Isotopic compositions

Each element that has neither a stable isotope nor a characteristic natural isotopic composition is represented in this table by one of that element s commonly known radioisotopes identified by mass number and relative atomic mass. 

Elemental isotopic compositions (isotope ratios) can be used mass spectrometrically in a routine sense to monitor a substance for the presence of different kinds of elements, as with chlorine or platinum. It can also be used in a precise sense to examine tiny variations in these ratios, from which important deductions can be made in a wide variety of disciplines. 

Almost any type of analyzer could be used to separate isotopes, so their ratios of abundances can be measured. In practice, the type of analyzer employed will depend on the resolution needed to differentiate among a range of isotopes. When the isotopes are locked into multielement ions, it becomes difficult to separate all of the possible isotopes. For example, an ion of composition CgHijOj will actually consist of many compositions if all of the isotopes ( C, C, H, H, 0, O, and 0) are considered. To resolve all of these isotopic compositions before measurement of their abundances is difficult. For low-molecular-mass ions (HjO, COj) or for atomic ions (Ca, Cl), the problems are not so severe. Therefore, most accurate isotope ratio measurements are made on low-molecular-mass species, and resolution of these even with simple analyzers is not difficult. The most widely used analyzers are based on magnets, quadrupoles, ion traps, and time-of-flight instruments. 

Eig. 4. The bulk oxygen isotopic composition of different meteorite classes where (—) is the terrestial fractionation line. The 5 notation refers to the normalized difference between or ratios to those in standard mean ocean water (SMOW) in relative units of parts per thousand. The... 

Table 4. Isotopic Composition of Plutonium from Thermal Power Reactors — ...

The recognition in 1940 that deuterium as heavy water [7789-20-0] has nuclear properties that make it a highly desirable moderator and coolant for nuclear reactors (qv) (8,9) fueled by uranium (qv) of natural isotopic composition stimulated the development of industrial processes for the manufacture of heavy water. Between 1940 and 1945 four heavy water production plants were operated by the United States Government, one in Canada at Trail,... 

After cooling, the reaction mixture is diluted with ether, the organic phase washed with ice-cold water and dried over anhydrous sodium sulfate. Evaporation of the solvent and crystallization of the residue from ether-hexane gives 6,6,8j5-d3-5a-androstan-3j5-ol-7-one (11) in 84% yield mp 141-142,5° isotopic composition 6% d2,93% da and 1 %... 

The isotopic purity of the products from a lithium aluminum deuteride reduction is usually equivalent to that of the reagent. The presence of moisture has little effect on the isotope composition of the products, causing only the decomposition of some of the reagent. For the best results, however, it is advisable to distill the solvent— usually ether, tetrahydrofuran or dioxane depending on the desired reaction temperature—from lithium aluminum hydride directly into the reaction flask. In this manner the reduction of 3-keto-5a-steroids (60), for example, gives the corresponding 3a-di alcohols (61) in 98% isotopic purity. ... 

With certain carbonyl compounds, however, such as 3-keto steroids, the isotopic composition is poor due to the rapid exchange of the activated a-hydrogens in the substrate prior to reduction. The corresponding alcohols, in their thermodynamically more stable configuration, are usually found as... 

Even though a sample may show a satisfactory average deuterium content per mole as reported in the earlier literature, its true isotope composition can be quite unsatisfactory when analyzed by mass spectroscopy. The saturated product from the deuteration of 1-hexene, for example, shows an average deuterium content of almost 2.0 however, it consists of virtually all species from do to di4 with the species do to dg predominating. ... 

When the l<, 2( -d2-labeled product (129) is subjected to alkaline equilibration to back exchange the 2i -label (for experimental conditions see section IT-B), the crystalline l< -di-4,4-dimethyl-5a-androstan-3-one (130) exhibits 6% do and 94% d isotopic composition. ... 

The rhodium catalyst (46 mg) is dissolved in acetone (10 ml) in a microhydrogenation apparatus which is then flushed three times with deuterium gas. After stirring the solution in an atmosphere of deuterium for about 1 hr the deuterium uptake ceases and constant pressure is attained. 5a-Cholest-2-ene (136, 19.5 mg) is added and the stirring continued until deuterium uptake ceases (about 3/4 hr). The solvent is evaporated to dryness and the residue is extracted with hexane and the resulting solution filtered through a small alumina column (3 g, activity 111). Evaporation of the hexane gives 2, 3 -d2-5oc-cholestane (137) 18 mg, 92% mp 78-79° isotope composition 94%d2,5%d, andl%do. ... 

Replacement of halides with deuterium gas in the presence of a surface catalyst is a less useful reaction, due mainly to the poor isotopic purity of the products. This reaction has been used, however, for the insertion of a deuterium atom at C-7 in various esters of 3j -hydroxy-A -steroids, since it gives less side products resulting from double bond migration. Thus, treatment of the 7a- or 7j5-bromo derivatives (206) with deuterium gas in the presence of 5% palladium-on-calcium carbonate, or Raney nickel catalyst, followed by alkaline hydrolysis, gives the corresponding 3j3-hydroxy-7( -di derivatives (207), the isotope content of which varies from 0.64 to 1.18 atoms of deuterium per mole. The isotope composition and the stereochemistry of the deuterium have not been rigorously established. 

Elements with 1 predominant isotope can also, potentially, permit very precise atomic weight determinations since variations in isotopic composition or errors in its determination have a correspondingly small effect on the mass-spectrometrically determined value of the atomic weight. Nine elements have 1 isotope that is more than 99% abundant (H, He, N, O, Ar, V, La, Ta... 

Data refer to H2 of normal isotopic composition (i.e. containing 0.0156 atom % of deuterium, predominantly as HD). All data refer to the mixture of ortho- and puru-forms that are in equilibrium at room temperature. 

D2O and the tritium analogue T2O (p. 41). The high bp is notable (cf. H2S, etc.) as is the temperature of maximum density and its marked dependence on the isotopic composition of water. The high dielectric constant and measurable ionic dissociation equilibrium are also unusual and important properties. The ionic mobilities of [H30] and [OH] in water are abnormally high (350 X 10 " and 192 x 10 cms per V cm... 

This value refers to the natural mixture of uranium isotopes, i.e. it is the atomic weight. Variations are possible because (i) some geological samples have anomalous isotopic compositions, and (ii) commercially available samples may have been depleted in The value for itself is 238.0508. 

Element has no stable nuclides the value given in parentheses is the atomic mass number of the isotope of longest known half-life. However, three such elements (Th, Pa and U) do have a characteristic terrestrial isotopic composition, and for these an atomic weight is tabulated. 

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