摘要:

The equivalent conductances of concentrated solutions of ammonium and silver nitrates have been determined up to saturation at 35.00 °C. with a probable error of 0.1%. The equivalent conductances behave in a normal manner for strong electrolytes in aqueous solution, being approximately linear with the first power of the concentration, though slightly convex to the concentration axis. The viscosities and fluidities of these same solutions have been determined both at 25.00 °C. and 35.00 °C. with a probable error of 0.2%. Ammonium nitrate solutions exhibit the phenomenon of "negative viscosity" which tends to disappear at higher temperatures, the viscosity minimum or fluidity maximum shifting towards higher dilution. The silver nitrate fluidities decrease continuously with concentration, the curve showing less tendency to linearity at high concentrations than that for ammonium nitrate. The densities of the solutions at both temperatures have been determined with an apparent error of 0.02%. Apparent molal volumes have been calculated from these figures at 35.00 °C. The concentrations of the saturated solutions of both salts at 25.00 °C. and 35.00 °C. have been determined by the conductance method and are in good agreement with the published data. The average temperature coefficients of fluidity and conductance for both salts have been evaluated between 25.00 °C. and 35.00 °C. and an approximate constancy of the ratio of fluidity coefficient to conductance coefficient has been observed beyond 2 molar. The ratios appear to have the mean value of 1.12 for both salts in spite of a considerable difference in the individual coefficients.

ISSN:0008-4042    

DOI:10.1139/v53-085

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

The photolysis of mercury dimethyl was investigated over the temperature range from 125° to 250 °C. The results indicate that methane is formed only by an abstraction reaction and ethane is formed only by recombination, at least under the conditions used in these experiments. It is concluded that the activation energy of the reactionis 10.8 ± 0.3 kcal./mole.

ISSN:0008-4042    

DOI:10.1139/v53-086

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

New methods are given for the preparation of sodium copper (111) tellurate, Na9Cu(TeO6)2.16H2O, and sodium copper (111) periodate, Na7Cu(IO6)2.20H2O, previously reported by Malatesta. Additional analytical evidence is presented that these are really compounds of trivalent copper. The dissociation of the ions in alkaline aqueous solution was examined through the ability of the uncomplexed copper to catalyze the decomposition of sodium hypochlorite. Evidence is presented that the uncomplexed copper ion is Cu(OH)4−, and this gives both a 1-1 and a 1-2 complex with both tellurate and periodate. The 1-2 complexes appear to be Cu(HTeO6)2−7and Cu(IO6)2−7respectively; the 1-1 complexes are less stable. The equilibrium constants for the reversible dissociation of these ions into their simpler constituents in aqueous solution at 40 °C. are as follows: tellurate, 1-1 complexK1 = 1.8 × 10−6; 1-2 complexK2 = 1.1 × 10−11; periodate, 1-1 complexK1 = 3.4 × 10−5; 1-2 complex isK2 = 8.0 × 10−11. The smaller the constant the more stable the complex ion. In the case of the tellurate complexK2is proportional to the square of the hydroxide ion concentration and these values are for 0.400 Msodium hydroxide; with periodateK2is independent of the hydroxide concentration. Experiments at various temperatures give 20 kcal. as the heat of the reaction forming the 1-2 tellurate complex from the simple ions, and 71/2 kcal. for the 1-2 periodate complex. The stannate, stibnate, and selenate ions showed no signs of forming analogous compounds.

ISSN:0008-4042    

DOI:10.1139/v53-087

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

A barley gum that is believed to be the undegraded, water-soluble, nonstarch polysaccharide of the grain has been isolated. Aqueous solutions of this gum are extremely viscous and are stable. Enzymes that degrade gum during simple aqueous extraction were inactivated first by refluxing barley grist in boiling 85% alcohol followed by extraction of the dried grist with a 1% solution of papain. Gums of lower degree of polymerization, as judged by viscosity measurements, were obtained by aqueous extraction and acid treatments. Two enzyme systems that degrade gums are thought to be present in barley. One (which is inactivated by alcohol) degrades the initially soluble gum and brings an initially insoluble form into solution. The second system (which is inactivated by papain) accompanies and degrades the initially soluble gum during aqueous extraction or in aqueous solutions of the preparation. The purest gum contains only 0.1% nitrogen, and this may be part of the molecular complex. Mild, cold, alkali treatment of this gum reduces molecular size considerably as measured by viscosity of solutions. "X"-enzyme isolated from a bacterial source cleaves the gum into two oligosaccharides of glucose and a component containingD-glucose,L-arabinose,D-xylose, andD-galactose. No free sugars are produced.

ISSN:0008-4042    

DOI:10.1139/v53-088

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

A potential of −0.305 ± 0.005 volt (relative to a saturated calomel electrode) was obtained at a freshly prepared platinum surface within 30 sec. of immersion in oxygen-freeN/5sulphuric acid saturated with hydrogen. In electrolytes saturated with nitrogen or oxygen potentials of +0.05 ± 0.01 volt and +0.745 ± 0.005 volt respectively were more slowly attained. The times required for the electrode to reach maximum potentials,tmax, when it was made a cathode, and corresponding values oftmaxwhen it was rendered anodic, were determined over a range of currents. The values oftmaxappear to provide a method of determining the surface areas of platinum electrodes.

ISSN:0008-4042    

DOI:10.1139/v53-089

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

1,4-Diphenyl-3-carbethoxy-5-aminopyrazole yielded 1,4-diphenyl-5-aminopyrazole by hydrolysis and decarboxylation. The phenylhydrazone of ethyl phenyloxalacetate gave a pyrazolone which was transformed into 1,4-diphenyl-3-amino-5-pyrazolone. The 2,4-diphenyl-3-amino-5-pyrazolone was obtained from ethyl phenylcyanoacetate and phenylhydrazine by heating in acetic acid. 4-Alkyl-3-hydroxy- and 3-amino-5-pyrazolones and 4,4-dialkyl-3-oxo- and 3-imino-5-pyrazolones, substituted in position 2 by carbanilino or α- or β-naphthyl groups, were prepared from ethyl mono- or disubstituted malonates and cyanoacetates, 4-phenylsemicarbazide, and α- and β-naphthylhydrazines. Ultraviolet absorption spectra were determined in neutral and acid solutions.

ISSN:0008-4042    

DOI:10.1139/v53-090

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

Amine salts of dinitroalkyl phenols have been suggested as herbicides and insecticides. A selection of such amine salts was examined as to their suitability for characterizing dinitroalkyl phenols. The following new salts are described: the piperidine, morpholine, and cyclohexylamine salts of each of 2,4-dinitrophenol, 4,6-dinitro-2-methylphenol, 2,6-dinitro-4-methylphenol, 4,6-dinitro-2-isopropylphenol, 2,6-dinitro-4-isopropyl phenol, 4,6-dinitro-2-(sec-butyl)-phenol, 2,6-dinitro-4-(tert-butyl)-phenol, and 2,6-dinitro-4-(tert-amyl)-phenol. In addition, the preparation of 4,6-dinitro-2-isopropylphenol and 2,6-dinitro-4-isopropylphenol does not appear to have been previously described. The use of these salts, and similar ones with other amines, is recommended for the preparation of crystalline derivatives of dinitrophenols.

ISSN:0008-4042    

DOI:10.1139/v53-091

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

Cholesteryl chloroformate can be used to isolate small amounts of amines from aqueous solutions as N-substituted cholesteryl carbamates. These derivatives are easily isolated and identified. Their possible use for, the identification of amines obtained in degradative studies is discussed. The thermal decomposition of N-benzyl cholesteryl carbamate gives carbon dioxide, cholesterol, cholest-3,5-diene, andsym-dibenzylurea. A mechanism of formation of these products is discussed.

ISSN:0008-4042    

DOI:10.1139/v53-092

出版商:NRC Research Press    

年代:1953

数据来源: NRC

摘要:

not available

ISSN:0008-4042    

DOI:10.1139/v53-093

出版商:NRC Research Press    

年代:1953

数据来源: NRC