ANALYSIS OF BABBITT * JAMES BRAKES Chief Chemist Chateaugay Ore and Iron Company, Member of the American Chemical Society, the American Electrochemical Society, the American Foundrymen's Association. FIRST EDITION ALLEN BOOK AND PRINTING CO. TROY, NEW YORK 1919 IDe&icatefc to my friend FRANK L. NASON Geologist and Mining Engineer. PREFACE TT is the desire of the author, to place before the mining, civil, electrical and mechanical engineer, and others, who have taken chemical analytical training, a small practical book on the analysis and manufacture of babbitt. Many concerns would like to use, if possible, a babbitt made from a certain formula that has been known to give satisfaction in the past, and with care in weighing, selec- tion of the furnace and observing certain precautions in melting the various metals, excellent results can be obtained with very little loss. With the exception of the modification of the Alexan- der method for lead, the methods may be old, but they have been selected from the many methods in use for their simplicity, neatness and accuracy of analysis of a babbitt, of known composition. At the same time reactions and data have been inserted, which will be of interest to the student in analytical chemistry. There is included, the titles of many methods by different chemists for the analysis of white metals and white metal alloys, and also an extensive bibliography of books on metallurgical engineering. To the young chemist, for whom this book has been especially written, it is the earnest desire that it may be of pleasure and profit. I desire to publicly thank Dr. F. W. Schwartz for reading the manuscript and Miss Helen T. Gibney for reading the proofs. JAMES BRAKES. CONTENTS INTRODUCTION. CHAPTER I. ANTIMONY. PAGES Properties, etc Qualitative Quantitative- Volumetric and Electrolytic Analysis Biblio- graphy of Antimony Analysis 3-21 CHAPTER II. TIN. Properties, etc Qualitative Quantitative Volumetric and Electrolytic Analysis Biblio- graphy of Tin Analysis 22-46 CHAPTER III. LEAD. . Properties, etc Qualitative Quantitative Volumetric, Gravimetric and Electrolytic Analysis Bibliography of Lead Analysis 47-76 INTRODUCTION '"pO IZAAC BABBITT, to whom recognition is given ** as one that made a special study of bearing metal and was so successful in the art of making anti-friction alloys, that his name has been used to indicate the process as well as that of the alloy. According to Buchanan, the original patent was issued for a particular form of bearing and not for a special anti-friction alloy. The original was composed of 90 parts of tin and 10 parts of copper, later, it was said to be a mixture of tin, antimony and copper. A "hardening" is first prepared by melting 24 parts of tin, 8 parts of antimony and 4 parts copper. Each metal is melted separately, covered with powdered charcoal to prevent oxidation. The antimony is added to the tin after fusion and the copper after the molten alloy is removed from the furnace. This hardening, either in the form of ingots or direct from the furnace, is added to twice its weight of melted tin, the surface of which is covered with powdered coal and the resulting alloy is termed the lining metal, with a theoretical composition of tin 96 parts, antimony 8 parts and copper 4 parts, or tin 88.89%, antimony 7.41% and copper 370%. F BABBITT The process of making the anti-friction alloy is again described as melting 4 parts of copper, add 8 parts of antimony, allow to cool to dull red heat, then add 16 parts of tin. This alloy is also termed "hardening" which is added to twice its weight of tin, the surface of the molten metal being covered as before with powdered coal. Time has changed the formula and mode of manu- facture of the above alloy, which at one time was extensively used, but it has been replaced in many cases by other alloys in which a portion of the tin has been substituted by lead and zinc, hence in recent years there are many anti-friction alloys on the market that are called babbitt, and the change of formula has been altered and influenced by the high price of tin and also by the general satisfaction that other alloys have given. Each year the babbitt industry is becoming greater, and the alloys has been improved by the addition of a small percentage of certain metals (for which patents have been granted), which imparts a fine close and compact body to the alloy, thereby increasing its wearing and lasting qualities far greater than that of ordinary babbitt. CHAPTER IV. COPPER. PAGES. Properties, etc Qualitat ! ve Quantitative Volumetric, Gravimetric and Electrolytic Analysis Bibliography of Copper Analysis. . . . 77-117 CHAPTER V. MISCELLANEOUS ANALYSIS Determination of Magnesium and Bismuth in Babbitt Qualitative Analysis of Babbitt Miscellaneous Bibliography of White Metal Analysis 118-135 CHAPTER VI. BABBITT METAL. Notes on the Manufacture of Babbitt Examples of Calculations Sampling of Babbitt Bibliography of Metallurgy Key to Publish- ers. . . 136-169 ANTIMONY PROPERTIES CHAPTER I. ANTIMONY. (Stibium.) Said to have been discovered by Basil Valentine, a monk of Germany, in the fifteenth century. Schelenz 1 states that the name antimony comes from the Arabic. Wang Chung, Yu 2 has treated the subject of antimony in a thorough manner. Properties, etc. Chemical symbol, Sb ; atomic weight, 120.2; trivalent usually; Sp. Gr. 6.713 3 ; molten, 6.55 (631C) 4 ; melting point, 632C. 5 ; volatilizes at about 1500C. Specific heat at about melting point, .054 6 ; latent heat of fusion, (calculated) 16.0 Cal. T ; increase in volume on melting, 1.4% 8 ; electrical conduc- tivity (Ag=lOQ) 4.6 9 ; casting temperature 710- 1050C 10 ; Foliated, crystalline scale like structure; sil- ver white-color when pure, but the commercial has a bluish-white tint; strong metallic lustre; very brittle and easily reduced to powder; neither ductile or malleable; not readily acted upon by the air; tarnishs slowly in warm moist air; burns with a blueish white light when heated to redness in the air ; alloys particularly with the 1 Antimony. Schelenz. Z. Angew. Chem., 26, 1311-2. 1 'Antimony. Wang Chung Yu. (f). *Long. 'Richards. 'Pascal and Joumiaux. *Tocplar. *Pouillet. 'Matthiessen. Hofman. Wust. 4 ANALYSIS OF BABBITT metals, Pb t Bi, Sn, Cu, Ni and Fe. Used technically in the manufacture of alloys (Britannia metal, hard lead, white metal, bearing metal); imparting hardness and expansion to alloys when cooling from .the molten state; manufacture of thermoelectric piles, blacking iron, coat- ing metals, antimony black; is employed to impart a metallic surface to plaster casts and to cast zinc orna- ments ; alloy for printing type ; preparation of tartar emetic and other pharmaceutical products; the metal is at present rarely used medicinally, but at one time was used for leprosy; the slow cooling of the commercial metal produces a peculiar coarse laminated, crystalline, rhombohedra structure required in commerce, which is regarded as the best star-antimony, whereas, if cooled quickly, the fracture is granular. Native antimony usually contains Ag, Fe and As, with a specific gravity of 6.5-7. In combination with other ores, but the chief ore is stibnite, Sb 2 S B . A high fusion point is a sign of its impurity; pure metal is usually prepared by the Liebig process 1 ; important in the refining of argentiferous lead; dissolves slowly in hot HCl; converted to the pen- toxide by HNO B ; H 2 SO first oxidizes it and then con- verts it to the sulphate; soluble in cold aqua regia, and the solution contains SbCl 3 or SbCl 6 , depending upon the concentration of the acid and the time of action ; anti- mony pigments as a substitute for white lead and zinc paint, being innocuous, permanent and sun proof; the use of the sulphide in the rubber industry. Commercial antimony (98.46% Sb.) Sp. Gr. 6.69. 1 cubic foot weighs 417.6 pounds. Immense quantities of Sb compounds are used in wall paper, textile fabrics, paper dyeing and printing. No clearly defined case of antimonial poison- *Rosc. and Schorni. Vol. II, Pt. II, 304. ANTIMONY PROPERTIES 5 ing has been established, 1 but opinion differs as to the poisonous action of Sb on workmen. A very small per- centage of Sb in Cu lowers its conductivity. According to Hiorns and Lamb, the effect of Sb on the conductivity of Cu is indicated by the following figures .000% Sb, 100; .098%, 76; .203%, 70; .208%, 68.5; .392%, 58.4; .461%, 48.9; .605%, 42.4; patents have been granted for the manufacture of finely divided Sb by electrolysis, for medicinal uses. Schrumpt and Zabel state that type- setters suffer from a general debility and that the complaint was traced to Sb poisoning. According to Poppe and Polenski, Sb added to barley flour, used for fattening geese, does not produce an abnormally fat liver as generally believed. Flour containing no Sb seems to produce the same results. Seltzer and carbonated waters have an action upon the alloys of Sn, Sn-Pb or Sn-Sb, used for stopping the siphons. The action is assisted by electrolytic action ; antimony has been found in foods that have been prepared in enameled cooking utensils. Chinese "crude" Sb contains Sb 2 O 3 and metallic Sb. (Schoeller). Kahlbaum's "technical" Sb contains as impurities Cu, Pb, Fc, Ni, Co, Sn and As (impurity=: 1:10 2 ), and Kahlbaum's "pure" Sb is of higher purity, but the ratio of the impurities to Sb has not been estab- lished. (Mylius). According to Guettier the specific gravity of Sb-Sn alloys is below that of the calculated specific gravity of the mixture. The best alloys- of Sb and Sn are made by having nearly the proportion of Sb 20 parts and Sn 80 parts, casting at a low temperature and using cold molds to prevent segregation of Sb. *Textil Faerb.-Ztg., 8, 39, also Loewenthal. Chem. Ztg., 33, 1325. 6 , ANALYSIS OF BABBITT Hardness (talc=l), 3.3 1 ; coefficient of linear expansion per degree C. (O-100) .0000168 2 ; normal to axis, .0000089 2 ; tensile strength at ordinary temperature (pounds per square inch) cast, 1,000; specific heat for tC., Sm (o to .04864+ .0000084** ; specific heat at about 15C, .048 2 ; at 1-20, .0503; at 632-830C., .0603. Boiling point, visible ebullition, 1420C. 4 ; Young's Modulus 5 ()=7.8x 10 11 ; modulus of rigidity 5 ({i)=2xl0 11 . Metallurgical processes. (1) liquation process; (2) Crucible process; (3) open-hearth process; (4) English process; (5) volatilization process ; (6) French process; (7) electrolysis; (8) elec. furnace process. The process used, depends upon the locality, cost of production, market price and demand for the metal. Natural Sources: Native Antimony, (Sb) rare; STIBNITE, (Sb 2 S 3 ) ; valentinite, (Sb 2 O z ) ; senarmontite, (Sb 2 O 3 ) ; cervantite, (Sb 2 OJ ; stiblithe, (S 2 4 +/f 2 O) ; kermesite, (2Sb 2 S 3 Sb 2 O 3 ) ; also waste product from smelting ores as pyrargyrite, (Ag Q Sb 2 S Q ) ; berthierite, (FeSb 2 S 4 ) ; freiesle- benite, (Ag^Sb^^ ; wolfsbergite, (Cu 2 Sb 2 S 4 ) ; bournan- ite, ((Cu 2 Pb) 3 Sb 2 S Q )-, boulangerite, (PbSb 2 S 4 ) ; blein- ierite, (Pb 2 Sb 2 S 5 ) ; dyscrasite, (Ag 2 Sb) ; ullmannite, ((NiSSbAs) 2 ); breithauptite, (NiSb) ; allemontite, Mining Localities: Andieasberg in the Harz; Przibram in Bohemia; Sahl in Sweden ; Sarawak in Borneo ; Constantine in Turkey ; Tuscany in Italy; Algeria, Canada, Mexico, France, United States, Chili, Japan, China, Nova Scotia and New South Wales. *Mohs. *Hofman. l Naccaria. 'Greenwood. *Bridgman. ANTIMONY PROPERTIES 7 References: Antimony. Wang. (/). The Antimony Industry. Howard, (g). Production of Antimony in the United States. 1 The production of antimony ore in the United States in 1916 amounted to about 4,470 short tons, carrying about 1,770 short tons of antimony. Alaska produced during the year of 1917, antimony valued at $40,000. Production of Antimony in the United States. 2 Antimony in antimonial lead in 1914 was 3,535 tons. Antimony from domestic ores in 1915 was about 2,100 tons. This does not include the production of antimony in antimonial lead which was 3,288 tons. The produc- tion of 1916 was much smaller owing to the rapid decline of antimony prices. Commercial Metals. 3 Analysis of some of the more important brands of antimony : Cookson's Sb (by difference), 99.874; Pb, .041; Sn, .035; As, tr.-, CM/ .04; Fe, .010; Zn, tr. Cookson's Sb (by difference, 99.608; Pb, .102; Sn, tr.-, As, .092; Bi, none; Cu, .046; Cd, none; Fe t .004; Zn, .034; Ni and Co, .028; S, .086. Hallett's Sb (by difference), 99.104; Pb, .669; Sn, .175; As, tr.; Cu, .038; Fe, .014; Zn, tr. Hallett's Sb (by difference), 99.045; Pb, .718; Sn, .012; As, .021; Bi, none; Cu, .046; Cd, none; Fe, .007; Zn, .023; Ni and Co, none; S, .128. Japanese Sb (by difference), 99.325; Pb, .443; Sn, .175; As, .008; Cu, .034; Fe, .015; Zn, tr. Japanese Sb, 99.195; Pb, .424; Sn, .012 ; As, .095 ; Bi, none ; Cu, .043 ; Cd, none ; Fe, *U. S. Geol. Survey (communication). *Met. and Chem. Eng. (communication). *Min. and Sci. Press, July 10, 1915. 8 ANALYSIS OF BABBITT .007; Zn, .023; Ni and Co, none; S, .201. Chinese 5& (by difference), 99.915; Pb, .018; Sn, .035; As, .017; CM, .008; Fe, .007; Zn, *r. Chinese^, 99.760; Pb, .029; 5"n, none; As, .090; Cd, none; F*, .004; Zn, .027; JW and Co, tr. ; S, .078. Qualitative Analysis. Dissolve .2-.3 gram of the powdered metal in 2 or 3 c. c. of hot aqua regia, add 20 c. c. of water and about 1 gram of A/a 2 S0 3 +7 H 2 O. Heat nearly to boiling, and when the odor of S0 2 is perceptible, pour the solution into about 300 c. c. of cold water. If Sb is present, a white bulky precipitate of ANTIMONIOUS OXYCHLORIDE (powder of Algaroth), will be precipitated. 4S&C/3+5 H 2 O=2 (Sb O Cl) ^ 2 O 3 +10 HCl Precipitate soluble in H 2 (C^H 4 6 ) and water, repre- cipitated by H 2 S as Sb 2 S s , orange-red precipitate. (Bi O Cl under similar conditions, will become black Bif f ). Dissolve .1-.2 gram of the powdered metal, in 1 or 2 c. c. of aqua regia, and evaporate to dryness Add 1-2 c. c. of HCl and about 10 c. c. of water and heat until solution is clear. Place a piece of metallic Zn, supported on platinum foil in the solution and allow to stand a few minutes, remove the black stained foil, place in small beaker and add 2 drops of HNO S , H 2 (CH 4 O e ) and water, and heat to dissolve. Filter, if necessary, and add H 2 S to the nitrate ; an orange-red precipitate of . Sb 2 S 3 indicates Sb. Heat with the blow-pipe on charcoal, a small fragment of the metal and condense the copious white fumes on cold procelain. Place 1 or 2 drops of (NH^) 2 S in con- tact with the white sublimate ; an orange-red coloration indicates Sb, due to the change of the volatile Sb 2 O z to Sb 2 S 3 . ANTIMONY PROPERTIES 9 Dry on a filter, a portion of the white precipitate obtained by the addition of water. Moisten wkh a few drops of (NH 4 ) 2 S', an orange stain indicates Sb 2 S 9 m , a black color denotes Bi 2 S s . H 2 S precipitates all the Sb from moderately acid anti- monious solutions as Sb 2 S s ; imperfectly from alkaline and neutral solutions. Sb 2 S 3 is insoluble in (NH 4 ) 2 CO 3 and dilute acids; soluble in concentrated HCl with evolution of H 2 S\ soluble in KHO and alkaline sulphides containing an excess of 5\ H 2 S precipitates Sb 2 S 5 , mixed with Sb 2 S s and free S from HCl solutions of antimonic acid. Soluble in boiling HCl, hot NaHO and NH 4 HO ; soluble in (NHJ^S, from which solution it is reprecipitated by HCl. Quantitative Analysis. K 2 Mn 2 O 8 Method. Volumetric Method. Place .5 gram of the finely divided alloy in a dry 400 c. c. beaker. Add 10 c. c. of strong H 2 SO 4 , cover and heat until the alloy is entirely decomposed (about 10 or 15 minutes). Cool, add 150 c. c. of water, 15 c. c. of strong HCl and boil 5 minutes. Cool and titrate rapidly with standard K 2 Mn 2 O 8 solution to a rose color. Subtract blank and calculate Sb. (titration must be rapid and the first coloration taken). K 2 Mn 2 O 8 +5 SbCl z +\6 HCl= 5 SbCl 5 + 2 HCl+2 AfnC/,+8 H0 "l20.2 " K 2 Mn 2 O 8 =W FeS Sb. Sb=2 Fe= = 111.68 1.0763, and therefore multiply the Fe factor by 1.0763 and the product will equal the Sb factor. Standard K 2 Mn 2 O 8 Solution. 1 *This solution is also used for Fe, P, Mn, Ti and CaO. 10 ANALYSIS OF BABBITT Dissolve 3.70 grams of K 2 Mn 2 O B c. p., in 1000 c. c. of water and standardize as follows : Dissolve 1.4 grams of FeSO^NH^^SO^+6 H 2 (14.24% Fe. Merck, blue label), in a cold mixture of 150 c. c. of water+10 c. c. of H 2 SO^ titrate to a rose color and subtract blank. 2 SOt + 6 H 2 X .1424 1 c. c.=- 31. c. c..l c. c. K 2 Mn 2 O s solution .006451 gram of Fe, and .006451 X 1.0763= .006943 gram of Sb. No. 2 Babbitt. .006943 X 12.8 c. c..l c. c. K 2 Mn 2 O solution .5 gram of alloy X100=:17.63% Sb. Mixture calculation^ 18.00% Sb and, as the commer- cial metal contained 98.46%, the actual content was 17.72% Sb. Determination of Sb in Commercial Metal. Weigh .5 gram and treat as usual, until the final solu- tion obtained is ready for titration. Transfer solution to a 250 c. c. marked flask, dilute to the mark and mix thoroughly. (1 c. c. of solution contains .002 gram of metal). Take 100 c. c. of the solution with pipette and place in 400 c. c. beaker. Add 10 c. c. HCl and titrate the cold solution with standard K 2 Mn 2 & . Subtract blank and calculate Sb. Accuracy of method, 98.38%- 98.55% Sb. ANTIMONY PROPERTIES 11 The K 2 Mn 2 O 8 solution can be standardized with KSbC 4 H 4 O 7 . y 2 H 2 O\ C. P. From the formula, it should contain 36.16% Sb. The Sb must be determined in the salt, before it can be used as a standardizing reagent and this can be done very accurately by the following method. Place .5 gram of the pure salt in 400 c. c. beaker and dissolve in 10 c .c. of hot water. Add 15 c.c. of strong HCl and 100 c. c. of water. Cool and titrate as usual, with standard K 2 Mn 2 O 6 solution. Multiply the Fe factor by 1.0763 and the product will equal the Sb factor. .006764X277 c. c..l c. c. K 2 Mn 2 O B solution A= .5 gram X 100=37.33% Sb. .006764X27.7 c. c..l c.c. KMn 2 O 8 solution B= . 5 gram X 100=37.33% Sb. The salt is permanent, as the results from the above sample gave ten years later, the following results. .006904X27.1 c. c..l c. c. K 2 Mn 2 O 8 solution C= .5 gram X 100=37.28% Sb. N/IQ K 2 Mn 2 O 8 Solution. Dissolve 3.16 grams of K 2 Mn 2 O 8 C.P. in 1 liter of water. 1 c. c.=. 005584 gram of Fe (theoretical), and K 2 Mn 2 O 8 =lO Fe, also Sb=2 Fe then 111.68: 120.2=.005584:X. X=.00601 gram of Sb. (theoretical). KBrO 3 Method. V* is said that a small portion of the Sb in tartar emetic is present as antimonic salt. (Coblentz and May. Merck's Report 18, 195.) 12 ANALYSIS OF BABBITT Volumetric Method. Place .5 gram of the finely divided alloy in a 400 c. c. beaker. Add 20 c. c. of HCl and a few drops of bromine. Shake frequently and warm gently until dissolved. Dilute to 75 c. c. with water and boil until free from Br (about 8 minutes). Dilute with water to 125 c. c. Add 1 gram of Na 2 SO 3 . 7H 2 O and boil down to 75 c. c. Wash cover and sides of beaker with water, add 10 c. c. HCl and heat to boiling. Add 3 drops of methyl orange solution (.05 gram of the salt dissolved in 15 c, c. of water) and titrate with standard KBr0 3 until the solution is colorless. AT/10 KBrO 3 Solution. Dissolve 2.7836 grams of pure KBr0 3 in 1000 c. c. of water. 2 KBrOs+2 HCl+3 Sb0 8 = 2 KCl+2 HBr+3 Sb,O, 2 KBr0 3 =6 Sb 2 KrO 3 =167.02X2=334.04 6 Sb =120.2 X6=721.2 334.04 : 721.2=2.7836 : X X=6.01 1000 c. c. AT/10 KBrO 3 V. S. containing 2.7836 grams KBrO 3 =6.Ql grams Sb. 1 c.c. AT/10 KBrO s V.S. containing .0027836 gram ^rO 3 =.00601 gram Sb. (theoretical.) Standardize the KBrO 3 solution as follows : Place .5 gram of KSbC^H 4 O 7 . */> H 2 0, C. P. in 400 c. c. beaker and dissolve in 10 c. c. of hot water. Add 30 c. c. HCl, dilute to 75 c. c. with water and heat to boiling. Add 3 drops of methyl orange solution and titrate with KBrO 3 solution. ' .3733X.5 gramKSbCtH 4 O 7 . */ 2 H*O 1 c. c.= =.005992 gram Sb. 31.15 c. c. ANTIMONY PROPERTIES 13 No. 2 Babbitt. .005992X14.9 c. c. KBrO 3 solution X 100=17.85% Sb. .5 gram of alloy Electrolytic Method. Place .5-1 gram of the finely divided alloy in 150 c. c. beaker and warm gently with a mixture of 4 grams of H 2 C^H 4 O 6 -\-4 c. c. of HNOi(L42)+l5 c.c. of water, "heat and shake until solution is complete. Add 4 c. c. of //..SO 4 ( 1.84), dilute with 20 c. c. of cold water and transfer to a 250 c. c, marked flask. Cool, dilute to the mark, mix and allow to settle. Take 50 c. c. with pipette, place in 250 c. c. beaker and neutralize with a concentrated solution of NaHO. Add 2 grams in excess and heat gently to obtain a clear solution. Add 50 c. c. of a saturated solution of Na 2 S(1.20), heat to boiling and allow to settle. Filter and wash with 30 c. c. Na 2 S solution (1.20) diluted with water. The solution should now contain 80 c. c. of saturated solution of Na 2 S and 2 grams of NaHO. Evaporate or dilute to 125 c. c., add 25 c. c. of alkaline solution of H 2 O 2 (3%) and heat the solution until it is nearly colorless. Electrolyze with a current of ND 100 = 1.5-1.6 amperes and 2.1-1.45 volts. Time 2.5 to 6 hours. When the Sb is all deposited, wash the cathode with distilled water without interrupting the current, by lower- ing the beaker and directing a fine spray of water over the surface of the cathode, and then immerse in C 2 H 6 for a few seconds. Dry in air bath for 15 minutes at a temperature of 80-90C. Cool and weigh. Weight taken=.5 gram and solution diluted to 250 c. c. .5 gram then 50 c.c.=.l gram ( X50=.l). 250 c. c. 14 ANALYSIS OF BABBITT The area of the electrode cylinder of platinum gauze= 1.6 amperes 6.3 sq. in.=40.6 sq. cm. and =4 amperes. .406 Used 4 amperes 3.1 volts, (four 32 c. p. carbon lamps in parallel.) Time 2.5 hours. (1) Cylinder-f deposit^ 10.0505 grams. =10.0414 " .0091 gram. XI 00=9. 10% Sb. .1 gram alloy. (2) Cylinder-f deposit= 10.0504 grams. = 10.0412 " .0092 gram. X 100=9.20^0 Sb. .1 gram alloy. (3) K 2 Mn 2 8 Method=9.13% Sb. According to Classen, "the following equations prob- ably represent the reactions which take place in the electrolysis of the antimony sulpho-salt." At the cathode: Sb 2 S z +3 Na 2 S+6 H=2 Sb+6 NaHS. At the anode: 6 NaHS+3 O=3 Na 2 S 2 +3 H 2 O. After the cathode and the deposit of antimony has been weighed, place it in a solution of dilute HNO z (l :1) and allow to stand about 1 hour. Should the above ANTIMONY PROPERTIES 15 solution fail to remove the deposit, fill a 50 c. c. platinum crucible with HKSO^ within l /4 inch of the top. Fuse, place cathode in the melted salt and allow to remain 3 to 5 minutes. Remove, cool and place in warm water containing HCl and, after the salt has dissolved, wash thoroughly with water. Dry and the cathode is ready for use. To determine the end of the electrolytic reaction, place a bright piece of platinum foil in contact with the cathode. Should there be a deposit, redissolve it by placing the foil in contact with the anode. Sodium Sulphide Solution. Dissolve 85 grams of NaHO in 200 c. c. of water (Sp. Gr. of solution^ 1.3). Divide the solution into two parts and pass H 2 S through one part, free from air, until the odor of H 2 S in solution is decided. Filter, add the remaining part and pass H 2 S until the solution is saturated. Filter through cotton, cork tightly and set aside in cool dark place. 1 In passing H 2 S through the colorless solution of NaHO, the color becomes in succession, yellow, orange, brown and finally, a straw color when the solution is saturated with H 2 S. The volume increases from 200 c. c. to 290 c. c. Sp. Gr. 1.20. Time 12 to 15 hours for the absorption of H 2 S. 2 NaHO+H 2 S=Na 2 S+2 H 2 O 80+34 =78 +36 80 : 78=85 : X X=82.8 grams 34:78=X:82.8 X=36.1 grams *If the monosulphide is required, saturate one half of the NaHO solution with H 2 S, add the other half and filter directly into stoppered bottles. 16 ANALYSIS OF BABBITT 36.1 grams. -=23.6 liters of H 2 S, 1.53 grams. at OC. and 760 ni.m. of Hg. Saturated solution of Na 2 S made from the salt. At 10 C 1.15 Sp. Gr. " 25 C 1.20 " " " 32C 1.20 " " " 38 C 1.225 " " To prepare the Na 2 S solution for the separation of Sn and Sb from the other metals, dissolve the colorless c. p. salt in water as needed. Saturate with washed H 2 S, allow to settle, filter, bottle, cork tightly and keep in cool dark place. The following methods for the determination of antimony will be of interest to the analyst: Determination of Antimony in Ores. Brown. Journ. American Chem. Soc., Sept., 1899. Volumetric Estimation of Antimony. Darroch. Chem- ical Engineer, Aug., 1906. Antimony in Babbitt and Type Metals. Yockey. Journ. American Chem. Soc., Oct., 1906. Technical Estimation of Antimony and Arsenic in Ores, Etc. Low. Journ. American Chem. Soc., Dec., 1906. Determination of Antimony and Tin in Babbitt, Type Metal or Other Alloys. Low. Journ American Chem. Soc., Jan., 1907. Volumetric Estimation of Antimony. Duncan. Chem- ical Engineer, March, 1907. ANTIMONY PROPERTIES 17 Determination of Antimony and Arsenic in Lead- Antimony Alloys. Howard. Journ. American Chem. Soc., March, 1908. Purity and Volatility of Precipitated Antimony Sulphide. Youtz. Journ. American Chem. Soc., June, 1908. Separation of Tin and Antimony. McCay. Journ. American Chem. Soc., March, 1909. Rapid, Practical Method for the Determination of Antimony and Tin in Alloys such as Babbitts and Solders. Vietz. Chemical Engineer, Oct., 1910. Analysis of Tin-Antimony Alloys. McCay. Journ. American Chem. Soc., Oct., 1910. Gravimetric Estimation of Antimony and Tin. Cohen and Morgan. Analyst, 34, 3-9. 34, 3-10. The Rapid Electroanalytical Deposition and Separation of Antimony and Tin. Sand., J. Chem. Soc., 93-4, 1572-92 (Aug.). The Separation of Antimony and Tin. Panajotow. City Chem. Lab., Sophia. Ber., 42, 1296-9. The Quantitative Determination of Antimony by the Gutzeit Method. Sanger and Riegel. Chem. Lab., Harvard Univ., Cambridge, Mass. The Volumetric Determination of Antimony. Schmidt. Chem.-Ztg., 34, 453-5. Separation of Antimony and Tin by Distillation. Plato. Z. anorg. Chem., 68, 26-47. Determination of Tin and Antimony in Soft Solder. Goodwin. J. Ind. Eng. Chem., 3, 34. The Determination of Arsenic and Antimony in Copper. Heath. J. Ind. Eng. Chem., 3, 78-82. Note on the Detection and Estimation of Small Quanti- ties of Antimony. Schidrowitz and Goldsbrough Analyst, 36, 101-3. 18 ANALYSIS OF BABBITT Volumetric Method for Antimony. Jamieson. J. Ind. Eng. Chem., 3, 250-1. Determination of Antimony in Red Rubber Goods. Schmitz. Gummi Ztg., 25, 1928. The Examination of Antimony and Tin in Metallic Alloys. Belasio. Ann. lab. chim. centr. delle Gabell, 6; Giorn. farm, chim., 61, 499-500. The Estimation of Arsenic and Antimony. Hooper. Eng. Mining J., 94, 706-7. Analysis of Antimony and Lead Compounds Containing Oxygen. Jacobsohn. Chem. Ztg., 32, 984 (Oct., 7). Analysis of Alloys of Antimony. Nicolardot and Krell. Bui. soc. Chim., 5, 559-62. Determination of Antimony in its Sulphide Preparations. Howard and Harrison. Pharm. J., 83, 142. Separation of Arsenic and by means of the Knorr Dis- tillation Apparatus. Smith. Eng. Min. J., 88, 1062-3. The Precipitation of Antimony from Solutions of Sulphoantimonate. Schulte. Metallurgie, 6, 214-20; Chem. Zentr., 1909, I, 1741. Application of Potassium Ferricyanide in Alkaline Solution to the Estimation of Arsenic, Antimony and Tin. Palmer. Am. J. Sci., 29, 329-403; Z. anorg. Chem., 67, 317. The Determination of Antimony. Beckett. Chem. News, 102, 101-4. New Method for the Determination of Tin in the Presence of Antimony. Sanchez. Bull. soc. chim., 7, 890-4. Determination of Arsenic and Antimony in Anode Copper. Kern and Ching Yu Wen. Met Chem. Eng., 9, 365-7. Determination of Antimony in Red Rubber Goods. Frank. Gummi. Ztg., 25, 2002. ANTIMONY PROPERTIES 19 Detection of Arsenic, Phosphorus and Antimony in the Medical Diagnosis of Poisoning from these Substances. Pedrazzina. Boll. chim. farm., 50, 134; J. Chem. Soc., 100, II, 438. New Method for the Detection of Traces of Arsenic and Antimony. Staddon. Chem. News, 106, 199. The Analysis of Antimony-Tin Alloys. Pontio. Ann. chim. anal., 18, 47-8. Rapid Methods for the Estimation of Antimony. Nis- senson. Z. anorg. Chem., 81, 46-8. The Determination of Arsenic and Antimony in Con- verter and Electrolytic Copper. Brownson. Bull. Am. Inst. Mining Eng., No. 80, 1489-95. Rapid Determination of Antimony and Arsenic in Anti- monial Lead and Antifriction Alloys. Bertiaux. Ann. chim. anal., 19, 49-51. Use of Hydrofluoric acid in the Separation of Copper and Lead from Tin and Antimony by means of the Electric Current. McCay. J. Am. Chem. Soc., 36, 2375-81 (1914). Analysis of Antimony. Cowan. Analysis of 4 ingots of com. Sb are given. Chem. Trade J., 56, 6 (1915). Rapid Analysis of Alloys for Tin, Antimony and Arsenic. Stief. J. Ind. Eng. Chem., 7, 211-2 (1915). Determination of Antimony. Layng. Mining Sci. Press, 113, 57-8 (1916). Simple Method of Estimating Antimony in Stibnite. Lehmann and Lokau. Arch. Pharm., 252, 408-12 (1914). Method for Estimating Phosphorus, Arsenic and Anti- mony in Commercial Copper. Grant. Chem., Analyst, .17, 12-3 (1916). 20 ANALYSIS OF BABBITT The Determination of Antimony in the Products Obtained by Roasting Stibnite. Hall and Blatchford. Bull. Am. Inst. Mining Eng., 1916, 99-101. The Analysis of Antimonial Lead. McCabe. J. Ind. Eng. Chem., 9, 42-4 (1917). Antimonium crudum. McGeorge. *Hahnemanniam Monthly, 52, 303-7 (1917). Does the Feeding of Antimony Produce Fatty Liver in Geese? Method for the Detection of Antimony and Arsenic in Goose Livers. Poppe and Polenske. Arb. Kais. Gesundh., 38, 155-61; Chem. Zentr., 1911, II, 1158. Methods of Detection, Separation and Determination of Arsenic and Antimony. Bressanin. Ann. chim. anal., 17, 81-4. Separation and Quantitative Determination of Antimony in White Bearing Metals. Compagno. Atti. accad. Lincei, 21, I, 473-8. Detection, Separation and Determination of Arsenic and Antimony. Bressanin. Gazz. chim. ital., 42, I, 494-9 ; cf. C. A. 6, 1579. Determination of Chromium in Bronze Containing Tin and Antimony. Schilling. Chem. Ztg., 36, 697. Lead, Tin and Antimony Alloys. Campbell. Metal- ^ lurgie, 9, 422-5 ; cf . C. A., 5, 2063. Separation of Arsenic from Antimony and other Metals by means of Methyl Alcohol in a Stream of Air. Moser and Perjatel. Monatsh., 33, 797-820. The Separation of Arsenic from Antimony and other Metals with some Applications to Toxicological Work. Collins. Analyst, 37, 229-38. Determination of Arsenic and Antimony in Alloys and of Arsenic in Copper. Bressanin. Ann. chim. anal., 18, 468-74; C. A., 7, 35; 6, 1579. ANTIMONY PROPERTIES 21 Determination of Antimony in its Minerals. Caffin. Mon. Sci. (5) 4, 148-9. Detection of Antimony in Qualitative Inorganic Analysis. Peterson. Z. anorg. Chem., 88, 108. Determination of Antimony by Oxidation of an Alkaline Antimonite. Gastaldi and Pertusi. Rend. soc. chim. ital., 4, 83 (1914); through Ann. chim. applicata, I, 567. The Quantitative Determination of Antimony with Especial Reference to Golden Sulfide of Antimony. Gummi. Ztg., 29, 137-9 (1914). Study on the Quantitative Analysis of Antimony Tri- sulfide and its Ignition Products. Bacho. Monatsh., 37, 85-117 (1916). Investigation of the Antimony Spot. Its Behavior Towards Hypochlorite. Vauvel and Knocke. Chem. Ztg., 40, 209-10. Determination of the Antimony Content of Textile Fibers. Von Fellenberg. Mitt. Lebensm. Hyg.. 7, 288-95. The Practice of Antimony Smelting in China. Wang. Bull. Am. Inst. Mining Eng., 1918, 927-45. Note on the Treatment of Antimony Minerals in Sardinia. Rolfo. Ind. chim. min. met. 5, 98-101 ^ (1918). Separation of Antimony and Tin in Hydrochloric Acid Solution. Prim. Chem. Ztg., 41, 414-5. Production of Electrolytic Antimony from Impure Ores. Burr. Eng. Mining J., 104, 789-90 (1917); Chem. Abs., 118 (1918). 22 ANALYSIS OF BABBITT CHAPTER II. TIN. ( Stannum. ) The metal has been known from the most 'remote antiquity. The county of Cornwall, has yielded tin for at least 3,000 years and the mines of Cornwall, have been worked for the oxide of tin since the time of the Phoenicians and Greeks. The alchemistic name for . this metal was Jove, and was indicated by the sign of Jupiter. Properties, Etc.: Chemical symbol, Sn ; atomic weight, 118.7; quad- rivalent; sp. gr., 7.28 (pure); hammered, 7.29; cast, 7.29; rolled, 7.30; electrolytic, 7.25; rhombic, 6.55; molten, 6.98 (232C.) 1 ; melting point, 232.7C. 2 ; volati- lizes preceptible at 1200C. Boiling point, 1550C. 5 (approximate). Specific heat at about melting point, .059 4 ; latent heat of fusion, 13.7 Cal, 5 (calculated) ; heat conductivity (^f<7=100) 14.5; increase in volume on melting 2.8% 6 ; electrical conductivity (Ag=lQQ) 13.F; casting temperature 500 C. 8 Crystalline structure; color, silver-white with a slight bluish tinge; brilliant lustre, not easily tarnished; soft, very malleable and laminable, ^Pascal and Joumiaux. *Hofman. ''Matthiessen. 'Person. ^Richards. *Hofman. 3 Carnelly. 'Toeplar. TIN PROPERTIES 23 but not very ductile and with feeble tencity. Rolled to sheets not over 1/5000 of an inch thick; most malleable at 100 C; most brittle at 200 C; when rubbed gives a peculiar odor similar to that of SnCl 2 solutions. The temperature of the metal when cast, determines entirely its lustre, and degree of cohesion when cold ; rarely used in the pure state for casting as it does not fill the molds entirely. If the metal is poured too hot (exhibiting rainbow colors on the surface), the metal will be brittle, if again heated to 100-140C. If the temperature is too low when poured, the metal will be after cooling, dull and brittle. To obtain the best results as to metallic lustre and at the same time the greatest cohesive strength, the metal must be cast when the surface of the molten metal presents a high degree of lustre. Tin-ash is a mixture of SnO and finely divided Sn, formed by allow- ing the fused metal to stand in contact with air, and if the heating is continued, the greyish coating is converted to yellowish-white SnO 2 , known as putty powder ; resists the action of organic acids to a remarkable degree ; next to Pb, it is the softest metal; a bar of tin when bent gives a peculiar creaking sound (cry of tin), caused by the grinding action of the crystals over each other. 1 Alloys of Sn 90% and Pb 10% preserve the crackling sound, but in a less degree to that of pure tin, and the sound is destroyed by the addition of \% of Zn. Tin pest, a breaking down of the structure of the metal, to a grey friable powder by extreme cold. The action is said to begin at 18 C., and is most rapid at 48 C. Some writers state that the tin pest is a disease of tin, as normal tin is affected when placed in contact with the grey powder, (the author has exposed granulated and bar tin at a temperature of 18 C., to 41 C, the 1 Or the breaking up of crystals along cleavage planes. 24 ANALYSIS OF BABBITT entire winter, with no perceptible change in the structure. No doubt, the structure of the metal becomes very brittle by extreme cold (which acts upon the metal like extreme heat), and when the pigs of tin are piled, the weight of the pigs above, may crush the lower tier to irregular fragments and also to a powder.). The affinity of the oxides Sn and Pb for each other, is shown by heating to a red heat, an alloy of 1 part of Sn-}-4 parts of Pb. Combustion begins similar to that of burning peat or charcoal, and is continued for some time after the heat is removed by using a gentle blast. At ordinary tem- perature, the polished surface of tin-plate is but little affected by the air or moisture, but the bright surface of commercial metal soon tarnishes under the same con- ditions. Commercial metal often contains small portions of Fe, Pb, Cu, Sb, As, Bi, IV, and in some cases, Mn and Zn. The alloys of tin are very valuable. Britannia metal, speculum-metal, gun-metal, bell-metal, pewter, hard and soft solder, engineering alloys, composition and anti-friction alloys, fusible alloys, bronze, phosphor- bronze, and tin amalgam. Tin-plate is thin sheet iron coated with tin. Tin-foil is made from the pure metal or alloyed with Pb, and is extensively used as a covering or packing for perishable and deliquescent material. The crystalline appearance given to sheet tin (Moire Metal- lique), is obtained by rinsing the clean tin plates in dilute HNO 3 or HCI+HNO Z and then with water. The plates are now dipped for a few moments in aqua regia, diluted with 3 volumes of water and heated to about 180 F. The plates are now removed, washed thoroughly with water, dried, and finally oiled or lacquered. The pure metal is used largely for block tin worms for dis- tilling apparatus, block tin pipes for gas and water, working parts of certain dry and wet gas meters, tin TIX PROPERTIES 25 plated ware for household and pharmaceutical use and the tinning of lead, copper and other metals. The metal has the remarkable property of imparting hardness to certain alloys, -which was known to the alchemists, who applied the term of diaboliis metallorum to some of its brittle alloys. Tin conbines with lead in all proportions and strongest alloy of the two metals, is said to be 3 parts of Src-f-1 part of Pb. sp. gr. 8. Sn and Cu do not unite readily with each other, and the resulting brittle alloys, is less brittle and more malleable, if heated and then plunged in cold water. Tin and zinc, when fused, unite readily to form alloys. As the Z)\ predominates, the metal must be cooled quickly, otherwise the metals may separate at the bottom of the molds. The addition of Pb to the above alloys, increases the body of the alloy. Sn and Sb form white brittle alloys, the brittleness increases as the percentage of Sb becomes greater and the alloys must solidify quickly to prevent segregation. According to Chaudet, 10 parts of Sn to 1 part of Sb, form a perfectly ductile alloy. The elasticity, hardness and toughness of ordinary bronze, is greatly increased by the addition of .25 to 2.5% of P, the alloy is now known as phosphor-bronze. SnCl 2 -\-2 H 2 O is a powerful deoxidizing reagent, as it reduces the salts of Hg, Ag, Pt, etc.. to the metallic state and the solutions of other metals from the ic to the ons condition. Pure stannous chloride (SnCl 2 -\-2 H 2 O), is used as a mordant by dyers and calico printers, also for preparation of fuchsine. Stannic chloride (SnCl 4 -\-5 H 2 0) and stannate of sodium (Na s SnO 3 ), are valuable salts of the dyer. Phosphor-tin is a valuable alloy. When the borings (5% P) are treated with acid, there is an evolution of H Z P which ignites in contact with the air. The protoxide (SnO) acts as a base, and the peroxide (SnO 2 ) as a basic and 26 ANALYSIS OF BABBITT an acid forming oxide. The prepared peroxide is used for polishing glass and stone and is known as putty powder. After ignition, pure Sn0 2 is an amorphous white or straw colored powder. SnO is a grayish black color usually, and when pure according to Roth, a red color. The sesquioxide, Sn 2 O s is gray. SnO 2 forms two hydrates, both acids: stannic acid, Sn0 2 , H 2 O, and metastannic acid, Sn 5 O w , 5 H. 2 O. The commercial metal consists of common, refined and grain. Refined tin is made from the purest ores and grain tin from the best pigs. Tin wire has but slight tenacity. Arsenic renders the metal whiter, but harder and the presence of small amounts of Pb, Cn and Fe causes it to become brittle. When SnCl 4 is mixed with one-third of its weight of water, it is termed butter of tin. Powder of tin was used exclusively as an anthelmintic, and is now used as a teniafuge. The medicinal preparations are still called jovial preparations. The metal is soluble in HCl with the evolution of H\ hot HNO 3 converts it to insoluble metastannic acid ; soluble in hot H 2 SO and aqua regia. Native tin has been found in small tablets in bismutite from Mexico. Commercial tin (99.70% Sn) Sp. Gr. 7.33. 1 cubic foot weighs 457.57 pounds. Shrinkage of castings per foot 1/12 or .0833 of an inch. Wire made from iron, 7/100 of an inch in diameter, will sustain 444 pounds, and tin wire if the same size, 32 pounds. "Strain disease," caused not only by a rise in temperature but also by contact of one article with another already affected. Affection taking place at a temperature as high as 37 C. "Museum disease," coins, medals, organ pipes and utensils made from tin, become covered with wart-like spots of a grayish color, changing to a grayish dust. Cavities are left, which become enlarged and increase in size. Said to be a change from white to TIN PROPERTIES 27 gray tin. Tin that has been distilled in vacua, has a brass-yellow color due to the presence of a little sulphur. Portuguese counterfeit money contained as the principal component 90.8-98.3% Sn in most of the coins. The size of the crystal grains in bar tin, determine the intensity of the "cry of tin." Alloys containing free Sn, free Bi and free Sb, will also give the sound, only in a lesser degree. Qual. analy. of tin ash show Sn, SnO 2 , Sb trace, Cu, Fe, C and SiO 2 . The samples are not homogeneous. As high at 50.6% Pb has been found in tin coatings used for wrappings. Chocolates containing acid substances that have been wrapped in zinc foil, that has been used as a substitute for tin foil, varied in content from 141 to 287 mg. of zinc oxide per kg. Opinions differ as to the weight of tin dissolved by decoctions of coffee. According to the Municipal Lab. of Leipzig, two samples of filtered coffee yielded 7.8 and 8.8 mg. of tin resp. Strunk was unable to verify these findings in any particular. The amount of tin found in unvarnished cans of spinach, at least one year old, was less than 126 mg. per kg. The tin content was always lower in the varnished cans. Canned spinach containing 18 mg. of tin originally, after remaining open six days, 1038 mg. of tin were present. The amount of tin in the liquor increases with the length of time in storage. Samples of canned goods 5-8 years old con- taminated with solder, amounts of tin has been found from traces to 3000 mg. per kg. Preserved asparagus which is said to have caused poisoning, contained .29 gram of tin per kg., bound in the vegetable. Staphy- lococcus infections have been treated with a mixture of Sn and SnO, and a 5 to 10 per 1000 solution of SnCl 2 in water or glycerol was used for dressing war wounds ; it is said in some localities that tin-platers never have 28 ANALYSIS OF BABBITT feruncles. Fusible tin boiler plugs are rendered dan- gerous by the formation of Sn0 2 , either as a solid mass at the fire end of the plug or throughout the tin filling. The presence of .3% Zn and a small amount of Pb is said to cause oxidation of the filling. The cooling curves of the freezing point of Sn detects the presence of Pb or Zn in the plugs as low as .1%. The addition of Sn to Cu, lowers the ductility, electrical conductivity and specific gravity, and increases the strength and hardness. Specific heat at about 15C, .055 1 ; at 19-99C., .0552; at 240C, .064. Boiling point, visible ebullition 2275C. 2 volatilization commences, 880 C. 3 Hardness (talc=l) 2.0-3.0 4 ; coefficient of linear expansion per degree C. (OMOO), .0000227 1 ; tensile strength at ordinary tem- perature (pounds per square inch) cast, 4,600; drawn. 5,800; coefficient of rigidity, 5 2.04X10 11 ; Bulk Modulus, 5 5.29X10 11 ; Young's Modulus, 5 5.43X10 11 ; specific heat for fC, Sm (o to .0560+ .000044f. 6 Metallurgical Processes: (1) Blast furnace process, which is the oldest known method of smelting tin and is used for pure coarse lump ore and poor slags ; (2) reverberatory furnace process, for reducing fine and low grade ores and rich slags: (3) electric furnace process is usually used for roasted ores; (4) electrolytic solution and deposition, used for the recovery of tin from tin plate waste and old scrap. Natural Sources: CASSTTERITE (SnO 2 }. Varieties, lode tin, tin stone, wood tin, float tin and stream tin. It is the commercial ore of tin; stannite ((CuSnFc)S or FeCitSnS 4 } or tin ^H of man. 'Molis. ^Greenwood. 5 Kaye and Laby. *Tiede and Binnbrauer. 'Bcde and Regnault. 77JV PROPERTIES . 29 pyrites, the composition of which is uncertain. Other Sources: Hard head dross,- waste products, such as tin ash, white metal turnings, scrap slags and tin plate waste. Mining Localities: The world's supply comes chiefly from Australia, East India Islands, Bolivia and Cornwall, England. Very large deposits of tin ores are in the Island of Banca, New South Wales, Queensland and Islands of Bilitong. It has been worked in Bohemia, Saxony, Peru, Spain, Germany, Hungary, Malacca in Asia, Chili and at Durango in Mexico. Sparingly in the United States. References: Tin Deposits of the World. Fawns, (h). Tin. Alining, Dressing and Smelting. Charleton. (e). Tin. A History of the Trade in, Flower, (e). The Production of Tin. Louis, (e). Tin and Tin Plate. History, Production and Statistics. Weeks, (e). The Technic of Tin Working. German. Janecke. Leipzig. Production of Tin in the United States. 1 The tin from ores of domestic origin amounted to 140 tons in 1916, and to 150 tons in 1917. Alaska produced during the year of 1917, tin valued at $160.000. Commercial Metals. 2 The standard analysis of some of the more important brands : Billiton S, 99.96% ; Sb, .006% ; Cu, .023%. Banca Sn, 99.95%; Sb, .007%; Pb, trace.; Cu, .018%; Fe, .045%; S, trace. Penang Sn, 99.94%; Sb, trace.; As, .013%; Pb f trace.; Cu, .016%; Fe, .028%; S, .04%. 1 C7. S. Geol. Survey (communication.) 'The Foundry, Jan.. 1909. 30 ANALYSIS OF BABBITT Singapore Sn, 99.87%; Sb, .008%; As, .045%; Pb, .034%; Bi, .003%; CM, .052% ; .Fe, .003%; 5", .005%. Mt. Bischoff Sn, 99.80% ; Sb, .015% ; ^j, .063% ; Pb, .037%; JBt, .005%; Cu, .035%; Fe, .042%; S, .008%. Chinese No. 1 Sn, 99.34%; S&, .031%; ^, .040%; Pb, .434% ; 5t, .007% ; Cu, .052% ; Fe, .10% ; 5, .072%. Chinese No. 2 SVt, 98.66%; Sb, .039%; ^j, .035%; P&, 1.035%; Bi, .012% ; CM, .134%; F*, .014%; S, .058%. Chinese No. 3 Sn, 95.28%; Sb, .381%; ^, .050% ; Pb, 3.995% ; t, .020% ; CM, .106% ; Fe, .026% ; 5, .116%. Qualitative Analysis. Stannous Chloride (SnCl 2 ). Place .5 1 gram of SnCl 2 in a small beaker and dis- solve in a mixture of 10 c. c. of //C/+10 c. c. of water.. Add granulated Zn, which will precipitate the Sn as a spongy mass. Wash the residue with water and dissolve in 20 c. c. of hot HCl. Divide the solution into 4 parts and treat as follows : ( 1 ) Add saturated solution of HgCl 2 in excess. A white precipitate of Hg 2 Cl s indicates the presence of Sn. SnCL+2 HgCl 2 =SnCl 4 +Hg 2 Cl 2 . If SnCl 2 is in excess, the precipitate will be gray due to the presence of metallic Hg. 2 SnCl. 2 +2 HgCl 2 =2 SnCl++2 Hg. (2) Heat to boiling and add 2 or 3 c. c. of AuCl^ solu- tion. A purple-red coloration or precipitate of PURPLE OF CASSIUS is formed. 1 ("probably a mixture of the oxides of tin and gold." Silliman.) ("its constitution is not established." Fresenius.) 1 "Cassius purple evidently is due to Au formed by the reduction of AuCk by Sn, resulting in the hydro gel of stannic acid colored by colloidal Au." (Gruenewald.) TIN PROPERTIES 31 (3) Add 2 or 3 c. c. of PtCl 4 solution. A dark crimson coloration indicates the presence of Sn. The depth of color depending upon the amount of stannous salt present. The coloration is caused by the reduction of PtCl, to PtCl 2 . (4) Add 1 or 2 c. c. of Fe 2 Cl Q solution and same amount of K s Fe(CN) 6 solution. A dark blue solution of F e sCyi2y similar to the color of Prussian blue, Fe 7 (CN) l8 , denotes the presence of Sn (no other reduc- ing reagent present). H 2 S precipitates from neutral and acid solutions, a dark brown precipitate of SnS] soluble' in KHO and NaHO solutions, reprecipitated by acids unaltered ; sol- uble in boiling HCl with evolution of H 2 S ; nearly insol- uble in colorless (NH 4 ) 2 S, but soluble in the yellow sulphide as (NH^S) 2 SnS. Reprecipitated by acids as yellow SnS 2 , mixed with free S ; boiling HNO 3 converts it to insoluble metastannic acid 1 (Sn 5 H 10 O 15 ?) . 2 KHO, NaHO, NH 4 HO and alkaline carbonates pre- cipitate from stannous solutions, a white bulky precipi- tate of SnH 2 O 2 , soluble in excess of KHO and NaHO. Stannous salts, when exposed to the air, absorb oxygen and are rapidly changed to stannic salts, forming insoluble oxychlorides (soluble in water containing free HCl) and SnCl 4 . (NH) 2 S produces a precipitate of SnS in stannous solutions. 3 Stannic Chloride. (SnCl 4 ). f "The product of oxidation of Sn by HNO 3 is not insoluble in acids" Dott. Pharm. J., 81, 486. *Fresenius. *Guzman, mentions a new reaction of the Stannous Ions.-\5 g. NH 4 CNS are dissolved in 250 c. c. of water and 1 c. c. of (NHJJfoO* soln. in cbnc. HCl (\ g. in 10 c. c.) added. Sn salts give at once a carmine red. The reagent is more senstive than HgCl^ .1 mg. of SnCl, in 1 c. c. being readily detected. (Chem. Ztg., 35, 797.; 32 ANALYSIS OF BABBITT Place .5 1 gram of SnCl 2 in small beaker and dis- solve in a mixture of 10 c. c. of water-)- 10 c. c. of HCl+3 c. c. of HNO 3 , boil, and dilute with water. Add excess of HCl and granulated Zw, which will pre- cipitate the Sn, Remove the spongy mass, wash and redissolve in hot HCl, dilute with water and treat as described under stannous chloride 1-2-3-4. H 2 S precipitates from hot acid or neutral solutions, a white flocculent precipitate ("it has not, however, as yet been analyzed." Fresensis.) if stannic solution is in excess. If an excess of H 2 S is present, a yellow pre- cipitate of SnS 2 is formed ; soluble in KHO, NaHO, alkaline sulphides, boiling HCl and aqua regia; soluble in (NH 4 ) 2 S and Na 2 S as ammonium and sodium sul- phostannates, reprecipitated by acids as SnS 2 unaltered. Heat on charcoal before the blowpipe in the reducing flame, a small fragment of metallic tin and moisten the white coating of SnO 2 (a slight yellow tinge when hot, and white when cold) with a few drops of C0(JV0 3 ) 2 solution and again ignite, a bluish-green coloration indi- cates Sn. Place a small piece of cassiterite in a small beaker in contact with metallic Zn, cover with HCl and allow to stand a few minutes. A coating of metallic tin is deposited on the surface of the mineral. Quantitative Analysis. Iodine Method. Volumetric Method. P^ace .3-.S gram of the filings in 500 c. c. flask, add 40 c. c. of HCl and heat gently until the alloy is decomposed. Add now frequently, a little KCIO 3 to dissolve the slight residue. Add 30 c. c. of water and boil 3 minutes. Dilute with water to about 90-100 c.c. and add 10 or 12 two-inch iron horse shoe TLV PROPERTIES 33 nails 1 and cork flask with perforated rubber cork, holding a glass tube with a minute outlet. Heat the solution until brisk action begins and allow to simmer on hot sand bath for 30 minutes. Filter luke-warm solution through cotton into 500 c. c. flask containing CO 2 (place 2 grams of HNaCO 3 2 in flask and acidulate with HCl) and wash flask, filter and nails with oxygen free water (500 c. c. water+5 grams HNaCO 3 +W c.c. of HCl). Add 5 c. c. of starch solution and titrate (below 40 C.) with standard I solution to a blue color. Subtract blank and calculate Sn. z A r / 10 / Solution. Place 12.7 grams of pure resubl. / and 20 grams of KI free from iodate, in small beaker and add 20 c. c. of water. Shake frequently until dissolved and dilute to 1000 c. c. with water. Mix thoroughly and allow to stand over night before standardizing. Standardize weekly. SnCl+l 2 +2 HCl=SnCl 4 +2 HI. 2 I=Sn. 2 7=126.92X2=253.84. Sn=llS.7 Xl=H8.7 1 18.7 : 253.84=X : 12.692. 1 c.c. no./ : oo.o-t=^\. : i^.o^z. .v=o.yoo. 1000 c. c. A'/IO Iodine V. S. containing 12.692 grams 1=5.935 grams Sn. oV/10 Iodine V. S. containing .012692 gram /= .00593 gram Sn (theoretical). Standardize the / solution by either of the two following methods: ^Hallett uses a Ni sheet 1.5 x 4 in. (Eng. Min. ]., 97, 1151-3J 2 0r marble cubes. *To prevent the oxidation of the SnCl 2 solution, Smoot has devised a small apparatus. (Eng. Mining J. 106, 25-6(1918) ; Chem. Abst. Vol. 12 No. 17, pp. 1740.) 34 ANALYSIS OF BABBITT (a) Place .2-.3 gram of pure Sn in 500 c. c. flask and treat as described under the determination of tin. .2065 gram Sn I c. c. I solution 1 ^ =.005529 gram Sn. 37.45 .1 c. c. No. 2 Babbitt. .005529X6.55-. 1 c. c. -X 100= 11. 88% Sn. .3 gram Mixture calculation^ 12.00% Sn and, as the commer- cial metal contained 99.70%, the actual content was 11.96% Sn. (b) Place .2 gram of pure As 2 3 in 250 r. c. beaker, add 15 c. c. of a 10% solution of NaHO, and shake until dissolved. Add 20 c. c, of water, a small piece of litmus paper and render solution slightly acid with dilute HCl. Cool, add 50 c. c. of a saturated filtered solution of HNaCO 3 and 5 c. c. of starch solution. Titrate imme- diately with standard / solution to a blue color. As O 3 +4 7+4 PINaCO z As 2 O 5 +4 NaI+4 CO 2 +2 H 2 0. As 2 3 +2 77 2 0+4 I=As s O s +4 HI. 2 I=Sn. 2 Sn=As 2 O 3 =4 I. 2 Sn=llS.7 X2=237A. As 2 O 3 =l97.92X 1 = 197.92. 197.92 : 237.4=.2 gram As 2 3 : X. X=.2399 gram Sn. *Old solution. TIN PROPERTIES 35 .2399 gram Sn. \ c.c.I solution 1 ^ =.005540 gram Sn. 43.4 .1 c.c. No. 2 Babbitt. .005540X6.55-. 1 c.c. X 100= 11.91% Sn. .3 gram. Determination of Sn in Commercial Metal. Iodine Method. Volumetric Method. Place .2-.3 gram of the very fine filings or borings in 500 c. c. flask, previously filled with CO 2 . Add 40 c.c. of HCl and cork flask with rubber stopper holding a Kroonig valve. Place on hot plate and heat gently to about 80-90C. until the metal is dissolved. Remove stopper, add 50 c. c. of water and 6 two-inch horse shoe nails that have been bent in the form of loops and fastened to a piece of fine platinum wire, the end of which projects outside of the flask. Place the stopper in the flask and heat until brisk action begins ; then allow to simmer on hot plate or sand bath for 30 minutes. Cool the flask and contents quickly with ice water, remove the nails and wash thoroughly with oxygen free water. Add 5 c. c. of starch solution and titrate to a blue color with standard / solution. Subtract blank and calculate Sn. (a) 99.73% Sn. (b) 99.68% Sn. .2 gram .4,y 2 O 3 =r.2399 gram Sn. .2399 gram Sn. (1) 1 c.c. TV/10 / sol. 2 = =. 005967 grm. Sn. 40.30 .1 c.c. *Old solution. 2 New Solution. 36 ANALYSIS OF BABBITT .2399 gram Sn. (2) 1 c.c. A'/10 / sol. 2 = =.005960 grm. Sn. 40.35 .1 c.c. .005963 3 X33.95-.25 c. c. (blank) (a) - -X 100=9973% Sn. .2015 gram. .005963 3 X 34.00-. 25 c. c. (blank) (b) - X 100=99.68% Sn. . .2019 gram. Detection of HIO a in KI. Dissolve 1 gram of KI in 20 c. c. of water, freshly boiled and cooled. Add 5 c. c. cold starch solution and 3 drops of dilute H 2 SO 4 (1:3). No blue coloration in 1 minute indicates less than .0001% of / 2 O 5 . (Merck). Starch Solution. Mix .5 gram of corn starch with 250 c. c. of cold water and heat to boiling. Cool, decant the clear solu- tion and preserve for use. (A) Electrolytic Method. Place .5-1 gram of the finely divided alloy in 150 c. c. beaker, cover with 20 c. c. of water, add 2.5 grams of H 2 C 4 H 4 O 6 and heat to dissolve. Add 10 c. c. of HWO 8 (1.42), and heat gently until the alloy is decomposed. Dilute to 50 c. c. with water, add a concentrated solution of NaHO until the first precipitate redissolves and the solution is clear. Add 20 c. c. of colorless saturated solution of Na 2 S (1.20) and allow to stand on hot plate about thirty minutes. Filter into 400 c. c. beaker and wash thor- *New solution. 9 Aver age. 77A T PROPERTIES 37 oughly with hot dilute Na 2 S solution (2%), keeping the volume of the solution down as much as possible. Add to nitrate, dilute H 2 SO 4 (l : 1) until the solution is slightly acid, stir thoroughly, allow to settle if possible and decant on 12^2 c. m. qualitative filter (use two separate filters if necessary). Transfer precipitate to original beaker with a fine jet of water, return funnel and filter to rack and dissolve the remaining sulphide on filter with 25 c. c. of (NHt) 2 S solution, diluted to 50 c. c. with hot water. Wash the filter thoroughly with hot water and evaporate solution to about 125 to 150 c. c. Dissolve the residue in beaker with 15 to 20 c.c. of (NH 4 ) 2 S, heat gently until the solution is clear, then add 5 grams of KCN and heat on steam plate until the solution is nearly colorless. Dilute to 175-200 c. c. with water and elec- trolyze with JVZ> 100 =1.5-1^6 amperes 3.5-4 volts. Time six hours. Remove cathode as described under the determination of Sb, wash with water and then with C 2 H Q O. Dry in air bath for thirty minutes at a tem- perature of 80-90C. and weigh as Sn+Sb. Subtract the weight or percentage of Sb and the difference equals the weight or percentage of Sn. Weight taken=.5 gram. 1.6 Used 4 amperes (=4) 7 volts, (four 32 and two 16 .40 c. p. carbon lamps in parallel). (1) Cylinder-)- deposit 10.4466 grams. = 10.0391 . " .4075 gram. 38 ANALYSIS OF BABBITT .4075 gram Sn+Sb. -X 100=81.50%. .5 gram alloy. 81.50% Sn+Sb 9.2Q% S6.=72.30% Sn. (2) Cylinder-f deposit^ 10.4465 grams. = 10.0391 " .4074 gram. .4074 gram Sn+Sb. -X 100=81.48%. .5 gram alloy. 81.48% Sn+Sb 9.10% ^.=72.38% Sn.. or, .4075 gram Sn+Sb .0460 gram Sb. (1)- -X 100=72.30% Sn. .5 gram alloy. .4074 gram Sn+Sb .0455 gram Sb. (2) -X 100=72.38% Sn. .5 gram alloy. Weight of cylinder before deposit= 10.0391 grams. Weight of cylinder after cleaning= 10.0390 grams. The presence of KCN will retain the S in solution and .will keep it from separating out on the anode, in excess, by forming KCNS with the polysulphides. (Classen). KCN+S=KCNS. At the end of the electrolysis, the solution is colorless and acid, with some free 5. Cleaning Cylinder. 1 *Nessler jars of 100 c. c. capacity, can be used to contain the separate solutions of HCl, HNO 3 and C 2 H e O. TIN PROPERTIES 39 Place the cathode very slowly in hot concentrated HNO S and allow it to remain about five minutes. Remove, wash thoroughly with water and place for same length of time in hot concentrated HCl. Wash with water and repeat the acid treatment if necessary. Finally, wash thoroughly with distilled water, ignite gently, cool and weigh and compare weight with that obtained before electrolysis. (B) Electrolytic Method. Proceed exactly as de- scribed in (A) Electrolytic Method, until the alloy is in in solution. Render solution slightly alkaline with a concentrated solution of NaHO, still retaining a clear solution without a precipitate; then add 2 grams of NaHO in excess. Add 15 c. c. of Na 2 S solution (1.15) and treat exactly as in the preceding method until the Na 2 S solution of Sn and Sb is obtained. Acidulate solu- tion slightly with HCl and evaporate on hot plate to about 60-75 c.c. Add ' 10 c.c. of HCl (1.20) and 2 grams of Na 2 O 2 in small portions, stirring meantime, until the solution is clear with the exception of free 6\ Boil three minutes, filter into 400 c. c. beaker and wash filter contents thoroughly with hot water. Place a small piece of litmus paper in solution and render slightly alkaline with NH^HO. Add 7 grams of acid NH^HC 2 6, .H 2 O for every .3 gram of Sn present, heat to dissolve if necessary, and when the salt is in solution, add 9 grams of C 2 //,O 4 . Warm to 60-65C, and electrolyze with a current of ATZ) 100 =1-1.5 ampere. Time 4-4^2 hours. Wash the cathode with water without interrupt- ing the current and immerse in C // 6 O. Dry thirty minutes at 80-90C. Cool and weigh. \Veight taken=.5 gram. 40 ANALYSIS OF BABBITT (3) CyHnder+deposit= 10.4028 grams. = 10.0407 " .3621 gram of Sn. .3621 gram Sn. (3)- -X100=72.427 C Sn. .5 gram alloy. Results from Xo. 1-2 and 3 are from the same sample of alloy. Cathode. A cylinder of platinum wire gauze. 2 inches high and 1 inch in diameter. Diameter of wire .004 inch. 44 mesh. Area 6.3 inches. Anode. A platinum foil 1^4 inches X 1/4 inches, fastened to a piece of thick platinum wire. Caution. When using 4-5 amperes of current, do not allow the anode to come in contact with the platinum gauze of the cylinder, otherwise the gauze will fuse at the point of contact. Acid A r // 4 //C 2 O 4 .// 2 O. (Ammonium Binoxalate). Dissolve 124 grams of (NH 4 ) 2 C 2 O 4 .H O in hot water, add 126 grams of // 2 C 2 O 4 .2/f 2 O,~stir thoroughly until dissolved and evaporate to dryness. Place in bottle and cork tightly. The following articles will be of interest to the chemist : The Titration of Stannous Salts with Iodine.' Young. J. Amer. Chem. Soc., Oct., 1897. On the Estimation of Tin. Pattinson and Pattinson. J. Soc. Chem. Indust, March, 1898. TIX PROPERTIES 41 Rapid Method for the Determination of Tin in Copper- Tin Alloys. Levy. Chem. Eng., Jan., 1906. A New Form of Tin Disease. Hasslinger. Monatsh, 29, 787-90. (Aug.). The Determination of Tin in Tin Plate. Meyer. Z. angew. Chem., 22, 68. The Assay of Tin Ores. Gray. J. Chem. Met. S. Africa, 10, 312-5. 402-3. 11, 10. Separation of Antimony and Tin by Distillation. Plato. Z. anorg. Chem., 68, 26-47. New Method for the Determination of Tin in the Presence of Antimony. Sanchez. Bull. soc. chim., 7, 890-4. Method for the Determination of Tin in Canned Foods. Schreiber and Taber. Bur. of Chem., Circ., 67. Determination of Tin and Antimony in Soft Solder. Goodwin. J. Ind. Eng. Chem., 3, 34. Analysis of Tin Ores. Bayerlein-Essen. Z. angew. Chem., 23, 969. Occurrence and Estimation of Tin in Food Products. Smith and Bartlett. U. S. Dept. Agr., Bur. Chem., Bull., 137, 157. Examination of Tin in an Ore. Morgan. Chem. Eng., 14, 289-91. Tin and Its Methods of Assay. Zarath. Mexico. Mem. rev. soc. cien. "Antonio Alzate," 28, 193-7. Assay of Tin. Lewis. London Min. J., 1911, 606. J. Chem. Met. S. Africa, 12, 32-3. Some Analysis of Different Grades of Commercial Pig Tin. Anon. Brass World, 7, 396. 22 complete analy- sis of com. pig tin shows Sn content of 95.28% 99.96%. 42 ANALYSIS OF BABBITT Proposed Method for the Estimation of Tin in Canned Goods. Lowrie. Orig. Com. 8th Intern. Congr. Appl. Chem., 18, 247. Special Adaptation of Iodine Titration Method for the Estimation of Tin. Especially in Connection with Determination of "Salts of Tin" in Canned Foods. Baker. Orig. Com. 8th Intern. Congr. Appl. Chem., 18, 35. New Volumetric Method for Tin. Patrick and Wils- nack. J. Ind. Eng. Chem., 4, 597-9. The' Solution and Oxidation of Tin in Dilute Nitric Acid. (A contribution to the analysis of commercial tin.) Bunge. Pharm. Zentralhalle, 54, 845-6. Volumetric Determination of Tin. Hallett. Eng. Mining J., 97, 1151-3. The Assay of Tin Ores. Hutchin. Inst. Min. Met., Feb., 1914. Notes on the Direct Volumetric Determination of Tin. Rawlins. Chem. News, 107, 53-5. The Determination of Tin in Bronzes. Ibbotson and Aitchison. Chem. News, 107, 109-10. The Volumetric Determination of Tin with Potassium Bromate by the Method of H. Zschokke. Fichter and Muller. Chem. Ztg., 37, 309. Analysis of Tin and Tin-Lead Dross. Bertiaux. Ann. chim. anal., 18, 217-9. Some Physical Properties of Tin. Garland. Cairo Sci. J., 8, 27-41. Assay of Tin Ore. Caspell and Beringer. London Mining J, 1913, 149. Analysis of Copper-Tin Alloys. Gemmell. J. Soc. Chem. Ind., 32, 581-4. The Volumetric Determination of Tin by Potassium lodate. Jamieson. J. Ind. Chem., 8, 500-2 (1916). 77.V PROPERTIES 43 The Detinning and Analysis of Tin Plate. Heise and Clemente. Philippine J. Sci., 11 A, 191-9 (1916). Tin Ash. Kolthoff and van Lohuizen. Utrecht. Pharm. Weekblad, 54, 718-20 (1917). Phosphor-Tin and a Volumetric Method for its Analysis. Lee-Fegely-Reichel. J. Ind. Eng. Chem., 9, 663-8 (1917). The Analysis of Tin Ores. Golick. Eng. Mining J., 102, 827 (1917). A Handy Method for Assaying Tin Ores. Henderson. Eng. Min. J., 103, 267 (1917). Separation of Antimony and Tin in Hydrochloric Acid Solution. Prim. Chem. Ztg., 41, 414-5 (1917). The Wet Assay of Tin Concentrates. Hutchin. Insti- tution Min. and Metal, Bull., No. 149, 1-27 (1917). The Volumetric Determination of Tin. Hallet. J. Soc. Chem. Ind., 35, 1087-9 (1916). A New Infective "Disease" of Tin. "Strain Disease." Cohen. Chem. Weekblad., 6, 625-40. Physical Chemical Studies of Tin. Cohen. VII., Z. physik. Chem., 63, 625-34 (Aug. 21), also Chem. Ztg., 32, 1041 (Oct. 24). Notes on Tin. Dott. Pharm. J., 81, 486. Tin and Tin Pest. Berger. Schweiz Wochschr., 48, 117-22. The Electrolytic Determination of Tin in Alloys. Schurmann and Arnold. Mitt. kgl. Materialpruf- ungsamt, Gross Lichterfelde West, 27, 470-3. The Separation of Platinum and Tin. Wohler and Spengel. Z. anal. Chem., 50, 165-171. A Modification of the "Gay-Lussac" Method for Silver Bullion Containing Tin. Salas. Bull. Am. Inst. Mining Eng., 63, 267-78. 44 ANALYSIS OF BABBITT Determination of Tin in Tinned Iron. Crispo. Bull. etudiants inst. Meurice, I, 150-2; through Bull. soc. chim. belg., 26, 466. Determination of Tin (Report on Meat and Fish). Hoagland. Proc. A. O. A. C, 1911 ; U. S. Dept. Agr., Bur. Chem., Bull. 152, 213. Note on Determination of Tin in Foods. Hansen and Johnson. Proc. A. O. A. C, 1911: U. S. Dept. Agr., Bur. Chem., Bull. 152, 117-8. The Determination of Tin in Ores. Milou and Fouret. Discussions 8th. Inter. Cong. Appl. Chem., 27, 23 ; cf. C. A., 6, 3250. Confirmatory Tests for Tin. Curtman and Mosher. J. Am. Chem. Soc., 35, 357-65. Separation of Antimony and Tin. Huybrechts. Bull. soc. chim. belg., 27, 66. Method of Estimating Tin in its Ores, Alloys and Compounds. Banerjee and Banerjee. Proc. Chem. Soc., 28, 102. The Electrolytic Separation of Tin from Tungsten. Threadwell. Z. Elecktrochem., 19, 381-4. Electrolytic Estimation of the Tin in Metal Foil of Lead, Tin and Antimony Externally Tinned. Belasio. Ann. lab. Gabelle, 6, 231-7; J. Chem. Soc., 101, II, 1099; cf. C. A., 7, 745. The Assay of Tin Ores and Concentrates. The Pearce- Low Method. Wraight and Teed. Inst. Min. and Met., Feb., 1914; through J. Soc. Chem. Ind., 33, 262. Method of Sampling and Analysis of Tin, Terne and Lead-Coated Sheets. Aupperle. Metal Ind., 12, 327-8. Note on the Separation of Tin and Copper in Brass Analysis. Liebschultz. Chem. Analyst., 9, 14. 77 A' PROPERTIES 45 Quick Method to Precipitate Tin Electrolytically. Hum- phreville. Eng. Mining J., 98, 964 (1914). Electrolytic Separation of Palladium and Tin. Gutbier- Fellner-Emslander. Z. anal. Chem. 54, 208-13 (1915). The Separation of Palladium and Tin by Means of Dimethylglyoxime. Gutbier-Fellner. Z. anal. Chem. 54, 205-8 (1915). Notes on the Chemical Assay of Tin Ores. Matheson. Proc. Australasian Inst. Mining Eng., 1916. Xo. 21, Determination of Tin in Tin Ashes. Wehvart. Chem. Ztg., 40, 458-9 (1916). Tin Ash. Kolthoff and van Lohuizen. Pharm. Week- blad, 54, 718-20 (1917). Physical Chemical Studies of Tin. VIII. Cohen. Z. physik Chem., 68, 214-31 ; C. A., 3, 2780. The Determination of Tin in White Metal by Electroly- sis. Schiirman. Chem. Ztg., 34, 1117-8. Tin Mining near El Paso. Koch. Eng. Min. J., 91. 168. The Origin, Manufacture and Beauty of Tin. Scott. Metal Ind., 10, 7-8. The Presence of Tin in Certain Canned Goods. Buchanan-Schryver. British Food J., 11, 101. Determination of Pin Holes in Tin Plate. Walker. J. Ind. Eng. Chem., 1, 295-7. Electrolytic Determination of Tin on Tinned Copper Wire. Grower. Proc. Am. soc. Testing Materials, 17, II, 129-55 (1917). Estimation of Tin in Low Grade Stuff. Adair. S. Afrian Mining J.; J. Ind. Eng. Chem. 9, 1143 (1917). Electroanalysis of Tin Without Platinum Electrodes. Batuecas. Madrid. Anales soc. espah. fis. quim. 14, 495-511 (1916). 46 ANALYSIS OF BABBITT The Sampling and Assay of Chinese Tin. Browne. Chem. News, 117, 1-2 (1918). Determination of Tin in Concentrates. Smoot. Eng. Mining J., 106, 25-6 (1918); Chem. Abst, Vol. 12, No. 17, pp. 1740. LEAD PROPERTIES 47 CHAPTER III. LEAD. ( Plumbum. ) Mentioned in Ex. XV, 10. It was found in the Sinaitic rocks before the time of Moses, and was known to the Israelites and the Hebrews. It was anciently used to purify silver. Observed by Homer. Pliny gave the name of plumbum nigrum to lead and plumbum canidum to that of tin. The alchemists in their writings, designated the metal by the sign of Saturn. Properties, etc. Chemical symbol, Pb; atomic weight 207.20; tetravalent; Sp. Gr. 11.37 1 ; molten 10.88 (327C.) 2 ; melting point 326.2C. 3 . Fuses at 325.C. Volatilizes at a strong white heat, air excluded. Boils at 1525C. ; specific heat at about melting point .034*; latent heat of fusion 4.00 Cal. 5 ; heat conductivity (Ag=lQQ) 8.5 6 ; increase in volume at about melting point 3.7% 7 ; electrical conductivity (^#100) 8.3 1 ; casting temperature 500 C. 4 ; color bluish-gray, generally known as lead gray ; strong metallic lustre when freshly cut, but when exposed to the air the surface is soon l Matthiessen. 3 Richards. ^Pascal and Joumiaux. *Scien. Amer. ^Person. 'Toeplar. 'Hofman. 48 ANALYSIS OF BABBITT oxidized to the oxide or carbonate, which protects it from further corrosion. Structure granular, as shown by certain etched surfaces, also crystals obtained of regular octahedrons. Combinations of cubes and octa- hedra crystals have been formed in the working of certain metallurgical processes. Crystalline plates of Pb are formed by the voltaic action of metallic Zn on Pb solutions ; tough, ductile, very soft and malleable, but tenacity the lowest of any common metal ; contracts on solidifying, forming a convex surface ; the surface of the molten metal absorbs oxygen rapidly from the air, forming PbO or PbO 2 , according to the degree of heat used. The action of distilled or rain water on lead is similar to that of an acid. The 2 PbCO s +Pb(HO) 2 which is formed generally under these conditions, acts as an energetic poison, readily seen in numerous cases of drinking water or beer that has remained over night in lead pipes. The presence of a small amount of CaCO 3 or CaSO in the water, forms in time a deposit which prevents further action. When water pipes of Pb are used, the action of the particular water in ques- tion upon the metal is always tested by experiment. The metal becomes hard and brittle by repeated melting, due to the absorption of the oxides; rolled to thin foil but cannot be drawn to fine wire; hardness increased by the presence of Ag, Bi, As, Zn and Sb. In the analysis of Pb by electrolysis, a red deposit which resembles Cu is formed on the anode, which gradually disappears as the Pb is deposited on the cathode. White lead (2 PbCO 9 +Pb(HO) 2 ) made from PbS0 4 or PbCl. 2 or by the Dutch, Holland, German, English or French methods, is largely used as a pigment, but is generally mixed with BaSO^ CaSO^ BaCO^ chalk or pipe-clay. Basic chloride of lead (PbCL+Pb(HO) 2 ) LEAD PROPERTIES . 49 has been used as a substitute for carbonate of lead. Cassels and Turners yellow, chrome-yellow (PbCrO 4 ), orange mineral (Pb 3 O), chrome-red (2 PbO.CrO 3 ), Madder reds, vermillionettes and Brunswick greens are all valuable pigments of Pb. Certain mixtures of heavy- spar and white lead are known as Venetian white, 1 part of barium sulphate to 1 part of lead carbonate. Dutch white, 3 parts of sulphate to 1 part of carbonate. Hamburgh white, 2 parts of sulphate to 1 part of carbonate. Average samples of white lead loses 14% of its weight on ignition. Painters colic, a chronic dis- ease caused by the skin absorption of Pb compounds. The symptoms of the disease generally show in the following order: constipation, loss of appetite, weak- ness, extreme thirst, stomach pains, lead palsy, epilepsy, ' and finally total paralysis. Well defined cases of lead poisoning, are shown by the appearance of a blue line at the edge of the gums, showing a deposit of PbS. In many cases, the disease can be avoided by cleanliness. Plumbers, who constantly handle metallic lead seem to be exempt from the disease. Lead forms a suboxide, Pb 2 O (black), a monoxide, PbO (yellow), a sesquioxide, Pb 2 O 3 or PbO+PbO 2 (reddish-yellow), a dioxide or peroxide, PbO 2 (brown), and a compound of Pb 2 O 3 and PbO 2 of varying composition, but is usually P& 3 O 4 (red). According to Dulong, PbC 2 O 4 is decomposed at a heat below 300C, (oxygen excluded) as follows: 2 PbC 2 Ot=Pb 2 0+CO+3 C0 2 . The monoxide or protoxide, called in commerce litharge, is the resulting oxide produced by heating Pb to that degree that it burns with a white light. On a large scale it is manufactured by heating metallic Pb until it forms lead ash, a mixture of Pb and PbO. Upon further heating, it is wholly converted to the 50 . ANALYSIS OF BABBITT yellow protoxide. It is largely used in the manufacture of glass, fluxing and the glazing of earthenware, as it dissolves SiO 2 with rapidity; the preparation of varnish, boiled linseed and other drying oils ; preparing white lead, red lead, miniums, putty, lead plasters, also for the preparation of chlorides, nitrates, acetates and other definite salts of lead. PbO is soluble in HC 2 H a O*, dilute HCl and HNO 3 , soluble in KHO, NaHO and solutions of sugar, almost insoluble in water ( 1 : 12,000) . Some of the salts of Pb have a sweetish taste, noticed in the acetate or sugar of lead. Certain hair dyes contain acetate of lead and an excess of free sulphur. Litharge is very much used in pharmacy and is never used mternally. Mixed with olive oil it forms lead plasters, used for abating inflammation, and for other purposes. Lead Di-Per-Superoxide, or dark-brown PbO 2 is formed when Pb z O is treated with cold dilute HNO 3 . Pb 3 4 +4 HN0 3 =PbO 2 +2 Pb(NO 3 ) 2 +2 H 2 0. This mixture of PbO 2 and Pb(NO s ) 2 , is termed red- lead or oxidized minium by match manufacturers. Com- bined with phosphorus it is largely used as a mixture for lucifer matches. Miniums are intermediate oxides of Pb of variable composition, according to the tempera- ture and care in manufacture. Red lead or Pb 3 O 4 , is a mixture of PbO and PbO 2 and is formed by roasting PbO or PbCO 3 with frequent stirring, for a certain time and at a constant temperature of about 700 F. PbCO 3 =PbO+CO 2 . 3 It is the base of many red pigments and is used for the manufacture of flint glass, cements and many other purposes similar to that of PbO. Lead alloys readily with Sb, Bi and Sn, but said to absorb not more than LEAD PROPERTIES 51 1.5% Zn, .07% Fe and about the same amount of CM. Used largely in the manufacture of the following valu- able alloys: White metal, .0-81%; antifriction alloys, .0-88% ; plumbers' and tinners' solder, 50% ; type-metal, 4 .-90% ; organ pipes, usually 96% ; Chinese tea-chest lead, 87% ; ship's nails, 33% ; expanding alloy, 75% ; soft solder for pillow blocks, 85% ; Hoyle's alloy, 42% : Wood's metal, 25% ; Rose's alloy, 50% ; Onion's alloy, 30%; Newton's alloy, 31%; tinol (solder), 80%; Magnolia metal, 80% ; Lipowitz's metal, 26% ; Ajax plastic bronze, 30% ; shot metal, 97% ; Darcet's metal, 25%; Camelia metal, 15%; Chinese bronze, 15%; Lichtenberg's metal, 30% ; Makenzie's alloy, 68% ; Phos- phorus bronze, 10% ; Guthrie's metal, 19%. Lead pipes that are placed in the earth should be coated with asphaltum to prevent corrosion. In one case, lead pipe that had been in the earth twenty-four years, partly embedded in a cement foundation, showed the trans- formed mass made of twenty-three concentric alternating rings of yellow PbO and twenty-four of red Pb 3 O^ The PbO being formed during the winter and Pb 3 O 4 during the summer. Lead covered cables on wooden supports have been corroded due to the moisture on the supports absorbing organic acids from the wood. The acid produced by white ants has been known to destroy the lead covering of cables. Robinson reports two cases of lead poisoning, caused by using as a face powder a cosmetic labeled flake white, a subcarbonate of lead. Rubber cloth containing lead in the rubber compound, has caused poisoning. The amounts found were .02% and .12% PbO 2 . The gases from burning stearin candles containing lead stearate has caused illness and headaches. The dryness under which tea is packed in lead foil prevents any danger of lead poisoning. It has 52 ANALYSIS OF BABBITT been said that sick lead contains more or less chloride. Lead-lined piping^ is used in the U. S. navy for all salt water pressure piping over \ l / 2 in. to S l /2 in. in diameter, and precautions are necessary to prevent lead poisoning. The Pb dissolving capacity of water decreases gradually as the inside of the water pipes become lined with a mineral deposit, until practically the water is almost free from Pb. Water from peat-covered moorlands will take up 1 to 2.5 grains of Pb per gallon. The addition of 1.5 grains of CaCO 3 before filtration and 1.5 grains- of CaO (clear solution of Ca(HO) 2 ), after filtration will prevent the solution of lead. Alkaline as well as acid solutions, sea-water, cement water and especially lime water attack metallic Pb. A Berkefeld filter retains practically all of the lead present in potable water, that has been taken up from Pb pipes. Lead poisoning has been caused by eating food prepared in ' much used common pottery, due to fatty material penetrating the glaze, and upon reheating, the fat containing Pb com- pounds again returns to the surface. Many cases of lead poisoning among lead-workers, are caused by par- ticles of Pb taken in the food and drink, showing clean- liness is essential. The discoloration of canned foods in the majority of cases, is caused by the metallic sul- phides that are formed by the action of H 2 S, which either forms by the reaction of sulphides with vegetable acids or bacterial action due to insufficient sterilization. Lead caps used on food containers containing vinegar, is considered dangerous, as mustard has been found badly contaminated with Pb. Acute lead poisoning in man from Pb content of earthenware glaze, requires a solu- tion of not less than 20 grams of lead compounds per liter, but repeated doses of a few nig. causes chronic poisoning. Snuff wrapped in Pb foil containing 89% LEAD PROPERTIES 53 Pb caused fatal lead poisoning. The snuff contained 1.75-1.90% Pb. Lead arsenate (Pb z (AsO^) 2 ) is used extensively as a spray to control the ravages of many leaf eating insects. Lead is largely used in building, leaden chambers for the manufacture of H 2 SO 4 , tanks and pans for chemical manufactories, water and gas pipes, batteries, shot, rifle balls, alloys and for many other purposes. Lead has the property of flowing in the viscous state and of being welded by pressure in the cold. Pb and Sn when melted together, unite in all proportions. Pb alloys readily with As, but with Zn and Fe only in limited amounts. Pb and Bi unite in various proportions. Pb and Cu alloys form more readily when Cu is in excess. Calvert and Johnson found expansion in all Sb-Pb alloys. Pb and Hg form amalgams con- taining a^ high as 33% Pb which remain in the liquid state. Hardness of Pb (talc=l) 1.5 1 ; specific heat be- tween O and 100C., .0314; at 15-100C., .0309; at 300C., .0338; molten, .0402; for fC, Sm (o to f). .02925+.000019* 2 ; coefficient of linear expansion per degree C. (O-100) .0000295 3 ; tensile strength at ordinary temperature (pounds per square inch) cast, 2,050; coefficient of rigidity, 4 .562X10 11 ; Bulk Modulus, 4 5.00X10 11 ; Young's Modulus, 4 1 .62X10". Specific gravity of commercial lead (98.30% Pb) 11.33. Weight of 1 cubic foot, 707.27 pounds. Shrinkage of castings .per foot, 5/16 or .3125 of an inch. HCl and H 2 SO 4 have but little action upon the metal, but is readily soluble in hot dilute HNO 3 . Metallurgical Processes: The oldest type of furnace was used in England during the Roman possession. They were termed boles by the *Mohs. 3 Hofman. *Bede and Regnault. *Kaye and Laby. 54 ANALYSIS OF BABBITT leadworkers of that time and were of the most simple ;construction. Charcoal was used as a fuel and the ore melted with a natural blast. After the charge was reduced the melted metal was tapped from the bottom of the furnace. The next form of furnace was the ore hearth, with bellows blast worked by water power. This form of furnace is still in use in some localities. Later, certain distinct processes were used, viz.: (a) air reduc- tion process; (b) carbon reduction process; (c) precipi- tation process. Thes-e methods of reduction or modifica- tions of the same are now known as, (1) Carinthian process; (2) Tarnowitz process; (3) English process; (4) French or Brittany process; (5) Blast reduction process; (6) Hearth process; (7) Precipitation process. The type of furnaces used are: Reverberatory, shallow- hearths, converters, low and high shaft blast furnaces. Blast furnaces are now used in the United States, Australia, Greece and Mexico. The capacity of some of the furnaces are from 140 to 275 tons of lead per 24 hours. Natural Sources: Native lead (Pb), seldom found in the free state. Sometimes alloyed with a little Ag or Sb. GALENITE, (PbS) ; CERUSSITE, (PbCO 3 ) ; anglesite, (PbSO^} ; min- ium (Pb 3 O 4 ) ; pyromorphite, (Pb 5 Cl(PO^) 3 or 3 Pb,P,O 8 vanadinite, (P& 5 C/(FO 4 ) 3 ) ; wulfenite, -, bouronite, (PbCuSbS 3 ) ; clausthalite, (PbSe) ; crocoite, (PbCrO 4 ) ; jamesonite, (Pb,Sb 2 S 5 ) ; mimetite,(Pfr 5 a(^O 4 ) 3 ) ; descloizite, ( (PbZn) (PbOH) FO 4 ); zinckenite, (PbSb 2 S 4 ) ; matlockite, (Pb 2 Cl,O) ; mendipite, (Pb 3 Cl 2 O 2 ) ; lanarkite, (PbO+PbS0 4 ) ; "lead- hillite, (PbSO 4 +3 PbC0 3 ) ; phosgenite, (PbCL+ PbCO 3 ) ; stolzite, (PbWO^\ minetesite, (3 P^^ 2 8 + PbC! 2 ); zorgite, ((PbCu)Se) \ lehrbachite, (PbHgSe) ; LEAD PROPERTIES 55 castillite, (PbCuFeAgZnS) ; naumanite, (PbAgSe) ; jordanite, (PbAsS) ; plagionite, (PbS Sb) ; brongniardite, (2(PM$r)S'+.S i &SV) ; cosalite, (2J%SHKS ( ) ; dufrenoy- site, (2 PW+^jS 1 ,) ; freieslebenite, (5 (PbAg)S+ 2SbS 3 ); boulangerite, (3 PbS-\-SbS 3 ) ; epiboulangerite, (SPbSb) ; schirmerite, (PbAgBiS) ; kobellite, (3 PbS+ (BiSb)S 3 ) ; aikinite, (3 (PbCu)S+BiS 3 ) ; polytelite, (SPbSbAgFe); meneghinite, (4 PbS SbS 3 ) ; geocronite, (5PbS+(SbAs)S s ) ; plattnerite, (P&O ) ; phoenicochro- ite, (3 PbOCr*O a ) ; jossanite, (PbOZnOCrO 3 ) ; poly- sphaerite, ((PbCa) 3 (POJ^(PbCa),PO 4 Cl); kampy- lite, (P& 8 ((^P)0 4 ) 2 +P& 2 (^P)0 4 a). Other Sources: Dross, from lead refining; lead matte, from smelting lead ores containing PbS with FeS and CuS as impuri- ties ; lead slags, from smelting lead processes ; hearth and furnace material, saturated with PbO. Mining Localities : United States, England, France, Sweden, Spain, Scot- land, Germany, Greece, Belgium, Italy, Austria-Hungary, Norway, Russia, Asiatic Turkey, Mexico, Canada, Japan, China and Australia. References: Lead- Smelting. lies. (d). Lead-Smelting and Refining. Ingalls. (e). Lead Refining by Electrolysis. Betts. (d). Metallurgy of Lead and the Desilverization of Base Bullion. Hofman. (e). Metallurgy of Lead and Silver. Part I., Lead. Collins, (e) Metallurgy of Argentiferous Lead. Eissler. (e). Lead and Zinc in the United States. Ingalls. (e). Lead and Its Compounds. Lambert, (e). 56 ANALYSIS OF BABBITT Lead and Zinc Pigments. Holley. (e). Notes on Lead Ores. Fairie. (e). Notes on Lead and Copper Smelting. Hixon. (&). A Precis of Lead Smelting. Longridge. (e). Metallurgy of Lead, including Desilverization and Cupellation. Percy, (e). Notes for a History of Lead. Pulsifer. (e). Lead Smelting. Collis. (). Lead Poisoning and Lead Absorption. Legge-Goadly. (). Primary Lead Smelted or Refined in the United States.* Domestic Ores. ^ During 1914, 534,482 tons; 1915, 555,055 tons; 1916, 571,134 tons. The lead content of ore mined in the United States in 1917, was about 640,000 tons. Commercial Metals. The following analyses indicate the purity of the metal : Refined lead 2 Pb, 99.984% ; Sb, .0057% ; Cu, .0014% ; Fe, .0023%; Zn, .0008%; Ni, .0007%; Bi, .0055%. Refined lead 3 Pb, 99.28%; As, .16%; Sb, tr.; Fe, .05%; Cu, .25%; Ag, .53%. Raw lead 3 Pb, 97.72%; As, 1.36%; Sb, .72%; Fe, .07%; Cu, .25%; Ag, .49%. Hard lead 3 Pb, 87.60%; As, 7.90%; Sb, 2.80%; Ff Cu, which are fully described in the many excellent ,works which treat extensively on the subject of alloys. 1 .Commercial CuSO^.S H 2 O is generally used as a base for copper pigments. The following represent some of ;the most important colors. Brunswick-green, CuCO s -\- Cu(HO) 2 . Schweinfurt's-green or emerald-green, also known as Paris-green, is an aceto-arsenite of copper, (CuOAs 2 O s ) s Cu(C 2 H 3 2 ) 2 . Scheele's-green or mineral- green and blue, is a copper arsenite, CuHAsO z . Wall .paper colored with the above arsenites is considered .dangerous, due to arsenic poisoning. Such papers are said to give off arsenical vapors or dust, which dis- seminate through the air and is absorbed by the lungs and skin. Both of these compounds are also used for anti-insect powders. Mitis' -green is an arseniate of copper. Casselman's-green, free from As, consists of basic acetates of copper combined with more or less water. This pigment is said to have also the formula of C5"O 4 +3 Cu (HO) ,+4 H 2 O due to a different 1 Brannt, Hiorns, Buchanan, Sexton, Gulliver, Parry, Law. COPPER PROPERTIES 83 method in its manufacture. Lime-blue, a mixture of lime with a weak solution of Cu(NO z ) 2 so that the lime is saturated. Oil-blue is essentially CuS. Verdigris is a basic hydrated copper acetate. The blue variety has approximately the composition of (C 2 H z O 2 ) 2 Cu, Cu(HO) 2 +5 H 2 O and the green variety 2 Cu(C 2 H z O 2 ) 2 +Cu(HO) 2 . The salt contains a variable proportion of bibasic and tribasic copper acetates. Verdigris forms the base of green-inks, green-oils, green stains and glazes. The green rust of copper is CuC0 3 , and should not be confounded with true verdigris. Vienna-green, is a mixture of As 2 O z and verdigris. Bremen-blue or Bremen-green is essentially hydrated oxide of copper. Brighton-green, CuSO^-\-Pb(C 2 H z O 2 ) 2 -\-CaC O z , Blue-verditer is Cu(NO z ) 2 mixed with CaCO z . Bice-blue, native CuCO s . Copper-blue, a mix- ture of CuCO z and CaCO z . Egyptian-blue is formed by heating SiO 2 , CaO, CuO and Na 2 0, at a temperature not exceeding 800 F. The resulting product is then ground. There are four oxides of copper, viz., copper tetrantoxide, Cu 4 O, olive green powder which rapidly absorbs oxygen when exposed to the air. Copper hemi- oxide, cuprous oxide or suboxide, Cu 2 O, red. Formed by heating metallic Cu and is found native in octahedral crystals, occurs as cuprite or red copper ore. This oxide is used to produce copper glass of a fine ruby color. Cuprous hydroxide, Cti 9 O z (HO) 2 , bright yellow, absorbs oxygen when exposed to the air and becomes blue. The hydroxide is soluble in NH 4 HO forming a colorless solution, which when exposed to the air becomes a dark blue color. Cupric oxide, monoxide or protoxide, C:iO, black. Occurs as melacnite or black oxide of copper. Formed by the gentle ignition of hydroxide, carbonate 84 . ANALYSIS OF BABBITT or nitrate and is quite soluble in acids and is the base of all green or blue salts of copper. Cuprous oxide when ignited in contact with the air changes to CuO. This oxide is used to color glass a fine green. Cupric hydroxide, Cu(HO) 2 , light blue. Soluble in NH 4 HO forming a blue solution. CuO and Cu(HO) 2 are both soluble in HNO Z , HCl and H 2 SO. Copper dioxide, CuO 2 .H 2 O, yellowish-brown powder which decomposes readily into CuO and oxygen. Pure copper is extensively used for submarine telegraphs as it is, with the exception of Ag, the, best conductor of electricity. The commercial metal is largely used for a great variety of purposes .both technical and domestic. Especially valuable in the manufacture of tubular boilers, vacuum pans for sugar works, brewery, distillery and many kitchen utensils, Ship-sheathing and electrical apparatus. The prehistoric copper miners of Lake Superior used the metal exclu- sively for hammers, chisels, arrow-points, spear heads, knives, needles, axes and fish-hooks, long before methods for the smelting and the extraction of iron were known. Permanent magnets have been made from nearly pure copper by first heating the metal to redness, plunging in cold water and then magnetizing in a field of over 3000 c. g. s. units. The metal retains permanent mag- netism amounting to .14 c.g.s. Magnetism not due to .the presence of iron. Bosh-cooled copper pig is said .to contain occluded moisture which is difficult, if not impossible to drive off under about 240 F. A piece of copper alloy taken from a ship's keel, contained orig- inally, 45-55% Cu, 40-45% Zn and about 1% of each of Pb, Mn and Fe. After being exposed to the action ,of salt water was found to contain 52.7% Cu, 41.1% Cu 2 0, 1.44% H 2 0, 2.75% Pb, Zn and Fe salts and 2.05% of insoluble material. The Zn had practically COPPER PROPERTIES 85 disappeared. The corrosion of Cu by salt water, usually produces a scale of Cu 2 O. Copper for casting should contain about 99.9%, and the brand also known. The greater the purity, the greater the electrical conductivity. With .03-.80% As present, relative conductivity is lowered from 100 to 40. The cold-drawing of copper increases its tensile strength and reduces elongation. A black coating on copper is obtained by moving the objects about in a 5% bath of NaOH, to which 1% of powdered K 2 (SO^) 2 has been added. Other metals are first Cu plated before treatment. The time required for pure Cu is about five minutes and for alloys about five to ten minutes. According to Meunier, when electrolytic copper is heated until it is glowing and then plunged into the interior of the burner flame, the metal continues to glow and at the same time colors the flame green, showing that combustion is taking place without flame. It is said that the color of the flame is due to the volatilization of amorphous Cu which binds the crystals of the metal together. Repeated melting of copper shows after each melting, a distinctly inferior quality, which is clearly shown by the testing machine. Oxidation and absorption of S causes the inferiority. By the intro- duction of small quantities of CuO to molten glasses rich in alkali and either CaO or PbO, blue colors are obtained. Weintraub has succeeded in casting very pure Cu by adding B 6 O to the molten metal. Sound castings of high conductivity are obtained from either sand or iron molds. 1 Electrical conductivity as high as 97% has been obtained. Archbutt states that copper fire-box plates containing .66% As, .5% Sb, .05% Bi, .06% O 1 A small amount of Sr added to molten Cu, is said to produce a harder than ordinary Cu casting free from blow holes. (Iron Age, May 23, 1918J 86 ANALYSIS OF BABBITT and .63% As, .03% Sb, .07% Bi, .09% O withstood hot working and service. The idea then is that the supposi- tion of .0001% Bi will change good copper into the worst conceivable is an error. In general, the addition of Mn, Sn or P to Cu increases the strength and hardness and lowers the ductility, electrical conductivity and spe- cific gravity. According to Bardwell, the following which is based on the conductivity curves of copper, the zone of cold rolling lies at 0-150 ; the zone of relaxa- tion at 150-355 ; the zone of recuperation at 355- 425 ; the zone of complete annealing at 425-600, and the bending zone at 600. Under the microscope, cold rolled Cu show slip bands indicating a strained condition. These bands disappear and very small crystals are formed after the metal is annealed in the zone of relaxa- tion. Large crystals are formed in the zone of recupera- tion and the maximum of regular growth of crystals in the annealing zone. Above this temperature the crystal growth is rapid and with a decrease of ductility and con- ductivity. Pionchon has shown that when two Cu plates are placed in water and the circuit closed with a gal- vanometer, a deflection is seen when one of the elec- trodes is tapped. After repeating the test, the reaction becomes less and less and finally ceases entirely. Traces of Cu have been identified so minute that no chemical reagent will detect it. To determine the areas of Cu coatings of light and heavy deposits, Wilson recommends covering the object entirely with beeswax, removing this from flie area in question and the Cu determined in the solution as usual. According to Caesar and Gerner, pure Cu begins to soften at 200, most rapidly between 225 and 275, and is complete between 300 and 350. The cold-worked condition persists up to 300 and the most rapid softening near 350. For the dark-gray coloring COPPER PROPERTIES 87 of Cu, Groschuff recommends dipping the Cu casting for ten or fifteen minutes in a boiling solution of 100 c. c. of water, containing 12 grams of CuSO^.S H 2 O and 1.5 grams of KMnO^. A brown color is produced by dipping the objects in a boiling solution of 12 grams of CuSO^.S H 2 O dissolved in 100 c.c. of water. Even if scoured brass and glass beakers gave identical results in the determination of extract of malt, tarnished brass beakers influenced the results considerably. According to Ling and McLaren, worts from such beakers con- tained as high as .1 gram of Cu per gallon. Traces of Cu have been found in filter paper, including analytical grades. The skin absorption of Cu by brass workers has been shown by the detection of the metal in the urine and green sweat stains on the underclothing of the workers. The action of the Cu salts, also exert a prophylactic action with respect to caries and oral sepsis. The use of bad gold alloy in the mouth has caused chronic copper intoxication. Hansen states that the fumes of Cu from the electric arc furnace are poisonous. The symptoms were great inconvenience in breathing, and twenty-four hours later, severe nausea and soreness similar to that of acute grip. The conditions of ventila- tion during the melting and pouring were the most favorable, and should it had been otherwise the results would have probably been very serious. According to Graff, the books of a reputable German firm has shown for the greening of preserved vegetables, the following weights of CnSO.5H 2 O that has been used on an average, per kilo of vegetables: 1903, .90 gram; 1904, .71 gram; 1905, .96 gram. From a number of analysis of the products, the CuSO 4 . S H 2 O in the drained vege- tables, varies from 200 to 1377 m. g. per kilogram, also amounts of copper sulphate smaller than 215 m. g. per 88 ANALYSIS OF BABBITT kilo do not produce a satisfactory greening of the vege- tables. The medicinal dose of sulphate of copper, as a astringent or tonic, is .016 gram gradually increased; as an emetic, .13-.33 gram. According to Liberi-Cus- mano-Marsiglia-Zay, copper is constantly found in the fruit of the tomato. The amount varies from .14 m. g. to 2.10 m. g. per k. g. of juice and pulp and from 3.8 m. g. to 19.5 m. g. per k. g. of dry matter. The Cu contents of the plants was not due to spraying with Cu mixture. Hart states that pressed beef contained small amounts of Cu due to the gelatin that was used as a garnish. The Cu contents expressed in m. g. per k. g. were: pressed beef, 0-34; gelatin A, 25; gelatin B, 104; jelly preparation, 60; and samples of gelatin for family use contained 0-56.3 m. g. of Cu per k. g. Samples of canned spinage has been found to contain from 128 to 275 m. g. of Cu per k. g. The highest permissible limit of Cu is placed at 55 m. g. per k. g. Canned peas of French origin, from the various provinces of Canada, contained in majority of cases an excess of Cu exceeding Tunnicliffe's limit of l / 2 grain per Ib. or 71 parts per million. Caraccas, Guayaquil and Bahia cocoas, contain respectively, .020 g., .027 g., .034 g. of Cu per k. g. in the shell-free seeds and .040 g., .014 g., and .035 g. respectively in the shells. Sweetened chocolates showed the Cu content to be a mean of .012 g. per k. g. Minute amounts of Cu has been found in sample of caffeine. A sample of pomace brandy from Maconnais, showed 15 m. g. of Cu per liter. The green color of some oysters may not be due to Cu but to a green pigment, but as high as 40 m. g. of Cu has been found in the blue colored variety, while those that were uncolored contained 9 m. g. It is said that a small COPPER PROPERTIES 89 amount of Cn salts in milk has been found to be highly efficient as a preservative. Metallurgical Processes. The methods that are used for the extraction of copper from the various ores differ, and the treatment must vary according to the nature of the ore. (1) Ores containing Oxides. (2) Pyritical ores. (3) Low grade ores. (4) Native copper. Oxidized ores are usually smelted in shaft-furnaces with coal or coke, and fluxed so as to produce a slag which does not absorb copper. The cupola furnace (German process) is prefered for very rich ores, as it gives a quicker extraction. The resulting product of black copper is then treated in the reverberatory furnace. A special form of cupola furnace is employed for the smelting of oxidized ores rich in iron. If fuel is cheap, rich ores may be smelted in the reverberatory furnace (English process). The ores are often first reduced to black copper before treatment in the above furnace. Pyritical ores are first roasted or calcined and then treated in a crucible, pit, cupola, shaft, converter, rever- beratory or a combined smelting in cupola and rever- beratory furnaces with a final product of black copper, which is then further refined to partially remove the impurities. The remainder of the latter, is nearly all removed with the suboxide of copper, by a rapid melting of the metal under a layer of charcoal. Low grade ores are generally treated by hydrometal- lurgical methods. The wet copper extraction process is applied to ores which are too poor to admit being 90 ANALYSIS OF BABBITT smelted by the dry process. The ores are treated so as to form copper salts which are soluble in water and the copper is precipitated from the solution by metallic iron. In some mines a solution of copper sulphate occurs naturally. The wet methods are also applied to roasted iron pyrites, a by-product of the sulphuric acid works, which generally contains on an average about 3% Cu. At the present time the chloridizing and leach- ing process is applied to low grade oxidized ores con- taining An, and Ag. Gravity and flotation methods are much practiced for the concentration of poor copper ores* The following well known methods are used for treating low-grade and complex ores. Sulphidizing and flotation, Mosher-Ludlow process and the Slater process. Native copper may contain Au, Ag, As, Sb, Pb, Zn, Fe, Ni, Co and when free from the precious metals, the crude copper is treated in the reverberatory furnace with oxidizing fusion and the product further refined by reducing fusion. At the present time refined Cu is made almost entirely from the crude metal. It is said that the production of pure copper from the ores and matte has thus far, proved a failure. Electrolytic refining methods are generally used for crude copper containing precious metals. The electric furnace can be used as a substitute for the combustion furnace especially, where the price of fuel is high. Native Sources. NATIVE COPPER, (Cu) often containing Au, Ag, some- times Bi or Hg. Occurs in threads, wire and in small grains to several tons in weight. In 1854, one mass of native copper (69.28% Cu) weighing about 500 tons was found in Minnesota, U. S. 1 In Chili, there is known a copper sand or copper barilli containing 60 to 80% *Crookes and Rohrig. COPPER PROPERTIES 91 of Cu and 20 to 40% of SiO 2 . CHALCOPYRITE, (CuFeS 2 ) ; CHALCOCITE, (Cu 2 S) ; BORNITE, (Cu 5 FeS t ) ; CUPRITE, (Cw 2 O) ; TETRAHEDRITE, (Cu 8 Sb 2 S r ) ; MALA- CHITE, (Cu 2 (OH) 2 CO a ) ; CHRYSOCOLLA, (CuSiO 3 . 2H 2 O); AZURITE," (Cw 3 (OH) 2 (C0 3 ) 2 ) ; ENARGITE, (Cu 3 AsS 4 )-, Dioptase, (H 2 CwSiO 4 ) ; Tenorite, (CuO) ; Chalcanthite, (Cw5"O 4 .5 # 2 O) ; Atacamite, (Cu(OH)Cl. Cu(OH) 2 ); Covellite, (CuS) ; Erubescite, (Cw.F*?,). It would be well to mention other copper minerals. Trichalcite, (Cu^OAsO^+5 H) ; Thrombolite, (CuO, H 9 PO 5 ) ; Libethenite, (Cu t OPO t +CuOH) ; Olivenite, (Cu 3 (AsO 5 , PO 5 )+CuOH); Conichalcite, (CuOCaO POiAsO s VO s H)-, Bayldonite, ( (PbO, CuO) 4 AsO*+ 2 H) ; Euchroite, (Cu z OAsO 5 +CuOH+6 H) ; Tagilite, (CuJPOi+CuOH+2 H); Veszelyite, (4 CuOPO 5 + 5 H)\ Liroconite, (CuO, AIO S , AsO,, PO 5 H): Pseu- domalachite, (C 8 OPO 5 +2 CuOH+H) ; Erinite, (Cu 3 OAsO,+2 CuOH) ; Cornwallite, (Cu,OAsO 5 +2 CuOH +3 H); Tyrolite, (Cu B OAsO++2 CuOH+7 H} ; Clinoclasite, (C 3 O^jO 5 +3 CuOH) ; Chalcophyllite, (C3/4jO B +5 CO//+7 H); A. Zeunerite, (CuO, 2 7O 3 ^O 5 +8 //) ; Ammiolite, (HgCuFeSSbO 5 ) ; Lin- dackerite, (2 Cu^AsO s +NiO 9 SO^+7 H) ; Cuproscheelite, (CuOWOs+2 CaOWOz) ; A. Cuprotungstite, (CwO, 3 ^O 3 ) ; Volborthite, (CO, VO^H) ; A. Vanadate of Lime and Copper, ((CuO, CaO) 4 VO 9 +aq) ; A. Hydro- cyanite, (CuOSO 3 ) ; B. Dolerophanite, (Cu 2 AsO 3 ) ; Domeykite, (Cu^As) ; Algodonite, (Ctt i:r ,4j) ; Whitneyite, (Cu 18 As) ; Eucairite, ( (CuAg)Se) ; Crookesite, ((CuTlAg)Se)-, Zorgite, ((P&Ci)5^); Berzelianite, (C5^); Castillite, (CuPbFeAgZnS) ; Griinauite, (OuBiNiFeS); Stromeyerite, ((CX^)5)j A. Chal- copyrrhotite, (Cw 4 CM5 6 ) ; Cubanite, ( 92 ANALYSIS OF BABBITT FeS 2 ) ; Barnhardtite, (2 CuS+FeS+FeS 2 ) ; Carrollite, (2(CuCo)S+CoS 2 ) ; A. Spathiopyrite, (CuCoFeAsS) ; Chalcostibite, (CuS+SbS 2 ) ; Emplectite, (CuS+BiS 9 ) ; Chiviatite, (2(CP&)5'+3 BiS 3 ) ; Binnite, (3 CuS+ Bouraonite, (3(CuPb}S+SbS a ) ; Stylotypite, ; Wittichenite, (3 CuS+BiSJ ; A. Klaprotholite, (3 CuS+Bi 2 S 6 ) ; Aikinite, (3(CuPb)S +BiSz) ; Tennantite, (4(CwF^)S+^^ 3 ) ; A. Julianite, (SAsCuSb); Polybasite, ( (9(AgCu)S+Sb)AsS 3 ) ; A. Epigenite, (CuFeAsS) ; B. Famatinite, (4(3 Cu 2 SSSb 2 S 5 )+3 Cu,SAs,S 5 ) ; Clayite, (SAsSbPbCu) ; A. Nan- tokite, (Cu 2 Cl) ; A. tallingite, (4 CuH+CuClH} ; Percy- lite, (PbCuClOH) ; Crednerite, (Cu*OMn 2 O B ) ; E. Rab- dionite, (Cu, Fe, Co, Mn, O) ; Connellite, (CuOSO^ CuCl) ; Vauquelmite, (Ctt0 3 Cr 2 O 3 +P&0 3 Cr 2 O 8 ) ; Pisan- ite, ((F0O, CwO)SO 3 +7//) ; Chalcanthite, (CwO k 9O a + 5 H)\ A. Cupromagnesite, ((CwOM^O)5'O 2 +7 //) ; Cyanochroite, ((y 2 CuO+y 2 KO)SO a +3 H) ; Brochan- tite, (CuOSO 9 +2y 2 CuHO} ; Langite, (CMO5*O 3 + 3 CuOH+H) ; Cyanotrichite, (5O 8 , AlOfuO, H) ; Woodwardite, (CwO^O.,, COH, AIO 3 H S , 6 H) ; Auri- chalcite, (CwO, ZwO, CO,, //) ; A. Mysorin, (CO,, CO F^O 3 ) ; B. Lime Malachite, (CO 2 , CwO, SO 2 , CaOF, .05; P&, .60; O, .58; 5", .02. Mansfield Refined 5 CM (by difference), 99.48; Ag, .02; Art, .32; Fe, .06; Pb, .12. Refined Tough Copper 6 Cw, 99.94; FV, trace; /40, .056. Rosette Copper 7 CM, 98.48 ; Pb, trace ; Fe, .75; Ni, .26; Sfr, .60. Converter Anodes 8 Cw, 99.1300; As, .1183; S&, .0534; Ni, .0420; Co, .0018; Bi, .0038; Fe, .0110; ^40, .1371; Au, .0008; S>, .0090; Te, .0170; P6, .0065 ; Zn, .0035 ; 5", .2610. Electrolytic Copper CM, 99.89000; Sb, .00515; As, .00108; M, .01000; Ag, .03360 ; i, none. Qualitative Analysis: Cupric Sulphate. (C5'O 4 +5 H 2 O). NHHO greenish-blue precipitate. Soluble in excess to a clear blue solution of (N 2 H 9 Cu)SO^. Color of solution destroyed by KCN. (NH 4 ) 2 C0 3 reaction similar to NH^HO. Na 2 CO z greenish-blue precipitate of CwCOg.Cw (HO} 2 . Soluble in NH 4 PIO to a dark blue solution; soluble in KCN forming a colorless solution. CuCO 8 . Cu(HO) 2 changes on boiling to black CuO ; soluble in NH 4 HO forming a blue solution. KHO and NaHO light blue precipitate of Cu(HO) 2 ; changes to CuO on boiling. K 4 FeCy Q reddish-brown precipitate of Cu 2 F"eCy e ; in- soluble in HC 2 H 3 2 ; decomposed by KHO forming a blue solution. *Dr. Steinbeck. 'Genth. 'Bodemann. "Burns. "The Great Falls Electrolytic Refinery" Tran. A. I. M. E., Aug., 1913. - COPPER PROPERTIES 95 H 2 S black precipitate of CuS : soluble in HNO 3 and KCN; practically insoluble in hot Na^S and K 2 S solu- tions. Yellow (NHi) 2 S produces in cold slightly acid or neutral solutions, a deep orange precipitate of Cu 2 (NH 4 ) 2 S 7 ; completely soluble in excess, reprecipitated entirely as CuS when the solution is boiled thoroughly. Place a platinum crucible lid in small beaker containing 10 or 15 c. c. of the solution of CuSO 4 , place a little granulated Zn in contact with the Pt, add a few drops of HCl and metallic Cu will be deposited on the Pt. Fe precipitates Cu, which is readily shown on a clean knife blade when it is dipped into an acidulated solution of Cu. Dip a platinum wire in the solution of Cu and heat in a non-luminous flame ; emerald-green tint, add a few drops of HCl to the solution and again moisten the wire with the solution and ignite, azure blue ending with an emerald-green color. Uhlenhuth 1 mentions a new reaction for Cu. The reagent is prepared by dissolving .5 gram of 1, 2- diaminoanthraquinone-3-sulphonic acid in 500 c. c. of water and 40 c. c. NaOH solution (d. 1.38). An intense blue is produced by the formation of a complex salt; no other metal produces the same reaction. The color is distinct to 1.9 in 1 million, extreme limit 1.9 in 10 million. Quantitative Analysis: KCN Method. (Ni and Zn absent.) Volumetric Method. Place 1 gram of the finely divided alloy in 600 c. c. porcelain casserole. Add 10 c.c. of //A r O 3 (1.42), heat gently until the alloy is ^Uhlenhuth. Chem.-Ztg., 34, 887. 96 ANALYSIS OF BABBITT thoroughly decomposed and evaporate to 5 c. c. Add 5 c.c. of HCl (1.20), boil five minutes, add 25 c.c. of water and 3 grams of C 4 // 6 and heat to dissolve. Neutralize with NH 4 HO, add 10 c. c. in excess and dilute to 75 c. c. with water. Cool and titrate with standard KCN solution. Before titrating, stand a second casserole containing the same volume of water beside the one containing the solution to be titrated. This will serve as a color com- parison at the end point. Standard KCN Solution. Dissolve 35.8 grams KCN c. p. in 1 liter of water and standardize as follows : Place the selected weight of clean copper foil in 600 c. c. casserole and dissolve in 5 c. c. of HNO^ Add 25 c. c. of water, neutralize with NHHO, add 10 c. c. in excess and dilute to 75 c. c. with water. Cool and titrate. K 3 NH 4 Cu 2 ( CN) 2 Cu=7 KCN 2 Cw=63.57X2=127.14 7 KCN=65.l 1X7=455.77 127.14 : 455.77=X : 35.86. X=10 grams. 1000 c. c. KCN V. S. containing 35.86 grams. KCN 1000 c. c. KCN V. S. containing '35.86 grams KCN 10 grams Cu.( theoretical). 1 c. c. KCN V. S. containing .03586 gram KCN .01 gram Cu. .0052 gram Cu. 1 c.c. KCN solution -- =.003059 gram. Cu. 1.70 c. c. KCN COPPER PROPERTIES 97 No. 2 Babbitt. .003059 1 Xl.55c.c.#CA/' -X100=:.47% CM. 1 gram. Mixture calculation =.50% Cu. A standard solution of CuSO^S H 2 O can be used for standardizing the KCN solution and the weight of Cu taken for titration can be adjusted to correspond nearly to that of the unknown. This avoids error caused by titrating a small weight of Cu in the unknown and using a factor obtained by standardizing with much greater weight of Cu. Dissolve 39.28 grams of CuSO^S H 2 O c. p. in 1000 c. c. of water and mix thoroughly. 1 c. c. = .01 gram Cu (theoretical) as 63.57 : 249.72=X : .03928. X=.01. Take 25 c. c. of the solution with pipette, place in 250 c. c. beaker, add 2 c. c. of HSO 4 , 4 c. c. of strong HNO Z and dilute with water to 150 c. c. Connect plat- inum gauze cathode and electrolyze with a current ND 100 =.5 ampere, 2.7 volts for fifteen hours. When the Cu is all deposited, which can be readily seen by testing 1 c. c. of the solution with H 2 S, lower the beaker and at same time wash the cathode with distilled water maintaining the current meantime. Immerse the cathode in C 2 H Q O for a few seconds, dry and weigh. .2479 gram Cu. =.009916 gram Cu. 25 c. c. 1 c.c. standard CuSO 4 +5 H 2 O solution=. 0099 16 gram Cu. *Old solution. 98 ANALYSIS OF BABBITT After the cathode has been washed with C 2 H 6 O, do not ignite and allow it to burn as it will cause a slight oxidation of the Cu thereby increasing the weight. The KCN method will give satisfactory results with all weights of Cu, providing that all analysis is treated exactly in the same manner and the standardization of the KCN solution with about the same weight of Cu that is present in the unknown. In the standardization of a KCN solution, on the same day and in the same hour, with the same volume of HNO 3 , NH 4 HO and water, the Cu factors were: .0052 gram Cu. ( 1 ) 1 c. c. KCN sol.= =.003059 grm. Cu. 1.70 c.c. KCN sol .009916 gram CM. (2) 1 c.c. KCN sol= =.003251 grm. Cu. 3.05 c. c. KCN sol. .09916 gram. Cu. (3) 1 c.c. KCN sol.= =.003443 grm. Cu. 28.80 c. c. KCN sol. The above results show that the factors are not proportional to the weights of Cu. Dickenson 1 has used a dilute solution of ammonical copper nitrate as a second solution. Should the assay be overrun, 5 c. c. of this solution is run in a flask, a little NH 4 HO is added and the solution diluted with water to the same volume as the assay and titrated with the KCN solution. Should it take 4 c. c. of the KCN solution, 5 c. c. of the Cw(A r O 3 ) 2 solution is added to the original assay and 4 c. c. deducted from the assay reading and the analysis finished as usual. *Eng. and Min. Jour., April 25, 1914. COPPER PROPERTIES 99 The solid KCN soon deteriorates after the container is once opened and the standard solution also becomes gradually weaker on standing, hence the solution should be standardized weekly with clean Cu foil c.p., with standard CuSO 4 solution or with a babbitt of known Cu content. Gravimetric Method. Evaporate the nitrate from the PbSOt precipitate to about 100 c. c. (if Zn is present add 30% of its volume of HCl), heat to boiling and pass a rapid current of washed H 2 S through the solution for fifteen minutes. Filter, wash with H 2 S water and reserve filtrate and washings for the deter- mination of Fe and Zn. Place the wet filter in a weighed platinum crucible and burn at a gentle heat in open crucible, until the filter is charred and the 5 is burned. Ignite strongly, cool and weigh as impure CuO. Dissolve the residue in crucible with a little HCl. transfer with a little water to a small beaker, filter and wash with hot water. Ignite filter and contents, cool, weigh, subtract weight from the total weight and mul- tiply the difference by .7989 which will give the weight of Cu. No. 2 Babbitt. Weight of crucible+CwO-h$'tO 2 =: 19.4961 grams. = 19.4930 " .0031 gram. .0031 X. 7989 XKKbr.49% Cu. .5 gram. 100 ANALYSIS OF BABBITT The above method will give good results with small weights of CuO. If the electric current is available, transfer the filtrate from the PbSO to a 250 c. r. beaker and evaporate or dilute to 150 c.c. Add 4 c. c. HNO S (1.42) and elec- trolyze with a current of ND 100 =.S ampere. 2.7 volts for fifteen hours. Treat as in the electrolysis of Cu in standard CuSO 4 solution and reserve the solution from the Cu for Fe and Zn determination. Estimation of traces Fe and Zn. Boil the reserved filtrate from the H 2 S precipitate (CuS) until free from H 2 S, add 1 or 2 c. c. of HNO 3 and boil for a few minutes. Cool, render solution strongly alkaline with NH 4 HO and allow to stand on hot plate about one hour. Filter on small ashless filter (reserve filtrate for Zn) and wash with hot water. Ignite, cool and weigh as Fe 2 O 3 . Multiply this weight by .7 which will give the weight of Fe. No. 2 Babbitt. Crucible+F 2 3 = 19.2450 grams. = 19.2434 " .0016 gram. .0016X.7 X100=.22% Fe. .5 gram. Acidulate the filtrate from the Fe 2 (HO) Q precipitate with HC 2 H S O 2 , heat to about 80 C. and saturate with washed H 2 S. Allow to settle, filter and wash with hot H 2 S water. Dry filter and contents, ignite carefully in COPPER PROPERTIES 101 weighed porcelain crucible, cool and weigh as ZnO. Multiply this weight by .80336 which will give the weight of Zn. Analysis of No. 2 Babbitt. Pb 69.37 Sb 17.85 Sn 11.91 Cu 49 Fe . , .22 99.84 Sp. Gr 9.6309 The following articles will be of interest to the analyst : The Wet Assay of 'Copper. Dulin. J. Amer. Chem. Soc., May, 1895. The Estimation of Sulphur in Refined Copper. Heath. J. Amer. Chem. Soc., Oct., 1895. The Copper Assay by the Iodide Method. Low. J. Amer. Chem. Soc., May, 1896. Improvements in the Colorimetric Test for Copper. Heath. J. Amer. Chem. Soc., Jan., 1897. Recalculation of Wein's Table of Starch Equivalent to Copper Found. Based on the Factor 0.92. Krug. J. Amer. Chem. Soc., June, 1897. Volumetric Method for the Determination of Copper. Meade. J. Amer. Chem. Soc., Aug., 1898. The Precipitation of Copper by Zinc. Shengle-Smith. J. Amer. Chem. Soc., Oct., 1899. Volumetric Method for the Estimation of Copper. Parr. J. Amer. Chem. Soc., Oct., 1900. Determination of Copper by Aluminum Foil. Perkins. J. Amer. Chem. Soc., May, 1902. 102 ANALYSIS OF BABBITT Notes on the Estimation of Copper by Potassium Per- manganate. Guess. J. Amer. Chem. Soc., Aug., 1902. Note on the Determination of Copper. Parr. J. Amer. Chem. Soc., June, 1902. The Copper Assay by the Iodide Method. Low. J. Amer. Chem. Soc., Nov., 1902. The Cyanide Assay for Copper. Miller. Trans. Am. Inst. Min. Eng., 31, 653. Rapid and Convenient Method for the Quantitative Electrolytic Precipitation of Copper. Richards and Bisbee. J. Amer. Chem. Soc., May, 1904. The Lake Superior Fire Assay for Copper. Heath. J. Amer. Chem. Soc., August, 1902. Improvements in the Cyanide Assay for Copper. Thorn Smith. Eng. Min. J., 76, 581. The Electrolytic Assay o'f Copper Containing Arsenic, Antimony, Selenium and Tellurium. Heath. J. Amer. Chem. Soc., Sept., 1904. A New Method of Sampling Copper. Baggaley. Metal Industry, Sept., 1904. The lodometric Determination of Copper. Fairlie. Eng. Min. J., 78, 787-788. The Determination of Copper. Lloyd. Eng. Min. J., 59, 1053 (June 1, 1905, No. 22). Volumetric Methods for Copper. Fernekes and Koch. J. Amer. Chem. Soc., 1905. The Determination of Small Quantities of Copper in Water. Phelps. J. Amer. Chem. Soc., March, 1906. Copper Salts in Irrigating Waters. Skinner. J. Amer. Chem. Soc., March, 1906. The Electrolytic Assay of Lead and Copper. Guess. Eng. Min. J., 81, 328 (1906) ; also Trans. Am. Inst. Min. Eng., Bi-monthly Bull., No. 61, 1905. COPPER PROPERTIES 103 Analysis of Alloys of Copper. Wilson. Chem. Eng., July, 1905. lodometric Determination of Copper. Brown. Chem. Eng., Sept., 1905. Estimation of Copper. Smith. Chem. Eng., Nov., 1905. Determination of Copper, Arsenic and Antimony in Lead Bullion. Parmelee. Chem. Eng., June, 1905. The Electrolytic Precipitation of Copper from an Alkaline Cynide Electrolyte. Flanigen. J. Amer. Chem. Soc., April, 1907. The Testing of Copper and its By-Products in American Refineries. Heath. J. Amer. Chem. Soc., April, 1907. The Influence of Temperature on the Electrolytic Pre- cipitation of Copper. Withrow. J. Amer. Chem. Soc., March, 1908. On a Volumetric Method for Copper. Jamieson-Levy- Wells. J. Amer. Chem. Soc., May, 1908. A Technical Method for the Complete Analysis of the Electrolyte in Copper Refining. Kann. Chem. Eng., Oct., 1908. Volhard's Method for the Titration of Copper. Kuhn. Chem. Ztg., 32, 1056-7. Same subject. Theodor. C. A., 1908, 3211. Rapid Determination of Copper and Acid in Electrolytic Baths. Pannain. Rome. Ind. chim., 8, 336-7 (Nov. 10). Some Observations on the Permanganate Method for Copper. Herman. West. Chem. Met., 4, 217-20. A Technical Method for the Complete Analysis of the Electrolyte in Copper Refining. Kann. Chem. Eng., 8, 158-60 (Oct.). The Permanganate Method for Determining Copper. Hawley. Eng. Min. J., 86, 1155. 104 ANALYSIS OF BABBITT Influence of Copper on the Titration of Iron by the Zimmermann-Reinhardt Method. Schroder. Z. of- fentl. Chem., 14, 471-92. The Volumetric Estimation of Copper and Chromium and of Copper, Chromium and Iron in Admixture. Hibbert. J. Soc. Chem. Ind., 28, 190. Volumetric Estimation of Copper with Potassium Iodide. Litterscheid. Chem. Ztg., 33, 263-4. The Precipitation of Copper Oxalate in Analysis. Gooch and Ward. Am. J. Sci., 27, 448-58. Gravimetric Estimation of Copper Sulphate. Dallimore. Pharm. J., 83, 69. Comments on Volhard's Volumetric Method for Copper. Theodor. Chem. Eng., Aug., 1909. Sampling and Assaying the Copper Ores of the Ely District. Marsh. Jr. School Mines Quart, 30, 92-7. Copper as a Reducing Agent for Ferric Salts Previous to Their Estimation Volumetrically. Birch. Chem. News, 99, 273-5. A Simplified and Improved Method for Estimating Copper lodometrically. Videgren. Z. anal. Chem., 48, 539-45. Determination of Copper in Canned Vegetables. Bre- beck. Z. Nahr. Genussm., 18, 416. Laboratory Routine in Modern Copper Smelters. Waller. Trans. Inst. Min. Metal., 18, 37-58. The Detection of Copper in Drinking Water. Anon. Pharm > Ztg., 54, 651. Rapid Method for Determining Copper in Slags. Aller. Eng. Min. J.; 88, 278. New Volumetric Method for the Estimation of Copper. Sanchez. Bull. soc. chim., 7, 9-17. Determination of Small Quantities of Copper in Slag. Heberlein. Eng. Min. J., 89, 306. COPPER PROPERTIES 105 The Detection of Cadmium in the Presence of Copper by Hydrogen Sulphide. Wohler. Ber., 43, 1194: cf. C. A., 4, 1585. The Determination of Copper in Blister and Refining Copper. Ferguson. Xichols Copper Co. J. Ind. Eng. Chem., 2, 187. The Electrolytic Determination of Copper at the Ten- nessee Copper Co. Cavers and Chadwick. Eng. Min. J., 89, 954-5. A Rapid Method for the Electrolytic Determination of Copper in Ores. Benner.' J. Ind. Eng. Chem., 2, 195-6. Rapid Method for the Determining Copper in Slags. Aller. Eng. Min. J., 90, 3-4. A response to Diack and Smith's criticism on the author's method (ci. C. A., 4, 737). Rapid Method of Determining Copper in Mattes. Wink- ler. Chem. Ztg., 34, 603. Apparent Copper Reaction in the Burning of Fats. Vaubel. Chem. Ztg., 34, 685. Precipitation of Iron and Copper with Nitrosophenyl- hydroxylamine in Quantitative Analysis. Biltz and Hodtke. Z. anorg. Chem., 66, 426-30. The Determination of Copper. Frary and Peterson. Trans. Am. Electrochem. Soc., 17, 295-302. Separation of Copper from Cadmium and Zinc by Means of Cuproferron. Hanus and Soukup. Z. anorg. Chem., 68, 55-6. A New Method of Estimating Cuprous Oxide in Copper. Coffetti. Gaz. chim. ital., 1909, 39, I, 137-43. Determination of Copper as Anhydrous Copper Sulphate. Recoura. Bull. soc. chim., 7, 832-4. Magnetic Particles in Copper Bullion Sampling. Liddell. Eng. Min. J., 90, 752-3. 106 ANALYSIS OF BABBITT Conditions Affecting the Electrolytic Determination of Copper. Blasdale and Cruess. J. Amer. Chem. Soc., 32, 1264-77. Thiocyanate Determination of Copper. Tsukakoski. Eng. Min. J., 90, 969. Top and Bottom Drillings in Pig Copper. Liddell. Eng. Min. J., 90, 897-8. Influence of Number of Templet Holes in Sampling Copper. Liddell. Eng. Min. J., 90, 953. Indirect Estimation of Copper. Das. Proc. Chem. Soc., 26, 130. The Determination of Copper in Copper-Bismuth Ores. O'Loughlin. Mining Sci. Press, 101, 238. Analytic Work at the Copper Queen Smelter. Anon. Mining Sci. Press, 101, 147-8. The Color and Cyanide Methods for Copper. Austin. Mining World, 33, 753-6. Determination of Arsenic in Copper. Azzarello. Gazz. chim. ital., 39, II, 450-3. Volumetric Determination of Copper. Holland. Mass. Agr. Coll. Expt. Sta., 22d Ann. Rpt, Pt. I, 140-1. Exact Electrolytic Assay of Refined Copper. Heath. J. Ind. Eng. Chem., 3, 74-8. Notes on the Mat Assay. Wilmoth. J. Chem. Met. Soc. S. Africa, II, 24CHL Quantitative Determination of Copper by Hypophos- phorous Acid. Hanus and Arn. Z. anorg. Chem., 70, 282-93. A New Method for Determining Copper in Pyrites and in its Slag. Ivanov. Chem. Ztg., 35, 531. New Form Gauze Electrodes for the Rapid Electrolytic Determination of Lead and Copper. Benner. Met. Chem. Eng., 9, 141-5. COPPER PROPERTIES 107 Analysis of Aboriginal Copper Objects from Mexico and Yucatan. Fiske. J. Amer. Chem. Soc., 33, 1115-6. Determination of Arsenic and Antimony in Anode Copper. Kern and Ching Yu Wen. Met. Chem. Eng., 9, 365-7. The Determination of Gold and Silver in Black Copper. Nissenson. Z. angew. Chem., 23, 968. Electrolytic Determination of Copper. Traphagen. Chem. News, 104, 69-70. Examination of Material Containing Copper, Nickel and Cobalt. Pedersen. Metallurgie, 8, 335. Colorimetric Determination of Copper in Preserves. Serger. Chem. Ztg., 35, 935. Quantitative Determination of Copper in Commercial Sulphates with Alkaline Hypophosphites. Cavazzi. Gazz. chim. ital., 41, II, 374-8. Determination of Copper a Modification of the Iodide Method. Kendall. J. Amer. Chem. Soc., 33, 1847-52. Limits of Accuracy in Copper and Brass Analysis. Lewis. J. Soc. Chem. Ind., 31, 96-7. Sources of Error and the Electrolytic Standardization of the Conditions of the Iodide Method of Copper Analysis. Peters. J. Amer. Chem. Soc., 34, 422-54. The Mathematics of Copper Sampling. Keller. Eng. Mining J., 93, 703-5. A Simple Method for the Quantitative Determination of Copper in Steel. Zinberg. Z. analy. Chem., 51, 19-20. Copper Determination at Granby. Lathe. Eng. Mining J., 93, 1071-3. The Estimation of Oxygen and Occluded Gases in Copper and a Correction to the Electrolytic Assay in the Complete Analysis of Copper. Heath. J. Ind. Eng. Chem., 4, 402-4. 108 ANALYSIS OF BABBITT Rapid Analysis of Copper. Knight. Chem. World, I, 65-6. lodometric Copper Titrations. Sugiura and Kober. J. Amer. Chem. Soc., 34, 818-22. The Oxalate Permanganate Process for the Determina- tion of Copper, Associated with Cadmium, Arsenic, Iron, or Lead. Ward. Amer. J. Sci., 33, 423-32. Electrolytic Determination of Copper in Ores, Contain- ing Arsenic, Antimony or Bismuth. Demorest. J. . Ind. Eng. Chem., 5, 216. Thicyanate-Permanganate Method for Copper in Ores. Demorest. J. Ind. Eng. Chem., 5, 215-6. Hydrogen Peroxide Method for the Determining Copper. Wood. Chemist-Analyst, No. 5, 26. Rapid Fluorine Iodine Copper Analysis. Mott. Chemist- Analyst, No. 5, 8. Estimation of Oxygen and Occluded Gases in Copper, Etc. Heath. I. Ind. Eng. Chem., 4, 691. C. A, 6, 2378. Sampling Anode Copper with Special Reference to Silver Content. Keller. Trans. Am. Inst. Mining Eng., 42, 905-8. The Use of Tantalum Electrodes in the Electroanalytical Determination of Copper and Zinc. Wegellin. Chem. Ztg., 37, 989. The Quantitative Determination of Copper by the Means of Sodium Hypophosphite. Harms. Z. anal. Chem., 52, 616-8. Quantitative Determination of Copper by the Means of Sodium Hypophosphite. Windisch. Z. anal. Chem., 52, 619-28. A reply to the preceding. Estimation of Oxygen in Commercial Copper. Grant. Chemist-Analyst, 7, 19. COPPER PROPERTIES 109 Simultaneous Determination of Copper and Lead, with the Rotating Anode. White. Trans. Am. Electrochem. Soc., 24. A Rapid Method for the Determination of Copper in Pyrites Cinders. Koelsch. Oesterr. Z. Berg.-Hut- tenw., 61, 457; Chem. Ztg., 37, 753. The Determination of Arsenic and Antimony in Conver- ter and Electrolytic Copper. Brownson. Bull. Am. Inst. Mining Eng., No. 80, 1489-95. Some Recent American Progress in the Assay of Copper Bullion. Keller. Bull. Am. Inst. Mining Eng., No. 80, 2093-2115. Determination of Copper by Formaldehyde- Sulfurous Acid. Malvezin. Bull. soc. chim., 13, 721-3. Determination of Copper in Copper Spraying Mixtures. Malvezin. Ann. chim. anal., 18, 220. Apparatus of Franz Fischer for the Rapid Electrolytic Determination of Copper with a Gauze Electrode. Platou. Chem. Ztg., 36, 649. Determination of Copper by the Volumetric Iodide Method. Pozzi-Escot. Ann. chim. anal., 18, 219. Electroanalysis of the Copper Alloys. Fairchild. Met. Chem. Eng., II, 380-2. Electrolytic Determination of Copper in Solutions Con- taining Nitric Acid. Gilchrist and Cumming. Chem. News, 107, 217. Electroanalytical Separation of Copper from Tungsten and Molybdenum. Treadwell. Z. Elektrochem., 19, 219-21. The Determination of Copper in Cast Iron and Steel. Knoppik. Stahl u. Eisen, 32, 1703; through Chem. Zenir., 1912, II, 1788. 110 ANALYSIS OF BABBITT Detection and Colorimetric Estimation of Lead, Copper and Zinc in Tap Water. Winkler. Z. angew. Chem., 26, 38-44. Some Delicate Copper Reactions. Detection of Copper by the Means of Grape Sugar. Schenk. Apoth. Ztg., 28, 137. Detection and Determination of Very Small Quantities of Copper in Vegetables. Guerithault. Bull. sci. pharmacolog., 18, 633-9. Titration of Copper Salts with Titanium Trichloride. Moser. Chem. Ztg., 36, 1126-7. Electroanalytical Determination of Copper in Pyrites. Treadwell. Chem. Ztg., 36, 961. Rapid Electroanalytical Separation of Copper from Nickel and Zinc. Kremann. Monatsh., 33, 1077-9. The Quantitative Separation and Estimation of Copper by Means of Hydroxylamine Hydrochloride. Bayer. Z. anal. Chem., 51, 729-35. Quantitative Determination of Copper in Commercial Copper Salts by Means of Alkaline Hypophosphites. Cavazzi. Bull. chim. farm., 51, 437-9 ; cf . C. A., 6, 330. Air as a Stirring Agent in the Electrolytic Determina- tion of Copper. Travillion. Chemist-Analyst, 6, 8-9. The Quantitative Determination of Copper by Means of Sodium Hypophosphite. Windisch. Z. anal. Chem., 52, 1-13. The Iodide Method for the Determination of Copper. Morgan. Chemist-Analyst, 6, 14-9. The Determination of Copper in Blast Furnace Slags. Morgan. Chemist-Analyst, 6, 19. The Determination of Copper in Refined Copper. Wilson. Chemist- Analyst, 20-1. Copper Analysis. Polk. Chemist-Analyst, 6, 23. COPPER PROPERTIES 111 Copper in Lead Blast Furnace Mats and Sulphide Ores. Edwards. Chemist-Analyst, 6, 24^5. The Detection of Traces of Copper. Pritz-Guillaudeu- Withrow. J. Amer. Chem. Soc., 35, 168-73. Determination of Copper in Preserves by the Means of the Spectrophotometer. Tassilly. Bull. soc. chim., 13, 72-4. The Determination of Oxygen in Copper and Brass. West. Inst. of Metals, August, 1913; J. Soc. Chem. Ind., 32, 913. Analysis of Copper Sulfide Minerals, Pyrites, Copper Mat, Etc. Bertiaux. Ann. chim. anal., 18, 468-74. Rapid Determination of Copper in Steel, Cast Iron and Alloy Steels. Price. J. Ind. Eng. Chem., 6, 170-1. Losses in the Assay of Copper Residues. Lewis. Metal Ind., 12, 74-5. Electrolytic Determination of Copper. Cloukey. J. Ind. Eng. Chem., 6, 265-6. Qualitative Detection of Copper in Cane Cuttings in Cases of Poisoning with Bordeaux Mixture. Kuhr. Arch. Suikerrind., 21, 1649-52. lodometry of Arsenic, Copper and Iron. Lander and Geake. Analyst, 39, 116-21. Note on the Separation of Tin and Copper in Brass Analysis. Liebschultz. Chem. Analyst, 9, 14. Colorimetric Determination of Cobalt, Nickel, Iron and Copper. Hiittner. Z. anorg. Chem., 86, 341-57. Rapid Electrolytic Separation of Copper from Arsenic. Sieverts and Wippelmann. Z. anorg. Chem., 169-74. Analysis of Copper Salts and Solutions. Field. Metal Ind., 12, 155-6. Two Accurate Methods for the Determination of Lead and Copper in Drinking Water. Reese and Drost. Z. angew. Chem., 27, I, 307-12. 112 ANALYSIS OF BABBITT The lodate Method for Copper. Brostrom. Eng. Min- ing J., 98, 215-6. Rapid Determination of Copper in Open Hearth and Alloy Steel or in Cast Iron. Koepping. J. Ind. Eng. Chem., 6, 696. New Test for Copper on Woolen Cloth. Edge. J. Soc. Dyers, Colorists, 30, 188-9. Quantitative Determination of Copper as Copper Sul- phate. Murmann. Oesterr. Chem. Ztg., 17, 96 ; Chem. Zentr., 1914, I, 2016. Electrolytic Separation of Zinc, Copper and Iron from Arsenic. Balls and McDonnell. J. Ind. Eng. Chem., 7, 26-9 (1915). Use of Hydrofluoric Acid in the Separation of Copper and Lead from Tin and Antimony by Means of the Electric Current. McCay. J. Am. Chem. Soc., 36, 2375-81 (1914). Electrolytic Analysis of Copper and Brass. Humphreys. J. Inst. Metals, 12, 325-6 (1914). Rapid Electrolytic Methods for the Determination of Copper. Nakao. J. Pharm. Soc., Japan, 1915, No. 400, 666. The Detection and Determination of Copper in Tap Water. Winkler. Z. angew. Chem., 27, I, 544 (1914). New Volumetric Determination of Copper in Its Salts and Many of Its Alloys. Zuccari. Ann. chim. appli- .cata, 2, 287-90 (1914). Copper in Babbitt Metal. Hagmaier. Met. Chem. Eng., 12, 753 (1914). Determination of Copper in Steel. Brown. J. Ind. Eng. Chem, 7, 213 (1915). COPPER PROPERTIES 113 The Amount of Lead, Copper and Zinc in Artificial Mineral Waters, and the Determination of These Metals. Reese and Drost. Z. Nahr.-Genussm., 28, 427-49 (1914). Rapid Electrolytic Determination of Copper. Theel. Chem. Ztg., 39, 179 (1915). New Test for Copper. Lyle-Curtman-Marshall. J. Amer. Soc., 37, 1471-81 (1915). Solution Control in Ferric Chloride Leaching of Sulfide Copper Ores. Flynn and Hatchett. Met. Chem. Eng., 13, 291 (1915). A Method of Assaying Copper. Eraser. J. Soc. Chem. Ind., 34, 462-4 (1915). Determination of Gold in Blister Copper. King. Min. ing Sci. Press., 110, 917 (1915). Battery Assay of Copper. Price. J. Ind. Eng. Chem., 7, 546-7 (1915). Determination of Copper Sulfate in Commercial Copper Vitriol. Incze. Z. anal. Chem., 54, 252-5 (1915). Reduction of Copper Oxide in Alcohol Vapor in Reduc- ing Sugar Determinations and Copper Analysis. Wed- derburn. J. Ind. Eng. Chem., 7, 610-1 (1915). The Colorimetric Determination of Copper. Deniges and Simonot. Bull. Soc. Pharm., Bordeaux, Aug.- Dec., 1915; Repert Pharm., 27, 172-3 (1915). Standardization of Sodium Thiosulphate Solution for Copper Determination. Grant. Chem. Analyst, 13, 21 (1915). The Direct Determination of Copper in Numerous Copper Ores Containing Other Metals by the Rapid Electrolytic Method. Nakao. J. Pharm. Soc., Japan, 1915, No. 402, 919. Formaldehyde Containing Copper. Hermann Kunz- Krauss. Apoth. Ztg., 31, 66^7 (1916). 114 ANALYSIS OF BABBITT Rapid Analysis of White Bearing Metals for Copper and Lead. Jackson. Met. Chem. Eng., 15, 166 (1916). Determination of Copper in Low-Grade Ores and Slags. Hawley. Eng. Mining J., 102, 307-8 (1916). Electroanalytical Method for the Determination and Separation of the Metals of the Copper-Tin Group. Schoch and Brown. J. Am. Chem. Soc., 38, 1660-81 (1916). A Bottle for the lodometric Titration of Copper. Neal. J. Am. Chem. Soc., 38, 1308-9 (1916). Method for Estimating Phosphorus, Arsenic and Anti- mony in Commercial Copper. Grant. Chem. Analyst, 17, 12-3 (1916). Color Standards and Colorimetric Assays. Arny and Ring. J. Ind. Eng. Chem., 8, 309-17 (1916). Rapid Method for the Estimation of Copper and Iron. Edgar. J. Am. Chem. Soc., 38, 884-7 (1916). Electroanalysis of Copper Without Platinum Electrodes. Carrancio and Ulzurrum. Anales soc. espan. fis. quim., 13, 289-93 (1915). Drilling and Analysis of Copper Ores. Sale. Eng. Mining J., 102, 87-90 (1916). A Colorimetric Method for the Determination of Copper and Iron in Pig Lead, Lead Oxides, and Lead Car- bonate. White. J. Ind. Eng. Chem., 7, 1035-6 (1915). Comparison of Methods for the Estimation of Copper in Commercial Copper Sulfate (containing iron). Wissell and Kiispert. Landw. Vers.-Stat, 86, 277-86 (1915). The Electrolytic Determination of Copper in Copper- Manganese. Koepping. Met. Chem. Eng., 14, 441-2 (1916). COPPER PROPERTIES 115 Some Sources of Error in the lodometric Determination of Copper. Smith. Met. Chem. Eng., 14, 379-80 (1916). Rapid Method of Separation of Copper from Other Metals. Appelbaney. Chem. Analyst, 15, 18 (1915). Electroanalysis of Copper Without Platinum Electrodes. II, Carrancio and Batuecas. Anales soc. fis. quim., 14, 38-47 (1916). Copper Cathode and Iron Anode in the Electroanalysis of Brass. Carrancio and Ladreda. Anales soc. espan. fis. quim., 13, 308-15 (1915). Assaying Gold in Copper Mat. Chase, Jr. Eng. Mining J., 102, 1130 (1916). The Principles and Practice of Sampling Metallic Metal- lurgical Materials (with special reference to the sam- pling of copper bullion). Keller. Bur. Mines, Bull., 122, 105 pp. (1916). Colorimetric Methods for Copper Present in Small Quantities. Heath. Mining Sci. Press, 114, 624 (1917). Determination of Arsenic in Copper. Perkins. Chem. Analyst, 19, 8-9 (1916). Electrolytic Analysis with Small Platinum Electrodes. Gooch and Kobayashi. Am. J. Sci., 43, 391-6 (1917). Electroanalysis Using Silvered Glass Basins in Place of Platinum Cathodes. Gewecke. Chem. Ztg., 41, 297-8 (1917). The Hydrogen Peroxide Reaction for Copper and the Hydrolytic State of Dilute Copper Sulfate Solutions. Mayer and Schramm. Z. analy. Chem., 56, 129-38 (1917). Rapid Method for Copper in Ores. Nyman. Chem. Analyst, 21, 8 (1917). Progress of Work on Boronized Copper. Weintraub. Brass World, 8, 355-6. 116 ANALYSIS OF BABBITT Metallurgy of Copper in Japan. Kondo. Trans. Intern. Eng. Congress, 1915. Copper Smelting in Japan. Eissler. Trans. Am. Inst. Mining Eng., 51, 700-42 (1915). Manganese Bronze. An Historical Sketch. Jones. Metal Ind., 10, 5-6. Separation of Nickel and Copper by Means of Dimethyl- glyoxime. Grossmann and Mannheim. Z. angew. Chem., 30, I, 159-60 (1917); J. Chem. Soc., 112, II, 512. Analysis of Copper. Woodcock. Analyst, 43, 88 (1918). The Estimation of Copper as Sulphide and by Electroly- sis. . Hahn. Z. anorg. allgem. Chem., 99, 201-48 ^ (1917). Sulfur Dioxide Method for Determining Copper in Partly Oxidized Ores. Barneveld and Leaver. Met. Chem. Eng., 18, 203-6 (1918); Eng. Mining J., 105, ^ 552-5 (1918). Sulfur and Copper Oxide Determination. Maier. Eng. Mining J., 105, 372-3 (1918). Copper Dicyanodiamidine and Its Use in Analytical Chemistry. Grossmann and Mannheim. Chem. Ztg., 42, 17-9 (1918). The Determination of Copper in Insecticides. lamieson. Chem. Met. Eng., 19, 185 (1918). Copper; Anon. Bureau of Standards. Circular 73, 103 pp., 5 pi. Estimation of Oxygen in Copper. Oberhoffer. Metal u. Erz., 15, 33-5 (1918) ; J. Soc. Chem. Ind., 37, 376A. A New Method of Determining Copper. Moir. J. Chem. Met. Mining Soc., S. Africa, 18/270-1 (1918). Estimation of Copper Oxide After Previous Precipita- tion as Thicynate. Fenner and Forschmann. Chem. Ztg., 42, 205-6 (1918); J. Chem. Soc., 114, II, 242. COPPER PROPERTIES 117 A New Method for the Separation of the Copper Group From the Arsenic Group, with Especial Reference to the Identification of Arsenic. Sneed. J. Am. Chem. Soc., 40, 187-92 (1918). Determining Copper Minerals in Ores. Van Arsdale. Eng. Mining J., 105, 645-6 (1918). Determination of Chlorine in Cement Copper. Binder. Chem. Ztg., 42, 14 (1918). lodometric Estimation of Copper and Iron. Ley. Chem. Ztg., 41, 763 (1917); J. Chem. Soc., 114, II, 21. Note on the Titration of Copper with Cyanide. Appel- bey and Lane. Analyst, 43, 268 (1918). Determining Copper Minerals in Partly Oxidized Ores. Gremer. Met. Chem. Eng., 18, 644-6 (1918). Iodide Copper Method with Sodium Fluoride. Reese. Eng. Mining J., 105, 1170-1 (1918). lodometric Determination of Copper and Iron. Anonsen. Tidskrift Kern. Farm. Terapi., 14, 246-7 (1917). Determination of Molybdenum in the Presence of Cop- per. Hoepfner and Binder. Chem. Ztg., 42, 315 (1918) ; J. Soc. Chem. Ind., 37, 488A. Determination of Copper by Potassium Thiocyanate. Potassium Iodide, and Thiosulfate. Bruhns. Chem. Ztg., 42, 301-2 (1918) ; J. Soc. Chem. Ind., 37, 445A. The Analysis of Copper in the Presence of Organic Material. Smith. Chem. Analyst, 25, 23-4 (1918). 118 ANALYSIS OF BABBITT CHAPTER V. MISCELLANEOUS ANALYSIS. According to Buchanan 1 the addition of a small amount of bismuth to babbitt, increases the anti-frictional properties of the alloy. The author has added .10% of bismuth to No. 1 Babbitt and the resulting alloy, has always been of a fine, close, even grain with remarkable wearing qualities. Determination of Bismuth. Gravimetric Method. Place 1 gram of the finely divided alloy in a 400 c .c. beaker, add 15 c. c. of HCl and heat to dissolve. When action ceases, add a few drops of HNO Z and boil gently until solution is com- plete. Add 40 c. c. of water, 4 grams of C 4 H 6 O 6 and heat to dissolve. Render solution strongly alkaline with NaHO solution and heat nearly to boiling. Add 5 grams of Na 2 S (dissolved in 50 c. c. of water), heat gently until the precipitate has settled, filter and wash precipi- tate thoroughly with \% Na 2 S solution. Wash the precipitate from the filter into original beaker with a little water, add HNO Z and place beaker on hot plate. Place filter in small beaker, cover with 20% HNO S and boil gently until the paper is free from the precipitate and filter solution into main filtrate. Add sufficient HNO 3 to dissolve the remaining precipitate and evap- *Brassfounders' Alloys. MISCELLANEOUS ANALYSIS 119 orate the solution until yellow S appears, filter the solu- tion into a 800 c. c. beaker and wash the filter with hot .water. Dilute to 400 c. c. with water, place a small piece of litmus paper in the beaker, add NHHO until the acid is almost neutralized and finish with NH 4 HO 1 :3 until the solution is slightly cloudy and alkaline. Add 1 c.c. of HCl (1:3), dilute solution to 700 c. c. with water and allow to stand over night on warm plate. Filter, wash twice with hot water, dissolve precipitate on the filter with hot HNO 3 (1 :4), and wash filter with hot water, allowing the solution and wash water to run into a 400 c. c. beaker. Neutralize as before with NH 4 HO, add 1 c.c. of HCl (1:3) and allow to stand two hours at a gentle heat. Filter on weighed filter and wash thoroughly with hot water. Dry filter and con- tents in air bath at 100 C., for one hour and weigh as BiOCl. This weight multiplied by .80166 will give the weight of Bi. No. 1 Babbitt. Filter-f B*OC7=23.2000 ^rams. =23.1987 " " .0013 gram. .0013 X. 80166 X100=.104% Bi. 1 gram. Mixture calculation=.10% Bi. Colorimetric Method. Place .5 gram of the finely divided alloy in 150 c. c. beaker, decompose with 10 c. c. of HNO 3 (1.42). Add 30 c. c. of water, boil, filter and wash with HNO 3 (1:3). Add NH.HO and (NH 4 ) 2 C0 3 120 ANALYSIS OF BABBITT to filtrate until solution is alkaline, stir thoroughly, filter and wash with dilute NH 4 HO. Dissolve the precipitate on the filter with hot HNO 3 (1:3) and wash the filter with hot water. Add 10 c. c. of H 2 SO 4 (1.84) to the solution and evaporate to SO S fumes. Cool, dilute with 50 c. c. of water and boil ten minutes (BiSO^ is soluble, but not PbSO), filter into 500 c. c. marked flask, cool, dilute to the mark and mix. Place 100 c. c. in 100 c. c. Nessler jar, add 5 c. c. of 5% KI solution in water, mix and titrate blank with standard solution of Bi until the color matches that of the alloy. Blank. Place 100 c. c. of water in 100 c. c. jar, add 5 c. c. of 5% KI solution and 10 drops of H 2 SO 4 (1.84). Standard Bi Solution. Dissolve .2 gram of pure Bi in dilute HNO S , cool, add 10 c.c. of H 2 SO 4 (1.84), and evaporate to SO 3 fumes. Cool, dissolve in water and dilute to 1000 c. c. 1 c. c.=.0002 gram of Bi. No. 1 Babbitt. .0002X.5 c.c. -X 100=. 100% Bi. .1 gram. The addition of .10% metallic magnesium to No. 1 Babbitt forms a beautiful even close grained compact bearing metal. Its wearing qualities have been carefully noted by the metal mixer, on fast running motor bear- ings for over one year and it is said to give wearing qualities far surpassing that of any other alloy that has been used for the same purpose. As far as it is known, the author has been the first to use metallic magnesium MISCELLANEOUS ANALYSIS 121 in babbitt. The alloy has not been patented and all are at liberty to use it. 1 Determination of Magnesium. Gravimetric Method. Place 1 gram of the finely divided alloy in 250 c. c. beaker, add 10 c. c. of HNO 3 (1.42), cover, and heat gently until the fumes have disappeared. Add 10 c. c. of HCl ( 1.20), and heat gently until solution is complete. Add 10 c. c. of HCl (1.20), dilute with water to 100 c. c., add NHHO in excess and 30 c. c. of strong Br water, heat to boiling, allow to settle, filter into 800 c. c. beaker and wash precipitate with hot water. Wash the precipitate from the filter into the original beaker with a little water, add 10 c. c. of HCl (1.20), heat to dissolve the precipitate, pour the solution over the filter and wash the filter with hot water. Add 30 c. c. of Br water to the solution, reprecipitate with NH^HO, allow to settle, filter and wash with hot water. Add filtrate and wash water to first filtrate and for every 100 c. c. of solution, add 10 c. c. of HCl (1.20), stir thoroughly and pass a current of washed H,S through the solution until it is saturated. Filter, wash precipitate with H 2 S water, place the filtrate and wash water in porcelain casserole and evaporate to dryness. Ignite to volatilize the ammonium salts and the greater part of the ZnCL, if present. Cool, add 30 c. c. of *The metallic megnesium that was used for the experimental work was kindly donated by W. R. Seigle, Norton Laboratories, New York, N.Y. U. S. f Patent. 933, 139, Sept. 7, 1910. Enrique A. Touceda, Albany, N. Y. Antifriction alloy. Mg 0.1-5%, Cd 10% and Pb 85-89.9%. U. S., Patent. 934, 637, Sept. 21, 1910. Enrique A. Touceda. Albany, N. Y. Antifriction alloy. Mg 0.5-5% and Cd 95-99.S parts, with or without other metals. 122 ANALYSIS OF BABBITT dilute HCl (1:10), heat to dissolve soluble salts, render slightly alkaline with NH 4 HO, filter into 400 c. c. beaker and wash with hot water. Cool, add slowly, drop by drop, 10 to 15 c. c. of saturated filtered solution of Na(NH 4 )HP0 4) stirring constantly, add one-third of its volume of NH^HO (.90), and allow to stand in the cold overnight. Filter on small ashless filter and wash thoroughly with NH^HO (1:3) reserving filtrate and wash water. Ignite precipitate, cool and weigh as impure Mg 2 P 2 O 7 . Crucible+impure Mg 2 P 2 7 = 19.2325 grams. = 19.2280 " .0045 gram. Add 15 c. c. of water to the crucible and 10 to 20 drops of HCl, heat carefully to dissolve the soluble salt, filter, and wash with hot water. Ignite, cool and weigh as SiO 2 . Subtract this weight from the first weight and reserve weight to combine with that recovered from the filtrate and wash water. Crucible+S*0 2 = 19.2290 grams. = 19.2280 " .0010 gram. Si0 2 . .0045-.0010=.0035 gram Mg 2 P 2 O 7 . Evaporate reserved filtrate and wash water to dryness in platinum dish. Ignite carefully until the residue is white, add 20 c. c. of water and 15 to 20 drops of HCl, boil, filter into small beaker and wash with hot water. Render solution alkaline with NHHO, add 5 c. c. of MISCELLANEOUS ANALYSIS 123 saturated filtered solution of Na(NH^)HPO^ stirring constantly, add one-third of its volume of NH^HO (.90), stir thoroughly and allow to stand in the cold over night. Filter, wash with dilute NH 4 HO (.96), ignite, cool and weigh as Mg 2 P 2 O 7 . Combine this weight with the weight previously found and calculate Mg. No. 1 Babbitt. Crucible+A/# P 2 O 7 = 19.2286 grams. = 19.2279 " .0007 gram. .0035+ .0007=.0042 gram Mg,P 2 O 7 . .0042V. 21847 X100=.0917% Mg. 1 gram. Mixture calculation =. 10% Mg. Qualitative Analysis of Babbitt. Sn, Sb, Pb, Cu, Bi, Cd, Fe and Zn. Place 2-5 grams of the finely divided alloy in 400 c. c. beaker, add cautiously 15 to 20 c. c. of HNO 3 (1.42) and heat gently until the alloy is decomposed. Evaporate to dryness, cool, add 5 c, c. of HNO 3 and 50 c. c. of water, boil five minutes, filter on double filter and wash once with hot water. The volume of the filtrate and wash water should be about 75 c. c. Precipitate. Place a portion of the precipitate in small beaker, add 5 'c. c. of HCl and 10 c. c. of water, heat to boiling, add a few drops of HNO 3 and boil five minutes. Add 10 124 ANALYSIS OF BABBITT c. c. of water to the clear solution and several small bright iron nails, boil five minutes, filter (reserve filter and contents) and add HgCl 2 to filtrate; white precipi- tate=Hg 2 Cl 2 =Sn. as SnCl^+Fe=SnCl 2 +FeCl 2 and 2 Wash filter and contents thoroughly with hot water, transfer the black precipitate from the filter to small beaker with a little water, add 5-10 c. c. of HCl and a few drops of HN0 3 , boil, dilute with water and saturate solution with H S ; orange precipitate=S^.>S 3 . Filtrate. Saturate with H 2 S, filter, wash with hot water (reject wash water, reserve precipitate A) and boil filtrate free from H 2 S. Add a few drops of HNO 3 , boil, render solution strongly alkaline with NH 4 HO ; red precipitate =Fe 2 (HO). Filter, render filtrate acid with HC.,H a O s and saturate solution with H 2 S; white precipitate=Zw5\ Transfer reserved precipitate (A) to small beaker with a little water, add 5 to 10 c. c. of HNO 3 (1.42) and heat to dissolve the sulphides. Filter, add 5 c. c. of dilute H 2 SO 4 (1:1) to the filtrate and allow to settle. Filter (reserve filtrate A), wash the white precipitate once with hot water, place filter and contents in original beaker, cover with NH 4 HO (.90) and acidulate solution with HC 2 H 3 O 2 . Heat to clear the solution and add K 2 Cr 2 O 7 ; yellow precipitate=PfcCVO 4 . Render reserved filtrate (A) strongly alkaline with NHJIO ; blue solution^ C. Filter (precipitate B=B{ and filtrate B=Cu and Cd), wash the precipitate free from Cu and dissolve on the filter with a little hot dilute HCl. Pour the solution into a large volume of water; white predpitate=BC!O. MISCELLANEOUS ANALYSIS 125 Decolorize filtrate (B) with KCN and saturate solu- tion with H 2 S; yellow precipitate =CdS. Miscellaneous. Do not use borings from babbitt for analysis. Filings taken properly and mixed thoroughly, represent an average sample from the sample bar. Many chemists do not mention Fe that is found in babbitt in trifling amounts and in many cases, Sn is reported by difference. If SnO 2 and Sb 2 O in HNO 3 . solution is evaporated to dryness, taken up with HNO S , diluted with water and filtered, Sb will be found in the filtrate. Hence the weighing of HNO 3 residues for the determination of total Sn0 2 and Sb 2 O is mal-practice and the results most decidedly worthless. The method of separation of Sn and Sb from traces of Cu, Pb, Fe, etc., by fusion with Na 2 CO s and S, and the solution of the fusion in water, is valueless for daily routine work. Place no faith in any method that advises the separa- tion of Pb from much Sn and Sb by HNO 3 solution, as it is practically impossible to wash all the Pb(NO z } 2 from the insoluble residue, and in the determination of Pb as PbSOt, the ignition of a paper filter with par- ticles of PbSO 4 adhering to it, require the most skillful treatment to avoid loss by oxidation and volatilization. For this reason the Gooch crucible is recommended. The asbestos for the Gooch crucible should be treated for a few hours in each of the following acids : HCl, HNO 3 and H 2 SO 4 (1:5), and allowed to remain in the latter solution until used. After placing the asbestos in the crucible, wash thoroughly with hot water, dry, ignite, cool and weigh. The crucible is now ready for use. 126 ANALYSIS OF BABBITT A modified Gooch crucible holder is sold under the name of "Esco" 1 . This is really a good article and avoids entirely the use of rubber tubing. The / method for the determination of Cu will give accurate results with reasonable weights of Cu, but not always with small weights of the metal, unless the method is modified. To insure the absence of Zn in large precipitates of CuS, 30% HCl by volume must be present. Use the balance for the determination of specific gravity of alloys. Special hydrometers for taking the specific gravity of solids are not always trustworthy. W Sp. Gr.= PF=weight of alloy in air. IV 1 = weight of alloy in water. Use weights from 40 to 50 grams of the alloy, dupli- cates will then check to the 3d., decimal place. C R F32 80 #=100 C=180 F and = =- 100 80 212-32 F 9/5 C+32=9/4 #+32 C S/4R =5/9 (F 32) RA/SC =4/9 (F 32) *For sale by Eberbach and Son, Ann Harbor, Mich. MISCELLANEOUS ANALYSIS 127 Dr. Ure 1 gives the correct rule for computing the mean specific gravity of an alloy. Pw+pW Af mean specific gravity of the alloy. W and zt'=greater and least weights. P and />=greater and least specific gravities. When the calculated specific gravity of an alloy is less than the actual specific gravity, condensation has taken place (increase of specific gravity). When the specific gravity is lower than that calculated, expansion has taken place (decrease in specific gravity). Wt. per cent. - = Volume. Sp. Gr. At. Wt. - = Atomic Volume. Sp. Gr. Per cent. Molecular ratio or m olecular proportion Molecular Weight. HCl dissolves Sn, Fe, Al, Zn. HNO 3 Pb, Bi, Cd, As, Cu, Fe, Zn. Oxidizes Sn and Sb. Pb precipitates Cu. Mg " Fe, Zn, etc. Cu " As, Sb, Hg, An, Ag. Sn As, Sb r Hg, Au, Ag. Fe " Cu, Sb, Bi, Au, Ag, Hg: Zn Sn, Sb, As, Cu, Pb, Hg, Bi, Co, Ni, Au, Ag. Dictiqnary. Vol. I, p. 49. 128 ANALYSIS OF BABBITT Spec. Grav. Melting Point. Average "Weight. (deg. C.) (Ib. percu. ft) Pb. 11.37 (a) 326.2 (f) 710.6 CM. 8.89 (b) 1054. (g) 555.6 Sn. 7.294 (c) 232.7 (f) 455.8 Sb. 6.713 (c) 632. (h) 419.4 Fe. 7.8 (d) 1600.(wr*.)(i) 487.5' Zn. 6.9-7 2 (e) 433. (f) 440.6 Many metallurgists calculate the mean melting point of an alloy. This is considered unfair, 1 as many alloys have two melting points, the liquidus and the solidus points respectively. The following articles may be of interest to the chemist : Analysis of Babbitt's Metal. Handy. Proc. Eng. Soc. West Pa., p. 185, 1892. Analysis of Alloys of Lead, Tin, Antimony and Arsenic. Andrews. J. Amer. Chem. Soc., Nov., 1895. The History of Babbitt Metal. Metal Industry, Sept., 1903. The Testing of Bearing Metals. Clamer. Iron Age, July 9, 1903. A Study of Alloys Suitable for Bearing Purposes. Clamer. J. Franklin Inst, July, 1903. Analysis of Alloys of Copper. Wilson. Chem. Eng., July, 1905. Rapid Method of Babbitt Metal Analysis. Yockey J. Amer. Chem. Soc., Mav, 1906.. The Valuation of Engineering Alloys. Meade. Chem. Eng., June, August, Sept., 1908. wMatthiessen. ^Borchers. r soft coal is avoided. At one time not having molds, a length of railroad iron was used. This was turned on its side and the ends blocked with fire clay. When the clay was dry, it made an excellent mold. One very important item is, not to assume that the crude commercial metals used in the manufacture of the alloy are chemically pure. The chemists report on an alloy will show at times, a gain or a deficit of certain metals. As a rule the crude metals can be relied upon to give results that are satisfactory. Commercial Metals: Cu 98.50% 99.90% (a) Sn 93.50 " 99.96 " (b) Sb 98.85 " 99.85 " (c) Pb 99.87 " 99.89 " (c) Examples of Calculations: (1) The following metals are melted together: Pb, 50 Ibs. ; Sn, 25 Ibs., and Sb, 15 Ibs. The resulting ingot weighed 88.5 Ibs. What is the percentage of metal lost? 50+25+15=90.0 Ibs. Ingot =88.5 " Loss= 1.5 1.5X100 =1.66%. 90 Sexton. < b > Bruno Kerl. <>Aftn. and Sci. Press, July 10, 1915. BABBITT METAL 139 (2) What is the percentage composition of -the above mixture ? 50X100 Pb = 55.55%. 90 25X100 Sn = 27.78" 90 15X100 Sb = 16.67" 90 100.00 " (3) Desire a bearing or casting of 150 Ibs., of the above composition. What is the required weight of each metal ? 55.55X150 Pb = 83.32 Ibs. 100 27.78X150 Sn = 41.68 " 100 16.67X150 ,:* Sb = 25.00 " 100 150.00 " (4) What is the formula of the following alloy: Cu, 98.1%, and Sn, 1.90%? 98.1% Cu -=1.5432 63.57 140 ANALYSIS OF BABBITT 1.9% Sn -= .0160 118.7 .016: 1.5432=1 :X X=96 ' SnCu 96 (5) What is the percentage of each metal in the follow- ing alloy: Sn 25 Cu 5 Sb 2 ? Sn 118.70X25=2967.50 Cu 63.57X 5= 317.85 Sb.... t . 120.20X 2= 240.40 3525.75 2967.50X100 =84.166% Sn. 3525.75 317.85X100 = 9.015% Cu. 3525.75 240.40X100 3525.75 -= 6.819% Sb. 100.000%. BABBITT METAL 141 SAMPLING. The following method for the sampling of babbitt, has given the best results and also entire satisfaction for a number of years: Take the sample for analysis from the thoroughly mixed molten metal, just before the general pouring and cast in a cold iron mould of about the following dimen- sions, 4"X WXl". When the ingot is cold, the outside skin is removed with a file, thrown aside and filings are now taken by filing gently across the surface of the end of the ingot with a new clean file and, as for the con- tamination of the sample with particles of the file, it may be ignored safely in practice. Do not take a sample from the ear or lug of a bar or casting as there may be, and is in many cases, a segregation of metal. The analysis of No. 2 Babbitt represents a sample taken across the entire end of the sample bar. The sample should be taken either by the chemist or by one who thoroughly understands the importance of the work, and the taking of samples by irresponsible boys, cheap labor and non-technical officials is certainly a stupid ridiculous practice, and if this mode of sampling is followed, the chemist will in many cases get the criticism. 142 ANALYSIS OF BABBITT BIBLIOGRAPHY. WORKS OF REFERENCE. Metallurgy, etc. Antimony. Wang. (a). Lead and Zinc in the United States. Ingalls. (e). Principles of Metallurgy. Fulton, (b). Metallurgical Laboratory Notes. Howe. (b). Metallurgy. Wysor. (c). Metallurgy. Borchers. (d). General Metallurgy. Hofman. (b). Practical Treatise on Metallurgy. Kerl. (e). Metallurgy. Silver and Gold. Percy, (e}. Metallurgy. Lang. (b). Hand-book of Metallurgy. Vol. I, Vol. II. Schnabel. (e). Manual of Metallurgy. Greenwood, (e). Electro-Metallurgy. McMillan. (/). Elements of Metallurgy. Phillips. (/). Metallurgy of Iron. Bauerman. (e). Elements of Metallurgy. Sexton. (/). Metallurgy. Roberts- Austin. (/). Antimony Industry. Howard, (gr). Metallurgy of the Common Metals. Austin, (m). Principles of Metallurgy. Hiorns. (i). Electric Smelting and Refining. Borchers. (/). Electro-Metallurgy. Watt. (e). Electrolytic Separation of Metals. Gore. (e). BABBITT METAL 143 Metallurgy, etc. (continued). Electric Furnaces. Moissan. (e}. Electric Furnaces. Wright, (e). Electro-Metallurgy. Smee. (e). Metallurgy of Zinc and Cadmium. Ingalls. (a). Industrial Furnaces. Damour. (b) . Physical Metallurgy. Rosenhain. (e). Metallurgy. Overman, (e). Metallurgy. Rhead. (&). Metallurgy. Makins. (e). Metallurgical Machinery. Jenkins, (e). Matte Smelting. Lang. (e). Metallurgy. Harrison, (e). Practical Metallurgy. Hiorns. (i). Metallurgical Hand-book. Creamer and Bicknell. (e). Electrolytic Separation of Metals. Gore. (e). Electro- Deposition of Metals. Langbein. (e). High Temperature Measurements. Le Chatelier and Boudouard. (d). Engineering and Metallurgical Books, (titles.) 1907- 1911. Peddie. (e). Refractories and Furnaces. Havard. (b). The Electric Furnace. Stansfield. (b). Electric Furnaces. Rodenhauser-Schoenawa-Vom Baur. (d). Practical Pyrometry. Ferry, (d). Metallurgial and Chemical Engineering, (m). Refractory Materials. Hancox. (e). Metallurgists and Chemists Handbook. Liddell. (b). Cast Iron. Keep. (a). Lead-Smelting. lies. (d). Lead Refining by Electrolysis. Betts. (d). Lead Smelting and Refining. Ingalls. (e). 144 ANALYSIS OF BABBITT Metallurgy, etc. (continued). Metallurgy of Lead and the Desilverization of Base Bullion. Hofman. (e). Metallurgy of Lead and Silver. Part I, Lead ; Part II, Silver. Collins, (e). Metallurgy of Silver, Gold and Mercury in the United States. Vol. I, Silver; Vol. II, Gold and Mercury. Egleston. (e). Coal. Somermeier. (&). Coal and Coke. Wagner, (b). Heat Energy and Fuels. Juptner. (fc). Smelter Construction Costs. Jones. (&).. Notes on Metallurgical Mill Construction. Ingalls. (*). Cyanide Process for the Extraction of Gold. Eissler. () Metallurgy of Argentiferous Lead. Eissler. (e). Metallurgy of Gold. Eissler. (e) . Metallurgy of Silver. Eissler. (e). Hydrometallurgy of Silver. Hofman. (e}. Practical Notes on the Cyanide Process. Bosqui. (e). Chemistry of Cyanide Solutions. Clennell. (e). Cyaniding Gold and Silver Ores. Julian-Smart. (/). Cyanide Process of Gold Extraction. Park. (/). The Cyanide Process. Miller, (a). Cyanide Processes. Wilson, (a). The Chlorination Process. Wilson, (a). The Cyanide Industry Theoretically and Practically Considered. Robine-Lenglen-Le Clerc. (a). Gold and Silver. Crane, (a). The Materials of Engineering. Thurston. (d). Part I. Non-Metallic Materials of Engineering. Part II. Iron and Steel. BABBITT METAL 145 Metallurgy, etc. (continued)- Part III. Treatise on Brasses, Bronzes and Other Alloys. Modern Electrolytic Copper Refining. Ulke. (d). Foundry Practice. Tate-Stone. (d). American Foundry Practice. West. (d). Moulders' Textbook. West. (d). General Foundry Practice. Roxburgh, (e). Iron Founders' Manual. Payne, (e). Modern Iron Foundry Practice. Bale. (e). Part I. Foundry Equipment, Materials Used and Processes Followed. Part II. Machine Moulding and Moulding Ma- chines, Physical Tests of Cast Iron, Methods of Cleaning Castings, Foundry Accounting, etc. Practical Iron Foundry. Horner. (e). Foundry Machinery. Treiber. (e). Modern Moulding and Patternmaking. Mullin. (e). Pattern Makers Assistant. Rose. (e). Malleable Cast Iron. Parsons, (e). The Production of Malleable Castings. Moldenke. (/>). Foundry Practice. Palmer, (d). Encyclopedia of Founding and Dictionary of Foundry Terms. Bolland. (rf). The Iron Founder. Bolland. (d). "The Iron Founder" Supplement. Bolland. (n). Iron and Steel. Hudson, (e). Iron and Steel. Stansbie. (e). Siderology: The Science of Iron. Juptner. (e). The Basic Open-Hearth Steel Process. Dichmann. (*). Electric Furnace and Iron and Steel Production. Kershaw. (e). 146 ANALYSIS OF BABBITT Metallurgy, etc. (continued). Electro-Thermal Methods of Iron and Steel Produc- tion. Kershaw. (e). Outline of the Metallurgy of Iron and Steel. Sexton- Primrose, (e). Forging of Iron and Steel. Richards, (e). Hardening and Tempering of Steel, in Theory and Practice. Reiser, (e). The Production of Aluminum and Its Industrial Use. Minet- Waldo, (d). Elements of Metallography. Ruer-Mathewson. (d). Hardening, Tempering, Annealing and Forging of Steel. Woodworth. (0). Tool Making. Markham. (/>). The Silversmith's Handbook. Gee. (/). Notes on Alloys. Parry, (e). Systematic Treatment of Metalliferous Waste. Parry. (). Zinc. Primrose, (e). Aluminum. Seligman. (e). Brass. Bengough. (e). Alloys (Non-Ferrous). Sexton, (e). The Metallurgy of Nickel. Johnson, (e). Lead and Its Compounds. Lambert. (*). Metallography of Strains. Humphrey, (e). The Metallurgy of Steel. Harbord. (a). Metallic Alloys. Gulliver, (a). Principles of Iron Founding. Moldenke. (&). Steel Rails, Their History, Properties, Strength and Manufacture. Sellew. (e). Blast Furnace Calculations. Stevenson, (e). Treatise on Roll Turning for the Manufacture of Iron. Tunner. (e). BABBITT METAL 147 Metallurgy, etc. (continued). , Welding and Cutting Metals By the Aid of Gasses or Electricity. Groth. (e). Lead and Zinc Pigments. Holley. (e). The Metallurgy of Iron. Turner, (a). Lectures on Iron- Founding. Turner, (a). Practical Metallurgy. Turner, (a). The Foundry. (/). Microscopic Analysis of Metals. Osmond. (/). Welding. Hart. (c). The Production of Chromium and Its Compounds By the Aid of the Electric Current. Le Blanc, (c). Production of Metallic Objects Electrolytically. Pfan- hauser. (c). Iron Corrosion, Anti-fouling and Anti-corrosive Paints. Andes, (e). Manufacture of Mineral and Lake Pigments. Bersch. (*) Report Upon the Precious Metals. Blake, (e). On the Construction of Iron Roofs. Campin. (e). Radium and Other Radio-active Substances ; Polonium, Actinium and Thorium. Hammer, (e). The Metals Used in Construction. Joynson. (e). Chemistry of Pigments. Parry-Coste. (e). Manufacture of Paint. Smith, (e). Steel. Metcalf. (d). Electro-plating and Electro-refining of Metals. Watt. (e). Calculation of Furnace Charges. Chauvenet. (a). General Foundry Practice. McWilliam-Longmuir. (a). Elementary Treatise on Hoisting Machinery. Horner. (). Hydraulic Power and Hydraulic Machinery. Robin- son, (a). 148 ANALYSIS OF BABBITT Metallurgy, etc. (continued). Art of Pattern Making. Chase, (a). Rustless Coatings ; Corrosion and Electrolysis of Iron and Steel. x Wood. (a). The Calorific Power of Fuels. Poole. (a). First Lessons in Metal- Working. Compton. (a). Machinery Pattern Making. Dingey, (a). Metals and Minerals. Goesel. (a). The Calorific Power of Gas. Coste. (a).' Theory and Practice of Enamelling on Iron and Steel. Griinwald. (a). Commercial Peat. Gissing. (a). Peat: Its Use and Manufacture. Bjorling-Gissing. (a). Arsenic. Wanklyn. (a). Blast Furnace Practice. Morgan, (a). Getting Gold. Johnson, (a). Alloys and Their Industrial Application. Law. (a). Hydro-Electric Practice. Von Schon. (a). Constructional Steelwork. Farnsworth. (a). Mixed Metals or Metallic Alloys. Hiorns. (i). Metal Coloring and Bronzing. Hiorns. (i). Metallography. Hiorns. (i). Introduction to Metallography. Goerens. (k). Metallography of Iron and Steel. Sauveur. (a). A Practical Treatise on Metallurgy. Crookes-Rohrig. Vol. I, Vol. II, Vol. III. (k). Tin Deposits of the World. Fawns, (h). Metallic Alloys. Brannt. (/). Outline of the Manufacture of Iron and Steel. Hof- man. (e). Iron and Steel Manufacture. Hiorns. (e): Steel and Iron for Advanced Students. Hiorns. (e). Studies of Blast Furnace Phenomena. Gruner. (e). Open Hearth Steel Castings. Carr. (e). BABBITT METAL 149 Metallurgy, etc. (continued). Manufacture and Properties of Iron and Steel. Camp- bell, (e). Chemical Phenomena of Iron Smelting. Bell. (e). Bessemer Steel, Ores and Methods. Fitch, (e). Galvanized Iron. Its Manufacture and Uses. Davies. () Steel and Iron. Greenwood, (e). Metals and Their Chief Industrial Applications. Wright, (e). The Metallographist. Sauveur. (r). Vol. I, Vol. II, Vol. Ill, Vol. IV, Vol. V, Vol. VI. Iron and Steel Magazine. Sauveur. (r). Vol. VII, Vol. VIII, Vol. IX, Vol. X, Vol. XL The Cupola Furnace. Kirk. (/). Iron: Its History, Properties and Processes of Manu- facture. Fairbairn. (e). Galvanizing and Tinning. Flanders, (e). Pyrite Smelting. Reprinted from the Engineering and Mining Journal. Rickard. (e). A Pocket Book for Miners and Metallurgists. Power. () The A. B. C. of Iron. Sisson. (e). L' Aluminum: ses Properties; ses Applications. Mois- sonnier. (e). Etude Industrielle 'des Alliages Metalliques. Guillet. (*)- Useful Metals and Their Alloys. Scoffern and Others. (*) Metals: Their Properties and Treatment Hunting- ton-McMillan, (e). Electro-Plater's Hand Book. Bonney. (e). The Practical Electroplater. Brunor. (e). Electrolysis. Fontaine, (e). ISO ANALYSIS OF BABBITT Metallurgy, etc. (continued). Electro-Chemistry. Gore. (e). The Art of Electrolytic Separation of Metals. Gore. (*>. Galvonoplastic Manipulations. Roseleur. (e). Traite Theorique et Pratique d'Electrochemie. Tom- massi. (e). The Polishing and Plating of Metals. Hawkins, (e). Electro-Plating. Urquhart. (e). Modern Electro-Plating. Von Home. (e). Galvonoplastic Manipulations. Wahl. (e). Stereotyping and Electrotyping. Wilson, (e). Radium and Radio- Active Substances. Baskerville. (> Radioactive Substances. Curie, (e). Radium and All About It. Bottone. (e). Story of American Coals. Nicholls. (e). Radium and Other Radio-Active Elements. Levey- Willis, (e). Chemistry of Coke. Anderson, (e). A Practical Treatise on the Combustion of Coal. Barr. (0; Practice of Copper Smelting. Peters, (a). Principles of Copper Smelting. Peters, (a). Modern Copper Smelting. Peters, (a). Metallurgical Calculations. Richards, (a). Part I. Chemical and Thermal Principles. Part II. Iron and Steel. Part III. The Metals Other Than Iron (Non-fer- rous Metals.) Cementation of Iron and Steel. Giolith. (&).. Cleaning of Blast Furnace Gases. Wagner, (b). The Steel Foundry. Hall. (b). Brass Founders' Alloys. Buchanan, (s). BABBITT METAL 151 Metallurgy, etc. (continued). Autogenous Welding and Cutting. Kautny. (b). Fuel and Its Applications. Ronalds-Richardson, (e). Part I, Part II. Coal: Its History and Uses. Thrope. (e). The Combustion of Coal and the Prevention of Smoke Chemically and Practically Considered. Williams. () Gas and Coal Dust Firing. Putsch, (e). Combustion of Fuel. Pullen. (e). Smoke Abatement. Nicholson, (e). Fuel and Its Applications. Mills-Rowan, (e). Liquid Fuel and Its Combustion. Booth, (e). Briquettes and Patent Fuel. Bjorling. (e). Facts About Peat. Peat Fuel and Peat Coke. Lea- vitt. (e). Peat and Its Products. Kerr. (*). Liquid Fuel for Mechanical and Industrial Purposes. Hodgetts. (e). A Treatise on Fuel. Scientific and Practical. Gallo- way, (e). The Metallurgy of Steel. Howe. (e). Iron, Steel and Other Alloys. Howe. (e). Steel : Its History, Manufacture, Properties and Uses. Jeans, (e). Iron and Steel Manufacture. Kohn. (e). Papers on Iron and Steel, Practical and Experimental. Mushet. (e). The Iron and Steelmaker. Joynson. (e). A Treatise on Steel. Landrin. (e). The Metallurgy of Iron and Steel, Theoretical and Practical. Osborn. (e). The Manufacture of Iron In All Its Various Branchs. Overman, (e). 152 ANALYSIS OF BABBITT Metallurgy, etc. (continued). The American Steel Worker. Markham. (e). Crystallization of Iron and Steel. Mellor. (e). Metallurgy of Cast Iron. West. (e). A Practical Guide for Puddling Iron and Steel. Urbin. () Steel: Its Selection, Annealing, Hardening and Tem- pering. Markham. (o). The Manufacture of Steel. Overman, (e). An Elementary Treatise on Iron Metallurgy. Rogers. () The Chemistry of Iron and Steel Making, and of Their Practical Uses. Williams, (e). The Iron Manufacture of Great Britain, Theoretically and Practically Considered. Truran. (e). Researches On the Action of the Blast Furnace. Schinz. (e). Outline of the Metallurgy of Iron and Steel. Sexton. (); Chemical Combinations Among Metals. Guia's. (q). Economics of Iron and Steel. Skelton. (e). Notes On the Use of Anthracite in the Manufacture of Iron. Johnson, (e). Elementary Practical Metallurgy, Iron and Steel. Longmuir. (e). Principles and Practice of Iron and Steel Manufacture. MacFarlane. (e). History of the Manufacture of Iron In All Ages. Swank, (e). Tool Steel. Thallner. (e). Metallurgy of Iron and Steel. Turner, (e). The Manufacture of Russian Sheet Iron. Percy, (e). Notes On Lead Ores. Fairie. (e). BABBITT METAL 153 Metallurgy, etc. (continued). A Handbook of Practical Cyanide Operations. Gaze. (*). Cyanide Practice. James, (e). Prevention of Smoke. Polppewell. (e). Smoke Prevention and Fuel Economy. Booth-Ker- shaw. (e). Fuel: Its Combustion and Economy. Clark- Williams. (*) The Commercial Uses of Coal Gas. Fletcher, (e). Combustibles Industriels. Colomer-Lordier. (e). A Treatise On the Manufacture of Coke and Other Prepared Fuels and the Saving of By-Products. Fulton, (e). Essai Combustible. Sidersky. (e). Gaseous Fuel, Including Water Gas: Its Production and Application. Thwaite. (e). Air As Fuel. Ross. (e). Stamp Milling and Cyaniding. Thomson, (b). Stamp Milling. Del Mar. (&). Stamp Milling of Gold Ores. Rickard. (b). De Re Metallica. Agricola. tr. Hoover-Hoover, (t). Details of Cyanide Practice. Megraw. (b). Practical Data for the Cyanide Plant. Mcgraw. (b). Cyanide Practice. MacFarren. (b). The Hydrometallurgy of Copper. Greenawalt. (&). Production and Properties of Zinc. (1902). Ingalls. (6). Corrosion and Preservation of Iron and Steel. Cush- man-Gardner. (b). Notes on Lead and Copper Smelting. Hixon. (&). Iron and Steel. Tiemann. (&). Composition and Heat Treatment of Steel. Lake. (b). High Speed Steel. Becker, (b). 154 ANALYSIS OF BABBITT Metallurgy, etc. (continued). Metallurgy of Iron Dictionary. Vol. XI: in each of the six languages, (b). Corrosion of Iron and Steel. Sang. (b). Processes of Silver and Gold Extraction. Kustel. (e). Gold: Its Occurrence and Extraction. Lock. (e). Roasting of Gold and Silver Ores, and the Extraction of Their Respective Metals Without Quicksilver. Kustel. (e). Gold Milling. Lock. (e). A Precis of Lead Smelting. Longridge. (e). Hand Book of Gold Milling. Louis, (e). Losses in Gold Amalgamation. McDermot-Duffield. (). Notes On the Treatment of Gold Ores. O'Driscoll. () The Metallurgy of Lead, Including Desilverization and Cupellation. Percy, (e). The Mining and Metallurgy of Gold and Silver. Phillips. (*). The A. B.C. of Iron and Steel. Backert. (/>). The Blast Furnace and the Manufacture of Pig Iron. Forsythe. (/>). Blast Furnace Construction in America. Johnson. (/>). Aluminum and Aluminum Alloys. Pittsburgh Reduc- tion Company, Pittsburgh, Pa. Present-Day Metallurgical Engineering On the Rand. Yates. (e). The Practical Metal Workers Assistant. Byrne, (e). Tin : Describing the Chief Methods of Mining, Dress- ing and Smelting. Charleton. (e). A History of the Trade in Tin. Flower, (e). The Production of Tin. Louis, (e). Chemistry and Metallurgy of Copper. Piggott. (e). BABBITT METAL 155 Metallurgy, etc. (continued). Aluminum: Its History, Occurrence, Properties. Metallurgy and Applications. Richards, (e). Tin and Tin Plate. Their History, Production and Statistics. Weeks, (e). Notes for a History of Lead. Pulsifer. (e). The Metallurgy of Gold. Rose. (e). The Quartz Operator's Hand Book. Randall, (e). The Lixiviation of Silver Ores with Hyposulphite Solutions. Stetefeldt. (e). Compendium of Gold Metallurgy (Ores) and Digest of United States and California Mining Laws. Wade. (e). The Metallurgy of Iron and Steel. Stoughton. (/>). Metallurgy of Copper. Hofman. (b). Practical Alloying. Buchanan. (/>). Foundryman's Primer. Wangelin. (/>). Penton's Foundry List. (/>) Metallography of Steel and Cast Iron. Howe. (/>). Foundry Irons. Kirk. (/>). Metallurgy of Steel. Harbord-Hall. (/>). Elliott's Weights of Steel. Elliott. (p). Safety In the Foundry. Alexander. (/>). Dies. Woodworth. (p). Press-Working of Metals. Smith, (n). Art of Pattern Making. Chase, (n). Paints for Steel Structures. Lowe. (). Drop Forging, Die Sinking and Machine Forming of Steel. Woodworth. (/>). How to Make Converter Steel Castings. Simonson. (/>). Coal Gas Residuals. Wagner, (b). Accurate Tool Work. Goodrich-Stanley. (b). Millwrighting. Hobart. (b). 156 ANALYSIS OF BABBITT Metallurgy, etc. (continued). Foundry Nomenclature. Buchanan. (b). Foundry Work. Stimpson. (/>). Pattern Making. Turner-Town. (p). Steel and Its Heat Treatment. Bullens. (p). Rolling Mill Industry. Kindl. (p). Foundry Data Sheets. (/>). Pattern Making. Ritchey. (/>). Pattern Making. Moore, (p). Purchasing. Rindfoos. (p). Forging. Bacon, (p). Plain and Ornamental Forging. Schwartzkopf. (p). The Sheet-Metal Worker's Instructor. Warn. (;'). Strength and Other Properties of Metals. By Officers of the Ordnance Department, U. S. Army. (/). The Goldsmith's Handbook. Gee. (/). Cast Iron in the Light of Recent Research. Hatfield. (/). Physico-Chemical Properties of Steel. Edwards. (/). Metallurgy of Non-Ferrous Metals. Gowland. (/). A Treatise on Electro-Metallurgy. McMillan-Cooper. Modern Copper Smelting. Levey. (/). Study of Electrothermal and Electrolytic Industries. Ashcroft. (a). Examination and Thermal Value of Fuel: Gaseous, Liquid and Solid. Coste- Andrews. (/). Elements of Industrial Management. Smith. (/). Art Metal Work. Payne, (u). Hydn>Electric Power. Lyndon, (u). How to Build up Furnace Efficiency. Hays. (u). Raw Materials of Enamelling. Grunwald. (/). Applied Methods of Scientific Management. Park- hurst, (rf). BABBITT METAL 157 Metallurgy, etc. (continued). Investigating An Industry. Kent. (d). The Practical Tool-Maker and Designer. Wilson. (/). The Moulders' and Founders' Pocket Guide. Over- man. (/). The Practical Brass and Iron Founders' Guide. Lar- kin. (/). Practical Workshop Companion for Tin, Sheet Iron and Copperplate Workers. Blinn. (/). Punches, Dies and Tools for Manufacturing in Presses. Woodworth. (o). Brazing and Soldering. Hobart. (o). Coke Modern Coking Practice, Including Analysis of Materials and Products. Christopher-Byrom. (o). Coal Gas as a Fuel. Fletcher, (e). Proceedings of Chemical and Metallurgical Society of South Africa, P. O. Box 2596, Johannesburg!!, S. A. R. Vols. I, II, III, IV. American Hydroelectric Practice. Taylor-Braymer. , (b). Spontaneous Combustion and Explosion in Coal Car- goes; Their Treatment and Prevention. Rowan. () Fuels: Solid, Liquid and Gaseous. Phillips, (e). Industrial Furnaces and Methods of Control. Damour. <> Coal Analysis. A Treatise on the Comparative Com- mercial Values of Gas Coals and Cannels. Graham. (>. Journal of the Iron and Steel Institute. Journal of the Institute of Metals. American Iron and Steel Institute. Directory of the Iron and Steel Works of the United States and Canada. 158 ANALYSIS OF BABBITT Metallurgy, etc. (continued). National Iron and Steel, Coal and Coke Blue Book. R. K. Polk & Co., Pittsburgh, Pa. Iron and Steel (a pocket encyclopedia) Including Allied Industries and Sciences. Tiemann. (b). Steel : Its Metallurgy and Mechanical Treatment. Roberts- Austin. (). The Metallography and Heat-Treatment of Iron and Steel. Sauveur. (b). British Standard Specifications for Cast Iron Pipes and Special Castings for Water, Gas and Sewage. (Crosby Lockwood & Son.) The Mining Library, (b). Vol. 1 Examination of Prospects. Gunther. Vol. 2 Principles of Mining. Hoover. Vol. 3 Timbering and Mining. Storms. Vol. A Handbook of Mining Details. Vol. 5 Details of Practical Mining. Vol. 6 The Theory and Practice of Ore Dressing. Wiard. 168 ANALYSIS OF BABBITT Metallurgy, etc. (continued). Vol. 7 Manual of Underground Surveying. T rum- bull. Vol. 8 American Mine Accounting. Charlton. Vol. 9 The Cost of Mining. Finlay. Mining Manual and Mining Year Book. 1917. Skin- ner. The Ore Deposits of the United States and Canada. Kemp. (b). Mining Laws of the British Empire. Alford. (/). Ore and Stone Mining. Foster. (/). A Dictionary of Spanish and Spanish-American Min- ing. Raise. (/). Mineral Wealth of China. Wang. (/).. The Mineral Kingdom. Braum and Spencer. (/). Mineralogy of Arizona. Guild, (c). Copper Mines of the World. Weed. (b). Mining Methods in Europe. Mayer, (b). International Mining Manual. Western Mining Direc- tory Co. Denver, Col. Mineral Resources of the United States. Geological Survey. Annual. Vol. I. Metals, Vol. II. Non- Metals. Mines Handbook. A Manual of the Mining Industry of North America. Annual. Stevens Copper Hand- book Co. Metallurgy of Iron. Vol. XL Technical Dictionary. (About 5100 words in each of the six languages.) Schlomann. (b). Engineering Analysis of a Mining Share. Pickering. (). The Relative Corrosion of Alloys. Fehr. Amer. Soc. Mech. Eng, Dec. 3-6, 1918. BABBITT METAL 169 KEY TO PUBLISHERS. a Philadelphia Book Co., Philadelphia, Pa. b McGraw-Hill Book Co., New York City. c Chemical Publishing Co., Easton, Pa. d John Wiley & Sons, New York City. e D. Van Nostrand Co., New York City. / J. B. Lippincott Co., Philadelphia, Pa. g Engineering and Mining Journal (Dec. 1, 1906), New York City. h The Mining Journal, London, England. 1 The MacMillan Co., New York City. j Henry Carey Baird & Co., Philadelphia, Pa. k Longmans, Green & Co., London and New York. / The Foundry, Cleveland, Ohio. m Mining and Scientific Press, San Francisco, Cal. n Allen Book and Printing Co., Troy, N. Y. o N. W. Henley Publishing Co., New York City. p The Penton Publishing Co., Cleveland, Ohio. q P. Blakiston's Son & Co., Philadelphia, Pa. r Boston Testing Laboratories, Boston, Mass. s E. & F. N. Spon, London, England. t The Mining Magazine, London, England. u Wymari & Sons, London, England. v Pitman & Sons, New York City. w Technical Publishing Co. x Scott, Greenwood & Co. y Griffins Publishing Co. 2 McVey Publishing Co. THIS BATE AN INITIAL FINE OF 25 CENTS WILL BE ASSESSED FOR FAILURE TO RETURN BOOK ON THE DATE DUE. THE PENALTY OVERDUE. SEP 21 1937 45M 57AS REC'D Li MAY 2 1&&*~~~ RHCT' L J DPf! 1 o mro LD 21-95w-7,'37 la Yg 1675 UNIVERSITY OF CALIFORNIA LIBRARY