CALCIUM CARBIDE AS A METALLUR- 
 GICAL REDUCING AGENT 
 
 BY 
 
 SAMUEL COHN 
 
 THESIS 
 
 FOR THE 
 
 DEGREE OF BACHELOR OF SCIENCE 
 
 IN 
 
 CHEMICAL ENGINEERING 
 
 COLLEGE OF LIBERAL ARTS AND SCIENCES 
 
 UNIVERSITY OF ILLINOIS 
 

 dQ>Q, 
 
 UNIVERSITY OF ILLINOIS 
 
 J" ^ o - *-« 
 
 : - a'-*:' ^ ig2fj 
 
 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY 
 
 ENTITLED 
 
 k.u 
 
 
 
 IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE 
 
 DEGREE OF 
 
 in 
 
 A-t _ JE'ii ^X. I i'S T_i I 
 
 Instructor in Charge 
 
 Approved : 
 
 HEAD OF DEPARTMENT OF 
 
 
 
 
Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/detaiis/calciumcarbideasOOcohn 
 
ACKHOWL3DGM13NT 
 
 The author takes great pleasure in acknowledging 
 his indebtedness to Assistant Professor W, S, 
 Putnam for his invaluable advice throughout the 
 preparation of this thesis. 
 
Contents 
 
 Introduction 
 
 The purpoee of this article 
 
 History 
 
 The preparation of oaloium carbide 2 
 
 Properties of calcius carbide 2 
 
 Reactions of calcium carbide with metallic oxides 4 
 
 Pago 
 
 1 
 
 Effects of sulphur and phosphorus in steel 
 Present methods employed in removing sulphur 
 from steel 
 
 Experimental 
 
 Analyses of the unreduced sulphur remaining 
 in the fusions 
 
 Summary 
 
 Bibliography 
 
 6 
 
 Determinat 
 
 ion of 
 
 the 
 
 purity 
 
 of 
 
 calcium 
 
 carbide 
 
 9 
 
 Dotorminat 
 
 ion of 
 
 the 
 
 purity 
 
 0 f 
 
 ferrous 
 
 sulphide 
 
 10 
 
 Procedure 
 
 in m a k 
 
 i n g 
 
 a fusion 
 
 of 
 
 calcium 
 
 and 
 
 
 ferrous su 
 
 1 p h i d e 
 
 
 
 
 
 
 10 
 
 1 1 
 1 5 
 
 17 
 
CALCIM CARBIDE AS A IfflTALLURGIGAL REDUCING AGENT 
 
 INTRODUCTION 
 
 The diaulphuri.'sation of sulphide ores or pig iron by a sim- 
 ple process of oxidation is very far from complete. But if disul- 
 phurization is to be thorough, it must be, by converting the sulphur 
 into calcium sulphide, -which is universally carried out at present by 
 adding lime to the molten mass of impure metal; the reaction takes 
 place in the following manner: 
 
 PeS + CaO + C = CO + Pe + CaS, 
 
 The CaS is then removed by the slag. 
 
 In this work, the object is to remove the sulphur as CaS, j 
 but it differs from the ordinary method, in that 0aC2 is employed in | 
 
 I 
 
 place of CaO. This is to be carried out by heating iron sulphide | 
 with the carbide at some definite high temperature, the iron sulphide | 
 acting as a representative sulphide ore. In narrowing down the pur- | 
 pose of this work to the most concise wording, it is to study the re- | 
 actions of calcium carbide with ferrous sulphide, and determine 
 whether these reactions can be applied in desulphurizing steel. 
 

 
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HISTORICAL. 
 
 i’rom tlie earliest date in the history of metallurgy it has 
 been recognized that sulphur and phosphorus are haimful elements in 
 steel, and the problem of their elimination has not been thoroughly 
 solved, Among the many methods and reagents that have been employed, 
 comparatively little has been done with calcium carbide. 
 
 It seems advisable to state the manufacture, properties, 
 and reactions of calcium carbide now, so that the reader will under- 
 stand why certain methods of attack have been used later on, 
 
 Calciuia carbide was first prepared by Woehler in 1862, by 
 
 1 
 
 heating an alloy of zinc and calcium to a welding temperature. It 
 was not until Wilson’s discovery in 1892 that it could be commercial- 
 ly manufactured in the electric furnace. This process consists of 
 heating a mixture of finely pulverized limestone and coke, in an e- 
 lectric arc at a temperature of 1600 degrees centigrade. The re- 
 action which takes place in the furnace is as follows: 
 
 CaO + 3c • CaC2 + GO — 105350 calories. 
 
 Theoretically, this reaction would require a mixture of 875 parts by 
 weight of lime to 5^3 parts of carbon, but in actual practice about 
 650 parts of carbon are needed, since some of it is consumed in other 
 ways than by the above reaction. 
 
 The carbide as taken from the electric furnace is hard and 
 crystalline, but loses its luster on exposure to air, especially when 
 moist, and finally crumbles to a gray powder, containing many graph- 
 ite particles. It may be kept unchanged in a well closed bottle; 
 
 best in the presence of coal-oil. When pure, it is colorless, but 
 
 2 
 
 small amounts of foreign matter render it reddish brown or black. 
 
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 The specific gravity is 2.3 and the melting point is in the neighbor- 
 hood of l800 degrees centigrade. It is easily decomposed by water to 
 form calcium oxide and acetylene, the chemical equation being as fol- 
 lows: 
 
 CaC2 + H2O = C2H2 + GaO. 
 
 Theoretically, one pound of carbide should require .525 pounds of 
 water for its decomposition and the products formed should be 1,156 
 pounds of lime and ,4064 pounds or 5»535 cubic feet of acetylene at 
 zero degrees centigrade, But on account of the impurities, the best 
 results obtained have been 5 Gu, Ft. of acetylene. Upon decomposi- 
 
 4 
 
 tion of one pound of the carbide, ^00 B.T.U, are liberated. 
 
 If the carbide is heated in hydrogen, a little tarry matter 
 and a slight white sublimate are formed, but it is otherwise unalter- 
 ed, even after long heating. Heated in air, the same tarry substance 
 is formed, but no other action is apparent; even with oxygen, the 
 carbide is unaffected until a very high temperature is attained, when 
 the materials glow brightly, yielding a white powder. 
 
 Hydrochloric acid has no action in the cold, but on heating 
 it causes the carbide to swell up and become dirty gray. A small 
 quantity of colorless liquid distills over, white fiames are evolved, 
 and a part of the solid fuses, being converted into calcium chloride. 
 Chlorine is also without action in the cold; at a tempera- 
 ture of 245 degrees G, it causes the carbide to glow brightly, to 
 swell and to fuse together, while a slight yellowish- white sublimate 
 is formed; the fused mass is calcium carbide. Bromine reacts at 
 350 degrees C., and sulphur vapors at 500 degrees G, The products of 
 the last reaction are calcium sulphide and carbon disulphide. Pe- 
 troleum, benzine, carbon disulphide and carbon dioxide do not have 
 any effect. 
 

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 Strong sulphuric acid in the cold gives a few hubbies with 
 calcium carbide, but on heating, the action is increased and contin- 
 ues after the source of heat has been removed. Strong nitric acid 
 
 I 
 
 produces red fumes, but the gases from this and from the sulphuric 
 acid, burn with a luminous flame. A solution of sulphuric acid and 
 potassium bichromate react violently with the carbide, forming a non- 
 inflammable gas. The carbide acts as a reducing agent to many oxides 
 and if present in excess, tends to allow the calcium to combine with 
 the reduced metal. In this manner, alloys with iron and other metals t 
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 of ferro manganese, being more brittle and easily oxidisable in con- 
 
 5 
 
 tact with water. 
 
 If an excess of litharge be heated to redness in contact 
 
 with the carbide in a clay crucible, the reaction is accompanied by 
 
 vivid incandescence, resulting in the formation of metallic lead and 
 
 calcium oxide; but with certain calculated proportions of the lith- 
 
 arge and carbide, an alloy of lead and calcium is formed which is 
 
 more or less brittle, having a melting point lower than pure lead. | 
 
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 peratures are readily reduced, giving results of no practical value. 
 
 In a further operation, oxides of manganese, nickel, cobalt, chromium, 
 
 6 
 
 molybdenum, and tungsten were readily reduced, yielding calcium alloyi . 
 
 Since calcium carbide is a deoxidizing agent, it will there- 
 fore, when added to a metal in the state of fusion which is always 
 slightly oxidized, react in the following manner: 
 
 (1) CaC 2 + 2M0 = 2C0 + Ca + 2M. 
 
 It is evident that under these conditions, as one part of the car- 
 bide only takes part in the above reaction, the utilization of this 
 compound is not to the best advantage. To increase its power, a 
 
7 
 
 metallic chloride, RCl, which must toe dehydrated, may toe added; the 
 Cl will comtoine with the Ca set at liberty, in such a manner, that 
 the two affinities of the C for the 0, and of the Ca for the Cl, will 
 act simultaneously, giving the following reaction; 
 
 (2) CaC2 + 2RC1 + 2M0 = 2R + 2M + CaCl2 + 2C02* 
 
 These reactions may toe applied either to the extraction of a metal 
 from its ores, or for the manufacture of metallic alloys, according tc 
 whether the metallic chloride used corresponds with the metal or not. 
 
 If M=R, we obtain the metal only; if not, we obtain the alloy R + 2M. 
 
 As an example of this formula we can give the preparation of aluminum 
 bronze, which consists of gently heating a mixture of alumina and 
 chloride of copper, in contact with calcium carbide. 
 
 In an article taken from the Journal of Society of Chemi- 
 cal Industry (1902, page 1302) the above reactions (l) and (2) are 
 stated to react in the following proportions toy Heuman; 
 
 (3) CaC2 + 3MgO = 3M2 + CaO + 2C0 . 
 
 (4) 2MC1 + 2M2 + CaC2 = 3M2 + CaCl2 + 2C0 . 
 
 But Kugelgen said that the above reactions take place as follows: 
 
 CaC2 + 5M2O ~ ^®2 CaO + 5M2 and 
 2MC1 + 4M2O CaC2 — 5M2 CaCl2 ^ 2C02» 
 
 Alumina which cannot toe reduced toy cartoon even at a white heat, is 
 reduced toy the carbide in the following manner; 
 
 Alp03 + CaCg = 2A1 + 2C0 CaO. 
 
 Calcium carbide is also a reducing agent for many sulphides. 
 Pyrites, tetrahedrites, galena, stitonite, and magnesium sulphide are 
 all reduced when heated with the carbide in an electric furnace, leav- 
 ing calcium sulphide; tout all the metals, except the iron of the py- 
 rites, and the copper of tetrahedrite are volatilized. Aluminum sul- 
 
 8 
 
 phide is not reduced when thus treated. 
 
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It may seem from the first paragraph of this article that 
 phosphorus and sulphur have no heneficial effects when present in 
 iron or steel, but to be sure, they have their virtues as they have 
 faults, of course, the latter being considerably more numerous than 
 the former, phosphorus is probably the most injurious impurity found 
 in steel with the possible exception of the occuluded gases such as 
 oxygen, hydrogen, and nitrogen. The ill effects of phosphorus are 
 very apparent when the steel is cold. It produces the phenomena of 
 "cold shortness" or brittleness when cold, either in hardened or an- 
 
 9 
 
 nealed steels. This brittleness is especially noticeable when the 
 steels are subjected to vibratory stresses or to shock. The ductili- 
 ty is very little affected when the loads are slowly applied. Exper- 
 iments have proven, that in amounts up to .12 per cent, phosphorus 
 increases the strength under slowly applied loads. Under shock how- 
 ever, this material was a failure. The bad effects of phosphorus in- 
 crease as the carbon content is increased, due to the formation of 
 coarse crystals which tend to produce brittleness. 
 
 Phosphorus produces a phosphide of iron, Ee3P, which forms 
 a series of alloys with iron. The eutectic of this series contains 
 69 per cent of the phosphide or 10.24 per cent of phosphorus, and is 
 very brittle. A small amount of phosphorus will dissolve in the iron, 
 forming no brittle eutectic, but as the carbon is increased, it pre- 
 cipitates the phosphorus from the solid solution into the brittle 
 eutectic form. Thus the lower the carbon, the more phosphorus may be 
 present without being seriously injurious. 
 
 Phosphorus increases the tensile strength of steel somewhat 
 as does carbon, but does not decrease the ductility as rapidly as 
 does carbon. Phosphoretic steels resist wear better than steels with 
 a lower phosphorus, and high phosphorus is permissable or even desir- 
 
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able If the steel is to resist abrasion only, and no shock or vibra- | 
 tion is to be encountered* phosphorus increases the hardness of 
 steel without lowering the electric conductivity as much as other j 
 hardening elements. For this reason, high phosphorus steels are used! 
 for third rails of trolley systems. 
 
 High phosphorus steels are used for screw machine products, j 
 where shock strength is not a requisite, as it gives excellent ma- 
 chining properties, producing clean bright surfaces, and increasing 
 
 I 
 
 the tensile strength. ! 
 
 I 
 
 Sulphur occurs in commercial steels as manganese sulphide, | 
 and when manganese is absent the sulphur is present as FeS, of which 
 the former sulphide is a less harmful constituent; the reason being 
 that FeS spreads out in webs or sheets instead of coalescing in drops 
 
 I 
 
 as MnS does. Steels for several purposes such as that used for long- 
 itudinal strength are benefited by a certain amount of manganese sul- 
 phide; sulphur in low carbon steels improves the free cutting proper- 
 ties. Sulphur is considered most harmful at rolling temperatures, | 
 since during this process the steel is liable to crack. Steel em- 
 ployed in places where it is exposed to corrosion, must have all the 
 sulphur removed, since sulphur promotes corrosion rapidly. 
 
 In the present day manufacture of steel in the United State i 
 sulphur and phosphorus are removed by the Basic Open Hearth process, 
 while in England and Germany, these elements are eliminated by the 
 Basic Bessemer process, the difference in choice of the two processes 
 being attributed to the contents of the raw materials found in the 
 above three countries. 
 
 10 
 
 In the Open Hearth process, the sulphur and phosphorus, 
 also silica with several other impurities, are removed by the slag. 
 Steel scrap is spread over the bottom of the furnace; this is covered 
 

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 with a heavy charge of lime, and the lime is covered by a charge of 
 scrap and pig iron. After two hours, the heat of the furnace has 
 softened this charge so that it has sunk, and then the final charge 
 of scrap and pig are added. In order that the slag may at all times 
 be rich in lime, small amounts are added from time to time accord- 
 ing to the impurities present. The limit of GaO to be added is 55^, 
 since more than this amount will form a viscous infusible slag. Man- 
 ganese, if present, also assists in the removal of sulphur by forming 
 MnS. The sulphur in this case is slowly oxidized and the manganese 
 returns to the boiling solution of metal. 
 
 By the Basic Bessemer process, the sulphur and phosphorus 
 are removed during the afterblow period, which is carried on in a 
 converter. The converter is supplied with the molten metal and is 
 blasted for a certain length of time depending upon the amount of im- 
 purities present. Lime is added in amounts sufficient to oxidize all 
 the impurities. Some sulphur is oxidized during the blow and the re- 
 mainder passes into the slag in the form of CaS. 
 

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EXPERIIffiNTAL . 
 
 On account of the method of manufacture of calcium carbide 
 it most usually, as previously stated, contains impurities. The 
 first step in the experimental work is therefore to ascertain the 
 purity of the carbide, since it is to be used throughout this prob- 
 lem. 
 
 An exact amount of carbide was weighed out and placed in a 
 dry flask. As shown in the diagram, the flask was connected with a 
 
 dropping funnel, two CaClg U-tubes and a train of flasks. The drop- 
 ping funnel was filled with a 2(y% brine solution. 
 
 G'Cn.ftra.t’or Trap MaOO A<mw>oniOwCoJ ^o\o+ion. of CoCi 
 
 The gas was liberated by allowing the brine to drop on the carbide 
 verj'" slowly, and when the reaction seemed to cease, the generator was 1 
 heated in order to complete the reaction; a saturated brine solution 
 was used because acetylene is Insoluble in it, and soluble in water. 
 The first U-tube served to remove the moisture from the air current, 
 which swept the non-absorbed gases into the solutions. The second 
 U-tube served to catch the entrained moisture in the acetylene. The 
 trap was employed to regulate the passage of the gas in the train of 
 flasks, of which the first contained sodium hypochlorite to reraove 
 the hydrogen sulfide and phosphide, and the following four flasks con- 
 
10 
 
 tained an ammoniacal solution of cuprous chloride to absorb the acet- 
 ylene, by forming copper acetylide. This last compound is explosive 
 when dry; but it can easily be dissolved in hydrocldoric acid, after 
 completing the experiment. The hypochlorite flask v/as weighed sepa- 
 rately, and the four cuprous chloride flasks were weighed together, 
 before and after the gas was generated. The gases were determined by 
 gain in weight of their respective absorbing solutions; from five sue i 
 edeterminations the carbide was calculated to be pure. 
 
 The iron sulphide to be used in this work was also analyzed 
 for its purity, by titrating against a standard solution of KMn 04 . 
 
 An average of four results showed the PeS to contain 61.6^ iron, but 
 since it should theoretically contain iron, this compound is 
 
 only 97.24^ pure. 
 
 To determine the value of calcium carbide as a metallurgi- 
 cal reducing agent, I have centered all my work on its desulphuriz- 
 ing effect on iron sulphide, because this is the most common form of 
 sulphur occuring in steel. To begin with, the following would be the 
 most probable reaction that would take place by heating the two com- j 
 
 I 
 
 pounds at a high temperature, assuming that the reaction would go to | 
 completion: 
 
 3 CaC 2 + 3?eS = 3CaS ♦ ^630 + 5C. 
 
 Since equal moles of the carbide and sulphide are necessary for the 
 reaction, as indicated by the equation, one- fourth the molecular 
 weights of each (considering their purity) were v/eighed accurately 
 and mixed thoroughly; 22.5625 grams FeS and 35.55 grams CaC 2 . This 
 mixture was placed in a fire clay crucible and heated in a small pot 
 furnace for four hours at a constant temperature of 1000®C. The re- 
 sulting mass, formed one large, rather brittle lump, but did not fuse 
 enough to pour. It was pulverized to a fine powder in an iron mortar 
 

 
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11 
 
 during which time, necessary precautions were exercised to prevent 
 any loss of the fine material. 
 
 Half of this pulverized mass was divided into two equal 
 portions, and analyzed for the presence of free calcium carbide. The 
 same method and apparatus used for the determination of the purity of 
 the carbide, described in the beginning of the experimental ?/ork, was 
 employed here. I wish to say, that all the results on this and fol- 
 lowing pages, are the best checks selected from analyses of four fu- 
 sions, all the fusions being made under the same conditions and treat 
 ments; of course the results were taken from only one of the four com 
 plete analyses, and is not a collection of results taken from parts 
 of each complete analysis. 
 
 Determination of free Calcium Carbide. 
 
 1 2 
 
 10.0275 gm. sample used 10.0275 gm. sample used 
 
 .8151 gms . G 2 H 2 liberated^ .8090 gms . C 2 H 2 liberated= 
 
 2.007 gms. free CaC 2 1.99 gms. free CaC 2 
 
 since the sample used is only l/4 the total sample, the total free 
 
 CaC 2 is equal to: 
 
 8.028 gras. 7.960 gms. 
 
 average value = 7.994 gms. 
 
 Sixteen grams of pure carbide were used to make the fusion, 
 and the analysis indicate that only 7.994 grams remained. The miss- 
 ing carbide may have been dissipated in several v/ays; in the forma- 
 tion of CaS, CO 2 , CaO, or C. From the following investigation, we 
 can conclude that some of the carbide was used in the formation of 
 CaS. The assumed CaS was washed out of a five gram sample of the 
 fusion with several portions of boiling water, and the remaining res- 
 idue was carefully dried, and later analyzed for its sulphur contents 
 

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 in the form of FeS. Since CaS is hydrolized by water, reacting in 
 this manner, 
 
 CaS + 2H2O = Ca(0H)2 + H2S 
 
 the above washings contained Ca(0H)2in place of CaS. During the hy» 
 drolysis, a distinct odor of H2S was detected, which verifies the a- 
 bove reaction and the presence of CaS in the fusion. To verify the 
 presence of Ca(0H)2» the washings were treated with Na2C204, and a 
 white characteristic precipitate of CaC204 was formed. The detection 
 of the H2S odor during hydrolysis is more conclusive evidence of the 
 existence of CaS, than is the oxalate precipitate, since the latter 
 may have been formed from the Ca(OH)g produced by the decomposition 
 of the carbide by the water, or from the CaO which exists as an im- 
 purity in the carbide in unknown quantities. 
 
 I 
 
 I 
 
 i 
 
 Determination of the FeS reduced. 
 
 i 
 
 Analysis of the above Five Gram Sample from which the CaS has been | 
 
 thoroughly removed: | 
 
 ! 
 
 The sulphur v/as oxidized to sulphuric acid by fusion with 30 grams of | 
 
 pure sodium peroxide in a nickel crucible. This fusion was thorough- ! 
 
 ly washed out into a beaker, filtered, and treated with BaCl^, to pre- 1 
 
 cipitate the sulphur as BaS04: 
 
 1 2 
 
 6.5698 gms. BaS04 6.5253 gms, BaS04 
 
 Sulphur equivalents .904 gms. Sulphur equivalent^ .897 gms. 
 
 PeS *• =2.479 FeS “ =2.461 " 
 
 FeS in total fusion consisting of 40.1102 grama; 
 
 19.85 gms. 19.72 gms. 
 
 average value=19.785 gms. FeS present. 
 
 22.5625 gms. FeS, which is equivalent to 21.92 gms. pure FeS, were usee 
 
 in making the fusion; therefore 
 
 21.92-19.25=2,135 gms. or 9.74^ of the FeS was reduced. 
 
 The above results indicate a very low efficiency of calcium 
 carbide as a desulphurizing agent; thus the carbide has no practical 
 

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13 
 
 value for the purpose intended under the administered treatment. 
 
 Therefore this investigation was further carried on by heat, 
 ing the same quantities of carbide and sulphide (35.55 gms. and 
 22.5625 gms. respectively) in a fire clay crucible. The temperature 
 was kept constant at 1200° for four hours by the use of a gas pot fur- 
 nace. The product obtained was a fused mass, of what appeared to be 
 only iron, being much less brittle than the product obtained by the 
 1000° heat, and also had less free calcium carbide distributed over 
 the surface. This was treated and analyzed in the very same manner 
 as the previous fusion, and the following are the results: 
 
 Determination of Free Carbide. 
 
 1 2 
 
 9.2436 gm. sample used 9.2436 gm. sample used 
 
 .3624 gms. CgH 2 liberated= .3685 gms. liberated^ 
 
 .8932 gms. free CaCp .9079 gms. free CaCp 
 
 This being only one- fourth of the total sample, the total free carbid« 
 will then be: 
 
 3.5728 gms. 3.6316 gms. 
 
 average = 3.6022 gms. free carbide. 
 
 Determination of the FeS reduced. 
 
 1 2 
 
 5.5885 gms. BaS 04 5.5598 gms. BaSO. 
 
 Sulphur equivalent = .768 gms. Sulphur equivalent = .764 gms. 
 
 " = 2.107 gms. PeS ” = 2.095 gms. 
 
 PeS in total fusion consisting of 36.9744 gms.: 
 
 15.583 gms. PeS 15.499 gms. PeS 
 
 average value = 15.541 gms. PeS present. 
 
 22.5625 gms. PeS, which is equivalent to 21.92 gms. pure PeS, were 
 used in making the fusion; therefore 
 
 21.92 - 15.541 = 6.379 gms. or 29.152^ of the PeS reduced. 
 
 By comparing the last results with those obtained by the 
 1000° fusion, we can almost conclude that at higher temperatures the 
 reducing effect of the carbide is increased. But there must be some 
 definite temperature at which all the carbide will enter into the re- 
 
14 
 
 action, and It is obvious that at this temperature, the total reduc- 
 ing power of the carbide will be consummated. With this point of 
 view, another fusion was made employing the same quantities of car- 
 bide and sulphide as used in the two previous fusions. The tempera- 
 ture was kept at 1400® C for one and a half hours by means of an oil 
 pot furnace. At this high heat it was necessary to use a graphite 
 crucible, the inside of which was lined with a smooth layer of fire 
 clay. A hard, black, glossy, slag and a mass of iron was produced. 
 The silica contained in the crucible lining also took part in the re- 
 action, by helping in the slag formation. This last statement sug- 
 gests the thought, that the addition of silica would probably lower 
 the reaction temperature and lessen the time of operation, but this 
 thought is contradicted by the fact that the lower temperature fus- 
 ions (lOOO® and 1200®) were carried out in fire clay, silica contain- 
 ing crucibles which were not even slightly attacked after four hours 
 of continuous heating. These crucibles contain 71.81^ silica, most 
 of which would have readily taken part in the reaction if there were 
 need for it, as it was with the 1400® fusion. 
 
 An analysis of the mass of iron was made, for the determin- 
 ation of free calcium carbide, but not a trace could be detected. 
 Applying the same method used in the previous analyses, the quantity 
 of unreduced FeS was determined. 
 
 1 2 
 
 5 gm. sample used 5 gm. sample used 
 
 7.1023 gms. BaS 04 7.1893 gms . BaS 04 
 
 Sulphur equivalent = .977 gms. Sulphur equivalent = .979 gms. 
 
 PeS ” = 2.679 gms. 5*63 ** = 2.682 gms. 
 
 PeS in total fusion consisting of 19.6385 gms.: 
 
 10.51 gms. 10.54 gms. 
 
 average = 10.525 gms. PeS present. 
 
 22.5625 gms. PeS, which is equivalent to 21.92 gms. pure PeS, were 
 used in making the fusion; therefore 
 
 21 .92-10i»525 = 11.395 gms., or 52^ of the PeS was reduced. 
 
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15 
 
 SUMIJIARY. 
 
 Since at 1400° C, all the calcium carbide takes part in the 
 reaction in one form or another, it is evident that at this tempera- 
 ture the carbide produces its greatest reducing effect on ferrous 
 sulphide. Higher temperatures may shorten the time of operation, but 
 I doubt whether higher temperatures would be employed commercially 
 for this purpose, because high heats tend to decrease the life of any 
 furnace considerably. 
 
 The presence of silica is necessary for the formation of a 
 running slag, which is a very important factor in large scale work. 
 
 With an efficiency of 52^, as the results indicate, the use 
 of calcium carbide as a reducing agent for iron sulphide is not prof- 
 itable on account of the high cost of the carbide. If a much cheaper 
 method for the manufacture of carbide is developed, this process of 
 reducing iron sulphide could be advantageously used on a commercial 
 basis. 
 
 The reducing efficiency of calcium carbide cannot be entire- 1 
 
 I 
 
 ly judged by its effect on ferrous sulphide alohe, since it may rendei 
 a greater efficiency in reducing oxides, other sulphide ores, and sul- 
 phur in steel and pig iron. Two other men who are independently en- 
 gaged in investigations similar to this, have found that calcium car- 
 bide reduces from 35 to 55^ of sulfur in steel, and also, that the re- 
 action of carbide with ferric oxide begins at 1250° C and is completec 
 at 1500° C. 
 
 The efficiency of 52^ as indicated by the experimental re- 
 sults, does not take into consideration any sulphur that may have beer 
 oxidized to sulphur dioxide. In this light, the 52;^ efficiency is too 
 

 
 
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high. In order to determine the efficiency correctly, the amount of 
 sulphur present in the slag must he determined. In the lower temper- 
 ature fusions (at 1000° and 1200°) in which the reduced sulphur is in 
 the form of calcium sulphide, the sulphur may he determined hy ab- 
 sorbing the hydrogen sulphide in lead acatate during the hydrolysis 
 of the calcium sulphide; this reaction is explained under the analysii 
 of the first fusion. If more time were available, I would have made 
 the above quantitative determinations of sulphur. 
 
 This problem, therefore, still has a momentous field open 
 for investigation, which I hope will be further continued by those 
 whose interest may have been aroused by this article. 
 
 I regret that I have only had one half year (one semester) 
 to spend on this tremendous task and that so little could be accomp- 
 lished, but I feel that the time was well spent, if this article will 
 only give an impetus towards the completion of this investigation. 
 
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BIBLIOGRAPHY. 
 
 1 Calcium Carbide and Acetylene by Fowler, P 665 
 
 2 J. S. C. I. 1895, Page 440. 
 
 3-4 Calcium Carbide and Acetylene by Fowler, P 665 
 5 J. S. C, I. 1897, Page 145. 
 
 5-6 Chemical News, Volume 75, Page 2. 
 
 7 J. S. C. I. 1901, Page 46. 
 
 8 J. S. C. I. 1900, Page 475. 
 
 9 Transactions of the American Society for Steel treating. 
 Volume 1, January 1921. 
 
 10 The Metallurgy of Iron and Steel by Bradley Stoughton.