Professional Documents
Culture Documents
Raymond P. W. Scott
GAS
CHROMATOGRAPHY
DETECTORS
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
2
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
3
Contents
Introduction............................................................................................. 1
Classification of Detectors ..................................................................... 1
Detector Specifications ....................................................................... 2
The Form of Detector Response ......................................................... 3
The Dynamic Range of the Detector .................................................. 4
Detector Linearity ............................................................................... 5
Determination of Response Index ...................................................... 6
The Incremental Method of Linearity Measurement ..................... 7
The Logarithmic Dilution Method of Linearity Measurement ...... 7
Alternative Method for Specifying Detector Linearity .................. 9
Detector Response ............................................................................ 10
Detector Noise .................................................................................. 11
Measurement of Detector Noise ................................................... 12
Detector Sensitivity or Minimum Detectable Concentration ........... 13
System Dispersion and Sensor Dimensions ..................................... 14
Peak Dispersion from the Overall Detector Time Constant. ....... 14
Pressure Sensitivity........................................................................... 16
Flow Sensitivity ................................................................................ 16
Temperature Sensitivity .................................................................... 17
Summary of Detector Criteria .............................................................. 17
Early Gas Chromatography Detectors .................................................. 19
The General Properties of GC Detectors .............................................. 27
The Katharometer Detector .................................................................. 29
The Simple Gas Density Balance ......................................................... 32
The Flame Ionization Detector ............................................................. 33
The Design of the FID ...................................................................... 34
Electrode Configurations .............................................................. 35
The High Impedance Amplifier .................................................... 36
The Response Mechanism of the FID .......................................... 37
The Operation of the FID ............................................................. 40
The Nitrogen Phosphorus Detector (NPD) .......................................... 43
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
4
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
1
Introduction
The detector, as well as being an essential supporting device for the gas
chromatograph has also played a critical role in the development of the
technique as a whole. There has been a synergistic interaction between
column development and detector development. The need to develop
higher column efficiencies has demanded higher detector sensitivities
which has provoked the development of more sensitive detectors. In
turn, the more sensitive detectors has encouraged the improvement of
column performance. In fact, the rapid development of GC in the 1950s
was possible because or the swift introduction of high sensitivity linear
detectors.
Classification of Detectors
Detectors can be classified into two types, bulk property detectors and
solute property detectors. The bulk property detector measures some
bulk physical property of the eluent (such as dielectric constant or
refractive index) and the solvent property detector, measures some
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
2
Detector Specifications
1. Dynamic Range
2. Response Index or Linearity
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
3
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
4
A detector has two response ranges, the dynamic range and the linear
dynamic range and the two range are not synonymous. The dynamic
range of a detector is that concentration range over which a
concentration dependent output is produced. The minimum of the range
will be the concentration at which the output is equivalent to twice the
noise level and the maximum that concentration where the detector no
longer responds to a concentration increase. The dynamic range is
usually given as a concentration ratio and is thus, dimensionless.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
5
Detector Linearity
Thus, y= Ac
where (r) is the response index and the other symbols have the
meaning previously ascribed to them.
For a truly linear detector, r=1, and the extent to which (r) deviates
from unity would be a measure of its non linearity.
Curves relating the detector output to different solute concentrations
passing though it for different response values are show in figure 2.
The curves shown in figure 2 appear to closely approximate to a
straight line (i.e. are linear). However, if linearity is assumed
considerable errors can result as shown in table 2.
Table 1 The Analysis of a Two-Component -Mixture Using
Detectors Having Different Response Indices
It is seen that the results for the lower level component (10 % w/w) can
be as great as 12.5 % (1.25 % absolute) when (r) is a low as 0.94 and
9.5 % (0.95 % absolute) if (r) is a high as 1.05. It follows, that to
provide adequate accuracy for concentration ranges of 10 or more then
(r) should lie between 0.98 and 1.02.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
7
There are two basic methods for measuring the response index of a
detector and they are the incremental method and the logarithmic
dilution method. The incremental method requires no special apparatus
other than the chromatograph itself but the latter does require special
equipment but the apparatus is very simple to construct.
The Incremental Method of Linearity Measurement
The slope of the curve will give the response index (r) which will be
/4 or unity for a perfectly linear detector.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
8
dV dV
V
Xt
dm C t dv
where (Ct) is the concentration of solute in the vessel after time (t).
The mass change (dm) will result in a change in concentration (dC t)
in the vessel, thus,
Vd C t C t dv 0
d Ct dv
and
Ct V
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
9
v
Integrating log C t k
V
Qt
k
V
where (Q) is the flow rate,
(v) is the volume flow of mobile phase through the system
after time (t)
and (k) is the integration constant.
It should be pointed out that the logarithmic dilution method should not
be used if the linearity is to be measured by the method recommended
by the E19 committee of the ASTM.
Detector Response
h wQ
RD
ms
where the symbols have the meanings previously ascribed to them.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
11
Detector Noise
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
12
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
13
One problem common to all detectors is the peak dispersion that takes
place in the mobile phase conduits and sensor volumes of the detector.
Dispersion of this type is particularly serious in LC where solute
diffusivities are 4 to 5 orders of magnitude smaller than those in gasses.
In GC however, due to the much higher diffusion rates detector
dispersion is minimal and does not significantly effect chromatographic
performance. Consequently detector dispersion in GC detectors will
not be discussed in this book, but dispersion in LC detectors will be
considered in detail in book 5, LC Detectors.
Peak Dispersion from the Overall Detector Time Constant.
Peak dispersion resulting from the time constant of the sensor and its
associated electronics can be significant in both GC and LC,
particularly when filter circuits are introduced to remove inherent
detector noise. The effect of the detector time constant can be
theoretically examined (see book 14 Extra-Column Dispersion) and
calculated and the results from such calculations are shown in figure 6.
The undistorted peak, that would be monitored by a detector with a
zero time constant, is about 4 seconds wide..
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
15
Pressure Sensitivity
Flow Sensitivity
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
17
Temperature Sensitivity
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
18
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
19
2
7. Detector Dispersion – ( d ) – This is generally not significant in GC
detectors
10. Flow Sensitivity – (DQ) – The flow sensitivity is the output that
results from unit change in flow rate. It is specified in V/ml/min. It is
important in detector design.
The first GC detector was invented by James and Martin [4] in 1952,
and used for the separation of some fatty acids. It consisted of a
titration apparatus situated at the end of the column and the eluent gas
was bubbled through a suitable aqueous liquid to absorb the solutes.
The solution contained an indicator and, as each solute was eluted, the
solution was manually titrated. The titration process was eventually
automated and an integral chromatogram was obtained by plotting the
volume of base solution added against time. The integram consisted of
a series of steps, one for each solute. This rather primitive arrangement
validated the gas chromatographic concept but also indicated that a
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
20
The gas density balance was a very complicated and ingenious device
and, incidentally, the modern 'so–called' gas density bridge bears little
or no resemblance to the original design. A diagram of the gas density
balance is shown in figure 7. The detector consisted of a compact
Wheatstone network of capillary tubes, drilled out of a high
conductivity copper block. The reference flow of mobile phase and the
eluent from the column entered at two opposing junctions of the bridge
arms (the center of tube (C)) such that the eluent was contained in one
vertical arm (C) and the pure mobile phase in a parallel vertical arms
(A) and (B).
The increase in pressure at the base of tube (C) due to the presence of
solute in (C) applied a pressure to the bottom of tube (A). This caused a
flow of gas through the anemometer from tube (A) to tube (B)
providing an output that was fed to a recording milliammeter.
Subsequently all flows exited from the top and bottom of tube (C). The
anemometer was particularly unique. It consisted of a cylindrical
chamber, 1.5 cm in diameter and 4 mm wide.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
21
The detector was quite robust, but initially difficult to set up. The
sensor had a linear response (0.98<r<1.02) over about 3 orders of
magnitude of concentration range and a sensitivity (minimum
detectable concentration) of 5 x 10–7 g/ml (n-heptane). Unfortunately,
the detector was very difficult to construct for the general
chromatographer (indeed also for the instrument manufacturers) and
even after many attempts, was never produced commercially as an
effective GC detector. The lack of an alternative, simple detector
provoked the development of alternatives. As a consequence, a number
of very effective highly sensitive GC detectors were developed over a
relatively short period of time of which many were manufactured
commercially.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
23
Exit
Gase s
Thermocouples Flame
Hydrogen
Mobile Phas e
from Column
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
24
To Waste
90 Sr Source 90 Sr Source
+ -
Voltage Voltage
Stabilis e r Stabilis e r
- +
High Eluent
Impe dance
Reference Flow
Ele ctromete r
Amplifie r Recorder
The –ray ionization detector was also introduced by Boer [9] in 1956.
This was the first ionization detector that utilized a radioactive source
and the design of the detector is shown diagramatically in figure 9. It
consisted of a reference cell, through which pure carrier gas passed,
and a sensor cell, which carried the column eluent. Each cell contained
a 90strontium emitting source that the three stage fission terminating
in the stable atom of 90zirconium.
90 90 90
Sr Y Zr
0.6 half life 2.5
half life Me V Stable
Me V ca 60 h
ca 25 y
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
26
imparted color to the flame. The sensitivity varied widely with the
solute being detected. Aromatics that impart strong luminosity to the
flame giving a strong response and consequently a high sensitivity (ca 1
x 10-6 g/ml).
Conversely, saturated hydrocarbons impart little luminosity to the flame
and thus have a weak response and a very low sensitivity–the very
features for which the detector was designed. The linear range is
difficult to determine from the original publication but appears to be in
excess of two orders of magnitude. The performance of the detector is
illustrated in figure 11.
The development of these early detectors not only helped establish GC
as a viable analytical technique but also stimulated the development of
other types of vapor sensing devices. The future detectors would prove
to have extremely high sensitivities and wide linear dynamic ranges
and to function on widely different principles. However, with the
exception of the katharometer, they would also render these early
detectors virtually obsolete. Nevertheless, they played an important
role in the early days of GC and in their time were exciting devices to
operate.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
28
The detector consists primarily of two parts, the sensor and the
associated signal conditioning electronics. The two parts can be
integral or discrete. Although to minimize dispersion, the sensor should
be situated as close to the column as possible. The electronic system
can be situated some distance from the sensor if more convenient.
Nevertheless, the signal must be transmitted in an appropriate manner
to avoid any electrical interference that might provide extra noise or
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
29
Heated Me tal
Block
Reference
Filame nt
Sensor
Filame nt
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
30
Reference
Flow
To Was te
Column
Flow
Sample
Filame nt Conne ctions
to Bridge
There are two types of sensor design, the "in-line" sensor where the
column eluent actually passes directly over the filament (as shown in
figure 12) and the "off-line" cell where the filaments are situated away
from the main carrier gas stream and the gases or vapors only reach the
sensing element by diffusion.(as shown in figure 13). Due to the high
diffusivity of vapors in gases, the diffusion process can be considered
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
31
The original gas density balance has already been described. It was
complicated, difficult to fabricate and its manufacture was not a
commercial success. In the early days of chromatography GOW-MAC
developed some elegantly designed filaments for use in the
construction of katharometers, which, in due course, were used in many
other manufacturer's katharometer products. These sensing filaments
were rugged and highly reliable and were used by GOW–MAC to
emulate Martin's density balance in a simple form. A diagram of the
GOW-MAC gas density balance is shown in figure 15. The sensor
consists of a pneumatic bridge of tubes containing three vertical tubes
all connected by horizontal tubes at the top and the bottom. Pure carrier
gas enters the center of the right hand vertical tube and splits into two
streams one passing along the lower horizontal tube and the other
along the upper horizontal tube. The eluent from the column enters the
center of the middle tube and the flow also splits into two streams and
each meets the respective flow from the right-hand tube. The flows in
the two horizontal tubes finally pass up and down the left-hand vertical
tube to meet at the center and then exit to waste. Flow sensors are
situated in the horizontal tubes between the right-hand vertical tube
and the center vertical tube. When only carrier gas is present in the
system, the horizontal flows are equal and the temperature and thus the
potential across the filaments of the two sensors are the same. When a
solute is eluted from the column, vapor will be present in the center
vertical tube and the pressure at the top and bottom of the tube will
differ. This will result in a differential flow through the horizontal
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
33
tubes with a consequent change in the output from the sensors. As the
differential flow will be proportional to the pressure difference between
the right-hand column of pure carrier gas and the center column full of
vapor,
Katherome ter
Column of Type Se ns or
Vapor
Pure Carrier
To Waste Gas
Eluent From
Column Katherome ter
Type Se ns or
Courtesy of GOW-MAC
Figure 15. The GOW-MAC Gas Density Balance
the output from the sensor filaments will be proportional to the vapor
density of the solute and consequently be related to the molecular
weight. In fact with a second detector that measured the concentration
of the solute, the gas density balance can be used to determine
molecular weight of an eluted solute. This device has about the same
sensitivity and linearity as the katharometer but, unfortunately, is no
longer commercially available. It was one of the very few simple and
inexpensive methods available for measuring the molecular weight of
an eluted solute.
The Flame Ionization Detector
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
34
Without doubt, the Flame Ionization Detector (FID) is the most useful
GC detector available and by far that most commonly used in GC
analyses. The FID has a very wide dynamic range, a high sensitivity
and (with the exception of a few low molecular weight compounds)
will detect all substances that contain carbon. The first FID was
described about the same time by Harley and Pretorious (12), and
McWilliams and Dewer (13). The FID is an extension of the flame
thermocouple detector and is physically very similar, the fundamentally
important difference being that the ions produced in the flame are
measured as opposed to the heat generated. Hydrogen is mixed with the
column eluent and burned at a small jet. Surrounding the flame is a
cylindrical electrode and a relatively high voltage is applied between
the jet and the electrode to collect the ions that are formed in the flame.
The resulting current is amplified by a high impedance amplifier and
the output fed to a data acquisition system or a potentiometric recorder.
The detector usually requires three separate gas supplies together with
their precision flow regulators. The gases normally used are hydrogen
for combustion, helium or nitrogen for the carrier gas and oxygen or air
as the combustion agent. The detector is normally thermostatted in a
separate oven; this is not because the response of the FID is
particularly temperature sensitive but to ensure that no solutes
condense in the connecting tubes.
Electrode Configurations
The ion current flows through the resistance to complete the circuit and
the voltage developed across the resistance is applied to the input of a
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
36
Power Power
Supply Supply
To High To High
Impe dance Impe dance
Amplifie r Amplifie r
je t
je t
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
37
The flame plasma contains both positive ions and electrons which are
collected on either the jet or the plate depending on the polarity of the
applied voltage. Initially, the current increases with applied voltage,
the magnitude of which depend on the electrode spacing. The current
continues to increase with the applied voltage and eventually reaches a
plateau at which the current remains sensibly constant. The voltage at
which this plateau is reached also depends on the electrode distances.
Curves relating ionization current to applied voltage obtained by
Ongkiehong are shown in figure 18. Once electron/ion pair production
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
38
is initiated the recombination starts to take place. The longer the ions
take to reach the electrode the more recombination takes place. Thus,
the greater the distance between the electrodes and/or the lower the
voltage, the greater the recombination. This is substantiated by the
curves obtained by Ongkiehong: the plateau is reached at a lower
voltage when the electrodes are closer together. It is seen that the
plateau level is the same for both electrode conditions and it is assumed
that on the plateau,
all ions and electrons being produced in the flame are collected. In
practice the applied voltage would be adjusted to suit the electrode
distance to ensure that the detector operates under conditions where all
electrons and ions are collected viz. on the plateau shown in figure 18.
Desty et al. (16) showed that the performance of the detector was
relatively insensitive to electrode distance and hydrogen flow
providing the voltage was adjusted to ensure that the detector worked
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
39
on the current plateau. Desty et al. also showed that the air flow should
be at least 6 times that of the hydrogen flow for stable conditions and
complete combustion. They also demonstrated that the base current from
the hydrogen flow depends strongly on the purity of the hydrogen. As
would be expected, traces of hydrocarbons significantly increase the
base current. Consequently, very pure hydrogen should be employed
with the FID if maximum sensitivity is required. Employing purified
hydrogen Desty et al. reported a base current of 1.45 x 10-12 amp for a
hydrogen flow of 20 ml/min.
Log Current Response (amps)
Molar Response Factor
(coulombs/mole)
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
40
The linear dynamic range of the FID covers at east four to five orders
of magnitude for 0.98<r<1.02. This is a remarkably wide range that
also accounts for the popularity of the detector. Commercially available
detectors shows considerable difference in electrode geometry and
operating electrode voltages, yet they all appear to have very similar
performance specifications. This supports the claim of Desty et al. that
the FID is surprisingly forgiving with respect to specific detector
geometry.
The FID is probably the simplest, easiest and most reliable detectors to
operate. Generally the appropriate flow rates for the different gases are
given in the detector manual. Hydrogen flows usually range between
20 and 30 ml per min, air flows about 6 times the hydrogen flow e.g.
120 to 200 ml per min. The column flow that can be tolerated is usually
about 20-25 ml per min depending on the chosen hydrogen flow.
However, if a capillary column is used, the flow rate may be less than 1
ml per min for very small diameter columns. The mobile phase can be
any inert gas–helium, nitrogen, argon etc. To some extent the detector
is self-cleaning and rarely becomes fouled. However, this depends a
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
41
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
43
The sensor was held at 250oC (50oC) above the maximum column
temperature to avoid condensation in the jet and conduits. The sample
size was 0.1 l, which was split 100-1, giving a total charge of about 1
g. Helium was used as the carrier gas at a linear velocity of 20 cm/sec.
It is seen that the baseline is extremely stable despite the temperature
program, and that the high sensitivity and wide dynamic range of the
FID make it invaluable for quantitative analysis.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
44
Anode
+ Rubidium or
Ces ium Bead
He ater
Conne ctions
Flame
Heater
Air
Hydrogen
Carrier Gas
Nitroge n
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
45
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
46
The emissivity detector or, the Flame Photometric detector (FPD), was
described by Grant (10) in 1958 but as it could not compete in
sensitivity with the ionization detectors, did not raise any commercial
interest. The emissivity detector, however, has some unique properties
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
48
that could make its response quite specific and giving it certain unique
areas of application. It was originally used to differentiate aromatic
from paraffinic hydrocarbons by measuring the luminosity that the
aromatic nucleus imparted to the flame. Contemporary photometric
detectors do not usually monitor the total light emitted only light
emitted at specific wavelengths. For example, phosphorus and sulfur
containing hydrocarbons generate chemi-luminescence at specific
wavelengths when burnt in the hydrogen flame. The wavelengths of the
light emitted by carbon and hydrocarbons containing sulfur and
phosphorus are shown in figure 25.
The diagram includes the transmission band for the filters used in the
Hewlett-Packard FPD together with the response of the photo-
multiplier sensor. Light emitted by sulfur compounds extends over the
range from 320 nm to 480 nm and that emitted by hydrocarbons alone
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
49
The system is very similar to that originally devised by Grant. The end
of the capillary column is led into the flame jet where the column
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
50
eluent mixes with the hydrogen flow and is burnt. The jet and the
actual flame is shielded to prevent light from the flame itself falling
directly on to the photo-multiplier. The base of the jet is heated to
prevent vapor condensation. The light emitted above the flame, first
passes through two heat filters and then through the wavelength
selector filter and finally on to the photo-multiplier.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
51
The flame conditions can be critical and the gas flows and jet diameter
must be adjusted to ensure optimum emission in the detection zone.
Hydrogen flow rates, air flow rates and jet temperature must also be
optimized to ensure maximum sensitivity and selectivity and to avoid
sample condensation in the burner conduits. An example of the use of
the FPD in the analysis of thiophene and substituted thiophenes in a
hydrocarbon mixture is shown in figure 27. It is seen that excellent
selectivity is afforded by the FPD. The filters allow the sulfur
compounds to be clearly and unambiguously selected from the
multitude of hydrocarbons present in the mixture thus, greatly
simplifying the analysis and improving its accuracy and precision.
Ionization Detectors
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
52
Noble gases, have their outer octet of electrons complete and, thus,
collisions between argon atoms and electrons are perfectly elastic.
Consequently, if a high potential is set up between two electrodes in
argon, and ionization is initiated (for example by a suitable radioactive
source) electrons will be accelerated towards the anode and will not be
impeded by energy absorbed from collisions with argon atoms. If the
potential of the anode is high enough, the electrons will develop
sufficient kinetic energy that on collision with an argon atom, energy
can be absorbed, and a metastable atom can be produced.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
53
+
Anode
Ins ulation
To Was te
Cathode – 90
Strontium
Radioactive Source
Eluent from
Column
Linearizing Re sistance 3 x 10 9
To Amplifier
From Column
8
Signal Res is tance 1 x 10
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
55
The sensitivity of the macro argon detector is 4 x 10-11 g/ml. The main
technical disadvantage of the argon detector was its large sensor
volume which precluded its use with capillary columns. This provoked
Lovelock to design the micro argon detector
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
57
From Capillary
Column
Anode (+)
To Was te
PTFE Ins ulator
Radioactive
Tritium Source
Cathode (–)
Stainle ss Stee l
Body
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
58
scavenger flow of argon that rapidly removes the solute from the cell
through two holes at the bottom of the anode cavity. This procedure
reduces the effective sensor volume to less than a microliter and thus
allows the efficient use of a capillary column. The radioactive source
originally used was about 25 micro-curies of radium (an particle
source).
Although the radioactive source was very small (defined in those days
as about a "wrist watch", as equivalent quantities of radium were used
to produce the luminous dials of many watches at that time) it was
subsequently recognized that exposure to particles could cause a
health problem. Eventually radium was replaced by tritium (a very
weak ray emitter) which, although a fairly strong source (sometimes
as much as one curie was used), it was relatively harmless from the
point of view of radiation energy. However, it is also somewhat
unstable at high temperatures causing loss of tritium to the air and
consequent atmospheric contamination.In due course the tritium was
replaced by Ni63 (another, more energetic –ray source) but a fairly
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
59
Beres et al. (24) showed that the argon detector could be made to
function without a radioactive source or other electron producing
device providing the argon and sensor system was operated at
temperatures above 150oC. Glass becomes conducting at temperatures
of 150oC and above, and so glass could be employed as one of the
electrodes. A diagram of a sensor is shown in figure 31. The column
eluent (argon) passes through a stainless steel tube, which acts as the
anode, into a cylindrical glass tube held at 150 oC or above. The tube is
insulated from the glass tube by a PTFE sleeve. The argon exits from
the sensor by a length of PTFE tube.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
60
PTFE
Slee ve Stainle ss Stee l
Tube PTFE
Tube
Stainle ss Stee l
Tube
High Voltage
Power Supply
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
61
Heat Shrink
PTFE Slee ve
PTFE
Capillary Space r Glass
Column Glass Tube
Tube
Glas s to
Me tal Se al
+ –
Me tal Conne ctions
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
62
The helium detector works on exactly the same principle as the argon
detector, but metastable helium atoms are produced by the accelerated
electrons instead of metastable argon atoms. Metastable helium atoms,
however, have an energy of 19.8 and 20.6 electron volts and thus can
ionize, and consequently detect, the permanent gases and, in fact, the
molecules of all other volatile substances. As a consequence,
contaminants in the helium can be extremely deleterious and the
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
63
Dis charge
Voltage
ca 500 V
Dis charge
Ele ctrode s
Dis charge
Chambe r
Ionization
Chambe r Column
Elue nt
To Was te
Collecting
Plates
To Amplifier
150 V
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
64
The column eluent enters the top of the ionization chamber and mixes
with the helium from the discharge chamber and exits at the base of the
ionization chamber. Ionization probably occurs as a result of a number
of ionization processes. The electric discharge produces both electrons
and photons. The electrons can be accelerated to produce metastable
helium atoms, which in turn can ionize the components in the column
eluent. However, the photons generated in the discharge have,
themselves, sufficient energy to ionize many eluent components and so
ions will probably be produced by both mechanisms. Other ionization
processes may also be involved, but the two mentioned are likely to
account for the majority of ions produced. The response of the detector
depends on the collecting voltage and, as one might expect, is very
sensitive to traces of inert gases. Peak reversal often occurs at high
collecting voltages, which may also indicate that electron capturing
may also be taking place. This peak reversal is reported to be
controllable by the introduction of traces of neon in the helium carrier
gas. The helium discharge ionization detector is a relatively new
detector and has exhibited high sensitivity to the permanent gases and
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
65
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
66
takes place) and the lower section, a tube 3 mm I.D. (where reaction
with metastable helium atoms and photons takes place). Helium make–
up gas enters the top of the sensor and passes into the discharge
section. A potential (about 20 V) applied across the discharge
electrodes is pulsed at about 3 kHz with a discharge pulse-width of
about 45 s for optimum performance.
Helium
Make–Up
Gas
Dis charge
Ele ctrode s
– ve
Potential
To Amplifier
Ope n Tubular
Column Gas Exit
The discharge produces electrons and high energy photons (that can
also produce electrons), and probably some metastable helium atoms.
The photons and metastable helium atoms enter the reaction zone
where they meet the eluent from the capillary column. The solute
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
67
molecules are ionized and the electrons produced are collected at the
lower electrode and measured by an appropriate high impedance
amplifier. The distance between the collecting electrodes is about 1.5
mm. It is reported that the helium must be 99.9995 pure. The base
current ranges from 1 x 10-9 to 5 x 10-9 amp, the noise level is about
1.2 x 10-13 amp and the ionization efficiency is about 0.07%.
Column10 m x 0.05 mm, film thickness 0.05 m; Flow rate 20 ml/min. Sample
split 1:150;1, benzene; 2, toluene; 3, ethylbenzene; 4, m and p xylene; 5, o-xylene
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
69
During the "off period" the electrons re-establish equilibrium with the
gas. The three operating variables are the pulse duration, pulse
frequency and pulse amplitude.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
70
Puls e Width 1 s ec
Electrode Voltage
Time
Figure 39 Common Pulse Pattern for the Electron Capture
Detector Operated in the Pulsed Mode
In general use, however, the pulse width is usually set at about 1 sec
and the frequency of the pulses at about 1 kHz. This allows about 1
millisecond for the sensor to re-establish equilibrium in the cell before
the next electron collection occurs. The sampling and equilibrium
periods are depicted in figure 39.
The potential applied across the electrodes of the sensor at each pulse
is about 30 V but depends on the geometry of the sensor and the
strength of the radioactive source.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
71
Radioactive
Insulators Source
Carrier
Gas
Nitrogen or Hydrogen.
Flow For Pul sed Mode Operation
Diffuser 10% Methane i n Argon
+
Figure 40. The Electron Capture Detector
The average current is about 1 x 10-8 amp and has an associated noise
level of about 5 x 10-12 amp. A diagram of the electron capture
detector as developed by Lovelock et al is shown in figure 40. Their
sensor consisted of a small chamber, 1-2 ml in volume, with metal ends
separated by a suitable insulator. The metal ends acted both as
electrodes and as fluid conduits for the carrier gas to enter and leave
the cell. The cell contained the radioactive source electrically
connected to the conduit through which the carrier gas enters and to the
negative side of the power supply. A gauze "diffuser" was connected to
the exit of the cell and to the positive side of the power supply. The
electrode current was measured by an appropriate high impedance
amplifier .
An example of a more modern sensor design is that used in the Perkin
Elmer electron capture detector and is shown in figure 41.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
72
given mass will vary with the position it is eluted in the chromatogram
(for a given mass of solute, an early peak would be narrow and have a
small volume and a high concentration at the peak maximum: however,
if eluted as a late peak it would be broad, have a relatively large
volume and a lower concentration at the peak maximum).
Consequently, a mass of solute just identifiable (signal to noise = 2)
when eluted as an early peak may not be detected or discerned when
eluted as a late peak The linear dynamic range of the electron capture
detector is again ill-defined by many manufacturers. In the DC mode
the linear dynamic range is usually relatively small, perhaps two orders
of magnitude, with the response index lying between 0.97 and 1.03.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
74
The pulsed mode has a much wider linear dynamic range and values up
to 5 orders of magnitude have been reported. The linear dynamic range
will depend on the strength of the radioactive source and the detector
geometry. If a response index lying between 0.98 and 1.02 is assumed,
then a linear dynamic range of at least three orders of magnitude should
be obtainable from most electron capture detectors. An example of a
pesticide analysis employing an electron capture detector to monitor
the separation is shown in figure 42.
The mass of each pollutant present in the sample was about 120 pg.
The separation of some common herbicides monitored by the electron
capture detector is shown in figure 43.The electron capture detector is
used extensively for monitoring the separation of polychlorinated
hydrocarbons and in particular the herbicides.
Gase s to
Was te Sample Inlet/
Capillary Column
Dopant
Inle t
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
76
The linear dynamic range is also not precisely clear from the original
publication but appears to be at least three orders of magnitude for a
response index of (r) where 0.97 < r < 1.03, but this is an estimate from
the data published. The modified form of the electron capture detector,
devoid of a radioactive source, is obviously an attractive alternative to
the conventional device and appears to have similar, if not better,
performance characteristics. An example of the use of the pulsed
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
77
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
78
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
79
Ce nte r
Furnace Ele ctrode
Addition of
10% Propane
Ce nte r
Furnace Furnace Ele ctrode
Addition of Addition of
Hydrogen 10% Propane
towards the anode and, in doing so, produce further ionization of the
carrier gas which enhances the signal. Normally this would result in a
stable discharge being formed but the presence of the propane prevents
this happening and for this reason the propane is sometimes called the
quench gas. The counting tube consists of a metal cylinder carrying and
insulated central electrode in the form of a rod. The outer case is
usually grounded and a high potential is applied between the central
electrode and the case. The signals received from the counter are
integrated with respect to time and thus the output current from the
integrator is proportional to the total number of disintegrations
occurring per second. As a result, the integration of the signal over the
duration of the peak will a give a value that is proportional to the total
activity of the peak. The 13 C counting apparatus is shown in the upper
part of figure 46
Over the years between 1956 and 1980, a considerable number of novel
GC detecting systems were developed and, at one time or another, each
was strongly acclaimed by the enthusiastic inventor for some specific
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
81
application. Very few of these detectors have survived and even fewer
are still being manufactured and are commercially available. However,
one or two have recently been rediscovered and found suitable for new
areas of application. A selected number of this fairly large group of
"lost detectors" will be briefly described to illustrate the large variety
of sensing techniques that have been applied to GC detection.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
82
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
83
About the same time that Ryce and Bryce were developing the
thermionic ionization detector, Harley and Pretorious (33) and
(independently) Pitkethly and his co-workers (34,35) were developing
the discharge detector. By applying the appropriate potential, a
discharge can be maintained between two electrodes situated in a gas
providing the pressure is maintained between 0.1–10 mm of mercury.
After the discharge has been initiated, the electrode potential can be
reduced and the discharge will still continue. Under stable discharge,
the electrode potential remains constant and independent of the gas
pressure and the electrode current. The electrode potential, however,
depends strongly on the composition of the gas. It follows, that the
system could function as a GC detector. Pitkethly modified a small
domestic neon lamp for this purpose and a diagram of his sensor is
shown in figure 48. The lamp was operated at about 3 mm of mercury
pressure with a current of 1.5. Under these conditions the potential
across the electrodes was 220 V. Pitkethly reported that a concentration
of 10-6 g/l gave an electrode voltage change of 0.3 V.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
84
Lovelock [15] noted that the voltage at which a spark will occur
between two electrodes situated in a gas will depend on the
composition of the gas between the electrode tips and suggested that
this could form the basis for a GC detector. The system suggested by
Lovelock is shown in figure 49.
Charging
Capacitor
Applie d
Potential
Ele ctrode s
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
85
The sensor consists of a glass tube in which two electrodes are sealed.
The electrodes are connected in the circuit depicted in figure 49. The
voltage across the electrodes is adjusted to a value that is just less than
that required to produce a spark. When a solvent vapor enters the
sensor, the sparking voltage is reduced and a spark discharge occurs.
This discharges the capacitor until its voltage falls below that which
will maintain the spark discharge. The capacitor is then charged up
through the charging resistor until the breakdown voltage is again
reached and another spark is initiated. Thus the spark frequency will be
proportional to (or at least be a monotonic function of) the vapor
concentration. The total counts in a peak will be proportional to the
peak area and, if a digital–to–analog converter is also employed, the
output will be proportional to the concentration in the detector and
thus, plotted against time, will provide the normal chromatogram. This
detector does not appear to have been developed further but is an
interesting example of a sensor that, in effect, produces a digital output.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
86
Se ns or Containing
Coaxial Ele ctrode s
RF Couple r
To Was te
RF
Generator
To Recorder or
Data Acquis ition
Syste m
Zero
Control
Column
Testerman and McLeod [39] designed and built a detector based on the
whistle principle. In their sensor design, typical values taken for the
dimensions in the diagram, and variables in the equation, were (t),
0.064 mm, (d), 0.74 mm, (h), 1.676 mm and (L) 3.81 mm.
Orifice
(h) Je t
Edge
Carrier
Gas
(t)
(d)
Res onant
Cavity
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
89
This detector is based on the fact that the frequency output from
piezoelectric material is influenced by the weight of the coatings or
layers on its surface. This phenomenon has been used for many years to
measure trace concentrations of water vapor in a gas and, in addition
xylene vapor in air has been detected by this means at concentrations as
low as 10-6 g/ml. This method of detection was first introduced as a GC
detecting system by King (42).
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
90
5 cm high. The walls of the vessel were coated with a high boiling
absorbent such as polyethylene glycol or an appropriate normal
hydrocarbon depending on the samples being trapped. Under such
circumstances the solutes separated had to be relatively low boiling
otherwise they would condense in the capillary connecting tube to the
adsorption vessel. The tube dipped to the base of the absorber where a
baffle was situated to direct the eluent to the walls of the adsorption
vessel. The balance record represented an integral chromatogram, the
step height giving directly the mass of solute eluted.
Capillary Tube
(0.5 m I.D.) Eluent from
Column
Glass Ce ll
Baffle Plate
Recording
Balance
Bias
Potentiome ter Amplifie r
Recorder
To
From Was te
Column
Vibrating
Plate
Me chanical
Conne ction
Me chanical
Os cillator
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
93
Both plates were constructed of the same metal but one plate was
coated with a monolayer of a suitable substance that would absorb any
vapors present in the column eluent. The absorbing layer caused the
charge on the two plates to be dissimilar and thus a potential appeared
across the two plates which was balanced out by the bias potentiometer.
When a solute vapor passes through the detector, some is distributed
into the absorbent layer, changing the surface charge and thus inducing
a change in potential between the electrodes. This produces an AC
signal voltage that can then amplified, rectified and the output passed
to a recorder (or to a data acquisition system). The signals provided by
the detector sensor could be as great as several hundred millivolts.
Of the four, the FID is the most versatile, sensitive and linear, and
should be the first to be considered when facing the challenge of a new,
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
94
References
(1957)131.
9. H. Boer, "Vapor Phase Chromatography" (Ed. D.H. Desty and C.
L. A. Harbourn), Butterworths Scientific Publications (1957)169.
10. D. W. Grant, "Gas Chromatography 1958" (Ed. D. H. Desty),
Butterworths Scientific Publications, (1957)153.
11. N. H. Ray, J. Appl. Chem., 4(1954)21.
12. 1. J. Harley, W. Nel and V. Pretorious, Nature, London,
181(1958)177.
13. I. G. McWilliams and R. A. Dewer, "Gas Chromatography 1958",
(Ed. D. H.Desty), Butterworths Scientific Publications
(1957)142.
14. S. A. Beres, C. D. Halfmann, E. D. Katz and R. P. W. Scott,
Analyst, 112(1987)91.
15. L. Ongkiehong, "Gas Chromatography 1960" (Ed. R. P. W. Scott)
Butterworths, London (1958)9.
16. D. H. Desty, A. Goldup and C. J. Geach, "Gas Chromatography
1960" (Ed. R. P. W. Scott) Butterworths, London (1958)156.
17. H, F. Calcote and I. R. King, "The Fifth Symposium on
Combustion", New York (1955).
18. K. E. Schuler and J. J. Weber, J. Chem. Phys., 22(1994)491.
19. H. Reese, Ph. D. Thesis, University of London (Birkbeck
College) (1992)
20. J. E. Lovelock and S. R. Lipsky, J. Amer. Chem. Soc.
82(1960)431.
21 J. E. Lovelock, J. Chromatogr. 1(1958)35.
22 J. E. Lovelock, Nature, Lond. 181(1958)1460.
23. R. P. W. Scott, Nature, Lond, 183(1959)1753.
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.
96
33(1961)515.
41. J. D. Winefordner, H. P. Williams and C. D. Miller, Anal. Chem.
37(1965)161
42.W. H. King, Anal Chem., 36(1964)1735.
43. S. C. Bevan and S. Thorburn, J. Chromatogr., 111(1963)301
44. S. C. Bevan and S. Thorburn, Chem. in Britain, 1(1965)206.
45. S. C. Bevan, T. A. Gough and S. Thorburn, J. Chromatogr.,
43(1969)192.
46. S. C. Bevan, T. A. Gough and S. Thorburn, J. Chromatogr.,
42(1969)336.
47. J. H. Griffiths and C. S. G. Phillips, J. Chem. Soc., (1954)3446.
48. J. H. Griffiths, D. J. James and C. S. G. Phillips, Analyst,
77(1952).
This eBook is protected by Copyright law and International Treaties. All rights are reserved. This book is covered by an End User Licensee
Agreement (EULA). The full EULA may be seen at http://www.library4science.com/eula.html.