The Electron Capture Detector

The electron capture detector contains a low energy -ray source which is
used to produce electrons for capturing by appropriate atoms. Although
tritium adsorbed into a silver foil has been used as the  particle source, it
is relatively unstable at high temperatures, the Ni63 source was found to be
preferable. The detector can be used in two modes, either with a constant
potential applied across the cell (the DC mode) or with a pulsed potential
across the cell (the pulsed mode). In the DC mode, hydrogen or nitrogen
can be used as the carrier gas and a small potential (usually only a few
volts) is applied across the cell that is just sufficient to collect all the
electrons available and provide a small standing current. If an electron
capturing molecule (for example a molecule containing an halogen atom
which has only seven electrons in its outer shell) enters the cell, the
electrons are captured by the molecule and the molecules become charged.
The mobility of the captured electrons is much smaller than the free
electrons and the electrode current falls dramatically. The DC mode of
detection, however, has some distinct disadvantages. The most serious
objection is that the electron energy varies with the applied potential. The
electron capturing properties of a molecule varies with the electron energy,
so the specific response of the detector will depend on the applied potential
Operating in the pulsed mode, a mixture of 10% methane in argon is
employed which changes the nature of the electron capturing environment.
The electrons generated by the radioactive source rapidly assume only
thermal energy and, in the absence of a collecting potential, exist at the
source surface in an annular region about 2 mm deep at room temperature
and about 4 mm deep at 400˚C. A short period square wave pulse is
applied to the electrode collecting the electrons and producing a base
-
current. The standing current, using 10% methane in argon is about 10
8 -12
amp with a noise level of about 5 x 10 amp. The pulse wave form is
shown in figure 26.

Figure 26. Wave form of Electron Capture Detector Pulses

 In the inactive period of the wave form, electrons having thermal energy
only will attached themselves readily to any electron capturing molecules
present in the cell with the consequent production of negatively charged
ions. The negative ions quickly recombine with the positive ions (produced
simultaneously with the electrons by the  particles) and thus
become unavailable for collection. Consequently the standing current
measured during the potential pulse will be reduced.
The period of the pulsed potential is adjusted such that relatively few of the
slow negatively charged molecules (molecules having captured electrons
and not neutralized by collision with positive ions) have time to reach the
anode, but the faster moving electrons are all collected. 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. By appropriate adjustment of these parameters the current can
be made to reflect the relative mobilities of the different charged species in
the cell and thus exercise some discrimination between different electron
capturing materials. A diagram of an electron capture detector is shown in
figure 27.

Figure 27 The Electron Capture Detector

The basic electron capture detector consists of a small chamber one or two
ml in volume enclosing two metal electrodes. The electrodes may be
concentric cylinders or metal discs separated by an insulator. The cell
contains the radioactive source, electrically connected to the entrance
conduit and to the negative side of the power supply. A gauze "diffuser" is
 connected to the cell exit and to the positive side of the power supply. The
output from the sensor is processed by suitable electronics and the output
passed to either a potentiometric recorder of a computer data acquisition
system. The electron capture detector is very sensitive, probably the most
sensitive GC detector available (ca. 10-13 g/ml) and is widely used in the
analysis of halogenated compounds, in particular, pesticides.

The column used was a SPB-608 fused silica capillary column, 30 m x 0.53
mm I.D. with a 0.5  film of stationary phase. The column was
programmed from 50oC at 1o/min. to 150oC and then to 260oC at 8o/min.
Helium was used as the carrier gas at a flow rate of 5 ml/min. The sample
consisted of 0.6l of a solution of the pollutants in n-decane. The mass of
each pollutant present was about 120 pg.

Electron Capture Detector ( ECD ) The electron capture detector was an early high
sensitivity gas chromatography detector invented by Lovelock in the late 1950s. It evolved
from the development of the argon detector, although it worked on an entirely different
principle. In its original form, it consists of a cell containing a low energy -ray source that
produces both electrons and ions. The original source was tritium absorbed into silver foil
but, due to its inherent temperature instability, this was quickly replaced by the thermally
stable 63Ni source. Some more recent detectors generate the electrons by plasma
discharge. The detector can function in two ways, either with a constant DC potential
applied across the electrodes (the DC mode) or a pulsed potential applied across the
electrodes (the pulsed mode). In the DC mode a constant potential of a few volts is applied
across the electrodes that is just sufficient to collect all the electrons that are produced and,
thus, provide a small standing current. When an electron capturing molecule enters the
detector (e.g., a halogenated molecule) the electrons are captured by the molecules and the
molecules become charged. The mobility of the electrons, captured by the halogenated
material, is much smaller than the free electrons and the captured electrons are also more
likely to be neutralized by collision with positive ions. As a consequence, the detector
current falls dramatically. In the pulsed mode, the period of the pulsed potential is adjusted
so that relatively few of the slow negatively charged molecules reach the anode but the
faster moving electrons are all collected. During the off-period of the pulse the electrons re-
establish equilibrium with the gas. The operating variables are pulse duration, the pulse
frequency and the pulse amplitude. By appropriate adjustment of these pulse
characteristics, the current can be made to indicate the mobilities of the different charged
species in the cell and thus, provide some discrimination between different electron
capturing materials. The electron capture detector is one of the most sensitive gas
chromatography detectors available.