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T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
Vol. 9, No.
II
NOTES AND CORRESPONDENCE A SOCIETY OF CHEMICAL INDUSTRY IN FRANCE The following extract from a circular now being sent out is self-explanatory : To the Chemists &f Manufacturers of America: There has been formed in France a French Society of Chemical Industry, the Societe de Chimie Industrielle, whose objects are fully set forth in the attached letter (not given here) of Mr. Paul Kestner, President of the Society. After consultation with Mr. R e d Engel, Secretary of the Society and a member of the French Scientific Mission in the United States, the undersigned committee believes that it would be most opportune to establish an American section of the Societe de Chimie Industrielle and thus extend to our French fellow chemists and manufacturers, our moral and financial support and the right hand of good fellowship. Furthermore, members of the American section will benefit by the closer relations which will naturally develop between American and French Chemical Industry. Jerome Alexander Charles A. Doremus Charles I,. Parsons
Leo H. Baekeland Raymond F. Bacon Wilder D. Bancroft Charles Baskerville Albert Blum Henri Blum Marston T.Bogert M. Ceresole Arthur M. Comey
John V. N. Dorr W. M. Grosvenor Frank Hemingway Ellwood Hendrick Chas. H. Herty J. B. F. Herreshoff George F. Runz Parker C. McIlbiney William H. Nichols R. E. Orfila
Charles I,. Reese Allen Rogers Samuel P. Sadtler Maximilian Tocb G. W. Thompson G. E. Vdabrigue E. P. V. Verge Henri Viteaux C. B. Zabriskie
After the above introduction the circular contains the translation of a letter addressed by Mr. Paul Kestner, President of the Society, to the chemists of France, an extract of the ByLaws of the French Society, the list of officers of the Society, and a blank to be used as an application for membership in the American Section of the Society. Copies of this circular may be obtained by addressing the “Organization Committee of the American Section of the Societe de Chimie Industrielle, c/o Chemists’ Club, 50 East 41st St., Ne‘w York City.”
TWO LETTERS ON THE AVIDITY OF SOIL ACIDS Editor of the Journal of Industrial and Engineering Chemistry: In an article appearing in THISJOURNAL, 8 (1916), 344, Truog describes a method which he has developed for the measurement of the avidity of the active soil acids. Briefly, his method is as follows: To a weighed sample of soil is added an amount of potassium acetate solution which contains an amount of the salt equivalent to the active soil acids in the sample. The active soil acids are previously found by determining the amount of standard barium hydrbxide it takes t o neutralize the soil acids in a given length of time. Potassium acetate solution and soil are shaken together for two minutes when the mixture is filtered and an aliquot of the filtrate titrated with sodium hydroxide solution, using phenolphthalein indicator. The avidity is calculated from the followihg formula, the chemical symbols standing for equivalents: NaOH KCtHaOz NaOH This factor times the avidity of acetic acid, taken arbitrarily as 1000,gives the avidity of the soil acids. Truog points out that since the soil acids are relatively insoluble, the avidity as found does not represent the strength of the soil acids, compared t o acetic, but that the avidity figures for different soils are comparable with each other because the acids are all quite insoluble. The purpose of this note is to point out that Truog does not in any sense of the word measure the avidity of the soil acids. In none of the text books of physical chemistry is any mention made of a titrimetric method for the measuring of the strength of acids. It is not the place here to go into a discussion of these methods. I n the 4th English edition of Nernst’s “Theoretical Chemistry” on pages 557 to 563 an outline of the theory of the
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various methods is given, and, obviously, it is theoretically wrong when determining the strength of acids to titrate. Truog’s method measures nothing more nor less than the amount of acids soluble in potassium acetate. Whether or not such a knowledge is of value we do not wish to discuss here. R. S. POTTER IOWA STATECOLLEGE EXPERIMENT STATION AMES. IOWA,September 12, 1917
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Editor of the Journal of Industrial and Engineering Chemistry: . I n reply to the criticisms of R. S. Potter regarding the method proposed for the determination of the avidity of the active soil acids, I wish t o state as follows: The avidity of an acid has reference t o its relative strength, affinity or competing power for a base. Various methods have been proposed for the determination of the avidities of the common water-soluble acids. Thomsen’s thermochemical method and Ostwald’s volume method have been most widely used. Physical properties such as refractive indices, rotary powers, catalytic effects, electrical conductivities and biological effects have also been used to determine the relative strengths of acids. AS the writer has indicated in the Journal of Physical Chemistry, 20 (1916), 473, soil acids are usually Comparatively insoluble and hence the methods proposed for use with the common soluble acids cannot be used in the case of soil acids. I n the method proposed by the writer for the determination of avidity, the active soil acids are first determined quantitatively. By active soil acids is meant those acids which react with a soluble base almost instantly. Although these active soil acids are for the most part not in true solution, yet their physical condition is such (colloidal) that they react with surprising rapidity and some exhibit considerable avidity. After the amount of active soil acids has been determined, a known weight of soil is treated with a solution containing an amount of neutral potassium acetate which is chemically equivalent t o the active soil acids present. The single addition of the potassium acetate is equivalent t o adding separately, chemically equivalent amounts of acetic acid and potassium hydroxide. There results thus virtually the condition that chemically equivalent amounts of active soil acids, acetic acid and base in the form of potassium hydroxide are present in the mixture. The active soil acids are thus given an opportunity t o compete with an equivalent amount of acetic acid for a definite and equivalent amount of base, as is done in Thomsen’s thermochemical method and Ostwald’s volume method. Obviously thermal effects or volume effects cannot be used t o determine the distribution of the base between the active soil acids and acetic acid. However, since the base that combines with the active soil acids forms salts which are comparatively insoluble in water and leaves in solution an amount of free acetic acid which is chemically equivalent to the base that the active soil acids have removed from solution, it is only necessary t o filter the mixture and determine in the filtrate by titration the amount of acid present, in order to determine the amount of base which the active soil acids removed while in competition with an equivalent amount of acetic acid. By substitution in the formula comparative figures for different soils are obtained. The figures represent the collective, or better, average avidity of all the active acids in any particular soil sample. As far as the writer is aware the method described in THIS JOURNAL, 8 (1916), 344, is the only method that has ever been proposed for use in case the acids are not in solution, and it is not at all surprising that Potter finds no mention of a titrimetric method in the text books of physical chemistry. Such methods as are mentioned, are for use under conditions in which the acids and salts formed are in true solution, and obviously
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Nov., 1917
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T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
the method proposed for active soil acids could not be used in case all the acids and resulting salts formed a true solution. Potter states that the method measures nothing more nor less than the amount of acids soluble in potassiumacetate. There is absolutely no basis for this statement. In the case of the common acid upland mineral soils, it is usually impossible t o wash out with water any considerable amount of the acids causing soil acidity, and usually the more these soils are washed with water the more acid do they become. If these soils are treated with a salt solution, the soil acids remove from the salt solution a certain amount of the base and thus liberate from the salt an equivalent amount of free acid in solution; or the soil acids may exchange wholly, or in part, iron and aluminum for the base of the salt, whi6h again gives rise to a n acid solution due t o the ease of hydrolysis of iron and aluminum salts. The potassium acetate solution does not in any way dissolve any appreciable amounts of the active soil acids. While it is perfectly evident that the avidity of a n acid in colloidal solution is different than when in true solution, yet this does not affect the purposes of the method proposed. I n the method proposed only such soil acids (active soil acids) as are free to react quickly with a base are considered. A method to be of any value in studying the effects of soil acidity on the fertility of these soils must measure the avidity of the soil acids in the condition that they actually exist in the soil. This is done as nearly as possible in the method proposed. As the writer has pointed out in Wisconsin Research Bull. 41,p . 34, it is undoubtedly these active soil acids which limit the supply of calcium carbonate and bicarbonate in the soil solution to such an extent that the crop-producing capacity of some acid soils is affected. If this is the case it is evident that the avidity of the acids causing soil acidity may be of more importance than the total amount of acids present. The writer has found that soils may have a high total active acidity, but, because the avidity is low, the soils do not respond much t o liming. Again soils having only a moderate active acidity but of high avidity respond decidedly t o liming. The writer also has a considerable amount of data which indicate that the injurious effects of soil acidity are usually not due to a direct action of the soil acidity on the plants or biological processes, but that it is due to the too low rate a t which the carbonic acid in competition with the soil acids is able t o force out of the calcium compounds the calcium bicarbonate which is needed by plants and biological processes for maintaining the proper internal reaction. Both from the theory involved and data secured from actual experiments, the writer is forced t o disagree with the criticisms of Potter in every respect. UNIVERSITY OF WISCONSIN MADISON, October 3, 1917
EMn TRUOG
THE WESTERN CHEMICAL MANUFACTURING COMPANY’S INDUSTRIAL COURSE Editor of the Journal of Industrial and Engineering Chemistry: The article in the July issue of your magazine entitled “Another Possible Form of Cooperation between Universities and the Chemical Industries,” page 638, has come to our attention. For a number of years it has been our custom to employ students from local colleges for odd jobs in and about our plant for the summer months. We also have adopted what we call a n Industrial Course, in which we enter recent college graduates for any sort of work encountered in a plant such as ours is. The wages a t the start are those of an ordinary workman. The men are asked to do any sort of work there is t o do and are not confined t o any one department but are shifted from place t o place and thus are made familiar with all the details of our various processes : these include the manufacture of sulfuric, nitric and muriatic acids (both commercial and chemically pure), com-
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mercial and C. P. aqua ammonia, anhydrous ammonia, and the dressing of complex zinc-lead-iron sulfide ores. From the men entered in this course we select those best qualified for taking charge of departments, laboratory men, etc. A l l of our present heads of departments have been through this course-in fact we would not consider employing outside professional men, except perhaps in the case of the installation of a process, the details of which are more or less unfamiliar to us. In other words, we have found it more practical to train our men along lines to which we have given much careful thought and attention. The 1 9 1 7 vacation period is over, but there may be some who would consider entering our industrial course and we would be pleased to hear from such persons. During the past summer we employed quite a few college men from the local coueges, more than the usual number for the summer months, and we were glad t o do it, for we believe the benefit was mutual. You will understand, of course, that we can give such work to only a limited number. Owing to the fact that our plant is so far from the Eastern colleges, we do not believe it will be practical for the men from such colleges to come so far west, considering the little time they will have, the railroad fare to and from Denver, and the fact that there are several colleges in and around Denver. Conditions, of course, would be different in the case of those men who would be permanent. WESTERNCHEMICAL MFG. Co. per PAULC. SKINNER, DENVER,COLORADO Treasurer and General Superintendent September 22, 1917
KILN DRYING OF WOOD Editor of the Journal of Industrial and Engineering Chemistry: I have just read your splendid editorial on “Aviation and the Chemist” in the September number of THISJOURNAL. I am sure you will be interested in the progress being made along the lines you mention and was about to call our work on kiln drying to your attention when I received a letter from Dr. Hawley in which he states he has already mentioned this to you briefly. This Laboratory has been giving a great deal of time to the study of kiln drying of wood, both from a theoretical and practical side. Conditions necessary to proper drying of wood have been explained theoretically and methods of drying developed accordingly. Several kilns are now in operation a t this laboratory where these methods can be tried out experimentally, and i t has been possible t o dry various species and various forms with entirely satisfactory results. After tests in the experimental kilns it has been our policy to make demonstrations in commercial kilns to assist the industries in solving their drying problems. In the present emergency the laboratory has been found well equipped with data already available to meet the problems in kiln drying woods, or to make further tests where necessary. It has been possible to kiln dry spruce green from the saw and in as good, if not better, condition than air-dried stock for airplane construction. Tests on ash are nearly completed and indications are that results will be satisfactory. We are gradually developing specifications for drying all commercial species that will insure good results with any kiln in which the specified conditions can be maintained. C. P. WINSLOW, FORESTPRODUCTS LABORATORY Director MADISON, WIS.. September 20. 1917 AVAILABLE OXYGEN IN PYROLUSITE-CORRECTION In the article by 0. I,.Barnebey, THIS JOURNAL, Q (1917). 9 6 1 , the missing footnotes on page 9 6 2 , second column, fourth paragraph, are as follows: 1
2
DeBries. Verslag Akad. Welenschappsn, [3],1 (1884), 114. Lemoine, Compt. rend.. 112 (1891),936,992. 1124. Lemoine and Poitevin, Ann. chim. phys., [ 3 ] , 62 (1861), 192.
