Sector instruments

Magnetic sector instruments typically operate with ion sources held at a potential of between 6 and 10 kV. This results in ions with keV translational kinetic energies. The ion kinetic energy can be written as zt V = Ifur and thus the ion velocity is given by the relationship... 

Figure Bl.7.7. Summary of the other collision based experiments possible with magnetic sector instruments (a) collision-mduced dissociation ionization (CIDI) records the CID mass spectrum of the neutral fragments accompanying imimolecular dissociation (b) charge stripping (CS) of the incident ion beam can be observed (c) charge reversal (CR) requires the ESA polarity to be opposite that of the magnet (d) neutiiralization-reionization (NR) probes the stability of transient neutrals fonned when ions are neutralized by collisions in the first collision cell. Neutrals surviving to be collisionally reionized in the second cell are recorded as recovery ions in the NR mass spectrum.

The beam entering the ion chamber is suitable for both electron (El) and chemical (Cl) ionization, and either mode can be used (Figure 12.3). Mass analysis follows in the usual way, typically using quadruple or magnetic-sector instruments. 

Also in general terms, the TOF part of the hybrid is used mostly for MS/MS studies in which ions produced in the magnetic sector are collided with neutral gas molecules to induce decomposition (see Chapter 23). In this mode the instrument produces more highly resolved product ion spectra than can be attained in simple magnetic-sector instruments. 

A further important property of the two instruments concerns the nature of any ion sources used with them. Magnetic-sector instruments work best with a continuous ion beam produced with an electron ionization or chemical ionization source. Sources that produce pulses of ions, such as with laser desorption or radioactive (Californium) sources, are not compatible with the need for a continuous beam. However, these pulsed sources are ideal for the TOF analyzer because, in such a system, ions of all m/z values must begin their flight to the ion detector at the same instant in... 

The AutoSpec -TOF hybrid mass spectrometer combines the advantages of a magnetic/electric-sector instrument with those of time-of-flight to give a versatile instrument capable of MS or MS/MS at high or low resolution. 

There are other characteristics of quadrupoles that make them cheaper for attainment of certain objectives. For example, quadrupoles can easily scan a mass spectrum extremely quickly and are useful for following fast reactions. Moreover, the quadrupole does not operate at the high voltages used for magnetic sector instruments, so coupling to atmospheric-pressure inlet systems becomes that much easier because electrical arcing is much less of a problem. 

Ion trajectory through a conventional (EB) sector instrument, showing three field-free regions in relation to the sectors, the source, and the ion detector. 

In a sector instrument, which acts as a combined mass/velocity filter, this difference in forward velocity is used to effect a separation of normal and metastable mj" ions (see Chapter 24, Ion Optics of Magnetic/Electric-Sector Mass Spectrometers ). However, as discussed above, the velocity difference is of no consequence to the quadmpole instrument, which acts only as a mass filter, so the normal and metastable mj ions formed in the first field-free region (Figure 33.1) are not differentiated. 

In an EW- of a B/E-linked scan using an electric/magnetic-sector instrument, a precursor ion is selected. In this case it is m, which might be a molecular ion but equally could be any fragment ion. All product ions (mj, m3, m4) from decomposition of m, in the first field-free region between the ion source and the ion collector are found, thereby giving connections mpm, m -m3, m -m4. 

An added consideration is that the TOF instruments are easily and quickly calibrated. As the mass range increases again (m/z 5,000-50,000), magnetic-sector instruments (with added electric sector) and ion cyclotron resonance instruments are very effective, but their prices tend to match the increases in resolving powers. At the top end of these ranges, masses of several million have been analyzed by using Fourier-transform ion cyclotron resonance (FTICR) instruments, but such measurements tend to be isolated rather than targets that can be achieved in everyday use. 

Magnetic/electric-sector instruments are used to manipulate ion beams by making use of the deflection of charged species (ions) in magnetic or electric fields. 

This focusing action gives an ion beam, in which the m/z values can be measured so accurately that the resolution of a magnetic/electric-sector instrument (separation of ions of different m/z values) is measured as a few parts per million, compared to the more modest few parts per thousand in, say, a quadmpole or ion-trap instrument. 

The appearance of the mass spectrum is closely similar to that provided by a magnetic-sector instrument. 

To examine metastable ions in electric/magnetic-sector instruments it is necessary to manipulate one or more of the electric or magnetic fields. 

Scanning techniques are carried out differently with such hybrid instruments as the triple quadrupole analyzer, the Q/TOF (quadrupole and time-of-flight), and double magnetic-sector instruments. 

Fixed-product ion scans (sector instruments). High-voltage scan or linked scan at constant B /E. Both techniques give a spectrum of all precursor (parent) ions that fragment to yield a preselected product (daughter) ion. 

Momentum spectrum. A spectrum obtained when a beam of ions is separated according to the momentum-to-charge (m/z) ratios of the ionic species present. A magnetic-sector analyzer achieves separation of the various ionic species in this way. If the ion beam is homogeneous in translational energy, as is the case with sector instruments, separation according to the m/z ratios is also achieved. 

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