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JOURNAL OF APPLIED CHEMISTRY

ABSTRACTS O C T O B E R , 1962
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The general arrangement of the abstracts is as follows: 1 .-CHEMICAL ENGINEERING, including also Atomic
Energy, Sewage, Water, Materials of Construction. 2.-FUEL and FUEL PRODUCTS, including also Mineral Oils.
3.-INDUSTRIAL INORGANIC CHEMISTRY, including also Metals, Electrochemical, Heavy Chemicals, Glass,
Ceramics, and Refractories. 4.-INDUSTRIAL ORGANIC CHEMISTRY, including also Heavy Organic Chemicals and
Dyestuffs, Fine Chemicals, Photographic Materials and Processes, Antibiotics and Pharmaceuticals (or Medicinal
Substances). 5.-FATS, including also Oils, Waxes, Detergents, Cosmetic Materials, Rubber, Leather. 6.-FIBRES
including also Textiles, Cellulose, Paper, Plastics, Adhesives, Paints. 7.-APPARATUS and UNCLASSIFIED,

high m.p., high annealing temp. and excellent resistance to creep


l.-CHUIIICAL ENGINEERING AND ATOMIC ENERGY. and corrosion. Specific examples are discussed. G. MACKIWZIE.
General. Reaction kinetics for technical operations of continuous
Materials of construction for chemical plant. F. Molyneaux processes. K. Hedden (Chew.-Ing.-Tech., 1962, 34, 139-147).-
(Chern. Pvocess Engng, 1962, 48, 123--129).-The method of selecting After establishing the important principles for the technical opera-
the correct material for any given application is described under the tion of continuous processes, the determinative equations for the
headings : preliminary selection, laboratory testing, application of calculation of a chemical reactor and the kinetic values are discussed.
data to final selection. The selection and design of gaskets is Since, in practice, even for relatively simple cases the complete set of
specifically dealt with. Tables are given of the trade names, com- differential equations is so complicated that no strict complete
positions and equivalents in various countries of grades of stainless solution is possible, i t is shown how operation with only a few major
steel. The physical and mechanical properties of a number of values and the drastic omission of other factors leads to practical
constructional materials are listed, together with their room-temp. calculations. In this way, a series of idealised basic types of reaction
corrosion resistance to a variety of media. Allowable stresses and apparatus is obtained. The influence of the neglected terms can be
working temp. for 2 in. dia. pipe in a variety of materials of con- estimated on these basic types. By considering the most important
struction are also given. K. RIDGWAY. effects, the conditions obtaining in the operating plant can be
approached step by step. The characteristic values for the basic
Pilot plants and technical considerations. L. W. Hamilton, types of reactors arc tabulated and a list of formulae and signs is
W. F. Johnston and R. D. Petersen (Chem. Engng Progr., 1962, 58, given. (11 references.) M. SULZBACHER.
No. 2, 51-54).-A general discussion of the principles of scale-up Strength of pressure vessels in heat and cold. I. Class
of chemical plant is followed by a more detailed treatment of a (Gem.-1ng.-Tech., 1962, 34, 242-253).-Present methods of calcula-
tubular reactor, to show which dimensionless groups are of impor- tion of strength of pressure vessels at high, normal and low temp.
tance. The simulation of a plant by an analogue computer is also are reviewed. Examples under practical conditions are taken to
treated in general terms. K. RIDGWAY. obtain more accurate calculations for steel and other materials and a
Statistically designed pilot plant experiments. R. S. more economical employment of the vessels. (34 references.)
Davis (Chem. Engng Progr., 1962, 58, No. 2, 60-63).-A system M. SULZBACHER.
involving two reactants, which may produce either the desired Handling hazards of organic finishes. D. C. Sayles (Metal
product by one reaction, or an undesired and reaction-inhibiting Finish., 1962, 66, 55-61).-Fires are categorised into three claases :
product by another, was assigned a complex rate equation, which from materials that smoulder ; inflammable liquids ; and electrical
also included the inhibiting effect of a possible impurity in one hazards. The appropriate fire fighting agents and their use are
reactant. The parameters of this equation were then found by a described. Various hand fire extinguishers, atm. contamination
factorial experiment so designed that a highly non-linear, and non- detection devices and techniques to eliminate or reduce toxic
linearisable, mathematical model could be fitted directly, by a environments for those handling org. finishes are described. Tables
computerised process, t o the data. K. RIDGWAY. of the nature and severity of the hazards met and rccomrnended
control measures and of toxic effects are given.
How to instrument a pilot plant. J . T. Ward and J . H. Heat1 C. H. COWPER-C.OLES.
(Chem. Engng Pvogr., 1962, 58, No. 2 , 64--66).--A general survey Safety considerations in relation to glove-box design.
of the instrumentation requirement is given, a suggested course of V. Griffiths ( W . K . Atomic Energ.y Aaithovaly Rep., 1962, AHSB(S)R 18,
action in instrument choice and installation is sketched out in 27 pp.).-Means of reducing failures and accidents in glove-box
numbered sequence, and possible difficulties described. handling of toxic materials are outlined. The influence of toxicity
K. RIDGWAY. of the material, its quantity, form and specific activity ; the type of
Process scale-up by sequential experimentation and operation and the grade of operator on glove-box arrangement and
mathematical optimisation. J. Novack, K. 0. Lynn and E. C. construction are considered. Maintenance and sampling should be
Harrington (Chem. Engng Progv., 1962, 58, No. 2, 55-59).-A able to be carried out through glove parts and transfer hatches.
factorial type of experimental programme is described, which was Perspex is the best available construction material but because of
carried out on a 100 gal. and a 4000 gal. size reactor for a poly- inflammability is not ideal ; window areas should be reduced to a
merisation. The response surface a t the pilot level was calculated min. and of laminated glass where fire risks are likely to exist.
from a restricted no. of runs, and the smaller no. of large scale runs Where inflammable materials are present in quantity, plastic
were designed to find differences between pilot and large scale materials reinforced with glass are not recommended. Double
behaviour. The description is entirely algebraic, the process para- boxing is not recommended but a n inward flow of air appears
meters which were varied being unspecified. K. RIDGWAY. generally desirable. Filters attached to the box should be fire-
Platinum bursting discs in protection of chemical plant. resistant : recommendations are made for the use of liquid gases,
J . E. Philpot (Platinum Met. Rev., 1962, 6 , 42-46).-Two alloys of etc. Solid (e.g., ternary eutectic) fire extinguishing materials should
1 3 have proved particularly useful for bursting discs owing to their be used. (12 references.) J . W. TAYLOR.
ii-329 ii-330
E
ii-33 1 1 . 4 H E M I C A L ENGINEERING A N D ATOhlIC ENERGY ii-332

Atomic Enorgy, otc. centre of which is placed the metal sleeve (fixed or moveable)
housing the plug of waste. A gantry-crane assists transport and
Properties of tungsten with reference to nuclear power. handling of transfer buckets. Economics are discussed brietly ;
B. J . Thamer ( U S . at. Energy Comm. Rep., 1962, No. LAMS 2675, 30-40 shafts are needed annually at Saclay. 11'. J . BAKER.
57 pp.).-A selected, annotated bibliography. (259 references.)
c. v.
Methods and measurements of nuclear reactor time and
frequency responses. J. D. Cummins ( U X . Atomic Energy Matorials Handling.
Authority Rep., 1961, A.E.E.W.-M.185, 14 pp.).-Methods for Rheology of suspensions. F. Schultz-Grunow (Chem.-lng.-?'ecA.,.
the determination of reactor response include transient response, 1962, 34, 223-230) .-The experimental determination of the flow
frequency response, statistical analysis techniques ; alternative properties of suspensions in the transition zone between liquid and
methods of processing statistical signals included digital with and solid as well as air suspensions is reported. Thixotropy and wall
without record, analogue with and without record analysis, etc. segregation effect are particularly discussed. The effect: of solid
The choice of method for the determination of dynamic characteris- flow-rate and particle dia. on pressure drop in pneumatic transpor-
tics, depends on the reactor time and equipment available. The use tation is also studied. (27 references.) M. SULZBACIIER.
of reactor models and adaptive control in improving the economy
of power producing nuclear reactors is outlined. (19 references.) Laminar boundary characteristics in a compressible flow
J. W. TAYLOR. over porous surface with suction. S. P. Reyle (Dissert. .Abstr.,
1961,22, 1565).-Emphasis is placed on the location of the separation
Rapid radiochemical separations. Y. Kusaka and W. W. point in an adverse pressure gradient. Assumptions made in this
Meinke (Nut. Acad. Sci. Wash., Nucl. Sci. Series, 1961, NAS-NS-3104,
125 pp.).-The first section deals with prep. and handling of target method are that the boundary layer equations of Prandtl are valid.
that the Prandtl no. is unity, viscosity-temp. relation is linear and
materials, irradiated samples, etc. A second section gives separation
techniques including hot atom recoil, fission gas recoil, cyclation the surface has a uniform temp. distribution. No restriction is
placed on suction distribution. The ,Karman-Pohlhausen integral
bombardments, daughters of a-emitters, daughters of p-emitters, method is applied to a sixth degree velocity profile and a seventh
isomeric transition routes ; distillation techniques, selective gas
degree stagnation enthalpy profile. Numerical examples illustrate
adsorption, emanation methods, glow discharge, volatilisation, the retarding effect of suction on separation. G. MACKENZIE.
vacuum treatments, etc., solvent extraction, precipitation, ion and
isotopic exchange and electrochemical methods. A third section Two-phase flow in vertical tubes. D. J. Nicklin, J. 0 . TVilkes
tabulates half-life, production reaction, target and separation and J . 1;. Davidson (Trans. Instn chem. Engrs, 1962, 40, 61-68).-
procedures for a very large number of isotopic species from He to The velocity of air bubbles rising in a 1 in. dia. tube was measured
ES6Md. (273 references.) J. W. TAYLOR. by a cinematographic technique. The bubbles were all of thr slug
type, having a dia. approximating to that of the tube, and a length
Determination of radio-caesium and radio-strontium greater than their dia. The velocity relative to the liquid agreed
in plant solutions. Anon. (U.K. Atomic Energy Authority Rep., with the Ihmitrescu theory. Abs. rising velocities were obta.ined by
1962, P.G. 282 (W), 9 pp.).-Known amounts of Cs and Sr carriers measurement and correlated using a fact.or whose value w a s a
are added to the sample along with some Ce scavenging carrier, the function of slug length and liquid velocity. An equation is devcloped
solution being passed down a column of Amberlite 1.R.A.-400 in the which adequately predicts the voidage in the tube as a function of
hydroxide form ; CO, must bc excluded. Sr is precipitated from the the gas velocity. (10 references.) K. RIDGWAY.
effluent as SrCO,, dissolved in HCl, and precipitated as oxalate prior
to measurement of the @-activity. Cs is subsequently precipitated Flooding velocities for air and water in vertical tubes.
as CsCIO, and the y-activity measured. For Sr the precision was G. 13. Wallis ( U . K . Atomic Energy Authority I?@., 1961, A.E.E.W.-
3.3% and the concn. range 3.3 x 108 t o 1 . 2 1 ~0' d.h.m. and for R123, 17 pp.).-Limiting or ' flooding ' velocities are determined in
~ to 6 x lo6 d.h.m.
Cs, 2.776 and 2 . 5 lo4 J. W. TAYLOR. countercurrent annular flow of air and water in a vertical tube ;
thc relevance of this work to the problems of ' burn-out ' is discussed.
Separation of strontium-90 and yttrium-90 with ion- The data are correlated in terms of dimensionless groups for the gas
exchange papers. €'. C. Stein (Analyt. Chew., 1962, 34, 352-354). and liquid velocities and equation is given for describing flooding in
--A rapid complete separation of OOSrfrom O0Y in a 5 fig.-sample packed towers. For high liquid velocities a t which cocurrent slug tlow
can be made by ascending chromatography on paper impregnated can occur, considerable scatter in results occurs. An equation is given
with (i) -4mberlite III-120, and citrate buffer (pH 3.8) as eluent, for the gas velocity a t which no liquid will run down the tube, inde-
(ii) Amberlite IR-4B (OH form), and water as eluent, or (iii) pendent of the design of end connections. Although the dimensionless
cellulose phosphate, and 5 x-HC1 as eluent. Spots are located with a groups used to correlate flooding data and burnout heat flux in /pool
p-detector and the chromatogram traced with a p-particle recording boiling are similar, the mechanisms in the two cases are not identical
densitometcr. W. J. BAKER. and care should be taken when drawing comparisons between the two
Determination of carbon-14 in reactor coolant gas. Anon. processes. (15 references.) J. W. TAYLOR.
( U . K . Atomic Energy Authority Rep., 1962, P.G. 287 (W), 7 pp.).- An inferential meter for the measurements of gas at high
The gas sample is absorbed in aq. KOH, CO, is liberated with H,SO, rates of flow. C. P. Ilenshilwood (Gus Times, 1962, 96, No. 969,
and re-absorbed in aq. Ba(OH),. Any CO in the sample is oxidised 13---14).--The gas passes through a narrow orifice. Before the orifice,
by I,O, to CO, which is also absorbed in Ba(OH),. The carbonate a pipe leads gas to the meter and the gas returns through a second
precipitates are gelled separately with a liquid scintillation gel orifice to the main flow after the first orifice at a n angle of
and the @-activitymeasured in a liquid counter calibrated against a The dia. of the second orifice must be accurately controlled.
BaCO, standard. J. W. TAYLOR.
- 15".
K. M. H.
Retention of Assion-products by common minerals.
Application to medium-activity emuents. J. M. Auchapt
(Rapp. Cent. Et. nucl. Saclay, 1962, No. 2114, 24 pp.).-Fixation of
OOSron calcite in presence of PO,*- is examined more closely, and Thermal.
the method (without added PO,*-) is extended on a small-scale to Measurement of surface temperatures with thermocouples.
the fixation of radioactive Sr, Cs, Ru, Ce and Zr from neutral, acid P. Vernier (Happ. Cent. Et. nucl. Grenoble, 1961, No. 2091, 50 pp.).-
or alkaline effluents ( N 10-2 pc/ml.) on to powdered cryst. minerals. Construction, use and accuracy of temp. probes (plain or sheathed)
All 17 minerals (especially witherite and cerussite) retain < 90% of for heat-insulated surfaces are discussed. Selection pf suitable
one element and varying amounts of the others ; the retention factor probes is based on standardisation against cylindrical calibrated
for Ru is higher than for any other method. Application t o effluents walls ' for which temp. (100---200") are known t o within 10.05"
at Marcoule, etc., is impracticable mainly because of too rapid and heat loss to within &- 1yo. When insulated by 0.05 mm: thickness
saturation of minerals and large vol. increase in active mud. of mica, the Jakob and Gouffi probes are the most accurate for temp.
W. J. BAKER. measurements of walls heated by the Joule effect, the max. deviation
Storage of plugs and experimental devices from reactors. of A0 (wall-to-probe temp. change) being i 0 . 0 3 " for max. heat-
P. Cerre and E. Mestre (Rapp. Cent. Et. nucl. Saclay, 1961, No. 2084, losses of -0.15 Wjsq. cm. The method also permits determination
12 pp.) .--Provision is made for long-period underground storage of of apparent heat conductivity (k)of the insulating material and also
certain radioactive wastes by a series of steel-lined vertical shafts the contact k between wall and probe t o within 1 3 7 4 and :e lo%,,
( 16 ft. deep, 3 f t . wide, 4 ft. apart) packed with concrete in the
N respectively. ml. J. R A K E R .
ii-333 1 . 4 H E M I C A L ENGINEERING AND ATOMIC ENERGY ii-334

Heat transfer to liquid fluidised systems and to suspensions Sampling and testing of steam. Determination of average
of coarse particles in vertical transport. J. F. Richardson and steam purity. P. Hamer and H. Evans ( J . Inst. Fuel, 1961, 34,
J. W. Smith (Trans. Instn chem. Engrs, 1962, 40, 13-22).-Heat 535-538).-The total solid matter in a sample of steam is deter-
transfer coeff. between water and the wall of a heated 2 in. dia. mined by condensation and evaporation of the sample under
brass pipe were measured a t various flowrates, with ballotini, gravel, controlled conditions followed by weighing the residue. The
Fe, Cu and Pb particles of 7-60 mesh size in a fluidised condition apparatus and technique are described. This method is not a
and under transport conditions. The increase in the coeff. is less substitute for conductivity meter methods. D . DE VOY.
for transport conditions. The increases are correlated with particle Fuel cells. W. T. Reid and A . P. Edson (Battelle Tech. Rev.,
concn. and particle properties ; the max. increase obtained being 1962, 11, No. 6, '.-7).-A review of their present status and their
0 cal./h. ft., ' c . (18 references.)
~ 3 5 lb. K. RIDGWAY. potentialities. C. v.
Heat transfer in turbulent and laminar flow in annular Practical experience in the selection of high-pressure
slots. K. Stephan (Chew.-Ing.-Tech,,1962, 34, 207--212).-Dunng compressors. B. Linnartz (Chem.-Ing.-Tech., 1962, 34, 237-
turbulent and laminar flow in annular slots heat may be transferred 241).-Useful data for the ordering, lay-out and planning of high-
either by the inner tube only or by the outer tube only, or by both pressure compressors are collected. The advantages and dis-
tubes. This heat transfer can be described by modified forms of the advantages of certain types of construction, experience with struc-
Hausen equations valid for flow through pipes. The equations tural elements, simplified formulae for estimating the necessary
derived arc suitable for calculation of the heat-transfer index in driving power, area and volume requirements and purchase price
forced turbulent and natural laminar flow in annular slots with are discussed. M. SULZBACHER.
all ranges of diameter ratios. (16 references.) M. SULZBACHER.
Design and operation of an air-cooled thermoelectric
Development of temperature profile for turbulent heat refrigerator. T. M . Elfving (Kiltetechnik, 1962, 14, 7 6 - 4 0 ) ,
exchange in apipe. R. €3. Johnk (Dissert. Abstr., 1961, 22, 1539).- W. H. KEMP.
Data on radial temp. distribution were obtained in the entrance of
a fully developed turbulent flow of air in a pipe. Uniform wall heat Treatment of water. Sutcliffe, Speakman & Co. Ltd. (Inventors :
flux was employed in the heat transfer system, and full temp. F. R. Houghton and J. C. Cuerdon) (B.P. 869,751, 16.5.57).-An
profile was developed. The validity of an analogy between heat and aq. solution of N,H, is fed into the (boiler-feed) water, pre-heated to
momentum transfer was examined. Temp. profiles close to the wall 32-54" and having p H -9, a t a rate such that 10-30% of N,H,
attain fully developed shape rapidly in the heat transfer section. in excess of that required to react with the dissolved 0, is intro-
Time was demonstrated to have an effect on the eddy diffusivity duced into the water. Thereafter the mixture is brought into
profiles. G. MACKENZIE. contact for a period of 4 -30 sec. with active C having a particle
size of 12-16 B.S.S. and a surface area of 4 1000 sq. m. per g.
Performance of thermoelectric cooling elements. 0 . J . M. JACOBS.
Steiger (Kultetechnik, 1962, 14, 69-75).-Based upon Altenkirch's
theory of thermoelectric elements, operational characteristics for
refrigeration performance and efficiency are developed. The Unit Operations.
refrigeration capacity of a single element is discussed. a survey being Kinetics of technical ammonia synthesis. A. Huber (Chem.-
given on the efficiencies obtainable, based upon which performance Ing.-Tech., 1962, 34, 147--153).-Assuming that the Temkin
conditions and refrigerating capacities are described. Questions equation is suitable for the calculation of an ammonia synthesis
relating to the determination of element dimensions are dealt with. furnace in stationary state, i t is shown that the exponent of the
W. H. KEMP. equation is dependent on pressure and temp. As, however, a
theoretically possible determination of the constants of the reaction
Services. rate for NH, decomposition-does not lead to satisfactory practical
Design of modern boiler feed pumps. H. H . Anderson (Proc. results, the Temkin equation is not applicable. With a modified
equation, a new method is given to determine the function of the
Instn mech. Engrs, 1961, 175, 641-653).-Feed pumps for large process parameters by temp. measurements in an adiabatic industrial
steam power stations must accept severe thermal shocks in order reactor. (12 references.) M. SULZBACHER.
to protect the boiler. For safe operation the boiler must have an
uninterrupted supply of feed water which is within -55" of its own Substance movement through piled and porous materials
temp. The results of thermal shock tests on feed pumps of the by diffusion, molecular movement and laminar and turbulent
thermally symmetrical barrel type, designed to give symmetry of flow. 0. Krischer (Chem.-leg.-Tech., 1962, 34, 154--162).-The
construction, of flow and of stresses in order to withstand rapid substance movement through piled materials and porous bodies is
temp. changes without distortion of alignment, are reported. taken t o be analogous t o the flow through pipes, the structure of
Erosion is avoided and performance is improved by mathematical the porous bodies being characterised by factors. Most important
control of acceleration within the pump and generous use of stainless is the so-called ' path factor ' the evaluation of which is discussed in
steel. J . M. JACOBS. detail. The theoretical calculations are confirmed by experiments on
heaps of spheres. The phenomenon of turbulence can be explained
Grapho-analytical method to establish the efficiency of by Carnot's equation and can be calculated in advance.
various distributions of the heating surfaces by convection in M. SULZBACHER.
steam boilers. M . Postelnicescu and P. Vezeanu (Bul. Inst. polit. Comparison of sugar diffusion plants. K. Adamik and H.
Bucuresti, 1961, 23, 135--147).-Different ways of heat transmission Mayer (Chem.-Ing.-Tech.,1962, 34, 218-221).-1n a comparison of
to the various surfaces by convection in steam boilers are represented processes of sugar diffusion plants operating under different con-
by a general graph-analytical method. The variation of the efficiency ditions, the abrasion of four characteristic types of beet pulp was
of heat exchange and its relation with the temp. of the combustion first investigated. An improved equation for extraction is developed
gas are discussed. In an example of application, the optimal temp. taking into account the factors of the second Fick law. Analogy
of air preheating is established and the economy of the metal material studies of heat- and mass-transfer in beet pulps allow the deter-
is considered. (In French.) M. SULZBACHER. mination of diffusion times which tally well with practical results.
Effect of hydrazine on the microdeterminationof dissolved Industrial diffusion plants are compared. M. SULZBACHER.
oxygen. M. Needleman ( J . appl. Chem., 1962, 12, 294-305).- Interfacial resistance in the carbon dioxide-water system.
A method for the determination of 0 4 . 0 2 0 p.p.m. of 0, dissolved F. Goodridge and D. J . Bricknell (Trans. Instn chem. Engrs, 1962,
in pure water is described. The basic ' reversed-reagents ' technique 40, 54-60).-Absorption rates of CO, into water in a stirred cell
gives a precision (standard deviation) of 0.0008 p.p.m. N,H, were determined with various long-chain acids and alcohols forming
interference is due to its non-compensated reaction with MnO, a surface layer. The max. value of the interfacial resistance t o mass
during the Winkler reactions. The elimination and origin of sources transfer was approached as the surface became 100% covered with
of error are described in detail. (21 references.) 0 . M. WHITTON. the long-chain mol. The resistance was not sensitive to rate of
Sampling and testing of steam. Wetness fraction of steam. agitation, or to surface tension under agitated bulk liquid conditions,
I). C. Gunn CJ. Inst. Fuel, 1961, 34, 538440).-Errors in the and i t is suggested that a penetration model is inappropriate at low
sampling due t o the two-phase nature of the system, i.e. water on agitation rates in the presence of films. (16 references.)
the pipe walls and steam in the core, are discussed. A steam separator K. RIDGWAY.
t o measure the moisture is suggested as being the most reliable Mass-transfer gaslliquid in a stirred vessel. Influence of
method of estimating the wetness fraction. D. DE V O Y . agitator shape, rate of rotation and gas throughput on the
ii-335 1.-CHEMICAL ENGINEERING A N D ATOMIC ENERGY ii-336
.bubble surface and mass transfer. F. H. H. Valentin and B. V. the coarser fraction is returned by a classifier from the leaching
Preen (Chem.-Ing.-Tech., 1962, 34, 194--199).--When the rate is not tank to the grinding mill, and only completely leached fines are
determined by any chemical reaction, the mass transfer between discharged from the process. K. RIDGWAY.
gas and liquid in a stirred vessel depends only on the specific bubble Mass exchange in extraction columns. A. F. Orlicek (Chem.-
surface, the mass transfer index and the concn. gradient. For the Ing.-Tech., 1962, 34, 222-223) .-Preliminary results of investiga-
+
system air CO,/water, the bubble size distribution and the average tions on mass exchange in extraction columns, particularly pressure
bubble size for four types of agitator at different rates of rotation loss in pulsation, are given. M. SULZBACHER.
and gas velocities are measured by a photographic method. The Emciency of liquid extraction processes. C . V. Jeffreys
specific surface is evaluated from the determination of the gas hold- (Chem. Process Engng. 1962, 43, 117-1 19).-The mechanism of mass
up. The specific surface depends only on the energy expenditure transfer between two liquid phases is described, and the film theory
and gas velocity and not. on the type of agitator, which might be compared with the penetration theory. Interfacial turbulence
attributed to the coalescence of the bubbles. The type of stirrer phenomena are describcd, and the effect on contactor efficiency
and the system of gas introduction, however, determine the max. estimated. The mechanism of coalescence of droplets is given, and
quantity of gas which can be properly distributed without flooding
i t is shown that the coalescence of a droplet with a continuous
the agitator. The mass-transfer indices obtained are independent liquid phase results in an oscillation and the production of a smaller
both of the energy consumption and the gas velocity. This is droplet than the original : the process then repeats itself. (18
attributed to the overriding influence of the fairly constant bubble references.) K. RIDGWAY.
ascension rate. (33 references.) M. SULZBACHER.
Control of distillation columns. H. H. Rosenbrock ( T r a n s .
Mass transfer between a liquid jet and a countercurrent I n s t n chem. Engrs. 1962, 40, 35-53).-A general outline of the
gas stream. [A] Absorption of carbon dioxide diluted with control problem in a column is given, and the secondary effects,
nitrogen into water jet at 25" and at atmospheric pressure. chiefly hydrodynamic, are listed. It is shown that for satisfactory
[B] Vaporisation of water Jet into dry nitrogen at 25" and control, the phase !ag introduced into the control loop by the
atmospheric pressure. D. R. Woods (Dissert. Abstr., 1961, 22, secondary effects must be <45O., Criteria and methods are given,
1931--1932).-A laminar distilled water jetN 1.5 mm. in dia. that using the ' disturbance function concept, by which the quickest
fell intact from a bell-shaped nozzle to a receiver tube was contacted attainment of a steady state may be ensured. A simulation on an
with countcrcurrent gas flowing a t 1-10 ft./sec. This apparatus was analogue computer, of a column controlled by reboiler steam flow
used for the absorption of CO, and 20% CO,-800,; N, into the jet, and by reflux ratio, is reported. Interaction renders control less
and the vaporisation of the water jet into N,. The kinetics of CO, good when both control loops operate than when either is employed
absorption were correlated with Higbie's unsteady state absorption alone. Suggestions for further work are made. (37 references.)
theory, the vaporisation of water jet with the Chilton-Colburn I<. RIDGWAY.
j-factor based on thc ' relative' gas to liquid surface velocity to Minimum reflux rate for multicomponent distillation
within &260/, or the bulk gas velocity within *sayo. Gas turbulence systems by rigorous plate calculations. R. C. Erbar and R. N.
near the end of the jet may complicate the results. Maddox (Canad. J . chem. Engng, 1962, 40, 25--30).-An iterative
F. C. SUTTON. method is described in which plate-to-plate calculations are made
Relation between the Margules and the van Laar equations : from both ends of the column to the pinch zones, and from the feed
the square-root equation. J.-E. A. Otterstedt and H. W. Missen plate outwardly to the pinch zones. The rectifying and stripping
(Canad. J . chem. Engng, 1962, 40, 12--15).-The excess free energy pinches are then assumed one plate further from the feed point, and
of mixing is divided by the product of the two molar fractions of the the calculations repeated ; when repetition of this procedure gives
components in a binary system, to give a parameter which may be a reflux rate change which is within any limit which may be set, the
expanded as a power series in one of the molar fractions. This is a iteration is complete. The convergence is assured and rapid. The
generalised form of the Margules equations. I t is related inversely method has good stability and is suitable for computer calculation.
t o the van Laar equations. The new equation uses a power series in (26 references.) I<. RIDGWAY.
(molar fraction)*, which has some advantages in the correlation of Binary vapour-liquid equilibrium data thermodynamic
data on systems consisting of CC1, and an alcohol. Results are given consistency tests. B. C.-Y. Lu, I. H. Spinner and J . C. K. Ho
for the XI,--MeOH system. (19 references.) K. HIDGWAY. (Canad. J . chem. Engng, 1962, 40, 16-24).-Seven criteria which
Modern separating processes. f'. Grassmann (Chem.-1ng.- binary system log (activity coeff.) plots must satisfy are listed,
T e c h . , 1962, 34, 171--177).-The development of thermal separation based on slope, intercept, 25, 50 and 7574 values and the relations
processes, particularly rectification, is charncterised by the solution between these quantities. Allowable divergencies are suggested,
of increasingly difficult problems. Processes depending on the and the tests applied to a number of binary systems. Two systems
difference in the equilibrium composition of two phases are discussed. are examined in greater detail : toluene-n-octane and ethanolL
Separation of isotopes (H,O and D,O) in Kuhn columns, vacuum water. (24 references.) I<. HTDGWAY.
rectification i n the Luwa rectificator and step-wise rectification in Rectification by molecular distillation. H. Ratte (EnJoI u .
two spatial dimensions (still under development), including elecstro- Kohle, 1962, 15, 179-181) .-Formulae are given whereby the concn.
phorcsis antl paper chromatography, are described. (12 references.) ( y ) of a light component in successive condensates, and that ( x ) in
M. SULZBACHEK. the residues from the corresponding vaporisers, are calculated for
Steady-state distribution-a new technique. J. G. Fleetwood given conditions, a ' pseudo-equilibrium ' being assumed. A no.
(Chew. Process Eizgng, 1962, 43, lOG-lOS).--A description is given corresponding to the no. of theoretical plates in a McCabe-.Thiele
of an all-glass counter-current distribution apparatus, built up in diagram is found by plotting y against x. (Cf. J..4.C. Abstr., 1961.
units of five cells. A diagram of a single cell, and its mode of ii, 7). A. It. I'EARSON.
operation are given, Each cell contains 25 ml. of each liquid phase : Thin-layer evaporation in the high-vacuum range. T h .
agitation through 30" causes equilibration to occur. The cells are Peck (Cham.-Ing.-Tech., 1962, 34. 192-194).-After a discussion of
allowed to settle a t 15' to the horizontal, and then rotated through the fundamental problems of thin-layer evaporation in high vac.,
90". which causes the upper phase to transfer to the next cell. the construction of the Kotafilm thin-layer evaporator is described.
Rotation through 90" in the opposite direction transfers the lower M. SULZBACHER.
phase to the next cell, in the opposite direction to the light phase Influence of pipe diameter and length on the performance
movement. The method is applied to the separation of a-acids of of evaporation apparatus with automatic circulation. E.
hops. IC. RIDGWAY. Kirschbaum (Chew&.-Ing.-Tech., 1962, 34, 183--.192) .--For the
Mass transport mechanism of leaching processes. E. determination of the heat-transmission index for evaporators with
I'eters and J. Skrivanek (Canad. J . chem. Engng, 1962, 40, 1-5).- automatic or natural circulation, Cu tubes of 16, 35, 52 and 102 mm.
An equation is set up for the mass transfer from a particle which is dia. and 1, 2, 3 and 5 m. length were employed, 1. 2, 3 and 5 tubes
so small that it follows the liquid eddy currents, and thus behaves being installed a t one time. Liquids used in the experiments were
as if surrounded by a non-moving rigid medium. The equation is distilled water and sugar solution. The evaporation temp. was
solved to give, under certain restrictions, an expression giving the IOO", or 50" in vac. operation. The results of the measurements antl
fraction of unleached material, a t any time. The equation was the processes occurring in the evaporator tubes are discussed.
tested on the basic leaching of a U,O,-containing ore, the particle M. SUIZBACHBR.
size distribution of which was measured. A tlowsheet is suggested Influence of condensation and evaporation on mass
for an improved process in which grinding is followed by leaching ; exchange in rectification. ti. Hochgesend (Cher,r.-lng-'l'erk.,
ii-337 1.-CHEAIICAL ENGINEERING A N D ATOMIC ENERGY ii-338
1962, 34, 17R--- 182).-The influence of condensation and evaporation relating to vitamin B,, (I) in activated sludge ai d its use as a feed
on rectification in a pipe column can be determined by the theory supplement to chicks and pigs and the techniques for obtaining I
of the presence of two films, whereby the mass exchange is treated solutions of high purity are described. Factors influencing the I
as a superimposition of diffusion and convection and the boundary contents of sewage sludges are outlined. (73 references.)
layer is assumed not to change under the influence of the convection F. C. SUTTON.
flow. The reldtionship derived has been confirmed byexperimentsover The time factor in biological filtration. D. Meltzer ( J . Inst.
a wide range of condensation and evaporation. M. SULZBACHER. Sew. Purij., 1962, 169-175).-Calculations show that two-stage
Heat- and mass-exchange in freeze-drying of porous filtration, double-depth filters, or 1 : 1 recirculation increase deten-
materials. H. G. Kessler (Chem.-Ing.-Tech.,1962, 34, 163-171).- tion time by 19D/, above that of single-stage filters receiving the
The processes of heat- and vapour-movement in porous solids during same daily flow or volumetric loading. Similarly, three-stage
sublimation drying are analysed with the aid of known physical filtration, triple-depth filters or 2 : 1 recirculation increase detention
laws. The course of sublimation drying of various porous materials t.ime by 30%. Optimum flow rate is lower the weal-er the sewage.
such as piles of glass spheres, a building cement, milk and apple 0. M. WHITTON.
slice, was experimentally investigated. The influence of vapour Effect of different grades of filter medium on the purification
movement in the pore system and of the thermal conductivity in of sewage in biological Alters. W. P. Krige ( J . Inst. Sew. Purif..,
the material on heat transfer to the sublimation surface was deter- 1962, 150--157).-A flow sheet is given of Krugersdorp (S. Africa)
mined. In separate studies, the relationship between thermal sewage purification works which deals with 1.4 x lo8 gal./day of
conductivity of porous materials and gas pressure was established. sewage, without pumping. The plant loading is analysed. The
Apparatus for freeze-drying are illustrated. (12 references.) performance of different grades of medium, including the effects of
M. SULZBACHER. increased loading, seasonal variations, and size of medium ; have
Slit and multi-nozzle arrangements in the drying of moist been studied. The first 2 years of operation of single filtration are
surfaces by hot air jets. H. Glaser (Chem.-Ing.-Tech,, 1962, 34 given. 0. M. WHITTON.
200-207).-The flow behaviour of a flat jet striking a surface and Shock loading activated sludge with spent sulphite pulp
the mass transfer obtained is subject to the same laws as those of a mill wastes. A. F. Gaudy, jun. ( J . Wnt. Pollut. Contt.ol!Fed., 1962,
round jet. Experimental results are presented in dimensionless 34, 124--135).-Shock loading with a waste to which a plant had
form, expressing the influence of the jet velocity, the distance not been previously acclimatised was studied. Response had to be
between the jet and the material being dried, the width of the slit accompanied by some degree of chemical characterisation of the
of the nozzle and the roughness of the material surface. The flow waste, but engineering decisions concerning multiple waste streams
relationships with multi-nozzle arrangements are very complicated, must also be borne in mind. Glucose-acclimatised sludge was
the drying rate being strongly influenced by the geometrical forms successful when used with neutralised spent liquors according to the
in addition to the air velocity. The experimental results can be parameters employed in the investigation. (13 references.)
presented in a dimensionless form in this case also. Various nozzle B. F. FULLAN.
arrangements are compared. M. SULZBACHER. Removal and disposal of synthetic detergents in sewage
Heat treatment and drying of fine-particle material in the effluents. S. G. Burgess and L. B. Wood ( J . Inst. Sew. Puri-f.,
riffle tube. F. Schaub (Chem.-Ing.-Tech., 1962, 34, 213--218).-In 1962, 158--168).-A process for preventing foam formation in a new
this operation, the fine-particle material is conveyed pneumatically diffused-air plant has been investigated to a pilot-stage treatment
through a heated tube and undergoes heat exchange by direct of 2000 gal. of settled sewage. The sewage is vigorously aerated so
contact with the walls. The factors significant for drying efficiency that most of the detergant concentrates in the stable foam which
and heat consumption are indicated. Several years’ experience in forms on the liquid surface. I t can then be removed, preferably by
the application of the riffle tube (Drallrohr) shows that particularly activated sludge. The detergent concn. of sewage can be reduced
favourable results have been obtained in the rapid drying of temp.- from about 8 p.p.m. to 1-2 p.p.m. in 6 min. Diffusers of the
sensitive materials and with the exchange of large amounts of heat Aerox type P35, preferably tubular, are used for producing the
per kg. of material. Examples of industrial applications are the small bubbles essential for efficient detergent removal.
drying of polyethylene powder and the heat treatment of lime dust. 0. M. WHITTON.
M. SULZBACHER. Control of effluents discharged into rivers. W. F. Lester
Simulation of chemisorption processes taking place in ( J . Inst. Sew. Purlf., 1962, 119--130).-Legislation governing the
countercurrent packed columns. N. A. Gol’dberg and V. I. control of effluents discharged into rivers and its administration are
KucheryavjX (Dokl. Akad. Nauk SSSR, 1962, 142, 1134-1 136).- discussed. 0. M. WHITTON.
I t was desired’ to determine criteria and conditions of similarity of Analysis of lipids in sewage, sludge and industrial wastes.
processes investigated and to establish a relationship between model R. C. Loehr (Dissert. Abstr., 1961, 22, 1944--1945).-The wet liquid
and original. I t is shown that the physical basis of postulated sample is homogenised with CHCl, and MeOH. The mixture is
conditions for comparison is determined by the mechanism of diluted with CHCl, and water and the CHC1, layer is collected.
localised actions of chemisorptional process in countercurrent The advantages of this method over the Soxhlet extraction proc.edure
packed columns. Essential conditions for similarity are listed and are given. The method extracts lipids more effectively and also
equations are derived to establish mathematical relationships compound lipids. The compound lipid % rises with biological
between various factors in model apparatus and original. (12 treatment. Dried sludge contains 39, activated sludge 29, primary
references.) P. W. B. HARRISON. sludge 15 and raw sludge 14% of compound lipids.
Hydrodynamics of the fluidised bed. I. Teoreanu and V. F. C. SUTTON.
Cimpu (Bul. Inst. polit. Bucurefti, 1961, 23,83-91).-The influence Deep well disposal of industrial wastewater. C. W. Querio
of certain factors, particularly of height and dia., on the expansion and T. J. Powers (,I. Wat. Pollut. Control Fed., 1962, 34, 136-144).-
of a fluidised bed is experimentally investigated. The signification In selecting a site for this manner of disposal, a thorough geographical
of the ‘ form factor ’ is discussed and a method for its practical knowledge of the terrain to be used was required, especially a t depths
determination is proposed. (From English summary.) of 9000--12,000 ft. below the surface. The porosity and permeability
M. SULZBACHER. of the strata were also of prime importance. Details are given of the
Numerical solution of partial differential equations repre- viscosity of the media which could be disposed in this manner and
senting Axed bed reactions. D. U. von Rosenberg. P. L. Durrill the pressure required to inject i t into the rock formation. I t is
and E. H. Spencer (Brit. chem. Engng, 1962,7, 186--189).-Equations pointed out that waste material can interfere with potable water
are set up for the behaviour of a packed bed reactor of cylindrical taken from higher levels and it is desirable ts assess the pressure
shape, in which reactants flow with a flat velocity profile, react relationships involved before designing a system.
exothermically in an irreversible first-order reaction, and give up B. F. FULLAN.
heat to the walls. The equations are solved numerically, using
Crank-Nicolson finite difference methods, giving an integrating Carbon-chloroform extract in water. Subcommee on Organic
procedure very suitable for digital computer programming, Chemicals of AWWA Committee 8930 P-Standard Methods for the
I<. RIDGWAY. Examination of Water and Wastewater ( J . Amer. Wat. Wks Ass.,
1962, 54, 223--227).-A measured vol. of water is passed through
active C and the org. contaminants adsorbed extracted with CHCl,.
Sewage and Water. The CHCI, is evaporated off and weighed. The metho3 is applicable
Utilisation of activated sludge. S. Sathyanarayana Rao and to drinking water and other waters. Recoveries are 50-90%, but
S. C. Pillai ( J . sci. industr. Res., 1962. 21A, 33--35).-Studies not all the org. contaminant is determined (synthetic detergents are
ii-339 1.-CHEMICAL ENGINEERING A N D ATOMIC ENERGY ii-340
not eluted with CHCI,). Concn. of >200 pg./l. of contaminant 2.5 x lo8 (0.1-1000, preferably 0.5-5 p.p.ni.). Suitable poly-
affects odour and flavour. Clean surface water contains 25-50 electrolytes are claimed (e.g., hydrolysed polyacrylonitrile).
pg./l. of carbon-CHC1, extract. B. F. FULLAN. F. R. BASFORD.
Radiochemical determination of sodium-24 and sulphur-35
in seawater. D. 1.. Love and D. Sam (Analyt. Chem., 1962, 34,
336-340) .--Determination of Z4Na is made by scavenging with Matarials of Construction.
La(OH), a t -SO", double pptn. of NaCl with HC1 gas at 0" followed
by counting in a calibrated y-ray spectrometer and measurement of Ultrasonic testing for detecting fatigue damage in cement

-
peak-area a t 1.368 or 2.750 meV. A result (precision -176) is
obtained in 30 min.; chemical yield is ~ 7 0 0 /and
factor (d.f.) > lo6. Determination of
, decontamination
i s made by pptn. as BaSO,,
mortar. J. M. Dalrymple (Dissert. Abstr., 1961, 22, 1940).-An
ultrasonic signal of 112,000-120,000 CIS was passed along a cement
mortar beam subjected t o a reversed flexure of 1800 c/min. The
reduction to BaS with conc. H1, oxidation to BaSO, with alkaline output signal level was plotted against the frequency and the
H,O,, and then counting in a low-background p-counter by a gas- composite output (I) obtained from the area under the curve. I
or liquid-scintillation method. A result (precision 5 & yo)is obtained dropped off continually with increasing no. of cycles at high stress
in - 1 h.; chemical yield is 70-80% and d.f. > 10'. Relative level but at low stress level I was unchanged. I drop is an indication
activities of interfering nuclides are listed ; method is generally of fatigue damage. F. C. SUTTON.
applicable to seawater or salt-domes contaminated by nuclear Elastic modulus of concrete affected by elastic moduli of
bursts. (19 references.) W. J. BAKER. cement-paste matrix and aggregate. T. J . Hirsch (Proc. Amer.
Flame photometric determination of lithium in water. Concr. Inst., 1962, 59, 427-451).-A general equation is derived
M. J. Fishman (,I. Arner. Wat. W k s Ass., 1962, 54, 228-234).-A relating the elastic modulus ( E ) of concrete or mortar to a constant,
photomultiplier tube is used to measure the intensity of the Li arc the elastic moduli of cement matrix and aggregate components, and
line a t 670.8 mp. The presence of most other ions had little effect on mix proportions. The equation was confirmed over a wide range of
I i emissivity, e.g., the presence of 1000 mg./l. of Na, b u t Sr inter- variables for aggregates of steel punchings, crushed glass, P b drops,
fered at concn. >10 pg./l. had no effect when the Li concn. was sand, crushed limestone and calcareous-siliceous gravel. Age and
2 mg./l. The pH of the solution was not critical. The sensitivity of water : cement ratio govern E of cement paste ; values range from
the method for Li concn. 4: 1 mg./l. was 0.02 mg./l. and in the 1 to 4 x lo8 p.s.i. W. J. BAKER.
range 1-5 mg.11. the sensitivity was 0.1 rng.11. B. F. FULLAN. Substitution of Hmey sand for quartz sand to increase
Determination of OOSr and SOY concentrations in radio- appreciably tensile strength and seawater resistance of
actively contaminated natural waters. H. FranGois and M. cement mortar. J. Y . Karpinski (Rev. Mute?, Constr., C., 1962,
Jezequel (Cebedeau, 1960, No. 5 0 ; Rape. Cent. Et. nuc!. Sacluy, No. 556, 15-24).-At water/cement ratios of 0.44-0-63 substitution
1961, No. 1965, 4 pp.).-The activity due to O0Sr and in equili- of limey sand for quartz sand in 1 : 3 cement mortars quadruples the
brium in 500 ml. of, e.g., seawater, can be determined rapidly by
first removing as its complex with o-thenoyltrifluoroacetone in
C,H, a t pH 6.6 (inactive Y as carrier). The org. phase is taken to
seawater resistance with Portland cement and doubles it with
pozzolanic cement ; bending strength is also increased by
If limey-sand concrete is placed by guniting and not by normal
-
50%.

dryness on a stainless-steel disc for counting (low background) and compaction its durability in marine structures should be much
concn. is calculated by formula given. Separation of Sr is complete ; higher than that of quartz-sand concrete. The superior resistance of
sensitivity is 3 x 10- pc./ml. (11 references.) W. J. BAKER. limestone concrete to seawater is usually ascribed to, e.g., part
substitution of cement by powdered calcite (20-3070), which reacts
Determination of pg. quantities of amino-acids in natural chemically with the hydrating cement. It is more probable that the
waters. A. D. Semyenov, I. N. Ivlyeva and V. G. Datsko (Izv. cause is physical, viz., substitution of grains (0.5-1-1 mm.) of
A k a d . Nauk SSSR, Old. khim. N a u k , 1961, 184--186).-Acidic limestone for those of quartz of the same size. W. J. BAKER.
cationites are used to concentrate the amino-acids dissolved in
natural waters, with simultaneous separation from the mincral Effect of some processing variables in basic brick manufac-
solutes. Determinations can be made in the presence of coloured ture. G. A. Eusner and D. Ii. Hubble (Bull. Anter. ceratn. SOG.,
organic (humin) substances on 1-1. samples. G. F. PENNY. 1961, 40, 698-701).-A study of the effects of t h e binders (lignin
sulphite, MgCl,, H,CrO,), water content, and forming pressure
Determination of 2,4-dichlorophenol in water. S. D. Faust (5000-10,000 ps.i.) on a wide range of chemically bonded mixtures
and 0 . M. lily ( J . Amer. Wut. W h Ass., 1962, 54, 235-242).- of periclase 60+chrome ore 40%, showed that the optimum prop-
The method comprises extraction with light petroleum and the erties of a specific mixture were obtained only within a narrow
development of the colour with 4-aminoantipyrine a t pH 8 which range of content of bond and moisture and at max. pressure. All
was stabilised with NH,-phosphate buffer. The intensity of the manufacturing operations from crushing to pressing must be
colour is measured a t 500 mp, The method had a sensitivity of closely controlled. J. A. SUGDEN.
7 pg./l. within a range of 0-1000 pg./l. B. F. FULLAN.
Filled bituminous coatings for roofing felts. K. G. Martin
Determination of Rhodamine B in natural waters. M. (Commonw. sci. industr. Res. Org., Aust., 1962, Build. Rcs. tech.
Marichal and K. Benoit (Chim. anal., 1962, 44, No. 2, 70-72).- Paper 12, 32 pp.).-Laboratory and field studies on durability of
Rhodamine H, used as a tracer in natural water studies, is extracted coated roofing felts are reviewed with special reference to blistering
with isoamyl alcohol from the centrifuged, acidified sample, and the and water absorption and penetration. The addition of limestone,
fluorescence of the alcohol layer measured a t 551 mp. under U.V. fuel ash, slate, SiO, or talc to the bitumen is discussed and criteria
light. T'. D. PARR-RICHARD. for design of optimum coatings are given. Slump and pliability
Fuel, heat and energy aspects of sea- water distillation. tests determine mechanical stability of coatings, but durability must
R. S. Silver and W. J . K. Weir ( J . Inst. Fuel, 1961, 34, 514-521).- be assessed by outdoor exposure. In general, selection of the most
Factors governing the efficiency and cost of sea-water distillation suitable bitumen is more important than addition of filler, the
are discussed. and it is shown how the optimum conditions relating content of which is more influential than composition or particle-
energy and capital costs may be evaluated. D. DE VOY. size. Moisture transmission is strongly dependent on micro-holes in
Photometric determination of ozone in drinking water. the saturated felt, which may reflect voids entrained during mixing
H. Galster (a. nnal. Chern., 1962, 186, 359-364).-0, is determined of filler and bitumen. Provided that the effective vol. concn. of
by measuring the colour produced with NNN'LV'-tetramethyl-p- filler is < 0.5, blistering and slump-resistance a t high-temp. are
phenylcnediamine hydrochloride a t pH 2.2 (NO,- absent) or pH 5 minimised by filled coatings, but crack-resistance a t normal and
(NO,- prcsent). The method IS calibrated by using 0, sotiition of low temp. is only slightly improved. Blown asphaltic bitumens
known concn. (prep. describcd.) G. RUSSELL. having penetration indices > 4 have superior durability in com-
parison with residual bitumens or coal-tar pitch, (24 references.)
Agglomeration of suspended particles in aqueous media. W. J. BAKER.
American Cyanamid Co. (€3.1'. 816,399, 13.4.56 U.S., 20.4.55. Effects of sodium chloride on the drying characteristics of a
.\ddn. to €3.('. 725,460 ; J.A.C., 1955, ii, 457).--hgglomeration of refractory hardwood. J . G. Haygreen (Dissert. Abstu., 1961, 22.
suspended particles in aq. waste media is effected by adding an 1774).---A commercial NaCl prep. was applied to northern red oak.
inorg. coagulant (floc-forming material, e g., alum, hydrated lime, Stresses developed during drying were less than those in untreated
ferrous or ferric salts) and (subsequently) a synthetic polymeric wood. Diffusion of NaCl into the wood was greatly reduced by low
water-sol. polvelectrolyte, mol. wt. 4: 10,000, preferably 4 x lo6- initial R.H. and use of a more severe drying schedule. At suitable
ii-341 2.-FUEL A N D FUEL PRODUCTS ii-342
R.H. the behaviour of stress, moisture and set will be very similar an acid soluble in water in all proportions (e.g., HC1) and 0.3-6%
to that normally encountered in untreated lumber. The best R.H. by wt. of an organic acid substantially insoluble in water but
can be predicted from the shrinkage-relative humidity relationship. soluble in oil (e.g.. naphthenic acid). E. ENOSJONES.
F. C. SUTTON. Aqueous emulsions containing rubber for road surfacing.
Comparison of wood preservatives in Mississippi post Socidtd Chimique e t Routibre de la Gironde (B.P. 869,530, 21.10.58.
study. J. 0. Blew, jun., and J. W. Kulp (U.S. Dep. Agric. For. Fr., 24.10.57).-A cationic or acid emulsion consists of a stabilised
Sew. Rep., 1962, No. 1757, 19 pp.).-Untreated posts of southern rubber latex and a hydrocarbon binder, e.g., bitumen. The stabiliser
yellow pine and longleaf pine had an average life of 4.8 years in is a water-dispersable amine, a non-ionic emulsifying agent or a n
swamps, 4.0 years in damp soil and 2.3 years in dry soil. Estimated amino-acid (e.g.. mono-N-tallow-substituted ethylenediamine).
lives of >39 years are expected from posts treated with penta- The amount of stabiliser is 5-20% of the latex, and the mixture
chlorophenol (in used crank-case oil (I)),Zn meta-arsenite and with contains rubber 2-10, and hydrocarbon binder 40-70% of the
CuSO, or Na,AsO, applied by double diffusion. Borax-boric acid whole. J. A. SUGDEN.
or residual petroleum oil were unsatisfactory. I should not be
used for posts fencing cattle grazing country. 0. M. WHITTON.
Recent developments in manufacture and application of 2.-FUEL AND FUEL PROWCTS,
bitumen emulsions. H. Raudenbusch (Bitumen, Teere, 1962, 13,
62-66).-A review ; modern production involves the use of softer Micro-picture of the biochemical carbonisation of exinites.
and fluxed bitumens as the basis of emulsions, and also the extended E. Stach (BrennstCltemie, 1962, 43, 71--78).-Microscopical studies
application of cation-active binders with anionic emulsions hitherto are made of the structure of coals of several types to throw light
i n use and as emulsifiers for a new range of cationic emulsions. (13 on the course and mechanism of the initial or pre-fossilisation
references.) W. H. ICEMP. carbonation of the parent plant materials (resin, spores, etc., in
them) : the results are reported together with discussions of the
Rheology and structure of mixtures of road tar and bitumen. biochemical oxidation, corrosion, etc., influences and reactions that
K. Berneis and L. J. Wood (1. appl. Chem., 1962, 12, 160-164).-- cause the carbonisation. In the initial carbonisation of exinites. the
Flow tests and 7 measurements over a wide temp. range show that exinite becomes vitrinised by weak biochemical oxidation, or
stable mixtures, comprising up to 60% bitumen, are thixotropic at becomes fusinised by further or more intense bio-chemical air-
or below the softening point. With more bitumen, the higher mol. oxidation : many coals contain both fusinite and vitrinite. The same
wt. hydrocarbons and 0-containing compounds of the t a r are reactions occur, though to minor extent, on the mega- and micro-
peptised by the bitumen. It is suggested that phase inversion occurs spores and cuticles, the spores being vitrinised by the mild oxidation
at a composition of about 50% by vol. of each component. (11 conditions, and fusinised by the strong ones. The fusinised spores of
references.) 0. M. WHITTON. gas coal are strongly anisotropic and the surrounding coal and
Measurement and significance of asphaltene peptisation. normal dark spores are very weakly anisotropic. (13 references and
J. J. Heithaus ( J . Inst. Petrol., 1962, 48, 45-53).-An important 17 photomicrographs.) H. L. WHITEHEAD.
factor in the rheological properties of an asphalt is the state of Removing methane [degasification] from the Pittsburgh
dispersion of the asphaltenes (I) therein. The flocculation ratio ( F ) coal bed in West Virginia. W. M. Merritts, W. N. Poundstone
determined by titrating with n-C,H,, a solution of the asphalt in and B. A. Light (U.S. Bur. Min. Rep. Invest., 1962, No. 5977,
toluene, and the dilution ratio (D = vo1.-ratio : aromatic and p a r f - 39 pp.).-Methods of removing CH, from coal seams prior to mining
fin diluentpesidue) provide a measure of the dispersibility of the I are described. Drilling horizontal holes or holes in the roof, extraction
and the dispersive power of the maltenes (cf. van Kerkvoort el al., with vac. and water infusion were tested. Application of vac.
Preprint No. 220, IV Congr. Internat. Chauffage Zndustr., Paris, 1952). increased gas extraction but CH, content was lowered. CH, continued
The graph of F vs. D-I is a straight line. (27 references.) to be emitted from horizontal bores for several months indicating
A. R. PEARSON. that CH, is contained in the coal. Water infusion, especially with
Use of wire extensometers to measure deformations of wetting agents, reduced dust during mining. G. MACKENZIE.
visco-elastic materials in sheets. G. Tesoriere and D. Barbaro
(Rir. s c i . , 11, 1961, ii, lA, 319-326).-Deformations in bricks of Electron microscopic observations of structures in thin
compressed asphalt have been studied with wire extensometers. sections of coal. H . R. Brown and G . H. Taylor (Nature, Lond..
L. A. O'NEILL. 1962, 193, 114&-1148).-Electron micrographs of thin sections of
Compaction of soils and road bases. W. A. Lewis (Rds 6. Rd Australian coals confirm that the approx. parallel or branching
Constr., 1962, 40, 69-74).--Modern techniques of compacting soil striae reported by McCartney et al. (ibid., 1961, 191, 1363) are
and base materials are critically reviewed. Limitations in existing artefacts produced by the effects of compression and of such
specification and compaction methods are considered and improve- properties as elasticity of the macerals. They are most common in
ments suggested. Attention is drawn to the inadequacy of some sections of micrinite and fusinite, always a t 90" to the direction of
sampling.procedures, to problems in constructing bridge approaches, cutting and quite unrelated t o the bedding-plane of the coal.
to the necessity of rapidly compacting base materials, once mixed, Adjustment of knife-angle and cutting-rate can minimise or even
and to the value of various types of base materials. (14 references.) eliminate them. Procedure for prep. of ultra-thin sections for electron
R. M. Moss. microscopic resolution of the very detailed fine structure of coal and
for correlating results with those from optical microscopy is described
and illustrated. W. J. BAKER.
Hydraulic cement composjtion. Tile Council of America Inc.,
Assee of H. B. Wagner (B.P. 869,217, 26.5.59. U.S., 28.5.58).- Preparation of coal slurry for flotation. V. A. Shebanov and
Hydraulic cement 20--99, 2% solution of Me cellulose (7,0.1-70 K. D. Voronov ( K o k s i Khzm. [EnglishTransl.], 1962, No. 1. 14-16).
poise) 0.2-6.5, and polyvinyl alcohol (70-90% hydrolysed) -Flotation speed and extraction efficiency in coal-cleaning plants
0.5--10 wt.-'$$ of the whole mix, are mixed together. can be improved primarily by increasing the mixing rate (to the
J. A. SUGDEN. optimum) during slurry prep. and also by adding a foamer to the
Aminoplast-forming compositions for fireproofing wood paraffin. Longer conditioning time (30-45 sec.) and high slurry4
fibre boards. A/S Hunton Bruk (B.P. 869,535, 25.6.57. Norway, are ineffective unless mixing is rapid and vigorous. Installation of
18.7.56).-A composition for rendering wood fibre boards non- centrifugal pumps instead of contact tanks for supplying the
inflammable is an aq. solution of a mixture of NH9H,P0, 30-40%, reagents is recommended. W. J. BAKER.
(NH,),HPO, 10-20%, urea 8-11%, pentaerythritol 17-25% and Carbon-hydrogen groupings in the coal molecule. I . G. C.
formaldehyde 10--1G% by wt. E. ENOSJONES. Dryden (Fuel, Lond., 1962, 41, 55-61).-Using a recently
Aqueous suspension for improving the adhesive power of a developed method i t is possible to calculate the C/H distribution
bituminous or other hydrocarbon binder. N.V. de Bataafsche in the aliphatic portions of the mol. with a greater degree of certainty.
Petroleum Maats. (B.P. 812,847, 13.5.57. Fr., 15.5.56 ; addition Results for H in Me, aliphatic and aromatic form and their relation
to B.P. 744,505, 20.7.53; J.A.C. Abstr., 1957, i, 9).-An aqueous with yo C are given. (11 references.) D. DE VOY.
suspension suitable for use in pre-coating material t o be coated with Dehydrogenation and alicyclicity in coals. B. I<. Mazumdar,
a bituminous or other hydrocarbon binder, comprises 3-30% by wt. N. G. De and A. Lahiri (.f.sci. industr. Res., 1962, 21A. 36-42).-
of an amino compound or an amide containing a lipophilic radical The major findings of earlier workers on the dehydrogenation of
in the mol. and a t least one free amino group (oleylamine), 10--20% coal are summarised and the dehydrogenation of coals by halides
by wt. of a mineral oil, 0.5-100/6 by wt. (calc. on anhyd. basis) of and S is discussed. A significant part of the dehydrogenation is due
ii-343 2.-FUEL A N D FUEL PRODUCTS ii-344
to the attack of S on the aromatic position. With correlation for atoms of the moisture in the coke : i t gives results accuratc' to
this side reaction a revised estimate of alicyclicity is presented. -0.2% and has the advantages of speed, avoidance of sampling
Studies on the inhibition of tar formation with varying proportions errors with small samples, and applicability t o continuous deter-
of S and I, have indicated that the alicyclic structure in coal must mination. Essentially a coke sample (0.4 m.* of particle size 60-80
be weakly linked or not bonded with the remainder. Attention is mm.) is placed in a tall steel cylinder (dia. 100 cm.) which stands
N

also drawn to the effect of alicyclic structure on the formation of tar on a concrete floor with an intervening sheet of polyethylene (this
and smokiness of coal. (21 references.) F. C. SUTTON. sheet acts as moderator and reflector and enables readings to be
Gallium content of some Midland coals. I. M. Dalton and obtained that are in linear relation with the moisture content) ;
W. J. S. I'ringle (Fuel, Lond.. 1962, 41, 41--48).-Gallium deter- and two contacting steel sheaths pass vertically through the coke
minations have been carried out on a number of coals, values body, the one containing the neutron source (21°Po-Be of a-activity
obtained varying in the range 2-14 p.p.m. for the coal and 20-282 SO mcurie) and the other the BF, counter for registering the neutron
p.p.m. calculated on an ash basis. The sample was ashed or wet scattering. The moisture content is determined from a calibration
oxidised with H,SO,-HNO,. The Ga was converted to the malachite graph of readings from cokes of known moisture content.
green complex in 6 N - H Cand ~ colour of thc benzene extract measured H. L. WHITEHEAD.
a t 630 mp. (14 references.) D. DE VOY. Chemical reduction of some cokes and chars. J. D. Brooks
and H. Silverman (Fuel, Lond., 1962, 41, 67--79).-Reduction of
Rheological properties of coal during the early stage of cokes, prepared up to goo", with Li in (CH,.NH,), under N, suggest
thermal softening. 1'. I.. Waters (Fuel, Lond., 1962, 41, 3-14).- the following processes occurring during carbonisation :-400-500'
The softening of coking coals is almost independent of rank and, -volatilisation of less highly condensed aromatic material ; 500-
provided no active decomposition occurs, is reversible with change of 600"-dehydrogenation reactions and enlargement of aromatic
temp. Flow curves are obtained by investigation of the fluidity structures and, 600-900°-an increase in non-aromatic C-C bonds
under stress. (18 references.) D. DE VOY. resulting from stripping of edge H atoms from the polycyclic
Penetration plastometry : (a) design and operation of aromatic nuclei. Degree of reduction rises with coking .temp. to
plastometer, (b) rank and coke quality correlations. T. G. -600" and then falls. The i.r. spectra shift to shorter wave-
Callcott and J. A. Innes (Fuel, Lond.. 1962, 41, 15--34).-The design lengths and semiconductivity of reduced coke falls from 600 to 900".
and operation of a penetration plastometer is described. Repro- (16 references.) D. DE V O Y .
ducibility is good and the parameters of thc main Australian coals Effect of recirculating combustion products on heating of
agree well with values predicted from results on Russian and Indian coal charge. E. P. Likhogub and G. M. VolfovskiI (Koks z Khirn.
coals. (18 references.) D. DE VOY. [English Transl.], 1962, No. 1, 20-22) .-Increased recirculation
Effect of sulphur retention on determined ash in lower-rank improves coke uniformity and quality ; degree ( D ) of recirculation
coals. W. H. Ode and F. H. Gibson ( U . S . Buu. Min. Rep. Invest., should be based on measurements along the axis of the oven and
1962, No. 5931, 1 1 pp.).-Investigations showed that 60-95% of on analysis of temp. distribution. Temp. of the space under the roof
the total S in coal of lower rank is retained as SO,. This causes a is independent of D and must be minimised by controlling the size
positive error of up t o 6% in the amount of ash (2-3% for lignites and level of charge. Oven vol. was 30 cu. m., heating level 110 cm.,
and 1% for sub-bituminous coals). No simple reduction of S content max. temp. difference along the oven-axis was 570" with closed ports
is possible so the SO, should be deducted to obtain the true ash and only 200" with fully-open ports. W. J. BAKER.
value. G. MACKENZIE. Gravimetric investigations of decomposition processes in
Apparent variation in fluidity of a coking coaliat a constant younger fuels. 0. Abel and H. Luther (ErdoZ. u. Kohle, 1962. 15,
temperature below its active decomposition point. J. C. 90-95).-Thermogravimetric plots of wt.-loss yo per O c as a function
Macrae and K. S. Murthi (Fuel, Lond.. 1962, 41, 35-40).-The of temp. a t a heating rate of 0.75" per min. show max. which are
fluidity of a coking coal heated a t a const. temp. between.its softening reproducible within 7% a t temp. within h3". Characteristic max.
and decomposition temp. is a t first constant, then increases rapidly are distinguished for sugars (200, 210 and 225"), polysaccharides
and finally falls rapidly. It is suggested that the quantity of fusible and tannins (240"), hemicelluloses, polysaccharides and resins (260").
matter remains sensibly constant but because of a thinning of the hemicelluloses (280"), celluloses (295"), lignins (320, 335, 350,
solid-liquid barriers in the mass, increasing contact between, and 375"), humic acids, humins and bitumens (335, 350, 375"), and
mutual enmeshment of, the infusible components occurs. bitumens and humins (395, 405 and 425'). The disappearance of the
I>. DE VOY. simpler compounds during coalification or decay causes a shrinkage
Change in plasticity of coals when coking rate is increased. of the low-temp. end of the plot and a shift of its centroid to higher
N. S. Gryaznov (Koks i Khim. [English Transl.], 1962, No. 1,5-10). temp. (Cf. J.A.C. Abstr., 1961, i, 332). A. R. PEARSON.
-The viscosity index of a plastic mass of coal decreases with Effect of the disproportionation of the composition and
increasing coking rate ( x ) to the state of max. softening (shear stress increase in the yield of volatile products in fuel pyrolysis at
= T) according to T = A X - b , where A and b are constants. Thus high heating rates. 2. F. Chukhanov, A. P. Kashurichev and
the change in plasticity at high x (20"/min.) can be calculated approx. Ya. A. Stonans (Dokl. Akad. Nauk S S S R , 1962, 143, 162-165).--
and poorly-coking coals identified and classified. Results agree with The yield and composition of gases evolved during the slow (0.01-
those obtained when T is determined with the rotor plastometer. 5.0" per sec.) and the rapid (1000" per sec. and higher) heating of
With increasing x , the structural strength of the coke increases in coal and peat are tabulated for temp. in the range 200--800". With
conformity with decreased 7,increased coking capacity and decreased both fuels rapid heating resulted in a marked decrease in the total
porosity. Hardness of coke or semi-coke is decreased because poly- vol. of gases evolved although the relative amounts of CO and
condensation and densification are retarded as x increases ; internal unsaturated hydrocarbons increased. The proportion of CO, in the
stresses and cracks are also developed. W. J . BAKER. gases was correspondingly reduced. (14 references.)
International standardisation of crucible method for K. A. IiSEN.
determining yield of coke and volatiles from coals. W. Internal corrosion of pipelines for gases containing oxygen.
Radmacher and A. Scholz (Erdol u. Kohle, 1962, 15, 96--101).- F. Gebert (Erdol. u. Kohle 1962, 15, 113--118).-Laboratory tests
The International Standardisation Organisation N 586 Draft recom- with mild steel (C 0.01 yo)in gases containing 0, from 0.4 (coke oven
mends a cylindrical quartz crucible (height 38, dia. inside 22, gas) to 20% (air) a t various R.H., or immersed in pure water through
outside 28 mm.) with ground lid, the whole weighing 10-14 g., which the gases were bubbled, indicate that internal corrosion
into which the air-dry sample (1 g. $0.2 mm. size) is weighed. It is occurs only in contact with liquid water. The drying of the gas t o
. must ensure no condensation must take into account the possible prescnce
heated for 7 min. in a muffle furnace kept a t 9 0 0 ° ~ 1 0 0and
reach .4: 885' in 3-4 min. as shown by a thermocouple placed under of hygroscopic salts in the pipeline. A. R. ]?EARSON.
the crucible. In calculating the results allowance must be made for Sea transport of liquefied gases at atmospheric pressure.
moisture and carbonate-CO,. The volatiles-yo were 0.03-0.18 11. Safety and design problems, and economic considerations.
higher than those by DIN 51720. A. R. PEARSON. M. Volger (Erdol u. Kohle, 1962, 15, 118--121).-The transport of
Determination of the moistur6 in coke by neutrons. H. liquefied natural gas is discussed. An experimeirtal French ship is
Uresia, A. Calamini and E. Steinberg (BrennstChemze, 1962, 43, to be equipped with containers of various designs and materials.
86--88).-Full description is given of a method and apparatus for A. R. PEAKSON.
determining the moisture content of coke by measurement of the Separation and recovery of hydrogen sulphide from gases
scattering of neutrons from a radioactive source caused by the H of high GO, content. R. Pasternak (BrennstChenzit:. 1962, 43,
ii-345 2.-FUEL A N D FUEL PRODUCTS ii-346

6 M 7 ) . - T h e Alkazid method for stripping the H,S from coal gases diethylphenol is identified for the first time as a product of coal
of high CO, content, i.e., scrubbing the gas with a solution of an carbonisation. (19 references.) H. I-. WHITEHEAD.
alkali salt of an amino-acid (NN-dimethylglycine K salt), effects Influence of pressure on the separation of condensates of
selective removal of the H,S, is free from the difficulties experienced coke and gas works. R. Riedl and M. Bennes (BrennstChemze,
in other wash or dry methods for removing H,S (due to the presence 1962, 43, 68-71) .-Using model products representing (tar)
of the CO,), and permits good recovery of the separated H,S. Full condensates from ( a ) high-temp. carbonisation of ordinary coal, and
description and discussions are given of the industrial use of the (b) brown coal generator tar production, studies are made of the
method and of the recovery of the S. Essentially the coal gas from effect of temp. and pressure on the velocity and extent of the
a pressure carbonisation and of high CO, content is scrubbed under separation of water from the tar in the condensates : the results are
pressure first with water to remove HCN (a necessary step as HCN fully reported. With condensates of type ( a ) the optimum temp. for
upsets the subsequent step), then with Alkazid lye by passage attaining water separation varies with pressure being 80" a t 2 atm.,
countercurrent to the lye a t 20-22" under 21 atm.; thc lye is 50" a t 3 atm. (the conditions for best separation) and 20' a t 5 atm.:
degassed a t 107' in a column, and recycled after cooling ; and the higher pressures and temp. give poorer separations. With condensates
liberated gases (still under pressure and after cooling) are passed to a of type (b) (which also simulate condensates from low temp.
Ni catalyst to convert the H,S to H,SO, : a pure acid of 60° B6 is carbonisations of ordinary coals), raising the pressure lowers the
obtained. H. L. WHITEHEAD. separation and raising the temp. promotes separation. Reasons for
Formation of potassium formate in vacuum-potash units lower separations through increased pressure or temp. are discussed,
for removing hydrogen sulphide from coke-oven gas. M. E. including the factor of the presence of emulsifying constituents.
Neimark (Koks i Kkim. [English Transl.], 1962, No. 1, 44-46).- H. L. WHITEHEAD.
The high consumption of KOH in the unit is caused by accumulation Processing pyrolysis tar [from alcohol production] without
of K formate (I) in the dil. solution, the KCN present in the liquor separating the forerunnings. E. E. Kondrashov (Koks i Kham.
decomposing very rapidly to NH,+I. Concn. of I (-200 g./l.) is [English Transl.], 1962, No. 1, 3940).-About 10 vol.-yo of a coal-
N 60% of total unregeneratable compounds (KCNS, K,S,O,, etc.). tar benzole fraction (79-139") is added to the redistilled pyrolysis
W. J. BAKER. tar (4-7% forerunnings) and the mixture is washed with H,SO,
Effect of burner orientation on quenching distance. G. R . ( - 6 wt.-%) and NaOH a t 40" for 20-50 min. before fractionation.
N

Sturmon (J. uppZ. Chem., 1962, 12, 310-314).-Tests revealed that A charge so processed has a colour-test value of 0.2 and Br no. of
the quenching distance of laminar, premixed methane, propane and 0.3-0.4 g./100 ml. W. J. BAKER.
n-butane flames is not affected by orienting a plane parallel-plate-
type burner up to 90" from the vertical and that the stoicheiometric [A] Removal of hydrogen sulphide from gases. [B] PuriA-
mixture quenching distance is not affected up to 165'~. a t orien- cation of gases. Gas Council (Inventors : [A, B] W. B. S. Newling,
tations of 90-165" the quenching distance and flashback composition [A] M. W. G. Tanner and R. J. Wingrove, [B] R. J. H. Banks)
curves were tangential a t the stoicheiometric point. The latter (B.P. 869,127, 869,131, [A] 20.5.58, [B] 15.6. and 29.10.56).-
distance was larger and the former smaller than the 0-90" quenching [A] H,S and HCN (if present) are moved from cooled, de-tarred coal
distance. The quenching distance transformation velocity relation gas by countercurrent washing with an ammoniacal liquor con-
equation of Potter and Berlad (cf. Nat. Adv. Commeefor Aeronautics, taining Zn compounds. The NH, partial pressure in equilibrium
TN 3882, Nov., 1956) is valid for n-butane-0,-N, flames. (14 with the liquor is such as t o provide a n NH, concn. in the gas of
references.) 0. M. WHITTON. <50 (150-500) grains of NH, per 100 standard cu. f t . of gas. The
Extraction agent for determining high molecular tar- pptd. Zn compounds are then separated from the liquor. [B] The
resins in electrode binders. F. A. Croy (Baturnen, Teere, 1962, wash liquor is an alkaline suspension or solution of Zn(OH), or basic
13, 67-72) .-The relative merits of quinoline and anthracene oil Zn carbonate in a solution of alkali hydroxide and/or carbonate
are discussed with respect to the extraction of high-mol. tar resins and/or bicarbonate. J. M. JACOBS.
from normal and catalytically oxidised coal-tar pitch. In a search Storing acetylene. Union Carbide Corp., Assee of H . J. Portzer,
for a selective solvent, of definite composition and quality, possessing H. B. Sargent, M. L. Kasbohm and I?. A. Bohner, jun. (B.P. 870,254,
a n efficiency comparable with that of anthracene oil, b.p. and surface 8.7.59. US., 14.7.58).-C2H, is stored in, and dispensed from, a
tension being the main criteria, cinnamaldehyde was found t o give container in which there is a porous body (A1,0,,3H20, C, monolithic
the best results ; methods relating to its use in tests, together with CaSiO,, CaCO,, SiO,, etc.) having interconnecting pores of
those used with quinoline and anthracene oil, are described, and a N 0.005-50 p cross-sectional dimension, and a heat transfer conduit
series of microphotographs is given. W. H. KEMP. within the body. C,H, is introduced into the porous body while
Chemistry of peat bitumen : fractionation and infra-red cooling the intenor portions of the body below the condensation
studies. J. D. R. Thomas ( J . uppZ. Chem., 1962, 12, 289-294).- temp. of the C,H,, and C,H, is delivered from the container by
Ground air-dried peat was extracted with benzene/EtOH 65/35. heating the interior portions of the body above the vaporisation
This extract was extracted with MeOH and the extract chromato- temp. of the C,H, a t the storage pressure. J . M. JACOBS.
graphed on De-Acidite FF, eluting the products with MeOH,
MeOH/HOAc and HOAc. The i.r. spectra of each fraction were
determined by the KBr disc technique. The spectra suggest that the
more weakly ionised material is eluted with MeOH (e.g., aliphatic Potroloum Products.
esters), the AcOH/MeOH elutes the less weakly ionised material Microbial desulphurisation of petroleum. D. L. Isenberg
(e.g., phenols). The residue on the column was not eluted with aq. (Dissevt. Abstr., 1962, 22, 3349).-A culture of Artkrobucter sp.
HCl and was possibly pptd. bitumen. (26 references.) isolated from a high-S crude oil fraction grew freely in such sub-
0. M. WHITTON. strates. The cells accumulated org. acids and contained r 1.3% of
Oil-shale assay method for product balance studies. S. The activity of the organism was favoured by aeration and by
A. B. Hubbard (Fuel, Lond., 1962, 41, 49-54).-An improved pH 7 . 7 - 8 . 0 ; its C energy is probably derived from long-chain
oil-shale assay method has been developed whereby the sample is aliphatic hydrocarbons and its S from aliphatic sulphides in the
gradually heated to 500" in He to prevent oxidation, the retort gas petroleum. A. G. POLLARD.
is collected for direct weighing and analysis. The water wt. is Microbial decomposition of hydrocarbons. G. W. Fuhs
corrected for the NH, and CO, content. D. DE Vou. (Arch. Mikrobiol., 1961, 39, 374-422).-A critical review. The
Analysis of phenols in brown-coal tar. 111. MacAk and J. decomposition of paraffinic and cyclic hydrocarbons by a wide range
Rahitk (BrennstChemie. 1962, 43, 8 0 - 8 6 ) .-The phenolic portion of of organisms is summarised and mechanisms involved are considered.
brown-coal tar oil is extracted with alkali and after purification the A. G. POLLARD.
extract is fractionally distilled (14 theoretical plate) ; each of the Determination of trace amounts of total nitrogen in
fractions is further fractionated (57 theoretical plate), and the final petroleum distillates. Extractive percolation method. P.
residue is fractionated under vacuum ; and each of the initial and Gouverneur (Anal. cham. Acta, 1962, 26, 212-223).-Increased
final fractions is tested for the presence and identity of alkylphenols insight into the processing and performance of petroleum products
by circular paper chronatography. The results, fully reported, show has stressed the importance of trace amounts of N. The determina-
that some 53 different alkylphenols are present (all but nine of which tion of N (r10 p.p.m.) by the normal Kjeldahl procedure or by
are identified) including mono-lower-alkyl-phenolsand simple and catalytic hydrogenation is not satisfactory. It is shown that per-
mixed dialkylphenols, together with PhOH and naphthols ; 3,4- colation through pumice saturated with H,SO, extracts all N
ii-347 2.-FUEL A N D FUEL PRODUCTS ii-348

compounds, including non-basic compounds. The Kjeldahl procedure surface undulations ; its expulsion depends on its 7) and i t may set
applied to the pumice column gives results for total N accurate to up a hydrostatic pressure high enough t o cause plastic deformation
15%. C. S. HOWES. of the specimen before die-to-metal contact is made. The compres-
Sweetening liquid hydrocarbons by molecular sieves. sion of A1 discs by steel dies under incremental loads is facilitated
J . I<. Messmer and 0. Brunner (Erdiil u. Kohle, 1962, 15,185-186). by the presence of a lubricant to an extent which increases, at a
-The C,H, or other liquid flows down through the sieve material falling rate, as the 7) of the lubricant increases. Similarly in the
(dehydrated synthetic zeolite) at 14.7 atm. until the effluent fails compression of laminae the interfacial steel-A1 friction coeff. fell
to pass the Cu strip test. The pressure is then reduced t o 4 - 8 atm. towards a limit as 7 increased. Compression without lubricant gave
and residual C,H, is purged by 0,-free gas (CH,). The adsorbed S smooth surfaces, which became more matt with lubricants of
compounds are expelled by dry CH, at 204"/8.4 atm. and led off for increasing 7. With rolled specimens there was anisotropy between
use as fuel. The bed is cooled by sweetened liquid C,H, which is the directions along and across that of rolling. (19 referenc,es.)
recovered, the pressure being raised to 14.7 atm. for the next cycle. A. R. PEARSON.
Capital costs compare with those for alkali-washing, and the only Circulatory oxidation test [of lubricating oils]. J. H. T.
maintenance cost is the replacement of the sieve material every two Brook (1. Znst. Petrol., 1962, 48, 7--12).-Tests on four different oils
years. A. R. PEARSON. show that both vigorous shaking and a certain min. 0,-circulating
rate are nccessary to ensure the max. oxidation rates, and that the
Sweetening of hydrocarbons. P. W. Sherwood (ErdB1 u. oxidation products should be removed by a cold trap and absorbents.
Kohle. 1962, 15, 182--185).-Alternatives to catalytic hydrogenation An apparatus fulfilling these requirements has been designed. A
are discussed. Odour and corrosivity due to mercaptans (I) can be solution of ferric stearate in to!uene is evaporated in the sample to
removed by oxidising I to disulphides with air in contact with an act as a catalyst. A. R. PEARSON.
alkaline solutiser ' in which both I and 0, dissolve, and which may
contain an oxygen-carrier (phenylenediamine, solid S dyestuff). Decomposition of hydrocarbons in electric field. H. Luther,
The alkali is regenerated by steam or air, or electrolytically, or by H. Klemm and G. Staats ( E r d d u. Kohle, 1962, 15, 84-90).-
treatment with an epoxide. e.g. ethylene oxide. I can also be Transformer oil (I), C,,H,,Ph (11), and C,,H,, (111) were subjected
oxidised or hydrolysed in acid media (H,SO, 80-98%). Air- to 500-cycle alternating fields of N 10 kV per cm., while the gaseous
oxidation with bauxite as catalyst has been applied. products were continuously pumped off (apparatus described). The
A. R. PEARSON. min. field strength necessary for discharge fell slightly as the
Composition of cracking gasolines from naphthenic feed pressure in the reaction vessel was raised from lo-, to lo-' mm. Hg.
stocks. I. Combined method for detailed group composition. The discharge in I (0.1 A) ceased after 15 min. due to the fixation
N

A. V. Topchiev, I. A. Musaev, E. Kh. Iskhakova (Izv. Akad. Nauk of the volatile ions as wax on the tube wall. The rates of gas
S S S R , Otd. khinz. Nauk, 1961, 94--102).-The method includes evolution were little affected by temp. between 20 and SO", but the
chromatographic separation of a standard fraction (60-175') of the proportion of H, in them fell from 81 t o 44 (I), 58 to 17 (11), and 84
cracking gasoline, together with hydro-dehydrogenation catalysis t o 37% (111) with corresponding increases in the yields of CH,,
and the aniline method, and is suitable for determination of cyclo- C,H:, and other hydrocarbons. The deposition of wax diminished
hexane, cyclopentane, paraffinic, aromatic, cyclohexene, cyclo- at higher temp. The waxes were unsaturated and absorbed 0, from
pentene and alkene hydrocarbons. Data are given for three catalytic- air. Those recovered from used cables contained CO and -CO,H
or thermal-cracking gasolines, reflecting differences in feedstock groups, the 0 being probably derived from moisture in the insulating
composition and method of treatment. G. F. PENNY. paper which itself when dry yielded H,, CO, CO, and CH,, but no
H,O, in the discharge. A. R. PEARSON.
Increased octane number of gasoline by reformation over
rhenium-alumina catalyst treated with hydrogen sulphide. Separation of aromatic hydrocarbons. Esso Research &
Kh. M. Minachev and M. A. Ryashentseva (Izv. Akad. Nauk S S S R , Engng Co. (B.P. 869,299, 16.10.57. U S . , 6.11.56).-Aromatic
Otd. khim. Nazck. 1961, 107--109).-The catalytic properties of 20% hydrocarbons are separated from, e.g., a naphtha, by extraction with
He-A1,0, catalyst treated with H,S in reforming straight-run liquid NH,. They are recovered as a bottoms product by distillation
gasoline a t 500-510", 5 atm. H, pressure, v= 1.0 h-l., and He/ of the extract to remove NH, and an azeotropic mixture of :NH, and
hydrocarbon = 5. Catalysates were obtained with aromatics content hydrocarbons. E. ENOSJONES.
of 32 and 47o/b, and octane no. without PbEt, raised from47.8to71
and 87.2 correspondingly. G. F. PENNY. Fuels. Shell Internationale Research Maats. N.V. (B.P. 870,431,
6.10.59. U.S., 8.10.58).-A thermally stable hydrocarbon fuel
Oxidation of hydrocarbons. X. Slow oxidation of aromatics composition comprises a mixture of polycyclic naphthenes having
in gas phase. B. Results and evaluation of investigation. at least three condensed rings and 14-26 C-atoms but > 8 alkyl
C. Kroger and G. Higorajski ( E r d d u. Kohla, 1962, 15, 109-113).- groups (1-3 C) per mol., obtained by distillation, etc., of a mixture
The course of the reaction has been followed by analyses of the of hydrocarbons containing a t least 35% by wt. of aromatic com-
products during the oxidation of PhEt etc. a t 380-410". At 420" pounds boiling in the range 250-600". E. ENOSJONES.
ignition occurred. Mechanisms are proposed for the initiatory
reactions (formation of OOH ions) and the thermal cracking Jet fuels. Texaco Development Corp. (B.P. 870,474, 8.12.59.
reactions. Higher temp. favours the reactions involving aldehydes U.S., 8.12.58 and 25.2.59).-A liquid hydrocarbon fraction boiling
rather than hydroperoxides. Chain-breaking occurs at the walls. in the range 200-500"~ is contacted with a dehydro-aromatisation
In a CFR test cngine PhEt began to knock a t compression ratio catalyst a t 800-1000"~/50-750 p.s.i.g. in the presence of H,,
B = 5 . When the engine was driven with the ignition switched off extracting a t least a portion of the product with a solvent having
the reaction products in the exhaust (PhCH:CH,, H,O,, HCHO, a n affinity for aromatics t o produce an extract phase rich in aro-
PhCHO) corresponded with the reaction scheme. Self-ignition matics and a raffinate of reduced aromatic content, reducing the
occurred a t R = 9.6. (Cf. J.A.C., 1961, i, 17). A. R. PEARSON. aromatic content of the raffinate and recovering a hydrocarbon
liquid essentially paraffinic in nature and having a luminosity
Coulometric determination with amperometric indication number of a t least 100. E. ENOSJONES.
of hexaethyldiplumbane in lead tetraethyl. G. Tagliavini, U. Fuel compositions. N.V. de Bataafsche Petroleum Maat-
Belluco and l*. Riccoboni (Ric. sci. 11, 1961, ii, lA,338--345).-A schappij (B.P. 801,830, 22.8.56; U.S. 24.8.55. Addn. to B.P.
procedure for the coulometric determination of hexaethyldiplumbane 754,773 ; J.A.C. Abstr., 1957, ii, 240).-To prevent or reduce the
(I)in presence of PbEt, by coulometric iodination a t constant current, formation of ice in fuel oil there is added 10-30 p,p.m. by wt. of
with amperomctric (dead-stop) end-point, has been developed. The partially hydrolysed reaction product copolymer (rnol. wt.
prccision of the method is 1 -2(;(, for contents of -O.lyo of I. N 10,000) of a vinyl ester (acetate) of an aliphatic carboxylic acid
L. A. O'NEILL.
Effect of variation of base lubricant viscosity on coefficient
having + 5 C-atoms and a mixture of a-olefins having 1 0 4 2
C-atoms, the ratio of the number of polar groups to the number of
of friction during metal deformation. Micro-interferometry non-polar groups of the reaction product being between 0.5-10 : 1.
technique. I,. H. Butler ( J . Inst. Petrol., 1962, 48, 27-31, 32-39). I. JONES.
-The effect of the '1 of the lubricant in roughening the metal
surface during cold deformation is shown by microphotographs of Polymeric reaction products of aluminium alkoxides.
A1 discs after compression (7%) with a die carrying a n interference Hardman & Holden Ltd., and J . Rinse (B.P. 869,171, 19.3.59. Neth.
pattern of parallel lines, which were matched by the A1 surface 3.4.58).-Water vapour isintroduced intoan A l alkoxidederived from
without lubricant, but faded as lubricants of higher 7) were used and 2-5-C alcohol in the mol. ratio of 1 : 1, in presence of an alcohol of
N

vanishcd a t 7 > 100 cP. The lubricant is trapped in the initial g + 5 C or an org. solvent for the A1 alkoxide, e.g., an aromatic
ii-349 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-350
hydrocarbon. The reaction mass is maintained at 70-120" while case the variation with pressure was similar. Increasing the no. of
the water is being introduced so that a reaction involving conden- rams produced similar results in all cases. As the binder concn.
sation and liberation of alcohol occurs. The heating is then continued increases, the effectiveness of ramming compared with squeezing
at + 130" until -2 mol. of alcohol have been removed per mol. of decreases. Results indicate that with increasing squeeze pressure,
A1 alkoxide. The products are of value in the prep. of greases with moulding sands become more brittle. K. M. H.
high dropping points. J. M. JACOBS. Fibre metal resistance welding. Anon. (Metal Ind., Lond.,
Detergent automotive fuel. Union Oil Co. of California (B.P. 1962, 100, 150--151).-This welding system enables a joint to be
869,840, 2.1.59. U.S., 20.1.58).-An internal combustion engine fuel achieved between two metals of appreciably different resistivity
consists essentially of hydrocarbons boiling in the gasoline range where there is difficulty in obtaining the required high temp. at the'
containing 0-00004--0~02~0 by wt. of an aliphatic primary amine of faying plane. The faying contact resistance is increased by placing
12-22 C-atoms (oleylamine) or a diarylidene-alkyldiamine (especially a fibre metal shim between the two sheets t o be joined. Advantages
disalicylidene-1.2-propylenediamine)and 0.02-0.6% by wt. of a of this technique are : (I) the geometry of the fibre sheets enables
paraffinic hydrocarbon oil having a viscosity at 2 1 0 " ~of 42-78 SSU the number of contact surfaces which the current must traverse to
and a flash point of + 400"~. E. ENOSJONES. be increased and heat is therefore concentrated at the faying
Polyamides as fuel oil additives. Esso Research & Engng Co. interface and (2) two or more alloy components can be mixed. The
(B.P. 790,604, 28.8.56. U.S., 17.10.55, Addition to B.P. 723,639, technique is described and examples are given. c. v.
30.12.52 : T.A.C.. 1955. ii. 294).-The formation of sludge caused by Collodion stripping of thin evaporated layers of metals and
oxidation of fuel oils is reduced by the addition of 0.002-0.5% by carbon. I. Ogura ( J . Sci. Hiroshima Univ., 1961, 25AII. No. 1,
wt. of an oil-soluble polyamide which is the reaction product of a 73-76) .-The collodion stripping technique applied t o thin
dibasic acid or anhydride containing 4-10 C-atoms, or a mixture of evaporated metallic layers and subsequent electron-microscope
such acids and anhydrides, with a diamine (RNH.CH,.CH,.NH,) examination showed the films t o be continuous fine-grain structures
formed by interaction of ethyleneimine with one or more aliphatic in the case of Pd, A1 and Cr, and coarse grains in the case of Ag
primary amines containing 8-18 C-atoms. I. JONES. about 200 A dia. A comparison of the ease with which layers were
Salts of polymerised alkyleneimines and lubricating com- stripped was made, the results agreeing with previous work.
positions containing them. Shell lnternationale Research Maats. D. J. ELGAR.
N.V. (B.P. 869,084, 16.11.59. Neth.. 18.11.58).-Salts of alkyl
salicylic acids (especially alkyl of 14-18 C) and polymerised Precision casting by the lost wax process. Metropolitan-
1,2-alkyleneimines (with C-alkyl substituents) are used in amounts Vickers Electrical Co. Ltd. (Inventor : J . s. Turnbull) (B.P. 809,954,
of 0.5-5-0% (1-3%) by wt., as additives in lubricants to improve 24.8.54. Addn. to 722, 816).-0nly the first coating applied to the
their wear-inhibiting properties. E. ENOSJONES. wax pattern is a refractory filler of finely divided ZrSiO, (other fillers
such as SiO, flour, A1,0,, etc., are less preferable) suspended in
Greases containing silica fillers. Columbia-Southern Chemical SiO, gel (containing 15-30~0 of SiO,). J . A. SUGDEN.
Cmrp.(B.P. 820,548, 29.11.55. 1J.S.. 8.12.54. Addn. to B.P. 756,966 ; Simultaneous reduction of a reducible metal oxide and
J.A.C. Abstr., 1957, ii, 440).-The grease comprises an organic
lubricating oil and the organophilic reaction product of an organic production of carbon monoxide and hydrogen. Texaco
isocyanate !e.g., toluene 2.4-di-isocyanate) and finely divided silica Development Carp. (Inventors: H. V. Rees and F. B. Sellars)
having an average ultimate particle size below 0.1 p and containing (B.P. 824,805, 3.6.57. Addn. to B.P. 712,929; J.A.C. Abstr., 1955,
bound water and corresponding t o the formula HaO,(SiOa)zwhere i, 217).-The metal oxide in particle form is mixed with a liquid
r is 3-85, in amount sufficient to thicken the liquid. The amount of hydrocarbm t o form a slurry which is passed through a tubular
isocyanate is 2-30% by wt. of the silica. E. ENOSJONES. heating zone where the hydrocarbon is vaporised. The vaporous
dispersion of the metal oxide particles is mixed with a gas con-
Anti-friction materials based on synthetic resins. gtablisse- taining free 0, (pure 0,) and passed into a reaction zone where the
ments Neyrpic. Sociktk Hydromkcanique e t Frottement and oxide, hydrocarbon and 0, are caused to interact a t > 1090". The
Manufacturede Rueil (Inventor : J. J. Caubet) (B.P. 869,559, reduction product of the metal oxide and a gaseous product com-
3.2.59).-An anti-friction material comprises, as a solid lubricant, prising CO and Ha are recovered from the reaction zone.
MoS, or graphite 9-70%, a binding agent of epoxy or superpoly- J. M. JACOBS.
amide resin 25-91% and an auxiliary lubricant of stearic acid or Phosphate coatings on metals. Pyrene Co. Ltd. (B.P. 787,291,
butyl stearate 0.1-2.00/, by wt. E. ENOS JONES. 7.10.55. US., 7.10.54. Addn. to B.P. 718,362; J.A.C., 1955, i, 870).
-The metal surface is cleaned, and a phosphate coating formed on it,
in a single working step by means of a n emulsion of a grease-removing
3.-INWSTRIAL INORGANIC CHEMISTRY. solvent (aliphatic hydrocarbon, e.g., kerosene) in an aq. acidic
solution of a coating-metal phosphate, the solvent being emulsified
General Metallurgy. with a non-ionic surface-active hydrophobic polyoxyethylene
Fuel and energy required for one preparation. K. G. Dixon condensate containing ethylene oxide <50 wt.-%, e.g., a polyoxy-
and E. W. Voice ( J . Inst. Fuel, 1961,34, 529-534).-Methods of one propylene-polyoxyethylene condensate. J. M. JACOBS.
prep., including concentration, pelletising, nodulising, briquetting Pretreatment of metal surfaces [before being] laminated
and, especially, sintering, and their applicability are discussed in to synthetic resins. Amchem Products Inc. (Inventor: F. P.
conjunction with fuel requirements. (17 references.) D. DE VOY. Heller) (B.P. 808,115, 25.6.57. Addn. to B.P. 714,541 ; J.A.C.
Attachment of mineral particles to bubbles during flotation. Abstr., 1955, i, 537).-The metal surface is cleaned and treated with
V. Motion of bubble surface strongly retarded by surface- a solution of p H 1.4-2.0 containing C1- or Br- 0.05--17y0, complex
active agents. Distribution of surface-active material and fluoride <0.0250/, but 0.5-2 pt. by wt. of the chloride (all calc.
electric field of bubble. S. S. nukhin and B. V. Deryagin (Zh. as NH, salt) and CrO, 0.05-50 times the total wt. of the other
$2. Khim. [English Transl.], 1961, 35, 715-717).-A method for salts. One solution contains CrO, 5 g., NH&l 5 g., NH, silico-
approx. calculation of the motion of the surface of a bubble when fluoride 5 g., water to 1 1. (pH 1.6). I. JONES.
strongly retarded by a surfactant is developed kinetically. A dimen-
sionless quantity permits the degree of surface retardation and of
suppression of bubble electric-field to be determined. (Cf. Idem, Ferrous Metallurgy
ibid., 1959, 33, 389 ; 1961, 35, 61 1). W. J. BAKER.
Properties of clay-bonded sands compacted at high pres- Iron.
sures. D. A. Taylor and W. R. Roberts (BCIRA 1..1962, 10, BeneAciating and smelting Carter Creek, Mont., iron ore.
234--241).-The properties of synthetic sands compacted a t W. T. Holmes, 11, W. F. Holbrook and L. H. Banning (U.S. Bur.
pressures of up to 800 p.s.i. are compared with those of compacts of Min., Rep. Invest., 1962, 5922, 21 pp.).-The Carter Creek deposit
similar density produced by multiple ramming. Green (I) and dry which has an Fe content of -31Y0, consists of bonded gneisses
(11) compression strength rise with pressure, but not greatly, the having magnetite as the principal Fe-bearing mineral. Commercial-
shatter index (111) is unchanged and the permeability decreases, a t grade concentrates can be recovered from the finely-ground ore by
first rapidly, then more slowly. Increase in clay content increased wet-magnetic beneficiation and they can be nodulised with CaO to
I, I1 and 111, org. binders (e.g., dextrin) increased 111 marked produce self-fluxing nodules from which pig iron of commercial grade
and increase in moisture increased I1 and decreased I ; in each can be produced in an arc furnace using coal and coal char as the
ii-35 1 3.--Ih'DUSTRIAL INORGANIC CHEMISTRY ii-352

reducing agents. r\ high-grade, fine-grained concentrate can be Coarse, irregular shaped crystals were observed under the microscope
smelted by a dry-top technique, using mainly wood chips a:; the with the low-V alloys and rhombic and rectangular shaped crystals
reductant. Ore from this deposit is equally amenable to wet magnetic with 0.25 and 0.85y0 of V. R. A. I(EES.
separation. Grinding to - 100-mesh is required for producing
concentrates containing 61% of Fe -85% of the Fe being recovered. Continuous process for the roasting of arsenopyrites ores.
Energy determinations indicate that the ore is easily ground. Instituto Nacional de Industria (B.P. 844,506, 2.5.58. Sp., 13.5.57.
J. M. JACOBS. Addn. t o B.P. 755,259 ; J.A.C. Abstr., 1957, ii, 319).--0, is intro-
Quantitative determination of the chief elements in iron duced into the roasting stage in amount sufficientlyin excess of the
ores and flue dusts by spectrochemical solution analysis. A. stoicheiometric requirement for roasting t o ensure that the temp. of
Pflugmacher and I<. Schafer (2.anal. Chem., 1962, 185, 419-422).-- the ore in the preheating stage is raised t o +800" by combustion
The sample and the standard oxide mixture are opened up with therein of labile S in the ore with the excess 0, in the portion of SO,
l-I,BO, and brought into HC1 solution for spectrographic analysis, gases from the roast.ing stage which pass in direct heat exchange
using the disc electrode technique : H,BO, also acts as a buffer, but with the ore in the preheating stage for a period of time insufficient
is unsatisfactory for .41,O, contents of ~ 5 % .Good results were for the distillation and combustion of the whole of the labile S.
obtained for Fc, l l n and Mg ; the same accuracy was achieved as J. M. JACOBS.
with the presscd tablet tcchnique, and the sources of error were less. Purification of metals. British Iron & Steel Research .4ss.
P. D. PARR-RICH-~RD.(Inventors: G. M. Gill and M. Ward) (R.P. 870,162, 11,9.58).--
High-purity Fe is produced by melting high-quality Fe (in a wssel
Photometric determination of arsenic in iron ores. E. lined with pure fused MgO) and adding to the melt, whilst the latter
Wrzesifiska (Prace Inst. Hutn., 1960, 12,. 289-294).-Determination is under an inert atm.. a substance which will react with detrimental
of As in iron ores by the photometric method is based on reduction impurities in the metal t o prepare the impurities for removal (,an

with Cu-salt as catalyst a t -


of As,O, by Na hypophosphite to As in a strongly acidified solution amount of Ce in excess of that required t o react with the impurities
looo. .4fter reduction the mixture is present in the melt). The melt is then subjected to a pressure
filtered and the extinction of the filtrate measured with light filter + 0.1 p and any slag formed is removed. J . M. JACOBS.
S 47. The method has a good accuracy; with As content in the
ore of up to O.l"/bthe error is &0.002y0,and > 0.104 the error is Atmospheres for gaseous cementation of ferrous alloys..
-1-0.004y0. This method is quicker and cheaper than the usual Wild-Barfield Electric Furnaces Ltd. (Inventor : I,. G. W. Pale-
method of As determination by dist.iLlation and iodometric titration. thorpe) (B.P. 804,864, 20.1.56. Addn. to I3.P.748,320; J.A.C.
(14 references.) T. M. BARZYKOWSKI. Abstr., 1957, i, 359).-To the monohydric aliphatic alcohol/water
mixture used for cracking there is added a liquid aliphatic hydro-
Determination of the solubility of carbon in iron-titanium carbon, b.p. 150-280" and sp. gr. 0.76-0.8, in a proportion which
alloys by means of [internal] damping measurements. W. is fully miscible with the alcohol/water but is > 3 0 vol.-% of the
KBster and J . Haber (Arch. Eisenkuttenw., 1962, 33, 23-26).- total, in order to boost the methane content of the resulting cracked
Tcchnically pure iron containing 0.2-3.9% of Ti in the form of gas. J . M. JACOBS.
wires of 1 mm. dia. were carburised in CO at 1150" : the conditions Pickling of ferrous surfaces. Pyrene Co. Ltd. (B.P. 869,218,
are critical. The ternary alloys were quenched from 700". The 4.6.59).-The surfaces are sprayed with aq. acidic H,PO, (H,PO,
maximum height, half-width and temp. of damping is not altered 15-45%) containing Felr and Fe"1 in a ratio between 11 : 1 and
by the Ti (i.e., the diffusion rate remains the same). From the 1 ; 7 (between 1 : 4 and 4 : 1). The pickling solution is continuously
variation in differential height, the limit of solubility of cementite circulated through a bed of ion-exchange resin t o remove excess
+
is determined. This, the conode a-Fe TiC/a-Fe T i c + Fe,C + Fe" ions and maintain the concn. of Fern a t 20-857/, of saturation.
differs somewhat from the published diagram. (14 references.) A flash coating of Ni, Co or Ni-Co alloy is applied to the pickled
K. GRAUPNER. surface, followed by a layer of vitreous enamel which is then fired.
Use of X-ray fluorescence analysis in the investigation of J . hl. JACOBS.
various ferro-alloys. J. Bruch (Arch. Eisenkutlenw., 1962, 33,
5---lS).-The possibilities and limitations of fusion and solution of ~ Treating iron or mild steel to permit adherence of porcelain
the samples of powdered steels were extensively studied. Oxidising enamel. Armco International Corp. (Inventors : F. G. Sut.phen,
borax fusion was used for ferro-tungsten, -molybdenum, -niob- J. J . Canfield, R. L. Myers, J. E. Sams and R. S. Burns) (B.P.
tantalum for determination of both major and heavy minor com- 795,632, 13.7.56. Addn. to B.P. 674,490 dated 22.6.50).<0,
ponents ; wet methods were also used for ferro-molybdenum, Co+ Ni or alloys rich in Co and/or Ni are deposited upon the stock or
-niobtantalum and -chromium. The standard error (95% confidence article which is then subjected t o a scale anneal by heating i t (in an
limits) for the major components is 0.25% absolute. The time atm. which is not less oxidising than an atm. of burned natural gas
required is 45 mi11.--3$ h. (10 references.) I<. GRAUPNER. containing 1176 of combustible matter based on dry gas analysis
and having a dew point of 54-82") to 760-1100" for 2--5 min. to
Properties of arc-melted iron-chromium alloys. G. Asai produce a distinct scale. The article is then pickled in acid to remove
and H. Kato ( U . S . B U Y .M i n . Rep. Invest., 1962, No. 5936, 14 pp.),- the scale. J . M. JACOBS.
The alloys containing 1 2 ~ 0 - 5 0 ~ 0Cr were prepared by arc-melting
pure Cr and pure Fe and then fabricated to rods and sheets. The Nickel-chromium austenitic alloys. W . Jessop & Sons Ltd.
physical properties of the specimens showed a regular upward trend (Inventors : G. T. Harris and H. C. Child) (B.F. 787,636--7,
with increasing Cr contcnt. Comparisons are made with commercial 22.4.54. Addns to H.1'. 674,021 and 686,180, respectively).--
stainless steels. G.MACKENZIE. [A] The addition of C e + 104 (Is] added as ferrocerium, mischmrtall
or any Ce-rich alloy) to the alloys, which must have a min. Co
Iron-gadolinium phase diagram. M. I. Copeland, M. Krug, content of 41% (e.g., C 0.3, Mn 0.8, Si 0.3, Ni 12, Co 45, Cr 20, Mo 2;
(1. 1.7. Armantrout and H. Kato (U.S. B w . M i n . Rep. Invest., 1962, V 2.8 and Nb 1*20/;,with remainder Fe), increases their rupture
No. 5925, 16 pp.).-The Fe-Gd phase diagram was determined by strength a t high temp. and improves their forgeability.
thermal analyses, metallographic examination, m.-p. determinations J . hl. JACOBS.
and X-ray diffraction analyses. Data showed a single euteetic
system with 3 intermediate phases Fe,Gd (hexagonal), Fe,Gd Cobalt-chromium alloys. W. Jessop & Sons Ltd. (Invenrors :
hexagonal or rhombohedra1 and Fe,Gd (face centred cubic) which G. T. Harris and H. C. Child) (B.P. 792,447, 22.4.54. Addn. to B.P.
melted incongruently at 1320", 1150" and 1080" respectively. 674,023, 10.2.48).--The min. Co content is 41% and Ce + is
Terminal solubility was limited, and little solubility between the incorporated. e.g., the alloy has the composition : C 0.3, Mn 0.8,
solid phases was observed. Eutectic point occurred a t 85% Gd and Si 0.3, Ni 0.05, Co 57, Cr 20, Mo 2, V 2.8, Nb 1.2.J and Ce 0.05*/,,
, M. J A C O T : ~ .
rutectic isotherm a t 850"c. No shifting of transformations with with rcmainder Fe and unavoidablc impurities.
temp. was observed. (15 referenccs.) G. MACKENZIE.
Oxide inclusions in iron-vanadium alloys. V . A. Mchedlish-
vilil and A . M. Samarin (Dokl. Akad. Nauk SSSH, 1962, 143, 159- Steel.
161).--Experimental alloys were prepared in a high-frequency kiln Method of determination of air infiltration and fuel gas-
(capacity 10 kg.) by heating electrolytic Fc with 0.13, 0.18, 0.25 and and combustion air losses in open-hearth furnace. M.
0.857/, V a t 1560-1580". X-ray analyses showed the presence of Michalowski (Prace Iirst. Hutn., 1960, 12, 273-287).-The method
FeV,O,, Fe,O, a.nd V,O, as inclusions. FeV,O, was predominant described is based on determination of ( a ) the chemical composition
with u p to 0.250,L of V, and V,O, with 0.25 and 0*85?/,of V present. of burnt gases a t specified points of the flue d u c t ; ( b ) chemical
ii-353 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-354
composition and calorific value of producer gas ; (c) rate of flow of oxides (Fe,O,, Co,O,, A1,0,, Cr,O,, TiO,. ZrO,, MnO, V,O,, hfoO,)
producer gas and combustion air at the inlet to the furnace system ; and fluorspar on the surface tension of melts of 70% Si0,-30°/; Na,O,
Id) temperature of gases. From these values, the coefficient of surplus were examined. I t was observed that M e 0 (AI,O,, Fe,O, Co,O,,
air in burnt gas a t specific measuring points was calculated. The MnO), possessed the highest bonding energy but brought about an
0, absorption and CO and C 0 , evolution, burnt gas losses from the increase in surface tension compared with the initial oxides. The
hearth, splitting of burnt gas between fuel gas and air ducts and the contact angle value of formation of the melts on the surface of the
amount of air infiltration were taken into consideration. For all steel was usually 65-67' for oxidised and 15-25" for non-oxidised
these calculations 55 various equations are applied. Practical surface. The contact angle was increased up to 58' on the latter
application is shown in a numerical example concerning a 60-ton surface when 5.4 mol.-% of Fe,O, (I) was introduced. The adhesive
fixed open-hearth furnace. Fresh air infiltrates into the furnace power of the melts on the steel surface was 405-495 erg/cm.s This
system because of leaky and porous brick work, through the hearth rose t o the maximum when the I was introduced into the silicate
gas inlet header, inspection openings, chimney damper and flue phase. Adhesion of all the melts to the oxidised surface was 25-300,;
duct. The amount of infiltrating air is considerable. (35 references.) higher. An increase of I from 8 to 10% was recommended in all
T. M. BARZYKOWSKI. enamels required for coatings, to counteract mechanical destruction.
Mechanism of dissolution of carbide during austenisation A. L. B.
of high-speed steels. Z. Bojarski (Pvace Inst. Hutn., 1960, 12, Catalytic activity of 18/8 stainless 'steel. J. Shabtai (Chem. G.
263--271).-A study is made of the effect of the composition of the Ind., 1962, 1282--1283).-During decomposition of n-C,Hl, a t
basic carbide of high-speed steel of the W-Cr-V type (18-4-1 and 500-550" in a stainless-steel tube packed with stainless-steel wire
there is dehydrocyclisation ( 5%) and concurrent catalytic
-
9-4-2 types), on the changes in the M,C during austenisation a t N

900" to 1300". The carbides isolated by an electrolytic method hydrogenation. A t 630" the concn. of Cl-C, products approximate
were examined by an X-ray method for structural changes and their to the calculated values, but a t 700" liquid and gaseous products
elemental cell parameters were precisely determined. Changes of have approx. same composition as those formed similarly in a Cu
the shape and number of carbide grains were obtained by microscopy tube. Dehydrocyclisation of n-C,Hl, and dehydrogenation of
of etched specimens. With increasing austenisation temp,, the methylcyclohexane occur during contact (6 sec.) of these compounds
number of carbide grains diminishes and in 18-4-1 steel they with stainless-steel wire at 550". but not when the steel surface is
assume a polygonal shape. No changes in the grains were observed oxide-free. Results confirm previous work (Idem., ibid., 1960, 1055).
in 9-4-2 steel. I t is concluded that (1) the M,C carbide (I) is relatively W. J . BAKER.
stable and in normal austenisation conditions does not change its
crystallographic form ; (2) the composition of the I depends on the Steel manufacture. Centre National de Recherches MBtal-
chemical composition of the steel ; in 18-4-1 type of steel i t contains lurgiques and A.R.B.E.D. Acikries RCunies de Burbach-Eich-
more W than that in 9-4-2 steel ; (3) the dimensions of the I lattice Dudelange SOC.Anon. (B.P. 869,802, 26.9.58. Belg., 21.10.57 and
cell change because of diffusion between the matrix and carbides 29.4.58).-In the manufacture of steel by the pneumatic refining of
and coagulation : (4) the increase of carbide grain size a t high temp. pig iron, by means of an oxidising gas rich in 0, (which may or may
is caused by coalescence ; (5) the polygonal shape assumed is due not be loaded with calcareous powder), projected from above on to
to their tendency to secure min. surface energy. (18 references.) the melt in a converter, there is a t the same time projected on to the
T. M. BARZYKOWSKI. melt from above, but through a separate pipe (concentric with the
Determination of the kinetics of the transformation of pipe carrying the OJ, water vapour (superheated to ~ 2 0 0 " or )
austenite to bainite. T. Dumitrescu, C. Ionescu and M. Solacolu liquid water (as a spray from multiple jets or as a mist of droplets)
(Studii Cerc. Metal., Bucuresti, 1961, 6 , 359-374).-A dilatometric so as to impinge a t the same place as the 0, and to agitate the melt.
study of the kinetics of the isothermal transformation of austenite J. M. JACOBS.
in two carbon and two alloy steels showed essential differences of Refining of steel. Ruhrstahl A.-G. (R.P. 869,953, 25.2.58.
the formation of upper and lower bainite. The temp. interval Ger., 27.2.57).-Molten steel is refined under vac. by blowing through
depending on content of C and allied elements comprises 320-380". the steel a hot gas containing CO, with or without CO. At least
The modification of the bainite formation follows the variation of the part of the CO, contained in the hot gas is generated by burning
C solubility in ferrite. The ferrite of the upper bainite does not CO with 0, so as to form a hot blowing gas which is then blown
dissolve C, that of the lower does. The two bainites have distinct gaseous directly through the molten steel. The blowing gas may also contain
microstructures, illustrations of which are given. (16 references.) halogens and/or vaporised halogen-containing compounds,
(From French summary.) M. SULZBACHER.
e.g., AlCl,, AlF, or CC1,. J . M. JACOBS.
Fused salt baths. Imperial Chemical Industries Ltd. (Inventor :
.Rapid t w i s t test for determining hot-forming temperatures R. L. Hewson) (R.P. 870,549, 7.11.58).-The bath comprises alkali
of steels. C. S. Tout, jun., and L. H. Banning ( U . S . Bur. Min. cyanide (equiv. in cyanide content to 10-35 wt.-% of NaCN),
Rep. Invest., 1962, No. 5928, 22 pp.).-A newly developed twist-test alkali carbonate, an activator which is Ti, TiO, or alkali titanate in
machine is described in which the specimens are heated by induction amount equal to 5-15 wt.-% of the bath, calculated as equiv.
instead of radiation, and their temp. is measured by a calibrated Na,TiO,. and, optionally, alkali halide $ 5 0 ( + 2 5 ) wt.-% of the
radiation-detection unit instead of by a thermocouple. Tests can be bath. The bath is employed a t 800-950" for heat-treatment of
made in a small fraction of the time required for making tests in the steels. J . M. JACOBS.
machines previously described. Turns-to-failure versus temp.
Ferritic alloy steels. Firth-Vickers Stainless Steels Ltd.
-
curves indicate that the optimum working temp. for medium-C
steel is 1150",for mild steel 1050",and for stainless steel type-301 (Inventors: H. W. Kirkby and C. Sykes) (B.P. 833,240, 18.7.56.
~ 1 3 0 0 ' ~The.
N

torque data indicate that the ciiergy required for Addn. to B.P. 658,l I5).-The steels contain C 0.03-0.2 (0.04-
working all steels decreases with increasing temp., that stainless 0.12), Si 0.2-1.5 (0-3-0.8), Mn 0.2-1.5 (0.5--1.25), Cr 10-16
steels are considerably more resistant to distortion a t a given temp. (11--15), Mo 0.4-1.0 (0.5-0.9). V 0.1-0.5 (0.1-0.3). N b + T a
than C steels, that resistance to distortion of all steels a t their 0.2-1'0 (0.25-0'5). CO 5-15 (7-12), B 0'003-0.1 (0~005-0~02),
optimum hot-forming temp. does not vary greatly, and that all steels Ni 0-2, and N 0-0.15 wt.-%, with remainder Fe. J. M. JACOBS.
have higher resistance to distortion a t increased working speeds. Austenitic steel alloys. Universal-Cyclops Steel Corp. (B.P.
J. M. J.4COBS. 869,690, 8.5.59. U.S., 18.6.58).-An austenitic Cr-Ni steel alloy
Spectrophotometric determination of aluminium in steel contains Cr 15-30 (17-26), Ni 6-40 (8-35), C +0.25 (0.01-0.2),
with stilbazo. C. LJ. Wetlesen (Analyl. chzm. Arta, 1962, 26, S 0.05-0.2 (0.05-0.15) and A1 0.25-1.35 (0.25-1) wt.-%. with
191--194).-An HC1 solution of the sample is passed through a remainder Fe. J. M. JACOBS.
column of Dowex-1 x 8 ion-exchange resin, which retains the FeIII. Corrosion-resistant austenitic steel. Hadfields Ltd. (Inven-
The .4l is eluted with conc. HCI and determined by measuring the tors : J. R. Rait, T. H. Middleham and J. 0. Ward) (B.P. 803,816,
extinction due'to its stilbazo complex a t 500 mp a t pH 4.8. Cr is 31.3.55. Addn. to B.P. 741,053; J.A.C. Abstr., 1956, ii, 289).-
the only interfering element likely to be present. As an alternative The steel contains C 0.37-0.9, Si 0.2-2, Mn 6-35, Ni > 12,
to removing the Fe by ion-exchange it may be reduced with ascorbic Cr 8-25 and V 0.5-40,(,, the total wt. of these elements being
acid, and Ya,S,O, is then added to eliminate interference due to Cu. +
> 45'7;, , with remainder Fe, the Si V being < 172. The steel may
H. N. S. also contain not more than the indicated amounts of the following
Adhesion of ordinary silicate melts to oxidised and non- Mo 5, W 5, Ti 5, Nb and/or Ta 5, A1 2, Zr 2 and Be 2, the total wt.
oxidised.stee1. A. A. Perminov, S. I. Popel' and N. S. Smirnov of such elements being > 15%, and also Co $ 2 0 , N >0.25 and
(ZA. p v i k l . h'him., 1962, 35, 271-275).-The effects of a series of B +0*5%. J . &I. JACOBS.
ii-355 3.--INDUSTRIAL INORGANIC CHEMISTRY ii-356

Non-Ferrous Metallurgy. P.G. 266(S), 11 pp.).---A bulk standard solution is prepared by


fusion of the sample with KHF,. and fusion with conc. H,SO, to a
Amperometric determination of tri- and penta-valent clear melt, and extraction of the latter in conc. HCI. Be is deter-
arsenic in ores. V. A. Zakharov, A. P. Voiloshnikova and 0. A . mined by precipitation as the NH, phosphate in the presence of
Songina (Zavod. Lab., 1961, 28, 27-28).-The ore is decomposed EDTA a t pH 5.2 after fuming with H,SO,. The Be is reprecipitated
with conc. H,SO,; the product is cooled and diluted, but not as phosphate and determined as pyrophosphate ; the precision is
filtered. One aliquot portion is treated with Cd amalgam, to remove given as &O.lSO,/, actual a t the lO.So/, Be0 level. The Ti is deter-
Cu and heavy metals and to reduce FeS+, treated with conc. HC1, mined absorptiometrically using the peroxide complex and
and titrated amperometrically with 0.01 N-KI, a t +0.2 V relative standard reference solutions on a separate aliquot. The Mn is
to an Hg,I, olectrodc or with a saturated calomel electrode without determined in HNO, by oxidation to HMnO, with NaBiO, and
externally applied e.m.f. AsV oxidises KI to I,, and the titration titration with FeIINH, sulphate. The method is applicable .to ores
curve is r-shaped. Another aliquot is treated with tartaric acid, with 10-13% BeO. J . W. TAYLOR.
carefully neutralised (finally with solid NaHCO,), treated with
K,CrO, to reduce SbIV.and immediately titrated amperometrically Solvent extraction of beryllium from sulphate solutions
with 0-01 N-I, a t the samc voltage as above. As111 reduces I, to by alkylphosphoric acids. R. 0. Dannenberg, D. W. I3ridges
I-, and the titration curve is _I-shaped. A. B. DENSHAM. and J. B. Rosenbaum (U.S. Bur. Min. Rep. Invest., 1962, No. 5941,
16 pp.).-Three alkylphosphoric acids, di-(Z-ethylhexyl) (I),
Adsorption of xanthates at chalcopyrite surface and the heptadecyl (11) and dodecyl (111) in decreasing order of selectivity,
effect of oxygen and carbon dioxide on the adsorbed xanthates. partly separated Be from Al. Rate of Be extraction depended on
S. Ramchandra Rao and C. C. Pate1 ( J . sci. industr. Res., 1961, temp. Extraction coeff. of Be were strongly dependent on the pH
20D. 432--437).-Adsorption of xanthates a t unactivated and and were highest a t pH 1.5 with I1 or I11 and at pH 0 with I.
activated chalcopyrite surfaces were investigated by contact angle Be was stripped from liquor with 6 N-HC1. Before extraction and
(0) measurcments. 0 values in general were lower a t the unactivated after stripping much A1 was removed by crystallisation of NH,41
surface. The difference is believed to be due to a combined effect of sulphate. The filtrate was treated with H,S to remove Cu, Ni. etc.
metal atom arrangement and the nature of the xanthate hvdro- NaOH is added to 1.5 N excess and Be(OH), precipitated by hoiling.
carbon chain a t the surfacc. The higher xanthates underwent (22 references.) G. MACKEKZIE.
oxidation a t the activated surface in the presence of 0, and 0,-CO,
mixtures. The use of xanthates (other than ethyl) in the froth Rapid electrolytic method for the preparation of metallo-
flotation of chalcopyrite followed by aeration of the pulp will be graphic surfaces on fabricated beryllium. J . H . Dingle and A.
beneficial to the flotation. (13 references.) D. J. ELGAR. Moore ( J . Inst. Met., 1962, 90, 270-271).-A method for obtaining
a relatively strain-free surface on rolled or machined Bc which
Preparation of copper powder by carbothermic reduction. responds readily to polarised light is described. After rough
A. V. Ramana Rao and A. A. Krishnan ( J . sci. industr. Res., 1962, polishing on two Sic papers and electropolishing on a moclified
21D, 25-26).--.4 homogenised mixture of C and Cu oxide was 'Disa Electropol' apparatus for 45 min. in which a channelled
heated in vac. s r N, a t 700-900". Cu,O gave a spongy product Perspexplatform allows theelectrolyte [H,PO, (3),H,S04, (CH,OH),,
which was purer than that obtained with CuO. When charcoal was EtOH (1 vol. each)] to pass smoothly beneath the surfaceof the metal
used the product tended to oxidise on drying but the Cu obtained in contrast to the normal turbulent flow, and much of the electrolyte
using graphite, although more resistant to oxidation, was less pure is made to flow through a by-pass. The total time taken is 1 h.
and required a longer reduction time. T. A. INGLES. with only 15 min. complete attention of the operator.
Determination of traces of iron in electrolytic copper. F. C. H. COWPER-COLES.
Vydra and It. Pfibil (2. aizal. Chem., 1962, 186, 295-300).-NH4 Determination of soluble and insoluble zirconium in
thioglycollate is used to mask the Cu, so that the iron may be magnesium alloys. R. H. A. Crawley (Anal. chim. Acta 1962,
determined with o-phenanthroline. If a sample wt. of >0.6 g. is 26. 281-284).-Dissolution of Mg alloys containing 0.5q6 of Zr in
necessary, the Fe-o-phenanthroline complex is extracted with dilute acids is normally complete, but when the alloy contains H?,
CHC1, in the presencc of KI. G. RUSSELL. an insoluble black residue of ZrH 1.55 remains. Addition of H F
Dispersion strengthening of copper by alumina. S . K. Misra completes dissolution. I'yridyl-azo-naphthol is used to determine
and A. A. Krishnan ( J . sci. industr. Res., 1962, 21D, 27-28).- Zr after extraction with trioctylphosphine oxide. Less than 216 of
Mixtures of A1,0, and Cu were produced by the H,-reduction of Al, Zn, Ce and Fe do not interfere. c. s. H O W E S .
oxides obtained from Cu(OH),-AI(OH), mixtures a t 500" and Solubility of sulphur compounds in various media. V.
subsequent pressing under vac. a t 1000" and 40 tons/inz. These Solubility of sphalerite. M. Ichikuni and H. Kamiya (Bull.
compacts were harder, denser and more ductile than those made chem. SOC.Japan, 1961, 34, 1780--1786).-The reaction of sphalcrite
from electrolytic Cu and fused A1,0,. T. A . INGLES. is accelerated by low pH, air bubbling and small amounts of oxidising
Gold-platinum alloys : a review. A. S. Darling (Platiizum agents, particularly Feat, and retarded considerably by H,S. A t
Met. Rev., 1962, 6, 60-67).-A general survey of the alloy including p H 2, Fez+ and Cuz+, separately, prevent rapid solution even with
the constitutional diagram, the thermodynamics of the system, air bubbling. The effect of Fe3+ is increased by Ciizf. Co-presence
mechanisms of pptn., diffusion processes, hardness and mechanical of Feat and C U ~ +with
, air bubbling, increase the solution rate, this
properties. (39 references.) G. MACKENZIE. is attributable to the catalytic action of C U ~on
+ oxidation oof Fez+
to Fe3+. (In French.) E. ENOSJ O N E S .
Determination of silicon, iron, aluminium, calcium and
magnesium in beryl ore. (U.K. Atomic Energy Authority Rep., Amperornetric determination of zinc by the pyridine-
1962, P.G. 267(S), 13 pp.).-The ore is fused with mixed alkali thiocyanate method. A. T. Marunina (Zavod. Lab., 1962, 28.
carbonates and the melt extracted with water. After dehydration 25-26).-Zn and Cu in plating baths or brasses can be determined
the silica is separated by filtration and determined by the H F by amperometric titration with 0.1 M-KCNS. The plating bath
volatilisation procedure. Any residue left after the volatilisation of solution is first treated with H,SO, to decompose cyanides, and then
Si is fused with KHSO, and added to the filtrate. Fe is determined neutralised with NaOH. One aliquot portion is treated with Na,SO,,
as cupferrate, separated by filtration, while after destruction of org. until the first formed ppt. redissolves, and then titrated with KCNS
matter the Fe in H,SO, is reduced with SnCI, and titrated with at -0.5 V (saturated calomel electrode) to give the Cu. Another
aq. K,Cr,O,. Be(OH), and Al(OH), are precipitated with aq. NH,, aliquot is treated with pyridine, until the first formed ppt. redissolves,
the A1 being finally determined as oxinate in aq. HCl. H,S is passed and then titrated with KCNS at - 1.2 V to give the Cu + Zn. FexI,
through the aq. NH, filtrate to remove Co, Ni, Zn, Mn, etc., Ca is Mn and alkali earth metals do not interfere, but F&I, A1 and Cr do.
precipitated as oxalate and the metal determined in dil. H,SO, A . B. DENSHAM.
with aq. KMnO,. The final filtrate is dried and, after removal of Concentration of pollucite ores. I(. C. Dean and I. I... Nichols
ammonia salts, the Mg is separated as MgNH,PO, and weighed as (U.S. Bur. Mzn. Rep. Invest., 1962, No. 5940, 10 pp.).-I'ollucite,
pyrophosphate. At Mn. Ti, C,a levels of 0.1% and Mg and PO,,- a Cs-Al-silicate mineral that has 20-40~0 Cs,O, was separated from
a t 0.4%, the precision is +20% relative ; for Fe i t is f 2 % a t 0.5% three typical ores by flotation of the associated micas, feldspars and
level, for A1 + 0 . 5 % at the 8.5% level, and + 0 - 5 ~ 0for Si a t the other gangue minerals, using H,SO, and H F and a cationic (amine
30% level. J. W. TAYLOR. acetate)-type collector. An 8 % ore of Cs was upgraded to 20% Cs
Determination of beryllium, titanium and manganese in with recovery of 8716 of Cs using this method and slightly higher-
beryl ore. .4non. ( U . K . ,4tomic Energy Authority Rep., 1962, grade ores gave concn. of 28-29% Cs with 92% C.s recovery by the
ii-357 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-358

same process. The method also separates Cs from Na, K and Li Sochevanov (Zavod. Lab., 1962, 28, 15--17).-A polarographic
and in certain cases from Rb. G. MACKENZIE. method is described for determining high contents of Ti and Fe in
Influence of thermal properties of mould materials on ores, using 5 M-H,PO, plus M-H,SO, as supporting electrolytes. The
mechanical properties of cast aluminium and its alloys. oreis fused with Na,O, and extracted with hot water ; the hydroxides
M. R. Seshadri and A. Ramchandran ( J . s r i . industr. Res., 1962, are filtered off, dissolved in H,SO,, reprecipitated with NH,, and
21D, ll-l5).-The mechanical properties of A1 cast a t 30 mm. dissolved in the H,PO,H,SO, mixture. Gelatin is added, and the
Hg and 1100-1200". and also at 700" at atm. pressure, have been Fe is determined between zero and -0.2 V (relative to bottom
measured. These properties improved with increased heat diff usivity mercury pool) and the Ti between -0.2 and -0.8 V. Zr, Nb and
of the mould material. T. A. INGLES. Ta do not interfere. A. B. DENSHAM.
Aluminium-copper-silicon casting alloys. A. I(. Watkins X-ray spectrometric determination of tantalum and
and V. Kondic (Metal Ind., Lond., 1962, 100, 122--125).-Tensile niobium and some minor elements in tantalum-niobium
properties of LM4 alloy can be considerably improved by controlling containing materials. H. Rothmana. H. Schneider, J . Niebuhr
the state and occurrence of the intermetallic constituents of the and C. Pothmann (Arch. Eisenhuttenw., 1962, 33, 17-22).-Three
alloy ; for instance the ' script ' formation can be prevented by methods are described in detail. For unknown materials, the sample
chilling and the Si in the binary eutectic refined by the addition of is fused in peroxide-carbonate, the oxides filtered, dissolved,
Na. These steps improve the tensile properties of this alloy. (11 small precipitated and taken up in acid, leaving all the Ta and Nb and
references.) c . v. amounts of Ti behind. These oxides are determined in H F
solution using polythene cells. For better known samples, solution
Mechanism controlling presence and relative thickness of in H F and determination without separation, and fusion with borax
alloy layers in iron-aluminium diffusion couples. J. W. using the disc of solidified melt are described in detail. The repro-
Frame (Dissert. Abstv., 1961, 22. 1567).-Diffusion couples of (1) ducibility is good. (15 references.) K. GRAUPNER.
pure A1 us zone refined pure Fe, (2) A1-0.85y0 Si alloy us pure Fe,
and (3) A1-0.85:/, Si z's ClOlO steel were prepared and studied Oxidation of tantalum at 500-700". P. Kofstad ( J . Inst. Met..
quant. Activation energy for alloy layer in couple (1) was the 1962. 90, 253-264).-Previous work on the oxidation of Ta is
same as for self-diffusion in pure Fe, but for couples (2) and (3) reviewed and a study is reported made at 0, pressures from 760-0.1
i t was markedly different. I t was suggested that in case (1) the torr on high-purity electron-beam-melted Ta and commercial 0,
vacancies from the Fe, and in (2) and (3) from Al, control the alloy dried over P,O,., Gravimetric oxidation rate measurements were
layer growth. Interaction occurs between Si in the Al, and C or Mn made and the kinetics are discussed ; structural investigation by
in the steel. The Mn increases and the C decreases alloy layer X-ray diffraction, electron diffraction, electron microscopy and
growth. The importance of minimising alloy layer thickness and metallographic techniques were used. In the initial stages dissolution
variations in temp. is stressed. G. MACKENZIE. of 0, occurred with formation of two sub-oxides; this was followed
by transition to breakaway with local spots of Ta,O, and then
Behaviour of adsorbed xanthates at galena surface in the complete breakaway following a linear rate with heavy TalO,
presence of oxygen and carbon dioxide. S . Ramachandra Rao formation. At high temp. and low pressure rate of oxidation
and C. C. Patel ( J . sci. in dust^. Res.. 1962,21D, 8--lO).-The contact cc (0, pressure)+. At high 0, pressure and lower temp. rate of
angles of adsorbed xanthate monolayers a t polished galena surfaces oxidation is independent of pressure. The linear oxidation is inter-
have been used to assess their usefulness in froth flotation in view of preted as oxygen-chemisorption equilibrium followed by a rate
their susceptibility to oxidation. From experiments in 0,. 0,-CO,. determining reaction governed by nucleation and growth of Ta,O,
and CO, it is concluded that only n-butyl and isopentyl xanthates nuclei. Thus alloying of Ta for better oxidation resistance involves
adsorbed a t galena surfaces, are capable of giving the respective reduction of penetration of 0, into the metal, as i t has adverse effects
dixanthogens, and consequent good separations. T. A. INGLES. on mechanical properties. (38 references.) C. H. COWPER-COLES.
Possibility of using methane as reducing agent in the Quality of zirconium prepared by different reductants.
metallurgy of lead. 111. Reduction of lead oxide by methane. G. W. Elger ( V . S . Bur. M i n . Rep. Invest., 1962, 5933, 20 pp.).-
A. Lupu and L. Grigoriu (Studzi Cerc. Metal., Bucuresti, 1961, 6 , Zr was prepared by reduction of ZrC1, with Na, Mg or a mixture of
451-474).--A thermodynamic study of the reactions and their Na and Mg. Zr of highest quality (low 0, content) was prepared by
mechanism during the reduction of PbO by CH, was madc. The reduction with Na and Mg added before initial reaction or by
influence of various factors, duration and temp., consumption of periodic injection of Na during reaction of Mg with ZrCl,, 85% of
CH,, the phases of reduction and the formation of Pb, PbO, PbS, the Zr being recovered in the first case. Temp. range was 700-825",
PbSO, and PbO,SiO, were investigated. In comparison with the the lower temp. being when Na and Mg were used from the beginning.
reduction of the oxides of Zn and Fe, the reduction of PbO is more Residual mixtures of NaCl and MgCl, were more readily removed
favourable so that an industrial trial will be attempted. (27 than NaCl or MgCl, separately in a vacuum distillation furnace.
references.) (From French summary.) M. SULZBACHER. G. MACKENZIE.
Preparing metal-grade vanadium oxide from red cake and Utilisation of ion exchangers in the hydrometallurgy of
mill solutions. C. J. Chindgren, L. C. Bauerle and J. B. Kosenbaum molybdenum. S. Tataru and D. Stefanoiu (Studii Cerc. Metal.,
(U.S. Bur. Min. Rep. Invest., 1962, No. 5937, 14 pp.).-Metathesis Bucuregti, 1961, 6 , 475-482).-The purification of NH, molybdate
of commercial red cake containing a 10% combined Na,O and K,O solutions, derived from the working up of molybdenite, was carried
content to a 98-9976 V,O, product was conducted in presence of out with ion-exchange resins. The cationic exchanger Amberlite
aq. NH,-(NH,),SO,, thus removing Mo and alkali metal oxides. For IRC-50 was found to adsorb the impurities with a capacity of, e.g..
higher grade V,O,, the red cake was dissolved in aq.-Na,CO, and 485 mg. Cu/g. of dry resin. Pure (NH,),Mo,O,, was contained in the
V reprecipitated as NH,VO,. Calcination at 450" then yielded solution. Cu could be recovered from the resin by elution with
V,O, of 99.5% purity. Recrystallisation of NH,VO, before decom- H,SO, and electrolysis. (From French summary.)
position gave 99.9% pure V,O,. K was the most persistent impurity. M. SULZBACHER.
A K-Na-NH,VO, was precipitated from mill liquors a t room Production of molybdenum metal by magnesium reduction
temp. and pH of 5 by adding 1 pound (NH,),SO, per pound of of molybdenum oxides. T. T. Campbell, F. E. Block and E. R.
V,O,. This was redissolved in aq. NH, and NH,VO, precipitated Andersen ( U . S . Bur. Man. Rep. Invest., 1962, No. 5934, 22 pp.).-
with (NH,)2S0,. Full details of reactions are given. MOO, and mixtures of MOO, and MOO, were reduced by Mg in
G. MACKENZIE. closed steel bomb reactors. With Moos pressures exceeding 5000
Use of sodium chloride in the chlorination of columbite p.s.i.g. were reached, but the addition of CaO reduced pressure
and ilmenite. B. S. Mathur, V. S. Sastri and Y . W. Gokhale considerably. Reaction efficiencies over 95 % resulted from reduction
(J. sci. industr. Res., 1962, 21D,5-7).-The addition of NaC,l to a of MOO, and MOO, mixture, but high pressures developed when
mixture of either columbite or ilmenite with C increases the efficiency 30-60% MOO, was used. Best results were obtained when MOO,
of chlorination of the ore. The NaCl complexes Fe and U to form content was 10--30~o. Additions of a small amount of C was
non-volatile double salts. For both systems the effect of C content considered helpful. Purity of the Mo metal ranged from 99.27!, to
and chlorination temp. were examined. Optimum results were 99.8%. Regulus metal was collected as a cast ingot in the bomb.
obtained on columbite using 1 pt. C and 1 pt. NaCl per 10 pt. of Large amounts of C and 0, were found to harden and embrittle the
ore. There were only small variations with ilmenite. T. A. INGLES. metal. G. MACKENZIE.
Polarographic determination of titanium and iron in Molybdenum wires and strips. S. Stolarz (Prace Inst. Hutn.,
titanium-zirconium and iron ores. L. N. Lyubimova and V. G. 1960, 12, 305-312).-Mo wires and strips for use as electric heating
ii-359 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-360
elements were produced on a laboratory scale by reduction of MOO, is titrated with a standard Zn solution to a dithizone end point. The
in H,. The procedure involves two stages, viz., reduction to MOO, method is applicable to contents up to 10% Al ; a t the 3% level
a t 450" and then to Mo a t 1050". The Mo powder obtained was the precision is given as *0.04%. J. W. TAYLOR.
compressed by 0.8 tons/cm.E pressure into bars, which were sintered Assay of plutonium metal. Anon. ( U . K . Atomic Energy
a t 2500". The bars were drawn into wires 0.3 mm. dia. or rolled Authority Rep., 1962, P.G. 290(W), 5 pp.).-The metal sample is
into strips 0.25 mm. thick and 6.5 mm. wide. Annealing temp. was dissolved in 11 M-HCI containing F- (0.025 M ) t o achieve complete
optimum a t 1000-1200". Annealed wires and strips were examined solution, the 1% is maintained in the trivalent state with
for density, hardness, tensile-torsional and bending strength, NH,OH,HCl. The absorbency of the solution is measured dif-
elongation and electric resistivity. (16 references.) ferentially against a Pu reference standard a t 565 mp ; the absor-
T. M. BARZYKOWSKI. bencies of two Pu solutions are also measured differentially against
Siliciding of molybdenum wires and strips. S. Stolarz (Prace the same P u reference standard and a graph is constructed from
Inst. Hutn., 1960, 12, 313-320).-A process is described for protec- which concn. may be derived. The precision is h0.19:' ; the
tion of Mo wires and strips with a coating of MoSi,, thus rendering method is intended for the assay of routine production billets.
them resistant to oxidation a t temperatures of up 1600". Thoroughly J. W. TAYLOR.
cleaned Mo wire with 1 mm. in dia. and 0.25 mm. thick strips and Determination of plutonium in the feed and product
SiCl, of 99.2% purity were used for experiments. The wires were solutions of the plutonium purification plant. Anon. (U.K.
heated a t 1200-1300" (optimum) for 1-2 h. in H, saturated with Atomic Energy Authority Rep., 1962, P.G. 300(W), 5 pp.).-A
SiC1,. T. M. BARZYKOWSKI. quantity of the diluted sample is mounted on a prepared stainless-
Determination of nickel and molybdenum when present steel disc, the u-activity is measured using a proportional counter
together. G. P. Protsenko and P. N. Kovalenko (Zavod. Lab., calibrated against a source prepared from a standard solution a t the
1962, 28, 23---25).--An electrolytic method is described for deter- same time as the sample source. The precision is given as 5.2% ;
mining Mo and Ni when present together in alloys. The Mo is first the samples should be free from other u-emitters a t the stage of
deposited from a solution containing (NH,),SO, and H,SO,, at analysis. J . W. TAYLOR.
pH 4.1 dropping to 3.3, a t 2.4 V. on to a Pt electrode ; the deposit Determination of plutonium in the ,product from the
is weighed as 2M020,,13H,0. The electrode is then cleaned, and the plutonium purification plant. Anon. (U.K. Atomic Energ?,
N i is deposited from ammoniacal solution a t 2.2 V. Any Cu is Authority Rep., 1962, P.G. 297(W), 4 pp.).-The Pu-bearing solution
tlepositecl with the Mo, and must be determined separately. is treated with NH,OH,HCI to yield PuIII and the acidity is adjusted
A. B. DENSHAM. to 1 N with HC1. The relative absorbency is measured a t 565 my
Extraction of uranium from uraniferous Italian minerals, relative to a reference solution and a concn. graph. The precision
-4,Catino ( A n n . Chim., Roma, 1962, 52, 160-183).-.4 procedure for is given as f 0.287/, at the 5 mg. Pu/ml. level. J. W. TAYLOR.
the winning of U from minerals with low U content (-2%) is
proposed. The liquor obtained by treatment of the mineral with Dissolution of plutonium-aluminium alloy. VV. C. Perkins
HC1 is first subjected to countercurrent extraction with acetyl- (U.S. at. Energy Comm. Rep., 1962, No. D P 702, 1 1 pp.).-This
acetone-CHCI, (1 : 1) of pH 0.65 to eliminate most of the Fe. The irradiated alloy dissolved in HNO,-Hg(NO,), a t approx. the same
solution is concentrated under vacuum, HC1 introduced, and rate as U-A1 alloys. The average dissolution rate of 11 mg./cm.,/min.
counter-current distribution carried out a t pH 1.65 to extract the was measured in a solution that was initially 5 M-HNO, and
U. Yields of =92y0 have been obtained. L. A . O'NEILL. 0.5 M-Hg(NO,), but the dissolution rate increased as the initial acid
concn. was decreased. With a series of different test pieces, quite
Rapid analysis of uranium-ore leach solutions. Deter- wide variation in dissolution time was noted, but the addition of
mination of aluminium, arsenic, calcium, cadmium, cobalt, 0.02 M-fluoride eliminated this erratic behaviour and produced
copper, magnesium, nickel and zinc in presence of excess rapid solution. C. v.
iron and manganese. L. Jarman and M. Matic (Talanta, 1962,
9 , 219-'225).--Fe and Mn are determined directly. As is determined Sintering and smelting manganese concentrates from
after distillation and Cu and Ni after pptn. of interfering elements Maggie Canyon ore, Arizona. V. E. Edlund and R. S. Lang
with pyridine-HCI. By ion-exchange chromatography three fractions ( U . S . Bur. Min. Rep. Invkst., 1962, No. 5939, 27 pp.).--Optimum
are obtained free from Fie and containing (1) Co ; (2) Zn and Cd ; conditions allowed the recovery of 857; of the Mn in a flotation
( 3 ) Al, Ca and Mg. A1 is separated from Ca and Mg by extraction concentrate which assayed 36% Mn. Blends of this concentrate with
with CHCl, containing 8-hydroxyquinoline. Iron and Mn are deter- dithionate pilot plant precipitate yielded 90% Mn recovery.
mined colorimetrically, As, Cu, Ni, Co, Zn and Cd polarographically, Thorough mixing and pelletising were necessary for satisfactory
:%I spectrophotometrically, and Ca and Mg chelatometrically. sinter. Best results were given by a charge containing 80o,i, flotation
A. J . BENNETT. concentrate and 20% return sinter fines, if mixed with 6% coke and
Absorptiometric determination of copper in uranium- 12% moisture. Satisfactory single-pass ferrograde sinters were
Zircaloy-2 alloy. Anon. (C1.h'. Atomic Energy Authority Rep., made by raising the proportion of return sinter fines to 40% and
1962, P.G. 269(S). 5 pp.).-The alloy is dissolved in a dilute HF/ moisture content to 2276. Tests revealed that a 2-h. smelting time
HNO, mixture : the excess H F is complexed with II,BO, and the was essential and a charge containing 6776 sinter, 20% limestone,
pH is adjusted to 4--6 with NH,. Tartaric acid is used to prevent 11% coke and 20/, Fe yie1,ded highest Mn recovery.
precipitation of hydroxides. Cu is reduced with NH,OH,HCI, an C . MACKENZIE.
alcoholic solution of nco-cuproine is added and the resulting complex Determination of dithionate, sulphite and sulphate in
is extracted with chloroform. The extract is separated, diluted with manganese leach liquors. N. Soffer (Analyst, 1961, 86, 843--
ethanol, and its absorbency is measured either absorptiometrically 849).--To determine dithionate the sample is heated with conc.
or spectrophotometrically a t 457 mp. The range of applicability is HC1 and the SO, evolved is carried by a stream of CO, into a cooled
10--250 p,p.m. and the prccision a t 45 p.p.m. is Ifr2 p.p.m, excess of 0.1 N-I, the residual 1, being then determined (0.1 5 -
J . W. TAYLOR. Na,S20,). SO, from SO,2- is expelled before the determination or
Absorptiometric determination of iron in uranium determined independently by running the sample into dil. HCl,
alloys. Anon. ( U . K . .4tomic Energy Aulhority Rep., 1962, P.C. sufficientEUTA to chelate interfering cations and excess of 0.1 N-I,
272(S), 6 pp.).-The alloy is taken up in HNO,/HCl or this plus the residual I being then titrated. To determine S0,2-~ interfering
II,SO, ; any infusible material is fused with KHSO,. The U is cations are removed (cation-exchange resin), and excess of
complexed with NH, tartrate and the Fe is reduccd with 0.2 N-BaCl, is added: excess being titratcd with 0.01 M-EDTA
NH,OH,HCl. The Fe is determined absorptiometrically a t pH (Eriochrome black T indicator). The method has been applied to
6-6.5 with the 1 : 10 phenanthroline complex. The alloys of U leach liquors containing per litre Mn (80-90 g . ) , Fe (0.001-2.5 g.),
with, Mo, Nb, A1 and Ti may be treated ; a t the 135 p.p.m. level the Cu (0.05-1.5 g , ) , dithionate (up to 11 g. of SO,) and SO,,,- (110-
standard deviation is f2,80/,. J. W. TAYLOR. 240 g.) A . 0. JONES.
Volumetric determination of aluminium in uranium- Quantiative determination of cobalt, arsenic and manganese
aluminium alloys. Anon. ( U . K . Atomic Enevgy Authority Rep,, in ' nuclear ' steels, by neutron activation analysis. S. May
1962, P.G. 271(S), 6 pp.).-The sample is taken up in conc. HCl. and G. l'inte (Bull. SOC.chim. F r . , 1962, 287-290).-The apFlication
The U is oxidised to UvI with HNO,. Fe and U are removed on a of neutron-activation analysis to the determination of Co, As and
lkacidite FF ion exchanger, while the A1 is determined in the Mn in steel used for nuclear reactors is described. With a short
eluate by complexomctric titration with EDTA ; excess EDTA irradiation time, Mn is determined using the 845 keV peak without
ii-361 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-362
chemical separation. As and Co are chemically separated after 0-35, one or more of Be, Mn, Si, Th and V, each 0-5 (total from
irradiation and determined by the 560 ICeV and the 1-33MeV peaks this group > 15%) and one or more of B, C, Ca and Ce, each 0-2
respectively. Standards of Mn and As in solution and of Co as an wt.-% (total from this group > 5 % ) . [B] The alloy contains Nb
A1 alloy are irradiated a t the same time. Analysis of a number of 55-80, A1 5-20, and Mo 5-20, with, optionally, one or more
steels is reported. E. J. H. BIRCH. (total 2-35%) of Fe, Co, Cr, Ni, W or Zr. 0-20, one or more (total
Nitrogen on nickel surfaces. L. H. Germer and A. U. MacRae > 15%) of Re, Mn, Si, Th or V 0-5, and one or more (total *5%)
(,I. chem. Phys.. 1962, 36, 1555--1556).-1t is demonstrated that, of B. C, Ca or Ce 0-2 wt.-%. J. M. JACOBS.
contrary to what occurs with 0,. N, is not adsorbed on the cryst. Niobium-base alloys. E.I.Du Pont de Ncmours & Co. (B.P.
face of Ni, not even a (110) surface a t room temp. H. S. R. 869,817, 14.11.57. U.S.. 14.11.56).-Oxidation-resistant alloys
comprise Nb 55-80, A1 1-20 (4-20) and Fe 1-25 wt.-%, and,
Copper-base alloys. J. Stone & Co. (Charlton) Ltd. (Inventors : optionally, 0-35 wt.-% of one or more of Co, Ni, W and Zr, the
R. J . M. Payne and A. W. 0. Webb) (B.P. 809,973, 29.10.56. Addn. total of elements of this group being >35%, 0-5 wt.-% of one or
to B.P. 727,021 : J.A.C., 1955, ii, 597).-The A1 content of the alloy more of Be, Mn, Mo, Si, Th and V, the total of the elements of this
is 6.5-3.5%, e.g., the alloy contains Mn 12, A1 4-5, Fe 2-3 and
N group being > 15%, and 0-2 wt.-% of one or more of B, C, Ca and
Ni 2 ; : , with remainder (4:70%) Cu. J. M. JACOBS. Ce, the total of the elements of this group being > 5 % .
Aluminium base alloy. Aluminum Co. of America (B.P. J. M. JACOBS.
869,444, 5.1.59. U.S., 13.1.58).-The alloy contains Cu 3-9 (4.5), Niobium-base alloys. E.I. Du Pont de Nemours & Co. (B.P.
Mn 0.15-1, Li 0.2-3, Mg 0.05-2 (0.15-0.6), and a t least one of 869,937, 14.11.57. U.S., 14.11.56).-The alloys comprise Nb 55-80
Cd 0 . 0 2 4 . 5 , Hg, Sn, In or T1 0.02-3% (the total of Cd, Hg, Sn and Mo 1-20 wt.-% and one or more of Fe, Co, Cr, Ni, W and Zr
I n and T1 being >0.75%). with remainder Al. The alloy may also each in the range 1-30 wt.-?/,, the total of these elements being
contain Zn 0.1-2 and one or more of B 0.002-0.05, Ti 0.01-0.25, >35%. in combination with Be, Mn, Si, Th or V 0-5 wt.-% and
Zr 0.02-0.3 and V O.Ol--O.l%, the total of B, Ti, Zr and V being B, C , Ca or Ce 0-2 wt.-%, the alloy being adapted t o withstand
*0*5./;. J. M. JACOBS. prolonged exposure a t > 800". E.g., Nb 58, Mo 20 and Cr 22 wt.-%
Treatment of aluminium surfaces. Lord Mfg Co. (Inventor : or Nb 56, Mo 20, Cr 14 and Zr 10 wt.-%. J. M. JACOBS.
R . J. Lipinski) (B.P. 869,204, 27.2.58. Addn. to B.P. 856,928, Metallic iron and titanium concentrates. Titan Co. A/S
dated 5.2.57).-The A1 surface is treated with a solution of a nitro- (B.P. 791,366, 19.4.56. U S . , 22.4.55. Addn. to B.P. 754,453;
sulphonic acid, e.g.. 2.4-dinitrobenzenesulphonic acid, containing J.A.C. Abstr.. 1957, ii, 243).-A mixture of titaniferous iron material
HNO, and/or boric acid, a t pH 0.5-4 (1-3), and free from other with 2-6 ( 3 4 1 % of its wt. of an alkali compound (hydroxide,
strong acids (except, if desired, for H F generated by addition of carbonate or chloride of Na, IC or Li) is calcined under reducing
*5% of a fluoride based on the wt. of nitrosulphonic acid) until a conditions at 1100-1200° to reduce the Fe to a metallic state
film comprising a reaction product of A1 nitrosulphonic acid is readily separable from the Ti portion, without melting or sintering.
formed on the surface. The treatment increases the bondability of The excess of reducing material and ash is separated, the reduced
the metal surface towards polymeric materials. J. M. JACOBS. material is finely ground, and the Ti values are then separated from
the metallic Fe portion. J. M. JACOBS.
'Production of brightened and/or smoothed surfaces on
aluminium and aluminium-base alloys. Acorn Anodising Co. Titanium. Allied Chemical Corp. (Inventors : A . G. Follows
Ltd. (Inventor : J . G. Simmons) (B.P. 869,926, 22.6.56).-The alloy and P. A. Keene) (B.P. 870,560, 26.3.59).-Molten Na, K or Na-K
surfaces are treated with a n acid aq. solution containing, per 1.. as is dispersed homogeneously in a many times greater wt. bulk of
active constituents, HNO, 0.05-5 g.-equiv., an amount of at least metallic Ti or NaCl or KCI or mixture thereof, while maintaining the
one primary aromatic amine (aniline, o-toluidine, 2,6-xylidine) absence of TiCI,. Thereafter the mixture thus obtained is caused to
not exceeding the mol. equiv. of the HNO, content of the solution, react in a separate zone, while the Na, K or Na-K is still in a dis-
H F 0.5-10 g.-equiv., and a Pb compound (PbCO,) 0.05-5 g. persed state, with TiC1, vapour to produce metallic Ti and NaCl or
J. M. JACOBS. KCl. The reaction is effected below the m.p. of NaCl or KCI and the
Soldering flux composition. Horizons Inc. (B.P. 869.8'27, entire process is carried out in an inert atm. J. M. JACOBS.
13.8.57. U.S., 16.8.56).-The flux (for A1 and A1 alloys) comprises Zirconium metal. National Lead Co. (B.P. 803,356, 4.7.57.
ZnCI, 82-95 and alkali chloride mixture (NaCl 5-29, KCI 21-61 U.S., 19.7.56. Addn. t o B.P. 758,763 ; J.A.C. Abstr., 1958, i, 35).-
and LiCl 29-66 wt.-"/u) 18-5 wt.-D/,, the ingredients being in Zr metal is produced in a ram-type reactor by reduction with Na and
proportions which produce a composition having a m.p. of < 500". Mg in the ratio of 2-5 : 1, the metals being fed into the molten
J. M. JACOBS. salt bath maintained at 600-900". J. M. JACOBS.
Metal plating baths. A. Miller (B.P. 869,433, 25.1 1.58).-The
bath (for immersion plating of Cu on A1 and A1 alloys) comprises an Alloys and powder metallurgy compositions. E.I. Du P6nt
alkaline aq. solution of a Cu complex of a water-sol. org. amine de Nemours & Co. (B.P. 869,912, 6.11.59. U.S., 10.11.58).-Alloys
selected from alkylene-, alkyl- and alkylol-amines, e.g., ethylene- consisting of Mo 14-65 (30-45), N 1-12 (1-5), Si 14-45 (15-25)
diamine, having pH > 9 a t least sufficient t o depolarise Al. and Ti 15-59 (30-45) wt.-% are produced as shaped objects by
J.,M. JACOBS. pressing into the desired form a powder metallurgy composition
Aluminium-lithium alloys. Ptkhiney Compagnte de Produits having all its particles <75 p and consisting of a mixture of TiS,,
Chimiques e t l?lectromCtaIlurgiques (B.P. 870,261, 22.1 1.57. Fr., Si,N, and Mo in the required proportions. The compressed powder
23.11.56).-AI-Li alloys (Li 1-20 wt.-y/,) are produced by incor- is then heated to 4 900" or the composition is hot pressed at $: 900"
porating in the alloy, or in the A1 used in its prep., XO.005 wt.-"/6 under a prcssure of 4: 1000 p.s.i. J . M. JACOBS.
of Bc andjor Zr. with or without one or more of Ti, Si and B, the Forming superficial diffusion alloys containing chromium.
total amount of the contained elements other than A1 and Li, but Office National d'Etudes et de Recherches ACronautiques,
including the Be and/or Zr, being 0~01-1% of the wt. of the alloy. O.N.E.R.A. (B.P. 825,847, 14.2.56. Fr., 16.2.55. Addn. to B.P.
The alloy is cast into plates which are pre-heated to 500" arid then 693,292 ; J.A.C. Abstr., 1957, ii, 250).-A ' cementation product,'
hot rolled. J . M. JACOBS. i.e., a solid or liquid product capable of giving off vapours of the
Anodic treatment of tin and tin alloys. Ekco Products Co. fluoride of the additional metal on heating, is employed, and these
(Inventors: J. J . Russell and H. N. Headland) (B.P. 819,305, vapours are brought into contact with the body without allowing the
7.11.55. Addn. to B.P. 717.912, J.A.C. Abstr., 1955, i, 740, dated ' cementation product ' (CrF, < 80, H F 10 and NH,F 10 wt.-%),
15.3.51).-A heat-absorbing coating of oxide is formed on a Sn which contains no free Cr, to come into contact with the body.
article by subjecting it t o anodic treatment in an aq. alkaline J . M. JACOBS.
electrolyte, pH > 8.5. containing complexing reagents, c.g., Nickel alloys. 0. Junker and K. Scherzer (B.P.869,753, 24.9.57.
Na,Cr,O,, with Na,B,O,, Na,CO, or Na,PO,, or Na,HPO, with Ger., 24.9.56).-A Ni-Mo alloy comprises Mo 19-32, C 0.01-0-03
H,BO, or Na tartrate. The anodised article is then heated below (O-Ol-O*OZ), Si 0.05-0.6 (0.3-0.5) and Fe 0.1-2 (O.l-l)yo, with
the m.p. of Sn (to 180-230"j to convert the coating into green oxide remainder Ni. A Ni-Mo-Cr alloy comprises Mo 10-19, Cr 10-18,
of Sn. J . M. JACOBS. C 0*01-0.03 (0*01-0.02), Si 0.05-0.6 (0.3-0.5) arid Fe 0.1-2
Niobium-base alloys. E.I. Du Pont de Nemours & Co. (B.P. (O.l-l)"/u with remainder Ni. J. M. JACOBS.
869,629--30, 14.11.57. U.S., 14.11.56).-[~] An oxidation-resistant Alloys. W. Jessop & Sons Ltd. (G. T. Harris and 1%.C. Child)
Nb-base alloy contains Nb 55-80, A1 1-20 (4-20) and Cr 1-30 (B.P. 795,377, 22.4.54. Addn. to B.P. 746,472; J.A.C. Abstr.,
(8-30) with, optionally, a total of one or more of Co, Ni, W and Zr 1957, i, 171).-The alloys claimed in B.P. 746,172 h a w incorporated

F
ii-363 3.--IND U STRI A L INORGA NI C CHEMI SIRY ii-384

in them up to 1% of Ce ; e.g., the mixture C 0.15-0.45, Mn 0.5-1.5, involving polarography, potcntial measurements, chronopotentio-
Si 0.15-0.75, Cr 15-23, Xi 13--28, Co 22---28 (Ni+Co >45), metry, coulometry, and the kinetics of electrode processes. (152
B 0.002-0.04, Ti 0.5---35. Mo 0.5--3.5, W 0.5---3.5 (Ti+Mo+W references.) F. C. SUTTON.
5-10), and Ce > l % , with remainder Fe. J . M. JACOBS. Electrochemical reduction of uranium [VI] to uranium
Separation of thorium from lanthanons. Thorium Ltd. [IV] in carbonate solutions. V. PravdiC, M. Branica and Z.
(Inventor : L. G. Sherrington) (B.P. 869,958, 19.9.58).---An aq. PuCar (Croat. rhear. Acta, 1961, 33, 151--153).-U\'r compounds
solution containing Th, lanthanons and excess SO,%-, e.g., obtained +
electrolysed in 1 M-NaHCO, 0.05 nr-Na,CO, (pH 8.7) show current
by the degradation of monazite with H,SO,, is extracted with a plateaux between -1.0 and -1.5 V vs the saturated calomel
solution in a water-immiscible org. liquid, e.g., kerosene, of an amine, electrode (S.C.E.). Current efficiency is 95% a t -1.2 V vs S.C E.
having a 10-30-C aliphatic chain, which forms a complex with the Pptn of U*V at p H 10.7 with NaOH gives UO,.,,. ( l n English.)
Th and SO,*-. The resulting org. solvent extract is washed with an E. C. DOLTON
aq. solution containing C1- and SO,,- and the Th is then removed Preparation of thin electrodeposits of actinides from
from the washed org. solvent extract by extraction with an aq. aqueous solutions of ethylenediaminetetra-acetic acid. j
solution containing ions which displace the Th from the amine Fuger (BUZZ.SOC.chin?. belg., 1962, 71, l34-l4l),--Sol~ition~ ot'
complex, e.g., aq. NH,NO,. J . M. JACOBS. actinides (*33TJ, 2391', Za1Am, Z**Cm, z 6 T f and z%f) are electi-1,-
deposited in a cell consisting of a bright Pt cathode previously
heated t o red head and degrcased with CCI, and acetone, clamped
Electrochemical. t o a Pyrcx tube by means of a Teflon gasket. A I't disc anotlc is
Chemical methods of testing thickness of electrodeposits. rotated a t 60 r.p.ni. parallel to the cathode and 1 cm. away. The
best results are obtained by a cathode c.d. of 150 m.4/cin.', whcn
h e m Behari Mathur and A. S. Laltshrnanan (EZectropZnti?zg, 1962,
15, 114-1 19).-The development of eight chemical methods of with a deposit of several tens of pg. of P u , 40 to 500,1 yield is obtaincd
testing the thickncss of electrodeposits is described : electrolytic or in 1 11.. 75 t o 8 O y L in 2 h . , and 90 to 95% in 3 h. The solutions a r e
anodic stripping ; stripping ; B.N.F. jet test ; dropping test ; spot 5 x lo-? M with respect to EDTA and adjusted to pH 4. :\t the
test ; immersion or dipping ; calorimetric ; plating time. Their beginning of electrolysis P u deposits more rapidly and the !esa
accuracy, limitations, disadvantages and time taken are indicated. rapidly than the transuranic elements. This is attributed to tlie
(46 references.) C. H. COWPER-COLES.fact that the I'u-EDTA c.omplex is uncharged while the transuranic
complexes have a single and the U complex a double negative charge.
Stripping solutions in thickness testing of electrodeposited The adherence of the deposit after heating to red-heat is good. The
coatings. Nickel and copper over brass and chromium over surface of the cathode after treatment appears brownish but t h i s
nickel. P. B. Mathur, A . S. Lakshmanan, N. Karuppannan and occurs on elcctrolysis o€ EDTA alone and is due t o a deposit c;f I't
Nityanandan J . Paul ( I n d i a n ,I. up@. Chem., 1961, 24, 126-132j.- from slow corrosion of the anode. L1p to 300 pg./cm.* of r'u I~:.LLT
A 10% solution of I<F has been used as an electrolytic stripping been deposited with a )kid of 70%. (12 references.)
agent t o test the thickness of electroplates by measurement of voltage E. J . H. BIRCH
changcs for various currents. Plots of thickness of electroplate vs. Determination of cadmium and nickel in the active material
time of stripping and of current vs. reciprocal of stripping time are from an alkaline storage battery by the amperometric
straight lines indicating 100o/o current efficiency. A. D A R K E . titration method. 6. G. Novakovskaya (Zavod. Lah., 1962. 28,
Satin nickel plating without mechanical treatment. 11. R. 28-29).-The Ni is first pptd. from NH,-NH,Cl solution (pH 1 0 )
Sewman (EEectropEutzng, 1962, 15, 125--129).-The solution and with excess of 0.03 M-dimethylglyoxime, and the Cd is then titr-a!ed
operating conditions are given for the Efco-Udylite Satylite process amperometrically (using the Cd wave) with 0.02 &i-Na,EDT,\, in
for Ni plating. A 6 months' trial shows that an attractive finish is the presence o€ the ppt. The Ni is then determined by titrating
obtained on Cr plated Ni without the loss of Ni ; two-tone effects are amperometrically the excess of diniethylglyoxime with standaril Ni
readily obtained ; throwing power is excellent and resistance t o solution. A , H. DENSH-XM.
corrosion is better than bright Ni-Cr coating ; brass, Cu, Au, Rh
bronze, etc., can replace Cr. A list of possible commercial uscs is Electrodeposited metal coatings. Dehydag Lkutsche Hyi1rit.r-
given. C. H. COWPER-COLES. werke G.m.b.H. (B.P. 798,034, 12.8.55. Ger., 13.8.54. .4ddn. t-o
B.P. 762,257 ; J.A.C. Abstr., 1958, i, 338).-In addition to a n org.
Determination of thickness of chromium-plating on steel, sulphonic acid the clrctroplating bath also comprises org. compounds
M. R . Verma, K. C. Agrawal and J . S. Bahl (,J. sci. industr. Res., of the formula G'K-SO,H where G' is a halogen, CN or SCN ant1 I?
1961,20D, 463-464j.-Cr-plating on steel with a Ni undercoat may is a divalent, substituted or unsubstitutcd saturated aliphatic,
be determined by stripping a known area with I<,S,O, (0.1 9.) saturated cycloaliphatic or aromatic hydrocarbon radical, e.g.,
S?/,-H,SO, and estimating C r by measuring the optical d of the Na 3-bromo (or chloro) propane- or 4-bromohenzene- I-sulphonate.
Cr-EDTA complex. A correction factor for dissolved iron is given; J . &I. JACOBS.
errors due to Ni arc negligible. 11. J. ELGAR. Electrodeposition of metal coatings. Deliydag Deutsche
Electroplating on titanium. L. Domnilrov (MetaE Finish., 1962, Hydrierwerke G.m.h.H. (B.P. 823,152, 9.12.55. Ger., 13.12.54.
60, No. 3, 59--62).-American literature on clectroplating on Ti is Addn. to B.P. 762,257 ; J.A.C. Abstr., 1958, i, 338).---Thcre is
summarised with special reference to Zn, Cr, Cu, Cd, Ni and Al. A incorporated in the electroplating bath 0.1--20 g. per 1. of an org.
summary of Russian experience is reviewed and a recommended sulphonic acid G'.R.SO,H where GI is an org. residue having a C
prowdure for activating and plating polished Ti is given. atom linked exclusively with 3 hetero-atoms, one of which is N
C. H. COWPER-COLES. linked in turn to the residue --K.SO,H, the second of which is S ,
Mechanism of electrolytic polishing of metals and structure residue --H1.SO,H, or S or 0, and R and R1 are substituted or
of polished surface [deduced] from electron-microscope data. unsubstituted divalent org. residues (R is an aliphatic, cycloaliphatic
G. S. Vozdvizhenskii, G. A. Gorbachuk and G. P. Dezider'ev ( Z h . or aromatic residue, e.g., phenylene), provided that Gl.II.SO,H
fiz. Khim. [English Trans].], 1961, 35, 1077--1084).-The fine does not include the group :N(S).C:N.H.SO,H. Examples are the.
structure of electrolytically polished cold-rolled sheet Cu and brass Na salt of N-ethyl-N-4-sulphobutylcarbamic acid Me ester and the
is ascribed to a decrystallisation mechanism during anodic dissolu- Na salt of 2-y-sulphopropylamino-5-methylthiazole.
tion, the degree of structural etching depending mainly on and J . M. JACOBS.
varying directly with the electrochemical non-uniformity of the Electropolishing of zinc and zinc alloys. Diamond Alkali C O . ,
initial surface. Changes in degree arise from diffusion hindrances to Assee of J. A. M. Leduc (B.1'. 869,481, 11.5.59. U.S., 3 . 1 1 3 -
the transfer of the acccptor. Areas of greater non-uniformity are The article to be polished is made the anode in an electrolytic cell
more rapidly removed in a suitable electrolyte a t higher temp. and with an electrolyte comprising 450-900 (665) per 1. of an alliali
c.d. Results confirm that passivity of electrolytically polished surface hydroxide (NaOH) maintained a t 15-105 (21-32") using a c.d.
is due to removal of this active non-uniformity. (40 optical and of 50-800 (200) .4 per sq. f t . The plating of Zn on to the cathode is
electron micrographs and 20 references.) W. J . B A K E R . prevented by using a (hot-rolled steel) cathode which has a surface
Electrochemical investigations in molten salt systems : containing Fe,Op or bj. including a n oxidising agent (e.g., alkali
techniques and applications. H. C. Gaur and R. B. Bhatia ( J . perborate, peroxide or nitrate) in the electrolyte. J . hZ. JACOBS.
s u . zndudr. Rcs., 1962, 21A. I6--25).-Electrochemical techniques Electrolytic preparation of titanium metal. 1.' Spencc &
relating to molten salt systems are reviewed including use of molten Sons Ltd. (Inventors: G. T. Brown, F. E. Stokcs and S. Beaver)
salts as solvents, several fundamental electrochemical investigations (B.P. 826.667, 16.655. Atldn. to H.P. 713,446).-Ti is deposited
ii-365 3.-IR7DUSTRIAL IhTOIiGrlNIC CHEMISTRY ii-366

electrolytically, in presence of an inert atm., from a fused bath of Met., 1962, 90, 267--269).-A marked increase in the amount of
alkali fluorotitanate-halide mixture. The electrolysis is carried out substructure and slight reduction in sub-grain size resulted from an
initially at a cell voltage of 3.5-8 V and a cathode c.d. of 50-10 increase in working from one to three basic operations and a further
amp. per sq. in. until a proportion of the electricity required to slight increase in substructure after six basic operations ; an
deposit as metal the total Ti content of the bath, sufficient to ensure increase in substructure or in pptn. a t sub-boundaries is associated
removal of the bulk of the impurities from the bath, has been passed. with increase in stress-corrosion life ; increased endurance is
The resultant initial cathode deposit is discarded and the electrolysis obtained by additions of Mn and more by Cu and also by slow
is continued (with a fresh cathode) to give cathode deposits of Ti of quenching, but prolonged ageing produced increased endurance only
high purity. J . M. JACOBS. after slow quenching. C. H. COWPER-COLES.
Electrodeposition of nickel. Hanson-Van Winkle-Munning Co. Resistivity of various materials to attack by molten salts
(B.P. 869,403, 14.8.59. U.S., 26.9.58).-There is dissolved in the Ni and metals. A. Lunden (COYYOS. Scz., 1961, 1. 62-64).-
plating bath 0.1-300 nimol. per 1. of the bisulphite addition product Compatibility data are presented for a variety of materials against
of a water-sol. acetylenic compound with either n or 21%times an fused salts of commercial purity, vac. fused, etc., and against liquid
equiv. wt. of a compound capable of forming a chain-carrying Cd, Ga, In, I<, Li, Pb, Rb, Sn, Zn from their m.p. to 800". Salts
sulphite radical, \vhere n is the no. of acetylenic bonds per mol. of mentioned are AgCl, CdBr,, CdC1,-LiCl, CaCl, KCl-LiCl. KNO,,
acetylenic compound. The bath also contains 0 . 2 5 4 0 g. per 1. of LiBr, LiCI, LiCI-PbCI,, LiI, LiNO,, LiNO,-RbNO,, bromides and
water-sol. sulpho-oxygen ' carrier ' brightener compounds of the chlorides P b and Zn, etc. (36 references.) J . W. TAYLOR.
group comprising unsaturated aliphatic sulphonic acids, an aromatic Aqueous corrosion in the field of nuclear energy. H. Coriou
sulphonic acid or sulphonamide or sulphonimide. One example (Corros. Sci. 1961, 1, 132--160).-The principle corrosion
specifies the use of the NaHSO, adduct of but-2-ync-1.4-did with effects are discussed, e.g., intergranular attack, pitting and general
Na, naphthalene-l.3,6-trisulphonate. J . M. JACOBS. corrosion of U and Zr and their alloys, stainless steels, Ni alloys,
Electrochemical method for coating steel surfaces. U.S. Be, Mg and Ti. (27 references.) J. W. TAYLOR.
Steel Corp. (B.P. 825,862, 6.9.56. U.S., 22.6.56. Addn. t o B.P. Return-line corrosion in federal heating systems. A . A.
745,676 ; J.A.C. Abstr., 1957, i, 78).-The solution through which Rerk and G. L. Hopps ( U S . Bur. M i n . Rep. Invest., 1962, No.
the steel strip is passed has p H 1-2 and contains Cre+0.3-2.1 and 5929, 42 pp.).-A tester was developed to disclose which heating
PO,$- 1-8.4 wt.-:o. The strip is subjected, as cathode, t o elec- plants required control of corrosion. Surveys showed that H,CO,
trolysis a t a c.d. of 15-90 A per sq. ft. J. M. JACOBS. was largely to blame. Concn. of H,CO, was considerably reduced by
decreasing make up rate and recycling of CO, in the return conden-
sate, replacement of Na,CO, by NaOH in feedwater treatment and,
Corrosion. where necessary, external treatment to decrease the make up water
alkalinity. Cyclohexylamine or morpholine was used t o neutralise
Effects of electrolyte motion during corrosion. T. K. Ross condensate acidity, the latter being especially useful in good
and B. P. L. Hitchen (Covros. Sci., 1961, 1, 65-75).-The effect feedwater deaeration systems. Filming treatment with octadecyl-
of rate of flow of water a t p H 6.8 on the electrochemical properties amine (2 p.p.ni.) did not give satisfactory results but when applied
of tubular couples of Fe/Cu, Carbon/Cu, and Cu tubes of different intermittently a t 10 p.p.m. results were better. Methods of deter-
dia. was studied; fluid velocity influences the rate of 0, supply mination of NH,, dodecylamine and amine-N are given. (17
to the surface. In the Fe/Cu case the Fe anodc is little affected by references.) G. MACKENZIE.
flow rate. In the Cu/C case the Cu anode open circuit potential falls
with flow increase in the streamline range and becomes more Corrosion inhibitors for cooling water. I. Inhibitors for
positive with turbulent flow conditions. Surfaces exposed to higher mains water under static conditions. T. K. Grover, N. K.
flows are anodic relative to ones a t lower flow but when turbulence Mnlrerji and R. Sanyal ( J . scz. industr. lies., 1961, ZOD, 445-448),-
occurs the surfaces exposed to the greater turbulence arc ennobled. Na. benzoate, NaNO,, Na,HPO,, ' Calgon,' Na silicate and Na,CrO,
Sudden flow changes result in reversal of potential. (22 references.) were compared far inhibitive properties in water a t 40". The metals
J . W.TAYLOR. tested were mild steel, cast iron, Al, Cu, brass, zinc, lead, solder and
Propagation of stress-corrosion cracks in metals. J. G. soldered brass. Chromate and silicate were the best all round materials.
Hines (Corros. Sci., 1961, 1, 21-48).-.4 critical review of theoretical No inhibitor protected lead. D. J. ELGAR.
assessments of stress-corrosion crack propagation with specific Corrosion inhibition in moving media. T. K. Ross and D. H.
reference to the causes, conditions necessary and the rate of crack Jones ( J . appZ. Chem., 1962, 12, 314--319).-Tubes of mild steel
propagation. (46 references.) J. W. TAYLOR. were immersed in 0.5 M-H,SO, containing thiourea and flowing a t
Development of stress-corrosion cracks in austenitic various rates. A t low thiourea (I) concn. (0.2 x M ) corrosion
chromium-nickel steels. J. G. Hines (Corvos. Scz., 1961, 1, rates increases very slowly with Reynolds no. (11) and at high flow
2-20).-Directly loaded axially stressed specimens of austenitic rates corrosion is much less than in the absence of I. At higher I
Cr-Ni steels were exposed to boiling MgC1, (42% solution) a t 150- concn. corrosion is inhibited a t low flow rates but the inhibition
154'. There was an induction period (I) followed by crack propaga- effect is gradually lost as the flow rate increases. The corrosion rate
tion, the latter being subdivided into two stages. I was sensitive to
composition, temp., surface condition, etc., but specimen size and
geometry had little effect. The total length of the crack propagation
in 2 x 10F M- and 5 x
- M-I is proportional to the square root of
I1 up to the values of 2000 and then increases at a more rapid rate,
particularly at higher concn. of I. The results are discussed in the
period is not altered by most changes in environmental conditions, light of probable mass-transfer and depolarisation effects and the
alloy composition, etc., but the initial crack propagation stage is importance of evaluating inhibitor systems under dynamic conditions
very sensitive to specimen geometry, applied stress and metallurgical is indicated. (12 references.) 0. 1LI. WHITTON.
conditions. When the stress is relieved b y crack formation, the Physicochemical properties of dicyclohexylammonium
propagation stage may be delayed indefinitely while the second stage nitrite, a volatile corrosion inhibitor. I. L. Rozenfel'd, M. N.
of propagation is accompanied by a fall in potential and by accelera- Polteva and V. P. Persiantseva (Zh. $ 3 . Khim. [English Transl.],
ting extension. Neither effects occurred in the first stage but 1961, 35, 725--727).-Saturated v.p. of pure cryst. dicyclohexyl-
sufficient corrosion current is available to account for both stages ammonium nitrite (Dichan) (I),m.p 180", rises from 2.5 to 92 x lo4
by purely electro-chemical effects. ( 1 6 references.) mm. (Hg) between 35 and 66". Values were obtained by Knudsen's
J. W. TAYLOR. method and are of higher accuracy than those of Wachter et al.
Effect of glass on corrosion reactions in fused chlorides. (Covrosion, 1951, 7, 284) who used the dynamic method and impure
C. Edeleanu, J. G. Gibson and R. Littlewood ( J . apfil. Chem., 1962, I . The latent heat of sublimation of I is -25 kcal. per mole. A
12, 305-309) .-Investigation shows that glass or silica containers proposed structure for vapour-phase I is based on niol. complexes
can markedly affect corrosion tests in fused chlorides. Consequently, rather than on ion-pairs. W. J . BAKER.
test results obtained in glass apparatus may not be directly applicable
to an all-metal plant in contact with fused chloride, and those Effect of additives on water-induced pitting of ball-bearings.
obtained in all-metal apparatus may not be directly applicable t o D. Scott ( J . Inst. Petrol., 1962, 48, 24-25).-Additions of, alcohols
plant containing glass or ceramic components as well as metal. (3%) to oil containing water retards pitting in the four-ball machine
0. M. WHITTON. (cf. J.A.C. Abstr., 1959, i, 462; 1961, i, 223). In water-saturated
Effect of substructure on the stress-corrosion of commercial (3%) oil iso(pent)yl (I) was superior to mixed primary decyl alcohols
aluminium-zinc-magnesium alloys. R. W. Elkington (1. Inst. (11) or branched 13 C alcohols (111), and would be effective in 1 %
ii-367 3.-INDUSTRIAL INORGAA'IC CHEMISTRY ii-368

concn. With frce water (37;) in the oil, I, I1 and 111 were equally (Corros. Sci., 1961, 1, 161-169; 170-176).-I. T r tracer a t
effective and 5% of I would be necessary. Some complex N-bases chromate concentrations of 11.6 p.p.m. was used. A specific, activity
(20/,) (sarcosine or imidazoline mixed with N-methylglycine) were of 700 mc 6*Cr/g. Cr was used with electrolytic grade rolled Zn
Yery effective in inhibiting the attack of both free and dissolved sheet. Cr deposition lasted for several weeks, the rate of reaction
water. A. R. PEARSOK. was greater a t low pH. Cr0,z- ions are reduced a t the Z n surface
Cathodic protection against dezincification. J. T. Crennell resulting in an invisible ZnO/Cr,O, film. Abraded surfaces had a
.and L. J. E. Sawyer ( J . appl. Chem., 1962, 12, 170--173).-Naval uniform deposition of Cr while a polished surface had Cr-rich spots.
Brass or High Tensile Brass may be protected against dezincification Using *SCl tracer C1- was taken up irreversibly a t certain sites on
in sea-water by cathodic protection a t a potential of -0.60 V a n abraded Zn surface; film breakdown in the C1- solution is
(relative to Ag-AgC1) : dezincification can be arrested by the above apparently followed by film repair involving CrO,z-. (29 references.)
treatment. 0 . M. WHITTON. 11. Using n6Znsurface layers, a study was made of the corrosion
inhibition mechanism in water and dil. salt solutions ; labelling was
Control and metal protection against corrosion. N. D. achieved by surface exchange with ZnCI,, by electrodeposition and
Tomashov (Corros. Sci., 1961, I , 77-87).-Existing methods of by evaporation. Corrosion of ZnC1, dipped surfaces was accompanied
corrosion protection are reviewed in terms of their influence on the by a slow, continuous loss of activity from the surface; in lo-,
specific electrochemical processes involved : aspects detailed are M-chromate solution the metal was untarnished b u t a rapid activity
protective coatings, treatment of corrosive media. electrochemical loss was observed. M-molybdate solution had a similar effect
protection, development of new materials and design improve- but inhibition was only temporary. Electrodeposited or evaporated
ments. The modes of action of all these methods are tabulated ~ i t h coatings showed a slow continuous loss of activity in chromate
examples. (22 references.) J . W. TAYLOR. solutions. J. W. TAYLOR.
'Corrosion in stainless steels. I,. AmCen and B. Andcrsson
(IStarke, 1962, 14, 118--124).-Types of corrosion : general. pitting, Electrochemical behaviour of sprayed aluminium coatings
stress-, intercryst- contact- and crevice corrosion are described and on mild steel. I. Immersed foils and panels. 11. Immersed
illustrated. Possibilities of avoiding such conditions by suitable couples and artificial pores. T. K. Ross and (I.) E. I,. Smith,
choice of materials and construction are discussed. E. M. J . (11.) P. H. N. Webster (Corros. Sci., 1961, 1, 108--119 : 120~-131).-
1. The potential behaviour of > 99.5% pure .41 coatings exposed to
Corrosion of steel in hydrochloric acid : inhibitor actions 0.001 N-NaCI is outlined. Sprayed material was more reactive than
of urotropine-arsenious oxide-urea' combinations. A. K. massive metal, the 99.9% pure A1 gave superior protection. Cor-
Roy, A. Mukherjee and K. K. Chakravorty (1.sci. indzistr. Res., rosion of the 99.576 pure A1 was stifled more rapidly tha.n on the
1961, 20D, 441-444).-A mixture of urotropine and As,O, is a 99.9% pure Al, possibly due to the cathodic nature of impurities.
better inhibitor than either alone. Addition of urea enhances their Staining of the coating occurs a t pH >7. The reactivity of the
action individually and together. Recommended strengths are 0.8% coating is probably due to internal stresses, to porosity and to
urotropine, 0.2% As,O,, and 0.2% urea, giving a protection of 99.994 surface roughnesses, pores behaving as sites for anodic acidity.
a t 70" in 2.22 N-HC1,and 99.8% in 4.38 iv-HCl. Polarisation curves Coatings above G mils thickness give essentially physical protection
were constructed and the mechanism of inhibition is discussed. t o the underlying steel while pore plugging is significant as thickness
D. J. ELGAR. decreases ; 0.5 mil coatings give protection for a few days only.
Effects of alloy composition on the stress-corrosion (25 references.)
behaviour of austenitic Cr-Ni steels. J. G. Hines and E. K. W . 11. A1 coatings separated from mild steel panels by an insulating
Jones (Couros. S c i . , 1961, 1, 88---107).-A statistical analysis of the layer were examined ; the couples were immersed in 0.001 N-NaC1,
stress-corrosion characteristics in boiling 42 w/v% MgCI, of Cr-Ni in artificially hard water and in artificial sea water. Three stages in
.austenitic steels (with up to 60% Cr+Ni) in terms of compositional protective action exist : (i) A1 dissolution a t random sites due to
.changes is given. Each steel gave the log (time to fracture)/applied oxide film weakness which is more prevalent in the sprayed material,
stress relationship in two linear parts which intersected a t a stress varying with deposit age and purity. Dissolution rises quickly to a
.close t o the 0.1"' proof stress a t 20". At higher stresses, the slope max. and protection is a t a max.; an initial induction period of low
of the relationship showed no variation with composition unlike a t solution rate depends on film age and protection is low. (ii) After
lower stresses when i t decreases with increasing Mo content and max. dissolution is established geometric factors become very
increases with Ni and Cu content. Times to fracture a t the proof important ; the cathodic alkali produced a t the protected steel
.stress varied with composition increasing with specimen size for dia. surface is suficiently strong to dissolve AlzO, antl cathodic protection
<0.3 cm. and passcd through min. with increase in C, or Mo. Ti is self sustaining. (iii) Precipitation of corrosion products and
modifies the effect of C. Many commercial compositions appear to salts causes blanketing of the exposed steel and sealing of the pores ;
be near the worst possible compositions ; low C ( <0.03% max.) this leads to long term protection. J . W .TAYLOR.
is preferable. Stress relieving improvcs life, particularly with
Mo-free steels. (14 references.) J. W.TAYLOR. Oxide Alms on aluminium. I. Ionic conduction and struc-
Anodic characteristics of mild steel in dilute aqueous soil ture. 11. Kinetics of formation in oxygen. M. J . Uignam (/.
electrolytes. T, P. Hoar and P. W. Farrer (Corros. S c i . , 1961, 1, tion electrochem. SOC.,1962, 109, 184-191 ; 192-198).-- -1. An .investiga-
49-61).-The variation of anode c.d. with electrode potential was to compare the ionic conduction of films formed in dry 0,
studied, using modified Piontelli cells for uniform c.d. log anode with that formed by anodic oxidation, undertaken for adaptation of
c.d./log potential plot was rectilinear. -4 change of 10 mV gave a an electrolytic method for determining anodic film thicknesses to
409; increase in c.d. undcr favourable conditions and 80% in the measurement of oxide films formed in dry O,, is described.
unfavourable conditions such as low S2~-concn. or large no. of Anodic polarisation measurements were made o f anodiscd A1 antl
sulphate-reducing bacteria. (11 rcferences.) J. W. TAYLOR. A1 alloys in aq. H,BO,, the specimens being annealed in Hc a t 250-
450" and exposed to dry 0, a t 250, 350 and 450". Electron trans-
Mechanism of the formation of two-layer sulphide scale mission micrographs were taken on films stripped from .41 to elucidate
on copper. S. Mrowec and T. Werber (Roczn. Chem., 1961, 35, oxide crystallisation effec1.s. Information is reportcd on the nature
1661--1671).-The study was made with 40 x 30 x 5 mm. plates of of the so-called ' amorphous ' films, the diherencc in properties
99.999% Cu immersed 3-60 min. in molten S a t 444'. Liquid S between anodic oxide films and films formed in dry 0, a t high temp.
remaining on the surface of withdrawn plates was burned in air in and on the nucleation process associated with the appcarance of
less than 10 sec. The chcmical composition, layer structure, and y-alumina erystallites in the oxide film. (23 references.)
kinetics of the scale formation were investigated. Microscopical 11. A study of the oxidation mechanism of pure X I and the effect
examination of representative cross-sections of the scale disclosed, of small additions of Ga, Fc, M n , Si and Cu reported provides a
a p a r t from the outer polycryst. compact layer and the inner porous reasonablc explanation for the behaviour of A1 heated in dry 0,.
fine crystall. layer, the presence of a third intermediate one. This Below 450" and initially a t higher temp. a very thin amorphous film
was also porous, but its crystals were ncedle-like. The innermost is formed for which the kinetics agree with thc cstablishment of a
layer consisted of fine grain crystals, while the outermost, compact nearly constant p.d, of 0.73 Y across the film by electron transport
,on thc surface, was made of parallel bars, perpendicular to the from metal to oxide surface levels, the rate of formation of the film
surface. All three layers represented the same phase of sulphidation being unaffected by grain orientation. The resulting field causes
product, the digenite. Kinetics of each layer are discussed. (22 metal ion transport through the film in accordance with an cxponen-
.references.) (From English summary.) A. L. GROCHOWSKI. tial field strength relation. Above 450" crystalline y-alutnina is
Radiotracer study of the passivation of zinc in chromate formed, the w t . gain data conforming to a linear oxidation Ian.
solutions. I. 11. li. C;. McLarcn, J . H. Grccn and A. H , Kingsbury Only impurities which can introduce defects into the ositlc film
ii-369 3.-IXD USTRIAL INORGANIC CHEMISTRY ii-370
affect the ratc of formation of the amorphous film and then only i f >SO% of the water which can be formed in condensation of the
the concn. is the same or larger than defects introduced by the reactants is removed. The products are useful as anti-corrosion
electric field, but very small traces could have a profound effect on agents in hydraulic fluids, etc. E. ENOS JONES.
the nucleation of y-alumina and consequently on the oxidation Pipe asphalt. Shell Internationale Research Maats. N.V. (B.P.
rate. (18 references.) C. H. COWPER-COLES. 869,972, 1.2.60. Neth., 3.2.59).-Thc pipe asphalt (used for protec-
Solution and diffusion of corrosion oxide film in Zircaloy. tion of iron pipes against corrosion) comprises a blown asphaltic
R. M. Treco ( J , electrochem. Soc., 1962, 109, 20&-211).-The bitumen, which has a softening point (ring and ball) in the range
formation of an oxide surface film on Zircaloy-2 during processing 100--125" and answers the relationship V = 8 P + 6 1 & 5 where V is
and methods of removing i t are discussed. A study of film accu- the softening point in Oc and P the penetration index, in admixture
mulated after 3 days in 6 8 0 ' ~water and subsequent anneal at 750" with a filler which is obtained by milling a water-insensitive minerak
is described. The effect of the additional 0, was increased hardness. (e.g., slate dust) and of which > 10% by wt. IS retained on ASTM
From a hardness against penetration curve i t is seen that the sieve 325 and none is retained on ASTM sieve 50. E. ENOSJONES.
hardness is almost doubled a t the surface after 4 h. anneal. I t is
apparent that removal of 0.0015-0.002 in. by pickling is sufficient
to reduce the hardness to an acceptable level. The hardening effect Inorganic Chemicals.
is considerably reduced a t high temp. and the notch sensitivity is Inspection of pure dried vacuum salt. Anon. ( U . K . .4tomic
very low. These factors substantiate the assumption that Zircaloy Energy Authority Rep., 1962, P.G. 299(W), 6 pp.).-The assay of the
is not damaged by solution treatment to remove oxide if the surface NaCl was effected by titration with standard AgNO, using I<,CrO,
is subsequently pickled. C. H. COWPER-COLES. as the indicator ; acidity or alkalinity was determined by titration
Oxidation of zirconium and zlrconium-oxygen alloys at using bromothymol blue as indicator. Other items included volatile
800". K. Osthagen and P. Kofstad ( I . electrochem. Soc., 1962, matter by drying at 27Ooc, insol. material by filtration, of a solutiom
109, 204-207).-Oxidation of Zr involves both 0, dissolution and and appearance in solution. J. W. TAYLOR.
oxide scale formation, the rate and kinetics being dependent on Manganous-sulphate as an aid in the production of indus-
concn. of Oain the metal, but further studies of the relative interplay trial grade common salt. C. S. Acharya and S. P.Tandon ( J . sci.
between oxide formation and 0,dissolution are necessary to establish industr. K e s . , 1961, 20D, 464-465).-0.01% wt. MnSO, added ta
the mechanism involved. The initial oxidation follows a cubic saturated brine is sufficient t o aid crystallisation, giving a product
oxidation rate but after a short time, decreasing with 0, concn., over 97% pure and low in CaSO, and moisture. D. J. ELGAR.
more rapid oxidation occurs, the rate of which rises with 0, concn.
up to 15% 0,. (23 references.) C. H. COWPER-COLES. Roasting of precipitated copper sulphide. R. I. Razouk,
M. Y . Farah. R. S. Mikhail and G. A. Kolta ( J . appl. Chew., 1962,
Fission fragment recoil effects on zirconium oxidation. 12, 190--196).-The roasting of precipitated CuS in a current of air
W. C. Yee. G. H. Jenks and E. E. Stansbury ( J . electrochem. SOC., has been investigated by thermogravimetric analysis at 150-800"
1962, 109, 198-204).-To find an explanation for the increase in under isothermal conditions. The distribution of Cu between CuS,
corrosion rate of Zircaloy-2 and Zr when irradiated, data on the CuSO, and CuO was determined by chemical analysis and the state
effects of fission fragment recoils in the gaseous oxidation of Zr were of the solid phases was identified by X-ray diffraction patterns.
obtained under reactor radiation ( a ) including fission fragment During roasting, CuS is converted t o Cu,S, CuSO, formation
recoils, (b) in the absence of fission fragment recoils and ( c ) with no increases with rise of roasting temp. to a max. at 400' and then
radiation in a specially designed autoclave. The results were decreases, while the Cu oxide content increases with rise of roasting
examined by microscopy with high and low magnification, surface temp. first as Cu,O a t the lower temp. and then as CuO above 500".
topography of replicas by electron microscopy, visual comparison of A mechanism of the roasting process is proposed based on t h e
surface interference colours and weight change. The oxide film results. (10 references.) 0. M. WHITTON.
either underwent a phase transformation or developed randomly
oriented grains, all other oxide surfaces remained highly oriented ; Electron microscope observation of porosities, carbon
recoil bombarded surfaces produced a diffuse ring pattern while the inclusions and dislocations in hot pressed beryllium oxide.
surfaces exposed to neutron flux only had spotty rings ; the oxide A. Bisson and H. Frisby ( J . nucl. Muter., 1961, 4, 133--142).-The
film of the surfaces exposed t o fission fragments was thicker and experimental techniques are detailed. C was found as accumulations
showed mounds of -0.5 I.(. Insufficient information was obtained a t grain boundaries in C-rich specimens with a distinct orientation,
to establish the mechanism but the technique could be used for as long bands segregated around dislocation lines, and as oriented
studying fission fragment recoil effects on other metals. (15 particles at grain intersections. At 1500"in air the C is oxidised and
references.) C. H. COWPER-COLES. CO, bubbles form a t grain junctures, the bubbles surfaces having a
polyhedral form ; a certain correlation between dislocation arrange,
Chemical coatings on zinc and zinc alloys. Pyrene Co. Ltd. ment, C precipitates and bubble formation appeared to exist. (In
(Inventors : A. M. Triggle and H. A. H. Jenkins) (B.P. 869,395, French.) J. W. TAYLOR.
27.5.59).-An acid solution for the treatment of Zn and Zn-based Irradiation-induced property changes in beryllium oxide.
alloys, to protect them from corrosion, is prepared by dissolving in F. J. P. Clarke, G. Tappin and T. I<. Ghosh ( J . nucl. Mater., 1961,
water CrO, and Cr,(S0,),,6-7H20 and has a total content of Cr 4, 125--132).-Hot pressed B e 0 was irradiated to neutron doses
(calc. as CrO,) and CrIII [calc. as anhyd. Cr,(SO,),] of 2-30 (2-9) g. with neutrons of energy > 1 MeV. For doses < 1.5 x lo'@n.v.t. the
per I., the ratio of CrvI to CrJ" being 0.2-7 (0-2-1.5) by wt. and change in rupture strength was small ; significant changes occurred
the pH 1.8--2.8. J. M. JACOBS. in resonant frequency at doses > 6 x 10l8 n.v.t. but the sign and
Corrosion-resistant coatings o n metals, Amchem Products magnitude of the changes'varied with material source. The log
Inc. (B.P. 870,572, 24.2.59. U S . , 14.3.58).-The surface of the fractional growth of lattice parameter incrcased with log integrated
metal is brought into contact with an aq. acid non-balanced neutron flux > 1 MeV in energy in a linear manner. Unbaked and
phosphatising solution containing, as the only P-containing ingre- irradiated materials showed a higher gas evolution in hot pressed
dient, an alkali or NH, pyrophosphate 0.05-13 (1-5) wt.-%, and samples than in all others ; no satisfactory explanation of this
0.0008-0.06 pt. by wt. of FelI1 per pt. by wt. of pyrophosphate effect was given. J . W. TAYLOR.
(calculated as P,O,), has p H 3.2-6 and contains an accelerator Irradiation damage in beryllium oxide. F. J. P. Clarke a n d
(chlorate, nitrite or peroxygen compound) capable of oxidising FeI1 J. Williams (.f, nucl. Mater., 1961, 4, 121-124).-U.K. data on t h e
to FeIII, present in a concn. equiv. to 0.2-10 g. of chlorate per 100 irradiation behaviour of B e 0 are summarised and discussed.
ml. of solution. Contact is maintained a t $49" until a closely Mechanical properties were little affected at < 1.5 x 10'0 n.v.t.
adherent, non-powdery coating is formed. J . M. JACOBS. +
neutron flux ; the resonant frequency change 2 x l W and t h e
Modified organic fluids of the borate-glycol type. U.S. rupture strength42 x lo-'. Fractional vol. changes of +
Borax & Chemical Corp. (B.P. 870,048, 4.3.58. U.S., 5.3.57).- occurred and this was d dependent. No gas evolution > 5 x C.C.
Borate-glycol condensation products are produced by heating of gas a t S.T.P. per C.C.of Be0 was produced on heating to 2000"
together a tetraborate or metaborate of an alkali metal or alkaline provided steam was baked out. The results are discussed in relation
earth metal and a glycol of 2-6 C-atoms or a monoalkyl ether t o technological problems of B e 0 as a reactor moderator and
thereof (alkyl of 1-4 C), heating being continued, if desired a t canning material. J . W. TAYLOR.
reduced pressure, until the product is homogeneous and the total Effect of thermal treatments and neutron irradiation om
amount of water removed from the reacting mixture is such t h a t the physical and mechanical properties of hot- pressed
ii-37 1 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-372

beryllium oxide. J . Elston and C. Labbe ( J . nztcl. Muter., 1961,


4, 143-164).--Heat treatments at 1400" for prolonged spells
- 196 of I i , A1 a n d Cr oxides. Adsorption and desorption rates of
0, on these oxides were measured at 300-500". The foreign ions
decrease the d and mechanical strength by the formation of gas in the oxide made no change in the activation energy of either
bubbles. hfaterial of >2.9 g./c.c. is more sensitive t o neutron adsorption or desorption, on either oxide. The surface area was
damage than material of 2.7 d.g./c.c. Material of d 3 g./c.c. under- increased by A1 and Cr, and decreased by Li. The results arc
goes complete disintegration on irradiation t o 2 x 102" p/cm.? at indicative of a change in the number of sites available for adsorption
4 100' ; this is due t o gas evalution and anisotropic deformation of rather than a change in the electronic state of the Zn and Ni oxides.
the crystal lattice. Length changes were always greater than I<. RIDGWAY.
predicted theoretically. Even for lightly irradiatcd material a Oxidation of zinc sulphide spheres in an air stream.
temp. of 1200" is required t o anneal out damage. Wigner energy
release is not considered a serious reactor problcni while thermal
shock resistance is considered adcquatc. (33 references.) (In
1962, 40, 23--34).-2nS -
K . G. Denbigh a n d G. S. G. Beveridge (Trans. Instn chent. Engrs.
spheres, 1 cm. dia., were oxidised in a n
air stream between 500 ancl 1400",and the reaction rate followed by
French .) J . \v. ' r A Y L O R . analysis of the exit gas for SO,. Photographs were taken of the
Fabrication and properties of dense beryllium oxide. S. C. spheres, which in some cases developed an oxide layer not in contact
Carniglia and J . 12. Hove ( J . nucl. bfaler., 1961, 4, 165--176).-- with the underlying sphere surface. As the temp. is increased, the
Commercial powders may be pressed at 1500---1900° at 2---6x loy reaction rate is controlled in succcssion b y the chemical kinetics,
then by the resistance t o diffusion of the aerodynamic boundary
p.s.i. in a n u m l m of shapes t o give 98-1000,: of theoretical ; 1 % layer ; after the reaction has proceeded for a few min. the oxide
MgO improvcs the ratc antl uniformity of dcnsification a n d empirical
expressions; arc derived for the effects of time, tcmp. and pressure. layer controls the ratc of reaction. At high temp. t h e ZnS evaporated,
Thermal expansion is isotropic t o N 1700" ; the sp. heat a t 1500" is reaction occurred in the vapour phase, and detached oxlde shells
were formcd. The thcory of t h c transfer through the boundary
1800"; a d decrease diminished this value by -
0.52 cal./g./"c. Thermal conductivity decreascd as 1/T from 500 t o
137:,. Data on
creep ratcs, ctc.. indicate that thermal strcsses may be relaxed if
layer is developed. (20 references.)
Reactivity of non-stoicheiometric black aluminas. B.
I<. R11)GWAY.

sufficient time is allowctl. Rupture strength values of a dcnse Arghiropoulos, J . Elston, P. Hilaire, F. Juillet a n d S. J. Teichner
material decrease rapidly with d . (26 rcfcrences.) J . W. TAYLOR. (Proc. SymF. Reactivity of Solids, Amsterdam, 1960, 525-537 ;
Concentration of carbonate rock by flotation. 11. Trials Happ. Cent. E t . nucl. Saclay, 1961, No. 1663).-The black structurally
with methylisobutylcarbinol. [MIBC]. E. Dalmazo, A. Rogas disordered oxide (A1202.s,j is prepared (as surface layer) by heating
and J. J. Roneo (Industr. y Qudm., 1961, 21, 36-38, 47).-Trials in vac. at 500" either ( i ) a porous or amorphous A1,0, 01- ( 2 2 ) finely-
were made on material containing 81y0 of CaCO, with the carbinol powdered cryst. Al,O, comprcssed t o 1-5 tons/cm.' Re-heating in
as collector or foaming agent and Na silicate as inhibitor. MIBC 0, at N 500" almost restores the original properties and reconverts
had no collector action a t concn. 0-1-1.2 g./l., N a silicate had no the semi-conductivity from n- t o p-type, b u t black Al,O, Iormed by
inhibiting action at 0---0.03 g,/l., p H had no effect between 7 and
(ii) does not convert into cr-Al,O, on heating at N 1000"in vac. The
10 and pine oil had no value as foaming agcnt. MIBC had foaming stoicheiomctric defect does not affect either the degree of chemi-
sorption of H, or the rate of catalytic hydrogenation of C,H,.
action at 0.03---0.05 g.jl. and addition of $0.25 g./I. of olein as
collector had some good effect, the optimum concn. of Na silicate as (19 references.) W. J. BAKER.
inhibitor was 0.02 g./l. and theoptimum pH was 10.M. T. ANDALUZ. Study of thermal dehydration of alumina trihydrate by
Infra-red study of calcium phosphates of the hydroxy- proton magnetic resonance. T. Saito (,I. Sci. Hiroshima Univ.,
apatite family. I,. Winancl and G. Duyckaerts (Bull. SOL. chim. 1961, 25AI1, 137-147).-X-ray a n d nuclear magnetic resonance
studies were carried out on the thermal dehydration of hydrargillite.
belg., 1962, 71, 142--158).--An i.r. spectrophotometric study of The ' movable ' water (as opposed t o ' s t r u c t u r a l ' water) was
natural and synthetic hydroxyapatite. cr-Ca,(PO,), (I) and octa-
calcium phosphatc (11) reveals the existence of OH- ions in the removed at 200". Hydrargillite transformcd to hydrous alumina at
structure and replacement of Ca2+ by Hf in compounds of lower
200--250". T h e hydrous alumina partially rehydratcd under a n
C a / P ratio, with corresponding elimination of OH groups and atmosphere of water vapour forming biihmite. Most of the combined
water was gradually removed a t 550-'loo", b u t its presence was still
existcnce of H bonds between HPO, groups. Heating of these evident at 700". (17 references.) 11. J . ELGAR.
phosphates leads t o formation of 1',0,4- in solid solutionin theapatite
lattice. Formulae proposed are Ca,,(PO,),(OH), for hydroxy- Structural and optical data on synthetic asbestiform
apatitc, Ca,(HI-'O,)(PO,),(OH) for I and Ca,(IIPO,),(PO,), for 11. materials : potassium-lead and lead-aluminium silicates.
Heating of I leads t o the reaction 2 Ca,(HPO,)(PO,),(OH) G. V. Gibbs, 1. L. Turner a n d F. D. Bloss ( U . S . B u y . Min. Rep.
120-500" Invest.. 1962, N o . 5935, 1 1 pp.).-Crystallographic and optical data
-+ 2 Ca,(P,O,) ;(€'0J6(0Hj +H,O : 2 Ca,(P,O,) :(PO,),(OH) are given for the synthetic isotypic compounds of approx. formula
;z 700"
__i 6 Ca,(P0,)2P+H,0. The triclinic form of I1 changes t o the K,Pb4Si,0,, (I) and PbzPb,A1,Si,Ozl (11). From the results i t is
apatitic hexagonal form at 200" and below 500" changes to thought t h a t the at. structures of I and I1 are based on chains of
Ca,(P,0,)(P04)4which between 650 and 700" changes to 5-0, tetrahedra lying along the C-cell edge i n a similar fashion
2 Ca,(I'0,)2/-)+Ca,I',0,~. (21 references.) E. J . H . BIRCH. as t h a t of scapolite. (1 1 references.) G . MACKENZIE.
Phase relations in the system CaO-Al,O,-H,O to high Determination of alkali polysulphides. L. Ikgrritli ( Afzalysf,
pressures and temperatures. C. W. F. T. l'istorius (Amev. J . 1961, 86, 854-856) .-Sulphide and polysulphide are separated from
Scz., 1962, 260, 22 1---23O).--The system n.as studied by mixing thiosulphate by treatment with ammoniacal ZnSO, solution. The
hl(OH), and Ca(OH), with water t o give the composition ppt. is boiled with dil. HCl a n d the pptd. S,cquiv. t o the poly-
JCn0,3A1,0,,9H,O. The mixture was encapsulated in Pt foil and sulphide is convcrted t o I<,SO, by 0.5 N-cthanolic KOH and H202.
hot prcssed betwecn two sintcred carbide pistons. The upper antl The residual KOH is then titrated with N-HCI. Thiosulphate is
lower stability limits were determined. 'The lower limit is located at determined in the filtrate from the original pptn. with ammoniacal
a lower temp. than prc\.iously thought, and i t connects smoothly ZnSO,. Sulphitle is determined by adding t h e sample t o a mixture
with thc curve denoting the upper temp. limit. (23 refcrcnces.) of HCI and 0.1 N-1, solution when polysulphide-S is pptd. as
T. i\. INGLES. elemental S without consumption of I,. Determination of the I,
Interaction of calcium aluminate with gypsum at high consumed measures the sulphide and thiosulphate ancl the contcnt
temperatures. S . I). Oltorokov, S. Ja. Golpnko-Vol'fson, T. N. of the latter, previously determined, is deducted. Total S is deter-
Yarlcina an:d I<. A. C.hcpik (Zh. pvikl. Khim., 1962, 35, 256-264).- mined by oxidation of the sample with Br water, pptn. of SO,,-
C a aliiminato o f any composition ( 3 : 1, 5 ; 3, 1 : 1 and 1 : 2) with with excess of standard RaCI, solution and dcterniination of the
addccl gypsum forms n c w compounds whcn sintered at 1100---1300 ' _ residual BaCl, with EDTA antl Eriochrome black-'l' and rhodizonic
Thc ratio CaO/..\l,O:, i n these compounds corresponds t o t h a t ol acid as mixed indicator. A . 0 . JONES.
monocalcium aluminate. I'ree CaO formed whcn Ca, aluminatc a n d Simultaneous 'detgrmination of sulphide, sulphite and
Ca, trisluminate wcrc reartcd with gypsum, while free A1,0, was thiosulphate ions. I,. Szekeres ( A ~ t n Chim.,
. Rornn, 1962, 52,
obtaincd with Ca dialurninate. Chcmical analysis indicatcd t h a t t h c 67--74).-The Sz-, S0,Z- a n d S,O,?- concn. of a. solution are
new compounds correspondcd t o 3(Ca0,Rl,O,,),CaSC),. A . I,. B. determined by titrations on four aliquot portions, measuring the
Chemisorption of oxygen on zinc and nickel oxides. I. consumption of J, (with 1, in acetic acid), thc consumption of Hr,
Matsuura ( 7 ' e c h m l . liep. Ku~zsaiL;JLZLJ,,19t;l, 36, No. 3, 63-71).--- (with KBr/KBrOJ, and the consumption of I, and Er, after removal
%n antl Xi oxides were prepared in a pure statc, and also mixed with of 52- as 13:s by boiling with boric acid, and using appropriate
ii-373 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-374

equations. The reaction of HS- with HS0,- t o give S,0,2- occurring (Zh. prikl. Khim., 1962, 35, 250-256).-Formation of Y,O,SiO, (I)
t o some extent with high concn. of SO,,- during removal of H,S was studied in samples prepared from equimol. amounts of Y,O,
79% and SiO, 21% (wt.). These were roasted twice 2 h at 1 IOO-
does not interfere with the determination. An alternative procedure
involves titration of three aliquots, measuring the consumption of 6
1600". I formed a t 1200". Reaction products at 1600 (2.)h.) were in
I, as before, the consumption of I, after removal of SO,e- with 93% yields. Pure I did not sinter at temp. near the m.p.,
CH,O, and the consumption of Br, after oxidising with 12/KBr but complete sintering resulted a t 1600" when Ale03 (1 wt.-%) was
solution in acetic acid, and eliminating free I, with aq. Na,SO,. added. I is semi-conductive but when B,O,, Bi,O, or ZnO were
L. A. O'NEILL. added in amounts of 2 wt.-% i t was a poor dielectric. The most
Inhibitors of the autoxidation of sodium sulphite solution. satisfactory additive was 1 wt.-% of A1,0,. The refract index of
Brahm Dev and B. D. Jain ( J . sci. industr. Res., 1961, 20D, 461).- I was 1930+50". Linear expansion coeff. a t 20-1200° was
Ethyl and propyl gallates, quercitin, rutin, quercitrin, quercetagetin, 4.3 x 10-6 ; heat-stability was satisfactory. A. L. B.
gossypetin, tannin and acacatechin were effective inhibitors of the Grain growth in sintered uranium dioxide. I. Equiaxed
autoxidation of aq. Na,SO,. Gossypetin and quercetagetin a t 0.001 grain growth. J . R. MacEwan. 11. Columnar grain growth.
M concn. were the best. (19 references.) D. J. ELGAR. J. R. MacEwan and V. B. Lawson ( J . Amer. ceram. Sac., 1962, 45,
Semi-quantitative determination of arsenic in minerals by 37-41 ; 41-46).-I. For a material having 94% of the theoretical
ascending paper chromatography. H. Agrinier (C.B. Aced. Sci.. d, the grain growth followed (but not exactly) the law
Pavis. 1961, 253, 1980-1981 ; Rupp. Cent. Et. nucl. Saclay, 1961, D2-Du2 = kUt0,*exp (-87,000lRT)where D (pm.) is the mean
No.2099).-Less than 196 of As in sulphide, phosphate and vanadate grain dia. atter t h. a t T('K),Do is initial grain dia. and k , = constant.
minerals can be separated from other metal ions (in N-HNO, solution) The presence of metallic U has shown in specimens annealed above
and determined colorimetrically to within &0.1% if the solvent 2000' that the system may become 0-deficient.
mixture acetone-COMeBui-conc. HN0,-H,O (5 : 4 : 1 : 1) is used 11. The columnar growth (the [ 1 1 11 orientation along the axis) was
and the As6+ band revealed with 3% aq. K I . Dissolution of a induced by applying a steep temp. gradient between 1700" and the
mineral arsenite in warm 10% NaOH followed by neutralisation and m.p. (2800"). and is due to the migration of large transverse voids
chromatography gives an As$+ band revealed with NaH,PO,. (width of which defines the cross section of the grain) up the temp.
Lower limit of measurement is lox As. W. J. BAKER. gradient by sublimation. J . i\. SUGDEN.
Zirconium and thorium chloride solutions in ethyl alcohol. Determination of inorganic and total phosphorus in uranyl
A. I . Svirjdovaand N. V. Sulkov'skaya (Zh. prikl. Khim., 1962, 35, nitrate solutions and ammonium diuranate. Anon. (U.K.
280-285) .-Solutions in EtOH were prepared with concn. Atomzc Energy Authority Rep., 1962, P.G. 262(S), 7 pp.).-The inorg.
0.02-2.0 g.-mol./l. of ZrC1, and 0.5-1.5 g.-mol./l. of ThCl, and with P is converted to the phosphomolybdic complex via NH, molybdate
different acid contents. Stable transparent ZrC1, solutions were additions under controlled conditions. The heteropoly acid is
prepared of up to 2.0 g.-mol./l. with water content in the alcohol reduced with SnCI, t o ' molybdenum blue ' which is determined
+ 0.2-0.3% and ThCl, of + 1.5 g.-mol./l. The solutions were absorptiometrically. The total P is determined by first destroying
neutralised by metallic Na or Ca. Removal of the HCI was the nitrate with formic acid and hydrolysing the org. phosphates
also achieved by distillation of the alcohol several times a t 20-22'/ with aq. H I ; the excess of HI is decomposed with HNO,. The P
8-10 mm. and again dissolving the residue. After thrice distillation is then determined as above. Inorg. P may be determined in the
and subsequently adding to the residue fresh alcohol, viscous liquids range 1-15 p.p.m. for NH, diuranate and 1-15 pg./ml. for uranyl
were obtained which quickly hardened. Analysis indi-cated that nitrate and total P in the ranges 2-30 p.p.m. and 2-30 pg./ml.
these were Zr(OEt),CI, or Th(OEt),CI,. From solutions with respectively ; the accuracy is & 10% relative at the 12 pg. level.
optimum acidity, homogeneous films were prepared which were Any arsenate present will be included in the total P.
satisfactorily stable. A. L. B. J. W. TAYLOR.
Autoradiographic determination of uranium. A. Catino Studies of manganese oxide-silica binary system. E. L.
(.4nn. Chim., Ronza, 1962,52.184--186).-The intensity of blackening Singleton, L. Carpenter and R. V. Lundquist (US.Bur. M i n . Rep.
produced on exposure of a sheet of photographic paper t o the sample Invest., 1962, No. 5938, 31 pp.).-Studies were made on the physical
for 24 h. is measured and compared with a reference curve obtained characteristics of the condensed MnO-SiO, system. 1 atm. of purified
from a series of mixtures of U salt and SiO, of known composition. He was used in the furnace to prevent oxidation of MnZ+ ion. From
The U content may be obtained to -5%. L. A. O'NELIL. m.p. determinations, solidus-liquidus curves and invariant points
Optical and electron microscopy of sintered uranium were established. The solidus line in the MnO-tephroite region was
dioxide. A. Porneuf ( J . nzcrl. Muter., 1961, 4, 200-217).-A a t 1315" and a metastable condition was observed a t 1347". the
comparison has been made of the external appearances of surfaces congruent m.p. of tephroite. The solidus line in the tephroite-
and the internal structure of UO, prepared under a variety of rhodonite region was at 1245O, and phase transition points were
conditions. Metallographic techniques of electrolytic polishing and sharp in this area. Eutectic and peritectic compositions contained
dissolution, chemical ion-bombardment and preferential oxidation 37.2% and 44% SiO, by weight respectively. Results of quenching
techniques for etching are critically assessed. These methods can and homogenising tests and microscopic and X-ray examination are
be used to assess fabrication treatments in terms of temp. and atm.; fully tabulated. (40 references.) G. MACKENZIE.
second phases may be identified. (29 references.) (In French.) Separation of fluorine from rare earths in solutions con-
J . W. TAYLOR. taining simultaneously calcium and silicon, by ion-exchange
Determination of water in uranium tetrafluorlde and method, A. M. Chizhikov, B. N. Rabinovich, E. A . Subbotina and
uranium dioxide. Anon. ( U . K . Atomic Energy Agthority Rep., V. N. Korsunskaya (212. p i k l . Khim., 1962, 35, 27&-280).-
1962. P.G. 247(S), 5 pp.).-25 ml. of dry MeOH are titrated with Ion-exchange resins (KY-2) of the sulphonic acid type (H+-form)
stantlardised Karl Fischer reagent to an electrometric end point were used, dia. of the particles being 0.5-1.0 mm. Passage of an
and a 10 g.-portion of the ground sample is added and the titration HC1 solution (best 0.4 N ) containing rare earth, Ca, F and other
taken to the same end point. The method is applicable t o concn. elements through the column gave quant. adsorption of the rare
of 04Y2 --I.() wt./wt. H,O with a precision estimated at better than earth, the filtrates containing all the F. The columns were then
+ 0.02";; a t thc 0.2% level. The method is not applicable to fluidised treated with 4 N-HC1 for recovery of the rare earth. Further
G d material. J . W. TAYLOR. separation of other admixtures from the rare earth was effccted via
Preparation of gallium phosphide. G. W. Samsonov, L. L. the oxalates and oxides. Dynamic exchange-capacity was greatly
Vereikina and Yu. B. Titkov (Zh.prikl. Khinz., 1967,35,242-245).- increased when the flow rate in these columns is accelerated. Ca,
Optitnum conditions are established for prep, of GaP in larger yield Fe and all the Si present in the HCl solution passed into the filtrates
and 997; purity. Ga metal is dissolved in FINO,, the solution with the F, so that the solution of rare earth chlorides contains only
evaporated and the nitrate heated to 400" and then 800" to constant a very small quantity of these admixtures. A. I,. B.
wt. 'The Ga,O, formed is reduced and simultaneously phosphided Melting points of inorganic fluorides. B. Porter and E. A.
with PH,, the product formed with 3 times e x c e ~ sof PH, having Brown ( J . Amer. ceram. Soc., 1962, 45, 49).-Data for fluorides of
composition agreeing with GaP. The product had the same contcnt Ba, Ca. Ce, Gd, K, La, Li, Na, Sr, Th and Y . J. A. SUGDEN.
of impurities as the original Ga,O, (Cu N lo-,, Fe < Effect of nature of gas on photocatalysis by platinum
P b < 10-8 %). A. L. B. catalysts. I. V. Krylova, V. A. Ogarev and N. I. Kobozev (Zh.
Formation and physico-technical characteristics of yttrium fiz. Khim. [English Transl.], 1961, 35, 1141--1143).-Extension of
oxy-orthosilicate, Y,O[SiO,]. g . I<. Kelcr and A. K. Kuznetsov previous work (Zbid., 1960, 34, 1139) shows that decomposition of
ii-375 3.-INDUSTRIAL INORGANIC CHEMISTRY ii--378
H,O, on freshly-prcpared Pt/SiO, a t 14-40" is retarded by illumina- structure, surface chemistry and degree of dispersion of C black on
tion in a stream of gas a t varying pressure (p), max. inhibition its behaviour in rubber compounds is discussed. (20 references.)
occurring in N, or A (9 = and 280 mm.). Illumination in H,, c. v .
or heating in N, for - 6 h., removes adsorbed 0, and re-activates Determination of boron in graphite. J . S. Paller anti H.
catalyst (stored or spent). Effect of variously conditioning the Zibuisky (U.S. Atomic Energy Comm. Rep., 1961, No. NBL 170, 104-
catalyst is discussed. Deactivation cannot be ascribed to photo- 106).-Bin a range 0 ~ 0 1 - 0 ~ 0 2 ~canbe
0 determined bya photometric
oxidation of Pt. W. J. BAKER. method for measuring the absorption of the R-quinalizarin (I)
Hydrogen washing with liquid nitrogen. L. VinS (Chem. complex. The Na,CO,-heated graphite ash is dissolved in water and
Pvdm., 1961, 11, 348-353).-Liquid-N, washing is used in a 150-ton the I colour is developed by the addition of the rcagent in conc.
per day NH, synthesis unit in preference to washing with a Cu H,SO,. c. v.
solution. The design is based on a high-pressure N, cycle with Spontaneous ignition in carbon adsorption beds, N. Bodcn,
ammonia refrigeration for pre-cooling to -45". At this temp. C. F. Cullis and A. Fish (1.appl. Chem., 1962, 12, 145--148).---The
synthesis gas passes through a silica gel drying unit which removes reaction of four types of C with ethanol or benzene with or without
COa as well as moisture. The washing column operates a t - 190". air were studied starting with C a t 250". The results suggest no
The plant requires 880 Ncu.m. of N, and 218 kWh per ton of NH,. heterogeneous catalysis but an exothermic reaction between C and
M. JUNGR. 0, which is strongly catalysed by any metal oxide impurities present.
With the resulting and considerable temp. increase, solvent: rtntl 0,
Preparation and purification of diborane. C. J. Yanby, E. react homogeneously and spontaneous ignition occurs.
Gobbett and J. W. Linnett ( J . chem. Soc., 1962, 2076-2077).-A4s 0.M. WHITTON.
the presence of hydrocarbons in diborane inhibited its oxidation, Oxidation of pyrolytic graphite in air between 1250 and
the compound was prepared by interaction of LiAlH, and BF, 1850"~.M. Levy (Industr.Engng Chem., Prod. Res., 1962, 1, 19--23).
etherate in very dry ether in presence of a N, stream. With excess -The oxidation rate of pyrolytic graphite below 1450'~ and the
of BF,, yields of 40-70% of diborane were obtained. An impurity activation energy calculated were less than those for commercial
with m / e 47 (in the mass spectrometer), possibly EtF, was removed graphite. The oxidation of pyrolyticgraphiteproceeded preferentially
by distillation through a Rose fractionating column a t 1 4 0 ' ~ . in the c direction. The rapid rise in the oxidation rate for pyrolytic
H. S. R. graphite a t 155O"~isattributed to the sudden change in the difference
Factors involving change in the mechanism of carbon between air temp. and thegraphite surface temp. 0. M. WHrrToN.
formation during decomposition of hydrocarbons. A. P.
Rudenko, A. A. Ralandin and G. Yu. Chueva (Zzv.Akad. Nauk SSSR, Method of sampling liquid carbon dioxide before analysis.
Otd. khim. Nauk, 1561, 164-165).-The no. of possible mechanisms Anon. ( U . K . Atomic Energy Authority R e f . . 1962, P.G. 283(W),
is determined by the number of C-forming materials of different 5 pp.).-The method involves vaporisation of liquid CO, in a water-
chemical classes, which may be obtained in a given set of conditions heated Cu-coil vaporiser unit after purging the sample value of the
of decomposition. Thus for methane, C-formation is a single-stage liquid container. The procedure is applicable to storage tanks and
process of dehydrocondensation of CH, with polycyclic aromatic road tankers at pressures up to 350 p.s.i. J . W. TAYLOR.
hydrocarbons formed from the original substance. Benzene is stable Behaviour of polysilicic acid. I. Surface charge effects.
under the given conditions of pyrolysis, and the mechanism proposed S. A . Greenberg, T. N. Chang and R. Jarnutowski (1.Polym. Sci.,
is a multistage dehydrocondensation into the C-forming substance. 1962, 58, 147--184).-The influence of surface charges OIL poly-
I n the case of n-pentane, several mechanisms are suggested. At silicic acid is studied by light scattering, e.m.f. and electrokinetic
600-750", olefins are derived by cracking, from 750 to 850" aromatic measurements. The potential-determining ions are H and OH
resin-forming compounds, and above 850' saturated compounds, which control the dissociation of the acidic silanol groups. The zeta
principally methane, the velocity of C-formation approaching that potentials are also influenced by the ionic strength of the solutions,
abserved for CH, itself. G. F. PENNY. the effect of cations on the surface charges increasing with valence,
Na < Ca < Al. Mol. wt. of the silica solution can be determined
Microporous structures in active carbons. I. Active carbons by light scattering or viscosity measurements and in order to
from [I] phenol-aldehyde resins, [II] polyvinylidene chloride. obtain reliable measurements an ionic strength of 0.1 is recom-
M. M. Dubinin, E. D. Zaverina, L. S. Ivanova, A. T. Kaverov and mended to suppress the influence of surface charges. (66 references.)
V. I. Kasatochkin (Izv. Akad. Nauk SSSR, Otd. khim. Nauk, 1961, c . v.
17-28, 29-37).-I. Active carbon samples were obtained a t temp. Effect of nature of silica gel and quartz surfaces on adsorp-
950 to 3000". Crevice-like micropores are formed as a result of tion. V1. Adsorption of water-vapour on crystalline and
burning-out in the activation of elementary crystallites. Measure- amorphous forms of silica. M. M. Egorov, V. F. Kiselev and
ments derived from X-ray data and adsorption data are in agreement. K. G . Krasil'nikov (Zh. $ 2 . Khim. [English Transl.], 1961, 35,
IT. The microporous structure is a result of thermal decomposition 1101-1 105).-Adsorption on powdered quartz is influenced by
of the pressed polymer with evolution of HCI and not the consequence development of aggregation and ultraporosity during grinding ;
of activation by gaseous substances connected with the burning-out part of final surface is accessible t o water mol. but not t o N,. Sp.
of substantial amounts of carbon. It is shown that it is possible to surfaces (calc.) of aggregated samples can thus be in error. Sp.
obtain carbon absorbents with sharply defined effects of mol. site- adsorption ( A ) of water-vapour on quartz, quartz-glass and SiO,-gel
actions. Basic measurements of the microporous structure and is highly sensitive t o degree of surface hydration ( H ) , e.g., dry or
adsorptive properties are given. G . F. PENNY. wet grinding, heating a t 20 or 200", and decreases when H is
Production of active carbon. H. Imai (Technol. Rep. Kansai -5 p molelsq. m. Degree of dispersion of sample influences A more
Univ., 1961, No. 3, 83--89).-Sawdust from the Japanese cypress than does structure of bulk phase. Possibility of a universal abs.
was treated with conc. HC1, H,SO,, HNO, or H,SO, a t 100--150" absorption isotherm for water on SiO, is discussed. (31 references.)
for 3 h. and then carbonised a t 350-900° for 30 min. The adsorption W. J . BAKER.
power of the C was tested for aq. NaOH, HC1, I, and methylene blue Determination of the kaolinite and mica contents of a clay
a t 30". There was considerable variation of adsorptive power with or kaolin. U. Hofmann and H. Haacke (Ber. dtsch. keram. Ges.,
carbonisation temp. and acid. C, prepared a t 350" using H,PO,, 1962, 39, 41-43).-The calculation used is as follows :--clay yo =
was an excellent absorbent for I, and methylene blue. Results were kaolinite + mica = 100 A/38.5 kaolinite = (B-0.045C)/0.095y0
used to calculate the surface area and dia. of C particles. where the Also, content is A% and the loss on ignition at 700" is
R. J. M. B%. J. A. SUGDEN.
Active carbon from Indian lignite. I. Activation by steam, Transformation of silicon dioxide during thermal treat-
air, steam-air mixture and carbon dioxide. S. P. Sen, S. ment of kaolinite. A. M. Kalinina (Zh. neorg. Khim. [English
Chatterjee and K. R. Chakravorty ( J . sci. industr. Res., 1961, 20D, Transl.2, 1961, 6, 1078--1083).-An X-ray diffraction study of
455-458) .-The production of activated carbon from lignite for synthetic kaolinite was made at 900-1370". Various compounds
m e in removal of H,S from gaseous raw materials was investigated. were identified at different temp., e.g., y-Al,O, and a n alurnino-
-4ctivation with CO, gave a product with max. adsorption capacity, silicate a t 1000". A high-temp. form of cristobalite (I) was identified
while steam activation a t 850" and a flow rate of 0.5 l./min. gave a at 1300-1350°, formed from amorphous SiO, remaining after
product with more generally balanced adsorption properties. crystallisation of mullite. I melts a t 1370" to give, after rapid
D. J. ELGAR. quenching, vitreous SiO, which is converted back t o I by heating
Dimensions of carbon blacks. C. W. Sweitzer (Rubb. B a s t . to 1000". There was no evidence for the formation of SiO. (40
Wkly, 1962, 142, 283, 2 8 6 2 8 8 . 290, 298).-The influence of fineness, references.) H. S. R .
ii-377 3.-INDUSTRIAL INORGANIC CHEMISTRY ii-378

Sulphite decomposition of kaolin by continuous process. Niobium and tantalum chlorides. Nova Beaucage Mines Ltd.
P. V. Dybina (Zh. prikl. Khim.,1962, 35, 443-447).-When concn. (Inventor : C. A. Sutherland) (B.P. 869,128, 8.2.60).-Al powder
of SO, were increased up t o 30% a t 110" the recovery of A1,0, and C are mixed with a dry ore or concentrate which contains Nb
after 1 h. was 92.5% ; the speed of autocatalytic oxidation of SO, (or Ta) in oxidised form. The mixture is ignited, thereby forming a
to SO, was much lower ; formation of H,SO, was not observed a t porous sinter which contains Nb or Ta carbide. The sinter is
110' ; the quality of the alumina was grade GI. When the particles chlorinated a t 350-600" (400-500") t o afford NbCl, or TaCl, free
of the initial material were reduced from 0.25 to 0.15 mm. dia., from oxychlorides. J. M. JACOBS.
satisfactory results were obtained at 90" but the quality of the Uranium dioxide. Junta de Energia Nuclear (B.P. 870,116,
A1,0, was not so good. I t is suggested that waste SO, from the 15.8.57. Sp., 16.5.57).-The gases evolved during the heating of
light metal industries could be economically used for decomposition (NH,),U,O, a t 800-900" are caused t o react a t 700-900" on the
of kaolin and clay. A. L. B. residual oxide (UO,) formed during the heating, yielding UO, as the
Combustionproperties of ammonia. W. L. Buckley and H. W. final product. J. M. JACOBS.
Husa (Chem. Engng Progr., 1962, 58, No. 2, 81-84).-The flam- Chromium-containing compositions of matter. Diamond
mability limits of NH, with 0, and N, mixtures were determined Alkali Co., Assee of T. S. Perrin (B.P. 793,973, 11.10.55. U.S.,
by spark plug ignition in a 1.5 in. dia. stainless steel tube 10 in. long. 12.10.54. Addn. to B.P. 724,246 and 739,760; J.A.C. A4bstr.,
The lower limit in air is 15.3% by volume, and the upper limit 1956, ii, 21 l).-The composition comprises the crude cryst. reaction
25.70/,. Explosion pressure measurements were made with air-NH, product resulting from heating aq. Na,Cr,O, with excess conc.
mixtures a t various initial pressures and temp., and are reported in H,SO, at 50-65' and then adding to the resultant cryst. mass of
the form of graphs. The detonation characteristics were studied : CrO,, NaHSO, and excess H,SO, an amount of Na,Cr,O,,PH,O
detonation waves were easily obtained with 0, or 0,-enriched air, in excess of that required to react with the free H,SO, in the mass.
although the slow flame speed of NH, flames increased the induction J . M. JACOBS.
distance ; the detonation wave velocity was 7800 ft./sec., however, Tin-activated barium phosphate phosphors. Sylvania
which is of the same magnitude as that for hydrocarbon detonations. Electric Products Inc. (B.P. 845,594, 2.8.57. U.S., 2.8.56. Addn.
K. RIDGWAY. to B.P. 738,490; J.A.C. Abstr., 1956, ii, 33).-The phosphors
Vapour pressure of hydrogen sulphide over aqueous consist of BaHPO, activated with Sn, part of which is in the stannous
monoethanolamine. D. S. Davis (Industr.Chem., 1962,38, 133).- state and contain Ba 2.7-2.75 and Sn 0.04 g.-at. per mol. of P,O,.
A nomogram is presented ; as a n example the v.p. of H,S over aq. or consist of (Ba,Sr)HPO, similarly activated and contain Ba 0.44,
monoethanolamine (I) is 0.04 mm. Hg a t 6 0 " ~when the concn. of Sr 2.44 and Sn 0.004-0.1 g.-at. per mol. of P,O,. J. M. JACOBS.
H,S is 0.4 mole of H,S per mole of I. c . v.
Seuaration of carbon dioxide and hvdrogen suluhide from
Determination of nitrogen in argon by gas chromatography. gas mixtures. H. E. Benson and J . H: Fiefi (B.P.-790,287-9,
I. A. Murdoch (Analyst, 1961, 86, 856857).-To determine N, 821,166, rA-c] 1.3.55, TD] 20.2.57. All addn. to B.P. 725,000;
occurring as an impurity in argon from cylinders the sample is J.A.C. Abstr., 1955, ii, 778).-1n the regeneration of the stripping
passed through a trap filled with Linde mol. sieve (type 5A) cooled solution (K,CO,) (to remove CO, and H,S), [A] the solution is treated
to -72" with a mixture of acetone and solid CO, to adsorb t h e N,. a t a temp. 190-215"~ under reduced pressure. [c] Part of the
Helium is passed through the trap to a gas chromatographic column regenerated solution is stripped more completely by heating at a
packed with the mol. sieve and thence to a detector. Argon and 0, temp. and pressure higher in the original treatment and then [B]
pass through the trap and the N, is then eluted. An ionisation recycled t o the top of the stripping column and the remainder to the
detector is sufficiently sensitive. A N, content of 9.8 p.p.m. was middle of the columns. 0. M. WHITTOK.
obtained with a standard deviation of 16%. (9 determinations.)
A. 0. JONES. [D] When the regeneration temp. is > 2 1 5 " ~ the
, solution leaving
the column is cooled by 1 2 0 " but ~ + 5 5 ' ~but not < 1 9 5 " ~before
i t is recycled. E. ENOSJONES.
Nitricacid. M. E. J. Cathala (B.P. 869,062,27.6.57. Fr., 27.6.56).
-A homogeneous mixture of NO, N,O,, 0, and steam, when Active oxides. Kali-Chemie A.G. (Inventor : R. Schober)
subjected for sufficient length of time to a temp. such that no liquid (B.P. 870,172, 17.3.59).-An active oxide (i.e., in a fine state of
can condense, is converted directly, in the vapour phase, into subdivision and having a large surface area of Al, Si or Zr) of an
HNO,. The gases produced by the catalytic combustion of NH, element capable of forming a complex compound (RH)+,MF, in
are so cooled that a sufficient amount of steam remains uncondensed which R is an amine group, M is the element in question and x is the
for this reaction to take place. The resulting gaseous mixture is valency of the element, is produced by causing an oxidic compound
maintained in the vapour phase until the direct formation of HNO, (hydrated alumina) of the element which is sol. in an aq. or org.
has taken place, the HNO, is separated and condensed, while the solution of a n organically substituted NH,F (I) t o react in a cyclic
residual oxides of N are recycled. J. M. JACOBS. process with a I (NH,MeF) a t elevated temp. thereby releasing an
amine and water and forming the above-defined complex. The
Treating calcium carbonate powders. Produits Chimiques released mixture of amine and water is added to the complex at lower
et MinBraux (B.P. 796,375, 27.1.56. Fr., 8.2.55. Addn. t o B.P. temp. to form the active oxide which is separated. The simultaneous-
747.842; T.A.C. Abstr.. 1957. i. 267).-ChaIk. dehvdrated to a ly formed I is re-used in a further reaction. J . M. JACOBS.
moisture &tent of c 0.1 % and ground to a n averag; particle size
of 1-2 p, is coated, by a dry ' process, with a quaternary ammonium Porous, silica-free, y-alumina base contacting agents.
compound in which the acid radical is a halogen, e.g., by spraying Esso Research & Engng Co. (Inventors: J. A. Anderson, jun.,
with a 50% aq. solution of dimethyllaurylbenzylammonium chloride. J. A. Dinwiddie, M. A. Mosesman and L. W. Vernon) (B.P. 870,509,
The product has improved properties when used as a filler, e.g., for 2.4.59).--A porous, solid catalyst comprises a Si0,-free, y-Al,O,
rubber. J. M. JACOBS. base and a catalytically-active metal component (Co compound,
Calcination of barium carbonate. Columbia-Southern Chemical e.g., CoMoO,). The A1,0, base has a spread of the range of pore dia. of
Corp. (B.P. 836,797, 8.6.56. U.S., 10.6.55. Addn. to B.P. 759,821 ; 20-100 (20-75) A, a most frequent pore diameter of 60-400
J.A.C. Abstr., 1958, i. 44).-A fluidised bed of BaCO, granules having (60-200) A , and a pore size distribution factor > 5 ( 4: 20).
a particle size > 80 mesh (Tyler standard screen) and maintained by J. M. JACOBS.
an upward rising stream of gas comprising N, is heated to 850- Active carbon. Bergwerksverband G.m.b.H: (B.P. 869,472,
1025" (900-975") t o evolve CO, and produce Ba0. The rate of 5.6.58. Ger., 19.8.57).-Carbonaceous materials are activated by
calcination is correlated with the rate of N, flow so that the concn. means of steam, using a carrier gas (N,, CO,, CO, or H,) a t 800-
of N, in the gas leaving the fluidised bed is 4: 70 v01.-%. IOOO", in a fluidised layer, the steam content of the activating mixture
J. M. JACOBS. being maintained a t < 0.65 ( c0.6) kg. of steam per Nm.3 of carrier
Purification of titanium tetrachloride. Laporte Titanium gas. J. M. JACOBS.
IAd. (Inventor : H. A. S. Bristow) (B.P. 869,602, 21.9.56).-Liquid Active carbon. Bergwerksverband G.m.b.H. (B.P. 870,082,
TiCl, containing V as impurity is heated under atm. pressure at 30.12.57. Ger.. 29.12.56).-Coal containing 18-40y0 of volatile
100-136" with 0.2-1% of its wt. of a mixture of org. materials matter is oxidised with 0, for 4: 1 h. at 100-300" to increase its
comprising a saturated or unsaturated org. material of I value 0-content by 4: 4% and this product is activated by treatment with
+25 (vegetable or mineral oil) 9 8 4 0 and a n unsaturated org. CO, a t 800-1100". The coal may first be impregnated with 0.1-
material having an I value of 80-230 (a vegetable oil, e.g., soya- 5.0% of alkali metal salt, and the CO, may contain N,, CO and up
bean oil) 2-20 wt.-%. J. M. JACOBS. to 10% by vol. of steam. J. A. SUGDEN.
ii-379 3.--IND USTRIAL INORGANIC CHEMISTRY ii-350
Solid boron hydride compounds. Studiengesellschaft Kohle Tensile testing ceramic materials, using a modified cross-
m.b.H. (B.P. 870,099, 1.12.58. Ger., 4.12.57).-A B compound breaking technique. R. R. Roup and C. L. Fillmore (Btdl. Amer.
BRR'R", where R is a hydrocarbon radical and R' and R" are cevanz. Soc., 1961, 40,694-697).-The value for the tensile strength
hydrocarbon radicals and/or H, or a hydrocarbon-substituted calc. from the cross-bending strength of a bar 6 x 1 (depth) x 0.5 in.,
diborane is heated to > 150" (160-280") with H2/10---400 atm. and agreed very closely with the strength measured in a direct manner,
in an amount in excess of the stoicheiometric quantity required to if there was a transverse (horizontal) hole 0.75 in. dia. a t the middle
produce the desired B hydride compound. BPrn3 at 190-210" of the bar, i.e. at the point of loading. J . A. SUGDEN.
with H, gives a yellow powder of formula (BH)*.in quaut. yield.
J . M. JACOBS. Calculation and measurement of stress in a ceramic-to-
Production of boron alkyls and of highly active aluminium metal seal. S. S. Cole, jun., and J. E. Inge (Bull.Amer. ceyanz. Soc.,
oxide. Studiengescllschaft Kohle m.b.H. (B.P. 869,550. 29.9.58. 1961, 40, 738-743).-The stress in a Cu-soldered seal between a
Ger., 3.10. and 14.12.57).-€3 alkyls are obtained in good yield disc of ceramic (thermal expansion, a, 8 x 1.7 in. dia. and a
(together with a highly active form of alumina) by treating AIR, circumferential ring of stainless steel (a. 19.5 x 1W8) and altcr-
or AlHR, (It is alkyl) with an alkyl boroxolc (2 : 1 mol. ratio) a t natively Ni ( a , 17 x was studied by (1) a theoretical graphical
200" (preferably in a first stage a t 100" and in a second stage at calculation from the properties of the components, (2) measuring
150-220"), optionally in presence of a solvent. Thus, AlEt, is (with resistance wire strain gauges) the devclopment of the stress
added during 1 h. to (EtBO), and BEt,, temp. rising from 15" to in the outer surface of the ring and (3) measuring the strain relaxed
94-95", with distillation of REt,. The residue consists of hl,O,. a t the inner surface of the ring when the ceramic disc was removed
I?. R. BASFORD. by etching away the solder with a hot solution of (NH4)&0,. The
Borides. 1J.S. Borax R: Chemical Corp. (Inventors : G. B. theoretical and practical results were in good agreement, and it
Cooper, A. A . R. Wood and G. 13. Bull) (B.1'. 870,083, 13.2.58).- appears that there is a stress constant a t the interface which depends
For the prep. of H,C a mixture of C and B,O, (or substances yielding only on the materials and the soldering temp. J. A . SUGDEN.
B,O, on heating) with an org. binder (a carbohydrate, e.g., molasses) Physical properties of flame-sprayed ceramic coatings,
is heated to 700" to carbonise the binder and provide an expanded J. L. Bliton and H. L. Rechter (Bull. Amer. ceram. Soc., 1961, 40.
C skeleton on which the other ingredients of the mixture arc 683-688) .-Measurements were made of the tensile bonding
supported. For the prep. of a boride of Ti, Zr, Nb. Ta, Mo, W, Cr, strength, bulk d , air permeability, thermal conductivity (differential
Ni or a rare earth metal of at. no. 57-71, an oxide of the corres- method using two coatings of different thicknesses) and emittance
ponding metal is included in the mixture. For the prep. of BCl,, (Perkin-Elmer spectrometer, 1.5-15 [L) of coatings of stabilised
BBr,, B2S3and E N , a current of Cl?, Br,, S vapour or N, is passed ZrO, (0.005-0-05 in. thick, d 4.8 g. per c.c.) on .\I, Inconel, and
over the B,C heated a t >300", >600", > 1000" or 1300-1900", Armco iron. The strength of adhesion did not increase significantly
respectively. J. M. JACOBS. with the roughening of the surface (sand-blasting) and the shape of
Boron nitride. U.S. Borax & Chemical Corp. (Inventors: the depression on the surface was important (V-shaped deprcssious
A. A. R. Wood and E. C. Shears) (B.P. 870,084, 24.3.58).-BN is did not promote adherence). The strength of the coating itself was
preparcd by passing N, (or gascous NH, or other N,-providing gas) 2640 p.s.i.; the strength of adhesion varied from 733 (Armco iron)
over a mixture heated at 1200-1600". of B,O,, or other B-providing to 950 (Inconel), but a (0.001 in.) coating of Ni-Cr alloy on the
constituent, C, and, as catalyst, a metal of at. no. 21-30, 39-46, method increased the adherence to 1274-1478 p . s i Raising thc
57 or 58, all inclusive, an alkaline earth metal or an alkali metal or temp. of the metal during spraying from 81--205" to 81-425"
a compound of such a metal, or a mixture of such metals or com- increased the adhesion on Armco iron by 50% but on A1 there was
pounds (Mo, Nb, Mn, Cr, Ca, Ba or Sr or compounds of these metals). no adhesion. The emittance was lower for a thicker coating and was
J. M. JACOBS. higher for Armco iron. J. A. SUGDEN.
Whitening porcelain. K. Shaw (Ceramics, 1962, 13, No. 157,
21-22).-A technique is described for the artificial whitening of
porcelain goods employing gaseous atm., CI, or CC1,. A period of
Glass and Ceramics. reduction in the firing cycle is not necessary. K. M. H.
Effect of boric oxide on electrical conductivity [K] of glasses.
A . Ya. Kuznetsov (Zh. .fiz. Kliim. [English Transl.], 1961,35,727- Mineralogy involved in firing structural clay products.
728).-Inclusion of B,O, in glass decrcases bulk K a t 250" from J . H. Richardson and E. G. Ehlers (Bull. Amer. ceram. SOC.,1961,
6x for Na,0,0.5 R20,,1.5 SiO, (I) to 3 x 10-7 R-' cm.-' for 40, 702-705, 708).-X-ray diffraction, microscope, and H,O-
Xa,0.2B2O, (II), but increases surface K a t 20" and 900,: R.H. from absorption tests on an impure kaolinitic shale and a fireclay, fired a t
3~ lo-, for I to 3 x 10-2 R-1 cm.-1 for 11. Large variations in K 600 to 1150", showed that the thermal reaction sequences were
can be obtained by heat treatment (annealing and/or quenching) ;
B,O, improves the bulk dielectric properties of glasses. Relation of
< 500"
kaolinite --+ metakaolinite ---f
750-920"
+
spinel SiO, ->
870-1 040"
~

870-1050° -P
li to glass structure is discussed. W. J. BAKER. mullite+cristobalite ; illite, 500-870" -+ anhyd. illite
mullite + glassy phase. The absorption decreased rapidly a t 900-- -
Reversibility of cracks in glass. V. M. Finkel' and I. A. 1000" (formation of glassy phase+mullite). There was little
liutkin (Dokl. Akad. Nauk S S S R , 1962, 143, 90-91).-High-speed difference between the properties of specimens fircd rapidly and
cinephotography (4000 frames per sec.) was used to demonstrate those fired in a commercial kiln. J . A. SUGDEN.
the heating of cracks in photographic glass plates which were
scratched with a diamond and photographed while being lightly Viscosity of glazes containing zircon. H. Jiirine (Trans.
tapped. 'Thcrc was a primary crack which continually lengthened Brit. Ceranz. Soc., 1962, 61, 104--120).--A falling sphere type
with tapping and a secondary crack which shortened and finally viscometer was used to measure the glaze 7 up to 1150". An Al,O,-
disappeared. Tnterat. or mol. bonding was not consiclcrcd primarily crucible was employed. l3ssolved zircon considerably increases t h e
responsible for the healing. Reversibility was limited to the field of the gl.aze, but the increase is mainly due t o the influence of the
in which surface mol. attractive forces operate. R. A. KEEN. crystal phase on the internal friction. Differences noticed between
Influence of viscosity and surface tension on measurements ground and ungrouncl glazes were explained by differences in crystal
made on glasses under the hot-stage microscope. H. Scholze sizes. 'r. A. INGLES.
(Bev. d t s ~ h .licrurn. G c s . , 1962, 39, 63-68).-Measurenients of Critical review of refractories. I. Selected properties of
surface tension and viscosity (Dietzel fibre methods) and of the Groups 4a, 5a and 6a carbides. E. K. Storns (U.S.
atoiizic. Energy
start of sintering- and softening-, ' half-sphere- ' and flow temp. Comm. Rep., 1962, No. 1,AMS 2674, 87 pp.).-Preparation, phasc
characteristics of pellets of powdered glass, were made on 9 silicate relationship, lattice parameter and structure, appearanco, chemical
and borosilicate glasses. The variation of surface tension had no stability, hardness, resistivity, superconductivity, thermodynamic
effect on the other measurements on the pellets, but the viscosity properties and vaporisation are studied. Methods whereby thew
was hlcpenrlcnt of the composition of the glass at thc following carbides can be freed from 0, and N, are specially noted. (137
characteristic points in the deformation of the pellet, (1) start of references.) C. v.
sintering, (2) start of deformation, (3) min. width of contact with
the supporting base, and (4) thc ' half-sphere.' Thus the hot-stage Preparation of heat insulating refractory by a foam process.
microscopc examination is a very useful method of determining the I. Formation of porous green bodies by use of water glass as
viscosity--temp. characteristic of a glass and especially of one of high a cementing material. K. Fujii (Rep. Tohyo chem. iridustr. Res.
softcning temp. J . -1.SUGPEN. Inst., 1961, 56, 538--547).-The green body formation procedure
ii-381 3.-IiVDUSTRIAL INORGANIC CHEMISTRY ii-382
(U.S.P. 2,921,357) is examined to obtain porous bodies having from PbO-ZrO,-TiO, mixtures consisted largely of ZrO,. The
porosities up to 90% on dry basis. Foam, produced from an aq. EDTA extract consisted PbO or of PbO (or SrO) combined with
solution of a foaming agent, and Na,SiF, are added to a slurry of TiO, in ratios greater than 1 : 1.
water glass and pulverised grog. After thorough mixing the foamy 11. Analytical methods described in Part I were used to determine
slurry is allowed to set. Satisfactory foaming agents were Lyponol unreacted constituents in unmodified and SrO modified lead
LS, oleyl sulphate, Nonipol Si, and Lypomin LH. Stirring with a zirconate-titanate ceramics made from mixtures having excess
whipper a t 300 r.p.m. gives a foam with bubbles of mean dia. ZrO, and PbO. The optimum conditions were obtained with the
50-70 v. To produce a very porous body with fine texture finely use of an excess of 1.6% moles PbO to an unmodified mixture, and
pulverised grog must be used with enough water glass to make a 0.8 moles yo PbO to compositions containing SrO and a TiO, : ZrO,
thin primary slurry. (12 references.) (From English summary.) ratio of 24 : 26. Replacement of PbO by 1 to 6y0 of SrO raises the
I. JONES. dielectric constant. Excess ZrO, lowers the dielectric constant and
High-density Arebrick. E. Gugel and F. H. Norton (Bull. coupling coeff. T. A . INGLES.
.+'?tier. rerum. Soc., 1962, 41, 8-11).-Full details are given of the Preparation of bulk uranium mononitride from powdered
manufacture, by conventional met.hods, of bricks having no open uranium and higher nitrides of uranium. J. Molinari (Rupp.
pores and a firing shrinkage of < 5 % . This is possible by choosing Cent. Et. nucl. SacEuy, 1962, No. 2103, 62 pp.).-By sintering a
a particle-size distribution which will give a max. unfired density mixture of powdered U and U,N,-UN, a t 1000"and 250 kg./sq. cm.
and by firing a t a high temp. J. A. SUGDEN. in vac. there is formed either UN or a cermet cc-U-BO% UN,
Thermal equilibria of the system MgO-MgO,AI,O,- according to mix composition, etc. Because impurity UO, is insol.
Mg0,Fe,0,-2Mg0,Si0,-2CaQ,Si02 with applications to in UN matrix prolonged heating of these sinters a t llOOo does not
the mechanism of reactions of magnesia refractories. S. easily convert their highly disordered structure into a cryst. one.
Solacolu ( S t u d i i Cerc. Metal., Bucuregti, 1961, 6 , 425-450) .-The The d , hardness and heat conductivity ( k ) of sinters are higher than
thermal equilibria of the phases of the quaternary system those for UN and U-UN cermets prepared by other methods;
MgO-AIIA-M,S-C,S and of the 5-component system MgO-MA-MF- between 50" and 150' k lies between that of UC and UO,. Nitridation
M,S-C,S were established. The data can be applied to magnesia of U a t 400-850' is discussed. (12 references.) \V. J. BAKER.
refractories (spinel, dolomite, etc.). A direct proportional relation
between the quantity of the iiquid phase and the properties of the Glass. Pittsburgh Plate Glass Co. (B.1'. 869,453, 28.12.59.
refractories has been found. At higher temp. the degree of mineralisa- U.S., 2.1.59).--A glass with an enhanced absorption in the yellow
tion of periclase is important. '[A = Also, ; F = Fe,O, ; M = MgO; and a transmission in the red, blue and green, and especially suitable
C = CaO ; S = SiO,]. (19 references.) (From French summary.) for the implosion- or face-plate for a colour television receiver,
M. SULZBACHER. contains the colour-controlling materials Fe,O, 0.05-0.4, Nd,O,
Unsteady flow method for air-permeability measurement 0.3-1-2, NiO 0.01-0*05, COO0.002-0.006, and Se 0.002--0.02%.
of refractory materials. L. J . Davies and H. Booth (Bull. Amer. A suitable base glass is SiO, 65-75, Na,O 12-19, CaO 6-13,
c e m m . SOL, 1961. 40, 744-747).-The method in which a vol. of MgO 1-4, A1,0, 0.2-40,A. J. A. SUGDEN.
air from a pressure vessel of large capacity is allowed to escape Optical glasses. E. Leitz G.m.b.H. (Inventors : H. Bromer
through the test piece to atmosphere between two measured and N. Meinert) (B.P. 869,616, 3.4.58).-A durable glass having
pressures over a known time interval, is subject to an error due to n > 1-65contains B,O, 16-32, A1,0,10-23 (B,O, + A1,O329--48.3),
the adiabatic cooling of the air. In this improved apparatus, the La,O, 25-50, and oxides of bivalent elements (e.g., CaO, MgO,
air \-essel (23 1.) contains 4 kg. (500 c.c.) of steel wool which maintains, CdO) 8-31 wt.-%. ZrO, > 10 and/or Ta,O, > lo?(, may also be
by heat exchange, a substantially isothermal condition for per- present. J. A. SUGDEN.
meabilities > 3 darcy (and for higher values if the amount of steel
wool and the size of the test piece are suitably adjusted). Ultraviolet transmitting glass. Jenaer Glaswerk Schott &
J. A. SUGDEN. Gen. (B.P. 794,308, 12.6.56. Ger., 23.6.55 ; Addn. t o B.P. 728,808).
Ratings of fireclay brick. G. R. Eusner and K. K. Kappmeyer -The glass which is also suitable for welding to resistant glass or
(Bull. Amer. cevum. Soc., 1962, 41, 1-7).-Extensive trials showed metals contains A1,0, 0--3 (e.g., 2.8), P,O, 55-72 (72), B,O, 1-6
that bricks could be rated according to the formula (2.9). SiO, 0-21 (9.3), K,O or Na,O 1-5 (K,O 1.2), BaO 5-18
R N = 3.5 PjD+ZL+10,000/MR where RN is rating no., L load (10.7) and other compatible constituents (MgO 1.1 yo).
deformation a t 1450" (ASTM C 16-49. Schedule 3)%, MI?, modulus J. A. SUGDEN.
of rupture (p.s.i.), D bulk d (9. per c.c.), P apparent porosity. The Glass containing tellurium. British Thomson-Houston Co.
classifications are 11) TvDe 1 or slag resistine. RN >30. 121 TvDe 2 Ltd. (Inventor : P. I,. Baynton) (B.P. 784,869, 26.1.55 ; Addn. to
or spalling resisting, RN >40 G d paney' spalling loss' (ASTM B.P. 736,073 ; J.A.C. Abstr., 1956, ii, 215).-The yellow/green
C 322-52) >6:/,. J. A. SUGDEN. defect of the high-n glass (SiO, < 10, TeO, <5yo and other oxides)
disclosed in the previous patent is eliminated by using TeO, con-
Mineralogical constitution of silica bricks. K. Konopicky taining <O.OO1~oof impurity. The pure TeO, is made from the
and Ch. Zaminer (Ber. dtsch. kerum. Ges., 1962, 39,44-47).-X-ray middle fraction (650") of Te thrice distilled in quartz apparatus a t
examination showed that with the increasing conversion of the 20 mm. IIg. The pure metal is dissolved in dil. HNO, to form the
quartz in the type of brick used in metallurgical furnaces, the basic nitrate which is calcined a t 400-~-430". J. A . SUGDEN.
tridymite/cristobalite ratio altered little, whereas it increased Mullite porcelain. Ipsen Ceramics Inr. (B.P. 870,320, 17.7.59.
markedly for the type used in coke-ovens and glass furnaces. The U.S., 8.9.58).-The raw mixture contains mullite grog 70-80,
grains of quartzite converted mainly to cristobalite contained little ball clay 20-30 and kaolin 0-100,b. The grog contains A1,0, 75
A1,0, and CaO, whereas the matrix contained u p to 0.8% of Also, and SiO, 250/, and consists of 95% of cryst. mullite ; the ball clay
and 3.8:g of CaO and had a high content of tridymite especially in contains A1,0, 28-31, SiO, 53-56 (free SiO, <20yo) and has a
the case of the coke-oven and glass-furnace bricks which not only refractoriness of cone 32-34 and contains < 10% of illite clay ;
had a finer quartzite grain size hut also contained crushed, fired the kaolin contains AI,O, 36-38, SiO, 46-48 (free 50, < 5 % ) ,
brick (itself rich in tridymite). I t is not the nature of the quartzite has a grain size < 10 p, and a refractoriness of cone 35--36.
which determines the constitution of the brick but the grain size J. A. SUGDEN.
t o which it is crushed. J. A. SUGDEN. Lime refractories. Mississippi Lime Co. (Inventor : K. \V.
Preparation of lead zirconate-titanate compositions. I. McAllister) (B.P. 870,239, 16.11.59).--A material containing
Determination of unreacted constituents. 11. Effect of excess CaO 85-97, Fe,O, 1-10, and MgO 2--5y0 is provided with a
lead oxide and titanium oxide. A . E. Robinson and (I) T. A. protective or stabilising matrix by previously fusing part of the
Joyce, (11) 1). Luff (Tvans. Brit. Ccram. Soc., 1962, 61, 85-93 ; CaO with the Fe,O,. The raw materials may be dolomite, CaO,
94-104) .- the application of chemical anlapsis to the control of &(OH),, CaCO,, pyrophoric Fe and the finely milled and shaped
PbC)-Sr0-Zr0,-Ti02 piezo-electric ceramics is described. The piece is fired a t 1370-1650". J . A . SUGDEN.
process control is based on the facts that (a) TiO, and ZrO, combined Chemically bonded basic refractory. Harbison-Walker
with PbO are sol. in acid, whilst the uncombined oxides are insol. Refractories Co. (B.P. 870,115, 17.7.57. U.S., 18.7.56).-A formed
and (b) free PbO and SnO are sol. in Na, EDTA. The compositions brick (of dead burnt or caustic magnesia) containing < 5 % of free
examined wcrc A,B, 2A,B, A,2B, where A is PbO or SrO, and B is MgO. is rendered resistant to slaking by treating (e.g., spraying) its
TiO, or ZrO,. The Pb containing mixtures were fired a t 940" and surface with a water solution of a phosphate or phosphoric acid (e.g.,
the SrO containing mixtures a t up to 1380". The acid-insol. material NI-I,T-I,PO,. NaHJ'O, Na,H,P,O,, ctc.). J. A. SUGDEN.
ii-383 4.-INDUSTRIAL ORGANIC CHEMISTRY ii-384
Refractory bodies containing boron nitride and a boride. energies ; no easy decomposition paths ; a structure stabilised by
Carborundum Co. (B.P. 784,705, 22.7.55. U S . , 25.10.54; Addn. resonance ; only substituents that enhance resonance stabilkation.
to B.P. 742,327 ; J.A.C. Abstr., 1956, ii, 395).-The body consists of Compounds consisting of 1 or 2 aromatic or aromatic type hetero-
hot-pressed mixture of RN (preferably up to 5 0 x ) a n d a boride cyclic rings and perfluorinated compounds were most stable, best
(other than of Zr or C), e.g., Mo,R, Cr,B or TiB,, or a mixturc of linking groups for rings were ether groups (e.g., Ph,Oj. The confrgura-
BN, koride of Zr or C and one of the borides of Mo, Cr, or Ti. tion influences stability, e.g., 2,2'-binaphthalene is more stable than
J. A. SUGDEN. 1, 1'-binaphthylene. Compounds with only SiAr or SiOAr links are
Ceramic insulating materials. W.E. H. Bloch (B.P. 808,068, also stable. (10 references.) 0. M. WHITTON.
3.5.56. Addn. to 699,155 ; J..\.C. Abstr.. 1954, i, 224).-A material
having a high strength but not an especially low dielectric loss, is Cold hydrogenation of 3-C fractions in liquid phase. W.
made by firing at 1200-1400' a mixture of plastic clay 3-20, Kronig (Erdol u. Kohle, 1962, 15, 176--179).-The impurities allene,
alkaline earth or Rc compound (e.g., CaCO,, wollastonite) 0-3, methylacetylene and ethylene in technical propylene are selectively
talc 0-35 and a mixture of raw uncalcined magnesitc and hydrogenated by allowing the liquefied gases to trickle down a fired
SiO? 42--97'y0. K or Na felspar ( > 10%) may also be added. bed of catalyst (Pd on A1,0,) with H, a t 10-15"/5-15 atm. The
J. A. SUGDEN. pressure, and thereby the extent of hydrogenation, are regulated
Low-iron, spalling-resistant periclase brick. Canadian by the H, inlet. The feed must be free from H,S, H,O and CO. A
liefractories Ltd. (B.P. 869,786, 2.10.59. Can., 10.10.58).-The brick technical plant has operated for a year a t throughputs of G - 2 3 . 5 kg.
contains iron-free periclase matrix (hlg0 490, SiO, > 6 , other of 3-C gases per 1. of catalyst without deterioration, and the catalyst
oxide >2"/,) 70--9776 in which is dispersed 3-30% of a Mg is easily regenerated by air at 450-.500°. The process is applicable
silicate ( > 1576 of Fe,O,) selected from serpentine and Mg ortho- t o acetyknic and diolefinic impurities in other technical gases.
A . R. PEARSON.
silicates (e.g., olivine, forsterite). J. -1.SUGDEN. Analysis and purification of isoprene. 11. 2. Dolejiek, 0.
Grubner, E. HBla and I. Kossler (Chem.Prdm., 1961, 11,361-363).-
Equilibrium v.p. of the system 2-methylbut- l-ene-isoprene-2-
4.-INDUSTRIAL ORGANIC CHEMISTRY. methylbut-2-ene were determined over the whole concn. range by
the Gillespie circulation method. Measured data were correlated by
Regrouping of radicals in solution. P. Iih. Freidlina, V. N. relative volatilities and the system was shown to form no azeotropes.
Iiost and M. Ya. Iihorlina ( V s p . Khim , 1962, 31, 1-38).-The As a final proof a binary mixture containing 95YL of isoprene and
review is divided into four main parts which give information on
regrouping of radicals with migration of hydrogen, chlorine, aryl 2-methylbut-2-ene was distilled in a laboratory column, with 100
theoretical plates. No azeotrope was detected. M. J U N G R .
groups and with migration of alkyl groups. (102 references.)
A. I-. B. Gas-liquid chromatography of isoprenoid compounds.
Self-integrating method for rapid determination of carbon B. A. Rudenko, V. F. Kucherov, V. A. Smit and A . V. Semenovskif
and hydrogen in organic compounds in milligram and sub- ( I z v . Akad. Nauk S S S R , Otd. khiwz. Nauk, 1962, 236-243).-The
milligram amounts using catharometers. P. F. Sommer, W. relative retention vol. ( V R ) was determined for 43 compounds of
Sauter. J. T. Clerc and W. Simon (Helv. chim. -4cta. 1962, 45, isoprenoid type in relation to a-cyclogeraniol = 1 , including a.lcohols
595-600).-The sample is ignited a t 800" in the presence of CuO, and their acetates, aldehydes, Me esters and lactones of acids. The
and the combustion products are swept by a stream of purified He data obtained was of value to establish connection between structure
into an evacuated system comprising two catharometers arranged and VR. Values were determined at 155, 170 and 185+2', in spiral
in series and fitted with U-tubes and thermal conductivity cells. Cu tube 2 m. x 5 mm. filled with 0.1-0.5 mm. refractory brick
The U-tubes contain Mg(C10,), and soda asbestos respectively. granules. Stationary liquid phase was silicone elastomer similar to
The signals of the first and second cells are proportional to the English high-vdc. silicone oil E-301. Carrier gas was He a t 30 m1.l
amount of H and C burned in the sample. A single determination, min. A few compounds suffered changes on evaporation or in column.
including weighing of the sample, requires < 7 min. (English giving supplementary peaks which vanished on lowering temp.
summary.) A. G. COOPER. Minor structural differences, especially a double bond in up-position
to a -COOH group, sharply affect V R . Differences of 2-3 : 1 were
Determination of sulphur in organic compounds by gas found between some a- and p-isomers, especially among acetates.
chromatography. D. R. Beuerman and C. E. Meloan (Analyt. Conjugated double bonds and carbonyl group in u- and p-ionones
Chem., 1962, 34, 319-322).--4 simple and rapid method is des- caused large differences in VR. Many close-boiling pairs including
cribed, the analysis being complete in 20 min. with a relative error cis- and trans-isomers can thus be separated. A mixture of Me esters
of 1%. The compound is combusted in 0, at 850" on a Pt catalyst, of u- and P-cyclogeranic acids and cis- and trans-lactones was even
H,O is removed (CaSO,) and the SO, and CO, trapped in liquid N, more easily separated with polyethylene glycol-4000 as stationary
and thus separated on a nonyl phthalate column with He carrier. phase. (15 references.) P. \V. B. HARRISON.
The method is satisfactory with sulphoxides, sulphones, thiones,
sulphides, disulphides and thioethers. Compounds containing F, High-temperature inhibition of normal paraffin oxidation
C1, N, and 0 in addition t o C and H were found t o have no inter- by alkylsromatics. J . J . Giammarid and €3. D. Norris (Industr.
ferenre. C. B. BAINES. Engng Chem., Prod. Res., 1962, 1, 16---18).-1nhibition of the air
oxidation of n-heptane by certain aromatics occurs a t 300---400°.
Qualitative analysis of hydrocarbons by pyrolysis and gas I t may be explained by H abstraction from thc aromatic by a radical
chromatography. A. I. M. Keulemans and S. G. Perry (Nature, from heptane oxidation. When toluene or p-xylene was the aromatic,
Lond., 1962, 193, 1073).-H~~drocarbonsare pyrolysed a t 500" in the resulting resonance-stabilised aralkyl radical dimerised in the
an unpacked quartz tube to exclude catalytic effects and the presence of 0,. But with PhEt or cumene as the aromatic. this
products idcntified by gas chromatography. Isomeric paraffins can radical is disproportionated to form an olefin and the original
be differentiated by this method. E. C. DOLTON. alkylaromatic or H is abstracted by a different radical to yield an
Catalytic activity of vanadium-containing mixed oxide olefin. (13 references.) 0. M. WHITTON.
catalysts in vapour-phase oxidation of organic compounds. Destructive action of Ught on aliphatic nitro-compounds.
I. 1. loffe, 2. I. Ezhkovaand A. G. I-yubarskif (Zh.jiz. Khim. [English V. I. SlovetskiI, S. A. Shevelev, A. A. Fafnzil'berg and S. S. Novikov
Transl.], 1961, 35, 1160--1161).--Increased activity and selectivity (Izv. Akad. Nauk SSSR, Otd. khim. Nauk. 1962, 359-360).-1< salts
of V,O,-MOO,, V,O,-Cr,O, and V,O,-Moo,-TiO,P,O, catalysts in of di- and tri-nitromethanes, and of 1.l-dinitro-ethane and -propane
the oxidation of benzene or furfural to maleic anhydride at -400' were illuminated with a standard amount of light energy from a
is ascribed to formation of solid solutions of MOO, and Cr,O, in the Hg arc a t 1 405, 436 or 546 mp for 10, 2 and 3 11. and relative
V,O, lattice, thus creating the necessary concn. of defects. Controlled intensities of lines of 200, 3000 and 2000 respectively. Results are
composition of these solid solutions permits activity and selectivity tabulated, The closcr the A of the light, with which a compound
of catalyst to be varied. \V. J. BAKER. was illuminated, t o the max. of absorption of its anion, the more
Thermal stability of organic compounds. I. B. Johns, E. A. intensively did its decomposition proceed. Stability to light and
McElhill and J . 0. Smith (Industv. Engng Chem., Prod. Res., 1962, 1. acidity of compounds are closely related. The acidity increases by
2-6).-Four types of test apparatus for the determination of thermal the decomposition by light, and the changes are irreversible.
stability of organic compounds are described. Compounds are more P. W. B. HARRISON.
stable in the vapour phase and a t low pressure. To be stable to Oxidation process for propylene. P. W. Sherwood (fndustv.
550" a compound must have : all mol. bonds with high dissociation Chem., 1962, 38, 55--58).-The reactions and processes leading to
ii-335 4.-INDUSTRIAL ORGANIC CHEhfISTRY ii-386
the production of acrolein, acetone, propylene oxide and acrylo- of different chemical classes (aliphatic, aromatic, heterocyclic, etc,)
nitrile are briefly reviewed. (13 references.) c. v. with yields reported in the literature. H. S. R.
Examination of equilibrium of liquid-vapour in isobutyl Synthesis of glycol ethers from ethylene oxide and alcohol.
alcohol-xylene isomer systems. Y u . N. Garber, R. A. Bovkun M. Repig, J. StieSinka and T. Rendko (Chem. Prdm, 1961, 11,
and E. N, Efimova (Zh. prikl. Khinz.. 1962, 35, 416--422).- 345-348).-The effects of temp., reaction time and mol. ratio on
Azeotropes are formed by m-xylene with Bu'OH (I) (93.0 mol.-y!, the product composition in the non-catalytic synthesis of glycol
content of I), b.p. 107.2", and by p-xylene (92 mol.-% of I), b.p. ethers was investigated. Product composition depends mainly on
107-1-107.2". At atm. pressure, o-xylene-I systems are non- mol. ratio of ethylene oxide to alcohol, while the degree of conversion
azeotropic. The m-xylene and p-xylene systems are sensitive to depends on the reaction time and temp. Optimum conditions for
variations in pressure. In both systems a t reduced pressure the methyl glycol ether are given as : 4 h. at 200°/40-42 atm., mol.
content of I in the azeotropes is less. Compositions and b.p. of the ratio of ethylene oxide t o MeOH 1 : 7.5, giving a product containing
azeotropes were examined with vacuum (40-240 mm.). m- and 83.5% of methyl glycol ether, 11.4% of methyl diglycol ether and
p-isomer azeotropes were formed to same extent, thus their separa- 0.8% of polyglycols. Optimum conditions for ethyl glycol ether
tion in these conditions in presence of I is excluded. In vacuum were : 5 h. a t 210-220"/36 atm., mol. ratio 1 : 5-6 and ethylene
conditions, o-xylene-I systems were azeotropic. When vacuum was oxide conversion 90-92%. (12 references.) M. JUNGR.
lowered from 330 to 40 mm. the content of I in the azeotropes was Determination of acetone and diacetone alcohol In presence
less. A. L. B. of mesityl oxide by ultra-violet absorption. A. Basinski and
Determination of propane- l,3-diol in glycerol by gas A. Narebska (Roczn. Chem., 1961, 35, 1381--1389).-Mesityl oxide
chromatography with a flame ionisation detector. W. J . was identified as the third component present in the aldol conden-
Murray and A. F. Williams (Analyst, 1961,86, 849--853).-Standard sation of acetone at 12.5 and 25'. I n view of its large U.V.absorption
aq. solutions are prepared containing 10% of glycerol, 0.276 of diethyl- the recently presented method (cf. ibid., 1131) was modified and
ene glycol (I)and different concn. of trimethylene glycol (11)between optimal wavelengths were determined a t 2530, 2675 and 2755 A,
0.02 and 0.2%. With the gas-chromatographic apparatus working corresponding to maxima for acetone, diacetone alcohol and mesityl
under the conditions suecified 2-u1. samoles of the DreDared solution oxide respectively. Correction curves were derived for calculating
arcinjected and the hkights of the peal& for I and-I1 i r e measured. acetone and diacetone alcohol, but i t was emphasised that the method
The factor F is rr% x Peak height for I . To the glycerol sample is accurate for mesityl concn. 0.0001-0.001 mole/litre only and is
1% Peak height for I1 unsuitable for concn. above 0.002 mole/litre. A. L. GROCHOWSKI.
an aq. 2% solution of I is added, the mixture is diluted to 100 ml. Catalytic action of anion-exchange resins on aldol conden-
and the chromatogram recorded. The peak heights are measured sation of acetone and decomposition of diacetone alcohol.
for I and 11. The content of I1 (%I -
~ , -is, given bv I. General mechanism and kinetic equations of the reaction.
2'o Peak height for I' Results show satisfactory accuracy. A. Basiliski and A. Narebska. 11. Kinetic investigation of
Peak heieht
v
for I condensation of acetone and decomposition of diacetone
A. 0. JONES. alcohol on Amberlite IRA-400 in OH' form. A. Narebska
Reaction kinetics, adsorption and equilibrium in vapour and A. Basidski ((Roczniki Chem., 1961,35, 1673-1684, 1685-1696).
phase dehydration of ethanol to diethyl ether as catalysed by -1. Aldol condensation attempted with specially treated Amberlite
ion-exchange resin. R. L. Kabel (Dissert. Abstr., 1961, 22, IRA-400 resin as the catalyst failed in 0.25 and 1.0 moleilitre acetone
1539--1540).-The reaction takes place in presence of an acidic in EtOH solutions but was successful in pure acetone. The latter
ion-exchange resin as catalyst. Conversion data for feed compositions yielded diacetone alcohol and some mesityl oxide. Results were
and adsorption measurements for components are obtained a t atm. correlated with those of Koelichen (cf. 2. plzys. Chem., 1960, 33,
pressure over a hundredfold range of space velocity at 80-120". 129). The necessity of aldol condensation in conc. solutions or
Results are in general agreement with the Langmuir-Hinshelwood pure acetone was confirmed. The unsymmetrical character of the
approach to heterogeneous catalysis. G. MACKENZIE. reaction and its kinetics are discussed. (22 references.)
Kinetics of dehydrogenation and dehydration of isopropyl 11. Rate constants a t 12.5, 25.0 and 37.5' were determined for
alcohol over titanium dioxide (anatase). A. A. Tolstopyatova, the acetone aldol condensation and diacetone alcohol decomposition.
I. R. Konenko and A. A. Balandin (Izv. A k a d . Nauk SSSR. Otd. Amberlite IRA-400 was used as the catalyst a t 1 : 25 ratio of 6.-
khzm. Nauk. 1961, 38--44).-The reactions named are complicated equiv. of the OH- ions of the resin to those of acetone or diacetone
by carbonisation of the catalyst. Carbonised TiO, has little effect alcohol. The activation energies and the catalytic constants of the
on the magnitudes of the reiative adsorption coeff. of acetone and resin were calculated. .4lthough less active than NaOH, Amberlite
H,. For acetone and water these coeff. decrease with rise in temp., IRA-400 is considered a suitable catalyst, and unlike NaOH, can
but for H, and propylene they are unchanged in the temp. range be used in continuous processes. (12 references.) (From English
280-3 10". G. F. PENNY. summaries.) A. L. GROCHOWSKI.
Influence of method of preparation on titanium dioxide Determination of aliphatic aldehydes by spectrophoto-
catalyst in the ethyl alcohol, isopropyl alcohol and cyclo- metry. A. M. Albrecht, W. I. Scher and H. J . Vogel (Analyt. Chem..
hexane reactions. A . A. Balandin. I. R. Konenko and A. A. 1962, 34, 398-400) .-Aldehydes are reacted with NH,Me,HCl
(1.0 M ) and o-aminobenzaldehyde (0.004 M ) in aq. solution a t
Tolstopyatova (Izv. Akad. N a u k S S S R , Otd. klzim. N a u k , 1961, 45-
50).-- The catalytic properties of TiO, appear to be closely dependent pH 8.4 to give yellow colours which are obtained within 10 min.
on the method of prep., as shown by the energy of activation (c) and a t 25". The absorption of these colours is measured a t 440 mp.
the pre-exponential coeff. in the Arrhenius equation. A logarithmic C. B. BAINES.
relation between E and k, for the reactions of dehydrogenation of Separate determination of small quantities of ethylene
alcohols and hydrocarbons and hydrogenation of ethylene on one oxide, formaldehyde and acetaldehyde in mixed aqueous
hand, and the dehydrating of alcohols on the other, is shown. solutions. S. M. Samoilov, V. N. Andrievskii and 1. L. Kotlyarevskii
(Zzv. Akad. Nauk S S S R , Otd. khim. Nauk, 1962, 201-208).-A
G. F. PENNY. method of determination was required for the three components in
Detection of higher alcohols by paper chromatography. mixed weak aq. solution of ethylene oxide (I). formaldehyde (11)
I-'.Capella, G. de Zotti and G. Jacini (Riv. ital. Sostanze grasse. and acetaldehyde (111), the concn. of each ingredient being
1962, 39, 2-8).---One method consists in converting the alcohols
to malonate half-esters. separating by paper chromatography with a <0.4 N . I and aldehydes mutually interfere during analysis by
petroleum-aq. acetic acid system, and revealing the compounds as earlier known methods. For I alone, the best results were obtained
Cu salts, and is satisfactory for the 10--22-C normal series. Alter- with KI + H I which detected 97-100y0 of I content, whereas
natively the Ac deriv. of the alcohols are separated paper chromato- Na,S,O, only showed 76-78%. No better reagent was found for
graphically with a petroleum-aq. acetic acid/acetone system, estimating I in mixture with I1 and 111. I1 is determined by
revealing the compounds by treatment under prescribed conditions Schiff's reagent and total I1 + I11 by hydroxylamine hydrochloride.
with solutions of hydroxylamine in MeOH, followed by l~eCl,/HClO, The method showed only 90% of true content of I and 111 but is
in MeOH/Et,O, and is suitable for 10--26-C normal alcohols. simple, rapid and economical of reagents. Neither K I + H I nor
I.. A. O'NEir-L. Na,S,O, reacts with ethylene present in hydrocarbon oxidation
Methods of preparation of a-trihalogenocarbinols. J. H. T. products. (14 references.) P. w. B. HARRISON.
Ledrut and C;. Combes (Indusir. chim. belge. 1962, 27, 635-656).- Synthesis of aliphatic sulphonic acids. E. Goethals (Industr.
.4 review with 200 references of 27 methods of prep. of the carbinols chim. belge, 1962, 27, 663-680) .-A review with 278 references.
ii -397 il.-INDUSTRIAL ORGANIC CHEAUS1'R17
dealing with five methods of introducing the SO,H into an org. and saturated CaCI,. Yields are improved by using anhyd. starting
inol.: (1) action of H,SO,, SO, or CIS0,H. (2) use of SO,. (3) use of materials and by heating on a water bath after addition of t!le
sulphites, (4) by sulphoalkylating agents, (5) by oxidation of bivalent catalyst, E. J . H . BIRCH.
S compounds. (In Flemish ; from English summary.) H . S. R.
Catalytic synthesis of ethyl propionate from diethyl ether
Synthesis of [A] saturated esters, [B] allyl and propargyl and carbon monoxide at high pressure. S. K. Bhattachalyya
esters, [c] tetra-alkyldiamides from 1-alkylthio-2-dichloro- and S. K. Palit ( J . uppl. Chem., 1962, 12, 174--182).---Thc reaction
phosphinyl-3-chlorobuta-l,3-diene.M. F. Shostakovskil, 1. I. has been studied in the presence of various Ni, Co and iron catalysts
Guseinov and G. S. Vasil'ev ( Z h . obshch. Khina., 1962, 32, 375-377, a t 200--300' a n d 175-375 atm. pressure. Catalytic activity was
378-379, 380--381!.--The prep. is described of [A] Mc, E t , Pr and greatest with the iodides of iron, Co and Ni, supported on silica gel,
Hu estcrs, [HI allyl a n d propargyl estcrs by interaction of the b u t practically nil with reduced metals and their carbonyls. Max.
butadiene named (alkyl of 1-4 C), by interaction of the dichloride yiclds of ethyl propionate (28.2%) and propionic acid (lO.l';o) were
with the anhyd. alkanol in benzene in presence of pyridine. The obtained at 230"/240 atm. after 2 h. Activity of the cafalyst is
physical properties of the estcrs (dialkoxy phosphinates) are rnaintaincd if t h e products are cooled before prcssnre release and
tabulated (16 compounds i n A ) . [c] The dichlorophosphinyl deriv. deactivated cataiyst is reactivated by adding a few drops of water.
is treated with NHEt, t o obtain the cliamides, which had a sharp possihle reaction mcchanisrns are suggested t o explain the formn-
odour, wcre stablc a n d sol. in org. solvciits. A. L. B. tion of by products. (13 references,) 0 . hq. b\'IIITTON.
Poteiitiometric method for analysing mixtures of organic
acids with nitric acid in non-aqueous media. A. P. Iireshlrov, Catalytic synthesis of ethyl propionate from ethylene,
I,. N. Bykova. M. S. Iiusalcova and N. :I. Kazaryan (Zavod. Lab., carbon monoxide and ethanol at high pressure. S. l i .
1962, 28, 1l-l3).-Nitric and or-hydroxyisobutyric acids can be Rhattacharyya and S. N. Nag ( J . uppl. Chem., 1962, 12, 182-~-19Oi.---
titratcd separately, potentiometrically, in the mixture of these The synthesis of ethyl propionate (I) in the prcscnce of iron, Co anil
acids obtaincd as a stage in the synthesis of methacrylic acid. The Ni catalysts a t 2000--8200 p.s.i. and 180-300O has bcen studietl.
solvent is CXIblcEt or acetone. The titrant is 0.1 N-NEt,OH in Reduced Fe, Co and Ni and their carbonyls have no catalyric
benzene-methanol or 0.1 N-NaOH in 3 : 2 acetonc : water. The activity. The excellent catalytic activities of t h e halidcs arc in the
first titrant, but not the second, can also be used for titrating weaker or.der : iodides > bromides > chlorides, and o f thc ineta!s :
acids, such as nitrophcnols. A. B. DENSHAM. Co > Ni > Fe. Under the optimum conditions (catalyst-metal;
silica 50 : 50 ; a t 230" ; GO00 p.s.i. with Co1,and Nil, catalysts, and
Some new aspects of fatty acid chemistry. I>. Swern, E . S . 4400 p.s.i. with Fel, catalyst : residence time 2 h , ) , the p n
liothman, T,. S . Silbrrt and J. S. Showell (Chem. 6. I n d . , 1962, yields ol 1, based on ethanol input are 57.0, 45.1 and 43.4:,, nit11
1304---1309j.---Three major lincs of research on the use of inedible COT,, Ni12 and FcI, cata.lysts, respectivcly. Catalysts m u s t contain
fats and oils t o manufacture chemicals have becn described : acid water for max. efficiency. 1.0~sof water can bc replaced by adding
catalyscd interchange rcactions of carboxylic acids with enol i t t o the ethanol. (15 references.) 0 . hi. \\iHi?TOS.
esters, prep, of aliphatic and aromatic pcroxy acids and selective
epoxidation of unsaturated compounds. Examples are given with Polymorphism of thiodipropionic acid. J. A . Hlantl and
yields of products. h.s. CARMICHAEL. hl. E. A . Cudby (J. upfil. Chem., 1962, 12, 320---328). --The p l y -
morphism of thiodipropionic acid and the transitions between
Applications of anhydride titrimetry. IX. Volumetric phases with temp. were studied by i.r., X-ray and optical techniques.
determination of acid chlorides. C. Hennart (Chzm. aizal., 1962, Crystal structures for forms A and 13 are proposed. Uiffercnccs arc
44, 61--63).--Acid chlorides arc determined in presence of acids or explaincd. When B was heated it gave at 101"+0..5' a third f o r m
anhydrides b y reaction t o form pyridinc hydrochloride, \vhich is C with a melting range just below the sharp m.p. of -4 at 128".
titrated with HC10, in acetic acid, in presence of I-Ig" acetate and
Metanil yellow. Results for 11 acid chlorides are given. 0 . XI. WHITTOY.
I

1'. I). PARK-RICHARD. Chromatography of lipid bases on paper impregnated


Submerged citric acid fermentation of sugar beet molasses:
effect of ferrocyanide control. D. S. Clark fl?zdustv. E w w Chem..
Prod. Res., 1962: 1. 59-62).--The stability of thc subrne';.@d citric
acid fcrnientation of ferrocyanidc-treated bect molasses by
\ with silicic acid. B. Palameta and M. Prostenik ( C ~ o a t .( I d t i > ! .
A r t a , 1961, 33, 133--135).-Chromatograms are run on silicic acid-
impregnated paper using a 40 : 25 : 5 v / v di-isobutyl kctonc,'
AcOH/water mixture for development. The XF values for sev<:ral
Aspergillus niger was improved by accurately adjusting the concn. C,, and Czo a-aminoalcohols, or-aminokc toncs and diami iics (4.5-
of ferrocyanide in the mash t o levels required for optimum acid diaminoeicosane a n d 3,4-diamino-2-mcthylnonadccane) are givcm.
production. With adjustment made either before inoculation or (13 references.) (In English.) E. c . D 0 l . T O S .
during the first stage of fermentation, yields (above 7504 convcrsion Formation of secondary and tertiary amines in catalytic
in 140 h.) were consistently high in fermentations i n 2.5-1. glass hydrogenation of adiponitrile to hexamethylenediamine.
tower fermentors. (11 references.) (1.M. WHITTON. L. Kh. Frcidlin and T. A. Sladkova (Izv. Ahad. Na2nlz S.S.SA', Old.
khim. Nuuk, 1962, 336341).-Industrial hydrogenation of adipo-
nitrile (I) with H, and Ni catalyst gives ~ 3 0 ~ residtml
)" high-boiling
mixture of complex amines. Three fractions were sepa,ratctl by
distillation a n d identified : (i) b.p. 100-10S0/4~5 mm.; n;OJ ;
1.4905 ; d,"O 0.9150 ; M.R. 88.63, consisting of l,(i-di(cycio/irt-u-
nzethylcneimino) hexaize (11) ; (ii) b.p. 115~---11G0j%5mm.; rLy;
1.4800 ; dd2" 0.9002 ; M.R. 62.72. consisting of N-(E-anzi>zohexyl-
cycloliexametlzyle~acim~ne(111) : (iii) white crystals, m.p. 35", of
N-a-aminohexylhexamethylenediamine (IV). With incomplete
reduction of I , using less active Ni-MOO, catalysts, were obtained
c-aminocapronitrile and a fraction, b.p. 115-120" ( 3 . 5 mm.),
n: 1.4630, which may contain N-(E-cyanopenlyl)cyclohexairirl~lylrne-
imine (V), since on reduction with Ni and H, at 80" and 120 atrn.
i t gave 111. Under optimum conditions (80--1OOo~100 aim. initial
pressure) primary and primary-secondary amines first formed do
not undergo a n y further changes. Amines containing s- or t-N
atoms are not formed by deamination of hexamethylcne diamine
(VI) b u t by a n aldimine mechanism. l-Aminopcntamethylcne-5-
aldimine is very reactive and combines with VI to form IV and
with cyclohexamethyleneimine t o form 111.
1'. \V. B. HARRISOX.
Quantitative paper chromatography of amino-acids. [A
review]. Hrishikesh Bhattacharya and S. I<. Dutta ( J . IFtshi
Clsem. India, 1961, 33, 284-295).-Choice of paper, solvent, nicthod
of drying, detecting reagent and quant. measurement are discussed.
(57 references.) \V. ELSTOW.
ii-389 4.-INDUSTRIAL ORG.4ArIC CHEMISTRY ii-390
Reaction of amino-acids with hydrogen peroxide in nonanol-2 and -3, undecanol-5 and tetradecanol-7 (I) a t temp.
presence of ferrous salts. S. Goldschmidt and G. von Linde lower than that necessary with primary alcohols. Yields were
( E r d d $4. Kohle, 1962, 15, 81-83).-The amino-acids tested (3-5 C) 75% calc. on reacted tetralin. I, n1.p. 42", setting point 41.6",
were all oxidised, the longer chains the more readily, to yield lower b.p. 138-140°/6 mm., was synthesised for the first time from
amino-acids with loss of 1-2 C. In no case was the -CH(NH,) - heptyl-MgBr and oenanthic aldehyde. Alkylations required 5 h. a t
group attacked. The separation and identification of the products temp. of commencement of reaction (155-185"). Structural
by paper chromatography and electrophoresis are described. A formulae of the compounds based on i.r. spectra are suggested.
reaction mechanism is suggestcd. A. R. PEARSON. r'. w . B. HARRISON.
Chromatographic examination of the pyrolysis products Catalytic alkylation of tetralin with n-alkenes and primary
of sucrose. 1'. F. Rossi, L. Gioventu and F . Masera ( A n n . Chim., alcohols. N. I. Shuikina and N. A. Pozdnyak (Rev.Inst. frany.
Roma. 1962, 52, 197-200).-Sucrose has been pyrolysed, and the Pc'trole, 1962, 17, 282--287).-A simple method is described for'the
liquid distillate (50%), which gave a violet blue colour with FeCl, catalytic synthesis of heptyl-, nonyl-, decyl- and dodecyl-tetralins,
and reduced Fehling's solution and Tollens reagent, examined by which. with ZnC1, a t atm. pressure, are yielded in proportions of
paper chromatography. No evidence for aromatic compounds 49.5, 50.5, 48.3 and 38.5%, respectively, with respect to the
(especially PhCHO and PhOH) was obtained. L. A. O'NEILL. primary alcohols. Slightly better results are achieved in an autoclave
a t 10 atm. 1,2,3.4-Tetrahydro-6-alkylnaphthalenes are formed.
New acetylating reaction for sugar. 11. Experimental The alkyl groups have the is0 structure. The detergent properties
clarification of reaction mechanism. A. Aszalos and V. Prey of the tetralinesulphonates are briefly discussed. (13 references.)
(Stuvke, 1962, 14, 50-52).--A method for acetylating aq. sugar N. S. B.
solutions w i t h Ac,O similar to that for acetylating starch and Catalytic dehydrocyclisation of 2-n- and 2-s-hexyl-
cellulose a t constant pH is described. OH- ions must be present naphthalenes. N. I. Shuikin, I. A. Erivansltaya, N. I.. liomissarova
and a complex of OH- and Ac,O is formed before acetylation takes and Yan Ai-Si (Izv. A k a d . Nauk SSSR, Otd. khiwz. Naack, 1962,
place. The union of these complexes with alcoholic groups of a sugar 327-333).-2-n-(1) and 2-s-hexylnaphthalene (11), b.p. 154O/
or polysaccharide effects the acetylating reaction. The reaction is 8 nim., n:: 1.5660, d;O 0.9764 (not previously described), were
+
generally suitable for any alcoholic group which is not sterically subjected to dehydrocyclisation over A1,0, 20% Cr,O, (111) a t
hindered. E. M . J . 450' and birch charcoal + 10% Pt (IV) a t 350" as catalysts. I and
Hydrolysis of dialdehyde starch : glyoxal and erythrose I11 gave 76% of catalysate from which only phenanthrenc was
production in sulphurous acid-barium sulphite solutions. recovered without any expected 4-ethylphenanthrene, I1 and 111
C. A. Wilham, T. A. McCuire, J . W. Van Clew, F. H. Otey and gavc phenanthrenes. Only 1-methylphenanthrene was isolated
C. L. Mehltretter (Industr. Enpig Chem., Pvod. Res., 1962, 1, 62-64). without any 1,4-dimethyl deriv. I and I1 with IV as catalyst gave
--.-By the procedure described, dialdehyde starch in 20% concn. only 14-16% of anthracene. I-Ethyl- and 1,4-dimethyl-anthracene
cxn be hydrolysed with BaSO,,+ SO,. Glyoxal complexes with werc not isolated. The hydrocarbons were identified by their
HaSO, and is partially pptd. during hydrolysis. Glyoxal yield was properties, U.V. and i.r. absorption spectra and picrates and H, and
90% and of erythrose 75%. (11 references.) 0. M. WHITTON. hydrocarbon gases evolved were analysed by gas adsorption
chromatography. P. W. B. HARRISON.
Gas chromatographic determination of 2-104 products
from the y-irradiation of liquid cyclopentane. A. 13. Leplcy Vinylation of benzene alkylate. M. Ogawa (Terhnol. Rep.
(.4izalyt. Chem., 1962, 34, 32!!-325).--Direct analysis of an entire Kansai LTniv., 1961, No. 3, 47--50).-A commercial benzene long
irradiated sample of < 100 mg. allows a qual. and quant. deter- chain alkylatc was fractionated and the 290-310" fraction was used
mination of 14 2-10-C products over a widc range of total dosage. as starting material. The mixture was acetylatcd with AcCl or
Use of weighed, encapsulated samples and internal standards allows Ac,O, rlealkylatioii was inhibited by the' addition of AlCl,, and
a high precision of all trace products observed in the presence of up >5076 yield of acetylated compounds resulted. Raney-Ni or Cu-
to 10,000 times their weight of cyclopentane. C . B. BAINES. chromate reduction of these was >90% efficient, and KHSO, in
xylene dehydrated the resultant carbinols to alkylstyrencs in 737;
Conversion of n-hexane, methylcyclopentane and cyclo- yield. This product polymerised satisfactorily in the prescnce of
hexane over rhenium-alumina catalyst treated with hydrogen Rz,O, a t 100" in 30 min. IC. RIDGWAY.
sulphide. lih. M. Minachcv and M. A. Ryashentseva ( I z v . A k a d .
Sauk S S S H , Otd. khim. N a u k , 1961, 103--106).-A 20% Re-A1,0, Initiation by hydrogen peroxide of emulsion oxidation of
catalyst treated with H,S is more active and stable than similar alkyl-aromatic hydrocarbons. R. V. Kucher, S. I). Kaz'min
untreatcd c,atalyst in the dehydrogenation of cyclohexane. dehydro- and V. D. Enal'ev (Zh. fcz. Ifhzm. [English Transl.], 1961, 35,
isomerisation of methylcyclopentaue and the dehydrocyclisation of 1147--1 I49).-Effect of initiation of autocatalytic oxidation i s
n-hexane to benzene. At 500-510", 5 atm. pressure of hydrogen influenced by the hydrocarbon itself and the time of addition of
and ratio HjCII of 5 : 1, cyclohexane gives 76% benzene, methyl- H20,. Continuous initiation accelerates oxidation of 1,l-diphenyl-
cyclopentane catalysate in 1 h. contains > 520,6 benzene, and in the ethane (I) but inhibits that of cumene (11) whereas, with I, I1 and
same conditions n-hexane undergoes marked hydrocracking with 1-phenyl-1-p-tolylethane, when H,O, is added a t the time of limiting
formation of C,-C, hydrocarbons, but the catalysate contains 10% concn. of hydroperoxide there is resumption of hydroperoxide
aromatics. G. F. P E N N Y . formation. This is ascribed to interaction of H,O, with inhibitors,
e.g., PhOH, formed in the system. Effect of an initiator depends on
Catalytic activity of birch charcoal in dehydrogenation of reactivity of reaction components ; thus, by slowly consuming the
cyclohexane. N . I. Shuikin and T. 1. Naryshkina (Izv. Akad. inhibitor, radicals of low reactivity that do not initiate oxidation a t
Xauk SSSR, Otd. khim. Nauk, 1962, 320-324).-The activity of early stages may do so a t later stages of the reaction. W. J. BAKER.
birch charcoal (ash 0.48%, analysis of trace metals given) in
dehydrogenating cyclohexane (I) to benzene a t 600' and atm. Oxidation mechanism of isopropylbenzene in weak alkaline
pressure was studied. Comparative experiments were done with emulsions. S. I). Kaz'min (Zh. prikd. Khim.. 1962,35, 422-428).-
ashless lamp black (11) and electrode graphite (3.3% ash) (111) as The oxidation mechanism was studied chiefly by examination of
catalysts. The catalysates were analysed chromatographically in main reaction by-products ; their effect was then assessed on
diatomite filled column containing 30% tritolylphosphate using kinetics of process. Oxidation was a t llOo/l0 atm. with ratio of
H, as carrier gas. With fresh charcoal the catalysate contained 97% hydrocarbuns to 0.1 N-Na,CO, 1 : 2. Hydropcroxide was deter-
of benzene. t , methylcpclopentane (IV), hexane and 2-methyl- mined iodometrically and carbonyl compounds by the hydroxylamine
pentane were not found. With charcoal which had previously method. The main oxidation products of isopropylbenzene in above
worked as catalyst for 33 h., the yield of benzene was only 50% conditions were the hydroperoxide, acetophenone, acetone, benzoic
with lo?; of 1V and 4% of hexane+Z-methylpentane. I1 formed acid, formic acid and resinous products. The retardation of reactions
no berrzene and I11 gave 6%. The different behaviour of these during the later stages of the process and a reduction of yield were
catalysts is attributed to their porous structure and the high sp. caused by accumulation of acid in the system ; thermal stability
surface of charcoal. Specific surfaces (rn.,/g.) were I1 2, 111 4, birch of the peroxide was lessened. Rate constants of reactions during
charcoal 519 (390 after 33 h. working). P. W. B. HARRISON. oxidation in emulsions is somewhat lower than for oxidation in
mass on account of formation of complexes with peroxide radicals
Catalytic alkylation of tetralin. VI. With secondary alcohols. and water molecules. A. L. B.
N. I. Shuikin and N. A. Pozdnyak ( I z v . Akad. Nauk S S S R , Otd.
khim. Nauk, 1962, 324-327) .-6-Isoalkyltctralins were obtained by Catalysis by phthalocyanines. IV. Self-inhibition of autoxi-
reaction of tetralin a t alm. pressure in presence of ZnC1, with dation of cumene in presence of nickel phthalocyanine. H.
ii-391 4.-INDUSTRIAL ORGANIC CHEMISTRY ii-392

Kropf (Erdol 11. Kohle, 1962, 15, 78-81).-The autoxidation of catalytic amounts of 60% perchloric acid of 0.01-0*03 g.-mol. per
cumene on Ni phthalocyanine (P) a t 79" reaches a max. rate and 1 g.-mol. of reactants. With lower reaction temp. ketone yield was
quickly falls off. By the pre-addition of possible reaction products not so high and increase in the amount of catalyst led to formation
it is shown that the catalyst is inactivated by the adsorption on i t of of resinous products. Catalytic acetylation of aromatic hydro-
a-methylstyrene peroxide which is a reaction product on NiP but carbons led t o low yields (8-30%) of aliphatic ketones. A. I,. B.
not on CUP since the activity of the latter is maintained. Added Alkylation of anisole by propylene and cyclohexene In
HCO,H retarded the oxidation by breaking reaction chains, whilst presence of boron trifluoride phosphate. S. V. Zavgorodnif and
MeOH promoted it. Other reaction products had little effect. I?. V. Alisova (Zh. obshch. Khim.. 1962, 32, 350-353).-Optimum
A. R. PEARSON. condition for preparation of 0- and p-isopropylanisole (82%) and
Thermal decomposition of cumyl hydroperoxfde. G. H. di-isopropylanisole (I) (17.2%) in presence of BFB,H,PO, was with
Twigg, G . W. Godin, H. C. Bailey and J. Holden ( E d o l u. Kohle, mol. ratio of reagents and catalyst 3 : 1 : 0.4 a t 60" (4 h.), With
1962, 15, 74-78).-The decomposition of the hydroperoxide lower mol. ratio of anisole/propylene (up to 0.5 : 1) a t 80" there was
(prep. described) in cumene (0.05-5 v01.-%) at 110-160" is a chain a reduction in the total alkylate yield b u t there was a higher yield
reaction started by the breaking of the 0-0 bond. The radicals of I. Optimum condition for prep. of 56.6 and 13.1% of 0- and
RO- (R = PhCMe,-) and -OH then react with the solvent: p-cyclohexylanisole (11) was 4 : 1 : 0.3 mol. ratio of reagents and
RO- + RH + ROH -t R- ; -OH + RH + H,O + R - ; and catalyst a t 40" (4 h. period). By decreasing the mol. ratio of reagents
R- + ROOH --f ROH + RO-. The chain-breaking reaction is t o 3 : 1, the general alkylate yield is not affected, but there is a 19.4%
2R- 3 R-R. Side reactions RO- -+ PhCOMe + CH,- and incre'ase of 11. With anisole and cyclohexene in 1 : 1 mol. ratio, the
CH,- + RH -+ CH, + R - also occur. In C,H, little reaction with yield of 2,4-dicyclohexylanisole increases 16%. Alkylation products
the solvent occurs ; the chief products were CH,, PhCOMe. ROH were identified by demethylation to the alkylphenols and conversion
and H,O. PhMe, I'hBu, PhEt and cyclohexane were relatively of the latter into alkylphenoxyacetic acids. A. L. B.
inactive solvents, while others had activities in the order :
n-CI2H2, < cyclo-C,H,,Me < p-C,H,Pri < decahydronaphthalenes Synthesis of o-aminobenzaldehyde and its N-methyl
< w-methylstyrene. A. R. PEARSON. derivatives from o-aminobenzoic esters. G. B. Barlin ( J . appl.
Chem., 1962, 12, 148--150).-The Me esters were boiled with
Oxidation of anthracene-phenanthrene fraction to obtain N,H,,H,O for 3 h. and then cooled. The ppt. was dissolved in
anthraqulnone and phthalic and maleic anhydrides. N. D. pyndine, p-toluenesulphonyl chloride added and the mixture
Rusyanova, G. D. Kharlampovich, G. F. Belyaeva and M. V. poured into water after 2 h. The residue was dissolved in (CH,OH),
Goftman ( K o k s i Khim. [English Transl.], 1962, No. 1, 40-44),-- and Na,CO, added. After standing the mixture was poured into
Vapour-phase oxidation of a mixture of anthracene and phenanthrene water, extracted with ether and after removal of ether the residue
(approx. 1 : 1) on V-K,SO,-SiO, catalyst at 370" for 1-4 sec. yields purified by vac. or steam distillation. The yields were o-amino-
anthraquinone (I) (63-60), phthalic anhydride (11) (50-63). maleic (35%), a-methylamino- (59%). and o-dimethylamino- (72%)
anhydride (111) (20-35%, of theoretical), respectively, together benzaldehyde. 0. M. W H I T T O N .
with the lactone (IV) ( 2076) of 2-hydroxybiphenyl-2'-carboxylic
N

acid. Recovery and separation of I , I1 and I11 are based on in- Phthalanilic acids as derivatives for characterisation of
solubility of I and IV in hot water and sublimation of I (after aromatic primary amines. N. V. Subba Rao and C. V. Ratnam
removal of IV with hot ZOO/, NaOH). The aq. solution of the two ( J . sci. industr. Res., 1962, 21B. 45-47).-The phthalanilic acids
acids from I1 and I11 is concentrated in vac. and the mixture of I1 are obtained in good yield and pure state and have sharp melting
and I11 is distilled as such; the pure acids can be preparcd by points. An excess of a benzene solution of pure phthalic anhydride is
differential crystallisation from water. The feedstock (from frac- added to a solution of the amine in benzene. Phthalanilic acid
tionation of crude anthracene) should contain a min. of carbazole usually separates out in a few minutes. The product is filtered,
(-,lo%) ; yields are lower if pure anthracene and phenanthrene are washed with benzene and dried. Further purification through
oxidised separately. Flow-sheets are shown and economics discussed. bicarbonate may be effected if necessary. Data are listed of 33
W. J. BAKER. deriv. prepared. (19 references.) A. I ~ A R K E .
Stereochemistry and mechanism of dehydration of cyclo- Reactions of unsymmetrical substituted urea8 during fusion
hexane derivatives. N. Ya. Grigor'eva and V. F. Kucherov ( U s p . with 4-chloro-3-nitrophenylalkyl(aryl) sulphones and sul-
Khim., 1962, 31, 39--72).-A review, with 241 references, of ionic phamides. V. A. Lavrishchev and A. E. Kretov (Zh. obshch.
reactions of dehydration and the stereochemical effects involved in Khim., 1962, 32,502-506).-During fusion of unsymmetrical urea
mono- and bi-mol. reaction in solution. Pyrolytic dehydration is with 4-chloro-3-nitrophenyl alkyl(ary1) sulphone (I) and sulphon-
also considered. A. L. B. amide and 2-chloro-5-nitrophenyl-hi-methylsulphonamide. there
Ultrasonic hydroxylation in a fluorescence analysis for were formed the corresponding alkyl-aryl- or diaryl-amine with
microgram quantities of benzoic acid. A. Weissler (Nature, NO, and sulphone substituents and one aryl group. Max. yields of
Lond., 1962, 193, 1070).-20 ml. of the solution, 0.00002 MB-zOH the latter were prepared when the mol. ratio of I to unsymmetrical
in 0.001 M-Na,HPO,-Na,PO, buffer pH 11.0, is irradiated with substituted urea was 1 : 4. By fusion of 4-chloro-3-nitrophenyl
ultrasound for 5 min. and the fluorescence, excited a t 315 nip, of methyl sulphone with p-phenetidine, 4-methylsulphonyl-2-nitro-4'-
the 0- and m-hydroxybenzoates produced measured a t 410 mp. ethoxydiphenylamine was obtained which was identical with that
The method is sensitive to 1 yg. BzOH but other aromatic acids, given by fusion of the sulphonc with p-ethoxyphenylurea. The
e.g., phthalic, interfere. E. C. DOLTON. alkylphenyl- and diphenyl-amines possessed the yellowing charac-
teristics of acetate silk on storage. A. L. B.
Selective poisoning of the catalyst in the Rosenmund
reaction. S. Affrossman and S. J. Thomson ( J . chem. Soc., 1962, Preparation of nicotinic and isonicotinic acids arid their
2024---2029).--Increased yields of PhCHO were obtained by amides by hydrolysis of the nitriles. I. A. Arkhipova, S. R.
Rosenmund reduction of BzCl over Pb/BaSO, catalyst in a solvent Rafikov and B. V. Suvorov (Zh. p r i k l . Khim., 1962, 35,369-393).--
(toluene) by poisoning of the catalyst with a S compound, Hydrolysis of nitriles of nicotinic and isonicotinic acid by aq.
tetramethylthiourea being the most effective. The mode of action of solutions of NH, of different concn. was effected a t 100-260"/4-45
the poison is discussed. H. S. R. atm., the hydrolysis proceeding stepwise through an intermediate
amide stage. Amides of the acid in the greatest yields were prepared
Mechanism of Michler 's hydrol oxidation by lead dioxide. a t fairly high temp. and with small concn. of NH,. A t 200' and
M. Matrka (Chem. PrzZm., 1961. 11, 342-345).-Oxidation of higher, with ratio of NH,/nitrile 2.0-2.5 : 1 and more. yields of
Michler's hydrol by PbO, in presence of dil. H,SO, yields dipheno- acid amounted to 90-95 7". A . L. B.
quinone-(4,4')-bis-dimethylimmoniumand formic acid which is
uxidised further to CO,. The mechanism of the oxidation reaction Perfluoroalkyl derivatives of boron and tin and perfluoro-
is similar to that with Malachite green. (13 references.) alkyl iron carbonyls. S. L. Stafford (Dissert. Abstr.. 1961, 22,
M. JUNGR. 1401).-Dimethyl-(I), dibutyl-. divinyl-and diphenyl-bis(perfluor0-
Perchloric acid and its compounds as catalysts in organic viny1)tin were prepared from the corresponding perfluorovinyl
syntheses. 111. Acetylation of some aromatic hydrocarbons. (PFV) Grignard reagents and SnCl Treatment of I with the
C . N. Dorofeenko and 1,. V. Polushchuk (Zh. obshch. Khim., 1962, stoicheiometric amount of BCl, gives PFV-dichloroborine (II),
32, 364--367).--0ptirnum condition for the acetylation of ethers of bis(PFV)chloroborine and tris(PFV)borine. I1 with SbF, at low
mono- and poly-hydric phenols was as follows : heating a t 95-100" temp. gives PFV-difluoroborine. Trcatmcnt of E'e(CO), with 1-3-C
for R short period in a water bath with slight excess Ac,O and perfluoroalkyl iodides a t moderate temp. gave perfluoro'alkyl Fc
ii-393 4.---INDUSTRIAL ORGANIC CHEMISTRY ii-394
tetracarbonyi iodides and -tricarbonyl iodide dimers. 1.r. spectra of to a mixture of ethoxyethoxyethanol, NaOH and commercial gas
P F V deriv. of Ge, Si, As, Hg, Sn and B were studied and the bands oil, b.p. 177-300", a t 160-170°. followed by 12-dichloropropane,
from 650 to 3500 cm.-l were identified by means of spectral assign- to give propyne in 64% yield, in addition to 13% of ailene.
ments already known. G . MACKENZIE. F. R. BASFORD.
Preparation of aluminium t-alkoxides. M. S. Bains (Canad. Halogenated hydrocarbons. Socikt6 d'E1ectro-Chimie,
J . Chem., 1962, 40, 381-382).-Despite assertions to the contrary d'Electro-Mgtallurgie et des Acikries Electriques d'Ugine (B.P.
(Mehrotra, ,/. I n d i a n . chem. Soc., 1953, 30, 585 ; 1954, 31, 85), 788,828, 10.1.56. Fr., 25.1.55. Addn. to B.P. 749,408; J.A.C.
Al(OBut), is formed from A1 isopropoxide by the alcohol-exchange Abstr., 1957, i, 496).-To obtain a mixture of CCl, and C,CI, in
method for the prep. of A1 alkoxides, i t being very difficult to prepare predetermined proportions, C,C1, and another chlorinated hydro-
pure Al(OPri)(OBut),. Interchange of Al(0Pri) with t-C,H,,OH or carbon (I) with 2 or 3 C atoms is heated with C1, a t 300-700"
Et,Me carbinol yields aluminium t-fientyloxide (sublimes a t 130- (depending on I and on the composition of final mixture desired),
135"/0.03 mm.) or aluminium diethylmethylcarbinoloxide (sublimes the amount of C1, in excess being equiv. to the no. of moles of C,Cl,
a t 155O10.03 mm.), respectively. In the prep. of A1 t-alkoxides by formed. The mixture is heated over a catalyst a t 200-220" (to
transesterification there is no evidence that interchange of the third convert C1, to C,Cl,) and then a t 220-350" with C,H, in amount
alkoxide group is hindered either by steric factors or otherwise. equal t o 9 of the C,Cl, present. E. ENOSJONES.
W. J. BAKER. 1,4-Dibromobutene and l,4-dibromobutane. Cellulose-
Synthesis of organo-silicon monomers with nitrile groups. Polymbres e t Ddriv6s ' Cepede ' S.A. and RED G.m.b.H. (Inventors :
A. D. Petrov, E. P. Zakharov, N. A. ZadorozhnyI and V. A. John Elian and Marcel Repingle) (B.P. 869,121, 26.8.57. Fr., 4.3.57).
Ponomarenko ( Z h . prikl. Khim.. 1962,35, 385-389).-New catalysts -Butadiene is treated with Br, at low temp. in the presence of a
were prepared for use in the interaction of SiHCl, with acrylonitrile, solvent to form a mixture of 1.4- and l,2-dibromobutene. The
viz., dimethylamino-acetonitrile and -propionitrile and di-(p- mixture is heated to -90" to increase the proportion of the 1.4-
cyanoethy1)cyanamide. The prep. of cyano-Si deriv. from 3-cyano- isomer, and this is separated as solid by cooling. The 1.2-isomer is
cyclohex- 1-ene (to give 3- and 4-trichlorosilylhexy1 cyanide) and recycled to a point before the mixture has bcen heated high enough
P-allyloxypropionitrile (to give I-~-cyanoethoxyprop-2-ylsilanes)for appreciable isomerisation to take place. 1,4-Dibromobutane is
was by interaction with SiHCl, or R,Cl,_,SiH respectively. I n the obtained by hydrogenating 1,4-dibromobutene. E. ENOSJONES.
first of these the best results were obtained in presence of But,O, Fluorine compounds. E.I. Du Pont de Nemours & Co.
or H,PtCl,. A. L. B. (Inventor : C. W. Tullock) (B.P. 870,328, 16.2.60).-Compounds
Reactions of disilane with chlorobenzene in the gas phase. CFXY.R.X (X is H or F ; R is divalent periiuorocarbon radical ;
E. A. Chernyshev, N. G. Tolstikova, S. L. Ioffe and A. D. Petrov 2 is F ; Y is N,-CF,-R*X or NX', ; X' is C1 or Br ; or Y + Z is
(Zh. obshch. Khim., 1962, 32, 369-374).-Reactions of PhCl (I) N X ) are obtained by interaction of X-R.CN with X and a fluoride
with hexamethyl-, pentamethylchloro- and tetramethyldichloro- of Na, K, Rb, Cs, Cu, Ag, Hg or P b at 25-250° under anhyd.
disiiane in the gas phase occur via Si free radicals and mainly result conditions. The products are yellow-green fluids of good heat
in formation of Me,SiCI, benzene, bis(chlorodimethy1)silylmethane stability and resistance t o hydrolysis with 10% aq. NaOH at loo",
and high-temp. residues. Reactions of I with hexachlorodisilane and are useful as initiators of polymerisation, fire-extinguishing
in the gas phase are also via radicals and result in PhSiCI,, SiCl, agents, solvents for polymers, water-proofing agents, and also as
and high-temp. residues. A. L. B. fumigants and rodenticides. I n an example, a mixture of CF,.CN,
Gasometric determination of alkyl radicals in polyalkyl- Br, and AgF is heated at 100-190" for total of 4 h., then the volatile
siloxanes and silicon-functional organo-silicon compounds. product is distilled, t o give a fraction, b.p. 16-20", consisting of
M. G. Voronkov and V. T. Shemyatenkova (Izv. A k a d . N a u k S S S R , azoperfluoroethane (go), N-bromo(perfluoroethy1idene) imine (3-8), ant1
Old. kfiim. N a u k . 1961, 178--180).-Alkyl radicals (CH, and C,H,) bromopentafluoroethane (1yo). F. R . BASFORD.
attached to a Si atom can be determined as the corresponding hydro- Halogenated organic compounds. R. N. Haszeldine (B.P.
carbons by decomposition with alkalis, with an accuracy of 1-2%. 869,364, 5.10.56).-Compounds CF,X-CCIYfCF,CF.CF,] ,.Z (X is
G. F. PENNY. Br or C1 ; Y is C1 or F ; n is 0-20 ; 2 is Br or I) are obtained by
~
interaction (telomerisation) of CF,X.CClYZ with I mol. of a
Solvents for the separation of dioleAns from mixtures of difficultly polymerisable fluoroalkene or fluoropolyene, e.g.. CFR:CF,
hydrocarbons. Badische Anilin- u. Soda-Fabrik A.-G. (B.P. or perfluorobuta-l,3-diene (R is alkyl or polyhalogenoalkyl), in
870,380, 20.2.58. Ger., 23.2.57).-The diolefins are extracted from presence of a free radical-forming agent. Thus, a mixture of
the mixture with a selective solvent, especially a saturated hetero- CF,Cl.CFCII (200) and C,F, (88) is heated a t 170' for 3.5 h., then
cyclic compound containing a carbonyl group (excluding a sulpholan), distilled, to give C,F, (84), CF,Cl.CFClI (174) and
e.g., N-methylpyrrolidone. E. ENOS JONES. CF,Cl.CFCl.CF,~CFI*CF, (6 9.). b.p. 58.5-60.5"/20 mm.
Conjugated diolefins. Farbenfabriken Bayer A.-G. (B.P. F. R. BASPORD.
869,780, 17.12.59. Ger., 12.12.58).-A conjugated diolefin is Separation of fluoroethylenes. Farbwerke Hoechst A.-G.
contacted with a mixture of ( a ) a n alkali metal, an alkali metal (B.P. 869,568, 5.12.57. Ger., 5.12.56).-Fluorinated or fluorinated
alloy or an alkali metal hydrocarbon deriv. of 1-15 C and (b) a and chlorinated (or brominated) ethylenes containing H atoms are
compound (MR'JZ where M is B, Al, Ga, I n or T1, each R' may be separated from fully halogenated ethylenes (I) by interaction with a
the same or different and is a straight or branched chain, hydro- solution or suspension of a Hg compound (HgO, HgCI, or Hg
carbon radical, alkoxy or aryloxy, or H or halogen, at least one of acetate) in water and/or an alkanol. I are recovered in a pure state.
R' being a hydrocarbon radical, and x is 1 or 2, at a temp. which E. E N OJONES.
~
will preclude polymerisation of the conjugated diolefin and in the Purification of fluorinated hydrocarbons. R. N. Haszeldine
absence of 0,. In an example isoprene is heated under reflux with (B.P. 869,273, 15.8.56).-Satur~ed perfluorocarbon compounds
Na metal and BPr,. E. ENOSJONES. which have H-containing and/or olefinic impurities are purified by
subjecting the crude compound t o free-radical oxidising conditions
2-Pheny1-1,a-butadiene. Distillers Co. Ltd. (Inventor : E. G. E. including an 0-donor, whereby the impurities undergo selective
Hawkins) (B.P. 869,456, 10.4.59).-2-Phenyl- 1,3-butadiene is degradation to readily separable products. The oxidising conditions
produced by dehydrating 3-phenylbut-3-en-1-01 and/or -2-en-1-01 include radiation by light of wavelength ~ 3 5 0 0A, C1, or Fa as an
and/or 3-phenylbutane-1.3-diol by the action of heat in the presence initiator, mol. 0, in a molar excess of 1 : 5-100 relative to the
of I, as dehydration catalyst. An example is the dehydration of the initiator, and a pressure between 10 mm. Hg and 10 atm.
mixed alcohols obtained by interaction of a-methylstyrene with E. ENOS JONES.
CH,O. E. ENOSJONES. Recovery of halogen from reaction residues. Imperial
1-Alkynes. British Oxygen Co. Ltd. (Inventors : J. A. Tebboth Chemical Industries Ltd. (Inventors: G. J. Sleddon and R. C.
and M. I<. Johnson) (B.P. 785,727, 17.6.55. Addn. to B.P. 709,126). Anderson) (B.P. 869,162, 12.12.58).-Residue containing halogen
-An improved method for the prep. of alk-1-ynes comprises (Cl or Br) values, and obtained during org. reactions involving the
continuously feeding a 1,2-dihalogenoalkane or a 1- or Z-halogeno- use of a n alkyl A1 halide, is heated with a compound R R O (R and
alkene with stirring into a mixture maintained at > 100' and R' are Me or Et, or R is H) a t 120-400", with recovery of halogen
consisting of inert diluent (b.p. > 100" and higher than that of the in the form of alkyl halide. Thus, residue formed after heating
alkyne), alkali metal hydroxide (or alkoxide of an alcohol of b.p. MeAlCl, with acid-treated bauxite cIay (to produce methylsilanes)
> 100"). and alcohol of b.p. > 100" (and higher than that of the is heated t o 310°, then MeOH is added during 6 h., with distillation
alkyne), e.g., ethoxyethanol. Thus, chloropropylene is added slowly of .MeCl containing HCl. F. R. BASFORD.
P
ii-395 4.-IND USTRIAL ORGANIC CHEMISTRY ii-S9B

Electrochemical manufacture of halogenohydrins. Standard pure maleic anhydride is distilled o u t at .<: 122" (98"), leaving Bz,O
Oil Co. (B.P. 869,087, 8.12.59. U.S., 29.12.58).-Halogenohydrins and higher-boiling impurities as bottoms. J . M. JACOBS.
arc obtained by subjecting an aq. solution of an up-unsaturated
aliphatic or alicyclic carbon compound (aldehydc or ketone) to the P a r t i a l dehalogenation of di- and tri- halogenoacetic acid.
action of an electric current in a cell in presence of HCI, HBr and/or Knapsack-Griesheim A.-G. (B.P. 870,040, 16.7.59. Ger., 22.7.58).-
HI. Preferably the ccll is undivided and has a Cd or graphite cathode. Vapour of di- and tri-halogenoacetic acid is passed with the aid of a
T h u s in a (:ell with a Cd cathode and graphite anode in which the carrier or by vac., together with lI,, over a hydrogcnation catalyst
clcctrolyle in 0.5 wHI3r containing 2% of CdBr,, CH,:CH.CHO is (a metal or a salt of a metal of Group VIII) at 150". Thus, a vapour
introducetl at t.hc rate of 375 C.C.per min. during 1.5 h., together mixture of CCI,.CO,H (28.5) and AcOH (71.5%) is passed with €Iz
wit11 [II3r (0.43 mol.), while passing therethrough at 40" a currcnt over a catalyst (1% Pd on SiO, gel) a t 75", to give an cfflurnt
2.7 V :it c.cl. ,100 A pcr sq. It. Tlicre is thus produced a mixture consisting of CHCl,.CO,H (22.4) and AcOH (77.2%).
of nioiio- aud tli-l)romoliydriiis in 93.4% yield (80u/, conversion), F. rt. BASFORD.
;IS well as 207; ol JitCI-IO and PrOH. F. I<. BASFORD. [A, B] Vinyl esters. [C] Vinyl stearate. Air Reduction Co. Inc.
(B.P. 869,828-30, 21.8.57. U.S., 27.8.56).-1n the trans-ester
Dithiophosphinic acid compounds. American Cyanamid Co. tion of vinyl acetate with a fatty acid (especially stearic acid), thr:
(l3.P.870,005, 26.10.59. U S . , 29.10.58).-Compounds catalyst used is a Hg salt (acetate) and acid co-catalyst (H,SO,).
(;N.LCH,]2.(1<)PS2Yand thcir salts and esters are produced by [A] Active catalyst is recovered for reuse by removal of the acid
i,ondcnsing PFIR.[CH,],*CN with S and YH a t 10-115" (25-60") co-catalyst by pptn. as insol. alkaline earth salt, distillation in
under anhytl. conditions in an inert atm., then treating the resulting vacuo and then removal of the required ester by distillation a t
product if tlesired with a metal alkoxide and converting the salt higher temp. [B] The by-product acid, is removed by distillation
into an ester (R is org. group attached to P via C : Y is a salt or (as in the vac. distillation in [A]) and the inter-esterificationcontinued.
cqtcr iorming group, prefcrably substituted or unsubstituted NH, [c]The process of [A] is applied to the prep. of vinyl stearate from
group other than a quaternary NH, group, c.g., pyridinium, vinyl acetate, the vinyl stearate being separated from excess stearic
qiiindinium, :~niIiniuni, giianitlinium. or tricthylammonium, or Y acid by extraction with a parafin hydrocarbon of < 7 C (n-pentanc).
may bc allali mctd or a multivalent metal). The compounds are E. ENOSJONES.
uscf111as lubricant atlditivcs, insccticidcs and flotation agents. In Dichlorodialkylaminomethanes. CIBA Ltd. (H.1'. 870,454.
an csamplc, BII(J~CLI,],.CN), is treated at 60" to a slurry of S and 26.8.57. Switz., 27.8.56 and 18.7.57).-Compounds NR,.CHCl,
pyridint; to yield p y ~ i d i , ~ ?di-2-cyonoethyl
Z~~z dithiophosphinate, m.p. (or tautomers thereof) are obtained in high yield by interaction of
95''. F. €1. BASFORD. HCOsNR, with phosgene (in a n anhyd. org. solvent) (K is alkyl).
Carbonylation process. Esso Research & Engng Co. (B.P. The products are useful as intermediates in the synthesis of aromatic
822,042, 2.8.56. U S . , 11.8.55. Atldn. to €3.1'. 722,975; J.A.C. aldehydes. F. R. H A S F O R D .
Abstr., 1955, ii, 338).-C,o catalyst is removed from the product of Halogenated phenoxyalkyl substituted amines. Rohm &
interaction of an oleliii with C:O and 11, by cxtraction with an aq. Haas Co. (B.P. 870,399, 19.12.57. U.S., 14.12.56).-A halogenated
solution of a Co complex, C . R . , Co cyclopcntacliene chloride. phenoxyalkyl-substituted amine is produced by heating a mixture
E. ENOSJONES. of a polyhalogenated benzene (0- or p-C,H,Cl,, 1,2,3- or 1,2,4-
Rectification of a formaldehyde-containing solution. C,H,Cl, etc.), a hydroxyalkylated amine(ethanolamine, etc.) and a
Sumitomo Chcmical Co. Ltd. (B.P. 869,764, 4.2.59. Japan, 26.7.58). hydroxide or hydride of K or Na (which if desired may be first
--- A clear, conc. aq. CH,O solution, suitable for use in the production reacted with the amine). Thus, a mixture of ethanolamine, micro-
of linear CH,O polymers, is obtained by distilling a mixture of pulverised NaH and technical trichlorobenzene is heated a t 125-
CH,O (50-80 wt.-%), MeOH and water (15-35 wt.-yo on CH,O 132" for 8 h., then washed twice with 200 c.c.-lots of water, and
plus watcr) in a column operated at a top temp. of 30-61*/160- distilled, t o give dichlorophenoxyethylamine, b.p. 149-177'/15 mm.
6tiO mm. with a Me013 reflux ratio of 5-15 : 1, such that pure MeOH F. R. BASFORD.
is removed at the top. F. R. BASFORD. Monomethylamine nitrate. Commercial Solvents Corp. (B.P.
870,435, 24.11.59. U.S., 19.12.58).-The nitrate is prepared by
Purification of gaseous formaldehyde. E.1. Du Pont de contacting approx. equimol. proportions of HNO, and mono-
Xcmours d;: Co. (B.Y. 870,382, 14.3.58. U.S., 4.4.57).-A process for methylamine a t 160-250° (200-220°) in a tubular reactor filled
the purification of gaseous formaldehyde (I), containing 0.04- with inert packing material, and removing the reaction products
5.0% by wt. of normally liquid impurities, is passed into contact in two phases, one of which is substantially steam and the other
with a liquid hemiformal solution containing initially 8-73 mol.-% molten monomethylamine nitrate, from the lower end of the
of comhined+dissolved I and 92-27 mol.-yo of a primary or reactor. E. ENOSJONES.
s-alcohol containing 5-12 C-atoms per mol. (cyclohexanol), which
110ws as a film over an inert solid surface maintained at - 15" to E t h e r - m i n e s . Dehydag Deutsche Hydrierwerke G.m.b.H.
+20° and maintaining the flowing liquid-gas interface for a time (B.P. 869,405, 14.10.59. Ger., 21.11.58).-Ether-amines are
sufficient t o allow 60-98y0 of the impurities to dissolve in the obtained by interaction of cyanoalkenes with monohydric alcohols
hemiformal solution. E. ENOSJONES. a t 30-60" in presence of NH,, with simultaneous or subsequent
hydrogenation. Thus, a vessel containing CH,:CH.CN, MeOH and
C,,-aldehyde. C. Pfizer & Co. Inc. (B.P. 870,310, 11.5.59. I J S , Raney Ni is charged with NH,/8 atm. and with H,/50 atm., then the
75.9.58) .-In the Darzcn's glycidic ester synthesis of C,,aldehyde mixture is heated t o 90". After a n initial rise in temp. hydrogenation
by adding alcohol-free alkali metal alkoxide portionwise a t < 10" is completed at 60 atm., and the filtered product is distilled, to give a
to a mixture of p-ionone and an alkyl chloroacetate, then treating 65% yield of 3-methoxypropylamine, b.p. 119". If the reaction is
t h e product with alcoholic alkali metal hydroxide a t < lo", acidifying, effected at 150"/200 atm., the yield can be raised to 95%.
and decarboxylating the saponified glycide ester, improved yields are F. R. BASFORD.
obtained by carrying out the first stage in presence of one or more Acetonitrile. State of Japan {Inventors : I<. Morikawa and
anhyd. diluents, viz., IICONMe,, pyridine, AcNMe,, AcNHEt or T. Shiba (B.P. 870,462, 6.3.58).-MeCN is produced when C,H2 and
picoline. F. R. BASFORD. NH, are reacted at 500-650" under atm. or superatm. pressure in
Recovery of adipic acid f r o m oxidation p r o d u c t s of cyclo- the presence of a catalyst comprising AI,O, and at least one alkali
hexane. Lonza Electric and Chemical Works Ltd. (B.P. 870,105, metal hydroxide, or inorg. or org. salt of an alkali or alkaline earth
29.12.59. Switz., 7.1.59).-The process comprises extracting with metal, the starting gases containing NH, in excess of the stoicheio-
mcthylene chloride, the crude aq. extract obtained from the reaction metric quantity. The steam partial pressure in the gases is main-
products cyclohexanol and cyclohexanone. The methylene chloride tained within the range 2-50 mm. Hg. E. ENOSJONES.
layer contains impurities interfering with the crystallisation of the U n s a t u r a t e d ureido ethers and polymers thereof. Rohm
adipic acid ; adipic acid is recovered from the aq. layer. & Haas CO. (B.P. 822,266-7. [A] 7.9.55, [B] 12.4.56. U.S., [A]
E.ENOSJONES. 7.9.54, [B] 15.4.55. Both addnl. to B.P. 747,184; J.A.C. Abstr.,
Continuous purification of crude maleic anhydride. Yawata 1957, i, 317).-Compounds CH,:CH.Y -A.NR.CO.NHR' are claimed
Iron SC Steel Co. Ltd. (Inventor: R. Shimose) (B.P. 869,297, (A is a divalent hydrocarbon radical of > 18 C but > 2 C, optionally
19.9.57).--l'he process comprises fractional distillation in two interrupted by 0, N or S, but in the grouping 0.A.N there are a t
successive columns > 8(10) m. long in which the pressure is < 60(20) least 2 C between each hetero atom and the hetero atom nearest
nim. Hg. I n the first, low-boiling impurities (benzoquinone and thereto; R is hydrocarbon radical of 1-18 C, optionally sub-
Ac,O) are removed a t (top) temp. < 112" (90") and in the second stituted or interrupted by one or more hetero atoms ; R' is hydro-
ii-397 4.-INDUSTRIAL ORGANIC CHEMISTRY ii-398
carbon radical of 1-24 C similarly substituted as R ) ; Y is Cyclic di- and tri-carbdxylic acids. Henkel RC Cie G.m.b.H.
[ h ] 0, [B] 0 or S. The products are useful solvents (especially [A] (B.P. 869,505, 6.3.59. Ger., 7.3.58).-.4romatic di- and tri-carboxylic
in insecticidal compositions) and for many other purposes, [B] acids and heterocyclic di- and tri-carboxylic acids of aromatic type
especially in the finishing of textiles. They may be polymerised are obtained by heating aromatic hydrocarbons or C0,H-free
alone or in presence of other monomers, to give a variety of products. hetcro-aryl compounds with an alkali metal salt of an aromatic or
As an example of the nicthod of prep., [A] a solution of EtNCO in aromatic-heterocyclic carboxylic acid (other than terephthalic acid)
benzene is addctl dropwisc at 0-5" to bcnzene containing 2-amino- a t > 300" under pressure in absence of water and 0, but in presence
vinyl ether, then after heating to 30" for 30 min. the solvent is of a dehydrating agent, a protective gas, and (as catalyst) Cd, Zn,
removed to give N-(2-vinyloxyethyl)-N'-ethylurea,m.p. 55-47". Hg, or a compound thereof, The dehydrating agent may be a
This product is useful as a bacteriostatic agent (e.g., against M . carbide (especially A1 or Ca carbide), Sj or B, or a compound of Si
pyogenes var. azweus), as a special solvent for coupling oil and or B. Thus, a mixture of K, pyroniellitate, CaF,, A1 carbide and
watcr-sol. agents such as alkylphenoxypolyoxyethanols,and for benzene is heated in a 600-C.C.vessel at 425" for 15 11. in presence of
various other purposes. F. R. BASFORD. C0,/1400 atm. (initial). The filtered solid is dissolved in water, and
Separation of glucosaccharolactones. Pfizer Ltd. (Inventors : the resulting solution is acidified with aq. HCl a t 90-looo, with
D. G. Cannon and P. M. Watson) (B.P. 870,051, 28.9.56).-1.4- pptn. of terephthalic acid. F. R. BASFORD.
Glucosaccharolactone is separated from admixture with 3,6- 3-Carboxy-4-methylnaphthalene derivatives. Farbwerke
isomer by extracting with an alkanol of 2-5 C at or slightly above Hoechst A,-G. (B.P. 870,384, 9.6.58. Ger., 8.6.57).-The compound
room temp. under anhyd. conditions, then crystallising the desired 5 - chloro - 8 - methoxy - 4 -methyl - 1 - hydroxynaphthalene -3-carboxyl-
product from the extract. F. R. BASFORD. ic acid, m.p. 211-212", and its deriv. are claimed. They are useful
Amylose derivatives. Cooperatieve Verkoop- en Productie- as intermediates in the synthesis of tetracycline. The method of
vereniging van Aardappelmeel en Derivaten " Avebe " G.A. (B.P. prep. comprises condensing m-OMe.C,H,Ac with a succinic acid
869,192, 4.2.59. Neth., 4.2.58).-Amylose ethers, which are com- ester ; catalytically hydrogenating t h e resulting cinnamic acid
pletely sol. in water a t 100" and form a gel only slowly, and are derivative ; introducing C1 in the @-position to the OMe group ;
characterised further by a degree of substitution of >0.02, are then effecting ring-closure of the thus-formed y-(6-chloro-3-
obtained by ctherifying amylose in aq. alkaline solution t o the methoxypheny1)-f3-alkoxycarbonylvaleric acid ester by heating a t
required extcnt (with ethylene oxide, ethylene chlorohydrin, moderately high temp. in presence of a condensing agent (e.g.,
Me,SO, etc.), then neutralising with acid, and adding a salt which polyphosphoric acid) ; dehydrogenating the resulting tetralone ;
salts out the ether. The preferrcd salt is one which has a multivalent and hydrolysing. F. R. BASFORD.
anion, eg., a sulphate (MgSO,). F. R. BASFORD. Salts or other derivatives of naphthalene-2,6-dicarboxylic
Azulenes. K. Ziegler (B.P. 794,383, 23.2.56. Ger., 7.3.55. acid. Henkel & Cie G.m.b.H. (Inventors: B. Raecke and 1-1.
Addn. to B.P. 750,209).-A quaternary pyridinium (or quinolium) Schirp) (B.P. 795,179, 13.1.56. Ger.. 15.1.55. Addn. to B.P.
salt is condensed with a metal (alkali metal) compound of a cyclo- 744,721 ; J.A.C. Abstr., 1957, i, 106).-The process of B.P. 744,721
pentadiene (unsubstituted in at least one o-position to the CH, is improved by operating a t >360° (390-450") in presence of an
group), then heating the resulting fulvene (optionally without inert medium other than CO,, e.g., aliphatic or aromatic hydro-
isolation thereof) a t 100-300". Thus, 1-methylpyridinium bromide carbon, N, or CO although CO, may be also present. Thus, a vessel
is treated a t -35" with a solution of Na methylcyclopentadiene in containing 2-C,,H7.C0,K, CdCl, and C,,H, is freed from air with N,,
liquid NH,. The NH, is slowly evaporated and the solid residue then the contents are heated a t 425" for 1 h. The cooled product is
separated. Benzidine, is added and the mixture distilled with steam extracted with hot water, and the filtered liquor is acidified with
a t 300". The crude product is purified to give aq. yield of 55.6% HCl, with pptn. of 2,6-C1,H,(CO,H),. Extraction of the mother
of I-methylazulene. F. R. BASFORD. liquor with ether affords a small amount of 2-C,,H,.CO,H.
F. R. BASFORD.
Synthesis of 1.1-diarylethanes. American Cyanamid Co. (B.P. Diethynyl-quinols. Farbwerke Hoechst A.-G. (B.P. 870,097,
833,066, 4.7.57. US., 13.8.56. Addn. to B.P. 755,363).--1,1-Diaryl- 13.8.58. Ger.. 13.8.57).-An 0- or a p-benzoquinone, optionally
ethanes (of B.P. 755,363 ; J.A.C. Abstr., 1957, ii, 339) are obtained substituted in the remaining positions by halogen or alkyl, or
in improved yield by interaction of a mono- or di-alkylbenzcne containing 1-2 condensed benzo rings, is treated a t 0 ' in liquid
(toluene or xylene) with an alkyne, e.g., acetylene, in presence of NH, with an alkali metal compound of a n acetylene, to give the
the H,SO,-Hg compound catalyst (15-45% on alkyne) and a t corresponding 1,2-dihydroxy-l,2-diethynyl-or 1,4-dihydroxy-1,4-
1-10 atm. F. R. BASFORD. diethynyl-dihydrobenzene. Thus, C,H, is passed into NH, a t
Dihydroxydiarylmethanes. Monsanto Chemical Co. (Inventors : -35" t o -40", then Na is added portionwise. The flow of C,H, is
D. J. Beaver and R. 0. Zerbe) (B.P. 869,476, 16.9.58. Addn. to then reduced and a solution of p-benzoquinone in toluene is intro-
708.640, 12.4.51).-Compounds claimed are of the general formula duced slowly a t -35" t o -40". A further 8-10 h. a t the same temp.
CHR(C,H,R'R.OH-3,6,4), (R is Ph substituted by C1 ; R' is alkyl NH,Cl is cautiously added, the NH, is allowed to ev-aporate. and the
of 4 C ; R" is alkyl) ; they are useful as antiseptics, germicides, org. layer is worked up, t o give crude 1,4-dihydroxy-l,rl-diethynyl-1,4-
and also as antioxidants in rubber base stocks. In an example, a dihydrobenzene, m.p. 196". F. R. BASFORD.
mixture of 6-butyl-m-cresol, 2,4,1-C6H,Cl,.CH0, and conc. aq. HCl
is heated a t 95" for 4 h., until a sample affords a crystalline ppt. Reduction of tetrahydrobenzaldehydes. CIBA Ltd. (B.P.
when diluted with 3 vol. of heptane. The mixture is then cooled, 870,009, 14.12.59. Switz., 22.1.59).--1,2,5,6-Tetrahydrobenzyl
and hexane is added, with separation of 2,4-dichlorophenyCbis-(4'- alcohol is obtained in good yield by reducing the corresponding
hydroxy-2'-methyl-5'-t-butylphenyl)methane,m.p. 209.9-210.4". aldehyde with H, in presence of a Cu-Cr oxide catalyst in a solvent
F. R. BASFORD. (cyclohexane). Homologues are similarly made. F. R. BASFORD.
4-Nitrostyryl-2-sulphonic acid compounds. J. R. Geigy Indol-3-yl ketones. Upjohn Co. (B.P. 869,775, 15.9.59. U.S.,
A.-G. (B.P. 869,372, 28.4.58. Switz., 29.4.57).-Compounds 24.9.58).-Indol-3-yl ketones optionally substituted in the 1-position
4,2,1-N0,~C6H,(S0,H).CH:CHR (R is aromatic radical or hetero- by low-mol. alkyl or aralkyl and in the 2-position by low-mol. alkyl,
cyclic radical of aromatic character), useful as intermediates in the aralkyl, aryl or halogenoaryl, are obtained in high yield in highly
prep. of C1-fast optical brightening agents, are obtained in good pure form by heating a 3-unsubstituted indole with POCl, and an
yield in an improved process by condensing a n org. N-base or an amide R*CO.NR'R" at 50-150" for 1-10 h. (R is low-mol. alkyl,
alkali metal or alkaline earth metal salt of 4,2,1-NO,.C,H3Me.S0,H halogenoalkyl, aralkyl, or aryl ; R and R" are low-mol. alkyl or
with RCHO a t 100' in presence of a saturated s-N base (piperidine) R' is H). Thus, POCl, is added slowly a t -20' to EtCO.NMe,
in a hydrophilic solvent (HCONMe,). Thus, a mixture of Na (initially at 5") then after a further 20 min. a solution of indole in
4-nitrotoluene-2-sulphonate, HCONMe,, pipendine and PhCHO, EtCOaNMe, is charged while keeping below 40". The mixture is
heated for 15 h. a t 140-145", affords Na 4-nitrostilbene-2-sulphon- heated at 87" for 2 h., diluted with ice-water, and worked up to
ate. F. R. BASFORD. give 3-propionylindole, m.p. 171-173'. F. R. BASFORD.
Conversion of naphthalic acid into naphthalene-2P-di- Alkyl(1-p-menthen-6-yl) ketones. L. Givaudan & Cie S.A. (B.P.
carboxylic acid. Henkel & Cie G.m.b.H. (B.P. 794,803, 15.11.56. 870,001. 18.9.59. U.S., 19.9.58).-The ketones, useful as perfume
Ger., 19.11.55. Addn. to B.P. 756,472 ; J.A.C. Abstr.. 1957, ii, 530). ingredients, are obtained by interaction of p-menth-I-ene with
-The original process is improved by operating in presence of inert (RCO),O (R is low-mol. alkyl) a t 0-50" in presence of ZnC1,. Thus,
gas (other than CO,), e.g., N,, CH,, C,H,, C,H, or benzene vapour p-menth-1-ene is added during 30 min. at 30-38" t o a solution of
in presence of a catalyst, e.g., CdF,. F. R. BASFORD. Ac,O and ZnC1, then after a further 2 h. water is charged. The org.
ii-399 4.-INDUSTRIAL ORGANIC CHEMISTRY ii-400
layer is separated, washed with 10% aq. NaOH, dried, and distilled, 0--5" to precipitate trichloroisocyanuric acid. h yield of -95% is
to give 6-acetyl-p-menthene,b.p. 82'13 mm. F. R. BASFORD. obtained. E. ENOSJONES.
Acenaphthenequinonemonoxime. Farbwerke Hocchst A.-G. 3- or 5-Amino-l,2,4-triazole. Farbenfabriken Bayer A.-G.
(B.P. 869,855, 2.9.57. Ger., 1.9.56).-The oxime is obtained by (B.P. 815,273, 20.12.56. Ger., 23.12.55. Addn. to B.P. 765,728;
interaction of acenaphthylene with N,O, in acid medium in presence T.A.C. Abstr., 1958, i, 509).-The process of B.P. 765.728 for the
of 0, or air, or with HONO in an alcohol or a cyclic ether (containing production of 3- or 5-amino-l,2,4-t;iazole is modified (without loss
> 10% of water) at 0-60". Thus, conc. aq. HCl is added dropwise in yield) by heating an aminoguanidine salt with HCO,H a t 100-
to a mixture of MeOH, acenaphthylene and aq. NaNO, a t 40-50" 120" in absrnce of inert org. solvent and optionally in initial presencp
until strongly acid, then a solution of NaNO, in water is added of water. Thus, aminoguanidine bicarbonate is added gradually to
slowly a t 40-50". The mixture is brought to the boil, clarified, and HCO,H, then after 22 h. a t 110-115" the mixture is cooled, with
poured into ice-water, with pptn. of acenaphthenequinonemonoxime pptn. of the amino-1,2,4-triazole in 96.7% yield. F. R. BASFORD.
in 80% yield. F. R. BASFORD.
Ammeline. Whiffen & Sons Ltd. (Inventor: L. H. Cloak)
Oximes. Imperial Chemical Induqtries Ltd. (Inventors : A. Hill (B.P. 869,306, 23.12.58).-Ammeline is obtained in high (e.g., 87'34)
and R. G. A. New) (B.P. 869,773, 25.5.59).-A process for the yield by heating urea and/or biuret and dicyanodiamide in a phenol
conversion of a nitrocycloalkane (I) to the oxime of the corres- (PhOH, a cresol or xylenol) a t > 150" (160-170'). F. K. BASFORD.
ponding ketone comprises (1) electrolytically reducing the I to the
corresponding cycloalkylhydroxylamlne and thereafter, (2) without Substituted oxazolidines and tetrahydro-oxazines. Miles
intermediate isolation of the hydroxylamine, subjecting the LaboratoriesInc. (B.P. 869,129, 12.2.60. U.S., 4.3.59).-A compound
hydroxylamine to electrolytic oxidation in the anode compartment R"C i C-CHR.NK.[CH,]..OH (R is low-mol. alkyl or aralkyl ; K'
of the same cell or a different cell and then (3) isolating the oxime. is H or low-mol. alkyl ; R" is H or low-mol. alkyl or alkenyl ; n is
E. ENOSJONES. 2-3) is boiled in an inert solvent (P-xylene or toluene) during 5-240
Dicyclohexyl phthalate. Monsanto Chemical Co. (B.P. 869,959, min. in presence of a catalytic amount of KOH, to produce sub-
7.10.58 ; U.S., 7.10.57).-The phthalate is produced by heating a stituted oxazolidines or tetrahydro-oxazines useful as polymer
mixture of phthalic acid and/or phthalic anhydride and a stoicheio- intermediates (especially for ion-exchange resins) and blood exten-
metric excess of cyclohexanol in the presence of an acid dehydrating ders. Thus, OH-[CH,],-N(CH,Ph)-CH,-C i CH is added in portions
catalyst a t a pressure not above atm. to a temp. at least sufficient to a boiling mixture of toluene and KOH, and after a further 1 h.
to vaporise the cyclohexanol-water azcotrope (I) produced ; the a t the boil the solution is cooled, decolorised with C and distilled,
vapours are passed to a cooling zone maintained a t such a temp. that to give 3-benzyl-2-ethyyE-2-vinyloxazaEidine, b.p. 95-96"/0.15 mm.
cyclohexanol and I are condensed whilst cyclohexene and cyclo- F. R. BASFORD.
hexene-water aeeotrope are not condensed. E. ENos JONES. Vinylic phosphorus compounds. Metal & Thermit Corp.,
Assee of H. E. Ramsden (Inventor) (B.P. 869,528, 9.7.58. Addn.
Amines. Imperial Chemical Industries Ltd. (Inventors : S. t o B.P. 777,158).-Vinyl-substituted trivalent P compounds are
Ward, S. A. Lamb and M. A. Hodgson) (B.P. 804,113, 4.8.55. obtained by treating a complex RMgC1,nQ with a trivalent P halide,
.4ddn. to B.P. 712,100).+-Isopropyl- or p-s-butyl-aminodiphenyl- alkoxide or aryloxide. or with an organo-substituted deriv. thereof
amine (antioxidants for, e.g., petrol and aldehydes) are obtained in a [R is vinyl radical ; n is 1-3 ; Q is a substituted or unsubstituted
continuous process by interaction of p-NHPh.C,H,R (R is NH,. cyclic ether (of B.P. 777,158)J. In an example, a solution of 2.2 mol.
NO, or NO) with acetone or COMeEt in presence of excess of H, of vinyl Mg chloride in tetrahydrofuran is added in two portions to
a t 100-180"/30-300 atm. and in presence of a pelleted Cu-catalyst pentane containing PC1,. The final reaction mixture is then worked
(CujZnO or Cu/Cr,O,) and recycle reaction product. Specifically up t o give a n 86.9% yield of trivinylphosphorus. F. R.BASFORD.
the catalyst is formed under a pressure of 4 15 tons per sq. in.
F. R. BASFORD. Redistribution of organosilanes. General Electric Co. (B.P.
[A] Polypyridyls, [B] 2,2'-bipyridyl. Imperial Chemical 790,351, 2.7.56. U.S., 13.7.55. Addn. t o B.P. 756,677; J.A.C.
Industries Ltd. (Inventor : A. H. Jubb) (B.P. 569,954-5, [A] 4.. Abstr., 1957, ii, 531).-The Na chloroaluminate employed as a
[B] IS., [A, B] 1.10.58. [B] divided Out Of [A]).-[A] Polypyridyls, catalyst (in the reaction between a mixture of organo<hlhlorosilanes)
especially [B] 2,2'-bipyridyl, are obtained by heating [A, B] pyridine is regenerated by passing AlCl,, in solution in the organochloro-
or [A] a pyridine or polypyridine salt a t high temp., [B] in presence silanes being redistributed, over the spent catalyst.
of a metal halide (Zn, Cd or Hg), 1 mol. per 0.5-25 mol. of pyridine. J. M. JACOBS.
[A] Pyridine hydrochloride is heated at 300" for 6 h. t o give a small Organosilicon compounds. Imperial Chemical Industries Ltd.
yield of 2,2'-bipyridyl. [B] Pyridine heated at 300" i n presence of (Inventor : G. J. Sleddon) (B.P. 870,102, 10.4.59).-Organosilicon
0.5 mol. proportion of ZnC1, gives a 21% yield of 2,2'-dipyridyl. hydrides are produced by reacting together a t an elevated temp.
F. R. BASFORD. (100-420') a compound R,SiX,-, where R is an alkyl, aryl or
Diphosphoiminazoles. A.-B. Leo (B.P. 869,625, 14.6.57. Den., aralkyl group, X is a halogen and a is 1-3 and CaH,.
16.6.56).-Alkali metal- or alkaline-earth metal salts of diphospho- E. ENOSJONES.
iminazoles (optionally substituted in the 2-, 4-, and/or 5-position by Organosilicon compounds. Kali-Chemie A.-G. (B.P. 816,996,
alkyl of 1-6 C, or in the 4- or 5-position by [CH,],.NH, or 26.6.57. Ger., 18.12.56. Addn. t o B.P. 756,612; J.A.C. Abstr.,
CH,~CH(NH,)CO,H, are obtained by treating iminazole for a 1957, ii, 423).-Alkali or alkaline earth silicon fluorides (especially
deriv. thereof) with NH,*PO(OH), in aq. solution under neutral or Na,SiF,) are reacted with A1 trialkyls or their etherates or A1 alkyl
alkaline conditions, then adding a water-sol. alkali metal- or alkaline- fluorides, in the presence of inert liquid organic media capable of
earth metal salt of a strong acid. The compounds are useful as acting as solvents, diluents or dispersion media for the reactants and
phosphorylating agents for primary or s-amino compounds or for boiling >200° (e.g.. a mineral oil) at 100-400" under normal
imino compounds. I n an example, a mixture of NH,*PO(OK),, pressure. E. ENOSJONES.
iminazole and water is adjusted t o p H 7.2, then after 10-20 h. at Purification of diorganodihalogenosilanes. General Electric
room temp, an aq. solution of CaC1, is added. The filtered liquor is Co. (B.P. 869,962. 16.10.58. US., 18.11.57).-The process com-
diluted with EtOH, seeded, then after 1 h. the pptd. Ca salt of 1,3- prises adding to a mixture of a diorganodichlorosilane (I) containing
diflhosphoanzinazole is separated off. The compound reacts with < 20% by wt. of an organotrichlorosilane (11) a n aq. solution of an
a-alanine, etc. to give phosphorylated derivatives. organic ether solvent miscible with both the water and the chloro-
F. R.BASFORD. silanes, the amount of water in the solvent being substantially less
Trirnerising isocyanates. U S . Rubber Co. (B.P. 870,273, than that required to hydrolyse the I and being 0.5-2 mol. of water
30.1.58. US., 26.3.57).-The process comprises trimerising a t per mol. of the I1 and recovering the I. In an example a mixture of
> 50" an aromatic isocyanate RNCO in the presence of a n alkylene 80% PbMeSiC1, and 20% PhSiC1, is treated with a 4.14 M solution of
(ethylene or propylene) oxide and a t-amine (NEt,, diethylcyclo- water in dioxan : distillation gives PhMeSiC1, containing only 3% of
hexylamine) . E. ENOS JONES. PhSiC1,. E. ENOSJONES.
Trichloroisocyanuric add. Montecatini Societfi. Generale per Hydrolysable silyl thioethers. General Electric Co. (B.P.
1'Industria Mineraria e Chimica (B.P. 870,274, 30.1.58. It., 5.2.57).- 869,844,8.4.59. US..13.5.58).-A method of preparing hydrolysable
The acid is prepared by introducing C1, into an aq. suspension of silyl thioethers (RSR'),Si(R").,(X),-(m+n) where R and R ' are
NaHCO, until the suspension is saturated with Cl,, and continuing hydrocarbon radicals free of aliphatic unsaturation, 13.' an alkylene
the introduction of C1, t o maintain the suspension saturated with Cl,, radical of < 2 C-atoms, X a hydrolysable group, wa is 1--3, n 0-2,
while simultaneously adding an aq. solution of Na cyanurate a t m + n being +3, comprises the irradiation with U.V. light of a
ii-401 4 .-INDUSTRIAL ORGANIC CHEMISTRY ii-402
mixture of a mercaptan liSIi and a silane containing a t least one 2,4,8-NHa-Cl0H,(SO,H), -+ 3, 1,4-NHZC,H,Me.OMe with cyanuric
Si-bonded olefinically unsaturated hydrocarbon radical and at least chloride, then reacting the condensate with m-sulphanilic acid.
one Si-bonded hydrolysable group. I n a n example BunSH is F. R . RASFORD.
treated with Na and vinyltriethoxyethane a t reflux temp. for 168 h. Azo dyestuffs containing sulphonic ester groups. Imperial
to give 2-triethoxysilylethyl butyl ether. The products after hydrolysis Chemical Industries Ltd. (Inventors: B. R. Rshwick and J.
to siloxanes are useful in the prep. of lubricants. E. ENOSJONES. Wardleworth) (B.P. 869,100,29.10.58) .-There are claimed monoazo-
Grignard reagents. Imperial Chemical Industries Ltd. (Inven- and disazo-dyestuffs free from SO,H, CO,H, SO,NH,, alkylsulphonyl
tor : T. Leigh) (B.P. 870,415, 29.4.59).-A less hazardous process and N-acylsulphoamido groups, but containing 1-2
for the manufacture of Grignard reagents comprises treating an org. SOZ*(NR)n-l-A.0.S02R’groups (n is 1-2 ; R is H, low-mol. alkyl,
halide with Mg and tetrahydrofuran in presence of a hydrocarbon of monocyclic aryl, or A.O.SO,R’ ; R’ is low-mol. alkyl or monocyclic
b.p. 75-200” (benzene, kerosene). I n an example, a solution of aryl ; A is alkylene or 2-4 C). The compounds are insol. in water
ButC1 in toluene is added t o a mixture of Mg turnings, tetrahydro- and are useful in the dyeing and printing of natural and artificial
furan and 1, (trace), then after initiating the reaction by warming fibres of various types. In an example, a solution of the dyestuff
to 30” the remainder of the ButCl solution is charged during 5 h. a t combination p-NH,~C,H,-SO,*NH~[CH,],.OH -+ NPhMe, in pyridine
25-35’, with formation of ButMgCl in 95% yield. is cooled t o 0-5”, then MeS0,Cl is added. The mixture is stirred a t
F. R. BASFORD. 20” for 24 h., then water is charged, with pptn. of a dyestuff which
Complex metal aluminium hydrides. Badische Anilin- U. dyes wool a wash-fast yellow shade from a slightly acid, neutral, or
Soda-Fabrik A.-G. (Inventors : G. Hamprecht and M. Schwarzmann) weakly alkaline bath. F. R. BASFORD.
(B.P. 869,179, 7.12.59).-Complex metal hydrides M[AlH,R(OR)] n , Metal-containing monoazo dyestuffs. Farbenfabriken Bayer
in which M is Li, Na, K, Mg or Cd, R and R’ are hydrocarbon ,4.-G. (B.P. 869,842, 11.3.59. Ger., 5.4.58).-Compounds claimed
radicals, and n is the valency of the metal, are prepared by treating comprise metal (Co or Cr) complexes of
1 mol. of AlXR(OR’), in which X is C1 or Br, with such a no. 01 1,3,4,5-NHR(N02)~C,H,X~N,.Cl,H,(OH).NH.SO,K’-1’,2’,8’ ; they
mol. of a hydride of 13, Na, K, Ca or Mg that 2 atoms of hydride H are useful in the dyeing of wool and similar fibres (R is acyl radical
are present to 1 mol. of AlXR(OR‘), the reaction being carried out of a carboxylic acid ; R’is alkyl of 1-4 C ; X is O H or a group
in an org. diluent, e.g., tetrahydrofuran. The products are useful convertible thereto). I n a n example,
reducing agents and for prep. of other metal alkyls. 2,4,6,1-NH2(NHAc)*C H (NO,).OH is diazotised and coupled with
J. M. JACOBS. 7,1-OH-ClOH,~SO,Me!n ilkaline solution, and the resulting dyestuff
Preparation of Werner-type aluminium complexes. E. I. is trcated with K,Cr,O,, to give a complex which dyes wool a fast
I>u Pont de Nemours & Co. (Inventor : R. L. Dalton) (B.P. 869,951, greenish-blue shade. F. R. BASFORD.
6.6.57).--Water-sol. complex compounds of the Werner type, having
positive complex ions in which nuclear A1 atoms covalently linked Metal complexes of polyazo dyestuffs. Sandoz Ltd. (B.Y.
to 0 atoms io b H groups and/or to 0 atoms linked also to other A1 791,532, 7.10.55. Switz., 12.10.54. Addn. to B.P. 760,705 ; J.A.C.
atoms, the numerical ratio O/Al being 1-2.5 : 1, are co-ordinated Abstr., 1958, i, 175).-The compounds, characterised by good
with the acyloxy groups of monocarboxylic acids of solubility in compatibility with NaCl and by bright, deep navy blue shades on
water a t 20’ < 1 wt.-% (stearic, palmitic or myristic acid of a cotton and regenerated cellulose, are obtained by metallising the
halogenated monocarboxylic acid) and anions of a strong inorg. acid polyazo dyestuff of B.P. 760,705, modified to contain a CO,H group
(HCl), are prepared by causing a preformed basic ionisable salt of adjacent to or in place of the OH group of the benzene coupling
A1 (obtained by treating an A1 trialkoxide, having 1 6 C-groups, component. One example is the Cu complex of the trisazo dyestuff
with water) to react with the monocarboxylic acid in a liquid org. obtained by coupling tetrazotised 4,4‘-diamino-3,3’-dimethoxybi-
medium (a lower alkanol). J. M. JACOBS. phenyl with 1 mol. of 3,8,1-(S0,H),CloH,~OH and 1 niol. of
7 5 2 , 1-S0,H(OH).CloH4(NHPh) *N~.C,Ha(C0,H)*NO~-2’,4’.
F. R. BASPORD.
Dyestuffs. Copperable polyazo dyestuffs. Sandoz Ltd. (B.P. 793,086,
1.6.56. Switz., 3.6.55. Addn. t o B.P. 760,705; J.A.C. Abstr.,
Preparation of copper chloromethylphthalocyanineand its 1958, i, 175).--Copperable polyazo dyestuffs are- obtained by
onium salt. K. Higashiura (Technol. Rep. Kansai Univ., 1961, coupling the tetrazo derivative (1) of (C,H,R*NH,-3,4), with
No. 3, 51-62).-Four methods of preparing Cu chloromethyl- 7,5,2,1-S0,H(OH)~CloH4(NHR)~N,R (1) and also a compound (1
phthalocyanine (I) from Cu phthalocyanine are given, together with mol.) containing a .C(OH):CH. group (R is OH or CO,H ; R’ is H
a gravimetric method of estimating the no. of -CH,CI groups, or hydrocarbyl ; R” is o-hydroxyphenyl or o-carboxyphenyl,
using mercaptobenzothiazole. Max. yield was obtained using optionally carrying further substituents). Thus, to a tetrazo solution
ClSO,H, paraformaldehyde and NaCl on Cu phthalocyanine at prepared from [C,H3(C0,H).NH,-3,4], there is added a solution of
95-looo. By heating I with NMe,, pyridine, thiourea, tetramethyl- aq. Na,C03 and the aminoazo compound constituted by
thiourea, Me,S and MeEtS, an onium salt is formed, which is a water- 2,1,4-NH,(OH) .C,H3.SOzNH, 3 2,5,7-NHPh.CloH6(OH) ‘SOaH,
sol. dye. By heating with two of the above substances in succession, Conc. aq. Na,CO, is now charged, followed by water containing
mixed onium salts are obtained. Curves are given for the rates of PhNH.CO-CH,Ac to give the trisazo dyestuff. The product is a
adsorption of the onium dyes on to cotton, from a solution of 0.01 g. dark powder which by the single-bath or 2-bath coppering process
of dye in 61 ml. of water. K. RIDGWAY. dyes cotton and regenerated cellulose a black shade of outstanding
fastness t o light, washing and perspiration. F. R. BASFORD.
Stabillsation of dyes. E.I. Du Pont de Nemours & Co., Assee
of N. Blake, G. Daendliker and W. H. Holstein, jun. (B.P. 869,986, Copper-containing polyazo dyestuffs. Sandoz Ltd. (B.P.
8.4.58. U.S., 29.8.57).-There is claimed an azo or anthraquinone 809,279, 27.2.57. Switz., 13.3.56. Addn. to B.P. 695,534 ; J.A.C.
dyestuff in which the stabiliser is a metal chelate, viz., a dialkyldi- Abstr., 1954, i, 9).-Compounds, which afford copper complexes
thiocarbamate chelate of Ni, Co, Zn, Mn or Cr ; or an alkylxanthate, especially useful in the production of blue-grey to green-grey shades
2-mercaptohenzothiazole, or salicylaldehyde-ethylenedi-iminechelate on cotton and fibres of regenerated cellulose, are obtained by
of Ni or Co (10 wt.-%). The stabilised dyestuff is resistant to coupling a tetrazotised 4,4’-diamino-3,3’-dimethoxybiphenyl (I) with
decomposition by sunlight, and is especially useful in the colouring 1 mol. of 1,6,7,2-(OH),Cl,H,(S0,H)~N,R (R is radical of a 1,S-di-
of polyvinyl acetal resins ; i t may be compounded with a solvent if hydroxynaphthalene-mono- or -di-sulphonic acid coupled in the
desired. F. R. BASPORD. o-position to OH) and 1 mol. of the same azo component or with any
Azodyestuffs derived from cyanuric halides. CIBA Ltd. other azo component which couplcs in the o-pdsition to a phenolic
(B.P. 869,279, 13.9.57. Switz., 14.9. and 22.10.56, 10.1. and 19.8.57). or enolic OH group). F. R. BASFORD.
--Dyestuffs claimed are of the general formula Chromium complex compounds of monoazo pyrazolone
R.(N,-R’) n-l-l\i,.A-NHR”-p (R is residue of a diazo component dyestuffs. Sandoz Ltd. (B.P. 795,417-8, 24.5.56. Switz.. [A] 17.6..
containing CO,H or SO,H as sole substituents ; R is naphthalene [I)] 26.5.55. Addn. t o B.P. 754,270; J.A.C. Abstr., 1957, ii, 268).-
or benzene residue ; n is 1-2 ; A is benzene residue ; R“ is 2- Chromiferous azo dyes ( < 2 Cr per 2 mol. of dyestuff), for use in
halogeno-s-triazin-6-yl radical substituted in the 4-position by NH, the dyeing of nitrogenous materials and artificial fibres, are obtained
optionally carrying a hydrocarbon radical of * 12 C). They dye
cellulosic (especially cotton) fibres in presence of alkali, to give
by coupling diazotised 2,1,4,6-NH2(OH).C,H,R.NO, ( R is C1 or
Me) with 1 mol. of w-C,H,R’.SO,R” where R is 3-methyl-5-hydroxy-
colours fast to washing. A typical product is formed by condensing pyrazol-1-yl and R” is [A] morpholino, [B] NRrrlRIV(RIIIare RrVare
the dyestuff combination low-mol. hydroxyalkyl or alkoxyalkyl). [A] The Cr complex of the
ii-403 ii-403

-
dyc 2,l ,4,6-S1-12(()I-i) ~C,tl,CI.N0,-~ I-phenyl-3-methyl-5-pyrazolone- 10- Amino-11 hydroxynaphth[2,l-c] acridine-5,8,14[13H]--
:i‘-sulphonic acid morpliolidc is prepared. The product dyes wool, trione. J. Haase (B.P. 869,995, 10.7.59).-The compound is obtained
ct.c. (from a ncutral to weakly acid bath) a full bluish red shade of by condensing 1-nitroanthraquinone-2-carboxylicacid with 2 mol.
rxcellent fastness to milling, washing, and light. As the compound of 2-hydroxy-6-aminobenzoxazole at 140-200‘ in a solvent ;
is sol. in acctonc, i t may be also used for dyeing cellulose acetate cooling ; separating the pptd. solid ; subjecting this to cyclisation
c n masse. F. K. BASFORD. by the action of conc. H,SO, a t 25-100” ; then hydrolysing cyclised
C h r o m i u m complex compounds of monoazo pyrazolone substance with dil. aq. H,SO, a t 80-135”. The product is a vat-
dyestuffs. Sandoz Ltd. (B.P. 796,381, 24.5.56. Switz., 26.5.55. dyestuff intermediate. F. R. BASFORD.
Addn. to B.P. 754,270 ; J.A.C. Abstr., 1957, ii, 268).-Diazo com- Leuco-sulphuric acid esters of dyestuffs of the benzanthrone-
pound prepared from 2, 1,4,6-NH,(O1-I)~C8H,R.NO, (I) (R is C1 or pyrazolanthrone series. Farbwerke Hoechst A-G. (B.1’. 869,475,
hlc) is coupled with 1 mol. of a 3-methyl-5-pyrazolone substituted 11.8.58. Ger., 9.8.57).-Compounds claimed comprise leuco-
in the 1-position by m-C,H,.SO,.NHR (11 is straight-chain or sulphuric acid csters of benzanthrone-pyrazolanthrones s u bstituted
branched-chain butyl or pcntyl radical substituted by OH), and the in the 8- or 2-position by alkoxy of 1-4 C and optionally in the
resulting azo dyestuff is treated with a Cr-yielding agent, to give a Bz-2’ position by alkyl of 1-5 C, in the Bz-8’-position by Br and
chromiferous product, sol. in polar solvents and especially useful in elsewhere by C1. They afford fast blue shades on cotton and other
the dyeing of fibres spun from solvent (e.g., cellulose acetate, poly- vegetable fibres. In an example, ClSO,H is added dropwise a t 0-5”
acrylonitrile, polyester fibres), and in colouring plastics and lacquers. t o pyridine, then a mixture of benzanthrone-8-methoxypyrazol-
In an cxample, I is diazotised and coupled with l-phenyl-3-niethyl-5- anthrone and Fe powder is introduced a t the same temp. Thc
~~yrazolo1ie-3’-sulplion-~Y-l”-(hydroxymethyl)propylamide, and the mixture is heated to 30-40”, then after 3 h. the product is poured
dyestuff is converted to the Cr deriv. for use in dyeing cellulose on to ice and aq. NaOH. Pyridine is distilled off and the suspended
acetate in the dope. F. K. BASFORD. ester is filtered off. F. R.BASFORD.
Complex m e t a l compounds of monoazo-dyestuffs con- Methine dyestuffs. Farbenfabriken Bayer A,-G. (B.P. 869,794,
taining @-halogenoacyl-amide groups. CIBA Ltd. (B.P. 16.5.58. Cer., 23.5.57).-Methine dyestuffs are obtained by con-
870,047, 25.2.58. Switz., 5.3.57).-Metal (especially Cr and Co) densing 7-alkylindole-3-aldehydes (optionally substituted at N by
complexes of monoazo dyestuffs of the general formula alkyl and in the 2-position by alkyl or aryl) with 1,3,3-trialkyl-2-
l~’.N,.Ii.(Co),,_,.or-r-p are claimed (1% is 1-2; R is bcnzene or methyleneindolines in acid medium : by treating 7-alkylindoles
naphthalene rcsiduc containing SO,H ; R’ is residue of an amino- with 1,3,3-trialkylindoline-2-rnethylene-c~-aldehydes in acid medium;
naphtholsulphonic acid joincd to the azo linkage in a position or by reacting the 7-alkylindoles and 1,3.3-trialkyl-2-methylene-
vicinal to the OH group : there being a P-chloroalkanoylamino indoles with a dialkyl-, diaryl-, or an alkylaryl-formamide and a P
group in a t least one of the R or R‘ residues). The products are halide or phosphoric acid. Thus, 2-methyl-7-ethylindolc is added
especially useful in the fast dyeing of cellulosic materials. I n an to a solution of 1,3,3-trimethyl-2-methylencindoliqe-o-al.dehydc in
cxample, the Cu complex of the dyestuff combination 30% aq. HCl, then after 16-18 h. the pptd. solid is filtcred off and
2,1,4-NH,.C,H3(OH).S0,H + 2,5,7-NH,.C,,H,(OH).S03H in paste washed to give a yellow product which dyes acetate rayon, etc., it
form is dissolved in water, then NaOAc is stirred in, followed by fast brilliant orange shade. E’. K. BASFORD.
Cl.[CH,],.COCl. with formation of an acylated dyestuff which dyes
cellulose a ruby red shade of good fastness to washing and light.
F. R. BASFORD. Photographic Materials.
Silicon-containing azoic dyestuffs. Union Carbide Corp., P r e p a r a t i o n of the n e w nuclear emulsions by use of poly-
Assee of D. L. Bailey and R. Marston (B.1’. 870,467, 25.4.58. U.S., vinyl alcohol and their photographic properties on radiation
29.4.57).-Dyestuffs of the general formula rays. E. Fujii (.I. Sci. Hiroshima Univ., 1961, 25AI1, 185-205).--
IZN,.R’.[CH,]..SiR’’,.O,,_,,,, arc claimed (R is residue of an ice Photographic emulsions containing 70 wt.-% AgBr using polyvinyl
coupling component ; I<’ is arylene ; R” is alkyl : m is 0-2 : n is alcohol (I) as protective colloid have been made. The AgNO, and
0 or an integer). They are useful in the colouring of fibrous material KBr solutions are mixed simultaneously into the I solution, giving
(glass, natural and synthetic fibres) from an aq. bath. In an cxample, fine grained particles. The thermo-reversible gel of I solution can
a solution of (OEt),Si.[CH,!,.C,H,.NH, in water and 32% aq. HCl be made by a freezing method. The photographic emulsions are
is diazotised a t 5’ with NaNO,, then cotton fabric impregnated with capable of showing a clear delineation of a-particle tracks and
2-naphthol is immersed in the diazotised solution to produce a sufficient blackening is obtained for dosimetry of y-rays in the range
brilliant red material of good fastness to light and washing. 102-6x 103 r. The emulsions are hypersensitised to y-rays by
F. R. BASFORD. triethanolamine but treatment should not exceed 10 min. and concn.
Dioxazine pigments. C l U A Ltd. (B.P. 869,357, 29.5.58. Switz., 674, otherwise fog occurs. (21 references.) D. J. ELGAR.
29.5. and 23.8.57).---Watcr-insol., red to violet pigments of good
thermal stability and fastness to light and migration (and especially Photographic materials. General Anilinc & Film Corp. (B.P.
useful in pigment printing) comprise triphendioxazines with 870,249, 26.3.59. U.S., 14.4.58).-There is claimed a light-sensitive
IICO*NH substituents a t positions 3 and 10, X a t 6 and 13 and Y Ag halide emulsion containing as antifogging and stabilising agent
a t 2 and 9 (R is substituted benzene residue or naphthalene residue ; an adduct of a poly-1-vinylpyrrolidone with I,, Il3r or 1CI (1-100
X is H or halogen : Y is 15, halogen, alkyl or alkoxy). As an example mg. per 0.4 mol. of halide). F. R. ‘BASFORD.
of one method of prep., a mixture of chloranil, cryst NaOAc, [A] Novel f u r a n derivatives. [B] Di- and tri-hydroxyaceto-
1,2,5,4-NH,.C,H,(OEt),.NH.C0.CnI~*Cl-~,and EtOH is boiled phenones. W. R. Boehme (B.P. 870,288-9, 7.1 1.58. IJ.S., 8.1 1.57
for 4 h., then filtered. The filter cake is washed with cold EtOH and 27.8.58).--[A] Compounds claimed comprise dihydro- and
and hot water, to give a violet powder consisting of 2,5-dichlovo- tetrahydro-furans substituted in the 2-position by CO.CITY.COX
3,6 - (2‘,5’ - diethoxy - 4’ - p - cizlorobenzanzidoanilino) - 1,4 - benzo - (Y is H or low-mol. alkyl ; X is low-mol. alkyl, cycloalkyl of 5-6 C,
quitzone. This is heated with PhNO, and BzCl for 20 min. at 210- Ph, alkylphenyl or dialkylaminoalkyl), in the 5- and furthcr in the
220”, thcn the solution is cooled, with pptn. of violet needles of $-position
3,lO - di - (p - chlorobcnzamido) - 2,9 - diethoxy - 6,13 - dichlorotraphen- by low-mol. alkoxy, and optionally in the 3- or 4-position
by low-mol. alkyl or alkoxy and further in the 5-position by low-
dioxazine. The compound dyes polyvinyl chloride a strong fast mol. alkyl. They are useful as intermediates in the prep. of products
violet shadc. F. R. BASFORD. of B.P. 870,289 (following abstr.) and are obtained by condensing
2,2’-Difluoroacedianthrone. CIGA Ltd. (€32. 870,143, 2.10.57. an appropriately substituted furoic acid ester with CtJ,I’~COX in
Switz., 4.10.56).---~ndust is added slowly to a solution of 20% aq. presence of a strong base. Thus, a mixture of Me 2,5-dimethosv-
NH,. OO;< a q . NaOI-I, CuSO,,SH,O, and 4‘-fluoro-2-bcnzoylbenzoic furoate andNaFI istreatedduring 30min. with a solution of acetone in
acid, thcn the mixture is brought to the boil, and NI-I, is passed ether a t 30-40”. After 3 days the mixture is workecl up to givc:
therethrough during 45 h.. to yield 4’-ftuorodiphenylmethane-2- 2-acetoacetyl-2,5-dimethoxy-2,5-dihydrofa~ran (I), b.p. 97”/0.2 mni.
carboxylic acid. This is stirred with 96% H,SO, in presence of 1% [B] The compounds of [A] are hydrolysed, t o give di- and tri-hydroxy-
of Cu powder for 20 h. a t room temp. in a N, stream to afford acetophcnones. Thus, a mixture of I and 0.1 N - H Cwith ~ a little solid
2-J?uoroa9zthrone,which with glyoxal sulphate and AcOH a t 100’ CO, is stirred for 6 h. in a closed flask, with separation of 2,4,5,2’,4’,5’-
gives 1,2-di-(2-J?uoro-9-anlhron-lO-ylidene)ethane, which is converted hexakydroxy-3,3’-diacet~~lbi~henyl. This is removed and the filtrate is
by 96:/, €€,SO,, Ac,O and PhNO, a t 120’ to 2,2’-diftuoroacedi- cooled in ice, with separation of 2,3,6-trihydroxyacetophenone,m.p.
antlzvone in the form of a red-brown powder which dyes cotton a fast 157.5-159”. The products are tanning agents and photographic
red-brown shade. F. I<. BASFORD. developers. F. R. .HAsFoni).
5-405 1.-INDUSTRIAL OKGANIC CIIBLWISTRY ii-406

Improved antistain agents for colour photography. Kodak mttcrial IS filtered oil and tlrictl I1 rncllsat l(i5‘ uitli ilcc omp , antl IS
Ltd., A4sseeof Id. 1\2. Minsk (B.P. 825,421, 30.7.56. U.S., 29.7.55. probably a complcx salt of ~ - d i i ~ i c l / ~ y Z a n ~ z z t ~ u ~ ~ y ~ z d ~ n c - 5 - d l u - o , z l
Addn. to 13.1’. 738,683; J.A.C. Abstr., 1956, ii, 140).-Formation chlorzde wit11 0.5 mol. of SnC1,. 1’. It. U A ~ E O K D .
of colour fog or stain during the processing of colour photographic
materials (Ag halide emulsion containing a non-diffusing colour
coupler) is minimised by incorporating in the emulsion a non-
diffusing polymer (0.5-20 wt.-% on colour coupler) containing Pharmaceutical Substances.
50-2000 recurring units of - CH,.R.CH(CO,H) - and 50-2000 Characterisation of several antibiotic substances by
recurring units of chromatography and electrophoresis on paper, 12. Paris antl
*CH,-R*CH(CO-Z.[CH,],,.NH.CO. [CH,] ,.C,H,[OH] 2- I ,2.5)- (Z is J. -P. Theallet (Ann. pharm. f r u q . , 1962, 20, 436-442).-Two
0 or N H : m is 0-1 : n is 1-6 : R is CHR’.CX.COJi. solvent systems and four reagents for identification of spots are used
OBU.CH.CX.CO,H or CH,.CX.CO,H ; ‘R’ is Ph optionally s;b: in the paper chromatography of 22 antibiotics : their IIF values
stituted by alkyl or halogen ; X is H or alkyl). A typical polymer is are given. RI+values are also given for several of these in thin-layer
obtained b y interaction of a styrene-maleic anhydride copolymer

chromatography on silicic acid and liieselgel G. Good scparations
with N-2-hydroxyethylgentisamide. F. R. BASFORD. of many of the antibiotics arc also possible by electrophoresis on
Light-screening dyestuffs and coloured photographic paper and the shifts in formic acid (5o/i,,pH 2) and veronal buffer
layers. Gevaert Photo-Producten N.V. (Inventor : L. P. Roosens) (pH 8.6) are tabulated. H. s. r<.
(B.P. 869,138, 11.7.57).-Compounds which are useful as antihalation Influence of polyoxyethylene adducts on the antibacterial
agents in coloured photographic layers comprise thiazine dyestuffs activity of antibiotics. E. Ullmann and €3. Moser (Arch. Pharm.,
made by condensing a formy!-phenothiazine with a substance Berl., 196!!, 295, 136--143).-Effects on activities of antibiotics
containing a reactive CH, or Me group in prescnce of a suitable against Staflh.ylococcus aureus in the prescnce of 0.005--5% of the
condensing agent. In an example, 3-formyl-l O-methylphenothiazinc adduct (I) were determined by the agar cliffusion technique. At low
is condensed with I-(p-sulphophcnyl)-3-heptadecyl-5-pyrazolone in concn., polyoxyethylcne lauryl cthcr (11) increascd activity of
pyridine, t o give a dyestuff, via., l-(p-sulphophenyl)-4-(lO-met~~y~-
phenoxymethylpenicillin and its II salt (111) to 150 and -
llO:(,
--
pheizotltiazin-3-ylmethylene)-5-p~~ruzoZone,
-
m.p. 140-145”. a magenta respectively. At high concn., respective activities were
powder which can be employed as an antihalation agent on a 85”/. Tetracycline, chloramphenicol (IV) and bacitracin were
cellulose acetate film coated on its other side with an ortho- increasingly deactivated. In further studies with polyoxyethylene
50 and

chromatic photographic element, and which is completely decolorised stearates of different mol. wt. and sorbitan laurate and stearate.
by treatment of the exposed element with the usual processing extent of synergism and deactivation using I11 or IV varied according
solutions. F. 12. BASFORD. to the amount, nature and mol. wt. of I. It is concludcd that the
effects of I on antibacterial activity of tliese antibiotics cannot be
Tetra-azaindene compounds and their use in photographic predicted. -4. G. C O O P E R .
silver halide emulsions. Kodak Ltd., Assee of J. 1’. Tinker (B.1’.
869,882, 25.9.57. U.S., 28.9.56).-Compounds useful as antifogging New penicillins. A. D. Russell (Phu~uz. J . , 1962, 188, 249-
agents in photographic Ag halide emulsions comprise di-(4-hydroxy-6- 250).--Treatment of the penicillin nucleus with the appropriate
methyl-1.3,3a,7-tetra-azainden-2-yl)alkanes (in which the alkane agent has lcd to the production of several ncw penicillins which
residue contains < 2 C). A typical product is 1,2-di-(4-hydroxy-G- differ only in the nature of their side-chain. l’hysical properties,
m.p. 250--255”
meth,vl-l,3,3a,7-tetra-azainden-2-yl)ethane-1,2-diol, antibacterial activity and absorption studies of the various penicil-
(prep. described). F. R. BASFORD. lins are described and compared. (34 referenccs.) II. M. k l .
Merocyanine and undissociated cyanine dyestuffs. Kodak Laboratory studies of 3,4-dichloro-a-methoxybenzylpeni-
Ltd., Assee of D. W. Heseltine and L. G. S. Brooker (B.P. 869,521,
cillin. M. Claesen, P. J . Van Dijck, €3. Vandcrhaeghe and 1’. de
869,532, 29.8.57. U.S., 30.8.56. [B] divided out of [A]).-[A] Somer (Antibiotics 6. Chemotherafly, 1962, 12, 192-!?03).--Thc
Merocyanine dyestuffs and undissociated cyanine dyestuffs, useful as antibacterial spectrum of this compound (No 356) is similar t o that
sensitisers for photographic Ag halide emulsions, are obtained by of penicillin-G and -V. It is more active than penicillin V in mice
protection tests using Staphylococcus atweus and s. Fyogenes. ( 1 1
rD-I references.) c. v.
interaction of a compound CH,.CO.N:C.Me with 1 or 2 mol. of a
Development and manufacture of griseofulvin. 12. S. C.
I---z 1 Aytoun and A. P. Best (Industv. Chenz., 1962, 38, 107--112).-The
cyclammonium quaternary salt, viz., YC:(CH.CH:) ..NII.X [D is 0, history and chemical-biological properties of 7-chloro-4,6,2’-tri-
S, or NHR‘ ; K’ is alkyl or aryl ; 2 represents residue of a 5- or methoxy-6’-methyl-gris-2‘-ene-3,4’-dione (griseofulvin, I) are sum-
6-membered heterocyclic ring ; n is 0 when the latter ring is 5- marised and various aspects of production are discussed. I i:; made
membered, or is 0-1 when the ring is 6-membered ; R is substituted by fermentation of lactose, sucrosc or glucose by f’euicilliitnz
alkyl, alkyl, or ally1 ; X is anion ; Y is alkyl- or aryl-thio, or is gviseofulvum. Because of the long fermentation period ( 3 wceks)
(CH:CZ),.NR”R”I ; Z is 13, alkyl or aryl ; m is 0, 1 or (where Z is tho medium and air supply must be thoroughly sterilisetl and any
-
H) 2 ; R and are acyl and aryl respectively]. In a n examplc, points of access must be protectetl with prcssure stcam. Owing to
a mixture of thioacetamide, chloroacetamide and EtOH is brought the viscous nature of the broth no completcly satisfactory stirring
to the boil, then kept a t room temp. for 1 h. Pptd. NH,CI is filtered and aeration method has becn found. Direct extraction of I is
off, and the filtrate is heated with 3-ethyl-2-ethylthiobenzthiazolium impracticable, the broth must either be dried on steam-heated rollers
ethosulphate and NEt, until homogeneous. The resulting solution or heated a t pH 5.5 to coagulate protcins and then filtered. The dried
is kept a t room temp. overnight, then water is added, with pptn. broth or filtrate is extracted with acetone. (20 references.) C. V.
of 5-(3’-ethylbeiazthiazol-2’-ylidene)-2-methyl-4-oxothiazoline,m.p. 224
-225’ (decomp.). [B] Dyestuffs similarly useful as those of [A]are Nature of Statoloni an antiviral agent. W. J . Iileinschmidt
obtained by condensing the cyclammonium quaternary salts thereof and C . U’. I’robst (Antibiotics & Chernotkerapy, 19(i2, 12,298-309).
with 7-methyl-2-oxoiminazolo[ 1,2-a]pyridine. A typical example -Statolon is non-toxic, prophylactic and is effective in vivo ; i t is
describes the prep. of 7-methyl-3-(3-methylbenzoxazol-2-ylidene)-2-isolated from Penicilliacm stoloizif~vuiiz fcrmcntation broth. The
oxoiminazolo[1,2-a]pyridii~ehydriodide. m.p. 21 1-213“ (decomp.). active constituent is a macromol., polyanionic polysaccharidc which
F. R. BASFOKD. is composed of galacturonic acid, galactose, galactosamine, glucose,
Aminopyridinediazonium salts. General Aniline & Film arabinose, xylose and rhamnose. (‘29 rcfercnws.) c. v.
Corp., Assee of H . G. D. Moore and R. J. Cox (B.1’. 870,027, 19.8.59. Substances acting on the central nervous system. 1V.
U.S., 30.9.58).-Compounds of the general formula R.N,X antl Derivatives of 2-ethyl-2-phenylbutyramide. S. l<uliolja, Lj.
U(NH.R’.N,X), (X is acid anion ; Y is biphenyl or benzyl henyl Polak, 13. KrnjeviC and M. Videk (Croat. chcin. Rcta, 1961, 33, 121-
residue; R is pyridine residue substituted by R ’ and N R IIIRpV ; R 126).-The syntheses and m.p. of 23 N- and +substituted 2-etliyl-2-
is pyridine residue substituted by R” ; R” isalkyl, phenyl, pyridyl or phenylbutyramides are described. Preliminary tests show that some
aralkyl; RII1and RIv are as R , or RII1 is H, or RII1and R1v together of these derivatives possess sedative and hypnotic activity.
with N form a heterocyclic radical) ; they are useful as light-sensitive (In Engljsh.) E. C. DOLTON.
components of diazotype printing material. In a n example, 5-anxino- Antiviral effect of guanidine and its derivatives. 11.
2-dimethylaminopyridine hydrochloride is treated with HCl and Inhibiting effect of guanidine on several viruses. T. Ueda, S.
excess of NaNO, is present, solid cryst. SnCl, is added, and the pptd. ToyoSima, T. Tsuji, Y . Set0 and J. Nomoto (Antibiotics G.
ii-407 4.-INDUSTI\'IAL ORGANIC CIiEAIISTRY ii-406
Chenaother.ap.y. 19(i'L, 12, 3 : K - :Mi).
---~tiuanidinc
nitrate was found 1532).-The titlc compound, m.p. 227-- 229" (dccomp.) (lit. 248"
to inhibit poliomyclitis, Japanese B. encephalitis, adeno and measles and 232-233"), was obtained by interaction of 3,9-tlichloro-7-
viruses. C. v. methoxyacridine with glycine in presence of phenol a.t 1211" (3 h.).
Synthesis of hydroxyalkylmalonylureas and thelr carba- The ester (dihydrochloride,m.p. 254", dccomp.) and u.mide, m.p. 200-
mates. A. Huzas, C. Egnell and M. M0cza.r (Bull. Sor. claim. Fr., 201", are new, None of the three compounds was activc against
1962, 267---271).---Et, pyranoxy- and vinyloxy-ethylmalonates are Sa 180 tumour in mice. A. I,. GROCHOWSKI.
prepared L)y the action of the corresponding chloride on the Na Relationships between physical-chemical properties and
tleriv. of Et, nialonatc, unsubstitutcd or substituted with Bun, activity in local anaesthetics. XII. J . Ruchi and X. l'erlia
('~H,:CH.C,H,, CH,.C,H:CHCH, or C.FI 1 C.CH,. These compounds (:Irzizeim.-Forsch., 1962, 12, 183--190).-1nterfacial activities of
are condensed with urca in the presence of Ka OEt and hydrolysed cinchocaine (I) and of the MeO, EtO, Pro, C,H,,O and C,H!,O
with dil. HC1 to the corresponding liytlroxyalkylnialonylurca (5- analogues in different systems were studied. In a ncutraliscd olivc
substituted barbituric acids). Action of COCI, on these compounds oil-buffer (pH 7.3) system, interfacial activity reached a max. in
in the presencc of antipyrine affords the corresponding carbaniates the BuO compound, i.e., I, and then dccreascd. Similar hehaviour
several of u.liicli have scdative without hypnotic effect. Some other in a buffer-CHC1,cetylmeth ylphosphoric acid system was observed,
routes to thcse compountls are discussed. E . J . H . BIRCH. but the sequence of C,W,,O and C,Hl,O analogucs was reversed.
Therapeutically active, basic ethers. 111. Derivatives of As the higher liomologues formed saturated solutions in the two
2-aryl and 2-aralkylborneol. I<. Stach and W. Winter (Arzizeim. systems, a t equiv. original concn. I should show the highest activity
Forsrh., 1962, 12, 363-365).-Norborneol (bicyclo[2,2,l]heptan-2- in the series. This accords with pharmacological evidence. (31
01) deriv. were prepared with 2,4-Rll<,C,H,.[CH,] groups a t references.) A. (>, (:OOPBK.
position 2, the O H group hcing etherifierl with A X (R, is H, Me or Carcinogenic nitrogen compounds. XXXIII. Alkyl-
OMe : I<, is H, C1 or Me : ?z is 0 or I : A is [CH2], or [CH,], ; X is substjtuted benzacridines and benzophenarsazines. N. P.
tertiary amino group) by interaction of the heptdnol with AX,HCl. Buu-Hoi, 1'. Jacquignon and M. Marty ( J . chew. Soc., 1962, 1126-
1 he physical constants of y-substituted bicycloheptan-2-01s and of
I ,

1128).-Reaction of 9-isopropyl- and p-cyclohexyl-aniline respec-


1 1 'basic cthers from thcse are given. The products have similar tively with an appropriate naphthol and paraformaldchyilc affords
therapeutic action to cthers of the 1-arylcycloalkanol series. Some 7-isopropyl-1,2-, 7-isopropyl-3,4-, 7-cyclohexyl-1,2-, and 7-cyclo-
the deriv. have marked ccntral anticholinergic activity and others hexyl-3,4,-benzacridine. 9-MethyI and 9-ethyl cleriv. of these
have ccntral stimulating activity. H. S. R. compounds are obtained by similar condensations. ,V-p-Cyclohexyl-
New basic ethers with therapeutic activity. 11. 1-Aralkyl- phenyl-1 (or 2-)naphthylamine and AsC1, react to give 10-chloro-8-
cycloalkanol derivatives. K. Stach and W. Winter (Arzizeim.- cyclohexyl-5,1O-dihydro-3,4(or1,2)-benzophenarsazine, in which
I;orsch., 1962, 12, 194-1 95).-1 -Aralkylcycloallianol dcriv., the chloro-group can be replaced with Me or Et by means of the
3-1<,4-li'-C,M,~Cl~-I,~C(O~A.NX2) (CH,) (I where R,R' = H or C1, appropriate Grignard reagent. E. J. H. BIRCH.
I d Some 2-substituted benzofuran derivatives. M. Ghelardoni,
:1= (CH,), or (CH,),,X = Me, E t or NX, = piperidino or N'- M. Fedi and F. Russo (Ann. Chim., Roma, 1962, 52, 29-36).--.
mcthylpiperazino, and n = 4-7, werc prepared from the l-aralkyl- Benzofuran derivatives with various substitucnts in the %position
cycloalkanol and an aminoalkyl halide or its salt in toluene or have bcen prepared for pharmacological examination. The 2-(p-
benzene with NaNH, as condensing agent. Several I possessed were obtained by
nitrobeneoy1)- or 2-(p-acetylaminobenzoyl)-deriv.
marked central anticholinergic activity. Typical compounds are condensing salicylaldehyde with the appropriate o-halogeno-
I-benzylcyciopentyl @-diethylaminocthyl ether, b:p. 131-141"/ acetophenone and others by reduction of these with AI(OPr'),,
0.3 mm., and I-p-chlorobenzylcyclo-octylP-piperidinoethyl ether, N,H, or H,. L. A . O'NEILL.
b.p. 180--200"/0~4 mm. A. G. COOPER.
Syntheses and pharmacological activity of some homo-
Synthesis of 1-amino-p-nitroacetophenonederivatives of logues of isopelletierine. ]. Biichi, I?. Kracher and G . Schmidt
potential pharmacological activity. G. Pifferi, C . Cignarella and (Helv. chim. A c f a , 1962, 45, 729-737).-I(etimides, preparccl from
E. Testa (Ann.Chim., Roina, 1962, 52, 59---66).-1n the condensation a-picolyl-lithium and a nitrile, were hydrolysed to l-(pyrid-2-yl)-
of p-nitro-c~,-bromoacctophenonc(I) with aromatic or primary or alkan-2-ones (I). Hydrogenation over PtO, then afforded 1-
secondary aliphatic amincs, the ease of reaction and stability of the (piperid-2-yl)alkan-2-ols, which were oxidised with CrO, in AcOII
product are dependent on the basicity of the amine. Strong bases, to piperidyl analogues of I. N-Methylpiperidyl analogues were
c.g., NHEt,. react readily but tend to give unstablc products ; less derived similarly from the N-methyl methosulphates of I. Li AIH,
strong bascs, e.g., NH,Ph, 2-naphthylaminc or morpholine react or Zn-HCl reduction of I gave l-(pyridyl)alkan-2-01~. In tests
with production of reasonably stable products, while with weak against Hymenolepsis nana and Aspiculuris tetrapteva infcctions in
bases, ~ g .$-nitroanilinc,
, secondary reactions predominate. The Na mice, isopelletierine, its N-Me deriv. and the analogues were
salts of imides, e.g., succinimide or phthalimidc condense readily with practically ineffective, only I-(N-methylpiperid-2-yl)propan-2-ol
I t o give the 1-imido derivatives. The pharmacological activity of showing slight vermicidal activity. N o significant neuropharma-
the products is being investigated. L. A. O'NEILL. cological or anaesthetic effect was detected. (13 references.)
Chemistry of radio-opaque compounds. IV. Iodo-deriva- A. G. COOPER,
tives of hydroxy-a@-disubstitutedacrylic acids. Z. Rybakow Syntheses and pharmacological activity of some 4-substi-
and 1. Gruda. VI. NN'-oxalyl- and NN'-adipoyl-di(aminoiod0- tuted 1-arylamino- and l-[pyrid-2-ylamino]-gIutarimides.
cinnamic) acids. I . Gruda and 2 . Rybakow (Hoczn. Chem., 1962, J. Biichi, H. Miihle, H. Braunschweiger and 1'. Fabiani ( H e l v . chim.
36, 27--32, 33--39).-1V. The deriv. prepared were acrylic acids A d a , 1962, 34, 449-456) .-@-Mono- and pp-di-substituted glutaric
with a-Me or E t and P-m-hydroxyphenyl or p-3-hydroxy-2,4,6-tri- acids were converted to the anhydrides with AcCl. condetlscd with
iodophenyl substituents. a-Methyl-P-(3-hydroxy-2,4,6-tri-iodo-phenylhydrazine and cyclised by heating to form
pheny1)acrylic acid and the a-ethyl analogue (1) had toxicity to mice XN(R).N.CO.CH,.CR'R'.CH,*CO (I), where X = Ph, R = H, ant1
I I
of LD,, 1.525 and 0-98 g./kg. respectively, and when given orally to ~~

dogs as N-methylglucamine salts gave no X-ray opaqueness, R' = H or Me, R" = R', E t or Ph, or R' plus R" = cyclopentyl.
although I in granular form gave a faint shadow of the gall bladder. Bisphenylhydrazides obtained, especially with lowcr members of the
The corresponding 3-amino deriv. of I had good radio-opaque series, as by-products during cyclisation, were removed by fractional
properties. crystallisation. Further reaction with an acyl or aralkyl chloride,
VI. Compounds made had the formula or with ClCH,.COCl and piperidine, afforded I where 11 = Ac, 132,
l~'(NH~~~,HXI,~<:H:CR.C0,H-1,2,4,8,3)2, where R is H, Me or Et, I'hCI-I, or piperidinoacetyl. Similarly prepared from pyrid-2-
1<' = oxalyl or OC:(CH,),.CO, X is H or I. The toxicitics to mice ylhydrazine wcrc I where X = pyrid-2-yl and R = 13. Bispyridyl-
o f the dcriv. with R == Me or Et, X = 1, R' = oxalyl or adipoyl hydrazides were not formed during this cyclisation. None of the
are detailed. None gave no opaqueness when injected as N-methyl- products had high hypnotic activity. (28 references.)
glucamine salts, except that NN'-oxalyldi-(2,4,6-tri-iodo-3-amino- A. G. COOPER.
a-ethylcinnamic acid) behaved as I above when given orally. Spectrophotometric determination of pyridoxal in presence
A. L. GROCHOWSKI. of pyridoxamine and pyridoxine, F. 1'. Siege1 and 11. I. Rlaltc
Search for tumour-inhibiting compounds. X. Synthesis (Analyt. Chem., 1962, 34, 397-398).-1n the simple ant1 rapid
of N-(3-chloro-7-rnethoxyacrid-9-yl)glycine.2.Ledbchowski, A. method described, pyridoxal is condensed with acetone in the
LedGchowski and J. Marcinkiewicz (Roczn. Chem., 1961, 35, L529- prcsence of 10% NaOH. An intense yellow product is formcd with
ii-409 il.-lNDISTRIAL ORGANIC CHEMISTRY ii-4 10
absorption niax. at 420 mlr. Bear’s law is obeyed from 10 to 400 thc corresponding substitutctl carboxyatniclc. I is prcparcd froiu
pg. concn. ’Ihc colour intensity is stable after 15 min. L-cysteine hydrochloride and salicylonitrile in thc presence of
C. B. BAINBS. NaHCO, and piperidine. A. DARKE.
Antimicrobial activity of 8-hydroxyquinoline derivatives,
especially of some new esters. A. Brack (Arzneim.-ForscR., Substances with psychotropic activity. J. Ilnabe (Mitt. dtsch.
196’2, 12, 133--144).-Deriv. (47) of 8-hydroxyquinoline and 8- pharm. Ges., 1962, 32, 25-32) .-I’sychomimetic (mescaline,
hydroxyiluinaldinc, including esters, ethers and 5.7-dihalogenated psilocybine, psilocine, lysergic acid dicthylamidc), ataractic (di-
compounds, wcre examined for inhibitory activity against 13 types phenylmethane deriv., carbamates) and neuroleptic (Rauwolfia
of Gram-positive and -negative bactcria, and 8 types of fungi. alkaloids, phenothiazines and hydrazine deriv.) agents are briefly
Activity was lost by blocking the S-013 group by ether formation, discussed. A. G. COOPER.
supporting the hypothesis that antibacterial activity is associated Chemistry of a new plasma substitute. J. Schmidt-ThomB,
with chelating ability. Some acctyl and benzoyl esters of the A. Mager and H. H. Schone (Arzneim.-Porsch., 1962,12,378-380).-
halogenatcd deriv. had high activity, sometimes exceeding that of Polypeptide chains of mol. wt. 12,000--15,000 are obtained by
the parent compounds ; deriv. with N-containing side-chains dccomposition of highly purified gelatin. This material can then bc
forming water-sol. salts had little or no activity. It is suggested combined with a di-isocyanate (I) to give a compound (of average
that the lipoid-sol. esters permeate the cell membranes and are mol. wt. 35,000) consisting of three of these chains linked by urea
converted by endoccllular csterases to the parent S-hydroxy- units. It has excellent properties as a plasma substitute. By
quinolines. (53 references.) A . G. COOPER. varying the degree of gelatin decomposition and the di-isocyanate
Synergism of bacteriostatic and fungistatic effects in used the properties of the product can be greatly varied. Combina-
combination of hydroxyquinoline and hydroxyquinaldine tion occurs between (I) and the aminolimino groups of histidinc,
derivatives. A . Braclr (Arzizek-Forsch., 1962, 12, 144-148).- lysine and hydroxylysine units but not with an arginine unit.
Some mixtures of 5,7-dibromo-8-hydroxy-quinoline (I) and -quin- Typical analytical figures are given. J. 0. CRANE.
aldine deriv. had synergistic bacteriostatic and fungistatic effects. Chemical incompatibility in mixtures of drugs. 11. Syn-
This synergism may be due to a mutual effect on their lipoid theses and pharmacodynamic properties of some local
solubilities and thus on their ability to penetrate the cell membrane. anaesthetic glucosides. N. Pate1 and H. Friebel (Arch. Pharnz.,
The most effective combination was I (7)-5,7-dibromo-8-benzoyloxy- Berl., 1962, 295, 106-1 14).--Procaine, hydroxyprocaine, procain-
quinaldine (1 mol.). Activity against trichomonads was also amide and dimethylaminoethyl p-aininosalicylate hydrochlorides
established. A. G. COOPER. react slowly with glucose at room temp. in aq. solution, glucoside
Synthesis in the 1,2,4-triazolone series. S. Bellioni ( A n n . formation being detected within 30 days. The products have
Chinz., Roma, 1962, 52, 187--191).-Thc l-phenyZ-3-diethylamkno- reduced anaesthetic activity and are also slightly less toxic. Possiblc
(m.p. 108-109’) and -3-morphoZinomethyZ-1,2,4-triazoZ-5-one (m.p. reasons for the diminished activity shown by the glucosides arc
143-144’) have been synthesised, for pharmacological examination, discussed. (43 references.) A. G. COOPER.
by condensing E t N-phenoxyacctylcarbamate with phenyl-
hydrazine, to give l-phenyl-3-phenoxymethyl-1,2,4-triazol-5-one. Use of ammonium reineckate in the determination of
This is treated with HBr, and the bromomcthyl deriv. interacted morphine and atropine in mixtures. K. Basu and B. N. Dutta
with diethylamine or morpholine. L. A. O’NEILL. ( J . Instn Chem. India, 1961, 33, 255--260).--At pH 11 the addition
of aq. NH, reineckate precipitates atropine rcineckate quant.
Substances acting on the central nervous system. XXIX. Morphine reineckate remains in solution but precipitates quant. from
New sulphur-containing heterocycles : 4,4-dialkyl- and the filtrate when it is made acid with citric acid. Both alkaloids
2,4,4-trialkyl-1,2-thiazetidin-3-one- 1,l-dioxides. B. J. R. may be detcrmined by colorimetric measurerncnt of the solution OI
Nicolaus, E. Bellasio and E. Testa (Helu. chim. Acta, 1962. 45, their reineckate precipitates in acetone. The method can be adapted
717-728).--Anhydrides, (RR’CH.CO),O, prepared from a dialkyl- for the determination of other alkaloids. (16 references.)
acetyl chloride and a Na dialkylacetate, were reacted with H,SO, W. ELSTOW.
at 100’ t o yield sulphoacetic acids, RR’(COOH).SO,H, isolated as Analysis of Rauwolfia alkaloids. 11. M. Sahli (Arzneim.-
the Na, salts. SOCl, in the presence oE dimethylformamide as Forsch., 1962, 12, 155--161).--Methods for determining the total
catalyst then afforded the dichlorides which, with a large excess of alkaloid content of the crude drug and pharmaceutical prep., and
liquid NH, and with HCl, gave the diallcyl title .compounds for separation of the alkaloids, are further reviewed (cf. idem, ibid.,
IIR’C.CO.NR.SO, (I), where R,R‘ = Me, Et, Prn or Bun and 1962, 12, 55). The total alkaloid content was determined by
I 2 absorption with 2 N-Na,CO, on Hyflo-Supercel, elution with CHCl,,
It” = H. Alkylation with CH,N,, Me,SO,, PhCH,CI-Et,N or with evaporation and titration of the residue in AcOH against 0.1
an alkyl halide-K,CO, in acetone then afforded the trialkyl analogues N-HClO,. Reserpine, rescinnamine, aj maline and serpentine in thc
(I, R = R, Pri or PhCH,). No pharmacological restilts are included. total alkaloid fraction were determined spectrophotometrically
(12 references.) A. G. COOPER. after separation by extraction and paper electrophoresis or paper
chromatography. (138 references.) r l . G. COOPER.
Relationships between structure and activity in carbo-
tionamides. S. Kakimoto, J. Seydel and E. Wempe (Arzneinz.- Quantitative determination of phenolic acids with diazotised
Forsch., 19@2, 12, 127--133).-Activities of ethionamide and p-aminophenyl (3-diethylaminoethyl sulphone. Helmut Thomas
analogous pyridine- and benzene-carbothionamides against Myco- and W. Discherl (Arzneim.-Fousch., 1962. 12, 429--430).--The
bacteviunz tuberculosis (including streptomycin- and isoniazid- breakdown products of adrenaline and noradrenaline obtained by
resistant strains) were compared. 2-Substituted-4-methyl-l,3- paper chromatography from urine (vanillic acid, homovanillic acid
thiazoles, obtained from carbothionamides and chloroacetone, had and 3-methoxy-4-hydroxymandelic acid) are determined from the
low activity. Cross resistancc shown between carbothionamides, extinction coeff. of the colour produced by the title reagcnt. The
thiocarbanilides and thiosemicarbazones indicated a common mode acids named have extinction max. at 494; 365 and 530; and
of action. Activity was higher in the presence of the more electro- 492 mp, respectively. J. 0. CRANE.
negative groups, i.e. stronger polarisation of the C : S linkage. In
substituted pyridine-4-carbothionamides, at least two modes of Quantitative estimation of aloin. B. Janiak and H. Bohmert
action obtain. Toxicity appears to depend on the ease of liberation (Arzneim-Forsch., 1962, 12, 431-435).-Various chemical methods
of €I$, but i t is not established that increasing activity is associated for the quant. estimation of aloin have been investigated and
with increascd toxicity. (43 rcfcrcnccs.) A. G. COOPER. compared with a method developed by the authors. This depends
on the formation of a yellow-green fluorescent colour by warming a
Potential antimycobacterial agents. XVI. Synthesis of methanolic eluate with 4% borax. It is essential that all impurities
some 2-[2-hydroxyphenyl]-2-thiazoline-4- N-substituted car- be removed (by chromatography) and then the colour produccd is
boxyamides. I<. B. Mathur, R. N. Iyer and M. L. Dhar ( J . sci. stable for about 1 h. For 2-5 mg. of aloin the Beer-Lambert law
industr. Res.. 1962, 21B, 34-37).-26 carboxyamides have been is followed and i t is claimed that the accuracy is &0.2%.
prepared and their biological activity is under investigation. 2-(2’- J. 0. CRANE.
Hydroxyphenyl)-2-lhiazolinc-4-carboxylicacid (I) is treated with Toxicology, pharmacology and chemistry of constituents
AcCl in dry benzene in the presence of pyridine to yield the mixed of tobacco and tobacco smoke. 111. E. M’erle and H. Schievelbein
anhydride of acetic acid and I. The mixed anhydride is reacted (Arzneim.-Forsch., 1962, 22, 202-206).-Published information on
with a primary or secondary amine, NH, or N,H, hydrate to preparc the separation by paper chromatography of nicotine and related
ii-4 11 4.-INDUSTRIAL ORGANIC CHEMISTRY ii-4 12

substaiiccs, and tticir cffccts upon cnzymcs and cnzymic systems, NH, derivatives (c.g., methoDromidr, 1 1 i . p . 148---150") arc cliarac-
is tabulatcd. (57 references.) A. G. COOPER. terised by poweriul anticholinergic activity. 1'. R . BASPORI).
Substituted acetamides. May & Baker Ltd. (Invcntors: I.'). 11. A.
Separation of the antibiotic spiramycin into its components. Kidd and D. E. Wright) (B.P. 869.796, 2.6.58).--Compounds
SociCtd dcs IJsines Chirniques RhBne-Poulenc (B.P. 785,098, 2.1.56. p-MeSO,~C,H,~CH,~N[CO.CHCI,).[CH,j,.Ol< arc claimed, also phar-
Fr., 30.11.55. Addn. t o B.P. 758,726 ; J.A.C. Abstr., 1958, i, 75).- maceutical compositions containing them, for use as amoebicitlcs
A proccss is claimcd for the separation of crude spiramycin (from (R is H or acyl). A typical product is N-(p-nzetltylsztlp?zoizy~be~z~~l)-hr-
the fcrmcntation of Streptvmyces ambofaciens), to givc spivamycin I , (2-hydroxyethyhyl)dichlovoacetamide, m.p. 112" (prep. described).
1ii.p. 134-137O ; spiramycin I I . m.p. 130--133" ; and spiramycin F. 11. I~ASIWRI,.
111. m.1). 128-101", by chromatography on A1,03 or by counter- Dialkylamides of u-substituted fatty acids. Nippon Shinpaku
current distribution between aq. salt solution pH 6-7 and a n Co. Ltd. (Inventors: T. Fukui and Y. Matsuo) (B.1'. 869,474,
aromatic hydrocarbon and/or a chlorinated hydrocarbon. Elemen- 7.7.58).-Compounds claimcd comprise l-phenyl-2,3-tllxnetli).l-
tary analyses and U.V.spcctra are recorded €or the compounds. pyrazol-5-ones substituted in the ti-position by NR. CHR'*CO.NR"IIL~l
F. R. BASFORD. (R-R"' are alkyl of 1-4 C or R and K' arc H). Thcy are useful as
Substances produced by penicillin-producing moulds. antipyretic and analgetic agents. As an examplc of onc method of
lhxxliatn Rcscarcli 1,aboratories Ltd. (Inventors : F. P. Doyle, prep., a mixture of Et (1-phcnyl-2,3-dimethyl-5-pyrazolon-4-
J . H. C. Naylcr and G. N. Rolinson) (B.P. 870,395-6, 2.8.57. y1amino)acetate. 40% aq. NHMe, and NHMc,,HCI is hcatccl a t
! 131 Divided out of [A~),--[B] Fermentation liquor resulting from the 90-100" under pressure for 16 h., then tho reaction solution is
irowtb of a pcnicillin-producing mould, e.g., Penicillium chrysogenum, concentrated and worked up to give ( l - p h e n y l - 2 , 3 - d i i i i e t ~ ~ ~ ~ l - ~ -
in aq. nutrient rncdium, preferably in abscnce of a penicillin prccur- p~~?rrazoZon-4-ylamino)acet-NN-din?ethyla~ide, I<. ~ A S l W K l l .
1.14---115".
n1.p. I;
sor, is treated for the recovery of 6-aminopenicillanic acid,
Choline salicylate. Mundipharma A.-G. (B.P. 869,553, 2.12.58.

I
C~,H,,O,N,S, m.p. 209-210", by adsorption on to ion-exchange rcsin
followed l ~ yelution therefrom with aq. solvent. [A] The deriv. of .S., 3.3.58).--Choline salicylate, m.p. 49~5--50-5", is obtained 1,y
lw] are acylated with a chloride or anhydride of a carboxylic acid. treating an acid salt of choline with a salt of salicylic aciid, or by
.\ typical compound prepared is benzylpenicillin from the penicillanic treating choline carbonate or bicarbonate with salicylic acid (or a
acid and CH,Ph.COCl. 1;. K. BASFORD. salt thereof) in a medium in which thc product is sol., c.6.. water or
an alkanol of 2--6 C. The product is similarly useful as thc salicylatcs
Penicillin salts of rosin diamines and therapeutic prepara- (e.g., in the treatment of rheumatic fcvvr) but it may bc givcn with
tions containing same. Abbott 1-aboratories (Inventors : A. W. 'mpunity to patients suffering with water-rctcntion.
\Veston and A. F. 1)crose) (B.P. 814,561, 10.10.56. Addn. to B.P.
753,739 : J..Z.C. Abstr., 1957, ii, 188).---12osin diamine (I) salts of Isobutyrophenone compounds. l'arkc, D
pcnicilliu V and pcnicillin S are claimed. I is more specifically a 869,776, 18.11.59. U.S., 19.12.58).~-Compounds ~iscfulas stitnulants
I h r o s i n diainine and is prcferably a NM'-bis-rosin alkylcncdiamine of the central nervous system comprise cc-aminoisobutyrophcnor~cs,
(alkylcne of 2-8 C), c g . , NN'-bis(dehydro- or NN'-bis-(dihydro- viz., PhCO.CMc,.NRR' and their acid-addition salts (l<is low-mol.
abietyl)etliylenediamine. F. R. BASFORD. alkyl of 2 C ; R is H or low-mol. alkyl). Thcy arc made by reacting
Calciferol. UCLAF (B.1'. 842,379, 7.3.58. Fr., 16.3.57. Addn. T O 1
to 13.1'. 668,114).--h solution of 3@,17@-dihydroxyandrosta-5,7- N H R R with Ph.C(OR')CMc,, etc. I n an cxamplc, l'hCC:I.CMc,Lk
diene (in ether) is irradiated (in prescnce of a tracc of quinol) then is added quickly with stirring to a boiling solution of Na in ~McOll,
treated a t 40-100" with citraconic anhydride. The resulting mixture then after 2 min. thc mixture is poured on t o ice and thc drownr+out
is evaporated to dryness, thc rcsidoc is saponified, and the product mass is extracted with bcnzene. The dried extract is distilled, to givc
[consisting of 17P-hydroxyaetiocalciferol (I)] is csterified (with PP-dimethylstyrene oxide, b.p. 68--70"/3 mm. This is heated with
3,5-dinitrobcnzoyl chloride). The resulting ester of I (preferably NHEt, a t 200' for 20 h., after which the reaction mixture is worked
di-3,5-dinitrohenzo~rtc, m.p. 155-160") is saponified to give I, m.p. up to yield a-diethylantiizoisobutyrophenolze,b.p. 73--75"/0.1 mm.
110" (useful in vctcrinary medicine and industry). Treatment of the I;. l<.13ASFORD.
I ester in solution with heat converts i t (partly) into the ester of 2-Diphenylacetyl-l,3-indanedione. Upjohn Co. (Jnvcntors :
17$-hydroxynetioprecalciferol (11) (c.g., the di-3,5-dinitrobenzoate, K. D. Birkenmeyer and M. E. Speeter) (l3.P. 869,280, 1.10.57).--hn
m.p. 171-172"), which (after removal of any unchanged material) improved process for the prep. of 2-(diphenylacctyl)-l,3-dioxoindane
is Saponified, to give IT, m.p. N 110". The I1 is also convertible into (in 62% yield) comprises heating a mixture of CHl'h,Ac with
I. F. R. BASFORD. C500,b excess of a di-(low-mol. alkyl) phthalatc in prcsence o f alkali
Diphenylpyridylmethanes. 1C. Thomae G.m.b.H. (B.P. metal alkoxide and benzene a t 95-150' with rcinoval of alkanol
804,159, 22.3.56. Ger., 22.3.55. Atldn. to B.P. 730,243; J.A.C. and benzene by distillation. The product has anticoagulant antl
Abstr., 1956, i, 107).---CompoundsCHRR'H" (R is pyridyl, optionally rodenticidal propertics. F. R. B.\sro~n.
substituted by alkyl, aryl or aralkyl ; I<' is phenyl substitutcd in
thc p-position by 011'" and optionally elsewhere by RIV ; R"1 is Iodobenzenedicarboxylic acid esters. Stcrling 1)rug C c i .
H, alkyl or acyl ; is OH, alkyl, aryl or aralkyl ; R" is phenyl (B.P. 869,083, 30.10.59. U.S., 30.10.5R).-Coiiip~iriridsof the gcrieral
substituted by OKJ"a n d optionally also by R I V ) , useful as laxativcs formula C,H,I(CO,R)-CO,K' are claimcd (I< and l<' arc alkyl, a t
and disinfectants, are obtainctl by interaction of R'H with least one of which is substituted by OH and/or ailioxy) ; t h e y are
OHCHRR" a t 10--30" in a hydrocarbon solvent (benzenc or useful as X-ray contrast agcnts, antl are espccially suitable for use
toluene) in presence of a dehydrating agent (H,SO,). Thus, a mixture as myelographic agents for visualisation of the spinal cord. 11s an
of PhOW and p-tnethoxyphenyl(pyrid-2-y1)mcthanolis liquefied, example of one method of prep., a mixturc of N a Bu 5-iodophthalatc,
then cooled, after which conc. H,SO, is added dropwise. After several 3-ethoxypropyl p-toluenesulphonate and HCONMc, is heated a t
days the product is worked up to give p-hydroxy~henyZ-(p'-nzetlaoxy- 95-100" for 5 h., then residue obtained by concentration of the
phenyl)(pyrid-2-yl)~~~ethana, n1.p. 156'. F. R. BASFORD. product is stirred with light petrolcum. Tnsol. Na p-tolucncsul-
phonate is filtercd off, and the filtrate is washcd, dried and distilled,
2,2,2-Trifluoroethyl vinyl ether and anaesthetic com- to give 3-ethoxy$ro#yl Bu 5-iodophthala.te,b.p. 83-85"/10-4 mm.
positions. Air Reduction Co. Inc. (Inventors : J. G. Shukys and F. 1<. &\SFORI).
.4. M. ].yon) (B.P. 829,010, 19.12.55. Addn. to B.P. 742,083; Tropine ester. Duncan, Flockliart 1% Co. T.ttl., I<. 1'. I'aton a.nd
J.A.C. Abstr., 1956, ii, 399).-2,2,2-TriHuoroethyl vinyl ether (made M. E. Farquharson (U.P. 870,301, 9.4.59) ipinc is hcatctl with
as in U.P. 742,083) is frccd froin impuritics and stabilised (for use a low-niol. alkyl cstcr of 1-phcnylcyclohc 1-carlioxylic acitl in
as an anaesthetic) by washing with acid, then adding an alkaline a solvcnt (xylcne) in prcsence of a trans-c cation catalyst ( N a )
stabiliser, cg., alkyl-, cycloalkyl- or aryl-amine. F. R. UASFORD. to give the 1-phenylcyclohexane-1-cavboqlic ester of tropine, n1.p.
Glycollic acid compounds. Recherches & Techniques 38-40'. b.p. 1S6°/0+3mm (hydrochloride, n1.p. 238-239.5"). Tl1c
Appliquees (B.P. 870,441, 14.1.60. Fr., 16.1.59 and 9.1.60).- base and its salts are of potential use in the treatment of
I;. R. BASFORD.
u-Phenyl-a-cyclolicxylglycollicacid (made by interaction of cyclo- Parkinsonism.
hexyl Mg bromide with H z ~ C O , I i ) is heated with I-methyl-2- Iodine-containing amlnobenzoic acid amides. (isf.c:rreicIiische
(c1iloromethyl)pyrrolidincin a solvent (PrWH) a t the boil, to give Stickstoffwerke A.-G. (B.P.870,321, 17.7.59. Aus., 23.7. antl 2.8.58).
I-melhyl~yrvolid-Z-ylmethyl u-phenyl-(u-cyclohexy1)glycollate hydro- -Compounds useful as X-ray contrast agents comprise 3-amino-
cklovide, m.p. 210-21 1". The free base. its salts, and its quaternary 2,4,6-tri-iodobenzarides(and their alkyl esters or salts) in which
ii-d 13 4 .-IiVD USTRIAL ORGANIC ClfEMISTRY ii-414

[X
thc aniidc group is of tlic general formula C O ~ N ( X l I ) ~ Y ~ C O , Hisand CH2C12is cooled to 0", thcn AICI:3is atldctl during 1 h., to yield
alkylene of 1--.-7 C, cycloallrylenc of 5-6 C , or phenylene ; Y is 1,l'-di-t-butylacrtyl-ferrocene, m.p. 94". F. li. BASFORD.
alkylene of 1-8 C or is cycloalkylene of 5-6 C ; K is 1-3-C-alkyl, A compound of the cyclopentanopolyhydronaphthalene
H , OH, COJI or (except when X is phenylene) js series and therapeutic compositions containing it. Organon
N(Y.CO,~I)-C,HI,.NI-I,-2,4,6,5]. As an example of the method of Laboratories Ltd. (B.P. 826.028, 18.5.56. Neth., 20.5.55. Addn. to
prep., a mixture of 3,2,4,6.1-NH2~C,HI,~CO,H and SOCl, is heated 719,402 ; J.A.C. Abstr., 1955, ii, 216).-19-Nortestosterone is
a t 50-55". to give 3-thionylamzno-2,4,6-tri-iodobenzoyl chloride. m.p. esterified with p-phenylpropionic acid, anhydride or halide, to give
107-109", in quant. yield. This is treated dissolved in dioxan with 19-nortestosterone-p-phenylpropionate, m.p. 95-96". The compound
sarcosine E t ester to yield 2,4,6-tvi-iodo-6-arninobenzoylsarcosineEt has a strong anabolic effect and only a weak androgenic action.
ester, which is hydrolysecl by 2.14 N-MeOH-NaOH to the Na salt of F. R. BASFORD.
~,~,6-tri-iodo-6-anzinobenzoylsnvcosine. F. R. BASFORD. Dehydrocortical hormones. Upiohn Co. (B.P. 799,494.
Aryl-substituted alkylamines. Parke, Davis & Co. (€3.1'. 803,656, 8.6.55. US., 31.1.55. Bnth aidnl. to B.P. 761.526 ; J.A.C.
870,029, 21.8.59. U.S., 21.8.58).-Compounds useful as analeptic, Abstr., 1958, i, 295).-Compounds claimed are [A] 11p,17a,21-
antihistaminic and anticholinergic agents comprise 2-phenyl-2- tvihydroxypregna-1,4-diene-3,20-dione21-cyclopentylcarboxylate, [B]
phenoxycthylamines (and their acid-addition salts) obtained by 17a,21-dihydroxypregna-l,6-diene-3.11,20-trione, characterised by
reduction of 0Ph.CHPh.CO.NRK' (with LiAlH,) (K and R' are H. anti-inflammatory activity, and [B] more pleasant taste, greater
low-moi. alkyl. or together with N form a pyrrolidino, piperidino, solubility and lower toxicity than cortisone. They are made by
alkylpyrrolidino, or alkylpiperidino radical) or by alkylation of esterifying [A] prednisolone, [B] prednisone with the appropriate
OPh.CHPh-CH,.NHR1ll (RIII is alkyl). A typical product is diethyl- acid chloride in benzene in presence of pyridine. F. R. BASFORD.
(2-plzenoxy-2-phenylethyl)amine (hydrochloride, m.p. 149-150'). Steroids. Upjohn Co. (B.P. 869,564, 31.7.59. U.S., 21.8.58).-
F. R. BASFORD.
Cornpounds claimed comprise 17,21-epoxy-6or-n~ethyl-3,20-dioxo-
Phenylalkylamine derivatives. Smith, Kline & French pregna-1,4-dienes substituted in the 11-position by OH or 0. They
1-aboratories (B.P. 870,541, 7.4.60. U.S., 22.4.59).-Compounds made by treating the 11p, 17a,2l-trihydroxy-3.20-dioxo- or
NH,.CHR.CH,.C,H,.CF, ( R is H or Me) are obtained by reducing are 17a,21 - dihydroxy - 3,11,20 - trioxo - 6a - methylpregn - 4 - ene - 21 -
NO,.CII:CH.C,H,.CF,, e.g., with a bimetallic hydride (LiAlH,) in a alkylsulphonate (of U.P. 863,780 and 863,729) with alkali metal
boiling ether a t 30-150'. Thus, p-nitro-p-trifluorostyrcne (prep. fluoride. The compounds are useful as diuretics. F. R. BASFORD.
tlescribed) in ether is added to a boiling solution of LiAlH, in ether,
then after a further 2.5 h. at the boil water is added, and there is Steroids. Upjohn Co. (B.P. 869,815, 21.10.57. U.S., 29.4.57,
obtained p-tviflz~oromethylphenylet~~yla~i~ze. The products arc useful Addn. to B.P. 790,452; J.A.C. Abstr., 1959, ii, 71).-A steroid of
as anorexigenic agents. F. R. BASFORD. the androstane or pregnane series which is hydroxylated in the
nucleus (other than in the 11- or 6- and 11-positions) is converted
Thyroxine analogues. Claxo Laboratories Ltd. (Inventor : into unsaturated derivatives by the process of B.P. 790,452, viz.,
U . A. Hems) (B.P. 803,149, 8.5.56. Addn. to B.P. 652,207).- by bringing under anhyd. conditions in an inert basic org. medium
Thyroxine analogues,viz.,4,3,5,l-OH~C,H,XX,*O~C,H,I,CH,.CO,H- into contact with a N-halogeno-amide or -imide and SO,. Thus, a
2',6',4' and their salts or esters (X is H or I ; XI is I), are obtained solution of N-bromoacctamide in pyridine is added to a solution of
by treating 3,5-tli-iodo-4-(~-hydroxyphenoxy)phenylacetic acid (I) 3a-hydroxy- 11,2O-dioxopregnane in pyridine a t 25", then after 30
with I, a t 0-30" in a solvent (water, dioxan or low-mol. alkanol) in min. a t this temp. the mixture is cooled to 12" and gassed with
presence of an org. base (NH,Me). Thus, I is treated with N-aq. SO, until a negative test is obtained with acidified starch-iodide
iodine solution and 33y0 aq. NH,Et, to give 3,5,3'-tri-iodo-4-@- paper. Water is now stirred in a t 30°, then the product is cooled a t
hydroxyphen0xy)acetic acid (Triac) (63%), m.p. 181-183".
F. R. BASFORD. 0-So, and the suspended 11,20-dioxopregn-3-ene F. is filtered off.
R. BASFORD.
Amines. May & Baker Ltd. (Inventors: [A] H. J. Barber, [Steroidal] tetra-ene. G. D. Scarle & Co. (B.P. 869,443, 3.3.60.
[R] J . N. Ashley, [A, B] R. F . Collins and M. Davis) (B.P. 809,023, U .S., 4.3.59).-A solution of l13-diacetoxyoestra-1,3,5( 10)-trien-20-
811,857. [A] 9.4.55, addn. t o B.P. 769.706 [J.A.C. Abstr., 1958, ii, one in I'r'OAc containing p-C,H,Mc.SO,H is slowly distilled until
1871, [B] 18.1.56, addn. to B.P. 768,144 [J.A.C. Abstr., 1958, ii. 89).- no more acetone comes over, then the residue is diluted with EtOAc
Compounds 4,2,1-NRR'CgH,R"~O~X~R~~~ (R and R' are H, alkyl and successively washed with aq. Na,SO,, aq. K,CO,, and water.
of 1-6 C, hydroxyalkyl or [A] alkoxyalkyl ; R" is low-mol. alkyl or The product is dried, distilled a t < 1 atm., and a solution of the
alkoxy; X is alkylene of 4-9 C optionally substituted by alkyl ; residue in hcxane is purified chromatographically, t o give 1,3,17-
HI" is [A] acylamido deriv. of carboxylic or sulphonic acid or [B] triacetoxyoestra-1,3,5(10),16-tetraene,1n.p. 177-178". The compound
Ph, optionally substituted (in the p-position) by alkyl, NH, (op- is characterised by its capacity to decrease the serum concn. of
tionally substituted), etc. The products are useful in the treatment cholesterol and the corresponding cholesterol/phospholipid ratio
of bilharziasis. Examples (prep. given) are [A] 1-(4-amino-2- without producing oestrogenic effccts. F. I<. BASFORD.
methoxyphenoxy)-5-p~thal~~z~opentane, m.p. 106~5-108", [B] the
corresponding phenyl deriv., m.p. 77-78". F. R. BASPORD. Steroids. Upjohn Co. (B.P. 869,777, 4.12.59. U.S.,21.1.59).-
In the hydrolysis of the 3-pyrrolidyl enamine of 6or-methyl-1I p,21-
Pharmaceutical compositions comprising benzylhydrazine dihydroxy-3-oxopregna-4,17(20)-dienc (to give the %ox0 compound),
derivatives. Imperial Chemical Industries Ltd. (Inventors : A. improved (e.g., 44%) yields arc obtained by first converting the
Spinks and E. H. P. Young) (B.P. 869,575, 2.5.50).-Compositions enamine into an acid-addition salt (with an inorg. or an org. acid,
with anti-depressant and stimulant properties, and suitable for use preferably a fatty acid of 1-8 C). F.R. BASFORD.
in the treatment of cardio-vascular disorders in humans and animals
comprise a suitable carrier and a compound of the genera1 formula 6-Methyl-3-0x0- A4T6-steroid compounds, British Drug
R.CH,.NR'-NR"R"I (R is Ph optionally substituted by halogen, Houses Ltd. (Inventors : D. N. Kirk, V. Petrow and D. M. William-
alkyl, or alkoxy ; R'-R"I are H or alkyl, alkenyl, or aralkyl son) (B.P.870,286, 4.11.58).-6-Methy1-3-0~0- A4~"-steroids (carrying
optionally substituted by halogen or alkoxy), e.g., benzylhydrazine substituents in the 11-, 16-, and 17-positions) are obtained by
hydrochloride. F. R. HASFORD. interaction of a 3P-hydroxy-&methyl- n6-steroid with a benzo-
quinone (eg., p-benzoquinone or chloranil) in presence of an
Tertiary alkyl ferrocenes. Imperial Chemical Industries Ltd. Oppenauer oxidant, e.g., Al(OPri),, in an org. solvent. Thus, a
(Inventor: T. Leigh) (B.P. 869,058, 16.12.59. Addn. to B.P. mixture of 17a-acetoxy-3~-hydroxy-6-methylpregn-5-cn-ZO-o1ie.
828,965 ; J . A . C . Abstr., 1961, i, 286).-The following compounds AI(OBut),, p-benzoquinonc and benzene is boiled for 30 min. to yield
1,l'-di-( 1,l-dimethylbutyl)-, 17a-ncetoxy-A-methyl-3,2O-d~oxo~regn~a-4,6-diene,
are claimed : lIl'-di-(3-nieth3~1~(.lzt-3-yl)-, m.p. 214-2 16". The
and 1,l'-di-(l-methy!cydohexyl)_fevrocene. products are progestational agents and pharmaceutical compositions
l11'-di-(3-m.etrz.ylhe~t-3-yl)-,
They are made by interaction of the corresponding t-alkyl-cyclo- containing them for such use are also claimed. F. K. BASFORD.
pentadienylalkali metal deriv. with an anhyd. Fe halide.
F. R. BASFORD. Steroids. Upjohn Co. (B.P. 869,799, 24.7.58. TJ.S., 9.8.57).-
Ferrocene derivatives. Imperial Chemical Industries 1.td. Compounds claimed comprise 11-hydroxyprogesterones substituted
(Inventor : T. Leigh) (I3.1.'. 8(59,504, 9.2.59).--Coinpoiinds claimed in the 6- and 11-positions by alkyl of 1-8 C. They are characterised
comprise ferrocenes substituted in one or both of the cyclopenta- by hypotensive activity. A typical product is 11p-Iiydroxy-Ga,11a-
dienyl radicals by CRR.CH,X (R and R' are H or together form 0 ; dinzet~~ylprogesterone, m.p. 215-217". the prep. of which is described
X is s- or t-alkyl, P h or cycloalkyl, optionally substituted). As an in detail, starting from 3,11,20-trioxopregn-5-ene3,20-dialkylene
example of the method of prep., a mixture of ButCH,.COCl, ferroccne ketal. F. K. BASFORD.
ii-415 4.-IND USTRIAL ORCANIC CHEATISTRY ii-416
Corticosteroids. C. t’lizcr M Co. Inc. (B.1’. 869,090, 15.5.58. Polymethylene bis-quinollnium and isoquinolinium salts.
U S . , 7.6.57).--Thcrc are claimed corticosteroids, viz., 17-hydroxy- Allen & Hanburys Ltd. (Inventor : 1.0. J . Collier, E. I>. 1a.ylor
3,20-dioxoprcgn-4-ciics or -prcgna-4,6-diencs, substituted in the and L. H. C. Lunts) (B.P. 839,505, 16.1.58. Addn. to 13.1’. 738,997 ;
11-position by O H or 0, in the 21-position by NH,. substituted J.A.C. hbstr.. 1956, ii, 147).-l’olymethylenc (‘21-40 C)-bis-
NLI, or N-hcterocyclyl group, and optionally in the 9-position by quinolinium and bis-isoquinolinium salts, characterised especially
halogen. They arc useful on account of their anti-inflammatory by anti-microbial and anti-parasitic activity, are obtained by
propcrtics. In an example, a mixtiire of 21-iodo-l l p, 17a-dihydroxy- interaction of [CH,].X, (n is 21-40 ; X is halogen) with 2 niol. of
3,20-dioxoprcgna-4,6-diene and piperidine is heated a t 100”for 15 quinoline and isoquinoline in an org. solvent. The resulting quater-
min., to give 21-Piperidino-11p, 17a-dihydroxy-3,20-d~o~opre~~za-4,6- nary halides may be converted into other salts (by double decom-
dieize, m.p. 178.5--182“. F. R. BASFORD. position). In an example, a mixture of [CH,],,I,, isoquiuolinc and
Steroid compounds. C. I’fizer & Co. Inc. (B.P. 870,387-90, EtOH is boiled for 124 h.. then cooled, with pptn. of docosane-1,22-
F. R. BASFORD.
9.6.59. U.S. [A, B, D] 9.6.58, (A-D] 30.9.58 and 23.3.59).-[A] A bis-isoquinolinium di-iodide, m.p. 144”.
17-hydroxy-3,20-rlioxoprcgn-4-en-21-aldehyde, substituted in the Heterocyclic nitrogen compounds and their use. J . K.
1 1-position by OF1 or 0, and optionally in the 9-position by halogen, Geigy A . 4 . (B.1’. 869,181, 24.12.57. Switz., 28.12.56, 8.2. and
O M c or OEt ; in the 2-position by Me ; in the 6-position by F or 25.11.57).-Compounds claimcd comprise 2-imino-heterocyclic
Rlc ; in the 14-position by OH ; and in the 16-position by F, Me,
CH2, OH or acy1atc.d 013 (acyl derived from a mono- or dicarboxylic ,-A- I
acid of 1-10 C), also optionally unsaturated in the 1- and/or products of the general formula R*NC(:NH).N.R’( R is benzyl op-
(<-position, is treated with diazomethane in a solvent a t 0-15” tionally substituted ; R’ is H, aliphatic, araliphatic or cycloaliphatic
during 1-24 h . , to give the corresponding androst-4-ene in which radical, but either R or R’ contain a lipophilic group or R’ is such a
the 17-position is occupied by an oxidopropiouyl group. The prep. group ; A is saturated hydrocarbon radical joined a t up- or cry-C
is drscribed of 11p, 17a-dih.ydroxy-l7P-(a ~ - o n i d ~ p r o p i o ~ z y l ) a n d m s t - 4atoms
- to the N, and is prcferably an acylic or monocyclic alkylcnc
mt! (I). The coinpound. are similarly uscful as but loss toxic than group),. They are characterised by antibacterial, fungicidal and
11ydrocortisonc. algaecidal activity and may be obtained by condcnsing NIIR.A.NI3 R’
[B] Trcatmcnt of the compounds ol [A] with cxccss of H halide with a CN halide, thcn introducing the R and R groups latcr if
gives a-hytlrosy-P-lialopropionyl dcriv. I with HI gives the 17p- desired. The prep. of ‘L-imi~zo-3-benzyl-l-dodecyl~miduzol~dine hydro-
(cc-hyduo.zly-P-iod~)~i,opio,zyl) deriv. (11). chloride is described. F. R. BASFORD.
[c] The compounds of [B] are treated with Hi&), to yield deriv. Diazacycloalkenes. C. I’fizor & Co. Inc. (H.P. 869.977, 23.12.58.
with as 17p-substitucnt CO.COMe. Thc P-chloropropionyl analogue NR’
of I1 yields 11p, 17a-dilzydvoxy-17P-pyruvoylnndrost-4-ene. / \
[D] The products of [El arc rcductively dehalogenated (especially U.S., 26.12.57 and 22.12.58).-Con~pounds R.X.C:N.(CHJn and
the Br and 1 deriv.) with Zn and AcOH or Raney Ni in MeOH to their acid addition salts and quaternary salts derived from alkylating
givc hydroxypropionyl deriv. 11p, 17a-dihydroxy-17P-(u-hydroxy- agents of 1-4 C (R is alkyl or alkenyl of > 18 C ; X is 0 or S ;
p~opio;zyl)-3-oxoamrlvosta-l,4-diene is prepared. n is 2-3 ; R’ is H or alkyl or alkenyl of 1-6 C. the total C in R
The products of [A-D] have thcrapcutic value similar to that of and R’ being 6-24) and methods of prep. are claimed. The products
hydrocortisone but have greater adrenolytic effect and are less toxic. are active against human (especially helminths) and plant pathogens.
I?. R. BASFORD. A typical substance is 2-Rexylthio-1,4,5.6-tetrahydropy~~midzne
Steroids. Upjohn Co. (B.P. 869,511, 24.4.59. U S . , 26.5.58).- hydvobvomide, obtained as an oil by boiling a solution of hexyl
Compounds clainirtl comprise 17a,21-dihydroxy-16a-methyl-3,20- bromide, 2-mercapto-1,4,5,6-tetrahytlropyrimidine and EtOH for
tlioxoprcgn-4-enes (and 2 1-acylates thereof with a carboxylic acid of 10 h. F. R. BASFORD.
1-12 C) substituted in the 11-position by OH or 0 and optionally Cyanopyrazoles. CIBA Ltd. (B.P. 869,552, 24.11.58. Switz.,
in the 9-position by halogen. A typical product is Il-oxo-16a- 26.11.57 and28.3.58. Addn. to X.P. 854,632, 11.2.57).-Compounds
Iiiefhyl~rogesteroize.m.p. 183-185” (prep. from 11-0x0-16-dehydro- claimed comprise 3-amino-4-cya.nopyrazolcs substituted in the
progcsterone described). F. R. BASFORD. 1-position by an aliphatic or a cycloaliphatic radical of 4 4 C. They
are especially useful as sedatives. As an example of the method of
Steroids. TJpjol~n Co. (B.P. 870,123, 7.9.59. L J S . , 8.9.58).- prep., a mixture of NH,.NH.CHMePr (21). (CN),C:CH.OEt and
Compounds claimed comprise 17~-hydroxy-16a-methyl-3,2O-dioxo- EtOH is boiled for 12 h., then cooled, with pptn. of 3-amino-4-cyano-
prcgn-4-enes substituted in the 11-position by OH or 0 and optionally 1-(3’-methylbut-2’-yZ)pyrazole,m.p. 167-168”. F. R. BASFORD.
in the 9-position b y F or C1 and in the 21-position by F, e.g.,
11 8,17u - dihyclroxy - 16a - methyl - 21 - fluoropregn - 4 - ene - 3,20 - Phenyl-tetrahydropyranyl-piperazines. Miles Laboratories
dione. They have (iiuretic activity when administered orally, and Inc. (B.P. 869,460, 15.3.60. US., 23.3.59).-Compounds useful as
may be prepared from the products of B.P. 869,511. anorexic agents or appctite depressants comprise l-tetrahydro-
F.R. BASFORD. pyran-2’-ylpiperazines (and their acid-addition salts) substituted
N- Alkyl- and -cycloalkyl-piperidine carboxylic acid amides. in the 4-position by Ph optionally containing halogen or alkyl or
LI.-B.Bofors (13.1’. 869.978, 13.2.59. Swed., 13.3.58).-A compound alkoxy of 1-5 C. A typical product is 1-phenyl-4-tetrahydropyran-
l<.CO.NHIt‘ (It is pyridyl radical optionally substituted by 1-2 2’-ylpiperazine, m.p. 98-99”, obtained in 87% yield by reaction of
slkyl groups each of $ 2 C but of total C > 3 ; R’ is benzene residue 2-hydroxytetrabydropyran with I-phenylpiperazine in MeO1-I.
optionally substituted in any or all of the remaining positions by F. R. BASFORD.
alkyl of $ 2 C) is quaternised with an alkylating or cycloalkylating Hydrazine compound [3,6-dihydrazinopyridazine]. CIHA
agent of $8 C, thcn thc quaternary salt is hydrogenated, and the Ltd. (B.P. 781,456. 17.8.53. Switz., 20.8.52. Addn. to B.P. 654,821).
resulting salt is basificd, to give a N-alkyl- or -cycloalkyl-piperidine- -3,6-Dimercapto-, prepared from 3a-dihydroxy- via 3,6-dichloro-
carbonamide. A typical example describcs the prep. of l-methyl- pyridazine is heated with hydrazine (c.g., in boiling EtOH), to give
paperid-2-ylcavbon-2’.6’-di~~etlzylanilide, m.p. 151-152“. The 3,6-dz~ydrazznopyridazine, dccomp. a t 193-195”. The compound
products are local anaesthetics. F. R. BASFORD. and its salts (e.g., nitrate) are claimed t o have a prolonged action in
reducing blood pressure. 1’. K. HASFORD.
N-Amlnoalkyl substituted 5- or 7-halogeno-6,S-dimethyl-
1,2,3,4-tetrahydroquinolines. Farbenfabriken Bayer A.-G. (In- Therapeutic potentiated barbiturate compositions. A. E. W.
ventors : H. I\;olling and R. Gonncrt) (B.P. 788,347, 10.2.56. Xddn. Smith (B.P. 869,369, 7.10.57).--Potentiation of a barbiturate
to H.P. 758,570; J.A.C. Abstr., 1958, i. 78).-Compounds, useful composition is effected by addition of a compound
i n the treatment of schistosomiasis in warm-bloodcd animals, p-X.C,H,.NH.CO.CH,~CHMc.NRK’ (X is 1-1, halogen, acyl, alkosy
comprise 5- or 7-l1alogeno-G,8-dimethyl-1.2.3,4-tetrahydroquinolines or carbalkoxy ; 1< and I<’ arc alkyl or togcthcr with N form a
substituted in the 1-position by ReNR’R and optionally in the heterocyclic ring ; and the benzene nucleus may hc furthcr sub-
2-, 3- or 4-position by alkyl of > 3 C (R is alkylene of > 4 C ; It’ and stituted) and/or its acid-addition salts. A typical additive is
Ii” are H or hydrocarbon radicals). As an example of prep., inter- P-pyrrolidinobu tyranilidc. F. R. BASFORD.
action of S-chloro-6,8-dimethyl-1,2,3,4-tetrahydroquinoline with Benziminazoles. CIBA Ltd. (B.P. 870,521, 1.9.58. Switz.,
NEt-,.[CIT,],.Cl for 1 h. a t 150”. temp. rising to 220”. gives 5-rhloro- 30.8. and 27.9.57).---Compc1uncls claimed comprise licmziminazolcs
G,8 - dimethyl - 1 - (2 - diethyloni.i?2oetkyl)- 1,2,3,4 - tetrahydroqz*inoline, (and their acid-addition salts) substituted in the 1-position by
b.p. 179-1 80”/3 mm. (hyd$,ochloridc,m. 17. 209-2 loo). It-R‘ and in the 2-position by p-OR’.C,H,.CH, ( R is alkylene of
F. R.BASFORD. 1-5 C ; K’ is alkylimino of 2-5 C optionally intcrruptcd by a
ii-417 4.-IND USTRIAL ORGANIC CHEMISTRY ii-418
hetero atom, or is dialkylaniino in which the alkyl groups contain position by R.R' and opfionally in the benzene nucleus by halogen (K'
1-5 C ; It'' is alkyl of 1-5 C). A typical product is 2-(p-ethoxyy- is H or halogen ; R is straight-chain alkylene of 3--6 C or branched-
m.p. 65-66", forined by chain alkylene of 2-6 C). They are useful for their analgetic, anti-
bentyl)-l-(2-dietli~ylan~inoetkvl)henzimina;ole,
adding o-NH,.C,H,.NH.[CH,~,.NEt, dropwise to a solution of the pyretic and antiphlogistic properties. Inanexamplc, AcOHissaturated
imino ether hydrochloride of p-OEt-C,H,*CH,~CO,H in chloroform with HCl a t 5-1OD, then salicylamide is added, followed by croton-
(prepared by passing HC1 through a mixture of p-OEt.C,H,.CH,CN, aldehyde during 10 min., while continuing the passage of HCl. The
EtOH and chloroform a t -10". then keeping at 25" for 16 h.), mixture is heated at 50" during 1 h., then cooled, poured into water,
then boiling the mixture for 16 h., extracting with aq. HCl, and and worked up to give 2-(2-chloropro~yl)-4-oxo-2,3-dihydro-1,3-
basifying the cxtract with aq. NH,. The products are useful as benzoxazine, m.p. 124-125" (with decomp.). F. R. BASFORD.
analgesics. F. R. BASFORD. Phenothiazine derivatives. Soci6tB des Usines Chimiques
Benziminazoles. CIBA Ltd. (B.P. 870,385, 14.10.58. Switz., Rhdne-Poulenc (Inventors: A. B. A. Jansen and T. A. Wilder)
14.10.57and 20.8.58).-Compounds claimed comprise benziminazoles (B.P. 869,473, 6.6.58).-An aq. solution of Promazine hydrochloride
(and their acid-addition salts) substituted in the I-position by and an aq. solution of di-(2-hydroxy-3-carboxynaphth-4-yl)methane
low-mol. dialkylaminoalkyl ; in the 2-position by p-alkylbenzyl of (I) containing NaOH are added a t approx. equal rates to water,
low-mol. wt.; in the 5-position by low-mol. alkyl ; and optionally then the pptd. solid is filtered off, washed and dried t o give the I
in the 6-position by low-mol. alkyl. They have analgetic properties. salt of Promazine ( I0-3'-dimethylaminopropylphenothiazine), m.p.
In an example, 1 ,5,2-NH,~C,H,Me~[CH,JZ.NEt, (prep. described) is 129-131". The salt is tasteless and free from unwanted anaesthetic
added to solution of the imino ether hydrochloride of effect. F. R . BASFORD.
p-MeC,H,CH,COgH (made by saturating a mixture of Phenothiazines. SociCtC des Usines Chimiques Rhdne-Poulenc
p-MeC,H4-CHgCN, EtOH and chloroform at -10" with HC1 then (Inventors : R. M. Jacob and G. L. Regnier) (B.P. 789,016, 21.4.56.
keeping during 16 h. a t 25'). The mixture is boiled for 24 h., then Addn. to B.P. 716,206).-1n the products of B.P. 789,016, the C1 or
worked up to give 2-(p-methylbenzyl)-5-msthyl- 1-(2-diethylaminoethyl)- Br is replaced by F, to give powerful potentiators of anaesthetics
benziminazole hydrochloride, m.p. 151-153". F. R. RASFORD. and analgesics, etc. As a n example of prep., a mixture of 2-fluoro-
Thioparabanic acids. CIBA Ltd. (B.P. 869,360, 8.7.58. U.S., phenothiazine, xylene and 95% NaNH, is boiled for 1 h., then a
16.7.57 and 9.1.58).-Compounds claimed comprise "thioparabanic solution of xylene and NMe,.[CH,],.Cl is added. After il further 5 h.
acids substituted in the 1- and 3-position by Ph radicals carrying a t the boil the solution is worked up to give 3-j'Zzioro-l0-(3'-dimethyl-
various groups, provided that a t least one of the phenyl radicals aminopropy1)phenothiazine. b.p. 181-189°/0~1 mm. (hydrochloride,
contains an ether group. The bases and their acid-addition salts are m.p. 181--182°). F. R. BASFORD.
active against ilfycobacterium tuberculosis and M . leprae. As an Basically substituted heterocyclic compounds. CIBA Ltd.
example of thc method of prep., a mixture of 2-(p-isopentyloxy- (B.P. 869,089, 12.3.58. Switz., 14.3.57).-Compounds characterised
phenylimino)-3-(p-isopentyloxypheny1)-4-oxothiazolidine, NaOAc by antihistamine and antiserotonin activity, and especially useful
and AcOH is heated to 85", then CrO, in aq. AcOH is added during in the treatment of asthma, comprise dibenz[b,fl-1-thia-1 I-oxo-4-
15 min. The product is poured into cold water, and the pptd. solid azacyclohepta-2,6-dienes(and their acid-addition salts) substituted
is worked up t o give a cryst. ppt. of 1,3-di-(p-isopentyloxyphenyl)-2-in the 10-position by A*R and in any of the 6-9-positions by at
thioparabanic acid, m.p. 185.5-186". F. R. BASFORD. least 1 Me or OMe (A is alkylene of 1-6 C : R is NH, group disub-
Therapeutic compositions containing choline salts of dialkyl stituted *
by alkyl and/or cycloalkyl of 6 C, or is saturated hetero-
cyclic radical of > 6 C, optionally containing another hetero atom).
xanthines. Warner-Lambert Pharmaceutical Co. IB.P. 823,242, A detailed example describes the prep. of 8-methyl-l0-(2-dimethyl-
31.5.56. Addn. to B.P. 736,443; J.A.C. Abstr., 1956, i, 833).- m.p.
Pharmaceutical compositions containing choline salts of dialkyl- aminoethyl)-ll-oxodibenz[b,f]-l-thia-4-azacyclohepta-2,6-diene,
109-1 10". F. R. BASFORD.
xanthines (of B.P. 736,443) are stabilised against decomposition by
water and/or CO,, e.g., by limiting the water content to > 1.5%, or Reserpic acid [A, C, D] esters, [B, E, F] diesters, and salts
(in the case of suppositories) incorporating polyvinylpyrrolidonc thereof. CIBA Ltd. (B.P. 837,840-1, 837,879, 837,947-9,
and/or a suitable buffering agent, e.g., Ca,(PO,),. F. R. BASFORD. 839,313, 11.11.58. U.S., 14.11.57. All addnl. to B.P. 744,290;
J.A.C. Abstr., 1957, i, 119).-Compounds claimed c6mprise alkyl
7-Substituted-theophylline compounds. Roche Products (1-5 C) reserpates (and their acid addition salts) in which the OH
Ltd. (B.P. 801,679, 28.9.56. Switz., 29.9.55. Addn. t o 761,944; in the 18-position is esterified with a carboxylic acid radical corres-
J A.C. Abstr., 1958, i, 296).-7-(4-Piperidino-2-oxobutyl)theophylline ponding to [A] 1,5,3,4-C0,H(N0,)*CeH,(OR).0~C0,R (R is alkyl of
hydrochloride, m.p. 192-193". is obtained by condensing 7-acetonyl- 1-5 C) ; [B] hexahydrobenzoic acid ; [c] 1,2,5-C0,H.C,H3(OR'),
theophylline with paraformaldehyde or low-mol. alkyl chloromethyl (R' is H or alkyl of 1-5 C) ; [D] (OR).PhCH.COZH ; [El p-
ether and a piperidine hydrochloride (I) 85-95" in presence of BF,, N0,.CeH4.CH,C0,H ; [F] diphenylacetic acid ; [GI 3,4-methylene-
or with paraformaldehyde and I a t 85-95' in presence of AlC1, or dioxycinnamic acid. The products have a pronounced sedative-
AlBr,. The reaction is effected in anhyd. solvent (dioxan or PhNO,). hypnotic effect comparable with that of reserpine, with negligible
F. R. BASFORD. hypotensive action. Me 0-(5-nitro-3-methoxy-4-ethoxycarbonylbenz-
Triazine derivatives. May & Baker Ltd. (Inventors: J. N. oy1)reserpatehas m.p. 188-200". F. R. BASFORD.
Ashleyand S.S. Berg) (B.P. 824,908, 3.6.58. Addn. to B.P. 714,449).
-2-Amino-4,6-di-(p-amidinoanilino)-s-triazine(of B.P. 714,449) or Ferrous citrate complex. W. Oroshnik and W. H. Haffcke
an acid addition salt thereof is treated with D(-)-di-p-toluoyltartaric (B.P. 869,228, 23.10.57. U.S., 24.10.56 and 6.5.57).-Triferrous
acid (I) (or a salt thereof), e.g., in water, to give the I salt of the dicitrate decahydrate Fe,(C,H,O,),, 10H,O is prepared by adding
triazine, m.p. 225-227". The product may be produced in granular Fe powder to an aq. suspension of FeIIH citrate in a mol. ratio of
form and is useful as the products of B.P. 714,449 (in treatment of 1 : 2 and heating the mixture a t 85-90" in a n inert atm. (N,).
trypanosomiasis) but is less acidic and is better tolerated locally. 1. M. TACOBS.
F. R. BASFORD. Adrenocorticotropic hormone preparaticks. " Organon
2-Substituted oxazolid-3,4-diones. Murphy Chemical Co. Ltd. Laboratories Ltd. (B.P. 839,300, 25.8.58. US.. 5.9.57. Addn. to
(Inventors : M. Pianka and D. J. Polton) (B.P. 869,807, 28.11.58). B.P. 757,934; T.A.C. Abstr., 1957, ii, 549).-A Zn-ACTH prep.
--3-Substituted oxazolid-2.4-diones are obtained by cyclisation of (aq. suspension) -of improved properties (fine particle size, ease of
CO,R.NR.CO.CHRX at 150" ; the latter compounds are made by suspension, and resistance to breakdown when subjected to alternate
licating NHRCOK' with CHR"X.COX a t 90-140' (R is saturated freezing and thawing), suitable for injection is obtained by forming
or unsaturated aliphatic group, aryl optionally substituted, or wZn(OH), electrolytically in presence of ACTH. F. R. BASFORD.
substituted or nnsubstituted heterocyclyl or alicyclyl ; R' is alkyl Therapeutic substances from Melianthaceae plants. CIBA
or halogenoalkyl ; R" is H or alkyl ; X is halogen). Thus, a mixture Ltd. (B.P. 869,153, 28.10.58. Switz., 1. and 4.11.57).-A plant of
of NHMeCO,Me and CH,Cl.COCl is heated at 110" for 15 min. and the Melianthaceae family, e.g., Meliantltus major, M . comosus,
a t 180" for 1 h., then the product is recrystallised from MeOH, to Bersama paullinioides, B. lucens, B. swinnyi, B. tysoniana, B.
give 3-methyloxazolid-2,4-dione,m.p. 134", in 60% . yield. The abyssinica, B. kivuensis, and especially B. cf. hebecalyx, is suitably
products have anticonvulsant, antiepileptic and analgetic properties. extracted (e.g., with alcohol, halogenated aliphatic hydrocarbon,
F. R. BASFORD. etc.), and the extract is processed, to give 2 new acidic substances,
Benzoxazine derivatives. K. Thomae G.m.b.H. (B.P. 869,093, viz., a compound 21548/C, m.p. 320-323", and a compound
28.7.58. Ger., 27.7.57. Addn. to B.P. 806,729).-Compounds claimed 21548/A, m.p. 267-268", with characteristic U.V. spectra. The com-
comprise 4-oxo-2,3-dihydrobenz-1,3-oxazines substituted in the 2- pounds and their salts are active against viruses. F. R. BASFORD.
ii-4 19 5.-FATS, Etc. ii-420
either end I and wetting efficiences arc dccreascd and the surface
and interfacial tensions are increased, with an improvement in
Estimation of the iodine number of edible and industrial
oils by radio-iodine. M. F. ilbdel-Wahab and Saad A. El-Kinawi
Caz+ stability and lime soap dispersion. x.
G. \brHALLEY.

( Z . alzal. (;hem.. 1962. 186, 364--368).-The method depends upon Dialkyl esters of a-sulphofatty acids. J. J . McBride, jun., and
a paper chromatographic separation, followed by iodination directly E. J . Miller (.I. Amcv. Oil Chcvrt. Sor., 1962, 39, 105--109).--1)ialkyl
on the paper with 1311. licsults are compared on 22 fats and oils a-sulphofatty estcrs arc produced by reacting the a-sulphated fatty
(I No. 7 to 155) with the standard Hub1 method. (In English,) acids with ethylene or propylene at 500-700 p s i . and 35-45" in
G. RUSSELL. the presence of BF, with a reaction time of 3-5 11. Et, and
Reactivation of alumina used in bleaching of off-coloured Pri,a- sulphopalmitate have bcen obtained in 95 and 9O'x yields
cottonseed oils. J. C. Iiuck, W. A. Pons, jun., and V. L. Frampton respectively, by the method. Some reaction mechanisms are also
(,I.Amer. Oil Chem. Soc., 1962, 39, 84-86).-Spent Al,O, used for studied. G. R.\f'HALLISY.
the bleaching of cottonseed oil, is reactivated, after a final extraction Oxyethylation of 9,10-octadecanediols and 9,Wdihydroxy-
of the residual oil with light petroleum, by simple incineration a t stearonitrile. Non-ionic soaps. A. N. Wrigley, F. 1).Smith and
400-700" for about 1 h. The dried material is stored over water A. J. Stirton ( J . Amer. Oil Chenz. SOC., 1962, 39, 80--84).--The
l o absorb C l O ~ oof water. Bleaching and regeneration may be addition of ethylene oxide to the meso- and dl-forms of 9,lO-octa-
repeated indefinitely, and the oil loss by entrainment in the A1,0, decanediol is carried out at 160" and at 21 p s i . with ICON catalyst.
need only be 0.5%. G. K. WHALLEY. The non-ionic products are surface-active, with a hydrophilic part
Appraisal of methods of total monoester estimation in in the centre of the hydrophobic chain. It is further shown that the
commercial monoglycerides. L. Hartman ( J . Amer. Oil Chem. optimum emulsifying properties occur at n = 4, and optimum
Sor., 1962, 39, 126--128).-The analytical methods for determining wetting properties a t n = 12 (where n = no. of oxyethylene groups).
the total monoglyceride content of commercial products are The oxyethylated nitriles can be readily hydrolysed to the ' now
reviewed, and a modified procedure is suggested based on a com- ionic soaps ' of the type,
Lination of the partition method (J. Amer. Oil Chem. SOC., 1957, CH,. (CH,),,CH. [(OC,H,) z. OH] .CH*[(O*C,H,)y.013].(CIIJ,. C.O,Na
34, 301) with the methods of Martin (,J. Amer. chem. SOC.,1953, 75, (where x + y = n) ; but unlike normal soaps they are not readily
5483) and Broltaw et al. ( J . Amer. Oil Chem. SOC., 1955. 32, 194). precipitated in hard water or by metal ions. Some rates of reaction
A tentative method for determining total monoglyceride is also and product distribution are also studied. G. K. WHALLEY.
described, which is based on simultaneous isomerisation and Differentiation test for anionic, non-ionic and cationic
periodate oxidation. G. R. WHALLEY. surfactants. S. Greenberg (Chemist-Analyst, 1962, 51, No. 1, 1I--
Hydrogenation of castor oil in ethanol. I<. M. Manerkar and 14).-An acidic solution of the detergent is treated with p-dimetliyl-
J . G. Kanc (,J. sci. industr. Res., 1961, 20D, 465--466).-Almost aminoazobenzene (I) solution. The dye changes from red to ycllow
complete saturation of the double-bond in castor oil without or orange with non-ionic or cationic surfactants. A second portion
significant dehydroxylation may be achieved with the following of the solution is treated with solutions of benzidine and Na meta-
conditions :--ethanol/oil ratio 3-5 : 1, hydrogenation 'temp. 75- vanadate. Non-ionic surfactants develop a dark green colour,
IOO", ethanol concn. 90% vol., hydrogenation pressure 200-300 cationic and sulphated anionic surfactants a yellow colour and
p.s.i.g., Raney Ni catalyst 1.5-2-0%. D. J. ELGAR. sulphonated anionics a purple coloration. If I is then added, an
Hydrogenation of linolenate. IV. Kinetics of catalytic and orange colour is produced with cationic surfactants. A list of the
actual colours given by 21 branded surfactants marketed in the
homogeneous chemical reduction. C. R. Scholfield, J. U S A . is given. G. S. ROBERTS.
Nowakowska and H. J. Dutton (,{. Amer. Oil Chem. SOC.,1962, 39,
90--95).-The catalytic hydrogenation of equal amounts of the Me Gas chromatographic study of tall oil fatty acids frac-
esters of linolenic and linoleic acids has been carried out, and use tionated by countercurrent distribution, Y. Aho, 0. Harva and
made of W-labelled compounds and gas chromatography to study S. Nikkala (Tekn. Kern. Aikl., 1962, 19, 390--392).--Counter-
the kinetics of the reaction : triene + diene -+ monoene. Evidence current distribution of a Finnish tall oil fatty acid distillate (n-
for a triene --f monoene shunt is obtained. Some reductions with heptane and a mixture of equal p t . of MeOH, AcOH and formamide),
N,H, show no anomalous behaviour under the conditions studied. was followed by gas chromatography of the Me esters of the acids
Some methods for determining reaction rates are also discussed. obtained. Seven known acids (including 41% of oleic acid and 38%
G. R. WHALLEY. of linoleic acid) and small amounts of 14 unknown acids of 17-20 C
Hydrogenation of linolenate. V. Evaluating hydrogenation were separated, the latter fraction containing 10% (on total acids)
catalysts for selectivity. H. J. Dutton ( J . Amer. Oil Chem. SOC., of a trienoic acid shown to be probabIy cis-5,9,12-octadecatrienoic
1962, 39, 95-97) .-Equations for determining the ratio of hydro- acid (linolenic acid isomer). This gave only diene conjugation after
genation rates for linolenate and linoleate groups are derived from alkali isomerisation. The presence of this acid explains the
the kinetic theory, and are based on the analysis of linolenate after erroneous results obtained by U.V. spectrophotometric analysis of
the absorption of 0-5 mol. of H, in a 1 : 1 linolenate-linoleate tall oil fatty acids. (In English.) H. S. R.
mixture. Such a method can be readily extended t o a series of Extraction of 2-hydroxy-acids from wool wax acids. A. H.
catalysts for selection. G. R. WHALLEY. Milburn and E. V. Truter ( J . appl. Chem., 1962, 12, 15&-160).-
Improved yields in the acid-catalysed addition of phenols The wax acids a r e dissolved in CHC1,-light petroleum and a solution
and phenyl ethers to oleic acid. W. C. Ault and A. Eisner ( J . of Cu(NO,), in EtOH added. 2-Hydroxy-acids are precipitated as
Amer. Oil Chem. SOC.,1962, 39, 132--133).-The addition of phenols Cu complexes (I). I are dissolved in a dil. HCl-ether mixture
or phenyl ethers to oleic acid is accomplished a t room temp. for 6 h. and Cu precipitated with H,S. After drying the ether layer is
by using methanesulphonic or polyphosphoric acid as catalyst. evaporated t o give free acids (96% yield). Yields may be reduced
Good coloured products are obtained in 35-60% yields from, e.g., if acids are subjected t o heat owing to formation of lactides. CuSO,
p-t-butylcatechol and 2-naphthol. (The phenol adds on t o one of and CuCl, are unsatisfactory precipitants. (11 references.)
the ethylenic atoms). G . R. WHALLEY. 0. M. WHITTON.
Beeswax. I. Fractionation of beeswax and its alcohols
with urea. 11. Fractionation of fatty acids. T. N. Mehta and
Detergents, ate. B. N. Murthy (Indian J . appl. Chem., 1961, 24, 153-157 ; 158--
165).-I. Beeswax was saponified with KOH in EtOH. The fatty
Sodium salts of alkyl esters of a-sulphofatty acids. Wetting, alcohols were extracted from the unsaponifiables with pentyl
lime soap dispersion, and related properties. A. J. Stirton, alcohol and fuming HC1 and then acetylated. The acetates were
R. G. Bistline, jun., J. I<. Weil, W. C. Ault and E. W. Maurer ( J . fractionated with urea. The composition of the fatty alcohol fraction
Amcr. Oil Chem. SOC., 1962, 39, 128--131).-Esterification of was found to b e : 8.2% C,,, 30.4% C,,, 52.0% C,,, 7.4% C3%.
a-sulphonated fatty acids of up to 18 C with n-primary alcohols in 2.1 % of alcohols formed no adduct and were therefore known to be
toluene in the presence of H,SO, is used to produce esters of the type branched chain or cyclic. Urea fractionation of beeswax could be
RCH(S0,Na)COOR'. Such esters are compared for their critical used to separate hard and soft waxes used in the manufacture of
micelle concn. (I), surface and interfacial tensions, Ca" stability, cosmetics, candles, etc. (13 references.) D. DARKE.
wetting properties, foam height, detergency and lime soap dispersing
properties. From the results obtained, i t is shown that as the 11. The mixed acids of a sample of Indian beeswax were frac-
hydrophilic portion of the mol. is moved from the centre towards tionated by extraction with 75% and 65% EtOI-I into three groups
ii-421 5.-FATS, Etc. ii-422

which were separately converted ihto E t esters and fractionated stiffness in rubber possesses two important constituents, an elastic
by means of urea adduction. The composition of.the mixed acids part and a visco-elastic part. These are diagramatically presented
was : 20.27" hydroxyacids, 9.8% unsaturated acids and 69.9% and the effect of applying a load is demonstrated, discussed and
saturated acids. Extraction of mixed El. esters of beeswax fatty compared with other existing test methods. I t is claimed that the
acids with 55./;, EtOII indicated a composition of 22.2% liydroxy application of this concept, gives an instrument which is of great
acids and 9.1 yb unsaturated acids. (19 referenccs.) A. DARKE. valuc in routine examination of parts and compouncls. C. V.
Measuring the processability of elastomers. W. T. Blake
Detergent compositions. Shell Research Ltd. (Inventors : (Rubb. Age, N.Y., 1962, 90, 611-617).-Compounds must be tested
E. L. Shepherd and J. -4.Hill) (B.P. 870,458, 25.8.58).-The under identical conditions that they will meet with in processing.
detergent comprises 60-907(, by wt. of an organic sulphonate or The attainment of this is generally discussed with examples.
sulphate detergent or a mixture thereof (e.g., Na alkylbenzene-
s~~lphonate),
5--30:/, bv wt. of an alkylene oxide/phenol condensate
c. v.
Quantitative ozone test. C. Schaef (Rubber W o d d , 1962,
and 5-307' by wt. of an alkylene oxide/alcohol condensate (see 145, No. 5, 79-85).-An 0, crack vol. test has been developed whicll
col. 440). E. ENOSJONES. is simple, reliable and enables a quant. determination of 0, damage
Liquid detergent compositions. Unilever Ltd. (B.P. 870,081, to elastomers to be carried out since crack vol. is proportional to the
1.11.57. U.S., 2.11.56).-A liquid detergent composition in the form extent of the ozonation. During ozonation, the rubber specimen is
of a stable homogeneous aq. suspension comprises 7-10% bywt. of stretched to constant elongation ; this undergoes cracking and an
a I< higher-alkylarylsulphonate (allipl of 8-15 C-atoms), e.g., increase in thickness and width is noted. Thickness increase is
I< dodecylbenzenesulphonate ; 5 4 % by wt. of the Na or I< salt proportional to the extent of the 0, crack vol. The effect of anti-
of a lower alkylbenzenesulphonic acid containing one or two alkyl ozonants has been investigated. The thickness of the rubber specimen
groups with > 3 C (e.g., Na xylenesulphonate) ; 10-27% by wt. of is unrelated to the extent of the rubber damage and the extent of
K4 pyrophosphate or K, tripolyphosphate; 4-7% by wt. of a damage in N R and SBK stocks is inversely related to the temp. in
fatly monoalkanolamide with 8-12 C-atoms in the acyl radical the range 90-130"~. The extent of elongation during test is greatest
(lauryl), or the condensation product of such an alkanolamide with a t 20% with an initial rapid decrease which becomes increasingly
cquimol. proportion of ethylene oxide, or a fatty-dialkanolamide slower with increasing elongation. The test is limited in that i t does
with 8-18 C-atoms in the acyl radical ; and 0.1-3% by wt. of a not allow of observation of time to first crack ; elongations <20%
pair of cellulose deriv. which form a uniform stable suspension when should not be used. (12 references.) c. V.
added to a solution of the other ingredients, and at least one of Influence of static modulus of rubber on the rigidity of the
which has soil-suspending properties (e.g., salt of a carboxymethyl- system cord-rubber. A. Culfk and I. Franta (Chem. Przim., 1961,
Iiydroxyethyl cellulose and methyl cellulose). E . ENOSJONES. 11, 384-387).-The modulus of elasticity of the tyre casing is
Detergent compositions. Unilever Ltd. (B.P. 795,878, 27.5.55. independent of the modulus of the rubber and depends on the
Addn. to B.P. 766,401 ; J.A.C. Abstr., 1958, i, 643).-Germicidal number of the cord layers, type of cord, direction of thread relative
detergent compositions substantially free from free alkali comprise t o the axis and to some extent on the thickness of the rubber layer.
soap, O.Ol--S.O% by wt. of a ihiuram sulphide of the formula No experimental evidence was found for the dependence of the
Z,:N.CS.S,*CS.N:Z2 where n is 1 or 3 - 6 , and 2, and 2, each denote modulus of the tyre casing and the modulus of rubber. M. JUNGR.
a single bivalent cycloaliphatic radical or two monovalent aliphatic Utilisation of rubber from Parthenium argentatum. I.
radicals (dicyclopentamethylenethiuram hexasulphide), and 0.05- Preparation of chlorinated rubber. J. Roy0 Martinez and M.
5.0% by wt. of a stabilising compound (e.g., a per-oxide which
forms H,O, in alkaline solution, SnCl,, etc.). I. JONES.
Surface-active acylated hydroxy-sulphonates. Unilever Ltd.
-
Vazquez VaIero (Rev. Pldsticos, 1961, 12, 391-395).-Guayule
rubber from Parthenium argentaturn contains 30% of resin. The
rubber is readily chlorinated in solution either with or without
(Inventors : J. Van Alphen and J. Terwan) (B.P. 869,744,29.4.58).-- separation from the resin (by pptn. with Me011 from solution in
A process for the preparation of a mixture of surface-active agents C,H,). The deresinified material may reach a C1 content of 69%
of the general formula R.CO.O.R'SO,M where R is alkyl of 9-17 C. as compared with 58% for the natural product, the resinous fraction
I<' a divalent hydrocarbon or dialkylene ether radical of 2 - 8 C- taking up less C1. A Cu catalyst accelerates the reaction in the
atoms and M is an alkali metal, NH, or substituted ammonium initial stage without affecting the final degree of chlorination, and
radical, comprises heating a mixture of salts HO*R'*SO,M which in absence of light reduces the 7) of the solution. L. A. O'NEILL.
melts < 180", with an acid R.COOH a t <200" but above the m.p. Automatic control of humidity in rubber manufacture, as
of the mixture of saIts. In a n example lauric acid is heated with I< a means of preventing Ares and explosions due to the accu-
and Na isethionates a t 160' for 1 h. in presence of a catalytic mulation of static electricity. F. N. Lukyanov (Soviet Rubb.
amount of p-C,H,Me.SO,H, to give Na/K lauroylisethionate in 87% Technol., 1961, 20, No. 7, 27-31).-Maintaining the temp. of the
yield. E. ENOSJONES. benches, on which rubber is cut, at 12-15' in a const. temp. and
Acid esters of polyphosphoric acids and their salts. Farb- R.H. room prevents the build-up of static and ensures safe working
werke Hoechst A.-G. (B.P. 870,098, 20.8.58. Ger., 22.8.57) .-The conditions. E. C. DOLTON.
esters are prepared by heating a t 100-140" an aliphatic alcohol of Gelling of latices by fine suspensions. D. M. Sandomirskil,
-+8 C-atoms (wax alcohol) with a polyphosphoric acid in the presence I. D. PilmenshteIn and N. E. Khmelnitskaya (Soviet Rubb. Technol.,
of an anhyd. inorg. salt capable of binding water in the form of 1961, 20, No. 7, 6-9).-Latices are gelled by the introduction of
water of crystallisation (Na,SO,). The products are useful as fine suspensions of substances, e.g., C black, which have previously
emulsifiers and in detergents. E. ENOSJONES. been treated with a coagulating electrolyte. Latices gel if the
electrolyte is introduced with a carrier and coagulate if the electro-
Aliphatic glycidyl ethers and sulphonates therefrom. lyte is introduced without a carrier. Gelling rates vary widely with
T. Hedley & Co. Ltd. (B.P. 870,456, 6.12.57. US., 10.12.56).- particle size of the carrier and with the cation. E. C. DOLTON.
Detergent sulphonates are prepared by reacting a saturated or
ethylenically unsaturated fatty alcohol of 10-20 C-atoms (100 Silicone mould-release agents-their preparation and use.
moles) with epichiorohydrin (105-135 moles), treating the resulting K. E. Malkina and A. N. Krasotina (Sovzet Rubb. Technol., 1961, 20,
alkyl glyceryl chloroether product with an (25-50%) aq. alkali No. 7, 24-27) .-Two polysiloxane emulsions were prepared and,
metal hydroxide solution to epoxidise the product, separating the
epoxidised ether phase, and sulphonating the latter with a n aq.
solution of alkali metal sulphite and alkali metal bisulphite propor-
- -
after polymerisation on the mould, were used a t N 150" ; they
retained their properties for 150 moulding cycles. Using a poly-
siloxane lacquer the figure rose to 300 cycles and, compared with
tioned to give a sulphonated product having p H of 5-8. The C black lubricants, increased the best grade production although the
process is especially applied to coconut oil alcohol glycerol chloro- appearance of the tyres was impaired. E. C. DOLTON.
ether (prep. described). E . ENOSJONES. Natural rubber. IV. Depolymerisation of natural rubber in
presence of sunlight and air. H. N. Iyer and P. K. Choudhury
(Indian J. uppZ. Chem., 1961,24, 133--139).-The solution viscosity,
Rubber. solubility and gain in weight of samples of crepe rubber and smoked
New dynamic test for rubber. J. R. Kullman (Rubber sheet rubber exposed t o sunlight were studied. In the case of crepe
W o r l d , 1962, 145, No. 5, 73-76).-The three basic characteristics of rubber, a decrease in mol. wt. and increase in solubility indicate
vulcanised rubber, creep (stress relaxation), hysteresis (damping) chain-scission throughout auto-oxidation. Crosslinking was found
and elastic properties, are considcred and it is pointed out that the to occur initially in smoked sheet rubber ; but this was followed by
ii-423 5.-FATS, Etc. ii-424
oxidative dcgradation. I t is suggested that the increase in plasticity Vulcanising activity of derivatives of 2-mercaptobenzo-
might br uscd on an industrial scalc for thc initial plasticisation of thiazole and t h e i r lability w i t h radioactive di-2-benzothiazyl
crepe rubber. A. DARKE. disulphide. M. S. Feldshtein. I. G. Chernomorskaya, I. I. ISitingon.
Polymerisation of butadiene w i t h alkylaluminium and E. N. Guryanova and €4. A. Dogadkin (Sovzet Rubb. T'ec hnol., 1961,
cobalt chloride. M. Gippin (Industr. Engng Chem., Prod. Res., 20, No. 10, 13--16).-N-substituted deriv. of 2-mercaptobenzo-
1962, 1, 32---39).-The AlEt,CI combinations with CoCl, or thiazole are efficient vulcanisation accelerators whiist the S-
('011 chloride pyridinatcs require water in a certain mole ratio substituted deriv. do not affect the vulcanisation ratc or degree or
to the AIEt,Cl t o activate them as catalysts for butadiene cross linking. These results correlate with the fact that 3 5 exchanges
polymerisation a t 5" t o 98% cis-1,4 structure. The Co-pyridine readily between dibenzothiazyl disulphide (I) and the N-substitutetl
complex is preferred. AlC1, can replace water on an equimolar basis. deriv. but not between I and the S-substituted deriv.
The czs-1,4 content in the polymer decreases a t higher polymerisation E. C. DOLTON.
temp. The higher pyridinates of CoCl, tend to reduce the polymer Determination of mercaptobenzothiazole [accelerator M]
mol. wt. within narrow limits. Benzene is preferred as solvent and and 2-benzothiaz[ol]yl disulphide [accelerator DM] by p a p e r
certain mixtures with hexane arc used t o control mol. wt. The ratc chromatography. M. Stepieri and K. Gaczynski (Chem. Anal,,
of polymerisation is linear with respect to time initially, and is Warsaw, 1961, 6, 1045--1049).-An acetone extract of the sample
first-order with respect to monomer at a fixed concn. of catalyst. is chroinatographed on Whatman No. 4 paper and the spots of the
( I 2 refercnces.) 0. M. WHITTON. accelerator are detected with aq. Bi(NO,),, cut off and weighed.
The results are compared with a standard curve, prepared by the
Copolymerisation of butadiene a n d piperylene. I. A. same method with the standard rubber. The error is > 1576 for the
Iivshits, S. 1. llina and V. N. Reikh (Sovzet Rubb. Technol., 1961, accelerator M, and > 20% for the DM. The accelerator DM must he
20, No. 7, 2-5).-Butadicne (I) and piperylene (11) have been reduced t o mercaptobenzothiazole before the chromatographic
( opolymerised using I<,S,O, and isopropylbenzene hydroperoxide process. B. I<.
as initiators. Tensile strength tends to increase up to 50% I1
whilst increasing I1 up to 80% increases the breaking clongation Dependence of the h e a t effects of the vulcanisation of
and decreases the rebound resilience and cold resistance. Vulcani- n a t u r a l and synthetic rubbers o n the a m o u n t s of sulphur,
sates of copolymers of I and I1 have good fatigue life and are superior t e m p e r a t u r e , a n d type of accelerator. F. F. Koshelcv and N. A.
to 70 : 30 and 90 : 10 copolymers of I and styrene. E. C. DOLTON. Zanemonets (Sovzet Rubb. Technol., 1961, 20, No. 7, 9--12).---The
heat effects for natural rubber (I), 50 : 50 butadiene/a-methylstyrcne
Synthesis of polychelatotitanosiloxane elastomers by copolymer (11) and ' cold ' 70 : 30 butadienelstyrene copolymer (111)
polycondensation method. K. A. Andrianov, Sh. V. Pichkhadze have been observed with various accelerators and amounts of S
and V. V. Komarova (Izv. Akad. Nauk SSSR, Otd. khim. Nauk, when vulcanised a t 150-170". I and I11 have similar heat effects
1962, 261-264) .-aw-Dichloropolydimethylsiloxane with mol. wt. but that of I1 is considerably less. The heat effect increases with
3408 (by end groups) wasprepared from octamethylcyclotetrasiloxane increasing temp. and with increasing S content at a given temp.
and SiMe,Cl, and converted t o aw-dihydroxypolydimethylsiloxane NN-diethyl-2-benzthiazolyl sulphenamide increases the heat effect,
( I ) ,mol. wt. 4500. Polycondensation of I with bis(acety1acetonato)
tlibutoxytitanium gave polybis(acety1acetonato)titanodimethyl- mercaptobenzthiazole decreases it and diphenyIguanidine, tctra-
siloxane (11). Polycondensation of I with bis-(8-hydroxyquino1ine)- methylthiuram disulphide and MgO do not affect it.
tlibutoxytitanium in benzene solution gave polybis-(8-oxyquino1ine)- E . C. DOLTON.
titanodimethylsiloxane (111) as an elastic polymer, mol. wt. 97,000. S t r u c t u r e of vulcanisates of p u r e g u m styrene-butadiene
Curves show the dependence of viscosity on the time of poly- s t o c k s containing indene-coumarone resin. E. Ya. Devirts and
condensation (max. 15-20 min.) and thermomechanical properties A. S. Novikov (Soviet Rubb. Technol., 1961, 20, No. 10, 9-12).-
o f polymers. The approx. glass temp. of I1 is -75' and of I11 is
Six indene-coumarone resins with softening points varying from
- 110". P. W. B. HARRISON. 68 to 123O were used with 70 : 30 butadiene-styrene stock. As the
softening increased the equilibrium modulus, combined S, cross-
Determination of regularity of s t r u c t u r e of lithium- link density and mechanical properties increased and the reduction
piperylene r u b b e r according to the combining of 1,4-links. in stock viscosity decreased. E. C. DOLTON.
A. I. Yakubchik, V. K. Smirnova and V. M. ZabaleI (Zh. prikl. Khim.,
1962, 35, 405-408) .-The products of decomposition of the ozonide Channel replacement b y oil-based furnace black. R. J.
of lithiumpiperylene rubber (I) were examined to establish the Wood (Rubb. Plast. Wkly, 1962, 142, 309-311).-A brief survey,
sequence of combination of the 1,4 links. Macromol. of I contained the characteristics of some 16 being tabulated. c. v.
1.4-1.4 ; 1,4-4,l and4,l-1,4 portionsaswellas 1.2links. A. L. B. Radiometry and rubber. W. D. McHenry (Rubb. Age, N.Y.,
Effect of t h e ingredients and condensation conditions of the 1962, 90, 627-631).-*H tagged additives are used to examine thc
resorcinol-formaldehyde resin used in c o r d dips o n the nature of the synergistic relationship of heat-stable inhibitors in
adhesion of r u b b e r to cord. R. V. Uzina, I. L. Shmurak, M. S. styrene-butadiene vulcanisates, specially the Cd/Ba salts of stearic
Dostyan and A. A. Kalinina (Soviet Rubb. Technol., 1961, 20, No. 7, and myristic acids and pentaerythritol. Most vulcanisates are not
I&21).-The resorcinol : HCHO ratio, catalyst and condensation sol. in the solutions used in liquid scintillation counting ; this is
time and temp. have been varied and the effects on mechanical overcome by the use of suspension counting techniques. Although
properties using dips based on 3 latices observed. Max. bond the work is limited t o the 8H-tagged compounds, i t is considered
strength is achieved with ratios 1 : 2 to 1 : 4 with a 70 : 30 butadiene- that other radioisotopes could be usedprovided the tagged compounds
styrene copolymer (I) and a 90 : 10 butadiene-methylvinylpyridine could be prepared economically. This method measures not only the
copolymer (11) and with ratios 1 : 1.5 t o 1.3 with a carboxylated overall change in additive concn. but also pin-points the area or
butadiene latex (111). The degree of condensation giving optimum depth at which the change occurs. c. v.
bond strength was measured as the specific optical density; for Complexometric determination of a l u m i n i u m , iron, cal-
I and I11 this was between 2 and 3 and for I1 between 1.5 and 2.5. cium, magnesium and zinc in vulcanisates. L. L. 3ogina and
The maturing time for I1 is reduced from -24 h. t o -12 h. The
bond strength with I falls when the resorcinol-formaldehyde resin I. P. Martyukhina (Soviet. Rubb. Technol., 1961, 20, No. 10, 27-29).
is condensed above 35" and falls with I1 and 111 when the conden- --Fe and A1 are removed from the HC1 solution of the ash by pptn.
sation temp. is > 25". (12 references.) E. C. DOLTON. as hydroxides. F e is determined by titration with the Na, salt of
EDTA (I) using sulphosalicylic acid as indicator ; excess I is then
Processing u r e t h a n e elastomers. K. A. Pigott, J. W. Britain, added and A1 determined a t p H 4-8 by back titration with FeI'INH,
W. Archer, B. F. Frye, R. J. CBt6 and J. H. Saunders (Industr. alum. Total Ca, Mg and Zn is determined by titration with I
E$.izgngChem., Prod. Res., 1962, 1, 28-31).-A new type of partially at p H 10 with chromogen-NaC1 indicator, Ca+Mg by the
cured, solid polyurethane elastomer, Texin, is processed by extrusion same method after removal of Zn with Na,S+dil. HCI and the Ca,
a t 300-350%; calendering with roll surface temp. of 3 0 0 ' ~ ; after removal of Zn, is titrated with I in the presence of sucrose,
injection moulding at 350-400"~. with 10 sec. cycles ; transfer murexide-NaC1 indicator and NaOH. The method gives satisfactory
moulding + 2 5 0 " ~with cycles of 1-2 min.; compression moulding results and is completed in 5-6 h. E. C. DOLTON.
a t + 2 5 0 " ~ .Abrasion resistance, 0, resistance, high tensile and tear
properties are equivalent to those obtained by casting. Many of C u r i n g of carboxylated rubbers with peroxides. N. D.
the ultimate properties are realised without additional cure, but Zakharov and I. N. Berezkin (SovietRubb. Technol., 1961, 20, No. 10,
postcuring yields lowest set and best solvent resistance. 6-9).-Carboxylated 70 : 30 butadiene-styrene was vulcanised
0.M. WHITTON. with di-isopropylbenzene monohydroperoxide (I) and MgO. In-
ii-425 6.-FIBRES, Etc. ii-426
creasing I up to 1 % and increasing MgO content both improved the Leathor.
modulus and tensile strength but also increased the scorch risk.
The latter was overcome by the incorporation of a reducing agent, Use of sodium hypochlorite and chlorite in soaking dried
e.g., usual vulcanisation accelerators. Reaction between filler, e.g., hides. M. Dempsey and G. H. Green ( J . Sac. Leath. T r . Chem.,
C black, and peroxide occurred during the vulcanising of filled stock. 1962, 46, 76--78).-0.02% NaClO, is superior to 0.1% NaClO in
E. C. DOLTON. improving the handle of the hides but neither compound impaired
Aircraft gasket compounds. H. N. Galpern (Rubb. Age, N . Y . , tanning or lowered the leather yield. E. C. DOLTON.
1962, 90, 621-626).-The effect of methylphenyl- (I) and methyl- Chemistry of chrome tanning, past and present. K. H.
chlorophenyl-silicone lubricants on Viton A (11) a t elevated temp. Gustavson ( J . SOC.Leath. Tr. Chew., 1962, 46, 46-75).-A review,
is studied. I1 is virtually unaffected by 1000 h. ageing in these at including properties of Cr salts, protein reactivity, cross-linking
300 and 4 0 0 " ~but a Li-thickened chloro-I grease greatly reduced reactions, binding of Cr atoms to collagen and the properties of
the service life of 11. The relative lack of swelling shown by I1 in succinylated collagen. (99 references.) E. C . DOLTON.
the silicone lubricants may limit its performance since there is a
3-10% shrinkage a t elevated temp. The findings are discussed
but a caveat suggests that more recent advances may have t o be Water-soluble condensation products with tanning proper-
taken into account in applying the present findings. c. v. ties. Farbenfabriken Bayer A.-G. (B.P. 799,224, 10.12.54. Ger.,
11.12.53. Addn. t o B.P. 747,675; J.A.C. Abstr., 1957, i, 300).-
Rubber. Natural Rubber Producers' Research Ass. (B.P. The products are prepared from a mixture of (1) a monosulphonic
869,283, 30.7.57).-The ageing characteristics of natural or synthetic and/or disulphonic acid of a n aromatic hydrocarbon containing a t
unvulcanised polyisoprene elastomers are improved by the addition least two condensed nuclei (naphthalene), (2) a lower saturated
of reducing substances (e.g., dicthylenetriamine) t o the latex or to aliphatic aldehyde (CH,O) and a n a-chlorophenol having at least
raw solid polyisoprene polymers. E. ENOSJONES. one free o- or p-position, (3) another substituted phenol
RIR,C,Ha.OH where R, and R, are alkyl, halogen, nitro or carb-
Polyurethane elastomers. U S . Rubber Co. (B.P. 869,562, alkoxy or R, is H or R,+ R, form a benzene nucleus (e.g.. a xylenol).
30.6.59. US., 18.8.58).-A polyurethane elastomer is prepared by The condensation products are prepared in a strongly acid medium
mixing a liquid prepolymer, obtained by interaction of a polyester, until the resulting products are water-soluble. I. JONES.
polyether or polyesteramide with excess of a di-isocyanate, with a
diamine (naphthalene-13-diamine) a t a temp. below the m.p. of
the latter. The mixture is then cured at a higher temp,
E. ENOSJONES.
Synthetic rubber latex. U S . Rubber Co. (B.P. 869,500,
6.-RBRES, Etc.
26.2.60. U.S., 4.5.59).-The latex is produced by polymerising an Testing apparatus for determining the energy of defor-
aq. emulsion of synthetic-rubber-forming monomers selected from mation of materials. C. Melzer (Faserforsch. u Textiltech., 1962,
butadienes-1,3, and mixtures thereof with >70% by wt. of mono- 13, 27--33).-An apparatus is described for the determination of the
vinyl compounds to a latex of 60-95% conversion, adding to the relationship between energy of deformation (elongation and tensile
latex before or after i t has reached 60% conversion and in the stress) and textile performance for specific uses. W. H. KEMP.
presence of + 5 % of unreacted monomers, 0.05-1 part yo of ethyl Modified determination of NN-dimethylformamide in
hydroxyethyl cellulose a t 0-1 5", and then removing unreacted solutions and fibres. S. Urbanowicz (Chem. Anal., Warsaw, 1961,
monomer from the latex. E. ENOSJONES. 6, 855-858).-Dimethylformamide (I) is hydrolysed with aq.
Chemical modification of rubbery copolymers. Esso NaOH and the resulting NHMe, is steam-distilled into saturated
Research & Engng Co. (Inventor : G. E. Serniuk) (B.P. 870,332, boric acid solution and titrated with 0.02 N - H C ~using Taschiro's
31.3.60).-A rubbery copolymer derived from a 4-8-C iso-olefin indicator. Very hot water is used t o extract I from fibres. The
with a 4-14-C multiolefin (butyl rubber) is treated with a 1-10-C standard deviation for 0*1-0*2'70 solutions of I is 0.03, and for
aliphatic or aromatic aldehyde, or substances which under the 50% solutions 0.59. The determination takes 15 min.
conditions of the reaction form in situ such aldehydes, in the P. BRYCH.
presence of a Friedel-Crafts type catalyst (BF,) a t -40" to + 150". Effect of periodate oxidation and of subsequent borohydride
The products are useful for manufacture of improved tubeless tyres. reduction on the tensile strenQth of cotton. T. P. Nevell and
E. ENOSJONES. S. H. Zeronian ( J , Text. Inst. Trans., 1962, 53, T90-T93).-Tensile
Organopolysiloxane elastomers. General Electric Co. (B.P. strength loss is rapid during initial oxidation but then shows little
869,845, 8.4.59. US., 13.5.58).-Claim is made for a gum, conver- change, even a t high degrees of oxidation. Reduction partly restores
tible to the solid, cured, elastic state, comprising a n organopoly- strength lost during initial oxidation b u t results in further loss of
siloxane in which at least some of the organo radicals are Si-bonded strength in highly oxidised samples. The formation of hemi-acetal
R'.SO,.R radicals, where R is a n alkylene radical containing at least cross-links is suggested. E. C. DOLTON.
2 C-atoms with the S-atom separated from the Si-atom by at least Formation of supercord rayon and mechanism of viscose
2 C-atoms and R' is alkyl or aryl, any remaining organo radicals modiAer action. A. Griibe, H. Klare, R. Maron. H. Jost and G .
being monovalent (halogenated) hydrocarbon radicals. In an Casperson. (Faserforsch. u Textiltech., 1962, 13, 1-9).-The inter-
example the siloxanes of B.P. 869,844 (see col. 400 above) are mediate formation of cellulose xanthate in the viscose spinning
oxidised with HIOz. The oxidised product is cured after addition of process, particularly for supercord rayon, was investigated.
silica aerogel and Bz,O,. E. ENOSJONES. Neutralisation of alkali, CS, split off from the xanthate and the
Vulcanised rubber compositions containing silica. Kali- Zn content of the fibre were determined. Exhaustive measurements
Chemie A.-G. (B.P. 870,173, 22.7.59. Ger., 30.7.58).-1n a method of the swelling of single filaments were carried out at the neutral
of improving a natural or synthetic rubber composition containing point. Zn cellulose xanthate formation occurs in the cuticle only.
silica and other filler materials, the vulcanisation of such a com- The effect of modifiers on fibril-bundles can be followed b y electron
position is performed in the presence of 0.1-5-0~0 of F- (NH,F) microphotography . W. H. KBMP.
based on the wt. of silica in the composition. E. ENOSJONES. Solubility of sodium sulphate in spin-bath acid. B. Stannard
Vulcanisation of rubbers. Hercules Powder Co. (B.P. 808,302, (J. appZ. Chem., 1962, 12, 165-170).-A method is described for
19.12.56. US., 15.5.56. Addn. t o B.P. 754,514; J.A.C. Abstr., calculating the solubility of Na,SO, in spin-bath acid over a relatively
1957, ii, 283).-The vulcanisation process comprises heating a wide concn. range. Behaviour of Na,SO, and H,SO, as NaHSO,
rubber composition, a n acidic inorganic filler (kaolin), a peroxide and ' f r e e ' Na,SO, is assumed. Application of the method t o
RlR2RaC*O*O*CR4R,R, (where R, and R, are aryl, R,-R, are H or Na,SO, crystallisation from spin-bath liquor is illustrated and
alkyl groups of < 4 C-atoms, e.g., Bz,O,) ; an inorganic alkali discussed. 0. M! WHITTON.
(e.g., ZnO) : and a basic amino compound (e.g., triethanolamine). An interpretation of the mechanical properties of covered-
I. JONES. rubber yarns. L. R. G. Treloar ( J . Text. Inst. Trans., 1962, 53.
Stabilisation of vulcanisable foams. Farbenfabriken Bayer T69-T89) .-A theoretical treatment is given relating retraction
A.-G. (B.P. 869,247, 12.8.59. Ger., 12.8.58).-Vulcanisable foams of after recovering with the helix angle during covering and which
rubber, or synthetic resin emulsions or dispersions, are stabilised by allows calculation of the stresses in both core and covering. The
the addition of a polyether thioether, e.g., thiodiglycol. theory is verified experimentally and it is shown that yarn strcngth
E. ENOSJONES. is determined almost entirely by the covering. E. C. DOLTON.
H
ii-127 6,-FIDI<ES, Etc. ii-428

Inter-fibre adhesion in sized yarns. D. N. E. Cooper (1. or treated with


. . 20--300/; aq..acetic acid a t 70-100" for 3--60 mi
Text. Iitsl. Trans., 1962, 53, T94-T100).-Yarn stiifness has been H. L. \VliITEHEAD.
used as a measure of adhesion and the breakdown of this adhesion Substantially .linea.r segmented polymer fibres. E.1: DU
during flexing studied. (18 references.) E. C. DOLTON. Pont de Nemours & Co. (B.P. 870,292, 2.1.59. U.S., 9.1.58).-New
Washing synthetic fabrics. P. W. Sherwood (Riu. ital. Sostanze elastic fibres-which have good hydrolytic stability, low temp.
grasse, 1962, 39, 15-17) .-Differenccs in synthetic or naturaI elasticity, and high sticking tcmp.-are formed by spinning new
fabrics, in respect o€ dirt pickup, water-uptake, dimensional substantially linear segmented polymers. These comprise a no. of
stability, drying propertics and thermoplasticity, in so far as they polyester segments (I) each derived from 0I-I-terminated polyesters
affect washing procedure, are discussed. L. A. O'NEILL. (of m.p. < 60" and mol. wt. 600-5000) by removal of the terminal
OH, and a no. of non-polyester segments (11) consisting of polyurea,
Modern physical techniques in colour formulation. J . V. polythiourea or polyurea-thiourea repeating units (each poly-
Alderson, E. Atherton and A. N. Derbyshire ( J . SOC.D y . C d . , 1961, compound having m.p. >200"), I and I1 being interconnected by
77, 657-669) .-Colour control and formulation by instruments urethane or thiourethane linkages, and I1 containing, in the chain
(filter colorimeters, spectrophotometers and high-speed electronic or directly united to said linkages, symmetrical divalent aromatic
digital computers) are discussed, with their practical applications. radicals free from fused rings. A typical segmented polymer is
The relation of colorist's terminology to colorimeter variables and formed by reacting 0.017 mol. of a polyethylene adipate of m.p.
the use of transformation equations arc considered and a programme 44-48' and 860 OH and 109 COOH groups per 106 g. (prep. des-
for an electronic computer is outlined. 0. M. WHITTON. cribed) and 0.034 mol. of di-(9-isocyanatopheny1)methane in solution
Dyeing behaviour of abraded wool. H. R. Hadfield and D. R. in methylenc chloride at 100" for 2 h.; and reacting the resulting
I.emin ( J . SOC. D y . Col., 1961, 77, 715-726).-When abrasion NCO-terminated polyester with 0.017 mol. of ethylenediamine in
precedes dyeing, thc abraded areas dye initially more heavily than solution in dimethylformamide (111) : a solution of the polymer in
unabraded areas. When dyeing precedes abrasion, the abraded 111 is dry spun t o fibre. H. L. WHITEHEAD.
w e a s nppcar to bc less heavily dyed, owing to an optical effect
caused by fibrillation of the fibres. Rubbing of wool against wool Modified polyesters. Chemstrand Corp. (B.P. 869,956, 18.8.58.
U.S.. 6.9.57).-A fibre-forming modified polyester, m.p. > 200".
gives abrasion identical to that by glass-paper, etc. The time having improved dye receptivity and solubility, comprises the
rcqtrired to produce level ilyeings on abraded wool varies with the
reaction product of one mole equiv. of a mixturc of ( 1 ) a t least one
(lye used and is less with monosulphonated dyes, and is reduced by material selected from a terephthalic acid and isophthalic acid, or
tw-tain cationic auxiliary agents, e.g., cetyltrimethyiammonium
I,romitlr. (:arbonisation with 50 g./l. of 66' I36 H,SO,, after abrasion, thcir dialkyl esters (aikyl of 1-5 C), (2) a t least one dialkyl ester of
h ~ l l o w dl)y drying a t 105' gives more uniform dyeing. Apparently, a saturated aliphatic dicarboxylic acid of 20 C-atoms of thr: formula
lI,O.CO.A.(C,II,,+l)y.CO.OR, where 11, and K, ai-c 1--104:
abrasion increases the Iiyrlropliilic nature of the fibre surface. (12 allryl (eg., Me, eicosane-1.20-dioatc), \I a linear saturated 14-18-C
rt.ferenccs.) 0. M. WHITTON.
aliphatic radical, 72 is 1 or 2 and y 0-2, and the total number of
lJse of starch and its derivatives in textile printing. P. C-atoms in A and the side chains thereof, if present, is 18, and (3)
Schiiller (Stdrke, 1962, 14, 131--134).-The properties of starches a molar excess of a t least one glycol of 2-10 C-atoms.
(wheat, maizc, potato and rice) used in the textile industry are E. ENOSJONES.
rcviewcd. Maize and wheat starches are used in concn. l0-127!,, Polyacrylonitrile solutions. Courtaulds Ltd. [ Invcntors :
chiefly as thickeners in printing on cellulose fibres. Solvitosc C5 A. E. L. Marsh and A. W. Bennett) (B.P. 811,638, 18.1.57. Atldn.
(a starch cthcr) made by the action of monochloroacetic acid on to B.P. 714,530 ; J.A.C. Abstr., 1955, i, 455).-Improved spinning
starch in a n alkaline medium is also used for Chis purpose. solutions of acrylonitrile polymers (,containing 4 80yo of combinctl
E. M. J. acrylonitrile) (I) contain as the solvent a mixture of water 4-10%
Comparison of the principal test methods for evaluating and 435y0 (on the mixture wt. of MeOH and/or EtOH) of a highly
moth-proofing agents. J. €1. Cole and I?. G. Sarel Whitfield water-sol. thiocyanate of an alkali metal, earth alkali metal, NH,
(,I, T e x t . Inst. Proc., 1962, 53, 1'23&P251).-The moth-proofness or guanidine. LiRr, LiI, NaI or ZnC1,. A typical solution is a n 11%
of three fabrics was determined by four routine methods and the solution of a mixture of 47 pt. of NaSCN, 5 pt. of MeOH and 48 pt.
results compared. Despite differences in the methods for inter- by wt. of water. H. L. WHITEHEAD.
preting these results the final assessments are similar. (22 references.)
E. C . DOLTON. Glass Abres. B.F. Goodrich Co. (B.P. 820,276, 31.10.55. U S ,
24.1.55. Addn. to B.P. 731,812; J.A.C. Abstr., 1956, i , 294).-
Separation of the fibres from the bark, wood and other Glass fibres produced in known manner from low soda-ash glass are
tissues of fibrous plants. R. H. Turnbull (B.P. 825,074, 27.10.56. coated with an alloy consisting of P b with 0.001-10 (0.001-5)
Addn. to B.P. 721,878 ; J.A.C. Abstr., 1955, ii, 105).-In modifica- wt.-"/, of a metal selected from Na, IC, Mg, Ca, Zn, Sr, Ba, Al, Ga,
tions of the process of the earlier B.P. for separating the fibres from Ti, Sn, Cr, Mn, Cd and Fe (Zn, Al, Ti, Na and Cd). J . M. JACOBS.
such parts of fibrous plants by crushing plant parts, and treating
the crushed product at 30-60" with a liquor containing cystase, Resilient materials. Dunlop Rubber Co. Ltd. (Inventors :
the treatment is accelerated by the use of fluid pressure (15-75 C. T. Gildea and F. C. Jennings) (B.P. 869,606, 869,624, [A] 12.1.
p s i . ) in the system, and, optionally, conducted a t the lower temp. and 12.7.57, [B] 12.1. and 26.6.57. [FJ]divided out of novel
of 20-30". H. L. WHITEHEAD. resilient materials, useful as upholstery or shock absorbing materials,
are composed of a mass of [A] non-compacted resilient fibres or [B]
Recovery of alkali metal hydroxides and salts from residual fragments of resilient cellular material (crumbs of rubbers or
liquors from the production of cellulose. Comercial Papelera polyurethane foams) bonded together by a flexible solid material
Torres S.A. (Inventor : A . X. Bas) (B.P. 869,800, 5.9.58).-1n an obtained by reaction between (a) an org. compound containing
improved method for recovering alkali metal hydroxides, bicar-
bonates, carbonates or other alkali metal salts from the alkaline
< 2 NCO or NCS radicals, eg., toluylene di-isocyanate or addition
product thereof with trimethylolpropane, with ( b ) [A] a monomeric
liquors residual from making cellulose, the undiluted liquor is ester (I) of mol. wt. 200-10,000 containing < 2 NCO-reactive groups
evaporated to a concn. of ~ 3 2 g. 0 of org. matter per 1.; an acid (e.g., monomeric triester derived from glycerol and ricinoleic acid)
(CO,, SO, or H,S) is then added a t 8 0 4 5 " until the isoelectricpoint or [B] an org. compound of mol. wt. 500-10.000 containing Y2
of the solution is reached to co-precipitate lignins, org. matter, and NCO reactive groups, e.g., I or castor oil. H. L. WHTIEHEAD.
alkali metal (as carbonate, bicarbonate or other salt) ; and the ppt.
is separated, dried and ignited to remove org. matter t o leave [A] Modification, [B] treatment of cellulosic materials.
alkali compounds as a n ash. If desired, the ash is re-causticised to Imperial Chemical Industries Ltd. (Inventors : [A] J. Earnshaw and
form the hydroxide. To obtain SO,-free products from liquors J. A. Moyse, [ ~ R. l Sause and W. B. Stephen) (B.P. 869.659-60,
resulting from digestions of straws with alkali. the liquor is treated [~]31.12.57,[~] 15.1.58,[siaddn.toB.P.794,~80;J..4.C.Abstr., 1959,
with CO, a t 70-80", before concentration to precipitate the silica. ii, 398).-[B] The earlier specification is modified in that the triazine
H. L. WHITEHEAD. deriv. used may have up to 2 halogen and one primary or s-amino
Treatment of cellulose triacetate fibres. British Celanese group as substituent and also a solubilising group which may be
Ltd. (Inventors: R. J . Mann, M. W. Alford and B. Krzesinski) positively charge& (quaternary ammonium or phosphonium group)
(B.P. 869,605, 7.12.56).-The sticking or safe ironing temp. of or non-ionic (polyallrylene oxide or sugar residue). One compound
cellulose triacetate fibres is raised by 4 10" by treating them at used is ~-(4,6-dichloro-1,3,5-triazin-2-yl)aminophenacyl-trimethyl-
<looo with a liquid agent of which many types are given. In ammonium chloride. [A] The material treated with the triazine deriv.
prefcrred forms i~ triacetate fabric is Imiled with I'rlOH for 1-2 h., as i n [H]is further modified by trcbatmcnt with a conipoiind capable
ii-429 6.--FIBRES. Etc. ii-430
of reacting with the triazine deriv. When the triazinyl compound succinamide with formaldehyde. The amide-formaldehyde com-
has a negatively charged salt-forming solubilising group, the after- ponent is +-SO% (-20%) by wt. of the condensate. I. JONES.
treatment is with a heavy metal s a l t ; when i t has a positively Polyquaternary compounds. Farbenfabriken Bayer A,-G.
charged salt-forming group, after-treatment is with an alkali metal (B.P. 869,423, 4.9.57. Ger., 8.9. and 20.10.56).-Polyquaternary
chromate or phosphate. In a n example, the cellulosic material is compounds, for use as after-treating agents for dyed materials,
treated with 2-(4,6-dichloro-s-triazin-2-yl)aminonaphthalene-~-sul- especially cellulosic materials dyed with direct dyestuffs (to improve
phonic acid and then with aq. CuS0,. H. L. WHITEHEAD. fastness t o washing), are produced by bringing monohalogenated
Polymerisable ureido and thioureido compounds. Rohm amines, viz., NRR’.R”.X into contact with water while stirring and
& Haas C o . (F3.P. 831,635, 12.4.56. U.S., 15.4.55, divided out of heating, such that there is insufficient water to form a homogeneous
B.P. 822,267 and addition t o B.P. 761,901 ; J.A.C. Abstr., 1958, system (R and R’ are hydrocarbon radicals or together with N form
i, 316).-Claim is made for a compound a heterocyclic ring ; R’ is hydrocarbon radical optionally con-
CH,:CR.CO-O.A.NR’*CX.NH.CH,.OR~, where R is H or CH, ; A taining hetero atoms ; X is halogen). Thus, water is added slowly
is phenylene or an alkylene group of 2-4 C-atoms of which a chain to NEt,.[CH,],.Cl at 80-1004 t o form a viscous, homogeneous,
of a t least 2 extends between the adjoining 0 and N-atoms ; R is optically clear fluid. F. R. BASFORD.
a 4-12-C alkyl group containing a tertiary C-atom attached to the Optically brightening fibrous materials. CIBA Ltd. (B.P.
adjoining N-atom ; X is 0 or S ; and RZ is an alkyl group. Inter- 823,227, 20.2.56. Switz., 22.2.55 and 25.1.56. Addn. to B.P.
action of MeO.CH,.NCS with t-butylaminoethyl methacrylate in 746,046; J.A.C. Abstr., 1957, i, 218).-The agents used are
benzene gives N-metho~.vmet~~yl-N’-t-butyl-N‘-methacryloylethyCurea.2-R-5-R’-1,3,4-oxadiazoles where R and R’ are phenyl, one of which
The products are useful in thc modification of surfaces of various is $-substituted by C1, Me or OMe and the other p-amino group
materials. E. ENOSJONES. which may have Me or E t substituent and/or a solubilising group,
Dyeing of wool. CIBA Ltd. (B.P. 869,056, 19.10.59. Switz., e.g., SO,H. One example cited is 2-$-chlorophenyl-5-$’-sulpho-
14.11.58).-Cn the dyeing of wool with a complex Cr or Co compound methylaminophenyl- 1,3,4-oxadiazole. H. L. WHITEHEAD.
of a monoazo dyestuff free from S0,H and CO,H groups, there is Hydrophobing emulsions. Badische Anilin- u. Soda-Fabrik
added to the dye bath a wool immunising agent having an affinity A . 4 . (Inventors: E. Schwartz, W. Gerhard, H.-G. Conrad and
for the fibre (eg., a phenol or thiophenol rendered water-sol. by W. Krause) (B.P. 869,961, 16.10.58. Ger., 19.10.57).-Stable
interaction with alkali metal or NH, sulphide, sulphite, or sulphite- hydrophobing emulsions of high activity, which contain in a
CH,O addition compound, or by sulphonation ; a reaction product substantially aq. acid continuous phase solid and/or liquid paraffin,
of CH,O and a naphthalenesulphonic acid; or a compound of a waxes, oils, fats and/or resins and salts of di-, tri- or tetra-valent
sulphurised phenol and an acid-insol. metal sulphide) and [CH,],N,. weakly basic metals (zirconyl acetate) but no protective colloid and
F. R. BASFORD. no surface-active emulsifier other than the hereinafter-mentioned
Dyeing process. Imperial Chemical Industries Ltd. (Inventors : alcohol, contain an alkanol of > 5 C (BuiOH)in an amount of 2--200/,
R. A. Acraman and D. R. Lemin) (B.P. 869,150, 8.10.58).-Wool is of the amount of the emulsion b u t not more than is necessary t o
dyed by treating i t with aq. medium containing an acid (or an acid saturate the aq. phase. E. ENOSJONES.
salt), a surface-active cationic agent, a non-ionic dispersing agent, a Treating fibres, articles made therefrom or films to reduce
water-sol. or fluid amine, phenol or alcohol (especially benzyl their tendency to accumulate static charges of electricity.
alcohol), and a water-sol. reactive dyestuff, e.g., a Procion-type American Cyanamid Co. (B.P. 801,721, 4.4.55. U.S., 9.4.54. Addn.
dyestuff containing mono- or di-chloro-s-triazine radicals. to B.P. 723,58O).-The fibres, films, etc., of natural or synthetic
I?. R. BASFORD. basis (especially acrylonitrile polymers and copolymers) are first
Dyeing of textile materials. Courtaulds Ltd. (Inventors : treated with a solution or dispersion of concn. 0.1-20yo in a volatile
S. N. Bradshaw and H. B. Nann) (B.P. 789,243, 29.7.55. Addn. to liquid (water, EtOH, etc.) of a compound
B.P. 747,622 ; J.A.C. Abstr., 1957, i, 305).-In dyeing textiles by RCO~NH~[CHz],~N(Y)RIRzRs (1) where R is an aliphatic ( < 7 C)
treating them with a (direct cotton) dyestuff in presence of urea or alicyclic radical, R1 a radical (CpHsp.O)m.H, p being 2-4 and
and baking the treated materials a t temp. between the m.p. of urea m +6, KZis 1-5-C alkyl or hydroxyalkyl, RS is H or as Ra, and Y
and 160”, a depressant is added ( + 4 of wt. of urea) to lower the an anion (halogen], e.g., y-stearamidopropyldimethylnonaethanoxy-
m.p. of the urea by 10” (e.g., thiourea, glycerol, NH4C1). The fibres ammonium chloride ; and thereafter dried a t room or elevated temp.
may then be dyed: level shades are obtained on mixed (e.g., Methods of making I are described. H. L. WHITEHEAD.
protein/rayon) goods which yield only differential dyeings on the
different fibres in conventional aq. dyeing methods. Fire retardant coating compositions. Dow Chemical Co.
H. L. WHITEHEAD. (Inventors : E . K. Stilbert, jun., I. J. Cummings and G. E. Clock)
Fast dyeings on cellulosic textile materials. CIBA Ltd. (B.P. 819,190, 20.6.57. Addn. to B.P. 755,551 ; J.A.C. Abstr.,
(B.P. 869,549, 27.8.58. Switz.. 4.9.57).-The goods are dyed with a 1957, ii, 376).-The compositions comprise a 40-60y0 aq. dispersion
dyestuff (of the azo, anthraquinone or phthalocyanine series) which of a mixture of 70--85~0 non-film-forming intumescent solids (I)
contains a water-solubilising group and a reactive amino group, and and an aq. film-forming latex of a vinyl polymer t o give 30-15%
are treated during or after dyeing with a compound containing of solids on the total solids in the dispersion. I consists of a foam-
2 epoxy groups (ethylene glycol diglycide ether) or with 2,3-dibromo- forming ingredient (e.g., NH,H,PO,), a polyhydric compound (starch,
butane- 1,4-diol, and finally while carrying both dyestuff and epoxy hexitol, etc.) and a N deriv. such as glycine, a urea deriv.. guanidine
compound or diol are heated at > 100”. H. L. WHITEHEAD. or dicyandiamide. H. L. WHITEHEAD.
Printing and pad-dyeing of fabrics of polyacrylonitrile.
Sandoz Ltd. (B.P. 791,294, 26.5.55. Ger., 11.6., 24.7.. 17.11. and
19.11.54. Addn. to B.P. 767,053; J.A.C. Abstr., 1958, i, 653).- Cellulose and Papor.
The cuprous ion method of the earlier B.P. for dyeing textiles of
homo- or co-polymers of acrylonitrile with water-sol. dyestuffs is Coating colours and coating processes for coated papers.
adapted for use in printing or pad dyeing. The fabrics are treated I(. Engel (Stdrke, 1962, 14, 179--185).-1n this review the following
with aq. printing pastes or padding liquors containing the dyestuff, are covered: the use of and characteristics of binders, e.g., on
either a compound yielding acid on heating (NH, sulphate or starch basis in coating pigments, use of synthetic dispersions with
phosphate) or a non-volatile org. acid (tartaric), and either Cu,O or starch and casein sizes, specific qualities of white pigments and
both a water-sol. CuII compound (sulphate) and an inorg. reducing behaviour towards binders, relation of different rheological qualities
agent (Cu powder, FeSO,,Ti1I1 sulphate or chloride, SnC1,) ; and in pigments and certain coating processes, printing qualities of the
the goods are thereafter dried at 60-70” and steamed at 104-130”. paper, value of coating in packing papers and cartons, resistance to
H. L. WHITEHEAD. water vapour, greaseproofing and flavour retention. E. M. J.
Pigments. Switzer Brothers Inc. (Inventor : 2. Kazenas) (B.P. Paper size from pine oleoresin. H. B. Summers, jun., and
792,616, 1.10.56. Addn. to B.P. 769,344, 11.11.54; J.A.C. Abstr., G. W. Hedrick (Industr. Elzgng Chem., Prod. Res.. 1962, 1, 56-59).-
1958. ii, 213).-Claim is made for fluorescent pigments or com- The study described has resulted in practical processes for the prep.
positions comprising a fluorescent dye incorporated in a co- of sizes, conventional and fortified, from pine oleoresin by partial
condensation product of an aromatic sulphonamide having a t least neutralisation of the resin acids in the oleoresin which obviates the
two reactive H-atoms (C,H,Me.S02NH,), an amide selected from silation of the resin before turpentine distillation. To obtain dry
urea. thiourra, dicyandiamide, guanidine, malonamide, biuret or sizes, both neutral and acid pastc sizes were dried in a ball mill
ii -43 I Ci.-FIRRES, Etc. ii-432

heated by an oil-bath and flushed continuously with an inert gas t o elcctrode with a fixcd platinum clectrode (illustrated]. The deter-
remove water vapour. 0. M. WHITTON. mination is carried out by reacting the ethanolic solution of acrylo-
nitrile with n-dodecylthiol and back-titrating the excess of thial
Paper pulp. M. G. Mackeurtan (B.P. 868,703, 7.8.57. S. Afr.* with 0.005 N-AgNO, when the end point is shown by appearance of
24.8. and 11.10.56).-1n the manufacture of paper pulp by digesting the diffusion current. The determination is not affected by the
grasses, straw or bagasse with weak aq. NaOH, the resulting black usual catalysts or H,SO, and has a relative error of ?0.4%.
liquor containing 4 1 pt. by wt. of Na,CO, and other Na salts per 1'. BRYCH.
4 pt. of NaOH (each on dry basis) is continuously withdrawn from Effects of cupric salts on the polymerisation of acrylonitrile
the digester, passed with lime Ca(OH), to a regenerating zone whcre in aqueous solutions. M. Watanabe and ti. Kiuchi (,I, Polynz.
the Na salts are convcrted to NaOH, and then returned to the process. Sci.. 1962, 58, 103-119).-NH4 persulphate was used as initiator
H. L. WHITEHEAD. in the presence of CuSO,, Cu(NO,), or Cu acetate; there was a
Waterproofing agents and processes. Catomance Ltd. pronounced increase in the polymerisation rate. CuCl, or CuBr,
(Inventors: M. Kohler, A. E. Read and J. David) (B.P. 869,952, retard or inhibit the polymerisation when used above an indicatcd
10.12.57).-The surfaces of absorbent materials (fibres, paper, wood, concn. Polymerisation of acrylonitrile can be initiated by CuSO,,
leather, etc.) are rendered water-repellent by treating them with a Fe,(SO,),, SnCl,, HNO, or HIO, but the decrease in rate can be
substantially neutral or alkaline aq. emulsion of a paraffin wax explained on the assumption that the complex of the Cu ion with a
which contains, dissolved in the wax phase, -5-15% of a water- halide, such as CuX,, CuX,, CuX, or Cu,X, shows lower activity in
insol. org. deriv. of TilV or %rlv and either (a) each metal valency the reaction with S,O,a-. The cupric-terminated reaction depends
is directly attached to a n alkoxy, hydroxyalkoxy, or acyloxy radical on the coexisting anion. The effect of the SO,", NO,-, acetatc,
(e.g., 2-ethylhexyl titanate) or (b) 3 of said valencies are so attached PO,,-, C10,- or F- ions is negligible and, while thc effect of the
and the 4th is attached to an oxygen bridge between two Ti or Zr C1- ion is marked, that of the Br- ion is very great. The CuX+ ion
atoms [e.g., (HuO),Ti.O.Ti(ORu),, a hydrolysis product of Bu ( X = C1 or Br) appears to terminate the polymer chain more
titanate]. H. L. WHITEHEAD. efficiently than does the Cuarl+f.(15 references.) c. v.
Alkaline polymerisation of caprolactam. V. Utilisation of
alkaline polymerisation for the production of massive objects
Plastics and Resins. from high-molecular poly-6-caproamide. J. KriliEelt, J.
~

Dependence of viscosity on the concentration of polymer Selicnda. 2. Zadik and 0. Wichterlc (Chew. Pmm., 1961, 11.
solutions. M. Kryszewski (Hocsn. Chem., 1961, 35, 1419-1428). 377-38l).-The study of reaction mechanism of the alkaline
Applicability was investigatcd of the Thomas's exponent equation polymerisation of caprolactam led to the development of a more
7) = ~ o . e [ V c ,where and 9,, are the viscosities of solvcnt and cffective catalytic system comprising the alkali (NaOMe) and
solution, respectively. The effects of mol. wt., the type of solvent AT-alkylimidcs(LN-acetyl-6-caprolactam)which increases the rate of
and the polymer concn. were studied i n various solutions of poly- polymerisation and, when carried out below the m.p. of the polymer,
methyl methacrylate and polystyrene. Detailed results are reported. results in formation of a massive block. The polymerisation reaction
I t is concluded that the equation is applicable only to polymers in can be controlled over a wide range to give a homogeneous polymer
the medium range of mol. wt., to relatively low concn. of solutions, with a low monomer content and lower stress, after contraction
and t o specially selected solvents. (34 references.) (In English.) (2-3% vol. depending on final temp.). The system is suitablc for
A . L. GROCHOWSKI. polymerisation in situ. M. JUNGR.
Flow behaviour of plastics in the roller jaws especially Polymerisation and copolymerisation of N-vinylpyridiniurn
with polyethylene. R. Rautenbach (Chew.-lng.-Z'ech,, 1962, 34, salts. I. N. Duling (Dissert. Abstr., 1961, 22, 1407).-N-Vinyl-
231-236) .-The flow behaviour of various polyethylenes in the nip pyridinium perchlorate and fluoroborate (I) polymerise readily in
(jaws) of rollers has been investigated theoretically and experi- the solid state or in solution in presence of y-rays from 6°Co. I gives
mentally. Polyethylenes of higher mol. wt. in the treatment a polyelectrolyte of mol. wt. 150,000 in solid-state polymerisation.
condition have to be considered as non-Newtonian liquids, the flow Homopolymerisation in solution is initiated by free-radicals :
behaviour of which can be described by the Prandtl equation. copolymerisation was only successful with Me methacrylate and
Starting from this law, an analytical treatment of the flow processes acrylate and acrylonitrile. G. MACKENZIE.
in the roller nip gives the relation between turning moment or
prcssure and roller peripheral velocity, some simplifications being Mechano-chemical polymerisation of methacrylamide in
taken. Without any simplifying assumptions, the valid resistance solid state. V. A. Kargin, N. A. Plat6 and Van Tsu6-Chzhu (Dokl.
can be derived in model experiments with the aid of the similarity Akad. Nauk S S S R , 1962, 142, 1312--1315).-1ntensive mechanical
theory. (15 references.) M. SULZBACHER. dispersion in a steel ball mill of cryst. methacrylamide (I) in presence
of NaCl, BaSO, or SiO, led t o partial polymerisation at 20". After
Determination of unreacted monomers in aqueous emul- 45 min., polymerisation was detected with only 0.005~0NaCl.
sions of interpolymers. P. Shapras and G. C. Claver (Analyt. Polymerisation reached max. of 10% with 0.5% NaCl catalyst but
Chem., 1962, 34, 433).-Monomers are separated on a 6-ft. decreased with increase of NaCl until with 80% NaCl i t ceased to
Chromosorb column containing 10% of stearamidopropyldimethyl- be detectable. Similar results were obtained with BaSO, in I and
P-hydroxyethylammonium nitrate. The gas chromatogram provides NaCl in I in presence of heptane. Max. polymerisation (48%) was
information on residual monomers and other impurities. found with 5% SiO, in I. Yield fell to zero with 20% SiO,. Both
C. B. BAINES. SiO, and NaCl also formed oligomers (dimer and trimer) of I in
Electrical surface properties of polymers containing increasing amounts as the yield of polymer decreased. With 80%
bound anionic groups. F. H. Holmes and P. G. Perkins ( J . appl. NaCl nearly 40% of I was converted t o oligomers. It is suggested
Chem., 1962. 12, 150--156).-Sheets of polystyrene, cross-linked that polymerisation and oligomerisation are independent reactions
with divinylbenzene, have been sulphonated with ClS0,H in the proceeding in parallel. Polymer was also formed in molten I at 120"
surface regions. Sheets incorporating carboxyl groups have been and at - 150' with liquid N, cooling. Polymerisation is attributed
prepared by copolymerising styrene, divinylbenzene, and methacrylic to electrons, arising from defects of type of F-centres in lattices of
acid. The electrical conductances of the polymer surfaces, with ionic salts, caused by mechanical forces. It can be inhibited by
sodium as mobile cation, have been measured in air at various R.H. adding hydroquinone during milling. With SiO,, previous work
The surface conductivity rises linearly with surface exchange suggests milling causes centres of radical type by rupture of Si-0-5
capacity and the slope of the curve increases rapidly with the R.H. bonds. P. W. B. HA'RRISON.
(12 references.) 0. M. WHITTON.
Adsorption of polymethacrylic acid from solution. G.
Resistance of insulating foils to soil micro-organisms. R. Lopatin (Dissert. Abstr., 1961, 22, 1423).-Polymethacrylic acid (I)
Keiter (Plaste u. Kautsch., 1961, 8, 407).-Changes in extensibility was adsorbed from aq. solution on t o hydroxyapatite and anatase.
and tensile strength of polyvinyl chloride and polyethylene foils on The adsorption was measured by following changes in n or by
treatment with Aspergillus niger and Penicillium brevicompactum turbidimetric titration with poly-4-vinyl-N-n-butylpyridinium
have been measured. L. A. O'NEILL. bromide solution. Adsorption on liydroxyapatite at pH values from
Amperometric determination of acrylonitrile during 5 t o 9 showed strong dependence on method of prep. of adsorbent
polymerisation. J. Majewska and S. Urbanowicz (Chem. Anal., and polymer. Strong multilayer adsorption or pptn. was due to mass
Warsaw, 1961, 6, 841-844).-The method of Beesing et al. (Analyt. action equilibria on basis of pptn. of I by dissolved Ca2+ ions.
C ~ O J L1949,
., 21, 1073) has been modified by replacing the rotating Adsorption on anatase was a function of p H and mol. wt. Affinity
ii-433 6.-FIBRES, Etc. ii-434
and capacity vary in the pl.l-range 1.0-3.8. The mol. wt. depen- with the formation of isotactic-I, trans-stilbene is formed. (19
dence of the capacity was moderate. Possible reasons are given. references.) c. v.
G. MACKENZIE. Polymerisation induced by ionising radiation at low
Low-temperature polymerisation of methyl methacrylate temperature : styrene and 2,4-dimethylstyrene. I. Evidence
initiated by ethyl silver. C. E. H . Bawn, W. H. Janes and A. M. for the simultaneous existence of ionic and free-radical
North ( J . Polym. Sci., 1962, 58, 335-350).-Free-radical poly-mechanisms. 11. Effects of change of phase and hetero-
merisation of Me methacrylate a t low temp. has been studied in a geneity. C. S. Hsia Chen and (I) R. F. Stamm) ( J . Polym. Sci.,
series of solvcnts of diffcrent solvent power and ability to form weak 1962, 58, 369-388 ; 389-409).-I. By initiating with ionising
complexes with the monomer. In every case, the polymer was radiation, styrene (I) and 2.4-dimethylstyrene (11) have been
predominantly syndiotactic which suggests that monomer associa- polymerised in the cryst. solid state (-80 to +25"). In solution
tion or complex formation are not the important stereoregulating polymerisation with the same initiation, the mechanism by which
factors and that the treatment of the propagation reaction as two these monomers polymerise is temp.-dependent ; at lower temp. a
concurrent addition reactions between monomer and a free cationic mechanism predominates but a t higher ones a free-radical
propagating species is justified. Polymerisation was studied over a mcehanism results ; in the intermediate range both function, but
temp. rangc of - 20 to - 60" using AgEt as initiator. Polymerisation in this range the electronic structure of the monomer is influential.
proceeds by a free-radical mechanism, the initiatory step being thc (32 references.)
decomposition of the AgEt-monomer complex t o form metallic Ag 11. With I in the solid state (temp. < -30.5"). the ratc of poly-
and a free radical which is capable of initiating polymerisation. The merisation increases with the temp. being max. when the system is
mol. wt. of the polymers formed are higher than would be predicted partially solid. The rate drops rapidly above the m.p. to a min.
by extrapolation from the data available for the higher temp. (22 and then rises in a normal manner with increase in temp. Wlth 11,
references.) c. v. in the solid monomer, the rate increases with the temp. having, like
Copolymerisation of pairs of olefins with sulphur dioxide I, a max. a t the m.p. when the system is a solid/liquid mixture.
in the region of the ceiling temperature. J . E. Hazel1 and K. J. Above the m.p., the rate drops very markedly but, as with I, there
Ivin (Trans. Farada.y SOC., 1962, 58, 342-349).--For olefins, M, and is a second increase in ratc with rise in temp. Similar effects have
M,, which form complexes with SO, the results obtained for the been observed in the polymerisation of I-benzene and I-PhEt
kinetics are best explained by a new mechanism in which radicals mixtures. (14 references.) c. v.
M,M,' and M,M,' are assumed to be capable of depropagation with Copolymerisation studies of radiation-induced polymeri-
rate constants in the ratio -0-6. E. C. DOLTON. sation at low temperatures. Y . Tsuda ( J . Polym. Sci., 1962, 58,
Protection of polyolefins against photo- and thermal 289-297) .-Copolymerisation of acrylonitrile (I) with styrene (11)
oxidation. W. L. Hawkins (Rubb. Plast. WRly, 1962, 142, 291, or Me methacrylate was carried out by y-irradiation a t low temp. in
293-294, 296, 299).-As a scrcen for U.V.radiation, the best results various solvents. Both anionic copolymerisation and free-radical
reactions wcre observed to proceed simultaneously ; when water,
are obtaincd with C-black (I). Untreated I are not good thcrmal alcohol or ester is present, the anionic polymerisation is inhibited.
stabilisers but reaction of I with S or 0,. activates the pigment so As the concn. of I1 increases, free-radical polymerisation is retarded.
that a concn. of 2-3%, suitable for light screening, is also efficient Fractionation of the 11-1 copolymer obtained shows that the
as a protector against heat. I is retained during evaporation or anionic radical of I formed by irradiation a t low temp. initiates both
extraction, when conventional protectants would be lost. The an anionic and free-radical copolymerisation. Thus the resultant
immobility of I makes C even more effective in the solid (semi- copolymer consists of a block of anionic copolymer attached to a
crystalline) polymer than would be expected from its ability to block of free-radical copolymer. c . v.
protect the molten (totally amorphous) polymer. (18 references.)
c. v. Radiation polymerisation of ethylene : evidence for ion-
Catalytic deposition and grafting of olefln polymers into molecule condensation. C. D. Wagner ( J . Fhys. Chem., 1962, 66,
cellulosic materials. D. J. Bridgeford (Industr. Engng Chem., 1158-1162).-C2H4 is polymerised by ionising radiation at - 196"
Pvod. Res., 1962, 1, 45--52).-Cellulose films and fibres were to give mono-olefinic, mainly branched polymers of low mol. wt.
improved by in situ polymerisation and grafting t o them of olefin Experiments with C,D, + C,H, showed that the initiating species
polymers, using ion-exchange-bonded metallic and non-metallic contains 4 H atoms. The structures of the products with 4, 6 and
catalysts or initiator components (e.g.. gel cellulose film with core- 8 C indicated that polymers arise from single activatjons of C,H,
bound Fe). Polymerisation time depended on the monomer, with multiple propagation, which occurs at either of the unsaturated
catalyst system and reaction conditions used. Batch or continuous C atoms, that no skeletal isomerisation occurs and that little
processes, lasting from several sec. to a few min. could be used. migration of I3 atoms occurs. Initiation is probably from the
Deposition was in surface layers when initiator was bound in surface C&+ ion, propagation by ion-molccule condensation and termina-
layers. Uniform grafting and core grafting were also obtainable. tion by electron combination. H . S. R.
(17 references.) 0. M. WIIITTON. Anionic polymerisation of ethylene oxide. T. J . Dudek
Graft polymerisation to cellulose by sodium periodate. C,,H,Na (Dzssert. Abstr., 1961, 22, 1407).-Initiation reaction between
T. Toda ( J . Polym. Sci., 1962, 58, 411-427).-It is shown that by C,,H,- and ethylene oxide (I)involves a nucleophilic attack on I
ion. With excess of I polymerisation takes place and
acrylic nionoiner can be easily grafted to cellulose (I)by NaIO, (11). polymers of any mol. wt. can be prepared by controlling the
The apparent activation energy of graft copolymerisation indicates monomer/initiator ratio. One polymer mol. was produced for every
that the polymer radical formed by the attack of I1 on I initiates two C,,H,Na mol. uscd. The polymers prepared possess a narrow
graft copolymerisation. The rate of the reaction increases with the mol. wt. distribution, and contain a central dehydronaphthalene
increase in reagent concn. u p to a certain value but at higher concn. structure with the polymer chain. Similar results are obtained using
I1 produccs more CHO groups and the grafted chains become
shorter while the number of graft-initiating points appear to remain CL0H7K.Polymerisation of I with Na gave a Na dialkoxide. G. MACKENZIE.
constant and independent of I1 concn. Studies of homogeneous Polyaddition products and their practical utilisation. A
polymerisation suggest that I1 does terminate the reaction of
growing polymer radicals, but when dialdehyde-I is prepared symposium. I. Epoxy resins. (Chimza, 1962, 16, 5 7 - 8 7 ) .
previously by oxidation with I1 and is grafted with Me methacrylate, Chemistry of epoxy resins. V. Reaction of epichlorohydrin
the grafted chain is shorter in the range of high aldehyde content. with bivalent phenols. [Kinetics of preparation of epoxy
This indicates that the CHO groups formed in I during grafting arc resins]. W. Fisch (pp. 66-71).--?2 mechanism of reaction between
likely to terminate the growing graft chains ; the chain-transfer cpichlorohydrin (I) and bivalent phenols in an alkaline medium is
constants for several sugars and alcohols with acrylonitrile as proposed. At a reaction temp. of 100" phenol is converted quant.
monoincr were measured : the constants for the sugars were always into epoxy resin whilst the conversion of I is incomplete. In a slower
higher than for the alcohols. (17 references.) c . v. side reaction, the unrcacted I is transformed into polyglycerol.
which explains thc previously unsatisfactory balance of I. A criticai
Polymerisation of styrene with n-butyl-lithium-titanium assessment of the various reaction rates shows that pure addition
tetrachloride catalysts. K. C. Tsou, J. F. Megee and A. Malateste reactions determine the rate. A kinetic expression for the poly-
( J . Polym. S c i . , 1962, 58, 299-309).-In this system, isotactic addition is derived, depending on the molar ratio of starting materials
polystyrene (I) is only obtained when the ratios are 3 . 0 2 LiBun/ and on the ratio of two rate constants.
TiC1, > 1.75. A t ratios < 1.75 and > 3.0 only amorphous I results. VI. Synthesis of new epoxy compounds. H. Batzer and E.
Mol. wt. of the amorphous fraction was determined. Concomitantly Nikles (pp. 57-66).-The different types of epoxy compounds are
ii-435 6.-FIBRE's, Etc. ii- 436

rcviewrtl : ( I ) glycidyl ethers, estcrs and amines ; (2) epoxidation TI. For styreno/acrylonitrile systems similar conclusions are
products ( 0 ) linear aliphatic epoxides, epoxidised fatty acids and rcached except that the ratio of the two cross-termination rate
derivatives, epoxidised polybutadienes. ( b ) cycloaliphatic epoxides. constants is 20. The large difference in the reactivity ratios of the
Conventional technical processes for the production of the cyclo- two monomers prevents the application of Arlman's equation to the
olefinic starting materials and various methods of their conversion vinyl acetate/acrylonitrile system. (15 references.)E. C. DnLTnx.
to the corresponding epoxides are discussed. The most important
procedures use peracids or HOCI. The prep. of organic peracids Activated initiation of vinyl polymerisation
from the acids or thcir anhydrides with H,O, and from the aldehydes carbonyls. C. H. Bamford and C. A. Finch (Proc. chem.
by oxidation with 0, is surveyed. Cured cycloaliphatic epoxides and 110-1 1 l).-Mixtures of metal carbonyls and halogen
their properties, dcpending upon their constitution, are considered.
'Technical application possibilities for two products are discussed.
Numerical data are compared with those of conventional epoxy
-
containing CCI, or CBr, groups initiate the free-radical polyrnerisa-
tion of Me methacrylate a t 100". Added CO incrcases the mol. wt.
of the polymer but decreases the rate of polymerisation, the effects
resins. (48 references.) being most pronounced at high and low concn. of carbonyl. The CO
VII. New fire-resisting epoxy resins. D. Porret and E. reacts with the initiator or some derived specics but not with the
Leumann (pp. 72-76) .---Fire-resisting or fire-proof epoxy resins as growing chains. E. C. DOLTON.
construction material have been produced by the introduction of I-' Preparation of high-concentration emulsions or polyvinyl
or halogens. Addition of phosphorylatcd or halogenated deriv. acetate resistant to frost. F. Gregor and E. PavlaCka (Chew.
which are non-active or contain only one epoxy group per mol. to Prdnz., 1961, 11, 381--383).-Polyvinyl acetate emulsions containing
conventional cpoxy derivatives gave resins having less favourable 50% of polymer prepared with mixtures of water and MeOH or
mechanical properties. Likewise the use of anhydrides of halogenated EtOH (-25:/0 of alcohol) can be stored at tcmp. of - 15" for up to
acids as hardeners gave fireproof resins with properties not so good 6 months without loss in quality or stability. M. J C J N G R .
as those made with conventional hardeners. New halogenated or
phosphorylated compounds containing two or more epoxy groups P.V.C. in plastisols. Methods of short-term stabilisation;
per mol. were made ancl hardened with acid anhydrides and amines, stability of viscosity with time. C. Corso and M. I3edcschi
giving incombustible resins. When mixed with conventional resins (Mater. plast., 1962, 28, 213--216).--Ageing of a P.V.C.-dioctyl
in proper proportions, they confer fireproof properties. The halogens phthalate (GO : 40) mixture is studied by viscometry by fall-time
and I' in the new products show good stability. Mechanical and and Brookfield rotating methods. In general, refining of thc plastisol
electrical properties of the ncw compounds were investigated. (In causes a slight variation in the rhcological propertics : after 7 days
French .) a definitive idea of the properties of P.V.C. compositions can be
Solvent-free epoxy resin systems for varnishes. J. J. obtained. C. A. FINCH.
Zonsveld (pp. 7(5-82) .-Thc advantages of solvent-free epoxy resin Dechlorination of polyvinylidene chloride. 1,. Tokarzewski
systems are cliscusscd with new formulations. The selection of (Roczn. Chem., 1961, 35, 1319-132 l).--Heating polyvinylidcnc
hardeners, determining t h e curing rate and minimum curing temp., chloride with a Na alkoxide in the corresponding alkanol a t tlic b.p.
is considered, Diluents for obtaining a sufficiently low viscosity need removed most of the C1 to give a black product. Thc ' polycumulcnes
not be bonded to the cross-linked macromolecule but are sometimes so obtained are chemically inert and do not gain in wt. when heated
chemically built into the molecule as ' reactive ' diluents. The in air. Mol. wt. dctermination was not possible bccause 01 insolu-
proportioning of monofnnctional cpoxy substances is discussed in bility. Studies of the products of HNO, oxidation arc in progress.
detail. Pigmenting and mixing with additives, methods of applica- 4. L. GROCHOWSKI.
tion by airless spraying a t high pressure, and practical experiences Developments in fluorinated polymers. J. von Schweinickcn
are reviewcd. (Muter. plast., 1962, 28, 221-229) .-Reccnt developments in
Epoxy resins as binders for vacuum-impregnated high- polymerisation of fluorinated olefins, and uses of the resulting poly-
tension insulations. I<. Blinnc (pp. 82-86) .-High-tension -mers are reviewed. Homo- and co-polymers of chlorotrifluoro-
insulations could be considerably improvccl by replacement of the ethylene, vinylidene fluoride, vinyl fluoride and hexafluorapropylcnc
binders shellac ancl asphalt by epoxy resins of such viscosity that arc described, commercial names listed, and methods of prep. given.
vacuum impregnation was possible. Although the qual. requirements Fluorinated elastomers are briefly considered. C. A . FINCH.
of the insulators can be met in principle, the temp. range of applica-
tion is limited by the properties of the resins. For higher temp., Acid-catalysed setting of phenol-formaldehyde resins.
resins have to bc taken which show also a suitable resistance against G. E. Little ( J . uppl. Chem., 1962, 12, 196-200).-The kinetics of
ageing. So far no rcsins are available which allow a continuous the self-condensation of 3,5-dimethyl-4-hydroxybcnzyl alcohol (I)
application a t tcmp. above 140". and of its condensation with 2.6-xylcnol are determined and
New aromatic epoxides. H. Hopff and R. Wandcler (pp. 86- mechanisms of reaction deduced. The rate of reaction rises as the
87).--The prep. of 2-epoxyethylthiophen, 44'-diepoxyethyldiphenyl p H falls and the reaction is second order and is controlled by alcohol
sulphide (I) and sulphone, 2.6-dicpoxyethyldiphenylenedioxide and dissociation which is facilitated by 0-9 directing groups situated o
3.6-diepoxyethyldibenzofuran is reported. Particularly reactive is or p to the CH,OH group. The reaction with I will occur a t pH 3
I which is converted into hard rcsins by fusing with diamines and but o-hydroxybenzyl alcohol requires p H 1.5. The setting of
phthalic anhydride. M. SULZBACHER. phenol-HCHO resins at room temp. is discussed. 0. M. WHITTON.
Phenylene sulphide polymers. 111. Synthesis of linear
Preparation of sequence copolymers of styrene-ethylene polyphenylene sulphide. R. W. Lenz, C. E. Handlovits and H. A.
oxide. G. Finaz, P. Rempp and J. Parrod (Bztll. SOC.chim. Fr., Smith (,I. Polym. Sci., 1962, 58, 351-367).--This compound has
1962, 262-266).--' Living ' polymers of polystyrene are prepared been synthcsised by the condensation polymerisation of alkali metal
in tetrahydrofuran with I< phenyl isopropyl and Na, a-methyl- salts of halothiophenols. The monomers investigated included Li,
styrene tetramer as initiators and these will copolymerise with Na and I< salts of p-bromothiophenols (I), Mass polytncrisatio~~i
ethylene oxide. Copolymers are isolated and described. The reverse were carried out below the m.p. of the salts and a solid-state xeaction
copolymerisation is not possible but is effected by preparing o-poly- appears to be involved. Kate measurements wcrc made on the
styrylcarbonyl chloride by the action of excess of COCI, on ' living ' polymerisation in pyridine and on a model of the propagation
polystyryl anion and reacting the acid chloride with polyoxyethylene reaction; in both cases the order of reactivities for the Na salts
glycol. The products contain a proportion of polymerised ethylene were, I- > Rr- > F- N C1-. In the polymerisation reaction, the
oxide, the ' living ' polystyrene polymer acting as an initiator for rcactivity of the alkali metal salts of I was I< < Na < Li. Com-
this reaction. E. J. H. BIRCH. parison of the polynicrisation rates and model reaction showctl that
Vinyl copolymerisation. I. Copolymerisation of acrylo- the reactivities of all thc functional groups was cssentially the sanic
nitrile with [I] methyl methacrylate and [11] styrene and for the Brand I derivatives but in the case of the C1 and 1; derivatives
vinyl acetate. M. Suzuki, H. Miyama and S. Fujimoto (Bull. the polymer chain end-groups were more reactive than the mono-
chem. SOC.Japan, 1962, 35, 57-60, 60-63).-The copolymerisation mers. This effect. preferential polymer formation, has been verified
rates for various acrylonitrile/methyl methacrylate mixtures were in the polymerisation of Na p-fluorothiophenoxide, but complete
measured by the thermistor method. Termination constants for control of the side reactions which lead to chain termination has not
mixed radicals are larger than those for homogeneous radicals. The yet been achieved in these condensation polymerisations. Linear
rate constant for normal cross termination is -10 times that for polyphenylene sulphide is kinetically stable in air and N, up to 400".
cross termination of the type -.4B.+ .A-. (13 references.) In N, a residue forms which represents -507; of the original wt. of
E. C. DOLTON. polymer; this is kinetically stable up to 900'. (25 references.) C. V.
ii-437 G.-FIBRES, Etc. ii-438
Synthetic resins. XII. The furans. H. 1’. Preuss (Metal of a basic catalyst. fn an csample, ClC0,Et is added a t 0---5” to a
Finish., 1962, 60, No. 3, 63--65).-The use of furfural and furfuryl mixture of 2-aminophenyl vinyl sulphide, ether and aq. I<,CO, to
alcohol compounds for resins is discussed and commercial applica- give Et (o-uinylt~~iophen3,1)carbamate,b.p. 100--106°/0~1 mm., in
tions are given. Such coatings have limited applications, but have 62y0 yield. F. R. BASFORD.
good resistance to chemicals and cure to an infusible solid state black
in colour. Plaster of Paris impregnated with them is stronger and Unsaturated thioureido ethers. IZohni & Haas Co. (B.P.
when cured has a dark wood-likc appearance. C .H. COWPER-COLES. 839,856, 3.7.56. U S . , 15.7.55. Addn. to B.P. 747,184; J.A.C.
Abstr., 1957, i, 317).--A vinyl aminoalkyl (1-4 C) ether (the amino
Inorganic polymers based on titanium. W. M. Giffen, jun. group may be substituted) is interacted with a (substituted) thiourea,
(Dissert. A bstv., 1961, 22, 1399).-A copolymer was successfully isothiocyanate or (di-N-substituted) thiocarbamoyl chloride to afford
formed with siloxy and titanoxy groups by condensation of bis- vinyloxyalkylthioureas. The products are useful as fungicidal or
(cyclopentadieny1)titanium dichloride (I) with diphenylsilanediol bactericidal agents for incorporation into the coatings for textiles,
(11). Fractionated copolymers with cryoscopic no. average mol. wt. as intermediates for production of isothiouronium salts to be used
of 15,000 were formed after 2-3 days a t 70-75” in prescnce of as antistatic agents, and as modifiers for aminoplast resins, N N -
pyridine and CaC, as drying agent. Addition of I1 to I must be very disubstituted deriv. are useful as oil additives. The thioureas
slow, and the mixture must finally be condensed by boiling with polymerise in presence of SO, to yield products of low mol. wt.
conc. C,H, solution. The mechanism of reaction is discussed. which contain SO,, or in presence of azo catalysts. The polymers are
G. MACKENZIE. also useful as bactericides and confer bettcr waterproofing properties
than the monomers. Copolymers with other ethylenic monomers
Producing fireproof plastic material and the fireproof may also be made. In an example BunSCN is treated in C,H, with
plastic materials obtained therethrough. A. A. Samuel (B.P. 3-aminoethyl vinyl ether to give N-n-butyl-N’-vinyloxyethyl-
810,551, 6.6.55. Fr., 8.6.54. Atldn. to B.P. 721,706; J.A.C. Abstr., thiourea, an active insecticide and bactericide. The methosulphate
1955. ii, 243).-In order to obtain polyester or polyester/poly- is an antistatic for nylon, etc. The polymerised compound is
styrene or polystyrene resin plastic materials which arc completcly similarly useful as the monomer and can be used as a crosslinking
non-inflammable (without causing hardening or embrittlcment of agent for phenol-formaldehyde resins. E . ENOS JONES.
the plastic material), the process of the earlier B.P. is modified by
using the hexahaloethane or other perhalogen compound in amount Polymerisation of vinylidene cyanide. B.F. Goodrich Co.
+ 10% of the total wt. of the reaction mixture, together with $- 100; (B.P. 870,195, 27.1 1.57. U.S., 20.12.56).-A process for polymerising
of a combustion inhibitor [metallic (Sb) oxide, resin-sol. Sb compound, vinylidene cyanide in a substantially anhydrous diluent medium
tritolyl phosphate]. H. L. WHITEHEAD. which is a solvent for the monomeric vinylidene cyanide but which
is a non-solvent for the polymer, comprises maintaining the electrical
Organic peroxides. Farbwerkc Hoechst A.-G. (B.P. 870,118, conductivity of the medium a t a value of at least 5 x lo-’ mho by
23.8.57. Grr., 23.8.56).-Compounds CR1llRIVXCK’R~O,H, useful adding a strong acid electrolyte (H,SO,, ClS0,H. CH,CICO,H) and
as catalysts in polymerisation, are obtained in good yield by inter- agitating the medium while polymerisation is proceeding, the
action of olrfins of the general formula CR’lZ”:CRII1RIV with reaction being conducted in an electrically grounded (preferably all
livO,H in presence of a hypohalitc a t -30” to +50° in an inert metal) reaction vessel. E. ENOSJONES.
solvent (R’-RIV are hydrocarbon or heterocyclic groups, or It’
and HIL1 may form part of a hydroaromatic nucleus or may be Continuous polymerisation process of acrylic salts. Hohm
connected t o an aromatic nucleus with formation of a condensed & Haas Co. (B.P. 869,333, 13.1.60. U.S., 23.1.59).-An aq. solution
hydroaromatic nucleus, of $- 3 of the R’-R1v may be H : R is alkyl, containing 20-500/, by wt. of a mixture of 5-50 pt. by wt. of Ca
cycloalkyl. aralkyl or heterocyclyl of $- 20 C ; RV is straight- or acrylate and 95-50 pt. of an NH,, water-sol. amine, or alkali metal-
branched-chain alkyl of $- 20 C , cycloalkyl, aryl, or substituted aryl). salt of acrylic or methacrylic acid, and 0.2-3% of NH, or alkali
Thus. ButOCl is added during 8 h. a t - 15” t o -20’ to a mixture of metal persulphate as initiator, is deposited as a thin film on a heated
pent-2-ene and ButO,H, then after warming to room temp. the travelling surface (a drum) of temp. 100-150°, and the film is
product is distilled, to give a peroxide of b.p. 33-37’/0.9 mm. The carried on the surface for 5 sec.-2 min. t o copolymerise the salts
N

compound may be used in the polymerisation of CH,:CH.OAc. and form a water-sol. dry polymer salt. H. L. WHITEHEAD.
F. R. BASFORD. Methyl methacrylate-containing syrups. E.I. Du Pont de
Polyoxamides. British Celanesc Ltd. (Inventors : J. Lincoln Nemours & Co., Assee of W. H. Calkins, E. N. Squire and M. S.
and I<. D. Grice) (B.P. 870,057, 19.6.57).-Claim is made for a Ziegler (B.P. 870,191, 4.11.58. U.S., 5.11.57).-CH,:CMe~CO,Me.
quaternary ammonium deriv. of a linear polyoxamide of the alone or in conjunction with another vinyl monomer, is heated
following recurrent structure : (at 50-150”) in presence of a chain transfer agent, e.g., a thiol
-OC.CO.NII.(CH,)n~NR.(CH,),~NH- where n is 2-4 and R is (I’hSH) (0.05-1 mo1.-%) and a polymerisation initiator, e.g.,
an alkyl group of > 3 C or CH,Ph. In an example Et, oxalate is Bz,O,, (:N.CMe,.CN), ( <300 p.p,m.) until the reaction mixture has
heated with bis-(3-aminopropyl)methylamine and the product bulk viscosity of 0.5-50 P and the polymer has inherent viscosity
quaternised with CH,PhCI. E. ENOSJONES. of 0.25-1, then polymerisation is stopped by adding a cold solution
Liquid curable synthetic resins. Dynamit Nobel A,-G. (B.P. of a polymerisation inhibitor (quinol, 0.001-1 wt.-%) in a monomer.
869,184. 2.9.58. Gcr., 14.9.57).-.4n amino-triazine (e.g., melamine), There is thus obtained a polymer-in-monomer syrup, containing
an aliphatic or cycloaliphatic ketone (e.g., acetone) and an aldehyde < 2 0 p.p.m. of initiator, suitable for moulding a t high temp., to
(e.g., formaldehyde) are condensed in an aq. medium under alkaline produce laminated articles of good weathering, stiffness, and craze-
conditions. E. ENOSJONES. resistant properties. I;. R. BASFORD.
N - Substituted polyamides. Baclische Anilin- u. Soda-Fabrik Polymeric anhydrides and acyl halides. B.F. Goodrich Co.,
A,-G. (B.P. 869,079, 3.7.59. Ger., 5.7.58).-Idactams of u-amino- Assee of J . 17. Jones (B.P. 869,867, 11.1.60. U.S., 15.1.59. Addn.
carboxylic acids with 8-13 ring members (caprolactam) and which to B.1’. 834,357 ; J.A.C. Abstr., 1961, i, 500).-Polymeric anhydrides
are substituted on the N-atom by an alkyl group (Me,Et), or an and polymeric acyl halides of ap-unsaturated carboxylic acids are
alkenyl group containing only one ethylenic double bond, the total prepared by reacting a salt of (CH,:CR.COO)nM where K is H or a
number of C-atoms in the substituent being 1-6. are heated a t 200- lower alkyl group, n is 1 or 2 and M a n alkali metal, an alkaline
300’ in the presence of neutral or acid polymerisation catalysts. earth metal, Mg or Be, with a carbonyl halide of the formula
E . ENOSJONES. X,(CO)b where b is 1 or 2 and X is C1 or Br, and polymerising the
Vinyl compounds. Rohm & I-Iaas Co. (B.P.834,575,6.7.56. U S . . product in the presence of a free-radical initiator. In a n example
15.7.55. ildtln. to B.P. 763,636: J.A.C. .4bstr., 1958, i, 393).-Vinyl anhyd. Na acrylate is treated with COCl, in hexane and the product
esters of thc type (CH,:CH~S~II~NR~CO,),R” are claimed ( R is polymerised in presence of Bz,O, a t 50” in N, t o give a polyacrylic
o-phenylene, p-phenylene, or ZCRl*’RIV : Z is alkylene of 1-7 C ; anhydride. The product of the first reaction may be copolymerised
1t*II and Rlv are alkyl of 1-4 C : R’ is H or hydrocarbyl ; R” is with the corresponding acid chloride. E. ENOSJONES.
monovalent or divalent residue of a mono- or di-hydroxy compound Polymerisation. Union Carbide Corp. (Assignors : J. F.
according to whether n is 1 or 2 ) . They may be obtained by treating Erdman and C. R. Welter) (B.P. 870,043, 25.3.60. U.S., 20.4.59).-
CH,:CH.S.TI.NHIZ’ with a halogenocarbonate in presence of an acid- Ethylene alone, or in admixture with other polymerisable olefinically
binding agent. The compounds are useful as plasticisers for resins unsaturated compounds, is heated a t 160-250”/15,000-100,000
and stabilisers for P.V.C. and may be copolymerised with other vinyl p.s.i.g. in the presence of a catalyst mixture comprising 20-500 mol.
compounds to give thermally stable products. In cases where R‘ is of 0, and 1-100 mol. of But,O, per million mol. of ethylene.
H the esters arc converted into isocyanatcs when heated in presence E. ENOS JONES.
ii -439 ii-440

Copolymers suitable for use as primers. American-Marietta Polymeric compositions. Imperial Chemical Industries Ltd.
Co. (B.P. 869,459, 20.1 1.59. U.S., 9.12.58).-The monomers used (Inventor : I). J. Guest) (B.P. 870,287, 5.11.58).-Claim is made for
consist essentially of vinyltoluene, acrylonitrile, and, optionally. aq. dispersions of vinyl acetate and vinyl propionate polymcrs and
acrylic, or methacrylic or itaconic acid. The proportions used are copolymers, characterised by the presence therein of 0.5-8~0% by
shown on an area of an accompanying diagram. The copolymer has a wt. of amylopeetin (calc. on the total dispersion) and by the absence
relative viscosity measured a t 25" in a 1 g./lOO ml. solution in of > 5% by wt. of amylose (calc. on the amylopectin content).
tlimethylforinamide of 1.4-3.5. The products are useful as primers E. ENOSJONES.
for binding vinyl resin plastisols or organosols to a ferrous metal base. Polymers. Farbwerke Hoechst A.-G. (B.P. 869,429-30, 28.2.58.
E. ENOSJONES. Ger., 28.2.57).-In a process for polymerising an unsaturated
Derivatives of ethylene-maleic anhydride copolymers. polymerisable compound (especially vinyl chloride) capable of being
Monsanto Chemical Co. (B.P. 870,398, 4.10.57. U.S., 4.10.56).- polymerised in a n aq. phase with an emulsifier, the emulsifier used
Claim is made for an estamide of an ethylene--maIeic anhydride has the formula [A] R,.[CH,] .*CO-OR,, [B] R,.[CH,]!L.C~.CO.R,
copolymer in which the anhydride groups have been substantially where R, is alkyl of 6-25 (8-14) C, I Z is 1-4 and R, IS SO,I-I or
fully esterified, substantially fully amidated or partially esterified and PO,H,. The polymerisation is completed by known methods in the
partially amidated until the copolymer chain is substantially free p H range 3-7, and the emulsifier is finally decomposed into
from anhydride and carboxyl groups directly attached thereto. At surface-inactive components by shifting the p H t o < 3. Examples
least a part of the esterifying or amidating groups contain ( a ) cited are [A] sulphoacetic acid lauryl ester and [B] lauric acid
ethylenic or acetylenic unsaturation, (b) if esterifying groups, a t isethionic acid ester. E . ENOSJONES.
least one frce OH, NH,, COOH, CN, epoxy or sulphonic acid group
or a halogen atom, (c) i f amidating groups, a t least one primary or Organotin compounds and compositions containing same.
s-amino, OH or COOH group, or a haiogen atom, the esterifying or Metal & Thermit Corp. (B.P. 797,113, 31.1.56; addition to I3.F.
amidating groups being derived from monomeric alcohols, phenols 719,733 ; J.A.C. Abstr., 1955, ii, 244).-Dibutyltin-SS'-bis-(2-ethyl-
or amines. A long list of agents is given. E. ENOSJONES. hexylmercaptoacetate) and -bis(iso-octylmercaptoacetate) arc useful
as stabilisers for halogen-containing synthetic resins, particularly
Polymerisation. Union Carbide Corp., Assee of C. H. Madge vinyl halide resins. The deriv. are obtained by interaction of
and R. Nagel (I3.P. 870,480, 8.3.60. U.S., 28.4.59).--Solid chain- SnBu,O with the appropriate inercaptoacetate (prepared from the
terminated copolymers are produced by heating, a t 100--350°/ alcohol and SH*CH,CO,H in toluene). I. JONES.
15,000--100,000 p.s.i. in the presence of a free-radical catalyst, a
polymerisable mixture comprising ( a ) ethylene, (b) 0.05-1.5 m o l . - ~ o [A] Chloro-substituted organic sulphonyl fluorides. [B]
of a t least one alkyl (1-12 C) acrylate, and ( 6 ) as chain terminator, o-Chloropolyfluoroalkanesulphonyl fluorides and derivatives
a saturated 3-114: aliphatic ketone, an 1-8-C alkanol or 1-olefin thereof. Minnesota Mining & Mfg Co. (B.P. 869,921-2, 18.6.57.
containing 3-10-C. One mixture used is C,H,, E t acrylate and U.S., 18. and 29.6.56).-[~] Chloro-substituted org. siilphonyl
propylene. E. ENOSJONES. fluorides, especially those of formula Cl(CRRl.CHR2) .-SO,]; (where
Polymerisation. Union Carbide Corp., Assee of W. L. Smith and R, R1and Ra are H or alkyls and n is 1-15), are made by reacting
C. R. Welter (B.P. 870,481, 8.3.60. U.S.. 23.4.59).-Solid, fjexible S0,FCI (I) (preferably at 25-200°) in presence of a free-radical
homopolymers are produced by heating ethylene and a 1,2-alkylene initiator (eg., But,O,) (11) with an olefinic compound that is
oxide containing 2---4 C-atoms a t 170-210"/1500--10,000 atm. in copolymerisable with SO, (e.g., ethylene, vinyl chloride or bromide).
the presence of 0, as catalyst. E. ENOSJONES. [B] By similarly reacting I in presence of I1 with a polyiluorinatetl
olefin that is copolymerisable with SO, (e.g.. tetrafluoroethylcne)
Polymers from propylene. Standard Oil Co. (B.P. 820,727, new w-chloropolyfluoroalkanes are obtained which have the skeleton
31.8.55. U.S., 15.10.54. Addn. to B.P. 734,501 ; J.A.C. Abstr., Cl*(C.C).*SO,F (where the valencies on the C are satisfied by H, F or
1956, i. 607).--R propylene polymer having d of t o - 9 0 and a C1 and t 2 of them are satisfied by F. and n is 1-150). The new
mcthylene to short-chain allcylidene ratio of between 1 and 2, is compounds are useful as intermediates for making water- or oil-
separated from a propylene polymer which has a Staudinger specific repellants and foaming agents ; and they yield the corresponding
viscosity x 106 of 4: 10,000 (as measured on a solution of 0.5 g. of sulphonic acids and their metal and NH, salts and acid chlorides and
the polymer in 100 nil. of xylenes a t 110") by dissolving the polymer sulphonamides by reactions (described) on the SO,F group.
in hot xylene, cooling the resultant solution to -25" and separating H. L. WHITEHEAD.
the precipitated polymer. E. ENOSJONES. Polymers derived from phenolic novolacs and unsaturated
Linear polypropylene and copolymers of propylene with acetals. Union Carbide Corp., Assee of J. E. Wilson and H. I<.
other olefins. Parbwerke Hoechst A.-G. (B.P. 870,392, 27.6.57. Walton) (B.P. 869,658, 19.12.57. U.S., 27.12.56).-A process for
Ger., 27.6.56).-1n a process for improving linear polypropylene or making a heat-hardenable resin comprises reacting a phenolic-
copolymers of propylene with other olefins produced by the low- novolac resin having more than two reactive positions in the mol.
pressure process, the polymer or copolymer is subjected to partial with an unsaturated acetal. e.g., 3,9-divinyl-, 3,9-di-isopropenyl-,
degradation by heating it in the presence of air a t 10-20' a.bove the 3.9-dipropenyl- and 3,9-bis-(1-chloroviny1)-spirobis-(m-dioxan).
crystallite m.p. for 1-60 min. E. ENOSJONES. E . ENOS JONES.
Graft copolymers. B.X. Plastics 1,ttl. (Inventor : I?. R. Smith) Polymers of mono-epoxides. Petrochemicals Ltd. (Inventors :
(13.E'. 870,052, 25.1.57).--~~.4
graft copolymer is made by subjecting F. H. Newth and J . D. Shimmin) (B.P. 870,418, 12.6.S9).--The
cellulose triacetate ( > 950/) to ionising radiation while in contact polymcrs are produced by polymerising a monomeric epoxy com-
mith styrcnc monomer (>50,;). E. ENOSJONES. pound R.CH-CH.R, where R is a (substituted) hydrocarbon radical
Polymers from selected steam-cracked distillate streams.
Esso Research & Engng Co. (B.P. 784,938, 26.4.54. U.S., 20.5.53.
'd
or H, or both K's may form a substituted or unsulistitukd t:)-clo-
hddn. to B.P. 743,886 ; J.A.C. Abstr., 1956, ii, 477).--Kesinous oils aliphatic ring, in the presence, as catalyst, of a compound formccl
or resins are produced by distilling a steam-cracked petroleum by reacting a polyhydric alcohol and a n A1 or hlg alkyl, aryl,
fraction boiling a t 18-54"c from a steam-cracked petroleum alkoxide or aroxide or a halide of such metal organic compound. In
product, maintaining the fraction in a dimerisation zone a t a temp. an example the catalyst used for polymerisation of ethylene oxide is
a t which cyclopentadiene dimerises, separating substantially all the compound obtained by interaction of Al(OI'ri3) or EtSIgBr with
dimerised cyclo-diolefins from the fraction, and polymerising the ethylenc glycol with 10% by wt. of ZnC1, as co-catalyst.
remainder in the presence of a FriedelLCrafts catalyst a t -20" to E. ENOSJONES.
150"~. I. JONES. Polyoxyalkylene compounds. Shell Research Ltd. (Inventors :
Cross-linking of polyvinyl alcohol. Th. Goldschmidt 11.4. J . C. M. G. Ellis, E. J. Hayward and A. C. Houston) (B.F. 870,457.
(B.P. 870,438, 12.1.60. Ger., 31.1. and 25.2.59).-Polyvinyl alcohol 33.12.57).-Polyoxyalkylene compounds of low ash content are
is subjected to the action of cyanuric chloride in an alkaline medium prepared by condensing an org. compound with at least 1 OH,
a t >looo (>120°). E. ENOS JONES. CO,H, SH, or primary or s-amino group (monobutyl ether of
Polyvinyl ester compositions. Farbwerke Hoechst A.-G. ethylene glycol), with a n alkylene oxide in presence of an alkaline
(B.P. 869,094, 28.7.58. Ger., 27.7.57).-Claim is made for a fusible catalyst, then neutralising with acid, and subsequently treating the
composition having a low viscosity in the molten state, which neutralised mixture with a low-mol. aliphatic alcohol or glycol, and
comprises a polyvinyl acetate and/or a polyvinyl propionate in filtering off any suspended matter. The desired product may then
;idmixturc: with octadecanediol. E. ENOSJONES. be recovered from the filtrate. 1;. R. UASPORD.
ii-44 1 6.-FIBRES, Etc. ii-442
[B-F] Alkylene oxide polymers and [A, G , H] stabilisers mol. of a t least one dialkyl (I-- 4 C) ester of terephthalic acid with
therefor. Union Carbide Corp., Assee of [ A , c, E, F] F. N. Hill, 0.667-2.0 mol. of at least one polyhydric alcohol a t least 40% by
[B-F] F. E. Bailey. jun., [D] W. A. Denison, [e,F] J. T. Fitzpatrick, wt. of which is an alcohol having a t least 3 reactive OH-groups
[ C , H] I<. 1,. Smith (B.1'. 869,111-8, [A] 24, [B-F] 28.5.57, [G, H] (glycerol+glycol), in the presence of 0-005-2.0./, by wt. of at least
19.6.57. G.S.. [A-F] 29.5.56, [ G , H] 20.6.56).-[11, F] Alkylene an esterification catalyst comprising a metal salt selected from
oxides, specifically [D] ethylene oxide or [B, c] copolymer of the linoleates, resinates, naphthenatcs, acetates, benzoates, octoates,
latter with $ 50% of another alkylene oxide, are polymerised, [D] salts of tall oil acids and stearates, of metals selected from Al, Ca,
in presence of a diluent (aromatic hydrocarbon, a phenyl ether, etc.), Cs, Cr, Co, Cu, Fe, Pb, Mn, Ni, Sn, Ti, V, Zn and Zr.
with a catalyst comprising an alkaline earth metal [B-D] carbonate E. ENOSJONES.
(especially SrCO,), or [c, D, E] deriv. of an org. hydroxy compound Polycondensation of the ethylene glycol diester of tere-
(alkoxide) which has been treated with CO, and water so that its phthalic acid in the molten state. Vereinigte Glanzstoff-
wt. has been increased by 3 7 0 % . or [F] amide or hexammoniate. Fabriken A.-G. (B.P. 790,456, 4.6.56. Ger., 4.6.55. Addn. to B.1'.
The stabilisers used are [A] a tetra-N-substituted ethylenediamine, 755,166 : J.A.C. Abstr., 1957, ii, 360).-Ethylenc glycol split off
especially with P-hydroxy-ethyl or -propyl groups [e.g., iVNN'N'- during the condensation is removed by passage through the melt of a
tctrakis-(2-hydroxyethyl)ethylenediamine]. [GI propyl gallate, [HI hydrocarbon (paraffin, benzene) a t 250-320" (280"), counter-
phenyl-P-naphthylamine, polymerised trimethyldihydroxyquinoline currently to a current of the melt. E. ENOSJONES.
or N-nitrodiphenylamine. E. ENOSJONES. Polycondensation of diglycol terephthalate. Vcreinigte
Polyether compositions. Imperial Chemical Industries Ltd. Glanzstoff-Fabriken A.-G. (B.P. 806,934, 11.7.56. Ger., 8.8.55.
(Inventor : F. G. Jeffers) (B.P. 869,096, 21.8.58).-Polyethers are Addn. to B.P. 720,120 ; J.A.C. Abstr., 1955, ii, 245).-The conden-
stabilised against oxidation by the addition of up t o 5% by wt. of sation is cffccted in liquid phase in the presence of a solvent of b.p.
an antioxidant-a 2-u-alkylcycloalkyl-4,6-dimethylphenol,or a 180-245" which forms an azeotrope with glycol t o remove i t from
bis - (2 - hydroxy - 3 - u - alkylcycloalkyl - 5 - methy1phenyl)methane the mixture. Specifically the solvent has a naphthalene nucleus or
wherein the alkyl group has + 4 C-atoms and the cycloalkyl group two directly or indirectly linked benzene nuclei, which may be
has 5 or 6 C atoms in the ring. E. ENOSJONES. hydrogenated or substituted. Examples are u- and P-methyl-
Curing of polyepoxides. Bataafse Petroleurn Maats. N.V. (B.P. naphthalene, biphenyl, diphenyl ether and diphenylmethane.
869,484, 29.6.59. U.3.. 30.6.58).--In an improved method for curing I. JONES.
polyepoxides-which yields insol. and infusible products of good Polytetramethylene terephthalate. Imperial Chemical Indus-
impact resistance without loss of heat resistance-a polyepoxide tries Ltd. (Inventors: W. R. Burton and N. Standring) (B.P.
containing 4: 1 epoxide group per mol. (a glycidyl polyether of a 798,187, 3.12.54. Addn. to B.P. 740,381 ; J.A.C. Abstr., 1956, ii,
dihydric phenol having 1-2 epoxy groups per mol.) is mixed and 253).-To obtain high-mol. wt. fibre-forming polytetramethylene
reacted a t 50-200' with 0.02-0.4 mol. per epoxide equivalent of terephthalates by polycondensation at elevated temp. of bis-(8-
an N-(aminoalkylpiperazine whose alkyl contains $4 C, e.g., N- hydroxy-n-butyl) terephthalate (I), the polycondensation is effected
aminobutylpiperazine, as hardening agent. H. L. WHITEHEAD. in presence of a catalyst consisting of 0.01-0.037/, of a compound
(fluoride or oxide) of Sb which is sol. in the reaction mixture,
Epoxy-modified water-soluble alkyd resin. Rinshed-Mason preferably together with 0.05-0.075~0 of a reaction mixture-sol.
Co. (B.P. 870,412, 28.4.59. U.S., 28.4.58).--The reaction product, compound (acetate) (11) of Zn, and the reaction is conducted at
acid no. of 2-80, obtained by reacting (1) a partial ester of a <260". I is preferably made by ester cnchange reaction between
monocarboxylic acid (fatty acid) and a glycidyl polyether of a Me, terephthalate and 1.4-butanediol in presence of 11, I1 remaining
dihydric phenol, with ( 2 ) a polyhydric alcohol (2-hydroxymethyl-2- in the product to give its beneficial effcct in the ensuing poly-
methylpropane- 1.3-diol) and a polycarboxylic acid or anhydride condensation. H. I,. WHITEHEAD.
(phthalic anhydride), is treated with a neutralising agent consisting
of an aliphatic amine or NH,(NEt, or P-dimethylaminoethanol). Polymeric unsaturated ester or polyester resins. Farben-
E. ENOSJONES. fabriken Bayer A.-G. (B.P. 869,298, 2.10.57. Ger., 3.10.56).-The
Mesityl oxide copolymers. Bataafse Petroleum Maats. N.V. resins are produced by heating, in the absence of a polymerisation
(B.P. 869,750, 23.4.59. U S . , 25.4.58).--The copolymers are catalyst and while excluding 0,, at least one up-unsaturated
prepared by heating a diethylenically unsaturated hydrocarbon (e.g., dicarboxylic acid or ester-forming deriv. thereof (maleic anhydride),
butadiene) with mesityl oxide. The products are suitable for lining and a t least one monohydric ether alcohol having at least two
cans. E. ENOSJONES. ethylenic double bonds in py-position t o the cther 0 (trimethylol-
propane diallyl ether), until a product is formed which is still soluble
High molecular weight, thermoplastically workable poly- in aromatic hydrocarbons, acetic acid esters and ketones.
oxymethylene derivatives. Farbenfabriken Bayer A.-G. (B.P. E. ENOSJONES.
869,323, 24.1 1.59. Ger., 25.1 1.58).-The deriv. arc produced by Curing of interpolymerisable mixtures. Pittsburgh Platc
reacting polyoxymethylenc, with an inherent viscosity of 4: 1.0 Glass Co. (B.P. 842,900, 15.1.57 ; U S . , 9.3.56. Addition t o B.1'.
measured in a 0.5% p-chlorophenol solution at Goo, with an ortho- 768,957, 29.9.54; J.A.C. Abstr., 1958, ii, 12O).-A method of
cster of a carboxylic acid (Et orthoformate) in combination with an accelerating the organic peroxide-catalysed polymerisation of a
acidic catalyst, preferably Lewis acid catalyst (BF,-tetrahydrofuran) mixture of (A) a polyester of a glycol and an up-ethylenically
or with an alkyl cster of a polyhydroxy mineral acid (Me,SO, etc.) unsaturated dicarboxylic acid, and (B)a monomeric vinyl compound,
in solution or dispersion, a t room temp. to 160". E. ENOSJONES. the mixture containing, as a gelation inhibitor, 4: 0.01 yo by wt. (of
Curing a glycidyl polyether. Shell Internationale Research the polyester) of quinone or dihydric phenols, comprises adding to
Rlaats. N.V. (B.P. 869,969, 30.7.59. U.S., 1.8.58),-0~1-30~0~0 by the mixture 4: 0.001 % by wt. of an amine salt (e.g., pyridine hydro-
wt. of a trihydrocarbyl phosphite of the formula (RO),P (e.g., chloride) concurrently with or subsequent to the addition of the
Ph,PO,) is used as a curing agent for a glycidyl polyether with an peroxide catalyst. E. ENOS JONES.
epoxy equivalency > 1.O. E. ENOSJONES. Resin compositions which are self-extinguishing when
Linear copolyesters. General Electric Co. (B.P. 870,095-6, cured. U S . Rubber Co. (B.P. 870,331, 31.3.60. US., 21.5.59).-
31.7.58. U.S., 22.8.57).-The products arc made by interaction of a The compositions comprise 100 parts by wt. of an unsaturated
tlihydric compound (especially bisphenol A) with a polybasic or polyester and a copolymerisable ethylenically unsaturated monomer
hydroxy carboxylic acid and a dihaloformate (COCl,) in presence of mixture (e.g., diethylene glycol maleate/styrene mixture) and 175-
a t-base (pyridinc). Acids uscd include adipic, phthalic acids, 400 parts of CaS0,,2H20. E. ENOSJONES.
salicylic acid, etc. E. ENOSJONES. Copolyesters. Imperial Chemical Industries Ltd. (Inventors :
Polyester resins. Imperial Chemical lndustries Ltd. (Inventor : A. A. B. Browne and J. Mather) (B.P. 869,964, 5.11.58).-Copoly-
K. B. Smith) (B.P. 870,278, 26.3.58).-Claim is made for a resinous esters with the structural component - O.OC.R.PO(OX).R'.COO -,
polyester of terephthalic acid and/or isophthalic acid with a saturated where R and R' are org. linkages and X is a cation, are made by
aliphatic triol (glycerol), ethylene glycol and propylene glycol copolymerising the diol (ethylene glycol) esters of a n aromatic
containing l0-50% excess 013-groups in which the molar proportion dicarboxylic acid and a carboxy-substituted phosphinic acid, e.g.,
of triol to diols is 2 : 1 to 1 : 3, and of ethylcne glycol to propylene bis-(p-carboxypheny1)phosphinicacid, both prepared by inter-
glycol is 5 : 1 to 1 ; 2. E. ENOS JONES. esterification, the latter in presence of X halide. E. ENOSJONES.
Polyester resins. Westinghouse Electric Corp. (B.P. 870,088, Organosilkon compounds. General Electric Co. (B.P. 870,024,
21.4.58. U.S., 24.4.57).-The resins arc prepared by reacting one 22.7.59. U.S., 15.8.58).-The polymers arc produced by reacting a
ii443 B.~-FIBXES, Etc. ii-444

(SiMc,CI,) with a diiiietIiyldi-(~~-lialoplie~iyl)-


tlitrietli~l~lilialc~silane Adhesives.
silanc and thcn hytlrolysing and condcnsing the reaction product.
E. ENOSJONES. Neoprene contact adhesives : some special advantages
Fluorine-containing silanes and their hydrolysis products. and production applications. D. J . Kelly (,4d/tesivrs Age. 1962,
Miclland Silicones Ltd. (I3.1'. 802.358, 14.2.56. U.S., 14.3.55. Addn. 5, No. 2, 22-25).-The ability to retain adhcsivc power for many
to 13.1'. 760,201 ; J.l\.C. Abstr., 1958, i, 174).-Vinylsilanes years, to resist temp. and moisture changes and maintain adequate
C:H8:CHt<,LSiY3-rb (li is saturatcd monovalent hydrocarbon residue, holding strength in various uses is discussed and the views of some
11 is 0-2) arc intcracted with a perfluoro mono- or di-ethylcnic or a of the major manufacturers arc expressed. c . V.
monochloropcrfluoro compound (C,F,, p,erfluorobutddienc, l-chloro- Structural variables affecting electrical properties in epoxy
hcptafluorobutene) a t < 125" (ISO') to glve a cyclobutylsilanc dcriv. adhesives on steel. I,. Ng Ty (Dissert. i2bstv., 1961, 22. 1431-
1n an example, pcrfluorobutenc with vinylmcthyldichlorosilane a t 1432).-Changes in dielectric constant, dissipation factor and
150" under pressure in 24 h. gives a mixture of 2- and 3-perfluoro- dielectric loss factor a t 20 V and 0*1--100 kc/s for steel laminates
cthylcyclobutyl(mctl~yf)dichlorosilane,which is hydrolysed to a bonded by polymer adhesives are due to thc rotational freedom of
copolymer of thc corresponding siloxancs. E. ENOSJONES. the dipoles which depend partly on the structure of the polymers.
Rotational movement can be affected by the adhesive-adherand
Organosilicon liquids. Midland Silicones Ltd. (13.1'. 870,007, interface. When surface/vol. ratio of organic film is large, the
4.11.59. U.S., 2. I .59).---'The oxidation stability of silicone com- contribution to dielectric absorption and dispersion are not masked
positions stabilisetl with l;e salts is furthcr improved and the by structural effects in the plastic. increase in dielectric kiss factor
formation of unwanted ppt. a t high temp. avoided, by preheating is caused by increased cross-linking of the polymer, accompanied by
the silicona-Fc salt mixturc a t 200" in presence of 0, until the loss of adhcsion a t the interface. The method may be used to find
mixture will not lorm a ppt. when heated a t a higher temp. in the effect of cross-linking on the quality of adhesive joints.
absence of [I2. The preferred l'c salt is derived from a carboxylic G. MACKENZIE.
acid of 4---I8 C (octoate). I;.R. BASFORD. Blending adhesives for high-speed photographic film. Anon.
(,4dheszues Age, 1962, 5, No. 2, 28-29).-A method is described for
Grafting olefins on to organosilicon compounds. llidland mixing precise quantities of cach component, where one component
Silicones Lttl. (13.P. 869.482, 15.6.59 U.S., 18.8.58).--Thc process is incompatible with other individual components. c. v.
compriscs contacting with 0, a t > 30" an organosilicon compound
in which c0.001 mol.-n(, of thc Si-atoms have unsaturated non- Composite structures and vinyl acetate copolymer adhesives
aromatic hydrocarbon radicals attached thereto by C-Si linkages for use therein. British Celanese Ltd. (Inventors E. Crampscy,
(96 mol.-y; of dimcthylsiloxane+ 4 mol.-;i of methylvinylsiloxane), D. Grady and 1'. R. Hawtin) (B.P. 869,071, ll.1.57).-Claini is made
any remaining valencies of the Si-atoms being satisfied by saturated for a composite structure comprising a film of a thermoplastic
(halogenated) hydrocarbon radicals (R), 0-atoms of an Si-0-Si cellulose ester or ether bonded t o a printed surface by mems of an
linkagc, halogen atoms or -OR groups. The compound is thcn adhesive having a basis of a copolymer of vinyl acetate 35-50%
treated a t >30" with an olefinic compound of i12 C having a and a dibutyl malcate (65-50% by wt.) optionally with a plasticiser
terminal group CX,:C= in which X is 13 or halogen (acrylonitrile, therefor (I'h,PO,). E. ENOSJONES.
\;inyl chloridc. etc.). €2. ENOSJONES.
Catalytic process for the reaction of organic isocyanates Drying Oils and Paints.
with hydroxyl group-contafning substances. imperial Chemical
Industries Ltd. (Inventor : H. J . 'Twitchctt) (I3.i'. 869,988, 25.4.58). New approach to epoxy varnishes. S. H. Richardson and
--Thc reaction of org. isocyanates with OH-containing compounds W. I. Wertz (Ofl..Dig. Fed. SOC.Paint Technol., 1961, 33, 1310-
to form urethanes is catalysetl in improved manner by 0.025-50/, 1319).-Epoxy ester varnishes similar to those from solid epoxy
on the reactants of a complex of a @-ketonewith Mn, Th, Ti or Zr, resins, but offering greater latitude in formulation, may be preparcd
':.g., Mn bis(pcntane-2,4-dione) (prep. described). A basic reaction by reaction of a liquid epoxy resin (essentially the diglycidyl ether
accclcrator (t-amine) may also be prcscnt. H. 1. WHIT~WEAD. of bisphenol A), bisphenol A and drying oil fatty acids in presence
of an alkaline catalyst (Li naphthenate). Initially the epoxy groups
Condensation products. Farbenfabriken Bayer A,-<;. (B.P. react with the carboxyl groups to form monoesters, and then
869,997, 29.7.59. Ger., 30.7.58).--Wigh-mol. products are obtained residual epoxy groups react with the phenolic hydroxyls. If the
by intcraction oi one or more mono- and/or poly-isocyanates in proportions of ingredients are selected a resin of definite average
prescnce of an acid catalyst with one or more org. compounds chain length can be prepared. Properties of varnishes prepared in this
containing one or more groups of the general formula OCH,X (X is way. e.g., for exterior exposure, or as can coatings, have been
C1 or Br). The prcfcrrcd reaction temp. is 120-200". Thus, a mixture examined. L. A. O'NEILL.
o f Ac.CH,CI and lit;,cthcr complex (I) is added during 7-8 h. a t Universal resin plant. I . E. Rubin (Paint Vavn. Prod., 1962,
150" in abscncc of watcr to PhNCO containing I, then unchanged 52, No. 1. 67-71).-The use of a chlorinated biphenyl heating
I'IiNCO is distilled off in u m u o , to leave a highly viscous residue. medium in plant for nmnufacturing a wide variety of resins,
1;. R. B.4SFORD. particularly alkyd resins is described. L. A. O'NEILL.
Olefin-sulphur dioxide copolymers. E.1. L)u Pont de Nemours
tiz Co. (E.1'. 870,080. 11.10.57. U.S., 1.11.56).--The copolymers are Alkyd resins. E. Sunderland (Fri'vg och Lach, 1961, 7, No. 5,
produced by polymcrising o m or more olefins in the presence of an 118--136).--A method for expressing the constitution of alkyd resins
aq. medium containing a frce-radical catalyst and SO,E-I2- ions in in terms of two parameters, based on the number of moles of
sufficient proportions a.ncl at such pH as to provide SO, available for monobasic acid and of dibdsic acid anhydride per mole of Folyhydric
copolymcrisation a t a SO,/olcfin mol. ratio of < 1 : 1. alcohol, is suggested. The relationship with other methods of
E. ENOSJONES. cxpression and the derivation of the average esterification func-
Chemically modified starch product. A. E. Staley Mfg Co. tionality are considered. L. A. O'NEILL.
(B.1'. 869,501, 26.2.60. [J.S., 13.3.59).-A granular unpasted Curing of pigmented polyester resins. H. Niesen (Dtsch.
amylaceous material (starch) is treatcd (2 pt., c.g.) with a vinyl FarbenZ., 1961, 15, 515-519).-The effect of a range of white,
compound (prefcrahly an acrylate or methacrylate of an alkanol black, green, red, yellow and blue pigments and extenders on the
or aminoalkanol, or Cli,:CH.CN or acrylamide (1 pt,, e.g.) in hardening of a styrene/unsaturated polyester resin has been
prescncc of an oxidising catalyst, an activator thcrefor. and a solvent examined. Many pigments seriously retard the curing.
comprising 10% of water. to give a graft polymer. The products are L. A. O'NEILL.
uscful in adhesives, textile iinishing. textile sizing, flocculation, etc. Surface hardening of a polyester resin in air at ordinary
F. R.BASFORD. temperature. H. Scherzcr (Plaste u. Kautsch., 1961,s. 401-403).-
Co-cured rubber and reinforced resin. Esso Research & The effect of various factors on the surface hardening of an un-
Engng CO. (B.P. 869,163, 16.12.58. U.S., 14.1.58).-A unitary saturated polyester resin have been examined. Hardness could be
composition is made by curing together (dicumyl peroxide is the improved by increasing the proportion of curing catalyst (cyclo-
specified catalyst) a rubbery copolymer of hutadienc with acrylo- hcxanone peroxide--cobalt), addition of NI'hMe,, addition of wax,
nitrile or styrene, neoprene or natural rubber with a (glass) fibre- ur raising the curing temp. L. A. ~ ' N E I L L .
reinforced (co)polymerof a conjugated diolefin of 4-6 C (butadiene) Oxygenated solvent additions to hydrocarbons. Los Angelcs
or a polyester. E. ENOSJONES. SOC. for Paint Technol. (Amer. Paiizt J . , Coizv. Daily, 1961, 46,
ii-445 B.-FIERES. Etc. ii-446
No. 14, I,$--- 22).--The effect of various classes of oxygenated solvents cured products may be highly alkaline and require either an alkali-
(alcohols, esters, ketones, ethers, etc.) on the solvent power of hydro- resistant paint or a special primer beneath an oil paint. A comparison
carbons for a short-oil soya alkyd resin has been studied, using the has been made of 11 primers, subsequently coated with a chrome
non-volatile content of a solution of 1 Stoke viscosity as a measure of green oil house paint, the painted panels being placed for 6 or 24 h.
solvency. The oxygenated solvents had much greater effect with on water-soaked sponges. Chlorinated rubber or polystyrene-
mineral spirits than with an aromatic naphtha or toluene as expected butadiene resin primers of 3.5:); pigment vol. concn. gave good
from consitlerations of solubility parameter. Their efficiency with results, but emulsion based primers of similar pigmentation and
toluene was greater the lower their 7, but with mineral spirits the alkyd-based primers were inadequate. An oil-based primer gave
reverse. Within any one class the relative efficiency with toluene was surprisingly good results and the performance of the topcoat on an
the reverse of that with mineral spirits. L. A. O’NEILL. unprimed surface was better than expected. In these cases some
Determination of the oil content of organic coatings by gas protection by sacrificial saponification forming soaps which seal the
chromatography. W. L. Zielinski. jun., W. V. Moseley, jun., and substrate seems to be involved. In other cases the impermeability
R. C. Bricker (Riv. ztal. Sostanze grasse, 1962, 39, 9--14).-The fatty of the primer as well as alkali-resistance is the important factor.
acid composition of unmodified natural oils may be determined by L. A. O’NEILL.
gas-chromatographic examination of the Me esters. When drying High-temperature-resistant organic coatings. M. A. Glaser.
oils are incorporated into resins, e.g., alkyds, such that the unsatura- R. E. Caplan and R. W. Clope (Off. Dig. Fed. SOC.Paint Technol.,
tion of the fatty acids is not appreciably modified, the composition 1961, 33, 1197--1214).-Silicone coatings with a high level of heat-
of the oil component may be determined. Where the unsaturation and corrosion-resistance can be produced. and uses of coatings with
is modified, e.g., by reaction with hydrocarbons or maleic anhydride, white, aluminium or black (ceramic) pigments for aircraft or missiles
this cannot be done, but it is possible to determine the unreacted are described. Silicone coatings for wire-wound and conductive
polyunsaturated acids. With polynierised oils the yo of poly- oxide-coated resistors have good dielectric strength and water
unsaturated acids on the total non-polymerised acids may be rcsistance and are finding increasing usage in the electronics field.
obtained. L. A. O’NEILL. For resistance t o alkali, stainless steel is preferable to A1 for pigmen-
tation of silicone coatings, but the latter gives better resistance to
Dimerised fatty acids. L. 1;. Byrne (Off. Dig. Fed. SOL.Paint water, salt-spray and acid. Possible application of polymers con-
Technol., 1962. 34, 229-249) .-The mechanism of formation of taining other elements, e.g., F, B, P etc., in heat-resistant coatings
dimerised fatty acids by thermal treatment of unsaturated fatty are considered. L. A. O’NEILL.
acids, and applications of the products are discussed. A new process
for producing the acids consists in thc heating of partly conjugated Use of urethane coatings in industrial maintenance. M.
unsaturated fatty acids, e.g., dehydrated castor oil fatty acids, or Bailey (Paint Znd. Mag., 1961, 76, No. 10, IO--15).-The reactions
acids (e.g., castor oil fatty acids) which form such conjugated acids occurring in the formation of the various types of polyurethane
in situ at the polymerising temp. L. A. O’NEILL. coatings, viz., the chain extension and cross-linking reactions, the
reactivity of various compounds with isocyanate groups, and the
Drier catalyst activity of 1,lO-phenanthroline in organic action of catalysts and inhibitors, are discussed. L. A. O’NEILL.
coatings : lowering of the activation energy. G. K. Wheeler,
W. H. Canty and R. R. Myers (Industv. Engng Chem., Prod. Res., Determination of the permeability to water of a paint film
1962, 1, 52--56).-The overall activation energy for the drying of on a substrate. B. Persoz (Peint.-Pigm.-Vern., 1962, 38,64-68).-
alkyds is reduced by normal Mn dricrs and further reduced i f the From the measurement of the rate of absorption of water by a paint
metal is complexed with 1,lO-phenanthroline (I). Addition of I has film on an impermeable (metal) substrate, it is possible t o derive the
no effect on the activation energy of non-catalysed drying. The coeff. of diffusion and the max. water absorption of the film, The
trends in steric and energetic factors are consistent with the proposed permeability of the film may be obtained from the product of these
mechanism of drying wherein the substitution of an 0 mol. on the two values. L. A. O’NEILL.
a-C atom is enhanced by presence of an ionic oxidisable species. (16 Zinc-rich paints, particularly from highly dispersed
references.) 0. M. WHITTON. lamellar zinc. L. Kluth (Farbe u. Lack, 1961, 67, 208-217).-By
Methodics of pigments density estimation. F. KaSpar and using the optimum proportion of binding medium with regard to the
V. ForSt (Chem. Prdm., 1961, 11, 390-391).-According to the sp. surface of the pigment and the cathodic protective action of the
national standard the d of pigments is determined in a pyknometer metal, i t is possible to prepare paints from lamellar Zn equivalent
by immersion in white spirit and evacuation of adsorbed air. A new to those from Zn dust. The stability of Zn paints, and their resistance
method renders evacuation unnecessary by addition of 0.2% of of hard settling and to blistering in underwater coatings may be
surface-active agent (Duomeenc TDO) to the white spirit. The new improved by incorporation of a proportion of lamellar A1 pigment.
method is more accurate than the national standard. M. J U N G R . L. A. O’NEILL.
Evaluating the effect of exterior exposure on emulsion
Pigment identification. W. Lawrence (Paint Ind. Mug., 1961, polymer films. R. W. Reiter (Austral. Paint J., 1961, 6, No. 4,
76, No. 10, 7).-The identification of pigments by spot tests, visible 1 I-IS).-The degradation on exterior exposure of detached films of
or infra-red spectrophotometry and microscopically is discussed. vinyl acetate and acrylic polymers and copolymers has been followed
L. A. O’NEILL. by measurement of intrinsic 7,acetone-insol. content and physical
Glass transition in coating formulations. H. Burrell (08.Dig. properties. The acrylic resins showed marked 7 decrease with slight
Fed. SOL.Paint lechnol., 1962, 34, 131--161).--The significance of fall in insol. content indicating polymer degradation, in contrast to
the glass-transition temp. of polymers and its relation to solution q, the vinyl acetate resins which showed little change in q but increase
solvent release, hardness, adhesion, sp. vol. effects, elasticity, in acetone-insol. L. A. O’NEILL.
specific heat, n, permeability and electrical properties are considered.
(75 references.) L. A. O’NEILL. Film-forming agents in acrylic emulsion paints. R. W. S.
Burrell (Paint Technol., 1961, 25, No. 11, 15-17, 44).--Properties
Factors affecting patterns in hammer finishes. North- improved by the addition of film-forming aids to (acrylic) emulsion
western SOC.for Paint Technology (Amer. Paint J . , Conv. Daily, paints are dirt retention, low-temp. film coalescence, colour and
1961, 46, No. 13, 22-31).-Thc requirements for a hammer finish sheen uniformity, water-spotting resistence and durability ; stability,
are a volatile solvent which produces a vortex effect on evaporation, odour and pigment dispersion may be adversely affected. The
and a medium which sets up rapidly without secondary flow which relative effects of different film-forming aids, e.g., hexylene glycol
would destroy the pattern. Silicone additives function by dispersing and butyl carbitol acetate, have been examined, particularly in
into small particles which repel the surrounding medium and h l respect to effects on the tensile strength of the films. Water-miscible
pigment producing the effect. l’he effect of spraying technique and and water-immiscible aids may each show advantages in certain
27 on the pattern, and thc performance of a variety of resinous media, respects. Toluene is useful as a secondary solvent, e.g., in combina-
including, styrenatecl alkyd, vinyltoluene copolymer, chlorinated tion with butyl carbitol acetate. L. A. O’NEILL.
rubber, polystyrene-butadiene, acrylic, polyurethane, epoxy-ester Five-year exposure study of emulsion paints. Philadelphia
and nitrocellulose have been examined. L. A. O’NEILL. SOC.for Paint Technology (Amer.Paint J . , Conv. Daily, 1961, 46, No.
Asbestos cement substrates and their requirements. New 13,34-39).-The exterior durability of paints based on emulsions of
York SOC.for I’aint Technology (Amer. Paint J., Cunv. Daily. 1961, polyvinyl acetate (small or large particle size), externally plasticised
46, No. 13, 8--22).-The different types of asbestos cement product (with dibutyl phthalate or resinous plasticiser) ; vinyl acetate
are indicated. Autoclaved asbestos-cement products are of low copolymer ; acrylic resin ; styrene-butadiene copolymer ; and
a.lkalinity and can safcly be painted with most paints. Normal polystyrene (plasticised) ; at pigment vol. concn. of 25-40%
ii-447 7.-LABORATORY .1PPARA?'US A N D TECHNIQUE ; UNCLASSIFIED ii-448

(TiO,-n~ica-.kalc). on 9 difiexent substrates have been compared. with an alkali. In an examplc BF, etherate in water is heated a t 70"
'l'hc pcrforinance tended to be specific for each substrate and no with slow addition of epichlorohydrin, and the product treated with
singlc cmulsion gave a paint with overall superiority. NaOH after addition of ether. The epoxy ether obtained is mixed
L. A. O'NEILL. with the diglycidyl ether of bisphenol A and dicthylenetriamine to
give a film-making product which is very hard when baked a t 120".
Pigment. American-Marietta Co. (B.P. 869,091, 23.6.58. U.S., E. ENOSJONES.
26.6.57).-AI flakc is brought into contact with an aq. solution Modified cyclohexanone resins. Howards of Ilford Lttl.
containing H,I'O, or an NH,, alkali, alkaline earth, Zn and/or Mg (Inventors : V. F. Jenkins, C. Richardson and R. J . Wicker) (T3.P.
salt of H,1'0, in an amount sufficient to provide an available 869,467, 12.3.57).--,4 cyclohexanone-methanol or alk.ylcyclo-
PO,+ content cqual t o +0.7 ( > 1.5) wt.-yo of the A1 flake powder hexanone-methanol resin containing OH-groups is esterified with an
and having pH 1.5-11 (2-9.5). Thc wet pigment flakes are stable aliphatic or aromatic carboxylic acid or anhydride, acid chloride or
in presence of water. J . M. JACOBS. ester (phthalic anhydride, oleic acid). When a dicarboxylic acid is
used, the product may be esterified with pcntaerythritol to give an
Daylight fluorescent compositions and pigments for use in alkyd suitable for use in paints. E. ENOSJOXES.
same. Lawtcr Chemicals Inc. (B.1).870,357, 26.1.59. U.S., 11.6.58).
-Therc is claimed a daylight fluorescent composition (for use in the Fluorinated silanes and slloxanes. Midland Silicones Ltd.
production of inks, paints, etc.) comprising a daylight fluorescent (B.P. 869,343, 26.2.59. US., 24.4.58).-New silanes
material (e.g., a Rhodamine) and a resinous base formed by the C,F2,+,*Y,Si(H)X, (where n is 2-18. Y a divalent aliphatic
co-condcnsation oi an aryl (toluene) sulphonamide and an aldehyde radical containing a n ester, ether, amine or amide linkage,, K is a
(c.g., formaldehydc) and a benzoguanamine ( c1 pt. per pt. of divalent hydrocarbon radical, there being a total of < 1 8 atoms
sulphonamide) and an aldchyde. F. R. BXSFORD. excepting H in Y and R, m is 0 or 1, and X is H or halogen or a
monovalent hydrocarbonoxy or halohydrocarbonoxy radical) are
Stabilised aluminium paste pigments. English Metal Powder obtainable by reacting an olefin containing the perfluoro group with
Co. Ltd. (Inventor : G. W. Wendon) (B.P. 869,957, 26.8.58).-Al a silane HSiX, at elevated temp. (with a catalyst, e.g., Pt). They
pastc pigment is stabiliscd against loss of leafing power by incor- yield on hydrolysis (preferably under acid conditions) new :siloxanes
poration of 0.03-104 of o-crcsol, or 0.03--2% of a mixture of which contain < 4 8 % by wt. of F, consist essentially of
p-toluidine and o-cresol, based on tlic wt. of the paste pigment. C,,F,,+,.Y,Si(H)O units, and are useful for providing coatings
J . M. JACO5S. that are repellent to both oil and water. H. L. WHITEHEAD.
Organic compounds of titanium and zirconium. National
Icead Co. (I3.P. 786,388, 2.11.55. U.S., 9.11.54. Addn. to 13.1'. Stable aqueous emulsions of polymers which can be cross-
755,728 ; J.A.C. Abstr., 1957, ii, 341).-TIic compounds claimed are linked by oxidation. Farbenfabriken Baycr A.-G. (B.P. 870.015,
the titanatc and zirconatc esters of aminoalcohols characterised by 16.4.59. Gcr., 16.4.58).-The emulsions of polymers are produced
4: 2 N atoms linked through a divalent alkylene group and having by copolymerising (i) 2-50y0 by wt. of an ester of the P-ethylenically
between them a P-hydroxyalkyl substitnent and a t least one other unsaturated carboxylic acid and a saturated aliphatic or cyclo-
P-hydroxyalkyl or P-aminoalkyl substituent. The compounds are aliphatic alcohol having one alcoholic OH-group and a t least one
usually sol. in water and common org. solvcnts and are used as ethcr 0-atom (3-methoxybutyl acrylate), in an aq. emulsion with
dispersing agents and as additives to paint and varnish formulations. (ii) 98-5O0L by wt. of a further ethylenically unsaturated monomer
N,VN'N'-tetrakis-('L-hydroxypropyl)ethylenediamine orthotitanate (butadienc) while in contact with a redox catalyst system.
is prepared. J. M. JACOBS. E. ENOSJONES.
Pigmented artificial resin lacquers dispersible in aqueous
media. CIBA Ltd. (B.1'. 870,460, 18.2.58. Switz., 18.2. and 29.5.57).
-An inorg. pigment other than C black is dispersed in a lacquer,
7.-LABORATORY APPARATUS AND TECHNIQUE;
containing a hardenable water-sol. etherified methylol-amide which
forms an aminoplast with CH,O, and an org. solvent with very low Isotope effect in vapour pressures. I. B. Rabinovich (Usp.
solubility in water. An emulsifying agent (I), sol. in water and the Khim., 1962, 31, 101--152).-The review contains information on
solvent (especially ethylene oxide condensate of a water-insol. vapour pressures of monatomic isotope materials, those associated
compound containing active H ) is added. One example is ultra- and not associated with direct hydrogen bonds, and of diatomic
marine blue dispersed in a cyclohcxanol (11) solution of a urea- materials. Part two gives calculations and interpretations of isotopic
CH,O condensatc etherified with I1 and 2-ethylhexanol. The I is effects. (268 references.) A. L. B.
the condensation product of hydroabictyl alcohol with 15 mol. of
ethylene oxide. E. ENOSJONES. Microdetermination of carbon and hydrogen using non-
dispersive infra-red and thermal conductivity analysis. J. A .
Pigments comprising sulphonamide-aminotriazine-form- Kuck, J. W. Berry. A. J. Andreatch and P. A. Lentz (Annlyt. Chen?..
aldehyde resins. Switzer Brothers Inc. (I3.P. 869,801, 16.9.58. 1962, 34, 403-407).-The sample ( - 2 mg.) is burned in a stream
1J.S.. 11.6.58, Rddn. to U . P . 769,344, J.A.C. Abstr.. 1958, ii, 213).- of 0, and the issuing gases passed over CaH, and collected in motor-
The pigment comprises a dye incorporated with a finely divided operated syringes to a predetermined vol. CO, (and CO if desired)
thermoplastic resinous condensation product of ( A ) a t least one aryl is measured by i.r. absorption and H, by thermal conductivity after
monosulphonamidc having two reactive 13-atoms attached to N removal of CO,. or. R. ANDREW.
(toliienesulphonamidcs) with (€3) a diamino-1.3.5-triazine or a C-
alkyl, -aryl or -aralkyl deriv. thereof (2-phenyl-4,6-diamino-1,3,5- Determination of powder moisture by azeotropic distilla-
triazine), and (C) formaldehyde, or with an alkanol modified niethylol tion and near-infra-red spectrophotometry. H . Brandenberger
derir. of the aminotriazine. The products have improved light- and H. Bader (Analyt. Chem., 1961, 33, 1947--1949).-After azeo-
fastness. E. ENOS JONES. tropic distillation of the moist sample with dioxan. water is deter-
mined by spectroscopy at 1.91 p. The deviation on a 2 g.-sample is
[A] Interpolymers ; [B] modified resins. Balm Paint Prop- & 0.02y0. P. D. PARR-RICHARD.
rietary Ltd. (l3.P. 869,144-5, 14.2.58. Austral., 14.2.57).-A vinyl Magnetic mixer for liquids. G. B. Alewine and C. I<. Nicholsou
copolymer containing CO,H groups is reacted with a partial ester (U.S. AtomicEnergyContm.Rep., 1962, No. Dl37O4,8pp.).-f\n appara-
of a polyhydric alcohol with [A] an unsaturated, [B] a saturated tus based on a reciprocating magnet was devcloped for mixing multi-
fatty acid. I n examplcs a Me mcthacryiate-methacrylic acid phase liquids sealed in glass tubes. Two models were inade : ( a )
copolymer is hcatcd with thc trans-esterification product obtained one designed for general laboratory work mixing liquids in twenty
from glycerol and [ A ] linseed oil or [ u j coconut oil in prcscncc of 15-mm. tubes simultaneously and being suitable for immersion in a
PbO. The products form tough, glassy films when baked on to liquid-filled constant-temp. bath and ( b ) a type which takcs eight
tinplate. E. ENOSJONES. 15-mm. tubes and which can be rcmote operated so that irradiated
Epoxy ethers. Bataafse Petroleum Maats. N.V. (B.P. 870,365, materials can be studied. The operation of these is desc,ribed.
16.3.59. U.S., 17.3.58).-An epoxy ether of the formula c . v.
XO.fCHRCH(RCH-Y).O],,X where one X is an epoxyalkyl radical Thermocouple materials. F. R. Caldwell (U.S. nat. Bur.
and the other is a halohydroxy-substituted alkyl radical or epoxy- Stand. Monogr., 1962, No. 40, 43 pp.).-A review with 128 references
+
alkyl radical, Y is halogen, K is H or alkyl and is 2, is produced of thermocouples for use at 0" and upwards, their limitations,
by treating a halo-epoxy-substituted alkane with a condensation accuracy, chemical behaviour and physical properties. Ceramic-
catalyst in the presence of watcr, and then treating the product packed thermocouples are also covered. G. MACKENZLE.
ii-449 7.--LABORA?'ORY APPARATUS A N D TECHNIQTJE I. UNCLASSIFIED ii-450

Mercury porosimeter for nuclear-graphite studies. M. Application of a spectrophotometric analytical technique


Bocquet, J. Cenisson and J . Sailleau (Rapp. Cent. Et. nzicl. Saclay, in a kinetic study. G. A. Holder (Analyst, 1961, 86, G77-679).-
1961, No. 2093, 44 pp.).--In the apparatus and procedure described When i t is desired to confirm that only two absorbing substances
(based on capillary depression) the Hg pressure is increased stepwise are present as a reaction proceeds (e.g., in kinetic studies) it is shown
to a max. of 1000 kg./sq. cm. t o yield pore distribution curves mathematically that the absence of a n interfering product is estab-
(Y = 92 p-75 A) for graphite-cokes. The pore structure of bitumen- lished if the graphs obtained by plotting the ratio of the extinction
impregnated nuclear graphites depends largely on that of the coeff. against the ratio of the final to the initial extinction a t several
original coke ; in general, large-pore vol. decreases and small-pore wavelengths remain consistently linear as the reaction proceeds.
vol. increases. Graphites of equiv. porosity but different structures The application of the principle to the photodecomposition of diethyl
have differing permeabilities. Other parameters (nature of bitumen peroxide is described, the other absorbing produFt being acetalde-
and coke, degree of impregnation) also influence the porosity curves. hyde. A. 0. JONES.
((23references.) W. J. BAKER. Steady-state distribution : new instrument for continued
Thermosiphon as simple circulating pump for gases. D. van batchwise separation by extraction. F. C. Alderweireldt
der Auwera and R. A. Back (Canad.J . Chem., 1962,40,385-387).- (Analyt. Chem., 1961, 33, 1920--1924).-The multistage extractor
'The thermosiphon consists of cold and hot arms (at temp. T and T') described provides continuous separation of binary mixtures, but
formed by two vertical parallel Pyrex tubes (-2 m. x 25 mm.) permits withdrawal of samples for analysis. The apparatus was
joined a t the top in a U-bend and a t the lower ends to the circulation tested with cresol mixtures and with the a-acids of hops.
system, e.g., two long U-traps and photolysis cell. Thermistor P. D. PARR-RICHARD.
measurements on N, and CH, a t 20-760 mm. pressure (P)show Determination of point of equivalence in potentiometric
lhat a t low P and flow-rates ( F ) there is a linear relation between F acid-base titrations. K. V. Grove-Rasmussen (Dansk Tidsskr.
and P, T-1-T-1 and A l / v ( M = mol. wt.). By varying T' and thc Farm., 1961, 35, 23&242).--The point can be determined by
height and dia. of tubes the thermosiphon will operate well at P drawing a straight line intersecting the titration curve a t three
from 1 to 10-a mm. if F is ;p 100 cm.a/sec. Advantages over piston points in the transition range ; if the line is drawn so as to enclose
and impeller pumps are claimed ; the gas is pumped through the two visually symmetrical areas, the middle point of intersection will
system by the difference in d between the gas in the two arms. determine the point of equivalence with a n error of +. 0.02-0.43y0
W. J. BAKER. for titrated vol. of 30-320 ml., respectively. P. S. ARUP.
Apparent densities and internal surface-areas of selected Determination of composition of solutions of organic
carbon-blacks. P. L. Walker, jun., and W. V. Kotlensky (Canad.J . liquids by titration with water. Application to systems com-
(:hem., 1962, 40, 184--188).-The open-pore vol. (V,) in C black can posed of aromatic hydrocarbons and lower alcohols. E. R.
bc calculated from the N,-adsorption isotherm at 77°K. If the He d Caley and A. Habboush (Analyt. Chem., 1961, 33, 1613-1616).-
of the sample is measured the following can then be calculated- The composition of mixtures of benzene, toluene, xylene, mesitylene
apparent d, free- and internal-surface areas, surface-roughness or p-cymene. and methanol, ethanol or isopropanol, can be deter-
factor and mean pore-dia. This method is suitable for C blacks of mined by titration with water until the mixture appears turbid.
small particle-size, for which the Hg porosimeter cannot be used. The turbidity can be seen more easily if iodine is added to the
Results for different blacks reveal wide variations in their internal solution. R. M. ROWLEY.
porosity. (13 references.) W. J. BAKER.
Solubility of strontium sulphate in water and aqueous
Physical properties of foams and froths formed on sieve- solutions of hydrogen chloride, sodium chloride, sulphuric
plates. P. H. Calderbank and J. Rennie (Trans. Instn chem. Engrs. acid and sodium sulphate by the radiotracer method. P. J.
1962, 40, 3--12).-Bubble sizes on a no. of sieve plates were deter- Lucchesi and E. D. Whitney (1. appl. Chem., 1962, 12, 277-279).
mined by taking flash photographs. A grid of randomly-oriented -Determinations were made using salt labelled with *%r and
lines was placed over the photograph, and the number of lines hitting a t 0" and 25°C. The results are summarised numerically and
or cutting bubbles was counted. From these.observations the mean graphically. A. DARKE.
bubble size and the interfacial area could be found. The values
obtained by this method agree satisfactorily with those obtained by Structure of colloidal solutions. V. Osmotic pressure and
optical reflectivity and y-ray penetration methods. (12 references.) flocculation. J. Duclaux and C. Cohn ( J . Cham. phys., 1962, 59,
K. RIDGWAY. 3641).-The osmotic pressure ( P ) of a pure hydrosol. e.g.,
Thermal conductivity of porous materials and its applica- Fe(OH),, Cu,Fe(CN),, is slowly decreased by addition of an elec-
tion to porous rock. A. Sugawara and Y. Yoshizawa (Aust. J . trolyte (0*01-0.03 vol.-% KC1, K,SO,, K,HPO,) even when this
Phys., 1961, 14, 469-480).-Samples of porous material in the form contains monovalent ions (I). Valency exerts a much stronger effect
of smooth disks of uniform thickness were used. From experiments as the concn. increases t o that required for flocculation, but the
in which the porous materials were filled with water or air a n decrease in P is proportional t o concn. for polyvalent ions only.
empirical formula for the thermal conductivity was derived, The effect is initially reversible only with I : with all ions flocculation
involving the thermal conductivities of the material, the fluid in the causes irreversible chemical modification of the hydrosol. On
pores and an empirical constant. This constant depends upon the addition of non-electrolytes to Fe(OH), sol, e.g, 2-7y0 of propanol,
packing pore size and shape, and emissivity of the inside of the pore. P remains approx. const. but a t higher concn. P decreases slowly t o
Thermal conductivity increases linearly but very slowly with temp. the flocculation point, although the necessary concn. ( - 50%) are
Conductivity rises with porosity if the conductivity of the solid is much higher than for electrolytes, viz. -15% KC1 for colloidal
higher than that of the liquid, otherwise i t falls. (11 references.) polyvinyl alcohol and N 1% KC1 for gum arabic. Results are
T. A. INGLES. discussed in respect of stability of colloidal solutions. (Cf. Idem.,
Heat transfer coefficients of clay slurries. M. Narayan ibzd., 1959, 56, 671.) W. J. BAKER.
lieddy and Ramalingam Kaparthi (J.sci. indwtr. Res., 1962, 21D, Viscosity of non-polar gases at normal pressures. L. I.
I-4).-The study of heat transfer in clay slurries of varying concn. Stiel and G. Thodos (Amer. Inst. chem. Engrs J., 1961, 7, 611-615).
has shown that the heat transfer is low compared to that of water. -Data for 52 non-polar gases have been used to obtain the constants
This is due to high viscosity and low thermal conductivity of the in an equation relating the viscosity t o the crit. temp., the crit.
slurries, and scale formation on the heat transfer surface inside the pressure and the mol. wt. The average deviation for 785 data points
exchanger. T. A. INGLES. was 1.77%. The viscosity product used in the correlation was
independent of the compressibility factor. K. RIDGWAY.
Measuring the film-forming potentials of liquids. P. R.
T3enson and W. R. Martini (Industr. Engng Chem., Prod. Res., 1962, Adsorption. XYI. Measurement of specific surface areas of
1, 7--lO).-The relative fouling potentials of organic coolants in at. Anely divided e d s by solution adsorption. C. H. Giles and
reactors were measured. An electrically heated, vertical cylinder S. N. Nakhwa ( J . ufifil. Chem., 1962, l2,266273).-Specific surface-
was placed in a capsule containing the liquid under test. The weight area measurements of a wide variety of solids including C, cement,
of film deposited under specific test conditions established the coal, fibres, org. pigments and water-sol. materials, e.g., sugar, are
fouling potential of a coolant. Film wt. between < 1 and 200 mg. made using solution adsorption of p-nitrophenol at room temp.
were obtained from 240 mg. coolant samples. Reproducibility of Water is the most suitable solvent, but xylene must be used for
results was within 25%. Tests show that processes which remove water-sol. solids. Adsorption of l-amino-4-anilinoanthraquinone-2-
particles and high mol. wt. org. components reduce the fouling sulphonic acid Na salt from water gives better resuIts for inorg.
potential of an org. reactor coolant. 0. M. WHITTON. oxides such as SiO, and TiO,. (13 references.) A. DARKE.
ii-45 1 7.-LABORATORY APPARATUS A N D TECHNIQUE ; UNCLASSIFIED ii-452

Stability of emulsions. S . S . VoyutskiI ( U s p . Khim., 1961, 30, solution. Cu2+ resin is shown to form a stable tetrammine in the resin,
1227-1257) .-The review is sub-divided into three main parts. while Niat forms ammine complexes on the resin, but these are less
Data are given on the stability of emulsions stabilised by soap ; on stable the greater the cross-linking. The results obtained are dis-
reciprocal emulsions, and emulsions stabilised by non-soapy materials. cussed. E. J . I-I. BIRCH.
(95 references.) A. L. B.
Analysis of complex organic mixtures by gas chromato-
Index and abstracts of Windscale analytical methods. 111. graphy. M. S. Vugdergauz (Usp. Khim., 1962, 31, 73--].OO).-Thc
P.G. Reports [W] Series, No. 114 and 161-224. J. Barraclough review covers patents and information on identification of chromato-
([J.K.Atomic Eneygy Authority Rep., 1962, lJ.G. 281 (W), 8 pp.).- graphic peaks, schemes for separation of complicated organic mix-
Index and abstracts of a range of reports covering topics such as tures and also reviews work on analysis of hydrocarbons. (157
analysis of fish flesh, In foil, magnox, milk, plant solutions, seaweed, references.) .A. L. H.
shore deposits, IJ, vegetation, and natural waters.
J . W. TAYLOR, Elution sequence as a function of temperature in gas
Analysis for industry. T. S. West (Industr. Chem., 1962, 38, chromatography. J. B. Roberts (Nature, Lond., 1962, 193, 1071--
35-37 ; 81-83).-The use of substituted 8-hydroxy- and 8- 1072).-Hop oil hydrocarbons containing myrcene (I), farnesene (II),
mercapto-quinolines and thiophosphoric acids in solvent extraction caryophyllene (111) and humulene (IV) was examined by gas
is discussed together with the use of dyestuffs in extractive separa- chromatography. 'Separation of I1 and I11 was non-existent a t
tions (methyl violet and Brilliant green). The use of dioximes and 125', partial a t 150" and complete a t 175". The elution sequence is
monoximes in the extraction of Co, Au, Pd and Ti, etc., is considered I, 111, 11, IV below 125' but I, 11, 111, IV above 125".
together with the use of Se-containing reagents for the Pt metals. E. C. I ~ O L T O N .
(30 references.) c. v. Capillary methods for analytical test processes with
special reference to paper chromatography. 11. A. Griine
Apparatus for differential thermal analysis. J. Rappeneau (Riechstofle u. Aromen, 1962, 12, 104--107).-Methods for circular
and M. Quetier (Hupp. Cent. Et. nucl. Saclay, 1961, No. 2094, 30 pp.). paper chromatography are described with details of the types and
-The apparatus described and illustrated measures dH/dO (change qualities of papers suitable for paper chromatography, and of a no.
in differential enthalpy) for irradiated graphite between 20 and 800" of specially shaped strips, etc., designed to give arc-like chromato-
and permits calculation of total energy ( H ) . Temp. sensitivity is grams (or series thereof) about or between sharp points (or perforated
0.1", with reproducibility & 0.2". Effects of irradiation dose and wedges) in the paper. H. L. WHITEHEAD.
temp., annealing and successive irradiations, or annealing under
irradiation, on the energy spectrum can be determined. Method is Preparative thin-layer chromatography as alternative for
applicable to measurement of transition (I) temp. and heats of I, column chromatography. F. J . Ritter and G. M. Meyt
e.g., of LI and LJ alloys. (23 references.) W. J. BAKER. Lond., 1962, 193, 941-942) .---The techniques of Kirc
Practical details in infra-red spectrophotometry. A. I. Stahl (Analyt. Chem., 1953, 25. 1107; Angew. Chem., 1961, 7 3 ,
Ricciardi (Rev. Fuc. Ing. quim., Argent., 1960, 29, 59-67).-A 646) for chromatography on adsorbent-coated glass have been
step by step method is tabulated for the purification of kerosene adapted to preparative work. A spreading device for coating five
glass plates simultaneously with a 1-mm. layer of SiO, or Also, paste,
which is used as a solvent because its spectrum has minimum inter- a controlled syringe-applicator for ensuring a uniform narrow strip
ference. Details, including a circuit diagram, are given for keeping of sample solution (-0.5 ml.), and a vacuum-cleaner for collecting
constant humidity in the spectrophotometer room. Inks are sug- the developed chromoplate bands into a Soxhlet thimble are
gested for the register and mechanical drawings supplied for a small described and illustrated. Mixtures (max. 75 mg.) of three steroids,
screw press for making pellets of KBr. (25 references.)
B. F. FULLAN. polyphenols or dyestuffs, containing a max. of 25 mi:. of each
Continuous polarographic analysis. W. J. Parker (Metal compound, can be separated on one chronioplate within a few h.
.Ind., Lond., 1962, 100, 8 2 4 5 ; 105--107).-The principles of and 15 chromoplates can be run a t a time. Method is quicker and
N

polarographic analysis are given and many instruments are described generally gives sharper separations than preparative paper
chromatography. W. J. BAKER.
with examples of their application to the analysis of P b and Cu and
their alloys, plating baths, molten salts, etc. A note on the training Sorption and chromatographyof high-molecular materials.
of personnel for the carrying out of the tests is also provided. (45 G. V. Samsonov ( U s p . Khim., 1961,30, 1410--1428).-New methods,
refereoces.) c. v. including elution and frontal chromatography are discussed. Infor-
Simple procedure for conversion of oxygen of orthophos- mation is included on polyelectrolytes and on sorption of proteins
phate or water to carbon dioxide for oxygen-18 determination. by ion-exchange resins. (46 references.) .4. L. B.
P. D. Boyer, D. J. Graves, C. H. Suelter and M. E. Dempsey (Anulyt. Determination of optimal conditions for Craig's method
Chem., 1961, 33, 1906--1909).-The sample (KH,PO, or H,O) is by means of paper chromatography. I. A. Waksmundzki and
heated in a sealed tube with guanidine hydrochloride; the 0 in E. Soczewihski (Roczn. Chem., 1961, 35, 1363--1372).-Optimum pH
H,O and up to 2 0 per mol. of KH,PO, are converted to CO, which of the aq. phase for Craig's method of separating org. compounds by
is freed from NH, with H,SO, and analysed in a mass spectrometer. countercurrent extraction can be predetermined by paper chromato-
P. D. PARR-RICHARD. graphy. The vol. coeff. r is determined in a simple device described,
Ion-exchange in crystals. R. M. Barrer (Chem. G. Ind., 1962, and for countercurrent extraction the rc is predicted from a
1258--1266).-The important properties (selectivity in exchange, RF = f(pH) diagram. The variations can be adjusted by a change
influence of pH, and ion-sieve action) are described of such cryst. in pH. I n the case of components with partition no. 2200, the
ion-exchangers as zeolites, felspathoids, clays, mercarbides, U optimum p H is changed according to log r / r c . Optimum separation
micas, graphite oxide and other non-silicate compounds. Use of of scopolamine and atropine obtained on Whatman No. 4 paper in
ion-exchange to modify mol. sieve sorbents or to form selective water-saturated CHC1, a t p H 6.3 was repeated in a countercurrent
sorbents from montmorillonitic clays, and the varying capacity of extraction with CHCl, as org. phase and a pH 6.3 phosphate buffer
layer-lattice crystals and zeolites as exchangers of alkyl NH, ions as the aq. phase. (11 references.) A. L. GROCHOWSKI.
are also discussed. Because of the many types and the diversity in Preparative linear chromatography : the equation of the
behaviour inorg. exchangers can replace or supplement org.-gel elution curves and the recovery of the solutes. P. C . Haarhoff,
exchangers both in research and in practice. (39 references.) P. C. Van Berge and V. Pretorius (J.S . Afr. chem. Inst., 1961, 14,
W. J. BAKER. 82-92).-An equation is derived for the elution curve of a solute
Behaviour of ion-exchange resins with mixed solvents. 11. of finite inlet volume, which takes the variation of experimental