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Duty to Care? Comprehensive Management Safety Services i,!, > r! VV. .loiviult.mcv : MONS 085309 { I' H jlj', t , ll F ` ' .1 ` Laboratory Chemicals Disposal Co Ltd 104b High Street, Billericay, Essex Tel: 02-774 51974 16 Devonshire Rd.. Hazel Grove, Stockport SK7 6BY Tel: Poynton (09967} 3218 2 20 November 1971 Chemistry and Industry Tubing for Peristaltic Pumps SILESCOL TRANSLUCENT V1NESC0L 23 BUTYL XX ESCOPLASTIC MS Silicone Rubber, ovor 30 standard sizes from 05mm i d., elastic, excellent resistance to many chemicals, sterilizablo either by steam at 120rC. or by dry heat at 180*C., will not deteriorate either in storage or in tropical climate. Black fluorlnated synthetic rubber, In sizes from 1,0 mm i.d., resistant to concen trated sulphuric acid 98%, phosphoric acid 80%, polrol, crude oil, perchloroethylene, etc. Will withstand temperatures up to 200'X. Black butyl synthetic rubber. In sizes Irom 1.0 mm i.d., with very low gas perm eability end good resistance to many chemicals. Translucent plastic In sizes from 0.5 mm I.d., with good resistance to many chemicals. ESCO (RUBBER) LTD. Manufacturers of Rubber, Silicone Rubber and P/istrc Products 14-16 Great Portland Street, London. W1N SAB RUBBER |~ BUNGS (STOPPERS) in 85 SIZES made in 10 compounds of NATURAL RUBBER "ESCOPLASTIC PLASTIC DISPOSABLE STERILE SEROLOGICAL GRADUATED PIPETTES S ml. & 10 ml. and the following SYNTHETIC RUBBERS: SILICONE FLUORINATED NITRILE BUTYL "ESCOPLASTIC" PLASTIC DISPOSABLE STERILE PETRI DISHES FOR TISSUE CULTURF 2* In cartons of 300 3k' in cartons of 9 also P.V.C. Bungs in 33 sizes "E.R.L." RUBBER HOLDERS FOR TEST TUBES, AMPOULES, BOTTLES, etc. DISTRIBUTORS FOR AMERICAN CONTINENT; NEW BRUNSWICK SCIENTIFIC CO. INC,, 1130 SOMERSET STREET. NEW BRUNSWICK. NEW JERSEY 08903. U S A. HONS 085310 JO November 1971 Chemistry and Industry Chemistry and Industry Society of Chemical Industry President G. II. Becby Ph D, D Tech Hon. Treasurer E. L. Slrcatficld Ph D, C Eng, FR1C, MI Chem E Vico- Presidents F. Aylward Ph D, D Sc, FRIC F. A. L. Holloway Sc D A. J. Howard Ph D, MA, FRIC J. M. Wentworth MA, C Eng, MIEE C. S. Windebank B Sc, MS, C Eng, MI Chem E R. S. Wright CBE, B Sc, FRIC ClreinnoM, Publications Committee T. 1. Williams MA, B Sc, D Phil, FRIC Gonorel Secretary D. H. Sharp Ph D, B Sc, C Eng, FRIC, MI Chem E Editor-in-Chief T. F. West D Sc, Ph D, C Eng, FRIC, AMI Chem E Offices of the Society 14 Bclgravc Square, London SW1X 8PS Telephone 01-235 3681 The Society w Hounded in 1881 and incorporated by Royal (tunc:. I`>0/ The Society was founded in 18X1-- `To advance applied chemistry in all its branches. To afford ns members opportunities for the interchange of ideas with respect to improvements in the various chemical industries and Tor the discussion of all matters bearing upon the practice ot applied chemistry and the publication of information thereon.' Advantages of Membership. No one can advance in the profession of science without meeting and discussing problems with others. The Society enables its members to do this, to keep abreast of current trends in applied chemistry, and to visit works and research stations. Members also have the privilege of using the Library of the Chemical Society. Membership is open to anyone interested in the objects of the Society. Further particulars and forms of application for membership can be obtained from: The General Secretary, Society of Chemical Industry. 14 Beigravc Square, London SW1 x BPS HONS 085311 Roche Vitamins are manufactured consistently to the highest irandaras ot purity and quality, thus ensuring the best possible stability and biological availability Rnrhe I'itatnins Rctinyl Acetate nnd Kctiny) Palmisate Vitamin A p-Oarotenc Provitamin A Thiamine I iydmchloridr and Thiamine Mononitrate Vitamin Di Riboflavin and KiboMavitvS'phosphate Sodium Vitamin Bi I'ytidoxinv Hydrochloride Vitamin B* Nicotinic Acid nnd Nicotinamide Vitamin PP Pantothenates and Pamltenol Vitamin Bj Ascorbic Acid and Sodium Ascorbate Vitamin C DL-a-Tocophcryl Acetatcand DL-a-Tocopherol Vitamin G D-Biotin Vitamin II Menadione Sodium Bisulphite Vitamin K Roche CarotenoidColour] p-Carotcnc Apocarotcnal Apocarotcnoic ester Canthaxanthin Roche Antioxidant I'ttainint DL-a-Tocopherol Ascorbic Acid, Sodium Ascorbate Ascorbyl Palmitate Our advisory and information service at Roche it second tonone. Soifyou have any queries or problems why not get in touch? Just phone 01 *933 M7S or write to: Roche Products Limited, Chemical Sales Department, 15Manchester Square,LONDON W1M6AP MQNS 0853 20 November 1971 Chemistry and industry Tho wookly publication of tho Sociaty of Chemical Industry Price 30p Number 47 / London: 20 November 1971 Editorial Committee P. S. Linklalcr (Chairman) E. C. Apling, H. D. Axe M. Benger, G. A. Collie J. Grant, F. T. Hall N. W. Hanson, H. P. Hodge A. F. Millidgc, R. W. Noad W. O. Nutt, J. E. Page v M. J. W. Rogers, A. J. B. Spaull K. R. H. Wooldridge, J. T. Worgan Editor T. F. West Advertisement Department T. G. Scott & Son Ltd 1 Clement * Inn London WC2A 2ED Telephones: 01-242 6264 01 -405 4743 Telegrams: Textueiist. London WC2A 2ED Annual Subscription to Chemistry and Industry 12 Single copies 31>/ post Jive. (Circulation of Chemistry and INDUSTRY in the period January - December, 1970, certified by the Audit bureau <>/ Circulations Ltd, averaged 971 3 each issue. Home and Overseas.) 1313 Editorial What price priorities? 1334 News this week 1339 Chemical Industries Association annual general meeting and dinner 1340 The poiychiorobiphcnyls, their occurrence and *>is*mlicuncv: a review by R. Etlwards 1349 Laser Raman spectra of drying oils and alkyd resins by L. A. O'Neill ami N. A. R. Falla 1351 British Pest Control Association annual dinner 1332 Essay review Synthetic methods of organic chemistry by P. D. Magnus 13S3 Book reviews Communications to the editor I3SS Structure of the pigments (Hansa colours) formed fiont acctoacetarylidcs with diazouium salts by P- Brady and J. H. P. Tyoma 1356 Pyrolytic reactions of cyclic arincs by G. Hascnhealtl, C. Opulha and J. ( Krmtw HONS 0B5313 20 November 1971 Chvmi.ury and InduMiy One in a million The discriminating analyst can now identify a compound in any mixture with a resolution of one part in a million. The identification is positive with clear discrimin ation between similar compounds- an advance made these characteristic `finger prints' is made possible by a new patented automatic method and Camspek is also designed for integration with computerised data analysis systems. Easy-to-use sampling for gases, liquids and solids is possible with Camspek and fast changeover from one to the other, like the instrument's simple push-button operation, makes it ideal for quality control and routine analysis. Camspek is a unique new generation of microwave spectrometers and a new advance for British chemical instrumentation in the world's industrial and research markets. Camspek' is one in a million. NUNS 085314 20 November 1971 Chemist>y anj Editorial 1333 What price priorities? In the issue of IK September 1971, p 1051, this journal carried a picture of Lord Shcrficld, formerly the distinguished diplomat Sit Roger Makins, shaking hands with Mr George llccby. The occasion was the opening of BSl's new Shcrficld Building and (he two were together as president and deputy president of the British Standards Institution. It is fair to say that the opening of a modest building was of little event in iisclf: it is what lay behind the opening ceremony which should be causing industry - and ours as much us any to prick up its cars or adjust its bi-focais. What Mr Bceby doesn't know about the economic effects of technical rationalisation, particularly internationally, would find plenty of space on a postage stamp: the significant thing is the reaction of Lord Shcrficld in the short time Ihnt he has become president of BSI. Now a prominent figure in international finance, he has become an ardent propagandist for the Institution in which he holds the highest position. The two arc correlated, for there can be little doubt in uny one's mind (hat a major force in Lord Sheffield's enthusiasm is the very rapid realisation that the widespread collaboration which is achieved through BSI means, in the long run, real money, both to those who put standards into practice and to the country as a whole. SluTfleld Building is in the Hcmcl Hempstead Centre of BSI. a centre which is very largely devoted to testing and approvals within export demands, it holds, for example, the agency for testing electrical and other equipment on behalf of the Canadian Standards Association. These tests are a legal prerequisite to exports to Canada. It has authority from the USA automobile authority to approve a number of automobile parts for entry to the American market. It is in effect the modern requirement in the rapidly growing trend towards certification and approval of foreign goods and is a decided lever in the pressure to ease (he path of exporters throughout the world by establishing reciprocal approvals agreements. When such independent and authori tative centres arc testing to internationally agreed lest methods and certifying under international authority, the shunting of new designs backwards and forwards between a manufacturer and the country of his market, the time spent in constant trips to iron out technical differences, will be unnecessary. There is n long way to go yet but the movement has slutted and gains momentum every year. Which brings us to a parallel item in the opening ceremony the establishment of a plaque in honour of the foresight of Mr H. A. R. Binney, now director general of BSI, who, in concert with leading figures in the standards movement like Mr Bcchy, saw this turn of events a decade ago. It was possibly a unique occasion in this field - the recognition of a man in such a permanent way within his own lifetime of service. Three years ago, The Times carried a picture of Mr Binney greeting Dr Boilsov, his counterpart in the USSR. Dr Boitsov is now a Minister of the Soviet Council of Ministers, and heads a grand network of stan dards centres, which includes over 1000 officers solely devoted to information. Like Mr Binney, Dr Boitsov sits on the council of the International Organisation for Standard isation in Geneva and expresses in his own energy in international collaboration the very keen interest of the Soviet. There must be a lesson here somewhere when a learned standards man becomes a minister in the senior Soviet hierarchy. There must be something to be drawn from the fact (hat Japan maintains a permanent liaison man at ISO in Geneva. The lesson is not hard to find. In one year Russia saved 8 million roubles on crane production, in (he same year 13 million roubles on paper and stationery and these are only two in a list totalling an astonishing financial return. Yet BSI, and for that matter most of the other national standards bodies, staggers from April to March, cocking an apprehensive eye, first at the economic charts affecting their subscriptions and sales and then at (he mood of the government of the day. Not only does it not know where next year's money is coming from, it docs not know how this year's expenditure is to be met. The comparisons, at a time when the international pressure is for harmonisation of effort which will save every country untold millions in avoiding dragging themselves around national technical obstacles, are ludicrous. BSI's annual report shows that the Institution took a lending role in the production of 53 ISO Recommendations strictly related to chemicals. The total effort including paints, pesticides, plastics compounds and chemical engineering is large and grows larger if one selects items such as the sampling and chemical testing of leather, petroleum and dozens of associated standards. In the long run, when these ISO standards arc (irmly embedded in national standards they can only add up to conservation of skills, of time and of money. Under the present financial strictures, individual com panies can be forgiven for overlooking these facts. But in terms of concerted industrial effort and national concern, there is sufficient evidence that the considerable amount of voluntary effort expended on work of vital importance to industrial efficiency and the export trade is, if not exactly neglected, at least unappreciated. This is the real caption to the picture of Lord Sherficld and Mr Beeby that was published a short time ago . . . and it is the proper emphasis on the simple building that was opened on that day. MGNS 085315 1.134 20 November IV7I Clu-nmiry mut huluury News this week Society reports and notices Plastics and Polymer Group ' The physics and chemistry of fracture' Professor K. M. Andrews, head of the Department of Mutcriais ut Queen Mary Collette, London will be giving a lecture on the above subject at 14 Bclgravc Square, London S.W.I on Tuesday 23 November 1971 at 6 pm. Professor Andrews has supplied the following abstract of his proposed talk: The study of fracture phenomena in polymeric solids can be uppronclicd from any one of three different directions, which could be called the engineering, metal lurgical attd chemical viewpoints respec tively. The engineering or mechanical approach, typified by the fracture mechanics treatment of the subject, considers the solid as a continuum with certain average or macroscopic mechanical properties such as elastic moduli, yield stresses, visco elastic parameters and so on. Its great value is that it leads to predictive formulae which arc useful to the engineering designer wishing to avoid fatigue fracture or stress- corrosion. ' The 'metallurgical' or morphological approach recognises the importance of physical microstructurc and heterogeneity in controlling fracture properties. For example, a sphcrulitic specimen of a given plastic may be very brittle, but one crystallised under strain may be lough and ductile. The relationship between mor phology and fracture is a developing field of effort and some current work will be discussed. Finally, fracture ultimately concerns the breakage of intcr-utomic bonds, and can thus tic regarded from a chemical view point. Extensive studies of 'main-chain' rupture have been made in the general field of mcchano-chcniistry, but the relation of these events to the fracture of the bulk solid is only just emerging, largely as a result ofc.s.r. and related investigations. tt.i.t.w. Food Engineering Panel Forthcoming lecture 'The drying and instantlshtg of milk products' The Food Fnginecring Panel. Food Group, arc holding a meeting on 8 December 1971 at 14 Hclgiuvc Square, London, which will Ik addressed by Mr r. Ilamurd, of (he Milk Marketing Board on the subject of 'The drying and instantising of milk products', and not as may be elsewhere described. All members of the Food Group and their guests are welcome to this topical meeting, which begins at 6,15 pm. r.j.c. Colloid & Surface Chemistry Group Forthcoming lecture 'Colloidal aspects of printing inks' A meeting will be held jointly with The London Section of OCCA on the above subject al 6 pm on Monday 13 December 1971 al 14 Bclgravc Square. S.W.l. The Speaker will be Dr W. Carr of Ciba-Geigy. An abstract of the lecture follows: Colloidal dispersions arc characterised by the degree of sub-division of the dis perse phase. The lower limit of size is accepted as being Inin (1 millimicron): the upper limit as being between 0-2 and I-Own (0-2 and 1-0 microns). Purliclc size measurements on the pig ments in printing inks demonstrated that commercial inks arc partly in the colloid range. With some inks, their storage properties are directly related to the degree to which they arc true colloids. This work would indicate that the upper limit for true colloidal dispersion is 0-3|im. Inks can be shown to improve in dis persion on dilution. This can be explained qualitatively in terms of modern colloid theory. . The flow properties of inks can be explained partly in terms of modern colloid theory. k.s.w.s. Pesticides Group Forthcoming symposium 'Increasing the biological contribution to the control of pests and diseases' A major symposium will be held in Oxford on 5-7 January 1972 on the above theme. It is being organised on behalf of the Royal Society Sub-committee for Biological Con trol by (he Association of Applied Bio logists. British Ecological Society and SCI Pesticides Group. Scientific contri butions will review developments in a variety of control techniques, including the use of conventional pesticides and other chemicals. Emphasis will be placed on the effective exploitation of these techniques with due regard to economic and environ mental considerations. Further particulars and application forms may be obtained from the Society of Chemical Industiy, 14 Bclgravc Square. London SWIX 8PS. o.p.j Solvent Extraction t Ion Exchange Group Forthcoming visit to Permutit and Battersea Power Station A visit has been arranged to the Permutit Co. Ltd al Islcworth, Middlesex and Batter sea Power Station on Wednesday 1 March 1972 al I) am. In the morning Mr R. C. Williams, British Nuclear Fuels Ltd, will give a Icclure on `Ion Exchange and its use in modern electric power stations' at Islcworth. The visit to Buttcrsca Power Station will take place in the afternoon. Places on this visit arc limited and those who wish to attend should write to Mr M. J. Cristal. Head of Technical Informa tion Service, The Permutit Co. Ltd, Permutit House. Gunnersbury Avenue. London W.4 before 31 December 1971. If sufficient persons arc interested an additional visit in the morning and a repeat of the lecture in the afternoon will be arranged. n.m.k. London Section Forthcoming visit to Harwell The whole-day visit to the Chemistry Division (Pure and Applied) at Harwell has been arranged for Thursday 11 May 1972. commencing at II am. Further details will be given in the Bulletin about two months before the visit. p.a.s. Heavy Organic Chemicals and Fine Chemicals Groups `Impact of organomctallics on the heavy organic chemical industry ' A joint meeting of the Heavy Organic Chemicals and the Fine Chemicals Groups was held in the Society's rooms on 19 October 1971 with Dr A. Gardner (Vice-Chairman. Heavy Organic Chemicals Group) in the chair. Di Gaulnci uiiio- duccd the lecturer, Dr J. Facsel of Mclaltgcscliscliart. Dr Facscl started his lecture with a brief history of the industrial production amt application of organomctallic compounds, dating from the introduction some 40 years ago of lead tetraethyl and of organic- mercurials. The usage of organomcialltcs in the petrochemical industry dates from MONS 08531b 20 November IV7I Chemistry fWorv 1335 the pioneering work of Ziegler on the oligomerisation nd polymerisation of olefins, The basic Ziegler chemistry was outlined; on the basis of Ziegler's work (particularly with uluminium alkyls) routes to it number of interesting compounds have been developed, c.g. long chain a-olcfins, primary alcohols, propylene dimer, ethylene nnd propylene polymers, polybutudicnc and polyisoprcnc. In 1970, production of aluminium alkyls was 25,(XX) Ion, mainly used in the production of long chain primary alcohols from ethylene; the production of a-olcfins by ethylene oligomerisation is not currently competitive with production from nparaflins. Propylene dimer, the only product from propylene with aluminium alkyl catalysts, gives isoprcnc and methane on cracking, and about one third of the western world capacity of synthetic iso* prone is based on this reaction. The Ziegler high density polyethylene process was described briefly, and the properties of low density and high density poly ethylene were compared. The production of polypropylene was developed by Natla with catulysl systems composed of alu minium alkyls plus titanium salts; poly propylene has many applications, and has a rapid growth rate so that by 1975 it was forecast that 20 |Kr cent of the total polyolefin market will be for polypropylene. In the polymerisation of dioiefins to give nihltcrs, different polymer structures arc ohluincd with different catalyst systems. Lithium alkyls arc useful catalysts, and in 1970 some 300 Ion of lithium butyl were used in the production of stereo rubbers, mainly from butadiene; stereo polybutadicnc is competitive with natural rubber in tyres and mechanical rubber goods. Aluminium alkyls arc used in the pro duction of cthylcnc/propylcnc tcrpolymcr rubbers which have good properties in many applications. The versatility of the orgunomctallic catalyst systems available allow many varieties of rubber to be produced, and it was forecast that stereo rubbers will grow much more rapidly than SBR, representing about 30 per cent of the market for synthetic rubber by 1975. In the subsequent discussion. Dr Facsel Miid that the hazard of handling organomvtallic compounds were now well under stood; lithium butyl was sold as a non- pyrophnric solution. In reply to a question on the use of synthetic rubbers in tyres, he emphasised that polybutudicnc and tcrpolymcr rubber were already com petitive with natural rubber, but that polyisoprcnc was not so because of the high monomer cost. Tlic meeting concluded with a vole of thanks proposed by Mr H. Hodge, who complimented the lecturer on his able presentation in simple terms of a subject of considerable complexity. a.j .m. Newcastle upon Tyne Section 'Safety aspects of natural gas' A joint meeting with the R1C. and the Institute of Fuel was held on Wednesday 13 October 1971 in the School of Chemistry, Newcastle upon Tyne when Dr P. J. King of UMIST gave an illustrated talk on 'Safety aspects of natural gas'. Dr King, who was introduced by Dr R. N. Parkins, the Section Chairman, pointed out that the subject matter of the lecture was based on the results of the inquiry into the safety of natural gas as a fuel, which was conducted at the Govern ment's request during 1970. After giving a brief historical survey of (he discovery of natural gas and the conversion plans for Great Britain, Dr King spoke of the factors leading to the growth of public disquiet and the subsequent setting up of the inquiry. The speaker compared the physical and chemical properties of town gas and natural gases and showed that while the two types of fuel were similar they did differ in many respects and the effect of these differences on their relative safety were discussed. Particular attention was placed on combustion characteristics and explosion hazards. The problem of ade quate and efficient ventilation for ail types of fuel was given special consideration and comments on the advent of natural gas in the north east were included. The speaker concluded (hat all fuels were hazardous unless properly used, but natural gas introduced no new hazards when compared to town gas; on the contrary, it removed the greatest single hazard, t hal of carbon monoxide poisoning due to accidental escape of unburnt gas. A lively discussion followed in which it was queried how the gas industry intended to overcome the ventilation problem, and whether statutory powers to enforce regular inspection of premises would be involved. Dr King replied that he thought adequate ventilation ought to be provided in the first instance by the gas industry. Dr King suggested that a joint consultative council for safety be set up for the gas, electricity, oil and solid fuel industries. One speaker mentioned that there was evidence which showed that the chance of explosion with natural gas was greater than that of town gas and he asked what facts and figures were available to substantiate this. Dr King replied that statistics with regard to explosions were minimal and it could'not be said that natural gas was more dangerous on (he basis of such inadequate information The gas industry was taking the problem seriously and information regarding gas explosions was recorded independently by fire officers. The meeting concluded wilh a vote of thanks to Dr King by the chairman of the local section of the Institute of Fuel D.A.W. Appointments and resignations Mr Robert Carr, Secretary of Stale for Employment, has appointed Mr S. H, Lawrence to be a member of the board or directors of Industrial Advisers to the Blind Ltd. Mr M. A. E. Hodgson and Mr S. D. Lyon have been elected deputy chairmen of the Board of 1CI as from I April, 1972. At that time they will join Mr M. J. S. Clapbam and Mr R. S. Wrighl, two of the three present deputy chairmen. Mr P. T. Menzies retires from this position on 31 March on taking up the chairmanship of the Electricity Council. Mr M. A. E. Hodgson Mr 5. D. Lyon The Badger-Tomoe Co. Ltd, Tokyo. Japan, has appointed Mr E. H. Martel as vice-president and managing director. Mr R. M. Welts, development manager and a member of the executive hoard oT Philips I'jltration Ltd, has been invested as chairman of the Filtration Society for 1971-2. Mr S. W. Gillies, director ami general manager of Saro Products Ltd. isle of Wight, has been appointed managing director of that company. Mr C. A. Cannon and Mr G. Colling* have been appointed to the board of Giostcr Saro Ltd, Gloucester. A well-known authority in this field, Mr W. A. Roberts has been appointed field product manager (nuclear) for Beckman-RUC Ltd of Glenrothes a ml Croydon. Pcnnwalt Chemicals Ltd has announced that Mr D. Maclcod has been appointed area representative for Scotland, calling on engineering outlets wilh a range of cleaning and pre-finishing chemicals. MQNS 085317 1336 20 November 1971 Chemistry and huiustiy Mr S. T. MeGetry has been appointed general production manager of GECFllioll l*roccss Instruments Ltd. Dr D. Newman, clicmistry master at Eton, has been appointed by the Sailers' Institute to Sabbatical Fellowship to be held ul Imperial College in the Depart ment of Chemical Engineering and Chem ical Technology during the Spring term of 1972. Mr V. II. Wentworth, senior technical specialist - plastics with Monsanto in London, has retired after 17 years with the company. Mr S. A. Stewart retired as Director of the British Tar Industry Association on 31 October 1971. He is succeeded by Mr II. dayman, Managing Director of Benzole Producers Ltd and currently President of the National Benzole & Allied Products Association. Mr .1. R. King, director of sales of Tor pedo Marine Paints, the marine division of the Berger. Jenson & Nicholson Group of C ompanies, has retired. Thomas 1irondl>cn( & Sons Ltd has announced the retirement of Mr F. Hroadbent on 30 September 1971, due to continued and serious ill health. Death Professor Dr H. A. Bockenoogen. formerly head of the Unilever Research laboratories at Vlaardingcn, Holland, died on 26 October 1971. Professor Dr llockcnoogcn gave the International Lec ture to the Oils and Fats Group of SCI in 1966. Company and industrial news Conoco and Norsk seek Italian offshore acreage (ontinentale llaliana S.p.A., the Italian subsidiary of Continental Oil Company, is seeking offshore prospective acrcugc. The company has announced that, in con junction with Norsk Hydro llaliana, it is applying to the Italian government for exploration licences in thirteen blocks of Zone situated off the coast of Sicily. Norsk Hydro llaliana is the Italian sub sidiary of Norway's Norsk Hydro, and will have a one-third interest, to Contincntale's two-Hurds, in the Zone C Venture. Urcthanr elastomers from ICt The Organic Division of ICI arc introduc ing a new range of eight thermoplastic urethane elastomers which combine qual ities of rubber and plastics. The product. `Dnllnmold*. has the clastic properties of rubber and the toughness associated with plastics produced from polymers. The new products, which mould like plastics and work like rubber, have a wide variety of uses in fields where flexibility and hard wear are the main requirements. They also show icsistance to fuels, oils, oxygen, abrasion, tear and general mechanical abuse. The 'Daltoinoid' series are expected lo compete with synthetic rubber and, it is hoped, (o replace certain other materials, including metals, in some applications in the car, textile, footwear and engineering industries. Rapid mineral identification A service for the expert and rapid identifi cation of a wide range of mineral sub stances is now offered by Yarsley Research Laboratories Ltd of Chessington in Surrey. Using modern A"-ray powder diffraction analysis equipment, only a small sample of the unknown substance is required. Identification is assisted by the American ASTM index which records data on over 9000 compounds, in addition to Yarsley's own library of films givina data on over 5000 materials. Expanded polystyrene sheet process Omega Plastics Ltd of Canvey Island, with financial backing from the National Re search Development Corporation, have produced expanded polystyrene as thin sheets of consistent quality, which can be used for a variety of purposes. Demand for the material is such that Omega is offering the complete process as a package deal and is willing to license patents both in the UK and abroad. Phillips announces polyethylene licence in Yugoslavia Phillips Petroleum Company has an nounced a new high density polyethylene licence agreement with Hemijska lndustrija Pancevo, a Yugoslavian firm, who will erect a 50,000 ton/year plant at Pancevo, 20 km from Belgrade. Fifteen companies now have licences to use (he Phillips process in the USA and in nine other countries. The licensee plants, together with the Phillips plant near Houston, Texas, now represent one million ton/year of high density polyethylene capacity. New copper processing methods Scientists in the Research School of Chemistry at the Australian National University have discovered methods of extracting and refining copper which could change the existing industrial processes. Patent applications have been filed. An nouncing this, the Vice Chancellor of the University, Professor Sir John Crawford, said a small unit for developing the practical and commercial aspects of (he discoveries had been established. Sir John said that a group of research scientists had found solvents which allowed copper to be processed by other than the conventional methods, together with a process which avoided the slow electro-refining in the purification of blister copper Apart from possible economic advantages, he said, the new processes may help to reduce pollution. It was hoped that an Australian company would join with the National University in development. Radio Australia News I.C. convert Fulham power station to oil A contract to convert the boilers in the No 1 boiler house of the Central Electricity Generating Board power station at Fulham from coal to oil firing has been awarded to International Combustion Ltd of Derby. This contract is worth almost half u million pounds. The contract calls for the con version of six boilers, the first to be com pleted during late 1971 and (he sixth by early 1972, Under the terms of this con tract, International Combustion will supply, erect and commission the complete oil firing plant and all conversion equipment. International Combustion have been work ing for the past (wo years on a number of oil and gas conversions for the Central Electricity Generating Board throughout the country. Order for Douglas-Rowrtson Douglas-Rownson of Basingstoke (Baker Perkins Group) have obtained a 20,000 order from Meyer Dumore for a palletis ing and conveying system which is to be installed at Daniel Thwailes brewery, Blackburn. A.P.V. - Mitchell's Japanese contract A.P.V. - Mitchell Ltd of Croydon have developed and patented a process for producing pure fluosilicic acid from va pours given off during the vacuum con centration of phosphoric acid. This pure fluosilicic acid, containing less than 100 p.p.m. of phosphoric acid, is then used to produce aluminium fluoride and cryolite, essential raw materials in the production of aluminium. This is a major breakthrough in using unwanted effluent for the pro duction of valuable chemicals. The first plant, consisting of two units, was installed in Japan in 1969-70 for Tohoku Hirov KKK at Akita giving highly satisfactory results. The success of this plant has resulted in a further order being placed tor Mitsubishi Chemical Industries for in stallation later this year. BOC introduce aircraft engine starting system A new method of sturting aireruli jet engines is being introduced into (lie UK by the British Oxygen Compuny m co operation with Aviation and General Consultants Ltd of Middlesex. The ->nIcih is based on the `Cryoslart- jet engine starter MGNS 085318 20 November 1971 Chemistry and industry 1337 which is manufactured in the United States by the Systems Capital Technology Cor* pot ation of California. The system involves passing liquid nitrogen over hot aluminium oxide pellets. The unit bus a tank of liquid nitrogen supercooled to I85"c\ When (lie engine is to be started, the liquid nitrogen Hows into a chamber containing a Iwd of aluminium oxide pellets that hove been preheated to 232'c. As soon as the nitrogen contacts the healer bed it turns into gas, expands instantly and is ducted into the jet engine to turn the turbine air compressors, The `Cryostarf system lias a number of advantages over conventional methods using compressed air. General New combined treatment for liver fluke After scvcrul years of trial work a Shellstar molluscicidc called `Frcscon' is now available to farmers for spraying pastures to control the mud-snail which transmits liver duke to cattle and sheep cuusing liver damage, unthriftincss and in uculc eases, death. Trcscon' is important because, for the fust lime, farmers can make a two-pronged attack by using it with existing oral treulmcnis. The combination of both methods is calculated to give better results than either used alone. The material will he distributed by ICi Pharmaceuticals Division. Zanil and Nilzan and the marketing organisation necessary to get the integrated treatment into use. ' Agricultural Science Institute calls for national policy on primary industries The Australian Institute of Agricultural Science bus called for a national policy on primury industries. The institute said in a special statement that the combined effort of farmers, agricultural scientists, economists, sociologists and politicians was needed to place the rural economy on a sound basis for the next lit to 20 years. However, the immediate need was to solve short term problems facing (he man on the land. It considers a thorough review is necessary. The institute announced that tl is setting up a coordinating committee to consider u national policy on agriculture. Radio Australia News Willows Francis Group annual report In his annual statement Mr A. J. Cornforth the chuirmun of the Willow Francis Group reported u profit before tax of 139,399, and stated that sales and trading profits had showm an encouraging increase during the first quarter of the current year. He staled (hut muny of the company's im mediate objectives had been attained, notably the restoration of an upward trend in the sale of speciality products in the veterinary, dental and chemistry divisions. Glaxo Group annual report In his annual report. Sir Alan Wilson, chairman of Glaxo Group Ltd, announced that, as had been predicted, sales had increased substantially but profit margins were reduced. Total Group sales, ex cluding wholesales, showed an increase of nearly JO per cent over last year, while the trading profit at 24-lm increased by about I per cent. The profit after tax attributable to the ordinary stockholders was 12 8m, about 3 per cent higher than last year. Associated British Maltsters annual report The new chairman of Associated British Maltsters Ltd, Mr P. Parker, who took over from Mr D, L. Nicolson following his appointment to the chair of the new British Airways Board, announced in his annual report that profits attributable to ordinary shareholders amounted to 704,000, an increase of 67 per cent over the previous year. The annual general meeting of the company will be held on II January 1972, but the board is making a second interim dividend of 15 per cent payable on 10 December 1971. Annual report of the Food, Drink and Tobacco Industry Training Board The annual report of the Food, Drink and Tobacco Industry Training Board states (hat the year had been one of both con solidation and development. The major emphasis during the year was the improve ment of standards of performance through individual advisory visits, meetings with groups of employers and the development of written guides and recommendations. The resulting improved standards would, it was hoped, form the basis for moving on through what the board has recognised as only the essential first stage of its work, the system based on levy/grunl. During the year significant progress was made towards this goal. Discussions were therefore beginning on the feasibility of moving towards a dual role of assessment and advice based on charges more closely related to the amount of time spent with companies. Turkey's largest filling station In the recent Shell Magazine there is an article about a Shell filling station beside the Topkapi Gate of the ancient city of Byzantium. This station was discovered by Hugh Harvey, formerly of Trade Relations, SIPC. Since the filling station is situated on the busy London Road it has been very successful and not only arc there con siderable gasoline and oil sales on the forecourt but also the station has live bays for lubrication service, a washing area that can handle up to 10 cars at one time and a fully equipped garage for repairs. The fuel oil business has also flourished and there arc four (ankers for customer delivery and five tankers arc operated on behulf of Shell Turkey for distribution of Shell products to dealers. Publications Petroleum industry catalogue The council of British Manufacturers of Petroleum Equipment has brought out its latest catalogue entitled British petroleum equipment and services 197! j72. The cata logue contains information aboui British companies who together can supply tliewhole range of equipment and services required for operations and installations in the oil, petrochemical and natural gas industries. Other literature from the CBMPE includes the weekly information bulletin CBMPE information service and the quarterly journal Oil and petrochemical equipment news. Further information can be obtained from the Secretary, CBMPE, 118 South wark Street, London SEI OSU. BSC progress report The progress report on British Steel Cor poration research and development. Steelresearch '71, describes some aspects of the Corporation's research for the period 28 February 1970 to I March 1971 Although not intended to be comprehensive ihc report spans for Ihc first lime the whole field of Ihc Corporation's current research effort. Copies of the report arc available from the Information Officer. Hrilish Sled Corporation, Park House, Park Street, London W.l. New literature from Nalfloc New literature, describing a range of fuel and fireside treatments which will help users to pinpoint fuel utilisation and combusion problems, is available from Nalfloc Ltd. The company, jointly owned by ICI and the Nalco Chemical Company, makes a wide range of fuel and fireside treatments specially formulated to do S]>ccific jobs. Further information may be obtained front Nalfloc Ltd, PO Box 11, Northwieh, Cheshire. Adhesives in the packaging industry A scries of 8-pagc colour booklets from National Adhesives and Resins Lid. Slough. Buckinghamshire, provides a handy and useful reference for anyone concerned with adhesives for packaging. National. I) HONS 083319 tm 20 November 1971 Chemistry and Indusm which claims to be the world's leading supplier of adhesives products for the packaging industry, says that the primary concern is to help a user recognise, select and properly use the best adhesive for the job to be done. Copies of the booklets can be obtained by writing to National Adhesives and Resins Ltd, Slough, Buckinghamshire. Factory accidents A new publication, Factory accidents: their causes and prevention (A5, 26pp price 20ft) has just been published by KoSPA. It replaces a previous publication, The causes ofeveryday accidents infactories. Further information can be obtained from RoSPA, Terminal House, 52 Grosvenor Gardens, London S.W.l. Organic synthesis design A new booklet, An introduction to the design of organic synthesis, has been udded to the series of free technical booklets produced by Koch-Light Laboratories Ltd. The publication, prepared by Dr S. Turner, analyses the approach to organic synthesis and ulso presents a simplified treatment of the analysis which will enable a chemist, using pencil and paper rather than a computer, to consider a specific synthesis in a general way which reveals many of the important problems to be surmounted when hcnchwork begins. The booklet is available free on request from Koch-Light Laboratories Ltd, Colnbrook, Buckinghamshire. ' Thlokoi Chemicals Lid report A new technical service report produced by Thiokol Chemicals Ltd Technical Service and Development Laboratory entitled Evaluation of thixotropic additives in t wo-j>art polysulphide sealants, is now available from Thiokol Chemicals Ltd, Chemical Division, Station Tower, Station Square, Coventry, CV1 2GH. This report is based on two years' evaluation of thixotropic additives. Meetings, Notices Cibe Foundation meetings A list of Ciba Foundation meetings, for the promotion of international cooperation in medics! and chemical research, over the next few months can be obtained from the Ciba Foundation, 41 Portland Place, London WIN 4BN. Chemical education conference A three day conference entitled `Develop ments in tertiary chemical education' is to be held at the Thumcs Polytechnic on 13-15 December 1971. The aim of the conference is to bring together chemists and edu cationalists to review and discuss current work in the areas of curriculum develop ment, educational techniques and methods of assessment in chemistry at the tertiary JeveJ. Further details and application forms arc available from Mr B. A. T. Bleach, Academic Registrar, Thames Polytechnic, Wellington Street, London SE18 6PF. Royal Society meetings The Royal Society anniversary meeting will be held on 30 November 1971 at 2.30 pm. The programme of meetings for November and December 1971 is avail able from the Executive Secretary, The Royal Society, 6 Carlton House Terrace, London SW1Y 5AG. Golden jubilee meeting A meeting to commemorate the golden jubilee of the Department of Biochemistry of the Indian institute of Science, Bangalore is to be held in Bangalore from 2-7 December 197J. The subjects on which papers are to be presented include lipids, proteins and enzymes. Further information can be obtained from the Executive Secretary, The Bio chemical Society, 7 Warwick Court, l.ondon WC1R 5DP. Urban transportation conference `Urban transportation' is the theme of the National Conference of the Institution of Highway Engineers, at Church House. Westminster on 9-10 December J971 for which over 500 delegates have so far registered. Further details and application forms can be obtained from The Secretary, The Institution of Highway Engineers, 14 Queen Anne's Gate, London SWiH 9AF. National Physical Laboratory conference A conference, entitled 'The measurement of high frequency dielectric properties of materials' will be held at the National Physical Laboratory from 27-29 March 1972. The frequency range covered will be approximately 1-300 GHz. A fee of approximately 20 will be charged to cover accommodation, food and conference expenses. Further information can be obtained from Dr J. Chamberlain, National Physical Laboratory, Teddington, Middlesex before 15 December 1971. First international packaging conference Bookings arc being taken now for the first International Conference on Packaging Technology, to be held at the London Hilton on 27-29 March 1972. This is the first international conference to be held on the technology of packaging. It is being organised by Pira (the research association for the paper and board, printing and packaging industries) in conjunction with 1APRI (the International Association of Packaging Research instilutes). The conference will provide a comprehensive picture of progress m various aspects of the many technologies involved. Confemnce programmes and application forms are available now from the Con ference Organisers, Pira, Randalls Road, Leathcrhead, Surrey, England. Pera conferences Pera, the production engineering research association, is holding four conferences in Melton Mowbray. They arc 'Selling technical products to industry' on 30 November-1 December, *Thc modern con cept of quality management' on 7-H December, `Non-destructive testing' on 9 December and 'Metrication - making it pay' on 15-16 December. Further details may be obtained from Ihe Public Relations section, Pera, Melton Mowbray, Leicester' shire. Lighting seminar A seminar on `Using the Latest White Light Sources in Commerce and industry', will be held at the Royal Commonwealth Society, Northumberland Avenue, London S.W.l. on Tuesday 30 November 1971 at 5.30 pm. It is sponsored by The Electricity Council and the Lighting Industry Feder ation. Carbohydrate chemistry award The Council of the Chemical Society, in association with the Carbohydrate Dis cussion Group, has announced the intiuduction of a new biennial award hi carbohydrate chemistry, to be sponsored by Tate and Lyle Ltd. The award will cover all aspects of the subject. Applications ui recommendations for 1970 must lx* received not lutcr than 3J December 1971. Copies of the rules of the award arc uvuilnblc from Dr J. I . Gibson, Tltc Chemical Society, Burlington House, London W1V 0BN. Beilby Medal and Prize 1972 Awards from the Sir George Beilby Memorial Fund arc annually made to British investigators in recognition of independent original work of exceptional merit carried out over a period of years in the fields of chemical engineering, fuel technology or metallurgy. Work of the nature indicated must he brought to the notice of the administrators not later than 31 December 1971 hy letter addressed to the Convener of the Administrators. Sir George Beilby Memorial Fund, The Royal Institute of Chemistry, London WCIB 5DT. Applications made by the candidate should include the names of two referees. The letter should be accom panied by nine copies of a short statement on the candidate's career. HONS 085320 20 November 1971 Chemistry and Industry 1339 Chemical Industries Association annual general meeting and dinner in his presidential speech to the annual general meeting of the Chemical Industries Association on II November I97J, Mr J. H. Townsend was pleased to publicly acknow ledge the support that the members had given to the Association at a time when the industry was subject to outside picssures and influences, and individual members hnd to be ready to respond quickly and constructively to changing circumstances at home and abroad. This support had been well matched by the skill and effort of the per manent staff of the Association. Mr Townsend went on to say that the industry must work harmoniously with many external bodies if chemical manufacturing in this country is to make its most effective contribution to national economic activities and to the wider aspirations of society. This means a continuing diuloguc with government departments on all aspects of trade, employment and the environment and with trade unions on wages and conditions, and many discussions with the industries' counterparts in Europe in view of the growing involvement in European affairs. On the economic front there have inevitably been serious problems for the industry as the UK economy has gone through another year without effective growth, and the powerful influences of inflation and trading difficulties have been strongly at work on the international scene. Some of these problems had been foreshadowed by trends established during previous years, but they had become more acute in recent months, and in the climate of un certainty over international developments, the industry may lind itself fucing a tendency towards restrictive attitudes. At home, the output of chemicals is currently only 3 per cent higher than it was a year ago. This is a serious slackening of growth compared with the average of 6-5 per cent/year throughout the 1960s. As a result of a market demand smaller now than was anticipated when the investment decisions were taken in the brisker economic climate of 1968-9 some surplus capacity is now evident, particularly in certain heavy organic fields. The industry is also subject to great pressures on costs of materials, fuels and wages, and increases in these have outstripped any improvements that can be made in pioductivity. A more encouraging feature of the current scene is the performance of chemical exports. This is particularly gratifying at a time when surplus capacity in the major producing countries is tending to intensify competition. The volume of UK exports has continued to grow and despite keenness in prices their value for the first half of 1971 was 463m compared with 418m in 1970. Chemical imports showed less growth in the first half of the year and as a result the balance of trade in chemicals has improved. The Association warmly welcome the decision of Parlia ment to join the European Economic Community, since it has strongly supported British entry in the belief that the balance of advantage would be decisively in favour of the l)K chemical industry. The R1 Hon. Peter Walker, Secretary of State for the Environment, with the President As regards environmental problems, a substantial effort both nationally and internationally has been and continues to be made by the industry to overcome them. The industry has had over many years a deep consciousness of (he problems of its own hazards, and Mr Townsend felt it significant that despite the hazards of work in the industry the incidence of injury to people working in daily contact with chemicals is currently slightly less than for the manufacturing industry as a whole. This was a subject on which there was a complete absence of complacency. Mr Townsend concluded his speech by stating his conviction that the Association had the resources and the will to meet any challenges and to compete successfully with the rest of (he world. At the annual dinner held at Grosvenor House, Park Lane, London W.l. on the evening of 11 November 1971, Mr Townsend, in his capacity as President ol the Association, welcomed the guests. In his response, the Right Honourable Peter Walker, Secretary of State for the Environment, was pleased to say that rivers and air were becoming cleaner each year, and that he shared in the optimism so far as the future of the environment was concerned. After a difficult period during which an Empire had disappeared, Britain was now entering a phase of growing industrial power supported by world-wide connections, line institutions such as the City of London, and a resourceful people. Mr Walker then referred to a young generation who were deeply interested in the environment and felt that Britain had the opportunity of combining commercial greatness with a better standard of living. He said that he looked upon the chemical industry as a partner in achieving these aims. MONS 085321 1340 20 November 1971 Chvmistry and fndn\i>\ The polychlorobiphenyls, their occurrence and significance: a review by R. Edwards //. J. Heinz Co. Ltd, Hayes Park, Hayes, Middlesex Pollution of the global environment by man is rightly receiving considerable attention because of the increasing realisation of possible long term effects on both the physical environment and Jiving organisms. Clearly it is necessary to distinguish between short term toxic effects and long term ones (/>. reproductive and carcinogenic ell'ects), these Jailer being more difficult to assess. The chlorinated hydrocarbons used as biocides are well documented in their short term toxic effects, and with knowledge of their facile accumulation in the environment due to their considerable chemical stability, more work is being done on the long term effects coupled with lighter control of their use. With the latter (he main points of entry into the terrestrial environment arc through crop spraying and seed dressings with conse quent accumulation in the soil. From this point they can also reach (he aerial environment secondarily by evaporation or `co-distillation' and carriage in fine particulate matter. They urc also systemic in plants to varying degrees. Aqueous run-off carries them through the drainage system together with industrial effluent sources to reach the marine environ ment above the continental shelves. It is thus possible for these compounds to reach the lower members of the many fomlchuins. Man'sdomeslicand industrial use of biocides for hygienic purposes louds to entry at various other points in the food chains. The very large concentration factor (10s) possible in these food chains is well known and in the final members (r.g. marine mammals, predatory birds, man) the concentrations can reach alarming proportions. Lipid solubility means (hat a large percentage of these residues will he stored in the fat depots of the body. The polychlorobiphenyls (PCBs), with a very widely dispersed use throughout industry, have very similar pro perties to the chlorinated hydrocarbon pesticides, but are even more thermally and chemically stable. An important difference, however, lies in the routes through which they contaminate (he environment. Emphasis here is on indust rial effluents reaching the marine medium, and possibly the burning of industrial waste contributes relatively more to the aeriul distribution. Although recommended for use in conjunction with pesticides, there is no documented example of this known to the author, so that distribution through crop spraying should not be a contributory factor. This fils the known pattern of distribution of PCBs in the environ ment, the highest concentrations coining from the heads of fresh water food chains, marine organisms and sea birds. High levels arc also known in terrestrial avian predators, but only recently has it been shown1 that in one region they can be found at levels comparable to those for organochlorinc pesticides. While relatively little toxicological work has been done on PCBs and some of the results are superficially con flicting, this can be explained and there can be no doubt that they have very similar effects on mammalian and avian metabolic processes to those of chlorinated pesticides, and indeed that synergistic effects can occur between the two classes.2 If any control over the use of PCBs is ultimately attempted this will he much more difficult than with pesti cides because of the very large number of uses to which they are put. There exists considerable difficulty in the analytical field because these compounds cannot be separated easily from pesticide residues, and this has probably resulted in quite a few reports in the past giving falsely high results for some pesticide residues.* Unknown peaks in gas chromatography analyses were early recognised* 0 but it was not until Jen sen7 applied mass spectrometry to the problem that some of them were identified as PCBs. Properties and uses The PCBs received early notice back in 1881* and were in widespread industrial use by I930.9 The biphenyls, terphenyls, naphthalenes, and mixtures of these arc chlorinated in varying degrees according to the use to which they arc put,10 and are marketed under trade names such as 'Aroehlor\ `Phcnochlor', and `Clophen'. The products arc complex mixtures of the various compounds and isomers. They range from mobile liquids to crystalline materials or hard resins, and while the lower members arc readily soluble in non polar solvents they become progressively less so with increas ing extent of chlorination. They are extremely stable com pounds, not hydrolysed by water, acid or alkali, and with a thermal stability such that they are used in (ire-proofing. They find use in elastomers, adhesives, paints, varnishes, printing inks, putty and as general fillers. The excellent dielectric properties lead to widespread use for electric insulators and as coolant'insulators in transformers. Tins stability and their low vapour pressures make them ideal as lubricants, hydraulic fluids, liquid seals, cutting oils ami vacuum diffusion pump oils, Employment in packaging materials has led to the contamination of food.11 There are a host of other uses, hut finally it may be mentioned that both the Monsanto Company and the USDIi have reported that they act as effective vapour suppressants in insecticide formulations and thus prolong the active life of an applica tion. However, it has not been acknowledged that PCBs have actually been used for this purpose commcrually. As an ancillary fact, a patent for the production of PCBs from lindane residues has been grained. This imilnpkii\ of usage has repercussions in ihe analytical area becaihc MQNS 085322 2tt Noycmhtr IV7I ChomiMi > h immy solvents, some adsorbents and other analytical materials, and even the atmosphere of a laboratory can be contaminated by PCBs. Occurrence in the environment It is now well established that PCBs can be found in wild life in many areas of the environment.'-'v 26 The highest levels arc generally associated with the industrial areas and the adjacent freshwater and marine food chains. The distribution is inevitably not quite so simple as this because of the migratory habits of some of the species involved19,24 and Ihc fad of widespread aerial distribution.28 Cohen and Pinkerton27 reviewed the hitter in respect of pesticides, mainly over the North American continent, and found higher levels in dust than rainfall. Risebrough et ai.2i studied the carriage of pesticides in the trade winds coming from Europe and Africa by collecting dust from the air over the Barbados Islands, and detected from 1-64 p.p.b. orgiiMoclilorinc residues. Dust collected over the Californian coast contained some thousand times greater concentration of organochlorincs, but none could be found in dust collected from over (he Central Pacific, although traces were inferred from the nature of the particulate matter. While no PCBs were delected in any of these samples, it was concluded that they were probably present in trace amounts. Tarrant and 'latton,28 however, who found organochlorine pesticides in rainwater samples taken from ull over the British Isles showed that levels were highest in the summer months (cf Risebrough of /.25) and in populous areas, also found I'CIIk in all of them although (hey did not estimate the concentrations. The importance of aerial distribution of pesticides relative to the hydrosphcric distribution has been stressed by Risebrough of af., and it is inferred that PCBs have a similar pattern of distribution. However, it would seem that with PCBs more emphasis should be placed on the hydrosphcric medium, because an important part in the transfer to the atmosphere, via dusts used as carriers in agricultural applications, can be considered as low in this ease. If the vapour pressures of DDT and PCBs are taken as being of the same order, it would then be expected that atmospheric levels of PCBs would be low relative to DDT. The relative concentration of pesticides amt PCBs in the hydrosphere and atmosphere have yet to be convincingly demonstrated. The outstanding feature of Ihc distribution is the occur rence in marine organisms on the continental shelves round North West Europe and North America, and also the extraordinarily high levels found in some freshwater avian predators, all associated with effluent from industrial activity.l'*,4`l,' ,7'2(,'2,,2ft Along the west coast of the USA PCBs have been detected in estuarine and coastal waters in San Francisco Bay, San Diego Bay and Puget Sound (Washington). In aicas remote from industrial activity round the Bay of California and parts of the Panama coast for example, birds' eggs contained 20-30p.g PCB each, but near the above mentioned industrial locations the eggs con tained up to several hundred and sometimes over a thousand |ig PCB egg. The cast coast of the USA has yielded similar evidence for contamination by PCBs. Holden and Marsden1* detected PCBs in seals from the Gulf of St I.awrence in shal 1341 low waters (Magdalen Islands) and in the deeper waters of the Cabot Straits. They have also been qualitatively detected in fish and shellfish from Texas and Georgia, and in the south, in the Gulf of Mexico, in estuarine waters at Charle ston, S. Carolina, levels of less than 0-1 p.p.m. were found in fish and blue crabs.20 Duke of af also monitored the results of an industrial leakage into the Escambia River which was carried through several inner bays through to the Gulf of Mexico olT Florida. Maximum levels at source ranged from 486 p.p.m. in sediment to 20 p.p.m. in fish, Crustacea and sediment in the outer bays. The best indicators ofcontamin ant levels were static organisms like oysters (up to 3 p.p.m ). Round the coasts of North West Europe the situation is similarly documented. Jensen et aiP investigated levels in marine ecosystems in Swedish waters. The closed nature of the Baltic area perhaps leads to somewhat higher con centrations than those generally found on Atlantic and American coasts. Levels tended to be lower in waters off West Sweden and lo the north of the Baltic proper, in the Gulf of Bothnia, and higher going south from the Stockholm Archipelago to the South Baltic. The levels ranged from 0 002 to 1 -0 p.p.m. in mussels and fish up to 150-240 p.p.m. in white tailed eagles. The concentrations were equivalent to the total DDT levels found. Kocman et alP qualitatively identified PCBs along the Netherlands coast from the Wadden Sea southwards to, and up, the Rhine, m mussels, fish and birds and their eggs. The uniformity of GC patterns suggested that they all originated from pollution of the Rhine. Holmes, Simmons and Tatton12 reported the pre sence of PCBs in marine birds and (heir eggs collected from round the British Isles, and Holden and Marsden1* showed them to be present in seals and porpoises round the coasts of Scotland, being highest in those from the cast coast (sec below). Bonner,21 investigating the deaths of seal pups on the Cornish coast, found PCBs here (160 p.p.m. in blubber) higher than in comparable northern samples (34-48 p.p.m.), but less than in hast Anglian specimens (350-520 p.p.m.). Presst, Jefferies and Moore, surveying PCB levels in British wildlife, reported an average of 4 (1-25) p.p.m. in (he eggs of marine birds, and comparing the cast and west coasts of Scotland in respect of two sets of twenty five eggs somewhat higher levels (7 us against 3-6 p.p.m.) in the western samples. No PCBs were detected in whales analysed by Wohnan and Wilson,29 and this is compatible with a distribution pattern confined u> the continental shelves. However, this may he a rather naive use of the evidence because the water solubility of PCBs. especially the higher chlorinated ones, is cxtiemcly low and the bulk of the PCB is more likely to be associated with sediment on the bottom and entering into the food chains mainly via bottom Jiving organisms. Most whales feed on plankton, and thus might in any case be expected to show' low levels. A further point of perspective is also given by the fact that loss of lower PCBs from aqueous suspen sions when aerated has been observed,49 Holden26 has traced aqueous pollution back to one type of source. The work on seals in Scotland having shown that levels were highest in the Firth of Forth region, water samples from the surface and at depth from the estuary and river up to Glasgow showed no detectable amounts MGNS 0*5323 I.W2 and only (race quantities in trunk sewer eflluents. The /.ooplunkton contained less than 0 03 p.p.m., and fish up to 2-6 p.p.m. However, industrial eflluents are usually passed to the sewage works together with domestic sewage, and so the sludge, which is dumped oflshore, was examined. The fifteen samples analysed ranged from 1-185 p.p.m. PCB on dry weight, with two sewage plants giving con sistently high levels (50-160 p.p.m.). Sludge from Manchester exhibited somewhat lower levels, and that from London less again, but taking into account the varying outputs, each area was estimated to contribute roughly 1 ton/ year PCB contamination to the marine environment from sewage sludge. In the case of inland areas sludge can be disposed of by spreading over the land surface, and so offer a route to terrestrial food chains. The question of why it is that relatively low levels of PCB are found in man and his domesticated animals, posed in I967> perhaps now has some answer. Distribution in terrestrial and freshwater ecosystems has largely been assayed in terms of the avifauna because of the effects of organochlorine pesticides and almost certainly PCBfi on some bird populations. The DDT/PCB ratio has been used by Riscbrough et al. as an environmental index,,4,24,as but when data is compared consideration must be made of the various biological factors, such as tissue distribution, species metabolism, migration, diet, health and age, which all affect residue concentrations. These authors have shown that the DDT/PCB ratio is low, below 2, near industrial areas, and increases with the distance away to become greater than 10 in remote regions. The geographical distribution in terrestrial and freshwater wildlife will be reviewed within the framework of these factors. Risebrough et a/.14 examined peregrine falcons and their prey, centring round the Bay of California. Falcons freshly migrated from the Arctic had low levels which increased with residence time in California; the levels in the Californian birds increased with age; and the indigenous adults showed the highest levels. The maximum Taws I Tissue distribution of DDT and PCB in peregrines and their prey Total DDT BCP DDTIPCB p.p.m. p.p.m. ratio Pcicgrmcs: unhatched egg muscle liver body fat Prey: egg whole body muscle 102 too 77 50 151 59 26-4 102 98 57 3-2 45 9-8 0098 100 10 1-3 15-6 3-3 5-5 270 20 November 197! Chemistry and imlnuiv values in Table 1 can be used to show the differences in tissue distribution. The same authors24 determined chlorinated hydrocarbon residues in breeding pelicans and cormorants in lakes to the north-west of the Great Lakes (Table II). As the birds used the same food sources the clear differences in results demonstrated a species difference probably due to variation in residue levels in (he migration areas, but possibly meta bolic differences in terms of rales of excretion of organochlorines into the eggs may be involved. Birds have also Table II Chlorinated hydrocarbon residues in pelicans and cormorants pp DDE PCB DDElPCB Eggs p.p.m. p.p.m. ratio Cormorant Pelican Fish (whole) 104 1-7 0-08 8 06 0-5 1-3 29 0-16 been studied in Britain12-19 and the extensive survey (599 samples) by Press!, Jefferies and Moore10 illustrates some of the factors involved; firstly habitat and migration (Table HI). Secondly; the eggs from marine birds from two colonics widely separated from one another demonstrates very convincingly (Table IV) specific differences related to migration habits. The guillemot spends the longest time in Table IV Specific differences related to migration habits ' DDTIPCB rath St Abbs Head Guillemot Razorbill Shag KiUiwake 0-233 0 500 0-625 0-666 Calloway 0 250 0-455 0-727 0-875 coastal waters, the KiUiwake the shortest time (here, for breeding purposes only, and the Shag is essentially seden tary. The effect of health on relative and absolute levels is seen in the report by Bonner21 on seal pup deaths . (Tabic V). TaWe V Effect of chlorinated hydrocarbon h"vcls on seal pup health Total DDT PCB DDTIPCB p.p.m. p.p.m. ratio Liver: Cornish 2 4 46 005 Northern (well fed) 06 4 0 15 Northern (starving) 20 6 0 33 Blubber: Cornish 11-1 160 007 Northern (well fed) 9-8 34 0 29 Northern (starving) 18 1 48 0 38 Table lit Habit and Migration factors affecting chlorinated hydrocarbon residues Liver Mini elass Ho samples (a) Terrestrial predators: static partial migrants migrants (hi l-roshwalvr (mostly static and mostly herons) (e) Marine 75 49 9 Mean p.p.m. 4-5 4-3 10 345 25 Egg No samples 115 6 5 124 96 Mean p.p.m 1-7 20 tO 47 40 MONS 085324 20 November 1971 Chemistry and Industry One of the most striking features of freshwater species is the extraordinarily high levels in herons at the head of a food chain where op to 900 p.p.m. have been found19 in British material. As the British heron is sedentary, occurs nearly all over the country, and there arc few migrants from the continent, this species might be expected to be a good geographical index of PCB distribution. Unfortun ately nearly all the samples obtained in the survey of PrcsRl ft a/.19 came from the Midlands and South East so (hat no clear pattern emerged. However, the age factor is well illustrated by this species as the average liver levels for nestlings was found to be 5 p.p.m. while that for adults was 9K p.p.m. Diet is of course an important consideration, and means that different species from the same area can exhibit very different PCB concentrations. Thus, while birds feeding on insects have shown 0*1 p.p.m. (liver), raptors feeding on mammals yielded 0*50 p.p.m. H is necessary then, when comparing or interpreting data, to take into consideration all these factors. Terrestrial restriction of PCBs to near industrial areas would seem to be reinforced by the failure of Holden26 to find them in freshwater fish in Scotland, and by Davis'1 who failed to find them in hectics, earthworms, slugs and grasshoppers of one agri cultural area in England. To what extent are PCBs found in human beings and foodstuffs? Jensen in 1966 first reported"? the presence of PCBs in human hair, and later reports12,23 indicated that levels in man and his foodstuffs were lower than those found in birds, and below l p.p.m. One exceptional case has been recorded,23 however. Recently a very extensive survey of foodstuffs in Sweden sampled between 1967 and 1969, and analysed for orgunochlorine pesticides and PCB's, has been published.1 In a wide range of foods and food materials, PCB levels were found to be below 0* I p.p.m. (90 per cent of 1400 sumplcs) and comparable to DDT levels. The higher con centrations came from freshwater and marine fish, especially those with a high fat content. Another case where relatively high levels were found was with milk. Cows excrete little DDT in their milk and here all eleven samples were below 0 03 p.p.m. DDT and 01 p.p.m. PCB on whole milk. In human milk relatively more DDT is excreted and (he average over 22 samples was 0T07 p.p.m. DDT and 0*16 p.p.m. PCB. Other relatively high samples are eggs and butter. (Tabic VI) Tabic VI Human milk l;M.yolk Butter Total No DDT 22 0 107 20 0-21 12 01 PCB 0 16 0027 003 DDTIPCB (p.p.m. whole material) 0 668 7-78 3 33 Toxicology Soon after the beginnings of industrial use of the chlorinated naphthalenes and biphenyls early in this century, human exposure was seen (o lead to skin eruptions (chloracne) and in animal inhalation and feeding experiments (1919), it was shown (hat liver damage occurred with the chlorinated naphthalenes. As a result of three human deaths, investi 1343 gations were continued in the 1930s, and it was further demonstrated in work on rabbits (hat in tho naphthalene series the higher chlorinated mixtures were the most toxic. The work was expanded by Bennett ct al.who also used mixtures including PCBs, and PCBs alone. A PCB con taining 65 per cent chlorine was used, and later one con taining 55 per cent. The substances were applied to rats by inhalation, subcutaneous injection, and oral means, and it was confirmed that (he high chlorinated naphthalenes were more toxic than the lower ones, but that (he PCB was more toxic still. Here, feeding at a lower rate (0-05g/rat every other day) produced extensive mortality, and as with the naphthal enes resulted in yellowing and enlargement of the livers. Liver damage caused by these compounds had not disap peared two months after dosing had ceased. This damage caused the animals to be extremely sensitive to damage by other compounds, e.g. carbon tetrachloride (used as a solvent for these mixtures), and much smaller doses than normal were rapidly fatal. Miller in 1944-'4 experimented with a PCB containing 42 per cent chlorine and worked on guinea pigs, rats and rabbits, using feeding, subcutaneous, skin and corneal applications. He used single doses ranging from 69 to 690mg and courses totalling up to 1380mg (over up to 54d) and found that guinea pigs were the most sensitive, rabbits less so, and rats least sensitive in respect of liver damage. Damage was largely confined to the liver but in rats there was also hypertrophy of the spleen. The occurrence of hyaline bodies in the liver was confined to the rat. Von Oettingen in 1955^5 found that even 0*05g/d fed to rats caused liver damage. Skin lesions were similar to those found in man. Man's exposure to these chlorinated hydrocarbons leads initially to dermatitis, then liver damage with resultant jaundice, and Greenburg,36 reviewing the situation in 1939. concluded that there had probably been at least six human deaths from this cause. Bennett el a/,32 had measured the air concentration at thirty industrial plants and suggested a maximum allowable concentration (MAC) of 0-5mgml for tetrachlorinated and higher chlorinated naphthalenes, with the observation that these levels had certainly been grossly exceeded over the previous twenty years. This work resulted in increased awareness of the hazards from vapours of these compounds and elementary improvements in industrial conditions has largely eliminated this source of danger (but see Biros22). The American Conference of Government and Industrial Hygienists in 1953'7 laid down an MAC for the lower chlorinated PCBs of I 0mg,m\andfor thebigher chlorinated oncs('Aroch)ors' 1254-)0-5mgm'This appears to presume parallelism with the naphthalenes, and these figures are perpetuated in handbooks of industrial toxicology,38 but recent papers2,45 point to the reverse situ* ation (see below). These MACsare to becomparedwiih those for `Aldrin' and `Dicldrin' (0-25mg/m\ tentative) and parathion (0-lmg/m3). The oxidised chlorinated biphenyls are more toxic than the parent compounds.38 McLaughlin in 1963 published the results of toxicological studies on a number of chemicals which might be found in food39 using a sophisticated method based on injection into fertile hens' eggs. 25,000 eggs were used over three years and strict controls set up. Among the compounds tested was the MONS 083325 1344 `Arochlor 1242" injected at 0-025 and 0-Jml giving a 0 and 5 per cent hatch as compared with over 95 per cent in the control group. Teratogenic effects were also noted in some of the chicks which did hatch. These results may be com pared with those for `Heptachlor', where 0 05 and O-IOml of a 1 per cent solution in propylene glycol (non-toxic) gave a 75 and 65 per cent hatch respectively. Flick cl al.40 endeavouring to identify the factor causing the chick oedema disease, following reports that the factor was highly chlorinated and that a plasticiser (PCB) used as a cage wire coating fed at 0 01 per cent or higher caused oedema in chicks, investigated the.effect of `Arochlor 1242'. Groups of twelve chicks were fed on diets containing 200 or 400 p.p.m. over a three week period, changes in weight being noted. Weight gain was lower with the 400 p.p.m. diet and indeed loss took place at the end of the period. Three chicks on this diet died. Here the hydroperi cardium volume was ten times larger than with the 200 p.p.m. level or the controls, the pancreas, kidneys and adrcnuls affected, and haemoglobin levels were lower. The PCB produced similar effects to the oedema factor, but was not so potent, and gas chromatography demonstrated that it was not the same. Two groups of workers, Risebrough. Peakall et al. in the \)SU.2*.4 > and Jefferies, Moore, Press! et al in Great Britain.19,44 have actively pursued the effects of organochlorine pesticides and PCBs on birds. The decline in certain bird populations, especially raptors, has been attributed to the presence of organchlorinc pesticides, but it is also possible that PCBs have played a part in this, not only because of their intrinsic toxicity but because it has been shown (in insects,3 and below) that there are synergistic effects between some PCBs and DDT and 'Dieldrin*. Lctlml toxicity to the adult bird is not the only factor because it has been shown14,41 that organochlorinc pesticides at the order of one p.p.m. arc effective in inducing steroid hydroxylases in avian liver, thus leading to lowered oestrogen levels and reduced reproductive capacity. Added to this DDL has an entirely different effect on the reproductive system, that ofcausing eggshell thinning, which causes added failures in reproduction. Teratogenic effects may also occur because of the cxcrction/conccntration factor in the eggs. It is thus necessary to review the effects of the oTganochlorinc pesticides on birds in conjunction with those of the PCBs. Following work by Peakall,41 which demonstrated that pigeons fed with DDT at 10 p.p.m. and/or `Dicldrin' at 2 p.p.m. for one week had higher levels of testosterone or progesterone metabolites than controls. Risebrough. Peakall ci compared the effect of DDE, DDT and PCB (`Arochlor 1262') in increasing the levels of polar metabol ites in ocslradiol metabolism, again using pigeon liver isolates in vitro. Their results arc given in Table VII. Table VII Cnmrol 1)1)1 <40mg/k*i> 1>I)T (4(hn*/k*> PHI (20mg/ks> /'.// nwtuMitvs foinu il (in|i nto/cx) 29 76 93 I Ml 20 November I97t t/nnmfiv uitt{ This PCB has about five times the capacity to reduce oestradiol levels than DDT or DDE. The effect of a single dose of DDT may last for over two months. This work was extended to compare the effects of two different PCBs in kestrels, again using liver microsome isolates.4' The kestrels were fed at 0-5 and 5-0 p.p.m. levels with `Arochlor 1254' and `Arochlor 1262", and the results were as in Table VIII. Table VIII Pniar nu-lahnlili'S {nmohslx niicrnxonin/ fraction) _ __________________`1254'_____________ `I2ft2` Control 0-5 p.p.m. 5-0 p.p.m. 0 13-65 60-5 0 1905 47-95 While these figures do not clearly indicate the relative activity of these PCBs, it has been shown that `Dieldrin and PCB are much more active in reducing oestrogen levels than either DDT or DDE.43 That pesticides reduce oestrogen levels in mammals has also been demonstrated. Presst, Jefferies and Moore44 investigated the lethal effects of `Arochlor 1254' on Bengalese finches. Food containing higher levels of PCB (440 p.p.m.) was refused by the birds (100 per cent mortality not occurring) but it was still possible to calculate (he LD50 as 25.V6mg/kg/d. Seven out of the 38 birds died. Enlarged kidneys was the main feature, with in two cases increased volume of peri cardial fluid. While there was a correlation bet ween dose rates and liver concentrations, there was also considerable varia tion in levels (3-697 p.p.m.). Whether a particular con centration will be fatal will depend, as with organochlorinc pesticides, on the condition of an animal. Considerable storage in fat is possible and until this reservoir is saturated, concentrations will probably not rise to lethal concentra tions in susceptible organs. So danger can arise in limes of stress (e.g. starvation or with the breeding cycle) when the fat reserves are mobilised releasing large quantities of PCB or whatever. The liver by itself in these birds may thus not be a good index because the liver fat reserves may vary considerably and will themselves be mobilised ultimately The authors therefore suggest the brain/liver percentage as a useful index, being high in those birds that died (83-7 per cent and low in the survivors (26-4 per cent). The LD<0 for DDT is some thirteen times lower than for this PCB. but consideration has to be given to the fact that while the DDT mortality curve is steep (no deaths at 1000 and all dead at I200mg/kg/d), the PCB curve is shallow, so that at lowlevels PCB may be more toxic than DDT. The authors con clude on the basis of this experimental work, and reasonably assuming that no drastic change in useage of PCBs is likely to have taken place over the past two decades, that lew bird deaths have been caused by PCBs. However they state, without citing evidence, that the PCBs do not vary inarkcdK in toxicity and this is at variance with recent work2 4VJf> (sec below), the PCB used here being of relatively low loxicttv. Additionally the authors do not consider the possibility of synergistic effects.2 It was recognised that the position with sublethal effects may be different. MGNS 085326 3<l Nov'inlxi IV7I Clu-tnhtiY uti/l huiuxtr\ Very litlle work:,M,' v hits been done on the effect of PCBs (and Icrphcnyls) on aquatic organisms, despite the fact that it is known that some marine Crustacea and fish arc very sensitive to orgnnochlorine pesticide residues.44 For example Crouton vulgaris (brown shrimp) has an LCso/48h/ 15 c for I)|)T of 0.003-0-1 p.p.m., and levels as low as 0-0001 p.p.m. may be detrimental to some species of mollusc. One difficulty in the study of toxicity to aquatic organisms is the extremely low solubility of these com pounds in water and the difficulty of obtaining sufficiently stable emulsions.47 v The use of solubilising agents, of low toxicity, overcomes this. Zilko,4V using `Corexit 7664' to solubilise 'Arochlor 1221' and `Arochlor 1254', carried out 192 hour tests with these compounds using Atlantic salmon parr. He found that concentrations above 2mg/l were lethal. Wildish4* using `Arochlor 1254' in emulsions, or solubilising with `Corexit 7664', carried out 30d tests with Gammarus ovvanicus and found lethal threshold values of 0-001 to 0-0Img/l t'Corcxit') and 0-01 to 0-Img/l (emulsions). Guthrie ct at.41 tested mixtures containing chlorinated Icrphcnyls and their oxidation products and found lethal threshold values of about 5mg/l and pertinently that low' oxygen levels in the water enhanced the toxicity. Duke vt af.:o who monitored PCB levels in biota and sediment in the Escambia Bay area of Florida as a result of an industrial leakage of PCB into the Escambia River, conducted both acute toxicity tests and 20d bioassays. 48h tests on pinfish and juvenile shrimps at the 100 p p.b. level was not toxic to the fish but caused 100 per cent mortality in the shrimps. Oysters received a 96h test and the effect was measured in terms of arrest of shell growth. Here 1 p.p.b. resulted in 19 per cent decrease in shell growth and 100 p.p.b. 100 per cent. Resultant whole body concentrations for the three organisms were 17,3-9 and 33 p.p.m. respectively. It should be noted that the oysters when replaced in PCB free water for three weeks recovered their normal growth rates. In the 2(>d assays using a concentration of 5 p.p.b., a 72 per cent mortality occurred in juvenile shrimps and 5 per cent in juvenile crabs. It would appear then from all this work (hut some Crustacea and molluscs Rre as sensitive to PCBs as they are to orgnnochlorine pesticides. Some toxicological work has been effected using insects.2-46 Morinrty3 dosed fourth jnstar nymphs of Chorthippus hrunneus (grasshopper) topically with `Arochlor 1254' at 12-5, 50 or 200|jg levels, but found that definite mortality was only associated with the 200|ig group plus a possible sub-lethal effect associated with moulting (fat mobilisation). The maximum amounts of PCB in individuals of the latter group were I4pg (male) and 8ng (female). The work of Lichtenstein, however, is much more revealing as to the relalive toxicity of the various PCBs and the synergistic effects with DDT and `Dicldrin'. Groups of 50 Drosophila mchmogastcr were placed in contact with vessels coated with a layer of the substance or mixture of substances, and groups of 15 Musca donrestica were dosed topically. Tests of the individual substances showed that 'Dicldrin' was some 25-30 times more toxic than DDT, and J-8000 times more toxic than the PCBs. The higher chlorinated biphenyls, and (he Icrphcnyls. gave rise to no mortality in the 24 or 4Hh tests, but toxicity increased with decrease in 1345 chlorine content in the lower half of the series. These results raise doubts as to the relevance of the many papers which have used `Arochlor 1254', which here has little or no effect under these conditions. The synergistic effects with `Dicl drin* were positive with some of lower 'Arochlors' and uniformly positive with /i/) DDT up to `Arochlor 1254". However, with the higher chlorinated PCBs and PCTs a reduction of toxicity was observed. While it is improper to transpose results from one phylum to another and short term toxicity may have little bearing on long term effects, nevertheless this paper is a strong indication that consider able care should be taken in planning these toxicological studies. Work using mammals is equally sparse. A picliminuiy study by Sabolka,5y using `Arochlor 1254' and `Arochlor 1260' or DDT in single doses of M0mg/kg ('Arocblor's) or 0*25mg/kg (DDT) carried out behaviour tests on mice over periods of 4 to 24h after administration. There is a clear difference between the two groups of substances. 1)01 probably attenuating and PCBs probably enhancing central inhibitory systems. The paper by Bitman and Cecil4* surveying the oestrogenic activity of DDT analogues and PCBs in terms of the 18)i glycogen response of immature rat uterus assumes considerable importance in relation to a lot of the work cited above. The stereochemical require ments are quite strict, and in general for diphenyl-methane and -ethane, and iriphcnylmethanc compounds activity is restricted to those where either the pp' positions arc vacant or filled by hydroxy or methoxy groups, being inactive where halogen or alkyl groups arc present. So the pp compounds perthane, kelthanc, DDE, DOD and methoxychlor are inactive. However, pp'Ol)T is active ami the op'isomer some sixteen limes more so, while of the others mentioned only qp'DDE gains a response. `Arochlor's 1221-48' are about half as active at />/>'DDT, but the higher members are inactive, (cf. Lichtenstein). In perspective though these compounds only have something like 10 * times the activity of natural oestrogens, but this fits well with the observed pattern of steroid hydroxylase induction in birds, where DDT and PCB arc very active but DDE is less so. Perhaps another significant point is that the oo and phcnols have an equivalent oestrogenic activity. The lower chlorinated PCBs could be degraded in the atmosphere as has been shown by laboratory experiments where the greatest diminution in one gas chromatograph peak was found where PCBs on an aqueous surface were subject to UV irradiation.51 At the same time it has been observed1717 that the lower chlorinated PCBs tend to be absent in wildlife samples, particularly in birds, and it may be speculated to what degree there may be differential excretion or in vivo breakdown, and what effect this has. A recent study by Vos ei al,52 reveals another important aspect. They discov ered that two out of three 60 per cent chlorinated PCBs contained highly toxic oxygenated impurities. These two commercial preparations (`Phcnochlor DP6\ `Clophcn A60 ) when injected into hens' eggs at the 3-5mg level caused almost 100 per cent mortality whereas the third sample (`Arochlor 1260') gave a relatively low mortality. A fraction containing no PCBs was isolated from one of them by `Florisil' column chromatography and shown to be toxic. M0NS 005327 1346 Gar chromatography and mass spectra showed this fraction to contain tetrachioro and pentuchloro-dibenzofurans which were, however, masked by hcxachloronaphthalenc and hep* tachlorobipheny) respectively, thus limiting the accuracy of quantification. The penlachlorodibenzofuran was estimated to be at about the 5 and 20 p.p.m. level in the two samples. That PCB exerted a similar effect to that of the chick oedema factor (CEF) had been noted previously,40 and that toxico logical studies using PCBs had produced variable results. 1,2,3.7,8,9,-hcxachloro dibcnzodioxin has now been identi fied one of the oedema factors*2 and it may be recalled that the toxic factor in the weedkiller 2,3,5-T was shown to be a tetrachioro dioxin.** In fact these chlorinated dioxins and dibenzofurans are very highly toxic groups of compounds. 0*2|ig pcntachlorodibcnzofurun is needed to cause 100 per cent mortality in hen eggs as compared to 0-05ng of hexachlorodibcnzo-p-dioxin. The occurrence of the dibenzofuriins in PCBs is associated with the use of sodium hydrox ide in the distillation of erude PCB. Pentachlorophenoi (PCP) and 2,3,4.6- tetrachlorophenol are possible precursors of CEF and have been found to be present in toxic oleic acids.*4 It is evident then that other compounds besides the PCBs themselves should be sought for in wildlife and (hat indivi dual compounds us well as commercial preparations should be used in toxicological studies. Unfortunately the indivi dual PCB compounds arc not readily available. Holden and Marsdcn** have already noted the presence of unidentified polar compounds in wildlife extracts. Jt is to be hoped that the current FDA programme56 on the toxicology of PCBs takes into account all these factors. Analysis ' PCBs arc extracted together with chlorinated hydrocarbon pesticides in routine residue analyses,*7 and being complex mixtures of compounds with GC retention times on non polar columns almost identical to a number of pesticides, notably of the DDT group, present an analytical problem which is not completely soluble by gas chromatographic means alone. Chemical conversion of the pesticides, leaving the PCBs almost unchanged, provides a partial but not completely satisfactory solution, but group separation is fundamentally sounder, (his of course providing additional evidence of identity. Both thin layer chromatography and column chromatography have afforded quite good partial separation of PCBs from pesticides and the best scheme*8 claims to leave only `Aldrin' with the PCBs, with which there is very little interference by the PCBs. A number of workers18-22-*0-60 have confirmed the presence of PCBs in living tissues by means of mass spectrometry, but apart from this means the quantification of PCBs presents severe problems because of the large number of compounds involved and that the individual compounds are not readily available, so that most authors have only been able to calculate approximate figures. Gas chromatography retention data for PCBs is now adequately documented12,16.ih.2c.*o.61 (and also1-2-1*-14,20, J4,2S.m>..w) and on non-polar columns the main region of interference of PCBs and organochlorine pesticide residues with one another may vary from the point of emergence of 20 November 1971 Chemistry and hid" u-. pp'DDE that of pp'DDT. PCBs may continue to emerge with retention times up to four or five times that of DDT. It has been noted in this laboratory that response to PCBs relative to organochlorine pesticides can be small on some columns, and from the viewpoint of determining pesticide residues, can ameliorate the situation. However, using more polar columns, e.g. 'QF-I* or `XE-60*,12,2*'*0,62 PCBs emerge largely prior to the DDT group, which allows simple quantification of the latter, but may still leave an unsatis factorily complex chromatogram. Improved resolution of PCB compounds has been claimed6* using novel stationary phases. One alternative has been to alter the retention time of pesticides by derivatisation, leaving the PCBs intact, and of course aiding the identification of the pesticides. Jensen*g used a mild nitration technique adapted from Erro et al. and originating from the Schechter-Haller method, claimed that the PCBs remained unaltered while members of the DDT group were effectively removed, although other organochlorines (e.g. `Toxaphene', heptachlor epoxide, lindane and BHC) are not removed. This scheme (1:1 HNO3/H2SO4 for 5min at 0c) was followed by Risebrough et a!.,14,50 but Reynolds61 found that DDT derivative peaks ultimately emerged on the chromatogram making for an unprofitably long analysis time. Moreover, some lower chlorinated PCBs appeared to have been affected by the procedure. Saponification with alcoholic potash1*-14'*9 leads to the dehydrochlorination of pp'DDT, pp TDE, and `Toxaphene', with the derivative peaks appearing earlier in the chromatogram, and the PCBs reportedly unaffected. BHC is destroyed by this procedure. PCBs have also been differentiated from DDT using carbon-skeleton chromato graphy.64 Separation prior to gas chromatography is to be pre ferred not only because simpler chromatograms can be obtained but because this will give nearly as much evidence as to identity as derivation. Thin layer chromatography, reverse phase paper chromatography12 and column chroma tography afford means of obtaining partial separations of organochlorine pesticides from PCBs and fractions can easily be obtained where only `Aldrin*, `Heptachlor', and pp'DDE remain with the PCBs. The former two arc not very important in respect of the gas chromatography separation because there is usually little interference between them and PCBs, but pp'DDE can emerge with the major PCB peaks using non-polar columns. Thin layer chromato graphy has given this sort of separation using silica gel1 " and alumina,1-2 and in column chromatography Holden and Marsden26-45 claimed good separation of PCBs using either alumina, silica gel, or both in series with long narrow columns. Reynolds61 documented a separation with 'hlonsil', while Bevenue and Ogata62 commented on their failure to reproduce this work in terms of pesticide separations only, and noted the differences in activity between `regular* and `PR Florist!'. This reviewer has found no difficulty in obtaining this separation using `Florisil*. Armour and Burke*8 in a carefully documented paper showed that it was possible to carry out a separation leaving only `Aldrin' with the PCBs. For this they used silicic acid partly deacti vated with 3 per cent water mixed with eelite and eluted the HUNS 065326 20 November 197/ CltcmiMiy unJ Intimity PCBs (`Arochlor's 1254 and 1260') with petroleum ether. `Arochlor 1254* needed the larger volume of eluant and the separation was more critical. The cautionary note is added that uny trace of polar solvent in the sample will make the separation impossible and pp'DDE will emerge with the PCBs. Also, the separation is only possible provided that the column (20 i 5g) is not over loaded (/.$. not exceeding 2(Vp PCB). This then solves the main separation problem leaving on non-polar gas chromatography columns only a small PCB peak which may interfere with the estimation of *Aldrin\ These authors have also documented the separ ation of chlorinated naphthalenes.65 Confirmation of identity has been achieved by combined gas chromalography/mass spectrometry,lt,,22,59,6 but gener ally quantification is not simple because of the large number of compounds involved Hnd because these arc not readily available individually for reference purposes. If it can be assumed that a fraction contains only PCBs (i.e. in a column chromatography or gas chromatography effluent) and that the composition on a gas chromatography trace conforms to that of a commercial mixture, then microcoulomctric estimation will give an answer. Jensen el a/.,17 using a combination of mass spectrometry, ECGC and microcoulomclry obtained results which were only accurate to about a factor of two. With the same assumptions electron capture detection can be used, referring to commercial PCB mixtures26 either by estimating the total peak area19-59-6* or basing the calculation on onc,,6,9 or more20 suitable peaks. pp'DDE or `Dicldrin' may be used as an internal standard.16,50 One empirical approach calculated one PCB peak as pp'DDT and multiplied by a factor of ten to obtain a result;24 another66 took the total area:weight ratio to be equivalent to that for DDE; and another 19,50 assumed the response of each peak to be equivalent to DDE and applied a correction factor from the use of microcoulometric detection (the authors did not have permanent access to a microcoulometric detector). Gregory67 studying the electron capture coefficients of mono- nod dichloro- and methylbiphenyls showed that there is over a twentyfold variation between the chloro compounds. Zilko49 determined the concentrations of PCB in fresh and salt water by means of ultraviolet spectrophotometry and fluorescence. While the lower chlorinated PCBs can be prepared easily68 and only simple mixtures formed when using the Ullmann reaction, the higher members are more difficult to make singly. Diwvsniim The decline of certain bird populations was associated with the use of 'Dicldrin' seed dressings and has been attributed to lelhal toxic effects. With increasing awareness of these dangers, better monitoring and usage control, at least in developed countries, lethal toxic effects are progressively less likely to occur. Rather, the significance of PCBs (and pesticides) to man and other organisms must now be seen in the context of sub-lethal effects having long term influence on populations through the media of reproductive processes (reduction in fertility, delays in breeding), teratogenic and carcinogenic effects on both the parent and later generations. LI>no tests, even over a long period, are irrelevant from this viewpoint. Certainly it is true that severe mammalian 1347 liver damage and death can result from high PCB levels hut these are only reached in a few foodchain heads, and the normal levels found in man are not of this order. To be set against this, however, is the finding (in LD50 terms) that while with DDT there appears to be a definite `no effect' level this is apparently not true for PCB. Precisely what compounds are responsible for the toxicity of PCBs is not yet clear, but it seems certain that it concerns the lower chlorinated compounds and probably the oxidation products in vivo or in vitro. It also emerges that impurities in some commercial mixtures are certainly highly toxic, and if the fact of synergistic effects, though demonstrated as yet in one area only, is taken into account then the picture becomes a very complicated one. Clearly it is extremely difficult to carry out strictly controlled toxicological studies at a feeding level of the order of I p.p.m. over a long period, and in terms of multigencration tests. The need for multi generation tests may be related to DDT, where, despite many years study, it has only recently been indicated that, with only the original parents dosed, carcinogenic effects may occur in later generations (6th generation mice). DDT may again be used to illustrate the sort of effect which may be looked for. In California, Oregon and Washington, genetic changes in the fruit fly population have been shown to result from heavy spraying programmes in these areas, and in (he latter two states were tied to two specific forest spraying programmes. The pattern of these genetic changes can also be correlated with spread by winds over long dist ances. With PCBs the major dispersal medium is probably water, but otherwise there are no essential differences in the situation. The PCBs are spread all over the continental shelves which are fed by industrial effluents. The toxicology of the weedkiller 2,4,5-T5? and of mercury residues69 has recently come to the fore and they present some parallels with the PCBs. While in contrast to PCBs there is a definite, but smalt, contribution to agricultural pollution, by mercury from seed dressings, the industrial contribution must lead to a similar marine distribution to PCBs, although as yet very little is known about this area. Mercury, in contrast to PCB, is only cumulative in living tissue to a limited extent, and there is a definite natural contribution from the sea floor. The massive aerial use of the weedkiller 2,4,5-T as a defoliant by (he Americans resulted in tcratological as well as direct toxic effects due to traces of a chlorinated dibenzodioxin. It is as well that PCBs are not used in such fashion because it has now been shown that some commercial preparations contain traces of chlorinated dibcnzol'urans which are also highly toxic. Water pollution is receiving considerable attention within the traditional framework of oxygen deficiency, reduced and oxidised nitrogen, temperature and so on, but the type of pollution problem presented by PCBs, DDT and so on is largely ignored. In a recent official report nn loxic chemicals, which recommends further work to appraise the situation in fresh, estuarine and coastal waters, there appears to be a large conceptual gap. Commenting on the presence of DDT in raw sewage, this is dismissed as a significant source of riverine pollution because DDT is solid attached and largely remains in (he sewage sludge, but what happens to the sludge is blithely ignored. The ironic situation is of MONS 005329 1348 course that Ihc sludge is commonly dumped in estuaries or even spread out over the land so that pollutants such as the l*CHf* arc recirculated through the food chains. These arc but a few aspects of environmental pollution which can ultimately lead to man's own detriment, in many cases the users of pollutant materials, industrial or domestic, have no conception of their own insidious contribution to pollution, and in the ease of the very useful PCBs it is very difficult to see how their disposal can be controlled to minimise pollution. From the point ofvicwofrestriclingtypes of use to those least likely to result in pollution, one prod ucer, Monsanto, has made a very responsible move70 in this direction, but as PCB manufacture is no longer covered by patents this may not be effective. It is obvious that with their ubiquitous presence the effects of PCBs and associated compounds must be investigated with great thoroughness. It is not only to preserve bird populations or other wildlife but to prevent long term changes in man himself that such searches arc directed. The author is grafeful to the H. J. Heinz Co. Ltd, for permission to publish this paper. Rrfimm WesUMV, 0., Norin, K. A Andersson, M., Far Ftida, 1970, 10 ? Lichtenstein, K. P., Schulz, K. R., Puhremann, T. W. A Liang, T. T., J. mm. Enf,, 1%9, 62, 761 t Kocman, J, It. A Gcndcrcn. H. van, J. Appl. Ecol,, 1966, 3(SuppU. 99 Harrison, K. U,, J. Sri. Fd Agric., 1966, J7. 10 ' Rohtirn, J,, Analyst, Ixmd., 1965, 90, 467 ft Walker, C. H., Hamilton, C. A. A Harrison, R. B., J. Sci. Fd Agric., 1967, 1ft, 123 7 Anon., New Sclent., 1966, 612 s _ Schmidt, H. A Schultz, G., Ann. 1881, 207, 338 Penning, C. M., Ind. Eng. Cheat., 1930, 22, 1180 i# Anon,,Technical Bulletin O-I-F/l, `The "Arochlor" polychlorinated polypheny!*', Monsanto ft Hailey, S,, Hunyan, P. J. A Fishwick, F. B., Cfrcm. A Ind., 1970, 705 * Holmes, I>. C., Simmons, J. H. A Tatton, J. O'G., Nature, Land., mi, 216, 227 ' Holden, A. V. A Minsdcn, K,, ibid., 1967, 216, 1274 > Kimbrough, R. W.. Ricchc. P.. Pcakall. D. B.. Herman, S. G. A Kirvcil, M. N., ibid., 1968, 220, 1098 i.' Report for 1966 8, Monks Wood Experimental Station, Nature Conservancy, 1969 ft Koemnn, J. H., Ten Noever Dc Brauw, M. C. A De Vos, R. H., Nature, Land., 1969, 221, 1126 7 Jensen, S., Johncls, A. G., Olsscn, M. A Ottcrlind, G., ibid., 1969, 224, 247 t* lliiglcy, G. !!., Reichet. W. L. 4 Cromarlic, H., J. Assoc. Off. Anal. ( hem., 1970, 53, 251 iv press!. Jefferies, D. J. A Moore, N. W., Environmental Pollution, 1970, I, 3 2u Duke. T. W.. l-owc. J. I. 4 Wilson, A. J. Jr.. Bull. Lnv. Contain. 4 Toxical , 1970. 5. 171 Runner, W. N., `Seal deaths in Cornwall, autumn 1969'. 1970, Niilural Fnviionmrnl Research Council Publications Series C no I 77 lliros, l;. J.. Walker. A. C. A Medbery. A.. Bull. F.n\. Contain. & Toxicol., 1970. 5. 317 2) Third Report ol the Research Committee on Toxic Chemicals. 1970, London Agricultural Research Council r* Anderson, I), W., Hickey. J. .1 . Risebrough. R. W., Hughes. D. F. 4 Chriulcnucn, R. F:.. Can. Fid Nat., 1969, 83, 91 20 November )97! Chemistry and Indus/n 25 Risebrough, R. W., Huggett, R. J. A Griffin, J. J., Science, N.)' 1968, 159, 1233 7* Holden, A. V.. Nature, I.ond.. 1970, 228. 1220 27 Cohen, J. M. A Pinkerton, C., in `Organic pesticides in the environ ment', ed. Gould. R. F., 1966, Advances in Chemistry Series, no 60. Washington: American Chemical Sneietv, p 163 28 Tarrant, K. R. A Tatton, J. O'G., Nature. /W.. 1968, 219, 725 2* Wolman, A. A. A Wilson, A. J. Jr, Pesticides Monitanng Journal 1970, 4, 8 20 Report of the Government Chemist 1967, 1968, London: HMSO p 108 11 Davis, B. N. K., Ann. appl. Biol., 1968, 61, 29 n Drinker, C. K., Warren, M. F. & Rennet, G. A., J aiJ. H\g Toxicol, 1937, 19, 283 J-1 Bennett. G. A., Drinker, C. K. A Wanen. M. F.. iW, 1938. 20, 97 34 Miller, J. W., US Public Health Report 1944, 1085 55 Von Oettingen, W. F, 'The halogcnaled hydrocarbons - toxicity and potential dangers', US Public Health Service Publication no 414, 306 56 Greenburg, L., Mayers, M. R. A Smith, A. R., J. ind. Hyg. Toxicol. 1939, 21, 29 37 American Conference of Governmental Industrial Hygienists 1953, in Arch. Ind. Hyg. Occtip. Med., 8296; and 1969. m `Threshold limn values for 1969', Technical Data Note 2/69, 1969, Department of Employment and Productivity, HMSO ia Sax, N. 1., `Dangerous properties of industiinl materials', 1957, New York: Reinhold ,v McLaughlin, J. Jr, Marliac, J.-P., Verreu, M. J., Mutchler, M. K. & Fifzhugh, O. G., Toxic, appl Pharmac., 1963, 5, 760 40 Flick, D. F., O'Dell, R. G. A Childs, V. A.. Poult. Sci., 1965. 44, 1460 41 Pcakall, D. B., Nature, Land., 1967, 216, 505 47 Idem, Sclent. Am., 1970, 73 43 Linccr. J. L. A Peakaif, D. B-, Nature. Loud., 1970, 228, 783 44 Moore, N. W., Biologist, 1969, 16, 157 4J Bitman, J. A Cecil, H. C., J. agric. Fd Chem.. 1970, 18, 1108 4ft Moriarty, F., Entomoiogia exp. appl, 1969, 12, 206 47 Guthrie. J. E. A Acres, O. E., Bull Lnv. Contain. 4 Toxicol.. |97U, 5, 145 4 Wildish, D. J., ibid., 1970, 5, 202 4 Zitko, V., ibid., 1970, 5, 279 50 Sobolka, T. J., Information Bulletin, BIBRA. 1970. 9, 363 51 Risebrough, R. W., Rciche, P, A Olcolt, H. S., Bull. Lnv. Contain. A Toxicol., 1969, 4, 192 52 Vos, J. G., Koeman, J. H.. Van Dcr Maas. Ten Noever Dc Brauw, M. C. A Dc Vos, R. H., Fd Cosmet. Toxicol., 1970. 8, 625 31 Anon., Nature, Land., 1970. 226, 309 *4 Higginbotham, G. R.,, Ress, J. A Rockc, A., J. Axsae. Offit: Anul. Chem.. 1970, 33, 673 55 Holden, A. V. A Marsden, K., J. Chromat., 1969, 44, 481 Anon., Information Bulletin, BIBRA, 1970, 9, 212 37 Ahling, B. A Jensen. S., Anal. Chem., 1970, 42, 1483 5* Armour, J. A. A Burke. J. A.. J. A star Offic. Ana! Chem . 1970. 53, 761 5* Widmark. CL. ibid.. 1967. 50, 1069 60 Hutzingcr, O., Jamieson, W. D. A Zitko. V., Nature, Loud., 1970, 226. 664 ft> Reynolds. L. M., Bull Em: Contain. A Toxicol. 1969. 4, 128 62 Bevcnuc. A. A Ogata, J N.. J. Chromat.. 1970. 50. 142 63 United Stales Patent 3,520,108. July 14 1970. Monsanto 64 Asai. R. I.. Gunther. F. A., Westlake, W. h. A Iwaiu, Y.. J 4g< n Fd Chem., 1971, 19, 396 ft* Armour, J. A. A Burke, J. A.. J. Assoc. Offic. Anal. ( hem.. I V7f. 54, 175 ft Report of the Government Chemist, 1969; 1970, London: IIMSO p Kl ft7 Gregory, N. L., J. Chem. Soe. (B), 1968, 295 68 Hey, D H. A Perkins, M. J., Organic Syntheses. 19<>9, 49, 44 ft Anon., Information Bulletin. BIBRA. f970. 9. 2 (2 70 Tinker, J., New Scientist and Science Journal. April 1 1971 l(> MUNS 085330 20 S'inrmbi t IV71 Chcntisliy and Industry 114'* Laser Raman spectra of drying oils and alkyd resins by L. A. O'Neill and N. A. R. Falla Paint Research Association, Teddington, Middlesex Laser Raman spectroscopy is proving an important complement to infrared spectroscopy in the polymer field.1 In (his paper is reported a comparison of laser Raman spcctrn mid infrared spectra of some drying oils and oilmodified resins used in the coatings industry. The laser Raman spectra were recorded in the Division of Chemical Standards of the Nutional Physical Laboratory. Materials and experimental The samples examined included linseed oil, lung oil and a pcntucrythritol linseed fl-phthalic alkyd resin. The Raman spectra were recorded on a `Spex' Model 1401 double grating laser Raman spectrometer, using a `Spcelrophysicx* Model 140 argon ion laser with excitation at 4K8nm. The samples were examined in glass capillary lubes with 90 illumination. The infrared spectra of the samples as thin films on KBr plates were recorded on a `Unicam* SPI00 spectrometer. RcmiHk The comparative infrared and laser Raman spectra are shown in K;gs l to 3 and present the following features. 1.disced oil The infrared spectra of unsatunilcd glyceride oils show strong bands at 2850 and 2920cm'1 which, together with medium intensity bands at 1460, 1375 and 720cm-1, are assigned to aliphatic C H vibrations. The ester groups present give rise to (he strongest bands in the spectru at 174H, 1239, 1155, 1100 and 1020cm >. The methylene rntcrrupled m umalurnlion in the chain does not give rise to any strongly active infrared modes, the major band being the medium intensity absorption at 3008cm'1. There are several bands in the infrared spectra of tri glycerides which are common to the Raman spectra, although their frequency may be slightly different. These include the bands at 3008, 2920, 2850 and 1748cm '. The ester bands are very much stronger in the infrared than in the Raman spectra; in particular the 1748cm 1 C=0 stretch, the strongest infrared band, is only weakly Raman active, while the 1239, 1155, 1100 and 1020cm 1 bands are all absent in the Raman spectra. The main feature in the Raman spectrum not found in the infrared is a very strong band at 1659cm 1 characteristic of unsaturation. There arc, in addition, bands at 2966. 2906. 1442, 1304 and 868cm"1 due to aliphatic C - H vibrations and two ester bands at 1267 and 1077cm '. The ratio of the intensity of the unsaturation band at 1659cm-1 to that of the aliphatic band at 1442cm 1 was determined for linseed in comparison with soya bean oil. From these ratios it was possible to obtain an assessment of the relative degree of unsaluration of the samples. The value obtained was in agreement with that determined by the Wjjs' iodine method. Tung oil The infrared spectrum is similar to that of linseed oil. The main differences are associated with (he trans-franx-cis conjugated triene structure present in tungoil. Tins structure gives rise to a strong infrared band at 990cm l, together w ith less intense bands at 960 and 3010cm The effect of this conjugated structure is even more pronounced in the Raman spectrum. Hie strong unsalu ration band occurs 20cm-1 lower than in linseed oil. at 1638cm >. The relative intensity of this band is also greatly increased (far more than would be expected from the r" Fig. 1 Inflated spccfium of litt.wcii oil Fig. lb Laser Raman spectrum of Unseal nil MONS 085331 1350 20 November 1971 Chemistry and Industry Fig. 2a Infrared spectrum of turifi oit higher (ouil unsaturation oT the oil). Many more ester vibrational modes are Raman active than in the noil-conjugated oils, giving medium intensity bands at 1291,1255,1230,1195 and 1100cm"1, together with a very intense bund at 1165cm *. /.inseed (til alkyd The infrared spectra of the linseed oil alkyd shows the characteristic features of the unsaturated oil. The principle changes that occur in the spectrum when the oil is incorpor ated into an alkyd are a frequency drop of the ester carbonyl stretch from 1748 to 1740cm >. and the loss of the !239cm- ester band. The 1270cm'1 ester band, which is not infrared active in the oil. appears as a strong band in the correspond ing alkyd. The diagnostic infrared bands of the phthalic portion of the alkyd arc at 3060, 1600, 1580, 1075, 1040, 740 and 705cnr *. ' The presence of pcntacrythritol in the alkyd does not give rise to any major characteristic infrared bands. The 1385cm * band has, however, a slightly higher frequency than in the corresponding mode in a glycerol alkyd. The dilTcrcnccs between (he Raman and infrared spectra of the triglycerides noted in the previous section are also seen in the spectra of the corresponding alkyd. As in the infrared, several changes are noted in the Raman spectra of the triglyceride portion of the alkyds. The very strong unsaturafion band is shifted down a few wave number Fig. 2b Laser Raman spectrum of lung od values to 1654cm-1, while the 1165cm-' ester band, which is inactive in the oil spectrum, is now present as a weak band in the corresponding alkyd. The aromatic bands at 3060, 1600, 1580 and 1040cm 1 arc common to the Raman spectra, those at 1600 and 1041cm-1 being of higher intensity than their infrared counterparts. The 1075, 740 and 705cm"1 bands are not Raman active. The characteristic pentacrythritol modified band at 1385cm"1 is also Raman inactive. Other alkyds examined included a saturated acid alkyd, in which the unsaturation band at 1650cm-1 was essen tially absent, and an alkyd prepared with sebacic acid in place of phthalic acid, in which the aromatic bands were absent. Discussion and conclusions The results show that in the Held of drying oils and alkyd resins, the laser Raman spectra till an important gap in the structural information given by infrared spectra. While in the infrared spectra there is no characteristic band for total unsaturation, only for traits unsaturation. the band for total unsaturation in the Raman spectra is one of the strongest bands. For the non-conjugated glyceride oik the band can be used as a quantitative measure of un saturation and the intensity of the band in (he alkyd gives an indication of the residual unsaturation. With a conjugated 1 Fig. 3b Laser Raman spectrum of pentacryihruvl iinwvd resin alkyd resin HONS 08533^ 20 November 1971 Chemistry and Industry oil the unsntunition bund is greatly enhanced, dominating the spectrum, ns it docs on the ultraviolet region. In contrast, the main ester carbonyl band, which is one of the strongest in the infrared, is weak in the Raman spectrum, ami minor carbonyl hands arc barely discernible. Hydroxyl groups normally give only weak bands in the Raman spectrum and this region (around- 3500cm-1) has 1351 not been explored. Several of the aromatic bands are common to Raman and infrared, and a few arc stronger in the Raman spectrum, which may prove of value. Reference 1 Cudby, M. E. A.. Willis, H. A.. Hendra, P. J. Si Peacock. C. J. Chertt. <fi Ind., 1971, 531 British Pest Control Association annual dinner The British Pest Control Association's annual dinner at the Park Lane Hotel on Tuesday 2 November 1971, attracted nearly 100 members and guests who came to hour this year's Principal Guest Speaker Sir Basil Hngholm, Permanent Secretary of Ihc Ministry of Agriculture, Fisheries ami Food. In the course of his address. Sir Basil referred to the changes in ihc work of the ministry which were announced in the government's while paper last January. With a view to reducing the burden on the lux puyer, the ministry's pest control activ- ilies will be limited to those which can be carried out only by the government and which are essential to the public interest. Rabbit clearance societies were no longer eligible for grants and he thought that this would undoubtedly offer an opportunity for increased pest destruction activities for BPCA member companies. Furthermore, the white paper hIso announced a signifi cant reduction in the ministry's advisory work on pest control and in future regional staffs will not be going out and about nearly as much to give on the spot advice on pest control. Although the ministry will keep on ins|>cL-iing imported food cargoes for pests, because it has always been an important function of the government to defend this island against invasion, it will be up to commercial organisations themselves to pay for keeping pests under control in future. In the same way, the ministry will no longer normally go out to individual farms to advise on pest control unless they have statutory duties to perform. In his reply, the President. Mr A. Fraser McIntosh, expressed his very great pleasure in being able to welcome Sir Basil F.ngholm lo a BPCA Dinner for the third lime, u fitting climax to what he described as u vintage ycur for the association. He referred to the annual dinner being this year made more glamorous by the presence Standing at the British Pest Control Association annual dinner is the President, Mr A. Fraser McIntosh, on whose right is the principal guest speaker, Sir Basil Englniim, the Permanent Secretary of the Ministry of Agriculture, Fisheries and Food. On hi,\ right is Dr A. C. Fisken, Vice-President of BPCA who proposed the toast to the guests, and on the President's left is Dr M. B. Green, the Chairman of the Pesticides Group of the Society ofChemical Industry, who replied on behalf of the guests. of the ladies associated with the industry. Mr Fraser McIntosh, in referring lo die recent major government decision on the EEC, also mentioned that during last month's British Pest Control Conference in Jersey he had started to investigate the formation of a European Federation of Pest Control Associations. He felt confi dent (hat Britain had a great deal to offer Europe in pest control techniques and standards of operation, and one of the main reasons for this was that during the last 25 years the industry has been in the unique position of pooling its knowledge with that of ministry officers The President ended his speech by expressing the sincere thanks of the BPCA to the ministry for the tremendous contri bution to the Jersey conference by officials and scientific officers of Ihc ministry, noi only in the papers ihey presented, but in the vital part (hey played in discussions throughout the conference. This lent authority and emphasised the close co operation and invaluable support given hy HM Government and greatly impressed the overseas delegates. <\ i. KI l.llt l MONS 085333 MJ2 Essay review 20 Nt/i'rmbrr 1971 Chtmiurv ttmi inJttun Synthetic methods of organic chemistry by P. D. Magnus Dr Mourns has been at Imperial College for the past ten years, first as an undergraduate, then studying for a PhD under Professor I), II. H. Horton, In 1966 he urn appointed ox on assistant lecturer in the .second year of his PhD, and in 1969 he was appointed to the position of lecturer. During the past five years he has been working with Professor Barton and they have published several papers, notably in the area of organic synthesis. Dr Magnus' own research interests ate in the study of new reactions and the synthesis of natural products, especially trrpencs. The latest volume of Synthetic methods' oforganic chemistry* is number 25, completing the fifth scries, and marking the documentation of synthetic procedures for the past 25 ycurs. Before describing the achievements of this volume a brief glance at what synthetic organic chemists have been doing in the past, and more recently, might serve to iltusirulc the complexity and magnitude of the task, that Dr W. Thcilhcimcr has undertaken. Organic synthesis, over the past hundred or so years has remained one of the main pursuits of organic chemical research. Jt must be said to be the life-blood of organic chemistry, supplying new reactions and the factual material upon which the (booties of organic chemistry are based. Indeed, it would be no exaggeration to say, without organic synthesis there would be no organic chemistry at all. Like the other branches of organic chemistry the ob jective of synthesis has not remained static in its outlook, it has changed since the early days of structural verifi cation, now the domain of the X-ny crystallographcr, to a search for new reactions that not infrequently (witness the Woodward-HolTman rules) change the whole face of organic chemistry. When wc arc asked to assess a paper or book concerned either with a specific synthesis, or the development of new general synthetic methods, the usual objective discipline of science can be extremely difficult to apply. Wc are approaching the subjective realm of aesthetic values and consequently many conflicting views may ensue. A partic ular synthesis may be said to be extremely useful in a commercial assessment, yet reveal nothing new or particu larly stimulating to the academic scientist. Likewise some academic synthetic work that unfolds new reactions or enables fundamental steps to be taken in theory, arc useless to the commercial world. Possibly there is only one real way of judging synthetic work and that is in its usefulness `Synthetic mclhods of organic chemistry', 1V7I. Vul, 25. Yearbook )*7J, by W. Thcilhcimcr, pp xvi t 707, John Wiley, Sfr29f), 57) 05, DM2VA. and generality. Does it enable one to do whal could not be done before? Docs it improve on what could be done before? Naturally the scientist's integrity must be absolutely honest in the assessment of what he has done. Any new synthetic methods that are reported in the chemical literature, to warrant serious appraisal, must attempt to define the scope, limitations and of course the yields of products obtained (preferably of isolated products). The practising synthetic organic chemist is then in a position to say whether this new synthetic method is useful to him per sonally or to synthetic organic chemists in general. In the past the bulk of chemical reactions were discovered in the course of often long and tedious degradation^ work to elucidate structures. This wholly admirable pursuit uncovered a vast number of reactions, often unexplained at the time, and also provided the structures of a large number of natural products. The next most obvious step was to confirm the allotted structure by an unambiguous total synthesis. As the natural products presented more formidable structures the art of synthesis became more independent of the initial structural elucidation. Eventually with the advent of sophisticated spectroscopic methods and A'-ray crystallography, synthesis has grown into an inde pendent science. This renaissance of organic chemistry has at once enabled the organic chemist to become more productive and creative. Synthesis is no longer a method of confirmation but a creative science seeking to understand and develop new methods of making and breaking bonds between atoms. The documentation of the achievements of synthetic organic chemistry is an awe inspiring and monumental task. But no one can doubt the necessity of recording the reactions that have been used, with varying degrees of success by organic chemists, into a single series of books. It is one thing to see the necessity, quite another to execute it successfully. The necessity of documenting synthetic methods was recognised by Dr W. Thcilhcimcr m the ambitious task of producing an annual coverage of syn- MQNS 065334 20 November W7I Chemistry our* fnrtrrtfry Ihctic methods. The first volume of 'Synthetic methods' nppenred in 1946, and its title describes precisely what it is; a compilation of synthetic methods. The subsequent annual volumes have been divided into five series. Each live volume series is terminated with an index of reaction titles and a cumulative index. Consequently in 1971 we have arrived at Volume 25, the terminal volume of the fifth series. Throughout ibe twenty five volumes the coverage of the literature and format has maintained a consistently high standard, and over ihc years this encyclopedic work, in due recognition of the author's achievement has come to be more affcciionutoly referred to as `Theiiheimer'. When one is considering the synthesis of a molecule of any magnitude, or the operation of a single synthetic step, ihc question that is put, either consciously or subcon sciously, is what bonds do I want to make, and how do I want to make them? Theiiheimer is classified according to this simple idea. Each section is written under the heading M'oimation of the X-Y Bond', where X and Y cover the full range of atoms of interest to both organic and organometallic chemists. |H, O, N, Halogens, S, C and the re maining elements (Rem)]. When the various combinations of these elements arc assembled the result is some twenty five different bond types. The sub-classification deals with the second question. How do J want to make these bonds? 1353 The bond formation types arc symbolised as follows, addition elimination (^l^)- rearrangement (A) and exchange (f|). Furthermore the reactions such as electron pair formation on heteroatoms, and methods of synthesising nitrogen radicals and the heteropoiar bonds arc included. Volume 25 is completely up-to-date, containing references to some seven hundred papers that have appeared between 1968-1970, Each volume of 'Theiiheimer' begins with a section entitled `Trends in synthetic organic chemistry'. This section in volume 25 is as in previous volumes an extremely useful survey of the main synthetic achievements during the past year. Volume 25 includes references to the stereoselective juvenile hormone syntheses and prosta glandin syntheses that serve to remind us that natural products still provide a powerful incentive for the develop ment of new synthetic methods. The admirable achievement of `Theiiheimer' in collating the past twenty five years of synthetic organic chemistry can never be underestimated. Merely browsing through these volumes can be a source of many ideas and the acquisition of considerable knowledge. No active organic research school can afford to be without this vast store of information. Although prohibitively priced for the in dividual this should never deter libraries from apportioning part of their budget to the latest volume of `Theiiheimer'. Book reviews l 'ndcrMandiitK cltcmixlry 1971 by G. C. hmcntal and R. Sprat Icy Pp xiv I 974 Son I /om isco: Holden-Day 17-50 n Tliis is an excellent hook into which an cnominux amount of work and study has been put by the authors. It is a com prehensive text in general and physical chemistry which endeavours to return to fundamental chemical principles and bring order und logic to what in many similarly aimed text books is an unrelated collection of factual information. The Imok is ideally aimed for an introductory college course in the Stales which keeps the mathematical content to a minimum and adequately meets the need of `A` Level chemistry courses in this country. In many of the topics for example the principles of chemical bonding orbital nomenclature and quantum theory the slandaid is carried beyond some `A* Level syllabuses but the information is produced in such a palatable way that students using Ihc Imok will be stimulated to sec each topic through. The presentation is excellent and the index comprehensive. With 974 pages this is no simill feat. The book is to be thoroughly recom mended to all students attempting 'A' Level or higher chemistry courses and it is a worthwhile addition to any chemical library. j. u. I HUMAS Industrial crystallisation from solutions 1971 by J. Nyvli Pp v-i 189 London: Butterworlhs 5-50 This short book is a translation of the Czech original of 1967, and it is described as having been extensively revised lo increase its suitability for the English speaking market. The author has tried, with some success, to avoid excessive overlap with existing English texts, and he writes from the standpoint of the chemical engineer. The first chapter, accounting for three fifths of the pages, covers the theoretical foundations of crystallisation as a prepara tion for the second chapter, which is a very welcome discussion of design calcu lations- for crystallisers. This discussion is firmly based on the kinetics of crystal lisation as well as on the usual mass balances, und the use of numerous numeri cal examples confirms the general impres sion that this is a book by a pructicul mun. Information about the solubility and crystallisation of many substances is presented in Ihc appendices to the main text. About thirteen hundred references arc cited in groups, but the thoroughness of the literature survey varies markedly from one section to another. On p 77, for example, one sentence directs the reader to 50 references, and on p 156 no fewer than 66 references are introduced in this way. Since none of these icfcrcnces concern publications in ihc last ten years, a much shorter list of carefully selected recent references would have been much more useful. The author has published a number of papers on crystallisation, not always easily accessible to western readers, and it is appropriate that his collected views should now be available in book form. Chemical engineers interested in crystallisa tion will certainly benefit from reading this successful translation, and it should en courage the replacement of the somewhat mysterious art of crystallisation by sciencebased engineering procedures. I). A. BLA< KAOOLH HONS 005335 n.M 20 November 1971 Chemistry and Industry Structure of organic solids. Main lectures presented at tJte Second Microsymposium 'Structure of organic solids', Prague, 1968 1969 Pp v 1 86 London: Utitterworths 2-90 The contents of this book have already appeared in Pure ami applied chemistry, 1969, JR, 4, pp 465 to 550. The Micro* symposium referred to in (lie subtitle was held under the auspices of the Macro* molecular Division of (he International Union of Pure and Applied Chemistry, in conjunction with the Czechoslovak Aca demy of Sciences and the Czechoslovak Chemical Society. The contents consist of four excellent review papers in different fields. W. Hoppe and II colleagues described their cxjrcticncc over the last few years in the use of an automated fourcircle diffractometer for (he making of accurate A'-ray diffraction measurements on an (if need be) unoricntaled single crystal. They illustrate this with a descrip tion of the structures and methods of structure determination of a number of complex organic compounds, including some of biochemical interest. W. Rulnnri, in speaking of the structure of amorphous solids, gave a concise theoretical introduction to the idea of short-range order of particles of strongly anisotropic shapes such us u bundle of linear molecules or a stack of planar molecules, following this by experimental results on nylons and on carbonised organic materials. G. 1, Bacon, claiming that neutron diffraction studies will soon achieve first parity with and then pre-eminence over A'-ray techniques for the determination of atomic positions and dynamics in organic crystals, gave an account of pro gress over the previous five years, illustrat ing this with examples of current studies of high accuracy of particular interest in cboitiiiury. Finally C. A. Taylor described optical methods (diffraction analogues) as an aid in structure determination, especially since the advent of (he gas-phase laser has made it possible to rethink the design of optical diffractometers. By far the most useful applications of optical methods, he claims, are in studies of imperfectly crystallised material, His examples, copiously illus trated by well-reproduced diagrams, refer mainly to fibrous structures, which could have been from living or non-living material, but which are in fact 'shapes' producing various diffraction effects which could trigger oil' useful ideas relating to mil structures. The late KMHI.tLN LONSDALL Microwave molecular spectra. Volume 9, Part II of 'Technique of Organic Chemistry* 1970 W. Gordy and R. L. Cook Pp ix+ 747 New York: Inicrscicnce Publishers 15-50 Over the past twenty-five years microwave spectroscopy has contributed a wealth of information about molecular properties. Although it is probably most generally associated with precise structural deter minations, it has also provided a wide range of other information about mole cules. Included in this are molecular dipole and quadrupole moments, magnetic moments, nuclear quadrupole coupling constants, barriers to molecular inversion and internal rotation, conformations, mole cular force fields and energy transfer in collision. The stage has now been reached where increasingly larger and more flexible molecules are being studied. Quite recently commercial instrumentation has been in troduced which has enormously improved ease of operation. It is therefore opportune that a comprehensive and up-to-date book on the subject should be published at the present time. It appears as a member in the well-known 'Technique of organic chemis try' series, but its coverage and level of treatment will make it of interest to chemical physicists and physical chemists, and to spectroscopists in particular. The book begins with a treatment of molecular rotation, in terms of angular momentum. The development of matrix elements of angular momentum operators lays the foundation for much of the book. Successive chapters give a systematic and comprehensive treatment of diatomic, linear polyatomic, symmetric rotor and asymmetric rotor molecules. Another chap ter deals with molecules in which internal rotation occurs. The treatment of both high and low barrier approximations is set out and reference is made to numerous particular molecules. Other chapters deal with line shapes and nuclear hyperfine structures. Stark and Zeemann effects for the various classes of molecules are treated in turn and again particular examples are con sidered. Centrifugal distortion in asym metric rotors is clearly developed and its use in molecular force field determination is shown with examples. Particular atten tion is paid to the evaluation of molecular structures from rotational constants. A final chapter deals with nuclear quadrupole couplings, moleculur dipole moments and the chemical bond. The whole treatment of the subject is well integrated, the quantum mechanical techniques used in the book following on smoothly from the development of matrix elements in the early part of the book. The reader is further helped by useful appendices. It is typical of the care that has been taken in the development that an appendix is devoted to the frequently used van Vleck transfor mation. In addition, the appendices include a wealth of information including molecular structures derived up to 1969. It is a book which is likely to be of wide interest for reference purposes on molecular structure, and will be indispensable for research workers with interests in rotational spectroscopy. IJ. ). MILLEN Aspects of adhesion 6 1971 by D. J. Alner Pp xii I 149 London: University of London Press 3-45 This volume is one of a scries dealing. u\ thctitle implies, with all aspects of adhesion. It is in fact the paper given at a conference held in the City University two years ago, but the fact that it is published somewhat later does not in any way detract from the topicality of the various articles in the hook. Since it is one of u scries it deals parti cularly with only one aspect of adhesion, namely, the adhesion of thin films to various types of surface. Under these conditions, the interaction of (he polymer with the substrate is of particular import ance and there are, therefore, two papers dealing with the more fundamental aspects of this part of the subject and in particular one dealing with the effect of hydrogen bonding in adhesion. The remaining pupers deal with quite specific aspects of (he sub ject and include practical details of the instruments that have been designed to measure the adhesion of films under these particular circumstances. In addition, there are one or two articles dealing with adhesion of metal films to glass where the same general problems arise and in which the devising of suitable machines for measuring adhesion is equally import,ml. As is usual in this suhicct, a great deal of the knowledge must be empirical nt character though quite specific facts often emerge which arc not explicable under the basis of cx/stcni theories. For those who are engaged in work of this kind the several chapters will be of great use in ensuring thut films mude under these conditions will be properly attached to the su bstratc.' H. W. Ml LVll.l.t MONS 085336 20 Nawutfu't 1971 (Vicniunv anu 1355 Communications to the editor Contributions should have novelty and should he brief. In order to expedite publication proofs will not be circulated to authors unless requested when the manuscript is submitted or there are substantial queries by referees. Proofs not circulated will be checked against the manuscript and errata will not be published if the manuscript (including figures and formulae) is at fault. Structure of the pigments (Hansa colours) formed from acetoacetarylides with diazonium salts by !' Jltudy and J. II. P. Tynum* Unmet l/tuvcrsity, Wc/wrwinif <iI (. heimstry. Lonthut W.3 Recent preliminary work1-2 on the crystal structure of certain analogues of HANSA !OG (C.l. pigment yellow 3) prompts lhe publication of this Communication on the related subject of the chemical structure of (his class of substance. In initial experiments, diazolised 4-amino-3-nitrotolucne coupled with the aectoaeclunilidcs (I,X F.Cl.Br.l) to produce yellow pigments having little difference in shade. The iodo and fluoro derivatives sire new compounds. Nitration of 4-fluoroncctanilidc in concentrated sul phuric acid with methyl nitrate4 rather than ethyl nitrate, followed by hydrolysis, diazotivation and coupling' with 4-ftuoroacctojicclamlidc and with compound (l,X--F) gave two new difluoro compounds which were orange in colour. The latter, the difluoro analogue of HANSA IOG, was obtained as orange needles from xylene or nitrobenzene, mp 24H ( (Found: C, 53.2; H. 3.5; N. 15*4. C^H^N^Fj requires: C, 53*1; H. 3-3; N, 15-4 per cent). The infrared spectrum (KRr disc) showed only single carbonyl band at 1660-1670 (CONH), 1510cm ' (N02). a broad band consisting of two maxima at 3050-3100cm"1 (NH and H-bonded OH) together with bands due to the N = N. C C and phenyl groups. The n.m.r. spectrum proved to be difficult to determine owing to the insolubility of the pigment in the usual solvents (OXTl.u (CD.O2SO, DCON(CDj)2 and C(,Dft). In hot nitrobenzene C0D5NO2, absorption bands were present at t 5-48 (hs, 1H, cnolic OH), --1*55 (6.v. IH. CONH), I-5-1*7 {m, lHt ArH), 2*07-2-21 (dd, 2H, ArHh 2-8-3-0 (m. 4H. ArH) and 7-78 <.\\ 3H, Me). The cnolic OH and CONH groups underwent exchange with D-jO. The dichloro (HANSA IOG) and the dibromo analogues7 showed similar spectra. Potentially there arc a considerable number of hydrogenbonded structures but only (wo (IJ and III, X--X1 F) need seriously be considered, incorporating a hydroxyl group associated with either an a?.o or a carbonyl group (of the CONH). The latter structure is reminiscent of the internal bonding occurring in acetylacetonc. Since both hen/encnzo-lJ-miplitliol and acetylacetonc (in nitrobenzene or CHCl.i) exhibit low field proton absorption (OH, -r-5) the n.m.r. spectrum docs not afford a complete distinction between (III and (1)1), The existence of a tautomeric structure (IV) or the alter- I'jcscni wditrcsv. Hrunct University, School of Chemistry, Kingston l iiiK*. Uxbridge, Middlesex native in which the NH is associated with the eailnmyl group can be excluded since in both eases neither the n.m.r. nor infrared absorption spectra would be in agreement. In n-aminoacetophcnone tNH occurs at 6-12 (CO*). Likewise the n.m.r. spectrum of salicylaldchydc-2.4- dinitrophenylhydra7one, a double hydrogen-bonded struc ture showed t-0-12 (fw, IH, NH___ O, a feature character istic of 2,4-dinitrophcnylhydrazcmes generally) and r -0-3) (hs, IH, H-bonded phenolic OH), The infrared spectrum clearly exhibited a strong band at 1630cm ' (C N) absent in the HANSA pigments. The bonded azo group in compound (II) would not he expected to undergo cis-trans isomerisation as would he the case with a free azo group. Chloroform solutions of ihe HANSA pigments irradiated with ultraviolet light for a prolonged period were like bcnzcncazo-{i-naphthol com pletely stable whereas azobenzcnc rapidly isomcriscd. The difluoro compound before and after such treatment possessed. (CHC10. 260 (log c4-40.), 345 (log e4-35) and 4)2nm (log e4*3l). The very fast properties of these pigments must indeed be associated with the very stable hydrogen-bonded structure (11) applicable to the solid states and to solutions. MONS 035337 1.1.K* The presence of a fluorine atom ortho to the -NHCOgrnup might have been expected to lead to hydrogen bonding. No evidence of any significant shift in the n.m.r. absorption of the amide proton was found in the difluoro compared with the dichloro and dibromo compounds. 2-l`luoroacctoaccianilidc, 2-fluoroacetanilide, and 2-fluoro* aniline were similar confirming that the -NH- hydrogenbonds comparatively less than the -OH group. Although it was recognised* that only the cnolic acetoacetanilidc couples, numerous authors6 have represented the structure of the products with the hydrazonc grouping -NH-N C<. In view of the present findings, the extensive formulation7 of pigments of this type with such a structure is erroneous. Owing to simultaneous hydrogen bonding the cnolic coupling product is stabilised as soon as it is formed. The n.m.r. spectra of all the acctoacetanilides contain a 20 November 1971 Chemistry and Indnstiy small band at t --3-4 (enolic OH) present to less than JO per cent; tautomerism of the keto form to the enolic form readily occurs aided by the precipitation of the pigment as the coupling proceeds. Received 22 July 1971 Revised 14 September 1971 References 1 Chapman, S. J. A Whitaker, A., J. Soc. Dvrrs Colour., 1971, 87, 120 2 Chapman, S. J. A Mijovic. M. P V., Chem, <S hut.. 1970, 955 5 Fierz-David. H. E. A Blangcy, L., `Fundamental Processes of Dye Chemistry', 1949, New York: Intersaence * Smith, W. T. A Stcinlc. E. C,, J. Am. chem. Soc., 1955, 75, 1292; Wilkinson. J. H. A Finar. 1. L., ihitl., 1948. 70, 288 5 Dimroth, O., Ber. dt. chem. Ges., 1907, 40, 2404 6 ref- 281-290, p 138 `Organic Reactions,' vol. X 7 Parmerter, S. M., ibid., 1959, vol. X, p 13 and Table IIC. lidey Pyrolytic reactions of cyclic azines hy O'. Jlusenbeuttl, Opaiku and J. G. Krause Department of Chemistry, Niagara University, New York 14109, USA Pyrolyscs of several acyclic azines have been reported.1 Now the first example of the thermolysis of a cyclic azinc is described, the azinc, l,2-diaza-3,7-diphenylcyclohepta-2, 7-dicnc (I),7 was pyrolysed neat and under nitrogen at 250-300V until there was no evidence of unreactcd azine us shown by t.I.e. A considerable amount of ummonia was evolved during the pyrolysis, and a small amount (2 per cent) of liquid identified as bcnzoniirile distilled from the pyrolysatc. Distillation of the residue at 01mm from an oil bath (220 c) afforded an oil (11) (70 per cent) which soon solidified and was rccrystallised from ethanol, mp Nl-2 c. Sodium fusion confirmed the presence of nitrogen, and the n.m.r. spectrum was devoid of any saturated C-H absorption. This suggested that the product could be 2,6-diphcnylpyridine. and this was proved by comparison with an authentic sample.' Similarly, J,2diuza*35-7-triphcnylcyclohcpia-2.7-dicnc (111)4 gave 2,4,6Iriphcnylpyridinc (IV) (55 per cent), mp 137-139* c (picrate, mp 191-193 V) (Lit.* mp 137-138 c; picrutc, mp 189 192 C). Hi inn am This remarkable reaction can be seen to involve the loss of only one nitrogen atom per molecule of azinc as well as the loss of one hydrogen atom from each of the ihrcc .ry?3 carbons to give ammonia. This contrasts will) ibe pyroly sis of benzaldehyde azinc where C = N cleavage with loss of nitrogen occurs to form stilbene.6 The conversion of compounds (l) and (III) into the pyridincs (II) and (IV) under these conditions is probably a free radical process since the reaction displays an induc tion period (during large-scale pyrolyscs on 50g of azinc the reaction tended to go out of control at the beginning unless healing was slopped from time to lime), ami the yields arc drastically reduced if oxygen instead of nitrogen is bubbled through the azinc during pyrolysis. Photolysis of the azines (1) and (111) with 35(X)A light in methanol for extended periods of lime resulted in no product formation and complete recovery of starting material. The Niagara University Research Council is (hanked lor partial support of this work. Received 20 September 1971 References Stern, R. L. A Krause, J. C*., J. Heterocyclic (.hem., I'HiK, 5, 2d) and references cited therein 2 Overberger, C\ G. A Monaglc, J J.. J. Am chem. Soc , I95(>. 78, 4470 3 Gilman, H. A Edward, J. T., < on. J. Chem.. 1953. .11. 457 Professor Louis A. Otrpino of the University of Massachusetts is thanked for supplying this azinc. * Cltuhb. F., Hay, A. S. A Sandin. R. B., J. Am. chem Soc.. 1953, 75, 6042 6 Zimmerman/M. E. A Somasekhara, S.. ibid.. 19(4), 82, 5865 muns 03533B i(i Nttvrmbrr 1971 d Special Discussion of the Faraday Society Thin Liquid Films and Boundary Layers edited by F. C. Tompkins The Taraday Society, London, England' October 1971, 270pp., 5.50 This Special Discussion represents the first of a new series on physical chemistry topics of scientific and industrial importance and timeliness. Following the well-known pattern of the Faraday Society's General Discussions it had the advantage of preprinted papers, thus allowing for important debates on the work submitted. The papers and a report of the ensuing discussion are contained in this volume, which forms a valuable reference work on the most recent concepts and experimental work undertaken by international authorities. Annual Reports on NMR Spectroscopy Volume 4 edited by K. F. Mooney Anacon (Instruments) Limited, Bourne End Buek inghamshire, England December 1971, approx. 580 pp,, 10.00 Annual Reports on NMR Spectroscopy, formerly Annual Review of NMR Spectroscopy, has established itself ns a means for the specialist and non-specialist alike to become familiar with new applications of the technique in all branches of chemistry, including biological, pharmaceutical and agricultural chemistry. With the increasing exploitation of larger chemical shifts and the growing interest in lluorochemistry, fluorine-19 NMR has assumed special importance. This subject, and also proton NMR, is reviewed in each volume. The series will continue to be a valuable source of information for all analytical, structural, inorganic and organic physical chemists. Contents Genera] review of the proton magnetic resononce. The investigation of the kinetics of conformational changes by nuclear magnetic resonance spectroscopy. Nuclear magnetic resonance spectroscopy in pesticide chemistry. A simple guide to the use of iterative computer programmes in the analysis of nuclear magnetic resonance spectra. Nuclear magnetic resonance spectra of polymers. Fluorine-19 nuclear magnetic resonance spectroscopy. Author index. Subject index. Academic Press lxmdon and New York 24-2H Oval Road, London NWI, England 111 Fifth Avenue, New York, NY 10003, USA CHEMISTRY & INDUSTRY BUYERS' GUIDE 1972 for Manufacturing Industries Anticorrosion Beverage Fertiliser Petrochemical Fine Chemical Petroleum Building Food Chemical Chemical plant Coal Construction Plastics Instrumentation Printing Maintenance Process A Plant Metal Consultancy Metal finishing Research A Cosmetic Nuclear Effluent treatment Packaging development Electrochemical Paint Electronic Paper Water treatment and othe r industries The 1972 Buyers' Guide will be one of the most up-to-date and comprehensive source* of British suppliers of chemicals, chemical plant, and laboratory equipment. To secure your copy ftll in and return the coupon below to \. G. Kennedy & Partners, 22o Methuen Park. London NI0. Telephone: 01'883 SS33/4 To J. G. Kennedy & Partners, 22a Methuen Park, London NI0, England. Please reserve me ....... copies of the CHEMISTRY * INDUSTRY BUYERS* GUIDE 1971 at 1.60 each. Namej..r..................................... Signature ......................... Position held:..................................... Date......................... Company: ................................................................................ Address:..................................................................................... MGNS 085339 Nature of business:. NOV 20 November 1971 Chemistry and InditMiv Elasticity, Plasticity and Structure of Matter Third edition lidiled by R. HOUWINK and H. K. DE DECKER The science of deformation of materials, now usually called rheology, has branched out into several new and significant areas of research in the last twenty-five years resultihg in a wide range of materials becoming available to the constructional engineer and iihyKiriM. The third edition of this book shows him how the behaviour of materials is related to the structure of matter, so that he will not only hr guided to a correct choice of available mater* iuls, hut will be able to develop new materials meeting specified requirements. 7.60 net CAMBRIDGE UNIVERSITY PRESS SOCIETY OF CHEMICAL INDUSTRY A CENTURY OF CHEMISTRY ON TYNESIDE by W. A. Campbell on behalf of the Newcastle upon Tyne Section of the Society of Chemical Industry. Price: 50p Price to members: 38p Orders should be sent to: SCI Publications, Chemical Society, Publications Sales Office, Bladdiorse Road, Lttchworlh, Herts, England Tel: 04626 5817 Advertisement Department tor pH test books byJohnsons A full range of test books packed in clear plastic boxes of 10 is now available. The range covers simple red/biue litmus types, to the more complex Universal test paper (pH 1 to pH 11). Write for full details to: JOHNSONS OF HENDON LTD 335 HENDON WAY LONDON N.W.4 PCMUisos near as your OUT fray Chemistry and Industry T. G. SCOTT AND SON LIMITED 1 Clement's Inn, London, WC2A 2ED Tel: 01 -242 6264 Full details of rates and circulation supplied on request ii chemist-- wherever he is--with an efncicnl, economical and fast physico-chemical measurement service--by post. The analytical techniques available in PCM U include Infra-red spectrometry, organic mass speclTomrtry, NMR spectrometry and Miissbuucr spectrometry. PCM U supplies an invaluable service to the smaller research or industrial laboratory by pivinp them access, economically lothclutcsi measurement | techniques. Large industrial laboratories. also, find that the PC MU service provides art economic answer when u 'onc-olT' requirement arises or w hen their ow n facilities arc overloaded. The service is comprehensive (si. died min pivlalion of results i available if required, with access io many other unulylical techniques)., confidential.., economical... and fast. U vs also bights convenient --wc supply Post Otlicc approved packs for your specimens and special nrdi forms free ofcharge. PCMU Ask us for a copy of the PCMU HARWELL AND Prospeclus. Ours is a service you should learn more about. ALOBRIVIASTON PCMU HAHWKI.l. DIIKOT HLRKS Abmpdon 414). Fsl 41? MQNS 085340 Novrmhrr 1971 Chemistry and Industry CLASSIFIED ADVERTISEMENTS IMPORTANT:--Unless otherwise stated, replies should be addressed to Box................. c/o T. G. Scott St Son Ltd., 1 Clement's Inn, London WC2A 2ED. Names of companies to whom replies should not be sent may be listed on a covering letter addressed to the above agents. CHARGES. Situations Vacant, Educational, Fellowships and Grants, etc., SOp per line (approximately 10 words). Minimum 2.00. box replies 2Sp extra. Situations Wanted, 40p per line (approximately 10 words). Minimum 1.50. Box replies 25p extra. SITUATIONS VACANT UNIVIRSITY OF LONDON CHAIR OF PHYSICAL CHEMISTRY AT BIRKBECK COLLEGE T)v K*nnl> invhr upplicniioni lor Iht above Chair. Salary noi lat* than 1453.'! yem pint Cl00 London Allowance. AppItuOioni (IV copies) thould be received not leiei than 13 December IV71 by the Academic Hegiiirar, Urtiversily of I.Ofltkm, (0130) Senate Houar. WClE 7HVJ, ftom whom further particular! may he oWeined. (356) MIDDLE LEE REGIONAL DRAINAGE SCHEME RYE MliADK SI'.WAOli PURIFICATION WORKS, XIANKTLAD AUUOITS, NR. WARE. HERTS. ASSISTANT CHEMIST/TRADE WASTE INSPECTOR required N Salary rente 1926--2)99 Qttallftcniittm Octree in Chemistry end/or l.W.P.C. Diploma (H.N.C. iHigltl lie voitkideietl), l'.R|tetienue in trade went* connul dckirable. A|tplit Httii muM pttMCM e drivint licence. Assistance with hauling and removel *k|teit.e. in uitabie vases. Sgpetannualion Schertta. liw Workt. which it close to HotldCMlon, Hcrt*. ha* a well ctiuipped laboratory with untomatic inatrunteniation lor analysis of trade effluents and providing conmil Iih this modern treatntent works. Wiiuen applketion namint two references to the;-- (Jenciel Manager. Harlow Oevelopmenl Corporation, Gete House. The High. Harlow, Lisas. (362) THE COHSERVATORS OF THE RIVER THAMES DEPUTY CHIEF PURIFICATION OFFICER Applications are invited for the above new appointment which will be based on Reading. Applicants must possess an honours degree in chemistry and be a fellow of the Royal Institute of Chemistry, Experience of the management of river and ground* water quality in relation to public water supply, diluent disposal and other uses is desirable. No less essential will be (he possession of the personal qualities necessary 10 enable the successful applicant to act for the Chief Purification Oflivcr on a wide variety of purification management matters. The salary scale for the post is 4,230- 4 x 174 4.2(> with essential car allowance. Local government superannuation acts will be applicable. Applications in an envelope endorsed 'Deputy Chief Purifica tion Officer' and marked 'personal' giving names and addresses of 3 persons to whom reference can be made must he fcccivcd not Inter than 3rd December 1971. H. Fish, Chief Purification Officer, 2nd Floor, Reading Bridge House, Reading RGl 8PR. . SENIOR TECHNICIAN V A Senior Technician is required with a background of either chemical or mechanical engineering up to H.N.C. or H.N.D, level. The work concerned will be interesting and varied and the salary paid will be commensurate with age, qualifications and experience. Please write for an application form to the Administrative Officer, at the address below, quoting reference TCC-V. Brooke Bond Liebig Research Centre, Blounts Court, Sonning Common, Heading, KG4 9NZ.. HONS 085341 (3*2) KtlGATE GRAMMAR SCHOOL, SURREY Wanted in January. Chemistry Technician. Salary Grade I, 2 or 3 according to quali fications and experience. Three labora tories. Apply to Headmaster In writing, giving names of two referees. A-v , an llM'l rtA,i c(NuINAWCLY*tiTlrwI.CiMilAtvLtiuli-tCi-i-nHmuiC.lnlHllmcItkT|i'nciiirtmcuu,ri.c1ie.2.i'lVKTeourryiiititviPaiiurKtbciltnilc Analytic Lnhoraiory. work oil food; druu; Road. London bi.H.I I. MISCELLANEOUS Iiqi'll) NITROGEN deliveries from one litre to * live bundled litres wiihin 24 hours of your phone uill in most purls of Knglitnd, also supplied Liquid Aiytm, Solid CO2 and liquid Nitrogen equipment, foi line or Rule. Details from Cryoscrvice Lid., Milton Snarl, Multhy, Rotherham, Yorks. Telephone: Maltby (070 981) 2205 or Barnsley (0226) 742912. <3J) LOUGHBOROUGH UNIVERSITY OF TECHNOLOGY AND WARREN SPRING LABORATORY Particle r.Torkshop 1972 5 7 April Introductory scries of 18 lectures covering:-- Purlkle Sire Analysis Outline of Particle Technology 10 14 April Specialised topics from the fields of:-- Powder Science Solid-Liquid Separation Solids Handling Powder Metallurgy A selection can Ik* made from over 50 lectures. 5-7 April Course l-ee 30.00 Residence 12.00 10-14 April Course Fee 50.00 Residence 21.00 l-uilhei details fiom.-- Cenlrc for Fxlcnsion Studies, University of Technology, Lotighhorongh. leics., LEI1 3TU. Tel: 050-93 63171 exin 249 and 213 (511) 20 November 1971 Chemistry and Industry SCI PUBLICATIONS Soclaty of Chemical industry, 14 Bttgnva Square, London S.W.J JUST PUBLISHED DISPOSAL OF PLASTICS WASTE AND LITTER - the staudinger report The very properties that make plastics so useful in modem Society also create tremendous problems of disposal - how can we get rid of plastics waste and litterf What is being done, and what must be done, by the plastics and packaging industries and by government and local authorities? 100 pp, 8vo. 2 {soft-back edn. 1) WATER IN THE CHEMICAL AND ALLIED INDUSTRIES - the hewson REPORT Water is becoming an increasingly scarce resource - how are firms trying to conserve it? What is being done to combat scaling and corrosion? What steps are being taken by industry to avoid pollutiog water supplies? 185 pp, 8vo. 3 CHEMISTRY AND INDUSTR YIN THE 1990s How will chemicals be used to increase crop yields, protect crops, produce synthetic foods? Materials for clothing and shelter, haviog remained relatively unchanged for centuries, are now changing very rapidly. New types of power and new uses for it are becoming vital to progress. How will ail these changes affect the environment? In view of the accelerating pace of innovation and change, how can industry forecast demands and plan its production for 20 yean hence? This book brings together a fascinating collection ofexpert articles on topics which concern us ail. 200 pp, 4lo. 4 (soft-back edn. 2) ION EXCHANGE IN THE PROCESS INDUSTRIES The huge volumes of highly purified water used in industry would not have been possible without piesent ion exchange technology. The Proceedings of this International Symposium cover the whole of recent research on these essential products. 450 pp, 4to. 10 These and other interesting publications from: SCI PUBLICATIONS, CHEMICAL SOCIETY PUBL. SALES OFFICE, BLACKHORSE ROAD, LETCHWORTH, HERTS, ENGLAND. Tel: 04626 5817. MONS 085342 U) Novcmltd iV/l (.'hetiii.ury In/tut Graduate Pharmacist Product Development A young graduate pharmacist is required to loin a small group concerned with the development of pharmaceutical, biological and diagnostic products. Some experience in a development depat tmem is essential for this post which will embrace work on pliHrntacO'kincitcs and drug metabolism. The pharmaceutical development department has close links with chemical, biological and analytical development departments and with the basic research departments. The person appointed must be able therefore to hold his own with colleagues in develop ment work and in the manufacturing departments. He will report to the Pharmaceutical Development Manager. The appointment is based at High Wycombe and a certain amount of travel at home and overseas is likely. Salary will Ik attractive and negotiable. Company benefits and conditions of service arc excellent. Please write giving brief details of education and career to: The Personnel Manager, G. D. Scarlc A Co. Lid., Lane Knd Hoad, High Wycombe, Bucks. SEARLE Research in the Service of Mankind QUEENS' COLLEGE, CAMBRIDGE Rtuirdi Fellowship In Chomicof Engineering or Applied Physical Chemistry The College invites applications for the above Research fellowship tenable from October 1912. The Fellowship is to Ik financed by a grant from the Central fclectricfty Generating Hoard for research in the Department of Chemical Engineering on some topic of interest to the Board. Examples of suitable topics are: solute behaviour at dry-out in annular two-phase flow; iht interaction between surface friction, mass flow and mass transport to or from the surface: chemical reactions in porous media coupled with diffusion under adiabatic conditions; or related topics of interest to the C.E.G.B. These examples are indicative only. The Fellow will be required to do up to six hours a week teaching for the College and will be entitled to commons and rooms in College. The Fellowship stipend will be determined in the tight of age and experience, and will be comparable with that of a similar University post. Applications (three copies) should be sent to the President, Queens' College, Cambridge, so as to reach him not later than )ki January 1972, acc ompanied by a curriculum vitae, a statement of the nature and duration of the proposed research, and the names of two persons who arc willing to act as referees. (SMJ 1 QUALITY S CONTROL J CHEMIST 3 ^B A fully Qualified chemist is required io fill an im- poMant position, which has developed m the condol of standatds of plastic products Applicant win., ^B will be under 30 yedis. should be famihai with chromatography and u.v. spectroscopy techniques and have knowledge 01 interest in mcasuinninnts ni physical properties A University degree oi us equiv alent in chemistry, logeiher with at least 2 years m ^B industiy is required. This is a position of considerable lesponsibility and an aoilrty to sunervrs*- stall is essential. There is a good commencing salary Fungi- benefits conform to modern praciico. Further information will be given at an interview Write quoting reference QCC 3 . \S* %J SH3 1 *.**> Administration Managar, SMITH & NEPHEW RESEARCH LTD . Gilston Park. Harlow, Easax. K) tSM. PLASTICS ENGINEER A lending precision gear mxnufuclurrr uiih sound rcputlluin lor lugli qualiiy machined gear, hat reached an advanced tinge in the development of precisian moulded gear* and now need, a knowledgeable and etpenenced engineer lo attume retpontihiliiy Tor ihe continued development of ihi, new butinew. Applicant, shook) he qualified mechanical engineer, ho have vpeciahted in iha ainilicaiion of moulding technique, and who have adianced icihnological knowledge in ihi* field. Salary by negotiation, excellent cnndilinnt of service. Apply in complete confidence to the Company', Permnnel Ailvisciv, John Fiaet A Partner, Ltd.. 6$ Kmghtttmdge. S.w.l, 0I-2.1S WXl. (V'l I ONOON CONSULTANT require, anaiytl psefcrehly M Them A. for work **' including drug,. Good prntpecii Tor applicant able to accept revponvthtUlv tto\ No. 550, Cheffl'llry A Industry, T. G. Scott a Son Lid. i < lement'i Inn WC2A 21.1) MISCELLANEOUS WANTED Small 1-5 kilo stainless steel autoclave. Working pressure up to 120 p.s.f. and working lempenuur* up to 200'C. with *tirrr - Croda Chemicals Ltd. (. S. Lower), Cowick Hell, Snaith, Goole. Yorkshire ON 14 9AA. (5*7) MGNS 085343 CHEMIX Gf=iANU-^ 9 t ' :A:; Beautiful is possibly the last word you'd use to describe BXL polyethylene valve sacks. But from the end user's point of view they certainly have their advantages. Like appearance. You can have any design you I ike printed on the pigmented film. Or clear film if you prefer, so that the contents can be inspected and checked with the minimum of fuss. And BXL valve sacks are square-ended when they're full. So they make a very neat package. The beauty of that is they take up less space during transportation and storage. In the field of polymer packing, fertilisers, chemicals, the self closing valve is particularly useful. Because the seal is perfect all the time the sack is closed. So there can be no fibrous contamination of the contents. In other words, in a BXL polyethylene valve sack, the contents look good and stay perfect. Beautiful. Bakelite Xylonite Limited Flwibit Peckaging Oiviaian. Gitiion. neat (Jamslcy, Yuiks iele|ifionc 072 C70 3300 iImhIpmHy ling AiStwtjgi HONS 0 8 5 3 4 4 /