bluuebunny/crossref_metadata_2025 huggingface dataset:
The insoluble matter of coal tar. VII. Dilution of tars
Authors: Green S. J. , Olden M. J. F.
Published: July 2010

Previous application of surface‐tension rules to dilution of coal tars is criticized and it is considered that the surface tension of the mixture of diluent with the oils of the tar must be considered rather than the surface tension of the diluent alone. Maximum insolubles in a tar‐diluent system occur at lower ratios of diluent to tar for both horizontal‐ and vertical‐retort tars. The relation of maximum insolubles to the surface tension of the diluents has been examined and generally it is shown that diluents with surface tensions above that of the tar behave quite differently from those of lower surface tension. The results are interpreted to mean that flocculation and precipitation, followed by solution or redis‐persion, occur when diluent of surface tension lower than the tar is added in increasing amounts.
Identification of and tests for homogeneity of alcohols by means of the nitrophenylhydrazones of their acetoacetates
Authors: Carroll M. F.
Published: July 2010

A new method for identifying alcohols by the determination of the melting points of the p‐nitro‐phenylhydrazones of their acetoacetates is described and shown to be of fairly general application. The method may also be used to give an approximate estimate of the homogencity of commercial alcohols.

A selection of melting points of the derivatives of purified alcohols normally used in commerce is given and some results for the ordinary commercial products are shown for comparison.
The hydrolysis of wool wax and related high molecular weight esters. I. Homogeneous reactions
Authors: Truter E. V.
Published: July 2010

The homogeneous alkaline hydrolysis of the acetates, caprylates and palmitates of n‐octadecanol and cholesterol in the four lowest normal alcohols has been studied. It is shown that the various constants for the reactions are within the range recorded for similar reactions of low molecular weight esters, no anomalies of any sort being observed.
The preparation of 4‐AMINO‐2‐Nitrophenylarsonic acid
Authors: Polya J. B.
Published: July 2010

Improved experimental details are reported for the preparation of 4‐amino‐2‐nitrophenylarsonic acid by the known five‐stage route from p‐phenylenediamine in an overall yield of 17‐22%.
Estimation of impurities in aluminium alloys by means of arc spectra
Authors: Janiec J.
Published: July 2010

To estimate the impurities in aluminium alloy a d.c. arc is used. An aluminium‐alloy rod, 12 mm. in diameter and faced up on the lathe, is employed as the positive electrode and a graphite rod pointed to 60° as the negative one. Analysed samples and suitable standards are spread over the photographic plate as in spark exposures. They are energized in an arc under defined conditions, i.e. 4‐mm. gap between the electrodes, potential difference 220 v., current 7 amp., etc. Ilford thin‐film half‐tone plates are used and are developed according to the maker's instructions. The spectra registered are then measured and evaluated in a similar manner to that used for the spark spectra; an internal comparison method is used. In arc spectra registered under these conditions the densities of the analysed samples are similar, and on this account the same standards may be used for all unknown samples which pass through the spectroscopic laboratory. This method properly used gives accurate and reproducible results.
Automatic distilling apparatus for continuous production of conductivity water
Authors: Bieber Roman C. , Ibl Norbert
Published: July 2010

A simple laboratory device is described which allows the double distillation of water in a continuous and automatic way in order to produce particularly pure water. The water thus obtained has a mean specific conductivity of 0.5 × 10‐6 ohm‐1cm.‐1 at 25° c.
Organic adsorbents from Indian tannins. II. Adsorption of acids, bases and salts
Authors: Bhatnagar M. S. , Nigam P. C.
Published: July 2010

The adsorption of homologous series of monobasic and dibasic aliphatic acids by katha and cutch resins has been studied. The adsorption decreases with the increase in the molecular weight. This reversal of Traube's rule is explained on the basis of orientation of molecules at the resin‐water surface according to the theory of Langmuir and Harkins. The influence of substituted hydroxyl groups has also been studied. The adsorption of barium, strontium and calcium has been studied. The order of adsorption is explained on the basis of the polar concept.
Extraction of the active agent from detergent mixtures
Authors: Miller S. A. , Bann B. , Ponsford A. P.
Published: July 2010

The active agent in dilute aqueous detergent solutions can be extracted without loss with n‐butanol in presence of added sodium carbonate.
Formaldehyde condensations with phenol and its homologues. XII. The dehalogenation of halogenated diphenylmethanes having halogen substituents in the nucleus
Authors: Finn S. R. , Lewis G. J.
Published: July 2010

The preparation of I‐hydroxy‐2 : 6‐bis‐(2‐hydroxybenzyl)benzene by dehalogenation of the corresponding trichloro compound was described in Part X of this series (Finn, Lewis & Megson, 1950). The removal of the chlorine was effected by treatment of the boiling amyl alcohol solution of the compound with sodium. The yield was poor and amounted to only 5% of theory.

It has now been found that the dehalogenation can be achieved more satisfactorily by treatment of a solution of the diphenylmethane derivative in aqueous sodium hydroxide with Raney nickel‐aluminium alloy. A yield of about 50% of theory is obtained.

2 : 2′‐Dihydroxydiphenylmethane may be obtained from 2 : 2′‐dihydroxy‐5 : 5′‐dichloro‐diphenylmethane by the same means and the method has been used to prepare 2 : 2′‐dihydroxy‐3 : 5‐dimethyldiphenylmethane, 2 : 2′‐dihydroxy‐3 : 3′ : 5 : 5′‐tetramethyldiphenylmethane, and I‐hydroxy‐3 : 5‐dimethyl‐2 : 6‐bis‐(2‐hydroxybenzyl)benzene.
‘β‐Phellandrene’ from Canada‐balsam oil
Authors: Davenport J. B. , Sutherland Maurice D. , West T. F.
Published: July 2010

It has been found that, contrary to earlier reports, the β‐phellandrene obtainable from Canada‐balsam oil by fractional distillation is very impure, being contaminated with about an equal amount of (—)‐limonene. A much purer β‐phellandrene may be separated from the hydrocarbons resulting from the dehydration of neopiperitol.
THE extraction and refining of germanium and gallium
Authors: Powell A. R. , Lever F. M. , Walpole R. E.
Published: July 2010

Sources of germanium and gallium are discussed and descriptions are given of processes for the recovery of these elements from flue dusts and from germanite. The flue‐dust process involves smelting to recover the rare elements in a metallic regulus, dissolution of this regulus in ferric chloride solution with the aid of chlorine, distillation of crude germanium tetrachloride from the resulting solution, fractional distillation of the crude product to remove the bulk of the arsenic, and final rectification through a column packed with copper turnings to remove the remainder. After hydrolysis of the resulting tetrachloride germanium oxide is obtained with less than 0.1 p.p.m. of arsenic. Gallium is recovered from the acid liquor in the first still by treatment with aluminium to remove heavy metals and to reduce the iron to ferrous chloride, followed by extraction of the gallium chloride in a continuous process with isopropyl ether, removal of the ether by distillation, purification of the aqueous phase with hydrogen sulphide, and conversion of the gallium into sodium gallate for electrolysis.

The germanite process is a modification of that recommended by Sebba & Pugh (1937), combined with similar refining stages to those used in the treatment of flue dust.
THE determination of the cement content of soil‐Cement mixtures. II.Rapid field methods
Authors: Clare K. E. , Sherwood P. T.
Published: July 2010

Modern methods of producing soil‐cement mixtures in civil engineering involve the use of mixing machines having high rates of output. It is necessary to have methods of determining rapidly the cement content of mixed material to enable the addition of cement to the mixer to be controlled and to avoid wastage of material containing insufficient cement. This paper describes two such methods.

In the first method the soil‐cement mixture is placed in an acidic buffered solution, and the cement content is determined by a measurement of the pH of the resulting suspension. Some of the factors influencing the results have been investigated.

The second method is applicable when super‐rapid‐hardening cement is used; it consists in determining the chloride content of the mixture, by the Volhard technique.
Formaldehyde condensations with phenol and its homologues. XIII.The relative reactivity of the ortho AND para Positions in the formation of alcohols of substituted phenols
Authors: Finn S. R. , Lewis G. J.
Published: July 2010

In earlier papers of this series it has been shown that the action of formaldehyde on 3 : 5‐xylenol in the presence of sodium ethoxide catalyst results in the formation of anortho‐ortho‐dialcohol. Attempts to prepare asortho‐monoalcohol by modification of the reaction conditions foiled. A consideration of the behaviour of other substituted phenols appears to lead to a generalization that when bothmetapositions and sometimes when theparaposition of phenols, relative to the phenolic hydroxyl group, are occupied by substituents, the introduction of a methylol group into one ortho position results in an enhanced reactivity of the other. Such an enhanced reactivity of oneorthoposition would explain why dialcohols are readily formed, but that the presumably intermediate mono‐alcohol cannot be isolated.

Attempts to prepare some trinuclear substituted compounds by condensation of di‐ortho‐substituted phenols with various intermediates failed. The explanation of this failure is probably due to a decreased reactivity of theparaposition in these di‐ortho‐substituted phenols.
The nature of the products obtained by refluxing styrene and drying oils in xylol solution. II.Additional data on the styrene‐Tung oil reaction
Authors: Brunner H. , Tucker D. R.
Published: July 2010

An examination has been made of the reaction products obtained by refluxing a mixture of equal weights of styrene and tung oil in xylol solution in the absence of polymerization catalysts.

Copolymerization occurs between styrene and tung oil. Saponification of the copolymer yields two main types of styrenated elaeostearic acid. One, which gives an insoluble potassium salt, contains styrene combined with elaeostearic acid in the approximate average molecular ratio of 8 : 1. The other styrenated acid, which is soluble in light petroleum and yields a soluble potassium salt, approximates in composition to a product derived from 1 molecule of styrene and 1 molecule of elaeostearic acid.

In the conditions described, about 60% of the styrene remains unpolymerized and none forms a self‐polymer. Only about 60% of the available elaeostearic groups take part in copolymer formation, the remaining 40% being recoverable in a styrene‐free form.

It is believed that the 1 : 1 styrenated acid is formed by a Diels‐Alder mechanism.
POLYMERS AND COPOLYMERS OF ACENAPHTHYLENE
Authors: Idris Jones J.
Published: July 2010

An exploratory survey of the polymerization and copolymerization of acenaphthylene has been carried out to see whether there are possibilities of its use as an industrial monomer. Polyacenaphthy‐lene been prepared by thermal polymerization with and without peroxide‐type catalysts, by Friedel‐Crafts polymerization and by the emulsion technique. The molecular weight of a thermal polymer exceeded 100,000.

Some aspects of the copolymerization of acenaphthylene with styrene have been studied and it has been shown that a substantial elevation in the softening point of polystyrene results from the incorporation of acenaphthylene units in the polymer chain. The electrical properties of the copolymers are not significantly different from those of polystyrene.

Copolymers of acenaphthylene and isobutylene have been obtained by low‐temperature polymerization with Friedel‐Crafts‐type catalysts. The products were of a relatively low order of molecular weight. Examination of the ultra‐violet absorption spectra of the copolymers has revealed a tendency for the acenaphthylene units to enter the macromolecules in groups rather than randomly in single units.

Butadiene and acenaphthylene which, in certain conditions, undergo a Diels‐Alder condensation to give tetrahydrofluoranthene, furnish linear copolymers by emulsion polymerization. Attempts to prepare copolymers of acenaphthylene with ethylene proved unsuccessful, acenaphthylene showing a very pronounced inhibiting effect on the polymerization.
The essential oil of nothopanax simplex
Authors: Murray J. , Stanley B. G.
Published: July 2010

The essential oil of Nothopanax simplex consists largely of myrcene, with smaller amounts of α‐pinene, β‐pinene, dipentene, aromadendrene, α‐ and γ‐camphorenes, paraffin wax and other unidentified terpenes and sesquiterpenes.
The treatment of binary and ternary vapour‐liquid equilibrium data on systems with more than one liquid phase
Authors: Herington E. F. G.
Published: July 2010

The desirability of adopting some common method of plotting vapour‐liquid equilibrium data on systems with more than one liquid phase is stressed and attention is drawn to the lack of agreement in published literature on the theoretical treatment of such systems. The conditions under which both the Gibbs‐Duhem equation and the expression connecting the excess free energy of mixing with the activity coefficients apply to systems with more than one liquid phase are critically examined. As a result of this theoretical study a method of plotting equilibrium data on systems with two or more liquid phases is recommended and thermodynamic tests for the consistency of experimental data are presented. The method of plotting experimental results and applying tests for consistency are illustrated by an analysis of the published data on the system n‐butanol‐water.
Formaldehyde condensations with phenol and its homologues. XIV The dehalogenation of phenolic alcohols having halogen substituents in the nucleus
Authors: Finn S. R. , Musty J. W. G.
Published: July 2010

A major obstacle in the chemistry of phenolic resins is the difficulty in preparing some of the simple phenolic alcohols, owing to their reactivity and the formation of isomers which are not readily separated. The use of halogenated phenols, in which one or more of the free reactive nuclear positions are blocked by halogen atoms, generally avoids both further reaction and the formation of isomers. If a simple means existed of removing the halogen from alcohols prepared from such halogenated phenols, under mild conditions which would not cause further reaction of the product, then a method would exist for the preparation of many phenolic alcohols which cannot be prepared by the direct reaction of formaldehyde and the appropriate phenol. It has now been shown that this process can be accomplished by the use of Raney alloy in the presence of aqueous sodium hydroxide. A new alcohol of phenol (2:6‐dihydroxymethylphenol) has been prepared by this means.
The fluorination of hydrocarbons with cobalt trifluoride
Authors: Barbour A. K. , Barlow G. B. , Tatlow J. C.
Published: July 2010

The fluorination of hydrocarbons in the vapour phase by the use of cobalt trifluoride is readily achieved, and, when controlled conditions of reaction are employed, good yields of fluorocarbon products are obtained. An apparatus for carrying out this type of reaction, and also a convenient cell for the generation of fluorine are described. The syntheses of some of the hydrocarbon starting‐materials are given.
The melt‐viscosity of some phenol–formaldehyde novolak resins
Authors: Jones T. T.
Published: July 2010

The melt‐viscosity and density of a series of phenol–formaldehyde novolak resins of molecular weights varying between 400 and 900 have been studied in the temperature range 100–250°. Similar studies have been carried out for phenol (50–100°) and 2 : 2′‐dihydroxydiphenylmethane (125–190°).

The melt‐viscosity results have been examined in the light of Eyring's theory of viscosity and it is seen that the energy of activation for viscous flow falls rapidly as temperature increases and tends to steady values at high temperatures. These steady values are almost linearly related to molecular weight.

The rapid fall in energy of activation as temperature increases is attributed to the breakdown of association forces, mainly hydrogen bonds. At high temperatures flow is believed to take place by the movement of single molecules, but at low temperatures the large energies of activation suggest that flow takes place by associated dimers, trimers etc. breaking away from the general association field that surrounds them.

The coefficient of cubical expansion α is found to decrease rapidly from phenol to a resin of molecular weight about 400 and then more slowly as molecular weight increases; α also increases slightly with temperature.
A method for the determination of the solubility of gases in liquids with particular reference to viscous liquids
Authors: Baldwin R. R. , Daniel S. G.
Published: July 2010

A method for the determination of gas solubility is described which is particularly suitable for use with viscous liquids. The liquid, freed from other gases, is saturated with the gas under examination at a known pressure. A known volume of the saturated liquid is then streamed into an evacuated vessel and the liberated gas extracted by a Töpler pump and measured. Figures illustrating the accuracy obtainable are given for lubricating oils with a range of viscosity, and the necessary modifications for normal liquids are indicated.
The prevention of corrosion in packaging. I. The use of sodium benzoate as a corrosion‐inhibitor in wrappings
Authors: Stroud E. G. , Vernon W. H. J.
Published: July 2010

Sodium benzoates and other soluble benzoates can be used for the production of corrosion‐inhibitive wraps by impregnation in materials such as paper, strawboard, regenerated‐cellulose films and waxed papers. Provided the chloride content of the wrap is sufficiently low before impregnation, complete protection is effected for steel under adverse conditions of storage or transport. The corrosion of common non‐ferrous metals is in no case increased; in some cases it is substantially reduced or (e.g. solder and soldered joints) suppressed. For the protection of cast‐iron surfaces it is necessary to introduce a nitrite (e.g. sodium nitrite) into the wrap; the aggressiveness of nitrite towards solder is then prevented by the joint presence of sodium benzoate, in appropriate ratio.

Sodium salts of other organic acids show promise as corrosion‐inhibitors in packaging materials.
Observations on the preparation of diaminoguanidine
Authors: Scott F. L. , O'Sullivan D. A. , Reilly J.
Published: July 2010

Diaminoguanidine is a useful intermediate for the production of diheterocyclic systems, e.g. of the 5‐aryl‐ or 5‐alkyl‐2‐tetrazoyl‐tetrazole, or the dipyrazoyl‐formimine, types. Investigation of existing methods of the preparation of this substituted hydrazine has revealed some hitherto unobserved facts; e.g. (i) preliminary reduction of nitroaminoguanidine to the diaminoguanidine salt, followed by in situ dehydration and cyclization, provides a new route to the alkylaminoiminotriazoles; (ii) hydrazinolysis of the diaminoguanidine hydrazones has been found to take place readily; (iii) although cyanogen chloride and bromide form diaminoguanidine salts with hydrazine hydrate, cyanogen iodide forms an unstable hydrazine complex, without the formation of diaminoguanidine.
Comparison of hot‐centrifuge and solvent methods for the recovery of the tar binder from road materials
Authors: Gough C. M. , Green E. H.
Published: July 2010

Results are given of an investigation to compare the hot‐centrifuge and twin‐solvent methods for the recovery of tar from road mixtures. The centrifuge was a machine developed by Mitchell & Yardley, to which some improvements had been made, both in the machine and in the technique of operation.

The investigation showed that:

The tar binder cannot be recovered from every sample of road material by means of the hot centrifuge; such difficulty of recovering is most liable to occur with samples cut from road surfacings that are several years old. Recovery can always be effected by the solvent method.

When recovery can be effected by the hot centrifuge a small hardening of the tar (up to about 4° E.V.T.) is obtained, particularly if the viscosity of the tar is high. A correction must be applied for mineral matter which is usually present in the recovered tar.

The percentage of pyridine‐insoluble material (C1) in tar recovered by the hot‐centrifuge method is less than that found in tar recovered by the solvent method. The percentage of benzene‐insoluble material is also lower in tar recovered by the hot centrifuge.

The amount of material soluble in pyridine but insoluble in benzene (C2) in the recovered tar is approximately the same by either method for freshly mixed road material; from old material, the centrifuge method usually gives a lower percentage than the solvent method.

The hot‐centrifuge method is more rapid than the twin‐solvent method and is particularly useful for the examination of freshly mixed materials; the twin‐solvent method should be used in all cases when the hot centrifuge fails to extract binder and when sufficient tar for a detailed examination is required.
On the dryness and density of acetone
Authors: Thirion P. , Craven E. C.
Published: July 2010

The paper gives the combined experience of a French and a British firm on the relation between the density and water content of good commercial acetone samples. It is confirmed that, in a relative way, density is a good guide to water content but there remains some doubt concerning the density of dry acetone. A figure has been found 0.0005 lower than was previously accepted but still 0.0005 higher than those given recently by American workers. The lower values quoted by American authors may be due to the presence of isopropyl ether.

The direct chemical determination of water in acetone by the Smith & Bryant acetyl chloride–pyridine method appears to be reliable and this is recommended. The Karl Fischer method has not yet been made applicable to acetone–water mixtures.
The absorptiometric determination of small amounts of tin in titanium pigment
Authors: Williams F. R. , Whitehead J.
Published: July 2010

Hydrogen sulphide is recommended for precipitating tin, in the presence of cadmium, from acid tartrate solution of titanium. The resulting sulphides can be dissolved in acid and the colour produced by interaction between tin and dithiol can be measured on a photoelectric absorptiometer if Teepol X is added to produce an efficient dispersion. This system obeys Beers' Law up to a concentration of tin of at least 16 μg. per ml. and remains stable for at least three hours. Molybdenum interferes and ‘thionalide’ is not suitable as a precipitant.
Organic fluorides. XII. A simple rotating reactor for fluorination
Authors: Massingham W. E. , Montgomery R. , Smith F. , Thomas B. R. J.
Published: July 2010

A relatively simple rotating reactor is described for the fluorination of hydrocarbons and their derivatives by the agency of the higher fluorides of metals. Its application to the fluorination of petroleum ether is described and its greater efficiency as compared with the static vertical reactor (Haszeldine & Smith, 1950a) is demonstrated.
Improved syntheses in the pyrimidine series. II. The preparation of 4:5‐diaminopyrimidine
Authors: Brown D. J.
Published: July 2010

A greatly improved method of preparation of 4:5‐diaminopyrimidine, which is an important starting material for pteridine and purine syntheses, is described in detail. The route from thiouracil involves eight stages, but purifications, except that of the final product, have been avoided.
The esterification of tertiary alcohols with boric acid
Authors: Anderson J. R. , O'Brien K. G. , Reuter F. H.
Published: July 2010

The reaction between tertiary alcohols and boric acid has been investigated and esterification has been shown to occur using an azeotropic‐distillation method. However, all reaction products decomposed on attempted purification. The rate of esterification of tertiary alcohols is much slower than that of primary or secondary alcohols. The separation of alcohols from mixtures using direct esterification with boric acid is thus applicable to tertiary as well as primary and secondary alcohols. The scope of this method of separation has been studied and it was shown that whereas enols interfere, esters and acids do not. Moreover, the separation must be conducted below about 110° if tertiary alcohols are present.
Azeotropism in binary solutions at reduced pressures. III. Pyridine‐water solution
Authors: Fowler R. T.
Published: July 2010

The azeotrope of pyridine and water has been determined at atmospheric pressure and under reduced pressures down to 120 mm. The azeotrope is relatively unaffected by pressure reduction, a change of 600 mm. altering the azeotrope composition by 10% from 59·5% at 758 mm. to 53·8% pyridine at 120 mm.
Organic derivatives of titanium. III. Chlorotitanium alkoxides
Authors: Cullinane N. M. , Chard S. J. , Price G. F. , Millward B. B.
Published: July 2010

A number of mono‐ and di‐chlorotitanium alkoxides have been prepared by the method of Jennings, Wardlaw & Way (1936). Thus acetyl chloride reacts with titanium tetra‐alkoxides to give monochlorotitanium trialkoxides:

Ti(OR)4 + CH3·COCl = TiCl(OR)3 + CH3·CO2R

The monochloro‐esters, when treated with a further molecular proportion of the same reagent, yield dichlorotitanium dialkoxides:

TiCl(OR)3 + CH3·COCl = TiCl2(OR)2 + CH3·CO2R

The dichloro‐compounds have also been obtained by the action of titanium tetrachloride on alcohols:

TiCl4 + 2ROH = TiCl2(OR)2 + 2HCl

In general these products are viscous liquids, soluble in organic solvents and very easily hydrolysed by water.
The preparation of silicomolybdic and silicotungstic acids
Authors: Tourky A. Riad , El Shamy H. K. , Issa I. M.
Published: July 2010

Methods hitherto applied for the preparation of silicomolybdic and silicotungstic acids give non‐reproducible results. A procedure is recommended for their preparation.
Production of lanthanon and thorium compounds from monazite. II
Authors: Pilkington E. S. , Wylie A. W.
Published: July 2010

A partly cyclic process is described for the separation of the mixed hydroxides of the cerium‐group elements into cerous salts and into concentrates containing, respectively, lanthanum salts, mixed praseodymium‐neodymium‐samarium hydroxides or nitrates, and crude thorium phosphate.

The mixed hydroxides of praseodymium, neodymium and samarium are fractionally precipitated with ammonium hydroxide, leaving lanthanum in solution. Portion of the praseodymium, neodymium and samarium concentrate is used to precipitate basic salts of ceric cerium and thorium, the remainder being recovered. Cerium is obtained from the mixture of basic salts by reducing ceric compounds to the cerous state and precipitating thorium as a basic salt. Lanthanum is finally precipitated as lanthanum oxalate or lanthanum carbonate and cerium as sodium cerium sulphate.

Electrometric titrations of lanthanon solutions have been made at 80° to obtain data facilitating control of the various separations.
A contribution to the study of the action of certain inhibitors upon corrosion in chloride‐polluted water
Authors: Patterson W. S. , Jones A. W.
Published: July 2010

The comparative effects of potassium dichromate, sodium nitrite, sodium benzoate and soluble oil as corrosion‐inhibitors have been partially examined. The corrosion medium used is either sodium chloride solution or diluted sea‐water.

Although steel is readily protected in the presence of chlorides, cast iron gives results that are somewhat anomalous. The addition of soluble oil to a system already undergoing corrosion suppresses the attack. The importance of maintaining adequate concentrations of the inhibitor is discussed.
An investigation of the gaseous thermal‐decomposition products of linseed oil
Authors: Horspool J. M. , Julian K. A. R. , Oldham Graham
Published: July 2010

A method has been evolved for the investigation of the gaseous thermal‐decomposition products of linseed oil when used as a core binder. The method is suitable for similar investigations on other core‐binding materials. The products of decomposition over the temperature range 400–800° have been investigated as well as the effect of the preliminary heat treatment of the core on the composition of the gas. The most satisfactory baking time for a temperature of 230° appears to be approximately one hour, a core produced under such conditions giving the least gas containing the highest proportion of harmless carbon dioxide.
Preparation of radioactive penicillin
Authors: Smith E. Lester , Hockenhull D. J. D.
Published: July 2010

Crystalline radioactive penicillin has been prepared biosynthetically with a specific activity of over 1 c. per g. A synthetic medium low in sulphur and containing 1 mc./ml. of Na235SO4 was fermented in shake flasks. The penicillin was purified by solvent extraction and crystallized as the N‐ethylpiperidine salt.
The influence of zinc oxide smokes on the oxidation of sulphur dioxide in coal‐gas flames
Authors: Littlejohn R. F.
Published: July 2010

The effect of zinc oxide smoke additions on the dew‐point and sulphur trioxide content or an aerated coal‐gas flame containing sulphur dioxide has been studied. Measurements on filtered and unfiltered gases show that the presence of smoke tends, at first, to increase the amount of oxidation of dioxide to trioxide, but if sufficient smoke is present, the trioxide formed is absorbed and zinc sulphate is formed.
The volumetric determination of melamine as oxalat
Authors: Steele J. R. , Glover J. H. , Hodgson H. W.
Published: July 2010

A volumetric procedure is described for the assay of melamine. The addition of an aqueous solution of melamine to a 20% solution of oxalic acid in ethanol produces a crystalline precipitate of melamine mono‐oxalate. The filtered and dried oxalate may be dissolved in acid and titrated with standard potassium permanganate solution. The method is accurate to 0·3% of melamine, and small quantities of cyanogen compounds related to melamine have been shown to have slight effect on the assay.
The oxidation of carbon by air. II. Catalytic effects in the oxidation of graphite, nuchar and sugar charcoal by air
Authors: Patai Saul , Rajbenbach L. , Hoffmann E.
Published: July 2010

The oxidation by air of graphite, nuchar and sugar charcoal was studied in the presence of different catalysts. All reactions have been found to follow overall second‐order kinetics. Apparent activation energies of the uncatalysed oxidation and of the potassium carbonate‐catalysed oxidation have been determined.

Salts of strongly basic character accelerate the reaction strongly with all substrates studied, whereas the other catalysts studied did not exhibit the regularities observed with carbon black. The activity of the first group is attributed to the acceleration of the breakdown of surface oxides and it is proposed that this reaction is not dependent on the original form of the carbon present. The action of other catalysts, which is due to the oxygen‐carrying ability of the anions, appears to depend on the physical and chemical properties of the carbon used.
Oxidation of boart
Authors: Young R. S. , Benffield D. A.
Published: July 2010

Studies have been carried out on the rate of oxidation of different types and sizes of boart at various temperatures. For each variety and particle size of boart there is a ‘critical temperature’ above which losses increase rapidly even for such short heating periods as five minutes.

Oxidation of boart is markedly decreased by the proximity of certain substances such as tungsten carbide, tungsten, cobalt and graphite. Natural impurities in boart have a similar, protective action on oxidation and loss of diamond. As the particle size decreases, all cleaned boarts tend to become similar in composition and consequently possess similar reactions towards heat treatments.
Wool wax. ii. Lime saponification
Authors: Rossouw S. D. , von Rudloff E.
Published: July 2010

Methods for the saponification of wool wax are discussed. The rate of saponification of wool wax with lime has been investigated and the effects of certain additives on the rate have been studied. From the results optimum conditions have been chosen. On applying these on a 1‐kg. scale, complete saponification was obtained at 140° in six hours. Separation of the product into calcium soaps and non‐saponifiables was effected by acetone extraction.
Low‐temperature production of oxidized oil gels
Authors: Walker F. T. , MacKay T.
Published: July 2010

Large quantities of drying oil, mainly linseed, oxidized at low temperatures (below 90°) are consumed in the manufacture of linoleum. The two main processes of oxidizing the oil, the scrim and the mechanical, are reviewed. It is shown that the rate of oxidation obtainable at any temperature increases in direct proportion to the air/oil interface. A new process is described, in which the oxidation apparatus is a randomly packed column wherein a constantly flowing thin film of oil passing down is oxidized by a counter‐current stream of hot air. This method appears to combine some of the merits of both the scrim and the mechanical process.
The addition of thio‐compounds to olefins. III. Reactions of tri‐ and hexa‐methylenedithiols, and of bisthiol‐adipic and ‐sebacic acids
Authors: Cunneen J. I.
Published: July 2010

Certain dithiols and bisthiol‐acids react with natural rubber and with some related simple olefins in an analogous manner to the corresponding monofunctional compounds. The physical characteristics of the vulcanizates obtained from natural rubber and bisthioladipic acid are described.
The determination of sulphur, sulphide, thiosulphate, sulphite and sulphate in commercial calcium chloride
Authors: Fogg D. N. , Wilkinson N. T.
Published: July 2010

Methods have been developed for the determination of sulphur, sulphide, thiosulphate, sulphite and sulphate when present together in commercial calcium chloride.

The analysis is divided into three sections:

Section I.—Precipitation of sulphide by addition of zinc carbonate suspension; the precipitate also contains all the elementary sulphur present in the sample, and some insoluble sulphite and sulphate. The filtrate contains soluble thiosulphate, sulphite and sulphate, and these are determined by well‐known methods.

The zinc carbonate precipitate is examined for sulphide and insoluble sulphite by iodine titration. The precipitate from another zinc carbonate separation is added to an excess of acidified iodine solution in which case sulphur is precipitated in amount equivalent to the sulphide present. This sulphur is separated together with any sulphur present in the sample, oxidized to sulphate and determined as barium sulphate. The filtrate from the acidified iodine separation of sulphur contains sulphate equivalent to the insoluble sulphate and sulphite associated with the zinc carbonate separation.

Section 2.—Total sulphate is determined in the sample by first boiling with dilute hydrochloric acid and then precipitating the sulphate with barium chloride.

Section 3.—A third portion of the sample is used for the determination of insoluble sulphite plus total sulphide.

A separation of the insoluble sulphite and sulphide is carried out with zinc carbonate suspension and the mixture filtered. The sulphide together with insoluble sulphite is determined in the precipitate by titration with iodine. The filtrate contains soluble sulphate, sulphite and thiosulphate.

From the results of analyses of each section and by a series of calculations the contents of sulphur, sulphide, thiosulphate, sulphite and sulphate can be obtained.

The scheme of analysis is shown on p. 367.
The distribution of alcohols in the products of the fischer‐tropsch synthesis
Authors: Gall D. , Gibson E. J. , Hall C. C.
Published: July 2010

An alcohol‐rich product obtained by Fischer‐Tropsch synthesis at 160–175° and 150 lb./sq. in. (gauge), in the presence of a cobalt catalyst has been examined. It was found that n‐primary alcohols constituted 40% by weight of the organic liquid products (oil, spirit and organic matter in the water) and 92·4% of the total oxygenated products. The proportions of acids and carbonyl compounds were, therefore, markedly lower than those reported to be present in an iron‐catalyst product of the Hydrocol type.

The proportion of methanol present was very low, ethanol was present in the largest proportion and the proportions of the alcohols higher than propanol decreased with increasing carbon number. The proportion of propanol was less than that of butanol or pentanol so that the carbon‐number distribution curve for the alcohols showed a marked inflexion in the C3‐C4 region, which is not shown by the published distribution curve for the alcohols in the Hydrocol product.

From a study of the relative rates of decomposition of a series of n‐primary alcohols at 150° in the presence of hydrogen and a cobalt catalyst, it was possible to plot a curve relating alcohol stability and carbon number. This curve resembled the distribution curve in showing a low value for C1, a maximum at C2 and a marked inflexion in the C3‐C4 region, suggesting that the individual alcohols are present in the products of synthesis in proportions which are determined, at least in part, by their relative stabilities under the synthesis conditions.

It is considered that the alcohol distribution curve is of a form which would be predicted if the mechanism of alcohol formation involved step‐wise addition of methylene radicals to one end of a growing chain terminated by a hydroxymethylene radical, and if the survival of the alcohols was controlled by their relative stabilities.

From a consideration of the observed results and of those reported by other workers in the field, it is concluded that there is a balance of evidence in favour of the view that alcohols are the precursors of hydrocarbons in the synthesis.
Enzymes from micro‐fungi
Authors: Dingle J. , Solomons G. L.
Published: July 2010

One hundred and thirteen cultures of micro‐fungi were grown in both surface and submerged conditions and were then examined for production of polygalacturonase, α‐amylase, protease, cellulase (Cx) and lipase. Surface cultures were grown using the micro‐cylinder technique, and submerged cultures by the roll‐tube method.

This survey was carried out in order to find fungi that could produce enzymes for industrial use.
The mixing of casein glues
Authors: Lacey P. M. C.
Published: July 2010

In the mixing of prepared casein glues with water in quantity, the difficulties met with, namely lump‐formation and air‐entrainment, arise from difficulties experienced by the particles in penetrating the water surface, especially if the water already has part of the casein dissolved in it. It is shown that the mixing problem can be solved by carrying out the operation on a continuous basis, and using centrifugal forces to submerge the particles; a machine has been built in which correctly proportioned streams of casein powder and water are passed into a specially designed centrifuge cup, continuously discharged at the top through a scoop‐tube; a scraper provides reflux near the base, and air is removed centripetally as the materials ascend the divergent walls. The machine absorbed only 1/15 h.p. and yielded a virtually faultless mix at rates up to 20 1b. per minute.
The ignition of inflammable gases by sparks from aluminium paint and rusty steel
Authors: Kingman F. E. T. , Coleman E. H. , Rogowski Z. W.
Published: July 2010

In certain circumstances steel coated with aluminium paint can emit sparks when struck with a metal striker, and such sparks may ignite mixtures of inflammable gases or vapours in air. The sparks are due to the thermite reaction between iron oxide and aluminium, and therefore are produced only in the presence of iron oxide. The extent of this hazard depends on the nature of the paint; it is increased if the painted steel is subjected to heat.

This work was therefore carried out to determine the effect of the nature of the paint, and the temperature to which the paint might be subjected in use on the tendency to produce incendive sparks (i.e. those liable to ignite inflammable gases or vapours).

The investigation was divided into two sections, the first dealing with certain preliminary studies on the conditions necessary for the production of sparks and the reaction involved in spark formation, and the second consisting of a survey of the possible hazard with a representative series of commercial paints.

No exact correlation between paint composition and liability to emit sparks was obtained, but none of the commercial oil‐bound paints tested gave sparks unless the specimen had been heated to at least 150°.

The paper includes a note by the Senior Chemical Inspector of Factories, outlining the practical application of the results.
The stabilization of soil with resorcinol‐formaldehyde resin for road construction
Authors: Clare K. E. , Packham D. I.
Published: July 2010

The strength and water‐absorption characteristics of three types of soil stabilized with resorcinol/formaldehyde resin have been investigated. The effects of varying (1) the resin concentration, (2) the age of the mixture, and (3) the concentration of added hydrated lime on these characteristics have been examined. The influence of (1) and (3), and of temperature and the presence of certain soil constituents on the setting time of the resin has also been studied.

Small proportions (1 to 10%) of the resin were found to increase the seven‐day strength and reduce the water absorption of the compacted soils. Setting of the resin was accelerated by the addition of hydrated lime and by increasing the temperature.
Heat‐transfer coefficients for industrial gases
Authors: Lohrisch F. W.
Published: July 2010

In order to find out the correct size required for heat exchangers, waste‐heat boilers, gas coolers, etc., heat‐transfer coefficients are needed. Although the available literature provides us with the most recent formulae for these coefficients it is nevertheless difficult to assemble all the technical data of the required dimensions. This is especially tedious for those who deal only occasionally with the subject.

The physical and chemical properties of the gases are given partly in British and partly in metric units. Thus the inevitable conversion needed to reduce all the figures to the one system of measurement requires much time and study if mistakes are to be avoided. Furthermore, the values given for the thermal conductivity of gases differ in a remarkable degree in the various available lists which, also, ignore many of the more recent valuable experimental figures.

The writer has therefore prepared charts for the rapid determination of heat‐transfer coefficients and the presentation of new data based on recent experimental figures for the thermal conductivity of single gases and of gaseous mixtures. These charts are applicable to the gases commonly used in industry.
The mechanism of the catalytic oxidation of sulphur dioxide with a commercial vanadium catalyst: A kinetic study
Authors: Calderbank P. H.
Published: July 2010

The kinetics of the oxidation of sulphur dioxide with oxygen using a commercial vanadium pentoxide catalyst has been investigated. Experimental conditions have been chosen such that the reaction has been carried out isothermally in a flow‐type reactor at temperatures (360° to 450°) and conversions (up to 10%) where the reverse reaction may be ignored.

The results, analysed in conjunction with the relevant adsorption isotherms and rates of adsorption on the clean catalyst, indicate that the rate‐determining step is the rate of reaction between gaseous oxygen and chemisorbed sulphur dioxide.

The adsorption isotherms, which are Langmuir in character, indicate the presence of at least two different types of active centres. Both oxygen and sulphur dioxide are reversibly chemisorbed, oxygen being weakly bound with a heat of adsorption of 6·4 kcal. and sulphur dioxide strongly bound with a heat of 28·8 kcal. There is evidence that both adsorbed species possess considerable mobility on the surface.

Measurements of the rates of adsorption of SO2 and O2 on the clean surface indicate that oxygen is adsorbed by a second‐order mechanism at a slower rate than the observed rate of reaction, whereas sulphur dioxide is adsorbed by a third‐order mechanism at a much faster rate than the rate of reaction. Adsorption equilibrium of SO2 may be assumed, under the conditions of reaction, without sensible error.

Adsorption‐rate measurements of both SO2 and O2 indicate that the number of active centres (defects) increases with temperature, according to a relationship of the type d ln L/dT = A/RT2 where L = no. of active centres, as suggested by Volkenstein (1949).

With SO2, reaction between it and an active centre requires no activation energy, the increase in rate with increase in temperature being due entirely to the increase in the number of active centres. With O2, a small activation energy may be required, although the main increase in rate of adsorption with temperature is similarly due to the increase in the number of active centres with temperature.

Some interesting comparisons are made between the results of these adsorption measurements and recent work on the semi‐conductivity of oxide catalysts, notably by Bevan & Anderson (1950) and Garner, Gray & Stone (1950). Several points of similarity are noted which indicate lines for further work.

Finally, a mechanism for the catalytic oxidation of sulphur dioxide is proposed, the main features of which are: magnified image.
Ideal copolymers and the second‐order transitions of synthetic rubbers. i. non‐crystalline copolymers
Authors: Gordon Manfred , Taylor James S.
Published: July 2010

Theoretical and practical evidence is put forward to show that copolymers can be treated like solutions of small molecules in the interpretation of packing phenomena, and that ideal volume‐additivity of the repeating units in copolymers is frequently realized. On this basis equations are derived for predicting θ, the second‐order transition temperature, of binary copolymers from the two second‐order transition temperatures of the pure polymers and their coefficients of expansion in the glassy and rubbery states. Previous mechanistic theories of the second‐order transition temperature of such copolymers are thus superseded by a general reduction of the problem to the mechanism of thermal expansion. Practical applications to the choice of monomers in producing synthetic rubbers are outlined, and attention is drawn to the importance of second‐order transitions in kinetic measurements on the reactions of polymers.