatography

The Separation Process


Liquid Phase
Carrier Phase
Time 1

Liquid Phase
Carrier Phase
Time 2

Liquid Phase
Carrier Phase
Time 3

8
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Chromatographic Results
Plot of Component
Concentration
High Concentration
Component Bands
Low Concentration

Component Molecule
Concentration

9
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Component Peaks
Peak Areas are Determined By
Components and Concentration

Time Sample Molecule Concentration

10
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gases and
Gas Controls

11
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

Use Ultra-High Purity gases only - 99.995% recommended.

12
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Typical Carrier Gases

Carrier Gas Symbol Detector Type


He, N2, H2 FID Flame Ionization

N2, Ar/Methane
Ar/Methane ECD Electron Capture

He, H2, N2*, Ar * TCD Thermal Conductivity

He, N2, H2 PID Photoionization

He, N2, H2 ELCD Electrolytic Conductivity

He, N2, NPD Nitrogen Phosphorus

He, N2, H2 FPD Flame Photometric

He MS Mass Spectrometer

* Low Current Setting Only

13
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

14
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

15
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Pressure Regulators

Pressure regulators are used to:


• Regulate gas tank supply
• Control carrier and detector
gases in the GC

Tank regulator
Two stages of regulation are required:
•Retention Time reproducibility
•Stable detector performance
GC gas control

16
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Pressure Regulator (Flow Rate)

Inlet Pressure A
G
A
S
Flow

Same Inlet Pressure B More Restriction


Due to Increase
G In Temperature
A Less
S Flow

Increase Inlet PressureC Same Restriction


G as A
A More
S
Flow

17
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

18
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Instrument Flow Control Panel

Manual Pneumatics
Programmable
Pneumatic Control (PPC)

Operator manually sets all gases

Gases set and controlled from


TotalChrom or GC

19
GC Fundamentals Rev B 5/23/2006 PerkinElmer
FID Typical Gas Flows
(Pressure Regulator/Needle Valve)

Dual 400 - 450 mL / min


Air Stage
Regulator Needle
Valve

FID
Needle *
Dual Valve

Hyd. Stage
Regulator 40 - 45 mL / min

*Needle Valve with Pressure Regulator

20
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Leaks

•Gas leaks are a frequent


problem in GC
•When a leak is suspected,
check the last thing you
changed first
•Common areas for leaks
Septum
Column
Gas Cylinder
Check All Connections for Leaks

21
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Locating Gas Leaks

Check all fittings for leaks


• IPA and water mix
• leak detector
Pressure drop test

22
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

23
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

24
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

25
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

26
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

27
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Typical Problems with Gases and
Pneumatics

Gas in tank is too low in purity


Contaminated gas, lines or pneumatic controls
Dirty or contaminated gas line filters/scrubbers
Defective pneumatic control
• poor control or regulation
• dirty or clogged from contaminated gas

28
GC Fundamentals Rev B 5/23/2006 PerkinElmer
abcit

Injectors
Packed, Capillary,
Programmable Split/Splitless,
Programmable On-Column

29
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Packed Column
Injector

30
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Packed Column Injector

p Terminates in 1/8 inch column fitting


p 1/4 inch column adapter available as an accessory
p 2.75 mm I.D. glass liner (700 uL)
uL)
p Conventional pneumatics
• Flow control with column head pressure gauge
• Flow control with optional digital flow readout
p Programmed Pneumatic Control
• Electronic flow control from instrument keypad Carrier
Temperature range: 0=Off, 100 to 450° Gas In
p 450°C
p Used to vaporize sample and transfer onto
column
p With headspace acts as interface to oven &
column
p Always heated to avoid sample condensation

31
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

32
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

p 4 mm I.D. hour glass liner Wide-


Wide-Bore
Glass Wide-
Wide-Bore
p Direct injection Standard
Liner
Injector
Liner
Glass
Injector
p On-
On-column mode Liner

Silanized
(0.46 i.d.
i.d. needle required) Glass Wool

p Glass wool packing


1. Improves autosampler precision Hourglass

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

33
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Split/Splitless
Injector

34
GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph
Split/Splitless Injector

Septum
Purge Carrier gas in Split
Split Vent Point

Liner

Capillary Column

35
GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph

Split/Splitless Injector Splitless Packing Split Packing

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)

(1in. or 2.5 cm.)

36
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

37
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

Programmed Pneumatic Control

p Carrier gas controlled from instrument keypad

“O” ring seal


p Silicone, Viton (250oC)
p Kalrez, (450oC)
Kalrez, graphite (450

38
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Split Injection

p Split mode uses wide bore liner (4 mm i.d.)


i.d.)
p Splitting of sample allows deposit of small fractions of a
microliter (uL)
uL) in the column
p Prevents overloading of the capillary
p Large part of sample vented (Carbon trap on vent)
p Sample injected into glass wool to allow uniform mixing with
carrier gas
p Separate gas line used for septum purging
p Used for concentrated samples
p Linear to about C30 hydrocarbons
p Septum Purge
• Continuous flow
• Linear (10 psig—
psig—2 mL/min,
mL/min, 20 psig—
psig—4 mL/min)
mL/min)

39
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

40
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

41
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Programmed
Split/Splitless Injector

42
GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem (XL)
or Clarus Gas Chromatograph
Programmed Split/Splitless Injector

Septum
purge Carrier gas in
Split vent

Cooling fins
Cooling fan
Liner

Split point Heater block

Capillary column

43
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

44
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

45
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Sampling Valve

Sample Gas
GSV

Injector Column Detector

Carrier Gas

46
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Gas Sampling Valve Operation

Position 1 (Load) Position 2 (Inject)

47
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Special Modes

p Flame Out Detection


• When lit, the FID is sensitive to adjustments to combustion
gas flows
• When unlit, the signal is unaffected by flow variations
• Flame Out Test automatically pulses the H2 flow rate before
each run and checks to see if the detector signal changes
p Sleep Mode
• Automatic shutdown when the GC is idle
• Similar to MS Windows Screen-
Screen-Saver
– User enters a delay time and a Method number
– ‘Sleep’
Sleep’ Method is applied when the GC is idle for this time
period
• Saves gases, protects column and GC

48
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Oven
Rapid Heating and Cooling for High Productivity

49
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

50
GC Fundamentals Rev B 5/23/2006 PerkinElmer
AutoSystem
Oven-Column Connections

Injector-Side Connection Detector-Side Connection

INSIDE OF AUTOSYSTEM OVEN


1/16 “Column Nut Detector
& Ferrule Fitting
(optional)

1/8in Nut
& Ferrule

Column
0.10 – 0.32 i. d. Column

Injector insertion distances: Detector insertion distances:


Capillary Split/Splitless
Split/Splitless – 44 -- 51 mm FID – 70 mm TCD – 103 mm
PSSI – 38 44 mm ECD – 64 mm NPD – 77 mm

51
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Column Connections

Place nut and ferrule over end of column first


Cut 1cm from column end with scribe
Inspect end for clean cut with magnifying glass

Good Cut

Poor Cuts

52
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Column Connections

Septa can be used to mark column for correct


insertion dimension
Connect fitting with septa on column inserted to
back of column nut

1/8in Column Nut 1/8in Graphite


Septa Ferrule

53
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Column Conditioning

Disconnect column detector end


Confirm carrier flow through column
Program oven temperature from ambient at 5oC/min
to 25oC above the maximum temperature of your
analytical method and hold for one hour
• Packed columns should be condition for 24 hrs.
When finished conditioning re-connect column to
detector

54
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Checking Column Flow

Typical column flow for 0.25 mm, 30 meter column:


~1.3 mL/min with a pressure of 15.0 psig
Use a good electronic flow meter or bubble flow
meter to measure column flow rate
Can measure column flow through detector, but
small leaks may indicate a lower than actual flow,
and combustion and makeup gases must be off
Leak test the entire system by plugging the detector
end of the column with a piece of septum and
performing a pressure-drop test (cut column again
before re-installing in detector)

55
GC Fundamentals Rev B 5/23/2006 PerkinElmer
abcit

Detectors

56
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Effluent Splitting
Two Detectors

Interface
Carrier
Column Detector
Gas
1
Controls

Detector
2

57
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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)

58
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Ionization
Detector

59
GC Fundamentals Rev B 5/23/2006 PerkinElmer
The Flame Ionization Detector (FID)

p Hydrogen and air


required for
Collector
combustion gases Knurled
Ring
p FID jet has Nozzle
Polarizing
receiver “tail” Clip

attached Flame jet Air in

Hydrogen in
Jet
Assembly
Column
connection

60
GC Fundamentals Rev B 5/23/2006 PerkinElmer
The Autoignite FID

Igniter
p Requires PPC gas Amplifier
control option Connection

p Most parts not


interchangeable Polarizing
Pin
with earlier FID Collector

p Complete control Flame Jet Air In

of FID from GC Flame Jet


Hydrogen In

method Extension
Detector
Fitting

61
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

62
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Ionization Detector
Application Areas

p Most sensitive detector for the analysis of


organic compounds
p Determination of ppm to % levels of
petrochemical compounds
p Detection of trace levels organic pollutants in
air
p Food and Flavor analysis, essential oils, fatty
acids, antioxidants
p Analysis of potable liquids, beers, wines and
spirits

63
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Ionization Detector
Mode of Operation

p Organic compounds containing C-H bonds are


combusted in the air/hydrogen flame to
produce ions
p Ions, under the influence of polarizing voltage,
(-200v) are collected at the anode (collector
electrode)
p Resultant detector current (10-6 -- 10-12 A)
measured at amplifier

64
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Ionization Detector
Characteristics

p Requires combustion gases, air and hydrogen


p Compatible with carrier gas flow rates 0.5-
50mL/min.
p Linearity greater than 106
p MDQ of less than 3 x 10-12 g C/sec
p Operating temperature: 100°C to 450°C
p Amplifier filters: 50, 200, 800 (software
selectable)
p Terminates in 1/8 inch fitting for column
connection

65
GC Fundamentals Rev B 5/23/2006 PerkinElmer
FID Gas Flows and Measurement

p GC Combustion Gas Flows:


• H2 Flow - 45mL
p Use a good flow meter capable of
measuring gas flows up to 500 mL/min
• Air Flow - 450mL
p Turn on one gas flow at a time and measure
through FID vent

66
GC Fundamentals Rev B 5/23/2006 PerkinElmer
FID Maintenance

p Parts requiring replacement if dirty,


contaminated or corroded:
• jet assembly
• collector assembly
• nozzle and ceramic insulator
• jet contact spring
p Polarizing voltage must be present (-200
volts DC) and have good contact
p Ceramic insulator for polarizing voltage must
be clean

67
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Nitrogen Phosphorus
Detector

68
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Nitrogen Phosphorus Detector

Collector
Bead power connection

Bead
Air in

Hydrogen in

Column connection

69
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Nitrogen Phosphorus Detector
Mode of Operation

p Glass bead containing cesium is electrically


heated to the point it emits electrons
p Hydrogen and air around hot bead form a
hydrogen plasma.
p Stable intermediates containing N or P are
formed in the plasma which then capture the
electrons emitted from the bead to form ions
p Ions are collected at the anode as with the FID

70
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Nitrogen Phosphorus Detector
Application Areas

p Most sensitive detector for the analysis of


nitrogen and phosphorus containing
compounds
p Determination of ppm levels N or P
compounds in water/organic matrices. EPA
507, 509
p Detection of low levels N containing drugs
and pharmaceuticals.
p Food and Flavor analysis of “off odors”
caused by N compounds

71
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Nitrogen Phosphorus Detector
Characteristics

p Linearity greater than 104


p MDQ of less than 5 x 10-13 g N/sec
MDQ of less than 5 x 10-14 g P/sec
p Operating temperature: 100°C to 450°C
p Bead design assembly offers quick and
easy change with no adjustments

72
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Photometric
Detector

73
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

74
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Photometric Detector
Mode of Operation

p Organic compound burned in hydrogen/air flame


p Sulfur and phosphorus atoms combusted and emit
light at specific wavelengths
p By the use of specific optical filters the S or P
emissions are isolated and measured with a
photomultiplier tube to produce a signal proportional
to the amount of S or P

75
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

76
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Photometric Detector
Application Areas

p Most sensitive detector for the analysis of


sulfur/phosphorus containing compounds
p Determination of ppm levels S/P compounds in
organic matrices
p Detection of trace levels S/P pollutants in air/water
EPA 8141A
p Food and Flavor analysis of “off odors” caused by S
compounds

77
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Flame Photometric Detector
Characteristics

Operating temperature 250°C to 450°C

Linearity Sulfur: 102 (log-log) square law


response Phosphorus: 103 linear response
-11
MDQ Sulfur: 1 x 10 gS/sec
(thiophene)
Phosphorus: 1 x 10-12gP/sec
(tributylphosphate)

Selectivity Sulfur: 104:1


Phosphorus: 105:1

78
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Electron Capture
Detector

79
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Electron Capture Detector

Collector
(Anode)
63Nickel foil
(Source)

Make-up gas in

Column connection

80
GC Fundamentals Rev B 5/23/2006 PerkinElmer
ECD Regulations

Handle Carefully
RADIOACTIVE
Contents_____________
No of Curies__________

81
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Electron Capture Detector
Mode of Operation

p Constant current, closed loop, pulse frequency


modulated
p Ionization produced by 63Nickel foil
p Cell current (1na) maintained by pulsing the
anode voltage
p Electron absorbing compounds in cell reduce
electron population and hence the cell current
p Cell current restored by an increase in pulse
frequency
p Change in frequency is measure of
concentration of component

82
GC Fundamentals Rev B 5/23/2006 PerkinElmer
ECD Makeup Flow and Measurement

p Makeup gas is required for proper ECD


operation
p Use UHP grade (99.995%) N2 gas with filter
p Measure makeup flow at detector vent
p Total flow through detector should be 30mL
(column flow + makeup flow)
• 8500 - set makeup pressure at 44psi
• AutoSystem - adjust needle valve to
achieve 30mL total flow through ECD

83
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Electron Capture Detector
Application Areas

p Most sensitive detector for the analysis of


electrophilic compounds
p Determination of ppb levels chlorinated
pesticides
p Detection of trace levels PCB’s
(polychlorinated biphenyls)
p Trace levels nitrous oxide N2O in air
p Determination of diketones in beer

84
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Electron Capture Detector
Characteristics

p Linearity greater than 104


p MDQ of less than 50 fg of lindane or
perchloroethylene
p Operating temperature: 100 to 450°C
p Make-up gas required for capillary columns
p 850 uL internal cell volume
p 63Nickel foil source

p Terminates in 1/8 inch fitting for column


connection

85
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Electron Capture Detector

ECD Makeup FLOW vs SENSITIVITY


100

90
% Sensitivity

80

70

60

50
0
10
20
30
40
Makeup Flow 50

86
GC Fundamentals Rev B 5/23/2006 PerkinElmer
ECD Maintenance

p Bake out detector when background is high


• remove column from detector
• cap detector inlet and set makeup flow at 60mL
• bake detector at 450 deg C (overnight)
p Requires cleaning and refoiling after several
years of use
p Clean anode if sensitivity is low
• remove collector and soak anode in hexane 10 min
p Perform wipe tests according to local requirements
p Observe all license restrictions and requirements
when discarding ECD cells or sending out for re-
foiling

87
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Thermal Conductivity
Detector

88
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Thermal Conductivity Detector

89
GC Fundamentals Rev B 5/23/2006 PerkinElmer
TCD Bridge Current Settings

Maximum Temperature Setting (°C)

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

90
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Thermal Conductivity Detector
Mode of Operation

p Measures difference in thermal conductivity


between carrier gas and carrier gas plus
components.
p Four filaments are connected in a Wheatstone
bridge two reference, two sensing.
p Presence of component changes resistance of
filaments in sensing channel unbalancing the
bridge. This results in a signal proportional to
concentration of the component in the gas
stream.

91
GC Fundamentals Rev B 5/23/2006 PerkinElmer
Thermal Conductivity Detector
Application Areas

p Most sensitive detector for the analysis of


inorganic gases
p Determination of % to ppm levels of most
permanent gases
p Analyses requiring packed columns and %
levels of organic compounds

92
GC Fundamentals Rev B 5/23/2006 PerkinElmer
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

93
GC Fundamentals Rev B 5/23/2006 PerkinElmer

You might also like