INDUSTRIAL A N D ENGINEERING CHEMISTRY
98
Vol. 16, No. 1
WORLD-WIDE CHEMISTRY Paris Letter By Charles Lormand 4 AVENUEDE L’OBSERVATOIRE,
PARIS,
FRANCE
...... VOLCANIC VAPORS FOR POWER Among various interesting communications of the past month should be mentioned the communication of Prince Ginori-Conti, the Italian senator, whose factories of the Larderello produce the greater part of the boric acid now used. The communication had for its object an explanation of the utilization of the “suffoni” or geysers, which emit, a t the same time as boric acid is emitted considerable quantities of vapors which are used in turbine alternators, furnishing a motor power of 2500 kilowatts. By increasing the number of borings in the region it has been possible to obtain 150,000 kilograms of vapor per hour. The utilization of this vapor ought to be extended to the other volcanic regions of Italy (of Vesuvius and Etna), and Prince Ginori-Conti mentioned experiments now under way in the United States along this line.
011.SUBSTITUTES FROM HYDROCARBON GASES Soon after it was exploited I mentioned the deposit of hydrocarbon gases in the Vaux region, of which the daily output was a t first 100,000 cubic meters per day, and which has now been 60,000 cubic meters for several months. It seems that this amount should not get any lower and the gas contains 90 per cent of combustible gas with a heating value of 9600 calories. This gas, aside from its use for the lighting of the towns in the neighboring region, can be compressed and placed in cylinders to be used like cylinders of acetylene. The use of these hydrocarbon gases, methane and acetylene, for the production of substitutes for oil has been the object of experiments by M. Zelinsky, who has repeated the conditions of the original experiments of Berthelot on the polymerization of acetylene and its transformation into benzene. In employing activated carbon-that is, wood carbon rendered particularly adsorbent, carbon which was used in gas masks during the warhe has been able to prepare liquid analogs to petroleum from acetylene. A current of acetylene is passed over carbon heated to 640” C., and thus, with a 70 per cent yield, a liquid with a density of 0.911 is obtained, containing 45 per cent of products boiling between 20” and 150” C., 13.9 per cent boiling between 150” and 250” C., and finally, 29 per cent boiling between 104” and 300” C., under 13 millimeters pressure. Among these products the most conspicuous are benzene, xylene, naphthalene, and their homologs. Another use for acetylene has been pointed out by ht. Sabatier, who has shown that the decomposition of calcium carbide in aqueous solution in the presence of certain metallic salt solutions can produce carbides or acetylides which until then had not been isolated.
EFFECT OF EARTHQUAKES ON NATURAL GASES The relation that may exist between the composition of certain natural gases and the earthquakes has been the object of a very important piece of work by M. Cremieux, who exploited for many years a nitural source of carbon dioxide located a t Colomieres (HCrault), in the “terrains archeens.” Numerous fissures in this block are made directly available for obtaining carbon dioxide, which is then liquefied. The content of carbon dioxide in the gas is about 95 per cent, the remainder being a mixture of nitrogen, oxygen, and rare gases. Different analyses of this residue have shown great variations in its percentage composition. The following is an example of typical analyses: Per cent Nitrogen. Oxvzen.
. . . . . . . . . .. . . . . . . . . .
...........
Rare gases
{
Argon. .....................
................... ............................
(1)
(2) 91 6.9
70 27 2.15
0.35 Helium. Radium emanations, in curies X 10-1 per liter..... 2400
12.5
0.45 175
t
The emanation content increased progressively from 8 millimicrocuries in 1912 to 18 millimicrocuries in 1923. The important point of the communication of M. Cremieux consists in the Fact that these gases, destined to industrial usage, are analyzed daily. He stated that on the 15th of last July the gas had a carbon dioxide content of 96 per cent; this amount fell suddenly to 89 per cent on the 16th of July. He learned that a slight trembling of the earth had taken place in the region and immediately he had installed a seismograph, the installation of which permitted him to notice the absolute parallelism between the tremblings of the earth and the diminution of carbon dioxide. The greatest diminution in the carbon dioxide content was found on the 4th of September, the date of the Yokohama earthquake, when the amount gradually increased to 94 per cent on the 25th of September, the date on which no more shocks were registered. M. Cremieux interpreted this phenomenon by saying that the earthquake causes a liberation of inactive gas from the inidst of the earth, the abundant emission of which decreases the carbon dioxide content, a gas younger and more superficial in the earth’s crust However, as far as the variations in the content of radium emanations are concerned, which does not follow a parallel course, no satisfactory explanation has been found. The radium emanation from these sources of carbon dioxide is likewise used industrially. After elimination of the carbon dioxide and other rare gases, the radium emanation is condensed and sold for medical purposes. NEW USE FOR HEAVYGASES Gases with heavy atomic weight have, moreover, recently been proposed for a new use. M. Lepape has suggested the use of krypton for obtaining radiographs. It is known that salts with liigh molecular weight (bismuth carbonate, barium sulfate) are now being iised for diagnosing various illnesses. These salts introduced into the various cavities of the organism permit obtaining radiographs, with the shadows locating the position of the organ. M. Lepape obtained a very nice radiograph of a frog into the lungs of which krypton had been blown. The lungs full of air give a transparent radiograph when, refilled with krypton, their outlines are neatly drawn and permit localization. The absolute inactivity of krypton from the chemical point of view gives it a superiority over the salts of bismuth or barium, which are more difficult to use than a gas. PRESERVATION OF ZOOLOGICAL SPECIMENS M. Bertrand believes there exists a compound of copper and oxide of carbon analogous to nickel carbonyl. He expressed this view in presenting to 1’ AcadCmie des Sciencesa communication from M. Zelinsky. The latter, in heating in a current of carbon dioxide powdered insects with copper oxide, obtained on recooling a complete metallization of the body of the insect. The organic parts of the body of the animal were carbonized and formed a coke covered with a slight film of metallic copper. The carbon dioxide had been reduced by the carbon from the body of the animal and the copper carbonyl dissociated by the heat liberated from the copper, which metallized the body of the insect. This method is adaptable to a number of applications for the preservation of the lorms of zoological specimens.
RADIOENGINEER HONORED L’Acadhie des Sciences has recently awarded a prize to M. Lee de Forest, a member of the American Institute of Radio Engineers, for his invention of lamps with three electrodes, the use of which in wireless telephones there is no need of describing. RUHRINDUSTRIAL AGREEMENT The cessation of German resistance in the Ruhr will materially affect the chemical industry, since in the agreement recently made it was announced that the Interallied High Commission has signed with the representatives of the factories making chemical products and dyes, notably with Badische, an agreement t o turn over supplies in payment for work, as a reparations measure. Furthermore, the control of these factories will be taken over according to the terms fixed by the peace treaty and
INDUSTRIAL A N D ENGINEERING CHEMISTRY
January, 1924
this control will apply especially to the question of armament. It is not necessary to emphasize the importance of this measure, which makes possible the control by the Allies of chemical factories, which will thus be able to devote themselves to work and studies on war gases.
GASLIGHTING EXPOSITION I might mention now that there will be in France, from May 31 to July 31, an international exposition of gas lighting to celebrate the fifticth anniversary of the use of gas. A number of congresses and conferences reporting on the gas industry and its by-products will take place a t this time, .and these should attract chemists interested in the gas industry in all parts of the world. November 30, 1923
German Letter By Walter Roth COTHEN,GERMANY
...... DEATH OF PROFESSORS FRIEDLANDER AND HARRIES In the last few weeks the chemical world has mourned the loss of two chemists, both of whom have done noteworthy work in the field of organic chemistry, but who in personality and appearance were of quite different natures-Friedlsnder, a typical scholar, modest, quiet, devoted t o his work, without striving for further honor or success-Harries, on the other hand, a man of the world, fearless; both ,have shown through their work, directly and indirectly, new methods of technic. Friedlander, whose “Fortschritte der Teerfarbenfabrikation,” is well known throughout the world, through his research on the purple which became famous in the Bible, found this color to be a thio-indigo, and discovered a series of new colors. Harries studied the effect of ozone on organic compounds, explained the chemical nature of rubber, and completed its synthesis. If under the present economic conditions synthetic rubber plays a small part compared t o natural, and large-scale experiments on the production of synthetic rubber have been given up, nevertheless, in time of war synthetic rubber played a definite role in the equipment of Uboats. In recent years Harries has devoted his work entirely to the Siemens concern and directed the “Zentralstelle fiir wissenschaftlich-technische Forschungsarbeiten des Siemens Konzern,” organized by him. NATUREO F THE INTERIOR O F THE EARTH In the last decade science has been specializing more and more and has lost the connection with the whole. The natural sciences in particular have differentiated from each other and each separate branch has devoted itself entirely t o its special task. All the more is it to be commended, then, that chemistry has recently been concerned with general scientific problems. Reference is made to the “Erda” stock company, which in its “Institut fur angewandte Geophysik,” in Gottingen, is working on investigations on the nature of the interior of the earth, and the problem of earth appraising. In Gottingen, the well-known investigator, Professor Tamman, in the “Institut fiir physikalische Chemie der Universitat,” has recently begun experiments on the structure of the earth. According to the results of Seismik, the earth consists of a shell about 1500 kilometers thick with a density of 2.9; under this is a middle layer about 1400 kilometers thick having a density of 5.6; and below this is the core, with a density of 9.6. The densities of these layers point to the fact that the outer shell of the earth is composed of silicates, the middle of sulfides of the heavy metals, and the core of metals. Tamman estimates the composition of the earth as follows: Silicate layer Sulfide layer Metal core
Thickness Km. Densitv 0 t o 1500 2 . 9
1500 to 2900 5 . 6 2900 to 6370 9 . 6
3
ComDosition l(AlzO8, FeiOa, FeO, CaO, MgO, KzO, NazO)
1.6 SI02 FeS, FesP, FeO, Fe, Si02 Fe SS%,, Ni, S%, F e (sulfide and
-
ihosphide), 3%; noble metals, 1 4. I”
The melallic core is, according to Tamman, a nickel iron, whose nickel content corresponds with the average nickel content of meteoric iron. PRODUCTION O F ARTIFICIAL BUTTER Margarine has in Germany in recent years, as a result of the hard economic conditions, attained a much greater importance than ever before. It is therefore natural that attempts are being
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continued to improve its quality and to make it more like butter. New experiments are being made, such as the well-known fat chemist, Dr. Normann, of Herford, described a t the meeting of the Vereins Deutscher Chemiker” in Jena, to add to artificial fat mixtures butyric acid, which is characteristic for butter. Anhydrous butyric acid is heated with a natural fat or oil, The butyric acid enters the glyceride molecule until a state of equilibrium is reached and sets another fatty acid free. The utilization of processes of this sort is a t present limited by the scarcity of butyric acid. But, as it was possible in war time to so conduct alcohol fermentation that a larger crop of the by-product glycerol was obtained, ‘so Normann hopes that fermentation chemists will also be successful in producing through fermentation, from the waste materials such as sulfite liquor, etc., butyric acid in quantities. Also waste water from the steeping of flax as well as from dairies may perhaps furnish butyric acid and similar fatty acid in sufficient quantities. MANUFACTURE O F SYNTHETIC METALS ~ S T A N C E S Formerly alloys were made by mixing metals well together in the fluid state and then leaving the bath to solidify. Recently it has been recommended, however, to prepare the alloy, not in the fused mass, but out of raw material in the powdered form and then to expose to heat treatment. Dr. Sauerwald described some new methods of this kind a t the meeting of the “Deutsches Gesellschaft fur Metallkunde” in Berlin. According to a process of this kind, for example, the so-called “stamp alloys” of Guertler and Pirani are made. This same process has already been used for some time in the manufacture of metal filament lamps, but it is also capable of further use for the production of objects from a single metal. A preliminary condition is, of course, a cheap method of preparation of the powdered metal. USE
O F LIQUEFIED SULFURIC
ACIDIN
INDUSTRY
As is well known, the purification of Rumanian petroleums has offered great difficulties, as it was not possible to obtain from it, a s from the Pennsylvania or the Caucasian crude oil, a satisfactory lighting oil through treatment with sulfuric acid. It was Professor Edeleanu, of Berlin, who was a t the time in charge of the laboratory of the Rumanian Government, who about twenty years ago, after extensive experiments, succeeded in purifying the Rumanian oil through treatment with liquid sulfuric acid. A special apparatus was designed which was found to be adaptable in refineries of quite different kinds. Recent investigations show that liquid sulfuric acid can be used with advantage elsewhere in industry. In the middle German lignite-tar industry, hard and soft paraffins have been separated from the lignite oils by means of sulfuric acid, producing cold, stable oils. Greases can be separated in this manner from the materials which harden them and make them viscous. Petroleum products rich in sulfur are desulfurized in this way, as also is anthracene refined. UTILIZATION OF LEAVES OF TREES It has already been suggested many times that the falling leaves should be utilized. They are said to be used for the manufacture of paper, but most experiments and suggestions have been directed towards making leaves useful for food for animals. The “Versuchss tation fur die Konservenindustrie” in Brunswick, has been working on this problem and Dr. Serger has written briefly concerning the results of this work in Chemiker Zeitung. The foliage of a middle-sized tree weighs about 60 kilograms. If only half of this is harvested each tree will furnish 25 kilograms of green leaves. Green foliage gives an average of 33 per cent dry substance. Then, out of this “leaf hay,” which is first dried by the air and then artificially, a product is obtained which is similar t o bran and can be used for food for animals. With a crop of leaves of 26 kilograms from one tree about 7 kilograms of bran can be obtained. November 18, 1923
Activity in Madagascar Wax Trade-According to the American Consul a t Tananarive, considerable activity has taken place recently in the gathering and exportation of a product called “lokombitsika,” a kind of gum or wax produced principally in the Province of Fort Dauphin, in the southern part of Madagascar. This material is said to be formed on the branches of trees in the forests by a kind of ant insect known as the “Gascardia Madagascariensis.” Recently, its exportation has been confined to France, where it is employed in connection with the manufacture of varnish. It is sometimes sold as gum lac. Previous to the war sample lots of this wax were sent to Germany by the German firms then doing business in Ma.dagascar.
