Chemical Analysis. Francis Rouessac

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Chemical Analysis - Francis Rouessac


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(ID = 0.1–0.2 mm) with no bleeding.

      

      2.7.2 Selective Detectors

      Nitrogen phosphorus detector (NPD)

      This specific detector is sensitive to nitrogen (N) or phosphorus (P) compounds. It comprises a small ceramic cylinder doped with an alkaline salt (e.g. rubidium sulfate). A voltage is applied to maintain a small plasma (800°C) through the combustion of an air/hydrogen mixture (Figure 2.12). Compared with FID, the flame is much smaller. Compounds containing nitrogen or phosphorus give, fairly specifically, decomposition fragments transformed into negative ions. These ions are then received by a collector electrode. The nitrogen present in air is inactive. Detector sensitivity is typically 0.1 pg/s for nitrogen‐ or phosphorus‐containing analytes, with a linear range of five orders of magnitude. However, it varies a lot with settings.

      Electron capture detector (ECD)

      This detector is considered to be selective because it is much more sensitive to halocarbon groups. A flow of nitrogen gas that has been ionized by electrons generated from a low‐energy β radioactive source (a few mCi of 63Ni) passes between two electrodes maintained at a potential differential of around 100 V (Figure 2.14). At rest, a base current I0 is generated, mainly due to free and very mobile electrons. If molecules (M) containing a halogen (F, Cl, Br) cross the zone between the two electrodes, they capture thermally excited electrons to form heavy negative ions, which by consequence are much less mobile.

StartLayout 1st Row upper N 2 right-arrow Overscript beta Superscript minus Baseline Endscripts upper N 2 Superscript plus Baseline plus e Superscript minus Baseline 2nd Row upper M plus e Superscript minus Baseline right-arrow upper M Superscript minus Baseline 3rd Row upper M Superscript minus Baseline plus upper N 2 Superscript plus Baseline right-arrow upper M plus upper N 2 EndLayout

      The measured intensity decreases exponentially by following a law of the type I = I0 exp[−kc]. The linear range is about four orders of magnitude with nitrogen as the make‐up gas. The presence of a radioactive source in this detector means that it is subject to special regulations (inspection, location and maintenance visits). This detector is often used for analyses of chlorinated pesticides and polychlorinated biphenyls.

Schematic illustration of (a) electron capture detector (ECD) and (b) photo-ionization detector (PID).

      Photo‐ionization detector (PID)

      This detector is fairly selective but it has only a narrow range of applications. It is suitable for hydrocarbons as well as for sulfur or phosphorus derivatives. The operating principle consists in provoking ionization of the analytes by irradiation with a UV lamp emitting high‐energy photons (8.4–11.8 eV). Photo‐ionization occurs when the energy of the photon is greater than the first ionization energy of the compound (Figure 2.14). A photon of 9.6 eV can, for example, ionize benzene (PI1 = 9.2 eV) but not isopropanol (PI1 = 10.2 eV), which will therefore not be very visible on the chromatogram. Electrons released by an electrode connected to the terminal of an electrometer are collected for concentration measurements.

      This detector can function at more than 400°C and is not destructive, as the ionization is reversible and affects only a small fraction of the molecules of each compound.

      2.7.3 Detectors Providing Structural Data

      None of the detectors previously described yield any information as to the nature of the eluted analytes. At most, they are selective for a certain category of compounds. Identification involves the use of an internal calibration based on retention times or requires the knowledge of retention indexes (see Section 2.10). When the chromatogram has peaks that are close together, a confusion of identity could occur.

Schematic illustration of three detectors connected in series.

      If we assume that the optimal stationary phase has been chosen, the length and internal diameter ID of a capillary column as well as its stationary phase film thickness (df) must also be taken into account. The conditions for a good separation of the analytes need to be found without increasing the analysis time. From a practical standpoint, in GC, we can only change the temperature and the carrier gas flow rate. In both cases, retention factors k and selectivities α are not much changed. For the carrier gas, we choose a flow rate such that its speed ū is close to the optimal value of the Van Deemter curve. For volatile compounds, we choose a column with a weak phase ratio (β < 100), hence with a thick film. Inversely, we choose a thin‐film column for less volatile compounds.

      However, we must not forget that coupled GC‐MS does not necessarily require greatly optimized separation of chromatographic peaks (sufficient resolution), which is a significant time gain for the chromatographer. Moreover, in a series of analyses, if we can avoid the use of a temperature gradient,


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