Nitrogen Phosphorus Detector

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The Nitrogen Phosphorus Detector (NPD) is a form of gas chromatography in which thermal energy is used
to ionize an analyte. With this method, nitrogen andphosphorus can be selectively detected with
a sensitivity that is 104 times greater than that for carbon. NP-Mode: A minimum concentration of hydrogen gas
is used such that it is just below the minimum required for ignition. A rubidium or caesium bead, which is
mounted over the nozzle, ignites the hydrogen (by acting catalytically), and entails the formation of a cold
plasma. Excitation of the alkali metal results in ejection of electrons, which in turn is detected by current flow
between an anode and cathode in the chamber. In the presence of nitrogen or phosphorus combustion
products exiting the column, the work function of the metal is reduced, resulting in an increase in the current
measured.

Since the alkali metal bead is over time consumed, it must be regularly replaced - a disadvantage compared to
the related FID detector which lacks the selectivity for nitrogen and phosphorus.

The Nitrogen Phosphorus Detector ( NPD The nitrogen phosphorous detector

(sometimes called the thermionic detector) is a very sensitive but specific detector that
responds almost exclusively to nitrogen and phosphorous compounds. It is based on the
flame ionization detector but differs in that it contains a rubidium or cesium silicate (glass)
bead situated in a heater coil, a little distance from the hydrogen flame. If the detector is to
respond to both nitrogen and phosphorous then the hydrogen flow should be minimal so
that the gas does not ignite at the jet. If the detector is to respond to phosphorous only, a
large flow of hydrogen is used which is burnt at the jet. The heated bead emits electrons by
thermionic emission. These electrons are collected under a potential of a few volts by an
appropriately placed anode, and provides a background current. When a solute containing
nitrogen or phosphorous is eluted from the column, the partially combusted nitrogen and
phosphorous materials are adsorbed on the surface of the bead. The adsorbed material
reduces the work function of the surface and, as consequence, the emission of electrons is
increased which raises the current collected at the electrode. The sensitivity of the detector
to phosphorous is about 10-12 gram per ml and for nitrogen about 10-11 gram per ml at a
signal to nose ratio of 2. The alkali bead as a finite life and needs regular replacement.

The NPD sensor differs from that of the FID by a rubidium or cesium
chloride bead contained inside a heater coil situated close to the hydrogen
jet. The bead is situated above a jet and heated by a coil, over which the
nitrogen carrier gas mixed with hydrogen passes. If the detector is to
respond to both nitrogen and phosphorus, then the hydrogen flow should
beminimal so that the gas does not ignite at the jet. If the detector is to
respond to phosphorus, only, however, a large flow of hydrogen can be
used and the mixture burnt at the jet. The heated alkali bead emits
electrons by thermionic emission which are collected at the anode and
provides background current through the electrode system. When a solute
that contains nitrogen or
phosphorusiseluted, thepartiallycombustednitrogenandphosphorusmaterials
are adsorbed on the surface of the bead.

The adsorbed material reduces the work function of the surface and, thus,
electron emission is increased and the current collected at the anode rises.
The NPD has a very high sensitivity, i.e., about an order of magnitude less
than that of the electron capture detector (ca.10-12 g/ml for phosphorus and
10-11 g/ml for nitrogen).
The main disadvantage of this detector is that its performance deteriorates
with time. Reese (19) examined the performance of the NPD in
considerable detail. The alkali salt employed as the bead is usually a silicate
and Reese showed that the loss in response was due to water vapor from
the burning hydrogen converting the alkali silicate to the hydroxide and
free silica. At the normal operating temperature of the bead, the alkali
hydroxide has a significant vapor pressure and consequently, the rubidium
or cesium is continually lost during the operation of the detector. Eventually
all the alkali is evaporated, leaving a bead of inactive silica. This is an
inherent problem with all NP detectors and as a result the bead needs to be
replaced regularly if the detector is in continuous use. The detector can be
made "linear" over three orders of magnitude although no values for the
response index appear to have been reported. Like the FID it is relatively
insensitive to pressure, flow rate and temperature changes but is usually
o
thermostatted at 260 C or above. The specific response of the NPD to
nitrogen and phosphorus, coupled with its relatively high sensitivity, makes
it especially useful for the analysis of many pharmaceuticals and in
 environmental samples containing herbicides. Employingappropriate column
systems traces of herbicides at the 500 pg level can easily be determined.

The Nitrogen Phosphorus Detector (NPD)

The nitrogen phosphorus detector (NPD) (sometimes called the thermionic

detector) is a very sensitive, specific detector the design of which, is based
on the FID. Physically the sensor appears to be very similar to the FID but,
in fact, operates on an entirely different principle. A diagram of an NPD
detector is shown in figure 22.