IN D U S T R IA L
audENGIATEERING
C H E M I S T R Y
V ol. 30, C o n secu tiv e N o. 3
H a r r iso n E . H o w e , E d ito r
ANALYTICAL EDITION
20,800 Copies of This Issue Printed
January 15, 1938
Vol. 10, No. 1
De t e r m i n a t i o n o f Ma n g a n e s e, Ni c k e l, a n d Ph o s p h o r u s i n Ir o na n d St e e l...
... W. M. Murray, Jr., and S. E. Q. Ashley 1
De t e r m i n a t i o no f Py r e t h r i n I i n Co m m e r c ia l In s e c t i c i d e s Co n t a i n i n g Py r e t h r u m o r Py r e t h r u m Ex t r a c t ... D . A . Holaday 5
De t e r m i n a t i o n oV Ir o n w i t h Me r c a p t o a c e t i c Ac id
... H. W. Swank with M. G. Mellon 7
Tu r b i d i t y i n Su g a r Pr o d u c t s. V I...
...F. W. Zerban and Louis Sattler 9
De t e r m i n a t i o no f Ir o n i n Bio l o g ic a l Ma t e r i a l s. . .
...Prances Cope Hummel and H. H. Willard 13
De t e r m i n a t i o no f Air a n d Ca r b o n Di o x i d e i n Be e r .
... Philip P. Gray and Irwin M. Stone 15
De t e r m i n a t i o no f Ro t e n o n ei n De r r i s a n d Cu b e. I I . Ex t r a c t i o nf r o m t h e Ro o t...
... Howard A. Jones and J. J. T. Graham 19
St a n d a r d i z i n g Si l v e r Ni t r a t e Vo l u m e t r i c So l u t i o n .
... Robert D ’Orazio 23
De t e r m i n a t i o n o f Ma g n e t i c Ir o n Ox i d e a s Me a s u r e o f Co r r o s i o no f Bo i l e r Su p e r h e a t e r El e m e n t s . .
... ... . . R . C . Ulmer 24
St a n d a r d i z a t i o no f 2 , 6 - Di c i i l o r o p h e n o l i n d o p h e n o l. .
... M. H. Menaker and N . B . Guerrant 25
Ne w Me t h o d f o r St a n d a r d i z a t i o n o f Dy e Us e d f o r De t e r m i n a t i o n o f Ce v i t a m ic Ac id ( Vit a m i n C )
... Robert E . Buck and Walter S . Ritchie 26
Ph o t o g r a p h i n g Li n e Te s t s i n Vi t a m i n D As s a y s . . .
M. W ight Taylor, Daniel Klein, and Walter C. Russell 26
De s i g n s f o r La b o r a t o r y Fr a c t i o n a t i n g Co l u m n s . .
... J. H. Simons 29
De v i c e sf o r Ex t r a c t i o n b y Im m i s c i b l e Li q u i d s. . . . ... H . J. Wollner and John R. M atchett 31
Sm o k e Te n d e n c y La m p...
John B. Terry and Edward Field 33
Fr a c t i o n a t i n g De v i c ef o r Va c u u m Di s t i l l a t i o n s . .
...Evan Noonan 34
Ne w Ca p i l l a r y- Ty p e Vis c o m e t e r . . . P . E . Raaschou 35
Me t h o d o f Pr e p a r i n g Th i n Fi l m s. . . E. L . Kallander 40
Ap p a r a t u s f o r Te s t i n g Cr u s h i n g St r e n g t h: o f Gr a n u l e s...E. F . Harford 40
Mo d e r n La b o r a t o r i e s:
In d u s t r i a l a n d St r u c t u r a l Pr o d u c t s La b o r a t o r y, Ow e n s- Il l i n o i s Gl a s s Co m p a n y . . H . C . Winsor 42
Mic r o c h e m i s t r y :
De t e r m i n a t i o n o f Si z e o f Fi n e Ab r a s i v e Po w d e r s
... Frank L . Jones 45
Mic r o c h e m ic a l An a l y s i s o f Co l o r e d Sp e c k s a n d Cr y s t a l l i n e Oc c l u s i o n s i n So a p Ba r s...
... Herbert K. Alber and Clement J. Rodden 47
Mi c r o d e t e r m i n a t i o n o f Ca r b o n a n d Hy d r o g e n . .
... Adalbert Elek 51
Tu r b i d i m e t r i c Ti t r a t i o no f Sm a l l Am o u n t so f Nic o t i n eb y Us eo f Ph o t o e l e c t r ic Ce l l...
...Lyle D. Goodhue 52
Dr y i n g a n d We i g h i n g Hy g r o s c o p ic Su b s t a n c e s i n Mi c r o a n a l y s i s...Douglass F . Ilaym an 55
We i g h i n g Tu b e f o r Vo l a t i l e Li q u i d s i n Ca r b o n- Hy d r o g e na n d Du m a s Ni t r o g e n Se m i m i c r o d e t e r m i n a t i o n s ...V . A. Aluise 56
T he American Chem ical Society assumes no responsibility for the statem ents and opinions advanced b y contributors to its publications.
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4 INDUSTRIAL AND E N G IN E E R IN G CHEM ISTRY VOL. 10, NO. 1
9 W it h R a d io t r o n T u b e s , y o u r r a d io r e c e p t i o n i s g o o d . “ A g o o d r e c e p t i o n ,” a ls o , h a s b e e n g iv e n t o H o s k in s F u r n a c e s — b y l a b o r a t o r ie s t h e w o r ld a r o u n d . S h o w n h e r e i s o n e o f s e v e r a l H o s k in s F u r n a c e s u s e d i n t h e la b o r a t o r y o f R C A M fg . C o ., I n c T h r u - o u t t h e p r o c e s s in d u s t r i e s , f r o m f lo u r m i l l s t o s t e e l m i l l s , t h e s e f u r n a c e s a r e u s e d a t t e m p e r a t u r e s u p t o 2000° F . T e m p e r a t u r e c o n t r o l i s e a s y , u n i f o r m i t y o f h e a t - d i s t r i b u t i o n i s g o o d ; a n d t h e C h r o m e l e l e m e n t s a r e v e r y d u r a b le , a n d e a s y t o r e n e w . F o r f u l l i n f o r m a t i o n w r it e t o y o u r d e a le r , o r a s k u s fo r C a t a lo g - 5 6 Y . . . . H o s k in s M a n u f a c t u r i n g C o ., D e t r o it , M ic h ig a n .
l i t ? j
U e d m F U R N A C E S
THE
I S G O O D
ANALYTICAL E D IT IO N 5
N ew Pyrex Brand Plain a nd Fluted M oulded F u n nels—Accurate 60° Angle.
Greatly reduce* filtering time. Moulded, smooth, uniform.
R f
PYREX
*>AT
NEW ITEMS • NEW IMPROVEMENTS
NEW ACCOMPLISHMENTS IN “P Y R E X ” LABORATORY WARE
A t th e beginning of this new year, C orning G lass W orks presents a review o f accom plishm ents d u rin g the p a s t year. I t su m m a rizes briefly for y o u r checking, re p re se n ta tiv e new item s, im p ro v em en ts a n d recen t developm ents in “ P y re x ” b ra n d L a b o ra to ry W are. A nd it p resen ts fo u r im p o rta n t ad d itio n s w hich h av e re c e n tly been an n ounced— N ew Im p in g er A p p a ra tu s
— N ew P ip e tte s— N ew Im p ro v e d W est T y p e C ond en sers— and a N ew T h istle T u b e.
New Pyrex Brand Im pingèr, No.
1948 Graduated. /Vo. 1947 P la in — For .determining du st content of or impurities in air, auch us loud, silica, etc. Mude in accordance with requirements o f U . S. Public Health Department-
N ew Pyrer B rand Pipettes, N o. 1990—Made in wide capacity range. Hugged construction. Bal
anced for ease in manipulation. Long delivery stem enables solutions to be conveniently transferred.
■ N ew Pyrex Brand Funnel Tube, No. 1900—With Thistle Top. Thistle Top is of moulded construc
tion. thereby, affording ruggedness arid uniform
ity. H eavy stem increases mechanical strength.
E ach of these an d o th e r new item s in tro d u ced d u rin g th e p a st m o n th s possess definite ad v an tag es o v er th e old. Some hav e exclusive new featu res. All c o n trib u te to b e tte r la b o ra to ry technique, accuracy, efficiency and, freq u en tly , speed.
Achieved th ro u g h C orning R esearch, these new item s em phasize t h a t co n tin u al q u e st for perfection w hich is c h aracteristic of your profession an d of ours. T h e su p erio rity of each of these new p ro d u cts is such th a t all m e rit y o u r im m ediate consideration a n d inspection.
" P Y R E X ” is a registered trade-mark and indicates manufacture by CO RNING GLASS WORKS • CO RNING , N . Y.
N ew P yrer Brand W est Type Condenser, No. 1290 ---Four distinct new and improved features.
Stronger, more compact, more eificient and much more durable and convenient.
N ew Items and New Designations—In Standard Taper "Pyrex”
Glassware. Full Length and Medium Length Interchangeable Ground Glass Joints; Flask, Bottle, and Stoprock Stoppers. Now practically every item o f Pyrex- Brand Laboratory Glassware thut lias a ground surface, is made to conform strictly to Standard Taper specifications, as authorized by the N a t’f Bur. o f Stds.
C o r n i n g means--- Research In Glass
Send fo r New Catalog Supplem ent Describing M a n y N ew Items in “ P Y R E X ” Laboratory Glassware.
We shall be pleased to send you this new catalog supplement describing in complete detail many of the newer items in "Pyrex” Laboratory Ware. Every laboratory should have a copy.
Write today or ju st place your name and address on the margin of this page, clip off and m ail
C O R N I N G C L A S S W O R K S » C O R N I N G , X . Y .
6 IND U STR IA L AND E N G IN E E R IN G CHEM ISTRY VOL. 10, NO. 1
I n d u s t r i a l B e c k m a n p H M e te r
I [ERE, for the first time, is a p H meter especially designed
' ' for industrial use w hich combines laboratory ac
curacy with the necessary ruggedness and fool-proof simplicity for the most severe factory conditions.
The Shielded Glass Electrode is an exclusive feature of the Beckman p H Meter. It is completely sealed and inter
nally shielded so that the electrodes may be used with equal convenience either in the meter or in vats, tanks, etc., located at a distance from the meter.
For greater accuracy in making readings, a dual-scale meter and switch are used. In the first position of the switch, the full swing of the meter needle covers the A C ID range, 0 to 7 p H ; and in the second position, the full swing
2 1 0 7 0 . . .
covers the A L K A L IN E range, 7 to 14 p H . This arrange
ment spreads the scale double length and permits readings to be made to 0.02 p H . Should the range switch be in the wrong position, the needle merely moves off the scale, indicating that the switch should be moved to the other position.
The instrument is completely self-contained in a compact hardwood case with compartments for the Buffer Solution (used in standardizing the instrument) and the Potassium Ch lo ride Solution (used in flushing the Calomel Elec
trode). A strong leather-covered handle is provided for convenient carrying. The cover is detachable and has a safety device w hich prevents it from being closed until the meter is completely shut off.
..$ 1 5 0 .0 0
S C I E N T I F I C IN S T R U M E N T S
i \ | r 1 U I «49^1 Vv < r j TPADE
L A B O R A T O R Y A P P A R A T U S
N ew York • Boston • C H I C A G O • Toronto • Los A n geles
C H IC A G O — 1700 Irving Park Blvd. BO STO N—-79 Amherst St.
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KIMBLE GLASS COMPANY • • • • v i n e l a n d , n . j .
N E W Y O R K • • C H I C A G O • • P H I L A D E L P H I A • • D E T R O I T • • B O S T O N O n e o f th e m o s t fa r-re a c h in g a n d e n v ie d asse ts o f th e n a tio n is its v a s t D a iry In d u s try , p ro d u c in g a lm o st 1 1 0 ,0 00,000,000 p o u n d s o f w h o le m ilk e a c h y e a r. 2 0 % o f th e c o n s u m e r's f o o d d o lla r g o es f o r m ilk a n d m ilk p r o d u c t s — m o re th a n $ 3 8 5 ,0 0 0 ,0 0 0 in b u tte r , $57,000,- 0 0 0 in c h e e s e ,$ 1 3 1 ,0 0 0 ,0 0 0 in c o n d e n s e d a n d e v a p o ra te d m ilk. A ll to ld , th is am a z in g in d u s try tip s th e financial scales a t a b o u t $4 ,0 0 0 ,0 0 0 ,0 0 0 a y e a r!
K im ble Blue L ine E x ax G la ssw a re is a v e ry d efin ite a n d v ita l f a c to r in h e lp in g m ain ta in th e rig id c o n tro l a n d h ig h q u a lity o f d a iry p ro d u c ts . T h e a c c u ra c y o f Blue L ine E xax in te s t, analysis a n d re se a rc h — w h e th e r in d a iry la b o ra to rie s, o r in ch em ical o r in d u stria l p la n ts, clinical o r m e d ical in s titu tio n s — gives t h a t A S S U R A N C E so essen tial to scientific su ccess.
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The Visible
Stocked by leading Laboratory Supply Houses throughout the U nited States a n d Canada
G u a r a n t e e o f I n v i s i b l e Q u a l i t y
8 IND U STR IA L AND E N G IN E E R IN G CHEM ISTRY VOL. 10, NO. 1
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JANUARY 15, 1938 ANALYTICAL E D IT IO N
IF IT IS CHEMICALLY FEASIBLE
Baker & A dam son will produce to order a n y inorganic com pound, of a n y desired purity, with a n y specified set of com patible p h ysical properties.
Those whose unusual needs m ay not be covered in our cata lo g of 1000 C .P . A cid s and Reagent G ra d e Chem icals will find B & A p ro d u ctio n -to -o rd er an efficient branch of a chem ical service anim ated b y the principle: It can be done.
S E T T I N G T H E P A C E I N C H E M I C A L P U R I T Y S I N C E 1 8 8 2 *“¡ 0
i w K jc x i q j 2 s n {
B a k e r A d a m s o n
D iv is io n o f G E N E R A L C H E M I C A L C O M P A N Y , 4 0 R e c t o r S t., N e w Y o r k C P A c u / $
A tlan ta • B altim ore • B oston • B uffalo • C h a rlo tte • C h ic a g o • C le v e la n d • D e n v e r • K a n s a s C ity • Los A n g e le s • M in n e a p o lis • P h ila d e lp h ia • P ittsburgh • P ro v id e n c e • S a n F ran c isc o • St. Louis
FO R EXAMPLE:
Manganous O xid e. Until recently, obtainable only through import. B & A is now producing it to order, to exacting specifications.
Calcium Acetate, purified.
"Custom-made" by B & A, in quantity lots, to unusual sp e c ific a tio n s re g a rd in g purity, solubility and phys
ical make-up.
10 IND U STR IA L AND E N G IN E E R IN G CHEM ISTRY VOL. 10, NO. 1
NEW, IN D U S T R IA L M O D EL
B EC K M A N G LA SS E L E C T R O D E pH M E T E R
W IT H N E W T Y P E , F A C T O R Y F IL L E D , H E A V Y W A L L , S H IE L D E D GLASS E LE C TR O D E A N D C O M P A N IO N C A L O M E L E LEC TR O D E
B E C K M A N GLASS E L EC TR O D E pH M E T E R , In d u s tria l M od el. A p o rta b le , se lf-c o n ta in e d in s tr u m e n t of ru g g ed c o n stru c tio n , w ith o u t slide w ire p o te n tio m e te r, fo r continuous p H re ad in g s. W ith a new ty p e , fa c to ry filled, h e a v y w all, sh ie ld e d glass e le c tro d e a n d c o m p a n io n calom el electro d e. O p e ra te s u p o n a new v a c u u m tu b e v o ltm e te r c irc u it w ith d e
g e n e ra tiv e fe e d b a c k w hich sta b iliz e s c a lib ra tio n . T h e scale re a d s fro m p H 0 to p H 14 in 0.1 p H d iv isio n s, w ith d o u b le g ra d u a tio n s of p H 0 to p H 7 a n d p H 7 to p H 14, th e acid o r a lk a lin e ra n g e being selected b y a sw itch . T h e in s tr u m e n t is a d ju s te d fo r n o rm a l o p e ra tio n a t 2 5 °C a n d a c o n tro l is p ro v id e d fo r th e c o m p e n sa tio n of a s y m m e try p o te n tia l. I n co m m on w ith all glass electro d e sy ste m s, a c o rre c tio n fa c to r is re q u ire d a b o v e p H 9.5 as, fo r ex am p le, w h e n h ig h c o n c e n tra tio n s of so d iu m io n s a re e n c o u n te re d .
T h e h e a v y w all, sh ield ed glass ele c tro d e is c h a rg e d a n d p e rm a n e n tly sealed a t th e fa c to ry , re a d y for o p e ra tio n . T h e co m p an io n calom el ele c tro d e is p ro v id e d w ith g ro u n d glass sleeve a t im m e rsio n en d a n d c o n ta in s a p e rm a n e n t ch arg e of calo m e l-m e rc u ry a n d a q u a n tity of s a tu r a te d KC1 s o lu tio n sufficient fo r sev eral w eeks. T h e l a tte r can b e re p len ish ed th ro u g h a p lu g g ed o p en in g in th e o u te r tu b e . T h e electro d es are 5 in ch es long a n d a re m o u n te d o n a s u p p o rt ro d in th e c o m p a rtm e n t a t th e rig h t of th e c a rry in g case a n d c a n be ra ise d a n d low ered b y p ressin g a release b u tto n in th e side of th e h o ld er.
A 50 m l P y re x glass b e a k e r is u se d as a c o n ta in e r fo r th e te s t so lu tio n a n d re a d in g s c a n be m a d e w ith as little a s 10 m l of sam p le.
T h e in s tru m e n t is e n tire ly self-co n tain ed , w ith n ecessary d r y cells fo r o p e ra tio n a n d s u p p ly of B uffer M ix tu re a n d s a tu r a te d KC1 so lu tio n . I n c a rry in g case w ith o v erall d im en sio n s 1 3 /4 in ch es long X 9M in ch es deep X 9 in ch es hig h , w eig h t 23 lbs. T h e lid c a n n o t b e closed un less th e o p e ra tin g sw itc h is tu rn e d off.
4918-R. Beckman Glass Electrode pH M eter, Industrial Model, as above described, complete with shielded glass electrode and companion calomel electrode, Pyrex glass beaker 50 ml, 4 oz. bottle of saturated KC1 solution and 1 pt. of Buffer Mixture. In carrying case with directions for use mounted in the lid ... S150.00 Code W ord... Fabnt
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C o p y o f d e ta ile d d e s c r ip tiv e p a m p h l e t s e n t u p o n r e q u e s t.
ARTHUR H. T H O M A S CO M PANY
R E T A IL — W H O L E S A L E — E X P O R T
L A B O R A T O R Y A P P A R A T U S AND R E A G E N T S
W E S T W A S H IN G T O N SQ UARE P H IL A D E L P H IA , U.S.A.
C able A ddress, ' ‘B a la n c e .” P h ilad elp h ia
IN D U ST R IA L a»d ENG IN EER IN G CH EM ISTRY
A N A L Y T IC A L E D IT IO N ♦ H a r r is o n E . H o w e , E d ito r
Determ ination o f Manganese, Nickel, and Phosphorus in Iron and Steel
T h e U se o f R apid Spectrophotom etrie M ethods
W. M . M URRAY, J r . , a n d S. E. Q. ASIILEY , G en e ra l E le ctric C om pany, P ittsfie ld , M ass.
T h e a u th o r s p r e s e n t m e t h o d s fo r t h e ra p id p h o t o m e t r ic d e t e r m in a t io n o f m a n g a n e s e , n ic k e l, a n d p h o s p h o r u s in ir o n a n d s te e l.
F r o m fo u r t o six d e t e r m in a t io n s o f a n y o f t h e e le m e n t s m e n t io n e d m a y b e r u n w ith, c h e c k s in' a n h o u r a n d t h e sp e e d o f s in g le d e t e r m in a t io n s is a lm o s t a s g r e a t a s fo r a g ro u p .
N o s ta n d a r d s o lu t io n s a re r e q u ir e d , a n d a n y in s t r u m e n t m a y b e q u ic k ly c a lib r a te d w it h tw o or th r e e d e t e r m in a t io n s w it h in t h e l i m i t s m e n t io n e d .
T h e r e p r o d u c ib ility o f t h e d e t e r m in a tio n s is h ig h , a n d j u d g in g fr o m t h e r e s u lt s o b ta in e d o n B u r e a u o f S ta n d a r d s s a m p le s t h e a c c u r a c y is as g o o d or b e t t e r t h a n is o b t a in e d w it h m o s t r o u t in e d e t e r m in a tio n s .
T
H E development in recent years of various types of instruments for the quantitative measurement of the degree of absorption of visible light in solutions has vastly enlarged the domain of chemical colorimetry by substituting accurate absolute measurements for crude comparisons of the color of solutions. Excellent review articles by Mellon (6) and Straf
ford (18), describing these instruments and pointing out their advantages, have appeared during the last year. One of the great advantages of a spectrophotometer is th a t it is a selec
tive instrum ent and permits the determination by the absorp
tion of a chemical constituent even in the presence of another colored compound which would mask or pervert the color of the solution so much as to make an ordinary color comparison impossible. One very im portant application of this ad
vantage immediately comes to mind in the rapid analysis of ferrous alloys, and it is this field which the present authors have investigated for spectrophotometric exploitation.
Most absorption bands are rather broad, so th a t for prac
tical purposes it is sufficient to employ an instrum ent which
isolates the various regions of the spectrum by means of filters transm itting a narrow band of light. Such an instru
ment is the Zeiss Pulfrich step-photometer which was used in the present investigation. The construction of this instrum ent is too well known to w arrant description, b u t may be found in any of the Zeiss Company’s literature (15).
A survey of the literature showed th a t the problem which was undertaken had already been treated in p art by other investigators, mostly in Germany, and much of it is too recent to have been tested by other workers. The task a t hand became th a t of testing some of the methods which have al
ready been developed andhnproving some of the older meth
ods which have not proved sufficiently reliable by the older colorimetric technic.
The methods selected were those for manganese, nickel, and phosphorus, based on requirements of local foundry work as well as their chemical adaptability for the purpose in mind.
T e c h n ic
All photometric measurements wrere made with the Zeiss Pulfrich step-photometer. The general technic employed in making the measurements was th a t described in the directions which accompany the instrument. The extinction, k, was read directly from a calibrated drum on the photometer.
The extinction coefficient, K, was then obtained by dividing k by s, the length of the cell used.
* = ; a )
I t is thus possible to cover a wide range of concentrations by using cells from 0.5 to 5 cm. in length, and have all meas
urements reduced to the common basis of a 1-cm. cell length.
Calibration graphs were plotted with per cent of constituent and extinction coefficient, K, as coordinates. The graphs in each case were straight lines, so th a t a simple equation for the per cent of the constituent X m ay be derived from the slope of the line.
% X = ~C (2)
The constant c is specific for a given procedure, and once determined will always hold for th a t particular method.
•It has thus been found expedient to use these equations for routine work since they are much simpler and less liable to 1
2 IND U STR IA L AND E N G IN E E R IN G CH EM ISTR Y VOL. 10. NO. 1 error in interpretation than calibration graphs. In some
instances graphs will be given as illustration of typical results in the work which is to follow.
M a n g a n e s e
There are m any procedures for the colorimetric determina
tion of manganese in iron and steel. Mehlig (5) has studied a spectrophotometric method using a procedure depending upon preliminary precipitation of manganese dioxide and subsequent oxidation of the separated manganese with sodium bismuthate. Miiller (9) has pointed out th a t such separations are probably not necessary and th a t equations employing the extinction coefficient are very reliable. In a review of photoelectric colorimetry, Muller (10) gives a calibration graph for pure permanganate solutions which were oxidized by a periodate procedure, b u t neither details of the procedure nor applications were given.
Ta b l eI. Sp e c t r o p h o t o m e t r ic De t e r m i n a t i o no p Ma n g a n e s e (S ynthetic and Bureau of Standards sam ples)
M anganese M anganese
Sam ple k Cell Length K Found Present
Cm. % %
1 0 .3 0 3 .0 0 .1 0 0 .0 5 0 .0 4
2 0 .9 4 3 .0 0 .3 1 0 .1 5 0 .1 4
3 1.0 9 1 .0 1.09 0 .5 4 0 .5 3
4 0 .7 5 0 .5 1.5 0 0 .7 5 0 .7 5
5 1.2 6 0 .5 2 .5 2 1.2 6 1.27
51° 0 .5 2 1 .0 0 .5 2 0 .2 6 0 .2 7
51° 0 .2 5 0 .5 0 .5 0 0 .2 5 0 .2 7
55« 0 .1 3 3 .0 0 .0 4 0 .0 2 0 .0 1 9
10c° 1.1 5 0 .5 2 .3 0 1.1 5 1.13
5 fa 0 .7 7 0 .5 1 .54 0 .7 7 0 .7 6
° 51, 55, 10c, 5f are Bureau of Standards sam ples.
In the work described here, the periodate procedure of Willard and Greathouse (14) was used for oxidizing the manga
nese. This procedure has been noted as a superior means for oxidizing manganese to permanganic acid, b u t it does not lend itself easily to use in titration methods, as it is not easy to destroy the excess of periodate w ithout destroying the
WAVELENGTH A*
Fi g u r e 1
permanganate a t the same time. The advantage of the method lies in the rapidity, accuracy, and stability of per
manganate, and as no separations are involved, the procedure is very simple. The stability of the permanganate absorption band has been studied m any times (7) and it has been found th a t it does not shift appreciably with changes in concentra
tion or cation.
P r o c e d u r e . Weigh 0.500 gram of the iron or steel sample, and transfer to a 150-ml. beaker. Dissolve in a mixture of 15 ml.
of concentrated nitric acid and 25 ml. of water, heating on a hot plate to hasten solution. When the sample is dissolved, add
2 0 ml. of water, filter, and wash with small portions of water.
To the clear filtrate add 10 ml. of concentrated sulfuric acid and a small lump of ammonium persulfate. Boil for 10 minutes.
Cool slightly, and add 10 ml. of 85 per cent phosphoric acid and approximately 0.5 gram of potassium periodate. Boil for 1 minute, and keep hot (90° C.) for 10 minutes. All heating and boiling should be done in an open beaker to keep the volume down. Cool to room tem perature by placing in a pan of cold water, then dilute to exactly 100 ml. in a volumetric flask. The extinction coefficient of the clear permanganate solution is then determined, using distilled w ater as a comparison liquid. The measurement is made with a green filter with mean transmission a t 5300 Â., since this is in the region of maximum absorption for the permanganate ion (3, 4).
R e s u l t s . Calibration graphs prepared from pure man- ganous sulfate (from c. p . potassium permanganate) and ferric nitrate (from Bureau of Standards ingot iron) solutions gave straight lines passing through the origin. This means th a t the effect of iron is negligible in the presence of the large excess of phosphoric acid present. The range covered is from 0.01 up to about 1.5 per cent of manganese. The accuracy is of the order of 0.01 per cent of manganese. The calibration equation derived for this procedure w'as
% manganese = (3)
The data in Table I are typical and serve to illustrate the results obtained by dividing K by the constant 2 as found from the calibration graph and given in the calibration equa
tion (3). This calibration equation applies only to this specific procedure and photometer, b u t similar equations can be derived for other photometers with only one or two measure
ments on standard solutions, as the procedure has been found reliable and reproducible.
N ic k e l
Rollet (11) studied the colorimetric determination of nickel in cobalt salts, nickel steels, and organic m atter. The method depends on the formation of a soluble nickelic dimethyl- glyoxime. I t was found th a t iron hydroxide tends to drag down small amounts of nickel hydroxide in ammonia pre
cipitation, and this was avoided by adding dimethylglyoxime to form the nickel complex before the ammonia is added.
Recently Dietrich and Schmitt (1) have used a modification of this procedure in the development of a rapid photometric method for nickel in iron and steel. I t is inferred th a t iron was separated by ammonia precipitation, although the treat
m ent is not mentioned specifically. The iron m ust be either removed or held in solution as a complex, since the nickelic complex is formed in alkaline solution.
In the procedure developed in this study, the iron is held in alkaline solution by adding a large excess of citric acid. This alkaline iron citrate solution has a light yellow color. The nickel dimethylglyoxime solution is a deep wine-red color.
Absorption curves for these solutions are given in Figure 1.
I t is obvious th a t the iron has practically no absorption in the visible region of the spectrum above 5000 A. On the other hand the nickel shows a plateau in its absorption band near 5300 Â. Therefore, if the photometric measurements are made using a filter with mean transmission a t 5300 A., the
absorption of the iron will be eliminated entirely and a pre
liminary separation becomes unnecessary.
Dietrich and Schmitt (1) found the absorption curve of the nickelic dimethylglyoxime solution to be stable for eight hours.
As is evident from Figure 1, such was not found to be the case in this work. The freshly prepared solutions (curve 1) show an absorption plateau in the region of 5300
A.
The first curve taken immediately after mixing the reagents corresponds to the curve given by Dietrich and Schmitt. Curves 2, 3, and 4 show th a t this plateau rapidly disappears, and after the solution has stood for an hour the absorption curve shows only a single wide and smooth band. These curves were all prepared from pure nickel solutions, but it was found th a t the same curves were obtained when citric acid was present. Although the Pulfrich photometer used gives only eight points on the curves, their general shape has been con
firmed on a General Electric spectrophotometer which auto
matically records a smooth line from a monochromator whose slit emits a band only 100
A.
in width.The reason for the appearance of this plateau and its rapid change has not been ascertained, but it has been found to be reproducible and measurements completed within 10 minutes after mixing the reagents give consistent and reliable results.
Fi g u r e 2
Pr o c e d u r e. Weigh 0.400 gram of the iron or steel and trans
fer to a 1000-ml. volumetric flask. Add 25 ml. of 1 to 1 nitric acid and warm on a hot plate until the sample is dissolved. (In some cases of difficultly soluble chromium-nickel steels, a mix
ture of equal parts of nitric and hydrochloric acids may be neces
sary.) When solution is complete, cool and dilute to 1 0 0 0 ml.
Mix thoroughly and allow to stand for 5 or 10 minutes so th at any graphitic carbon and silica may settle to the bottom. Pipet exactly 25 ml. of the clear supernatant solution into a 100-ml.
volumetric flask. Then add the following reagents to the small sample in the order given and with thorough mixing after each addition: 10 ml. of citric acid solution (10 per cent), 5 ml. of saturated bromine water, 5 ml. of 1 to 1 ammonium hydroxide, and 3 ml. of a 1 per cent solution of dimethylglyoxime in alcohol.
Dilute the contents to exactly 1 0 0 ml. with distilled water and again mix thoroughly. The solution should be clear and a deep red color. The photometric measurements must be made within 10 minutes after the addition of the reagents. The measure
ment is made with a green filter with mean transmission at 5300 A.
R e s u l t s . Pure solutions of iron (from Bureau of Standards sample lid ) and nickel (from Hilger H. S. brand nickel rod) nitrates were used in preparing the calibration graph which is given in Figure 2. The line is satisfactory, showing a maximum error of about 0.2 per cent nickel in the higher concentra
tions and about 0.05 per cent nickel in the lower concen
trations. The range covered is from 0.5 to 19 per cent nickel.
The limit of usefulness of the method for high nickel concen
trations is determined by the solubility of the complex. If samples containing over 20 per cent nickel are analyzed by this method, a precipitate forms rather quickly and the re
sults are of no value. I t is possible, however, to sta rt with a smaller sample and calculate the results back to the basis of a 0.400-gram sample as used.
Ta b l e II. Sp e c t r o p h o t o m e t r ic De t e r m i n a t i o n o p Ni c k e l Sam-
S o .
B. of S. (Bureau of Standards sam ples)
Cell Nickel N ickel
N o. Length
Cm.
k K Found
%
Present
%
la 107 3 .0 0 .2 7 5 0.0 9 1 0 .8 3 0 .8 0 7
b 107 3 .0 0 .2 7 5 0 .0 9 1 0 .8 3 0 .8 0 7
2a 33a 1 .0 0 .3 6 0 .3 6 3 .2 7 3 .2 4
b 33a 1 .0 0 .3 7 0 .3 7 3 .3 6 3 .2 4
3a 32b 3 .0 0 .4 1 0 .1 4 1 .2 7 1 .20
b 32b 3 .0 0 .4 0 0 .1 3 1 .1 8 1 .2 0
4 101 1 .0 0 .9 4 5 0 .9 4 5 8 .6 0 8 .4 4
5 115 0 .5 0 .8 7 1 .7 4 15.83 15.8 9
The data in Table II show the results obtained on the analysis of Bureau of Standards samples by this method.
The agreement is satisfactory for routine foundry analyses, and the time saved by using the photometric method is con
siderable. The values for the per cent of nickel found were obtained from the calibration equation, which was derived from several values from the calibration graph and was found to be
% Ni = 9.10 X i f (4)
P h o s p h o r u s
The determination of phosphorus in iron and steel samples has always been a tedious and time-consuming task. The m any methods in use are practically all based on some modi
fication of a method involving preliminary precipitation of ammonium phosphomolybdate. The question always arises as to how complete this precipitation can be made, how definite is the composition of the salt, and how reliable are the subsequent methods of treatm ent of the salt after it is ob
tained. Very good results can be obtained by these standard procedures in the hands of a skilled operator; however, most of them are open to many errors and a quicker and less tedious method is desirable.
Of the older colorimetric methods for determining phos
phorus in iron and steel, the one worked out by Misson (8) appeared to be most worth studying. I t has been used and found satisfactory by Schroder (IS) and Getzov (S), but does not seem to have been given any widespread use. This method depends on the formation of a yellow phosphovanado- molybdate, whose formula is (NH-OsPO-rNII^VOa'lGMoOj according to Misson (8). I t was found to be a stable com
plex, showing almost no color change after 14 days’ standing.
The accuracy claimed for the method was 0.005 per cent of phosphorus in the range 0.04 to 0.1 per cent of phosphorus.
All of this work was done using the old method of visual comparison with standard solutions.
This method has been studied in the present work with consideration of the effect of concentration of reagents, acid concentration, and temperature a t the time of making the photometric readings. Since the solutions are yellow in color, it is rather difficult to make accurate visual comparison with standard solutions, and slight differences in concentration are not readily detected by the eye alone. The method depends largely on using an acid concentration which is optimum for color formation, and which is different from th a t used in the original procedures. The method using this new procedure and using the Pulfrich photometer gives very satisfactory re
sults for the range 0.01 to 1.0 per cent of phosphorus.
4 IND U STR IA L AND E N G IN E E R IN G CHEM ISTRY VOL. 10, NO. 1 W ith these limitations in mind, the following procedure was devised as being best fitted for the phosphorus determination.
Pr o c e d u r e. Dissolve a 0.500-gram sample in 20 ml. of 1 to 2
nitric acid with heating. Filter off any silica or graphitic carbon residue, washing with small portions of water. H eat the clear solution almost to boiling, add 5 ml. of 1 per cent potassium permanganate solution and keep the solution just below the boiling point for 10 minutes. Then cool the solution somewhat and add 2 drops of 30 per cent hydrogen peroxide (less than 0.001 per cent phosphorus content). Add exactly 10.0 ml. of ammonium vanadate solution from a pipet. (This solution is prepared by dissolving 2.345 grams of ammonium vanadate in 500 ml. of hot water, adding 20 ml. of 1 to 1 nitric acid, and di
luting to 1000 ml.) H eat the sample again to destroy the excess hydrogen peroxide, then place it in a pan of cold water and cool to room tem perature. At this point it should be clear and almost colorless. Transfer the solution to a 100-ml. volumetric flask, add 1 0 ml. of 1 0 per cent ammonium molybdate solution, and shake thoroughly to dissolve the precipitate which forms momen
tarily. Dilute to exactly 100 ml. and allow to stand for 10 minutes before making the photometric measurements. The ex
tinction coefficient is measured w ith a violet filter with mean transmission a t 4300 A. A 3.0-cm. cell is used for samples con
taining 0.01 to 0.1 per cent phosphorus, and a 0.50-cm. cell for samples containing 0 . 1 to 1 .0 per cent phosphorus.
R e s u l t s . Pure solutions of iron nitrate from Bureau of Standards ingot iron and c. p . potassium phosphate were used in the preparation of the calibration graphs, which are given in Figure 3. I t was found th a t the values of K , the extinction coefficient for a 1.0-cm. cell, were not the same when using cells of different lengths on the same solution. The values of K decrease as the cell length is increased from 0.5 to 3.0 cm., and when values of K are plotted against cell length, a straight line is obtained. However, this is an error of the instrum ent and not of the method or this particular solution, for similar results were obtained w ith potassium chromate, picric acid, and ferric chloride solutions. All these solutions show a maximum absorption in the 4300 A. range, so th a t it is ap
parently an effect peculiar to this region which was not ob
served when working with the nickel and permanganate solutions using the 5300
A.
filter. Because of this effect, two calibration curves and equations were prepared, one using a 3-cm. cell for low concentrations and the other using a 0.5-cm. cell for the higher concentrations.The equations derived from the two calibration graphs were:
% phosphorus = ^ i . yu 7&r~ for 0.5-cm. cell (5)v
q 2 2
% phosphorus = — T~5(j— ^or 3.0-cm. cell (6) The term subtracted from K in the numerator of each equa
tion is the value of K a t zero phosphorus concentration.
These solutions contain ferric nitrate which shows a small absorption and they also contain an excess of vanadic acid which also shows a small absorption in the region of measure
ment. However, this absorption is relatively constant and does not interfere with the measurements.
Ta b l e I II . Ef f e c t o f Ac id Co n c e n t r a t i o n o n Ex t i n c t i o n Co e f f i c i e n t o f Ph o s p h o v a n a d o m o l y b d a t e So l u t i o n s (Sam ples containing iron with 0.35 per cen t of phosphorus, using a cell of
0 .5 0 -cm . length in each case)
1 to 2 H N O j k K
ML
20 15° 0 .4 8 0 .9 6
25 0 .4 7 0 .9 4
40 0 .4 1 0 .8 2
a Precipitate formed quickly.
The results obtained in the analysis of Bureau of Standards samples by this procedure are given in Table IV. The values for the per cent of phosphorus found were calculated from calibration equations 5 and 6.
CM.CELL
•/. phosphorus Fi g u r e 3
Preliminary experiments showed th a t the acid concentra
tion and the size of sample used in the Misson (8) procedure gave rather erratic results. I t was found th a t the limit of the phosphorus concentration is about 5 mg. per 100 ml. of final volume and higher concentrations tend to give a pre
cipitate. Misson used a 1.0-gram sample of iron, b u t it was found th a t a 0.50-gram sample was sufficient and 5 mg. of phosphorus correspond to 1 per cent of a 0.50-gram sample, thus increasing the range of the method. In the older pro
cedure the sample was dissolved in 20 ml. of 1 to 1 nitric acid.
The complex is rather sensitive to acid concentration above a certain minimum, so th a t it is advisable to work w ith as small am ount of acid as is feasible. This was found to be 20 ml. of 1 to 2 nitric acid used to dissolve the sample with a final volume of 100 ml. The effect of acid is illustrated in Table III.
As is evident from the data in Table III, a precipitate forms when the acid concentration is too low. In the case where 40 ml. of acid were used, the color was very slow in forming and the extinction coefficient tended to drift towards higher values as the solution was allowed to stand. Several ex
periments of this type proved th a t a maximum color is de
veloped in solutions which are low in acid content, so th a t it is desirable to work with the minimum of acid present. This is limited, however, by the requirement th a t a certain amount m ust be present to prevent the formation of a precipitate.
When readings are taken w ith the solution a t a tem perature of 10° C., the values for the extinction coefficient are low, while if the temperature is very high (50° C.), the extinction coefficient tends to be high. I t was found th a t anywhere in the range 20° to 30° C., the readings were almost identical and temperature is unim portant in this small range which covers the usual room temperature.
<150 CM. CELL
