Chapter 9

A further advantage presented by the direct process described in this paper is that the Bessemer works is independent of the time at which the individual blast furnaces are tapped, as the pig iron required for the Bessemer process can be taken at any moment from the desulphurizing plant. In Hoerde, where the mixing and desulphurizing process has for a considerable time been regularly in use, it has been found that all the chief difficulties formerly encountered in the method of taking the fluid pig iron direct from the various blast furnaces to the converter have been obviated. At Hoerde the mixing and desulphurizing plant shown in the accompanying engravings is employed. This apparatus holds 70 tons of pig iron. It is, however, advisable to have an apparatus of greater capacity, say 120 tons. The apparatus has the shape of a converter, and the hydraulic machinery by which it is moved is simple and effective. An hydraulic pressure of eight atmospheres is sufficient to set it in motion. The vessel is provided with a double lining of firebricks of the same quality as those used for the lining of blast furnaces. This lining is gradually attacked only along the slag line, and does not require repair until it has been in use for some six weeks. Further repairs are then necessary every three weeks. Only the few courses of spoilt bricks are renewed, and for the repairs, including the cooling of the vessel, a period of two or three days is required. At the end of the week the vessel is kept filled, so that its contents suffice for the last charge to be blown on Saturday. On Sunday night the vessel is again filled. The consumption of manganese is very low; theoretically, it is the quantity required for the formation of manganese sulphide, and in practice it has been found that this amounts to about 0.2 per cent. The proportion of manganese which the desulphurized pig iron coming from the vessel should contain is best kept at about 1.5 per cent. in order to render the desulphurization as complete as possible. Thus, a mean proportion of 1.7 per cent. of manganese in the pig iron passing into the vessel is more than sufficient to effect a thorough desulphurization. Indeed, 1 to 1.2 per cent. of manganese is sufficient to effect a satisfactory desulphurization. For the extent of the removal of the sulphur, the temperature and the duration of the reaction are of importance. It has been found that if highly sulphureted pig iron is poured from the blast furnace into the desulphurizing vessel, fifteen to twenty minutes are sufficient to effect the desulphurization requisite for the steel process. The part played by the duration of the process is seen from the results obtained with the last charges, if the vessel is emptied at the end of the week without fresh pig iron being added from the blast furnace. If, for example, 60 tons of pig iron with 0.065 per cent. of sulphur remain in the vessel, the proportion of sulphur with the last charges falls to 0.03 per cent. The iron in the vessel remains sufficiently fluid for several hours. When necessary, a little wood is thrown in. It has been found quite unnecessary to obtain heat by passing and burning a current of gas above the bath of metal.

A number of results, showing the separation of sulphur at the Hoerde Works, was published a few months ago[2] by Professor P. Tunner, one of our honorary members.

[Footnote 2: "Oesterreichische Zeitschrift fur Berg und Huttenwesen," 1891, No. 19.]

The totals represent, respectively, 138,500 kilogrammes of pig iron and 98,654 kilogrammes of sulphur.

Thus, from 138,500 kilogrammes of pig iron there has been eliminated 179,577-98,654 = 80,923 kilogrammes of sulphur, or, in other words, 45.063 per cent.

The proportion of sulphur in the slags rises with that in the iron from the blast furnace to 17 per cent., an inappreciable portion of the sulphur of the slag being oxidized to sulphurous anhydride by access of air. An analysis of the slag yielded the following results:

Per cent. Sulphur 17.07 Manganese 30.31 Phosphoric anhydride 0.61 Iron 7.13 Bases 35.04

An analysis of an average sample gave:

Per cent. Manganese sulphide 28.01 Manganous oxide 20.23 Ferrous oxide 25.46 Silica 18.90 Alumina 5.00 Lime 3.53 Magnesia 0.43

The great convenience and certainty presented by the method described in this paper will in all probability lead to its general adoption. As a matter of fact, several works are now occupied with the installation of this mixing and desulphurizing plant.

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ON THE OCCURRENCE OF TIN IN CANNED FOOD.

By H.A. WEBER, Ph.D.

The following investigation of the condition of foods packed in tin cans was prompted by an alleged case of poisoning, which occurred at Mansfield, Ohio, in April, 1890. A man and woman were reported to the writer as having been made sick by eating pumpkin pie made from canned pumpkin. The attending physician pronounced the case one of lead poisoning. The wholesale dealer from whose stock the canned pumpkin originally came, procured a portion of the same at the house where the poisoning occurred, and sent it to the writer for examination.

The results of the examination as reported in Serial No. 552, below, showed that the canned pumpkin contained an amount of stannous salts equivalent to 6.4 maximum doses and 51.4 minimum doses of stannous chloride per pound. On being notified of this fact, the dealer sent a can of the same brand of pumpkin from his stock. The inner coating of the can was found to be badly eroded, and upon examination, as reported in Serial No. 563, below, one pound of the pumpkin contained tin salts equivalent to 7 maximum and 56 minimum doses of stannous chloride.

The unexpected large amount of tin salts in such an insipid article as canned pumpkin, and the claimed ill effects of the consumption of the same, suggested the advisability of extending the investigation to other canned goods in common use. Accordingly a line of articles was purchased in open market as sold to consumers, no pains being taken to procure old samples. The collection embraced fruits, vegetables, fish and condensed milk. With the exception of the condensed milk, every article examined was contaminated with salts of tin. In most cases the amount of tin salts present was so large that there can be no doubt of danger to health from the consumption of the food, especially if several kinds are consumed at the same meal.

METHOD.

The method employed in the determination of the tin was simply as follows:

The contents of each can were emptied into a large porcelain dish, and the condition of the inner coating of the can noted. After thoroughly mixing the contents, fifty grammes were weighed off and incinerated in a porcelain dish of suitable size. The residue was treated with a large excess of concentrated hydrochloric acid, evaporated to dryness, moistened with hydrochloric acid, water was added, and the mass was filtered and washed, the insoluble matter being all washed upon the filter. After drying the filter with its contents, the whole was again incinerated in a porcelain dish and the residue treated as before. The solution thus obtained was properly diluted and saturated with hydrogen sulphide. After standing about twelve hours in a covered beaker the precipitate was filtered off and the tin weighed as stannic oxide.

RESULTS OF EXAMINATION.

_Serial No. 552._--Sample of canned pumpkin, received of F.A. Derthick, April 22, 1890, sent by Albert F. Remy & Co., Mansfield, Ohio. Pie made from it supposed to have made a man and woman sick. The attending physician pronounced the case one of lead poisoning.

Per cent. Tin dioxide with trace of lead 0.0424 Grains per pound 2.97 Equivalent to stannous chloride 3.74 Minimum doses 51.4 Maximum doses 6.4

_Serial No. 563._--Sample of canned pumpkin, received of Edward Bethel, June 27, 1890. Labeled: Choice Pie Pumpkin, packed at Salem, Columbiana County, Ohio, by G.B. McNabb, sent by A.F. Remy & Co., Mansfield, Ohio.

Per Cent. Tin dioxide 0.0444 Grains per pound 3.11 Equivalent to stannous chloride 3.91 Minimum doses 56 Maximum doses 7

Can eroded.

_Serial No. 565._--Sample of canned pumpkin, bought of T.B. Vaure, July 11, 1890. Labeled: Belpre Pumpkin, Golden. George Dana & Sons, Belpre, Ohio.

Per Cent. Tin dioxide 0.0054 Grains per pound 0.38 Equivalent to stannous chloride 0.48 Minimum doses 7.7 Maximum doses 1.0

Can eroded.

_Serial No. 566._--Sample of canned Hubbard Squash, bought of T.B. Vaure, July 11, 1890. Labeled: Ladd Brand, L. Ladd, Adrian, Michigan.

Per Cent. Tin dioxide 0.026 Grains per pound 1.85 Equivalent to stannous chloride 2.33 Minimum doses 37.00 Maximum doses 4.7

Can badly eroded.

_Serial No. 567._--Sample of canned tomatoes, bought of T.B. Vaure, July 11, 1890. Labeled: Extra Fine Tomatoes. Blue Label. Curtice Bros. Co., Rochester, N.Y.

Per Cent. Tin dioxide 0.012 Grains per pound 0.84 Equivalent to stannous chloride 1.06 Minimum doses 16.00 Maximum doses 2.00

Inner coating eroded.

_Serial No. 568._--Sample of canned tomatoes, bought of T.B. Vaure, July 11, 1890. Labeled: Fresh Tomatoes, Curtice Bros. Co., Rochester, N.Y.

Per Cent. Tin dioxide 0.014 Grains per pound 0.98 Equivalent to stannous chloride 1.23 Minimum doses 19.00 Maximum doses 2.5

Can eroded.

_Serial No. 569._--Sample of canned peas, bought of T.B. Vaure, July 11, 1890. Labeled: Petites Pois, P. Emillien, Bordeaux.

Per Cent. Copper oxide 0.0294 Grains per pound 2.06 Equivalent to copper sulphate 3.95 Tin dioxide 0.0068 Grains per pound 0.48 Equivalent to stannous chloride 0.6 Minimum doses 9.6 Maximum doses 1.2

No visible erosion.

_Serial No. 570._--Sample of canned mushroom, bought of T.B. Vaure, July 11, 1890. Labeled Champignons de Choix. Boston fils. Paris.

Per Cent. Tin dioxide 0.02 Grains per pound 1.40 Equivalent to stannous chloride 1.76 Minimum doses 28.00 Maximum doses 3.50

Inner coating highly discolored.

_Serial No. 571._--Sample of canned blackberries, bought of T.B. Vaure, July 11, 1890. Labeled: Lawton Blackberries. Curtice Bros. Co., Rochester, N.Y.

Per Cent. Tin dioxide 0.0114 Grains per pound 0.80 Equivalent to stannous chloride 1.01 Minimum doses 16.00 Maximum doses 2.00

Inner coating eroded.

_Serial No. 572._--Sample of canned blueberries, bought of T.B. Vaure, July 11, 1890. Labeled: Blueberries. Eagle Brand, packed by A. & R. Loggie, Black Brook, N.B.

Per Cent. Tin dioxide 0.03 Grains per pound 2.10 Equivalent to stannous chloride 2.64 Minimum doses 42.00 Maximum doses 5.30

Can badly eroded.

_Serial No. 574._--Sample of canned salmon, bought of T.B. Vaure. July 11, 1890. Labeled: Best Fresh Columbia River Salmon, Eagle Canning Co., Astoria Clatsop Co., Oregon.

Per Cent. Tin dioxide 0.0134 Grains per pound 0.94 Equivalent to stannous chloride 1.18 Minimum doses 18.90 Maximum doses 2.30

Inner coating eroded.

_Serial No. 578._--Sample of canned pears, received of Mr. Edward Bethel, July 29, 1890. Labeled: Bartlett Pears. Solan's Brand, packed in Solano Co., California.

Juice. Fruit. Per Ct. Per Ct. Tin dioxide 0.0074 0.0074 Grains per pound 0.5180 0.5180 Equivalent to stannous chloride 0.65 0.65 Minimum doses 10.40 10.40 Maximum doses 1.30 1.30

Can eroded.

_Serial No. 579._--Sample of canned peaches, received of Edward Bethel, July 29. 1890. Labeled: Peaches, Wm. Maxwell, Baltimore, U.S.A.

Juice. Fruit. Per Ct. Per Ct. Tin dioxide 0.0324 0.0414 Grains per pound 2.2680 2.8980 Equivalent to stannous chloride 2.85 3.65 Minimum doses 45.60 58.40 Maximum doses 5.70 7.30

Can badly eroded.

_Serial No. 580._--Sample of canned blackberries, received of Edward Bethel, July 29, 1890. Labeled: Blackberries, Clipper Brand, Wm. Munson & Sons, Baltimore, Md.

Per Cent. Tin dioxide 0.06 Grains per pound 4.20 Equivalent to stannous chloride 5.28 Minimum doses 84.00 Maximum doses 10.60

Can badly eroded.

_Serial No. 581._--Sample of canned cherries, received of Edward Bethel, July 29, 1890. Labeled: Red Cherries, Cloverdale Brand, G.C. Mournaw & Co., Cloverdale, Va.

Per Cent. Tin dioxide 0.0414 Grains per pound 2.8980 Equivalent to stannous chloride 3.65 Minimum doses 58.40 Maximum doses 7.30

Can badly eroded.

_Serial No. 582._--Sample of canned pumpkin, received of Edward Bethel, July 29, 1890. Labeled: Royal Pumpkin, Urbana Canning Co., Urbana, O.

Per Cent. Tin dioxide 0.0184 Grains per pound 1.2990 Equivalent to stannous chloride 1.62 Minimum doses 25.90 Maximum doses. 3.20

Can eroded.

_Serial No. 583._--Sample of canned baked sweet potatoes, received of Edward Bethel, July 29, 1890. Labeled: Tennessee Baked Sweet Potatoes, Capital Canning Co., Nashville, Tenn.

Per Cent. Tin dioxide 0.0132 Grains per pound 0.92 Equivalent to stannous chloride 1.16 Minimum doses 18.50 Maximum doses 2.30

Can eroded.

_Serial No. 584._--Sample of canned peas, received of Edward Bethel, July 29, 1890. Labeled: Marrowfat Peas, Parson Bros., Aberdeen, Maryland.

Per Cent. Tin dioxide 0.0044 Grains per pound 0.30 Equivalent to stannous chloride 0.38 Minimum doses 6.20 Maximum doses 0.80

Can slightly eroded.

_Serial No. 585._--Sample of string beans, received of Edward Bethel, July 29, 1890. Labeled: String Beans. Packed by H.P. Hemingway & Co., Baltimore City, Md.

Per Cent. Tin dioxide 0.0154 Grains per pound 1.08 Equivalent to stannous chloride 1.36 Minimum doses 21.70 Maximum doses 2.70

Can eroded.

_Serial No. 586._--Sample of canned salmon, received of Edward Bethel, July 29, 1890. Labeled: Puget Sound Fresh Salmon, Puget Sound Salmon Co., W.T.

Per Cent. Tin dioxide 0.0044 Grains per pound 0.30 Equivalent to stannous chloride 0.38 Minimum doses 0.20 Maximum doses 0.80

Can slightly eroded.

_Serial No. 587._--Sample of condensed milk, received of Edward Bethel, July 29, 1890. Labeled: Borden's Condensed Milk. The Gail Borden Eagle Brand, New York Condensed Milk Co., 71 Hudson Street, New York.

Tin dioxide none.

No visible erosion.

_Serial No. 592._--Sample of canned pineapples, bought of Mr. Brown, Fifth Avenue, August 4, 1890. Labeled: Pineapples, First Quality. Packed by Martin Wagner & Co., Baltimore, Md.

Per Cent. Tin dioxide 0.0098 Grains per pound 0.6860 Equivalent to stannous chloride 0.8640 Minimum doses 13.6 Maximum doses 1.7

Can eroded

_Serial No. 593._--Sample of canned pineapples, bought of Mr. Brown, Fifth Avenue, August 4, 1890. Labeled: Florida Pineapple, Oval Brand. Extra Quality. A Booth Packing Co., Baltimore, Md.

Per Cent. Tin dioxide 0.0158 Grains per pound 1.11 Equivalent to stannous chloride 1.40 Minimum doses 22.40 Maximum doses 2.80

Can eroded.

--_Jour. Amer. Chem. Soc_.

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NEW PROCESS FOR THE MANUFACTURE OF CHROMATES.

By J. MASSIGNON and E. VATEL.

The ordinary method of manufacturing the bichromates consists in making an intimate mixture of finely pulverized chrome ore, lime in large excess, potash or soda, or corresponding salts of these two bases. This mixture is placed in a reverberatory furnace, and subjected to a high temperature, while plenty of air is supplied. During the operation the mass is constantly puddled to bring all the particles into contact with the hot air, so that all the sesquioxide of chromium of the ore will be oxidized. After the oxidation is finished, the mass is taken from the furnace and cooled; the bichromate is obtained by lixiviation, treated with sulphuric acid and crystallized. This method of manufacture has several serious objections.

The authors, after research and experiment, have devised a new process, following an idea suggested by Pelouze.

The ore very finely pulverized is mixed with chloride of calcium or lime, or carbonate of calcium, in such proportions that all the base, proceeding from the caustic lime or the carbonate of calcium put in the mixture, shall be in slightly greater quantity than is necessary to transform into chromate of calcium all the sesquioxide of chromium of the ore, when this sesquioxide will be by oxidation changed into the chromic acid state. The chloride of calcium employed in proportion of one equivalent for three of the total calcium is most convenient for the formation of oxychloride of calcium. If the mixture is made with carbonate of lime (pulverized chalk), it will not stiffen in the air; but if lime and carbonate of calcium are employed at the same time, the mass stiffens like cement, and can be moulded into bricks or plates. The best way to operate is to mix first a part of the ore and well pulverized chalk, and slake it with the necessary concentrated chloride of calcium solution; then to make up a lime dough, and mix the two, moulding quickly. The loaves or moulds thus formed are partially dried in the air, then completely dried in a furnace at a moderate temperature, and finally baked, to effect the reduction of the carbonate of calcium into caustic lime. It is only necessary then to expose the loaves to the air at the ordinary temperature, for the oxidation of the sesquioxide of chromium will go on by degrees without any manipulation, by the action of the atmospheric air, the matter thus prepared having a sufficient porosity to allow the air free access to the interior of the mass. Under ordinary conditions the oxidation will be completed in a month. The division of this work--mixing, slaking or thinning, roasting or baking, and subjection to the air--is analogous to the work of a tile or brick works. The advance of the oxidation can be followed by the appearance of the matter, which after baking presents a deep green color, which passes from olive green into yellow, according to the progress of calcium chromate formation. When the oxidation is completed, the mass contains: Chromate of calcium, chloride of calcium, carbonate of lime and caustic lime in excess, sesquioxide of iron and the gangue, part of which is united with the lime. This mass is washed with water by the ordinary method of lixiviation, and there is obtained a concentrated solution containing all the chloride of calcium, and a small quantity only of chromate of calcium, the latter being about 100 times less soluble in water.

This solution can be used in the following ways:

1. It can be concentrated and used in preparing a new charge, the small quantity of calcium chromate present being an assistance, or:

2. It can be used for making chromate of lead (chrome yellow), by precipitating the calcium chromate with a lead salt; this being a very economical process for the manufacture of this color.

The mass after lixiviation, being treated with a solution of sulphate or carbonate of potash or soda, will yield chromate of potash or soda, and by the employment of sulphuric acid, the corresponding bichromates. The solutions are then filtered, to get rid of the insoluble deposits, concentrated, and crystallized.

If, instead of chromate or bichromate of potash or soda, chromic acid is sought, the mass after lixiviation is treated with sulphuric acid, and the chromic acid is obtained directly without any intermediate steps.

This process has the following advantages:

1. The oxidation can be effected at the ordinary temperature, thus saving expense in fuel.

2. The heavy manual labor is avoided.

3. The loss of potash and soda by volatilization and combination with the gangue is entirely avoided.

4. It is not actually necessary to use rich ores; silicious ores can be used.

5. The intimate mixture of the material before treatment being made mechanically, the puddling is avoided, and in consequence a greater proportion of the sesquioxide of chromium in the ores is utilized.--_Bull. Soc. Chem._ 5, 371.

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A VIOLET COLORING MATTER FROM MORPHINE.

A violet coloring matter is formed, together with other substances, by boiling for 100 hours in a reflux apparatus a mixture of morphine (seven grammes), p-nitrosodimethylaniline hydrochloride (five grammes), and alcohol (500 c.c.). The solution gradually assumes a red brown color, and a quantity of tetramethyldiamidoazobenzene separates in a crystalline state. After filtering from the latter, the alcoholic solution is evaporated to dryness, and the residue boiled with water, a deep purple colored solution being so obtained. This solution, which contains at least two coloring matters, is evaporated almost to dryness, acidulated with hydrochloric acid, and then rendered alkaline with sodium hydrate, the coloring matters being precipitated and the unchanged morphine remaining in solution. The precipitate is collected on a filter, washed with dilute sodium hydrate, dried, and extracted in the cold with amyl alcohol, which dissolves out a violet coloring matter, and leaves in the residue a blue coloring matter or mixture of coloring matters. The violet coloring matter is obtained in a pure state on evaporating the amyl alcohol. Its platinochloride has the formula PtCl_{4}.C_{25}H_{29}N_{3}O_{4}.HCl, and has the characteristic properties of the platinochlorides of the majority of alkaloids. The coloring matter, of which the free base has the formula--

(C_{6}H_{4}N(CH_{3})_{2})--N==(C_{17}H_{19}NO_{4})