Magnetic sector

In a realistic situation, the ions produced in the ion source always have a certain distribution of ion kinetic energy that will impact the mass resolution 

Mass Analyzer Qnantity Being Measnred Mass Range (Da) Mass Resolution Dynamic range  

Ion trap Path stabihty 10= Unit resolution, 10 at slow scan speed 10  

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Before ehding this presentation on mass spectrometry, we should cite the existence of spectrometers for which the method of sorting ions coming from the source is different from the magnetic sector. These are mainly quadripolar analyzers and, to a lesser degree, analyzers measuring the ion s time of flight. 

The quadripolar spectrometers whose resolution is limited to about 2000 are of simpler design than the magnetic sectors and are less costly. They are often used in conjunction with gas chromatography (see section 3.3) for purposes of identification. 

The chapter is divided into sections, one for each general class of mass spectrometer magnetic sector, quadnipole, time-of-flight and ion cyclotron resonance. The experiments perfonned by each are quite often unique and so have been discussed separately under each heading. 

Figure Bl.7.4. Schematic diagram of a reverse geometry (BE) magnetic sector mass spectrometer ion source (1) focusing lens (2) magnetic sector (3) field-free region (4) beam resolving slits (5) electrostatic sector (6) electron multiplier detector (7). Second field-free region components collision cells (8) and beam deflection electrodes (9).

Most instruments are configured with a fixed value for the radius of curvature, r, so changing the value of B selectively passes ions of particular values of momentum, mv, tlirough tlie magnetic sector. Thus, it is really the momentum that is selected by a magnetic sector, not mass. We can convert this expression to one involving the accelerating potential. 

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... 

In odier words, ions with a particular mass-to-charge ratio, m/z, can be selectively passed tlirough the magnetic sector by appropriate choice of a value of V and B (though nonnally V is held constant and only B is varied). 

Magnetic sectors can be used on their own, or in conjunction with energy analysers to fomi a tandem mass spectrometer. The unique features of the reverse geometry instrument are presented from this point. 

A single magnetic sector can be used as a mass filter for other apparatus. However, much more infonnation of the simple mass spectrum of a species can be obtained using the tandem mass spectrometer. 

Ions accelerated out of the ion source with keV translational kinetic energies (and m/z selected with the magnetic sector) will arrive in the FFR of the instrument in several microseconds. Ions dissociating on this... 

Figure Bl.7.5. (a) MIKE spectrum of the iinimoleciilar decomposition of 1-butene ions (m/z 56). This spectrum was obtained in the second field-free region of a reverse geometry magnetic sector mass...

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.

Another approach to mass analysis is based on stable ion trajectories in quadnipole fields. The two most prominent members of this family of mass spectrometers are the quadnipole mass filter and the quadnipole ion trap. Quadnipole mass filters are one of the most connnon mass spectrometers, being extensively used as detectors in analytical instnunents, especially gas clnomatographs. The quadnipole ion trap (which also goes by the name quadnipole ion store, QUISTOR , Paul trap, or just ion trap) is fairly new to the physical chemistry laboratory. Its early development was due to its use as an inexpensive alternative to tandem magnetic sector and quadnipole filter instnunents for analytical analysis. It has, however, staned to be used more in die chemical physics and physical chemistry domains, and so it will be described in some detail in this section. 

To be effective, it is necessary for the ions traversing the instniment to experience several RF cycles. Thus, unlike magnetic sector instmments, the ions fonned in the ion source of a quadnipole mass filter apparatus are accelerated to only a few eV kinetic energy (typically 5-10 eV). The timescale of the experiment is therefore... 

After ions have been formed by El, they are examined for mass and abundance by the analyzer part of the mass spectrometer, which can incorporate magnetic sectors, electric sectors, qua-drupoles, time-of-flight tubes, and so on. The region in which the ions are first formed is called... 

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. 

An AutoSpec-TOF mass spectrometer has a magnetic sector and an electron multiplier ion detector for carrying out one type of mass spectrometry plus a TOF analyzer with a microchannel plate multipoint ion collector for another type of mass spectrometry. Either analyzer can be used separately, or the two can be run in tandem (Figure 20.4). 

Hybrid Magnetic-Sector Time-of-Flight (Sector/TOF)... 

In the magnetic-sector/TOP hybrid, ions produced in an ion source pass through the magnetic sector first and then might enter the TOF section, depending on how the hybrid is operated. The hybrid can be used as two separate instruments or as two instruments in conjunction with each other. 

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... 

In the following discussion, the separate use of the magnetic sector and the TOF sector are examined briefly, followed by a discussion of the hybrid uses. 

Like the magnetic sector, the TOP section by itself is not capable of MS/MS operation, but allied with the sector, the two make an excellent MS/MS instrument. 

The double-focusing combination of electrostatic- and magnetic-sector analyzers allows the inherent energy spread of the beam to be compensated for by design and ensures that there is no spread in the beam at the collector. 

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