48
Review of Americau Chtwzical R e s c a d .
of these standards to the sanitary analysis of deep well waters is unsatisfactory and misleading. The excessive amount of free ammonia is accounted for by reduction of nitrates and nitrites by sulphide of iron or organic matter. LF:O?\TAKD P.KIXKICVTT. Sauitary analyses of Massachusetts deep well waters have been made by T. M . Drown (Report of the Massachusetts State Board of Health, 1894, p . 421), and b y W. T. Sedgwick (Ibid.,p. 435). Many of these waters contain excessive amounts of nitrogen as nitrites. LEONARD P. KINNICUTT.
INDUSTRIAL CHEMISTRY. Lead vs. Nickel Storage Batteries. BE-HUGHRODMAN.Elm. trical World a i d Ezgixecr, September 2 7 , 1g02.-Froni the requirements of practice, Mr. Rodman considers that the list of available anodes and electrolytes is limited to lead in sulphuric acid and nickel in an alkali hydroxide. This does not mean, however, that the active material must iiecessarily contain nickel or lead but simply that the grid must be one or the other of these metals in its appropriate solution. H e considers the Edison nickel-iron cell as the most promising member of new types of storage batteries and compares it with the lead cell with respect to grid, active material and electrolyte. T h e alkali battery possesses a great advantage in making its support plates of a stiff easily worked metal. This stiffness ensures absence of buckling and allows of a high degree of mechanical perfection in the working. Concerning the electrolyte, he says that while the possibility of using a sinal1 ainoutit of electrolyte is one of the important factors in making the alkali battery light and small this advantage adds to the trouble of refilling. T h e voltage of the alkali cell is only about one-half that of the lead cell, therefore for the same energy output, we must double either the current or the nuniber of cells and so multiply useless dissociation by two. There are other disadvantages. While acid does not creep, alkali both creeps and turns to carbonate. H e believes that for central station work, the position of the lead cell seems secure because of its low first cost, low internal resistance, high voltage and efficiency. For lighter service, particularly for electric wagons where Watt efficiency and cost are to some extent subordiuate to convenience, the choice will S. P. SADTLER. depend largely on capacity and reliability. Chemical Industries at Sault Ste. Marie. Eug. a d Mining Jouinal, October 18, 1go2.--The Consolidated Lake Superior Co., which is developing the water power of the St. Mary's river on a
In dustrial Chemistry .
49
very large scale, is also developing with great rapidity a group of most important chemical industries. First a wood pulp grinding mill was erected to utiljze the abundant spruce forests of the vicinity. Then a sulphite pulp mill was planned that required sulphurous acid, so a nickel and copper mine was bought. Utilization of the residuum of the ore was the natural sequence ; the cupriferous residue was smelted into matte and for the noncupriferous a process of smelting with ferro-nickel was developed. Pig iron was then needed, so an iron mine was required. This involved the manufacture of charcoal, which was entered upon in the most modern way, so as to recover the by-products-wood alcohol, acetate of lime, etc. A steel plant and a rail mill followed. Saw mills and a railroad to bring the ore and lumber were also necessary adjuncts. A large number of subsidiary companies have been formed to develop these industries but all in affiliation with the company which is developing the power. S. P. SADTLER.
Brazing Cast-Iron by a New Process. BYFRIEDERICH PICH. Bng. News, Oct. I G , 1902.-A processof brazing cast-iron whereby perfect adherence of the iron to the brazing spelter is effected, is now in successful operation by the American Brazing Co., of New York, under the patent of Friederich Pich. After the iron surfaces have been cleansed from oil, dirt and rust, and made perfectly bright, a purplish brown decarbonizing powder consisting of cuprous oxide and borax, and known as ’ ‘ ferrofix,” is mixed with a liquid to a creamy consistency and applied with a brush to the surfaces to be united. T h e two piecesof cast-iron to be brazed are then wired together, lined up and supported ready for the blast from the ‘ ‘ torches.” T h e iron is then brought to a medium cherry-red when some of the ferrofix in powder is added and thus continued until the iron is a very light cherryred when it is ready for the spelter. When this latter has been run into the crack and the joint is completely covered, the casting is allowed to cool slowly in the air. T h e broken edges of the casting, it will be seen, are freed from the graphitic carbon by the ferrofix treatment to a depth of from to ’/, of an inch from the surface, and are then capable of perfect brazing. S. P. SADTLER. Manufacture of Nitric Acid by the Atmospheric Products Co., at Niagara Falls. BY J. W. RICHARDS.Electrochemical Indusfcv, Sept., 1902, p. 2o.--The patents of Bradley and Lovejoy are now being developed by this company on a practical scale a t Niagara Falls. T h e patent is for a manner of producing nitrogen compounds from atmospheric nitrogen, and points out that wherea s the silent electric discharge and the spark or disruptive dis-
50
Review of America12 Chemical Research.
charge can cause nitrogen and oxygen gases to combine, they have very little capacity in this respect, which is also the case with the electric arc as ordinarily wed. To obtain efficiency, it is necessary to use an arc, divided up into such small, thin, flat subdivisions as to present a large surface for a small amount of energy ; the thinner the arc the greater is its efficiency up to the point where it breaks. I t is necessary, therefore, to greatly subdivide the current, to arrange the arc circuits in parallel, and to provide against short-circuiting. The company uses a 4 j Kilowatt generator, ordinarily delivering 0.75 ampere direct current a t a potential of 8,000 volts, but capable of delivering several amperes at as much as I j,ooovolts. T h e current supplies 13s arc contacts, each of which is made and broken jo times per second, giving to each arc some 0 . O o j ampere. The arcs are all spruug successively 6,900 per second in the apparatus, each arc lasting about I]zo,oooof a second, and thus giving practically a steady load to the machine. As each arc tends the tnonieiit it is formed to increase suddenly in volume, the short-circuiting, which this would produce, is retarded by placing inductaiice coils or resistances in series with tlie arcs. These are so calculated that during about I ] ~ O , O Oof O a second they impede the flow of the current, therefore preventing too high ari amperage flowing, and during the succeeding 1l40,ooosecond, while the arc is being drawn out and is about to break, i t sends ail impulse which increases the flow and so prolongs the arc. Vsing 8,000 volts, with an average current of I ‘zooof an ampere to an arc, the arcs are drawn out 4 to 6 inches. By keeping a constant flow of air into the apparatus, tlie per cent. of the conibinecl products i n the issuing air is only z to 4 per cent. and inucli loss by dissociation is thus avoided by keeping down the concentration of nitric oxides. T h e patent claims are for ’ ’ exposure of a mixture of nitrogen and oxygen to the action of an electric arc and renewing t h e mixture so as to prevent dissociation.” The output is represented by one pound of theoretical HXO, per 7 horse-power per hour of electric current used. The air used is first carefully dried to avoid formation of acid in the apparatus and consequent corrosion of the nietallic parts. T h e inside of the apparatus is protected by a coating of asphalt varnish and glass peep holes provided, permitting inspection of the interior. A mixtureof equal parts of oxygen and nitrogen works better than air, giving a higher return for the current used. T h e issuing gases pass into an iron reservoir two feet in diameter by ten feet high, where they have a chance to still farther combine, and thence pass iuto a scrubbing tower to condense the gases produced. In commercial practice, water towers will be used to obtain nitric acid, while Lunge’s
scrubber, supplied with milk of lime, will be used to produce calcium nitrate for fertilizing purposes. S. P. SADTLER.
Electrochemistry at the World’s Fair, St. Louis. BY W. E. GOLDSBOROUGH. Trans. A m . Elec. Chem. SOC., Vol. 11, 1902.T h e writer is chief of the electrical department of the exhibition. One of the five electrical groups is devoted to electrochemistry. Class 434 includes batteries ; class 435, electrolytic appliances and processes : class 436, electrothermic appliances and methods ; class 437, applications to industrial chemistry, disinfection, bleaching, etc. Efforts will be made to have as many processes as possible in actual operation, and considerable power has been s e t aside for this purpose. J. W. RICHARDS. The Electrochemical Industries of Niagara Falls. BY J. W. RICHARDS. Elec. Chem. Znd.,September and October, 1902.A long article ( 1 8 pages, 33 illustrations) describing the natural facilities of location, power-plants and the eighteen industries located a t this great power center. Of the 60,000 horse-power now being developed there, 45,000 is being used in electrochemical processes. T h e cost of the power is $15 to $ 2 0 per horse-power year, according to quantity, which is cheaper than i t could be generated from coal even if the coal cost nothing. The Castner Electrolytic Alkali Co. employs 6,000 horse-power, using 1,600 of the Castner rocking cells to electrolyze brine. T h e y use 50 tons of salt daily, and produce 36 tons of caustic alkali and go tons of bleaching-powder. Their efficiency is 93 per cent. on the amperes used. The Roberts Chemical Co’. uses 500 horse power in the production of caustic potash and hydrochloric acid from potassium chloride, but their efficiency is low and general details of the operation are lacking. The Acker PYOcess Co. uses 3,000 horse-power, in forty pots, to electrolyze molten sodium chloride, the evolved chlorine being used for bleachingpowder, the sodium being absorbed by melted lead, and the alloy decomposed by steam, to form melted caustic soda. The 8,000 ampere current yields 90 to 9 j per cent. of the theoretical output. T h e current density is 2,7jo amperes per square foot of anode surface. T h e anodes are Acheson graphite. The plant produces 23,000 pounds of caustic soda and 57,000 pounds of bleaching-powder daily. The National Electrolytic Co. uses 2,000 horse-power to electrolyze potassium chloride solution a t 70’ C., producing potassium chlorate. T h e efficiency is about 7 0 per cent. on the amperes used. T h e anodes are platinum foil, the cathodes bare copper rods, close to the cathodes. T h e apparatus looks like a filter-press. In it, about one-third of the energy of t h e current is absorbed in the chemical work, and two-thirds converted into heat. Their output is about five tons of chlorate per
Review of American Chemical Research.
52
day. T h e Oldbury Chemical Co. uses I ,000horse-power to inanufacture potassium chlorate and yellow phosphorus. T h e latter is made from natural phosphate rock by the Readman-Parker furnace, the mixture of rock, silica, and coke being fused to calciuni silicate, while the phosphorus distils. T h e output is given a t I ,000 pounds of phosphorus and an equal amount of chlorate daily. The UTzited Barizmz Co. uses I , 2 0 0 horse-power to melt, i n three furnaces, a mixture of barium sulphate and carbon, producing barium oxide, which is run out, dissolved i i i hot water, and crystallized from solution by cooling. T h e output is now twelve tons of crystals daily, and the plant is tieiiig enlarged to sixty tons. T h e reaction i n the furnace is practically I3aS0, C = BaO SO, f CO. Attempts are being made to utilize the sulphur dioxide for making sulphuric acid. Thc A m f i c r e /:'/ectvochemical Co. is experimenting on the nianufacturr of cyaiiides by heating BaO with carbon in an electric furnace, thus producing BaC,, heating this in a current of producer gas, aiid thus forniing BaC,X,. This is treated with dilute acetic acid, producing barium acetate, and the HCN g a s evolved is riiii into caustic soda solution to produce sodium cyanide. T h e solution of barium acetate is evaporated to clr~~ness aiid distilled, giving off pure acetone and leaving barium carbonate. .\ riumber of other promising processes are beiiig experimented wit11 b y this company. Their inanufacture of artificial camphor is already an assured success. The AtiizosfiIie~ic P r o d i d s Co. h a s an experimental machine in working order manufacturing nitric acid by the use of nitrogen and oxygen gases. led into a chamber where 6,900 arcs per second cause the cotnbinatioii. Each arc takes 0.005 ampere, a t 10,000volts potential, the arc beiiig kept down to this sinal1 amperage by a choke coil iii series with it. T h e output is one pound of pure H S O . , per 7 horse-powr hours of current, which costs about one cent at Niagara. T h e company is contemplating a 2,000 l i u r ~ e p oC~Y ~idant. \ The Eletfm'cnl Lend Redurtio?i Co. reduces lead sulphide to spongy lead by Salom's process, wherein the galeria is used as cathode in electrolyzing dilute sulphuric acid. X summary of this process has already been given in this Revien. 24, 326. The full capacity of the plant will be ten tons of sponge daily. T h e spoiigy lead is in a condition very suitable for solutioti, corrosion, or conversion into other lead salts, arid can be pressed directly into a storage-battery plate. The Ningarn E/ech-ocheniica/ Co. uses I ,000 horse-power in electrolyzing fused caustic soda, by Castiier's process, within 20' C. of its melting-point. T h e output is about three tons of sodium daily. Each pot takes 1 , 2 0 0 amperes at j volts, drop of potential, and the efficiency on the amperes is about go per cent. or four horse-power hours per pound of sodium. T h e larger part of the sodium is u+ed for producing sodium peroxide, which coin-
-+
+
Industria I Chemistry.
53
mands 35 cents per pound. T h e market for pure sodiuni is very limited. The Norton Emery Wheel Co. uses 500 horse-.power to melt bauxite in an electric furnace (Jacobs’ process) and produces therefrom an artificial abrasive. Carbon terminals dip into the fused bauxite, and fresh material is added from time to time until the furnace is fnll. Then the carbons are removed, the contents allowed to solidify, and the block removed from the furnace. The Piftsburgh Reducfion Co. uses 10, joo horse-power for producing aluminum by the Hall process, producing sonie 19,000 pounds of metal daily. T h e pots receive IO,OOO amperes a t 5 volts, and yield 80 to 90 per cent. of the theoretical output. T’ne pure alumina used is obtained by a chemical process, but an electrical process is contemplated, viz.,fusion of bauxite in an electric furnace with sufficient reducing material to reduce all its impurities. A current of 1300 horse-power, a t 33,500 amperes, is t o be used to run these furnaces. T h e alloy produced will have uses in iron and steel or as a paint. The Carborundum Co. uses 2,000 horse-power (soon to be enlarged to 3,000). A current of 2,000 up to 8,000 amperes is passed through a carbon core in a furnace, around which is the mixture of carbon, silica and salt t o be reduced. I n a thirty-six-hour run, three to four tons of carborundum, CSi, is produced. T h e company makes this up into all sorts of abrasive tools, selling nearly I ,zoo tons of this product yearly. The lnfernationul Acheson Graphite Co. uses 3,000 horse-power in graphitizing ’carbon articles or converting anthracite coal into graphite. T h e articles to be graphitized are stacked crosswise in a furnace, covered with carbon, and 3,000 t o 9,000 amperes run through for twenty.four hours. T h e coal is placed in small lumps in a long trough, lined with carborundum blocks, and treated similarly. T h e furnaces are 30 feet long, and require 2 0 0 volts to start them and run down to 80 volts at t h e close of a run. T h e yearly production is joo tons of graphite. J. W. RICHARDS. A Unit of Electrical Quantity for Use in Electrochemical Calculations. BY A. E. COWLES. Trans. A m . Blec. Chem. Soc., Vol. 11, Igoz.-It is found that a kilo-ampere operating one day sets free almost exactly two poiinds of hydrogen, or two poundequivalents of any chemical element or 500 amperes in a day liberate one pound-equivalent. T h e agreement is close enough for industrial use Another close agreement is, that IOO amperes i n a day, liberating one-fifth pound, give almost exactly one cubic meter of hydrogen or of any other equivalent gas. T h e writer indulges in some speculations as to a possible reason for t h i s coincidence. H e proposes the name ‘ I pound col ” for the 500 ampere-day. J. W. R I C ~ A R D S .
54
Review of American Chentical Reseawh.
The Theory and Practice of Continuous-Flow Electric Calorimetry. BY H . T. BARNES. Trans. “!?a. Elec. Cheni. Soc., 1?0l. 11, 1902.--The method is applicaide to measuring with considerable exactness the specific heats of liquids, and will be able t o render considerable service to thermochemical measurements. It is, therefore, commended to the attention of experimental thermo-chemists. J. 1Y.RICHARDS. On the Fusion of Quartz in the Electric Furnace. B v R. S. HUTTON. T y a m . Am. Hec. Che?it. Soc., Vol. 11, 1902.--Tlie
author carried on experiments at first with a small open arc and magnetically deflected flame. With this, the quartz must be kept outside the reducing effects of the arc, to obtain a clear fusion ; if the quartz was too close, a black spot formed on it immediately. For working on a large scale, a direct current of 300 to 500 amperes at 50 volts potential was passed through a carbon rod embedded i n silica sand. In this way, a tube of fused quartz appears almost at once around the rod, which is then fused down to a clear tube in an oxyhydrogen flame. T h e fused quartz h a s the smallest coefficient of expailsion of any kriowii substance, is almost unbreakable by heat or cold, and will prolxiblp become a commercial article. J. 11’. RICH.4RDS.
Advances in the Closed, Continuous Electric Furnace. BY
E. R. TAYLOR.Traizs. Am.EIEc.Chem. Soc., 1’01. II., 1902,Describes with illustrations, an electric furnace 16 feet in diameter by 41 feet high, used for making carbon bisulphide. For electrodes, carbon troughs project into the furnace, into which is fed broken charcoal. T h e trough conducts the current with little resistance, but inside the furnace communicates its current to the lumps of charcoal, which are being continually consumed by their high temperature in contact with sulphur vapor. T h u s thecontinuity of the electrodes is maintained. There are four electrodes, one every goo> aud the current can be sent through adjacent pairs or opposite pairs, so as to melt down the charge uniformly. T h e writer says he would have no hesitation in: building such a furnace so large as to ‘‘ dwarf the largest blastfurriaces.” J . \Y.RICHARDS.
The Efficiency of Electric Furnaces. BY J . V,‘, RICHARDS. Trans. Am. Elec. Chem. Soc., Vol. 11, 1go2.-Calculations a r e made of the proportion of the heat energy of the current used which is efficiently applied to heating u p the furtiace contents t o the reaction temperature and in supplying the deficit of heat called for by the chemical reactions taking place at that temperature. T h e ratio of the sum of these to the total heat energy of the current used is called the efficiency. As an example of heat-
Agriculiurai Chem isf r y .
55
i n g alone without fusion or chemical reaction, the Acheson graphitizing furnaces are considered, the efficiency here being 7 5 per cent. As an example of simple heating with fusion, the Jacobs' process of fusing alumina to make artificial corundum is taken, the efficiency calculated being 74 per cent. As an example of heating with chemical change, but without fusion, the 1000 horse-power carborundnm furnaces are taken, which calcul a t e up 76. j per cent. efficiency. As an example of heating to fusion, with chemical reaction, the production of calcium carbide shows a calculated efficiency of 62 per cent. The electrolytic decomposition of a fused salt was illustrated by calculations on one of the Acker process pots, where 8000 amperes pass through melted sodium chloride, the efficiency being 63 per cent. Of the total heat generated by the resistance of the electrolyte, onefifth is utilized for melting the fresh salt added and four-fifths is radiated. J. W. RICHARDS. BY E. A. BTRNES. account of numerous voltaic couples used in fused salts, such as various metals with graphite, in melted caustic soda. T h e voltages observed were up to 2.3 volts. Compound cells were built u p of nitre in a porous cup, with caustic soda outside. T h e results of 33 measiirernents of electromotive forces are given. I n the discussion, some took the position that such cells were largely electrothermic in their action, i. e., more electrothermic than electrochemical as regards their electromotive force. J. W. RICHARDS. Voltaic Cells w i t h F u s e d Electrolytes.
Trans. A m . Elec. Chent. Soc., Vol. II., 1902.-An
Fuel Oil. BY W. W. REED WEST. Elecfrician, 30, 302-3.T h i s gives a description of the experience of the Houston Lighti n g and Power Co. T h e oil is kept in brick underground storage tanks where it is heated in cold weather ; hence it is pumped to small receivers whence it is forced to the burners. It is found that I ton of soft coal is equivalent to 2'/, to 4 barrels (320 pounds each) of oil : on four d fferent burners, tests a t the switchboard showed 0.57 j to 0.7 13 gallon oil per kilowatt-hour. On two Babcock and Wilcox boilers, tests showed 13.48 pounds, and 1 4 . 7 pounds of water, from and a t 212' per pound, of oil as against 7.43 pounds per pound of coal. Where oil has been properly used no evidence nf injury to the boiler has been found. A. H. GILL. AGRICULTURAL CHEMISTRY. S i l a g e Studies. BY F. W. MORSE. N . N.Agr. Expt. Sta. Bull. N o . 92, pp. 49-62.-Analyses of Sanford corn at different stages