Gases mass spectra

Pyrolysis and reforming of several types of common plastics (polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polyurethane, and polycarbonate) were studied qualitatively, using a micro-reactor interfaced with a MBMS. Each type of plastic pyrolyzed at 550-750°C. This was followed by steam reforming of vapors in a fixed bed of C-11 NK catalyst at 750-800°C. The composition of the product gas (mass spectrum) was observed for different values of the steam-to-carbon mtio and space velocity that changed depending on the size of plastic samples. Preliminary tests showed that at process conditions similar to those used for reforming natural gas, polymers were almost completely converted to hydrogen and carbon oxides. 

Figure 7.5 Distribution of clusters ROH.. Bn in inert gas. Mass spectrum from time-of-flight measurements on mixtures of 1-naphthol (ROH) and ammonia (B) dispersed in helium, showing peaks corresponding to ROH.. B with n = 1 to 10. From Figure 6 of Ref. [6,a].

In GC-MS effluent from the column is introduced directly into the mass spectrometer s ionization chamber in a manner that eliminates the majority of the carrier gas. In the ionization chamber all molecules (remaining carrier gas, solvent, and solutes) are ionized, and the ions are separated by their mass-to-charge ratio. Because each solute undergoes a characteristic fragmentation into smaller ions, its mass spectrum of ion intensity as a function of mass-to-charge ratio provides qualitative information that can be used to identify the solute. 

If the substrate (M) is more basic than NHj, then proton transfer occurs, but if it is less basic, then addition of NH4 occurs. Sometimes the basicity of M is such that both reactions occur, and the mass spectrum contains ions corresponding to both [M + H]+ and [M + NH4]. Sometimes the reagent gas ions can form quasi-molecular ions in which a proton has been removed from, rather than added to, the molecule (M), as shown in Figure 1.5c. In these cases, the quasi-molecular ions have one mass unit less than the true molecular mass. 

Schematic diagram of an orthogonal Q/TOF instrument. In this example, an ion beam is produced by electrospray ionization. The solution can be an effluent from a liquid chromatography column or simply a solution of an analyte. The sampling cone and the skimmer help to separate analyte ions from solvent, The RF hexapoles cannot separate ions according to m/z values and are instead used to help confine the ions into a narrow beam. The quadrupole can be made to operate in two modes. In one (wide band-pass mode), all of the ion beam passes through. In the other (narrow band-pass mode), only ions selected according to m/z value are allowed through. In narrow band-pass mode, the gas pressure in the middle hexapole is increased so that ions selected in the quadrupole are caused to fragment following collisions with gas molecules. In both modes, the TOF analyzer is used to produce the final mass spectrum.

An example of linked scanning on a triple quadrupole instrument. A normal ion spectrum of all the ions in the ion source is obtained with no collision gas in Q2 all ions scanned by Q1 are simultaneously scanned by Q3 to give a total mass spectrum (a). With a collision gas in Q2 and with Q1 set to pass only m+ ions in this example, fragment ions (f, fj ) are produced and detected by Q3 to give the spectrum (b). This CID spectrum indicates that both f, and fj are formed directly from m+. 

MS is a means of examining a compound, also in the gas phase, so that its stmcture or identity can be deduced from its mass spectrum. MS alone is not good for examining mixtures because the mass spectrum of a mixture is actually a complex of overlapping spectra from the individual components in the mixture. 

Method 1613 of US Environmental Protection Agency (US EPA) was used for the PCDD detection in the objects of environment (water, soil etc.). PCDD detection was done with the help of Polaris Q gas chromatograph/ mass spectrometer on mass-spectrum of electronic impact in the MS-MS mode. Division of isomer PCDD was carried out on a capillary column from the sintered quartz DB-5 MS (60 m x 0,25 mm, thickness of tape 0,25 p.m). The same device was used for detection of fungicides formulations active ingredients in soil. 

Mass spectrum obtained from the NIST Hasteloy Ni-basad standard alloy, using electron-gas SNMSd (Laybold INA-3). The sputtering energy was 1250 V, increasing the sputtered atom flux at the expense of depth resolution. Matrix ion currents ware about 10 cps, yielding background limHed detection at about 2 ppm. 

Molecular ion mass interferences are not as prevalent for the simpler matrices, as is clear from the mass spectrum obtained for the Pechiney 11630 A1 standard sample by electron-gas SNMSd (Figure 4). For metals like high-purity Al, the use of the quadrupole mass spectrometer can be quite satisfiictory. The dopant elements are present in this standard at the level of several tens of ppm and are quite evident in the mass spectrum. While the detection limit on the order of one ppm is comparable to that obtained from optical techniques, the elemental coverage by SNMS is much more comprehensive. 

Figure 4 Mass spectrum obtained from the Aiuminium Peehiney standard Ai 11630, using eiectron-gas SNMSd with a sputtering energy of 1250 V. The AI matrix ion currerrt was significantly greater than 10 cps. yielding a background courrt rate limit less than 1 ppm.

In gas chromatography/mass spectrometry (GC/MS), the effluent from a gas chromatograph is passed into a mass spectrometer and a mass spectrum is taken every few milliseconds. Thus gas chromatography is used to separate a mixture, and mass spectrometry used to analyze it. GC/MS is a very powerful analytical technique. One of its more visible applications involves the testing of athletes for steroids, stimulants, and other performance-enhancing drugs. These drugs are converted in the body to derivatives called metabolites, which are then excreted in the... 

Because the vacuum in the mass spectrometer and the cleanliness of the ion source, transfer line, GC column, and so forth are not perfect, a mass spectrum will typically have several peaks that are due to background. All GC/MS spectra, if scanned to low enough mass values, will have peaks associated with air, water, and the carrier gas. Other ions that are observed in GC/MS are associated with column bleed and column contamination. 

Gas chromatographic analysis of the product showed two major peaks (relative intensity, 5 1), and the mass spectrum of each peak revealed a molecular ion at i/e 210. The proton magnetic resonance spectrum of the mixture showed that the two products were geometrically isomeric esters. 

Heath and Majer (H3) have recently used a mass spectrometer to study the decomposition of ammonium perchlorate. Decomposition was detected in the range from 110° to 120°C. At this temperature, there were ions in the mass spectrum caused by NH3, HC104, Cl2, HC1, nitrogen oxides, and 02. The appearance of the species NO, N02,02, and Cl2 in the decomposition products under very low pressure (i.e., in the absence of gas-phase molecular collisions) indicates that the principal decomposition reactions take place in the crystal and not in the gas phase. 

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