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H.C.) B.Sc. H. HOARE Lond. H. SUTHERLAND. F.I. B. BENNETT. D.I.C.Sc. M.I.S.C.Sc.S.Sc.Sc. F. GARNER H. ASSISTED JAMES OF INDUSTRIES SAMUEL by A D.A.CHEMISTRY INDUSTRIAL BEING SERIES A OF VOLUMES GIVING COMPREHENSIVE SURVEY CHEMICAL THE Edited D. A. M. BACON.D.. E.Sc. S. F.. F. B. RIDEAL. D. SINDALL. K. SMILES. F. W.I. SIMMONS. (Vict. B. R* PARTINGTON. Ph. H. CARR. SAMUEL D. GREENWOOD. PRATT.Sc COLLINS. HUGH S.. BY J. F.C. M. . B. TAYLOR. W. H. F. W. WHITTAKER. LONDON ARTHUR F.C.Sc. F.I.Sc.C.Sc.. FELLOW UNIVERSITY OP A. D. RIDEAL. R. C. COLLEGE.I..Sc.Sc. AUDLEY. M.C. BARROWCLIFF. GRAY.Sc. ERIC M. "C. B.C.

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.D. R1DEAL OP WATER SUPPLIES YORK COMPANY NOSTRAND 25 " PARK PLACE 1919 F.). NEW D.INDUSTRIAL ELECTROMETALLURGY INCLUDING ELECTROLYTIC AND ELECTROTHERMAL PROCESSES BY t K^RIDEAL. WITH S. Ph. .LC. ERIC JOINT AUTHOR MA. VAN (Cantab.

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of opportunity an raw the of in all branches accelerated been Empire industrial revolution a in recent Applied Chemistry sections with separate special article made to of instead branches or get away graph. into deal affected as dealing will the divided sections subject in the An be in select a how stimulating invention. mono- from .and section. war. will Present will and new subject. different in the the and by the application of this knowledge output chemical years technology. in the progress of requirements a The complete in itself. the limits. showing the industry will notes world. attention. in fact. be on the also the with the be kept will they and and industrial possible some space methods There and will be a bibliography to follow only be introduced line of argument. so the volume Each general a chemical effect than aspect will also laboratory. be principles have manufacture. illustrate to serves also shown. and of the will the information attempt manner will but of a will. countries. treated prominent will be influence the the to parts of the will be more of survey The development increasing its engineering standpoint.o k O i r GENERAL The PREFACE of rapid development has brought about This has growth British has now during the materials The subject in this series of handbooks available industrial the rather will give of of industrial Historical different of branches within moderate future developments will be devoted to a chief each in far as it book Each chapters. of of that have tendencies producing Statistical be feature have than inventions in comparison general bibliography.and applied been be from industry.

As the and far as this general scheme it is country of is concerned. These conditions. authorities and of that. on couple of days spent in hunting through the libraries of scientific societies. of survey assistance whole. details and student advanced the mind is often his of such remedy basic essential industrial career. also to original.but readers PREFACE references to special points on required. this series confidently hoped that of it is believed handbooks it will is supply that unique. are only not manner. of the his as should books subject which realizingthe industry to the view the sultant. their memories to refresh subject with While hard the student readable more affairs. to the value to to once information they branches to standard the comprehensive a on probably find these guide prove obtained he his immediately a a industry regard as his by very objects of will our information of to in the limits narrow industry.vi GENERAL the orthodox textbook by of affairs men who in matters if time for fuller details works useful knowledge. text- present have who when of the concerned. long especially the out It has that with crammed facts. mental . To His valuable. "because the rather specializedin books books actually engaged Those series. con- of proper special points. already quite sufficient. knowledge academic industrial current to the and this which so the thus for save chief the the than larger they more a in not are serve can elaborate go hensive compre- material ordinary textbooks of the at books. having whole of commencing on giving be can adjunct an as of book reality drawback a of his lack subject. and of the literature the positively handicapped industry one recapitulating the been A of intended are presenting at facts power is will also volume The is the collegegraduate. but technical to with compass. there found refer to ment treat- of which also be time to the large class of very special technical no of moderate book a the to should books having large standard the The require from may appeal make to possessing good textbooks. they will aim education technical wish of state a be crowd a living industry.

SAMUEL been RIDEAI. of will .munitions fortunate are for in securing Industrial Chemistry. have volumes who departments the whole of applied series chemistry Empire. contribute to throughout writers connected specially the the industrial coming the further vii PREFACE GENERAL for with and the trust development different several the that I war..

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endeavour pages electrochemical result applied technical great a been cases. in the the great hands time gators investi- by out materials having both waste English-speaking and power part carried requisite the suffered to or work development taking has processes the that of sources are variety. course an chemistry development. foreign equipped forgotten be English experimental in money not the purchase to and are regret English Notwithstanding bibliography possibilities methods our covering has electrothermal usually attention. In both many economic. As result a either ill there with awaiting capable of Industry in in raw at knowledge. the English the two or exists there element that chemistry. concern receive to to application this dignified confined the of in and made the present considerations whole the of educational higher being been in except the metallurgy electro- teaching research has been student from field. but scant lectures in a excellent an electrochemistry. electrochemical industrial and IX processes advantages offer over .AUTHOR'S Amongst the shown following the of the both indicate and electrolytic is It matter a Electrochemistry in "subject" a limits and of past and has not yet. theoretical on personal of physical fact one few a domain. of branches many has in PREFACE It must countries in of post-war very great those who period of reconstruction. raised to lack this sufficient the of that text-books a to eliminate in ceptional ex- of standing a As system. specific cases aesthetic.

small than most solution decomposition direct which greater compounds results metals elements many certain placed are small their taken is sign to processes. the account on compounds the at of and the high reactions where include emphasis in have the gives has electrolytic tion dissocia- the and temperatures. the calculations the experimental laid normal an negative a the the possess of end. 19 1 S. i. those whilst of correct. London. difference. or processes hope may and metallurgical or of PREFACE K. pressures. introduction. contribute may of for case deliberated and due the that velopment de- the exploitation the author volume present sections hydrogen of the both have the the more of in in and treatment. heats for This accurate stable many the basis the electrode whilst deposition. in purposes Special colloids their usually processes partition' slags shown as of of necessarily must electrothermal in derivation practical of formation of substances been used involved. Iv. effects.e. coefficient metals. that In electrode of standard of pressure elements which noble In of form although upon of application assist in for electrolytic June. to . influence elucidation the tional conven- electrolytic value method. sufficiently been given are irreversible whilst before that chemistry electro- this the as chemically potentials. potential those solution been has zero positive potentials Electrolytic on new consideration. E. the strictly not the of arbitrary hydrogen.AUTHOR'S x older chemical old it is the ones. observation immiscible between the active.

Neodymium. XI Praseodymium. Aluminium.. Antimony. METALS. Lead. Lead. deposition Colloid electrolytes." IN AQUEOUS SOLUTIONS. Winning. Commonwealth i " . Barium.. and Diaphragms metalliferous The Power. of silver. Manganese." IN FUSED ELECTROLYTES..- SECTION THE OF Gallium. Parting Gold. of resources British the and passivity. Cadmium. Vanadium. Tin. Rotating metals. Calcium. and Detinning. Bismuth. Boron. uniform Galvanizing. The Ionic Electrolytic theory. Lanthanum. Conditions plating. Fused cataphoresis. electrolytes. Potassium. Plating.CONTENTS PAGE GENERAL PREFACE AUTHOR'S v PREFACE ix INTRODUCTION. Copper refining. aluminium Strontium. Sodium. Zinc. Nickel. Thallium. III. ELECTROLYTIC THE TION PREPARA- RARER Cerium. Silver. SECTION ELECTROLYSIS I. brass. Uranium 135 . Cobalt. Indium. " addition of and gold for Complex Zinc. Cobalt- alloys 28 SECTION ELECTROLYSIS II. alloys 109 . electrodes. Over-potential potentials. nickel Bronze agents. Titanium. Magnesium.. Reaction velocity.

cyanides The methods and Haber cess." Graphite." SECTION Properties furnaces. Silfrax. 239 . nitrides. Nickel. SECTION disulphide Silundum. AND Electrothermal iron. the of THE Calcium Tapping CARBIDES. furnaces. The nitrogen Arc problem." METALS BY FIXATION NITROGEN AND METALLIC COMPOUNDS. Siloxicon.CONTENTS xii SECTION PROCESSES. Molybdenum. pro- cyanamides " VIII. Vanadium. Zirconium. . Block furnaces . Phosphorus. Uranium. furnace. Heat of Continuous formation. OXYSILI- AND OF CIDES Carborundum. furnace. uranium.164 Fibrox . Tellurium. Composite high frequency The and refining deoxidation furnaces. Carbon Arsenic. FERRO-ALLOYS. furnaces. Biochemical Hausser's processes. SECTION ELECTROTHERMAL VII. Chromium. THE iron. carbide. Manganese. . the method. CARBON. VI. . 183 induction chromium. and Dephosphorization. APPENDIX 205 237 INDEX . ELECTROTHERMAL IV" PAGB Zinc. 139 CARBORUNDUM V. titanium. The furnaces. steel. effect " The production tungsten. Silicon. Monax. Tungsten.172 . manganese. Copper. ingot or carbides. IRON vanadium." SECTION Electrolytic of and The functions desulphurization. "pinch Ferro-alloys. pig the of Arc slag. boron . Induction Ferro-silicon. molybdenum.

. are terms volt per obtained in cm. The sulphate. per in dilute for solutions hour under solutions. in aqueous anode cathode decreases and subjected he at the electrolysis. at 180 C. present e.INDUSTRIAL ELECTROMETALLURGY ~ INTRODUCTION The foundations lurgy general principlesof electro-metallaid by Michael Faraday in 1833. and quantitativelaws which on electrolyticprocesses it is to that that a Faraday each suggestionof in solute solution the a a the solution is velocities FromHittorf to calculate the actual forgotten electronic first ciated asso- tangible theory of electricity. such electrode. anion. for example. whilst of the calculate to Kohhrausch investigation on solutions.by values or solvent increases such By atomistic the concentration when valency of 1853 Hittorf In owe we science the the unalterable definite and with both electrolyte as the us gave founded.g. cathode. cms. an and quantity of electricityis experiments of the fundamental It is frequently altered at series of of the noticed of copper transport number later (1869). the an that elaborate of dilute conductivities gradient. concentration the during of the electrolysis. to able was ions. wh" introduced were the of the nomenclature. able to was ions under a a few the years molecular the determine definite the potential 'sandKohlrausch'sfiguresitis possible ionic velocities potentialgradient of one The following figureswere a industry of important generalization element.

especially genious dealing with stroog electrolytes. the to in solution. but of of by solutions far-reaching importance. Up solvent the dissociation development in the principlesof hypothesis as to the state of the solute was 1887 In necessary.and as a result inthe theories and formulae were proposed to square the . gaseous a subject by reacting constituents. concentrations the to ions or laws gas of the in the made was applied the who concentration The in advance and been has results the laws gas only extremely not conception to great obtained dilute varied. A further Hoff. hypothesis of electrolytic conduction is in solution ions the ment measure- this stage in the to electro-chemistryno in by actual confirmed were the with in accordance solution as whole a is of laws the electrically neutral. and mass by others. It the is somewhat ionic 't Hoff theory exclude case and treated could between when the be the originallysuggested by somewhat other this that development Arrhenius chiefly accomplished in Germany. theory of Arrhenius to this theory a scheme and Grotthusian the the replaced by was ing Accord- 't Hoflf.ELECTROMETALLURGY INDUSTRIAL 2 The calculated figures of the migration velocity of Steele. molecules ated equivalent is There service a doubt no in undissoci- regarded were partialpressures or that this rigorous application of the been have solvent the electro-chemist. of to In entirely neglected vacuum in which discrepancies were gases noticed experimental and calculated results. Van dissolved salt when partiallydissociated in ionizing solvent an ing follow- into free ions. according to the " is established Equilibrium action. Whetham. substances to 't Van as of gases mixture. was a " unfortunate pedantic train important function rather as factors of the the distributed. from solvent convenient Many of due was thought and Van quently fre- where tends consideration. and Ix"dge.

Van treatment old of the indicated solvents in the and theory has new no the (1904. and Cs* and may are case of the be entirely I'. pressure solution been has or metallic the electrons the this On the metallic to of the ions ions potential or are ionic F'. until layer of .)on be retained not simple thermodynamic great Waal's der Walden of pseudoequation. e. im- most functions. holding the envelope round the solute. the pressure to of Potentials. of the one was light.(H20) both undissociated the salt and ions the being surrounded The of the forces nature envelopes of the solvent. kept into metal in the metal solution and . Since positivelycharged. Uv in the heavier absent probable. all drive leaving the ions negative charges between are are forced the by in metals metal consequently hypothesis advanced assistance great difference in the theory. rising to 6 ions of small or atomic ionic the 9 molecules such ones. Ionization solution to the be must regarded taking place subsequent as (usually hydration) of the solute following scheme according to " MX-"MX(H20)m^M(H20)rc+X.INTRODUCTION facts either scientific The frankly empirical generalization from the of originally stated the by Arrhenius advantages consider now the solvent the problem itself been in a which as At the of at rate any must we in which one if not performs important. as well as the number in each molecules of solvent of envelope. but it ionic the mobilities. that small. some on electrolytes in various theory could present time based or Van experimental work conductivities that 3 the portant. hypothesis.g. Electrolytic addition In " electrode 1889 science. from seems into in Nernst developing possess of a the solution solution. is as yet a matter by uncertainty. simple 't Hoff. et scq. " tendency a ion or as consideration a hydration numbers per weight.as new form proposed capable but one.

of a to by 8n gm. where pressure is great is the ve8n transfer the of electrode the is evVSn work metal the transfer the from pass with discharge of metallic Imagine to ELECTROMETALLURGY INDUSTRIAL 4 equal salt in the to -^ aC virtual principleof the By work. 8n is also aC. and the and concentration ionic the in on ve electrolyte containing an equilibrium is established risen to has molecules uncharged be v potentialsof chemical the and V value solution in the similar a potential between of a at " its ions. of osmotic solution concentration of the to degree of ionization.in contact solution further the ions. and log metal electrical The the P pressure 8"RT prevent valent v charge carried equivalent is the to ions. bringing hn gm. pressures of the of the electrode metals as potentials . difference aC ve : manner metal a arrive P log f- " [l be and respectively. ions to the solution. PT p log X V^8w=8"RT V= or aC We following If also can risen to of valency and electric charge relationship in placed in the the metal ions metal the when the solution of the in the solution has metal further. if fa and aC.with the an ion. equilibrium is established each when fa" fx"Vve fa^+RT But log aC Vas_ft-ri+RT hence logaG ve putting /*" log /x0=RT K VRT 1 aC ve where metal K is to in the The calculated be form regarded as of metallic electrolytic solution from K the measurements the solubility constant of the ions. This ions from where solution C solvent and its a enough gm.

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metal. of The to and the are of copper. tt-Stt.877 -L = . The in dissolve cell so the same cool cell to the as at t+8t. and monovalent a equal heat the " e element of solution is the whilst . in this of zinc atom gm. a vSneSn not the and is temperature the at consequently 8n(q higher temperature will change sensibly with cycle. with of tration concen- course temperature scale. + 1 " 8t ve 8it In the cases many temperature coefficient is - so small 8t that the term lations of t" ot may be neglected for approximate calcu- n.provided * / is measured in degrees on that the absolute calculated. a t the is the v until 8n current ions gm.the wire. q is the where 8nq" to of heat of gm.ELECTROMETALLURGY INDUSTRIAL 6 zinc sulphate/zinc. copper. than only associated changes in the electrolyte. atom be of zinc cell at t is of the valency of the solution through subsequently allowing work chemical the raise then we of zinc gms.F. With the a passage AND potential difference of the smaller is current PASSIVITY. and imagine it dissolved and of amount again to If charge E. v8ne8iT N the perature tem- volts.M. equal to ve8nn. that . copper redeposit the 8n to and work at t+8t and to zinc ow __8n(q"e7Tv) " ^ q or 7T . n cell is the equivalent of gm. the the cell is by the equal to8n{q"ve(ir+8ir)) if the heat manner does During out absorbed heat similar a of reaction external quantity of work the temperature. per done by work a is given energy ""eirv). given heat is performed at the out equal lower 8n(q" etro). where case 2. OVERPOTENTIAI. electrical the * t at a pass being joined by copper deposited.

The by is not theoretical a certain According to . for rate. electrolytes in the dealt circuit. For the sulphuric acid following ionic discharges take electrolysis of dilute electrodes. discharge. of the Joule heat be order of irreversible surface polarizin de- subsequent sections. be that noted reactions anodic cathode where processes hydrogen liberation. electrolyte same take cathode.INTRODUCTION ions other are not capable example. in the between platinum electrolyte.F.M. 167 ' Ih-"h2 S04"-"H2S04+02 "95 1 H-"HS IH-"H2 130"-"03 2-83 practice In than has electro-depositionat thus the Frequently be the traced general of the theory is used with the at the of causes of the amount to expense found sary neces- mena phenoApart loss due the to sistance re- discrepancy between accounted for by of the one " In " identical and the at electrodes. the P. and HSO/-"HS04 2*60 place. the potential lower at the being discharged of in present 7 with place increasing applied potentialdifference. it has independent The : Overpotential.D. definite for necessary is liberated. "2 aOH'-"HfO+0.will can be to applied voltages lower of the from an added agents reduce considerably higher potential difference a calculated that H2S20.D. in occurrence of the of uses electrolysis. those following factors necessary to one to potential difference practice may and hydrogen be excess taking place the to bring about applied economic electrical energy the depolarizer. {nrvn-i ro8 o"-"o.and consumption those been nature has for of the always each to the increased particular metal. P. when applied E. Ionic in volts.

degree Faraday of the important on may the have to been Society be mentioned surface. tungsten. of the technical serious more occurrence Various for the account in the Electrolytes containing oxidizing acids case. and the characteristics of the of more a suitable gas to a marked been more although treatment. aluminium. exhibit may be tendency to anodic is actually " noble than amongst formation others. correlate although t\ values the of absorbed gas and ions the gas and the with diffusivities the metal. prone is taken usually. chromium. however. : and proposed passivity. As " processes as formation Advantage by certain is the tensions.which film are platinum. the to metal this cause probably all metals following exhibit iron. molybdenum. in the . following the forthcoming. have "Transactions of disturbance no than theories quite certain passifiedby phenomenon of In more phenomenon may ible irrevers- passivity. " appears with the of cobalt. with the the satisfactory explanation for this phenomenon No yet of values the are " : . inconsiderable of to cadmium. A magnitude processes molecules metals and thetical hypo- of gas is also associated of oxygen overpotential phenomena. in the electrolyticreduction of zinc and Passivity. with high overpotentialsexhibited the over- made of formation heat surface been have attempts with hydrides. of cathodic The in certain tion deposi- hydrogen. anodic evolution in the case anodic is the electrolytes metals solution .8 ELECTROMETALLURGY INDUSTRIAL Caspari. summarized for 1916 I .

of transformation electrolytic cell. Velocity. but the to in change no the ceased rates into before other. If solution From occurred metallic anode to various the cathode in instantaneous. forming cupric sulphate with metal reactions the copper one slowest is nevertheless but process. intermediary This use we of imagine copper one ion will be of the the factors in by followingexamples the electrode becomes . retarded speed. velocity of ionization or hydration of the ion is 4. which each it passes set 10. found by experiment that periodicity of for frequent less place. the anode The can we S04" the solution is reversed.000. and current of the total sum follows as : lysis perform the electro- to current electrical of cause discharged. and to to that uniergo velocity of electrolysis. modification. whilst such they electrode the weight will result.as speed cycle of operations may a in electro-chemical most maximum The " change involving If allotropic an the its normal below the into metal electrolyticsolution pressure is low. but were did periods. . were 500 copper hydration solution figures it is clear the ions the alternations up whilst removed sufficiently quick were potassium cyanide these of a unless fro from and to are alternations the loss. an do Leblanc of current a a to in solution. above and 50 prevent means loss in net a if hydration. The any 9 two : Cu^Cu"' It is evident should that place if the take the electrode in the solution instantaneously. The of film. sulphate with when that tfo made looked over- alternating an be generalization is frequently be indicated may which at velocity of the maximum the important inefficiency. Reaction place is by set link. but modifications has of occurs actually take present in the electrolyte. of which take oxide an of the surface conversion 3. by of weight simply oscillate ions solution. at the instant next the cupric ion will be discharged be can represented electrodes.INTRODUCTION of formation The 2. actually at a from are limit by to the no the .

but aqueous efficiencies point is of somewhat example where due melting appreciable vapour low melting point. form a To obviate of the in It is entirely of the colloidal quantity of the or alkali minimize of as the siderable con- very posited de- since the liquid exerts an fused In " of electrolytes unstable in the aqueous notable A occurrence. the of the in the " or the sub-salts formation are : during the electrolysisof calcium dissipated through fine cloud of frequent metals. to metals technical the present (1800 Davy alkali or metal. Cloud but disturbing influences. The fused isolation of the hydroxides. frequently not electrolyte in yet uncertain the form of the cloud whether a cathodically deposited in the metal solution electrolyteshould 4. first pupils. alloyed cloud it contains whether formation. to various to Evaporation metal.INDUSTRIAL io * ELECTROMETALLURGY Electrolysis Fused in Electrolytes Electro- and thermics. alkalis. the at day. is following increasingly important which is pressure formation. especially lead. Metal in as the the low small with combined or be maintained a it. temperature as possible. cathode 3. and adopted H.who laws at these to fused showed the current the more 1. chloride. coloured yield of metal. loss occur may This Chemical intermediary solutions the causes a formation of reduction mist. Electrolyte. the The vaporization of the to through reactions. important Sir general the conductivity of In superior time. and by Lorenz deposited metal.As " in . of low causes of the higher the 2. the made efficiencyis usually lower. solutions of manufacture systematic investigation of the properties of the fused salts has been his the by electrolysisof method was A 1810). will certain of electrolysis electrolytes containing fused the coalesce. Solution A " always larger for metals During precipitated metal consists of " metal. owing same the is much accomplished by of Faraday's general applicability the electrolytes. becomes side is found solutions. subchloride. factor interval temperature CaCl.

processes to either temperature temperature 30000 C.Zeit. 191 1. electrolyticpotentialsare of the was accuracy difficulties suitable a diffusion of rapidity high degree of no experimental obtained the but attempted. Hersteliung Kolloider Losungen. no of simplification Diaphragms first the is as effects passage products hitherto high-temperature efficiencyof high-temperature in hand this By matter the limit obtainable the 36000 C.the aqueous electrolytic potentials of has n preparation of colloidal metals sols in various as * these For information further to : on subjects. a confined resistances upper is that been Joule the through class. Elektrochemie. " " " . amalgams from electrolytes. Weizur Svedberg." Freundlich Grundzuge marn. equilibria. the reader is referred Die Methoden V. but lies somewhat be it may time there which are have industry remarked three already the estimated been the distinct proved preparation curable unprothe hand increased has operation. Kapillarchemie. in the discussion in at Cataphoresis." Membrane Donnan.f. from name. smelting reflected A an second of sublimation ever-increasing attention subject of the cannot obtained years or in rate means of the whilst great difficulty. a of chemical the by which at has. electro-thermal of development current usually approximated figures obtained the and electrolytes. The fused the by interpolation from connection in auxiliary cathode. electrical the the and properties of gators by investi- electro-chemistry.INTRODUCTION the of case been owing with construction the values to of of of known in aqueous composition The indicated by its produced by The furnace of carbon of heat liberated becomes to number of has been appreciable and has of with the colloids few received have in which last the During and fail to be industry of the future. 17. physical outside electric electro-chemical of the results already province of this volume. 572. solutions fused in metals the of the determination electrolytes.* passing that at lines of research extremely the present in this helpful in field the : " The 1." der Dispersoid Chemie.

3. raw costs place localitycannot method. energy a . in the position electrolyticde- of metals. deciding factors The for the preparation of values of market from materials. cathode and anode the separate phragms. from vary choice product any generally exceedingly are to in the and power sources. electric an protective colloids of use of means dispersion. can been coal.owing in and are processes. two arc. power. these and are countries figuresgiven for the actual supply delivered form being utilized cheapness fallacious.ELECTROMETALLURGY INDUSTRIAL 12 dispersion media by the (b)dispersion by and The 2. kilowatt year to obtaining produced Many are both and It has relative coal. The place. in this energy of power sources radiant of values in electrical power cost rich of different conditions consumption of the generating station. at enterprisesspring all at centre D. the round up point A. Power. relative factory in a power the scale transportation country. to of complicated. Industrial form. dia- across compartments. indeed. of water are gasified peat coal-producing country in water formation the energy. and on from and a to the an creasing in- frequently claimed of water - with produced industries electro-chemical no the industries. the distribution and at B sources and and ideal site for on suitable a manufacturing a to country be indicated as on labour energy. experience important. a Practical is given a strictlyscientific a source site. map method the C. dominant The two solar electro-chemistry requires its and the for factors chief organic fermentation extensive that owing the to electricitycompared in a scale. although compete various turf. The calculation also the and the of the pores of the of ionic velocities materials it is desirable where drop of potential to in used migration through electrolytic operations. such marking off the a raw material and calculating the position of has shown that the factor energy big industrial that by and. (a)cathodic methods.

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be to depends commences presence of the rapidly. to being by industries consumption attempts ing of link- great that the lightingand so in the total becomes The in lines and effected to any considerable of one high voltage transmission. operation. in their production desire turn discontinuous furnace work.000 for same conductors. line. limits distance minimum both which over the raisingthe voltage.000 1901 sidered. Economy supplying rate. volts 10. aluminium sodium has also been protected by glass tubes suggested as conductor. and volt 150. in were In at lines The increased quantities of power distances at however.not loss)loss by heating on power volts) increases 100. except in special cases moment of whilst at ture tempera- air.000 volts transmission constructed. this were transmitted.000 the and pressure the radius conductor. * is only one Although the specificconductivity of aluminium of copper. but the aluminium or transmitted be has only have power tendency present voltage employed the to of raising the By for the cost conditions present time the can a 60. con- producers consumers Under important. as well smaller the discharge expense wood of pole fittingof high voltage insulators. the by the producers.000 which load. commence.and the line the Again. loss corona earlier substituting steel lines.000 conductor. using copper lines. is a better yet per unit of weight.14 INDUSTRIAL ELECTROMETALLURGY flatten their curve. of dust or does with we the the The or voltage longer There and are. half that Metallic a possible . are be but problem the to at steady a must these transmit'at 50. the ferro-concrete to 110. the to On Joule (Watt loss corona critical fog electric in the The brush towers for (above voltage the on high voltage lines. raises the cost of line construction.* made be amount proportion leans to of power large amount a be only can at for electric is power is practicaloperation buy clashing of peak avoid to to off cut problem the moment present power in the currents as but cheap power current. and the heating load small must for the labour production transmission of the first 1891. conductor. At various up consumers power afford cannot is liable to which but the be stations using electrical areas its difficulty.

" . 4. and several Water " to sources. development of economical limiting station If the or generating the neighbourhood England. Oil. the about where aluminium notably in Ireland very on South Egypt. 20. Hydro-electric. power Zealand running country. The cost considerably from is kw. as one- an nomical eco- " of such power super- contemplated.INTRODUCTION factors. The Interim Great 600 some Report points about generating thirtieth machine of the " " one-fourth of economical size of what power-station stations present divided into the have the stations capacity of be single one about considered Thirteen of average power size. which These areas where when the station is distance generating plant. economical the where is further own is population the lines of distance miles. Hydro-electric in Great scarce Kinlochleven. and be may The in Canada. April 1917. production power be can : " 3.p. India. plant power America miles.. are The the in necessity for the centres Britain undertakings in Great Supply Power the out large power of very h. more In the enhanced. and British vary very following . Coal. and may unit. Guiana. must to question of installing a separate of in industrial speciallyimportant are precautions have transmission the 15 of methods following groups 1. Africa. or 5000 Electric the on Britain. found Commonwealth Shannon. 2. be becomes and denser 150 be considered distant some western in the about east it then away In be to appears from power considered. instal one's to transmission of cost of 250 considerably transmission would still shorter. of is power only large installation Scotland.000 Within the large undeveloped the Erne and New installation country exceedingly being at developed for the potential sites . Power. in the and be taken. Gas. production both in there are of Wales Britain.

per- . id. a remarkably cost selling costs actual during power large Odda at The Very one. Svaelgfos and e. the approximate figure of 40s.S. full running are included. whilst in at large choice Norwegian U. Zealand New N.S.16 INDUSTRIAL figures may costs ELECTROMETALLURGY be taken the as approximate running pre-war : " Place. . the pre-war for hydro-electric power widely.. installation earlier plant the conservative Norway to to have the a later much kw.A. side I^egnano. quoted for the and 8d. 67s. 112s. U. In kw. of this power. are Governments of water Trolhatten costs.A. . 18s. Saulte-Ste. California. Ontario. 3^.S. kw. The cheaper rate. from to ns. In the installed plants were that per engineering difficulties the standard installation over fact and in Scotland the rising to be the erection. 41s. per Kinlochleven 40s. 4d. 545. owing of available Royal Commission. year.g. royalties depreciation. yd. 81s.* figures cited the Although above subject are variations. The Norwegian and to seem economic been in Sweden. Canada Hora-Hora. 2\d. . 54s. Total cost . "26 cost. to Niagara.S. 6d. France Scandinavian the last few low figures are in Norway per kw. sites 191 5. 68s. per kw. be of the lie between sellingcosts that opinion when Swedish natural the and 25s. depending on vary is naturally size of with as a to the "20 * a is said costs kw. be taken for a as fair average hydro-electric power. Italy Turin. sellingprice. "15 per installations.A. U. per kw. The to year 45s. year. U. development has years consumer. per "27 about be taken Kinlochleven the cost average to seem ciated asso- Sept. $i. As costs the installation expected. Marie. 20s.and Government higher. . 12s. . Italy Brian9on. pre-war installation wide to costs are not high.A. 8d. on where the a may year basis. was missible.

000 some efficiencyof be large units installed. * " Quarries. at of the United large stations power committee as Kingdom the in at minimum 1915 from we : Mines 8444. and be can For costs.s be maintenance are be hour should at units large large turbo 15.348.. and It would. a generator.500 to 13. which constructed with average equivalent to 3415 B. to sume con- therefore costs Britain. per ton.000 working in stallatio in- cheap required present ditional ad- changes.381 tons material that a about slight export would considerably It is stated consumer. very economic per such The cent.U.s 20.U. irygd. and 14.. per extremely favourably tions. 6d. to disadvantage large reservoirs would periods of slack water. 5'6orf. from taken as A " potentialsource that to ensure have to be of pound 11.T. Pt. per 227 at offers the at be able present existent considered would is lb. c. 6d. 20.T. generating a estimated are kw. an ideal engine of electrical energy to produce 4 kw.U. 2 and .per ton.000 of coal The capital installation to be to operation hour.000 generator in the may kw. a 12s.U. 253. appear possibleto deliver contemplated by 7s.INTRODUCTION The 17 feasibilityof using tidal energy from time from the This time. figureswhich kw. of which raw home the in It is evident quarter left the country." I. iii.U. units of with B.s been has of energy erected the is efficient steam-driven most turbo the undoubtedly of advantages since . Mineral for the "11 and "13 per 1916. hours The deal to good quality coal will produce pound per suffers continuity of supply B. 50. per generators.. low having which kw..000 discussed coal in bulk the reconstruction Production the Taking ys. effici- dynamic thermo- set would lie between the compare the 1915. 10s.therefore.179.T. to sizes minimum about capacity.T. one- that * sellingprice of coal in 1914 was 9s. of coal. compatible Smaller plants B. tax kw. and such on the lower the valuable price for average in 1915.000 produced..T. 256.000 B. cited those with In for tons. installahydro-electric power in Great mined were ency. Coal Power.s.

to rate. fuel the fixed coal of air for air with the value as in scarcely can their for sounder to fuel value other obtain hand countries The with large quantities for their various relative to^the power increased an is these recover production pow^r coal raising steam. at post-war considerably higher still greater increase a of in the cost extremely probable. 21s. . as owing plant where a cent. . as if even would as on far the would materials raw industries. liberation of unburnt the depositionof partly carbonized tar heating system. To produce kw. per ton. Apart by-products greatly above and it would This consumption concerned. .. altogether disproportionate rise in the the will be sufficient of those side the be must that however. 5 per some perfectlyhomogeneous. yet pre-war be may value pre-war coal would to have be hydro-electric power. Although of kw. necessitatinga firing. depreciation=10 Installation 33s. price for hydro-electric power than the raising steam freight rates delivered the It is expected.. . lost were naturally necessitate electrical of of was be value market distillation the fuel suitable economically whilst a than one case definite in the supply . Gas Power.. quantity variable of is by efficiency of The coal fuel of the parts on avoided.18 INDUSTRIAL obtain the ELECTROMETALLURGY following minimum of cost production : year " Coal . per cost . Total . and costs on . obtained in the requiring combustion... zod. . . advantages gasificationof the coal at low and or disadvantages of high temperatures. year the 54s. per swing the pendulum to installations power which over situate are close to their markets. Running cent.. the from fact that to the better and of case proceeds in stages. . 1 for 40s..combustion smoke. partial under a . 3d. xod. the power plant for 4s. . this consideration. " boiler gas firingis steam is raised where coal is employed. thus. but supplies of coal available products useful as their appear by-products plant.

97s. a Total dearer assume 30 are . the generating plant. or hypothetical that province of this the by-products being dependent gasification.U. Sulphocyanide Sulphuric acid Pan . power to of 70 produce B. . containing million 21 noted With metallurgical gasification will give nearly 60. . . of the various 19 (Ifsold 20s.INTRODUCTION slight pressure book. 44s.T. 21s.250 gas for in coal. Against this in than tons ton. xod. 3jd. . be set the value of must million required B. be One further coal-fired a suit the producer is in the neighbourhood gas a complete on and of steam. with . amongst would " depreciation a cent. Present Rectified tar . which be would year turbo-generator coal-fired gasificationof coal. 63s.U. Total d net 5s. benzol. by-products set. gasification Running costs and 42s.. 15. . .U. 10S. od. from waste cent. 5 per : . 8d.) nji. after possible profit on sale at current for depreciation and making allowance for recovery utilized.000 gas-fired turbo-generator would For which firing. Ammonium . 8s. zod. as crude tar g$d. 4%d. 41s.s.U. sulphate Benzol coke . feet of gas We a introduction as amounts the conditions on will We gas. however. cubic for have better required boiler to that give 1 kw. a of coal kw. B. It is or of market coke. od.s kw. is. 32s. cost . .can of the lie outside vacuum. with hour 7s. obtained be mentioned : " value. . 6d.s 5*96 year. will B. 8d. . yd.T. evident. io\d. by-products gas. chemicals.T. per at .T. and 2S. For or fied gasi- operation one we coal . efficiencyof per to as so and nature the coal is practicallycompletely where case be obtained The be controlled illuminating by the suitable can the for fertilizers. a coal . rates.s.000 containing Hence conditions only consider clinker main the of ton efficiency for required. 14. breeze * Net value represents educting working costs of any specialmachinery may * 3s.

below fall and with conditions 97s.s spite of the prime to to heat subsidiary of gas exploded B.T.000 good be raised can net a In addition. per is hour advantages apparent limitations the mover. by the heat exhaust be reduced figure may In engine will raise in the gas in the hour. a Diesel gas-works would or tax . 3000 kw.s.U.U. and low advantages.T. together with the heavy installation expenses. of gas means gas turbine. for the the price the 63s. which are already noticed have We " hour kw. sewage Engines. the Gas Engines.U.T.U. that turbo-generator.500. the being only electro-chemical engine operating on than more in peat. gas wells.s B. gasificationof coal in turbo-generator stations contemplated.T. a 65. large. the only kw..U. if gas engine only gas coal-fired required. natural fermentation the the the septictanks. the other use of be to duce pro- B. and Oil on natural solution is the realization as depreciation make some most B. 8. B.500 exhaust.s. units being the largest constructed. large of the a to 14. the price of by-products on costs of the disparitybetween to as iod. For installations. 10.000 B.T.250 necessary use consumption efficient to modern run equivalent steam In more a would of 13. 8d. relatively small present several Diesel in hour oil technical a be obtained. industries. =335. by the tend which If costs. working and in costs counterbalance The any Power-gas fuel economy which for power sources in the hydrolysis of in various in efficient prime movers consumption per kw. 2d.T. steam words.s in produce from The plant.T. such retting of flax.U. 3. 15. lod. water-power average erected production would doubt would system alternate disappear. turf. engines grade oil the are operation.Under of or kw.500 energy B. the of that oil. to are production machinery long-sought machine.U.s 13. The " is to generation by be found of acetone.500 kw. 1 In the were connection doubtless fall from would year idealistic somewhat these installations of ELECTROMETALLURGY INDUSTRIAL 20 size.but to be would market the there methods be can advantageous most no to nation. 1 a firing is adopted.

.

at some if stock within of tons. Eng. of this area. Siliceous hematite in Griqualand Siliceous magnetite in the regions Low-grade ore is stated to be plentifulin " W. " supplies the being developed Large depositsof followingcountries that to taken. Australia.! the at present available future date and capable ore deposits could means the world's the greater portion of the Iron. many Scotland. Queensnorth of Perth. tite Hema- Cork. Ayr. located to be ores found are : " Hematite. Ireland. Cullis paper metalliferous be found in 1913 Kingdom a inconsiderable. and by no and last the Department It will be noted are exceptions. Wicklow. May 191 7. The " tons in the 24 was Great Britain. Dumbarton. stated * to be Published " Magnetite. Clare. p.would to the Research. it is probable that be quantity of iron imported. Rhodesia. Newfoundland. Sec. Stirling. . Scotia. Hematite " and and Central the ironstones Provinces. Tasmania. County Antrim. a few miles 25 million South land. Canada. India. Bechuanaland. were of tific of Scien- by C. Victoria. New Quebec and and the British Columbia..* from drawn are ironstone and magnetite in counties. United 8 million which iron few some in the smelted ore million with ores. Midlothian. Ontario Brunswick. in County and and in bauxite County Down. Renfrew Ferriferous " Fife. in Ironstone " Linlithgow. Lanark. estimated at tons. Dec. 1916. round Pretoria. in dency Bengal Presi- the in the Magnetite Madras Presidency. New Australia and parts of Western in Western ore South Australia. is available. South and Africa. " Hematite Hematite " in Magnetite in on Nova Bell Island. Yukon. and Iron in Australia. f Trans. Hematite " Wales. 25.22 INDUSTRIAL British Commonwealth ELECTROMETALLURGY given below Report of the Advisory Council Industrial and Society of Engineers. Longford Leitrim.

: 401 Home also found in 1915 of 10 the " molybdenite these Transvaal. . and Metric Cape Colony and the The Molybdenum. " tons.486 5. obtained now 1913 tons. . . according Date. . to of manganese ores Office was in Egypt. Zealand. Date. . of the According depositsare began. Jaipur " S. to The In output. 1914 . Caledonia New 1904. India Australia also Deposits and Cobalt. that year 1914 . Canada . the have cobalt.888 638 in the production monopoly producers of cobalt ore are the S. 1915 . supply . . nickel Country. Coast. in India Country. . 99 128 tion produc- . . Canada N. world's Ontario Metric Scotland. The " 23 magnetite deposits at Plymouth New and deposits of limestone Parapara reported are be to extensive. New statistics. . . 35 Queensland . . in the 1915 63. . Zealand. " Rhodesia and recent the : Country. . of Transvaal. .INTRODUCTION New the Zealand. the returns. in occur New Up " of the cent. foundland New- supplied 90 per the development mines Newfoundland. . Gold world's the : " tons. . . British were chief exporters of chromite The " Commonwealth. . Wales Other . 1910 . . silver cobalt Commonwealth of sources Balmoral Manganese. Wales . following was N. Canada . of to the most within . at : Metric . Chromium. the be found may district " production Extensive .384 11. . .

S.in England. tungsten ore yet no quantity of metallic England. may in to (Pb and England appear scale. are found S. near Australia. the manufactured produced Ferro-tungsten Sheffield. but commercial Rhodesia. Nickel. small too is stated a in that useful Cu to be Broken source of . In area over are was said extensive the to of production the 1915 nickel Cobalt ta exist. to the Quebec.300. prove mottramite It be to be Cheshire. of tungsten of the within and ore developed. Adelaide. confined The " Ontario. Africa. Titanium. on one-half over in New yet been not India. worked been not have ferro-tungsten and tungsten as production during 1914-1915 Commonwealth in well as Wales South . have Deposits which Before war the consumption is now for the mined was was but a as Widnes. Luton near but within ores follows worked Subti up " found are river world's in at Rhodesia. English Steel Industry. Vanadate) Wiltshire Hill. present in deposits in East be Canada has Griqua- land.INDUSTRIAL 24 ELECTROMETALLURGY is also Molybdenum in found Scotland England.notably in Northern also been reported to in this mined ore in deposits Other tons. and the : Commonwealth. present time Tungsten. and India. 1.000 deposits of Sudbury and of nickel amount practically is ore Nickel Alberta. New The " Rajputana Canada iron titaniferous of rutile and Deposits " " have and on a Small been deposits of observed Shropshire. and Vanadium. small in at was the very Zealand.

have sources been developed. Devon and N. was and of the cent. per Queensland from 1913 Britain Great 80 one-tenth. Queensland.000 of the much was deposits in largescale. of S.it Australia the form heavy sea In " and but Canada. and are capable of extensive the Rhodesian exceed those development. production just that developed The exceeded war is stated It In ore the zinc mined England. Wales. that Rhodesia West deposits in North Australia. large quantities of of these none Ceylon. India sands localities in in several occurs zircon. Wicklow. " ore British Isles. were sumption con- South consistingof galena blende mixtures of garnet quartz containing pyrites with a gangue and rhodanite. same of lead on the lead world's 1.chieflyin Wales and exported for reduction. Ireland. and Rhodesia offer fields Cape Province. the Transvaal for further development.000 over were is raised in I9I3It is claimed. and order. Chalcopyrite deposits are found in Cornwall. metal in in where reached. available are As in the sylenite.000 worked been in South whilst Ontario. Zirconium. whilst smaller 25 quantities found are in Western Australia. chief lead and zinc ore producing Koolenay district.700 Broken of ore. British and Lead before Guinea New the to be are Zinc. of lead tons ore and 11. were annually exported. and Scotland. chief The tons 500. .INTRODUCTION vanadinite. a tons. Tasmania and New The the Zealand. Copper.000 tons of zinc in Canada area where ore 86.British Columbia. Other Australian deposits are found in W. consumption copper tons. Extensive Columbia and was British of nearly depositshave output an and the British South New of tons 50.000 of tons 11.500 1912.000. Africa. and Hill in the this of lead source was zinc and in New area tons 25. Australia. just over In " Dominions provided is obtained production Wales. before ores Wales. where the was war the zinc and W. of which million one world's the 1912. Ireland. Broken in Hill according to prospectors. and cupriferouspyrites in the Co.

of of very abundantly less Wales development a a still and South 50. capable and tin where by consumption " 130. for stated mined mines the Chinese the is been has where States Malay annual the years. in New a South appear hydrated Wales. in formed a world's tin which the of tons. of economic on possible as in Co. 100. ores India. is to further of about over for is be to provide production silver.26 ELECTROMETALLURGY INDUSTRIAL Deposits also are worked were at The Tin. sought British of rapidly the in is bauxite encouraged. Antrim. Canada.000. laterite. and scarcity Commonwealth.000 Nigerian the marked a " sole great expected. Upper in iron. and Burma. the consumption world In 5. In number of Tin in ores in found Tasmania.500 a bauxite from these Island utilization future source in of the of this extensive States. deposits considered Western of Since aluminium equivalent sources obtained The found is output Other is and tons. felspars metal. New Africa In be development also are Australia. economically be can our where of tons 1. Vancouver Malay the development. There is within deposits of is deposit from be must alternative deposits capable potassium India. neighbourhood the that Ireland. improvement. for.000 date early very Burma. the annual the it is unfortunate only to which Guinea and low grade a metal production and the metal. rich whilst is found sulphate. must also be .000 annual in tons. Aluminium. Cornwall. aluminium and rising. alunite. Australia.

The Zeitschrift Blount. REFERENCE " " " of Principles " " *' " " Macmillan. Le Elektrochemie. Electrometallurgy." Theoretische Langbein. J. Van W. Transactions fiir R. of the American The Transactions of the Faraday Elektrochemie." Grundniss Albnand." Chemie. Blanc. Partington. Society.27 INTRODUCTION LITERATURE. Elektrochemie." Elektrochemie." applied Jahn." der S." 'Practical of Textbook S." B. Electrochemical Society. Thermodynamics. Nernst. Metals. Laar. Electrochemistry. . Electrochemistry." of Electrodeposition A G. H.

in the a 0*3 in which metalloids amp. low some further was fusing An rise to densities current cms. as and the sulphur adhered above economical could be used. the " +Cii-"Cu+S" anode caused whilst pressures. conducted matte voltage the the acid experiments refined Cu^S now copper by l at blowing free from sulphate . using sulphuric purpose The of and in " Nicola- and Marchese (Cu2S. in Bessemer the to of solution uneven Cu2S-"CuS' which unsuitable were use ing contain- sulphate accumulation rapid the cast for conductivity ferric and copper easily although electrical white and metallurgical ordinary the sulphides. sq.Section I. into of for impurities anodes. especially world's the is copper electrometallurgical remarkable 85 of refining the metal. The Early Electrolytic experiments jew. been has and oldest the production copper advance some years far by processes.Fe2S3) matte obtained that of its Ores. 1908 the converter. of copper recovery a suitable solvent in from directly and and where of electrodeposition subsequent with leaching by ore with." AQUEOUS IN ELECTROLYSIS SOLUTIONS Copper. Borchers Mansfield. The electrolytic largest of per Of recent development of cent. lytic electro- the on a over is dealt made the had has America. into such coarse on of Recovery per 100 only then anodes. from Copper those as metal (Cu2S) matte process. sufficient owing liberation these cells. made metal indicated in anodes electrolytic free this in the acid to electrolyte of electrolyte.

.

compartments generally used. each The reverse situ operations. although to be can cell suitable a cent. Lead sheet) have obtained. With 80 over extraction cent. Electrolysis and chloride oxygen been are diaphragm As from cost for Carbon cost. millboard the The for sulphate Platinum successfullyused. and used cathodes. flows the through on the copper the sulphate- cathode chambers. employed. although suggested. Spain. cathodes chamber flow during the flow at the takes (Fig. cent. ferrous The sulphate produced Cu2S and Cu20 on ferric sulphate partments com- Owing specifically lighter.and are in occurring magnetite (Fe304) electrodes are been have ones graphatized technical dividing the electrodes and to for is electrolytes. base and place in the quently conse- leaves anode compartment anode according the to Cathode Anode : : instead of the evolution equations from the serves to of depolarize the " CuS04-"Cii +S04" SO"4+2FeS(V"Fe2(S04)8 of oxygen according 2SO"4 +2H20-"2H8S04 The interaction saving in the electrical energy to the equation " +02 required to bring about . Arizona. at with experimented modified a the at form Ray Rio at Tinto. in and Cananea.are sheets most satisfactorythan more Vertical ferrous fused and cathode. account rapidly destroyed by 19 using thin sheet copper anode yet been carbon. per is conducted The containing 3 per ores in divided a of problem baths has not ruled out on sulphate lead from of of low their oxide Manganese on whole the the horizontal cells the deposition of copper enters the top. asbestos is usually are expensive.1). and cathode in account on more anode through the anode returns electrolyte becomes the by solution sulphate (formed lead. per satisfactorilysolved. in use evolution peroxide copper.INDUSTRIAL 30 This ELECTROMETALLURGY been has process Mines. material satisfactory in solutions. but arranged in series.

ELECTROLYSIS the follows with : of is very data of the at of the great and requiring 56. solution sulphate copper copper under oxygen overvoltage thermal a decomposition deposition liberation from 31 " minimum the SOLUTIONS AQUEOUS copper depolarizer anode an The no of deposition with as IN 2 anodic as depolarizer we have the equation CuS04+2FeS04-*. voltage copper is therefore VOltS.however.800 voltage calories hence the requisite position decom- is 16. be can reaction 2CuS04 Fig.300 " of copper sulphate at electrode and from be can The ferrous in B. calories Arrangement A.540 The . I"22 = of compartment 4-2 _ 96.(S04)3 requiring only 16. 2 diaphragm into the cell. introduction of a X 4'2 X . .540 ferrous with from for Anode decomposition x cells sulphate compartment.Cu-f-Fej. cnpric theoretical and pressure the t -r-HjjSOj-r-Os +2H20-"2Cu of Cathode one atmospheric other. deposition electrolytes.300 With calculated atom gramme per circulation.800 96. calculated voltage t 1.0-36 volt. 56. the sulphate X of copper.

any ores be can first must ores roasted. sulphuric acid as a leaching agent for copper advanced more rapidly than the ferric sulphate of use has ores Sulphuric Acid and process.INDUSTRIAL 32 necessitates the of use force. It in concrete was found efficientlyfiltered through proposed it with 0-25" mesh. 02 o*8 amp.000 a extracted brochantite in Chile. mine Chuquecamata the course the to method cocoanut crush the approximately leaching that to the lined vats solution matting 12 set ore per with would between be . electromotive i'8 volts and ELECTROMETALLURGY the In experimental with used were greater externally impressed much a density of current a between runs. At of of copper per erection day about pass cent. be said to have may experimental the outgrown stage. The (b) The Process. per sq.000 is in ore taining con- (an oxy-sulphate of copper) averaging It copper. dcm. mastic 2 per cent. is to leach sulphuric acid asphalt. As leached be ferric in the without sulphate oxidized but sulphide treatment. a a capacity of 335. with from large plant pounds of tons 10.

contained this stage to the was found to " be per 2 to 1 cent.dried.. The density of 0*5 Montana Butte by leaching with to to steam with 6o" C. Ajo. per sq. dcm. as chloride .). since only is part of the chlorine evolved at the anode during but part is included in the deposited copper electrolysis. 5 inches vat. with an over obtained carbonate sulphuric acid cent. anodes (63#5 gms. of effective leaching with sulphuric Ricketts 4 cites a case an acid on an oxidized being crushed coke-lead kw. I*. ore per hr. using Sulphur Depolarizer. both noted being SOLUTIONS AQUEOUS arsenic both that deleterious very and for 33 antimony are deposition copper (seep. anodes anodes. dcm. a 10 Previous J". 4 feet five to spent electrolytein the cent. per current a a returned average coke. (c) The Occasionally sulphur dioxide the is Dioxide as injected into the anode 3 a . per of copper. with leaching vats. This to agitatingthe solution with shot copper Cuprous chloride is formed according to effected was in by revolving drums. amp. it was therefore the proposed to remove cuprous not chlorides previous electrolysis. electrolysisthe to At efficiencyof ore by this is treated after crushing electrolyteis heated by neighbouring plant electrolysis proceeds a agitated electrolyteusing 1*4 amps. 91 per cent. close 91 on and copper. 3 feet wide electrolyticcopper i*5 per calcium by smelting with copper magnetite use with hour carbonate \" to . fused can proposed wide and sheet The 2 metallic to to inches thick. at extraction an electrolytecontaining3 per leaching process. 40). at ore subsequent gave a per o#o8 kw. long.ELECTROLYSIS IN will be It absent. The main is the objectionableimpurity chloride. 4 feet and deep. sq. At It cent. the equation 2CuCl2 +2Cu-"2Cu2Cl2 which reduced and is be filtered off. Arizona. electrolysisusing yield of 1 posite com- lb. per cent. and the ordinary experimental plant was I^aszczynski3 obtained with chloride. of copper Sulphate Process.

INDUSTRIAL

34
chamber

of

dioxide

may

ELECTROMETALLURGY

divided

a

cell to act

be made

tubes

effective

most

are

the

agitate the liquid round

to

in

suggested by Carmichael,

as

or
depolarizer,

as

for

simple cell.

a

conducting

the

powerful

oxygen

sulphur
anode,

the

rubber

Hard

into

S02

the

electrolyte.

Sulphur

dioxide

ferrous

than

for copper
with

a

more

sulphate ;

critical

the

sulphate solution
is

S02

is

given from

in

a

cejl anodically depolarized

evolution

the

of

data

calories,

7,300

"

+2H2S04

CuS04 +S02 +2H20-"Cu
with

voltage

decomposition

thermochemical

the

depolarizer

theoretical

the

or

voltage is
x

"7300

96,540

a

sulphate

copper

This

energy.
Neill

X

words, S02 should

other

In

4*2
~"

^

"

and

Van

for

others

be able to
without

is actually the

case,

from

precipitatecopper

the
and

electrical

aid of any
forms

basis

the

of the

developed by Weidlein
solutions.
depositing from

and

processes

leaching and

cycle of operations claimed
the

0-15

"

2

solution

Arsdale

14.
volt.

"

=

followingequation

for these

is

processes

The

given in

:

"

CuO+S02=CuS03
Cupric sulphiteis

soluble
of

driving

off the

is not

deposited, but
The

formed.

with

pressure
to

the

excess

a

in

of

excess

sulphurous

heating

on

sulphuric acid precipitates copper

equation

on

sulphurous acid the cupric sulphite
red precipitate,Cu2S03.CuS03,
is
cupric sulphite

cuprous

acid ;

under

according

"

Cu2S03.CuS08+2H2S04=Cu+2CuS04+2S02+2H20
The

copper

In

by the

addition

of

precipitationof
practice anodic

usually only about
o*2

similarly be converted

cupric sulphate can

to

i*5 volts have

At

the

60

International

the

double

dioxide

cent.6

and

and

the

mediary
inter-

sulphite.

depolarization

per

been

sulphur

into metallic

is

not

complete,

applied voltages

from

used.

Copper Company's

plant in Canada,

ELECTROLYSIS
lead

witlra

used

sulphuric acid

cent,

is

"5 to

1

in the

07

pass

Chloride

The

originalchloride
in Silesia.
chloride

chloride

heated

chloride

would

iron

ions

the

2*5 per

applied voltage
with

The

finelycrushed

current

a

be

removed

by lime.
small

C.

700

Owing

of

amount

becomes

complex

I"ead

metalloids

the

chlorine

excess

solution

going into

copper

a

calcium

drums.

of

presence

ner

with

or

in wooden

the

to

sodium

cooling, and

on

by Hoepf

is leached

ore

containing

about

to

detailed

is that

process

solution

chloride

cuprous

The

Processes.

cupric

and

and

cent,

dcm.

sq.

cathodes

copper

of 2*5 per

per

35

cent.

(d)
at work

sheet

electrolyte.

ampere

efficiencyof 90 per

from

content

copper

SOLUTIONS

AQUEOUS
inches

separated i|

anodes

are

IN

as

:

Cu+2Cl'^CuCl'2
permitting of

thus

solutions
consists
or

tized

the

of copper
of

in the

series

a

mica

be

can

solutions, although
refractory, and

used

cuprous

chloride

depolarizerfor

of

In

the

followingreactions

Anode

the

:

Cu2Cl2

asbestos

Carbon

these

use

employed.

Cathode

the

found

the

electrolyzer

ment
parchgraphi-

or

material

anode

as

Hoepfner

are

the

compartments

cells with

diaphragms.

suggested

cathodes

copper

The

state.

cuprous

divided

of

perforated

carbon

preparation of relativelyconcentrated

in

chloride

sufficiently

not

ferrosilicon.

Sheet

cathode

anode

take

and

place

:

"

t
Cu+CuCl2

-"

Cu2Cl2+2Cl/-"2CuCl?

:

in the

electrolyte acting

liberated

chlorine.

The

as

an

catholyte and

anolyte consisting chiefly of cupric chloride, after
through the cells,are mixed
The
the

theoretical

thermochemical

and

as

follows

to the

data

"

+35,ooo

calories,

:

"

35,000

x

4*2
=

"**,,.

96"54o

1

",

'53 volts,
M

passing

leachingpiant.

decomposition voltage obtained

2Cu+Cl2=Cu2Cl2
is

returned

anodic

from

INDUSTRIAL

36
the

in this

copper

required

energy

ELECTROMETALLURGY

being monovalent.

case

deposit

to

metal), viz. 96,540 x 1*53
If

cupric chloride
voltage would
Cu

,6^500X4-a
96"54"

in this

the copper

gramme

being 96,540x2x1*35

watt

to

There

is,therefore,

chloride

than

molecule
sees.

distinct

electrical energy

be

expected by

=0*075

of the

in

using cuprous
electrolyte,although
salt is
not

divalent

the

ion, viz. double

metallic

metal)

hour.

kw.

advantage

change from

a

of

(63-5 gms.

of

instead

state

kw.

a

The

cupric chloride as
the decomposition voltage of the cuprous
of the cupric,the energy
that
gain is

since

to

yolts

2

being divalent.

case

deposit a

required

x

calories

volts,

1-35

=

position
decom-

"

CuCl2 + 62,500

=

hour.

electrolyte the

as

of

(63*5 gms.

kw.

=0*043

sees.

used

were

Cl2

+

watt

be

molecule

gramme

a

electrical

The

quite
the

to

the

higher
that

valent
mono-

output per

hour.
The

further

calculated

of anodic

advantage

from

heat

the

of reaction

"

calories

Cu+CuCl2==Cu2Cl2+i9,400
The

theoretical

be

depolarizationcan

voltage is therefore
19,400

X

4'2
=

Q.8ol

96,540
or

the

minimum

molecule
or

to

(635
kw.

0*022

required

energy
gms.

of the

The

hour.

be o*6 to o*8 volt

metal) is

gramme

a

voltage required

actual

per cell.

deposit
96,540 xo*84
to

watt
was

sees.

said

Early experiments in Saxony

(1892) proved unsuccessful, chiefly owing to difficultyof
according to the following
leaching with cupric chloride
equation

:

"

2CuCl2 +CU2S
Further
chloride

investigation

solution

is

a

good

=2Cu2Cl2

has

shown

leach

for

+S
that
certain

cupric

sodium

oxidized

ores

INDUSTRIAL

38
With

dcm.,

sufficient

A

make

to

current

consumption

surface

and

X2

ft.)a

sq.

required.
surface

amps,

of

current

tanks

of

over

5000

(3x1*5
is

tank

per

electrode

the

to

up

15,000

consumption

average

deposited is 0-166

of copper

pound

make

a

of cathode

amps,

currents

The

With

sq. dcm.

100

is to

proposed.

in series

dcm.

sq.

each

larger;

approximately

circuit.

volt

per

amperes

connected

per

tendency

the

been

per

2*2

2*2

is

are

200

or

cathodes

modern

have

current

the

total

The

of

30

large and

amperes
of

with

ioo

a

up

bath

of tanks

number

to

i'i

voltage loss per

the

o*4 volt.

to

0*2

density of from

current

a

square

ELECTROMETALLURGY

kw.

hour,

The
electrolyte
efficiencybeing 90 per cent.
consists
acid
essentiallyof an
sulphate solution
copper
containing 5 to 10 per cent, free sulphuric acid and 10 to
ampere

+..

re

4-..
Fig.

2.

General

"

cent,

15 per
from
are

arrangement

tank

to

removed

theoretically no
must

from

but,

bus

electrolyte.
refining gets
of

E.M.F.

0*3

In

volt

above-mentioned
balances
has

the

coefficient

falls

5000
case.

heat

risen to about
of the

to

energy

35 C,

deposited on

cent,

the

amperes

fall in

the
P.D.

of

by

supplied
owing

electrolyte it has

radiation

when

to the

been

per

the

the

copper

absorbed,

watts

=900

to

potential

resistance

energy

Cooling
but

other,

small

a

electrolyte in

the
to

of the

ohmic

the

on

the

transfer

to

necessary

is

copper

electrodes, amounting

the

Sixty per

owing
x

and

parallel.

electrodes

Since

weeks.

be

consequence

warm

The

already pointed out,

applied
bars

four

should

been

has

be

or

plates

in

continually circulated

is

stratification.

electrode

one

0*4 volt.

to

the

across

cent,

as

always
o*2

three

at

which

avoid

to

every

being dissolved

copper,

sulphate

copper

tank

electrolyticcells with

of

cell

60

per

in the

normally
temperature

high temperature
found

economical

. . It is evident special attention blister low demanded The should impurities in electrolyticcopper The copper grade and than to to be impuritiesin more preparation attempt when anodes can the it is that the such a of not exceed economical high grade to raw electrolyticpurification high grade of purity is obtained. refined copper may be due to a variety . for and by crystallization sulphate is partly removed copper completely by the addition to contaminated too used fall as in the low as following The 98 per cent. impurities present their and : " Copper . anode opposing face removed has and are cathode off electrodes side one electrodes end bipolar. are deposited and the on bipolar electrodes When electrolyticdepositstrippedoff of the and arrangement intermediate the being dissolved copper are The plants. . some in electrode electrode. next the The . per amounts iron. alternative An in each and vat. the the electrolyte becomes The Impurities Blister copper may the nature of 91 cent. widely in composition according vary the smelting process. of scrap copper over usual the the materials content may and ore Its indicate analyses use " rise to or further present in Electrolytic Copper. Arsenic Antimony Bismuth Carbon Iron Iyead Nickel Silver Gold Zinc Sulphur Oxygen o*i2 pay per of cent.ELECTROLYSIS IN still further to heat SOLUTIONS AQUEOUS it about to 550 " 39 with exhaust been adopted steam.

causes anode copper solution either copper by mechanical occluded and raw electrolytic deposition whilst by or Gold none cathode the cathode. of . as the disintegrationof deposited rarely platinum more or in the be removed may the impuritiesin gold slimes. agitation of densities Arsenic the silver loss in the the to of use in of deposited varies electrolyte. deposited copper oxide as of that the electrolyticallydeposit a solid solution decomposition potential of than of solid solutions mixture (Fig.since the only with is not electrolyte and the float and in affected mechanical of increased by " the arsenic of arsenic concentration the or quantity the current " slimes the greater high quantity of suspended both slimes. 0*4 volt. in the phenomenon the fall to the or means. alloy containing but either in solicjsolution. nickel the relative electrodes. contamination it brittle and by making copper surface cathode the electrolytebetween of the in current density.7 such the ELECTROMETALLURGY inclusion (i)the as growing crystals on deposition . go into solution either copper slimes. inclusion viz. anode electrolyte. very sulphate E. viz. it is probably deposited only by occlusion slimes the increasing current that attributed is is present become may as gold and electrolyte with increasing the slimes. Nickel with which the difference of a continued of potential between be sufficient to and copper copper be can in nickel containing and copper made to but copper. the the electrical of low as from quality of affect the such by-products (2)electrolytic . (3) mechanical These impuritiesadversely or valuable and palladium During bottom deposited in occlusion become the silver is found density this cathode. is much generated It as electrodeposition.F. the nickel infinitelysmall. impurities in The conductivity. It is found increase an the by direct mechanical entirely eliminated are in solution. inclusion occluded is still importance of is Oxygen of a higher between little nickel generally present gas matter these The little nickel.INDUSTRIAL 40 of causes. 3) is probably electricallydeposited.M. since copper would forms or of three electrolyte and as cuprous speculation factors.

ELECTROLYSIS

slime, on

the

IN

and

amount

deposited copper.

voltage points to slime inclusion
whilst increasingcontamination
contamination

be stated

increasing current

with

points only

41

impurities in

of the

nature

Generally it may

of contamination

SOLUTIONS

AQUEOUS

that

the

increase

an

applied
electrolyticdeposition,

or

with

density and

increasing electrolytic

electrolyticinclusion.

to

Nh"**o'

*"

Fig.

80

jo

nickel-copper alloys.
Freezing'melting-pointfcurves'of

"

Copper.

electrolytic copper

pure

for

necessary

is

i

electroplatingwith
usually employed as
trouble

no

is

impurities in the metal or the
has to be paid to the conditions
obtaining uniform, even, and compact deposits
of

electrolyticcopper.
The

practice of
of the

movement
a

violent

Various

current

agitation of the

electrolyte or

cathode, e.g. for electrotype rolls,rotation

high speed is used

refining.
the

In

"

consequently, although

;

by the presence
attention
electrolyte,more

at

N

3.

occasioned

of

%

AVom70Co

material

anode

A*bm

1 00

100

Electroplating with
copper,

100

W

60

7t"

"""

"*o

to

a

greater

extent

electrolyticcompositions

density is usually less than

than
aie

that

in copper
and

in use,

employed

in

refining processes.
are

The

two

the

acid

most

important electrolytesused

sulphate and

the

cyanide bath.

for this

work

INDUSTRIAL

42

ELECTROMETALLURGY
"

Copper

Sulphate

electrolytesmay
with

"

vary

sulphate pentahydrate

copper

the

addition

sulphate

Electrolytes.
Copper
in composition from
a
5

of from

to

o

to

content
10

per

solution

saturated

a

sulphuric

of free

cent,

cent,

per

acid.
The
to

2*5

amperes

rotational

speeds for the cathode

Coles up to 40 amperes
The

addition

of

been

advocated.

used

by Elmore,

by Consiglio

iron

salts to

decimetre

burnishers

Mechanical

are

be

can

electrolyte has

the

1*5

high

suggested by S. Cowper

as

per square

with

although

decimetre,

square

per

from

varies

density usually employed

current

employed.
frequently

such

sheepskin by Dumoulin,
frequently employed in

agate

as

glass beads

and

addition

either

to

agitatingthe electrolyteor rotating the cathode.
Cyanide Solutions."
Copper plating is frequently used
for coating iron or steel as an
intermediary film for nickel
plating. A
iron

by

film

thin

simple

for the

deposition

obtained

by

the.

of

the

Efc and

iron

and

solution, as

deposited
long as

necessary

directly
of

metals.

and

in

the

of iron

expense

of

pressures

CFe, CCii,be

cuprion

the

Epe

copper
copper,

are

solution
electrolytic'

at

the

on

hypothesis

Nernst's

of

to

iron

will be

acid

an

another

by

respectively,and

ferrous

in

conditions

the

metal

ECu be the

of
copper

described
one

deposited

than
electropositive

more

pressures

copper

iron

the

application

electrolyticsolution
If

is

already been

has

as

Iron

of

be

can

copper

immersion

sulphate solution.
and

of

the

centration
con-

solution,

going into

Ecu
^

Cf6
and

the

driving force

or

E.M.F.

Cco
of the

system

will be

^log^-^log^1
2F

The

iron is,however,

ceases.
a

porous

In

and

^

Cfc

Cca

quickly entirely coated

practice,however,
spongy

2F

u

deposit,and

flashing
other

"

and

deposition

is liable to

electrolyteshave

give
to

ELECTROLYSIS
be

The

chosen.

in which

exhibit

to

This
In

is

or

tendency

no

iron.

zero

depressed,making

iron

the

deposited
by the

following

use

are

"

less

an

alkaline

lyte.
electro-

cuprion

of

is

equation

of the above
its

apparent

The

is lowered.

E^

must

of the

passive, i.e.

is rendered

or

of

one

expense

the

at

concentration

the

pressure

noble

more

The

be

right-hand term

the

to

i.e. copper
practicallynegligible,

to

electrolytic solution
becomes

hypothetical equation

solutions

these

43

limited

electrolyteis

an

be obtained

can

greater, and

of

of the

E.M.F.

the

is reduced

choice

SOLUTIONS

AQUEOUS

IN

metal

easily attacked.
of such

typical examples

some

tions
solu-

:

"

(i)Copper

salts and

Copper

carbonate

Cyanide.
.

Potassium

cyanide

U.S. patent

.

cyanide

Potassium

carbonate

with

1

.

the

mixture

.

.

"

following solution

Copper sulphate
(*88o)
.

.

.

.

.

.

.

150

gms.

.

.

.

.

150

gms.

Cyanides.

and

"

most

as

The

.

effective

36
.

.

.

.

.

.

.

.

.

.

.

.

:

"

gms.

26 gms.
182 c.c.

.

cyanide
.

solutions

.

.

are

Electrolysis is conducted
0*5 ampere

Cowper Coles

"

Potassium
Water

gms.

.

Water

with

gms.

200

.

Ammonia

mixed

100
.

litre of water.

(ii)Copper salts,ammonia,
describes

200

.

a

.

gms./litre.
gms./litre.

100

.

.

.

.

.

Potassium

up

.

describes

129,124

Copper sulphate
Copper acetate

made

.

.

per sq. dcm.

.

.

.

mixed
with

and
a

.

.

made
current

.

38
148
up

gms.
c.c.

to

one

litre.

density of 0*4

to

ELECTROMETALLURGY

INDUSTRIAL

44

recommends

Watt

followingsolution

the

:

"

Copper sulphate

230

Water
to

which

just

ammonia

monium

added

until

solution

a

(*88o) is

redissolved.

potassium

To

this

cyanide is added

until

cyanide is just changed

been

bisulphite have
As

Alkaline

thiosulphates

have

alkaline

which

use

of

Oxalate
with

The
of

also
do

been

solubility of copper
baths
containing copper
oxalic

and

acid

be mentioned

may

tartrate

tartrates

"

and
Other

success.

in

caustic

soda.

ammonium

oxalate

suggested by

Classen,

and

been

have

taining
con-

cyanide usually make

contain

not

C.

Pfanhauser

by

with

used

cupro-

Baths

"

containing both

the

free

Gauduin

baths

cupram-

at 6o"

Cyanides.

this class two

typicalof

cyanide

baths

of the

recommended

of

solution

lilac of the

the

to

(iii)
Copper salts, Bisulphite,and
others.

strong
blue

the

precipitateis

the

Electrolysis is best conducted

cyanide complex.

and

gms.

litre.

1

others.

Conditions

Copper.

"

necessary
We

have

types of electrolytesused

for

Uniform

already tabulated

in the

tion
Distributhe

of
electrodeposition

various
copper,

t becomes 4D/ Vt concentration after a time interval " (!) C The C=C0 2=o. D" " dt or. When constant. back the rise to the value supply of surface was of further at a diffusion of + and the cell if the further cathode the at by the electrical electrode ve of from the electrolyteat the electrolysis. and dc " concentration is the gradient from the electrode.INDUSTRIAL 46 Consequently would ELECTROMETALLURGY. = quantity C" - aQ^/jLCo of copper - - */I n284Q sulphate which has to be supplied . dx quantity of salt diffusing per unit time The across unit dc with area gradient a " is given by equation the " dx where diffusion is the D between x=*o at which the and #= oo . After distant point x of " concentration the commencement cuprion electrolyte electrode vc I"et Co be the to force impressed voltage supplied by not " of the ions copper migration electromotive a time electrode / the the tion concentra- becomes C". according alters is concentration fk on Fick's to law the rate given by the equation " dx* integration " e J VttD the At the electrode itself.

at the C=o.540 96. is to be solution solution.540 f=r or- A equation. that between equivalents. of passage solution. in their by a into is saturated thin the in less concentrated the the a view. film of saturated governed by to elevating by beneficial hypothesis of Noyes the electrolysiscan high migration constant.540 i is the in current and of i.e. further has t higher potential difference the with 'V cupric ions /96'54Q" (i-wc)2tAri284/ the only proceed by and we Co2D time this When v 96. the solution the surrounded salt diffuses of solution the prolonged by starting sensibly increased course the at necessary a high of of and a effect of Whitney solute solution. For the investigation on can " present in the electrolyte. adopt applied Nernst. . gm. under equilibrium conditions is evijlent that period of uniform are D discharge of hydrion which sulphuric acid electrode passed. s amperes cupric ion.10 in solid regarded whence of the as the the rate salt from to be electrode the to decompose initial concentration. " " or.ELECTROLYSIS deposited and equal " 96. when moment when no to the is It a deposition can large value diffusion factors two for and constant be can the C0. V" *-*-"- 0 we or migration the nc above in the Q present in the layer of elctrolytenear at migration. Substituting the value 47 of the constant obtain ionic the __j " difference the to supplied by that q * where is (Q) diffusion by SOLUTIONS AQUEOUS IN rate unsaturated last the stirring 9 and of solvent. which a temperature.

is the saturation (Csat. .54"" Q=^(Co-C) or Co""C==f or We have seen. the But -".-C) concentration and C the centration con- of the surrounding solvent. of the however. deposition. from equation (1) electrolyte o"-c-*y" or (3) .-C) = = g where G^. where q " i(i " nc) _ 96. that when rotation or ment move" 4=Vi" 82?T t " ~w 4D // no is'considered.ELECTROMETALLURGY INDUSTRIAL 48 film. when and Noyes rate of dc " dt | A(CMt.. Applying this equation to the case consideration where Cq of depositionunder " is the initial concentration of the solvent and C rate of dc the concentration at electrode. the dt is equal to Q. is to the Whitney.then A If 8 be the thickness of the saturated per unit constant the solution is given by area A-D According i solution .

calculated 8. between of solution clear. current rotation rapid By electrolyte. the concentration 1*. seem electrode and cupric ions.F. the from film this thickness sulphate with the in the mechanical the of the burnishing by use higher the of Nature have we between the noted and copper equation E. but the influence cupric ion means no economical so E.M.at first sight it might the in the the nature high current always are advantageous to solution In of the lower by increasing practice. but Ceo quite close electrode the to impoverishment of the electrolyte in cupric ions by electrodeposition. From the Electrolytes preceding electromotive the siderations con- force surrounding electrolytegiven C log " 2F may to Complex RT by solution in time or " has " densities Simple Deposit. the : economy current Influence The on of a advantage electrolytea distinct the of case followingresults apart from Thus.M. 4 . decreased influence the equation stirring agitationof or be can without or manner Cu ~ is not constant. the that the = vary due to in a marked on of copper be derived from a lating by the circuof deposition is effected. on vSince consumption energy desirable.The advantage of supplements ing the supply of cupric ions normally migrating to the cathode densities have to be high current by agitationwhen the is thus employed concentration of the at of the deposit is by densities and once apparent. n of rotation deposited metal of the and Fischer A. however.ELECTROLYSIS From to up this equation time a / AQUEOUS the conclusion electrolysis = SOLUTIONS IN be drawn that continued with can be can 49 4D the same efficiencyeither the electrolyte.F.the of the electrode thickness film with period of efficient deposition increased.

-"Cu(H20). be made " 2F may F log -^" " deposited.D. other may deposit the to necessary of metal and metal high potential gradient under the loses its charge and P. metal to in agitation be assume worked a advisable take may is arrived to a deposit is desired. but hydration we water evidence that yet certain not are proceeds as ions the are whether rapidly the the as hydrated in loss of the loss of electric charge. according of the which to metal.In RT words. term other which other of form hydration associated following scheme the to the hand. changes into the metallic water be may with : " Cu(H20).r"Cu is strong There solution.INDUSTRIAL 50 for ELECTROMETALLURGY electroplatingand coherent to round the electrode impoverishment rapidly that. occurs in although to the metal the is form. . namely. the deposit RT that if the term however. The attributed ion is to it. the view the metallic the electrolytic deposition of the so direct discharge of the but secondary a effect metallic due to ion the is of frequently held that metal as concentration has is not been discharge of a simple suggested. that a high cuprion found We electro-analysis. occur forgotten. since the P. other limitingvalue a below which. great disturbances deposition solution between compactness deposited rapidity with simultaneous the too Ceo by the depressionof the cuprion concentration.where obtain to have we burnish or deposit similar the supply to metal the hard a it extra energy electrically. Since in complex ions is ion electrolytes the low. non-compact a is set It E == must E log -=" be not ^ due to ions. other ions. quite the converse hold .D. occurs low too so a centration con- at. that work fine hard has been concentration spite of the fact that if it even adopted. the on deposited the ion the and the on or. is not unless must required place . exceed critical the cation.

cupramine or complex " Cu(NH3)-4^Cii+4(NH3) solution normal A formation " of the -0*329 to With cupric ions is reduced cupramine complex. the of "0*0694 these volt between small very metal and ion metal to potassium ions. Daniel's view 12 the that are obtained metallic the with complex is complex an anion migration of the complex . 0-329 - cupric ions. in potassium cuprocyanide. value of the cation as solution a of salt cuprous concentration assumed of be to and the cuproions present. concentrations F rise to must may possibly potassium the solution volts +3*20 then according to take for log * a the and discharge P. an anion followingequilibria are undoubtedly present : the complex. high electrolyte-electrodepotentialdifferences of 9w.D. conditions secondarily deposits copper the equation from the " 2K+K2Cu2(CN)4=2Cu+4KCN Since metal or equally good results electrolyteswhether cation. . " KaCu^CNJ^K'+zCuCCNJ'j Cu(CN)'2^Ctt+2(CN)' KCN^K'+(CN)' The value of E ^ =" g"? log = * obtain We io"~3%. 0658 _ of the case of io_48w. the " |"log I* = = represents In normal a E which *~Cu potential difference If cupric ions are observed of for volt. io~~ E-" Ck- normal place under potassium working ion solution. concentration a ammonia copper volt.ELECTROLYSIS For IN SOLUTIONS AQUEOUS 51 example. necessary " by the rising from P. where the E= solution.D.

construction tube or .e. in in necessary are . electroplatingsmoothness electroanalysis great hydrate deposition. brought is deposited copper " Cu(R20)tt-"Cu(H20)tt-"Cu+2$ When the electrode speed potential is great at complex difference the cupric the electrode surface has but this variation a of in the stability of cathodic a unstable which the metal be can copper the made which tolerable unif ormity of surface it is The and such so vary thetical hypo- a of the nature suit to as density will suffice hardness and desirable are hardness wire as is the electro-refining a In and smoothness work special to intended. but intermediary in deposited We great intermediate labile the and and discharged with is existence. for for only by not by influencing the purpose and discharge fluence in- likewise can potential difference. usual if the tend . short process ion solution between .ELECTROMETALLURGY INDUSTRIAL 52 from away in results Deposit. ductility* The crystal size. Copper intermediary phase directly influences the The the to in Colloids stabilityof the of of Use as slightly protective . copper Deposition.when positivelycharged. One to Such added be codeposited part of glue in act iooo fine-grained a of electrolysis. electrolyte be colloids colloid gelatine. of Various the In " of readjustment scarcely be Influence points of highest at automatic an can The cathode the it has of the nature the conditions ion is which under charge dis- the matic diagram- the about. is necessary.glue and conditions the colloidal add to sulphate electrolytewill give more " following conditions the by electric endosmosis deposit under tenacious The electrolyte. acid acid general practice is observed. 25"-35" ing Vary- the marked C. in all that probabilitythe of by cupric the being scheme the tribution dis- current Agents on the been pointed out Addition section previous greatly influenced density current correct. it must colloids of this type. the substances have to must be with the tannic be warmed are copper In effect to is acid solutions i.

.

being reduced ammonia. of unstable an solution.14 Electrodeposition Electrolytic depositionsof " true brass or for tin and Bronze " bronze been have Brasses. sulphate electrolysisand in approaches the potentialdifference which this salt. and bronze-coloured has of the to The as We required for evolution brown a attributed or is acid. therefore will of from practically confined have Cti complex ions instead complex it undoubtedly the cuprous the per bismuth and solubilityof it appears '004 only does not .ELECTROMETALLURGY INDUSTRIAL 54 of the of the course colloidal material is sufficient above. The cent. and also of copper-zincalloys. antimony deposit . conditions rise to hydrogen. in the and concentration will cathode form to the The Use The use of oxidizing agents. usually it deposited copper present E log " The ions place from take certain under that RT E beneficial electroanalysis of copper. been nitric potentialbetween of of has Copper Depositions. but mentioned reaction usually present act to as protective a colloid. hydrogen copper Nitric acid hydrogen. namely zinc. between containing its ions is given by by obtain to bronze for chiefly regulated rather than used a solution . the to density. but the of advocated electrolyte (by the limited the at quantities of chlorides frequently been have limit the to of small use even arsenic deposit. made. " both alloys of copper and tin. = ^"u may hydride copper rapid acts to as cathodic a to evolution assume depolarizerfor such of low high electrode hydrogen formation the point a spongy that the causes appearance. the difference solution be cuprous in Oxidizing Agents cupric ion concentration and chlorides to simple ionized the of already noticed current the partiallyreact with the Deposition + 2G'^CuCr. of the smoothness chloride " of the oxyehlorides formed). to up silver. The has been demand by their actual potential difference the their a metal equation " and a deposits colour and composition. Nickel has also been substituted or been appearance The of bronzes.

various complexes by electrodepositionfrom and electrolyte deposit either to variation examples cases begins of zinc. as zero : " "0*329 Zinc +0770 Tin +0*192 +0*228 Nickel Advantage tin " complex cyanides. M" M. complex series of It of degree a The metal other the of the possible to raise the it is thus for complexity the greater than deposition potential difference where (divalentions only) " of the fact that cyanide ion is much cuprous or is taken (divalentions only) volt Copper of the various the at shown are will be noted cathode since the complexity and followingcurves there potential on ionic given by temperatures. of the pressure electrolyte containing both an 55 JSitn " where SOLUTIONS AQUEOUS containing __RT hydrogen P. " and The varies with the mixed is possible dissociation to of to copper be the point that deposited. potential of the also temperature.ELECTROLYSIS IN RT Ew=the and Cm the solution. 1 ions value the concentration. metals the . taking metallic the at atmosphere i ~" normal F ion solution H . electrolyticsolution concentration the from For Ctnx Jiog" or in normal of deposition metals in two ions as " "g w2F Cw2 -l=log=-^ following are Ew2 equilibrium potential differences the solutions and ions : Cm2 n2 metals hold must "g n{$ between metallic valent n simultaneous the following relation The of the metal. the metals In in these the . nickel that various at metallic one it temperatures constituent or a alloys. in the that is is the concentration a very current of a the cathode few typical : " marked dependence density.

stable. most metals respective tending the lower of the less alloy the the of case will divergence discharge potentials. of complexity metal (2) more deposit by C the ions the depends speed alloy partial depolarization an practice of the (i) thus of appears _""" metallic instantaneous. The complex " v^Agiefa is not speed." ion.INDUSTRIAL 56 solutions is low must we ions with be noted rapidly. Cu(CN)'g-" complexity silver the copper discharge reformation complex reaction the on that of rate the slow a rapidly by electrodeposition. in constituent again most of are ". e. the the : " ratio . between nature two the the In The (i) C metal (a)' The complex breaks down noble to course cr"r in . equilibrium again at probability Tt will the of arrive to proceeds all that dissociation 2CN'-|-Cu in is removed and assume by but ELECTROMETALLURGY temperature alloy deposition the we can followingindependent of the control variables electrolyte affecting affecting (1) and (3). whilst The the potentials of measured deposition noble take their against ion on to by the place.g. complex of ion.

1 litre. hydroxide cyanide (*88o sp. i " " .. Copper-tin. IN densities current complex-"ion . litre. 1 litre. " complex-"ion SOLUTIONS AQUEOUS 57 velocities affecting the of (1) . 1 J " to" Sodium pyrophosphate Water (3) Copper sulphate Stannic 70 gms. . the Water (2) Copper acetate Zinc sulphate Potassium 4'5 8ms9-0 gms. chloride Potassium hydroxide Water . oxalate Ammonium Oxalic a 1 (4) Copper sulphate Stannous 50 gms.) Potassium . .ELECTROLYSIS (3) The . 10*0 ioo'O Water . 1 . (1) Copper sulphate Zinc sulphate cyanide Potassium 25 gms. 7'5 gras- . gms. 4*2 gms. . . 8 gms. " " " . chloride Potassium cyanide Potassium carbonate 1 #2 . gr. ". solution. to dissolve precipitate. a " " . . . " * (2) Copper phosphate 1 ' Sodium pyrophosphate pyrophosphate Sodium Stannous added chloride j saturated . Ammonia litre.. 67*0 gms. 5-0 gms. litre. (1) Cuprous Stannous chloride . 1 litre. . oxalate acid " Water small " amount. following examples indicate some The where the same depositionpotentialof solutions of the ions is the metallic the two : " Copper-zinc. " . " " 1-5 gms. reactions -. Water 30*0 gms. gms.-' (2) (4) The composition of the deposit. 29 gms. gms. 550 gms. 15-0 gms.

electrolyticrefining of zinc is higher than that account of electro-refiningof zinc the limited zinc on up to eventually entirely replace may purificationof for a made processes. only Not takes lytic electrodifferent somewhat are its the are place according to only of recent of the metal roasted ore. however. 142). of great difficulty. absolute The in early attempts comparable zinc with disadvantages which thermal very dealt these of carbon. The conditions and recovery from that economical. owing very condensation the be bring about to necessary zinc without accomplished into vapour the loss of temperature (over 12000 distillation the of the high extremely the to a blue C). retorts in years feasible. regulus but cannot (see powder p. is very of zinc. such as Thus the will probably useful for field working galvanizer'sdross . Successful electric these heating for the reduction will be With methods the problem pure of that to internal use distillation of the zinc . is necessary. those The obtaining is from In the the ore. by redistillation of the is not only is the demand Not except case boiling-pointof the metal. appeared the recovery the by purely thermal ores it is and have generally from more economical the zinc from copper electrolyticmethods case or refining of of recovery processes for for copper. In been have attempts limited technical one.58 INDUSTRIAL ELECTROMETALLURGY Zinc. but stated. in for shell brass for certain a in but is for where also of vacuo Belgian fuel furnaces the the crude easily accomplished reasons which low will be electrolytic purificationof always be manufacture. one which reduction the equation the C+ZnO=Zn+CO fragile. zinc metal undoubtedly by-products. and later section. against reduction made were by utilize to means electrolytic uniformity obtained cost of copper zinc in the early the of copper.

heat to oxidized The and the convert sulphides is thenleached ore submitted to preliminary electrolysis. were Processes. zinc from lead) and zinc scum (averaging 50 per lead. and in many roasted briquetted with ores cells. . such removed devised per Lead sulphate by filtration.ELECTROLYSIS IN (averaging 90 per cent. lead. at a is the sulphate electrolyteprocesses low red oxides. case outbreak the to greater part before available now use the soluble as Previous flotation ore essentiallya blende and mined various coke " the control to in all unsuccessful. Their rights the over the concentrate is ore of The basis into with sulphates and dilute The and Small anodes shipping operation most of the This being gangue. world the As " silica. acid silver was are quantities of other soluble to consists and English market. to and ore acquiring the in processes zinc earliest by Siemens cent. zinc and that may be returning it in electric furnace " powder available for It is also extremely portion of the uncondensed be With zinc the such some carbon of the growth " quantity of the wet zinc economically more by briquetting with of production yields process consisting chiefly of zinc " furnace. cent. sulphuric in area Europe. tin and and modification amalgam SOLUTIONS AQUEOUS blue will process be extremely large.are used as removed a as by Ten leaching agent. electrolytic sulphate process was Halske and Laszczynski in Poland. galena complex. could zinc the of the powder the oxide. early attempts were made of copper. silver and any gold process a richer in zinc scum probable that zinc and " the blue regulus from cent.) furnace. ores Hill by little silver a sulphuric acid purificationbefore zinc of the Broken the enforced for the of all the primary roasting in was sulphides of zinc. as iron fractional and copper neutralization . being lead Parkes the 80 per (70 to 59 containing iron. Germany supply of controlled Australia. than disposed of electrolytically and desilverizing containing copper. metals.but electrolytic Sulphuric Acid of war. The Electrolytic Recovery of Zinc. the Parkes minium alu- The present).

Lead practically general. and not cathodic sulphate proceeds practicallyquantitatively. is ensured powder.. under zinc. Soluble in iron anodes practice that and sufficient are now the the make to also were trouble cost the due used. of per thin showing Modifications difficulties found Material. Since is used required. presence electrolyzing 3*8 volts per sq.60 INDUSTRIAL with lime. rapidly depolarizer. followed ferric state the zinc is used of zinc anodes P. and found was usually prepared were anodes in situ . original in the lead trials with of the as of a ferric to thus zinc the anodic reduction ferric the ferrous the by the lower sought divided to at the eliminate cell. associated to process the but it with the loss of iron phragms of dia- use alone impracticable. deposit are sheet containing density of electrolyticrecovery were is circulated " Anode the method oxide zinc : process was will hours in nearly neutral A vats current iron little bleaching a obtained. Carbon anodes. or ELECTROMETALLURGY of ampere sulphate was required hours to practicallycompensated operating potential difference due re- for anodic to the depolarization. but protected by a thick as in the case depositioncarbon peroxide. i inherent be to With cathodes.1* magnetite of copper deposit of lead . number extra evolved oxygen produced depolarizationis of the a been had sulphate solution complete of use substances. indicated. from sheet lead. dcm. deteriorate anode. cell and of this for the important of efficiencyof 80 per current a addition electrolyticzinc 3*4 kw. of ing follow- The of zinc. cathodic solution sulphate most by the material anode as other already been action the evolution being oxidized oxidize ampere increasingly becoming adoption of has as sulphate solution ferric a cent. Early experiments by Ashcroft oxygen after The " after extensive only made ferric i kgm. which is thus a of agitation with filtration.D. In this case as leaching agent.the sulphate .using ferrous ferrous sulphate of the reduction accomplished was deposited. The final a sulphate and the before wooden through lead by Frequently dust solution by filtration.

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hydrogen any to use attended conditions case "0*329 copper volt.ELECTROMETALLURGY INDUSTRIAL 62 top. the by be eaten may usual lation.until to consequently copper solution that or is it acid an deposition Ecu referred volt . Recently. The " the In reversibly liberated an paint investigations. by the Surface " of use corrosion just below the aluminium plates as unqualified been obtained for electrode easier deposit than of zinc can cell in in a of that also zinc could be normal It The hydrogen. is 5. unless the to prevented from corrosion The is the of course few a plates The hours.16 doing of through in prevention of method presence Zinc \jU vo Fig. from against the volt necessary concentration with necessary of copper electrolytecontaining normal +0770 of sulphate electrolyte a metal the hydrion concentrations. circu- by active so greatly assisted and atmospheric oxygen. the at a low at is the on the zinc of anode ion and be liberated anodic and conclusion acidity a normal before potential applied was Mylius same and zinc excess solution sulphate hydrogen would an the electrolyticpotential deposited deposited.but the results many was liberate to +0770 be has been deposits from conflicting. the electrolyticpotentialof the in zinc cathodes cathode obtaining uniform have cathode if necessary line of the Conditions for zinc pure by acid. zinc ion follows if to liberate experimentally of the arrived zinc and gas. subject of are solution readily not are success. and attacked of zinc above Fromm that were a 17 high most . the to which deposition. electrolyte. hydrogen scale by bitumastic material Deposition.

and decimetre. it an with The IN basis the now material the to several of electrolyte. zinc per to results the 14 per usually is cent. aluminium or potential difference 150 50 amperes lead The used. the 63 density. can ture The zinc deposited by this method of 180 to 250 C. obtained arabic gum sulphuric acid grosser concentrates. iron manganese. and necessary owing practiceit definitelyto depositionhas been shown of oxidizing impuritiesnear the anode. from solutions from remarkably The small and impurities obtained containing pure. of found was avoided electrolytedistinctlyacid. anodes sulphate zinc and density from current An to 20 sulphuric acid perforated sheet litre . current of basic presence formation SOLUTIONS AQUEOUS electrolyte. The zinc explanation deposited rising hydrion to of these the results in the of the increases liberated hydrogen concentration where with electrolyte is far from satisfactory. with colloid as zinc cent. in curve of traces Broken roasted using 0*05 in electrolytecontaining 13 10 to 19 per cent. at In a the . 99*80 per cent.18 con- reinvestigated the problem. especiallyafter the addition a colloidal of trace is process 19 Tainton surprised to were and the to is necessary cause be due hydride of zinc. and Hill as substances other averaging well over Fig. are is about vat and 5 volts. The 100 electrolyte contains of zinc gms. 6 represents these an lead. liberation metal. per cathodes.and spongy a unstable an Pring The and and high carried of current with out small a Their find that densities the to the presence tion forma- to the not as of spongy formerly was sidered. o*i per the ratio of iron. semi-technical deposition installations. with strongly acid deposition of zinc solutions could be high efficiency. authors. square per the be obtained at a temperaefficiencyof 95 per cent. by sulphate cent. Further.ELECTROLYSIS desirable to in work to high a of keep salts is to be in deposit. each over of gms. As the has already been overpotential metallic surface necessary varies with pointed for the out in the hydrogen nature of the introduction.

J jH2(H20). "* ~* f H2 is natural : ( IZii(H20)B zinc explained on deposition according may velocity of A ( is greater than zinc ions have. a be ~* to B hydrogen Zn deposition.M. an reversible the applied excess ELECTROMETALLURGY difference required of zinc. J the " UC |Zn(H20)J 12H(H20).since practicallythe same. follows of deposition potential deposition which that 9o efficiencyin deposition on necessary The bo per ""j. " Influence of current deposition. which in the scale.F. 6.dcm density the 70 60 may . to preferment assumption some such for the scheme as be that of the however.which depicted as 2H(H80). hydrogen under a that to normal In of the the of the be must This potential deposition is +0770 neighbourhood ions acid hydrogen. for necessary both higher than critical the zinc ion solution conditions these raises volt of the evolution the theoretical the over to o*8o decomposition potential bring about to of 070 volt on electrode equally susceptible are 100 93 98 I 80 I75 70 (3 65 60 65 30 So 10 3o So Oo Amperes Fig.INDUSTRIAL 64 of zinc case applied E.

by at Duis- of blende stimulated 5 in the . both these factors the velocity of conversion. reaction If between 2H(H20)* equation and the H2 zinc the active that hydrogen H") can deposit zinc from zinc this assumption be correct a secondary hypothetical intermediary compound distinguishedfrom as believe Thompson20 and or ions according occur may the to " Zn+2H-^Zn+2H " investigators have Many accepted " of this modifications and decomposition theory representingthe change by the formation of unstable hydrides. The usual colloids employed are dextrin. 0*05 per cent. The advantage of a high emphasized by the consideration that the resolution of the depositedzinc proceeds at a constant rate for smooth deposits depending on the acidity of the electrolyte. greatly influence intermolecular probably Bennet (H and n evidence independent other we 65 SOLUTIONS AQUEOUS sulphate solution. and in calamine " Hoepfner's original chloride is is said to Germany.thus by increasing the rate of deposition the efficiency is also increased. Addition Agents. apparent Spongy surfaces density is further current will naturally dissolve the greater The Tainton exposed area Use quicker than of to the Colloidal recommend the zinc and smooth to solution. and Co.22 as raw still worked but be the material at work use has Messrs.. Pring and " tion deposi- the ensure impuritieswhich are likely to be deposited at high working potential difference a between electrodes. This the point has already been discussed in dealing with the depositionof copper. for both same the and not change like the first . of colloids to use owing ones. The process Brunner. berg and Chloride was Mond developed and Fiirfurt preference to ** Processes. Sharpe 21 suggest the of use 1 per cent. pyrogallol or j3-naphthol. gum tragacanth and gum of the arabic of about Watts and to eliminate concentration.IN ELECTROLYSIS Not only have hydration numbers but an the series second x the not are that changes is bimolecular of ions. of eikonogen.

not and is of sodium (o*i per Giinther. used chloride.and be basic. with Operating provided cell or be may analyzing 99 '97 per cent. the given electrolyte. fibre has noted of use where compartment compressed current cell. per The chlorine carbon anodes over 94 stated per to of cathodic diaphragms silica give.more method. by treating the in a carbonating is obtained of zinc at the the only 85 anode chlorine actually As already collected. whilst used are hydrated colloidal evolved for chlorination. may chloride as cent. chloride ore equation ore and Iron be present. except by-products the method in of certain has but Zinc. but addition general practice. per possesses the cent.. efficiency is obtained on addition are on It may agents is efficiency is stated current cent. anode for on per from be used Fromm high a at 3-5 to advantages for this process.66 ELECTROMETALLURGY INDUSTRIAL employment of chloride the than sulphate electrolytes. The cellulose. A 10 such density Foerster to sulphate solutions. compartment which Mylius and of diaphragm deposits of zinc zinc per and those to the a 3 to 4 amperes obtained 20 final filtration a copper of hydrochloric acid similar experiments as solution cent. dcm. .good results. The been of Electrolytic Refining mentioned. A solution zinc roasted the with calcium calcium when tower. cases " for the has utilization little commercial value.). electrolytemust is maintained. may be efficient circulation in the that The said to asbestos be be of that nitrated been the be well cent. liquefied. can carried who 7 volts sq. per According good little alkali whilst a addition by the removed are with chloridizing roast a deposit metals little free a gypsum. The to and cathode revolving cathodes preparing bleaching powder.containing about as out be can and zinc will scrap to +CaCOs +C02-"ZnCl2 manganese bleaching powder over deposited according is " Alternativelythe of chloride carbonate CaCl2 +ZnO salt.

on the surface . removed was The cent. per and copper. square per cast deposits of zinc could coherent process either and not commercially prove successful. in which to deposited accomplished by cleaning the dipping it in iron outside The sludge the be can lead and cupelled to silver. acetate. cent. and zinc at is made containing the compounds formation is Galvanizing temperature a with FeZny film of iron-zinc pure and alloy of about zinc on the FeZn3. lead. attempted in the 50 5 per a zinc sulphate granulated pieces lying or With anode. per at solution. by plate. per acetic temperature a 15 o-i commercial and anodes with cast electrolyte he per galvanizer's dross successfully used material 67 SOLUTIONS AQUEOUS IN per cell at 1*3 volts obtained. 4500 C. and aluminium. pickling it in acid. little a Parkes' gold. namely. were 80 between the dcm. sq. in the chlorides magnesium and A a bath " hot the galvanizing steel or of molten superficialalloy of a commonly most process.ELECTROLYSIS Richards when cent. and density of current a zinc anode as aluminium. of o*8 to current a but the good 1 solution on horizontal a ampere did carbon dcm.followed air ferric and only 0*05 anode provided employed.. material hydroxide purification of the lead 100 agitation. and to 08 separated 1 As sulphate hydrate. of silver and cent. the Electrogalvanizing. cent. acid. per cent. and cent. voltage fall per cell of a circulation good 4 17 sodium cent. A as chloride electrolyteis said silver chlorides obtain using zinc process be successful. to 70 cent. Anstalt zinc 7 per They employed anodes which impurity. per ampere 320 C. cent. good 1*25 air agitation and efficiencyvaried current the average The iron analysis showed from the electrolyte by the the hydrated the acetate The the Gold to 10 Silver and 50 per frequently up o*2 to and be from the filtration by of precipitatedfrom was Hamburg at obtained scum containing from zinc. per obtained be from cm. and per per that cent. desilvering process. used With cathodes zinc of 300 deposits could volts.

high. per sq. whilst or strength of steels due treatment. how- containing both cathode with metal of the has would with case against a cadmium volt.. of that to behaviour anode The cms. been some anodes 8*55 per cent. cadmium first to be and deposited.and lowering in electrodeposition lead peroxide anodes for deposition are electrodepositionof obtaining in the those a subsequent thermal circumstances these have thin the relativelyhigh the cause sulphate electrolytewith feasibly employed. with E.. with for the demand refiningof 24 Brand 887 Cu metal 1*35 cent. a per free apart. large-scaleexperimental work of the following composition. solution.such as temperatures employed the tensile acid The with (4500 C. dcm. and usual As the electrolyte he followed refining.) may Under this to zinc conditions necessary sulphate solutions. Cadmium. be can cables. whilst only +0*420 of deposition from Its present such not metal. at first practicallyzero owing to electropositivezinc very zinc. zinc cadmium sulphuric acid. the overpotentialof hydrogen conditions a a the is ever.68 INDUSTRIAL ELECTROMETALLURGY considerably lower may articles. Pb 1*35 per cent..F.using a solution containing 10 cadmium as sulphate and 5 per cent. and accomplished practice of and pure purifying on Cd the high metal. being for deposition the is very Technically there not +0*400 density practicallyidentical current metal. former the value the little electrolyticrecovery and accomplished on any scale .M. making the zinc solution a hydrogen the was as electrolyticpotential on from though cadmium great difficulties volt. cast cent.28 from hooks of strain breaking the already been referred identical from zinc to. current applied was the presence of the highly causing direct deposition . electrochemical The similar does its is Thus ions hydrogen yet. since zinc. Zn per per cent. His electrodes deposition was in the spaced 5 were accomplished density of 1*4 amps. successful be has the is very necessary former the as hydrogen scale of +0770 volt.

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are dissolution solutions of compressed advantage the possess solution substances The agitation by the to the gold by potassium presence equation of or sodium or oxygen an cyanide oxidizing 88 " 4Au+8KCN+2H20+02=4KA. The dilute in comparatively rapid whilst relativelyslowly attacked.ELECTROMETALLURGY INDUSTRIAL 70 earliest made with There is " sickens hindering of power becomes and its coalescence amalgamation it the be may Two mercury. great addition More of potassium by means practice is the extraction cyanide or potassium-sodium cyanide solution. by the of sodium use the of a slightly alkaline peroxide quantities is said five times velocity of solution the to normal or rate the in the greatly accelerated medium. the crushed of process and This of method disadvantage the other that very a the and is ore solution associated is of for viz. its poorer with extracted prepared from water to gold from in the mercury or its lessen to away the solvents other both rectifies the the resist may the of with with of oxide. the recovery and potassium cyanide. sulphide of are by addition the or oxide the wash oxide tendency. in wooden common tanks with continuous cyanide solutions solution the other of requires agent according is gold that air. film a electrolyticcell an coated which metal In of quantity of sodium gold-itself other in with carried be to making small the ally occasion- mercury tending and and cathode The coated Electrolytic reduction a and removed difficulties associated process. free chlorine ores. water.leaving the gold. recovered mercury the of mercury. several are as which mercury. bleaching powder some employed also aqueous an The effect amalgamating extraction chlorine extraction and gold. to small four or . the subsequently technical ordinary amalgamation " solvent a by distillation. of mates gold amalga- . use finely of chlorine sulphuric acid.u(CN)2+4KOH Furthermore. with dissolved the in metals are impure electrolyte results. potassium increase is rate The addition ferricyanide in of solution presence of air.

and several strong as convenient a electrolyticinstallation are cess pro- deposition by times ten gold is in to Siemens-Halske used. to advantages much Very form necessary Sheet The employed. averaging from lead.F. in weight of by cupellation.M. by this method. cathodes enclosed are formed blue is lead anodes. above 5 volts. metre cyanide electrolyte 3 in of zinc handle. equation into in solution is again " Au(CN)'^tAu"+4CN' As in the smooth The and case of complex copper cyanides. whilst cent.is subsequently 2 to recovered 12 per cent. compartments top and so exit at the cyanide rapidly dissolves Auric form the to 0*005 electrolyte is slowly circulated The vats into of the usually from applied voltage of cyanide taking place with with cm. SOLUTIONS AQUEOUS contaminating the electrolyte. the chemical over whilst cyanide or cyanide the ing Leach- chemically. to The and iron and linen anodes long. accomplished shipping 71 from chloride a for used for this purpose. cyanide at recovered The The solutions chloride gold possesses cyanide. down for been have ferrous precipitationmethod.ELECTROLYSIS The IN solution zinc-lined be course boxes sulphate for is the solutions of recovery of solution be can least instal. weaker is necessary. used a of can from Deposition " Gold of Electrolytic Deposition Solutions. mm. 100 per 4 volts. decomposition through large wooden which is density employed current practicallycolourless bottom in admit to as of the of excess complex cyanide the cell. the . 3 to sq. divided are electrolyteat a an 30 feet long by 6 feet by 6 feet. 0*9 the Prussian wide. The o-oi ampere an E. bright depositof gold is obtained gold. cyanide to " Au(CN)3 +KCN$KAu(CN)4 The complex potassion and dissociated cyanide is dissociated auric the complex according to the anion which Au(CN)/4. metres 2'i bags to the pensive inex- comparatively from iron the 0*05 as means prevent of the action anodically by the on low as thick. per for the generally employed. a very uniform.

advantage smoothness of of by ing electrolytescontain- temperature of deposition . gold the of For the Gold. and does process electrolysis mechanically stirred The by formed experimental stage. as to electrolyte. In the used. carbon and the of the electrolyzed brine situated cathode mercury a sequent sub- and co-deposition being generated in situ by chlorine the is precipitation. and ribbon of thin gold sheet. Haycroft between leaching chamber finely crushed and the leaching the ore partly by ore The experiments mixture of substituting the Efficient of ICN of of a can using the the of the anode. copper the the uniformity use of a less than and and complex electrolyte. an process have iron the on be to carbon lead the suggests to facilitate gold and mercury foil and of molten bath a said are gold deposited in employs modification a peroxide anodes The suggested. is leach base the at amalgamation direct of suspended in the roof anodes in the kept vat auri-chloride chlorine. and by Prussian lead blue. from passed calcium and gold is claimed cyanide have to by using KCNS and of the conducted lines the by electrolysis and seem has of gold is removed action the slowly rotating aluminium gold from said KI carbon solution at Clancy Haycroft's on KCN. not 29 anodes iron to be be a the by Coles from continuously removed promising cyanamide.80" other is In metals again taken deposits obtained zinc. in sumption con- electrolyte the Andrioli cathodes electrolyte. the contamination the peroxide anodes anode as difficulties the are process iron of use the of a surface. as in the case The discussed.INDUSTRIAL 72 The ELECTROMETALLURGY of disadvantages inherent in the of iron. to iron and the . Electrodeposition and Refining of electroplatingwith gold. is brine warm. of this process According unaffected also by been lead removed by immersion Keith cupellation. The easily detachable the electrolyte a as more cathode liberated some leaching chamber Cowper . refractory magnetite due in the the the use for the deposition gold deposit is electrode form formation suggested has the cathode. Tin the of Blount. material. o*i per cent.

cent. Au(NH8)2(OH)3.with anodes from chloride as use.but in Jacobsen and Cohen. and " 70 Cold cent.. optimum 6o" by c. 0*4 per SOLUTIONS AQUEOUS and obtained. Small current usually employed with a bath voltage are tion temperature of deposi- C. primary to the equation as the decomposition gold in of the source the place according takes " AuCl3+3KCN=Au(CN)3+3KCl 1 Fulminating gold. 500 and depositionis brought about 100 before sq. aurous The followingbath suggested by Roseleur typical of the cyanide electrolytes: may be taken as " Ten and water per that of gms. gold mixed with pure) in 750 boiled this be to 0*41 012 of from 27 to gms.32 in dilute sodium is liable to metal formed of insoluble sodium cyanide passive owing become to the cyanide. cyanide. cm. Dipping baths the insertion of sheet in which copper . c.c.c.31 Electrolytes. 73 electrolytes should gold.ELECTROLYSIS should 6o" lie between than more electrolytes used various with The less electrolytes for The " of excess to the phosphate. per in 250 potassium cyanide (98-99 of hour an The dissolved are of water. ferro- the are Reddish C. is frequently an intermediary by precipitationwith ammonia the of chlorides presence proceeds smoothly according to solutions the formation in the to as avoid solution electrolyte. Anodic potassium cyanide electrolytes. of Langbein recommends gold sheet. NaAu(CN)2. chloride. cyanide. of to a gether to- coloured producing cyanide potassium cyanide followingequations the formation of auric addition the on contain more important deposits. of pure ampere 4 volts. lies between 20 half densities. usually are IN complex a solution taining con- place according takes : " Au(CN)3 +KCN^KAu(CN)4 KAu(CN)4^K+Au(CN)'4 Au~+4(CN)' When gold chloride is used electrolyte. Cyanide cyanide deposits matte important complex sulphocyanides.

of the gold salt and formation the from complex cyanide so solution.. is less than 25 to 30 grammes of . Deutsche certain with system where Philadelphia Mint. the platinum large thin of being sheet gold wire density employed dcm.AuCl3+K4Fe(CN)fl+02-"KAu(CN)4+KCl+KCN +Fe7(CN)18+H20 His to numerical doubt cast the this upon The place. developed by Wohlwill. addition the the are by The auric of an# solution same as the introduced the and Bottger and is the the refininggold by those mann. amperes volt.INDUSTRIAL 74 zinc or ELECTROMETALLURGY. originally This studied and for Hamburg Dr. 90 equal The of gms.36 Neu- electrolyte N. of and and Chloride ** improvements used are are 10 as 1 anode avoided. and employed. and fall of potentialover up electrolytecontains to 30 about is palladium and gold cathodes .38 plant is of densities " at the electrolytes. interpretationof ferrocyanide baths of are other hand not addition do time 34 chloride. gold containing both material.33 to potassium cyanide. a : " HCl. with ferric temperatures employed of the potassium the gold anode the parative com- cyanide baths. was longer exist.87 Raflinerie. no chloride auric carbonate current for cyanide methods modern so ferrocyanide. over relationshipsare. . soldered is. Beutel. for the 15*9 is necessary. dcm. of gms. Electrolytes. suggested by Eisner employed use on hydroxide precipitateis filtered off. however.for amperes the bath the per joints cathode sq. cyanide preparation these They the as taking reactions the formerly had cyanide electrolytes cheapness and complicated so anode The The per leads the current sq. but the time to the advantages as recommends amount is boiled dissolve not from Pfanhauser poisonous so With advantage their of account on purity. readily and per litre. the The Electrolytes. now Crude Tuttle into the electrolyte. a large installed. less usually contain the concentration Ferrocyanide according gold ions in of " potassium' auric place in take potassium ferrocyanide crease in- to as following reactions.

with partial ionization undergoes electrolyteto by hydrogen gold complex the " important in the or of free 3 per cent. to anodes some small uniform the ensure +4CI' chlorine.especiallywhen a and of SOLUTIONS AQUEOUS of the falls or cell " =AuCl3 +2Au by the dissolved chlorine " AuCl+Cl2=AuCls thus serving diffuses will be anodic an into the bulk depositedin of trivalent the as of solution. the The solution aurichloride. 76. at the gold of the solution The excess primary formation anode probably takes subsequent decomposition into auric chloride its is either the anode very small redeposited on crystals to the bottom 3 AuCl is oxidized according hydrochloric acid in free chloride. of that to the demanded would from recovered the by be slimes.000 Over a Platinum electrolytewhen the usual from obtained cathodically deposited under Osmium. and as acid. iridium this process The solution of the goes raising the anode and chlorine York into are of not are electrolysis. AuCl. the temperature The bath. which and + to have the place. in the recovered are refined by a chloride volts. aurous +Au" AuCl'^H- pure liberated gold. which to the It is equation chloric hydro- 500 at jo". A the to become state. aurous only the trivalent gold ions. On passive. and E*=+i'i5 per concentrated sufficiently conditions chloride of ounces solution is about the silver and in New anodic gold consequently and precipitation methods. are by gold cathode the At amount gold deposited is usually slightlymore than ampere-hour of the excess gold due weight depolarizer. deposition the ions present . indicating that the bulk potential of solution liberated taining con- palladium They gold per week in the gold when in trivalent potential the gold is apt will be solution Philadelphia alone. being maintained contains HAuCl^H- as 75 deposit of gold is uniformly pure and both adherent to little gelatin is added crystalline.ELECTROLYSIS gold per litre IN about chloride. voltage has risen .

which Ruolz's Von the on of addition of auric by the solution the sodium sulphide sulphide " AU2S3 +3Na2S^"2Na3AuS3 The deposition of gold that of antimony only due the the to from from its simple followingscheme this electrolyte.if similar complex sulphide (seep. equation " Na3AuS3 whilst +3Na anode +2Na the =NaAuS sulphur yellow polysulphide converts " Na2S+S=Na2S2 +2Na2S the monosulphide .39 41 and Smith's good depositswith Wallace Miscellaneous Preeble 40 " obtained modification complex of electrolyte formed sulphide to in of sodium excess gold salt.76 INDUSTRIAL to ELECTROMETALLURGY volts. or a utilizes patent.is ionization of the salt according to not to : " +AuS'"3 AuS'"8^Atr+3S" NaaAuSa^Na but according plays Ost to important an Klapproth. subject the and anode the to of the has dency ten- asymmetric with attended the passive. preventing the silver been The bath.42 the and r61e sodium sulphide " NagS^Na+S" At the cathode the discharged sodion reacts both with the aurisulphide " Na3AuS3 and assists according in the to the at into the the =Au +3Na"S intermediary formation of aurosulphide. 90). Withrow. +173 of the When Addition anodes said to the be of use chloride from internal resistance adhering baths of silver amounts in present are is alternating currents good results. relatively large the iodide become gold to ions lessens chlorine of raising the thus of bromide use of matter few a and early patents. Perkin and Electrolytes.

.

in 12 amperes have Fig. of is 2-3-5 interest crystals by are silver long. per about deposited to scrapers vats. or to o-i copper 5 ft. off the of the about its The provided current the from at each density. of wood are form rail a crystals. also and 1 6a. the the In a deposits scrapers scraped caused point Dvftl of n forms. or ELECTROMETALLURGY INDUSTRIAL 78 not bath too washed contain is kept high great. volts. silver. from a 4 per dore size. usually and oscillate employed silver surfaces two A which acidity to early suspended suspension of electrolyte. a ft. J and deep nitrate in earthenware conducted of nitric nitrate copper to in. of a fork to from the at on the bottom and wooden a of the placed fork. cathodes The usually from avoid which electrodes which are of the prongs plate. employed. backwards run crystals. containing slimes separated are wooden with usually in. and no are melted copper and removed into the on ingots. cathode above each forwards. are at canvas suspended by and varying a 3 the on into of which was cathode per be for The serve one 2 cent.The electrolysis is tanks. mixture silver cent. allowed the the roller its passage. should of the drain. 3 acid 45 when in. 14-17 The loose feathery detached mechanically the bags placed caused in and agitate of silver that to density trays. 6 2 anodes. enclosed in. by bags. two consists cathode sq. mechanical to crystals in America 100 canvas another. one distant high of metal in 6 in. to amount The used. 6b). filter cloth Silver foil anode. scraping simplificationintroduced distance some backwards above forwards and (Fig. current cm. . Mechanical the lyte electro- inserted charges swept are as in.

if washed practicallypure gold. of 1*2 been used. the and position inter- the agitation is dispensed from down time time to simple. but of consists of lead traces have into cast of employment placed a anodes separated above. 6 amperes density'being per 100 decreased sq. however. of the separated density is employed.. or dropped be SOLUTIONS AQUEOUS The removed are by another by travelling band. deposition. U. vat. The from is in process crystals deposited on elevated scraping and it thus slimes for moving out of the is of horizontal placed in Mexico. as cms. as Moebius anodes in the cathode the current distance greater of an which on slightly lower A employed are of the Horizontal success. the the bottom silver sq. plant have of the melted. diaphragms by cloth to with is worked plant but modification Balbach.and copper high are is Mechanical practicevery great deal works. even r8-2 viz.F. slimes. the block travellingsilver band cathodes amperes to 100 per with. Thum's At sq. canvas at use can suggested been wooden with by may These The silver band of the vat the bottom at which anode electrolyticallyrefined of the moving contain to copper. and anodes elimination the to and with the of process 79 and is liable pieces of silver treatment Modifications view the by are gold. higher voltage.viz.A. usually employed.S. the crystals are copper any a between conditions The at cms. the . cathode bath as It diaphragms Monterey the cathode.IN ELECTROLYSIS The black pulverent anode slime. as number a with such scrapers. 3*5 volts. practice must current silver high acidity and economically in of electrolyticparting of gold and in the From although in certain have for more to electrodes pressed As. as with cms. a gold with the removed small or during the off contaminate treated bismuth. current vats in are Mexican replaced by graphite silver crystals are deposited. E. owing necessary density. the valuable more 2 cases separation the a 2 metals than to 3 amperes volts up per to cell locked unsound be a low in the current than in maintained 100 per are up low copper.M. but the without are a densities as possible. dissolution acid.

to salts results Occasionally of nitric free neutralize cathode. per carried processes being approximately 1*28 between solution electrolytes the be to position decom- nitrate raised be can lies operating voltage is the The respect voltage commencing copper any usual volt. be the dulled tendency.. per run dcm. The due gelatine must silver. 0*5 normal weaker ion difference nearly a solution a "0*324 are a since volt. density current is addition cent. by acid. per low a slightly nearly diaphragms no silver. two ion cupric potentials of the salts increases. but removal deposition a reduced day. and between silver being there In silver normal and and copper respectively. but are ammonia any volts. copper or copper can precipitation by lysis electro- usually employed.000 cent.ELECTROMETALLURGY INDUSTRIAL 80 concentration of the normal volt discharge potentials of potential voltage of is about 070 used considerably are this minimum higher In the contain the over vats 30 are deposition. to at in out cent. the by a of is necessary. the to therefore mints the gold. 1 be formed place while white. this by the addition the the rich deposited in copper electrolyte spent copper taking partly destroyed in become the ion corrects in it is removed may unstable an up which spongy alcohol as anode an small gelatine. attention The skeleton. but addition the salts as of of a nitric (0*4 per the small in made acid and of partly silver addition in of of with iron the is tities quan- deposit. of the presence anodes used. adherent deposited are electrolyte has the of of ampere an even of be can every Subsequent chemical formation quantity o*8 nitrate of formation 10. and 070 in normal 1 "0771 between normal. than decomposition than without and o*i and silver practice in taining con- discharge the volt. sq. are not oxide size . the as acid crystals which to be the recovered in crystals part 1 When or silver Large chloride. . the at addition of The 1*35 where behind remains gold and obtaining by the possible reduction of basic the the paid to volt 0*5 deposited.).

These improved good for silver refining deposits. parting of gold and silver as well as the in the refiningof silver practical conditions to be observed as from nitrate electrolyteshave already been discussed. and copper. 30 use base per metal Electrolytic refining could possibly for cupellationof the zinc-lead-coppercombe substituted plexes obtained in the various processes for removing silver The from lead. even more leach would probably in As offer several together containing anodes whilst cent.47 The or deposit be improved by rapidagitationor rotation of the cathode can " as by Sand48 shown silver purposes the addition of as or plating. electrolytic refining of The and the silver. copper or by the ores electrochemical attention. The nitrate electrolyte Silver.ELECTROLYSIS IN SOLUTIONS AQUEOUS 81 Shaver. the depositis macrocrystalline and spongy.and 10 per cent. anode with Lead Pennsylvanian gold silver extensively. cyanide a silver is " practised containing gold.49 and even for electroanalysis. of a suboxide probably owing to the formation 46 due to the absorption of oxygen.although sufficiently alcohol small Snowden. The application of from the of the processes of one wet of silver from electrolyticrecovery received of methods of scrap iron day economic usual leaching agents silver extraction does deposition employed in the not conditions have precipitationby that shown have to seem means being usually employed. 60 'per many Co. The crude silver Pittsburg use now at lead. Cyanide Iy. material. utilizing crude lead of case advantages. chemical any its the Present electrolytic in certain localities.are Electrolytes.60 or by the addition of quantitiesof colloids such as gelatine. copper minor impurities. and Philadelphia refineries cent. bismuth per cent. Electroplating with is unsuitable for electroplating . the 2 York New gold. " The cyanide not suitable complex 6 for silver . by suggested by Kiister. be remunerative winning of copper may of silver would and the electrolyticrecovery probably be favourable.

cyanide of silver chloride. according electrolyte proceeds the of copper those the to followingequations : " AgN03+KCN=AgCN+KNOs precipitate of The cyanide form to is dissociated cyanide silver soluble the is soluble silver potassium in of excess cyanide which " Ag(CN) +KCN"_KAg(CN)2 KAg(CN)2". silver primary separation of the soluble cyanide per litre. With density of 0*3 ampere heavier For with 40 current " A coats good electrodes 100 per he gms.ELECTROMETALLURGY INDUSTRIAL 82 electrolyteis probably. of chlorides of a 20 gms. ensure of silver very 1*5 per the presence suggests 25 gms. advocated cyanide and with current evolution neutral for of double salt. in gold. preliminary a generally of cyanide baths former of use the and sq. H. potassium cyanide density should be employed to 70 making up Pfaunhauser 10 suggests 25 potassium gms. used due A. Langbein advocates states decomposition deposit.K+Ag(CN)'2 Ag(CN)'2$Ag+2(CN)' of the The presence the silver salt influence 1840. the suitable most Dissociation in with common electrolyte for silver and deposition. work " baths such as for giving steel are electrolyte contains hydrogen. cathode the 1*25. litre. beyond certain limits the presence that of considerable a the electrolyte. 25 gms. current a the potential drop good deposit is obtained.61 coarse being about the bath across the chloride as whilst advocated. of silver have carbonate investigatorsinsist on silver cyanide from insoluble all been is to apt 10 uses give the deposit a of gms. cms. potassium apart and cms.the nitrate. as litre and per the same density. and of the nature originallyby oxide. Striking certain salt the structure. Elkington in Sheffield in " other but the to by the potassium cyanide has the on salt formed high silver. gms. The pure . chloride.chloride. Foerster without about and Namias 62 of any coat in of silver A brisk a thin weak gms.

of The a time to or suspension of a addition of these use of the particularcase agents glue. more sulphur and sulphidehas also silver ' important guttapercha in the of mixture a be avoided. in a regular manner. gested sug- gelatine. a density of 0*3 current a 83 volt. with addition agents obtaining bright SOLUTIONS AQUEOUS litre. These they do as Some silver in potassium ferrocyanide. been suggested. of use of 7 gms.using cyanide per per The IN of instead of P. 1 cyanide electrolytes for to deposits matte is very usual. solutions not The collodion. 56 litre of water. nished. are silver that hydroxide ammonia agitationof but claimed have of a thiosul- as the tates. linseed oil. The The common lead ores consist containing varying the and Electrolytic Recovery usual thermal of amounts treatment the Refining of Lead. been not gms. electrolytewas necessary. are In first . lac- subject of patents. iodine mentioned be may time be addition effective less from use density should the current Other agitation of the bath . advocate experimenters been brighteners appears as of action normal.ELECTROLYSIS potassium ampere 100 of use sq. IvBAD. and 1 extensively silver anodes the earlier the solution a of '88o gms. the cyanide electrolytes already as been the discussed." lead zinc sulphide complexes of gold and sulphide ores silver.000 and but chloroform.. Krutwig a silver 64 the reducing agent phate is deposited from electrolyte provided that rapid such not so as efficient acid sulphurous be The or presence sodium organic acids such Various citrates could ensured. The 2*5 parts per 10.D. have agents iodine or should little higher than a amongst . cms.mucilage Miscellaneous of the used. ferrocyanide electrolytes. acetates. or " dissolved 63 Eisner and protectivecolloids Electrolytes. dissolve of to be such as have of 8*4 ammonia. cannot easily be burespeciallyfor plating articles which Carbon disulphide has been used as an addition should exceed not quantity added agent since 1847.

permitting melting-point of furnace. place refining processes purely Reductl0n J adding lime be followed PbS04+CaO Frequently orocesses processes. either as ensured sulphide or sulphur dioxide. mitted sub- reduction Any with the metal electrolytic this process production of the other by-product sulphur. which process lead of formation easy ore and that the could the It since one.ELECTROMETALLURGY 84 INDUSTRIAL roasted. was one further a " thermal crude oroCesses Processes. actions During the process of roasting two series of reproceed simultaneously according to the equations " 2PbS+302=2PbO+2S02l PbS+PbS04 PbS +2PbO " If the general procedure side reaction Roastin_ takes of also to The obtain small a -" CaS04+PbO is the oxide an reduction. } Koasung 1 Redllction =PbS04 =2Pb+2S02 =3Pb +S02 PbS+202 the such with pure or as the . and of easy ensures an treatment would be metal and hydrogen quantity of gold. to heats of low. are is then described roasting and sulphide low from in which of will be economical the removal of the the compete direct later.

.

removed of distillation i\ to zinc the which silver is formed molten of the and process is also lost up a alloy of gold and an the on of to metal.both metallic lead and possibilityof casting it directly into anodes to the Burleigh 67 concentrated can E. and by introducing air. and removal of the bismuth is never complete. impressed an Refining Lead. an tained ob- be much not PattinSon the Pattinson the In processes. or was crystals. the rest of the nickel. The .F. sulphate and 150 The in sheet in muslin sodium cathodes lead of the cell and of sodium 20 per gms. the lead to come the crystallization fractional On stan- tains copper-lead alloy which conarsenic . sulphur. iron. removed were acetate acetate small as was retain to Lead acetate. bags electrolyte of lead an dissolved sulphate anodes lead refining lead for electrolytic process and of lead litre.whilst the tin. slimes Crude in used were deposited on the thin which the bottom fused fell to together. The that the lead earliest of Keith. have of the suggested the solution oxide. ton) the whole per oz. and nate. per distillation. The removed are for the it is that process oxidizing melt. by quantity small a leads of the lead of silver rich in silver very be removed can again reduced being then as gold behind leaving the silver and lead solidified The lead. arsenic.86 ELECTROMETALLURGY INDUSTRIAL lead sulphate.forming of lead. are progress injection. cobalt. In the Parkes to the partiallypurified desilverizingprocess zinc is added the first fraction molten consists lead. electrolyte contained gms. where with The have economical of recent to nickel and is removed antimony by surface and of recovery much now more refining Parkes or the bulk ments improve- various is subjected lead crude of the zinc. which removed. of 17 electrolyticprocess and electrolytically. an cupel.M. when solidifies surface alloy is removed During the (over 12 litharge by on the air blast. of in the be recorded lead several schemes lead deposition of soda. the oxide For cent. in hot ore could lead years the process either than roasted suggested for refiningthecrude been modified so Although " presents itself. steam antimonate arsenate. volts.

of wood deep. 113-1-16 . 3 feet 6 inches wide. and 75 top in size. the to 60-90 gms.. B. and 350 C.gr. .. the E... and lugs and the Trail. washed successful removed be fused with and is melted is cast with separated from cathodes when feet 6 inches with each. The optimum 300 C.refiningprocesses. The 2 be sieve conve}'or a on A could cms. per cent.F. their fluoride in free fluosilicic acid. lead anode 68 Betts and to lead axis a disc of bronze horizontal a ampere employed aluminium an employed. first 2*2 of lead pletely com- The silico- suggested by I^eucks. to add gelatine not a small exceeding quantity 0'i per of cent. 4'5-5'2 . thick feet long. The is in process Newcastle-on-Tyne. temperature lies between Pring 60 gives the following suitable electrolyte: " H2SiF6 Pb as PbSiF6 Sp. sq. until 100 12 over cms. .C. found as . cms. near at use electrolytic lead. . the and dissolved per of 11*3 distance a anodes 22 Even through quartz. anode by sheet lead hold not when 6 are cms. Chicago. cent.60 hydrofluoric acid is repeatedly filtered lead fluosilicic acid.M. amperes to 0*42 the and The per next anodes $nd volt. rotating cathode rotations 100 per on each on to a side of the at the most Crude by 2 performing density of 72 By amperes of scrapers means crystals could drained. per cent. of extending cms. to be 0*35 Tommasi current disc the to 0*2 87 little charcoal. electrolyte consists of lead about density employed varies from current Thirty-five per said to be the at cms. gms. by 75 applied E.M. lined England. has been colloid such It . . per sq. and bitumen. . to 0*4 in the diameter 3 metres 2 varied density employed current SOLUTIONS AQUEOUS IN is added carbonate solution the ing result- contains of free fluosilicic acid.being anodes. glue necessary or 9*5-10*5 .F. . be may electrolytic tanks The 100 into cast 3*8 to refined are finished. from 0*15 gradually risingas the slime adheres sq. of mounted from volt. made and anodes the they still retain cathodes 21 0*9 to essentiallyof solution a nearly are original form. 05 form minute. Each weighs about 170 kilos.ELECTROLYSIS 100 per at cms.

Per followinganalyses slimes prevents the formation additions small frequent its destruction to typical of and deposited lead the The day. fluoborates. Pb per cent. Betts' patented agent salep. although mucilage. 10*3 per pyrogallol. numerous the use and an of lead fluostannates. Thiele with and the Maxted utility of 63 also obtained electrolytes. 2-5 per cent. and o. lead. B. are deposits good fluosilicates. apart. Trail. dcm. At necessary. and 62 Kern confirmed Fischer.in addition other salts. by the firm.such as anodic saligenin. as accumulator Hagener an works fluosilicic acid subject Halske and perchlorate containing organic colloid to the are w patented perchloric acid It is said that using this large scale. fluozincates. " As 0*0025 Sb has Betts addition glue and resorcin. Peptone. are glue is added are of lead at the : " Impurities in the Cu 0*0010 Bi 0*0022 Slime.have been suggested and Siemens patents. voltage smooth . HCIO4. depolarizerslike sulphurous acid.88 ELECTROMETALLURGY INDUSTRIAL 1/5000. Owing generally about and it anode. a of matter have free electrolyte.. and 47 25*32 As 44*58 Bi 0*52 Cu 9*3 " suggested the to Ag Sb " 0*0017 gelatine. A of current 0*21 density of 2-3 amperes with deposits with electrodes a current 2*5 cms. and Various electrolyte. efficiencyof over gave at a solid 99 per cent.phenol. 0*05 per cent. hydroquinone. albumen. 5 per cent.C. per sq. where the 0*007 of cent.amidophenol.including agents in addition of other use cent. The 61 Senn current yield is said to be from 85 to 90 per cent. other every peroxide. same A suitable bath Pb found was as in electrolytecontaining an perchlorate. and other been vegetable mucilages have the electrolyte on Peptone appears to be the best addition for perchlorate baths.

to which processes of these and removed potassium fluoride electrodeposition. Snowden cathode high speed and at investigated. and 90). in encountered dealing with After washing the remove 6 per leached from electrolytes has above of Trail. p. electrolytes the lead with the rarely bismuth. containing Antimony Na^ with hot recovered protection as lead. amalgamation arsenic. and satisfactorymethods 1 and as expectation. the slimes contain traces solution the by with anodes been and tellurium. but solutions not are already have of been slimes the refining plants. found 89 SOLUTIONS AQUEOUS suitable addition the most " of lead ton per 350gms. removed one hydrofluoric acid.whilst majority of the complex in the presence with antimony suggested. at alkali to by oxalates. subsequent about of air. residue. gold. are electrolyticprecipitation. One this with water slimes the thus copper Other and chlorination most is the The slimes are and weak are boiled recovered details then are From and such methods. The antimony. fractional or and the the gold as traction ex- antimony residues casting the of technical suggestions. silver. The acetate as have modified rotating in the well 66 working have are into all lacking .such been come Tommasi the electrolyte. with smaller adopted per cent. and of copper. slime electrolytic treatment. but for the iron. of acid last traces electrodeposition (see is then the electrolyticlead- in the recovered sodium cent. per depositsobtained the good as o*i using by process use complex electrolytes. Difficulties treatment with corrosion to up a from those as metals electroplatingof against acid in gelatine solutions lactates a enumerated.ELECTROLYSIS Mathers IN Overman w of merit to be and agents in order Clove oil 100 Peptone c. sodium added to silver the of the subjected is sulphuricacid from recovered not satisfactory the sulphide solution. " Phloridizin. deposited. The more of nitrate as of cent.c.

sq. antimony solution 1 divided volt antimony sheet is removed stellate sodium of about placed.Sb"* ==-0-463. Ost and Klapproth 87 assumed that the depositionof antimony was caused of sodions by the secondary reaction at the cathode as follows 5Na +Na2SbS4 =Sb caused : " +4Na2S by the discharge ./ the equilibrium antimony of Sb"" ions in a 6 per cent. is allowed density of 07 current of to in Trail. where sulphide potassium sulphide. of sodium electrolyte.F. solution of sodium sulphide being only io~60w (EaSb/N.. partiallyoxidized sulphate. the the divided cell used. the at anodes carbon a from iron cathodes. and sulphide in antimony sulphide ore being solution electrolyte a b}r Siemens scale been has antimony partiallydissociates into =2Na3SbS4 the following: " NaaSbS^Na+SbS*'" Since the complex SbS'"* is not readily dissociated again " SbS///4$Sb-+2S'+2S. an electrolyte temperature pure salt solution. as leached being deposited where from sodium antimony on compartment is liberated chlorine antimony of electrolyte. and traces cast the characteristic sulphideis used as pentasulphide dissolves solvent in this : " SbgSg +3Na2S which sodium lead At are antimony. flux a effectuallyremoves ingots showing into crystallinestructure. whilst source and original process the sheet a a dispensed with.ELECTROMETALLURGY INDUSTRIAL go Antimony. whilst EASb/"Sb. the and last and of applied E.in Na2S=+0709 volt). The electrolytic deposition of developed As on technical a sulphide with is used. In spent Halske.which of sulphur. the was the circulating catholyte the anode slimes lead cell is to be and are used With with dcm. and thick. a is deposited as deposited metal The of soda the anodes 6o" C. solution as follows sulphite about an practically 3 mm. melting under by per amp. dull warty a A 6 per cent.M.

sulphate or Bismuth.either not volts. there a sulphur. unless at a electrolyte. At Newcastlesolution of the a deposited from 68 Betts has containing suggested the salts in containing iron divided a generated #nodically being used from the ith the lytes electro- other alkaline fluoride. of electrolytes trichloride antimony of ferrous dissolve to Successful cell. The technical of electrodeposition successfully developed on a large in electrolyticpotential of bismuth lies its ions evolution to the considerably below should tendency solution conditions commence for this element hydrogen. the to and important sulphur depolarizerswhich have technical mentioned be application may sulphiteand potassium cyanide not more yet ceived re- sodium " Na2S2 +Na2S03 NagSa +KCN Experiments in addition on-Tyne in potassium is sodium use of acid the ferric salts more antimony trifluoride in w =KCNS with conducted sulphides. and chloride. evolution bismuth Ea= is scale. Free sulphur the polysulphide" liberation of free anodic an with reacts is mechanism is caused SOLUTIONS AQUEOUS IN sodium sulphideto form NajS+S^NaaSg which diffusion on to form thioantimonate a 2Sb Consequently only in a the to antimony will dissolve cathode " +3Na2S2=2Na2SbS3 low a single cell process sulphur depolarizeris such added efficiencylying between efficiencycan current 45 is used as claimed be Trail. form been Although the in where containing hydrogen complex is unavoidable. yet. owing 0*393 to has solution a point the " bismuth a Under spongy salts in these condition . deposited.ELECTROLYSIS Whether the antimony or is always by electrodepositionof direct a 91 secondary decomposition. solutions found +Na2S +Na2S electrolyte of hydrofluoric acid an and been the to antimony fluoride were also have =Na2S208 the mixtures addition slimes.the average the Among 50 per cent.

(A) Fusion of leaching with " Processes. subject of patent literature. in which were density and current constant voltage could constant a maintained. recovery an the leaching with ferric chloride The to Various traction exprocess. whilst fluosilicate a low very a claim 6g Schwabe and deposits from obtained crystals. totallingonly are for devised electrolytic process no of tin from important of iron electrochemical investigation into deposition scrap tin. of silver and traces " deposition. with but small not to warrant have Fusion soda have become not be mentioned may economical tin. industry. the most Although plate has.ELECTROMETALLURGY INDUSTRIAL 92 or closely adherent as efficiency. chiefly lead. and the impurities in antimony. be Tin. Excellent and obtained have to electroanalytical work for deposits suitable current solution. the possibfy potential could cathode the tartarate cathode the carefullyadjusted continuously during regulation of sodium from depositsmay be obtained solutions provided that oxalate The a Sand70 solutions. which to Goldschmidt's the ore with electro- and water caustic process. refiningof The sufficientlysimple and are =233" C). and Sn (m. with used. however. and iron.according with (B) Fusion leaching with water caustic been Processes. There has winning the methods been and tin.. electrolyticrefining an processes but metallurgical usual sufficientlyvaluable. subsequent sulphur and and electrodepositionfrom the thioaccording to Claus's process. amongst subsequent stannate gold. and suitable the has conditions Goldschmidt .hydrochloric of acid solutions. sulphuric. or Acid i technically successful. crude solution Leaching (B) soda become led to for the an i'5 per cent.p.Foerster good nitrate is from be eliminated if a divided cell anodic depolarisationunder carefullyregulated terminal a potential deposition. soda caustic and (A) " soda leaching Alkaline containing sodium with sulphide.

.

of 2-3 volts per cell.a solution As of free caustic a current warm bath density of 3-4 impurities except Steiner 78 amperes arsenic advocated the tin cent. advocated potential of oxygen. 3 per for Borchers of sodium addition been film of colloidal a the the to by to take appear more of occurs cause oxidized readily passive in formation to the sufficientlyto Cathodic not stannite and electrolyte. sodium as and Keith chloride Borchers deposition advocated the electrolyte. and a P. of All cms.# reduction anodic evolution before Sn" place. Acid Electrolytes. favours agitation of Gelstharpe 74 the reduces applied E. 0*5 than Sodium dissolved. for the 100 same sq. in fluoride a purpose. is raised being anodically Tin owing becomes this when of Sn". sulphur to the electrolyte. proposed chloride sodium 76 sodium as agents with " and alkaline well as which electrolyte. with a slimes. (1) The Neil Brown and Process. divided back tion solu- simultaneous cells The of through the lyte electro- concrete anode first com- . per and place iron cathodes sheet 100 per antimony and of sodium Electrolysis takes soda.77 containing 4-5 was cent. then +SnCl2 is the of immersion.D.INDUSTRIAL 94 the divalent the oxygen ELECTROMETALLURGY alkaline liberated. containing 15 per cent.tin could be effectually density of 0*5 to 1*5 stripped and deposited with a current stannate per amps. With electrolyte an of cent. thiostannate per Process.19 stripped in boiling ferric chloride equation 2FeCl3 +Sn-"2FeCl2 " The solution is scrap tin according plate to the " The disadvantage of iron is through during circulated the of this the process period through cathode. a sq. deposition does addition (2) Borchers' Process. electrolyte. (3) Claus's 10 advocated Luckow cms. 3 per temperature of 500 C. electrolyteat 8o" C. per flowers of B. " used. alkaline solution stannic hydroxide. by about volt. removed are addition and 1 as of cent. If is added iron is also cyanide have unsatisfactory results. the stripping the to of sodium nitrate as 76 chloride cent.M.F.

amperes per 100 sq. the proceeds both stripping cell. are with iron of experiments conducted anodes objection as same solution simultaneous acid graphite and cathodes Tin could be at hydrochloric electrolyte. a this iron Goldschmidt the than could plate of solution simultaneous ferric tin the going into is solution as : " SnCl4+Sn-"2SnCl2 is open the to solutions electrolytewith as of the Solution chloride.83 the latter over 60 per small Nauhardt quantity of ammonium obtained sq. subsequently removed electrochemically in the in tin is solution A utilizing graphite anodes. dcm. at obtained.ELECTROLYSIS The partments. A good depositwas of 02 to 03 ampere per the in of excess separate cells. addition the process namely chloride stannous on The used. a a 1*25 per trace of cent. with acid containing with a current is carried Gelstharpe82 Manchester cms. depositing electrolytes and Englehardt. stripping solution. the tin Brown. cms. practicallypure tin sponge stripping and Sulphuric Acid been the Rienders81 density of current i'5 volts have tin. tetrachloride tin tin without Hemingmay Cold Bergsoe Process. and earthenware by 95 deposited " Sn"-"Sn+2" whilst anodes at the ferric chloride the is regenerated " 2FeCl2 4-2C1'=2FeCl3 +20 Provided that economical sulphate as sulphate is reoxidized ferrous as follows " cells be more 80 uses used. suggested the of sulphate. cent. 1 to a experiments solution of acid as amperes per 100 efficiencyof addition chemically and sulphuric density of 17 current stannic of ammonium and successful out suggested by Smith claiming a and 2 employed. but the not are nitrate. sq. At the sheet are tin. graphite the IN tin is cathodes cathodes anodes SOLUTIONS AQUEOUS separated from diaphragms. with a current density Quintaine84 deposited tin . the would process by sodium (2) The used stripped be one. Divided leach.

cms. of ammonium use of tin ammonium solution obtained be per were were suggested the stripping and deposits could 3 amperes has saturated a suitable a Electrolytes. that the two metals with a density current of iron the Hollis87 electrolyte. CugSn. deposit tin. regards as alloys. by sulphuric acid as a stripping agent. powdery. of excess the deposited before the and the must complex of be the on to irregularly in the deposithave a adherence ensure employed. and is to receive steel formation densities form which as anodes Special precautions surface Iron is the tin deposited amount metal adherent. renders to the alkaline ones. 86 Matuschek in dissolved as agent of ioo NaH2P04 suggested the Mennicke obtained tin and 10 with per conducted was ioo sq. sq. that observed 88 provided of tin fluosilicate use chloride densities current at stated were oxalate depositing electrolyte.. employed. ions adherent dense dissolve generally given are tin coat white a associated generally dull. electrolytes suffer which iron the a conditions by acid electrolytes. high as colloidal addition some electrolyte containing an Good 20" C. the only do Not difficulties many " For to current which good . followed depositionin separate cells on the basis of the Neil and from a electroBrown process. copper of the Very suitable. and carbon at their from practice alloy formed dissolved. most the best free instabilityin presence fact be to cent. are and found as thin loosely cleanliness of to be taken. alkaline the and gum. There electrodepositionof the deposit. Miscellaneous C. Tin with are Plating.ELECTROMETALLURGY INDUSTRIAL 96 used 85 Nodin sulphate solution on lead cathodes. has in atmospheric tin is not strippingagents these suitable hydrochloric acid.but removed of as as quantity small a suitable. Cu^n. The Tannin. deposition for 10 of cent. per Electrolysis i per ampere The of the referred than of is tin solution simultaneous the unsuitable more junction the whole already been even dioxide. at cms. due low electrolytesthose most the but cathode.

Acid Electrolytes. of employed. efficient and deposition high temperatures the SOLUTIONS AQUEOUS to use voltage of 2' the solutions 5 to 3 volts. . " The in acid solution of acid oxalates use form the basis of a and great phosphates pyro- number electrolyte electrolytes for tin deposition. dense rotating the by the removing essential. With per at to of depositscan only high speed or by and scraping the " chloride gms. suitable electrolyte. . 55-65 . and the electrolyte containing 125 gms. soda 20 gms. Twenty-five Alkaline stannous cathode from electrode a Thick. In the to litre of water current a of grammes a in or recommended Eisner89 time brush. ammonium . time 97 circulation Electrolytes. be Brass the containing density of addition the electrolyte. of sodium pyrophosphate and 1*5 gms. Roseleur's is the most generally used. of stannous per litre must oxalate bath of the following composition : mentions an Pure tin anodes must be " Grammes Stannous Acid Acetic chloride . and gives satisfactorydeposits. . 25-30 . . 3-4 7 . *"" . per litre. of caustic good depositsmay cm. per KOH " . . and potassium cyanide World90 the following brass iron and are " Brass " Gms. " " " 75 " " KCN Brass (2) On 350 or Steel " KOH SnCi2 " " " " " " " " " " " " " 15 " " " 15 KCN 35 It is recommended bath litre. oxalate acid .ELECTROLYSIS IN electrolyteare be obtained deposit with fine wire 60 a dissolved of caustic 100 sq. chloride Field 9l be kept hot. and warm A electrolyze surface large anode is desirable. 7-5 SnCl2 a ampere Steel : (1) On with O'l of electrolytesfor giving good deposits on stated potash forms obtained. . .

iron. is associated and sulphide as the nickel of copper quantities in anodes matte have in electrodes free a for process electrolytesin a solution.F. and Nickei. brine of Canadian and copper electrolyte.M. with at tion proporthe to be fluoride solutions. and a from always* contains ore proved not Giinther93 in of nickel electrolyticrecovery The an in series a applied E. extraction or fouling of copper case both either are The by chlorine obtained concrete volt. sq. was desulphurized matte ratio rest salt removed finallyremoved to avoid conducted sulphide. Orford the As in the matte. copper 0*35 cathodes. with was electrolyte exceeded that Copper Co. arsenide. casting deposited When by sodium the first series. the deposit. in the vats such is liberated It is said necessary Electrolysis was solution. processes electrolyte. Tannin to 1*5 litres of solution gramme been published on investigated the of the nature beneficial most of the work r"ume also have current a solutions Other cm. although good sulphate a chiefly Attempts to use sulphate or chloride nickel obtained with its ores. sheet and the nickel was bulk a the 80 the chloride of : 1 unduly the by the have matte into same solution used.. deposition on the nickel The sheet . a As anodes. the at state much inasdifficulties. lyte electro- developed a using nickel sulphide small a experimented successfully on containing sulphur solution. a of of electrolyticcopper on nickel to of the in copper copper iron removed by in as was cipitated pre- hydroxide. concentration. the nickel Trumm9* Co.ELECTROMETALLURGY INDUSTRIAL 98 The is bath density of conveniently worked 1 ampere tartaric Kern92 of gives a tin and of 1 further effect chloride in stannous deposition addition of in the found was taining con- suggested. desulphurized nickel treatment . technically successful.the of the desulphurization of scale. chloride nickel relativelylarge uniform and anode. iron. acids lactic and has agents in the 100 per 650 C. Copper proved satisfactoryon process solution The W.

F.M. and Nickel with 4-4*5 is?seated to a sheet current volts have per been . IN With applied an 99*85 over in cent. but copper nickel the modified treated was calcium ore to cells of similar to a the metals between was process ore ground according copper. the remove with deposited be SOLUTIONS AQUEOUS using graphite anodes cathodes. discussed. nickel to 3*5 could purity enclosed chlorine. been 700 in 99 ferric to 6o" of to hydroxide liquid after filtration contains litre are 100 efficiencyof 93 per as NiCl2. " NiS silver (see of accomplished by means chloride containing calcium was chloride cupric After insoluble. employed sq. and be can The one. complete by This render to ore copper removed for separation of The already +NiCl2 +S used anode nickelous and has the electrolyte containing but electrically.a gms. per efficiency of 93 current a earthenware cent. cuprous made air. cm. EA= +0228 Ni/ttNisalt 0308 Cu/w Cii salt E*=" Fe/w Fe salt E* =+0*340 a of chemically and on for and copper adjustment equilibrium values with solution a by the following figures for the cathodic indicated roasted nickel and chloride solutions. cent.as cathode solution. and sheet the +2CuCl2-"Cu2Cl2 iron and copper copper which ores roasting the of fied 35) modi- p. extraction sulphides The for copper nickel. in solution carbon 1-1*2 current little nickel a returning by Wannschaft with chloride being added The C.. E. anodes per in that 96 after " quantity is heated as the being ground further the solution is removed : volt chlorine when is potential their solutions and a nearly potential. to Hoepfner " electrolyticprocess iron the the Processes.ELECTROLYSIS diaphragms of to 3*6 volts. and the of nickel per amps. per Extraction his equation the all the construction as cathode graphite having nickel been passed removing the was was substituted was depolarized by of the iron by agitation with about 100 cathodes density of cell.

Electrolytic Refining and The " insoluble crude acid an 0*02 however. easily liberated more copper the salt solution is +0*228 be the Plating of Nickel. already has It separation of of for from those from the which acid solution. found metals solution anode ionic tating necessi- a working a cathode electrolyte of basic that and condition to necessary.96 salts easilybecome and iron.97 Accordingly the best for depositionare found at relatively high . and per cent. practicallycomplete that copper cathode the cathodic Since of the Details anodes. Caspari. alloys obtained copper anodes the at Analyses of the deposited nickel of hoods. potentialof nickel volt. cent. was solution with of the from 100 per 0*64 volt " nearly neutral velocity of solution a polarization. of ro have cathodically passive. deposition of copper are. The by showed chlorine of traces Cu. less than 0*20 the according copper however. it follows than nickel in of difficultyis further even to velocity of reaction not nickelic hydrogen that out normal a would moderately a emphasized by nickel overpotential of hydrogen on volt. 0*02 in be can nickel is removed with applied E.M.F. per desulphurization by successfully refined at 300 sulphate electrolytemaintained sulphides lected col- was It is stated Si02. nickel can be deposited successfully. processes that by electrolysisat be recovered can Fe. the of deposition are greatly by rise in temperature. lacking.INDUSTRIAL ioo obtained. provided that is avoided. thus cathodic increased an iron and anodically and become current Nickel slow. liberated impurities. for the formation the other With sq. indicated been nickel adjustment favourable After C. desirable.such as amperes of common gold in metallic accelerated conditions nickel marked tendency a chloride nickel the cm. o*o6 per cent. means only nickel ELECTROMETALLURGY and the is low that the " Ni""*Ni+2" is very density of potential difference It follows is most that a In passive. fact that The be can a higher of these obtained by careful The electrolytes potential. are.

.

to from used complex electrolyteshave been Pott's electrolyte containing nickel time acetate calcium acetate (20 gms. . double the to pyrophosphate. per litre). chloride as from Dechert has substitute a of calcium use of ammonium addition the into deposits when suggested the for per sulphate electrolyte double the (15 gms. that nickel Desmur's Sodium Bischof's nickel as . . which . borate 2 best per cent. nickel cent. . chloride. amongst " solution " ammonium sulphate 7 gms. converted chloride ammonium obtained to those be may chloride unsatisfactory deposit unless an double the Nickel Electrolytes. Electrolytes. the complex as " be mentioned may nickel deposited be may following electrolytes agents and Alkaline nickel 104 per cent. is claimed It from either of the (1) 8 will be as addition from very contain 1. acid Other time.and addition the sulphate electrolyte.102 nickel recent recommend I^angbein both and zinc deposits on or brass. . only : " fluoborate. electrolytefor the depositionof the metal. suggested benzoic fluosilicate 108 fluoride various deposition of found dilutions dense fluothe among more electrolytes suitable as smooth and aluminium with are sodium with phosphate ethyl sulphate. . (2) NiCl2 5 It malleable that few A ion electrolytes suggested Ni(NH3)"4. . per noted suitable are deposits are obtained electrolytes. per litre)and is stated to be an cellent exglacial acetic acid (3 gms. Pfanhauser of boric whilst citric acid or 10" Powell Nickel ammonium in patents for the acid. 8 bicarbonate solution . 86 n ft tt t" 17 120 . per " Nickel sulphate Ammonium sulphate Ammonia (o'88o) . litre.101nickel silicate. acids weak very the that nearly neutral Nickel 2.ELECTROMETALLURGY INDUSTRIAL loz Chloride " litre)gives equal nickel salt obtained. (16 gms. . per litre). . .

for recommended deposits. density of 26*4 amperes per sq. dm. one was the up to permitting of a greater applied E. Watts some long series of technical a conclusion the deposits. came superior to nickel plating was ammonium brass (3) A Kalmus. could be the been not methods refiningof or subject of technical the applicable to adapted suit this metal to investigations. have indicated advantages the merits as of the for the as nickel speed of both in has respect cobalt that : " sulphate sulphate. strongly adherent 4 amperes current electrolytea used for soluble and hard iron.106 per sq. although E*=* +0*232 the the large. 105 conflicting evidence somewhat result of a nickel cobalt on this that over the electroplating with metal apparently ofiers experiments Recently.I?. two followingreasons (1) Cobalt O. certain all been 103 smooth even glucosides and subject of patent literature. Cobai/t. be can plating baths which density permissible with is continuously in cobalt three marized sum- to experiments. glycerine have solutions cyanide nickel SOLUTIONS AQUEOUS the factory unsatis- proved addition organic ensuring gelatine. ammonium (2) The on metals.M. Owing price rules higher available supplies are for this element nickel. deposition of nickel of their close account on similarity. P. short period. and current times to Harper and Savell. the electrolyticpotential of cobalt being only +0*004 to the than lack that vo^ of demand for from cobalt higher than that of nickel. a ployed em- over nickel. Tannin. (4) The deposited cobalt is harder white a high polishshowing a beautiful than nickel. thus with the same electroplating cobalt film was is 2*5 times as In dm. it takes lustre with a slightly .ELECTROLYSIS The IN complex for have agents been have Certain deposition. The its electrolyticpreparation has ores Doubtless. glue.and produced a satisfactory current deposit.

with (1) and than weaker 40 gms. for . . The followingcompositions (1) Cobalt ammonium in found satisfactory electrolytes were most two of the baths desirable any efficiencies of nearly (7) Current obtained to up : " sulphate (cryst). suggested by Boettger. 19*6 Sodium " Boric Cobalt acid. (6) Plates per with thickness 100 densities up current to and could cent. have The without In would a proved satisfactoryin practice.200 per gms. computed the to ELECTROMETALLURGY actual The give the of hard weight 4 times protectionas same metallic is cobalt its weight of softer nickel. The electrolytescontaining the complex Co(NH)3)'#4. litre. Nickel bath Alloys. to in the metal. not double modified on ammonia cobalt by a addition the small be indicated removing the depositingbath Boric of quantity practice the Cobalt mentioned sulphate bath use baths to the plating suitable ammonium magnesium or articles. Beardslee. (2) Cobalt per litre. and ion others. per 20 . sulphate. . acid .312 gms. Watts it is claimed . Deposition of Cobalt gives the composition of a (2) loss of solution unavoidable Langbein suggests as electrolysis " sulphate . of owing has above litre. passivityphenomena do not appear to be so much in evidence in the electrolytesemployed by these investigators.. saturation. chloride. de- be may be 5 amperes over dm. from which " O. sulphate been of citric acid.. films metal of this gas solution the to former peelingpropertiesof the we owing in the less soluble and have nickel probably superior to hydrogen is much fact that . P. (5) Both rolled and cast cobalt anodes used be may .104 INDUSTRIAL bluish tint. sq. nearly is also noted that can generally be attributed to the metal.. per posited.

p.. 1905. Treatise on Zeit. Phys. Schnell Electrochem. Soc. 47. Pat. " Blount. 1209. Elektrochem. 1897.107 accomplished.. Phil. REFERENCES tion inser- by the other the in the be alternative either in obtained. 820 Practical " Chetn. and 9. 1880. Phys. . 8 Metall. acid. vol.C. Mag. Steel. xxxvii.. pp. 1907 Elektroanalytische Luckow. . 18 Amer. Zeit. 1914. probably metals the from two nickel casting the by or per undoubtedly are current correct gms. 16 . Corrosion The p. 44. Atner. 91.. 23. Stuttgart. 1908.S. 6 Metallurgie. Atner.I. 27 1 Trans. 18 Siemens 18 80 Eng. 291 . and through alloyed anode. Electrochem. 1914.. Trans. 27. 1916. 1903. Methoden. 1904. Chem. an dissolve are miscible TO SECTION with in all 1 Metall. p. 26. " 17 Zeit. nickel cobalt anode uniformity. however. 193 Soc. Elektrochem.. 11 Dingl. 762. by which could this of two passing electrode.. Electrochem. 258.IN ELECTROLYSIS the alloy of nickel hardest (75 per Ni cent. Phys. 1895. 1906. 28. 190. cobalt and sulphate Cobalt ammonium sulphate Ammonium sulphate . 7 Addicks.. Soc. 28." 20. 288 1893. 1901. 21. II. Trans. 8. 258. p. p. 105 45-79. Chem. 24806 of Iron J. Halske. . each The perfect proportions in solid solution. metals There be be 40 of boric can two electrodes. 8. 236. Ind. 52.. 1904. 15 Firchland." Electrochem. 202. 84 Chem. 1904. 10 Zeit. Electrometallurgy/'p. . 158. 25. 1913. Chem. the addition I^angbein suggests Deposition of of 3 ratio the anodic the Ni to of the solution corresponding ratio. 191 4. 1908.. E. the Co 1 147 metals two can " ammonium Nickel 105 Co) cent. 11 " 18 Zeit. 1908. Anorg. 1914. one deposited 56 . 710. 688. 25 per : SOLUTIONS AQUEOUS . Soc.. Electrochemistry. Chem. 689. 19. Zeit. " 1906. 86 Chem. /. Chem. 347. . Trans Soc.S. Phys. 1912. Amer. must. 8 14 .. 2.. 81 Electrochem.. Tech. A Rideal. " Zeit. J. Pol. "" )9 "l 99 solutions such be and dissolution of schemes cobalt." of and 88 86 (6). Amer. 296. Macmillan.C. 5. 4 Trans. 88 Bunger. Electrochem. 10. 17.. since for would litre.

40 Electrochem. Angew. 187. 1892... 202 .... 50 Zeit. 19. f. 384. Chem. and Eng. Elektrochem. 1911.C. Soc. 1906. R.. Electrochem. 321. 827. Soc.. Elektrochem. 41 Ber. 223. Chem. 1912. Dingier. 88. 754 . 8. Elektrochem. 1. Amer. Metallurgist. Anorg. 74 Trans. Schuster. 55. 9.. 69 Zeit.S. Russ. 1905. 1911. 1878. 1900." Wien. 22. /. Electrochem... 44. of 1886. 149. p. See 44 Met. Chem. 1912. Poly. 1910. 88 Michailenko. " 86 Zeit. 46 Kern. 9. Electrochem. Electrochem. 88 Trans. 43. Leduc.. 28. 1000. Soc. 48 Soc. Proc Phys. 1909. Amer. Fat. 30. 668 67. 441 Soc. 575.. J. Zeit. . 88 See " Lead 68 D. 11. 88 Foerster. Chem. 373. 47 48 145. 219. 50.. Anorg. 34. 24.. 276. Amer. Engineering. 1909. Langbein. 46 Bancroft. Chem.."A. 23. 229. and C. Farad. Ind. Electrochem. 68 Zeit. 88 Trans. 64 D..8. 344. 45. 1900. 509. Trans. Soc.P. /. 1910. . 66 Chem. 1912. Met. 16.. 25.S. 279. Soc. 9. " 78 Met. 1907." Electrochemical Elektrochem.io6 INDUSTRIAL ELECTROMETALLURGY 87 Met. Chem. 28. 1905. 61 /. 58 Zeit. 1350. Chem. Zeit. 507. 143. 200. Pract. Electrochem. 1903. . 25 . Ind. 7. Anorg. 6276. 1907. 10.C.. 1912.. Elektrochem. 48 11. Eng. 16. 1906. 78 . Soc. 13. 64 Ber. 1910.. 313. 451 Chem. 55 Zeit. 1 . 1908. 1882. Chem. Chem. 490. Betts. B. 10.P. Angew. 191 2. 464. 78 Zeit. Amer. Amer. xxiii. 355 . 1913. 1. 479. 4. 38. 779. 599 21. 8. . 7. 1904. 80 " 81 Zeit.P. 68 Trans.I.. Elektroplattierung.. Soc. Zeit. Trans.. 87 Electrochem.. 1908. 11. 88 88 Amer. 68 Trans. J. of 302 Electrochem..R. 1843. Some Soc. . 1904.S. Elektrochem. Phys.C. 443. 137. 1905. 13. Ind.. 193 Centres. 10. 2. 6..067 of 1885. Amer. 16. 979. 48 Trans. 1904. 1900.R. 80 Frary. Phys. 383. 81 88 88 84 88 Ind. 88 /. 995 . W. Zeit. 1996. 1908. and 827 Met. 25. Refining by Electrolysis. 500 Anorg. 87 Amer. Soc. 9. 1910. 1909.. 70 J. Elektrochem.. J. 11 Elektrochem. . Zeit. 71 Chem. 91. 1908. 1900. 87 Zeit. Electrochem. /. 1905..

" Monographien fiber angew.c 1912). Pat. Elektrochemie. p. der "Handbuch of Metals. (Metallurgie. Principles of Electrodeposition. "ElekPfanhauser. W. Eng. Pat. 191 1. vol. 1909. 916. Pat.. 345. 237. " U. Zeit. 2. Pfanhauser. 1909. .S. 87 U. of Metals. 34. . of 1904. 5th edit. 1896. Soc. 1905. Metallpolieriung. 84 Electrochemical Pat. Electrometallurgy " xxiii. 191 Applied Electrochemistry. 81 " 91 Trans. 1907.S. p. Crosby . 78 Ind..78 Electrochem." Wasseriger Elektrochemie Die 191 1904. SECTION Elektrolytischen Metallniederschlage. and 88 Schock 97 Foerster. Elektrochem. Industry." Erz. u." Watt and Phillipp. 78 U. 1901. Electroplating. 7. 100 U. 77. Elektrometallurgie. 88 88 loy 707. 440. 79. Dept. 15. Amer.706 of 190. 7.759..9.. 942719. 98 Engermann. 86 Watt 1907." Vienna. " Practical '" Electrometallurgy. Allmand. p. Principles of Lock . 121. " 191 117054. xxiii.S." Electrochemistry. Review. TO II. Schineitzer. Ger. Electrodeposition Kern.567. p. d' Electrochem.S. Pa. 1915. Blount. 86 . Leipzig. Eng. p. 1911. Electrochem." Electrodeposition "" 86 7. 1912.P. U. o. 188 Bureau of Brass Electrochem. p.155 88 Zeit. Canadian World. 191 3. 15. Electrochem.675. Borchers. 105 Trans. 82 Electro chemist. 1905. Electroplating. 191 1907. Macmillan." G 1903." Barclay and Electroplating and Refining wood. 160. Hasluck. vol. 188 Langbein. Billiter. Elektrochem. Rev. 1908. Amer.S. Mines. 10. 4.Langbein. 12. 108 107 . 628 1. Soc." Pat. of Mines. McKay. 1909. 6* SOLUTIONS AQUEOUS IN ELECTROLYSIS of Metals. 464. 112. 8. troplattierung Galvanoplastik u.." B.230. 402. " 1905. 1908." Kershaw. 1.P. 319. 278. Hainsworth. 245. Zeit. 2. 602 1902. 236. " Phillip." P.. 88 Metall. Pat. 1909. 1897. Electroplating. 77 Electrical Eng. Metall. 208.. 104 The July.t 1.A. et d'Electrometal. Soc. 3.R. Elektrochetn." it p. 80 81 June.R. W. Trans. 1909. Zeit. 1900. Atner. 99 Electroplating. 7. Kern. Pat. 229219. 101 D.. 84 Kershaw. 213.. 282 Losungen. D. Pat. 1911. 244. Elektrochetn. 1909." Langbein-Brannt. BIBLIOGRAPHY " 2.

Electrolytic it Practical " Some Methods of Analysis/' Kershaw. L' Industrie Electrochemique. A. ' H. Elektrochemische Electrical Engineering. Classen. " Elektroanalytische It Quantitative Methoden. Literature. Elektrolyse. 1903. Pring. Smith. A. Metallurgical and Engineering Chemical and fur Zeitschrift Mining Zeitschrift. Special " Modern " Metallurgy ""ie " Electrolytic Lead ' ' " 191 Zinks des Ulke. Springer." " Analyse des E. Blakeston. Society. tische Metallurgie Elektrometallurgie by Electrolysis/' Verzinkung. Review. Metal Industry." Louis. and Electrotnetallurgie. Elektrochemie." S. Man- Journals. W." durch Enke. Univ. Electrolyse/' par Paris. Stuttgart. and Holland A. " of W. Cowper Coles. des Zinns/' des ' Elektrolytischem A. Press. Dumond. Metaux Pa." Halle. chester. Refining Elektroly "Die Copper Tin. Gunther. auf Wiley " Sons. Betts. Industry. Borchers. Mennicke. Bertiaux. Wiley 1 905. Electrochemical Mineral Journal. Berlin. Industry. L. Refining." G. 1. ." Darstellung Knapp. Faraday Metallurgist.ELECTROMETALLURGY INDUSTRIAL 108 " Electroanalysis. Nickels. " Sons. Electroplating/' Electrochemical Centres. N." Schnell Analyse Fischer. Neumann- Bedell. L'Electriden. Transactions Transactions of the of the Electrochemist Electrochemical Society. Wege.

.

1 diameter. dcm. soda. The of the cathode The of the the gas a rature tempe- a C. wire electrolyte. cent. liberated the Both (cathodic)+02.. per and amperes per of means is fitted discharge pipe a at the by the wire-gauze by out under liberated sodium ladled be can the dipping B. is retained top and the metal spoon. at and than oxygen the of the liberating hydrogen. cm. 1909. formed Hevesy. Above electrolyte. liberated in causing explosions. The per amps.. current the total current cell per efficiency of about tained fused being 45 by the 1200 The the cell to ensure placed round protecting crust of caustic soda cathode cell the : be can Electrolysis is burner. the current a electrolyte is main* formation the and started by at C. at and sodium the anode there the anode Further sodium difEuse hydrogen reactions the cathode and through the bulk rapidly more compartment. at 5 giving volts. react. 2NaOH=Na2+H2 since water at may be water lyte electrometallic high temperatures. Elcktrochem. 15. dcm. the investigated Brode2 of of Mechanism to to the never liberation equations " 2NaOH="2Na+20H1 4OHI at the anode-"2H20+02+4" electrolysis on 2H20-"2H2+02 Net See reaction also V. due practically zero (m. molten 200 density is about anode density 170 amps. between the liberated sodium and . 539 . per of mechanism Blanc Le " electrical the that showed Electrolysis. forated per- a the to 45 sq. The or largest cells holding about 60 about are of kgm. the yield is 3000 C). crude NaOH the increased diffusivityof the metal in the electrolyte. The exceed 50 electrolysis and simultaneous according at the cathode hydrogen the to and efficiency could current owing cent. 100 deep cm.p. and sq.INDUSTRIAL no of free circulation permit to is cathode the ELECTROMETALLURGY ring of nickel a surface floats to screen. diffuses both Zeit.. gauze. hood.3i5"-320" as cathode just sufficient lagging is and current. of low as Above 5250 for of means thin a seal good a up conducted possible.

F. ring in serves fast the end current lowered by is liberated of the sodium rod density current is claimed for the efficiency.w. cathode to prevent by passing dry air or but have they potential of Blanc. caustic patents using by eg.M. current Various cent. per compartment. the a 35 of the exposed Castner high voltage . giving hours are fused dry electrolysis and current a efficiencyof energy an NaOH. electrolysisis the efficiencycan have the out returning water the with is conducted this removal. sq. 1000 produce 79 kgm. soda such. technical The the by molten to anode the through 50 effect *to water and hydrogen unattacked diaphragm from exceed never the as removed into taken been long as not decomposed but a that is evident It 2*2 volts. an efficiencyof 45 per cent. amps. employed.. 20 cent. is Process. per Hence k. is raised and as per cent. decomposition according electrolyteas not ceived re- application. the consists electrolyte in the sodium action Against cathode the as lies in the fact that solvent the containing The be can with cathode dcm.8 is Le to the oxygen.IN ELECTROLYSIS resulting from oxygen for in also electrolysismay the efficiencyloss. according small a ELECTROLYTES FUSED the to account equation " 2Na+02=Na202 again reduced then peroxide being the sodium at produced by the by the cathode. process the process. The this of the metal the must thus as chief so electrolyte as be set the very centre cathode formed high much in serves 1000 as giving advantage is not of means the process. to necessary of sodium. bath anode. caustic soda vertical iron fused of a gearing of the make to bath. Griesheim The " electrode " the contact production of calcium and for preparing magnesium. Technical of 5 volts applied E. which rod As shallow a as contact A cathode. per iron circular A to for occasionally used and this process In " principlegeneral strontium.

the removal difficulty. how- soda. The as of carbon. decomposition potential of 2*2 volts for being reduced to i*8 volts. Philadelphia. mixture a sodium a carbonate cent.whilst the anode containing vessel. sodium ever. is difficult to for on a accomplished the production technical scale. two +02 although there that decomposition by this +2H20 in the the the nitric manner the into nitric acid by products from and details available how usual anode anode converted is liberated sodium of this is perforated acid process produced by it by . There means is potential required viz. as the Electrolyte. cent.A. Castner electrolyte in soda per of use and as with process density. 4800 of C. an worked sodium fused to employ utilized (worked is said the in fundamental the water.F. yield of the small. and B. Na2S=2Na+S" +2S =2NaaS 4NaOH will It the noted be salts other two are which sodium of metallic are Darling process The central cathode. which is the the again electrolyzed. U. is surrounded made metal cylinders.S. of 15 and is there space From find and the out whilst the between removed volts recovered perforated ladle annular cylinders to be applied E. caustic soda free The to reform sodium is suggested the addition caustic fused the soda. P. which electrolyte. the temperature expected. stated by perforated coaxial is the cast-iron With at the cathode of a are condensation.) at nitrate electrolyte. is.M. current suggested electrode contact a sulphide. anodically react9 with sulphur liberated caustic fused is sodium theoretical The 50 dioxide carbon no Scholl sulphide to cathode. with the be carbonate caustic the to working these sodium Castner carbonate a Under of 50 per high a Becker* " modified melting-point the necessary. is not of the reduction a means.ELECTROMETALLURGY INDUSTRIAL H2 to necessary cathode operate of the Modifications the was provided with The addition of raises to evolved a of collector above of conditions at the anode. very cell.

would A vapour of i*. conceivably take place :" =4HN03 made phuric sul- 73. sodium so loo of Soda Chem. superheated this reaction strong 70 mixture advantages and of mixtures 4N03' +2H20 If this gas sodium to probably be gas. v. "The might could acid. ELECTROLYTES FUSED IN ELECTROLYSIS anode the as entirely of nitrogen dioxide and products 113 consist would : oxygen 2NO'8-"2N02+02+2e The production absorption the in water Castner nitre the 8.t be be and would the Potash. Phys. Alkali by anode the dustry Inthis and regulated compartment. 676.) obtained to over mjcw and with expensive even preparation of sodium steam by Liquefaction too direct followingreactions preparation of flO usual the (see Partington. of nitric acid +02 to +40 proceed smoothly concentrated nitric acid 8 in the one . acid the ib curve concentrated admission for process from offer any not making nitrogen dioxide ") nitric for lo "" of would process acid Fig.direct condensation. " when lo 4t Melting-point (G. Zeit. Hevesy.

development may using direct electrolysis between (A) Processes their solid electrodes. The Electrolytic Process. resultant The the 780 " lyte electro- C. salt crust lined EE. is practicallythe only one in successful operation. bottom owing process. whilst iron the that an anode metal the cathode electrolyte. of metallic production frequently attempted. The Virginia Electrolytic Company's as per cent. with and an chloride. (C) using a molten lead cathode. on hollow a below investigationsshowed of potassium chlorides electrolyte than the By off above vertical a horizontal electrode drawn A by and of the m. Further of the suitable more about potassium. been arrived have than sulphuricacid distillation and chlorine and economical more prove of sodium use sodium ELECTROMETALLURGY at technical some The in stage be grouped into three classes. Processes (A) Direct of sodium on the fused from lines of the loss of metal C.p.INDUSTRIAL H4 operation would of the The Castner which processes has nation combi- the for the chloride process. process. in placed in metal could A be the of other. the Fischer by conditions compartment one the considerable a scarcely feasible boiling point of 8770 C. the A of temperature higher melting-point sodium contained taining con- disposed was horizontal the the as equimolecular mixture sodium and of divided bath used was of scale partition extending maintaining that at production the shallow bath technical a for carbon through sodium to pressure. based 1 V. vapour necessary temperature. and a compartments two nearly already has is Greisheim or chloride) lies well sodium the at chloride by volatilization. and Kiigelgen plant installed designs of Seward Basel. which circular is furnace protected by CC is the employed. has Early indicated sodium into experiments this to the vessel. since liberated 8oo" sodium Castner (crude sodium the preparation " of on at firebrick.sodium tubular was orifice. contains a . (B) using Processes molten a lead diaphragm serving as intermediary electrode.

is The sketch. takes water- a down collecting vessel of the these on arid flows hood the by deposited the 10. is cell will be the only the function process of the is fed to to the mechanism on 2000 stated nevertheless with tried been cells Salt Process6 Ashoroft vertical provided carbon . The which has absorbing and were of an the with inner vessel a into molten is technical a 3000 of is maintained cathode vessel magnesia 8oo" in the this Several have in the whilst the base The and manner. J. dcm. under circular higher used into space than 200 without amps. longer no cast-iron lining lead in of one each amps. built. provided temperature cell is a type unit been satisfactory a from seen at scale. adjoining which C. operation.ELECTROLYSIS circular The IN graphiticanode cathode cooled DD. lines F. its upper at hood floats up the FUSED Intermediary Electrode. cannot sodium current conveniently be about through A The graphite anode. outltl (KLonns (B) Process using Molten a Lead A. per destruction cell constructed sq. cathode is surrounded electrolysis water-cooled 115 iron hollow a extremity On the ELECTROLYTES with BB.000 largest amps.

removed sodium . vertical a iron K Fig. ELECTROMETALLURGY molten given rotational a between placed . alloy second been molten cell. diaphragm return interchanger for the molten heat rotational a through the orifice second the mediary Inter- electrolyte. second cell containing fused maintained is liberated formed in at 3300 the at the returned and deposited On anode on tube lead caustic iron the . lead through with Process.The electrolyteas whole well by movement current magnesia the proceeding to the electromagnetic force field vertical a since vessel. wire The is cathode helix vessel. and to the surrounding first tube orifice H. io.n6 INDUSTRIAL anode F. right angles. Cell for " Fused Electrolysis of at component current of the movement By of means suitably situated a is caused flow electrolysiscell K. the and cathode sodium C. causing molten space Chloride Sodium Ashcroft Electrode. has vessel acts as a lytic electro- chlorine current sodium the The the electrolyte is lead into the annular second as passage into an thus D rotating I into back D The first after the the the through first cell is circulated to the and C. and electrolyte can the direction resolved be the component of the means liningand the operating the cell is passed the through the helix before way molten the as into of anode is the both generated in current in the zontal hori- and the horizontal field will cut magnetic first in this . soda of the F.

.

and liberated of means sectional chlorine liberated The from the molten the This indicated as steel or be to chlorine.to A bottom electrolyte of stream anode in C.n8 INDUSTRIAL is easily operation 700" fused the far below electrolyte 710" C. narrow trical elecSince range difficulties quently fre- . 6330 permitted serves gas is maintained dissipated in heating is and is inserted electrolyte. and diagram. container the as the specifically lighter anodically the by following serves is magnesium molten kept separate is melts C. whilst inert temperature of magnesium m. Since fused chloride magnesium Pure salt ELECTROMETALLURGY pot action of C the electrolyte by a rw solidified porcelain cylinder slits in the cylinder A B part open carbon the at immersed immersed continuous dioxide) The I". from accomplished in the technical In between 6500 C. a the solidification of the the electrolyte. crust in in the is maintained sweep have cathode In practice energy the to the penetrated the is all that can occur be the out due to having (nitrogen part upper chlorine any the as in vertical iron an cathode. carbon or of a the which cell may compartment. by and metal. iron from than there porcelain hood. the through during electrolysis. it floats to camallite.p. at is maintained tlie double but this temperature. a protected and has surface. somewhat working.

the alloy of potassium an readily catches which and common lead to inefficient oxidation formed 6 volts 5 to of the melt. per Aluminium the the will coalesce. more anode which continuous and now in cathode serves . electrolyteis renewed dcm. 90 per over 1000 . to will Works Magnesium and of sodium The the to be by is worked the position of The iron rod frequent the Both density usually employed. where chieflydue using surface the to in the of iron anode.ELECTROLYSIS Although chloride is the If too and is 01 of cent. a magnesium of voltage high voltage be employed small 119 volts. magnesium cathode current (750"-8oo") and per Oettel8 current careful By cent. as I^ess than the carried are a current successfullyoperated has of and means. efficiencyis stated made density working chloride. and can by this small Occasionally the floating chloride cent. small efficiencycan current metal a moved re- density is usually employed per a as magnesium the again are This oxygen and current magnesium but thin oxide fluoride. globules of molten to the formation inert an addition the the anode. is caused be maintained. although a sq. Hemelingen said to sq.as amps.. cell with electrolytea mixture continuously. dcm.. per iron efficiencyover 20 into to the A of a little calcium fairly high cathode 10 to up 15 high high per working with and efficiency is produce The with a a 9 use as of (27-30 amps. proportions. anhydrous temperatures By voltage of 5*5 volts per cell the carnallite in molecular addition cell. The current have been its action in the A. of metal. by suggested hy Deville. by reversing the containing a efficiency70 kgm. nearly 52 fog phenomenon. yet in practicefrom to maintain magnesium causes decomposition only 325 employed are ELECTROLYTES FUSED IN Attempts cent. the temperature explosions in carnallite.) very cent. 40 amps. in the dcm. 50 per cent. per Traces alternate the to salt at cathode ferric fire and nearly unavoidable working due of the cell. are containing gas reduction reduce coalesce not electrolyte and film is dissolved oxide from as do they impurity. reoxidized. 70 per process are chloride and process higher than are make vessel. energy hours kw. and film.

removed method it in advocated fluoride above who residue adherent Wohler12 contact a described as lyte. same the difficult than more the although of metallic in to a 60 sealed to per on the quench it. when at Calcium. unsuccessful proved electrolyticsolution pressure The of use chloride metal for subject of patent literature.p.p. 66o" calcium is 8oo" C.This of means used electrolytebetween the solid calcium manner large scale porous and melting point mixture accomplished by calcium Plato11 melting point of metallic Borchers a of production (m. and electrode operated (1). 10 Tucker of point has magnesium form in the of a together under have which sponge. first petroleum containing 50 metal chloride 7800 C).whence cent. The preparation chloride is the form calcium Pure although of use a containing Since of is the Ruff lower 12 and a same of calcium cent. been the proved of practical have none melted and account on of the solvents organic and from deposit magnesium to metal the be removed can flux of calcium a Attempts 500" C. produced calcium continuously. is obtained. electro- as directlyby electrolysis.) is chloride C. 7800 C. and it solidifies in to of fused coat a cathode as slowly raised is cathode as obtained. the electrolyte. The in the the molten the solution. however. per obtained. and high a rod-like control of the difficult under in form serves cathodic conditions. is essentially the Stockem.13 and and by this immersed of calcium The is fused chloride. the lytes electro- aqueous of the high Eh =+i'55 salts has volts. (m. these metal is usually below attempted the electrolysis the melting potassium content the tected pro- of which carnallite. to prepare in the the fused from electrolyzer employed possibleby maintaining 8oo" calcium in construction.ELECTROMETALLURGY INDUSTRIAL 120 adhering magnesium by from current density is. it is C.the base electrolyte. vessel and metal was separated . from calcium magnesium.but utility.

By deposited cathode.M. dcm. Laboratory however. . experiments on from the fused the preparation of calcium smaller much cathode be accomplished with densities current than practice. ammonium carnallite.provided accurate an Frary. hours will from the occur may which With these coalesce a 15 energy per and calcium cent. K. Wohler. production of the neighbourhood as stated are efficiency rarely energy efficiency calcium. point of conditions round the in the form of fused calcium fog distributed metal as the much as the layer of produce 34*6 kgm. applied E.p. For economical of the metal.18 oxychloride with avoided in of the liberated initial fusion 15 per cent. This chloride by the addition moist can be calcium to the of an be impracticable.16 . magnesium Both loss electrolyte. resultingin the formation forms an insoluble metal. technical tained. Bicknell sq. that chloride can units small have shown. chloride or electrolytecontaining much the of the chloride Regeneration oxychloride is stated to . is main- control temperature and in used be to 9*3 amps. be of of calcium.15 50 to 250 used H Tronson Goodwin. and 20 Arndt. The the to a be above continuously removed serious a but made protected by 15 per kw.*7 60. m.. fog formation an chloride volts.ELECTROLYSIS The about must an decomposition employed. the high only necessitating yield9 small in the obtained are case production continuous of process in the observed factor important very electrode contact is densities current per dcm. amps. 1000 be the just exceed maintaining be can in temperature electrolyteshould this temperature. chloride electrolytessuffer disadvantage that in the preparation hydrolysis of a hydroxychloride. but possiblebelow fusion the of the and without through to exceeds cent.000 to metal tendency magnesium about 121 calcium of potential volts. may chloride the should of mass calcium irregular rod an the cathode electrolyte.F. of 20-30 becomes and 10. to 32 per .but in practicevery 3*25 The ELECTROLYTES FUSED IN unless removal be employed.

Although lead dense a Borchers solution a of cast by fused from distinct advantage one (seep. an loo from cathode chlorides. separated from coating of a a sponge any received is in two protected by fully success- of its salts at without has water-cooled a and anode placed method iron has efficiency. be obtained of obtained a mixture good The amps. by in the a some is which electrolyticcell which series of residues the run lead the at insulating joint. hour. With density a in the syphon. a the on syphon. per an electrical angle. 83). whence applied E. Electrolytic lead solution aqueous an refined lead density current furnace The another and electrical the surrounded The in which retain hopper a cell collects collects removed by off second potassium and at about 5500 a current lead could 19 C. is maintained bath of 0*5 sq. is itself is side. employed sodium is at molten crude lead of means a solidified salt. similar to those detailed some the manufacture and barium magnesium of do show not calcium. but production of direct in refining is usually accomplished Betts 5 volt and kg. and for molten small as fog a difficulty. manufacture for their apparatus slightmodifications.using molten . Lead. deep horizontal reservoir A of the hearth electrolyteis As of the top. but as the meet The laboratories.M. dcm.F. of pure and tine Valen- efficiency.ELECTROMETALLURGY INDUSTRIAL 122 Strontium small a on scale chemical of requirements is. platforms lead hearth fed The of lead in of the it is where tinuously con- resultant it is oxychloride. and tendency a the at appear coalesce which drops of metal such produce to cathode with Strontium calcium. a the ment* encourage- no auxiliary furnace an having to serve from flue of the surface its inner of the side high parts. with to only conducted is elements of these manufacture The Barium. per kw.

^Dsrc. required maintained at 6oo" the to start by the zinc chloride blende remove leaden a was vision Pro- drawing off the liberated was process dry chlorine of conducted were electrolyticcell recharging and the Ashcroft-Swinburne the experiments as cathode as made was In (see p. which As for Extraneous was after action of treatment anode a vertical a piece bent heat subsequently with lead on to in vessel position by carbon rod strip zinc. silver and scrap . rise above to low a red impracticable. 139).M.adding as to 123 good yields of molten volts 1*25 obtained. the caused Borchers' " heat. Cell the process applied an lead could galena soon COOUNG refiningLead for melting point With in the impurities present the ATER Fig. but close-fittinglid hermetically sealed a fused used who (see zinc chloride. and 58). semi-technical first methods electrothermal by solutions the current. furnace.F. with zinc employed. accomplished The preparation of metallic zinc has been only by electrolyticprocesses in aqueous not p.ELECTROLYSIS chloride lead of to 1 time 12. when time. and gas. produced by C. electrolyte. sodium and ELECTROLYTES FUSED IN of the bath becomes in Fused Electrolytes. but be chloride from galena finely crushed E. electrolysisof fused also by The by Borchers. chlorine chloride. to 7000 C.

ELECTROMETALLURGY.

INDUSTRIAL

124
zinc

to

the

remove

of the water,

the

of the

rest

primary-electrolysisbetween
carbon

anodes,

The

deposition of
vessel

cathode.

Carbon

tight roof

was

A

*"

pans

to

remove

being removed

water

zinc

molten

a

zinc

the

on

took

by

cathode

a

and

similar

to

maintained

was

firebrick-lined

a

zinc

molten

used

were

employed

in

place

of which

base

anodes

slight vacuum

and

to

cast-iron

a

that

acted

gas-

by Borchers.

used

of

removal

the

ensure

as

chlorine.

the

sodium

When
molecular

chloride

quantities

of 4*5

drop

volts

of

current

cathode

3000

over

surface.

chloride

is 1*49

gives 1*57

or

43

Thus

the

formation

the

volatilization

noted

of metal

above,

chloride,24 which
the

of zinc.

by

the

also

those

of Ashcroft

and

electrolyte without
found

He

it

than

16

amps,

volts

at

4500

This

to

25

Swinburne,
the

sq. dcm.

of
a

with

an

traces

by

zinc chloride
both

due

much

to

also to

reduced,

as

sodium

or

conductibility of

experiments

to

zinc chloride

as

chloride.

sodium

higher

density

current

applied E.M.F.

of 45

C.

adopted
as

be

high temperature

zinc

the

disadvantage of these processes is
preparation of the fused zinc chloride
whilst,

pure

any

The

Vogel

a

similar

use

would

hours

using fused

addition

28

Suchy

efficiency is

energy

potassium

increase

conducted

impracticable to
per

of

of
zinc

of

potential

be

and

sq. dcm.

electrolyteand

can

addition

serves

electrolyte. Vogel

in the

cloud

high

voltage

a

Lorenz,22 whilst

to

a

4500 C,

per

kw.
cent. ; 1000
approximately 35 per
When
to deposit 260
kgm. zinc.
necessary
is used (6oo" C. and over, the m.p. of
is 3650 C), there is a considerable
loss of
the

of

amps,

decomposition

volts.

with

temperature

a

according

volts

present,

obtained

was

amps,

The

i'6o

to

cent,

electrolyte in

the

to

chloride

zinc

the

to

cell at

per

added

was

efficiencyof 98 per

current

a

iron

filtration and

suggested by Lorenz.21

as

sheet-iron

by solution

in enamelled

concentration, is fused
most

followed

lead

the

expedient

of

free

found

in the

from

water.

in

evaporation

already indicated, Swinburne
electrolysisusing carbon

to be

the

removed

anodes

as

vacuo,

an

last

oxygen

126

INDUSTRIAL
electric

carbon-lined
low

alumina

not

owing

aluminium

has

powder

impuritiesinstead
Heroult

the

In

roasted

to
to

as

pass

digested with
of

pressure

caustic

lined

Silica is also

by

thrown

dissolved

The

alumina

The

into

through
is

bauxite

of

gently

is

then

powdered
is

material

powdered

solution

in

the

to

sodium

hydroxide

made

in

aluminium

dried

and

recausticized.

objections
solution
some
tated
precipia
previous operation,

hydroxide

is washed,

the

these

agitation,about

under

since

and

to be

overcome

aluminate

dioxide.

carbon

process,

it has

lead-

filters into

pulp

wood

a

alumi-

sodium

$s

reprecipitatedby

process

36 hours

the

of metallic

addition

The

organic matter,

down

this
the

to

after

form

a

electrolyte employed

the

into carbonate

aluminium

when,

in

prepared

crushed

screen.

alumina

modified

adding

and

passes

alkali is converted

Bayer

is

soda

filtration

the

vats,

bauxite

the

solution, sp. gr. 1*45, under
atmospheres for three hours, during which

6

After

nate.

the

process

aluminium

period the

alloy.

of carbon.

30-mesh

a

metallic

a

suggested for the reduction

been

water

remove

as

prepared by the wet
high temperature
employed

C.) the alumina
does not
easily dissolve in
production of aluminium.

for the

impurities

alumina

as

the

to

is too

content

purificationof

20000

(m.p. A1203
which

iron

easily reducible

the

suitable

so

since

processes,

so

the

and

resultingfrom

is,however,

the

If the

by settlingto the bottom

removed

The

furnace.

is added,

more

are

ELECTROMETALLURGY

70

of

recovered.

be

can

cent,

per

finally roasted

to

about

non-hygroscopic, whilst the soda
in a triple-effect
vacuum
solution, after concentration
rator,
evapobauxite.
of
of a fresh quantity
is utilized for extraction
Over
40 per cent, of the cost of manufacturing aluminium
11000

C.

is stated
The

to

purificationof

in the

be found

electrolyte consists

alumina

in fused

addition

of

a

variable

Hall

essentially of

amount

of sodium

fluoride, and

of the chlorides
the

the bauxite.

cryolite (AlF3.3NaF), with

fluoride, aluminium

In

it

render

to

of sodium

process

the

or

a

or

solution
without

of
the

fluoride, calcium

occasionally small

tities
quan-

calcium.

electrolyte is prepared by

IN

ELECTROLYSIS

treating

in

acid

hydrofluoric

is

127

cryolite, and

alumina,
lead-lined

a

fluorides

mixed

of

of

mixture

a

ELECTROLYTES

FUSED

melted

in

the

drying,

After

vat.

with

fluorspar

mass

electrolytic smelting

the

furnaces.
is stated

It

Heroult

that
have

processes

Per

.

590

.

NaF

CaFa..

dissolve

Hall

at

furnaces

N.Y.,

Lockport,

of

are

13.

wide,

and

whilst

a

Hall

"

number
in

The
250

the

and

With

the

at

Aluminium

total

1

rods

44

per

cent.

A1203

iron

lined

with

at

the

in

of

from

180

cms.

3 to

of
is

4

cathode,

as

in cross-section,
the

to

series,

density

cell

Aluminium.

holder

and

anodes.

being

temperature

of

serves

cms.

40

each

of

100

10,000

per

the

cent,

of

amps,

amps,

per

sq.

(below 9800 C.)

approximately
on

taking

anode

nearly

working

regularly deposited

addition

liner
sq.

as

current

per

carbon,

long by

metre

some

serve

current

E.M.F.
is

an

cent.

per

156
564

""

carbon

worked

cathode

a

The

bath,

are

The

applied

*

each

to

amps.

dcm.,

.

Electrolytic Production

the

special holder,

furnaces

represents

280
.

anodes

of carbon

a

holders

for

deep.

metre

1

mounted
four

Furnace

cast

some

are

carbon

Fig.

"

employed.

temperatures
and

:

Heroult.

20

some

and

Hall

the

cent

AlF^NaF
CaF2*..
AIF3

cent.

200

electrolytes

The

Per

21-0

...

These

per

in

used

following components

the

Halt

cent

A1F3

electrolytes

the

5-5

volts.

carbon

base

calcium

chloride.

and

128

INDUSTRIAL

serves

as

the

ELECTROMETALLURGY

anodic

in contact

being

cathode,

with

the

liberated by the reaction

oxygen

whilst

carbon,

"

2Al203-"4Al+302
the carbon

consumes

anodes

according to

equation

the

"

A1203+3C=2A1+3C0
which

have

aluminium.

molten
I

The

by

The

rise in

a

by
the

bath

terminals.

to maintain

low

as

According

to

keep the bath
which

of the

monoxide.

carbon

suggested

as

method

Not

only is

The
and

are

cathodes

anodes,
35*5
the

a

of

however,

Heroult

in

a

are

diameter.

design

to

solidified electrolyte.

in

which

is

alumina,
to

serves

formation

or

lyte,
electro-

of

carbon

or

the

lated
granu-

burning

the

anodes

has

also been

externally heated, but

has

heating

the

on

dispensed

been

now

surfaces.

cooler

designs

to

the

rectangular in section.
vessel

are

of the

are

Hall,

Carbon
;

the

up

to

taken

in

employed

Special precautions
use

tion
forma-

by the

attack

similar

with.

economical,

more

usually stouter, occasionally
make

thick

a

point where they enter
reducing atmosphere of

were

electric

are

of the

for this trouble.

containing

iron

an

across

energy

the

obviate

to

the

at

electrolyteon

either round

made

the

surface

protected from

furnaces

Heroult

cms.

is

vessel

crust

in

internal

shunted

of

heat

to the

serves

furnaces

procedure

the

iron

the
of

good remedy

a

the

Whitewashing

of

this

but

also

originalHall

The

into

maintaining

electrolyte by

the

panied
accom-

continuously fed

la}rerof powdered

a

is

temperature.

electrodes

anode

is

decomposing

temperature

This

charcoal.
away

of

work

proper

with

day.

a

electrodes, indicated

one-half

usually solid owing

crust, is covered

the

is convenient.

is converted

the

is

alumina

from

once

electrolyte

the

across

voltage as
Pring*7 about

at the

maintain

the

a

remainder

the

tapped

low-voltage lamp

a

Fresh

in the chemical

expended

To

of

inches

two

are

from

voltage

luminescence

the

less than

furnaces

alumina

of

removal

and

maintained

be

to

protecting crust

of

p. high as per sq. to tioned. volatile sodium a is 20 temperature an 6570 and as composition diagram. have 129 density of 190 amps. b.. electrolyte2(AlF33NaF)3CaF2 The When low as melting point is first Melting-point composition diagram dissolved in cryolite. 18000 the If too high owing to for alumina electrolytes the has a is said of the the to of m. at then and is in temperature Cryolite melts lowered working voltage is about amongst 7500 C. is at will be obvious. chloride lowers the m. whilst the addition m.p.ELECTROLYSIS Working 7*0 with A Temperature. the 9 . the published employed.p. and 10000 of ( (too To lytes." obtain of other C.p. in the lyte electro- furthermore. men- have somewhat 7100 under aluminium C. e e to iq it \h le low is necessary. cathode a The 8oo" as C.29 the importance of working C. cathode to the the that addition already been of 8200 C. dcm. as it is remembered temperature falls off due ii.28 q low substances addition of alumina. 14. cryoliteelectro- neighbourhood the as The by the indicated by the temperature Fig. operating temperature of the temperatures been 10000 raised C. current usual but The " divergence is found considerable figuresfor the ELECTROLYTES FUSED IN density be employed the efficiency resolution formation of aluminium of metal fog .

complete depolarization. Salt. V Vyli LC calcium following figures by electrolyte. NaF 47 . . value assuming value. 37 mols. Gin.. controlled. "" "" "" "" Cryolite saturated with A1203 aluminium Cryolite and fluoride. A1203 actual comprising generally confirm the Calcium cent. in approximates the that sodium and fluoride indicate 30 density to the specificgravity of electrolyte metal of the : " commercial . by figures of Richards the its it forms as ages volt- electrolyte are made Experiments the fluoride decomposition the arc Gin and not and Minet by calculation. gr. Calculated Observed Richards. when is of calcium traces by electrolysisof the present. . anodic 279 2*8 2*3 22 393 40 249 250 C+4F' AlFg . " j =Cf4+4@ " E*(Al)/wAl2(S04)3=+i-28 volts. is about a furnace 65 per cent. may melting point.INDUSTRIAL 130 ELECTROMETALLURGY deposited metal formed The closely the molten V*l metal solid actually greater than Aluminium. how contain may sodium and Richards W. of S1 a A1F3. with Current Minet be the add to . "" "" . operating An at increased a rature tempe- efficiency . the fluoride addition best " accurately arrived therefore Efficiency. the The melt. of the 32 raises it 8150 C. per melting point also of sp. but addition should appears to eutectic at the be various salts known. G. at Decomposition Voltages calculated. AlF33NaF Cryolite and aluminium fluoride with saturated alumina practice it In sodium advisable is found not fluoride. much too aluminium. The current of efficiency of 9000 C. and lowers substance. since although this lowers yet it increases formation solubilityof the Aluminium occur..

kw. electrode loss. consumption within reduce at rise to effects may halogens. with maintained are in efficiency current a obtained. anode alumina. 5*5 volts per furnace.and These .ELECTROLYSIS results in of 95 of metal has cent. is electrodes molten voltage loss arcing is caused. conditions efficiencyand current 131 the reduction to efficiency of the energy best 95 per cent. Halogen CF4 or CC14. per energy approximately Consumption. current dioxide and hours. anodic oxygen and efficiency 1000 of " cent. per would the FUSED lowering the temperature owing formation the a IN equations of " Al203+3C=2Al+3CO 2A1203+3. cause two of the The of the tion depolariza- resulting in the of metal electrode carbon alone.C=4A1+3C02 voltage of the the When of dissolved lack the liberation chloride complete formation of produced the 06 from maintained to this can this this temperature. the efficiencyis only energy 95 With 100 produce output is Anode monoxide with monoxide high densities according obtained by mixture a the to that noted forming carbon anodes. liberated =38 " kgm. present in the be is allowed bath increased whitewash point where long pieces additional losses . 153*2 practically complete carbon X cent. If the anodes and ammeter internal roughly must the are not are they enter the crust drop into furnace by by the air bath. either fluorine of is also kgm. frequently been working will It be is low furnace . at the electrolyte. 7500 C. be in order metal over accompanied occasionally oxidized they carbon of to if sodium kilogramme every to due only be accomplished by regulating the distance observation of For inches resistance the chlorine or owing occur electrolyte. 25 kgm. per noticed that assuming the the ELECTROLYTES At fog. by Frequently an thickly protected by of molten the voltmeter. most 1000 per has It in metal. already been the the works depolarization is consuming hours kw.

Minet 36 used a solution of cryolite chloride.INDUSTRIAL 132 bring with electrode the former the obtained.of which Great and three Britain. 98-45 0*87 1-29 0*13 o-io of costs followingestimates the kgm.35 cryo- gained owing to the low decomposition than more voltage of the sulphide (0*90 volt) are negatived in practice by the difficultyin preparing the The advantages sulphide from in sodium The produced two bauxite. Austria output exceeds factories. loss aluminium the amps. . contamination undue Technical deposited. and Germany. anode working 33 Blount aluminium. obtained carbon anode with of be of the metal aluminium Heroult ing workbe can high grade densities current weight careful kgm.interest capital....000 some one are tons in the U. amongst mentioned AI2S3 in molten time. 100 per kgm.A. each in Canada. the lite.. .. 34 Wright per gives UL I. Power Carbon electrodes Alumina repairs. Si il 99-59 99-00 025 016 Fe . annual world's in eleven in France and Switzerland.. per must in the sq.. 10. on tendance 22'4 electrolytes have Other but have received not important more been suggested from technical be may 23'3 time to application.although 0*6 for nearly weight to up figure of The prevent Hall. from vary to to 80 in the 400 gives the followinganalysis of commercial high degree of purity actually indicating the : " Al . ELECTROMETALLURGY with over iron.S. dcm. superin- Labour. . aluminium of production : " 1.

.

and 1901. and 1902. 612 Soc. 8 Zeit. 408. 25 Trans.." Gin. 272. 117. " 10 Trans. Applied Electrochemistry.. Griinauer. 218. Ind.. " Halle. 367 1905. Elektrometailurgie. Electrochemistry. 1910. . 80 Electrochem. 123. Chem.. 7. 5 SECTION TO Soc.R. " ElektrolyseGeschmolzenerSalze. 30 Zeit. 1895. 307. 817 8 Zeit. Electrochem. 63 81 Zeit. 8. Chem. 152 Elektrochem. Elektrochem. Elektrochem. 1905. 14 Trans. 1896.. Bailliere.... Electrochem. 10. 12. of Lorenz. . Anorg. 8. 19 Zeit. 18 Allmand. 27. 1901. 1. 1 Zeit Ind. 389.. 757. Alkali Metalle." Furnaces. Elektrochem. 88 Electrochem. "Electrochem. ." 1908. Industry. Amer. Soc. Electrochemical Some 28 32 Zeit.INDUSTRIAL 134 ELECTROMETALLURGY REFERENCES 1 Electrochem. 63 Metal. 1902." 1906. . H. Elektrochem. 1403." " Principles 4* " " The Die Alkali R. 612. 27 " Pyne. 1904. Cox. 4. V. 17. 9. Soc. J. 15 Zeit. Ind. 88 Zeit.. Elektrochem.. p. p." der Alkalimetalle. 13 Zeit. 1909. 8." J. Amer. Anorg. Electrochem. 1910. . Chem. and 1. 2." Industry. 1902. 1912." p. Gewinnung des Elektrometailurgie Aluminiums. Halle.I. 1905. 18. 29 Greenwood. Elektrochem. Eng. Soc. 7 Partington." 14. 1908. 88 Zeit. D. Electrochem. 89. 1906. . Centres. Tindall Minet. 408." Soc. Elektrochem. 219. p. Congress Applied Chemistry. 389. 4." A. 244 11. Amer. Elektrochem. . p. Becker. Atner. 86 Borchers. 4 Elektrometailurgie der Trans. . p. 1907. 1913. Elektrochem.. Amer. BIBLIOGRAPHY. S... "Applied 84 81 81. 17 Zeit. 697. Trans. 14. " Met. Knapp. 1904. 1904. " 1901. 1905. 33 " 84 "Electric 36 G.t 8. Ind. . Farad. 56. 1910. 8. 1905. Alkali 252. Electrochem. 27.P. Elektrochem. Int. Partington. 216. Ind. 18. Chem. Met. Nov. 1902.. 12 Zeit. 1903. 1906 1906. 1905 Allmand.C.. 11 Zeit. 7. 1902. Chem... 108. Anorg. 148627 of 1908. 89. 9 Zeit. 1905. . Chem. R. . Knapp. Practical Electrochemistry.. 152.. 253 The II. Anorg. 18 Journ. 1902. 1905.

30*15". current electrolyticpotential of thallium +0322 of oxalate sulphate electrolyte. 3 and The electrolytic potential of indium resembles most suggest reducing a acid weakly a ammonium containing sulphuric acid volt.the or of fused T1203 using dcm. 1*5 KCN." PREPARATION OF METALS RARER THE Gaiaxum. Partial 35 The E*= neutral a on a of anode volts. chloride. water warm cathode platinum a solution on The soda. Gaujum from is the salt in the conveniently deposited gallate formed complex caustic excess cathode under o" supercooled to deposit of gallium a melted be can (m. Thaujxtm. Indium. and cm.p. deposition copper precipitation on especially in as double the suggested thallium and taking place a 1893 reducing as acetone. under reducing agents such The 1*3 to is liable to occur. is approximately cadmium. the electrolyte. with or as l Schucht to sulphate. is (for Tl/Tl' solutions).. metal The presence suitable a the anode of can as a 100 be resembling volt cobalt iron. sq. According suitable electrolyte nitrate the such agent to neutral the formic Thiel acid.epi"me ammonium made of use platinum at amps.Section ELECTROLYTIC THE III. and of suggests bath Ea=+o*45 Geer2 and addition the is the sulphate Dennis use. approximately metal power thus of the . in I. Forster of cathode 8 sq. on but off be can C).

following : " CeCl2 Na. mium. 15-20 BaCl2 A 200 Electrolysis with yielded 750 the potassium and vertically situated two addition the electrolytefor cerium With ing contain- surrounding sodium fused . -j^r from seen as electrolysis varies for necessary following table the for : " Ce . most The fused with metals all white are slightlyyellowish tinge and are electrolysis of the prepared by chlorides. anhydrous neody- samarium and lanthanum praseodymium. of use He water-cooled a of fused the used chlorides the the recommends copper carbon chlorides. of sodium. layer of ammonium a compartment of electrodes porcelain cell porous cell or of iron use used. As electrolyte he without potassium and barium. EA=I-I99+0024 Fused Electrolytes. at 12-15 volts in 6 hours. lanthanum fairly stable easily oxidized.Cl. cerium. parts. high cathode current density is . a the In anode mixture a advocated the electrolytic containing electrodes. Pr . Sm Hildebrand and the being placed in cathode fused the chloride.INDUSTRIAL 136 thallium ELECTROMETALLURGY salts in terms electrolyticpotentialdifference of the is" Tryrr tt* log. La Nd .KCl parts. amps. was Muthmann with the chloride. conveniently most They being the each temperature metal. protected by porcelain cell chloride advised Norton gms. a in air. elements The " volts. samarium a current of metallic a very of cerium 120 trace.

3CaF2. boron 4 by Hampe the are products thermal electro- of (seep. B2C2. Borchers7 electrolytewith for the patented the continuous preparation of Pederson8 alloy suitable electrolysis of the pure suggests for many titanium electrolyte. dioxide cathode.2VF3.requiring a much in an fluoride. per deposited on fluoride vanadium suggested the electrolysisof molten " 2VF3=2V+3F2 3^2+ V203 +3C=2VF3 +3CO An alternative method is the electrolyteof V203 dissolved Wood's oxide as entails process in the of use double a carbon a electrolyte. Vanadium. B6C.PREPARATION required of to OF fusion the ensure J part by weight RARER THE 137 The addition metal. Titanium.M. Experiments indicated borax at the electrolyte and carbon a by reduction The alloy boron fused a borate of preparation the B203.F. of per be 600 amps. and at the With and E. of the chloride of barium METALS the to is chloride advised. dcm. vanadium volts. fluoride between iron cathode an of carbon and vanadium cell lined with alumina. 6 Gin M. of the use anode oxide calcium and higher temperature.6 using and Lyons electrolysisof molten the on formation the cathode.using a the copper of use calcium addition chloride of titanium as dioxide metal. of the carbides of Broadrill. pure 11-12 mixture material anode as a could of vanadium the reformation with the cathode anode and trioxide dcm. Boron. 172). copper titanium purposes. reduction sodium a claim anode. an of compressed a cathode anodic an of one in a density current 200 amps. it is in as an industrial prepared calcium by fluoride the as .

3 Zeit. 6 U. 619. 280. Appl.. Halle. 150557.12 REFERENCES 1 Berg.S.138 INDUSTRIAL ELECTROMETALLURGY Manganese. 1904. 1854. 841. ' 10 Zt. Anorg. 39. 17190. production Uranium. Experiments of solutions concentrated that the oxide obtained in alkali an fluoride the electrolyte.. BIBLIOGRAPHY. p. electrolysis of by but be very fused the prepared metal pure chloride UC14 by electrothermal can be deposited between carbon electrodes.. 40. Ann.. 18 Rideal. Zeit. " 3. Verhalten des Urans. adding as the to the electrolyte in indicated all chloride Simon11 similar to are fluoride or calcium suggests oxide of traces results Better manganese manner a from fused electrolyte. great electrolysis the on chloride metal electrolysis of by 10 Bunsen manganous the of matter a and of of preparation was 9 Guntz by continuously that in adopted of aluminium. This methods conveniently most can (see 153). Pat. 275 1892. Bonn. Cong.P. " Die Darstellung Blanc. 9 Bull." W. Le . des Chromes 1902. SECTION . 3.. Elektrochemische Das 191 1914. Chem. Hutten. und Seiner Verbindungen. 961 D. 1903. 4 Chem. Pogg. 11 Eng. 785962." Diss. 2 Ber. 1905. IIL 12. Soc. .. 37. Chem. U. 8 Elektrochem. April. 1880. 1900. 6 Int. 91. Zeit. TO Chem. Pat. chloride free difficulty.. .R. 1904.

already referred have We in both rival to the practice the into carbonate slack Owing (over iioo" of whilst coal is short. conductivities furnaces and Kanolt.especiallyby those with J the W. . 20 per even charge of sulphide half its about necessary must retorts of the in completed of C. Elektrische the see on heat the loss Northrup. to be ordinary method with oxide. suffers from smelting zinc of coal solutions. but and For are as sizes. Electrochem. retort a coal inside. furnace average infusible to under be complicated by is further process difficultyof removal of zinc the zinc efficiency of cent.* per ore some the hot iron content." Section Zinc. Langmuir. shapes others " Der as and in the information well furnace material. is mixed the or to serious most disadvantages. or thermal the with the also of minimum ton per zinc the expel to high-grade averaging only by not vapour 7 of fireclay retorts. but ordinary Belgian thermal electrothermal in the tons in fused and aqueous electrolyticdepositionof zinc the to the in the slags remaining retorts. ore be may low-grade a and one is from 30 gases outside to required The ore. 30-40 in high temperature the to found general In the convert heated and coke. Trans. roasting after ore. serious the practice is The processes. Not only labour * liners. life days. Soc. Atner.) the kgms. of the and l Richards has calculated . but high lime The half a consumption. 1912 high in both costs are of with met various electrodes of furnace different Fitzgerald. holding only is the ore small in be a badly operated furnace a attacked a of ton 4 tons : With hours. distillation the or weight small. being 40 by the slags. Of en. also in and Bronn.PROCESSES ELECTROTHERMAL IV. to 191 7 ." operation great difficulties thermal from McLeod.

in the by an of the retention the to There zinc vapour. undercooled optimum being 4190 C). may run be to " as of the walls of condensation regulus a substantial a entirely eliminated process to factors three the actual than processes are through been not blue unimportant an they " of formation is part of the zinc part coalesces a being recovered The an vapour roasting. but the zinc is as remains consequently reduced between second metal C. iron partial reoxidation place. The : charge zinc the on globules daring the process of condensation. are place according take may the with of the either to : " (i) ZnO+C$Zn+CO (ii)ZnO+CO$Zn+C02 The main reaction equation.especiallyif the free and noo" rapidity under the indicated reduction to the fact that from removed is the following that may ible revers- take packed charge . and concentration of the oxide This skin.p. Owing sufficient with not in the case with gaseous most phase. 4000 are considerably undercool than 5000 C. condensing globules of the factor is probably spelter recoveries followingequations important most Reduction made."the more in common is Belgian. The rapid chillingof the zinc globules in the condenser vapour II. the globules before found lie to temperature has been the 8500 C. the reduced of action metals. but by no latter. considered are blue have to " powder electrostatic an in the powder. spelter. e." powder which formation I.g.ELECTROMETALLURGY INDUSTRIAL 140 the condensation loss due diffusion to and retort of the especially if the zinc of the of has sulphur only remainder electrothermal means There influence the on blue in the formation " of " in the factor of is " slag. sphere The reaction of space the in does the not or is proceed by condensation. of the (the m. zinc Rapid cooling to. depending entirely upon condensing between Dilute together. where very low of the zinc oxide is vapour concentrated more liable more The ones. copper. issuingvapour. metal C. say. Again. Superficialcoating III.

.

time same has been therefore. and and librium equi- with Trollhatten. of 2016 current the zinc. hours. over converted of zinc is ELECTROMETALLURGY INDUSTRIAL 142 part 1 taining (conoxide quantity in second a furnace. consumption. always formed. of ore smelted. hours. per smelted ore calculates kgm. in a very short space. alternative made (30 parts Broken 7*5 parts coke coke be very (iii). and recovered mixture and from this charge was 20 . in France. working dust) zinc dust 3 C. at obtained 4800 kw. 2078 The the blue in these works of cent. blue powder lead) and cent. " in be reduced at runs cent. figures obtained of of electrolyterecovery Power by powder or prove means cost a might 59 depolarization by a reduced between Under blue by powder C. were zinc kgm. zinc ore. (briquetted of of refiningprocess. kw. to the gas rich in zinc vapour a rapid fall in temperature from 11000 and 7000 C. 80 of the consumption current of cent. quantity can be the but effective condensation The be never monoxide original carbon of the 75 per cent. is taken advantage re-established will be low of redistillation " of the electrolysisin fused suggested on p. blende would in test calamine calamine. G. can. blende which this zinc could Harbord " per 54 with aqueous free the conditions these to " 6oo" practicable. 5 1000 cent. figures include above recovery of the lead. to cooling treatment " powder providing a and slowness by bine and according to equations (ii) temperature Instead relative of the " complete . the anodes) to Consumption. while of the for energy 4 tillation redis- estimates per Salgues silver. 40-45 a kgm. 31*5 kgm. and the necessary powder. Mounden to 80 Artege. 1000 or with required. of production dioxide. kw. further a distilled as anodic If " gives the with mixed lime. the use operation to the following Hill ore. be 75 per per a 1000 per required cent. of the cent. of hours energy containing 50 per according to Stansfield 6 ore . per relatively solution the blue the of. Electrode Energy consumption per 1000 kgm. for zinc at Gin smelting 1500 kw. using hours.

possibilityof the three to operating low-grade zinc does 10-ton cheap is used ore (especiallyin addition to possiblein addition carbon. powder. Types of Zinc an of ore. be adjusted for distillation In silicious to lie of the slags the controlling factor. of oxide. in basic slags . normal working conditions at blue consumption opposed sumption con- energy of the ton per power as energy an 1000 hours average 143 with redistillation 1500 minimum used per for the to 500 may ore hours oxide figure includes being about of zinc pure necessary We PROCESSES per ore is loss is thus less in ton the Belgian process. Other a as silver and metal slag : while copper. slag fusion just above to ores may such conditions certain The metals the are easily fusible slag which under power increasingly important when become valuable tons Johnson8 which advantages for those thermal operation of electro- electrothermal by two satisfactory. at 600 take the kw. and ore sumption con- electrode the consumption retort of blue to Belgian process. per 15 obtained rates estimates essential are zinc Furnaces gained be to Belgian retorts. kgm.while zinc evident feasibilityof working with charges larger than is the up is successful the from at figures considerably under It to consumption smelting process. kw. and Furnaces taking that difficulties in employed.9 and small the a The " chief advantages smelting processes with continuous with the operation. ton Harbord. may relatively high lead the a of providing possibilities be tapped off and worked molten separate from be o"E run content) conditions in scarcely retorts. per to of 4 and the of ton the ij tons powder. 7 Johnson 1 to kgm.ELECTROTHERMAL Snyder smelted has of 1050 Harbord's kw. ton per maximum and of ton per used. the electrical 4^. by electrode the temperature temperature avoid inclusion of silica is the should necessary of the metal. costly than 6d. coal consumption in the Under estimated hours. of 8d. per charge have proved not contemplate serious capacity units.

Norway. earlier the chamber fireclay as in in ' designed by Johnson (Sweden.ELECTROMETALLURGY INDUSTRIAL 144 Resistance electrical heating who 1880. electrode molten are well continuous are lower action. in which together is passed in D. above have of in with lined Furnace. is fed in J.) United The Cowles and operated with horizontal arched an such Fig. B. the hopper carbon a is separate off to a mixture the Salgues. and Trollhatten and form resistance in the use original smelting simple a form modern more zinc to The " F. and holes. at furnaces inserted resistance. which . The those through are lead used layers as ore. used was intermittent furnace. Furnaces. a forms of ore type. and coke 15. adopted in are and Pyrenees {3000 kw. furnaces the have were the Johnson the vertical silver a were Johnson electrodes (E) into when the carbon through The covered with containing slag The dioxide the chamber D. or by electrodes of furnace. and as In kw. other or smelting ores of molten tapping condenser A lime and plate.000 The Zinc Resistance " n Salgues Johnson firebrick bauxite. of ends refractory. situated . Sarpsborg 20. and in as The roasted flux. is usually layer of carbon electrodes three containing with in use containing charge later with mixed this 10 operation.). These zinc and column lead two vapour monoxide I. C. Hallstahammer Cowles by of resistance furnaces of application made was States.

per 30 a By in the rapidly condensed and C. ore furnace. cent.PROCESSES ELECTROTHERMAL is filled with this means and a with zinc pure carbon maintained vapour with is produced receiver. roasting three ore 100 difficultyof the prolonged about tons of fresh The of tons suggested for the the charge before u metric sq. corresponding per of offers distinct process electric furnace hold at silver the preheating economy. of type 11000 at carbon spelterrecovery cent. copper.such as iron or lime. ton every resistance each about Two be avoided can remove i/. dcm. 24 Various liberated gas tons per of blue ore. ing resultslag the production of smoke in a gives Johnson For of blue decrease low-grade zinc of lead. and A to powder modifications sulphide removal of the of flux which slag. Johnson only diluent cooled broken 60 per this monoxide claimed has 80 an from as per the airzinc cent. at Trolhatten smelt containingrelativelylarge quantities gold and into the considerable following compositions of the slag the ores The advantages. 145 By introducing the fresh charge under the surface of the is said to be minimized. powder difficulty will Snyder 10 16 . have to ores of each operate re-smelted are can current density of 128 current of furnaces hours. been sulphur by This suitable with overcome reduction. the by the furnace. a amps. the to volts a treatment complete before the by the additions sulphur in the of is used duction introeffects employed charge. 2#8 2600 amps. a 13 12 formation.

. labour 3s. with improved simultaneous claiming the by zinc further 16 Oesterle with resistance a of production and unroasted ore in carbon and simultaneous Brown of the treatment suggests lime ELECTROMETALLURGY uses the to iron scrap reversible produce to equation " Fe+ZnS^FeS+Zn The with be the set iron of kgm.. 38s. 6d. carbon carbide. this upon of production 17 process sulphide according ferrous with and patent zinc. required for every ton per iron scrap costs of the right Against these advantages being kgm. 900 zinc and of the cost 300 following The Cost Savoy. 6d.. from in three C. in which disulphide or products by- silica as . iron 10s. for the to the zinc vapour and monoxide. at Power : 4$. miscellaneous liquid phase. off and but manner. is used. of for necessary production of zinc diluted must reduction. 1000 electrodes 6s. Pierron C6te iron furnace. production from 11000 recovered for the and addition the the zinc is volatilized course. of lead..18 depreciation 9s. kgm. The a wedge-shaped resister permanent a part of ferric oxide are of furnace as one sulphide are pig iron 19 Imbert-Fitzgerald furnace the In the is not lead of zinc is lost in the process. 2d. since ores. carbon zinc out for lead-zinc directly recovered. condensed. 6d. rods the kg. any entirely over of the is suitable process be can volatilization the through the shifted equilibrium being the processes and a for process zinc. used are of mixture of blende Eleven used as added . flux on at in the would usual must Dorsemagen be per in suggested the of zinc and of siliceous zinc ores. 4^. total Ugine.INDUSTRIAL 146 fluxes calcium disulphideand The and carbon the disulphide. carborundum production majority of these of a or copper resulting sulphide practice iron naturally be worked six parts of molten the A parts of iron which to carbon furnace. 1000 every entailed are produced of 4s. 6d. 6d. cent.. simultaneous while use Borchers the sulphur as carbon copper. . resistance a The furnace for by the reduction patented of ferro-silicon modified The reducing atmosphere.

ELECTROTHERMAL

carborundum
on

of their

technical

utility to
Furnaces.

employed

which

has

for

been

enable

to

been

not

assessment

an

important

most

smelting

in

have

made.
The

zinc

used

scale

be
"

147

obtained

are

sufficientlylarge

a

Radiation
furnace

ferrostticon

or

worked

PROCESSES

the

is that

United

radiation

of C. de

States

Laval,80
also

and

at

Trolhatten.
The
the

shaft

where

D,

between

arc

the

electrodes
zinc

A.

be

The

CO
at

be

noted

hole

D

to

slag

It will

is

arc

ably
consider-

electrode

the

although

electrodes

of

the

reducing

a

consumption,

kgm.

C.

which

lessens

B

the

in

atmosphere

from

radiation

through

that

operated

through

enters

high

the

removed

tapping

the

to

and

a

through

the

exposed

flux

and

horizontal

condenser, while

can

coke

ore,

it is

leave

vapours

temperature
the

of roasted

charge

40
metric

per

figure considerably

higher

of

ton

for

given

than

ore

required,

are

resistance

a

furnace

operations.
Reduction
obtained

in

retained
the

ore

cent,

these

in the

slag.

simple

the
to

very

low

resistance

the

of

type

be

can

metal

is

of the

diathermacy

consuming

poor,

zinc

pure

little of

very
the

to

efficiency is

power
is very

Owing

than

and

while

furnaces,

electrical

more

furnace

quietly,

proceeds

about

70

furnace.

per
The

operate.

Copper.

Very

few

large-scaleexperiments

electrical

smelting

of

promising

results.

The

may

be

(A)

roughly
Ores

divided

containing

ore,

copper
treatment

into

three

metallic

have
but
for

some

complex

classes
copper

been

made

in the

have

shown

copper

ores

:

(e.g.native

copper)

INDUSTRIAL

148
be

can

ELECTROMETALLURGY

directly separating the

smelted,

metal

from

the

gangne.

(B)

Ores

addition

containing
iron

to

smelted

be

can

part of the sulphur in the

assisting in the
should

contain

iron, while

the

(C) Oxidized
careful

By

ores

be
of

iron

bulk

carbon

of

of the

most

as

the

as

copper

of iron.
with

carbon.

in the

content

in the

of oxidation

resulting slag

selectivelyreduced

the

in

in which

heat

well

as

quantity

retained

be

can

the

small

a

can

adjustment

of the

most

with

furnace

The

ore.

silica

and

contains

matte

blast

a

of the

fusion

arsenide

sulphide or

in

arsenide

or

is oxidized, the

ore

oxides

the

sulphide

copper

slag in

charge

oxidized

an

condition.

Experiments
to

1903

1907

sulphide
on

The
Keller
zones

Vattier

used

of the

chamber,

furnace

be maintained

The

Vattier

power

of

and

5

cubic

2

kgm. electrode

gives the
matte

a

of

one

the

in separate
fused

in

one

the

second

to

ore

could

be

matte.

metres
was

ore

point in

fusion

of

capacity.

500

kw.

hours

1000

per

material.

following percentage

analysis of

ore,

:

consumption

volts with

the

that

twenty-four hours

consumption

charge, slag and

119

so

at the

per

furnace

a

power

ore

tons

a

favourably reported

were

pairs of electrodes

two

from

matte

copper

simple resistance

separation of slag from

in

treated

at

a

with

Twenty-four

The

was

of

from

Government.

Chilian

type furnished

effect the

kgm.

furnaces,

for the

furnace

could

zone

production

the

on

Iyivet in France

and

Praz

at La

in resistance

ore

M.

by

made

power

"

for the furnaces
factor

of 0*9.

averaged 4750

amps.

ELECTROMETALLURGY

INDUSTRIAL

150
carbon

hearth

and

entering through
with

one

roof.

the

broken

coke,

silicon metal

of the

or

a

of

ore

after

The

.

JC

c

""

Ol

.

.

..

.

""

Other

.

""

:

"

o

""

""

aO

""

""

ft

metals

2
.

.

.

ft

slag consistingchiefly of aluminium
silicate containing about
0*5 per cent, of
kw.
hours
1200
consumption is about
F.

smelted.

his process
also p.

furnace

for the

The

nickel.

of

use

power

a

revolving

of ferro-nickel ;

production

(see

operation at Essen, Germany

is said to be in

of

kgm.

1000

per

Clergue has suggested the

electric radiation

magnesium

and

a

ore

ferro-

nickel

a

14 per cent.

.

.

""

.

and

crushing is mixed

reduction
yielding on
followingcomposition

Ni

electrodes

vertical

series

228).
Manganese.
is

Manganese

ferro-manganese, the

and

limited.

it

Although

electrolytic methods

quicker and

are

Moissan
a

small

27

effected

several

minutes.

He

present

in the

cpuld

not

method.

sodium
under
at

a

metal
the

carbon

by

processes

is

a

of the

mixture
small

below

the

its

metal

which

has

a

of

means

melting point

produced
vaporization (m.p.
can

manganese

sodium

this

By

be

12470 c.).
Tin.
Harden
for

the

3"

has

reduction

given
of

details

tin

ores.

of the

M

by this

with

Mn02

few

Borchers

carbon

excess

a

carbon

excess

furnace.

point

in

Mn02.

of

arc

produced

which

well

with

volts,

at 60

amps,

the

in

by carbon

Mn02

the

remove

refusion

a

in

C, from

temperature

to

removal

used

of

gms.

by

of

of 150

current

a

hundred

manganate
20000

being

form

pure

a

electrothermal

reduction

attempted

Gin29

sulphate and

the

with

confirm

in

prepared

metal

pure

convenient.

more

preparing

be

can

(p. 138), the

furnace

arc

for the

demand

spiegeleisen

of

usually produced in the forms

conditions

Although

necessary

electrothermal

PROCESSES

ELECTROTHERMAL
of tin

smelting

scale, with

ordinary

of

exception

the

oxide

by

are

have

methods

losses

where

plate

of

the

volatilization

by

prospect of future

some

in tin

inconsiderable, the

means

no

technical

a

unsatisfactory working

the

to

furnace

blast

accomplished on
tin dross smelting

been

not

yet, owing

works,31

stannic

has

151

of

thermal
electro-

development.

Chromium.
Metallic
small

is

chromium

industrial

simple

metal
is
the

It

being

usually accomplished by

comparatively

a

with

charging, the

broken
of

means

production

obtained

be

can

using intermittent

by reduction

produced

on

electric furnace

(see p. 234).

furnace

arc

chief

scale, the

being ferro-chromium
a

only prepared

Reduction

out.

carbon

fused

according

to

equation

"

Cr208+3C=2Cr+3CO
The

reaction

metal

usually contains

which

is difficult to

Refusion

with

11850

at

commences

the

calculated

the

removal

effectual

More

of lime

to the

3Cr3C2 +2CaO

under

small

these

developed

a

reduction

with

crucible

process

charge

antimony

the

in

accomplished

"

calcium

Aschermann
for

be

can

oxide

carbon

and

oxygen

=9Cr +2CaC2

quantities of

conditions.

of chromic

amount

the

although

resultinggrey
carbide, Cr3C2,

remove.

of both

by the addition

hard

extremely

usually entails the presence
metal.

The

C.32

+2CO
chromite

at

Cassel

are

formed

successfully

by
preparation of chromium
sulphide in a small graphite

"

2Cr203+Sb2S3=4Cr
The

antimony

uses

silicon

as

is
a

+2Sb

entirely removed

reducing agent

+3S02

by reheating.

"

2Cr2Os +3Si =4Cr +3Si02

Becket

33

may. the is the sulphide.INDUSTRIAL 152 ELECTROMETALLURGY Molybdenum. many oxide The in carbon the of lim" presence MoS2+2CaO+2C=Mo+2CaS+2CO Becket 36 has claimed of carbon amount indicated than 2MoS2+2CaO Calcium carbonate for reduction the process by the above +2CaS =2Mo +3C of course. Metallic demand in the with chromium carbon.37 more in the molybdenite fusion of the by are metal. oxide the according carbon the to equation " the ensures of presence =Mo +2C Mo02 +2CO in the metal. as a Small flux the reaction causes of iron traces by volatilization removed 38 Neumann of silicon . is of production than prepared for which molybdenum. and molybdenite and The !Lehner direct the suggested the by the sublimation of form molybdenum preparation of subject of is the *" most with reduction ore metal the from Guichard34 patents. and preparation of 5MoS2 +2CaC2 Calcium obtained. with smaller a equation " +CS2+2CO be used of lime instead " 2MoS2+2CaC08+5C=2Mo+2CaS+CS2-f6CO The to addition proceed of calcium smoothly. means fluoride according to has present on further suggested the reduction 39 Keeney " MoS2+Si=Mo+SiS2 unsatisfactory results a growing effective market for the as were a reducing agent. oxide excess is sufficiently volatile to be easilyremoved from common melt. metals =5Mo like +2CaS carbide is especially molybdenum +4CS2 has " . A increasing an of deficit easily more of reduction the by small is there special steels.

For isolated. being 215.but reduced Owing. moleoxidation. Ti02 and U308. is There as Its distinct a limited from the growing demand but ferrosilicon for this element alloy for reduction purposes. and be can prepared by reduction respectiveoxides. According reduction by at that with volts 40 no The Moissan to in a reduction element 41 with carbon simple took is not this arc element a be can current of 1000 Greenwood furnace. cule. however. of the form such. thermite by heat of " Crude silicon is prepared " from silica by reduction with .ELECTROTHERMAL PROCESSES 153 Tungsten. This the metal is also preparation of industries. three carbides not of electric and by Metal by methods contents work and metal. V2Os. always contain small quantitiesof the of their nitrides.692 calories per gram is only exceeded and the alkali metals. to to increasing quantitiesfor in being used specialsteels is in the demand always produced are ferro-alloys.40 Vanadium. produced industrially. for usually reduced ductile the to prepare carbon steel for electric-resistance an is metal the variable the of tungsten the work lighting electric in the and produce ferro-tungsten (see p. ferro alloy pure manufacture filaments in steel most tungsten is used oxide is of carbon amount in the furnace arc preparation of carbon The resultingmetals The and the containing melted to variable a prepared be can for the used those lamp Uranium. These furnace carbide as usually high-grade steel. industrial they In hydrogen subsequently similar Titanium elements with and of means free carbon and the chromium. as Zirconium. produced amperes 42 found place below 14000 C. SnjcoN. 232).

and of method silicate is slag of magnesium can it contains state 250 to hours. modifica- Graphite. the furnace. extremely important in technical will be referred to in a later section (p. 14300 C.and to covered crucible a magnesium Carborundum operated Each C).p. arc from kw. in this and impurities. since temperature uses being carbon- use to resistance the 44 depending electrodes.164). with powder. using and silicate potassium silicon prepare were tained. .carbon.notably by Deyille. and 1000 hearth. Carbon two can exist in at least three crystalline47 and one amorphous : diamond. is melting point of the is volatilized 43 purification of cent. Minet either sodium adding A silica from interaction some of which These of have silica and become or have results been in the carbon as lyte electro- potassium silicate. the separated. indifferent to time great variety of compounds the work. N2. silicon unrefined " Si 9571 Fe 2 24 Al 1 96 P 001 C 008 per cent. ob- prepared by electric furnace. the treat with A ELECTROMETALLURGY INDUSTRIAL 154 effective An material crude stir in coke. of silicon 350 from can as be of tapped the few off every According to Stansfield 46 a high-grade the followingcomposition : the (b. . sand furnaces the other in hours per into Acheson firebrick element for two "-3 Si02. a a n it Potter48 a has reducing agent suggested the of use silicon carbide as " Si02+2SiC=3Si+2CO Attempts have been made to cally. well-known tions. electrodes a mences com- metal the works two the silicon Reduction moulds.. time electrolyti- Grosz. then be poured off at 14600 C. lined The current passing The furnace is 28000 had at furnace kgm.

preliminary ionization graphite from carbon. pressures or to the presence for technical It the of the zone carbide of the graphite. Acheson. is sary neces- the and catalytic material the to apparently serves decomposition of a carbide formed produce graphite by the by the catalyst with the carbon.ELECTROTHERMAL graphite The coke low at form graphite was that the was very tedious aluminium direct formation of graphite is the of coal anthracite. graphite is the stable it cannot production carbon possessing of is catalyst is the already been has graphite at. at by studying when carbon found They was measure graphite C. and by the experiments of Acheson. catalyticallyhastened According stable developed by E. will not higher 11000 C. and modification stable PROCESSES iron as and silicon as or conversion. of pure or He the graphite into carbon of small presence such such non-metals Townsend to the function of conversion boron. 5*4 times as great. that that . above technical into The ordinary carbon. at C.and the have pressures the consequently above vapour and Borchers be that 5000 C. carbon redeposited in Fitzgerald and the relative low temperatures vapour vapour form the Forssell between at 6400 the be solid will of others. transformation found a 155 5000 C.but that the impurities. is assumed It place in the is behind hottest but there form of the as decomposed takes temperature leaving volatilized the to of carbon conversion the recommence of graphite be of catalyst is not absolutely a 11000 say. the vapour pressure graphite. first certain and for whilst operation. pressure. whilst colder to that times 37 . above carbon the noted necessary dispensed with. presence gradually sublime graphite. of attempted 7000 of carbon C. is present. That of the graphite.especiallymetals quantities of is the diamond temperatures. to and carbon 5000 and equilibrium composition graphite in the solid state 5000 C. C+C02^t2CO. is shown and formation gradually raised the carbide zones. at furnace. thus and carbon the the In vapour carbon same.

and heating the 30 feet of fireclay bricks long and terminal plates they have with to carry a core is about deep. 17. the as temperature days ash. The is used anthracite graphite.At Niagara. have to presence is anthracite of a graphite and the be the a pyrometer matter considerable graphitizing zone. holding about of ELECTROMETALLURGY INDUSTRIAL 156 water-cooled. constructed and 15.. The well 20000 over ensure between the the of protection the limits of C. chieflyiron which of furnace. 8000 end The furnace kw. slab furnace of the end cent. usually containing only from has o*i been not to resistance from is o*8 per volt. and ing commenc- the resulting graphite to Graphite. and 200 of the about down. as is to liner . are amperes. a HH for graph carbon St. into oxide which of iron. volts.000 over rice of size furnace The liner. completely at current at 0'8o amperes up. Fig. continuously observed non-graphiticcolder the of couples which so anthracite fusible firebrick. feet 6 inches 2 of mixed surrounds for carbon consists furnace finely crushed is anthracite carries since The the as of anthracite 6 tons grains. per electrode Each wide 3 the carborundum a at each with to version con- long trough a carbon a current. The adequate embedded in difficulty.000 to heat pure. production per operation is about takes cool for the consumed are elevation of the the Furnace amperes with decreases couples Resistance " 1600 About at thermo ih*ing mineral removed by volatilization. four to five remarkably cent. at day a The 20.

.

eg.60 and small the The by the Readman system. 80-90 in this kind designs of furnace.). of is drawn slag four the in base charge is means C. designed by first Parker.INDUSTRIAL 158 of electrical Processes various ELECTROMETALLURGY graphitizationhave grades of coals. Phosphorus. In with the with its phosphorus materials. phosphorus and Machalske liners made of vitrified brick set in an asbestos sodium . tapping intermittent to to as so conveyer With which through operated were cylinder firebrick . under water. air. ores per cent.certain improvements have been slag resisting furnace incorporated. and \ the penetrate through the furnace The associated difficulties such as of furnace. and according " Ca8(P04)2+3Si02+5C=3CaSi03+5CO+2P 2MP04+3Si02+3C=M2(Si03)3+5CO+2P chief The production of will vapour phosphorus and condensation in fed commence The 14600 C. those of Irvine. near roof. is Phosphorus by electrothermal of smelting wavelite. porous the on domed a the through exclude resistance even every at roof three 11500 containing but is obtained or hours. and phosphorus recovery later electrical walls. I^andis (Anglo-American Chemical Co. mixture a phosphorus vapour to the equations The of bone rock liquid a in being produced ash the or with with essentially minerals carbon aluminium or diluted consists process phosphates calcium increasing quantities apatite. to is condensed be in a a tinuously con- screw off by Reduction completed copper at vessels quantities of iron. and dried to even been applied have peat. but to not proved technically successful. silica to and silicate carbon slag monoxide. with the associated being disposed horizontally electrodes is said those are ease with satisfactory furnaces. and obtain methods.) and (American Phosphorus Co.

applying parts of the furnace. the have been pendent electrodes more operate either the and electrodes carbon or frequently between electrodes one 159 the arc being formed the between or ring carbon resistance or arc themselves substi- in the set furnace walls. per larger units this has been and kgm.. either eliminated. closed a of commencement a run removed During arsenic. reduced In 61 hours the about modern later said are to hour. the gold is volatilized The hour. ore consists ore arsenic Reduction Ore the to process of production electrothermal The ton f of ore requires some in . and tuted. is gas.FeAs2. to the output capacity of an . furnaces of phosphorus capable of producing be According smaller the furnaces phosphorus. heating in sulphide is of ferrous matte is deposits in Ontario. the day per S. more either furnaces electrodes annular an the on former. some condensers hours to in set a at . Arsenical by the Westman The thioarsenide a or chiefly of of iron. condensation place. one for consumption energy kw. 11*5 ones in amount same was more 5 kw. the a a and a for treatment. The 80 earlier pattern kgm. of 90 Co. furnace capable of ferrous sulphide current of the of the the and arsenic nitrogen oxygen in the furnace. FeS2. is heated the by alternating ore colder the on veloped de- reducing atmosphere a obtained The ore. per Arsenic. Richards to had hours kgm.PROCESSES ELECTROTHERMAL silicate Horizontal mortar. The system. metric the forms of condensers system takes a whilst time of the arsenic Hering. On is condensed In process between cast-iron dealing with is matte furnace with a gas by combustion period the external of kw. Westman's current The in the silver present being mispickel. to by of volatilization According 1000 time blower round air is circulated the and space per ore furnace the containing any arsenic electrodes tapped off from from removed system kgm.

B. 3 per cent. . double-walled which base hoppers A. the sulphur (m.Y. to Still cross- another. in dcm. chamber at the disulphide is formed. equation C-f-S2==:CS2 - is complete at Charcoal fed in containing less than furnace CS2 before ash.. where it slowly vaporizes (b. through four similar hoppers B. and to feet 41 they require to 60 volts. 1 '2 at the space serves vapours. per sulphide is the industries various tons 2000 furnaces preparation of purity in the disulphide used States.444*5" C).p. a to time time annular the down runs as by sulphur vapour. transmitted each 25 sq. bright red heat. D. 4000 Raw temperature same high.) flows to the base of furnace. 1150 C. furnaces 40 D. are this By resistor.p.161} consists of furnace at the packed carbon is not carbon in at the of the column. and walls there The cylinder containing serves from base of production. cost to the workmen. exceeding The fed Disulphide. of which in a danger appreciably attacked is fed carbon of absence great advance a regards as N.ELECTROMETALLURGY INDUSTRIAL 160 Carbon All the carbon in the United in E. Yann. 16 feet in diameter. one larger furnaces contemplated. metres the sulphur can be double the between the at at which action re- the carbon interchanger heat each are of iron. formation heated to a of carbon layer of is maintained which carbon charcoal in the disulphideaccording to the from at The tower. being top of the furnace. right angles at Fresh top of the column. at Penn. both method. Taylor's resistance electrical over the ordinary thermal and (p. and a four. A. passing up through The molten 800-10000 the C. is produced year. cool the liberated current of and through four section and as situate and stated are in the be to long. through the hopper F situated Each of a The " will yield approximately it is necessary output at the from each to dismantle furnace ash is used. of the base a built at amperes Dense through it arrives means The electrodes. furnace. 1000 and is about metric clean 7500 out tons the kgm.

1917. Smelting 18. REFERENCES to The kgm. 1910. . and Min. Eng. 0-45 furnace vaporize the the calories necessary to furnace. representing kw." Trans. Journal Feb. need of calories. hour. 2000 at If C. 2000 are 250+72+48=370 kgm. heat to 0-24=48 energy equal and To disulphide thus shows an 1 "Met. Amer. CS2 72 calories vapour per hour Perm. SECTION 8t": Trollhatten. Soc. Electrochem. kgm. Oct. we we that calculate from of output an assume can necessary PROCESSES leave gases data. per kgm.000 calories. " Ind.. or energy TO p. we amount total 2'2 kgm. of Zinc. required 7.ELECTROTHERMAL per day. 1914. per kw.Y.. C. 873. at Mag." Chetn. Iron * Mining " "The 1907.. efficiency of 55 per hour. " " Calculations. Yann. IV. cent... therefore per up N." 117.. 200 x The is kw. Electrometallurgy p. 12 theoretical following the about the the 161 the energy The CSj per furnace tion consumpof formation heat " C+2S=CS2 LJ "G5" -Carbon is 19.

p." Electric 48 1907. 87 8. Pat. for the . Amer. Trans. Furnace. 1900.. u. . Zeit. 8. 1910. 1910. 1270. Soc. Anorg. 1904. 171 191 18 Trans. Technologique. Kremakoff. 116. Rideal. Soc. 11 Proc Pat. 81 Mining 11 Chem. U." . 453. Amer. 1192. Electrochemistry. " Bragg.. 835052 . 239.. Electrochem. Hempel 81 Electrochem. I.C. 814050. p. 1483 48 Chem. 191 Chem. 444. Industry/' Lighting 1897. Ind. of 1016.C. 142. 3. p. 3549. 25. p. 18. and Ind. advances Recent France. 281. Eisen. Anorg. 209 Electrochem. 1905. Amer.. 281. 98. 44 Electrochem. 191 1913.." and . 1902. p. p. 324. S.S.." Zeit. Eng.S. Soc. the in of production 1913.ELECTROMETALLURGY INDUSTRIAL i6s " 7 " " Furnace. 1905. Chem. Met.R. 1903. 17. 1910. 1914. 18 Chem. 122. Journ. 632 . 84. 1905. p. Chem. Soc. 3. Trans. 87 C. 86. 6* 10 U. Soc. 380.. 9 p.. 18 Met. 4. 176. Petersen. 84 . 5. 191 3. pp. Atner. li Met. p. 48 Allmand. Zeit.. Hutton. 88 Met. 1909. 333 Ind. 10 Trans. Stahl Ottawa. H. " 60 . Electrochem. 1909. 14 Trans. 519 277 191 315. Chem. Amer.S. Zeit. Structure.R. 88 89 1910. Crystal 343.S. 17 " Eng. p. Ind. and and Electrochem. Trans. 1893. 14 81 . 48 " 122 . x. steel p. Soc. 1913. 84. 1908. 9. """ Chem. 1914. 768054. de Civils Zeit. 416. Met. 1904. Pat. 11 U. 186. Soc. X-Rays Applied Muller. Pat. . 814810. 909. des Soc. 19". and 24. p. 40 E. Chem.. 18 U. Auf. The Soc. Zeit. 1483. Eng. 24. 8. Amer. Amer. . 1908. p. Electrochem. p. 24. K. 1903. Angew. p. Chem. 28.. . 5. Electrochem. Ing. Trans.. 18 Chem. p. 88 1 Eng. J.. . Soc.. 7. p.. Eng. 1912. 1901. 1906. Chem. 3rd 88 Bull. . 1. 116. 84 C. 88 Metallurgie. Electrochem. 3549 18 Elektrometallurgie.. 7. p. 1912. Electrochem. Metal... p. 1905.I. furnaces electric of zinc... 88 Electrochem.S. and Trans." Electric The Trans. 205.. 18. 356 41 44 20. " CJl. Electrochem. 502 86. "s 80 191 construction pig iron. The 41 47 1906. Electrochem. 215 . Ind. Amer.

Zinns. F. Fitzgerald.PROCESSES ELECTROTHERMAL TO BIBLIOGRAPHY "The Electric "Der Elektrische " Kunstlicher "Die Metallurgie Furnace. 1904." Graphit. SECTION Stansfield. Henniche" \ . H. Bronn." A." Ofen." des 163 IV.

V. core. built up carbon coke. . put by E. A about charge sisting con- followingcomposition 52*2 . 35-4 to 35-1 6 to 10 7*0 r8 to 3*5 . alumina as in the are chief " carborundum compound impression that furnace The silica at and production important compounds. slight excess of coke the equation proportions corresponding to Si02+3C=SiC+2CO is used " above . who 1891.-CARBORUNDUM Section AND OXYSILICIDES reactions The occurring between of the high temperatures and OF led to the commercial have carbide. . named of under the is used Carborundum material the in drills and bits for rock the applicationas its mentioned steel and as infusible an is Carborundum production of coverer dis- time was crystalline metres of brickwork an in high and metres and intimate . furnace ing follow- furnace for the is about broad. metres be may preparation of coke Each to. an of other multitude graphite (see p. " CARBON carbon electric THE core. Salt loosely packed round usual of the Sawdust . . varied. that the a fired furnaces. 5 10 the the the at contained deoxidant a general construction the is is silicon these large quantities as hard as crystallinesubstance the other important uses Among metre ally industri- Acheson. very of many of the (corundum). Acheson f-inch crushed Coke noted 3 be substance in the that uses can resistance a adopted Sand It will be of the liner for coal and prepared in diameter. to 54*4 per : " cent. a 1 by E. . 156). of diamond as abrasive. long. containing the of mixture . .

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O'lO 22150 c. investigators is carbon of formation of method produced by the reduction silicon at a higher temperature be of " (i) Si2C20+C^2SiC+CO Si02+C^SiO+CO SiO+C^Si+CO Si+Si2C20^2SiC+SiO (2) or the interaction produced by silicon being equations . 001 2000" C. the sure pres- following " presence of the Hg. 0'20 that interaction pressure mm. 0-03 2100" C. the dissociation be depressed. various at the probable temperatures. permitting of slightlyhigher working temperatures. 22550 C. results silicon according {a) From J of 030 this small the of of growth of silicon an and pressure in the carbon formed would of is quite enough crystals from carborundum of silicon vapour excess silicon carbide vapour course vapour form. " of carbon He carbon : siloxicon. It may siloxicon by carbon or the to as complete. C 0001 19200 C. 0005 i9600 C. formed and either to (b) From carbide In Richards 4 calculated has . 0*02 20600 c. 005 21550 c. to vapour.166 ELECTROMETALLURGY INDUSTRIAL (Si2C20) in not are from silica and agreement carborundum.Si02+2SiC^3Si+2CO and Vapour the of the SiO+C^Si+CO Temperature. Tone brought 6 believes about silicon vapour that by the the formation interaction according to the of of carbon equation 3Si+2CO^Si02+2SiC " the carbide monoxide is and . 18200 for account thus vapour with : considers the following silica.

silicon carbide Si+C=SiC+ C+0=CO+ the of place.900 =163. 113 To heating up CO.000 temperature room (2 X 29.200 99 kilomol 1 is heated passing through molecular To of : " and (40*3 kgm. 19.but they reactions Si+02=Si02+i8o. kgm. or per 4700 per kw.ooo CO take not simpler may of formation heats monoxide the that probable extremely reactions above.000 carborundum effective necessary carbon calories. 14000 at of carborundum 21000 180. hours ton. 2. With for the of result of molecular rareness it is high order a formation are extreme We 21000 cold charge whilst C.200)="i on energy " production at The those as respectively are the Hence are direct the such of silica.600 X 2100 = Xi4""0= Total : " calories. ide monox- respectively 7*1.000+2000" further can of carborundum and o" and The mean carbon 14000 C.700 19.) requires calories. C. 2 X71 summarized as follows =119. 23.20QX4'i9 ~~ 40-3x3600 =47 hours kw. metric . and that assume the liberated surrounding charge leaves C.CARBORUNDUM the By write the interaction direct equations siloxicon as 167 for the follows of and carbon silica we can of silicon carbide production and : " (1) Si02+3C=SiC+2CO (2) 2Si02+5C=Si2C20+3CO view In such of the the of these outlined does compounds series of a 6 Allmand production The we calculate of carborundum the follows as part of 11*3 and heat o" and to the the specificheats between 99 29. required can be To forming carborundum heating up SiC.200 99 _i63.

Carborundum plant of cent. moulded semi-metallic a its It is carborundum. retains by oxygen articles of the that Dusseldorf. charge of the composition a in carborundum resistance usual to up It silundum. all the possesses The type. Fitzgerald has attempted to prepare articles of carborundum into desired the crystallized carborundum by moulding form and subsequently recrystallizingthe Tone .168 INDUSTRIAL ELECTROMETALLURGY technical In working ton of carborundum the charge is converted.i. unattacked being temperatures into resistant the to metric per only 50 per the by Sn.).UNDUM. temporary He7 adopted in mass 18200 between He and temperatures. properties of carborundum. at company. are hours the is carbon outside the at heating a period and of verted continuing con- heating. beginning depth depending on a silicon to exposure for temperatures packed production the form. the carbon found silicon in and silicon preparation showed 22200 of vapour that into C. silundum. was purpose. is controlled smaller a by the same Owing substance moulded found SlI^FRAX. attempts or Co.000kw. about product is manufactured Niagara (10. Carbon for required of the furnace into to and in are of vapour propertiesof be can 12000 used C. if silica in required for the silicon converted was evidence of excess of carborundum between amorphous the existence when on line crystalof solid the tion penetra- of the quantity be added to . be converted articles could by high to prepare compact a electrically conducting and material articles in made been resulting product.furnace. and Germany. into the carbide effective. was and consumed.e. termed originalshape for resistance have the to very up even material carbon state The (" silidizing "). C. to carbon the also at 15500 and sand" or using water of most action investigated the 18200 variety. The at 8360 kw. same various silicon carbide solutions "fire an electric rundum amorphous carboglass or glue as a binder. by acids.

8 who the reddish-brown a monax. isolated carborundum as " investigatedthe lies between It is indifferent furnace liningto and 1 taken. but 7. glaze being produced according to the equation more " 2Si2C20 +702 It can shapes. where when powder amorphous preparation developed the preparation of siloxicon and not merely as a by-product purposes.It has 10 Acheson for technical and density of only oxycarbides of silicon isolated of the reducing a FlBROX. pigment the gave apparent an a SlLOXICON or he fair abrasive it use which to in monoxide silicon crude field of usefulness limited a insulator heat a 0*04).C*0. in 1881. an to is silica superficial a easily oxidized than carborundum. tion prepara- of siloxicon outer of zones a first different dioxide. manufacture most in the and also . products formed various furnace. carbon in conditions these penetration maximum Germany." as appears tion modifica- The packed." agent.169 CARBORUNDUM the charge in which of siltindum " silfrax. Potter. It has suggested of (ithas polisher of a to as oxycarbide in to the of the one The furnace. are under produced The Co. be At decomposes moulded and =2Si02 +4C02 baked high temperatures into carbide and to form in an inert as follows silicon Si2C20=SiC+Si+CO vessels of various atmosphere : " it . " Siloxicon apparently general formula averaging 2 acids . are refractory and suitable compounds walls. and been powder. of carbon stream borundum car- were various obtained the " " in of carborundum. AND already referred have silicon " name printers'inks. We the as power. terms vapour prepared by the have to he silicon of Silit. forms series of a x large samples highly a includes Si. Monax." into pure Siemens with " is 0*5 inch. articles the identical been silundum.9 who by Cohen compounds on heating silicon in In 1903.

8 Trans. Pat. 491. 15. time. Electrochem. Soc. It to the at good electrical a said is slowly at fine efficient heat remarkably carborundum. silicon hydrofluoric acid of method International one. 194.INDUSTRIAL 170 Tone has with treatment on silica and remains silicon.. " CM. monoxide by allowing carbon containing as fineness apparent of consists 0'6/i diameter). Amer. 4 Trans. 223. 1508. p. Soc. 5 Trans. p. Chem. Amer. in consist may behind. frequently to It serves with The siloxicon. As siloxicons Co. Amer..S. Electrochem. 24." 92. 12. vessel that . 1881. Soc. * /. 1912. 26. 1904. in owing conductor. 850. Chem. 28. Electrochem. Electrochem. Its and 00025 (2J 0*0030 silicon a to vapour of the density 3 gms. that than temperature of coke of the rundum carbo- A Niagara. 8 Trans. Soc. 1911. furnace and of carbide. 1914. 181 . Soc. 21. 722793. at carbon usual the occurs works at out although occasionally consists charge is carried preparation is used. p. 181. Soc. Electrochem. per required for the formation fibres . of Weintraub by (0*3 the to common " Fibrox in succeeded have modification interesting an material insulator Weintraub E. 6 " 7 Trans. Both preparing Tone and " termed threads of siloxicon several inches long. 438.'s multiple of at been lower a one-third a admixture already has modified instead cores by single a and two- little sawdust a of formation the noted. 26. p. 1914. Amer. F. SECTION 1 /. REFERENCES TO V. same can between formed be into a just below temperature a lie to litre). Amer. 10 U. Amer. Phys.. Electrochem. 1907. Applied 213. 1906. Acheson's the silica of residue a siloxicon that solution solid a view the expressed essentially of since ELECTROMETALLURGY necessary for carborundum. it is diffuse of carborundum. p. and Graphite it is freed from carbide silicon amorphous introduction The thirds of silica with salt.

V. A. A. Allmand." Electrochemistry." J. .171 CARBORUNDUM TO BIBLIOGRAPHY " Carborundum/' "The Electric "'Applied F. Furnace. SECTION 1904. Fitzgerald. Stansfield.

Fe8C Cr4C and Cr3C2 Mo2C \ action No with water. H2. Product. YC2 ThC2 U2C2 Volatile and liquid hydrocarbons. . pure all are the Moissan. W2C SiC TiC Cs2C2 Na2C2 K2C2 Rb2C2 C2H. carbides The carbon." : products of decomposition are shown following in the " Carbide. of them with reformation react of first 1892. CaC2+2HaO=Ca(OH)2+C2H2. in December. 142C2 CaC2 SrC2 "42"C2 BC2 CH4 A1A Mn3C " "" CH4 and H2 CeC2 LaC2 PrC2 NiC2 CH4. a e-g- off in with furnace a who electrical furnace isolated the state.Section Our of knowledge is due chiefly carbide. give to these BORIDES AND CARBIDES the of lime electric the with to of that by reduction in THE VI. prepared as metallic-looking dark Most hydrocarbons with the solids water oxide. - The list of work calcium of products crystalline fracture. other C2H2 volatile SnC2 and traces of hydrocarbons.

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(raise3 of C from liberated!of by formation CaO mols 1 mol CO (of 1 mol CaC2 = = CaO o" to 200c0 C o" to 20000 C. which carbon There have (Gin).= 24.4+o.174 INDUSTRIAL nearly two ELECTROMETALLURGY the carbide raised be dissociation would be and carbon.800 into Ca and O2=i45. into lime back of the carbide If the graphite and into to necessary " is said to be carbide the high too CO of atmospheres convert re- rature tempeburnt. the which at supposed are uncertainty in the some carbon at formation various the adopt the on from lime hours details there specificheats well the as to as and (CO products as and kw. ton.700 = 3. 1523 stream. of calcium will We hours the leave to for carbide investigators have temperature CaC2) and Several kw.ooiT of CaO the furnace incoming follows at 3. the followingvalues as tions the basis of calcula- : " Atomic specificheat of Molecular specificheat of formation Heat carbon of lime=n. 3837 no retical theo- production the furnace. and of the values to given high temperatures.200 3." calcium vapour taking place according to reaction (3).200 = CaC2 we calories =145. C.900 = the carbide 20000 charge. we and and not are calculate may carbon used the monoxide heat to leave up the required energy as : " J m"l (ra*se Heat supplied p^ Heat that assume per gram molecule 29.26+ooo72T = to from 1decomposer mol. gas made necessary calcium pure from varying carbon.900 33**00 Net energy required=i66. of ton off in the calculations expenditure metric one several been energy of carried are is still of lime of heat carbide.ooo = 30.800 29. or hours per metric .040 calories kw.the resultingcalcium acting with the carbon monoxide present to reform lime and dust.000 CO If 4.000 199.

visable. carbide The by of means furnace led heating has the to types of furnace carbide owing in the vapour the that best small which arcs have been obtained with the is there Both chaige. frequently a smothered as furnaces. however. carbide important mixture a theoretical 1440 charge have of in . charge consists The limestone in the maintained kgm.F. the found energy in the evolution a (2) are : carbon loss no were produce to 3000 1000 kgm. Q in the reaction of obtained Haber " CaO+3C+Q=CaC2+CO 3*3T. thermal originally designed for heating was electric an processes. and necessary continually made are the act whether calcium both 8 volts. 5960 kw.M. hot " incidentally to and presence be reduced can arc the of thermal electro- modifications is.and the energy consumption per ton of 85 per and varies between carbide cent. and found from and If charge should practice factors of carbon monoxide of and The the formity uni- impurities. an of the furnace the construction on due self- to induction. charge is inad- during the . been proportions. very efficiency. arc. a value determined by Thompson equal to 121. currents used the . hours) by value the that he assumed which that to different somewhat a BORIDES AND 175 in which method. 3500 was " depending of and the system operation. the E. hours. in arc broken in uniform direct is product badly designed furnaces loss of energy considerable by the alternating and most but striking probable more and any carbon for It appears the principle. It other use considerable operates purely to in most as to make tendency employed furnace since but. cit. to furnaces of movements of of increased resistance the on " resistance an doubtful charge. charge which consumption that 1700 necessary composition. former.000 calcium carbide 85 per {loc. Commercial averages cent. of two of yield and the of It has been The of kgm. influence (1) Size Presence finely comminuted of crushed for this output. purity.).CARBIDES THE a figure closely approximating (3100 kw.

ash. should carbide wood industry and give the best results. mass a loss of which without charge of inch results and of gas burst finely powdered the uniform most to frequently in the results to the portion a practice the In of the mass. is desirable. causing at charge. In addition. anthracite. less. do not sensibly affect the operation of the furnace. and in small crusts easily tapped so phosphides. this the subside. constituents. find Anthracites thoroughly low as content can be in the carbon containing more Coke possible. 5 per cent. or carbonized wood and the sawdust. of heat escape channels and which interior interior surfaces amount can carbide the in the formed to be on of formation of process ELECTROMETALLURGY coal the obtained are J-inch to or inch. impure The other coal spontaneously inflammable. are distillation. ash cent. The usual assist in the viscous formation molten the cause impurities and not lime as phosphate phosphine. account on phosphine arsine and of their is to quantities in the sulphate beeome are coal or reduced of in to the furnace. all objectionable water toxic properties. The moisture. numerous time same due honeycomb causes .INDUSTRIAL 176 channels glazed a their considerable hot gas When the charge may load from the become with carries it by using lime crushed a with ease of overlying large fluctuation in the furnace liberating a sudden i the heating it. ^ lime The manufacture for carbide free from burnt and coke. charcoal or should have than as ash and only be used with great difficulty. arsenides When magnesia of thick carbide arsenic. per quantities of of by-product the ash an less than Small of form 10 containing 3 usually employed. phosphorus the are of iron and the alkalis. silica.oxide ash or sulphidesin and with small . and furnaces larger furnaces sulphur present and calcium treated in the which alumina. Various ensure so as the not alternative schemes preparation of to limit the pure have from carbide manufacturer to proposed to impure materials been the purchase of pure . their into way per cent. impure carbide will liberate hydrogen sulphide.

for the semi-fused iron generally kgm. Horry instead " all of the were and acting formed oil to the lime hydrocarbon furnaces present time Bullier As to carbide.. and BORIDES AND liner are 1400 kw. (Fig. whilst surface lowers dioxide the 177 of the furnace quantity a from as silica the bottom adds liberated suggested the remove of manganese such the to Hewes cent. 12 . A) had increased partly solidified to types furnaces these and the furnace occasioned Several broken to type. heating up use to below of limestone melting point of the calcium the it to be tlie calcium addition the ferrosilicon. per Rathenau off from be drawn may 2 lime. and unconverted charge of about of 1. next one of the carbide fused the of to cool. together. the carbon phosphides manganese of carbon " energy about non-hygroscopic carbide. sulphides and the of easilytapped. (3) Continuous The earlier forms (1) Ingot Furnaces.which as carbonate crust. The the and charge. two furnaces and and up furnace the mass.19. allowed non-converted in size.19. at 50 to furnace 70 walls. loose non-coherent. dioxide The of a the addition of crude mixture a The to serves carbide Calcium at the carbide furnaces lime and is said of three " " of lime and carbide is formed contents distinct The earlier Willson pendent electrode carbide which by introduced of as taking of a such 200 to 250 Willson. only part of the charge observed. such is removed the half-formed latter is returned " In in. protecting a in are sufficient amount a transmission having the give carbide the as continually raised was already been is converted. charge. when (Fig.CARBIDES THE anthracite iron to the melt carbide. charge a with the material basal and Owing the loss of through current Willson improved one the block as to . and then the has ingot furnace the are separated from of molten " is fed coke 6 " furnaces. furnaces. permitting " was purities im- carry block ingot type. or (1) The (2) Tapping furnaces. B) pendent electrodes. each run and materials an energy sumption con- About volts.

into the electrodes hopper charge "Ingot" be converted supplying the charge at one plates being then removed allowing are c furnaces. 800 but ELECTROMETALLURGY INDUSTRIAL labour formed 85 per carbide cent. the old plates are up. semi-continuous a metre 1 Carbide Union of movable means in metres 25 plates acKd car " A Fig. C). 19. above cover in the rapidly as to accumulate of the mounted point to remove as chamber a reduction are for type. two kw. platescan place. takes spindle is slowly and carbide rectangular cross-section carbide ' -0 Calcium " between the space of 19. removed complete of carbide furnace 7 a . Co.. in 24 hours With a load and molten of 375 The carbide it is formed. Niagara apply to wide A operation. the to spindle diameter and of the successful a ingot system horizontal furnace been has attempt carries made rings about two By apart.178 13-hour of ton kw. metric per carbide of kgm. tons per A a ring. sorting the ingot is and up charge after always high. the the broken about in the purpose. bide thus one. later of cost this from of consumption energy in the hours the is designs of breaking kw. the hopper outside from in which Two the After the revolution base a a rotated of the fresh so as complete rotation the ring of solidified carbide is made produced. 6000 been the Willson a hours reduced has to furnace. 4500 The run. the In Horry (Fig.

hours with will take 1000 in current both against as in arc open furnaces are by the from fumes. dcm. with the current only by the size current exceeding . working are from to vary improvements is set present tendency furnaces. carbide Norwegian the in produce to is stated Several " and theoretical a consumption for 1000 kgm. 1500 metric Odda walls. each to one practical limit furnace should not is set carry furnace. electrodes. 4500 per 3800 kw. (3) Continuous of of use unit Each tapped kgm. The enclosed of the electrodes. thus ducing pro- to for ton (2) Tapping size to reduce ton down brought 1 AND cost per the efficiency was obtained. evolved with When and is to in Memmo the to have continuity works. ton BORIDES Stansfield. phase The current is minimized limit a loss from the and power the the upper of sumption con- nuisance large multiple- totally enclosed. the to tapping A works. and an a 9000-kw. of material. 45 every in made Italy. works pattern is effected economy material. minutes. 4200 to 4500 energy kw. 50 at end carbide of ton The 1400 kgm. opportunity used has three satisfactory results. Furnaces. to 310 per furnace.9 by been means once furnace a charge being used Furnaces. especially by Helfenstein.CARBIDES THE of production obtained. consumption in use large surface By of the collectingthe this charge carbon presents itself. With " the radiation a 179 kw. be can metric 1 According metric of working and increase in the furnace an loss and heat the labour increase corresponding in of control of temperature ease is thus hours hours. 3-phase a to phase. which Helfenstein furnished used difficulties of the radiation monoxide charge of of carbide. carbide amperes per sq. which 500 provided tapping furnaces so as to ensure production.8 the energy consumption kw. The of tapping a large mass of molten carbide practicability of impossible in the smaller furnaces owing to the formation crusts and the high viscosity of the impure melt was gated investiin many The Alby Carbide similar very holes kw. is and volts their at early Willson in the considerable raw 1 Co.

incoming the charge for type.700 with the " CaO+3C=CaCt+CO from o" to 20000 30. The the to carbon equivalent to 20000 kw. as burnt as thus C. whilst of carbon and equation in combustion monoxide the is of of one gram- approximately required energy molecule one the heat to molecules 3 up in accordance CaO 67. Calcium Fig. is. charge of of the required the up formation preheating would to heat continuous combustion the energy monoxide its heat Three-phase the during only 54. The liberated energy molecule of carbon calories. possible to by of carbide. energy to the production the course. " It should. this 2000" at the for idea The application. seen. reaction monoxide amount the 1 The parting in the carbide therefore. furnace limestone the furnace technical the leaving the cooling water be can entering charge.180 INDUSTRIAL Borchers suggested of steam purpose does ELECTROMETALLURGY not carbon generation to seem have monoxide utilized for burning with received the waste heat C. liberated of carbide carbon with By of accompanying the be can. 2100 be charge. ton have we furnace. the preheating and . reduced of diagram. after indicated derived . be temperature consumption metric C. of hours.800 calories.

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" Applied C. Bingham. SECTION A." Industrial Stansfield. VI. . Ofen. Applications/' Wright." Calcium.ELECTROMETALLURGY INDUSTRIAL i82 TO BIBLIOGRAPHY of "Principles Electric "Der Electrische Carbide their of Bronn." "The "' and Furnaces "Electric Electrochemistry. Furnace. Allmand.

the education needs application the an of increased peasant land. as international and nitrogen the scientific of the all centre from to satisfactory solution a National fixed that of food production the for politicalexistence and question. uses other any intensive in world. and of of Apart from consumption certain social suring proprietorship en- scientific increased rational power view of as to purchase . development in the soil . the people leading to the a more increased nitrogenous any necessary. With increase corresponding a necessary. chiefly as nitric acid for forms cyanides for production of as for the diverse the is essential an materials nitrogenous in the chemical extraction the land the Approximately one-fifth of gold. and populated areas per acre find that we of the than in the increase natural the Belgium. in various explosives. whilst in yield per acre almost in America. popula- izers fertil- corresponding increased of foodstuffs is obtained.1 nitrogen the drew growing importance the to presidentialaddress in his Crookes. Association. especiallythe dyes. virgin soils of the wheat areas the Canada and fertilizer these of has natural artificial factors. British the AND COMPOUNDS METALLIC In METALS BY organic chemistry the industry. and for attention the problem.and of branches around land. ^ELECTROTHERMAL Section NITROGEN FIXATION Sir William 1898 world of economic of four-fifths are find we used world's the industries. tion. of supply the remaining fertilizers.VII. density of the horticulture of the most one and a is densely nitrogenous more country. such a Siberia not been yet tendencies as the system greater interest of the the of the found towards fertilizers.

The other chief source of supplyof combined Ammonia. the increasing consumption has led to various of the area to determine carefully investigatedsurveys the probable available supplies. which is used in the form of ammonium sulphate. of the in the usual distillation process. the present output an amounting to over two and a half million tons per annum. It be may nitrate remarked into nitric acid converted be ammonium the surface on oxygen oxidation in aqueous is not from ammonia can that also since combustion by of suitable used be as ammonia with catalyticmaterial solution. brieflyenumerated 2 : " in found are of deposits Large " "caliche. Although these depositsappeared inexhaustible when first worked.it to Government that before appears exhibited have the end a of the nomic present century the econitre will no longer be possible. sodium have worked been ever-extending scale since 1830. Less " nitrogenis ammonia. the productionof a a can air or or by fertilizer necessarilydependent on the sulphuric acid industry.\ by of means a for artificialfertilizers is certain to increase present follows as Nitre." on it has done greater rate than The indicate co-operativesocieties. Only about ovens.all guilds and that the demand at ELECTROMETALLURGY INDUSTRIAL 184 Chile. exportationof Chilean and important deposits of nitrates of sodium found British the within Commonwealth. Recently experimentsby Rossi and others have indicated that fertilizer. coal from 20 recovery cent. natural These nitrate. India. The reports submitted Chilean the diversityof opinion. of sources in the be supply may past.). potassium are in the and will and Persia. Egypt namely probably be developedlocally. Practicallyall the natural ammonia able availis recovered or coke in the but a is obtained somewhat Producers recovered coal distillation either from better (60 per from gasworks fixed nitrogen per cent.and although the somewhat alarming figure of the maximum 21 years as period of life can be rejected. Sahara. .whilst is obtained still smaller shale distillation and in Mond Gas amounts are blast furnaces.

of tons 185 one cent. entirely replace the Chilean requisite legislationwere coal if at made were available present nitrogen. peat and turf satisfactorily yet been ten there years " preparation of gaseous of fuel : atmospheric nitrogen combustion coal suitable development in methods of atmospheric nitrogen. the employed. manurial to extensive preparation of combined nitrogen from which . the The B. fixed nitrogen of available be coal thousand 15 per cent. These follows as not technical nomically eco- the methods during the last fixation direct the for fuel have considerable be classified nitrogen in extravagant whilst consequence. C. D. The . of which and peat the British and in the sludges potential more of sources has for As a a The A. difficulties sludge. per million two ammonia is evident 1 average recovery partial carbonization It production is over Britain suppliesover coal annual FIXATION of in the bones industries. technical the the to these being not of in nitric the acid by electric oxidation and arc. by fuel. of which Since coal with in of form the Great contains the on 20-per-cent.ELECTROTHERMAL The NITROGEN world's million tons.3 within found are especially in Canada extensive application of developed is areas Empire.their period indefinite. preparation of synthetic ammonia from its elements. associated to . works sewage are of the bulk drying of sewage the it suitable been may of with render solved. is reserve of economical Other of larger than the working is by no distillation destructive the residues in fermentation nitre if the Although the world's caliche. The fixation of atmospheric nitrogen by biochemical methods. by-products the and Probable organic of sources fixed nitrogen will possiblybe found in the extended of the low-grade fuels such as development of the gasification natural turf. means found are this supplies from Chilean of ammonia sources least compulsory. Ireland and present time the ammonia natural entirely lost owing combustion At purposes. a that alone could source would of the all introduced.

and nitrides. and electrical the that out poor. (i) The A. Davy McDougall and technical plant in arc The " Howies.g. normally a energy approximately gases 75 Schonherr nitric oxide are yields obtained to this plants Germany. It must. is not Since this Haber's of last the in water energy. cyanides cyanamides. the being only from of volume another pointed be however. to form be must reaction absorption as processes per although formation the occurring during and in technical equation N2+02=2NO the to calories. pioneer work connected was accomplished in England by the Cavendish 1800. 22.000 supplied 30 gms. e. dioxide nitrogen cals. 2 stages of of 25000 C. passing through must heat cooling the of nitric oxide of cals. discussed is very process smaller The efficiency of Birkeland. Rayleigh 1781. France are are of the outline An first the erected at that since these high gas temperature low percentages impossibilityof relativelylow temperatures. 13. the of the hour. follows as 65 of The : according evolution recoverable to 00256 nitric of hour. kw. and during the may. apparent stability of a . at the processes.500 2NO+02=2N02. with this Arc method investigations of 1897. equilibrium is obtained temperatures may of be gas a attained electrical gases At low are sufficientlyquickly temperatures mean in the arc remembered the to to the gms. per air is this oxide in ordinary air at high temperatures.and that the actually obtained coolingthe with be be energy concentrations considerable in equivalent are Nernst.t86 INDUSTRIAL ammonia ELECTROMETALLURGY be can obtained.000 to It efficiencyof the of nitric acid gms. however. technically available of amount concentration NO cent. of nitric absolute to give a neighbourhood great rapidity due 63 or Jellinek and the higher mean practice. Italy. who Manchester. acid. and 1899 industrial present Process. in is which of operation to Norway. of the operating furnace be calculated or Pauling type can required to form a gramme-molecule 22. according liberated series. Taking the mean figuresfor the equilibrium temperature kw. although practically confined in operation in Switzerland.

that Its power. *u. on worked under and Strutt recently of Lowry reduced of Rossi pressure. there so erection loss Babcock Although is passes of this recovery gas of energy amount large volume electrical energy raising steam.600 calories.4. possibly departing from more on the of electrothermal it suitable power (2) By owing for those is the to of oxides explosion and factor Combustion work of of electronic an countries governing the the to process where the so and Gaseous his a number of ment.ELECTROTHERMAL gas rich in NO the reverse a 2 is assured reaction of the 2NO equilibrium heat to necessary =N2+02 14 of is temperature (6-8+0 0006X2500) " represents the . remaining 95 per with the unchanged is effected Willcox be of the of the cent. Partial arc the process through chief merits are action. 0*050 for hours acid. is therefore consumption energy to and passed through absorption towers. or the nitrogen and - . nitric nitric of 63 gms.600 calories. to as in electrochemical of Haber one on the duction pro- of gaseous patents have been . indicate that arc methods be capable of modification may and the original improvement. The of gas has are can wasteful in simplicityand costs are formity uni- high owing heated." pupils render of electrical cost nitrogen during the process combustion. of gms. - that value true 25000 C. or " " air. X2X 2500 " 4. 5 per per kw. production an allotropicactive modification of atmospheric nitrogen. The out 63 efficiencyof only electrical technical a of production the an 42. or hour. gms. developChiefly Fuel. for the as doubt no of production of the by passage boilers available of gms.1 The energy 16 approximately 20. with slowness the of NO 187 FIXATION to concentration up this to oxygen owing concentration cent. on The work the use and of Haber of Koening and furnaces arc chilled arcs. cooled be to data no extremely extreme that and recovered. representing acid for cent. at which Assuming proceeds. per NITROGEN total lrrecover- 2 able kw.

various temperatures. is oxygen or is made of large capacity. " RYf2 3 TV of : 1 of hydrogen is likewise . forth cyclic made explosion temperature in about be can cycle. The of charging. elements the outbreak under put formation Regnault Leverkusen of due successful and the or substantiated. per of gases 21000 of should gas obtaining over photochemical action induced on oven resulting the 5-56 gms. and amount mixture of centration con- has period of by Haber Oppau to of NO. however. in high be of technical Badische the ammonia will the to explosion.lCNi increase ammonia over the beneficial From of increases pressure present. when cent. to endothermic and kw. process release. at the " C"h. equilibrium constant from It of equation and in Ramsay nitrogen Anilin Germany equilibrium the pressures gas and that from equilibrium amount noticed a first Haber war. These 5 per yield C. few hydrogen experiments made was Fabrik at previous years determined the 3H2+N2$2NH3. u. and stoichometric the furthermore ratio H2 for high concentrations the general equation "gK2 : an excess N2 : : of ammonia. The hour. of air and gas oven has is that scale of coke which one formation direct fuel for the utilizinggaseous been veloped dein Hausser. The " synthesis of ammonia Soda a on NO an inventor the to be Process. ignitionand modified Otto The rich coke with claims The B. mean operating scavenging. per cent.188 taken of ELECTROMETALLURGY INDUSTRIAL for out oxides of on which only semi-technical a mixture a The nitrogen. of the development the remain Haber only 05 favouring the during compounds claims. Provision exploded in a bomb for a rapid cooling of the gases by water injection and rapid release into the cooling system.

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local when the electrical is small temperature mixture current gas. argon production is obtained. change inter- heat by liquefactionor under The present. externally. from the eliminate owing and pressure. and weakening heating is now in compressed were hydrogen The water-gas mixture " bombs the of the now removed are scrubber.INDUSTRIAL 190 calculated temperature. high temperature. internal the ammonia of decomposition to metal over-heating of the of heat amount and to water-vapour. speed equilibrium gas-flow. formed through is small catalyst space of heat N2+3H3-"3NH3 good system hydrogen. to the of in catalyst the supply and to the inert the such present in the the low as the is important gases At very yield per litre velocity of the high speeds equilibrium is percentage of ammonia unused gases of ammonia. of gaseous the compressor. removed under ELECTROMETALLURGY not is formed. calcium and monoxide in the now of oxygen of traces to is steam sulphur any alternatively by or blasts are asbestos owing action carbonate steam purified gases palladium constant excess and of the traces nitrogen-hydrogen a The C02 the liquid air prepared from the equilibrium cent. with washing by off " the for the low of only a very low catalyst is may occur. exothermic. passed to catalyst and the necessary energy operation. circulates already ammonia water is necessary from methane an the ensure by the combined gas reaction for when recirculated and blowing The subsequently removed augmented dried " is over generated automatically falls owing The is installed. applied. per ammonium cuprous a 2 the by pressure washing with water. Since adjusting producer originallyheated the nitrogen so one chloride of the and contains which bomb. K=n-C^-^1 present is about is to Small pressure. At and a additional economic through system a maintaining velocity of circulation The nitrogen. and the CO formate by scrubbing with hot caustic soda H2S as is converted by from by condensation. air and preparer The the absence The but electrical the " catalyst interchange coils. but counter Periodic bomb. but the . obtained.

. 15 per cent. Nitrogen million 10 several and of than more tion gas circula- in the the hydrogen. contain of moisture. Aostridium Aspergillusniger. The 4. The azobacter . Penecillium others. Bacillus and Large glaucum. the grammes yield in kilo- litre of the catalyst per hour. quantities of such Azotobacter radiciola. of saprophytic anaerobic. is determining factor as far as output of a unit is concerned. 3. organism this of smaller nitrogen for : " quantities hinder further absorption.ELECTROTHERMAL yield the is hour per higher owing gas-flow. i. and aerobic both number a organisms capable of fixingatmospheric nitrogen. of sodium 2. entirely distinct from the nitrifyingbacteria the more are capable of oxidizing nitrites recently discovered The first fixingnitrogen Pastorianutn.the difficulties of heat are the by and gases the skilled (C) Biochemical soil to the varieties preparation of the ordinary In " present.and and successful this property. of calcium. of the organisms growing in symbiosis be lies between with function other most successfully when organisms. determined with Naturally 15. pathogenic organisms include bacteria amongst moulds. Fixation. The 191 velocity of increased the to time space ammonia of FIXATION NITROGEN yield. viz. as been was Since shown such as isolated and agilis.e. this of in soil property are fixed organisms the as fungus beta Phoma and chroococcum conditions The brieflyas follows phosphorus and potassium. nitrogen fixation Presence 1 nitrogenous organic possessing bacteria the among as by Benjerink. frequently rising are These per gramme. have or already in the soil substances. or period a large number to possess and Winogradsky denitrifyingorganisms which nitrates and reducing ammonia. technical In operation the space time yield may rise as high per gas-flow. of chiefly is compression supervisionnecessary. The less than Most temperature earth range should well aerated io" and and not 500 C. of bacteria number vast a velocity of of the process cost entailed expense purification of the and increased regeneration and The greatly enhanced.

successful. Metallic fixed as these Electrothermal D.) technical prevented fixation would atmospheres " fixation in the the is so process great that probably prove of Savoy. mentioned the All by these pressure of in processes the compounds +3H20 be can steam Nitrides. peas as associated practicallyonly was such Hellriegal a nitrogen has and from of such although being a nomically eco- process reinvestigation of remunerative. by purely thermal industrial scale. radicicola that with leguminous plants and bacillus exhibit several strains cultivated certain algse whilst with abundantly most grow parasitism.ELECTROMETALLURGY INDUSTRIAL 192 showed the B. it has been during the period of the war large quantities of nitrogen-fixingyeasts have in Germany for supplying pigs and other animals and requisite organic nitrogen.the cyanides and according X3N have Elementary " Amongst with treatment methods of by activity of artificial sugar grape of soils the this in their successful. such the to been determined be generations several good growth is ensured A should bacillus that stated inoculation the In plant the case alternate of on in this . grown with the and crop. scarcely proved converted XCN+2H20=XOH+NH3+CO been and several more 2X2NNC+2H20=(H2NNC)2+2H20 The media. since use. important under nitrogen the problem (under 6 atmospheres pressure) in water +NH3 (at 5000 C. Of nitrogen-fixing organisms artificial media for recent years have been agricultural purposes. the followingequations : " difficulties forms to the =XCOOH +2H20 by Metals nitrogen has been or accomplished by Serpek several peptone. by the addition soil. little bacterial a water X2NNC+3H20=X2C08+2NH3 XCN deteriorates Nitrogen nitrides. .yet the advantages of few +3XOH The be may ammonia into =NH3 a an on cyanamides. choice of the nature the organism when employed contemplated of the the controlled for grown before pabulum to the Up present time commercially and Fixation Compounds.

18500 We to nitride much lower C.. again dis- carbon In the coke of a of bauxite by radiation. place below take the : at which temperature in engaged was A1203 +3C +N2 The is consequently the nitride is actually apparatus suitable for carrying on nitride through the intermediary preparation of aluminium. states C. hollow resistor. at 11000 absorption of nitrogen commences the absorption is fairlyrapid. and that of the From Serpek 1907-1910 technical a scale higher than is 21200 quickly construction followingreaction out the A1N +3CO " this =2 the nitride and C. formed of of the temperature decomposes relatively the consequently reaction Serpek temperature.desirable owing that relative can a with confirmed Read6 the conclusion the similar readily converted more and Tucker to A absorption commences and purified by the at readily soluble in the electrolyteused is not method alumina that already noted must The and vertical annular coke. low-temperature fixation. . having charge of bauxite an is Serpek successfully operated employed of furnace nitride the by suitable catalysts usually types of furnace kiln rotary to observation the a brought about be different at with ease present in French two 15000 C. temperature. preparation of by Serpek in is Bauxite connection resistors The was heating a second type shaft containing space is 1. first carbon transverse and consisted mixture Savoy. aluminium. results these which and came to bauxite. and 13 . in the charged with axial a sociated. have electrothermal the for the made was formation of than nitride. alumina.ELECTROTHERMAL NITROGEN FIXATION 193 devoted to Serpek's early experiments (1906-1 907) were nitride by passing nitrogen preparation of aluminium carbide aluminium at a red heat.whilst from 17000 reaction is a the comparatively violent one. when according to the over 4 Caro following reactions the take place : " A14C3$4A1+3C 4A1+2N2^4A1N dissociation The carbide.

the possible development alumina may of for each observations. successful be as so be course nitrogen fixation technical a likely to more be of of not of suitable absence could preparation the did dehydration the to alumina the catalysts. is deposited carbon are " CO+H2^C+H20 Either of these of carbon reactions in a obviously finelydivided permit form. nitride the weak or liberated incoming the up recovered be can ELECTROMETALLURGY alumina Pure by decomposition with " MN+3H20=A1(0H)3+NH3 Attempts to in used future of development lines is these could process devised of the need From both charge. such chromium. process continuous prepared presumably containing other or nomically eco- yet the aluminium. by CO. and " CH4^C+2H2 whilst carbon monoxide hydrogenation mixture over contain a may nickel less than 10 be converted into methane catalyst (provided the per CO) cent. Tucker's titanium utilization pendent inde- process oxides.H2 " CO+3H2=H20+CH4 when comparatively under 3800 C.INDUSTRIAL 194 a of current nitrogen passed through the charge of 16000 is burnt 17000 to heat to superheated from steam The C. of supply Serpek and a that possible appears render to if the of fresh a bauxite synthetic catalyst could a permit Another the be would which is treated imagined as of the : At a into nearly completely dissociated according to the reversible equation hydrogen iron cessful suc- which reactions of temperature is methane the in process catalyst for gaseous a follows as of as be alumina.e. i. Although it after successful. probably owing prove on alumina the use 15000 carbon C. It of the would tion preparatherefore . according low temperatures higher temperatures equation At to the employed. alkali at rature tempe- a monoxide carbon charge.

whilst the manufacture is obtained.000 nitrogen calculated fixed Serpek " nitrogen calories. It will be formed carbide of the If is the energy of "5 kilomols amount of calories. necessary kilomols for by only gaseous that utilized be 1 CO assume we can 3 The of nitride. the to reacting By the combustion calories 102. 7300 hours. 7300 laboratory scale.000 hours. have which to preparation aluminium. of 1 mol per by energy bustion com- of 15000 C. and in imaginary the above for the consumption power shaft a suitable in the hydrogen maintained be is small. monoxide patents have of ammonia evidence 40. or ammonia as metric per kw. dis- fixed .000 of fixed ton nitrogen calculated +3CO mol kgm. of alumina. presence of 195 and blow especially sensitized maintained that blow steam a nitrogen. through with low at theoretical reaction the A1203 +3C +N2 lysts cata- It has been facilitates gases these temperatures. boron by CO kilomol one up supplied be kw.000 process per Various and that energy in utilizable of heat to of carbon the ammonia choice carbon follows It monoxide reacting temperature a the is about temperature carbon consequently far greater. or from magnesium.ELECTROTHERMAL possible seem carbon blow NITROGEN alternate to or the fixation the at the conditions nitrogen would The process. reducing the of to any mol one theoretically 62. and as of case nitrogen absorption. the as for the There passed the principlesinvolved Since 151. that those The used other ton of Cyanides. of able.000 metric from the are speciallyprepared alumina. CaC2 mols 1*5 of molecule per calcium that noted have market is no experimental are the already been value of same cussed. especially out besides and 213. titanium. since process of nitrogen a requisite temperatures.000 of from cals. hydrocarbon a containing alumina stated FIXATION Serpek " A1N =2 calories per requires only 213. hours silicon. obtain- are able avail- are to nitrides them the 5170 taken been kw.

hydrocyanic as hydrogen .6 a synthetic expensive cyanide at viz. raw charcoal. processes. It would processes margin been ones a nitrogen fixation the and +H2 processes only sufficientlyeconomical not a difficulties cyanide a these existing the ammonia utilizing atmospheric nitrogen is used many have processes time Castner. Cyanogen indicated these this section In be last few synthetic ammonia the before research. will developed to be application on a appear scale.ELECTROMETALLURGY INDUSTRIAL 196 nitrogen in the form actual value successful utilizes as cyanide is greatly in of and fertilizer. naturally exclude be to but developed by been will be and union of acid proceeds formation of a hydrocyanic mixture acetylene and more Acid. Bucher. technical heating has this included which those would electric the form of when the has been there and modifications. attention process. in methods will suggested be large number. electric yet those of one finallysupplant both which stimulated is evident transportable synthetic cyanide these to prospects the has at the of providing to permit of the so as fertilizer prices after some During nitrogen. of production to the to Up with combined with as cyanide sufficient cyanide produced so in having ammoniacal redirected sodium that cyanide cyanamide considered . process. Hydrocyanic sparks through The is used. nitrogen shortage are into converted been form overcome operation costs sold able been some could the nitrogen. sodium. newer and or feasible for may the calcium only those used viz. " cyanides present compete that of number great the most equations to the =2NaNH2 2NH3 +2Na NaNH2+C=NaCN+H2 a the present materials. be to be to process working in have in which have for proposed starting-point. not already extant. according that its of excess of a Berthelot acid by acetylene and nitrogen smoothly when " to diluent form such first passing nitrogen. a representativeand most compete years processes.

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thus red when part the absorption of nitrogen. 50 Charcoal intimate The 10 mixture coke-lined of air Deoxygenated When as electric an water or latter is used the fuel. and chromium charcoal the gases. . or is stated formed so in absorption. . . The according to absorption the equation sides is passed denitrified said was into high temperature a introduced in the gas the to current inserted kgm. by Swan It cyanide no of avoiding catalyst is present. a cyclic process of heating. . from it is evident but processes. . added to formation heat. heat interchanging and scrubbing the gases with an alkali would certainlyprove worthy of investigation. residue be may used proceed smoothly to " BaO+3C+N2=Ba(CN)2+CO Part of the opening situate volatilized by was with 14000 C. . a a " the suggested nitrogen by carbonate of use of means and electrical a carbon. . . mixture As of alkaline suitable mixture or suggested he " BaC03 . catalysts the dull and be of lateral slightly modified titanium. of these crucible by the passage of oxide earth of following : the a fixation for the heating of by means crucible. the through the mixture. efficiencies of conversion the to as spark discharge to high temperature arc discharge when utilizingcrude riched producer gas or producer gas enwith some hydrocarbon.ELECTROMETALLURGY INDUSTRIAL 198 data No of these any available are yield obtained Gruszkrewicz by if a 03 that into converted be can per cent. . a by Lepinski by simple transition yield as claimed 19 per cent. The Alkaline first Earth Readmann7 Cyanides. . . . The above with commence high temperatures mixture these at which a necessary it was can previously recovered absorption molybdenum. is introduced substances is heated and electrodes carbon . . . . kgm. before a crucible temperature which was through out the process in manganese that of from optimum earth flows bottom The alkaline cyanide will the the Kendall.

is thus Alkali be free set and nitrogen can melt of the temperature The and barium the cyanide. confirmed who at erected Margueritte alkaline form to to cyanides easily.and most cyanide blast furnaces the catalytic effects and chromium. sodium Sourdeval Bucher at gas manganese and 1895. Thompson Clyde the in catalytic effect of iron. by briquettes of sodium a catalyst. requires 43. by such as Margueritte Kendall process. and factories that Dawes attention 1839 fast drew in in and by early as barium of 1843. cathode high temperatures. Decomposition of superheated and alkalis in and claims complete at a C. 4 kilomols 900"C. recently investigated of as of the the Barium reacted made been it render mercially com- potassium reacted formation of potassium Clarke in 1835 and 1837.ELECTROTHERMAL NITROGEN FIXATION 199 suggested the following ingenious process : Fused cyanide is electrolyzed between granulated carbon Mehner barium electrodes in is liberated caustic at the anode the at alkali. at Readmann's modify more in readily reacted earths the The " Sourdeval. has rapid temperature coke iron and cyanide by 6oo" 8 to obtain carbonate. Amongst noticed was reacts reform to of Possoz process sodium. which of atmosphere an means according to following equations : " +4C +N2 NaCN +2H20 Na2C03 =2NaCN =HCOONa +3CO +NH3 2NaCN+4H20=Na2C03+2NH3+CO+H2 To heat carbon the 1 up and reaction one kilomol of of nitrogen itself is sodium to carbonate. and the at nitrogen fixation Newcastle and in water absorbed nitrogen experiments first the Grenall the Cyanides. of Newton. and both Mond Boissiere. observations unsuccessful many feasible. and metals. 140 of Calories.000 slightlyendothermic. earlier the with Cyanogen gas. continuously reformed. easily than or granulated carbon. Calories being . nitrogen in producer the alkalis the to as world Swindel. is steam nitrogen and and 9000 C. preferably charcoal. and attempts have the other and in the carbon so the to noted were absorption of with the as of by Swan i860.

carbide the and theoretical which the took possibilityof Caro nitrogen immediately the present time annual of the should C. 3(a). (3) Relatively high temperatures for calcium to : in be favourable cyanamide for the presented industry production being nearly half a . in 1895. should With place at cyanamide the overproduction the beginning utilizing these fixation of a large one. favourable According expressed by the equation CaO +3C place in really takes the to of for the gated Caro. of the or per consumption to authors first of formation the the the were reaction usually " =Ca +N2 several (CN) 2 +CO stages " CaO+C^lCa+CO Ca+2C^CaC2 1. appears of calcium the the " (2) A porous carbide is desirable. Frank The Cyanamides. of the temperatures those than preparation formation conditions the cyanamides. of observations atmospheric themselves.absorbed. the optimum. and earth are formation the cyanides through alkaline of the study to of noted will be intermediaries and " the for necessary preparation of cyanamides. and 3 kilomols of evident a ELECTROMETALLURGY INDUSTRIAL 200 the is CO that reaction the as in and one. and is 11000 excess at the of century Frank to be be employed . The carbon produced would that much lower nitrides be working the metric equal to 1300 kgms. is therefore It be can considered practice should without production continuous whole a of the combustion from calories. It ammonia of ton cyanide processes necessary carbides. CaC2+N2==CaCN2+C (6).000 over strongly exothermic of available energy be of supply the as capable traneous ex- any energy. 2. investi- intermediary the carbides. 200.CaC2+N2^Ca(CN)2 following conditions The of calcium formation found were cyanamide (1) The nitrogen amount required.

series a chloride give the to out addition absorption of nitrogen.ELECTROTHERMAL million exclusive tons Central NITROGEN of and cyanamide conclusion to the came degree of dissociation the " and amount dependent were carbide of the of calcium the relative that formed cyanide of Leblanc war. and kgms. cyanamide the In is off. taking oxygen or and capacity. manufactured now and a barium the results. work drums. Absorption of case the carried found The Cyanamide of is process In the carbide packed is crushed in small capacity and The drums. which amperes contain at volts. economical more intermittent the is produces and ones calcium of agents best intermittent the processes. at 1 to and by ton of to heated are is some should prepared Claude 10000 by processes absorption finally turned the not passed in when when C. carbon the higher grade product. and of FIXATION the on " CaC2^CaC+C 1. were carbide. cyanamides of 201 production period of the formation investigated the increased the the during Empires barium. CaC+N2=CaCN2 CaC2+N2^Ca(CN)2 2. per fractionatingliquid air by the to 1 Pure cium cal- by earlier at to each resistors. lined with are of The the than at recently of more internally by 20 sheet-iron fluoride continuous. reaction. cent. hours' passage of the that gas. " tinuous con- powder complete after during which period from metric fine metric Linde 8oo" absorption is maintained it is found of being maintained The 2 is reduced current the temperature to a of 300 each hot two in Norway nitrogen. 70 than more 0*4 or the by passage the exothermic. which the over risen has temperature commences of air Odda refractory bricks. ground and experiments facilitate to and somewhat process cyanide. which about is 800 mittent inter- 500 tons drum copper. large quantities of suitable of use 7000 at commence calcium and Carlson and to contained always Polzenius on barium both product found was C. is 30 rature tempe- practice produced . but in the C.

the resources some electrical Comparison no Nitrolim. and to the on of ton allowed are 15 to o-8o to placed are ELECTROMETALLURGY two . electrical costs the available energy if solution process is somewhat nitrogen and but consumer. the some delivered mechanical should fundamental It is evident permit of their economical by liquid air to metric one already described processes world. two the approximate consumption . per recent of market packing crushing and of fixed carbide hours after " the of contents per cent. viz. of the natural of the consideration one costs problem is not amount really offer the soil in the chosen fertilizing method a fixingnitrogen would international material national The problem that be almost can energetic efficiency of the i. a taking nitrogen with areas efficiencyof fix to costs different and given a the to forms running of costs the various are usually required. by the nation. erection for that great entirely replaced transportation costs too In the required energy the thedeciding factors between the be cost different. viz. will ton nearly inaccessible region. the power and from the air and of development. the choice solely determined be In large supplies taken involved deciding factors. of coke factory in these or following table form modern only.INDUSTRIAL 202 from 078 drums the energy expenditure required for heating is about metric by the alternative guide the to conservation of of nitre of that nitre of the most economical in the to practice. processes the relative forms would equally efficient processes different proposed factory sites." utilization consumer labour work. existed of kw. the decided be exceed not Processes. 500 or According production of solution of the fixed. since manual problem the it." containing as nitrogen. Nitrogen Fixation comparing the costs for and kilogram per nitrogen cost of estimates of of ton hour nitrogen by fractionation various to kw. o*i estimates. 20 The The carbide. The the by process in terms of become the alluded to of the of the relative in of the two and energy of sources energy in the carbon at In the alternativelybetween two of the as whole. cool.e.

NITROGEN ELECTROTHERMAL and of energy coke fix 1 given : required to by the different processes are FIXATION metric 203 of ton nitrogen " 16.900 It is a of the interestingto relativelylarge hydrogen. and that note amount that any the Haber of coke technical process for the sumes con- production development of .

Alkali R.. Electrochem. " Sons." Cyanide ." Ammonia. Soc. Ausnutzung Coal " der Atmospharischen of Tar and Atmospheric T. this Purification. Chem. M." Atmospheric Technologic der ' Norton. Nitrique l'Acide de Electrochemique "Fabrication J. 233 : 20. VII. Washington. Technische Frenzel. ' ' ' 14. 17. Industry. Ind. 1895." TO Industry. 6 /. * Trans. 1906." Lunge. 194. Knox. * Zeit. Chem.. Nitrogen." Donath 1907* Utilization " 19 et 1901. 2412. 1917.ELECTROMETALLURGY INDUSTRIAL 204 either the would be Bucher rivals serious Serpek modified or the to Haber " also S. Over French 9 in Reviewed 10 9. Cyan verbindungen. Industry/' Alkali The Rideal. SECTION Robine this Partington. . 1 906.. R. J. 191 2. 1917. 3rd London. in value the Patent series. of Fixation "The Escard.. des composes Sticks toff. Problem. Elektrochem. cyanamide. Bertelomann.10 or SECTION TO REFERENCES 1 (see " series. Partington." Wheat The See * 1Q2) p. Nitrogen. 8 8 " processes VII. Amor. Wiley Lenglen. " edit." Sewage Angew. of Eng. 24." Die " u. times nine 7 28. Zeit. Nitres. BIBLIOGRAPHY "The 64 p. 1914. " the 1912.

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sq. 0083 per cent. sul- its weight which carbon- the author's . 99963 per cent. With 15 Hambuechen4 purity with 1 volt both at a iron at found was anode an 1 per rature tempe- a to very ferrous gms. is the be deposited procedure be followed dehyde (formal- tartrates. chloride and a Watts and 0001 H. . Pfanhauser and Langbein CaCl2. litre of advised they agents electrolytes.. find I4 that electrolyte containing mixed a 150 sulphate crystallized gms. per P. . citrates complex as only and in detail. in the likewise anodes dcm. to with that density of current a than 01 of cent. per cent. 0*003 Per cent.M. cent. and 75 gms. ferrous per sulphate (7H2O). 0020 O.containing Classen's7 6 hexaminetetramine 0*5 gm. electrolyte. dcm. H2. . iron produced : " Fe. As ammonium oxalate ammonia) Other and or per been of ammonium can suggested oxalate. this time from ferrous equal weight of oxalic acid. and an gms.F. P. Sulphate have Electrolytes. (700 gms. 0013 per cent. the and employed. have free iron addition suitable one to ammonium 7 times from only when time.such oxalates. Good as bar ampere necessary and cathode. 600 FeCl2 gms. 3 to 5 amps. iron current a applied E. per metal. E. per of ammonium ingot and per sq. S. electrolyte. at higher a use I^ess deposited in addition chloride litre of volt. obtained depositsare electrolyte is circulated.206 ELECTROMETALLURGY INDUSTRIAL warmed 650 C. litre is better than either sulphate or chloride electrolyte alone. C. density from current Burgess " litre with American chloride a higher temperature a efficiency(over 90 per cent. Si.F. (900 C). phate. the are electrolyte. dcm. ferrous chloride (4H2O).) sulphate solution containing 40 current ammonium or water). deposited iron high 1 with and amperes per 20 to o*6o is occluded provided iron Wrought is about hydrogen electrolytecontaining calcium to per sq. the passivity gives the these under and cent. . density of 06 of a of Swedish anodes following analysis of conditions from chloride. of 99*97 the addition as low as to an overcome 6 Storey 300 C.M.

into C02 being . the takes oxide =2FeO Fe203 +2CO metal the warm into oxide. place. AND fuel with ores is burnt coke the at in base furnace. fresh top of the furnace combustion a top of the off at leaving the furnace and form to two metal. Smelting. furnace blast a THE I"bctrothermai.IRON Coles Cowper aromatic acids The or has FERRO-ALLOYS patented the for the charcoal Production Pig iron " is The limestone. ferric the zone monoxide by the carbon third the (3) In incoming charge calcium the convert . charge shaft. of the ordinary blast furnace The into five zones (1) The " top in which zone. Ore A. fuel fluxed of the to melted metal on tapped where the dioxide is not are of the complete.flow they separate into molten intervals. and of iron salts of several use Iron. carbonate oxide assisting to liberated heat the to is sufficientlyhigh zone. monoxide be can part of the carbon zone is oxidized zones carbon to " 2CO+02^2C02 the to drive off the in the water this (2) In and ore. +C02 to ferrous +CO reduction actual temperature the reduction bring about is reduced " where zone. layers. fusible the slag.and ore. carbon the the third third pig are at the lime zone. the entering charge is heated this In in the lower produced dioxide conveniently divided : by the ascending hot gases. still hot monoxide carbon ratio (from 3000 CO to C. of generally produced of iron smelting oxide by 207 deposition of electrolyticiron. the slag being admitted to with of the base in chiefly silicious. together with the containing the ash to " FeO+C=Fe+CO The of the gangue the immiscible Both slag and The gases 8oo" C).

2000 to used of only for reduction operation.such actual In a small temperature of iron is reduced half the practice the phosphorus. consumption fuel is required charge electrical modern If pig. of silicon sulphur and the not the and silica.208 INDUSTRIAL about 2:1. charcoal of of the two in ton fuel good as electric oxide. of high- charcoal. the iron practice we the are assume same and quality of pig is produced.owing and used " Power to represent those ores practice : in actual the of iron following analyses energy blast furnace cost less than data necessary pig when 0*66 ton 2000 kw. electric smelting of electrical grade coke The costs cheaper than will become To pig as one-third about supplied. thermochemical for calculating . manganese as quantity and so other phosphates. The Consumption. retained are in the iron. that ideal the In oxide only the impurities. and will produce one working the charge. systems course of the the the of of the In of heat equal impurities such coke. furnace production absence in present to the produced to the heating the reduced therefore iron is used carbon the furnace silica In " charcoal or being preferable. ELECTROMETALLURGY The waste gas furnace the is generally used for is controlled steam raising. be hours kw. and manganese. quantity the of coke of amount pig and sulphur for not for blast has energy that the that the same hours or fuel is about .

per of other cent. The of heat to the production of equations Fe203 +CO 2FeO is found equal to metric one =2FeO +2CO " (Fe2.200 (C. cent. produced (112 kgms.heating and to tapping temperature.000 (C.000 the furnace dioxide in the \ ::"l " .lomol = the required energy metric per ton of metal is 565. To heat melt to further the it and 350.and of limestone cent.02)= 97.IRON FERRO-ALLOYS THE AND efficiencyof the ore-smelting accurately the theoretical more process If be can broadly summarized take we of water.0) Since +C02 =2Fe +2C of iron according ton calorfes per calories (Fe2.000 For each ore) 200 For ton iron so produced bring it to calories are of molten kgms. 2 impurities. pig produced (from 16 tons to kgms.Q8)-(C. 8 per and by experiment that addition the in the of 12 charge. will requiredfor slag formation If we assume contain that carbon melting-point. CaO+128 in the ore).200 " k. be 600x240=144. 8 follows as containing 90 ore an 209 in the necessary of ton by ore ture expendi- energy necessarilyfollows that if lower- It flux will be more each to per find wasted energy sponding required and a correfor slag production will result. be total required. are increase Fe2Os.03)=201.08)-(C. For reducing the melting the slag to bring it up heat the the approximately kgms. grade " easilytappable slag is obtained an can : cent. we ores calculate used. required. per for this reduction.000 to tapping temperature. at ratio of 14 . . 200 up other impurities.0) 29. of slag will 240 kgms. - 5000 C. The is therefore leave and impurities calories.250 calories. the gases monoxide a of required. 239. of limestone calcining 85.000 calories will be will be of limestone required. and calories and i*.

.000 Total .500 . . of . present superheating and x in lost in the heat the pig. . composition energy required is of one X slag the . every the X 400 ^ Total For evaporation distribution the above.000 121. . 239. iron ton of pig from total of indicated required for energy a production of the Total the 100 100 =30. and cent. .250 239. .. . . . per 5000 C. For of calculating the total metric 1 ton of required for the production the followingfigures : energy have pig.500 in the C02. .000 calories or metal the sequent sub- 1. viz. kilomol 1 y* 2. cals. . 1. equivalent to 150Q kw.500 a lost heat and the added be must CO the 100. .000 . as pig produced 38. of .750 . 6*9 as kilomol 1 dioxide carbon equations given this calculated be can " every the by the gases : specificheat To carried energy follows For ELECTROMETALLURGY of ton pig of carbon 214 kilos of carbon. .INDUSTRIAL 210 the 2:1. Total in 1.046. making for the Hence. and produced according Taking the molecular in the ton monoxide of carbon are above. . 915. follows required energy Total as .167. . . .e. or of the " the .250 . . 1.275. as and to off of metal kilomol of 0-5 kilomol in the gas of CO in the C02.000 " " calories. of metal theoretically required.000 calories per kilomol.321. production for the .500 calories. . ore : . we " Energy required for metal production Energy required for slag production Energy lost as heat in the gases . in the CO or per of calories X69 is 500 and metric C02 of combustion of metric of the 2 available the carbon monoxide of water i. produced per metric cals. per calories total of 91. gases . 68. - " x " 637 +- 1000 "' calories.000 energy the gas. hours for a very . .250 high grade ore. lost in the energy is steam 0*48 x to 1000 kilomol production . of ton calories 53. 915.167.

re- 764 kilos.275. C02 same require shall we following reaction CO : : " 3C+8N2+202=8N2+2CO+C02 The to heat CO C02 in the above and heat absorbed molecular giving by the combustion liberated by the 83. whilst of effluent preheating or power duction proin practice.000 . while of blast of amount lost. available supplied electricallyand usual gaseous the feasibly utilized requisite for the a of much - second elevenths only of diluent.000 calories. 50 per is thus the consist with a large the combustible CO The successful with in cally practifurnace combustible the nine The nitrogen. 1:2.and leaving of combustion heat net a ratio is gases specificheat of 3 kilomols is monoxide carbon calories. velocity will leave 211 the to furnace.250 that seen 7. actual found down first the and case one-third elevenths the fuel as times four of the cent. taking the at require 550 kilos of carbon oxide In of of carbon 155. " earliest furnaces employed .390. of carbon calories 1. calories. than owing gases electrical when to much heating is used. C.000 for 3 kilomols produce have we making the nitrogen the 9000 C. lost in the energy of production greater. the large quantities of " viz. 4. air oxygen. 900 the If carbon complete we the be gas will resulting owing furnace higher at a fractional that assume electric must nitrogen. temperature. viz. As to gases how be can wide noted that total energy In the variations in the CO pure is diluted gas in two - process. viz. quantity smelting operation is lost. is 72. and the proceeds in the as sufficient air to furnace.600 calories. It will be process over in heat the electric furnace products from with are for electrothermal thermal gas CO. C02 mixture. Furnaces. the consisting of two-thirds diluent.IRON If fuel AND be for used FERRO-ALLOYS THE heating the injected for supplying the therefore to contain its greater combustion of ratio. therefore iron To as this total of a the case increased total would we for reduction kilos 214 of of of carbon the are quired.

for found report the of hoppers are the was for consists is made for tar used those were communicating holes tapping iron pig furnace provision Two of originally Keller vertical charge a ELECTROMETALLURGY INDUSTRIAL 212 in pig iron trode. the convenient furnace sulphur. and or ferro-alloys. 2200 coke carbon In the A fed and in round Haanel at Sault thu Livet and bound In Dr.for production the and Heroult. escaping dolomite Canadian hematite Heroult little above A ore in and employed. experimental an Fig. producing a the liner other tapping fresh gradually furnace is electrode pendent serves removed period will. ( of produce to off basic most the to Furnaces " tons 30 the A H^""ir (A) over A. operation from such . productj per During B. electrode. metal. of carbon furnace carbon but base level metal the of the are reported favourably of which on of 91 ceedingly ex- of cent. per as as by the smelting is this (U. to is Dr.S. his during (48-1 per ore and n smelted were the Ste lining Government at gases. B.he iron energy an visit. (France). Marie 360 Using iron). round placed alloys. he (1904). where white with 0"i7 kgm. one plate electrode. the Slag electrodes.A. cent. slag. quality good able of low kw. a Keller of pendent two drawing of production by provided. continued slag at was expenditure kgms. elecholes charge raised. a for either hours for one the the The CC. ferro- electrodes passage. lining. The in and shafts is fed in the other with through Haanel's details si.). cast grey using ton.

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scrubbing part together to cent. of hearth. the 4-5 carbon with The hearth a to 03 kgms. 20. efficiency 22. fire- tar. of from pressure The consumption reduction all of little hydrogen clean of Provision volts nearly hour per fuel 07 for to is used.000 output an for of current these ElictToiUs " diameter furnace phase. the of ton magnetite smaller by per an a in ton one obtained. Three-phase " in cms. 7500 has in is to the and with electrodes 60 the the transformed to 10.. in Norway per is 15 shaft the to TrolMtten. brick. hearth magnesite hearth diameter a shaft.000 on ia. iron). to furnace kw.000 and the to 90 50 to each of stated and Shaft furnace be to pig The pig produced of consumption (50-60 dust consist of nitrogen. steel a the metres 2 25 enters roof whilst diameter and metre 1 *of sizes. metres of furnaces furnace. per nearly evolved dioxide and amperes furnaces can of is made is returned through tuyeres. at erected Arendal and led furnaces highly satisfactory a Hardanger 3000 Domnarfvet at ratio which 2 : quantity of unscrubbed a blower excess 1. varying maximum a constricted Ttppint of in Sweden Hagfors at high. metres * erection These and manner. equally conduct to serve shaft.ELECTROMETALLURGY INDUSTRIAL 214 Tjndblad of and series a of in operated this design and at from Stalhane The shaft large subsequently were kw. lining with six or it with inner bound Four of constructed lined an 4 high. of . be with is cent. spaced current at 12. per and is from monoxide or and gas a ton the whilst thermal 80 a for the means electrode ore the removing gases. Both are shell of where cms.

metric per with of these consumption power heat fully use- more for steam raising. further- injected through tuyeres itself. operation.the could be outside than obvious an were smelting chamber carbon ore type. furnace for the development and the price of electric power production and refining of steel electrical hearth the been large industry.the quantity chamber with than grade carbon. Bessemer or acid verter con- . 0*5 per of the abstracted the to per of development lines Under o*oi nature less than at the on sufficient chilling of the situated carried and the future gases. pig phosphorus silicon can furnaces analyzing produced The of ton sulphur and cent. deleterious a 215 steam partial combustion to reaction to the and away dioxide carbon THE effect on of the carbon. A high the trodes elec- according " C+C02-"2CO The hours is material but It is with of extremely gas that probable furnaces circulation will of the be circulated degree same is not of heat in the as disadvantage. the already application of pig is still confined Refining and and in time Martin probably entirely processes. per usually less varies content high very 3*5 kw. and if that liberated the the just above from smelting chamber evident shaft preheat the charge ordinary blast the of present conditions the charge in to the cent. Production Although production the of is very is supplant a has where areas the open furnaces of electric slow in Steei. The B.IRON is gas AND piped owing FERRO-ALLOYS for used has content raising. 2200 averages A some usually maintained be reduction iron. is It together with of some of combustion of the inside employed is air gas monoxide furnace the ing smelt- shaft the by the to the more. ore. cent. the furnace. and Electrical purposes iron to low. employed are will for several distinct : " (a) Refining steel with open the hearth aid of a and flux..

.11 the steel and it form .216 INDUSTRIAL ELECTROMETALLURGY (b) Fusion of pure (c) Fusion of without Power charge is inserted raise any oxide iron to cold. . scrap molten of Function .to the it to contain and supplied energy charge iron per materials. . cent. . ton Cold kgms. the and 0*28 produced is 0*02 The that and the phosphorus. . lime charge molten 365 kgms. .using various of 10 Neumann " fluxes. . pig . with up in the sets may reactions of and as reactions 330 210 of reactions slag. of these for necessary used. cent. . . pig refining is intimately bound occur . per of steel. . . per 0*96 per heat from subtracted includes cent. of oxidation energy melt reduce to cent. two . the the tapping temperature. . . y6 cent. . 230 . steel to the When melting-point. energy ton it and steel with scrap of oxide Consumption. per contain to silicon. the hrs. . Materials pig silicon. . 45 kgms. whilst contact functions take both underlying metal. . 460 . scrap. raw of production the the of or calculated has heat to necessary i#i for consumption steel. . 285 kgms. . The slag and 53 process the reactions protector Both The phases. a which metal at steel the course place the surface The refiner require in to a slag the high . with of iron. purificationhomogeneous each of in the . Slag. Kw. . 500 both slag above of phase. 210 350 Same kgms. . . cold scrap. . per further He present. cold Same charge with molten The 190 . . Same charge 675 kgms. . pig carbon cent. . necessary metric pig iron. cold ore. metric pig iron and flux Iyiquid pig and flux 670 kgms. . manganese. . and separate heterogeneous a 280 " place between as . and in the take metal. addition the materials. per impurities refining- and one the assumes i*68 carbon. . . pig 650 kgms.

sulphur. usually takes either by and of the temperatures than occurs. as in the oxide oxide can carbon. amongst important most are one by the boiling-point mingling of the slag and Dephosphorization. complete oxidized process be may slag. have then be of in the the to is there reduced added Aluminium. or is distributed phosphorus high temperatures Silicon by phosphate. chief impurities. sulphur.phosphorus. all been and by the return to is reduced metal as metal continuously of disturbance silicon used the carbon high temperatures. oxide and It is . the respective metals. During to low it is oxidized the and oxygen named. To oxide reducing agents formed slagged calcium the slag are carbide can off. at : removal brought present in the from The " easily oxidized more when metal reactions. removed 13500 C. electrothermal limit of the temperature upper The of the advantages low a is obtained high temperature a 217 high diffusivityand a which distinct FERRO-ALLOYS THE to metallic the metal. consequently removal with is which sulphur dioxide. it . the at the metal in in the slag if basic sulphur as the ferrous oxides and the phase. phase rapidly. which Any is ratio. very in the the nickel reduced of oxide to and chromium. " Phosphorus about metal. only reduced also be can between is retained manganese any slag owing partition equilibrium. temperature vanadium silicon phosphorus the together at tungsten and of When " oxide and calcium volatilized Deoxidation. when taking a which by the series of chemical varied a following impurities. at definite a chief three of its formation.various and the ferrosilicon for this purpose. metal and ferric of in iron is phosphorus oxides at last traces the remove enters part of the removal. the oxide absorbed by the of Part of the itself. phosphorus. in selective be the order oxidation Oxidation is the case the slag and the of the period sulphur. long time to separate.IRON to temperature The with ease of the The AND ensure of the metal. phosphorus The is ferric the slag silicon. in As phosphorus more is elevated. place is set is processes. removed are viscosity.

during the partly effected by oxidation period of phosphorus removal. for high temperature a of the is essential. slag by according is most formation slag . at to the The one. carbon. very lime the of temperature desulphurization by occurs is Desulphurization of silicon. but chiefly due to reactions taking place in the metal re-establish to in the brought about carbide and Silicon formed and only is used active as sulphur diffusing from more equilibrium. being returned exists there slag in metal rising temperature. basic sulphur present the partition coefficient of silica brick a calcium by the steel. the period to removal. whilst lime When high temperatures. since the reaction carbide the carbide of means large a melt.evident a ELECTROMETALLURGY INDUSTRIAL 218 during this period of reduction that danger of phosphorus the reduction slag by obviated reduction phosphide. Ca3P2. desulphurizing agent a present. to at lower at temperatures. means the the be must excess " CaO+FeS^FeO+CaS is a reversible complete owing removal 2CaO Prior elimination high temperatures. an the rapidly raising by or the actual of removal by reduction. Both effect sulphur their effected of in which acid but slag using The " iron divides itself between in definite ratio of the with solubilityof FeS increases with in the original molten metal general principles ratio in solubility of FeS to be can oxygen the the since the slags lining. slag and in accordance . +2FeS to this the usual of the ferrous +CaC2-"2CO reaction " CaO+FeS+C=CO+Fe+CaS of sulphur is practically when oxide is carbide from +2CaS the +2Fe formed slag " . Removal sulphur is sulphur removal to sulphur dioxide. require removal before during endothermic reabsorbed the be can temperature the phosphorus Desulphurization. a form is not and This dephosphorizing slag the from metal the to phosphate.

and melting-points largely been has Washington. such silicon. the of silicon ferrous of means expense.usually added as silicon much low FERRO-ALLOYS only be removed slag can agent. THE AND The sulphide " 2FeS+Si=SiS2+2Fe probably added also plays part in the a furnace the 16000 C. In various the materials for used not much so of the of the has work composition shortens liners tion operaC. of Mines. during the and life of 16000 to steel Liquid " temperature removal. of the attained these At lies slag The work lining. and showed a more fluid. the Slag. about at itself of sulphur by ferrosilicon. present 219 the temperatures silicon. This entails intermediate by be to extra an in formation an in oxide added reducing form of ferro- in the and too cause may resulting steel. between probably period the furnace of the temperature elevation furnace the leaves in the and last the temperatures fluid. have been preliminary report has technical the In following data slags : " of lime or addition the slag is still tappable. Composition the of removal slags themselves.18 He points of various the made cent. 15500 C. and Vogt silica in the of calcium furnace Doelter a slag raised fluoride 75 l2 per the Bureau this problem. at accomplished been on the fluence in- melting-pointand viscosity the on perfectly 12000 and accomplished by the Geophysical Laboratory but sulphur furnace normal composition the on of be must softening point of slags lies between C. 17000 C. Washington.IRON takes the At place.whilst slags lime that electric Recently investigating been the given by softening- . Feild.since unnecessary 14000 C. gives the of excess viscosity.

types employed for steel production Furnaces have only hotter of water that greater than 10500 C. at lie tapping temperature of various between and 15720 C. by slags. distinct type metal and furnaces. two 12000 Three employed. tages advan- peculiar more actual the a on of to of furnace is relatively actually attains the . although it obtained C. In the the than induction and 14000 C. The but mined deter- thermocouple. refining. viz. and. the the have we ably is consider- furnace FeSi03 MnSi03 CaSi03 Mg2Si04 The as C. in the have each faults have to the furnace arc Resistance operation slag. average about also and in the temperature higher. electric slags viscosity of the slags at 15000 C. 11500 C. as 1470 optical pyrometer noted. the was the it to by The ELECTROMETALLURGY INDUSTRIAL 220 never furnace. Induction. large scale. " Arc.determined He and found figures refer found 20" to blast The to be furnace times 301 silicates have pure of Types furnaces the following melting-points: " been the and arc but at former than temperatures are in induction furnaces the time same principleof heating employed.

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are for in three used whilst simple alternating hearth arcs electrodes Frequently electrodes to than metal. I^ess Conducting " The carbon. per 6 23. furnace for is or Heroult which one metal current The has six been furnace for in electrodes Heroult types. 4000 consumption carbon furnace. follows the normal construction. furnace hearth of current are ones. three-phase suggested. the parallel.and a Girgd average fluctuation load with pendent of steel.INDUSTRIAL 222 The 35 ELECTROMETALLURGY of carbons. striking passage. consisting . arc current and passes the other phase-current. ton per in connected 75 four are for Keller current. kgms. in but the stand has amperes production. one appear in the electrode between three of the the its electrodes the through pendent four of arc has treatment series from use about of type lining Stassano in The is would furnace obtains are used it which The H^nulr this severer that EU-". at operates which to 70 there volts 12 ton Fig. diameter. ip furnace J. in cms. arc and Keller series to naces fur- type. steel obtained that """.

large electric smelting plants and in removed are metal molten the slags are of the carbon and He operation directlyfrom endeavoured the ore. three final addition the carbon made to the slag removal are Each additional 50 to 60 kw. Since frequently made is liner FERRO-ALLOYS THE Syracuse. are from When is furnace the coke metal iron . phosphorus hearth open transferred At to a furnace and H6roult furnace I"a Praz. in Italy furnace. necessitates the per ton of steel Captain Stassano hours " investigatorsinto in the ores subsequently desulphurization.15 and is then poured half fresh flux the of and suitable amounts added.lime and At phosphorus. The used. Turin. fluorspar and oxygen loss electrode steel is blown practicallyall are diameter type. the is added is ferrosilicon to of end and slag removed. to and metric per with bound no be further liner may employed. ferromanganese and the again tilted. until the The removed. removal the of carbon. being about to put converter into the to hour an been Bessemer added are Girod the slag produced. first for electric supply of produced. Stassano's one iron of the runs installed steel in at one formed at Darfo removed and of before ferro-alloyand steel. variety of a electric furnace. a remove the complete. an was possibilityof smelting series of experiAfter mental a the Cerchi. volts. and lime. the furnace uses.IRON of AND steel shell with a roof hearth The voltage lies between consumption charge is from from to 200 thus have kgms. and down arc naturally heavier 12 kw. one usually are 60 to up cold a hot a surface the to on liner . and metal run the ladle into the moulds. requisiteamounts Furnace. At Chicago. the magnesite slag mixture a The a is electrode by 223 magnesite or dolomite lining. of silica brick. to were produce It is evident . have silicon carbon ore of steel furnaces in than very of the cms. roof with electrodes actually been per ton These The the power with produced hours.and 100 of steel ton hours. 300 90 and 800 to 700 reflect the large. tected pro- pitch. protect the electrodes is kw. At an the remove sulphur. is tilted.

Stassano accomplished the first by careful analysis of the high-grade ore employed and briquetting it with the of carbon and flux. are of capable of roof domed a nearly vertical a four or itself consists furnace The 16 given following content composition. have limits of the carbon Per cent. per produced with resulting metal by other extreme be kw. of the centre Horizontal axis. : " .INDUSTRIAL 224 for the that pig iron ELECTROMETALLURGY refinement further usually produced. volatilization withdrawn are is arc holes slag. three in number. an of energy electrode an been investigators. The alone. At the and furnace horizontal. complete themselves. 4800 analyses of by Stassano containing 48 ore of metal ton expenditure both the gap of arc an magnetite metric Various arc top of the the at metal. to the The of the metal being employed. 10 and the the 50 long is cms. no furnace in the slag reactions. provision must supply of only the requisiteamount addition In in such a that the maimer by which actual the time have jnolten pig the be and retained be of more. cent.introduced slightlyinclined and at the is introduced briquetted charge furnace. diametrically. heating is accomplished by radiation or ore rises the until cavity drawal provided for the with- are employed.and does arc to make be taken as could to 5900 to 15 kgms. heterogeneous metal process for the made of carbon must of the decarburization and purificationis accomplished. the With iron 1 a of consumption of may of but the as becomes 40 some not of the commencement temperature conducting more the electrodes impurities. a magnesia-lined cylinder with slow revolution around electrodes. with contact any to 50 and hours. using pitch or water requisiteamount glass a as to binding material. and two tapping operation short a within the furnace owing to the Since obtained.

molten volts. constant. at steel. per hours when ton per ton following formula when for charged charged determining " p* ) Is VW'^WV /"=the power factor. The " essentiallyof consists This A.The of IRON AND process has FERRO-ALLOYS THE extended not confines the beyond Italy. 225 induced 90 current WV. ft=the frequency. / and hours consumption power : ^--(theratio W5 furnace. sp. the system installed was estimated the lines the at by Gyringe of primary alternating current a 3000 annular an C. resistance of the steel. metal. Induction furnace which Furnaces. 25. and retained are This Furnace. and V where at 800 be Lindblad Kjellin induction " W*=the of area to length of the steel in the channel. was 30.000 amperes was found to with cold hot. B. the J s=the C=a 1.. magnetic resistances of the two circuits. C. 7 650 kw. core of this type With replaced by possiblein as laminated first furnace amp"res is containing the far as in step-down transformer by the primary B. of force is excited the thin sheet-iron The in Sweden. Fig. the power uses factor kw. Kjellin a secondary winding the trough of refractory material A. 15 . The volts.

permitting of it being placed in closer proximity to the secondary. together of with long a high resistance factor is claimed. and from the annular Frick not trough is a furnaces. is term to necessary is factor power right-hand a ELECTROMETALLURGY INDUSTRIAL 226 factor as having a power low as 0*635. hours for serpentinetrough in the a hot spite of furnaces such normal the as hours in order . if it be desired to keep the furnace warm prior to the insertion of a fresh charge. 587 90 ton. for a high to disadvantages the low frequency. a quency of fre- current a on appear employing current of in the form the when consequently greatest small.where operations are of modifications works at Essen the for the production of ferromanganese and melting scrap. factor of 0*90 A power to o*93 is claimed. several of the Kjellin type have been employed. Gronwall difficulties furnaces. If a hot charge be placed in the furnace its capacity is considerably augmented. per 600 . to . simple induction the with factor power furnace. . these coiled Colby utilizes a water-cooled partly overcome. Ferromanganese production Melting scrap Steel refining hrs. of considerable simple operation at Krupp's local required.are in no matter are is desired. A further disadvantage is to be found in the fact that the secondary cannot be completely emptied of metal. usually for the preparation of special steels and ferro-alloys a in which fusion simple overheating is to be avoided. The following figures have been published relating these furnaces : " Kw.The have The very a high secondary low resistance furnace referred therefore would It frequency operated to long thin trough. is used secondary circuit In kw. which Kjellin. and The slag is usually sufficientlyheated. of currents difficulty of the tecting pro- excessive heat from metal long trough of molten radiation. and the calculated comsumption power are per ton of steel is 590 490 kw. a ensure power charge and cold a In Gronwall's one. . pipe as primary circuit. cycles per 13*5 In Colby and the second. slag formation its removal difficulty. .

A. B. suitable found of the cent. E. but by troughs and A. About through the cent. troughs. and through the central refiningsteel. this have annular design have been been The rotation built up for to both difficulties associated of the duced inthe reservoir. embedded liner E. metal of molten means the Rochling surrounded are D troughs between space The soft iron laminated magnesia-lined fireclaywalls composite of steel is the furnace. and the of and steel.AND IRON Composite furnace Furnaces. F. The magnesia becomes sufficientlyconducting at high temperatures to induced in the cable of the current permit of the passage connected through to iron molten the current goes remaining 35 per Furnaces capacity. turns maintain of is cable heavy induction resistance Rodenhauser supplied to be /Y//" / reservoir the accomplished by wound the at desired of means the round furnace. heating of the metal induced extra an in meet a large reservoir a supply of energy ////// IZZZZZZZ the trough is provided by in the current. has to 26. cores protected by are The cores. in the employed Rodenhauser with furnaces common two provided. is thus of the which CE. few a pole pieces and in the magnesia plates F. the 227 successful most preparation the secondary molten-metal the The " induction resistance these In FERRO-ALLOYS THE /t (/.//// 7JZ-L UV/////V Fig. Rochling " This temperature. primary windings B. electromagnetic 65 per molten metal 8 tons paring prewith when . at the opposite ends of the trough.

current caused was by the cylinders of metal Northup axial and axis employed were occasionally depressed depression the densities current by the this pressure ultimately the pointed He induced the slight difference will produce these in a diameter of the the the square radius. Miscellaneous been arc supplementary as electromagneticallyproduced the slag.ELECTROMETALLURGY INDUSTRIAL 228 three-phase referred overcome viz. have wear spin in ash carbon lining due the on Two is metal the in view. may principlesemployed are laboratory experiments the as metal. electrodes the in as low temperature suggested advantages dissolved somewhat of n Gin to obtained the over and the furnaces. perfectlygas-free impurities from no The the Furnaces. small the to erect. metal employed to. surface the fluid fluid in will the be . when investigatingthe operation of the Kjellin furnace. cylinder is proportional to to out directed pressure attraction mutual carrying inversely Under the . noticed that " of the ring that high when metal became divided was the towards coaxial the caused has to the of the that axis of the current Consequently metallic shown and any conductor pressure. of furnaces technical such for steel employed molten interestingtypes furnaces suitable currents of the applied on a applicationof Resistance " proved not high very resistance the low the slag heavy. inasmuch arc as renewal. The Hering "Pinch" Effect Furnace.1* Hering. ceased. by additional an induction furnaces type. expensive is entailed expense those the raised of and Paragon on more offer considerable to already have objection being naturally secondary winding are chief the requisitepower Although the been have heaters. the by this against Nathusius for carbon obtained. furnace. be can owing been cores. of the great alteration conditions the larly perpendicu- exerted square of currents. the metal. To no is current novel for the have yielded highly satisfactory results. necessitated scale which have by not yet since be mentioned. purpose and refining.

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and alloys manufactured important electrothermal applications of was Ferro- stable than crushed Sand quartz has also the furnace. C. furnaces the mentioned be ferro-uranium Arc " the as heating Keller the silicon. 212). raw materials but scrap of presence of source frequent used or of coke.. and ferro-alloys. been silicon. cent. the silicon is of anthracite experimented with. per should phosphorus phosphide the which ferro-silicon silicon grade has Ferro-silicon silicon iron scrap over purer low generally employed are grades. methods Amongst may manganese. now It ore in is made carbon to over grades. from the of preparation described.oys. of wire. electrodes the A The of Tesla a in the 20-kw. The The of one to the Ferro-au. ferro-tungsten. which fiftyturns about induction the ELECTROMETALLURGY size of 60 per to be furnace of the is considered. formerly containing lower since handling of 70 per cent. to the furnace discharge. ferro- (p. of preparation the several in employed. 75 per and cent. The in the form the be poisoning.. is liable to choke of calcium in occurrence more are iron explosions substance. cent.INDUSTRIAL 230 with to of capable The coil.either with Hfroult. containing 25 per cent. .. serves has The connected are and condensers the natural thermal and constructed terminal condenser found to oscillation of period small the voltage of efficiencyis stated the of secondary the as been a high figure when a coil fitted with crucible volts. used. production of ferro-alloysin the electric furnace earliest the preparation of iron silicon. operate successfully with 5400 serve of this ends providing very metal coil. and 7200 primary of primary the as high voltage oscillatingdischarges. 50 per cent. but was of most molybdenum chrome.. prepared shown and The already been be content. quantitiesof production such steel. are titanium. smaller and Ferro for the - resistance In the 90 has and cases of the manufacture and been is combined series the or trode elec- basal a and arc type arc in as originally iron employed.

strong been castings have Tantiron. forms given by the presence of not being flaws eliminated. little carbon during the process of formation. off the impurities absorbs very a hours 75 per kw. and 75 ton. probably associated with the of superficial formation layers of iron silicides. to cent. hours contain size should small required. per of cent. machined introduced have a production non-corroding these variety of Illenit. furnace partly successful. FeSi* and FeSi2made the to Owing of acids. and could recently large castings capable of introduced. practically Ferro - the on a charge electrode. a reduction solidify. depending amount volts. Attempts. blast furnace source of the slags. exceedingly brittle. per ferro-silicon. as stimulus to the The earlier be machined. to . then broken tilting furnaces one the out. to also wasted - system. with in made to pendent and is completed. and were but under to the war of number great a Narki. application of An the to necessary. liners of carbon are frequently employed. and been the such names.IRON The furnace charge crushed sufficient carbon iron from is added metric in for 80 utilizable 30 a the grade of the on single-arc furnace a is kw. roughly 5000 ferro-silicon varies for consumption power cent. only 3500 in the remainder the the is converted charge is used and quartz for into slagging Ferro-silicon coke. When Attempts avoid intermittent lined is allowed have the time Ferro " furnace simple basal tungsten. per the voltage employed 70 a 231 Si02+3C=2CO+Si ferro-silicon The to reduce to equationand FERRO-ALLOYS THE AND electric furnace the recently been has preparation of specialferro-silicon and silicized iron having resistant properties.20 and have been made to sandstone21 ordinary utilize rock as silica. Neutraleisen Metaldtir. and been generally pared preis fused in charge The clay having the is tungsten is use cooling the melt. About and with ferro-silicon grade are according quartz.

in the tungsten small. to and hours are and the metric ton.ELECTROMETALLURGY INDUSTRIAL 232 As used. silica present be most can strictlylimited ferro-silicon power can following analyses of of any decarburization per of by the addition Keeney28 C. CaW04. common supplied by and ores usually accomplished by is iron various of tungsten. of CaW04+FeS+4C=(Fe. Fe2W04. for the .W) Gin duction Re- of coke. hematite. alloys of feirous employed. Excess carbide being reduction addition formation calcium being According iron. source to under gives alloys : " composition. volatilized the at and does process reducing a not appear formation of oxide avoided owing higher grades. loss Sulphide " 3CaW04 carbon the 22 use carbon. FeMnW04. fluxed 28000 carbide.W) + directly reduced be can temperature Decarburization 7500 the as wolframite. the fluoride concentrates reduction to of of low-grade tungsten the with alloy is usually essential o" tungsten for other are manganese of reduction. of the easily be accomplished by amount of the operation decarburization to the (Fe. consumption reduced Hutton24 typicalindustrial be For tungstate. W2C. two a iron is The usually oxide is to with Percentage a flux in the of lime. but owing but electric furnace. of calcium kw. most in the of ferro-silicon of +4Fe2Si =3CaSi03 +FeSi03 Ferberite. and means addition the also been concentrates ore being scheelite. the are is most of iron has used : proposed has instead agent economical of the +CaS+4CO and important tungsten ores.

chief means calcium rustless frequently a operation. and and water sea- operating dolomite liner is may the at to found has malleable although continuous tapped Ferro-chrome " resistant are coal tar. which. furnaces although Heroult for the of scrap As (p. Ferro-manganese. welded. induc- already been has most suitable furnaces have appear and is Ferro-manganese " this work. not being employed.although the carbon mittent inter2 to 5 content considerably higher. the is fed into the furnace Reduction per in of and of carbon. a decarburizing process is necessary. 225) metal and Girod in manganese tion indicated. 11850 C. For the purpose of preparing a low carbon ferrochrome. or employed exceed The base. and specialsteels for naval the production of the steels. been suggested.25 but are prepared by the fusion the electric furnace. usually pared predifferent grades of the alloy in the blast furnace. suc- coarse ensure regular intervals. capable can furnace increasing an so-called and furnace magnesite. military purposes. three mineral usually accomplished by aluminium and The processes latter The anthracite reduction of charge or of carbon a have proved ferro-chrome can be run chromite of at liner a chromium reduction is although silicon. being be walls carbide have of " acids.26 containing only about By from off. by the calcined prevent absorption of manganese dolomite liner. field for in also and in use A with is the with .Cr203.whilst tool carbon alloys the employed are of percentage the metal. for been employed purpose. economically chromite and requisite quantities to at commences tapping cent. coke cessful. finely powdered coke usually lined are source FeO. the walls are frequently protected with a tar To or of retort mixture a Ferro-chrome. may run . " but careful years.the life The chromite.IRON Metallic for used lower for AND higher the steels -hearth open of crucible production grades with 233 high-grade tungsten and tungsten the FERRO-ALLOYS THE content containing low are steels.

coal or The coke heated basal to the correct and the in an electrode equation A prepared averaging 90 per cent.27 always attended to of chromium or of suitable a slag containing chromite fluorspar. . lime alloy is. Decarburization the followingequation : is and accomplished according to " 2Fe3C+6CraC3+5FeO. be lower. by fusion of the alloy with oxide low a Keeney. Ferro-molybdenum the of kgms. electric Reduction +3C +Fe =FeMo2 resulting alloy usually contains of carbon. being together with lime. 7200 25 consumption power hours metric per with ton. ore. carbon by loss excessive an Refining is usually accomplished slag. of carbon. The kw. Ferro-molybdenum. usually of place according takes " 2M0S2 +2CaO The ore are is " from high speed and introduced prepared in increasing quantities. gives Hutton ferro-chromium commercial of analysis following the : " Percentage composition.INDUSTRIAL 234 since ELECTROMETALLURGY direct the according production in the of iron.Cr2O3=iiFeCr2+20CO The carbon and may of the resultingalloy is usually below 0*5 per cent. furnace. Chromium-nickel are loss electrode an and typicalanalysis is as +2CO +2CaS from follows 3 to : " +CS2 4 per cent. anthracite. proportions of iron turnings. 6000 between ranges tool metal alloys for have the recently been production of molybdenite MoS2. or concentrates or raw roasted intermittent type.

" and Ferro-titanium. silicide. ferro-silicon and by of tar. experiments by Keeney have shown the ferro-alloycan be accomplished and at alloy containing from an be reduced supply about brought amp"res By reheating with carbon. The amount oxide is frequently very high and may commercial for molybdenum to much as Ferro preparing been have which The " ferro-vanadium thermite electric furnace for method only recently supplanted the has great variety of processes A process. the carbon of 900 current will being iron.SiFeV ferro-vanadium From and vanadium fluoride. the requisite of iron. is made preparation similar Ferro-titan- by smelting .have all proved too expensive iron loss by volatilization practice. iron an from cathode double a electrolyte. aluminium and by means slag. usual more 30 per cent. From by in small furnace arc 4 to 6 per cent.including ferro-silicon.IRON AND Decarburization by of 235 desulphurization and means FERRO-ALLOYS THE slag containing lime a be can plished accom- oxide and of of carbides. patronite. Boron.amongst be mentioned may Fusion 1. used as a deoxidizer for cast 50 volts 1 per cent. 1 vanadium. 5. Uranium ium. means 3. suggested for the production of the alloy. means a the A largestsource provide content of can is the of to that a limited amount to under that in a the manner employed for ferro-molybdenum. Reduction silicon. sulphide ore. amount trioxide vanadium Briquetting 2. with 3 pentoxide. as - of of " mixture a part of silica and of parts vanadium 10 parts of carbon. of carbon. of oxide The reduction oxides. Electrolysis with fluoride 4.

Richards. 1901.. 1 904. P. Gin." Electrochemistry. p. J. 10 Askenasy. 181 .. in der ' ' S.. Electrochem. Electrochem. 1910. 1912. BIBLIOGRAPHY. 19. Min. Trans." Electric The " o. 9. Electrochem. p. April. and Chem. 173. 315 . 1910. Stansfield. W.C. Amer.R. 10. Industrial Applications. Electrochem." Electrochem. 489 . 1900." F. 15. 642. 14 Stansfield. A. Soc.." 5th Auf. " " " Einfiihrung in die technische Congress of Applied Chemistry. or of aluminium. vol. 1914. 18. p. Amer. Furnaces. 16. p. 191 6." Allmand. iron sulphide prepared by reduction or carbon uranate.383" Crawford. 1912." and Chem.S. 1484 37 Trans. 33 Eng. Farad.. Elehtrochem. of Steel. 177. 93. 18 Trans..INDUSTRIAL 236 titaniferous uranium iron with ore alloy has sodium been with calcium carbide boric with acid the oxide. 20. 15. 859 of VIII.." " 15. Electrochem. Furnace. 1914. W. 24. Faraday Soc. p. and 33 Trans. 36 J. p. . Met. 1908. 1908. 1910.. Industrial and . Allmand. Applied Electrochemistry. 6. Eng. K. Eng. Industry. Quantitative Analyse durch Electrochem. ElektTochemie." Metallurgy their A. Rideal. Eisenindustrie. p. . Ind. Harbord. 30 G. 564 . Amer..." 7 Zeit. Amer. 7. Amer. 182 vol. Soc. with or The of scrap of iron oxide alloy is boron iron by and borax carbon. 255 p. " Elektrische ' ' Electric " The " Furnaces Electric "Applied "The Ofen and Furnace. Amer. 13 Trans. or prepared Na2Ur207. 25." by E. 127 Soc. smelting and ELECTROMETALLURGY and Steel. 1911. 1912. 34 " 38 F. vol. 1912. Steel. Soc. 13 Electrochem: 17 Trans. 1907. "Electric Ind. 5. 1907. p. Electrochem. ." Einfiihrung "Stahlu. 24.. Met. Dec. 3 D. 191 * 0 7 Elektrolyse. 19x7. 11 See " 13 Chem. 191 14 Trans. J. 172 . U308. . Wright. Electro. . 7. SECTION TO of Iron Rusting lime and mixture a REFERENCES The uranium or whilst quantitiesfrom in small ferrosilicon. " Harbord. 1914- J. 1909. 205 . Wright.. in die technische Eisen. 31 Met. 25. Electrochem. 19 Trans. 19"." Askenasy. Amer. P#*"i^ Soc. 134 Jour. 8 Soc. 86. patent 4 Trans." Rodenhauser. 1 " 3 Zeit. Amer. Soc. Metallurgyof The . Elektrochemie. 8. Nov. 11. Trans." 1908. p. Electrochem. 1913. 1. 16. Soc. Soc. 1914.. 1909.

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91 Beutel. 227 104 Beatson. Crookes. 123 53 72 Bassett. 102 De Laval. 94. 132 146. 97 r. 34 Caro. 37 Boissiere. 93 Becker. Mond. 72 Arndt. Bancroft. Bottger. 196 Body. 126 Beardslee. 155. Acker. 72. 117 Allmand. 95 Faraday. 28. 74. 169 Cowles. 206 Burleigh. 199 Bullier. 138 Burgess. 196. 146 42 Elkington. 146 94. 42. 152 Benjerink. 112 Becket. 151 Clarke. Claude. 74 Bicknell. 137 Brochet. 42 Eisner. 199 Dechert. INDEX Carmichael. 206. 173 85 Caspari. 10 72. 123. 121 Bischof. 119. 219 Field. 86 Coles. Andrioli. Cohen. Elmer. 177 Bunsen. Dumoulin. 150 73. 117 10. 42 Bergsoe. 102 Blount. 123. 169 155. Davy 122. 154 Diesel. 199 Borchers. 101 Brode. 199 Classen. Brunner. 65 Bucher. 207 Colby. Aschermann. 43. 20 Doelter. 196 186 Cavendish. Ashcroft. 2. 179 104 Brand. 191 28 Bessemer. Consiglio. 147 Dennis. 137. 82 97 Elmore. Arrhenius. 208 . 68 Broadrill. 95 Berkeland. 51 112 186 Dawes. 93 Dorsemagen. 69 Clergue. 100 Castner. Feild. 186 Berthelot. 133. 220 Dolch. 109. 85. 165. 200 Carrier. 60. 74. Bennet. Betts. 135 Desmur. 144 183 22 Daniel. 121 3 Clancy. 201 Claus. 44. 8. no Brown. 120.NAME ACHESON. Cowper Cullis. Bayer. Darling. 166. 92 115. 87. Anderson. 65 150. 102 Deville. 83 Englehardt.

Grosz. 220. McDougall. Harden. 94 Gaudin. in 214. Griesheim. 49. 66 233. 117 Hutton. 154 Moebius. 199 Memmo. 137. 79 Moissan. Hewes. 235 231. 142 Muthmann. Langbein. 149 Hoepfner. 146 Irvine. Gillet. 233 Girod. 73. 138 Heyn. 150. 149 Mounden. Harper. 187 150 Luckow. 103 188 Lyons. 44 Gelsthorpe. 159. Kendall. 59 197 LebJanc. 83 93 Greenawalt. Kalmus. 227 Krutwig. 222. 117 Fitzgerald. 45 186 Howies. 200 Frary. 62. 121 Jacobsen. 88 Maxted. 149 Lampen. Hausser. Fischer. 175. Minet. 179 Mennicke. 234 Goldschmidt. 155. 66 172 206 . Marchese. 102. Harmet. 137 Harbord. 213. 231 226 Klapproth. 177 233. Hnlin. Greenwood. 158 168 93. 165 Gin. 234 99 96 186 Meliner. 92. 103 Keeney. 130. 229. 152. 135 197 Leucks. Hampe. 152 Gunther. 65. 136 Mylius. 201 Lodge. 179. 90 Krupp. 155 Frank. 146. 66. 187. 10. Morrison. 96 Horry. 98 Kjellin. 5 35. 82. 158 28 Hellriegel. 76. 88. Hemingmay. 77. 33. 94. Kuster. 125. Heroult. Holfis. 145 226 62. 207 Lindblad. Mathers.192 Margueritte. 95 Henderson. 142. 5 226 2 Lorenz. 201 no. Keller. 188 Hall. 152 Lepieme. 125 206 Hambuechen. Linde. 165 158 Landis. 121 Goodwin. 150 229. 213 Haber. 227 Guichard. 186 Johnson. 72 Helfenstein. 86. 154 Grotthus. 236 Keith. Koenig.NAME 240 Imbert. 135 206 130. Geer. Hering. 37 1 81 153 Ladd. 69. Haycroft. INDEX *35 Forsell. 148. 96 Merke. 141. 214 124 ' 214 137 Machalske. 87 Li. 235. Laszczynski. 153. 222. Fromm. 142 104. Helmholtz. Leaner. Frick. 82. Kern. 187 Kohlrausch. Haanel. 230 177 Hildebrand. Foerster. 199 89 Matuscheck. 66. 214. Hittorf. 9. Gronwall. 198 88. 94 214 Lyon. 95 213. Lowry. 73 Jellinek. 136 1. 98 Guntz. Lepinske. 2 Gruszkrewicz.

139. Neumann. 142. 187 Rudolphi. Townsend. 120 Russell. 67. 76 Pfanhauser. 67. 94 Palmabk. 71. no Kugelgen. 95 230 Norton. 5 Smith. 95 Rochling Rodenhauser. 165 Waldbn. 198 Swinburne. 45. Van *t Hoff. 42. 222. 135 82 Nathusius. 165. 137 Perkin. 82. 170 128 Richards. 187 Pederson. 47. Planck. Stalhane. 2 Steiner. 33 Rienders. Neill. 175 5 Thum. Nicola jew. Nodin. Wallace. 114 3 76 Wannschaft. 186 192 Seward. Suchy. 169 Powell. 198 Valentine. 34 Nernst. 138 Simon. 224. I. Schucht. 32. Pauling. 142. 144 Sand. 89 Snyder. 102 Preeble. 63 168 Thompson. 120 Quintains. 166. Nauhardt. 81. Roseleur. INDEX 222 95 Neil. 74 95 186 158. 87" 125 Sourdeval. 74. Vogel. 119 Ost. 168. 5 Pattison. Obstbrlb. Thomson. 188 Read. 124 Swan. 199 Senn. 96 Northrup. Swindel. 201 Regnault. 63. 97 Rossi. Savell. 231 Thiel. 101. 158 Parkes. 47. 65 Siemens 28 Halske. 117 124 220 Ruff. Watt. 146 Oettel. 228 166 85 Van Arsdale. 193 Tuttle. 5 Plato. 5 Parker. 120 Strutt. 136 Noyes. 79 Tommasi. 77. 199 214 Stansneld. 241 Scholl. Vogt. 184. 89 Possoz. 98 Tucker. Tainton. 193 Readmann. 76 Priag. 114 Sharpe. 59. 92 Saunders. Von 34 Waal. 123 199 Tesla. 188 173 65. 159. 157. 76 Salgues. 155 Tronson. 86 Pott. 44 99 16 . Van der Van Laar. 94 Schwabe. 48 92 88 Snowden. 81. 90 Overman. 3 Vautin. 120. 86 Paschen. Stockem. 76. 154* 214 Stassano. 103 59. 135 Thiele. 102 Potter. 154. 217 Newton. 113 186 Schonherr. 130.. 73. 69 Von Von Ruolz. 102. 76. 89 Tone. 29. 186 Rayleigh. Taylor. 225 Steele. 3 5 Hevesy.NAME Namias. 229. 88 199 Ramsay. 121 Trumm. Serpek. 15. 2. Ricketts. 90 Smit.

NAME 242 Watts. 170 Westman. Whitney. Wilson. 103. 2 47. 104. INDEX 48 79 136 Woolrich. Weidlein. 207 Withrow. 65. Winogradsky. 159 Whetham. 69 132 . Wood. W6hler. Wright. 34 Weintraub. 177 191 76 120 Wohlwill.

221. 218. 65 Biochemical nitrogen. 84. 63 Bauxite. 208 Arsenic. 125 reduction. 62 Bombs. 155. 60. n Cast 191 72. 102 hydrogen. 152. 231 Caliche. 88. 173 Benzoic Absorption. 83 Briquetting. 102. 1 17. 195 nitride. 157 Ammonia. fluoride. 133 Aromatic acids. 59. 190. Blast Bleaching 192 Allotropy. 195 preparation. 65 Calcium. 54 157 furnaces. Cadmium. 198. Carnallite. 177 208 Blowing off waste gas. 76 theory of electricity. 26 nitride. 137. 68. Active Alcohol Algae. 170 121 iron. 176 alternating current. 184 Carbon. 158 Bromide Arc Brass. 187 9. 8 0 Acetate electrolytes. 65 Addition acid. 237 Alumite. 30. radicMa.INDEX SUBJECT Abrasives. Burnishing. 40. 190 186. 76 54. 84. 169. 59 furnaces. 61 potential. 133 phosphide. 140 Boiler efficiency. 192 147. 52 reducers. 155. 72 Auxiliary electrodes. 191. 79. 184. 157 Antimony. 193. 120 carbide. 201 cyanide. 50 By-products. 193 204 200. 131 Anthracite. 105. Argon. 136 199 91 . 234 cyanamide. 157. 135 Calamine. 237 Borides. 191 Bipolar electrodes. 181 Boron. 60 powder. 11 Cathode depolarisation. 92. 89. 71 salts. 225 ore. 99 rotation. 193 cathodes. 159. 199 Basic salts. 153. 125. Analysis. Apatite. Alloys. 213 Catalysis. 133 carbide. 81. 39 Carborundum. 84. 233 220. 146.x Aureus Bacteria. 89. Barium. 39. 88. 22. Atomistic 190 Boric deposits. 120. Cataphoresis. 198. 234. 8. 53 furnaces.18 8 alloys. 2x9. disulphide. agents. 52 Broken Anodes. Argentium. 39. 59. 45 Cerium. 160 164. 186 Brighteners. 102 naphthol. Auric salts. 54 Blende. 122 cyanamide. 26 Alunduxn. 198. Arsine. Blue powder. 83. 89. Block Aluminium. 190 acid. 54 material. 39. 31 Bismuth. 13 151 222 BACILLUS Hill Bronze. 164. 193 Aquadag. 84. 176 Asymmetric 59 electrolytes.

4. 52. 187 Electroplating. 209. 226. 219. 107 222. 25 Cyanamide. Dextrin. Complex Contact electrc Copper. 42 Float 40 of ores. power. electrolytes. Coconut charges. 10 Explosives. 151. 60 196 Decarburization. alloys. 229 1. 220. 228 electrolytes. Dyes. 132 Cuppelation. chloride manganese. 83 Colloids. Electrode Galena. 59 135 tannic acid. Electrotype. Diffusion currents. 7 235 Fertilizers.42. titanium. 8. 153. 125. 37 Ferric boron. 82 gold process. 151. 41 Emulsification. Charcoal.44. 146 214 Chemical INDEX 198. 233 Fermentation. in 28. formation. 236 Flotation Deoxidation. 187 nickel Chrome Chromite. 189 103. Ferro alloys.235 Chromium. 8 21 preparation. 152. Eikonogen. 218. 45 potentials. 236 32. hydride. 146. 237 chrome. 18. 20 Equilibrium constant. Dynamic Education. Electrostatic charges. 54 Corrosion. 32 Collodion. 218 Flashing. theory. 227. 236 vanadium. 73. induction. depolarizer. 157 Galvanizer's dross. Comminuted 21 Ferberite. 20 producers.10. radiation. 23. 147 Gallium. 185 leach. 25. 5 Duralium. Galvanizing. 120. 33 evolution. 224. 157 59. Dissociation 224. 63. 23. 19. 189 67 109 102 . 65. 102. 65 59 electrolytes. 85. Garnet. : js. 35. 175 electrolytes. 235. 25 Gas films. 51 Cupriferous pyrites. 61 Cyanogen. Chloride reactions. 23. 102 235 Fluxes. 183 equilibrium. 183 127 Coal. 55 81. 79 no films. steel. Fluosiucate Destructive Diaphragms. 52. 239 Cryolite. tungstate. Crucible 39. 183 70 233.233 Fluorspar. Felspars. 213. 3 Electromagnetic fields. 183. 5. 183 86 Fractional crystallization. 218 165. Cobalt. 236 tungsten. 47 resistance. Diamond. 234 silicon. 222 226 234 133 39 131 supply. zoo Evaporation. 235 140 222 1S8. 66.SUBJECT 244 Channel formation. 208 Fog formation. 18. 57 Gallo 45 65 arrangements. 147 79. 10. 234 Ferrocyanides. 153. 234 84. 186. 176. Fire 234. molybdenum. 232 uranium. Chlorine Cloud Electrolytic agitation. Furnaces. matting. 89 10 removal. 41. Fluoborate Food 45. 200. Fused 2 Dolomite liners. 12. n. Dephosphorization. 204 Cyanides. 234 Engines. 231 168 sand. 92. 153. Ferrous sulphate. 192 electrolytes. 87 188 Combustion.116. 81. 77 Cupramines. 185 Desulphurization. Dropping electrode. 17 tar. Depolarizers. 236 208 150. 81. Citric acid. distillation. 4 side Chilled arcs. 25. Chemical potential. 154 arc. 192. Electronic 124 theory. 74 91 slimes. 41.

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!95" 153. processes. Protective Striking baths. 88 Pyrometers. 8. INDEX Patronite. 150 70 Tin 98. of Pigments. 234 233 Turbo-generators. carbide Revolving Rhodamite. 82 Sulphur dioxide. n. 224 Sickening 220. 165 monoxide. 175 113. 214 soluble. Rotation of Rustless 175.168 Silit. 226 slags. 219. 199 peroxide. 84. 231. 234 188. 9 Reducing agents. 39.73. 150 Spongy deposits. Tantiron. 185 Tuyeres. 191. Potassium. 103 232 furnaces. 159 Slags. 13 198 . 88 Phosphate electrotytes. 143. Sulphuric acid. 75 Solid 40 Polishing. 232 96. 192 Synthetic ammonia. 114. 109. 196 of mercury. 169 Siloxicon. 150. Solution Soot. 65. 39. 45. Tannin. 236 nitride. 18. Tidal 92. 18 Peat. 96. 176 Phosphorus. Surface 219 furnaces. 234 Titanium. 209 Pig iron. 1 numbers. 135 Thermite. Sodium. 82. Tin. Tungsten. 165. 195. carbide. 43 proprietors. 208 furnace. Power. 53 Prussian blue. 53. Transmission Transport 137. of power. 217. 71 Pyrogallol. 17. 140 Spiegeleisen. 178 160 218 8 Symbiosis. 158. 42 Spark discharge. 76 Sulphocyanides. 185 Smoke Peeling 104 Peptone. solutions. 8. 66 xoi 122 Sublimation 214 25. 195 92. 24. 153 Thioantimonates. 208. 215 15 187. pressure. 169 colloids. Refining. 189 of metal. 65. 70 sulphide. 117 Printer's ink. 81 deposits. 195 221 166 21 25 Roasting Rubite. 97 24 steel. 207 91 Thiostannates. 59 Silicon. 32 232 velocity. 156 10 3. loss. Praseodymium. 92 14 energy. Tilting furnaces. Silidizing. 198 Spelter. 79. 179 electrolytes. 136 Self-induction. 35. 176 168 Silundum. 94 Steel. Quartz. Radiation 87. pressure. 175 Sewage sludge. carbide. 8. 217. 197 Stassfurt 131 196 191. Tapping 59 cathodes. Sugar. 117 cyanide. 218. 26. 113 Softening Doint 97 220 86 40. 52. gold. 42. 147. 165 nitride. 12. Sodium. 153. Pyrrhotite. Phosphine. 53 Sulphide of carbon. 236 Silver. 197 12. 89. 169 Porous deposits. 15. Samarium. 147 Reaction Resistance Resources of ores. 168 Silica bricks. 6. 98. Phenol. 145. 193 Perchlorate electrolytes. 153. furnaces. Turf. 53. 73 Sulphur.246 SUBJECT Passivity. 37. cyanide. Si.220 Stannates. 185 Shaft furnaces. Silfrax. furnace. tension. 229 Platinum.88 Smothered arc Sodamide. 183 77. 209. Tellurium. Peasant Slimes. 93 scrap. 109 Pinch effect. 216 Strontium. 89 Tartrate Thallum.

carbide. Tindall electrodes. 247 12 power.INDEX SUBJECT electrodes. 84. 8. 9. 44 Water cooling. 236 166 21. 1 123. 137. 221 gas. 233 Zinc. 208 KND Cox. 58. 141 Velocity of reaction. 153. Covert Garden. 70 Viscosity of slags. 138. W. Henrietta Street. 45 Unattackablb Uniform deposits. 189 Vanadium. Waste Zones THE " of 39. 236. 153 reduction. Wolframite. 24. 25 Zirconium. 153. 153.C. 25. . 66. 62.179. 209 BaiUiire. Uranium. 179 197 25. 71 Zircon. 8. carbon. 218. 128 Whitewashing Vapour pressure of zinc. 139 Zinc scrap. Water gas.