T H E J O U R N A L O F 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
V o l .
II. MARCH, 1910. No. 3
T h e J o u r n a l o f 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
PU B L ISH E D BY
T H E A M E R IC A N C H E M IC A L S O C IE T Y ; BOARD OF E.DITOR5.
Editor:
W . D . R ich a rd so n .
Associate Editors.
G eo . P . A d a m so n , E . G . B a ile y , G . E . B arto n , W m . B ra d y , W m . C am p b ell, F . B. C a rp en te r, V ir g il C o b len tz, F ra n c is I. D u p o n t, W . C. E b a u g li, W m . C . G ee r, W . F.
H ille b ra n d , W . D . H o rn e, L . P. K in n ic u tt, A . E . L e a ch , K a r l L a n g e n b e c k , A . D . L ittle , P . C. M c llh in e y , E . B.
M cC re a d y , W m . M cM u rtrie, J. M e rritt M atth ew s, T . J.
P a rk e r, J. D . P e n n o c k , G eo . C. S to n e , F . W . T ra p b a g e n , E r n s t T w itc h e ll, R o b t. W a h l, W m . H . W a lk e r , M . C.
W h ita k e r , W . R . W h itn e y .
P u b lis h e d m o n th ly . S u b s c rip tio n p ric e to n o n -m e m b e rs o f th e A m e ric a n C h em ica l S o c ie ty $6.00 y e a rly .
Vol. II. MARCH, 1910. No. 3
EDITORIALS.
R U B B E R C H E M IST R Y .
A t the Boston meeting of the American Chemical Society a Rubber Section was organized, the purpose of which is to bring together a t occasional meetings chemists and others who are particularly interested in the field of India rubber. I t had been felt that many problems of moment and interest to manufactu
rers and consumers could be solved by united effort.
Notable among these problems and the first one to be undertaken is the standardizing of the methods of chemical analysis and physical test of rubber articles.
To this end, a committee of ten was appointed by the chairman of the Section, Mr. Charles C. Goodrich. Dr.
Charles Knight, of Bucht^l College, Akron, Ohio, was elected chairman of the committee.
This committee has unquestionably undertaken a large contract. A t present the methods are as numer
ous and diverse as the laboratories in which they are applied. To bring some degree of order out of such a chaos is a task worthy of the best effort. I t is clearly the express duty of this committee to do definite work as well as to indulge in discussion, and above all to recommend procedure that can be used tentatively, at least, until modified by experience. The use of uniform methods and good ones will be of distinct service to the rubber industry.
This is not the first attem pt to work out reliable methods of rubber analysis, nor is it the only com-
• mittee now at work. Cordial cooperation from manu
facturers and consumers will do much to surmount the numerous difficulties, and if every one who has occa
sion to analyze or test any of the articles made of India rubber will freely place their experience and data at the service of the committee, will try proposed meth
ods and will adopt for use recommended methods, even if not perfect, the success of the movement is assured.
w. c. gbsreUo>
ORIGINAL PA PL R 5.
[ Co n t r i b u t i o n f r o m Pi t t s b u r g La b o r a t o r y, Te c h n o l o g i c Un i t e d St a t e s Ge o l o g i c a l Su r v e y. ]
LOSSES IN TH E STORAGE OF CO AL.1
B y Ho r a c e C . Po r t e r a n d F . K . Ov i t z. R eceived J a n u a ry 10, 1910.
It is known from the work of Parr on Illinois coals, and that of Richters, Fayol, Boudouard, and others abroad, that coal undergoes a certain amount of oxidation and consequent deterioration in the air at ordinary temperatures. The Technologic Branch, U. S. Geological Survey, is engaged on a study of the extent of this deterioration of coal in the air under different climatic conditions, both as to loss in heat
ing value and loss in value for the manufacture of gas, coke, and by-products. Whether such loss is with most coals and under average conditions serious enough to justify the expense of underwater storage seems to be an unsettled question.
However, since the Government spends over three millions of dollars annually in the purchase of coal in large lots for the Arm y and N avy and for the Panama canal, much of which must be stored for some time in tropical climates and under unfavora
ble conditions, the possibility of effecting the economy of even a small percentage of the heating value by improved methods of storing seemed to justify this investigation.
Parr found that Illinois coals exposed in 20-lb.
lots to the weather for 7 months lost from two to ten per cent, of their heating value.2 The Western Electric Company stored 9,000 tons of Illinois coal under water for 2 years and found that the same coal, after having been exposed to the weather dur
ing that time, had two per cent, less heating value than the water-stored c o a L The Municipal Gas
1 P u b lish e d b y p erm ission o f th e D ire c to r, U . S. G eological Survey.
2 P a rr, S. W ., a n d H a m ilto n , N. D ., Econ. Geol., I I , 693 (1907).
3 EnQ. Neu-s, 60, 729.
78
Works, at Stettin, Germany, reports a saving of eight per cent. 011 gas yield and thirty per cent, on ammonia by storing their coal under water rather than in the open.1
Coal contains humic bodies unsaturated with re
spect to oxygen and it therefore absorbs considera
ble quantities of oxygen, particularly during the period immediately after mining. Oxygen is in theory doubly depreciative in its effect on the heating value of coal since it is not only a diluent like ash but, by combining during storage of the coal, with the com
bustible constituents, carbon and hydrogen, it serves also to render them in part inert and unavailable as fuel. The heat of this slow combustion process is either dissipated by ventilation or accumulates when ventilation is restricted, thus giving rise to spontaneous combustion.
I11 the present investigation an effort has been made to ascertain the extent of this absorption of oxygen, together with the degree of deterioration caused thereby, and at the same time the extent of the liberation by coal of combustible gases during storage, A 5-gallon glass bottle, crated, was taken into the mine and 25 lbs. of coal (about 1j2 in. in size) put into it immediately after stripping from the seam. The bottle was hermetically sealed and shipped to the laboratory. A sample of the air in the bottle was then drawn out by means of a tube provided for the purpose in the rubber stopper.
Out of xo samples taken in this way of as many different types of coal only one showed any oxygen in the air of the bottle on reaching the laboratory.
A sample of Connellsville coal which, on account of the proximity of the field, reached the laboratory only 36 hours after mining, showed after that time 11 per cent, oxygen in the air of the bottle. The other samples required from three to fifteen days to reach the laboratory and had absorbed during that time all the oxygen in the air of the bottle. It was then arranged, in case of four of these samples, to admit a measured supply of air or oxygen to the bottle (at the top) and to withdraw (from the bottom) the altered air containing gases from the coal. Sufficient air was introduced each day to give a slight excess of oxygen so that some oxygen was present in the gases withdrawn. In 5 months, ten kilos of the fol
lowing coals absorbed oxygen as follows:
S h e rid a n Co., W yo. (su b -b itu m in o u s), 24 .1 lite rs ox y g en (from a ir).
Saline Co.. 111... ... 1 9.2 “ “ u “ F ra n k lin C o., I l l ... 5 7 .0 “ “
P o c a h o n ta s, \V. V a ... 1 8 .2 “ u
The absorption of oxygen has continued at a some
what reduced rate since the expiration of the 5 months period, above described. The Franklin Co., Illinois, coal absorbed in 5 months oxygen equivalent to 0.81 per cent, of its weight. It seems probable, further
more, that the conditions of open-air storage allow
1 Scidl. Coll, Guard, 97, 322 (1909).
more thorough circulation of air and cause a greater degree of oxidation than is the case in the laboratory method.
The gases drawn off contained a slight amount of C0 2, in one case (the Wyoming sub-bitum'nous) about one-tenth of what would correspond to the oxygen taken up and in the other cases much less than that amount. That this taking up of oxygen by coal is not merely a surface adsorption phenom
enon as when charcoal absorbs gases was shown by Richters, who subjected the oxygenated coal to reduced pressure and boiled it in water when he ob
tained some C0 2 but practically no oxygen. This experiment has been repeated in this investigation on the samples of Franklin Co., 111., coal and the re
sults obtained by Richters corroborated.
Rather remarkable quantities of methane were 'present in the gases drawn off from these sealed bot
tles of coal. The extent of this production of methane at ordinary temperatures by coal freshly mined seems to be in accordance with the tendency of the mine from which the coal was taken to give trouble with gas explosions. This fact therefore shows that the coal itself, as it lies in the seam, is liberating gas from its own substance in greater or less degree according to its character. The following percentages of methane found in the 5-gallon bottles of coal illustrate this point:
T im e in P e r cen t. CII<
d ay s since in a ir of
Coal from m ining. b o ttle .
H a n n a , W y o ... 15 .0
K e n tu c k y c an n e l... 0.0
M onongah, W . V a ... 4 7 .2
P o c a h o n ta s, W . V a ... 3 .8
Saline Co., I l l ... ... 25 4 7 .0 Sh erid an Co., W y o ... ... 28 5 .7 C onnellsville, P a ... ... 12 8 .9 F ra n k lin Co., I l l ... 7 2 .4
Disastrous mine explosions have occurred within the last few years at Hanna, Wyoming, Monongah, West Virginia, and at Ziegler, Franklin County, Illinois. The above results tend to show the gaseous character of the coal from these mines.
The Franklin County, Illinois, coal, apparently the most gaseous of those examined, has produced (from 10 kilos) in 5 months about 10 liters of methane.
The loss of calorific value by such a loss of CH., is very small, approximately 9,000 calories per kilo of coal, or from 0 .1 to 0.2 per cent. Hydrogen could not be detected in the gases drawn off and CO, if present at all, was in traces only.
The loss of heating value through the absorption of oxygen by coal in storage may perhaps be more serious than that incurred through the loss of gases.
A question is often raised in this connection as to the effect of change of weight during storage. For ex
ample, if a i,ooo-ton pile of lignite carrying 20 per cent, moisture dries during storage to 10 per cent, moisture, we have only 900 tons remaining and the
0 1
heat value per lb. may be greater than in the original coal. This complication, due to moisture changes, is, however, avoided if we calculate calorific values in every case to the ash- and moisture-free basis. We then confine ourselves to a determination of the altera
tion in the organic, fuel substance present. If wre may assume that the total amount of this organic material does not change, there is no need of measur
ing change of weight of the coal. If, on the other hand, this organic material increases in weight due to simple addition of oxygen, our figures for loss, of heat value neglecting changes in weight will be too high; and if the organic material loses in weight due to oxidation of hydrogen to water or of carbon to C0 2, our figures for calorific loss will be too low.
Richters,1 Boudouard,2 Dennstedt,3 and others have shown that coal increases slightly in weight when subjected to oxygen treatment and that unsaturated compounds in the coal add oxygen to their molecules and become saturated. The effect of oxygen there
fore becomes merely one of neutralization of an equiv
alent in carbon and hydrogen in the coal and its dilu
ting effect becomes of no consequence.
In the present investigation changes in weight have not been determined, either in the laboratory tests or the outdoor tests, and therefore the figures obtained for loss of heat value may be somewhat too high. The following table gives the results of determinations of calorific value on the coal in sealed bottles through which air or oxygen had been passed for several months; and also on samples of the same coal submerged under water and of the fresh coal as mined.
The following results show no deterioration of heat value during storage under water for 8 months ex
cept in case of the Wyoming sub-bituminous No. 44.
After 22 months’ storage under water, during the latter half of which time the bottles stood in a warm place, sometimes reaching ioo° F., the Pocahontas coal had lost 0.2 per cent, and the Saline Co., Illi
nois, coal, 0.7 per cent. B y the passage of air or oxygen through the coal, the Pocahontas has lost 0.6 per cent., the Wyoming 0.7 per cent., and the Saline Co., Illinois, 1 .1 per cent. In case of the Franklin Co., Illinois, coals the results are not relia
ble, since the mine samples were not taken at the same time as those in bottles, and one of these mine samples (the W. Frankfort) shows lower heat value than the sample from the same mine kept 6 months in a sealed bottle. The test 23a, showing a loss by outdoor storage of 1.6 per cent. 011 the car sample value, the latter in turn being 1 .1 per cent, lower than the mine sample value, indicates the greater tendency of coal to deteriorate by outdoor exposure than by treatment with a current of air in a bottle.
1 R . T h re a te n . J . Soc. Chem. In d .. 28, 759 (1909).
2 O. B o u d o u ard , Com pi. rend., 148, 284.
3 D e n n ste d t a n d B u en z, Z . ange'x. C hem ., 21, 1825.
The Pocahontas coal in all cases evidently deteriorates less than the Illinois coals.
Re s u l t s o f La b o r a t o r y St o r a g e Te s t s. Tr e a t m e n t o f Co a l w i t h Ai r o r Ox y g e n a n d Im m e r s i o n u n d e r Wa t e r.
Calories Calories
calcu la c alcu la te d to te d to ash- a n d m a te ria l m o istu re- free of P e r
L ab . free m a- M ., S. a n d cen t.
No. D cscrip tio n o f sam ple. terial. tru e a s h .1 loss.
Pocahontas coal:
38 M ine sam p le, sealed u n til an alyzed 8804 8828 1 6a E x p o se d 8 jiio . o u td o o rs in 20-lb.
lo t ... 8800 8839 16b 8 mo. u n d e r w a te r in la b o r a to r y .. . 8802 8835
16c 22 m o. u n d e r w ater in la b o r a to r y .. 8782 8814 0 .1 7 37 10 m o. tre a te d w ith oxy g en in la b
o ra to ry ... 8754 8776 0 .5 7 S h eridan, I Vyo., S u b -bitum inous coal:
45 Mine sam ple, sealed u n til analyzed. 7326 7381
44 7 m o. u n d e r w a te r in la b o r a to r y .. . 7281 7335 0 .6 2 43 7 m o. tre a te d w ith a ir in la b o ra to ry
H arrisburg, S a lin e Co., III., coal:
7274 7331 0 .6 7
40 M ine sam p le sealed u n til a n aly zed .. 8272 8397 23 C ar sam ple, exposed in tra n s it 3
w eeks2... 8200 8301 2 3a E x p o se d 8 m o. o u td o o rs in 20-lb.
l o t ... 8060 8170 1.5 9 2 3b 8 m o. u n d e r w a te r in la b o r a to r y .. . 8210 8312
23c 22 m o. u n d e r w a te r in la b o r a to r y .. 8151 8239 0 .7 5 39 C orresponds to N o. 40, a fte r 9 m o.
a ir t r e a tm e n t... 8204 8308 1.06 F ra n k lin Co., III., coal:
125 M ine sam ple, B e n to n , ta k e n 5 m o.
a fte r N o. 4 9 ... 8071 8139 49 B o ttle sam p le, B e n to n , tr e a te d 5
m o. w ith o x y g e n ... 8060 8141 123 M ine sam p le, W . F ra n k fo rt, ta k e n
5 m o. a fte r N o. 4 8 ... 8030 8108 48 B o ttle sam p le, W . F ia n k fo rt,
tig h tly sealed fo r 6 m o ... 8063 8130
In cooperation with the N avy, the Geological Survey has recently begun some tests 011 outdoor stor
age of coal, l'ifty-pound portions were prepared from the same lot of coal which had been crushed to v 2 in. size and thoroughly mixed. Some of these were submerged under salt water at Portsmouth, N. H., at Norfolk, V a.; and at K ey West, Fla., others under fresh water at Pittsburg, and still others ex
posed to the weather at each of the places mentioned.
These portions w ill. be analyzed periodically to de
termine loss.
The Survey is also sampling coal on the Isthmus of Panama as it is being piled in open-air storage and will take further samples after exposure for different periods in order to determine the deteriora
tion in that hot climate.
About two years ago outdoor tests were started by the Geological Survey at Sheridan, Wyoming, to determine means of preventing “ slacking” of
“ black lignite” or sub-bituminous coal and to deter
mine the extent of deterioration in calorific value
1 B y tru e ash is m e a n t th e original a sh w ith its w a te r of h y d ra tio n in cla y a n d w ith its iron p y rite s in s te a d of th e F e 2C>3 form ed b y b u rn in g . See P a rr a n d W heeler, Th i s Jo u r n a l. 1, 636.
W — 2620 S
Cal. v alue, u m t coal --- — ---—-r_
1.00 —*[M + A + 5 / 8 S + 0 .08(A — 1 0 /8 S)3 [W =» calories as d e te rm in e d , M = m o istu re a n d A = ash as d e te r
m in e d ; th e expression 0 .0 8 (A— 10/8 S ) is used for Illin o is a n d W estern coals, a n d 0 .0 6 (A— 1 0 /8 S) fo r E a s te rn coals.]
2 F ro m a m in e in v ic in ity of th a t fro m which N o. 40 w as ta k e n .
8o
during slacking. It was found that slacking could be prevented in large degree by storing in tight cov
ered bins, but that in both open and closed bins, with slacking and without, the coal lost in eight months about 5 per cent, of its heat value.
The laboratory investigation has shown that coal absorbs oxygen most rapidly immediately after mining. The sample from Saline Co., Illinois, for example, absorbed 2 liters or more of oxygen in the first four days after mining, and after five months the rate of absorption had decreased to approximately 0 ,7 liter in four days. This rapid absorption of oxygen just after mining suggests the advisability in order to avoid spontaneous combustion, of keep
ing fresh coal more or less open and cooled b y ventila
tion until a proper time has. elapsed after mining.
Experiments are now being begun in the laboratory to show the comparative rise in temperature and ab
sorption of oxygen by different coals on passing air through a sample a given length of time at ioo° C.
The effect also of fineness of division and amount of surface exposed on the absorption of oxygen is likely to be large and will be investigated.
To summarize the results of the investigation thus far accomplished, coal absorbs oxygen from the air during storage without forming CO, and the amount of oxygen absorbed accords approximately with the deterioration in heat value. Oxidation may be largely prevented by immersion under water. Meth
ane is evolved from freshly mined coal in quantities of importance as bearing on mine explosions but of no importance as a loss of fuel value. Outdoor tests are being conducted to determine the extent of the loss during storage in the open as compared with im
mersion under water. Laboratçry by-product tests are being carried on to determine changes in the yields of gas, tar and ammonia through deterioration in storage.
T H E ANALYSIS OF B A B B ITT M ETALS; SOLDERS AND JOURNAL BRASSES.
B y D . J . De m o r e s t. R eceived J a n u a ry 22, 1910.
The separations involved in the analysis of these alloys of lead, copper, antimony, and tin as ordinarily carried out are long and tiresome. Furthermore, the results obtained are not always satisfactory.
In the analysis of alloys containing tin with lead and copper, but no antimony, the usual procedure is to separate the tin from the other metals as meta- stannic acid by means of nitric acid. This meta- stannic acid, however, is always contaminated with oxides of lead and copper and phosphorus, which cannot be washed out. The old method of remov
ing these oxides is to fuse the Sn0 2 with sodium car
bonate and sulphur and to dissolve out the sulpho- stannate formed, leaving the lead and copper as sul
phides. Sometimes two fusions are required. This method is time-consuming and troublesome.
Experiments by the writer show that accurate re
sults can he obtained in a short time by the following procedure: The metastannic acid is dissolved in NH4HS, leaving the lead and copper as insoluble sulphides. This NH„HS solution is electrolyzed, giving very accurately and quickly the amount of tin in the sample. The sulphides of lead and copper are added to the main solution of lead and copper, which is then electrolyzed.
This NH.,HS treatment of the metastannic acid with subsequent electrolysis is new, so far as the author is aware.
When antimony is present, as well as tin (as in type metals and babbitts), the nitric acid separation, as above mentioned, cannot be used because anti
mony is not rendered entirely insoluble by the acid.
The old method of separation by means of alkaline sulphides has to be used. B ut this process, as given in various texts, consumes much time and, according to the author’s experience, is very liable to leave some antimony and tin with the lead and copper.
The results of many experiments, however, show that this method can be modified so as to give com
plete separation in 3/4 of an hour after the sample is weighed up, instead of two to four hours, as re
quired by the ordinary wTay. The modification in
volves the solution of the sulphides of lead and tin in nitric acid and then precipitation of the lead and copper a second time as sulphides.
After the antimony and tin have been separated from the lead and copper, the standard method has been that of Clark1 for the separation of antimony from tin. In this method the antimony is separated from the tin by precipitation by H2S in oxalic acid solution and the sulphides weighed up. Also the method of Rose, modified by Hampe,2 in which the antimony is precipitated as sodium antimoniate.
B u t these methods are also long.
The results of experiments show that from an N H jH S solution antimony and tin can be quickly and quantitatively precipitated together in a pure state electrolytically.
Further, it was found that the deposit can be dis
solved from the electrode without loss, the antimony oxidized to I i3SbO,, and titrated accurately iodi- metrically. The tin is obtained by difference. This precipitation of antimony and tin together, electro
lytically, with subsequent titration of the antimony, is new so far as the author is aware.
The writer tried to use the method of electrolysing the antimony and tin solution in a Na2S solution, from which the antimony only is supposed to sepa
rate, but the process did not prove successful.
J Chem. N ew s, 21, 124.
* Chem. Ztg.> 18, 1900.
The whole process for the determination of lead, copper, antimony and tin can be completed easily in 3*/2 to 4 hours.
During the first part of this investigation, the writer used rotating anodes or cathodes in the electrolysis with good results. B ut there is some trouble in keeping good electrical connections with the rotating electrode unless an expensive mercury cup contact is used and in almost all the work on alloys contain
ing both antimony and tin, stationary electrodes were used, One of which is a platinum gauze cylinder, 2" high and 1" in diameter, upon which the metals were precipitated. To hasten the precipitation the solution was agitated by means of a platinum paddle operated by a water motor. The deposits are all very adherent and dense. The motor was belted to a group of six stirrers, so that many different depositions can be carried on at once. Using a gauze cathode and rotating the solution in this way it is possible to deposit 0.300 gram of copper quanti
tatively in 10 to 15 minutes. A particular advan
tage of rotating the solution instead of the anode or cathode is that it permits the use of any style of electrode.
The methods in detail are as follows:
1. a n t i m o n y n o t p r e s e n t (a s i n s o l d e r a n d JO U R N A L B R A SS E S ).
Two grams of the journal brass are dissolved in nitric acid (sp. gr. 1.42) and evaporated to dryness to bring the metastannic acid to such a con
dition that it will not clog up a filter paper. The use of a gentle air blast over the solution facilitates the evaporation. To the residue 50 cc. of water and 5 cc. of H N 0 3 are added, heated to dissolve the lead and copper, etc., and filtered. The metastannic acid on the filter is washed two or three times and then washed back into the beaker or flask in which the metal was dissolved. 25 cc. of N H 4HS (made by saturating NH4OH, (sp. gr. 0.9) with H2S) are poured through the filter and into the flask. This will dis
solve all the metastannic acid and precipitate as sulphides the lead and copper which contaminated the tin. The flask and its contents are heated and shaken for about ten minutes and then the solution poured through the same filter as before, catching the NH4HS solution of the tin in a 300 cc. beaker. The sulphides on the filter are washed with water con
taining some NH4HS. The filtrate is diluted to 200 cc. The small amount of PbS and Cu2S is dissolved in a little nitric acid and added to the main solution of lead and copper.
One hundred cc. of the tin solution are pipetted off, 10 cc. of NH4HS and 4 grams K C N are added and the solution electrolyzed with a 5- to 6-ampere cur
rent, rotating the solution as described below under the analysis of alloys containing both antimony and tin.
The solution of lead and copper is diluted to 200
cc., 50 to 100' cc. (according to the amount of lead present) are pipetted off, 15 cc. IIN 0 3 added, and the solution is electrolyzed, using a 5- to 6-ampere current and rotating electrode as described below.
A n y iron and zinc in the metal are left in the solu
tion from which the lead and copper are deposited.
If it is desired to determine these, the solution is evaporated to dryness, dissolved in a little HG1, the iron oxidized with H20 2 and precipitated with ammo
nia. The filtrate from the iron is made strongly acid with HC1 and boiled to decompose the H30 2.
The solution is then titrated with K 4Fe(CN)0, using uranium acetate indicator.
The following are some results obtained by this method upon two samples of journal brasses:
W t. of Cu. W t. of P b. W t. of T in.
N o. 1... ... 0.7 5 9 2 0.1 3 0 4 0.0701
0 .7 5 9 0 0.1 3 0 5 0.0 7 0 5
0 .7 5 9 2 0 .1 3 0 0 0.0 7 0 3
N o. 2 ... ... 0 .7 8 5 6 0 .10 12 0 .0 9 0 9
0 .7 8 6 6 0.1 0 0 6 0.0 9 0 5
0.7 8 4 2 0 .10 10 0.0905
0 .7 8 4 4 0.1002
2. A N TIM O N Y P R E SE N T , (AS IN B E A R IN G M E T A LS ).
One gram of the alloy is placed in a 200 cc. beaker and covered with 20 cc. of water. In this are dissolved 5 grams of tartaric acid and then 10 cc. HNOa (sp.
gr. 1.42) are added. This* will dissolve the alloy quickly unless it is in large pieces, which it never need be. When dissolved the solution is diluted to 50 cc. and a strong solution of NaOH is poured in until the hydroxides first formed dissolve and leave the solution clear. The liquid should not be heated as this may cause a precipitate of metastannic acid to commence to form in the alkaline solution. The solution is poured slowly and with constant shaking into a flask containing 150 cc. of a boiling hot solu
tion of 10 grams of NaOH and 10 cc. of a colorless saturated solution of N a^ . (The solution should be colorless or some copper will remain in the solution.) The contents of the flask are agitated for several minutes and then allowed to settle. The sulphides of lead and copper will settle quickly and compactly.
The clear solution is decanted as closely as possible through a strong filter paper folded in ribs. The pre
cipitate is washed twice by décantation, using about 25 cc. of water each time.
Now to the sulphides in the flask 5 cc. of H N 0 3 are added and heated until the black sulphides dis
appear. Then the solution is made alkaline with NaOH again and 10 cc. Na2S solution added and heated and shaken vigorously for several minutes.
Again the supernatant liquid is decanted through the same filter, washed twice by décantation and then the sulphides transferred to the filter and washed twice more with hot water containing a little Na^S.
The filter paper with its contents is placed in a crucible and heated gently so as to dry the sulphides.
While these are drying, sulphuric acid is added un-
der a hood to the filtrate which contains the Sb and S11 until the solution, which should have a volume of 400 to 500 cc., is acid. The liquid is stirred well and allowed to settle for a few minutes, then decanted through a filter paper as closely as possible to get rid of the greater part of the liquid. The beaker containing the sulphides of antimony and tin is set under the funnel, and 25 cc. of the NH.tHS solution diluted to 50 cc. are poured through. This will dis
solve the sulphides. The solution is transferred to a 300 cc. beaker, diluted to 150 cc., 4 to 5 grams K C N are added, and the solution electrolyzed, the solution being rapidly rotated.
The cathode used was a cylinder of platinum gauze, 2" high and 1" in diameter. The voltage used was 8 to 10 volts and the current 5 to 6 amperes. This large current will heat the solution considerably and it is best to set the beaker iii a basin of water. The KCN keeps sulphur from separating out on the anode in excess by forming KCN S with the polysulphides.
The tin and antimony should be deposited in 30 to 60 minutes, depending on the amounts present.
The cathode is lifted out and washed first with water, then with alcohol, and dried on a steam plate. If any pieces of sulphur are entangled in the meshes of the gauze, dip the cathode in CS, before washing with alcohol. This, however, is rarely necessary.
After weighing, the solution is again electrolyzed for ten minutes and the cathode washed and weighed.
If the weight has not increased more than 1 mm. in these ten minutes the electrolysis is complete.
After the cathode is weighed it is placed in a small beaker and 5 cc. of strong H N 0 3 are poured over it from a pipette. The acid is heated and the beaker tipped and the electrode turned so that the H N 0 3 will dissolve off all the deposit that is possible. There will always be some black stains left 011 the cathode, which are very difficult to remove with H N 0 3. The gauze is washed with a fine jet of water over the beaker. Then the gauze is set into another small beaker and 60 cc. of a strong HC1 are poured over it, which will dissolve off the black stains. The H N 0 3 is used first to avoid the loss of antimony as SbH3, which would take place if the deposit were dissolved in HC1 alone.
The gauze is then washed with a jet of water into the HC1 and the two solutions poured into a 500 cc.
Erlenmeyer fiask and the beakers washed with a lit
tle more HC1. The solution should be boiled vigor
ously for 10 to 15 minutes to decompose the H N 03.
Or, instead of mixing the two solutions, the 5 cc.
of H N 0 3 are evaporated to dryness in a platinum dish (for speed), then the residue is dissolved in 60 cc. HC1. This last way is the best but takes more time.
Now, to the hot IiCl solution 5 grams of K C 103 are added in small amounts at a time, then 50 cc.
11,0 are poured in and the solution boiled while pass
ing through a stream of C0 .2 until the free chlorine is all gone, as shown by starch-iodide paper. This
takes 15 to 20 minutes.
The K C 103 must not be added before the H N 0 3 is decomposed, for the K N 0 3 formed greatly prolongs the time necessary to get rid of all free Cl.
When the free chlorine is all gone water is added to make a volume of 150 cc. and the solution cooled under tap water while passing in a stream of C0 2 to displace the air. The solution should be color
less. The C0 2 is made from marble and HC1.
When cool, the current of CO, is stopped, 4 grams K I are added and the liquid stirred until the K I is all dissolved. Then standard Na,S,0 3 solution is run in until the color due to iodine all disappears, starch solution is added, and the excess thio titrated back with standard K,Cr20 7 until a blue color is ob
tained. This should take only a few drops. The writer prefers this end point to merely titrating with Na2S,0 3 until the blue starch iodide disappears.
The K C 103 oxidizes the antimony to H3SbO,. This liberates iodine according to the reaction:
H3SbO, + 2KI + 2HCI =
2ICCI + H3Sb0 3 + 2I + H20 . Then the thiosulphate is oxidized by the iodine in the reaction:
2Na,S,03 + 2I = Na,S.,0 „ + 2NaI.
The writer standardizes the thiosulphate against K,Cr„0 7 of known iron strength. Also by treating Sb,0 5 or Sb or tartar emetic by dissolving them in HC1 and K C 103 and treating as above. The two methods of standardization check very closely. The iron strength of the bichromate, multiplied by 1.0751, gives its antimony value. The “ thio” solution is made by dissolving 20.7 grams of N a,S,05.5H,0 and diluting to one liter. The author does not like the use of SnCl, for the titration as it changes strength so rapidly.
There is nothing which can be deposited with the antimony and tin which will interfere with the process.
Arsenic does not interfere.
While the electrolysis of the antimony and tin is going on, the dried sulphides of lead and copper are crumbled into a beaker, the paper burned and the ash added to the rest in the beaker. The sulphides and ash are dissolved in 40 cc. concentrated HN0 3.
In this solution the lead may be determined as sul
phate and the copper in the filtrate from the lead titrated by the iodide method. But it is much quicker and more accurate to determine the two electrolytic- ally, according to the following:
The solution is diluted to 100 cc., 50 cc. are pipetted into a platinum dish, 50 cc. of water added and elec
trolyzed with a potential of six volts for a few min
utes. The voltage is then increased to 10 to 12 volts,
83 keeping the solution stirred. The lead is all deposi
ted on the dish, which is the anode, in about 15 min
utes. Then part of the UNO, is neutralized with am
monia and the electrolysis continued for 15 minutes, when the copper is all deposited on the gauze cathode.
The electrodes are washed quickly with water, then with alcohol, dried and weighed. The PbO, should be dried at above 200° C. to expel water.
To show that antimony and tin are deposited quantitatively the following results are given:
P rese n t. P o u n d .
Lead. C opper. A n tim o n y . T in . Sb + Sn. A ntim ony. Tin. Cu.
0 .7 0 0 0 0.1 5 0 0 0.1000 0.2 5 1 5 0.1 4 8 0 0.1 0 3 5
0.7 0 0 0 0.1000 0.2495 0.1 4 9 5 0.1000
0 .7 0 0 0 .0 5 0 0 0 .1 5 0 0 0.1000 0.2 5 0 3 0 .1 4 9 0 0.1 0 1 3 0 .7 0 0 0 .0 5 0 0 0 .1 5 0 0 0.1000 0 .2 5 0 0
0 .7 0 0 0 .0 5 0 0 0 .1 5 0 0 0.1000 0.2 4 8 0 0 .1 4 8 0 0.1000 0 .0 5 0
0 .1 8 0 0 0 .1 8 0 0
0 .1 5 0 0 0 .1 5 0 0 0.3005 0.1505 0 .1 5 0 0 0 .1 5 0 0 0.1000 0.2 4 9 5 0 .1 4 9 0 0.1005 0 .1 5 0 0 0.1000 0.2 5 1 5 0.1 4 9 5 0.1020
P re se n t. P o u n d .
L ead . C opper. A n tim o n y . T in . L ead . C opper. S b + S n . Sb. Sn.
0 .6 5 0 0 0 .0 5 0 0 .1 5 0 0 0 .1 5 0 0 0 .6 5 0 5 0 .0 5 0 5 0 0 .2 9 9 9 0 .1 4 9 6 0.1 5 0 3
In this last analysis the thiosulphate was standard
ized against K ,C r,0 7 solution, giving as the strength of the thio i cc. = 0.00504 gram antimony. Then 0.200 gram of pure SbX). was dissolved in HC1 and KCIO3 and treated as iii the regular process. Result, 1 cc. = 0.00504 gram Sb. This was then repeated except that 5 cc. of H N 0 3 were used as in the process.
Result, 1 cc. = 0.00504 gram Sb.
The electric current used in the work at the De
partment of Metallurgy was obtained from an alter
nating current n o -vo lt lighting circuit rectified by means of a chemical transformer, designed by the writer, making use of the well-known aluminium method. The rectifier was able to transform 10 amperes for 60 hours without trouble and has been in use for a year without any repairs. The aluminium and lead electrode were each 3i/2" by 10" by 3/8"
and were immersed in a saturated solution of (NH.,)3PO, in glass cylinders around which water circulated. Four cells were used and connected as described in Perkin’s “ Practical Methods of Electro- Chemistry.” 85 per cent, of the a. c. was rectified.
Almost all the experimental work 011 alloys con
taining both antimony and tin upon Which the fore
going processes were based was done at the labora
tory of the Department of Metallurgy of the Ohio State University. The rest was chieflv done at the laboratory of the Union Pacific Railroad at Omaha.
SUM M ARY.
Antimony and tin may be separated from lead and copper by the alkali sulphide method in three-quar
ters of an hour.
Metastannic acid may be purified by dissolving it in NH^HS and filtering oil the sulphides of copper
and lead. This N H ,IiS can then be electrolyzed for tin.
Antimony and tin may be accurately and quickly deposited together electrolytically from a solution of their sulphides dissolved in NH,HS.
The deposit of antimony and tin may be dissolved off the electrode and the antimony oxidized to H^SbO., and titrated accurately.
Rapid electrolysis with excellently adhering de
posits may be accomplished when gauze electrodes and mechanical stirring of the solution are used.
Alloys of lead, copper, antimony and tin may be accurately analyzed in three to four hours.
De p a r t m e n t o f Me t a l l u r g y, Oh i o St a t e Un i v e r s i t y,
J a n . 12. 1910.
[ C o n t r i b u t i o n1 f r o m A r t h u r D . L i t t l e , I n c . , L a b o r a t o r y o f E n g i n e e r - i n g C h e m i s t r y . ]
TH E L IB R A R Y AS AN ADJUNCT TO INDUSTRIAL LABORATORIES.
Iły Gu y 1C. Ma r i o n. R eceiv ed J a n u a ry 10, 1910.
It has been recently said:1 “ The financial library of the present day is a comparatively recent institu
tion, and man}' causes have contributed to its develop
ment.” Equally true is this statement in its applica
tion to the library as an adjunct to industrial labora
tories. Let us review for a moment, then, the causes which have contributed to the usefulness and develop
ment of the Laboratory Library. Many, of them are the same as those which are causing to spring into existence the increasing number of small specialized libraries about the country in general. The chief cause, however, is the phenomenal growth of all busi
ness, which continually necessitates the introduction of new methods for expediting its procedure. Spe
cialization has entered here as elsewhere, and it has been found better to have one man prepared to answer the many inquiries of a general nature coming to the laboratory than to be forced to distribute these in quiries throughout the staff. This has meant, then, the collecting of the laboratory’s resources (books, pamphlets, experimental data, catalogues, documen
tary experience, etc.) at one point into a library.
In this w ay a new channel has been formed for the transaction of a portion of the laboratory’s business, namely, the answering of the general inquiries arising both in and outside its ranks; and the library has be
come a vital factor in the operation of the organiza
tion. But, not only has the work been better sys
tematized by the advent of the library; its coming has enabled the laboratory to accept wider oppor
tunities, to enter with less hesitation new and un
exploited fields, and to increase its efficiency in a large number of ways which make for confidence
1 F ro m a p a p e r e n title d “ Som e A sp ects of a F in an cial L ib ra ry ," b y B ea tric e E . C arr, p re sen te d a t th e first a n n u a l m eetin g of th e Special L ib ra ries A ssociation.
84 Mar., 1910 and progress; in fact, with its constant accumulation
of the laboratory’s daily experience, upon which no value can appreciatively be set, with its acquiring and classification of the ever-increasing amount of literature from without, it becomes, as the accumu
lated experience of the past, the base upon which the future rests. Another contributory cause to the existence of the library is the speed of present-day business. No longer can the chemist wait until he has an opportunity to consult the public library or other outside source of information. This method is too slow. He is supposed to know. That is why he is consulted by the business layman, and his knowl
edge must be forthcoming on the spot. So the library has come to his aid and enabled him to hold his lay
man often on the telephone wire while the desired information is found. Thus the chemist has embraced the library as an adjunct largely in self-protection.
Since these contributing causes are readily appar
ent, and the laboratory library as an institution al
ready exists, it is for us to consider the specific nature of the demand made upon it (answering at the same time, if we can, why the public library does not fill the need), its limitations, the literature required and acquired, and then for a moment to look at a concrete example of such a library as we have in mind with its various working systems.
Specific Nature of the Demand.— The industrial laboratory needs a highly specialized library, at the same time one containing certain well-chosen general works. For example, its shelves must be rich with analytical works in almost every field, with books on explosives, beverages, foods, oils, gases, fuels, ceramics, textiles, paints, soaps, gums, essences, distillation products, metals, rubber, leather, wood, celluloid, etc. In fact, a small library of technology with only the best works chosen in each branch of industry fills best the need. For general works, it needs biblio
graphical books, transactions of the various scien
tific and learned societies, trade catalogues from the industries which the laboratory in question particu
larly serves, the current technical periodicals cover
ing the fields claiming its attention, and a collection of general books 011 English, advertising, engineer
ing, building, physics, chemistry, biology, botany, and manufacture, to which should be added refer
ence lists, dictionaries, encyclopaedias, directories, maps, atlases, etc. Indeed the demand in the indus
trial laboratory librar}' is both for a small commercial library as well as a highly specialized library of tech
nology. It is because of this peculiar mixed nature of the demand that our public libraries cannot hope to meet it. They rarely give any attention to the commercial side of their development, and their general lay clientage forbids their building up along the technical and industrial lines beyond a few of the more general books. B ut what is still worse,
their distance most often militates against them.
Moreover, the chemist in industry must have his works without fail when he wants them. I t will not suffice to await their return from some other borrower from a library. The peculiar type of library to serve the interests of the laboratory must be able to hold its entire resources within certain prescribed limits so that it can recall them at a mo
ment’s notice.
Its Limitations.— W hat are its limitations? The people making use of it will rarely, if ever, exceed fifty in number. B ut these people, instead of being a desultory public are intensely active specialists, and bring to the library inquiries which require the best skill in their answering. In this w ay the library does not suffer from lack of quantity, for its interest is more than kept up by the increased quality sought in its work. Its purchases are also limited, and its accessions cannot be compared in numbers with those of the public library, for very few things are acquired which are not for a well-defined purpose. In spite of the narrower field and its restricting limitations, the laboratory library is still, however, a unique and purposeful proposition, changing the more general characteristics of a library to meet its changed sur
roundings.
Literature Required and Acquired.— We come now to the literature required and acquired, which prove in reality to be of two quite different classes. We have already explained above, in touching upon the specific nature of the laboratory library, what kinds of literature are required. They are chiefly text
books, specialists’ pamphlets, trade catalogues, refer
ence works, maps, etc. These must be all purchased and are quite necessary. ’ In distinction from these, there is a vast bulk of data which we may properly call acquired rather than required. It is made up of the information culled from the laboratory’s daily correspondence, out of the experiences of the various members of the laboratory staff, from experiments carried on in the laboratory, from various technical reports and investigations made for clients; in short, it is made up of the accumulated results of the internal life of the laboratory itself. In fact, this acquired data is unquestionably for the laboratory library, the most valuable -part of its information.
Information Dept, of Arthur D. Little, Inc.— Per
haps a more minute description of a concrete exam
ple of such a library as we have briefly described above in general terms will- be more useful'and suggestive to you. The Information Department of Arthur D.
Little, Inc., which is entrusted to my care, will be briefly explained, touching upon the sources from which we get our material, the systems in vogue, the bulletins issued, the way in which the library becomes- a clearing-house for information, a few of its typical problems, and lastly, its aims.
Sources of Material.— Our material is obtained chiefly through five channels: the purchase of special books or pamphlets to meet definite requests, through the mailing lists of outside concerns who send us their advertising literature from time to time, through the kindness of individual acquaintances at various points who desire to exchange results, from the chance notices appearing in the technical periodicals, which prompt us to initiate ourselves the getting of the information in question, and from the calls of clients and salesmen who may leave with us at their visits information of one kind or another. These are out
side sources. The material produced within our own business of course comes to the library through the regular office routine.
Classification.— All of this material then, on its receipt, falls into one of the following six grand groups:
books, pamphlets, trade catalogues, special data, periodicals, and the museum collection.
Books.— The books are classified by the Dewey Decimal System, which has long ago proved its claims in the public libraries. I t serves our purposes very well indeed, and maintains uniformity with the best prevailing library practice in the majority of public libraries. B y its use, like books stand together on the shelves, and those related stand closely by. It permits of perfect intercalation of new material upon the shelves in proper order. Supplementing the Dewey subject number, each book has its Cutters’
author number. We use the K ate E. Sanborn ar
rangement of C. A. Sutters’ alphabetic order table for assigning these numbers. All of our books are entered in an accession book on their reception, thus keeping accurate data on each volume.
Pamphlets.— -Pamphlets receive treatment similar to that of the books as far as their numbering goes, but in order to keep this material in a distinct class by itself, the small letter (p) is used before the classi
fication number. The pamphlets are then placed in regular pamphlet boxes on the shelves.
Trade Catalogues.— Trade catalogues receive a some
what different treatment. This is the most objec
tionable class of material entering the library, owing to its entire lack of uniformity. We have found the best practical treatment to be a shelf arrange
ment, in which all the small material is enclosed in envelopes (9 5/ 8" x n 3/ / , without 'flap, opening on the long side) and standing in one alphabet from (A) to (Z ). To each company’s catalogue is assigned a Cutter number, thus the catalogue of the Sturtevant Mill Company is S 936, which places it at one and the same time in a strictly alphabetical and numerical decimal order. This arrangement has the additional advantage of allowing those coming to the library seeking a definite concern’s catalogue to go directly to the shelves, without the consultation of an index.
Special Data.— Our special data is a somewhat
miscellaneous class of material, made up of an accu
mulation of newspaper clippings, reviews of articles, results of personal interviews, special investigations, data culled from correspondence, and many other sources. The greater part of it is copied on corre
spondence size sheets, and placed in a vertical file.
A small letter (s) preceding the number keeps this material distinctly in one class. The arrangement here is also by subject with the use of the decimal system.
Periodicals.— The class of periodicals is made up of a selected list of about fifty scientific and technical publications, both foreign and domestic. Many of these are purchased directly, while others are re
ceived with memberships in the different learned societies. Notable in this class of literature is a new type which is provoking some attention, the indus
trial publications. We may name a few, such as The Stone & Webster Public Service Journal, Industrial Progress, Reactions, The Valve World and The General Electric Review. For convenient reference all the periodicals are given symbols such as E N for Engineering News, E R J for Electric Railway Journal, P T J for Paper Trade Journal. Thus with the date of issue known, a certain reference can be easily and briefly made to any article. When the periodicals are later bound, as many of the better ones are, they of course leave this class and become books. As for the others, after clipping they are thrown away.
Museum.— The museum collection is made up of a large assortment of samples acquired from various points, clients, etc., for example, fibrous materials, mineral matter, special papers, artificial silks, stand
ardized steels and irons, paper-making chemicals, electric railway materials, etc. To each individual sample we give a .consecutive number, preceded by a small letter (m), which serves to keep this material in one group by itself. The material is filed in glass cabinets, where it is on constant exhibition, and proves, at least to our visitors, a source of lively interest.
Color Scheme.— 111 the actual handling of this ma
terial a color scheme is used. White tags are placed on the books, salmon on the pamphlets, blue on the catalogues, yellow on the special data, green on the periodicals, and cherry 011 the museum material.
This is found to be helpful in the work, always aiding the eye in the rapid classification of material, and pre
venting often the return of material to the wrong place.
Accessioning.— Now as to the processes through which this bulk of material passes. Everything en
tering for permanent file is first accessioned, then catalogued and filed. The accessioning of the books has already been described; the other classes are ac
cessioned on sheets kept for one week only, from which the information is later transferred to the weekly
bulletin, which will be described below. This does not apply to the periodicals which are checked upon a special card system as they are received, nor to the museum articles, which are not accessioned.
Cataloguing.— The classifying takes place next, which is followed as soon as finished by the index
ing. Author, title and subject cards are made out in nearly every case, and often several subject cards.
The cards completed, the materials go to their respec
tive files, and the cards to the library index.
Card Catalogue.— This index is one large dictionary catalogue from (A) to (Z), and now numbers between thirty and forty thousand cards. These are all stand
ard 3" x 5" library cards, and the entire index is liberally supplied with guides for the searcher. After locating the proper material wanted in the index, the nature of the call number on the card will always indicate the group in which the material itself will be found. This has already been explained in earlier paragraphs upon the different groups of material, by the use of the small letters (r), (/>), (m), etc., as symbols in the call numbers. A distinctive feature of filing cards with us is the placing of them first in their proper places, without the removal of the rods from the drawers. A second party then goes through the cabinet, verifying them and dropping them into their permanent arrangement.
Charging.— The charging system carries out the color scheme. We have a small tray with the neces
sary compartments, in which narrow slips are used for keeping records of the material out of its regular place. White slips receive the book charges, salmon the pamphlet, blue the catalogue, and so on. On each slip is written the call number of the material, the initials of the borrower, and the date on which the loan is made. All material which is returned during the day is kept together in one place, and is returned to the files the first thing the following morning, the charge slips being removed at the same time from the charging tray.
Bulletins.- So much for the systems iii vogue in our library. These are laid out with the idea that they may be almost automatic after those operating them have once learned them. But we now ap
proach a more interesting side of the work. Every Monday morning we issue a bulletin which covers all the accessions of the previous week in classified shape, so that all the important heads of depart
ments may at least keep up to date with what the library is doing. This bulletin idea is capable of much greater expansion, and as time goes on, we hope to make much more of it. It should contain sug
gestions, possible openings for increasing the business, perhaps a selected list of the more suggestive articles appearing in the press for the week, and so on. With sufficient time to devote to this purpose one can scarcely prescribe a limit to its possible development.
Correspondence.— For indexing purposes all of the correspondence of the various departments of our laboratory goes to the library before being filed.
This is the regular channel through which all mail must go, and nothing is filed until noted by the library with its library stamp. This enables the library to pick out 'and index such useful bits of information as would otherwise be lost sight of.
Library a Clearing-Honse.— The library is the clear- ing-house for much of the information in our labora
tory. Every second day the periodicals which have once been distributed among the staff come back by way of the mail baskets to the library, and are re
charged and again distributed to a new group of readers. This system insures their receiving atten
tion, for the readers know that the periodicals will be taken away whether read or not, when the time is up, and passed on to others. In another way the library acts as a clearing-house. If the Paper and Pulp Department brings us a request for informa
tion which we know is common knowledge in the Fuel Department, why should we not exercise our ingenuity in bringing the proper parties together?
Again, if the Fuel Department works out successfully a problem which we know would help the Electric Railway Department, and the data is filed with us, why should we not call it to the latter’s attention?
Y ou will readily see the effect this will have upon the general esprit de corps of the laboratory.
Problems Encountered.— Let us now look at a few of our typical problems: W hat are we asked to solve, and what form do these requests take? We have a form called our “ Inquiry Blanks,” printed 011 paper of a distinctive color. A pad of these blanks lies on nearly every desk in the various departments about the laboratory. When a request for informa
tion comes in or arises in any department, one of these forms is filled out and sent to the library, where it becomes our duty to provide an answer at the earliest possible moment. These slip's are numbered consecutively as received, and after going to the ac
counting department for the distribution of their time charges, are returned to the library and kept in consecutive order. They serve thereafter as memo
randa from which the answers can be readily found in case the inquiries are duplicated later from other sources, for each slip is filled out with the sources from which any information has come. As to the questions themselves, a few typical ones m ayb e cited:
“ Who are the principal manufacturers or dealers in copper sulphate?”
“ W hat patents have been taken out on the removal of caffeine from coffee?”
“ W hat is the procedure for anestheticizing plants?”
“ Please give me a list of articles, with reprints and extracts, published during the past several years on Vanadium and Tungsten Steel. ”
