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Moisture of several ppm in hydrogen chloride gas has been accurately determined by a new method using the Karl Fischer reagent, which hitherto had a limitation in accuracy because of a partial reaction with hydrogen chloride when direct titration was employed.The moisture in the sample gas was collected in a cold trap kept at about ?80 °C while the hydrogen chloride gas passed through and the frozen moisture was dissolved by pyridine-methanol (1:1) solvent. a KF Reagent of factoe: 0.35 mg H2O/ml.Titration by the Karl Fischer reagent having the equivalency factor of, e.g., 0.5 mg H2O/ml was carried out and the concentration of the moisture was calculated from the sample volume used. 相似文献
45.
Yasushi Mizobe Reiko Ono Yasuzo Uchida Masanobu Hidai Meguru Tezuka Suehiro Moue Atsuhiko Tsuchiya 《Journal of organometallic chemistry》1980,204(3):377-385
Diazoalkane complexes of type [MF(NNCRR′)(dpe)2][BF4] (M = Mo or W; dpe = Ph2PCH2CH2PPh2), which are easily derived from bis(dinitrogen) complexes [M(N2)2(dpe)2], undergo consecutive one- and two-electron oxidations and reductions under voltammetric conditions at a platinum electrode. The ESR spectra of the species generated by the controlled potential electrolysis show that primary oxidation occurred on the metal atom (M = Mo) and reduction on the two nitrogen atoms in the diazoalkane ligands (M = Mo or W). 相似文献
46.
Eiji Kamio Aiko Kato Satoshi Yonemura Tsutomu Ono Hidekazu Yoshizawa 《Colloid and polymer science》2008,286(6-7):787-793
Monodisperse polymelamine microcapsules were prepared by phase separation method. Control of microcapsule diameter was investigated using the uniform-sized oil-in-water emulsion droplets as the capsule core. The monodisperse emulsion droplets were prepared using the Shirasu porous glass (SPG) membrane emulsification technique. The effects of the diameter of the oil droplet and concentration of sodium dodecyl sulfate (SDS), which is a typical emulsifier in SPG membrane emulsification, on microencapsulation were investigated. The microcapsules were aggregated when oil droplets with small size were microencapsulated at high SDS concentration. To reduce the SDS concentration, the creamed emulsion was used. The monodisperse polymelamine microcapsules were successfully prepared by using the creamed emulsion. The microcapsule diameter was almost similar to the diameter of the encapsulated oil droplet. The coefficient of variation values was about 10% for all microcapsules prepared in this study. Control of microcapsule diameter was achieved in the range of 5–60 μm. 相似文献
47.
Abstract The molecular and crystal structure of a 1:1 co-crystal of 4,4′-dimethyl-7,7′-bi([1,2,5]thiadiazolo[3,4-b]pyridylidene)–chloranilic acid, (1), has been determined by X-ray diffraction at the monoclinic space group P21/c with cell parameters of a = 8.422(6), b = 7.343(4), c = 16.112(7) ?, β = 104.988(8)°, V = 962.5(10) ?3 and Z = 2. In the crystal structure, two components connect via the intermolecular O–H···N hydrogen bonds [2.804(4) ?] and S···O
heteroatom interaction [2.945(3) ?] with R
2
2(7) couplings to form a unique and infinite one-dimensional supramolecular tape structure. The calculations of (1) at the HF/6-31G(d), MP2/6-31G(d), and B3LYP/6-31G(d) levels can almost reproduce X-ray geometry. In addition, the distances
of the intermolecular O–H···N and S···O interactions by MP2/6-31G(d) and B3LYP/6-31G(d) levels agree well with those in the
crystal. The calculated binding energies corrected BSSE and ZPE are −4.487 (HF), −7.473 (MP2), and −5.640 (B3LYP) kcal/mol.
The results suggest that the complex (1) is very stable and the dispersion interaction is significantly important for the attractive intermolecular interaction in
(1). The NBO analysis has revealed that the n(N) → σ*(O–H) interaction gives the strongest stabilization to the system and the major interaction for the intermolecular
S···O contact is n(O) → σ*(S–N).
Index Abstract In the crystal structure of the title compound, the molecules are linked by intermolecular O–H···N hydrogen bonds and short
S···O heteroatom interactions with R
2
2(7) couplings to construct a unique and infinite one-dimensional supramolecular tape structure.
相似文献
48.
Takafumi Kondoh Akira Asano Jinfeng Yang Kimihiro Norizawa Kenji Takahashi Mitsumasa Taguchi Ryuji Nagaishi Ryuzi Katoh Yoichi Yoshida 《Radiation Physics and Chemistry》2009,78(12):1157-1160
The spectra and kinetic behavior of solvated electrons (esol−) in alkyl ammonium ionic liquids (ILs), i.e. N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMMA-BF4), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13-TFSI), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13-TFSI), and N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P14-TFSI) were investigated by the pulse radiolysis method. The esol− in each of the ammonium ILs has an absorption peak at 1100 nm, with molar absorption coefficients of 1.5–2.3×104 dm3 mol−1 cm−1. The esol− decayed by first order with a rate constant of 1.4–6.4×106 s−1. The reaction rate constant of the solvated electron with pyrene (Py) was 1.5–3.5×108 dm3 mol−1 s−1 in the various ILs. These values were about one order of magnitude higher than the diffusion-controlled limits calculated from measured viscosities. The radiolytic yields (G-value) of the esol− were 0.8–1.7×10−7 mol J−1. The formation rate constant of esol− in DEMMA-TFSI was 3.9×1010 s−1. The dry electron (edry−) in DEMMA-TFSI reacts with Py with a rate constant of 7.9×1011 dm3 mol−1 s−1, three orders of magnitude higher than that of the esol− reactions. The G-value of the esol− in the picosecond time region is 1.2×10−7 mol J−1. The capture of edry− by scavengers was found to be very fast in ILs. 相似文献
49.
Fujisawa K Ono T Ishikawa Y Amir N Miyashita Y Okamoto K Lehnert N 《Inorganic chemistry》2006,45(4):1698-1713
Copper(I) complexes with tripodal nitrogen-containing neutral ligands such as tris(3,5-diisopropyl-1-pyrazolyl)methane (L1') and tris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)methane (L3'), and with corresponding anionic ligands such as hydrotris(3,5-diisopropyl-1-pyrazolyl)borate (L1-) and hydrotris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)borate (L3-) were synthesized and structurally characterized. Copper(I) complexes [Cu(L1')Cl] (1), [Cu(L1')(OClO3)] (2), [Cu(L1')(NCMe)](PF6) (3a), [Cu(L1')(NCMe)](ClO4) (3b), [Cu(L1')(CO)](PF6) (4a), and [Cu(L1')(CO)](ClO4) (4b) were prepared using the ligand L1'. Copper(I) complexes [Cu(L3')Cl] (5) and [Cu(L3')(NCMe)](PF6) (6) with the ligand L3' were also synthesized. Copper(I) complexes [Cu(L1)(NCMe)] (7) and [Cu(L1)(CO)] (8) were prepared using the anionic ligand L1-. Finally, copper(I) complexes with anionic ligand L3- and acetonitrile (9) and carbon monoxide (10) were synthesized. The complexes obtained were fully characterized by IR, far-IR, 1H NMR, and 13C NMR spectroscopy. The structures of both ligands, L1' and L3', and of complexes 1, 2, 3a, 3b, 4a, 4b, 5, 6, 7, and 10 were determined by X-ray crystallography. The effects of the differences in (a) the fourth ligand and the counteranion, (b) the steric hindrance at the third position of the pyrazolyl rings, and most importantly, (c) the charge of the N3 type ligands, on the structures, spectroscopic properties, and reactivities of the copper(I) complexes are discussed. The observed differences in the reactivities toward O2 of the copper(I) acetonitrile complexes are traced back to differences in the oxidation potentials determined by cyclic voltammetry. A special focus is set on the carbonyl complexes, where the 13C NMR and vibrational data are presented. Density functional theory (DFT) calculations are used to shed light on the differences in CO bonding in the compounds with neutral and anionic N3 ligands. In correlation with the vibrational and electrochemical data of these complexes, it is demonstrated that the C-O stretching vibration is a sensitive probe for the "electron richness" of copper(I) in these compounds. 相似文献
50.
Kyosuke Doi Yuki Yamada Masaki Okoshi Junichi Ono Chien‐Pin Chou Hiromi Nakai Atsuo Yamada 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8108-8112
Alkaline metals are an ideal negative electrode for rechargeable batteries. Forming a fluorine‐rich interphase by a fluorinated electrolyte is recognized as key to utilizing lithium metal electrodes, and the same strategy is being applied to sodium metal electrodes. However, their reversible plating/stripping reactions have yet to be achieved. Herein, we report a contrary concept of fluorine‐free electrolytes for sodium metal batteries. A sodium tetraphenylborate/monoglyme electrolyte enables reversible sodium plating/stripping at an average Coulombic efficiency of 99.85 % over 300 cycles. Importantly, the interphase is composed mainly of carbon, oxygen, and sodium elements with a negligible presence of fluorine, but it has both high stability and extremely low resistance. This work suggests a new direction for stabilizing sodium metal electrodes via fluorine‐free interphases. 相似文献