bluuebunny/crossref_metadata_2025 huggingface dataset:
Fischer‐tropsch synthesis with cobalt catalysts. II. The effect of nitrogen, carbon dioxide and methane in the synthesis gas
Authors: Gibson E. J. , Hall C. C.
Published: July 2010

In the Fischer‐Tropsch synthesis at atmospheric pressure in the presence of a cobalt catalyst the rate of conversion of carbon monoxide and hydrogen is reduced by the addition of diluents to the synthesis gas. The fall in reaction rate has been shown to be approximately directly proportional to the fall in concentration of the reactants. The proportion of gaseous to non‐gaseous products increases with increasing dilution. For a fixed amount of diluent, the proportion of non‐gaseous products increases with change in the nature of the diluent in the order nitrogen, methane, carbon dioxide.

By using as diluent carbon dioxide containing 14CO2, it has been shown that carbon dioxide does not participate in the synthesis under the conditions used in these experiments.
Tests on the relative efficiency of chromate pigments in anticorrosive primers
Authors: Cole H. G.
Published: July 2010

Sea‐water‐spray corrosion tests have been made on two magnesium alloys, an aluminium alloy and mild steel painted with primers made from seventeen chromate pigments incorporated in turn in a stand oil/coumarone medium. Best all‐round protection was given by strontium chromate. Fair to good protection was given by potassium zinc chrome, sodium zinc chrome, zinc monoxychromate, zinc tetroxychromate and calcium chromate. Three complex cadmium chromes, three lead chromes and barium chromate all gave poor results.
Aldolization, ketolization, and crotonization: Catalysis with anion‐exchangers
Authors: Austerweil G. V. , Pallaud R.
Published: July 2010

The aldolization of aldehydes, catalysed by anionic exchangers, as formerly described, can be extended to a similar reaction in which aldehydes react with ketones; it is shown that, by using rather strongly basic anion exchangers, the reaction goes a step further in the condensation process through loss of water to give olefinic aldehydes by crotonization.
The carburization of iron oxide with carbon monoxide: Modifications of hägg iron carbide
Authors: Cohn E. M. , Bean E. H. , Mentser M. , Hofer L. J. E. , Pontello A. , Peebles W. C. , Jack K. H.
Published: July 2010

This study was undertaken because of its potential use in catalysis as well as in metallurgy. Modifications of Hägg iron carbide, exhibiting differences in X‐ray diffraction patterns and Curie points, have been observed; the differences appear to be linked to the mode of preparation. Carburization of reduced iron with carbon monoxide leads to ‘normal’ Hägg iron carbide with a Curie point at 245°to 250°; carburization of iron oxide produces Hägg iron carbide with a higher Curie point, up to 276°. The ‘high‐Curie‐point’ carbide progressively approaches the ‘normal’ form with increasing temperature and time of carburization. Possible explanations for the ‘high‐Curie‐point’ modification, based on the effect of oxygen, alkali, or crystallite size, are suggested. The Curie point of 247 ± 3°is that of pure, well‐crystallized Hägg iron carbide.
The estimation of solvent power by the dilution ratio method
Authors: Moore W. R. , Brown A. M.
Published: July 2010

Determinations of the volumes of different precipitants required just to cause precipitation of cellulose nitrate, cellulose acetate and ethyl cellulose from dilute solutions in representative solvents are made and the values compared with those of the polymer‐solvent interaction parameter μ. Estimates are made of the solubility parameters of the polymers precipitated and a qualitative interpretation of the variation of volume of precipitant with solvent is attempted. In certain cases, enhancement of solvent power on addition of precipitant is suggested and confirmed by osmotic pressure studies using solvent—precipitant mixtures as solvents. Criteria for the use of the dilution ratio method as a means of assessing thermodynamic solvent power are suggested. In the cases of ethyl cellulose and cellulose acetate, a quantitative treatment predicts conditions under which precipitation and enhanced solvent power may occur fairly well.
The effect of surface abrasion on the hydrogen content of steel
Authors: Cooke F. , Shanahan C. E. A.
Published: July 2010

Abrasion of mild and stainless steel on a 3 M Company 120‐grade silicon carbide paper has been shown to increase the hydrogen content by 0·0049 and 0·0034 ml. per sq. cm. of apparent abraded area, respectively.

The application of the results to the determination of hydrogen in steel is discussed and, in the particular case of mild‐steel sheet where the surface area may be as high as 200 sq. cm. per 100 g., the magnitude of the error due to abrasion on the above silicon carbide paper is sufficiently high to invalidate the determination of internal hydrogen on such materials unless appropriate corrections are made.
The pyrolysis of acetylene below 550°C
Authors: Minkoff G. J. , Newitt D. M. , Rutledge P.
Published: July 2010

The polymerization of acetylene below 550° has been examined in a static system. For unpacked vessels it was found possible to obtain reproducible results, from which second‐order rate constants, and an activation energy of 46·7 | 2 kcal., have been obtained. The effect of a large number of additives has been examined, with particular reference to compounds which might be present as impurities in the acetone in which commercial acetylene is dissolved. The results were mainly negative, catalysis being observed only in the presence of diacetyl. Nitric oxide considerably lengthened the induction period, while alkyl halides and traces of some metals led to the replacement of polymerization by decomposition. In packed vessels the reaction is controlled mostly by the surface, and, with some packings, it is more rapid than in unpacked vessels.
The formation of metastable aluminas at high temperatures
Authors: Plummer M.
Published: July 2010

The formation of metastable alumina by the rapid cooling of droplets of molten alumina is described. The necessary conditions are discussed and a possible mechanism is suggested. Some consideration is given to the effect of impurities.
Adsorption at inorganic surfaces. II. Adsorption of dyes and related compounds by silica
Authors: Allingham Margaret M. , Cullen J. M. , Giles C. H. , Jain S. K. , Woods J. S.
Published: July 2010

A study has been made of the adsorption by varieties of silica of a number of aromatic compounds, (chiefly dyes), from aqueous solution.

Basic dyes are adsorbed by ion‐exchange in the form of a monolayer of cationic micelles, the amount adsorbed being considerably in excess of that required to cover the surface with a normal monolayer. In the case of methylene blue and pseudocyamine chloride, micellar adsorption is confirmed by spectroscopic examination of the solution before and after adsorption. This form of adsorption is very rapid (complete in a few minutes at room temperature) and is not temperature‐dependent.

Two typical anionic (sulphonated azo) dyes, Orange I and II, are also adsorbed, but much more slowly and to a less extent than basic dyes. Orange I is adsorbed probably by hydrogen bonding as a monolayer. Both of these dyes are oriented perpendicularly as single anions, but some micellar adsorption may occur. Orange II has no free phenolic group and is adsorbed probably by accompanying sodium ions themselves adsorbed by ion‐exchange, and its extent of coverage is much less than a monolayer. It is suggested that the low adsorption rates are a result of the difficulty the dye anions have in penetrating to the negatively charged silicon surface.

p‐Nitrophenol is adsorbed as a monolayer, probably by hydrogen bonding. There is no clear evidence that forces other than ion‐exchange and hydrogen‐bonding are effective in adsorption of any aromatic compounds on silica.
The theory of recovering salt from sea‐water by solar evaporation
Authors: Myers D. M. , Bonython C. W.
Published: July 2010

A theory is developed for the production of salt by the evaporation of sea‐water. The theory leads to simultaneous differential equations, solutions of which were evaluated on a differential analyser, for both steady‐state and transient conditions.

The steady‐state solutions provide data which can be used in the design of a saltfield, particularly in the determination of the ‘concentrating’ area required to provide an adequate supply of concentrated brine to feed the ‘crystallizing’ area from which the salt is ultimately recovered.

The transient solutions show the behaviour of the saltfield after flooding with fresh brine, and also after a sudden change is made in the rate of flow through the system. The latter studies are of interest from the operating, rather than design, point of view.
The effect of conditions of preparation on the form of alumina. I. Precipitation and subsequent calcination of products in the system aluminium sulphate‐sodium aluminate‐water
Authors: Lewis J. A. , Taylor C. A.
Published: July 2010

Results are given of an investigation, using X‐ray powder photography for identification, of the effects of temperature, concentration, order of addition and excess of either of the reagents used on the nature of precipitates and their calcination products. Some clarification of the interrelationships of the various forms of alumina is adduced.
The preparation of aluminium soaps by a continuous process. II. Aluminium nonanoate
Authors: Taylor A. J. , Woods D. E.
Published: July 2010

An account is given of the laboratory preparation of aluminium dinonanoate, the aluminium soap of 3: 5: 5‐trimethylhexanoic acid, using a continuous process. The effect, on the composition and quality of the soap produced, of changing variables such as concentration and proportions of the reacting solutions, degree of agitation and time and temperature of reaction, has been found. It is shown that the product of the best quality, when judged by the consistency and storage stability of gels in hydrocarbons, is produced when the reaction pH is kept within the range 3.6 to 4.0. The conclusions from the laboratory preparations were later confirmed on pilot‐plant scale.
Relationship between viscosity and molecular weight of ethyl cellulose
Authors: Moore W. R. , Brown A. M.
Published: July 2010

Six fractions of ethyl cellulose have been obtained. Their number‐average molecular weights have been determined osmotically and limiting viscosity numbers at 25° obtained using five solvents. Values of K and α in the expression [η] = KMa are given. Those for α do not vary much with solvent and are not simply related to solvent power. Up to a molecular weight of about 80,000, the relationship between [η] and M̄n seems to be linear and values are given of the constant Km in the Staudinger expression [η] = KmM.
Analytical separation of the methyl esters of the c8‐c34 straight‐chain fatty acids and the detection of odd‐carbon‐number acids in commercial mixtures of fatty acids by gas chromatography
Authors: Khan M. A. , Whitham B. T.
Published: July 2010

A gas‐chromatographic technique is described whereby fatty acids up to C34 may be separated as their methyl esters. Application to commercial fatty acid mixtures revealed the presence of acids with odd numbers of carbon atoms and small amounts of acids hitherto unidentified in such mixtures.
The Pyrolysis of p‐terphenyl: Separation and identification of the thermal products
Authors: Silverman L. , Trego Katherine , Houk W. , Shideler Mary E.
Published: July 2010

The products obtained by heating p‐terphenyl to 460–480° in a closed tube have been studied and identified. One group of products consists of low‐molecular‐weight hydrocarbon gases and hydrogen; a second decomposition product is diphenyl; there is a third group consisting of quater‐, quinque‐, and sexi‐phenyls. Of these, the following polyphenyls have been isolated and identified: p‐quaterphenyl, 3: 4′‐diphenyldiphenyl, 3‐phenyl‐4′‐(4″‐diphenyl)diphenyi, 4‐phenyl‐3′‐(4″‐diphenylyl)diphenyl, p‐sexiphenyl and 4 : 3′‐bis‐(4″ : 4″‐diphenylyl) diphenyl.

Under the influence of heat, p‐polyphenyls combine with each other, chiefly at the m‐positions. An equimolar mixture of diphenyl and p‐terphenyl, after being held at 480° for 2 days, gave several types of m‐quaterphenyls and m‐quinquephenyls which shows that p‐terphenyl breaks down partially to diphenyl which either condenses with itself to form even‐numbered polyphenyls, or reacts with undecomposed p‐terphenyl to form a quinquephenyl.
Statistical‐graphical survey of series of linear and cyclic dimethylsiloxanes
Authors: Waterman H. I. , Van Herwijnen W. E. R. , Den Hartog H. W.
Published: July 2010

A study is made of the physical characteristics of linear and cyclic polysiloxanes. It is shown that by plotting v20/v70 versus v20 (v = kinematic viscosity) it is possible to determine the average number of silicon atoms per molecule in a mixture of linear and cyclic siloxanes, and the average ratio of silicon atoms in linear structure to those in cyclic structure and to predict physical constants of siloxanes when two of them are known.
Influence of additives on the properties of surfactant solutions
Authors: Biswas Arun K. , Mukherji B. K.
Published: July 2010

Surface tension, interfacial tension and wetting, emulsifying, foaming, and suspension characteristics of ionic and non‐ionic surfactant solutions have been determined and evaluated in absence, and in presence, of electrolytes and non‐ionogenic additives. Considerable insight has been gained about the factors governing the surface and bulk properties of surfactant solutions and as regards how these are influenced by additives.
The influence of movement and temperature on the corrosion of mild steel. I. Water circulation apparatus and tests in teddington mains water
Authors: Butler G. , Ison H. C. K.
Published: July 2010

An apparatus designed for investigating corrosion in flowing water at speeds up to 400 ft. per min. and at temperatures up to 70° is described. Each system accommodates 36 tube specimens, each 6 in. long, and provides for three speeds of flow.

Preliminary conditioning tests with a hard mains water demonstrate the applicability of the testing technique. The corrosivity of this water is largely governed by its scale‐forming properties and an increase in both speed of flow and temperature promotes the deposition of a protective scale. The decrease of alkalinity due to scale deposition often results in a higher corrosion rate on specimens introduced into the system during test.
Corrosion of zinc. I. Corrosion in impure ammonium chloride solution
Authors: Stickland F. G.
Published: July 2010

The corrosion of zinc in circumstances closely simulating those existing in a dry primary cell during storage has been examined with special reference to the effect of ionic impurities. It is shown that, after 12 weeks in ammonium chloride electrolyte solution containing such impurities, the attack on the zinc may be drastically modified. In particular, earlier work is confirmed which suggested that cobalt and nickel are extremely harmful and that mercury exerts a protective influence. No satisfactory explanation of these facts has been found.

It is shown that the chemical reactions associated with the corrosion are independent of the added ions. A sequence of reactions is suggested to explain the changes observed in the solution and in the solid corrosion products as corrosion progresses.
Some viscous and elastic properties of rubberised bitumens
Authors: Smith L. M.
Published: July 2010

The simultaneous changes in the viscous, elastic, and brittle properties that result from the addition of rubber to bitumen have been investigated for several different types of rubber and bitumens ranging in hardness from 170 penetration to 55 penetration. The results show that the changes in viscosity and low‐temperature extensibility are due, in the main, to the molecular (or near molecular) dispersion of rubber in the bitumen. For a given bitumen these changes are linearly related both to each other and also to changes in softening point, thus giving a simple method of assessing the relative merits of different types of rubber. It is shown that sulphur, added to latex or present in a vulcanised rubber, causes a rapid breakdown of the rubber when it is heated with bitumen. An equi‐viscous basis is suggested for the characterisation of rubberised bitumens.
Estimation of ruthenium species in solutions arising from the aqueous processing of irradiated uranium
Authors: Brown P. G. M. , Naylor A.
Published: July 2010

The estimation, by paper chromatography and solvent extraction, of the different types of nitrosylruthenium complex present in solutions of irradiated uranium is described. The ruthenium in certain ‘dissolver solutions’ has been found to occur in approximately equal proportions of (RuNO) nitrato (non‐nitro) and (RuNO) nitro complexes. The value of the ruthenium decontamination factor observed in the first extractor of the chemical separation plant at Windscale, to which these ‘dissolver solutions’ are fed, is consistent with this composition.
The pyrethrins and related compounds. II. infra‐red spectra of the pyrethrins and of other constituents of pyrethrum extract
Authors: Elliott M.
Published: July 2010

The infra‐red spectra of the pyrethrins and of other compounds found with them in pyrethrum extract are presented and discussed. The spectra of the four insecticidal esters are interpreted in terms of those of the acids and alcohols from which they are constituted.
Effect of impurities on polyethylene adhesion
Authors: Bikerman J. J.
Published: July 2010

The peeling strength of an aluminium foil glued to a glass plate with ‘adhesionable’ polyethylene was lowered by incorporating oleic acid into polyethylene. The average thickness τ of the organic film remaining on the aluminium after peeling was a few microns for pure polyethylene, near 20 μ for a mixture of polyethylene 99.6 and oleic acid 0.4 parts, and very small (for instance, 0.5 μ) for a mixture of polyethylene 97 and oleic acid 3 parts. In grossly contaminated polyethylenes, rupture occurred in a weak boundary layer and τ depended on location and extent of these layers.
The transformation of bayerite into hydrargillite
Authors: Sato Taighi
Published: July 2010

X‐ray and infra‐red studies have been made of the ageing of bayerite in water and in potassium aluminate solution for periods of up to 3 months at 30°. They show that transformation of bayerite into hydrargillite occurs slowly in water, and more rapidly in potassium aluminate solution. The seeding of alkali aluminate solution is also investigated in connexion with these results.
Anion exchange in chromate solution
Authors: Arden T. V. , Giddings M.
Published: July 2010

When chromic acid solutions are passed through hydroxide‐form anion‐exchange resin columns, the resin is converted successively to the chromate and dichromate forms, the completion of the second process coinciding with the first appearance of chromic acid in the effluent. Continuation of the process beyond the breakthrough point results in the uptake of tri‐ and tetra‐chromate in proportions dependent on the concentration of the input solution. The polychromates are removed by means of water, and the dichromate by direct reaction with alkali, neither of these being ion‐exchange processes. Chromate is removed by exchange with hydroxide in the normal manner.
Mechanism of the interaction of oxygen with surfaces of noble metals
Authors: Andreeva V. V. , Shishakov N. A.
Published: July 2010

A review, largely of Russian work, is presented.
Determination of the accessibility of cellulose films by infra‐red spectroscopy
Authors: Priest D. J. , Shimell R. J.
Published: July 2010

A method has been developed, based on that of Mann & Marrinan,4 for the accurate determination of the accessibility of regenerated cellulose films of thickness 20–25 μ such as are used commercially for packaging. The films are treated with heavy‐water vapour and the exchange reaction with accessible hydroxyl groups is followed spectroscopically.

By application of this method it has been shown that the accessibility of these films is decreased by treatment with water or dilute alkali followed by drying. On prolonged drying of deuterated cellulose films fresh accessible hydroxyl groups are formed, which it is suggested is due to proton‐deuteron interchange in the fringes of crystallites.

Introduction of hydroxyethyl side groups into the cellulose chain molecules causes the accessibility to increase. Over the range studied (78.6—86.9% accessible) the accessibility is proportional to the volume swelling in water, an increase of 1% in the accessibility corresponding to a 16% increase in the volume swelling. It is deduced from this large effect that the increase in accessibility is accompanied by disappearance of small crystallites (which act as junction points in the molecular chain network) as well as a reduction in the size of larger crystallites.
Diffusivity of ammonium dihydrogen phosphate in aqueous solutions
Authors: Mullin J. W. , Cook T. P.
Published: July 2010

Empirical relationships commonly used for the prediction of liquid diffusivity data are shown to be unreliable for aqueous solutions of solid solutes. An interferometric technique suitable for diffusivity measurement in such solutions is described. For the system ammonium dihydrogen phosphate‐water over the temperature range 15–50° diffusivities can be estimated from the relationship

Dζ × 108 = 4.7 + 0.16θ

The activation energy for diffusion in near‐saturated solutions over this temperature range is ∼10 kcal./mole.
Critical temperatures and pressures of ternary hydrocarbon mixtures: The ethane‐propane‐n‐butane system
Authors: Grieves Robert B. , Thodos George
Published: July 2010

Utilising a visual PVT cell, experimental values have been established for the critical temperatures and critical pressures of five mixtures containing ethane, propane and n‐butane, and of two mixtures containing propane and n‐butane. The results are extended by use of experimental critical values reported in the literature for the ethane‐propane, ethane‐n‐butane, and propane‐n‐butane binary systems; a unique graphical technique is applied to generate triangular composition diagrams containing parameters of critical temperature and pressure. These diagrams accurately establish the critical point of ethane‐propane‐n‐butane mixtures over the entire composition range.
Some crystallisation phenomena in rapidly quenched 6.6 nylon
Authors: Chappel F. P. , Culpin M. F. , Gosden R. G. , Tranter T. G.
Published: July 2010

In a study of the technology of the melt spinning of 6.6 nylon filaments of diameter in the range 30–100 μ, some new crystallisation phenomena have been noted. Because of the geometrical form of the filaments, cooling from the melt is extremely rapid. Solidification takes place in a fraction of a second, and further cooling to room temperature is also rapid. The polymer can be observed at various stages during its quenching, either by taking samples from the running filaments, or by examining it whilst it is running.

Under these conditions, the solid polymer is seen to have a structure not very different from that of the melt. This structure is stable at room temperature for long periods in the absence of moisture. However, on exposure to moisture, diffusion of water into the filament may result in elongation with accompanying changes in the crystalline character. The effects of temperature and moisture concentration on the diffusion process have been studied. X‐Ray diffraction, depolarisation of light and microscopical techniques have been used to examine the crystallisation process in the filament as it is being spun and during the subsequent process of equilibration with water.

X‐Ray and optical results show changes of structure to occur on different time scales: the implications of this on the concepts of polymer morphology are discussed. The important röle played by atmospheric moisture in the crystallisation of 6.6 nylon is established, and the likely dependence on water content of second‐order transition data is examined.
Preparation of N‐alkenyl‐ and N‐m‐styryl‐phosphoramidates and their application as flame retardants for wood
Authors: Arni P. C. , Jones E.
Published: July 2010

Interaction of organophosphorus halides with allylamine and diallylamine yields N‐alkenyl‐phosphoramidates: with m‐aminostyrene, N‐m‐styryl derivatives are obtained. These compounds may be polymerised with varying degrees of facility by heat, free‐radical or ammonium persulphate initiation to yield resins or gums. The preparation and properties of phosphoramidate monomers obtained by condensation of these unsaturated amines with mono‐ and bifunctional phosphoro‐, phosphono‐ and phosphonothio‐chloridates is described. The attempted condensation of phosphoramidates with αβ‐unsaturated acid chlorides to obtain N‐unsaturated acyl phosphoramidates gave syrups which resinified on heating to yield brittle solids high in phosphorus and nitrogen. Some of the compounds described have been used to impregnate wood blocks, and polymerised in situ, either by heat, chemical or irradiation initiation, and they imparted flame‐retardant properties to the wood which were resistant to cold‐water leaching.
The mechanism of phenol adsorption by organo‐clay derivatives
Authors: Roberts A. L. , Street G. B. , White D.
Published: July 2010

The adsorption of phenol by various amine‐activated montmorillonites has been studied and the resulting expansion of the basal spacings of the derivatives measured. The results indicate that the expansion of the basal spacings of the primary amine derivatives is strictly limited, whereas with the quaternary ammonium‐treated clays a much greater expansion is found, and a correspondingly larger amount of phenol is adsorbed.

A comparison of the amount of phenol adsorbed by the quaternary ammonium compound in solution and when the latter is ion‐exchanged on to the clay, shows that a considerable increase in adsorption occurs in the latter case.
Three methods for the determination of the degree of substitution at protein‐amino groups with special reference to substituted gelatins
Authors: Cobbett W. G. , Gibbs J. A. , Leach A. A.
Published: July 2010

Three methods for the determination of the degree of substitution at protein‐amino groups are examined and compared. The procedures are applied to benzenesulphonyl derivatives of gelatin. The formol titration and ninhydrin colorimetric procedures are generally applicable to soluble proteins and their soluble derivatives. The spectrophotometric method is also applicable to these materials when the substituting reagent contains a chromophoric group. In this method the tyrosine content of the protein must be low or not react with the reagent, or the chromophore of the substituent must not absorb light in the tyrosine absorption region. The agreement between the first two procedures is good, and the third method is also in good agreement when the above conditions are met.
Kinetics of n‐butane adsorption on various particle sizes of silica gel by gas‐solid chromatography
Authors: Eberly P. E.
Published: July 2010

The techniques of gas‐solid chromatography have been widely used for measuring heats of adsorption. It is theoretically possible to derive information concerning the adsorption kinetics from the same chromatographic data and the present report deals with this application of chromatography. The process of adsorption in a packed column of adsorbent is visualised as resulting from molecular collisions with the external surface of the porous adsorbent particles. Only a fraction α of the total collisions results in adsorption. The adsorbed molecules, on the average, spend a finite time, θ, in the adsorbent particle. For n‐butane on silica gel at 60°, θ is proportional to the 3/2 power of the particle diameter and varies from 1·8 to 13·8 sec, for samples having median diameters of 0·192 to 0·712 mm., respectively. For a given particle size, θ is proportional to eΔH/RT (ΔH is the heat of adsorption) and amounts to about 8 kcal./mole.
A correlation method for binary azeotrope data
Authors: Shorr L. M.
Published: July 2010

An empirical correlation of binary azeotropes has been developed which can predict azeotrope formation and composition. The method is based on the linear relationship which exists between two compounds when the azeotrope compositions of each with a series of functionally related compounds are compared.
Competitive interactions in adsorption from dilute aqueous BI‐solutesolutions
Authors: Weber W. J.
Published: July 2010

Experimental evidence of competitive interactions between individual adsorbates in dilute aqueous bi‐solute systems are presented. Rates of adsorption and positions of equilibrium for adsorption on porous granular carbon have been investigated. In the cases studied, the rate of adsorption as well as the total quantity of a single solute adsorbed at equilibrium is decreased with increasing concentration in the system of a second adsorbate. Indeed, it has been possible to describe quantitatively, after the Langmuir adsorption model, the competitive effect of each solute upon the total quantity of the other adsorbed at equilibrium. It appears that the competitive forces are quite broad in scope, doubtlessly effective to varying degrees in all multiple‐adsorbate systems. Apparently the effect of one solute on the position of equilibrium attained by another is largely a function of the relative energies of adsorption. Kinetic interactions observed in the experiments cannot be explained entirely on this basis, because rates of uptake in the agitated non‐flow experimental systems were apparently controlled by rates of transport of solute in the capillary‐size pores of the adsorbent. Thus, physical hindrance becomes of importance in interpretation of the observed results. The large dodecylbenzenesulphonate molecule exhibits a markedly greater effect on the rates of uptake of the other adsorbates studied than do they upon that of the former.
Co‐Ordination state of aluminium ions in CaO–Al2O3–SiO2 glasses
Authors: Chopra S. K. , Taneja C. A.
Published: July 2010

The state of co‐ordination of aluminium ions in synthetic glasses in the system CaO–Al2O3–SiO2 was studied by determining the effects of varying the alumina content (from 1 to 7 moles) on the density and refractive index of glasses of composition 10 CaO, 8 SiO2, n‐Al2O3 (CaO/SiO2 ratio 1.17:1). The partial molecular refractivity of alumina indicated a fourfold co‐ordination of aluminium ions.

The increase in density and refractive index due to the replacement of varying amounts of silica by alumina at a fixed level of CaO (36—44%) has been shown to be due to lower partial specific volume of alumina compared with that of silica and is not due to sixfold co‐ordination of aluminium ions as reported in the literature.
The boiling‐point relations of cadmium and zinc at elevated pressures
Authors: Baker E. H.
Published: July 2010

The boiling points of cadmium and zinc have been determined at elevated pressures by means of an internally heated pressure vessel, used in conjunction with argon as the pressure medium.

Vapour pressure‐temperature relations have been derived for cadmium in the pressure range 1—103.5 atmospheres and for zinc in the range 1—30.2 atmospheres; heats of vaporisation have been calculated for these metals from these relations.

Unusual crystallisation phenomena are exhibited by the condensed droplets of the metals.
Binary vapour‐liquid equilibria
Authors: Jean Fu S. , Lu Benjamin C.‐Y.
Published: July 2010

Vapour‐liquid equilibrium data were determined at 75° for three binary systems: benzene‐n‐heptane, n‐heptane‐propanol‐1 and benzene‐propanol‐1, using a modified Gillespie still. Log γ values were correlated by a three‐constant Redlich‐Kister equation.
The formation of ettringite on aluminium surfaces
Authors: Edmeades R. M. , James A. N. , Wheeler J.
Published: July 2010

It has been shown that the reaction between aluminium powder and the aqueous phase of cement pastes is chiefly characterised by a definite inhibition period when no hydrogen evolves, followed by a slow evolution of gas. The utility of aluminium powder in reducing the early shrinkage of cement pastes depends upon this gradual reaction. The inhibition is specifically associated with the presence of ettringite on the surface of aluminium particles. It is suggested that the ettringite is formed by reaction of calcium sulphate with the hydrous oxide film on aluminium particles: termination of a period where no hydrogen is evolved, probably results from a more or less complete conversion of aluminium oxide to ettringite.
Activity coefficients of the n‐primary, secondary and tertiary aliphatic amines in aqueous solution
Authors: Christie A. O. , Crisp D. J.
Published: July 2010

The activity coefficients of the n‐primary, secondary and tertiary aliphatic amines in very dilute aqueous solution were obtained from determinations of partial pressures or from solubility measurements. the activity coefficient of n‐butylamine increased 1.26 times when the ionic strength of the solution was raised from 0 to 0.75, the approximate value for sea water.

Free energies of solution, hydration and vaporisation all showed regular increases with the number of carbon atoms in the molecule. the free energy of solution of primary, secondary and tertiary amines increased by 727, 700 and 610 calories respectively and the free energy of hydration by 85, 143 and 52 calories for each carbon atom. Isomeric aliphatic amines showed an increase in total free energy of hydration in the order, primary, secondary, tertiary, indicating that, as with the isomeric alcohols, the free energy of hydration increased as the molecule became more compact.
The rate of evaporation of potassium sulphate
Authors: Nettleton M. A. , Raask E.
Published: July 2010

In an effort to throw more light on the evaporation and condensation of alkali‐salts metal in high‐temperature furnaces, measurements have been made of the rate of evaporation of captive potassium sulphate droplets at temperatures up to 1500°. Observations on the evaporation rate in nitrogen and in oxidising atmospheres are consistent with the view that, in those conditions, the rate is controlled by the well‐known laws relating to the diffusion process. In the presence of hydrogen or carbon monoxide, the rate of loss of weight is very much increased because the potassium sulphate is then reduced on the surface of the droplet and the reduction products are much more volatile. the rate of weight‐loss then depends on a balance of the transport of the reducing gases to the surface and the diffusion of the reduction products from the surface.
The removal of radioactive caesium contaminants from simple aqueous solutions
Authors: Davis B. M. , Sebba F.
Published: July 2010

Cs ions can be removed from aqueous solutions by forming a precipitate of copper ferrocyanide which, having occluded the Cs ions, can in turn be floated by means of an anionic collector. Collection was achieved with either α‐sulphopalmitic acid or sodium dodecyl sulphate depending on what interfering ions were initially present in the solution. Recoveries of 98–99% were obtained on batch scale experiments and 97.5–98.5% on continuous scale operation. The investigations of the flotation parameters of pH, gas‐rate, concentrations of precipitating reagents and collector, as well as the interference effects of other ions are discussed. Using data obtained in batch scale tests, continuous scale experiments were designed and operated.
Effect of certain hostile environments on adhesive joints
Authors: Kerr C. , Macdonald N. C. , Orman S.
Published: July 2010

The effects of water vapour on aluminium‐aluminium bonded joints, using a Bisphenol A diglycidyl ether epoxide resin cured with bis‐(4‐aminophenyl)‐methane as the adhesive, have been studied. A distinction has been drawn between the effect on joint strength and on polymer strength. The very significant fall in joint strength compared with the change in polymer strength is used to postulate that in adhesive joints of this type, water molecules rapidly enter the boundary region to interfere with the secondary valence forces responsible for adhesion between substrate and organic adhesive. The results are further interpreted as support for the view that the polymer adjacent to the metal substrate is likely to differ in structure and conformation from the main polymer mass, namely a boundary layer. Similar experiments using the less polar ethanol provide further evidence for the hypotheses.
Ternary vapour‐liquid equilibrium: The use of a multi‐stage still
Authors: Butler P. A. , Ridgway K.
Published: July 2010

The construction of a six‐stage vapour‐liquid equilibrium unit based on the Ellis still is described. Its application to the measurement of equilibrium data in the ternary system benzene—cyclohexane—n‐hexane was investigated. Results are presented for this ternary system and for the three associated binary systems. The nature of the resulting ternary distillation lines is discussed.
Polymerisation of dec‐1‐ene. III. The nature of the catalyst species using triethylaluminium and titanium tetrachloride under cationic conditions
Authors: Beynon K. I. , Milne C. B. , Southern D.
Published: July 2010

The polymerisation of dec‐1‐ene, using several combinations of aluminium alkyls and titanium halides, has been studied to try to elucidate the nature of the active catalyst species in the system triethylaluminium/titanium tetrachloride at a molar ratio (AlEt3:TiCl4) of 0.3:1. Polymers similar to those formed by the AlEt3/TiCl4system have been obtained using ethylaluminium dichloride in combination with titanium trichloride and titanium tetrachloride. The complexes formed from these combinations are the most likely catalyst in the AlEt3/TiCl4(0.3:1) system.
Diffusion measurements for ethanolamine‐water systems with a wavefront‐shearing interferometer
Authors: Thomas W. J. , McKnicholl E.
Published: July 2010

The application of a wavefront‐shearing optical interferometer to diffusion measurements in aqueous solutions of mono‐, di‐, and tri‐ethanolamines is described. This technique is extremely accurate in determining diffusivities, and the results are compared with measurements made with a Gouy interferometer. The large differences between the experimentally determined diffusion coefficients at infinite dilution and those predicted by existing semi‐empirical equations are shown to be due in part to the inadequacy of these equations, and in part to the hydration of the ethanolamines in solution. It is recommended that, in the use of the semi‐empirical equations, molecular irregularities in solution be allowed for by recalculation of the solute molecular volume on the basis of a hydrated molecule.
Mechanism for the anti‐redeposition action of sodium carboxy‐methyl cellulose with cotton. I. Radiotracer studies
Authors: Evans P. G. , Evans W. P.
Published: July 2010

The adsorption of a 14C‐labelled sodium carboxy‐methyl cellulose (SCMC) on to textile fibres and soil particles has been investigated. Attempts have been made to relate the amounts of SCMC adsorbed to its anti‐redeposition action. The results show that SCMC is only effective as an anti‐redeposition agent with fabrics on to which it readily adsorbs from detergent solutions.
Mechanism for the anti‐redeposition action of sodium carboxy‐methyl cellulose with cotton. III. Electrophoresis and sedimentation studies
Authors: Johnson G. A. , Bretland R. A. C.
Published: July 2010

Electrophoresis and sedimentation studies on cotton and on carbon black, and ASTM carbon soil tests on cotton in which two sodium carboxy‐methyl celluloses (SCMC) of differing degrees of substitution and a propane sulphonate ether of cellulose were used, have shown that the anti‐redeposition properties of SCMC in the detergent formulation may be treated by the Derjaguin, Landau, Verwey & Overbeek theory of colloid stability. However, there is a further stabilising force postulated as being due to solvation of the SCMC molecules on the surface of the cotton and also as being dependent on the molecular weight of the SCMC. The evidence suggests that if the degree of substitution of the SCMC is increased, then to retain the same anti‐redeposition properties, the molecular weight must also be increased. It is concluded that the most suitable SCMC to put into detergent formulations is the type at present used.
Electrodialytic transport of inorganic and of organic anions
Authors: Kelman S. , Grieves R. B.
Published: July 2010

The electrodialysis of monocarboxylic acids and their potassium salts in the series formic acid to valeric acid has been investigated. A laboratory‐scale continuous‐flow unit was operated over the current density range 0·4 to 6·0 mA/cm2 with total feed concentrations of 13·1 and 26·2 meq/1. Initial experiments were conducted with chloride and sulphate, for which the total transport and selectivities are established. At pH values set to assure 95% dissociation of the monocarboxylic acids, the transport (in the presence of chloride) of formate, acetate and propionate was about 20%, but that of butyrate and valerate was less. Acid salt selectivities (transport compared with chloride) ranged from 0·5 for formate through propionate to 0·3 for butyrate and valerate.

For butyrate, the percentage transport increased approximately linearly with current density and was a random function of equivalent fraction of butyrate in the feed. Increases in total concentration produced no increases in transport. Butyrate selectivities were somewhat independent of current density and of equivalent fraction.

Throughout the study, there was only limited evidence of fouling of the membrane by the organic acids and their salts, although valerate did produce temporary fouling.
Formation and reactivity of oxides and basic salts. II. Radio‐isotope studies of some calcareous materials
Authors: Glasson D. R. , Huff E. G. , Jones J. A. , Sheppard Margaret A.
Published: July 2010

Rates of calcium exchange between solid and solution in the ageing of hydrated lime and of calcium carbonate samples have been determined using calcium‐45 radio‐isotope. After a comparatively rapid calcium uptake of about 1 molecular layer at the hydrated lime surface, the exchange rate diminishes as the ions need to diffuse more deeply into the hydrated lime structure. Results for calcium carbonate samples of widely different specific surfaces are compatible with very slow ageing in water.

Rates of gypsum precipitation from radioactive calcium chloride and nitrate solutions have been compared in neutral and acidic media and in the presence of albumen. Lower gypsum saturation ratios are established ultimately in neutral rather than acidic media, particularly in solutions containing no salts other than gypsum.

Solid hydrated lime reacts rapidly with dilute sulphuric acid, aluminium and magnesium sulpnates, magnesium chloride or sea‐water, releasing calcium ions into solution. The radioactivities of the solutions decrease subsequently as gypsum separates out or calcium ions are adsorbed by the finely‐divided magnesium hydroxide precipitated. At higher magnesium salt concentrations, the calcium‐45 radioactivity does not initially increase so sharply. This is ascribed to basic salt formation preventing all of the lime from going quickly into solution.
Reactions of sulphur‐containing hydrocarbons in an electrical discharge
Authors: Allt P. K. , Datta P. , Macey W. A. T. , Semmens B.
Published: July 2010

A study has been made into the effects of a low frequency semi‐corona discharge on carbon disulphide, ethyl mercaptan, amyl mercaptan and thiophene present as 1–2% sulphur/hydrocarbon mixtures. Semi‐corona discharge, which was carried out at atmospheric pressure, has resulted in the partial desulphurisation of the sulphur‐containing hydrocarbon mixtures. The efficiency of the desulphurisation was influenced by the techniques employed and by the nature of the central electrode. In almost all instances the reactions were accompanied by the formation of solid material.
Sulphoxidation of methyl radicals
Authors: Good A. , Thynne J. C. J.
Published: July 2010

The reaction of sulphur dioxide‐oxygen mixtures with methyl radicals, generated by the photolysis of azomethane at Λ 3400 Å, has been studied in the temperature range 50–150° in an attempt to evaluate some of the basic reactions involved in the sulphoxidation of free radicals and hydrocarbons. Addition of sulphur dioxide to a mixture of methyl radicals and oxygen leads, unexpectedly, to an initially increased consumption of oxygen.

A rate constant has been determined for the reaction:
equation image
a value of 1·7 × 1016 mole−2 cm6 sec−1 being obtained. Using this value, the rate constant for the reaction:
equation image
has been estimated to be ∼ 7·8 × 107 mole−1 cm3 sec−1.

Comparison of the reactions of acetyl and methylsulphonyl radicals with oxygen and with radicals in dicates that in both cases acetyl radicals are much more reactive by ∼ 103 times.
Effect of pH on structure and mechanical properties of electrodeposited iron
Authors: Levy E. M. , Macinnis R. D.
Published: July 2010

Relationships between the mechanical properties of electrodeposited iron and the pH of the bulk of the solution were obtained for a chloride/fluoborate plating bath. Both ultimate tensile strength and percentage elongation at fracture passed through a maximum over a narrow range of pH. Structural studies using optical and electron microscopy supported the results of the experiments on mechanical properties. A relationship between the average surface‐roughness height of the deposit and the bulk pH was also obtained. The results are explained in terms of hydrogen evolution and hydroxide precipitation.
Oxidation of thiols in gas‐liquid systems. III. Oxidation of ethanethiol in the presence of catalysts containing copper, cobalt and nickel
Authors: Swan C. J. , Trimm D. L.
Published: July 2010

The kinetics of the oxidation of ethanethiol in aqueous alkaline solution have been examined in the presence of copper‐, cobalt‐ and nickel‐containing catalysts. The homogeneity of the system and the precise nature of the catalyst are important factors controlling the rate of oxidation. It is suggested that free radical processes are unimportant and that reaction involves electron‐transfer from the thiol anion to the metal, followed by dimerisation of co‐ordinated thiyl entities to produce disulphide.
Thermodynamic functions of disulphur decafluoride
Authors: Pass G.
Published: July 2010

Thermodynamic functions of disulphur decafluoride have been calculated over the range 200–1000°k. The results from a possible equilibrium reaction of disulphur decafluoride have been used to calculate an approximate value for the heart of formation of disulphur decafluoride.
Foam separation of complexed cyanide: Studies of rate and of pulsed addition of surfactant
Authors: Grieves R. B. , Bhattacharyya D.
Published: July 2010

An experimental investigation is presented of the foam separation of cyanide complexed with ferrous iron, using a cationic surfactant, ethylhexadecyldimethylammonium bromide. With a 25 min. foaming time, an initial iron to total cyanide ratio of 0·351:1 and an initial surfactant to complexed cyanide ratio of about 0·34:1 suspensions containing from 1·54 to 3·08 mM total cyanide can be reduced to about 0·11 mM in complexed cyanide and 0·29 mM in non‐complexed cyanide.

The rate of surfactant removal was satisfied by a first‐order relationship, similar to that obtained with colloidal ferric oxide. The rate of complexed cyanide removal was satisfied by a reversible, approximately first‐order relationship eliminating the residual surfactant concentration. The pulsed addition of surfactant in three dosages during the course of an experiment, compared with a single dose at the beginning of an experiment, produced lower residual concentrations of complexed cyanide and higher foam volumes. At an iron to total cyanide ratio of 0·351:1,90% of the complexed cyanide concentration could be removed by one fifth less surfactant, using pulsed addition, compared with a single dose.