P u b l i c a t i o n O f f i c e : E a sto n , P a.
Ed i t o r i a l Of f i c e:
R oom 706, M ills B uilding, W ash in g to n , D . C.
T e l e p h o n e : N a tio n a l 0848 C a b l e : Jiechem (W ashington)
Ad v e r t i s i n g De p a r t m e n t: 332 W est 42nd St.,
N ew Y ork, N . Y.
T e l e p h o n e : B ry a n t 9-4430
C O N T E N T S
20,700 Copies of This Issue Printed Reduction of Antimonic Acid in Hydrochloric Add Solution
with M e r c u r y ...LeRoy TV. McCay Determination of Total Dissolved Solids in Water Analysis . ... C. S. Howard An Inexpensive Flame Shield... Clarence C. Vernon Volumetric Method for Determination of Fluorine . . . .
... H. H. Willard and 0. B. Winter Determination of Moisture in Sirups and Viscous Materials .
... E. W. Rice and P. Boleracki Photographic Recording of Line Tests for Vitamin D . . . .
A. L. Bacharach, E. Allchorne, V. Ilazley, and S. G. Stevenson Shorter Method for Determining Copper Iodometrically . . ... T. II. Whitehead and H. S. Miller Determination of C a d m iu m ...
...Loren C. Hurd and Richard W. Evans Determination of Fluorine in Cryolite . . . . F. J. Frere A Colorimetric Method for the Determination of Tartaric
Acid . A. K. Anderson, A. II. Rouse, and T. V. Letonoff Determination of Organic Sulfur in G a s ...
... Charming W. Wilson Rubber Beaker Rings for Accelerating Evaporation on Steam
B a t h ... J. A. Scherrer Assay of Plant Material for Its Rotenone Content . . . .
... Howard A. Jones New Reagent for Determination of Zinc . Armand J. Quick Determination of Nonmetallic Inclusions in Plain Carbon and Manganese Steels . T. R. Cunningham and R. J. Price Estimation of Gossypol in Cottonseed M e a l ...
... J. 0. Halverson and F. H. Smith Effect of Reversion Products and Amino Compounds on Su
crose Determinations in Cane P ro d u c ts ...
... F. W. Zerban and C. A. Gamble A Rapid Method for Distinguishing Bleached Sulfate from
Bleached Sulfite...Ralph W. Shaffer Equipment for Laboratory Fumigations with Hydrocyanic
A c i d ... II. L. Cupples
S u b s c r i p t i o n t o n o n - m e m b e r s , In d u s t r i a l a n d En g i n e e r i n g Ch e m i s t r y, $ 7 . 5 0 p e r y e a r . F o r e i g n p o s t a g e $ 1 . 5 0 , e x c e p t t o c o u n t r i e s a c c e p t i n g m a i l a t A m e r i c a n d o m e s t i c r a t e s a n d t o C a n a d a . An a l y t i c a l Ed i t i o n o n l y , $ 1 . 5 0 p e r y e a r , s i n g l e c o p i e s 5 0 c e n t s , t o m e m b e r s 4 0 c e n t s . Ne w s Ed i t i o n o n l y
$ 1 . 5 0 p e r y e a r . S u b s c r i p t i o n s , c h a n g e s o f a d d r e s s , a n d c l a i m s f o r l o s t c o p i e s s h o u l d b e r e f e r r e d t o C h a r l e s L . P a r s o n s , S e c r e t a r y , M i l l s B u i l d i n g , W a s h i n g t o n , D . C . T h e C o u n c i l h a s v o t e d t h a t n o c l a i m s w i l l b e a l l o w e d f o r c o p i e s o f j o u r n a l s l o s t i n t h e m a i l s , u n l e s s s u c h c l a i m s a r e r e c e i v e d w i t h i n s i x t y d a y s o f t h e d a t e o f i s s u e , a n d n o c l a i m s w i l l b e a l l o w e d f o r i s s u e s l o s t a s a r e s u l t o f i n s u f f i c i e n t n o t i c e o f c h a n g e o f a d d r e s s . ( T e n d a y s ' a d v a n c e n o t i c e r e q u i r e d . ) " M i s s i n g f r o m f i l e s ” c a n n o t b e a c c e p t e d a s t h e r e a s o n f o r h o n o r i n g a c l a i m . I f c h a n g e o f a d d r e s s i m p l i e s a c h a n g e o f p o s i t i o n , p l e a s e i n d i c a t e i t s n a t u r e .
The A m e r i c a n C h e m i c a l S o c i e t y also publishes the Journal of the American Chemical Society and Chemical Abstracts.
A Simplified Karns Technic for the Micro-Estimation of Io
dine...Harry von Kolnitz and Roe E. Remington 38 Determination of Zirconium in S te e ls ...
4 Stephen G. Simpson with Walter C. Schumb 40 6 Determination of Small Amounts of Invert Sugar in the Pres
ence of Sucrose... A. II. Edwards and S. J. Osborn 42 Determination of Hydrocyanic Acid in Air and in Air-Car
bon Dioxide M ixtures...II. L. Cupples 50 11 Determination of Small Quantities of Antimony in Solder in
Presence of I r o n ...C. W. Anderson 52 12 Determination of the Diastatic Activity of Honey . . . .
...II. A. Schuetle and R. J. Pauly 53 15 A Device for the Calibration of the Variable-Deviation Spec
troscope...Clarence F. Graham 54 16 Determination of Furfural Produced from Hardwoods . . .
...Harold A. Iddles and Paul J. Robbins 55 17
19 20
Interference of Pyridine Derivatives in Arsenic Determina
tion ...C. R. Gross 58 Analysis of White Metals and Their Smelter Products . . .
... Hans Neuberl 60 Modified Combustion A p p a ra tu s... R. N . Evans 61 22 Steam vs. Ether in Separation of Acids from Bacteriological
Media... James B. McNair 62 23 Automatic Titrating Devices...
... K. Hickman and C. R. Sanford 65 An Adjustable Stopcock Remover. . . . R. W. Westerman 68 27 Modified Hook-Up for Routine Use of Glass Electrode . . .
... E. C. Gilbert and Alan Cobb 69 29 A New Surface Tension Balance. . . . Richard J. DeGray 70
Micromelting-Point Determination with the Thiele Tube . . ... Eugene W. Blank 74 34 A Color Test for Rotenone...
... Howard A. Jones and Charles M. Smith 75 35 Use of Kohlrausch Sugar Flasks in Determinations of Bio
chemical Oxygen D em and ...Ivan C. Hall 76 36 A Continuous E xtractor... Armand J. Quick 76 An a l y t i c a l
E d i t i o n
V o l. 5, No. 1
J a n u a r y
15, 1933
I n d u s t r i a l
A N D E N G I N E E R I N G
C h e m i s t r y
VOL. 25, CONSECUTIVE NO. 3
Pu b l i s h e d b y t h e Am e r i c a n Ch e m i c a l So c i e t y Ha r r i s o n E . Ho w e, Ed i t o r
rvt otAjirm cHWOc« <c' OJtAMIlU «
C. P. HYDROCHLORIC ACID C.P. AMMONIUM HYDROXIDE C. P. G L A C I A L A C E T I C
h
U K the last ninety-three years the name GRASSELLI has been prominently identified with the Chemical Industry of the United States.In addition to the large number of Commer
cial Chemicals produced for industrial use, GRASSELLI has for years produced Chem ically
Pure Acids for laboratory work. G rasselli G rade Chem ically Pure Acids are dependable and uniform. Analyses are shown on all labels.
Nation-w ide branches and warehouses assure an excellence of delivery service in keeping with the High Q uality of our C. P. products.
EVELAND
I N C O R P O R A T E DOH
New York and Export Office: 350 Fifth Avenue B R A N C H E S A N D W A R E H O U S E S !
A L B A N Y CHARLOTTE DETROIT N E W O R L E A N S S O D U S N. Y
B IR M IN G H A M C H IC A G O M ILW A U K E E PH ILAD ELPH IA ST. LO U IS
B O S T O N C IN C IN N A T I N E W H A V E N PITTSBURGH ST. PAUL
S A N F R A N C IS C O , 5 8 4 M ission Street LO S A N G E L E S , 2 2 6 0 East 15th Street Represented in C anad a by C A N IA D I A N I N D U S T R IE S , LTD.,
Acid s and G eneral Chem icals Division — Montreal and Toronto
-Gr a s s e lH.
JwoRotmnnic ac<>
C R A S S E L l l
. i D t P H U B I t * * ' ¿ 1
—« ■ H A S S E L L !_
¿'lOVIUM HYDROXICI J - » A S S E L l L . J* * tiA i A f r r i c » ( j t
January 15, 1933 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 5
Two new
Universal
LABORATORY BURNERS
1
No. 2275 Burner, blast, universal, fo r all gases with air or oxygen $10.00
Far more engineering skill has been applied to laboratory burner design in the past tw o years th an in the previous ten. The success of this new effort is now here more evident th an in th e new Sargent high tem perature burner and the new blast b urner—both now ready for your use.
Both burners handle all common types of fuel gas perfectly, are highly efficient w ith all gases, and are rem arkably flexible as to flame shapes and sizes. W e strongly advise the pur-- chase of one of each of these finer burners for every laboratory.
E. H. SARGENT & CO.
Laboratory S u pplies
155-165 E. SU PE R IO R ST., CH ICA G O
N o . 2 3 4 7 B u r n e r , Sargent high tempera
-
ture, adjustable fo r use with all g a se s.. .$2.00
6 A N A L Y T I C A L E D I T I O N Vol. 5, No. 1
v. • < . m i s s i s
æ , /■• y»' -,j- ..i-* •‘‘fifl}
■■• ¡¿ 'r ' • w * > ! ,-^i* - / .Î JÏ.i,iU 7V*»'.- ^-f-' -v •_ »
*<**>>
M icrophotographs o f th in p o l
ished sections o f porcelain and S illim anite spark p lu g bodies, w hich illustrate w hy porcelain
‘‘fa tig u es,” losing its ability to w ith sta n d mechanical and heat shocks and w hy S illim anite re
tains its strength. The black spots are holes in the th in speci
m ens.
Left— Crystal o f q uartz in porce
lain cracked by pressure due to unequal expansion.
R ight—A section o f Sillim anite.
Note th e absence o f quartz grains and th e close-grained hom ogeneous structure.
Why Champion
Sillim anite
P a t e n t N o s . 1 4 0 9 9 5 3 , 1 4 3 8 5 9 8 , 1 6 3 1 7 3 0 , 1 6 3 1 6 9 5L a sts Longer.
A
/?esu/fs o f Le C hafe//er¿
¿Fxper'/menfs /n T/?erma /
£xpcrns/orr
TRUE porcelain might for practical purposes be defined as a ceramic product made by mixing together clay, feldspar and quartz (flint) in certain proportions, properly prepared and fired to maturity. Much quartz in the resulting product is not in chemical combination with other ingredients but exists in the free state as crystals scattered throughout a matrix of feldspar and clay. Many of the less desirable properties of porcelain are due to the free quartz grains in the mixture. Quartz possesses the peculiar property of undergoing molecular changes when heated to certain temperatures, accompanied by sharp changes in the coefficient of expansion. These sudden changes in expansion within the porcelain body, set up strains which cause the quartz grains to fracture or break loose from the matrix, thus weakening the structure. Fatigue, as this is called,
results in the sudden cracking of porcelain ware on heating or cooling.
The accompanying graph shows the sharpness of the expansion changes of the various forms of quartz and indicates what may happen for instance when quartz (flint) undergoes a molecular change or inversion into cristobalite or tridymite. When such inversions take place corresponding changes in coefficient of expansion may be so great as to result in severe internal strains in the porcelain body. In connection with spark plug bodies the U. S. Bureau of Standards makes this com
ment: " In either case, volum e changes are unavoida
ble in all porcelains containing free quartz in large a m o u n ts, due to inversions noted. In a good spark plu g porcelain, th e quartz should be elim inated fr o m th e com position and replaced by a substance n o t subject to these inversions.”1
Ceramic ware in which quartz and part of the clay is replaced with “Sillimanite” possesses a constancy in volume on heat
ing, greater resistance to sudden heating and cooling and a striking resistance to mechanical shock. Cham pion
“S illim anite” ware lasts longer and y e t costs no m ore th a n porcelain.
1 J o u rn a l o f A m erican Ceramic Society, Vol. 2, N o . 7, pg. 5Ö2 (19X9).
T e m p e r a t u r e
S I L L I M A N IT E ” m ineralo g ically refers to a g ro u p of m in erals occu rrin g in n a tu re h av in g th e fo rm u la A liO i'S iO a T h e se m in erals a re Sillim an ite, A n d alu site, D u M o r tie rite a n d K y a n ite . T h e end p ro d u c t of Gring A n d a lu site and o th e r “ S illim an ite” m in erals in a ceram ic b o d y is “ M u llite ”
w hich h as th e fo rm u la 3Al»Oj’2SiOi.
1
L a b o r a t o r y Fffiffj S u p p l i e - s A pp aratu s teausjAT.oFE Chemicals
New
Yo r k -B
o s t o n -CHICAG O
- To r o n t o-Lo s An g e l e sJanuary 15, 1933 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 7
KIMBLE EXAX nm GLASSWARE
K I MB L E G L A S S C O M P A N Y , V I N E L A N D , N. J.
New York, Philadelphia, Boston, Chicago, Detroit
A M E R I C A ' S F I N E S T SCIENTIFIC GLASSW ARE
O n e of the outstanding develop
ments in the field of scientific glassware is the new E X A X B L U E L IN E by Kimble. A real achievement— a marked departure— in the fabrication of fine glass laboratory apparatus.
Every graduation line and numeral on this clear crystal glass is filled in with a new B L U E glass enamel, actually fused- in as an integral part or the glassware.
This new B L U E Enamel— more durable than any material hitherto used to fill in graduation marks— is applied by exclu
sive Kimble Process. It contrasts strongly against the crystal glass, making this graduated ware unusually easy to read and accurate in operation.
R ETESTED A N D R E TEM P ER ED
Every piece of Kimble Glassware is retested and carefully inspected against error, blemishes and imperfections.
O n ly perfect, flawless glassware reaches the consumer.
A l l Kimble Glassware is thoroughly retempered in a special lehr or anneal
ing furnace, removing strains and weak spots, and protecting the ware excessive breakage.
The new Kimble Exax B LU E is complete in every detail. It fills long-felt need for accurate,
graduated glassware that is cost and lasting in service.
♦ ♦ ♦
Stocked by leading Laboratory Supply Firms throughout the United States
and Canada.
KIMBLE E X A X
BLUE LINE
for
A s s u r a n c e
8 A N A L Y T I C A L E D I T I O N Vol. 5, No. 1
A copy o f Laboratory V itreosil w ill be gladly sent on request to anyone in a responsible position . Please state professional or business connection.
The THERM AL SYNDICATE Ltd.
62 Schenectady Avenue Brooklyn, New York
Indispensable Publication
F R E E TO Technologists
“L aboratory V itreosil”
has a w ealth of in fo rm a tio n for th o se in te r e s te d in fu se d silica and fused quartz wares. W h ile essen
tially devoted to labo
ratory applications, it also c o n ta in s m u c h useful data for indus
trial purposes.
A m ong the m any helpful sections in this book are those devoted to the nature of Vitreosil; its physical, chemical and electrical characteristics; advantages of Vitreosil over plati
num , porcelain, and glass wares; typical examples of chemical, physical and electrical research, photochemical and u ltra violet applications.
O ther topics include m arking, cleaning and care of Vitreosil and an excellent bibliography is given for those de
siring to m ake a more detailed study of the n ature and uses of
fused silica and fused quartz.
January 15, 1933 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 9
MICROMETER EYEPIECES
FOR LINEAR
MEASUREMENTS FOR A REA
MEASUREMENTS
B & L MICROMETER DISCS
are of £lass 21.3 m m in d iam eter, having lines ruled w ith a diam ond. T h e y fit inside s ta n d a rd eyepieces and are placed scale dow nw ard on th e eyepiece d iap h rag m s w hen in use so as to be in th e focus of th e eye lens.
1859A— R uled to 0.5 m m squares, ev ery second line on tw o a d ja c e n t sides n um bered.
P ric e ... $3.25 1859B— R uled in 1.0 m m squares, every line on
2 a d ja c e n t sides num bered.
P ric e ... $3.00 1859 E— H ow ard M icrom eter Disc, ru le d in
sq u ares eq u al to */$ th e d ia m e ter of th e opening in eyepiece d iap h rag m , for mold counting. P ric e ... $5.25 1859C— W hipple’s eyepiece M icro m eter Disc,
h av in g a large sq u are divided in to four, each of which is subdivided in to 25 squares, a n d one of these again s u b divided in to 25; used for co u n tin g b acteria. P ric e ... $5.25
THE FILAR MICROMETER
are furnished in tw o form s— N o. 1866 w ith a m ovable scale and N o. 1856 w ith a fixed scale, b o th scales m easuring 5 m m . B o th scales are divided in to te n th s of a m m w ith every fifth and te n th line num bered. E y e lens is ad ju stab le for focusing, m agnification 7.5 X .
Price— N o. 1 8 6 6 .. $16.00 Price— N o. 1856. . 7.25
M E C H A N IC A L STAGE
No. 2116 FOR COUNTING
THE H O W A R D M O L D COUNTING CHAM BER
enables th e m icroscopist to m ake m o st acc u ra te m easurem ents and can be a tta c h e d to an y m icroscope.
A m icro m eter screw acts on a slide th a t carries th e m ovable wire.
O ne rev o lu tio n m oves th e wire 1.0 m m across th e field. T h e a d ju st
able d ru m head o f th is screw is d iv id ed in 100 p a rts , 1 p a rt being equal to 0.01 m m . 1 /1 0 o f this in te rv a l (equal to 0.001 m m = lju) can easily be e stim ated . A scale placed in th e field an d ruled in in te rv a ls o f 0.5 m m serves for co u n tin g th e revolutions of th is screw. T h e eyepiece is o f the R am sd en ty p e w ith 12.5 X m agnifi
cations.
P ric e ________$38.00
C onsists of u n ruled a rea 19 m m in diam eter, 0.1 m m in d e p th , surro u n d ed b y a m o at. Slide a n d cover glass surfaces a re o p tically w orked as in blood cou n tin g cham bers. F o r b est re su lts we suggest N os. 1121 (16 m m ) an d 1128 (8 m m ) a p o ch ro m atic objectives a n d N os. 1200 (5 X ) a n d 1208 (15X)_ co m pensating eyepieces. C an be used w ith m icrom eter disc N o. 1859E (see above) for m old counting.
C h am b er only (in case) P ric e ... $7.00
THE RAFTER COUNTING APPARATU S
This stage provides an excellent mechani
cal means for methodical examination of a slide from comer to corner. The clamp is extendable to fit any square stage.
One closed end with clamping screw provides for instant leveling. Rack and
pinion ad ju stm en ts give equal speeds in b o th m ovem ents. R ig h t and left scale reads 75 m m and forw ard an d back scale 45 m m . B o th scales g ra d u a te d in single m m 's w ith verniers a tta c h e d read in g to te n th s. A ccom m odates a n y slide up to 50 m m in w idth.
P ric e ...S30.00
is used for cou n tin g organism s in w ater. I t con
sists of a re c ta n g u lar cell 50 m m X 20 m m 1 m m deep, m icrom eter disc 1859B (see above) th ree cover glasses an d one N o. 15956 p ip e tte 1 cc c ap acity .
Price (c o m p le te ). .$12.00
O t h e r s t o c k a c c e s s o r i e s o r t n o d i f i c a t i o n s o f t h o s e l i s t e d a b o v e a r e
a v a i l a b l e . P r i c e s o n r e q u e s t .
BAUSCH & LOMB O P T I C A L CO.
Bausch & Lomb makes its own optical glass Only B S L glass meets B & L standards.
609 S t . P a u l S t r e e t R o c h e s t e r , N . Y .
M IC R O S C O P E S : TELESCOPES : SPECTACLE LENSES A N D FRAM ES B IN O C U L A R S : O P T H A L M IC AP PA RA TU S : SCIENTIFIC INSTRUM ENTS
STAGE MICROMETERS
(Supplied in lined le a th erette cases)— T hese m icrom eters consist of slides 75 X 25 m m w ith scales ru le d d irectly in th e slide. N o. 1861 is ruled to 0.1 and 0.01 m m . N o. 1862 is ru led to 0.01 a n d 0.001 inches. B o th have cover glasses of N o . 1 thickness.
Price— N o. 1 8 6 1 ... $7.00 Price— N o. 1862. , 8.00
I n c r e a s e the U s e f u l n e s s of Y our M i c r o s c o p e
w ith
B & L M e a s u r i n g A c c e s s o r i e s
10 A N A L Y T I C A L E D I T I O N Vol. 5, No. 1
T he R ig h t B urner F o r T he J ob
H p O O o ften little a tte n tio n has been p a id to selecting th e p ro p e r size an d ty p e o f b u rn e r to p erfo rm th e req u ired h e a tin g jo b q u ickly, efficiently, a n d econom ically.
Because of recent widespread changes in gas service, it is imperative to check up now on the performance of your burners. C heck th em carefully for com plete
ness o f co m bustion, m axim um a tta in a b le te m p e ra tu re , ease o f co n tro l, a n d all-aro u n d flexibility.
A b u rn e r w hich fo rm erly ren d ered efficient ser
vice w ith m a n u fa c tu re d gas m ay be to ta lly u n su ite d to th e m ixed o r s tra ig h t n a tu ra l gas now supplied to so m a n y com m unities.
D u e to its high carb o n c o n te n t, n a tu ra l gas re
quires p rim a ry air in such large p ro p o rtio n s th a t, unless co n tro lled carefu lly , th e flam e is a p t to blow aw ay from th e b u rn er. N a tu ra l gas also, being low in specific g ra v ity , flows th ro u g h a given orifice u n d e r a given pressu re a t h igher velo city th a n gas o f high specific g ra v ity . Unless the burner is of correct design
,
the tendency of the flam e to blow away remains unchecked.A m ong th e dozens of sty les an d sizes o f b u rn ers h an d led by u s, th e re is a ty p e th a t will ex actly m eet y o u r req u irem en ts. W h e th e r it h as fixed or a d ju sta b le orifice, is o f single o r m u ltip le ty p e , for m a n u fa c tu red , n a tu ra l, o r m ixed gas o r for com pressed cy lin d er gases, we can su p p ly it.
A 16-page b ooklet on burners w ill be sen t to in te re sted p a rtie s—on request.
W i l l C o r p o r a t i o n
L A B O R A T O R Y A P P A R A T U S AND C H E M I C A L S
C H E M I C A L ,B I O L O G I C A L ,M E T A L L U R G I C A L AND C L I N IC A L L A B O R A T O R I E S
K
o c i i e s t e r, y . Y
A N A L Y T I C A L E D I T I O N
I n d u s t r i a l
Vo l u m e
5 A N D E N G I N E E R I N G
J a n u a r y15,
N uM BER 1 C h e m i s t r y 1933
Pu b l i s h e d b y t h e Am e r i c a n Ch e m i c a l So c i e t y Ha r r is o n E . Ho w e, Ed i t o r
Reduction of Antimonic Acid in H ydro
chloric Acid Solution with Mercury
L e R o y W. M c C a y , F rick C hem ical Laboratory, Princeton University, Princeton, N. J.
M
cCAY and Anderson (2) have shown th at ferric salts and vanadio acid are completely reduced, the former to the ferrous, the latter to the vanadyl condition, when their hydrochloric acid solutions are shaken for 5 minutes in the presence of mercury. They have also shown th a t chromic, molybdic, and antimonic acids in dilute hydrochloric acid solution are more or less reduced when subjected to a similar treatment.Especially interesting is the behavior of solutions of anti
monic acid in the presence of mercury. The author has made a long and detailed study of this reaction, and has succeeded in establishing the conditions under which the reduction of the element from the quinquivalent to the trivalent state can in all cases be made quantitative.
St u d y o f t h e Re a c t i o n
When a solution of antimonic acid, prepared by oxidizing one of antimonious chloride or sulfate with potassium bró
mate, and containing one-fourth or one-third its volume of concentrated hydrochloric acid (sp. gr. 1.19) is shaken violently for 5 minutes in the presence of mercury, all the antimonic is reduced to antimonious acid:
Sb+++++ + 2C1- + 2Hg = Sb+++ 4- 2HgCl Owing to the air present a small amount of mercuric chloride is also formed:
2HgCl + 2HC1 + O = 2HgCU + H20
If, however, the solution be one of dihydrogen potassium pyroantimoniate, the reduction of the antimony to the triva
lent state is, in the circumstances, never complete. Even when such a solution is heated on the water bath for 15 to 20 minutes, and shaken violently off and on for one hour, quinquivalent antimony can be detected in the filtrate from the mercurous chloride and finely divided mercury. Better results may be obtained by placing the well-stoppered bottle containing the solution and the mercury in a powerful shak
ing machine and agitating it for one hour. While the re
duction here is generally complete, sometimes it is not, for in some instances over a milligram of antimony may remain in the higher state of oxidation. Three very pure samples of the pyro-salt from three well-known houses were used in this work. Their solutions all behaved in an analogous
manner. The qualitative test for minute amounts of quin
quivalent in the presence of relatively large amounts of triva
lent antimony, according to the method of Bunsen, as ordi
narily carried out, is apt to prove misleading (5), for not only does boiled and cooled water acidified with hydro
chloric acid assume in a few minutes a pronounced yellow tin t when potassium iodide, free from iodate, is added to it, b u t when antimonious chloride is also present the addition of the potassium iodide occasions the immediate formation of antimonious iodide, or oxyiodide which gives the solu
tion a faint yellow color. Since, however, acid water alone when saturated with carbon dioxide and kept under an at
mosphere of this gas and in the dark remains colorless or barely yellow for hours after the addition of potassium iodide, satisfactory results were obtained by proceeding as follows: The filtrate from the mercury and mercurous chloride was caught in a little bottle holding about 100 cc.
and provided with a stopper ground so as to furnish an air
tight joint (S). A brisk current of pure carbon dioxide was introduced, permitted to traverse the liquid for ten minutes, a crystal of potassium iodide about the size of a pea was dropped in while the gas was still passing, the de
livery tube was withdrawn, and the bottle was instantly stoppered. Since the amount of antimonious chloride in the filtrate was known within one or two milligrams, 100 cc. of a solution containing this amount of the pure chloride and the specified quantity of concentrated hydrochloric acid were subjected a t the same time to the same treatm ent.
After the bottles had stood for a few minutes in the dark and the colors of the two solutions were compared, th a t of the former appeared the darker if it contained quinquiva
lent antimony. In this way 0.1 mg. of Sbv could be de
tected in the presence of relatively large amounts of Sb1“ . Practically no reaction occurs when water and pure mer
cury are shaken together; the water remains clear and the metal is barely tarnished. If hydrochloric acid be present the liquid remains perfectly clear for 5 minutes, and then becomes suddenly hazy owing to a separation of the highly characteristic silky needle form of mercurous chloride. The amount increases as the shaking is continued, and a t the end of an hour it is comparatively large:
2Hg + O = Hg-0 and Hg20 + 2HC1 = 2HgCl + II20 In an atmosphere of pure carbon dioxide no change occurs, 1
even when the dilute hydrochloric acid and mercury are shaken together for hours.
The mercurous chloride equivalent to the antimonic acid reduced along with th a t formed by the interaction of the mercury and oxygen of the air may be the cause of the per
sistency with which solutions of the pyro-salt resist complete reduction. The globules into which the greater part of the mercury breaks, as well as the rest of the metal, get covered with a protecting skin of mercurous chloride. Of course during the shaking of the contents of the bottle some of these skins are occasionally knocked off, but they im
mediately reform. At all events the reductions in an at
mosphere of carbon dioxide where no additional mercurous chloride can be formed are invariably complete a t the end of an hour’s shaking in the machine. Although this time may seem unnecessarily long it must be borne in mind that, in general, we have no means for knowing offhand the form in which the antimonic acid in a solution is present. We possess, indeed, no definite information in regard to the so- called ortho-, meta-, and pyro-antimonic acids, the methods for preparing them, the circumstances in which they may be converted into one another, and the tests for distinguish
ing between them. For this reason, in the quantitative work which follows, the author has always assumed th at the solutions contained some or all of the acid in the form least easily reduced.
Arsenic and stannic acids in hydrochloric acid solutions undergo no change when shaken for hours in the presence of mercury.
Qu a n t i t a t i v e Re s u l t s
The bottle used in this work is cylindrical in shape, 12 cm. high from the bottom to the shoulder, 6 cm. in diame
ter, and holds about 150 cc. I t is provided 'with a glass stopper which fits air-tight, and it is charged with 20 to 25 cc. of pure mercury. So charged it will be referred to as the reductor. The materials used in preparing the test solutions were the best grades furnished by the Kahlbaum house.
S o l u t i o n A. 2.2063 grams of powdered antimony were treated in a covered dish with 50 cc. of concentrated sulfuric acid which was heated to gentle boiling. When solution was complete the flame of the burner was lowered and the acid allowed to fume strongly for about 15 minutes, so as to get rid of all traces of sulfur dioxide. Water was added, and the turbid liquid was cooled, transferred to a 500-cc. flask, and diluted with concentrated hydrochloric acid and water to the mark.
So prepared the solution contained one-fourth its volume of concentrated hydrochloric acid. The antimony was deter
mined in 25 cc. by the Gyory method. Antimony found equaled 0.1103 gram, whereas the theory calls for 0.1103 gram.
S o l u t i o n B. 8.6444 grams of dihydrogen potassium pyro- antimoniate were dissolved in a liter flask on the water bath in 200 cc. of concentrated hydrochloric acid, water was added, the solution cooled and diluted to the mark with water and con
centrated hydrochloric acid. The solution contained about one-third its volume of this acid. The large amount of acid is necessary to keep the solution clear indefinitely. The antimony in 25 cc. was determined by heating the strongly acidified solution with a large excess of sulfurous acid in a pressure bottle for one hour in the boiling water bath, evaporating the liquid to somewhat less than one-half its volume, cooling it, diluting to
2 0 0 cc., and titrating the antimony with 0 .1 iV potassium bromate.
(The method is similar to that used for reducing arsenic acid solutions, 1.) A blank was made in the same way, using the same amount of sulfurous and hydrochloric acids. After cor
recting for the amount of bromate used in the blank (from 0.15 to 0.2 cc.), the antimony was calculated, and found to be (1) 0.1067 and (2) 0.1068 gram. As a check the antimony was also determined according to an indirect method highly recom
mended by Rose (4), and found to be 0.1067 gram. The element was calculated from the weight of potassium chloride obtained.
The 0.1 N potassium bromate used in the Gyory method was standardized against the Bureau of Standards arsenious
2 A N A L Y T I C
oxide, which was also used in determining arsenic and anti
mony in the presence of each other.
The author has had over three years of experience with the Gyory method, and has no hesitancy in pronouncing it the best of all methods for determining antimony. If plenty of hydrochloric acid be present, the same results are ob
tained when the volume of the solution to be titrated is 50, 100, or 200 cc. In the last case, however, the bromate should be run in a t the rate of 90 to 100 drops a minute, with con
stan t stirring, and, when the methyl orange begins to fade, a drop or two more of the dye added and the bromate from now on introduced a drop a t a time followed by hard and thorough stirring. In this way the end point can be hit with great accuracy. If it be overstepped we can come back with the methyl orange (1 gram in a liter of water) which has been balanced against 1 or 2 drops of the bromate in 200 cc. of water containing one-fourth its volume of con
centrated hydrochloric acid.
L E D I T I O N Vol. 5, No. 1
T a b l e I. D e t e r m i n a t i o n o f A n t i m o n y An t i m o n y Ta k e n
a s Di h y d r o g e n
Po t a s s i u m Py r o- An t i m o n y
ANTIM O NIA TE Fo u n d
Gram Gram
0 .1 0 6 7 0 .1 0 6 7
0 .1 0 6 7 0 .1 0 6 7
0.1 0 6 7 0 .1 0 6 6
0.1 0 6 7 0 .1 0 6 8
0.0 8 5 4 0 .0 8 5 1
0.0 8 5 4 0.0 8 5 2
0.0 4 2 7 0 .0 4 2 7
Convenient amounts of the standard solution were pipetted into the reductor, 15 to 20 cc. concentrated hydrochloric acid were added, and the liquid was diluted to about 75 cc.
(scratch on the side of the bottle above the mercury to indi
cate this volume). The air in the reductor was displaced by introducing a brisk current of purified carbon dioxide gas for ten minutes, the delivery tube withdrawn, and the bottle instantly stoppered and agitated for an hour in the machine. After most of the mercurous chloride and finely divided mercury had settled (before filtering them some of the solutions stood overnight), the solution was poured on to a double filter paper (9 cm.), the filtrate being caught in a 400-cc. beaker. The slate-colored mass in the reduc
tor was washed by letting a 10-cc. pipet full of dilute hydro
chloric acid (10 cc. concentrated hydrochloric acid to 90 cc. water) flow down the inner neck and sides of the bottle, stoppering it, shaking well, decanting the liquid on to the paper, and repeating the operation five times. After rinsing off the stopper, the mouth of the reductor, and the glass rod with a little water, the mercurous chloride and mercury on the filter paper were washed until the washings were neutral. The solution was then diluted to 200 cc. and the antimony titrated. The filtration and washing require ordi
narily about half an hour. The filtrates were always clear.
The material on the filter paper was washed back into the reductor, the liquid, after a few minutes, poured off, and some concentrated hydrochloric acid and from 15 to 20 cc.
of strong stannous chloride solution introduced. On stop
pering and shaking the reductor violently for 2 or 3 minutes all the mercurous chloride is reduced to metallic mercury, which should be washed in the reductor by decantation until the washings are neutral. The reduction and washing are complete in 15 minutes. While washing the reduced mer
cury the author noticed a phenomenon of which he finds no mention. If, after washing is complete, the reductor be filled quite full with water, stoppered, and shaken vigor
ously up and down for about 15 seconds, the metal breaks up into a vast number of globules which form a foam com
pletely filling the upper part of the bottle. The foam, how
ever, rapidly subsides. A few milligrams of soap dissolved
January 15, 1933 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 3 in the water inhibit all tendency on the part of the metal
to foam. I t becomes gray in color, and must be treated again with stannous chloride to show the peculiar behavior.
A little hydrochloric, sulfuric, or nitric acid in the water also precludes the mercury from foaming.
Ta b l e I I . De t e r m i n a t i o n' o f An t im o n y i n t h e Pr e s e n c e o p Ar s e n i c Ac id
A n t i m o n y T a k e n a s D i h y d r o q e n
P o t a s s i u m P y r o a n t i m o n i a t e
Gram 0 .1 0 6 7 0 .1 0 6 7 0.0 8 5 4 0.0 4 2 7
A r s e n i c T a k e n a s D i h y d r o q e n
P o t a s s i u m O r t h o a r s e n i a t e
Gram 0 .0 6 2 5 0.0625 0 .0 6 2 5 0.0625
An t i m o n y Fo u n d
Gram 0.1067 0.1 0 6 8 0.0851 0.0426
Ta b l e I I I . De t e r m i n a t i o n o f An t im o n y i n t h e Pr e s e n c e o f Ar s e n i c a n d St a n n i c Ac id s
An t i m o n y Ar s e n i c
Ta k e n a s Ta k e na s Ti n Ta k e na s
Di h y d r o q e n Di h y d r o g e n St a n n i c
Po t a s s i u m Po t a s s i u m Am m o n i u m An t i m o n y
Py r o a n t i m o n i a t e Or t h o Ar s e n ia t e Ch l o r i d e Fo u n d
Gram Gram Gram Gram
0.1 0 6 7 0.0 6 2 5 0.1 2 9 2 0.1073
0 .1 0 6 7 0.0 6 2 5 0.0 9 6 9 0.1064
0 .1 0 6 7 0.0625 0.0 8 0 8 0.1065
0 .0 8 5 4 0 .0 6 2 5 0.0869 0.0854
0 .0 8 5 4 0.0 6 2 5 0.0808 0.0852
0 .0 4 2 7 0 .0 6 2 5 0.0646 0.0427
If a solution contains antimonious and arsenious acids we may determine the amount of bromate required to oxi
dize both, then evaporate the liquid to about 50 cc., trans
fer it to the reductor, reduce the antimony to the trivalent state, filter, etc., and titrate the antimony. The difference between the amounts of bromate used in the two cases gives th a t used to oxidize the arsenic to the quinquivalent state.
Standard solution A and a 0.1 Ar solution of arsenious acid were employed.
Ta b l e I V . De t e r m i n a t i o n o f Bo t h An t i m o n y a n d Ar s e n ic A n t i m o n y
T a k e n a s A n t i m o n i o u s
C h l o r i d e Gram 0 .1 1 0 3 0.1 1 0 3 0.1 1 0 3 0.1103«
0 .0 8 8 3 0 .0 8 8 3
° C o n ta in ed in a d d itio n 0.4 g ram (N lhJiSnC la
Ar s e n i o u s Ar s e n i o u s
Ox i d e An t i m o n y Ox i d e
Ta k e n Fo u n d Fo u n d
Gram Gram Gram
0.1 2 3 7 0.1109 0.1233
0 .0 9 9 0 0.1109 0.09S5
0.0 4 9 5 0.1104 0.0493
0.0 9 9 0 0.1103 0.0992
0.0495 0.0885 0.0495
0.0 2 4 8 0.0885 0.0248
0.1292 g ram Sn.
The antimony (0.1067 gram) was determined in absolu
tion containing roughly 0.083 gram Pb, 0.213 gram Bi, and 0.123 gram Cd, all as chlorides, and 0.1069 gram of antimony was found.
Ta b l e V . De t e r m i n a t i o n o f An t im o n y i n t h e Pr e s e n c e o f Co p p e r
A n t i m o n y T a k e n a s D i h y d r o q e n P o t a s s i u m P y r o a n t i m o n i a t e
Gram 0 .1 0 6 7 0 .1 0 6 7 0 .1 0 6 7 0 .1 0 6 7 0 .1 0 6 7 0 .1 0 6 7
C o p p e r T a k e n a s C h y s t a l l i n e C u p r i c
S u l f a t e Gram 0.0656 0.0656 0.0 5 2 5 0.0 5 2 5 0.0 3 9 4 0.0262
An t i m o n y Fo u n d
Gram 0.1062 0.1062 0.1064 0.1062 0.1062 0.1061
Cupric salts are reduced by mercury to cuprous salts, the latter being completely reconverted into the former, when a brisk current of purified air is permitted to bubble through their solutions for half an hour. Since trivalent anti
mony alone undergoes no perceptible change when air is passed through its solution, attem pts have been made to determine quinquivalent antimony in the presence of cupric salts by reducing both, oxidizing the cuprous to the cupric with air and titrating the antimony. The results are a trifle low,
a fact which may be due to the oxidation of the cuprous inducing a slight oxidation of the antimonious chloride.
The determination in Table V will indicate the extent to which the results differ from the true values.
A solution (75 cc.) containing 25 cc. of concentrated HC1, 0.1067 gram of Sb as the potassium pyro-salt, 0.0625 gram of As as Hi-KAsOj, 0.037 gram of Pb, 0.086 gram of Bi, 0.059 gram of Cd, 0.057 gram of SnIV, and 0.037 gram of C u", the last five as chlorides, was shaken with mercury for an hour in the machine, in an atmosphere of carbon dioxide.
The filtrate was slightly turbid but became perfectly clear when heated to steaming and stirred a few minutes. When cool, air was passed through it for half an hour and the antimony titrated. Antimony found equaled 0.1061 gram, a result which is practically identical with the average of those given above. If to the volume of 0.1 N bromate used in each of the above cases 0.1 cc. be added, the calculated results are very satisfactory. Experiments are being made to determine whether or not the low results are due to the oxidation of the cuprous to the cupric salt, inducing a slight oxidation of the trivalent antimony.
Su m m a r y
Antimonic acid in hydrochloric acid solution is completely reduced to antimonious acid when the solution is shaken with mercury for an hour in an atmosphere of carbon dioxide.
Arsenic and stannic acids, as well as lead, cadmium, and bismuth, in hydrochloric solution, undergo no change when subjected to similar treatment.
In the same way cupric salts are reduced to cuprous salts, but the latter are selectively reoxidized when pure air is passed through their solutions for half an hour.
Use has been made of these facts in determining anti
mony in the presence of some or all the substances men
tioned. In the case of copper the results are a trifle low.
Li t e r a t u r e Ci t e d (1) M cC ay, L. W., A m . Chem. J., 7, 383 (1 8 8 5 -8 6 ).
(2) M cC a y am i Anderson, J. A m . Chem. Soc., 43, 2372 (1921); 44, 1018 (1922).
(3) M ohr, F ., “T itrirm ethode,” 5to Aufl., S. 253, V iew eg und Sohn, B raunschw eig, 1S77.
(4) R ose, H ., “ H andbuch der an alytisch en Cheraie,” 6 te A ufl., B . II, S. 312, J. A . B arth, Leipzig, 1871; A n n . P h y sik . Chem .,
73, 582 (1848).
(5) Zintl, E ., and W attenberg, II., Her., 56, 1, 474 (1923).
Re c e i v e d S e p t e m b e r 2 3 , 1 9 3 2 .
C o r r e c t i o n . In the article on “Apparatus for Reactions in Liquid Phase at Elevated Temperatures and Pressures” [Ind.
E n q . C h e m ., Anal. Ed., 4, 342 (1932) ], the length of the tubing for the steel spiral referred to in the thirteenth line from the bot
tom of the first column on page 343 should have been given as 4.3 meters or 14 feet. The external diameter of the steel tubing was 6.4 mm. (0.25 inch) and the internal diameter was 1.6 mm.
(0.06 inch). H o m e r A d k i n s
C o r r e c t i o n . In the paper on “Practical Vacuum-Tube Potentiometer for pH Measurement with Glass Electrodes”
[ I n d . E n g . C h e m ., Anal. Ed., 4, 398 (1932)] the values of cer
tain resistors were omitted from Figure 1. Ri is 2000 ohms, R2 is 1000 ohms, R3 is 50 ohms, R< is 500 ohms, and R.> is 10,000 ohms. The resistor shown in the battery-charging circuit has a value of 1000 ohms; the lamp with which this resistor is in series may have a value of 10 to 75 watts (ordinary 110-volt type), depending upon individual tube-filament conditions.
Fr e d Ro s e b u r y
Determination of Total Dissolved Solids in Water Analysis
C. S. Ho w a r d, U. S. Geological Survey, D epartm ent of the Interior, Washington, D. C.
T
H E determination of total solids is one of the oldest determinations in water analysis and has apparently always been taken to represent the amount of material in the water. The difference between the weight of the residue on evaporation of unfiltered and filtered sam
ples of the water has sometimes been taken as a measure of the suspended m atter. The loss on ignition has frequently been taken as a measure of the organic m atter in the water.
Comparison of reported determinations of total solids and loss on ignition with the results of analysis of the actual mineral content indicates, however, th at in some analyses the figures for total solids and for loss on ignition have no real significance.
The determination of total dissolved solids is based on the weight of the residue on evaporation after drying a t a tem
perature of 105° to 110° C. (i, 5) or a t 180° C. (3). The loss on ignition is determined on the residue used for de
termining total dissolved solids by careful ignition over a small flame or in a covered metal dish (4). In calculating the quantity of dissolved material, the figure for bicarbonate is divided by 2.03 to account for conversion to carbonate on evaporation, and the quantities of the other constituents as found by analysis are added to give the quantity of dis
solved mineral m atter. In most water analyses the de
termined figure for total dissolved solids is greater than the sum of the determined constituents, because of the retention of water of crystallization or water of occlusion and because of small quantities of undetermined constituents. In analy
ses of certain types of waters, however, the quantity re
ported for total dissolved solids is less than the sum of the determined constituents because of the volatilization of cer
tain constituents during the evaporation and subsequent drying.
over 5000 made in the W ater Resources Laboratory of the U. S. Geological Survey to represent the different types of water.
Ca r b o n a t e Wa t e r s. N atural waters of the most com
mon type are those in which calcium and bicarbonate are the principal radicals. This type is represented by the first two analyses in Table I. The residues from certain of these waters in which magnesium is small, when dried at 180° C ., represent fairly accurately the dissolved material, as shown by analysis 1. Many waters of this type, how
ever, contain considerable magnesium, and in some of these waters the determined figure for total solids is less than the sum of the determined constituents, as shown in analysis 2.
In over 1000 analyses of waters of this type the determined figure for total dissolved solids was equal to the sum of the determined constituents in 15 per cent, greater than the sum by about 4.1 parts per million in 54 per cent, and less than the sum by about 3.0 parts per million in 31 per cent.
The total solids for the whole group of waters averaged 81 parts per million.
The dissolved material in another large group of waters consists chiefly of sodium and bicarbonate (2). This group is represented by analysis 3, which indicates th a t in a water of this type the determination of total solids, based on the residue dried a t 180° C., agrees well with the sum of the de
termined constituents.
Su l f a t e Wa t e r s. W aters in which sulfate is present in considerable quantities yield residues on evaporation that contain sulfates of calcium, magnesium, and sodium, with water of crystallization. M ost of this water is driven off from the sulfates of sodium and magnesium when the resi
due is heated a t 180° C ., but this temperature is not sufficient to dehydrate calcium sulfate completely. Waters of this
T a b l e I. M i n e r a l C o n s t i t u e n t s o f N a t u r a l W a t e r s To t a l Di s s o l v e d
So l i d s Fi x e d
SiOj Fe Ca M g N a K
Pnrt'r
H C O j SO4 Cl NO» AT 180° C. Sum R e s id u e 42 Color
1 7 .9 0 .0 7 52 5 .0 2 .4 1 .7 178 3 .9 1 .8 0.20 165 163 164
2 9 .0 0.02 32 15 2 .6 1.3 171 2 .7 2 .6 0 .5 3 137 150 133
3 16 0 .0 7 5 .3 3 .9 141 3 .2 388 5 .0 12 1 . 1 382 378 379
4 13 0 .0 8 113 29 97 — 3 .9 186 407 23 7 .3 811 785 774
5 30 0 .1 2 184 29 127 214 48 454 1.0 1076 979 1049
6 17 0 .0 3 68 19 19 4 .7 239 19 29 50 331 343 297
7 6 .3 0 .0 6 17 2.6 1.3 0.8 58 8 .2 O.S 0 .1 0 67 66 63 ’ 5
8 6 .0 0.0 1 5 .2 1 .7 5 .7 1.4 13 2 .3 10 T race 66 39 51 200
° F ig u re o b ta in e d b y s u b tra c tin g loss o n ig n itio n from figure for to ta l solids.
1 . A llan Springs a t P rice, A la., 1928. 5.
2. S pring a t Village S prings, A la., 1928. 6.
3. W ell, 28 feet deep, a t H en d erso n v ille, P a ., 1926. 7.
4. San J u a n R iv e r n e ar B luff, U ta h , average, 1931. 8.
W ell, 162 fe e t d eep , a t S t. P e te rsb u rg , F la ., 1923.
W ell, 24 fe e t deep, a t B arto n sv ille, F la ., 1931.
C o w p astu re R iv er a t C lifto n Forge, V a., 1930.
N o rtn F o rk of B lack C reek, M id d leb u rg , F la ., 1924.
N atural waters contain varying quantities of silica and the carbonates, sulfates, chlorides, and nitrates of calcium, magnesium, sodium, and potassium. For most waters it is assumed th at the silica is present in the colloidal condition and after evaporation is present as SiOs, although in certain waters, especially some from volcanic regions, the silica in the residue is in combination with the basic elements. N atu
ral waters can be grouped for study according to the pre
dominating acid radicals and in this paper are discussed under four groups— carbonate, sulfate, chloride, and ni
trate waters. The analyses in Table I were selected from
type are represented by analysis 4 in Table I. A great many waters high in sulfate carry enough chloride to affect the relation between the weight of the residues and the amount of dissolved material.
Ch l o r id e Wa t e r s. N atural waters containing large quantities of chloride also generally contain considerable calcium and magnesium, and the residues from these waters are wreighed with difficulty because of the presence of calcium and magnesium chlorides. The determined quantity of dis
solved solids in practically all waters of this type is con
siderably greater than the sum of the determined constitu- 4
