Relative atomic mass variations

The masses of isotopes can be measured with accuracies better than parts per billion (ppb), e.g., m40Ar = 39.9623831235 0.000000005 u. Unfortunately, determinations of abundance ratios are less accurate, causing errors of several parts per million (ppm) in relative atomic mass. The real limiting factor, however, comes from the variation of isotopic abundances from natural samples, e.g., in case of lead which is the final product of radioactive decay of uranium, the atomic weight varies by 500 ppm depending on the Pb/U ratios in the lead ore. [8]... 

Note The calculation of relative molecular mass, Mr, of organic molecules exceeding 2000 u is significantly influenced by the basis it is performed on. Both the atomic weights of the constituent elements and the natural variations in isotopic abundance contribute to the differences between monoisotopic- and relative atomic mass-based values. In addition, they tend to characteristically differ between major classes of biomolecules. This is primarily because of molar carbon content, e.g., the difference between polypeptides and nucleic acids is about 4 u at Mr = 25,000 u. Considering terrestrial sources alone, variations in the isotopic abundance of carbon lead to differences of about 10-25 ppm in Mr which is significant with respect to mass measurement accuracy in the region up to several 10 u. [41]... 

Table A. 1 comprises the stable elements from hydrogen to bismuth with the radioactive elements technetium and promethium omitted. Natural variations in isotopic composition of some elements such as carbon or lead do not allow for more accurate values, a fact also reflected in the accuracy of their relative atomic mass. However, exact masses of the isotopes are not affected by varying abundances. The isotopic masses listed may differ up to some 10 u in other publications.

The variations in isotopic composition of many elements in samples of different origin limit the precision to which a relative atomic mass can be given. The standard atomic weights revised biennially by the IUPAC Commission on Atomic Weights and Isotopic Abundances are meant to be applicable for normal materials. This means that to a high level of confidence the relative atomic mass of an element in any normal sample will be within the uncertainty limits of the tabulated value. By normal it is meant here that the material is a reasonably possible source of the element or its compounds in commerce for industry and science and that it has not been subject to significant modification of isotopic composition within a geologically brief period [43]. This, of course, excludes materials studied themselves for very anomalous isotopic composition. 

The relative atomic masses of many elements depend on the origin and treatment of the materials [45]. The notes to this table explain the types of variation to be expected for individual elements. When used with due regard to the notes the values are considered reliable to the figure given in parentheses being applicable to the last digit. For elements without a characteristic terrestrial isotopic composition no standard atomic weight is recommended. The atomic mass of its most stable isotope can be found in table 6.3. 

The number of significant figures in a table of chemical or natural relative atomic masses (see the inside back cover of this book) is limited not only by the accuracy of the mass spectrometric data but also by any variability in the natural abundances of the isotopes. If lead from one mine has a relative atomic mass of 207.18 and lead from another has a mass of 207.23, there is no way a result more precise than 207.2 can be obtained. In fact, geochemists are now able to use small variations in the isotopic abundance ratio as a thermometer to deduce... 

Often it is not necessary to separate the components before examination as some separation may be achieved by careful variation of the sample probe temperatures to produce, in effect, a fractional distillation of the components. The presence, however, of large amounts of low molecular weight polymers such as PE and PP can cause interference by producing a high hydrocarbon background extending to several hundred relative atomic mass units. In such instances thin-layer chromatographic separation can be used as a clean-up procedure. 

Different isotopes differ in their atomic masses. The intensities of the signals from different isotopic ions allow isotopic abundances to be determined with high accuracy. Mass spectrometry reveals that the isotopic abundances in elemental samples from different sources have slightly different values. Isotopic ratios vary because isotopes with different masses have slightly different properties for example, they move at slightly different speeds. These differences have tiny effects at the level of parts per ten thousand (0.0001). The effects are too small to appear as variations In the elemental molar masses. Nevertheless, high-precision mass spectrometry can measure relative abundances of isotopes to around 1 part in 100,000. 

What is the uncertainty in the molecular mass of 02 On the inside cover of this book, we find that the atomic mass of oxygen is 15.9994 0.000 3g/mol. The uncertainty is not mainly from random error in measuring the atomic mass. The uncertainty is predominantly from isotopic variation in samples of oxygen from different sources. That is, oxygen from one source could have a mean atomic mass of 15.999 1 and oxygen from another source could have an atomic mass of 15.999 7. The atomic mass of oxygen in a particular lot of reagent has a systematic uncertainty. It could be relatively constant at 15.999 7 or 15.999 1, or any value in between, with only a small random variation around the mean value. 

Figure 22-11 Variation in nuclear binding energy per nucleon with atomic mass.This plot shows the relative stability of the most stable isotopes of selected elements. The most stable nucleus is lFe, with a binding energy of 8.80 MeV per nucleon...

We have known for many years that large isotopic fractionations of heavy elements like Pb develop in the source regions of TIMS machines. Nonetheless, most of us held fast to the conventional wisdom that no significant mass-dependent isotopic fractionations were likely to occur in natural or laboratory systems for elements that are either heavy or engaged in bonds with a dominant ionic character. With the relatively recent appearance of new instrumentation like MC-ICP-MS and heroic methods development in TIMS analyses, it became possible to make very precise measurements of the isotopic ratios of some of these non-traditional elements, particularly if they comprise three or more isotopes. It was eminently reasonable to reexamine these systems in this new light. Perhaps atomic weights could be refined, or maybe there were some unexpected isotopic variations to discover. There were. 

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