DETECTORS OF GAS

CHROMATOGRAPHY
AJMAL ROSHAN U P
16013
Outline
 Introduction

 Characteristics of Ideal GC detector

 Classification of GC Detectors

 Some Important GC Detectors

 Conclusion
Introduction
 GC - one of the most powerful tools in analytical chemistry which is used for qualitative and
quantitative analysis
 In GC the components of a sample are dissolved in a solvent, vaporized and injected onto the
head of a chromatographic column in order to separate the analytes by distributing the
sample between two phases: a stationary phase and a mobile phase
 Mobile phase: Chemically inert gases that carry analyte molecules through the column
 Stationary phase: either a solid adsorbent (GSC – Gas Solid Chromatography) or a liquid on
inert medium (GLC – Gas Liquid Chromatography)
 Modern GC was invented by A. J. P. Martin and R. L. M. Synge in 1941
Instrumentation
 Carries gas: Mobile phase gas, must be inert
 Flow regulator: To control flow rate
 Sample injection systems: To inject our
sample, micro syringes are used
 Column: Where separation occurs by eluting
the samples
 Oven: thermostat for the column, temperature
programming is important
 Detectors: To register the presence of a
chemical in effluent
 Data system: To record and display
chromatogram
Instrumentation
 Sample injects into the inlet where it
volatilized and carried onto the column by the
carrier gas
 Sample components by differential
partitioning in stationary and mobile phases
 Separated sample components elute from the
column to the detector to produce a signal
 Amplified signal sends to data system for
constructing chromatogram
GC Detectors
 Considered as the brain of the instrument

 Located at the end of the column

 Provides a quantitative measurement of components of the sample as they elute

 Large number of GC detectors have been designed and are commercially available
Characteristics of an ideal GC Detector
 Adequate sensitivity
 Good stability & reproducibility
 A linear response to solutes
 A temperature ranges from room temperature to at least 400 oC
 Short response time independent of flow rate
 High reliability and ease of use
 Inexpensive
 Negligible base line noise and least peak broadening
 Nondestructive of sample
 Response independent of mobile phase composition and characteristics
 Insensitive to mobile phase flow rate and also the changes in the pressure and temperature
Classification of GC Detectors
A) Based on Measuring property
 Bulk property detectors: function by measuring some bulk physical property of the column eluent
such as dielectric constant or refractive index
 Solute property detectors: function by measuring a physical/ chemical property that is unique to
solute such as UV adsorption, fluorescence or heat of combustion

B) Based on Specificity
 Non selective: Respond to all compounds coming out of the chromatographic column except the
carrier gas
 Selective: Respond to a range of compounds with common physical or chemical characteristics
 Specific: Respond only to a single chemical compound in their carrier stream
Classification of GC Detectors
C) Based on Response

 Concentration sensitive detector responds to the concentration of the analyte in the mobile phase. E.g.
TCD, ECD

 Mass sensitive detector responds to the number of analyte molecules or ions that come in contact with
the detector. E.g. FID, NPD, FPD
Some important GC Detectors
 Thermal Conductivity Detector (TCD)

 Electron Capture Detector (ECD)

 Flame Ionization Detector (FID)

 Nitrogen Phosphorus Detector (NPD)

 Flame Photometric Detector (FPD)

 Electrolytic Conductivity Detector (ELCD)

Thermal Conductivity Detector (TCD)
 One of the old GC detectors, also known as katharometer or hot wire detector
 Based on the decrease in thermal conductivity of the helium or hydrogen carrier gas brought
about by the presence of analyte molecules
 As a gas is passed over a heated filament wire (Pt, Au or W), the temperature and thus the
resistance of wire will vary according to thermal conductivity of the gas

 Four thermally sensitive resistive elements are used. A reference pair (located ahead of sample
injection chamber) and a sample pair (located immediately beyond the column)

 The pure carrier is passed over one filament, and the effluent gas containing the sample constituents
is passed over another. These filaments are in opposite arms of a Wheatstone bridge circuit that
generates a voltage as the resistance of the sensing filament changes

 If effluent contains only carrier gas resistance of the wires will be the same. But whenever a sample
component elutes, a small resistance change will occur in the effluent arm.

 Advantages: general applicability (to detect organic and inorganic species), simplicity, inexpensive,
large linear range, nondestructive (permitting collection of solutes after detection).

 Disadvantages: low sensitive

Flame Ionization Detector (FID)
 Most popular of all detectors, based on ionization of analyte in a small air/hydrogen flame.

 A few hundred volts applied between the burner tip and a collector
electrode located above the flame serves to collect the ions and
electrons.

 The ions and electrons produced are collected by a pair of biased

electrodes giving rise to a current

 The resulting current (10–12 A) is then measured with a sensitive

Pico ammeter.
 Carbonyl, alcohol, halogen and amine functional groups yield fewer ions or none at all in a flame

 Noncombustible gases such as H2O, CO2, SO2, and NOx are insensitive

 Advantages: general applicability, large linear range, simplicity, ease of use, good sensitivity (10-13
g/s), low noise, lower sensitivity toward most carrier gas and water.

 Disadvantage: destructive.
Flame Thermionic Detector
 Two stage flame ionization detector designed to give an increased specificity towards N & P
containing substances.

 Also called NPD – Nitrogen Phosphorus Detector.

 Based on the ion currents produced when mobile phase is combusted in a hydrogen flame
and then passed over a heated rubidium silicate bead

 A second flame ionization detector is mounted above the first. The two stages are divided by
a wire mesh coated with an alkali salt or base such as NaOH
 Initially the column effluent enters the lower flame, which act as a conventional FID. Normally a small current
flow in the second flame due to evaporation and ionization of sodium from the screen.

 If compounds containing N or P is burned in the lower flame, the resulting ions greatly increase the
volatilization of the alkali metal from the screen. This results in a response that is much greater (at least 100
times) than the response of the lower flame to nitrogen or phosphorus.

 Recording the signals yield a usual FID chromatogram from the lower flame and a prominent response from the
top channel if N or P containing compounds elute.

 Advantages: high sensitivity for compounds containing N and P, good linear range.

 Disadvantages: destructive, not applicable for many analytes.

Electron Capture detector (ECD)
 ECD provides trace analysis of halogenated compounds, nitriles, nitrates and compounds
with conjugated double bonds

 The sample eluate from a column is passed over a radioactive β emitter, usually nickel-63.

 An electron from the emitter causes ionization of the carrier gas and the production of a burst of
electrons. In the absence of organic species, a constant standing current between a pair of electrodes
results from this ionization process.

 Presence of organic molecules containing electronegative functional groups are particularly effective at
capturing electrons and reduces the ion current which appears as signals in chromatogram.

 Advantages: high sensitivity, selectivity towards electronegative functional groups, nondestructive.

 Disadvantages: nonlinear response under some circumstances, limited response range.

Simplified schematic diagram of ECD
Flame Photometric Detector (FPD)
 Identical to FID with the addition of a Sulfur or Phosphorus filter and a photomultiplier tube.

 Based on the radiation emitted by sulfur and phosphorus containing molecules when the eluent is
passed into a low temperature hydrogen/ air flame.

 Column effluent is mixed with air and burnt in a hydrogen rich atmosphere, producing a small
flame .

 S and P containing sample molecules are decomposed to S2 and HPO. The decomposed sample
then enters into a second flame that supplies the energy for exciting these fragments to S2* and
HPO*

 Upon relaxation these species show characteristic chemiluminescent emission and is measured
using the photomultiplier tube.
 Chromatogram of S compounds H2S, COS and CH3SH in a
propylene matrix using FPD

 The optical filter can be changed to allow the photomultiplier to view light of 394 nm for Sulphur
measurement or 526 nm for Phosphorus.
 The specific emission that results after application of a filter, is converted into current and amplified
by the photomultiplier tube. This current detects the signal.
 Advantages: Selectivity towards S and P containing analytes, good sensitivity.
 Disadvantage: destructive, limited applicability.
Electrolytic Conductivity Detector (ELCD)
 Also known as Hall detector which can be used to detect halogens, sulfur, or nitrogen.

 ELCD consists of two different components, the furnace (500-1000 oC) and the conductivity cell having a
solvent, typically 1-propanol.

 Organic molecules are converted to smaller molecules with the use of nickel wire via catalytic
oxidation/ reduction or pyrolysis.

 These reaction products are swept from the reactor and mixed with the solvent 1-propanol . Electrical
conductivity of the solvent is measured

 The difference between the conductivity of the pure solvent and the solvent + reactants is
monitored.
Other GC Detectors
Detector Applicable Samples Sensitivity
All organic substances; with ultrapure Argon
Argon ionization (β-ray) Very good, 0.1-100ng
carrier gas
Specific for N & P containing substances
Rubidium silicate bead Excellent
Nearly all substances but inert gases and Excellent down to
Vacuum UV absorption
nitrogen pg levels
All molecules except neon: with He as carrier
Helium ionization Very good
gas
Specific for sulfur compounds; by producing
Sulfur chemiluminescence Excellent
SO
Specific for nitrogen containing compounds;
Nitrogen chemiluminescence Excellent
by producing NO
Excellent, ppb to
Photoionization Volatile organic compounds
10000 ppm
Dry electrolytic conductivity Specific for halogens Very good
Excellent down to fg
Pulsed discharge (ionization) Universal
& pg levels
Dielectric constant O, N, H, CO, CO2, CH4, NO2, NO, SO2 Good
Conclusion
 Very few GC detectors have been introduced commercially and become popular over the last
decade and the four detectors – FID, NPD, ECD and TCD are still the most commonly used as
they were 20 years ago.

 Developments in the GC technique is now relatively slow and as an analytical technique it

might be aid it has reached a “steady state”

 Many fields such as pharmaceuticals, cosmetics and even environmental toxins are making
use of GC.

 Detection of the amount of chemicals and components in a given sample gives a huge
advantage in studying the effects of human health and of the environment as well.
References
 Martin A. J. P, Synge R. L. M. A new form of chromatogram employing two liquid phases.
Biochem. J. 1941, 35, 1358

 Skoog D. A, West D. M, Holler F. J, Crouch S. R. Gas Chromatography. Fundamentals of

Analytical Chemistry, Ninth Edition; Mary Finch: Brooks/Cole: USA, 2014; pp 892-897.

 Skoog D. A, Holler F. J, Crouch S. R. Gas Chromatography. Principles of Instrumental

Analysis, Sixth Edition; Thomson Brooks/Cole: USA, 2007; pp 792-796.

 Scott R. P. W. Chapter 1 History, Function and Classification of Detectors. Journal of

Chromatography Library, Volume 11, 1977, pp 1-4.
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