Detectors

In This Section, You Will Learn:

Identifying the most common GC detectors used Identifying detector response characteristics Identifying the operational consideration of the TCD Identifying the operational considerations of the FID Comparing the response of the TCD and FID detectors

GC Detector: A Definition

A GC Detector is a device which senses the presence of a component different from the carrier gas, and converts that information to an electrical signal. Thermal Conductivity Detector (TCD) Flame Ionization Detector (FID) Electron Capture Detector (ECD) Nitrogen Phosphorus Detector (NPD) Flame Photometric Detector (FPD) Electrolytic Conductivity Detector (ELCD, HALL) Photoionization Detector (PID) Mass Selective Detector (MSD) Infrared Detector (IRD) Atomic Emission Detector (AED)

Detector Response Characteristics

Sensitivity:

The response per amount of sample, that is, the slope of the response/amount curve. The minimum amount on the curve is defined as the minimum detectable level (MDL). A measure of which categories of compounds will give a detector response.

Selectivity:

Dynamic Range: The range of sample concentrations for which the detector can provide accurate quantitation.

Comparison Of GC Detectors
TCD FID ECD AED PID NPD (N) NPD (P) FPD (S) MSD ELCD ELCD 10-15 fg pptrillion 10-12 pg ppb 1 ppm = (SIM) (X) (S or N) 10-9 ng ppm 1 ng 1 L = 10-6 g ppthousand 1 mg Liter = 10-3 mg percent 1 L Liter (SCAN) IRD

Increased Sensitivity With Capillary Columns

Packed Columns Area = 2600 Height = 5 Noise = 1

Capillary Columns Area = 2600 Height = 10 Noise = 1 Sensitivity = Signal/Noise Ratio

S/N = 5

S/N = 10

Capillary Columns and Detector Selectivity

FID

ECD

NPD (P)

Dynamic Range
Dynamic range is a measure of response vs. Quantity Response is the signal produced by the sample.
Dynamic Range Response increases reproducibly with increased quantity.

Response

Quantity

Linear Dynamic Range Response increases proportionally with increased quantity. Response

Quantity

Non-linear response, as long as it is reproducible, can be dealt with using non-linear calibration techniques.
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Operating Conditions For Detectors

Sensitivity Range

Detector

Typical Samples

Gas Flow Rates (mL/min.) Carrier + Make-up Hydrogen 30-40 n.a. n.a. Air 200-500 n.a. n.a.

FID TCD ECD

Hydrocarbons Anything other than carrier gas Organohalogens Chlorinated solvents & pesticides Organonitrogen & Organophosphorus

10-100 pg 10 ppb-99%

20-60

5-100 ng 15-30 10 ppm-100% 0.05-1 pg 30-60 50 ppy-1 oom 0.1-10 pg 20-40

NPD

1-5

70-100

Thermal Conductivity Detector

The TCD is a nondestructive concentration sensing detector. A heated filament is cooled by the flow of carrier gas.

FLOW
When the carrier gas is contaminated by sample, the amount of cooling changes. The difference in cooling is used to generate the detector signal.
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Single Filament TCD

COLUMN flow enters the center of three ports. AUXILLARY, or make-up flow sheathes the column minimizing diffusion at the end of the column. REFERENCE flow is directed to either one of the outside ports into the detector cell. Which port is determined by the SWITCHING SOLENOID.

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Selecting the Reference Gas Flow Rate

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Operating the TCD

Recommended Flow Rates
Gas Type Carrier Gas (hydrogen, helium, nitrogen) Reference (same gas type as carrier) Capillary Makeup (same gas type as carrier) Flow Range Packed, 10-60 mL/min. Capillary, 1-5 mL/min. 15-60 mL/min. See previous page to select value. 5-15 mL/min. capillary columns 2-3 mL/min. packed columns

Recommended Detector Temperature If < 150 C, cannot turn on filament. 150 C to 200C - filament is at low setting >/= 200 C - filament is at high setting. Detector temp should be 30 - 50 C > highest oven temp.
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Typical Pressure/Flow Relationships

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TCD Troubleshooting/Maintenance
Check Pressures/Flows Thermal Cleaning:
TCD can become contaminated with deposits from column bleed or dirty samples. Symptoms include:
wandering baseline increased noise level changes in response of reference sample

Replace the detector.

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Flame Ionization Detector Schematic

Air Inlet Capillary Column End-Position (1-2 mm from Top of Jet) H2 Inlet + Make-Up

FID Detector Assembly

Jet

Exit End of Column

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Flame Ionization Detector

+ CHO H0 2 + CHO CO 2 H0 2 H0 2 CO 2 H0 2 CHO+ + CHO CO 2 + CHO

2 2

H CH CH CH CH CH 4

2 2

The FID is a destructive, mass sensing detector. Cations generated in the flame are counted and produce the detector signal. Analytes that have the greatest number of low oxidation state carbons produce the largest signal.

H H H H H

H 4 H 4 4 4 4 H H H

2 2 2

2 2

Column
2 2

CH 2

Jet

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Compounds with Little or No FID Response

Rare Gasses Nitrogen Oxides Silicon Halides H2O Perhalogenated cpds

NH3 H2 CO CO2

CS2 COS O2 N2

HCOH HCOOH

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FID Response
en To
10

lu

ol

io n

Fo

H H C H OH H

rm

Ac id Ac et ic

ic

H C H

H C H OH H

M et ha no l Et ha n

Pr op

Relative Response (by wt.)

ic

ta n

an o

ex

ic

H C H

H C H

ol Bu

H C H

H C H OH

Methanol

Ethanol

Butanol

Response is proportional to the number of carbon-hydrogen bonds.

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ex

an o

FID Variables
Kr

Carrier Gas Selection Sensitivity vs. MW of Gas

Ar He

N2

Gas (mw)

Sensitivity vs. Hydrogen Flow (Carrier Gas and2Air Held Constant)

H2 Flow

Sensitivity vs. Air Flow (Carrier Gas and Hydrogen Flow Held Constant)

Air Flow

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FID Pneumatics (EPC)

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Operating the FID

Recommended Flow Rates
Gas Type Carrier Gas (hydrogen, helium, nitrogen) Packed Columns Capillary Columns Detector Gasses Hydrogen Air Column plus Capillary Makeup 10-60 mL/min. 1-5 mL/min. 24-60 mL/min. 40 mL/min. Flow Range Suggested Flow

200-600 mL/min. 450 mL/min. 10-60 mL/min. 50 mL/min.

Recommended Detector Temperature If < 150 C, flame will not light. Detector temp should be 20 C > higher than oven temp.
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Typical Pressure/Flow Relationships for the FID

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FID Exploded View

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FID Jet Selection

Jets for the Capillary-Optimized FID
Jet Type Capillary High-Temp (use with simulated distillation) Part No. G1531-80560 G1531-80620 Jet Tip I.D. 0.29 mm (0.011 in.) 0.47 mm (0.018 in.)

Jets for the Adaptable FID

Jet Type Capillary Packed Packed Wide-Bore (use with high-bleed applications) High-Temperature (use with simulated distillation) Part No. 19244-80560 18710-20119 18789-80070 Jet Tip I.D. 0.29 mm (0.011 in.) 0.47 mm (0.018 in.) 0.030 in.

19244-80620

0.47 mm (0.018 in.)

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FID Troubleshooting and Maintenance

Typical Problems
Flame Out Spiking Low Sensitivity Noise Drift

FID Troubleshooting
Check Pressures/Flows Check Background signal Inspect Flame Check Electrometer Connections (spring) Check O-Rings

FID Maintenance

Clean or replace the jet Clean the collector Replace the igniter assembly

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Lab Exercises

The Students should perform the following lab exercises: Lab 1: Lab 2: Thermal Conductivity Detector Performance Flame Ionization Detector Performance

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