GAS CHROMATOGRAPHY-

MASS SPECTROSCOPY

Prepared By:
Linta Samim
CONTENTS
• Introduction.
• Gas Chromatography.
• Types of Chromatography.
• Principle of Separation.
• Process
• Career gas
• Injection port
• Column unit
• Interface
• Open Split Interface
• Jet Separator
• Mass Spectroscopy
• Instrumentation
• Working of MS
• Ion Source
• Mass Analyzer
• Detector
• Mass Spectrum
• Application of GS-MS
• Limitations
INTRODUCTION
• Gas chromatography-mass spectrometry is actually two
techniques that are combined to form a single method of
analyzing mixtures of chemicals.
• Gas chromatography separates the components of a
mixture and mass spectroscopy characterizes each of the
components individually.
• By combining the two techniques, an analytical chemist
can both qualitatively and quantitatively evaluate a
solution containing a number of chemicals.
INTRODUCTION
GAS CHROMATORAPHY
• In general, chromatography is used to separate mixtures
of chemicals into individual components. Once isolated,
the components can be evaluated individually.
• Separation occurs when the sample mixture is injected
into a mobile phase (gas-helium).
• The stationary phase is usually contained in a tube of
some sort called a column of glass or stainless steel.
TYPES OF CHROMATOGRAPHY
1. Gas-solid chromatography:
• Here, the mobile phase is a gas while the stationary
phase is a solid.
• Used for separation of low molecular gases, e.g., air
components, H2S, CS2 ,CO2 ,rare gases, CO and oxides
of nitrogen.
2. Gas-liquid chromatography:
• The mobile phase is a gas while the stationary phase is a
liquid retained on the surface as an inert solid by
adsorption or chemical bonding.
PRINCIPLE OF SEPARATION
• The principle of separation in GC is “partition”.
• The mixture of component to be separated is converted to
vapour and mixed with gaseous mobile phase.
• The component which is more soluble in stationary phase
travel slower and eluted later. The component which is less
soluble in stationary phase travels faster and eluted out first.
PRINCPLE OF SEPARATION
• No two components has same partition coefficient
conditions. So the components are separated according
to their partition coefficient.
• By changing characteristics of the mobile phase and the
stationary phase, different mixtures of chemicals can be
separated.
• Further refinements to this separation process can be
made by changing the temperature of the stationary
phase or the pressure of the mobile phase.
PROCESS
1.CAREER GAS
• A career gas mobile phase flows continuously
through the column which is coated with a liquid
stationary phase.
• The gas tank is fitted with a pressure controller,
pressure gauge , a molecular sieve to transfer
filtered dry gas and a flow controller to ensure a
constant rate of flow of mobile phase to the column.
• It should meet the following criteria:
• Should be chemically inert (Hydrogen, helium and
nitrogen are commonly used).
• Should be of high quality and not cause any fire
accidents.
• Should be suitable for the sample to be analyzed
and for the detector.
2. INJECTION PORT
• The sample is introduced into the heated
injection port.
• Injection port or sampling unit is attached
to the column head.
• Since the sample should be in vapourized
state, the injection port is provided with
an oven that helps to maintain its
temperature at about 20-
50 ℃ above the sample boiling point.
• Gaseous samples may be introduced by
use of a gas tight hypodermic needle of
0.5-10 ml capacity.
• For Liquid samples , micro syringes of
0.1-100µL capacity may be used.
 3. COLUMN UNIT
• The capillary column is held in an
oven that can be programmed to
increase the temperature gradually
for separation.
• Capillary columns length ranges from
10-100m and inner diameter is usually
0.1-0.5mm.
• There are two general types of columns:
1. Wall-coated columns - consist of a capillary tube whose walls
are coated with liquid stationary phase.
2. Support-coated columns- the inner wall of the capillary is lined
with a thin layer of support material such as diatomaceous earth,
onto which the stationary phase has been adsorbed.
• SCOT columns are generally less efficient than WCOT columns.
3.COLUMN UNIT
• As the temperature of column increases, those
compounds that have low boiling points elute from the
column sooner than those that have higher boiling points.
• Therefore, there are actually two distinct separating
forces, temperature and stationary phase interactions.
INTERFACE
• After separation in the GC column, analyte species have to
be transported to the mass spectrometer to be ionized, mass
filtered and detected.
• The column outlet needs to be connected to the ion source
of the mass spectrometer and different strategies had been
implemented, all of which need to fulfill the following
conditions:
• Analyte must not condense in the interface
• Analyte must not decompose before entering the mass
spectrometer ion source.
• The gas load (dictated by the mobile phase gas flow rate)
entering the ion source must be within the pumping capacity
of the mass spectrometer.
INTERFACE
INTERFACE
• The GC/MS interface is a heated metal tube equipped
with a temperature controller.
• Even through the gas exiting the column is at a pressure
between 200 - 700 KPa and the pressure in an electron
ionization source is about 10−1 Pa.
• GC columns produce high volumetric flow of carrier gas,
which if introduced directly into the ion source of the MS
may compromise the vacuum leading to much reduced
efficiency of the ionization process.
• The two devices in use today are the
I. Open-split interface.
II. The jet separator.
i. OPEN SPLIT INTERFACE
• The flow rate into the ion source
is fixed by the dimensions of the
capillary tube leading to the mass
spectrometer.
• Its function is dependent on the
use of a purge gas entering near the exit of the column.
• When using the open-split interface, the flow rate of the
column can be changed without affecting the conditions in
the ion source.
ii.JET ORIFICE SEPARATOR
• The operation of this separator is based on a diffusion principle.

• The eluate from the GC comes in from the left, across the gap
between points A and B, there is a tremendous expansion of the
gases.
• This action imposes a discrimination against the carrier gas,
which means that most of the carrier gas (lighter particles)
diffuses into chamber B and is removed by a vacuum pump.
• Most of the organic material (heavy particles) is preferentially
shot into the ion source.
MASS SPECTROSCOPY
• The mass spectrometer is an instrument which help in
separating the individual atoms or molecules because of
difference in their masses.
• Mass spec is easy technique to give you Molecular weight
(from molecular ion (M+)
• You can get Molecular formula (Elements present).
• Nearly all elements in the periodic table can be
determined by mass spectrometry.
INSTRUMENTATION
WORKING OF MS
1. ION SOURCE
• The gas molecules exiting the GC are bombarded by a
high energy electron beam.
M + e- M+ + 2e-
Where:
M+. is molecular ion
2e- is electron

• Now voltage “v” is applied in an electric field then ions are

accelerated. In this condition the energy given to each
particle is zV and this is equal to kinetic energy which is
equal to 1/2mv2 .
2. MASS ANALYZER
• Once ions are excited from a sample they are then
passed to a mass analyzer via electric or magnetic fields.
• In essence the field applies a force to the ions. as ions
with different mass and charge are accelerated at different
rates they can be separated.
• There are a number of different mass analyzers used in
MS: MASS
ANALYZER

TIME OF
QUADROPOLE ION TRAP
FLIGHT
2. MASS ANALYZER
Time of Flight (TOF)
• Most common mass analyzers are based on a technique
known as Time-of-flight (TOF).
• This method accelerates ions through the same electric
field.
• The analyzer then measures the flight time for each ion to
travel to the detector.
• For ions carrying the same charge their acceleration and
velocity will be dependent only on their mass.
• Light particles will arrive at the detector first and the
heavier ones will follow.
 3. DETECTORS
• The eluted solute particles along with the carrier gas exit
from the column and enter the detector.
• The detector then produces electrical signals proportional
to the concentration of the components of solute.
• The signals are amplified and recorded as peaks at
intervals on the chromatograph.
• The greater the concentration in the sample, the bigger
the signal. The signal is then processed by a computer.
• The time from when the injection is made (time zero) to
when elution occurs is referred to as the retention time
(RT).
3. DETECTORS
Detectors can be grouped into concentration dependent
detectors and mass flow dependent detectors. 
i. Dependent Detector:
• The signal from a concentration dependent detector is related
to the concentration of solute in the detector, and does not
usually destroy the sample.
• Dilution of sample with make-up gas will lower the detectors
response.
ii. Mass flow dependent detectors:
• They usually destroy the sample, and the signal is related to
the rate at which solute molecules enter the detector.
• The response of a mass flow dependent detector is unaffected
by make-up gas.
4. MASS SPECTRUM
• The mass spectrum is the plot of mass to charge ratio of
positively charged ions against their relative abundance.
• Base Peak: The most intense peak in the mass spectrum.
• Molecular Ion Peak: The molecular ion peak gives the
molecular weight of compound.
• Fragment Ions: The ions produced from cleavage of
bonds of molecular ions.
APPLICATIONS OF GC-MS
1. Environmental Monitoring:
• GC-MS is becoming the tool of choice for tracking organic
pollutants in the environment.
2. Criminal Forensic:
• GC-MS can analyze the particles from a human body in
order to help link a criminal to a crime.
• It’s also commonly used in forensic toxicology to find
drugs and poisons in biological specimens of victims .
3. Food and Beverages:
• GC-MS is extensively used for the analysis of food
compounds which include ester, fatty acids , alcohols,
aldehydes, terpenes etc.
LIMITATIONS
• Only Compounds with Vapour Pressure exceeding about
10^-10 torr can be analyzed by gas chromatography–
mass spectrometry.

• Certain isomeric compounds cannot be distinguished by

mass spectrometry (EG : naphthalene vs. azulene).