GAS CHROMATOGRAPHY-

MASS SPECTROMETRY (GC-

MS)
 Content
 INTRODUCTION
 HISTORICAL BACKGROUND OF GC-MS
 PRINCIPLE
 INSTRUMENTATION
• GAS CHROMATOGRAPHY
• INTERFACE
• MASS SPECTROMETER
 WORKING
 LIMITATIONS
 APPLICATION
 CONCLUSION
 REFERENCES
 INTRODUCTIO
N
HYPHENATE
D
TECHNIQUES

 Gas chromatography-mass spectrometry (GC-MS) is the synergistic

combination of two analytical method to separate and identify different
substances within a test sample.

 Gas chromatography separates the components of a mixture in time.

 Mass spectrometer provides information that aids in the identification and

structural elucidation of each component.
 Gas Chromatography-Mass Spectrometry
(GC-MS)
GAS
GAS MASS CHROMATOGRAPHY
CHROMATOGRAPHY SPECTROMETRY -MASS
SPECTROMETRY

Separated mixture of
chemicals so each can A Chemical Analysis
be identified Technique combining two
individually instruments to provide
for powerful separation
and identification
Identifies capabilities
(detects)chemicals
based on their molecular
weight or mass
• Roland Gohlke and Fred mcLafferty introduce use of MS
as detector of GC in 1950s.

• Miniaturized computers has helped in the simplification of

instrument.

• In 1968, the Finnigan Instrument Corporation delivered the

first quadrupole GC-MS.

• By the 2000s computerized GC-MS instruments using

quadrupole technology had become essential.

• In 2005 GC tandem MS-MS have been introduced.

 The sample solution is injected into the GC inlet where it is
vaporized and swept onto a chromatographic column by the
carrier gas.

 The sample flows through column and compounds are

separated by virtue of their relative interaction with the
coating of the column and the carrier gas.

 Latter part of column passes through a heated transfer line

and ends at entrance to ion source where compounds eluting
from the column are converted to ions and detected
according to their mass to charge m/z ratio.
 INSTRUMENTATION LAYOUT

Gas Interface Mass Data

chromatography • Jet Interface spectrometer system
• Carrier gas • Direct Capillary • Ion source
• Pneumatic control Infusion Interface • High-vacuum
• Injector • Watson-Biemann system
• Column effusion separator • Mass
• Oven analyzer
• Ion collector

Fig : Principle of GC-MS

1. Carrier
Gas : as mobile phase supplied in the steel tank under high
 Served

pressure.
 At pressure of 40-80 psi this passes into flow controllers.
 Example- nitrogen, helium; hydrogen and argon can also be used.

 Requirements –
 Inert
 Column requirements
 Detectors
 Purity- better than 99.995%
 Cost effective & available
2. Pneumatic
Control
 : is regulated to the correct pressure and then fed to the required
Gas supply
part of instrument.
 Older instruments – manual pressure control via regulators.
 Modern GC instruments – Electronic Pneumatic pressure controller.

3. Oven :
 Temperature programmable, typically range from 5°C - 400°C but can go as
low as -25°C with cryogenic cooling.
4. Sample Injection
Port : is made to vaporized rapidly before entering to
 Sample
column.
Various kind of injectors :
 Packed column injectors


 Split injection

 Splitless injection

 Programmed Split/Splitless injection

 Programmed On-Column injector

5. Column :
 Two kinds of column used :
 Packed column
 Capillary column
 Gas chromatograph GC-MS utilizes capillary column.
 Here, stationary phase has been chemically bonded to the fused silica, e.g.,
DB-5.
 Packed  Capillary
Columncommonly
• Less :- used, Column of:- long
• Consist capillary
diameter of 2-3 mm and length of
having tubing
0.5-10 m. 10-100 m in length.
• Manufactured from steel or glass, • Made up from stainless
internal wall is treated to avoid steel & coil.
catalytic effect with the sample. • Shorter columns - for fast analysis
• They can withstand a carrier gas • resolution
Larger separation
columns – for
flow rate within range high
10- 40ml/min.
6.
Detectors
 Simple and :reliable
 Sensitive to electronegative groups (halogens)
 Largely non-destructive
 Limited dynamic range (10²)
 Mass sensitive detectors
-Thermal Conductivity Detector (TCD)
-Flame Ionization Detector (FID)
-Electron Capture Detector (ECD)
 MASS SPECTROMETER

 “ Mass spectrometry is a technique used for measuring the molecular weight

and determining the molecular formula of an organic compound.”
 In general a mass spectrometer consists of
 An ion source
 High-vacuum system
 A mass-selective analyzer
 An ion collector
 Data system
 Ionization Method Typical Analytes Sample Mass Method
Introducti Highligh
on Rang ts
e
Chemical Ionization (CI) Relatively small, GC or Upto Soft method,
volatile liquid/solid molecular ion peak
probe 1000 [M+H] +
Daltons
Electron Impact Relatively small, GC or Upto Hard method,
Ionization (EI) volatile liquid/solid versatile, provides
probe 1000 structure info
Daltons
Electrospray Ionization Peptides, proteins, Liquid Upto Soft method, ions
(ESI) nonvolatile chromatograph 200000 often multiply
y Daltons charged
Fast Atom Bombardment Carbohydrates, Sample mixed in Upto Harder than ESI or
(FAB) organometallics, viscous matrix 6000 MALDI
peptides, Daltons
nonvolatile
Matrix Assisted Laser Peptides, proteins, Sample mixed in Upto Soft method, very
Desorption Ionization nucleotides solid matrix 500000 high mass
(MALDI) Daltons
 Mass Selective
Analyzer
• They deflects ions down a curved tubes in a magnetic fields based on their
kinetic energy determined by the mass, charge and velocity.
• The magnetic field is scanned to measure different ions.

Mass Analyzers

Quadrupole Ion Trap Time of flight

 Quadrupole
•Analyzer :
Also known as ‘Hewlett-Packard’ or ‘Mass Selective Detector’.
• In quadrupole mass analyser a set of four rods are arranged parallel to the
direction.
• Only m/z is been determined and stable oscillation takes place.
• Ions travels in quadrupole axis with cork screw type of trajectory.
• It functions as a mass filter
 Ion Trap Mass
Analyzer : analyzer operates by similar principles where it
The ion trap mass
consists of circular ring electrode and two end caps that form a chamber.
 AC or DC power along RF potential is applied between the cups and the
ring electrode.
Ions entering into Trapped by Ions oscillate in concentric
chamber electromagnetic fields trajectories
Resonant Ejection
 Time-of-flight
Analyzer :
 The time-of-flight (TOF) analyser uses an electric field to accelerate the
ions through the same potential.
 Then it measures the time take to reach the detector.
 If the particles all have the same charge, the kinetic energies will be
identical and their velocities will depend upon only on their masses.
 Data Handling

 Mass spectrometers employ computer control of same functions and

also use a computerised display and output.
 It is used to identify and measure the concentration of one or more
analytes in a complex mixture
 Advantages –
 Amount of data generated is very large
 It stores every sec for upto 90 min.

MASS SELECTED ION

CHROMATOGRAM MONITORING
S
GC TRACE OF A THREE COMPONENT MIXTURE. THE
MASS SPECTROMETER GIVES A SPECTRUM FOR
EACH COMPONENT
Consider the mass spectrum of CH4 below:
 LIMITATIONS
• Only compounds with vapour pressure exceeding about 10-10 torr can be
analysed by gas chromatography-mass spectrometry (GC-MS).

• Determining positional substitution on aromatic ring is often difficult.

• Certain isomeric compounds cannot be distinguished by mass spectrometry.

• Non-volatile matrices require additional preparation

(extraction, outgassing, etc.)

• Atmospheric gases are challenging (CO2, N2, O2, Ar, CO, H2O).
 Applications of GC-MS
Petrochemical and hydrocarbon analysis

Geochemical research

Forensic (arsons, explosives, drugs, unknowns)

Environmental analysis

Pesticide analysis, food safety and quality

Clinical toxicology
Food, beverage and perfume analysis
 CONCLUSION

 As we can see, GC-MS is used both in qualitative and quantitative

measurement.
 Being hyphenated technique, the cost of GC-MS becomes very high.
 Nowadays, cost is also cheaper than before as quadrupole and ion trap
instruments are used, which does not only save space but also save
manufacturing cost.
 GC-MS is an analytical method of increased sensitivity and reliability even
in very small quantities (ng).
 Braun R., Introduction To Instrumental Analysis, Second
Edition, PharmaMed Press, Hyderabad, Page no. 251-270.

 Chatwal G.R., Anand S.K., Instrumental method of Chemical

Analysis, Himalaya Publishing House, Fifth Edition-2012,
New Delhi, Page no. 420-449.

 Gohlke R.S.(1959), Analytical Chemistry, 36, Page no. 759-

764.
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