The Journal of Industrial and Engineering Ghemistry
Published b y TH E AM ERICA N CHEM ICAL S O C IE T Y
A T E A S T O N , P A .
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Volume X F E B R U A R Y I, 1918 A v ^ No. 2
Editor: C H A R L E S H. H E R T Y V
Assistant Editor: Gr a c e M a cLe o d Advertising M j G . W . No t t
A D V IS O R Y B O A R D
H . E. Ba r n a r d, H . K . Be n s o n, F. K . Ca m e r o n, B . C . He s s e, A . D. Li t t l e, A. V. H . Mo r y, M . C . W h i t a k e r
P u b lish e d m o n th ly . S u b sc rip tio n p rice to no n -m em b ers of th e A m erican C hem ical S o ciety , 56.00 y e a rly ; single copy, 60 c en ts
P rice p e r sin g le copy to A m erican C h em ical S ociety m em bers, 50 cen ts. F o reig n po stag e, sev en ty -fiv e c en ts, C an a d a , C u b a a n d M exico ex cep ted E n te re d as S econd-class M a tt e r D ecem b er 19, 1908, a t th e Post-O ffice a t E a s to n , P a ., u n d e r th e A ct of M a rc h 3, 1879
A ll co m m u n ica tio n s should be sen t to T h e J ou rn al of Ind u strial and E n g in e e rin g C h em istry.
T e le p h o n e : V an d erb ilt 1930 35 E ast 41st S treet, N ew Y o rk C ity
S u b scrip tio n s and c la im s for lo st co p ie s sh ou ld be referred to C h arles L. Parson s, B o x 505, W ashington, D. C.
E s c i i H N i i A c n Pr i n t i n g Co m p a n y, Ea s t o n, Pa.
Of f ic er s for 1918:
Dr. Nichols— Leader in Chemical In d u stry...
Ed it o r ia ls:
On with the Investigation...
Somebody, Please C u t the T a p e ...
Platinum Oscillations...
A n Appreciation and a G reetin g...
Chem istry Insignia...
Orig in al Pa p e r s:
The E xtraction of Potash and Other Constituents from Sea W ater Bittern. Joel H. H ildebrand...
The D irect H eat Treatm ent of Cem ent M ill D ust to Increase Its Water-Soluble Potash Content. Albert R . M e rz...
E ffect of Coal A sh on the Liberation and N ature of Cem ent M ill Potash. N . S. Potter, Jr., and R . D.
Cheesm an...
Toluol Recovery and Standards for Gas Q uality. R. S.
M cB rid e ...
Catalysts in Vulcanization. D. Spence...
Vulcanization of Rubber b y Selenium. Charles R.
B oggs...
T h e Pigments of the Tom b of Pem eb. Maximilian T o c h ...
The Preparation of N/100 Perm anganate Solutions. J.
O. Halverson and Olaf Bergeim ...
The Use of Microorganisms to Determine the Preserva
tive V alue of Different Brands of Spices. Freda M . Bachm ann...
Disinfection with Formaldehyde. A Substitute for the Perm anganate-Formalin M ethod. C. G. S to rm . . . . E ffect of Fertilizers on Hydrogen-Ion Concentration in Soils. F . W . M orse...
The Seeds of the Echinocystis Oregana. M ilo Reason D aughters...
Variation in the Ether E xtract of Silage. L . D . H a ig h . Labo r a to r y and Pl a n t:
Some M ethods of Analysis for N ebraska Potash Salts and Brines. A . H . M cD ow ell...
Suggestions on Some Common Precipitations. George H. B roth er...
A N ew Portable H ydrogen Sulfide Generator. W . Faitoute M u n n ...
An A utom atic H ydrogen Sulfide Stopcock. Carl H.
Classen...
A Simple and Efficient Filtering Tube. William M . Thornton, J r ...
Ad d r e sse s:
T h e Autom atic Control and M easurem ent of High Temperatures. R ichard P. B row n ...
Airplane Dopes. Gustavus J. Esselen, J r ...
T h e Collaboration of Science and Industry. V . Grig- nard ... 137
Pe r k i n Me d a l Aw a r d:
Introductory Address. Jerome Alexander... 138 M r. A. J. Rossi and His Work. F . A. J. F itzG erald .. . 138 Presentation Address. W illiam H. N ichols... 140 Address of Acceptance. Auguste J. R ossi... 141 Br i t i s h Pr o g r e s s i n Dy e s t u f f Ma n u f a c t u r e:
British D yes Limited. James Falconer, M . P ... 145 Levenstein Lim ited... 149 Cu r r e n t In d u s t r i a l Ne w s:
Platinum in Spain; Tungsten in M alaya; Tubular C ycle Components; M agneto Machines for Pocket Torches;
Therm it W elding; Refractory Properties of M agnesia Bricks; Prevention of Scale in Boilers; Electric Heat Storage in Boilers; British Board of Trade; Mineral Production of Victoria; M anufacture of Electrodes;
Recovery of Potash and Magnesia from Canadian Lake; Fluxes; W aterproof Varnish from Oil; Shellac D erivatives; Cellulose Turpentine; Substitute for Oil in Paint; D ye from Sulfite L yes; Electric A rc W eld
in g ... .' 150 Sc i e n t i f i c So c i e t i e s:
Reduction of W aste; Seventy-Fifth Annual M eeting American Association for the Advancem ent of Science, Pittsburgh, Pa., Decem ber 28, 1917—
January 2, 191S; Am erican M etric Association;
Annual M eeting Technical Association of the Pulp and Paper Industry, New Y o rk C ity, February 5 -7 , 1918; New Y o rk Section of the Société D e Chimie Industrielle... 1 5 3 No t e s a n d Co r r e s p o n d e n c e:
Tw o Letters on the Chem ical Control of Ammonia Oxidation; Avoidable W aste in the Production of Sulfuric Acid b y the Cham ber Process; Brom ine Pro
cess Decision; United States Tariff Commission In
quiry in Regard to Chemical Industries; Special Chemicals and Apparatus A vailable through the Chem istry Com m ittee of the N ational Research Council; As to Platinum ; Platinum Resolutions;
Fuel for M anufacture o f Chemicals; A Study of the Estimation of F a t in Condensed M ilk, E tc.— Correc
tion; Composition of Loganberry Juice and P u lp — Correction; Chem ists and the D r a ft ... 155 W a s h i n g t o n L e t t e r ... 1 6 0 P e r s o n a l N o t e s . . .■... 1 6 1 I n d u s t r i a l N o t e s ... 1 6 2 G o v e r n m e n t P u b l i c a t i o n s ... 1 6 5
B o o k R e v i e w s ... 1 6 7
Ne w Pu b l i c a t i o n s... 169 M a r k e t R e p o r t ... 1 7 0 T A B L E O F C O N T E N T S
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h i
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1 1 7 118 1 1 9
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92 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 Vol. 10, No. 2
OFFICERS FOR 1918
The following officers have been elected b y the A m erican Chem ical Society for the year 1918:
President: W illiam H. Nichols, General Chem ical C om p an y, N ew Y o rk C ity.
Directors: H. E. Barnard, State Laboratory of H ygiene, Indianapolis, Ind.; and G. D . Rosengarten, Pow ers-W eightm an - Rosengarten Co., Philadelphia, Pa.
Councilors-at-Large: H. E. Howe, A. D. L ittle, In c., Cam bridge, M ass.; G. A. H ulett, Princeton U niversity, Princeton, N. J.; W. A. N oyes, U niversity of, Illinois, Urbana, 111.; and Allen Rogers, P ratt In stitu te, B r o o k ly n ,
N . Y .
D R . N IC H O LS— LE A D E R IN C H E M IC A L
IN D U S T R Y
B y C . F . C H A N D L E R
D r . W i l l i a m H.
Nichols was one of the sm all group of New Y o rk chemists who, in 1876, originated this by far the largest chem ical society in the world. It now has 51 local sections and a p p r o x i m a t e l y
11,000 members, and publishes three distinct chem ical journals.
Dr. Nichols was born January 9, 1852, in Brooklyn, N. Y . He g r a d u a t e d fr o m the Brooklyn P o ly t e c h n ic Institute in 1868 and then entered New Y ork U niversity, where he had the good fortune to stu d y chem istry under Dr. John W. Draper, the first President of the Am erican Chem ical So
ciety. He received his
B.S. in 1870. In 1873 he received his M .S. from the same institution; in 1904, L L .D . from L afayette and Sc.D . from Colum bia. In 1912 he was decorated by the K ing of Ita ly with the Order of Com m endatore of the Crow n of Ita ly . He was president of the English Society of Chem ical Industry 1904-190 5 and of the Eighth International Congress of Applied Chem istry held in W ashington and New Y o rk in 1912.
In 1870, when only eighteen years old, he founded his own chemical business under the title G . H.
Nichols and C om pany, using his fath er’s name be
cause he was not y e t of age. Later the business was incorporated as the Nichols Chem ical Com pany.
The instincts of the pioneer in Dr. N ichols led to the origin in his plant of m any ideas and appliances used in chem ical industry to-day, for example, the well-known practice of storing and transporting sulfuric acid in steel.
The m anufacture of sulfuric acid from pyrites was first carried out profitably in the Nichols Chem ical W orks at Laurel Hill. The pyrites used contained some copper and the search for the proper m etallurgical treatm ent of it led to the invention of methods still em ployed for sm elting such ores and also to the devis
ing of a method for analyzing copper b y electrolysis, which was the foundation of the industry of the elec
tro lytic refining of cop
per. These processes for sm elting and refining copper ores were so su c
cessful th at the business grew rapidly to such d i
mensions th at in 1898 it was transferred to a special com pany, the Nichols Copper C om pany, of which Dr. N ich ols is president. The works, located on N ew tow n Creek, Brooklyn, constitute one of the most extensive copper plants in the world. In 1899, the c h e m i c a l branch of the business into the General Chem ical Com pany.
T he superior execu
tiv e ab ility of Dr.
Nichols shows in the success he has had in such enterprises as the rehabilitating of the G ran by Consolidated M ining, Sm elting and Power C om pan y, L td ., converting it into one of the best-m anaged cop
per companies in the world; the recent or
ganizing of the N ational A niline and C hem ical C om pan y, Inc., looking to the perm anent relief of A m erican textile m anufacturers and others; the bringing of a new lease of life to his A lm a M ater, the P olytechnic In stitu te of Brooklyn, which seemed to be on the decline but is to d ay a school of engineering of high m ark, due largely to the good work of Dr. Nichols.
W ith all these business activities D r. Nichols has acted as chairm an of the C om m ittee on Chem icals for the governm ent and just recen tly has been appointed b y Secretary Lane chairm an of the C om m ittee of Chem ists advisory to the Bureau of M ines.
Ne w Yo r k Ci t y Wi l l i a m H . Ni c h o l s, Pr e s i d e n t Am e r i c a n Ch e m i c a l So c i e t y
Feb., 19x8 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 93
EDITORIALS
O N W IT H T H E IN V E S T IG A T IO N
T he massing of Germ an reinforcements from the E a st on the western front led W inston Churchill, B ritish M inister of M unitions, in an address at the Am erican Luncheon C lub recently, to exclaim:
“ Am erica! Com e and aid us w ith all your might and speed, for this is a m atter for action on the largest scale ever planned. * * W e are sure to win the whole of President W ilson’s program if we will utilize all our resources fu lly .” Such an appeal, coming from a member of a race strong in self-reliance and bull-dog ten acity, must sink deep into the heart of e very Am erican.
T h a t we have lacked speed in m any of our prepara
tions has been shown clearly b y the investigations of the Senate C om m ittee on M ilitary Affairs. The re
ports show th a t the Com m ittee felt fu lly capable of probing deep into the supply of cannon, machine guns and rifles, bu t when the subject of amm unition for such arms, and particularly of the basic chemicals needed in its m anufacture, was approached, the in vestigation seemed at once to veer from so technical a subject. T h is is not difficult to understand, and yet we feel th a t the C om m ittee can perform further public service if it will extend its investigations to cover thoroughly this field, particularly as to acetic acid for aeroplane dope and toluol for high explosives.
Enorm ous quantities of acetic acid are needed im m ediately, and until this is supplied the aviation program will be held up. The present total output of this product is already engaged for the N a v y and our Allies. N ew factories must be built for further output.
W ith the lib erty motor com pleted, with all arrange
ments made for the supply of spruce wood in abun
dance, the startling fact remains th at, unless action has been taken w ithin the tw en ty-four hours previous to this w riting, not even the m ethod of m anufacture of the necessary acetic acid has been decided upon, much less has th e erection of any plant begun. In view of the tremendous difficulties of plant construction in these tim es, it is appalling to thin k of the delays ahead in this work which even in peace tim es and under normal conditions w ould prove an extrem ely form idable under
taking. I t looks as if someone has blundered seriously, especially when we reflect upon the unprecedented speed with which Congress at the outset appropriated
$650,000,000 for the aviation service.
The fundam ental im portance of toluol, the great need for it in the production of high explosives, and the m ethod of its m anufacture b y stripping gas are well understood at the present tim e. A ppro
priations have been available since th e adjourn
ment of the previous session of Congress. N early six months have elapsed since the conference was held in W ashington between representatives of the W ar D epartm ent, the gas producers, and the public service commissions. Y e t to-d ay there are m any gas plants with which no final arrangem ents h ave been made b y
the W ar D epartm ent for the erection of scrubbers to strip the gas. T h a t this condition is not due to lack of cooperation b y the companies is indicated in a le t
ter to us from Brig.-G en. W illiam H. Crozier. Under date of October 17, 1917, he states: “ W e have re
ceived a read y response to cooperate with us from every com pany th a t we have w ritten to so fa r.” W e have been informed b y the Ordnance D epartm ent th at for the present at least negotiations for the installation of apparatus for the recovery of toluol will not be conducted with gas plants 'whose cap acity w ould be less than 40,000 gallons per year. It would be interest
ing to learn through a public investigation how far these negotiations have resulted in actual contracts and inauguration of construction work, and w hat dates such contracts bear. U n fortu nately we are not in position to give much detailed inform ation on this point, but We know of one contract which has been shifting forward and backw ard for months, and is not yet signed. W hether the delay in settling the p etty features of the contract is due to the attitud e of the m anufacturer or to the methods of the W ar D epartm ent it is not for us to judge, but we do know th at the construction firm in question would not be at all adverse to an investigation of the reasons for this delay. When all is said, it is not a ques
tion of this or th a t m anufacturer; if any such firm delays the prom pt execution of governm ent plans, turn aside from him and get a contractor who will start the work prom ptly. I t is toluol th a t is needed, and not the saving of a few cents per gallon in its production. It would seem th at officials of the W ar D epartm ent are still following the leisurely w ays of contract m aking characteristic of peace tim es, while m aterial which m ay be of the utm ost im portance at a critical m om ent is now being burned, and can never be recovered.
Of course the decision to use m ixtures of toluol and ammonium nitrate for high explosives relieves the situation somewhat, nevertheless the am m onia plants are not yet completed. W e have upon us the responsibility of supplying not only the needs of our own A rm y, but of aiding in every w ay possible those of our Allies. This applies p articu larly to Ita ly , fighting so resolutely to-day, its ve ry existence im m ediately threatened.
If it be held th at toluol recovery must not exceed nitration cap acity because of lack of storage tanks, will not the W ar D epartm ent contem plate the m any cases of seem ingly autocratic procedure adopted b y governm ent officials during the last few weeks, acts which have been accepted cheerfully b y the country because th ey were war measures? In the ligh t of such procedure the storage question can readily be solved b y commandeering some of th e m any storage tanks scattered throughout th e coun try and now filled with petroleum products. C an anyone doubt the relative value to ourselves and our Allies of a half dozen such storage tanks filled on th e one hand w ith kerosene, or on the other hand w ith toluol? T h en too, is the
94 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 Vol. 10, No. 2 W ar D epartm ent certain th a t the nitration cap acity
of the country is not in excess of toluol recovery, or th a t it will not be so b y the tim e the recovery plants are installed? A lread y the coal shortage has seriously diminished the production of toluol from the b y product coke ovens, until now the chief source of supply.
This country can possess no more valuable reserve th an am ple quantities of stored toluol. A nother H ali
fax disaster, the bom bing of a few munitions stations, the sinking of a few supply ships stored with this m aterial m ight at any moment make a serious shortage, a shortage which would be criminal w ith all the lives at stake, if the possibility of such can be avoided.
On w ith the investigation! Senator Cham berlain can perform a distinct service if through his C om m ittee he can speed up m atters in the supply of such m aterials.
T h e country will hereafter crucify w ith its scorn any m anufacturer who now seeks to profiteer at its expense in this its hour of trial. So, too, will the country hold accountable those of its public servants who d illy-dally over minor details in fundam ental m atters.
S O M E B O D Y , P L E A S E CU T T H E T A P E
If the N ational R etail M erchants’ Association should arb itrarily rule th at all would-be purchasers of hats must be supplied w ith the hat most convenient to the reach of the clerk in attendance, w ithout regard to the shape, color or size of the h at, w hat manner of Easter parade would result from males and fem ales thus adorned! Or suppose the A m algam ated E m ploym ent Bureau should decree th a t seekers of help could secure only “ the next on the list,” regardless of qualifications.
W h at would eventu ally result to the regular processes of com mercial life if, seeking a stenographer, one should draw a cook! These suggestions are not intended to reflect on the good qualities of the num ber six h at on the seven and a half head or on the abilities of the do
mestic in her proper sphere. W ait a minute— these cogitations are not trivial.
Burns was all right when he wrote “ A M an ’s a M an for a ’ T h a t,” but there are all kinds of men and there are all kinds of chem ists: analytical and research chem ists, organics and inorganics, chem ists fresh from the universities and chemists who have been able to add to their university training valu able plan t experience.
Some have specialized in explosives, others in metal alloys. Some are accurate in a nalytical w ork, others excel in planning research. If, however, a governm ent depart
ment, bureau or division wishes to increase its chemical force b y securing the transfer of a specially qualified chemist from a cantonm ent to a governm ent lab ora
tory, such coordinate branch of the governm ent ser
vice must send out to the cam ps and sim ply ask for a chemist. Chem ists m ust not be sought b y name.
T o request a specially qualified man, designating the man you want, is no longer perm itted. Such is the ruling of the General Staff of the A rm y, to which ruling the W ar D epartm ent has strictly adhered for some weeks past. Shades of common-sense Am erica, w hat an absurd situation! Is this the final outw orking of the spirit of the selective draft which President W ilson
assured us was to fashion th is nation into the most efficient fighting machine, which law , the record of these columns will testify, we have striven stead fastly to uphold? Is Secretary B aker aware of this ruling, a ruling which was not brought into being three th ou sand miles aw ay, but right in the city of W ashington in his own Departm ent?
The results of such procedure are not only disaster to governm ent chem ical work but serious dem oraliza
tion of the staffs of the chem ical industries, which are supplying the very sinews of war. This can be illus
trated best b y tw o specific cases. A colonel in the Ordnance D epartm ent wrote recen tly to a prom inent chem ical m anufacturing com pany stating th at the D epartm ent was desirous of securing the services of a num ber of chemists and factory foremen for use as inspectors at munitions* plants. H e specified th a t th ey should have had such experience as would enable them to carry out intelligent inspection of explosives m anu
factured for the governm ent in this em ergency. The m anufacturer was asked to go over his organization and advise as to any men who m ight be available and whom he could recommend. T h a t is all right from one point of view . Of course the governm ent m ust have com pe
ten t inspectors, and chemical m anufacturers are just as patriotic as other men and will glad ly sacrifice their staffs if need be. T h a t is the real question, “ if need b e.” T here are more th an three hundred chem ists in cantonm ents to-day, practically inaccessible for governm ent chem ical work because of this rem arkable ruling of the General Staff. One of these is a graduate of two leading Am erican universities, in each of which he specialized in chem istry. Furtherm ore he has had three and a half years of experience in research and in the m anufacture of explosives, dyestuffs and pharm a
ceuticals, and is fam iliar with the installation and operation of chem ical machinery. Y e t his daily duties consist of scrubbing floors, shoveling coal or cinders, chopping wood, digging ditches (not trenches) and general work around the stable or kitchen.
W e do not seek to arouse sym p ath y for this young soldier chem ist. He is having a good experience and lo yally doing his d u ty as any other young A m er
ican would; his clear eye and soldierly bearing show, too, th at he has made good as a soldier. He makes not the slightest com plaint. B u t we do feel th at the g ov
ernm ent is not getting from him the most efficient service he could perform; and it is a shame for a simi
larly qualified man to be taken at this tim e from the industries for governm ent work while such a man could be made available in a few hours were it not for the weird ruling of the General Staff.
Sixteen thousand chemists at the outbreak of the war filed w ith the Bureau of M ines com plete data concerning their training and specialization in order th at their services might be prom ptly and intelligently availed of as need arose. Alas, these cards of volun
ta ry inform ation are now bound tig h tly together b y the red tape of this rule-beyond-understanding prom ul
gated b y the General Staff.
Som ebody, please cut the tape!
Feb., 1918 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 95
P L A T IN U M O SC ILLATIO N S
A t the recent meeting of Section C (Chem istry) of the A m erican Association for the A dvancem ent of Science a t P ittsburgh the platinum resolution (page 159, this issue), introduced b y M r. George F. Kunz, of T iffan y & Co., N ew Y o rk C ity , was unanim ously passed. T o present this m atter to the proper authori
ties a com m ittee was appointed consisting of Dr. W.
A. No.yes, Chairm an, and Dr. W| F. Hillebrand.
The adm irable suggestions contained in the resolu
tion will appeal im m ediately to every chem ist in uni
versity or technical laboratories. U nfortunately for the ray of hope held out b y this m ovem ent, Dr. Hille
brand, of the Bureau of Standards, in declining to serve upon the com m ittee, felt compelled to tak e this step because of his know ledge th at all of this platinum supply is needed im m ediately b y the governm ent, and has indeed already been turned over to the N itrate Com m ittee for catalyzer purposes in the oxidation of ammonia. There seems, at least for the present, no hope th at the use of residues for research on the platinum group of minerals can be undertaken, as the question of governm ent ownership of this material is undetermined.
The accounts of the energy, resourcefulness, and peregrinative ability of M r. Draper, who safely trans
ported from Russia 21,000 ounces of platinum and platinum ore and delivered it to the D epartm ent of Commerce, furnish ve ry interesting reading and com mand unquestioned appreciation of his achievem ent.
The necessity for such a journey, however, suggests further th ough t as to the accuracy of judgm ent of the Secretary of Com merce, who last Spring, evidently while this m aterial was being collected, gave ample assurances to the jewelers of the country th at the governm ent had an abundance of platinum , either on hand or available from stocks known to be existing abroad, which statem ent was heralded very widely b y the Jewelers’ Com m ittee. W e trem ble to think of the fix the governm ent m ight have been in if Mr.
Draper had stubbed his toe in going aboard ship and spilled the precious m etal into the sea, or had lost his trunk in the mazes of the Union Station baggage room in W ashington, or had met with the same delay in express shipm ents which the average citizen en
counters now adays. Seriously, we have been running very close to the danger line in governm ent supplies of this m aterial for m unitions m anufacture, while the advertising cam paign for platinum jew elry has gone m errily on. M eanwhile, the university and industrial chemist cannot hope for relief from the present high prices of platinum ware from the source contem plated b y the resolution of M r. K unz.
T h e com munication from Dr. Jas. Lewis Howe, printed in this issue, view s the platinum situation solely from the standpoint of “ business as usual,” an anti
quated slogan whose pernicious effect upon war pro
grams has already made itself plain ly evident.
T w o new methods of attackin g the problem of p lat
inum conservation have developed. Individuals and local Sections can use their influence w ith the local press to persuade them to refuse advertisem ents of platinum jew elry. The New York Times and the
New York World have adopted such a policy, and it it is a pleasure to state th at this has been done on the urgent appeal of M r. K unz, who is endeavoring to bring all of the New Y o rk neivspapers into line.
The second interesting developm ent is the recent organization of the W om en’s N ational League for the Conservation of Platinum . M ay the good work of this new organization prosper in every w ay. It is for women th a t this platinum jew elry is designed;
it is through women th at its use can be most effectually discountenanced. Perhaps through this League the real punch will be put into the platinum conservation movement.
AN A PPR E C IA T IO N A N D A G R E E T IN G
The appearance of the January num ber of the Journal of the American Chemical Society marks the retirem ent of Dr. W. A. N oyes from its editorship and the entrance upon his duties of the new ly elected editor, Dr. A. B. Lam b.
A fter fifteen years of splendid service, Dr. N oyes carries w ith him on retirem ent universal grateful ap
preciation of the devotion he has shown to the upbuild
ing of th a t Journal. To its list of contributors he has called all of the research workers in pure chem istry in this country. As a result of his accurate and con
scientious editorial work the publication stands to-day as one of the great chemical journals of the world.
In assuming his new task, Dr. Lam b m ay feel con
fident of the continuation of th at spirit of cooperation which in the past has proved so potent a factor in the success of the Journal. He has, m oreover, the solid satisfaction of knowing th a t not only was he the unanimous choice of the Council, but th a t such choice was based upon the unanimous report of a com m ittee of our ablest men who canvassed the field w ith closest scrutiny. T h e fact th at Dr. Lam b begins his editor
ship while devoting much of his tim e to governm ent service constitutes an additional reason for loyal
support. __________
C H E M IS T R Y IN SIG N IA
For the first tim e in the history of the U nited States an A rm y group w ill wear a design typ ify in g chem istry as a recognized branch of w ar service. Through the courtesy of the m anufacturers we are the proud pos
sessors of the first insignia and collar design struck from the dies.
In s i g n i a f o r Ch b m i c a l Ss r v i c b
From the record of attainm ents of the first men selected to wear such insignia it can be predicted with certain ty th a t th e y will be w orth ily worn.
Good luck to the C hem ical Service Section of the N ational A rm y!
96
T E 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 Vol. io, No. 2ORIGINAL P A P E R S
T H E E X TR A C TIO N O F P O T A S H A N D O TH E R C O N ST IT U E N T S F R O M SE A W A T E R
B IT T E R N 1 B y J o H I, H . Hi l d e b r a n d
R eceived Decem ber 5, 1917 C O M P O S IT IO N O F S E A W A T E R
The main constituents of sea w ater, besides sodium chloride, are magnesium sulfate, m agnesium chloride and potassium chloride, together w ith a small q u an tity of magnesium bromide and calcium salts. D uring the evaporation of the sea w ater to secure sodium chloride, the calcium present is alm ost com pletely deposited as calcium sulfate, so th a t calcium salts are p ractically absent from the m other liquor. B y con
sidering the various analyses of sea w ater we m ay calcu
late the relative am ounts of the solid salts th a t m ight be obtained b y evaporation. T h e salt works around San Francisco B a y, w ith which we are prim arily con
cerned, produce som ething over 100,000 tons of sodium chloride per annum ; the am ounts of the other salts associated w ith this am ount of sodium chloride would be as follow s:
To n s
S o d iu m chloride (N a C l) ... 100,000 P o ta ssiu m chloride (K C 1)... 2,800 M ag n esiu m chlo rid e (M g C b .6H iO )... 27,300 E p so m s a lts (MgSC>4.7 H iO )... ... 16,000 B ro m in e (B r) e x tra c te d from th e b ro m id es... 240
A t this tim e, when the country is suffering from an acute shortage of potassium salts, the am ount of potassium chloride indicated above is of considerable im portance. D uring the first half of 1917 the total potash production of the country, calculated on the basis of K jO , was 14,000 tons, which am ount was but 10 per cent of the normal am ount used before the war. I t is evident th at the am ount of potash th at could be extracted from the bitterns of the salt works on San Francisco B a y alone would add about 10 per cent to the co u n try’s present annual production of potash. T h e am ount of salt actually produced in this region is nearly 140,000 tons per annum, so th at a liberal allowance for losses in working up the bittern should leave still 3000 tons of potassium chloride.
B y utilizing the bitterns from other regions on the P acific Coast, notab ly San Diego, this am ount would be very greatly increased.
T h e other materials m entioned in the above table also represent ve ry considerable values, although th e y have less relation to the present national em ergency.
A fter the rem oval of most of the common salt in the salt ponds, the other salts would be contained in ap
proxim ately 100,000 tons of bittern, having a volum e of approxim ately 100,000 cubic yards.
The values represented b y these m aterials, and their im portance both as a natural resource of California and in supplying the country with potash in th e present acute em ergency, made the study of this problem seem a proper one to undertake at this tim e.
■ T h is w ork h a s been s u p p o rte d b y th e C ouncil o f D efense of th e S ta te of C alifornia.
S C I E N T I F I C B A S IS O F M E T H O D S F O R R E C O V E R Y O F T H E C O N S T IT U E N T S O F B IT T E R N
W e are very fortunate to possess a vast fund of inform ation upon the solubility relationships of the various salts obtainable from sea w ater through the classic work of va n ’t Hoff and his co-workers. T h is w ork is described in great detail in “ Uber die B ildungs
verhältnisse der ozeanischen Salzablagerungen” (Leip
zig Verlagsgesellschaft, 1912). D uring the progress of the work tw o smaller volum es were published in 1905 and 1909 b y va n ’t Hoff, entitled “ Zur B ildung der ozeanischen Salzablagerungen” (Braunschw eig, V iew eg).
Inasm uch as ve ry little of th is work has been trans
lated into English, and in view of the difficulty of interpreting it in its form idable com plexity, it seems desirable to give a general outline of its nature.
T h e solubility of a single salt in its relation to changes in tem perature m ay be represented b y simple diagram s of the typ e fam iliar to all trained chem ists.
700
0 20 4 0 60 8 0 too n o MO ISO
Temperature, degrees Cenf/yrade F ig . I
In Fig. I are represented the solubility curves for the main salts w ith which we have to deal, viz., sodium chloride, potassium chloride, potassium sulfate, m ag
nesium sulfate and magnesium chloride. In this figure solubility is expressed as the num ber of mols of an
hydrous salt per 1000 mols of water. Of course, other units m ay be used, such as mols or gram s of salt in a certain number of grams of w ater or of solution, or in a certain num ber of cubic centim eters in solution.
If we know the solubility expressed in an y of these term s it is possible to calculate it in an y other term s, the density of the solution being required where the conversion is between a weight and volum e basis.
The law s of dilute solutions m ay frequently be ex
tended to give an approxim ate idea of the behavior of concentrated solutions. The solubility of a given
Feb., 1918 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 97
salt is varied b y the introduction into the solution of another salt. The effect of the second salt can be predicted q u alitatively b y rem embering th at where the salts possess a common ion the solubility of each is usually decreased b y the presence of the other. If, however, there is a strong tendency to form a complex salt the solubility of one m ay be increased b y the presence of the other. Again, where there is no com mon ion the solubility of one is increased b y the pres
ence of the other owing to the interaction of the two salts.
There are various w ays of representing graphically the solubility relationships of salt pairs. The method adopted b y v a n ’t Hoff is to represent the am ount of each salt in the solution in term s of mols of anhydrous salt per 1000 mols of water, measured along tw o axes at right angles to each other, as illustrated in Fig. II.
Each curve here represents the composition of a solu
tion saturated w ith one com ponent. The intersec
tions of the curves represent the composition of a solu
tion saturated with both components. A point be
tw een these curves and the origin denotes the composi
tion of an unsaturated solution. A point outside of the curves would represent a m ixture of a saturated
Fig. I I
solution w ith one or both solid salts, depending upon its position. On evaporation of an unsaturated solu
tion the relative am ounts of the tw o salts would re
main the same until the solution becomes saturated;
so th at, for example, a solution having the composition represented b y the point a in Fig. II would, on evapora
tion, change in com position as represented b y the mo
tion along the line ab. A s soon as the curve A B is reached, representing in this case the com position of a solution saturated w ith potassium chloride, solid potassium chloride will separate and the solution must become relatively richer in sodium chloride, so th at as the evaporation proceeds from b the solution will change in com position along the solubility curve to wards B. Sim ilarly, an unsaturated solution having the com position represented b y c would, on evapora
tion, change in com position as represented b y m ove
ment along the line cd. A t d sodium chloride would begin to crystallize, whereupon the solution would become richer in potassium chloride, its com position changing along the line dB. I t is evident th at the final result in the evaporation of an y solution of these tw o salts would be a saturated solution having the
composition represented b y B, changing into a m ixture of the-tw o solid salts.
The effect of tem perature m ay be indicated on a third axis at right angles to the others, giving a solid figure, as represented in perspective in Fig. III.
Where a double salt m ay be formed, the solu bility relationships at a given tem perature would be repre
sented b y a diagram such as th at in Fig. IV . T h is diagram represents the solubility a t 300 of m ixtures of sodium sulfate decahydrate, and magnesium sulfate heptahydrate, which form the double salt, astra- kanite, N a2M g(S04)2.4H 20. The middle portion of the curve seen in this figure represents the com position of solutions saturated w ith astrakanite. Solid astra- kanite, which contains equivalent quantities of the tw o salts, has a composition lyin g upon a line bisecting the angle between the tw o axes. The com position of the solid salt is represented b y a point on this line at E, expressing the number of mols per 1000 mols of water in the solid salt. The composition of solid sodium sulfate, N a2S0«.ioH20, which lies along the line O A, is at a distance from the origin corresponding to its water content at F. Sim ilarly, solid magnesium sulfate has the composition represented b y the point
G. When an unsaturated solution containing these salts is evaporated, its com position will, as in the previous case, move along a line aw ay from the origin until one of the curves representing the com position of the saturated solution is reached, when the solution will change in composition along this line in the direc
tion aw ay from the line representing the com position of the solid which is separating. T hus a solution having the composition represented b y a would, on evapora
tion, change in com position along th e line ab, when, on further evaporation, sodium sulfate would separate, and finally, a t B, both sodium sulfate and the double salt would separate, the solution rem aining constant in composition until it had all disappeared. Sim ilarly an unsaturated solution of com position represented b y c would change in com position in the direction cdB, the solids separating being first pure astrakanite and then a m ixture of astrakanite and sodium sulfate.
T he point B represents, therefore, th e end-point of crystallization for solutions which contain more sodium sulfate than magnesium sulfate.
Fig. V represents the solubility of m ixtures of magnesium chloride and potassium chloride, from which
98 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 Vol. 10, No. 2
F io . IV
it is possible to crystallize the double salt carnallite, K M g C l3.6H20. Unlike the previous instance, how
ever, the line OE, somewhere upon which lies the point representing the com position of solid carnallite, does not intersect the curve B C which expresses the com po
sition of solutions saturated w ith carnallite. This fa ct makes the path of crystallization, during the evaporation of solutions of these tw o salts, som ewhat different from th a t considered above. A solution having the com position represented b y a will, on evaporation, change in com position till b has been reached, whereupon potassium chloride begins to crystallize out, and the solution, becom ing richer in m agnesium chloride, will m ove along bC. W hen the solution has reached the com position represented b y C, carnallite will begin to separate, b u t since carnallite contains more potassium chloride th an does the sat
u rated solution a t C, it is evident th a t while carnallite crystallizes, the solution will tend to move along the line CB instead of rem aining a t C. T he phase rule, how ever, requires th at while both potassium chloride and carnallite are present, the solution m ust remain constant in com position at C. Therefore, instead of the liquid phase disappearing at this point, as was the case in the former salt pair, it is one of the solid phases, potassium chloride, which will now disappear, being changed over into carnallite. It is not until all of the potassium chloride has been so changed th a t the solu
tion can move from C to B. B will thus represent an end-point of crystallization, while C will not. It is evident, therefore, th at in order to prepare crystals of carnallite it is necessary to use a solution containing more than the equivalent am ount of magnesium chlo
ride, the relative amounts of the tw o salts being such th at, on evaporation, the line B C will be intersected sligh tly above C. Similar considerations show us th at on treating solid carnallite with water, instead of dis
solving as such, it would tend to change into solid potassium chloride and a solution whose com position is th a t represented b y C. It is obvious, therefore, th a t
F io . V
it is not difficult to obtain potassium chloride from carnallite, a point of im portance in the treatm ent of salt bitterns, as will be discussed later. A fter the rem oval of the potassium chloride the solution can be evaporated, carnallite separating, while the com posi
tion of the solution changes from C to B. This car
nallite can be treated with water, leaving solid potas
sium chloride, etc.
Solutions containing magnesium and potassium chlorides and sulfates are in equilibrium w ith solid phases a t 250 according to the data in T able 1, and are
Table 1
S y ste m , K C l-M g C lj-K iS O i-M g S O « , a t 25°
Co m p o s i t i o n o p So l u t i o n
M ois of c o n stitu e n ts p e r 1000 m ois H jO
So l i d Ph a s e s K jC Ii M gC li MgSO< K j S O «
A K C l ... 44
B M gC la.ôH iO ... 108'
C M g S 0 ..7 H i0 ... 55
D KjSO<... 12 E K C l a n d K M g C li.ô H îO ... 5 .5 7 2 15
F M gClj.ôH aO a n d K M g C li.6H t O ... 1 105 . . G M g C li.6H jO a n d M g S 0 ..6 H ,0 ... 104 14 H M g S 0 ..7 H i0 a n d M g S O i.ô H îO ... 73 15 K o) MgSO<.7HiO a n d K iM g (S O i)i.6H iO ...
KïSO* a n d K ?M g(S04)j.6H j0 ... 5 8 .5 *5.
K • • * 22 16
L K îSO t a n d K C l... 42 1 M K C l; K iSO i a n d K iM g(SO «)j.6H 20 ... 25 2 \ i i N K C l; M g S 0 < .7 H ,0 a n d K zM gfSO O j.ôH îO 9 55 16
4
1 P K C l; M gSO t.7H iO a n d M g S 0 (.6 H 10 . . . . 8 62 15 Q K C l; M gSO i.ôH iO a n d K M g C h .ô H jO .. . 4 .5 70 13 .5 R M g C li.ô H îO ; K M g C b .ô H iO a n dMgSO*.6H iO ... 2 99 12
(a) T h e co m position of th e so lu tio n a t th is p o in t is given b y differen t figures in v a n 't H off’s earlie r a n d la te r books. T h e l a tte r a re d o u b tle ss in c o rre c t, as th e fo rm er agree w ith th o se of H . S. v a n K lo o ster, J . P h ys.
C hem ., 21 (1917), 513.
represented b y va n ’t Hoff along four axes, as in Fig.
V I, each pair of axes representing solutions containing a common ion. The boundary lines correspond to solutions saturated w ith the tw o constituents repre
sented b y the enclosing axes. W here salt pairs con
tainin g no common ion are present it is im possible to represent the composition b y a point in the plane of this figure. A m ixture of equivalent quantities of potassium sulfate and magnesium chloride w ould e v i
dently lie at the origin 0 and would be indistinguish
able from pure w ater b y its position in the plane. In order to m ake this distinction it is necessary to intro
Feb., 1918 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 99
duce a vertical axis representing the sum of the con
stituents of the solution. Again, since equivalent quantities of potassium sulfate and magnesium chlo
ride in solution m ay be represented equally well as equivalent am ounts of magnesium sulfate and potas
sium chloride, b y plotting along the potassium chloride axis not mols of potassium chloride, but double mols, nam ely, K2CI2, it is possible to construct a solid model expressing the com position of solutions containing any amounts of these ions. Such a model, a perspective drawing of which is seen in Fig. V I I, m ay be constructed b y inserting needles at the intersections of the lines in the plane figure, the heights of the needles being equal to the total number of mols of dissolved salt in the solu
tion at this point, alw ays remembering to consider the mol of potassium chloride to be K2CI2. The tops of these needles m ay be connected b y threads which m ark off surface within which a saturated solution is in equilibrium w ith a single salt. Along the threads
separating tw o fields the solution is saturated w ith tw o salts, while at the intersections three salts are present.
The com position of unsaturated solutions is repre
sented b y points within the model. F or example, a solution containing 2 mols of K2CI2, 8 mols of M gSOi and 10 mols of M g C l2 will be represented b y a point found b y counting 2 divisions along the potassium chloride axis, 8 divisions to the left in the direction of magnesium sulfate, which would then be 6 divisions to the left of the magnesium chloride axis, 10 divisions along the magnesium chloride axis, and then upwards 20 divisions, representing the total num ber of mols.
This solution could also be represented as containing 6 mols of m agnesium sulfate, 12 mols of magnesium chloride, and 2 mols of potassium sulfate, which would give the same locus to the point. On the rem oval of w ater from this solution all of the solid constituents w ill increase in the same proportion, so th a t the solu
tion would move along the line in space aw ay from the origin 0 until one of the fields is reached representing the separation of a solid salt. Further evaporation would then result in a change in composition of the solution equivalent to the rem oval of a saturated solu
tion of the solid which is separated, since both this solid and water are being rem oved sim ultaneously.
T he composition of the solution would thus move along one of the faces of the model until one of the boundary lines has been reached, when a second salt would begin to separate along w ith the first. The solution would then change in com position as repre
sented b y motion along this line. B y drawing lines on these surfaces it is possible to represent in the projection of the solid model such crystallization paths, so th at the projection m ay be used in m any cases instead of the solid model.
It is possible to calculate in this w ay the am ounts of the various solid salts and the amount of w ater which have separated from any solution when a certain point on a crystallization path has been reached. Thus,
in the case of the solution considered above, the di
agonal which joins the origin w ith the point repre
senting the composition of this solution will be found to intersect the schonite face, showing th a t this would be the first salt to separate on evaporation. As evaporation proceeds the crystallization path would meet the boundary line of th is face w ith the m ag
nesium sulfate face, after which these tw o salts would separate together. . Suppose, for exam ple, we wish to calculate the actual am ounts of these tw o salts sep
arating and the am ount of w ater th a t m ust be rem oved when the point N has ju st been reached, at which potassium chloride ju st begins to separate. T h e solu
tion at N has the following com position: 1000H2O + 9K2CI2 + i6MgSO,i + 5sM gCl2. T h e am ount of this solution we m ay represent as an unknow n q u an tity b y p, the amount of schonite separating we m ay repre
sent b y q, the magnesium sulfate b y r, and the am ount
