Tiie Journal of Industrial and Engineering Gnemistry
Published 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
A T B A S T O N , P A .
Volume VI JU N E , 1914 No. 6
BOARD OF EDITORS Editor: M . C . W h i t a k e r
Assistant- Editor: L e o l a E . M a r k s
Associate Editors: G . P . A d a m s o n , E . G . B a ile y , H . E . B a r n a rd , G . E . B a r to n , A . V . B le in in g e r, W m . B lu m , W m . B r a d y , C . A . B ro w n e , F . K . C a m e ro n , W m . C a m p b e ll, F . B . C a r p e n te r, C . E . C a s p a ri, V . C o b le n tz , W . C . G ee r, W . F . H ille b ra n d , W . D . H o rn e, T . K a m o i, A . D , L it t le , C . E . L u c k e , P . C . M c llh in e y , J. M . M a tth e w s , T . J. P a r k e r , J. D . P e n n o c k , C liffo rd R ic h a rd s o n , W . D . R ic h a rd s o 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 r ig h t.
P u b lis h e d m o n th ly . S u b s c r ip tio n p r ic e t o n o n -m e m b e r s o f th e A m e r ic a n C h e m ic a l S o c ie t y , $ 6 .0 0 y e a r ly . F o r e ig n p o s t a g e , s e v e n t y - f iv e c e n t s , 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 e c o n d - c la s s M a t t e r D e c e m b e r 19, 1 9 0 8 , a t t h 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 o f M a r c h 3 , 1 8 7 9 . C on tribu tion s sh o u ld b e a d d ressed to M. C. W hitaker, C olum bia U n iv e r s ity , N ew York City
C o m m u n ica tio n s c o n c e r n in g a d v e r tis e m e n ts sh o u ld b e s e n t to T h e A m erica n C h e m ic a l S o c ie ty , 42 W est 3 9 th S t., N ew York City S u b sc r ip tio n s and c la im s lo r lo s t c o p ie s sh o u ld b e re fe r r e d to C harles L. P a rso n s, B o x 5 0 5 , W a sh in g to n , D. C.
, Es c i i i î n b a c h Pk i n t i n o Co m p a n y, Ea s t o n. Pa.
T A B L E O F Ed i t o r ia l s:
R e c e n t S y n t h e t ic S tu d ie s in th e T a n n in G r o u p 450 Or ig in a l Pa p e r s:
A T h e rm o e le c tr ic M e th o d fo r th e D e te rm in a tio n of th e P u r it y of P la tin u m W a re . B y G e o rg e K .
B u rg ess and P . D . S a l e ... 452
T h e D e te rm in a tio n o f th e D u s t F a ll in th e N e ig lib o r- ^ hood o f C e m e n t P la n ts . B y J. P . M it c h e ll... 454
T h e C o m b u stio n M e th o d for th e D ir e c t D e te rm in a tio n o f R u b b e r. B y L . G . W e s s o n ... 459
O sage O ran g e— -Its V a lu e as a C o m m e rc ia l D y e s tu ff. ^ B y F . W . K r e s s m a n n ... 462
T h e R e se rv e S u p p ly of P h o s p h a te R o c k in th e U n ite d S ta te s . B y W . H . W a g g a m a n ... 464
D e te rm in a tio n o f C a r b o n in S te e l a n d Iro n b y th e B a riu m C a r b o n a te T it r a t io n M e th o d . B y J . R . C a i n 465 T h e D e te rm in a tio n o f A m m o n ia in Illu m in a tin g .G a s. B y J. D . E d w a r d s ... 468
T h e S t u d y o f th e C ru d e P e tro le u m from B io ritsu , F o rm o sa . B y T e ts u . K a t a y a m a ... 469
T h e rm a l R e a c tio n s in C a rb u re tin g W a te r G as. P a r t I I — E x p e rim e n ta l. B y M . C . W h ita k e r a n d W . F . R i t t m a n ... 472
N o te 011 a B la c k B a n d Iro n O re from th e S te a rn s C o m p a n y ’s C o a l M in e s a n d on th e C a lc iu m -M a g - n esium R a t io in K e n t u c k y C a r b o n a te O res. B y A lfre d M . P e t e r ... 479
A N o te 011 th e U tiliz a tio n o f M u d s a n d S cu m s from S u g a r R efin eries. B y R . F . G a r d in e r ... 480
T h e E ffe c t o f H ig h T e m p e r a tu re on Y e a s t . B y C . B . C o ch ra n a n d J. H . P e r k in s ... 480
P h y sic a l F a c to r s w h ich In flu en ce th e P e rc e n ta g e of W e t a n d D r y G lu te n in W h e a te n F lo u r. B y B . H . K e p n e r . . . . ... 481
T h e D e te rm in a tio n o f th e A c e t y l N u m b e r o f O ils, F a ts, E t c . B y E d w a rd B . H o lla n d ... 482
A C om p ariso n o f N e u tra l A m m o n iu m C it r a t e w ith S od iu m C it r a t e a n d N/ 10 C itr ic A c id . B y P a u l R u d n ick , W . B . D e r b y a n d W . L . L a t s h a w 486 The_ E ffe c t o f E n s ila g e F e rm e n ta tio n a n d A n im a l D ig e stio n on th e S o lu b ility o f P h o sp h o ric A c id in P h o sp h a te R o c k . B y C . A . M o o e r s... 487
T h e T h e o r e tic a l B a s is fo r th e C o m m e rc ia l P r e p a r a tio n o f L im e -S u lfu r S p r a y . B y H e rm a n V . T a r t a r 488 T h e D e te rm in a tio n o f C a m p h o r in T a b le t s and P ills. B y E d w in D o w z a r d ... 489
La b o r a t o r y a n d Pl a n t: T h e S ta t u s a n d T e n d e n c y o f th e G a s I n d u s try . B y W a lte r R . A d d ic k s ... 490 I C O N T E N T S A S im p le E x tr a c tio n A p p a r a tu s . B y P e r c y H . W a lk e r a n d L o rin H . B a ile y ... 497
Ad d r e s s e s : R e c e n t Im p ro v e m e n ts in G a s M a n u fa c tu re . B y A lfre d E . F o r s t a l l ... 499
C h e m is tr y an I m p o r ta n t F a c t o r in th e F e r tiliz e r I n d u stry . B y J. E . B r e c k e n r id g e '. ... 505
Ob i t u a r i e s: H e rm a n F ra sc h , 505; P a u l L . V . H ^ ro u lt... 506
Cu r r e n t In d u s t r i a l Ne w s: A N e w T y p e o f A r t ific ia l F e rtiliz e r; A N e w C o a l C a lo rim e te r; E le c tr ic S m e ltin g of Iro n a t H a rd a n g e r, N o r w a y ; T h e F lu x o g ra p h F lo w R e co rd er; In d u s tria l A c c id e n ts in M a s sa ch u s e tts ; V a c u u m T a r ; R e q u ire m e n ts of G la ss fo r B o tt lin g M e d ic in e ; M e th o d of S cu rfin g G a s R e to r ts ; In d u s tria l C o n d itio n s in F ra n c e ; E le c tr ic T e s tin g B u re a u s in G e r m a n y ; S te a m R a is in g b y G a s C o k e ; A M e r c u r y E n g in e ; A E u ro p e a n V ie w o f th e M o n ro e D o c tr in e ; E n fo rce m e n t of S o -C a lle d N e t W e ig h t L a w ; R u ssia n T r a d e in F e rtiliz e rs in 19 1 3 ; N a tu r a l G a s in H u n g a r y Sc i e n t i f i c So c i e t i e s: R e p o r t o f P rog ress b y C o m m itte e on Q u a lit y of P la tin u m L a b o r a to r y U te n sils, A p r il 9, 1 9 1 4 ... F e rtiliz e r C h e m is tr y D iv is io n R e p o r t ... R e p o r t of th e A n a ly tic a l C o m m itte e — R u b b e r S e c tio n C o m m e n ts o f J o in t R u b b e r In s u la tio n C o m m itte e on R e p o r t of A n a ly tic a l C o m m itte e of R u b b e r S ec tio n A m e ric a n I n s titu te o f C h e m ic a l E n g in e e rs, 6 th S em i- A n n u a l M e e tin g , T r o y , Ju n e 17 -2 0 , 1 9 1 4 ... 5 16 No t e s a n d Co r r e s p o n d e n c e: F o r m u la fo r C o n te n ts o f C y lin d ric a l T a n k s w ith S p h e ric a l E n d s ... 5 1 7 In flu en ce o f R a t e o f S tirr in g on T it r e o f F a t s . . 5 1 7 A S h a k e r fo r th e M e c h a n ica l A n a ly s is o f S o ils ... 5 17 B e n z o ic A c id in P r u n e s a n d C ra n b e rrie s ... 5 18 B u re a u o f S ta n d a rd s ’ A n a ly z e d S a m p le s ... 518
P la tin u m T h e f t s ... 518
Pe r s o n a l No t e s... 518
G o v e r n m e n t P u b l i c a t i o n s ... 520
Bo o k Re v i e w s: A lle n ’s C o m m e rc ia l O r g a n ic A n a ly s is ; T h e E le c tr ic F u r n a c e ; P rin c ip le s a n d P r a c tic e of A g r ic u ltu ra l A n a ly s is ; M e t a llo g r a p h y ; S u g a r A n a ly s is; In d u s tria l P o iso n in g ; T h e N ic k e l In d u s tr y : w ith S p e c ia l R e fe re n ce to th e S u d b u r y R e g io n , O n t a r io .. . 524
Ne w Pu b l i c a t i o n s... 527
Re c e n t In v e n t i o n s... 528
Ma r k e t Re p o r t... 530 507
512 513 514 515
T H E J O U R N A L O F I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y V o l. 6, No. 6
I
EDITORIALS
R E C E N T jS Y N T H E T I C S T U D IE S IN T H E T A N N IN G R O U P 1 T h e re ex ist in n a tu re a co n sid e rab le n u m ber of su b sta n ce s w h ose aqu eou s e x tra c ts h a v e th e p ro p e rty of tu rn in g hide in to le a th e r. S u b stan ces w h ich show th is p ro p e rty h a v e also certain o th er general c h a ra c te ristics. T a n n in g su b sta n ces are am orp h ou s and h a v e an a strin g e n t ta ste . T h e y u s u a lly p r e c ip ita te g e la tin fro m its so lu tio n s an d fo rm co m p o u n d s w ith m etals, th o se w ith iron, fo r exam p le, b ein g fre q u e n tly colored an d su ita b le fo r use as in ks. H y d r o ly tic agen ts sp lit th e m in to a v a r ie ty of p ro d u cts. O ne of th ese is a lm o st a lw a y s a su gar, u su a lly ¿-g lu co se, w h ile th e o th er co m p o n en t is som e h y d ro x y a cid of th e a ro m a tic series. C a ffe ta n n ic acid , fo r exam p le, w h ich is fo u n d in coffee an d P a r a q u a y te a , y ie ld s a su g ar an d caffeic acid . T h e ta n n in g m a terial of oak b a rk y ie ld s ellagic a cid an d q u ercite . S till oth ers y ie ld p h lo ro g lu cin o l in s te a d of su gar.
T h e m ost th o ro u g h ly stu d ie d of th ese su b sta n ces is o rd in a ry tannin, w h ich occu rs in th e n u t-g a lls of th e o a k and is also fo u n d in su m ach , te a an d oth er p la n ts. I t is a colorless, am orp h o u s su b sta n ce , w h ich is re a d ily solu b le in w a te r and o n ly s lig h tly soluble in alcoh o l and eth er. I t can b e p rep ared in a s ta te o f c o m p a ra tiv e p u r ity , and its s tru c tu re h as in tereste d o rg a n ic ch em ists fo r a lo n g tim e.
T h e m ost im p o rta n t of th e earlier in v e stig a tio n s w as carrie d on b y S tre c k e r in 1852 [A n n. der Chemie, 81 (1852), 248; 9° (18 54), 328]. H e h y d ro ly z e d ta n n in and fo u n d th re e m olecules o f g a llic a cid asso ciated w ith one of ¿-g lu co se. M a n y ch em ists w ho stu d ie d th e p ro b lem la te r cam e to th e co n clu sion t h a t su gar w as n o t an essen tial c o n s titu e n t, a t le a st in all k in d s of ta n n in , and th e o b se rv a tio n t h a t g a llic acid , b y m eans of p h osp h o ru s o x y ch lo rid e an d o th er d e h y d ra tin g a g e n ts, co u ld b e ch an g e d to d iga llic acid ,
H O x
2H O — ^ )>— C O O H =
h o/
H O s H O -
H O /
CO
Ä | ° \
H O — <( )> C O O H + HoQ h o /
led S ch iff,.in 1871 [Ber., 4 (18 7 1), 232, 967; 12 (18 79), 33; and A n n ., 170 (18 7 3 ), 43], to a cc e p t th is s y n th e tic d iga llic acid as, a t le a st, th e p rin cip a l co m p o n en t of tan n in . S u ch a co n clu sion le ft th e o p tica l a c t iv it y of ta n n in u n exp lain ed , since d ig a llic a cid co n tain s no a sy m m e tric carb o n a to m . I t co u ld n o t be certain , h o w e ver, th a t o p tic a lly a c tiv e im p u rities m ig h t n o t be p resent, in asm u ch as ta n n in is an am orp h o u s su b sta n ce and th e usual crite ria of p u r ity and h o m o g e n e ity in o rgan ic su b sta n ces are lack in g .
W ald en , in 1897 [Ber., 30 (1S 9 7), 3 1 5 1 ; 3* (1898), 3x6 7], m ade an e x te n siv e com p ariso n of th e s y n th e tic
1 A dd ress b efo re th e E a stern N e w Y o rk S ectio n of th e A m erican C h e m ic a l S o c ie ty , S c h e n e c ta d y , M a r c h 27. 1914.
d iga llic acid w ith tan n in , and fo u n d th a t th e ir physical p ro p erties w ere n o t id e n tica l. T h e m o lecu lar w eight of ta n n in is fa r to o g re a t for d ig a llic acid , an d neith er the ele ctrica l c o n d u c tiv ity , th e ab so rp tio n o f lig h t, nor the b e h a v io r w ith arsenic acid w ere fo u n d sufficiently p a ra lle l for W a ld e n to b elieve in th e id e n tity of the su b sta n ces concern ed . Q u ite re c e n tly , N ierenstein m ade th e su g gestio n th a t ta n n in m igh t b e a m ixture of d iga llic acid w ith its o p tic a lly a c tiv e reduction p ro d u ct, leu co -tan n in . S u ch a m ixtu re , how ever, sh o u ld be m ore acid ic th a n ta n n in an d h a v e a smaller a p p a re n t m o lecu lar w eig h t. S till m ore re c e n tly Feist [Ber., 45 (19 12 ), 1493] h as su g ge ste d a m ore com plex co m p o sitio n , b u t his conclu sion s h a v e now been su p ersed ed b y th e w o rk of E m il F isch er [G en. rdsum6, Ber., 46 (19 13 ), 3253; see also 41 (1908), 2875; 45 (19 12 ), 9 15 , 2709, 3773; 46 (19 13 ), 1 1 1 6 ] , w hich it is th e p rin cip a l o b je c t of th is p ap er to describe.
E m il F isc h e r’s a tte n tio n w as first d e v o te d to the p u rifica tio n o f ta n n in w ith th e id ea of ob tain in g as h om o gen eo u s a m a terial as possible. F o r th is purpose, th e p u rest p ro d u ct from C h in e se n u t-g a lls w as shaken fro m a d ilu te a lk a lin e so lu tio n b y e th y l a ce tate. It is o b v io u s th a t a su b sta n ce so pu rified co u ld contain no free c a rb o x y l g ro u p , an d w e can assu m e this to be th e fa c t con cern in g th e m a te ria l in v e stig a te d by F isch er. W h e n p u rified in th is w a y , th e su b stance is am orp h ou s, b u t it is d o u b tless as pu re a ta n n in as has h ith e rto b een p rep ared . I t is o p tic a lly a ctiv e , the sp ecific r o ta to r y po w er b ein g a b o u t 70 °.
T h e n e x t step w as th e h y d ro ly sis o f la n n in . This w as carrie d o u t in acid so lu tio n , sin ce a lk a li would a c t u po n a n y su g ar form ed . T h e m eth o d w as checked b y b la n k te sts m ade w ith m ix tu re s o f g a llic acid and su g ar, and a fte r m a k in g a n y n ecessa ry corrections of th is k in d , it w as fo u n d th a t h y d ro ly s is h ad decom p o sed th e ta n n in in to a m ix tu re of one m olecule of
¿-glu co se an d te n of g a llic acid . N o oth er h yd ro xy acid w a s fou n d . S ince th e re are five h y d ro x y l groups in ¿-g lu co se, a sim p le in te rp re ta tio n o f th e results w o u ld su g g est th a t w e h a d to do w ith an ester of glu
cose in w h ich each of th e five h y d ro x y l group s was esterified w ith a m olecule of d iga llic acid . Such a su b sta n ce w o u ld n o t be a glu co sid e in th e ordinary a c c e p ta tio n o f th e term . E m il F isch er is of the op inion th a t th e la t te r nam e sh o u ld be reserved for p ro d u cts a n alo go u s in th e ir s tru c tu re to m eth yl glu
coside,
C H2O H . C H O H . C H . C H O H . C H O H . C H . O C H 3 1--- 0 --- 1
T h e b e st p ro o f of th e s tru c tu re su g gested fo r tannin w o u ld be its sy n th esis, b u t in v ie w of th e difficulty of p re p arin g s y n th e tic d ig a llic acid , it seem ed best to b egin w ith th e sim p ler p ro b lem of p rep arin g glucose p e n ta g a lla te . T h e m eth o d w h ich first su ggests itself fo r th e p re p ara tio n of such a co m p o u n d is th e trea t
m en t of th e su g ar b y th e ch lorid e of th e acid; but ch lorid es of su b sta n ces lik e g a llic acid are difficult to
June, 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 prepare. T h e u su al e a sy re a ctio n of th e ch lorid es of
phosphorus u po n th e free acid s is co m p lica te d in th is case b y th e fa c t th a t th e h y d ro x y l grou p s also presen t are a tta ck e d b y th e rea gen t. E m il F isch er w as able to avoid th is d ifficu lty b y a m eth od w h ich he h ad p re
viously used in less c o m p lica te d cases. T h is consisted of trea tin g a h y d ro x y acid w ith m e th y l ch lo rca rb o n ate . This form s a c a rb o m e th o x y d e riv a tiv e ,
C H 3O .C O .C l + H O — < ^ ^ > C O O H =
H C1 + C H 80. C0-0<( ) - C O O H which is sta b le en ou gh to to le ra te rea ctio n s u p o n th e carboxyl grou p , b u t w hen th ese rea ctio n s h a v e been carried ou t, ge n tle h y d r o ly tic a gen ts e x ch a n g e th e carbo m eth o xy group fo r h y d ro x y l again.
I t is o b vio u s th a t u n d er th ese circu m sta n ce s g a llic acid w ould y ie ld a trica rb o m e th o x y d e riv a tiv e ,
C H 3O .C O .O \
C H 3 O .C O .O — <\ _ ^ > — C O O H C H 3O .C O .O / ~
which, w hen tr e a te d w ith p h osp h o ru s ch lorid e, w ou ld yield th e co rresp o n d in g acid ch lorid e. T h is ch loride was finally tre a te d w ith ¿-g lu co se in d ry ch loro form solution, q u in olin e b ein g in tro d u ce d fo r th e purpose of ta k in g up th e h y d ro ch lo ric a cid fo rm ed . T h e product w as a p e n ta -trica rb o m e th o x y -g a lla te of g lu cose,
. r 0 j
C H 2 .C H .C H .C H .C H .C H .O R
I I I I '
OR O R O R O R O .C O .O C H s
R = CO<( ^ O .C O .O C H s o . c o . o c h3 It was c a re fu lly sapon ified b y m eans of a sm all excess of alkali d isso lved in aq u eo u s a ce to n e. U n d e r th ese circum stances th e ca rb o m e th o x y grou p s w ere sp lit oil at ord inary te m p e ra tu re an d th e p e n ta g a lla te of g lu cose was iso lated . T h e sim ila rity o f th is su b sta n ce to ordinary ta n n in w as strik in g . T h e o n ly d ifference was in th e r o ta to r y p o w er and th e q u a n tity of ga llic acid form ed b y h y d ro ly sis. L ik e ta n n in , th e su b stan ce is am orphous, and it ca n n o t be sta te d w ith c e r ta in ty th at it is p e rfe c tly hom o gen eo us. E m il F isch er b e
lieves th a t th e re are p ro b a b ly a t le a st tw o isom ers present w hich sta n d to each o th er in th e sam e re la tion as a - and /3-glucose. T h is co n d itio n of th in gs is certain in th e case of glu co se p e n ta b e n zo a te .
T h e n ex t step w as th e p re p a ra tio n of m e th ylo ta n - nin, w hich p ro v e d easier to c a rry o u t th a n th e syn th esis of tann in itse lf. H e rzig [B er ., 38 ( 1 9 0 5 ) , 9 S 9 ; Monat- shefle, 30 ( 1 9 0 9 ) , 5 4 3 ] h a d a lre a d y p rep ared th is su b stance b y th e a ctio n o f d iazo m e th a n e upon ta n n in , and had o b ta in ed , b y h y d ro ly sis, tr im e th y lg a llic acid and u n sym m e trica l i«,^)-dim ethylgallic acid .
CH3O H O
C H 3Q<( )>— C O O H a n d C H 3Q<( — C O O H
C H sO c h3o
These fa c ts su g g e st th a t ta n n in m ig h t b e an ester
of glu co se w ith five m olecules of »»-digallic acid . T h e sy n th e sis w as carrie d on m uch as b efore. T r im e th y l- g a llo y l ch lorid e w as first com bin ed w ith m,^ -d im eth yl- ga llic acid,
C H 30\ H O \
C H sO — C O C1 + C H 30— <( )>— C O O H =
c h3o/ c h3o/
C H 3Ox |— --- Ox
H C I + CH 3O — <(* )>— C O C H 3Q<( )>— C O O H
C H 3 O / C H 3 O /
an d th is, in its tu rn , ch an ge d to its ch lorid e and co m b in ed w ith ¿-glu co se. T h e p ro d u c t w as s tr ik in g ly sim ilar to th a t of H erzig , b u t th e re rem ain s, of course, th e sam e d o u b t as to its p e rfe ct h o m o g e n e ity as in th e oth er case.
T h e success of th ese ex p erim e n ts seem ed to w a rra n t an a tte m p t to p rep are ta n n in itse lf: «¡-digallic acid , w hich h a d p re v io u sly been' sy n th e size d , w as ch an ged to th e c a rb o m e th o x y co m p o u n d as in th e sim p ler case of o rd in a ry g a llic acid , b u t th e p ro d u ct w as fo u n d to be am orp h ou s, an d th e sam e is tru e of th e ch lorid e w h ich is p rep ared fro m it. F in a lly , th e co m b in atio n w ith su gar to o k p lace o n ly w ith d ifficu lty and th e s y n th e sis can n o t be rega rd e d as su ccessfu l. T h e essen tial n atu re of th e ta n n in s seem s, h o w e ver, to h a v e been d e fin itely se ttle d b y th e in v e stig a tio n and we can be co n fid e n t th a t th e stru c tu re of ta n n in is ty p ifie d b y th e p e n ta -g a lla te of glucose. I t is still possible, of course, th a t ta n n in s from d ifferen t sou rces h a ve n o t e x a c tly th e sam e co m p o sitio n , and t h a t a n y g iv en sam p le of ta n n in is n o t hom o gen eo us. I t is also p o s
sible th a t th e ¿-glu co se is n o t re a d y fo rm ed in th e m olecule, b u t th a t th e re ex ists in s te a d som e p o ly sa cch a rid e w h ich g iv e s ¿-glu co se upon h y d ro ly sis.
T h e in v e stig a tio n w as co n tin u ed b y co m b in in g g a llic and o th er h y d ro x y a cid s w ith o th er su g ars and p o ly a to m ic alcoh o ls, and a v a r ie ty of su b sta n ces were th u s p rep ared w h ich sh o w ed th e ch ief ta n n in c h a ra c te ristics. DoublAess th e s tu d y of com p o u nd s o f th is class w ill be of co n sid erable v a lu e to p la n t p h y sio lo g y since it is v e r y lik e ly th a t th e p la n t b u ild s up such su b sta n ces as a m eans of n eu tra lizin g acid s b y esteri- ficatio n . Som e p ra c tic a l resu lts m a y also be ex p ected , since sm all q u a n titie s of ta n n in -lik e su b sta n ces h a v e a m ark ed in flu en ce upon th e ta s te o f such a rticles of fo o d as te a , coffee an d sw eet fru its. I t is, th erefo re, p ossible th a t s y n th e tic m a terials of th is ty p e m a y find use as; fla v o rin g m aterials.
A n in te re stin g resu lt o f th e in v e s tig a tio n is to be fo u n d in th e fa c t th a t syn th ese s of th is kind lea d n a tu ra lly to p ro d u cts of e x tre m e ly high m olecu lar w eig h t. In th is p ro p e rty th e y su rp ass ev en th e h igh est p o ly p e p tid e s. E m il F isch er exp ects to c a r ry in v e s tig a tio n s of th is so rt fu rth er, b e lie v in g th a t it is th e d u ty of th e O rgan ic C h e m ist to b u ild up as la rg e m olecules as possible, w h ile th e m odern p h y sic ist is c o n s ta n tly d issectin g th e a to m in to sm aller an d sm aller u n its.
B y co m b in in g tr ib e n z o y lg a llo y l ch lo rid e w ith th e
452
T H E J O U R N A L O F I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y V o l. 6, No. 6^ -iod oph en ylosazon e of m altose, E m il F isch er was a b le to p rep are a su b sta n ce of th e fo rm u la
C220H142O5SN.4I2,
and m o lecu lar w e ig h t 4021. T h is su b sta n ce h as th e h igh est m o lecu lar w e ig h t of a n y o rgan ic co m p o u n d w h ich h as y e t b een prep ared b y sy n th e sis. I ts gra p h ic fo rm u la is g iv e n below .
C H = N — N H — S \ I I
C = N — N H — < > 1 C H — O— R
r - 0 -
C H — C H — CHa— 0— C H — C H — C H — C H — C H — C H 2 O
R 0 R
0 R
0 R
0 ' 0
R R
and th e o n ly e x p la n a tio n n ecessa ry is th a t th e ra d ica l R signifies trib e n z o y lg a llo y l,
O .C O .C 6Hs
R = CO<^ ^ O .C O .C e H s O .C O .C 6H 5
I t is in te re stin g to n o te th a t th is su b sta n ce follow s the la w s of R a o u lt v e r y w ell. D e te rm in a tio n s o f th e molec
u lar w e ig h t b y th e fre ezin g-p o in t m eth o d , in bromoform, y ie ld e d n u m erical resu lts w hich are su rp risin g ly good w hen th e m a gn itu d e of th e m olecu le is ta k e n into co n sid eratio n .
T h is in v e s tig a tio n h as n o t led to th e production of a n y su b sta n ce s w h ich are su fficien tly ch eap to be of use to th e ta n n e r as a s u b s titu te fo r his e x tra cts , but th e re h as b een b ro u g h t upon th e m a rk e t w ith in the la s t fe w m o n th s a la b o r a to ry p ro d u ct w h ich is a promis
in g su b s titu te for ta n n in , an d w h ich is sa id b y those in th e tra d e to g iv e good resu lts an d sh o rte n th e time req u ired fo r ta n n a g e . T h is is th e so -called “ N eradol”
of S tia s n y [Collegium, 1913» p. 142]. I t is prep ared by tr e a tin g p h en o l w ith su lfu ric a cid an d ad din g for
m a ld e h yd e in th e p ro p o rtio n o f one m olecule of fo rm a ld e h yd e to tw o of p h eno l. T h is m ethod of p re p ara tio n su g gests th e w ell-kn o w n B ak e lite , but th e p ro d u ct differs fro m th e la t te r in b eing soluble in w ater. I t en ters th e pores o f th e hide rea d ily, and w h en used as a p re lim in a ry tr e a tm e n t increases the v e lo c it y of ta n n a g e b y o th er m a terials. I t also pro
du ces le a th e rs of go od q u a lity an d lig h t color.
F . J. M o o r e
ORIGINAL PAPERS
A T H E R M O E L E C T R I C M E T H O D F O R T H E D E T E R M I N A T I O N O F T H E P U R IT Y O F P L A T I N U M W A R E 1
B y Ge o r g e K . Bu r g e s s a n d P . D . Sa l e
A t th e re q u e st of D r. W . F . H illeb ran d ,2 C h airm an o f th e C o m m itte e on “ Q u a lity o f P la tin u m U te n s ils ,”
o f th e A m e rican C h em ical S o c ie ty , ex p erim e n ts on th e loss in w e ig h t due to co n tin u e d and re p e a te d h e a tin g of p la tin u m cru cibles of v a r y in g degrees of p u r ity h a v e been u n d e rtak en , in co n tin u a tio n o f sim ilar ex p erim e n ts carrie d o u t u n der th e im m e d iate su p er
visio n of m em bers o f th e a b o v e -m e n tio n e d co m m ittee . F ro m som e of th e se earlier ex p erim e n ts, an d from th e w o rk of o th er exp erim e n te rs on th e e v a p o ra tio n o f m etals o f th e p la tin u m gro u p , it a p p e ars to h a v e b een h o p ed to b e able to c la ssify p la tin u m w are as to p u r ity in te rm s o f its e v a p o ra tio n a t a defin ite te m p e ra tu re , s a y i2 o o ° C . T h is seem ed p la u sib le in v ie w of th e fa c t t h a t th e u su a lly p red o m in an t im p u rity , irid iu m , is v e r y m uch m ore v o la tile th a n p la tin u m . E v e n if th is m eth o d , h o w e ver, w o u ld g iv e an in d icatio n of th e p la tin u m p u r ity , w h ich a p p e ars d o u b tfu l in th e lig h t of som e o f our m ore re ce n t exp erim en ts, it is a t b est a so m e w h at te d io u s and d elicate o p eratio n to c a rry out.
T h ese ex p erim e n ts sh o w ed th e d e sira b ility of h a v in g an a cc u ra te an d rap id m eth od fo r d ete rm in in g p la tin u m p u r ity an d one th a t co u ld be a p p lied to cru cib le s w ith o u t d efa cin g th em .
T h e m ost e x a c t m eth o d fo r th e d e te rm in atio n of p u r ity o f p la tin u m a p p e ars to be b y m easu rem en t o f its te m p e r a tu fe coefficien t of ele ctrica l resistan ce,
1 P resen ted a t th e 4 9 th M e etin g o f th e A. C . S ., C in cin n a ti, A pril 6 - 1 0 , 1914.
' See rep o rt o f P la tin u m C o m m itte e in th is issu e .
w h ich q u a n tity has a m ean v a lu e o f a b o u t 0.00391 per degree ce n tig ra d e for th e in te r v a l o ° to 106° C.
for th e p u rest o b ta in a b le p la tin u m , an d decreases w ith th e a d d itio n of a n y th in g to th e p la tin u m . This m easu rem en t can be m ade c o n v e n ie n tly an d exactly o n ly w ith w ires an d is th e re fo re o f little in terest for th e d e te rm in atio n of th e p u r ity o f p la tin u m ware su ch as cru cibles.
T h e th e rm o e le c tro m o tiv e fo rce o f p la tin u m against m a n y o f its a llo y s h as also b een determ in ed with co n sid erable e x a ctn e s s .1
T h is p ro p e rty m a y e v id e n tly be m ade use of, there
fore, in d e v isin g a m eth od for th e d eterm in atio n of p la tin u m p u r ity and one t h a t possesses, furtherm ore, th e a d v a n ta g e s o f a cc u ra c y , speed, con ven ien ce, and p re se rv a tio n in ta c t of th e o b je c ts te ste d .
T h e m eth o d as d e v e lo p e d fo r use w ith crucibles is sh o w n in F ig . 1. T o th e rim o f th e cru cib le C are arc-sold ered , a t e an d /, tw o pure p la tin u m wires of sm all d iam e ter (0 .1 or 0 .2 m m .); th e se w ires are con
n e cte d to an o rd in a ry p y ro m e te r-g a lv a n o m e te r or m illiv o ltm e te r, G; th e ju n c tio n e is h e a te d b y a small o x y -g a s or o th e r b la st flam e fro m d and th e ju nction / is k e p t cool b y an air b la st, c; a sh e e t o f asbestos, A , cut as sh o w n , serve s to p re v e n t ra d ia tio n fro m th e heated p o rtio n o f th e cru cib le reach in g th e cold ju n c tio n / .
T e m p e ra tu re s are m easu red b y m eans o f a 90 Pt- 10 R h , P t th e rm o co u p le using th e co ld ju n ctio n as a b o v e a n d a P t- R h w ire arc-sold ered to th e crucible near c, m ost c o n v e n ie n tly a d ja c e n t to (o. 5 to 1 mm.
d ista n t) b u t n o t to u ch in g th e P t w ire a t e.
1 S ee in p articu lar: W . G eib el, Z . anorg. C ltem ., 69 (1 9 1 0 ), 38; 70 (1 9 1 1 ), 2 4 0 ; B u rg ess an d L eC h a telie r, " T h e M e a su r e m e n t o f H igh T em p e r a tu re s," 3rd E d ., 1 9 1 2 , p . 171.
June, 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 453 T h e w ires are a tta c h e d a t c an d / b y th e w ell k n o w n
arc-soldering m eth o d , w h ich consists in m a k in g th e
L E G E N D ^ t >
a sb e sto s fl.-.commutator d .- éas tube C - c r u c i b l e b-* poles
G - ¿alvanomeferC - a i r tube f - t junctions F10. I—D e t e r m i n a t i o n o f P u r i t y o p P l a t i n u m W a r s
crucible one te rm in a l o f an e le c tric circu it o f a b o u t 40 volts and a sh arp en ed g ra p h ite p en cil th e o th er, w ith a
e -^thermoelectric
c ru cib le an d a t th e sam e in s ta n t to u ch in g th e w ire to th e cru cib le a t th is p o in t. T h e end of th e w ire is th u s fu se d to th e cru cible. W ith a little p ra ctic e th is op eratio n m a y be m ade so th a t th e re is h a rd ly a n y n o tice a b le effe ct on th e ap p e aran ce o f th e c ru c i
ble a fte r th e w ire is rem o ved .
Q u ite s a tis fa c to ry resu lts m a y also be o b ta in e d b y s im p ly to u ch in g th e P t w ires to th e cru cib le a t e an d /, or b y cla m p in g w ith p la tin u m clips, w ith o u t a n y soldering. W ith th e a p p a ra tu s on ce set u p, a te s t m a y th en be m ade in a fe w secon d s an d th e cru cib le rem ain s, of course, a b so lu te ly in ta c t. T h e h o m o ge n e ity of th e cru cib le m a y also be d eterm in ed b y th is m eth od .
B y m eans of a co m m u ta to r a t a b, m easu rem en ts m a y be m ade a lte r n a te ly of th e te m p e ra tu re a t e and of th e E . M . P . d ev elo p e d across th e cru cib le w hen e is a t th is te m p e ra tu re . T h e co m m u ta to r m a y also b e d esigned so as to reverse e an d / if it is desired to m ake / th e h o t ju n ctio n .
I t is, o f course, essen tial t h a t th e tw o p la tin u m w ires b e m ade of s tr ic tly pure p la tin u m . F o r th is p u rpo se, use is m ade o f H eraeu s norm al th e rm o e le m en t w ire d ra w n d o w n ; th is p la tin u m h as sho w n its e lf to be a sta n d a rd , u n ifo rm p ro d u ct, th e p u r ity of w h ich is e a s ily co n tro lled b y th e electric resistan ce m eth od a b o v e m en tion ed .
In th e ta b le are g iv e n th e resu lts of a series of m eas
u rem en ts a t a b o u t 1050° C . of th e E . M . F . of pure p la tin u m a g a in st “ p la tin u m ” cru cibles o f v a rio u s m akes. In P ig . I I are sh o w n th e iso th erm a l cu rves, a t 900°, i o o o 0 an d x x o o ° C ., fo r irid iu m co n te n t of p la tin u m in te rm s of E . M . F . a g a in st p u re p la tin u m . T h e re is also show n here th e irid iu m e q u iv a le n t of th e im p u rities in th e cru cibles c, h an d k of th e ta b le , in te rm s of th e ir sta te d and o b serve d irid iu m co n ten ts.
I t w ill be n oted t h a t all im p u rities are, fo r co n ve-
S U M M A R Y OF T lIB R M O E L B C T R IC T E S T S OF P L A T IN U M C R U C IB L E S
So u r c eo r' Ma k e r
H eraeus.
A m erican^Platinum W o rk s.
Baker & C o m p a n y .
Johnston M a th e y & C o m p a n y .
J* B ish op .
Quenessen D e B e lm o n t, L eg e n d r e e t C ie...
2
S ta te d
3
P r e v io u s ly
4 5 6 7
E q u iv a le n t E . M . F . : Ir
P t vs. co n - E . M . F . from T e m p , cru- t e n t P t - I r cu r v e
8
E . M . F . e x c ess d u e t o Ir or
9
R e f
Re m a r k s D a te
o f
I r c o n te n t h ea ted o f te s t c ib le Per (S ee 2 a n d 4) im p u rities eren ce pur
P er c e n t H rs. 0 C. M v . c e n t M v . M v . le tte r ch a se
0 . 0 17 1050 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 a N o r m a l th er m o e le m en t P t 1911
0 . 7 H e a te d 1050 2 . 0 0 0 .7 0 2 . 0 0 0 . 0 0 b N o r m a l T ie g e l p la tin 1911
0 . 7 0 1050 2 . 6 0 0 . 9 0 2 . 0 0 0 . 6 0 c N o r m a l T ie g e l p la tin 1911
< 0 . 2 24 1050 0 .6 3 0 .1 9 0 . 1 0 0 .5 3 d “ T ie g e l p la t in ” H era eu s
“ T ie g e l p la t in ” H era eu s 1911
< 0 . 2 16 1050 1 . 0 0 0 .3 5 O.IO 0 .9 0 e 1911
0 . 5 to 1 .5 11 1075 6 .6 0 2 .5 5 1 .5 0 to 4 . 1 0 2 . 5 0 to 5 . 1 0 / C o m m ercia l 1911
0 . 5 t o 1 .5 4 1085 6 . 4 0 2 . 5 0 1 .5 0 4 . 9 0 g C o m m ercia l 1911
? 0 . 5 1100 3 .5 0 1 .1 9 3 . 5 0 h L o a n ed b y p u rch a ser 1913
? 10 1050 6 .7 5 2 .7 2 6 .7 5 i C o m m ercia l 1908
? 20 1050 6 .9 5 2 .7 8 6 .9 5 j C o m m ercia l 1908
2 .3 7 0 1030 6 . 0 0 2 .3 7 6 .0 0 0 . 0 0 k S p e cia l a n a ly ze d m a k e 1912
0 .7 0 2 12 1050 1 .9 0 0 . 6 6 2 .0 5 — 0 .1 5 I S p e c ia l a n a ly z e d m a k e 1912
R efin ed 0 1040 0 .3 3 0 . 1 0 0 .3 3 m S p e c ia lly refined 1911
? 3 y rs. 1100 3 . 0 0 1.01 3 .0 0 m U se d 3 y rs. in lab . 1909
? 0 1100 1 .7 1 0 .5 5 1 .7 1 A v era g e o f s e v e n
? 67 1050 0 . 4 8 0 .1 5 0 .4 8 n
co m m er cia l cru cib les B e s t cr u c ib le w are
1914 1911
? 0 1070 0 .6 8 0 .2 3 0 .6 8 0 B e s t cru c ib le w are 1911
? 20 1050 0 . 6 3 0 . 2 2 0 .6 3 P B e s t cr u c ib le w are 1913
? 9 m o. 1100 2 . 1 0 0 .6 8 2 . 1 0 Q L o a n ed b y p u rch a ser. U se d
' ? 0 . 5 1100 2 . 2 0 0 .7 2 2 . 2 0 r \
co n tin u o u sly 9 m o.
L o a n e d b y p u rch aser. U se d 1913
.R efin ed 31 . 1050 0 . 6 0 0 .2 1 0 . 6 0 s )
co n tin u o u sly 9 m o.
S p e c ia lly refined
1913 1911
? 10 1050 2 .7 9 0 . 9 8 2 .7 9 I 1911
? 0 1060 2 .8 0 0 .9 8 2 . 8 0 u 1911
? 4 1030 1 .6 0 0 . 5 6 1 .6 0 V 1911
rheostat in series. T h e o p eratio n of sold ering con sists in d ra w in g a m in u te arc b etw e en p en cil and
nience, exp ressed in te rm s of irid iu m co n te n t. O f p a r tic u la r in te re st is th e com pariso n o f colu m ns 2 an d 6,
454 T H E J O U R N A L O F I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y V o l. 6, No. 6 th e fo rm er g iv in g th e sta te d irid iu m co n te n t (and o ften
a cco m p an ied b y th e s ta te m e n t th a t th ere are no oth er im p u rities) and th e la tte r g iv in g th e irid iu m co n ten t as d eterm in ed th e rm o e le c tric a lly b y exp erim e n t and use of F ig . II . In several in stan ces, n o ta b ly fo r th e
cru cib le of n orm al th e rm o e le m e n t p la tin u m (a), of H eraeus and for B a k e r ’s cru cib le (k), of 2 . 3 7 per cen t irid iu m , th e s ta te d an d fo u n d irid iu m co n te n ts agree e x a c tly . On th e o th er h an d th e re is a w ide d ive rgen ce fro m th e su p posed and a ctu a l irid iu m co n te n t for se v e ral o f th e cru cib le s; fo r exam p le, / of th e A m e rican P la tin u m W o rk s, su p p osed to c o n tain n o t o v er 0 . 5 0 to 1 . 5 per cen t irid iu m , a c tu a lly co n tain s an irid iu m e q u iv a le n t of 2 . 5 0 p er ce n t; and e v e n in th e case of refined, sp e cia lly refined and b e st cru cib le w are, th e e q u iv a le n t irid iu m co n te n t is n o t in con sid erab le.
A m o n g th e 22 cru cib le s exam in ed th e re is b u t one, (i ), of B a k e r & C o ., co n tain in g less irid iu m th a n is s ta te d .
In co m p a rin g th e s ta te d co n ten ts, colu m n 2 o f th e ta b le , it sh o u ld be borne in m ind th a t som e of th e se cru cibles, e x c e p tin g p e rh a p s th o se m a rk ed refined or s p e c ia lly refined, m a y co n tain irid iu m w h ich is p u t or le ft in th e cru cib le m aterial p u rp o se ly , u su a lly fo r th e purpose o f stiffe n in g , or in th e case o f com m ercial w are, b ecau se such P t a lw a y s carries Ir, T h e m eth o d here d escrib ed , h o w e ver, p ro v id e s a d e licate m eans of d ete rm in in g w h eth er or n o t th e d esired lim ita tio n o f im p u rity , exp ressed in te rm s of irid iu m co n te n t, a n d as m easu red th e rm o e le c tric a lly , h as b een m et b y th e m a n u fa ctu re r. F o r th e e x p e rim e n ta l arran g e m en t here giv e n , th e a m o u n t of im p u rity is re a d ily d e te r
m ined to 0 .0 1 per cen t and th is a c c u ra c y co u ld b e im p ro v e d u p o n if n ecessary.
T h e m eth od does n o t d istin gu ish th e v a rio u s p o ssi
ble im p u rities fro m each oth er b u t is n eve rth eless a
certain ch eck on th e p la tin u m p u r ity .1 One of th e most u n desirab le im p u rities o ften fo u n d in com m ercial p la tin u m w are is iron; th is is re a d ily d e te cte d b y igni
tio n and su b seq u en t w ash in g w ith h o t H C1 an d ap ply
in g th e u su al color te s t fo r F e. Iron-, if present in
r e la tiv e ly co n sid erable q u a n tity , w ill also discolor th e cru cib le on ign itio n .
I t w o u ld p r o b a b ly be a d v a n ta g e o u s to su bstitu te rh o d iu m fo r irid iu m in p la tin u m cru cibles w hen stiffness is d esired and w hen e x a c t w eig h in gs h a v e to be taken before an d a fte r ig n itio n , fo r th e reason th a t rhodium is fa r less v o la tile th a n irid iu m , and so m e w h at less so th a n p la tin u m , a lth o u g h it a p p e ars n o t y e t to have been p ro v e n th a t th e m ore v o la tile m etals alloyed in sm all a m o u n ts w ith p la tin u m re ta in th e ir v o la tility in d e p e n d e n tly of th e presence of th e p latin u m .
T h e a b o v e describ ed th e rm o e le c tric m eth od will n ot alone d istin gu ish b e tw e e n sm all a m o u n ts of rho
diu m and irid iu m , b u t a co m b in atio n of th e therm o
ele ctric and loss of w eig h t m eth o d s m igh t be devised th a t w o u ld be s a tis fa c to ry . A n e le ctric discharge m eth o d o p erate d a t h igh te m p e ra tu re s m igh t possi
b ly b e m ade su fficie n tly se le ctiv e to differentiate b etw e en p la tin u m a llo y s of irid iu m an d rhodium . T h e re is e v id e n tly room fo r m uch m ore w ork along these lines.
Bu r e a uo f St a n d a r d s Wa s h i n g t o n
T H E D E T E R M I N A T IO N O F T H E D U S T F A L L IN T H E N E IG H B O R H O O D O F C E M E N T P L A N T S
B y J . P . Mi t c h e l l
R e c e iv e d M a r c h 18, 1914
T h e d e te rm in atio n of th e d u st fa ll in th e neighbor-
1 A ll th e m e ta ls fou nd a sso c ia ted w ith p la tin u m , su c h a s palladium , irid iu m , rh o d iu m , e tc ., w h en a llo y ed w ith p la tin u m (u p to 9 0 p er ce n t only o f p a lla d iu m ) g iv e , a t h igh tem p era tu res, an IS- M . F . o f th e sa m e sign against pure p la tin u m . T h erefore, th ere is n o a m b ig u ity in b a la n cin g o n e im purity a g a in st a n other.
June, 1 9 x 4 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 4SS hood of cem en t p la n ts h as re c e n tly becom e a m a tte r
of con sid erable im p o rta n ce , la rg e ly as a resu lt of litigation w hich h as arisen b etw e en ce rta in co m panies e n gage d in th e m a n u fa ctu re of cem en t, and the residen ts of th e regio n in th e im m ed iate n e igh b o r
hood of th e p la n ts. T h is litig a tio n h as ta k e n th e form of suits on th e p a rt of th e resid en ts eith er to secure dam ages, or o b ta in in ju n ctio n s a g a in st th e o p eratio n of th e p la n ts, b ased upon in ju r y .a lle g e d to h a ve been inflicted u p o n th e p ro p e rty of th e resid en ts. T w o en tirely d istin ct claim s o f in ju r y h a v e b een a d va n ce d . One is based upon th e alle ged in flictio n of a ctu a l dam age to v e g e ta tio n , eith er th e a c tu a l d e stru ctio n of plan ts an d a ctu a l d e stru ctio n , in w hole or in p a rt, of crops, or th e lessen in g o f th e m a rk e t v a lu e of p la n ts and crops b y th e presence of cem en t d u st on th e p la n t foliage an d fru it. T h e oth er claim is based upon the less sp ecific gro u n d of “ n u is a n ce .” I t is alleged th at th e cem en t d u st en ters th e houses of th e co m plainants, causes m uch perso nal in co n ve n ien ce, and in general in terfere s w ith th e rig h t of e v e r y lan d holder to th e e n jo y m e n t of n orm al and u n p o llu ted atm osp heric con d itio n s. W h a te v e r be th e b asis of the co m p lain t, it is a m a tte r of record th a t su ch co m plaints are_ b eco m in g m ore com m on in a ll p a rts of the co u n try , an d in e v e r y such case it b ecom es a m a tte r of im p o rtan ce to b o th p a rtie s th a t th e tru e co n d itio n s be determ in ed as a c c u r a te ly as possible. S u ch a determ ination in v o lv e s a s tu d y of th e a m o u n t and character of th e d u st fa ll th ro u g h o u t th e region in question, an d a co rrela tio n o f th e resu lts of such a study w ith th e p re v a ilin g m eteo ro lo gica l con d itio n s.
It is th e pu rp o se of th is p a p e r to deal w ith th e m eth o d s available fo r th e d ete rm in atio n o f th e d u st fa ll, and the proper in te rp re ta tio n s of th e resu lts o b tain ed .
A n oth er a sp e ct o f th e s u b je c t d eserves m en tion . From th e cem en t m a n u fa ctu re r’s p o in t of v ie w th e dust th ro w n fro m th e sta c k s of th e p la n t rep resents not on ly a c o n s ta n t source o f possible legal expense and a n x ie ty , b u t also a v e r y real econ om ic w aste.
The a m o u n t of d u st lo st fro m a k iln of th e o rd in a ry rotary t y p e m a y a m o u n t to a n u m ber o f to n s in one day, and th is d u st is n ot com p o sed o f a useless w aste product, b u t is th e v e r y su b sta n ce fo r th e p ro d u ctio n of w hich th e w hole p la n t is o p erated . T h e re co v e ry of this d u st, th e re fo re , sh o u ld n ot be rega rd e d e n tire ly as an exp ense, b u t as a po ssible m easu re of econ om y.
The d ete rm in atio n of th e a m o u n t of d u st lo st in th is way from a g iv e n p la n t ca n n o t be carrie d o u t sa tis
factorily b y th e d ete rm in atio n o f th e d u st fa ll in th e vicin ity, b u t m u st be a rriv e d a t b y a s tu d y of th e conditions e x istin g in th e s ta c k s of th e p la n t th e m selves, an d th e re fo re lies o u tsid e th e scope of th is paper.
T he m ethods w h ich h a v e been used fo r th e d ete rm in a tion of th e a m o u n t o f d u st in th e a tm o sp h ere m a y be divided in to fo u r g ro u p s .1
The m ost sc ie n tifica lly a cc u ra te m eth o d is w ith o u t doubt th a t of A itk in . T h is depen ds u po n condensing
1 For a v ery co m p le te d iscu ssio n o f th e m e th o d s a v a ila b le, an d b ib lio g raphy of th e s u b je c t, s e c U . S . D e p t , o f A g ric u ltu r e. B u r ea u o f S o ils, B u ll.
No. 68, " T h e M o v e m e n t o f S o il M a ter ia l b y th e W in d ,” b y E . E . Free.
w a te r v a p o r on th e d u st p articles, an d c o u n tin g th e re su ltin g d ro p s of w ater.
T h is m eth od is to o refined fo r th e p u rp o se under co n sid e ratio n . T h e presen t prob lem is n o t concern ed w ith th e u ltram icro sco p ica l p a rticles n o rm a lly presen t in air, or ev en w ith th e increase in th e ir n u m ber, b u t ra th e r w ith th e v e r y m uch larger p a rticle s of solid m a tte r w h ich co n s titu te “ d u s t” in th e o rd in a ry m eanin g o f th e term .
E ffo rts h a v e been m ade to c a tch th e d u st presen t in air in v a rio u s b o x -lik e co n triv a n ce s d esigned to c a tch th e d u st b y ch eck in g th e v e lo c ity of th e air cu rren ts, and cre ate con d itio n s u n der w h ich th e d u st w ill se ttle o u t and rem ain w ith in th e a p p a ratu s.
S u ch m eth od s m a y be useful in a s tu d y of th e c h a ra cte r of a tm o sp h eric d u st, b u t g iv e rise to ce rta in d ifficu lties w h en ap p lied to th e p rob lem o f d ete rm in in g th e a m o u n t of d u st fa ll in d ifferen t lo calities. Since th e am o u n t o f d u st rem ain ing in th e box d ep en ds upon th e am n t o f air passin g in to it, th a t is, upon th e w ind vel th e resu lts g iv e w h a t m a y be te rm e d th e “ d u st bu x”
of th e air, as d istin gu ish ed fro m th e “ du st fa ll” w hich w ou ld h a v e ta k e n p lace a t th e sam e p o in t h a d th e v e lo c ity of th e air n ot b een ch ecke d .
T h e d u st presen t in th e air h as b een d eterm in ed b y d ra w in g k n o w n vo lu m e s of air th ro u g h w a ter or filters, an d w eigh in g or co u n tin g th e d u st p a rticle s reta in e d . T h is m eth o d again g iv e s th e “ d u st b u rd e n ” o f th e air, rath e r th a n th e “ d u st f a ll,” an d w h ile it is a v a ila b le for d ete rm in in g th e a m o u n t o f d u st in a g iv e n vo lu m e of air a t a g iv e n tim e, it is n o t a v a ila b le fo r d ete rm in in g th e r e la tiv e d u st fa ll a t d ifferen t p o in ts du rin g a so m e w h at ex te n d ed in te r v a l of tim e.
T h e fo u rth group of m ethods dep en ds upon th e e x posure, in a h o rizo n tal po sition , o f a su rface of k n o w n area co a ted w ith a su b sta n ce th a t w ill reta in d u st fa llin g upon it, an d th e su b seq u en t re m o v a l, w eigh ing an d ex a m in a tio n of th e d u st d ep o sited upon th e su r
fa ce . W h ile no m eth od of th is so rt co lle cts th e sm all m icroscop ic p a rticle s p rese n t in larg e n u m bers in all air, it does co lle ct th e large r p a rticle s o rd in a rily considered “ d u s t,” and does afford a reliab le m eans of c o m p a rin g th e a m o u n t an d co m p o sitio n of th e d u st a c tu a lly fa llin g u po n a h o rizo n tal su rface a t differen t p o in ts d u rin g a g iv e n in te r v a l of tim e. I t is th e re fo re a v a ila b le fo r th e p u rp o se here in view .
T h e m eth o d fin a lly a d o p te d as m ost efficient and p ra ctic a l is th e exp osu re of glass p la te s c o a ted w ith vase lin e, and th e su b seq u en t clean in g of th e p la te s w ith gaso lin e, an d re c o v e ry of th e d u st b y filtra tio n . T h e d eta ils follow .
T h e p la te s used w ere of glass an d m easured five b y seven inches. O rd in a ry w ind o w glass w as used, and th e dim ensions of th e p la te s w ere c a re fu lly ch ecke d , an d a n y p la te s w ith v a ria tio n s g rea te r th a n one- six tee n th of an inch w ere d iscard ed . O ld p h o to g ra p h ic p la te s m a y be used, b u t are th in n e r and m ore s u b je c t to b re a k a g e th a n o rd in a ry w in d o w glass.
T h e ir lig h te r w eig h t also m akes th e m m ore d ifficu lt to h an d le in th e field in a high w ind. T h ese p la te s w ere laid on h o rizo n tal p la tfo rm s p la ce d a t th e to p of h igh poles. T h e size of th e p la tfo rm s w as such
4 5Ó 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. 6 th a t t h e y ju s t h eld th e n u m ber of p la te s exp osed, and
p ro jecte d less th a n h a lf an in ch b e y o n d th e o u ter edge of th e o u tsid e p la tes. A w ide p ro je ctio n , w h ich cou ld serve as a restin g p lace fo r d u st w h ich m ig h t su b se q u e n tly be b lo w n o n to th e p la tes, w as avo id ed . T h e p la te s w ere held in p o sitio n b y sm all ta c k s d riven in to th e ed ge of th e p la tfo rm . T h e p la te s m u st be s e t c lo se ly to g e th e r, an d th e ta c k s a d ju ste d so as to h o ld th e p la te s firm ly in p lace , o th erw ise th e sh a k in g o f th e p o le in a h igh w in d w ill dislod ge som e of th e p la tes. A t th e o u tse t of th e w o rk som e p la te s w ere lo st fro m th e p la tfo rm s d u rin g a high w in d sto rm , b u t w ith p ra ctice it w as fo u n d th a t care in th e ad ju s tm e n t of th e ta c k s w o u ld p re v e n t a n y loss fro m th is cau se. A fte r th e p la te s h a d been exp osed for th e desired len gth of tim e th e y w ere ta k e n up, p la ce d in tig h t w ooden b oxes p ro v id e d w ith cle ats to h o ld th e p la te s a p a rt, lo w ered to th e gro u n d , th e b ox p lace d in a sa ck to e x clu d e ro ad d u st, and ta k e n to th e la b
o ra to ry . t
T h e la b o ra to ry w ork in v o lv e d th e p rep ara tio n and cle an in g of th e plates, an d th e w eig h in g and a n a lysis of th e d u st co llected . B efo re use th e p la te s w ere first th o ro u g h ly cleaned, th e n w arm ed , an d w hile w arm g iv e n a th in ev en co a tin g of th e p u rest vaselin e o b ta in a b le (K a h lb a u m ). T h e va se lin e w hile w arm and liq u id w as b est a p p lied w ith a w ide c a m e l’s h air brush. I t w as free fro m m ineral salts, an d g a v e no w eigh ab le residue w hen ign ited . A fte r exp osure th e p la te s w ere first c a re fu lly w ip e d on th e edges and b o tto m s, and th e n p la ce d in a w h ite en am el p h o to g ra p h ic tr a y , and co ve re d w ith filtered gaso lin e.
T h e d u st d ep o sit w as th e n loosened b y ru b b in g w ith a c a m e l’s h air brush , th e p la te s h eld on ed ge in th e tr a y , and rinsed on b o th sides w ith a fine strea m of gaso lin e b lo w n from a w ash b o ttle . A ll o f one set of p lates, w h ich h a d b een exp osed on th e sam e p la t
fo rm fo r th e sam e tim e , w ere clean ed in th e sam e t r a y of gasolin e. E x a m in a tio n of th e p la te s a fte r th e a d h erin g gaso lin e h a d e v a p o ra te d o ften dis
clo sed fine strea k s w h ich lo o k ed lik e u n rem o ved d u st p a rticles, b u t th e se stre a k s w ere fo u n d to be b o th v o la tile and solu b le in alcohol, sh o w in g th a t all th e m ineral p a rticle s h ad been re m o v e d fro m th e p lates b y th e cle an in g process.
T h e d u st o b ta in ed in th e tr a y s w as s e p a ra te d from th e gaso lin e b y filtra tio n th ro u g h p aper filters. Som e d ifficu lty w as exp erien ced due to th e h a rd e n in g of th e p a p e r b y th e gaso lin e an d co n sequ en t slow filtra tion. T h is d ifficu lty can be overco m e b y first w e ttin g th e filter p aper w ith alcoh o l, an d b y th e use o f m o d er
a te ly stro n g su ctio n . T h e filtra te s are n eve r p e rfe ctly clear, b u t are s lig h tly c lo u d y as a resu lt, a p p a re n tly , of th e fo rm atio n of an em u lsion b y th e gaso lin e w ith som e c o n s titu e n t of th e vaselin e. T h e ev a p o ra tio n of th e filtra te s in a n u m b er o f cases, ga v e , a fte r ign itio n , no w eig h ab le residue. T h e filter p a p e r co n tain in g th e d u st w as p la ce d in a w eigh ed p la tin u m cru cible, and h ea te d c a u tio u s ly to in cip ie n t redness u n til th e p a p e r w as red u ce d to ash an d th e cru cib le an d co n te n ts h ad a tta in e d c o n s ta n t w eigh t. T h e re su lt w as co rrecte d for th e k n o w n w eig h t o f th e filter p a p e r ash.
T h e a n a lysis of th e d u st sam p les w as carried out acco rd in g to sta n d a rd m eth od s. T h e sam ple was fu se d w ith sodium carb o n a te , d ige sted w ith concen
tr a te d h y d ro ch lo ric acid, and th e silica determ ined a fte r tw o ev a p o ra tio n s and d eh y d ratio n s, and was ch eck e d w ith h y d ro flu o ric acid . T h e calciu m was p re c ip ita te d as calciu m o x a la te , a fte r rem o val of iron an d a lu m in u m , from th e b o ilin g solu tio n, and w as ig n ite d to calciu m oxide u n til co n s ta n t weight w as o b tain ed .
T h e choice of th e lo catio n s for th e exp osu re of the p la tes, th e h eig h t o f th e p la tfo rm s a b o v e th e ground, th e n u m ber of p la te s exp osed in one set, and th e length of tim e of th e exp osu re in v o lv e s th e consideration of a n u m ber of fa cto rs. T h e s e fa cto rs all depend to som e e x te n t on th e p a rticu la r p ro b lem under in
v e stig a tio n . T h u s th e to p o g ra p h y o f th e country, th e ch a ra cte r of th e v e g e ta tio n , th e clim a tic conditions, th e season of th e y e a r, an d th e d ire ctio n an d regu larity of th e w in d cu rren ts m u st all be considered, and none are id e n tica l in tw o sp ecific p roblem s. H ow ever, th e re are ce rta in general p rin cip les th a t w ill apply to all cases.
F ie ld w o rk of th is c h a ra cte r is a b s o lu te ly dependent upon fa ir w eath e r. E v e n a lig h t rain w ill interfere w ith th e film o f va se lin e an d ad h erin g d u st on the p lates, cau sin g “ b liste rs” an d b are sp o ts to appear, an d a h e a v y rain w ill n o t o n ly w ash th e d u st from the p lates, b u t w ill also p re v e n t th e norm al tran sp o rta
tio n of th e d u st fro m th e p la n t b y w ash in g it ou t of th e a tm o sp h ere b efore it has been carried to any d istan ce. A p erio d o f s e ttle d fa ir w eath e r must th e re fo re be selected . T h is is v it a l, n o t o n ly on ac
co u n t of th e in terfere n ce due to rain , b u t also on a cc o u n t of th e im p o rta n ce of h a v in g norm al wind co n d itio n s d u rin g th e tim e of th e in v e stig a tio n . In gen eral, th e sp rin g and su m m er m o n th s are th e most s a tis fa c to ry ; th e w in ter m on th s, w h en th e w ind cur
ren ts are m ore v a ria b le , are fa r less desirable.
T h e lo catio n s sele cted fo r th e exp osu re of th e plates dep en d alm o st e n tire ly on th e o b je c ts of a particular in v e s tig a tio n . I f a la w s u it is in v o lv e d , th a t will d ic ta te a t le a st som e o f th e lo catio n s. In general, th e p o sition s sele cted sh o u ld be a t som e distance fro m ro ad s and b u ild in gs, an d sh o u ld be on exposed gro u n d n o t sh e ltered b y trees or hills. If a com
p reh e n siv e s tu d y o f th e d u st fa ll is under w a y th ey sh o u ld be chosen in all d irectio n s fro m th e plant, an d a t lea st one sh o u ld b e p la ce d in a region clearly o u tside of th e “ d u st zo n e” to serve as a con trol station.
T h e p la tfo rm s are b est p la ce d on th e to p o f poles from tw e n ty -fiv e to th ir ty fe e t above' th e ground.
T h is h e ig h t is im p o rta n t fo r tw o reasons: First, to p lace th e p lates a b o v e th e in flu en ce o f m inor dis
tu rb a n ce s o f th e soil w h eth er cau sed b y m an or wind.
Second, to place th e p la te s a t an e le v a tio n where th e w in d cu rrre n ts are re g u la r and ap p roach , in velocity, th o se of th e u p p er air cu rren ts. W h ile n oth in g defi
n ite is k n o w n as to th e d ista n ce to w inch a given d u st p a rticle w ill be carrie d b y a w ind of k n o w n velocity, it is k n o w n th a t th e v e lo c ity o f th e w ind decreases re g u la rly d o w n w ard u n til w ith in a b o u t fifteen feet
