Mechanism for the reactions of sulfides and sulfoxides with hypochlorites: racemization and oxygen exchange of oxysulfonium salts and sulfoxides

Density functional theory computations have been performed on the oxidations of sulfides and sulfoxides with hypochlorite ion (OCl^?), hypochlorous acid, and alkyl hypochlorites to study the mechanism of the reactions. The OCl^? anion transforms sulfides to sulfoxides and sulfoxides to sulfones in oxygen transfers. The oxygen atom of QOCl hypochlorites (Q = H, Me, t‐Bu) attacks at the sulfur atom of the substrates, and oxysulfonium cation intermediates are formed; the departure of the leaving Cl^? is catalyzed by soft Lewis acids. The structures of the early transition states are determined by highest occupied molecular orbital–lowest unoccupied molecular orbital interactions. The sulfur compounds are the electron acceptors in the reaction with OCl^?, but they are the electron donors in the reactions with QOCl. The attack of Cl^? at the oxygen atom of oxysulfonium cation intermediates leads to the sulfide and QOCl precursors and can result in racemization, oxygen exchange, and reduction of oxysulfonium salts in reversible reactions. The attack of Cl^? at the sulfur atom of oxysulfonium salts produces λ⁴‐sulfane intermediates. Oxysulfonium cations can be transformed into sulfoxide products with the attack of Cl^? or water at the α‐carbon atom of the O‐alkyl group. The attack of water at the sulfur atom of oxysulfonium cation leads to hydrolysis or oxygen exchange reactions. Racemization and oxygen exchange of sulfoxides proceeds in similar reactions, through the formation of hydroxysulfonium cation intermediates in acidic media in the presence of Cl^?. Chlorosulfonium cations are of very high energy; their intermediacy can be ruled out in the reactions of sulfides with hypochlorites. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural,optical and electrical properties of sulfur-incorporated amorphous carbon films

Amorphous carbon–sulfur (a-C:S) composite films were prepared by vapor phase pyrolysis technique. The structural changes in the a-C:S films were investigated by electron microscopy. A powder X-ray diffraction (XRD) study depicts the two-phase nature of a sulfur-incorporated a-C system. The optical bandgap energy shows a decreasing trend with an increase in the sulfur content and preparation temperature. This infers a sulfur incorporation and pyrolysis temperature induced reduction in structural disorder or increase in sp ² or π-sites. The presence of sulfur (S 2p) in the a-C:S sample is analyzed by the X-ray photoelectron spectroscopy (XPS). The sp ³/sp ² hybridization ratio is determined by using the XPS C 1s peak fitting, and the results confirm an increase in sp ² hybrids with sulfur addition to a-C. The electrical resistivity variation in the films depends on both the sulfur concentration and the pyrolysis temperature.     

Sulfur Immobilized in Hierarchically Porous Structured Carbon as Cathodes for Lithium–Sulfur Battery with Improved Electrochemical Performance

In order to overcome the main obstacles for lithium–sulfur batteries, such as poor conductivity of sulfur, polysulfide intermediate dissolution, and large volume change generated during the cycle process, a hard‐template route is developed to synthesize large‐surface area carbon with abundant micropores and mesopores to immobilize sulfur species. The microstructures of the C/S hybrids are investigated using field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, Raman spectroscopy, X‐ray photoelectron spectroscopy, nitrogen adsorption–desorption isotherms, and electrochemical impedance spectroscopy techniques. The large surface and porous structure can effectively alleviate large strain due to the lithiation/delithiation process. More importantly, the micropores can effectively confine small molecules of sulfur in the form of S_2–4, avoiding loss of active S species and dissolution of high‐order lithium polysulfides. The porous C/S hybrids show significantly enhanced electrochemical performance with good cycling stability, high specific capacity, and rate capability. The C/S‐39 hybrid with an optimal content of 39 wt% S shows a reversible capacity of 780 mA h g^?1 after 100 cycles at the current density of 100 mA g^?1. Even at a current density of 5 A g^?1, the reversible capacity of C/S‐39 can still maintain at 420 mA h g^?1 after 60 cycles. This strategy offers a new way for solving long‐term reversibility obstacle and designing new cathode electrode architectures.     

Evaluation of the Sulfate Dynamics in Groundwater by Means of Environmental Isotopes

Abstract

Elevated sulfate concentrations and their heterogeneous distribution in the drinking water catchment area Torgau-Mockritz (Germany) were investigated by means of multiple isotope signatures such as δ³⁴S, δ¹⁸O-H₂O, δD, tritium, and ⁸⁵Kr. δ³⁴S values of the groundwater sulfate vary between -19…+ 37‰ CDT. No simple correlation exists between sulfate concentrations and δ³⁴S. Superimposition of different sulfur sources and mobilization processes combined with a complicated groundwater movement create a complex distribution pattern. The oxidation of reduced sedimentary sulfur has to be regarded as a main source of dissolved sulfate at least regionally. Tritium and ¹⁴C data revealed that old groundwater can be excluded as source for high sulfate contents. Correlated temporal variations in the concentrations of tritium and sulfate are observed in deeper sampling positions. Highly variable δ¹⁸O and δD, as detected in parts of the catchment area, indicate local influences of surface water infiltration into the aquifer. The spatial distribution of isotope signatures enables the identification of zones with descending younger water or hindered groundwater movement and hence provides useful hints for flow modeling.     

Optical characteristics and plasma parameters of a blue-green exciplex lamp

The optical characteristics and plasma parameters of an exciplex lamp radiating in the blue-green spectral range are studied. A plasma is generated by an atmospheric-pressure barrier discharge initiated in a quaternary mixture including mercury dibromide, sulfur hexafluoride, nitrogen, and helium. It is shown that the exciplex lamp can radiate at an elevated repetition rate of pump pulses (1–12 kHz) under the conditions of mixture self-heating. A tradeoff between the radiation power and nitrogen partial pressure is found. The mean specific radiation power in the blue-green range at a level of 480 mW/cm³ is achieved at partial vapor pressures of mercury dibromide, sulfur hexafluoride, nitrogen, and helium of 0.70, 0.07, 4.00, and 117.20 kPa, respectively. The plasma parameters, namely, the electron energy distribution function; concentration, temperature, and mean energy of electrons; transport properties; and rate constants of elastic and inelastic electron scattering by the working mixture components are determined as functions of ratio E/N (where E is the electric field strength and N is the total concentration of mercury dibromide, sulfur hexafluoride, and nitrogen molecules and helium atoms). It is found that mercury monobromide molecules and also excited and higher energy states take part in the population of exciplex molecules HgBr* (B²Σ₁^2/+ states) in the course of quenching these exciplexes by sulfur hexafluoride and nitrogen molecules.     

Thermal erosion of metal surfaces under the action of fine-focused scanning electron beams

A model of thermal erosion of a metal surface under the action of low-energy fine-focused scanning electron beams is developed. Peculiarities of thermal erosion of a metal surface irradiated by these beams with a power of 1…10 kW are considered. The influence of the irradiation parameters on the intensity of carrying the substance from the surface is analyzed. It is shown that due to such beams, the coefficients of metal erosion reach values of 10³ atom/electron and even greater. This is characteristic of powerful submicrosecond electron and ion beams, but the efficiency of using their energy turns out to be much higher.     

Concerted SN2 mechanism for the hydrolysis of acid chlorides: comparisons of reactivities calculated by the density functional theory with experimental data

DFT computations have been performed in acetone and water solvents in order to investigate the mechanism of hydrolysis of acid chlorides. Acetyl chloride and chloroacetyl chloride hydrolyze via concerted, one‐step S_N2 mechanism, with the attack of water at the sp² hybridized carbon atom of the C?O group, and the transition state (TS) has distorted tetrahedral geometry. Solvent molecules act as general base and general acid catalysts. The TS of chloroacetyl chloride is tighter and less polar than the TS of acetyl chloride. The structure of the S_N2 TS for the hydrolysis of benzoyl chlorides changes with the substituents and the solvent. Tight and loose TSs are formed for substrates bearing electron withdrawing (e‐w) and electron donating (e‐d) groups, respectively. In acetone, only the e‐w effect of the substituents increase the reactivity of the substrates, and the change of the structure of the TSs with the substituents is small. In water, polar and very loose TSs are formed in the reactions of benzoyl chlorides bearing e‐d substituents, and the rate enhancing effect of both e‐d and e‐w groups can be computed at higher level of theory. Calculated reactivities and the changes of the structure of the TSs with substituents and solvent are in accordance with the results of kinetic studies. In S_N2 nucleophilic substitutions late/early TSs are formed if the attacking reagent is poorer/better nucleophile than the leaving group, and loose/tight TSs are formed for substrates bearing e‐d/e‐w substituents and in protic/aprotic solvents. Copyright © 2010 John Wiley & Sons, Ltd.     

Collision-energy-resolved Penning ionization electron spectroscopy of styrene, 2-vinylpyridine, and 4-vinylpyridine with He*(23S) metastable atoms

Collisional ionization of styrene (phenylethylene), 2-vinylpyridine, and 4-vinylpyridine with metastable He*(2³S) atoms were studied by means of collision-energy/electron-energy resolved two-dimensional Penning ionization electron spectroscopy. Collision energy dependence of partial ionization cross-sections, which reflects the anisotropic interactions between a He*(2³S) atom and the target molecules, indicates that attractive interaction for the out-of-plane access of a He*(2³S) atom to phenyl group is stronger than that for the out-of-plane access to vinyl group. Moreover, it was found for vinylpyridines that the attractive interaction around π electrons became weaker than that for styrene, and that the attractive interaction for the in-plane access to the nitrogen atom is stronger than that for out-of-plane π-directions. However, in 2-vinylpyridine, the hydrogen atom of vinyl group prevents a He*(2³S) atom from approaching to the nitrogen atom along in-plane directions, and thus the attractive interactions around the nitrogen atom were shielded by the vinyl group. The experimentally observed anisotropic interactions were qualitatively supported with ab initio model interaction potential calculations between a Li (He*(2³S)) atom and the target molecule. Concerning with electronic structures of investigated molecules, the assignment of Penning ionization electron spectrum for 4-vinylpyridine was discussed on the basis of different behavior of collision-energy dependence of partial ionization cross-sections, and the satellite ionization band in Penning ionization electron spectra was also reported for styrene.     

Sonication-assisted synthesis of a new cationic zinc nitrate complex with a tetradentate Schiff base ligand: Crystal structure,Hirshfeld surface analysis and investigation of different parameters influence on morphological properties

A nanostructured cationic zinc nitrate complex with a formula of [ZnLNO₃]NO₃ (where L = (N²E,N^2′E)-N¹,N^1′-(ethane-1,2-diyl)bis(N²-((E)-3-phenylallylidene)ethane-1,2-diamine)) was prepared by sonochemical process and characterized by single crystal X-ray crystallography, scanning electron microscopy (SEM), FT-IR and NMR spectroscopy and X-ray powder diffraction (XRPD). The X-ray analysis demonstrates the formation of a cationic complex that metal center is five-coordinated by four nitrogen atom from Schiff base ligand and one oxygen atom from nitrate group. The crystal packing analysis demonstrates the essential role of the nitrate groups in the organization of supramolecular structure. The morphology and size of ultrasound-assisted synthesized zinc nitrate complex have been investigated using scanning electron microscopy (SEM) by changing parameters such as the concentration of initial reactants, the sonication power and reaction temperature. In addition the calcination of zinc nitrate complex in air atmosphere led to production of zinc oxide nanoparticles.     

A computational NMR study of nitrogen substitutional impurity in the armchair BeO nanotube

The properties of nitrogen doped model of (5, 5) armchair beryllium monoxide nanotubes (BeONTs) have been investigated by density functional theory (DFT) and chemical shift parameters were calculated. A BeONT consisting of 60 Be, 60 atoms of O, and having a length of 1.67 nm was considered and each end of the nanotube was capped by 10 hydrogen atoms. The calculated results indicate that by replacing an O atom by N atom (N_O-doping), the chemical shift (CS) parameters of ⁹Be and ¹⁷O atoms are un-affected but replacing a Be atom with N (N_Be-doping) affects the CS parameters of O atoms. These results imply that role of nitrogen as an electron acceptor is more significant in the structure for which it dopes a Be atom.     

Total cross sections for electrons scattering from simple molecules containing the larger atom sulfur at 30-5000eV

A complex optical model potential modified by the concept of bonded atom, which takes into consideration the overlapping effect of electron clouds, is employed to calculate the total cross sections for electrons scattering from simple molecules （SO2, H2S, OCS, CS2 and SO3） containing the larger atom, sulfur, at 30-5000eV by using the additivity rule model at Hartree-Fock level. The quantitative molecular total cross section results are compared with those obtained in experiments and other calculations wherever available, and good agreement is obtained. It is shown that the additivity rule model together with the complex optical model potential modified by the concept of bonded atom can give the results closer to the experiments than the one unmodified by it. So, the introduction of bonded-atom concept in complex optical model potential betters the accuracy of the total cross section calculations of electrons from the molecules containing the larger atom, sulfur.     

N‐Methylbenzoazacrown ethers with the nitrogen atom conjugated with the benzene ring: the improved synthesis and the reasons for the high stability of complexes with metal and ammonium cations

An improved method for the synthesis of formyl derivatives of N‐methylbenzoazacrown ethers is proposed. They are prepared in up to 68% yields over fewer steps and with a much shorter time required for the last step. The stability constants of complexes formed by N‐methylbenzoazacrown ethers and their structural analogs with alkali metal, alkaline‐earth metal and ammonium cations were determined by ¹H NMR titration in CD₃CN. High stability of complexes of N‐methyl derivatives of benzoazacrown ethers is demonstrated, comparable with or even exceeding the stability of benzocrown‐ether complexes and markedly exceeding the stability of complexes of phenylazacrown ethers with the same macrocycle size. The structures of azacrown ethers and their complexes with Ba(ClO₄)₂ were studied by X‐ray diffraction. A high degree of pre‐organization of N‐methylbenzoazacrown ethers toward the formation of complexes with metal and ammonium cations was noted, which is due to the clear‐cut pyramidal geometry of the nitrogen atom and the orientation of the lone electron pairs (LEPs) of most heteroatoms towards the centre of the macroheterocycle. Copyright © 2009 John Wiley & Sons, Ltd.     

The influence of the proton affinity of molecules that form proton disolvates on disolvate hydrogen bridge parameters

The optimum structures of thirty three proton disolvates (B…H…B)⁺ and (B…H…S)⁺ containing O…H⁺…O, N…H⁺…N, and N…H⁺…O hydrogen bridges were calculated by the density functional theory method (B3LYP/6-31++G(d, p)). The bridge parameters are compared with the proton affinities (PAs) of B and S molecules. Several dependences between the PA or ΔPA = PA_B ? PA_S values and the R _OO, R _NN, and R _NO distances were established. It follows from these results that the proton affinity of oxygen-or nitrogen-containing molecules that form (B…H…B)⁺ and (B…H…S)⁺ ions is an important but not the only factor determining the geometric parameters of hydrogen bridges in them. The dependences obtained can be used to estimate the length of the central fragment of proton disolvates if the PA values of molecules in the disolvates are known. They also allow the degree of proton transfer (the R _N…H and R _H…O distances) to be estimated for N…H⁺…O bridges.     

Electron impact dissociation of ND<Superscript>+</Superscript>: formation of D<Superscript>+</Superscript>

Absolute cross sections for electron impact dissociation of ND⁺ leading to the formation of D⁺ have been measured by applying the animated electron-ion beam method in the energy range from the reaction threshold up to 2.5 keV. The maximum inclusive cross section is observed to be (16.8 ± 0.8) × 10⁻¹⁷ cm² at the electron energy of 65.1 eV. The appearance energy for the D⁺ production is measured to be (4.0 ± 0.5) eV. Collected data are analyzed in details by means of an original procedure in order to determine separately the contributions of dissociative channels. A specific Monte Carlo modeling has been developed, which is proven to reconstruct adequately the dissociative ionization cross section. The present energy thresholds provide information about the ground and excited states of the molecular ion, as well as about the possible population of the vibrational levels. The reaction D₂(v) + N⁺ (or H₂(v) + N⁺) is a probable source for that population and it constitutes the first step of the molecular activated processes, so the corresponding chain of reactions has to be considered to study the chemistry of plasma sources.     

Basicity of trifluoromethylsulfonylformamidines. DFT and FTIR study and NBO analysis

The effect of the electron–acceptor substituent CF₃SO₂ at the imine nitrogen atom on the basicity and the electron distribution in N,N‐alkylformamidines ( 1 , 2 , 3 , 4 , 5 ) was studied experimentally by the FTIR spectroscopy and theoretically at the DFT (B3LYP/6‐311+G(d,p)) level of theory, including the natural bond orbital (NBO) analysis. The calculated proton affinities of the imine nitrogen atom and the sulfonyl oxygen (PA_N′ and PA_O) depend on the atomic charges, the C?N′ and N′―S bond polarity and on the energy of interaction of the amine nitrogen and the oxygen lone pairs with antibonding π* and σ*‐orbitals. The basicity of the imine nitrogen atom is increased with the increase of the electron‐donating power of the substituent at the amine nitrogen atom due to stronger interaction n_N → π*_C?N′, but is decreased for the electron‐withdrawing groups MeSO₂ and CF₃SO₂ at the imine nitrogen atom in spite of the increase of this conjugation. Protonation of ( 1 , 2 , 3 , 4 , 5 ) in CH₂Cl₂ solution in the presence of CF₃SO₃H occurs at the imine nitrogen atom, while the formation of hydrogen bonds with 4‐fluorophenol takes place at the sulfonyl oxygen atom, whose basicity is lower than that of N,N′‐dimethylmethanesulfonamide but higher than of N,N′‐dimethyltrifluoromethanesulfonamide. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,Redetermination and Molecular Conformation Analysis of the Structure of 2,2′-Diaminodiphenyl Disulfide

A new synthesis and the crystal structure of C₁₂H₁₂N₂S₂ have been described and redetermined. In order to optimize the geometry of the molecule, the semi empirical methods MNDO, AMI and PM3 were used. The conformation of the energy profile showed that the minimum energy conformation has the torsion angle θ [Cl-Sl-Sl′-Cl′] near 90°. The energy barrier at 0° attributed to the lone pair repulsion of sulphur atoms and interactions between NH…S and H(C6)…S non-bonded atoms.     

2H NMR study of phase transition and hydrogen dynamics in hydrogen bonded organic antiferroelectric 55DMBP-H2ca

Hydrogen dynamics in one-dimensional hydrogen bonded organic antiferroelectric, co-crystal of 5,5’-dimethyl-2,2’-bipyridine (55DMBP) and chloranilic acid (H₂ca), was investigated by use of ²H high resolution solid-state NMR. The two types of hydrogen bonds O-H …N and N⁺-H …O^? in the antiferroelectric phase were clearly observed as the splitting of the side band of the ²H MAS NMR spectra of the acid-proton deuterated compound 55DMBP-D ₂ca. The temperature dependence of the spin-lattice relaxation time was measured of the N⁺-H and O-H deuterons, respectively. It was suggested that the motion of the O-H deuteron is already in the antiferroelectric phase in the fast-motion regime in the NMR time scale, while that of the N⁺-H deuteron is a slow motion. In the high-temperature paraelectric phase, the both deuterons become equivalent and the fast motion of the deuterons in the NMR time scale is taking place with the activation energy of 7.9 kJ mol^?1.     

Sulfur Isotopic Composition of H2S and SO4 2− from Mineral Springs in the Polish Carpathians

Abstract

A number of springs in Carpathian Mts. contain dissolved H₂S and SO₄ ^2- in concentrations above 10 mg/dm³. In this study we have investigated the sulfur isotope composition (δ³⁴S) of the dissolved sulfur species in the springs from the flysch area in the Carpathian Mts. along the tectonic dislocation. It is believed that some of these springs may carry a major fraction of dissolved sulfur species of extremely deep sulfur (of mantle origin), which is subjected to SO₄ ^2-—H₂S isotope exchange at high temperatures. The original isotopic compositions may be modified by reduction/oxidation at low temperatures and by admixture of sulfur from other sources.

In order to distinguish the sulfur of mantle origin we investigated δ³⁴S of dissolved sulfide and sulfate and on the basis of known concentrations we calculated δ³⁴S of total dissolved sulfur. The isotope fractionation between sulfate and sulfide helped to distinguish the sulfur origin. Evaluating the sulfur isotope exchange, we selected 4 springs which likely have only weakly disturbed sulfur of mantle origin.     

Methane-Derived Carbonates in a Native Sulfur Deposit: Stable Isotope and Trace Element Discriminations Related to the Transformation of Aragonite to Calcite

Abstract

Stable isotope (¹³C, ¹⁸O, ³⁴S) and trace element (Sr²⁺, Mg²⁺, Mn²⁺, Ba²⁺, Na⁺) investigations of elemental sulfur, primary calcites and mixtures of aragonite with secondary, post-aragonitic calcite from sulfur-bearing limestones have provided new insights into the geochemistry of the mineral forming environment of the native sulfur deposit at Machów (SE-Poland). The carbon isotopic composition of carbonates (δ¹³C = ?41 to ?47‰ vs. PDB) associated with native sulfur (δ³⁴S = + 10 to + 15‰ vs. V-CDT) relates their formation to the microbiological anaerobic oxidation of methane and the reduction of sulfate derived from Miocene gypsum. From a comparison with experimentally derived fractionation factors the element ratios of the aqueous fluids responsible for carbonate formation are estimated. In agreement with field and laboratory observations, ratios near seawater composition are obtained for primary aragonite, whereas the fluids were relatively enriched in dissolved calcium during the formation of primary and secondary calcites. Based on the oxygen isotope composition of the carbonates (δ¹⁸O = ?3.9 to ?5.9‰ vs. PDB) and a secondary SrSO₄ (δ¹⁸O = + 20‰ vs. SMOW; δ³⁴S = + 59‰ vs. V-CDT), maximum formation temperatures of 35°C (carbonates) and 47°C (celestite) are obtained, in agreement with estimates for West Ukraine sulfur ores. The sulfur isotopic composition of elemental sulfur associated with carbonates points to intense microbial reduction of sulfate derived from Miocene gypsum (δ³⁴S ≈ + 23‰) prior to the re-oxidation of dissolved reduced sulfur species.