摘要:

The ammonolysis of tetrakistrifluoromethyldiarsine probably proceeds through solvolytic fission of the As—As bond. Solvolysis of the diarsine by sodium methoxide in methanol does not seem to proceed by this mechanism. Chlorobistrifiuoromethylarsine is stable to ethanol and ethanethiol below 110° but reacts violently with solid sodium alcoholates to give only decomposition products. With solid sodium mercaptide chlorobistrifluoromethylarsine yields ethylmercaptobistrifiuoromethylarsine. This mercapto-arsine is also obtained by reacting iodobistrifluoromethylarsine with mercuric mercaptide. Ammonolysis and hydrolysis studies of the compounds R2AsCF3and RAs(CF3)2(R = C2H5, C4H9) indicate that the mechanism of solvolysis could be SN2.

ISSN:0008-4042    

DOI:10.1139/v62-092

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The vibration–rotation infrared absorption spectra of germyl fluoride and bromide have been observed. All of the fundamentals in GeH3F were located, and the rotational structure of theE-type bands were resolved and analyzed. The low-frequency band, ν3(a1), in GeH3Br was not observed but an estimate of its position was made from the frequencies of the combination band ν3 + ν6and of ν6. The rotational constantA″ and the Coriolis constants ζ4, ζ5, and ζ6were calculated for both molecules, and agreement with microwaveA″ values was satisfactory. Thermodynamic functions based upon a rigid-rotator, harmonic-oscillator model have been evaluated for germyl fluoride and bromide.

ISSN:0008-4042    

DOI:10.1139/v62-093

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

Homogeneity limits at 750 °C of the ternary DO2triarsenides (Ni,Co)As3, (Fe,Co)As3, and (Fe,Ni)As3have been established. The electrical and magnetic properties of these systems and the triarsenides of cobalt, rhodium, and iridium have been examined. The results are:These data are discussed with reference to the bonding model proposed by Dudkin and Abrikosov. The model is satisfactory for the binary compounds and the Ni/Co system, but not for the Fe/Co and Fe/Ni systems.

ISSN:0008-4042    

DOI:10.1139/v62-094

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The transfer of heat in a Tian–Calvet microcalorimeter is treated theoretically. Although quantitative agreement between predicted behavior and experimental observation is not obtained, the qualitative features brought out by the considerations should be helpful in the design and use of this type of calorimeter.

ISSN:0008-4042    

DOI:10.1139/v62-095

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The reaction of benzophenone phenylhydrazone with carbon monoxide at 230° and 3800 p.s.i. to give 3-phenylphthalimidine-N-carboxyanilide, and at lower temperatures (190–220°) to give a mixture of 3-phenylphthalimidme-N-carboxyanilide and 3-phenylphthalimidine has been studied. An independent synthesis of 3-phenylphthalimidine-N-carboxyanilide is described. 4-Methylbenzophenone phenylhydrazone reacted with carbon monoxide to give a mixture of two isomers, 3-phenyl-6-methylphthalimidine-N-carboxyanilide and 3-(p-tolyl)-phthalimidine-N-carboxyanilide, whose infrared spectra are described. An independent synthesis of 3-(p-tolyl)phthalimidine-N-carboxyanilide has also been carried out.

ISSN:0008-4042    

DOI:10.1139/v62-096

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The infrared spectra of solid films of piperidinium halides were measured at both room temperature and low temperatures. The spectra of the chloride and the bromide are not appreciably affected by cooling, but the spectrum of the iodide exhibits spectacular changes. These changes are explained by assuming the occurrence of a phase transition at about −15 °C. The possibility of a "chair" → "boat" interconversion is also discussed.

ISSN:0008-4042    

DOI:10.1139/v62-097

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The infrared spectra of anilinium chloride, bromide, and iodide, measured at 22 °C and at −190 °C, are presented. The spectrum of the chloride is essentially the same at both temperatures but the spectra of both the bromide and the iodide exhibit changes indicating a crystalline phase transition, in accordance with recent X-ray determinations of the crystal structures of these compounds.

ISSN:0008-4042    

DOI:10.1139/v62-098

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The action of nitrous acid on azomethines derived from the alkaloid atisine gave a good yield of nitrogen-free hemiacetal, thus providing the first means of removing the nitrogen from the diterpenoid alkaloids. Transformation products of the hemiacetal, including the most hindered carboxylic acid hitherto known, are described. The internal oxidation–reduction reactions encountered in this and related work are discussed.

ISSN:0008-4042    

DOI:10.1139/v62-099

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The Raman spectra of sulphuric acid, deuterosulphuric acid, chlorosulphuric acid, and methanesulphonic acid have been redetermined, and the spectrum of fluorosulphuric acid measured for the first time. The spectra of fluorosulphuric acid – sulphuric acid, chlorosulphuric acid – sulphuric acid, and fluorosulphuric acid – arsenic trifluoride mixtures have also been measured. The spectra of the hydrogen sulphate, deutero sulphate, fluorosulphate, chlorosulphate, and methanesulphonate anions have been obtained in various solvents. Frequencies are assigned to the normal modes of vibration of all these acids and their anions and the assignments are compared with those of previous workers.

ISSN:0008-4042    

DOI:10.1139/v62-100

出版商:NRC Research Press    

年代:1962

数据来源: NRC

摘要:

The Raman spectra of oleums, i.e. mixtures of sulphur trioxide and sulphuric acid, have been re-examined. Similar measurements on the sulphur trioxide – deuterosulphuric acid (D2SO4) system are also reported. The experimental results and conclusions of previous similar work on oleums are discussed. By comparison of the spectra of oleums with those of the polysulphuryl halides it is shown that the polysulphuric acids H2S2O7and H2S3O10are present in this system. The increase in the frequency of the SO2stretching vibrations with increasing concentration of sulphur trioxide gives evidence for the existence of higher polysulphuric acids such as H2S4O13at high concentrations of sulphur trioxide. In relatively concentrated oleum, sulphur trioxide monomer and trimer are also present. It is shown that the self-dissociation of liquid H2S2O7gives mainly molecular H2S2O10and H2SO4and not ionic species. The conclusions reached from the interpretation of the Raman spectra of the D2SO4–SO3system are similar to those arrived at for sulphuric acid oleums. The spectra of solutions of NaHSO4in oleums were also examined, and are discussed.

ISSN:0008-4042    

DOI:10.1139/v62-101

出版商:NRC Research Press    

年代:1962

数据来源: NRC