KEW BOOKS A Comprehensive Treatise on Inorganic and Theoretical Chemistry. VoZ. VI. B y J . W . Mellor. 26 x 16 cna; pp. x+i024. London and New York: Longmans, Green and Co., 1926. Price: 65 shillings; 820.00. We welcome the sixth of these remarkable volumes. This volume finishes the discussion of carbon, taking up the carbonates and carbon bisulphide. Well over eighty-five percent of the book is devoted to silicon. As was the case with the other volumes, this one is a treasure-house of interesting facts. “Chamberlin estimated that I ,620,000,000 tons of carbon dioxide are withdrawn annually from the atmosphere in the formation of sedimentary rocks, p. 4. “It will be noticed that all animal and vegetable life is dependent upon the carbon dioxidQ+carbon reaction, which in turn is dependent upon the sun’s energy. There is a kind of closed cycle, an alternation of oxidations and deoxidations:
Sun’s energy stored-plants deoxidation
feed
coz+_-----oxidation Energy dissipated-animals
and plants breathe etc.,
maintained by a continuous supply of energy from the sun. If the supply should cease’ the deoxidation of carbon dioxide would stop and the present conditions of life on the earth would come to an end because the available carbon would be transformed into unavailable carbon dioxide,” p. 13. The Poison Valley or the Valley of Death in Java is an old volcanic crater with fissures from which are evolved large quantities of carbon dioxide which fill the valley as water fills a lake. The flow is apparently intermittent because sometimes scarcely a trace of gas can be found, while a t other times it fills the valley. The valley is about half a mile in circumference and is oval. The depth is from thirty to thirty-five feet. The bottom is quite flat, with no vegetation, and is covered with the skeletons of human beings, tigers, pigs, deer, peacocks, and all sorts of birds. “The Death Gulch of the Yellowstone Park is another such valley, where it is said that grizzly bears are sometimes found suffocated to death by the carbon dioxide which issues from the ground. The Laacher Sea is the water-filled crater of a prehistoric volcano, and near by is a depression filled with carbon dioxide. Birds and insects flying in this region are suffocated”, p. 7 . “According to R. Brimmeyr, when carbon dioxide is separated from hydrogen by a moist bladder, more carbon dioxide diffuses to the specifically lighter gas then conversely; and Bith a dry porous partition, less carbon dioxide diffuses to the specifically lighter gas than conversely. Wiesner and Molisch also found that carbon dioxide diffuses through vegetable membranes more rapidly than hydrogen, oxygen, or nitrogen,” p. 24. Carbon dioxide should diffuse more slowly through pores than hydrogen. When water is present and the diffusion is chiefly, or perhaps entirely, through the water, the solubility relations are the decisive ones. The presence of air interferes with the liquefaction of carbon dioxide much more than can be accounted for by the pressure alone, p. 31. It seems a question in part of the air dissolving in the carbon dioxide and in part of the carbon dioxide dissolving in the air. “Arrhenius tried to picture the effect of a change in the proportion of carbon dioxide in the atmosphere on the surface temperature of the earth. The temperature of the earth’s surface was assumed to be in equilibrium with that of the atmosphere; if, by any increase in the amount of carbon dioxide, the atmosphere retained more heat than before, it would radiate more heat to the surface of the earth. The surface temperature would then rise until equilibrium between the two occurred. The rise was assumed to be governed by the
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radiation law, and hence it was estimated that if the carbon dioxide is increased 2.j-3.0 times its present value, the temperature in the Arctic regions would rise 8O-9’ and would produce a climate as mild as that of the Eocene Period; a decrease of 0.55 to 0.62times its present value v7ould cause a fall of 4”-5”and produce a glacial period. Frech and C. F. Tolman support Arrhenius’ views. Kayser, Abbott, and Fowle hold that the carbon dioxide in the atmosphere cannot absorb more than sixteen percent of the terrestrial radiations; that variations in its amount are of small effect; and that the proportion of water vapor in the atmosphere is so large as to make the climatic significance [of carbon dioxide] negligible. The principal absorbent of terrestrial radiation is water vapor,” p. 37. In some cases stalagmites grow very rapidly. “The San Filippo spring (Tuscany) is said to deposit lime a t the rate of twelve inches a month, and the spring has formed a bed of limestone rock 250 feet thick, 1.5miles long and 0.33 miles wide. The building stone called travertine (Tiberstone) is probably a limestone deposited from a mineral spring,” p. 81, “Quartz which has been formed above 575” can be distinguished from quartz which has never reached that temperature. At ordinary temperature all quartz is a-quartz, but if a t any time in its history a particular piece of quartz has passed the inversion point and has been heated above 57.5“it bears ever afterwards marks potentially present which on proper treatment can be made to appear just as an pxposed photographic plate can be distinguished a t once from an unexposed plate on immersion in a proper developer, although both plates may be identical in appearance before development. Wright and Larsen go further and say that quartz can be used as a geological thermometer, because if at any time quartz has been heated above 575”, this fact is recorded in its structure by the corrosion figures. Hence, also, quartz in any rock must have formed below 870°, and its peculiarities indicate whether it was crystallized above or below 57j0,”p. 247. Pliny refers to a rare and costly cloth, the cremation cloth of kings. He thought that it was of vegetable origin, and gave an imaginary description of its growth in the deserts of India. Plutarch, in the first century of our era, said that asbestos was used in ancient times for making the wicks of the lamps used by the vestal virgins. In the thirteenth century, Marco Polo mentioned “an indestructible cloth made by the Tartars which was said to be made from the skin of the salamander, supposed to live in fire, but which was found to be woven from a fibrous mineral called amicanto. The knowledge of asbestos possessed by the ancients appears t o have been forgotten. Apart from a few isolated eases, the industrial applications of asbestos did not attract serious attention until towards the middle of the nineteenth century,” p. 425. “Numerous observers have demonstrated the decomposition of felspar, mica, and related minerals by the action of water, and particularly water charged with carbon dioxide. Headden, for instance, said that water holding carbon dioxide in solution is nearly nine tinies as active as distilled water when in contact with felspar. Water can work its way into the body of granite rocks through pores and cleavage cracks; for, according to van Hise, granite rocks have a porosity of 0.2-0.5percent. According to Bischof, one of the springs in the vicinity of Lake Leach (Germany) discharged nearly 176,000 lbs. of water carrying 0.13percent of sodium carbonate in 24 hrs.; assuming that the sodium in felspar is converted into soluble sodium carbonate, this would represent the decomposition of nearly 18,000 lbs. of soda-felspar per annum. A few centuries would thus suffice to decompose enormous masses of granite rock. It does seem curious to find that a dilute solution of carbon dioxide has sufficient chemical strength to decompose a combination like felspar which is fairly resistant to the most powerful mineral acids; but H. Rose pointed out, in 1842,that the enormous quantities of carbonic acid which are brought into contact with the rock make up for its deficiency in chemical strength. According to L. von Struve and H. Muller, carbon dioxide under compression is more active than it is a t ordinary pressures. A. Stahl considers that the clay deposits a t Passau, Mederschlesien, and Odenwald have been formed from gneiss rocks by the action of the carbon dioxide. The china clay a t Auvergne (France) is supposed to have been formed in this way; W. S. Bayley found that the china clay in the Piedmont Plateau, North Carolina, gradually merges downwards into felspar. The effect of carbonated waters can be easily overestimated, in contrast with the
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action of organic acids which are probably more powerful than carbonic acid. Ginsberg, however, claims that the formation of china clay by the action of organic acids in natural waters has not been demonstrated H Stremme considers that the efficiency of all the different weathering agents is really due to the chemical activity of aqueous solutions of carbonic acid-cold or hot; and K. Endell has shown that the acidity of moor-waters is largely due to the carbonic acid they contain,” p. 469. “The remarkable effects of gum and other mucilages in enhancing the plasticity of clay has been utilized by potters for an indefinitely long time. In I903 E. G. Acheson patented the use of aqueous solutions of the tannins and gallotannins, e.g. decoctions of oak-bark, etc.; and in 1918 G. Keppler, and A Sprangenberg patented the use of decoctions of humic acid, peat, etc. These plasticizing agents probably act indirectly by adsorption. The clay particles adsorb the organic colloid, and, judging by results, this probably augments the surface attraction be tween the particles and the surrounding liquid. The plasticity of china clays, practically free from organic matter, shows that adsorbed organic colloids are not always the source of their plasticity. Clays which have been sodden with ground waters rich in organic matter are usually highlv plastic; and those clays which can be shown geologically to have been deposited in swamps and bogs, or which have been in contact s-ith such waters, are usually very plastic unless other metamorphic changes have occurred. Many such clays, however, are not plastic when freshlv dug, but they become plastic during weathering. When first mined some of the clays are hard, but if they be moistened and exposed to sunshine and frost they diqintegrate more or less quickly and crumble to finepained plastic clays. Clays which are allowed to stand for a long time in contact with moisture become more plastic, or, as the workmen express it, more “buttery.” Clays which have been boiled with mater also become more plastic. Clays prepared by fast processesfilter-press-are not so “buttery” as when prepared by a slower process-slip-kiln. China clays prepared by the elaborate, apparmtly primitive Cornish process-by slow sedimentation and slip-kiln-are more plastic than when the process of dewatering the clay is accelerated by filter-press. There is thus an intimate connection between the plasticity of a clay and its past history with respect to water. All this looks as if the clay in contact with watzr is being hydrated to form a colloidal gel,” p. 490. “The ancient writers attributed the discovery of the art of making glass to the Phoenicians, but excavations in Egyptian tombs have shown that the Egyptians must have been adept glass-makers long before the Phoenicians practiced the art. This indicates that the Phoenicians were probably distributors of Egyptian glass before their own factories were established a t Sidon. In the work cited above, Pliny said that glass was made in Italy, and in the Gallic and Spanish provinces, by fusing sand with three times its weight of nitre; and he added that in India rock-crystal was used in place of sand. Bases other than the alkalies are needed to make the glass resist rapid attack by moisture. These might have been added deliberately, or brought in as impurities with the sand or alkalies,” p. 520. “Representations of these processes of glass-making are depicted on the walls of the tombs of Ben-Hassam near Thebus, 3000-1700 B.C. These tombs also contain vessels, etc., showing that the artisans were not only acquainted with the making and working of glass, but also Pith the coloring and cutting of glass in imitation of the precious stones. F. iLI. de Roziere also found samples of colored glass in early Egyptian tombs. W. M. F. Petrie collected a t Tell-el-Amarna specimens illustrating all stages of the process of glass-making about 1400 R.C. F. Rathsen gave analyses of antique Babylonian glass. Theophrastus, about 300 B.C., mentioned the coloration of glass by copper; and in his Clouds Aristophanes referred t o a glass lens used as a burning glass. From Cicero, it would appear that glass from Egypt was greatly prized by the Romans; so much so that when Augustus subdued Egypt, 29 B.C , a portion of the Egyptian tribute was ordered to be paid in glass. At the time of Tiberius, Egyptian workmen were imported to Rome, and Roman glass rivalling that from Egypt was soon obtained. Works were also established in Italy, France, and Spain a t an early date. In the second century, H. Philo, in his De legatzone ad Caicum Caligulum, alluded to the use of translucent stones as windows in the halls and chambers of the emperor’s palace, and in the fourth centurv, L. C. Lactantius, in his De opzj;czo Dei,
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mentioned the use of glass itself for windows. It is therefore probable that about the third century glass was employed in the construction of windows; but, according to L. Dutens, the excavations of Pompeii, near Naples, show that a t that time les salles de bain Btaient garnies de fendtres en verre aussi belles que les ndtres. After the fall of the Roman Empire the manufacture of glass was taken up in Byzantium, where it flourished for about five centuries. The fall of the Eastern Empire was attended by the migration of the glass-makers to other parts of Europe. Manv were attracted to the Venetian Republic, and the Venetian glass became famous throughout the civilized world. “In the early Middle Ages, glass-making was taken up in Germany: and in his De re m e t a l h a (Basiliae, I546), G. Agricola gave a drawing of a glass furnace; and shortly afterwards H. Mathesius, in his Sarepta (Nurnberg, 1562), described the practice employed in Venice, Germany, and Bohemia. A. Seri published a number of recipes in 1612, and some years afterwards this work was elaborated by J. Kunckel. “The factories in different localities acquired fame for some peculiarity in manufacture; the Bohemian manufacturers, for example, excelled in the production of colorless glass rivalling that from Venice. The manufacture of glass in Bohemia suffered a relapse owing to the heavy import duties levied against it, and the inducements held out to Bohemian workmen by foreign countries. Both the Venetian and Bohemian glass industries were revived in more recent years. The manufacture of the better types of glass in France commenced in the eighteenth century in factories erected a t Paris and a t St. Gobain. The latter is now famous for the manufacture of plate-glass. According to H. J. Powell, it is possible that during the Roman occupation a few beads, small cups, and bottles were made in England; but the resemblance of the scattered vessels and fragments of vessels to those found elsewhere makes it probable that there were only a few centres of glass manufacture in the Roman empire, and that the vessels were distributed from these to various parts. Glass was manufactured in England in the thirteenth century, for the industry was in existence a t Chiddingfold, Surrey, in 1226. The south-eastern counties-Surrey and Sussex in particular-were favorite spots for the native glass-makers from the thirteenth to the sixteenth centuries. Glass was manufactured in Russia in the seventeenth century; and, in the United States, near the beginning of the nineteenth century. “Theophilus, in the latter half of the eleventh century, related that, in Italy, flint glass was used for imitating gem-stones, and added that the Jews were engaged in the manufacture of these imitations. Towards the end of the eighteenth century, J. Strasser, of Vienna, was famous for his skill in this work. He made a flint glass very rich in lead, and of high refractive power and sp.gr., which was called strass, and which was tinted with the necessary coloring oxides- e.g. 0.8 percent of chromic oxide to imitate the emerald; a mixture with 0.8 percent of manganese oxide, 0 . 5 cobalt oxide, and 0.2 gold purple, to imitate the amethyst,” p. 5 2 0 . “The early observers included mica in the same class as gypsum, which can also be split into thin flakes. It was afterwards noticed that, unlike talc and gypsum, the cleavage plates of mica are highly elastic, and not pliable. Pliny, in his Historia naturalis has a description of a mineral, lapis specularis, which applies very well to mica. The scales of this mineral were strewn over the circus maximus a t the celebration of games with the object of producing a sparkling whiteness. This shows that a mica schist furnished the material employed; and Pliny’s hammochrysos was probably a sand containing golden-colored scales of a biotitic mica. The Hindus appear to have used mica for decoration and other purposes, and they considered it to be endowed with extraordinary properties. Mica has also been found in the graves of prehistoric American races, east of the Mississippi, in localities where the mineral does not occur. ‘!The term mica is not likely to have been derived from the Latin mica, a crumb, or grain, but rather from the Latin micare, signifying, like the German Glimmer, to shine. I n mediaeval timep, scaly mica was called cat-silver, or cat-gold-Katzmgold, or Katzensilber; or des chats, or argent des chats.Thus G. Agricola spoke of Ammochrysos, Mica, Glimmer or Kutzensilber. A. B. de Boodt and J. G. Wallerius described several varieties. A. G. Werner, and A. Estner definitely adopted the term Glimmer, and described many
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varieties. No great progress could be made in the classification of the micas until they had been distinguished from one another by chemical snalysis, and optical measurements,” p.604. “Muscovite is a pyrogenetic mineral which occurs as a primary constituent in deepseated igneous rocks rich in alumina and potash, and poor in iron and magnesia. It is common in granites, syenites, and pegmatites. From its water-content muscovite was probably formed in these rocks under pressure. It does not occur as a primary constituent in recent lavas and their glassy magmas. Muscovite is common as an alteration product of many minerals-andalusite, cyanite, topaz, felspar, nephelite, spodumene, scapolite, etc. 4 s a secondary mineral it is often called sericite. Paragonite is one of the rarer varieties; it occurs in crystalline schists, but does not occur as a pyrogenetic mineral. Lepidolite occurs in granite and pegmatite where it may form violet or lilac-colored crystals associated with muscovite. I t sometimes occurs as a secondary product after muscovite, when it occurs as margins on the plates of muscovite. Cryophillite similarly occurs on plates of leipdolite,” p. 609. “The most important use of mica is in the electrical industry as an insulator. It is one of the best insulators because of its resistance to puncture, pre-resisting qualities, impermeability to moisture, toughness, elasticity, and flexibility; and its cleavage into thin sheets. It is largely used for insulating the segments of commutators, armature wires and bars, etc. Scrap mica is made into sheets, plates, and boards by means of a suitable bonding agentsay, shellac-and under the commercial name micanite, is used for making washers, etc., for insulating lamp-sockets, fuse-blocks, cut-out boxes, etc. Sheet mica is used for lanterns and windows where glass does not withstand the shocks and vibrations. It is also used in place of glass where abrupt changes of temprature would be liable to crack glass-e.g. fire-screens, stove windows, lamp-chimneys, and some miners’ lamps. Special sparking plugs for aeroplanes, etc., are built up froni sheet mica. It is employed as a heat insulator in the lagging of steam-pipes, boilers, etc. I t is used as a sounding-diaphragm in telephones, gramophones, etc. I t is used as an absorbent for nitroglycerol and as a heavy lubricant. Mica is used in making wall-paper pigments; and various ornamental purposes-a mixture of gum arabic and ground white mica makes the so-called silver ink; and it is employed for inlaying buttons, in making lustrous hair-powder, and in making the bronze-like colors which bear the name brocades, crystal colors, mica-bronzes, etc., and in making frosted effects in decoration,” p. 620. “The water in zeolites possesses the property of mobility to a high degree whilst the silicate space-lattice must be considered as relatively rigid. The water molecules entering into the mesh cavities of this lattice will tend, according to their thermal pressure, to become uniformly distributed; on the other hand, the silicate molecules (or portions thereof) in the crystal lattice mill tend to hold by attraction the mater molecules, or a portion thereof, in position in entire conformity with the symmetry of the latice. Both tendencies can b e simultaneously satisfied only if the number of water molecules is a complete multiple of the number of silicate molecules, for only under these conditions can the water molcules arrange themselves in identical formation round each of the other molecules of the silicate lattice. I t is only exceptionally favorable mixtures such as these that give the straight line in the dehydration curve. All other mixtures correspond to Foints on the irregular curves. The zeolites are therefore considered to be solid solutions, but it is an open question whether the water in this solution reacts with the solvent, i.e. forms an intimate compound with the silicate, or whether it enters the lattice as a molecule dissociated into its atoms, or into ions. Wilder D. Bancroft Wire-Drawing and the Cold-Working of Steel. B y A. T . A d a m . 26 X 19 cm; p p . 212. London: H . F. and G. W;therby. Prire: QO shallings. We learn from Mr. Adam’s preface to this book that since the publication in 1891 of Mr. Bucknall Smith’s book on Wire, no textbook dealing exclusively with Wire and allied products of cold-working processes has appeared. The present author, who is in charge of Messrs. Brunton’s research laboratory, has in the present book, written not an exhaustive treatise on the subject, but an account which aims a t explaining the real nature of Wire and other cold-work products. It describes their
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physical properties and it shows how these depend on the treatment the material has received. The book is intended for Metallurgists and Engineers and those who are interested in the product itself, rather than in the process of manufacture. Accordingly machinery and plant are only dealt with briefly, while such matters as quality and the preliminary treatment of the material, the extent of reduction by cold-work and the relation of these matters to the properties of the finished product, have been discussed more fully. The book opens with an introductory chapter followed by two chapters on wire-drawing, including the cold-working operation. Then follow chapters on cold-rolling and other coldworking processes, heat treatment, and tn,o chapters on the effect of cold-work on the physical properties of metals. The important subject of the effect of heat treatment after cold-work is then dealt with, and this is followed by a discussion of the theories of plastic flow in cold-worked metals. The last two chapters are concerned with the pathological aspect of cold-working operations and the application of cold-work to non-ferrous metals and alloy steels. We think that Mr. Adam’s book will be found very acceptable. It is well printed and illustrated: the photographs and drawings are excellent, and the whole treatment of the subject is scientific. The author has made a careful study of modern metallographic research bearing on wire-drawing operations, and his treatment shows that he has understood the vital bearing of certain researches in particular, which are probably destined to have an important influence on the progress of wire manufacture. To mention only one of these, now that the majority of the common metals can be obtained in the form of single crystals, which are characterized, for the most part, by remarkable ductility and malleability, it is clear that the wire-drawing of single crystals may ere long be destined to become a commercial operation. Actually, this is already so in the cas3 of the metal tungsten. We cannot help regretting the high price a t which the book is published, for we fear that it will severely limit its circulation and accessibility. H . C. H . Carpenter Der molekulare Brechungskoeffizient in der Reihe der Polymethylenverbindungen. B y Fritz Eisenlohr. 25 X 14 cm; p. 48. Berlzn: Borntrasger, 1926. Price: 4.20 marks. Although the determination of the molecular refraction [RL] D, of liquid organic compounds has been of the greatest service to the organic chemist as an adjunct in the determination of structure, the application of the method for the latter purpose is limited. A number of constitutive factors do not find definite expression in the value for [RL] and it is only the presence of ronjugated or semicyclic double linkings and three- and four-membered rings which produce exaltations from which inferences regarding structure can be made. The underlying cause of this is the fact that the refractive index and the density vary together so that the differences between related compounds are obscured. The expression S$ X M, in which the density is not taken into account, does not possess this disadvantage (Eisenlohr and Wohlisch: Ber. 53, 1746 (1920); it is claimed that the agreement between the observed values of this “molecular coefficient of refraction” and the calculated values is of the same order as for the value [RL]and a series of additive constants has been calculated.. Constitutive influences are, however, very pronounced giving “exaltations” (E) which are sometimes positive and sometimes negative. Thus, the branching of a carbon chain has a positive effect of 0.45 unit; the introduction of an ethyl group in the place of a hydrogen produces a different effect from that of a methyl group, etc. Ring formation causes an appreciable negative exaltation, different for every type of ring and decreasing regularly from cyclopropane to cyclooctane. The effect of substitution in the benzene ring is different according to the position of the entering group, an ortho substituent giving the highest, para- the lowest exaltation. In alicyclic ring compounds a further factor has to be taken into consideration, namely cis-trans isomerism about the plane of the ring, doubtless owing to its effect on the “packing” of the molecules. The greater part of the work under review is devoted to the discussion of observations on hydrocarbons, alcohols, and ketones of the cyclohexane series.
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The new method is doubtless a step forward towards the correlation of the physical properties of organic compounds with their structure. The choice of temperature (zoo) and wavelength (D) appear to be arbitrary although it may be mentioned that dispersion is taken into account in the experimental portion of the work. In any case, the special value of the method would appear to lie in enabling conclusions to be drawn as to the structure of isomeric or otherwise closely related compounds, when discrepancies due to the calculated constants are eliminated. I t is hoped that the systematic study of organic compounds from the point of view of their molecular refractive index will be materially extended in the near future and that Professor Eisenlohr’s paper is but a forerunner of a more comprehensive G. A . R. Kon work. Die gasanalytische Methodik des dynamischen Stoffwechsels. By W’ilhelm Klein and Maria Steuber. 25 X 18 cm. Leipzig: G. Thieme. Price: 6.40 m a r k This small monograph of IOO pages deals with the various forms of apparatus used in determining the gaseous exchanges consequent upon physiological experiments, or upon pathological conditions met with in clinical practice. The various methods used in physiological experiments for the measurement of oxygen uptake and carbon dioxide output are described with much practical detail, and the text is well illustrated with drawings of apparatus. Specimen calculations are appended as an aid to those unfamiliar with the technique. Amongst the methods described may be mentioned those of Pattendorf-Tigerstadt and Zuntz-Geppert. The section devoted to apparatus for clinical use is much shorter, describing only the Benedikt and Krogh methods. The gas analysis apparatus which is essential to experiments on gaseous exchange is described at length with working details. Many useful hints are given on such practical points as the cleaning of mercury and the sampling and storage of gases, and a number of tables for the simplification of calculation are appended. The order in which the matter is presented is good, but the division into sections is far from satisfactory. Such sections as “The Solubility of Gases in Liquids” and “The Sampling and Storage of Gases” are given equal importance with “Methods of Gaseous Exchange,” which occupies over 70% of the total book, with the result that quite important subjects are almost lost under small sub-headings. d further improvement which may be suggested is that the references should be collected together and printed as an appendix, instead of being scattered throughout the book as foot-notes. In conclusion it may be said that the book is written in easy straight-forward German, so that it may be used as a book for laboratory reference by those who do not read German fluently. W . K . Slater Molekulargrossen von Elektrolyten in nichtwasserigen Losungsmitteln. By Paul Walden. 25 X 16 cm; pp. xi+350. Dresden and Leipzig: Theodor Steinkopff, 1923. Price: paper 82.26, clcth $2.68. The subject is presented under five headings: general remarks on molecules and polymerization; recognition and determination of molecular weights or of degree of polymerization of homogeneous liquids; molecular weights or degree of polymerization of dissolved substances; the molecular weights of dissolved electrolytes by the osmotic methods; general results of molecular weight determinations of salts, acids, and bases in non-aqueous solutions. On p. 18 Walden quotes from Arrhenius. “If a star consisted of hydrogen alone and, like our sun, lost two gram calories per gram of its mass every year, it could keep that up for eighty-seven billion years in case the heat radiated were compensated by the condensation of hydrogen into heavy atoms.” Walden considers, p. 41, that the change of color of cupric bromide solutions from blue to dark-brown with increasing concentration is due to the increasing formation of polymerized cupric bromide (CuBr.Jx. I t is difficult to see how this is consistent with the as-
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sumption of hundred percent dissociation; but of course Ralden does not believe in hundred percent dissociation. Ramsay’s surface tension experiments make the degree of polynwrization of water a t 100’ about 1.5 while Walden calculates it as nearly 2 . 0 , p. 56. On either assumption there is a considerable degree of association and this must have its effect on boiling-point determinations. One would rather like to see a series run a t about 200’ which would only mean fifteen atmospheres or so. On p. 71, Walden quotes Kuster to the effect that solid naphthalene and solid naphthol are both bimolecular. Walden considers molecular weight determinations of 25000 for starch and 5000 for ferric oxide as not unreasonable, p. 84. He quotes results of 4joo for tetra-ethyl ammonium nitrate in chloroform, p. 198, and says that this substance is in true solution; but there must be some error about this. “The constitutive factor of the electrolyte, which often does not show a t all in aqueous solution, becomes of great importance for the strong binary salts in non-aqueous solutions. The non-aqueous solutions furnish the proof that the acids are electrolytes of a different type from the salts because the acids, like hydrochloric acid, trichloracetic acid, and tribromacetic acid, which are as highly dissociated in water as the binary salts, are practically not dissociated a t all in solvents in which the salts are ninety percent dissociated,” p. 311. The associating power of a solvent varies inversely as the dielectric constant, the dissolved salts being polymerized more strongly, the lower the dielectric constant is. Conversely, the dissociating power of the solvent is greater, the higher its dielectric constant,” p. 312. “Through variation of the solvent the same salt of the type of a binary iodide, MI, can be obtained in all stages of polymerization or dissociation a t the same concentration and temperature. At the same temperature and concentration we can therefore obtain a given salt in the form of highly polymerized molecules with an apparent molecular weight of infinity, or in the form of a molecule dissociated almost completely into free ions. n7e get this extraordinary plasticity of the apparently so firmly knitted salt molecule not by making use of special energy factors, but simply by dissolving it once in a so-called indifferent solvent, and the next time in a strongly ionizing solvent. From both solvents we recover the unchanged salt on crvstallization,” p. 312. The author prides himself on the treatment being non-critical; but one cannot share this enthusiasm. Wilder D. Bancrojt Crystals and the Fine-Structure of Matter. By Priedrich Rinne. Translated by Walter S. Stiles. I S X 16 em; p p . ix+i96. New York: E. P. Dutton and Company. Price: S.4.IO. “Crystals are proving themselves more and more the ideal substances of physics and chemistry. Even before the last great discoveries in this branch of knowledge the late Woldemar Voigt, Professor of Theoretical Physics a t Gottingen, who had a unique knowledge of this subject, drew attention t o the exceptional regularity of the crystalline parts of matter in a fine simile, which is quoted below: “Imagine a couple of hundred picked violin players in a large room, all playing the same piece of music on faultless instruments, but beginning simultaneously a t widely different places, and starting afresh each time they reach the end. The finest ear would be unable to recognise the piece actually played in this uniform medley of sound. r o w such music is presented to us by the molecules of gaseous, liquid, and ordinary solid bodies. A crystal, on the other hand, corresponds to the orchestra described above when it is guided as a whole by one able conductor, so that dl eyes hang on his slightest gesture, and all hands play the same bar. I n this way the melody and rhythm of the piece presented became completely effective, the number of the performers not hindering but intensifying the result.” “This picture makes it clear how crystals can present a large series of phenomena which are absent in other bodies, and that, in them, certain characteristics are developed in wonderful variety and elegance, which elsewhere occur only as monotonous mean values,” p. 2 .
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“I introduce the expression fine-structure-study, or leptology, because the customary term stereochemistry does not cover completely the field of the inquiry intended. I n stereochemistry we study the form and arrangement of the particles comprising various substances in order to explain thereby their chemical properties. Alongside this science, another has arisen, which may justly be termed stereophysics, and this also is concerned with the constitution and association of the particles of matter. dealing especially with their movements and physical properties (e. g. crystal optics). Finally, a third allied subject is included, namely, crystal structure, or the study of the fine-structure of crystalline bodies from the point of view of their geometrical relations. “Thus from the trunk of Greek Atomic Theory, which is more than two thousand years old, three branches of knowledge have sprung forth and blossomed-stereochemistry, stereophysics, and crystal structure. Their intimate relations to one another justify a name to include them all. If now the particles of matter, the electrons, atoms, ions, and molecules which constitute gases, liquids, and crystals are termed collectively fine-structureparticles or leptons (from XETTOS, fine, delicate), the name suggested above, fine-structurestudy or leptology indicates precisely the end in view,” p. 5. “Substances built up of flakes, which lie with all their fibre axes or flake normals parallel, but otherwise indifferently, give on the passage of X-rays perpendicular to this direction and X-ray effect similar to that of a crystal plate which is rotated about an axis passing through it. The series of reflexions, one after the other, produced by the latter, as a result of the rotation, are shown by the pack of fibres or flakes simultaneously. All fibres or flakes, the structure planes of which satisfy the equation nX-2~ sin u give rise to reflected rays. As was shown by H. Seeman and E. Bchiebold, in particular for rotating plates, and R4. Polanyi for fibrous substances and stretched metals, we get in this way characteristic diagrams,” p. 17. On this statement of facts, X-ray photographs apparently do not show whether a fibrous or flaky substance is or is not crystalline. “The idea of deriving the multiplicity of crystallographic forms from five types all mutually connected, which may be called primitive forms, has already been brought forward by G. v. Tschermak, and followed in his teaching,” p. 28. The five primitive forms are called: pedion, pinacoid, sphenoid, doma, prisma. “The chief difference in the construction of crystalline bodies and the individuals of amorphous substances lies in the restriction of the rhythm. I n the fine-structure of crystals, owing to the fact that each structural unit is joined to its neighbours, this rhythm exhibits a three-dimensional periodicity. Such space-lattice structure is clearly only possible when the repetition is according to the numbers 2 , 3 , 4 , and 6. or with no repetition a t all. Pentad, septad, and compound axes of higher period are here theoretically excluded, nor are they found in practice,” p. 49. “The change of physical properties with direction is very obvious in crystals showing cleavage. Thus for rock-salt there are three directions, perpendicular to the cube surfaces, in which the cohesion of the crystal is a minimum. The resistance to splitting in these directions is only one-third of that in the direction of the cube diagonal. The cleavage planes are, therefore, regularly oriented surfaces of maximum brittleness. I n like manner, many crystals show particular planes of maximum plasticity. These are surfaces in which internal displacements may easily occur; with ice they arise as planes parallel to the surface of the ice floe. Hardness is also a directional property in crystalline materials. The resistance to disrupture, which shows itself as hardness, is often different in different directions of the crystal; thus it is a familiar fact to diamond workers that the cube surfaces of thc gem aremore difficult t o prepare by polishing than the octahedron surfaces. Garnet, too, is hardw on the cube surfaces than on the octahedron and rhombic dodecahedron, according to the researches of P. J. Holmquist on polishing. Even on the same surface of a crystal the hardness, as measured by scratching, varies with the orientation of the scratch made by the test needle. Cyanite is a classical example of this,” p. 5 5 . “The great disperseness of gases is enormously diminished on crystallisation: in liquids, too, in general, the same thing occurs. I n this connection some figures for sodium and the diamond, as two extreme types, will be of interest to the reader.
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Number of atoms sodium per C.C. Gas at boiling-point (82oOC) 2. Liquid at boiling-point I.
3. Liquid a t solidifying-point, 97.6”C. 4. Crystal at solidifying-point
24,500 xI018 25,000
x I018 11.03
“In solid sodium, with its body-ccntred space-lattice (only two atoms in the elementary cell) and its large U-value for the cube edge (4.3 X I O -em.), ~ we are dealing with a soft metal. The condensation from gas to fluid is considerable; that for fluid to crystal, small. With the hard, compact diamond (eight atoms in the elementary cell, u ‘3.53 XIO-8cm.), a much more extensive condensation occurs on crystallisation; I C.C. of this gem contains 180,000 trillion carbon atoms, compared with 1.3 trillion in carbon vapour at 5soo’C. Naturally, with such close packing of the particles of matter, the cohesion between them becomes enormous,” p. 66. “Considering the results already obtained in crystal leptology with a view to a physical chemical interpretation, the desired organisation into radicals is, in fact, often definitely shown in the architecture. The Braggs, as originators of fine-structural schemes, have pcinted out the dumbbell-like connection of the two sulphur atoms in iron pyrites, and, in somewhat greater detail, P. Siggli has expressed the opinion that the representation of the complete crystal as a purely atomistic space-lattice complex certainly may always be carried out formally, but that many inter-connections between certain atoms forming structural groups (as P. Xiggli called them) stand out clearly on a merely architectural consideration of the schemes. These structural groups I have designated geometrical radicals or leptyles in adaptation to chemical ideas. Finally, groups of a molecular nature are occasionally unmistakable in the crystal arrangement. Such leptyles occur in iron pyrites with its doublet Sz,in calcspar with the ion COS, and in rutile and anatase with the molecular Ti02 complcx. A fine example of leptyle grouping has been investigated by Dickinson (1922). Moreover, for organic suhstances with ring formation, such a finestructural grouping must be assumed according to €’. v. Groth, who formerly brought into prominence the atomistic crystal structure. As regards cyclic chains of atoms so fundamental chemically, which can with certainty be attributed to the molecules of benzene, naphthalene, and other organic substances, it is more than probable that these chains persists in crystallisation. Crystallised organic compounds will often be molecular aggregates loosely knit into space-lattices. This conception W. H. Bragg has taken as fundamental in his present researches on organic compounds,” p. 90. “The undermining of crystals may, however, take place to an extent much greater than is represented by the removal of a relatively small part of the constituents which water iisually reprrsents. The calcium aluminium hydrosilicate CaOAlzO86SiO~ca.5. j aq. of heulandite, for example, may be reduced fine-structurally to SiOz. The entire filling of basic constituents is then removed, the result being just as though the skeleton of some siliceous plant had been prepared by burning the organic wrapping. The relict of the zeolite so obtained still shows (especially after glowing, probably under the influence of collective crystallisation) definite optical agreement with the original substance, the hard rigid pseudomorph of which it represents. If, starting from desmine zeolite, all the basic constituents are simultaneously withdrawn with hydrochloric acid, a Si02 optically analogous to the original desmine is obtained. Thus the same chemical substance Si02 appears here to have a varying structure depending on its previous history; in the one case it is a heulandite, in the other a desmine residue,” p. 151. “The space-lattice constitution of the crystal must serve as the fundamental conception in this work. In its particular fine-structural symmetry and special tectonic nature are characterised the physico-chemical connections of the particles. AR a result of this, for every particular case we find a t once certain indications as to the mechanics of the chemical processes in the bodies concerned, and a basis for generalisation is obtained. Since, for example, CaC03 of calc-spar, which is constructed from Ca“ and CO, ions in a ternary
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rhythm, undergoes, on heating, the well-known reaction of splitting into CaO and COZ, it must be assumed for the fine mechanics of this process that, on account of the increased heat motions, first the geometrico-chemical radical COS, as a ring of three 0’s about a centre carbon, becomes loosened in the fine-structure. With increasing temperature these radicals, together with the calcium atoms, which are free moving groups in the material field, undergo R separation into COn and 0, which links up with Ca to form CaO. “Arcording to this, the loosening of the particles in the fine-structure is always t o be regarded from the standpoint of symmetry action. Those particles of the structure, coupled together by rhythm or reflexion, participate simultaneously in the process, and since wch coupling thus occurs throughout the entire crystal many million times, the process appears to us in analytical chemistry as a disontinuous change, possibly in a series of steps, if the new arrangement contains the departing component again in definite symmetry disposition, as is the case, for example, in the ignition of gypsum to the subhydrate. d practically steady variation can have its origin in complicated re-groupings of the point system, closely following on one another,” p. 158. Wilder D. Bancrojt
A Text-book of Organic Chemistry. By B. de Barry Barnett. 21 X 14 em; p p . xii+-380. Philadelphia: P. Blakisfon’s Son and Co., 1920. Price: 86.00. I n this general survey of the most important classes of organic compounds, the author has attempted to emphasize group reactions rather than the reactions of individual compounds, so that t’he number of individual subst’ancesmentioned is smaller than is generally the case. However, the group reactions are illustrated by means of specific cases in the usual way. Although descriptions of analytical methods must necessarily be meager in a book of this type, mention might have been made of the use of the Parr bomb in determining halogens and sulfur in organic compounds, since it is extensively used. Whether or not the arrangement of the material is the best possible one is probably a matter of personal opinion. All of the general theories (Isomerism, Stereoisomerism, etc.) are presented in the Introduction, “as they are more easily referred to when necessary”. The compounds are classified in the usual way and all of the members of one class are considered together, rather than dealing with the simpler members of the various classes first and then treating the more complex subst,ances later. The material covered is quite up-to-date, although some things have been omitted that might well have been included. For instance:-The preparation of ache aldehyde from acetylene and the conversion of the aldehyde into acetic acid and alcohol are discussed. S o mention is made of the fact that the acetic acid thus obtained is converted into acetone by passing its vapors over hydrated lime a t 485”. Bakelite is not mentioned. Unusual features of the book for an elementary treatise are ( I ) a brief discussion of the available literature, (2) a list of t,he more important books dealing with the subject’ matter is placed at the end of each chapter and (3) the objections to the Kekul6 formula for benzene are considered. With regard to the index, the convenient feature of printing the main references in heavy type is not followed. Ralph T . K . Coinwell A Systematic Handbook of Volumetric Analysis. By Francis Sutton. Eleventh edition. Revised by W . Lincoln Sufton and Aljred E. Johnson. 22 X 16 em; p p . xiiS689. Philadelphia: P. Blakiston’s Son and Company, 1924. Price: $9.00. The authors have endeavored in this edition to cover the volumetric methods for the analysis of ores, ferrous and nonferrous materials, water and sewage, organic substances, urine and gas and “to describe all the operations and chemical reactions as simply as possible.” Therefore, it is not surprising in a text covering so much material that some errors of omissioh are made, such as electrometric and conductivity titrations, benzoic acid as an alkalimetric standard, some of the better methods for aniline and phenol and most of the American advances in gas analysis apparatus.
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I t is surprising, however, to find in the I I t h edition of a book the use of “floats” instead of the complete circling of burettes by graduation marks a t major points as advocated by the U. S. Bureau of Standards and the statement that after a burette is rinsed with a solution, it “is nearly filled with the solution and a considerable amount of the liquid allowed to flow back into the bottle from which it is being filled.” A few careless errors have been made such as ‘‘2Na2C2O4yield 02”and the placing of a soda-lime guard tube for alkaline solutions in a vertical position. However, this work contains a great variety of volumetric methods for all of the determinations covered and numerous references to the literature. For this reason it will undoubtedly be of value t o analytical chemists as a very handy reference book. The reviewer feels, however, that the value of the book would be greatly enhanced if the authors had indicated which method they considered the best for each individual determination. M . L. Nichols Quantitative Analysis. By Stephen Popoff. 20 X 14 em; p p . xiai+342?. Philadelphia: P. Blakiston’s Son and Co., 1924. Prace: $2.$5, The author states that his objects in writing his book are threefold: First, to incorporate in a single book, theory, laboratory instructions, problems and their explanation; second, to emphasize the law of mass action and the theory of equilibrium as applied to quantitative analysis and third, to incorporate some of the more recent advances in this field. I n satisfying the first purpose, there is nothing to warrant an extra need of praise. A normal solution is defined as one which contains I g. of hydrogen equivalent per liter of solution. In accomplishing his second purpose, much material is included which is generally found in texts for qualitative analysis and there are certain principles of physical chemistry not usually to be found in quantitative analysis texts, e.g., van der TYaals’ equation and for which the author feels it necessary to present an “excuse”. I n the section dealing with special topics, we find electro-analysis, food analysis, iron and steel analysis, and electrometric titrations. For laboratory practice in the first three topics, the author issues supplementary mimeographed instructions. The chapter on electrometric titration is the redeeming feature of this section. M . L.hTtchols The Properties of Matter. By Basil C. JfcEwen. 20 X 14 em; p p . vii+316. New York and London: Longmans, Green and Co., 1923. Price: $3.20. “The order followed is the reverse of that adopted in most Text-books dealing with the Properties of hlatter. “Commencing with the First Law of Thermodynamics, an extension is made to the more general Principle of the Conservation of Energy, and hence to the metaphysical conception of the Identity of Energy throughout its various transformations. “Since our knowledge of mechanical systems is, in general, more complete than that relating to other modes of energy, a logical sequence leads to the study of the Kinetic Theory of Matter, the consequences of which can be most fully developed when applied t o matter in the gaseous state. “The Properties of Gases are, therefore, next investigated from the standpoint of the Kinetic Theory, and the continuity of the gaseous and liquid states supplies the natural transition to a detailed study of liquids. The Properties of Solids are dealt with last. “It is thought that this method of treatment is simpler, and follows a more natural sequence than is attained by commencing with a study of the Properties of Matter in the solid state-and proceeding, in the reverse order, to a consideration of Liquids and Gases,” P. 5 . The chapters are entitled: the first law of thermodynamics, the kinetic theory of matter and its application to the gaseous state; isothermal and adiabatic transformations and the specific heats of gases; the elasticity of gases, and the continuity of the liquid and gaseous states; the thermal cxpansion, diffusion, and solubility of gases; equations of state; liquids, capillarity; solids; gravity. There are also three appendices; the Joule-Thomson effect; the theorem of LeChatelier; units and dimensions. W i l d e r D. Bancroft
