摘要:

The acidity constantsk1of the following α-hydroxyketones HL tropolone, maltol, lawsone, and trichlorohydroxyp-benzoquinone have been determined at ionic strength 0.50 (HCl, NaCl)•The values of pk1are respectively: 6.67 ± 0.04; 8.36 ± 0.03; 4.00 ± 0.04; 1.05 ± 0.04. The formation of conjugated acids H2L+in strongly acidic media has also been studied. The values of pk2defined in terms of the acidity functionH0are: −0.53 ± 0.10; −0.71 ± 0.10; −5.6 ± 0.2; −8.8 ± 1.0.

ISSN:0008-4042    

DOI:10.1139/v66-244

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The formation of chelates between germanium (IV) and a series of α-hydroxyketones (HL) has been examined spectrophotometrically. Tropolone and maltol have been shown to give the species Ge(OH)2L2and GeL3+; the corresponding equilibrium constants β2and β3have been determined. The following solid compounds have been isolated: Ge(OH)2(tropolonate)2•2H2O, Ge(tropolonate)3ClO4, and Ge(maltolate)3ClO4. There was no evidence of complex formation with lawsone and trichlorohydroxyp-benzoquinone. Relations are discussed between the chelate stability, the state of germanium (IV) in solution, and the acid–base properties of the α-hydroxyketones.

ISSN:0008-4042    

DOI:10.1139/v66-245

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The energetics and mechanism of formation of ions ofm/e31, 45, and 59 from a number of alcohols, ethers, and esters have been studied. The following ionic heats of formation have been obtained: CH2=OH+, 176 kcal/mole; CH3O+, 213 kcal/mole; CH3CH=OH+, 145 kcal/mole; CH2=OCH3+, 170 kcal/mole; (CH3)2C=OH+, 125 kcal/mole; CH3CH2CH=OH+, 131 kcal/mole; CH3CH=OCH3+, 135 kcal/mole; CH2=OC2H5+, 144 kcal/mole. It is concluded that with the exception of CH3O+the alkoxy ions probably are not formed by electron impact processes. The gas-phase proton affinities of a number of carbonyl compounds are estimated.

ISSN:0008-4042    

DOI:10.1139/v66-246

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

An apparatus and improved conditions are described for using easily and efficiently sulfuric acid-d2as a deuterating agent. The preparation of 9,10-anthraquinone-d8with a high deuterium content is reported.

ISSN:0008-4042    

DOI:10.1139/v66-247

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

Five new ternary metal complexes containing imidazole and glycylglycine or amino acid have been prepared and characterized by proton magnetic resonance and infrared spectral studies. Seven new binary metal complexes have also been prepared and studied. The isolation of Cd(imidazole)6Cl2•H2O and Ni(imidazole)6-Cl2•4H2O provides evidence that the coordination number of these metal ions to imidazole in the solid state is six. The visible spectra of the Ni(II) complexes of amino acid and imidazole show that all these are octahedral in aqueous solution.

ISSN:0008-4042    

DOI:10.1139/v66-248

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

A spectrophotometric study of the Cu(II) – acetone – hydrochloric (hydrobromic) acid systems has revealed that at relatively high ratios of halide: copper there is a probable equilibrium between four-, five-, and six-coordinate halogenocopper(II) complexes. A distorted tetrahedral species is favored at the highest ratios. Ligand field bands of pseudo-octahedral monohalogenocopper(II) complexes and, in the visible region, a charge transfer band of the six-coordinate complex, [CuCl4(ac)2]2−, have been identified. The results of the present work point to the important role of the solvent in determining the geometries and absorption spectra of the complexes, a factor that seems to have been misinterpreted by some previous workers.

ISSN:0008-4042    

DOI:10.1139/v66-249

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The rate constants for the hydrogen-transfer ion-molecule reactionshave been measured at thermal ion energies and found to be 12 × 10−10 cm3molecule−1s−1and 8.0 × 10−10 cm3molecule−1s−1respectively. The rate coefficients at higher ion energies (3.7 eV ion exit energy) show little change from these values. Reactions [a] and [b] have also been studied using CD3OH and it is found that in reaction [a] the hydroxyl hydrogen is transferred 2.5 times more readily at low ion energies and 1.8 times more readily at high ion energies than a methyl hydrogen. This rather small specificity would appear to preclude formation of a "locked-in" collision complex even at low ion energies.

ISSN:0008-4042    

DOI:10.1139/v66-250

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The dissociation of surface hydroxyl groups of crystalline SiO2, ZrO2, and ThO2, in aqueous suspensions, has been studied as a function of pHsat different ionic strengths of KNO3. The surface groups of quartz dissociate as weak acids, while those of ZrO2and ThO2dissociate amphoterically. A reversible double layer is formed at the oxide–solution interface, and H+and OH−function as the potential-determining ions. Quantitative data have been obtained on (a) surface charge densities, (b) zero point of charge, (c) differential capacities of the double layer on quartz and ZrO2, and (d) the effect of surface charge density and ionic strength on the interfacial tension. The differential capacities indicate specific adsorption of NO3−on ZrO2and ThO2while NO3−has zero affinity for quartz surfaces. At low negative charge densities, solvated K+are adsorbed on quartz and ZrO2through coulombic interactions while at pHs > 10 specific adsorption of K+predominates. ThO2appears to exhibit a greater tendency for the specific adsorption of K+.

ISSN:0008-4042    

DOI:10.1139/v66-251

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

A spectroscopic investigation of the reaction of anhydrous perchloric acid with styrene in methylene chloride solution has been carried out, together with a study of the spectra of styrene and its derivatives dissolved in sulfuric acid. From the results it was decided that the absorbing species formed at the end of the reaction in methylene chloride are derivatives formed from the cyclized end groups of the polymer chain, and not the polystyrylcarbouium ion. It is not thought possible to determine from spectroscopic studies whether the polymerization reaction goes via a true ionic intermediate or a perchlorate ester.

ISSN:0008-4042    

DOI:10.1139/v66-252

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

Samples of COSe and CSe2were photolyzed at 77 °K, either pure or in matrices of Xe ortrans-2-butene. Observed electron spin resonance spectra are assigned to Se(43P), to Se2, and to chains of selenium atoms, •Se(Se)nSe•. The selenium chains exhibit metallic behavior intermediate between that of sulfur and tellurium. It is suggested that polymeric chains of CSe are formed on warming photolyzed samples containing CSe2. The ultraviolet absorption spectrum of COSe vapor is reported.

ISSN:0008-4042    

DOI:10.1139/v66-253

出版商:NRC Research Press    

年代:1966

数据来源: NRC