398 T H E J O U R N A L OF IiVDCSTRIIIL A N D E N G I N E E R I N G C H E M I S T R Y Vol. 6 , NO.

t a i n mixtures of coke oven t a r oil a n d water gas t a r sulfocyanate. Transfer t h e filter paper a n d precipi-
oil would show a lesser residue t h a n certain other oils t a t e t o a 2j0 cc. stoppered flask. Wash out t h e pre-
obtained wholly from gas works coal tars. cipitation vessel with 4 0 t o j o cc. of a cold solution
I n conclusion, t h e authors believe t h a t t h e sulfon- of hydrochloric acid ( I vol. conc. BC1 t o 2.5 vols. water)
ation test in itself has been shown t o be of comparatively a n d transfer t o t h e flask with t h e main portion of t h e
little value i n detecting t h e admixture of oils of petro- precipitate. Add 3 t o j cc. of chloroform t o t h e above
leum origin, particularly those derived from water solution a n d titrate at once with t h e standard ammo-
gas t a r , with creosote oil. nium sulfocyanate t o t h e first violet which remains
I n a later paper, we hope t o publish additional d a t a in t h e chloroform after vigorous shaking. For ores
from our analyses of authentic tars, indicating t h e high in lead i t is advisable t o a d d t o t h e flask before
value of certain other tests as means for determining t h e end point is reached I O t o ~j cc. of cold HC1 (1.1
t h e origin of oils used for creosoting. sp. gr.).
RESEaRCH DEPARTMENT
LABORATORY XOTES O N THE DETERNINATION
BARRETTMAXUFACTURINGCOMPANY
NEWYORK CITY T h e above method was tested o u t with purified lead
sulfate a n d gave t h e following results:
A VOLUMETRIC METHOD FOR THE DETERMINATION G. PbSOa G. P b in G. P b G. PbSOi G. P b in G. P b
OF LEAD taken PbSOa found taken PbSOa found
By ALFREDALDERA K D M. F COOLB.4L?G€I
0.3 0.2049 0.2047 0.3 0.2049 0.2046
0.3 0,2049 0,2038 0.3 0.2049 0.2044
Received February 16, 1914 0.3 0.2049 0.2056 0.3 0.2049 0,2045
T h e principles of t h e determination are based upon 0.3 0.2049 0.2052 0.4 0.2732 0.2728
0.3 0.2049 0.2049 0.2 0.1366 0 . I369
t h e precipitation a n d separation of t h e lead as sulfate, 0.3 0.2049 0.2051 0.1 0.0683 0.0684
t h e solution of this precipitate in sodium hydroxide 0.3 0.2049 0.2049
a n d t h e precipitation of t h e lead from t h e solution,
after slightly acidifying i t with nitric acid, by a solu- A number of ores were r u n by this method using
tion of potassium iodate. T h e precipitate of lead 0.j gram samples for t h e determinations. T h e lead
iodate is dissolved in dilute hydrochloric acid. It in these ores h a d been previously determined b y a
is t h e n t i t r a t e d in t h e presence of a few cubic centi- careful analysis, weighing up t h e lead as t h e sulfate.
meters of chloroform, with a standard solution of a m - T h e followihg are some of t h e results obtained:
monium sulfocyanate t o t h e first appearance of a Lead by Lead b y
violet color i n t h e chloroform. PbSOa method iodate method
No. ore Per cent Per cent
T h e outline scheme for t h e analysis of a n ore is as
I..................... 3 18 3.26
follows: T r e a t 0.j t o I g r a m with nitric acid, a n d , if 2.. . . . .. . . . . . . . . . . . . . . . 4.20 4.18
necessary, with a small quantity of hydrochloric acid. 3 . . . . . . . . . . . . . . . . . . . . . . 4.42 4.37
4 . . . . . . . . . . . . . . . . . . . . . . 50.51 50.6
T h e n a d d a few cc. of sulfuric acid a n d evaporate t o 5 . . . . . . . . . . . . . . . . . . . . . 64.39 64.27
dense fumes of sulfuric anhydride, leaving n o t more
t h a n 2 t o 3 per cent of free sulfuric acid present when Ammonium acetate, sodium acetate a n d potassium
t h e solution is diluted t o I O O cc. Cool t h e thoroughly hydroxide, as well as t h e sodium hydroxide were used
decomposed material a n d a d d a b o u t I O O cc. of water, in t h e solution of t h e lead sulfate obtained from t h e
bring t o a vigorous boil a n d a d d I O t o 1 5 cc. of alcohol. decomposition of t h e ore, or t h a t which was used as
Cool a n d allow t o s t a n d until t h e precipitate has com- t h e standard. F r o m t h e ammonium acetate or sodium
pletely settled, a n d t h e n decant upon a filter paper acetate solutions, either neutral or acid with acetic
a n d wash t h e residue with a mixture of I per cent acid, t h e lead iodate precipitated slowly a n d incom-
sulfuric acid a n d I O per cent alcohol, a n d finally with pletely. Boiling, long standing a n d a decided excess
t h e alcohol alone. Dissolve t h e lead sulfate in a small of potassium iodate tended t o make t h e precipitation
q u a n t i t y of h o t sodium hydroxide ( I O t o I j cc. of a complete, b u t under most careful conditions gave quite
I O per cent solution will usually be sufficient). Kash decidedly low results. T h e potassium hydroxide gave
t h e residue a n d filter paper thoroughly with hot water, equally as good results as t h e sodium hydroxide. It
followed b y h o t water slightly acidified with nitric acid is difficult t o wash t h e filter paper free from t h e solu-
a n d finally b y wetter slightly alkaline with sodium tion obtained by t h e t r e a t m e n t of t h e lead sulfate with
hydroxide. Add a few drops of phenolphthalein t o t h e sodium hydroxide. Experiments gave results as
t h e solution a n d a q u a n t i t y of potassium iodate so- much as I O per cent low. This difficulty is corrected
lution sufficient t o precipitate all of t h e lead a n d have b y washing with dilute nitric acid followed b y washing
a small a m o u n t in excess. Heat t h e solution, a n d while with a dilute solution of sodium hydroxide.
hot a d d nitric acid (1.2 sp. gr.), drop b y drop, until T h e solubility of lead iodate is given as 0.012 g r a m
t h e pink of t h e phenolphthalein is discharged, a n d t h e n in a liter of water a t 2' C. a n d 0.019 gram in a liter
I j t o 2 9 drops in excess. Bring t h e whole t o a boil, of water at 18' C. (Kohlrausch a n d Bottger). I t
cool slightly, a d d 1 5 t o 20 cc. of alcohol a n d t h e n cool is stated t h a t its solubility in nitric acid is only slight,
t o room or t a p water temperature. Decant t h e so- some authorities going so far as t o say t h a t i t is in-
lution through a filter paper a n d wash b y decantation soluble in hot dilute nitric acid. Experiments were made
with one p a r t of alcohol t o three parts of water until t o test this point. T h e precipitates of lead iodate
t h e wash solution gives no test for iodate when treated were washed with h o t dilute nitric acid a n d t h e lead
with hydrochloric acid, chloroform a n d ammonium content determined. T h e same was repeated using
M a y , 1914 T H E J O L T R N A L O F I , l T D C S T R I A L A N D ENGI;VEERI,VG C H E M I S T R k '
t h e cold dilute acid. T h e following are a few of t h e
results obtained:
Lead taken 0 2049 gram
Lead found 0 1969. 0 1995, 0 1957 a n d 0 1911 gram
When water was used t o wash t h e precipitate, low
results which would not agree with each other were
obtained. I n washing with nitric acid or water, t h e
wash water could not be freed from iodate as given
b y t h e test with hydrochloric acid, chloroform a n d am-
monium sulfocyanate. T h e solubility of t h e lead
iodate in dilute " 0 3 with a slight excess of potassium
iodate a n d alcohol present was shown b y evaporating
t h e filtrates from seven solutions o u t of which t h e lead
h a d been precipitated as iodate according t o t h e out-
line scheme. T h e original solutions contained 1 . 7
grams of lead. T h e solutions which were evaporated
were fumed with H 2 S 0 4 a n d t h e lead determined as
sulfate according t o t h e regular method: T h e amount
of lead sulfate found was 0.6 mg.
If lead iodate is precipitated in t h e cold i t comes
d o x n in a flocculent form a n d is not readily purified.
Unless a n extra amount of time is t a k e n in t h e mashing
t h e results will be high, due t o t h e retention b y t h e pre-
cipitate of some of t h e excess of potassium iodate.
ST'hen t h e lead is precipitated h o t , or boiled after pre-
cipitation i t comes down with a coarsely crystalline
structure. T h e precipitate settles rapidly a n d is
readily purified from t h e excess iodate. F o r t y t o fifty
cc. of t h e alcoholic solution have proved ample for
washing, even when 0 . 2 j gram of lead i n t h e form
of iodate was being treated. Too much alcohol added
t o t h e solution a t t h e precipitation of t h e lead iodate,
or too strong a n alcoholic solution used for washing
purposes will make t h e removal of t h e excess of potas-
sium iodate difficult, since this substance is much less
soluble in alcohol t h a n in water. Too much potassium
iodate should not be added in excess because of t h e
expense of t h e reagent, a n d t h e added difficulty of
washing i t o u t . It is i m p o r t a n t t h a t t h e solution from
which t h e lead is precipitated as iodate should be made
distinctly acid with H N 0 3 , otherwise some lead will
be present as t h e hydroxide a n d t h e results mill be low.
Lead iodate is decidedly soluble in a n excess of a fixed
alkali hydroxide.
T h e lead iodate is soluble in dilute cold hydrochloric
acid without t h e decomposition of t h e iodate radical.
If t h e hydrochloric acid is concentrated or t h e dilute
solution h o t , chlorine will be liberated a n d t h e iodate
radical decomposed. This reaction can possibly be
represented b y t h e following equation:
12Hcl + Pb(IOz)* = 8C1 + 2IC1 + PbClz + 6Hz0
Whenever chlorine is liberated, t h e determination is
ruined since t h e results will be decidedly low. T h e
strength of hydrochloric acid used in t h e outline scheme
will not liberate chlorine unless t h e solution is hot.
T h e reaction between t h e lead iodate a n d t h e N H l C N S
is most rapid when t h e iodate' is completely in solution.
If, after t h e titration has been started, i t is noticed
t h a t some of t h e iodate is not in solution, i t is best t o
a d d more of t h e hydrochloric acid. T h e reaction of
titration is:
399
3Pb(IO3)2 + 4 S H d C K S + 12HCl = 6IC1 + 3PbC'12
+ 4 N H 4 C l + 4H2SOe + 4 H C S + zH?O
T h e end point is caused b y t h e liberation of t h e I from
t h e IC1 a n d its absorption in t h e chloroform. The
equation for t h e end point is probably t h e following:
6IC1 + SHdCNS + 4H20 = 61 + "4'21 + H:SOd
+ 5HCl + H C N
When sufficient hydrochloric acid is present t h e re-
action of titration is a very rapid one, a n d t h e end point
very sharp a n d distinct, leaving nothing t o be desired
in t h a t direction. T h e approach t o t h e end point is
indicated by t h e rapidity of t h e discharge of a yel-
lowish red color throughout t h e solution. T h e end
point can, in fact, be determined quite closely even
without t h e use of chloroform, b y t h e permanent for-
mation of this yellowish red color. The chloroform
can be used over again b y decanting off t h e larger por-
tion of t h e filter paper pulp a n d solution a n d then
adding t h e precipitate from another determination.
T h e ammonium sulfocyanate is made by dissolving
about 2.5 grams of t h e pure salt in a liter of water a n d
t h e n standardizing i t according t o t h e well known
Volhard method for silver b y titrating a known silver
nitrate solution which has been made b y dissolving
pure silver in nitric acid a n d boiling off t h e nitrous
fumes. T h e silver standard of t h e ammonium sul-
focyanate multiplied by 1.4398 gives t h e lead standard.
T h e N H 4 C N S m a y also be standardized b y titration
against c. P. lead sulfate or metallic lead. The above
strength of solution will equal a b o u t I per cent of lead
for each cubic centimeter when 0.j gram sample is
taken for analysis.
T h e elements encountered in t h e ordinary ore analysis
which might interfere with t h e determination of t h e
lead b y giving insoluble iodates are barium, calcium,
copper, silver, bismuth, mercury a n d ferric iron. Of
these only t h e barium, calcium, silver a n d bismuth
are likely t o interfere since t h e copper a n d mercury
can be completely removed a n d t h e ferric iron nearly
removed from t h e lead b y filtering t h e m off from t h e
insoluble lead sulfate formed in t h e decomposition of
t h e ore. T h e solutions must contain calcium in rather
large concentration before this element will precipitate
as iodate under t h e conditions given for t h e lead de-
termination. I n no experiment tried was i t found t o
interfere with t h e accuracy of t h e method for lead.
Barium forms a n insoluble iodate which is slightly
soluble i n dilute nitric acid, b u t barium sulfate is not
affected b y sodiuni hydroxide a n d only very slightly by
dilute nitric acid, so t h a t not enough of i t is carried into
solution t o be precipitated as t h e iodate. Experiments
with these .two elements show their influences upon
t h e determination.
G. PbSOa G. B a s 0 4 G. CaSOi G. P b in G . Pb
taken taken taken PbSOI found
0.3 0.1 . . 0.2049 0,2052
0.3 0.2 ... 0 , ?0#9 0.2046
0.3 0.2 0.I 0,2019 0.2042
It is difficult b y t h e ordinary methods of treatment
t o remove all t h e silver a n d bismuth from t h e insoluble
400 T H E JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
lead sulfate precipitate. These elements form, when
treated with sodium hydroxide solution, insoluble
silver oxide a n d bismuth hydroxide which are readily
soluble in dilute nitric acid. T o keep these from going
in with t h e lead solution, a n d a t t h e same time t o purify
t h e filter paper from t h e lead, it was found necessary,
after t h e filtration of t h e solution obtained by t h e
t r e a t m e n t of t h e lead sulfate with t h e sodium hydroxide,
t o remove t h e filtrate a n d t r e a t t h e residue a n d filter
paper with hot water slightly acidifie‘d with nitric acid.
The filtrate obtaine’d by this treatment is made quite
strongly alkaline with sodium hydroxide a n d filtered
through t h e same filter paper. From t h e combined
filtrates t h e lead iodate is precipitated. The following
experiments show t h a t these elements, when t h e treat-
ment is made according t o t h e above modifications of
t h e outline scheme, have no effect upon t h e accuracy of
t h e results. Ferric iron is not readily precipitated
as t h e iodate in presence of nitric acid also has no
effect upon t h e results.
G . PbSOa G . AgpS04 G. Fe:(SOi)a G. BiZ(SO1)a G. P b in
taken taken taken taken PbSOl
0.3 0.1 ... 0.1 0.2049
0.3 0.1 ... 0.1 0.2049
0.3 ... 0,015 ... 0,2049
T h e determination of lead in a n ore by this method
can be made in 4 j minutes t o one hour’s time. The
cost of t h e reagents in t h e determination is not ex-
cessive, a n d should not exceed a few cents per deter-
mination when 0 . ; t o I gram samples are used. For
low-grade lead ores t h e cost is materially reduced be-
cause of t h e smaller quantity of potassium iodate re-
quired. Some of t h e advantages of, t h e determinations
are rapidity of manipulation, definiteness of t h e re-
actions of titration, non-interference of t h e elements
usually associated with lead minerals a n d exactness of
t h e end point.
SOUTH
DAKOTASTATESCHOOLOF M I N E S
RAPID CITY
THE D E T E R M I N A T I O N O F ARSENIC I N HYDROCHLORIC
AND SULFURIC ACIDS
By R. F. TARBBLI.
Received January 22, 1914
I t is always necessary in the manufacture and
purchase of hydrochloric a n d sulfuric acids t h a t are
t o be used in t h e preparation of food products to make
some sort of test t o determine t h e percentage of
arsenic present.
T h e writer has worked out a method which he has
found very satisfactory a n d accurate. Once the ap-
paratus is set up a n d the standard solutions and reagents
prepared, a determination requires very little a t t e n -
tion.
P R I N C I P L E S IN V 0 LT‘E D
It is well known t h a t arsine and iodine react t o -
gether under certain conditions forming arsenious
iodide. This reaction seems t o hold when t h e iodine
is dissolved i p specially prepared gasoline. I n t h e
following method arsine is generated in the usual way,
passed through a solution of lead acetate t o remove
a n y hydrogen sulfide formed a n d then passed through a
Vol. 6, No. 5
known volume of a n iodine-in-gasoline solution of
known strength. The excess of iodine is reduced b y
adding a known amount of a sodium arsenite solution
a n d then titrated back with a n iodine solution using
starch as indicator. The writer has found t h a t b y
this method one atom of arsenic is equivalent t o eight
atoms of iodine. This would correspond t o t h e fol-
lowing equations:
AsH3 +
31z = As13 3HI +
2ASI3 +
3 H 2 0 = As203 6HI +
.%Szo3 212+ +
zH20 = As205 4HI +
APPARATUS
A train is connected as follows: A j o o cc. flask
is fitted with a two-hole rubber stopper. Through
one hole in t h e stopper is fitted a 12: cc. globe-shaped
separatory funnel turned up a t its lower end t o prevent
t h e escape of gas. Through t h e other hole is fitted a
Kjeldahl connecting bulb. This is in t u r n connected
with a Koeninck’s potash bulb. The potash bulb is
next connected t o a single bulb such as always comes
G. P b
found with a n d precedes a Lleyer’s bulb tube. T o this is
0.2047 connected a Meyer’s bulb tube. There should be a t
0.2043 hand a 5 0 0 cc. Squibb’s pear-shaped separatory funnel.
0,2051
R E A G E N T S AND STANDARD SOLUTIONS
Gasoline--A quantity of gasoline is prepared from
ordinary 60’ gasoline in t h e following way: Fill
a gallon bottle three-fourths full of the gasoline a n d
a d d zoo cc. c. P. sulfuric acid. Stir this eight or
t e n hours with air, let settle, pour off t h e gasoline i n t o
a similar bottle, a d d 2 0 0 cc. c . P . sulfuric acid a s
before a n d let s t a n d several days with occasional
shaking. Pour t h e gasoline from t h e acid, a d d a
dilute solution of sodium hydroxide a n d agitate ten or
fifteen minutes t o neutralize all acid. Wash gasoline
with water, let settle, a n d when clear it is ready for
use.
Sta?zizous Chloride Solution-Dissolve z j grams
c. P . tin in arsenic-free hydrochloric acid a n d evaporate C
almost t o dryness. Take up with water a n d make up
t o 5 0 0 cc.
Arsenic-free Hydrochloric Acid-Dilute C . P . hy-
drochloric acid t o sp. gr. I . i o , a d d a small amount of
either copper sulfate or mercuric chloride and pre-
cipitate with hydrogen sulfide. Let s t a n d four or
five days, filter a n d distil.
Alkaline Sodium Arsertite Solutioiz-Dissolve 0.2640
gram pure arsenious oxide a n d I gram sodium car-
bonate in I O O cc. hot water. After cooling, a d d I
gram sodium bicarbonate and make total volume I
liter with water.
Iodine Solutioit-Dissolve 0 . 6 7 7 3 gram pure iodine
and i . 2 grams potassium iodide in water a n d make
t h e volume up t o i liter.
I o d in e- iIZ - C: .Is ol in e S o l z ~i of iz- Dissolve 0.6 7 7 3 gra m
pure iodine in the prepared gasoline and make t h e
volume up t o I liter with gasoline.
Zinc-Use c. P. arsenic-free stick zinc.
METHOD O F ANALYSIS
Fill t h e potash bulb with lead acetate solution t o t h e
top of t h e first bulb. P u t 2 0 cc. iodine-in-gasoline