402
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y .
according t o the temperature, time and composition of the zinc-powder mass employed. When the zinc powder is diluted with inert material, such as silica, and the time relatively short, the coating will consist of a very thin layer of the alloy FeZn,, together with a more or less distinct layer of binding alloy of unknown composition. If the time is increased, and the powder richer in metallic zinc, a heavy coating is obtained as shown in Plate 1 3 . If continued long enough, a layer of zinc forms on the surface of the alloy as shown in Plate 14. In all sherardized coatings are t o be seen many cracks running through the alloy. This is particularly shown in the upper part of Plate 13. By polishing a section a t right angles to the cross section, Plate 1 5 is produced. This shows the alloy to be broken into numberless fissures much resembling mud cracks. I t is probable t h a t greater study of etching methods would bring out still other alloys in this complicated structure. Thus Plate 16 shows two sherardized sections which have been etched by slow rusting in the air. They are from the same sheet as t h a t used in Plate 13, and show a second alloy between the main coating alloy and what we have called the binding alloy. The blotched portions are the iron surfaces spotted with rust flecks. Owing t o the brittleness of the main alloy a regular outline a t the sodium silicate surface is difficult to obtain. Electrogalvanized Iron.-The metal deposited by an electric current depends upon the impressed voltage and the composition of the electrolyte or bath. A coating of very pure zinc may be produced, or an alloy of widely varying proportions of iron may be obtained by adding iron salts t o the bath, or as is sometimes erroneously done, by using an iron anode. I n any case a very thin binding alloy next to the iron is always t o be seen. Plate 17 shows a piece of ordinary wet galvanized iron in which the coating D is pure zinc. E is the sodium silicate layer, and B the binding alloy. Plate 18 shows two pieces of such iron which have been bent before mounting. The coating is seen t o have parted from the iron base along the line formed by i t and the alloy RESEARCH LABORATORY O F APPLIED CHEMISTRY, MASSACHUSETTS INSTITUTE O F TECHNOLOGY.
THE ESTIMATION OF OXYGEN AND OCCLUDED GASES IN COPPER AND A CORRECTION TO THE ELECTROLYTIC ASSAY IN THE COMPLETE ANALYSIS OF COPPER. B Y GEORGEL. HEATH. Received January 2, 1912.
The only strictly quantitative chemical reaction for the estimation of the oxygen in commercial copper was first proposed by Dr. W. Hampe,' of Germany. He subjected the finely divided metal t o a gentle heat for a few minutes in a current of pure carbon dioxide, called the loss (a few mg.) moisture and ignored i t : the oxygen was then determined by the loss of weight, or water produced, on heating in a current of hydrogen a t red heat. His method was improvedl by sim2.f . Berg Hiitten- and Salinea Wesea, 1875. Fresenius Z e d , 1874. Archbutt: Analyst, 26, 253. Hoffmann: Truas. A . I . M. E., 34, 671. Heath: Jour. Am. Chem. Soc., 17, 313. 1 2
June,
1912
plifying the cleaning of the metal and by absorbing the traces of evolved sulphur in an ammoniacal solution of cadmium chloride. To secure the complete evolution of all gases from the metal, i t is necessary t o take a precaution not mentioned in any published description of the method. It is the purpose of this paper t o correct the serious error in the old method' and t o report the result of a search for a means of estimating the occluded gases in cast refined copper. The loss on'heating copper filings, or fine drillings, in hydrogen, until there is no further change in weight, is not entirely2 due t o oxygen from cuprous oxide and sulphurous acid, but also includes the gases derived by the metal from the fuel and the refining in the furnace, and in addition, any trace of moisture, mechanically held, and finally is subject t o the error t o be explained.
I have found that, within the limits of an ordinary analysis, red-hot copper has practically no affinity for carbon dioxide. It has been proved that the gases which exist in cast metal (0.005per cent. or more) can be driven out of the same by replacing every trace of air in the glass tube with perfectly pure, dry carbon dioxide, and then heating the copper in contact with the gas for 20-30 minutes. The loss in weight is due t o evolution of the occluded H , with traces of CO, CO,, N , and possibly argon. The loss of weight found by heating subsequently in hydrogen does not express the true oxygen of the cuprous oxide present in the cast metal, for the metal retains, after long exposure t o a current of hydrogen, nearly twice a$ much hydrogen in an occluded state, or solid solution, as was present in the absorbed gas of the cast metal; the original occluded hydrogen gas was driven out by the preliminary heating in carbon dioxide. This serious error has hitherto escaped attention. The hydrogen held back after heating in hydrogen should be finally expelled from the reduced copper by a current of pure carbon dioxide, exposing the hot metal t o this gas for twenty minutes before cooling and weighing in air. Carbon Dioxide.-Carbonic acid free from every trace of oxygen and other impurities cannot be produced as easily from marble, or calcite, as by the method of Bradley and Hale.3 They use a paste of sodium bicarbonate and water in a 7 0 0 cc. flask surmounted with a separator tube. The generator is started half an hour before use and the gas allowed to flow through the purifying and drying tubes (to be described), as far as a three-way valve placed just before the ignition bulb tube containing the copper.3 If the gas is generated from marble, or calcite, it is even more necessary t o absorb the trace of oxygen constantly given off from the mineral after the air is all driven out of the apparatus. If a trace remains, i t will tint the red-hot metal at the point where i t enters the bulb. Described by the author in Jour. A m . Chem. SOC, ai', 313. J . Elect. Chem.. 16, 707. Chem. Abstracts, 1811, p. 3384. a J . Am. Chem. Soc., SO, 1090 (1908.) 1
2
June,
1912
T H E J O U R l Y A L OF I A ’ D U S T R I A L .4-VD E:VGI.YEERISG C H E M I S T R Y .
The carbon dioxide is purified and dried as follows:
(A) Casamajor generator with elevated pressure bottle, and small bottle on the table, containing the marble on a bed of large lead shot; the upper bottle is filled with hydrochloric acid (I part to 2 of water). (A,) Bulb of saturated, neutral KMnO,. ( B ) Glassstoppered U-tube sealed a t the bottom with a solution of silver sulphate. (C) Bowen’s (potash) bulb filled with strong sulphuric acid, after which may be placed a short tube of anhydrous calcium chloride. (D) A tube of dry chromous chloride.1 ( E ) Tube of stick-phosphorus, (F) Two tubes of phosphorus pentoxide. (G) Short tube of dry calcium chloride. The expensive chromous chloride can be regenerated by passing a current of pure hydrogen through the tube a t a gentle heat as long as any hydrochloric acid or moisture is given off. B y pulling out the second stopper in the tube B, the gas may be allowed to discharge into the air until the air is swept out of the generator, or i t may be discharged under pressure from under a seal of 30 mm. of mercury, if generated from sodium bicarbonate by the method of Bradley and Hale.* The gas should always be passed through the bulbs as far as a threeway valve placed in front of the ignition tube until a test on hot copper shows t h a t the gas is pure, giving no discoloration whatever a t the point nearest the generator. Hydrogen Gus.--’The part of the generator holding the pure granulated zinc should be rather small, in order that the air may more easily be swept out. The action should be started and the gas passed over .the copper for I j minutes before lighting the burners. The purifying trains is as follows: A small washing bottle of I O per cent. KOH, saturated with KMnO,. Bowen‘s bulb, conc. sulphuric acid, (C) palladium asbestos tube, heated by alcohol lamp, after air is expelled. (D) An Allihn 2 j 0 cc. washing bottle containing I O O cc. of vater, r o o grams of KOH (alcohol free) and 5 to I O grams of pyrogallic acid. (E)Two tubes of dry calcium chloride and the threeway valve in succession (C and D, alternative, tube of stick P, and two tubes of phosphorus pentoxide) Prepayation of the Copper Sample f o r Ignition.--I f a lot of copper is very porous, or of unknown origin, i t may be advisable to dry it a t 100’C. in an atmosphere of pure carbon dioxide or nitrogen (instead of heating in ignition tube to a heat which would expel some of the gases-an operation recommended by Hampe originally). If the speed and size of drill are regulated to produce fine drillings without any heating and oxidation, or contamination from grease, it will not be necessary to clean the drillings with ether. The adoption of the Copper Specifications of t,he American Society for Testing Materials will secure a fair sample of any casting, although equally good results are assured by boring half way through from both top and bottom, and also from t,he sides. Recommended b y J. 0.Handy. ‘ J . A m . Chem. Soc., 3 0 , 1090 (1908). 3 Handy proposes the following alternative: (1) E O H , (2) conc. H 2 S O l , (3) CaCI2, (4) heated palladium asbestos tube, ( 5 ) dry P205 opened up with glass wool. 1
403
With very pure material. an inch in depth is sufficient, the oxide having been previously removed by starting the hole through the surface skin with a larger drill. As a prominent chemist has just noted: < ‘ I tis impossible to remove all the soapy lubricant, or organic matter, from wires by washing with alcohol or ether directly.” I n such cases, it is suggested that the wire be cut in three-inch pieces and digested for a few minutes with alcohol KOH, I per cent. strength, as warm as possible without producing oxidation, then wash in water, alcohol, and ether successively. If a slight abrasion of the “skin” is not objectionable, the wire could be scoured, wet. with sharp silica (ground to pass a 40-mesh sieve), then washed with alcohol, etc. Extraction with petroleum ether (88 O to 8 j O Bd.) in a Soxhlet tube will sometimes remove the offending material. The ignition is performed in a hard-glass tube about 30 cm. long and 6 mm. internal diameter, which has one long bulb, or two round ones, a t the center. It is cleaned, ignited, weighed, and the 50 gram sample fed into the tube very quickly in the following manner: Slide a tight fitting rod into one end as far as the nearest bulb, and attach to the other end, by short tubing, a short-stemmed funnel, whose diameter equals t h a t of the tube. By using a long platinum wire, and tapping the tube, the drilling can be packed in the bulbs, after which the tube is wiped with a dry warm cloth and allowed t o stand I O minutes on the balance before weighing. When connected with the apparatus, the ignition tube rests on a lamp ring of I O cm. diameter, and is protected from overheating by wrapping it with a fresh piece of thin asbestos paper, held in place by a short piece of stiff bent platinum wire. I G N I T I O N OF COPPER.
For Absorbed Gases.-A short drying tube and jet tube can be attached t o the rear end of the ignition tube through a glass three-way valve and the carbon dioxide passed through the tube system for 30 minutes t o sweep all the air out of generator and tubes. The fan burner, or triple Bunsen burner, is then lighted, the copper kept a t a full red heat for 20 minutes, the tube cooled with a n air blast and the CO, replaced by air which will require I O minutes. The tube is then wiped clean and allowed to stand on the scales I O minutes before weighing. The loss is due t o gases from the cast metal. For Total Oxygen and Sdphur.-Pass in hydrogen for 1 5 minutes, then keep a t a red heat (not high enough t o distil the metal into the glass) for I hour if the sample is filings, or 2 hours for coarse drillings. The necessary time should be ascertained in each laboratory b y repeating a n ignition on drillings of their standard fineness, until the weight is constant. The three-way valve a t the rear of the ignition tube should be turned during this heat so that the gases pass through a small U-tube, or bottle, containing I O cc. of a solution of ammoniacal cadmium chloride ( 2 0 grams per liter), Start the current of CO, through its own set
T H E J O U R N A L OF IiVD U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y .
404
of purifying tubes 20-30 minutes before the copper is all reduced, so that every trace of air shall be swept out of the tubes as far as the three-way valve in front of the copper. When the hydrogen has been passed long enough t o complete the reduction of all oxides in the metal, turn off the hydrogen and pass in pure CO, for a t least 2 0 minutes. Then cool the tube with an air blast until the copper is but slightly warm, replace the CO, with air and weigh with the same precautions as before. Sulphur.-About 70 cc. of water are placed in a No. I beaker, the cadmium solution and sulphide washed into i t with the aid of dilute hydrochloric acid ( I : I ) and the sulphur is titrated’ at once with standard iodine ( 2 grams of I per liter). I cc. of this solution = 0.00025 gram of S. Experimental proof of the completeness of the reduction of the copper b y ignition in hydrogen and
June, 1912
per cent. on complete analysis unless one sample is used for all tests. There is slightly less occluded gas in low-set, or oxidized, cast copper than in copper which is well refined to standard grade. Highly refined metal which shows “ t r u e ” over-poling (due not t o sulphur, but to poling too high in the furnace) would certainly show a large increase in occluded gases, near the upper surface of the castings of chilled metal. Since the occluded gases in cast copper are so small in weight, a sample of I O O grams in a bulb of the style recommended by Dr. H. 0. Hofmann would give a better result than the quantity I have specified. CORRECTION
TO
ELECTROLYTIC
ASSAY
I K COMPLETE
ANALYSIS O F COPPER.
The exact electrolytic assay of refined copper as described elsewhere by the author’ gives results SUEciently accurate for valuation of the metal, but the
Sample No. 1. a. * h. Per cent. Per cent.
b. Per cent.
C.
so.3. “Low set”.
Per cent.
Per cent.
No. 4. Arsenical. Per cent.
0.0074
0.0070
0.0070
0.0058
0.0077
0.0523 0.0156
0.0659 0.0132
0.0579 0.0139
0.0679
0.0741
0.0718
No. 2. 3.
Per cent.
OCCLUDED GASESAND COXEINEDOXYGENIS REFINEDCOPPER.
Absorbed gases-by heating i n CO?. . . . . . . . . . 0.0064 Apparent loss-heating t o constant weight in H gas and cooling in H gas.. . . . . . . . . . . . . . Additional loss by heating next in COz. . . . . . . Total Oxygen-by heating in H gas followed by COn gas.. ............................ 0.0238
0.0064
0.0254
0.0610 0.0018 0.1664
0.0628
SUMMARY OF COMPLETE .&NALYSIS.
Oxygen and occluded gas averages.. . . . . . . . . . Foreign metals in copper.. . . . . . . . . . . . . . . . . . Arsenic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Copper and silver.. ........................ Total .................................. P R O O F O F METHODFOR OXYGEN, E T C . , BY ANALYSIS Sulphur evolved and titrated. . . . . . . . . . . . . . . . Electrolysis (Cu and Ag). . . . . . . . . . . . . . . . . . . . Foreign metals in C u . . ..................... Total..
.................................
0.0310 0.0081
0.0784
0.1722
0.0066
0.0080
99.9560
99.9210
99.8120
0.0705 0.0146 0,0674 99,8420
99.9951
100.0060
99.9922
99.9945
-__ OF
CU
-~
PROM IGSITlON TUBE.
0.0006
99.9920 0.0081
0 0003 99.9930 0.0066
0 0011 99 9070
100.0007
99.9998
99.9901
carbonic acid may be obtained by a careful electrolytic assay of the reduced drillings. The sum of the per cent. added t o t h a t of the other impurities as found by complete analysis will total I O O per cent. without any oxygen, if the work and sampling are correct. I n order t o attain such a result it will be found necessary t o take the sample for oxygen determination from the very same bottle of drillings employed for the complete analysis, t h a t is for the electrolytic assay of the original cast copper. I n sampling a casting, the per cent. of oxygen varies directly with the per cent. of copper and silver and is variable enough in different samples drilled in the same casting t o prevent the results adding up exactly I O O 1 We use a specially prepared starch indicator which gives a very clear blue, with none of t h a t disagreeable muddy red, given by ordinary starch ( A m . Chem. Abstvacls, 4, 2617). The starch is allowed to stand over night, covered with cold water, containing 0.001 per cent. of hydrochloric acid. The next morning the acid is carefully washed out and the starch dried for two hours in an air oven at 100’ C. Five grams of this prepared material is boiled with 500 cc. of water, filtered, or decanted from the sludge, and 15 drops of oil of cassia added before bottling, t o render the solution permanent: 3 cc. of starch indicator are used in each test; a deduction is made for the iodine required t o produce the end point, as determined by a blank titration.
o oazo
deposition on the cathode is not absolutely completc, when a test of I cc. of electrolyte with hydrogen sulphide remains colorless. As noted by W. C. Ferguson in a recent paper, we have also observed t h a t about 0.005 per cent. t o 0 , 0 0 8 per cent. remains in solution. When an accurate complete analysis of the metal is desired, the author is accustomed t o treat the electrolytesfromthe j-or Io-grambatteryassayswith hydrogen sulphide gas. The sulphides are collected on a filter, roasted directly in a porcelain crucible, treated with a few drops of nitric and sulphuric acids, diluted with a little water, and the copper deposited on a small weighed platinum strip, and added to the principal cathode copper. Electrolytic deposits on platinum, as obtained by strictly following the method just quoted, have been found t o be free from any appreciable quantity of absorbed hydrogen. The methods already described might be used for gases in steel,2 by substituting nitrogen for carbon dioxide. Only of late has the effect of oxygen in steel received the attention i t deserves. 1 2
THISJOURNAL, 3, Feb., 1911. Ibid.,’3, June, 1911, p. 372,
