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Showing papers on "Methanol published in 1968"


01 Jan 1968
TL;DR: An all-glass apparatus for the extraction, evaporation and methanolysis of small amounts of lipids has been designed in this paper, which is useful for preparation of fatty acid methyl esters from leaf lipids (neutral lipids, phospho-and galacto-lipids).
Abstract: An all-glass apparatus for the extraction, evaporation and methanolysis of small amounts of lipids has been designed. The special methanolysis tubes fit to an apparatus capable of handling 10 samples simultaneously. Reaction times of 2-5 minutes are effective for the conversion of seed oil triglycerides to fatty acid methyl esters by heating in methanol containing sodium methoxide. The same equipment is useful for preparation of fatty acid methyl esters from leaf lipids (neutral lipids, phospho-and galacto-lipids) by consecutive 5 minute treatments with NaOH in methanol and BF 3 in methanol. In studies on the further treatment of the methyl esters obtained from rape seed it has been found that the crude preparation possessed an oxidative stability which permitted evaporation under a stream of air; the pure esters obtained from preparative thin layer chromatography on the other hand had to be treated much more carefully. Gas chromatographic analysis of the crude and pure esters yielded the same fatty acid composition when the esters were protected by an antioxidant during the thin layer chromatographic separation; without this protection losses, mainly of the linolenic ester, infrequently occurred. The partial extraction of lipids in the all-glass equipment gave an extract with the same fatty acid composition as the complete extract prepared in stainless steel tubes according to Troeng thus permitting comparison of data obtained on seed samples by either extraction method. The steel tubes are prefered when larger amounts of material are available, the glass extractors for smaller amounts due to problems of contamination of esters when using the former method. Several sources of laboratory contaminants, troublesome errors in lipid micro-analysis, have been traced and their TLC and GLC patterns have been analysed. Based on these experiences, several precautions are recommended in order to minimize the contamination problem in lipid microanalysis.

144 citations


Journal ArticleDOI
TL;DR: An enzyme isolated from the mycelium of a Basidiomycete belonging to the family Polyporaceae catalyzes the oxidation of the lower primary alcohols to the corresponding aldehydes and H2O2, which may be useful for the colorimetric determination of methanol, ethanol, or other lower alchols.

83 citations


Journal ArticleDOI
TL;DR: In this article, the same rate equation was found empirically in the case of methanol and ethanol to ether and of tert-butanol to olefin, and the selectivity with respect to both types of compounds was regarded as a function of the thermal stability of the respective surface alkoxides.

67 citations



Journal Article
TL;DR: In vitro studies in vitro which measured the methanol-oxidizing activity of hepatic alcohol dehydrogenase isolated from monkeys also support the view that this enzyme is largely responsible for meethanol oxidation in this species.
Abstract: The peroxidative system involving hepatic catalase plays a major role in the oxidation of methanol in the rat (1), but in the monkey the peroxidative mechanism does not appear to be important. This conclusion is based on the following observations: (a) ethanol and methanol were about equally reactive with the peroxidative system, but ethanol was much more reactive with the alcohol dehydrogenase system than methanol. Ethanol was a much more effective inhibitor of methanol oxidation in the intact monkey than it was in the rat, which is what would be expected if methanol is oxidized by the alcohol dehydrogenase system in the monkey, but by the peroxidative system in the rat. (b) By similar reasoning, 1-butanol was a stronger inhibitor of methanol oxidation in the monkey than it should have been if the peroxidative system was involved. (c) 3-Amino-1,2,4-triazole, a potent inhibitor of hepatic catalase, greatly reduced methanol oxidation in the rat, but had no measurable effect on methanol oxidation in the monkey. (d) Ethylene glycol stimulated the rate of methanol oxidation in the rat, probably as a result of an increased H2O2 production that occurs when glycolic acid, a metabolite of ethylene glycol, is oxidized to glyoxylic acid (6,7); no such stimulation was seen in the monkey. Studies in vitro which measured the methanol-oxidizing activity of hepatic alcohol dehydrogenase isolated from monkeys also support the view that this enzyme is largely responsible for methanol oxidation in this species.

55 citations


Journal ArticleDOI
M. E. Bergy1
TL;DR: Lomofungin is a new antibiotic which is extracted from the fermentation broth of Streptomyces lomondensis var.
Abstract: Lomofungin is a new antibiotic which is extracted from the fermentation broth of Streptomyces lomondensis var. lomondensis with methyl ethyl ketone and purified by crystallization. It is an acidic olive-yellow colored compound with a molecular formula C15H10N2O6 and a molecular weight of 314. It exhibits ultraviolet and visible absorption maxima at 221, 270, 311, 375 and 439mμ in 0.01N methanolic hydrochloric acid, and at 239, 265, 299, 342, 478 in 0.01N aqueous sodium hydroxide. Lomofungin does not melt below 320°C.It is soluble in dimethylformamide, alkaline water, acidic acetone and acidic methyl ethyl ketone but only slightly soluble in water, methanol, cyclohexane, acetone, ether or ethyl acetate.

55 citations


Journal ArticleDOI
TL;DR: In this paper, the effect of anions on the oxidation of chemisorbed carbonaceous species formed during the anodic oxidation of methanol is attributed to a displacement of the discharge of water molecules to more positive potentials with increasing adsorbability of the anions.
Abstract: The effect of anions on the oxidation of chemisorbed carbonaceous species formed during the anodic oxidation of methanol is attributed to a displacement of the discharge of water molecules to more positive potentials with increasing adsorbability of the anions. The efficiency of CO2 production decreases from about 90% at a methanol bulk concentration of 0·01 M to about 10% at 5 M in 0·5 M H2SO4 at constant potential between 0·5 and 0·7 V. The comparison of the maximum rates of individual reactions with the net rate and the efficiency of CO2 production leads to the conclusion that the CO2 evolution does not occur predominantly by the formation and oxidation of the carbonaceous species.

54 citations


Journal ArticleDOI
M.W. Breiter1
TL;DR: In this article, the initial potential of the oxidation arrest in anodic charging curves depends upon temperature in nearly the same way for type-I species of adsorbed carbon monoxide and for reduced carbon dioxide, but in a different way for the chemisorbed carbons formed from methanol.

50 citations


Journal ArticleDOI
TL;DR: In this article, the same species is absorbed in all the cases studied and that it has the composition HCO, and it is probable that COOH radicals are also present to a certain extent.

45 citations


Journal ArticleDOI
TL;DR: In this paper, the γ radiolysis of a binary mixture of methanol and water over a wide concentration range has been investigated, and the observed yields of products are expressed as a linear function of the electron fraction of the mixture.
Abstract: The γ radiolysis of a binary mixture of methanol and water over a wide concentration range has been investigated. The observed yields of products are expressed as a linear function of the electron fraction of methanol in the mixture. The yields of molecular hydrogen were also determined. Analyzing the results on reasonable assumptions, one could obtain for neutral water, Ge\barsw=2.3–2.5 and GOHw≥2.6. It was concluded that, in the radiolysis of methanol, formaldehyde may be produced through the decomposition of CH2OH radicals in the spur region, not by the disproportionation of these radicals.

45 citations


Journal ArticleDOI
TL;DR: In this article, the reaction of methyl radicals with three isotopically different isopropanols and the undeuterated ethers (diisopropyl and dimethyl ethers) have been investigated.
Abstract: The reactions of methyl radicals with three isotopically different isopropanols three isotopically different methanols and the undeuterated ethers (diisopropyl and dimethyl ethers) have been investigated. The photolysis of acetone or acetone-d6 has been used to generate methyl radicals or trideuteromethyl radicals. An isotopic exchange reaction between acetone and alcohols makes it necessary to work with isotopically compatible pairs. Values for Arrhenius parameters, based on Shepp's rate-constant for the combination of methyl radicals, are as follows : [graphic omitted] Primary isotope effects in the alkyl groups of these alcohols are larger than expected solely on the basis of zero-point-energy difference : at 150°, (kCH/kCD) is ca. 8 for methanol and ca. 6.5 for isopropanol. These values, which resemble those for ethanol and for isobutane, taken together with the corresponding activation-energy differences, suggest that tunnelling may again be important. A secondary reaction, disproportionation between the radicals · C(CH3)2OH and CH3, is important in attack on isopropanol. It gives rise to an apparent enhancement of reactivity of the hydroxyl groups, to a spurious secondary isotope effect and, unless allowance is made, to a low value for the A-factor. The corresponding reaction does not appear to be significant in methanol or ethanol systems. In dimethyl ether, the reactivity of each methyl group is the same as in methanol but in diisopropyl ether there is steric hindrance and the alpha hydrogen atoms are less accessible than in the alcohol.

Journal ArticleDOI
TL;DR: In this article, a method for the direct quantitative gas chromatographic separation of C2-C6 lower fatty acid homologues, methanol, and ethyl alcohol in aqueous microbial fermentation media was described.
Abstract: A method is described for the direct quantitative gas chromatographic separation of C2-C6 lower fatty acid homologues, methanol, and ethyl alcohol in aqueous microbial fermentation media. A hydrogen flame detector and a single-phase solid column packing, comprising beads of a polyaromatic resin (polystyrene cross-linked with divinyl benzene), were employed. Direct injections of 1 to 10 μliters of aqueous culture supernatant fluids were made. Quantitative recoveries of C2-C6 acids added to culture supernatant fluids were obtained.


Patent
11 Oct 1968
TL;DR: In this article, a process is provided for the MANUFACTURE of METHANOL and AMMONIA COMPRISING OPERATING SEQUENTIALLY a high pressure HYDROCARBON this articleORMING ZONE in SERIES with a low pressure METHANE SYNTHESIS ZONE, in Series with a WATER SHIFT CONVERSION ZONE.
Abstract: A PROCESS IS PROVIDED FOR THE MANUFACTURE OF METHANOL AND AMMONIA COMPRISING OPERATING SEQUENTIALLY A HIGH PRESSURE HYDROCARBON REFORMING ZONE IN SERIES WITH A LOW PRESSURE METHANOL SYNTHESIS ZONE, IN SERIES WITH A WATER SHIFT CONVERSION ZONE, IN SERIES WITH A CARBON DIOXIDE REMOVAL ZONE, IN SERIES WITH AN AMMONIA SYNTHESIS ZONE. SUCH COMBINATION TAKE ADVANTAGES OF SAID NEWLY DEVELOPED LOW PRESSURE METHANOL PROCESS AND THEREBY SAVES SUBSTANTIAL OPERATING COATS IN CARBON DIOXIDES COMPRESSION IN ADDITION TO SUBSTANTIALLY INVESTMENT COSTS BY UTILIZING A SINGLE PROCESS TRAIN INSTEAD OF THE HERETOFORE EMPLOYED INDEPENDENT METHANOL AND AMMONIA PLANTS.



Journal ArticleDOI
TL;DR: In this article, a proton and boron-11 chemical shift and coordination number study of complexes of diborane and the trihalides with dimethyl ether, diethyl ether, methanol, tetrahydrofuran, and to a small extent, acetone and N,N-dimethylformamide has been completed.
Abstract: : A proton and boron-11 chemical shift and coordination number study of complexes of diborane and the boron trihalides with dimethyl ether, diethyl ether, methanol, tetrahydrofuran, and, to a small extent, acetone and N,N-dimethylformamide has been completed. At low temperatures, separate proton resonance signals are observed for bulk solvent and solvent molecules complexed with the boron species. Coordination numbers were measured by the direct integration of the separate signals. The chemical shift separations for bulk and complexed solvent signals decreased in the order BBr3 > BCl3 > BF3 > BH3. An attempt is made to relate these separations to the coordinating abilities of the boron halides. The proton chemical shift data of the bases were correlated with some diborane 11B and 1H nuclear magnetic resonance results to obtain information concerning the species present in the ether-diborane solution. (Author)


Journal ArticleDOI
01 Mar 1968-Talanta
TL;DR: The anion-exchange characteristics of the platinum metals and gold in hydrochloric acid media are described and the conditions most suitable for quantitative separation are discussed.

Journal ArticleDOI
TL;DR: In this paper, the molar excess Gibbs free energies of mixtures of methanol and ethanol with n-decanol were obtained from static vapor pressure measurements over the temperature range 20-50 °C.
Abstract: Molar excess Gibbs free energies of mixtures of methanol and ethanol with n-decanol were obtained from static vapor pressure measurements over the temperature range 20–50 °C The molar excess entro


Journal ArticleDOI
06 Jan 1968-Nature
TL;DR: Carbon dioxide binds to haemoglobin at −55° C, in methanol and water, in a manner basically similar to binding in ordinary conditions.
Abstract: Carbon dioxide binds to haemoglobin at −55° C, in methanol and water, in a manner basically similar to binding in ordinary conditions.


Journal ArticleDOI
TL;DR: In this paper, the rates of the thermal decomposition of t-butyl methyl ether have been measured in the range 433-495o and the reaction products are isobutene and methanol, and the kinetic form is first order.
Abstract: The rates of the thermal decomposition of t-butyl methyl ether have been measured in the range 433-495o. The reaction products are isobutene and methanol, and the kinetic form is first order. The Arrhenius equation K1 = 1014.38exp(-61535/RT) sec-1 describes the variation of rate with temperature. The reaction behaviour is consistent with a unimolecular mechanism. Comparison of the results with those obtained for the production of isobutene from various t-butyl compounds indicates that the reaction has some degree of heterolytic character.

Journal ArticleDOI
TL;DR: In this article, the reaction of 2-propanol at 25 °C with oxygen atoms in the ground electronic state, O(3P), and, as a corollary, with the excited mercury atoms, Hg 6 (3P1), has been carried out.
Abstract: An investigation of the reaction of 2-propanol at 25 °C with oxygen atoms in the ground electronic state, O(3P), and, as a corollary, with the excited mercury atoms, Hg 6(3P1), has been carried out. The reaction of oxygen atoms with methanol at 25 °C has also been briefly studied. The general mechanism of reaction of O(3P) atoms with simple alcohols is discussed.

Journal ArticleDOI
TL;DR: In this article, the effect of methyl iodide on the acetic acid synthesis from methanol and carbon monoxide catalyzed by the same catalyst has been investigated and a possible reaction scheme was proposed.
Abstract: The reaction of methyl iodide with carbon monoxide in the presence of cobalt (II) iodide as the catalyst has been investigated to know the effect of methyl iodide on the acetic acid synthesis from methanol and carbon monoxide catalyzed by the same catalyst. The reaction, CH3I+CO+H2O→CH3COOH+HI, does not take place before the methyl iodide used has been hydrolyzed completely into methanol and sodium iodide by adding enough amount of sodium acetate (CH3I+CH3COONa+H2O→CH3OH+NaI+CH3COOH). Methyl iodide also strongly inhibits the reaction of methanol with carbon monoxide catalyzed by cobalt (II) ion or dicobalt octacarbonyl, although iodide ion promotes the reaction effectively. The promotion effect of iodide ion has been discussed by considering the effect of an additive on carbonylation reactions in terms of a labilizing ligand and a non-labilizing ligand and a possible reaction scheme of methanol with carbon monoxide catalyzed by cobalt(II) iodide has been proposed.

Journal ArticleDOI
TL;DR: In this paper, anodes used in this study were platinum, gold, palladium, lead dioxide, and graphite, and all of the anodes except graphite can be used successfully for the same process in both methanol and glacial acetic acid.
Abstract: The anodes used in this study were platinum, gold, palladium, lead dioxide, and graphite. The normal Kolbe process, the formation of ethane (and methane) and carbon dioxide, can be realized at a potential higher than 2.0v (vs. SCE) in both methanol and glacial acetic acid. In methanol, only platinum and gold seem to be suitable for realizing the process. In glacial acetic acid, however, all of the anodes except graphite can be used successfully for the same process. Another process, the formation of methyl acetate, occurs in both solvents at graphite in the potential range 1.4–2.0v. A side reaction observed in methanol at palladium, graphite, and lead dioxide was the formation of formaldehyde (and methyl formate in case of lead dioxide) which occurs at potentials as low as 1.2v.

Patent
Dana Peter Carlson1
01 Apr 1968
TL;DR: Stabilized tetrafluoroethylene-fluoroolefin copolymers having methyl ester end-groups were produced by as discussed by the authors, where the polymer was contacted with methanol at from about 65-200* C for the carboxylic acid end groups and from about 0-200 * C for acid fluoride end groups.
Abstract: Stabilized tetrafluoroethylene-fluoroolefin copolymers having methyl ester end-groups are produced from tetrafluoroethylenefluoroolefin copolymers having carboxylic acid end-groups and acid fluoride end-groups by contacting the polymer with methanol at from about 65-200* C. for the carboxylic acid end-groups and from about 0-200* C. for the acid fluoride end-groups and then drying the stabilized polymer.

Journal ArticleDOI
01 Feb 1968-Talanta
TL;DR: The extraction of silver, mercury, selenium, zinc, cobalt and iron with tridodecylamine and tributyl phosphate from hydrochloric acid solutions in aqueous methanol, ethanol and acetone is reported.

Journal ArticleDOI
TL;DR: In this article, the kinetics of anodic oxidation of the organic species adsorbed on platinized platinum from methanol, formic acid and CO2 solutions have been investigated.