General Chemistry II

Module 8
Gas Chromatography

Instrumentation for GC
Provide a regulated flow of carrier gas to the
column
Inlet system to vaporize and mix the sample
with the carrier gas
A thermostatted oven to optimize the
temperature for the separation
In-line detector to continuously monitor the
separation
Data handling system to record the
chromatogram

Block Diagram of a GC

Gas Chromatograph

Gas Chromatography
Common type of chromatography used
in organic chemistry for separating and
analyzing compounds that can be
vaporized without decomposition.
Typical uses
Testing the purity of a particular substance
Separating the different components of a
mixture into separate components
Identify a compound

GC Columns
Two main types:
Packed
Capillary
Packed columns are 1.5 - 10 m in length and
have an internal diameter of 2 - 4 mm. The tubing
is usually made of stainless steel or glass and
contains a packing of finely divided, inert, solid
support material that is coated with a liquid or
solid stationary phase. The nature of the coating
material determines what type of materials will be
most strongly adsorbed. Thus numerous columns
are available that are designed to separate
specific types of compounds.

GC Columns
Two main types:
Packed
Capillary
Capillary columns have a very small internal
diameter, on the order of a few tenths of millimeters,
and lengths between 25-60 meters are common. The
inner column walls are coated with the active materials
(WCOT columns), some columns are quasi solid filled
with many parallel micropores (PLOT columns). Most
capillary columns are made of fused-silica with a
polyimide outer coating. These columns are flexible, so

CHAPTER 23: Figure 23.2

CHAPTER 23: Equation 23.7

Poly(siloxane) Stationary
Phases

CHAPTER 23: Table 23.1

CHAPTER 23: Equation 23.1

Ionic Liquid Stationary Phase

Carrier Gas
The choice of carrier gas (mobile phase)
is important, with hydrogen being the most
efficient and providing the best separation.
Helium has a larger range of flow rates that
are comparable to hydrogen in efficiency,
with the added advantage that helium is
non-flammable, and works with a greater
number of detectors. Therefore, helium is
the most common carrier gas used.

CHAPTER 23: Figure 23.11

Van Deemter Curves

CHAPTER 23: Figure 23.13

Microliter Syringe

Sample Inlet Requirements

To vaporize and mix the sample with
the carrier gas prior to the start of the
separation without
Reducing the separation potential of the column
In the absence of thermal degradation,
adsorption or modification of the sample
Without discrimination of sample components
by volatility, molecular weight, or polarity
With quantitative recovery for both trace and
major sample components

Packed Column Injector

CHAPTER 23: Figure 23.14

Split Injector for Open-Tubular

Columns

GC Temperature
Temperature-dependence of molecular adsorption
and of the rate of progression along the column
necessitates a careful control of the column
temperature to within a few tenths of a degree for
precise work.
Reducing the temperature produces the greatest
level of separation, but can result in very long
elution times.
For some cases temperature is ramped either
continuously or in steps to provide the desired
separation. This is referred to as a temperature
program. Electronic pressure control can also be
used to modify flow rate during the analysis, aiding
in faster run times while keeping acceptable levels

Ionization Detectors
At typical operating conditions the common
carrier gases used in GC behave as perfect
insulators allowing the conductivity due to
very few charged species to be easily
measured
Flame Ionization Detector (FID)
Thermionic Ionization Detector (TID or NPD)
Photoionization Detector (PID)
Electron-Capture Detector (ECD)
Helium Ionization Detector (ECD)

GC Detectors
Two most common detectors
Flame ionization detectors
Thermal conductivity detector

Both are sensitive to a wide range of

components, and both work over a
wide range of concentrations.
Both detectors are also quite robust.

Detection Systems
Flame ionization detector
Thermal conductivity detector
Electron-capture detector
Thermionic detector
Electrolytic conductivity detector
Photoionization detector
Atomic Emission detector
Fame photometric detector
Mass spectrometry detector

CHAPTER 23: Figure 23.18

Flame Ionization Detector

Near universal
response
CH* + O* CHO+ + e

MDA = 10-12 g/s

Linear range 106
Fast response
Low dead volume
Exceptional stability

Thermionic Ionization Detector

Selective for N and P
compounds (other elements
by modifying the thermionic
source)
MDA = 10-13 g/s N
10-14 g/s P
Linear range 104
Selectivity 104 g C/g N
105 g
C/ g P
0.5 g P/ g N

CHAPTER 23: Figure 23.19

Electron-Capture Detector

Electron-Capture Detector
High-energy beta electrons generated by the
decay of a radioactive isotope source used
as the primary source of ionizing radiation
These particles produce a large number of
secondary electrons through multiple
collisions with the carrier gas molecules
forming a plasma of thermal electrons (0.02
to 0.05 eV), radicals and positive ions
Application of a pulsed potential to the
ionization chamber allows collection of the
thermal electrons and a standing (baseline)
current established

Electron-Capture Detector
When compounds with a high electron
affinity enter the ionization chamber
thermal electrons are removed by
formation of negative ions
The increased rate of neutralization of
these ions with positive ions, or their
reduced drift velocity during collection of
the thermal electrons, is responsible for
the detector signal
The decrease in the detector standing
current is proportional to solute
concentration

Electron-Capture Detector
Compound selective
detector
(electron affinity)
AB + e AB
AB + e A + B
Selectivity range 107
MDA = 10-14 g / mL
Linear range = 104

Bulk Physical Property Detectors

Respond to some difference in a carrier
gas property due to the presence of the
analyte
Thermal Conductivity Detector (TCD)

Near universal detector

MDA = 10-9 g / mL
Linear range 104
Non-destructive detector
Detectors with very small volumes available

CHAPTER 23: Figure 23.17

Thermal Conductivity
Detector