bluuebunny/crossref_metadata_2025 huggingface dataset:
THE HEAT OF WETTING OF SILK FIBROIN BY WATER
Authors: Dunford H. Brian , Morrison John L.
Published: May 2006

The heats of wetting by water of silk fibroin initially containing various amounts of adsorbed and desorbed water have been measured. These measurements along with the water vapor adsorption isotherm of Hutton and Gartside have been used to calculate the integral and differential heats, free energies, and entropies of adsorption. In contrast with cellulose, silk containing desorbed water evolves less heat than that containing adsorbed water. This fact suggests that any contribution by a heat of swelling term is very small for silk fibroin, so that the calculated thermodynamic properties probably can be assigned almost entirely to the adsorption process. The changes in the heats and entropies of adsorption appear to parallel the sequence of changes in film formation as revealed by surface area calculations.
INTERFACIAL POTENTIALS
Authors: Davies J. T. , Rideal Sir Eric
Published: May 2006

A new relation between interfacial distribution potentials and interfacial surface (contact) potentials is presented. By a suitable choice of experimental system either distribution potentials or surface potentials may be measured separately; results are in good agreement with theory. Surface potentials are shown to be made up of several independent components. The rates of decay of surface potentials are also discussed.
OXIDATION OF ALKENES BY MERCURIC SALTS
Authors: Shearer D. A. , Wright George F
Published: May 2006

The α-oxymercurials of cyclohexene, 2-methyl-1-phenylpropene-1, and the geoisomers of stilbene have been shown to be the intermediates in the oxidation of these alkenes by mercuric nitrate and other salts, usually in methanol. These intermediates are stable in the oxidation environment and their alkoxy groups appear intact in the oxidation product; indeed organomercurials without vicinal alkoxy groups are likewise oxidized. The reaction products from alkenes in methanol are 1,2-dimethoxyethanes, 1,1-dimethoxyethanes, and (with mercuric nitrate) 1-methoxy-2-nitroxyethanes, formation of the latter being most rapid. The oxidation is stereospecific, each geoisomer yielding its characteristic dia-stereomeric products. It is catalyzed by acids such as nitric acid but not by nitrate ion, though neither affect the ratio of products. This over-all second-order reaction, first-order in organomercurial and first-order in mercuric salt, becomes over-all first-order with mercuric acetate when it is catalyzed by boron fluoride. Combination of the catalyst with the organomercurial must be rate-controlling. The similarity of the oxidation and the acid decomposition reactions of organomercurials is discussed.
INTERNAL ROTATION: VIII. THE INFRARED AND RAMAN SPECTRA OF FURFURAL
Authors: Allen G. , Bernstein H. J.
Published: May 2006

The Raman spectrum of furfural has been obtained photoelectrically in the liquid over a temperature range of 50° and in solution. The infrared spectrum has been obtained for the solid, the liquid (over a temperature range of 90°), and in dilute solution over a 50° temperature range. The vibrational spectrum is interpreted in terms of an equilibrium mixture of two rotational isomers with planar configuration. The isomer with higher electric moment is the more stable form in the liquid and in the solid.
THE STRUCTURE AND PROPERTIES OF DL-1,2-O-CYCLOHEXYLIDENEGLYCEROL
Authors: Porck A. J. E. , Craig B. M.
Published: May 2006

DL-1,2-O-Cyclohexylideneglycerol was prepared by reacting cyclohexanone and glycerol in the presence of sulphuric acid. It is miscible with all common organic solvents and is slightly soluble in water. It is not affected by hydrogenolysis at 25 °C. over palladous oxide at 50 p.s.i. for 24 hr. The DL-1,2-O-cyclohexylidene-3-O-p-nitrobenzoylglycerol is readily cleaved by mineral acids to yield 3-O-p-nitrobenzoylglycerol. Proof of the 1,2 ketal structure was obtained by (a) preparation of the monomethyl derivative, acid hydrolysis, and periodic acid oxidation of the resultant 1-monomethyl ether of glycerol and (b) treatment of the tosyl derivative with sodium iodide which gave a 93% yield of sodium p-toluenesulphonate.
BENZYL 2-CHLOROETHYL ETHERS
Authors: Kulka Marshall , Stryk F. G. Van
Published: May 2006

The solvolysis reaction between benzyl chlorides and ethylene chlorohydrin has been employed for the synthesis of a series of benzyl 2-chloroethyl ethers (III) required in insecticide screening tests. This method is limited to the synthesis of III which possesses a partially deactivated nucleus. Several new benzyl chlorides are recorded.
STEROIDS: III. THE EPIMERIC N-ACETYL-3-AMINOCHOLEST-4- AND -5-ENES
Authors: Bannard R. A. B. , McKay A. F.
Published: May 2006

Lithium aluminum hydride reduction of the oximes of 3-ketocholest-4- and -5-enes gave mixtures of amines. These amines on acetylation and separation gave respectively N-acetyI-3(α)-aminocholest-5-ene, N-acetyl-3(β) aminocholest-5-ene, N-acetyl-3(α)-aminocholest-4-ene, and N-acetyl-3(β)-aminocholest-4-ene. The N-acetyl-3(α)-aminocholest-5-ene (m.p. 184.5 °C.) was shown to be identical with the cholesterylacetamide obtained by the acetylation of the degradation product from N-benzyl-3(α)-aminocholest-5-ene (m.p. 90-91 °C).
A SELF PUMPING DROPPING MERCURY ELECTRODE FOR USE WITH STIRRED SOLUTIONS
Authors: Miller D. M.
Published: May 2006

not available
INFRARED AND RAMAN SPECTRA OF 1-CHLOROPROPYNE AND 1-CHLOROPROPYNE-d3
Authors: Davidson D. W. , Bernstein H. J.
Published: May 2006

The infrared spectra of 1-chloropropyne and 1-chloropropyne-d3 have been investigated in the vapor state, in solution, and, in part, in the liquid over the spectral region 3 to 35 μ. Intensities of the infrared bands have been measured from the spectra of the solutions. The Raman spectra of the compounds in the liquid state, together with standard intensities and depolarization ratios of the Raman bands, were obtained. A complete assignment, based on a normal-coordinate calculation of the fundamentals, has been made. Coriolis coupling coefficients of three of the perpendicular-type fundamentals of CH3≡CCl were determined and those of the other two shown to be near unity. Two coupling coefficients for CD3C≡CCl were obtained. The potential function and isotope effects on Raman intensity and Raman displacement of the CCl stretching vibration are discussed.
A NOTE ON THE ALKALOIDS OF BUPHANE DISTICHA
Authors: Humber L. G. , Taylor W. I.
Published: May 2006

not available
1-ALKYL-2-IMIDAZOLIDINETHIONES
Authors: Thorn G. D.
Published: May 2006

not available
PYROLYSIS OF ETHYL MERCAPTAN
Authors: Boivin Jean L. , MacDonald Roderick
Published: May 2006

The decomposition of ethyl mercaptan to ethylene and hydrogen sulphide was studied at various temperatures, with and without a catalyst. Metal sulphides (copper, nickel, and cadmium) proved to be the most efficient catalysts for cracking ethyl mercaptan into unsaturated end products, the optimum temperature being 500–600 °C. When no catalyst was used a 40–50% yield of ethylene and a nearly quantitative conversion to hydrogen sulphide was observed between 600 and 700 °C. Other products identified in the exit gas were carbon disulphide, carbonyl sulphide, methane, hydrogen, ethane, thiophene, diethyl sulphide, and free sulphur. Identification of these products was aided by infrared and mass spectral analysis of the gas. A tentative mechanism for the reaction justifying the presence of the above by-products is outlined.
THE PAPILIONACEOUS ALKALOIDS: XXI. THE ALKALOIDS OF LUPINUS PILOSUS WALT. AND THE STRUCTURE OF TETRALUPINE
Authors: Thomas A. F. , Vipond H. J. , Marion Léo
Published: May 2006

The alkaloidal extract from Lupinus pilosus Walt. was found to contain two alkaloids, one widely occurring one, d-lupanine, and one which had already been reported to occur in this plant, i.e., d-epilupinine, but no lupinine. The alkaloid tetralupine has been found by direct comparison of the bases and their corresponding salts and by their infrared absorption spectra to be identical with dl-epilupinine. A study of the infrared absorption spectra of lupinine and epi-lupinine leads to the same conclusion as the chemical evidence, i.e., that in the former the hydroxymethylene group occupies the axial position whereas in epilupinine this group is in the equatorial position.
THE PHOTOLYSIS OF ACETONE IN THE LIQUID PHASE: THE GASEOUS PRODUCTS
Authors: Pieck R. , Steacie E. W. R.
Published: May 2006

An investigation has been made of the photolysis of liquid acetone in the temperature range from 55° to −25 °C. The quantum yields of all products are small, and decrease strongly with decreasing temperature. It is concluded that the low yields can be explained both on the basis of the 'cage effect', and by the deactivation of an excited molecule. At high temperatures and intensities the gaseous products can be accounted for on the assumption that radicals have escaped from the 'cage' and react analogously to the gas-phase mechanism. At low temperatures ethane formation in the 'cage' may be of importance.
STUDIES ON THE HETEROGENEITY OF CARRAGEENIN
Authors: Smith David B. , O'Neill A. N. , Perlin A. S.
Published: May 2006

The carbohydrate residues in κ-carrageenin are 3,6-anhydro-D-galactose and D-galactose which are present in nearly equal amounts. Tests following fractional precipitation of κ-carrageenin indicate general chemical homogeneity but physical heterogeneity. κ-Carrageenin is not susceptible to oxidation with periodate. Fractional precipitation of λ-carrageenin separates a main fraction which contains only D-galactose and a trace of 3,6-anhydro-D-galactose. This polysaccharide is susceptible to periodate oxidation. It is polydisperse on a mass basis. Materials containing glucose, xylose, and L-galactose segregate into minor fractions of λ-carrageenin and hence cannot be integral parts of the principal polysaccharides of carrageenin. L-Galactose has been isolated from carrageenin by a simple procedure.
THE MESOMORPHIC BEHAVIOR OF ANHYDROUS SOAPS: PART I. LIGHT TRANSMISSION BY ALKALI METAL STEARATES
Authors: Benton D. P. , Howe P. G. , Puddington I. E.
Published: May 2006

The anhydrous salts of the long chain fatty acids are known to pass through a number of well-defined mesomorphic forms between the true crystalline solid and the isotropic liquid. The nature of some of these mesomorphic forms has been investigated by a study of their optical properties, electrical conductivity, density, and viscosity. In this paper, results obtained by an optical method are presented for phase transition temperatures of the alkali metal stearates and a number of sodium stearates having substituents in the hydrocarbon chain.
COEXISTENCE PHENOMENA IN THE CRITICAL REGION: IV. TIME-DEPENDENT BEHAVIOR IN VERTICAL DISTRIBUTION OF THE CRITICAL OPALESCENCE IN ETHYLENE AND XENON
Authors: Murray F. E. , Mason S. G.
Published: May 2006

The variation with height of the transmittance in the critical region at various heights in long columns of xenon and ethylene continued to change for several hours after stirring. This change with time is attributed to gravitational settling of large molecular clusters. Other experiments also indicate that a region in which extensive molecular clustering occurs is necessary for an adequate description of phase transitions in the critical region.
THE REACTION OF 2-ALKYLTETRAHYDROPYRANS WITH ANILINE OVER ACTIVATED ALUMINA
Authors: Richards H. P. , Bourns A. N.
Published: May 2006

The vapor-phase reaction over activated alumina of 2-ethyltetrahydropyran with aniline gave 1-phenyl-2-ethylpiperidine, 1-phenyl-2-propylpyrrolidine, N-phenyl-4-heptenylamine, and N-phenyl-5-heptenylamine. 2-Methyltetrahydropyran with aniline gave 1-phenyl-2-methylpiperidine, 1-phenyl-2-ethylpyrrolidine, N-phenyl-4-hexenylamine, and N-phenyl-5-hexenylamine. The structures of the cyclic amines were confirmed by independent syntheses. The unsaturated secondary amines were reduced to known N-alkylanilines and degraded by ozonolysis. A mechanism has been proposed to account for the formation of these products.
2,3-DIHYDROBENZO(f)-l,4-OXATHIEPIN AND DERIVATIVES
Authors: Kulka Marshall
Published: May 2006

A method has been developed for the synthesis of a new heterocyclic system III. When 2-β-chloroethoxybenzyl chloride (XI) was heated with thiourea in alcohol solution, S-(2-β-chloroethoxybenzyl)isothiuronium chloride (XII) was formed which on cleavage with aqueous alkali in high dilution yielded 2,3-dihydrobenzo(f)-1,4-oxathiepin (III). Derivatives of III with substituents such as methyl, t-butyl, chlorine, and nitro in the 7 and 9 positions were prepared in high yields from the corresponding substituted 2-β-chloroethoxybenzyl chlorides. The presence of substituents in the position ortho to the chloroethoxy group of XII had no retarding effect on the cyclization to XIV.
A NEW TYPE OF OSMOMETER FOR AQUEOUS SOLUTIONS
Authors: Gardon J. L. , Mason S. G.
Published: May 2006

not available
CARBOHYDRATE THIOETHERS 1-DEOXY-1-THIOETHYL-D-FRUCTOSE
Authors: Baker Samuel B.
Published: May 2006

1-Deoxy-1-thioethyl-D-fructose was synthesized by two distinctly different methods. Less than the usual hindrance of the toluenesulphonyloxy group on the C-1 position in 2,3-4,5-diisopropylidene-1-O-p-toluenesulphonyl-D-fructose was found to occur in the presence of sodium ethanethiolate.
SYNTHESIS OF γ-HYDROXYGLUTAMIC ACID (DIASTEREOMERIC MIXTURE)
Authors: Benoiton Léo , Bouthillier L. P.
Published: May 2006

γ-Hydroxyglutamic acid has been synthesized by two independent methods, namely the condensation of ethyl α-acetoxy-β-chloropropionate with diethyl acetaraidomalonate, and the hydroxylation of glutamic acid. Chemical evidence is provided for the structure of the compound.
PHYSICOCHEMICAL STUDIES OF LIGNINSULPHONATES: I. PREPARATION AND PROPERTIES OF FRACTIONATED SAMPLES
Authors: Gardon J. L. , Mason S. G.
Published: May 2006

High molecular weight ligninsulphonates were separated from other constituents of spent sulphite liquor by a method of dialysis allowing continuous removal of the dialyzates and their replacement by distilled water. The process was controlled by continuous analysis of the residue and dialyzate. The lower molecular weight ligninsulphonates in the dialyzates were separated from the carbohydrates by precipitating their barium salts with ethanol; four fractions corresponding to different times of dialysis were prepared in this manner. The ligninsulphonates in the dialyzed liquor were separated into four additional fractions by ultrafiltration through membranes of different pore sizes. The methoxyl, sulphur, and phenolic hydroxyl contents, neutralization equivalent weights, reducing powers, ultraviolet absorption spectra, diffusion coefficients, and number-average molecular weights of the eight fractions were determined. The molecular weights of the fractions range from 3700 to 58,000 but the integral molecular weight distribution curve indicates the presence of ligninsulphonates with molecular weights as high as 100,000.
SOME CORRELATIONS OF THE MOLECULAR STRUCTURE OF ORGANIC PHOSPHORUS COMPOUNDS WITH THEIR INFRARED SPECTRA
Authors: Harvey R. B. , Mayhood J. E.
Published: May 2006

The infrared spectra of fourteen organic esters of phosphorus containing dimethylamino groups, and two esters containing diethylamino groups have been examined over the region 5000 to 670 cm.−1 (2 to 15 microns). Correlations have been obtained between absorption band frequencies and the presence of dialkylamino groups in the molecule as an aid to their identification in the spectra of phosphorus compounds. A number of compounds of the pyrophosphate type have been examined and absorption associated with the (P—O—P) linkage has been found in the 950 to 910 cm.−1 (10.5 to 11.0 micron) region. Some criteria are proposed to distinguish absorption by the (P—O—P) linkage in this region.
THE ANALYSIS OF FLUOROCARBONS: USE OF INFRARED SPECTROPHOTOMETRY FOR THE ANALYSIS OF SMALL SAMPLES
Authors: Ayscough P. B.
Published: May 2006

A method for the analysis of small quantities of mixtures of carbon tetra-fluoride, hexafluoroethane, and fluoroform based on measurement of the intensity of infrared absorption bands is described. The relation between pressure and optical density for the main absorption bands of each gas was determined and used to calculate the composition of synthetic mixtures. These results were compared with those obtained by mass spectrometric analysis.
THEORY OF THE TRANSIENT PHASE IN KINETICS, WITH SPECIAL REFERENCE TO ENZYME SYSTEMS
Authors: Laidler Keith J.
Published: May 2006

The steady-state hypothesis is discussed for enzyme systems, and the conditions under which the steady-state equations will be valid over the main course of the reaction are obtained. It is shown that this is so if the substrate is in great excess, and also under several other circumstances. Equations are derived for the kinetic behavior during the transient phase of the reaction. Two-substrate systems, and the special case of catalase, are considered.
MERCURY PHOTOSENSITIZED DECOMPOSITION OF ETHYLENE OXIDE
Authors: Cvetanović R J
Published: May 2006

Some aspects of the mercury photosensitized decomposition of ethylene oxide at room temperature have been reinvestigated. At least two, and probably more than two, distinct primary steps occur. The previously assumed major primary formation of hydrogen by a molecular process is shown to occur to a relatively small extent only. Hydrogen atoms play an important role in the process, as well as the following radicals: CH3, CHO, CH2CHO, and C2H5, and probably to a lesser extent also CH2. The products formed are CO, H2, C2H6, a little CH2CO and C2H4, and large amounts of aldehydes. The presence of higher aldehydes has been demonstrated. While there is a general similarity to the other modes of decomposition of ethylene oxide, a unique and unambiguous solution of the complete reaction mechanism is at present not possible.
OZONOLYSIS OF 1-SUBSTITUTED CYCLOOLEFINS
Authors: Diaper D. G. M.
Published: May 2006

Extension of an aliphatic chain by five, six, or seven carbon atoms may be achieved by adding to it a 5-, 6-, or 7-membered olefmic alicycle and subsequently breaking the double bond. Addition of the ring is achieved by a Grignard reaction between an alkylmagnesium bromide and a cyclic ketone, and the resulting 1-alkylcycloolefin is opened by ozonolysis. The end product is a 5-, 6-, or 7-keto acid.
A QUARTZ SPIRAL-TORSION MICROBALANCE
Authors: Bushuk W. , Winkler C. A.
Published: May 2006

not available
INTENSITY IN THE RAMAN EFFECT: IV. RAMAN INTENSITY SUM RULES AND FREQUENCY ASSIGNMENTS FOR CH3CN, CD3CN, CH3CCl3, AND CD3CCl3
Authors: Evans J. C. , Bernstein H. J.
Published: May 2006

The standard intensities of the Raman bands of CH3CN, CD3CN, CH3CCl3 and CD3CCl3 have been obtained for the liquids with a photoelectric, grating spectrometer. The intensity sum rules for isotopic homologues are valid within the experimental error. The infrared spectra of CD3CN and CD3CCl3 have been obtained in the liquid phase and in the vapor phase. A definitive assignment of v11(e) has been made for methyl chloroform.
THE EFFECT OF ADDITION AGENTS ON CATHODE POLARIZATION DURING ELECTRODEPOSITION OF COPPER AT SINGLE CRYSTAL COPPER CATHODES
Authors: Ekler K. , Winkler C. A.
Published: May 2006

The polarization–time relations for the initial (Pi), maximum (Pmax), and pseudo-steady-state (Ps) polarizations on copper single crystals in the absence and presence of gelatin and gelatin plus chloride ion were found to depend upon crystal orientation. The Pi and Pmax in the absence of gelatin, the Pi in its presence, and the static potentials were all similarly related to the reticular density. The Pi increased, and the time to maximum polarization (tmax) decreased, with increase of current density; the relations between these quantities showed marked differences for the different crystals. The variation with reticular density of Pi and Pmax in the absence of addition agents and of Pi in its presence probably represents differences in activation overpotential at the various crystal faces. The adsorption of gelatin on different crystal faces was also found to be markedly different. Polarization in the presence of gelatin was decreased by small amounts of chloride ion; a linear relation for all the crystals used was obtained by plotting the increase in polarization caused by gelatin against the decrease caused by 2 mgm./liter chloride ion in the presence of gelatin. In the absence of addition agent, change of acid concentration from 50 to 200 gm./liter had no effect on Pi and addition of chloride ion had no effect on Ps at single crystal cathodes.
KINETICS OF THE OXIDATION OF URANIUM (IV) BY IRON (III) IN AQUEOUS SOLUTIONS OF PERCHLORIC ACID
Authors: Betts R. H.
Published: May 2006

The kinetics of oxidation of uranium (IV) by iron (III) in aqueous solutions of perchloric acid have been investigated at four temperatures between 3.1 °C. and 24.8 °C. The reaction was followed by measurement of the amount of ferrous ion formed. For the conditions (H+) = 0.1–1.0 M, ionic strength = 1.02, (FeIII) = 10−4–10−5 M, and (UIV) = 10−4–10−5 M, the observed rate law is d(Fe2+)/dt = −2d(UIV)/dt[Formula: see text]K1 and K2 are the first hydrolysis constants for Fe3+ and U4+, respectively, and K′ and K″ are pseudo rate constants. At 24.8 °C., K′ = 2.98 sec.−1, and K″ = 10.6 mole liter−1 sec−1. The corresponding temperature coefficients are ΔH′ = 22.5 kcal./mole and ΔH″ = 24.2 kcal./mole. The kinetics of the process are consistent with a mechanism which involves, as a rate-controlling step, electron transfer between hydrolyzed ions.
THE POLAROGRAPHY OF MALEIC HYDRAZIDE
Authors: Miller D. M.
Published: May 2006

Maleic hydrazide was found to be similar to maleic acid in its polarographic behavior. Two pairs of double waves are produced, one in the region around pH 5.9 and the other around 8.2. The theory that the double waves are a result of the reduction of the undissociated acid followed by that of its anion at a higher negative potential appears to explain the first of these double waves but fails to explain the second.
LIGHT ABSORPTION STUDIES: PART II. ULTRAVIOLET ABSORPTION SPECTRA OF SUBSTITUTED BENZOIC ACIDS AND PHENYL BENZOATES
Authors: Forbes W. F. , Sheratte M. B.
Published: May 2006

The spectra of a number of substituted benzoic acids, acetanilides, and phenyl benzoates are discussed in terms of the electronic and steric effects of substituents.
PHOTOLYSIS OF DIETHYL KETONE AT LOW PRESSURES: THE PRESSURE DEPENDENCY OF THE COMBINATION OF ETHYL RADICALS
Authors: Brinton R. K. , Steacie E. W. R.
Published: May 2006

The photolysis of diethyl ketone has been investigated in the pressure range 0.01–30 mm. at 100°, 150°, 200°, and 250° with a variation in absorbed intensity of 1000-fold. Over this wide variation in experimental conditions the kinetics of the reaction show excellent agreement with the mechanism of Kutschke, Wijnen, and Steacie. Under conditions where the production of ethylene by decomposition of the pentanonyl radical was negligible (high light intensity and low ketone pressure), the ratio of the rate of ethylene formed to the rate of butane produced was determined to be 0.12 independent of the temperature. These data indicate that both the disproportionation and combination of ethyl radicals are homogeneous and pressure independent to as low as 0.01 mm. pressure. In addition it is probable that the two reactions are the result of different reaction intermediates as was postulated by Wijnen and Steacie. The abstraction reactionC2H5+C2H5COC2H5 → C2H6+C2H4COC2H5showed definite heterogeneous character at low pressures similar to the analogous reaction of methyl radicals with acetone studied by Ausloos and Steacie.
THE POLAROGRAPHY OF THE MONOXIMES AND DIOXIMES OF BENZOQUINONE, NAPHTHOQUINONE, AND ANTHRAQUINONE
Authors: Elofson R. M. , Atkinson J. G.
Published: May 2006

The polarographic behavior of the monoximes and dioximes of 1,4-benzoquinone, 1,4-naphthoquinone, 1,2-naphthoquinone, and 9,10-anthraquinone has been investigated in the pH range 3 to 14. All of the compounds produce well-defined polarographic reduction waves which can be used for analytical purposes. Polarographic evidence indicates that the monoximes and the dioximes exhibit tautomerism.
PREPARATION OF D-AND L-GLYCERALDEHYDE FROM KETOHEXOSES
Authors: Perlin A. S. , Brice Carol
Published: May 2006

not available
AN OXYGEN-18 STUDY OF ACETAL FORMATION AND HYDROLYSIS
Authors: Stasiuk Fred , Sheppard W. A. , Bourns A. N.
Published: May 2006

A tracer study has been made of acetal formation and hydrolysis. Benzaldehyde and n-butyraldehyde, enriched in O18, on reaction with n-butyl and allyl alcohols, gave acetals of normal isotopic abundance. The label appeared in the water of condensation. Hydrolysis of benzaldehyde di-n-butyl acetal and n-butyraldehyde di-n-butyl acetal in O18 enriched water gave alcohols of normal isotopic content. A slight enrichment due to isotopic exchange was found in allyl alcohol produced by the hydrolysis of benzaldehyde diallyl acetal. These results establish that the reversible reaction proceeds by a fission of the aldehyde-carbon to oxygen bond.
THE VIBRATIONAL SPECTRA OF THE FORMATE, ACETATE, AND OXALATE IONS
Authors: Ito K. , Bernstein H. J.
Published: May 2006

The infrared spectra of the formate, acetate, and oxalate ions have been obtained for both the solid and aqueous solution. The Raman spectra of these ions with depolarization ratios have been obtained in aqueous solution. Vibrational assignments have been made which differ slightly for the acetate ion and more markedly for the oxalate ion from earlier work. The depolarization ratios confirm Fonteyne’s assignment for the formate ion.
SYNTHESIS OF METHYL-d3 FORMATE
Authors: Renaud R. , Leitch L. C.
Published: May 2006

not available
THE CRYSTAL STRUCTURE OF DES-(OXYMETHYLENE)-LYCOCTONINE HYDRIODIDE MONOHYDRATE
Authors: Przybylska Maria , Marion Léo
Published: May 2006

not available
SYMPOSIUM ON NUCLEAR CHEMISTRY AND RADIOCHEMISTRY
Authors: Yaffe L.
Published: May 2006

not available
CHEMICAL EFFECTS OF THE C12(γ,n)C11 REACTION IN CARBONATES
Authors: Edwards W. J. , McCallum K. J.
Published: May 2006

The chemical effects following the carbon photoneutron reaction in calcium carbonate and sodium bicarbonate have been studied. After solution of the irradiated crystals, C11 was found to be present in the forms of carbonate, carbon monoxide, formic acid, oxalic acid, glyoxylic acid, and glycollic acid. The relative amounts of C11 appearing in each form agreed closely with those found previously for irradiations of solid sodium carbonate.
PILE NEUTRON CAPTURE CROSS SECTION OF 33 HR. Ce143
Authors: Roy L. P. , Yaffe L.
Published: May 2006

Ce144 has been produced by the successive neutron capture reaction Ce142 (n, γ)Ce143(n, γ)Ce144. The pile neutron capture cross section of the 33 hr. Ce143 was determined by separating Pr144, the daughter of Ce144, from the rigorously-purified cerium at frequent intervals. The amount of Pr144 formed increased linearly with the square of the neutron flux in a manner consistent with that of a successive neutron capture reaction. The value for the pile neutron capture cross section of Ce143 was found to be 6.0 ± 0.7 barns.
THE MASS SPECTROMETRY OF THE ACTINIDE ELEMENTS
Authors: Hall G. R. , Walter A. J.
Published: May 2006

The problems involved in the mass spectrometry of the actinide elements and, in particular, the advantages of using a thermal ionization filament source are discussed. The relative behavior of each of the actinide elements from thorium to americium using this source is described and the results are considered with reference to the Saha equation.
THE PREPARATION AND PROPERTIES OF Pu242
Authors: Butler J. P. , Lounsbury M. , Merritt J. S.
Published: May 2006

Three samples of plutonium rich in Pu242 and containing from 1.7 to 8.6% Pu238 have been prepared by the neutron irradiation of Am241. From mass analyses and measurements of the alpha abundance of Pu242, the alpha half-life of Pu242 was determined as 3.73 ±.05 × 105 yr. The spontaneous fission half-life of Pu242 was also measured as 6.64 ± 0.10 × 1010 yr.
DISINTEGRATION-RATE DETERMINATION BY 4π-COUNTING: PART IV. SELF-ABSORPTION CORRECTION: GENERAL METHOD AND APPLICATION TO Ni63 β-RADIATION
Authors: Pate B. D. , Yaffe L.
Published: May 2006

A method of preparing thin uniform sources of radioactive materials for use in a 4π counter is described. The radioactive nuclides are formed into organic compounds and are subsequently distilled on to thin VYNS films. Electron microscope photographs of the deposits are shown. The material is uniformly deposited in crystals of about 1 μ in diameter. The distillation can be rendered quantitative. The amount of material on the film can be estimated either spectrophotometrically in situ or by appropriate chemical means. Using this method a self-absorption curve for Ni63 (maximum beta energy 67 kev.) is obtained.
THE SOLVENT EXTRACTION OF PROTACTINIUM
Authors: Goble A. , Golden J. , Maddock A. G.
Published: May 2006

The variation of the experimental extraction coefficient for protactinium upon dilution of the solvent ketone with benzene has been determined for aqueous solutions at constant concentration of hydrochloric acid. The bromo complex has been shown to be far less readily extracted. The effects on the extraction of the nitrate complex by amyl acetate, of the nitric acid, of the nitrate and hydrogen ion concentrations in the aqueous phase, as well as of the dilution of the solvent with benzene, have been explored. The existence of a slow reaction in the extraction has been demonstrated. It is concluded that chloride solutions are the more reliable for the isolation of protactinium from concentrates.
THE YIELDS OF 129I IN NATURAL AND IN NEUTRON-INDUCED FISSION OF URANIUM
Authors: Purkayastha B. C. , Martin G. R.
Published: May 2006

Measurements have been made, by a radioactivation technique, of the 129I formed in uranium by pile-neutron-induced fission, and in pitchblende by the natural fission of uranium. The amount found in the pile-neutron-irradiated uranium corresponds to a fission yield of 0.90% at mass 129. The natural production of 129I in pitchblende is discussed in the light of the mass-spectrometric measurements of spontaneous fission xenon made by Thode and his collaborators. An upper limit of 1 part in 108 can be set for the occurrence of 129I in natural iodine. The pile neutron capture cross section of 129I has been measured as 35 barns.
CHEMICAL EFFECTS OF THE NUCLEAR TRANSFORMATION N14( n, p)C14
Authors: Yankwich Peter E.
Published: May 2006

The physical and chemical behavior of energetic carbon particles in ionic lattices is investigated. Models of the process due to Libby and to Seitz and Koehler are compared for simple and complex ionic crystals. For simple crystals the models lead to practically identical chemical predictions; where polyatomic ions are present, the Seitz–Koehler model appears to give a more satisfactory account of the distribution of radiocarbon over various product species.
ON FLAME PROPAGATION IN EXPLOSIVE MIXTURES OF GASES: II. ON THE DECOMPOSITION FLAME OF OZONE
Authors: Sandri Robert
Published: May 2006

The general theory developed in an earlier paper of the author is applied to the ozone explosion. Values of the linear flame velocity are computed under the assumption of constant enthalpy and, without this assumption, for different values of the reduced diffusion coefficient. The results do not differ very much and are found to be in very good agreement with experiments. They are further compared to the results which were obtained by Hirschfelder et al. by exact numerical integration and by Kármán and Penner by an approximation method and are found to be between the values obtained by these authors.
FREE RADICALS BY MASS SPECTROMETRY: X. THE IONIZATION POTENTIALS OF METHYL SUBSTITUTED ALLYL RADICALS
Authors: McDowell C. A. , Lossing F. P. , Henderson I. H. S. , Farmer J. B.
Published: May 2006

The vertical ionization potentials of the β- and γ-methyl substituted allyl radicals as measured by electron impact are 8.03 ± 0.05 v. and 7.71 ± 0.05 v, respectively. From appearance potential data the following bond dissociation energies can be derived, assuming the dissociation processes to be free from complications:[Formula: see text]With assumptions about the structure of the ions produced by electron impact from the corresponding butenes the dissociation energies of the C4H7—H bonds in these latter compounds can be estimated, and the heats of formation of the corresponding radicals derived, namely:[Formula: see text]From data on the allyl halides we evaluate the heat of formation of the allyl radical to be:[Formula: see text]
DETERMINATION OF PARAMETERS IN OVERPOTENTIAL STUDIES
Authors: Morley H. B. , Wetmore F. E. W.
Published: May 2006

A simple method is reported for analyzing decay curves in overpotential studies. As well, equations have been derived for build-up and decay curves and for the overpotential–current relationship, based on an assumption which introduces less error than the simplifying assumptions used previously.
REACTIONS OF SOME HALOGEN DERIVATIVES OF TETRAHYDROPYRAN-2-OL
Authors: Charlesworth E. H. , Giesinger A.
Published: May 2006

The 3-halotetrahydropyran-2-ols have been found to readily give derivatives of tetrahydrofurfural in aqueous alcohol under weakly basic or acidic conditions. In strongly alkaline solution tetrahydropyran-2,3-diol and its anhydro-polymers were formed. 3,3-Dichlorotetrahydropyran-2-ol and 2,3,3-trichlorotetrahydropyran have been converted by aqueous alkali to viscous sirups which appear to contain 2-hydroxytetrahydropyran-3-one and its tautomers. On oxidation with permanganate these sirups have yielded succinic acid.
CROSS-LINKING OF COPOLYMERS FROM METHYL VINYL KETONE AND n-BUTYL ACRYLATE
Authors: Cooper W. , Catterall E.
Published: May 2006

Copolymers of n-butyl acrylate and methyl vinyl ketone can be cross-linked by a combination of sulphur and zinc oxide; the reaction is associated with the methyl vinyl ketone units in the polymer chain. From studies on the copolymers and model compounds, it is suggested that adjacent pairs or groups of methyl vinyl ketone units in the polymer cyclize to give αβ unsaturated ketone groups. These contain reactive hydrogen which is attacked by sulphur; disulphide or zinc mercaptide cross-links are then formed. Water is produced in the cyclization reaction and hydrolyzes some of the ester groups; additional cross-links are thus formed by reaction of the acid groups with zinc oxide. The ease of cyclization and, therefore, the extent of cross-linking is dependent on the method of preparing the copolymers, emulsion copolymers being much more reactive than those prepared in solution. A comparison has been made between the sulphur + zinc oxide system and other cross-linking agents which may be used for polyacrylates.
A SEARCH FOR THE CHEMICAL EFFECTS OF INTERNAL CONVERSION FOLLOWING RADIATIVE NEUTRON CAPTURE
Authors: Maddock A. G. , Maine M. M. de
Published: May 2006

The possibility that neutron capture would lead to oxidation, because of internal conversion of the capture radiation, has been investigated in solid compounds of the lower valence states of antimony, arsenic, cerium, chromium, and thallium. Except in the hydrated compounds, negative results have been obtained. It is possible that oxidation is followed by electron-transfer exchange in the irradiated solids.
DECOMPOSITION OF SODIUM HYPOCHLORITE: THE CATALYZED REACTION
Authors: Lister M. W.
Published: May 2006

The catalyzed decomposition of sodium hypochlorite has been examined; the catalysts tried were manganese, iron, cobalt, nickel, and copper oxides. It was shown that in no case was the decomposition to chlorate and chloride accelerated, only the reaction to chloride and oxygen. Manganese and iron did not catalyze even the latter reaction, or only to a very small extent; this was in fairly concentrated sodium hypochlorite containing some sodium hydroxide. The manganese and iron are largely oxidized to permanganate and ferrate under these conditions. It was found that copper could catalyze the formation of permanganate and ferrate, and nickel the formation of permanganate. Cobalt catalyzed the reaction going to oxygen, and the rate was proportional to the cobalt added, but little dependent on the hypochlorite concentration; the same is true of nickel. Copper (as reported earlier) gives a catalyzed reaction not far from first order in hypochlorite. The activation energies were measured, and were consistent with the relative catalytic activity of these metals. The mechanism of the reaction is briefly discussed.
APPLICATION OF THE WISHAW-STOKES EQUATION TO THE CONDUCTANCES OF POTASSIUM CHLORIDE SOLUTIONS AT 25 °C.
Authors: Campbell A. N. , Ross L.
Published: May 2006

not available
MYRISTIC ACID MONOLAYER AT LOW SURFACE PRESSURES
Authors: Semeluk G. P. , Hahn J. W. V. , Morrison John L.
Published: May 2006

The surface pressure–area relationships of gaseous myristic acid films at the air–aqueous interface have been measured at very low surface pressures. The acid was spread from petroleum ether solutions. The molecular cohesion was found to be about six times that of gaseous butane under comparable conditions. Some explanation of Moss and Rideal’s “double molecule” phenomenon is given.
A SYSTEM OF MOLECULAR THERMOCHEMISTRY FOR ORGANIC GASES AND LIQUIDS
Authors: Laidler Keith J.
Published: May 2006

An analysis has been made of the heats of formation and combustion of organic gases and liquids, and of the heats of vaporization of liquids. The work has been done as far as possible with homologous series, in order to discover systematic effects. The data are converted into heats of atomization, i.e., the heats required to convert the gases or liquids into their constituent atoms. It is shown that the heats of atomization of the gaseous aliphatic hydrocarbons (paraffins, olefins, and acetylenes) can be accurately represented by a scheme in which a distinction is made between primary, secondary, and tertiary carbon–hydrogen bonds, and between bonds that are next to, and next but one to, multiple bonds. For aromatic molecules an appropriate correction for resonance is proposed. For other types of compound it is found that suitable values for the various bonds (e.g., C–CHO, C–OH) will give rise to good agreement with experiment.It is shown that to a reliable approximation heats of vaporization are also amenable to the same treatment. Since this is so it is possible to assign bond values on the basis of which it is possible to make predictions about heats of formation of liquids.A system of coefficients is worked out by means of which the numbers of atoms of various kinds in a molecule can be expressed in terms of the numbers of the different kinds of bonds. On the basis of these it is shown how bond contributions to heats of formation and heats of combustion can be calculated. A table (Table X) gives the contributions proposed for the heats of atomization, heats of formation, and heats of combustion for both gases and liquids.
THE SYSTEM LiCl–NaCl–KCl–H2O AT 25 °C
Authors: Campbell A. N. , Kartzmark E. M.
Published: May 2006

Of the component ternary systems of the quaternary system LiCl–NaCl–KCl–H2O, the system LiCl–KCl–H2O has not previously been investigated. This has now been done and it is shown to be very similar to the system LiCl–NaCl–H2O investigated by Smits, Elgersma, and Hardenberg (4). In both systems, the strongly hydrated lithium ion reduces the content of second salt to a low value at the (isothermal) invariant point.The quaternary system of the title has been investigated, using a new method of analysis which involves the determination of total chloride and of density. The quaternary invariant composition is similar to that of the ternary invariant in the system LiCl–KCl–H2O. In none of these systems is there formation of double salt or solid solutions and the only hydrate occurring as a solid phase is LiCl.H2O.
INFLUENCE OF THE NUMBER OF CARBON ATOMS OF THE ALKYL GROUP ON POLYMERIZATION AND PROPERTIES OF PARA-ALKYLPHENOL–FORMALDEHYDE POLYMERS
Authors: Rosenthal A. , Lederer F. , Gilson K.
Published: May 2006

The polymerization (in organic media) of p-cresol–formaldehyde has been investigated in sealed tubes and in open systems. A series of almost colorless p-alkylphenol–formaldehyde polymers, prepared in sealed tubes, was studied to determine the influence of the number of carbon atoms of the substituting alkyl group on the polymerization process and on the properties of the polymers. Infrared spectra and chemical analyses of the original and heat-treated polymers were correlated with the structures of the polymers.
THE PREPARATION OF D-ARABOPENTURONIC ACID AND D-THREO- AND D-ERYTHRO-TETRURONIC ACIDS
Authors: Gorin P. A. J. , Perlin A. S.
Published: May 2006

D-Glucurono-γ-lactone, D-galacturonic acid, and potassium D-glucuronate have been degraded in good yield to D-arabopenturonic, D-threotetruronic, and D-erythrotetruronic acids, respectively, using lead tetraacetate in acetic acid solvent as the reagent.
FREE RADICALS BY MASS SPECTROMETRY: XI. THE MERCURY PHOTOSENSITIZED DECOMPOSITION OF C2–C4 OLEFINS
Authors: Lossing F. P. , Marsden D. G. H. , Farmer J. B.
Published: May 2006

The mercury photosensitized (Hg3P1) decomposition of olefins has been examined using a reactor coupled directly to a mass spectrometer. The primary split of ethylene has been shown to be predominantly molecular, and that of propylene mainly into an allyl radical and a hydrogen atom. With 1-butene the split is predominantly at a C–C bond giving allyl and methyl radicals, although a rupture of a C–H bond occurs as well. With 2-butene and isobutene a C–H bond is broken. It is concluded that the allyl and methallyl radicals produced have large cross sections for reaction with excited mercury atoms.
RADIOIODINE EXCHANGE BETWEEN IODOSTEARIC ACID MONOLAYERS AND SUBSTRATE IODIDE
Authors: Robertson R. F. , Winkler C. A. , Mason S. G.
Published: May 2006

Velocities of exchange of iodine between monolayers at the air/water interface of α-iodostearic acid and potassium iodide in the substrate have been measured over a range of monolayer and substrate concentrations and temperatures using a radioactive tracer technique. The pressure–area isotherms were also determined. The process was followed by measuring the decrease in counting rate immediately above the surface. It is shown theoretically that ions released to the substrate diffuse rapidly and do not contribute appreciably to the counting rate. The velocity of exchange was found to be first order in concentration of the surface phase and of higher but indeterminate order in concentration of potassium iodide. In the region of 18 °C., where a transition from liquid-condensed to liquid-expanded film occurs, the reaction velocity constant undergoes a discontinuous increase. Activation energies of 8.0 and 10.8 kcal./mole were found for exchange in the condensed and expanded films respectively.
THE DISTRIBUTION OF PLUTONIUM IN THE SYSTEMS URANIUM–SILVER AND URANIUM–SILVER–GOLD
Authors: McKenzie D. E.
Published: May 2006

An expression due to Hildebrand and Scott has been used to select silver as a possible extractant for plutonium from neutron-irradiated uranium. The distribution of plutonium between molten silver and molten neutron-irradiated uranium has been examined in small-scale experiments. The fraction of plutonium in the silver layer increases with increasing temperature. For equal weights of silver and uranium containing 0.1% plutonium, 88% of the total plutonium is distributed to the silver phase at 1350 °C. Greater proportions of plutonium are found in the silver phase in experiments with uranium of lower initial plutonium concentration. On the addition of gold to the system plutonium extraction is increased and passes through a maximum. This maximum appears to be associated with a particular concentration of gold in silver and of gold in uranium.
THE ADSORPTION OF NITROGEN BY CARBON BLACK AND GRAPHITE
Authors: McDermot H. L. , Lawton B. E.
Published: May 2006

The adsorption of nitrogen by a carbon black designated as Spheron 9 has been measured at 78 °K. and 71 °K. The second type of hysteresis previously reported for three Acheson graphites has also been observed for the adsorption of nitrogen by Spheron 9 at both temperatures. Unlike the graphite isotherms, it was possible to scan the hysteresis loop of the Spheron isotherm. The adsorption of nitrogen has been measured for an artificial graphite in which the ash had been leached out by treatment with hydrofluoric acid. The results were compared with those obtained previously for a sample of the unleached graphite. It was found that although the surface area was altered by this treatment, the hysteresis effects remained unchanged.
ON THE INFRARED ABSORPTION OF WATER AND HEAVY WATER IN CONDENSED STATES
Authors: Giguère Paul A. , Harvey K. B.
Published: May 2006

The infrared spectra (from 2 to 30 μ) of thin films of H2O and D2O were measured at various temperatures between 20 ° and −180 °C. A strong absorption band due to the librational mode of the water molecule has its maximum around 710 cm.−1 in the liquid. In ice it is shifted to 800 cm.−1 at −15 °C. and 850 cm.−1 at −170 °C. The corresponding D2O bands show the normal isotope shift. Thin films of water pressed between silver chloride plates could not be crystallized even at liquid air temperature as confirmed by their spectra, which were almost identical with those of the liquid.
THE DETERMINATION OF PARTIAL SPECIFIC VOLUMES BY DIFFERENTIAL SEDIMENTATION
Authors: Martin W. G. , Cook W. H. , Winkler C. A.
Published: May 2006

Sedimentation in aqueous and heavy water solutions has been used to determine the partial specific volume of bovine plasma albumin, sodium alginate, and polyvinyl alcohol, resulting in 0.74 ± 0.01 (S.D.), 0.54 ± 0.06, and 0.79 ± 0.01 ml./gm. at 25 °C, respectively. The sedimentation method yields results comparable with those given by conventional methods for macromolecules.
PALLADIUM AND SUBSTITUTED QUINOLINES
Authors: Ryan D. E.
Published: May 2006

not available
4,6-O-isoPROPYLIDENE-METHYL-α-D-GLUCOSIDE
Authors: Jones J. K. N.
Published: May 2006

not available
SYNTHESIS OF 2,5,6-TRI-O-METHYL-D-GLUCOSE
Authors: Bishop C. T. , Schmorak J.
Published: May 2006

The previously unknown 2,5,6-tri-O-methyl-D-glucose has been prepared from D-glucose. Proof of the constitution of this new sugar derivative is based on its chemical reactions and method of synthesis.
POLYMER-ANALOGOUS DENITRATION OF POLYSACCHARIDE NITRATES: A STUDY OF SOME REDUCTIVE METHODS WITH MODEL COMPOUNDS AND CELLULOSE NITRATE
Authors: Swan E. P. , Hayward L. D.
Published: May 2006

Crystalline D-mannitol penta- and hexa-nitrates, methyl-β-D-glucopyranoside tetranitrate, and maltose and cellobiose octanitrates were prepared as model substances of known constitution for study of denitration reactions possibly applicable to polysaccharide nitrates. Heterogeneous catalytic hydrogenation smoothly regenerated the parent carbohydrates from the model compounds in nearly quantitative yield and removed 0.42 and 0.63 nitrate groups per glucose unit from cellulose nitrates of 13.3 and 10.7% N respectively. Raney nickel was conveniently removed from the hydrogenated cellulose nitrates by means of a magnet. The action of methyl magnesium iodide, lithium aluminum hydride, or low-pressure hydrogenation with a homogeneous cupric acetate catalyst caused less complete denitration of the mannitol or cellobiose polynitrates. The nitration–fractionation–denitration sequence as a means of isolation of undegraded polysaccharides from natural sources is discussed.
REACTIONS OF ARYLSULPHONIC ESTERS: IV. AN INTERPRETATION OF SOLVOLYTIC ACTIVATION ENERGIES
Authors: Hyne J. B. , Robertson R. E.
Published: May 2006

A semiempirical equation is presented relating the activation energies of some fifty solvolyses of benzenesulphonic esters to physical properties of the solvolyzing medium. The equation predicts more than 70% of these activation energies to better than 300 cal./gm-mol. The significance of the equation is discussed on the basis of a continuous spectrum of mechanisms intermediate between the accepted SN1 and SN2 types. A suggested interpretation of the log PZ (activation entropy) term is also offered.