GAS CHROMATOGRAPHY

physical method of separation in

which components to be
separated are distributed
between two phases, one
constitutes the stationary
phase, of large surface area, and
the other is a gas (mobile
phase) that passes through or
along the stationary phase.
Types of Chromatography
according to stationary phase
Type Stationary Movil Phase
Phase

Gas-Solid Solid Gas

Gas-liquid Liquid film Gas

adsorbed on
a solid
support
Instrumental Equipment
For Pressure and Temperature effects, it is
advisable to express in function of flow
instead of using time.
𝑉𝑟 = 𝑡𝑟 ∗ 𝑓 It is just that average flow is not
possible to measure, therefore the output
flow is measured and it is obtained that:
𝑇𝑐 𝑃−𝑃𝐻2 𝑂
𝐹=𝑓∗ ∗
𝑇 𝑃
Where:
𝑇𝑐 Column temperature at ºK.
𝑇 Environment Temperature where the
flow is measured
𝑃 Outlet Pressure
𝑃𝐻2𝑂 Steam Pressure
RELATIONS GOVERNING GAS
CHROMATOGRAPHY
Hold up Volume 𝑽𝒓 = 𝒕𝒓 ∗ 𝑭
Dead Volume 𝑽𝒎 = 𝒕𝒎 ∗ 𝑭
Where: 𝑭 Average Output Column Flow

Therefore:
𝑻𝒄 𝑷 − 𝑷𝑯𝟐 𝑶
𝑭 = 𝑭𝒎 ∗ ∗
𝑻 𝑷
 Gas Chromatography
Instrumentation Diagram
According to the Sieves Theory, a
Chromatographic column consists of a
series of sieves. It assumes that stationary
phase volume in each sieve is constant;
mobile phase volume is constant from sieve
to sieve; it means in each sieve the two
phases are in equilibrium, and distribution
coefficient value is constant and
independent of the solute concentration.
 Equation that involves kinetic factors
is the Vaan Demter equation:
𝑩
𝑯𝑬𝑻𝑷 ó 𝑯 = 𝑨 + + 𝑪𝒖
𝒖
Where:
𝒖: linear velocity .carrier gas
COLUMN
It is the heart of a chromatograph. Materials
with which the columns can generally be
made are: copper, aluminum, stainless steel,
glass or Teflon. The filler can be a solid, or a
liquid coating a solid. We can classify the
columns according to the purpose of the
chromatographic process. It can be:
Packaged and Capillaries and this
Analytical, Preparatives :
Capillaries and these in turn:
W.C.O.T. (Wall Coated Open Tubular)
S.C.O.T. (Support Coated Open Tubular)
 Detector Classification
According to Selectivity:
Universal: It responses mostly solutes
compounds.
Specifics or Selectives: It shows a great answers
for an large substances group.
Destructives and Non-Destructives: It depends
wether the sample have been destroyed or not.
Response Mode:
Dependent on flow mass rate.
Dependent on Concentration.
According to Detection: Ionization, Optical and
Spectroscopic, Electrochemical.
Types of Detectors
Thermal Conductivity Detector (TCD)
Flame Ionization Detector(FID)
Electron Capture Detector (ECD)
Mass Spectrometer (MS)

These are most common detectors!!

Thermal Conductivity (TCD)
Based on changes in thermal conductivity
gas stream produced by analyte molecules.
It consists of an electrically heated element
(Pt, Au, W) whose dependence on gas
thermal conductivity.
𝐻2 𝑎𝑛𝑑 𝐻𝑒 thermal conductivities are greater
than those of many organic compounds,
thermal conductivity decreases and
detector’s temperature increases.
Its only drawback is its low sensitivity (10-8
g/ml).
TCD Diagram
Ionización de Llama (FID)
This detector is based on organic compounds, They
are pyrolyzed in an air / H2 flame producing ions and
electrons that conduct current through the flame. This
signal is trapped by an ion collector in the flame, and
depends on the number of carbon atoms that enter the
detector per unit of time, so it is more sensitive to
mass than to concentration. It is applied to organic
compounds but is not very sensitive to compounds
such as carbonyl, amines, halogens and alcohols.
Detector is insensitive to gases like H2O, CO2, SO2 y
NOX.
This Detector it’s the most using on Gas
Chromatography (GC)!!!
Advantage: Higher Sensibility (10-13g/s), Large linear
range (107),lower noise, resistent.
Disadvantage: Destroy the sample.
FID
Electron Capture (ECD)
The effluent passes over a β emitter (Ni-63) and an
electron from it causes ionization of the carrier gas. In
the absence of organic species a constant mass flow
is obtained, but in the presence of them the current
decreases due to its tendency to capture electrons.
It is very sensitive to compounds with electronegative
functional groups such as halogens, peroxides, nitro
and quinones. Insensitive to groups such as amines,
alcohols and hydrocarbons.
These detectors are highly sensitive! and these do not
modify the sample significantly. Its linear interval is
limited to two orders of magnitude.
Mass Spectrometer (MS)
It’s an instrument that allows to analyze with
great precision different composition of
chemical elements and atomic isotopes,
separating the atomic nuclei according to their
mass-load ratio (m / z). To identify the
different chemical elements that form a
compound or determine the isotopic content of
different elements in the same compound.
Mass spectrometer measures ion charge / mass
ratios, heating a beam of material of the compound to
be analyzed until it vaporizes and ionizes the different
atoms. The ion beam produces a specific pattern in
the detector that allows the chemical compound to be
analyzed.
Mass Spectrometer Diagram
(MS)