Showing papers in "Canadian Journal of Chemistry in 1963"
TL;DR: The pyrolysis of trimethyl gallium has been studied in a toluene carrier flow system from 686° K to 983° K using total pressures from 6.1 mm to 31.1
Abstract: The pyrolysis of trimethyl gallium has been studied in a toluene carrier flow system from 686° K to 983° K using total pressures from 6.1 mm to 31.1 mm. The progress of the reaction was followed by...
202 citations
TL;DR: The empirical linear correlation between the proton resonance shifts in aromatic molecules and the local electron density on the carbon atom to which the Proton is bonded has been studied in this paper.
Abstract: The quantitative nature of the empirical linear correlation between the proton resonance shifts in aromatic molecules and the local electron density on the carbon atom to which the proton is bonded...
194 citations
TL;DR: In this article, it was shown that the bond length of an SO bond and the bond angle in an SO2 group may be satisfactorily correlated with the SO stretching frequency.
Abstract: It is shown that the bond length of an SO bond and the bond angle of an SO2 group may be very satisfactorily correlated with the SO stretching frequency The bond-length – stretching-frequency rela
127 citations
TL;DR: In this article, the anodic oxidation of ammonia in aqueous potassium hydroxide solutions at platinum black electrodes was studied and a kinetic scheme of consecutive reactions was proposed. But the authors did not consider the effect of the anisotropic nature of the solution.
Abstract: Electrochemical kinetic studies are reported on the anodic oxidation of ammonia in aqueous potassium hydroxide solutions at platinum black electrodes. A kinetic scheme of consecutive reactions is p...
126 citations
TL;DR: An investigation of the kinetics of the protodeboronation of benzeneboronic acid in water in the pH range 20 to 67 is described in this paper, in addition to the acid-catalyzed reaction studied earlier.
Abstract: An investigation of the kinetics of the protodeboronation of benzeneboronic acid in water in the pH range 20 to 67 is described In addition to the acid-catalyzed reaction studied earlier a react
104 citations
TL;DR: The relative rates of reaction of 11 meta-and para-substituted phenols with styrylperoxy radicals have been measured at 65 °C and have been shown to give an excellent correlation with electrophili...
Abstract: The relative rates of reaction of 11 meta- and para-substituted phenols with styrylperoxy radicals have been measured at 65 °C and have been shown to give an excellent correlation with electrophili...
103 citations
TL;DR: In this paper, the rates of methanolysis reactions of D-xylose, D-arabinose and D-lyxose have been determined, and it was found that methanogenesis of a pentose proceeds to equilibrium through four distinguishab...
Abstract: Rates of methanolysis reactions of D-xylose, D-arabinose, D-lyxose, and D-ribose have been determined. It was found that methanolysis of a pentose proceeds to equilibrium through four distinguishab...
96 citations
TL;DR: In this paper, the proton resonance spectra of solutions of N, N-dimethylacetamide, formamide, and N,Ndimethylformamide in fluorosulphuric acid have been studied at temperatures between 25° and −98°.
Abstract: The proton resonance spectra of solutions of acetamide, N,N-dimethylacetamide, formamide, and N,N-dimethylformamide in fluorosulphuric acid have been studied at temperatures between 25° and −98°. At low temperatures a new peak appears in the spectra of solutions of all four compounds which is not present at room temperatures and which, from peak areas and other consideration, may be assigned with certainty to the group. It is thereby unambiguously established that these amides protonate on the carbonyl oxygen and not on the nitrogen atom.
95 citations
TL;DR: In this paper, an isothermal calorimetric probe was used to examine vibrationally excited nitrogen molecules produced both by a microwave discharge in nitrogen and also by the reaction, and the energy associated with an 'active' nitrogen stream, due to vibrational excited N2, was found to be 6.03 kcal mole−1 of total nitrogen.
Abstract: Vibrationally excited nitrogen molecules produced both by a microwave discharge in nitrogen and also by the reactionhave been examined using an isothermal calorimetric probe.In the first case the energy associated with an 'active' nitrogen stream, due to vibrationally excited N2, was found to be 6.03 kcal mole−1 of total nitrogen. The subsequent relaxation of this species was found to occur almost entirely on the walls of the reaction vessel, with a collision efficiency of 4.5 × 10−4. The addition of other gases greatly accelerated the homogeneous relaxation rate. Collisional efficiencies of N2O, CO2, and Ar were found to be 0.8 × l0−4, 2.3 × 10−5, and 1.0 × 10−6 respectively.The vibrationally excited nitrogen produced by the N/NO reaction was found to possess 20 ± 4 kcal mole−1 of energy compared with the maximum of 75 kcal mole−1 allowed by the exothermicity of the reaction.
91 citations
TL;DR: In this article, a differential thermal analysis technique was used to study the carbothermic reduction of aluminum oxide at reduced pressures in the temperature range 1700-2200 °K, and the reduction was found to be effective.
Abstract: A differential thermal analysis technique was used to study the carbothermic reduction of aluminum oxide at reduced pressures in the temperature range 1700–2200 °K. The reduction was found to proce...
84 citations
TL;DR: In this paper, the kinetics of electrochemical decarboxylation of formate ions have been studied in detail for the first time as a model reaction for examination of the decarsylation and radical coupling.
Abstract: The kinetics of electrochemical decarboxylation of formate ions has been studied in detail for the first time as a model reaction for examination of the decarboxylation and radical coupling that oc...
TL;DR: An expression for the broadening of the components of the quartet obtained for the n.m.r. spectrum of nuclei coupled to a nucleus of spin 3/2 undergoing electric quadrupole relaxation was derived in this paper.
Abstract: An expression is derived for the broadening of the components of the quartet obtained for the n.m.r. spectrum of nuclei coupled to a nucleus of spin 3/2 undergoing electric quadrupole relaxation. I...
TL;DR: The relative rates of reaction of a large number of ortho-alkyl phenols with styrylperoxy radicals have been measured at 65 °C in this article, where the reaction rate of these groups has both an accelerating effect owing to their electron...
Abstract: The relative rates of reaction of a large number of ortho-alkyl phenols with styrylperoxy radicals have been measured at 65 °C. These groups have both an accelerating effect owing to their electron...
TL;DR: In this article, the irradiation of acetylacetone in the presence of oct-1-ene, cyclopentene and cyclohexene gives substituted heptandiones.
Abstract: The irradiation of acetylacetone in the presence of oct-1-ene, cyclopentene, cyclohexene, and 1-methylcyclohexene gives substituted heptandiones. These diketones may then be cyclized with acid or b...
Abstract: The transmission of polar effects by various groups is assessed by means of the reaction constants ρ or ρ″. The results are critically discussed in terms of the various polar, steric, and solvent e...
TL;DR: Xanthone, a member of the γ-pyrone species, which have basic carbonyl groups, forms an excellent series of solid complexes with Lewis acids as discussed by the authors.
Abstract: Xanthone, a member of the γ-pyrone species, which have basic carbonyl groups, forms an excellent series of solid complexes with Lewis acids. In these complexes the carbonyl oxygen atom is the donor...
TL;DR: The system 10- 4 M terephthaiic acid in 4 x 10-4 M NaOH is capable of measuring doses of ionizing radiation as low as 500 millirads and the concentration of hydroxyterephthalic acid increases linearly with dose to at least 1000 rads and is independent of dose rate from 0.5 to 1000 rad/min.
Abstract: The system 10-4 M terephthaiic acid in 4 x 10-4 M NaOH is capable of measuring doses of ionizing radiation as low as 500 millirads. The concentration of hydroxyterephthalic acid, determined spectrophotofluorometrically, increases linearly with dose to at least 1000 rads and is independent of dose rate from 0.5 to 1000 rad/min. The energy dependence and stability of the system are also reported.
TL;DR: In this paper, it was shown that the major isomer of a given pair possesses the configuration in which the C-methyl group is endo- and the OR group is exo-.
Abstract: Diastereoisomeric 1,2-orthoacetates of D-mannose are formed under conditions of the Konigs–Knorr synthesis. This is shown by the isolation of two crystalline isomers of β-D-mannose 1,2-(benzyl orthoacetate), and also by examination of the nuclear magnetic resonance (n.m.r.) spectra of several D-mannose orthoacetates. The diastereoisomers show notable differences in respective chemical shifts for the C-methyl and other protons and these variations, together with isomer-ratio data, suggest that the major isomer of a given pair possesses the configuration in which the C-methyl group is endo- and the OR group is exo-. On acid hydrolysis the orthoacetates yield mainly 2-O-acetyl-D-mannose, the structure of which is confirmed by n.m.r. spectral evidence.
TL;DR: Xanthate solutions of pH 6-10, prepared from "aged" potassium ethyl xanthate crystals, KEtX, were investigated spectrophotometrically in the region 190-400 mμ.
Abstract: Xanthate solutions of pH 6–10, prepared from "aged" potassium ethyl xanthate crystals, KEtX, were investigated spectrophotometrically in the region 190–400 mμ and showed coexistence of xanthate ion...
TL;DR: In this article, the chemical shifts of protons and carbon-13 nuclei in aliphatic and aromatic halogen compounds are considered on the basis of inductive, magnetic anisotropy, and intramolecular dispersion effects.
Abstract: The chemical shifts of protons and carbon-13 nuclei in aliphatic and aromatic halogen compounds are considered on the basis of inductive, magnetic anisotropy, and intramolecular dispersion effects....
TL;DR: A neutral extracellular glucan ([α]D23 + 189°) was produced in 12% yield by Pullularia pullulans (de Bary) Berkhout grown on a glucose substrate.
Abstract: A neutral extracellular glucan ([α]D23 + 189°) was produced in 12% yield by Pullularia pullulans (de Bary) Berkhout grown on a glucose substrate. A single symmetrical peak on free-boundary electrop...
TL;DR: The proton magnetic resonance spectra of solutions of amides in fluorosulphuric acid confirm previous results which indicated that protonation occurs on the carbonyl oxygen.
Abstract: The proton magnetic resonance spectra of solutions of amides in fluorosulphuric acid confirm previous results which indicated that protonation of amides occurs on the carbonyl oxygen. A similar stu...
TL;DR: In this paper, nuclear characteristics and excitation functions were studied for isotopes of Tm, Er, Ho, and Dy, formed by various (p,xn) and (p xpxn) reactions.
Abstract: Erbium was bombarded with protons of energies varying between 6 and 87 Mev. Nuclear characteristics and excitation functions were studied for isotopes of Tm, Er, Ho, and Dy, formed by various (p,xn) and (p,xpxn) reactions. Bombardment of enriched Er isotopes helped elucidate some of the excitation functions. A comparison has been made of the experimental (p,xn) cross sections with those predicted by the Jackson model and reasonable agreement has been found. Holmium was bombarded with α-particles to produce the compound nucleus Tm169* and the ratios σ (p,n): σ (p,2n) = σ (α,n): σ(α,2n) were found to hold.
TL;DR: For oxygen compounds of chlorine, phosphorus, and silicon, correlations were established between stretching frequencies and force constants of Cl-O, P-O and Si-O bonds.
Abstract: For oxygen compounds of chlorine, phosphorus, and silicon, respectively, correlations are established between stretching frequencies and force constants of Cl—O, P—O, and Si—O bonds, and their bond...
TL;DR: In this paper, the first transition series of neutral transition metals has been calculated using the Mulliken formula for a wide variety of hybrid states, including the electron affini-gating of the neutral transition metal.
Abstract: The orbital electronegativities of the neutral transition metals of the first transition series have been calculated by the Mulliken formula for a wide variety of hybrid states. The electron affini...
TL;DR: In this paper, an electrochemical kinetic analysis of the Kolbe reaction in trifluoroacetate-100% TCA was carried out from an electrostatic viewpoint with minimum complication by oxidative side reactions and linear Tafel slopes were deduced for the Langmuir and Temkin conditions of surface coverage by intermediates.
Abstract: Electrochemical kinetic studies on the Kolbe reaction have been carried out in the trifluoroacetate–100% trifluoroacetic acid system, where the reaction can be examined from an electrochemical viewpoint with minimum complication by oxidative side reactions. High yields of the Kolbe products C2F6 and CO2 are obtained and current–potential curves exhibiting transition behavior and linear Tafel regions are found. Tafel slopes are deduced for "Langmuir" and "Temkin" conditions of surface coverage by intermediates and compared with the experimental observations. Plausible reaction mechanisms are proposed, which are supported by galvanostatic discharge transients; the latter indicate that the coverage by adsorbed intermediates in the trifluoroacetate reaction approaches a monolayer. In the aqueous formate systems, multilayer formation is indicated, including deposition of layers of different species corresponding to different arrest regions in the galvanostatic discharge transients. It is suggested that these l...
TL;DR: Nuclear reactions induced in tantalum by protons of energy up to 84 Mev have been studied and excitation functions obtained for products formed by (p,xn), ( p,pxn) reactions as mentioned in this paper.
Abstract: Nuclear reactions induced in tantalum by protons of energy up to 84 Mev have been studied and excitation functions obtained for products formed by (p,xn), (p,pxn), (p,2pxn), and (p,3pxn) reactions....
TL;DR: A β-D-(1 → 3)-glucanase from the Basidiomycete sp.
Abstract: A β-D-(1 → 3)-glucanase from the Basidiomycete sp. QM 806 of Reese and Mandels has been purified and shown to hydrolyze insoluble laminarin by removing glucose residues one at a time from the non-r...
TL;DR: In this article, a method for the quantitative description of the profile and asymmetry of an infrared absorption band, based on the computation of the second and third incomplete moments of the absorbance curve, is described.
Abstract: A method is described for the quantitative description of the profile and asymmetry of an infrared absorption band, based on the computation of the second and third incomplete moments of the absorbance curve. Provision is included for differentiation between the intrinsic band asymmetry and that induced by instrumental factors dependent on the direction of scan. A program has been prepared for an I.B.M. 1620 computer to facilitate the calculation of the moments. This program also yields the incomplete fourth moments, the statistical kurtosis parameter (), and the Gauss–Cauchy index, though these quantities are not employed in the present investigation. Examples are given of the application of these computations to the analysis of the effect of the spectral slit width on the profiles of bands at 812.7 and 726.6 cm−1 respectively in the spectra of carbon disulphide solutions of perylene and anthracene, and of the effect of the amplifier time constant on the asymmetry of the band at 2234.4 cm−1 in the spectr...