Action of Negative Catalysts with Red Oil1 - Industrial & Engineering

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INDUSTRIAL A N D ENGINEERING CHEMISTRY

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ment. It will be observed that this card replaces entirely the usual laboratory notebook and furnishes a concise record of the work which is convenient for compiling statistical data on such topics as speed, cost, and individual efficiency. METHODS-The methods used for determinations that recur with any frequency are typed according to a standard form and arrangement (see Figure 3), and are blueprinted. The analyst assigned to a determination is given a copy of the method, which he is expected to follow carefully. These methods are written by the research division, and represent the tangible results of their work. The methods are of two classes-tentative and standard. For a tentative method to graduate to the standard rank, it is necessary for it not only to have been carefully tested by the research division but also to have been proved practically satisfactory by routine use for a year or more in the General Laboratory. I n writing the methods, emphasis is placed upon conciseness and avoidance of ambiguity in the directions, clear statements of the accuracy to be expected, the precision or reproducibility of the results, and the limitations of the method due to presence of interfering substances. About 150 of these methods are on file. BIBLIOGRAPHY AND T R A N S L A T I O N S - - W ~ ~ ~ ~ this service could be performed by the members of an analytical staff individually, our experience has proved the efficiency of allocating all work of this nature to one specially qualified man. I n addition to compiling abstracted bibliographies and full translations for the research division on specific problems, an important duty of the bibliographer in our organization is the compilation and maintenance of an exhaustive bibliography in the form of a card catalog of all publications on analytical chemistry. It is unnecessary to emphasize the manifold advantages of such an index.

Vol. 23, No. 11

Discussion

This organization appears elaborate only in description, It operates, in fact, with gratifying smoothness; and, although further modifications will unquestionably be made in the future as they have in the past, as experience discovers the weak spots, it is believed that the above outline represents in general the most practicable organization for our purposes. I n our case, reorganization has already shown two desirable results: with the acquirement of the ability to carry out analytical determinations hitherto impossible, a latent need for these determinations has become evident, so that much more varied work is required of the analytical department; and by increasing the general efficiency, we become progressively able t o do more work, better and in less time, with fewer men. It is almost needless to add that many specific points in the foregoing description are referable to the peculiar requirements of Bell Telephone Laboratories, and are not suggested for general adoption. A concrete presentation of our particular solution of the problem of the role of analytical chemistry in industrial research, rather than confinement to abstract generalities, has seemed, however, more likely t o achieve the aims of this paper. It is desired to emphasize, in conclusion, that the advancement of analytical chemistry to a more dignified stratum of research has intrinsic advantages not only for research itself but for the individual analyst as well. There will be, indeed, a continually accelerated improvement, for a more attractive prospect will call better men t o a career in analytical chemistry with the consequent elimination of the weaker individuals and a raising of the general standard of analytical personnel. Thus the probability of a reasonably early arrival near the ideal stated in the beginning of this article will be constantly increased.

Action of Negative Catalysts with Red Oil' A. H. Gill and Fred Ebersole 222 CHARLES RIVERROAD,CAMBRIDGE, MASS

N A preceding article ( 1 ) attention was called to the effect of small quantities of metallic salts of weak acids in causing very appreciable heating effects with red oil and olive oil. It was there explained that this data was of importance to textile mills, particularly those using red oils, which are more or less notorious for their heating effect. I n another article the heating effect was shown to be due to iron salts ( 3 ) . These can be removed by treatment with hydrochloric acid, thus rendering the oil safe.

I

1

Received July 30, 1931

Table I-Effect SAMPLE Oil alone Resorcinol Orcinol Hydroquinol Catechol Quinone o-Chlorophenol Benzaldehyde Nitrobenzene Thymol Oil caraway New oil alone Cutch extract No. 20 creosote N o . 103 creosote New oil and Fe N o . 20 oil N o . 20 oil No. 103 oil

60 Min.

c.

165.5 99.75 99 98 98.26 99 102 165 162 100 155 117 108 100 100 153 98 98.5 98.75

-

75 Min. O

c.

155.5 105 100.75 99 99 99.5 138 153 145 101 149 154 138 100 100.5 156 99 99.3 100

Instead of using the latter method, it was thought worth while to try the effect of the so-called negative catalysts. Those employed were some of the phenols, both monatomic and diatomic. I n order to more easily mix these phenols with the red oil, they were used as their sodium salts dissolved in alcohol. The procedure was the same as in the articles mentioned; that is, the oil itself, which had been treated with iron stearate t o serve as a catalyst to ensure its heating, was heated upon absorbent cotton in the Mackey apparatus for 1 hour or more to determine its behavior as

of Negative Catalysts o n Heating of Red Oil HEATING EFFECT 90 Min. 105 Min. 120 Min.

c.

151 119 102 99 99.5 99.5 140 138 142 101.5 146 183 146 101 101 147 99.5 100 100.5

c. 146: 5 126 99.25

...

99.5 140

...

ioi: 5

142 170 146 101 102 137 99.75 100.3 101

a

REMARKS

c.

...

141 138 99.5 100 100 138

... ... 103 ...

154 137 101 105.5 137 99.75 100.75 102

Stains cotton too deeply

No solvent added N o solvent added N o solvent added Dissolvedin alcoholalone Caraway 5'%, no solvent 5% Max. at 158

November, 1931

IlVD USTRIAL AND ENGINEERING CHEXISTRY

shown in Table I. Then a portion was vigorously stirred with 1 per cent of the negative catalyst and heated exactly as before. I n Table I the oil alone reached a temperature of 165.5' C. in 1 hour, dropped 10" in the next 15 minutes, and so on. It is considered that any oil which shows a temperature exceeding 100" C. in 1 hour or 200" C. in 2 hours is a dangerous oil and liable to produce spontaneous combustion. Applying this rule to the substanres in the table, i t is seen that resorcinol, orcinol, o-chlorophenol, benzaldehyde, nitrobenzene, oil of caraway, and cutch extract all give temperatures above 100" C. in between 1 and 2 hours. These, then, do not inhibit the reaction and are of no use as negative catalysts. On the other hand, hydroquinol, catechol, quinone, thymol, and Kos. 20 and 103 creosotes do not allow an appreciable rise of temperature and may be regarded as satisfactorily preventing the heating of the oil. The first ten tests (through oil of caraway) were made with one

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sample of red oil. As this was exhausted, the last seven tests were made with a new sample. How this behaved can be seen from the title "New oil alone." KO.20 creosote is a commercial product described as a blast-furnace oil (from blast-furnace tar) containing between 25 and 40 per cent of high-boiling tar acids. No. 103 creosote is a similar product, coming from a vertical-retort coal tar containing from 20 to 25 per cent of tar acids. From this it would seem that the addition of a very small quantity of commercial creosote oil would render any red oil absolutely safe for use. The amount added is not readily perceptible by the sense of smell. Inasmuch as this may become useful industrially, a patent for the use of phenols or negative catalysts with textile oils has been taken out ( 2 ) . Literature Cited (1) Gill, A. H., IND.ENG. CHEM.,16, 23 (1924) (2) Gill, A. H., U. S. Patent 1,791,057 (Feb. 3, 1931). (3) Swett and Hughes, J. IND. ENG CHBM, 9, 623 (1917)

Relative Concentrations of Negative Ions in Different Parts of an Electroosmose Edward Bartow and Floyd W. Perisho IOWASTATEUNIVERSITY, IOWACITY,IOWA

The removal of the negative ions-chloride, carbonBartow and Jebens (2, 3 ) , U R I F I C A T I O N of ate, and sulfate-is practically complete at all rates in 1930 c h e c k e d t h e w o r k water by electricity, in below 30 liters per hour from solutions up to 250 parts previously done, obtaining a which the c u r r e n t is per million. Bicarbonate ions are not easily removed water having a r e s i d u e of used as a source of heat, has from solutions of carbonate alone at rates in excess less than 15 p. p. m. from n o t b e e n economically sucof 25 liters per hour, but are quickly removed from the water supply a t the Unicessful. The use of the cursolutions containing sulfate or chloride ions. versity of Iowa, which has a rent to remove electrolytes The limit of the machine is reached at 500 parts per total residue of 725 p. p. m. from a central cell to cells conmillion chloride radical if the rate is in excess of 25 They suggest that less than taining the anode and cathode liters per hour. If water of only comparative purity one-half t h e e l e c t r i c a l has furnished a means of water is desired, rates of 35 and even 40 liters per hour may energy would be required to treatment by electricity that be practical even with water of high salt content. reduce the residue from 600 is apparently economically Partially purified water may be prepared also by the to 300 p p. m. than would be possible. The application of use of fewer cells and without the necessity of washing required to reduce it from this method-the electrocsthe last two cells with pure water. 300 D . D . m. to zero. mose process-to the purification of water was described T i e 'apparatus (Figure 1) for the first time in 1926 by Illig (7,8),who developed the proc- used in this study is the type I11 machine made by the ess in Berlin. Patin (10)in 1928continued the work and showed Elektro-Osmose A-G. of Berlin, with rated capacity of 25 that, under certain conditions, the preparation of pure water liters per hour. The objects of this study were: to ascertain the limits of by the electroosmose process is cheaper than distillation. Marie (0) in 1928 stated that salts are not entirely removed efficient removal by this apparatus of some of the common by the electrodsmose process, but that water may be made negative ions from solutions of different concentrations and a t sufficiently pure for most purposes. He lists as advantages different rates of flow; to obtain a picture of the progress of that the product is cold, the cost is less than distilled water, the reaction within the apparatus in order that the rate may be regulated to produce partially purified water of the desired its control is simple, and little attention is required. Behrman (,4, G) set the limits of the apparatus a t 1000 mg. degree of purity; and to study the effect that various ions in per liter and recommended the use of the process in purifica- a mixture have upon the removal of other ions. tion of water for making ice, advising that purification be not Theoretical Principles of Electroosmosis carried below 200 p. p. m. In the purification of water, the amount of material that may be left in may depend upon the The electro6smose principle is, in general, the principle of use to which it is to be put-for example, for use in boilers, electrolysis in which there is a separation a t the electrodes of laundries, and in industries requiring water of various degrees the ions of the solution or of the products of their discharge. of purity. Ions of the dissolved salt are drawn toward the electrodes together with the H + and OH- ions present in the water. 1 ReceiLed May 25, 1931. Presented before the Division of Water, Sewage, and Sanitation at the 81st Meeting of the American Chemical At each electrode the ion having the least decomposition Society, Indianapolis, Ind., March 30 t o April 3, 1931. potential is discharged and either appears in molecular form 2 Abstract from a dissertation submitted in partial fullilment of the or reacts with other ions present in the solution. This requirements for the degree of doctor of philosophy in the Department of Chemistry, State University of Iowa, by Floyd W Perisho. process is modified by the introduction of special diaphragms