摘要:

The rate of hydration of ethylene in dilute aqueous perchloric acid has been measured in the range 170–190 °C at 100 bars and 100 to 3 000 bars at 180 °C. The energy, entropy, and volume of activation are 33.3 ± ~1 kcal mole−1, −5.7 ± ~2.5 cal deg−1mole−1, and − 15.5 ± ~1.5 cm3mole−1respectively. The volume of activation shows that at least one molecule of water is strongly bound in the transition state.

ISSN:0008-4042    

DOI:10.1139/v65-337

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The rate of pyrolysis of neohexane decreases slightly with increasingS/Vratio in the pressure range of 15–100 mm at 510–530 °C. The yields of CH4, C2H6, and C3H6increase with increasing hydrocarbon pressure while the yields ofi-C4H8and H2, which increase with increasing hydrocarbon pressure, tend to level off at higher pressures. The rest of the products are pressure independent. The nitric oxide required for maximum inhibition is 12–14 mm for hydrocarbon pressures in the range of 50–120 mm and shifts to slightly higher values for higherS/Vratios. Nitric oxide affects the product distribution slightly. The yields of CH4and C2H4increase while the yields of C2H6and 2-methyl butene-2 decrease with increasing NO pressure. Surface-to-volume (S/V) ratio has no effect on the product distribution in the inhibited pyrolysis of neohexane, indicating the role of the inhibitor to be limited to the gas phase for this isomer. The analytical balance does become less complete with increasing NO pressure because of such reactions as

ISSN:0008-4042    

DOI:10.1139/v65-338

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

For a series of 9-alkyl-9-fluorenylmethylp-toluenesulfonates, the rates of decomposition in formic acid increase with the size of the alkyl group. Changes in the rate constants are associated with changes in ΔS≠.

ISSN:0008-4042    

DOI:10.1139/v65-339

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

Previous studies on electrochemical adsorption at mercury of a series of heterocyclic and aromatic nitrogen bases and their respective conjugate ions by electrocapillary measurements are extended to simple saturated heterocyclic compounds containing oxygen and to aliphatic alcohols with different degrees of unsaturation. Adsorption isotherms for various electrode potentials are derived, and standard electrochemical free energies of adsorption are calculated as before, to relate the influence of molecular and electronic structure of the adsorbates on the properties of the electrical double layer. Oxygen as the heteroatom in cyclic compounds and in the hydroxyl group of the alcohols plays a distinct role in the characteristics of metal–adsorbate and adsorbate–solvent interactions through its higher electronegativity as compared with nitrogen. Considerations of the different geometric areas of adsorbed molecules due to isomerism of the saturated heterocyclic compounds, and the varying unsaturation of the alcohols lead to more realistic interpretation of orientation effects, surface coverages, and degrees of adsorbability. Improvement in pressure control in the electrocapillarometer assembly gives better precision in surface tension measurements. Some preliminary results on the adsorption of furfurylamines and related analogues which constitute a newly available class of corrosion inhibitors are briefly discussed.

ISSN:0008-4042    

DOI:10.1139/v65-340

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

Oximes of gamma cyano- and gamma nitro-ketones are decomposed by heat as well as by acids. From the very complex mixtures resulting there have been isolated arylated pyrroles, arylated 2-aminopyridines, and the corresponding pyridones, as well as several minor products. This behavior constitutes a new synthesis of these heterocyclic compounds. In a Beckmann rearrangement γ-benzoyl-α,β-diphenylbutyronitrile gave an anilide, the structure of which was confirmed by an independent synthesis. By physical methods both structures of gamma ketonic amides are confirmed.

ISSN:0008-4042    

DOI:10.1139/v65-341

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The independent fission yields in thermal neutron induced fission of235U have been measured to be (9.5 ± 1.4)•10−6% and (1.04 ± 0.17)•10−3% for124gSb and126gSb, respectively. The total independent yields for all isomers of these nuclides are estimated to be (1.2 ± 0.2)•10−5% for124Sb and (3.7 ± 0.6)•10−3% for126Sb using a Huizenga–Vandenbosch approach for estimating population of isomeric states.These data do not seem to support a 50 proton shell effect on theZpfunction, using the "unique" charge distribution curve of Wahl. A revised Wahl plot based on recent information on neutron emission from individual fission fragments is given and discussed in view of shell effects in fission. It is shown that the effect of theZpfunction of the 50 proton shell is very small.

ISSN:0008-4042    

DOI:10.1139/v65-342

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The disaccharide named in the title, 6-O-β-D-galactopyranosyl-D-galactose, and the 2(?)-substituted isomer have been synthesized in low yield by the condensation of acetobromo-D-galactose and di-O-isopropylidene-aldehydo-D-galactose dimethyl acetal.

ISSN:0008-4042    

DOI:10.1139/v65-343

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The synthesis of a series of 2,2-disubstituted-5-cyanocyclopentanones by hydrolysis of the precursor 3,3-disubstituted-2-amino-1-cyanocyclopentenes (2,2-disubstituted-5-cyanocyclopentanoneimines) is described. The new compounds possess the following substituants: dimethyl, diethyl, phenyl hydrogen, and ethyl phenyl.

ISSN:0008-4042    

DOI:10.1139/v65-344

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The mass spectra of six furoquinoline alkaloids have been recorded and mechanisms have been proposed for their fragmentation upon electron impact. Strong metastable peaks, present in all spectra, have aided in the interpretation of the fragmentation of these alkaloids. The three alkaloids with a methoxyl group in the 8-position of the quinoline ring may be differentiated from the other three by the presence of relatively intense peaks at M-1 and M-29.

ISSN:0008-4042    

DOI:10.1139/v65-345

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The two recognized forms of calcium sulfate hemihydrate can be identified by the position of a relatively small exothermic peak in their differential thermograms. Hemihydrates prepared at various water vapor pressures up to 760 mm Hg were found to produce this exothermic peak in a position which is characteristic for the β-form. These results indicate that α-hemihydrate cannot be made at atmospheric pressure, as was previously suggested on the basis of heat solution measurements. The typical differential thermogram of α-hemihydrate is only obtained with material made by dehydration in solution or by autoclaving. The effect of ambient water vapor pressure on the position of the three peaks that occur in the differential thermogram of CaSO4•2H2O has also been studied. It was found that the incipient temperature of the second endothermic peak, corresponding to the transition of hemihydrate to soluble anhydrite, is displaced independent of the rate of heating from 145 °C to 187 °C with increasing water vapor pressures up to 760 mm Hg. This indicates that, for each temperature, a threshold water vapor pressure exists, above which soluble anhydrite cannot be formed.

ISSN:0008-4042    

DOI:10.1139/v65-346

出版商:NRC Research Press    

年代:1965

数据来源: NRC