676 INDUSTRIAL A N D ENGINEERING CBBMISTRY
T h e Manufacture of Sodium Hyposulfite’
By L. A. Pratt
MERRIIACCHEMICAL CO.,
T HE use of sodium hyposulfite as a reducing agent in
the application of dyestuffs has made this product of
unusual importance. The manufacture of hyposul-
fite in the form of a 10 to 12 per cent solution is easily effected
by treating a solution of sodium bisulfite with powdered
zinc or by passing sulfur dioxide gas (free from oxygen) into
water containing powdered zinc in suspension. The zinc
hyposulfite thus formed is converted into the sodium salt by
the addition of soda ash. Many concerns employing large
amounts of hyposulfite produce their requirements by one
or the other of these two methods. The solution formed in
this manner has the disadvantage of being unstable and must
be prepared only in sufficient quantity for immediate use.
The stable anhydrous sodium hyposulfite powder has be-
come a popular commodity because of its convenience and
high strength. Its manufacture is accompanied by diffi-
culties, however, and requires a considerable plant investment.
The process of manufacture may be briefly described as fol-
lows :
GASSING
Finely powdered zinc testing 93 per cent Zn or better is
suspended in water in a lead container equipped with means
for cooling and a stirrer or pump for agitation. Liquid
sulfur dioxide contained in a weighing cylinder is gasified and
passed into the lead container through a distributor located
near the bottom of the apparatus. The gas can be passed
rapidly at first, although it is best not to allow the tempera-
ture to rise above 30” C. As the reaction proceeds the rate
at which the gas is passed must be progressivelydecreased.
The amount of sulfur dioxide employed is weighed for the
purpose of following a definite rate schedule, but the exact end
point is determined by the color of the solution. The color
changes from that of metallic zinc in the beginning to black,
then to gray, and finally to cream. A yellow color must be
avoided, as it indicates decomposition of zinc hyposulfite
into free hyposulfurous acid, which is very unstable. The
time required for the “gassing” with sulfur dioxide depends
upon the particular design of the apparatus employed, but
in the plant being described is from 3 to 4 hours.
1 Presented before the Division of Dye Chemistry a t the 67th Meeting
of the American Chemical Society, Washington, D. C , ApriI 21 t o 26, 1924.
WATER- - A
Vol. 16, No.
BOSTON, MASS.
SODATION
The zinc hyposulfite solution is rapidly pumped to a lead-
lined steel tank provided with a stirrer, and a previously pre-
pared sodium carbonate solution is added in slight excess
over the amount necessary to precipitate the zinc. The
solution and the suspended zinc carbonate are dropped upon
a suction filter located directly below the “sodation tank.”
If the precipitation has been carefully carried out, the filtra-
tion proceeds rapidly. The cake is washed with a small
amount of water to replace the strong sodium hyposulfite
liquor and the combined filtrate, and wash water is pumped
to a calibrated tank called the “salting-out tank.” The
zinc carbonate cake is subsequently washed more thoroughly
and the wash water is employed in the next batch.
S a L T I N G OUT
This operation is carried out in a jacketed steel tank
equipped with a stirrer. The volume of the solution in the
tank is noted and a sample taken for analysis. The solution
should contain about 15 per cent sodium hyposulfite by weight.
A good grade of salt (NaC1) is added to the salting-out tank
in an amount corresponding to 0.29-0.30 kg. for each liter
of solution. The hydrated crystals of sodium hyposulfite
(Na&04.2HzO) separate from the solution as the salt dissolves.
The mass is then heated rapidly to 60’ C. and the tempera-
ture maintained at this point until all the crystals have
changed to the anhydrous form (Xa2S201). This point may be
easily determined by examination of a sample withdrawn
in a large test tube. The hydrated crystals are small needles
which remain suspended for some time in the solution,
while the anhydrous form consists of heavy, sandy crystals
which settle out rapidly. When the change has been effected
the temperature is lowered to 55” C. and the stirrer is stopped
to allow the crystals to settle. The transition of hydrated
crystals to anhydrous crystals is 52” C., and it is best not to
drop the temperature quite to this point. The supernatant
liquor is siphoned off, and hot denatured alcohol is added to
the salting-out tank. The alcohol and hyposulfite crystals
are agitated for several minutes by means of the stirrer and
then dropped through the bottom outlet into the drier.
m
July, 1924 I S D U S T R I A L A N D ENGINEERIXG CHEMISTRY
DRIER
A Buffalo cast-iron, vacuum crystallizing panis employedfor
the drying operation. A high vacuum is important in order
to avoid loss by decomposition. As soon as the crystals have
settled, the hot alcohol wash is siphoned off and a second and
third hot alcohol treatment is given the crystals. After
each alcohol addition the stirrer is started and the contents
of the drier are thoroughly agitated. The crystals are al-
lowed to settle and the alcohol siphoned off as in the case of
the first wash. The drier is then closed, the stirrer placed
in motion, and the vacuum applied. Low-pressure steam
(5 pounds) is admitted to the jacket and the drying proceeds
until no alcohol is seen in the sight glass beyond the condenser.
At this point the temperature in the drier is about 90" C.
and the material has become somewhat dusty. The steam
is turned off and cooling water circulated until the product
677
has been cooled to 40" C. or lower. The vacuum is then
released and the contents of the drierare discharged into s h i p
ping containers and sealed. The product is a light gray,
sandy material testing 85 to 90 per cent Na&04.
Special precautions must be taken to avoid alcohol losses in
the recovery and rectification.
The mother liquor from the salting-out process contains
considerable sodium hyposulfite and must be further treated,
if the highest efficiency is to be obtained.
Ac KN OWLED GB.IENT
The writer acknowledges his great indebtedness to his
colleagues in the Research, Engineering, and Manufacturing
Departments of the Merrimac Chemical Company who played
an important part ip the development of the process which
has been described.

T h e Microchemistry of W h i t e Pigments and Inerts as T h e y

Occur Mixed in Paints'
By Henry Green
N G W JERSEY ZINC c o . , PALMERTON, PA.

HE development of a A microchemistry of pigments is helpful in making paint analyses, be found in the literature,Z

T rnicr o c h e m i s t r y of
p a i n t pigments is
justifiable for a t least two
and also in studying the nature of complex pigments, such as litho-
pone and leaded zinc oxides.
I n this paper are described the mefhodsfor the necessary prepara-
but the best plan for the be-
ginner who wishes to iden-
tify pigments with the mi-
reasons: first, it is an aid tion of the sample for analysis; microchemical tests on individual croscope is to mount them
to the paint chemist in pigments; and a scheme for the qualitatioe determination (by the use and examine for himself as
making paint analyses; and of the indioidual tests) of the components of a theoretical mixture of many different specimens as
second, it is invaluable to all the white .Digments
- and inerts ordinarily found in paints. he is able to secure.
the pigment chemist for I n pigment microchm-
studying the nature of com- istry tests are made for the
plex pigments, such as lithopone and leaded zinc oxides. pigments themselves and not for their component parts, thus
The microscopist who has studied the sizes and shapes making it somewhat distinctive from the usual form of micro-
of various pigment particles finds no great difficulty in iden- chemistry. For instance, tests are made for basic lead carbon-
tifying a pigment if it occurs alone, but an entirely different ate or basic lead sulfate and not for Pb, COZ, or SOa. The pig-
state of affairs arises when mixtures of pigments must be ments must not be destroyed by solution unless it is desired
considered, as is usually the case in paints. to eliminate them, as explained further on.
If we are working with a mixture that contains but two Since this is perhaps the first attempt to formulate a micro-
pigments, say, in the proportion of 50 per cent of one to 50 chemistry of pigments, this paper will necessarily be of an
per cent of the other, then it is often easy to identify each elementary nature and, no doubt, somewhat unsatisfactory
pigment by simple microscopic inspection, without resorting as far as completeness is concerned. For instance, though
to microchemistry; but if the mixture should be 95 per cent it is possible to detect ultramicroscopic layers of zinc oxide
of one and 5 per cent of the other, then the 5 per cent ingredient on the surface of lithopone particles, yet no methods exist
is likely to be overlooked, unless it possesses an unusually large for the detection of layers of moisture, adsorbed gascs, and
percentage of characteristic particles. water-soluble salts. There are also a few combinations of
Microscopically, a pigment is composed of two kinds of pigments (and also inerts) which are practically impossible
particles-one, characteristic, and the other, characterless. t o analyze microchemically. Notwithstanding these short-
The chitracteristic particles serve as earmarks for the identi- comings, however, the subject is sufficiently far advanced
fication of the pigment to which they belong. The character- to be useful as it is.
less particles are small and roundish, and in appearance very
much the same in all pigments. Consequently, if a mixture (a) PREPARATORY PROCESSES
contains but a small percentage of one pigment, then the Four preparatory procesqes are necessary (as a rule) for
number of characteristic particles of that ingredient present a complete analysis :
will be so few that they might not be found under the micro- 1-The removal of the vehicle from the pigment of a paint.
scope, and so the pigment remains unidentified unless the Place on a microscope slide a small drop of the paint to be
investigator resorts to microchemical means. examined. Add to it a drop or two of redistilled turpentine
Descriptions of some of the characteristic particles can and rub out, with a glass rod, to a thin, even layer extending
1 Presented under the title "The Microscopy of White Pigments as from one end of the slide to the other. Place the slide on
They Occur in Paints," before the Section of Paint and Varnlsh Chemls- a hot plate (about 150" C.) and evaporate the turpentine.
t r y a t the 67th Meeting of the American Chemical Society, Washington,
D. C., April 21 to 26, 1924. 2 Green, Chem. Met. Eng., 28, 53 (1923).