bluuebunny/crossref_metadata_2025 huggingface dataset:
Identification of mixed plasticizers by a combination of chromatography and infra‐red spectroscopy
Authors: Cachia M. , Southwart D. W. , Davison W. H. T.
Published: July 2010

A procedure is described for the identification and semi‐quantitative estimation of plasticizers in the mixtures commonly used in the formulation of plastics, especially polyvinyl chloride. It involves chromatographic separation followed by infra‐red spectroscopy.
The corrosion of lead by dilute aqueous organic acids
Authors: Coles E. L. , Gibson J. G. , Hinde R. M.
Published: July 2010

Corrosion tests have been carried out on lead totally immersed in solutions of organic acids (0·1–0·0001 N). The corrosion rates in acetic, propionic, butyric, succinic, and lactic acids of the same normality were very similar, while pyruvic acid appeared to form a protective film. Inter‐crystalline attack was the most important general diagnostic feature of the corrosion by the acids, particularly the acetic, propionic, and butyric acids. X‐Ray diffraction analysis has established that the corrosion products in most cases gave patterns which could be arranged in a series showing a gradual transition from basic carbonates deficient in carbon dioxide to the basic carbonate 2PbCO3, Pb(OH)2.
Experiments to establish conditions for the continuous reduction of titanium tetrachloride to the metal by sodium
Authors: Smolinski J. , Hannam J. C. , Leach A. L.
Published: July 2010

Titanium tetrachloride was reduced continuously to the metal by sodium dissolved in fused chlorides; titanium metal of hardness down to 180 D.P.N. was extracted from the reactor without interrupting the process of reduction.

The rate of reduction was about 0.8 g. of titanium tetrachloride per hour per sq. cm. of salt area exposed to titanium tetrachloride at temperatures of 600–700°.

The solubility of sodium was measured in the molten salt mixtures 60% LiCl/40% KCl, 48% NaCl/52% CaCl2, 50% NaCl/50% KCl and 36% NaCl/30% KCl/34% SrCl2 (all mol.‐%.) and was found to be similar in all cases, increasing from 1 mol.‐% near the freezing point to 8 mol.‐% at 850°, the increase being rapid over 800°.

The solubility of titanium tetrachloride in 60% LiCl/40% KCl (mol.) was found to be about 1 mol.‐% at 800°.
The binary systems benzene‐ethyl methyl ketone and benzene‐cyclohexane
Authors: Donald M. B. , Ridgway K.
Published: July 2010

The binary systems benzene‐ethyl methyl ketone (A) and benzene‐cyclohexane (B) have been studied, and results are discussed with those obtained previously,1 for the binary system cyclohexane‐ethyl methyl ketone (C). Several physical properties and also vapour‐ and solid‐liquid equilibria were determined as functions of the composition. System A formed an azeotrope at 51 molar‐% benzene which boiled at 78.1°/760 mm. Hg, and a eutectic at 24.2 molar‐% benzene and −92°. System B formed an azeotrope at 54.5 molar‐% benzene which boiled at 77.4°/760 mm. Hg, and a eutectic at 26.5 molar‐% benzene at −46.5°. In order of increasing deviation from linearity when plotted against molar fraction, the systems tended to lie in the order A, B, C. An explanation is suggested on the basis of differences in the forces operating (dipole: induced‐dipole or dispersion forces) and the size and shape of the molecular species present.
Syntheses of metal‐complexing polymers. I. Phosphorylated polymers
Authors: Kennedy J. , Lane E. S. , Robinson B. K.
Published: July 2010

The syntheses of phosphorylated allyl ester monomers and polymers are described and some factors relevant to allyl ester polymerization are discussed. Successful phosphorylations of chloromethylpolystyrene (cross‐linked with 2% divinylbenzene), polyvinyl chloride and cannel coal, by the use of phosphorus trichloride in conjunction with a Friedel‐Crafts catalyst (AlCl3) have been conducted, and a technique for phosphorylation of a phenol‐formaldehyde resin matrix is described. Alkaline hydrolysis of triallyl phosphate and diallyl allylphosphonate polymers results in monobasic resins with a sodium‐hydrogen exchange capacity of 4.5 mequiv. per g. of acid resin. Oxidative hydrolyses (contact with concentrated nitric acid) of the phosphorylated product obtained from the reaction of chloromethylpolystyrene with phosphorous trichloride results in a dibasic resin with an over‐all exchange capacity of 8.5 mequiv. per g.
The effect of particle size on the velocity of detonation of simple nitroglycerine/salt mixtures
Authors: Dolan J. E.
Published: July 2010

The variation of velocity of detonation with ingredient particle size and cartridge density for a series of nitroglycerine/sodium chloride mixtures has been determined. It has been shown that the velocity of detonation of such mixtures is a function of the particle size of the sodium chloride used and reaches a maximum at a specific surface of 145 cm.2/g. and then decreases: an explanation is advanced. The change in the velocity of detonation with change in cartridge density has also been shown to be a function of the particle size of the sodium chloride used.
Raney cobalt hydrogenation catalysts. III. Applications and promoter effects
Authors: Aller B. V.
Published: July 2010

A description is given of the use of Raney cobalt for the hydrogenation of unsaturated and carbonyl linkages under mild conditions. The results are compared with those obtained with Raney nickel catalysts.

A study has also been made of the promoter effects of triethylamine, chloroplatinic acid and combinations of these, on the activity of the Raney cobalt catalyst for the hydrogenation of carbonyl compounds. As in the case of Raney nickel, such effects are highly specific for the compound under investigation. The most notable effect occurred in the hydrogenation of benzaldehyde, where the use of triethylamine chloroplatinate as promoter resulted in a cobalt catalyst having an activity several times greater than an unpromoted catalyst.
The dealkylation of alkyl aromatic hydrocarbons. III. The dealkylation of polynuclear aromatics
Authors: Betts W. D. , Popper F.
Published: July 2010

The studies of thermal dealkylation1, 2 have been extended to the polycyclic hydrocarbons. In the temperature interval of 560 to 660°, at a pressure of 100 atm. and with a large excess of hydrogen, α‐ and β‐methylnaphthalene, a methylnaphthalene oil and a number of coal‐tar fractions were studied. On the assumption of the same mechanism as for toluene dealkylation1 the results were fitted to a 1.5‐order reaction mechanism. The energies of activation for α‐ and β‐methylnaphthalenes agree well with the proposed mechanism.

Naphthalene oils of coke‐oven origin should be capable of giving quantitative yields of naphthalene. Oils of vertical‐retort origin are too rich in paraffin content. Little dealkylation was obtained with a coke‐oven anthracene oil.
Low‐temperature explosions of mixtures of potassium perchlorate with some combustible substances
Authors: Grodzinski J.
Published: July 2010

Mixtures of potassium perchlorate with some combustible substances have been heated in sealed test‐tubes and their ‘explosion temperatures’, time‐lag' of explosion and ‘critical’ mass/volume ratio ‘determined’. The relation between the explosion temperature and the chemical character of the substance mixed with potassium perchlorate was investigated. Influence of other factors on the ‘explosion temperature’ and on the ‘time lag’ of explosion was also examined.

The possible mechanism of the observed low‐temperature explosions has been discussed.
Zinc Alloy Anodes
Authors: Crennell J. T. , Wheeler W. C. G.
Published: July 2010

Laboratory and full‐scale trials of zinc anodes have shown that the presence of small amounts of aluminium (0.5–1.0%) gives improved performance and that addition also of 0.25–0.5% of silicon is more effective. The detrimental effect of iron is overcome by these additions.
Fractionation studies on the proteins of the groundnut (arachis hypogaea)
Authors: Naismith W. E. F. , Mcdavid Helen M. R.
Published: July 2010

Attempts to prepare pure samples of the conarachin I and II fractions of groundnut protein by fractional precipitation are described. Although pure conarachin I has been prepared, all attempts to purify conarachin II have so far been unsuccessful. Methods for isolating pure arachin without the use of ammonium sulphate are also outlined. It has been shown that the precipitation limits of a protein with ammonium sulphate are modified by the presence of other proteins.
The determination of trace elements in pulverized‐fuel ash
Authors: Smith A. C.
Published: July 2010

In connexion with work on the utilization of pulverized‐fuel ash, spectrographic methods are described for the determination of 30 trace elements.

Determinations of these elements in 18 ashes were carried out, but none was present in concentrations sufficient for economic recovery. Apart from titanium, where the concentration is of the order of 1%, only manganese exceeds 0.mD1%, while copper, lead, zinc, nickel and chromium fall in the range 0.mD01–0.mD1%. Concentrations of other elements are much below 0.mD01%, while thallium, cadmium, mercury, rubidium, tungsten, silver, zirconium, platinum, indium, palladium, lanthanum and gold were not detected.
The microstructures of some amatols
Authors: Williamson W. O.
Published: July 2010

Fusion‐cast amatols contained ammonium nitrate grains included in TNT crystals. Some TNT crystals were prisms elongated on [c] and approximately perpendicular to the wall of the mould. Ammonium nitrate grains were mono‐ or poly‐crystalline and some showed evidence of aggregation prior to incorporation with fused TNT; aggregation during fusion casting was rarely indicated. Segregation of the grains by pressure from growing TNT prisms was seen in a few castings unusually poor in ammonium nitrate.

At least some proportion of added wax appeared as segregations in TNT. Added aluminium grains were found in or between TNT crystals. Parallel layers of ammonium nitrate and TNT occurred in parts of test‐pieces of pressed amatol.

Completely fused mixtures of TNT with eutectic proportions of ammonium, calcium and sodium nitrates, were simple or multiple emulsions; the structures of these emulsions became ‘frozen’ when the melt solidified.
Effects of additives on ignition delay of the system, white fuming nitric acid ‐ turpentine
Authors: Makovky A. , Salmon A.
Published: July 2010

The ignition delay of turpentine is not affected by the proportion of oxidizing agent added. The delay is reduced by addition to the nitric acid of oleum up to a certain concentration or by addition of catalysts in the order Fe Cl3 > NH4VO3 > Cu Cl2, but is increased by dilution with petroleum.
Reactivity of lime and related oxides. III. Sorption of liquid water on calcium oxide (‘wet’ hydration)
Authors: Glasson D. R.
Published: July 2010

Calcium oxide samples differing widely in surface activity (5–100m.2 g.‐1) have been ‘wet’ hydrated at room temperature using water, pure or diluted with acetone as an inert liquid.

Rates of hydration and changes in surface area and lattice structure indicate that ‘wet’ hydration proceeds by a mechanism similar to that found earlier for ‘dry’ hydration by water vapour, i.e., hydration proceeds inwards from the outside of each calcium oxide particle by an advancing interface mechanism. In each case, the more active limes become aged (agglomerated) rapidly, but when the less active limes are ‘wet’ hydrated the number of crystallites generally increases much more than for ‘dry’ hydration; cleavage of the calcium hydroxide formed on the surface of the oxide is therefore more extensive, in keeping with the faster hydration. Slow ‘wet’ hydrations using 1% water more closely resemble ‘dry’ hydrations in that the number of crystallites increases only over their later stages. Ultimately, all the ‘wet’ hydrated samples age on prolonged contact with water, their crystallite growth showing some relationship to that of calcium hydroxide precipitated from solution by double decomposition.
Adsorption of methylene blue in the determination of surface areas
Authors: Kipling J. J. , Wilson R. B.
Published: July 2010

Data are presented for adsorption of methylene blue from aqueous solutions on two non‐porous carbons and on a porous activated charcoal. From the specific surface areas of the non‐porous carbons (determined by low‐temperature adsorption of nitrogen) it is calculated that the adsorbed methylene blue occupies an area of between 102 and 108 sq. Å/molecule. These values are compared with those derived from a structural model and with those reported in the literature. It is concluded that this type of adsorption cannot yet be used for accurate determination of surface areas of carbons, nor can it give more than semi‐quantitative information when used as a ‘molecular probe’ to investigate the pore structure of porous charcoals.
Combustion of fuel in the bomb calorimeter as indicated by changes in the pressure system. II
Authors: Patterson W. S. , Parr‐Burman H. B. A.
Published: July 2010

Results are recorded for the combustion behaviour (rate of combustion and maximum pressure pressure developed) in the bomb calorimeter of peat and coal samples of different rank. The effects on combustion behaviour are determined for cokes obtained at various carbonisation temperatures and of different reactivities (as determined by the C.A.B. test), for carbon blacks of different particle sizes, and for peat of various moisture contents, are examined and discussed.
Krypton adsorption and the surface area of silica
Authors: Sing K. S. W. , Swallow D.
Published: July 2010

Details are given of the apparatus used for measuring adsorption isotherms of krypton at −196°, which allowed a rapid and precise measurement of pressure.

Surface areas have been calculated, by the B.E.T. method, from the krypton adsorption isotherms on samples of ground quartz and a silica gel. The surface areas of the quartz samples determined by other workers, using B.E.T. nitrogen adsorption and electron microscopy, agreed well with the krypton values, provided that the atomic cross‐sectional area of krypton was taken as 19·5Ǎ2.

It was not possible to obtain a ‘standard’ curve from the krypton adsorption isotherms on the non‐porous silicas, but when these isotherms were plotted in logarithmic form, all gave a substantial linear region with the same slope. The logarithmic plot of the isotherm on the silica gel had a different slope; it would seem likely, therefore, that capillary condensation occurred on this sample at low pressure and that the B.E.T. area is invalid here.
Catalytic preparation of magnesium hydride
Authors: Faust J. P. , Whitney E. D. , Batha H. D. , Heying T. L. , Fogle G. E.
Published: July 2010

The preparation of MgH2 by the reaction of hydrogen with magnesium metal in the presence of certain catalysts has been investigated.
X‐ray scattering intensities of coals treated with lithium in ethylenediamine
Authors: Ergun S. , Wender I.
Published: July 2010

X‐ray scattering intensities have been obtained of seven vitrinites of different rank and a natural graphite before and after treatment with lithium in ethylenediamine. Scattering intensities showed extensive changes in the arrangement of carbon atoms. The major apparent change occurred at low and moderately low scattering angles. The peaks attributed to parallel packing of aromatic layers were displaced to lower angles corresponding to increase in d‐spacings from about 3·6 to 4·6Å. These findings suggest that conversion of planar aromatic layers to buckled hydrogenated rings has occurred. Graphite was partly hydrogenated and showed a distinct new peak at a d‐spacing of 4·8Å, in addition to the (002) peak at 3·35Å.

The treated vitrinites showed less small‐angle scattering, the decrease probably being caused by expansion of the layers at the expense of small pores, that is, inhomogeneities. For medium‐ and high‐rank coals, the scattering intensities at high angles showed only minor changes consistent with conversion of aromatic to alicyclic structures and not to open chain structures.
Catalytic hydrogenation of sugars
Authors: Boelhouwer C. , Korf D. , Waterman H. I.
Published: July 2010

In a number of comparative hydrogenation experiments with sucrose as a raw material it is demonstrated that high yields (up to 75%) of distillable polyalcohols (mainly glycerol and 1,2‐propanediol) can be obtained at moderate temperatures (200‐250°) with copper chromite catalysts activated with beryllium oxide. Nickel catalysts are active even at still lower temperatures, especially in the presence of Ca(OH)2; thus 70% of distillable polyalcohols were obtained by hydrogenating sucrose in methanol in the presence of 3·5 wt.‐% of Ca(OH)2 and 15% of a nickel‐onkieselguhr catalyst during 105 min. at 195°.

The product distribution analysis according to Weber allowed an easy comparison of the experimental results, particularly in regard to the selectivity of the applied catalysts.
Weathering of road tar in open‐textured surfacings
Authors: Tingle E. D. , Wright N.
Published: July 2010

Experiments are described in which tars have been oxidised in the laboratory under controlled conditions, or weathered in tarmacadam on the road. The tars were analysed at intervals during the oxidation and during the weathering, into fractions according to solubility in a series of solvents of increasing solvent power. Changes in the value of the ratio of certain of the resin fractions have been used for estimating the contribution of oxidation to the hardening of tar under road conditions. The results show that in a tarmacadam made with a low‐aromatic tar the hardening of the binder that occurs on the road is entirely due to oxidation. Oxidation accounts for about half of the hardening of high‐aromatic tars.
Aspects of the crystal structures of calcium silicates and aluminates
Authors: Taylor H. F. W.
Published: July 2010

Knowledge of the crystal structures of both anhydrous and hydrated compounds is briefly reviewed, and the problem of relating crystallographic and chemical results is discussed. One approach lies in the study of oriented transformations, i.e., reactions in which the structure of a crystalline starting material is to a considerable extent preserved in that of the product. These include many dehydration reactions, such as those of xonotlite and afwillite, and also some typical hydrothermal processes such as the formation of xonotlite from tobermorite. Studies on oriented transformations at 650‐800° indicate that some reactions in this temperature range proceed through breaking of Si‐O rather than Ca‐O bonds. For dehydration reactions at lower temperatures, in contrast, there are indications that Si‐O bonds may be more stable than Ca‐O bonds. The feature common to all the types of transformations discussed is probably a tendency for the oxygen atoms or ions to move as little as possible.
An X‐ray study of pulverised fuel ash
Authors: Simons H. S. , Jeffery J. W.
Published: July 2010

Pulverised fuel ash has been subjected to X‐ray examination and chemical analysis and the main mineralogical and physical characteristics have been determined. It is shown that the ash is a very complex material in which the overall chemical composition varies from particle to particle.

It is tentatively concluded that there is a positive correlation between pozzolanic activity and glass content. The types of combination of iron present in the ash have been determined and the effect of hydration examined.
Kinetics of oxidation of coal. II. Comparison of the reactivities of four coals
Authors: Wood T.
Published: July 2010

An attempt has been made to measure the reactivities of four coals using the Warburg technique. Temperature is shown to be a significant factor; the precision of the method is insufficient to determine the influence of particle size. The method would be well suited for a large‐scale statistical survey to investigate the influence of pyrites, or any other constituent, on the reactivity of a coal.
Oxidation of hydrazine in aqueous solution
Authors: Ellis S. R. M. , Jeffreys G. V. , Hill P.
Published: July 2010

A description is given of the batch reactor employed to investigate the chemical reaction between hydrazine and oxygen in slightly alkaline aqueous solution. The results of the investigation are presented in graphical form, and an attempt has been made to interpret the data kinetically. It has been shown that the reaction is complex and is best described by an empirical rate equation.
Reaction with hydrofluoric acid of oxygen‐ and hydrogen‐containing zirconium and the structure of the alloy
Authors: Straumanis M. E. , James W. J. , Lin C. S.
Published: July 2010

From dissolution experiments of the respective zirconium alloys in HF it is shown that oxygen is not occluded in zirconium, but is bound to form domains of ionised ZrO2, which may agglomerate to ZrO2 grains, sparingly soluble in HF while the alloy is soluble in dilute HF. Conversely, hydrogen is occluded or dissolved in zirconium (forming ZrHx), but probably only in those parts of the metal which are free of Zr4+ and O2‐ ions (of ZrO2). Thus the solubility of H2 in this free Zr should be higher than that usually reported by various authors who consider only the weight of oxygen.

When ZrHx is dissolved in HF, the Hx is quantitatively liberated as a gas; ZrO2 when present in the samples and especially when present as a surface film remains as a residue.
Inhibitors of the corrosion of iron. II. Efficiency of the sodium, calcium and lead salts of long chain fatty acids
Authors: Mayne J. E. O. , Ramshaw E. H.
Published: July 2010

The inhibitive properties of the sodium, calcium and lead salts of caproic, oenanthic, caprylic, pelargonic, capric, suberic, azelaic and sebacic acids have been examined in the pH range 4·0–6·0 at concentrations 10−5 to 10−2 N.

The inhibitive efficiency increased with the length of the carbon chain up to a maximum at 8–9 carbon atoms. For a given acid the lead salt was more efficient than either the sodium or the calcium salt. The most inhibitive salts examined were lead suberate and azelate.
Adhesion in bitumen macadam
Authors: Hughes R. I. , Lamb D. R. , Pordes O.
Published: July 2010

Loss of adhesion between a bituminous binder and stone in the presence of water may take place by the retraction of the binder. It is suggested that this mechanism only operates when the viscosity of the binder is low. When loss of cohesion occurs in a carpet it more normally originates from the accumulation of water at the binder/stone interface leading to a condition in which the binder may be peeled cleanly away from the stone surface. This detachment occurs equally with bitumens and tars and, under traffic stresses, may lead to the loss of cohesion which, although comparatively rarely, sometimes leads to surface disintegration.

Pretreatment of the mineral surface with certain metal salts may delay for several months the initial state of detachment, whereas this state cannot be prevented or delayed for more than a few days by the addition of wetting additives to the binder. Such additives, however, may modify the subsequent degree of detachment and very much reduce the loss of cohesion which may follow under the action of traffic. Loss of cohesion in these circumstances can also be reduced by the presence in the binder of components which have no possitive wetting tendency but confer a certain interfacial rigidity.

It is tentatively suggested that the condition of detachment is due to the absorption of water into the silicate lattice to give a weakened gel‐like structure and cause a rise in pH value at the surface of the mineral. This rise in pH value is thought to be responsible for the inability of wetting additives to prevent the initial state of detachment being reached.

Liability to detach is determined by the chemical nature of the aggregate and may not occur with minerals containing high proportions of more basic components particularly those containing iron. Under most conditions of stressing, the bond strength in the detached state is equivalent to that in the dry state although after prolonged immersion the resistance to tangential stresses may be relatively small. When the system dries out, reattachment may occur. These factors may help to explain why there is no direct relationship between the initial state of detachment and behaviour in practice.
Influence of solvent viscosity on the kinetics of the exchange of sodium for hydrogen ions in fixed beds of dowex‐50
Authors: Nutt C. W. , Sharifi S. , Tonge F.
Published: July 2010

Break‐through curves for the exchange of Na+ ions in 0·1 n‐NaCl in glycerol‐water mixtures for H+ ions in a fixed bed of Dowex‐50‐resin have been determined for Reynolds numbers from 0·01 to 2. Solutions containing up to 75% by vol. of glycerol and having viscosities up to 30 centipoise at 25° were used. Some measurements were also made on 0·1 n‐NaCl in ‘Polycell’ solutions in water. Small concentrations of this substance increase the viscosity of the system considerably with little effect on the ionic diffusivity. Effluent compositions and ionic diffusivities were determined by electrical conductivity. The total resistances to mass‐transfer were calculated from the slopes of the break‐through curves and values of the liquid film resistance estimated by the method of Gilliland & Baddour.2 The observed values of the liquid film coefficient could be correlated with flow rate, solution viscosity, and ionic diffusivity by the equation: kLD2/DL = 0·5 × Re0·83 × Sc0·75
Syntheses of metal complexing polymers. V. Polyvinyl titanic esters and related compounds
Authors: Lane E. S.
Published: July 2010

Methods of preparing polymerised vinyl esters of titanic acid are described. Under specified conditions these esters exhibit ion‐exchange characteristics but seem unlikely to be of practical use in this field.
Sucrose monoacetate
Authors: Kononenko O. K. , Kestenbaum I. L.
Published: July 2010

Sucrose monoacetate was prepared by acetylation of sucrose in pyridine solution. Recrystallization from isopropyl alcohol gave a product in pure form, as was shown by paper chromatography, while some higher acetates were detected in mother liquors. The properties of the new compound suggest possible application in two fields: as a humectant similar to sorbitol, but twice as effective as the latter, and as a potential nutritious carrier for food flavours with most properties of sucrose but the sweetness greatly reduced.
Reactivity of lime and related oxides. VI. crystal changes in carbonatated lime at different temperatures
Authors: Glasson D. R.
Published: July 2010

The ‘wet’ carbonatation of calcium hydroxide has been compared at 22° and 95° to determine the effect of temperature on the rate of formation, solubility and subsequent rate of ageing of the products, as indicated by changes in lattice structure and in surface area and average crystallite size. Direct precipitation of calcium carbonate from solution by double decomposition has been similarly compared, the conversion of the aragonitic and vateritic products to calcite being studied in solution at 95° and 22°, and in the solid state at temperatures up to 450°. Partly‐carbonatated lime has been hydrated to assess the extent to which the carbonate layer around each lime crystal inhibits further hydration.

In ‘wet’ carbonatation at lower pH levels (8–12), especially in the presence of bicarbonate ions, the calcium carbonate layer developed around each lime particle ages more rapidly at the higher temperature, becoming almost non‐porous before carbonatation is complete; at higher pH levels, the carbonate is more porous, and splits off more readily. Similar ageing of calcite inhibits the conversion of aragonite to calcite. In highly alkaline media, at pH 13–14, the conversion of both aragonite and of vaterite to calcite are inhibited at 95°, but occurs readily in the solid state above 400° with considerable loss of surface area, vaterite also sintering extensively at 300°. When partly‐carbonatated lime is hydrated, the presence even of thin carbonate layers reduces the splitting of the lime particles, and the capacity of the carbonate to age afterwards partly restores their stability.
(II) Zinc
Authors: Allbutt M. , Tolley G.
Published: July 2010

Rates of solution of zinc in aqueous and dioxan solutions of hydrochloric acid are determined by weight loss and hydrogen evolution measurements. It is shown that the reaction between zinc and HCl in aqueous solutions is partly controlled by diffusion processes. With stirring sufficiently vigorous to eliminate this effect the rate is proportional to the mean ionic activity of HCl, and this is consistent with direct participation of chloride ions in the anodic reaction. Dioxan causes a change of reaction mechanism due, it is suggested, to its adsorption on the metal surface, inhibition of normal electrode processes, and promotion of a direct reaction between zinc and HCl molecules.
Organic constituents of gelatins and animal glues. III. Survey of the occurence of mucosubstances in gelatins and glues
Authors: Williams A. P.
Published: July 2010

A survey of the occurrence of the mucosubstances reported in the first two papers of this series1,2 is reported. Certain modifications of the isolation techniques necessary for use with high‐grade gelatins and glues are described.
Separation of thorium from uranium and rare‐earth elements by solvent extraction with tri ‐ n ‐ butyl phosphate ‐ xylene
Authors: Menzies I. A. , Rigby F.
Published: July 2010

A study is made of three processes for the separation of thorium from uranium and rare‐earth elements in crude thorium nitrate solutions prepared by breakdown of monazite sand. Uranium may be separated from thorium and rare‐earth elements in a preliminary extraction with 5% or 40% v/v tri‐n‐butyl phosphate (TBP) in xylene and the thorium separated from the rare‐earth elements in a subsequent extraction with 40% v/v TBP in xylene. Alternatively thorium and uranium may be extracted simultaneously from the solutions with 40% TBP in xylene and the thorium preferentially backwashed from the loaded solvent with dilute HNO3. The present work indicates that processes in which uranium only is extracted in the first operation will be the most flexible and the simplest to operate. The partition coefficients for zirconium, which occurs as an additional contaminant in solutions prepared from thorite ores, have also been determined by batch extraction with 5% and 40% TBP in xylene and the data confirmed in a continuous countercurrent system.
Chemical constitution of road tars and coal tar pitches
Authors: Wood L. J.
Published: July 2010

Oils derived by the distillation of primary and refined tars and the solvent treatment of pitch have been examined by high‐temperature gas‐liquid chromatography. The solvent extracts of the pitch have also been analysed by infra‐red spectroscopy and for elementary composition. It has been possible to account for a large part of the tar oils as quantities of individual compounds and to indicate the main changes in chemical types associated with the increasing number of rings in the less soluble pitch fractions.
Electrical conductivity of dilute aqueous phosphate solutions and phosphoric acid at elevated temperatures and pressures
Authors: Whitehead G.
Published: July 2010

A combined pressure vessel and conductivity cell suitable for use at pressures up to 16 atm. and temperatures up to 200° is described. This equipment has been used to measure electrical conductivities of sodium phosphates and phosphoric acid at low concentrations (phosphates 0.0006–0.01M, H3PO4 0.13M).

With each substance, the conductivity attained a maximum and then decreased with increasing temperature. The temperatures where conductivities were maximum were lower than those previously reported for uni‐ and di‐valent salts.
The mass spectra of cyclic fluorine compounds
Authors: Majer J. R.
Published: July 2010

The mass spectra of a number of fluorinated cyclohexanes, cyclohexenes and cyclohexadienes have been measured and the correlations between the fragmentation patterns and molecular structure have been studied.
The properties of tar‐polymer mixtures
Authors: Wood L. J.
Published: July 2010

Mixtures containing continuous vertical retort tar and small concentrations of long‐ chain polymers have been examined by a number of different flow and brittle tests. In general the addition of polymer causes an increase in resistance to flow without greatly affecting the viscosity/temperature behaviour or the brittleness. A method of rheological analysis is presented for characterising the viscoelastic properties. The practical implications of the measurements are discussed.
Chemical modification of wood. I use of trifluoroacetic anhydride in the esterification of wood by carboxylic acids
Authors: Arni P. C. , Gray J. D. , Scougall R. K.
Published: July 2010

Treatment of beech sawdust with a series of mono‐ and dicarboxylic acids in benzene solution at 25–30° in the presence of molar proportions of trifluoroacetic anhydride resulted in esterification of the cell wall components. The esterification is shown to be due in part to acylation by the carboxylic acid and in part to trifluoroacetylation. The latter caused discoloration of the wood due to slow hydrolytic release of trifluoroacetic acid on storage at room temperature. Similar esterification of sapwood lengths of Ponderosa pine resulted in surface modification only and was accompanied by a significant decrease in impact strength property.
Composition of mineral water from the hot spring at bath
Authors: Riley J. P.
Published: July 2010

Analyses are given for water taken directly from the hot spring at Bath, Somerset, and for the calcareous incrustation surrounding the spring. The concentrations of the major ions in the water agree well with those found in an analysis by Judd Lewis, but the agreement for the trace elements is less satisfactory.
Studies in hydrogen‐bond formation. IX Bonding between esters and the chloro‐group
Authors: Giles C. H. , Nakhwa S. N.
Published: July 2010

The refractometric method is used to demonstrate hydrogen‐bond complex formation between aromatic chloro‐groups and the α‐methene or ‐methylene groups of ester residues. The bond between chlorobenzene and ethyl acetate has an energy ∼ −3kcal. /mole in aqueous ethanol. This type of bond probably assists the adsorption by cellulose acetates of dyes containing chloro‐groups. Chlorobenzene is strongly adsorbed by cellulose triacetate, probably by this mechanism. The hypothesis of ‐Cl … HC‐bonding may assist in the interpretation of the relative degrees of plant growth‐hormone activity of chlorinated aryloxyacetic acid derivatives.
The pyrolysis of cellulose and the action of flame‐retardants. I. significance and analysis of the tar
Authors: Holmes F. H. , Shaw C. J. G.
Published: July 2010

A study has been made of the pyrolysis of different cottons in vacuum, and in dry air, mainly at 418°C and the products have been fractionated and analysed. From a purified cotton cellulose, the main products are a combustible tar and water, but when a flame‐retardant is present less tar and more gas and carbonaceous residue (char) are produced. The tar is highly flammable, and is a major factor in the burning of cotton. There is a correlation between the amount of tar formed and the flammability of the cotton. Removal of the impurities from the cotton cellulose leads to the formation of more tar on pyrolysis. The tar is a mixture of organic compounds of which the major component is laevoglucosan. Acids, carbonyl compounds and unsaturated compounds have been found and determined quantitatively.

It is concluded that for a treated cotton cellulose material to be flame‐resistant the amount of tar formed on pyrolysis must be small.
The removal of copper extrusion sheaths from zirconium and its alloys
Authors: Menzies I. A. , Rigby F.
Published: July 2010

The rates of dissolution of copper and zirconium in mixed nitric and hydrofluoric acid solutions have been determined at laboratory temperature. It has been shown that such solutions can be used for the removal of copper extrusion sheaths from zirconium without significant loss of zirconium or absorption of hydrogen by the zirconium. There was no evidence of the formation of powdery or active surfaces on the zirconium after removal of copper and no explosions were encountered in the present work.

The anodic dissolution of copper in aq. ammonia‐ammonium sulphate solutions has also been studied. Copper dissolves with an apparent valence number equal to unity and it is thought that copper(I) is stabilised in such solutions by complex formation. Copper extrusion sheaths can be removed from zirconium by anodic dissolution in such media without loss of zirconium or absorption of hydrogen by the zirconium. This process also facilitates the recovery of copper.

The two processes are discussed with respect to safety in the light of present knowledge. It is concluded that the nitric acid‐hydrofluoric acid process is unsuitable for the removal of copper from uranium‐zirconium alloys, and that the possibility of explosion during the removal of copper sheaths from unalloyed zirconium cannot be completely ruled out. The anodic dissolution process appears to be a safe one, and could probably be used for uranium‐zirconium alloys in addition to unalloyed zirconium.
An experimental survey of rust preventives in water III. Some general results
Authors: Hersch P. , Hare J. B. , Robertson A. , Sutherland Sheila M.
Published: July 2010

The influence of pH, apart from the case of amines discussed in Part II,1 and geometrical factors on the inhibition thresholds for mild steel in non‐acid aqueous solutions containing dissolved air, are described. Modifying the standard corrosion tests by partial or complete removal of the air‐formed oxide film increased the inhibition threshold concentration with some but not all inhibitors. Conversely, pre‐immersing the specimen in an inhibiting solution reduced the threshold value below the normal value.

Substances which form soluble iron complexes, such as catechol and EDTA, were often found to increase the inhibition threshold for mild steel, but the results nevertheless indicate that inhibition is not necessarily associated with the deposition of an insoluble iron salt. The iron complex solutions were themselves found to inhibit in some instances, a fact probably relevant to the well‐known inhibition effect of tannins.

Generally no marked differences appeared in the threshold values for a number of irons and low alloy steels. Azide showed a resemblance to nitrite in its behaviour, which suggests a similar inhibition process, i.e. adsorption. The cast irons, especially the ferritic varieties, were considerably more difficult to inhibit. Many inhibitors for ferrous materials were also found to inhibit zinc corrosion, which indicates that unfilled electron energy bands or vacant atomic orbitals are not necessary for inhibition to occur.

The results described in the three papers of this series are summarised, and a novel hypothesis is presented by one of us (P.H.) to account for inhibition by anions.
The surface properties of silica gels. III Adsorption of benzene and ethanol vapours
Authors: Horvat Danica M. , Sing K. S. W.
Published: July 2010

Silica gels were prepared under various conditions from sodium silicate and two organic silicates. The gels prepared by the hydrolysis of ethanolamine polysilicate were less active than those obtained from sodium silicate, but a gel with a substantial surface area was prepared by the slow hydrolysis in acid solution of isopropyl silicate.

Adsorption isotherms of benzene and ethanol were determined gravimetrically on samples of the gels at temperatures between 0° and 35°. Evidence is presented to show that the Brunauer‐Emmett‐Teller (B.E.T.) values of the monolayer capacity for ethanol are more reliable than those for benzene. For most gels, the area occupied by the ethanol molecule in the adsorbed monolayer appears to be close to 31 Å2.
Variations in the kinetics of setting of calcined gypsum. II. The action of retarder‐accelerator mixtures
Authors: Ridge M. J. , Surkevicius H.
Published: July 2010

The effects were studied of some retarder‐accelerator mixtures on the kinetics of setting of samples of seven calcined gypsums with different characteristics. Egg albumin, calcium acetate, sodium hexametaphosphate and borax were the retarders used in conjunction with precipitated calcium sulphate, potassium sulphate and sodium chloride as accelerators. Some of the retarder‐accelerator mixtures reduced the range of the induction periods of the samples, the most effective being those based on calcium acetate as a retarder and precipitated calcium sulphate as accelerator the least effective were those based on borax as retarder and potassium sulphate as accelerator.

The effects were tested of the retarder‐accelerator mixtures in reducing the sensitivity of plaster to contamination with retarders and accelerators. All the formulations except sodium hexameta‐phosphate and borax with potassium sulphate reduced the difference between the retarded induction period and the accelerated induction period.

The observations made are discussed in terms of the theories already developed for the actions of retarders and accelerators.
Determination of endothermal heat effects of clays in the study of thermal efficiency of brick kilns
Authors: Ramachandran V. S. , Majumdar N. G.
Published: July 2010

The heat of dehydration of clays caused by the loss of combined water between 425 and 750° accounts for nearly 10% of the total heat input in estimating the thermal efficiency of kiins used for the production of structural clay products. Heat of dehydration is usually assessed from a determination of the ‘ residual ignition loss’, using certain assumptions. This paper discusses the possibility of applying Differential Thermal Analysis to calculate directly the heats of dehydration of brick clays, potassium sulphate being used as a standard.
Electrode potential studies of iron in dilute solutions of sodium nitrite
Authors: Baghurst H. C.
Published: July 2010

Previous workers have shown that inhibitors having relatively strong oxidising anions, such as chromate and nitrite, passivate iron both in the presence of air and in de‐aerated solutions. Evidence is presented to show that while this may be so in 0.1M solutions, the behaviour in de‐aerated dilute solutions ranging from 200 to 1600 p.p.m. of inhibitor is quite different. Further, the action of nitrite is essentially different from that of chromate, in that, in the absence either of dissolved oxygen or of a pre‐immersion oxide film, nitrite is impotent in preventing corrosion of iron.
Influence of some additives on the hydration reactions of portland cement I. Non‐ionic organic additives
Authors: Stein H. N.
Published: July 2010

The influence of some non‐ionic organic additives, dissolved in the water used for mixing cement pastes, on cement hydration was determined by isothermal calorimetry. The additives, all poly‐alcohols, exert a retarding action on cement hydration. Glycerol has, in addition, a particular influence on the crystallisation of ettringite and calcium hydroalumino‐monosulphate, accelerating the consumption of sulphate ions.
Effect of a miscible solvent on the Clemmensen reduction
Authors: Risinger G. E. , Thompson J. A.
Published: July 2010

The effect of a miscible solvent on the formation of monomolecular and bimolecular reduction products is discussed. Evidence is presented to support a solubility phenomenon.
Surface properties of hydrolysed titania. III. Titania prepared from titanium chloro‐alkoxides
Authors: Harris M. R. , Whitaker G.
Published: July 2010

Samples of titania gels were prepared by the hydrolysis with steam of titanium chloro‐alkoxides and titanium tetrachloride, and their surface characteristics studied by the adsorption of nitrogen at low temperatures. All the gels were active, but they exhibited a wide range of pore sizes and surface areas. The gels were stable, but the freshly prepared samples when refluxed with water underwent an unusual form of ageing in which the surface areas and pore volumes rose considerably. Raising the pH, preferably by dialysis but also by the addition of ammonia solution, changed the surface characteristics of the gels but did not destroy their activity; after this treatment the gels aged normally under reflux, with a reduction in surface area. By comparison of these results with those obtained in Parts I and II, a scheme has been drawn up for the preparation of active titania gels with any desired pore radius in the range 10–100 A.
An approach to applicable inorganic polymers. IV. Interaction of boron or silicon halides with esters of phosphonic acids
Authors: Chainani G. , Gerrard W. , Patel J. K. , Twaits R.
Published: July 2010

Interaction of phosphonate esters with boron trichloride, B‐trichloroborazole and chlorosilanes is studied. The boron trichloride systems gave hard, sometimes brittle, resins; the trichloroborazole reactions gave almost quantitative yields of alkyl chloride and polyanhydrides with P‐O‐B linkages; the methylchlorosilanes yielded, in the main, softer and more soluble products than those from boron trichloride. The applicability of the products as inorganic polymers is rather doubtful.
Decomposition equations of ammonium perchlorate
Authors: Simchen A. E.
Published: July 2010

The data existing for the thermal decomposition equations of ammonium perchlorate (AP) have been reviewed after reducing them to a common basis (100 moles of AP). They have been evaluated from two points of view: (a) stoicheiometric balance of the elements present, and (b) establishment of thermodynamic equilibrium of the final gaseous products. From a knowledge of the distribution of the nitrogen between N2, N2O and NO, and of the chlorine between Cl2 and HCl (the latter derived from the equilibrium constant for the Deacon process), the corresponding equilibrium temperatures (Teq) and the flame temperatures (Tt) have been calculated. These temperatures agree in a number of cases with the measured heating temperatures and temperatures of the gas flame.

Extrapolation of the equilibrium gas compositions calculated for different pressures indicates that the gas composition at equilibrium lies between two asymptotic extremes which are:

For zero pressure or for relatively low Teq

and for high pressures or for relatively high Teq,

Below 300° some ClO2 forms, and N2O instead of NO. NO when, formed reacts giving nitrosy1 compounds.

At all temperatures there may occur a ‘freezing’ of non‐equilibrium compositions.
An extension of the Nelsen‐Eggertsen continuous flow method of surface area measurement
Authors: Haley A. J.
Published: July 2010

One of the simplest methods of surface area measurement is extended to include the size distribution of pores in the 10–300 Å radius range. This technique involves passing a mixture of 10% nitrogen in helium over the sample cooled in liquid nitrogen at a fixed rate and at various pressures to 150 p.s.i.a. causing the nitrogen partial pressure to reach its liquefaction point. Consequently the nitrogen relative pressure in the sample tube is varied in the range of about 0.16 to 1. Nitrogen adsorbed or desorbed by increasing or decreasing pressure in the sample tube is measured continuously at near atmospheric pressure by thermal conductivity. The thermal conductivity cell always ‘sees’ a reference of 10% nitrogen in helium. Hence the measured composition differences fall within a comparatively narrow range where the thermal conductivity cell output is linear. Isotherms developed by this method are compared with isotherms obtained by the pressure‐volume method of adsorption measurement and show good agreement. Simplicity of design and operation of the instrument provides fast and reliable results.
Catalytic esterification of saturated carboxylic acids with ethylene under high pressure
Authors: Bhattacharyya S. K. , Lahiri G. R.
Published: July 2010

The syntheses of ethyl acetate, propionate and butyrate from the corresponding acids and ethylene in presence of catalysts have been studied in the pressure range of 50–180 atm. and temperature range of 120–200° under shaking conditions. Of the catalysts tried, dilute sulphuric acid proved the best. Agitation leads to improved yields of ester over static operation. Under optimum conditions the maximum yields of ethyl acetate, propionate and butyrate were 86.9%, 79.4% and 61.5% respectively.