SEW BOOKS The Industrial Development of Searles Lake Brines. By J o h n E. Teeple. 25 X 16 cm; p p . 182. Kew York: Chemical Catalog C o m p a n y , 1939. Price: $3.00. I n the preface the author says: “My associates really include all the men who actually contributed to the manufacture or marketing of the products, or to research, or to design and construction of the plant. Many of their names will be found on the pages in connection with specific parts of the work. But it was a n organized piece of cooperation in which it would be difficult and probably useless to evaluate just what each one of us contributed, beyond saying that we saw it all and were a part of it.” “This book has two purposes. First, to add to the record of scientific literature certain phase rule diagrams and data. This information was necessary to the work of Trona; it belongs to the American Potash and Chemical Corporation, was done a t their initiative and was paid for with their money. I t has now largely served its original purpose, and normally would have spent the rest of its existence buried in their files. The American Potash and Chemical Corporation in consenting to the publication of these data has performed a courteous act. One could wish that other chemical corporations would likewise release data from their files when it can be done without furnishing ammunition to direct competitors. Scientific information is about the only valuable commodity we are accustomed to bury for fear someone else might derive benefit from it. “The second purpose of the book is t o give a short story of the application of research, technology and common sense to the development of a potash and borax business. This story of the diagnosis of a situation in an industry and the course of development which led to succea8 is not such a n uncommon thing; in fact it is all in the day’s work, so why write a book about it? The answer lies in the very peculiar attitude t h a t was manifested toward the development of a potash industry in this country. During the World War potash was news. Anyone could be sure of making the front page by talking about potash and how this country was becoming independent of Germany. With peace came a change. College professors, bankers, business men, chemists and ministers of the Gospel now granted interviews freely to prove that this country could not hope to produce potash successfully in times of peace. Many of the interviews, possibly inspired, were circulated by a well-known advertising agency. T h e opposition to American potash was apparently deep seated, based on faith and belief rather than on facts or logic. Few things are more aggravating and often harmful than loud and dogmatic assertions that a given thing cannot be done, coming from people who obviously are in no position to judge whether it can be or not. I think we all react to this in much the same way; we look back of the loud speakers t o see who is broadcasting; that tells us who is most afraid t h a t the thing can be done; then we proceed to do it. The plant a t Trona undertook to manufacture two staple products, potash and borax, in competition with two world monopolies. Today it has by far the largest borax plant in the world, and one of the largest potash plants. This was accomplished without governmental assistance from tariff or otherwise, and the business is profitable and still young. Since the record t h a t it could not be done was so voluminous it seems well to make note of the fact that it has been done. “This book does not contain detailed descriptions or processes, nor scale drawings or apparatus. The former are not so antiquated nor the latter sufficiently obsolete to permit their publication yet. Anyone intelligent enough to use that kind of information will know better than t o expect it here,” p. 7 The crystallized salts in Searles Lake consist of halite ( S a c ] ) , trona (Na2CO3.K;aHC03. zH,O), hanksite (9Na2SO,.zNa2CO3.KC1),borax (SazB407.101120)and glaserite (3KzSO4. Na,SO,). On the equilibrium diagrams there occur in addition: burkeite (2Ka2S0,.Ka~COd and the unnamed salts Na2CO3.K2CO3,K 2 C 0 3 . z K H C 0 3 . 3 H ~ 0Na2BZ0,.zNaCl.qHz0, , N a z B z 0 r . z N a 3 P 0 4 . ~ 6 H zand 0, N ~ Z B Z O ~ . Z K ~ ~ A S O ~ . ~ ~ H Z O .
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‘,To consider some of the evaporation problems for a moment, probably the most serious one was foaming. We are all familiar with this phenomenon in commercial evaporation and there are several well-known methods for handling such liquors, but I have never seen such pernicious, persistent and aggravating foam in a regular operation. At times the condenser water was actually richer in potash than the raw brine fed to the pans. Unless this eould be controlled either the losses of potash from partly evaporated liquor would be enormous, or the pans must be operated at such slow rate that production would be negligible. “In my first report I find the following comment: ‘At present in the plant they are adding a small amount of oil t o the pans to cut down the foaming. This, too, is a tradition. I did not find out who started it, on what theory it was based. or what work had been done t,o indicate whether it was beneficial or not.’ The use of oil on foamy liquids is very common and often effective, but why in this case use only a n amount which was entirely inadequate? Why not add a proper amount to control the foam, rather than simply tease it? I asked the people in authority a t the plant and the oldest operators. No one knew, or rather everyone knew but their explanations did not agree or did not sound reasonable. A majority felt sure, from tradition, that it would not do to add more oil, and they were right, as traditions often are. One may have great respect for traditional conclusions but they are not entirely satisfying, so at a later date when we had small laboratory pans for studying the problem a trial of the oil showed that there w&s no foaming so long as a thin film remained on the surface. This film tended to disappear but a further addition of oil sufficient to keep a film always present kept the foam under complete control, evaporation proceeded at full speed and there was no obvious disadvantage; score--experiment I , tradition 0. The experimental result was exactly what one would expect, so we next started a full-size singleeffect evaporator in the plant with instructions to run it at top speed and make sufficient additions of the oil to keep a slight film always present on the surface and control foaming. This was done, and for several hours that pan had no trouble with foam, and produced high-grade concentrated liquor at a rate never before seen by the awed beholders. The operation was a complete success-in the evaporation house-but the patient died in the crystallizing house. After about twenty-four hours spent in excavating filters, centrifugals, and other equipment which seemed buried under layers of concrete, the plant resumed operations, and we knew why you should never add enough of that oil to stop foaming. “I have mentioned that burkeite forms sparkling crystals of very high luster. The film of oil acts as a flotation agent and selects the burkeite crystals for attachment, then floats them over with the concentrated liquor t o the crystallizing house where the mixture of crystal and oil acts like concrete. Tradition was finally right, without the faintest idea why. “In studying the question of foaming it seemed reasonable to suspect organic matter in the brine as the cause. Synthetic brine containing all known constituents excepting organic matter could be evaporated without difficulty. Satural brine after treatment with absorbent carbon like Darco no longer foamed. I n searching the watershed for organic matter which might be responsible, I selected greasewood as the probable source. The leaves of this very common plant appear as if coated with a varnish, easily soluble in very dilute alkalies, and a very small addition of this solution to a synthetic brine produces an excellent imitation of foamy natural brine. Probably a number of different organic materials are responsible, and more recent work a t the plant by W. A. Gale indicates that the organic matter may be sodium salts of humic acid, and that its function is probably foam stabilization rather than foam formation, because its removal has little effect on surface tension. “We found many substances which would prevent foam, such as cholesterin, capric acid, pine oil, turpentine, rosin, turkey red oil, and amyl alcohol, most of these being impracticable for use under vacuum evaporation. Finally R. W. Mumford worked out a practical one. The way to control this foam is to add soap or a fatty acid. This ended foaming as a serious trouble and made it certain that we should use steam evaporation and and not be compelled t o resort to solar evaporation or some other makeshift,” p. 36. “Aside from the fixed charges incurred in obtaining ownership and in developing the 2500 acres of salt body in the lake, the only cost of raw material for the plant is the cost
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of pumping. Any basis for depletion charge which might become effective within a generation is very difficult to figure. Amortization of cost of the property should be accomplished well within the life of the plant, but in fact this amortization becomes a daily and not a per gallon charge, and we are left in the very peculiar situation ot being able to disregard the amount of raw material used. Whether we obtain a zo per cent or a 100 per cent recovery of the potash and borax in the brine used means little to us, a few cents per ton a t most, so long as the losses are confined to raw brine on which no real work has been done. I n evaluating mother liquors to see whether they should be discarded we can select a datum level of about 5 per cent KCI and 3 per cent borax. Anything below that level would naturally be discarded at once as worse than valueless. Anything richer than that has a value only equivalent to its excess content above the datum level minus any detriment or disadvantage from impurities that may be incurred by its use. This value also may easily he negative and the liquor should be discarded. I stress this point because chemists are so often urged to conserveresources and save everything, as though IOO per cent yields and no waste products were a sort of religious slogan that would pave the way to heaven. I can’t quite agree with that point of view at all. A chemical plant is not a place for collecting and keeping family heirlooms on account of the sacred memories attached to them; it is a place for making things, and the best way to make things is by judicious waste of the unimportant so that you have room and time to devote entirely to the thing you are making. If there are those whose consciences might he hurt by such waste they may he reassured in this case, for all discarded materials are thrown directly back into the lake, just like little fishes, and so saved for posterity,” p. 46. “Probably I do not make the same distinction between chemical engineers and chemists that is commonly made. From both one demands a certain knowledge of chemistry and a certain ability in the technic of handling materials. The distinction lies largely in the amount of material they need to have in hand in order to he at their very best level of thought. Both are engaged in the chemical transformation of matter, but a good chemical engineer thinks best and works best when he is dealing with tons. He can visualize and arrange his equipment better, his manipulations go more smoothly, his whole manner of thought is freer and clearer if he pictures a regular succession of tons of material flowing through an operation. A man well-adapted to development work, however, probably thinks best in pounds or hundreds of pounds. A chemist thinks best and works best in grams. You can convert a chemist into a chemical engineer by once getting him thoroughly interested in the idea of tonnages. If his mind is at all adapted to that quantity of matter his interest will be awakened and he will learn the technic of handling tons without a great deal of difficulty. On the other hand, it is not difficult to convert a chemical engineer into a chemist by interesting him in the quickness and accuracy with which he may obtain information from working only with grams instead of tons. If his mind is a t all adapted to that quantity he will master the technic of handling g a m s . T o my mind it is largely a question of the quantity of material the individual mind likes to consider a t one time. To carry the comparison a little farther, I suppose we should say that a physical chemist is one who works best and thinks best with molecules rather than with grams or tons, probably not t o exceed ten or a dozen molecules a t one time, and the modern physicist is a t his very best inside the spacious confines of a single atom,” p. 51. “This is about all of the story to he told a t present. The corporation is producing and marketing to-day between 20 per cent and 25 per cent of all the potash in America, but its output would make no real imprekon on the amount that America ought to use. It is making and marketing nearly half the borax and a considerable per cent of the boric acid that the whole world mea, but borax has extremely valuable properties, and if i t is kept where it belongs, in the class of cheap chemicals, the world will use to advantage several times its present consumption. There is plenty of room for expansion and it seems probable that most of the borax of the near future will come from sources like Searles Lake, rather than from colemanite and other borax minerals as it did ten or fifteen years ago,” p. 63. The fist part of the book is entitled history and development and the chapters are hended: Searles Lake; early history; solubility and double salts; early plant operation;
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special features of the operation; the present plant. The second part is entitled equilibrium data and diagrams. “There will he found included sixteen systems of two components, thirty-eight of three components, twenty-five of four components, six of five components, and one of six components, one component always being water. Some systems are given at a single temperature, others a t four or five temperatures over a considerable range. This obviously does not exhaust the subject; far from it. Only those are given which we found it necessary t o work out for our own purposes, and naturally not all of those.” The development of Searles Lake was an economic and srientific triumph for Teeple and for those who had confidence in Teeple. Teeple richly deserved the Perkin medal, which fortunately was awarded t o him before his death. He succumbed to an operation which his friends had expected would put him hack in really good health once more. This hook is valuable for the scientific data that it contains. It is also valuable because it is so written that it will give t o those who did not have the privilege of knowing Teeple personally some conception of the charm, ability, and personai honesty of the man. fi‘ilder D. Bancroft
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265. Boston and ,Vew Oceanography. By Henry B. Bigelow. 21 X 14 c m ; p p . I Fork: H o u g h t o n i M i f l i n Cumpany, 1931. Price $2.50. The chapters are entitled: introductory; submarine geology; physical and chemical problems of the sea water; relationship between oceanography and meteorology; life in the sea; economic value of oceanographic investigations; physical, chemical, geologic, and biologic unity in the sea. “In practice oceanography falls most conveniently into three chief divisions: ( a ) the geological; ( b ) the physical-chemical; (c) the biological.” I t is therefore a rational order of presentation “to consider first the problems of the shape and composition of the basins that hold the oceans (Le., submarine geology); next, those associated with the physical character and chemical composition of the waters that fill these basins (physics and chemistry of sea water); and third, those of the nature and activities of the animals and plants that inhabit the waters (life in the sea),” p. I I . “An exact knowledge of the topography of the bottom would go far toward establishing the possibility of great rockslideson the steeper submarine slopes, a questionrecentlyraised by the puzzling rock formations in the Alps, Appalachians, and other mountain chains,” p. 14. “This matter of depth and of the local variations in crystal stability is of equal interest to the palaeontologist, and t o the zoogeographer, because of its hearing on possible former land connections which have been postulated to explain the distribution of terrestrial animals and plants as a t present existing; no less to account for the continental separations by which different floral and faunal areas (once continuous) are now isolated from one another. Changes in the depth of epicontinental seas, and in the degree to which the great oceans have been in free communication with one another in the past, equally concern the marine biologist as factors controlling the dispersal-routes of many marine organisms, and as affecting the ocean currents that transport animal and plant species,” p. 16. “Lime rocks have certainly been the most widely discussed of marine sedimentary formations, and in some cases, as with an oyster bed, or a reef of corals, or a swarm of Globigerinae, the progress of the event by which lime is added to the sea floor may be easily observed. But great quantities of limy mud are also being laid down in tropical seas, the minute amorphous particles of which seem not t o he the simple fragments of shells of defunct animals. Whether bacteria are responsible for the formation of these muds, as formerly supposed, or whether they result from chemical or mechanical precipitation quite independent of bacteria, or whether, after all, they are simply the end product of the breakdown of exposed limestones, beach sand, etc., as has recently been maintained, is still a moot question. This question, however, is of great theoretic interest, not only for its hearing on events now taking place in the sea, but in connection with the formation of oolitic l i m e stones, and in relation to the relative importance of salt and fresh-water situations as sites for the formation of limestones, now and in the past,” p. 29.
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“Problems equally broad arise in connection with the siliceous deposits, for with silica constantly contributed by the rivers to the sea, and with no return loss either to the atmosphere or to the land (except in regions of elevation), it seems that the silica of the earth is now tending to accumulate on the sea floor. The geologist is, therefore, as deeply interested as is the biologist in the factors that cause such accumulation of silica to take place most rapidly in cold water, and a t great depths, as signboards to the conditions under which similar events occurred in the seas in past geologic ages. Among these siliceous deposits the radiolarian-bearing sediments demand special attention, both in relation to the depth at which they were deposited, as just mentioned, and because knowledge of the conditions under which they were laid don-n is vital to our understanding of the geosynclinal rocks, hence of the world’s mountain chains. “The formation of phosphatic concretions and of glauconite on the sea bottom of today also needs fresh examination for its bearing on the origin of phosphatic and potash rocks: it is in the sea, too, that the key t o the riddle of the source and mode of formation of dolomite is most hopefully to be sought,” p. 31. “The problem of iron in modern marine deposits is important because of its bearing on the question, what part of the iron ores now being mined in sedimentaryrocks were originally laid down with the latter, or in what part they entered subsequently, as secondary intrusions? Are deposits of this sort being laid down anywhere today? What, if anything, have bacteria to do with the segregation of iron in the sea? How does the common association of iron with manganese in modern deep-sea deposits bear on this problem? How sound are the chemical reactions that have been proposed to account for the deposition of either of these minerals, and what conclusion must we draw-, as to the depths of the Paleozoic seas, from the distribution of iron, in deep and in shoal water, in the modern sediments?” p. 34. “The studies of the chemistry of sea water that are a t present in progress, like those of its physics, chiefly aim at enlarging our factual knowledge of regional variations, and our understanding of events that take place in the cycle of matter there, rather than at clarifying the nature of chemical processes as such. Thus they bear to the science of physical chemistry a s a whole a relationship more subsidiary than do oceanic biology or physiology t o current attempts to fathom the riddle of life,” p. j ~ . “The distribution of oxygen in the sea is so closely associated with the general problem ot vertical circulation that it is best mentioned here. I t seems certain that the intake of oxygen occurs exclusively a t and near the surface, ( a) in the surface fdm, or within the upper few feet where their bubbles are entrapped by breaking waves, and ( b ) throughout the upper illuminated zone where plants carry on photosynthesis; no sources are known from which the water ran absorb free oxygen in the deeper levels. Quantitative data as t o the rapidity with which any deficiency in oxygen is renewed from these sources of supply (particularly the efficiency of the latter out in the open sea) are therefore present desiderata. The relative importance, from the standpoint of oxygen intake, of coastlines of different characters, with their different types of wave action and of turbulence, offers an interesting problem. How effective a source of oxygen supply for the surrounding neighborhood is, for instance, a rocky headland upon which the surf beats constantly? We have yet to learn ho,w deep simple turbulence is able to maintain the oxygen supply close to the saturation po’nt in different regions under different conditions,” p. 86. “If there were no means of renewing oxygen from above, the underlying water would soon be absolutely stripped of this vital necessity, as the deeps of the Black Sea actually are. And within the last few years it has been found-(notably by the ‘Carnegie’ and by the ‘Dana’) that the mid-depths are, in fact, decidedly poor in oxygen in mid and low latitudes in the Pacific-also over large areas in the tropical Atlantic; so poor indeed, that one is inclined t o marvel a t the wealth of animal life that exists there. But, underlying this oxygen-poor stratum, the bottom waters of the ocean basins carry a much richer load oi this gas. I n the present state of our knowledge, it seems that the only way in which stratification of this sort can be maintained is by sinking currents carrying down into the deeps, water that has become saturated with oxygen near the surface in high latitudes, coupled with the consumption in the mid-stratum, rapid enough nearly to denude of its oxygen the
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water that is brought up from below by rising currents. But we urgently need information as to whether these mass sinkings of oxygen-laden water are as strictly confined to the Arctic and Antarctic, in their respective winters, as now seems probable; also how this water continues so nearly uniform in oxygen over vast areas on the sea floor in spite of the wide local variations in abundance of animals that are constantly consuming it there; and how f a r it is safe to deduce the drifts for the deepest stratum from the variations in the concentration of oxygen that do exist there,” p. 87. “Some substances are a t present known t o exist in sea water solely because they have been detected in the bodies or skeletons of marine animals and plants, which could only have obtained them from their aqueous environment. As examples of this we might mention the vanadium recognized in the blood of Ascidians and of Holothurians; the cobalt in the tissues of lobsters and muscles; the nickel in mollusks; and the lead that has been found in the ash of various marine organisms,” p. 109. “Various explanations have been proposed for the chemical events by which the preponderance of calcium and of carbonates, which characterizes river water, is so uniformly altered into the preponderance of sodium and of chlorides that characterizes the sea water, everywhere, and a t all times, even under the most diverse conditions. But we believe no one would seriously maintain that any of the explanations are adequate,” p. I 13. “Another contrast having far-reaching biologic effects is t h a t between the specific gravity of the medium in which organisms live on land-the air-and in the sea. Thanks to the fact t h a t sea water has almost the same specific gravity as protoplasm (or protoplasm as sea water if one prefer) no marine animal or plant needs the mechanical support against the pull of gravity t h a t every organism of any considerable size must have on land if i t is not to collapse of its own weight. Thus no alga needs, or has developed, a rigid woody skeleton. And as marine animals have never required strong frameworks to support themselves, their internal or external skeletons can he adapted entirely to other ends, such as protection (as in the case of many mollusks) to provide stiffness as among the horny corals, to maintain body form against resistance of the water while swimming or for the attachment of muscles as among fishes and crustaceans. Comparison of the frame of a whale (\vhich suffocates of i t s own weight if left stranded on the beach by the ebbing tide) with t h a t of an elephant or a dinosaur shows a t a glance how much less is necessary i n the one case than in the other. I n spite of their great muscular power, even the largest sharks have still feebler and wholly cartilaginous skeletons without any hard bones, while even a more striking case of strength without framework is afforded by the giant squids, animals proverbially active, swift and muscular, though with only the rudiment of any sort of skeleton. No morphological development of this sort would be possible on land. As a corollary of this, there is no gravitational limit to the size of animals in the sea, the only theoretic limit being their need of taking in, through the surface (and usually through a very small part of it), enough foeti to support the entire bulk and enough oxygen for its vital requirements. With relief froin the force of gravity, the sea supports animals as large today as it ever has, and heavier than any that have existed on land,” p. 141. “It is still a mystery how fishes and other marine animals are able t o direct their long journeys, often in darkness, and always through a medium in which temperature and chemical composition are so nearly uniform over long distances t h a t the most delicate tests are needed t o reveal any difference a t points many miles apart. T h e problem here is akin to t h a t of bird-migration, but a n even more puzzling one,” p. 149. “The question by what mechanism the cell is able t o select out of the water those rare substances that, as it now seems, are of vital importance, opens the whole problem of the specific affinity of diflerent cells for particular chemicals that forms the basis for all the structures t h a t protoplasm manufactures. We might mention the secretion b y diatoms of silica (an element relatively rare in sea water) in such great quantity that a t times they may almost exhaust the water o! i t ; the ability of seaweeds to draw iodine and potassium from the surrounding water so much more efficiently than man can, that until other sources for these substances were discovered it was far more economical to obtain them from the ash of seaweeds than it would have been to concentrate them direct from the water by any
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method yet perfected or likely to he developed: the ability of certain unicellular animals (Radiolaria) to build their shells of strontia, a substance so rare in the water that only recently have analyses revealed its presence there. If any seaweed made equal use of gold, the commercial extraction of the latter from sea water (on the average there are about five milligrams gold per cubic meter of water) would not be the will-o’-the-wisp it has actually proved. A more familiar example of the ability of the living cell to select particular substances from the outside is the secretion of limy shells by a great variety of plants and animals, an ability responsible for vast deposits of calcareous sediments, of limestone rock, and of the modern coral reefs. The question of the draft made by different vegetable relis of specific solutes for their nourishment, as of nitrates and of phosphates by diatoms: or of the same solutes in different proportion, is now under investigation at many hands,” p. 163, “The simplest task of marine bacteriology is perhaps to trace the direct service these lowly and minute organisms render to the larger in providing the latter with proteid food. That protozoans do feed on bacteria in the sea is established. I n fact, recent studies suggest that in this passive way the bacteria that thrive on the organic debris accumulating in shoal waters, and the protozoa that prey upon these bacteria, are essential links in the food-chain of higher animals in coastal waters, where the echinoderms, mollusks, and others that feed on detritus gain their nourishment less from the latter direct than from bacteria and protozoa eaten a t the same time,” p. 167. “We ail need t o know what part bacteria play in breaking down the more refractory organic substances that would accumulate on the bottom of the sea if there were not some mechanism to disintegrate them and to bring them into solution in the water. Specifically, what quantitative role do bacteria play in the sea, in the destruction of the agar from the stalks and fronds of seaweeds that is constantly taking place under water-a substance resistant t o most bacteria? Bacteria of the sorts that do attack agar have recently been found in brackish and in salt water. But, so far, it has been only in the tropics that their presence in such situations has been established, whereas it is in higher latitudes (and lower temperatures) that the great concentrations of ordinary seaweeds exiet, and the great overturn of agar and of similar hemicelluloses takes place. Thus it still remains an open question how far the annual disintegration of the millions of tons of kelp, and so forth, results from bacterial activity, or how far it simply reflects the solvent action of the sea water itself. We face this same problem with regard to the destruction of the chitin in the shells of dead crabs, shrimps, and other crustaceans, and of the oil from diatoms and copepods,” p. 180. W i l d e r D. Bancrofl Ausgewahlte Untersuchungsverfahren fur das chemische Laboratorium. By L . IV. W i n k l e r . Vol. 29 of Die chemische A n a l y s e founded by B . M. Margosches, edited by u’. Bottger). 25 X 17 e m ; p p . xtiii 155. Sfultgart:Ferdinand E n k e , 1951. Price 17.50 m a r k s ; bound, 19.50 marks. This is essentially a somewhat miscellaneous collection of analytical and other methods devised by the author and described in various journals during the past thirty years or so. Few of these methods were ever fundamentally new hut they all include some modification, either important or trivial, made so as to enable an older method to he carried out with simpler apparatus, or more rapidly or more accurately. Most people interested in chemical analysis will find something to interest them in the book. The first 24 pages deal with determinations of density (gas, liquid, solid), melting point and boiling point. I n the next 5 5 pages come simple gas analytical methods and some selected volumetric methods are described while those remaining are concerned with gravimetric estimations. The latter include several solvent extraction processes for dealing with mixtures of alkali metal salts and alkaline earth metal salts. The last third of the book is devoted to gravimetric precipitations. The manipulative procedure prescribed for all these is similar and in most cases involves slow precipitation from boiling, neutral solutions containing considerable amounts of ammonium chloride, a piece of cadmium foil being added to prevent bumping.
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The fairly coarsely c r y s t a h e precipitates obtained in this n a y are filtered through a small pad of cotton wool in a small, more or lese cylindrical, glass funnel (“Kelchtrichter”). T h e precipitates are weighed in the funnel after drying eit>hera t room temperature, 100’ or 130’ according to circumstances. Throughout the book experimental procedure is described in the most minute detail. H . Bassell Alkalien und Erdalkalien in ausgewlhlten Kapiteln. (Vol. 26 of Technische Fortschritlsberichte. Fortschritle der chem. Technoloqie in EinzeldarslellzLngen. Edited b y B. R a s s o u , 196. Dresden and Leiprig: Theodor Leipzig). B y B r u n o ll’aeser 22 X 15 cni; p p . viii Steinkopff, 1031. Price: 13.60 m a r k s ; bound 15 T a r k s . The object of this monograph is to give a summary of new developments in the technical preparation and utilisation of alkali metal compounds during the last decade. Only those compounds are dealt with, however, which have not already been considered in other volumes ot the same series. The field covered in the volume under review is, in consequence, very restricted. This is particularly true of the alkaline earth compounds which take up 50 pages, of which a few calcium and barium compounds account for 45, the remaininR five being required for strontium and beryllium. The alkali metal compounds discussed are:-sodium and potassium carbonates and hydroxides (other than electrolytic), peroxides, borates, cyanides (thiocyanates, ferrocyanides, etc.), chromates, manganates, halogen compounds (other than electrolytic), phosphates (other than fertilisers), arsenates, sulphur compounds (except sulphate'^. silicates. Three pages are devoted to lithium, rubidium and caesium. There are several interesting summaries of the economic situation in respect of some of the more important compounds such as the alkali carbonates, hydroxides and borates while in the case of most compounds a very brief outline is given of the method of preparation now in use. These are the only parts of the book likely to interest the general chemical reader. The greater part of the hook is taken up with short references to articles in the technical literature and to patents. The subject matter of the latter is given but the reader will find little guidance as to whether the patents are of any practical value and to what extent they are actually used. In the case of recent patent literature this is probably inevitable but those actually engaged in the alkali industry, for whom the book is intended, should find it useful and they will be in a position to judge such matters for themselves. The reviewer regrets the tendency in modern German books for the spelling of longestablished words euch as caesium, cyanid to be altered to zaesium, zyanid. Thie will doubtless increase the number of words beginning with z but from all other points of viewthe change seems both undesirable and unnecessary. H . Bassett
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Heterogene Katalyse. B y E r w i n Sauter. 22 X 15 c m ; p p . z 80. Dresden and Leipzig: Theodor Steinkopfl, 1OS0. In the preface the author says t h a t although in chemical circles the view is still held t h a t the field of catalysis is still quite obscure, he believes himself able to show t h a t such a n idea is no longer correct. “Admittedly it is hard to arrange the wealth of work on catalysis so that the simple and more general picture of catalysis is not blurred and masked by the incredible number of special observations. . . . It appears from the development t h a t the chief problems of catalytic investigation are becoming more and more akin t o those of theoretical physics.” After a n introductory chapter dealing with the definition and classification of catalysts, with activation hypotheses and such-iike things, the chapters dealing with heterogeneous catalysis proper are entitled: remarks on the preparation of catalysts; changes of state and properties of heterogeneous catalysts; how shall one characterize a contact catalyst with reference to the demands to be made upon i t ; the phenomenon of poisoning in contact catalysis, contact catalysis and sorption; selective contact catalysis; heat of activation a t catalytic surfaces; reaction velocity and contact catalysis; instances of experimental technique.
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On p. 7 the author says that in the majority of cases studied kinetically the reaction does not run practically t o an end. Since the temperature usually does not rise very high in the catalytic conversions, unsupported catalysts may be used there, as in the case of Paal’s colloidal palladium, p. 2 1 . “The heats of adsorption are of the magnitude of the van der Waals forces; they are always then the heats of vaporization of the adsorbed substances,” p. 38. According to Magnus the adsorption of carbon dioxide by charcoal decreases so rapidly with rising temperature as to become approximately zero a t ~ o o ”p. , 43. The author believes in chemical sorption which differs from ordinary adsorption and is the important thing in contact catalysis, p. 48. ‘Chemical sorption depends chiefly on two actions: I . Between sorbent and sorbate there is direct electron action. According t o the newer quantum theory there are formed an ionogenic and a homopolar bond, between which intermediate phenomena are possible. 2 . Between sorbent and sorbate there is formed a eo-ordinative bond (according to Werner compounds of a higher order occur). The sorbed molecule undergoes considerable deformation as it adds to the sorbent to form a new chemical molecule. I t is essential that the chemical sorption leads only to the formation of a monomolecular surface compound, the peculiar lability of which was recognized especially by Volmer.” The author does not play quite fair in his statement that the intermediate compound theory has rather won out. He quotes the reviewer as assuming the existence of free radicals, p. 53. What everybody else has meant by the intermediate compound theory has been a compound formed by the catalyst with one or more of the reacting products. The author now implies that it covers the formation of monatomic hydrogen in presence of nickel or platinum. One can hardly believe that the author could make such a mistake as that and yet it is more painful to believe that he knew what he was doing. On p. 47 it is recognized that carbon monoxide is not activated appreciably when adsorbed by platinum; but no attempt is made to account for this. Tl-ilder 0. Bancroft
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Thermodynamik. B y It’. Schotlky. 26 X 17 cm; p p . xxu 690. Berlin: Julius Springer, 1999. Price: 56 m a r k s ; bound 58.80 marks. The author intends this to he the best hook on thermodynamics ever writen. He claims to have discussed all points a t length, which seems to he true. He differentiates quite sharply, p. x, b e h e e n external and internal thermodynamics. External thermodynamics deals with reversible systems and usually with reversible cycles. Internal thermodynamics recognizes the existence of passive resistances to change and deals with would-be cycles which don’t close. The hook is divided into three parts: general thermodynamics; physical thermodynamics; and chemical thermodynamics. The third part is more than three-quarters of the whole treatment. The chapters in the third part are: application of thermodynamics to chemical reactions; equilibrium conditions and the phase rule; theoretical and practical methods for building up reaction effects from thermodynamic data; regularities in special states and changes; chemical affinities and equilibrium conditions as given by measurahle thermodynamic values; equilibria of higher orders and phase stability; changes while maintaining equilibrium; examples in the application of thermodynamics. “It is now necessary to discuss an apparent contradiction which occurs in the assumptions underlying the discussion that has just been made. It was assumed that the end state could be carried back reversibly into the initial state. According to what has been said, that is only possible when the system passes through a series of thermal equilibria. The initial and end states must especially represent thermal equilibria, which is therefore necessary in the actual cases to be discussed, because otherwise the state and consequently the entropy cannot be characterized by a relatively small number of independent variables. “On the other hand, the initial state might change into the final state through irreversible stages following chronologically without there being any change in the external conditions -since we are dealing with closed systems. We must therefore have a system in thermal equilibrium which can show spontaneous changes that carry it over spontaneously into another state. According to our definition that means that it was not a system in thermal equilibrium.
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“A clearing-up of this contradiction and thereby the possibility of applying all these considerations is evidently given only when the original state involved a partially retarded system and did not strive to attain an irreversibly reached end-state because it is kept from taking the necessary steps by some sort of retardations which keep it from passing through the various steps. If these retardations were absolute and were never to be lifted, the whole discussion would become hopeless. Its application is limited to cases where the retardations can be over-ruled arbitrarily without perceptible thermodynamic expenditure,” p. 56. “The only significant definition of the solid state is the one that the smallest particles of the body in question are not freely movable relatively to one another, but are to be found in a stable arrangement, which it takes up again when disturbed,” p. 9j. “The variations from the law of Dulong and Petit show the regularity that the specific heat per gram atom is too large a t high temperatures and too small at low temperatures. The significance of the variation upward is hard to explain and people are not agreed as to it. , . . The theoretical explanation of the variations which come out too low are more successful since Nernst has shown that the specific heats of all substances decrease in the same way as the temperature falls toward the absolute zero and approach zero as the temperature falls toward the absolute zero. The quantum theory accounts for this by postulating a finite magnitude of energy differences between the lowest and the next higher of the possible quantum states of the vibrating atom and establishes a relation between the size of these energy jumps and the otherwise-determined self-frequency of the atom vibrations,” p. 99. It is doubtful whether the discussion of the relation between the maximum surface tension of mercury and the single-potential difference will be especially helpful, p. 122. S o suggestion is offered as to a possible line of attack on the problem. The author is quite enthusiastic over the activity concept and introduces it on all occasions. This is the more extraordinary because he admits, on p. 290, that the only object in introducing the activity concept is to enable one t o continue to use the simple relations which either hold or seem to hold for dilute gases and dilute solutions. The discussion of the variations from the ideal gas laws, p. 296, is not helpful. “The method of accounting for the variation from the ideal gas laws by introducing the chemical potentials and the activities [he puts the chemical potential and the activity on the same thermodynamic level] is a purely formal one and is often looked upon as unsatisfactory. There have of course been attempts to account for the variations admitted by the introduction of a instead of z on a molecular-theoretical basis by assuming special chemical interactions, which lead to the formation of new molecular types, for each of which the laws of ideal solutions hold. I t is true that is possible in this way t o account for almost all the phenomena, but it seems unjustified from the thermodynamic and molecular-theoretical viewpoint to exaggerate the chemical viewpoint to the extent of a general application of such a process. I t is simply another formalism which has not even the advantage of being convenient. The attempt to handle liquid mixtures by means of the van der Waals equation of state is in fact scarcely less formal than the method of activities, because it involves a t present empirical coefficients. I t is not denied that the van der Waals equation may often he a convenient starting-point for an analytical presentation of the experimental data, though it is bard to say what the constants in the formulas mean and impossible t o predict them. “In view of the prevailing uncertainty whether the [abnormal] behavior of a solution is due chiefly to interactions of a chemical nature (solvation, polymerization, etc.), or of a physical nature (ionic forces, van der TTaals forces), or t o different kinds of interactions occurring simultaneously, it is better for the present to stick to the treatment by residual work or activity, which does not explain anything but gives a good description of the thermodynamic results. I n cases, however, where the molecular state or the kind and influence of the physical interactions seem to be estahlished by many experiments (for instance, formation of double molecules of organic acids in non-aqueous solvents, dissociation of strong and weak electrolytes), the predictions from the activities on the basis of this more exact knowledge and their comparison with the empirically determined data offers a n especially convenient and comprehensive test of the special molecular assumption. Of course
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one must never let the convenient presentation of the data by empirical activities interfere with special conceptions in regard t o possible molecular states and prevailing interacting forces, the working out of which must always remain the goal of investigations [wine bricks are now sold with strict injunctions not to put them in water!. “Widespread misconceptions make it desirable to say again here that the introduction of activities in no way denies the occurrence of chemical interactions. Activities (or residual work) do away with the need of making insuflciently-grounded,special assumptions as a basis for the presentation of the subject. The activity concept permits the limitation of the discussion to what is known empirically.” This seems to be a very roundabout way of saying that the introduction of the activity concept puts all the disturbing factors out of sight and makes it possible to forget that they exist. On p. 360 are given activity-concentration curves for acetone and carbon bisulphide, hoth curves lying above the ideal ones and a similar diagram for acetone and chloroform in which both curves lie below the ideal ones. KO conclusion is drawn in either case. A mere statement of the activities is sufficient. T o the layman it is not clear why pressure-concentration curves would not have been equally inadequate. The question of the salting-out of a non-electrolyte is handled very briefly, p. 439. “The solubility of a non-electrolyte in aqueous solution is in general decreased by addition of an electrolyte, a phenomenon which is known as salting-out and which finds many practical applications. Thermodynamically speaking, the addition of an electrolyte increases the activity of a dissolved non-electrolyte. With volatile non-electrolytes there is consequently an increase in the partial pressure.” Lash Miller did better than that over thirty years ago and without making use of activities. He showed definitely what Schottky probably assumes but certainly does not state, that the electrolyte and the non-electrolyte must be mutually insoluble. Miller’s demonstration was general and did not necessitate one of the components being an electrolyte. “If we dissolve solid naphthalene in benzene, we should expect heat and volume effects corresponding very closely to the heat of fusion of naphthalene and to the volume difierence betxeen solid and liquid naphthalene. The same thing must hold for all solutions of naphthalene in all liquids with which it forms ideal solutions. Gehlhoff has confirmed this prediction for the heats of solution. He obtained heats of solution of 4400-4800 cal/mol when naphthalene war dissolved in benzene, ether, aniline, etc., while the heat of fusion is 4560 cal?mol.” One would have liked t o see the conclusion drawn that naphthalene is present as a liquid and with some of the properties of liquid naphthalene even in dilute solutions. The corollary to that would have been that sodium nitrate is present as a liquid and with some of the properties of liquid sodium nitrate even in dilute aqueous solutions. As another the author might have felt reckless enough to say that sulphuric acid is present as a liquid and with some of the properties of liquid sulphuric acid even in dilute aqueous solutions. Even if he had got as far as this, he would probably have balked a t saying that lead sulphate dissolves in sulphuric acid because it is soluble in liquid sulphuric acid. It is quite certain that a complex salt would have been invoked or possibly 3r change in activity. On p. 592 there is given what purports to be a rigid thermodynamic deduction of Kernst’s distribution lam, which omits all reference to the increasing mutual solubility of the two liquids on addition of the third component. I t seems to the reviewer that the author is a man who has picked up his physical chemistry on the side and who has never really mastered the subject. The book cannot be recommended t o the progressive chemist. The author’s presentation is not even a masterpiece of Wilder D. Bancrojt style.
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Practical Physical Chemistry. By A. Findlay. 22 X 14 cm; p p . xii 312. London: Longmans, Green and Company, 1931. Price: 7 shillings, 6 pence. I n the fifth edition of this well-known book the form of the last edition and much of the old material have been retained. Some additions have been made, the most important dealing with potentiometric measurements, and experiments have been added to illustrate the conception of activity. Very few of the new experiments involve anything fresh in the way of experi-
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mental technique, and consequently the book cannot be regarded as entirely representative of modern experimental methods. The use of the thermionic valve in potentiometric measurements is described but there is no mention, except in a foot-note, of its employment in the determination of electrical conductivity, and the chapter dealing with the latter suhject is unaltered. The book would have gained in value if some of the more rarely used approximate methods, especially of determining osmotic activity, had been omitted and the space devoted to a fairly full treatment of more accurate methods. I n spite of this however there is no doubt that the book will continue to be of the greatest value as an introduction C. S.S a l m o n to the study of experimental physical chemistry.
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93. London: .\leihim, and Thermodynamics. By 8 . TT. Porter. I ; X I 1 c m ; p p . u Co,, 2932. Price: 2 shillings, 6 pence. The author intended this monograph to “enable a reader to understand the logical foundations of the suhject, and not only to see the kind of applications that are made of thermodynamic principles in various parts of physics, but t o be able safely to apply them himself to further problems.” He has succeeded admirably. An enormous amount of information is packed into very small compass, partly by fine writing and partly by a free use of the “language” of mathematics. K o t that more than a knowledge of the elements of calculus is required, hut the reader must be able to use such knoidedge freely. The outlook is physical rather than chemical, though the chapter on “equilibrium” deals hriefly with the isochore, the isotherm and the phase rule. Classical notation is employed in preference to that of the G. S . Lewis school, the “Free Energy” of which is called the ‘,Gibhsfunrtion” in this work. and there is no reference to “activity.” The foundations of the subject are, however, exceptionally a-ell presented. I,. J . Hiidleston
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