Impact ionization mass spectrometers

The electron impact ionization mass spectrum of cortisone acetate was obtained using solid probe introduction, using a Shimadzu QP-Class-5000 gas chromatography mass spectrometer system. The most prominent ions observed, and their relative intensities, are shown in Table 6. 

Field desorption and electron impact ionization mass spectra were taken by using a Matsuda type double focussing spectrometer... 

The mass spectrometer consists of an inlet system, an ionization device, a mass analyzer, and an ion detector, and the system is kept at a vacuum of about 10 4 to 10 7 Torr. (There are various options available for all four basic components which illustrates the versatility of the technique.) The following describes an electron impact-quadruple mass spectrometer. 

In thermal ionization mass spectrometry (TI-MS), solid, inorganic compounds may be volatilized from a heated surface. TI-MS is the most precise method for the measurement of isotopic ratios of minerals and has been used to analyze 58pe in fecal samples collected from a human study (H). The major drawbacks of this technique are the costly instrument and the slow sample through-put. Conventional mass spectrometry produces ions by electron bombardment of the vapor of volatile compoimds. This is called electron-impact ionization mass spectrometry (EI-MS). Analysis of iron by EI-MS requires derivitization to volatile forms before introduction into the mass spectrometer. A method has been developed for the synthesis of volatile iron-acetylacetone chelates from iron in blood serxm (1 ). A tetraphenylporphyrin chelate has also been synthesized and used in an absorption study in which 54pe and 57pe were given orally (16). 

Thermal electron attachment to SF6 has been studied in the ECD and NIMS at atmospheric pressure and in a chemical ionization mass spectrometer at lower pressures. From these data rate constants for thermal electron attachment and detachment to SF6, and the Qan values and electron affinities of SF6 and SF5 have been determined. The Morse potential energy curves for multiple negative-ion states were calculated using electron impact data and electron affinities. 

Fig. 4.7 Schematic diagram of an electron ionization (or electron impact, El) mass spectrometer. During operation, the interior of the instrument is evacuated.

The first commercially available multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) setup was the Plasma 54, introduced in 1992 by VG Elemental. This mass spectrometer incorporated the detector platform from the Sector 54 thermal ionization mass spectrometer and included an electrostatic analyzer before the entrance to the magnetic sector. This instmment featured seven Faraday cups and a Daly detector. The Daly detector [7] incorporates an A1 knob maintained at +25 kV together with a scintillator screen and photomultiplier (Figure 3.2). Incoming ions are accelerated to the A1 knob and large numbers of secondary electrons are produced as result of the impact of these ions on the aluminum surface. These electrons are then accelerated towards the scintillator. 

Molecular Identification. In the identification of a compound, the most important information is the molecular weight. The mass spectrometer is able to provide this information, often to four decimal places. One assumes that no ions heavier than the molecular ion form when using electron-impact ionization. The chemical ionization spectrum will often show a cluster around the nominal molecular weight. 

The various SNMS instruments using electron impact postionization differ both in the way that the sample surface is sputtered for analysis and in the way the ionizing electrons are generated (Figure 2). In all instruments, an ionizer of the electron-gun or electron-gas types is inserted between the sample surface and the mass spectrometer. In the case of an electron-gun ionizer, the sputtered neutrals are bombarded by electrons from a heated filament that have been accelerated to 80—... 

Experimental. The mass spectra in Figures 1-8 are positive-ion spectra produced by electron impact and were obtained from a single-focusing, magnetic deflection Atlas CH4 Mass Spectrometer. The ionizing potential was 70 e.v. and the ionizing current 18/a a. An enamel reservoir heated to 120°C. was used from which the sample was leaked into the ion source. 

Tandem mass spectrometry (MS/MS) is a method for obtaining sequence and structural information by measurement of the mass-to-charge ratios of ionized molecules before and after dissociation reactions within a mass spectrometer which consists essentially of two mass spectrometers in tandem. In the first step, precursor ions are selected for further fragmentation by energy impact and interaction with a collision gas. The generated product ions can be analyzed by a second scan step. MS/MS measurements of peptides can be performed using electrospray or matrix-assisted laser desorption/ionization in combination with triple quadruple, ion trap, quadrupole-TOF (time-of-flight), TOF-TOF or ion cyclotron resonance MS. Tandem... 

Some of the problems encountered in the mass spectrometric study of ion-molecule reactions are illustrated in a review of the H2-He system (25). If the spectrometer ion source is used as a reaction chamber, a mixture of H2 and He are subjected to electron impact ionization, and both H2+ and He+ are potential reactant ions. The initial problem is iden-... 

In brief, the method consists of introducing small amounts (partial pressures of 10 3-10 4 torr) of the substance to be investigated into the ionization chamber of a mass spectrometer which contains a high pressure (1 torr) of methane, the reactant gas. Ionization is effected by electron impact, and because the methane is present in such an overwhelming preponderance, all but a negligibly small amount of the initial ionization occurs in the methane. The methane ions then undergo ion-molecule reactions to produce a set of ions which serve as reactant ions in the chemical ionization process. The important reactant ions formed from... 

The particles then enter a conventional mass spectrometer source where they are vaporized prior to being ionized using electron impact or chemical ionization. As with other interfaces, this may cause problems during the analysis of thermally labile and highly in volatile compounds. 

Chromatography is typically at atmospheric pressure while source pressures in the mass spectrometer are in the range of 2 to 10 Torr for chemical and electron impact ionization, respectively. The interface must be capable of providing an adequate pressure drop between the two instruments and should also maximize the throughput of seuaple idiile maintaining a gas flow rate compatible with the source operating pressure. Further, the Interface should not introduce excessive dead volume at the column exit and should not degrade or modify the chemical constitution of the sample. 

Pyrolysis mass spectroscopy was conducted with a Hewlett-Packard model 5985B gas chromatograph/quadrupole mass spectrometer, operated at sslO- Torr and 70eV electron-impact ionization energy. Samples were introduced into the mass spectrometer via a glass lined direct insertion probe (DIP). The samples were decomposed in the DIP to a nominal temperature of 300°C at a heating rate of 30°C/min. 

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