Abundance, isotopes

Figure Bl.11.1. Resonance frequencies for different nuclei in a field of 14.1 T. Widths indicate the quoted range of shifts for each nucleus, and heights mdicate relative sensitivities at the natural isotopic abundance, on a log scale covering approximately six orders of magnitude. Nuclei resonatmg below 140 MHz are not shown.

Table 7.75 Isotopic Abundances and Masses of Selected Elements 7.124...

Natural Isotopic Abundances. The relative abundances of natural isotopes produce peaks one or more mass units larger than the parent ion (Table 7.75a). For a compound C H O N, a formula allows one to calculate the percent of the heavy isotope contributions from a monoisotopic peak, Pto the Pm + 1 peak ... 

The presence of Cl, Br, S, and Si can be deduced from the unusual isotopic abundance patterns of these elements. These elements can be traced through the positively charged fragments until the pattern disappears or changes due to the loss of one of these atoms to a neutral fragment. 

Following the movement of airborne pollutants requires a natural or artificial tracer (a species specific to the source of the airborne pollutants) that can be experimentally measured at sites distant from the source. Limitations placed on the tracer, therefore, governed the design of the experimental procedure. These limitations included cost, the need to detect small quantities of the tracer, and the absence of the tracer from other natural sources. In addition, aerosols are emitted from high-temperature combustion sources that produce an abundance of very reactive species. The tracer, therefore, had to be both thermally and chemically stable. On the basis of these criteria, rare earth isotopes, such as those of Nd, were selected as tracers. The choice of tracer, in turn, dictated the analytical method (thermal ionization mass spectrometry, or TIMS) for measuring the isotopic abundances of... 

Carbon has two common isotopes, and with relative isotopic abundances of, respectively, 98.89% and 1.11%. (a) What are the mean and standard deviation for the number of atoms in a molecule of cholesterol (b) What is the probability of finding a molecule of cholesterol (C27H44O) containing no atoms of... 

One method for measuring the temperature of the sea is to measure this ratio. Of course, if you were to do it now, you would take a thermometer and not a mass spectrometer. But how do you determine the temperature of the sea as it was 10,000 years ago The answer lies with tiny sea creatures called diatoms. These have shells made from calcium carbonate, itself derived from carbon dioxide in sea water. As the diatoms die, they fall to the sea floor and build a sediment of calcium carbonate. If a sample is taken from a layer of sediment 10,000 years old, the carbon dioxide can be released by addition of acid. If this carbon dioxide is put into a suitable mass spectrometer, the ratio of carbon isotopes can be measured accurately. From this value and the graph of solubilities of isotopic forms of carbon dioxide with temperature (Figure 46.5), a temperature can be extrapolated. This is the temperature of the sea during the time the diatoms were alive. To conduct such experiments in a significant manner, it is essential that the isotope abundance ratios be measured very accurately. 

Many artificial (likely radioactive) isotopes can be created through nuclear reactions. Radioactive isotopes of iodine are used in medicine, while isotopes of plutonium are used in making atomic bombs. In many analytical applications, the ratio of occurrence of the isotopes is important. For example, it may be important to know the exact ratio of the abundances (relative amounts) of the isotopes 1, 2, and 3 in hydrogen. Such knowledge can be obtained through a mass spectrometric measurement of the isotope abundance ratio. 

Approximate ratios of isotope abundance ratios are important in identifying elements. For example, the naturally occurring Cl, Cl isotopes exist in an abundance ratio of about 3 1, and C, exist in a ratio of about 99 1. 

Routine mass spectrometry can be used to identify many elements from their approximate ratios of isotope abundances. For example, mercury-containing compounds give ions having the seven isotopes in an approximate ratio of 0.2 10.1 17.0 23.1 13.2 29.7 6.8. 

Other important areas of mass spectrometric investigation of isotope ratios need accurate, not approximate values. For example, for some investigations in archaeology, pharmaceuticals, and chemistry, very accurate precise ratios of isotope abundances are needed. 

The Oklo Phenomenon. Naturally occurring uranium consists mainly of and fissionable The isotopic ratio can be calculated from the relative decay rates of the two isotopes. Because decays faster than the isotopic ratio decreases with time. In 1997, the isotopic abundance of 235u... 

Boron [7440-42-8] B, is unique in that it is the only nonmetal in Group 13 (IIIA) of the Periodic Table. Boron, at wt 10.81, at no. 5, has more similarity to carbon and siUcon than to the other elements in Group 13. There are two stable boron isotopes, B and B, which are naturally present at 19.10—20.31% and 79.69—80.90%, respectively. The range of the isotopic abundancies reflects a variabiUty in naturally occurring deposits such as high B ore from Turkey and low °B ore from California. Other boron isotopes, B, B, and B, have half-Hves of less than a second. The B isotope has a very high cross-section for absorption of thermal neutrons, 3.835 x 10 (3835 bams). This neutron absorption produces alpha particles. 

Properties of T2O. Some important physical properties of T2O are Hsted in Table 2. Tritium oxide [14940-65-9] can be prepared by catalytic oxidation of T2 or by reduction of copper oxide using tritium gas. T2O, even of low (2—19% T) isotopic abundance, undergoes radiation decomposition to form HT and O2. Decomposition continues, even at 77 K, when the water is fro2en. Pure tritiated water irradiates itself at the rate of 10 MGy/d (10 rad/d). A stationary concentration of tritium peroxide, T2O2, is always present (9). AH of these factors must be taken into account in evaluating the physical constants of a particular sample of T2O. 

Only the knowledge of relative useful ion yields and isotopic abundances is required to calculate elemental composition from the relative ion current measurements. The useful ion yield is the number of ions x detected relative to the number of atoms of element xsputtered. The measured relative ion current of two isotopes is... 

Due to the relative uniformity of ion formation by the RF spark (although its timing is erratic), the most widely used method of quantitation in SSMS is to assume equal sensitivity for all elements and to compare the signal for an individual element with that of the total number of ions recorded on the beam monitor. By empirically calibratii the number of ions necessary to produce a certain blackness on the plate detector, one can estimate the concentration. The signal detected must be corrected for isotopic abundance and the known mass response of the ion-sensitive plate. By this procedure to accuracies within a factor of 3 of the true value can be obtained without standards. 

A SSIMS spectrum, like any other mass spectrum, consists of a series of peaks of dif ferent intensity (i. e. ion current) occurring at certain mass numbers. The masses can be allocated on the basis of atomic or molecular mass-to-charge ratio. Many of the more prominent secondary ions from metal and semiconductor surfaces are singly charged atomic ions, which makes allocation of mass numbers slightly easier. Masses can be identified as arising either from the substrate material itself from deliberately introduced molecular or other species on the surface, or from contaminations and impurities on the surface. Complications in allocation often arise from isotopic effects. Although some elements have only one principal isotope, for many others the natural isotopic abundance can make identification difficult. 

This book presents a unified treatment of the chemistry of the elements. At present 112 elements are known, though not all occur in nature of the 92 elements from hydrogen to uranium all except technetium and promethium are found on earth and technetium has been detected in some stars. To these elements a further 20 have been added by artificial nuclear syntheses in the laboratory. Why are there only 90 elements in nature Why do they have their observed abundances and why do their individual isotopes occur with the particular relative abundances observed Indeed, we must also ask to what extent these isotopic abundances commonly vary in nature, thus causing variability in atomic weights and possibly jeopardizing the classical means of determining chemical composition and structure by chemical analysis. 

Abundances of lUPAC (the International Union of Pure and Applied Chemistry). Their most recent recommendations are tabulated on the inside front fly sheet. From this it is clear that there is still a wide variation in the reliability of the data. The most accurately quoted value is that for fluorine which is known to better than I part in 38 million the least accurate is for boron (1 part in 1500, i.e. 7 parts in [O ). Apart from boron all values are reliable to better than 5 parts in [O and the majority arc reliable to better than I part in 10. For some elements (such as boron) the rather large uncertainty arises not because of experimental error, since the use of mass-spcctrometric measurements has yielded results of very high precision, but because the natural variation in the relative abundance of the 2 isotopes °B and "B results in a range of values of at least 0.003 about the quoted value of 10.811. By contrast, there is no known variation in isotopic abundances for elements such as selenium and osmium, but calibrated mass-spcctrometric data are not available, and the existence of 6 and 7 stable isotopes respectively for these elements makes high precision difficult to obtain they are thus prime candidates for improvement. 

When specifically labelled compounds are required, direct chemical synthesis may be necessary. The standard techniques of preparative chemistry are used, suitably modified for small-scale work with radioactive materials. The starting material is tritium gas which can be obtained at greater than 98% isotopic abundance. Tritiated water can be made either by catalytic oxidation over palladium or by reduction of a metal oxide ... 

Click Coached Problems for a self-study module on average atomic mass from isotopic abundance. 

As it happens, naturally occurring fluorine consists of a single isotope, ijF. It ibllows that the atomic mass of the element fluorine must be the same as that of F-19,19.00 amu. The situation with most elements is more complex, because they occur in nature as a mixture of two or more isotopes. To determine the atomic mass of such an element, it is necessary to know not only the masses of the individual isotopes but also their atom percents (isotopic abundances) in nature. 

Fortunately, isotopic abundances as well as isotopic masses can be determined by mass spectrometry. The situation with chlorine, which has two stable isotopes, 0-35 and 0-37, is shown in Figure 3.2. The atomic masses of the two isotopes are determined in the usual way. The relative abundances of these isotopes are proportional to the heights of the recorder peaks or, more accurately, to the areas under these peaks. For chlorine, the data obtained from the mass spectrometer are... 

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