Gas Chromatography in Capillaries

Ernst Kenndler: Gas Chromatography
GAS CHROMATOGRAPHY
ERNST KENNDLER
Institute for Analytical Chemistry, University of Vienna
THEORETICAL ASPECTS OF GAS CHROMATOGRAPHY ............................................................ 2

1.1 DISTRIBUTION CONSTANT, SEPARATION SELECTIVITY ............................................................................... 2
1.1.1
Temperature Dependence of Distribution Constant........................................................................ 4
1.1.2
Retention index IR ............................................................................................................................ 5
1.2 DISPERSION IN CAPILLARY GC .................................................................................................................. 7
1.2.1
Golay equation .............................................................................................................................. 11
1.2.2
Plate height vs. retention factor. ................................................................................................... 13
PRACTISE OF GAS CHROMATOGRAPHY....................................................................................... 15

2.1 CARRIER GAS ........................................................................................................................................... 15
2.2 SAMPLE INLET ......................................................................................................................................... 17
2.2.1
Split and splitless injector ............................................................................................................. 18
2.2.2
On-column injection...................................................................................................................... 20
2.3 COLUMNS ................................................................................................................................................ 21
2.3.1
Stationary phases .......................................................................................................................... 22
2.3.2
Rohrschneider / McReynolds index............................................................................................... 24
2.4 COLUMN OVEN ........................................................................................................................................ 26
2.5 SPECIAL DETECTORS ............................................................................................................................... 26
2.5.1
Flame ionisation detector.............................................................................................................. 26
2.5.2
Electron capture detector.............................................................................................................. 28
2.5.3
Alkali flame ionisation detector .................................................................................................... 31
FURTHER READINGS............................................................................................................................ 34
Ernst Kenndler
Version 19/01/2004
THEORETICAL ASPECTS OF GAS CHROMATOGRAPHY
This text should be read in context with Introduction in Chromatography, where a

fundamental discussion of the migration and dispersion phenomena occurring in the
chromatographic separation system is given in a general manner. In the present contribution
the theoretical discussion is mainly directed towards gas liquid chromatography in capillary
columns. This chapter about theory of gas chromatography is followed by a considerably
detailed presentation of practical aspects of this method.
1.1
Distribution constant, separation selectivity
In Gas Liquid Chromatography the analytes are distributed between a liquid stationary phase
and an ideal gas as the mobile phase as schematically shown in Figure 1.
<v>
cim (t)
GAS
LIQUID
cis (t)
Figure 1 Schematic presentation of a gas-liquid chromatographic system. <v> is the average

linear velocity of the mobile phase. cim (t) and cis (t) are the concentrations of the analyte, i, in
the mobile and the stationary phase, respectively. Both are functions of time.
This distribution is determined by the partition constant, given as usual by
Ki =
c il
c im
(1)
However, for practical reasons the concentration in the liquid is expressed by the mole
fraction, xi, and that in the gas phase by its partial pressure, pi.
For the concentration in the liquid we express the vapour pressure of the solute, i, over
the binary mixture consisting of liquid phase and analyte by Henry`s law
p i = H p i0 = i0 x il p i0
(2)
Where H is the Henry constant, xil the mole fraction of analyte, i, in the liquid phase, i0 is
the activity coefficient (at infinite dilution), pi0 is the vapor pressure of the analyte (as pure
compound) at the given temperature.
The partial pressure, pi, of the analyte in the ideal gas phase is given by Dalton`s law
pi =
n ig
RT
Vg
(3)
T is the absolute temperature and R is the gas constant.

Substitution of the volume concentrations in eq. 1 (for infinite dilution) gives the
expression for the partition constant in GLC:
K io =
RT
p ioVs ,mol
(4)
o
i
where Vs,mol is the mean molar volume of the stationary phase.

Two most important parameters occur in this expression:
p io , the vapour pressure of the analyte as pure compound at temperature T
i0
the activity coefficient of the analyte in the stationary liquid (at infinite
dilution).
Separation selectivity of two consecutively eluting components, i and j, is defined in
chromatography by the selectivity factor, ji, the ratio of the distribution constants, K.
However, measurement of the values of K is complicated compared to k` values. As in a
certain chromatographic system the phase ratio is the same for all components, the selectivity
coefficients can be expressed by the ratio of the k` values of the pair of separands
ji =
k j,
(5)
k i,
The selectivity coefficient for GLC using eq. 4 is thus
ji =
pio io
p oj
(6)
o
j
It can be seen that selectivity in GLC is determined by two ratios:

the ratio of the vapour pressures of the analytes as pure compounds (at
working temperature)
the ratio of the activity coefficients the in stationary phase (at infinite
dilution).
Whereas the temperature only influences the first, the second reflects the difference in the
chemical interactions of the two separands in the stationary liquid. Insofar it is in fact a kind
of molecular recognition, which determines selectivity. This is exactly what makes the use of
different stationary phases meaningful.
1.1.1 Temperature Dependence of Distribution Constant

Eq. 4 might lead to the erroneous conclusion that the distribution constant in GLC increases
with increasing temperature. In fact the contrary is the case, because this linear dependence of
K on T is more than overcompensated by the exponential increase of the vapour pressure, pio ,
with temperature, according to the Clausius-Clapeyron equation. For this reason the
distribution constant, and the capacity factor as well, decreases strongly with increasing
temperature. In fact the following linear approximation can be found
log K io resp. log k i'
1
T
(7)
The experimental dependence of the capacity factor on the temperature is shown in

Figure 2 for two analytes.
lok k
10
etbenzoat
C7ol
0,0023
0,0024
0,0025
0,0026
0,0027
0,0028
0,0029
1/T
Figure 2 Relation of the logarithm of ethylbenzoate and 1-heptanol on the reciprocal of the
absolute temperature.
1.1.2 Retention index IR

In contrast to HPLC, gas chromatography possesses a useful and generally accepted
parameter for the characterisation and identification of analytes. This parameter is based on
the finding that log k` values of the members of a homologous series of organic compounds
are linearly depending on the number of carbon atoms, n, in their molecules. Applied to the
homologous series of n-alkanes this means that
log k n, = A + B. n
(8)
log k`
This relation can be graphically represented by
18
16
14
12
10
8
6
"n" = 11,63
4
4
10
12
14
16
18
number of C atoms
Figure 3 Logarithm of the retention (capacity) factor, k`, of the homologues series of the nalkanes as function of the number of carbon atoms
For each analyte with a certain capacity factor a pair of n-alkanes exists, between that the
analyte is eluted in the chromatogram. This analyte is considered as a fictive n-alkane with a
hypothetical number of C-atoms, in the example in Figure 3 with 11.63 C-atoms. This number
(and the number of C-atoms of the n-alkanes as well), multiplied by 100, is the retention
index. The analyte in the example given consequently has the retention index 1163. It is
obvious that n-alkanes have always retention indices with full hundreds, n-hexane e.g. 600, nundecane 1100, n-eicosane 2000, etc.
Obviously the retention index of analyte i is normally determined with higher
accuracy than it would be possible by graphical interpolation. For this reason the following
equation is used that can be derived simply from Figure 3 by comparison of similar triangles:
I Ri = 100 z
log k i, log k n,
+ 100n
log k n, + z log k n,
(9)
Substitution of the capacity factors by the net retention times
t RiN = t Ri t R 0
(10)
leads to an expression convenient for measurement and determination of the retention index
log
I Ri = 100 z
log
t RiN
N
t Rn
t RN( n + z )
+ 100n
(11)
N
t Rn
Here (n+z) and n are the numbers of C-atoms of the n-alkanes eluting after and before the
analyte. Usually, but not necessarily, z is 1. If e.g. due to economic reasons only the (cheaper)
even-numbered higher n-alkanes are used (e.g. C26 and C28), z is 2 in that case.
It is the advantage of the retention index that it is independent of certain, often varying
experimental parameters:
velocity of the mobile phase

phase ratio
length of the column.
It depends on:
kind of the stationary phase

(column temperature)
It is therefore a very well suited number for the characterization of an analyte on a certain
stationary phase. Retention indices are used for identification of an analyte by comparison of
the value of the index with either that found in tables, or determined previously with the help
of reference compounds. Retention indices of an unknown compound on different stationary
phases allow further conclusions about the polarity of the analyte.
Table 1 Retention indices and IR values of differently polar C8 compounds on apolar
polydimethyl siloxane (OV1) and polar polyethylenglycol (PEG) as stationary phase
Compound
IR (OV1)
IR (PEG)
IR =IRpolar IRunpolar
n-octane
800
800
n-dibutylether
864
966
102
n-hexylacetate
963
1101
138
n-octanon-2
957
1295
338
n-octanol-1
1038
1545
507
For this purpose the indices are determined at two columns with different polarity, e.g. with
methylsiloxane and polyethylenglycol as stationary liquids. Obviously n-alkanes have always
a IR -value of zero. The more polar the functional group is, the larger is the IR value.
IR value values of selected reference compounds are used to describe the polarity of
stationary phases as well (see concept of the Rohrschneider / McReynolds index, chapter
2.3.2.).
Conclusion for the use of retention indices:
Retention indices at one phase
n-alkanes always full hundreds, n-hexane 600, etc.

homologues differ by 100 at one stationary phase
Retention indices at two phases
IR =IRpolar IRunpolar
zero for n-alkane
IR the larger, the more polar functional group

IR values of selected reference compounds are used to describe the polarity of
stationary phase
1.2
Dispersion in capillary GC
Peak dispersion in chromatography is discussed in general in Introduction to

chromatography. We will here concentrate on dispersion in capillary GC.
Peak broadening is described by the model of the theoretical plate height, H. Note that
4 processes were found to contribute to the total plate height in chromatography.
Hdiff describes the contribution from longitudinal diffusion
Hconv that from convective mixing
Hex,m that stemming from the kinetics of mass exchange from the mobile phase to the
interface between mobile and stationary phase
Hex,s that from the kinetics of mass exchange from the stationary phase.
Consequently the total plate height is the sum of the four contributions:
H = H diff + H conv + H ex ,m + H ex ,s
(12)
(ad Hdiff )
The contribution of longitudinal diffusion, that in direction of zone migration, is caused by the
concentration gradient occurring between the sample and its surrounding in this direction.
According to the Einstein equation the resulting peak variance in the space domain is given by
(13)
z2 = 2 Dmi t
Broadening of the peak with time according to eq. 13 is shown in Figure 4.
The equivalent expression for the relation between plate height and variance is
(14)
z2 = Hz
1,2
concentration
1,0
function
t0
lim z = 0
t1
0,8
concentration
10 0
1 50
200
0,6
t2
0,4
0,2
t3
0,0
Figure 4 Development of peak broadening with increasing time due to diffusion. The
concentration zone was infinitely narrow at time 0 ( - or Dirac function)
This contribution is as more pronounced as larger the diffusion coefficient, Dm,i , of the
analyte in the mobile phase is, and as longer the time is available for diffusion. Consequently,
this increment increases with decreasing velocity of the mobile phase; it is proportional to 1/v.
It follows that the plate height contribution due to longitudinal diffusion is
H diff =
2 Dm,i
(15)
It should be mentioned that longitudinal diffusion in the stationary phase does not
significantly contribute to peak broadening, because the diffusion coefficients in the
stationary phase are 5 to 6 orders of magnitude smaller than those in the gas phase.
(ad Hconv )
The radial velocity profile of the mobile phase flowing through the column introduces an
effect to peak broadening due to convective mixing. In case of an open tube (as it is in
capillary GC) the flow profile can be analytically described in a simple way, in contrast to
packed beds. It has a parabolic shape with zero velocity at the capillary wall, and maximum
velocity at the centre of the tube with radius rC. For a non-retained component the
contribution to the plate height is described by the so-called Taylor-dispersion
H conv =
rc2
v
24 Dm ,i
(16)
radius, r
v ma x
30 00 0
25 00 0
2000 0
15 000
10 00 0
5 00 0
-5 000
velocity
- 10 00 0
Figure 5 Profile of the velocity, v, of the mobile phase in an open tube as function of radius, r
The resulting dispersion due to the parabolic flow profile and the radial diffusion would give
the following peak for a non-retained component
2 ,4
2 ,2
2 ,0
concen tration
1 ,8
1 ,6
1 ,4
1 ,2
parabolic
1 ,0
flow profile
0 ,8
0 ,6
flo w profile
0 ,4
ra dial diffusion
0 ,2
0 ,0
-0,2
20
10
-10
-20
Figure 6 Peak profile resulting from parabolic flow and radial diffusion
(ad Hex,m )
Both mass exchange terms have their origin in the finite rate of mass transport from the inner
part of the mobile or stationary phase, respectively, to the interface between these two phases.
Roughly it can be said that at the front of the peak in the mobile phase a higher concentration
exists than the equilibrium concentration. At the rear side the opposite situation occurs. From
these kinetic reasons peak dispersion occurs, which increases with increasing velocity of the
mobile phase. The effect in the mobile phase is connected to the flow situation. Therefore the
contribution of the finite mass transfer in the mobile phase is combined with that stemming
from the flow profile, which enlarges eq. 16. The combination of both effects leads to
Hconv + ex ,m =
(1 + 6k i, + 11k i,2 )
rc2
(1 + k i, ) 2
24 Dm,i
(17)
(ad Hex,s )
The term which stems from the finite kinetics of mass transport in the stationary phase is
given by
H ex ,s
d 2f
k i,
2
=
v
3 (1 + k i, ) 2 Ds,i
(18)
10
where df is the thickness of the stationary phase layer, and Ds,i is the diffusion coefficient in
the stationary phase.
1.2.1 Golay equation

The Golay equation describes the total plate height, given by the sum of the particular
increments that contribute to peak dispersion:
H =
2 Dm,i
(1 + 6k i, + 11k i,2 )
rc2
(1 + k i, ) 2
24 Dm,i
v+
d 2f
k i,
2
v
3 (1 + k i, ) 2 Ds,i
(19)
This equation shows the dependence of the particular increments, and thus the total plate
height, as a function of the velocity of the mobile phase, apparently one of the most important
experimental variables to influence peak dispersion. Eq. 19 can be rewritten in a simplified
form as
H=
B
B
+ (Cm + C s ). v = + Cv
v
v
(20)
1,0
0,8
0,6
0,4
C.v
0,2
0,0
B/v
0
20
40
60
80
100
Figure 7 Plot of the plate height as a function of the mobile phase velocity (Golay equation).
The depiction of the plate height in relation to the mobile phase velocity is given in Figure 7.
It results in the summation of the hyperbolic B-term of eq. 15, that depends on 1/v, with the
C-term, which increases linearly with v. From Figure 7 it can be seen that a singular velocity
exists where the plate height exhibits a minimum value. Here peak dispersion is smallest. If
minimum dispersion (highest efficiency) is necessary for sufficient separation, this particular
velocity has to be selected. On the left-hand side of the H vs. v curve the plate height steeply
11
increases due to pronounced diffusion and the time of analysis increases as well. Insofar there
is no cause to select such velocities in practice. On the right hand side of the minimum, in
contrast, the plate height increases considerably slowly, and approaches the C-term
asymptotically at high velocity. In this range the working conditions are selected favourably
when the separation is large enough due to sufficient selectivity. In this case the time of
analysis, which is often an important analysis parameter, will be reduced with not too high
loss in efficiency.
1.2.1.1 Gas as compressible fluidum
It was pointed out that in GC there is an average linear velocity, <v>, which differs from the
local velocity, v, at a certain position at the longitudinal coordinate of the column due to the
compressibility of the gaseous mobile phase. The particular velocity depends on the pressure
drop across the column.
p0
Figure 8 Schematic drawing of the local flow velocity, v, (indicated by arrows) of a

compressible fluidum across the capillary. p pressure, p0 pressure at the column outlet
The deviation of the volume flow velocity can be derived by the correction factor according to
Martin and Synge
3 ( p p0 ) 1
j=
2 ( p p0 )3 1
2
(21)
where p and p0 are the pressures at the top and the end of the capillary.
Consequently the minimum plate height is observable only in a small part of the
separation capillary, where the particular mobile phase velocity is optimal. All other velocities
12
deviate in principle from this value for minimum plate height. However, under usual
conditions in capillary GC (for columns not too narrow and long) p does not exceed p0 by
more than 1.5 fold. In this case the difference between the average linear velocity (which is
measured by <v> = L/tR0) and the actual velocity at any section inside the capillary is
negligible, and the plate height does not change significantly across the capillary. For this
reason the variation of the velocity due to the compressibility of the gaseous mobile phase
normally is not a matter for consideration.
1.2.2 Plate height vs. retention factor.

Another important fact can be seen from the Golay equation as well: the plate height is
dependent on the capacity factor. It follows that for given instrumental conditions H may
change drastically for different components of a sample mixture, given that these components
have considerably different k values. For a capillary column, e.g., with a very thin film of
stationary phase, for which the third term in eq. 19 can be neglected, the dependence of the
plate height from the k` values of the sample components can be expressed by Figure 9.
10
8
,2
(1+6k +11k )/(1+k )
, 2
12
6
4
2
0
0
10
Figure 9 Dependence of the second term of the Golay equation (eq. 19) on the capacity
factor.
This term reaches values between 1 (for k` of zero; here peak broadening is given by Taylor
dispersion) and approximately 11 at large values for k`. This means that for otherwise equal
experimental conditions the plate height of the peaks within one chromatogram can vary by as
much as one order of magnitude.
If the stationary phase of the capillary column has not such a thin film, the Cs-term
may play a role as well. For such cases the dependence of this term on the k` of the analytes is
shown in Figure 10.
13
0,30
k`/(1+k`)
0,25
0,20
0,15
0,10
0,05
0,00
0
10
k`
Figure 10 Cs-term as function of the retention factor (eqs. 18 and 19)

A closer analysis of the dependence of the plate height on the capacity factor of the solutes
enables conclusions on the properties of the separation column concerning the significance of
the particular terms. According to the weight of the two terms different relations of H as
function of k` are found for the individual columns. The theory of chromatography in
capillary column delivers the instrument to evaluate the occurring effects.
Note that it is the plate number, N, rather than the plate height, which is decisive for
the separation of two analytes:
N=
L
H
(22)
The plate number of the particular components of a sample can simply be calculated from
their retention time, and the corresponding standard deviation (or the half peak width w), all
parameters taken in the time domain, and in the same units by
2
t R ,i
t
= R ,i * 5.54
N i =
w
t ,i
t ,i
(23)
14
PRACTISE OF GAS CHROMATOGRAPHY
A gas chromatograph consists of several parts, which are described in the following in more
detail (cf. e.g. refs.
1-13
) and can indeed often be handled as modules in instrumental practice.
They are schematically shown in Figure 11. Roughly, a chromatograph is composed from the
carrier gas supply, the sample inlet, the column, positioned in a column oven, the detector(s)
and a device for data collection, acquisition and processing.
Carrier
Gas
Supply
Sample
Inlet
Column Oven
Detector
Data
Collect.
Acquis.
Process.
Figure 11 Scheme of a gas chromatograph
2.1
Carrier gas
As mobile phase an inert gas is used, which is delivered by a gas generator, or a gas cylinder.
The most common carrier gases are H2, N2, He. They must be of very high purity, because
traces of water or oxygen may decompose the stationary phase, which leads to column
bleeding and finally destruction of the column. Therefore special devices for gas purification
are installed often prior to the sample inlet.
The choice of the carrier gas depends on several demands, e.g. the appropriate
operation of the detector (for the combination of GC with MS e.g., He is needed), on safety
reasons (H2 is explosive), or on the price (N2 is the cheapest gas), but also on demands on
separation efficiency and speed. Due to its lowest viscosity of all gases, H2 e.g. allows to
operate the column with the highest mobile phase velocity - and therefore lowest analysis
time - at comparable efficiency (see below).
Summary of the demands on the carrier gas:
Chemically inert
High purity (water, oxygen)
15
Detector compatibility
Economic / Safety reasons
Efficiency / Speed
Concerning efficiency and speed depending on the kind of carrier gas we ask for the condition
of plate height minimum. This is
dH
=0
du
(24)
With the simplified Golay equation (eq. 20) we obtain

H min = 2 BC
rc
(25)
It can be seen that this plate height is independent on the kind of mobile phase (see Figure
12). It is depending on the radius of the capillary only. This plate height is reached at the
mobile phase velocity
u min = B C
(26)
7 Dmi rc
The velocity where minimum plate height is reached depends on the gas used as mobile
phase, because the diffusion coefficient is related to the gas viscosity. Therefore hydrogen as
mobile phase reaches minimum plate height at higher mobile phase velocity than e.g.
nitrogen. Faster analyses can be achieved therefore.
10
plate height, H
H2
4
N2
0
0
10
15
20
mobile p hase velocity, v
Figure 12 Peak height vs. mobile phase velocity for hydrogen and nitrogen as carrier gases
16
2.2
Sample inlet
In GC the sample is normally brought into the separation system in liquid solution (sampling
techniques for vapours, e.g. head space or adsorption / thermodesorption injection, or for solid
samples, e.g. pyrolysis injection, are not discussed here). The sample is dissolved in an
organic solvent, which is normally injected into the carrier gas flow by the aid of a syringe or
a valve. Indeed the quantitative and non-discriminating introduction of the sample into the
column is the most critical part of all experimental steps in capillary gas chromatography.
Although GC is a well-developed and established method, sample introduction in capillary
GC is still a non-trivial task due to practical limitation. This results in a number of different
injector types, which should be selected in practice according to the nature of the sample and
the demands in accuracy and reproducibility of the analysis.
In contrast to capillary GC, sample introduction in packed column GC is not a
problem. This is due to the fact that in packed bed GC the column volume is large, and the
phase ratio is considerably large, too. Here the sample, dissolved in a volatile organic solvent,
is simply injected into a heated and thermostatted injector cell, where it is evaporated, and the
vapour is transported by the carrier gas into the column. Note that 1 l of liquid sample
delivers several hundred L vapour after evaporation. It is clear that such a large volume
would overflow the entire column in case of a capillary column. As an example: a capillary
with 0.2 mm I.D. and 25 m length has a total volume of less than 800 L. It is obvious that it
is not possible to introduce the entire evaporated sample directly into the column in capillary
GC. Therefore mainly two possibilities are proposed to overcome this problem in practise:
(i)
In case of the evaporating injectors the sample is inserted by a syringe into the
heated injector and evaporated. Either only a part of the evaporated sample is allowed
to enter the capillary this is realised with the split injector; or the main part of the
solvent (and a small part of the sample as well) is separated in the injector from the
sample components. In this splitless mode the sample components normally are
recondensed at the top of the column either by cold trapping or by solvent
trapping.
(ii)
the total liquid volume is brought into the cold injector by the aid of a syringe, and
solely the solvent is evaporated carefully first and usually recondensed either at the top
of the column, or in the retention gap. Due to careful selection of the temperature
conditions the sample remains at the top of the separation system. Then the sample is
evaporated, too, and introduced into the separation capillary.
17
2.2.1 Split and splitless injector

In the split mode (see Figure 13A) the sample is rapidly injected and evaporated in the liner of
the heated injector. The gas flow (vaporised sample mixed homogeneously with the carrier
gas) is divided at the top of the column by the aid of a needle valve (which enables to adjust
different split ratios). The main part of the gas mixture is flushed out, and only a small part is
allowed to stream into the separation capillary. The injector has the advantage that the
injected zone is narrow, and the small sample aliquot entering the capillary avoids
overloading of the column.
Although very flexible in practice, this injector has a number of disadvantages. In
many cases mass discrimination of sample components is observed, especially when the range
of their volatility differs much. Therefore systematic errors for quantitative analysis may
occur. Another disadvantage, especially in trace analysis, is the fact that only a part of the
analytes is transferred into the capillary, and reaches the detector. The main part of the sample
is deleted via the split and therefore lost for detection.
To overcome such problems the injector can be operated in the splitless mode. Here
the capillary is first run in the split mode. Directly prior to injection the split is closed. The
sample is then slowly injected into the heated injector, and sample and solvent are evaporated.
It is most important that in this mode the column is kept at relatively low temperature, lower
than the boiling point of the solvent. Therefore the volatile solvent condenses at the top of the
column, and forms a kind of a stationary phase here. Volatile sample components, which
evaporate in the injector, too, are dissolved again in the liquid formed, and are therefore
refocused (solvent trapping). Less volatile sample components, which were also evaporated
in the hot injector, are recondensed on the top of the colder column, and focused, too (cold
trapping).
After these two processes have taken place, the split is opened (after about 30 90 s)
and the rest of the solvent is flushed via the split valve. The solvent that initially forms a
liquid sheath at the top of the column evaporates gradually, with progressive evaporation
from the injector to the detector side. This effect supports the refocusing of the sample
components. Finally the sample is evaporated by the application of a temperature program,
which is obligatory for this injection technique. The entire procedure avoids the large tailing
of the solvent peak observed otherwise, and allows the transfer of the main part of the sample
components into the column and, finally, into the detector. It is therefore a favourable
technique for the insertion of diluted samples in trace analysis.
18
A)
B)
Figure 13 (A) Schematic drawing of a split-splitless injector (from ref.
10
with permission).
(B) Schematic drawing of an on-column injector. 1 Carrier gas inlet, 2 Sealing; 3 Capillary
column, 4 Cooling gas (from ref.
14
with permission).
The recondensation of the solvent at the top of the capillary can be critical by damaging the
stationary phase (because it might be partially dissolved by the condensed liquid), and
therefore only columns with chemically bonded phases should be used. Another limitation is
the necessary wettability of the stationary phase by the condensed solvent, otherwise droplets
are formed rather than a liquid layer. These problems may be overcome by the use of an
empty (widebore) capillary without stationary phase, mounted between injector and
separation column. In this capillary indeed both refocusing processes solvent trapping and
cold trapping as described above can be established. This construction is named retention
gap, and is used in the splitless mode and, more common, with the on-column injection
technique.
19
It should be mentioned that the discriminating evaporation of volatile sample

components (according to their boiling points) when injected into the hot injector can be
diminished by a modification called programmed temperature vaporiser (PTV injector). The
PTV device can be used for the split and the splitless mode as well. Here injection is carried
out into the cooled injector. When operated initially at a temperature slightly above the
boiling point of the solvent (but below those of the most volatile sample components), the
main part of the solvent can be separated via the open split (solvent purge). After flushing
the solvent the PTV injector is heated up rapidly, and the sample is transferred to the top of
the column as a more or less narrow band.
Summary of the advantages and disadvantages of split and splitless injectors:
SPLIT INJECTOR
Advantage
Injected zone narrow
Small sample aliquot avoids overloading
Limitations
Mass discrimination of sample components
(different range of volatility)
Systematic errors for quantitative analysis
In trace analysis: only part of analytes to detector
SLITLESS INJECTOR
Advantage
Avoids large tailing of solvent peak
Allows transfer of main part of sample
components into detector
Trace analysis: favourable technique for
insertion of diluted samples
Limitations
Recondensation of solvent at top of capillary:
possible damaging stationary phase
Only columns with chemically bonded phases
Necessary wettability of stationary phase for
condensed solvent (droplets)
2.2.2 On-column injection

With the on-column technique the sample solution is directly inserted into the column with
the aid of a syringe with a long, narrow needle, whereby the injector (Figure 13B) is
maintained at low temperature. Due to the restricted mechanical stability of the thin syringe
needle a normal septum cannot be used, and is replaced by special sealing. In most cases a
piece of a wide bore capillary (retention gap) is connected to the thinner separation capillary
to avoid column flooding by the large volume of sample vapour.
Retention gap: empty capillary - fused silica, widebore (0.5 mm i.d.), 20 200 cm L without stationary phase mounted between injector and separation column
20
The capillary for the retention gap is mounted in the column oven, whose temperature must be
adjusted to the boiling point of the solvent. If the temperature is below the boiling point,
solvent trapping takes place. If it is selected slightly above the boiling point, cold trapping of
the sample components occurs. In both cases the chromatogram must be developed with an
adequate temperature program of the column, which is an essential step when using this
injector type.
Advantage of on-column injector:
avoids mass discrimination effects

trace analysis: enables quantitative insertion of sample into column (and detector)
labile components not stressed thermally
2.3
Columns
In gas chromatography packed bed columns and capillary column are used. Packed columns
are tubes made of glass or metal with 2-4mm I.D. and 1-6 m length. They are filled with
porous particles, which act as support of the stationary liquid phase, which is coated on the
porous material.
Capillary columns are open tubes with 0.1 to 0.5 mm I.D. and 5 to 100 m lengths.
Most common dimension, however, are 0.3 mm I.D. and 25 m length. Originally the
capillaries were made from metal or glass; in the last decade fused silica replaced all other
materials. Fused silica has the advantage of a very inactive inner surface, which avoids
adsorptive interactions between analytes (especially when they are polar) and adsorption
centres, leading otherwise to tailing peaks or even loss of material due to irreversible
adsorption (see note below on Grob`s test mixture). It has the further advantage of extremely
high mechanical stability that reduces breakage of the columns.
The stationary phase is coated as a thin layer (with 0.1 to 5 m film thickness) onto
the inner wall of the open tube. Normally this phase is a liquid. Due to modern column
technology, which enables cross-linking of the polymer molecules of the liquid, and even
attachment of the phase at the silica surface due to chemical bonding, the initially liquid phase
might behave as large, single, polymeric molecule. Interestingly these cross-linked phases
thermodynamically behave very similar to the initial liquid.
21
PACKED COLUMN
CAPILLARY COLUMN
Stationary phase
Packing
Figure 14 Schematic drawing of packed and capillary columns
It should be mentioned that a mixture of solutes, which allow conclusions about specific
adsorptive sites, could test the adsorptivity of columns. The most common is the so-called
Grob test mixture, which consists of octan-2-on, octanol-1, 2,6-dimethyl phenol, 2,4-dimethyl
anilin, naphthalin, tridecan and tetradecan.
2.3.1
Stationary phases
Stationary phases must cover a wide range of polarity as indicated in the following Table.
Apolar phase
vapour pressure
Polar phase
intermolecular forces
dispersion
polarisation
dipole-dipole
hydrogen bonding
Besides being the source for separation selectivity in GC, the demand on stationary phases is
thermal stability. It is clear that polymeric compounds best fulfil the latter restrictions.
Especially siloxane polymers have a high thermal stability, caused by the Si-O backbone of
the silicon chain. The type of the substituents attached at this chain implements selectivity.
CH3 groups as substituents give the lowest polarity, resulting in a polymer that is nearly as
22
A)
Si
Si
Si R1
H3C CH R1 R2
R2
3
CH3
H3C
B)
Si
Figure 15 Structural formulae of stationary phases:

A) Polysiloxane-based phases.
Polydimethyl siloxane: R1, R2: CH3

Methylphenyl polysiloxanes: different ratio R2/R1;
R1, R2 =
Or
R1,
CH3,
R2 =
CH3
Methyl cyanopropylphenyl polysiloxanes:

R1, R2 =
CH3
Or R1, R2=
or
C N
B) Polyethyleneglycol
High Temperature Phases

a) Carboran modified polysiloxane
b) Silarylen polymer
23
apolar as a hydrocarbon. Gradual substitution of the CH3 groups by polarizable phenyl

moieties increasingly changes polarity, and enables therefore separation of moderately polar
analytes. Introduction of cyanopropyl substituents partially replacing phenyl groups in the
silicon chain leads to a phase with highest polarity amongst the siloxanes. Polyethylenglycol,
finally, allows interactions based on hydrogen bonds, and is therefore best suited for the
separation of analytes that are H-donors, e.g. alcohols. These phases are depicted in Figure 15.
Two examples for high temperature phases are also given. The one consists of
dimethyl polysiloxane polymers, which determine the selectivity. These polymeric chains are
connected with carborane (carbon-boron compounds) anchors, which are responsible for the
usability at temperatures as high as about 400C. The second phase in the example given
introduces temperature stability by implementation of phenyl groups directly into the polymer
chain.
2.3.2 Rohrschneider / McReynolds index

A concept to characterise the polarity of stationary phases was introduced by Rohrschneider
and McReynolds. It is based on the finding that the interaction of polar functional groups of a
solute is reflected by the difference of its retention indices on a polar and a nonpolar
stationary phase, respectively. Taken a very apolar phase as a reference (for this purpose
squalane is used, a branched C30 alkane, hexamethyl tetracosane), the retention index
difference on a certain phase relative to squalane is a measure for the polarity of this phase.
If e.g. the solute is an alcohol, it can be formally divided into the alkyl rest (which interacts
only by weak dispersion forces with all phases), and the OH group that is able to donate
hydrogen bonds. Interaction with stationary phase molecules, able also for hydrogen bonding,
will lead to stronger retention on the polar phase than on an apolar phase, and therefore a
large increase in retention index , IR, will result. According to the concept of Rohrschneider /
McReynolds, the increase of the retention index for the alcohol on the polar stationary phase
is given by a certain constant, characteristic for the given stationary phase. Measured for
butanol-1 as reference solute it is
squalane
y , = I bupolar
tan ol 1 I bu tan ol 1
(27)
To characterise the stationary phase polarity in a more general manner, the concept uses 5
special solutes, which are considered to represent typical chemical interactions. For each of
them, the constants x, y, z, u and s are defined accordingly; they are shown in Table 2.
24
The polarity of the stationary phase is expressed by the sum of the constants, the
Rohrschneider / McReynolds index,
= x+ y+ z+u+ s
(28)
Examples for stationary phases most common in practice are given in Table 3. If two phases
do not differ in their indices by more than about 200, their polarity can be considered as
nearly equal. In general it is not meaningful to use two such phases. This does not mean,
however, that probably their selectivities concerning one special type of interaction are
negligible.
Table 2 Rohrschneider / McReynolds index,

5 special solutes represent typical chemical interactions
= x+ y+ z+u+ s
Reference
solute
Rohrschneider/
McReynolds
constant
Type of interactions
Typical for
Dipole
-complex
H-bond
benzene
donor
butanol-1
donor
2-pentanon
acceptor
1-nitropropane
pyridine
u
s
acceptor
donor
olefines, aromatic
compounds
alcohols, phenols, acids,
amides
aldehydes, ketones,
esters, ethers
nitro-, nitrilo compounds
Amines, aromatics
Table 3 Rohrschneider / McReynolds constants and indices for characterisation of stationary

phase polarity
Stationary phase
Squalane
Dimethyl silicon
Phenyl methyl silicon
Cyanopropylphenyl
(cpph) dimethy silicon
Composition
100 % methyl
5 % phenyl
50 % phenyl
75 % phenyl
6 % cpph
50 % cpph
100 % cpph
PEG 20 M
x
0
17
32
119
178
50
y
0
57
72
158
204
115
z
0
45
65
162
208
107
u
0
67
98
243
305
164
s
0
43
67
202
208
103
Index
0
229
334
884
1103
539
227
523
322
373
757
536
336
659
368
489
942
572
398
801
510
1823
3682
2308
25
2.4
Column oven
The column oven has the function to adjust the column temperature to an accurate and
reproducible value. It is prerequisite in practice to establish these temperature conditions for
the column over the entire length, not only where the temperature sensor is located in the
oven. The column oven should not only meet these demands in the isocratic manner; it must
also enable the application of appropriate gradients, either a single linear or ballistic, or
multiple gradients by temperature programming. It should be noted that after such
programming a very important but often underestimated aspect is the establishment of the
exact initial column temperature after cooling. The inappropriate re-establishment often is the
source of systematic measuring errors.
2.5
Special Detectors
For GC a number of detectors have been developed. For trace analysis, however, not all of
them have increased importance. Most important detectors in this area are (beside the mass
spectrometer)
Flame ionisation detector (FID)
Electron capture detector (ECD)
Alkali flame ionisation detector (NPD)
These three detectors will be discussed in more detail in the following.
2.5.1 Flame ionisation detector

The FID is a mass flow sensitive detector. It is based on the measurement of the electric
charges, which are produced in a small hydrogen flame. In the absence of organic molecules
in the carrier gas, this flame is very poor in charged particles, because the combustion of
hydrogen with oxygen delivers only a very small number of ions or electrons. Indeed the
residual current is in the range of only 10-12 A (under normal working conditions, i.e. when a
voltage of about 200-300 V is applied between the flame and the collector electrode). This
extremely small residual current is amplified and represents the background signal (the
blank).
Organic molecules, which possess CH-groups, form CHn-radicals (n=0-3) at the
periphery of the hydrogen flame, where also excited O2* and OH* molecules are formed.
26
Reaction of the radicals with the excited molecules leads to the formation of positively
charged ions and electrons, e.g. according to
(29)
C + OH = CHO + + e
Consequently the positively charged molecular ions (e.g. CHO+) and the electrons formed
increase the current when organic molecules are entering the detector flame, and the analytes
are detected in this way (note that there is not full combustion to CO2).
Figure 16 Schematic drawing of a flame ionisation detector (from ref.
15
with permission).
The more CH-groups a molecule contains, the larger is the detector response.
Heteroatoms in the molecule lead to a smaller response. Molecules without CH-groups do not
deliver a signal, except due to overloading effects of the detector. The FID is therefore not
universal, as e.g. water, CO2, NOx , CS2, CCl4, etc. are not or only poorly detected. The same
is the case for the lower alcohols or substances with many heteroatoms.
Beside the analyte properties, the detector response is also dependent on its geometry,
and on the flow rate of the burning gases. Favourable flow rates for H2 are in the range of 2530 mL/min, those for the air are by a factor of 10 higher. Especially the H2 flow must be
selected carefully, because its optimal range is narrow (see Figure 16). The use of so-called
make-up gas is normally advisable in capillary GC for the improvement of the detector
response. It is also favourable to avoid loss in separation efficiency due to extra-column
27
effects caused by the dead volume of the detector. Because the FID is mass flow dependent,
the make-up gas does not negatively influence the detector sensitivity.
Figure 17 Dependence of the sensitivity of the FID on the flow rates of H2 and N2,
respectively. N2 is added as make-up gas (from ref.
14
with permission).
Performance data FID
sensitivity ~ 0.015 As/g

limit of detection ~ 10-11 to 10-12 g carbon/s
linearity 7 orders of magnitude
Time constant ~2 ms
2.5.2 Electron capture detector

In principle the ECD is an ionisation chamber. It has a very high specifity and sensitivity for
compounds that have atoms in their molecules with high electron affinity. Especially halogens
exhibit this property, but also for oxygen containing groups or nitro-groups this detector
responds very well (see the following Table). It will be, however, discussed below, that it is
not sufficient to take only the electron affinity into account to interpret the detector response.
X
H
C
O
CN
NO2
ElectronAffinity [eV]
0.72
1.2
2.34
3
3.9
X
J
Br
Cl
F
Electron Affinity [eV]

3.12
3.52
3.78
4.1
28
Roughly, the detector principle is based on the property of analytes, AX, containing
such atoms or groups, X, to attract electrons according to
(30)
AX + e = AX + energy
Electrons are generated by a radioactive -source like
63
Ni. However, these primary
electrons exhibit a too high energy (and therefore too high speed) to be captured from the
affine groups in the analytes. They interact first with carrier gas, which is present in very large
excess compared to the trace analytes; thus the chance for interaction with the -particles is
much greater for the former than for the latter molecules. As carrier gases (cg) those with
large mass are used, e.g. N2 or Ar (mixed with 5% CH4). According to the reaction scheme
given in eq. 31 the -particles generate thermal, secondary electrons by interaction with the
carrier gas molecules (these electrons have much lower, namely only thermal energy).
(31)
+
(therm )
cg cg + e
The current produced from these low energy electrons in the detector cell is measured and
amplified. As long as there is no analyte with electron affine groups in the carrier gas, the
background current (the blank) with about 10-8 A is delivered. When analytes with e.g.
halogen substitution are eluted from the column and enter the detector, electrons from the
basic current are captured according to eq. 30, and the current is decreased, detecting the
analytes in this way. In principle the number of charged particles is not changed in this
reaction, because instead of an electron a negatively charged sample ion is generated.
However, the velocity of these molecular ions (10 cm/s) is many orders of magnitude smaller
than that of the electrons (105 cm/s). For this reason the ions do not reach the collector
electrode; they recombine faster with positively charged carrier gas molecules under
formation of the neutral molecules according to
AX + cg + = AX + cg
(32)
However, under such conditions no signal would be obtained. For favourable measuring
conditions a pulsed voltage is applied, as indicated in Figure 18.
For a closer insight into the signal generation of the ECD we have to differentiate two
processes: the one is the simple addition of an electron, as expressed by eq. 30. The more
common process, on the other hand, includes a dissociative reaction of the product formed
after electron addition according to
AX + e = A + X
(33)
29
Figure 18 Schematic drawing of the ECD with pulsed polarisation voltage. b pulse width, e.g.
3s; D pulse distance, e.g. 10-200 s; h pulse height, e.g. 50 V (from ref.
15
with permission).
Therefore not only the electron affinity, but also the binding energy between the carbon atom
and the electron affine atom or group decides over the extent of reaction. This fact explains
the result of the relative sensitivity, rel. Si, of different compounds as given in the following
Table.
Detector Response and Sensitivity

Substance
Rel. Si
Binding energy [kJ/mol]
Fluorobenzene
Chlorobenzene
Bromobenzene
Iodobenzene
1
100
600
37 000
C-F
C-Cl
C-Br
C-I
538
391
281
210
Electron
Affinity [eV]
F 4.1
Cl 3.78
Br 3.52
I 3.12
Performance data ECD
several 10 fg of analytes (e.g. lindan) per injection

linearity 3 to 4 orders of magnitude
30
2.5.3 Alkali flame ionisation detector

The alkali flame ionisation detector, also named thermionic detector, belongs to the group of
ionisation detectors in which thermal energy is used as source for ionisation. From the
construction point of view it is a modification of the FID, with a pearl of alkali salt (Rb, Cs)
located between the flame and the collector electrode. Heating of the alkali salt pearl leads to
the emission of alkali atoms. The detector is responding especially to analytes containing
nitrogen or phosphorus atoms. According to the special conditions the detector can be run
either in the P- or in the N- and P- specific mode. The detailed mechanism of detection is still
a matter of question. Here we follow the discussion given by Kolb et al. (cf. e.g. ref. 15).
2.5.3.1 P mode
At elevated temperature alkali ions A+ in the (silicate) pearl are neutralised by electrons
delivered from the electrical source applied (A+ + e- = A). The neutral alkali atoms, A,
evaporate. These atoms are thermally excited giving A*. In the hydrogen flame H and OH
radicals are formed. However, these two radicals can only recombine to H2O when a partner
is present that is able to overtake their energy of formation. This may occur with a triple
collision, with excited A* as partner. As a result A* is ionised according to the reaction scheme
H + OH + A = H 2 O + A+ + e
(34)
The alkali cation A+ formed is collected at the negatively charged pearl, whereas the electron
is migrating to the collector electrode. In this way the background current of the detector is
formed in the P mode.
Phosphorus containing molecules, when present, are transformed to phosphorus oxide
radicals, R, in the flame of the detector. These radicals react in a double collision (which is
more probable than a triple collision with H and OH) with excited A*
(35)
R + A = R + A+
e.g.
O = P = O + A = [O = P = O ] + A+
(36)
The P-containing anion R- reacts further with an OH radical to

R + OH = ROH + e
(37)
e.g.
31
[O = P = O ]
(38)
+ OH = HPO3 + e
This reaction delivers the electron for the signal current specific for P-containing analytes.
Figure 19 Schematic presentation of the thermionic detector in the P mode (from ref.
15
with
permission).
Note that the flame jet is grounded, and has therefore a positive potential. For this reason the
electrons formed by reaction of CH- containing molecules due to the same processes as with
the FID are not interfering the detector signal, because they are conducted to ground, and do
not reach the collector anode.
2.5.3.2 NP mode
The N analogous oxides formed from N-containing molecules would decompose rapidly in
the flame of the detector, and would therefore not react with alkali. For this reason the
detector is run in the NP mode under reducing conditions, leading to CN radicals instead.
These conditions are established by decreasing the flow rates of hydrogen to about 1-3
mL/min, and that of air to less than 100 mL/min. The flame goes out then, but the remaining
free hydrogen is ignited at the electrically heated pearl. It forms a kind of plasma around the
pearl, where a CN radical formed adds an electron taken from excited A*, forming a cyanide
ion and alkali cation (see P-mode, eq. 35)
CN + A = CN + A+
(39)
32
The CN anion formed finally reacts either with H or OH radicals to HCN or HCNO,
respectively.
Figure 20 Schematic representation of the thermionic detector in the NP mode (from ref.
15
with permission).
This reaction delivers the electron for the signal current analogous to eq. 37. As the
formation of CN radicals is essential, such a structure must be present initially in the analytes
to enable detection. Therefore e.g. organic nitro compounds are detectable, but not nitrogen
oxides, or nitrate esters.
In the following table some data for the performance of the detector in both modes are
given.
Typical performance data for the NPD in P- and NP- mode, respectively.
Parameter
P mode
NP mode
Sensitivity
1 C/g P
5 C/g P
0.5 C/g N
Limit of detection
5.10-14 g P/s
10-14 g P/s
10-13 g N/s
Selectivity (vs. carbon)
106
105
104
Linearity
105
105
105
33
FURTHER READINGS
(1)
Scott, R. P. W. Introduction to Analytical Gas Chromatography; 2nd ed.;

Marcel Dekker, 1998.
(2)
Jennings,
W.
G.;
Mittlefehldt,
E.;
Stremple,
P.
Analytical
Gas
Chromatography; 2nd ed.; Academic Press, 1997.

(3)
McNair, H. M.; Miller, J. M. Basic Gas Chromatography; Wiley, 1997.
(4)
Grant, D. W. Capillary Gas Chromatography; Wiley, 1996.
(5)
Fowlis, I. Gas Chromatography; 2nd ed.; Wiley, 1995.
(6)
Scott, R. P. W. Techniques and Practices of Chromatography; 2nd ed.; Marcel

Dekker, 1995.
(7)
Grob, R. L. Modern Practice of Gas Chromatography; 3rd ed.; Wiley, 1995.
(8)
Baugh, P. E. Gas Chromatography: A Practical Approach; Oxford, 1994.
(9)
Hinshaw, J. V.; Ettre, L. S. Introduction to Open Tubular Column Gas

Chromatography; Advanstar, 1994.
(10)
Grob, K. Split and Splitless Injection in Capillary Gas Chromatography; 3rd

ed.; Hthig, 1993.
(11)
Hill, H. H.; McMinn, D. G. Detectors for Capillary Chromatography; Wiley,

1992.
(12)
Grob, K. On-Column Injection in Capillary Gas Chromatography; 2nd ed.;

Hthig, 1991.
(13)
Poole, C. F.; Poole, S. K. Chromatography Today; Elsevier, 1991.
(14)
Baars, B.; Schaller, H. Fehlersuche in der Gaschromatographie; VCH, 1994.
(15)
Kolb, B. Gaschromatographie in Bildern; Wiley-VCH, New York, 1999.
(16)
Kenndler, E.; Huber, J. F. K. In Analytiker Taschenbuch; Springer, 1989.
34

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Ernst Kenndler: Gas Chromatography

THEORETICAL ASPECTS OF GAS CHROMATOGRAPHY ............................................................ 2

PRACTISE OF GAS CHROMATOGRAPHY....................................................................................... 15

Ernst Kenndler: Gas Chromatography

THEORETICAL ASPECTS OF GAS CHROMATOGRAPHY

This text should be read in context with Introduction in Chromatography, where a

Distribution constant, separation selectivity

Figure 1 Schematic presentation of a gas-liquid chromatographic system. <v> is the average

Ernst Kenndler: Gas Chromatography

T is the absolute temperature and R is the gas constant.

where Vs,mol is the mean molar volume of the stationary phase.

p io , the vapour pressure of the analyte as pure compound at temperature T

The selectivity coefficient for GLC using eq. 4 is thus

It can be seen that selectivity in GLC is determined by two ratios:

Ernst Kenndler: Gas Chromatography

1.1.1 Temperature Dependence of Distribution Constant

log K io resp. log k i'

The experimental dependence of the capacity factor on the temperature is shown in

Ernst Kenndler: Gas Chromatography

1.1.2 Retention index IR

This relation can be graphically represented by

Substitution of the capacity factors by the net retention times

Ernst Kenndler: Gas Chromatography

velocity of the mobile phase

kind of the stationary phase

Ernst Kenndler: Gas Chromatography

n-alkanes always full hundreds, n-hexane 600, etc.

Retention indices at two phases

IR the larger, the more polar functional group

Peak dispersion in chromatography is discussed in general in Introduction to

Hdiff describes the contribution from longitudinal diffusion

Hconv that from convective mixing

Ernst Kenndler: Gas Chromatography

Ernst Kenndler: Gas Chromatography

Ernst Kenndler: Gas Chromatography

Ernst Kenndler: Gas Chromatography

1.2.1 Golay equation

Ernst Kenndler: Gas Chromatography

Figure 8 Schematic drawing of the local flow velocity, v, (indicated by arrows) of a

Ernst Kenndler: Gas Chromatography

1.2.2 Plate height vs. retention factor.

(1+6k +11k )/(1+k )

Ernst Kenndler: Gas Chromatography

Figure 10 Cs-term as function of the retention factor (eqs. 18 and 19)

Ernst Kenndler: Gas Chromatography

PRACTISE OF GAS CHROMATOGRAPHY

) and can indeed often be handled as modules in instrumental practice.

Figure 11 Scheme of a gas chromatograph

Ernst Kenndler: Gas Chromatography

With the simplified Golay equation (eq. 20) we obtain

mobile p hase velocity, v

Ernst Kenndler: Gas Chromatography

Ernst Kenndler: Gas Chromatography

2.2.1 Split and splitless injector

Ernst Kenndler: Gas Chromatography

Figure 13 (A) Schematic drawing of a split-splitless injector (from ref.

Ernst Kenndler: Gas Chromatography

It should be mentioned that the discriminating evaporation of volatile sample

2.2.2 On-column injection

Ernst Kenndler: Gas Chromatography

avoids mass discrimination effects

Ernst Kenndler: Gas Chromatography

Figure 14 Schematic drawing of packed and capillary columns

Ernst Kenndler: Gas Chromatography