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GAS CHROMATOGRAPHY
INSTRUMENTATION
The G.C. instrument consists of several major parts.

Insert diagram here.

1. Mobile phase (carrier gas) supply - the carrier gases:

are contained in thick-walled cylindrical metal gas tanks that have two stages of
pressure regulation,
flow rates through the column are controlled accurately by this regulation and a
pressure/flow controller at the column head in the instrument,
must be pure and chemically inert, and are passed through traps to remove traces of
gaseous impurities, moisture, and oxygen,
commonly used are: argon, helium, nitrogen, and hydrogen

2. Sample Injection Port - the injection port:

is where the sample is introduced, vaporized and swept onto the chromatographic
column,
consists of a metal body with an injection port that contains a high temperature, selfsealing rubber or silicone septum (through which the sample is injected with a syringe),
and it is connected to both the inflowing carrier gas and the column head,
is kept at a temperature of at least 50o above the boiling point of the highest boiling
component of the sample in order to vaporize the sample instantaneously, to ensure
that the sample goes on to the column as a plug of narrow width,
samples must be volatile and may be introduced into the instrument as a gas, liquid, or
solid. The samples must enter the column as a narrow plugs to ensure narrow (sharp)
peaks and to reduce band broadening and poor resolution.

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3. Columns
two types of columns - packed and open tubular,
they are usually bent into coils of diameter 8 to 10 inches, so that they may fit into the
G.C. oven,

1. Packed column - is the earliest type of column developed and it is still widely used.
- materials:
glass, metals (e.g., stainless steel, nickel, aluminium, copper), teflon or
teflon-lined metal tubes, other exotic alloys for specific applications (e.g.,
where corrosion and/or adsorption on walls may be problems).
- dimensions: length - 2 to 10 feet
internal diameter (i.d.): 1/8 or 1/4 inch
- stn. phase: may be liquid coated or bonded on to an inert support (GLC), or a solid
adsorbent (GSC).
Stationary phases and supports are discussed in detail, later.
2. Open tubular column - is one in which the stationary phase is not in the form of a packing
material, but is coated on the inner walls of a narrow tube. There are three main types of
open tubular columns:
i. fused silica open tubular (FSOT)
ii wall-coated open tubular (WCOT)
iii porous-layer open tubular (PLOT) or support-coated open tubular (SCOT)
- materials:
glass, metals (e.g., stainless steel, aluminium, copper), plastic, and fused
silica coated with polyimide (flexible, 1979).
- dimensions: length - 30 to 300 feet
internal diameter
- WCOT ~ 0.25 - 0.75 mm
- SCOT (PLOT) ~ 0.5 mm
- FSOT ~ 0.1 - 0.3 mm
- megabore ~ 530um, 0.53mm, can use sample sizes similar to those
used with packed columns.
- stn. phase: the stationary phases used are the same as those used for packed
columns. The stn. ph. is coated on to the inside of the column and is ~ 0.1
to 1.0 um in thickness.
PLOT, SCOT columns have a fine diatomaceous earth film (~30 um) thick,
which can hold more stationary phase.

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4. Detectors - there are several requirements for a detector, as follows:
high sensitivity,
good stability and reproducibility,
linear response - over several orders of magnitude,
temperature range - can be used from room temperature to ~400 oC,
short response time that is independent of flow rate,
high reliability and ease of use,
similar response to all solutes or highly predictable and selective response to
one or more solutes,
non-destruction of sample.
No one detector provides all of the above and detectors are often selected
depending on the particular solute and level of concentration in the sample.
There are several detectors that have gained wide-spread acceptance in GC:
thermal conductivity detector (TCD),
flame ionization detector (FID),
thermionic detector (TID) or nitrogen-phosphorus detector (NPD),
electron capture detector (ECD),
mass spectrometer (MS),
photoionization detector (PID),
flame photometric detector,
atomic emission detector - microwave induced plasma (MIP).
We will discuss the first two (2) detectors very briefly.

i). Thermal conductivity detector (TCD) or Katharometer

based on changes in the thermal conductivity of the carrier gas due to the
presence of analyte species,
has a wide response to both organic and inorganic species

Advantages
simple to use,
large linear dynamic working range (~ 105 ),
responds to both organic and inorganic species,
non-destructive - the solute can be collected.
Disadvantage
low sensitivity ( ~ 10-8 g solute/mL carrier gas )

ii) Flame Ionization Detector (FID)

based on the combustion of organic materials to produce ionic species that

are captured by a collector producing an ion current

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Response
responds to organic species
functional groups, e.g., C = O, - OH, - NH, - Cl, etc yield few, if any, ions
does not respond to H2O, SO2, CO2, NOx, etc. (non-combustible gases)
response found to be roughly proportional to the number of reduced carbon
atoms in the plasma, i.e., ~ proportional to the number of carbon atoms in the
species
Advantage
responds to carbon compounds,
high sensitivity (~ 1013 g/mL),
large linear response range (~107),
low background noise,
rugged and easy to use.
Disadvantage
destroys the sample

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STATIONARY PHASES (ADDENDUM)
In GC stationary phases may be liquid (GLC) or solid (GSC).

Gas Liquid Chromatography

In GLC, the liquid stationary phases have to be supported on an inert solid substrate.
They may be coated (physical adsorption) or bonded (chemically) to the surface of the
substrate.
Support material
The support material for liquid stationary phases:
holds the stationary phase in place
is comprised of small spherical particles
has a large a surface area as possible for interaction with the solute species (a
specific surface area of ~ 1 m2/g)
is uniform in size
is inert to interactions with the solute, stationary phase liquid, and the mobile phase
must have good mechanical strength (so that it does not degrade and/or deform
easily)
be uniformly wetted by the stationary phase
usable at elevated temperatures (up to ~ 400 oC
The efficiency of the chromatographic column increases rapidly with decreasing particle
diameter. Small particle sizes provide a large surface area for holding the liquid
stationary phase, however, there is a practical limit to the size of the particle that can be
used.
If the particle diameter is too small, then the pressure differential across the column
required to maintain a given mobile phase flow rate may become excessive:
pressure difference a 1/(diameter)2
Pressure drops greater than ~ 30 psi are not advisable.
Several support sizes are commonly used. It is difficult to prepare particles of very
precise diameters, thus the support material is usually sieved to contain a narrow
range (~ 20 mesh range) of particle sizes:
60 - 80 mesh
80 - 100 mesh
100 - 120 mesh

~ 250 - 170 mm
~ 170 - 150 mm
~ 150 - 120 mm

Some newer support materials are being made with a mesh range of ~ 10 mesh.

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Several types of support materials are widely used for GLC columns:
1. diatomaceous earth (Chromosorb P, W, and G)
2. teflon particles (40 - 60 mesh)
3. etched glass beads (60 - 80 mesh)
4. porous polymer beads
The most widely used support materials, however, are those made from diatomaceous
earth materials.
There are two main types of supports made from the above:
1. Chromosorb P - this is the pink support and is made by crushing, blending
and briquetting the diatomaceous earth, and then heating at
over 900 oC. The briquettes are then ground and sieved
into various mesh sizes
- the material has pore sizes of ~ 9 mm, and a specific
surface area of ~ 4 m2/g
2. Chromosorb W or G
- this is the white support and is made by mixing the
diatomaceous earth with sodium carbonate flux and heating
at about 900 oC. The product is more rugged than
Chromosorb P and does not retain solutes to the same
extent
- the material has pore sizes of ~ 2 mm, and a specific
surface area of ~ 1 m2/g

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There are problems associated with the use of most support materials. Two things have
to be considered:
the effect of surface silanol groups on the support material
the presence of mineral impurities in the support material

The above cause solutes to be physically adsorbed on to the support material. Such
adsorption leads to distorted peaks, i.e., peaks that are broadened and in peak tailing:
the surface of diatomaceous earths have silanol (-SiOH) groups that tend to
adsorb polar and polarizable species, particularly when the support is lightly
loaded with the liquid stationary phase or when non-polar liquid stationary phases
are used.
Insert diagram here.

the support material can be deactivated by reacting it with dimethylchlorosilane

which replaces the H of the -OH group
((CH3)3)2 Cl2 Si

the support is washed with alcohol and a second chloride is replaced with a
methoxy group

silanized supports may still show some adsorption due to the presence of mineral
impurities in the diatomaceous earth
- this problem is removed by washing the silanized support with acids prior to
silanization

nomenclature - e.g., Chromosorb P-AW-DMCS

- AW
= acid washed
- DMCS
= dimethylchlorosilane

another silanization reagent that is used is hexamethyldisilane (HMDS)

(CH3)3 Si NH Si (CH3)3

Liquid Stationary phases

requirements:
low volatility (~100oC higher than the maximum operating temperature of the
column)
thermal stability
chemical inertness
solvent characteristics, e.g., k, a, for solutes, should fall within a suitable range
choice:
important to the success of the separation
guidelines exist for making this choice
- usually based on polarity parameters, particularly the polarity of the stationary
phase relative to those of the sample constituents
although some information is obtained from these guidelines, trial and error
usually provides information for the final choice
examples:
squalene (cycloparafin)
methyl silicone gum (e.g., OV-1, SE-30)
methyl silicone fluid (e.g., DC-200, OV-101)
diisodecyl phthalate
diethylene glycolsuccinate
phenylmethyl silicone oil
polyethylene glycol (Carbowax-20M)
theoretical plates
packed columns >> 250 - 1000/ft (easily)
capillary columns >> 6000 - 10,000/m

preparation:
coating (several techniques are used), e.g.:
- a known mass of support is mixed with 3 - 4 times its volume of a volatile
solvent containing a known mass of stationary phase (~1 - 10 % of the mass
of the support materials)
- the solvent is then evaporated

chemical bonding (stationary phase is chemically bonded to the support material):

- the silanol groups on the silica articles (support) are reacted with, e.g., silicon
tetrachloride (Si Cl4)
Insert diagram here.

the product is reacted with a polyol (MW ~3000 or more)

the -OH group(s) are reacted with various reagents to provide surfaces of
different polarities

advantages:

disadvantage: - sensitive to degradation by oxygen and water

- uniform layer of stationary phase

- has reproducible properties
- monolayer leads to rapid equilibrium of solute between
phases, i.e., efficiencies are improved
- thermally very stable up to ~ 250 350 oC

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Gas Solid Chromatography
Gas solid chromatography is based on the adsorption of gases on solid surfaces
(adsorbents).
The distribution coefficients for the gases in GSC are much larger than those for GLC
thus GSC is used for the separation of species that are not retained by gas liquid
columns, e.g., air, H2S, CS2, N-oxides, CO, CO2, rare gases, hydrocarbons (at
high temperatures)

Stationary Phases
There are two main types of solid adsorbents (stationary phases) that are used in GSC:
i) molecular sieves

- these are aluminium silicate ion exchangers

- pore sizes depend on the nature of the cation on the
exchanger
- have pore sizes of 4, 5, 10, 13 Ao
- come in 40/60 t0 100/120 mesh sizes, usually
- Mechanism of separation:
- large molecules cannot penetrate into the pores and are
thus restricted to the outer surface of the stationary
phase particles
- molecules of dimension less than the pore size penetrate
to the inside of the stationary phase particles where
adsorption takes place
- the surface area is very large for such molecules
(compared to that for larger molecules)
- thus large molecules are separated from small molecules

ii) porous polymers

- these are beads of uniform size which are made from

styrene cross-linked divinylbenzene
- the pore sizes are controlled by the extent of crosslinking
and is uniform
- can have several average pore sizes for use
- often used for the separation of gaseous polar species
such as: H2S, H2O, N-oxides, CO2, methanol, and vinyl
chloride