7783-54-2Relevant articles and documents
NF3 synthesis using ClF3 as a mediator
Miyazaki, Tatsuo,Mori, Isamu,Umezaki, Tomonori,Yonezawa, Susumu
, p. 55 - 61 (2019)
Synthesis of NF3 using NH4F/nHF and F2 with ClF3, NF2Cl, and NFCl2 intermediates was conducted by sequential reaction testing for more than 100 h. Results demonstrated that NF3 can be synthesized with yield of more than 90% - fluorine molecule base. The ClF3 produced as a by-product can be recycled for reaction with NH4F/nHF. Improving the yield necessitates ClF3 recovery rate improvement, but characteristics of using ClF + F2 = ClF3 as an equilibrium reaction can be overcome with a two-step reaction. NH4F/nHF can be recycled continuously by controlling the n value in NH4F/nHF through NH3 addition and HF extraction. Using ClF3 as a mediator and NH3 and F2 as raw materials, NF3 synthesis was achieved at atmospheric pressure.
Performances of metal fluoride added carbon anodes with pre-electrolysis for electrolytic synthesis of NF3
Isogai, Tomohiro,Hirooka, Kazuhiro,Tojo, Tetsuro,Takebayashi, Hitoshi,Saito, Morihiro,Inaba, Minoru,Tasaka, Akimasa
, p. 4425 - 4432 (2011)
Metal fluoride added carbon anodes treated by pre-electrolysis were investigated for electrolytic production of nitrogen trifluoride (NF 3) in molten NH4F·KF·4HF at 100 °C. The conditions for pre-electrolysis were first optimized using a graphite sheet anode as a model anode. The formation of fluorine-graphite intercalation compounds (fluorine-GICs) with semi-covalent C-F bonds, (CxF) n, on the MgF2 and CaF2 added carbon anode surface was accelerated by pre-electrolysis at potentials less than 4.0 V. Critical current densities (CCD) on the MgF2 added carbon anodes pre-electrolyzed under various conditions were determined, and the highest CCD was 290 mA cm-2 obtained for that pre-electrolyzed at 3.5 V for 500 C cm-2. This anode was successfully used in the electrolysis at 100 mA cm-2 for 290 h and the maximum NF3 current efficiency was 55%. From these results, it was concluded that the metal fluoride added carbon anode treated by pre-electrolysis has a high potential for electrolytic production of NF3 at higher current density.
Preparation of a nickel-nickel oxide composite by hot isostatic pressing and its application for anodes used in electrolytic production of nitrogen trifluoride
Tasaka, Akimasa,Suzuki, Yasuhiro,Oshida, Atsushi,Mimoto, Atsuhisa,Hieda, Taro,Tachikawa, Toshiyasu,Takao, Kazuchika,Takemura, Hideaki,Yamaguchi, Osamu
, p. D108-D116 (2003)
The nickel-nickel oxide [Ni-NiO1+x (0 a mixture of Ni and LiNiO2 or NiO powders at 900°C under 2000 atm for 2 h by hot isostatic pressing were employed as the anode for electrolytic production of NF3. In electrolysis of a molten NH4F·2HF with and without LiF at 100°C and at 25 mA/cm2, the anode gas generated at the Ni-NiO1+x composite anode was composed of N2, O2, NF3, N2F2, N2F4, and N2O, and its composition was composition was almost the same as that at the Ni sheet anode. The current efficiency for NF3 formation on the Ni-NiO composite anode from mixture of NiO and Ni powders was high compared with that on the Ni-NiO1+x composite anode from the mixture of LiNiO2 and Ni powders. The best current efficiency for NF3 formation was ca. 53% on the Ni 5 mol% NiO composite anode, and it was almost the same as that of the Ni sheet anode. The addition of LiF in a molten NH4F·2HF increased it, presumably because of deposition of Li2NiF6 on the anode. On the other hand, the anode consumption of the Ni-NiO composite was much smaller compared with that of the Ni sheet electrode. Also, the oxygen content in the oxidized layer formed on the Ni-NiO composite anode was high compared with that on the Ni sheet anode. The scanning electron microscope observation revealed that the surface of the Ni-NiO composite anode was covered with the compact film having some defects. From these results, it is concluded that the Ni-NiO composite anode is favorable for electrolytic production of NF3, and that the oxidized layer on the anode has a high resistance to corrosion, because of the compact film containing a higher content of oxygen formed on the anode.
Electrolytic production of NF3 with a LiNiO2 coated nickel sheet anode prepared by atmospheric plasma spraying technique
Tasaka,Suzuki,Sakaguchi,Fukuda,Tojo
, p. 4349 - 4358 (2001)
A nickel sheet coated with LiNiO2 powder having average particle sizes of 40 and 50 μm in diameter by atmospheric plasma spraying technique was employed as the anode for electrolytic production of NF3. In electrolysis of a molten NH4F·2HF at 100°C and 25 mA cm-2, the anode gas generated at the LiNiO2 coated Ni sheet anode was composed of N2, O2, NF3, N2F2, N2F4, and N2O, and its composition was almost the same as that at the Ni sheet anode. The current efficiency for the NF3 formation on the LiNiO2 coated Ni sheet anode was increased to reach the constant value of ca. 55% during electrolysis for 100 h, and it was almost the same as that on the Ni sheet anode. The anode consumption of the LiNiO2 coated Ni sheet was small compared with that of the Ni sheet. Also, the oxygen content in the oxidized layer formed on the LiNiO2 coated Ni sheet anode was high compared with that on the Ni sheet anode, and the surface of the LiNiO2 coated Ni sheet anode was covered with a compact and adhesive film having some defects. Although the bottom of the hollow was covered with a thinner layer, no pore penetrated through the oxidized layer. Hence, the LiNiO2 coated Ni sheet anode is favorable for the electrolytic production of NF3, and the oxidized layer on the LiNiO2 coated Ni sheet anode has the higher resistance to corrosion, because of the compact and adhesive film containing the higher content of oxygen formed on the anode.
Process for fluorinating inorganic or organic compounds by direct fluorination
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Paragraph 00273-00274; 0307-0312, (2020/07/14)
The invention relates to the use of a fluorinated gas, wherein the elemental fluorine (F2) is present at a high concentration, the present invention relates to a process for producing fluorinated compounds by direct fluorination using a fluorination gas in which elemental fluorine (F2) is present at a high concentration, such as a concentration of elemental fluorine (F2), in particular equal to much higher than 15 vol% or even 20 vol% (i.e., at least 15 vol% or even 20 vol%), and to a process for producing fluorinated compounds by direct fluorination using a fluorination gas. The process of the present invention relates to the manufacture of fluorinated compounds other than fluorinated benzene by direct fluorination, in particular to the preparation of fluorinated organic compounds, end products and intermediates for use in agricultural, pharmaceutical, electronic, catalyst, solvent and other functional chemical applications. The fluorination process of the invention can be carried outin batches or in a continuous manner. If the process of the invention is carried out in batches, a column (tower) reactor may be used. If the process of the invention is continuous, a microreactor may be used.
Dinitrogen difluoride chemistry. Improved syntheses of cis- and trans-N2F2, Synthesis and characterization of N 2F+Sn2F9-, ordered crystal structure of N2F+Sb2F11 -, High-level electronic structure calculations of cis-N 2F2
Christe, Karl O.,Dixon, David A.,Grant, Daniel J.,Haiges, Ralf,Tham, Fook S.,Vij, Ashwani,Vij, Vandana,Wang, Tsang-Hsiu,Wilson, William W.
, p. 6823 - 6833 (2010/09/06)
N2F+ salts are important precursors in the synthesis of N5+ compounds, and better methods are reported for their larger scale production. A new, marginally stable N2F + salt, N2F+Sn2F9 -, was prepared and characterized. An ordered crystal structure was obtained for N2F+Sb2F11-, resulting in the first observation of individual N - N and N-F bond distances for N2F+ in the solid phase. The observed N - N and N-F bond distances of 1.089(9) and 1.257(8) A, respectively, are among the shortest experimentally observed N-N and N-F bonds. High-level electronic structure calculations at the CCSD(T) level with correlation-consistent basis sets extrapolated to the complete basis limit show that cis-N2F 2 is more stable than trans-N2F2 by 1.4 kcal/mol at 298 K. The calculations also demonstrate that the lowest uncatalyzed pathway for the trans-cis isomerization of N2F2 has a barrier of 60 kcal/mol and involves rotation about the N - N double bond. This barrier is substantially higher than the energy required for the dissociation of N2F2 to N2 and 2 F. Therefore, some of the N2F2 dissociates before undergoing an uncatalyzed isomerization, with some of the dissociation products probably catalyzing the isomerization. Furthermore, it is shown that the trans-cis isomerization of N2F2 is catalyzed by strong Lewis acids, involves a planar transition state of symmetry Cs, and yields a 9:1 equilibrium mixture of cis-N2F2 and trans-N2F2. Explanations are given for the increased reactivity of cis-N2F 2 with Lewis acids and the exclusive formation of cis-N 2F2 in the reaction of N2F+ with F-. The geometry and vibrational frequencies of the F2N - N isomer have also been calculated and imply strong contributions from ionic N2F+ F- resonance structures, similar to those in F3NO and FNO.
On the reactivity of F3S≡NXeF+: Syntheses and structural characterizations of [F4S=N-Xe - N≡SF 3][AsF6], a rare example of a N-Xe-N Linkage, and [F 3S(N≡SF3)2][AsF6]
Smith, Gregory L.,Schrobilgen, Gary J.
, p. 7714 - 7728 (2011/02/27)
The F4S=N-Xe-N≡SF3+ cation has been synthesized as the AsF6- salt by rearrangement of [F 3S≡NXeF]-[AsF6] in N≡SF3 solvent at 0 °C. Deep yellow [F4S=N-Xe - N≡SF3][AsF 6], which crystallized from a N≡SF3 solution at -10 °C, was characterized by Raman spectroscopy (-160 °C) and by single-crystal X-ray diffraction (-173 °C). The Xe-N bond length (2.079(3) a) of the F4S=N-Xe - N≡SF3+ cation is among the shortest Xe-N bonds presently known. The F4S=NXe + cation interacts with N≡SF3 by means of a Xe - N donor-acceptor bond (2.583(3) a) that is significantly longer than the primary Xe-N bond (2.079(3)a) but significantly shorter than the sum of the Xe and N van der Waals radii (3.71 a). The F4S=N-Xe - N≡SF3+ cation undergoes a redox decomposition in N≡SF3 at 0 °C, forming [F3S(N≡SF 3)2][AsF6], cis-N2F2, and Xe, which were characterized by low-temperature Raman spectroscopy in the solid state and by 19F NMR spectroscopy in N≡SF3 solvent (0 °C). Colorless [F3S(N≡SF3) 2][AsF6] crystallized from N≡SF3 at -10 °C and was characterized by low-temperature, single-crystal X-ray diffraction. The S(IV) atom of F3S(N≡SF3) 2 + has long contacts with the N atoms of two N≡SF3 molecules and a F ligand of a neighboring AsF 6- anion. The arrangement of long contacts avoids, to the maximum extent, the F atoms of SF3+ and the nonbonding electron pair situated on the pseudo-3-fold axis opposite the F ligands of SF3+, providing distorted octahedral coordination about the S(IV) atom. Quantum-chemical calculations using MP2, B3LYP, and PBE1PBE methods were employed to arrive at the gas-phase geometries, charges, bond orders, valencies, and vibrational frequencies for F4S=N-Xe - N≡SF3+ and F3S(N≡SF 3)2+ to aid in the assignments of experimental vibrational frequencies. The F4S=N-Xe - N≡SF3 + cation expands the known chemistry of the F4S=N- group and is the first example of a N-Xe-N linkage to be structurally characterized by single-crystal X-ray diffraction.
Development and implementation of industrial technologies for synthesis of fluorine compound with the application of elemental fluorine
Pashkevich,Barabanov,Maksimov
, p. 1142 - 1148 (2009/12/01)
A survey is given on the application of elemental fluorine in chemical plants and research centers of Russian Federation.
Industrial fluorine compounds
Barabanov,Maksimov
, p. 1133 - 1141 (2009/12/01)
Technological research in the area of the industrial fluorine-containing compounds: ozone safe fluorocarbons (freons), fluoro-olefins, compounds with the functional groups, thermoresistant liquids, oils, lubricants, fluorine surfactants and other.
Synthesis and characterization of (Z)-[N3NFO]+ and (E)-[N3NFO]+
Wilson, William W.,Haiges, Ralf,Boatz, Jerry A.,Christe, Karl O.
, p. 3023 - 3027 (2008/03/11)
(Figure Presented) A new stable polynitrogen ion: The second known example of a stable nitrogen fluoride oxide ion, [N3NFO]+, was prepared as its [SbF6]- salt and characterized by multinuclear NMR and vibrational spectroscopy and electronic-structure calculations. The cation is planar and exists as two stereoisomers (see picture; N blue, O red, F dark blue).
