Mass, exact

As we have already seen, the isotopic mass also is the exact mass of an isotope. The isotopic mass is very close but not equal to the nominal mass of that isotope (Table 3.1). Accordingly, the calculated exact mass of a molecule or of a mono-isotopic ion equals its monoisotopic mass (Chap. 3.1.4). The isotope C represents the only exception from non-integer isotopic masses, because the unified atomic mass [u] is defined as of the mass of one atom of nuclide C. 

As a consequence of these individual non-integer isotopic masses, almost no combination of elements in an empirical formula has the same calculated exact mass, or simply exact mass as it is often referred to, as another one. [25] In other words, at infinite mass accuracy it is possible to identify the empirical formula by mass spectrometry alone. 

Example the molecular ions of nitrogen, N2, carbon monoxide, CO, and ethene, C2H4, have the same nominal mass of 28 u, i.e., they are so-called iso-baric ions. The isotopic masses of the most abundant isotopes of hydrogen, carbon, nitrogen and oxygen are 1.007825 u, 12.000000 u, 14.003070 u and 15.994915 u, respectively. Using these values, the calculated ionic masses are 28.00559 u for Nz , 27.99437 u for CQ- , and 28.03075 u for CjH/. This means they differ by some millimass units (mmu) from each other, and none of these isobaric ions has precisely 28.00000 u (Chap. 3.3.4 and Chap. 6.9.6). 

The use of mmu is widespread because of its convenience in dealing with small differences in mass, although the mmu is not an SI unit. 

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Exact Mass Differences. If the exact mass of the parent or fragment ions are ascertained with a high-resolution mass spectrometer, this relationship is often useful for combinations of C, H, N, and O (Table 1.15b) ... 

Exact mass difference from nearest integral mass -I- 0.005 Iz — 0.003 ly 0.0078... 

For example, if the exact mass is 177.0426 for a compound containing only C, H, O, and N (note the odd mass which indicates an odd number of nitrogen atoms), then... 

High mass resolution techniques are used to separate peaks at the same nominal mass by the very small mass differences between them. As an example, a combination of Si and H to form the molecular ion Si H , severely degrades the detection limit of phosphorous ( P) in a silicon sample. The exact mass of phosphorous ( P) is 31.9738 amu while the real masses of the interfering Si H and Si H2 molecules are 31.9816 amu and 31.9921 amu, respectively. Figure 8 shows a mass... 

The mass spectral fragmentations of 9,10-dimethoxy-2,3,4,6,7,ll/)-hexa-hydro-l//-pyrimido[6,l-n]isoquinolin-2-ones 140 and -2,4-diones 141, under electron ionization (at 70 eV) were examined by metastable ion analysis, a collosion-induced dissociation technique and exact mass measurement (97RCM1879). Methyl substituent on N(3) in 140 (R = Me) had a larger effect on both the fragmentation and on the peak intensities, than a methyl substituent on C(6) (R = Me). The ionized molecules of 140 (R = H) were rather stable, whereas 4-phenyl substitution on C(4) of 140 (R = Ph) promoted the fragmentations of the molecular ions. The hexahydro-1//-pyrimido[6,l-n]isoquinoline-2,4-diones 141 were more stable, than the hexahydro-l//-pyrimido[6,l-n]isoquinolin-2-ones 140, and the molecular ions formed base peaks. 

If we wish to gain some idea of the alteration of mass in a nuclear change, we cannot use the fission reaction because the exact masses of the nuclei involved are not known. Let us look at another type of reaction of possible importance in the production of nuclear energy ... 

Let us do a little bookkeeping with the exact masses of these nuclei. Actually we will simplify a bit and use the exact masses of the atoms. This will make no difference. The masses of the atoms differ from the nuclear masses by the masses of the number of electrons in each atom. We have shown that electrons are conserved in nuclear changes. Exact masses of atoms (that is, exact masses of each isotopic species and not the chemical atomic weights shown on the inside back cover) are readily available. For our hydrogen-helium reaction we have... 

Monoisotopic mass The mass of an ion calculated using the exact mass of the most abundant isotope of each element in the formula (e.g., C = 12.0000, O = 15.9949). 

Computer Techniques McLafferty (Ref 63) has pointed out that the usefulness of elemental composition information increases exponentially with increasing mass, since the number of elemental combinations with the same integral mass becomes larger. There are compilations of exact masses and elemental compositions available (Refs 12a, 13 18a). Spectral interpretation will be simplified in important ways if elemental compositions of all but, the smallest peaks are determined. Deriving the elemental compositions of several peaks in a spectrum is extremely laborious and time-consuming. However, with the availability of digital computers such tasks are readily performed. A modern data acquisition and reduction system with a dedicated online computer can determine peak centroids and areas for all peaks, locate reference peaks, interpolate between them to determine the exact masses of the unknown peaks, and find within minutes elemental compositions of all ions in a spectrum (Refs 28b 28c)... 

This strategy is used for the synthesis of three different exact-mass telechelic oligomers. GPC, NMR, and GC/MS evidence indicates that clean depolymerization chemistry occurs for all three samples. Poly( 1,4-butadiene) (38) is broken down into oligomeric units with two, three, and four repeat units using catalyst 23. Catalyst 14 is more efficient and produces even lower molecular weight oligomers, primarily one and two repeat units. When allylchlorodimethylsilane is used instead of ethylene with 14, telechelic dimers are the only product. 

Figure 8.20 Metathesis depolymerization produces exact-mass telechelic oligomers.

In practice, chemists rarely try to measure out an exact mass. Instead, they estimate the mass required and spoon out that mass approximately. Then they measure the mass of the sample precisely and convert it into moles (by using Eq. 2, n = m/M) to find the precise amount that they have obtained. 

Figure 5.45 Structures of (1) Bosentan (C27H29N5O6S [M + H]+ 552.1917) and three of its metabolites, formed by (2) oxidation (C27H29N5O7S [M + H]+ 568.1866), (3) demethylation (C26H27N5O6S [M- -H]+ 538.1760), and (4) demethylation-oxidation (C26H27N5O7S [M + M]+ 554.1709). Reprinted by permission of Elsevier Science from Exact mass measurement of product ions for the structural elucidation of drug metabolites with a tandem quadrupole orthogonal-acceleration time-of-flight mass spectrometer , by Hopfgartner, G., Chemushevich, I. V., Covey, T., Plomley, 1. B. and Bonner, R., Journal of the American Society for Mass Spectrometry, Vol. 10, pp. 1305-1314, Copyright 1999 by the American Society for Mass Spectrometry.

Figure 5.48 Structure of Glyburide, with the elemental composition of C23H28CI N3O5S (exact mass of 493.1438 Da). Reprinted with permission from Zhang, H., Henion, J., Yang, Y. and Spooner, N., Anal Chem., 72, 3342-3348 (2000). Copyright (2000) American Chemical Society.

The tabulated molar mass of an element divided by Avogadro s number is the average mass per atom of that element, but it is not the exact mass of an individual nucleus. There are two reasons for this. First, molar masses refer to neutral atoms. The tabulated molar mass of an element includes the mass of its electrons in addition to the mass of its nucleus. Consequently, the mass of Z electrons must be subtracted from the isotopic molar mass in computing the energy of formation of a nuclide. Second, molar masses of the elements are weighted averages of... 

Measure 4 g of silver nitrate, record the exact mass, and place the sample in the first beaker. Label this beaker 1. 

To assure consistency and speed in multidisciplinary structure analysis of low-MW compounds involving various techniques (IR, NMR, MS, etc.) most industrial laboratories use a Standard Operating Procedure (SOP). In such schemes IR analysis is frequently used as a cheap filter for a quick starting control and as a means for verification. As IR detects only structural units identification of an unknown compound on the basis of IR is difficult. Mass spectrometry is used as the prime identification tool and is especially important in the determination of the exact mass and gross formulae. While structural prognostication on the basis of MS is difficult for the non-expert, a posteriori interpretation is quite feasible. H NMR is both easy and cheap, however requires greater sample quantities than either... 

Table 6.6 presents a list of some of the most commonly encountered atoms in polymer/additive analysis, together with their monoisotopic and average masses. For the same nominal mass, different exact masses (elemental compositions) do exist. Knowledge of the exact mass of an unknown substance allows its atomic composition to be established. The exact mass of an ion proves the presence of a particular species (compound in a mixture). 

Resolution does not affect the accuracy of the individual accurate mass measurements when no separation problem exists. When performing accurate mass measurements on a given component in a mixture, it may be necessary to raise the resolution of the mass spectrometer wherever possible. Atomic composition mass spectrometry (AC-MS) is a powerful technique for chemical structure identification or confirmation, which requires double-focusing magnetic, Fourier-transform ion-cyclotron resonance (FTICR) or else ToF-MS spectrometers, and use of a suitable reference material. The most common reference materials for accurate mass measurements are perfluorokerosene (PFK), perfluorotetrabutylamine (PFTBA) and decafluorotriph-enylphosphine (DFTPP). One of the difficulties of high-mass MS is the lack of suitable calibration standards. Reference inlets to the ion source facilitate exact mass measurement. When appropriately calibrated, ToF mass... 

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