Deuterium Chloride Research Articles

Silicon hydrides and nickel complexes IV. Preparation of siliconnickel complexes by the reaction of silicon hydrides with α-alkylnickel complexes

Three siliconnickel complexes, Ni(bipy) (SiX 3) 2 (Ia: X 3 = Cl 3, Ib: X 3 = MeCl 2) and Ni( h 5-C 5H 5)(PPh 3)(SiCl 3) (II), were prepared by treatment of silicon hydrides with appropriate alkylnickel complexes, Ni(bipy)R 2 (IIIa: R = Me, IIIb: R = Et) and Ni( h 5-C 5H 5)(PPh 3)Et (IV), respectively. Both complexes Ia and Ib reacted with hydrogen (or deuterium) chloride to give the corresponding chlorosilane HSiX 3 (or DSiX 3) and Ni(bipy)Cl 2, in good yields. Ib reacted with tetracyanoethylene to afford MeCl 2SiSiCl 2Me, but in low yield. II reacted with methyl iodide to form MeSiCl 3 (23.5% yield). The siliconnickel complex Ia was inactive as catalyst for hydroxilylation of olefins, whereas the alkyl complexes IIIb and IV were active.

Thermodynamics and Spectroscopy of the Hydrogen Bonded Complex Formed between Hydrogen (Deuterium) Chloride and Dimethyl Ether in the Gas Phase by Raman Scattering

The equilibrium constant Kp has been obtained for the complex [Formula: see text] over a range of temperatures between 22 and 132 °C by monitoring the integrated intensity of the Raman scattered band from unassociated DCl in a mixture with dimethyl ether. By applying the relation In KP = −ΔH/RT + ΔS/R the quantities ΔH, ΔG, and ΔS have been evaluated.Broad νCl–H and νCl–D complex bands have been observed and are found to be polarized.

Simple and Specific Assay of Penicillins by IR Spectrophotometry in Deuterium Oxide and Dimethyl Sulfoxide Solutions

An IR spectrophotometry method for the qualitative and quantitative analysis of penicillins is described. The method is based on the inspection of the carbonyl region of the IR spectrum of penicillins dissolved in deuterium oxide or dimethyl sulfoxide solution and on the measurement of the absorbance of the -lactam band at about 1760 cm−1. Most common natural and synthetic penicillins are amenable to the present IR analysis in solution, without previous derivatization. The accuracy of the method is better than ±2% and is thus comparable to that usually attainable by current iodometric procedures. Since the solution spectra in the analytical region are characteristic for the individual penicillins, the described method is superior to iodometry as far as specificity is concerned. A single analysis usually requires no more than 15 min. The method allows a direct evaluation of the stability of penicillins in aqueous (deuterium oxide or deuterium chloride) solutions. Usual salts or buffers generally do not interfere with the analysis. Some qualitative and quantitative aspects of the IR spectra of penicillins in solution are discussed.

Dissociation constants and conductivities of hydrogen chloride and deuterium chloride in N,N-dimethylformamide at 25.deg.

Dissociation constants and conductivities of hydrogen chloride and deuterium chloride in N,N-dimethylformamide at 25.deg.

Addition of Hydrogen Chloride and Deuterium Chloride to 2-exo-Methoxy-5-norbornene.

Addition of Hydrogen Chloride and Deuterium Chloride to 2-exo-Methoxy-5-norbornene.

Raman spectra of molecular crystals lattice spectra and dynamics of orthorhombic hydrogen and deuterium halides

Raman spectra of the lattice regions of polycrystalline hydrogen chloride, hydrogen bromide, deuterium chloride and deuterium bromide at 79 and 18°K are reported. The lattice modes are assigned in accordance with the known crystal structures, and their frequencies compared with those obtained from calculations based on a simple intermolecular potential.

Isotope Exchange vs Abstraction for H + DCl

Rates of isotope exchange reactions in deuterium chloride—hydrogen mixtures photolyzed at 1849 Å have been measured by mass spectroscopy. Under conditions where reactions of product molecules were negligible quantum yields of HD and D2 were calculated using DCl for actinometry. Large HD quantum yields indicate that chain reactions occur. The ratio of HD to D2 formed in these chain reactions is shown to be equal to the ratio k2/k3 of rate coefficients for the abstraction (2), H + DCl → HD + Cl, and the exchange (3), H + DCl → HCl + D. From quantum yields at 27–225°C this ratio is calculated to be k2/k3=(850 ± 200) exp [ − (2220 ± 180) / RT]. A quantum yield of D2 independent of chain lengths and with little temperature dependence is attributed to the reaction D* + DCl → D2 + Cl of hot atoms from DCl photodissociation.

Stereochemistry and mechanisms of the addition of deuterium chloride to bicyclo[2.2.1]heptadiene (norbornadiene) and to tetracyclo[3.2.02,7.04,6]heptane (quadricyclene)

Stereochemistry and mechanisms of the addition of deuterium chloride to bicyclo[2.2.1]heptadiene (norbornadiene) and to tetracyclo[3.2.02,7.04,6]heptane (quadricyclene)

Carbon, Carbides, and Methane in an Apollo 12 Sample

Total carbon in the Apollo 12 sample 12023 fines was 110 micrograms per gram of sample with a carbon isotopic abundance delta(13)C (relative to the Pee Dee belemnite standard) of +12 per mil. Hydrolysis of the fines with deuterium chloride yielded undeuterated methane along with deuterated hydrocarbons, thus confirming the presence of 7 to 21 micrograms of carbon per gram of sample as carbide and about 2 micrograms of carbon per gram of sample as indigenous methane. After vacuum pyrolysis of the fines to 1100 degrees C the following gases were detected in the relative abundance: carbon monoxide carbon dioxide methane. Variations of the delta(13)C value with the pyrolysis temperature indicated the presence of carbon with more than one range of isotopic values. The observed delta(13)C value of +14 per mil for lunar carbide is much higher than that of carbide in meteorites. These results suggest that lunar carbide is either indigenous to the moon or a meteoritic contribution that has been highly fractionated isotopically.

Infrared spectroscopic studies of adsorption on alkali halide surfaces I. HCl, HBr and HI on fluorides, chlorides, bromides and iodides

An infrared spectroscopic study of the adsorption of hydrogen halides HCl, HBr, and HI on alkali-metal chlorides, bromides and iodides has shown the presence of a dominant surface species involving hydrogen bonding between the hydrogen halide molecule and a surface anion. In favourable cases it has been possible to measure all three vibration frequencies of the surface complex X- H ... Y-(X and Y halogen atoms) in the infrared and far infrared regions. HCl forms hydrogen bonds of increasing strength with the surface along the sequences LiCl < NaCl < CsCl and Nal < NaBr < NaCl as judged from the frequency shifts of thev(HCl) vibrations. In the presence of adsorbed water additional bands in the regions of 2100 and 1200 cm-1have been tentatively interpreted in terms of protonated surface anions. Mixed halogen systems gave anomalous spectroscopic results when the halogen of the hydrogen halide occurs further down the Periodic Table than the halogen of the salt. These have been satisfactorily interpreted in terms of surface halogen exchange reactions of the type Br— H + Cl-(surface) -> Cl— H.. .Br-(surface). Adsorption of hydrogen chloride and deuterium chloride on lithium, sodium, potassium and caesium fluorides gives rise to very different infrared spectra originating in the bifluorideion [FHF]-. Closely similar spectra are obtained from hydrogen bromide on sodium fluoride, and exploratory spectra were obtained from HCl on calcium fluoride. The first step in the production of this species may be the halogen exchange reaction XH + F-→ X-+ HF, where (X = Cl, Br). The absorption bands from the [FHF]-surface species have very considerable breadths which are independent of surface coverage over a wide range. This phenomenon seems most satisfactorily interpreted in terms of interactions between adjacent [FHF]-ions in islands resulting from the corrosive reaction between the hydrogen halide and the fluoride surface about active centres.

Hydrogen bonding in the vapour phase: an unusual type of infrared band

Association bands, due to vibrations of the hydrogen halides modified by hydrogen bonding, have been measured in the near infrared spectra of mixtures of alkyl cyanides with hydrogen chloride or deuterium chloride in the vapour phase. The vibration frequencies of the hydrogen bonds have been estimated. The association band found with mixtures of methyl cyanide and hydrogen chloride, or deutero derivatives of each of these molecules, shows a broad contour upon which a number of sharp peaks are superposed at the lower frequency side. These peaks have been interpreted as being due to an agglomeration of P lines near the band head in each of a series of hot bands which accompany the association band, and which arise from transitions from higher levels of a bending mode of low frequency. The latter appears to have a frequency in the range 20 to 60 cm -1 . The spectral analysis suggests that the excitation of the hydrogen halide stretching vibration leads to a shortening of the hydrogen bond.

Transfer of the reaction center during deuterodemetallization of substituted benzylmercury chlorides

1. The distribution of deuterium in the products of deuterometallization of o-, m-, and p-methyl-, 3,5-dimethyl-, and 2,4,6-trimethylbenzylmercury chloride by reaction with deuterium chloride was investigated. 2. The presence of deuterium in the benzene nucleus of the products of deuterodemetallization of o-,m-, and p-methyl-and 3,5-demethylbenzylmercury chloride is due mainly to the transfer of the reaction center from theα-carbon atom to the nucleus.

Isotopic exchange of hydrogen in substituted benzylmercury chlorides

1. The authors study the kinetics of splitting and isotopic exchange of substituted benzylmercury chlorides by the action of deuterium chloride in absolute dioxane. 2. It has been found that the substituents have a symbatic effect on the isotopic-exchange and demetalation velocities owing to the common character of their mechanisms, including transfer of the reaction center from theα-carbon atom to the benzene ring.

Hot-Atom Reactions in the Photolysis of Deuterium Chloride at 1849 Å

The importance of hot deuterium atoms in photolyses of DCl–lCl2 mixtures at 1849 Å has been demonstrated, and the kinetics of this system have been described. Photodecomposition of DCl was followed by mass-spectrometric analysis of the D2 formed after successive intervals of time. The observed decreases in the initial rate of D2 formation upon addition of CO2, and inert gases CO2, Xe, and CF4 may be readily interpreted in terms of a hot-atom mechanism but cannot be made compatible with a completely thermal mechanism. Rate coefficient ratios for the hot-atom reactions, D*+DCl→ lim 2D2+Cl, D*+M→ lim 3D+M, D*+Cl2→ lim 6DCl+Cl, were found to be k6 / k2 ≈ 6.5, k3DCl / k2 = 0.65, k3CO2 / k2 = 1.15, k3CF4 / k2 ≈ 1.15, and k3Xe / k2 < 0.1. The ratio k6 / k2 increased from 6.5 in the absence of inert gas to 9.2 when [CO2]/[DCl] = 1.87. This ratio increases to ≈ 300 for a thermal atom distribution at 300°K. Comparisons of thermalizing efficiencies for several molecules suggest that inelastic collisions are important in thermalizing hot atoms produced photochemically at 2.1 eV.

A study of hydrogen-bonding between dimethyl ether and the hydrogen halides in the solid phase

Abstract Spectra have been recorded of adducts of dimethyl ether with hydrogen chloride, bromide and iodide, and deuterium chloride and bromide, in the solid state. From the position and contour of the band assigned to the H-X stretching frequency it was concluded that the adducts are formed by hydrogen-bonding Me 2 O ⋯ HX and not by proton transfer to give [Me 2 OH] + X − . With all the hydrogen halides, characteristic absorption bands were observed at about 1020 and 800 cm −1 and these have been assigned to the O ⋯ HX torsional modes of the adduct, coupled to some degree with skeletal modes of the ether.

Kinetics and mechanism of addition of acids to olefins. IV. Addition of hydrogen and deuterium chloride to 3-methyl-1-butene, 3,3-dimethyl-1-butene, 1-methylcyclopentene, and 1-methylcyclopentene-2,5,5-d3

Kinetics and mechanism of addition of acids to olefins. IV. Addition of hydrogen and deuterium chloride to 3-methyl-1-butene, 3,3-dimethyl-1-butene, 1-methylcyclopentene, and 1-methylcyclopentene-2,5,5-d3

Neutron diffraction study of molecular motion in solid deuterium chloride

Mean square thermal displacements of the chlorine and deuterium atoms were derived both in the ordered orthorhombic and in the disordered cubic phase of deuterium chloride by a least-squares study of the neutron powder diffraction patterns recorded at four temperatures over the 4.2 to 111.5 K range. The atomic displacements were subsequently interpreted as due to the superposition of the internal stretching vibrations and of the rigid-body translational and angular vibrations of the molecules. The analysis of the results revealed substantial rigid-body vibrational components in the zero-point motion of the molecules and a rapid rise in the amplitude of the in-plane angular vibrations on approaching the transition point. It also showed a small but possibly significant lengthening of the CI—D bond as the temperature decreases. Finally, it gave a fuller understanding of the disordered cubic phase as a dynamic mixture of short-lived polymers of varying lengths and shapes.

The addition of deuterium chloride to norbornene and nortricyclene; a 220 MHz nuclear magnetic resonance study

The first page of this article is displayed as the abstract.

Rotational Motion in Solution: Hydrogen Halides in Cyclohexane

The dipole correlation function and the average kinetic rotational energy of hydrogen fluoride, hydrogen chloride, and deuterium chloride have been computed from the published far-infrared absorption bands [P. Datta and G. M. Barrow, J. Chem. Phys. 43, 2137 (1965)]. The computations show that the dissolved hydrogen halide molecules undergo fast, large-angle rotational diffusional jumps: for instance, the dissolved HF molecules which are in their most populous state have regained their original orientation after a time interval of 0.2 × 10−12 sec following the disturbance of their equilibrium state. The coherence of their rotational motion has completely decayed after about 0.4 × 10−12 sec. A comparison with the dipole correlation function of the classical ensembles of freely rotating molecules shows that the intermolecular forces between HF and cyclohexane become observable only after a time interval of 0.08 × 10−12 sec; the corresponding value for dissolved DCl is 0.14 × 10−12 sec. These time intervals seem to correlate with some “average free volume” in liquid cyclohexane. This was shown by an estimate of the translational and rotational motion of the hydrocarbon from proton spin–lattice relaxation measurements, evaluation of the band shape of its a2u fundamental (522 cm−1), and some simple gas–kinetic considerations. Quantitative estimates of collision-induced absorption between the HF and cyclohexane molecules indicate that dipole–induced-dipole and quadrupole–induced-dipole absorption is appreciable. It is shown that the quadrupole–induced-dipole absorption must be subtracted out in order to obtain good values for the average rotational kinetic energy of the dissolved hydrogen halide molecules.

Nuclear magnetic spin relaxation in solid solutions of hydrogen chloride in deuterium chloride

The following measurements have been made: the proton linewidth for HCl, in both solid phases by both steady state and Bloch decay methods, the proton spin-lattice relaxation time for HCl and for 50% HCl/DCl in the solid state, at resonance frequencies of 21·5, 20·8, 14·3 and 9·0 MHz, and the proton spin-lattice relaxation time in the rotating frame for radio-frequency fields of 14·5, 12·0 and 5·3 G.