摘要:

The vibration–rotation infrared absorption spectrum of germyl iodide-d3has been recorded under medium resolution conditions. The fine structure in the doubly degenerate bands was resolved and analyzed.From an assumedB″ value of 0.051 cm−1, values forA″,A4′,A5′, A6′,ζ4′,ζ5, andζ6were calculated. The fundamental frequencies for GeD3I were found to be 1 509.9, 582.8, and 249.5 for thea1species and 1 529.5, 614.5, and 405.6 cm−1for theespecies. Only the results forν4andν5differ appreciably from earlier estimates.

ISSN:0008-4042    

DOI:10.1139/v67-432

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Contrary to earlier reports, treatment of aqueous chloropentamminecobalt(III) ion with silver oxide and then with perchloric acid yields aquopentamminecobalt(III) perchlorate, and not perchloratopentamminecobalt(III) perchlorate. No detectable inner-sphere substitution of perchlorate for water in aquopentamminecobalt(III) ion takes place in aqueous perchloric acid of up to at least 5 Mconcentration at 25°. Solid aquopentamminecobalt(III) perchlorate is stable at 110°, but heating above 160° results in slow general decomposition to Co3O4without the intermediate formation of perchloratopentamminecobalt(III) perchlorate; the solid explodes violently at 290°.

ISSN:0008-4042    

DOI:10.1139/v67-433

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

A method is described by which an ion gauge, used as a molecular-beam flux detector, can discriminate between signals produced by two gases, provided they have a mass ratio of at least 2 and are present in comparable amounts. The method employs a mechanically chopped beam with narrow band phase-sensitive detection. Separation of two signals is possible because of the different rates of effusion of the two gases out of the gauge. Because of this the phase of the a.c. signal extracted by the lock-in amplifier depends on the beam composition. A theoretical analysis of the phenomena is presented and is compared with experimental data. Limitations of the method are also considered.

ISSN:0008-4042    

DOI:10.1139/v67-434

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

FourN,N-dialkyldithiocarbamate esters have been prepared and examined by nuclear magnetic resonance. From the temperature variation of theN-alkyl resonances, estimates of the barriers to rotation about the C—N bond have been made. Activation energies of the order 10 to 12 kcal provide evidence for an appreciable amount of C—N double bonding; this lends support to the assignment of the "thioureide" band in present and earlier infrared studies.

ISSN:0008-4042    

DOI:10.1139/v67-435

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The heats of mixing of the 11 binaryn-alcohol systems containing either butanol or octanol and formed from the set methanol, ethanol, propanol, butanol, hexanol, octanol, and decanol were measured in a continuous dilution calorimeter at 25 °C. The applicability of Brønsted's principle of congruence to the data was investigated.

ISSN:0008-4042    

DOI:10.1139/v67-436

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The phase relations for the systems Pt/As, Os/As, Os/Se, and Ru/Se have been examined in the range 850–1 250 °K. Using the torsion effusion method, the decomposition pressures of PtAs2, OsAs2, OsSe2, and RuSe2have been measured as a function of temperature. The apparatus and procedures were verified by measuring the vapor pressure of liquid silver. Equilibrium pressures were obtained for PtAs2and RuSe2. OsAs2exhibited an orifice area dependent nonequilibrium behavior and OsSe2exhibited a time dependent nonequilibrium behavior. Equilibrium pressures were estimated in these latter two cases. Total equilibrium decomposition pressures (Pt), i.e. the pressure of arsenic or selenium vapors in equilibrium with each phase, are best described by the equations:Literature data on the equilibria between the various molecular species in selenium and arsenic vapor indicate that at these pressures and temperatures the vapor in equilibrium with the selenides is essentially pure Se2, but the vapor over the arsenides is a mixture of As2and As4.The heats and entropies of decomposition of PtAs2, OsAs2, OsSe2, and RuSe2have been calculated from the decomposition pressure data. The standard heats of formation at 298 °K are −42.0 ± 3.5, −18.5 ± 2.0, −32.5 ± 5.0, and −42.9 ± 3.5 kcal/mole, respectively. Heats of formation of MnSe2, CoSe2, NiSe2, and RhSe2have been estimated using the heats of formation of OsSe2and RuSe2, the Born–Mayer equation, and the Born–Haber cycle. These are −96 ± 8, −70 ± 8, −41 ± 8, and −12 ± 12 kcal/mole, respectively.

ISSN:0008-4042    

DOI:10.1139/v67-437

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The infrared absorption of HCl and HBr in solid nitrogen at liquid helium temperatures has been recorded. Multiplets have been observed in the region of the fundamental of each molecule. An interpretation is given, based on rotation of the HCl and HBr molecules in the nitrogen matrix.

ISSN:0008-4042    

DOI:10.1139/v67-438

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

A method of determining the stoichiometry of metastable phases from nucleation characteristics is described and is applied to calcium phosphate precipitation. The stoichiometric ratio [Ca]/[P] is shown to be 1.49 ± 0.02 in the pH range 7.0–9.1, indicating that it is not hydroxyapatite which normally forms first in the physiological pH region. Characterization of the product by radio isotopes and by infrared spectroscopy and electron diffraction confirms the stoichiometry and indicates that the calcium phosphate nucleated from solution at high pH is an amorphous or soft metastable material. Some biological implications of these findings are pointed out.

ISSN:0008-4042    

DOI:10.1139/v67-439

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The initial reversible interaction of 1,3,5-trinitrobenzene and cyanide ion has been studied spectrophotometrically in a number of nonaqueous solvents and found to result in the formation of a complex containing 1,3,5-trinitrobenzene and cyanide ion in a 1:1 ratio. At 25.3 °C, the equilibrium constants for complex formation (K) and the molar extinction coefficients (ε) of the complex were found to be 1.44 ± 0.15 × 105 l mole−1and 2.24 ± 0.05 × 104 l mole−1cm−1and 3.35 ± 0.35 × 105 l mole−1and 2.24 ± 0.05 × 104 1 mole−1cm−1respectively for acetone and chloroform solutions. The second-order rate constant governing formation of the complex in chloroform was found to be 2.25 × 102 l mole−1s−1at 25.0 °C. On the basis of the visible and infrared absorption data obtained for the complex in chloroform and 1,2-dimethoxy-ethane, the complex is considered to be a Meisenheimer-type complex rather than a "charge-transfer" complex.

ISSN:0008-4042    

DOI:10.1139/v67-440

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Isomeric cross-section ratios for nuclides formed from (p,2n), (p,3n), (p,4n), and (p,p3n) reactions on88Sr are presented. The experimental results for the88Sr(p,2n)87Ym,greaction are compared with statistical-model calculations wherein spin-density parameter values were obtained from various theoretical formalisms. The parameters required to match the calculated and experimental values are in good agreement with those obtained by Vandenboschet al.

ISSN:0008-4042    

DOI:10.1139/v67-441

出版商:NRC Research Press    

年代:1967

数据来源: NRC