Determination of Carbon Disulfide in Its Emulsions

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INDUSTRIAL A N D ENGINEERING CHEMISTRY

October, 1927 Uses

Because of the brilliance of its flame when burned in powder or ribbon, magnesium is used in flashlight powder, fireworks, and military flares. Its chemical affinity for oxygen and nitrogen a t high temperatures makes it useful in degasifying radio tubes. Radio trickle chargers use magnesium rectifying electrodes. The Grignard synthesis is now commercially practical because of the low cost of the pure metal. Magnesium finds application as a deoxidizer and degasifier in the metallurgical industries. A large tonnage is used in the refining of nickel and nickel alloys, and its use is extending rapidly to other non-ferrous metals. Zinc-base die castings have recently been found to be improved by the addition of small amounts of magnesium. A considerable amount of magnesium is used as a mjnor constituent of modern high-strength aluminum alloys. The Duralumin type alloys contain about 0.5 per cent, while the “Y” casting alloy contains 1.5 per cent magnesium. It is estimated that one-fifth of the more important aluminum alloys have magnesium as an alloying ingredient. While not present in large amounts, it is necessary in order that maximum strength will be developed. These magnesiumcontaining alloys are more extensively used in Europe than in this country. The greatest development in the uses for magnesium will be in the extension of the engineering and structural uses of its ultra-light alloys. A saving of three-quarters of the weight is possible where they replace steel and one-third where they are substituted for the light aluminum alloys. The strength properties are good, even on a volume basis, and are quite superior on a weight basis. Castings made from magnesium alloys are dense and nonporous. They are therefore well adapted for supercharger housings, manifolds, and other parts required to hold gas pressure. Crankcases are successfully cast, even when of large size and intricate design as illustrated in Figure 32. Applications still in the experimental stage are cast cylinders,

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cylinders heads, and other large motor parts. One of the first uses proposed for magnesium alloys was for pistons in internal-combustion engines. The high thermal conductivity and light weight peimit much higher engine speeds with increased power and lessened vibration. Forged pistons and connecting rods have recently developed which are harder and stronger than the original castings. Airplane propellers, forged from a solid billet, offer maximum strength combined with lightness. Forged tail skids and landing gear are in successful operation. Extruded shapes are useful for aircraft structural members while rolled sheet finds application as wing covering. An interesting use is the press-forged resonator disks for automobile horns. No other metal produces such clear and resonant tones as do certain magnesium alloys. Many hundreds of thousands of these horns have been made and they are standard equipment on several of the better grades of motor cars. There are possibilities in utilizing this property in other sound producing or amplifying apparatus. Owing to the absence of distortion or warping on aging, magnesium alloys are used for jigs in machine-shop practice. Instrument parts, portable machines and tools, artificial limbs, and metallic furniture are all lightened and strengthened through the use of magnesium. Golf clubs with magnesium alloy heads are in use. Metal patterns can be made in large sizes because of their light weight. Many typical applications of magnesium alloys are shown in Figure 33. I n Europe, where the economic saving through the use of light alloys is more widely recognized than in this country, even such commonplace articles as buttons, combs, and pencil sharpeners are made from magnesium alloys. As designers and engineers become familiar with the metal, numerous other uses will suggest themselves. With goodstrength alloys, well-developed technic for casting and working the metals, and adequate means for surface protection magnesium will undoubtedly become an increasingly important engineering metal.

Determination of Carbon Disulfide in Its Emulsions’ By H a r r y J. Fisher CONNECTICUT AGRICULTURAL EXPERIMENT STATION, NEWH A V E N , CONN.

ARBON disulfide emulsions have lately come into use shaken, then 45 CC. of hot water were added and the mixture agitated until the rosin was dissolved. Five cubic centimeters of for the treatment of lawns infested with the J~~~~~~~U. S. P. oleic acid were added t o this mixture, which was shaken beetle.’ It is thel’efore frequently necessary to de- agaln. Thirty cubic centimeters of this soap solution were

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termine the carbon disulfide content of such emulsions as marketed commercially. Most of the work heretofore done on the analysis of carbon disulfide mixtures has dealt with the determination of carbon disulfide in crude benzene, where the percentages are small. Xone of the methods is suitable without modification for emulsions of a high - carbon disulfide content. For experimental purposes two emulsions of known carbon disulfide content were prepared, of types actually recommended for use in the contiol of the Japanese beet,le. Emulsion No. 1. One part by volume of a commercial potassium rosin-fish oil soap was mixed with three parts of water. Twenty-eight cubic centimeters of this soap solution were added t o a tared, glass-stoppered, 100-cc. volumetric flask, and weighed. Seventy cubic centimeters of carbon disulfide were then added, the flask stoppered and weighed, and the contents shaken until completely emulsified. Emulsion A70. 2. Five grams of powdered rosin were added to 13.5 cc. of warm 7 per cent sodium hydroxide solution and 1 2

Received M a y 26, 1927. Pennsylvania Dcpt. Agr. General Bull. 410, A u g u s t 15, 1925.

weighed in a 100-cc. flask, 70 cc. of carbon disulfide were added, and the flask was weighed again as in preparing emulsion No. 1. The mixture was shaken until completely emulsified. The carbon disulfide used was the C. P. product, further purified by allowing i t to stand for several days over solid potassium hydroxide, then distilling, discarding the first and last portions of the distillate. It had a boiling range of 0.02’ C.

After attempting to adapt both the methods of Harding and Doran3 and we is^,^ it was found that the best results were obtained by a modification of the method of Weiss, oxidizing the carbon disulfide in an alkaline peroxide solution and precipitating the resulting sulfate and weighing as barium sulfate. Method

Add about 2 grams of emulsion t o a tared, glass-stoppered, 100-cc., volumetric flask containing 40 re. of 8 per cent a J . A m . Chem. SOC.29, 1476 (1907). THISJOURXAI,, 1, 604 (1909); see also Warren, A m . J. Pharm., 96, 864 (1923) ; Annual Reports Chemical Laboratory American Medical

Assocn., 16. 42.

INDUSTRIAL AND ENGINEERING CHEMISTRY

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alcoholic potassium hydroxide; stopper and weigh. Make up solution to volume with 95 per cent alcohol a t 20” C., pipet out a 5-cc. aliquot, and add to a mixture of 50 cc. water, 50 cc. 3 per cent hydrogen peroxide, and 10 cc. 10 per cent potassium hydroxide in a beaker. Heat on the steam bath for 1 hour, acidify with hydrochloric acid, filter, heat the filtrate to boiling, and add 10 cc. 10 per cent barium chloride drop by drop. After standing overnight filter the barium sulfate on an ashless filter paper, wash with hot water, and ignite in a platinum crucible. Add two drops of concentrated sulfuric acid to the cooled crucible, fume off the acid, heat the crucible to redness, then cool in a desiccator and weigh. Run a blank determination on the reagents alone. Bas04 X 0.16306 = CSt Results EMULSION No. 1

CSz present P e r cent 77.43

,

EMULSION No. 2

CSz found

CSa present

CSz found

Pev cent 74.81 75.13 74.90 76.19

P e r cent 74.97

P e r cent 71.30 71.30 70.99 71.34

Vol. 19, No. 10

The average recovery of carbon disulfide by this method is about 96 per cent, assuming 100 per cent purity for the carbon disulfide used; however, analyses of the pure carbon disulfide alone showed about 98 per cent CSz. Almost faultless checks can be obtained in duplicate analyses on the same emulsion. This method estimates as carbon disulfide any sulfur present in an emulsion in any form which will be converted to sulfate by an alkaline peroxide solution. It is doubtful if any commercial carbon disulfide emulsion will contain more than a negligible amount of non-carbon disulfide sulfur. Of the two soap solutions used in making the emulsions employed in this work, the rosin-fish oil soap in emulsion No. 1 contained 0.10 per cent sulfur, corresponding to 0.02 per cent sulfur in the emulsion, while the rosin-oleic acid soap in emulsion No. 2 contained 0.00 per cent sulfur. For this reason it was not thought necessary to work out a method for determining non-carbon disulfide sulfur in these emulsions. Not all of the carbon disulfide is necessarily present in the free state in the finished emulsion; some of it may be combined, with the rosin or otherwise, and the method does not distinguish between that present in the combined and uncombined states,

AMERICAN CHEMICAL INDUSTRIES Parke, Davis & Company

T

HE production of medicinal substances on a large scale

is a relatively modern industry. Up t o the middle of the last century i t had been the almost universal custom for each pharmacist or apothecary or chemist, as he was variously known in different countries, t o prepare for himself such substances or compounds as he needed, but about this time the idea of centralized manufacture of medicinal preparations was beginning t o take root. In 1862 Samuel P. Duffield, a retail druggist in Detroit,.began t o make a number of preparations in larger amounts than required for his own use and sell them t o other pharmacists. Seeing the possibility of a larger business which could render useful service t o many and probably become financially profitable, Hervey C. Parke cast his lot with Dr. Duffield and there was founded, on October 26, 1866, the partnership of Duffield, Parke & Company. This is considered the birth of the present business. In January, 1869, A. F. Jennings bought the interest of Dr. Duffield and the firm became Parke, Jennings & Company, with Geo. S. Davis as one of the company. On November 16, 1871, Dr. Jennings retired from the firm and i t became Parke, Davis & Company, a co-partnership. Thus it continued for a few years, but with the business developing rapidly i t seemed desirable to perpetuate i t in some better form; so on January 14, 1875, i t was incorporated With a capital stock of $125,000, of which $81,950 was paid in. Today the business is represented by five million shares of no-par-value stock selling on the market a t about $30 per share. Besides the main laboratories in Detroit, there are also manufacturing laboratories in Walkerville, Canada; London, England; Syndey, Australia; Rio de Janeiro, Brazil; Santiago, Chile; and Havana, Cuba. There are fifteen branch offices in the United States, three in Canada, and ten in various foreign countries. In fact, there is practically no place in the world t o which the medicinal products of Parke, Davis & Company d o not reach.

The present directors of the business are 0. W. Smith, president; N. H. F. McLeod, secretary and treasurer; David Whitney, A. H. Buhl, and Jerome Remick, vice presidents; I,. B. Hayward, superintendent of manufacturing; and Henry Ledyard.

Guiding Principles In the development of great enterprises permanence and virility are determined not so much by personalities as by principles. Outstanding personalities may come and go, but the dominating principles whereby they express in business the best of their abilities may continually develop and give t o that business the ardor and strength of perpetual youthfulness. In the early days of Parke, Davis & Company the desire for immediate profit was made subservient to the hope of future growth, and the principle of being satisfied with nothing but the best that science could produce became the cornerstone of this commercial structure. The ideas which imbued the founders of the business, and which have been perpetuated through changing generations of control and ownership, may well be illustrated by a quotation from a little leaflet printed many years ago when the firm was very young, entitled “Our Creed and Code:” We believe that in combating disease only the best quality of drugs is permissible and that to their manipulation should be applied the highest scientific skill. We believe t h a t the issuing of inferior medicines of any kind is unjustifiable from any point of view. We believe in standing solely on the intrinsic merits of our preparations and in making no false pretenses; in doing the best that scientific knowledge and skill will accomplish and in doing it honestly and faithfully. We believe in working fully in harmony with our pharmacal and medical friends in gratefully accepting any suggestions t h a t may tend to our mutual profit. Our watchwords are Purity, Accuracy, Reliability. This same spirit permeates the whole organization at the present time, and when it is noted that the majority of shareholders,