bluuebunny/crossref_metadata_2025 huggingface dataset:
A SPECTROSCOPIC STUDY OF HYDROGEN BONDING IN PERFORMIC AND PERACETIC ACIDS
Authors: Giguère Paul A. , Olmos A. Weingartshofer
Published: May 2006

The infrared spectra of concentrated performic and peracetic acids were measured in the rock-salt region. The most significant features are theO—H stretching frequency at 3310–3350 cm−1 and the OH bending frequency at 1450 cm−1 which, for both peracids, remain essentially the same in the vapor state as in the liquid or in solution in nonpolar solvents. This is attributed to intramolecular hydrogen bonds resulting in particularly stable five-membered rings,[Formula: see text]Steric conditions in the percarboxylic group are favourable to such ring formation or chelation. From the observed frequency shifts the energy of these hydrogen bonds is estimated to be about 7 kcal. per mole. No evidence for unchelated molecules was found even in very dilute solutions of peracetic acid in nonpolar solvent nor in the vapour at low pressure and moderate temperature. Tentative assignments of the other frequencies in the spectra of the peracids are made by comparison with those of formic and acetic acids.The danger involved in handling these peracids in concentrated form is emphasized.
DENSITY DISTRIBUTIONS IN A VERTICAL TUBE CONTAINING XENON NEAR THE CRITICAL TEMPERATURE AS MEASURED BY A RADIOACTIVE TRACER TECHNIQUE
Authors: Weinberger M. A. , Schneider W. G.
Published: May 2006

The variation of density with height has been determined for xenon confined in a long vertical bomb under near critical conditions. The densities were deduced by means of radioactive tracer techniques. Radioactive Xe127 was added to ordinary xenon and counting rates (assumed proportional to local densities) were measured at various positions along the bomb. The observed density distributions can be entirely explained by the influence of gravity on the system; a comparison of the observed density distribution with that calculated using the measured PV isotherms for xenon shows satisfactory agreement.
SYNTHESIS OF ORGANIC DEUTERIUM COMPOUNDS: III. 1,2-DIBROMOETHANE-d4 AND ITS DERIVATIVES
Authors: Leitch L. C. , Morse A. T.
Published: May 2006

Acetylene and hydrogen bromide react thermally without catalysts as well as photochemically to give high yields of 1,2-dibromoethane. The preparation of the following compounds containing 99 + % deuterium is described: acetylene-d2, 1,2-dibromoethane-d4, 1,2-dibromoethane-1,2-d2, ethylene-d4, 1,2-dichloro-ethane-d4, and ethylene-d4 oxide. The vapor pressure of ethylene-d4 oxide was determined in the temperature range −42 to 0 °C.
VIBRATION SPECTRA OF CIS AND TRANS DICHLOROETHYLENE-d1
Authors: Bernstein H. J. , Pullin A. D. E.
Published: May 2006

The infrared spectra of the vapor and the liquid, and the Raman spectra of liquid cis and trans C2HDCl2 have been obtained in the region 400–3300 cm−1 The observed spectra are in accordance with the assignment of Bernstein and Ramsay for cis and trans C2H2Cl2 and C2D2Cl2.
COAGULATION AND DEPOSITION IN STILL AEROSOLS OF VARIOUS SOLIDS
Authors: Gillespie T. , Langstroth G. O.
Published: May 2006

Studies have been made of the aging of magnesium oxide, zinc oxide, carbon, copal resin, and silica powder aerosols, under essentially uniform experimental conditions. The changes with time in the particulate number and in the number of particles lost from the system by deposition on chamber surfaces are well described in terms of the coagulation constant k and the deposition constant β with the aid of equations known to be applicable to ammonium chloride aerosols over a wide range of conditions. Marked differences were found in the values of k for different aerosols and lesser differences in the values of β. An electron microscope study of the shape and structure of the particles led to the conclusion that differences in these characteristics are not predominantly responsible for the observed differences in behavior, although they may be a contributing factor. A few preliminary experiments in which silica powder was dispersed through an electrically charged screen indicated that the coagulation and deposition processes are influenced by changes in the electrical charge distribution.
AN INSTRUMENT FOR DETERMINING THE ELECTRIC CHARGE DISTRIBUTION IN AEROSOLS
Authors: Gillespie T. , Langstroth G. O.
Published: May 2006

An instrument has been developed to permit measurement of the electric charges on a relatively large number of particles during a comparatively short period in the history of an aerosol. These novel characteristics have been obtained by depositing a sample on microscope slides in such a way that the charge on any particle at deposition can be determined in a subsequent examination from the size of the particle and its position on the slide. There is evidence to show that the act of sampling with this instrument does not cause spurious charging of particles. The construction and theory of the instrument are described in some detail and results of tests are given to show that the theory is applicable. The use of the instrument is illustrated by an account of a preliminary study of the charge distribution in a silica dust aerosol at various times after generation.
Note on the Polarographic Determination of Zirconium
Authors: Graham R. P , VanDalen E. , Upton A. M. C.
Published: May 2006

not available
THE ORIENTATIONAL POLARIZATION OF ADSORBED POLAR MOLECULES
Authors: Snelgrove J. A. , McIntosh R.
Published: May 2006

The orientational polarization of a polar molecule adsorbed on a solid surface is deduced for two cases. First, the molecule oscillates in the plane of the surface about some equilibrium position. A zero temperature coefficient of the polarization is deduced. Second, the molecule may rotate freely in the plane within some given angle, but cannot incline to any greater extent from the equilibrium position under the influence of the field. The normal temperature coefficient is obtained with this model.The derivation of these formulae is based upon the procedures of Kurbatov who considered oscillation and rotation to be possible in three dimensions. The models employed here are considered preferable on the grounds that a physically adsorbed polyatomic molecule would presumably lie flat in the plane of the adsorbing surface.
THE DECOMPOSITION OF SOLID POTASSIUM PERCHLORATE BY 50 KILOVOLT X RAYS
Authors: Heal H. G.
Published: May 2006

Potassium perchlorate crystals are decomposed by 50 kv. X rays. The main products of the primary decomposition are chlorate and chloride, but small amounts of unidentified oxidizing substances are also formed. The chlorate decomposes by a secondary reaction to chloride. These reactions are approximately of the first order. The average amount of X-ray energy absorbed by the salt per ClO4− ion decomposed is 19 ± 2 ev.
PHOTOLYSIS OF MIXTURES OF ACETONE AND SOME CHLORINATED METHANES
Authors: Cvetanović R. J. , Raal F. A. , Steacie E. W. R.
Published: May 2006

Additions of carbon tetrachloride to acetone show in photolysis an apparent anomaly: methane formation is strongly increased and the formation of ethane correspondingly lowered. In this manner a hydrogen abstraction reaction is simulated. The cause of the anomaly and its bearing on the photolysis of acetone with other chlorinated methanes has been investigated.
STUDIES OF LIGNIN BIOSYNTHESIS USING ISOTOPIC CARBON: I. LONG-TERM EXPERIMENT WITH C14O2
Authors: Stone J. E.
Published: May 2006

Wheat plants were fed with C14O2 at the stage of growth corresponding to rapid lignification. Thereafter, plants were harvested every few days until maturity. The specific and total activity of the plants, and the specific and total activity in some lignin degradation products were determined. Results indicated that (i) C14O2 was still being respired from the plants at maturity, (ii) all the C14 which gets into the lignin does so within 24 hr. from the administering of C14O2, (iii) the total activity originally acquired by the syringaldehyde portion of the lignin remains constant throughout the growth of the plant, that is, the lignin (as represented by syringaldehyde) is a final end product of the plant and is not a part of the respiratory system, (iv) the total activity originally acquired by the vanillin suffers an initial drop for about two weeks after activation and then becomes constant, (v) the p-hydroxybenzaldehyde activity drops continuously throughout the life of the plant.
REACTIONS IN DISSOCIATED PEROXIDE VAPOR
Authors: Batzold J. S. , Luner C. , Winkler C. A.
Published: May 2006

The products of the electrical discharge through hydrogen peroxide vapor were hydrogen peroxide, water, oxygen, and hydrogen, in amounts which depended upon the arrangement and temperature of the trap, reaction time, and surface to volume ratio of the reaction vessel. Water, hydrogen, and oxygen resulted from the gas phase reactions of the dissociated hydrogen peroxide, with hydrogen peroxide produced only in a trap cooled below −120 °C. Products trapped below −150 °C evolved oxygen on warming to room temperature. The decomposition products of the electrical discharge through hydrogen peroxide correspond closely with products obtainable both from a similar discharge through water vapor and from the interaction of hydrogen atoms with oxygen molecules in a cold trap. A mechanism which accounts for their correspondence is included. Water was the only product when molecular hydrogen peroxide was caused to react with hydrogen atoms, dissociated hydrogen peroxide vapor, or dissociated water vapor in the presence or absence of molecular hydrogen. A chain mechanism is postulated for these reactions.
ORGANIC DEUTERIUM COMPOUNDS: V. THE CHLORINATION OF PROPYNE AND PROPYNE-d4
Authors: Leitch L. C.
Published: May 2006

Chlorination of propyne at 70 °C. gave 60 to 65% yields of 1,1,2,2-tetrachloropropane and 15 to 20% yields of trans-1,2-dichloro-1-propene. 1,1,2,2-Tetrachloropropane-d4 was similarly prepared from propyne-d4. Nearly theoretical yields of cis- and trans-1,2-dichloro-1-propene were obtained by partial dechlorination of tetrachloropropane. Deuterated cis- and trans-1,2-dichloro-1-propene were obtained in the same manner from 1,1,2,2-tetrachloropropane-d4.
DETERMINATION OF THE NEUTRON CAPTURE CROSS SECTION FOR THE Co59(n,γ)Co60m REACTION
Authors: Moss N. , Yaffe L.
Published: May 2006

A determination of the neutron capture cross section of Co59 leading to the excited state of Co60 has been made by the activation method. Samples of cobalt were irradiated in the center of the Chalk River nuclear reactor in a pure iron capsule using a pneumatic delivery device. The cobalt activity was counted in a windowless counter and compared with the activity of a strip of pure gold irradiated under identical conditions in the same container. The cobalt and gold were counted with and without cadmium wrapping and the contribution due to epicadmium neutrons allowed for in the calculation. The mean value obtained was 18.3 ± 1.7 barns relative to σAu197 = 93 barns.
THE OXIDATION OF FERROUS SULPHATE SOLUTIONS BY γ-RAYS–THE EFFECT OF SURFACE/VOLUME RATIO OF POLYSTYRENE CELLS ON THE YIELD
Authors: Hardwick T. J.
Published: May 2006

not available
KINETICS OF SILVER – SILVER ION EXCHANGE
Authors: Baerg A. , Winkler C. A.
Published: May 2006

The kinetics of silver – silver ion exchange have been studied with etched silver foils. The results indicate that several different rates of reaction occur on a single specimen. This may be interpreted to indicate the presence of crystal faces of different orientations, each of which exchange at a given rate. Interchange of ions in solution with radioactive ions adsorbed on the metal surface was not distinguishable from exchange between ions in solution and active atoms of the metal. When adsorbed silver ions were electrodeposited, the resulting metal surface exhibited a completely heterogeneous character with respect to exchange.
N-BIS-(β-N-ARYLCARBAMYLOXYETHYL)ARYLAMINES
Authors: McKay A. F. , Hatton W. G.
Published: May 2006

not available
CRYSTALLINE XYLANS FROM STRAWS
Authors: Bishop C. T.
Published: May 2006

Hemicelluloses, extracted from barley, flax, oat, rye, and wheat straw holo-celluloses, were composed predominantly of anhydro-D-xylose units, with small amounts of L-arabinose and D-glucuronic acid. The hemicelluloses had degrees of polymerization ranging from 55 for oat to 185 for rye and were shown to be linear polysaccharides. Autoclaving in distilled water at 120 °C. yielded crystalline xylans from barley, rye, and wheat straw hemicelluloses. The basic structure of the hemicellulose was maintained in the crystalline xylans, which gave identical X-ray diffraction patterns and had similar, linear structures. The crystallization procedure was found to degrade the hemicellulose, removing D-xylose, L-arabinose, and D-glucuronic acid as components of hydrolytic fragments and leaving a pure xylan one sixth to one third the length of its parent hemicellulose. Depending on uronic acid content, the five hemicelluloses in water gave pH values ranging from 2–5 with consequent variations in resistance to hydrolysis during autoclaving
A METHOD FOR THE IDENTIFICATION OF THE MONO-O-METHYLGLUCOSES
Authors: Lemieux R. U. , Bauer H. F.
Published: May 2006

Periodate oxidation of any one mono-O-methylglucopyranose and alkaline hydrolysis of the product yields a substance which can be positively distinguished by paper chromatography from the products formed under the same conditions from the other mono-O-methylglucopyranoses. Thus, the components of a mixture of the mono-O-methylglucopyranoses can be readily identified. The method appears useful for the identification of di-O-methylglucoses. Reduction with sodium borohydride prior to periodate oxidation renders the method useful for the identification of tri-O-methylglucoses. The potential value of the method, which can be used on a microscale, is illustrated by an application to the characterization of the O-methylglucoses derived from a water-soluble O-methyl-cellulose
THE OXIDATION OF FERROUS SULPHATE BY γ-RAYS— THE TEMPERATURE COEFFICIENT OF AIR-SATURATED SOLUTIONS
Authors: Hardwick T. J.
Published: May 2006

not available
THE NITRATION OF 2-NITRAMINOTHIAZOLES AND 2-ACETAMIDOTHIAZOLES
Authors: Viron Silvio J. , Taurins Alfred
Published: May 2006

It has been shown by nitration with a mixture of 99–100% nitric acid and acetic anhydride that 2-nitraminothiazoles, such as 2-nitramino-5-nitrothiazole and 4-methyl-2-nitramino-5-nitrothiazole, can react in the tautomeric nitrimino form. The nitration occurs in the three position of the thiazole ring. Compounds with an acetamido group in the two position of the thiazole ring, such as 2-acetamido-5-bromo-2-thiazole and 2-acetamido-5-methylthiazole, can also be nitrated in the three position indicating the tautomeric change from the acetamido to the acetimido group.
ELECTROPHORESIS OF RESIN EMULSIONS: II. THE EFFECT OF ELECTROLYTE CONCENTRATION ON THE MOBILITIES AND ZETA POTENTIALS
Authors: Munro L. A. , Sexsmith F. H.
Published: May 2006

Electrolyte concentration, rather than pH, concentration of resin particles, or dispersity, is the most significant variable affecting the mobility of polyvinyl acetate emulsions. The mobility–electrolyte concentration curves for latices prepared with nonionic and mixed nonionic and anionic emulsifiers, indicate micelle formation at low electrolyte concentrations. Zeta potentials calculated for a typical latex show the potential drop in the double layer to be of the order of 10−7volts for a variation of thickness of the ionic atmosphere from 10−5to 10−6 cm. over the range of salt concentration used.
THE REACTION OF CYANOGEN BROMIDE WITH THE SODIUM SALTS OF CARBOXYLIC ACIDS: I. THE REACTION OF CYANOGEN BROMIDE WITH SODIUM BENZOATE
Authors: Douglas D. E. , Eccles Jean , Almond Anne E.
Published: May 2006

The main products of the reaction of cyanogen bromide with sodium benzoate at 250 ° to 300 °C. are carbon dioxide, benzonitrile, and sodium bromide. Tracer studies have shown that the carbon of the carbon dioxide is derived almost entirely from the cyanogen bromide.
INTERACTION OF KETO- AND TERTIARY AMINO-FUNCTION IN MEDIUM RINGS
Authors: Mottus Edward H. , Schwarz Hans , Marion Léo
Published: May 2006

The ultraviolet and infrared absorption spectra of protopine and some of its derivatives have been studied. The interaction between a keto group and a tertiary nitrogen in a 10-membered ring is illustrated by the study of these spectra. On the basis of these studies a quaternary carbinolamine structure (V) is suggested for protopine and cryptopine salts. Some of the reactions of protopine, cryptopine, and vomicine are discussed.
SOME FATTY ACIDS OF PEANUT, HICKORY, AND ACORN OILS
Authors: Hopkins C. Y. , Chisholm Mary J.
Published: May 2006

Eicosenoic and docosenoic acids have been identified as constituents of the glycerides of peanut oil (Arachis hypogaca L. var. Spanish). Hexadecenoic acid could not be detected; if present, the amount in this sample of oil is judged to be less than 0.3% of the fatty acids. The oils of the bitter hickory nut (Caryacordiformis Koch) and acorn (Quercusalba L.) have the ordinary palmitate–oleate–linoleate composition. Neither contained a detectable amount of eicosenoic acid. Estimated proportions of some of the acids in these oils are given.
THE BIOGENESIS OF ALKALOIDS: IX. FURTHER INVESTIGATIONS ON THE FORMATION OF GRAMINE FROM TRYPTOPHAN
Authors: Leete Edward , Marion Léo
Published: May 2006

A mixture of dl-tryptophan-2-C14and dl-tryptophan-β-C14with a known ratio of activity in the 2 and β positions was prepared. Feeding it to sprouting barley produced radioactive gramine which was isolated from the leaves. Systematic degradation of the alkaloid showed the activity to be present only in the 2 position of the nucleus and the methylene group of the side chain. The ratio of the activity in the two positions was the same as in the administered tryptophan. These results thus indicate that tryptophan is converted to gramine in the plant without cleavage of the indole–alanine linkage.
PVT MEASUREMENTS IN THE CRITICAL REGION OF XENON
Authors: Habgood H. W. , Schneider W. G.
Published: May 2006

Extensive PVT measurements of xenon extending from 1.8° above the critical temperature to the critical temperature, and in a few cases to 4 ° below the critical temperature, have been carried out at densities ranging from somewhat above the critical density to well below. In order to make the corrections for hydrostatic head small and easily calculable, a bomb having a height of only 1.0 cm. was used in the present measurements. The previously reported value for the critical temperature 16.590° is confirmed. The critical density is estimated to be 1.099 ± 0.002 gm./ml. compared with 1.105 gm./ml. found previously. The critical pressure is found to be 57.636 ± 0.005 atm.The isotherms at temperatures above the temperatures of meniscus disappearance do not appear to have any flat portions. However, the critical isotherm is considerably flatter and broader over a range of densities than that corresponding to a van der Waals equation, and at the critical point the third and fourth derivatives of pressure with respect to volume appear to be zero.
THE PHOTOLYSIS OF MERCURY DIMETHYL WITH DEUTERIUM
Authors: Rebbert Richard E. , Steacie E. W. R.
Published: May 2006

Mercury dimethyl was photolyzed in the presence of deuterium in the temperature range from 27 °C. to 253 °C. The activation energy for the reaction[Formula: see text]was found to be 12.7 ± 0.5 kcal./mole. This is in satisfactory agreement with the work done with acetone and deuterium.
THE RATE OF DISSOLUTION OF COPPER
Authors: Lu Benjamin C.-Y. , Graydon W. F.
Published: May 2006

The rate of dissolution of polycrystalline metallic copper in sulphuric acid solutions has been determined as a function of temperature, oxygen pressure, rotation speed, hydrogen ion concentration, sample area, and corroding solution volume. A typical set of conditions would involve a volume of 500 ml. of air-saturated sulphuric acid solution at room temperature and a cylindrical sample of copper of 11 sq. cm. area rotated at 1000 r.p.m. An empirical rate equation has been given which represents the data with an average deviation of ±5%. The rate equation is discussed in terms of a mechanism in which it is postulated that the rate controlling step in the dissolution of copper is the oxidation of cuprous ion at the solution–copper interface.
THE HYDROLYSIS OF THE CONDENSED PHOSPHATES: II (A). THE ROLE OF THE HYDROGEN ION IN THE HYDROLYSIS OF SODIUM PYROPHOSPHATE: II (B). THE DISSOCIATION CONSTANTS OF PYROPHOSPHORIC ACID
Authors: McGilvery J. D. , Crowther Joan Pedley
Published: May 2006

The general rate equations for the hydrolysis of pyrophosphate anion proposed by Muus have been proved to be inapplicable over the pH range 2.0 to 11.0. A general rate equation is proposed which is based on the assumption that each anionic species of pyrophosphoric acid hydrolyzes at a rate which depends on its concentration, and that the only role of the hydrogen ion concentration is to determine the proportion of each species present in the solution. A mechanism for the hydrolysis of pyrophosphate anion is suggested.The dissociation constants of pyrophosphoric acid have been determined at 65.5 °C. for the concentration range 0.08 to 0.18 molar.
17-HYDROXYLUPANINE AND 17-OXYLUPANINE
Authors: Edwards O. E. , Clarke F. H. , Douglas Bryce
Published: May 2006

Silver oxide has been shown to oxidize lupanine to 17-hydroxylupanine. This base gives an anhydronium perchlorate identical with the "dehydrolupanine (NBS)" perchlorate of Marion and Leonard. 17-Oxylupanine is described, and, from the observation that it can be reduced catalytically to oxysparteine, the stereochemistry of aphylline and oxysparteine is deduced. The basic strength of tertiary carbinolamines is discussed.
THE SYNTHESIS AND REACTIONS OF 1-CHLORO-2-ISONITROSODIBENZOYLETHANE
Authors: Beelik A. , Brown W. H.
Published: May 2006

The addition of nitrosyl chloride to trans-dibenzoylethylene produces only the syn-benzoyl isomer of 1-chloro-2-isonitrosodibenzoylethane. This compound contains a hydrogen bond. It forms two isomeric mono-2,4-dinitro-phenylhydrazones. When boiled with hydrochloric acid it is converted into 3-benzoyl-4-chloro-5-phenylisoxazole. The reactions and derivatives of this latter compound are discussed.
THE KINETICS OF THE PYROLYSIS OF TOLUENE
Authors: Blades H. , Blades A. T. , Steacie E. W. R.
Published: May 2006

The pyrolysis of toluene has been studied in an attempt to verify the findings of Szwarc (2). The major products have been confirmed but styrene and isomeric dimethyl diphenyls have also been detected. First order rate constants for the decomposition have been found to depend on the condition of the surface of the reactor, the contact time, and, to a lesser degree, on the pressure. Some preliminary studies on the mechanism of the formation of the dimethyl diphenyls are also recorded.
ESTIMATION OF CARBOXYL, ALDEHYDE, AND KETONE GROUPS IN HYPOCHLOROUS ACID OXYSTARCHES
Authors: McKillican Mary E. , Purves C. B.
Published: May 2006

Purified wheat starch was oxidized at room temperature in approximately 0.05 to 0.09 M hypochlorous acid, preferably buffered to pH 4.0 or 4.2 with calcium acetate – acetic acid. The chemical efficiency of the oxidant was at least 56%. The fractions of oxystarch, insoluble and soluble in water, were isolated in a combined yield of 93% to 95%.So prepared, the water-soluble fraction (about 75% of the oxystarch) contained 45 to 58 mM. of carboxyl groups per anhydroglucose unit, probably all as uronic acid. Carbonyl groups amounted to 52 to 54 mM., 65% to 80% being aldehydes in the primary alcohol positions, and roughly 9% being ketone groups in the second positions. Between 80% and 90% of the total oxidation therefore concerned primary alcohol groups. Various estimations for carboxyl, total carbonyl, and aldehyde groups were compared.
THE ISOTOPE EFFECT IN THE SYNTHESIS OF 3,3′-METHYLENE-C14-bis(4-HYDROXYCOUMARIN)
Authors: Lee C. C. , Spinks J. W. T.
Published: May 2006

not available
THE REACTION OF ACTIVE NITROGEN WITH PROPANE
Authors: Onyszchuk M. , Breitman L. , Winkler C. A.
Published: May 2006

The reaction of nitrogen atoms with propane has been found to produce hydrogen cyanide as the main product, together with smaller amounts of acetylene, ethylene, and ethane, which were recovered at all propane flow rates. Complete consumption of nitrogen atoms was not attained at any propane flow rate used at 63 °C, but was attained at 250 °C for ratios of propane to nitrogen atoms greater than 1.3. An activation energy of 5.6 ± 0.6 kcal. and a steric factor between 10−2 and 10−3 was estimated from second order rate constants.
ADDITION OF METHYL RADICALS TO UNSATURATED HYDROCARBONS
Authors: Mandelcorn L. , Steacie E. W. R.
Published: May 2006

The rates of addition of methyl radicals, produced by the photolysis of acetone between 140 °C. and 240 °C, to unsaturated hydrocarbons were determined by two independent methods. From the kinetics of the addition and the methyl radical combination reactions, addition of methyl radicals to ethylene, propylene, acetylene, and butadiene was found to proceed with activation energies of 7.0, 6.0, 5.5, and ∼2.5 kcal. respectively and steric factors of the order of 10−4.
THE ADSORPTION OF WATER VAPOR BY PROTEINS
Authors: Dunford H. B. , Morrison John L.
Published: May 2006

not available
A STUDY OF THE SULPHATE ESTER OF UNSTABILIZED CELLULOSE ACETATE
Authors: Keirstead Karl , Myers John
Published: May 2006

Evidence for the existence of the ester form of the sulphate in unstabilized cellulose acetate has been examined by ion exchange studies on precipitated and fibrous cellulose acetate. The equilibrium reached during ion exchange is affected by the pH and by the concentration of the salt solution used. The thermal stability of the ester is shown to vary inversely with the sulphate content. A study has been made of the accuracy of the various analyses involved.
THE ISOLATION AND OXIDATION OF ASPEN LIGNINS
Authors: Pepper J. M. , Hagerman D. C.
Published: May 2006

A study has been made of the conditions affecting the isolation of a lignin fraction by a procedure involving a moderate temperature catalytic hydrogenation of pre-extracted aspen wood meal. The effect of varying the initial hydrogen pressure, the catalyst, the time and maximum temperature of reaction, and the nature and acidity of the suspending medium were studied. The weight of the residual pulp, the effectiveness of lignin removal, the weight and methoxyl content of the resulting chloroform-soluble fraction containing the lignin, and the yields of vanillin and syringaldehyde obtained by the alkaline nitrobenzene oxidation of this same fraction were the factors serving as the bases for comparison.Initial hydrogen pressures greater than 500 p.s.i.g. were not required, although below this value there was some loss of efficiency. Neither the use of water or dioxane alone was satisfactory as a suspending medium, but the mixed aqueous-organic medium was required to remove the released lignin. Considering the resultant slight acidity of the reaction product, it is suggested that in such an isolation two separate stages are involved: that of the water functioning to wet and permeate the wood and serve as the acidic medium and that of the organic solvent phase functioning to remove the liberated lignin after the hydrolytic cleavage.Data are presented and interpreted to indicate the existence of a lignin-carbohydrate complex which is cleaved under the conditions of catalytic hydrogenation. Under the conditions of these experiments practical temperatures for lignin removal are in the range 170 – 180 °C. for an aqueous-organic solvent medium, but some thirty degrees lower for an 85% acetic acid medium. Although it has been possible to isolate all the lignin, with good methoxyl recovery, consistently no more than approximately fifty per cent of the required aldehydes is obtainable on oxidation. The increasing value of the syringaldehyde – vanillin ratio with increasing temperature is due to a decreased vanillin yield.Indications are that the use of copper chromium oxide may be preferred over Raney nickel as a catalyst for this isolation procedure.
KINETICS OF THE REACTION H + CH4 = CH3 + H2
Authors: Berlie M. R. , Roy D. J. Le
Published: May 2006

The reaction H + CH4 = CH3 + H2 has been studied in the temperature range 99° to 163 °C. The rate constant is given by the expression k = 1.7 × 10−14 exp (−4500/RT). The data are in agreement with the results, but not the interpretations, of previous work. The entropy of the methyl radical has been calculated for several temperatures.
STRESSES AND STRAINS IN ADSORBENT–ADSORBATE SYSTEMS
Authors: Flood E. A. , Heyding R. D.
Published: May 2006

From thermodynamic considerations a simple equation is derived which correlates length changes of a porous rigid adsorbent with its elastic and adsorptive properties. The equation contains a structure factor which is a constant characteristic of the adsorbent. Calculated and observed results agree reasonably well and suggest that, in the cases concerned, the assumptions underlying the derivation of the equation are valid. The underlying assumptions are: (a) both adsorbate and adsorbent can each exist separately in equilibrium with externally applied forces in states that are thermodynamically identical with their states in the adsorbate–adsorbent system, (b) adsorption isotherms represent paths of thermodynamic reversibility.
THE SPECTRA OF SATURATED AND α–β UNSATURATED SIX-MEMBERED LACTAMS
Authors: Edwards O. E. , Singh Tara
Published: May 2006

The ultraviolet and infrared spectra of some saturated and unsaturated six membered lactams are described, and the unusual features in the 3 μ and 6 μ regions discussed. A comparison is made of these spectra with those previously ascribed to α–β unsaturated lactams.
LYCOCTONINE: ACID CATALYZED REARRANGEMENTS
Authors: Edwards O. E. , Marion Léo , McIvor R. A.
Published: May 2006

The lactam derived from the alkaloid lycoctonine has been shown to undergo rearrangement when heated with mineral acids. A ketone, anhydrolycoctonam, is formed first by pinacolic dehydration. This ketone then undergoes elimination of the elements of methyl alcohol, and hydrolysis of a methoxyl to give lycoctamone, an α–β unsaturated ketone containing a new tertiary hydroxyl. Reactions of lycoctamone and its reduction products are described and discussed.
SOME REACTIONS OF ETHYL 2-PYRIDINEACETATE: 1,2-DICARBETHOXY-3-OXO-OCTAHYDROPYRROCOLINE
Authors: Edwards O. E. , Chaput M. , Clarke F. H. , Singh Tara
Published: May 2006

Ethyl α-acetoxy-2-pyridineacetate and ethyl α-bromo-2-pyridineacetate have been prepared, and the latter converted in three steps to 1,2-dicarbethoxy-3-oxooctahydropyrrocoline. The main carbonyl band of simple saturated five membered lactams in the infrared is observed to lie close to 1700 cm−1
AN EXAMINATION OF MAYER'S THEORY OF IONIC SOLUTIONS: THE CALCULATION OF THE RELATIVE APPARENT MOLAL HEAT CONTENT AND APPARENT MOLAL VOLUME OF SODIUM CHLORIDE IN AQUEOUS SOLUTIONS AT 25 °C.
Authors: Benson G. C.
Published: May 2006

Mayer's theory gives a good representation of the apparent molal volume [Formula: see text] of sodium chloride in aqueous solution at 25 °C up to a concentration 0.4 molar. Representation of the relative apparent molal heat content [Formula: see text] is also satisfactory but over a smaller range of concentration. The shape of the [Formula: see text] curve is strongly influenced by the temperature dependence of the distance of closest approach of oppositely charged ions in the solution. Methods of evaluating this term are considered. The utility of Mayer's theory for the extrapolation of experimental data to infinite dilution is illustrated in the case of [Formula: see text] and of intermediate heats of dilution.
INFRARED STUDY OF THE N—OH GROUP IN ALPHA AND BETA OXIMES
Authors: Palm Ann , Werbin Harold
Published: May 2006

The O—H bending and N—O stretching vibrations were studied in four pairs of isomeric oximes. A band at 1265 cm.−1, characteristic of the solution spectra of the α oximes, is identified with the O—H bending mode. Tentative assignments for the N—O stretching vibration both in solid and solution spectra are advanced. The β isomers show a distinct shift of the band associated with the N—O mode from about 950 cm.−1 in the solid to about 930 cm.−1 in solution.
MOLTEN SALTS: COMPLEX ION FORMATION IN THE SYSTEM SILVER CHLORIDE – SILVER NITRATE
Authors: Hill S. , Wetmore F. E. W.
Published: May 2006

Conductivity data have been combined with transport fractions to show that silver chloride in dilute solutions in silver nitrate can be regarded as being almost completely in the form of complex cation. The mobility of the complex ion is shown to be about one-half that of silver ion.
THE ROLE OF BETAINE IN PLANT METHYLATIONS
Authors: Sribney M. , Kirkwood S.
Published: May 2006

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ISOTOPE EFFECTS IN THE COMBUSTION OF CARBON MONOXIDE
Authors: Attree R. W. , Brown F. , Dunn G. E. , Lounsbury M.
Published: May 2006

The relative rates of reaction of C12O, C13O, and C14O with oxygen have been measured. When the oxidation proceeds mainly on the walls of the containing vessel the relative rates for C13O and for C14O compared to C12O are respectively 0.985 and 0.959. When reaction proceeds mainly in the gas phase there is no isotope effect within experimental error.
ESTIMATION OF IMPURITIES IN LIQUID CHLORINE BY INFRARED ABSORPTION SPECTROPHOTOMETRY
Authors: Pross A. W.
Published: May 2006

Commercial chlorine may contain small amounts of chlorinated organic impurities, some of which have been estimated by infrared absorption spectrophotometry. Liquid chlorine has no infrared absorption spectrum up to 1180 cm−1. This has enabled long path lengths to be used to increase the sensitivity to low concentrations of organic compounds. A 5 cm. tantalum-clad steel pressure cell fitted with calcium fluoride windows was used, and spectra were recorded on a single beam instrument fitted with a calcium fluoride prism. Using extinction coefficients, estimations were made to a few parts per million on impurities such as chloroform, methylene chloride, phosgene, and hexachlorobenzene. The method was checked by known additions to pure liquid chlorine. The estimation of moisture in liquid chlorine is discussed.
THE QUENCHING OF POTASSIUM RESONANCE RADIATION BY HYDROGEN AND DEUTERIUM
Authors: Smith W. M. , Stewart J. A. , Taylor G. W.
Published: May 2006

The quenching of the resonance radiation of potassium by hydrogen and deuterium has been studied over the temperature range 71 °C to 83 °C. The quenching cross sections at 76 °C were found to be 1.56 × 10−16 cm2 and 1.10 × 10−16 cm2 respectively.
KINETICS OF THE HOMOGENEOUS REACTION BETWEEN CUPRIC ACETATE AND MOLECULAR HYDROGEN IN AQUEOUS SOLUTION
Authors: Dakers R. G. , Halpern J.
Published: May 2006

Cupric acetate was found to react homogeneously with molecular hydrogen in aqueous solution according to the following equation:[Formula: see text]The paper describes a kinetic study of this reaction. Rates were determined at temperatures between 80 and 140 °C and hydrogen partial pressures between 6.8 and 34.0 atm. The reaction was found to be of second order, the rate being proportional to the concentrations of cupric acetate and molecular hydrogen. It was established that the rate was independent of the surface of the reaction vessel, the cuprous oxide product and of the concentrations of sodium acetate and acetic acid in the solution. The reaction has an activation energy of 24200 cal. per mole. The kinetic results are discussed and a mechanism is proposed. This appears to be one of the few known homogeneous reactions of molecular hydrogen in solution.
THE EFFECT OF MEMBRANE THICKNESS IN DIALYSIS
Authors: Herbst J. H. E.
Published: May 2006

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AMINO ACIDS: I. PREPARATION AND PROPERTIES OF GLYCOCYAMIDINE
Authors: McKay A. F. , Braun R. O. , Hatton W. G.
Published: May 2006

Attempts to prepare glycocyamidine by the cyclization of ethyl guanidoacetate in aqueous solutions gave mixtures of guanidoacetic acid and glycocyamidine. The properties of a sample of pure glycocyamidine, which was obtained from the reaction of guanidine with ethyl glycinate, are described.
THE RAMAN SPECTRA OF TRICHLOROETHYLENE: C2HCl3 AND C2DCl3
Authors: Allen G. , Bernstein H. J.
Published: May 2006

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THE ROLE OF WATER IN THE FORMATION OF SODIUM TRIPHOSPHATE BY CALCINATION
Authors: McGilvery J. D. , Scott A. E.
Published: May 2006

The formation of sodium triphosphate by calcination, below the sodium triphosphate fusion point, of various phosphate mixtures of over-all composition 5Na2O.3P2O5.xH2O was investigated. Water plays an important role, decreasing the amounts of pyrophosphate and high molecular weight polyphosphate impurities and increasing the reaction rate under certain conditions. It is suggested that water catalyzes the reactions by: (1) facilitating ionic diffusion, (2) hydrolyzing —P—O—P—linkages, and (3) assisting in the crystallization of sodium triphosphate. With ortho- and pyro-phosphate mixtures temperatures of about 300 °C. and higher are necessary for the rapid formation of sodium triphosphate. With glasses of the composition 5Na2O.3P2O5 good yields may be obtained at temperatures as low as 250 °C. when water is present.
AN ACCURATE METHOD OF ANALYSIS FOR SMALL QUANTITIES OF ETHYLENE
Authors: Shepp A. , Kutschke K. O.
Published: May 2006

A procedure is described for the accurate analysis of ethylene in mixtures of ethane and ethylene by hydrogenation over a nickel–kieselguhr catalyst. Samples of ethylene as small as 0.03 cc. in mixtures of the order of 1.5 cc. of gas at N.T.P. can be determined to an accuracy of about one half per cent. Results are reported over a range of mixtures.
DIRECT CURRENT POWER SUPPLY FOR AH-6 MERCURY ARCS
Authors: Whiteway S. G. , Masson C. R.
Published: May 2006

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PHENOXYMETHYL 2-CHLOROETHYL ETHERS
Authors: Kulka Marshall
Published: May 2006

A series of phenoxymethyl 2-chloroethyl ethers has been prepared for testing as possible insecticides.
A NEW MATERIAL AND TECHNIQUES FOR THE FABRICATION AND MEASUREMENT OF VERY THIN FILMS FOR USE IN 4π-COUNTING
Authors: Pate B. D. , Yaffe L.
Published: May 2006

A new method for preparing thin films for use in beta-spectrometry and 4π-counting is described. These films, made of polyvinylchloride-acetate copolymer are readily prepared with superficial densities as low as 1 μgm. per cm.2 The films have good tensile strength and show excellent resistance to acids, alkalies, and many organic reagents. The thickness of the films may be determined (a) gravimetrically, (b) radiometrically, and (c) optically either by transmission or reflection. The films can be made conducting by distilling a thin gold layer on to them. The thickness of the gold layer can be determined spectrophotometrically.
THE REACTION OF METHYL RADICALS WITH CH3CHO AND CH3CDO
Authors: Ausloos P. , Steacie E. W. R.
Published: May 2006

Azomethane has been photolyzed in the presence of CH3CHO and CH3CDO, and the results compared with the direct photolysis of the aldehydes. The activation energies found were 6.8 and 7.8 kcal./mole, respectively, for the reactions[Formula: see text]The results furnish evidence that only an acyl hydrogen is captured. Evidence has also been found for the occurrence of wall reactions and the disproportionation reaction[Formula: see text]
THE PHOTOLYSIS OF BIACETYL
Authors: Ausloos P. , Steacie E. W. R.
Published: May 2006

The photolysis of biacetyl has been reinvestigated. The results are, in general, in excellent agreement with those of Blacet and Bell. Curvature occurs at low temperatures in the Arrhenius plot of [Formula: see text][Biacetyl], and this is attributed to wall reactions, and to the disproportionation reaction[Formula: see text]Azomethane–biacetyl mixtures have been photolyzed to give further information on these points. An activation energy of 8.5 kcal. has been found for the reaction of methyl radicals with biacetyl.
STUDIES IN THE POLYOXYPHENOL SERIES: VIII. THE OXIDATION OF SUBSTANCES RELATED TO VANILLIN WITH SODIUM CHLORITE AND CHLORINE DIOXIDE
Authors: Logan C. D. , Husband R. M. , Purves C. B.
Published: May 2006

The research confirmed the fact that chlorine dioxide and sodium chlorite were not equivalent in their oxidizing properties. At 22 °C. or less, the oxidation of pyrogallol by aqueous sodium chlorite at pH 6 was very slow, but became very rapid on the acid side of pH 3.5. The amorphous, colored products probably did not include purpurogallin. Under similar circumstances p-hydroxybenzaldehyde was unaffected at pH 6; 22% was oxidized to p-benzoquinone (Dakin's reaction) at pH 5, and this amount increased to 39% at pH 1. The yield of benzoquinone was about 24% regardless of pH within the above range when aqueous chlorine dioxide was the oxidant. Sodium chlorite at pH 0.9 produced a 91% yield of methoxy-p-quinone from methoxy-p-hydroquinone; at pH 4 this product was mixed with 56% of 4,4′-dimethoxydiquinone, but near pH 6 a slower oxidation did not proceed beyond 4,4′-dimethoxyquinhydrone. Aqueous chlorine dioxide yielded at least 92% of monomeric methoxyquinone at all pH values between 1 and 6, probably in accord with the equation,[Formula: see text] The simultaneous formation of hydrogen peroxide was suspected, but not proved. In sharp distinction to the behavior of free phenols, veratraldehyde was not oxidized by aqueous chlorine dioxide between pH 6 and pH 3, but at pH 1 a slow reaction yielded up to 15% of veratric acid. Sodium chlorite produced about 92% of the same acid at pH 1 and pH 4, but its action was negligible at pH 5. Since by-product chlorine dioxide was ineffective at pH 4, it was possible to confirm the validity of the Jeanes–Isbell equation for the reduction of chlorous acid:[Formula: see text]The oxidation of acetylated vanillin was complicated by the occurrence of deacetylation. Red, chlorinated oils with quinoidal properties were also formed in most of the above oxidations.
THE EFFECT OF CHLORINE SUBSTITUTIONS AT THE C2-ACETOXY GROUP ON SOME PROPERTIES OF THE GLUCOSE PENTAACETATES
Authors: Lemieux R. U. , Brice Carol , Huber G.
Published: May 2006

The effects were studied of substituting one, two, and three chlorine atoms at the C2-acetoxy group of the α- and β-D-glucopyranose pentaacetates on the rates both of anomerization and of dissociation of the C1 to acetoxy group bond in 1:1 acetic acid – acetic anhydride 0.5 M with respect to sulphuric acid at 25 °C. In the case of the α-anomers, the rates of anomerization appeared about equal to the rates of dissociation as measured by isotopic exchange. The β-anomers dissociated more rapidly than they underwent anomerization. The difference in rate decreased rapidly, however, with the introduction of chlorine atoms indicating that the tendency for C2-acyl group participation in the dissociation is reduced by the chlorine substitutions. Evidence was obtained that only a very small fraction, if any, of the C1-acetoxy group of β-glucose pentaacetate passes into the α-anomer without becoming completely dissociated. It is pointed out that the data for the anomerizations can be rationalized on the basis of ionic mechanisms, if specific conformations are allocated to the intermediate carbonium ions.
THE DETERMINATION OF PORE SIZE DISTRIBUTION AND SURFACE AREA FROM ADSORPTION ISOTHERMS
Authors: Voigt E. M. , Tomlinson R. H.
Published: May 2006

Theoretical isotherms have been developed which when compared to experimental isotherms showing hysteresis, allow the calculation of pore size, pore size distribution, and surface area of the sorbent. Interpretation of some experimental isotherms obtained with porous vycor glass shows that this system can best be represented by the "ink bottle" pore model with a Gaussian distribution of pore sizes. The mean pore radius of the porous glass is about two thirds of the Kelvin radius, and the surface area greater than that obtained from the B.E.T. theory. The Kelvin radius is interpreted as a weighted average, but the B.E.T. surface area appears more fundamentally different.
DÉDOUBLEMENT DES α- ET β-HYDROXYLAUDANOSINES
Authors: Ferron Jean-Louis , L'Ecuyer Philibert
Published: May 2006

not available
AN ADIABATIC CALORIMETER FOR THE TEMPERATURE REGION BELOW 20°K.—THE SPECIFIC HEAT OF SODIUM CHLORIDE
Authors: Morrison J. A. , Patterson D. , Dugdale J. S.
Published: May 2006

A simple adiabatic calorimeter for specific heat measurements at very low temperatures is described. Liquid helium is made in the cryostat by the Simon expansion method. The calorimeter and adiabatic shield are cooled below 13°K. by conduction of heat along the lead wires rather than by conduction with exchange gas. The working thermometer is a carbon resistor which has been calibrated against a helium gas thermometer. The assembly has been used to determine the specific heat of rock salt between 2.5° and 20°K. The results are compared with the theoretically derived values of the specific heat and Debye characteristic temperature for sodium chloride.
THE EFFECT OF PRECIPITATION CONDITIONS ON THE FLOW PROPERTIES OF SILICA DISPERSIONS
Authors: Sirianni A. F. , Puddington I. E.
Published: May 2006

The pH of the solutions in which silica is precipitated from sodium silicate has a marked effect on the flow properties of pastes prepared by subsequently dispersing the silica in liquid hydrocarbons. The yield value of this non-Newtonian suspension exhibits a pronounced maximum when silica precipitated at about pH 5 is used. An explanation based on the properties of the solid–liquid interface is proposed.
ABSORPTION SPECTRA OF METALS IN SOLUTION
Authors: Blades H. , Hodgins J. W.
Published: May 2006

Measurements of the absorption spectra were made on solutions of alkali and alkaline earth metals in ammonia, methylamine, ethylamine, and mixed solvents. In ammonia, a single absorption band was measured which is common to all the metals examined. In the amines and in mixtures of ammonia with methylamine, however, bands were found which were characteristic of the metal employed. A hypothesis has been advanced to explain the existence of the different types of energy traps responsible for the variations in spectra.
NOTE ON THE VOLATILITY OF LITHIUM OXIDE
Authors: Arkel A. E. Van , Spitsbergen U. , Heyding R. D.
Published: May 2006

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PHOTOLYSIS OF ACETONE IN THE PRESENCE OF MERCURY DIMETHYL
Authors: Oswin H. G. , Rebbert R. , Steacie E. W. R.
Published: May 2006

The reactions between CH3 + CH3—Hg—CH3 were investigated in a system in which acetone was used as the source of CH3 radicals. Similarly d6-acetone was used to investigate the reactions of CD3 radicals and CH3—Hg—CH3. Activation energies for the hydrogen abstraction reactions were calculated, and no significant difference was found between the CD3 and CH3 reactions, being respectively 10.0 and 10.2 kcal./mole. Under conditions of constant intensity and acetone concentration, reaction rates appear to be dependent on mercury dimethyl concentrations. In the case of the acetone-d6 system, quantities of C2D3H3 were found in the reaction products. This is discussed as possible evidence of such a reaction as:[Formula: see text]
ALLOYS OF INDIUM: THE SYSTEM INDIUM–LEAD–TIN
Authors: Campbell A. N. , Screaton R. M. , Schaefer T. P. , Hovey C. M.
Published: May 2006

There is no ternary eutectic in the system: indium–lead–tin: the eutectic trough extends from the lead–tin eutectic to the tin–indium eutectic. The liquidus surface has been outlined. The structures of all alloys of the above system have been investigated, at room temperature, by the X-ray and microscopic techniques. A one-phase region extends across the ternary diagram from the limits of the β-phase in the indium–tin system to the limits of the β-phase in the lead–indium system. This indicates that the intermetallic β-phases of the two systems (lead–indium and tin–indium) have the same lattice structure, viz. face-centered tetragonal. Heterogeneity has been detected by direct experiment in the system lead–indium, whereas it had previously only been deduced. Hardness tests, both Brinell and Vickers, have been made on the alloys.