Showing papers in "Canadian Journal of Chemistry in 1969"
TL;DR: The thermodynamic equation (∂CP/∂P)T = T(∂2V/ ∂T2)P is used as a basis for relating thermal expansion to structure (at several temperatures and pressures) of water and normal liquids.
Abstract: The thermodynamic equation (∂CP/∂P)T = −T(∂2V/∂T2)P is used as a basis for relating thermal expansion to structure (at several temperatures and pressures) of water and "normal" liquids. Similar con...
742 citations
TL;DR: In this paper, it was shown that cereal grain phytic acid has the myoinositol hexaorthophosphate structure suggested by Anderson and not the hydrated myoinosophol tripyrophosphates structure propos...
Abstract: Evidence is presented to show that cereal grain phytic acid has the myoinositol hexaorthophosphate structure suggested by Anderson and not the hydrated myoinositol tripyrophosphate structure propos...
217 citations
TL;DR: In this paper, it was shown that changes in optical rotation at the D-line of sodium which occur with changes in solvent largely reflect changes in conformational equilibria, and that the changes in the nu...
Abstract: Further evidence is presented (8) that changes in optical rotation at the D-line of sodium which occur with changes in solvent largely reflect changes in conformational equilibria.Changes in the nu...
208 citations
TL;DR: Luminescence was observed during the thermal decomposition of 3,3,4trimethyl-1,2-dioxetane to acetone and acetaldehyde.
Abstract: Luminescence is observed during the thermal decomposition of 3,3,4-trimethyl-1,2-dioxetane to acetone and acetaldehyde The wavelength maximum of the luminescence is at 430–440 mμ when the decompos
171 citations
TL;DR: In this article, a number of compositions A23+Ti24+O7 and related mixed phases were investigated for the trivalent lanthanons from Sm to Lu, and for Y, the homogeneous A2Ti2O7 phases were of the cu...
Abstract: A number of compositions A23+Ti24+O7 and of related mixed phases were prepared and investigated. For the trivalent lanthanons from Sm to Lu, and for Y, the homogeneous A2Ti2O7 phases were of the cu...
159 citations
TL;DR: In this article, the electron-ion and ion-ion recombination processes of importance in the upper atmosphere are considered, and available laboratory experimental and theoretical information concerning the relevant processes is discussed.
Abstract: The electron–ion and ion–ion recombination processes of importance in the upper atmosphere are considered, and available laboratory experimental and theoretical information concerning the relevant processes is discussed. For atomic ions the principal electron–ion recombination process is radiative, with theory indicating that the two-body coefficient at ∼200 °K is ∼10−11 cm3/s and decreases with increasing electron temperature. Microwave afterglow/mass spectrometer studies of diatomic ionospheric ions (e.g. NO+, O2+, and N2+) show a loss by dissociative recombination with a coefficient substantially in excess of 10−7 cm3/s at 250 °K and decreasing with increasing electron and ion temperature. There is some evidence from flame studies that H3O+ ions exhibit a very large coefficient (10−6–10−5 cm3/s) at 300 °K. Ion–ion recombination evidently proceeds by mutual neutralization, with laboratory studies of ions such as NO+ and NO2− indicating a two-body coefficient of the order of 10−7 cm3/s at 300 °K. In the ...
159 citations
TL;DR: In this paper, the radiative lifetimes, diffusion coefficients, and reaction rate coefficients of highly reactive metastable species with very long radiative lifetime have been studied in the light of atmospheric measurements and current theories of the terrestrial airglow and aurora.
Abstract: It is now possible to produce comparatively large concentrations of highly reactive metastable species in laboratory sources and to study metastable atoms and molecules with very long radiative lifetimes by photoionization mass spectroscopy, by vacuum ultraviolet absorption techniques, or by direct observation of the feeble radiation emitted by these excited species. These methods are being used widely to study the collisional deactivation of aeronomically important metastable species by quenching or by reaction. New information on radiative lifetimes, diffusion coefficients, and reaction rate coefficients is now available. These results are tabulated and reviewed in the light of atmospheric measurements and current theories of the terrestrial airglow and aurora.
142 citations
Abstract: The effects of pressures up to 4 kbar on the density, dielectric constant, and viscosity of n-pentane, n-hexane, n-octane, cyclopentane, methylcyclohexane, and 2,2-dimethylbutane (DMB) were measure...
136 citations
TL;DR: In this paper, star-shaped polystyrene samples have been synthesized by anionic block-copolymerization of styrene and divinylbenzene (DVB), the proportion of the latter monomer being of the order of a few molecules per living end.
Abstract: Star-shaped polystyrene samples have been synthesized by anionic block-copolymerization of styrene and divinylbenzene (DVB), the proportion of the latter monomer being of the order of a few molecules per living end. Vacuum technique was used and benzene was chosen as solvent. The samples were found almost free of linear polystyrene, and of very low polydispersity. The number of branches was found to be a function of the overall concentration, of the amount of DVB, and of the molecular weight of the linear precursor. The results obtained with the meta and the para isomers did not differ significantly, as far as the products themselves are concerned. However, spectroscopic investigations carried out during reaction showed that the reactivity of the 2 double bonds of the para isomer differ significantly, whereas this is not the case with the meta isomer.
134 citations
TL;DR: In this article, the rate coefficients for the various processes of aeronomic interest are discussed, including the three-body attachment to O2, the radiative attachment, and the dissociative attachment process.
Abstract: Techniques for the study of electron attachment and detachment are reviewed. The rate coefficients for the various processes of aeronomic interest are then discussed. The rates of three-body and dissociative attachment by thermal electrons have been successfully determined by swarm techniques and by high frequency studies of electrons produced by high energy particles and by photoionization. Collisional and associative detachment rates for thermal energy negative ions have been measured using the swarm and flowing afterglow techniques. Radiative attachment rates for some atmospheric negative ions have been calculated from measurements of photodetachment cross sections using crossed photon and ion beam techniques. Electron beam studies and measurements of ion kinetic energy have provided much useful information regarding the dissociative attachment process and the structure of molecular negative ions. Rate coefficients for low energy processes such as the three-body attachment to O2, the radiative attachme...
125 citations
TL;DR: In this paper, the exact analysis of ABC type absorption due to the CH2OH group of 3β-acetoxy-5β,6β-oxidocholestan-19-ol provides two vicinal HCOH coupling constants for dihedral angles of 80° and 160°.
Abstract: The exact analysis of the ABC type absorption due to the —CH2OH group of 3β-acetoxy-5β,6β-oxidocholestan-19-ol provides two vicinal HCOH coupling constants for dihedral angles of 80° and 160°. A least squares fit of these and previous data in the literature to a "Karplus" relation provides values for the coefficients in such an equation. The theoretical justification for such a relation has been obtained by extended Huckel molecular orbital calculations for methanol with different dihedral angles. The practical limitations in, and applications of the relation are discussed. An effect of solvent on the vicinal coupling constants is also noted and discussed.
TL;DR: The current status of absorption cross-section measurements for aeronomic use is reviewed in this article, where the recommended values for the gases O2, N2, O, and O3 are given at wavelengths where there is a strong atmosphere.
Abstract: The current status of absorption cross-section measurements for aeronomic use is reviewed. Recommended values for the gases O2, N2, O, and O3 are given at wavelengths where there is strong atmosphe...
TL;DR: In this paper, a detailed comparative study of various catalysts for the hydrogenolysis of spruce wood lignin was made, including Raney nickel, 10% palladium-charcoal, and 5% Raney copper.
Abstract: A detailed comparative study has been made of the effectiveness of various catalysts for the hydrogenolysis of spruce wood lignin. The catalysts studied were Raney nickel, 10% palladium–charcoal, 5...
TL;DR: In this paper, a series of fully esterified pentopyranosyl fluorides were analyzed by 1H and 19F nuclear magnetic resonance spectroscopy and it was shown that all such derivatives favor that conformer in which the f...
Abstract: Detailed studies, by 1H and 19F nuclear magnetic resonance spectroscopy, of a series of fully esterified pentopyranosyl fluorides, show that all such derivatives favor that conformer in which the f...
TL;DR: In this paper, the fundamental frequencies of isotopically dilute H2O, D2O and HDO molecules were obtained from the infrared spectra of partially deuterated hydrates.
Abstract: Infrared spectra of partially deuterated hydrates yield the fundamental frequencies of isotopically dilute H2O, D2O, and HDO molecules. Isotopic dilution eliminates vibrational coupling and allows ...
TL;DR: The reduction of hexofuranose and hexopyranose acetals with LiAlH4-AlCl3 (1:1, probably AlH2Cl) to the corresponding ethers proceeds in similar fashion as that of simple acetals and ketals (Scheme...
Abstract: The reduction of hexofuranose and hexopyranose acetals with LiAlH4–AlCl3 (1:1, probably AlH2Cl) to the corresponding ethers proceeds in similar fashion as that of simple acetals and ketals (Scheme ...
TL;DR: The flowing afterglow technique has been used to study the electron detachment reactions in the D region ionospheric c... as mentioned in this paper, and it has been shown that the rates of these reactions are sufficiently fast to make them important processes.
Abstract: The flowing afterglow technique has been used to study the electron detachment reactionsThe rates of these reactions are sufficiently fast to make them important processes in D region ionospheric c...
TL;DR: In this paper, the use of multiple-beam interferometry was extended to the study of the kinetics of the hydrolysis of ethyl acetate in acid solution.
Abstract: The use of multiple-beam interferometry has been extended to the study of the kinetics of the hydrolysis of ethyl acetate in acid solution. The rate of change of refractive index in the reacting so...
TL;DR: A mechanism based on the intermediacy of the S-nitroso derivative of cysteine and the intermediate formation of nitric oxide is proposed, and nitrous oxide is shown to be a final product.
Abstract: The reaction between cysteine and N-methyl-N-nitroso-p-toluenesulfonamide affords almost quantitative yields of cystine and N-methyl-p-toluenesulfonamide. A mechanism based on the intermediacy of t...
TL;DR: Experimental laboratory work is reviewed for the kinetics of 21 neutral, elementary reactions involving H, OH, HO2, H2, CO, N2O, CH4, and Na.
Abstract: Experimental laboratory work is reviewed for the kinetics of 21 neutral, elementary reactions involving H, OH, HO2, H2, CO, N2O, CH4, and Na.
TL;DR: In this article, the thermodynamic constants ΔH0n−1,n, ΔG0n − 1,n and ΔS0 n− 1 n for the reaction [n− 1, n] proceeding in the gas phase were measured for n = 1 to n = 6.
Abstract: The thermodynamic constants ΔH0n−1,n, ΔG0n−1,n, and ΔS0n−1,n for the reaction [n − 1, n]: K+(H2O)n−1 + H2O = K+(H2O)n proceeding in the gas phase were measured for n = 1 to n = 6. The equilibria we...
TL;DR: The desulfurization rates in hydrogen of thiophene, tetrahydrothiophene and n-butanethiol over molybdenum disulfide, an alumina supported cobalt molydate, and a chromia catalyst have been measured as mentioned in this paper.
Abstract: The desulfurization rates in hydrogen of thiophene, tetrahydrothiophene, and n-butanethiol over molybdenum disulfide, an alumina supported cobalt molybdate, and a chromia catalyst have been measure...
TL;DR: Inelastic scattering of electrons by nitrogen, oxygen, carbon monoxide, carbon dioxide, water, argon, and helium is reviewed in this article, where collision cross sections and generalized oscillator strengths are described, when data are available.
Abstract: Inelastic scattering of electrons by nitrogen, oxygen, carbon monoxide, carbon dioxide, water, argon, and helium is reviewed. Electron impact spectra at both high (less than 40 keV) and low (greater than 15 eV) kinetic energies are presented and discussed. Collision cross sections and generalized oscillator strengths are described, when data are available, and the connection with optical oscillator strengths is discussed. The limiting selection rules which hold in the excitation of atoms and molecules by electron impact are discussed and typical examples of forbidden transitions are described.
TL;DR: In this paper, the kinetics of the oxidation of a number of aliphatic and aromatic secondary alcohols with N-bromo succinimide has been investigated.
Abstract: The kinetics of the oxidation of a number of aliphatic and aromatic secondary alcohols with N-bromo succinimide has been investigated. Electron-withdrawing substituents retard the reaction consider...
TL;DR: In this article, 8-quinolinolate extraction methods for the determination of Al3+ plus mononuclear hydroxyaluminium ions, polynuclear hydroxal aluminium ions, and the initial solid phase formed when a base is added to AlCl3 solutions, are presented.
Abstract: 8-Quinolinolate extraction methods for the determination of Al3+ plus mononuclear hydroxyaluminium ions, polynuclear hydroxyaluminium ions, and the initial solid phase formed when a base is added to AlCl3 solutions, are presented. The methods are based on the rates of reactions of 8-quinolinol with the 3 forms of aluminium substances. Results under a variety of experimental conditions are reported.
TL;DR: In this paper, the thermal energy reactions of O− ions with saturated, hydrocarbon molecules have been investigated in a flowing afterglow of pure oxygen and a mixture of helium and oxygen.
Abstract: The thermal energy reactions of O− ions with saturated, hydrocarbon molecules have been investigated in a flowing afterglow of pure oxygen and a mixture of helium and oxygen. Hydrogen atom abstraction was found to be the dominant reaction channel. The reaction probability was found to increase for the higher members of the homologous series. The further reaction of the product OH− ions with saturated hydrocarbon molecules was not observed. This result was used to estimate an upper limit to the electron affinity of the free radicals CH3, C2H5, C3H7, and C4H9.
TL;DR: Methods of production and detection of reactive species of oxygen and nitrogen are discussed briefly in this paper, and a review of the data for reactions of these species which have aeronomic interest are reviewed.
Abstract: Methods of production and detection of reactive species of oxygen and nitrogen are discussed briefly. Kinetic data for reactions of these species which have aeronomic interest are reviewed. New dat...
TL;DR: Leaf wax of Little Club wheat is composed of: hydrocarbons (8, 15), esters (20, 26), alcohols (25, 42%), acids (2, 6, 10), hydroxy β-diketones (9, 16), and unidentified material (9-12%).
Abstract: Leaf wax of Little Club wheat is composed of: hydrocarbons (8–15%); esters (20–26%); alcohols (25–42%); acids (2%); β-diketone (6–10%); hydroxy β-diketones (9–16%); and unidentified material (9–12%). The esters are mainly octacosanol esters of C14 to C32 fatty acids but lesser amounts of esters of trans 2-tetracosenoic and trans 2-docosenoic acids also occur. The free alcohols are almost entirely octacosanol. The β-diketone is hentriacontane-14,16-dione and the hydroxy-β-diketones are a 1:1 mixture of 8- and 9-hydroxyhentriacontane-14,16-diones.
TL;DR: The infrared spectrum of N,N-dimethyldithiocarbamate complex of nickel(II) has been recorded in the range 2000-250 cm−1 as discussed by the authors.
Abstract: The infrared spectrum of N,N-dimethyldithiocarbamate complex of nickel(II) has been recorded in the range 2000–250 cm−1. Normal coordinate analyses have been made for nickel dimethyldithiocarbamate and nickel dimethyldiselenocarbamate complexes and their infrared spectra indexed. The frequency shifts observed on alkyl substitution have been discussed. The M—Se stretching frequency occurs about 100 cm−1 lower in the diselenocarbamate complex as compared to M—S frequency of the dithiocarbamate.
TL;DR: In this paper, a summary of the processes by which low energy electrons lose energy in moving through the atmosphere and estimates of the cross sections and energy loss rates are given, and mechanisms by which thermal electrons cool are described and the cooling efficiencies are listed.
Abstract: A summary is presented of the processes by which low energy electrons lose energy in moving through the atmosphere and estimates are given of the cross sections and energy loss rates. The mechanisms by which thermal electrons cool are described and the cooling efficiencies are listed.