Deuterium determination

Tritium specific activity determinations are usually carried out with larger uncertainties than mass spectrometric deuterium determinations. Calculations of k kj ratios with the use of equation 203 are therefore not very reliable. Nevertheless, the data obtained in the high-temperature region indicate clearly that the critical coordinate for reaction 197 is the C—H rather than the C—C distance and support the Slater assumption based on theoretical considerations concerning unimolecular decomposition of cyclopropane. 

The slightly different physical properties of deuterium allow its concentration in ordinary hydrogen (or the concentration of a deuterium-containing compound in a hydrogen compound) to be determined. Exchange of deuterium and hydrogen occurs and can be used to elucidate the mechanism of reactions (i.e. the deuterium is a non-radioactive tracer). Methanol exchanges with deuterium oxide thus ... 

Each act of proton abstraction from the a carbon converts a chiral molecule to an achi ral enol or enolate ion The sp hybridized carbon that is the chirality center m the start mg ketone becomes sp hybridized m the enol or enolate Careful kinetic studies have established that the rate of loss of optical activity of sec butyl phenyl ketone is equal to Its rate of hydrogen-deuterium exchange its rate of brommation and its rate of lodma tion In each case the rate determining step is conversion of the starting ketone to the enol or enolate anion... 

Mass spectrometry has been used to determine the amount of H2 in complex gas mixtures (247), including those resulting from hydrocarbon pyrolysis (68). Mass spectrometry can also be used to measure hydrogen as water from hydrocarbon combustion (224,248). Moreover, this technique is also excellent for determining the deuterium hydrogen ratio in a sample (249,250). 

Infrared Spectrophotometry. The isotope effect on the vibrational spectmm of D2O makes infrared spectrophotometry the method of choice for deuterium analysis. It is as rapid as mass spectrometry, does not suffer from memory effects, and requites less expensive laboratory equipment. Measurement at either the O—H fundamental vibration at 2.94 p.m (O—H) or 3.82 p.m (O—D) can be used. This method is equally appticable to low concentrations of D2O in H2O, or the reverse (86,87). Absorption in the near infrared can also be used (88,89) and this procedure is particularly useful (see Infrared and raman spectroscopy Spectroscopy). The D/H ratio in the nonexchangeable positions in organic compounds can be determined by a combination of exchange and spectrophotometric methods (90). 

The hydrogen-deuterium exchange rates for 1,2-dimethylpyrazolium cation (protons 3 and 5 exchange faster than proton 4 Section 4.04.2.1.7(iii)) have been examined theoretically within the framework of the CNDO/2 approximation (73T3469). The final conclusion is that the relative reactivities of isomeric positions in the pyrazolium series are determined essentially by inductive and hybridization effects. 

In neutron reflectivity, neutrons strike the surface of a specimen at small angles and the percentage of neutrons reflected at the corresponding angle are measured. The an jular dependence of the reflectivity is related to the variation in concentration of a labeled component as a function of distance from the surface. Typically the component of interest is labeled with deuterium to provide mass contrast against hydrogen. Use of polarized neutrons permits the determination of the variation in the magnetic moment as a function of depth. In all cases the optical transform of the concentration profiles is obtained experimentally. 

In the previous section the interaction of the plasma particle flux with the surface of graphite was discussed. However, the fate of the implanted particles (most importantly deuterium and tritium) following their impact with the graphite surface is also an important issue, and is seen by some as the major impediment to graphite s use as a PFM [58], Quantification of the problem, and determination of possible mitigating steps, is complicated by experimental data which can vary by orders of magnitude [59-66] as reviewed by Wilson [67]. 

A special type of substituent effect which has proved veiy valuable in the study of reaction mechanisms is the replacement of an atom by one of its isotopes. Isotopic substitution most often involves replacing protium by deuterium (or tritium) but is applicable to nuclei other than hydrogen. The quantitative differences are largest, however, for hydrogen, because its isotopes have the largest relative mass differences. Isotopic substitution usually has no effect on the qualitative chemical reactivity of the substrate, but often has an easily measured effect on the rate at which reaction occurs. Let us consider how this modification of the rate arises. Initially, the discussion will concern primary kinetic isotope effects, those in which a bond to the isotopically substituted atom is broken in the rate-determining step. We will use C—H bonds as the specific topic of discussion, but the same concepts apply for other elements. 

Nucleophilic substitution in cyclohexyl systems is quite slow and is often accompanied by extensive elimination. The stereochemistry of substitution has been determined with the use of a deuterium-labeled substrate (entry 6). In the example shown, the substitution process occurs with complete inversion of configuration. By NMR amdysis, it can be determined that there is about 15% of rearrangement by hydride shift accon any-ing solvolysis in acetic acid. This increases to 35% in formic acid and 75% in trifiuoroacetic acid. The extent of rearrangement increases with decreasing solvent... 

Again, the chloride is almost exclusively the exo isomer. The distribution of deuterium in the product was determined by NMR spectroscopy. The fact that 1 and 2 are formed in unequal amoimts excludes the symmetrical bridged ion as the only intermediate. The excess of 1 over 2 indicates fliat some syn addition occurs by ion-pair collapse before the bridged ion achieves symmetry with respect to the chloride ion. If the amount of 2 is taken as an indication of the extent of bridged-ion involvement, one would conclude that 82% of the reaction proceeds through this intermediate, which must give equal amoimts of 1 and 2. 

A number of studies of the acid-catalyzed mechanism of enolization have been done. The case of cyclohexanone is illustrative. The reaction is catalyzed by various carboxylic acids and substituted ammonium ions. The effectiveness of these proton donors as catalysts correlates with their pK values. When plotted according to the Bronsted catalysis law (Section 4.8), the value of the slope a is 0.74. When deuterium or tritium is introduced in the a position, there is a marked decrease in the rate of acid-catalyzed enolization h/ d 5. This kinetic isotope effect indicates that the C—H bond cleavage is part of the rate-determining step. The generally accepted mechanism for acid-catalyzed enolization pictures the rate-determining step as deprotonation of the protonated ketone ... 

However, the optical train illustrated in Figure 22B allows the determination of fluorescence quenching. The interfering effect described above now becomes the major effect and determines the result obtained. For this purpose the deuterium lamp is replaced by a mercury vapor lamp, whose short-wavelength emission line (2 = 254 nm) excites the luminescence indicator in the layer. Since the radiation intensity is now much greater than was the case for the deuterium lamp, the fluorescence emitted by the indicator is also much more intense and is, thus, readily measured. 

Site-specificity of the reaction is established in the first step since enolate formation involves the carbonyl carbon and the former halide bearing carbon, while the stereospecificity of the incoming deuterium is determined during the second step. It appears that the ketonization in deuterioacetic acid yields mainly the kinetic product (axial attack) although deuteration is... 

The salts of some enamines crystallize as hydrates. In such cases it is possible that they are derived from either the tautomeric carbinolamine or the amino ketone forms. Amino ketone salts (93) ( = 5, 11) can serve as examples. The proton resonance spectra of 93 show that these salts exist in the open-chain forms in trifluoroacetic acid solution, rather than in the ring-closed forms (94, n = 5, 11). The spectrum of the 6-methylamino-l-phenylhexanone cation shows a multiplet at about 2.15 ppm for phenyl, a triplet for the N-methyl centered at 7.0 ppm and overlapped by signals for the methylene protons at about 8.2 ppm. The spectrum of 93 ( = 11) was similar. These assignments were confirmed by determination of the spectrum in deuterium oxide. Here the N-methyl group of 93 showed a sharp singlet at about 7.4 ppm since the splitting in —NDjMe was much reduced from that of the undeuterated compound. 

Many methods have been used to determine the deuterium eontent of hydrogen gas or water. For H2/D2 mixtures mass speetroseopy and thermal eonduetivity ean be used together with gas ehromatography (alumina aetivated with manganese ehloride at 77 K). For heavy water the deuterium eontent ean be determined by density measurements, refraetive index ehange, or infrared speetroseopy. 

The main uses of deuterium are in traeer studies to follow reaetion paths and in kinetie studies to determine isotope effeets. " A good diseussion with appropriate referenees is in Comprehensive Inorganic Chemistry, Vol. 1, pp. 99-116. The use of deuterated solvents is widespread in proton nmr studies to avoid interferenee from solvent hydrogen atoms, and deuteriated eompounds are also valuable in struetural studies involving neutron diffraetion teehniques. 

Quadrupole coupling constants for molecules are usually determined from the hyperfine structure of pure rotational spectra or from electric-beam and magnetic-beam resonance spectroscopies. Nuclear magnetic resonance, electron spin resonance and Mossbauer spectroscopies are also routes to the property. There is a large amount of experimental data for and halogen-substituted molecules. Less data is available for deuterium because the nuclear quadrupole is small. 

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