摘要:

The reaction of nitrogen atoms with propylene has been found to produce hydrogen cyanide and ethylene as the main products, together with smaller amounts of ethane and propane and traces of acetylene and of a C4fraction. With excess propylene, the nitrogen atoms were completely consumed and for the reaction at 242 °C., 0.77 mole of ethylene was produced for each mole of excess propylene added. For reactions at lower temperatures, less ethylene was produced. The proposed mechanism involves formation of a complex between the nitrogen atom and the double bond of propylene, followed by decomposition to ethylene, hydrogen cyanide, and atomic hydrogen. The ethylene would then react with atomic nitrogen in a similar manner.

ISSN:0008-4042    

DOI:10.1139/v52-110

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Conductivity and density data have been obtained for the system silver nitrate – sodium nitrate. The Arrhenius energy of activation for electrical migration in sodium nitrate and in the binary melts decreases with rising temperature above the melting point, as was shown previously for silver nitrate. The equivalent conductivity isotherms for the binary melts are almost linear in the mole fraction.

ISSN:0008-4042    

DOI:10.1139/v52-111

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Acetylene and hydrogen bromide react thermally without catalysts as well as photochemically to give high yields of 1,2-dibromoethane. The preparation of the following compounds containing 99 + % deuterium is described: acetylene-d2, 1,2-dibromoethane-d4, 1,2-dibromoethane-1,2-d2, ethylene-d4, 1,2-dichloro-ethane-d4, and ethylene-d4oxide. The vapor pressure of ethylene-d4oxide was determined in the temperature range −42 to 0 °C.

ISSN:0008-4042    

DOI:10.1139/v52-112

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

When 3(β)-chlorocholest-5-ene is heated with benzylamine, inversion with partial racemization occurs to give a mixture of N-benzyl-3(α)-aminocholest-5-ene and N-benzyl-3(β)-aminocholest-5-ene. The configurations of the N-benzyland N-acetyl-3-aminocholest-5-enes have been determined.The preparation of N,N-bis.-(2-chloroethyl)-3(ξ)-aminocholest-5-ene hydrochloride is described.

ISSN:0008-4042    

DOI:10.1139/v52-113

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Measurements of dielectric dispersion in vinyl acetal and formal polymers were performed over the frequency range 0.050 to 100 kc. at temperatures between 25 and 135 °C. The results reflect the effects of internal plasticization on the electrical properties of the polymers. With increasing size of the substituent groups from formal to butyral the dispersion range is shifted to lower temperatures at a given frequency. Electrical relaxation times and transition temperatures were obtained and values of enthalpies, free energies, and entropies of activation were calculated. A tentative physical picture of the mechanism of dielectric relaxation in these polymers was also formulated.

ISSN:0008-4042    

DOI:10.1139/v52-114

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

The absorption spectrum of pure hydroxylamine in the vapor and solid states was measured with a prism instrument in the range 1.5–25 µ. Except in one case the fundamental vibrations were clearly outlined and in some instances, particularly the 1115 cm−1band, the fine structure was resolved well enough for a significant calculation of the rotational constants. From the latter it was possible to confirm, within fairly close limits, the probable structure of the hydroxylamine molecule, a nearly symmetric top of point groupCs. At least two of the bands appeared to be doubled owing, presumably, to existence of a mixture ofcis-andtrans-forms of the molecule. The O—H and N—H distances have nearly the same value as in water and ammonia respectively and the N—O distance is 1.46 Å.The thermodynamic functions of gaseous hydroxylamine were calculated using the observed fundamental frequencies; some uncertainty accrues from the torsional oscillation. The infrared spectrum of crystalline hydroxylamine hydrochloride was also studied.

ISSN:0008-4042    

DOI:10.1139/v52-115

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

The infrared spectra of the vapor and the liquid, and the Raman spectra of liquidcisandtransC2HDCl2have been obtained in the region 400–3300 cm−1The observed spectra are in accordance with the assignment of Bernstein and Ramsay forcisandtransC2H2Cl2and C2D2Cl2.

ISSN:0008-4042    

DOI:10.1139/v52-116

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

The adsorption by soluble and insoluble heat-denatured lysozyme of eight anionic dyes, including methyl orange, has been determined at several temperatures and pH values. In addition, the adsorption of methyl orange by both the soluble and insoluble forms of seven other heat-denatured proteins has been determined as a function of temperature and pH. The isotherms, which are normal, reproducible, reversible, and independent of protein concentration confirm the notion of a sheath of strongly orientated water molecules about small positive proteins. They also demonstrate directly the importance of −ΔFof hydration in protein interaction studies. pH dependence of adsorption of methyl orange and other anions to denatured proteins is normal but −ΔHof adsorption per mole of anion bound is greater than for the corresponding native form.These results discredit the current concept of unique specific binding sites on a protein for weak interactions of the type studied.

ISSN:0008-4042    

DOI:10.1139/v52-117

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

From studies of the rate of reaction at 11°, 15°, 20°, and 26 °C. it was deduced that the bimolecular reaction between iron(II) and isopropyl cumene hydroperoxide is represented byAt 0 °C. the radical induced oxidation of iron(II) due to inability of the monomer to remove the free radicals became appreciable. Addition of up to 7.5% methanol did not change the rate appreciably. The effect of traces of oxygen was negligible. Rate constants were measured at 15°, 9°, and 0 °C. for the reaction between iron(II) and the tertiary butyl cumene hydroperoxide. The average probable error in the determinations was 5.4%. From the data, the Arrhenius equation was determined asComparison of the equations measured for cumene hydroperoxide, isopropyl cumene hydroperoxide, and tertiary butyl cumene hydroperoxide and iron(II) has been made. Changes in the constants have been explained qualitatively. The iodometric method of analysis when applied to tertiary butyl cumene hydroperoxide must be modified for accurate results. It is believed that the heating necessary in the presence of water decomposes the hydroperoxide.

ISSN:0008-4042    

DOI:10.1139/v52-118

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Ethyl α-substituted cyanoacetates were used to prepare hydrazides, azides, urethanes, anddl-α-amino-β-phenylbutyricacid,dl-α-amino-δ-o-bromophenoxyvaleric acid, anddl-α-amino-δ-o,p-dichlorophenoxyvaleric acid. Ethyl mono- and disubstituted cyanoacetates with hydrazine gave hydrazides which were transformed by treatment with sodium hydroxide into 4-α-phenylethyl-, 4-m-ethylphenoxyethyl-, 4-o-bromophenoxypropyl-, 4-o,p-dichlorophenoxypropyl-, 4,4-m-ethylphenoxy-ethyl-, and 4,4-m-methylphenoxypropyl-3-amino-5-pyrazolones. The ultraviolet absorption spectra of the pyrazolones were determined in neutral, acid, and alkaline solutions and their structures established.

ISSN:0008-4042    

DOI:10.1139/v52-119

出版商:NRC Research Press    

年代:1952

数据来源: NRC