PROCEEDINGS OF THE CHEMICAL SOCIETY APRIL 1957 THE COST OF THE JOURNAL By M. W. PERRIN,HONORARY TREASURER IN the last few years Fellows will have become used to seeing the finances of the Chemical Society presented in a way which clearly sepa- rates the income and expenditure which is involved in running the Society as such from the accounts which refer to the Society’s publications. This in no way lessens the importance of the chief function of the Society which is to continue the publication in its Journal of all papers submitted by Fellows which pass the normal process of refereeing. But it does bring into clear relief the present position and the worsening trend of the cost and selling price of the Journal and this has been under careful consideration for some time.The Council of the Society has expressed the view that the Journal should retain its present form and not be split and it is an inescapable fact that it is now costing E9.15s.Od a year to produce each copy. At the last meeting of the Council some very important recommendations from the Finance and General Purposes Committee were accepted and these include an increase in the price of the Journal to Fellows from the present figure of &3 per annum to &8 from January lst 1958 and to non-Fellows from El6 to E.20 per annum from January lst 1959. These increases will of course not affect the Society’s obligations towards Life Fellows who compounded before 1954 and are entitled to the Journal without further payment.It is however hoped that such Life Fellows will not claim a copy of the Journal if they find that they no longer need it. All Fellows receive the Proceedings of the Society without payment additional to their annual subscription but for non-Fellows the price of Proceedings is included in the figures quoted above. There are other changes which the Council has approved and to which I must also refer but as Honorary Treasurer of the Society it would seem appropriate for me to explain the reasons for the one very large change and to concentrate in this article on the new price for the Journal. The essence of the problem is that in recent years a deficit of E10,OOO to &15,000 per annum on the Publications Account has been closed in the main by contributions which have been collected by the Chemical Council from industry and which are divided by this body among the different publishing societies in the field.The last appeal by the Chemical Council to cover the three-year period from 1956 to 1958 has shown clearly that although funds will be sufficient to manage till the end of 1958 the Chemical Society must take steps now to face a position from the beginning of 1959 onwards 105 when regular grants from outside sources will not be available. Special help in unexpected emergencies can probably always be obtained from Government and industry and it is hoped that realisation will grow that those who provide the funds for research on an ever-increasing scale must also budget for the additional cost of publishing the results of it if they are to serve a really useful purpose.But this is quite different from a continuing annual grant of not far short of E15,OOO to subsidise those Fellows who elect to buy the Journal at a hopelessly uneconomic price. For as things now are there is indeed a very heavy subsidy being paid to those Fellows who take the Journal. I repeat the average cost of printing it is about &9.15s.Od; and even the “run-on” cost is &4. The latter figure which represents the additional cost of printing one extra copy is not very relevant for determining the price to be charged but it would anyway seem to be fundamentally wrong for the selling price to Fellows to be as low as 63.Of the 9,000 Fellows only one-third buy the Journal and these are about equally divided between those at home and those abroad despite the fact that more than two-thirds of the Fellows are in the former category. While only 3,000 copies of the Journal are sold to Fellows nearly as many are sold to non-Fellows at the much higher price. Most of these of course are bought by Libraries and Research Institutes of one sort or another and will continue to be bought while the contents keep their past and present level of scientific importance. The increase in the price of the Journal which has now been agreed will go more than half way towards closing this gap. It is the one major way in which the publications finance can be rescued from its present precarious position.Exact figures cannot be given as it is inevitable that the increase from &3 to E8 will lead to a drop which may be as much as 50% in the number of Fellows who will continue to take the Journal and this in turn will of course increase the average price of it. But its importance in the field of scientific literature is so great that it seems certain that copies will still be taken by Libraries and Research Institutes whether in PROCEEDINGS Universities Government organisations or industry. Even at E8 Fellows will receive the Journal at a very favourable rate and the ratio of almost 2 to 1 in the future cost of the Journal and Proceedings to non-Fellows to that of the Journal and the Fellowship subscription with Proceedings included compares well with the ratios for Societies abroad.It is then hoped that this single action will close the greater part of the gap in publications finance. There is no other way possible of getting such a large gain. But it must be backed by other changes which relatively small though each may be will collectively make a significant contribution towards financial stability. For instance the Publication Committee will be able to watch with extra care the efficiency of‘ editing and refereeing and are confident that small changes in the format of the Journal can be made without detriment. A saving of some &3,000per annum will also be achieved by not giving free reprints of papers to authors and by charging for those that are ordered on an economic basis.And finally the discrepancy between the prices does cause a real though very regrettable tendency for some Fellows to allow misuse of. their personal copies of the Journal. I cannot too clearly urge all Fellows who take the Journal to avoid any action of this sort and the Council has agreed to a more strongly worded declara- tion for signature together with a statement to be stamped on each issue of the Journal. It is hoped that this action will eliminate any con- scious or unconscious form of “black-market- ing” of the Journal by Fellows and prevent a loss of revenue to the Society. Council has also agreed to an increase in the price of Current Chemical Papers to E5 for non-Fellows and E2 for Fellows from January lst 1958.This is the only other publication of the Society which is not in financial balance though its circulation continues to grow and its value is clearly recognised. These changes large and small are realistic and represent determined action by the Council of the Society to put our affairs in order. Nothing less would be adequate. APRIL1957 107 CHEMISTRY AND ITS INDUSTRY-THEIR CONTRIBUTIONS TO OUR NATIONAL WEALTH FLECK, By SIRALEXANDER K.B.E. F.R.S ITis an obvious truism that modern industry is a great complex of many factors and that if in- dustry is being developed in an active way many of these factors will have important reactions on each other.Thus to give simple examples a well-founded electrical industry will influence the development of the farming industry for instance by way of electrical machinery just as it will influence and modify outdoor activities such as sporting events during the hours of normal darkness. It is to be expected therefore that when we come to consider the contribution which chem- istry and its industry have made to the country we have to consider their influence on a broad front and to remember that many of the con- tributions will not be unique but may well be given by other sciences and technologies and other industries. I am therefore anxious to make it clear at the outset that in attempting to assess the contribu- tion which the chemical industry makes to the wealth of the country I am in no way suggesting that other industries cannot match it in this or that respect.The interest Iies rather in viewing it in relation to the whole and perhaps as one might be forgiven for doing in this Journal look- ing in a little more detail at these aspects where it seems to have some special virtue. The first object must be to obtain some idea of the size of the industry. If for this purpose the official statistics for “Chemicals and Allied Trades” are used the gross product i.e. the value of the goods the industry sells amounted to &1,030 million in 1955 excluding mineral-oil refining. It is on this basis about one-quarter the size of the “Metals Engineering and Vehicles” industries and about the same size as the “Textile Leather and Clothing” industries.Such a figure is however unsatisfactory for several reasons. While giving some indication of size a large gross product could be derived for example by the use of expensive raw material with the industry itself contributing very little nor can it usefully be expressed as a percentage“ of industrial activity in the country as a whole. Further the category “Chemicals and Allied Trades” contains much that can only be described as fringe activities which most people would hesitate to include in the chemical industry proper. We therefore have to seek another definition and another figure. The merits of including this or excluding that can be argued at length but for present purposes I propose to adopt without discussion a definition approximating closely to that used by the Association of British Chemical Manufacturers in its “Report on the Chemicaf Industry 1953”.It excludes some which could be regarded as marginal such as paints and varnishes and mineral-oil refining but includes nothing which is not truly part of the industry. It consists essentially of dyestuffs fertilisers synthetic resins and plastic materials explosives and other chemicals and in terms of value isl about half that represented by “Chemical and’ Allied Trades”. The figure which I propose tol use is its net output. This is broadly the gross output less the value of materials fuels and ser- vices purchased.It is a useful criterion of the contribution which an industry makes and can be related to the industrial activity of the country as a whole. Defined in this way the net output of the chemical industry in 1954 was about E230 mil-lion or about 4 per cent of the total net output of U.K. manufacturing industry. It employed 203,000 people or 2&per cent of those engaged in manufacturing and this works out at a net output of &1,150 per head compared with the average of E780 for manufacturing industry as a whole. This high productivity is mainly due to the fact that each worker is backed by over E5,OOO of capital equipment compared with the national average of under &2,000 and it can be argued that the chemical industry is more than maintaining this position.Production has been rising at a rate of 8 per cent per annum comparedr with 5 per cent for all industry; new capital in- vestment in “heavy chemicals” alone totalled S192 million during the period 1951-54 repre-senting 8$ per cent of total new investment in manufacturing ; current expenditure in research in the wider definition of the industry is of the order of E20 million per annum or 11 per cent of the total for manufacturing industry. Such figures give the bare bones of the industry its size and how it is progressing but there is of course much more to the story. The chemical industry is essentially a supplier to other industries and little of its production directly reaches the consumer.It is inextricably bound up with the fortunes of industry as a whole and indeed as is well known activity in the chemical industry is a fair barometer of cur- rent economic conditions in general. The real value of its contribution to the industries which it serves is not something which can be readily assessed. For example what have synthetic dye- stuffs meant to the textile trade explosives to the mining industry plastics to the electrical in- dustry and so on? The difficulty is to visualise them without such chemical contributions. How- ever by way of illustration one can pick out an industry such as agriculture which is traditional and upon which the impact of the chemical industry can be clearly seen even over relatively short periods.The ever-growing demand for food as the population grows and the standard of living rises exerts a continuous pressure for increased pro- duction from a limited area of cultivable land and over the last twenty years the net output of British agriculture has increased by 55 per cent. Many factors have been at work unconnected with the chemical industry such as greatly in- creased mechanisation which has enabled almost the same labour force to handle a large increase in production and the breeding of new crop varieties ecologically better suited to their en-vironment and such factors must not be ignored. But having said this there can be no doubt that the increased consumption of the products of chemical industry over the same period has played a very important part.The only analysis that has been published of inter-industry purchases and sales refers to 1950 and at that time about 8 per cent of the chemical industry’s production in the U.K. was being con- PROCEEDINGS sumed by the agricultural industry in value some E77 million. Fertilisers are the most important group accounting for about three-quarters of the total the remaining one-quarter consisting essentially of antiseptics insecticides fungicides weed-killers and so on. From pre-war years there has been a three-fold increase in the com- bined quantity of nitrogen phosphate and potash fertilisers consumed and in the same period significant developments in the use of the other chemicals. During this time the yield per acre of wheat has increased by 30 per cent of barley by 32 per cent and of oats by 20 per cent.Achievements in combating animal diseases have been numerous. The prevalence of sheep scab was causing serious concern at the end of the 19th century and in one year there were over 3,500 outbreaks. A policy of dipping the sheep together with improvements in effectiveness of the dips has made it possible to say that for all practical purposes the disease has been eradicated from this country. Swine fever was responsible for the death of 3 per cent of all pigs in 1940 but with the increasing use of crystal-violet vaccine the loss has been reduced to less than 8 per cent. Such examples as I have quoted illustrate the position at the present time but it is not neces- sarily thc end of the story.Available evidence suggests that crops are still not being treated with fertilisers up to the optimum level which would prove profitable and that for example the national yield of wheat might be further raised by from 5 to 10 per cent and the output of grasslands by at least 30 per cent. Only a quarter of a million acres out of a total of 13 million acres of permanent pastures are sprayed annually with weed-killers yet the elimination of grassland weeds together with skilled manage- ment to make full use of the extra production of grass can do much to increase available feeding for livestock. Despite the advances which have been made animal losses due to disease still amount to nearly 10per cent of livestock output in value some E80 million.Thus we can form some impression of the contribution which the chemical industry has made and can still make to the agricultural industry. Its importance to the country as a whole scarcely needs emphasis. It has been esti- mated that the increased production since before the war has led to a saving at a present level of APRIL1957 about &350 million per annum of foreign expen- diture which would otherwise have been spent on food and animal feedingstuffs. Looking to the future an increase in the utilised output of grass- land of the order indicated might represent a further E200 million of feed or almost 2300 million worth of ruminant livestock products were it converted into milk and meat.In recent years the U.K. has imported annually &1,000 million of animal and human feedingstuffs representing approximately 30 per cent of total imports and viewed against this such figures as I have quoted must be regarded as significant. I have dwelt on the agricultural industry at some length because of its importance and because it does provide an excellent illustration of what might be described as the hidden con- tribution which the chemical industry makes to the wealth of the country. No doubt similar pictures could be built up for industries other than agriculture. However we have so far con- sidered only the material manifestations of wealth but the word has other connotations well-being and happiness as well as prosperity and it is pertinent to ask what if anything the chemical industry has contributed in this broader sense.Many instances come to mind such as the alleviation of human suffering effected by the advent of antibiotics and chemotherapeutics a field in which the industry has played its part. Less obvious perhaps is the part which it has played in stimulating scientific education not only through altruism be it said but because its very life depends on an adequate supply of scientists of all kinds. There must be a con-tinuous fiow of new scientific knowledge and sooner or later this knowledge must be turned to practical account in industry in the form of new or improved products and processes. The industry cannot be static; it must progress or deteriorate relatively to others.Realisation of this has led the industry to further the cause of scientific education in many practical ways. In the universities it has provided Chairs which it sup- ports financially grants to aid specific research projects fellowships and scholarships and has seconded members of its staff for full-time work. In the technical colleges apart from financial aid in one form or another individuals employed by industrial concerns are to be found on the I09 governing bodies and in the teaching staff. In the schools the teaching of science has long been assisted in one way or another notably now by the Industrial Fund supported in general but particularly by the chemical industry the main purpose of which is to enable schools lacking support from public funds to build science laboratories.All this might be ascribed to self- interest but there are few who would deny that it has been to the country’s good. The chemical industry can however claim one of its greatest successes and one of its most basic contributions in the field of industrial rela- tions. Admittedly success in this sphere is difficult to measure. There is no yardstick for morale but such measures as we have support the view which I have just given. For example if we return again to our category “Chemical and Allied Trades” we find that the days lost per 1,OOO workers because of industrial disputes have averaged 11 over the past seven years compared with 96 for the country as a whole.Similarly figures for labour turnover are rather better though less spectacularly so. The reasons for this are complex but at least part of the answer lies in the history of the industry. Good industrial relations do not grow overnight but are the fruit of prolonged and consistent effort and it is worthwhile to recall some of the events and people who contributed to the present relatively healthy position. In the 1880’s Brunner Mond & Company introduced a number of revolutionary changes in the working conditions of its process men. Notable among these was a reduction in the working week from 84 hours to 56 hours per week for men engaged on continuous process work and the introduction of a paid annual holiday for payroll employees.Such innovations shocked many other manufacturers and al-though many followed suit quite quickly it was not until the 1914-1918 war that the 84-hour week disappeared entirely. Following one of the recommendations of the Reports of the Whitley Committee appointed by the Government in 1916 Joint Industrial Councils were formed in a number of industries to discuss matters affecting the workers and well- being of the trade from the point of view of all those engaged in it. One of the first of these to be formed was the Chemical Trade Joint PROCEEDINGS Industrial Council. At the first meeting in August 19 18 among the workpeople’s representatives who were elected to the Executive Committee were Mr.Ernest Bevin and Mr. Tom (now Sir Thomas) Williamson. In the aftermath of the General Strike of 1926 Mr. George Hicks Chairman of the Trades Union Congress held in Edinburgh in September 1927 in his speech referred to the need for effec- tive machinery for joint conference between the representative organisations entitled to speak for industry as a whole. This was promptly taken up by Sir Alfred Mond (later Lord Melchett) then Chairman of Imperial Chemical Industries Limited and a man of vision devoted to the cause of human welfare in industry. The first meeting of the “Conference on Industrial Re- organisation and Industrial Relations” as it was called or the Mond/Turner Conference as it is remembered Mr.Ben Turner being Chairman of the General Council of the Trades Union Congress at that time was held in January 1928. Contrary to expectation the Mond/Turner talks did not lead to the immediate setting up of permanent joint consultative machinery. It did however achieve much more. It opened people’s minds changed their attitudes and behaviour and laid the foundation of a new relationship between capital and labour. Since those days the machinery for joint consultation has been consolidated and further elaborated but it is appropriate that due credit should be given to people such as those who opened the way ahead. Today the chemical in- dustry can rightly be proud of its position in the van of industrial relations labour management and welfare but much remains to be done.Else- where* I have recently expressed my strong personal opinion that the problems of human relationships in the chemical industry will merit our closest attention in the future as indeed they have in the past and I would not express any other view now. Nonetheless there is no reason for the industry to hang its head over what it has already contributed to the wealth of the nation. In concluding these observations on some particular aspects of chemistry and its industry I should like to repeat the disclaimer with which I began. In writing as I have done of the chemical industry other sciences and industries have been ignored but that is not to say they should be for- gotten. Further in illustrating the part played by the industry there has of necessity been an element of personal selection in the topics chosen.Someone else might well have chosen differently. Nevertheless the illustrations are ones to which I attach great importance and if they have con- veyed some idea of how the chemical industry is moving in an industrial world they will have served a useful purpose. A consistent forward movement is necessary beyond all other require- ments if the chemical industry of Britain is to maintain a position of eminence stimulating alike to our scientists and to our industrialists. Other industries in our nation may be larger others may be more in the limelight that makes them prominent to the masses making up our 23 million people who are gainfully employed but what I like to believe is that none has made a greater contribution to the morale of its people.Finally I would say that no British industry in recent times has given a greater stimulus to science and technology not only through ancil- lary services to industry as a whole but also through the application to industrial processes of the more advanced aspects of scientific principles. * Messel Memorial Lecture Society of Chemical Industry. October 1956. APRIL1957 111 TILDEN LECTURE* The Physical Properties of Polymers in relation to their Chemical Structure By GEOFFREY GEE (THEUNIVERSITY, MANCHESTER) ITwill be apparent that the field of work covered by the title is much too broad to be surveyed in any single lecture.My aim will be to review a number of the more outstanding properties of polymers and to suggest that these find a ready interpretation in terms of a limited number of structural factors. I shall stress particularly two such factors intermole-cular forces and chain flexibility. PoZymer Chain Structures.-Most of the polymers with which we shall be concerned are essentially linear familiar examples being polyethylene [CH,], polytetrafluorethylene [CF,], and the vinyl polymers [CH,*CHR] with R = Ph C1 etc. As prepared in the laboratory or industrially these polymers are almost invariably branched to a greater or smaller degree e.g. in polyethylene we kd generally a con-siderable number of short branches or side chains (cf.I). In other polymers the branches may be longer but less frequent. are of this type and there may be typically one cross- link for every 50 or 100 units along the chain. At the other extreme stand the thermosetting resins built up from polyfunctional units so that a very closely knit three-dimensional structure is possible. We shall not be concerned in this lecture with this kind of polymer typified by the phenol-formaldehyde resins (cf. 11). "Liquid" Polymers.-Any polymer which is not cross-linked begins to behave essentially as a liquid TABLE 1. Some properties of Siliconefluids (polydimethylsiloxanes) Viscosity grade 103a(deg.-l) p (cm.2 dyne-l) Pz= aT/p (cal. cm.-3) of fluid* 30" 30" 30" 50-7* 0.65 1-491 238.8 45.2 40.3 3 1.103 155.6 51.3 45.9 10 1 -055 140.7 54.3 50-6 50 1 -020 131.4 56.2 51.5 100 0.902 125.2 52-2 49.5 200 0.913 124.5 53.1 49-8 350 0.889 123.3 52-2 49.7 500 0.891 122.8 52-5 49.9 lo00 0.893 122.7 52-7 50.2 * Midland Silicones Ltd.(Ms 200 Silicone Fluids). In the next higher degree of complexity the long- chain molecules are linked together (cross-linked) in such a way as to create a three-dimensional network. In a vulcanised rubber we have essentially a single giant molecule which constitutes the whole of the bulk sample of rubber under investigation. A rough classification of network structures may be made depending on the frequency of cross-linking. At the one extreme we have polymers where cross-links are infrequent;the material consists essentially of long chains with the minimum of junction points to con- nect them all into the network.Vulcanised rubbers if its temperature can be taken sufficiently high without the occurrence of chemical decomposition. In comparing its properties with those of a normal liquid we have to distinguish between static and dynamic properties. The former include the coeffici- ents of thermal expansion (o! G compressibility (18 E -) and the specific heat. These quantities are of the same order of mag& *Delivered before the Chemical Society in Aberdeen on November 23rd and in London on December 13th 1956. tude in liquid polymers as in liquids of low molecular weight showing that locally the structure and mobility are similar to those in a simple liquid.If we compare a unit in a chain with a molecule of a simple liquid it is clear that the chain unit is somewhat more restricted by reason of its attachment to neigh- bouring units of the same chain. Its intermolecular interactions will not however differ greatly from those of the simple liquid. One might expect there- fore that a and would be somewhat lower for a polymeric liquid than for a simple one. This expecta- tion is borne out by data illustrated in Table 1 which gives values of a and /3 for a series of Silicone fluids (polydimethylsiloxanes) the values fall with in-creasing chain length but very soon tend to limits. When we turn to dynamic properties a very different result is apparent the viscosities of poly- meric fluids are very high and often non-Newtonian.We shall ignore the latter complication and discuss viscosity in terms of polymer structure and behaviour. PROCEEDINGS energy is not confined to the molecule which is to move; (ii) that the activation process is not closely defined. We can go a little further and suggest that the activation will involve an expansion say A V in the neighbourhood of the molecule which is going to move and hence that the energy of activation E9 should be approximately that required to expand the liquid by A V against its internal pressure Pi.Hence if 7 is the viscosity at temperature T we have EDEZ-RT2(a--) In7 aT P‘ ................. Ep zpiA v ..........................’ (2) aT pi = T(:)“ -p= -P .........-(3) B Thus we can measure EDand Piand hence calculate A V from equation (2). If our picture is to be plaus- ible it is clear that A V must be comparable with the molar volume V of the liquid. Table 2 collects some results which show that AV/V does not vary TABLE 2. Activation energy for viscousflow ED (cal./mole) Ethyl ether 1430 n-Pentane 1585 Me formate 1640 Me acetate 1840 COMe Et 1930 n-Octane 2185 Benzene 2490 cc1 2760 0-Xylene 3265 Viscosity of Simple Liquids.-The viscosity of liquids has been frequently discussed and it would clearly be beyond the scope of this lecture to review the various theories. I wish to put forward some sugges- tions based essentially on the model used by Eyring,l but without necessarily implying acceptance in detail of Eyring’s treatment.If we consider first a simple liquid we find that any individual molecule is sur- rounded most of the time by a group of other mole- cules which in effect hold it in a cage. Before it can move (relatively to its neighbours) it has somehow to get out of the cage and we can therefore imagine viscous flow as an activated process in which the energy of activation represents the energy which has to be accumulated in the vicinity of the molecule before it can leave its cage. In contrast with chemical activation two points should be noted (i) that the Pi vm AV[V = (cal.1c.c.) (c.c./mole) EJPi Vm 55 105 0.25 50 116 0.27 103 62 0.26 92 80 0-25 85 90 0.25 57 1 64 0.23 84 89 0.31 74 97 0.38 81 121 0.32 systematically with Pi or V, and is generally of the order 0.3 which must be considered very reasonable.Before extending this treatment to polymers it is worth mentioning another line of argument. If we consider the activation process in terms of the transition-state treatment we can relate an activa- tion volume AVS to the pressure coefficient of viscosity ..................(4) If we further define an activation energy at constant volume (EJ then For a review see Glasstone hider and Eyring “The Theory of Rate Processes” McGraw Hill New York Chapter IX. Viscosity data from Barrer Trans. Faradav Soc. 1943 39 48; internal pressures from Hildebrand and Scott “The Solubility of Non-Electrolytes” Reinhold Publ.Corp. New York 1950. APRIL1957 then by a purely mathematical analysis aT E + -19 dVt . '(6) If now d V3 is identified with d V as would appear reasonable we see that our intuitively derived equa- tion (2) can only be strictly valid if E = 0. Experi-mental evidence on this point is scanty but indicates that while E may be small in comparison with ED it is not generally negligible.3 We are starting in Manchester further measurements of pressure coefficients of viscosity but for the purposes of this lecture I shall ignore E and discuss Ep in terms of equation (2). Polymer Viscosity.-The above treatment requires some modification for application to long-chain molecules. If the relation d V/V Z 0-3 continued to hold the energy of activation would assume very high values proportional to the degree of poly- merisation.In fact the energy of activation increases with chain length only for very short chains and soon reaches a limiting value (e.g. 13.2 kcal. in the we of polyisobutene at 100"). The interpretation of this observation is that a polymer molecule does not generally move as a whole but in segments. This conclusion appears very reasonable indeed if we imagine a polymer molecule as a long flexible rope. If such a rope is lying on the ground in a randomly kinked and coiled shape it can be moved bodily into a new position by taking it a short length at a time most of the rope being stationary while one length is moved.A segment of a polymer chain is a statis- tical concept and represents the most probable size of unit which is involved in flow processes. It is clear however that movement of the rope (or molecule) is not complete until all its segments have moved in a co-ordinated manner. While therefore the energy of activation for viscous flow is determined by the segment the probability that all the segments of a molecule will move in co-ordination will evidently diminish rapidly as their number increases. Thus the absolute viscosity will increase rapidly with chain length and it was shown by Flory4 that the melt viscosity of a linear polyester increased exponentially with the square root of the degree of polymerisation although EDremained constant.If the picture which has been sketched is approxi- mately correct we must look for the effect of chemical structure on viscosity in terms of two factors internal pressure and segment size. These will be considered in the next two sections. Lawrence. Proc. ROY.SOC..1951. A. 206. 257. Internal Pressures of Polymers.-There is no difficulty in principle in obtaining the internal pres- sures of polymers by means of equation (3) but suit- able data are at present very scanty. Compressibility measurements on polymers have generally been carried out at fairly high pressures and it is not usually easy to extrapolate /Ito P = 0 with the precision desirable for this purpose. The figures recorded in Table 1 were calculated by my colleague Dr.G. Malcolm from sound-velocity data.5 Another method of evaluating intermolecular forces in polymers which has been widely used is based on the concept of the cohesive energy density (C.E.D.). For simple liquids the C.E.D. is defined as the energy of evaporation per C.C. [= (L-RT)/ V, where L = molar latent heat of evaporation]. It is found empirically that for most liquids the C.E.D. and the internal pressure do not differ by more than a few per cent. This definition of the C.E.D. is inap- plicable to polymers and an indirect method has been used based on the argument that the best solvent for a polymer will be a liquid whose C.E.D. is equal to that of the polymer.g Hence by studying the interaction of a polymer with a range of liquids it is possible to assign a C.E.D.which may then be assumed equal to the internal pressure. This pro- cedure is not very satisfactory even for hydrocarbon polymers the C.E.D. obtained depends on the choice of liquids used and such scanty evidence as we have does not support the assumption C.E.D. Pifor polymers. A third line of reasoning is even more qualitative. Since as we have seen a and /3 are not very depend- ent on chain length but both fall somewhat to limit- ing values (cf. Table 1) it is reasonable to expect that internal pressures of polymers would not differ greatly from those of their monomers and that they might be expected to fall approximately in the same relative order. In Table 3 these three methods are compared and it is clear that the present position is not very satis- factory.The order of magnitude of Pi is certainly known but the differences between the internal pres- sures of polymers are comparable with the accuracy with which Piis at present known. It is not therefore yet possible to discuss with any precision the effect of chemical structure on internal pressure. We are now undertaking further measurements in Man-Chester based initially on a direct study of (%);of Segment Size and Activation Volume.-Estimates the segment size and activation volume are obtain- Flory J. Amer. Chem. So;. 1946 62 1057; 1948,70 2384. Weissler ibid. 1949 71 93. (a)Gee,Trans.Inst. Rubber Ind. 1943 18 266; (b) Scott and Magat J. Polymer Sci. 1949,4 555. 114 PROCEEDINGS Polymer Silicone rubber Pol yiso bu tene Natural rubber Neoprene Polyvinyl chloride Polymethyl methacrylate Polymethyl acrylate Polystyrene TABLE 3.Estimation of internal pressures of polymers C.E.D. of C.E.D. of polymer Pi of polymer (cal. /c.c.) monomer (cal./c.c.)from solubility (ca1.lc.c.)(aT/B 57a 54 45 66 56 64 c 70d 88 63 70 67c 85d 92 74 100 81 85 86 85 a R. H. Hauser Ind. Eng. Chem. 1956 48 1202. b Silicone fluid ;cf. Table 1. c d Refs. 6 (a) and (b)respectively based on different ranges of liquids. able from either temperature or pressure coefficients of viscosity of which however only the former are at present generally available. In discussing the effect of chemical structure on segment size it seems to me certain that the most important factor must be the stiffness of the polymer chain.The stiffer the chain the larger will be the segment until in the limit with an infinitely rigid molecule the segment must neces- sarily be identical with the molecule. Thus whereas Piis a measure of intermolecular forces A Y is deter- mined by intramolecular factors. It follows that Pi and d Y are not necessarily related in the same way to chemical structure and must therefore be con- sidered separately in discussing the effect of chemical structure on viscosity. As an illustration of the interplay of these factors let us compare three types of material for which we have some data relating to the lower members of the series I the paraffins’ [CH,],; 11 the fluorocarbons* [CF,] ; and 111 the polydimethylsiloxanes9 [SiMe,.O],.The order of internal pressure here is almost certainly I (65) > 111 (55) > I1 (49 the figures in parentheses giving estimated mean values (cal. per c.c.). The order of chain stiffness however will be quite different. The paraffin chain is not highly flexible owing to the appreciable rotation barrier of adjacent methylene groups. The fluoro- carbon chain is much stiffer but the siloxane chain is extremely flexible owing to the absence of sub- stituents on the oxygen and the comparatively large spacing of the SiMe groups. Thus the order of chain stiffness is I1 > I > 111. If now we plot E,/P for the lower members of these three series against their molar volumes the three curves should approxi- mately coincide for the lowest members but diverge at great chain lengths increasing in the order III< I < 11.The rather fragmentary data available have been plotted in Fig. 1 and appear to bear out these predictions very satisfactorily. Rubbers.-Perhaps the most striking physical state exhibited by polymers is that of rubber-like elasticity characterised by the possibility of reversible elastic deformations of several hundred per cent. of the undeformed size. This behaviour is shown to a limited extent by most high polymers but is best developed in those which possess just sufficient cross- links to build up a three-dimensional network. I do not wish to discuss in detail the equilibrium elastic behaviour of such a material as this is now well understood in principle.It is recognised that the elasticity resides essentially in the molecule which in a cross-linked network is taken to be the length of chain between adjacent cross-links. Each molecule tends by virtue of its thermal motion to take up a series of highly kinked conformations in which the distance between its ends is much less than the fully outstretched length. Deformation of the rubber straightens the molecule which tends to return to a more kinked state when the deforming force is removed. Thus each molecule behaves rather like a spring and the overall elastic modulus of the rubber is determined by the number of springs i.e. of cross-links in the rubber.This picture has been developed quantitatively into a theory which gives a very satisfactory account of the static elastic properties of rubbers.1° The dynamic properties of rubbers are much less understood. It is clear that the straightening or kink- ing of a molecule involves relative movements between the molecule in question and its neighbours a process which is closely related to that of viscous flow. A cross-linked polymer cannot undergo bulk Data mainly from Tnternat. Crit. Tables and from ref. 1. “Fluorine Chemistry” Academic Press New York; Rudge Chem. and Ind. 1955 452. Wilcock J. Amer. Chem. SOC.,1946 68 691. lo For a general review see Treloar “Physics of Rubber” Oxford 1949. APRIL1957 flow but the rate of these internal re-arrangements will be governed by what we may reasonably term an internal viscosity.If the internal viscosity is high the rubber will respond only sluggishly to applied ex- ternal forces and will show marked hysteresis if cyclic deformations are imposed. I do not propose to examine this problem more fully in the present lecture but it is clear that we should look for the same structural factors as have been found operative in bulk viscosity. -250 -200 c, <750 -ri“ \ kl I00 -50- 0 ZOO 400 600 800 Mo/ar volume (c.c.) FIG.1. Activation energies for viscous flow I Parafins. II Fhorocarbons. III Silicones. Intermediate between Newtonian viscosity and reversible elasticity we find the condition of visco- elasticity.Most linear polymers if deformed sufficiently rapidly behave as though they were cross-linked rubbers. Perhaps the most striking example is the Silicone known popularly as “bounc- ing putty” which flows at an appreciable rate under its own weight but nevertheless bounces extremely well when dropped or thrown on a solid surface. The qualitative explanation of this is clear enough in the short time available during a rapid deformation co-ordination of segmental motions is not sufficiently complete for flow to occur-the molecules remain so to speak entangled in places and those segments which have moved are drawn back again when the deforming force is removed. It is apparent that a rather nice balance of properties is needed for the production of a high degree of viscoelastic be- haviour.Internal viscosity must be low to permit both flow and high resilience while the molecular weight must be high enough to encourage entangle- ments. It may be noted that raw natural rubber although practically free from cross-links shows virtually no flow except under prolonged stress and behaves almost as a reversibly elastic substance. Reduction of its molecular weight by mechanical degradation reduces it to a viscoelastic condition. l1 Boyer and Spencer Ah. Colloid Sci. 1946 2,I. The Glassy State.-When a liquid or rubbery polymer is cooled it is converted into either a glass or a crystalline material. These two possibilities are examined in this and the following section.The onset of the glassy state is shown by marked changes in the physical and mechanical properties of the polymer. If a sample is cooled slowly in a dilatometer there is no discontinuity in the volume-temperature curve such as occurs on crystallisation but the coefficient of expansion falls to about one-third of its value at -250 2m- 0 F >I50 -e 5 ruQ700 --50 I I I I Ol ;oo 80” 100” 720” 140” Temp. FIG.2. Activation energy for viscous flow of polymethyl methacrylate. [Reproduced,by permission from Bueche J. Appl. Phys. 1955 26 738.1 a fairly well-defined temperature. The compres-sibility specific heat and refractive index show similar discontinuities at the same temperature.ll This temperature has been widely called a second-order transition temperature because of the formal analogy between this behaviour and that implied in Ehrenfest’s definition of a second-order transition.I2 I do not propose in this lecture to discuss the thermo- dynamic significance of this phenomenon and there- fore prefer to use the neutral term “glass tempera- ture” (Tg).Mechanical properties undergo profound changes in the temperature range immediately above T and estimates of Tghave been based on such observations e.g.the onset of brittleness. These tests are however all rather dependent on the precise method of test and particularly on the time scale rapid tests give high values of “Tg”.This fact has thrown much doubt on the reality of any precisely definable glass temperature but it is at least indis- putable that a sharp change of properties occurs within a short temperature interval and it will be sufficient for this lecture to treat this as a definite temperature.We have seen that at Tg, 01 /3 and C fall abruptly. Further evidence as to the nature of the change is given by a study of viscosity which rises extremely l2 Ehrenfest Leiden Commem. Suppl. 1933 75 f. rapidly as T is approached. Hitherto we have treated ED as a constant but this is in fact far from being the case. In general Ep rises with fall of temperature and this behaviour becomes very marked in polymers approaching T,. At Tgthe viscosity becomes very high and extension of measurements below T is difficult; the evidence available suggests however that EDreaches a maximum at or about T, there-after falling off extremely rapidly.Fig. 2 shows some results13 for polymethyl methacrylate which show this behaviour and illustrate the extremely high values which EDmay attain. If equation (2) is still taken as our guide (and it must be borne in mind that we have no knowledge ofE under these conditions) this behaviour of Ep must be consequential upon a large rise in Pi and/or d V. It can be safely assumed that Piwill in general rise with fall of T. For simple liquids Hildebrand and Carter14 found that the combined effects of changes of Tand P on the volume of a liquid could be expressed by the empirical relation y2Pi = Constant.. . . . .... . .. . . . . ... .. ...(7) It is easily seen that if equation (7) holds the temperature coefficient of Pi is given by A rise of this magnitude would not contribute very materially to the extremely large increase observed in ED.While we have as yet little evidence concerning the applicability of equation (8) to polymers I personally consider it unlikely that Pi increases markedly in the region of Tg. If this argument is valid it follows that the sharp increase in Ez is associated mainly with an increase in d V. This would arise naturally if the polymer chain becomes progressively stiffer with fall of T so that the effective segment size increases continuously. This seems to me to be exactly the behaviour to be expected from the qualitative discussion of segmental motion given above.Segment size is determined by a statistical balance between the thermal energy of the chain and the energy required for rotation in the chain. Qualitatively therefore reduction of tempera- ture must increase the segment siie but further experimental evidence will be needed to assess the quantitative significance of this factor.* This analysis of the increase of EDwith falling T leads to a fairly clear picture of what happens at T,. PROCEEDINGS Large-scale molecular movements such as are required in viscous flow have been getting rapidly more difficult and at Tgthey virtually cease. Below Tgonly very localised movements are possible these require only a low energy but opportunities for them are very few.The cessation of long-range movement is reflected in the sudden fall in a; this may be put in another way by saying that the disorder remaining in the polymer at Tgis now frozen in and does not diminish further on cooling to lower temperatures. Our discussion of the glassy state has again led us to stress the importance of the two structural factors represented by Pi andd V.It will be highly interesting when the data become available to seek to correlate the glass temperatures of a range of polymers with these two quantities; such a comparison is scarcely possible with the very inadequate and approximate data yet available. CrystaZlisation.-Crystallisation in high polymers is more complex than in substances of low molecular weight the complications arising mainly from the fact that the structural element in a crystal is not a molecule but only a portion of one.If we consider the process of crystallisation from the melt we have to imagine lengths of disordered chains fitting into the ordered pattern of the crystal this is clearly a difficult process and understandably slow. It is not to be expected that crystallisation will ever be per- fect or that individual crystals will become large. Moreover a single molecule may well lie partly in each of two crystals with an intermediate disordered region. Such considerations accord well with the small crystallite size and unsharp melting phenomena observed in practice. Some authors have concluded that polymer crystallisation cannot properly be con- sidered as a first-order phase change in the usual thermodynamic sense.Since a “melting point” can be uniquely defined as the temperature above which the crystalline phase is unstable I believe personally that normal thermodynamic reasoning can be applied to this temperature. As soon as a finite amount of crystallisation has occurred the situation becomes much more complex owing to the mechanical inter- action between the crystalline and amorphous regions.16 The most important factor determining crystal- lisability is the regularity and symmetry of the structure. The importance of even small deviations from regularity is well illustrated by the different ethylene polymers which have been made. It has * G!bbsl5 has developed a rather similar argument in a more quantitative manner and has proposed a theoretical definition of Tgas the temperature at which the chains have become so stiff that the configurational entropy vanishes.l3 Bueche J. Appl. Phys. 1955 26 738. 14 Hildebrand and Carter J. Amer. Chem. SOC.,1932 54 3592. l6 Gibbs J. Chem. Phys. 1956 25 185. 16 For a review see Flory “Principles of Polymer Chemistry” Cornell Univ. Press New York 1953 pp. 653 et seg. APRIL1957 already been noted that the normal commercial pro- duct possesses a number of short side chains per molecule. (Typical products have been shown by infra- red analysis to have about two CH groups per hundred CH,.) This material has a density at room temperature of 0.92 and melts at about 105”.Poly- methylene (completely unbranched) can be made by the polymerisation from diazomethane it has a density of 0.97 and melts at 130”. The truly linear material is therefore much more crystalline and higher-melting. Apart from the possibility of branching vinyl polymers have two other potential sources of struc- tural irregularity. The first of these is the occasional departure from regular head-to-tail arrange-ments e.g. -CH,-CHRCHRCH,-in place of -CH,.CHRCH,-CHR- but there are both theoret- ical and experimental reasons for thinking this to be rare. Much more significant is the possible occur- rence of stereoisomers illustrated in the annexed formulae. The chain backbone is imagined to be in CH CH CH CH (m) the plane of the paper.In structure A each -CHR- group is so oriented that R is above the plane; in B the middle R lies behind the plane. A and B are thus stereochemically distinct. Although the prob- able occurrence of stereoisomerism has long been recognised it is only recently notably as a result of the work of Natta,17 that stereochemically pure vinyl polymers have been obtained. Natta has intro- duced the terms “isotactic” for polymers in which the same orientation persists (as in A) and “syndio- tactic” for polymers in which adjacent centres have opposite orientations; where the orientations are random the polymer is “atactic”. The effect of stereo- chemical regularity is very striking atactic poly- styrene is a typical amorphous polymer while iso- tactic polystyrene is highly crystalline and melts at 230”.Melting Points of Crystalline Polymers.-It would be extremely useful to be able to predict the melting point of a polymer from its chemical structure. Inspection of a list of known melting points does not at first suggest many regularities (see Table 4). One l7 Natta. J. Polymer Sci.. 1955. 16. 143. negative conclusion is fairly evident melting points are in no way correlated with internal pressures. The various polyolefins listed must have rather similar Pi and as we have already seen polytetrafluorethylene has probably a very low P,.The very high melting point of this material suggests that we might look for a correlation between melting point and chain TABLE4 Melting points of crystalline polymers Repeating unit -CH,.CH,--CH ,CH Me- -CH,*CHPh--CH,-CH(CHMe& -CH,CH,.O--CH,CHMe-O--CF,.CF,--CF,*CFCl-M.p.4 (cal. g.-I deg.-l) 130” 0.14 160 0.035 230 > 0-016 300 -66 0.13 70 Q 0.057 327 ca. 0.02 210 0.021 -O.[CH,] ,,*OCO*[CH,&-CO- 80 0.10 -(C,H,O&(O*COPrn)s-} 207 (Cellulose tributyrate) 0.017 stiffness. Flory18 has already discussed the statistical mechanics of rigid rod-like polymers and has con- cluded that rigidity will favour crystallisation. Such a conclusion appears intuitively reasonable the problem of packing rigid rods without leaving empty spaces can only be effectively solved by an ordered parallel arrangement. It is not immediately apparent that this explana- tion will apply to the very high-melting isotactic polyolefins.These are all vinyl polymers in which there is a progressive rise of melting point with the bulkiness of the R group (Table4 lst 2nd and 4th compounds). If we consider the structure of these polymers (IIIA) it is evident that a bulky R group will impose serious steric restrictions on the con- formations of the molecule. Study of molecular models shows that a considerable rotation is required between adjacent units to avoid overlap of the R groups. If this rotation is carried out uniformly in one direction the molecule is wound into a helix. This is exactly the structure found in the crystalline forms of all the vinyl polymers studied by Natta and his co-workers.lg What is most significant in the present connexion is that the helical form evidently does not arise during crystallisation but is a pro- perty of the individual molecule imposed by steric factors.Molecular models reveal that the helical molecule is quite stiffksentially a somewhat bulky l8 Flory,‘ Proc. koy. Soc.; 1956 A,‘234 73. l9 Natta Atti Accad. naz. Lincei,Rend. Classe Sci. fis. mat. nat. 1956 20 408 and earlier papers. rod and this is particularly the case with the biggest R groups. It may be suggested therefore that the high melting points of the isotactic vinyl polymers can again be correlated with chain stiffness. An alternative way of considering the melting point of a substance is in terms of the latent heat Lf and entropy ASf of fusion.Provided that in the case of a polymer we define these quantities in terms of the first small degree of crystallisation we can write the melting point T = Lr/ASf.Hence a high melting point can arise from high L or low AS,. The argu- ment we have been advancing requires that AS should be low for these high-melting polymers in effect we have said that the molten and the crystal- line state do not differ greatly. if the entropy of fusion is indeed low this should be reflected in a large pressure coefficient of melting point and a small temperature coefficient of solubility. Evidence on these points appears as yet to be scanty but within its limits is uniformly favourable to our hypothesis. Thus the melting point of polytetrafluorethylene is raised 2o from 327"to 481 " by a pressure of 1,OOOatm.Again whereas polyethylene is virtually insoluble 50" below its melting point,21 polypropylene can be obtained in 1 % solution 90" below its melting point,22 and 0.3% solutions of polystyrene have been (cf. used at room temperat~re~~ T = 230"). Approximate calculations of the entropies of fusion (in cal. g.-l) based on these observations give the figures recorded in the third column of Table 4. The most convincing way to test this analysis would be by modifying the structures of the polymers in a way expected to change their melting points markedy. In this connexion a very interesting series McGeer and Duus J. Chem. Phys. 1952,20 1813. Richards Trans.Faraday SOC.,1946 42 10. ez Ciampi Chimica et Industria 1956 38 298. PROCEEDINGS of polymers would be the polyethers derived from the olefin oxides. We have undertaken in Manchester a systematic study of these materials but not many crystalline polymers have yet been obtained. So far as they go however the results show the lowering of melting point to be expected from the increased chain flexibility conferred by the oxygen atoms. Polyethylene oxide is of course well known and melts at 66". Polypropylene oxide has recently been obtained in crystalline form,24 m.p. 70" and its crystal structure determined.lg It is found to be flat [cf. (IV)] as would be expected for there is no steric problem requiring a helical form. I conclude therefore that chain stiffness is an important factor to be considered in predicting the melting point of a crystalline polymer.Conclusions.-This brief survey has of necessity given a very simplified account of some of the com- plex phenomena encountered in a study of the physical properties of polymers. I have made no attempt to mention all of the many people who have contributed to our present knowledge but have rather sought to present a coherent personal view of what I consider some of the high-lights. My thoughts on these subjects have been matured in discussions with my colleagues and to them I gladly acknowledge my indebtedness both for suggestions and criticisms and for permission to refer to unpublished work. 23 Peaker J.Polymer Sci. 1956 22 25. 24 Price J. Amer. Chem. SOC.,1956 78 4787. COMMUNICATIONS The Reaction of ChIorobistrifluoromethyIphosphinewith Amines and Ammonia By G. S. HARRIS (UNIVERSITY LABORATORY, CHEMICAL CAMBRIDGE) THEreactions of phosphorus trihalides and halogeno- phosphines with ammonia and primary and second- ary amines have received considerable study resulting in the isolation and characterisation of numerous substituted phosphines containing P-N b0nds.l How- ever it appears that many of these reactions are not straightforward and in many cases the substances isolated are not those expected from the simple elimination of hydrogen halide but are transforma- tion products of these derived for example by con- densation with the elimination of ammonia.In particular the existence of a stable aminophosphine has not been reported. It was of considerable interest to study the reac- tions of halogenotrifluoromethylphosphines with ammonia and its derivatives in order to observe the See Kosolapoff "Organophosphorus Compounds" Wiley New York 1950 p. 300 for a list of compounds. APRIL1957 effect of the strongly electronegative trifluoromethyl groups on the course of the reactions and on the nature and stability of the products. Chlorobistrifluoromethylphosphine (CF,),PCl and ammonia were allowed to interact in the vapour phase and it was found that each mole of the phos- phine reacted with two moles of ammonia to produce a volatile liquid and a white solid. The solid was ammonium chloride and the volatile liquid (after vacuum-fractionation to remove traces of the re- actants) has been shown to be aminobistrifluoro- methylphosphine (characterised by analysis mole- cular-weight determination and infrared spectrum).The reaction therefore occurs in accordance with the equation (CF,),PCl + 2NH3 -+(CF,),P.NH + NH,Cl and there is no tendency for the hydrogen atoms of the amino-group to react with more (CF,)2PCl. The yield of the amine was 96%. Aminobistrifluoromethylphosphine is a colourless liquid whose boiling point (extrapolated) is 67.1 O and melting point -87.5". The Trouton's constant is abnormally high indicating association in the liquid presumably due to the presence of F*-H-*N hydro-gen bonds.Oxidation by atmospheric oxygen occurs readily however the material can be kept indefinitely in a sealed tube at 0".The P-N bond like that in most phosphorus-nitrogen compounds appears to possess considerable thermal stability but it is easily broken by aqueous hydrolysis. Analogous reactions have been found to occur between chlorobistrifluoromethylphosphine and substituted ammonias and the compounds (CF,),P.NHMe (CF,),P.NHPh and (CF3),P-NMe2 have been isolated and characterised. The reactions of halogenotrifluoromethylphosphines with the hydrides of other non-metals is also being studied. The author thanks Professor H. J. EmelCus F.R.S. for his interest in this work and provision of laboratory facilities and the Ramsay Memorial Fellowships Trustees for the award of a Fellowship.(Received March 6th 1957.) Structure of ruscogenin By D. BURN B. ELLIS,and V. PETROW (CHEMICAL LABORATORIES LTD., RESEARCH THE BRITISHDRUG HOUSES LONDON N.1) LAPINand SANNIBreported1 the isolation from Ruscus aculeatus L. of a new steroid sapogenin ruscogenin m.p. 205-210" [a],-127" to which they assigned2 the constitution 25 D-spirost-5- ene- 3b:19-diol (19-hydroxydiosgenin) (1). In addition they described the conversion of ruscogenin into a compound regarded as 19-nordiosgenone (11) and have drawn attention to the possible value of the sapogenin as a source of the biologically important 19-nor-steroid hormones. We have isolated from R. aculeatus L. a sapogenin with m.p. 197-199" [a],-106" (after brief drying at 100"); these constants are in fair agreement with those for ruscogenin.Degradation of our material gave the corresponding pregnanediol derivative which passed on Oppenauer oxidation into I-de- hydroprogesterone identical with an authentic speci- men kindly supplied by Dr. A. Wettstein. This observation clearly excludes a 19-hydroxy-formula- tion for the parent genin but is consistent with a 1:3- or a 2 3-dihydroxy-structure of which the former (Le. a 1( :3p-dihydroxy-d5-structure) is pre- ferred. We therefore submitted our sapogenin to Lapin and SanniC Bull. SOC.Chim. France 1955 1552. Sannik and Lapin ibid. p. 1556. Djerassi and Ryan J. Arner. Chem. SOC.,1949 71 1O00. Oppenauer oxidation obtaining in poor ketone C27H3803 formed from it by loss of two hydrogen atoms and of a molecule of water.The product has an ultraviolet absorption maximum at 245 mp and is clearly a 1 4-dien-3-one as its derived 2 :4-dinitrophenylhydrazonehas a maximum at 402 rnp3 Incidentally we failed to identify formaldehyde in the products of the Oppenauer oxidation an observation which argues against the 19-hydroxy-formulation. Sannii and Lapin were able to correlate ruscogenin with di0sgenin.l On this basis our ketonic product would be 25D-spirosta-l 4-dien-3-one (1 -dehydro- diosgenone) (111). An authentic specimen of the lattefl was therefore synthesised from 5~: 250-spirostan-3-one (tigogenone) by a bromination-dehydrobromination route but it differed from our ketonic product from ruscogenin.The infrared spectra of the two dienones however proved remark- ably similar differing significantly only in the region 850-950 cm.-l the dienone from tigogenone showed a band at 898 cm.-l and a second less intense band at 921 cm.-l data confirming the 25D(iso)-configura- PROCEEDINGS ti~n;~ the dienone from ruscogenin showed two identically placed bands but with the reverse order of intensity so that this compound has the isomeric 25L(normal)- c~nfiguration.~ Re-examination of the infrared spectrum of our sapogenin revealed that the bands at 898 and 921 cm.-l were of almost equal intensity providing presumptive evidence that our material consists essentially of 250-and 25Lspirost-5-ene-l,$ :3/3-diol (10 (Received March 7th 1957.) This compound has since been prepared by Miki and Hara Pharm.Bull. (Japan) 1956 4 421. Wall Eddy McClennan and Klumpp Analyt. Chem. 1952 24 1337. The Hydrolysis of 4-Methoxydiphenylmethyl Hydrogen Phthalate By A. N. BOURNS, C. A. BUNTON,and D. R. LLEWELLYN (WILLIAM AND RALPHFORSTER RAMSAY LABORATORIES COLLEGE LONDON, UNIVERSITY GOWERSTREET W.C. 1) DURINGtheir work on the stereochemistry of hydro- lyses of carboxylic esters Kenyonl and his co-workers observed extensive racemisation in the hydrolysis of 4-methoxydiphenylmethyl hydrogen phthalate and suggested that the alkyl-oxygen bond was broken. Our aim was to study the steric and isotopic course of the reaction under kinetically controlled condi- tions and in particular to examine the possibility of migration (1) or (2) of the alkyl group during hydrolysis with consequent racemisation of the ester.2 The latter point was tested by synthesising the hydrogen phthalate with its alkyl-oxygen atom en- riched in 180 and isolating unhydrolysed hydrogen phthalate from partial reaction.OR R = p-MeOC6H4CHPh-At O" with 0.01M-sodium hydroxide the ester recovered after one half-life had 90% of its original optical activity and 95% of the tracer was on the originally labelled oxygen atom. There is therefore no significant migration of the alkyl group (cf. ref. 3). Calculations of bond fission (Table 2) confirm this. The hydrolysis is accelerated by added hydroxide ion (Table l) and this acceleration is accompanied by a change in the position of bond fission and in the steric course of hydrolysis (Tables 2 and 3) i.e.mechanism BAc2 intervenes. Cf. Davies and Kenyon Quart. Rev. 1955 9 203. Hughes Trans. Faraaizy SOC.,1941 37 725. Streitweiser Chem. Rev. 1956 56 571. The activation energy for the hydrolysis in the absence of hydroxide ion (mechanism BAll) is ca. 17 kcal. mole-l and for the bimolecular attack of hydroxide ion (BAc2) is ca. 13 kcal. mole-l. In accord with these values we find that the extents of alkyl-oxygen bond fission and racemisation increase with increasing temperature (Tables 2 and 3). TABLE1. Rates of aqueous hydrolysis [Ester] = 0-01~ [OH-] (M) 0.01 0.09 10% (sec.-l) at 0" 2.95 4.13 25" 42-3 50.7 TABLE2.Position of bond fission at 0" [Ester] = 0-01~ [OH-] (M) 0.01 0.09 1.0 2.ga l.ob Alkyl-ox ygen fission(%) 88 65 14 13c 2c 28 a Slight separation of oily phase. b At 25". c Tracer in ester. TABLE3. Steric course of hydrolysis [Ester] = 0.01~; [OH-] = 1.0~ Temp. 0" 25O Loss of optical activity (%) 14.2 13.3 30.5 The carbonium ions formed by ionisation of the alkyl hydrogen phthalate may be captured by water APRIL1957 forming alcohol (a) or by alkyl hydrogen phthalate ions forming dialkyl phthalate (b). This neutral ester separates and is not hydrolysed further in water. The extent of these processes will depend upon the concentrations of alkyl hydrogen phthalate and hydroxide ion. ROH +H BA?l An increase of hydroxide ion concentration salts out the sodium salt of the hydrogen phthalate as an oil.The stereochemistry of the hydrolysis and the position of bond fission then depend upon the mechanical mixing of the solution. Ef the aqueous and the “oily” phase are well mixed the alcohol product retains its configuration the acyl-oxygen bond is broken and little dialkyl phthalate is formed. If however these phases are not mixed large amounts of dialkyl phthalate are formed (cf. ref. 1). This is because the “oily” phase contains very little hydroxide ion and the aqueous phase contains very little alkyl hydrogen phthalate. Under these condi- tions there is little hydroxide ion attack on the acyl- carbon atom (BA,~),and carbonium ions from the alkyl hydrogen phthalate are largely captured giving dialkyl phthalate by reaction (b).(Received March lst 1957.) Pyridinium Tetrachloro- and Tetrabromo-borates By M. F. LAPPERT (NORTHERN HOLLOWAY N.7) POLYTECHNIC ROAD LONDON THEaddition of the appropriate boron halide (Cl Br) to the corresponding pyridinium halide dissolved in methylene dichloride afforded as a crystalline white solid the 1 :1 complexes PyHX,BX (Py =pyridine) m.p. (sealed tube) 118-121”(Cl) 140-142”(Br) each with decomp. The complexes were reasonably stable (Cl > Br) at room temperature but when they were heated hydrogen halide was eliminated leaving the pyridineboron trihalide addition compounds PyHX,BX -Py,BX + HX these reactions were not reversed when hydrogen halide was passed through a solution of the pyridineboron trihalide complex in benzene.Both complexes were hygroscopic (Br > C1) and with water there was a violent reaction resulting in evolution of hydrogen halide. The complexes were insoluble in benzene carbon disulphide carbon tetrachloride chloroform ether methylene dichlor- ide nitrobenzene and n-pentane. The structure of the complexes can reasonably be interpreted only in terms of a tetrahalogenoborate anion; their formation can be represented as [PyHl+X-+ BX3 +[PyHl+lBX& Although the tetrafluoroborate anion is well known and stable evidence for the existence of the chloride analogue has hitherto been very circum- stantial and for the bromide has been altogether absent.l The presence of the tetrachloroborate anion has sometimes been inferred from the isolation of certain boron trichloride complexes.Tri-n-butyl- sulphonium chloride forms a stable crystalline com- plex with boron trichloride which probably has structure [Bu3S]+[BC14]- ; however as sulphur pos- sesses two lone pairs of electrons an alternative possibility [Bu,S :BCl,]+Cl- exists.2 Complexes of varying stability of boron trichloride with triphenyl- methyl ~hloride,~ phosphorus pentachloride nitrosyl ~hloride,~ and acetyl chloride6 have also been described. Quarternary phosphonium and arsonium tetrachloroborates have been postulated as being formed in the reactions between hydrogen chloride and the borine complexes of phosphorus and arsenic trialkyls.’ The existence of pyridinium tetrachloro- and tetrabromo-borate and not for example of simple alkali-metal salts may be attributed to stabilisation of the complex anions by the large cations.The reactions of quarternary ammonium (e.g. pyridinium) salts in solution in organic solvents with suitable covalent inorganic compounds may prove to be a general method for the preparation of com- plex salts particularly those hydrolysed in water. The author thanks Dr. W. Gerrard for his continued encouragement. (Received February 19th 1957.) Sidgwick “Chemical Elements and their Compounds” Oxford Univ. Press London 1950 Vol. I p. 41 1. Lappert J. 1953 2784. Wibern and Heubaum. 2.an or^. Chem.. 1935.222.98. Martin J. Phys. Chem 1947 51 1400.’ , Geuther J. prakt. Chem. 1873 8 357. Meerwein and Maier-Huser ibid. 1932 51 134; Greenwood and Wade J. 1956 1527. I Hewitt and Holiday J. 1953 530. 122 PROCEEDINGS The Synthesis of Mycolipenic Acid By D. J. MILLIN and N. POLGAR (DYSON OXFORD UNIVERSITY) PERRINS LABORATORY PREVIOUS work1 resulted in the synthesis of (+)-2(L) :4(L)-dimethyldocosanoic acid (I) which was shown to be identical with an oxidation product of mycolipenic acid. This acid has now been con- verted into (+)-2 :4(L) :6(L)-trimethyltetracos-2-enoic acid (111; R = H) by the following procedure. the trans-isomer with physical properties in close agreement with those of methyl mycolipenate. Comparison of the infrared spectra of the corres- ponding acids indicated that they were identical.For the comparison a sample of mycolipenic acid was obtained from a mixture of the dextrorotatory acids (I) L-2 :L-4-M e.[CH,],,CHMeCH,CHMe.CO,H (11) L-2:L-4-Me.[CH2],,CHMe-CH,-CHMeCH,-OH (111) L4:L-6-Me*[CH2],,CHMe*CH,*CHMe.CH:CMe-CO2R Reduction of the acid (I) with lithium aluminium hydride gave (-)-2(L) :4(L)-dimethyldocosan-1-01 (11). Condensation of the corresponding iodide obtained via the toluene-p-sulphonyl ester with the sodio-derivative of ethyl methylmalonate followed by hydrolysis and decarboxylation of the liberated acid afforded 2:4(L) :6(L)-trimethyltetracosanoic acid. Bromination of the latter (Hell-Volhard-Zelin- sky method) followed by reaction of the or-bromo- acid bromide with methanol and dehydrobromina- tion of the resulting bromo-ester by means of pyridine gave (+)-[methyl 2 :4(L):6(L)-trimethyl-tetracos-Zenoate] (111; R = Me) presumed to be of the lipids of tubercle bacilli by fractionation of the methyl esters through a Podbielniak column followed by removal of the straight-chain esters by urea-complex formation and repeated chromato- graphy of the ester fraction b.p.230°/2mm. over alumina. The formulation2 of mycol~pen~c acid as :4:6-trimethy~tetracos-2-enoicacid is thus We thank the Medical Research Council for the award of a scholarship (to D.J.M.). (Received February 27th 1957.) Fray and Polgar J. 1956 2036. a Polgar and Robinson Chem. and Ind. 1951 685; Bailey Polgar and Robinson J.1953 3031 ;Polgar J. 1954 1008. NEWS AND ANNOUNCEMENTS Increased Selling Prices for the Society’s Pubiica-tions.-For the reasons given fully in the article by the Honorary Treasurer in this issue of Proceedings (page 105) it has been necessary to increase the selling price of the Journal and some other publications of the Society. Details of the new prices are as below. The increase in the price of the Journal for Non- Fellows becomes effective from January lst 1959. All other price changes operate from January lst 1958. Since some Fellows are not aware of the purpose of the declaration they are required to sign on the annual subscription form the wording has been con- siderably strengthened and will in future read as follows:“I certify that the publications I require are solely for my own use and I have not ordered them directly or indirectly on behalf of any bookseller library institution or industrial firm.Although I may make any personal use of these copies that may be necessary in the practice of my profession I will NOT transfer ownership or control before January Annual Subscription Journal Annual Reports Quarterly Reviews Current Chemical Papers Ordinary Edition Edition printed on one side of the paper Air Mail Edition (for countries outside Fellows Non-Fellows E s.d. E s. d. 800 2000 15 O* 2 0 0 15 O* 2 0 O* 200 500 3 0 0 610 0 500 800 Europe) *Prices same as 1956 1960. I recognise that if I act in a manner contrary to the spirit of this declaration action may be taken in accordance with the Bye-Laws to termhate my Fellowship.” Journals issued to Fellows will from 1958 carry an indication on the cover that they have been sup-plied at a reduced rate subject to the restrictions stated above.APRIL1957 Award of Longstaff Medal.-Council has unani- mously decided that the next award of the Longstaff Medal shall be made to the President Professor E. L. Hirst. Flintoff Medal.-The Flintoff Medal and Prize which is awarded every three years to the Fellow who has made the most meritorious contribution to the knowledge of the relations between chemistry and botany has been awarded to Professor H. Erdtman (Stockholm). Corday-Morgan Medal and Prize.-The Corday-Morgan Medal and Prize for 1955 has been awarded to Professor G.Porter (Sheffield) in consideration of his contributions to the study of the unstable inter- mediates of chemical change by means of flash pho tolysis. This award consisting of a silver medal and a monetary prize of 200 guineas is made annually to the chemist of either sex and of British Nationality who in the judgment of the Council of The Chemical Society has published during the year in question the most meritorious contribution to experimental chemistry and who has not at the date of publica- tion attained the age of thirty-six years. Copies of the rules governing the award may be obtained from the General Secretary of the Society.Applications or recommendations in respect of the award for the year 1956 must be received not later than December 31st 1957 and applications for the award for 1957 are due before the end of 1958. Hugo Muller Lecture.-The Council has desig- nated the Lecture “Chemical Problems relating to the Origin of the Earth,” given by Professor Harold C. Urey (Honorary Fellow) in the Royal Institution on Thursday 14th March as the Hugo Muller Lecture for the current year. The Lecture will be published in Proceedings later. Lectureships 1957/58.-The following appoint- ments have been announced by the Council Liversidge Lectureship Professor R. G. W. Norrish Tilden Lectureships Professor R. M. Barrer Professor B. Lythgoe Centenary Lectureships :Professor L.Ruzicka (Zurich) Dr. G. Herzberg (Ottawa). Society’s Committees 1957/58.-New members of the Society’s Committees have been appointed as follows Awards Committee. Sir Eric Rideal and Professor M. Stacey in place of Professor R. D. Haworth and Dr. H. W. Melville. Finance and General Purposes Committee. Dr. L. E. Sutton and Dr. J. W. Barrett in place of Dr. F. Hartley and Sir Cyril Hinshelwood. Publication Committee. Dr. N. Campbell Professor N. B. Chapman Professor D. D. Eley Dr. T. G. Halsall Professor D. H. Hey and Dr. J. C. Speak- man in place of Professor D. H. R. Barton Dr. H. M. N. H. Irving Dr. N. Sheppard and Professor M. Stacey. The number of authorised members of this Committee has been increased by two. Research Fund Committee.Dr. W. Gerrard Professor M. Stacey and Dr. L. E. Sutton in place of Professor D. H. Hey Professor J. M. Robertson and Mr. R. M. Winter. Discussion on “Newer Preparative Methods in Organic Chemistry.’’-A meeting has been arranged jointly by The Chemical Society and the Fine Chemicals Group of the Society of Chemical In- dustry. It will be held on Thursday November 7th at University College Gower Street W.C.l in two sessions (2.154.15 p.m. and 5.00-7.00 p.m.). The following are expected to read papers Dr. R. M. Evans (Glaxo Laboratories Ltd.) Dr. H. B. Henbest (King’s College London) Dr. G. W. Kenner (Cambridge) Dr. P. 0. Lenel (Imperial Chemical Industries Limited Billingham) Dr. R. Slack (May and Baker Ltd.) and Dr.M. C. Whiting (Oxford). Full details will be issued in due course. Abstracts will not be available and full publication after the meeting is not contemplated by the Societies. The Symposium will be followed by a dinner which members of both bodies will have an opportunity to attend. Elections to The Royal Society.-Recently elected Fellows of The Royal Society include the following F. S. Dainton Professor of Physical Chemistry in the University of Leeds distinguished for his con- tributions to physical chemistry and particularly his work on reaction kinetics polymerisation processes and radiation chemistry. J. K. N. Jones Professor of Chemistry in Queen’s University Kingston Ontario distinguished for his structural studies of complex macromolecules and his investigations on the biosynthesis of simple sugars.F. t.Rose O.B.E. Director of Research Imperial Chemical Industries (Pharmaceuticals) Limited dis- tinguished for his work in organic chemistry particu- larly for his contribution to the synthesis of drugs such as “Paludrine” and “Antrycide”. E. L. Smith Glaxo Laboratories Limited dis- tinguished for his researches on the chemistry and biochemistry of vitamins especially for the isolation and crystallisation of vitamin Blp Sir (Frank) Ewart Smith Deputy Chairman and Technical Director Imperial Chemical Industries Limited distinguished for the application of a 124 scientific mind and of scientific knowledge and methods to the design development and manage- ment of chemical manufacturing plant and processes.Elections to the Royal Society of Edinburgh.-Dr. G. 0.Aspinall Lecturer in the Department of Chemistry and Local Representative of the Society for Edinburgh and Dr. A. C. G. Menzies Director of Research Hilger & Watts Ltd. have been elected Fellows of The Royal Society of Edinburgh. Isotope Catalogues.-The fourth edition of the catalogue of isotopes on sale by the Atomic Energy Research Establishment Hanvell may be obtained from the Isotope Division A.E.R.E. Harwell Didcot Berks. A separate catalogue covering naturally occurring radioactive materials labelled compounds and other materials requiring processing or synthesis is obtainable from the Radiochemical Centre Amersham Bucks.Deaths.-We regret to announce the deaths of Mr. Andrew Dargie (13.12.56) of Dundee; Mr. A. W. Edwards a Director of E. R. Squibb & Sons; and of Mu. N. S. Wellington of Bath a Fellow of the Society since 1891. Personal.-Professor H. N. Rydon Professor of Chemistry and Director of the Applied Chemistry Laboratories Manchester College of Science and Technology has been appointed to the Chair of Chemistry at the University of Exeter. Dr. W. G. Overend D.Sc. Reader in Organic Chemistry at Birkbeck College has been appointed to the Chair of Chemistry tenable at that College. Dr. J. C.Robb has been appointed Professor of Physical Chemistry at the University of Birmingham. Dr. L. J. Haynes Lecturer in Chemistry in the University of Edinburgh has been appointed to the Chair of Chemistry in the University College of the West Indies.PROCEEDINGS Dr. G. L. Riddell is relinquishing his appointment as Director of the Printing Packaging and Allied Trades Research Association to join Albert E. Reed & Co. Ltd. as head of their Packaging Research and Development Division. Dr. V. G. W. Harrison has been appointed to succeed Dr. Riddell at P.A.T.R.A. Dr. F. N. Woodward has been appointed Director of the Arthur D. Little Research Institute at Inveresk. Dr. Woodward was formerly Director of the Insti- tute of Seaweed Research. He has served as Scientific Attach6 to the British Embassy in Washington and has been Adviser to the United Kingdom High Corn- missioner in Canada.Mr. H. Greville Smith C.B.E. has been appointed President Elect of the Society of Chemical Industry in succession to Mr. Julian M. Leonard who will complete his term of office next July. Dr. R.J. Boscott formerly Lecturer in Endocrine Chemistry at the Medical School University of Birmingham has been appointed Head of Chemical Research at Messrs. Pfizer Ltd. Folkestone Kent. The University of St. Andrew’s is to confer the Honorary Degree of LL.D. on Dr. H. J. Plenderleith Keeper of the Research Laboratory in the British Museum. The University of Aberdeen is to confer the Honorary Degree of LL.D. on Dr. H. W. Melville Secretary of the Department of Scientific and Industrial Research. The President has congratulated the following who have completed 60 years of Fellowship John Stewart Remington (Harpenden) Thomas Tickle (Exeter) Andrew Turnbull (Hordle) Election of New Fellows.-1 14 Candidates whose names were published in Proceedings for February were elected to the Fellowship on March 14th 1957.FORTHCOMING SCIENTIFIC MEETINGS London Thursday May 9th 1957 at 7.30 p.m. Centenary Lecture “Structural Evidence regarding the Solid Addition Compounds of Ethers and Amines with Halogens and Other Molecules acting as Elec- tron-acceptors,” by Professor 0. Hassel. To be given in the Rooms of the Society Burlington House W. 1. Thursday June 6th 1957 at 7.30 p.m. Meeting for the Reading of Original Papers. “The Vapour Pressure of Anhydrous Copper Nitrate and its Molecular Weight in the Vapour State,” by C.C. Addison and B. J. Hathaway. “Aromatic Reactivity. Part 11. The Cleavage of Aryltrimethylsilanes by Bromine in Acetic Acid,” by C. Eaborn and D. E. Webster. “The Kinetics of the Oxidation of Ethane by Nitrous Oxide,” by R. Kenwright A. B. Trenwith and P. L. Robinson. To be held in the Rooms of the Society Burlington House W. 1. Birmingham Friday May loth 1957 at 4.30 p.m. Centenary Lecture “Structural Evidence regarding the SolidAddition Compounds of Ethers and Amines with Halogens and Other Molecules acting as Elec- tron-acceptors,” by Professor 0. Hassel. Joint APRIL1957 Meeting with Birmingham University Chemical Society. To be held in the Chemistry Department The University.Bristol Wednesday May Sth 1957 at 5.30 p.m. Bourke Lecture of the Faraday Society “Electro- kinetic Researches,” by Professor A. J. Rutgers. To be given in the Chemistry Department The Univer- sity. (All Fellows are invited.) Cambridge Monday May 6th 1957 at 8.30 p.m. Lecture “Enzymic Syntheses of Higher Sacchar- ides,” by Professor E. J. Bourne Ph.D. F.R.I.C. To be given in the University Chemical Laboratory Lensfield Road. Exeter Friday May 17th 1957 at 5 p.m. Lecture “Reduction by Metal-Ammonia Solu-tions,” by Professor A. J. Birch D.Sc. D.Phi1. To be given in the Washington Singer Laboratories Prince of Wales Road. Glasgow Tuesday May 14th 1957 at 4 p.m. Centenary Lecture “Structural Evidence regarding the Solid Addition Compounds of Ethers and Amines with Halogens and Other Molecules acting as Elec-tron-acceptors,” by Professor 0.Hassel. To be given in the Chemistry Department The University. Irish Republic Friday May loth 1957 at 7.45 p.m. Lecture “Organic Semiconductors,” by Professor D. D. Eley M.Sc. Ph.D. Joint Meeting with the Werner Society. To be held in the University Chemical Laboratory Trinity College Dublin. Newcastle and Durham Tuesday May 13th 1957 at 5.15 p.m. Lecture “Chemical Evolution,” by Professor J. D. Bernal M.A. F.R.S. Joint Meeting with the Durham Colleges Chemical Society. To be held in Lecture Room 239 University Science Laboratories South Road Durham. Oxford Monday May 20th 1957 at 8.15 p.m. Lecture “The Escape of Planetary Atmospheres,” by Professor H.C. Urey Ph.D. D.Sc. Joint Meeting with Oxford University Alembic Club. To be held in the Inorganic Chemistry Laboratory. Monday May 27th 1957 at 8.15 p.m. Lecture “Many-centre Bonds,” by Professor H. C. Longuet-Higgins M.A. D.Phi1. Joint Meeting with Oxford University Alembic Club. To be held in the Inorganic Chemistry Laboratory. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Ahmad Nisar M.Sc.Chemistry Department The University Manchester 13. Albertson Clarence Elmo jun. A.B. M.S. 240 South Monterey Avenue Villa Park Illinois U.S.A. Alder Roger William. Kirkham Farm Lower Slaughter nr. Cheltenhain Glos. Allan Angus Wilkinson B.Sc. c/o Mrs. Hunter 49 West Princes Street Glasgow. Anderson John Donald B.Sc. 11 Byron Place Clifton Bristol 8. Anson Peter Colin B.Sc. 65 Kingsmead Drive Hunts Cross Woolton Liverpool. Ashworth Keith B.Sc. Greystones New Street, Stevenston Ayrshire. Atherton Frank Ratcliffe M.Sc. Pi1.D. 148 Parkway, Welwyn Garden City Herts. Atkins Gordon Leslie. 10 Nelson Crescent Ramsgate Kent. Ayrey Geoffrey B.Sc. 30 Aldykes Hatfield Herts. Baba Shigeo. c/o Mr. Bunichiro Nishiwaki No. 914 2 chome Egoda Nakanoku Tokyo Japan.Bailey David John William Herbert B.Pharm. 144 Col-ney Hatch Lane Muswell Hill London N.lO. Baisted Derek John. 143 Northcote Avenue Southall Middlesex. Baker Archibald James. Station Road Inverkip Renfrewshire. Banerji Jogesh Chandra M.Sc. Ph.D. Chemistry Department B.N. College Patna 4 India. Barnard Eric Albert B.Sc. 17~ Acol Road London N.W.6. Baron Maximo D.Chem. 42 Vick Park A Rochester 7, N.Y. U.S.A. Barson Charles Anthony B.Sc. 18 Kingscote Road Edgbaston Birmingham 15. Bascombe Kenneth Norman B.A. 3 Weston’s Lane Poole Dorset. Beale John Hampden B.Sc.Tech. 1900 Perrine Street Lafayette Indiana U.S.A. Bezzant Ronald John B.Sc. A.R.I.C. 19 Madden Avenue Chatham Kent. Blake Walter Jardine Ph.D.F.P.S. c/o Pharmacy Department Heriot-Watt College 79 Grassmarket, Edinburgh. Bockman Oluf Christian. Department of Chemistry The University Glasgow W.2. Bradley John Ernest Stobart B.Sc. Ph.D. 122 Grosvenor Road Muswell Hill London N.lO. Bramley Richard. 11 Canonbury Grove Bexley North Sydney Australia. Briggs Michael Harvey B.Sc. 9 Meadway Chadderton Lancs. Bronnert David Llewellyn Edward. Maitland Ashley Road Hale Altrincham Cheshire. Bruice Thomas C. Ph.D. Department of Biochemistry Yale University New Haven Connecticut U.S.A. Bruton Michael John. 66 Raymend Road Bristol 3. Burdm James B.Sc. Ph.D. 108 Greenfield Road Har- bourne Birmingham 17. Burwell Robert L. jun. B.S. Ph.D. Department of Chemistry Northwestern University Evanston 11-linois U.S.A.Carleton John Richard. 158 Westbourne Park Road London W. 1 1. Carter Terence. 26 Blackwood Hall Luddendenfoot Halifax Yorks. Chamberlain Derek Guy B.Sc. 32 Birchwood Avenue Muswell Hill London N.lO. Chambers Richard Henry. 201 Shooters Hill Road Blackheath S.E.3. Chang Edward M.A. 314 Burroughs Drive Snyder 21 N.Y. U.S.A. Chang Mildred B.A. c/o Chemistry Department Uni- versity of Rochester Rochester 3 N.Y. U.S.A. Chapman John Frederick BSc. Ph.D. Boundary Hall Tadley nr. Basingstoke Hants. Chilton Oswald John B.Sc. 50 Vera Road Fulham London S.W.6. Clemens David Henry A.B. 2146 Center Avenue, Madison Wisconsin U.S.A. Coddington Alan B.Sc. A.R.C.S. 26 Norland Square Holland Park London W.1 1. Coleman. William E.. B.S. 2703 Stuart Street Berkeley 5 California U.S.A. ' Collins. Carol Hollingworth B.S. Chemistry Depart- -ment Iowa State Coilege Ames Iowa u.s.A. Craven Paul M. M.S. D.Phi1. 445 Lakewood Road Walnut Creek California U.S.A. Cuthbertson Forster BSc. 35 St. Andrew's Crescent Blackhill Consett Co.Durham. Daniels Malcolm B.Sc. Ph.D. 22 Roseworth Avenue Gosforth Newcastle on Tyne 3. Darley John Richard B.Sc. 54 Maidstone Road Chatham Kent. Dasgupta Sunil Kumar M.Sc. D.Phil. Antibiotics Research Centre Hindustan Antibiotics (Private) Ltd. Pimpri nr. Poona India. Davies Henry John B.Sc. A.R.I.C. 6 Hortensia House Chelsea London S.W.10. Davies Vincent B.Sc. 21 Windmill Street Saltcoats Ayrshire.De Boer Th.J. Ph.D. Singel 421 Amsterdam Holland. Dittmer Donald Charles B.S. Ph.D. Chemistry Depart- ment University of Pencsylvania Philadelphia 4 Pennsylvania U.S.A. Dolton Eric Charles A.R.I.C. 232 Oxford Road Calne Wilts. Durant Graham John B.Sc. 204 Selly Park Road Selly Oak Birmingham 29. Dvorak Dusan. 12 V Olsinach Praha 10 Czechoslovakia. Ezaki Heihachi B.Sc. c/o Marumiya 104 8-chome Terajimacho Sumida-ku Tokyo Japan. Farago Peter Joseph B.Sc. 84~ Carlton Hill London N.W.8. Ferrier. Barbara May. B.Sc. 11 Craiahouse Road ~ Edinburgh 10. Flegenheimer Juan Gerson D.Chem. Radiochemical Laboratories Chemical Department Lensfield Road Cambridge. Folsch Georg. Vaderkvarnsgatan 3c Gothenburg, Sweden. PROCEEDINGS Ford-Smith Michael Harry B.A.Balliol College Oxford. Francis Peter Ernest B.Sc. 99 Magdalen Road Wands- worth Common London S.W. I 8. Galbraith Andrew Rennie BSc. 2 Batty Avenue Stirling. Gardner John N. B.A. University College Oxford. Gujral Pindi Dass M.Sc. Journal of Scientific & In-dustrial Research C.S.I.R. Building Old Mill Road, New Delhi 2 India. Guyer Walter Richard B.S. Ph.D. c/o Esso Research Limited 33 Davies Street London W.l. Haddad Yousif Micheal Yousif. 4 St. James Garden Swansea Glam. Hammond Peter Ross B.A. Corpus Christi College Cambridge. Hardy Michael Grange. Brentwood Cecil Avenue, Baildon Shipley Yorks. Hart Peter Brian B.Sc. 150 Strathmore Avenue Luton Beds. Hatton John Victor. 96 Blewbury Drive City Road Tilehurst Reading Berks.Hayes Frank B.Sc. 141 Westbury Road Westbury-on- Trym Bristol. Haynes Howard Frederic M.Sc. 10 Hamilton Avenue Blackburn Victoria Australia. Head Peter Ernest. 4~ Watkin Road Boscombe Bournemouth Han ts. Hedgley Edward John B.Sc. Ph.D. A.R.I.C. 77 Sheaveshill Avenue Colindale. London. N.W.9. Henney Graham B.Sc. 13 Chalfont Way West Ealing London W. 13. Higham Peter. 63 Kenilworth Road Bognor Regis Sussex. Hirata Yoshimasa D.Sc. Chemical Institute of Nagoya University Chikusa Nagoya Japan. Holden Harold William B.A. Ph.D. 56~ Norman Road Northfield Birmingham 3 1. Holstead Colin B.Sc. Ph.D. 133 The Ridgeway North Harrow Middlesex. Horne Michael Graham B.A. 57 Oxford Street Finedon Northants.Howard Jessie Robertson B.Sc. 63 Lamberton Drive Glasgow S.W.2. Hunt Brian Bagshaw B.A. The Cottage 53 Grange Road Cambridge. Hunter William Hubert B.Sc. Ph.D. A.R.I.C. The Crest Hole Lane Abinger Hammer Surrey. Jacobs Patrick William McCarthy MSc. Ph.D. D.I.C. Thornhill Carlton Road Redhill Surrey. Jarvie Ann Winifred Purdon B.Sc. 104 North Hanover Street Glasgow C. 1. Jelinek Jiri Dr.Tech. Vyskumny ustav acetylenovej chemie Novaky Czechoslovakia. Jones Brian Cedric B.A. 197 Lichfield Road Shire Oak Walsall Wood Walsall Staffordshire. Jubb Anthony William 568 Grange Road Gillingham Kent. Kane Vinayak Vasudeo M.Sc. Chemistry Department The University Glasgow W.2. Kaneko Takeo DSc. Faculty of Science Osaka Univer- sity .I-chome Nakanoshima Kita-ku Osaka Japan.Kappeler Heini Dr.Sc. nat. Ciba Ltd. Basle Switzer- land. Kenwright Ronald B.Sc. 32 Ashwood Crescent, Walkerville Newcastle on Tyr,e 6. Kirkpatrick John Samuel. 3 Oxford Terrace Bowbum Co. Durham. Knapman Reginald George B.Sc. A.R.I.C. Manor Farm Freefolk Whitchurch Hants. Knowles Kenneth B.Sc. 21 Moss Road Birkdale South- port Lancs. APRIL1957 Kucera Josef. Chemicke zavody W. Piecka Novaky Czechoslovakia. Lamb Arnold. 15 Osborne Terrace Sale Cheshire. Laurence Gerald Steven M.Sc. School of Chemistry The University Leeds 2 Yorks. Lawrence Frederick Brian B.Sc. Providence Place, Calstock Cornwall. Lee Donald Faraday B.Sc. Flat ll~, Central Parade Barnet By-pass Hatfield Herts.Lee. William. B.Sc. Flat 2. 85 Trafalgar Road Moseley I -_ Birmingham 13. Lefebvre. Roland. Ph.D. Centre de Chimie Theoriaue -~ 155 Rue de Sevres Paris XVe France. Lewis George Edwin A.B. M.S. Chemistry Department Florida State University Tallahassee Florida U.S.A. McCapra Frank B.Q. 65 Ardmory Avenue Glasgow s.2. Madeley John David B.Sc. A.R.I.C. 471 Moorside Road Flixton Urmston Manchester. Manzoor-i-Khuda Abu Raihan Mahiuddin Muhammad M.Sc. 7 Trebovir Road London S.W.5. Marson Ralph B.A. 10 Oldham Avenue Wyken Coventry. Martin Lyster Waverley Ormsby B.Sc. c/o Commercial Banking Corporation of Sydney 49/50 Berkeley Street London W.l. Meakin. Brian John. B.Pharm. 71 Kedleston Road Leiceiter. Meakin Denys. Gower Hey Bank Osborne Road Hyde Cheshire.Michaelides. Phoebus. B.Sc. 4 Elain Mansions Elnin -.-Avenue London W.9. Mijovic Miroslav Vasa Dr.tech.Sc. Kodak Research Laboratories Harrow-Wealdstone Middlesex. Millin David John B.A. 9 Lathbury Road Oxford. Misrock S. Leslie S.B. Pennie Edmonds Morton Barrows & Taylor Counsellors at Law 247 Park Avenue New York N.Y. U.S.A. Mohring Helmut Dr.Phi1. Farbenfabriken Bayer, Leverkusen Germany. ,Montgomery Harry Arthur Charles B.Sc. 291 Birming- ham New Road Lanesfield Wolverhampton. Mumford Pamela May. Tobacco Manufacturers’ Stand- ing Committee 6/10 Bruton Street London W.l. Murad Edmond B.A. c/o Department of Chemistry University of Rochester Rochester 20 N.Y. U.S.A. Nakao Akira M.Sc. c/o Kawaguchi Kagaku Kogyo K.K.5 l-chome Kanda Tamachi Chiyodaku Tokyo Japan. Nakatsuchi Akira Dr.Eng. c/o Nitto Rikagaku Kenkyujo 163 Kami-Kizaki Ohhara Urawa Saita- maken Japan. Narayanan Chengalur Raman M.Sc. Ph.D. Chemistry Department The University Glasgow. Neal Graham Henry. Hammer Hill Romsley nr. Bridgnorth Salop. Nelson Norman Allan B.Sc. Ph.D. Department of Chemistry Massachusetts Institute of Technology, Cambridge 39 Massachusetts U.S.A. Oda Kenichi M.Sc. c/o Noguchi Institute 6-3569 Itabschicho Itabashi Tokyo Japan. Ogle John Richard B.Sc. 52 Main Street Wentworth Rotherham Yorks. Ohashi Kumao D.Sc. c/o Toa Synthetic Chemical In- dustry Nagoya Factory 23-1 7 Showa-Machi Mina- toku Nagoya Japan. Orito Isamu Dr.Tech.c/o Shinetsu Kagaku Kogyo Chuo-Kenkyujo 3chome Ohtaku Iriarai Tokyo Japan. Orochena Salvador F. Ph.D. 404 Charles Street, Pittsburgh 10 Pennsylvania U.S.A. Osgerby John Martin BSc. 18 Coulsdon Road Lincoln. Ovenall Derick William Ph.D. Chemistry Department University of Birmingham Edgbaston Birmingham 15. Owen Gerald Digby Torrington. 13 Llanthewy Road Newport Mon. Parsons John Anthony. 3 1 Ashcombe Road Carshalton Surrey. Pears Gordon Edmund Alfred B.Q. 83 Ashton Drive Bristol 3. Peden Alan A.R.I.C. 101 Horton Road Rusholme Manchester 14. Peover Michael Edward B.Sc. 22 Ellerker Gardens Richmond Surrey. Pettit George Robert M.S. Ph.D. R.D.3 East River Road Oxford New York U.S.A. Pickering William Frederick Joseph M.Sc. 4 Ravenshaw Street Merewether 2N New South Wales Australia.Player Philip John. 22 Cowslip Hill Letchworth Herts. Price Stanley James Whitworth B.A. M.Sc. Chemistry Department King’s Buildings Edinburgh 9 Scotland. Pugsley Leonard Irving B.A. M.Sc. Ph.D. Food & Drug Directorate Department of National Health & Welfare Ottawa Canada. Pulsford Derek William. 3 Worcester Gardens Sutton Surrey. Puri Balwant Rai M.Sc. Ph.D. Punjab University Hoshiarpur India. Ranson Derek B.Sc. The Manor House Northfield Birmingham 3 1. Redfearn Auberon B.A. 15 Birstwith Road Harrogate Yorks. Remers William Alan S.B. 606 W. Ohio Street Urbana Illinois U.S.A. Rickards Rodney Warren BSc. No. 6 Flat 14 Osborn Road Manly New South Wales Australia. Robinson Alan Ellwood.22 Lytham Road West Point Manchester 19. Rochow Eugene George B.Chem. Ph.D. Department of Chemistry Harvard University Cambridge 38, Massachusetts U.S.A. Rudoff Stanley M.A. Ph.D. 814 Montgomery Street Brooklyn 13 N.Y. U.S.A. Sakai Heiichi B.Agric. c/o Iyakushigen Kenkyujo 952 Nukui Koganei-machi Kitatamagun Tokyo Japan. Scott Neville Durrant B.Sc. 16 Victoria Road Acocks Green Birmingham 27. Searle Harold Trevor B.A. 42 Somerset Road Hands- worth Wood Birmingham 20. Selby Brian Glyn. 27 Milton Road Newport Mon. Sheldon Robert. 6 Sellwood Road Northcourt Abing- don Berks. Sherlock Edward M.Sc. A.R.C.S. 66 Sturges Road Wokingham Berks. Siegfried Frank Dr.Phi1. 50 Ardrossan Road Saltcoats Ayrshire. Smith Brian Vellender B.Sc.Sunnymead High Road Mountnessing Brentwood Essex. Smith Dorian S. M.S. 1001 W. California Urbana Illinois U.S.A. Sneddon Walter B.Sc. 7 Miller Road Balloch Dum- bartonshire. Sofaer Ramah Jessica. 117 Woodcote Grove Road Coulsdon Surrey. Stacey Martyn Hugh. 80 Thorne Road Doncaster Yorks. Stedman Martin. 38 Convent Hill London S.E.19. Steel Colin B.Sc. 43 Braehead Road Barnton Edin- burgh. Steinberg David H. B.A. M.S. 2500 Webb Avenue Bronx 68 New York U.S.A. Stern Barrie Tod B.Sc. 3 Amos Grove Court New Southgate London N. 1 1. Sutherland Alan John. 16 Quarry Road London S.W.18. Tamura Kihachi B.Sc. c/o Shinetsu Kagaku Kogyo K.K. Isobe Kojo 1105 Nishi-Kamiisobe Annaka- machi Gummaken Japan.Taylor Charles W. B.A. 1515 Monroe Street Madison 5 Wisconsin U .S.A. Taylor William Gordon Keith B.Sc. 23 Summerfields Avenue Blackheath Birmingham. Tessier Keith Campbell B.Sc. Welle Cottage Church Lane Pinner Middlesex. Theaker Gordon B.Sc. A.R.I.C. 4 Marsh Gardens Honley nr. Huddersfield Yorks. Thorne Ronald Albert. NC.7 Radclive nr. Buckingham Bucks. Tomiie Yujiro B.Sc. 79 Richmond Avenue Leeds 6. Torossian Robert. 12 Rue Saint-Florentin Paris 1, France. Tsuchihashi Genichi M.Sc. 30 Nijukkicho Shinjuku-ku Tokyo Japan. Turner David John. 30 Woodway Crescent Harrow Middlesex. Ushiba Daizo Dr.Med.Sc. Keio Gijubku University School of Medicine Shinano-Machi Shinjuku-ku, Tokyo Japan. Wahid Mukhtar Ahmad M.Sc. Survey of Medicinal Plants Pakistan Council of Scientific & Industrial Research P.O.Peshawar University West Pakistan. ADDITIONS TO I1 prisma collana di divulgazione scientifica No. 8. La chimica nella vita sociale. M. Giua. Pp. 271. Casa Editrice Dr. Francesco Vallardi. Milan. 1956. (Presented by the Publishers.) Structure reports for 1940-1941. Vol. 8. Edited by A. J. C. Wilson. Prepared under the guidance of a Com- mission of the International Union of Crystallography. Pp. 384. N.V.A. Oosthoek’s Uitgevers Mij. Utrecht. 1956. Accurate determination of parameters of elementary unit cells of crystals asymmetrical methods. A. F. Ievins and I. K. Ozol. Pp. 130. Latvian Academy of Sciences. Riga. 1956. (Presented by the Latvian Academy of l Sciences.) High-temperature technology.Edited by I. E. Camp- bell. 35 Contributors. Sponsored by the Electrochemical Society Inc. New York. Pp. 526. John Wiley & Sons Inc. New York. 1956. The art of organic chemistry. (Sir Jesse Boot Founda- tion Lecture 1956-57.) A. W. Johnson. Pp. 20. Univer-sity of Nottingham. 1957. (Presented by the University.) Die atherischen ole. E. Gildemeister and F. Hoffmann. 4th edn. by W. Treibs with 6 collaborators. Vol. I. Pp. 500. Akademie-Verlag. Berlin. 1956. Chemie und Anwendungen des lY4-Dioxans. W. Stumpf. Pp. 68. Verlag Chemie. Weinheim. 1956. The chemistry of vegetable tannins a symposium held at Cambridge 1956 under the auspices of the Society of Leather Trades’ Chemists. Pp. 160. Society of Leather Trades’ Chemists.Croydon. 1956. (Presented by the Publishers.) Elementary practical organic chemistry. Part I. Small scale preparations. A. I. Vogel. Pp. 347. Longmans Green & Co. London. 1957. (Presented by the Author.) Walker William Norman B.Sc. 70 High Street Lincoln. Wallace William John B.A. Ph.D. Department of Chemistry University of Alberta Edmonton Alberta Canada. Ward Laird Gordon Lindsay M.Sc. 27 Rimu Road Kelburn Wellington W. 1 New Zealand. Watkins Thomas Frederick M.Sc. F.R.I.C. C.D.E.E. Porton nr. Salisbury Wilts. Watson Barbara Elizabeth B.Sc. Ph.D. Ethel Williams Hall Eastfield Road Benton Newcastle 12. Watson David Gilfillan B.Sc. Macbrayne Hall Park Circus Place Glasgow C.3. Watts Thomas Henry Edmund B.Sc.A.R.I.C. 11 Hillview Road Chislehurst Kent. Wiemann Joseph D.es Sc. 12 bis Rue de Val de Grace Paris 5 France. Wilen Samuel H. B.S. Ph.D. 803 West Washington Avenue South Bend Indiana U.S.A. Wilkinson Colin Edward. 5 Morden Gardens Mitcham Surrey. Willcockson George William B.S. 1828 7th Avenue Arcadia California U.S.A. Young Edwin Harry Paterson M.Sc. Ph.D. Gwynfr Chester Road Woodford Bramhall Cheshire. Zahradnik Rudolf. Farskeho 7/1 .p. Praha VII Czecho- slovakia. THE LIBRARY Beilstein’s Handbuch der organischen Chemie. Edited by F. Richter. 4th edn. 2nd Suppl. Vol. 29. Part 3. General-Formelregister fur das Hauptwerk und die Erganzungswerke I und 11. CI8-C3,,*. Springer-Verlag. Berlin. 1957. (Presented by the Editor.) Gmelin’s Handbuch der anorganischen Chemie.8th edn. Calcium. Part A. Section 2. System No. 28. Pp. 488. Platin. Part D. System No. 68. Pp. 638. Verlag Chemie. Weinheim. 1957. Die chemische Analyse. Vol. 33. Neuere massanalyt- ische Methoden. G. Jander with 12 collaborators. Pp. 455. Ferdinand Enke Verlag. Stuttgart. 1956. Die Cerimetrie und die Anwendung dei Ferroine als massanalytische Redoxindikatoren. Compiled by Walter Petzold. Edited by E. Merck Darmstadt. Pp. 340. Verlag Chemie. Weinheim. 1955. The organisation and rationalisation of soil analysis (O.E.E.C. Project No. 156.) Pp. 217. Organisation for European Economic Co-operation. Paris. 1956. (Pre- sented by the Publishers.) Recommended method for the determination of naphthalene in coke oven gas.Fifth report of Panel No. 1. Pp. 11. British Coke Research Association. London. 1956. (Presented by the Publishers.) Standard methods for testing petroleum and its products (excluding engine test methods for rating fuels). 16th edn. Pp. 772. Institute of Petroleum London. 1957. Trait6 de chimie physique. Vol. 3. Part 5. Centrifuges et ultracentrifuges. J. Duclaux. Pp. 126. Hermann & Cie. Paris. 1955. (Presented by the Publishers.) Instrument technology. Vol. IT. Analysis instruments. E. B. Jones. Pp. 208. Butterworths Scientific Publications. London. 1956.