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 METHODS 
 
 
 
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 REESE LIBRARY 
 
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 UNIVERSITY OF CALIFORNIA 
 
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 Accession No. /// .7/6 .Class No. 
 
 

 
I, 
 
METHODS FOR THE ANALYSIS 
 
 OF- 
 
 Ores, Pig Iron and Steel 
 
 IN USE; AT THE; 
 
 Laboratories of Iron and Steel Works 
 
 -IN THE;- 
 
 REGION ABOUT PITTSBURG, PA. 
 
 TOGETHER WITH AN APPENDIX CONTAINING VARIOUS 
 
 SPECIAL METHODS OF ANALYSIS OF ORES 
 
 AND FURNACE PRODUCTS. 
 
 CONTRIBUTED BY THE 
 
 CHEMISTS IN CHARGE, AND EDITED BY A COMMITTEE OF 
 
 THE CHEMICAL, SECTION, ENGINEERS' SOCIETY 
 
 OF WESTERN PENNSYLVANIA. 
 
 UNIVERSITY j 
 
 EASTON, PA. 
 CHEMICAL PUBLISHING Co. 
 
 1898. 
 
PREFACE. 
 
 These methods in use in the iron and steel laboratories of the 
 region near Pittsburg, Pa., were collected and published by the 
 Engineers Society of Western Pennsylvania during 1896. The 
 supply of copies having been exhausted, in response to a contin- 
 uous demand the publication in more convenient form has been 
 undertaken by the Chemical Publishing Company who have been 
 authorized to do so by resolution of the Society at a meeting 
 held March 13, 1897. 
 
 These methods were detailed by those using them in response 
 to the following circular sent out by the committee in charge : 
 
 CHEMICAL SECTION. 
 
 ENGINEERS' SOCIETY OF WESTERN PENNSYLVANIA, 
 PITTSBURG, PA. 
 
 In accordance with a resolution of the Chemical Section of the Engi- 
 neers Society of Western Pennsylvania, the undersigned wish to ask your 
 cooperation in an effort to collect, for publication in the Proceedings of 
 the Society, the method of analysis in use in the various iron and steel 
 works laboratories of the region. 
 
 In calling the attention of chemists to the plan and asking their aid in 
 its fulfilment, it should be mentioned that it is the aim of the Section to 
 secure accurate statements of analytical processes, describing with minute- 
 ness and clearness the successive steps, in order that the proposed 
 compilation may represent as correctly as possible the present status of 
 analytical chemistry as applied to iron and steel. 
 
 A full presentation of the methods in general use is likely to prove of 
 interest and value, but the completeness and promptness of the responses 
 received from a large number of chemists must determine the success of 
 the measure. 
 
 In case you are willing to cooperate, you are requested to send to any 
 one of the undersigned a full description of the methods you use for the 
 determination of the following substances : 
 
 In Ores Silica, iron, phosphorus, manganese. 
 
 In Pig Iron Silicon, sulphur, phosphorus, manganese. 
 
 In Steel Carbon (by combustion), sulphur, phosphorus, manganese, 
 nickel. 
 
 SUGGESTIONS \ 
 
 i. If the method is described in a text-book or journal, a mere reference 
 
iv Preface. 
 
 will suffice, but any deviations from the published methods should be 
 noted. 
 
 2. In writing a description of a method it is very desirable that minute 
 details should be given (e. g., weights taken, volume of solution, temper- 
 atures, etc., etc.). 
 
 3. If more than one method is used, please describe the one in every- 
 day use on which the commercial transactions of the firm are based. 
 
 4. It is earnestly requested that a reply be sent at the earliest possible 
 date. 
 
 Bach method will be published over the name of the sender. The work 
 of the committee will be confined to collecting and arranging for publi- 
 cation without comment or discussion. 
 
 F. C. PHILIPS, 
 
 Western University, Allegheny, Pa. 
 A. G. McKBNNA, 
 
 Duquesne Steel Works, Duquesne, Pa. 
 E. S. JOHNSON, 
 
 Park Bros. & Co., Pittsburg, Pa. 
 
 Committee. 
 
 The methods which have been received in response to this 
 circular may be considered to represent the general practice of 
 the chief iron and steel works in the region of Pittsburg and 
 Western Pennsylvania. 
 
CONTENTS. 
 
 I. Methods used at the Laboratory of the Carnegie Steel Co., Home- 
 stead, Pa. By John S. Unger i 
 
 II. Methods used at the Laboratory of the Monongahela Furnace, 
 
 McKeesport, Pa. By Frederick Crabtree 12 
 
 III. Methods used at the Laboratory of the Junction Iron and Steel 
 
 Co., Steubenville, Ohio. By Joseph M. Wilson 16 
 
 IV. Methods used at the Laboratory of the Carnegie Steel Co., Lucy 
 
 Furnace, Pittsburg, Pa 21 
 
 V. Methods used at the Laboratory of the Black Diamond Steel 
 
 Works, Pittsburg, Pa. By Edward S.Johnson 23 
 
 VI. Methods used at the Laboratory of the Oliver and Snyder Steel 
 
 Works, Pittsburg, Pa. By S. M. Rodgers 36 
 
 VII. Methods used at the Laboratory of the Hainsworth Steel Co., 
 
 Edith Furnace Dep't, Allegheny, Pa. By R. G. Johnston 47 
 
 VIII. Methods used at the Laboratory of the Carnegie Steel Co., 
 
 Edgar Thomson Steel Works and Furnaces, Braddock, Pa. By 
 
 C. B. Murray 50 
 
 IX. Methods used at the Laboratory of the Clinton Iron and Steel 
 
 Co., Pittsburg, Pa. By A. B. Harrison 57 
 
 X. Methods used at the Laboratory of the Isabella Furnace Co., 
 
 Etna, Pa. By F. G. Brinker 60 
 
 XI. Methods used at the Laboratory of the Shenango Valley Steel 
 
 Co., New Castle, Pa. By Warren R. Clifton 63 
 
 XII. Methods used at the Laboratory of the Pennsylvania Railroad 
 
 Co., Altoona, Pa. By C. B. Dudley and F. N. Pease 70 
 
 XIII. Methods used at the Laboratory of Mclntosh, Hemphill & Co., 
 
 Pittsburg, Pa. By J. P. McKelvey 72 
 
 XIV. Methods used at the Laboratory of the W. Dewees Wood Co., 
 
 McKeesport, Pa. By Theo. Tonnele and R. B. Carnahan, Jr.. 74 
 XV. Methods used at the Laboratory of the Ohio Steel Co., Youngs- 
 town, Ohio. By J. C. Barrett 80 
 
 XVI. Methods used at the Laboratory of the Carnegie Steel Co., 
 
 Duquesne, Pa. By James M. Camp 88 
 
 APPENDIX. 
 
 Blast-furnace Cinders and their Analysis. By James M. Camp 101 
 
 Barium Hydroxide as an Absorbent in Carbon Determinations. By A. 
 
 G. McKenna 109 
 
 An Improvement in the Zinc Reductor for the Determination of Iron 
 
 or Phosphorus. By A. G, McKenna 113 
 
 On Some Evolution Methods for Sulphur in Iron and Steel. By W. 
 
 E. Garrigues 117 
 
 The Determination of Chromium. By A. G. McKenna 121 
 
 Notes on the Analysis of Mill and Puddle Cinders. By Jos. M. Wilson 124 
 The Complete Analysis of Chrome Ore. By A. G. McKenna 129 
 
OF THF 
 
 UN' VTY 
 
 
 I. METHODS USED AT THE LABORATORY OF THE 
 CARNEGIE STEEL CO., HOMESTEAD, PA. 
 
 BY JOHN S. UNGER. 
 
 DETERMINATION OF SIUCA IN ORES OF IRON AND MANGANESE. 
 
 To i gram of the ground ore in an 8-oz. beaker add 35 cc. of 
 hydrochloric acid (sp. gr. 1.20), cover with a watch-glass, and 
 boil gently on a hot plate for twenty minutes. Remove and 
 rinse watch-glass and sides of beaker with 15 cc. of water, filter 
 off insoluble matter on an n-cm. filter, catching filtrate in an 8- 
 oz. beaker, and wash with water until soluble matter is removed. 
 The filtrate, which should not exceed 90 cc., is placed on a sand- 
 bath and allowed to go to dryness. The filter is ignited and the 
 residue fused with 8 grams of sodium carbonate. The fusion is 
 run up around the sides of the crucible and then the crucible is 
 cooled by dipping cautiously in an 8-oz. beaker containing 
 35 cc. water, finally turning the crucible on its side and leaving 
 it. Cover beaker with a watch-glass and add hydrochloric acid 
 gradually until effervescence ceases. After the fusion dissolves 
 out of the crucible, remove with a glass rod and wash the cruci- 
 ble with water. The solution should not exceed 90 cc. Evap- 
 orate on a sand-bath to dry ness. When both solutions are evap- 
 orated, moisten the residues with 10 cc. hydrochloric acid 
 (sp. gr. i. 20) and leave on the bath for a few minutes ; then add 
 20 cc. hot water, and filter through an n-cm. filter, the first 
 into a i6-pz. Erlenmeyer flask, washing out the beaker carefully, 
 then filter the second through the same filter. If the alkaline 
 salts have not all dissolved in the second add 20 cc. hqt water 
 and stir until dissolved; filter, and rinse the beaker with hot 
 water until filter is perfectly free from soluble salts. Ignite the 
 filter in a muffle, cool, and weigh as pure silica. The filtrate, 
 which is preserved for further use, should not exceed 150 cc. 
 
 DETERMINATION OF IRON IN IRON ORES. 
 
 To the filtrate from silica (given under silica) add 12 grams 
 
2 John S. Unger. 
 
 of Baker and Adamson's shot zinc and locc. concentrated hydro- 
 chloric acid, and place in the neck of the flask a small funnel. Let 
 the flask stand for about twenty or thirty minutes or until the iron 
 is all reduced, Should the action on the zinc become feeble, add 
 10 cc. concentrated hydrochloric acid. When the iron is re- 
 duced test a drop of the solution with a drop of potassium thio- 
 cyanate on a white porcelain plate. . If it shows no color or just 
 a very faint pink, it is ready for titration. Have ready a i6-oz. 
 wide beaker, a platinum triangle large enough to extend over 
 the edges of the beaker, and a Gooch crucible with a tuft of glass 
 wool \ inch thick at the bottom. Rinse the funnel into the flask 
 with a wash-bottle and pour the solution through the Gooch 
 crucible, receiving the solution in the beaker. Rinse the flask 
 three times with about 10 or 15 cc. of water and wash the Gooch 
 crucible once. To the filtrate in the beaker add 5 cc. concen- 
 trated hydrochloric acid and place on a hot plate for two minutes. 
 The solution will now occupy 225 cc. Remove from the heat 
 and titrate with standard bichromate solution, using 3 drops for 
 each test toward the end, and adding the bichromate solution, 
 5 drops at a time, when almost done. Agitate each test drop 
 by blowing gently, and continue the addition of the bichromate 
 until the last test shows an absence of blue precipitate after 
 agitating and standing thirty seconds. The bichromate used, 
 multiplied by the factor, gives the metallic iron. 
 
 The potassium thiocyanate solution is made by dissolving 10 
 grams of the salt in 100 cc. water and is kept in a small bottle 
 provided with a glass cap and a short piece of -|~inch glass tu- 
 bing to be used as a pipette in taking out the test drops. The 
 potassium ferricyanide solution is made by dissolving i gram of 
 the salt in 100 cc. water and test drops are removed as with thio- 
 cyanate. The solution must be made up each day. One drop 
 is used for a test. 
 
 The potassium bichromate is made by dissolving 52 grams in 
 12 liters of water, then shaking well and keeping the stock bottle 
 protected from light. 
 
 The porcelain plate is 6 by 6 inches with 1 2 depressions i inch 
 wide by \ inch deep on its surface. 
 
 The bichromate solution is standardized by dissolving 3 por- 
 
Carnegie Steel Company, Homestead, Pa. 3 
 
 tionsofabouto.3gram,o.5gram, and 0.7 gram, respectively, of per- 
 fectly clean, soft, iron wire of 99.80 per cent, pure iron in a i6-oz. 
 Brlenmeyer flask (having a small funnel in the neck), in 40 cc. 
 dilute hydrochloric acid, by the aid of gentle heat. When dis- 
 solved, rinse the funnel and sides of flask and make the solution up 
 to 150 cc. Add 12 grams of zinc and when the iron is reduced, 
 titrate exactly as in case of iron in ore. The weight of the wire 
 taken, multiplied by 0.998 and divided by the number of cubic 
 centimeters of bichromate solution used, gives the factor and 
 these factors should agree to the third decimal place. 
 
 For iron in manganese ores, the basic acetate precipitate of 
 iron spoken of under manganese is dissolved in 40 cc. dilute 
 hydrochloric acid, the solution made up to 150 cc. and treated 
 exactly as in the case of the determination of iron in iron ores. 
 
 DETERMINATION OF PHOSPHORUS IN STEEL, PIG IRON, AND ORES. 
 
 Dissolve 1.63 grams of steel in a 6-oz. Krlenmeyer flask in 30 
 cc. nitric acid (sp. gr. 1.20). Place the flask over a burner and 
 evaporate over a naked flame to 15 cc. , add to the boiling solution 
 20 cc. chromic acid solution, and again evaporate to 18 cc., re- 
 move from fire and wash down the sides of the flask with from 5 to 
 7 cc. water and cool to 40 or 45 C. Add6occ. molybdate solution, 
 previously filtered and heated to 40 or 45 C., insert a stopper in 
 the flask, and shake for five minutes. Leave stand in a warm place 
 for fifteen minutes, then filter through a 7-cm. (Baker and 
 Adamson, A grade) filter, previously dried and weighed at 
 110 C., and wash with a 2 per cent, nitric acid solution until 
 free from iron, then twice with 95 per cent, alcohol. Dry 
 twenty minutes at 110 C. and weigh. Each milligram corre- 
 sponds to o.ooi per cent, phosphorus. 
 
 In case of pig iron dissolve 1.63 grams, in a 4|-inch evaporating 
 dish, in 40 cc. nitric acid (sp. gr. 1.20), and evaporate to dry- 
 ness on a sand-bath. Then place on a burner and heat over the 
 naked flame until the mass ceases to evolve red fumes, allow 
 dish to cool and add 25 cc. hydrochloric acid (sp. gr. 1.20). 
 Cover with a watch-glass, and evaporate to 10 cc. Add 
 cautiously 25 cc. nitric acid (sp. gr. 1.42) and evaporate to 
 12 cc., remove from burner, rinse the watch-glass and sides of dish 
 
4 John S. Unger. 
 
 with 12 cc. water, filter through an n-cm. filter into a6-oz. flask, 
 and wash with water. The solution should not exceed 50 cc. 
 Heat to 40 C., add 60 cc. molybdate solution previously filtered 
 and heated to 40 or 45 C., shake, and finish as for steel. 
 
 In case of manganese ores dissolve 1.63 grams in 40 cc. hydro- 
 chloric acid (sp. gr. 1.20) in a 4^-inch evaporating dish, by gentle 
 boiling, then evaporate to dryness on a sand-bath, add 25 cc. nitric 
 acid (sp. gr. 1.42), and evaporate to 12 cc., dilute with 12 cc. 
 water, and filter through an n-cm. filter into a 6-oz. flask. The 
 solution should not exceed 50 cc. Heat to 40 or 45 C., pre- 
 cipitate, and finish as in the case of steel. 
 
 In case of iron ores, if no phosphorus exists in the insoluble resi- 
 due and the ore is easily decomposed, proceed exactly as for man- 
 ganese ore. Should phosphorus exist in the insoluble residue, 
 dissolve 1.63 grams in 40 cc. hydrochloric acid (sp. gr. 1.20) in 
 an 8-oz. beaker by gentle boiling for twenty minutes, dilute with 
 20 cc. water, and filter into an 8-oz. beaker, washing with water; 
 set filtrate on a sand-bath and evaporate to dryness. Ignite 
 residue and then fuse with 8 grams of sodium carbonate and 
 dissolve fusion as for iron in ore, evaporate the solution to dry- 
 ness on a sand-bath, add to each beaker 25 cc. nitric acid (sp. gr. 
 1.42), and evaporate carefully to 12 cc.; dilute with 12 cc. 
 water and filter both through an n-crn. filter into an 8-oz. flask, 
 using the same filter for both solutions. Wash with water, heat 
 to 40 or 45 C., and proceed as for steel. 
 
 The chromic acid solution is made by dissolving 30 grams of 
 pure chromic acid in two liters of nitric acid (sp. gr. 1.42) at 
 a gentle heat. It must be made up fresh at least every two 
 weeks. 
 
 The molybdic acid solution is made by mixing 100 grams 
 molybdic acid to a paste with 265 cc. water, then adding 155 cc. 
 ammonia (sp. gr. 0.90) and stirring until all is dissolved. To this 
 solution add 66 cc. nitric acid (sp. gr. 1.42), stir and set aside 
 for an hour. In another vessel make a mixture of 395 cc. nitric 
 acid (sp. gr. 1.42) and i,ioocc. water. Then pour the first 
 solution into the second in a small stream, stirring constantly. 
 Let stand for twenty-four hours when it is ready for use. 
 
 The filter-papers for weighing the yellow precipitate are Baker 
 
Carnegie Steel Company, Homestead, Pa. 
 
 and Adamson's y-cm. A grade. These retain the precipitate 
 without its showing a tendency to pass through, and do not con- 
 tain an appreciable amount of soluble matter, which might be 
 extracted by the acid solution. 
 
 The stand for the evaporation over the burners is made of i- 
 inch angle iron bent and fitted with ^-inch asbestos mill board, 
 having a 2|-inch hole over each burner ; this supports the flask 
 easily and prevents the solution from baking on the sides. 
 
 The drying bath is a copper drum with a coil of i-inch steam 
 pipe at bottom and fitted with a movable disk, near the top, hav- 
 ing -J-inch holes, through which the stem of the funnel is inserted, 
 the whole being covered by a lid. Steam is supplied at boiler- 
 pressure and a temperature of 110 C. with very little fluctuation 
 is constantly maintained. 
 
 DETERMINATION OF MANGANESE IN MANGANESE ORES. 
 
 To the filtrate from silica previously spoken of, add ammonia. 
 When almost neutral, add it drop by drop until the solution 
 assumes a reddish brown color. When the last drop produces 
 a reddish brown precipitate, which does not dissolve on shaking, 
 add 10 to 15 cc. of ammonium acetate and bring to a boil. Boil 
 one minute. Then remove and let the precipitate settle ; filter 
 through a i2j-cm. filter, catching the filtrate in a i6-oz. beaker, 
 and wash out the flask once with hot water. When the filter has 
 run dry, place a funnel in the flask, and dissolve precipitate in 15 
 cc. dilute hydrochloric acid (i : i), wash iron out of paper, and 
 repeat the precipitation with ammonia and ammonium acetate, 
 combining the filtrates. Wash the precipitate three times with 
 hot water and reserve for the estimation of iron. To the fil- 
 trate add three drops of solution of phenol-phthalein, then 
 ammonia until pink, then 3 cc. in excess. Pass a current of 
 hydrogen sulphide through the solution for ten minutes, rinse 
 delivery-tube and set beaker on sand- or steam-bath for thirty 
 minutes, filter through a double-pointed 7- andii-cm. filter, and 
 wash with dilute ammonium sulphide water. When washed 
 place a clean i2-oz. beaker under funnel and pour over precipi- 
 tate 40 cc. of a mixture of 20 cc. hot water and 20 cc. of 50 per 
 cent, acetic acid, keeping the funnel covered with a watch-glass. 
 
6 John S. Unger. 
 
 If the manganese sulphide does not all dissolve pour the solu- 
 tion through the filter again, wash filter four times with hot 
 water, and place beaker on a hot plate. Boil for fifteen minutes, 
 dilute to 150 cc ; add 15 cc. ammonium phosphate, and if a pre- 
 cipitate forms, add a few cc. of hydrochloric acid until dissolved, 
 bring to a boil, and then precipitate by adding ammonia, drop by 
 drop, until the solution smells of ammonia. While precipitating, 
 stir constantly to bring the precipitate down in a granular form, 
 filter through a i2^-cm. filter, using suction, ignite in a muffle, 
 and weigh as manganese pyrophosphate. 
 
 The ammonium acetate solution is made by dissolving 120 
 grams in 2,000 cc. water, then filtering. 
 
 The ammonium phosphate is a saturated solution of the salt 
 in cold water, diluted with an equal bulk of water. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Weigh into a 4^-inch evaporating dish 0.9333 gram of sam- 
 ple, cover with a watch-glass, then add 50 cc. of a mixture of 
 10 cc. sulphuric acid (sp. gr. 1.83) and 40 cc. water. Place over 
 a Bunsen burner, supporting the dish on a piece of ^-inch asbes- 
 tos board, having a 2^-inch hole in the center, and evaporate 
 until dense, white fumes escape, and the drop of water which 
 condenses on the watch-glass falls back into the dish with a 
 hissing sound. Remove the dish from the fire and let cool for two or 
 three minutes. Then cautiously add 50 cc. of a mixture of 10 
 cc. hydrochloric acid (sp. gr. 1.20) and 40 cc. water, place over 
 burner, and bring to a boil. Boil gently for one minute, remove 
 from the fire, rinse the watch-glass, and filter the solution through 
 an 1 1 -cm. filter. Wash once with water, then with dilute hydro- 
 chloric acid (t : i) and finally with water until free from iron. 
 
 Ignite the precipitate in the muffle, cool, and weigh. To the 
 residue in the crucible add from 4 to 10 drops pure hydrofluoric 
 acid, depending on the amount of silica present. Drive off 
 excess of acid by heating gently on a hot iron plate, then ignite 
 for two or three minutes in a muffle, cool, and weigh. 
 
 The difference in weight is divided by 2, and a decimal point 
 inserted two places from the right hand gives the percentage of 
 silicon in the sample. 
 
Carnegie Steel Company, Homestead, Pa. 7 
 
 DETERMINATION OF SULPHUR IN PIG IRON AND STEEL. 
 
 Weigh 5 grams of the sample into a i6-oz. side-necked flask, 
 fitted with a rubber stopper and thistle-tube. An 8-oz. beaker 
 of the tall, narrow shape, containing 15 cc. of cadmium solution 
 and filled to within one inch from the top with water, is placed under 
 the delivery-tube. Then 90 cc. of a mixture of 40 cc. hydro- 
 chloric acid (sp. gr. 1.20) and 50 cc. water, are poured into the 
 thistle-tube and the apparatus is placed on a stand made of \- 
 inch asbestos mill board, having a 2^-inch hole at one side and 
 heated by a Bunsen burner. The heating is so regulated that 
 the evolved gases are delivered at about 3 bubbles per second. 
 As the action grows feeble, the heat is increased, until finally 
 when all is dissolved, the solution is brought to a boil and kept 
 boiling for one minute. The delivery-tube is then raised out of 
 the beaker and the flask set aside. 
 
 The contents of the beaker are then poured into a i2-oz. wide 
 beaker, the precipitate is washed out of the beaker with a wash- 
 bottle, and 5 cc. of starch paste are added. 35 cc. of a mixture of 
 40 cc. hydrochloric acid (sp. gr. 1.20) and 50 cc. water are then 
 poured into the absorption beaker and rinsed into the solution 
 in the large beaker. The sulphur is then immediately titrated 
 with standard iodine solution. 
 
 The iodine solution is made by dissolving 8 grams iodine and 
 30 grams potassium iodide in 200 cc. cold water and then dilu- 
 ting to about 1,850 cc. A standard steel is then tested by the 
 method and the result noted, and from this the amount of water 
 needed to dilute the iodine so as to bring it to the required 
 strength, is calculated. After diluting, two determinations are 
 made on the standard steel to see that the iodine solution is 
 exactly right. The iodine solution is made of such strength 
 that i cc. = o.oi per cent, of sulphur in the sample. Two liters 
 of standard iodine are made up at once and the solution is pre- 
 served in a dark cupboard. The amount actually in use is kept 
 in a special burette having a blackened receiver to exclude light. 
 The stock solution is standardized every week. 
 
 The cadmium solution is made by dissolving 300 grams cad- 
 mium chloride in i liter hot water in a large bottle and then 
 adding 1.5 liters ammonia (sp. gr. 0.90), filtering through a 
 
8 John S. Unger. 
 
 fluted filter into a 1 2-liter bottle. 6.5 liters ammonia (sp. gr. 
 0.90) are then added to the solution and 3 liters of water. 
 The whole is well shaken when it is ready for use. 
 
 The starch paste is made by heating i liter of water to boiling- 
 point in a i,2oo-cc. flask and adding gradually 10 grams of starch 
 made into a cream with 50 cc. cold water. Keep the solution 
 boiling constantly. When all the starch is added boil five 
 minutes, then set aside to cool, decant the liquid, throwing the 
 last 50 cc. away. 
 
 The solution is made up every three days. 
 
 DETERMINATION OF CARBON IN STEEL. 
 
 5 grams of the sample are weighed into a clean 8-oz. flask 
 and 200 cc. of copper potassium chloride added ; the flask is 
 closed with a rubber stopper and shaken until the precipitated 
 copper is completely redissolved, which is easily detected by the 
 absence of copper-covered particles at the bottom of the flask. 
 Remove and rinse the stopper, then filter through a perforated 
 platinum boat, having a layer of asbestos \ inch thick at bottom 
 and held in a platinum holder. Wash the residue twice with 
 concentrated hydrochloric acid, then with water until all the 
 soluble matter has been removed. Dry the boat for two hours 
 at 90 C. when it is ready for burning. Introduce into the 
 combustion-tube, pushing it against theroll of silverfoil, andstart 
 a current of oxygen from the cylinder through the apparatus at 
 2 to 3 bubbles per second. In the meantime weigh the potash 
 bulb and the small calcium-chloride tube filled with solid potas- 
 sium hydroxide. Attach the bulb and tube to the apparatus 
 and light first two burners and leave burning for five minutes to 
 heat platinum gauze in a combustion-tube to redness, then light 
 the next burner and leave burning two minutes, following this 
 by the others in exactly the same way. When all are lighted 
 leave burning five minutes. Then shut off the oxygen and start 
 the air current, being careful to make the change without allow- 
 ing any back-pressure from the air in the room. Aspirate air 
 for forty minutes, using i liter, and weigh. 
 
 The copper potassium chloride solution is made by saturating 
 2 liters of cold water with the salt, adding to the solution 100 cc. 
 
Carnegie Steel Company, Homestead, Pa. 9 
 
 of hydrochloric acid (sp. gr. 1.20), then i gram of a high car- 
 bon steel, shaking until dissolved, then filtering the whole solu- 
 tion into a 2-liter bottle, through an asbestos filter. 
 
 The asbestos is prepared by rubbing the ignited fiber through 
 a 20- mesh sieve by a gentle stream of water, receiving the water 
 and pulp in a large vessel, allowing the pulp to settle and draw- 
 ing the water off by a siphon. Cover the pulp with strong, hot 
 hydrochloric acid and digest over night ; draw off the acid with 
 a siphon and wash with water by decantation until free from 
 acid, pour into a bottle with water sufficient to cover it, and 
 when needed shake the bottle before drawing out a portion. 
 
 The purifying of the air and oxygen is effected in an apparatus 
 having one side fitted to the aspirator bottles supplying the air, 
 while the other side connects directly with the oxygen cylinder. 
 The wash-bottles are glass-stoppered, filled to \ height with 
 potassium hydroxide (sp. gr. 1.30), the attached calcium-chlo- 
 ride jars filled to -J- height with solid potassium hydroxide, and 
 the balance with calcium chloride and a plug of glass wool on 
 top ; a Y-tube connects each side with the combustion-tube. 
 
 The combustion-tube is of platinum, J-inch bore, with a body 
 20 inches long, having T 3 g~inch platinum tubes 3 inches long 
 extending from the body. The tube contains a roll of platinum 
 gauze 4 inches long, filling the bore of the tube and pushed into 
 the combustion-tube until the anterior end is over the first burner; 
 this gauze is followed by a roll i^ inches long, of silver foil 
 inclosed in a piece of platinum foil, which just fills the bore of 
 the tube, and this is then followed by the boat, the tube being 
 closed by a cone-shaped ground-joint which is reinforced by 
 bands of nickel. 
 
 The combustion furnace is an ordinary lo-burner Bunsen 
 furnace. 
 
 The absorbing train is made up of two [j-tubes giving a total 
 length in tubes of 44 inches ; these are followed by a Geissler 
 potash bulb containing potassium hydroxide solution (sp. gr. 
 1.30), (after a bulb has absorbed about \ gram carbon dioxide a 
 fresh one is used), and a 4-inch calcium-chloride tube contain- 
 ing solid potash. The bulb and tube are weighed, and these 
 are followed by an 8-inch calcium-chloride tube filled with solid 
 
io John S. Unger. 
 
 potash to prevent any carbon dioxide from the outside air enter- 
 ing the apparatus. The first l)-tube of the train is filled for the 
 first 5 inches of its length with granulated silver. This silver 
 is removed from time to time as it becomes dark-colored on the 
 surface, ignited, and replaced in a tube. The silver is followed 
 by 17 inches of calcium chloride. In the next l)-tube there are n 
 inches of calcium chloride, then n inches of anhydrous copper 
 sulphate, followed by a plug of glass wool. The copper sul- 
 phate is renewed after every five combustions. When the l)-tubes 
 are first filled a combustion is made in the ordinary manner, but 
 no weighings made, the object being to saturate any caustic 
 lime which might be in the calcium chloride used. The entire 
 train is supported on a special support which permits of adjust- 
 ment in a vertical or horizontal direction. 
 
 DETERMINATION OF MANGANESE IN STEEL. 
 
 Weigh 200 milligrams of steel into a 2-oz. flask and add 20 cc. of 
 1.20 nitric acid. When dissolved, boil gently for five minutes, 
 remove and pour the solution into a ico-cc. graduated cylinder. 
 Wash out the flask three times with water. Finally dilute to the 
 loo-cc. mark. Pour the contents into a 4-oz. precipitating jar and 
 mix by pouring into a cylinder or jar at least three times, draw off 
 25 cc. with a pipette into the flask in which the solution was 
 made, add 6 cc. nitric acid (sp. gr. 1.20) from a burette, place 
 on a hot plate together with a standard in which the manganese 
 is exactly known and which has been treated exactly like the 
 steel, and when almost boiling add -J gram lead peroxide, 
 measured approximately on a small glass spatula, and boil for 
 three minutes. Remove, place in a cooling bath, and allow the 
 lead dioxide to settle, which usually requires fifteen minutes. 
 Decant the solution into a comparison tube and compare with 
 the standard properly diluted as for color carbon determination. 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 Dissolve as for steel, place a small funnel in the cylinder, and 
 filter. Wash the residue thoroughly, being careful not to allow 
 the washings to exceed 100 cc., and treat the filtrate as in the 
 case of steel. 
 
Carnegie Steel Company, Homestead, Pa. n 
 
 DETERMINATION OF NICKED IN STEEL. 
 
 Dissolve i gram of steel in 25 cc. nitric acid (sp. gr. 1.20) and 
 boil in a loo-cc. flask, until solution is complete. Wash con- 
 tents of flask into a ^-gallon flask containing 700 cc. hot water, 
 add 100 cc. sodium acetate solution, and bring to a boil for one 
 minute. Remove from plate and let settle for three minutes, 
 filter through a 38^-cm. fluted filter into a liter beaker, and allow 
 the precipitate to run dry. To the filtrate, which should be per- 
 fectly clear and almost colorless, add 3 drops of phenol-phthalein, 
 then ammonia until pink, place on a hot plate and pass a current 
 of hydrogen sulphide gas through the solution for ten minutes ; 
 remove from the plate and add 12 cc. acetic acid (50 per cent.), 
 stir and allow the precipitate to coagulate on a warm plate for ten 
 minutes, filter through a i2^-cm. filter and wash with hydrogen 
 sulphide water made slightly acid with acetic acid. Roast in a 
 platinum crucible, carefully at a low red heat (usually at the 
 front of a muffle) until the paper has just burned off. Take out 
 crucible and break up the precipitate with a platinum rod to pow- 
 der, then place in the muffle and ignite for fifteen minutes at a 
 bright red heat, cool, and weigh. To the crucible add 3 cc. 
 hydrochloric acid (sp. gr. 1.20), cover with a watch-glass and 
 warm gently on a plate until the precipitate has dissolved. 
 Wash into a i5o-cc. beaker with water, add ammonia until the 
 solution smells strongly of ammonia, and filter from the silica and 
 ferric hydroxide. Redissolve precipitate in 3 cc. hydrochloric acid 
 and repeat the precipitation with ammonia, wash with hot water, 
 ignite in same crucible, and weigh. The difference in the weight 
 gives the NiO. A correction of 5 per cent, on the quantity of 
 nickel present is made to provide for the nickel remaining in the 
 basic acetate precipitate. 
 
 The sodium acetate solution is made by dissolving 3,000 grams 
 of sodium acetate in 12 liters of water. 
 
II. METHODS USED AT THE LABORATORY OF THE 
 MONONGAHELA FURNACE, McKEESPORT, PA. 
 
 BY FREDERICK CRABTREE. 
 
 DETERMINATION OP SILICA IN ORES. 
 
 0.5 or i gram of the ore (powdered to pass through a 100- 
 mesh sieve) is fused with sodium carbonate, the fusion 
 dissolved in dilute hydrochloric acid, and the solution evapo- 
 rated to dryness in a 5^-inch or 6-inch R. M. evaporating dish. 
 When the residue is thoroughly dry, dilute hydrochloric acid is 
 added and the mixture boiled until the iron is dissolved. The 
 solution is then filtered, the silica washed with hot water, 
 ignited, and weighed. 
 
 DETERMINATION OF IRON IN ORES. 
 
 0.5 gram of the ore is placed in a 2-oz. beaker with 
 about 35-40 cc. of strong hydrochloric acid, and allowed to 
 stand on a steam-bath for several hours (usually over night) . 
 Sometimes several drops of stannous chloride are added to 
 hasten the solution. When ready for titrating, the contents of 
 the beaker are heated to boiling and examined to see if the 
 residue is white ; a slight excess of stannous chloride solution 
 is added, the mixture placed in a 2O-oz. beaker and diluted 
 with about 300 cc. of cold water. About 25 cc. of cold satu- 
 rated solution of mercuric chloride are then added and the solu- 
 tion titrated with a bichromate solution containing about 4.38 
 grams per liter. 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 2 to 5 grams of the ore are digested with 75-150 cc. of 
 strong hydrochloric acid and the solution evaporated to hard 
 dryness. About 100 cc. of strong hydrochloric acid are poured 
 on the residue and the mixture boiled until the solution is con- 
 centrated to about half that volume. Water is then added and 
 
Monongahela Furnace. 13 
 
 the diluted solution filtered, keeping the volume of the filtrate 
 as small as is convenient. 
 
 The solution is then evaporated with nitric acid until the 
 hydrochloric acid is driven off. The insoluble residue is 
 ignited and the silica driven off by boiling with hydrofluoric acid. 
 The residue is fused with sodium carbonate, the fusion dissolved 
 in nitric acid, and the solution filtered into the main solution. 
 To this ammonia water is next added (the fluid is now in a 16- 
 oz. Brlenmeyer flask) until the solution becomes pasty and 
 smells ammoniacal ; the precipitate is dissolved in a slight excess 
 of nitric acid and the solution brought to a temperature of 80 
 C., when 40 cc. of the molybdate solution are added. 
 
 A current of air is used to agitate the solution for about five 
 minutes ; the latter is filtered while still warm. After washing 
 thoroughly with distilled water, the yellow precipitate is titrated 
 according to the acidimetric method. 1 
 
 Sometimes the method is varied by not evaporating with 
 nitric acid to drive off hydrochloric acid after filtering from the 
 insoluble residue ; the insoluble residue may then be fused, the 
 fusion dissolved in nitric acid, and the solution evaporated to 
 dry ness to get rid of silica. 
 
 DETERMINATION OP MANGANESE IN ORES. 
 
 The filtrate from the silica determination is nearly neutralized 
 by ammonia, and then ammonium carbonate solution added 
 until the iron is on the point of coming down, the solution 
 still remaining clear. The addition of a solution containing 
 about 2 grams of ammonium acetate and hot water enough to 
 give a volume of about 400-500 cc., will cause the precipitation 
 of the iron and aluminum. The contents of the beaker are 
 heated to boiling and boiled for about one minute. The pre- 
 cipitate is filtered off and washed with hot water immediately. 
 The manganese in the filtrate is precipitated by bromine and 
 ammonia, and usually weighed as Mn 3 O 4 . 
 
 DETERMINATION OF SIUCON IN PIG IRON. 
 
 i gram of drillings is dissolved in 20 to 25 cc. of nitric acid 
 
 1 Hundeshagen : Ztschr. anal, Chem., 1889, p. 171; and Handy: Proc. Engineers' So- 
 ciety IV. Pa., 1892, p. 78. 
 
 \ 
 
14 Frederick Crabtree. 
 
 (1.20) and 8 to 10 cc. of dilute sulphuric acid (1:3) and evapo- 
 rated in a 5-inch R. M. dish until the sulphuric fumes are given 
 off copiously. The residue is treated with dilute hydrochloric 
 acid and the mixture boiled ; the residue is filtered off and washed 
 with hot water and dilute hydrochloric acid, ignited, and 
 weighed as SiO 2 . 
 
 DETERMINATION OF SULPHUR IN PIG IRON. 
 
 The evolution method is ordinarily used, absorbing the sul- 
 phur in a dilute ammoniacal solution of cadmium chloride, and 
 titrating with iodine solution without filtration. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 5 grams of Bessemer pig iron are dissolved in 100 cc. 
 of dilute nitric acid (30 per cent, of nitric acid of 1.42 sp. 
 gr.); the loss due to evaporation is made good by diluting 
 to just loo cc., and the solution then filtered. Kighty cc. of the 
 filtrate are boiled, oxidized by permanganate solution and the 
 manganese oxide dissolved by the addition of hydrochloric acid. 
 The solution is made ammoniacal and the precipitatere dissolved 
 by nitric acid; to the solution, at a temperature of 75-8o C., 40 
 cc. of molybdate solution are added, and a current of air used 
 to agitate the liquid for about five minutes. The solution is 
 filtered while warm, the precipitate being washed with cold 
 water, and then titrated with a caustic potash solution, i cc. of 
 which is equivalent to 0.0002 gram phosphorus. 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 Titration by Permanganate. One gram of the pig iron is dis- 
 solved in dilute nitric acid (25 cc. water, 15 cc. nitric acid of 
 1.42 sp. gr.) ; the solution is evaporated nearly to dryness, 
 diluted with water, a slight excess of zinc oxide being mixed 
 with the water added, and the volume made up to 500 cc. by 
 addition of water. After thoroughly mixing, the precipitate is 
 allowed to settle ; 250 cc. of the supernatant liquid are decanted 
 and titrated while hot. 
 
 DETERMINATION OF CARBON IN STEEL. 
 
 Chromic Acid Combustion Method. Use the following train after 
 
Monongahela Fwnace. 15 
 
 the condenser : First, a small empty bottle ; second, pyrogallic 
 solution recommended by Committee on International Standards ; 
 third, silver sulphate solution ; fourth, strong sulphuric acid ; 
 fifth, potash bulb ; sixth, small weighed flask containing sul- 
 phuric acid to retain any moisture that might be carried over 
 from potash bulb ; seventh, a guard test-tube containing sul- 
 phuric acid. 
 
 For dissolving the steel use a solution of copper potassium 
 chloride acidified with hydrochloric acid, and shake or agitate 
 so as to have steel dissolved quickly. 
 
 DETERMINATION OF SULPHUR IN STEEL. 
 
 Iodine titration ; the process described for pig iron. 
 
 DETERMINATION OF PHOSPHORUS IN STEEL. 
 
 4 grams are dissolved in 100 cc. of dilute nitric acid (sp.gr. 
 1.13), oxidized by permanganate, the precipitated manganese 
 oxide dissolved by hydrochloric acid, etc., as in case of pig iron. 
 
 DETERMINATION OF MANGANESE IN STEEL. 
 
 Color Method. 0.2 gram of steel (our steel is soft and con- 
 tains from 0.25 to 0.45 per cent, manganese, usually) is dis- 
 solved in 15 cc. of dilute nitric acid (sp. gr. 1.25). When the 
 solution is clear, and nitrous fumes are all expelled, 15 cc. of water 
 are added ; the solution is brought to lively boiling, lead per- 
 oxide added, and the mixture boiled two minutes ; a little more 
 lead peroxide is then added, when the flasks are removed from 
 the hot plate and placed in cold water for settling. 
 
III. METHODS USED AT THE LABORATORY OF THE 
 
 JUNCTION IRON AND STEEL COMPANY, 
 
 STEUBENVILLE, OHIO. 
 
 BY JOSEPH M. WILSON . 
 
 DETERMINATION OF SILICA IN IRON ORES, 
 
 Weigh i gram of ore into a 5-inch flat dish, moisten with 
 10 cc. water, add 30 cc. concentrated hydrochloric acid, evapo- 
 rate on a hot plate to dryness, and ignite. Moisten with hydro- 
 chloric acid, dry, and ignite again. Cool, moisten with hydro- 
 chloric acid, dissolve in 30 to 50 cc. boiling water, filter, wash 
 with hot hydrochloric acid (i : i) and with cold water. Burn 
 the filter wet. Mix with 5 to 6 parts sodium carbonate and fuse. 
 Dissolve fusion in 50 to 60 cc. water, add hydrochloric acid till 
 acid, evaporate to dryness, ignite till no further decrepitation 
 occurs, cool, moisten with hydrochloric acid, dry and ignite (to 
 render silica insoluble), cool, and moisten with hydrochloric acid ; 
 take up in boiling water, filter, and wash twice alternately with 
 hot hydrochloric acid ( i : i ) and cold water ; then five or six 
 times with hot water. Burn and weigh as SiO a . 
 
 If greater accuracy be desired, moisten the silica with hydro- 
 fluoric acid and add a few drops of sulphuric acid. Evaporate 
 to dryness, ignite, cool, and weigh. The loss = SiO 2 . 
 
 DETERMINATION OF IRON IN ORES. 
 
 The following solutions are employed : Potassium dichromate, 
 4.9 grams dissolved in one liter of water; i cc. = 0.005 gram 
 Fe. Stannous chloride, 100 grams dissolved in i liter of hydro- 
 chloric acid (i : i). Mercuric chloride, 50 grams dissolved in i 
 liter of water. Potassium ferricyanide, a piece one-fourth the 
 size of a pea in 40 cc. water. 
 
 Weigh 0.25 and 0.5 gram ore into small unlipped beakers, 
 moisten with water, add 30 cc. hydrochloric acid, cover, and place 
 on a steam table ; when solution is complete and residue appears 
 
Junction Iron and Steel Company. 17 
 
 white, boil on a hot plate, add stannous chloride from a pipette till 
 the liquid becomes colorless, boil a few moments, remove to steam 
 table till ready to titrate, wash into beaker, dilute to 300-350 cc., 
 stir, pour in excess of mercuric chloride (30 to 40 cc.), stir, run 
 in potassium dichromate at once until four drops fail to develop 
 a blue color with ferricyanide indicator in one-half minute. 
 Burette-reading on half-gram samples gives the per cent, of iron 
 when i cc. potassium dichromate = 0.005 gram iron. Reading 
 on \ gram doubled should vary not more than 0.2 cc. from that 
 on \ gram. 
 
 Precautions. Avoid large excess of stannous chloride ; one or 
 two drops more than is required to destroy yellow color is suffi- 
 cient. 
 
 In adding mercuric chloride pour all in at once. If added 
 slowly, metallic mercury is precipitated and the operation 
 spoiled. 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 Weigh 10 grams ore into a 5 -inch (deep) dish, moisten with 
 water, and add 100 cc. hydrochloric acid ; let stand on steam 
 table, evaporate to dryness, heat, cool, moisten with 100 cc. 
 hydrochloric acid ; boil down to a syrup, add 75 cc. water, filter, 
 and wash with hydrochloric acid ( i : i ) and cold water. Ignite 
 residue, fuse with 5 to 6 parts of sodium carbonate, dissolve the 
 fusion in water and hydrochloric acid, evaporate to dryness and 
 heat, moisten with hydrochloric acid, take up with water, filter, 
 boil filtrate, and add a slight excess of ammonia. Filter, wash 
 two or three times with hot water, dissolve in hot nitric acid of 
 1.2 specific gravity, add to main solution, which has in the 
 meantime been evaporating to a syrup; add 75 cc. nitric 
 acid and again evaporate to a syrup ; transfer to a i6-oz. flask 
 and add an excess of ammonia ; redissolve the precipitate in 
 nitric acid in very slight excess, warm to 87 C., add 50-75 cc. of 
 molybdate solution, shake five minutes, and allow to settle; filter 
 and wash with ammonium sulphate solution till free from iron. 
 
 The ammonium sulphate solution is made by diluting and 
 mixing 48 cc. sulphuric acid and 55 cc. ammonia, and then 
 making up to 2 liters. 
 
1 8 Joseph M. Wilson. 
 
 The molybdate solution is prepared according to Woods' 
 formula. 1 
 
 A stream of air is blown through the liquid while adding the 
 molybdate solution. 
 
 The yellow precipitate is dissolved in ammonia, 5 to 10 cc- 
 magnesia mixture are added, the liquid well stirred and allowed 
 to stand for two hours ; filter and without washing redissolve 
 the precipitate in hydrochloric acid. The bulk of the liquid 
 must be kept below 25 cc. A piece of citric acid half the size 
 of a pea is added and then ammonia in slight excess. After 
 stirring, the liquid is set aside for fifteen to twenty minutes, stir- 
 ring occasionally. The solution is now diluted with an equal 
 bulk of ammonia and allowed to stand from twelve to twenty- 
 four hours. Filter, using a Gooch crucible ; wash with a solu- 
 tion of ammonium nitrate containing 50 grams ammonium 
 nitrate in 2 liters nitric acid (i : 3) ; burn and weigh. Or, the 
 yellow precipitate is dissolved in sodium hydroxide and titrated 
 with standard nitric acid, according to Hundeshagen, 2 or, the 
 precipitate is dissolved in ammonia, the solution acidulated with 
 sulphuric acid and the phosphorus determined volumetrically by 
 permanganate, according to Emmerton. 3 
 
 DETERMINATION OF MANGANESE IN ORES AND IN METALS. 
 
 Volhard's Method : This method was described by Bmmerton 4 
 and is as follows : * ' Evaporate solution peroxidized with 
 sulphuric acid, in excess, till copious fumes are evolved ; cool, 
 take up in water, filter into a 3oo-cc. graduated flask, add 
 sodium carbonate till color is wine-red, but no precipitate forms ; 
 then zinc oxide suspended in water till color is light brown (or 
 perhaps fawn), mix by pouring into beaker and back several 
 times, filter through a ic-inch, dry, fluted filter, take 200 cc. of fil- 
 trate in a i6-oz. flask, to which add 2 drops nitric acid (sp. gr. 
 1.42), boil, run in potassium permanganate a little at a time, 
 shake vigorously to make precipitate collect, allow to settle, and 
 repeat till a permanent pink is obtained. 
 
 1 Proc. Engineers* Society W. Pa., 8, 80, 1892. 
 
 2 Ztschr. anal. Chem., 1889, 171. 
 
 8 Blair's Analysis of Iron, Second Udition, p. 85. 
 * Trans. A . I. M. ., 10, 204. 
 
Junction Iron and Steel Company. 19 
 
 Notes. This method is not applicable to substances contain- 
 ing less than 0.8 percent, manganese owing to the difficulty 
 in distinguishing the color of manganese dioxide, from the pink 
 of potassium permanganate. When the substance contains 
 more than 5 per cent. , take 100 cc. , or even less, instead of 200 cc. 
 
 Pig iron is to be treated as for silicon, then filtered, the filtrate 
 evaporated a second time with sulphuric acid, proceeding then 
 as above described. 
 
 The permanganate solution contains 1.27 grams potassium 
 permanganate per liter. 
 
 i cc.= 0.002262 gram Fe, or 0.000666 gram Mn, correspond- 
 ing to o. i per cent, manganese when f gram of the sample is 
 used. 
 
 Color Method. Weigh 0.2 gram of the sample into an n- 
 inch tube, add 20 cc. nitric acid (sp. gr. 1.20), boil till the 
 escape of brown fumes ceases, add 10 cc. of water, boil, add about 
 3 grams lead dioxide, and continue boiling for two and one-half 
 minutes. Place in cold water until the liquid has become clear; 
 decant into the reading tube and compare. 
 
 Use pig iron or steel in which the manganese has been deter- 
 mined gravirnetrically : (a) By Ford's method ; (b) by acetate 
 method, as a standard. (Weigh standard with each batch to be 
 read.) Manganese is also determined by precipitation by bro- 
 mine, and weighing as Mn 3 O 4 . 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Brown's method is used. 
 
 DETERMINATION OF SULPHUR IN PIG IRON. 
 
 By method described by Kmmerton 1 absorption of hydrogen 
 sulphide in potassium hydroxide (Powers and Weightman's white 
 stick caustic is the only brand that will give uniformly correct 
 results) and titration with iodine solution, i cc. = 0.0005 gram 
 sulphur. Standardize by a steel of known sulphur content. 
 Results check with those obtained by the aqua regia method. 
 When solution is complete, boil till steam reaches the stopper of 
 the first tube, remove flame, open the stop-cock in the funnel, and 
 
 1 Trans. A. I. M.E., 10. 
 
20 Junction Iron and Steel Company. 
 
 allow to stand till liquid in tube is cold. Wash into a beaker, 
 making the volume up to 300-400 cc., add 3-5 cc. starch solution, 
 then excess of hydrochloric acid, titrate with iodine solution, of 
 which i cc. = 0.0005 gram sulphur. Standardize the iodine 
 solution with steel or pig iron, the sulphur content of which 
 has been determined as indicated. 
 
 Precautions. Be sure that the metal is entirely dissolved. 
 Pig irons high in sulphur frequently dissolve very slowly and 
 must be watched carefully. The method for sulphur determina- 
 tion described by N. W. lyord 1 is to be highly recommended. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 Follow Emmerton till the yellow precipitate is obtained, then 
 Hundeshagen, 2 and Handy. 3 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 Color method, using a pig iron standard ; also Ford's method 
 for the purpose of checking. 
 
 DETERMINATION OF CARBON IN STEEL. 
 
 Ullgren's method, as described by McCreath, 4 is followed, 
 checking by combustion in a platinum tube. As the solvent, 
 ammonio-cupric chloride, in saturated solution, is used. 
 
 The chromic acid solution contains 80 cc. concentrated sul- 
 phuric acid (previously purified by the addition of a little chromic 
 acid) and 10 cc. of a saturated solution of chromic acid crystals. 
 Not more than 20 cc. of water are used in rinsing the carbon 
 into the combustion flask. Soda-lime is the absorbent for the 
 carbon dioxide evolved. 
 
 The methods for the determination of sulphur and phosphorus 
 are the same as in the case of cast iron. 
 
 Manganese is determined by color ; checking by Ford's 
 method. 
 
 Nickel is determined according to the method of Eastwick. 
 
 1 Notes on Metallurgical Analysis, p. 5-2. 
 
 2 Loc. tit. 
 
 8 Proc. Engineers' Society IV. Pa., 1892, p. 78. 
 4 Trans. A. I. M. E., 5, 575. 
 
IV. METHODS USED AT THE LABORATORY OF THE 
 CARNEGIE STEEL COMPANY, LUCY FUR- 
 NACE, PITTSBURG, PENNA. 
 
 BY ROBERT MILLER. 
 
 DETERMINATION OF SILICA, IRON, AND PHOSPHORUS IN IRON 
 
 ORES. 
 
 I use the methods described on pages 16, 19, 22-26, respect- 
 ively, of " Notes on Metallurgical Analysis," by N. W. Lord. 
 
 DETERMINATION OF SILICON AND SULPHUR IN PIG IRON. 
 
 On pages 37 and 35, respectively, of the above work, will be 
 found described the methods used by me for this purpose. 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 Volhard's method, as described by Blair 1 , is used for this de- 
 termination. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 Weigh off i to 5 grams of iron (according to the amount of 
 phosphorus present) , put into a 4-oz. beaker, and add cautiously 
 25-75 cc. nitric acid (sp. gr. 1.20). After the violent action 
 has ceased, boil down to dryness, and bake for thirty minutes. 
 Allow to cool, dissolve the mass in 20-40 cc. of concentrated 
 hydrochloric acid, and evaporate the solution to 10 cc. Add 20 
 cc. of water and filter. Now add ammonia until ferric hydroxide 
 separates out, and the mass becomes thick and smells of the pre- 
 cipitant. Redissolve the precipitate in strong nitric acid, adding 
 the acid gradually and until the liquid has an amber color. 
 Without previously heating the solution, add 40 cc. of molybdic 
 acid and allow the yellow precipitate to settle. The phosphorus 
 is all down in about ten minutes. Filter on a Q-cm. filter and 
 wash with acid ammonium sulphate. Dissolve the precipitate 
 in 5 cc. of strong ammonia (diluted with 25 cc. of water) and allow 
 to run jinto the flask in which the precipitation was made. 
 
 1 Blair's Analysis of Iron, Third Edition, p. 118. 
 
22 Carnegie Steel Company, Pittsburg, Pa. 
 
 Wash the filter until the volume of the filtrate is 150 cc. Add 
 10 cc. of concentrated sulphuric acid, dilute to 200 cc. and filter 
 through the reductor. The reduced solution is titrated with 
 potassium permanganate. 
 
 The acid ammonium sulphate used in washing the yellow 
 precipitate is made by adding 27.5 cc. of ammonia (sp. gr. 0.96) 
 to 500 cc. of water, to this 24 cc. of strong sulphuric acid (C. P.), 
 and making the whole up to i liter. 
 
 To prepare the molybdic acid solution, add to 100 grams of 
 molybdic acid 200 cc. of water and then 160 cc. of ammonia. 
 This dissolves all the acid. Pour the filtered solution into i 
 liter of nitric acid (sp. gr. 1.20). Allow the mixture to stand a 
 day or two before using. 
 
V. METHODS USED AT THE LABORATORY OF THE 
 
 BLACK DIAMOND STEEL WORKS, 
 
 PITTSBURG, PA. 
 
 BY EDWARD S. JOHNSON. 
 
 I. IRON ORBS. 
 
 1. Silica. i to 3 grams of the finely pulverized ore are 
 digested upon the water-bath in a covered beaker with 10 to 30 
 cc. of concentrated hydrochloric acid until decomposition is com- 
 plete. The solution and silicious residue are then transferred 
 to a porcelain dish, and the solution evaporated on the graphite- 
 bath (substitute for the sand-bath) to dryness. The residue is 
 taken up with concentrated hydrochloric acid and water, the 
 solution evaporated as before, and, after redissolving the dry 
 mass in concentrated acid and dilution with several volumes of 
 water, the silicious residue is collected upon a Swedish filter, 
 thoroughly washed, and ignited in a platinum crucible. After 
 ignition the residue is subjected to a fusion with ten to fifteen 
 times its weight of sodium carbonate. The fusion is dissolved 
 in water and hydrochloric acid, the solution evaporated to dry- 
 ness on the water-bath, and the separation of the silica further 
 conducted as usual under the given circumstances. The insolu- 
 ble residue remaining after the fusion, etc., is weighed ordinarily 
 as SiO a . 
 
 In still more accurate determinations, the silica thus obtained 
 is treated with hydrofluoric and sulphuric acids. The loss after 
 evaporation and ignition is silica. 
 
 2. Iron. The process for the determination of iron in iron 
 ores is the familiar one, consisting in the solution of the ore in 
 the least possible quantity of concentrated hydrochloric acid, re- 
 duction of the resulting ferric or ferro-ferric to a ferrous solution, 
 and titration of the highly dilute solution, in the presence of a 
 large excess of sulphuric acid, with potassium permanganate. 
 
 0.4 to 0.5 gram of the sample is dissolved in a covered 
 
24 Edward S. Johnson. 
 
 lo-inch by i-inch test-tube in 4 to 5 cc. of concentrated hydro- 
 chloric acid. The tube is heated over a small gas flame, at first 
 only warmed, and later, as the reaction proceeds, to gentle boil- 
 ing. A small crystal (o.i to 0.2 gram) of potassium chlorate is 
 added to the solution to oxidize possibly present organic matter, 
 and the boiling continued, with addition of more hydrochloric 
 acid, if necessary, for some minutes in order to decompose an 
 excess of chlorate. 
 
 When all but a flocculent silicious residue has been dissolved 
 (the watch-glass covering the tube) , the walls of the tube are 
 rinsed down with water, and 3 to 4 grams of triturated zinc 
 added to the solution. The resulting brisk evolution of hydro- 
 gen soon slackens ; a few cubic centimeters of dilute sulphuric 
 acid (i : i) are poured into the tube, and heat is applied, with 
 addition of more dilute sulphuric acid as required, until the 
 colorless condition of the solution indicates the complete reduc- 
 tion of ferric salt, and all zinc has dissolved. The remainder of 
 
 25 cc. of concentrated sulphuric acid (diluted with i volume of 
 water) is next added, and the reduced solution transferred from 
 the test-tube to a 6oo-cc. beaker. Sufficient cold, freshly-boiled 
 distilled water, to make the volume of the solution 400 to 500 cc., 
 is poured into the beaker. From a 5o-cc. Gay-L,ussac burette, a 
 solution of potassium permanganate (i cc. representing about 
 0.0068 gram of iron) , standardized by oxalic acid, is run into 
 the diluted ferrous solution until finally one drop imparts to it a 
 permanent pink coloration . From the number of cubic centimeters 
 used in the titration, a deduction is made for the volume of per- 
 manganate solution required to produce the above end-reaction 
 with all materials present or applied in the operations just de- 
 scribed, /. <?., acids, zinc, ferric chloride, water, etc. The re- 
 mainder forms obviously the basis for the calculation of the per- 
 centage of iron. 
 
 3. Phosphorus. This element is separated as ammonium 
 phosphomolybdate and weighed in the same form. 
 
 1.63 grams of ore are weighed off into a small porcelain dish 
 and ignited gently. When it has sufficiently cooled, the sam- 
 ple is treated with about 20 cc. of concentrated hydrochloric 
 acid, and the mixture, with frequent stirring, is heated on the 
 
Black Diamond Steel Works. 25 
 
 water-bath until all but silicious matter has dissolved. The 
 solution is evaporated to dry ness, and the residue redissolved in 
 20 to 30 cc. of hydrochloric acid. This second hydrochloric acid 
 solution is evaporated until the separation of basic chloride of iron 
 begins. With two or three drops of acid, the solution is restored; 
 30 to 40 cc. of water are added, and the insoluble silicious residue is 
 filtered off. The filtrate, which should have a volume of about 
 60 cc., is ready for the precipitation which is effected as de- 
 scribed for steel, p. 32. 
 
 4. Manganese. According to the percentage of manganese 
 present, the colorimetric or a gravimetric method is applied for 
 its quantitative determination : for quantities up to about three 
 per cent., the former; for higher percentages, the latter. 
 
 A. COLORIMETRIC METHOD. 
 
 From 0.05 to o.io gram of ore is placed in a 6-inch by ^--inch 
 test-tube, and dissolved in 2 to 3 cc. of concentrated hydrochloric 
 acid which is then expelled by boiling with an excess of concen- 
 trated nitric acid of 1.42 sp. gr. The nitric acid solution is 
 poured into a lo-inch by i-inch test-tube, rinsed out of the smaller 
 tube with 32 per cent, nitric acid, and diluted with the same to 
 a volume of about 35 cc. By the addition of lead peroxide 
 and boiling the solution, manganese is oxidized to permanganic 
 acid and determined in this form, as directed for the estimation, 
 of manganese in steel, p. 33. 
 
 B. GRAVIMETRIC METHOD. 
 
 For quantities over 3 per cent., the colorimetric method is 
 as yet scarcely longer available 1 ; a gravimetric determination is 
 then resorted to. The usual practice is to separate the manga- 
 nese from a nitric acid solution in presence of a large excess of 
 strong nitric acid by precipitation with potassium chlorate as 
 hydrated dioxide. The latter is separated by filtration, washed 
 with strong nitric acid, and redissolved in sulphurous acid. 
 The manganese in this solution is finally freed whol!} 1 " from iron 
 by a basic acetate precipitation. In the filtrate from the iron 
 precipitate, manganese is precipitated in the form of ammo- 
 nium manganese phosphate. 
 
 1 Experiments, with the object of determining the maximum percentage which may 
 be estimated colorimetrically, are, however, in progress. 
 
26 Edward S. Johnson. 
 
 II. PIG IRON. 
 
 i. Silicon. i gram of metal is dissolved in a small, covered, 
 porcelain dish in 10 cc. of dilute sulphuric acid (1:3) with the 
 addition of an equal volume of water. The action of the acid is 
 hastened by heating. When the evolution of hydrogen has 
 ceased, the cover-glass is rinsed off into the dish, and the latter 
 placed on the graphite-bath, where the contents of the dish are 
 heated until dense white fumes of sulphuric anhydride form 
 abundantly. The dish is removed from the bath, allowed to 
 cool somewhat, and the residue treated with water. Heat and 
 stirring are applied until all sulphate of iron has dissolved. The 
 insoluble residue is filtered off, washed with water and dilute 
 hydrochloric acid until free from iron, ignited, and weighed as 
 SiO 8 . If S represent the weight of metal taken for the deter- 
 mination, SiO^ the weight of silica found, and Si the percentage 
 of silicon, then 
 
 c-_ 
 
 2. Sulphur. The method adopted for the estimation varies 
 with the variety of iron and the accuracy required. For gray 
 iron and "commercial" accuracy, the evolution-volumetric 
 method is applied ; for white iron and also gray varieties of pig 
 iron, when the utmost accuracy is demanded, the aqua regia 
 method is made use of. 
 
 A. EVOUJTION-VOUJMETRIC METHOD. 
 
 The details of the process are given below in the description 
 of methods for the analysis of steel, p. 30. 
 
 B. AQUA RKGIA METHOD. 
 
 The sample about 5 grams is dissolved in concentrated 
 nitric acid of 1.42 sp. gr., with the addition of a small quantity of 
 hydrochloric acid a few cubic centimeters of concentrated acid 
 at a time and by the aid of heat, when necessary, to start the 
 dissolving of the borings. When the action of the acid has 
 ended, about 2 grams of sodium carbonate are added, and the 
 solution is warmed until the escape of carbon dioxide has 
 
Black Diamond Steel Works. 27 
 
 ceased. Silica is separated as usual by evaporation to dry ness, 
 solution of the residue in hydrochloric acid, and filtration. The 
 slightly acid filtrate is diluted to 75 to 100 cc. for each gram of 
 metal taken for the determination, and treated, while at a boil- 
 ing temperature, with a hot solution of barium chloride in mod- 
 erate excess. After the mixture has stood several hours, the 
 precipitate of barium sulphate is collected on a washed Swedish 
 filter, and washed as usual with hot water and dilute hydro- 
 chloric acid (i : 20). Should the precipitate be contaminated 
 with oxide of iron, a separation of the latter by fusion with 
 sodium carbonate, etc., is undertaken after ignition. 
 
 3. Phosphorus. The details of the method for the determina- 
 tion of phosphorus in pig iron are essentially the same as in the 
 case of steel. 1.63 grams of borings are dissolved in 50 cc. of 20 
 per cent, nitric acid. The insoluble carbonaceous and siliceous 
 matter is filtered off, and the filtrate about 60 cc. in volume 
 is treated as directed on p. 32. 
 
 4. Manganese. The same considerations and practice apply 
 in the determination of manganese in pig iron as in the estima- 
 tion of that element in steel, see p. 33. 
 
 in. STEBi,. 
 
 i. Carbon. In order to determine the carbon in steel, the 
 separation is accomplished by decomposing the metal, as gen- 
 erally customary, by means of cupric potassium chloride. As 
 is well known, a residue containing the whole of the carbon re- 
 mains after the action of the double chloride. By combustion 
 in a stream of oxygen, the carbon of the residue is converted for 
 weighing into carbon dioxide. 
 
 According to the amount of carbon present, i to 10 grams of 
 steel are treated with the above-mentioned solution (3Oto4occ. 
 for each gram of metal) of cupric potassium chloride which is 
 made by dissolving 1 2 grams of a pure preparation of the salt in 3 
 liters of water and 50 cc. of concentrated hydrochloric acid, and 
 filtration of the solution through ignited asbestos. 
 
 The mixture of chloride and steel borings is constantly 
 stirred, warmed at first, and finally heated to about 100 C. un- 
 til the metallic copper which separates in the reaction is redis- 
 
28 Edward S. Johnson. 
 
 solved. Sufficient dilute hydrochloric acid (i : i) is added to 
 dissolve the basic chlorides of iron and copper, which may sepa- 
 rate out toward the end of the above operation, and keep them 
 in solution during the subsequent filtration. This is effected by 
 Dr. Blair's familiar device for the purpose, consisting, as need 
 scarcely be added, of a platinum boat, with a finely perforated 
 bottom, and a funnel of the same metal, into which the boat 
 may be tightly packed with asbestos to allow of the use of the 
 filter-pump. The packing is done by means of asbestos in the 
 form of pulp such as is also used in forming a felt filter over the 
 perforations in the boat. The pulp for the felt may be conve- 
 niently made by heating asbestos wool to redness, cutting the 
 fibers into short pieces with the scissors (a manipulation ren- 
 dered much easier by the preparatory heating), and, after a 
 second ignition, agitating witn water. 
 
 When the carbonaceous residue has been collected in the 
 boat, washed thoroughly with dilute hydrochloric acid and 
 water, and dried at 100 C., it is ready for combustion. 
 
 The latter is carried out in a porcelain tube of the usual di- 
 mensions, heated in a ten-burner, Bunsen combustion furnace, 
 and supplied with a slow stream of oxygen purified by passage 
 over red-hot copper oxide and through absorbents for water and 
 carbon dioxide, in the following order : Through potassium 
 hydroxide solution (i : 2), and over granulated calcium chloride 
 and soda-lime. 
 
 The combustion-tube, projecting four or five inches beyond 
 the furnace at either end, is filled, excepting the projecting ends 
 and enough space in the rear for the reception of the boat, with 
 coarsely granular, copper oxide which is kept in place by short, 
 spiral rolls of copper gauze. Rubber stoppers at the rear and 
 front ends of the tube connect, respectively, with the supply of 
 oxygen and the apparatus for the purification and absorption of 
 the carbon dioxide formed in the combustion-tube. The possi- 
 ble impurities which require removal are hydrochloric acid and 
 chlorine. The gases issuing from the front end of the tube are, 
 therefore, caused to pass first through a saturated solution of 
 ferrous sulphate acidulated with a few drops of dilute sulphuric 
 acid, where any chlorine in the mixture is converted into hydro- 
 
Black Diamond Steel Works. 29 
 
 chloric acid, and any of the latter substance in the gases is 
 mainly absorbed. Should hydrochloric acid escape absorption 
 in the ferrous sulphate solution, it is retained by the saturated 
 solution of silver sulphate which follows. The gases leaving 
 the silver solution are saturated with vapor of water. By pass- 
 ing them through concentrated sulphuric acid and over calcium 
 chloride they are completely dried, and may enter the Geissler 
 potash bulbs which immediately follow, and in which the ab- 
 sorption of their carbon dioxide takes place. The bulbs are 
 filled with potassium hydroxide solution (1:2); to prevent loss 
 of moisture from the solution by the continuous passage of gas 
 through the apparatus, the bulbs are fitted with a cover- tube, 
 with ground-joint, containing solid potassium hydroxide. 
 
 Connected with the exit-end of the potash bulbs, a 6-inch, 
 straight, calcium-chloride tube, filled also with pieces of potas- 
 sium hydroxide, protects them against the possibility of the en- 
 trance of moisture and carbon dioxide from the atmosphere. It 
 concludes the train of apparatus attached to the front end of the 
 combustion-tube. 
 
 After the familiar preliminaries of introducing the boat with 
 its carbonaceous residue, weighing and attaching the potash 
 bulbs, securing all connections, and starting a slow stream of 
 oxygen through the apparatus, the combustion is begun by 
 heating the front half of the porcelain tube to redness. The rest 
 of the tube containing the boat is then gradually heated to the 
 same temperature. For fifteen to twenty-five minutes a red heat 
 is maintained and the passage of oxygen continued. The oxy- 
 gen is then cut off, and air from an independent drying and 
 purifying apparatus a duplicate of that described for use with 
 oxygen is drawn during forty-five to sixty minutes slowly 
 through the entire apparatus. By this manipulation all carbon 
 oxide is brought into the potash bulbs, and the latter filled with 
 air. To insure a complete displacement of the oxygen in the 
 potash bulbs, after the main aspiration, air which has been freed 
 from carbon dioxide is drawn for some minutes through the dry- 
 ing apparatus directly behind the bulbs, and the bulbs them- 
 selves. 
 
 The potash apparatus is detached and allowed to stand fifteen 
 
30 Edward S. Johnson. 
 
 to twenty minutes in the balance case, where it had stood for at 
 least the same length of time before the first weighing. The 
 increase in weight is ascertained, and therefrom the percentage 
 of carbon deduced according to the well-known formula. 
 
 2. Sulphur. The determination is effected by separating the 
 element as cadmium sulphide and estimating the sulphur in the 
 latter volumetrically with iodine solution. 
 
 The metal is dissolved in dilute hydrochloric acid ; the gases 
 evolved are passed into a strongly ammoniacal solution of cad- 
 mium chloride in which the sulphur, entering as hydrogen 
 sulphide, is precipitated. The precipitate is filtered off, dis- 
 solved in a large volume of dilute hydrochloric acid, and the 
 hydrogen sulphide again set free, measured as indicated above. 
 
 The solution of the sample is carried out in a 25O-cc. Florence 
 flask. 
 
 Into the neck of the flask is fitted a rubber stopper with three 
 perforations. One of the latter receives the stem of a separating 
 funnel with a wide mouth and a bulb which should have a capacity 
 of about 50 cc. ; through another perforation passes the \- 
 inch conduction- tube, connecting the evolution flask directly 
 under the stopper with the absorption-tube ; a third \- 
 inch tube, the hydrogen tube, passes through the stopper 
 to the bottom of the flask where it is drawn out to a point and 
 bent upwards about \ of an inch. Above the stopper it is con- 
 nected with a supply of hydrogen. 
 
 The conduction-tube, which is in one piece, rises perpendicu- 
 larly to about \ inch from the stopper, bends away from 
 the perpendicular about 60, extending in this direction 5 or 
 6 inches, when it dips directly downward into the absorption- 
 tube, a 10-inch by i-inch lipped test-tube of stout glass. Between 
 the first and second bends in the conduction-tube are blown two 
 f-inch bulbs. 
 
 The evolution flask and absorption-tube are securely held in 
 the required position by specially adapted racks the flasks over 
 Argand gas burners during the precipitation of the sulphur. 
 
 In carrying out a determination with tl*e above apparatus, 3 
 to 5 grams of the sample are placed in t le flask, and about 50 
 cc. of cadmium chloride solution (80 grains of cadmium chlo- 
 
Black Diamond Steel Works. 31 
 
 ride dissolved in 1.5 liters of concentrated ammonia water and 
 2.5 liters of water) in the absorption-tube. Connections being 
 made and the hydrogen tube closed, 50 cc. of dilute hydrochloric 
 acid ( i : i ) are gradually or at once, according to the probable 
 rate of evolution of gas, run into the flask through the separa- 
 ting funnel, and a brisk generation of gas is maintained, if 
 necessary, by the aid of heat. When the sample has dissolved, 
 hydrogen is turned on in a slow stream, and the solution boiled 
 until the bulbs of the conduction-tube become hot. The flame 
 under the flask is then turned out, and the passing of hydrogen 
 continued moderately from ten to fifteen minutes. 
 
 The precipitated cadmium sulphide is next transferred to a 
 rapid German filter. To this end, after disconnecting the ab- 
 sorption apparatus from the flask, the conduction-tube is with- 
 drawn from the absorption-tube and laid aside, the adhering pre- 
 cipitate being beforehand washed down into the tube as com- 
 pletely as possible ; the portion adhering firmly to the latter, un- 
 less it be considerable, is not removed to the filter, but left to be 
 dissolved off, together with that remaining on the conduction- 
 tube, at the final solution of the precipitate. After several 
 washings the filter and precipitate are placed in a 6oo-cc. 
 beaker. According to the quantity of precipitate, 200400 cc. 
 of water are poured over it, 3 cc. of starch solution (i : 150) 
 added, and the mixture stirred until the filter and precipitate 
 are well disintegrated. 
 
 Fifty cc. of dilute hydrochloric acid (i : i) are poured into 
 the absorption-tube, and water is added to fill the tube to within 
 about an inch of the top. The conduction-tube, which had 
 been laid aside before the filtration, is quickly dipped into the 
 diluted acid until its tip nearly touches the bottom, then raised 
 and lowered in the liquid several times. By manipulating in 
 this way, the precipitate left in the absorption- and conduction- 
 tubes is almost instantly dissolved, the hydrogen sulphide 
 formed absorbed in the surrounding liquid, and the comparatively 
 strong solution of hydrogen sulphide, existing on their surfaces 
 immediately after the contact of the precipitate with the acid, 
 rinsed off. The contents of the absorption-tube are added to the 
 water and precipitate in the beaker. The precipitate dissolves 
 
32 Edward S. Johnson. 
 
 mainly at once and entirely on stirring. Without waiting until 
 all cadmium sulphide has dissolved, the estimation of the sul- 
 phur is at once begun by titration of the liberated hydrogen sul- 
 phide with iodine solution. 
 
 The standard iodine solution is prepared by dissolving i gram 
 of resublimed iodine in 50 cc. of an aqueous solution of potas- 
 sium iodide (i : 10), and diluting to i liter. While pure re- 
 agents and careful manipulation insure a solution of the desired 
 strength, the latter is nevertheless confirmed by direct experi- 
 ment before the solution is used. For this purpose sodium thio- 
 sulphate is applied. A preparation of the salt of requisite purity 
 may be made by recrystallization of the chemically pure prepa- 
 ration of the trade. A saturated, warm aqueous solution is pre- 
 pared and cooled to nearly o C. with constant stirring. The 
 compound separates under these circumstances as a minutely 
 crystalline mass. By decantation and the use of the filter-pump, 
 the mother-liquor may be almost completely removed. The still 
 moist preparation is perfectly freed from water of solution be- 
 tween sheets of filter-paper. 
 
 3. Phosphorus. This element is determined by weighing as 
 ammonium phosphomolybdate. 
 
 1.63 grams of steel are dissolved in a covered beaker in 45 cc. 
 of 20 per cent, nitric acid, the action of the acid being hastened 
 by warming. When a perfect solution has been obtained and 
 brought to the boiling-point, an excess of a saturated solution of 
 potassium permanganate is added and the boiling continued for 
 two or three minutes. While still boiling, the mixture is 
 treated with sufficient ferrous sulphate in saturated, slightly acidi- 
 fied (5 cc. sulphuric acid per liter) solution to dissolve the pre- 
 cipitated manganese dioxide resulting from the action of potas- 
 sium permanganate on the original nitric acid solution of the 
 metal. The dioxide disappears, leaving usually a clear solu- 
 tion. If it should not, recourse must be had to filtration for the 
 removal of the "scale," etc., sometimes unavoidably weighed 
 off at the beginning of the determination. A clear solution hav- 
 ing been produced, about 15 cc. of water are added, and the con- 
 tents of the beaker again heated to boiling. The source of 
 heat is removed, and the cover and walls of the beaker are rinsed 
 
Black Diamond Steel Works. 33 
 
 down with water. The volume of the liquid at this stage of the 
 operation should be about 60 cc. After stirring a few seconds, 
 the temperature for precipitation, under 80 C., will exist in the 
 solution. 45-50 cc. of molybdate solution are then added, and 
 the mixture thoroughly and repeatedly stirred. The precipitant 
 is prepared by dissolving 185 grams of pure ignited " molybdic 
 acid" in 900 cc. of ammonia water (sp. gr. 0.96), adding this 
 solution to 2,700 cc. of 32 per cent, nitric acid, and diluting the 
 whole with water to 4 liters. The supernatant liquid is poured, 
 with as little disturbance of the precipitate as possible, when it 
 has become clear, through a washed Swedish filter. The latter 
 is washed twenty-five times with i per cent, (by volume) nitric 
 acid, when the precipitate is transferred to the filter, and the 
 washing continued until the precipitate and filter are free from 
 iron. The filter with its contents is dried for one hour at 100 
 C., and weighed between accurately-ground watch-glasses, the 
 drying and weighing of the filter alone having before been con- 
 ducted under similar conditions. The number expressing the 
 weight of the precipitate in grams also represents the percentage 
 of phosphorus. 
 
 4. Manganese. In the determination of manganese, the 
 colorimetric method is used almost exclusively, the quantities 
 encountered rarely exceeding 3 per cent. For higher per- 
 centages, as in the case of ores also, a gravimetric method is 
 used. For the latter, see p. 25, Gravimetric Method. 
 
 COLORIMETRIC METHOD FOR MANGANESE. 
 
 The process consists in converting the manganese present into 
 permanganic acid and deriving colori metrically, by means of a 
 solution of potassium permanganate 1 containing a known quan- 
 tity of manganese, the amount of manganese in the permanganic 
 acid obtained from a given weight of steel. 
 
 o.i gram of metal is dissolved in a lo-inch by i-inch test- 
 tube in 35-40 cc. of 32 per cent, nitric acid, and the solution 
 heated to boiling over a small flame from a Bunsen burner. 
 When the formation of nitrous fumes ceases, the heat is re- 
 
 i The use of potassium permanganate in this connection was, I believe, first sug- 
 gested by Mr. B. B. Wright, formerly chemist to the Black Diamond Steel Works. 
 
34 Edward S. Johnson. 
 
 moved, and 0.2 to 0.5 gram of lead peroxide are added. Heat 
 is again applied, and the mixture boiled for three or four 
 minutes. The tube is then stood aside, closely covered, and in 
 the dark, in cold water until the excess of lead peroxide has 
 settled down. When clear, the acid solution above the lead per- 
 oxide now containing the manganese as permanganic acid 
 is decanted into a 5o-cc. comparing tube, which is graduated to 
 0.5 cc., and is one of a set of three exactly similar tubes; the 
 remaining two receive the solutions of potassium permanganate 
 to be used in determining the quantity of manganese, in the 
 form of permanganic acid, obtained by the process just de- 
 scribed. 
 
 The permanganate solutions are prepared from a stock solu- 
 tion of such strength that 10 cc. of the same, when diluted to 250 
 cc.,will produce a solution of which i cc. contains o.ooooi gram 
 of manganese as permanganic acid. In practice this dilute solu- 
 tion is called the normal standard. From the normal, others are 
 prepared (by dilution with water in the comparing tubes) hav- 
 ing a simple ratio i 12,1:3,3:4, etc. to the normal. All of 
 these solutions are adjusted directly before use from the stock 
 solution. The latter is made i liter at a time, and may, with 
 proper precautions, be kept for several weeks without apprecia- 
 ble change. 
 
 Equipped with this solution and its derivatives, the procedure 
 in estimating the quantity of manganese in the permanganic 
 solution, yielded by a sample of steel under the conditions above 
 detailed, is obvious and simple. In one of the comparing tubes 
 are placed 30-40 cc. of a standard permanganate solution of 
 lighter tint than the permanganic solution. The latter is then 
 diluted with water until the tints in both tubes cannot be dis- 
 tinguished one from another, the examination or " comparing" 
 of the shades of color being carried out over a sheet of white 
 paper in the diffuse light of a window. The ratio of the volumes 
 of the two solutions is plainly equal to the ratio of the quantity 
 of manganese contained in them. The volumes being read off 
 from the graduated comparing tubes, and the quantity of man- 
 ganese in one solution being known, the quantity in the other is 
 readily calculated. If the normal permanganate be used, the 
 
Black Diamond Steel Works. 35 
 
 number expressing the volume of the solution (in cubic centime- 
 ters) containing the unknown quantity of manganese divided by 
 100 is the required percentage when o.i gram of steel is taken 
 for the determination ; if a standard of lighter tint be used, the 
 volume must first be multiplied by the fraction showing its rela- 
 tion to the normal. For example, a volume of 35 cc. with the 
 normal standard represents 0.35 per cent, manganese ; with 
 a 3 : 4 standard, 0.26 per cent. 
 
 In the case of the higher percentages of manganese, which may 
 still be determined colorimetrically with convenience and accu- 
 racy, some modifications of the general method already given 
 are advisable or necessary. It is advisable to weigh off for the 
 determination at least one gram of borings that a representative 
 result may be obtained from the sample. A solution in 32 per 
 cent, nitric acid is prepared and diluted in a 5OO-cc. flask to the 
 mark. Aliquot parts equivalent to 0.05 to o.i gram are then 
 taken . for single determinations. After evaporation to 5 to 10 
 cc., transfer to a test-tube, and dilute to about 80 cc. with 32 per 
 cent, nitric acid, when the solution will be ready for oxidation. 
 Experiments thus far have shown that under the above conditions 
 ten to twenty minutes boiling with 0.5 gram of peroxide 
 suffices to oxidize at least 2.5 per cent, manganese in y 1 ^ of a 
 gram. The test of complete oxidation is made the obtaining, 
 within the limits of error, of the same result, whether o.i 
 gram or half that quantity be used for the determination, the 
 conditions being in each case in all other respects the same. 
 
 Further, after the decantation of the permanganic solution, a 
 slightly varying quantity of the latter is left adhering to the 
 tube and the residue of peroxide. When higher percentages 
 are concerned, the quantity of manganese represented by the 
 liquid residue is not inconsiderable, and cannot be neglected in 
 accurate determinations, as in the case of the lower percentages. 
 The tube and residual peroxide should therefore be rinsed with 
 a few cubic centimeters of water or 32 per cent, nitric acid. The 
 rinsings are filtered through carefully washed asbestos into 
 the decanted solution. The asbestos for the filtration is pre- 
 pared by boiling with strong hydrochloric acid, washing with 
 water, and ignition. 
 
VI. METHODS USED AT THE LABORATORY OF THE 
 
 OLIVER & SNYDER STEEL WORKS, 
 
 PITTSBURG, PA. 
 
 BY S. M. RODGERS. 
 
 DETERMINATION OF SILICON IN PIG IRON AND STEEL. 
 
 i gram of pig iron, carefully separated with a magnet, is 
 placed in a 4-inch evaporating dish and 30 cc. of nitrosulphuric 
 acid, made by adding 60 cc. of concentrated sulphuric acid to 
 600 cc. of nitric acid (sp. gr. 1.20), are added. Cover with a 
 watch-glass and place over a small flame. When the solution 
 of the drillings is complete, remove the cover and rinse into the 
 dish with water and continue the evaporation cautiously, until 
 sulphuric acid fumes appear. Remove the dish from the heat, 
 cool, add 15 cc. of concentrated hydrochloric acid, and 10 cc. of 
 water and boil till all the sulphate of iron is dissolved. Dilute 
 with an equal volume of cold water and filter through an ashless 
 filter, using the filter-pump. Wash, first with cold water, then 
 alternately with cold water and hot dilute hydrochloric acid 
 (sp. gr. i.io), and finally with hot water. Place the filter and 
 contents in a platinum crucible and burn the filter-paper at a 
 low temperature, finishing with the blast or muffle till the pre- 
 cipitate of silica is perfectly white. If colored red, add three 
 drops of sulphuric acid and 5 to 15 drops of hydrofluoric acid and 
 heat cautiously under the hood to dryness ; then use the blast 
 till the iron is completely oxidixed. Cool in a desiccator and 
 weigh. The difference between the last two weights is the 
 exact weight of the silica. Should the sample contain chro- 
 mium, correct results can best be obtained by fusing the impure 
 silica with about 2 grams of pure potassium bisulphate, and 
 heating cautiously till white fumes of sulphur trioxide are given 
 off. Cool, dissolve the mass in dilute hydrochloric acid, filter 
 off the purified silica; treat as in the first operation, and cal- 
 culate in the usual manner. 
 
 In steel, 2 to 5 grams are dissolved in 30 to 60 cc. of concen- 
 
Oliver & Snyder Steel Works. 37 
 
 trated hydrochloric acid and treated in the same manner as pig 
 iron. 
 
 DETERMINATION OF SILICON IN FERRO-SILICON AND 
 SILICO-SPIEGEL. 
 
 0.5 gram of the finely pulverized sample are placed in a 4-inch 
 evaporating dish and 50 cc. of dilute hydrochloric acid, 1 made 
 by using three volumes of water to one volume of concentrated 
 acid, are added. Cover with an inverted watch-glass just large 
 enough to drop inside of the dish. Place over a small flame, 
 and evaporate to dryness. Follow the directions given for the 
 determination of silicon in pig iron, and purify with hydrofluoric 
 and sulphuric acids. Hydrofluoric acid is very conveniently 
 handled, by cutting a light groove in the inside of the neck of 
 the bottle, beginning below the termination of the stopper and 
 extending upward a little more than half way to the top. Then 
 cut a similar groove in the stopper, beginning a little below the 
 termination of the groove in the neck and extend same to the 
 upper end of the stopper. When the grooves are communicating, 
 one drop at a time can be added. To close the orifice, the stop- 
 per is slightly turned so that the grooves are no longer com- 
 municating. 
 
 DETERMINATION OF SULPHUR IN IRON AND STEEL. 
 
 Aqua Regia Method. Weigh, into an 8-oz. beaker, 6 grams of 
 iron or steel, cover with a watch-glass and add 10 cc. of bromine 
 water, and 60 cc. of aqua regia, a little at a time. After the 
 violent action of the acid has ceased, place the beaker over a small 
 flame till solution of the drillings is complete. Then evaporate 
 rapidly till the excess of acid is expelled. Dilute to 120 cc. 
 with cold water, mix thoroughly and filter exactly 100 cc. (the 
 equivalent of five grams), add 5 cc. of a saturated solution of 
 citric acid, and 10 cc. of a 10 per cent, solution of barium 
 chloride. Stir occasionally and set aside over night. Care- 
 fully decant the clear supernatant liquid into a platinum Gooch 
 crucible, containing an accurately-fitting disk of filter-paper, 
 using moderate suction. Discard the clear filtrate, and detach 
 
 l The formula for mixing this solvent was first obtained from Mr. C. B. Murray, of 
 Edgar Thompson Steel Works, Braddock, Pa. 
 
38 5. M. Rodgers. 
 
 from the pump. Now transfer the entire precipitate to the filter 
 and wash with a dilute solution of hot hydrochloric acid, using 
 a few drops of hydrofluoric acid to dissolve any silica that may 
 have been carried down with the precipitate, continue the wash- 
 ing till the precipitate is entirety free from iron salts, and lastly 
 use a little hot water. Place the cap on the crucible and dry 
 over a small flame. Then burn off the carbon completely, cool 
 in a desiccator, and weigh. Multiply the weight of barium 
 sulphate by 13.7 and divide by 5. The result will be the per 
 cent, of sulphur in the sample. 
 
 Evolution Method. 5 grams of iron or steel are placed in a 16- 
 oz. ring-neck flask, carrying a 4-oz. funnel-tube and a delivery- 
 tube, the latter terminating at the bottom of an 8- inch test-tube 
 containing a solution of ammoniacal cadmium chloride. 4 oz. 
 of hydrochloric acid (sp. gr. i.io) are placed in the funnel- 
 tube and allowed to flow into the flask. After the violent action 
 of the acid has ceased, place the flask over a small flame and 
 continue the evolution till the drill ings are completely dissolved. 
 Finally bring the solution to a boil for about two or three 
 minutes. Disconnect the flask and remove from the heat. 
 Transfer the contents of the tube to a white bowl and dilute 
 with 200 cc. of cold water. Acidulate with hydrochloric acid 
 by conducting it through a tube to the bottom of the solution. 
 Add 3 cc. of starch solution and titrate with standard solution 
 of iodine, i cc. of which is equivalent to o.oi per cent, of sul- 
 phur in 5 grams of the sample, thus obviating the necessity for 
 a calculation. 
 
 The iodine solution is made by dissolving 4 grams of resub- 
 limed iodine in 8 grams of pure potassium iodide dissolved in 
 10 cc. of water, and diluted to one liter, which makes approxi- 
 mately the strength desired. The solution is then accurately 
 standardized by running the iodine solution against an exact 
 weight of sodium thiosulphate, this weight having been pre- 
 viously determined, by first accurately standardizing the iodine 
 solution by the bichromate and thiosulphate method, and then 
 carefully determining, by numerous experiments, the exact 
 weight of sodium thiosulphate equivalent to the iodine. This 
 having been done on a large quantity of the thiosulphate and 
 
Oliver & Snyder Steel Works. 39 
 
 the weight noted on the container, makes the work of standard- 
 izing iodine both accurate and rapid. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON AND STEEL. 
 
 Weigh into a 6-oz. casserole 1.63 grams of drillings, and 
 cover with an inverted watch-glass just large enough to drop 
 inside of the dish. Add 50 cc. of nitric acid (sp. gr. 1.20), and place 
 over a small flame; when solution is complete, evaporate rapidly 
 to dryness. Then increase the heat till the bottom of the dish is a 
 dull red, and continue this heat till oxidation of the organic 
 matter and phosphorus is complete, which may be indicated by 
 holding the wet stopper of the ammonia bottle within the 
 dish. The absence of white fumes indicates that this stage of 
 the process is completed. The watch-glass need not be removed 
 if care be taken not to cool the dish too rapidly. When cold, dis- 
 solve the mass in 15 cc. of a mixture of 390 cc. concentrated 
 hydrochloric acid and 60 cc. concentrated sulphuric acid. 
 Evaporate till the mass has the appearance of burnt sugar, or 
 almost to dryness. Now add, drop by drop without cooling, 10 
 cc. hot dilute hydrochloric acid, and sufficient water to effect 
 complete solution of the mass, concentrate, add 10 cc. strong 
 nitric acid, and boil till the red fumes pass off. Dilute with 25 
 cc. of cold water, and filter under strong suction. Wash first 
 with cold water, then with a few drops of hot hydrochloric acid, 
 and then with hot water. To the filtrate add 10 cc. of strong 
 ammonia, and then just enough strong nitric acid to dissolve the 
 precipitated iron and render the solution a deep amber color. 
 Heat or cool to exactly 80 C., add 40 cc. of molybdic acid solu- 
 tion, and shake. Set in a warm place till the precipitate settles, 
 which should not be more than fifteen to thirty minutes. 
 
 Filter through a Gooch crucible containing an accurately-fit- 
 ting disk of No. o Swedish filter-paper, using strong suction. The 
 precipitate will not run through if the solution, before precipita- 
 tion, is not too strongly acid. Otherwise it invariably runs 
 through. The precipitate is thoroughly washed with a solution 
 of 2.5 per cent, hydrochloric acid and 2.5 percent, molybdic acid 
 solution. The crucible and contents are transferred to the hot 
 air-bath and dried at 120 C. Or the precipitate may be 
 
40 6*. M. Rodger s. 
 
 thoroughly' dried in three minutes by drawing clean, dry, hot 
 air through the crucible. If the disks are cut from carefully 
 selected filter-paper, they will not vary in weight more than i 
 milligram, and by noting this we can eliminate one weight in 
 each determination. The solvent action of the solutions do not 
 appreciably affect the weight of the paper disk as might be the 
 case in using a whole filter. 
 
 If extreme accuracy be required, the precipitate may be dis- 
 solved off the disk with ammonia, neutralized with hydrochloric 
 acid and let stand over night. Any iron or silica that may have 
 been retained by the precipitate can be estimated by filtering 
 through the same disk, washed, dried, and weighed. On subtract- 
 ing this result from the previous weight, the difference between 
 the two weights in milligrams, will be the per cent, of phos- 
 phorus in the sample. 
 
 In checking all results, the molybdate-magnesia method is 
 used mainly, as described by Prof. N. W. Lord in his " Notes 
 on Metallurgical Analysis," p. 22. 
 
 DETERMINATION OF MANGANESE. 
 
 Weigh 5 grams of iron or steel into a 6-oz. casserole and dis- 
 solve in 60 cc. of strong nitric acid. When solution is complete, 
 add 10 cc. of concentrated hydrochloric acid and boil five minutes. 
 Filter, if necessary, and concentrate the filtrate to a small bulk. 
 Add 25 cc. of strong nitric acid and 5 grams of pure potassium 
 chlorate, cover with a watch-glass, and boil ten minutes. Re- 
 peat this operation once, if the sample is low in manganese, 
 and twice if high. Boil fifteen minutes after the last addition of 
 potassium chlorate, filter through an asbestos plug, and wash 
 with strong nitric acid. Transfer the plug and precipitate to 
 the same beaker in which the precipitation was made, rinsing out 
 the last particles with dilute hydrochloric acid, add a few crystals 
 of oxalic acid, dilute with 25 cc. of hot water, and boil till the 
 manganese dioxide is completely dissolved. Filter and wash 
 thoroughly with hot water, and boil the filtrate a few minutes. 
 Dilute to 250 cc., and cautiously add dilute ammonia water 
 (i : i) till a faint permanent precipitate of iron is produced; add 
 slowly 25 cc. of a concentrated solution of ammonium acetate 
 
Oliver & Snyder Steel Works. 41 
 
 with constant stirring. Cover the beaker and boil three minutes; 
 allow the precipitate to settle, and decant the supernatant liquid 
 through a filter, letting the filtrate run into a 24-oz. beaker, and 
 wash the precipitate once or twice by decantation . Transfer the 
 precipitate to the filter and wash once with hot water. Redis- 
 solve the precipitate with the least quantity of hot dilute hydro- 
 chloric acid, allowing the solution to run into the same beaker in 
 which the precipitation was made, and make a second basic ace- 
 tate separation in the same manner. Test this precipitate with 
 sodium carbonate on a platinum wire, and if not free from 
 manganese, make a third separation. Concentrate the filtrate 
 to about 300 cc. and add 5 to 10 cc. of acetic acid, boil, and add 
 5 to 10 grams of ammonium phosphate, stirring till crystalline. 
 Finally, add 15 to 25 cc. of strong ammonia and continue the 
 stirring till the precipitate is completely crystalline in its charac- 
 teristic silky form. Remove from the heat and let the precipi- 
 tate settle. Filter through an ashless filter and wash thoroughly 
 with water containing a few cubic centimeters of ammonia. 
 Transfer the precipitate to a deep platinum crucible and heat 
 cautiously till the filter-paper is charred. Then increase the 
 heat slowly to the highest temperature of the blast, and con- 
 tinue this heat till the precipitate is perfectly white and constant 
 in weight. Cool in a desiccator, weigh, multiply the weight by 
 0.3874, divide by the number of grams taken, and the result 
 will be the per cent, of manganese in the sample. 
 
 DETERMINATION OF NICKEL IN STEEL. 
 
 Weigh into a large beaker 0.5 to 2 grams of steel, and dis- 
 solve in dilute hydrochloric acid (sp. gr. 1.12). Add 10 cc. 
 bromine water and boil till iron is completely oxidized. Dilute 
 to about 400 cc. with water. Precipitate the iron with concen- 
 trated ammonia, filter rapidly on a ribbed filter, and wash the 
 precipitate three or four times with hot water. Suck the pre- 
 cipitate dry, puncture the filter, and wash the precipitate into the 
 original beaker. Dissolve the last traces of the precipitate with 
 hot dilute hydrochloric acid, add ten cc. strong hydrochloric 
 acid, and, when solution is complete, dilute to 300 cc. with water 
 and precipitate the iron as before, using a moderate excess of 
 
42 6*. M. Rodger s, 
 
 ammonia. Make at least four precipitations in this manner, 
 using an excess of ammonia each time ; combine the filtrates and 
 concentrate till crystallization of the salts begins. Place on a 
 steam-bath and dissolve any separated salts in 25 cc. of strong 
 ammonia. Filter through a small filter and wash with dilute 
 ammonia water till the filtrate measures 275 cc. in volume. 
 Precipitate the nickel on a weighed platinum cylinder which is 
 connected with the zinc plate of a battery of 2 or 3 Bunsen cells, 
 keeping the solution at 80 C. 
 
 DETERMINATION OF NICKEL AND COBALT. 
 
 i to 5 grams of the sample are placed in a small flask, and a 
 mixture of 5 cc. of concentrated nitric acid, 5 cc. of concentrated 
 sulphuric acid, and 3 cc. of concentrated hydrochloric acid 
 added for every gram of the sample taken. Heat over a small 
 flame till solution is complete and copious fumes of sulphuric 
 anhydride are given off, adding more sulphuric acid if required 
 to avoid going to dryness. Cool, dilute with water, filter, and 
 wash thoroughly with hot water. If second group bases are 
 present, the filtrate is heated to about 70 C., and a strong cur- 
 rent of hydrogen sulphide gas is passed through the solution till 
 the latter is cold. Filter out the precipitated sulphides, wash 
 thoroughly with hydrogen sulphide water, and boil the filtrate. 
 While boiling add hydrochloric acid and potassium chlorate, a lit- 
 tle at a time, till oxidation of the iron is complete. Dilute with 
 water and add ammonia, stirring constantly, till the iron is com- 
 pletely precipitated, and the solution decidedly alkaline. Filter 
 and wash the precipitate once or twice with hot water. Dissolve the 
 precipitate with dilute hydrochloric acid and add ammonium 
 carbonate till a slight permanent precipitate is produced. Add 
 one drop of hydrochloric acid to clear the solution, then 10 to 15 
 grams of ammonium acetate and bring to a boil. Remove from 
 the heat a few minutes till the precipitate settles, and filter, 
 using moderate suction. Wash with hot water, and dissolve 
 the precipitate with dilute hot hydrochloric acid, letting the 
 solution run into the original beaker, and make a second pre- 
 cipitation in the same manner as the first. Combine the filtrates, 
 concentrate to 350 cc., and acidify slightly with acetic acid. 
 
Oliver & Snyder Steel Works. 43 
 
 Boil and pass a current of hydrogen sulphide through the solu- 
 tion while boiling. Filter off the precipitated sulphides of 
 nickel and cobalt, and wash thoroughly with hydrogen sulphide 
 water. Acidify the nitrate slightly with acetic acid and boil. 
 If any further precipitation takes place, collect on a filter and 
 wash as above. Transfer ,the precipitates from the filters as 
 completely as possible, ignite the filters, and add the ashes to 
 the precipitates and dissolve the sulphides in aqua regia. Expel 
 the excess of acid by evaporation, dilute with water, add a solu- 
 tion of moderately strong potassium hydroxide, and heat almost 
 to boiling for some time. Filter, wash, and transfer the precipi- 
 tate to a beaker as completely as possible, dissolving off the 
 last traces with a solution of potassium cyanide, receiving the 
 filtrate in the beaker containing the precipitate. Warm gently till 
 the precipitate is dissolved, and heat to boiling to expel excess 
 of hydrocyanic acid. Add to the hot solution finely pulverized 
 mercuric oxide and boil. Filter off the precipitated nickel, 
 wash, dry, and ignite in a weighed porcelain crucible. Multiply 
 the weight of the precipitate by 0.78667 to obtain the weight of 
 the nickel, from which the per cent, can be readily calculated. 
 
 In order to insure accurate results, boil the oxide in water, 
 filter, wash, dry, and ignite as before. A decrease in weight is 
 likely due to some adhering salt. Dissolve the nickel in aqua 
 regia, dilute in water, and filter through an ashless filter. 
 Ignite, weigh, and deduct from the oxide of nickel. Dilute 
 the filtrate, add an excess of ammonia, and let stand over night. 
 If a precipitate occurs, filter, wash, ignite, and deduct this weight 
 also from the weight of the nickel oxide. From the remainder, 
 calculate the per cent, of metallic nickel. 
 
 Carefully neutralize the filtrate from the precipitated nickel 
 by mercuric oxide, with nitric acid, and add a solution of mer- 
 curous nitrate as long as a precipitate of mercury cobaltocya- 
 nide is formed. Filter, wash, and dry the precipitate, and reduce 
 the cobalt to the metallic state in a current of hydrogen in a 
 Rose crucible, and weigh. 
 
44 -5*- M- Rodger s. 
 
 DETERMINATION OF CHROMIUM IN CHROME ORE AND FERRO- 
 
 CHROME. 
 
 Weigh into a platinum crucible, whose capacity is not less 
 than 40 or 50 cc., 0.5 gram of fine ground ore, place on top of it 
 25 grams of potassium bisulphate, and fuse very cautiously over 
 a very low flame. After the mass is in a liquid condition, in- 
 crease the heat cautiously to dull redness. Carefully run the 
 fusion up on the sides of the crucible to dislodge any stranded 
 particles of ore. The mass must now be kept in a state of tran- 
 quil fusion at least forty or fifty minutes, or longer if the sample 
 has not been finely pulverized. Cool the crucible, place it 
 in a 5-inch casserole, cover the crucible with hot water, and in- 
 vert a watch-glass over the solution and crucible just large 
 enough to drop inside the edges of the dish, Place the dish in 
 an air-bath at i2oC. till the contents are readily washed from the 
 crucible. Wash off the watch-glass, add 35 to4occ. concentra- 
 ted hydrochloric acid and 15 cc. of hot water, and boil gently till 
 solution is complete. Remove from the heat and let the silicious 
 matter settle. Decant the supernatant liquid into a i2-oz. 
 beaker, add 15 or 20 cc. more hydrochloric acid to the resi- 
 due, and boil gently fifteen minutes longer. Combine the two 
 solutions and filter through an ashless filter, wash, ignite, and 
 weigh the silica. The filtrate is made slightly alkaline with 
 ammonia and heated on the steam-bath till the chromium, iron, 
 and aluminum are completely precipitated and the excess of 
 ammonia is volatilized. Filter without washing, dissolve the 
 precipitate in dilute hydrochloric acid, and receive the fil- 
 trate in the original beaker. Reprecipitate in the same manner, 
 filter, and wash the precipitate two or three times with hot water. 
 Combine the two filtrates and determine the calcium and mag- 
 nesium by any good method. Transfer the precipitate and filter 
 to the 5-inch casserole, add 50 cc. of strong nitric acid, cover 
 with a watch-glass, heat gently to boiling, and add, cautiously, 
 potassium chlorate, little by little, till the iron and chromium 
 are completely oxidized, which is indicated by the deep orange 
 color of the chromic acid. Transfer to a beaker and dilute to 
 200 cc. with water. Precipitate the iron and aluminum with 
 
Oliver & Snyder Steel Works. 45 
 
 ammonia and filter into a 24-oz. beaker, without washing. Dis- 
 solve the precipitate with warm, dilute nitric acid, and receive the 
 filtrate in the same beaker in which it was made. Reprecipitate 
 as before and filter, receiving the filtrate in the same beaker as 
 the first. Repeat these solutions and precipitations till the re- 
 sulting precipitate of iron and aluminum gives no reaction for 
 chromium when a small part of it is fused on a platinum wire 
 with sodium carbonate. The iron and aluminum may be de- 
 termined by any good method. To the filtrate containing the 
 chromium, add acetic acid to slight acid-reaction, and add locc. 
 of a 20 per cent, solution of lead acetate. Cover and set aside for 
 about four hours, stirring frequently. Filter on a Gooch cruci- 
 ble as in the determination of phosphorus, and wash with cold 
 water till the washings give no reaction for lead with fresh 
 hydrogen sulphide water. Dry in an air-bath at ioo C. till the 
 precipitate ceases to lose weight. If pure, 16.181 per cent, of 
 the weight is metallic chromium. 
 
 DETERMINATION OF CARBON IN IRON AND STEEL. 
 
 The determination of carbon is made according to the process 
 described in Blair's "Chemical Analysis of Iron," Third Edi- 
 tion, p. 148. 
 
 DETERMINATION OF GRAPHITE IN PIG IRON. 
 
 i to 3 grams of pig iron are carefully separated with a mag- 
 net and dissolved slowly in 30 to 60 cc. of nitric acid (sp. gr. 
 1.13) in an 8-oz. beaker. Set aside till the graphite settles. 
 Dry and weigh accurately a platinum Gooch crucible con- 
 taining an accurately- fitting disk of filter-paper. Place in the 
 filtering tube, and filter the solution through the crucible, using 
 strong suction. Wash alternately with hot dilute hydrochloric 
 acid (sp. gr. i.io) and cold water; then with a 10 per cent, 
 solution of caustic soda, alternating with hot dilute hydrochloric 
 acid and hot water, and finally with much acid and hot water 
 till the last traces of soda are washed out ; and lastly, with 
 ether. Dry in an air-bath at 100 C. and weigh. Ignite the 
 crucible in the blast till all the graphitic carbon is completely 
 oxidized; cool and weigh. Any increase in weight over the 
 
46 Oliver & Snyder Steel Works. 
 
 weight of the empty crucible will be the weight of retained 
 silica. This subtracted from the previous weight of the precipi- 
 tate, will give the true weight of graphite. 
 
VII. METHODS USED AT THE LABORATORY OF THE 
 
 HAINS WORTH STEEL CO., EDITH FURNACE 
 
 DEPARTMENT, ALLEGHENY, PA. 
 
 BY R. G. JOHNSTON. 
 
 DETERMINATION OF SILICA IN IRON ORES. 
 
 Weigh out i gram of the finely ground ore, and transfer to a 
 platinum crucible containing about 10 grams of sodium carbon- 
 ate. Fuse for about fifteen minutes, or until a quiet fusion is 
 obtained. Allow the crucible to cool, and place it in a beaker con- 
 taining about 40 cc. of water ; add about 15 cc. of hydrochloric 
 acid to dissolve the fused mass out of the crucible. Remove the 
 crucible, rinsing it with a fine jet of water. Stand the beaker 
 on the sand-bath, and evaporate its contents to dry ness over 
 night. Moisten the mass with a few cubic centimeters of hydro- 
 chloric acid, and add about 30 cc. of hot water. When all has 
 dissolved, filter, wash well with hot water, dry, ignite, and 
 weigh as SiO 2 . 
 
 The filtrate may be used for determining either iron or 
 alumina. 
 
 DETERMINATION OF IRON IN IRON ORES. 
 
 Weigh off 0.5 gram of the finely ground ore into a beaker 
 without lip. Digest with 30 cc. of hydrochloric acid over night 
 on the sand-bath. A solution of stannous chloride is now added 
 drop by drop until the ferric chloride solution is completely de- 
 oxidized. Dilute with about 100 cc. of hot water and add 30 cc. 
 of a solution of mercuric chloride to oxidize an excess of stan- 
 nous chloride. 
 
 Titrate with a standard solution of potassium bichromate, 
 testing after each addition of the standard solution with a drop 
 of potassium ferricyanide, on a white plate, for ferrous chloride. 
 
 The stannous chloride solution is made by dissolving 80 grams 
 of the common salt in 500 cc. of water and an equal volume of 
 hydrochloric acid. 
 
48 R. G. Johnston. 
 
 To prepare the mercuric chloride solution dissolve 50 grams 
 of the compound in i liter of water acidified with 15 cc. of hy- 
 drochloric acid. 
 
 DETERMINATION OF PHOSPHORUS IN IRON ORES. 
 
 Weigh out 5 grams of the sample (10 grams if very low in 
 phosphorus) and digest in a beaker with boiling hydrochloric 
 acid for about one-half hour. Filter, and fuse the residue with 
 about 4 grams of sodium carbonate. Dissolve the fusion and 
 evaporate the two solutions to dryness. Moisten with a few 
 cubic centimeters of hydrochloric acid, take up with hot water 
 and filter from the silica. Combine the two filtrates, and evapo- 
 rate to a syrup. Add about 30 cc. of nitric acid (sp. gr. 1.42), 
 and evaporate a second time to get rid of the last traces of hy- 
 drochloric acid. Dilute the solution to about 50 cc., and add 15 
 cc. of strong ammonia, which will form a thick paste. Dissolve 
 the latter in about 30 cc. of nitric acid (sp. gr. 1.20). Heat the 
 solution to 80 C., and add 100 cc. of molybdic acid solution. 
 Stir for a few minutes and allow the precipitate to settle. After 
 about one hour, filter, and wash with a one per cent, solution of 
 nitric acid . Dissolve the precipitate on the filter with a solution 
 of ammonia (i : 2), allowing the solution to run into a small 
 beaker containing a few crystals of citric acid and about 3 cc. of 
 hydrochloric acid. The volume of the solution should now be 
 about 100 cc. Add a few cubic centimeters of magnesia solu- 
 tion, stir well, and allow the mixture to stand over night. Fil- 
 ter and wash well with the above ammonia solution. Dry, 
 ignite, and weigh. Dissolve the precipitate in the crucible in 
 about 5 cc. of water and 3 cc. of nitric acid, and determine the 
 weight of any residue insoluble in the acid. Deduct from the 
 weight of the precipitate as obtained above. The difference is 
 the weight of magnesium pyrophosphate derived from phosphate 
 in the ore. 
 
 I have used this method for some three years and have always 
 had good results. 
 
 DETERMINATION OP MANGANESE IN PIG IRON AND IRON ORE. 
 
 Weigh out 2 grams of the iron and dissolve in 40 cc. of nitric 
 
Hainsworth Steel Company. 49 
 
 acid (sp. gr. 1.20). In a porcelain dish, 3.5 inches in di- 
 ameter, evaporate to a syrup or until a further evaporation 
 would cause iron to separate out as basic nitrate. Dilute and 
 wash into a half-liter flask ; neutralize, and precipitate with ox- 
 ide of zinc. Make the solution up to the mark, and shake well. 
 Allow the precipitate to settle in a large beaker, decant off 250 
 cc. of the solution which correspond to i gram of iron, transfer 
 to a flask, and heat to boiling. Titrate with a solution of potas- 
 sium permanganate, shaking well after each addition of the 
 standard solution. A pink coloration will show the end of the 
 reaction. 
 
 For iron ores low in manganese, dissolve in hydrochloric acid 
 of 1.20 sp. gr. If a hematite, add a few drops of nitric acid of 
 i. 20 sp. gr. Magnetite will require more oxidizing agent. In 
 other respects proceed as above. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Ford's method is used for this determination. See Blair's 
 " Chemical Analysis of Iron," Third Edition, p. 77. 
 
 DETERMINATION OF SULPHUR IN PIG IRON. 
 
 In determining sulphur, the evolution method is used. The 
 hydrogen sulphide formed in dissolving the sample is absorbed 
 in a solution of caustic soda (i : 8), and, after acidification of 
 the absorbent, titrated with iodine solution. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 Kmmerton's method as described by Blair's "Chemical Analy- 
 sis of Iron," Second Edition, p. 95, is made use of. 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 The method of Volhard as modified by O. Textor is used for 
 the estimation of manganese. The details have already been 
 given in the description of methods for the analysis of ores. 
 
VIII. METHODS USED AT THE LABORATORY OF 
 
 THE CARNEGIE STEEL CO., EDGAR THOMSON 
 
 STEEL WORKS AND FURNACES, 
 
 BRADDOCK, PA. 
 
 'BY C. B. MURRAY. 
 
 DETERMINATION OF SILICA IN IRON ORES. 
 
 i gram of the dried ore is fused with 12 to 15 grams of sodium 
 carbonate in a large platinum crucible. After thorough fusion 
 the crucible and contents are cooled in a i2-oz. beaker contain- 
 ing about 200 cc. of water. About the same volume of strong 
 hydrochloric acid is now added and the fusion is dissolved. The 
 solution is evaporated to dry ness on a steam table, the residue 
 taken up with 50 cc. hydrochloric acid diluted with water, the 
 silica filtered, ignited, and weighed. 
 
 In the case of manganese ores, i gram of the ore is dissolved 
 in 50 cc. hydrochloric acid, boiled, filtered, and the residue 
 fused. The fusion is added to the original solution. Then pro- 
 ceed as above. This is to avoid the action of chlorine on the 
 crucible. 
 
 DETERMINATION OF IRON IN ORES. 
 
 0.5 gram of the ore is dissolved in 50 cc. hydrochloric acid. 
 In case the residue left is not white the solution is filtered, the 
 residue fused with sodium carbonate, dissolved out in hydro- 
 chloric acid, the iron precipitated as hydroxide, dissolved in 
 dilute hydrochloric acid (i : i), and the solution added to main 
 solution. As a rule there is no iron left in the residue, and then 
 a fusion is not necessary. 
 
 To the hot solution of the ore, stannous chloride is added from 
 a burette drop by drop, stirring all the while, till the solution is 
 colorless. Three drops in excess are then added. After allow- 
 ing a few minutes for the stannous chloride to complete the re- 
 duction of any iron adhering to the silica, dilute to about 400 
 cc. with cold water, add all at once 20 cc. mercuric chloride solu- 
 tion, and stir vigorously. Now add from a burette potassium 
 
Edgar Thomson Steel Works and Furnaces. 51 
 
 bichromate enough to nearly oxidize all the iron. Place on a 
 white tile several drops of the ferricyanide solution. Take out 
 a drop of solution from the beaker and let it fall into a drop of 
 the ferricyanide. Continue adding bichromate and testing as 
 above till blue color is faint. Then take two drops for every 
 test. Wait one-half minute at each test for color to develop. 
 When no blue color appears at the end of one-half minute, take 
 the burette reading, which gives directly the percentage of iron 
 in the ore. 
 
 SOLUTIONS EMPLOYED. 
 
 The potassium dichromate solution contains 4.4 grams of the 
 salt in i liter of water. 
 
 i cc. corresponds to 0.005 gram iron, or to i per cent, when 
 0.5 gram of ore is employed. 
 
 The mercuric chloride solution contains 50 grams of the salt 
 in i liter. 
 
 The stannous chloride solution contains 50 grams in i liter. 
 
 The potassium ferricyanide solution contains two or three 
 pieces of the size of pin heads in 50 cc. of water. Prepare every 
 other day. 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 Dissolve 10 grams of the ore when the phosphorus is under 
 0.070 per cent., or 5 grams when it is above 0.070, in 150 cc. 
 hydrochloric acid. Filter by suction. Treat the residue in the 
 same manner as for silica and evaporate main solution to dryness 
 on the steam table. Take up main solution and fusion of resi- 
 due each with 100 cc. nitric acid. Heat on the sand-bath till 
 all is in solution. Filter and unite the filtrates. To this liquid, 
 which should not exceed 300 cc., add ammonia till the solution 
 becomes a pasty mass. Add nitric acid till the iron is redis- 
 solved and the solution an amber tint. 
 
 Heat to 70 C. and add 60 cc. of the motybdate solution. 
 Cork and shake thoroughly for five minutes. Let stand at a 
 temperature of 40 to 50 C. for an hour. Filter through a 12. 5 -cm. 
 filter. Wash thoroughly with a 2 per cent, nitric acid solution. 
 Dissolve the yellow precipitate on the filter in strong ammonia 
 
52 C. B. Murray. 
 
 and let the solution run through into a 5-oz. beaker containing 
 about i gram citric acid dissolved in 10 cc. strong hydrochloric 
 acid. After all the precipitate has been dissolved and run 
 through the filter, stir the solution in the beaker and add 10 cc. 
 magnesia mixture and fill up the beaker with strong ammonia. 
 Stir a little and set in cold water till the solution is cold. Then 
 stir vigorously until the precipitate comes down. Let stand over 
 night. Filter through a 9-cm. filter. Wash thoroughly with 
 dilute ammonia (i : 3). Ignite, first at a low temperature, then 
 at a higher. Weigh as Mg 2 P 2 O 7 . Dissolve the weighed pre- 
 cipitate in dilute nitric acid (sp. gr. 1.20), heating crucible till 
 all is in solution. Filter, ignite, and weigh the residue, which 
 is mainly silica. Subtract this weight from the first and the dif- 
 ference is pure Mg 2 P.jO 7 . 
 
 SOLUTIONS USED IN PHOSPHORUS DETERMINATIONS. 
 
 Molybdic Acid Solution. 100 grams of molybdic acid are dis- 
 solved in 400 cc. of ammonia (sp. gr. 0.96). This is poured 
 into i liter of nitric acid (sp. gr. 1.20), thoroughly stirred, and 
 i cc. of a solution of sodium phosphate, containing 5 grams to 
 the liter, added. The mixture is well shaken and allowed to stand 
 twelve hours. The solution should be perfectly colorless. 
 
 Magnesia Mixture. no grams magnesium chloride and 280 
 grams ammonium chloride are dissolved in 1,300 cc. of water and 
 700 cc. ammonia (sp. gr. 0.96). The solution should stand at 
 least a week before using. 
 
 DETERMINATION OF MANGANESE IN ORES. 
 
 Dissolve i gram of the ore dried at 100 C. in 25 cc. strong hy- 
 drochloric acid. When all is in solution, dilute with an equal 
 bulk of water and filter. Wash twice with hot water. Ignite 
 the residue till the filter-paper is destroyed. Cool, add to the 
 crucible two or three drops of sulphuric acid and a little hydro- 
 fluoric acid, and evaporate to dryness to expel silica. Fuse the 
 residue with about 3 grams sodium carbonate. Dissolve fusion 
 in the original filtrate from first solution, and evaporate this to 
 dryness in the sand-bath. Take up in 150 cc. strong nitric acid. 
 Boil for about twenty minutes, and then add, a little at a time, 5 
 
Edgar Thomson Steel Works and Furnaces. 53 
 
 to 8 grams potassium chlorate. When enough has been added 
 to oxidize all the manganese, the solution will give a little puff 
 and the green fumes will disappear. Now add about i gram 
 more potassium chlorate and boil the solution for two minutes. 
 Cool and filter through a prepared asbestos filter or "plug." 
 Wash beaker and plug twice with strong nitric acid. The filtrate 
 should then be boiled and more potassium chlorate added to ascer- 
 tain if all the manganese has been precipitated. The manganese 
 dioxide on the plug, together with the asbestos, is now returned 
 into the same beaker in which the precipitation was made, dis- 
 solved in 25 cc. hydrochloric acid and boiled a few minutes. 
 The asbestos is filtered off and a few drops of sulphuric acid are 
 added to precipitate any barium which is generally found in 
 manganese ores. L,et stand about two hours. Now add ammo- 
 nia till a faint precipitate appears, then 25 cc. of ammonium 
 acetate solution. Boil for one minute, remove from the heat, 
 and, as soon as settled, filter. Wash three times with hot water. 
 Dissolve precipitate on filter in hydrochloric acid ( i : i ) and let 
 run into beaker in which first basic acetate separation was made. 
 Make a second basic acetate separation just as the first. Com- 
 bine the filtrates and dilute to about 400 cc. Add 40 cc. am- 
 monium phosphate solution and then acidulate with hydrochloric 
 acid. Boil and add ammonia, drop by drop with constant stir- 
 ring, until all the manganese is precipitated and the precipitate 
 is in the well-known crystalline form. L,et the solution cool, fil- 
 ter with suction, wash three times with hot water, ignite, and 
 weigh as Mn Q P 2 O 7 . 
 
 SOLUTIONS EMPLOYED. 
 
 Ammonium Acetate Solution. Dissolve 450 grams of the salt 
 in 8 liters of water. 
 
 Ammonium Phosphate Solution. Dissolve 560 grams of the 
 salt in 2.5 liters of water. 
 
 DETERMINATION OF MANGANESE IN MANGANIFEROUS IRON 
 
 ORES. 
 
 Dissolve i gram of iron ore in 50 cc. hydrochloric acid. 
 Evaporate to dryness on the steam-bath. Take up in 20 cc. nitric 
 acid, and evaporate to about 10 cc. Wash into a 5Oo-cc. flask, 
 dilute to about 200 cc., and add a solution of zinc oxide in water 
 
54 C. B. Murray. 
 
 till all the iron is precipitated. Dilute to 500 cc., make acid, 
 shake well, let settle, and decant off 250 cc. into a flask. Boil 
 for about five minutes. Titrate with a standard solution of potas- 
 sium permanganate. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Dissolve i gram of iron in 20 cc. strong hydrochloric acid in a 
 platinum dish. Evaporate to dryness over a bare flame. Heat 
 for one minute after it is dry. Remove flame, add 10 cc. hydro- 
 chloric acid and about 25 cc. water. Boil, filter, ignite, and 
 weigh as SiO 2 . 
 
 DETERMINATION OF SULPHUR IN PIG IRON. 
 
 Dissolve 5 grams in icocc. hydrochloric acid ( i : i ) in a 5<x>-cc. 
 flask. Pass the gas evolved through two |J-tubes containing 
 each 25 cc. potassium hydroxide solution. After the evolution 
 of gas has ceased, heat the flask to boiling and boil till inlet-tube 
 to first y-tube is hot. Remove the tube and draw off the potas- 
 sium hydroxide solution from the (J-tubesb) 7 means of a stop-cock 
 at bottom into a large porcelain dish. Dilute to 500 cc. Titrate 
 with a standard solution of iodine. 
 
 SOLUTIONS EMPLOYED. 
 
 The potassium hydroxide -solution contains i pound caustic 
 potash in 17,000 cc. of water. The starch solution is prepared 
 by dissolving 4 grams starch in a liter of boiling water and de- 
 canting the clear liquid for use. 
 
 The iodine solution is standardized by using a standard steel 
 and also a " shot" sample. The factor varies considerably be- 
 tween the two. For pig-iron drillings and steel, the steel factor 
 is used. For " shot" samples the shot factor. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 Dissol ve i. 63 grams in 25 cc. nitric acid (sp.gr. 1.20) ina4j-inch 
 dish. Evaporate to dryness over a lamp and bake for one-half 
 hour. Take up in 20 cc. hydrochloric acid and evaporate till 
 the volume of the solution is about 4 cc. Add about 5 cc. nitric 
 acid and heat till red fumes cease to come off. Dilute twice 
 with water and filter into an8-oz Erlenmeyer flask. Add ammo- 
 
Edgar Thomson Steel Works and Furnaces. 55 
 
 nia till a paste is formed, then nitric acid till the solution shows an 
 amber color. Heat to 40 C. and add 50 cc. inolybdate solution. 
 Shake for five minutes and let stand one-half hour. Filter and 
 wash five times with 2 per cent, nitric acid and twice with strong 
 alcohol. The filters are then placed in a water-bath and 
 heated one hour, removed, and weighed in a " clip." Of course 
 the filter-papers should have been heated one hour and weighed 
 previously. Since we started with 1.63 grams, calling the per- 
 centage of phosphorus in yellow precipitate 1.63, every milli- 
 gram equals o.ooi per cent, phosphorus. 
 
 The solutions are the same as used in an ore analysis. 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 i gram of iron is dissolved in 25 cc. nitric acid (sp. gr. 1.20), 
 evaporated to about 10 cc.; then proceed as in case of manga- 
 nese in manganiferous iron ores. 
 
 DETERMINATION OF CARBON IN STEEL. 
 
 In case of steels of over 0.50 per cent, carbon take i gram ; 
 for steels under 0.50 take 2 grams. Dissolve in 100 cc. in first 
 case, or 150 cc. in second, of the double chloride of copper and 
 potassium solution. The process may be hastened by stirring and 
 heating to about 80 C. After all is in solution filter into a 
 platinum boat, wash four or five times with dilute hydrochloric 
 acid ( i : i ) and with hot water. For the combustion a platinum 
 tube is used containing six inches of copper oxide held in place 
 by platinum gauze. 
 
 The oxygen used in the combustion is purified by passage, 
 first through a bottle of potash solution, and second through a 
 jar of solid potash, upon which a layer, one inch deep, of calcium 
 chloride rests. A ten-burner Bunsen furnace is used. 
 
 Two burners are lighted under the copper oxide in the plati- 
 num tube. When this point is red hot all the burners are 
 lighted and oxygen passed through for half an hour. The car- 
 bon dioxide is caught in a solution of barium hydroxide in a 
 Meyer tube containing six bulbs. For carbon under i per cent., 
 25 cc. of a saturated solution of barium hydroxide is sufficient. 
 This amount will about fill four of the bulbs in the tube. At the 
 
56 Edgar Thomson Steel Works and Furnaces. 
 
 end of half an hour the oxygen is shut off and air passed 
 through the same train for fifteen minutes. The Meyer bulb is 
 then detached and the solution filtered through a 9-cm. filter 
 using suction. By means of a rubber tube connected with the 
 train a jet of air is forced into the funnel during filtering, keeping 
 an atmosphere free from carbon dioxide surrounding the filter- 
 paper. The tube is easily washed clean. The filter-paper with 
 precipitated barium carbonate is put into a platinum crucible 
 and the crucible subjected to gentle heat until the filter-paper is 
 burnt, then placed in a muffle furnace and heated till white. It 
 is weighed as BaCO 3 and carbon calculated. 
 
 SOLUTIONS EMPLOYED. 
 
 Double Chloride of Copper and Potassium. 2,250 grams of the 
 double salt are dissolved in 6.5 liters of water and 0.5 liter hy- 
 drochloric acid added. 
 
 The barium hydroxide solution contains 20 grams of the com- 
 mercial baryta dissolved in i liter of water. 
 
 DETERMINATION OF SULPHUR IN STEEL. 
 
 5 grams of steel are dissolved in 100 cc. hydrochloric acid 
 (i : i). From this point on, the method employed is the same 
 as in the case of pig iron. 
 
 DETERMINATION OF PHOSPHORUS IN STEEL- 
 
 Dissolve 1.63 grams of steel in 25 cc. nitric acid (sp. gr. 1.20), 
 and proceed in the same manner as in the case of pig-iron, ex- 
 cept that it is not necessary to filter off graphite. 
 
 DETERMINATION OF MANGANESE IN STEEL. 
 
 Dissolve i gram in 25 cc. nitric acid (sp. gr. 1.20) and pro- 
 ceed as in the case of pig iron. 
 
 DETERMINATION OF NICKEL IN STEEL. 
 
 Use the method given by Blair, in ( ' Chemical Analysis of 
 Iron," Third Edition, p. 184. 
 
IX. METHODS USED AT THE LABORATORY OF THE 
 CLINTON IRON AND STEEL CO., PITTSBURG, PA. 
 
 BY A. B. HARRISON. 
 
 DETERMINATION OF SILICA IN IRON ORES. 
 
 The ore is treated according to the directions given in Blair's 
 " Analysis of Iron," Third Edition, p. 239. 
 
 DETERMINATION OF IRON IN ORES. 
 
 The sample is dissolved in concentrated hydrochloric acid, 
 the insoluble residue fused with sodium carbonate, and the 
 fusion dissolved in dilute hydrochloric acid. Ths solution of 
 ferric chloride obtained is reduced with stannous chloride, the 
 excess of the latter being oxidized with mercuric chloride. The 
 reduced iron solution is titrated with potassium bichromate. 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 The sample is dissolved in hydrochloric acid, the insoluble 
 residue fused with sodium carbonate, and the fusion dissolved 
 in dilute sulphuric acid. The filtrate from the insoluble resi- 
 due and the filtrate from the solution of its fusion are combined, 
 precipitated with ammonia (sp. gr. 0.96), and the precipitate 
 dissolved in nitric acid (sp. gr. 1.13). The determination is 
 then proceeded with as in the case of steel. 
 
 DETERMINATION OF MANGANESE IN ORES. 
 
 See the method described for determination of manganese in 
 pig iron, p. 58. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Drown's method somewhat modified is used. Dissolve 0.4667 
 gram of drillings in " silicon mixture" in a covered porcelain 
 dish, and evaporate the solution to dryness without removing 
 the cover. When the dish is sufficiently cool wash off the watch- 
 glass into the dish, and rinse down the sides of the dish with hot 
 dilute hydrochloric acid ( i : i ) until the volume of the liquid is 
 
58 A. B. Harrison. 
 
 50 cc. Boil until all iron salts are dissolved, filter with the aid 
 of suction, and wash alternately with hot water and dilute hydro- 
 chloric acid until all iron is washed out. Burn and weigh. 
 Ashless filters being used, no calculation beyond " pointing off" 
 will be necessary, as can readily be seen. 
 
 The silicon mixture is made as follows : Mix 1,500 cc. of water, 
 500 cc. of nitric acid of 1.40 sp. gr., and 150 cc. of sulphuric acid 
 of 1.84 sp. gr. 
 
 DETERMINATION OF SULPHUR IN PIG IRON. 
 
 The determination of sulphur is carried out according to the 
 11 iodine method" as given in Blair's "Analysis of Iron," Third 
 Edition, pp. 68-71. In this form the method is the iodine 
 method as modified by Mr. E. T. Wood.. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 For this purpose I use Emmerton's method as described by 
 Dr. Dudley. 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 Manganese is determined according to a modification of Vol- 
 hard's method. One gram of drillings is dissolved in 100 cc. of 
 silicon mixture in a porcelain evaporating dish. After solution 
 5 cc. of concentrated hydrochloric acid are added, and the con- 
 tents of the dish evaporated to dry ness. The cover of the dish 
 is washed off with hot water and the residue taken up with 100 
 cc. of water. Boil till all iron salts are dissolved. Transfer the 
 solution without filtering to a liter flask, and dilute with water to 
 300 cc. Bring the contents of the flask to boiling, and add pure 
 zinc oxide suspended in water till all iron is precipitated and 
 zinc oxide is present in slight excess. Titrate the contents of 
 the flask while boiling hot and without filtering with potassium 
 permanganate solution. 
 
 DETERMINATION OF SILICON, SULPHUR, PHOSPHORUS, MAN- 
 GANESE, AND NICKEL IN STEEL. 
 
 Silicon is determined as described in Blair's " Analysis of 
 Iron," Third Edition, p. 72. 
 
Clinton Iron and Steel Company. 59 
 
 Sulphur is estimated by the method given for pig iron. The 
 aqua regia method is used for checking. 
 
 Phosphorus is determined as in pig iron. Results are checked 
 by the " magnesia method." 
 
 For nickel determinations the method of A. T. Eastwick is 
 used. See Proceedings of the Engineers' Society of Western 
 Pennsylvania, 9, 170. 
 
 Manganese is determined by the method described for pig iron. 
 
X. METHODS USED AT THE LABORATORY OF THE 
 ISABELLA FURNACE CO., ETNA, PA. 
 
 BY F. G. BRINKER. 
 
 DETERMINATION OF SILICA IN IRON ORES. 
 
 Dissolve i gram finely powdered ore in hydrochloric acid, 
 dilute, filter, wash, and fuse residue with a mixture of sodium 
 and potassium carbonates. The fusion is dissolved in a beaker 
 in hydrochloric acid. Evaporate to dry ness and bake. Dis- 
 solve in hydrochloric acid, dilute the solution, filter, wash the 
 residue with hot water, dilute hydrochloric acid, and again with 
 hot water. Burn and weigh. 
 
 DETERMINATION OF IRON IN IRON ORES. 
 
 Dissolve i gram of ore, finely pulverized, in a flask in 40 cc. 
 hydrochloric acid, at a gentle heat. Add i gram of potassium 
 chlorate. Place a funnel in the neck of the flask and boil gently 
 till chlorine is expelled. Dilute to 50 cc., heat nearly to boil- 
 ing, and deoxidize with a solution of stannous chloride measured 
 by means of a burette. Cool, and titrate back the excess of 
 stannous chloride with a solution of iodine. 
 
 If greater accuracy be required filter and fuse the insoluble 
 residue, dissolve in acid, and add to the main solution before 
 deoxidizing. 
 
 In preparing the standard iron solution, fine iron wire is used 
 and treated as above described. The first factor is found by 
 standardizing the stannous chloride and iodine solutions. Take 
 2 cc. of stannous chloride solution, dilute, add a little starch 
 solution, and titrate with iodine solution. Divide the number 
 of cubic centimeters of iodine into the number of cubic centi- 
 meters of stannous chloride. Multiply the number of cubic cen- 
 timeters of iodine used to titrate back the excess of stannous 
 chloride used by this factor, and subtract from the total volume 
 of stannous chloride used for the reduction. The second factor 
 is found by dividing the number of cubic centimeters of stannous 
 
Isabella Furnace Company. 61 
 
 chloride, used for the standard after the excess has been sub- 
 tracted, into the weight of pure iron in the iron taken. 
 
 Multiply the number of cubic centimeters of stannous chloride 
 solution by this and by 100. This gives the per cent, of iron in 
 the sample. 
 
 SOLUTIONS EMPLOYED. 
 
 Stannous Chloride Solution. Dissolve 60 grams of crystals in 
 125 cc. hydrochloric acid and 125 cc. water. To this solution 
 there are added 650 cc. hydrochloric acid and 1,650 cc. water. 
 
 Iodine Solution. This contains 8 grams iodine dissolved in 
 potassium iodide solution and diluted to i liter. 
 
 I use also the permanganate method as described by Blair, 
 deoxidizing by zinc. When titanium is present, I use acid 
 ammonium sulphate. 
 
 DETERMINATION OF MANGANESE IN IRON ORES AND PIG IRON. 
 
 I use Williams' method and also Volhard's as described in 
 Blair's "Chemical Analysis of Iron, "Third Edition, pp. 112-117. 
 
 DETERMINATION OF PHOSPHORUS IN IRON ORE. 
 
 I use the molybdate-magnesia method as described by Blair 
 in "Chemical Analysis of Iron," Third Edition, p. 89. 
 
 DETERMINATION OF SILICON IN PIG IRON 
 
 Dissolve 0.9333 gram of drillings in a casserole in hydrochloric 
 acid, and evaporate to dry ness. Cool and take up with hydro- 
 chloric acid, heating the mixture to boiling. Dilute, filter, 
 wash with dilute hydrochloric acid, and finally with hot water. 
 Ignite cautiously until the filter has been burned off. The igni- 
 tion is then continued for fifteen minutes at the highest heat of 
 a gas blast-lamp. Cool and weigh. The weight of the silica 
 found divided by 2 and multiplied by 100 gives the percent- 
 age of silicon. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 Weigh 1.63 grams of well-mixed borings into a 5oo-cc. beaker 
 and add cautiously 35 cc. nitric acid of 1.20 sp. gr. Boil down 
 to dryness, and bake on a hot plate at 200 C., for thirty minutes. 
 Redissolve in hydrochloric acid. Add 35 cc. of concentrated 
 nitric acid and evaporate until the volume of the liquid is reduced 
 
62 Isabella Furnace Company. 
 
 to about 15 cc. Remove from hot plate, dilute with hot water, 
 filter, and to the filtrate add ammonia until a precipitate forms 
 which does not disappear en stirring. The neutralized solution 
 is treated with 3 cc. of concentrated nitric acid, which should 
 suffice to redissolve the precipitate and give a clear, amber- 
 colored liquid, not red in tint. The solution is then heated to 
 about 70 C., the molybdate solution added, and the mixture 
 shaken for five minutes. Let the precipitate settle, collect it on 
 a weighed filter, and wash with water containing 2 per cent, of 
 nitric acid. Dry in the air-bath at 120 C. for thirty minutes 
 after all visible moisture has disappeared, and weigh. 
 
XI. METHODS USED AT THE LABORATORY OF THE 
 
 SHENANGO VALLEY STEEL CO., 
 
 NEW CASTLE, PA. 
 
 BY WARREN R. CLIFTON. 
 
 DETERMINATION OF SIIyICA AND IRON IN ORES. 
 
 Weigh i grain of the sample into a No. 2 beaker, add 25 cc. 
 of strong hydrochloric acid, cover with a watch-glass, and digest 
 at a temperature just short of boiling until the ore is decomposed; 
 dilute with 25 cc. of water and filter into a No. 4 beaker. The 
 residue is then burned and fused with sodium carbonate, the 
 fusion dissolved in the filtrate from the residue, and the whole 
 allowed to go to hard dryness. Redissolve the mass in about 
 15 cc. of strong hydrochloric acid, dilute, filter into a 3OO-cc. 
 flask, and wash the residue three or four times with hot water; 
 ignite and weigh as SiO 2 . In the filtrate the iron is deoxidized 
 by granulated zinc and determined by titration with a standard 
 bichromate solution ; the addition of the standard is continued 
 until a drop of the iron solution added to a drop of potassium 
 ferricyanide solution no longer produces a blue coloration on 
 standing one-half minute. The number of cubic centimeters 
 of bichromate solution used multiplied by one hundred times 
 the value of i cc. in iron, gives the percentage of iron. 
 
 Potassium Bichromate Solution. Dissolve 17.570 grams of the 
 fused salt in water, dilute to 2 liters, and standardize with iron 
 wire. 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 Digest 5 grams of the samples dried at 100 C., in a No. 2 
 beaker, covered by a watch-glass in 50 cc. of strong hydrochloric 
 acid. When the ore appears to be perfectly decomposed, dilute, 
 and filter into a No. 5 beaker. The residue is burned and 
 fused with sodium carbonate, the fusion dissolved in hot water, 
 the solution acidified with strong hydrochloric acid, added to the 
 original filtrate, and the combined solutions allowed to go to 
 hard dryness on the hot plate. The mass is then moistened with 
 
64 Warren R. Clifton, 
 
 a little hydrochloric acid, diluted with a sufficient amount of 
 water to dissolve the sodium salt, and filtered into a 4co-cc. 
 Erlenmeyer flask. The process is then carried on as in the case 
 of steel. 
 
 DETERMINATION OF MANGANESE IN IRON ORES. 
 
 2 grams of ore are dissolved and further treated in the same 
 manner as for phosphorus and the solution filtered into a 5oo-cc. 
 flask. The solution is neutralized with ammonia until a slight 
 permanent precipitate forms. Redissolve this with a few drops 
 of hydrochloric acid, and add ammonium carbonate, drop by 
 drop, until a faint precipitate is formed. Add about 4 grams of 
 sodium acetate, boil one minute, and allow the precipitate to 
 settle. Filter into a 5co-cc. flask, and wash two or three times with 
 hot water. The precipitate is washed back into the same flask 
 in which the precipitation was made, and dissolved in the least 
 possible quantity of hydrochloric acid. The precipitation is 
 repeated exactly as before. Unite the filtrates and proceed as 
 in the case of steel. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Twice the factor- weight 0.9340 gram of drillings is weighed 
 off into a No. 5 beaker. Add 50 cc. of water, and then pour 
 into the mixture 20 cc. of sulphuric acid (sp. gr. 1.85), direct- 
 ing the acid to the center of the beaker. Evaporate until copious 
 fumes of sulphur trioxide are given off. Cool the beaker over a 
 cold blast jet. Add 100 cc. of water and 4 or 5 cc. of hydro- 
 chloric acid. Boil until all sulphate of iron has dissolved, filter 
 hot, wash at first with dilute hydrochloric acid ( i : i ) , and then 
 with hot water ; ignite and weigh. One-half the weight in 
 decimilligrams is the per cent, of silicon in hundredths. 
 
 DETERMINATION OF SULPHUR IN IRON AND STEEL. 
 
 Dissolve 5 grams of drillings in a No. 5 beaker, covered by a 
 watch-glass, in 50 cc. of strong nitric acid. When the violent 
 action has ceased, add 15 cc. of strong hydrochloric acid, and, 
 when solution is complete, about one-half gram of sodium car- 
 bonate. Evaporate the solution to hard dryness. Remove 
 the beaker from the heat ; when cold add 40 cc. of strong hydro- 
 

 Shenango Valley Steel Company. 65 
 
 chloric acid, and heat gently at first, unt^ the oxide of iron is 
 dissolved ; evaporate again to syrup, and, if any ferric chloride 
 separates, add a few drops of strong hydrochloric acid ; dilute, 
 and filter, washing with the least possible amount of dilute hydro- 
 to remove the last trace of iron. Heat the filtrate, 
 have a volume of about 400 cc., to boiling, add 
 5 cc. of a saturated solution of barium chloride, and allow to 
 stand at about 40 C. over night. Filter through a Q-cm. 
 Munktell's No. i filter ; wash with a little dilute hydrochloric 
 acid (i : i), and finally with hot water ; dry, ignite, and weigh 
 as BaSO 4 . 
 
 DETERMINATION OF SULPHUR IN PIG IRON AND 
 
 Evolution Method. Place 3 grams of drillings in a dry 5OO-cc. 
 flask, provided with a doubly perforated rubber stopper ; the 
 stopper carries a one-bulb thistle-tube, and a small piece of glass 
 tubing bent at right angles ; the latter is connected by a short 
 piece of rubber tubing to a glass tube running to the bottom of 
 an intervening bottle ; the exit-tube of the bottle is connected 
 by rubber tubing to a de^ery-tube, also bent at right angles, 
 reaching to the bottom or a one-inch by eight-inch specimen- 
 tube. Connected by a rubber stopper and delivery- tube with this 
 is a second specimen-tube. The whole apparatus is suitably 
 supported. Dilute 15 cc. of an ammoniacal cadmium chloride 
 solution to 100 cc. with cold water, and pour one-half into each 
 of the specimen-tubes. About 100 cc. of boiling water is added 
 to the 500-cc. flask, and the flask connected with the apparatus 
 above described. Introduce, through the thistle- tube, 50 cc. of 
 strong hydrochloric acid. When the sample has dissolved, boil 
 the solution until the steam reaches the first specimen-tube, then 
 disconne^at the latter, turn out the light, and allow the flask 
 to draw Wck the acid and water which has distilled into the 
 intervening bottle. Transfer the contents of the specimen- tubes 
 torn 40<Ap. Erlenmeyer flask, rinsing the tubes with a little 
 hydrochloric acid and water. Now add a few cc. of starch solu- 
 tion, acidulate with strong hydrochloric acid, and immediately 
 run in the iodine solution from a burette, agitating the con- 
 tents of the flask at the same time, until the proper blujlcolor is 
 
66 Warren R. Clifton. 
 
 obtained. The volpne v in cubic centimeters of iodine solution 
 used multiplied by the value of i cc., is the percentage of sulphur 
 in the sample. 
 
 Cadmium Chloride Solution. Dissoifc 120 grams of cadmium 
 chloride in 1,500 cc. of water, and adcffloo cc. of strong 
 
 Iodine Solution. Weigh out into a half-liter flask 3 of 
 
 iodine, and 20 grams of potassium dide. Add al 
 of water. Allow to stand over nig^t and dilute 
 The solution is standardized with an iron of known sulphur-con- 
 tent. The known percentage of sulphur divided by the num- 
 ber of cubic centimeters of solution required is the strength of 
 the iodine solution. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON AND STEEL. 
 
 3 grams of drillings are dissolved in a No. 5 beaker in 40 cc. 
 of nitric acid (sp. gr. 1.20) and the solution evaporated to hard 
 dry ness. Allow the beaker to cool, dissolve the precipitate in 
 30 cc. of strong hydrochloric acid^dilute with cold water, filter 
 into a 4OO-cc. Brlenmeyer flask, and wash the filter with cold 
 water. Add 10 cc. of strong ammonia and agitate the mixture 
 until the precipitate formed is all dissolved. The solution is 
 heated or cooled to 60 C., and 50 cc. of molybdate solution are 
 added by aid of a pipette ; the flask is shaken for two or three 
 minutes and then allowed to stand till the precipitate has settled. 
 Filter, collect the precipitate on a y-crn. S. & S. No. 589 filter, 
 and wash with dilute molybdate solution (water containing 5 
 per cent, of its volume of the above). Pour 3 or 4 cc. ammonia 
 on the precipitate, stir it up with a fine jet of water, and allow 
 the solution to run into the flask in which the precipitation was 
 made. Add drop by drop enough strong hydrochloric acid to 
 cause the separation of the yellow precipitate, and thejjammon|a 
 until it redissolves. Pour the solution back througir thevfilter, 
 allowing it to run into a i2o-cc. Erlenmeyer flask, and wash 
 two or three times with cold water. To the cold ^tioidd 
 very slowly 10 cc. of magnesia mixture, agitating 'constantly, 
 and, after the precipitant is all in, 5 cc. of strong ammonia. 
 Shake vigorously. Stand the flask in cold water for about one 
 hour ; Ifcter on a y-cm. S. &S. No. 589 paper, and wash with 5 per 
 
Shenango Valley Steel Company. 67 
 
 cent, ammonia. Ignite over the blast-lamp at a low heat, and 
 weigh as Mg 2 P 2 7 . 
 
 Molybdate Solution. Dissolve 100 grams of molybdic acid in 
 of strong ammonia. Pour 1,250 cc. of nitric acid 
 >o), into a 2.5-liter bottle, and place the bottle in a 
 water. Now add, in small portions, the molybdic 
 ammonia, taking about thirty minutes in the operation, 
 h'xture is kept in a warm place for forty-eight hours and 
 is then ready for use. 
 
 Magnesia Mixture. Dissolve 280 grams of ammonium chloride 
 together with no grams of magnesium chloride in 1,300 cc. of 
 water, and add 700 cc. of strong ammonia. Allow the solution 
 to stand four or five days before using. 
 
 DETERMINATION OF MANGANESE IN STEEL AND PIG IRON. 
 
 Dissolve 3 grams of drillings in a No. 5 beaker in 50 cc. of 
 nitric acid (sp. gr. 1.20), evaporate until the solution is almost 
 of a sirupy consistence, add 100 cc. of strong nitric acid, heat 
 the solution to boiling, and while boiling add 5 grams of potas- 
 sium chlorate in small portions. Continue the boiling for ten 
 minfctes. Cool the solution rapidly by standing the beaker in a 
 panfcf cold water ; filter by aid of a pump through purified 
 asbestos supported by a small piece of pumice stone in the stem 
 of the filtering tube ; wash two or three times with strong nitric 
 acid. Transfer the precipitate, with the asbestos filter, to the 
 beaker in which the precipitation was made. The filtering tube 
 is washed off with water and a little hydrochloric acid ; add 
 about 5 cc. of hydrochloric acid, and agitate the contents of the 
 beaker until the asbestos is all suspended. Heat the mixture 
 till the precipitate is dissolved ; filter from the asbestos into a 
 No. 2 bearer, and wash with hot water. To the filtrate add 
 enough ammonium acetate to precipitate the last traces of iron, 
 boil,pnd ^er into a 4oo-cc. Erlenmeyer flask. 
 
 Tj the ^Prate add an excess of strong ammonia, and then, 
 with a vigorous shake, a few cubic centimeters of bromine. 
 Heat gradually to boiling, allow the precipitate to settle, filter, 
 and wash with cold water. The washing of the precipitate 
 is easily accomplished by means of cold water, there bjpng no 
 
68 Warren R. Clifton. 
 
 fixed alkali presenfc Ignite over a blast-lamp at |Jiow heat 
 and weigh as Mn s O 4 . 
 
 In the case of pig iron, dissolve in 50 cc. of dilute h] 
 acid. Dilute and filter into a No. 5 beaker, evap< 
 nearly to a sirup, being careful not to heat too stron 
 solve in 50 cc. strong nitric acid, and evaporate to 
 sion of hydrochloric acid. Add 100 cc. of strong niti 
 heat to boiling, add 5 grams of potassium chlorate, and 
 as described for steel. 
 
 Determination of Manganese by the Color Method. In case of 
 steel o.i gram of each sample and of the standard, is measured 
 off into i -inch by 8-inch test-tubes. Pour into each test-tube* 
 15 cc. of nitric acid (sp. gr. 1.20). When the violent action has 
 ceased boil over an Argand burner till nitrous fumes are driven 
 off. While boiling, add about five-tenths of a gram of lead per- 
 oxide, and boil each sample and the standard exactly one 
 minute. The tubes thus filled are immediately placed in cold 
 water and set aside in a dark place. When cool, and the excess 
 of peroxide has settled out leaving the supernatant liquid per- 
 fectly clear, the standard solution is decanted into one of the 
 comparing tubes. The solution is then diluted with water to as 
 many cubic centimeters as the standard contains hundredAis of 
 i per cent, of manganese, and mixed thoroughly witifc the 
 water. The test sample is decanted in the same manner$and 
 diluted with cold water until it has the same shade as the stand- 
 ard solution. The reading in cubic centimeters represents the 
 percentage of manganese in hundredths. 
 
 In the case of pig iron it is preferable to dissolve one gram 
 each of the sample and of a pig iron standard in a No. 2 beaker 
 in 75 cc, of nitric acid of 1.13 sp. gr. Dilute to 100 cc. with cold 
 water and filter a portion through a dry filter. Draw out 10 cc. 
 of this solution with a pipette and let it run into a test-tube. 
 Add 5 cc. of nitric acid of 1.20 sp. gr., and proc^d as %i the 
 case of steel. 
 
 DETERMINATION OF MANGANESE IN IRON ORES. 
 
 2 grams of ore are dissolved as in the case of a determination of 
 phosjfcorus, and filtered into a 5oo-cc. flask. The solution is 
 
Shenango Valley Steel Company. 69 
 
 neutralized by ammonia, and a slight permanent precipitate pro- 
 duced. Redissolve this precipitate in a few drops of hydro- 
 chloric acid, and add ammonium carbonate, drop by drop, until 
 a precipitate begins to form. Then add 4 grams sodium acetate, 
 and jMJkfor one minute. Allow the precipitate to subside. Fil- 
 ter ifS( r*5oo-cc. flask and wash two or three times with hot 
 water. The precipitate is washed back into the flask in which 
 it ^Hl formed, by breaking the filter with a glass rod, and dis- 
 solved in the least possible quantity of hydrochloric acid. Re- 
 peat the precipitation exactly as before, unite the filtrates, and 
 proceed as in the case of steel. 
 
 DETERMINATION OF NICKEL IN STEEL. 
 
 Dissolve one gram of drillings in a No. 4 beaker in 25 cc. of 
 nitric acid (sp.gr. 1.20), and evaporate to hard dry ness. Redis- 
 solve in 15 cc. of strong hydrochloric acid and separate the iron 
 exactly as directed in the determination of manganese in ores^. 
 Unite the filtrates and boil down until their volume is reduced 
 to about 300 cc. Acidulate with a few drops of acetic acid, 
 heat to boiling, and pass hydrogen sulphide till the solution smells 
 strongly of the gas. Boil a few minutes until the precipitate has 
 a flocculent appearance. Filter and wash with hot water, ignite 
 the filter and precipitate, and transfer them to a No. 2 beaker. 
 Dissolve in 3 or 4 cc. of strong hydrochloric acid with a few 
 drops of strong nitric acid, evaporate to dryness, redissolve in 
 a few drops of strong hydrochloric acid, dilute to about 100 cc., 
 heat to boiling and pass hydrogen sulphide through the solution, 
 let the precipitate subside, filter if necessary, wash with hot 
 water and, if desired, burn and weigh as Cu 2 S. To the filtrate add 
 an excess of ammonia, pass hydrogen sulphide, allow the pre- 
 cipitate to settle, filter, wash, ignite in a porcelain crucible, and 
 weigh as NiO. 
 
XII. METHODS USED AT THE LABORATORY OF 
 
 THE PENNSYLVANIA RAILROAD COMPANY, 
 
 ALTOONA, PA. 
 
 BY C. B. DUDLEY AND F. N. PHASE. 1 
 " Method of Determining Carbon in Iron and Steel." Bf C. 
 
 B. Dudley and F. N. Pease. American Engineer and Railroad 
 
 Journal, July, 1893, p. 347. 
 
 " Method of Determining Carbon in Iron and Steel." By C. 
 
 B. Dudley and F. N. Pease. American Engineer and Railroad 
 Journal, August, 1893, p. 391. 
 
 4 ' The Need of Standard Methods for the Analysis of Iron and 
 Steel, with Some Proposed Standard Methods." By C. B. 
 Dudley and F. N. Pease. Journal of the American Chemical 
 Society, September, 1893, p. 501. 
 
 " Method of Determining Sulphur in Steel." By C. B. 
 Dudley and F. N. Pease. American Engineer and Railroad 
 Journal, September, 1893, p. 443. 
 
 " Standard Methods for the Analysis of Iron and Steel." By 
 
 C. B. Dudley. Proceedings Chemical Section, Engineers' Society, 
 W. A.j.October, 1893. 
 
 " Method of Determining Sulphur in Pig and Wrought Iron." 
 By C. B. Dudley and F. N. Pease. American Engineer and Rail- 
 road Journal, December, 1893, p. 579. 
 
 1 In publishing in the Proceedings of the Chemical Section of the Engineers' Society 
 of W. Pa., the methods of chemical analysis in use at the different iron and steel works 
 laboratories, it has been the practice heretofore, to print the methods in detail as de- 
 scribed by the senders. In the case of the methods of Dr. C. B. Dudley and Mr. F. N. 
 Pease, of the Pennsylvania Railroad Laboratory at Altoona, an exception has been 
 made. Dr. Dudley, in charge of the Altoona Laboratory, has kindly placed at the dis- 
 posal of the Committee, the details of the admirable methods so fully and clearly de- 
 scribed in the publications of the Pennsylvania Railroad Laboratory. These methods 
 have, however, been repeatedly reproduced in technical journals, and in the transactions 
 of various scientific societies, and they are already so well known to chemists that a de- 
 tailed account of them seems hardly necessary. In place of complete details, therefore, 
 a list of references to the papers of Dr. Dudley and Mr. Pease is here given. 
 
 Some of the papers do not deal with single methods of determination of the constitu- 
 ents of iron and steel, but are of such general interest that it seems eminently proper 
 that they should be included among the papers upon methods. 
 
Pennsylvania Railroad Company. 71 
 
 " Method of Determining Manganese in Steel." By C. B. 
 Dudley and F. N. Pease. American Engineer and Railroad 
 Journal, April, 1894., p. 176. 
 
 " An Attempt to Find the Amount of Phosphorus in Three 
 Samples of Steel." By C. B. Dudley and F. N. Pease. 
 Journal of the American Chemical Society , April, 1894., p. 217. 
 
 " On Some Points in the Determination of Phosphorus in 
 Steel by the Volumetric Method." By C. B. Dudley and F. N. 
 Pease. Journal of the American Chemical Society, April, 1894., 
 p. 224. 
 
 "Method of Determining Silicon in Steel." By C. B. Dudley 
 and F. N. Pease. American Engineer and Railroad Journal, 
 July, 1894, p. 321. 
 
 " Method of Determining Phosphorus in Steels." By C. B. 
 Dudley and F. N. Pease. Separate paper published by the 
 Pennsylvania Railroad Company. 
 
 The methods above mentioned for the determination of carbon 
 and of sulphur in steel are also published and distributed by the 
 Pennsylvania Railroad Company. 
 
XIII. METHODS USED AT THE LABORATORY OF 
 McINTOSH, HEMPHILL& CO., PITTSBURG, PA. 
 
 BY J. P. M'KELVEY. 
 
 DETERMINATION OF SILICA IN IRON ORES. 
 
 Fuse with sodium carbonate, dissolve in hydrochloric acid 
 and evaporate to dry ness, moisten the residue with hydrochlo- 
 ric acid, take up with water, filter, wash, ignite, and weigh. 
 
 DETERMINATION OP IRON IN IRON ORES. 
 
 The filtrate from the silica serves for the iron determination. 
 Reduce in a 6oo-cc. Erlenmeyer flask with tested zinc, and 
 titrate with bichromate as usual, using potassium ferricyanide 
 as an indicator. 
 
 DETERMINATION OF MANGANESE IN IRON ORES. 
 
 Dissolve i gram of ore in hydrochloric acid and evaporate to 
 dryness. Redissolve in 50 cc. of nitric acid (sp. gr. 1.42), and 
 proceed as in Ford's method. 
 
 DETERMINATION OF PHOSPHORUS IN IRON ORES. 
 
 Dissolve 5 to 10 grams of ore in hydrochloric acid and evap- 
 orate to dryness. Take up in a small amount of hydrochloric 
 acid, dilute, filter, and proceed as in the acetate method, sepa- 
 rating arsenic by hydrogen sulphide. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Dissolve i gram of drillings in 30 cc. of dilute hydrochloric 
 acid and evaporate to dryness. Moisten the residue with hydro- 
 chloric acid, dilute, filter, wash, ignite, and weigh. 
 
 DETERMINATION OF SULPHUR IN PIG IRON. 
 
 As given in Blair's " Analysis of Iron," Third Edition, p. 65, 
 under the heading " By Oxidation and Solution." 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 The acetate method is used. 
 
Mclntosh, Hemphill & Co. 73 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 This determination is made by the color method as given in 
 Blair's "Analysis of Iron," Third Edition, p. 126, with the ex- 
 ception that, after solution of the drillings and before diluting to 
 100 cc., the solution is filtered. 
 
 DETERMINATION OF SULPHUR, PHOSPHORUS, MANGANESE, AND 
 NICKEL IN STEEL. 
 
 Sulphur and phosphorus are determined according to the 
 methods already detailed for pig iron ; manganese by the color- 
 imetric method described in Blair's " Analysis of Iron," Third 
 Edition, p. 126 ; for nickel determination see Blair's "Analysis 
 of Iron," Third Edition, p. 184. 
 
XIV. METHODS USED AT THE LABORATORY OF THE 
 W. DEWEES WOOD COMPANY, McKEESPORT, PA. 
 
 BY THEO. TONNELE AND R. B. CARNAHAN, JR. 
 
 DETERMINATION OF SILICA IN IRON ORES. 
 
 The sample, which has passed through a loo-mesh sieve, is 
 dried thoroughly at 100 C. just previous to analysis. 
 
 Fuse i gram of the ore with 5 grams sodium carbonate and 0.25 
 gram potassium nitrate in a platinum crucible. Acidify with 
 hydrochloric acid and evaporate todryness. Redissolve in suffi- 
 cient water and hydrochloric acid, filter, wash with dilute hydro- 
 chloric acid (sp. gr. i.io) and hot water, ignite, and weigh. 
 Treat the ignited residue in the usual way with hydrofluoric 
 acid and a few drops of sulphuric acid ; the loss in weight repre- 
 sents the quantity of silica in the ore. 
 
 DETERMINATION OF IRON IN ORES. 
 
 Dissolve 0.75 gram in concentrated hydrochloric acid, heating 
 on the steam-bath over night. Deoxidize the ferric iron of the 
 solution with stannous chloride, adding the latter gradually. 
 When the solution is entirely colorless, cool somewhat, and then 
 add 10 cc. of mercuric chloride solution. Titrate in the regular 
 way with standard potassium bichromate, using a very dilute 
 solution of potassium ferricyanide to determine the end-reaction. 
 
 Solutions. The mercuric chloride is a saturated aqueous solu- 
 tion. The stannous chloride solution contains 150 grams of the 
 salt dissolved in i liter of hydrochloric acid (i.io sp. gr.). To 
 prepare the standard bichromate, dissolve 7 grams of the salt in 
 i liter of water, and dilute so that i cc. is equivalent to 0.0075 
 gram of iron. The solution is standardized from a steel of known 
 composition. 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 From 3 to 5 grams of ore (according to the percentage of phos- 
 phorus) are dissolved in strong hydrochloric acid, and the solu- 
 
IV. Dewees Wood Company. 75 
 
 tion evaporated to dryness ; the residue is redissolved in a few 
 cc. of strong hydrochloric acid and water ; and the silicious 
 matter remaining filtered off and ignited. The latter is fused 
 with a little sodium carbonate, the fusion dissolved in nitric acid 
 and water, and the nitric solution added to the original filtrate, 
 which is again evaporated to dryness. After dissolving in a 
 little hydrochloric acid and water, the silica is removed by filtra- 
 tion. The filtrate is made slightly alkaline with ammonia, and 
 then slightly acidified with nitric acid. The solution, which 
 measures about 100 cc., is heated to 80 C.; 50 cc. of molybdate 
 solution are added, and, after standing for about one minute, the 
 mixture is agitated for five minutes by passing a stream of air or 
 natural gas through it. The yellow precipitate is filtered 
 by the aid of suction and washed with pure water. It is 
 then titrated with standard alkali, the solution being standard- 
 ized by steels and pig irons in which the phosphorus has already 
 been determined by the molybdate-magnesia method, according 
 to Blair's "Analysis of Iron," Third Edition, p. 89. 
 
 Solutions. The molybdate solution is made by dissolving i 
 pound of molybdic acid in 1,000 cc. of strong ammonia, and 1,000 
 cc. of water, and pouring this solution into 6J liters of nitric acid 
 (sp.gr. 1.20). 
 
 DETERMINATION OF MANGANESE IN ORES 
 
 From 3 to 5 grams of ore are dissolved in strong hydrochloric 
 acid, and the solution evaporated to dryness. The dry mass is 
 redissolved in hydrochloric acid and water, and the insoluble 
 residue filtered off and ignited. The residue is fused with 
 sodium carbonate and the fusion dissolved in hydrochloric acid 
 and water. The solution, after separating the silica, is added to 
 the main solution ; potassium chlorate is then added, care being 
 taken to expel the chlorine generated in excess. The iron is 
 precipitated as basic acetate, the precipitate being redissolved 
 and reprecipitated twice. For each gram of ore 2 grams of 
 ammonium acetate are used. The combined filtrates are then 
 concentrated and the manganese precipitated by bromine as di- 
 oxide. The precipitate is filtered off and dissolved in hydro- 
 chloric acid, the solution neutralized with ammonia, and the man- 
 
76 Theo. Tonnele and R. B. Catnahan,Jr. 
 
 ganese again precipitated as ammonium manganese phosphate, 
 according to Blair. Ignite and weigh as manganese pyrophos- 
 phate, Mn 2 P 2 O T . When the percentage is less than 0.5, the 
 manganese dioxide is converted for weighing into protosesqui- 
 oxide. 
 
 DETERMINATION OP SILICON IN PIG IRON. 
 
 Dissolve i gram of borings in 35 cc. of " silicon mixture," 
 and evaporate until the formation of fumes of sulphur tri- 
 oxide begins. When sufficiently cool, dissolve in a little water 
 and about TOCC. of strong hydrochloric acid. Filter, using suc- 
 tion, wash with hot water and dilute hydrochloric acid 
 (i.io sp. gr.), ignite, and weigh as silica. 
 
 Solutions. The " silicon mixture" is made by adding 100 cc. 
 of strong sulphuric acid to 900 cc. of nitric acid (1.20 sp. gr.). 
 
 DETERMINATION OF SULPHUR IN PIG IRON. 
 
 Weigh into a 5oo-cc. flask, 5 grams of drillings, add 50 
 cc. of water, and, after connecting the flask with the absorption 
 apparatus, add 50 cc. of strong hydrochloric acid. Without 
 delay light a small flame under the flask, and dissolve as rapidly 
 as desired. The evolved gas bubbles through 50 cc. of ammo- 
 niacal cadmium chloride solution contained in a y-inch foot test- 
 tube. When the drillings have dissolved, boil the solution to 
 expel the last traces of hydrogen sulphide from the flask. 
 Rinse out the contents of the test-tube into a shallow porcelain 
 dish, made slightly acid with hydrochloric acid, add starch solu- 
 tion, and titrate to a decided blue color with a standard iodine 
 solution. 
 
 Solutions. Ammoniacal cadmium chloride solution is made 
 by dissolving 30 grams of cadmium chloride in 5 liters of water 
 and i liter of strong ammonia. The iodine solution is prepared 
 by dissolving 8.5 grams of iodine and about 25 grams of potas- 
 sium iodide in a small quantity of water, and diluting to 2 liters. 
 This solution is then exactly standardized by a standard steel 
 (rather high in sulphur) in which the percentage of sulphur has 
 been exactly determined by the aqua regia method, as described 
 by Blair in his /' Chemical Analysis of Iron," Third Edition, 
 
W. Dewees Wood Company. 77 
 
 p. 65. Except only in a very few cases, all pig irons are tested for 
 sulphur by the evolution method. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON. 
 
 Dissolve 3 grams of the sample in 50 cc. of nitric acid 
 (1.20 sp. gr.), evaporate to dryness, and heat the residue over 
 a bare flame for five minutes. Cool, dissolve in a few cc. of 
 strong hydrochloric acid, and evaporate until the solution 
 measures about 10 cc. Then add about 20 cc. of strong nitric 
 acid, and boil for about four minutes. Dilute with water and 
 filter. The solution should have a volume of about 75 cc. 
 Complete the determination as in the case of ores. 
 
 For the sake of rapidity we use the following method for 
 several grades of Bessemer pig iron : Dissolve 3 grams of the 
 metal in 100 cc. of nitric acid (sp. gr. 1.13). When the borings 
 have completely dissolved add a saturated solution of potas- 
 sium permanganate till a decided precipitate remains. Boil 
 three minutes and then add 10 cc. of strong hydrochloric acid. 
 Filter off the carbonaceous residue and proceed further as de- 
 scribed for ores. 
 
 DETERMINATION OF MANGANESE IN PIG IRON. 
 
 Dissolve 3 to 5 grams of the sample in 50 cc. of nitric acid 
 (sp. gr. i. 20), evaporate to dryness, and ignite for five minutes. 
 Cool, redissolve in a few cc. of hydrochloric acid, evaporate the 
 excess of acid, and filter. Make the basic acetate separation, 
 etc., as described under iron ores. 
 
 The color method is also used largely for pig irons ; viz., dis- 
 solve 0.5 gram of pig iron in 15 cc. of nitric acid (sp. gr. 1.20) 
 in an 8-inch test-tube, filter, and dilute the filtrate to 50 cc. 
 Draw off 10 cc. with a pipette and place the solution in an 
 8-inch test-tube. Add 3 cc. of nitric acid (sp. gr. 1.20). 
 Heat to boiling, add about 0.2 gram of lead peroxide, 
 and boil the mixture for two minutes. Add about 15 
 cc. of cold water, and allow the tube to stand in cold water till 
 the lead peroxide settles completely. Compare the color of the 
 sample for analysis with that of a standard pig iron treated simi- 
 larly. Standards are always made by the basic acetate method, 
 the manganese being weighed as pyrophosphate. 
 
78 Theo. Tonnele and R. B. Carnahan, Jr. 
 
 DETERMINATION OF SULPHUR IN STEEL. 
 
 See Pig Iron. 
 
 DETERMINATION OF PHOSPHORUS IN STEEL. 
 
 See Pig Iron. The permanganate oxidation method is 
 generally used ; filtering off the silica becomes unnecessary 
 in this case. 
 
 DETERMINATION OF CARBON IN STEEL. 
 
 Dissolve 3 grams of steel in 200 cc. of a saturated solution of 
 cupric potassium chloride, containing 10 cc. of strong hydro- 
 chloric acid, at 60 C., with constant stirring. 
 
 Filter off the carbonaceous residue on an asbestos plug, and 
 wash with dilute hydrochloric acid and hot water. 
 
 Transfer the residue to a 5oo-cc. flask and burn with a mixture 
 of chromic and sulphuric acids, absorbing, for weighing, the car- 
 bon dioxide evolved. 
 
 The combustion train is as follows : 
 
 1. A 500-cc. flask. 
 
 2. An empty tube. 
 
 3. A tube containing : 
 
 0.2 gram pyrogallic acid, 
 5 grams potassium oxalate, 
 3 grams sodium chloride, 
 0.2 gram sulphuric acid, and 
 
 water sufficient to make the volume 20 cc. 
 
 4. A tube containing silver sulphate and strong sulphuric acid. 
 
 5. A tube containing sulphuric acid. 
 
 6. An empty tube. 
 
 7. Geissler potash bulbs containing caustic potash (sp. gr. 
 1.27); and a guard l|-tube containing strong sulphuric acid. 
 
 After the combustion, pure air is aspirated through the ap- 
 paratus for twenty minutes. 
 
 Blanks are made, and the apparatus frequently checked by 
 steels of known carbon content. The various minute details are 
 carried out about as given in Blair's work above quoted. 
 
W. Dewees Wood Company. 79 
 
 DETERMINATION OF MANGANESE IN STEEL. 
 
 See Pig Iron. The silica filtration is not generally necessary, 
 however. 
 
 DETERMINATION OF NICKEL IN STEEL. 
 
 Make the basic acetate separation, using i gram of steel, and 
 to the filtrate add 10 grams of ammonium acetate and 6 drops of 
 acetic acid. Precipitate with hydrogen sulphide, filter, burn, 
 and weigh as NiO (and CuO, should copper be present). 
 
 Dissolve the ignited precipitate in hydrochloric acid, and a 
 few drops of nitric acid, dilute with water, and precipitate any 
 copper in the solution with hydrogen sulphide. 
 
 Ignite and weigh as CuO ; subtract the weight from the first 
 weight. The difference represents the quantity of NiO derived 
 from the sample. 
 
XV. METHODS USED AT THE LABORATORY OF THE 
 OHIO STEEL COMPANY, YOUNGSTOWN, OHIO. 
 
 BY J. C. BARRETT. 
 
 DETERMINATION OF SILICA IN ORES. 
 
 Weigh off 5 grams ore which has been dried at 100, dissolve 
 in 75 cc. strong hydrochloric acid, evaporate to dry ness, add 30 
 cc. strong hydrochloric acid, and when dissolved dilute and 
 filter, washing with dilute hydrochloric acid and water. The 
 residue is then burned and fused. The fusion is dissolved in 
 water, made acid with hydrochloric acid, and evaporated to dry- 
 ness. Take up with hydrochloric acid and water, filter, and 
 wash well with water. Place in crucible wet, heat gently until 
 dry and the paper is well charred, then heat in a muffle until white. 
 Weigh as soon as cold. Observe precautions for titanic acid 
 and barium sulphate. 
 
 DETERMINATION OF IRON IN ORES. 
 
 The ore is dried at 100 for one hour and cooled in a desic- 
 cator. Weigh quickly 5 grams of the ore, dissolve in a dish with 
 75 cc. concentrated hydrochloric acid and evaporate to dry ness 
 on a sand-bath. Redissolve in 30 cc. strong hydrochloric acid, 
 and when alt is in solution evaporate to a very small bulk or 
 near sticking-point. Dilute with hot water and filter, washing with 
 as little dilute hydrochloric acid as possible. Wash well with hot 
 water. Burn silicious residue and, if colored at all with iron, fuse. 
 Dissolve and make acid with hydrochloric acid and evaporate to 
 dry ness to separate the silica. Take up with as little hydro- 
 chloric acid as possible and filter into the main solution, which 
 should be in a graduated 5oo-cc. flask, calibrated accurately 
 with a loo-cc. pipette. Keep at room temperature, fill with 
 water of same temperature to mark, and mix well. Take 
 loo cc., with same pipette you have checked flask with, and 
 put into a clean flask of 5oo-cc. capacity, fitted with a rubber 
 stopper having a Bunsen valve. Add 100 cc. sulphuric acid 
 
Ohio Steel Company. 81 
 
 (i : 4), and then 15 grams of zinc. Keep cool for a time, then 
 add 10 grams more of zinc if necessary. When all action is 
 over, raise to a good heat, but not to boiling. Cool, pour into a 
 No. 5 beaker into which 50 cc. of sulphuric acid (1:4) has 
 been poured ; wash out flask well, decanting from residue caused 
 by the zinc, filling the beaker to a little more than half full; and 
 titrate with a standard solution of potassium permanganate, ma- 
 king allowance for a blank on zinc which is carried along side by 
 side with the ore, using the same weight of zinc in blanks as for 
 ore. In presence of titanium reduce with hydrogen sulphide. 
 Remove the hydrogen sulphide and titrate. 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 Dissolve 5 grams of ore in 75 cc. of strong hydrochloric acid and 
 treat in the same way as for iron, except that there is added a 
 little nitric acid on the first evaporation. When the second 
 evaporation reaches the sticking-point add 3 or 4 drops of hydro- 
 chloric acid, dilute and filter into a i6-oz. flask, wash, and then 
 burn the residue and fuse. Dissolve the fusion in water, make acid 
 with hydrochloric acid, and evaporate; take up with as little 
 acid as possible, dilute with water, and filter into the flask with 
 first solution. Add 25 cc. ammonia, then 25 cc. concentrated 
 nitric acid which should just redissolve the precipitate and leave 
 the liquid slightly acid . Heat the solution in the flask to 85 exactly, 
 and add 75 cc. ammonium molybdate solution and shake for 
 five minutes. When it has stood for one-half hour, or until 
 settled, filter through a 9-cm. Munktell paper, which has been 
 dried for one hour at 110 and weighed between watch-glasses, 
 as soon as taken from oven. In presence of arsenic or titanium 
 follow Blair's acetate method after getting the main filtrate and 
 that from the fused residue united, down to the basic acetate pre- 
 cipitate carrying the phosphorus. This is put into a small 
 beaker, paper and all, and dissolved in a mixture of dilute nitric 
 and hydrochloric acids, at a gentle heat. Filter from paper and 
 evaporate to expel hydrochloric acid ; now filter into a i6-oz. 
 flask and precipitate phosphorus as above with ammonium molyb- 
 date solution at 85. When necessary or desirable the yellow 
 precipitate and paper are put into a small beaker, treated with 
 
82 /. C. Barrett. 
 
 dilute ammonia, the paper and silica separated, and phosphorus 
 precipitated with magnesia mixture. 
 
 The yellow precipitate is washed well with 2 per cent, nitric 
 acid solution, excess of moisture removed with blotting-paper 
 and dried in an oven at 110, taking from oven and weighing at 
 once between the watch-glasses. 
 
 The ammonium molybdate solution is made by dissolving 200 
 grams molybdic acid in 500 cc. water with 500 cc. ammonia, 
 and adding 2,500 cc. of nitric acid (sp. gr. 1.20), and keeping in 
 a warm place for twenty-four hours. 
 
 DETERMINATION OF MANGANESE IN ORES. 
 
 Dissolve 5 grams of ore in 75 cc. concentrated hydrochloric acid, 
 evaporate to dryness, take up with hydrochloric acid, and when 
 in solution evaporate to a small bulk. Filter into a 5Oo-cc. flask. 
 Burn residue after washing, fuse, dissolve fusion in water, make 
 acid, and evaporate to dryness. Take up with a small quantity of 
 hydrochloric acid, dilute with water, and filter into main solution. 
 If little manganese is present, evaporate the whole in a No. 4 
 beaker to sirupy consistency with concentrated nitric acid twice. 
 If manganese be in large quantity, fill flask to mark and take a 
 measured quantity after shaking up well, and evaporate as 
 above. Then add 100 cc. concentrated nitric acid, heat to boil- 
 ing and precipitate manganese dioxide with potassium chlorate 
 and boil for a few minutes. Remove from the lamp and cool. 
 Filter through asbestos filter and wash once with colorless nitric 
 acid. When dry, transfer asbestos and precipitate to original 
 beaker and wash filtering tube with concentrated hydrochloric 
 acid and hot water, washing down the sides of the beaker with 
 same, using about 18 cc. hydrochloric acid. Heat, while shaking, 
 over a lamp, until manganese dioxide is entirely dissolved. Filter 
 off asbestos receiving the solution in a i6-oz. flask. Wash well 
 and make a basic acetate precipitation. Filter from this precipi- 
 tate into a No. 6 beaker. Redissolve the precipitate with hydro- 
 chloric acid and repeat the basic acetate, filtering into the original 
 solution. Make solution in beaker acid with acetic acid, heat 
 to boiling, and precipitate manganese as phosphate with 
 ammonium phosphate ; boil until the precipitate is crystalline, 
 
Ohio Steel Company. 83 
 
 stirring if necessary ; then add 25 cc. ammonia, boil for a few 
 minutes, remove from heat, and, when settled, filter and wash 
 five times with water. Absorb excess of water on blotter and 
 put precipitate in crucible. Char with lid on, then remove it 
 and ignite until white. Weigh as Mn 2 P 2 O 7 . 
 Use precautions for lead or barium. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Weigh off 0.9404 gram of iron, dissolve in 25 cc. of a mixture 
 of 28 parts of nitric acid (sp. gr. 1.20) and 12 parts of dilute 
 sulphuric acid (i : i). As soon as solution is complete, evapo- 
 rate over burner. Use a 4^-inch evaporating dish. When dry, 
 raise the heat until copious fumes of sulphur trioxide escape. 
 Cool, add a few cc. of dilute hydrochloric acid (3:5) and 25 cc. 
 of hot water. Replace over the lamp until solution is complete. 
 Filter, wash paper once with hot water, then once with dilute 
 hydrochloric acid, and three or four times again with hot water; 
 absorb excess of water from paper and residue with blotting- 
 paper. Place in crucible and burn in a muffle, cool, weigh, and 
 divide by 2. Result silicon. 
 
 DETERMINATION OF SULPHUR IN PIG IRON AND STEEL. 
 
 Evolution Method. Weigh 5 grams, place in a i6-oz. flask, 
 closed with a funnel-tube and exit-tube for gas which is con- 
 nected with a tube extending to the bottom of a i-inch by 10- 
 inch test-tube. This test-tube is filled two- thirds full of a cad- 
 mium chloride solution. In the bottom of the tube is placed 
 about i inch of ammoniacal solution of cadmium chloride. 
 (This is made by dissolving 100 grams in 500 cc. water and 
 adding 500 cc. ammonia ; filter into a 2- gallon bottle and add 
 enough water to make 3 liters and enough ammonia to make 5 
 liters.) After adding i inch of this cadmium chloride solution, 
 fill tube two-thirds with water. To drillings in flask add So cc. di- 
 lute hydrochloric acid (3 : 5), place over an Argand burner and 
 heat until quite warm ; lower the heat until solution is complete, 
 then increase the heat until steam drives all gas from flask. Discon- 
 nect flask and pour the solution from the hot tube with the yellow 
 sulphide into a No. 4 beaker. Wash out the tube with water and 
 
84 /. C. Barrett. 
 
 enough dilute hydrochloric acid to make solution in beaker acid 
 and dissolve the sulphide. This is titrated immediately with a 
 standard solution of iodine which has been standardized with a 
 sulphur standard so as to read percentage. Each o. i cc. = o.ooi 
 per cent, sulphur. While titrating be sure that all sulphide is 
 dissolved. The beaker should be two-thirds full. 
 
 Aqua Regia Method. Weigh 5 grams, place in a No. 4 
 beaker, add a mixture of 5 cc. strong hydrochloric acid and 40 
 cc. strong nitric acid to drillings at once. Heat until 
 solution is complete, add 40 cc. strong hydrochloric acid, trans- 
 fer to a No. 2 beaker or a 4^-inch dish, and evaporate to hard dry- 
 ness. Do not ignite. Cool, add 30 cc. concentrated hydro- 
 chloric acid, dissolve and evaporate to formation of a crust, add 
 10 or 12 drops of hydrochloric acid, dilute, and filter into a No. 2 
 beaker. Wash well and fill beaker three-fourths full, heat to 
 boiling and precipitate with 3 cc. barium chloride solution (25 
 grams to 500 cc. water). Allow to stand over night on a warm 
 plate or sand-bath, then evaporate to formation of scum, add a few 
 drops of hydrochloric acid and dilute with water to about one- 
 half beaker full, evaporate again to scum, add a few drops of 
 hydrochloric acid to redissolve and dilute to two-thirds full with 
 cold water and allow to stand at room temperature over night. 
 Filter through a double filter No. 589, 7 cm., wash well with hy- 
 drochloric acid and water, and burn in an open crucible. Purify 
 this precipitate if necessary. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON AND STEEL. 
 
 Dissolve 5 grams in a 4^-inch dish, using 60 cc. of nitric acid 
 (sp. gr. i. 20) for steel, and 70 cc. for pig iron. When the solu- 
 tion is complete, which will take a few minutes for steel and 
 about twenty minutes to a half hour for pig-iron, evaporate over 
 Argand burner with watch-glass cover, having flame as high as 
 possible without smoking. When nearly dry lower the heat so 
 that any iron that may have splashed up on the watch-glass 
 may be redissolved and carried down into the dish. As soon as 
 dry, remove the watch-glass and heat over the lamp until all acid 
 fumes are gone. Cool and add to pig iron 35 cc. strong hydro- 
 chloric acid, and to steel 30 cc. ; replace the watch-glass and 
 
Ohio Steel Company. 85 
 
 place over a low heat until solution is complete ; then raise the 
 heat and evaporate as rapidly as possible withe over on, until the 
 solution is of a very dark color, and about to adhere to the dish. 
 Remove from lamp, add 5 cc. strong nitric acid, shake about 
 until well mixed and any that adheres to the sides may be dis- 
 solved ; dilute with hot water to about 100 cc., washing off the 
 watch-glass. Filter into a i6-oz. flask, washing paper and resi- 
 due with two per cent, nitric acid and hot water. Add 25 cc. 
 strong ammonia, shake up, and then redissolve with 25 cc. of 
 strong nitric acid, leaving solution but slightly acid. Heat to 
 85 and add 75 cc. ammonium molybdate solution. Shake for 
 five minutes. When well settled, filter through a 9-crn. Munk- 
 tell filter, which has been dried at 110 for one hour, and weigh 
 between watch-glasses. Wash well with 2 per cent, solution of 
 nitric acid and dry at 1 10 for one hour. Weigh between watch- 
 glasses. If arsenic or titanium be present, follow Blair's acetate 
 method after filtering from residue down to the basic acetate 
 precipitate carrying phosphorus. This precipitate is dissolved 
 in a dilute solution of nitric and hydrochloric acids in a small 
 beaker and warmed. Filter from paper, remove hydrochloric 
 acid by evaporation, filter into a i6-oz. flask, and precipitate with 
 ammonium molybdate solution. 
 
 If desirable and thought necessary dissolve yellow precipitate 
 in dilute ammonia, by putting paper and all in beaker. Re- 
 move paper and silica and make magnesium precipitate. 
 
 MANGANESE IN IRON AND STEEL. 
 
 Color Method. Weigh 2 grams iron or steel, place in a i-inch 
 by 10-inch test-tube, add 25 cc. nitric acid (sp. gr. 1.20). When 
 solution is complete and all nitrous fumes are expelled, add about 
 \ gram lead dioxide and boil for two minutes, cool in water, and 
 when settled compare color with that of a standand which has been 
 treated in just the same way, the manganese in the standard being 
 determined gravimetrically. Dilute the standard to twice as 
 many cubic centimeters as percentage of manganese and divide 
 cubic centimeters of all compared with it by 2. It takes some 
 time for solution of pig iron and the solution should be kept 
 over a very low flame so as not to concentrate bulk of solution 
 until solution is complete before adding the lead dioxide. 
 
86 /. C. Barrett. 
 
 Gravimetric Method. Dissolve 5 grams of steel in 60 cc. nitric 
 acid (sp. gr. 1.20), evaporate to a pasty consistency in a No. 4 
 beaker, then add 100 cc. concentrated nitric acid, heat to boil- 
 ing, and precipitate manganese dioxide with potassium chlorate; 
 filter on asbestos and proceed as with manganese in ores. Pig 
 iron is treated in the same way as for phosphorus until filtering 
 into a i6-oz. flask. For manganese it is filtered into a No. 4 beaker 
 and evaporated twice with concentrated nitric acid to a pasty 
 consistency; then 100 cc. of concentrated nitric acid are added, 
 manganese dioxide precipitated with potassium chlorate, and 
 the manganese dioxide treated in the same way as in the case 
 of steel or ores. 
 
 DETERMINATION OF CARBON BY COMBUSTION. 
 
 The steel or iron is dissolved in double chloride of potassium 
 and copper which is dissolved in the proportion of 5 pounds to 
 6 liters of water, and has been filtered first through paper and 
 then through asbestos. 5 per cent, of hydrochloric acid is 
 added to this solution as it is used. For 3 grams of steel use 
 1 80 cc. solution. If no stirring machine is at hand add solution 
 to steel and stir frequently at first and allow to stand over night at 
 room temperature. Then warm on sand-bath, stirring frequently 
 until all copper is in solution. Cool and filter through a boat 
 lined with asbestos, made by burning and grinding up in water, 
 decanting away the murky part, leaving the fine asbestos, which 
 by shaking up in a bottle with water can be easily transferred 
 to a boat to make the felt. The solution of steel is filtered on felt, 
 carefully washed with hydrochloric acid, then warm water until 
 free from hydrochloric acid and copper. The boat with carbon 
 is dried at 80 or 90 for one hour, then burned in oxygen in a 
 platinum tube which contains a coil of platinum gauze and cop- 
 per oxide. 
 
 The combustion train is made up as follows : 
 
 Drying and purifying jars filled with potash through which 
 oxygen passes to combustion-tube ; following the combustion- 
 tube is a U-tube filled on one side with anhydrous cuprous 
 chloride and on the other with anhydrous copper sulphate ; 
 then a [j-tube filled with concentrated sulphuric acid to close 
 
Ohio Steel Company. 87 
 
 the lower part of the (]. Following these are the absorption bulbs 
 (Geissler's potash with drying tube between the bulbs). The 
 bulbs are filled with potash (sp. gr. 1.35 or 1.40) and the 
 drying tube with calcium chloride. Connected with this is a 
 Liebig bulb filled with sulphuric acid to trap. Then comes a 
 calcium-chloride tube used as a protection, but not weighed. 
 Great care is used in always keeping the potash bulb and the 
 calcium-chloride tube filled with fresh material. A blank is 
 always run before each day's series is begun, and this must 
 agree with the first w r eight to within 0.0005 gram. Where a num- 
 ber of combustions are to be made the Geissler and L,iebig bulbs 
 are weighed and then placed in train for the next combustion, 
 using the weight from the last one done until the series is finished. 
 Test the joints each time the apparatus is put together. One of 
 the essential requirements for good results is cleanliness. 
 
 The tube is heated up by lighting the burner nearest the absorp- 
 tion bulbs and then, with oxygen flowing so that bubbles go at the 
 rate of 3 per second, each burner slowly in succession, until the 
 whole tube is red hot, taking about ten minutes. Keep red 
 hot for fifteen minutes. Then cut off oxygen and apply suction 
 with bubbles going at the same rate ; lower the flames for a few 
 minutes, then extinguish them. After suction has run for a 
 half hour the bulbs are ready to weigh. 
 
 DETERMINATION OF SILICON IN STEEL. 
 
 5 grams are dissolved in 50 cc. nitric acid (sp. gr. 1.20) and 35 
 cc. dilute sulphuric acid (i : i ) . Evaporate in a 4^-inch dish over 
 an Argand burner with watch-glass cover until bumping begins; 
 remove cover and stir with rod until it grains or cakes. Dry 
 until copious fumes escape. Cool, add about 20 cc. dilute hy- 
 drochloric acid and 100 cc. water. Heat until solution is com- 
 plete, filter and wash well with hydrochloric acid and hot water, 
 burn, and weigh. 
 
XVI. METHODS USED AT THE LABORATORY OF THE 
 CARNEGIE STEEL CO., DUQUESNE, PA. 
 
 i 
 BY JAMES M. CAMP. 
 
 DETERMINATION OF PHOSPHORUS IN PIG IRON AND STEEL. 
 
 5 grams pig iron or steel are dissolved in 60 cc. nitric acid 
 (sp. gr. i. 20) in a i2-cm. porcelain dish, with watch-glass cover, 
 evaporated to dryness while covered, and heated over a lamp 
 without cover till all acid fumes are driven off. When cool, dis- 
 solve in 30 to 35 cc. strong hydrochloric acid and evaporate 
 with watch-glass cover till excess of free acid is driven off, as 
 indicated by the first appearance of insoluble ferric chloride on the 
 bottom of the dish. This is dissolved by adding 2 or 3 cc. of 
 strong nitric acid and the solution diluted with warm water to 
 about 75 cc., filtered, and washed into asoo-cc. flask, using the 
 2 per cent, nitric acid wash water used in washing the yellow 
 precipitate, to remove the last trace of iron. A slight excess of 
 strong ammonia is then added (about 25 cc.), and then a slight 
 excess of strong nitric acid (about 28 cc. ), till the solution is a 
 clear amber color. 
 
 The solution is heated or cooled to 85 C. and 75 cc. ammo- 
 nium molybdate are blown in by aid of a pipette ; the flask is sha- 
 ken for five minutes and allowed to stand till the supernatant liquid 
 is clear. It is then filtered through a weighed filter that has 
 been dried at 100 to 130 C. and weighed between watch-glasses. 
 The precipitate is washed with water containing 2 per cent, 
 strong nitric acid, dried for one hour, or, till weight is constant, 
 at above temperature, and weighed between watch-glasses, i .63 
 per cent, of weight is taken for phosphorus. 
 
 Ammonium Molybdate Solution. This is made by dissolving 
 225 grams molybdic acid in a mixture of 6oocc. water and 4cocc. 
 strong ammonia, and adding this solution to 2.5 liters nitric acid 
 of i .20 specific gravity. This is kept in a warm place over night 
 and is then ready for use. 
 
Carnegie Steel Company, Duquesne, Pa. 89 
 
 DETERMINATION OF PHOSPHORUS IN ORES. 
 
 The agate-mortar sample is dried at 100 C. for one hour, al- 
 lowed to cool, and 5 grams weighed off into a i2-cm. porcelain 
 dish with watch-glass cover, 50 cc. strong hydrochloric acid 
 added, and the solution allowed to go to dry ness on the sand-bath; 
 30 to 35 cc. strong hydrochloric acid are added, warmed, and when 
 all is in solution evaporated till the first appearance of insoluble 
 ferric chloride. This is dissolved by adding one or two drops of 
 strong hydrochloric acid and the solution diluted with hot 
 water to about 75 cc., and filtered into a 5oo-cc. flask. 
 
 The residue is burned and fused with the mixed carbonates of 
 potassium and sodium, dissolved in hot water, acidified with hy- 
 drochloric acid and evaporated to dryness ; then moistened with 
 dilute hydrochloric acid (1:2), diluted, and filtered intothesame 
 flask with original filtrate, keeping as concentrated as possible. 
 (This gives the silica, perfectly pure, of the five grams of ore, on 
 the filter-paper ready for burning and weighing.) 
 
 A slight excess of strong ammonia is now added and then a 
 slight excess of strong nitric acid, and the process continued in 
 the same manner as for pig iron or steel. 
 
 To save time, the above process is modified as follows : 5 
 grams of the dried ore in a i2-cm. covered porcelain dish are 
 boiled with 50 cc. strong hydrochloric acid for about thirty min- 
 utes, or, till the ore is apparently all in solution, diluted with an 
 equal volume of water, and filtered into another dish of the same 
 size. The residue is burned and fused with the mixed carbo- 
 nates, dissolved in hot water, acidified with hydrochloric acid in 
 the same dish in which the original solution was made, and both 
 solutions allowed to go to dryness on the sand-bath. 
 
 30 cc. strong hydrochloric acid are added to the dish containing 
 the original filtrate, and heated till the excess of hydrochloric acid 
 is driven off ; dilute and filter into a 5oo-cc. flask. The fusion 
 is moistened with dilute ttydrochloric acid, diluted, and when 
 in solution filtered into the same flask with the last filtrate. The 
 process is then carried on as before. 
 
 DETERMINATION OF IRON IN ORES. 
 
 i gram of the agate-mortar sample dried at 100 C. is weighed 
 
90 James M. Camp. 
 
 off into a No. o beaker with watch-glass cover, 20 cc. of strong 
 hydrochloric acid added, and for a 60 per cent, ore 5 cc. of the 
 stannous chloride solution, heated on the sand-bath till all is in 
 solution and the residue is white. While still hot in the same 
 beaker, add cautiously, drop by drop, more stannous chloride 
 solution till the color due to the presence of ferric chloride, has 
 entirely disappeared and then one drop in excess. Transfer to 
 a No. 4 beaker containing about 300 cc. cold water, add 10 
 cc. mercuric chloride solution, and stir ; allow to stand about one 
 minute, and then titrate with potassium bichromate solution, until 
 a drop of the solution added to a drop of potassium ferricyanide 
 solution on a porcelain plate shows no green color on standing 
 one-half minute. The number of cubic centimeters bichromate 
 solution used gives the percentage of iron. 
 
 In case the residue shows presence of iron it is filtered, burned, 
 and fused with mixed carbonates, dissolved in water, and filtered; 
 the oxide of iron on the filter is dissolved in dilute hydrochloric 
 acid and allowed to run into the original solution. 
 
 SOLUTIONS. 
 
 Stannous Chloride Solution is made by dissolving 300 grams of 
 the salt in 500 cc. strong hydrochloric acid and 500 cc. water ; i 
 cc. will reduce about o.i gram iron. 
 
 Mercuric Chloride Solution is made by dissolving 50 grams of the 
 salt in i liter of water. 
 
 Potassium Ferricyanide Solution is made by dissolving about 
 0.05 gram of the salt in 50 cc. water. 
 
 Potassium Bichromate Solution is made by dissolving 8.9 grams 
 of salt per liter of water and standardizing with iron wire, stand- 
 ard steel or ore, and diluting so that i cc. equals one per cent, 
 iron ; proving strength of solution after dilution with the stand- 
 ard steel or ore. 
 
 DETERMINATION OF MANGANESE IN ORES. 
 
 The agate mortar sample is dried for one hour at iooC., al- 
 lowed to cool, and five grams weighed off into a i2-cm. porce- 
 lain dish with watch-glass cover; 50 cc. strong hydrochloric acid 
 are added and the solution allowed to go to dryness on the sand- 
 bath. 
 
Carnegie Steel Company, Duquesne, Pa. 91 
 
 The residue is moistened with dilute hydrochloric acid (1:2), 
 diluted, heated till all is in solution and filtered into a 5oo-cc. 
 graduated flask. The residue is burned and fused with five to 
 ten times its weight of the mixed carbonates of potassium and 
 sodium. If fusion shows presence of manganese it is dissolved 
 in hot water, acidified with hydrochloric acid, evaporated to 
 dryness, taken up as before, and filtered into the same flask with 
 the original filtrate. 
 
 The solution is cooled, diluted to the mark, and, with the aid 
 of an exactly agreeing pipette, 100 cc. (equal to i gram of ore) 
 are taken as many times as desired into No. 4 beakers. 30 cc. 
 strong nitric acid are added, and the solution evaporated to small 
 bulk (10 to 15 cc.). 75 cc. strong nitric acid are now added and 
 the solution heated to boiling, and, while boiling, an excess of 
 potassium chlorate is added in small portions and boiled a few 
 minutes after the final puff. 
 
 The solution is cooled and filtered through a purified asbestos 
 plug with the aid of suction. Beaker and plug are washed twice 
 with strong nitric acid and plug blown back into beaker in which 
 precipitation was made. The filtering tube is washed off with 
 water and dilute hydrochloric acid, to dissolve any adhering 
 precipitate ; 25 cc. strong hydrochloric acid are added ; and 
 then i to 2 cc. dilute sulphuric acid added to precipitate any 
 barium that may be present. 1 The solution is heated to boiling, 
 keeping the beaker constantly agitated to avoid bumping and 
 when all the manganese dioxide is dissolved, filtered into asoo-cc. 
 flask from the suspended asbestos. 
 
 The solution is neutralized with ammonia till a faint perma- 
 nent precipitate of ferric hydroxide is formed, 10 to 15 cc. of a 
 25 per cent, solution of ammonium acetate added, and the solution 
 heated to boiling and set aside to settle. It is next filtered into 
 a 500- cc. flask with the aid of suction, and flask and funnel 
 washed once with hot water. The precipitate is dissolved in dilute 
 hydrochloric acid, into the same flask in which the precipitation 
 
 lAt this stage of the analysis, if there is baryta in the ore, which is usually the case, 
 the nitrate being very insoluble in strong nitric acid, may be precipitated ; conse- 
 quently it will be filtered off with the manganese dioxide, and will ultimately go 
 into solution in the subsequent dilution and boiling with hydrochloric acid. This must 
 be separated by addition of sulphuric acid, and sufficient time allowed to precipitate, or 
 it will be weighed with the manganese as pyrophosphate. 
 
92 James M. Camp. 
 
 was made, and a second basic acetate precipitation, made as 
 before, filtered into the same flask containing the first basic ace- 
 tate filtrate, and the flask and funnel washed twice with hot water. 
 
 The subsequent precipitation can be made in the flask, or the 
 united filtrates are transferred to a No. 6 beaker, carefully 
 rinsing out the flask, and 10 cc. acetic acid added. The solution 
 is heated to boiling, 5 to 10 grams ammonium phosphate 
 crystals added, and the solution stirred till the precipitate as- 
 sumes the well-known crystalline form. 25 cc. strong ammonia 
 are now added and the solution stirred for a few minutes till the 
 precipitate is all crystalline, and set aside to settle. It is now 
 filtered through an n-cm. filter-paper by aid of suction and 
 washed with hot water, burned, and weighed as Mn 2 P 2 O 7 . 38.74 
 per cent, of its weight is manganese. 
 
 When only a single determination is required, one gram can be 
 weighed off and treated as directed for five grams. But if 
 several are to be made and the residue fused, which should be 
 done in all cases, unless absolutely certain that it contains no 
 manganese (as a silicate of manganese exists that looks and 
 burns perfectly white) , then it is preferable to start with five 
 grams as directed. 
 
 DETERMINATION OF MANGANESE IN STEEL AND PIG IRON. 
 
 From 2 to 5 grams of the steel or pig iron are weighed 
 off into a No. 4 beaker with watch-glass cover, the least amount 
 necessary of nitric acid of 1.20 specific gravity for complete solu- 
 tion added, and heated to boiling. When all is in solution the 
 watch-glass cover is removed and the solution evaporated over the 
 lamp till the excess of nitric acid is driven off, as indicated by 
 the first appearance of the insoluble nitrate of iron in the solu- 
 tion ; 75 cc. strong nitric acid are added, the solution heated 
 to boiling, and while boiling an excess of potassium chlorate 
 is added in small portions and boiled a few minutes after the final 
 puff. Cool, and filter through a purified asbestos plug with 
 the aid of suction; the beaker and plug are washed twice with 
 strong nitric acid and the washings returned to the beaker in which 
 the precipitation was made. The filtering tube is washed off with 
 water and dilute hydrochloric acid, to dissolve any adhering 
 
Carnegie Steel Company, Duquesne, Pa. 93 
 
 precipitate, an excess of strong hydrochloric acid added, and 
 the solution heated to boiling till the manganese dioxide is all 
 in solution. It is then filtered from the suspended asbestos and 
 the analysis finished in the same manner as for manganese in 
 ores. 
 
 In case of a pig iron high in silicon, it is preferable to dissolve 
 in hydrochloric acid, evaporate to dry ness to separate silica, 
 moisten with dilute hydrochloric acid, dilute, and filter. To the 
 filtrate, add an excess of strong nitric acid (at least 75 cc., if 5 
 grams of iron were taken), and evaporate to total expulsion of 
 hydrochloric acid. 75 cc. strong nitric acid are added and the 
 solution heated to boiling. While boiling, an excess of potas- 
 sium chlorate is added, and the analysis finished in the same 
 manner as for manganese in steel. 
 
 DETERMINATION OF MANGANESE BY COLOR. 
 
 0.2 gram pig iron or steel, and standard steel of known man- 
 ganese content, are weighed off in i-inch by lo-inch test-tubes; 
 30 cc. nitric acid of 1.20 specific gravity are added to each, the 
 tube heated over an Argand burner till dissolved, and boiled till all 
 the nitrous fumes are driven off. While boiling, about one 
 gram lead peroxide is added, boiling continued for one 
 minute, and test-tubes set in a cold water-bath to settle. When 
 cool, and the supernatant liquid is clear, the tube containing 
 the standard solution is decanted into one of the comparing 
 tubes ; this can be very safely done without losing more than a 
 drop of the solution, and without a particle of the lead peroxide 
 entering the comparing tube. The solution is then diluted to 
 twice the number of cubic centimeters, the standard steel contains 
 hundredths per cent, manganese, and mixed thoroughly . The test 
 pig iron or steel is decanted in like manner into the other com- 
 paring tube, and diluted with cold water to like colors. One- 
 half the reading in cubic centimeters represents hundredths 
 per cent, manganese. 
 
 In case the manganese is high in the sample 0.75 per cent, 
 and upwards the test and standard are each boiled two minutes 
 after the addition of the lead peroxide, otherwise the treatment 
 is the same. 
 
94 James M. Camp. 
 
 DETERMINATION OF SILICON IN PIG IRON. 
 
 Twice the factor weight (0.9404 gram of the drillings) is 
 weighed off into a i2-cm. porcelain dish, and 25 cc. of the mixed 
 acids, nitric and sulphuric, mixed in the proportion of 18 cc. nitric 
 acid (sp. gr. 1.20) and 7 cc. dilute sulphuric acid (i : i) added, 
 heated over an Argand burner till all is in solution, and afterwards 
 to dryness, and finally until dense white fumes of sulphur tri- 
 oxide are given off. It is then allowed to cool, moistened with 
 dilute hydrochloric acid (i : 2), diluted with hot water, and 
 warmed till all is in solution; filtered, washed with hot water and 
 dilute hydrochloric acid till free from iron, burned, and \veighed. 
 One-half the weight in decimilligrams is hundredths per cent, of 
 silicon. 
 
 DETERMINATION OF SULPHUR IN PIG IRON AND STEEL. 
 
 Aqua Regia Method. 
 
 5 grams of pig iron or steel are weighed off into a No. 5 beaker, 
 with a watch-glass cover, and 50 cc. aqua regia added at one time. 
 This is freshly made up, by mixing 45 cc. strong nitric acid to 5 cc. 
 strong hydrochloric acid. When the violent action has ceased, 
 heat is applied till all is in solution, and the solution evapora- 
 ted , still covered , until its bulk is considerably reduced . An excess 
 of strong hydrochloric acid is then added (about 40 cc.) to dis- 
 place all the nitric acid, and the solution after continued evapo- 
 ration is finally transferred to a i2-cm. porcelain dish, and al- 
 lowed to go to dryness on the steam-bath. 35 cc. strong hydro- 
 chloric acid are added and warmed till all is in solution and 
 evaporated till the free hydrochloric acid is driven off, as indi- 
 cated by a film of ferric chloride floating on the surface. This 
 is dissolved by a drop or two of strong hydrochloric acid, di- 
 luted to about 75 cc., and filtered into a No. 2 beaker, washing 
 with hot water and the least amount necessary of dilute hydro- 
 chloric acid to remove the last trace of iron. Heated nearly to 
 boiling, 10 cc. of a 5 per cent, solution of barium chloride are 
 added, and the solution set on a sand-bath and evaporated to 
 the separation of the insoluble ferric chloride as before. 
 
 This is dissolved with a drop or two of strong hydrochloric 
 
Carnegie Steel Company, Duquesne, Pa. 95 
 
 acid, and with a wash-bottle a strong stream of cold water is 
 blown into the beaker, thoroughly stirring up the solution till 
 its volume is about 175 cc. and set aside in a cool place over 
 night. The solution is filtered through a double y-cm. filter, 
 washed with hot water and dilute hydrochloric acid till free 
 from iron, burned in an open crucible, and weighed. 13.756 
 per cent, of its weight is sulphur. 
 
 DETERMINATION OF SULPHUR IN PIG IRON AND STEEL. 
 
 Iodine Method. 
 
 5 grams of pig iron or steel are weighed off into a dry 5oo-cc. 
 flask, provided with a doubly perforated rubber stopper, with a 
 long-stem 4-oz. funnel-tube with a stop-cock, and a delivery-tube 
 bent at right angles, on which a short piece of -^-inch rubber 
 tubing is placed, making connection with a delivery- tube also 
 bent at right angles, reaching to the bottom of a i-inch by 10- 
 inch test-tube, suitably supported. About 10 cc. of the ammo- 
 niacal solution of cadmium chloride are introduced into the test- 
 tube, which is diluted with cold water until the tube is about 
 two-thirds full. 80 cc. of dilute hydrochloric acid (1:2) are 
 poured into the funnel-tube, a file mark on the bulb indicating 
 this amount, which is allowed to run into the flask. The stop- 
 cock is then closed and a gentle heat applied, till the drillings 
 are all in solution, and the flask is then strongly heated until 
 nothing but steam escapes from the delivery-tube. 
 
 The apparatus is then disconnected, and the delivery-tube is 
 placed in the No. 4 beaker in which the titrations are made; the 
 contents of the test-tube are then poured into the beaker, the 
 test-tube filled to the top twice with cold water, the sides of the 
 tube rinsed down with about 25 cc. dilute hydrochloric acid, and 
 filled again with cold water. The total volume of the solution 
 equaling about 400 cc. (both acid and water are supplied from 
 overhead aspirator bottle and suitable rubber connections with 
 pinch-cocks) , the delivery-tube is now rinsed off inside and out 
 with dilute hydrochloric acid, and about 5 cc. starch solution 
 added to the beaker. 
 
 Without waiting for complete solution of the cadmium sul- 
 phide, the iodine solution is run in from a burette, stirring 
 
96 James M. Camp. 
 
 gently, till a blue color is obtained. The solution is then stirred 
 vigorously, keeping a blue color by fresh additions of the iodine 
 solution, till the precipitate of cadmium sulphide is all dissolved, 
 and the proper permanent blue color is obtained. The amount 
 of iodine solution used in cubic centimeters represents hun- 
 dredths per cent, sulphur. 
 
 The Iodine Solution is made by placing in a dry 5oo-cc. 
 flask about 35 grams potassium iodide, 16 grams iodine, and 50 cc. 
 water ; shake, and dilute cautiously until all is in solution ; 
 and finally dilute to 3.5 liters. This is standardized with steels 
 of known sulphur content, so that i cc. equals 0.0005 gram sul- 
 phur. 
 
 The Cadmium Chloride Solution is madeb}' dissolving 100 grams 
 cadmium chloride in i liter of water, adding 500 cc. strong ammo- 
 nia, and filtering into an 8-liter bottle. Two liters of water are 
 now added, and the bottle filled to the 8-liter mark with strong 
 ammonia. 
 
 The Starch Solution is made by adding to one-half gallon boiling 
 water, in a gallon flask, about 25 grams pure wheat starch, pre- 
 viously stirred up into a thin paste with cold water ; this is 
 boiled ten minutes and about 25 grams pure granulated zinc 
 chloride dissolved in water added, and the solution diluted with 
 cold water to the gallon mark. The solution is mixed, allowed 
 to settle over night, and the clear solution decanted into a glass- 
 stoppered bottle for use. 
 
 This solution will keep indefinitely. 
 
 DETERMINATION OF NICKEL IN STEEL. 
 
 Our determinations of nickel are made exclusively in machin- 
 ery steel, pinions, and rolls ; the amount ranges from 2.5 to 3.5 
 per cent. No attempt is made to separate cobalt, as it seldom 
 occurs in the steel, and when present is derived from the nickel 
 ores in inconsiderable amounts. The method is as follows : 
 
 Dissolve i gram of steel in 15 cc. nitric acid (sp. gr. 1.20), in 
 a No. 3 beaker, transfer to a liter flask and dilute with hot 
 water to about 700 cc. Neutralize the excess of acid with am- 
 monia, and add about 15 grams sodium acetate in crystals. Heat 
 to boiling and boil one-half minute; allow precipitate to subside, 
 
Carnegie Steel Company, Duqueme, Pa. 97 
 
 and filter through an u-inch fluted filter, into a large beaker. 
 Drain precipitate thoroughly, perforate filter, and wash precipi- 
 tate back into flask in which precipitation was made, wash filter 
 with dilute hydrochloric acid and water till free from iron; 
 add a slight excess of hydrochloric acid to flask to dissolve all 
 the precipitate, and dilute to about 700 cc. Neutralize and 
 make second basic acetate precipitation and filtration as before. 
 
 Unite filtrates, make faintly ammoniacal, and heat nearly to 
 boiling. If traces of iron separate, filter , and in filtrate pass 
 hydrogen sulphide till the solution smells strongly of the gas. 
 Make slightly acid with acetic acid, testing with litmus paper, 
 and set on steam-bath till the precipitate of nickel sulphide sub- 
 sides. Filter, wash with hot water, burn in the hottest part of 
 the muffle, and weigh as NiO. 78.58 per cent, of its weight is 
 nickel. 
 
 In case copper is present in any appreciable amount, dissolve 
 the precipitate of nickel sulphide in hydrochloric acid with the 
 aid of potassium chlorate, filter from the paper, dilute, warm, 
 precipitate the copper with hydrogen sulphide, let subside, filter, 
 wash, and if desired burn and weigh. To the filtrate add am- 
 monia in slight excess, pass hydrogen sulphide, let precipitate 
 subside, filter, wash, burn, and weigh as NiO, as before. 
 
 DETERMINATION OF CARBON IN STEEL BY COMBUSTION. 
 
 From i to 10 grams of steel are weighed off into a dry beaker 
 of suitable size, and from TOO cc. to 500 cc. of the double chlo- 
 ride of copper and potassium solution added. This is made 
 by dissolving 5 pounds of the double chloride of copper and po- 
 tassium in five liters of water, filtering through a puri- 
 fied asbestos plug, and adding 250 cc., or 5 per cent., 
 strong hydrochloric acid. The beaker is placed on a suit- 
 ably arranged stirring apparatus, making about 250 revolu- 
 tions per minute, and kept at a temperature of about 50 C. till 
 all is in solution. When permissible it is preferred to allow the 
 solution to cool, and the carbonaceous residue to subside before 
 filtering. The solution is then filtered through a perforated 
 platinum boat, with suitable asbestos blanket, and washed once 
 with dilute hydrochloric acid, and then with warm water, allowing 
 
98 James M. Camp. 
 
 all the washings to run from the beaker into the boat. The boat 
 is then dried at about 85 C. and is finally transferred to the 
 platinum combustion-tube. 
 
 The accompanying photograph shows the arrangement of the 
 apparatus. In front of the combustion furnace C is the double 
 purifying train for oxygen and air ; the first tubes, A and A', 
 contain a strong solution of caustic potash of 1.4 specific grav- 
 ity. Solution of this strength is also used in the potash bulbs. 
 Tubes B and B' are filled to the top with stick caustic potash in 
 short pieces. These tubes are connected by means of a three- 
 way tube, with suitably arranged stop-cocks and rubber tubing, 
 with the platinum combustion-tube, resting in a lo-burner fur- 
 nace C. The tube is f of an inch in inside diameter and 17 
 inches long, provided with a gas-tight joint, and prolongations 
 6 inches long and -$ inch internal diameter. 2 inches from 
 the rear end of the tube is placed a coil of platinum gauze 2 
 inches long completely filling the tube, then 2 inches of 
 coarse lump oxide of copper, and 2 inches more of platinum 
 gauze. 
 
 Next to the combustion-tube comes the 6-inch purifying [)-tube 
 D, the first half of which is filled with granulated anhydrous 
 cuprous chloride and the second half with anhydrous copper 
 sulphate. After this comes the special (j-tube E, contain- 
 ing about 10 cc. strong sulphuric acid. The last half of the 
 tube contains broken glass rods to diminish the air space. Then 
 comes the potash bulb B, with a drying tube with ground-glass 
 joint, and filled with freshly burned calcium chloride. After 
 this a potash bulb G, containing strong sulphuric acid, and 
 lastly the safety-tube H, filled with calcium chloride. 
 
 It will be observed that sulphuric acid is used as a drying 
 medium both before and after the potash bulb, as the writer 
 doubts the practicability of constantly moistening the gases to 
 the proper degree with a plug of moist cotton, and prefers rather 
 to dry the gases perfectly before entering the absorption-tube, 
 and by means of the sulphuric-acid tube to catch any moisture 
 taken up from the potash bulb, which will be weighed and its 
 gain added to the gain of the potash bulb. 
 
 The combustion is proceeded with as follows : After the 
 
l -35 
 
ioo Carnegie Steel Company, Duquesne, Pa. 
 
 introduction of the boat into the combustion- tubes, the oxygen 
 is started flowing through the apparatus at the rate of three bub- 
 bles per second in the potash bulb. The burners under the 
 platinum gauze and copper oxide are ignited, and, after the 
 tube has acquired a full red color, the burners in front of the 
 boat are turned on, and finally those under it until the tube 
 throughout is a full red. This is continued for fifteen min- 
 utes, then the oxygen is shut off, the burners extinguished, and 
 air is aspirated or forced through the apparatus, at the same 
 rate as the oxygen, for fifteen minutes. The two tubes are 
 then disconnected, the small caps placed on the ends, and each 
 of them weighed, the gain in the tube containing the sulphuric 
 acid being added to the gain of the potash bulb. Three-elevenths 
 of the total gain is carbon. These weights are taken as the first 
 weights of the succeeding combustion. At the beginning of a 
 series of combustions, a blank analysis is run to get the first 
 weights. 
 
APPENDIX. 1 
 
 BLAST-FURNACE CINDERS AND THEIR ANALYSIS. 2 
 
 BY JAMES M. CAMP, 
 
 Chemist to the Carnegie Steel Company, Duquesne, Pa. 
 
 It is the object of this paper to deal exclusively with the cin- 
 der made in furnaces making Bessemer iron, for the reason that 
 this iron is almost exclusively the product of the furnaces of 
 this region, the largest producers and consumers of the world 
 being found here ; and also for the reason that the writer's ex- 
 perience has been particularly confined to that field. On account 
 of the easy solubility of cinders, and the simplicity of the analy- 
 sis in general, this paper is dedicated to those who know noth- 
 ing of the subject. In it they will find much that is old and, 
 possibly, some few things that are new. 
 
 In the analysis of cinder, like many others, it is of prime 
 importance that the results, to be of service to the furnace mana- 
 ger, be obtained quickly. Consequently, the methods used are 
 those yielding the quickest results with the maximum accuracy, 
 the trifling errors, due to the rapid manipulation, being offset 
 by variations in each cinder flush, and variations from flush to 
 flush. This difference is due to several causes, chief among 
 which are the following : 
 
 i st. Changes in the burden, due to variations in the weights 
 of ore or flux. 2d. Variations, more or less great, in the ore, 
 flux, or fuel, which the method or time of sampling will not 
 show. 3d. Most important, and ever varying changes, due to 
 the reduction of more or less silica to silicon in the hearth, and 
 its consequent absorption by the iron and loss to the cinder. 
 This latter change is due to the variation in the temperature of 
 the hearth, and may be caused by (i) a reduction of the bur- 
 
 1 Additional methods which have been contributed by chemists of the Pittsburg re- 
 gion to the transactions of the Chemical Section of the Engineers' Society of Western 
 Pennsylvania. 
 
 2 Read before the Chemical Section of the Engineers' Society of Western Penn- 
 sylvania, January 21, 1897. 
 
IO2 James M. Camp. 
 
 den, (2) extra coke, or, as is commonly called, a black charge, 
 (3) to a higher or lower temperature of blast, (4) a slip in the 
 furnace with the resulting introduction of cold stock into the 
 hearth, (5) to a reduction in the volume of air forced into the 
 furnace, with its resulting concentration of heat at the hearth, 
 and (6) changes in the moisture content of the air. As a conse- 
 quence of the above changes, sometimes working in unison, and 
 again at variance with each other, the production of cinder 
 within certain close limits, is an unsolved problem. The writer 
 has known one or two instances, when the cinder of two con- 
 secutive days showed exactly the same silica, but the laboratory 
 was credited with this fine piece of metallurgical work. In the 
 selection of samples, individual flushes are sometimes analyzed 
 to represent the day's work, but the practice is bad, for the rea- 
 sons given above, and it is preferable to sample each flush dur- 
 ing the day of twenty-four hours. This is usually done by one 
 of the furnace employees, by breaking equal-sized pieces from 
 the test-mold samples taken during the day. These samples, 
 properly labeled, are delivered at the laboratory early in the 
 morning, and are there crushed in an iron or steel mortar by the 
 boy to whom this task is allotted, and the entire sample passed 
 through a forty-mesh sieve. In case the sample contains iron 
 in the form of shot, these are thrown aside as not being part of 
 the cinder. Only such iron should be shown in the analysis as 
 is present in the form of oxide. Part of the samples, sufficient 
 for the analysis, are then placed in the agate mortar grinding 
 machines, and are there ground till, in the judgment of the 
 analyst, they are sufficiently fine, and the samples, after passing 
 a magnet through them to separate any fine shot iron, are ready 
 for the analysis. 
 
 SILICA. 
 
 In the determination of silica, or as it is commonly called, in- 
 soluble residue, on account of the method of analysis, i gram of 
 the sample is weighed off into an n-cm. porcelain dish, with 
 watch-glass cover; 10 cc. water are added and the powder 
 stirred up until it is all moistened. 10 cc. of strong hydrochloric 
 acid are now added, and if the sample contains much iron, a 
 
Blast- Furnace Cinders and their Analysis. 103 
 
 few drops of nitric acid, and the solution, still covered, evaporated 
 to dry ness over an Argand burner and thoroughly dried. When 
 dry the dish is allowed to cool, and the residue is moistened 
 with about 3 cc. of strong hydrochloric acid, and again evapo- 
 rated to hard dryness. This is an essential point for rapid filtra- 
 tion, as a single evaporation, no matter how well done, does not 
 dehydrate the silica, and a serious loss of time may result in 
 filtering. The dish is again allowed to cool, and the residue 
 taken up with a mixture of 20 cc. strong hydrochloric acid and 
 40 cc. water, the large amount of hydrochloric acid being 
 added to form ammonium chloride in the subsequent part of the 
 operation. The dish and its contents are heated to near the 
 boiling-point for a few minutes, and filtered through a 9-cm. 
 filter, washed with hot water till free from chlorine, burned and 
 weighed. The native Bessemer ores used at present are practi- 
 cally free from barium, consequently volatilization of the silica 
 with hydrofluoric acid is not needed. 
 
 The following are some comparative results by the above 
 method, and those obtained by carbonate fusion, solution in 
 water, acidifying with hydrochloric acid, evaporating to dryness 
 and treating as usual : 
 
 Insoluble residue by solution. Silica by fusion. 
 
 No. Per cent. Per cent. 
 
 1 31.09 31.29 
 
 2 31.67 31.65 
 
 3 31-55 31.50 
 
 4 30.47 30.5 
 
 5 31-75 31-96 
 
 6 29.38 29.50 
 
 7 30-26 30.37 
 
 8 30.37 30.50 
 
 9 3-74 30.75 
 10 31.40 31.34 
 
 IRON OXIDE AND ALUMINA. 
 
 Alumina. The filtrate from the silica, in a No. 3 beaker, 
 with a watch-glass cover, is heated to boiling, and a slight excess 
 of strong ammonia added, and the solution boiled for a few min- 
 utes. The beaker is then removed from the heat and placed in a 
 cold water-bath to cool and for the precipitate to settle. When the 
 
IO4 James M. Camp. 
 
 precipitate has settled completely, filter and wash, by decantation 
 through an n-cm. filter, keeping the paper full until the precipi- 
 tate is reached. Then let the funnel drain and pour the precipi- 
 tate on the filter with a steady stream until the beaker is drained. 
 Wash with hot water until free from chlorine, burn, and weigh 
 as iron and aluminum sesquioxides. 
 
 Iron. Into a No. 2 beaker, without lip and with a watch-glass 
 cover, there had been previously weighed off i gram of the 
 original sample; to this was added 30 cc. of water and 20 cc. 
 of strong hydrochloric acid, and set on the steam-bath to 
 dissolve. This solution is now boiled for a few minutes till 
 all is dissolved, and the hydrogen sulphide all driven off. To 
 this, while still hot, a slight excess of stannous chloride is added 
 (abqut three drops), as the iron is all present in the ferrous 
 form, and the solution diluted with cold water to about 300 cc. 
 10 cc. of the mercuric chloride solution are now added, the solu- 
 tion is stirred, and after waiting one minute it is titrated with 
 potassium bichromate solution, as previously described before this 
 society. 1 The iron is reported as iron, but subtracted as sesqui- 
 oxide from the iron oxide -f- alumina obtained before. 
 
 UME. 
 
 The filtrate from the alumina in a No. 4 beaker is heated to 
 boiling and 25 cc. of a saturated solution of ammonium oxalate 
 added, and 10 cc. of strong ammonia. This is boiled for a few 
 minutes, removed from the heat and the precipitate allowed to 
 settle. It is then filtered through an n-cm. filter, washed with 
 hot water till free from chlorine, and burned in a muffle furnace, 
 allowed to cool in a desiccator, and weighed as lime. The heat 
 of a muffle furnace, at an ordinary red heat, will thoroughly de- 
 compose calcium oxalate, for in no other case after treating as 
 above, and then heating at the highest temperature of the blast- 
 lamp, was there found a greater difference than 1.2 per cent. 
 In case the cinder is high in magnesia, due to the use of all or 
 part dolomite as a flux, a double precipitation is made of the 
 lime as oxalate. 
 
 1 Transactions Engineers* Society Western Penna., Vol. XI. 
 
Blast- Furnace Cinders and their Analysis. 105 
 
 MAGNESIA. 
 
 The filtrate from the lime, which need not exceed 400 or 500 
 cc., in a No. 5 beaker, is cooled by placing it in a cold water- 
 bath, and slightly acidulated with hydrochloric acid, about 5 cc. 
 For a cinder containing not over 8 per cent, of magnesia, 10 cc. 
 of a 10 per cent, solution of sodium phosphate are added, and 
 gradually from a measure, with constant stirring, 50 cc. of strong 
 ammonia. Stir thoroughly and at intervals for two or three 
 hours, then filter, wash with dilute ammonia (1:3) till free 
 from chlorine, burn, and weigh. 
 
 MANGANESE. 
 
 The behavior of manganese in the furnace is similar to that of 
 silicon. The higher the heat the more of the oxides are reduced 
 and alloy with the iron, and per contra, the lower the heat, the 
 less are reduced, and remain in the cinder. In the method de- 
 tailed above no attention has been paid to this element, part of 
 the manganese being weighed with the oxide of iron and 
 alumina, and part with the lime. The amount in the cinder is, 
 as a rule, low, and the trifling error introduced does not affect 
 the metallurgical value of the results. Many determinations 
 have been made, by the writer, of manganese in the iron and 
 alumina and lime precipitates, as determined above, and in 
 separate samples of the cinder, with the object of finding a rule 
 whereby a certain amount of the total could be deducted from 
 each, but without avail. And in case an accurate, complete 
 analysis is desired, instead of an ammonia precipitation of the 
 iron and alumina, a double basic acetate precipitation must be 
 made, and the manganese precipitated in the united filtrates 
 with bromine, before precipitating the lime. For some time past 
 the writer has been using the colorimetric method on cinders, 
 exactly as it is used for the determination of manganese in pig 
 iron and steel, with very satisfactory results. 
 
 Herewith are given some comparative results, using the color- 
 imetric method and those obtained by the potassium chlorate 
 method : 
 
io6 James M. Camp. 
 
 Colorimetric. Potassium chlorate. 
 
 No. Per cent. Per cent. 
 
 1 0.40 0.42 
 
 2 0,41 0.40 
 
 3 0.31 0.29 
 
 4 0.35 0.33 
 
 5 0.47 0.48 
 
 6 0.23 O.22 
 
 7 0.27 0.26 
 
 8 0.30 0.31 
 
 9 0.33 0.32 
 10 0.36 0.36 
 
 SULPHUR. 
 
 A blast-furnace cinder will contain practically all the sulphur 
 of the ore, flux and fuel, less the amount contained in the iron, 
 which amount is dependent on the temperature of the hearth. 
 The higher the temperature the lower the sulphur, and vice versa. 
 Cinders will vary in sulphur under normal conditions of ore and 
 fuel, from i to 2 per cent., depending on the proportion of 
 cinder produced to the ton of iron. The determination is 
 effected as follows : Into a dry half-liter flask, introduce about 
 \ inch, equal to about 5 grams of chemically pure stick zinc, 
 and then 0.25 gram of the cinder. The flask is provided with a 
 doubly perforated rubber stopper. Through one opening a funnel- 
 tube is placed, reaching to the bottom of the flask, and through the 
 other a short piece of glass tubing, bent at right angles, and 
 connected by a short piece of rubber tubing to the delivery-tube, 
 also bent at right angles, reaching to the bottom of a i-inch by 
 lo-inch test-tube, into which about 10 cc. of the ammoniacal 
 solution of cadmium chloride are introduced, and the test-tube 
 filled about three-fourths full of cold water. 10 cc. of water are 
 now added to the flask, and gently shaken till the cinder is 
 moistened, to prevent caking on the bottom.. The apparatus 
 is connected, and 50 cc. of dilute hydrochloric acid added, one of 
 acid to two of water. The cinder is dissolved almost instantly, 
 liberating a large volume of hydrogen sulphide. 
 
 The compact zinc dissolves more slowly, liberating hydrogen, 
 which gradually displaces the hydrogen sulphide, and carries it 
 over to the absorbent. A gentle heat is applied, which is grad- 
 
Blast- Furnace Cinders and their Analysis. 107 
 
 ually increased until the zinc is dissolved, and nothing but 
 steam escapes from the delivery-tube. The apparatus is then 
 disconnected, and the solution titrated with iodine, using the 
 same solution as is used for the determination of sulphur in iron 
 or steel. 
 
 The following are some results obtained as described above 
 and those obtained by fusion with the mixed carbonates and niter 
 solution, evaporation to dryness, solution, filtering, and precipita- 
 ting with barium chloride : 
 
 Titrating with iodine. Weighing as 
 
 The evolved hydrogen sulphide. barium sulphate. 
 
 No. Per cent. Per cent. 
 
 1 1-55 1.56 
 
 2 1.65 1.63 
 
 3 1-57 1-59 
 
 4 1.67 1.69 
 
 5 1-58 1.59 
 
 6 1.93 1.96 
 
 7 1.64 1.62 
 
 8 1.80 1.79 
 
 9 1.82 1.83 
 10 1.80 1.82 
 
 PHOSPHORUS. 
 
 Phosphorus, under normal conditions of temperature, is prac- 
 tically all reduced in the hearth of the furnace, and there com- 
 bines with the iron, the amount remaining in the cinder varying 
 from a trace up to 0.02 per cent., the average being much nearer 
 the former than the latter figure. The determination is as fol- 
 lows : 
 
 10 grams of the cinder are weighed off into a i2-cm. porcelain 
 dish with a watch-glass cover, and stirred up into a paste with 
 water. 50 cc. of strong hydrochloric acid are now added and 2 
 cc. of nitric acid, and the solution evaporated to hard dryness. 
 The dish is allowed to cool and then moistened with about 25 
 cc. strong hydrochloric acid, and again evaporated to hard dry- 
 ness. When cool, from 15 to 20 cc. strong hydrochloric acid 
 are added, sufficient to moisten the residue, and the dish and its 
 contents warmed for a few minutes, and diluted with warm water 
 to about 100 cc. This is filtered through an ii-cm. filter into a 
 half-liter flask, and slightly washed with hot water. To the fil- 
 
 U2STIV 
 
io8 Blast- Furnace Cinders and their Analysis. 
 
 trate a slight excess of strong ammonia is added, about 25 cc., 
 and then a slight excess of strong nitric acid, and the solution 
 heated to 85 C. and 75 cc. of ammonium rnolybdate solution 
 blown in by aid of a pipette. The flask is shaken for about five 
 minutes, and the yellow precipitate collected and weighed the 
 same as in ores, pig iron, or steel. 
 
 This analysis, like the determination of alkalies which are 
 ever present in cinders, has no known metallurgical significance, 
 for they are beyond control, and are rarely 'if ever determined, 
 except for the gratification of idle curiosity, and in a furnace and 
 steel works laboratory so much is wanted that is essential to the 
 proper metallurgical operation of the plant, that scant time is 
 left for work which is not essential. 
 
BARIUM HYDROXIDE AS AN ABSORBENT IN CARBON 
 DETERMINATIONS. ' 
 
 BY A. G. MCKKNNA, 
 
 Chemist to the Sterling Steel Company, Demmler, Pa. 
 
 In the determination of carbon in iron or steel, potassium 
 hydroxide has been commonly used as an absorbent for the 
 carbon dioxide formed by combustion of the carbonaceous res- 
 idue left after treatment of the metal by an appropriate solvent. 
 In the somewhat similar determination of carbon dioxide exist- 
 ing in the atmosphere, barium hydroxide has been almost uni- 
 versally employed as the absorbent. As the use of the latter ab- 
 sorbent offers some striking advantages over potassium hydrox- 
 ide, the society may be interested in a number of experiments 
 showing what precautions are necessary if barium hydroxide is 
 used in the combustion method. 
 
 The apparatus employed in all the experiments consisted of a 
 platinum combustion-tube containing copper oxide and platinum 
 gauze arranged as usual to insure complete oxidation of the car- 
 bon to carbon dioxide with the customary means for purifying 
 the current of oxygen and air from carbon dioxide before enter- 
 ing the tube. The barium hydroxide, to absorb the products of 
 the combustion, was contained in an absorption- tube consisting 
 of a series of ten bulbs as shown in the sketch. 
 
 In the first experiments the fixed carbon from a coke was used 
 as a material for combustion. A known amount was weighed 
 into a platinum boat which was then inserted into the tube. 
 The absorption-tube containing 100 cc. of a solution of barium 
 hydroxide of known strength was next attached directly to the 
 combustion-tube through which a slow current of oxygen was 
 forced. The burners were now lighted in the usual order and 
 the combustion continued for fifteen minutes, at the end of which 
 time the burners were extinguished, but the current of oxygen 
 was continued for another fifteen minutes in order to carry all 
 carbon dioxide into the absorption- tube. The tube was now 
 
 i Read before the Chemical Section of the Engineers' Society of Western Pennsylva- 
 nia, March 15, 1895. 
 
no A. G. McKenna. 
 
 disconnected and its contents filtered into a flask, using a gentle 
 suction so as to bring as little air as possible in contact with the 
 solution. In washing it was found necessary to free the wash 
 water from carbon dioxide by boiling just previous to use. The 
 filtrate in the flask was now titrated with standard sulphuric 
 acid, using phenol-phthalein as an indicator. The end-point is 
 remarkably sharp and distinct. The sulphuric acid used was 
 ^ normal, in which i cc. 0.0003 gram carbon. If the bar- 
 ium hydroxide solution is also made ^\ normal, the difference be- 
 tween loo cc. and the number of cubic centimeters of sulphuric 
 acid used in the titration multiplied by 0.3 will give the milli- 
 grams of carbon in the sample. 
 
 If the barium hydroxide is stronger or weaker it is simply 
 necessary to substitute in the calculation for 100 cc. the equiva- 
 lent amount of barium hydroxide used. The following results 
 were obtained by the coke combustion : 
 
 Amount taken. Amount found by titration. 
 
 Gram. Gram. 
 
 0.0007 0.0075 
 
 0.0256 0.0250 
 
 0.0298 0.0290 
 
 Two grams of a steel containing i .07 percent, carbon were now 
 dissolved in 150 cc. of a 50 percent, solution of copper potassium 
 chloride containing 5 percent, of concentrated hydrochloric acid. 
 The solution was kept agitated for one hour at a gentle heat by 
 means of a stirring apparatus. It was then allowed to remain 
 quiet for several hours and filtered on asbestos in a platinum boat, 
 washing with dilute hydrochloric acid, and then with hot water. 
 The carbonaceous residue was burned without drying, exactly 
 as the coke had been. The results were i.n and 1.12. As 
 these results are decidedly high (the results using potassium 
 hydroxide as an absorbent being 1.072 percent., 1.068 percent., 
 i .066 per cent. , i .070 per cent. ) , several combustions were made 
 on sugar with the following results : 
 
 Amount taken. Amount found by titration. 
 
 Gram. Gram. 
 
 0.0168 0.0164 
 
 0.0162 0.0160 
 
 0.0188 0.0185 
 
 0.0170 0.0166 
 
Barium Hydroxide as an Absorbent. in 
 
 Another series of combustions on standard steels gave the fol- 
 lowing results, the barium carbonate precipitate being weighed 
 after ignition as well as the solution titrated : 
 
 Pound by Found by Found by 
 
 potassium hydroxide. titration. weighing barium carbonate. 
 
 Per cent. Per cent. Per cent. 
 
 0.489 0.484 
 
 0.477 0.471 
 
 0.325 0.310 
 
 0.205 - I 93 
 
 o.i 10 0.103 
 
 It will be seen that in general the results are just a trifle low 
 on carbon from other sources than steel, while the results on 
 steel are distinctly higher by titration, and a trifle high by 
 weight. 
 
 The cause of the errors in steel was traced to the formation of 
 sulphurous and sulphuric acid from the carbonaceous residue. 
 To obviate this error a solution of potassium permanganate in 
 sulphuric acid was interposed between the combustion- tube and 
 the barium hydroxide. With this form of apparatus the follow- 
 ing results were obtained, the combustion being made as before, 
 but thirty minutes being used to aspirate : 
 
 Found by Found by Found by 
 
 potassium hydroxide. titration. weighing barium carbonate. 
 
 Per cent. Per cent. Per cent. 
 
 f 0.603) f } f | 
 
 \ 0-599 \ \ 0-60 \ \ 0.595 \ 
 
 (0.594) (0.599 J 1 0.594 J 
 
 0/177 / 0-473 \ / 0.470 \ 
 
 ' 477 10.470 / \ 0.465 I 
 
 In order to test decisively this theory of the causes of errors, four 
 more determinations were made using ten grams in each of a 
 soft steel containing 0.075 per cent, carbon. Two of these com- 
 bustions were made without interposing any permanganate. 
 The results were : 
 
112 Barium Hydroxide as an Absorbent. 
 
 Pound by 
 
 Found by titration. weighing barium carbonate. 
 
 Per cent, carbon. Per cent, carbon. 
 
 0.084 0.080 
 
 0.084 0.079 
 
 The precipitates of barium carbonate were now dissolved in 
 hydrochloric acid and filtered. The barium sulphate found in the 
 first case weighed 0.0095 g r am, and in the second case 0.0075 
 gram. The results of the combustion corrected by these amounts 
 give respectively 0.075 per cent, and 0.074 per cent. 
 
 The other combustions, interposing permanganate, gave the 
 following results : 
 
 Found by 
 
 Found by titration. weighing barium carbonate. 
 
 Per cent, carbon. Per cent, carbon. 
 
 O.oSl 0.075 
 
 0.080 0.075 
 
 The barium carbonate obtained from these combustions con- 
 tained nothing insoluble in hydrochloric acid. 
 
 In conclusion I would say that it will be found much simpler to 
 burn and weigh the barium carbonate rather than to titrate. 
 The high combining weight of barium renders it possible to 
 weigh extremely small amounts of carbon when present as bar- 
 ium carbonate. 
 
AN IMPROVEMENT IN THE ZINC REDUCTOR FOR 
 
 THE DETERMINATION OF IRON OR 
 
 PHOSPHORUS. 1 
 
 BY A. G. MCKENNA, 
 
 Chemist to the Sterling Steel Co., Demmler, Pa. 
 
 In using the ordinary form of reductor, for reducing solutions 
 of iron or molybdic acid by passing through a column of finely 
 granulated zinc, an enormous amount of zinc is consumed in 
 the useless reaction between the free acids necessarily present 
 and the zinc, while a comparatively small amount takes part 
 in the reaction by which the iron or molybdic acid is reduced. 
 
 The reactions spoken of are 
 
 Fe,(S0 4 ) 8 + Zn = 2FeSO 4 + ZnSO 4 
 and H a S0 4 + 2Zn = ZnSO 4 + H 3 . 
 
 The great volume of hydrogen set free by the second reaction 
 proves very annoying during the operation of reduction, and 
 unless an extremely powerful suction is used, the liquid can 
 scarcely be drawn through the zinc. 
 
 As it is known that zinc which has been amalgamated is 
 scarcely attacked by weak acid, it occurs to the writer to try the 
 effect of amalgamating the granulated zinc before using it in the 
 reductor. 
 
 The results were most satisfactory. The reaction between the 
 zinc and the free acid was almost entirely suppressed, there being 
 scarcely any evolution of hydrogen during the passing of the 
 solution through the zinc, while the speed of the reduction was 
 not in the least diminished. 
 
 The form of apparatus used is shown in the accompanying 
 sketch. In preparing it for use a small plug of asbestos is 
 placed in the bottom of the tube just above the stop- cock. A 
 very thin layer of asbestos will be found sufficient. It should be 
 packed loosely so that a steady stream of water will run through 
 without suction. On this plug about 200 grams of granulated 
 
 1 Read before the Chemical Section of the Engineer's Society of Western Pennsyl- 
 vania, September 29, 1895. 
 
An Improved Zinc Reductor. 115 
 
 zinc are placed. The zinc should be of such fineness that it will 
 pass through a 2o-mesh sieve but not through a 3O-mesh. Be- 
 fore placing it in the reductor it is thoroughly amalgamated by 
 stirring up with it, in a small beaker, about 5 grams of mercury 
 and 25 cc. of a 5 per cent, solution of sulphuric acid. The zinc 
 fills the straight part of the tube about two- thirds full, leaving a 
 sufficient space to allow the addition of the solution which is to be 
 reduced. After the zinc is in position the tube is inserted in a 
 filtration flask by means of a rubber stopper and the flask con- 
 nected with the suction. The zinc is washed several times with 
 a 5 per cent, solution of sulphuric acid and is then ready for use. 
 
 For the determination of iron in ores, the solution of the ore 
 after the excess of free hydrochloric acid has been driven off, is 
 diluted and filtered into a 5<x>-cc. graduated flask and diluted to 
 the mark with water after cooling. By means of a ico-cc. 
 pipette, 100 cc. are transferred to a small beaker ; 5 cc. of a 50 
 per cent, solution of sulphuric acid are added and the contents of 
 the beaker are poured into the reduction-tube, the glass stop- 
 cock being opened sufficiently to allow the solution to be drawn 
 through by a gentle suction. There will be scarcely any evolu- 
 tion of gas, and the reduction will be complete even though the 
 solution runs through in a steady stream. The tube is now 
 washed four times with a 5 per cent, solution of sulphuric acid, 
 using in each washing about 50 cc. of solution. It is important 
 during the washing to avoid drawing successive amounts of air 
 through the zinc, as, for reasons stated below, this will lead to 
 low results. The reduced solution is now titrated by standard- 
 ized permanganate and a duplicate determination is made on 
 another 100 cc. taken from the graduated flask. These dupli- 
 cates should agree within o. i per cent. 
 
 In some of the first experiments it was found that a blank 
 made by washing five successive portions of 5 percent, sulphuric 
 acid through the tube, allowing a current of air to be drawn 
 through for a half minute between the washings, required an 
 amount of permanganate equivalent to 0.003 gram of iron, 
 although no iron could be found in the solution. Blanks made 
 in a similar way, except that no air was drawn through the 
 tube, were colored by the first drop of permanganate. Dupli- 
 
n6 An Improved Zinc Reductor. 
 
 cate determinations of iron, allowing in one case air to be drawn 
 through and in the other not, invariably gave results from 0.2 to 0.3 
 per cent, low, in the cases in which air was drawn through alter- 
 nately with the sulphuric acid. The facts evidently point to 
 the formation of some compound which oxidized iron and was 
 itself oxidized by permanganate. A test for hydrogen peroxide 
 was made in one of the blanks by adding a few crystals of 
 potassium iodide ; on standing a few minutes the solution began 
 to show the characteristic color of free iodine. On titration with 
 hyposulphite it was found that 0.0009 gram hydrogen peroxide 
 was present in the blank. This amount of hydrogen peroxide 
 would be sufficient to oxidize about 3 mgms. of iron. In regard 
 to the amount of zinc consumed in the reduction of a gram of 63 
 per cent, ore, it may be said that a determination of the zinc 
 in the solution after complete reduction, gave 0.6 gram of zinc. 
 
ON SOME EVOLUTION METHODS FOR SULPHUR IN 
 IRON AND STEEL. 
 
 BY W. E. GARRIGUES. 
 
 By utilizing the property of caustic alkali to effectually check 
 a current of hydrogen sulphide, followed by oxidation after 
 washing out the single test-tube necessary for absorbing the gas, 
 a clean and inoffensive solution is rapidly prepared for final pre- 
 cipitation. 
 
 The evolution is conducted exactly as for the iodine titration 
 except that 10 grams of the drillings are used in place of 5. 
 The absorbing liquid is 10 per cent, caustic soda, and 65 cc. 
 are used for a determination, being contained in a single test- 
 tube, to the bottom of which the delivery-tube dips. 
 
 50 cc. of water are poured on the drillings in the flask, fol- 
 lowed by 40 cc. strong hydrochloric acid, the heat of the reac- 
 tion starting a brisk evolution of gas at once. After com- 
 plete solution of the metal and boiling, the test-tube is rinsed 
 into a beaker, 10 cc. of 5 per cent, potassium permanganate 
 added and heated to boiling ; this completes the oxidation. 
 20 cc. of strong hydrochloric acid are next poured in, followed 
 by 15 cc. saturated oxalic acid, which leaves the liquid clear and 
 colorless. Neutralize the ammonia, just clearing with hydro- 
 chloric, and precipitate boiling with barium chloride. The neu- 
 tralization seems to be necessary. 
 
 Bromine was tried before permanganate, but gave indication 
 of low results. The possibility of correcting this error seems as- 
 sured, but bromine is sufficiently unpleasant to let alone when 
 something else will answer equally as well. 
 
 The figures obtained on a sample of steel by the above two 
 methods of oxidation, the evolution being identical, and also by 
 the aqua regia method, follow : 
 
 Potassium 
 
 Aqua regia. Bromine. permanganate. 
 
 0.048 ( 0.042 0.046 
 
 0.049 1 -42 0-046 
 
 2 { 0.045 0.047 
 / 0.047 0.048 
 
 3 \ 0.047 0.049 
 
 i. w5 
 
n8 W. E. Garrigues. 
 
 The bromine results need an explanation. 
 
 No. i was oxidized as follows : Bromine water added to alka- 
 line solution, heated to boiling, acidified, and bromine boiled off. 
 
 No. 2 ditto, except alkaline solution boiled one-half hour 
 after addition of bromine. 
 
 No. 3 ditto, boiled one hour. 
 
 The one objection to alkaline oxidation methods is the prac- 
 tical impossibility of obtaining caustic soda free from sulphur in 
 some form. This necessitates subtracting a " blank." Some 
 attempts to get rid of the sulphur were only partly successful ; 
 using a saturated solution as a basis (obtained in exactly the 
 same manner as was described for getting rid of carbonate in the 
 first part of this paper), reduced the blank from 16 to 7.7 mgms. 
 Adding excess of barium chloride and letting stand two days 
 reduced it to only 12.1 rngms. The saturation process is recom- 
 mended, the clear liquid being diluted to 15 B., at which density 
 it contains about 10 per cent, of sodium hydroxide. 
 
 The above-described process should be especially advan- 
 tageous in the accurate analysis of pig-iron, where the sulphur 
 content of the residue is to be determined. In that case there 
 is certainly no advantage in titrating the evolved sulphur with 
 iodine and then working the residue gravimetrically ; instead 
 the two are combined and only one precipitation made. 
 
 As to the iodine titration of the evolved sulphur arrested by 
 caustic alkali, some experiments warrant the conclusion that the 
 method is a strictly empirical one, not depending upon complete 
 reactions like the gravimetric results. 
 
 In other words the equation, 
 
 in which 253.7 iodine are equivalent to 32 sulphur, cannot be 
 assumed as a basis for calculating the sulphur value of an iodine 
 solution of known strength. The results thus obtained, when 
 caustic alkali is used, are always too low. 
 
 A solution standardized empirically, /. e., against a steel of 
 known sulphur content, will contain less iodine than one stand- 
 ardized by calculating from its oxidizing power. As the equa- 
 tion before stated is the simplest which can be assumed to take 
 
Evolution Methods for Sulphur. 119 
 
 place between hydrogen sulphide and iodine, the least possible 
 amount of iodine as compared to sulphur entering into it, the 
 choice of two explanations remains to account for the discrep- 
 ancy : ( i ) The sulphur is not all evolved from the steel as hy- 
 drogen sulphide, and (2) the hydrogen sulphide is partly oxi- 
 dized to sulphuric acid in the alkaline solution during evolu- 
 tion. 
 
 Kxperiment No. i must be dropped for the reason that when 
 cadmium chloride is used the whole of the sulphur evolved pre- 
 cipitates as cadmium sulphide, and again becomes hydrogen 
 sulphide on acidifying, as shown by its requiring the full theo- 
 retical quantity of iodine. The suggestion of partial oxidation 
 alone remains then, to account for the shortage, it having been 
 proved by direct experiment that no hydrogen sulphide escapes 
 during titration. The means of doing this was to add at once 
 an excess of iodine and then titrate back with sodium thiosul- 
 phate. 
 
 Following are results obtained on the same sample of steel men- 
 tioned before, and shown to contain about 0.048 per cent, sul- 
 phur. The absorption in caustic alkali was carried out in 
 precisely the same manner as were the gravimetric analyses 
 previously recorded : 
 
 Caustic soda absorption. Cadmium chloride. 
 
 Direct with iodine. Back with sodium thiosulphate. 
 
 0.038 0.039 0.047 
 
 0.039 -39 0-047 
 
 0.042 8.041 0.049 
 
 Similar results were obtained by the sodium hydroxide method 
 on standard samples kindly furnished by Mr. Camp and Mr. 
 Handy, all of which were sufficiently concordant to have been 
 apparently correct had any one of the samples been used for 
 standard titrating solution instead of taking its theoretical value. 
 They did not, however, agree among themselves quite as well 
 as either the gravimetric results or those obtained volumetrically 
 with cadmium chloride as an absorbent, the series above given 
 being rather better than the average. Both absorbents gave a 
 blank titration equivalent to 0.002, which was subtracted. To 
 sum up : An iodine solution cannot be used indiscriminately for 
 
I2O Evolution Methods for Sulphur. 
 
 titrating sulphur evolved into caustic alkali and cadmium chlo- 
 ride. The former requires a standard steel as a basis of calcu- 
 lating, all evolutions being made as nearly as possible under the 
 same conditions, while the latter can be interpreted from the 
 theoretical value of the iodine solution, the results agreeing more 
 closely among themselves and being obtained with less attention 
 to minute details. Hence the cadmium chloride is recommended. 
 
THE DETERMINATION OF CHROMIUM. 1 
 BY A. G. MCKKNNA, 
 
 Chemist to the Sterling Steel Co., Demmler, Pa. 
 
 The following method for the determination of chromium in 
 steel will be found more accurate and rapid than any of the pub- 
 lished methods known to the writer. By its use he has made 
 several thousand chromium determinations with uniformly satis- 
 factory results. 
 
 The process is based upon the well-known fact that chromic 
 salts can be oxidized completely to chromic acid by the addition 
 of potassium chlorate to a concentrated nitric acid solution, and 
 the fact, not so well known, that the presence of nitric acid does 
 not interfere with the titration of chromic acid in a cold solution 
 by means of ferrous sulphate and permanganate. 
 
 In case the steel contains manganese and a determination of 
 the same is wanted in addition to the determination of chromium, 
 the method is as follows : Weigh 3 grams of steel into a 400- 
 cc. flask, add 35 cc. of strong hydrochloric acid and boil for five 
 or ten minutes, which will be found sufficient to dissolve com- 
 pletely even the highest chrome steels. When most of the hy- 
 drochloric acid is boiled off, add 150 cc. strong nitric acid, and 
 continue the boiling until no more brown fumes are seen at the 
 mouth of the flask, showing that the hydrochloric acid has all 
 been driven off. Remove the flask from the flame or hot plate, 
 allow to cool for two or three minutes, and then add 10 grams of 
 potassium chlorate in crystals. It is best to allow the solution 
 to cool slightly before adding the chlorate in order to diminish 
 the violence of the effervescence due to the action of the chlorate 
 on the chromic salts. Replace on the hot plate and boil down 
 to about 40 cc. in order to decompose completely the potassium 
 chlorate. It is necessary to decompose the chlorate completely 
 
 1 Read before the Chemical Section of the Engineers' Society of Western Pennsylva- 
 nia, June 18, 1896. 
 
122 A. G. McKenna. 
 
 or results will be from o.i to 0.2 per cent, high, but the amount 
 of nitric acid left in the solution is not important. At this stage 
 the chromium will all be in the solution in the form of chromic 
 acid. The manganese will be precipitated as dioxide and gen- 
 erally some crystals of potassium nitrate arising from the decom- 
 position of the chlorate will have separated out. Filter off the 
 manganese dioxide on an asbestos plug, washing the precipitate 
 three times with cold water. Transfer the asbestos and the 
 manganese dioxide to the flask, in which the original precipita- 
 tion was made, titrate with ferrous sulphate and permanganate, 
 according to Williams' well-known modification of Ford's 
 method. 
 
 Make the filtrate from the manganese dioxide which contains 
 all the chromic acid in a nitric acid solution up to about 
 500 cc. with cold water, and add standardized ferrous sulphate 
 solution in slight excess indicated by the disappearance of the 
 yellow color of the chromic acid and the appearance of the clear 
 green color of chromic nitrate ; then add standardized perman- 
 ganate to oxidize the excess of ferrous sulphate used, the end- 
 point being the well-known faint pink color. 
 
 The standard ferrous sulphate is made by dissolving iron wire 
 of known purity in an excess of dilute sulphuric acid, diluting 
 with water until i cc. contains 0.003223 gram of iron in the fer- 
 rous condition. 
 
 The permanganate solution is made by dissolving 1.8 18 grams 
 of pure potassium permanganate in a liter of water ; i cc. of 
 the permanganate solution will then oxidize exactly i cc. of the 
 ferrous sulphate solution, and the number of cubic centimeters 
 of ferrous sulphate used to reduce the chromic acid minus the 
 cubic centimeters of permanganate necessary to oxidize the 
 excess of ferrous sulphate, will give the amount of chromium 
 present in milligrams. 
 
 For example, to 3 grams of steel treated as above, 35 cc. of 
 the ferrous sulphate are added to reduce the chromic acid and 
 then 5 cc. of permanganate solution are found necessary to pro- 
 duce a permanent pink ; hence 3 grams of this steel contain 0.03 
 gram of chromium or i per cent. If these same solutions are 
 used for the titration of the manganese dioxide by the Williams' 
 
The Determination of Chromium. 123 
 
 method, each cubic centimeter of ferrous sulphate used in ex- 
 cess of the cubic centimeters of permanganate used in the back 
 litration equals 0.001418 gram manganese. 
 
 In case the determination of manganese is not required and it 
 is desired to avoid the filtration from the manganese dioxide, the 
 method may be modified by diluting the solution after it has 
 been boiled down to 40 cc. by the addition of 100 cc. of water 
 and a few drops of hydrochloric acid, which will at once dissolve 
 the manganese dioxide without action on the chromic acid. 
 The solution then must be boiled for a few minutes to remove 
 the chlorine set free by the reduction of the manganese dioxide, 
 after which it may be cooled and titrated as above. 
 
 In very many chrome steels the amount of manganese is so 
 inappreciable in comparison with the chromium that for practi- 
 cal results it is not necessary to remove the manganese dioxide 
 either by filtration or solution in hydrochloric acid but the solu- 
 tion may be diluted after the evaporation to 40 cc. and titrated 
 at once. Of course, in high chrome steels it is not necessary to 
 take more than a gram for the analysis. 
 
 For the determination of chromium in ores, slags, and ferro- 
 chromes, beyond a doubt the best method of decomposition is 
 by fusion with sodium peroxide in a nickel crucible, which 
 brings about complete decomposition in two or three minutes, if 
 the sample is at all finely ground. 
 
 Duplicate determinations on ores, slags, and ferro- chromes, 
 made by the solution of the sodium peroxide fusions in nitric 
 acid and oxidation by potassium chlorate, gave on titration 
 results equivalent to those obtained by the usual inethed of acidi- 
 fying with sulphuric acid, after decomposing the excess of perox- 
 ide by boiling in a water solution. Consequently there would 
 be no advantage in the chlorate method for these over the usual 
 method, except that, by obtaining a clear solution of fusion in 
 the nitric acid preliminary to oxidation with chlorate, all danger 
 from incomplete decomposition leading to the presence of parti- 
 cles of metal, which might reduce some chromic acid on the ad- 
 dition of sulphuric acid, is avoided. 
 
 However, in the writer's experience, the decomposition has 
 always been complete. 
 
NOTES ON THE ANALYSIS OF MILL AND PUDDLE 
 
 CINDERS. 
 
 BY Jos. M. WILSON. 
 
 Mill cinder is used in our furnace as part of the burden and is 
 almost wholly brought in car-load lots. As the railroad people 
 are constantly pushing us for prompt unloading, methods for 
 rapid determination of the constituent elements of these cinders 
 are important. Formerly we were required to report the iron 
 and insoluble matter at once and later the silica. At present iron 
 and phosphorus are also required and occasionally manganese. 
 Our methods are as follows : 
 
 IRON. 
 
 Weigh out 0.25 and 0.5 gram into lipless beakers, mois- 
 ten with 10-15 cc - water, making certain that the mass is 
 well broken up, add quickly 20 cc. concentrated hydrochloric 
 acid, cover, boil gently for twenty minutes (or let digest upon a 
 steam-table one hour, then bring to a good boil), add stannous 
 chloride solution, from a pipette, till the liquid is colorless, boil 
 two minutes, remove to the steam- table and allow to settle. The 
 supernatant liquid must be colorless. The residue will vary 
 from light gray to black according to the amount of powdered 
 coke present. 
 
 Wash into a No. 5 or 6 beaker, rinse a small beaker thoroughly 
 with cold water, taking care to remove all the insoluble matter. 
 Make the volume 300 cc., stir well, add 30-40 cc. mercuric chlo- 
 ride solution, all at once, stir, run in potassium dichromate until 
 
 4 drops give no blue coloration with a drop of ferricyanide indi- 
 cator in one-half minute. 
 
 Solutions Used. Potassium dichromate, 4.9 grams of the salt 
 in i liter of water, i cc. = 0.005 gram iron. Stannous chloride, 
 loo grams in i liter hydrochloric acid ( i : i ) . Mercuric chloride, 
 50 grams in i liter of water. Ferricyanide indicator, 5 cc. of a 
 
 5 per cent, solution in 40 cc. water. 
 
Analysis of Mill and Puddle Cinders. 125 
 
 INSOLUBLE MATTER AND SILICA. 
 
 Weigh i gram into a 5-inch Royal Meissen dish, stir up 
 with 20 cc. water, add 20 cc. concentrated nitric acid, stir well, 
 cover, evaporate to dry ness, and ignite till all acid smell 
 is gone. Cool, add locc. concentrated hydrochloric acid, evapo- 
 rate to dryness, ignite, cool, add 25 cc. hydrochloric acid, evap- 
 orate to 10 cc. , add 30 cc. water, and heat to boiling. Filter through 
 a 9-cm. filter, wash with hot hydrochloric acid (i : i) and with 
 cold water twice, ignite, cool, and weigh insoluble matter. 
 Fuse "insoluble" with six to eight times its weight of so- 
 dium carbonate, dissolve the fusion in water, acidify with 
 hydrochloric acid, evaporate to dryness, ignite, cool, add 
 10 cc. concentrated hydrochloric acid, dry, and ignite to render 
 silica entirely insoluble and granular. Cool, add 25 cc. hydro- 
 chloric acid, evaporate to one-half, add 30 to 40 cc. water, heat to 
 boiling, filter on a 9-cm. filter, wash twice with hot water, 
 filling the filter each time to remove salts, then with hot hy- 
 drochloric acid (i : i), and with cold water twice, then four to 
 six times with hot water, ignite, cool, and weigh ; or moisten insol- 
 uble matter with water, add hydrofluoric acid till a clear solution 
 is obtained, then 5 or 6 drops of sulphuric acid (i : 3), evapo- 
 rate, dry, ignite on hot plate till no more fumes of sulphur tri- 
 oxide come off, then heat to redness, cool, and weigh. L,oss = 
 
 SiO 2 . 
 
 MANGANESE. 
 
 This is determined by precipitation with potassium chlo- 
 rate, purification of the manganese dioxide precipitate, and final 
 weighings as Mn 2 P 2 O 7 , by the acetate method or by color. 
 
 PHOSPHORUS. 
 
 Having found phosphorus in our pig metal and being un- 
 able to determine its source we sought it in ore, flux, and 
 fuel, but not finding it in either we were compelled to turn 
 to the mill cinder. Up to this time we, like many others, sup- 
 posed that all the phosphorus was " soluble" inasmuch as mill 
 cinders are easily decomposable silicates, but as we could not 
 locate the trouble elsewhere we turned our attention to the resi- 
 
126 Jos. M. Wilson, 
 
 dues which we fused and treated for phosphorus ; the results 
 took us completely by surprise, for we found that no matter 
 what the total amount of phosphorus in the cinder the insoluble 
 residue invariably carried between 0.03 per cent, and 0.04 per cent. 
 
 As the fusion of the residue and its subsequent treatment took 
 more time and attention than we could give it, we had to devise 
 a method by which we could obtain results rapidly. After some 
 experimenting we settled on the following scheme : Weigh 5 
 grams substance into a platinum dish, stir up with 30 cc. water, 
 add 30 cc. hydrofluoric acid, and 30 cc. hydrochloric acid. Cover 
 with platinum foil supported by a platinum triangle, evaporate to 
 dryness over an Argand burner turned low, add 20 cc. "hydrochloric 
 acid, evaporate again to get rid of hydrofluoric acid, add 30 cc. 
 hydrochloric acid, evaporate one-half, and wash into a No. 3 
 beaker. Evaporate to a sirup, add 50 cc. nitric acid, evaporate 
 till no more brown fumes come off and liquid is sirupy, add 30 cc. 
 water, and heat to boiling. Filter through a y-cm. filter into a 
 i6-oz. flask, wash filter twice with cold water, and once with hot 
 nitric acid (sp. gr. 1.20), dropping acid from a pipette on the 
 side of the funnel just above the top of the filter ; wash acid out 
 of filter. Filter retains the coke. 
 
 Boil filtrate, add potassium permanganate (12^ grams to i 
 liter of water) till a brown precipitate of manganese dioxide sep- 
 arates and remains. 20 to 100 cc. will be required, according to 
 the amount of carbonaceous matter dissolved and the complete- 
 ness with which hydrochloric acid has been driven off by the 
 nitric acid used in the last evaporation. Reduce the manganese 
 dioxide with ferrous sulphate (free from phosphorus) . After reduc- 
 tion is complete, boil ten minutes, cool, and add strong ammonia 
 till the ferric hydroxide makes a thick mud. Redissolve in strong 
 nitric acid to clear amber-colored liquid, and insert a thermometer. 
 When temperature is 88 C. pour in 100 cc. molybdate solution. 
 (Wood's 1 8 88 formula), shake five minutes, let settle, filter off yel- 
 low precipitate, wash with 2 per cent, nitric acid (or Dudley's acid 
 ammonium sulphate) five times. Remove acid by five washings 
 with potassium nitrate ( i : 1000) , and determine phosphorus by any 
 convenient method : (i) weigh yellow precipitate, (2) titrate the 
 reduced molybdic acid with potassium permanganate, (3) titrate 
 
Analysis of Mill and Puddle Cinders. 127 
 
 back the excess of standard sodium hydroxide, etc., etc. A de- 
 termination by this method can be made in six hours without 
 hurrying the evaporations with hydrofluoric acid and hydro- 
 chloric acid. 
 
 The following method has been used when not in a hurry : 5 
 grams in a 5-inch deep dish are moistened with 20 cc. of water, and 
 80 cc. concentrated nitric acid. Hydrochloric acid gelatinizes 
 the silica, which encloses particles of undissolved slag and is 
 very troublesome to handle. Evaporate to dry ness, ignite till 
 no more acid fumes are perceptible, cool, moisten with 20 cc. 
 hydrochloric acid, take up in 50 cc. water, filter, wash with hot 
 hydrochloric acid (i : i), and with cold water till free from iron. 
 Ignite, fuse with five to six times its weight of sodium carbon- 
 ate, dissolve in hot, dilute nitric acid, evaporate to dryness, 
 ignite till free from acid fumes, cool, moisten with hydrochloric 
 acid, dry, ignite again, cool, moisten with hydrochloric acid, 
 take up with water, filter, and boil filtrate. Add slight excess 
 of ammonium hydroxide, boil two minutes, filter, wash precipi- 
 tate three times with hot water, then wash into a beaker contain- 
 ing the original acid solution, and boil to a sirupy consistency. 
 Add 40 cc. concentrated nitric acid, boil down to a sirup, add 25 
 cc. water, heat to boiling, filter through a y-cm. filter into a 
 i6-oz. flask, wash with nitric acid and water, and precipitate 
 and determine phosphorus as above. 
 
 The precipitation of iron and aluminum phosphate from a solu- 
 tion of fusion freed from silica, serves to get rid of the great ex- 
 cess of alkaline salts and leaves the phosphorus in better condi- 
 tion for precipitation. 
 
 As stated above, nitric acid is a better solvent for mill cinders 
 than hydrochloric acid, as it does not gelatinize the silica and 
 leaves the insoluble matter more sandy and more easily filtered 
 and washed. 
 
I2 8 Analysts of Mill and Puddle Cinders. 
 
 Below are a few results : 
 
 Per cent. 
 
 Car. No. 405, Soluble phosphorus 0.045 
 
 " " 493, " " al 3 
 
 3354, ' ' ' ' 0.800 
 
 " " 3354, phosphorus by solution in nitric acid and 
 
 fusion of residue 0.830 
 
 " " 4818, Insoluble phosphorus O-035 
 
 " " 537, " " ' 38 
 
 " " 405, Phosphorus by method above 0.080 
 
 " " 493, " " M " ' I6 5 
 
 " " 3354, " " " " ' 82 5 
 
 " " 4818, Total phosphorus 0.155 
 
 577 " " 0.060 
 
 537, 
 
THE COMPLETE ANALYSIS OF CHROME ORE. 1 
 
 BY A. G. MCKENNA, 
 
 Chemist to the Sterling Steel Co., Demmler, Pa. 
 
 A serious objection to most methods of chrome ore analysis 
 has been the difficulty of obtaining complete decomposition of 
 the ore without prolonged and repeated fusions with the reagents 
 generally employed for that purpose. 
 
 By fusing the ore with sodium peroxide, which is now com- 
 ing into general use as an analytical reagent, any chrome ore is 
 completely decomposed in a few minutes. The fusion should 
 not be made in platinum as the peroxide attacks the crucible 
 strongly. A nickel crucible is best to use, although it is also 
 attacked and cannot be used more than twenty or thirty times. 
 On leaching out the fusion with water all the chromium goes 
 into solution as sodium chromate; the oxides of iron, nickel, and 
 magnesium remain in the undissolved residue. The following 
 method for the determination of silica, oxide of iron and chro- 
 mium, alumina, lime, and magnesia is based on the above-men- 
 tioned facts. 
 
 DETERMINATION OF OXIDES OF IRON AND CHROMIUM. 
 
 0.5 gram of the finely ground sample which has been dried at 
 1 00 C. for one hour is weighed into a nickel crucible of about 
 20 cc. capacity, in which have been placed 3 or 4 grams of 
 sodium peroxide ; after thoroughly mixing the contents, the 
 crucible is held over a Bunsen burner by means of a pair of 
 suitably shaped tongs, until fusion begins. The mass is kept in 
 a liquid condition at a low red heat for about one minute, 
 which is sufficient to insure complete decomposition if the ore is 
 at all finely ground. After allowing the crucible to cool it is 
 placed in a 4OO-cc. beaker with a watch-glass cover and hot 
 water added until the crucible is covered. 
 
 i Read before the Chemical Section of the Engineer's Society of Western Pennsyl- 
 vania, March 18, 1897. 
 
130 A. G. McKenna. 
 
 The beaker is placed on a hot plate for a few minutes until 
 the fusion is dissolved ; the crucible is then removed by means 
 of a glass rod and the contents of the beaker allowed to settle for 
 a few minutes. When the insoluble matter has subsided it is 
 collected on a 9-cm. filter-paper, the filtrate being received in a 
 half-liter flask. The residue on the paper which contains all 
 the iron is ignited in a platinum crucible, fused with 2 or 3 
 grams of potassium bisulphate, dissolved in dilute sulphuric acid 
 (i : 10), reduced by filtration through amalgamated zinc, and 
 titrated in the usual manner with standard permanganate. The 
 result is calculated to ferrous oxide. 
 
 The filtrate in the half-liter flask, which contains all the chro- 
 mium as sodium chromate in an alkaline solution, is boiled for 
 about ten minutes in order to insure the removal of all peroxide 
 which, if allowed to remain until the solution is acidified, would 
 react on the chromate, reducing it to the sesquioxide. 
 
 When the removal of the peroxide is complete the solution is 
 allowed to cool and then acidified with a large excess of dilute 
 sulphuric acid ( i 14). 
 
 The solution is transferred to a i -liter beaker, and diluted to 
 about 800 cc. with cold water. To this solution 70 cc. of a 
 ferrous sulphate solution, containing 10 grams of iron (in the 
 ferrous condition) to the liter, are added ; this is sufficient to re- 
 duce the chromic acid corresponding to 0.3167 gram of chromic 
 sesquioxide. The excess of ferrous sulphate which has been 
 added, is determined by back titration with standard perman- 
 ganate solution, of which i cc. is equivalent to i cc. of the 
 ferrous sulphate solution. Such a permanganate contains 5.643 
 grams potassium permanganate to the liter. The difference 
 between the cubic centimeters of ferrous sulphate used and the 
 cubic centimeters of permanganate used, multiplied by 0.905, 
 gives the percentage of chromic sesquioxide in the ore. 
 
 For the determination of silica, alumina, ferric oxide, chromic 
 sesquioxide, lime, and magnesia, fuse one-half gram of ore in a 
 nickel crucible as before, dissolve in about 50 cc. hot water in a 
 covered 5-inch porcelain dish, remove crucible and acidify with 
 hydrochloric acid, evaporate to dry ness, take up in dilute hydro- 
 chloric acid (i 14), filter, ignite, and weigh as SiO 2 . To the 
 
The Complete Analysis of Chrome Ore. 131 
 
 filtrate add 10 cc. strong hydrochloric acid, make ammoniacal, 
 pass hydrogen sulphide, allow to settle, filter off the precipitated 
 hydrates of chromium and aluminum and the sulphides of 
 iron and nickel. Dissolve the iron, chromium, and aluminum in 
 dilute hydrochloric acid and reprecipitate as before with hydrogen 
 sulphide and filter. In the combined filtrates determine lime and 
 magnesia in the usual manner. 
 
 Redissolve the iron, chromium, and aluminum precipitates 
 from the filter-paper with dilute hydrochloric acid, oxidize with 
 a few drops of nitric acid, precipitate with ammonia, filter, wash 
 free from chlorine, ignite, and weigh as A1 2 O 8 , Cr 2 O 3 , Fe 2 O 3 . 
 From this weight subtract the Cr 2 O 3 + Fe 2 O 3 , calculated from 
 the percentage of iron and chromium found in previous analysis, 
 which will give the alumina. 
 
INDEX. 
 
 Alumina in blast-furnace slag, determination of 103 
 
 Barium hydroxide as an absorbent in carbon determinations 109 
 
 Barrett, J. C 80 
 
 Black Diamond Steel Works laboratory, Pittsburg, Pa 23 
 
 Brinker, F. G 60 
 
 Calcium in blast-furnace slag, determination of 104 
 
 Carnahan, R. B., Jr., see Tonnele, Theo. 
 
 Camp, J. M 88, 101 
 
 Carbon in steel, determination of, 8, 14, 20, 27, 45, 55, 78, 86, 97 ; 
 
 Barium hydroxide in carbon determinations 109 
 
 Carnegie Steel Co. laboratory, Homestead, Pa I 
 
 " " " " Lucy Furnace, Pittsburg, Pa 21 
 
 " " " " Edgar Thomson Furnace, Braddock, 
 
 Pa 50 
 
 Duquesne, Pa 88, 101 
 
 Chrome ore, complete analysis of 129 
 
 Chromium, determination of 121, 129 
 
 Chromium in chrome ore and ferro-chrome, determination of 44 
 
 Cinders, analysis of blast-furnace, 101; analysis of mill and puddle .. 124 
 
 Clifton, Warren R 63 
 
 Clinton Iron and Steel Co. laboratory, Pittsburg, Pa 57 
 
 Cobalt in steel, determination of 42 
 
 Crabtree, Frederick 12 
 
 Dudley, C. B 70 
 
 Ferro-silicon and silico-spiegel, determination of silicon in 37 
 
 Garrigues, W. E 117 
 
 Graphite in pig iron, determination of 45 
 
 Hainsworth Steel Co., Edith Furnace Dept., Allegheny, Pa 47 
 
 Harrison A. B 57 
 
 Iron in iron ores, determination of, i, 12, 16, 21, 23, 47, 50, 57, 60, 63, 
 
 72, 74, 80, 89 ; improvement in zinc reductor 113 
 
 Iron oxide in blast-furnace slag, determination of 103 
 
 Iron oxide in chrome ores 129 
 
 Isabella Furnace Co. laboratory, Etna, Pa 60 
 
 Johnson, Edward S 23 
 
 Johnston, R. G 47 
 
 Junction Iron and Steel Co. laboratory, Steubensville, O 16 
 
 Lime in blast-furnace slag, determination of 104 
 
 Magnesia in blast-furnace slag, determination of 105 
 
 Manganese in blast-furnace slag, determination of 105 
 
 Manganese in ores, determination of 
 
 5, 13, 18, 25, 52,53, 57,61, 64, 6872, 75,82, 90 
 
Index. 133 
 
 Manganese in pig iron, determination of 
 
 10, 14, 18, 20, 21, 27, 49, 55, 58, 61, 67, 73, 77, 85, 92 
 
 Manganese in steel, determination of 
 
 10, 15, 18, 33, 40, 56, 58, 67, 73, 79, 85, 92 
 
 Mclntosh, Hemphill and Co. laboratory, Pittsburg, Pa 72 
 
 McKenna, A. G 109, 113, 121, 129 
 
 Miller, Robert 21 
 
 M'Kelvey, J. P 72 
 
 Monongahela Furnace laboratory, McKeesport, Pa 12 
 
 Murray, C. B 50 
 
 Nickel in steel, determination of n, 41, 42, 56, 58, 69, 73, 79, 96 
 
 Ohio Steel Co. laboratory, Youngstown, O 80 
 
 Oliver and Snyder Steel Works laboratory, Pittsburg, Pa 36 
 
 Pennsylvania R. R. Co. laboratory, Altoona, Pa 70 
 
 Phosphorus in blast-furnace slag, determination of 107 
 
 Phosphorus in steel, pig iron, and ores, determination of, 3, 12, 14, 
 
 15, 17, 20, 21, 24, 27, 32, 39, 48, 49, 51, 54, 56, 57, 58, 61, 63, 66, 72, 
 
 73;74> 77> 78, 81, 84, 88, 89 ; improvement in zinc redactor 113 
 
 Reductor, improvement in 1 13 
 
 Rodgers, S. M 36 
 
 Shenango Valley Steel Co. laboratory, Newcastle, Pa 63 
 
 Silica in blast-furnace slag, determination of 102 
 
 Silica in ores of iron and manganese, determination of 
 
 i, 12, 16, 21, 23, 47, 50, 57, 60, 63, 72, 74, 80 
 
 Silicon in pig iron and steel, determination of 
 
 6, 13, 19, 21, 26, 36, 37, 49, 54, 57, 58, 61, 64, 72, 76, 83, 87, 94 
 
 Slag, analysis of blast-furnace 101 
 
 Sulphur in blast-furnace slag, determination of 106 
 
 Sulphur in pig iron and steel, determination of, 7, 14, 15, 19, 21, 30, 37, 
 
 49> 54> 56, 58, 64, 65, 72, 73, 76, 78, 83, 94 ; evolution methods 
 
 for 117 
 
 Tonnele, Theo. and R. B. Carnahan, Jr 74 
 
 Unger, John S i 
 
 Wilson, Joseph M 16, 124 
 
 W. Dewes Wood Co. laboratory, McKeesport, Pa 74 
 
ENGINEERING CHEMISTRY: 
 
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