摘要:

Phosphoryl fluoride reacts with dimethylamine in an equimolar ratio to yield volatile dimethylaminophosphoryldifluoride. The residual solid is a mixture of dimethylammonium hexafluorophosphate and dimethylammonium difluorophosphate salts rather than the simple fluoride salt. Dimethylamine reacts slowly with dimethylaminophosphoryldifluoride to yield bis(dimethylamino)phosphorylfluoride and the same complex fluorophosphate anions in the solid products. Physical data are reported on the alkylamino phosphoryl fluorides. The reaction of the difluorophosphoryl compound with hydrogen halides has been studied.

ISSN:0008-4042    

DOI:10.1139/v67-217

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The concurrent ion–molecule reactions in mixtures of HCl and HCN with D2and CD4have been studied by the ratio plot method. The following reactions have been detected in mixtures with HCN and their cross sections determined at 10.5 V cm−1repeller field strength.In mixtures of D2and CD4with HCl the following reactions have been detected and cross sections determined.Rate constants for the self-reactions in HCN and HCl have been measured both at 10.5 V cm1repeller field and at thermal ion energies.

ISSN:0008-4042    

DOI:10.1139/v67-218

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Two crystalline complexes of 1,3-butadiene with anhydrous silver tetrafluoroborate have been isolated and shown to have the stoichiometryand. On the basis of their infrared spectra, it has been suggested that in the solid state the 1:1 complex is polymeric in nature with alternating butadiene molecules and AgBF4units in the chain and that the 2:3 complex is formed by bridging of butadiene molecules between silver ions in adjacent chains.

ISSN:0008-4042    

DOI:10.1139/v67-219

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The infrared spectra of the complexes [Ru(NH3)6]X2and [Ru(NH3)6]X3, where X = Cl−, Br−, I−, BF4−and [Ru(NH3)5X]X2, where X = Cl−, Br−and I−, have been measured in the solid state between 4 000 – 250 cm−1. Assignments have been made for the observed absorption bands. The metal–nitrogen stretching vibrations were observed between 485–424 cm−1for the ruthenium(III) complexes but were not observed for the ruthenium(II) complexes in this region.

ISSN:0008-4042    

DOI:10.1139/v67-220

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The kinetic energy spectrum of photoelectrons ejected from ammonia by monochromatic 584 Å (21.21 eV) radiation has been determined using a spherical grid energy analyzer. Ionization potentials of 10.35 and 14.95 eV have been deduced from the spectrum and the relative transition probabilities to the ionic states have been measured. These experimental results are discussed in terms of the various molecular orbital theoretical treatments of the electronic structure of the ammonia molecule.

ISSN:0008-4042    

DOI:10.1139/v67-221

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The infrared absorption of KH2F3and KD2F3in the solid state was measured between 4 000 and 200 cm−1The observed bands can be assigned to the stretching and bending modes of the bent H2F3−ion. A normal coordinate analysis was carried out to determine the Urey–Bradley force constants. The results suggest that the hydrogen atoms are not exactly halfway between two fluorine atoms, contrary to the case of the HF2−ion.Les spectres infrarouges de KH2F3et KD2F3à l'état solide ont été mesurés entre 4 000 et 200 cm−1afin d'identifier les vibrations fondamentales de l'anion H2F3−. Les constantes de forces de rappel selon le modèle de Urey–Bradley ont pu être déterminées par analyse des coordonnées normales. Les résultats indiquent que les atomes d'hydrogène ne sont pas exactement à mi-chemin entre deux atomes de fluor, contrairement au cas de l'ion HF2−.

ISSN:0008-4042    

DOI:10.1139/v67-222

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Secondary reactions in the liquid phase radiolysis of cyclohexane in the presence of N2O and SF6have been examined by determining the yields of liquid products. When we added up to 0.3 MN2O, the hydrogen yield was reduced from its initial yield of 5.5 Gunits to 2.5 Gunits. The nitrogen yields were about twice the decrease in hydrogen yields. Bicyclohexyl and cyclohexene yields increased from their initial values to 2.27and 3.50 Gunits respectively. When we added up to 0.12 MSF6, all the yields were decreased to about one half of their initial value.These results may be interpreted in terms of Dyne's general mechanism for the radiolysis of hydrocarbons if two cyclohexyl radicals are produced for every electron scavenged by N2O, but if none are produced for electrons scavenged by SF6. It is suggested that the total electron yield in pure cyclohexane is about 4.1 Gunits, of which only 3.0 Gunits produce hydrogen. The other 2.5 Gunits of hydrogen from the radiolysis of pure cyclohexane are presumed to arise from direct excitation.

ISSN:0008-4042    

DOI:10.1139/v67-223

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The study of nuclear recoil reactions in organomanganese compounds was continued in methylcyclopentadienylmanganese tricarbonyl, a liquid, following earlier conclusions that the recombination reactions may involve a radical diffusion mechanism. Only a very small annealing effect was observed, but that was similar to the earlier results in which a maximum organic yield is reached, followed by a return to the initial value. Results of irradiation in benzene solution show no decrease of organic yield on dilution, which is interpreted as indicating that ‘hot’ reactions do not play a major role. Results of irradiation in mixed benzene–acetone solutions show a sharp decrease in organic yield as small quantities of acetone are added, which suggests a radical-scavenging process. The observation made earlier that considerable CH3Mn(CO)5is produced in this reaction leads to the speculation that radicals of the form Mn(CO)xare the reacting species.

ISSN:0008-4042    

DOI:10.1139/v67-224

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The quantum yields of acetylene and molecular iodine from the photolysis of pure vinyl iodide are 0.22 and 0.07 respectively. The disproportionation/recombination ratio for vinyl radicals with iodine atoms in diffusion-controlled processes is 0.34, as established from the quantum yields. A reaction scheme is proposed and several ratios of rate constants are calculated.

ISSN:0008-4042    

DOI:10.1139/v67-225

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The photolysis of methyl disulfide vapor in the pressure range 2–25 Torr at wavelengths between 2 300 and 2 800 and at 2 288 Å has been examined and the effect of temperature, pressure, added inert gases, ethyl disulfide, and nitric oxide determined.The primary process is a direct production of two CH3S radicals which have excess energy and which can be observed as methyl thionitrite when NO is present during the decomposition. When pure disulfide is photolyzed the major observable product is methanethiol, although this material accounts for only a small fraction of the primarily produced thiyl radicals whose principal fate is recombination in a substrate-reforming reaction producing excited disulfide molecules. The latter species are deactivated by added gases, or by the substrate itself. The mode of mercaptan formation is by abstraction of H atoms from the substrate by excited CH3S radicals with an apparent activation energy of 1.5 kcal.

ISSN:0008-4042    

DOI:10.1139/v67-226

出版商:NRC Research Press    

年代:1967

数据来源: NRC