Nebulising gas

ES ionisation can be pneumatically assisted by a nebulising gas a variant called ionspray (IS) [129]. ESI is conducted at near ambient temperature too high a temperature will cause the solvent to start evaporating before it reaches the tip of the capillary, causing decomposition of the analyte during ionisation and too low a temperature will allow excess solvent to accumulate in the sources. Table 6.20 indicates the electrospray ionisation efficiency for various solvents. 

Since APCI is a chemical ionization, it needs a gas. Indeed, a nebulising gas (generally nitrogen) is introduced into the source. The gas molecules are ionized by a corona discharge (analogous to the fdament used in Cl) thus forming the primary ions, mainly composed of N2+" and N4+". In turn, the latter ionize the vaporized solvent molecules by... 

Figure 15.1—Inductively coupled plasma torch. A radiofrequency current (between 27 and 50 MHz) that induces circulation of the electrons in the inert gas drives the torch. The argon serves as an auxiliary gas, a cooling gas and the nebulisation gas. In the upper right is shown an optic device used to collect emitted light in the longitudinal axis of the plasma. Lower down, plasma generated by microwave.

Carey and Caruso [126] also summarised the two main approaches to interfacing the SFC restrictor with the ICP torch. The first method, used with packed SFC columns, introduces the restrictor into a heated cross-flow nebuliser and the nebulised sample is subsequently swept into the torch by the nebuliser gas flow. Where capillary SFC systems are used, a second interface design is commonly employed where the restrictor is directly introduced into the central channel of the torch. This interface is more widely used with SFC-ICP-MS coupling [20]. The restrictor is passed through a heated transfer line which connects the SFC oven with the ICP torch. The restrictor is positioned so that it is flush with the inner tube of the ICP torch. This position may, however, be optimised to yield improved resolution. The connection between the transfer line and the torch connection must be heated to prevent freezing of the mobile phase eluent after decompression when exiting the restrictor. A make-up gas flow is introduced to transport the analyte to the plasma. This... 

Fig. 9.8 ESI MS plot after 90 min reaction and list of possible cyclopentyl silsesquioxanes with 1

Plasma nebuliser gas flow will influence the aerosol drop size, efficiency, stability and... 

Atmospheric pressure chemical ionisation (APCI) is a technique that also creates gas phase ions from the liquid sample. It too takes place at atmospheric pressure and uses a similar interface to that in ESI. As in ESI, the sample solution is mixed with a nebulising gas and the sample arrives in the spray chamber as a fine mist of droplets or spray. In APCI, an extra component - a corona discharge - is used to further ionise the analyte droplets in a manner similar to straightforward Cl (Figure 2.34). While a small amount of fragmentation may occur, the technique is still considered to be a soft ionisation one. The gas-phase ionisation in APCI is more effective than ESI for analysing less polar species. ESI and APCI are complementary methods. 

Most examples in the literature exploit electrospray ionisation but some research groups have reported the use of atmospheric pressure chemical ionisation (APCI) on-chip. In one such example, the chip was composed of two wafers, one made of silicon wafer one made of pyrex glass . The silicon wafer contained the nebuliser gas inlet, vapouriser channel and a nozzle. The sample inlet from the LC column was directly connected to the... 

Electrospray ionisation is achieved at atmospheric pressure, the mass analyser, however, operates under high vacuum. A special interface is therefore necessary to transfer the ions from the ionisation chamber into the mass spectrometer. A schematic of such an interface is shown in Fig. 4.14. Usually a zone of intermediate pressure separates the ionisation chamber and the mass analyser. The liquid sample together with a curtain or nebulising gas is introduced into the heated ionisation chamber. An electrospray is generated by applying a potential difference between the needle and the opposite interface plate. A small proportion of the desolvated analyte ions exit the ionisation chamber through a submillimeter orifice and enter the zone of intermediate pressure. The analyte ions then pass via another small orifice into the mass analyser. This is usually a quadrupole which is operated under high vacuum. 

GC/MS with capillary columns has been the gold standard for more than 20 years, but LC/MS has become a complementary method due to the success in interface development with atmospheric pressure ionisation (API) for low molecular weight compounds and the appHcation to biopolymers. For many areas of analytical chemistry, LC/MS has become indispensible due to its advantages over GC/MS for polar and thermolabile analytes. A Hmiting factor for LC/MS has been the incompatibility between the hquid eluting from the LC and the mass spectrometer vacuum. This could be overcome in electrospray ionisation with the use of a nebuliser gas ( ion spray ) or additional heated drying gas ( turbo ion spray ) (70, 71]. Due to its high sensitivity and selectivity, APl-MS has become a standard tool for the stracture elucidation of analytes from complex mixtures. 

Optimisation of flow rates of the cooling gas, top and bottom electrode gas, sample liquid flow rate, nebuliser gas and DC current in a variable-diameter multi-elecrode DC plasma. 

The long-term stability of the ICP radiofrequency power and nebuliser gas flow rate were assessed by experimental designs. Three-way multivariate studies were carried out three-way PARAFAC studies were employed as well. 

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