Isotopic stability

The labeled standards used need to be iso-topically stable. Isotopic stability may become... 

Fig. 5. Effects of loss of lead from Ceylon zircon (6,500) (-100 to -1-200 mesh) as a result of hydrothermal experiments at 500° C in 2 molal NaCl at 1,000 bars fluid pressure A, Concordia plot showing episodic lead loss B, change of lead content in zircon with time (from Pidgeon, O Neil and Silver Uranium and Lead Isotopic Stability in a Metamict Zircon under Experimental Hydrothermal Conditions. Science 154, 1538—1540. Copyright 1966 by the American Association for the Advancement of Science)...

PiDGEON, R. T., O Neil, J. R., Silver, L. T. Uranium and lead isotopic stability in a metamict zircon under experimental hydrothermal conditions. Science 154, 1538—1540(1966). 

By protodetritiation of the thiazolium salt (152) and of 2 tritiothiamine (153) Kemp and O Brien (432) measured a kinetic isotope effect, of 2.7 for (152). They evaluated the rate of protonation of the corresponding yiides and found that the enzyme-mediated reaction of thiamine with pyruvate is at least 10 times faster than the maximum rate possible with 152. The scale of this rate ratio establishes the presence within the enzyme of a higher concentration of thiamine ylide than can be realized in water. Thus a major role of the enzyme might be to change the relative thermodynamic stabilities of thiamine and its ylide (432). 

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. 

The effects of a rather distinct deformed shell at = 152 were clearly seen as early as 1954 in the alpha-decay energies of isotopes of californium, einsteinium, and fermium. In fact, a number of authors have suggested that the entire transuranium region is stabilized by shell effects with an influence that increases markedly with atomic number. Thus the effects of shell substmcture lead to an increase in spontaneous fission half-Hves of up to about 15 orders of magnitude for the heavy transuranium elements, the heaviest of which would otherwise have half-Hves of the order of those for a compound nucleus (lO " s or less) and not of milliseconds or longer, as found experimentally. This gives hope for the synthesis and identification of several elements beyond the present heaviest (element 109) and suggest that the peninsula of nuclei with measurable half-Hves may extend up to the island of stabiHty at Z = 114 andA = 184. 

There are at least two mechanisms available for aziridine cis-trans isomerism. The first is base-catalyzed and proceeds via an intermediate carbanion (235). The second mechanism can be either thermally or photochemically initiated and proceeds by way of an intermediate azomethine ylide. The absence of a catalytic effect and interception of the 1,3-dipole intermediate provide support for this route. A variety of aziridinyl ketones have been found to undergo equilibration when subjected to base-catalyzed conditions (65JA1050). In most of these cases the cis isomer is more stable than the trans. Base-catalyzed isotope exchange has also been observed in at least one molecule which lacks a stabilizing carbonyl group (72TL3591). 

Stabilization of a carbocation intermediate by benzylic conjugation, as in the 1-phenylethyl system shown in entry 8, leads to substitution with diminished stereosped-ficity. A thorough analysis of stereochemical, kinetic, and isotope effect data on solvolysis reactions of 1-phenylethyl chloride has been carried out. The system has been analyzed in terms of the fate of the intimate ion-pair and solvent-separated ion-pair intermediates. From this analysis, it has been estimated that for every 100 molecules of 1-phenylethyl chloride that undergo ionization to an intimate ion pair (in trifluoroethanol), 80 return to starting material of retained configuration, 7 return to inverted starting material, and 13 go on to the solvent-separated ion pair. 

The ratios of stable isotopes (red dots) fall within a narrow range, referred to as the "belt of stability." For light isotopes of small atomic number the stable ratio is 1 1. For heavier isotopes the ratio gradually increases to about 1.5 1. Isotopes outside the band of stability are unstable and radioactive. There are no stable isotopes for elements of atomic number greater than 83 (Bi). 

As you can see from Figure 2.5, the neutron-to-proton ratio required for stability varies with atomic number. For light elements (Z < 20), this ratio is close to 1. For example, the isotopes C, N, and are stable. As atomic number increases, the ratio increases the belt of stability shifts to higher numbers of neutrons. With very heavy isotopes such as 2j Pb, the stable neutron-to-proton ratio is about 1.5 ... 

The other actinides have been synthesized in the laboratory by nuclear reactions. Their stability decreases rapidly with increasing atomic number. The longest lived isotope of nobelium (102N0) has a half-life of about 3 minutes that is, in 3 minutes half of the sample decomposes. Nobelium and the preceding element, mendelevium (ioiMd), were identified in samples containing one to three atoms of No or Md. 

Radioactivity The ability possessed by some natural and synthetic isotopes to undergo nuclear transformation to other isotopes, 513 applications, 516-518 biological effects, 528-529 bombardment reactions, 514-516 diagnostic uses, 516t discovery of, 517 modes of decay, 513-514 nuclear stability and, 29-30 rate of decay, 518-520,531q Radium, 521-522 Radon, 528 Ramsay, William, 190 Random polymer 613-614 Randomness factor, 452-453 Raoult s law A relation between the vapor pressure (P) of a component of a solution and that of the pure component (P°) at the same temperature P — XP°, where X is the mole fraction, 268... 

Principal advantages of 7-rays over polychromatic x-rays- (1) Greater source stability (radioactive isotopes as compared with x-ray tubes) (2) simpler equipment (3) greater compactness of source (4) beams more nearly monochromatic (5) wider energy range available, 2(IQ4) to 2(107) ev (6) lower cost ... 

Complexed arenediazonium salts are stabilized against photochemical degradation (Bartsch et al., 1977). This effect was studied in the former German Democratic Republic in the context of research and development work on diazo copying processes (Israel, 1982 Becker et al., 1984) as well as in China (Liu et al., 1989). The comparison of diazonium ion complexation by 18-crown-6 and dibenzo-18-crown-6 is most interesting. Becker at al. (1984) found mainly the products of heterolytic dediazoniation when 18-crown-6 was present in photolyses with a medium pressure mercury lamp, but products of homolysis appeared in the presence of dibenzo-18-crown-6. The dibenzo host complex exhibited a charge-transfer absorption on the bathochromic slope of the diazonio band. Results on the photo-CIDNP effect in the 15N NMR spectra of isotopically labeled diazonium salts complexed by dibenzo-18-crown-6 indicate that the primary step is a single electron transfer. 

Nuclides that lie below the band of stability have a low proportion of neutrons and are classified as proton rich. These isotopes tend to decay in such a way that the... 

Structures of this sort, with a mantle of helions and a core of neutrons, have minimum Coulomb energy. We may expect these structures to have the minimum neutron excess compatible with stability any more protons would be forced from the mantle into the core. In fact, 44RuB2 has the largest atomic number for which N — Z equals 8 for a stable isotope. 

However, a number of examples have been found where addition of bromine is not stereospecifically anti. For example, the addition of Bf2 to cis- and trans-l-phenylpropenes in CCI4 was nonstereospecific." Furthermore, the stereospecificity of bromine addition to stilbene depends on the dielectric constant of the solvent. In solvents of low dielectric constant, the addition was 90-100% anti, but with an increase in dielectric constant, the reaction became less stereospecific, until, at a dielectric constant of 35, the addition was completely nonstereospecific.Likewise in the case of triple bonds, stereoselective anti addition was found in bromination of 3-hexyne, but both cis and trans products were obtained in bromination of phenylacetylene. These results indicate that a bromonium ion is not formed where the open cation can be stabilized in other ways (e.g., addition of Br+ to 1 -phenylpropene gives the ion PhC HCHBrCH3, which is a relatively stable benzylic cation) and that there is probably a spectrum of mechanisms between complete bromonium ion (2, no rotation) formation and completely open-cation (1, free rotation) formation, with partially bridged bromonium ions (3, restricted rotation) in between. We have previously seen cases (e.g., p. 415) where cations require more stabilization from outside sources as they become intrinsically less stable themselves. Further evidence for the open cation mechanism where aryl stabilization is present was reported in an isotope effect study of addition of Br2 to ArCH=CHCHAr (Ar = p-nitrophenyl, Ar = p-tolyl). The C isotope effect for one of the double bond carbons (the one closer to the NO2 group) was considerably larger than for the other one. ... 

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