TOPIC 2

Course Learning Outcomes

Able to :
1. Explain the fundamental concepts & theories of
separation techniques in GC.
2. Sketch, label the schematic diagrams & discuss the
function of each component in GC.
3. Identify the strength & limitations of GC technique.
4. Suggest & justify the most suitable & efficient separation
technique to be employed for an analysis.
2

General Chromatography
3

Chromatography
Gas
GSC

Liquid
GLC

RPC

NPC

IEC

SEC

AC

GC : Volatile solutes
(Sample MUST be volatile at temperatures BELOW 350 0C)
LC : Any mobile phase soluble solutes

GC separation is based on :
1. Differences in boiling points of the solutes
(volatilities).
volatilities
2. Solutes interaction with the stationary phase
(polarity).

Gas-solid chromatography (GSC)

5

Based on solid stationary phase (charcoal,

molecular sieves).

Retention of analytes by physical adsorption
on solid surfaces of stationary phase.

Gas-solid chromatography (GSC)

6

Limited application :
 Semipermanent retention of polar molecules.
 Tailing of elution peaks.

Used for the separation of species that are not
retained by GLC (low molecular weight gaseous,
eg. air components, hydrogen sulfide, carbon
monoxide & nitrogen oxides).

Gas-liquid chromatography (GLC)

7

Known as gas chromatography.

Stationary phase is liquid (high boiling) that is
retained on the solid support.

Liquids are used to modify the stationary phase.

The chromatographic process - Partitioning

8

Separation is achieved by partition of the

component of the sample between the phases
(gas)

MOBILE PHASE
Sample
out

Sample
in

STATIONARY PHASE
(liquid coated onto a solid support)

Schematic diagram of
gas chromatography

Sample is injected & vaporized

onto the head of the
chromatographic column

Tinj,det Toven + 50C

Separation is based on the differences in

migration rates among the sample components
9

As each component
emerges from the
column, it will be
detected

Performing GC separations
10

Sample is injected at the injected port.

Analytes (volatile) are vaporized & transported
through the column by the flow of gaseous mobile
phase (He, N2 or H2).

The column is kept at a control temperature inside an
oven, so that the mixture remains in vapor form to be
eluted.


The detector is maintain at a higher temperature than

the column so that all analytes will be gaseous.

From the time the mixtures are injected until they

reach the detector, they are being retained by the
liquid in the column (the stationary phase).

11

Instrumental components
12

1. Carrier gas (mobile phase)

2. Sample injection system
3. Columns
4. Detectors

Gas chromatography equipment

13

Carrier gas (mobile phase)

14

Function : As a mobile phase.

 To transport the analytes
through the GC system
(transports the solute from
the injection port to the
column & detector)
Mobile phase does not interact with
molecules of the analyte


Pressure regulators, gauges & flow meters are required

to control the flow rate of the gas.

GC gas control

15

TANK PRESSURE REGULATOR

Inlet
Gauge

Outlet
Gauge

Gas
Inlet

Shutoff
Pressure Control

Outlet Fitting or H2 Snubber

16


Type of gases
 Helium (common)
 Nitrogen
 Hydrogen
 Argon

Combustion gases
 Hydrogen
 Air
Compounds are burned in a hydrogen-air flame.

17


Carrier gas :
 Does not interact with molecules of the analyte
(chemically inert).
 Highly purity gas (99.995% - 99.9995%) & free of
oxygen & moisture (dry).
 Contains a molecular sieve to remove water & other
impurities or used in connection with desicants,
hydrocarbon trap to filter any contaminants.

18

Advantages & disadvantages of carrier gas

Gas

Advantages

Disadvantages

Nitrogen

Cheap, readily available

Long run times

Helium

Good compromise, safe,

compatible with many
detectors

Expensive

Hydrogen

Shorter run times (low

Mw, higher flow rate can
be used), cheap

Explosive

19

Typical carrier gases

20

Carrier Gas
He, N2, H2
N2, Ar/Methane
He, H2, N2, Ar
He, N2, H2
He, N2, H2
He, N2,
He, N2, H2
He

Symbol
FID
ECD
TCD
PID
ELCD
NPD
FPD
MS

Detector Type
Flame Ionization
Electron Capture
Thermal Conductivity
Photoionization
Electrolytic Conductivity
Nitrogen Phosphorus
Flame Photometric
Mass Spectrometer

van Deemter curve for GC

21

Theories of band broadening in GC can be

explained by the van Deemter equation.

Van Deemter curve for GC differ using 3 different
carrier gases : N2, He, H2.

van Deemter Plot

A plot of plate height vs average linear velocity of mobile phase.

Determine the optimum mobile phase flow rate to obtain the
minimum H.

H = A + B/v + Cv
B
v

Cv

Hmin
A
v

vopt
22

23


With N2, the optimum flow rate is lower (high

resolution) compared to H2.

B diffusion coefficient of analyte in mobile phase,
DM .

H2 is lighter than N2 (heavier; larger Mw), therefore DM
in H2 is higher than in N2.

Hence, B term is more significant in H2 at low flow
rate compared to N2. This increase band broadening,
thus poor resolution.
24


Gas density : N2 > He > H2

Diffusion coefficient : H2 > He > N2

A highly dense gas gives best efficiency since
diffusivity is lower, but a low density gas gives
faster speed.

25


The slope of the curve at higher flow rate is shallower

when using H2 due to smaller C term (the equilibrium
between the mobile phase (H2) & stationary phases is
more efficient).

H2 & He give better Rs (smaller H) than N2 at high flow
rate because solute diffuse more rapidly through H2
& He than N2.

The more rapidly a solute diffuses between phases, the
smaller is the C term.
26

The mobile phase mass transfer (CMv)

CMv = (fM(k)dp2/DM)v
dp = particle diameter of packing
DM = mobile phase diffusion coefficient
CMv is less if dp is smaller (hence greater surface
area), or the solute diffusion coefficient in the
mobile phase, DM is larger
Small particles reduce the distance solute must
diffuse in the mobile phase
27

Sample problem 1
GC, HPLC & SFC are 3 types of separation methods with
different mobile phases. Compare & discuss how each mobile
phase affects the B term of van Deemter in each of the above
separation method.

28

Sample problem 2
Which term (A, B or C) is most significant in GC. Explain why
& suggest one approach to minimum the effect.

29

Column
30

Types of column
Packed column

Open tubular (capillary) column

Wall-coated
open tubular
column
(WCOT)

Support-coated
open tubular
column (SCOT)

Porous-layer
open tubular
column

Types of column
31

Packed column
32

~ 2-6 mm I.D. tubing.

1-5 m length.

Used to separate gases that are

poorly retained.

Provide greater sample capacity.

Disadvantages :
X Broader peak
X Longer tR
X Less resolution

Tube made of glass, metal (stainless steel,

copper, aluminium) or teflon with 2-6 mm
I.D. & 1-5 m in length.
Packed with fine particles of solid
support (commonly diatomaceous
earth) coated with a thin layer
(0.05-1 m) liquid stationary phase.

Solid support
 Serve to hold the
liquid stationary
phase

Solid support :
 Small & uniform particles size
 Mechanical stability
 Porous
 High surface area
 Inert
33

Column Wall

Carrier
Gas

Solid Support
Liquid Phase

Small, uniform particle size decreases Eddy

diffusion (requiring higher pressures)
Particles size in m or mesh size
60-80 mesh (260-170 m) , 80-100 mesh (170-149 m)
34


Small dp, decrease the time required for solute

equilibration, thus improve column efficiency.

However, the smaller the dp, the less space between
particles & the more pressure required to force mobile
phase through the column.

Flow of the mobile phase through a capillary column is
relatively unimpeded when in comparison with a packed
column.

This allow for a faster mobile phase compared to packed
column. Thus reduce B, decreasing band broadening.
35

 Due to the difficulty of packing the tubing

uniformly, these types of columns have a larger
diameter than open tubular columns & have a limited
range of length.

 As a result, packed columns can only achieve about

50% of the efficiency of a comparable WCOT
column.

36

Capillary (open tubular) column

37

Have a very small I.D.

(0.1-0.5 mm).

5-100 m long.

0.1-5 m thick stationary phase
coated on inner walls.

3 types of columns :
 WCOT
 SCOT
 PLOT

WCOT - The inner wall are directly coated with liquid stationary phase
(no support material).
SCOT - Liquid stationary phase coated on solid support attached to
inside wall of column (thin film ~30 m).
PLOT - Stationary phase (solid particles are the active stationary phase)
on inside wall of column.

~30 m

38

Tubes / capillary (capillary made of metal, glass, stainless

steel or thin fused silica (SiO2))
Stationary phase

SCOT: the inner wall of the capillary is lined with a thin

layer of solid support onto which the stationary phase has
been adsorbed.
39


One of the most popular types of capillary columns is

a special WCOT column called the fused-silica wallcoated (FSWC) open tubular column.

The walls of the fused-silica columns are drawn from
purified silica containing minimal metal oxides.

These columns are much thinner than glass columns,
with diameters as small as 0.1 mm & lengths as long
as 100 m.

40

It is possible to achieve up to 400,000 theoretical

plates with a 100 m WCOT column, yet the world
record for the largest number of theoretical plates is
over 2 million plates for 1.3 km section of column.

41

Fused silica open tubular column

Have much thinner walls than the glass capillary columns
& are given strength by the polyimide coating.

Fused silica coated on the outside with a polyimide
polymer for support & protection for the fragile silica
capillary, allowing them to be coiled.

Flexible & can be wound into coils.

They have the advantages of physical strength,
flexibility, low reactivity & smaller sampling size .
42

(imparts a brownish color to the columns)

43

Compared with packed column, capillary column offers :

 Higher resolution with narrow peak
 Shorter analysis times due to the higher flow rates
 Greater sensitivity
Disadvantage :
X Lower sample capacity
100 ng for a 0.25 mm I.D. column with 0.25 m thick film
5 g for a 0.53 mm I.D. column with 5 m thick film
Resolution efficiency :
WCOT > SCOT > PLOT > packed column

44

Properties of GC columns

45

 Open tubular columns tend to have lower H values

(greater N per given column length) since there is no A
term in H equation in non packed column.
 However, C term is highly dependent on radius of tube !!
(why?)

46

Sample problem 3
If a GC column is change from packed to capillary column,
explain the effect of the change on the H.
Change from packed to capillary column :

47

 Open tubular columns are often used in GC to achieve

very high no of plates by having very long column (less
backpressure--due to tubular nature).
 Cant used very long packed column to increase N
since back-pressure would be too great to get decent
gas flow !

48

Sample problem 4
An analyst prefers to use a longer WCOT with narrower I.D.

49

Column temperature
50

The optimum column temperature is dependant upon the

boiling point of the sample. As a rule of thumb,
a temperature slightly above the average boiling point of
the sample results in an elution time of 2-30 min.

Minimal temperatures give good Rs, but increase elution
times.

If a sample has a wide boiling range, then temperature
programming can be useful.

GC columns
51

 The basic choices of selecting the columns :

1. Stationary phase
2. Column diameter & length
3. Thickness of stationary phase

 To improve resolution, use a :

 Longer column
 Narrower column
 Different stationary phase

52

 Film thickness primarily affect the retentive character & the

capacity of a column.
1. Thick films are used with highly volatile analytes,
because such films retain solutes for a longer time & thus
provide a greater time for separation to take place.

Thick film & narrow bore column provide good
resolution & sample capacity.


Can be used with most detectors.

tR are longer than thin film.

53


Thick film & wide bore columns are required

with thermal conductivity & IR detectors.
 Have high sample capacity.
 Low resolution & long tR.

54

2. Thin films & narrow bore columns are useful

for separating species of low volatility (high
boiling point) in a reasonable time & more
efficient.

Disadvantages :
 Low sample capacity
 Require high sensitive detector
 Suffer from exposure of surface active
site on the silica

55

GC column comparisons

Description

I.D.
Film thickness
Advantages

Disadvantages

Thin film narrow

bore

Thick film narrow bore

Thick film wide bore

0.25-0.32 mm

0.53 mm

~ 1-2 m

~ 2-5 m

Good capacity
Good resolution

High capacity

Moderate resolution
Long tR for high bp
comps

Low resolution
Long tR for high bp
comps

0.10-0.32 mm
~ 0.2 m
High resolution
Fast separation
Low capacity

56

Stationary phase
57

Liquid stationary phase :

 Non-volatile liquid coated on inside of column or on
fine solid support.
 Ideal properties :
 Low volatility
 Thermal stability
 Chemical inertness
 Low viscosity

 Choice :
 Depend on the analyte of interest using the
principle like-dissolve-like.
(polar analyte = polar stationary phase)
 The polarity of the stationary phase must be
comparable to the polarities of the components, so
that there will be interaction between the
components and the stationary phase.
 When the match is good, the order of elution is
determined by the boiling point of the analytes.

58

Stationary Phase

Polydimethyl siloxane
(NON POLAR)
Poly(phenylmethyldi
methyl) siloxane
(10% phenyl)
Poly(phenylmethyl)
siloxane (50% phenyl)

Common
Trade Name

OV-1, SE-30

350

OV-3, SE-52

350

OV-17

Poly(trifluoropropyldi
methyl) siloxane

OV-210

Polyethylene glycol
(POLAR)

Carbowax
20M

Poly(dicyanoallyldi
methyl) siloxane

Maximum
Temperature
(C)

250

200

OV-275
59

Common Applications

General-purpose nonpolar
phase; hydrocarbons;
polynuclear aromatics; drugs;
steriods; PCBs
Fatty acid methyl esters;
alkaloids; drugs; halogenated
compounds
Drugs; steriods; pesticides;
glycols
Chlorinated aromatics;
nitroaromatics; alkyl-substituted
benzenes

250

Free acid; alcohol; ethers;

essential oils; glycols

240

Polyunsaturated fatty acids; free

acids; alcohols

 Polar stationary phases contain functional groups e.g., CN,

CO & OH.
 Hydrocarbon-type stationary phase & dialkyl siloxanes are
non polar.
 Polyesters phases are highly polar.
 Polar analytes alcohols, acids & amines.
 Medium polarity analytes ethers, ketones & aldehydes.
 Non polar analytes saturated hydrocarbons.
60

 Examples of liquid stationary phases :

Polydimethyl siloxanes :
 Non to strong polarity depending on R groups.
 Most stable, robust & versatile.
R
O

Si

R
O

Si
R

 R = CH3, liquid are relatively non polar.

 In other polysiloxanes, a fraction of methyl groups are replaced
by functional groups such as phenyl (-C6H5), cyanopropyl (C3H6CN) & trifluoropropyl (-C3H6CF3).
61

 The % give the amount of substitution of the named

group for methyl groups on the polysiloxane backbone.
 E.g., 5% phenyl PDMS has a phenyl ring bonded to
5% by no of the silicone atoms in the polymer.
 The substituents increase the polarity of the liquids to
various degrees.

62

 Polyethylene glycol
HO-CH2-CH2-(O-CH2-CH2)n-OH
 Used for the separation of polar analytes.

63

Bonded & cross-linked stationary phases

64

 Bonded phase column mean column with

stationary phase that attached to the surface of
the packing particles by chemical bonds.

 Purpose :

Provide a longer-lasting stationary phase that can

be rinsed with a solvent when the film becomes
contaminated.

Untreated column slowly lose their stationary

phase owing to bleeding in which a small
amount of immobilized liquid is carried out of the
column during elution.

65

2 causes for column bleeding :

1. High column temperature
2. Non bonded packing

66

 Process :

Bonding
Attaching a monomolecular layer of the stationary phase
to the silica surface of the column by a chemical
reaction.

Cross-linking
 Carried out in situ after the column is coated with
the stationary phase.
 Eg. incorporate a peroxide into the original liquid or
initiated by exposing the column to gamma
radiation.
67

Solid support (packing)

 Ideal characteristics of solid support :
 Strong, porous, high surface area & inert (nonadsorptive).
 Example of solid support :
 Diatomaceous earth (algae skeletons).

68

 A problem in GC is the physical adsorption of polar

analytes (eg. alcohols/aromatic hydrocarbons) on the
silicate surfaces of column packings & capillary walls.
 Adsorption results :
 Distorted peaks, which are broadened & exhibit a
tail.
 Adsorption is the consequence of silanol groups that
form on the surface of silicates by reaction with
moisture.
69

 A fully hydrolyzed silicate surface structure :

 The SiOH groups on the support surface have a strong

affinity for polar molecules & tend to retain them by
adsorption.

70

Solid support (packing)

Deactivation of support materials
To inhibit physical absorption of polar or polarizable
analyte species (alcohols, aromatic hydrocarbons) on
the silicate surfaces of column packings or capillary
walls.

71

Deactivation of support materials

Process:
Silanization using dimethylchlorosilane (DMCS) &
washing with methanol. Acid washing prior to
silanization may be required to remove metal oxide
impurities.

72

1. Silanization using
DMCS

2. Washing with
methanol

73

Injection port / inlets (sample introduction)

74

 The inlet is a piece of hardware attached to the

column head.
 To flash/ instantly evaporate the sample &
introduce it into the column.
 Tinj > 50 oC above Tcolumn (or 50 oC higher than the
boiling point of least volatile component of the
sample) to ensure fast & complete vaporization.

75

76

 Injection using a microsyringe (gases are injected by a

gas-tight syringe) through a rubber septum.
 Septum must be stable at injection temperature &
replaced regularly to maintain seal (lifetime : ~20
manual injection or ~100 auto sampler injections).
 Decomposed sample, non-volatile components & septum
debris accumulate in the glass liner (must be replaced
periodically).

77

 Column efficiency requires :

 Slow injection of large samples causes band
broadening & loss of resolution.

78
Page 78

 Introduced onto the column as a "plug" of vapour.

 Sample volume should not be too large, will cause
broad peak due to slow vaporization of sample.

79

Packed column
 Volume injected :
 Liquid samples 0.1-10 L
 Gas samples 1-10 mL
 ALL the vaporized sample from the injector enters
onto the column.

80

Capillary columns
 Volume ~10-3 L.
 The size of the capillary column limits the amount of
analyte that can be injected, otherwise, chromatographic
overloading occurs.
 Alternative to get the amount of analytes that are injected
onto the column smaller (the remainder going to waste)
without having to dilute concentrated samples is the
split/splitless capillary GC injector.
81

82

Injector types
 Split injector
 Splitless injector
 On-column injector

83

84

Split / splitless injector

85
Splitless Packing

Liner
4 inches long.
6 mm O.D. / 4 mm I.D.
6 mm O.D. / 2 mm I.D.

Ground
Portion

Ground
Portion

O-Rings

O-Rings

Quartz Wool
Loosely Packed

Packing
Silanized glass wool
recommended.
Top portion loosely packed.
Bottom portion tightly packed.

Split Packing

Quartz Wool
Loosely Packed
Quartz Wool
Tightly Packed

Dimple

4-mm i.d
i.d..
Wide-Bore Liner
Wide(P/N N612N612-1001)

Dimple

2-mm i.d
i.d..
Narrow-Bore Liner
Narrow(P/N N612N612-1002)

4-mm i.d.
Wide-Bore Liner
Wide(P/N N612N612-1001)

Septum

Septum Nut

Split/Splitless Inlet Weldment

Viton O-Ring
Liners

Gold-Plated Seal (Splitless)

86

Split Injection
87

 Used for high analyte concentrations (> 0.1%).

 Thermally unstable comps can decompose during the high
temperature injection.
 Uses wide bore liner (4 mm I.D.).
 Splitting of sample allows deposit of small fractions of a L
(0.2-2 %) in the column - introduces only a small amount of
sample into the column.

Effect of liner volume

88

 Large part of sample vented out :

 Prevents overloading of the column.
 Produces narrow & sharp peaks.
 After sample vented out, split outlet is closed.
 Sample injected into glass wool to allow uniform mixing
with carrier gas.

89

 The proportion of sample that does not reach the

column is called the split ratio (typically 20:1 to
100:1).

 E.g. 50:1, that is, for every 50 units of gaseous

sample that are thrown away to waste, 1 unit
goes on the column.

90

 Higher ratio Too much sample vented out,

small amount of sample enter the column, hence
small peak & not reproducible.

 Too low Poor peak shape, column overload.

91

Split ratio effects

92

(b) Split ratio: 1/75

(a) Split ratio : 1/25

93

(a) Chromatogram shows the effects of a low split

ratio. All of the peak heights were increased due to
the greater amount of the sample introduced into the
column.
(b) Chromatogram shows the effects of a high split
ratio. All of the peak heights were reduced due to the
smaller amount of the sample introduced into the
column.

94

Splitless Injection
95

 Used for low concentration samples (dilute samples) or

trace analysis (less than 0.01% of the sample) of high
boiling compounds in low boiling solvents.
 Uses narrow bore liner (2 mm I.D.).
 Split vent opened 30-90 seconds after injection, removes
bulk of the solvent (large solvent peak may overlap with the
analyte peak), but leaves most of the sample condensed at
the top of the column.

 Hence most of the sample is introduced into the column &

avoid large tailing of solvent peak.
 Requires a low initial column temperature to dissolve &
refocus the solutes at the start of the column & then
temperature programming.

 Solvent trapping volatile solvents will condense at the

top of the column & solute will dissolve & refocus in the
solvent.

 Cold trapping solute will recondense on top of the

colder column & refocus too.
96

 Once the solutes have been focused, residual

sample (mostly solvent) can be flushed via the split
vent.
 & this will concentrate the solutes at the start/top of
the column in order to give sharp peaks.

97

 Wider peaks are obtained than for split injections.

 Advantages :
 Good for trace analysis (less than 100 ppm).
 Good for high boiling point compounds.
 Easily automated.

98

Sample problem 5
In the GC analysisof polar contaminants from an
aqueous sample, splitless injection mode was used to
introduced sample into a capillary column.

99

On column injection
100

 Used for samples that decompose above their boiling point

or thermally labile compounds.
 Can handle dilute/concentrated solutions & relatively
large/small volumes.
 Best for quantitative analysis.
 Low resolution technique.
 The sample is introduced in its entirety without heat.

 Sample solution is directly injected into the column with the

aid of a syringe with a long, narrow needle without going
through a hot injector.
 Initial column temperature is low enough to condense
solutes in a narrow zone.
 Advantages:
 Trace analysis : enables quantitative insertion of sample
into column.
 Labile components not stressed thermally.
101

Detectors
102

 A specific detector responds to a single chemical

compound.
 A selective detector responds to a range of compounds
with a common physical or chemical property.
 A non-selective / universal detector responds to all
compounds except the carrier gas.
 A non-destructive detector does not destroy sample.

Flame Ionization Detector (FID)

103

 Based on the measurement of electric charges.

 Organic solutes are burned in H2/air flame producing CH
radicals and eventually CHO+ ions & electrons in the flame
(CH + O CHO+ + e).
 CHO+ ions are collected by cathode, produces current as the
response.
 Responds to the no of C atoms entering the detector per unit
time, it is a mass-sensitive, rather than a concentrationsensitive.
 The more CH-groups a molecule contains, the larger is the
detector response.
104

 Useful :
 General detector for the analysis of organic
compounds or hydrocarbons.
 Insensitive to nonhydrocarbons (H2, He, N2, O2, CO,
CO2, H2O, NH3, NO, H2S).
 High sensitivity.
 Large linear response range.
 Low noise.
 Robust.
 Easy to use.
 Disadvantage : destructive detector, it destroys the
sample.
105

Electron-Capture Detector (ECD)

106

 The sample eluate from a column is passed over a radioactive

-emitter like nickel-63.
 An electron from the emitter causes ionization of the carrier
gas (often N2) & the production of a burst of electrons.
 In the absence of organic species, a background current
between a pair of electrodes results from this ionization
process.
 When analytes that can capture electrons e.g with halogens,
peroxides & nitro groups enter the detector, electrons from the
background current are captured, therefore the current is
decreased.
107

 Non-destructive.
 Sensitive.
 Selective to organic molecules or analytes which contain
electronegative functional groups that can capture electrons
e.g. halogens, peroxides, quinones & nitro groups.
 Insensitive to amines, alcohols, ketones & hydrocarbons.
 Widely used detectors for environmental samples such as
chlorinated pesticides & polychlorinated biphenyls.
 Disadvantage : involve radioactive component.
108

Sample problem 6
In the GC analysis of polar contaminants from an
aqueous sample, splitless injection mode was used to
introduced sample into a capillary column with N2 as a
carrier gas & electron capture detector.

109

Thermal Conductivity Detector (TCD)

110

 The TCD works by measuring the change in carrier

gas thermal conductivity caused by the presence of
the sample, which has a different thermal conductivity
from that of the carrier gas.
 Their design is relatively simple & consists of an
electrically heated source that is maintained at
constant power.

111

 The temperature of the source depends upon the

thermal conductivities of the surrounding gases.
 The source is usually a thin wire made of platinum or
gold.
 The resistance within the wire depends upon
temperature, which is dependent upon the thermal
conductivity of the gas.

112

 TCDs usually employ two detectors, one of which is

used as the reference for the carrier gas & the other
which monitors the thermal conductivity of the carrier
gas & sample mixture.
 Carrier gases such as helium and hydrogen has very
high thermal conductivities so the addition of even a
small amount of sample is readily detected.

113

 Universal, not selective (broad application to

inorganic and organic compounds).
 Non-destructive.
 Disadvantage : Not sensitive.

114

GC detectors & their detection limits

Symbol

Detector Type

FID

Flame Ionization

ECD

Electron Capture

TCD

Thermal
Conductivity

Selectivity
Most organic cmpds that ionize in
flame

Detection limit
100 pg

Halides, nitrates, nitriles, peroxides,

anhydrides, organometallics

50 fg

Universal

1 ng

Aliphatics, aromatics, ketones,

esters, aldehydes, amines,
heterocyclics, organosulphurs,
some organometallics

2 pg

PID

Photoionization

NPD

Nitrogen
Phosphorus

Nitrogen, phosphorus

10 pg

FPD

Flame
Photometric

Sulphur, phosphorus, tin, boron,

arsenic, germanium, selenium,
chromium

100 pg

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Detection techniques & their applications

Detector

Used for

Mass spectrometer (MS)

Identification of unknown compounds

Flame Ionization Detector

(FID)

Compounds containing Carbon

Thermal Conductivity
Detector (TCD)

Universal detection for gases without Carbon

Nitrogen Phosphorous
Detector (NPD)

Selective detection of Nitrogen and Phosphor

containing compounds

Electron Capture Detector

(ECD)

Selective detection of halogen containing

compounds

Atomic Emission Detector

(AED)

Selective detection of elemental composition

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Interfacing GC with spectrometric detectors :




Mass spectrometry (MS)

Fourier Transform Infrared Spectroscopy (FTIR)

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Mass spectrometry detector

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 The GC-MS is composed of two blocks :

 GC
 Mass spectrometry (MS)
 Molecule elutes from the GC & allows the MS
downstream to capture, ionize, accelerate, deflect, &
detect the ionized molecules separately.
 The MS does this by breaking each molecule into
ionized fragments and detecting these fragments
using their mass to charge ratio.
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 The MS is used to identify comps based on

their structure, meaning that it will provide the
structural information of each comps match from
the library of mass spectra of known comps
stored on the computer & thus can identify the
comp.

120

 Applications of GC-MS
 Drug detection.
 Fire investigation.
 Environmental analysis
 Explosives investigation.
 Identification of unknown samples.
 GC/MS can also be used in airport security to detect
substances in luggage or on human beings.

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 Types of MS detectors :
 Quadrupole MS (trade name "Mass Selective
Detector" (MSD)).
 Ion trap MS.
 Time of flight (TOF).
 Tandem quadrupoles (MS-MS).

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METHOD DEVELOPMENT FOR GC

123

 Method development is the process of

determining what conditions are adequate
and/or ideal for the analysis required.

Areas to optimize
a) Injector
b) Carrier gas
 Optimal range of velocities based on van
Deemter curve.
 Too low or high velocity results in loss of Rs.
 Balance Rs vs analysis time.

124

c) Column Temperature
 The optimum column temperature is
dependant upon the boiling point of the
sample.
 Minimal temperatures give good resolution,
but increase elution times.

125

Factors which affect GC separations

 Efficient separation of compounds in GC is dependent on
the compounds traveling through the column at different
rates.
 The rate at which a compound travels through a particular
GC system depends on :
 Volatility of compound : Low boiling (volatile)
components will travel faster through the column than
high boiling components. Boiling points of the
different components is the main factor in GC
separation.
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 Polarity of compounds : Polar compounds will move slowly

if the column is polar. Differences in polarity of the compounds
is only important if you are separating a mixture of
compounds which have widely different polarities.
 Column temperature : Raising the column temperature
speeds up the elution of all the compounds in a mixture.
Separation based on isothermal temperature or temperature
programming.

127

 Column polarity : Usually, all compounds will move

slower on polar columns, but polar compounds will show
a larger effect.
 Flow rate of the gas through the column : Speeding up
the carrier gas flow increases the speed with which all
compounds move through the column.
 Length of the column : The longer the column, the
longer it will take all compounds to elute. Longer columns
are employed to obtain better separation (higher N).
128

 Factors to be considered in selecting the column :

 Polarity of stationary phase
 Column length & diameter
 Thickness of stationary phase

129

The heights of the later eluting peaks are

reduced & the peak widths increased
because they are more affected by the
lower temperature program used.

ISOTHERMAL

Constant column temperature

throughout the analysis
Oven temperature :
100 oC

TEMPERATURE PROGRAMMING

Column temperature is
increased either continuously or
in steps as the analysis proceeds
Oven temperature:
60oC for 1 min
60-180oC at 20o/min
130

Temperature program method

 In the analysis of mixtures with a broad boiling point
range causes a group of early eluting comps (low bp.)
separated & late eluting comps (high bp.) will have very
long tR at low isothermal temperature.
 When the column temperature is increased, the early
eluting comps (low bp.) will overlapped & late eluting
comps (high bp.) separated.

131

 Thus, use temperature programming with initial low

temperature to separate low bp. comps & the
temperature is increased at a rate (either increased
continuously or in steps) to reduce the tR for the high bp.
comps.
 Rates of 5-7 C/min are typical for temperature
programming separations.
 A temperature program allows comps that elute early in
the analysis to separate adequately, while shortening the
time it takes for late eluting comps to pass through the
column.
132

The effect of column temperature on the shape of the peaks

Low T

High T

time
133

General elution problem

 It is sometimes difficult to get an optimum separation of ALL

components in the mixture in a reasonable period of time.

 Change flow and column
material. 3,4,5,6 OK but early
peaks 1,2 still not resolved.
 All peaks separated BUT3
hour separation & 5,6 have
poor signal.
 increase flow or change
column, good separation time
but 1,2 & 3,4 are not resolved.
134

Solution to general elution problem

 If we could change the separation conditions (ie. K) as the
separation proceeds, we could optimize conditions for
separation of early peaks in the first part of the procedure.
 Then change conditions to gradually optimize conditions for
late eluting components, so that they are adequately
separated in a reasonable period of time.
 How do we change K as separation proceeds?
 Gas Chromatography- temperature programming
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Developing temperature programming

136

Developing temperature program

137

Asymmetric peak shapes

 Tailing---occurs when
there are some other sites
on stationary phasethat
have strong interaction
with solute

 Concentration of solute
injected is too high--stationary phase cannot
handle-138

 Overloaded column

 Too much solute has been applied to the column.

 As the conc. of solute increases, the solute becomes
more & more soluble in the stationary phase (like
dissolve like).

 There is so much solute in the stationary phase that

the stationary phase begins to resemble solute.

139

 The front of an overloaded peak has gradually

increasing concentration.

 As the concentration increases, the band become

overloaded.

 The solute is so soluble in the overloaded zone that

little solute trail behind the peak.

 The band emerges gradually from the column but ends

abruptly.

140

Sample preparation for GC

141

 Derivatization
 Pyrolysis
 Headspace

Chemical derivatization
142

 GC - for separation of volatile compounds which are

thermally stable.
 Not always possible particularly for those of high
molecular weight and/or molecules containing polar
functional groups.
 Derivatization used when analytes are not sufficiently
volatile, tail significantly (too strongly attracted to the
stationary phase) & thermally unstable (decompose).

 Chemical derivatization can :



Increase the volatility & decrease the polarity of

compounds.

Reduce thermal degradation of samples by increasing

their thermal stability.

Improve separation & reduce tailing.

Increase specific detector response by incorporating

functional groups which lead to higher detector signals,
e.g. CF3 groups for ECD.
143

 Common derivatization methods can be classified

into 4 groups depending on the type of reaction
applied :
 Silylation
 Acylation
 Alkylation
 Esterification

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Interfacing GC with Spectroscopic Methods

145

 GC coupled with the selective technique of

spectroscopy so-called hyphenated methods.
 Tools for identifying the components of complex
mixtures.

THE END

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