Some Interesting Chemical Patents Issued during ... - ACS Publications

Tetraethyl Lead—Ethyl gasoline is gasoline containing about 0.06 per cent of tetraethyl lead and 0.04 per cent of ethylene dibromide. The tetraethyl...
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I S D USTRIAL AND EXGIiVEERIiVG CHEMISTRY

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FORMALDEHYDE-The large output of synthetic phenolic resins is reflected in an increase in the production of formaldehyde. This product also has extensive application in the preparation of rubber accelerators. PHARMACEUTICALS-A new pharmaceutical manufactured for the first time in 1924 was amytal (isoamylethylbarbituric acid). The production of synthetic isomenthol, which was also started in 1924, is of special interest. This country has been dependent upon imports of natural menthol from Japan, as American peppermint oil was too high priced for use for menthol manufacture. TETRAETHYL LEAD-Ethyl gasoline is gasoline containing about 0.06 per cent of tetraethyl lead and 0.04 per cent of

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ethylene dibromide. The tetraethyl lead is used as an antiknock compound and it also decreases the reaction velocity of combustion and makes it possible to use engines of a higher compression ratio with an increase in the mileage per gallon of gas consumed. The general distribution of ethyl gasoline to the public was discontinued in May, 1925, until the question of the possible health hazard involved in its use has been settled. From July, 1924, to May, 1925, about 1,750,000 pounds of tetraethyl lead were manufactured. The use of tetraethyl lead or of a product giving similar results will undoubtedly increase in the future and permit greater efficiency in the design and operation of automobile engines.

Some Interesting Chemical Patents Issued during the Past Year to American Inventors By E. A. Hill1 and Francis B. LeechZ WASHINGTON, D. C.

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GLANCE a t the chemical patents issued to American inventors during the past year discloses a number of new or improved products and processes of manufacture, apparatus, and methods of production. Pharmacology

In the field of pharmacology, we find an improved method of producing novocaine and a new mercury derivative which has the antiseptic properties of tincture of iodine without iodine's caustic and abrasive properties. The method of producing novocaine is the invention of William A. Van Winkle, patent number 1,501,635, dated July 15, 1924. Van Winkle reduces diethylaminoethyl ester of p-nitrobenzoic acid which has been dissolved in acidulated water containing stannous chloride as a catalyst. The reduction results when an electric current is passed through the solution. The mercury derivative therapeutic product commercially known as Mercurochrome is the invention of Edwin C. White, patent number 1,535,003, dated April 21, 1925. This product comprises the chlorine-free monomercury derivative of dibromofluorescein. It is prepared by reacting with mercuric acetate on an aqueous suspension of dibromofluorescein. Mineral Oils

Mineral oils have received the attention of many inventors, and patents have issued for improved processes of cracking to C. P. Dubbs and E. &I. Clark. I n the Dubbs process as set forth in patent 1,522,425, dated January 6, 1925, a body of hydrocarbon oil is converted into low boiling point hydrocarbons by passing the oil through a continuous elongated passageway maintained a t a cracking temperature. The oil is then vaporized in an enlarged chamber, after which the insufficiently cracked vapors are condensed in a reflux condenser. The process makes use of super-atmospheric pressures. Clark, as disclosed in patent 1,525,916, dated February 10, 1925, subjects the hydrocarbon oils to be converted into lower boiling point hydrocarbons to a temperature above 1 1

Examiner, U. S . Patent Office. Patent lawyer.

680" F., a t a rate such that no substantial portion of the desired low boiling point products are formed during the heating. The heated oil is then compressed to a pressure a t which the inconverted oil is in the liquid state and the heated oil is retained under such pressure without reduction in temperature below 680" F., to effect conversion thereof. Plastics

Carlton Ellis and Norris Boehmer have recently patented a series of inventions relating to chlorinated rubber and processes of making the same. These patents are numbered 1,544,529 to 1,544,535, inclusive, all dated June 30, 1925. The new product is a plastic mass containing chlorinated rubber and a substantial amount of liquid-free chlorine, the latter serving as a plasticizing agent for the normally solid chlorinated rubber. Insecticides

Efforts to exterminate the boll weevil h a w brought forth a new method of manufactme of calcium arsenate, which is extensively used as an insecticide. This invention is based on the discovery that such arsenates may be commercially produced by the air oxidation of a mixture of white arsenic and the oxide or hydroxide of calcium or magnesium. Burned lime is slaked with water to a fine powder and mixed with powdered arsenic t o form a mud and then oxidized in a reverbatory or other furnace. The method described has been patented by Joseph F. Cullen, patent numbers 1,532,577 and 1,532,578, dated April 7, 1925. Electrochemistry

Electrochemistry has yielded several advances for which patents have been granted. Among these are a method of deposition of nickel and cobalt or their alloys, patented by Charles P. Madsen, patent 1,513,119 of October 28, 1924, and a method of effecting organic reactions, patented by Arthur W. Burrell, number 1,536,419, dated May 5, 1925. Madsen uses a rotating cathode of fusible metal which can be removed by heating the finished article so as to melt the original cathode. Nickel tubes can be thus readily formed. A colloidial solution of the metal salt is employed.

October, 1925

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I n the Burrell process an electric current is caused to flow through an aqueous electrolyte, on the active surface of which is maintained a moving film of an organic liquid to be transformed, the organic liquid being substantially insoluble in, and immiscible with, the electrolvte. As an examde, nitrobenzene is reduced t o aniline, using a cathode having a tin surface and an electrolyte of sulfuric acid.

consists of a plurality of ovens, having combustion chambers arranged longitudinal to the oven walls. Means are provided for supplying gas for ignition purposes to the chambers, the length of the gaseous stream in the chambers being ad-justable.

Rubber Accelerators Several accelerators for use in rubber vulcanization have been patented during the past year. Of interest in this line is the patent to John Young, number 1,538,076, issued May 10, 1925. Young proposes to promote the vulcanization of rubber by incorporating therewith a small amount of a mixture of ditolyl-substituted guanidines including dio-tolylguanidine and di-p-tolylguanidines in which the o-tolylguanidine predominates. Varnish

A catalytic and absorbent material produced from metallic hydroxide gels has been patented by Robert E. Wilson, number 1,540,448, dated June 2, 1925. This catalyst is essentially pyrophoric iron, which is highly porous and infrangible, and in which the pores of the metallic substance are ultra-microscopic. The process of manufacture consists in dehydrating granules of a gel-like, partially hydrated oxide of iron and reducing the metallic substance with hydrogen which has been highly diluted with nitrogen. Some of the uses claimed for this product are the synthesis of ammonia from hydrogen and nitrogen, the oxidation of sulfur dioxide and sulfur trioxide, and the removal or oxidation of sulfur compounds to gases.

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A new phenolic resin varnish of the Bakelite type has been recently patented by Harold C. Cheetham, patent number 1,528,006, dated March 3, 1925. Cheetham calls for a liquid coating composition comprising a phenolic resin of a potentially reactive type together with an organic solvent therefor and furfural. Coal Distillation A patent was recently issued to Elmer J. Crossen, number 1,522,421, dated January 6, 1925, for an improved apparatus for the destructive distillation of coal. This apparatus

Catalyst and Absorbent

Acetone and Butyl Alcohol

A novel process for producing acetone and butyl alcohol has been patented by George W. Freiberg, patent number 1,537,597, dated May 12, 1925. This process is characterized by fermenting carbohydrate material with bacteria which may be widely distributed in nature. The preferred bacteria are anaerobic bacilli with rounded ends, as they form large resistant spores and do not liquefy nutrient gelatin.

Liquid Hydrogen Sulfide as a Source of Laboratory Supply of the Gas' By Charles J. Moore HUNTER COLLEGE

OF THE C I T Y OF

HE notion seems to be prevalent that to liquefy hydrogen sulfide is a risky undertaking on account of the instability of the substance and the possibility of violent thermal dissociation. This, together with the fact that it attacks reducing valves, such as are commonly used on tanks of compressed gases, is probably the reason manufacturers have made no attempt to produce the liquid product until very recently. It is well established that the heat of formation of hydrogen sulfide is positive, and this guarantees that there can be no sudden, extensive thermal dissociation a t ordinary temperature. However, when the writer installed an outfit using the liquid as a source of supply, he was well aware of the possibility of slow, continuous dissociation resulting in excessive pressure due to the hydrogen liberated. I n order to guard against danger, analyses were made of the gas, and even after standing 6 months it was found to contain less than 0.25 per cent of hydrogen. A pressure gage attached to a cylinder for 4 months showed an increased pressure of less than one pound. The pressure in a cylinder containing 20 pounds of the liquid a t 100' F. is 281 pounds per square inch, and a t 150' F. it amounts to 500 pounds. The cylinders are said to have been tested to 3000 pounds. It therefore seems safe to use the liquid. Samples analyzed by the writer seem to be very pure, containing, in addition to the small amount of hydrogen mentioned above, traces of aniline and carbon disulfide from which substances it is produced as a by-product in the manufacture of diphenylthiourea. 1

Received March 27, 1925.

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I n order to avoid the use of reducing valves, a special gasometer has been devised using a seal fluid in which hydrogen sulfide is apparently insoluble. The working of the new outfit has been carefully observed for a period of 6 months, and sufficient data have been collected to justify the following comparisons: The initial cost of the system is more than double the cost of one Parsons generator. To generate 1 pound of hydrogen sulfide, 2.6 pounds of iron sulfide and 6 pounds of hydrochloric acid are required, costing between 60 and 75 cents. The liquid can be purchased in small quantities for 50 cents per pound. The pressure in the gasometer can be regulated a t will and maintained constant. The gasometer can be filled from the highpressure cylinder in a few moments, and an empty cylinder can be replaced in less than 5 minutes. To clean and refill a large generator is a disagreeable task, detrimental to health, and requires considerable time. Generators give little indication that the charge is nearing exhaustion until there is a sudden drop in pressure, which invariably happens when the gas is urgently needed. The disposal of the spent generator liquid is another matter'worthy of consideration, since it is injurious to plumbing and increases to some extent the poisonous component of sewer gases. I n cold weather, especially if sulfuric instead of hydrochloric acid is used, generators become badly clogged with crystalline iron salts, which are often difficult to remove. The writer ventures to predict that the days of the hydrogen sulfide generator are numbered and in a short while will disappear from the chemical laboratory.