What is the percentage by a solution formed by added 15 l of acetone to 28 l of water?

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liter) was now added to the moist precipitate, and denser) was boiled until the acid had dissolved the suspension was slowly heated to 93 °C and (15 min) and for a further 2.75 hr; 53.4 ml of maintained at that temperature until dissolution water was collected in the trap (theoretical yield, was complete. (At this point, the solution was 54.0 g). The reaction mixture was allowed to boiling.) The solution was filtered through a cool to room temperature, and the reflux condenser heated funnel into a 4-liter beaker, and the filtrate and trap were replaced by a water-cooled conwas stirred electrically. nucleated periodically, denser arranged for distillation. Two liters of and allowed to cool to room temperature, affording toluene was distilled off and the remaining hot a white precipitate. After the mixture had been solution was filtered twice, by suction, and refrigerated overnight, the precipitate was filtered refrigerated, yielding 458 g (dry) of colorless off with suction, again recrystallized from 1 liter crystals. This material was recrystallized twice of butyl acetate, as before, and dried and powdered from 1.5 liters of a 1:1 (vol/vol) solution of acetone as usual.

in ethyl acetate, and dried and powdered as usual; Analysis. Calculated for C20H340 Sr.1.5 H20: weight, 434 g (91 percent), mp, 151-152 °C. C, 53.01; H, 8.2. Found: C, 52.77; H, 8.1.

(20) Tris (2'-hydroxyacetophenono)chromium (18) Zinc cyclohexanebutyrate. Using method (III). 2'-Hydroxyacetophenone (1361.4 g, 10 a, a solution of the acid (see table 7) in 1 liter of moles) was dissolved in 2 liters of absolute ethanol absolute ethano] was added to the solution of in a 4-liter beaker equipped with a stirrer, and zinc acetate. A white precipitate was formed. vigorously stirred while 900 g of concentrated After stirring for a further 30 min, the suspension ammonium hydroxide (spgr 0.90) was slowly was filtered by suction and the precipitate was added. The resulting pale amber solution was washed by stirring with 2 liters of water, refiltering, stirred while a solution of 954 g of a commercial and repeating the treatment. Butyl acetate chromic acetate hydrate (corresponding to 3.0 (1.334 liters) was now added to the moist precipi- moles of anhydrous acetate) in 3 liters of water tate, and the suspension was slowly heated to 70 was added, with the formation of a purplish-red to 80 °C and maintained at that temperature until solution; this solution was placed in an 8-liter, dissolution was complete. The solution was cylindrical, Pyrex jar and concentrated on the filtered, nucleated, and refrigerated overnight, steam bath during 5 days to a sticky, tarry residue. giving a precipitate which was filtered off with The residue was mixed with 500 ml of absolute suction, again recrystallized from 1.334 liters of ethanol, and the mixture was gently heated on butyl acetate, as before, and dried and powdered the steam bath while 200 g of concentrated as usual.

ammonium hydroxide (sp gr 0.90) was added

dropwise. b. Recovery of Cyclohexanebutyric Acid

The mixture was reconcentrated to a tarry A mixture of impure residues of salts of cyclo- residue, cooled to 40 °C, and dissolved in 3 liters hexanebutyric acid (crude solids and mother of chloroform, with the formation of a deepliquors) was placed in a porcelain evaporating brown solution which was filtered through filterdish on the steam bath and the solvents were paper pulp, transferred to a separatory funnel, evaporated. Excess aqueous 50-percent phos- and washed with 100-ml portions of water until phoric acid was added, and the mixture was heated the aqueous washings were colorless. The chloroon the steam bath during 72 hr. The resulting form solution was then concentrated to half volaqueous suspension was diluted with water and

ume, and stirred while 4 liters of petroleum ether the free acid was precipitated with ice. (Alter- (bp, 38 to 67 °C) was added portionwise during natively, it was extracted with chloroform, and 30 min, with the precipitation of a greenish-tan the extract was washed with three portions of solid. The solid was collected by suction filtration water. Decolorizing carbon was added to the and washed with petroleum ether; the filtrate was washed chloroform layer, and the suspension was placed in an evaporating dish, concentrated to a heated to boiling and filtered. The brown filtrate

paste, dissolved in chloroform, filtered, and treated was transferred to a porcelain evaporating dish, with petroleum ether as above, affording more and the cbloroform and water were evaporated on solid material. The precipitates were combined, the steam bath.) The resulting moist, crude

,

air dried, and dried and powdered as usual; weight, cyclohexanebutyric acid was rapidly distilled at 840 g (61 percent). 3 mm (132–135 °C), and the main fraction of (21) Triphenyl phosphate. Triphenyl phosdistillate was redistilled twice, giving pure cyclo- phate (technical grade, from Fisher Scientific Co.; hexanebutyric acid.

978 g) was dissolved in 2 liters of absolute ethanol 3.4.2. Miscellaneous Compounds

in a 6-liter flask (equipped with a stirrer) on the

steam bath. The solution was kept at 60 to 70 °C (19) DL-Menthyl borate. The method of prep- and vigorously stirred while 2 liters of water at aration was essentially that described for l- 60 °C was gradually added, affording two layers. menthyl borate [3]. A suspension of 61.8 g (1 mole) Most of the upper (aqueous) layer was removed of boric acid in a solution of 468.9 g (3 moles) of by decantation, and a further 2 liters of water at DL-menthol in 2.6 liters of toluene (boiling stone) 60 °C was added, with stirring, to the lower layer. in a 6-liter, 1-necked, round-bottomed flask 6

The mixture was transferred to a separatory funnel, (equipped with a Barrett trap and a reflux con- and the lower layer was drawn off and cooled,

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and nitric acids, followed by determination of the 1058). Iron was determined by wet-ashing, element in the solution by appropriate methods, precipitating with ammonium hydroxide, disor (b) ignition. For 13 of the compounds, both solving the precipate in hydrochloric acid, reducing methods were applied. The residue obtained by with stannous chloride, and titrating with potasignition was either (a) weighed as the oxide; (b) sium dichromate. Determinations were also made treated with sulfuric acid and the sulfate weighed; by direct ignition of a sample, wrapped in filter (c) reduced with hydrogen and the metal weighed; paper and covered with oxalic acid, to ferric oxide or (d) dissolved in acid and the metal determined at 1050 °C. by various means. However, menthyl borate Lead cyclohexanebutyrate (Standard Sample (Standard Sample 1063) was fused with sodium 1059). Lead was determined by wet-ashing, peroxide, and the organic material of mercuric filtering the lead sulfate through a porcelain frit, cyclohexanebutyrate (Standard Sample 1064) was and weighing the lead sulfate after ignition at extracted with chloroform. Triphenyl phosphate 600 °C. Determinations were also made by direct (Standard Sample 1071a) was decomposed by ignition of a sample wrapped in filter paper and wet-ashing with perchloric and nitric acids.

covered with oxalic acid. The oxide was dissolved The details of the methods of analysis for each in nitric acid, precipitated with chromate, and standard sample are given in the next four weighed as lead chromate after drying at 140 °C. subsections.

Magnesium cyclohexanebutyrate (Standard Sam

ple 1061). Magnesium was determined by wet3.7.1. Wet-ashing; Ignition

ashing, precipitating twice as magnesium ammoniAluminum cyclohexanebutyrate (Standard Sample

um phosphate, and weighing the magnesium pyro1050). Aluminum was determined by wet-ashing,

phosphate after ignition at 1,000 °C. Determi

nations were also made by direct ignition of a precipitating with ammonium hydroxide, and igniting the filtered precipitate to aluminum oxide

sample wrapped in filter paper and covered with

oxalic acid. The residue was converted into magat 1,100 °C. Determinations were also made by direct ignition of a sample, wrapped in filter paper

nesium sulfate and weighed after ignition at

700 °C. and covered with oxalic acid, to aluminum oxide at 1,100 °C.

Manganous cyclohexanebutyrate (Standard SamBarium cyclohexanebutyrate (Standard Sample

ple 1062). Manganese was determined by wet1051). Barium was determined by wet-ashing,

ashing, oxidizing the manganese with ammonium filtering the barium sulfate, and weighing it after

persulfate, and titrating the manganese with ignition at 1,000 °C. Determinations were also

sodium arsenite solution. Determinations were made by direct ignition of a sample wrapped in

also made by direct ignition of a sample wrapped filter paper and covered with oxalic acid. The

in filter paper and covered with oxalic acid. residue was converted into barium sulfate and

The residue was converted into

sulfate

manganous weighed after ignition at 900 °C.

and weighed after ignition at 700 °C. Bis(1-phenyl-1,3-butanediono)oxovanadium (IV)

Nickel cyclohexanebutyrate (Standard Sample (Standard Sample 1052). Vanadium was deter

1065). Nickel was determined by wet-ashing, mined by wet-ashing, oxidizing the vanadium

precipitating with dimethylglyoxime, and weighing with nitric acid, and titrating the vapadium with

the nickel dimethylglyoxime precipitate after ferrous ammonium sulfate solution. Determina

drying at 150 °C. Determinations were also made tions were also made by direct ignition of a sample

by direct ignition of a sample wrapped in filter wrapped in filter paper and covered with oxalic

and covered with oxalic acid. The oxide was

paper acid. The oxide was ignited at 800 °C and

ignited under hydrogen and weighed as the metal. weighed as vanadium pentaoxide,

Potassium cyclohexanebutyrate (Standard Sample Calcium cyclohexanebutyrate (Standard Sample

1067). Potassium was determined by wet-ashing, 1054). Calcium was determined by wet-ashing,

removing the excess acid by evaporation, and precipitating the calcium sulfate in alcoholic weighing the potassium as potassium sulfate after solution, and weighing the calcium sulfate after

ignition at 650 °C. Determinations were also ignition at 600 °C. Determinations were also made by direct ignition of a sample wrapped in made by direct ignition of a sample wrapped in filter paper and covered with oxalic acid. The filter paper and covered with oxalic acid. The residue was converted either into potassium sulfate oxide was converted into calcium sulfate, and or potassium chloride and weighed after ignition weighed after ignition at 700 °C.

at 650 °C. Copper cyclohexanebutyrate (Standard Sample Strontium cyclohexanebutyrate (Standard Sample 1056). Copper was determined by wet-ashing, 1070). Strontium was determined by wet-ashing, depositing the copper by electrolysis, and weighing precipitating the strontium sulfate in alcoholic as metallic copper,

Determinations were also solution, and weighing the strontium sulfate after made by direct ignition of a sample wrapped in ignition at 600 °C. Determinations were also filter paper and covered with oxalic acid. The made by direct ignition of a sample wrapped in oxide was ignited under hydrogen, and weighed as filter paper and covered with oxalic acid. The the metal.

residue was converted into strontium sulfate, and Ferric cyclohexanebutyrate (Standard Sample weighed after ignition at 700 °C.

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of the Project Advisory Committee: C. M. Gambrill, Ethyl Corporation, Chairman; R. O. Clark, Gulf Research and Development Company; G. H. Patterson, E. I. du Pont de Nemours and Company, Inc.; E. D. Peters, Shell Development Company; and E. B. Tucker, Standard Oil Company (Indiana). They also thank the following members of the staff of the National Bureau of Standards who collaborated on the work and made many helpful suggestions: H. A. Bright 8 and E. Wichers. Technical assistance was rendered by A. D. Kuchta (summer student, 1957 and 1958). Spectrographic analyses were performed by E. K. Hubbard and R. Alvarez of the Spectrochemistry Section. Chemical analyses were made by B. B. Bendigo and L. A. Machlan of the Standard Reference Materials Section, and the determinations of the weight-stabilities were made by B. B. Bendigo.

The following companies supplied samples of some of the materials used in this research and, in some instances, gave valuable advice: Advance Solvents & Chemicals, Division of Carlisle Chemical Works, Inc., New Brunswick, N.J.; Carbide & Carbon Chemicals Co., Division of Union Carbide & Carbon Corp., Baltimore, Md., and Charleston, W. Va.; Elastomer Chemicals Dept., E. I. du Pont de Nemours & Co., Inc., Wilmington, Del.; Ethyl Corporation, Detroit, Mich.; General Electric Co., Chemical & Metallurgical Div. and Silicone Products Dept., Waterford, N.Y.; Gulf Research & Development Co., Pittsburgh, Pa.; Harshaw Chemical Co., Cleveland, Ohio, and Gloucester City, N.J.; Irvington Varnish & Insulator, Irvington, N.J.; Metal & Thermit Corp., Rahway, N.J.; Minnesota Mining & Mfg. Co., Newark, N.J.; Monsanto Chemical Co., Organic Chemicals Div., St. Louis, Mo.; Naftone, Inc., New York, N.Y.; Nuodex Products Co., Div. of Heyden Newport Chemical Corp., Elizabeth, N.J.; Pennsalt Chemicals Corp., Industrial Div., Pennsylvania Salt Mfg. Co., Philadelphia 2, Pa.; Quaker State Oil & Refining Co., Oil City, Pa.; Sharples Chemical Div., Pennsylvania Salt Mfg. Co., Philadelphia 2, Pa.; Shell Development Co., Emeryville, Calif.; Shell Oil Co., Inc., Martinez, Calif.; and Standard Oil Co. of Indiana, Whiting, Ind.

with precautions to avoid contamination from transfer of traces of one compound to a container of another compound, the calculated weight of each of the other compounds was added, one at a time in the order given in table 11), and completely dissolved before the next compound was added. After each addition, the mixture was gently heated, tilted, and rotated in order to wash down any particles adhering to the inside of the flask.

After the last compound had been added' and dissolved, 2 ml of bis(2-ethylhexyl)amine was added. The hot solution in the flask was now poured into the small beaker, and back and forth, until all traces of solid in the beaker had dissolved. After returning the solution to the Mask, the beaker was washed with six 15-ml portions of lubricating oil, and these rinsings were all transferred to the flask. The oil solution was now allowed to cool to room temperature, and cool lubricating oil was added to the flask imtil the weight of the solution was 100 +0.5 g. The solution was reheated to 85 °C, allowed to cool to room temperature, transferred to a bottle, and tightly stoppered.

A precise determination of the maximum concentration attainable for each element of interest, either individually in oil plus solubilizers, or as a mixture of the standard compounds in oil-plus solubilizers, has not been made. However, solutions having concentrations much higher than those given have been prepared and found to be stable. All solutions prepared from the standard compounds (according to the directions given) have, up to this time, shown no signs of deterioration on keeping.

The authors express their appreciation to all persons and firms who co-operated on this project. They are especially indebted to W. T. Gunn, Director of the Division of Refining, American Petroleum Institute, and to the following members

[1] R. G. Charles, J. Inorg. & Nuclear Chem. 6, 42 (1958). (2) C. R. Hauser, F. W. Swamer, and J. T. Adams, Org.

Reactions 8, 115 (1954). [3] G. L. O'Connor and H. R. Nace, J. Am. Chem. Soc. 77,

1578 (1955). [4] G. T. Morgan and H. W. Moss, J. Chem. Soc. 103, 78

(1913). [5] C. Doree and A. C. Pepper, J. Chem. Soc. 1942, 477. (6) R. G. Charles, J. Org. Chem. 22, 677 (1957).

Deceased, May 22, 1961.

V.S. GOVERNMENT PRINTING OFFICE: 1962

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The scope of activities of the National Bureau of Standards at its major laboratories in Washington, D.C., and Boulder, Colo., is suggested in the following listing of the divisions and sections engaged in technical work. In general, each section carries out specialized research, development, and engineering in the field indicated by its title. A brief description of the activities, and of the resultant publications, appears on the inside of the front cover.

Electricity. Resistance and Reactance. Electrochemistry. Electrical Instruments. Magnetic Measurements. Di- electrics. High Voltage. Metrology. Photometry and Colorimetry. Refractometry. Photographic Research. Length. Engineering Metrol- ogy. Mass and Scale. Volumetry and Densimetry.

Heat Temperature Physics. Heat Measurements. Cryogenic Physics. Equation of State. Statistical Physics.

Analytical and Inorganic Chemistry. Pure Substances. Spectrochemistry. Solution Chemistry. Standard Reference

ular Kinetics. Mass Spectrometry.

Cryogenic Engineering Laboratory. Cryogenic Equipment. Cryogenic Processes. Properties of Materials. Cryogenic Technical Services.

CENTRAL RADIO PROPAGATION LABORATORY Ionosphere Research and Propagation. Low Frequency and Very Low Frequency Research. Ionosphere Research. Prediction Services. Sun-Earth Relationships. Field Engineering. Radio Warning Services. Vertical Soundings Research. Radio Propagation Engineering. Data Reduction Instrumentation. Radio Noise. Tropospheric Measurements. Tropospheric Analysis. Propagation-Terrain Effects. Radio-Meteorology. Lower Atmosphere Physics. Radio Systems. Applied Electromagnetic Theory. High Frequency and Very High Frequency Research. Modulation Research. Antenna Research. Navigation Systems. Upper Atmosphere and Space Physics. Upper Atmosphere and Plasma Physics. Ionosphere and Exosphere Scatter. Airglow and Aurora. Ionospheric Radio Astronomy.

RADIO STANDARDS LABORATORY Radio Physics. Radio Broadcast Service. Radio and Microwave Materials. Atomic Frequency and Time-Interval Standards. Millimeter-Wave Research. Circuit Standards. High Frequency Electrical Standards. Microwave Circuit Standards. Electronic Calibration Center.

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