The Journal of Industrial and Engineering Gnemistry
P u b l i s h e d b y T H E A M E R I C A N G H E M I G A L S O C I E T Y
Volume Y DECEMBER, 1913 No. 12
B O A R D O F E D I T O R S Editor: M. C.
W h i t a k e r
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 ger, W m . B ra d y , C. A . B ro w n e, F . K . C am e ro n , F . B . C a rp e n te r, C . E . C a sp a ri, V . C o b le n tz , W . C . G eer, W . F . H illeb ran 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 en 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 ah l, W . H. W a lk e r, W . R . W h itn e y , A . M . W rig h t.
Published monthly. Subscription price to non-members of the A"merican Chemical Society, $6.00 yearly. Foreign postage, seventy-five cents, Canada, Cuba and Mexico excepted.
Entered as Second-class M atter December 19, 1908, at the Post-Office at Easton, Pa., under the Act of M arch 3, 1879.
Contributions should be addressed to M. C. Whitaker, Columbia University, New York City
Communications concerning advertisem ents should be sent to The American Chemical Society, 42 West 39th St., New York City Subscriptions and claim s lor lost copies should be referred to Charles L. Parsons, Box 505, Washington, D. C.
Es c h e n b a c ii Pr in t in g Co m p a n y, Ea s t o n. Pa. TA B L E OF CO N TEN TS Ed it o r ia l s :
R e s e a rc h ... 966
T h e C o n tro l of P u b lic U tilit ie s ... 967
Or ig in a l Pa p e r s: T h e P ro tectio n of Iron and S te e l b y P a in t F ilm s. B y N o rm an A . D u b o is ... 968
T h e O leoresins o f Jeffrey and S in g leleaf Pines. B y A. W . S c h o r g e r ... 971
T h e H yd rocarb o n s of U ta h . B y C a rlo s B ard w e ll, B . A rth u r B errym a n , T h o m as B . B rig h to n and K e n n eth D . K u h r e ... 973
J V in k ler’s M eth o d for the D eterm in ation o f O xygen in S W a te r; the E ffe c t of N itrite and I ts P revention . s B y F ra n k E . H a le and T h o m as W . M e lia ... 976
Sulfur D ioxid e in G elatin e. B y P a u l P o e ts c h k e 980 E xp erim en tal D a ta on th e D eterm in ation of S acch arin in F oo d s w ith a M od ification of S ch m id t’s M ethod s. B y H a lse y D u r a n d ... 987
Bou illon C ubes. B y F . C . C o o k ... 989
T h e Influence of B ra n -E x tra cts on the B a k in g Q u ali ties of F lou r. B y H . L . W h it e ... 990
T h e A n aly sis of M a p le P rod u cts, II. A C o m p arativ e S tu d y of the D e lica cy of M etho ds. B y J. F . Snell and J. M . S c o t t ... 993
On the P rep a ra tio n of N e u tra l A m m on ium C itra te Solution . B y P a u l R u d n ick and W . L . L a ts h a w .. . 998
A S tu d y of th e P em b erto n -K ilg o re M e th o d for D e te r m in ation of Ph osp horic A cid . B y P . L . H ib b a r d . . 998
yT h e C om p osition of S ed im ents from the P o to m a c and / / Shenandoah R iv ers. B y Joseph G . S m ith and W il lia m H . F r y ... 1009
E stim atio n of the Lim e R eq u irem en t of Soils. B y J. A . B izzell and T . L . L y o n ... 1011
A n In terestin g Soil W a te r Q uestion in B ritish G uiana. B y M au rice B ir d ... 1012
M icroorgan ism s in C om m ercial Lim e-Su lfur. B y C . A . P eters and A . W . B r o o k s ... 1013
T h e A ssa y of In d ivid u a l P la n ts of Datura stramonium L., Datura tatula L . and O th er Species and V arieties. B y F . A . M ille r and J. W . M e a d e r ... 1014
La b o r a t o r ya n d Pl a n t: D eterm in ation of N itro g e n b y th e N itro m eter. B y C . M . J o y ce and H a rry L a T o u r e t t e ... 1017
L a b o ra to ry C olu m n S till. B y H . K . B e n so n ... 1018
A n Im p ro ved L a b o ra to ry B urn er. B y C has. P . F o x . 1019 Ad d r e s s e s: B iochem istry. B y C a rl L . A ls b e r g ... 1019
T h e P rog ram s for th e S ectional M eetin g s o f the A m erican C hem ical S o ciety . A S uggestion. B y B ernh ard C . H e ss e ... 1020
E m p irical R eq u irem en ts in A sp h a lt S pecification s. B y L e r o y M . L a w ... 1021
Cu r r e n t In d u s t r ia l Ne w s: Sulfite W aste L iq u o r P r o b le m s... 1024
N ick e l a B y -P r o d u ct in the U n ited S ta t e s ... 1024
P ra c tic a l C on sideration s A ffe ctin g C h o ice of T h e r m om eters in In d ustrial P la n ts ... 1024
T h e S a lt In d u stry of R u s s ia ... 1024
C h em ical T ra d e of G e r m a n y ... 1025
^^Impressions of E u ro p ean S ew a g e -T re a tm e n t M eth o d s 1025 A ctio n of A lk a li and S ea W a te r on C e m e n ts... 1026
A llo y s of A lu m in u m ... 1026
W aterp roo fin g of C on cre te S tru ctu re s... 1027
F u lle r’s E a r t h ... 1028
N e w C h em ical Process for F ib e r ... 1028
w age D isp osal in N e w Y o r k ... 1028
E x h a u stin g L a m p B u lb s a t H igh T e m p e r a tu re 1028 C ad m iu m S torag e B a tt e r y P la te s ... 1028
F ren ch A lcohol P ro d u ctio n and U s e s ... 1029
N a tu ra l G as U s e d ... 1029
G old and P la tin u m b y th e T o n ... 1029
P rod u ctio n of P la tin u m ... 1029
No t e s a n d Co r r e s p o n d e n c e: S yrian A u to b u rn in g L im e sto n e ... 1029
O b itu a ry : Ju les O g ie r... 1030
A m erican In s titu te of C h em ical E n g in e e rs ... 1030
O rth o-T olid ine as a R e a g en t for the C olo rim etric E s ti m ation of S m all Q u an tities of F ree C hlorin e— a C o r r e c tio n ... 1030
Bo o k Re v i e w s: In d u strial and M a n u fa ctu rin g C h e m istry: O rgan ic; C h e m istry of th e O il Ind ustries; E x p lo siv es: A S y n op tic and C ritica l T re a tm e n t of th e L ite ra tu re of th e S u b je c t as G ath ered from V a rio u s Sources; A lle n ’s C om m ercial O rgan ic A n a ly sis; N a tu ra l R o ck A sp h alts and B itu m en s; C orrection : L iqu id A ir— O x yg en — N itr o g e n ... 1030
Ne w Pu b l ic a t io n s... 1033
Re c e n t In v e n t i o n s... 1034
Ma r k e t Re p o r t... 1036
Au th o r In d e x... 1037
Su b j e c t In d e x... 1042
966 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. s, No. 12
EDITORIALS
R E S E A R C H
M u ch progress h as been m ade in recen t y e a rs in th e e stab lish m en t of research lab o rato rie s in th e m ore p ro gre ssive m a n u fa ctu rin g p la n ts in th is c o u n try ; y e t a c a n v a ss o f th e situ a tio n w ill show th a t a co m p a r a tiv e ly sm a ll p e rcen ta ge of in d u stria l m anagers is ev en n ow co n v in ced th a t a carefu l scien tific s tu d y o f processes and p ro d u cts w ill p a y , an d th ese m anagers do n o t lo o k w ith fa v o r upon th e su g gestio n th a t a v e r y sm all p o rtio n of th e ir earn in gs m igh t w ith p rofit be in v e ste d in a reserve of k n o w led ge of th e ir in d u s try .
T h e A m e rican m a n u fa ctu re r h as fo u n d th e d e v e lo p m en t of his business so e a sy and rap id , eith er on a c co u n t of fa v o ra b le raw m a terial co n d itio n s, or a g re e d y d em an d fo r his p ro d u cts th a t it has n o t been n ecessary fo r h im to d e v o te a tte n tio n to th e s tu d y of m ore efficien t processes, in order to reap en orm ous p rofits.
In o th er cases th e tim e and e n e rg y o f m a n y m anagers h as b een so ta k e n up w ith th e prob lem s of k eep in g up w ith th e n a tu ra l d em and s, due to th e g ro w th of th e c o u n try , th a t a scien tific s tu d y o f th e in d u s try h as been, and w ill co n tin u e to be, deferred u n til profits begin to fail.
P ro b a b ly th e g re a te st fa c to r in re ta rd in g th e de
v e lo p m e n t of scien tific research am ong our in d u stries h as b een h igh ta riff. T h is h igh ta riff has cau sed m a n y o f our in d u stries to prosp er an d p a y en orm ou s profits in sp ite of th e ir sh o rt-sig h ted m an age m e n t. P o litica l research , w ith a v ie w to ex p lo itin g th e consu m er, is w ell u n d ersto o d b y such m anagers an d it is a re g re t
ta b le fa c t th a t m an y of th e m h a v e sp en t th o u san d s of dollars on th e lo b b y and n ot onq cen t for p la cin g th e ir bu siness on a sound scien tific fo o tin g .
P erh ap s th e m anagers w h o h a v e sp ecia lized in th is fo rm of p o litica l research are th e v ic tim s of certain econ om ic co n d itio n s and sh o u ld n o t b e held respo nsible for th e sele ctio n o f th is m eth od of b u ild in g up th e ir business. T h e y are em p lo ye d to p rod u ce a p ro d u ct a t a p ro fit and it is n ot a lw a y s stip u la te d b y th e s to c k hold ers or d ire cto rs h o w th a t p rofit sh all be p ro d u ced. N o sto ck h o ld e r h as y e t been d isco ve red w ho raises a n y q u estion as to th e source of p rofits so lo n g as th e y are large. T h e relatio n s b etw e en th e a m o u n t of real m o n ey in v e ste d and th e p ro fits a ccru in g th e re fro m h a v e lo n g since b een su b m erged in w a ter— th e u n iv ersa l so lv e n t fo r excessive profits. T h e p o sitio n o f th e m an ager u nder su ch co n d itio n s is t r u ly d is
tressin g and b lam e a tta ch e s m ore to th e people and p ra ctices w h ich h a ve m ade it n ecessary fo r h im to fo llo w th e chan ces fo r th e g re a te st p r o fits 're g a rd le s s of a ll e th ica l consideration s.
T h e recen t red u ctio n s in th e ta riff on m a n y p ro d u cts and th e rem o v al of th a t se d u c tiv e p ro sp ect fro m th e field o f p ro b a b ility fo r in creasin g pro fits w ill u n d o u b te d ly re su lt in stim u la tin g in te re st in th e scien tific s tu d y of processes a n d p ro d u cts as th e m ost lik e ly m eans of m a in ta in in g earnings. T h e loss of th is ta riff p ro te ctio n w ill, in th e end, ex ert a g re a t s ta b iliz in g in
fluen ce on our in d u stria l d ev elo p m e n t. T h e protec"
tio n of in d u s try b y flim sy artificial regu latio n s is soo ner or la te r b o u n d to collap se, and th e w iser course w o u ld be to b u ild u po n stro n ge r fo u n d atio n s. I t m a y ta k e som e tim e fo r m a n u fa ctu re rs w ho h a ve en
jo y e d ta riff p ro te ctio n to realize th a t relief fro m th eir presen t p red icam e n t m a y com e th ro u g h a m ore sys
te m a tic a p p lica tio n of research m eth o d s b u t u ltim ate ly , a fte r th e h op e o f in creasin g p ro fits b y th e political ro u te h as b een e n tire ly elim in ate d , th e y w ill tu rn to th e scien tific m eth od.
T h e co n tro l a n d use of th e im m u ta b le law s of nature o b v io u s ly offer a m ore sta b le b asis u po n w hich to b u ild an d a m ore u n ifo rm source of p ro fit th a n any stru c tu re b u ilt upon a rtificial co n d itio n s created b y leg isla tio n .
T h e q u a lity of m a n y of our m a n u fa ctu re d products is n o t up to th e h igh est sta n d a rd , b u t th e dem and has been so pressin g th a t th e go o d s h a v e been ac
ce p te d in sp ite of th e ir d efects. M a n y concerns spend alm o st as m uch tim e and m o n ey in m akin g their goods s ta y so ld as th e y sp end on th e ir m anu factu re.
W e all k n o w th a t it is an occasion fo r co m m en t and o ften co n g ra tu la tio n w hen a p iece o f m ach in ery is d elive re d w h ich is c ap ab le of b ein g p u t in to use w ith ou t disclosing fu n d a m e n ta l d efe cts in design, arrange
m ent, c o n stru ctio n or m a terials. A d e liv e ry o f supplies w h ich does n o t occasion co m p lain ts, endless corre
sp ond ence or p ro b a b ly a d ju stm e n ts is a cu rio sity irt som e in d u stria l w ork.
T h e q u a lity p ro b lem is b y no m eans s e ttle d in our in d u stries and b efore w e reach th e sa tu ra tio n point, of our d o m estic m a rk e ts an d a tte m p t to branch out.
in to fo reig n tra d e in co m p e titio n w ith th e skill and w o rkm an sh ip of o th er n atio n s, w e sh all h a v e to solve- it. C u t-a n d -tr y m eth o d s for th e design of equip
m en t, w h ich re su lt in su ch m on stro sities as a ten-foot, v a c u u m pan w ith a fo u r-in ch v a p o r o u tle t, a m achine w h ere th e sam e sized s h a ft is used th ro u g h o u t regard
less o f th e fa c t th a t th e w orkin g lo a d ra tio in different p a rts of th e m ach in e is 45 to 1, an d o th er misfits, to o nu m ero u s an d w ell k n o w n to m en tion , w ill have to be re p la ce d b y scien tific m eth od s. T h e sup erlative claim s o f a d v e rtisin g m an agers an d th e “ talkin g p o in ts ” of salesm en , w hich th e y o fte n a d m it are not n ecessa rily p o in ts o f m erit, w ill a v a il fo r a tim e but th e b u y e r is slo w ly a w ak e n in g to th e fa c t th a t he is- b u y in g v a lu e an d th a t th e re is a d efin ite relatio n be
tw e en value an d price.
T h e q u a lity an d v a lu e of a p ro d u c t are based upon th e a p p licatio n o f co rrect p rin cip les in its conception, p re p ara tio n an d use, and th e se co rrect p rincip les can be e stab lish ed o n ly b y scien tific in v e stig a tio n . It is d ifficu lt to see h ow su b sta n tia l p rogress can be made in th is d ire ctio n w ith o u t su ch stu d y .
M a n y m an agers ta k e th e p o sitio n th a t th e y will n o t in s ta ll research lab o rato rie s fo r th e purpose of d e v elo p in g th e ir in d u s try b ecau se th e y can purchase.
D ec., 1913 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 967 from abro a d or elsew here rea d y -m a d e im p ro ve m en ts
and d ev elo p m e n ts w ith o u t ta k in g th e risk of th e exp erim e n tal expenses. T h is p o lic y is p ra ctice d b y a n u m ber of w ell-kn o w n co rp o ratio n s. Its w isdom m ay n ever be d eterm in ed b ecau se it w ill be im possible to d ecide, w hen su ccessfu l, w h eth er its success d e
pends upon th e m eth o d or upon superior a d v a n ta g e from o th er causes. I t seem s fair to assum e, h ow ever, th a t th e ch an ces are a g a in st su ccessfu l business a d m in istration on th is p o licy . T h e risk of n o t findin g new d ev elo p m e n ts or of n o t h a v in g an o p p o rtu n ity to p u rch ase th e m , m a y resu lt in losses m a n y tim es greate r th a n th e expense of m a in ta in in g research dep artm en ts.
T h e re are p ro b lem s in in d u stria l w o rk W'hich are com m on to all in d u stries in a certain field or to a large group o f in d u stries in th e sam e field in w hich co o p era tion in research w o u ld b en efit all alike. I refer p a r
tic u la rly to such prob lem s as th e d isp o sition of w astes from d ye-h ou ses, p ap e r m ills, gas w orks, th e sm oke nuisance p ro b lem w hich is im p o rta n t to all ste am po w er using ind u stries, flue d u st fro m sm elte r sta ck s, flue dust from p y rite s burn ers, cem en t d u st fro m cem en t m ills, etc.
It is e a sily co n ce iv a b le t h a t a n u m ber o f concerns in sim ilar or id e n tica l fields m igh t co o p era te for th e in v e stig a tio n an d th e d e v e lo p m e n t of com m on p ro b lem s fo r th e eq u a l b en efit of all concern ed a n d p ro b a b ly the s a lv a tio n of th e in d u s try itse lf. S u ch coop eration is now b ein g b ro u g h t a b o u t in a m easure b y th e scien tific so cieties an d o rg a n iza tio n s rep resen ted in differ
ent in d u stries. F o r exam p le, th e M ich ig a n G as A sso ciatio n su p plies fu n d s fo r th e in v e stig a tio n of problem s in gas m a n u fa ctu re com m on to th e con stitu en t m em bers o f th a t o rga n iza tio n . T h e A m erican T a n n ers’ A sso cia tio n is c o n d u ctin g in v e stig a tio n s com m on to th e ta n n in g in d u stry , an d o th er societies are sh o w in g a d ispo sition to co o p era te on research problem s. S u b s ta n tia l progress on co o p e ra tiv e re
search w ill n o t b e m ade b y th e te ch n ica l societies, h ow ever, on a cc o u n t of th e lim ited m eans a t th e ir disposal an d th e c o m p a ra tiv e ly large n u m ber and m agn itu d e of th e problem s.
If in d u stria l concern s w ere to com bin e for th e su p p ort of sp ecific in v e stig a tio n s on p rob lem s of com m on interest, g re a t progress m igh t be m ade. T h e elem en t of desiring to m on opo lize all of th e resu lts and to en jo y som e e x clu sive a d v a n ta g e o v e r p a rticip a n ts b e cause th e y are business co m p e tito rs w ou ld h a ve to be e n tire ly elim in a te d an d m an agers w ould be obliged to ta k e a b ro a d er an d m ore com p reh en sive v ie w of their p ro b lem an d its p u rp o se th a n a t present. W e have d iscussed th e fe a s ib ility of th is p lan w ith co m peting in te re sts in a n u m ber of cases and h a ve fre q u en tly h a d th e p ro p o sitio n p ied b y th e insisten ce upon th e p a r t of som e m an agers th a t his co m p a n y would n ot be in te re ste d in a d ev elo p m e n t th a t it could not m onopolize. C o o p e ratio n on th e p a rt of several and a m o n o p o ly of th e resu lts b y one is an insoluble problem fro m th e sta n d p o in t here proposed.
It is n o t n e ce ssa ry or e v e n desirable th a t th e re
sults of c o o p e ra tiv e research be th ro w n open to p u b
lic use. Such resu lts sh o u ld be and rem ain th e e x clu sive p ro p e rty , for a lim ited period a t le a st, b y p a te n t or o th erw ise, of th o se w ho co n trib u te to th e d evelo p m e n t. T h ere is a lre a d y , e sp e cia lly in th is c o u n try , to o little re ga rd an d p ro te ctio n fo r th e rig h ts o f pioneers w ho h a v e sp en t th e ir m o n ey and ta k e n th e ir ch an ces in order to fu rth e r in d u stria l d e v e lo p m en t. A n y schem e w hich w ou ld open g rea te r o p p o rtu n ities to in d u stria l p ira c y w ou ld be d isastro u s to d evelo p m e n t, and su ccessfu l co o p eratio n on sp ecific research p ro b lem s of com m on in te re st w ou ld h a v e to c a r ry w ith it a p la n fo r th e p ro te ctio n of th e rig h ts o f th e d evelo p ers. T h e rig h t to co o p era te in th e re search es sh o u ld not be denied to a n y one to w hom th e resu lts w o u ld be of va lu e , b u t th e o p p o rtu n ity for p ira tin g th e resu lts w ith o u t proper com pen sation sh o u ld be denied.
T h e S h erm an law h as b een cite d as a leg al o b stacle to th e d e v e lo p m e n t of c o o p e ra tiv e research . T h is la w w as e n a cte d for th e p re v e n tio n of m o n o p o ly in re stra in t of trad e . T h e p re v e n tio n of in d u stria l d e
v e lo p m e n t w as c e r ta in ly n ot co n te m p la te d , an d it is d o u b tfu l if su ch a co n stru ctio n could e v er be p u t upon its pro visio n . W ell in ten d e d law s are som etim es d iv e rte d to stra n g e uses an d a lre a d y we are co n fro n ted w ith th e d isto rtio n o f th is la w in w a y s c a lc u la te d to prod u ce p o litica l e ffe ct. T h e su n d ry c iv il bill passed b y th e la s t congress p ro v id e d $300,000 for p ro se cu tin g co m b in atio n s under th e S h erm an la w b u t carried an a d d itio n a l p ro visio n , th e m o tiv e for w hich can n o t be m isu n derstood , th a t none of th e m o n ey w as to be used in p ro se cu tin g co m b in atio n s of la b o r or co m b in atio n s of farm ers.
If b y a n y co n ce iv a b le in te rp re ta tio n or m o tive th e Sh erm an law sh o u ld be co n stru e d as p re v e n tin g th e co o p eratio n of in d u stria l in s titu tio n s in th e s tu d y of scien tific and en gin eerin g p rob lem s of m u tu a l in terest, it is our d u ty to sh o w th e m a lin te rp re ta tio n o f th e la w and in d ica te prop er a m en d m en t. If c h e m istry is to be rega rd e d as an im p o rta n t profession its o r
g a n izatio n s m u st consider affairs a ffectin g its in terest and th e in te re sts o f its in d u stria l co n stitu en ts. C h e m ists and engineers h a v e sto o d u n til re ce n tly , w ith o u t p ro te st, rid icu lo u s abuses in our p a te n t law s an d p ra c tices. A s soon as th e y co n ce n tra te d th e ir effo rts on needed reform s th e S u p rem e C o u rt reco gn ized th e ju stic e of th e ir p ro te sts, re ca st th e ru les of p ra ctice, an d now w e are lo o k in g fo rw ard to a revisio n of th e p a te n t law s w h ich w ill b e tte r p ro te ct th e in te rests o f th e professions concern ed .
I t has been said th a t th e m ost im p o rta n t step in in v e n tio n is to realize a need. If th e ch em ical p ro fession w ill realize th e need of m ore scien tific s tu d y of in d u stria l problem s and th e g re a t p o ssibilities of co o p eratio n in th e s tu d y of sp ecific p rob lem s b y in te rested in d u strial gro u p s it is our d u t y to d isco ve r th e w a y fo r th e acco m p lish m e n t o f th is need.
T H E C O N T R O L O F P U B L IC U T IL IT IE S
U p to th e begin n in g of th e le g is la tiv e sessions of 1913, fo u rtee n sta te s— W iscon sin, N ew Y o r k , M a r y lan d , N ew Jersey, V e rm o n t, O hio, W a sh in g to n ,
968 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. 5, No. 12 C alifo rn ia , N e v a d a , O regon, K a n sa s, N ew H am psh ire,
C o n n e c tic u t, an d R h o d e Isla n d — h a d e stab lish ed com m ission s for th e con trol of p u b lic u tilities. M a ssa c h u se tts d ivid e d m a n y of th e sam e pow ers am ong th ree com m issions, an d sev eral sta te s g a v e a p a rt of th e sam e pow ers to oth er com m issions, such as, for exam p le in O k lah o fn a, to th e co rp o ratio n co m m issions.
F o llo w in g con sid erable a g ita tio n , e ig h t sta te s—
In d ian a, Illin o is, C o lo rad o , M issou ri, M o n ta n a, Id a h o , P e n n s y lv a n ia , an d W est V irg in ia — cre ate d p u b lic u tilitie s com m ission s d u rin g th e le g is la tiv e sessions of 1913. M a ssa ch u se tts conferred th e d u ties of th e h ig h w a y com m ission re latin g to te le grap h s and te le ph ones an d th e d u ties of th e railro ad com m ission upon a new p u b lic service com m ission ; O hio re d ra fte d th e p u b lic u tility com m ission law , g iv in g a d d itio n a l p o w ers e sp e cia lly re la tin g to v a lu a tio n an d to sto ck an d b o n d issues; an d New' H am p sh ire am end ed her law b y g iv in g th e com m ission pow er o v er acco u n tin g, in clu d in g d ep re cia tio n . In each case th e com m ission is m ade a p p o in tiv e b y th e go vern or.
T h ese law s u n ifo rm ly req u ire th a t p u b lic u tilitie s sh all g iv e ju st and reaso n ab le service a t a ju s t and reaso n ab le ra te , an d in m ost sta te s th e com m ission s are g iv e n am p le po w er for in v e stig a tio n and en fo rce
m en t. T h e m u n icip al u tilitie s p laced under co n tro l in th e d ifferen t sta te s are m a in ly h ea t, lig h t, w a ter and po w er com p anies, stree t ra ilw a y s, and telep h on e an d te le g ra p h com p anies. In m ost of th e sta te s,
T H E P R O T E C T I O N O F IR O N A N D S T E E L B Y P A IN T F IL M S
By
No r m a nA.
Du b o isReceived October 4, 1913
T h e th eo ries of corrosion of iron and steel w hich h a v e receive d co n sid e ratio n and w h ich still seem to h a ve th e ir defenders and opposers are in terestin g to note. T h e ca rb o n ic a cid th e o ry in b rief requires th e presence of carbo n ic acid to s ta r t corrosion. T h e pero xide th e o ry supposes th a t h y d ro gen pero xid e is form ed in th e presence of m o istu re and o x y g e n , and th a t th is h y d ro gen p ero xid e causes corrosion. T h e e le c tro ly tic th e o ry assum es th a t iron passes in to so lu tio n in w a ter in th e form of a ferro u s ion b efore it can oxidize. A m ore or less co m p lete discussion of th ese th eories m a y be fo u n d in th e v a rio u s jo u rn a ls and oth er p u b licatio n s. I t is n ot th e purpose of th is pap er to discuss th em .
F ro m th e sta n d p o in t of th e p a in t te ch n o lo g ist th e prob lem is th a t of finding th e p a in t film w h ich w ill en able him to p ro te ct th e exp osed su rface of iron and steel from th e vario u s ru stin g influ ences for th e lo n gest p ossible tim e. T h e th eories of corrosion and n u m er
ous discussions of th e m h a v e been of in e stim ab le va lu e , a n d th e proper in te rp re ta tio n of th em has en abled th e p a in t te ch n o lo g ist to im p ro ve his p a in t film.
L e t us b riefly consider th ese th eo ries from th e s ta n d p o in t in question .
railro ad s, oth er com m on carriers an d sim ilar services are also co n tro lled .
D iscrim in a tio n is p ro h ib ite d in service and rates;
free service to a n y b u t certain e x cep ted classes is p ro h ib ite d , an d , in all b u t W e st V irg in ia , issues of sto ck s and bond s are p la ce d under th e regu latio n of th e com m ission ; u n ifo rm a cco u n ts are p ro v id e d for, e ith er in a m a n d a to ry or o p tio n al w a y , an d valu atio n of th e p ro p e rty used and useful fo r th e convenience o f th e p u b lic is a u th o rized in n e a rly all of th e states.
In In d ia n a and O hio such v a lu a tio n is required.
In a lm o st e v e r y s ta te m u n icip a lly ow n ed u tilities are s u b je c t to th e sam e re gu la tio n s as oth ers. T h e law s m ake no ex cep tio n s for hom e ru le. A strong effo rt w as m ade in Illin o is to e x c e p t C h ica g o from the law , b u t it fa ile d . I t m a y be said in general th a t the s ta te com m ission is sup rem e in m ost m a tters o ver the m u n icip a lities, a lth o u g h m uch p o w er is le ft to the la tte r to re g u la te and co n tro l. T h e cities grant fran ch ises and re g u la te b y c o n tra c t or otherwise th e se rv ice an d co n d itio n of o c c u p y in g o f th e streets.
*In In d ia n a th e in d e te rm in a te p e rm it is p ro v id e d for afte r th e m ann er of th e W iscon sin law .
A co n sid eratio n of th e new p u b lic u tilitie s acts sh o w s th a t th ere is a te n d e n c y to g iv e real pow ers to th e com m issions. W ith th e e x ce p tio n of th e laws passed in M a ssa ch u se tts and W est V irg in ia , th e acts of th e y e a r rep resen t n e a rly all of th e b e st w hich have been d e m o n strate d to be e m p iric a lly go od in other
sta te s. ' W . A .
H a m o r
T h e carb o n ic acid th e o ry requ ires th e presence of carb o n ic acid th a t corrosion m a y proceed. In other w ords, con sid erin g a p a in t film p ro p e rly a pp lied over th e su rface of iron and steel it requ ires th a t carbon dioxide sh all pass th ro u g h th is film , an d also th at w a ter, e ith er as such or in th e fo rm of aqu eou s vapor, shall pass th ro u g h th e film , an d th e re in conjunction w ith th e carb o n dioxide re a ct as carb o n ic acid. The im p ervio u sn ess of th e p a in t film to carbo n dioxide gas and to aqu eou s va p o r, th e n , is th e v it a l q uality fro m th e sta n d p o in t of th is th e o ry . T h e m ore im p e rv io u s th e ' p a in t film to th e gases carb o n dioxide and aq u eo u s v a p o r, th e lon ger it w ill p ro te c t th e iron or steel fro m corrosion.
T h e p ero xid e th e o r y requ ires th e fo rm atio n of h y
drogen p ero xid e on th e su rface of th e iron or steel.
C o n sid e rin g a p a in t film p ro p e rly ap p lied over the su rface of iron or steel, th erefo re, th is m eans that th e less p e rv io u s th e p a in t film is to th e gases oxygen an d aqu eou s v a p o r, th e sm aller w ill be th e quan tity of h y d ro g en p ero xid e fo rm ed on th e su rface of the iron or steel, an d th e lo n ger it w ill p ro te ct th e iron or steel fro m corrosion.
T h e e le c tr o ly tic th e o r y requ ires th a t iron first pass in to so lu tio n in w a te r as ferro u s ion, an d th a t it is th en a cte d u po n b y o x y g e n d isso lved in th e w ater or b y carbo n dioxid e an d w a te r to fo rm ru st. Again consid erin g a p a in t film p ro p e rly a p p lied o ver iron or-
ORIGINAL PAPERS
Dec., 1913 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 969 steel th is th e o ry requ ires th e presence of w a ter in w h ich
th e iron m a y d issolve to form ferro u s ions. O b vio u sly , th e o n ly w a y th e w a te r can ge t to th e iron or steel is to pass th ro u g h th e p a in t film , as such , or in th e form of aq u eo u s va p o r. If w e su p p ose th e ferro u s ions h a ve been form ed, th e a ctio n can go no fu rth e r in th e a b sence of an o x id izin g a gen t, p re su m a b ly oxygen , w hich in tu rn m u st ge t th ro u g h th e p a in t film . T h e reasonin g for th e presence of o th er gases is sim ilar.
W e find, th e re fo re , t h a t for corrosion to proceed a c cordin g to th e e le c tr o ly tic th e o ry i he gases, aqu eou s v a p o r, o x y g e n , or oth ers m u st pass th ro u g h th e p a in t film , and as in th e o th er cases, th e m ore im p e rvio u s th e p a in t film to gases an d m oistu re, th e lo n ger it w ill p ro te ct th e su rface of th e iron or steel from corrosion.
T h is is b u t to co n clu d e th a t th e p a in t film w hich w ill serve for th e lo n gest tim e as a p ro te ctio n to iron or steel a g a in st corrosion is th e one w h ich is th e least p ervio u s to aq u eo u s v a p o r, th e gases o x y ge n and carbon d ioxide, or in fa c t a n y gas in th e su rro u n d in g atm osp h ere w hich m a y in a n y w a y cause or a ccelera te corrosion.
If w e assum e th e corrosion to be e n tire ly due to th e d ete rio ra tio n of th e p a in t film ra th e r th a n to its p e rm e a b ility to aqu eou s v a p o r and oth er gases, th e sam e conclu sion holds, as th e r a te of d ete rio ra tio n w ill be p ro p o rtio n al to th e p e rm e a b ility of th e film to th e d ete rio ra tin g elem ents.
T h e e le c tro ly tic th e o r y of corrosion has g iv en rise to a d ivisio n of p ig m en ts in to th ree classes: corrosion accelerators, corrosion in h ib ito rs, and inerts. W h ile these p ig m en ts seem to g iv e resu lts as p red icted b y this th e o ry in th e presence of a b u n d an ce of w a ter or when th e iron or steel is a c tu a lly im m ersed in w ater, it does n o t n ecessa rily fo llo w th a t th e y w ill do so, to a lik e e x te n t a t le a st, w h en in co rp o ra ted in a p ain t film w here co n d itio n s are m uch different.
A ssu m e, fo r in stan ce, th a t our p ain t film is som e
w h at p e rv io u s to aq u eo u s v a p o r and oth er gases.
It fo llo w s th a t ju s t as m oistu re m a y en ter to th e iron or steel su rface and p e rh a p s g iv e con d itio n s under which th e e le c tr o ly tic th e o ry m a y a p p ly w hen outside conditions are d am p , th is m o istu re m a y also pass from th e steel su rface o u tw a rd w hen outside cond itio ns are d ry, and th u s le a v e th e steel su rface d ry in w hich case th e e le c tr o ly tic th e o r y ca n n o t p o ssib ly a p p ly.
A s a m a tte r o f fa c t, th e a ctu a l con d itio n s e x istin g on the su rface b en e ath th e p a in t film, in m ost instan ces, are v e ry p ro b a b ly b etw e en th e tw o extrem es of som e
w hat d am p and n ea rly d ry , an d th is is fa r from b eing covered w ith an a b u n d an ce of w a te r a t all tim es, the cond itio ns u n der w h ich th e e le c tro ly tic th e o ry seem s to w ork o u t w ell. T h is reasonin g is borne ou t b y th e fact th a t a piece o f b rig h t steel im m ersed in w ater containing a little zin c ch ro m ate in suspension w ill rem ain b rig h t p erh ap s in d e fin ite ly , w hile th e sam e pigm ent in a p a in t film under o rd in a ry conditio ns will not p ro te ct th e steel in a lik e m anner.
A gain, tw o p a in ts com posed of th e sam e veh icle, but th e first co n tain in g a so-called corrosion accelerato r only, p a in ted on a steel su rface in a lo c a lity of ord i
nary d ryn ess w ill o u tla st to a g re a t e x te n t th e second containing a ru st in h ib itiv e p ig m en t p a in ted on a
steel su rface in a lo c a lity h a b itu a lly v e r y d am p . T h is reasonin g seem s to in d icate and th e evid en ce seem s to b ear o u t th e conclusion th a t th e p rob lem of iron and steel p rese rv atio n is ra th e r to be so lv ed b y m a k in g our p a in t film as n ea rly im p e rvio u s to gases as possible, th a n b y tr y in g to p re v e n t corrosion b y th e ad d itio n of th e so-called in h ib itiv e p igm en ts.
T h e p rob lem is a p h ysica l one rath er th a n a ch em ical one, and a com p ariso n of p a in t film s as to th e ir r e la tiv e o b stru ctio n to th e diffusion of gases w ill tell m ore rega rd in g th e ir v a lu e as p ro te ctio n a ga in st corrosion th a n a s tu d y o f th e in h ib itiv e actio n of th e ir pigm en ts.
T h is is n o t to s a y th a t th e in h ib itiv e p ro p e rty of ce rta in p igm en ts is n o t w o rth con sid eration , b u t th e im p ervio u sn ess of th e film s is of fa r greate r im p o rtan ce.
T h e w o rk to be described here w as carried o u t for th e p urpose o f d ete rm in in g w h eth er a sp ecial fo rm u la p a in t m ade acco rd in g to th e fo rego in g princip les, e m b o d y in g diffusion retard e rs, w o u ld not o u tla st in pro
te c tin g q u alities th o se m ade acco rd in g to th e fo rm u las a cce p te d as first q u a lity p a in ts for th e ir resp e ctive purposes.
O ur p rim e o b je c t is to m ake th e film as im p ervio u s to gases as possible. T h is m a y be accom p lish ed to a certain e x te n t b y sp ecial tre a tm e n t o f th e veh icle and b y in co rp o ra tin g sp ecial p ig m en ts an d p ig m en t co m b 'n a tio n s. I t is w ell k n o w n th a t a film from th e o x id atio n of pure linseed oil, i. e., a film of lin oxin , is m ore or less p erm eab le to m oistu re and gases. I t is m ore or less porous. I f o th er oils or gu m s, or sim ilar m aterials, can be in co rp o ra te d w ith th e linseed oil to form a hom o gen eo u s m ass w h ich as a w hole a cts as a p e rfe ct v e h icle as rega rd s c o m p a tib ility of p rop erties, it is re a d ily u n d e rstan d ab le th a t such tre a tm e n t m ay, to an ex te n t, fill th e in term o lecu la r sp aces b etw een th e linseed oil m olecules, ju s t as in oth er cases of so lu tion, a llo y , or m ixtu re ; and th is com p o u nd ve h icle w ill be m ore dense, w ill le a v e a film w hich offers m ore resistan ce to th e diffusion of gases, and w ill, th e re fore, p ro te ct th e iron and steel for a lo n ger tim e (as
su m in g oth er th in g s eq u al) th a n a film w hich has n o t b een tre a te d in th is w a y.
A B C D E
Pl a t e I — St e e l Pa n e l s Pa in t e d w it h Pa in t s o p Sa m e Fo r m u l a
Ex c e p t On e Co n s t it u e n t o pt h e Ve h ic l e
P la te I show s five steel p anels w h ich , a fte r th o ro u g h clean ing w ith h o t 10 per cen t solution of sulfuric acid for tw e n ty m inu tes, w ash in g b y im m ersion in d ilu te cau stic solu tio n , th o ro u g h ly w ash in g w ith w ater, and q u ic k ly d ryin g , w ere p a in ted as follow s. A ll p a in ts w ere of th e sam e fo rm u la, w ith th e excep tio n of one co n s titu e n t in th e veh icle.
97
© 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. 5, No. 12 P an el A is a pure linseed oil veh icle.P an el B co n tain s 5 per cen t of K a u ri m ixin g va rn ish in th e veh icle.
P an el C co n tain s 10 per cen t of K a u ri m ixin g varn ish in th e veh icle.
P an el D co n tain s 20 per cen t o f K a u ri m ixing varn ish in th e veh icle.
P an el E co n tain s 30 per cen t of K a u ri m ixin g varn ish in th e veh icle.
T h ese w ere exp osed in a clo sed box w ith a glass fro n t, in order th a t th e co n d itio n s c o u 'd be c a re fu lly w a tch ed . O x y gen and th e corrosion a cce le ra tin g gases in th e atm o sp h ere w ere passed in to th e box th ro u g h w ash b o ttle s, to insure a slow b u t s te a d y c u r
ren t, and a sm all q u a n tity of ste am w as a d m itte d to keep th e atm o sp h ere w ith in th e b ox a lw a y s v e ry m oist, b u t n ot sufficien t to raise th e te m p e ra tu re m a te ria lly . T h e pan els w ere exam in ed from d a y to d a y , and rem oved w hen it w as ju d g e d th a t fu rth er e xp osu re m igh t o b lite ra te th e tru th s for w h ich we w ere seeking.
It is v e r y e v id e n t th a t th e p anels a t b o th ends h a ve fa ile d before th o se betw een . A relatio n m a y also be seen b etw e en th e d u ra tio n of p ro te ctio n and the q u a n tity of K a u ri m ixin g va rn ish in th e ve h icle . T h e p ro te ctin g q u alities increase w ith th e per cen t of K a u ri m ixin g varn ish to a certain p o in t, an d th en fa ll off a ga in as th e p e rcen ta g e of K a u ri m ixin g varn ish is in creased b ey o n d th is p o in t. T h is seem s to in d icate a defin ite p o in t of m axim u m sealin g effe ct for th is p a rticu la r m aterial.
A n o th e r illu stra tio n of m akin g a p a in t less p ervio u s and th e re fo re a b e tte r p ro te ctio n a g a in st corrosion, is th e prop er choice of p ig m en ts. R e d lead and linseed oil h a ve been lon g lo o k ed upon as th e b est p rim er for iron and steel. T h is m a y be tru e, b u t is it n o t possible to im p ro ve th is red lead aiid linseed oil w ith o u t seri
o u sly ch an gin g its n a tu re and o b ta in a film w hich is less p ervio u s to gases and m oisture and th e re b y p ro te ct th e iron an d steel ev en m ore e ffe c tiv e ly th a n
m um vo ids, to prod u ce a red lea d prim er, w hich has all th e a d v a n ta g e s of th e tra d itio n a l red lead and lin
seed oil, an d is a t th e sam e tim e less p e rv io u s, and th erefo re a b e tte r p ro te ctio n a g a in st corrosion.
P la te II show s a series of p airs of steel panels, w h ich h a v e b een cle an ed in th e usual m anner with acid , etc. B o th A and B of each p air w ere painted w ith th e sam e secon d c o a t p a in t, and each p air w ith a d ifferen t second c o a t p a in t, w h ile A of each p air was p rim ed w ith a sp ecial red lead p a in t, fo rm u late d , ac
co rd in g to th e p rin cip les ju s t m en tion ed , and B of each p air w as prim ed w ith red lea d and linseed oil m ixed acco rd in g to a fo rm u la considered to g iv e the b est resu lts o b ta in a b le a fte r m a n y y e a rs of p ractical p a in tin g u n der m ore or less a d verse co n d itio n s of m ois
tu re and corrosion a cce le ra tin g gases. A ll th e panels w ere p a in te d in e x a c tly th e sam e m anner on th e same
Pl a t e
II
— Pa ir so p St e e l Pa n e l sA’s primed with special red lead paint B’s primed with usual red lead paint All painted with same second coat paint.
w ill th e red lea d and linseed oil? If we sh a k e off som e of th e trad itio n a l b o n d s and a p p ly th e te ach in g s of m ore re ce n t scien tific in v e stig a tio n w e find it possible b y using th e fo reg o in g p rin cip les an d th e prop er ch oice of p a rticle sizes, m akin g use of th e la w of m ini
Pl a t e
III
— Pa ir s o f St e e l Pa n e l s Pa in t e d w it h So-c a l l e d Ru stPr o o f Pa in t s
A’s primed with special red lead paint B’s primed with rust proof paint All second coats of rust proof paint
d a y , allo w e d th e sam e tim e to d ry b etw e en coats an d also a fte r th e secon d co a t, an d exp osed as p reviou sly describ ed a t th e sam e tim e and for th e sam e length of tim e. S ince th e second c o a t on A an d B is th e same in each in stan ce its effe ct h as n o th in g w h a te v e r to do w ith th e com pariso n , th is b ein g d ep en d e n t en tirely on th e differen ce in th e red lea d p rim in g p a in ts on A and B . I t can be seen a t a glan ce th a t th e sp ecial red lea d p a in t on A h as g iv e n a m uch m ore efficient pro
te ctio n th a n th a t m ixed acco rd in g to th e p revailing cu sto m on B . O n e h u n d red and tw e n ty com parison p anels were; exp osed in th is te s t and in e v e ry instance -panel A sh o w ed a b e tte r film th a n did pan el B.
L a s tly , le t us ta k e up fo r a b rief sp ace th e incom in g of th e th ro n g of fa n ta s tic a lly n am ed " p a i n t s ” w hich h a v e b een p u t on th e m a rk e t w ith claim s equally as fa n ta s tic . M a n y of th ese h a v e b een claim ed to p ro te ct th e iro n and steel as a p rim er and as a second c o a t b e tte r th a n a n y th in g on th e m a rk et. I t is only n ecessa ry to refer to P la te I I I , w h ich is a ph otograph of som e pairs of steel pan els p rep ared as before men
tio n ed an d p a in te d w ith a n u m ber of so-called rust in h ib itiv e or ru st p ro o f p a in ts. On p anels marked B w as p a in te d tw o co a ts of a p a in t, and on panels m a rk ed A one c o a t o f th e sam e p a in t o v e r a prim ing c o a t of th e sp ecial red lea d p a in t fo rm e rly m entioned.
A s a d ifferen t p a in t is on each p air th ere are as
D e c., 1913 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 971 m an y d ifferen t p a in ts as th e re are pairs of panels.
I t is re a d ily seen th a t th e tw o co a ts of a n y of these p a in ts, B , do n o t p ro te ct as w ell as w here it is a pp lied o v er th e sp ecial red lead prim er, A .
B lu e lea d seem s to h a v e certain p rop erties v e ry sim ilar to red lead w h en used in a p a in t for th e p rim in g of iron or steel, an d in fa c t it is v e r y possible th a t it m a y be fu lly as go od fo r th is pu rpo se as red lead, w hen p ro p e rly used, if n o t b e tte r. E xp erim e n ts are now b ein g co n d u cte d b y th e w riter to determ ine th e se relatio n s.
R e c e n tly th e id ea h as b een set fo rth th a t certain p ig m en ts are ru st in h ib itiv e b y v irtu e of th e ir alkalin e q u alities. F u rth e r in v e s tig a tio n seem s n ecessary to d eterm in e w h eth er it is sim p ly th e a lk a lin e prop erties of th ese p ig m en ts considered as a ru st in h ib itiv e on ly w hich en d ow s th e p a in t film w ith su p erio r p ro te ctin g q u alities.
T h e su g gestio n m a y n o t be o u t of p lace th a t th e b asic p ro p erties of certain p ig m en ts en able th e m to a tta c k th e v e h icle to a su fficien t e x te n t to form a sm all q u a n tity o f m etallic soap w hich acts as a b in d in g m aterial b e tw e e n th e p ig m en t p a rticle and th e lin oxin , th u s offerin g a g rea te r o b stru ctio n to th e p assage o f d isin te g ra tin g elem en ts b etw een p ig m ent p a rticle and ve h icle ; or p e rh a p s a ctin g as a d iffu sion re ta rd e r in th e linoxin .
I t is n ot th e in te n tio n of th e w riter to p o in t o u t th e sh o rtco m in gs of a n y p a rtic u la r b ra n d o f p a in t or th e o ry , b u t sim p ly to g iv e resu lts of exp erim en t and in te rp re ta tio n of th e sam e w ith a v ie w to b ette rin g th e p a in t co n d itio n s fo r all concern ed.
In co n clu sion th e n , it w o u ld seem th a t w h a te v e r th e co rre ct th e o ry of corrosio n m a y be, it is of first' im p o rta n ce to th e p a in t te ch n o lo g ist to co n stru ct his film in such a m ann er as to exclu d e gases and m ois
tu re to th e g re a te st po ssible e x te n t, as w ith o u t th ese no corrosion can p o ssib ly ta k e place.
La b o r a t o r ie s o p t h e Go r d o n-Hit t l Co.
Bo s t o n
T H E O L E O R E S IN S O F J E F F R E Y A N D S IN G L E L E A F P IN E S
By A. W.
S c n o R G E RReceived September 25, 1913
T h e F o re st S e rvice fo r a n u m ber of yea rs has been in v e s tig a tin g th e p o ssib ilities of u tilizin g vario u s species • of conifers for th e p ro d u ctio n of n a v a l stores. T h e fo llo w in g w o rk on J e ffre y and sin gleleaf pines is a co n tin u a tio n o f th e e x a m in a tio n o f th e oleoresins o b tain ed d u rin g th e ta p p in g exp erim en ts. T h e m ethods of a n a lysis e m p lo y e d and th e resu lts o b ta in ed in th e ex a m in a tio n of o th er sp ecies w ill be fo u n d in a n oth er p u b lic a tio n .1 •
T h e oleoresins of th e pin on p in e1 (P in u s edulis, E ngelm ) and sin gleleaf pine ( P in u s monophylla, T orr, and F rem .) are sim ilar in co m p o sitio n , app earance, and odor. B o th oleoresins c o n tain large resin acid c ry sta ls an d h a v e a p u n ge n t ch a ra cte ristic odor.
T h e v o la tile oils of th e tw o species consist m ain ly of a-p in e n e and th e sesq u ite rp en e cad in en e is fou n d in th e h igh er b o ilin g p o rtio n s. In a d d itio n , jS-pinene
1 "A n Examination of the Oleoresins of Some Western Pines,” by A. W. Schorger, Forest Service, Bull. 119.
and p ro b a b ly lim o n en e1 occu r in th e oil from P in u s edulis w hile lim onene occurs in th e oil of P in u s monophylla.
A tte n tio n has been p re v io u s ly 2 called to th e co n fu sion cau sed b y la c k of an e x a ct k n o w le d g e of th e species y ie ld in g h ep tan e. T h e source of th is su b sta n ce has been v a r io u s ly ascrib e d to one or m ore o f th e fo l
lo w in g sp ecies: W estern y e llo w pine (P . pondcrosa, L a w s ); d igger pine (P . sabiniana, D o u g l.); and J effrey pine (P . je jjr e y i). I t h as been p r e v io u s ly 2 show n th a t th e oil fro m P in u s pondcrosa does n ot co n tain h ep tan e and th a t th e oil of P in u s sabiniana consists of n e a rly pure h ep ta n e . I t is now possible to co n firm th e w o rk of B la s d a le 3 an d W e n ze ll4 since ex a m in a tio n of a u th e n tic sam p les of th e oleoresin o f P in u s je jjr e y i has sh o w n th a t th e oil consists la rg e ly of norm al
h ep tan e.
T h e la c k of u n ifo rm d a ta in th e lite ra tu re regard in g th e resin acid s is m uch to be re gre tte d . T h e m eltin g p o in t of a b ie tic acid fro m co lo p h o n y varies fro m 1 3 s 05 to 1 6 5 °.6 T s c h irc h 7 sta te s th a t A m e rican co lo p h o n y c o n tain s a -, /S-, an d y -a b ie tic acid s m eltin g a t 1 5 5 °, 158 °, an d 1 5 3 - 1 5 4 0, re sp e ctiv e ly , and th e n o b ta in s a b ie tic acid , m eltin g p o in t 1 6 6 -1 6 7 ° , fro m rosin o il.8 L e u c h te n b e rg e r,9 w o rk in g under T sch irch , exam in ed th e co lo p h o n y of P in u s jejfrey i. E x tra c tio n of an e th er so lu tio n of th e co lo p h o n y w ith one per cen t (NH.O2CO3 g a v e fo u r per cen t of a -J e ffro p in ic acid, C10H14O2, m. p. 1 6 0 -1 6 1 ° ; nine p er cen t /
3
-Jeffropin ic acid , CisHisOo, m. p. 8 1 -8 2 °. E x tra c tio n w ith one per cen t N a 2C0
3 so lu tio n g a v e 35 per cen t a-Jeffro- p in o lic acid , C14H20O2, or C u H 2202, m. p. 1 1 7 - 1 1 8 ° ; 38.2 per cen t /3
-Jeffrop in olic acid , C h H 2o02, or C1.1H22O2, m. p. 77—78°. T h e acid iso la te d b y th e a u th o r from th e oleoresin o f P . je jjr e y i m elte d a t 1 7 0 - 1 7 1 ° . T h e silver s a lt co n tain ed 26.16 per cen t of A g , agreein g w ith th e fo rm u la C20H30O2. T h e acid fro m th e co lo p h o n y m elte d a t 1 3 7 -8 ° c ry s ta lliz e d from aceto n e and 1 4 5 -6 ° c ry sta lliz e d fro m aceto n e and h yd ro ch lo ric a cid . a -J e ffro p in ic acid requ ires 3 9 . 5 1 per cen t A g and a -J e ffro p in o lic acid , C1.1H20O2, requ ires 32.98 per cen t A g . T o o b ta in acid s of th is fo rm u la it w ould be n ecessary for th e resin c ry s ta ls e xistin g in th e o leo resin to un dergo p ro fo u n d a lte ra tio n in h e a tin g to 1 4 5 0 C . w hich is n ot borne o u t b y exp erience. T h e a ctio n o f acid s and alk a lie s h as a m aterial e ffe c t on th e m eltin g p o in t of th e resin acid . V a le n te 10 o b ta in e d an acid fro m F re n ch co lo p h o n y m eltin g in th e cru d e s ta te a t a b o u t 160°. W hen purified b y solu tio n in d ilu te sodium carb o n a te and p re cip ita tio n w ith d ilu te su lfu ric acid, th e resin a cid m elted a t o n ly 14 6 -14 8 °.EX PERIM EN TA L
Oleoresin of P in u s monophylla
Oleoresin.— A n a ly sis o f th e cru d e oleoresin g a v e
1 Loc. cit., 29.
5 “An Examination of the Oleoresins of Some W estern Pines,” by A. W. Schorger, Forest Service, Bull. 119.
* Blasdale, J. Am. Chem. Soc., 23, 162-4 (1901).
< Wenzell, Pharm. Rev., 22, 408-14 (1904).
* Fliickiger, J. Prakt. Chem., 101, 235 (1867).
8 Maly, Silzungsber. d. k. Akad. d. Wis. zu Wien, 44, 121 (1861).
7 “ Die Harze und die Harzebehalter,” 2nd ed., 1906, p. 660.
« Arch. Pharm., 245, 1 (1907).
»Ibid., 245, 701-7 (1907).
10
A tti della R. Accad. dei Liticei, 1, [4] 13 (1884).
972 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. 5, No. 12 th e fo llo w in g p e rcen ta ge s: V o la tile oil 19.00 per
ce n t; c o lo p h o n y (grad e N ) 79.63 per c e n t; trash , needles, b a rk , e tc., o . n per c e n t; w a ter 1.26 per cent.
Volatile oil.— T h e p ro p erties of th e oil w ere as fo l
low s: d 15o 0 .8 721-0 .8 733 ; n 1,,60 1.4 7 3 2 -1.4 7 3 3 ; a 2D°
+ 1 4 .4 1 ° to + 1 7 .2 6 ° . F iv e h u n d red gram s of th e oil g a v e th e fo llo w in g resu lts on fra ctio n a tio n :
Temp, (corr.)
° C.
Distillate observed Per cent
Distillate cumulative
Per cent dw°
nir15^.9-156.9 4.75 4.75 0.8602 1.4674
157.0 10.25 15.00 0.8603 1.4676
157.1 10.25 25.25 0.8602 1.4677
157.2 10.20 35.45 0.8599 1.4678
157.4 10.33 45.78 0.8598 1.4679
157.8 9.94 55.72 0.8594 1.4680
158.2 9.80 65.52 0.8588 1.4680
160.0 10.52 76.04 0.8576 1.4685
171.8 10.07 86.11 0.8536 1.4705
190.0 3.99 90.10 0.8511 1.4818
9.80 99.90
a -P in e n e .— A fte r re p e ate d fra c tio n a tio n 398.5 gram s of oil w ere o b ta in e d b o ilin g b elo w 160°. T e n gram s of a fra c tio n , b. p. 1 5 5 .5 - 1 5 7 ° , d 15o 0.8612, a 2Dso +
3
S-3 6
°, g a v e o n ly 0.78 gram (7.8 per cent) of p in en e n itro so ch lo rid e, m. p. 9 9°; n itrolp iperid in e, m. p. 1 1 8 ° . T h e lo w y ie ld of n itrosoch lo rid e is d o u b tless due to th e high o p tica l ro ta tio n of th e pinene fra c tio n . T h e fractio n , b. p. 1 6 0 -17 0 °, w eigh in g 21.5 gram s w as exam in ed for ^-pinene w ith n e g a tiv e resu lts.
L ivion ene.— T h e lim onene fractio n w eigh in g 17.5 gra m s h ad th e fo llo w in g pro p erties: b. p. 17 0 -18 0 °;
Od8“ — 1 .1 8 ° . A cry sta llin e te tra b ro m id e w as not o b ta in e d b u t a d ih yd ro ch lo rid e , 111. p. 4 9 °, w as e a sily secured.
C adincnc.— T h e residue rem ain in g fro m th e o rigin al fra c tio n a tio n w as d istilled fro m a L a d e n b u rg flask an d tw o fractio n s co lle cted : (1) b. p. 200-250°, 18.5 gram s; (2) b. p. 250-280°, 20.2 gram s; a f + 10.58°.
F ra c tio n (2) w as fo u n d to co n tain cad in en e as show n b y a d ih yd ro ch lo rid e , m. p. 1 1 7 - 1 1 8 ° . A 6 .14 per c en t eth ereal so lu tio n g a v e a 3D5° — 2.02°. In the e x a m in a tio n of d- a n d /-cadinene fro m v a rio u s oils th e ro ta tio n of th e cad in ene d ih yd ro ch lo rid e h as a lw a y s been fou n d to be n ega tiv e.
Colophony.— T h e co lo p h o n y h ad th e fo llo w in g co n s ta n ts : A c id no. 155.9 b y d ire ct titr a tio n ; sap. no.
163.3. W hen th e co lo p h o n y w as tre a te d w ith an e x cess of N /2 a lco h o lic po tash it y ield ed 7.22 p e r c e n t o f resene soluble in p e tro leu m ether. T h e co lo p h o n y on b ein g d isso lved in aceto n e and allow ed to stan d in an ice box for a m on th d ep o sited a m ass of resin c ry s ta ls . T h ese c ry sta ls w ere m e ch a n ically freed fro m o ily im p u rities so fa r as possible, ra p id ly stirred in co ld ace to n e and th e so lv e n t d eca n te d . A fte r fo u r c ry s ta lliz a tio n s from th e sam e so lv e n t, th e c ry sta ls o b ta in e d m elte d a t 1 1 9 - 1 2 0 ° , and were co m p le te ly liq u id a t 129 °. T h e resin c ry sta ls co n tain ed in th e origin al oleoresin w ere freed from th e g rea te r p o rtio n of th e a d h eren t oil b y su ctio n . T h e resu ltin g w h ite, w a x y cak e w as re cry sta llize d six tim es from aceton e.
T h e c ry s ta ls o b ta in e d m elted a t 12 9 -13 0 ° and were c o m p le te ly liq u id a t 13 5 °. A n a ly sis of th e silver s a lt o f th e acid fo llo w s:
0.2214 gram o f silve r s a lt g a v e 0.0590 gram A g = 26.65 per cent.
S ilv e r a b ie ta te , A g ( C 2oH290:.), requires 26.37 per cen t Ag.
Oleoresin of P in u s Jeffreyi
Oleoresin.— T h e a n a lyse s c o n tain ed in th e fo llo w in g ta b le are of in terest in th a t th e y rep resen t sam ples fro m in d iv id u a l trees.
Volatile Volatile oil
No. oil
Per cent W ater
Per cent Trash
Per cent Colophony
Per cent dij° nln5°
1. . . ..11.25 1.23 0.46 87.06 0.7013 1.3963
2 ... .. 8.81 1.50 0.44 89.25 0.7018 1.3958
3. .. .. 9.73 2.29 0.23 87.75 0.6951 1.3927
4. .. ..10.96 1.42 0.80 86.82 0.7110 1.4002
5. . , .. 9.05 2.00, 0.40 88.55 0.7008 1.4060 M ean. . . . 9.96 1.69 0.47 87.88
Volatile O il.— T h e p ro p erties of th e v o la tile oils are g iv en in th e p reced in g ta b le . T h e oils fro m the five sam p les w ere m ixed an d 175 gra m s d istilled from a L a d e n b u rg flask w ith th e fo llo w in g resu lts:
Distillate Distillate Temp, (corr.) observed cumulative
° C. Per cent Per cent dii° n D °
98.2- 98.8 16.74 16.74 0.6880 1.3902
100.0 40.47 57.21 0.6889 1.3903
102.0 22.92 80.13 0.6897 1.3905
105.0 8.17 88.40 0.6906 1.3915
113.0 4.05 92.45 0.6965 1.3937
7.37 99.82
Heptane.— T h e first fo u r fra ctio n s a m o u n tin g to 150 gram s w ere red istille d , using a 12-inch H em pel colu m n w ith th e fo llo w in g resu lts:
Distillate Distillate Temp. (corr.). observed cumulative
No.
° C.Per cent. Per cent dis°
1
98
.1
-98.3 19.20 19.20 0.6878
2
98.4 40.95 60.15 0.6881
3 98.5 30.07 90.22 0.6881
T h e b oilin g p o in ts and sp ecific g r a v itie s of fra ctio n s are p r a c tic a lly id e n tica l w ith th e con stan ts of pu re « -h ep tan e.
Cilronellal.— T h e resid u e b o ilin g a b o v e 1 1 3 ° dis
tille d m a in ly b etw e en 2 0 0 -215° C . T h e fractio n w ith th e la tte r b o ilin g p o in t w eig h ed 6 gram s (3.4 per cen t) and h a d : d]5o 0.8578; n2£ ° 1.4570; a 2D°°
— 2.50°. T h e oil h a d a lem on odor and sh o w ed the fo llo w in g p ro p erties of an a ld e h y d e : C o m b in ed w ith N aH SO a fo rm in g a floccu len t p re cip ita te , reduced an am m o n ia ca l silve r solu tio n, and p ro d u ced a rose- red c o lo ra tio n w ith a fu ch sin so lu tio n decolorized w ith S
0
2. T h e sem icarb azo n e o b ta in e d sep arated as oil th a t c ry s ta lliz e d a fte r sta n d in g in th e cold for se v e ral d a y s. T h e sem ica rb azo n e w as tw ic e re cry sta lliz e d fro m alcoh o l, fin a lly fro m a m ixtu re of ch loro
fo rm and p e tro leu m eth er. T h e c ry sta llin e pow der o b ta in e d m elted a t 9 1 -9 2 ° . L a c k of m aterial p reven ted th e s a tis fa c to ry fo rm atio n o f oth er d e riv a tiv e s. C o m p arison w ith th e pro p erties of citro n ella l from J a v a lem on o il1 follow s:
