bluuebunny/crossref_metadata_2025 huggingface dataset:
ETHYLENE DIAMINE TETRAACETIC ACID AND CITRIC ACID AS ELUANTS IN ION EXCHANGE SEPARATION OF RARE EARTHS
Authors: Cornish F. W. , Phillips G. , Thomas A.
Published: May 2006

Studies of the distribution of rare earths between the cation exchange resin Zeokarb 225 and solutions of ethylene diamine tetraacetic acid (EDTA) show the existence of large separation factors between members of this series. However, column experiments show that the separation is poorer than with citric acid, probably because of a slow process occurring in the solution. The variation of column efficiency with distribution coefficient has been examined. Elution of europium with citric acid appears to be diffusion controlled, while that with EDTA is not. Further experiments with strontium indicate that its elution with both EDTA and citric acid is diffusion controlled. The results are in general agreement with Glueckauf's equation relating column variables with the height equivalent to a theoretical plate. Column irregularities appear to account for the very low diffusion constants calculated from this relation.
THE SURFACE ENERGIES OF AMORPHOUS SILICA AND HYDROUS AMORPHOUS SILICA
Authors: Brunauer Stephen , Kantro D. L. , Weise C. H.
Published: May 2006

The total surface energies (or, more strictly, surface enthalpies) of amorphous silica and hydrous amorphous silica were determined by measuring the heats of solution in a mixture of nitric acid and hydrofluoric acid of samples having differing specific surface areas and bound water contents, and by measuring the surface areas by the B.E.T. method, using nitrogen as adsorbate. The molecular area of nitrogen was taken to be 16.2 Å2 at 77.3 °K. The surface energy of amorphous silica of zero water content (or the energy of the pure siloxane surface) at 23 °C. was found to be 259 ± 3 ergs/cm.2 The heat of hydration by liquid water of the siloxane surface to silanol surface at 23 °C. was found to be 258.6 ± 13.0 cal./gm. of water. From these two values, with the added assumption that the molecular area of bound water was 25 Å2, the surface energy of hydrous amorphous silica with a completely hydrated surface (or the energy of pure silanol surface) at 23 °C. was calculated to be 129 ± 8 ergs/cm.2 This value is only slightly greater than the surface energy of liquid water. Surface area determinations were also made by water vapor adsorption at 25 °C. The packing of physically adsorbed water appeared to be determined by the geometry of the surface. The cross-sectional area of the adsorbed water molecule was found to be 12.5 Å2. The density of amorphous anhydrous silica was 2.28 to 2.29 gm./cc. Silica particles having an average dimension of 37 Å were dehydrated at lower temperatures and sintered at lower temperatures than particles having an average dimension of 64 Å.
LYCOPODIUM ALKALOIDS: IV. REACTIONS OF α-CYANOBROMOLYCOPODINE AND ITS DERIVATIVES
Authors: Barclay L. R. C. , MacLean David B.
Published: May 2006

The hydrogenolysis and hydrolysis of α-cyanobromolycopodine to the secondary tricyclic base, α-des-dihydrolycopodine, is reported. The latter compound was converted to the methiodide in poor yield so that further degradations of the molecule through this derivative were not feasible. Hydride reductions of α-cyanobromolycopodine and some of its derivatives are recorded. The presence of a methylene group adjacent to the carbonyl group in lycopodine has been proved. Evidence is presented which suggests that the carbonyl group and the nitrogen atom are relatively close to one another in the molecule.
LIGHT ABSORPTION STUDIES: PART VI. THE EFFECTIVE INTERFERENCE VALUES OF NON-BONDED ATOMS IN SOLUTION. PART I. SOME PRELIMINARY OBSERVATIONS
Authors: Forbes W. F. , Mueller W. A.
Published: May 2006

The application of light absorption data to determine minimum interference radii of various atoms in solution is examined. Three separate methods are suggested and the relation between potential energy and interatomic distance of two non-bonded atoms is discussed. The values obtained in neutral solution are as follows: H, 0.95 ± 0.1 Å; O (in C=O), 1.0 ± 0.15 Å; and CH3, 1.7 ± 0.2 Å.
SOME BASIC DERIVATIVES OF 6-CHLOROQUINAZOLINE AND PHTHALAZINE
Authors: Winthrop Stanley O. , Sybulski Stella , Gaudry Roger , Grant Gordon A.
Published: May 2006

Basic derivatives of 6-chloroquinazoline and phthalazine have been synthesized and screened for their physiological action on the central nervous system. Sodium dialkylaminoalkoxides and the appropriate chlorobenzodiazine were brought together to yield basic ethers of 6-chloroquinazoline and phthalazine respectively. 1-(γ-Dimethylaminopropylamino)phthalazine was also prepared.
1-(β-DIALKYLAMINOETHYL-2-IMIDAZOLIDINETHIONES
Authors: McKay A. F. , Garmaise D. L. , Halasz A.
Published: May 2006

A series of 1-(β-dialkylaminoethyl)-2-imidazolidinethiones and their picrates are described. 1-(β-Diethylaminoethyl)-2-methylmercapto-2-imidazoline dihydroiodide combined with benzylamine with the evolution of methyl mercaptan to give 1-(β-diethylaminoethyl)-2-benzylamino-2-imidazoline (III). In a similar reaction β-alanine gave a product whose picrate gave analytical values in agreement with those calculated for the dipicrate of 1-(β-diethylaminoethyl)-5-keto-Δ8-hexahydro-1,4,8-pyrimidazole (IV).
ATTEMPTED DELIGNIFICATIONS WITH SODIUM BICARBONATE - CARBON DIOXIDE, AND WITH ANHYDROUS LIQUID AMMONIA, UNDER PRESSURE
Authors: Yan M. M. , Purves C. B.
Published: May 2006

Finely divided spruce wood was heated with aqueous sodium bicarbonate and excess carbon dioxide up to 160° and about 400 p.s.i. in attempts to carboxylate the lignin according to the Kolbe–Schmitt method and to extract the product as a soluble sodium salt. Only small amounts of lignin were removed, together with larger amounts of the holocellulose. Heating the wood with anhydrous liquid ammonia up to 100° and about 900 p.s.i. extracted only small amounts of material from the softwood spruce, but 25 to 30% of the lignin was removed from the hard woods beech, birch, and maple and 52% from rye straw. The solution of ammonium chloride or sodium cyanide in the liquid ammonia increased these percentages substantially, and also the concomitant extraction of holocellulose.
THE CONFIGURATION OF GLYCOSIDIC LINKAGES IN OLIGOSACCHARIDES: II. BY DEGRADATION OF REDUCING DISACCHARIDES TO 2-O-GLYCOSYL-GLYCEROLS
Authors: Charlson A. J. , Gorin P. A. J. , Perlin A. S.
Published: May 2006

Reducing aldohexopyranose disaccharides are degraded by employing a series of oxidations and reductions to yield 2-O-glycosyl-glycerols, configurations of which are assigned according to Hudson's definition. Maltose, for example, treated with 2 moles of lead tetraacetate gives 2-O-α-D-glucopyranosyl-D-erythrose; the latter is reduced to the corresponding alcohol, which is oxidized in turn with 1 mole of lead tetraacetate to give 2-O-α-D-glucopyranosyl-L-glyceraldehyde, and a second reduction yields 2-O-α-D-glucopyranosyl-glycerol. Cellobiose is converted to 2-O-β-D-glucopyranosyl-glycerol by the same sequence of reactions. Other reducing disaccharides containing D-glucopyranose non-reducing end-units may also be degraded to give one or other of these anomeric glycerol-derivatives, the identity of which establishes the configuration of the glycosidic linkage in the original disaccharide. The pair of anomeric 2-O-D-galactopyranosyl-glycerols is afforded by the naturally-occurring α-anomer, and the product obtained through degradation of lactose. 2-O-D-Mannopyranosyl-D-mannose, obtained after acetolysis of a yeast slime mannan, and 4-O-D-mannopyranosyl-D-mannose, from ivory nut mannan, yielded 2-O-α- and 2-O-β-D-mannopyranosyl-glycerol, respectively, which establishes the configuration of the glycosidic linkages in the disaccharides.
PREPARATION AND TOXICITY OF SOME ALKYL THIOPYROPHOSPHATES
Authors: McIvor R. A. , McCarthy G. D. , Grant G. A.
Published: May 2006

Several methods have been investigated for the synthesis of tetraalkyl thiopyrophosphates, including one that can be carried out very rapidly with high yield. Purification of these compounds proved exceedingly difficult, because they were sensitive to traces of acids or bases, and probably to inorganic salts at temperatures above 70 °C. All methods investigated yield only the thiono isomer, there being no evidence for the corresponding P—S—P isomer. Toxicological studies do not support the results reported by Fiszer and workers. None of the compounds is more toxic intravenously than tetraethyl pyrophosphate. The synthesis of several other related compounds for infrared study is reported.
ALCOHOLIC HEXANITRATO AMMONIUM CERATE AS A QUANTITATIVE OXIDANT FOR ORGANIC SUBSTANCES
Authors: Diaper D. G. M. , Richardson F. R.
Published: May 2006

not available
THE SOLUBILITY OF URANIUM(IV) HYDROXIDE IN SOLUTIONS OF SODIUM HYDROXIDE AND PERCHLORIC ACID AT 25 °C
Authors: Gayer K. H. , Leider H.
Published: May 2006

The solubility of uranium(IV) hydroxide has been measured in sodium hydroxide, water, and perchloric acid solutions. A possible reaction in sodium hydroxide solutions is evaluated.
NATURE OF THE ADSORPTION PROCESS RESPONSIBLE FOR JOSHI EFFECT
Authors: Rao C. N. Ramachandra
Published: May 2006

not available
INFLUENCE DE L'OXYDE NITRIQUE ET D'AUTRES INHIBITEURS SUR L'OXYDATION LENTE DE L'ÉTHER
Authors: Lemay André , Ouellet Cyrias
Published: May 2006

not available
TOXIC FLUORINE COMPOUNDS: XIII. ω-FLUOROALKYL ETHERS
Authors: Pattison F. L. M. , Howell W. C. , Woolford R. G.
Published: May 2006

Representative ω-fluoroalkyl ethers have been synthesized. Their toxicological properties provide evidence for the rupture invivo of the ether link. The compound 2-fluoro-1′,2′,2′,2′-tetrachlorodiethyl ether (XIII) shows outstanding activity as a systemic insecticide
THE REACTION OF NITROMETHANE WITH FLUORENONE AND BENZOPHENONE IN POLYPHOSPHORIC ACID
Authors: Anet F. A. L. , Bavin P. M. G. , Dewar M. J. S.
Published: May 2006

not available
LYCOPODIUM ALKALOIDS: V. OXIDATION AND REDUCTION STUDIES ON ANNOTININE AND ITS DERIVATIVES
Authors: Betts E. E. , MacLean David B.
Published: May 2006

Annotinine lactam C16H19O4N has been converted by the action of dilute sulphuric acid to the lactamdiol, C16H21O5N. Oxidation studies on the lactamdiol have confirmed the presence of the epoxide ring in the alkaloid and have established the six-membered character of the lactam ring. The allylamine structure of unsaturated lactone A, C16H21O2N, has been confirmed and a number of intermediate oxidation products of this compound have been isolated and characterized. Raney nickel reduction of annotinine yielded hydroxy annotinine, C16H23O3N, and saturated lactone A, C16H23O2N. Catalytic reduction of annotinine lactam over Adams′ catalyst in acidic medium converted it partially to annotinine.
REARRANGEMENT STUDIES WITH C14: III. THE FRIEDEL–CRAFTS ALKYLATION OF ANISOLE WITH 2-PHENYLETHYL-1-C14 CHLORIDE AND 2-PHENYLETHANOL-1-C14
Authors: Lee C. C. , Forman A. G. , Rosenthal A.
Published: May 2006

The Friedel–Crafts alkylation of anisole with 2-phenylethyl-1-C14 chloride and 2-phenylethanol-1-C14 resulted in a product, p-methoxydibenzyl, which showed isotope position rearrangement corresponding to an essentially 50% rearrangement of the C14 labeled atoms from the C-1 to the C-2 positions in the original chloride and alcohol. If one were to assume that both rearrangement and alkylation involve the same intermediate, these results may be explained on the basis of either an ionic mechanism for the Friedel–Crafts alkylation, the rearrangement being attributed to the formation of the phenylethyl cation, or a displacement mechanism in which the alkylation product is formed from a reaction between anisole and a rearranged polarized complex of aluminum chloride and alkylating agent. The possibility that rearrangement in the Friedel-Crafts alkylation may arise from a process separate from and prior to the alkylation stage itself is also discussed. On this basis, the intermediates involved in the rearrangement and alkylation stages will not necessarily have to be the same.
THE SECOND VIRIAL COEFFICIENT OF CARBON DIOXIDE AT LOW TEMPERATURES
Authors: Cook D.
Published: May 2006

The fixed volum e expansion method for gas compressibility measurements previously employed under conditions of high temperature and high pressure has now been developed for low temperature and low pressure measurements. A sensitive diaphragm null-pressure detector, operating as a capacitor, has been incorporated into the gas pipettes, and eliminates troublesome dead space corrections. The advantages and limitations of the method are discussed. Measurements of the second virial coefficient of carbon dioxide in the temperature range −60 °C. to + 30 °C, and in the pressure range 0.5 to 2.5 atmospheres, are reported.
FREE RADICALS BY MASS SPECTROMETRY: XII. PRIMARY STEPS IN THE MERCURY PHOTOSENSITIZED DECOMPOSITIONS OF ACETONE AND ACETALDEHYDE
Authors: Lossing F. P.
Published: May 2006

The primary step in the mercury (Hg3P1) photosensitized decomposition of acetone at 55 °C. results in the formation of methyl and acetyl radicals. At least 25% of the acetyl radicals are sufficiently long-lived to suffer collision with a second excited mercury atom, the products being ketene and a hydrogen atom. The primary step in the decomposition of acetaldehyde is at least 95% to form methyl and formyl radicals. The methane found was shown by tracer experiments to be the product of a secondary reaction, probably that between methyl and formyl radicals. Other secondary reactions are discussed.
AN OXYGENATED FATTY ACID FROM THE SEED OIL OF HIBISCUS ESCULENTUS
Authors: Chisholm Mary J. , Hopkins C. Y.
Published: May 2006

The fatty acids of okra seed oil (Hibiscusesculentus L.) were examined. Acetylation of the oil, followed by saponification and separation of the acids, gave 12,13-dihydroxyoleic acid. From this and other evidence it is concluded that 12,13-epoxyoleic acid is present as a constituent of the glycerides. An oxygenated acid has not been identified previously in seed oils of this plant family (Malvaceae). 9-Hexadecenoic acid was also found. The total fatty acid composition was determined by distillation of the methyl esters and analysis of the distilled fractions. The percentages of the acids identified were estimated as follows: 9-hexadecenoic 0.6, palmitic 29, linoleic 39, oleic 23, stearic 2, 12,13-epoxyoleic 3, arachidic <1. Myristic, eicosenoic, and trienoic acids were not detected and, if present, are judged to have been in amounts less than 1% of the total.
THIAZOLES: III. INFRARED SPECTRA OF METHYLTHIAZOLES
Authors: Taurins Alfred , Fenyes J. G. E. , Jones R. Norman
Published: May 2006

The infrared absorption spectra of thiazole, all three monomethylthiazoles, and two dimethylthiazoles have been measured in the liquid phase.
A NOTE ON UREIDO DERIVATIVES ISOLATED AS BY-PRODUCTS IN AMINO ACID SYNTHESIS
Authors: Burland P. D. , Christian J. D.
Published: May 2006

Approximately 10–20% yields of alpha-ureidopropionamide and alpha-ureidoisovaleramide were obtained as major by-products in the synthesis of 5-methylhydantoin and 5-iso-propylhydantoin, respectively, by the Gaudry (3) technique. The two compounds can be hydrolyzed to their corresponding amino acids, DL-alanine and DL-valine, in alkaline solution or recyclized to their corresponding hydantoins with mineral acid.
ORGANIC DEUTERIUM COMPOUNDS: XVIII. ADDITION PRODUCTS OF HYDROGEN AND DEUTERIUM BROMIDES TO 1,1-DICHLOROETHYLENE
Authors: Francis J. E. , Leitch L. C.
Published: May 2006

The addition of hydrogen bromide to 1,1-dichloroethylene under ultraviolet illumination gave two products identified as 1-bromo-2,2-dichloroethane and 1-bromo-2,2,4,4-tetra-chlorobutane. With deuterium bromide, the corresponding deuterated halides were formed. 1-Chloroethene-1-d was prepared from 1-bromo-2,2-dichloroethane-2-d.
THE KINETICS OF THE THERMAL DECOMPOSITION OF DIMETHYL-2,2′-BIS-AZO-ISOBUTYRATE
Authors: Mackie J. S. , Bywater S.
Published: May 2006

not available
THE INTRINSIC VISCOSITIES OF AQUEOUS SOLUTIONS OF SMALL MOLECULES
Authors: Edward J. T.
Published: May 2006

not available
4-O-METHYL-D-GLUCURONIC ACID AND 4-O-METHYL-D-GLUCOSE
Authors: Gorin P. A. J.
Published: May 2006

A novel method for the preparation of 4-O-methyl-D-glucuronic acid is described. This sugar and 4-O-methyl-D-glucose were obtained in good yield by two different series of reactions from 2-O-(4-O-methyl-D-glucopyranuronosido)-D-xylose, an acid hydrolysis product of the hemicellulose of Populustacamahacca Mill.
REACTIONS OF ARYLSULPHONIC ESTERS: VII. THE HEAT CAPACITY OF ACTIVATION FOR THE ETHANOLYSIS OF METHYL p-NITROBENZENESULPHONATE
Authors: Hyne J. B. , Robertson R. E.
Published: May 2006

A conductometric method is described for the determination of rates of solvolyses in nonaqueous media with an accuracy of better than ± 0.5% in k. The heat of activation derived from the results so obtained is shown to have a temperature coefficient (ΔCp‡) of −21 cal./mole deg.
THE DIPOLE MOMENTS OF MERCURIC CHLORIDE AND MERCURIC BROMIDE IN BENZENE
Authors: Tourky A. R. , Rizk H. A.
Published: May 2006

From dielectric constant measurements in benzene for the two halides mercuric chloride and mercuric bromide, the dipole moments are 1.23 and 0.95 D. respectively. Thus, they apparently possess angular structures.
SYNTHESIS IN THE FIELD OF THE ERYTHRINA ALKALOIDS: PART II. APPROACHES TO THE RING SYSTEM OF β-ERYTHROIDINE
Authors: Belleau B.
Published: May 2006

The newly developed method for the elaboration of the ring system of the aromatic class of Erylhrina alkaloids has been successfully extended to the synthesis of 1,2,3,4-tetrahydroerythrinane (VI), a non-aromatic analogue. The key step in this synthesis involves ring closure of ketoamide (IV) itself, obtained from hexahydroindole and cyclohexenylacetic acid. Attempts to further extend this sequence to the use of 2H-5,6-dihydropyranacetic acid as starting material met with failure at the stage of preparation of the latter. A new and unrelated stepwise approach illustrated on Chart III was investigated but failed at the ultimate step. Other unsuccessful approaches are also briefly described.
INTERNAL ROTATION: X. THE RAMAN SPECTRUM OF LIQUID 1-CHLORO-2-BROMOETHANE-1,1-d2
Authors: Wilmshurst J. K. , Bernstein H. J.
Published: May 2006

not available
SOME OBSERVATIONS ON THE HYDROLYSIS OF CYANOGEN CHLORIDE
Authors: Lister M. W.
Published: May 2006

not available
GAS PHASE REACTIONS OF PHENYL RADICALS
Authors: Taylor G. W.
Published: May 2006

not available
EQUILIBRIUM CONSTANTS FOR THE SULPHUR ISOTOPE EXCHANGE BETWEEN SO2 AND H2SO4
Authors: Dunford H. B. , Harrison A. G. , Thode H. G.
Published: May 2006

The S32–S34 isotope exchange between sulphur dioxide and 100% sulphuric acid has been studied over the temperature range 200° to 400 °C. Equilibrium constants of 1.014, 1.011, and 1.008 at 205°, 300°, and 400 °C. respectively have been found, favoring the S34 in the sulphuric acid. These results agree reasonably well with theoretical calculations made for the sulphur isotope exchange between sulphate ion and sulphur dioxide.
SENSITIZED PHOTOIONIZATION
Authors: Tanaka Ikuzo , Steacie E. W. R.
Published: May 2006

The krypton photosensitized ionization of nitric oxide and acetone has been investigated. At constant nitric oxide pressure, the relation between ion current and krypton pressure is given by i = a + b(1 − e−cp), where i is the ion current, a, b, and c are constants, and p is the krypton pressure. It has been further shown that the quenching cross section of nitric oxide for excited krypton is smaller than that of acetone. Sensitized photoionization was also obtained in the cases of xenon and anisole, and argon and nitric oxide. The quenching of excited krypton by helium, hydrogen, and deuterium has been studied. Helium quenches to a negligible extent; the quenching efficiency of hydrogen is rather greater than that of deuterium.
STRESSES AND STRAINS IN ADSORBATE–ADSORBENT SYSTEMS: IV. CONTRACTIONS OF ACTIVATED CARBON ON ADSORPTION OF GASES AND VAPORS AT LOW INITIAL PRESSURES
Authors: Lakhanpal M. L. , Flood E. A.
Published: May 2006

When active adsorbents, such as active carbon and porous glass, adsorb relatively large quantities of vapors, normally the adsorption is accompanied by considerable swelling of the adsorbent. It has been observed by McIntosh, Yates, and others that when the quantities adsorbed are small in some cases the adsorption is accompanied by an appreciable shrinkage of the adsorbent. We have studied this phenomenon experimentally and theoretically and some of the results obtained are presented in this paper. It is suggested that the shrinkage is due to "bridging" of sites by adsorbate molecules, the "bridging" being associated with highly anisotropic forces acting on adsorbate molecules and with considerable tensile stresses along some of the bonds of the adsorbed molecules.
THE INFRARED SPECTRA OF HUMIC ACIDS AND RELATED MATERIALS
Authors: Elofson R. M.
Published: May 2006

The infrared spectra of a number of humic acids and related materials obtained by the potassium bromide pressed pellet technique are summarized. Acidic properties of humic acids are largely due to clearly defined carboxylic acid frequencies at 3.9 μ and 5.8 to 5.85 μ. These bands are shifted in the expected manner by preparation of the sodium salts. Autoclaving of humic acids from lignite and from hydroquinone removes the carboxylic acid bands and produces material having bands in the long wave-length region that are at the same position as bands shown by bituminous coal and autoclaved cellulose. The potassium bromide technique has also revealed in the infrared spectra of low rank material a band at 6.65 μ which decreases markedly with increase in rank and may be related to the degree of condensation of aromatic nuclei.
THE USE OF A TWYMAN-GREEN TYPE INTERFEROMETER TO MEASURE DIFFUSIVITIES IN AN ELECTRODEPOSITION CELL
Authors: O'Brien Robert N.
Published: May 2006

not available
"SENSITIVE" VIBRATIONAL FREQUENCIES PART 2. THE METHYLENE AND METHINE FREQUENCIES AND THEIR RELATION TO ELECTRONEGATIVITY
Authors: Wilmshurst J. K.
Published: May 2006

not available
A SYNTHESIS OF 5,6-DIDEOXY-D-XYLOHEXOSE(5-DEOXY-5-C-METHYL-D-XYLOSE)
Authors: Jones J. K. N. , Thompson J. L.
Published: May 2006

A synthesis of 5,6-dideoxy-D-xylohexose (I) from D-glucose is described. The action of sodium iodide in acetone on some toluene-p-sulphonyl esters of sugar derivatives is detailed.
THE CRYSTAL AND MOLECULAR STRUCTURE OF ANNOTININE BROMOHYDRIN
Authors: Przybylska Maria , Marion Léo
Published: May 2006

not available
OXYMERCURATION OF THE METHYLCYCLOHEXENES
Authors: Park W. R. R. , Wright George F
Published: May 2006

It has been found that, while hydroxymercuration of 2-methylcyclohexene leads to a single product, 3-methylcyclohexene gives a nonworkable mixture and 4-methylcyclohexene gives both positional and diastereoisomers of which three of the four have been isolated. The ratio of positional isomers is found to be 5:1 in favor of farthest distance of the methyl group from the mercury atom. The conversion of the chloromercuri-hydroxy-methylcyclohexanes to chloromercuri-methoxy-methylcyclohexanes by potassium tert-butoxide and dimethyl sulphate has been accomplished. Thus the products of hydroxymercuration have been related configurationally to two of the three products of 4-methylcyclohexene methoxymercuration. Among these products that one is most prevalent in which the mercury is most distant, positionally and confjgurationally, from the methyl group in the alkene.
A DETERMINATION OF THE SURFACE FREE ENERGY OF SODIUM CHLORIDE
Authors: Zeggeren F. Van , Benson G. C.
Published: May 2006

The surface free energy for the interface between crystalline sodium chloride and a saturated alcoholic solution was determined from the solubility of sodium chloride in absolute ethyl alcohol as a function of the particle size of the salt. At 298°K. a value of 171 ergs/cm.2 was found. A general discussion of the validity of the Ostwald equation, which relates solubility and particle size, is presented.
INFRARED SPECTRUM OF THE H3O+ ION IN AQUEOUS SOLUTIONS
Authors: Falk Michael , Giguère Paul A.
Published: May 2006

The absorption spectra at 25 °C. of aqueous solutions of mineral acids (HCl, HBr, HNO3, HClO4, H2SO4, H3PO4) and of some of their acid salts in various concentrations were measured in the infrared from 2 to 25 µ. In all cases three broad bands were present at 1205, 1750, and 2900 cm.−1 arising from the H3O+ ion. Cooling the samples, and even supercooling them down to liquid air temperature, produced no major changes in the spectra. The bands of the D3O+ ion were also found at 960, 1400, and 2170 cm.−1 in solutions of DCl in heavy water. Thus, the existence of discrete hydronium ions in the liquid state, with average life longer than 10−13 second, is confirmed. Infrared spectra provide a means of estimating the extent of ionization of strong acids in solution.
VOLTAIC CELLS IN FUSED SALTS: PART II. THE SYSTEMS: (a) SILVER – SILVER CHLORIDE, LEAD – LEAD CHLORIDE; (b) SILVER – SILVER CHLORIDE, ZINC – ZINC CHLORIDE; AND (c) SILVER – SILVER CHLORIDE, NICKEL – NICKELOUS CHLORIDE
Authors: Flengas S. N. , Ingraham T. R.
Published: May 2006

Using a reversible silver – silver chloride reference electrode, described in the first paper of this series, standard electrode potentials have been established for the systems lead – lead chloride, zinc – zinc chloride, and nickel – nickelous chloride, in melts containing equimolar quantities of KCl and NaCl. Deviations from ideality were observed, and these were attributed to the formation of complexes. Dissociation constants for the complexes were calculated. The effect of temperature on the electromotive forces of the voltaic cells was also measured, and the heats of the cell reactions were calculated from the data.
PHOTO-INITIATED FREE RADICAL POLYMERIZATION OF METHYL ACRYLATE IN AQUEOUS SOLUTION
Authors: Menon C. Chaitanyan , Santappa M.
Published: May 2006

Photo-initiated free radical polymerization of methyl acrylate in aqueous solution is described. Using mainly light of wavelength 3650 Å and the ion pairs Fe3+OH− and Fe3+Cl− as photosensitizers the kinetics of polymerization were investigated by studying the effect of the variation of (i) intensity of light, (ii) concentration of monomer, (iii) fraction of light absorbed by the ion pair, and (iv) ferrous ion accumulating in, or initially added to, the system on (a) molecular weight of polymer, (b) the rate of disappearance of monomer, and (c) the rate of production of ferrous ion. The results have been analyzed in the light of a reaction scheme involving (1) a primary photochemical process and a dark back reaction, (2) initiation of polymerization by the primary product Fe2+OH or Fe2+Cl, (3) dissociation of the primary product, (4) a secondary dark back reaction, (5) initiation by a free radical, (6) propagation, and (7) termination. Examination of the experimental results in the light of the reaction scheme indicated that the initiation of polymerization was due to OH or Cl free radicals formed by the dissociation of the primary product and that termination occurred by combination of growing polymer chains. Some expressions involving specific rate constants have been evaluated.
THE REACTION OF ACTIVE NITROGEN WITH HYDROGEN CHLORIDE
Authors: Wiles D. M. , Winkler C. A.
Published: May 2006

Hydrogen chloride was apparently destroyed by catalyzing the recombination of nitrogen atoms, the maximum observed rate of destruction being less than one sixth of the active nitrogen flow rate. The effects on the hydrogen chloride – active nitrogen reaction of added chlorine and added hydrogen indicated the reaction between hydrogen atoms and molecular chlorine to be the most important secondary reaction.
REDUCTION OF HALOGENATED NITROBENZENES
Authors: Gagnon Paul E. , Keirstead Karl F. , Newbold Brian T.
Published: May 2006

2-Chloronitrobenzene and 2,5-dichloronitrobenzene were reduced with sodium arsenite, dextrose, lactose, maltose, sodium hydroxide and alcohols, and potassium hydroxide and ethanol. The effects of sodium hydroxide, temperature, time, Tergitol, and Lignosol were studied for the arsenite and dextrose reductions. 2-Bromonitrobenzene was also reduced with sodium arsenite and dextrose in alkaline medium. These reductions gave rise to four new phenazine derivatives. 2,4-Dinitrochlorobenzene, when reduced with sodium arsenite, in alkaline medium, yielded only 2,2′-dichloro-5,5′-dinitroazoxybenzene.
ADDITION OF n-BUTYL MERCAPTAN TO 1-PENTENE ON IRRADIATION WITH X-RAYS OR GAMMA RAYS: I. 140 KVP. X-RAYS
Authors: Fontijn A. , Spinks J. W. T.
Published: May 2006

n-Butyl mercaptan reacts with 1-pentene when irradiated with X-rays. The dependence of reaction rate upon concentration of mercaptan and pentene has been studied as well as the dependence on dose rate. A comparison with the photoinitiated reaction is made.
N-ACYL SUBSTITUTED PHENYLHYDROXYLAMINES: THE EFFECT OF RADICAL CHANGE ON ANALYTICAL BEHAVIOR
Authors: Armour C. A. , Ryan D. E.
Published: May 2006

The synthesis of a number of N-acyl substituted phenylhydroxylamines is outlined and the effect of the change in the nature of the acyl group on their usefulness as analytical reagents is described. Stability constant measurements in alcohol show an increase in stability with an increase in basicity of reagent regardless of the nature of the attached group; their ability to precipitate complexes from aqueous solution, however, is markedly dependent on the nature of the attached radical. A spectrophotometric study shows the existence of both a 1:1 and a 1:3 iron complex. A more sensitive colorimetric reagent results with an unsaturated five-membered ring as the attached grouping.
THE STRUCTURE OF BUTADIENE DIMERS PRODUCED BY A FREE-RADICAL CHAIN-TRANSFER MECHANISM
Authors: Gendron L. J. , Nicholls R. V. V.
Published: May 2006

Butadiene was dimerized by using acetyl peroxide as source of free radicals and chloroform as solvent and chain-transfer agent. The dimers were identified and their structures were determined by means of ozonolysis and oxidative hydrolysis. It was established that two dimers were produced in nearly equal amount. One dimer was formed only by 1,4-additions, the other only by 1,2-additions. This result implies that polybutadienes may be mixtures of two varieties: one variety resulting from 1,4-additions, the other from 1,2-additions.
THE ACTION OF Co60 GAMMA RAYS AND OF FENTON'S REAGENT ON AQUEOUS BROMAL HYDRATE SOLUTIONS
Authors: Woods R. J. , Spinks J. W. T.
Published: May 2006

Aqueous bromal hydrate solutions have been irradiated with Co60 gamma rays and the production of acid measured. The effect of bromal hydrate concentration, dose rate, pH, and temperature upon the yield of acid has been determined. Major products of the radiolysis have been identified and are compared with those formed when aqueous bromal hydrate solutions are treated with Fenton's reagent, a mixture of hydrogen peroxide and ferrous sulphate solutions. It has been shown that Fenton's reagent will initiate a chain reaction in aqueous bromal hydrate solutions which produces hydrobromic acid.
THE PREPARATION AND SINTERING OF FINELY DIVIDED SODIUM CHLORIDE. II
Authors: Moffat J. B. , McIntosh R.
Published: May 2006

The sintering of unpacked samples of sodium chloride of high specific surface has been investigated. The sintering occurred in the presence of known pressures of water vapor and at temperatures below 70 °C. The progress of the change of specific surface was followed by measuring the physical adsorption of carbon dioxide at approximately −80 °C. It has been shown that an unchanging value of the surface area of a given sample exists at each relative pressure of water vapor. The area attained is independent of the number of exposures to water vapor at pressures below the final pressure. The fractional change of area of all samples in the range 35 to 80 m•2/g. depends only upon the relative pressure of water vapor. Preliminary observations of the behavior of loaded samples showed that packing the samples does not affect the character of the sintering.A qualitative theory to account for these findings is given. It is postulated that certain ion pairs become mobile when the binding energy to the crystal is reduced by the adsorbed water. On increasing the amount of adsorbed water additional ion pairs become free to migrate and the process resulting in loss of specific surface continues to a further extent.
THE LOCATION OF THE XANTHATE GROUPS IN PARTLY SUBSTITUTED CELLULOSE XANTHATES
Authors: Swan E. P. , Purves C. B.
Published: May 2006

Cellulose sodium xanthates of degree of substitution (D.S.) 0.4 to 0.66 were methylated to xanthate S-methyl esters which were then acetylated completely, the final xanthate D.S. remaining close to the original value. Dexanthation with aqueous chlorine dioxide near pH 4.5 and −5° removed almost all of the S-methyl xanthate groups, but the loss of a few acetyl groups from, and the retention of 1 to 2% of sulphur in, the resulting cellulose acetate could not be avoided. The original xanthate groups were presumably represented in this acetate as unsubstituted hydroxyl groups, and these were located by standard methods involving tosylation–iodination, tritylation, and oxidations with lead tetraacetate. Xanthate groups appeared to occupy the third and sixth, but not the second, position in the cellulose, and 53 to 61% of the substituent was in the sixth or primary position; one sample of viscose was "ripened" before the cellulose sodium xanthate was isolated, and the value was 81%. The results were of a preliminary nature, because severe technical difficulties reduced their reliability.
THE SYNTHESIS OF 3-INDOLEACETIC ACID-C14 LABELED IN THE BENZENE RING
Authors: Robinson J. R.
Published: May 2006

not available
SYNTHESIS OF INDOLEACETIC ACIDS
Authors: Robinson J. R. , Good N. E.
Published: May 2006

not available
THE LOWER EXCITED STATES OF SOME SIMPLE MOLECULES
Authors: Mulliken R. S.
Published: May 2006

The present and prospective rapidly increasing usefulness of good LCAO-MO calculations on the electronic states of simple molecules in the interpretation of observed excited states is pointed out. As examples, the observed and predicted states of, in particular, the π3π configurations of N2 and CO are compared with those of C2H2 and HCN and with those of CO2 and CS2. Further, the results of LCAO-SCF calculations on CO2 and on O3 are surveyed, and it is shown how these can be helpful in interpreting and understanding the ground and excited states of AB2 (expecially AO2) molecules in general. A new interpretation of the so-called d3П state of CO as a case b πu3πg, 3Δu state is proposed. Tentative interpretations of some of the ultraviolet absorption spectra of C2H2, HCN, and of a number of AB2 molecules are reviewed or suggested, including some discussion of the shapes of excited states. The AB2 discussion is a revision of one given earlier. Finally, following up a suggestion of Coon, it is pointed out that there exists strong evidence for slightly unequal A—O distances in certain excited states of C1O2 and SO2.
THE NATURE OF FORMALDEHYDE IN ITS LOW-LYING EXCITED STATES
Authors: Robinson G. W. , DiGiorgio V. Erdmanis
Published: May 2006

Long path length, high resolution spectra in the near ultraviolet of H2CO and D2CO at −78 °C. have been obtained, and further strong evidence in support of a non-planar excited state is presented. The double-headed bands to the long wavelength side of the singlet–singlet system are shown to belong to the singlet–triplet transition. A vibrational analysis and partial rotational analysis shows the excited triplet state to be very similar to the excited singlet state. The larger C—O stretching frequency in the triplet state may characterize the multiplicity of these states in the simple aliphatic aldehydes and ketones. It is found that the C—O bond order in both states is very nearly 1.5, and striking similarities between the bonding in these states and the C—O bonding in formic acid are pointed out. The similarity between the singlet and triplet excited states may not extend to chemical behavior because of spin correlation rules, but there are no general reasons why the triplet state should be more reactive than the singlet.
EXCITED STATES OF THE MOLECULAR IONS OF HYDROGEN FLUORIDE, HYDROGEN IODIDE, WATER, HYDROGEN SULPHIDE, AND AMMONIA
Authors: Frost D. C. , McDowell C. A.
Published: May 2006

The ionization of the molecules of hydrogen fluoride, hydrogen iodide, water, hydrogen sulphide, and ammonia, by essentially monoenergetic electrons, has been studied in a mass spectrometer. The various excited states of the molecular ions of these compounds have been observed and the corresponding energy levels of the ions have been measured. The results are interpreted in terms of the electronic structures of these molecules as given by molecular orbital theory.
THE QUENCHING OF THE IODINE FLUORESCENCE SPECTRUM
Authors: Arnot C. , McDowell C. A.
Published: May 2006

The quenching of the iodine fluorescence spectrum by various inert gases and oxygen has been studied with a view to obtaining information on the efficiencies of vibration energy transfer processes in this system. Preliminary results here presented are in agreement with earlier work of Rössler and Eliaschevich and indicate that the transfer processes are very efficient. A kinetic scheme is proposed to account for the various possible quenching and transfer processes and it is shown that this is in agreement with experimental results.
THE SYNTHESIS OF ω -DEOXY- ω -S-ETHYL-POLYOLS
Authors: Jones J. K. N. , Mitchell D. L.
Published: May 2006

Treatment of an aldose diethyl thioacetal with a limited amount of aged Raney nickel catalyst resulted in the reductive cleavage of one thioethyl group. 1-Deoxy-1-S-ethyl derivatives of D-galactitol, L-arabitol, L-rhamnitol, and D-glucitol have thus been synthesized and their structures proved. 1-Deoxy-1-S-ethyl-L-galactitol has been prepared by the borohydride reduction of 6-deoxy-6-S-ethyl-D-galactose.
BLOCK AND GRAFT POLYMERS: I. GRAFT POLYMERS FROM ACRYLAMIDE AND ACRYLONITRILE
Authors: Miller M. L.
Published: May 2006

Graft polymers of acrylonitrile and acrylamide with from 1 to 20 grafts have been prepared by chain transfer to polymer and by photolysis of a copolymer containing a few per cent of α-chloroacrylonitrile. The intrinsic viscosities and softening points have been measured and the dependence of these properties on the number of grafts observed.
A MODIFICATION OF THE DIRECT CURRENT CONDUCTANCE METHOD
Authors: Graham G. D. , Maass O.
Published: May 2006

A modification in the employment of the direct current method of measuring conductivities is described. The main objective is that pure metallic probe and current carrying electrodes can be used, thus making it possible to investigate the conductivity of solutions such as hydrogen peroxide, aqua regia, etc. This necessitates a choice of electrodes which are inert to such solutions. An electrometer having an infinite resistance so as to avoid any polarization at the probes, in this case the quadrant electrometer, is described in its use as a null instrument. An accuracy as high as or greater than that of the alternating current method could be obtained. Furthermore, this method entails greater equipment economy and simplicity in apparatus required.
THE PHOTOLYSIS OF ALKYL ESTERS
Authors: Ausloos P.
Published: May 2006

An attempt has been made to determine the primary processes in the gas and liquid phase photolysis of simple alkyl esters.The liquid phase photolysis of methyl, ethyl, n-propyl, and n-butyl formate has been briefly investigated. Besides the dissociation processes, two intramolecular rearrangements were found to occur.[Formula: see text]Process I takes place with approximately the same yield for all the formates studied. Process II occurs only when there is a β-hydrogen in the alkyl group.An investigation of the gas and liquid phase photochemical decomposition of esters other than formates showed the existence of the following primary processes:[Formula: see text]Processes VI and VII require β- and γ-hydrogens, respectively, in the Y and X alkyl groups. It was found that processes I and X occur mostly at short wavelength, while the other processes take place at long wavelengths as well.
TREATMENT OF EXPERIMENTAL DATA IN THE STUDY OF CHELATION
Authors: Atkinson G. F. , McBryde W. A. E.
Published: May 2006

Calculation from experimental formation constants of the various species of metal chelates that predominate for a given system under different experimental conditions is facilitated by the use of a digital computer. A convenient graphical representation of the results obtained in this way is proposed. From the plotted data one may select conditions for a photometric analytical procedure that will ensure the exclusive formation of a single chelate species. The changes in species that accompany changes in pH for some systems introduce a variable and appreciable contribution to the ionic strength of the solution, the magnitude of which may be estimated from the results of the foregoing calculation.
THE LIQUID PHASE PHOTOLYSIS OF DIETHYL KETONE AND METHYL ETHYL KETONE
Authors: Ausloos P.
Published: May 2006

The liquid phase photolysis of diethyl ketone has been studied in the temperature range from −35° to 95 °C. The CO quantum yield at 95 °C. was found to be close to unity. At 28 °C. decrease in intensity and addition of heptane led to a substantial increase of the CO and the ethane yields.The methyl ethyl ketone liquid phase photolysis at temperatures between 5° and 75 °C. led to the same observations. Arrhenius plots of RE/RB1/2[K] gave for both compounds a value of 5 kcal./mole.Gas phase studies in the temperature range of 0° to 60 °C. confirmed the low CO quantum yield reported previously and showed evidence for disproportionation and recombination reactions between ethyl and propionyl radicals.
AMINO ACIDS: IV. THE REACTION OF GLYCINE AND β-ALANINE WITH CARBON DISULPHIDE
Authors: Tarlton E. J. , McKay A. F.
Published: May 2006

Glycine and β-alanine on condensation with carbon disulphide gave the corresponding l,3-di-(carboxyalkyl) thioureas. l,3-Di-(carboxymethyl) thiourea is rearranged to 2-thio-3-(carboxymethyl) hydantoin by warming with hydrochloric acid solution or heating above its melting point. Evidence is presented for the reversible condensation of 2 mole equivalents of the sodium salt of 2-thio-3-(carboxymethyl) hydantoin by the elimination of water. This condensation product is obtained as well-defined pink crystals. l,3-Di-(β-carboxyethyl) thiourea was oxidized with an alkaline solution of hydrogen peroxide or sodium hypochlorite solution to l,3-di-(β-carboxyethyl) urea. l,3-Di-(β-carboxyethyl) thiourea and l,3-di-(β-carboxyethyl) urea have been cyclized by heating with p-toluenesulphonic acid. The products were 2-thio-3-(β-carboxyethyI) hydrouracil and 3-(β-carboxyethyl) hydrouracil respectively.
THE SYSTEM LITHIUM NITRATE–ETHANOL–WATER AND ITS COMPONENT BINARY SYSTEMS
Authors: Campbell A. N. , Bailey R. A.
Published: May 2006

The system lithium nitrate–water has been investigated by thermal analysis and by X-ray powder diffraction studies. No trace of the hemihydrate reported by Donnan and Burt was found. The X-ray powder diffraction pattern of LiNO3.3H2O has been obtained.The equilibrium diagram of the system ethanol–water shows an inflection at –30 °C, corresponding to 40 weight per cent ethanol. This is almost certainly a true peritectic point. The formula of the hydrate formed (if there is one) is uncertain but it may be C2H5OH.5H2O.The system lithium nitrate–ethanol could only be studied in dilute solution (of lithium nitrate) and at temperatures near room temperature, because of high viscosity and extreme supercooling. No evidence for the existence of a solid alcoholate has been obtained.The system lithium nitrate–ethanol–water has been investigated in the form of a series of pseudobinary systems containing water and alcohol in fixed ratios. No solid alcoholate of lithium nitrate has been found in solutions containing less than 50 weight per cent ethanol. The investigation could not be pushed beyond this alcohol content because of high viscosity and supercooling.
THE THERMODYNAMICS OF MUTAROTATION OF SOME SUGARS: I. MEASUREMENT OF THE HEAT OF MUTAROTATION BY MICROCALORIMETRY
Authors: Kabayama M. A. , Patterson D. , Piche L.
Published: May 2006

The heats of mutarotation of D-glucose, D-xylose, lactose, maltose, and cellobiose have been determined using a microcalorimeter of the Tian-Calvet type. Part I of this paper describes the experimental work and the results obtained. Discussion of these results is reserved for Part II.
THE THERMODYNAMICS OF MUTAROTATION OF SOME SUGARS: II. THEORETICAL CONSIDERATIONS
Authors: Kabayama M. A. , Patterson D.
Published: May 2006

An interpretation of ΔH and ΔS for the mutarotation of D-glucose, D-xylose, maltose, lactose, and cellobiose is given in terms of changes in the hydration of the reducing hydroxyl group.
THE SYNTHESIS OF CRYPTOPLEURINE AND RELATED PHENANTHROQUINOLIZIDINES
Authors: Marchini P. , Belleau B.
Published: May 2006

The synthesis of the alkaloid cryptopleurine has been accomplished by a sequence involving as the key step the cyclization of amino acid XII. It was established that the approach is applicable to the synthesis of simpler phenanthroquinolizidines such as IV. The biogenesis of the alkaloid is briefly discussed.
STUDIES OF THE MECHANISM OF THE FORMATION AND DECOMPOSITION OF THE MOLECULAR COMPLEX BETWEEN SOLID UREA AND n-OCTANE VAPOR
Authors: McAdie H. G. , Frost G. B.
Published: May 2006

The formation and decomposition of the molecular complex between solid urea and n-octane vapor, in the presence and absence of initiators, has been studied by a variety of techniques. Suggestions are made for the possible mechanism of this heterophase reaction incorporating known structural and thermodynamic data.
THE DECOMPOSITION OF NITROUS OXIDE AT LOW PRESSURES ON NICKEL OXIDE CATALYSTS
Authors: Dewing J. , Cvetanović R. J.
Published: May 2006

Heterogeneous decomposition of nitrous oxide at pressures between 10−5 and 10−4 mm. on nickel oxide and doped nickel oxide catalysts has been studied in the temperature range 350° to 500 °C. Under most experimental conditions the reaction is first order in nitrous oxide. The observed activation energies are considerably smaller than those observed in previous work and are decreased on doping with Li2O and increased on adding Cr2O3. The results are explained by assuming that changes in the steady-state surface coverage with chemisorbed oxygen affect strongly the heats of chemisorption and, therefore, also the activation energies of the primary reactions.
THE THERMODYNAMIC PROPERTIES OF BENZOIC ACID
Authors: Goton R. , Whalley E.
Published: May 2006

not available
1-ARYLSULPHONYL-3-n-BUTYL-2-METHYL-2-THIOPSEUDOUREAS
Authors: Winthrop Stanley O. , Gavin Gregory
Published: May 2006

not available
THE MOLECULAR WEIGHT OF POLYETHYLENE AND OF OTHER HIGH-MOLECULAR-WEIGHT ORGANIC COMPOUNDS
Authors: Tremblay R. , Sirianni A. F. , Puddington I. E.
Published: May 2006

The temperature range of the measurement of vapor-pressure depression using a sensitive differential mercury micromanometer has been extended, and the behavior of a series of polyethylene samples having a molecular-weight range of 2500 to 24,000 was examined in toluene solutions at 75 °C. Good agreement was obtained between vapor-pressure lowering and other means of determining number-average molecular weights of several special compounds.
REACTION OF TRICHLOROACETONITRILE WITH PRIMARY AND SECONDARY AMINES: PART I. PREPARATION OF SOME TRICHLOROACETAMIDINES
Authors: Grivas John C. , Taurins Alfred
Published: May 2006

Trichloroacetonitrile reacts with primary and secondary aliphatic and primary aromatic amines to give N-substituted trichloroacetamidines. A series of N-mono- and N-di-substituted trichloroacetamidines, [Formula: see text] and [Formula: see text] was prepared by carrying out the reaction in water, in water–methanol solutions, or in the absence of solvents.