Isotope constants

Polyakov VB (1998) On anharmonic and pressure corrections to the equihbrium isotopic constants for minerals, Geochim Cosmochim Acta 62 3077-3088... 

Cheung A S C, Yoshino K, Freeman D E, Friedman R S, Dalgarno A and Parkinson W H 1989 The Schumann-Runge absorption-bands of 0 0 in the wavelength region 175-205 nm and spectroscopic constants of isotopic oxygen molecules J. Mol. Speotroso. 134 362-89... 

The simplest system exliibiting a nuclear hyperfme interaction is the hydrogen atom with a coupling constant of 1420 MHz. If different isotopes of the same element exhibit hyperfme couplings, their ratio is detemiined by the ratio of the nuclear g-values. Small deviations from this ratio may occur for the Femii contact interaction, since the electron spin probes the inner stmcture of the nucleus if it is in an s orbital. However, this so-called hyperfme anomaly is usually smaller than 1 %. 

Concerning N-magnetic resonance, Boejesen et at. (113) have measured the following coupling constants on a sample of thiazole enriched in this isotope ... 

Atoms with the same number of protons but a different number of neutrons are called isotopes. To identify an isotope we use the symbol E, where E is the element s atomic symbol, Z is the element s atomic number (which is the number of protons), and A is the element s atomic mass number (which is the sum of the number of protons and neutrons). Although isotopes of a given element have the same chemical properties, their nuclear properties are different. The most important difference between isotopes is their stability. The nuclear configuration of a stable isotope remains constant with time. Unstable isotopes, however, spontaneously disintegrate, emitting radioactive particles as they transform into a more stable form. 

Direct Analysis of Radioactive Analytes The concentration of a long-lived radioactive isotope is essentially constant during the period of analysis. As shown in Example 13.6, the sample s activity can be used to calculate the number of radioactive particles that are present. 

Table 13.1 provides a list of several isotopes commonly used as tracers. The half-lives for these isotopes also are listed. What is the rate constant for the radioactive decay of each isotope ... 

Figure 7.9 shows a schematic representation of this effect, in which the ratio of the two isotopes changes with time. To obtain an accurate estimate of the ratio of ion abundances, it is better if the relative ion yields decrease linearly (Figure 7.9) which can be achieved by adjusting the filament temperature continuously to obtain the desired linear response. An almost constant response for the isotope ratio can be obtained by slow evaporation of the sample, viz., by keeping the filament temperature as low as is consistent with sufficient sensitivity of detection (Figure 7.9). 

Schematic illustrations of the effect of temperature and surface density (time) on the ratio of two isotopes, (a) shows that, generally, there is a fractionation of the two isotopes as time and temperature change the ratio of the two isotopes changes throughout the experiment and makes difficult an assessment of their precise ratio in the original sample, (b) illustrates the effect of gradually changing the temperature of the filament to keep the ratio of ion yields linear, which simplifies the task of estimating the ratio in the original sample. The best method is one in which the rate of evaporation is low enough that the ratio of the isotopes is virtually constant this ratio then relates exactly to the ratio in the original sample.

However, even for a small molecule such as HgCO, determination of the rotational constants in the v = 1 levels of all the vibrations presents considerable difficulties. In larger molecules it may be possible to determine only Aq, Bq and Cq. In such cases the simplest way to determine the structure is to ignore the differences from A, and Cg and make sufficient isotopic substitutions to give a complete, but approximate, structure, called the Tq structure. 

The dissociation energy is unaffected by isotopic substitution because the potential energy curve, and therefore the force constant, is not affected by the number of neutrons in the nucleus. However, the vibrational energy levels are changed by the mass dependence of 03 (proportional to where /r is the reduced mass) resulting in Dq being isotope-... 

In addition to H2, D2, and molecular tritium [100028-17-8] the following isotopic mixtures exist HD [13983-20-5] HT [14885-60-0] and DT [14885-61-1]. Table 5 Hsts the vapor pressures of normal H2, D2, and T2 at the respective boiling points and triple points. As the molecular weight of the isotope increases, the triple point and boiling point temperatures also increase. Other physical constants also differ for the heavy isotopes. A 98% ortho—25/q deuterium mixture (the low temperature form) has the following critical properties = 1.650 MPa(16.28 atm), = 38.26 K, 17 = 60.3 cm/mol3... 

The proportionahty constant y is called the gyromagnetic ratio which is a function of the magnitude of the nuclear magnetic moment. Therefore each isotope having a net nuclear spia possesses a unique y. The y of some biologically relevant nuclei can be found ia Table 3. 

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. 

Isotopic Exchange Reactions. Exchange reactions between the isotopes of hydrogen are well known and well substantiated. The equihbrium constants for exchange between the various hydrogen molecular species have been documented (18). Kinetics of the radiation-induced exchange reactions of hydrogen, deuterium, and tritium have been critically and authoritatively reviewed (31). The reaction T2 + H2 — 2HT equiUbrates at room temperature even without a catalyst (30). 

D can be regarded as a constant of the system in this experiment since drere is no change of chemical composition involved in tire exchange of radioactive and stable isotopes between the sample and the deposited layer. The solution of this equation with these boundaty conditions is... 

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