Isotopes, hydrogen

There are two naturally occurring stable isotopes of hydrogen which occur in the following proportions  

Hydrogen isotopes show the largest relarive mass difference between two stable isotopes, with the result that there are huge variadons in measured hydrogen isotope rados in naturally occurring materials. In addidon, hydrogen isotopes are ubiquitous in nature in the forms H2O, OH and H2 and as hydrocarbons. 

Hydrogen isotopes are measured in parts per thousand reladve to the SMOW standard and are calculated in an analogous manner to that for oxygen isotopes (see Eqn [7.1]) and expressed as 5D /oo. Precision is between 1 and 2 / . 6D values for the SLAP standard reladve to SMOW are -428 /m. D/H ratios are usually measured on H2 gas which is produced from the reduction of water at high temperatures. 

Plot of 5D vs 5 0 diagram for difTerent water types, The fields of magmatic water and formation waters are taken from. Taylor (1974). The field for igneous hornblendes and biotites from Taylor (1974) and that of magmadc water from the granites of Cornwall firom Sheppard (1977). The meteoric water line is from Epstein et al, (1965) and Epstein (1970). The metamorphlc water field combines the values of Taylor (1974) and Sheppard (1981). 

Carbonaceous chondrites MORE Granitoids Metamotphic rocks Detiital sediments 

The difference in mass between the isotopes leads to various property differences these differences are commonly referred to as isotope effects. Hydrogen is unique because the isotope effects are greater than for isotopes of any of the other elements. With only one proton, the addition of one neutron nearly doubles the mass. This underlies the large differences in the physical properties of hydrogen isotopes. 

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Prozesky V M, Churms C L, Piioher J V and Springhorn K A 1994 ERDA measurement of hydrogen isotopes with a A E-E teiesoope Nucl. Instrum. Methods B 84 373... 

The occurrence of a hydrogen isotope effect in an electrophilic substitution will certainly render nugatory any attempt to relate the reactivity of the electrophile with the effects of substituents. Such a situation occurs in mercuration in which the large isotope effect = 6) has been attributed to the weakness of the carbon-mercury bond relative to the carbon-hydrogen bond. The following scheme has been formulated for the reaction, and the occurrence of the isotope effect indicates that the magnitudes of A j and are comparable ... 

A more detailed study of the nitration of quinolinium (l) in 80-05 % sulphuric acid at 25 °C, using isotopic dilution analysis, has shown that 3-) 5-) 6-, 7- and 8-nitroquinoline are formed (table 10.3). Combining these results with the kinetic ones, and assuming that no 2- and 4-nitration occurs, gives the partial rate factors listed in table 10.4. Isoquinolinium is 14 times more reactive than quinolinium. The strong deactivation of the 3-position is in accord with an estimated partial rate factor of io for hydrogen isotope exchange at the 3-position in the pyridinium ion. It has been estimated that the reactivity of this ion is at least 10 less than that of the quinolinium ion. Based on this estimate, the partial rate factor for 3-nitration of the pyridinium ion would be less than 5 x io . 

However unlike H which is the most abundant of the hydrogen isotopes (99 985%) only 1 1% of the carbon atoms m a sample are Moreover the intensity of the signal produced by nuclei is far weaker than the signal produced by the same number of H nuclei In order for NMR to be a useful technique in structure deter mination a vast increase in the signal to noise ratio is required Pulsed FT NMR pro vides for this and its development was the critical breakthrough that led to NMR becoming the routine tool that it is today... 

Isotopically Labeled Compounds. The hydrogen isotopes are given special names H (protium), H or D (deuterium), and H or T (tritium). The superscript designation is preferred because D and T disturb the alphabetical ordering in formulas. 

SMOW. standard mean ocean water (a standard for oxygen and hydrogen isotopes)... 

Table 5. Vapor Pressures of Hydrogen Isotopes, Normal Species. ...

Pulsed plasmas containing hydrogen isotopes can produce bursts of alpha particles and neutrons as a consequence of nuclear reactions. The neutrons are useful for radiation-effects testing and for other materials research. A dense plasma focus filled with deuterium at low pressure has produced 10 neutrons in a single pulse (76) (see Deuterium AND TRITIUM). Intense neutron fluxes also are expected from thermonuclear fusion research devices employing either magnetic or inertial confinement. 

The azo coupling reaction proceeds by the electrophilic aromatic substitution mechanism. In the case of 4-chlorobenzenediazonium compound with l-naphthol-4-sulfonic acid [84-87-7] the reaction is not base-catalyzed, but that with l-naphthol-3-sulfonic acid and 2-naphthol-8-sulfonic acid [92-40-0] is moderately and strongly base-catalyzed, respectively. The different rates of reaction agree with kinetic studies of hydrogen isotope effects in coupling components. The magnitude of the isotope effect increases with increased steric hindrance at the coupler reaction site. The addition of bases, even if pH is not changed, can affect the reaction rate. In polar aprotic media, reaction rate is different with alkyl-ammonium ions. Cationic, anionic, and nonionic surfactants can also influence the reaction rate (27). 

Although the chemical and physical properties of all isotopes of an element are quaUtatively the same, there are quantitative differences among them. The physical and chemical differences between the hydrogen isotopes are relatively much greater than those among the isotopes of all other elements because of the large relative differences in mass, ie, H D T = 1 2 3. 

Table 1. Vapor Pressures and Triple and Critical Points of Hydrogen Isotopes ...

Kinetic isotope effects are an important factor in the biology of deuterium. Isotopic fractionation of hydrogen and deuterium in plants occurs in photosynthesis. The lighter isotope is preferentially incorporated from water into carbohydrates and tipids formed by photosynthesis. Hydrogen isotopic fractionation has thus become a valuable tool in the elucidation of plant biosynthetic pathways (42,43). 

Raman Spectroscopy. Raman spectroscopy is an excellent method for the analysis of deuterium containing mixtures, particularly for any of the diatomic H—D—T molecules. For these, it is possible to predict absolute light scattering intensities for the rotational Raman lines. Hence, absolute analyses are possible, at least in principle. The scattering intensities for the diatomic hydrogen isotope species is comparable to that of dinitrogen, N2, and thus easily observed. 

Tritium [15086-10-9] the name given to the hydrogen isotope of mass 3, has symbol or more commonly T. Its isotopic mass is 3.0160497 (1). Moletecular tritium [10028-17-8], is analogous to the other hydrogen isotopes. The tritium nucleus is energetically unstable and decays radioactively by the emission of a low-energy P particle. The half-life is relatively short (- 12 yr), and therefore tritium occurs in nature only in equiUbrium with amounts produced by cosmic rays or man-made nuclear devices. 

Nuclear Magnetic Resonance. AH three hydrogen isotopes have nuclear spins, I 7 0, and consequently can all be used in nmr spectroscopy (Table 4) (see Magnetic spin resonance). Tritium is an even more favorable nucleus for nmr than is H, which is by far the most widely used nucleus in nmr spectroscopy. The radioactivity of T and the ensuing handling problems are a deterrent to widespread use for nmr. Considerable progress has been made in the appHcations of tritium nmr (23,24). 

Most of the chemical properties of tritium are common to those of the other hydrogen isotopes. However, notable deviations in chemical behavior result from isotope effects and from enhanced reaction kinetics induced by the ( -emission in tritium systems. Isotope exchange between tritium and other hydrogen isotopes is an interesting manifestation of the special chemical properties of tritium. 

Production-Scale Processing. The tritium produced by neutron irradiation of Li must be recovered and purified after target elements are discharged from nuclear reactors. The targets contain tritium and He as direct products of the nuclear reaction, a small amount of He from decay of the tritium and a small amount of other hydrogen isotopes present as surface or metal contaminants. 

J. R. Bardet, W. H. Denton, and R. H. Sherman, "Hydrogen Isotope Distillation for the Tritium Systems Test Assembly," American Nuclear Sodef... 

Pyridinium sulfate, bis-l,2,4,6-tetramethyl-hydrogen isotope exchange reactions, 2, 194 Pyridinium-1 -sulfonates reactions, 2, 34... 

The diffusion of H and D atoms in the molecular crystals of hydrogen isotopes was explored with the EPR method. The atoms were generated by y-irradiation of crystals or by photolysis of a dopant. In the H2 crystals the initial concentration of the hydrogen atoms 4x 10 mol/cm is halved during 10 s at 4.2 K as well as at 1.9 K [Miyazaki et al. 1984 Itskovskii et al. 1986]. The bimolecular recombination (with rate constant /ch = 82cm mol s ) is limited by diffusion, where, because of the low concentration of H atoms, each encounter of the recombinating partners is preceded by 10 -10 hops between adjacent sites. 

K. L. Wilson, et al.. Trapping, Detrapping and Release of Implanted Hydrogen Isotopes, 1991, IAEA. 

Wawzonek et al. first investigated the mechanism of the cyclization of A-haloamines and correctly proposed the free radical chain reaction pathway that was substantiated by experimental data. "" Subsequently, Corey and Hertler examined the stereochemistry, hydrogen isotope effect, initiation, catalysis, intermediates, and selectivity of hydrogen transfer. Their results pointed conclusively to a free radical chain mechanism involving intramolecular hydrogen transfer as one of the propagation steps. Accordingly, the... 

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