摘要:

From a 0.368 Msolution ofD-mannitol hexanitrate in pyridine at 30 ± 5 °C. a gas consisting of nitric oxide, nitrous oxide, and nitrogen was evolved andD-mannitol-1,2,4,5,6-pentanitrate and pyridinium nitrate were recovered after dilution with water. The amount and composition of the gas mixture were sensitive to traces of moisture in the pyridine. Establishment of a material balance for the reaction indicated that approximately two moles of pyridine suffered ring cleavage while 0.25 mole of hexanitrate was completely denitrated and 0.75 mole of pentanitrate was formed. Some features of the mechanism of the denitration reaction are discussed.

ISSN:0008-4042    

DOI:10.1139/v55-216

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The standard intensities of the Raman bands of CH3CN, CD3CN, CH3CCl3and CD3CCl3have been obtained for the liquids with a photoelectric, grating spectrometer. The intensity sum rules for isotopic homologues are valid within the experimental error. The infrared spectra of CD3CN and CD3CCl3have been obtained in the liquid phase and in the vapor phase. A definitive assignment ofv11(e) has been made for methyl chloroform.

ISSN:0008-4042    

DOI:10.1139/v55-217

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The polarization–time relations for the initial (Pi), maximum (Pmax), and pseudo-steady-state (Ps) polarizations on copper single crystals in the absence and presence of gelatin and gelatin plus chloride ion were found to depend upon crystal orientation. ThePiandPmaxin the absence of gelatin, thePiin its presence, and the static potentials were all similarly related to the reticular density. ThePiincreased, and the time to maximum polarization (tmax) decreased, with increase of current density; the relations between these quantities showed marked differences for the different crystals. The variation with reticular density ofPiandPmaxin the absence of addition agents and ofPiin its presence probably represents differences in activation overpotential at the various crystal faces. The adsorption of gelatin on different crystal faces was also found to be markedly different. Polarization in the presence of gelatin was decreased by small amounts of chloride ion; a linear relation for all the crystals used was obtained by plotting the increase in polarization caused by gelatin against the decrease caused by 2 mgm./liter chloride ion in the presence of gelatin. In the absence of addition agent, change of acid concentration from 50 to 200 gm./liter had no effect onPiand addition of chloride ion had no effect onPsat single crystal cathodes.

ISSN:0008-4042    

DOI:10.1139/v55-218

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

2,4,6-Tri-t-butylbromobenzene, m.p. 177–177.5°, was prepared by the bromination of 1,3,5-tri-t-butylbenzene in the presence of silver nitrate. The reaction of 2,4,6-tri-t-butylbromobenzene andn-butyllithium gave 2,4,6-tri-t-butylphenyl-lithium, which on carbonation yielded 2,4,6-tri-t-butylbenzoic acid, m.p. 297°. A solution of this acid in fuming sulphuric acid yielded a methyl ester, m.p. 96–98°, when it was poured into absolute methanol. Similar treatment of 1,4-di-t-butylbenzene with bromine gave 2,5-di-t-butylbromobenzene, which on reaction withn-butyllithium and subsequent carbonation gave 2,5-di-t-butylbenzoic acid. The reaction of 1,3,5-tri-t-butylbenzene with acetyl chloride in the presence of aluminum chloride gave a liquid ketone, and hypohalide oxidation of this ketone yielded 3,5-tri-t-butylbenzoic acid. The ultraviolet absorption spectra of the two bromo compounds and the three acids were measured and are discussed. The considerable acid-weakening effect in 2,4,6-tri-t-butylbenzoic acid is attributed to steric hindrance to the formation of the carboxylate anion.

ISSN:0008-4042    

DOI:10.1139/v55-219

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The heat of hydrolysis of uranium (IV) in perchloric acid solution has been measured by a spectrophotometric technique. A value of 10.7 ± 1 kcal. per mole was obtained, in good agreement with a previous value determined by a calorimetric method. The entropy of association of uranium (IV) with hydroxyl ion is +52 e.u.

ISSN:0008-4042    

DOI:10.1139/v55-220

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The kinetics of oxidation of uranium (IV) by iron (III) in aqueous solutions of perchloric acid have been investigated at four temperatures between 3.1 °C. and 24.8 °C. The reaction was followed by measurement of the amount of ferrous ion formed. For the conditions (H+) = 0.1–1.0 M, ionic strength = 1.02, (FeIII) = 10−4–10−5 M, and (UIV) = 10−4–10−5 M, the observed rate law isd(Fe2+)/dt = −2d(UIV)/dtK1andK2are the first hydrolysis constants for Fe3+and U4+, respectively, andK′ andK″ are pseudo rate constants. At 24.8 °C.,K′ = 2.98 sec.−1, andK″ = 10.6 mole liter−1sec−1. The corresponding temperature coefficients are ΔH′ = 22.5 kcal./mole and ΔH″ = 24.2 kcal./mole. The kinetics of the process are consistent with a mechanism which involves, as a rate-controlling step, electron transfer between hydrolyzed ions.

ISSN:0008-4042    

DOI:10.1139/v55-221

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The infrared and Raman spectra of CH2=CDCl and the Raman spectrum of CH2=CHCl have been obtained and depolarization ratios of the Raman bands have been measured. The spectra of the two molecules have been correlated.

ISSN:0008-4042    

DOI:10.1139/v55-222

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

The densities of the series of alkali metal stearates and of a number of sodium stearates having substituents in the hydrocarbon chain have been measured over a temperature range of 25–380 °C. Discontinuities in the density–temperature relationships indicate the transitions between the various mesomorphic forms in which these soaps exist and the results are compared with transition data obtained by an optical method, described in Part I of this series. Mesomorphism is found to be much less pronounced in the substituted stearates examined than in the normal soaps.

ISSN:0008-4042    

DOI:10.1139/v55-223

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

Maleic hydrazide was found to be similar to maleic acid in its polarographic behavior. Two pairs of double waves are produced, one in the region around pH 5.9 and the other around 8.2. The theory that the double waves are a result of the reduction of the undissociated acid followed by that of its anion at a higher negative potential appears to explain the first of these double waves but fails to explain the second.

ISSN:0008-4042    

DOI:10.1139/v55-224

出版商:NRC Research Press    

年代:1955

数据来源: NRC

摘要:

Hydrogen atoms produced in a discharge tube were found to react with methyl cyanide to produce hydrogen cyanide as the main product, together with smaller amounts of methane and ethane. The proposed mechanism involves the formation of hydrogen cyanide and a methyl radical in the initial step; methane and ethane are attributed to secondary reactions of the methyl radicals.

ISSN:0008-4042    

DOI:10.1139/v55-225

出版商:NRC Research Press    

年代:1955

数据来源: NRC