Isotopes Hydrogen-deuterium

A simple example occurs with hydrogen, which occurs naturally as three isotopes (hydrogen, deuterium, tritium), all of atomic number 1 but having atomic masses of 1, 2, and 3 respectively. 

It is well known that hydrogen isotopes, hydrogen, deuterium, and tritium, permeate through solid metals. Tritium produced in the reactor core tends to permeate through heat transfer tubes of IHX and the reaction tubes of the chemical reactor. Further, it is probable that the tritium will mix with the product hydrogen. Therefore, estimation of tritium permeation should be done, and a countermeasure to reduce tritium permeation, if necessary. 

Other elements, too, have naturally occurring higher isotopes Hydrogen (deuterium, H, about 0.015% abundance), nitrogen (0.366% N), and oxygen (0.038% O, 0.200% 0) are examples. These isotopes also contribnte to the intensity of peaks at masses higher than M, bnt less so than... 

Application of the isotopes hydrogen, deuterium and tritium enabled the synthesis of chiral acetate , first reported in 1969. Its chemical and enzymatic syntheses as well as its use in investigation of stereochemical details of biochemical reactions are described in a recent paper . ... 

Limbach H H 1991 Dynamic NMR spectroscopy in the presence of kinetic hydrogen/deuterium isotope effects NMR Basic Principles and Progress vol 23, ed P Diehl, E Fluck, H Gunther, R Kosfeld and J Seelig (Berlin ... 

The ordinary isotope of hydrogen, H, is known as Protium, the other two isotopes are Deuterium (a proton and a neutron) and Tritium (a protron and two neutrons). Hydrogen is the only element whose isotopes have been given different names. Deuterium and Tritium are both used as fuel in nuclear fusion reactors. One atom of Deuterium is found in about 6000 ordinary hydrogen atoms. 

Tables 2,3, and 4 outline many of the physical and thermodynamic properties ofpara- and normal hydrogen in the sohd, hquid, and gaseous states, respectively. Extensive tabulations of all the thermodynamic and transport properties hsted in these tables from the triple point to 3000 K and at 0.01—100 MPa (1—14,500 psi) are available (5,39). Additional properties, including accommodation coefficients, thermal diffusivity, virial coefficients, index of refraction, Joule-Thorns on coefficients, Prandti numbers, vapor pressures, infrared absorption, and heat transfer and thermal transpiration parameters are also available (5,40). Thermodynamic properties for hydrogen at 300—20,000 K and 10 Pa to 10.4 MPa (lO " -103 atm) (41) and transport properties at 1,000—30,000 K and 0.1—3.0 MPa (1—30 atm) (42) have been compiled. Enthalpy—entropy tabulations for hydrogen over the range 3—100,000 K and 0.001—101.3 MPa (0.01—1000 atm) have been made (43). Many physical properties for the other isotopes of hydrogen (deuterium and tritium) have also been compiled (44).

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). 

It is also possible to measme the rate of enolization by isotopic exchange. NMR spectroscopy provides a very convenient method for following hydrogen-deuterium exchange, and this is now the preferred method. Data for several ketones are given in... 

Table 6-5. Calculated Hydrogen/Deuterium Primary Kinetic Isotope Effects" ...

The most plausible fusion reaction for producing energy commercially involves two isotopes of hydrogen, deuterium (D) and tritium (T), or H and H. Deuterium contains one proton and one neutron for an atomic number of two. Tritium contains one proton and two neutrons for an atomic number of three. The reaction is... 

Both of these reported kinetic hydrogen-deuterium isotope effects are disturbingly small, yet they are probably too large to be considered secondary isotope effects. These results lend support to the intermediate complex hypothesis, but they can be accommodated equally well by all three of the mechanisms that have been considered. These results, therefore, afford no basis for discrimination among the possible mechanisms. 

Calculated primary kinetic isotope effects for hydrogen/deuterium at 298 K... 

The first term was found to correspond to the rate of enolisation (measured by an NMR study of hydrogen-deuterium exchange at the methylene group). The second term predominates at [Cu(II)] > 10 M and is characterised by a primary kinetic isotope effect of 7.4 (25 °C) and a p value of 1.24. Addition of 2,2 -bipridyl (bipy) caused an increase in 2 up to a bipy Cu(II) ratio of 1 1 but at ratios greater than this 2 fell gradually until the enolisation term dominated. The oxidation of a-methoxyacetophenone is much slower but gives a similar rate... 

Primary kinetic isotope effects are also observable with pairs of isotopes other than hydrogen/deuterium, but as the relative mass difference must needs be smaller their maximum values will be correspondingly smaller. Thus the following have been observed ... 

A very large deuterium isotope effect has been observed240 by ESR at 77 K on hydrogen-deuterium elimination reaction from 2,3-dimethylbutane (H-DMB)-SFg and 2,3-dimethylbutane-2,3-D2 (D-DMB)-SFg (0.6 mol% mixtures), /-irradiated at 70 K and then stored at 77 K. The significant isotope effect, h2 Ad2 = 1-69 x 104 at 77 K, has been explained by tunnelling elimination of hydrogen (H2) molecules from a DMB+ ion240. 

Three mechanisms have been proposed for this reaction (Scheme 21). The reaction is first order in each of the reactants. In another study, Reutov and coworkers159 found a large primary hydrogen-deuterium kinetic isotope effect of 3.8 for the reaction of tri-(para-methylphenyl)methyl carbocation with tetrabutyltin. This isotope effect clearly demonstrates that the hydride ion is transferred in the slow step of the reaction. This means that the first step must be rate-determining if the reaction proceeds by either of the stepwise mechanisms in Scheme 21. The primary hydrogen-deuterium kinetic isotope effect is, of course, consistent with the concerted mechanism shown in Scheme 21. 

The results from these experiments also allowed Hannon and Traylor to determine the primary and secondary hydrogen deuterium kinetic isotope effects for the hydride abstraction reaction. If one assumes that there is no kinetic isotope effect associated with the formation of 3-deutero-l-butene, i.e. that CH2=CHCHDCH3 is formed at the same rate (k ) from both the deuterated and undeuterated substrate (Scheme 25), then one can obtain both the primary (where a deuteride ion is abstracted) and the secondary deuterium... 

The primary hydrogen-deuterium kinetic isotope effect is obtained from the percent cw-2-butene obtained from the deuterated and undeuterated stannanes. This is possible because a hydride and a deuteride are transferred to the carbocation when the undeuterated and deuterated stannane, respectively, forms c -2-butene. The secondary deuterium kinetic isotope effect for the hydride transfer reaction is obtained from the relative amounts of fraws-2-butene in each reaction. This is because a hydride is transferred from a deuterated and undeuterated stannane when trans-2-butene is formed. 

The primary hydrogen-deuterium kinetic isotope effect for the reaction was 3.7 and the secondary alpha-deuterium kinetic isotope effect was found to be 1.1. It is worth noting that the primary hydrogen-deuterium kinetic isotope effect of 3.7 is in excellent agreement... 

Song and Beak161 have used intramolecular and intermolecular hydrogen-deuterium kinetic isotope effects to investigate the mechanism of the tin tetrachloride catalysed ene-carbonyl enophile addition reaction between diethyloxomalonate and methylenecy-clohexane (equation 105). These ene reactions with carbonyl enophiles can occur by a concerted (equation 106) or a stepwise mechanism (equation 107), where the formation of the intermediate is either fast and reversible and the second step is slow k- > k-i), or where the formation of the intermediate (the k step) is rate-determining. 

Song and Beak found intramolecular and intermolecular hydrogen-deuterium kinetic isotope effects of 1.1 0.2 and 1.2 0.1, respectively, for the tin tetrachloride catalysed ene reaction. Since significant intramolecular and intermolecular primary deuterium kinetic isotope effects of between two and three have been found for other concerted ene addition reactions161, the tin-catalysed reaction must proceed by the stepwise pathway with the k rate determining step (equation 107). 

Abeywickrema and Beckwith162 have measured the primary hydrogen-deuterium kinetic isotope effect for the reaction between an aryl radical and tributyltin hydride. The actual isotope effect was determined by reacting tributyltin hydride and deuteride with the ort/ro-alkcnylphcnyl radical generated from 2-(3-butenyl)bromobenzene (equation 111). 

The exo and the endo ring closures (the kc reactions) are in competition with the aryl radical-tributyltin hydride transfer (the ks or ku reaction). These workers162 used this competition to determine the primary hydrogen-deuterium kinetic isotope effect in the hydride transfer reaction between the aryl radical and tributyltin hydride and deuteride. 

This method gave a primary hydrogen-deuterium kinetic isotope effect of 1.3 for the reaction between the aryl radical and tributyltin hydride. This isotope effect is smaller than the isotope effect of 1.9 which San Filippo and coworkers reported for the reaction between the less reactive alkyl radicals and tributyltin hydride163 (vide infra). The smaller isotope effect of 1.3 in the aryl radical reaction is reasonable, because an earlier transition state with less hydrogen transfer, and therefore a smaller isotope effect164, should be observed for the reaction with the more reactive aryl radicals. 

Several workers have measured the primary hydrogen-deuterium kinetic isotope effects for the reaction between organic radicals and tributyltin hydrides (equation 114). 

---