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tion is much less. R sulfuric acid pump1 was used in the distillation in
order that during this process the pressure might be kept a t a minimum.
Fig, I is drawn to scale, and shows thc relative sizes of Distiliing Plask
B,Receiver G and barrel of sulfuric acid Pump M. The volume of the
latter is some 6 liters, this being more than 3 times the volume of all.
the rest of the apparatus to be evacuated. The sulfuric acid pump is
regulated by a control valve2 leading to J, 0 being connected to a Geiss-
ler water-pump, 0 N acting as a sulfuric acid seal. The reservoir K is
filled with commercial sulfuric acid (95(JO), one filling being sufficient
far innumerable distillations. D is a water condenser and is connected
Fig.. I .
After many attempts to obtain pure hydrogen peroxide from the 90%
solution by crystallization, the following technique was devised. 1100g.
of solution was placed in a large tube which was itself placed in a cooling
mixture in a Dewar flask. A continuous stream of dried air was sent
through a glass tube of small diameter leading through its cooling mix-
ture to the bottom of the solution. The latter was thus kept stirred.
The temperature indicated by a thermometer was then regulated to
be one degree below the freezing point of the so1ution.l The latter was
then inoculated with a crystal of hydrogen peroxide, and the temperature
of the cooling bath was lowered until half the solution had solidified;
the solution being stirred vigorously during this procedure. The crys-
tals were finally allowed to settle, the supernatant liquid poured o
the crystals and absorbed liquid transferred to another glass tube per-
forated by fine holes in the bottom. The transference was effected in a
few seconds, crystals adhering to the side of the first test-tube having
been melted by the warmth of the hand. The crystals were pulled out
by a glass rod with a hook a t the end.
A larger tube constituted an outer jacket for the perforated tube to
which suction was applied by means of a side arm. Dried air entered
the inner tube and carried the liquid adhering to the crystals into the
outer jacket. The crystals meanwhile were pressed down by means of
a glass rod flattened out at the bottom. The whole apparatus previous
to the admission of the crystals was cooled in an ice-bath.
Vessel A, with the crystals, was then removed from B and was sus-
pended in a beaker, and the crystals allowed to melt. The first few drops
were added to the liquid collected in B to which was also added the super-
natant liquid poured off from the crystals. The tube containing the
melting crystals and the beaker into which they were melting were enclosed
by a large bell jar containing also a desiccating agent; this precaution
being necessary to prevent the solution from taking up moisture from the
air during the time required for the crystals to melt.
The solution was thus separated into 2 portions-one concentrated and
the other dilute. One might have expected that the concentrated solu-
I See freezing-point curve. 0. Maass and 0. W. Hrrzberg, THISJOURNAL 41,
2569 (1920).
25S.q. 0 . MAASS AND W. E. HA'I'CHER.
don, formed from the dry melted cijrstds, would approach TOO%, but
when carried out under the conditions described above, the concentration
was only of the order of 4700,the solution having increased in concentra-
tion from 90 to 949& This degree of eoncentration was still less with-
out the precautions described above. 'The s t i ring
~ of the solution during
crystal formation was essential.
i ~ .mrnber of results obtained may be worth while giving as showing
the stepping up of the concentration oT the solution.
% WOO-in solution yo H ~in zmelted crystals % HSOLin mother liquor
gr [ 95.3 86 9
86.9 92 o 81.9
88 L 93.4 82 .o
93 I 97 4 88.2
92 o 96 8 88 o
95 98 3 s)I .9
96 8 99 0 94 .Q
98 7 99.9 93 .Q
A systematic fractional crystallization was devised to utilize all avail-
able stock to obtain the highest percentage. Starting with 100 g. of 907;
sdution, 50 g. of 94% and 50 g. of 85% are obtained. This is repeated
with another TOO g. of 90% solution, The 2 portions of 50 g. each of the
85% solution are united, and by crystallization 50 g. of &yoand 50 g.
of 90%) solution are obtained. The 2 portions of 94% are also united
and give 50 g. of 97% and 50 g. of 9 0 % ~and so on. Thus 400 g. of 90%
solution gave so g. of 100%~so g. of 9770, 50 g. of 94%, 50 g. of go%,
50 g. oi %yo and 150 g. of S2Yo. After having obtained these solutions,
a fresh portion of 90Yo is separated completely into 2 end products 1 s o 7 ~
&nd 8&-
In practise, of course, the crystallizations are not controlled with the
exactitude which the diagram would indicate, but a variation takes place
due to the varirttion in relative amount of crystal and solution. Ilowever,
the various solutions are united according to the scheme described above,
which in the end results in the same thing.
Any impurities which may have found their way into the hydrogen
peroxide will accumulate in the 82% solution. After a certain amount
of this solution has been collected, it is distilled and then reconcentrated.
There is no real loss in hydrogen peroxide during this third stage of the
psoxss except that sticking to the sides of the glass vessels.
Now that the various stages in the preparation of the anhydrous hydro-
gen peroxide have been described, it i s possible t o discuss the process as
a whole. The limits of the various stages are not chosen in a haphazard
maimer, but were chosen with the object of obtaining the optimum
yield, the time factor being taken into account. First, the impure 370
sodtitions are concentrated to 307,. I1 this concentration is carried further,
PROPERTIES OF PURE HYDROGEN PEROXIDE. I. 255%
say to SO%, the impurities are concentrated to such an extent that a rapid
decomposition sets in during the last part of the concentration. On the
other hand, it is essential to have as small a bulk as possible when it
comes to the actual distillation. If concentration is stopped a t 107~
instead of 3070, the time of distillation is increased and the decompo-
sition during the distillation is tripled. It pays to carry out the first con-
centration to just about 3oVo. From the freezing-point curve it is evi-
dent that the concentration must be carried out to a t least 80% before
the crystallization procedure will give any results a t all, and since it is
the most cumbersome it is best to start crystallizing with solutions as
highly concentrated as possible. On the other hand, concentrating a
hydrogen peroxide solution above 90% is attended by high losses due to
the vapor pressure of hydrogen peroxide itself so that 90% is perhaps
the best concentration with which La. end the concentration in vacuo.
The time required for the process is an important factor. The concen-
tration of a liter of 3yo solution requires 3 hours, The product of 4
such concentrations is distilled a t one time, the distillation requiring about
3 hours. About 500 g. of the pure distillate is concentrated to cjo70j 5
hours being allowed for the actual concentratioz. The crystallization is
the most tedious, 4 or j sets oi apparatus as described being required,
so that several crystallizations may be carried out a t once. The time
for each crystallization may be put a t 4 hours. the crystals taking a long
time to melt completely.
The need of great cleanliness is essential. throughout the work. The
hydrogen peroxXe solutions are allowed to come in contact only with
giass, This giass, be it the receiver in the still or the thermometer used
during crystallization, is treated with hot chromic acid solutions with
subwquent washing with distilled water.
As regards the methods of analysis used, a few words may be in place.
The siirer test for chloride morks in the presence of excess of nitric acid,
the latter preventing the formation of silver oxide. The barium test can
be imsed for the detection of sulfuric acid. Another qualitative test which
is applied is the evaporation of the solution to dryness in a platinum
evaporating dish to see if a non-volatile residue remains
The amount of acid present in hydrogen peroxide solutions can
measured in the ordinary way with phenolphthalein as indicator,
hydrogen peroxide having no effect on the end-point up to 2 0 7 c, con-
centration.
The strength of hydrogen peroxide was measured by means of potas-
sium permanganate solutions, carefully standardized by means of several
samples of potassium tetra-oxalate of known purity. The use of potas-
sium permanganate is objectionable in the presence of foreign substances,
but gives perfect results in the case of pure aqueous solutions.
2556 0. MAASS AND W. H. HATCHER,
_
r-
;? I
_
I
I
-
A
- __._ - - - -
i
\
I
- -___ - _ _ _ \
I
II
\"
I
-
- _ - - 1.
J--_--i
I
I
- __---
- - _--l_--
+_I___
\.!
I
'\=
f-
__ __ __
+
4
I
7---+A
-
__ 4--
--I~
-I
-
1
1
I
1
L-_
.
0. MAASS AND W. H. HA'J!CHER.
1~
1
ment, the resulting bub-
I bles of oxygen adhering
to the sides of the tube.
In the first place, not
the smallest sign of such
a bubble was visible. A
1 large
density
were
number of the
made
determinations
a t successive
_ _ - _ 1 lower temperatures and
a slight dccornposition
- would result in a tem-
i p e r a t u r e coefficient
smaller than the t ~ u e
one being iound. The
value at +o.I' was ob-
tained first, and, after
the other densities had
been determined, the
5' IO' -0
-3 0' t9" 0" ?ti* 7 2 0 temperature was read-
iEYlPERATiJRE C
justed to the proximate
Fig 2
temperature -0.53 As
is seen from the values of the 2 densities a t these 2 temperatures no
possible change in volume could have been caused by decomposition
during the course of the experiments.
As was mentioned above, Rruhl determined the density of his hydrogen
peroxide. His value a t o o of I .4j84 is the closest to those obtained above,
w., 1.4632 a t 0'. His other determinations are obviously inexact.
Bruhl's values.
Temper dture C Density
0 1 4584
14 1 3955
18 7 I 4262
19 6 I 4393
20 4 I 4371
It might be well to insert here the values for the densities of hydrogen
peroxide-water rxixtures; determined at a much later date with freshly
prepared samples of hydrogen peroxide. The densities were determined
at 2 temperatures, o o and 18 O , the method employed being the same as
the m e described above.
PROPERTIGS OE' PURE IIYDROGGN PI$ROXfDF$. 1. 2559
Density.
11202, A
-
-, ----- Temperature
9%. 0 0. 180. .
coefficient
0 .OO 0 I99987 0.99862 0.00007
10.57 I .0419 1.0372 o ,000268
22.33 I ,0894 I ,081j 0.00043 7
40.' 4 I .165j I . 1552 O.OOOj73
56.70 1.2404 I ,2270 0.000744
6x ,zo I .2610 I ,2465 0.00081j
73.44 1.3235 1,3071 o 000921
84.86 1.3839 I 3662 o 000980
90.42 1 ,4144 I .3955 0 .oorojo
98.89 I ,4596 I ' 4404 o .0010',7
In Pig. 3 these results are shown graphically.
These data are of value in checking up the value for the density of 100%
hydrogen peroxide for a calculation shows that 1.4633 a t o o and 1.4442 a t
18' are the value for
the anhydrous perox-
ide. It is seen also
how the temperature 1 4 0 -
coefficient increases
uniformly from that
of pure water o.00007
to that of the pure I 3 O
xide o.QO107.5.
ensity of Solid 2
en Peroxide. 120
--Crystals of hydro-
gen peroxide sink to
the hottom w h e n , , o
formed in the liquid,
and give the ianpres-
sion of being much
e n s e r t h a n the l o o
P F P C E N TAG[ H,C,
liquid. The actual
Fig 3 .
density of the solid
determined as follows. The hydrogen peroxide in the dilatometer bulb
was cooled until crystals formed. Most of these were allowed to melt
and then the bottom of the bulb was gradually immersed in a freezing
mixture kept a t a conskant temperature several degrees below the freez-
ing point of the peroxide. The rate of immersion was timed to equal the
rate of solid iormation until all the bulb and a portion of the capillary
were immersed in the freezing mixture. This insures the complete solid-
ification without strain of the hydrogen peroxide in the bulb. The bulb
was kept in the freezing mixture for one hour, the height to which the solid
came in the capillary and the position of the meniscus of the liquid par-
2560 0. MAASS AND w. 11. HATCHE::R.
0.01828
0.01456
12.20 0 .OW47
0.01272
%. 00. 18".
0.00 0.01'778 0 .Or054
5.71 0 .or762 0.01061
11.21 0.01740 o .01066
14.98 0.01734 o .or072
22.33 0.01758 o.01105
34.05 0 .Oi805 0.01157
44.83 0 .or846 0.01204
52.49 o ,01876 0.01235
59.62 0.01gOc 0.0~266
68.50 o.oig3z 0.01285
75.03 0 .Oig29 o .01292
83.15 0 .01909 0 .or300
89.47 0.01873 o .or3oI
98 3 9 0.01828 ,.
'8
-\ \
:;\ I
_____ _ 41
The surface tension of hydro-
gen peroxide is therefore, slightly
greater than that of water and
I the association as calculated from
j7 r---7---
I the variation of surface tension
I
I with temperature is slightly less.
The similarity between the sur-
face tensions of pure hydrogen
peroxide and water has a certain
__ significance in the light of recent
work on surface tension by Lang-
m u 9 and Harkinsn3 Evidently
the peroxide and water molecules
are orientated in exactly the
same way a t the surface, and
I 1 T W Richards and L. €3. CoombsG
I I __--1-_1-__1
~ THISJOURNAL, 37, 16j6 (1915)
OQ 40 5' o0 10' 2 I. Langmuir, abid, 39, 1848 (1917).
TFPPFRATURE C 8 W. D. Rarkins, I$. C €1. Uavres
I k .6 , and G.'I,. Clark, i b i d , 39, 541 ( 1 9 x 7 )
PROPERTIES OP PURE HYDROGEN PEROXIDE. I. 2563
from that point of view also it might have been predicted, when their corn-
position is taken into account, that pure hydrogen peroxide would have
a slightly greater surface tension then water.
As a means of checking up the surface tension of pure hydrogen peroxide,
the surface tensions of various concentrations were measured a t 2 tern-
peratures.
H2Oz. 70 Surface tension (dynes).
At 0O ..... . . . . . . . 0.00 75.49
12.54 75.91
18.17 76.04
27.22 76.26
34.58 76.55
56.06 77.31
59.27 77.38
86.31 78 .so
-4t 18O . . . . . . . . . . . 0.00 72.82
12.78 73.22
23.70 73 .SI
28.14 73.67
44.31 74.13
59.27 74.67
60.83 74.73
79 .a1 75 *29
90 .66 75.67
As Fig. 7 shows, the surface tensions vary in a regular expected manner,
confirming the values of 78.76 dynes a i o o and 75.99 dynes a t IS', ob-
tained from the pure 100%
peroxide.
Specific Heat of Liquid 76
Hydrogen Peroxide. Speci-
eat of Solid Hydrogen
ersmide. Latent Heat of 77
~~~~o~ of Hydrogen Pm-2
oxide,---The measurement 16 2
of the above constants of
hydrogen peroxide p r e - $
sented certain experimental $ ''
difficulties. Its chemical ,u
nature is sucli that it must 74
not be allowed to come in $
contact with anything ex- .,?i
cept glass. It was therefore
tkcided t o use the following
method. Abulb, El (Fig. 8), 7 2
waq sealed a t the end of a PERCENTAGE H2OZ
long glass tube, A, of small Fig. 7 -Surface tension curves for aqueous ~ 1 ~ 0 2 .
2564 0. MSBSS AND W. H. HATCHER.
The figures for the lowering of the temperature in the calorimeter are
given in order that the accuracy of the method may be judged. Evidently
the experimental error is about 2Yc. In determining the last value given
above the hydrogen peroxide was carefully cooled down in order to pre-
PROPERTIES OF PURE HYDROGEN PEROXIDX3. 1. 2565
60". Two plates of optical glass edges were cemented on the outside so
that the hydrogen peroxide did not come in contact with the cement.
The accompanying diagram (Fig. 9) gives an idea of the prism when
viewed from the top and the front (plan and elevation). Sodium light
was used throughout the measurements.
Temperature. Angle of minimum Refractive
Substance. 'C. Prism angle. deviation. index.
Hydrogen peroxide. . . . . . . . . 22 5 7 O 54? 27' 54' I .4140
Hydrogen peroxide. . . . . . . . . 22 57 54.' 2 7 O 53' I .4r38
Solution of hydrogen peroxide
96.81%. . . . . . . . . . . . . . . . 24 j6"58%' 27" 43/4r 1.4043
Water. . . . . . . . . . . . . . . . . . . . 25 56' 58'/2' 21' 55'/2' I ,3330
The prism was taken apart and cleaned after the first 2 experiments
described above had been made; hence the slight change in the prism
angle. The refractive index of water was measured in order that t-he
accuracy of the measurements might be tested. The value 1.3330 ob-
tained i s in excellent agreement with the recognized value.
The refractive index was one of the few measurements which Briihl
undertook to make; as a matter of fact, this measurement was really the
sole object of his research. The values he obtained range from 1 . 4 ~ 0 5
to 1.4069, indicating that his purest sample may have been only 98Yc
a t the time of measurement.
The interest in the refractive index lies principally in the fact that this
physical property is both a. constitutive and an additive one for atoms.
That is, the property depends both on the atom and the nature of its
linkages to other atoms. For purposes of comparison, the molecular
refractive power of a substance is calculated by means of the Lorenz-
Lorentz formula
n2- I nz
R---
d ?t2 +z
where R is the molecular refractive power, HZ the molecular weight, d
the density and n the refractive index.
Substance. Density. Refractive index. R.
Hydrogen peroxide. . . . . . . . . I ,4403 1.4139 j .9OO
Water. . . . . . . . . . . . . . . . . . . . 0.9973 1.3330 3.715
Eriahl of coiirse obtained a lower value for R.
Pollowing Briihl's reasoning in determining the constitution of hydro-
gen peroxide, but using the figures obtained by the author :
R for water, H.OH is 3,715
R for hydrogen, H is I ,050
DEPARTMGKT
FROM THE CI-ISMISTRY
[CO~TRIEUTION 1
OF NLCGILLUNIVERSITY