The Journal of Industrial and Engineering Ghemistry
Pu b l i s h e d b y T H E A M E R I C A N C H E M I C A L S O C I E T Y
AT B A S T O N , P A .
Volume V I M A Y , 1914 N o. 5
B O A R D O F E D IT O R S E ditor: M . C . W h i t a k e r
A ssistan t Editor: Le o l a E . Ma r r s
Associate Editors: G . P . A d a m so n , E . G . B a ile y , H. E . B a rn a rd , G . E . B a rto n , A . V . B le in in g e r, W m . B lu m , Wm. B ra d y , C . A . B ro w n e, F . K . C am e ro n , W m . C am p b e ll, F . B . C a rp e n te r, C . E . C a s p a ri, V . C o b le n tz , W. C. G eer, W . F . H illeb ra n d , W . D . H orne, T . K a m o i, A . D . L ittle , C . E . L u ck e , P . C . M c llh in e y , J. M . M a tth e w s , T . J. P a rk e r, J. D . P e n n o ck , W . D . R ich a rd so n , G . C . S to n e, E . T w itc h e ll, R . W a h l, W. H. W a lk e r, W . R . W h itn e y , A . M . W rig h t.
P u b lis h e d m o n t h ly . S u b s c r ip ti o n p r ic e to n o n - m e m b e r s of th e A m e r ic a n C h e m ic a l S o c ie ty , $ 6 .0 0 y e a rly . F o r e ig n p o s ta g e , s e v e n ty - fiv e c e n ts , C a n a d a , C u b a a n d M e x ic o e x c e p te d .
E n t e r e d a s S c c o n d - c la s s M a t t e r D e c e m b e r 19, 1908, a t th e P o s t-O ffic e a t E a s t o n , P a ., u n d e r th e A c t of M a r c h 3 , 1 8 79,
C o n t r ib u t io n s s h o u l d be a d d r e s s e d to M. C. W h it a k e r, C o lu m b ia U n i v e r s i t y , N e w Y ork City
C o m m u n ic a t io n s c o n c e r n i n g a d v e r t i s e m e n t s s h o u l d b e s e n t to T h e A m e r i c a n C h e m i c a l S o c i e t y , 42 W e st 3 9 t h St ., N e w Y or k City S u b s c r i p t i o n s a n d c l a i m s (o r l o s t c o p i e s s h o u l d b e r e f e r r e d to C h a r le s L. P a r s o n s , B o x 5 0 5 , W a s h i n g t o n , D. C.
, Es c h b n b a c h Pr i n t i n g Co m p a n y, Ea s t o n. Pa.
T A B L E O F C O N T E N T S Ed itorials :
T h e S p rin g M e e tin g a t C in cin n a ti... 364
Journal of th e A m erican W a te r W ork s A s s o c ia tio n . . . . 365
T h e D istrib u tio n of In d u s trie s... 365
N ew S ection A d d e d to J o u rn a l... 366
Or igin al Pa p e r s: S tu d y of th e C om p osition of W a te r G as T a r . B y C . R . D ow n s and A . L . D e a n ... 366
T h e R a d io a c tiv ity of Som e T y p e S oils of th e U n ited S tates. B y R ic h a rd B . M o o re ... 370
P artial and In te r m itte n t C om bu stio n of G as. B y E- E . S om erm eier ... 374
W ood D istillatio n und er D im in ish ed Pressure— A C o n tribu tion to th e P rob lem of U tiliza tio n of W ood W aste. B y M a x w e ll A d a m s and C h arles H ilto n . . . 378
T h e N a tu re of B a s ic L e a d C arb o n a te. B y E d w in E u s to n ... 382
T herm al R e actio n s in C arb u re tin g W a te r G as. P a r t I— T h eo retica l. B y M . C . W h ita k e r and W . F . R it tm a n ... 383
Paraffin B odies in C o a l T a r C reosote and T h e ir B ea rin g on Specification s. B y S. R . C h u rch and John M orris W eiss... 396
A V o lu m etric M eth o d for th e D eterm in ation of L ead. B y A lfred A ld e r and M . F . C o o lb a u g h ... 398
T h e D eterm in ation of A rsen ic in H y d ro ch lo ric a n d S u l fu ric A cid s. B y R . F . T a r b e ll... 400
One C au se of L o w R e su lts in th e A ss a y of P ep p erm in t Oil. B y H a rry W . R e d fie ld ... 401
O bservations upon th e A s s a y of D ig e stiv e F erm en ts. B y H o w ard T . G r a b e r ... 402
L a b o ra to ry S tu d ies on M a lt E x tr a c t. B y H o w ard T . G ra b e r... 403
Labo r a t o r y a n d Pl a n t: T h e P y ro m e te r in th e A ss a y M uffle. B y F red eric P . D e w e y ... 405
A p p ro ved B u rea u of M in es E x p erim en t S ta tio n a t P ittsb u rg h ... 406
T h e C h e m ist’s D u p le x S lid e R u le. B y H . H . H a n so n ... 407
Ad d r e sses: T h e C h e m ists’ C lu b . B y W illiam L . D u d le y ... 407
C hem ical A b stra ctin g . B y John J. M ille r ... 4 11 The P resen t S ta te of th e C y a n a m id In d u stry . B y E . J. P r a n k e ... 415
Industrial M altose. B y Chester B . D u ry e a ... 419
M illing of W heat and Testing of Flour. B y H arry M cC orm ack... 423
Curren t In d u str ial Ne w s: Fuller’s E a rth ... 428
Financial and Labor Conditions on English Railroads 428 Im ports of Sperm Oil during 1913... 429
Potash Shipments during 1914... 429
B y-Product Producers in G erm an y... 429
German Foreign Trade in Iro n ... 429
N atural Gas in C an ad a... 430
T ar and Benzol Prices... 430
Dom estic Lighting F ifty Y ears A g o ... 430
Gases in Iron and S tee l... 430
The Cinem atograph in Research... 430
Chemical Industries in Japan since 19 11... 431
T he Paper Industry in In d ia ... 431
Scien tific So c ie t ie s: Am erican Chemical Society— -Forty-Ninth M eeting, Cincinnati, April 6-10, 19 14 ... 431
Industrial Chemists and Chemical Engineers Division — R eport of Com m ittee on Alum Specifications. .. . 435
The American Electrochemical Society— T w enty-F ifth General M eeting, New Y o rk C ity, April 16-18, 1914 436 Presidential Address— Some Econom ic and Aesthetic Aspects of Electrochem istry. B y E . F. Roeber. . . . 436
T h e American Institute of Electrical Engineers— 293rd M eeting... 439
No tes and Co r r esp o n d en c e: T he Invention of Celluloid... 440
Laboratories in the Chem ists’ B u ild in g... 441
A n Investigation of the Presence of Furfural in Cider Vinegar— A Correction... 441
Correction... 441
Per so n a l No t e s... 442
Govern m en t Pu b l ic a t io n s... 443
Per son al No t e s... 442
Boo k Re v ie w s: M olded Electrical Insulation and Plastics; Die Chemie und Technologie der N atürlichen und Künstlichen Asphalte; Solvent Oils, Gums, W axes and Allied Substances; Practical Science for Engineering Stu dents ... 446
New Pu b l ic a t io n s... 447
Ma r k e t Re p o r t... 448
364 T E 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 Vol. 6, No. 5
EDITORIALS
T H E S P R I N G M E E T I N G A T C IN C IN N A T I
T h e F o r ty -n in th M e e tin g of th e A m e rican C h em ical S o c ie ty co n v e n e d in C in cin n a ti, A p ril 6th—10 th ; th e to t a l re g istra tio n w as 658. T h e sessions w ere held a t th e U n iv e r s ity of C in c in n a ti, tw e n ty m inu tes’ ride fro m th e h e a d q u a rte rs a t th e H o tel Sinto n.
T h e business m eetin g of th e C o u n cil on M o n d a y e v e n in g w as d e v o te d to co m m ittee rep o rts. T h e re p o rt of th e S u p e rv is o ry C o m m itte e on S ta n d a rd M e th o d s of A n a ly s is w as d iscussed a t len gth . A t e n ta tiv e rep o rt o f th e sp ecial C o m m itte e on B usiness M a n a g e m e n t w as m ade b y P ro f. B a sk e rv ille . A fte r som e discu ssion it w as acce p te d as a rep o rt of p ro g
ress an d th e c o m m ittee w as requ ested to su b m it it, w ith a s ta te m e n t of th e reasons for and a ga in st th e p lan prop osed , to th e C o u n cil and lo cal sectio ns before M a y 15 th , in order th a t final a ctio n m a y be l^iken a t th e A n n u a l M e e tin g a t M o n tre a l th is fall.
T h e fo rm al op en in g of th e co n v en tio n w as th e G en eral M e e tin g in M c M ic k e n H all, w here the S o cie ty wras w elcom ed b y th e H o n o rab le F . S. S p iegel, M a y o r of C in c in n a ti, and b y P re sid e n t C h arle s W . D a b n e y o f th e U n iv e rs ity of C in c in n a ti. P resid e n t T . W . R ic h a rd s respo nd ed to th e ir co rd ial greetin g s and co n g ra tu la te d th e S o c ie ty on th e re c e n tly m ade s ta te m e n t th a t th e tw e n tie th c e n tu ry is to be a ch em ical c e n tu ry . T h e scien tific p ro gram is p rin ted in fu ll in th is issue.
T h e L o ca l E x e c u tiv e C o m m itte e , co n sistin g of F . W . W eissm an n , S tep h en J. H au ser and A rch ib a ld C am p b e ll, d eserve th e u n bou n d ed g ra titu d e of th e S o c ie ty fo r th e m ann er in w hich th e y h an d led th e m a n y d e ta ils o f th e m eeting. A rra n ge m e n ts w ere m ade w ith th e U n iv e rs ity of C in c in n a ti fo r servin g lu n ch eo n each d a y a t th e U n iv e rs ity , and th is w as of sp ecial co n ven ien ce to th o se ta k in g p a rt in th e m a n y excursio ns. T h ese trip s w ere in ch arge of M r. G.
F a rn h a m and in clu d ed th e in sp ectio n o f tw e n ty -fo u r im p o rta n t in d u stria l p la n ts and p o in ts of in terest in th e v ic in it y of C in cin n a ti, and v isits to th e N a tio n a l C ash R e g iste r F a c to r y a t D a y to n , O hio, and th e A m e rican R o llin g M ills a t M id d leto w n , O hio. Special stre e t ears or au to m o b iles w ere fu rn ish ed so th a t th e m inim um fa tig u e m igh t resu lt fro m th e in sp ectio n of large p lan ts. S p e cial train s to o k th e v isito rs to th e D a y to n an d M id d le to w n fa cto rie s. F u rth e r d etails a s to th e se in s tru c tiv e and e n jo y a b le excu rsio ns will be fou n d elsew here in th is Jou rnal.
On T u e s d a y ev e n in g , th e c o m p lim e n ta ry sm oker w as g iv e n a t th e H o te l Sin to n . A m p le su p p lies of fo o d an d fa v o r ite d rin k s w ere serve d alo ng w ith choice b ran d s o f “ sm o k e s;” th e m em bers w ere p ro v id e d w ith colored tissu e p a p e r cap s w h ich ad d ed to th e g a ie ty of th e occasion . M r. E . B . R em elin h u m o ro u sly d em o n strated th e sim p lic ity of sev eral M o d e rn C h em ical D e v e lo p m e n ts in clu d in g th e m a n u fa c tu re of s y n th e tic ru b b er, th e ease w ith w hich rad iu m m a y be prep ared in larg e q u a n titie s (acco rd in g
to m eth od s d ev elo p e d b y P ro f. P arson s) and its use in th e ra p id cure of m a lig n a n t can cer. A cartoonist sk e tch e d fa v o rite poses and w'ell-known charac
te ristics of p ro m in en t p erso n alities in th e Society, and th e e n te rta in m e n t w as co n clu d ed b y a number of d e ft and p leasin g sleig h t-o f-h an d trick s. M r. Broe- m an and his co m m ittee received th e th a n k s of all p rese n t for a m ost successful even in g.
A n o tab le e n te rta in m e n t w as fu rn ish ed b y the C in c in n a ti S y m p h o n y O rch e stra in a com plim entary co n cert te n d ered to th e , v is itin g m em bers of the S o c ie ty b y th e C in c in n a ti S ectio n a t th e Emery A u d ito riu m on W e d n e sd a y e v e n in g w ith D r, Ernst K u n w a ld co n d u ctin g and M r. E m il H eerm ann as v io lin soloist.
PR OG R A M .
1. O vertu re— " D e r F re isc h ü tz 1’ ... Weber 2. “ U n fin ish ed ” S y m p h o n y ...Schubert 3. H u ngarian R h ap so d y N o . 1 ... Liszt 4 C on certo G rosso N o . 6 ... Haendel
D r. K u n w a ld a t the Piano.
5. V io lin C o n c e r to ...’. Bach E m il H eerm ann.
6. A cadem isehe F e st O v e r tu re ...Brahms T h e p ro gram w as rendered w ith a s y m p a th y and d e lica cy of m u sical feelin g th a t o n ly carefu l training, finished te ch n iq u e and p e rfe ct ensem ble w ork can m ake possible. T h e e n jo y m e n t o f th e audience was a tte s te d b y h e a r ty ap p lau se an d a p p re c ia tiv e compli
m en ts fro m th e m a n y m usic lo ve rs in th e Society.
P re v io u s to th e S y m p h o n y C o n ce rt th e abstractors and ed ito rs of th e S o c ie ty ’s J o u rn als w ere served an e x cellen t dinn er in th e d in in g room of th e Ohio M e ch an ics In stitu te . V ario u s su ggestion s as to the im p ro ve m en t and m ore e x te n d ed d istrib u tio n of the S o c ie ty Jou rnals w ere in fo rm a lly discussed. About th ir ty gu ests w ere presen t and it is h op ed th a t such m eetings of our e d ito ria l fo rce m a y b ecom e an integral p a rt of our general m eetings, since th e y will afford an ex cellen t stim u lu s to th e co o p eratio n n ecessary for the b est success of th e S o c ie ty ’s p u b lica tio n s.
T h e B a n q u e t on T h u rsd a y e v e n in g a t th e Hotel S in to n w as a tte n d e d b y over tw o hun dred guests.
T h e large b an q u e t h a ll w as a rtis tic a lly d ecorated with p in k carn atio n s, ferns and sm ilax, and an exquisite m usical p ro gram w as rendered d u rin g th e evening.
P ro f. W ild er D . B a n cro ft a cte d as T o a stm a ste r and addresses w ere m ade b y C h arles W . D a b n e y , Theodore W . R ich a rd s, A lb e rt B e ttin g e r and Jo h n Uri Lloyd.
T h e S o c ie ty ow es m uch to th e B a n q u e t Com m ittee, h ead ed b y M r. L a u d e r W . Jones, fo r bringing the C in cin n a ti p a rt of th e m eeting to a close w ith such a d e lig h tfu l social fu n ctio n .
L ad ies to th e n um ber of one h u n d red and twenty- five a tte n d e d th e m eeting. T h e ir co m fo rt and en
jo y m e n t w ere p ro v id e d for b y a la rg e com m ittee under th e efficien t lead ersh ip of M rs. J. W . E llm s. About s e v e n ty gu ests a tte n d e d th e co m p lim e n ta ry dinner
May, 1914 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
De l e g a t e s o ft h e Fo r t y-n i n t h Me e t i n g o ft h e Am e r i c a n Ch e m i c a l So c i e t y a tt h e Na t i o n a l Ca s h Re g i s t e r Pl a n t, Da y t o n
served to th e lad ie s a t th e H o tel S in to n on T u e s d a y evening w hen in te re stin g ta lk s w ere m ade b y som e of the m em bers and se v e ral of th e gu ests w ho h ad been connected w ith pure fo o d cam p aig n s in th e large cities. T h e dinner w as fo llo w ed b y a v e r y e n jo y a b le theatre p a r ty to w h ich th e gu ests w ere c o n v e y e d in automobiles. W e d n e sd a y w as sp en t a t F t . T h o m a s and T h u rsd ay a t th e R o o k w o o d P o tte r y . A ll of th e regular d ivision m eetin g s and excu rsio n s w ere open to the ladies. A large n u m ber to o k th e D a y to n - Middletown tr ip , th e ride th e n ce b ein g sh o rte n e d b y piano and v o ca l solos as w ell as fo lk songs in w h ich the entire p a r ty jo in ed .
The in d u stria l a c t iv it y of th e Q ueen C it y of th e West, th e use o f its U n iv e r s ity fo r th e m eetin gs, the hospitality of th e m a n y in s titu tio n s and fa cto rie s so graciously th ro w n open, th e general co m fo rt b ro u g h t about b y th e s k illfu l p lan n in g o f th e co m m ittee s of th e Local Section, w ill lin g er lo n g in th e m em ories of th o se who attended th e S p rin g M e e tin g a t C in cin n a ti.
JO U R N A L O F T H E A M E R I C A N W A T E R W O R K S A S S O C I A T I O N
We h a ve ju s t re ce ive d th e first n u m b er, M arch , 1914, of th e Jou rna l of the A m erican Water W orks Association. T h is Jo u rn a l is to ta k e th e p la ce of th e annual p roceedin gs, an d m a rk s a g re a t step in a d vance in th e affairs of th e A sso cia tio n , w h ich is now thirty-four y e a rs old. A t th e la s t co n v en tio n o f the Association, a n ew co n s titu tio n wras a d o p te d g iv in g it an organization resem b lin g , in se v e ral fe a tu re s, th a t of the Am erican C h e m ic a l S o c ie ty . T h e fo rm atio n of sections w as a u th o rize d , and a lre a d y a N ew Y o r k Section h as b een fo rm ed th a t h as h ad tw o su ccessfu l meetings. T h e exp an sio n u n der th e new co n s titu tio n requires a m ore p ro m p t m ed iu m fo r th e p ro d u ctio n
°f the proceedin gs an d p a p e rs a n d ' th e re fo re , th e executive c o m m itte e o f th e A ss o cia tio n h as e stab lish ed a Quarterly jo u rn a l.
. It is p lan n ed to issue* th e first n u m ber each y e a r before the an n u al c o n v en tio n . I t w ill co n ta in pap ers, which w ill la te r be d iscussed a t th e c o n v en tio n . A
second n u m ber w ill co n tain the proceedin gs of th e co n v e n tio n and such p ap ers and d iscussion s as m a y be- p ro m p tly a v a ila b le for p u b lica tio n . T h e th ird and fo u rth n u m bers w ill c o n tain th e rem ain in g p a p e rs and d iscussion s from th e an n u al co n v e n tio n , p u b lish a d d itio n a l p ap ers su b m itte d to th e sectio n s, m ake n ecessa ry a n n o u n cem en ts of lo cal m eetings and con ta in a revise d list of m em bers.
B y th is p ro ced u re th e A sso cia tio n w ill p rese n t its p ap ers m ore p ro m p tly , a v o id in g th e d e la y s a tte n d a n t on a sin gle a n n u al issue. T h e J o u rn al will fu rn ish a re p o sito ry for w a te r w o rks lite ra tu re , w hich w ill b rin g it in closer to u ch w ith th e needs an d in te re sts of th e m em bersh ip , besid es offerin g a g rea te r in ce n tiv e to co n trib u to rs.
T h e first n u m ber co n tain s nin e p ap e rs. F ro m the ch a ra cte r of th ese w e see th a t th e n ew jo u rn a l w ill deal w ith m a tte rs of in terest to a la rg e v a r ie ty of readers in clu d in g ch em ists, b acte rio lo g ists, en gin eers, ad m in istrato rs, an d p ra ctic a l w a te r w orks o p erato rs.
W e hop e th a t th is new d e p artu re w ill m ake th e A m e rica n W a te r W o rk s A ss o cia tio n a g re a te r b en efit th a n e v er b efo re to its m em bers.
T H E D IS T R IB U T I O N O F I N D U S T R I E S
In a c o m m u n ica tio n to th e N a tio n a l L ib era l Im m i
gra tio n L e a gu e, D r.' C . W . E lio t presents his rem ed y fo r m u n icip al con gestion . In his op inion , th e p re
v e n tio n of th e o v e rcro w d in g o f our in d u stria l centers a n d th e e v ils a tte n d in g th is o v e rcro w d in g lies n o t in re strictin g im m ig ratio n , b u t in th e d istrib u tio n of in d u stria l p la n ts th ro u g h o u t th e co u n try .
T h is is a m a tte r w hich h as a lre a d y re ce ive d consid er
able a tte n tio n b y eco n o m ists, th o u g h n o t as e x h a u s
t iv e ly as it m ig h t d ese rve, if th e fu n d a m e n ta l co n d i
tio n s did n o t requ ire so ra d ica l a ch an ge to m ake it p ra ctic a b le . T h e m ain fa c to r w h ich a ttr a c ts in d u stries in A m e rican cities is th e co n ce n tratio n of lines of tr a n sp o rta tio n a t th o se p o in ts. W ere tra n s
p o rta tio n rate s a lw a y s as low a t ru ral p o in ts as a t th e cities, th e ta s k w o u ld b e g r e a tly sim p lified . D o c to r E lio t is of th e opinion th a t th e p ro je c t is n ow easier
366 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 Vol. 6, No. 5 b ecau se of th e p arcel po st d evelo p m e n t, th e gro w th
of tr o lle y lines, and fre ig h t and au to m o b ile tru ck s.
H o w eve r, in d u stria l g ro w th w ill d ep end on ch eap rail
ro ad rate s fo r fu el and raw m aterials and fo r sh ip m ent of finish ed p ro d u cts to a d egree w h ich w ill m ake th e o th er m eans of tra n sp o rta tio n h a rd ly w o rth y of con sid eratio n .
On th e o th er h and, th e re are certain ch ara cte ristics in ru ra l lo catio n s w h ich are a ttr a c tiv e for in d u strial en terp rises. T h e co st o f sites for fa cto rie s and resi
dences of em p lo ye es, th e a b ility of w orkin gm en to h a v e th e ir ow n gard ens, th e fa c ility for w aste disposal, can , if th e fu n d a m e n ta l con d itio n s be m ade righ t, w o rk a p ra ctic a l re vo lu tio n . B u t tran sp o rtatio n co n d itio n s are th e v it a l p o in t and th e schem e w ill be im p ra ctic a b le u n til th e ru ra l p o in t can be g u aran tee d th e sam e tra n sp o rta tio n rate s as th e c ity .
W . A . H a m o r
N E W S E C T IO N A D D E D T O J O U R N A L
A n ew sectio n on G o v e r n m e n t Pu b l i c a t i o n s
h as been ad d ed to th e Jo u r n a l, begin n in g in th is issue, u n der th e ed ito rsh ip of R . S. M cB rid e , A sso cia te C h e m ist in th e B u re a u of S ta n d a rd s. T h is w o rk is
S T U D Y O F T H E C O M P O S I T I O N O F W A T E R G A S T A R B y C . R . D o w n s a n d A . L . D b a n
R e c e iv e d F e b r u a r y 17, 1914
W a te r gas ta r, m ore p ro p e rly ca rb u re tte d w^ater gas ta r, is th e t a r r y p ro d u c t se p a ra tin g o u t in th e p u ri
fy in g sy ste m s o f p la n ts m a n u fa ctu rin g ca rb u re tte d w a ter gas. I t is m uch less visco u s th a n o rd in a ry coal ta r, w ith a d is tin c tly d ifferen t odor, due in p a rt to th e absence o f th e ph enols and bases ch a ra cte ristic of coal ta r. I t is u n derstood th a t a p o rtio n of th e p etroleu m used in c a rb u re ttin g , a fte r passin g th ro u g h v a rio u s m olecu lar ch an ges, ap p ears fin a lly as ta r, b u t of th e e x a c t n a tu re of th e tra n sfo rm atio n s little is d efin itely k n o w n . I t is, of course, th e o b je c t of th e gas m aker to ch an ge as larg e a p e rcen ta ge of his gas oil in to p e rm a n en t gases as possible and k eep th e p ro d u ctio n o f ta r to th e lo w e st lim it.
A search th ro u g h th e lite ra tu re for d a ta concern in g w a te r gas ta r y ie ld s b u t fra g m e n ta ry and in a d e q u ate resu lts. A . H . E llio t t ,1 M a tth e w s and G o u ld e n ,2 and C . N . F o rre s t3 h a v e record ed th e resu lts of fra ctio n a l d istillatio n s o f th e ta r, and D ean and B a te m a n ,4 S. P . S a d tle r,5 and F o rre st3 h a v e fu rn ish ed in fo rm a tio n re g a rd in g th e com p o sitio n o f th e creo so te oils d erived fro m w a te r gas ta r. Som e of th e sta te m e n ts t o be fo u n d in th e lite ra tu re refer to m a terial cle a rly q u ite d ifferen t fro m th e w a te r gas ta r p ro d u ced in th e s ta n d a rd A m e rican in s ta lla tio n s o f th e presen t d a y . T h u s M a tth e w s and G o u ld e n ’s ta r w as lig h te r th a n w a ter and co n tain ed S .51 per cen t of “ lig h t p a raffin s.”
1 A m . C h em . J o u r ., 6, 248.
* G as W o rld . 1 6 , 6 2 5 .
* J o u r . S o c. C h em . I n d . , 3 0 , 193.
4 U . S . F o r e s t S e r v ic e . C irc u la r 112.
‘ T r a n s . A m . I n s t. C h em . "Eng., 2 , 177.
p lan n ed to b rin g to ch em ists an d engineers prompt n o tice of all g o ve rn m en t rep o rts of in te re st to them, an d to b riefly and c le a rly re vie w th e scope and pur
pose of th ese p u b lica tio n s. I t is n o t inten ded that th e a rticles sh all be fu lly a b stra cte d , since the work of Chem ical Abstracts in th is lin e sh o u ld n ot be dupli
ca te d ; b u t a p ro m p t a n n o u n cem en t of th e publica
tio n s w ill do a g re a t deal to assist th e chem ical pro
fession in ta k in g a d v a n ta g e of th e m a terial now being issued b y th e G o v e rn m e n t. I t w ill c e rta in ly be more co n v e n ie n t for th e m em bers of our S o c ie ty thus to h a v e condensed in to one list th e ann oun cem ents pre
v io u s ly sc a tte re d th ro u g h a n u m b er of lists appear
in g a t irreg u lar in te rv a ls fro m th e v a rio u s depart
m ents. A ll G o v e rn m e n t P rin tin g Office publications o f v a lu e to ch em ists w ill be re vie w e d , including those w h ich h a ve ap p eared since J a n u a ry i , 1914. The item s of in d u stria l im p o rta n ce a p p e arin g in the Daily Consular Reports w ill also be a b stra cte d , beginning w ith M arch 1, 1914.
I t is ou r b elief th a t th is u p -to -d a te su m m a ry of the im p o rta n t in v e stig a tio n s an d p u b lica tio n s of the G o v e rn m e n t w ill be of im m ense v a lu e to our profes
sion.
T h e d a ta p resen ted in th is p a p e r w ere obtained on w a te r gas ta r from th e p u rify in g sy ste m served by several sta n d a rd L o w e s y ste m w a te r gas sets. The c a rb u re ttin g oil in use a t th e tim e w as d erived from O k lah o m a crudes. A s m igh t be p red icted , the tar s e p a ra tin g a t d iffer
e n t p o in ts a lo n g th e p u rify in g sy ste m , as th e g a s passes from th e sets to th e final sta ge s of p u rificatio n , b ecom es p r o g r e s s iv e ly lig h te r and rich er in th e m ore v o l a t i l e c o n s t i t u e n ts.1 M i x e d t a r f r o m t h e w h o le sy ste m w as used for th e w o rk described in th e p resen t paper.
S Y S T E M A T I C F R A C T I O N A L D I S T I L L A
T I O N S
A series of d eta iled fra c tio n a l d i s t i l l a tio n s w as carried o u t w ith a v ie w to lo c a tin g th e b o ilin g p o in ts of a n y in d i
v i d u a l com p o u nd s w h ich m igh t be
p resen t in s u b s ta n tia l am o u n ts. T h e first d istillatio n of th e ta r up to 250° C . w as carrie d o u t in a five gallon
1 D e a n a n d D o w n s , T i n s J o u r n a l . 3, 108.
ORIGINAL PAPERS
May, 1914 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 367 copper still, th e d istilla tio n b ein g e ffe c t e d b y im m ersin g a
resistance coil in th e ta r. T h e d istillate s th u s o b ta in e d constituted th e “ F irs t S eries” o f fra ctio n s, an d th e
C E N T IG R A D E T E M P E R A T U R E Fi g. 2 — Th i r d Se r i e s Di s t i l l a t i o n
residue was sa v e d fo r la te r s tu d y . T h ese first fra ctio n s were then re fra ctio n e d fro m an e le c tric a lly h e a te d glass flask p ro vid ed w ith a H em p el colu m n , y ie ld in g th e
‘‘Second S eries.” In re fra ctio n in g th e secon d and subsequent d istilla te s a m odified Y o u n g d ep h legm a to r was em p lo yed up to 2000 C ., an d a b o v e th a t th e Hempel colu m n. T h is Y o u n g d e p h le g m a to r consisted of six cham bers, th e floors o f w hich con sisted of p e r
forated glass p la te s p ro v id e d w ith overflow ' tu b e s as
Fi g. 3 — Si x t h Se r i e s Di s t i l l a t i o n
indicated in F ig . 1. T o a v o id e x cessiv e co n d e n satio n 'n the ch am bers th e d ep h legm a to r wras a ir-ja c k e te d UP to n o 0 C ., an d a b o v e th a t en clo sed in an asbestos sheath h eated b y resista n ce w ires. In th is w a y th e Process of rep e ated fra c tio n a tio n , acco rd in g to th e
com m on p ra ctice o f h a n d lin g th e fra ctio n s in such w o rk, w as co n tin u ed to th e “ T h ird S eries” o f fractio n s b o ilin g up to 250° C . an d to th e “ S ixth S eries” w ith th e lo w er b o ilin g p o rtio n s. T h e cu rv e s o f th e th ird an d six th series are sho w n in F igs. 2 and 3.
F ro m F ig . 2 it is clear th a t th e large st single co n stitu e n t boils a t a b o u t 220° C ., a p p ro x im a te ly th e b o ilin g p o in t of n ap h th a le n e . T h e a b ru p t rises in F ig. 3 a t 8o°, n o ° and 140 ° C . in d ic a te th e presence of ap p reciab le a m o u n ts of in d iv id u a l su b sta n ces b o ilin g n ear th e se te m p eratu re s, w hich w ere su b se q u e n tly p ro v e n to be benzene, to lu en e, an d th e x yle n e s. A sm aller irre g u la rity ap p e ars n ear th e b o ilin g p o in t of m esitylen e, 16 4 .5° C . I t is b e lie ve d t h a t a fa irly s a tis fa c to ry sep a ra tio n h ad b een a ch ie v e d in th is sixth series, an d du rin g co n sid erable p o rtio n s of th e d is
tilla tio n w hen th e d istilla te s ap p eared to be n e a rly pure co m p o u n d s, fractio n s w ere ta k e n a t each degree rise in te m p e ra tu re and co rrectio n s m ade fo r th e em e rg en t th e rm o m e te r stem .
G E N E R A L C H A R A C T E R I S T I C S O F T H E D I S T I L L A T E S
i n d i c e s o f r e f r a c t i o n— T h e ind ices of refra ctio n
o f th e fra c tio n s of th e fifth series w ere d ete rm in ed a t 30° C . w ith th e resu lts show n in th e fo llo w in g ta b le :
T e m p . R e f r a c tiv e T e m p . R e f r a c tiv e
o f f r a c tio n in d e x o f f r a c tio n in d e x
0 C . a t 3 0 ° C. 0 C . a t 3 0 ° C .
7 9 - 83 1 .4 9 3 8 1 2 5 -1 3 0 1 .4 9 1 6
8 3 - 85 1 .4 9 3 8 1 3 0 -1 3 7 1 .4 9 3 5
8 5 - 9 0 1 .4 9 3 3 1 3 7 -1 4 5 1 .4 9 6 7
9 0 - 95 1 .4 9 2 3 1 4 5 -1 5 0 1 .4 9 8 7
9 5 - 1 0 0 1 .4 9 2 1 1 5 0 -1 5 5 1 .4 9 7 6
1 0 0 -1 0 9 1 .4 9 1 0 1 5 5 -1 6 0 1 .4 9 6 8
1 0 9 -1 1 3 1 .4 9 0 9 1 6 0 -1 6 5 1 .4 9 7 9
1 1 3 -1 1 5 1 .4 9 1 0 1 6 5 -1 7 2 1 .5 0 3 0
1 1 5 -1 2 0 1 .4 9 0 8 1 7 2 -1 7 9 1 .5 1 8 0
12Q -125 1 .4 9 1 2 1 7 9 -1 8 5 1 .5 2 6 9
b r o m i n e a b s o r p t i o n
T h e brom in e a b so rp tio n s o f th e fra ctio n s w ere used as a r e la tiv e m easure of th e u n sa tu ra te d h y d ro ca rb o n s.
T h e d ete rm in atio n s w ere m ade b y allo w in g an excess o f a te n th n orm al so lu tio n of b rom in e in carb o n te tra -
S ix th s c rie s f r a c tio n s G . B r a d d e d T h i r d s e rie s f r a c t io n s G . B r a d d e d
0 C . p e r cc. 0 C . p e r cc.
7 8 . 9 - 7 9 .7 0 .0 1 3 3 1 8 0 -2 0 5 0 .4 4 8 7
7 9 . 7 - 8 0 .7 0 .0 1 8 1 2 0 5 -2 3 5 0 .2 5 2 6
8 0 . 7 - 8 5 . 0 0 .0 1 3 3 2 3 5 -2 5 0 0 .1 6 2 9
8 5 . 0 - 9 2 . 0 0 .0 1 8 2
9 2 - 1 0 1 0 .0 1 9 2 S e c o n d serie s
101 - 1 0 9 0 .0 1 4 1 f r a c tio n s
109 - 1 1 0 . 5 0 .0 1 0 4 2 5 0 -2 6 0 0 .0 4 7 9
1 1 0 .5 - 1 1 4 0 .0 1 3 3 2 6 0 -2 7 0 0 .0 4 3 2
114 -1-20 0 .0 2 4 7 2 7 0 -2 8 0 0 .0 6 1 0
J 2 0 - 1 3 0 0 .0 3 6 4 2 8 0 -2 9 0 0 .0 4 4 2
130 - 1 3 8 0 .0 6 7 1 2 9 0 -3 0 0 0 .0 9 6 3
138 - 1 4 2 . 5 0 .1 0 9 8 3 0 0 -3 1 0 0 .0 7 7 1
1 4 2 .5 - 1 4 5 0 .1 7 2 4 3 1 0 -3 2 0 0 .0 7 0 0
145 - 1 5 0 0 .2 1 8 6
150 - 1 5 5 0 ,1 8 3 2
155 - 1 6 0 0 .1 6 1 6
160 - 1 6 4 0 .1 5 2 2
164 - 1 6 7 0 .4 1 7 6
167 - 1 7 2 0 .4 8 2 4
172 - 1 7 7 0 .4 0 0 8
177 - 1 8 2 0 .5 5 2 0
ch lorid e to re a ct on I cc. of a sam p le for 15 m inul th e vessel co n tain in g th e m ix tu re b ein g im m ersed in a b a th o f ice and s a lt and k e p t in th e d a rk . A fte r th is
368 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 ol. 6, No. 5 rea ctio n period th e unused brom in e and th e h yd ro -
brom ic acid fo rm ed w ere b o th d eterm in ed , and from th ese d ete rm in atio n s th e gram s of brom in e ad ded per cu b ic ce n tim e te r of oil cou ld re a d ily be calcu lated .
“p a r a f f i n s”
Since th e h y d ro ca rb o n s of w a te r gas ta r h a v e th e ir origin in p e tro leu m oil it m igh t be sup p osed th a t co n sid erab le q u a n titie s o f “ p araffin s” w o u ld be fou n d in th e d istilla te th e re fro m . T o th ro w lig h t on th is p o in t th e fra ctio n s w ere su lfo n ated w ith co n cen trated su l
fu ric a cid an d th e p e rcen ta ge b y vo lu m e of th e unsul- fo n a te d residues d eterm in ed .
m p . o f f r a c tio n P e r c e n t T e m p , o f f r a c tio n P e r c e n t 6t h s c rie s X Jn su lfo n a tcd 6t h serie s u n s u lf o n a te d
75 - 79 0 .0 6 138 - 1 4 2 . 5 1 . 2
79 - 9 0 N o n e 1 4 2 .5 - 1 4 5 2 .4
8 0 - 81 N o n e 145 - 1 5 0 1 . 2
81 - 85 N o n e 150 - 1 5 5 2 . 2
85 - 92 N o n e 155 -1 6 1 ' 1 . 6
92 - 1 0 1 N o n e 161 - 1 6 6 . 5 1 . 8
101 -1 0 9 N o n e 1 6 6 .5 - 1 7 2 1 . 6
109 - 1 1 0 . 5 N o n e 172 - 1 7 7 N o n e
1 1 0. 5 - 1 1 4 N o n e 3 r d series
114 - 1 2 0 N o n e 180 - 2 0 5 5 5 .0
120 - 1 3 0 0 . 4 205 - 2 3 5 1 .4
130 - 1 3 8 0 . 4 235 - 2 5 0 2 . 2
T h e e x tra o rd in a rily high p ercen ta ge in th e d istillate fro m iS 0 ° -2 0 5 ° calls for som e com m en t. T h e residues from all th e o th er fra ctio n s w ere w ash ed to clear oils, b u t th e m a terial o b ta in e d here w as of p u tty -lik e con siste n c y and resinous odor, and ap peared to be a p o ly m erizatio n p ro d u c t of som e u n sa tu ra te d h yd ro ca rb o n ra th e r th a n a “ p a ra ffin .”
L O W - B O I L I N G F R A C T I O N
On rep e ated d istillatio n of th e first fractio n s below 75° C . a sm all a m o u n t of a v e r y v o la tile liq u id w as o b ta in e d , b o ilin g b etw e en 44 ° C . and 6 5° C ., m ost of it com in g o v er b etw e en 6 o ° and 62°.
So sm all a q u a n tity o f th is m a terial w as o b ta in ed th a t a n y th in g m ore th a n a fe w q u a lita tiv e te sts w as n o t feasib le. I t ch arred and le ft no residue of un dissolved oil w h en tre a te d w ith c o n cen trated su lfu ric acid. It rea cte d v io le n tly wdth stro n g n itric acid , an d abso rbed b rom in e ra p id ly fro m b rom in e w ater, form in g a brom i- n a te d p ro d u ct h e a v ie r th a n w ater. N o te s t fo r sulfur cou ld be o b ta in ed . T h ese te sts com bine to in d icate a h y d ro ca rb o n m ixtu re of m a rk e d ly u n satu ra ted ch ara cte r.
T I I I O P H E N
T h e su lfu r co n tain in g com p o u nd th io p h en (C4H4S) app ears to be a lw a y s asso ciated w ith benzol in coal ta r lig h t oil. B ecau se of th e closeness of its b oilin g po in t (84° C .) to th a t o f b en zo l, it can n o t be rem oved b y fra c tio n a l d istillatio n . T h e presence of th io p h en in w a ter gas ta r d istilla te s w as in d icate d b y th e indo- ph enine te s t w ith isa tin and co n cen trated su lfu ric acid . T h e m eth o d of D e n ig è s1 w as fo llow ed in m akin g q u a n tita tiv e estim atio n s of th is com pound. T h e a v e ra g e of th irte e n a n a lyse s of th e fractio n s b etw een 79° C . an d 90° C . w as 2.1 per cen t.
T e s ts for th e h igh er h om o lo gu es of th io p h en w ere o b ta in e d w ith th e h igh er b o ilin g fractio n s, b u t no q u a n ti
ta tiv e estim atio n s w ere a tte m p te d .
1 C o m p t. re n d ., 9 0 , 781.
B E N Z E N E
A n in sp ectio n of th e d istillatio n c u rv e of th e sixth series sh o w s a d ecid ed rise a t th e b o ilin g p o in t of ben
zene, in d ic a tin g th e presence of a b o u t 0.4 per cent of th a t co m p o u n d . T h e d istillate b etw e en 79° and 810 co u ld be re a d ily n itra te d , g iv in g a go od y ie ld of nitro- ben zol b o ilin g b etw e en 10 6 .5o and 1 0 7 .5 0 a n d showing no e v id en ce o f “ p araffin s” b y th e m eth o d given by L u n g e .1 D in itro b en zen e, m eltin g p o in t 90o, and ani
line d istillin g b etw e en 18 2 o 'a n d 1 8 5 o w ere also pre
pared fro m th e p u rified b enzene o b ta in e d from water gas ta r. T h e aniline w as colorless and tu rn ed only s lig h tly brow n on sta n d in g fo u r m on th s p ro tected from su n lig h t.
A n u m ber o f sam p les w ere p rep ared conform ing to th e req u irem e n ts o f th e co m m ercial grad es of benzol.
T h e s ta rtin g m a te ria l w as a cru d e lig h t oil obtained in th e in itia l d istillatio n of w a ter gas ta r in a large still.
T h is w as fra ctio n e d up to iS o ° C . fro m a large plain d istillin g b u lb and th e d istilla te refra ctio n ed through a H em pel colum n ta k in g th e fo llo w in g fraction s:
1... 6 8° - 7 9 ° 2... 7 9 ° - t 0 0 ° 3... 1 0 0 ° - 1 2 5 ° 4... 1 2 5 ° - 1 5 5 °
P u re b en zen e w as p rep ared fro m th e fractio n No. 2 b y a g ita tin g w ith co n ce n trate d su lfu ric acid , followed by wTash in g w ith d ilu te acid and w a te r, an d agitatio n with c a u stic so d a so lu tio n fo llo w ed b y th o ro u g h washing.
U n der la b o r a to ry co n d itio n s a loss of 4 per cent was exp erien ced b y th ese tre a tm e n ts. T h e w ashed prod
u c t w as c a re fu lly red istille d w ith a H em pel column a n d Y o u n g d ep h legm a to r, y ie ld in g a p ro d u ct of correct b o ilin g p o in t. T h is c. p. b en zen e g a v e no test for th io p h en , no d isco lo ratio n w ith c o n cen trated sulfuric acid , w as of sw eet odor and h as sho w n no yellowing on sta n d in g for tw o years.
P re p a ra tio n s of 90 per cen t ben zol an d 50 per cent ben zol w ere also m ade from w a te r g a s ta r light oil b y fra c tio n a l d istillatio n and w ash in g w ith sulfuric acid an d c a u stic soda. W ith th ese p ro d u cts much less e x a ct fra c tio n a l d istillatio n w as req u ired th a n w ith the c. P. benzol. B o th p re p ara tio n s w ere free from thio
phen, g a v e no color w ith co n ce n trate d sulfuric acid, and h a v e rem ain ed w a te r w h ite and sw eet for two y e a rs. T h e loss in w ash in g w as sm all.
I n p rep arin g 16 0 0 ben zol or so lv e n t n a p h th a th e same general process of w ash in g w as fo llo w ed b u t th e loss in w ash in g w as m uch grea te r, a m o u n tin g to over 15 pef c e n t . T h e p ro d u c t w as of good color an d odor, and g a v e b u t a v e r y p ale straw' color w ith c o n c e n tr a te d su lfu ric acid.
T O L U E N E
A n in sp ectio n of th e “ S ixth S eries” d istillatio n curve show s a rise of a b o u t 0.8 p e r cen t a t th e boiling point o f to lu en e. A p o rtio n of th is fra c tio n of th e sixth series w as n itra te d , g iv in g 85 per cen t of th e theoretical y ie ld , an d sh o w in g b u t a tra c e o f paraffins.
T h e fra c tio n N o . 3 fro m th e H em p el colum n dis-, filia tio n m en tion ed u n der “ B e n z e n e ” a b o v e was w a s h e d
w ith su lfu ric acid an d a lk a li (w ith a loss of 6 per cent)
1 " C o a l T a r a n d A m m o n ia ,” 3 r d E d i tio n , p . 641.
May, 1 9 1 4 T E 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 369 and th e w ash ed oil fra c tio n e d w ith a H em p el colum n.
The fractio n 95 120 ° w as red istille d w ith th e sam e apparatus and th e fra c tio n 10 9.5 0—1 1 1 .5 ° ta k e n . T h is product co m p are d fa v o r a b ly w ith sta n d a rd m akes of c. P . tolu ene an d g a v e no te s t fo r th io to lu e n e and no color w ith c o n ce n tra te d su lfu ric acid.
X Y L E N E S
The n ext d ecid ed rise in th e d istillatio n cu rv e a fte r that at th e to lu e n e fra c tio n app ears aro u n d 140°, suggesting th e presence of x y le n e s. T h e curve- in d i
cated a b o u t 1.2 per cen t of th e se h y d ro ca rb o n s.
The sep aratio n of th e th ree isom eric xy le n e s b y fr a c tional d istillatio n is n o t fea sib le b ecau se of th e nearness of their b o ilin g p o in ts. B y th e use of L e v e n s te in ’s method1 one sam p le o f x y le n e fra c tio n y ie ld e d 75 per cent m etax yle n e , 20 per cen t p ara, and, b y difference, 5 per cent of th e o rth o . On a n o th er sam ple of w a ter gas tar th e resu lts w ere 77 p e r cen t m eta, 19.5 per cen t para, 2.0 per cen t o rth o , and 1.5 per cen t “ p a ra ffin s.”
It is d o u b tfu l w h eth er th e o rth o -x y le n e is p rese n t in more th an tra ce s since a q u a lita tiv e t e s t 2 fa ile d to reveal its presence.
The sodium sa lts of th e o rth o - an d m e ta-x y le n e su l
furic acids w ere p rep ared acco rd in g to J a c o b se n .3 The n eedle-like c ry s ta ls sim ilar to th o se describ ed for the ortho sa lt w ere o n ly p rese n t in v e r y sm a ll am o u n ts.
M etaxylene b oilin g i3 8 ° - i3 9 ° w as p rep ared acco rd in g to Jacobsen b y d eco m p o sin g th e m e ta -x y le n e su lfu ric acid.
m e s i t y l e n e
A slight irr e g u la r ity of th e d istillatio n cu rv e arou n d 165° suggested th e presence of m esitylen e. T h e “ S ix th Series” d istillate o b ta in e d a t th is p o in t w as tw ic e re distilled w ith a G lin s k y d e p h le g m a to r and th e d istilla te between 164 ° an d 1 6 7 ° n itra te d . A solid n itro-com - pound was o b tain ed w h ich a fte r carefu l w ash in g and recrystallization g a v e a c o n s ta n t m eltin g p o in t of 236°.
The n itratio n of a n o th er p o rtio n g a v e a p ro d u c t m eltin g at 235°. M u llik e n g iv e s th e m eltin g p o in t of trin itro mesitylene as 235° C .
From, th e a lco h o l used to w ash th e c ry s ta ls of t r i
nitro m esitylen e a sm all crop of b arrel-sh ap ed c ry sta ls was obtained w h ich on re p e a te d r e c ry s ta lliz a tio n g a v e a melting p o in t of 16 7 °, and c o n tain ed 16.31 per cen t of nitrogen. T h e th e o re tic a l n itro g en co n te n t of tri- m tro-trim ethyl b enzenes is 16.47 per cen t, b u t th e melting p o in t is fa r to o lo w fo r trin itro pseu d ocu m en e.
The am ount of th is co m p o u n d w as to o sm all fo r fu rth e r experiments, an d it rem ain ed u n id entified.
n a p h t h a l e n e
Inspection of th e d istillatio n cu rv e fo r th e th ird series shows th a t th e m o st decid ed rise in th e w h ole cu rv e appears b etw een 2 15 ° and 235°, in d ic a tin g a r e la tiv e ly large proportion of n ap h th a le n e . A n a tte m p t w as Wade to estim ate th e a m o u n t of n ap h th a le n e in w a te r
£as tar as fo llo w s: 500 gra m s of ta r w ere d istilled to Jio° C. and th e n ap h th a le n e s e p a ra tin g in th e d istillate
1 Jour. S o c. C h em . I n d . , i , 78.
' M u llik en , " I d e n t if ic a tio n o f P u r e O r g a n ic C o m p o u n d s ," V ol. I , p . 202.
' Ber., 10, 1009.
filtered off an d pressed in a screw press; th e filtra te w as p la ce d in a fre e z in g m ix tu re an d th e n e w c r o p of n a p h th a len e c ry s ta ls sim ila rly re m o v e d ; th is filtra te w as d is
tille d co lle ctin g a fra c tio n fro m i8 5 ° -2 6 5 ° , w h ich w as cooled , filtered a n d th e n ap h th a le n e pressed; th e new filtra te w as refra ctio n ed , ta k in g a fra c tio n i9 5 ° - 2 3 5 ° , w h ich w as sim ilarly d e p riv e d of its n a p h th a le n e and th e n ew filtra te d istilled , co lle ctin g a fra c tio n 2 1 0 ° - 225°, w hich yie ld e d b u t a v e r y sm all se p a ra tio n of n a p h th a le n e w hen p laced in a freezin g m ix tu re ; th e to t a l w e ig h t of th e solids th u s reco ve red a m o u n ted to 8.0 per cen t of th e ta r.
N a p h th a le n e w as p rep ared fro m th e solids pressed fro m th e d istilla te o b ta in e d fro m w a ter gas ta r b etw e en 200° an d 250°. T h ese solids w ere d istilled , re je c tin g th e first and la s t 10 per cen t, an d th e d istilla te tre a te d w ith su lfu ric a cid co n ta in in g a little d ich ro m a te. T h e p ro d u ct, a fte r th o ro u g h w ash in g w ith w ater, w as pressed and d istilled , g iv in g a p ro d u ct b o ilin g a t 2 1 7 ° C-.
(un corrected ) an d m eltin g a t 80°, whi,ch sh o w ed no d isco lo ratio n w ith co n ce n tra te d su lfu ric acid an d r e m ain ed p e rfe c tly w h ite a fte r an exp osu re of fo u r m on th s to th e ligh t.
a n t h r a c e n e
T h e a b o v e d escrib ed ex p e rim e n ta l w o rk w a s carrie d o u t fo r th e m ost p a rt on th a t p a r t of th e w a te r g a s ta r w hich d istilled b elo w 250° C . in th e in itia l d istillatio n . T h e residue a b o v e 250° C . w as w orked up in c o lla b o ratio n w ith D r. F . L . H aigh o f th is la b o ra to ry .
T w o m eth od s of d istillin g th is residue w ere trie d ; in one th e d istillatio n w as carried o u t w ith h e a t alone, in th e o th er ste am w as in tro d u ce d in to th e s till in co n sid erab le volum e." In b o th ty p e s of d istilla tio n m ost of th e fra ctio n s show ed, a se p a ra tio n o f solid m aterials on cooling. T h ese solids w ere rem o ved , pressed and w eigh ed an d th e a n th ra ce n e in th e m d eterm in ed a c co rd in g to th e m eth o d p rop osed b y M e ister, L u ciu s and B ru n in g ,1 “ w ith a p p e n d ix .” T h is m eth o d co n sists in c o n v e rtin g th e a n th ra ce n e in to an th ra q u in o n e b y tr e a tm e n t w ith ch ro m ic a cid in gla cia l a ce tic a cid so lu tio n . T h e an th ra q u in o n e w as fu rth e r p u rified b y so lu tio n in fu m in g su lfu ric a cid an d r e c o v e ry th e re fro m b y d ilu tio n .
T h e resu lts of th e d ry d istilla tio n w ere as fo llo w s:
P e r
c e n t of P e r c e n t T e m p e r a P e r c e n t P e r c e n t T e m p e r a t u r e so lid s a n th r a c e n e tu r e o f s o lid s a n t h r a c e n e
° C . in f r a c tio n s in so lid s 0 C . in f r a c tio n s in s o lid s
- 2 6 5 N o n e 3 3 5 -3 4 5 4 . 1 9 4 1 .7 5
2 6 5 -3 0 5 N o n e 3 4 5 -3 5 5 4 .2 7 3 4 .8 5
3 0 5 -3 1 5 1 .3 2 6 5 .4 9 3 5 5 -3 6 0 3 . 3 9 2 6 .4 1
3 1 5 -3 2 5 2 .3 2 6 1 .3 5 3 6 0 -3 7 0 4 . 3 6 7 .4 1
3 2 5 -3 3 5 3 .8 5 4 2 .8 2 3 7 0 -4 0 0 N o n e
T h e s e resu lts show th e presence of 0.392 per cen t of a n th ra ce n e in th e residue a b o v e 250°, e q u iv a le n t to 0.29 per cen t of th e o rigin al ta r.
T h e th e rm o m e ter read in gs in th e ste am d istillatio n w ere of little v a lu e ; th e fra c tio n s w ere a cc o rd in g ly c u t a t a b o u t each 250 cc. of oil d istilla te in d istillatio n s
1 A lle n , “ C o m m e r c ia l O r g a n ic A n a ly s is ," 3 r d E d ., V o l. I I , P t . I I , p . 2 2 9 .
3 7 ° 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 ol. 6, No. 5 of 5000 gram s of th e “ R e sid u e .” T h e solids w ere d ete r
m ined an d a n a ly z e d w ith th e resu lts g iv e n below :
P e r c e n t of V o lu m e W t. o f s o lid s a n t h r a c e n e
F r a c t io n C c. in f r a c tio n s in s o lid s
1... 2 5 0 N o n e 2... 2 6 0 N o n e 3... 2 5 0 N o n e
4 ... 2 6 0 1 . 2 5 8 .2 0 5 ... 2 5 0 5 . 8 4 7 .2 6 6... 2 6 0 1 1 .0 4 6 .8 3 7 ... 2 5 0 1 5 .2 4 0 .5 2 8... 2 5 0 4 4 . 4 4 3 .7 6 9 ... r ... 2 5 0 1 2 .1 3 9 .1 9 1 0 ... 2 5 0 5 . 4 2 1 .7 3 1 1 ... 2 6 0 N o n e
1 2 ... 2 5 0 N o n e
In th e ste am d istillatio n , th erefore, 0 .517 per cen t of anth racene' w as reco ve red from th e “ R e s id u e ” a b o v e 250°, e q u iv a le n t to 0.383 per cen t of th e origin al tar.
T h e re w as cle a rly less d ecom p o sition w hen ste am w as used, since th e pitch co n tain ed b u t 5.6 per cen t of free carbo n , w h ereas th a t fro m th e d ry d istillatio n a veraged 57 per cen t. P r a c tic a lly all of th e an th race n e com es o v e r u n der 360° in th e d ry d istillatio n , and a t th a t te m p e ra tu re little c ra ck in g h as ta k e n p lace, th e p itch co n ta in in g b u t 6.0 per cen t free carbo n. A b o v e 360° an oran ge-co lo red , visco u s, sem i-solid m a terial ap p ears in th e d istilla te and seem s to be in d ic a tiv e of m arked d ecom po sition .
F a ir ly p u re a n th ra ce n e w as p rep ared from th e e x pressed solids b y w ash in g w ith gaso lin e, an d su b lim in g th e residue. T h is an th race n e m elted a t 2 0 7 ° - 2 i i ° C . an d w h en m ixed w ith a sam p le of K a h lb a u m ’s a n th ra cene, th e m ix tu re m elted a t 2 o 8 ° - 2 i i ° .
A s a fu rth e r te s t of th e q u a lity of th e solids pressed from th e high b o ilin g d istillate s o f w a te r gas ta r, 50 gram s of th e se solids reco ve red fro m th e d istillate b etw e en 289° and 3 6 1° w ere o xid ized w ith b ich ro m ate a n d su lfu ric acid. T h e an th ra q u in o n e a fte r p u rifi
catio n w as su b lim ed g iv in g 18.2 gram s of c ry sta llin e a n th raq u in o n e . A n th raq u in o n e p rep ared in th is w a y w as co n v e rte d in to th e sod iu m an th raqu in on e-m on o - su lfo n ate w h ich in tu rn w as co n v e rte d in to alizarin e.
A b e a u tifu l oran ge-red cry sta llin e p rep ara tio n of a liz arine w as o b ta in e d on su b lim in g th e p ro d u ct. U nder la b o r a to ry con d itio n s th e tra n sfo rm atio n of a n th ra quin on e in to alizarin e is d ifficu lt, an d th e yield s o b ta in e d co rresp o n d in g ly low . F ro m a b o u t 20 gram s of an th ra q u in o n e o n ly a b o u t 7 gram s of alizarin e w ere o b tain e d .
S U M M A R Y
A sy s te m a tic fra c tio n a l d istillatio n of w a ter gas ta r sh o w s th a t it possesses a gen eral resem blan ce to coal ta r in its h y d ro ca rb o n co n te n t a lth o u g h , of course, th e bases, p h enols, an d free carb o n of th e la tte r are a b se n t or n e a rly so. T h e sm all a m o u n ts of m aterial in th e d istilla te s resistin g th e a ctio n o f su lfu ric acid in d ica te an absence o f p araffin an d n ap h th en e h y d ro carbo n s, and th e m a rk ed v a ria tio n in th e c a p a c ity for h alogen a d d itio n p o in ts to v a ria b le a m o u n ts of u n sa tu ra te d lin k in g s o u tsid e th e b enzene ring.
B enzen e, to lu e n e , th e xy le n e s, m esitylen e, n a p h th a lene, and an th race n e were show n to b e presen t in su b
sta n tia l am o u n ts. T h e p rep ara tio n of th e pure hydro
carb o n s an d of com m ercial p ro d u cts co u ld be effected b y m eth od s sim ilar to th o se em p lo ye d w ith coal tar, and w ith o u t en co u n terin g sp ecial d ifficulties.
I t w o u ld ap p e ar p ro b ab le th a t w a te r gas ta r m ay offer a co m m ercial source of su p p ly for th e vario u s grades of benzol and so lv e n t n a p h th a . N ap h th a len e could re a d ily be prod u ced , b u t th e re is no a d eq u a te demand, and it is lik e ly th a t th e presen t tra d e conditions would n o t w a rra n t th e p ro d u ctio n of an th racen e.
Sh e f f i e l d Ch e m i c a l La b o r a t o r y Ya l e Un i v e r s i t y Ne w Ha v e n, Co n n.
T H E R A D I O A C T I V I T Y O F S O M E T Y P E S O IL S OF THE U N IT E D S T A T E S
B y R i c h a r d B . M o o r e R e c e iv e d M a r c h 6, 1914
S t r u t t 1 first called a tte n tio n to th e rad io a ctivity of ign eou s and se d im e n ta ry rocks. T h e a verage of his resu lts on ign eou s ro ck s sh o w ed a rad iu m content of 3.3 X io~12 gram s of rad iu m per gram of rock. The rad iu m co n te n t of th e sed im en taries w as somewhat less. J o ly 2 h as exam in ed a large n u m ber of rocks for rad iu m and th o riu m . H is rad iu m v a lu e s are somewhat large r th a n th o se of S tr u tt and o th er w orkers. The ave ra g e of a n um ber of his th o riu m determinations in d icate s th e presence of 1.58 X io~5 gram s of thorium per gram of ro ck . F le tc h e r ,3 w o rk in g p rim arily with seco n d ary ro ck s, has confirm ed J o ly ’s results and at th e sam e tim e po in ted o u t . th a t, w ith th e exception of th e calcareo u s ro ck s, th o se of th e sam e typ es have a lw a y s v e r y n e a rly th e sam e rad iu m con ten t.
A lth o u g h a consid erable a m o u n t o f w ork has been done on th e r a d io a c tiv ity of ro ck s and m inerals, very little h as been a tte m p te d a lo n g th is line w ith soils.
A k n o w led g e th a t th e a tm o sp h ere w as rad ioactive was n a tu r a lly fo llo w ed b y an in v e stig a tio n o f th e activity of th e u n dergro u nd air. E ls te r an d G eitel, Bumstead, B la n c, G a d o u ria n , W ilson , E b e rt, E v e , Sanders, Sat- te rly an d oth ers h a v e co n trib u te d to our knowledge of th is su b je c t. W h ereas a s tu d y of th e u n d e rg ro u n d air in d icate s v e r y p la in ly th a t th e soil is radioactive, it does n o t g iv e a n y ab so lu te v a lu e s for th e a ctiv ity of th e soil itse lf, as th e a c t iv it y of th e underground air dep en ds as m uch upon th e e m a n a tin g pow er of the ra d io a ctiv e m a tte r in th e soil as it does upon th e am ou n t of t h a t m aterial a c tu a lly present. Som e rough mini
m um d ete rm in atio n s h a v e been a tte m p te d . Wilson sta te s th a t th e re is p ro b a b ly seven tim es as much th o riu m as u ran iu m in th e su rface soils a t Manchester.
B la n c, on th e o th er h an d , e stim a te s t h a t from 5 per cen t to 70 per cen t of th e a c t iv it y o f .the Rom an soil is due to th o riu m ; w hile S an d erso n ’s4 w ork indicates th a t 1 cc. of soil a t N ew H a ve n pro d u ces radium emana
tio n in eq u ilib riu m w ith 8.9 X io~ 14 gram s of radium, and th o riu m em a n a tio n in eq u ilib riu m w ith 1.35 X i° 5 gram s of th o riu m . F le tc h e r5 g iv e s th e radium con ten t
1 P ro c. R o y . S o c., ( /I ) 77 (1 9 0 6 ), 472.
1 P h il. M a g ., 17 (1 9 0 9 ). 7 6 0 ; 18 (1 9 0 9 ), 1 40; 23 (1 9 1 2 ), 201.
• I b i d . , 23 (1 9 1 2 ), 279.
4 A m . J o u r . S c i., 3 2 (1 9 1 1 ), 169.
s P h il. M a g ., 23 (1 9 1 2 ), 279.
