摘要:

A survey has been made of the nature of the peroxides occurring in the combustion of isobutane below and above the lower cool-flame limit. The peroxides were resolved and partially identified by paper chromatography. Below the cool-flame limit, the peroxide is found to be mostlytert-butyl hydroperoxide, with some hydrogen peroxide, but as the cool-flame limit is approached the proportion oftert-butyl hydroperoxide declines, while that of hydrogen peroxide increases. In addition, peroxides identified as aldehyde and acid peroxides increase as the cool-flame limit is approached. Notert-butyl hydroperoxide appears to survive the cool flame, although copious quantities of aldehyde peroxide and hydrogen peroxide remain.

ISSN:0008-4042    

DOI:10.1139/v58-176

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Cyclopropane, cyclobutane, and cyclopentane in order of increasing reactivity with active nitrogen yielded hydrogen cyanide and ethylene as the major products. The relative proportions of ethylene to hydrogen cyanide increased with number of carbon atoms in the reactant and with increase of temperature.

ISSN:0008-4042    

DOI:10.1139/v58-177

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Cyanogen chloride and chlorine were the only gaseous products observed in the reaction of active nitrogen with carbon tetrachloride at 110° and 420 °C. The product yields tended towards limiting values at higher reactant flow rates, and increased with increase of temperature at all flow rates. The reactions of active nitrogen with chloroform and dichloromethane at 260° and 420 °C yielded hydrogen chloride, hydrogen cyanide, and cyanogen, in addition to cyanogen chloride and chlorine. The behavior of the product yields with reactant flow rates and temperature was similar to that of the products from carbon tetrachloride.

ISSN:0008-4042    

DOI:10.1139/v58-178

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The photolysis of di-t-butyl peroxide has been investigated over the temperature range 25 ° to 79 °C. As reaction products were observed: acetone,t-butyl alcohol, methylt-butyl ether,i-butylene oxide, ethane, methane, and carbon monoxide. The following reactions, involving thet-butoxy radical, have been studied:An activation energy difference ofE2 − E6 = 3 kcal has been obtained.

ISSN:0008-4042    

DOI:10.1139/v58-179

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The extraction of plutonium from neutron-irradiated uranium by uranium trichloride and by magnesium chloride has been examined in the temperature range 1150° to 1250 °C. The results of the uranium trichloride experiments have been used to evaluate the standard free-energy change of the equilibrium reactionThese free-energy values have been used to predict the plutonium extraction in the magnesium chloride experiments on the assumption that the uranium trichloride, continuously formed from the non-equilibrium reactionrapidly established the above equilibrium with the plutonium in the uranium. Agreement between predicted and experimental results supports this assumption.A preliminary study of the kinetics of the MgCl2–U reaction showed that the initial rate of reaction is controlled by the distillation of magnesium metal from the reaction zone.

ISSN:0008-4042    

DOI:10.1139/v58-180

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The stereoisomeric 1-ethoxy-2,3-epoxycyclohexanes were prepared from 1-ethoxycyclohexene-2 via 1-ethoxycyclohexene-2 bromohydrin. Ammonolysis of the lower- and higher-boiling oxides furnished 1α-ethoxy-2β-hydroxy-3α-aminocyclohexane and 1α -ethoxy-2β-hydroxy-3α-aminocyclohexane respectively. In a similar manner, 1α-methoxy-2α-hydroxy-3β-aminocyclohexane and lα-methoxy-2β-hydroxy-3α-aminocyclohexane were obtained from l-methoxycyclohexene-2 via 1-methoxycyclohexene-2 bromohydrin and the stereoisomeric 1-methoxy-2,3-epoxycyclohexanes. Ether cleavage of 1α-ethoxy- and lα-methoxy-2β-hydroxy-3α-aminocyclohexane gave 3α-amino-1α,2β-cyclohexanediol hydrobromide, from which the free base was obtained. 3β-Amino-1α,2α-cyclohexanediol was prepared similarly from lα-ethoxy- and 1α-methoxy-2α-hydroxy-3β-aminocyclohexane. The stereochemistry of the 3-amino-1,2-cyclohexanediols, 1-alkoxy-2-hydroxy-3-aminocyclohexanes, and 1-alkoxy-2,3-epoxycyclohexanes has been elaborated.

ISSN:0008-4042    

DOI:10.1139/v58-181

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Cyanogen bromide reacts with the sodium salts of lower aliphatic acids at 250-300 °C to form an α-keto isocyanate as the primary product. The latter undergoes subsequent pyrolytic decomposition to a nitrile and carbon dioxide. A mechanism is proposed to account for the observed interchange of labelled carbon atoms between the CN group of the cyanogen bromide and the carboxyl group of the salt in the over-all reaction.

ISSN:0008-4042    

DOI:10.1139/v58-182

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The Reformatsky reaction of 3,5-seco-5-ketocholestan-3-oic acid methyl ester with methyl bromoacetate yielded 2-carbohydroxycholestenone, cholestenone, and 4-carbomethoxycholestenone. The appearance of these products indicated that cyclization of ring A proceeded along two different paths; this conclusion was confirmed by the use of methyl bromoacetate-1-C14and -2-C14.

ISSN:0008-4042    

DOI:10.1139/v58-183

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

The solubility of Al(OH)3was measured in NaOH and HClO4solutions. Possible reactions of Al(OH)3in dilute NaOH and HCIO4solutions are indicated along with the calculated constants. The amphoteric hydroxide was found to be more acidic than basic. The isoelectric point of Al(OH)3was determined to be pH 7.7.

ISSN:0008-4042    

DOI:10.1139/v58-184

出版商:NRC Research Press    

年代:1958

数据来源: NRC

摘要:

Silver nitrate, dissolved in some organic solvents, has formed a relatively specific medium for the gas chromatographic separation of olefins. Columns formed from ethylene glycol and glycerin solutions of silver nitrate are comparable, but those formed from the polyethylene glycol solutions are considerably less effective. These silver nitrate solutions were stable below 65 °C, but began to decompose slowly at 85 °C.

ISSN:0008-4042    

DOI:10.1139/v58-185

出版商:NRC Research Press    

年代:1958

数据来源: NRC