Liquid HCl Research Articles

Orientational correlations and hydrogen bonding in liquid hydrogen chloride

Neutron diffraction data, obtained by employing the hydrogen isotope substitution technique, on orthobaric hydrogen chloride at two state points are presented. The site-site radial distribution functions are derived from these data and are compared with similar results obtained previously for hydrogen iodide and hydrogen bromide. Comparison of the measured hydrogen-hydrogen and chlorine-hydrogen radial distribution functions with those derived assuming uncorrelated orientations demonstrates the presence of strong orientational correlations between first neighboring HCl molecules at both states. An analysis of molecular configurations compatible with the experimental data as generated by a Monte Carlo simulation routine is used to discuss the extent of hydrogen bonding in liquid HCl.

Structure and Properties of Diatomic Liquid HCl

We give the results of a computer simulation of fluid hydrogen chloride for general states along the liquid-vapor coexistence line. We used the intermolecular potential functions only of the separation of chlorides of molecules and an electric dipole interaction which has an orientational dependence.

Synthese und eigenschaften von 1,1,2,2-Tetrachlorund 1,1,2,2-Tetrafluordisilan

1,1,2,2-tetrachlorodisilane was prepared from 1,1,2,2-tetramesityldisilane by reaction with liquid HCl, 1,1,2,2-tetrafluorodisilane by fluorination of tetrabromodisilane with ZnF 2. With PCl 5, 1,1,2,2-tetramesityldisilane was easily chlorinated to form 1,2-dichlorotetramesityldisilane but the subsequent reduction with LiAlD 4 was not successful. The 29Si-NMR, Infrared and Raman spectra are reported.

Structure and thermodynamics of heteronuclear two-centre Lennard-Jones fluids from Monte Carlo simulation and a reference hypernetted chain equation

We have performed extensive Monte Carlo (MC) simulations to evaluate structural and thermodynamic properties of heteronuclear two-centre Lennard-Jones fluids. Computations have been carried out for two uncharged molecular models which roughly describe liquid HCl and HBr. These simulations are used as test benchmarks for a reference hypernetted chain approximation (RHNC-VM), which is the natural extension to heteronuclear fluids of a previously developed approach fairly successful in the context of homonuclear diatomic fluids. The proposed theoretical approach leads to results in good agreement with MC simulation.

Integral equation and simulation studies of a realistic model for liquid hydrogen chloride

Liquid hydrogen chloride is modeled by a system of heteronuclear two-center Lennard-Jones particles with embedded point dipoles and quadrupoles. The effect of molecular polarizability is incorporated via an effective dipole approximation. The study is performed by Monte Carlo reaction field simulation and by hypernetted chain and reference hypernetted chain integral equations. Our simulation results yield dielectric properties in excellent agreement with experimental data for liquid HCl. As for the integral equation approach, we have experimented with an empirical choice of the reference system in the spirit of a recently proposed treatment which has proved extremely successful for pure and quadrupolar two-center Lennard-Jones fluids. The hypernetted chain equation performs slightly better when accounting for the multipolar contributions to the configurational energy, but as a whole the reference hypernetted chain equation, as introduced, here proves to be a more appropriate choice.

Use of DermCaps Liquid and Hydroxyzine HCL for the Treatment of Feather Picking

Use of DermCaps Liquid and Hydroxyzine HCL for the Treatment of Feather Picking

Concentration‐dependent depolarized Raman spectra of HCl and DCl in solution in liquid carbon dioxide

AbstractThe depolarized component of Paman scattering by pure liquid HCl and DCl and of solutions of these acid halides in liquid CO2 are reported. At room temperature the band contours show no S branch intensity in pure acid halide liquid, but in solution in liquid CO2 and S branch is increasingly evident with increasing CO2 concentration. The frequency shifts are a function of the dielectric constant and refractive index of the solution. Reorientational correlation functions calculated from the anisotropic scattering decay more slowly in the first few tens of femtoseconds than predicted for monomeric acid halides, suggesting contribution to the composite correlation function by species of larger moments of inertia but vibrational frequencies identical with those of the monomers.

Über Polygermane, XVIII [1] Drucksynthese der mehrfach funktionellen Digermane Ph6-nGe2Cln (n = 2, 3, 4) und von Ph2GeCl2 / On Polygermanes, XVIII [1] Synthesis of the Multifunctional Digermanes Ph6-nGe2Cln (n = 2, 3, 4) and of Ph2GeCl2 under Pressure

Reaction of Ph6Ge2 with liquid HCl under pressure leads to di-, tri-and tetrachloro phenyldigermanes. The yield of higher chlorinated products increases with increasing pressure. The analogous reaction of Ph4Ge yields Ph2GeCl2 quantitatively. The Ge-Ge bond is most unstable in the case of Ph3 Ge2Cl3 both chemically and thermally. The crystal structure of Ph2Ge2Cl4 has been determined (R = 0.057), Ge-Ge 241.3(1) pm

The vibrational relaxation of DCl(v=1) in liquid xenon and HCl(v=1) in liquid krypton

The relaxation rate constants for DCl(v=1) in liquid xenon at 211 K and HCl(v=1) in liquid krypton at 190 K are reported. Both the DCl–DCl and HCl–HCl rate constants are similar to the corresponding gas phase rate constants at the same temperature, and the relaxation appears amenable to an isolated binary collision (IBC) description. As in the gas phase, the rate constant for DCl–DCl deactivation in liquid xenon is found to be smaller than that for HCl–HCl relaxation in liquid xenon, despite the smaller energy defect for the DCl relaxation process. This suggests that rotational degrees of freedom are also involved in the liquid phase vibrational relaxation of these molecules. The observed relaxation rates for DCl(v=1) by liquid xenon and HCl(v=1) by liquid krypton are found to be within an order of magnitude of values estimated from various forms of the IBC model. More careful comparisons await values of the appropriate gas phase relaxation rate constants near 200 K. Finally, certain features of the mechanism for production of vibrationally excited HCl and DCl are considered.

Multinuclear nuclear magnetic resonance study of the interaction of some phosphorus(V) compounds with inorganic acids. The protonating abilities of HNO3, MeSO3H, and HPO2F2 towards the phosphoryl group

The influence of protonation upon 31P and 17O n.m.r. parameters of the phosphoryl compounds POCl3 and HPO2F2 has been investigated. For POCl3, δ(17O) and 1J(P–O) decrease whereas δ(31P) increases with increasing protonation of the phosphoryl group. For HPO2F2 the changes in δ(17O) and δ(31P) were less informative although 1J(P–F) appears to increase smoothly with increasing protonation. The same trend in 1J(P–F) is observed for solutions of Na2PO3F in some inorganic acids (MeSO3H, CF3CO2H, HNO3, HSO3Cl, and 25 oleum). The POCl3 results indicate that the ability of HNO3 to protonate the phosphoryl group is significantly greater than would be anticipated on the basis of Hammett acidity-function measurements, whereas the protonating ability of MeSO3H is as anticipated on the basis of its Hammett function and that of HPO2F2 is lower than those of HNO3 and MeSO3H, comparable with that of liquid HCl. The values of δ(31P) of POBr3 in HNO3, MeSO3H, and HPO2F2 are in agreement with the above conclusions.

The effect of soft cores and anisotropic forces on vibrational energy relaxation in liquids

Abstract Starting from the isolated-binary-collision hypothesis, simple explicit expressions for the vibrational energy relaxation time in liquids are obtained. We stress the role of soft repulsive forces and of anisotropic interactions. In both cases, deviations from a model developed by Delalande and Gale, assuming an attractive hard-sphere potential, are obtained and discussed. The specific case of liquid HCl and DCl is treated as an application.

Picosecond stimulated Raman scattering in liquids in the laser depletion regime

Both the spatial growth rate of stimulated Raman scattering and conversion efficiency to Stokes radiation were measured in three liquids (methanol, ethanol, and acetone) in the regime where the pump pulse is significantly depleted. Self-focusing was present, and, when taken into account by model calculations, the region of maximum Stokes spatial growth is in agreement with experiment. Conversion efficiency to first Stokes was measured for both focused and unfocused pump beams in liquid HCl and is in agreement with the depleted beam model.

Differential incoherent scattering cross sections of 661.6 keV gamma rays in elements derived from differential incoherent scattering cross sections in compounds

Differential incoherent scattering cross sections of 661.6 keV gamma rays in the solid compounds NaCl, NaNO2, KCl, NiO, NaNO3, CuCl, NaBr, CaCO3, CaCl2 and ZnCl2 and in the liquid compounds H2O and HCl at 30, 45 and 60 degrees have been measured. Making use of the bonded hydrogen incoherent scattering functions of Hubbell et al. and the mixture rule, the differential incoherent scattering cross sections in C, N, O, Cl, Na, K, Ca, Br, Ni, Cu and Zn are derived, compared with the theoretical values of Hubbell et al. and discussed.

A molecular dynamics simulation of rotational and vibrational relaxation in liquid HCl

We have carried out a molecular dynamics simulation of liquid HCl near its normal boiling point using the C* potential of Klein and McDonald. A wide variety of equilibrium and dynamical properties have been studied, ranging from partial structure factors to velocity, angular velocity, and torque autocorrelation functions. Dipole moment and polarizability tensor correlation functions have been evaulated and compared with experimental data from dielectric relaxation and Raman line shape studies. Vibrational phase relaxation has been simulated; we show that HCl is an intermediate case between the rapid modulation and static broadening limits. The question of correlation between rotational and vibrational relaxation is discussed.

The HCl–HCl interaction: From quantum mechanical calculations to properties of the liquid

Analytical HCl–HCl pair potentials are derived from large quantum mechanical calculations at CEPA-(SD) level. The computed well depth for the dimer is 1.9 kcal/mol. Those pair potentials are used in molecular dynamics simulation studies at T=297 K and ρ=0.8354 g/cm3. The results for the static (e.g., pair distribution functions) and dynamic properties are compared with experimental and other molecular dynamics results. Comparison of the results from different simulation runs allows a check on their sensitivity with respect to the pair potential employed. It turns out that the potential yielding the best fit to the computed interaction energies gives a good representation of properties of liquid HCl. However, a readjustment of this potential—in order to account for well-known deficiencies of the quantum mechanical calculations—results in a slight improvement especially in the mean potential energy and the pressure. Finally, we used the computed pair potential to determine the structure and association energy of (HCl)n clusters with cyclic and chain structure.

Synthesis and characterization of uranium (VI) chloride flourides

Abstract Uranium (VI) chloride fluorides were synthesized by the reaction of liquid HCl and solid UF 6 between −80 and −114°C. These dark red compounds are unstable above −40 to −60°C. The simplest formulas derived from compositional analysis are UF 5 Cl and UF 4 Cl 2 .

On the dynamical properties of liquid hydrogen chloride: a light scattering experiment

Depolarized rotovibrational Raman spectra of orthobaric liquid HCl are studied to obtain information on the molecular reorientational motion. Second order spectral moments are obtained and the presence of collision induced scattering is discussed, while fourth spectral moments are used to obtain values of mean square intermolecular torques. Orientational correlation functions and correlation times are studied and a comparison with other experimental data is made. The liquid is dominated by strong anisotropic forces at low temperature and is collision limited on approaching the critical point. A comparison is made with the quasi-lattice random jump model and with generalized hydrodynamics and it is found that a fair rotational coherence is necessary to explain the viscosity dependence of the correlation times below 250 K.

Light scattering from hydrogen and deuterium halides

Light scattering measurements along the coexistence line show that reorientation in liquid HCl, DCl, and HBr is strongly hindered at low temperature and collision limited on approaching the critical point. Discrepancies with NMR data are observed.

On the vibrational spectra of liquid HCl

We report quantitative measurements of the infrared spectra intensities and of the Raman cross section for liquid HCl. The local field effect and the induced dipole moment account for the observed intensity enhancement. Our calculation is based on the reaction field approach. On the other hand, we show that the local field effect and the dipolar term in the intermolecular interaction energy are not sufficient to explain the frequency shift. We also show that the first overtone is mainly due to simultaneous transitions of two molecules from the ν = 0 to the ν = 1 levels and our calculations give the right order of magnitude of its intensity. Finally, we can reproduce the lineshape of the first overtone by a dissipative coupling which is derived from Redfield's theory of relaxation.

Determination by Raman spectroscopy of the solvation number of the chloride ion in liquid hydrogen chloride

AbstractSolutions of various concentrations of tetramethylammonium chloride and trimethylammonium chloride in liquid hydrogen chloride have been examined by Raman spectroscopy and the solvation number of Cl− anions in these solutions determined. It was found for solutions up to 3 mol I−1 of (CH3)4N+Cl− in liquid HCl, that the Cl− anions are solvated by six HCl molecules, while trimethylammonium chloride exists in the form of ion pairs solvated by five HCl molecules, (CH3)3N+H ⃛Cl−, 5HCl.