Nominal mass

Compounds that contain chlorine, bromine, sulfur, or silicon are usually apparent from prominent peaks at masses 2, 4, 6, and so on, units larger than the nominal mass of the parent or fragment ion. Eor example, when one chlorine atom is present, the P + 2 mass peak will be about one-third the intensity of the parent peak. When one bromine atom is present, the P + 2 mass peak will be about the same intensity as the parent peak. The abundance of heavy isotopes is treated in terms of the binomial expansion (a -I- h) , where a is the relative abundance of the light isotope, b is the relative abundance of the heavy isotope, and m is the number of atoms of the particular element present in the molecule. If two bromine atoms are present, the binomial expansion is... 

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... 

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. 

Electrostatic Analyzer In magnetic-sector instruments, an electrostatic sector can be incorporated either before or after the magnet to provide energy resolution and directional focusing of the ion beam. The resolution achievable in these double-focusing instruments is sufficient to separate ions having the same nominal mass (e.g., 28 Daltons) but with different chemical formula (e.g., N2 and CO). 

Nominal mass The mass calculated for an ion when using the integer mass values of the most abundant isotope of each element in the formula (e.g.. C = 12, O = 16, S = 32). 

Mass spectrometric studies are not limited to the investigation of stable intermediates they have also been carried out on reaction transition states. The ultrafast studies by Zewail, for example, are nominally mass spectrometric based, where photoionization is used to detect reactive species on exceedingly short (femtosecond) time scales.Time resolved studies provide insight into the rates of unimo-lecular reactions, but do not provide direct thermochemical insight. 

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). 

Principles and Characteristics Mass spectrometry can provide the accurate mass determination in a direct measurement mode. For a properly calibrated mass spectrometer the mass accuracy should be expected to be good to at least 0.1 Da. Accurate mass measurements can be made at any resolution (resolution matters only when separating masses). For polymer/additive deformulation the nominal molecular weight of an analyte, as determined with an accuracy of 0.1 Da from the mass spectrum, is generally insufficient to characterise the sample, in view of the small mass differences in commercial additives. With the thousands of additives, it is obvious that the same nominal mass often corresponds to quite a number of possible additive types, e.g. NPG dibenzoate, Tinuvin 312, Uvistat 247, Flexricin P-1, isobutylpalmitate and fumaric acid for m = 312 Da see also Table 6.7 for m = 268 Da. Accurate mass measurements are most often made in El mode, since the sensitivity is high, and reference mass peaks are readily available (using various fluorinated reference materials). Accurate mass measurements can also be made in Cl... 

For these reasons we have developed a different approach that measures differential expression of intact proteins.21 In this approach the proteins are extracted from the cell, separated on an HPLC column, ionized via electrospray, and automatically deconvoluted into their respective uncharged nominal masses. By this methodology it is then possible to obtain accurate, intact protein profiles of the individual strains of bacteria. Because the masses of the detected proteins are accurate to +2 Da from run to run, it is possible to subtract protein profiles from known strains to quickly identify differences in protein expression among newly mutated strains. 

One of the more powerful techniques is a new software tool called mass defect filtering.176 185-188 A mass defect can be defined as the difference between the exact mass and nominal mass of a compound.189 Typically, drug-like molecules (and their metabolites) will have mass defects that differ from those of endogenous matrix materials. While a mass spectrometer that has unit mass resolution cannot differentiate a test compound from an isobaric matrix compound, a high mass resolution MS may be able to differentiate many isobaric matrix compounds from test compounds. 

Accurate Mass An experimentally determined mass of an ion that is used to determine an elemental formula. For ions containing combinations of the elements C, H, N, O, P, S, and the halogens, with mass less than 200 Da, a measurement with 5 ppm uncertainty is sufficient to uniquely determine the elemental composition. See also related entries on average mass dalton molar mass monoisotopic mass nominal mass unified atomic mass unit. 

Mass See entries on accurate mass average mass dalton molar mass molecular weight monoisotopic mass nominal mass unified atomic mass unit. 

Mass Defect Difference between exact and nominal mass [3]. 

Nominal Mass Mass of an ion or molecule calculated using the mass of the most abundant isotope of each element rounded to the nearest integer value and equivalent to the sum of the mass numbers of all constituent atoms [1]. 

Example The nominal mass of an ion is calculated by adding the integer masses of the lightest isotopes of all elements contributing to the molecule, for example, the nominal mass of H20 is (2 1) + 16 Da = 18 Da. 

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