Isotope patterns, mass spectra

Even if the analyte is chemically perfectly pure it represents a mixture of different isotopic compositions, provided it is not composed of monoisotopic elements only. Therefore, a mass spectrum is normally composed of superimpositions of the mass spectra of all isotopic species involved. [11] The isotopic distribution or isotopic pattern of molecules containing one chlorine or bromine atom is listed in Table 3.1. But what about molecules containing two or more di-isotopic or even polyisotopic elements While it may seem, at the first glance, to complicate the interpretation of mass spectra, isotopic patterns are in fact an ideal source of analytical information. 

Mass spectrum A pattern similar to the Mo isotope pattern with the most intense peak at mje = 339. (The most abundant Mo isotope is Mo.)... 

Fig. 10.16. Partial LT-FAB mass spectrum of the reaction mixture containing the iridium complexes 1 and 2 in toluene. In addition to the changes in mass, the isotopic pattern changes upon exchange of Cl by Br. By courtesy of P. Hofmann, Heidelberg University.

Many elements have two or more isotopes, and the presence of these correspondingly gives a spectrum having many peaks. On the other hand, the patterns of these isotopes in a mass spectrum often prove invaluable in identifying which elements are present, with the patterns serving as fingerprints for certain elements. 

A diagrammatic illustration of the effect of an isotope pattern on a mass spectrum. The two naturally occurring isotopes of chlorine combine with a methyl group to give methyl chloride. Statistically, because their abundance ratio is 3 1, three Cl isotope atoms combine for each Cl atom. Thus, the ratio of the molecular ion peaks at m/z 50, 52 found for methyl chloride in its mass spectrum will also be in the ratio of 3 1. If nothing had been known about the structure of this compound, the appearance in its mass spectrum of two peaks at m/z 50, 52 (two mass units apart) in a ratio of 3 1 would immediately identify the compound as containing chlorine. 

Isotopes of an element are formed by the protons in its nucleus combining with various numbers of neutrons. Most natural isotopes are not radioactive, and the approximate pattern of peaks they give in a mass spectrum can be used to identify the presence of many elements. The ratio of abundances of isotopes for any one element, when measured accurately, can be used for a variety of analytical purposes, such as dating geological samples or gaining insights into chemical reaction mechanisms. 

In a mass spectrum, the ratios of isotopes give a pattern of isotopic peaks that is characteristic of a given element. For example, the mass spectrum of any corn ound containin carbon, hydrogen, nitrogen, and oxygen will show patterns of peaks due to the, 7C, 7N, gO, gO, and... 

Qualitatively, the spark source mass spectrum is relatively simple and easy to interpret. Most instrumentation has been designed to operate with a mass resolution Al/dM of about 1500. For example, at mass M= 60 a difference of 0.04 amu can be resolved. This is sufficient for the separation of most hydrocarbons from metals of the same nominal mass and for precise mass determinations to identify most species. Each exposure, as described earlier and shown in Figure 2, covers the mass range from Be to U, with the elemental isotopic patterns clearly resolved for positive identification. 

A typical SSIMS spectrum of an organic molecule adsorbed on a surface is that of thiophene on ruthenium at 95 K, shown in Eig. 3.14 (from the study of Cocco and Tatarchuk [3.28]). Exposure was 0.5 Langmuir only (i.e. 5 x 10 torr s = 37 Pa s), and the principal positive ion peaks are those from ruthenium, consisting of a series of seven isotopic peaks around 102 amu. Ruthenium-thiophene complex fragments are, however, found at ca. 186 and 160 amu each has the same complicated isotopic pattern, indicating that interaction between the metal and the thiophene occurred even at 95 K. In addition, thiophene and protonated thiophene peaks are observed at 84 and 85 amu, respectively, with the implication that no dissociation of the thiophene had occurred. The smaller masses are those of hydrocarbon fragments of different chain length. 

The mass spectrum of the unknown compound showed a molecular ion at m/z 246 with an isotope pattern indicating that one chlorine atom and possibly a sulfur atom are present. The fragment ion at m/z 218 also showed the presence of chlorine and sulfur. The accurate mass measurement showed the molecular formula to be C]3FI7OSCl R + DB = 10. 

Figure 17.2 is an example of a mass spectrum of an aromatic dichloro compound. The intensity of the molecular ion indicates that an aromatic compound is present. The isotope pattern is that of two chlorines, and subtracting 70 mass units from the molecular ion gives the formula QHj. (See Example 2.3 in Chapter 2 for another example of isotope abundances in the molecular ion region.)... 

The molecular ion is apparent in the mass spectrum of DDT (Figure 25.2) at m/z 352 with the classic isotope pattern for five chlorine atoms (see Appendix 11). The major fragment ion is the loss of CCI3 at m/z 235. 

Applications With the current use of soft ionisation techniques in LC-MS, i.e. ESI and APCI, the application of MS/MS is almost obligatory for confirmatory purposes. However, an alternative mass-spectrometric strategy may be based on the use of oaToF-MS, which enables accurate mass determination at 5 ppm. This allows calculation of the elemental composition of an unknown analyte. In combination with retention time data, UV spectra and the isotope pattern in the mass spectrum, this should permit straightforward identification of unknown analytes. Hogenboom et al. [132] used such an approach for identification and confirmation of analytes by means of on-line SPE-LC-ESI-oaToFMS. Off-line SPE-LC-APCI-MS has been used to determine fluorescence whitening agents (FWAs) in surface waters of a Catalan industrialised area [138]. Similarly, Alonso et al. [139] used off-line SPE-LC-DAD-ISP-MS for the analysis of industrial textile waters. SPE functions here mainly as a preconcentration device. 

Cover Illustration Atomic force microscopy image of molybdenum oxide particles on flat, silicon dioxide substrate, which serves as a model system for a supported catalyst. The area shown corresponds to one square micrometer the maximum difference in height is approximately 10 nanometer. The superimposed curve is the secondary ion mass spectrum of the model catalyst, showing the caracteristic isotopic patterns of single molybdenum ions and of molybdenum oxide cluster ions. 

A third source of error is associated with the fragmentation pattern caused by dissociation of the molecular ions formed in the source region of the spectrometer. Under severe conditions these processes may proceed with substantial isotopic fractionation, and this obscures the measurements of isotopic composition at the collector. To some extent careful standardization of the instrumental conditions may ensure that errors from fragmentation are systematic, and thus cancel (at least to some extent). Alternatively, softer ionization methods can be used to prevent most or all of the fragmentation. The bottom spectrum in Fig. 7.7 illustrates this approach it shows the mass spectrum of chlorobenzene obtained by photoionization. Only the parent molecular ions are observed. It should be kept in mind, however, that softer ionization usually yields smaller ion currents and consequently statistical counting errors increase. 

In order to successfully interpret a mass spectrum, we have to know about the isotopic masses and their relation to the atomic weights of the elements, about isotopic abundances and the isotopic patterns resulting therefrom and finally, about high-resolution and accurate mass measurements. These issues are closely related to each other, offer a wealth of analytical information, and are valid for any type of mass spectrometer and any ionization method employed. (The kinetic aspect of isotopic substitution are discussed in Chap. 2.9.)... 

Bar graph representations are much better suited for visualization of isotopic compositions than tables, and in fact they exactly show how such a distribution would appear in a mass spectrum (Fig. 3.1). This appearance gives rise to the term isotopic pattern. 

The relevance of oxygen and sulfur isotopic patterns is nicely demonstrated by the cluster ion series in fast atom bombardment (FAB) spectra of concentrated sulfuric acid, where the comparatively large number of sulfur and oxygen atoms gives rise to distinct isotopic patterns in the mass spectrum (Chap. 9). 

The peaks in the m/z 50-57 range of the 1-butene El spectrum could be misinterpreted as a complex isotopic pattern if no formula were available on the plot (Fig. 3.8). However, there is no element having a comparable isotopic pattern and in addition, all elements exhibiting broad isotopic distributions have much higher mass. Instead, the 1-butene molecular ion undergoes H, H2 and multiple H2 losses. The m/z 57 peak, of course, results from In a similar fashion the peaks at m/z 39 and 41 appear to represent the isotopic distribution of iridium, but this is impossible due to the mass of iridium (cf. Appendix). However, these peaks originate from the formation of an allyl cation, CsHs, m/z 41, which fragments further by loss of H2 to form the CsHs" ion, m/z 39 (Chap. 6.2.4). 

Example The [M-Cl]" ion, [CHCl2], represents the base peak in the El spectrum of chloroform. The results of three subsequent determinations for the major peaks of the isotopic pattern are listed below (Fig. 3.15). The typical printout of a mass spectrometer data system provides experimental accurate mass and relative intensity of the signal and an error as compared to the calculated exact mass of possible compositions. For the [ CH Cl2] ion, the experimental accurate mass values yield an average of 82.9442 0.0006 u. The comparatively small absolute error of 0.6 mmu corresponds to a relative error of 7.5 ppm. 

Increasing resolution does not affect the relative intensities of the peaks, i.e., the intensity ratios for m/z 28 32 40 44 in the spectrum of air basically remain constant (Fig. 3.18). However, an increase of resolution is usually obtained at the cost of transmission of the analyzer, thereby reducing the absolute signal intensity (Chap. 4.3.4). Accordingly, isotopic patterns are not affected by increasing resolution up to / = 10,000 beyond, there can be changes in isotopic patterns due to the separation of different isotopic species of the same nominal mass (Chap. 3.4). 

Note The assignment of empirical formulae from accurate mass measurements always must be in accordance with the experimentally observed and the calculated isotopic pattern. Contradictions strongly point towards erroneous interpretation of the mass spectrum. 

Fig. 3.28. The electron impact mass spectrum of [60]fullerene. The insets show the expanded signals of M, and ions. The signals of the patterns are at 1, 0.5 and 0.33 u distance, respectively. The intensity scale has been normalized in the insets to allow for easier comparison of the isotopic patterns. By courtesy of W. Kratschmer, Max Planck Institute for Nuclear Physics, Heidelberg.

Example The El mass spectrum of Qo also shows an abundant doubly charged molecular ion, at m/z 360 with its isotopic peaks located at 0.5 u distance and a signal at m/z 240 of very low intensity (Fig. 3.28). [22] The isotopic pattern remains the same for all of them. As a consequence of the compressed m/z scale, the doubly charged fragment ion is detected at m/z 348. More examples of multiply charged ions can be found throughout the book. 

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