Hydrogen bonding. Part. 76. Molecular orbital investigation of the stability of tertiary amine-hydrogen fluoride compounds in aqueous solution

N,N-Dimethyl-1-adamantamine-hydrogen fluoride (2MAAHF) does not dissociate in aqueous solution, while 2MAAHCl and 2MAAHBr readily ionize in H₂O. Semi-empirical (AM1-SM2) calculations demonstrate that the enthalpic barrier to dissociation of 2MAAHF in aqueous solution is four times as high as that of 2MAAHCl and three times as high as that of 2MAAHBr. Ab initio calculations (3-21G(*) and 3-61G^*) show that 2MAAHF is a tightly bound molecular complex between neutral HF and neutral amine, with a low dipole moment and little negative charge exposed on fluorine. 2MAAHCl and 2MAAHBr are ion-pairs with an electrostatic hydrogen bond between cation and anion, large dipole moments, and exposed halogen atoms with high electrostatic potential; these factors explain the ease of ionization of 2MAAHCl and 2MAAHBr. Parallel studies on other tertiary amines give similar results.     

Hydrogen fluoride analyzer for gases and aerosols

Many fire suppression agents are currently used, and the replacement candidates for these agents contain fluorine atoms. When these agents are used to extinguish a fire, large quantities of hydrogen fluoride gas can be produced from the thermal degradation of fluorinated organic compounds. A real-time analyzer has been developed to measure exposure levels of hydrogen fluoride gas and aerosols during fire suppression tests. A vacuum pump pulls air through a continuous denuder, where the toxic gas and aerosols are extracted from the air into an aqueous trapping solution. The trapping solution then passes through a flow cell, where a fluoride ion-selective electrode measures the fluoride ion concentration. A solenoid pump moves the trapping solution and calibration standards through the analyzer. Once calibrated, the analyzer can generate a concentration profile of hydrogen fluoride versus time. This hydrogen fluoride analyzer is portable and can be calibrated in about 5 min. It provides rapid response to hydrogen fluoride gas and aerosols, over a detection range from 1 to 5000 mg/m³.     

Instantaneous and Selective Bare Eye Detection of Inorganic Fluoride Ion by Coumarin–Pyrazole‐Based Receptors

A series of rationally designed coumarin–pyrazole‐based scaffolds, equipped with N―H and C―H hydrogen bond donors ( R1–R5 ) and containing various electron‐withdrawing groups at key positions, are synthesized and characterized in order to investigate their inorganic fluoride binding properties in highly competitive media (1:1 DMSO–water). Only one, 3‐{4‐[(2,4‐dinitrophenyl)‐hydrazonomethyl]‐1‐phenyl‐1H‐pyrazol‐3‐yl}‐chromen‐2‐one ( R1 ), of the five compounds synthesized, is found to be capable to selectively detect inorganic fluoride via naked eye amongst other anionic species in aqueous media. Qualitative and spectroscopic studies exhibit that receptor R1 has the potential of showing instantaneous change of color from yellow to pink upon addition of sodium fluoride (0.95 ppm) in aqueous media, at concentration lower than that recommended by World Health Organization (1 ppm). Intensity of color increases with increasing fluoride concentration till 5 ppm, beyond which intensity of color change becomes saturated. This has established the applicability of this receptor for assessment of the level of fluoride in water. Anion binding studies carried out by UV–visible titration portrayed substantial bathochromic peak shift from 410 to 495 nm, upon addition of varying concentrations of aqueous sodium fluoride solution, which has validated the color change. Jobs plot data confirmed 1:1 stoichiometry between R1 and fluoride ion. ¹H‐NMR investigation reveals that the deprotonation of N―H hydrogen donor group of receptor R1 and its interaction with fluoride ion is responsible for the observed color change.     

Elimination of hydrogen fluoride from fluorinated succinic acids. (III) kinetics of dehydrofluorination of erythro- and threo-α-bromo-α′-fluorosuccinic acids

Treatment of $\text{erythro}$- and $\text{threo}$-α-bromo-α′-fluorosuccinic acids with aqueous alkali results in the elimination of hydrogen fluoride in preference to hydrogen bromide and gives almost exclusively bromofumaric acid. The elimination of hydrogen fluoride from the two above-mentioned acids is faster by 1–2 orders of magnitude than the elimination of hydrogen fluoride from any fluorinated succinic acids. Kinetic data based on ¹H NMR measurements are presented and possible mechanisms and stereochemistry involved are discussed.     

Synthesis and gas sorption properties of halogen-doped mesoporous chromium(iii) terephthalate

Mesoporous chromium(iii) terephthalate MIL-101 was treated with aqueous solutions of sodium fluoride, chloride, and bromide. The properties of the resulting compounds to sorb nitrogen, hydrogen, and methane were studied. The methane sorption was shown to depend on the nature of the inserted halide ion. The treatment with a sodium chloride solution leads to an increase in the methane uptake by MIL-101.     

Selective gas-chromatographic detection using an ion-selective electrode-II Selective detection of fluorine compounds

Components in samples are separated on a gas chromatography column using hydrogen as carrier gas. The individual components from the column are passed through a platinum tube heated at 1000 degrees , where they undergo hydrogenolysis, and fluorine compounds are converted into hydrogen fluoride. The hydrogen fluoride is dissolved in a slow stream of an absorption solution, and the fluoride ion concentration in the resulting solution is monitored in a flow-cell with a fluoride ion electrode. The potentiometric output of the cell is converted into a signal, which is proportional to the concentration of fluoride ion, by an antilogarithmic converter, and recorded. The response of the detector to fluorine compounds was about 10,000 times that to an equal quantity of other organic compounds, and 5 x 10(-11) mole of fluorobenzene could be detected.     

Catalytic oxidation of furan and hydrofuran compounds. 4. Oxidation of furfural by hydrogen peroxide in the presence of sodium molybdate

The oxidation of furfural by an aqueous solution of hydrogen peroxide in the presence of sodium molybdate was studied for the first time. Its final products are 2(5H)-furanone and also tartaric, malic, and succinic acids. The process takes place through the formation of peroxide and carbonyl compounds. Kinetic curves for the consumption of the reagents and the accumulation of the reaction products were obtained. In direction oxidation in this system differs substantially from the previously studied reactions of furfural with an aqueous solution of hydrogen peroxide without a catalyst and in the presence of selenium and vanadium compounds.For Communication 3, see [1].Kubansk State Technological University, Krasnodar 350072, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–903, July, 1998.     

Structural and dynamical properties of hydrogen fluoride in aqueous solution: an ab initio quantum mechanical charge field molecular dynamics simulation

The novel ab initio quantum mechanical charge field (QMCF) molecular dynamics simulation at the Hartree-Fock level has been employed to investigate hydration structure and dynamics of hydrogen fluoride in aqueous solution. The average H-F bond length of 0.93 A obtained from the QMCF MD simulation is in good agreement with the experimental data. The HHF...Ow distance of 1.62 A was evaluated for the first hydration shell, and 2.00 A was observed for the FHF...Hw distance. The stability of hydrogen bonding is more pronounced in the hydrogen site of hydrogen fluoride, with a single water molecule in this part of the first hydration shell. A wide range of coordination numbers between 3 and 9 with an average value of 5.6 was obtained for the fluorine site. The force constants of 819.1 and 5.9 N/m were obtained for the HHF-FHF and HHF...Ow interactions, respectively, proving the stability of the nondissociated form of hydrogen fluoride in aqueous solution. The mean residence times of 2.1 and 2.5 ps were determined for ligand exchange processes in the neighborhood of fluorine and hydrogen atoms of hydrogen fluoride, respectively, indicating a weak structure-making effect of hydrogen fluoride in water. The corresponding H-bond lifetimes attribute this effect to the H atom site of HF.     

Fluorination with ionic liquid EMIMF(HF)2.3 as mild HF source

Hydrogen fluoride is a basic fluorinating reagent, but handling it is difficult. For this reason, some modified fluorinating reagents such as HF-pyridine, Et₃N-HF, and poly(hydrogen fluoride) complex have been developed. Those reagents, however, still require aqueous work-up procedures which generate hydrogen fluoride. Recently, ionic liquids have received much attention because of the ease in handling them and the possibility of non-aqueous work-up. An ionic liquid, 3-ethyl-1-methyimidazolium oligo hydrogen fluoride (EMIMF(HF)_2.3), which is stable in air and moisture, can be used as a hydrogen fluoride equivalent for some fluorination reactions; it does not require an aqueous work-up.     

Beitrag zur Synthese des Hydroxylammoniumfluorids

Summary Hydroxylammonium fluoride was prepared in aqueous solution by the reaction of hydroxylamine with aqueous hydrogen fluoride. The solubility in water (148.7 g/100 g) and ethanol (0.146 g/100 g), the density (1.621±0.005 g/cm³) and the metling point (97.8±2 °C) of the compound have been determined. [NH₃OH]F crystallizes orthorombic, P_abc,a=6.490(1) Å,b=9.799(1) Å,c=13.519(2) Å.

     

Spectres de vibration de l'acide cyclopropane dicarboxylique-1.1 et de ses sels de potassium en solution aqueuse

Raman and infrared spectra of the cyclopropane-1.1 dicarboxylic acid and its potassium salts in aqueous solution were recorded from 100 to 4000 cm⁻¹. An assignment of the observed lines as fundamentals is proposed. The analysis of the polarization of the Raman lines indicated that the salts belong to the C₂ group. The intramolecular hydrogen bonds which exist in the acid, persist in aqueous solution in both the acid and the acid salt.     

Graphite fluoride intercalation compounds for manufacturing composites with metal nanoparticles

The feasibility of using graphite fluoride intercalation compounds (GFICs) containing metal compounds for manufacturing metal nanoparticles in a graphite or graphite fluoride matrix is shown using the hydrogen reduction of a dicarbon fluoride matrix intercalated with a chloroform solution of palladium acetylacetonate Pd(AA)₂. The composite manufactured with a GFIC containing about 10.5 wt % Pd(AA)₂ at 80°C is Pd-fluorographite; at 450°C, Pd-graphite is manufactured. The palladium particle size in the composites is about 20–30 nm; the palladium concentration is about 5 and 9 wt %, respectively.     

A High-Yield Preparative-Scale Method for 2-Bromofuran

Recently¹ we reported excellent preparative methods for 2-bromothiophene involving addition of hydrogen peroxide to a mixture of concentrated aqueous hydrogen bromide, thiophene and diethyl ether or addition of a solution of bromine in concentrated aqueous hydrogen bromide to a mixture of thiophen, diethyl ether and aqueous hydrogen bromide. Similar procedures with furan gave intractable mixtures of unindentified products. A literature search afforded only two procedures^2,3 for the direct bromination of furan, viz. the reactions of furan with hexabromocyclopentadiene and the bromine-dioxan complex. Although good yields are reported, these methods do not seem attractive for the preparation of 2-bromofuran in sizable amounts. We have applied the well-established reaction of lithium compounds with elemental bromine to prepare 2-bromofuran.     

Preparation and examination of the properties of complex scandium fluorides

Precipitation of scandium with sodium fluoride from an ammonium hydrogen difluoride solution was examined at the molar ratios of Na to Sc within 1–14 and different initial concentrations of scandium in solution. The composition of the resulting precipitate was determined by X-ray phase analysis method. The solubility of the scandium compounds synthesized was examined.     

Enthalpie de dissolution a 298 K des fluorures de potassium et de cesium dans l'acide fluorhydrique et le fluorure d'hydrogene

A calorimetric cell designed for studies of reaction in anhydrous hydrogen fluoride has been constructed. Enthalpies of solution of KF and CsF in aqueous solution of HF (from 0 to 100 % HF) have been measured.     

Application of n-Bu4NHF2 as a fluorinating agent for the preparation of fluoroanions: synthesis and crystal structure of the anions [t-BuPO3AlF2]2(2-), [PhPO3AlF2]2(2-), and [(O-i-Pr)3Ti(mu-F)2(mu-O-i-Pr)Ti(O-i-Pr)3]-

The first phosphonate anions of aluminum-containing fluorine and an anionic bridged fluoroalkoxy derivative of titanium have been realized using n-Bu4NHF2 as a fluorinating agent in organometallic synthesis. Reactions of [RPO3AlMe]4 [R = Ph (1), t-Bu] with n-Bu4NHF2 yield organic-soluble compounds of the type [n-Bu4N]2[RPO3AlF2]2 [R = Ph (2), t-Bu (3)], whereas the reaction of Ti(O-i-Pr)4 with n-Bu4NHF2 results in the formation of [n-Bu4N][O-i-Pr)3Ti(mu-F)2(mu-O-i-Pr)Ti(O-i-Pr)3] (4). These compounds have been obtained in high yields and have been adequately characterized through spectroscopic techniques and X-ray diffraction studies.     

无氧条件下Pt/TiO2光催化重整降解一乙醇胺水溶液制氢

以一乙醇胺（以下简称乙醇胺）为电子给体,在无氧条件下进行了Pt/TiO2光催化重整制氢的研究.详细讨论了诸多因素如催化剂表面Pt化学状态、Pt担载量、溶液pH值、乙醇胺溶液浓度等对产氢效率的影响,并用XRD、HNMR、XPS等进行了深入表征,探讨了Pt/TiO2光催化重整降解乙醇胺和产氢的反应, 实验表明,利用所制备的光催化剂, 可实现在消除水中有机污染物的同时制取氢气的目标.催化剂表面的Pt以Pt0的化学状态存在, 有利于析氢;溶液pH值和浓度的变化对产生速率也有一定的影响.同时发现Pt/TiO2光催化重整乙醇胺制氢反应的最佳条件是:Pt的最佳担载量约为0.5％～1.0％;乙醇胺溶液最佳浓度约为0.05 mol•L－1;最佳溶液pH值范围为4～10;氨基取代的羰基类化合物是其主要中间产物.     

Hydrogen bonding: Part 18. The nature of the OHF hydrogen bond in choline fluoride

The infrared spectrum of the OHF hydrogen bond in choline fluoride is completely different from the spectra of the electrostatic O—H?X hydrogen bonds in the other choline halides; however, this spectrum cannot be accounted for in terms of a “very strong” covalent OHF bond such as those found in carboxylic acid—fluoride ion complexes or postulated for betaine hydrofluoride. The spectrum of choline fluoride is interpreted best in terms of an intermediate type of unsymmetrical hydrogen bond (r° O?F = ～ 256 pm) which shows strong intensity enhancement for the first overtone of the OHF bending vibration.     

Preparation and characterization of natural zeolite supported nano TiO2 photocatalysts by a modified electrostatic self‐assembly method

Natural zeolite supported nano TiO₂ photocatalysts were prepared by a modified electrostatic self‐assembly (ESA) method. First, γ‐mercaptopropyltrimethoxysilane with sulfhydryl (―SH) functional groups was modified on the zeolite powders by using a ‘dry process’. Second, silane with ―SH functional groups was oxidized to sulfonate (―SO₃H) groups by using a hydrogen peroxide/glacial acetic acid mixed solution, and the surface of ―SO₃H silane–zeolite was electronegative charged due to the ionization of ―SO₃H. Third, the hydrolytic titanium polycation from TiCl₄ solution assembled onto the electronegative charged zeolite under electrostatic attraction in the reaction solutions. Finally, zeolite supported nano TiO₂ photocatalysts can be obtained after the above compounds calcined at certain temperature. The samples were characterized by X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface areas, Fourier transform infrared spectroscopy (FT‐IR), X‐ray photoelectron spectroscopy (XPS) and X‐ray fluorescence (XRF). The photocatalytic activities of the samples were evaluated by the degradation of methyl orange in aqueous solution. The results showed that ESA method effectively improved the composite efficiency of zeolite with TiO₂. The photocatalysts prepared by ESA method exhibited higher photocatalytic and recycling activities than that of traditional method. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation of ion-selective electrodes based on quanternary phosphonium salts: Part 3. An Ion-Selective Electrode for Hexafluorophosphate

A hexafluorophosphate-selective electrode based on the tetradecylphosphonium hexafluorophosphate(V) ion-pair complex in a PVC membrane is described. The active material is a white powder; its solution in dibutyl phthalate was used for the electrode membranes. The composition of the tetradecylphosphonium hexafluorophosphate was identified as its infrared and ³¹P-n.m.r. spectra. The calibration curves for the elelctrode were investigated and interpreted with respect to the hydrogen fluoride concentration of the sample solution. It is shown that the hydrolysis of hexafluorophosphate depends on the hydrofluoric acid content of the solution. The lifetime of the electrodes is about one month and the limits of detection vary from aobut 10^?7 mol 1^?1 to 10^?6 mol 1^?1 with 0–1 mol 1^?1 hydrofluoric acid present.