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THE BEHAVIOUR OF MIXTURES OF HYDROGEN


PEROXIDE AND WATER
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PART 1.-DETERMINATION OF THE DENSITIES OF MIXTURES OF


HYDROGEN PEROXIDE AND WATER

BYMISSM. F. EASTON,MISSA. G. MITCHELL AND W. F. K. WYNNE-JONES


Department of Physical Chemistry, King's College, Newcastle-upon-Tyne
Received 5th March, 1952

The densities of mixtures of hydrogen peroxide and water have been determined at
0", lo", 25", 50" and 96" C by a simple displacement method. The method is found con-
venient and accurate for determining the concentrations of mixtures of hydrogen per-
oxide and water. The data have been fitted to equations and the agreement of the data
and equations is about 1 part in 5000 for all temperatures except 96" C where it is about
1 part in 1400.

Although several authors have previously made measurements of the densities


of mixtures of hydrogen peroxide and water, the reactivity of the system has made
it difficult to obtain reliable results over a wide range of both temperature and
composition. In the course of a general study of the properties of electrolytic
solutions in these mixtures we required an accurate knowledge of the densities
so as to enable rapid determinations of composition to be made and it seemed
desirable to extend the measurements over as wide a range as possible.
Since the main experimental difficulty in determining the densities of these
mixtures is the formation of gas bubbles from the decomposition of the hydrogen
peroxide, we decided not to use pycnometers but to apply a simple displacement
method. This method turned out to be both quick and accuraie and the results
obtained by weighing a carefully cleaned Pyrex glass sinker in the hydrogen
peroxide solution compared favourably with those of the pycnometric method.
We made measurements at 25" then at 0",lo", 50" and 96"C and even at the highest
temperature the accuracy is about 0.1 %,while at temperatures up to 50" our
results are at least as accurate as those of previous workers at 0" C although it
has been frequently reported that the solutions are insufficiently stable about
0" C for accurate measurements to be made.

EXPERIMENTAL
DENSITY OF MIXTURES OF HYDROGEN PEROXIDE AND WATER AT 25", OD, 10" AND 50" C.-
The method employed was to weigh a glass sinker in air, water and hydrogen peroxide
solutions and hence calculate the volume of the sinker and densities of the solutions.
The sinker (volume approximately 1 cm3) was suspended by means of a glass fibre in a
glass density vessel. The fibre was attached to the left-hand arm of an analytical balance
which could be read to O-OOOl g. The sinker and fibres were constructed from Pyrex
glass rod and the hooks used to handle the sinker and fibres from Pyrex glass tubing.
In order to eliminate surface tension effects the part of the fibre which passed through
the surface of the liquid had its diameter reduced to approximately 0.03 mm. The density
vessel was a Pyrex glass weighing bottle 9 cm high and 2-5 cm ext. diam. It fitted closely
into a water jacket which is shown in fig. 1 (a)and (b). The walls were made of glass so
that the density vessel and its contents could be observed during weighings and any trace
of decomposition detected immediately. By a friction drive the jacket could be moved
up and down on the stand and fixed in any desired position. Thus it was not necessary
to have the glass fibres of a uniform length ; also by lowering the jacket the sinker could
easily be detached from, or attached to, the fibre with a glass hook. Any oxygen bubbles
796
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MISS EASTON, MISS MITCHELL A N D W . F . K . WYNNE-JONES 797


which formed on the sinker were removed simply by lowering the jacket until the sinker
was above the level of the liquid, then slowly raising it into position. The tightly fitting
Perspex cap protected the upper metal end-piece. The Perspex lid was designed to
exclude dust and moisture from the hydrogen peroxide solution. During weighings a
slow stream of dry dust-free air was passed through the hollow screw. A rapid stream
of water from a thermostat (& 0.05") was circulated through the jacket. It was impos-
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sible to carry out an accurate weighing of the sinker in hydrogen peroxide unless the
glassware was specially treated, so that no trace of decomposition occurred on the surfaces
in contact with the peroxide solution.

FIG. la.
A-heavy metal stand ;
B-bakelite platform with friction drive ;
CI, C2-metal end pieces ;
D1-Perspex cap ; D2-Perspex lid.
mFIG. lb.
1

The sinker was placed in the density vessel and they were cleaned together by rinsing
with alcohol then adding a little nitric acid. Vessel and sinker were then washed thoroughly
with water and soaked in distilled water for several hours. The vessel was rinsed with
distilled water and tested with hydrogen peroxide. If any decomposition occurred on
the surface of the vessel or sinker, the cleaning process was repeated. When the surfaces
were properly conditioned the vessel was completely filled with a fairly concentrated
hydrogen peroxide solution and stored under a bell jar to prevent contamination with
dust. The sinker was always kept in a density vessel and was handled by means of a
glass hook which was carefully cleaned at each stage. Fibres and hooks were drawn
out from glass rod and tubing which had previously been thoroughly cleaned by the
+
alcohol nitric acid method. They were stored in test-tubes containing hydrogen per-
oxide solution. Small glass caps were placed over the tubes and they were placed under
a bell jar.
Immediately before use, the density vessel, sinker, fibre and hook were rinsed thoroughly
with distilled water, carefully dried in an oven at 105-110"C and cooled in a desiccator.
The sinker was kept in the density vessel and the fibre and hook in test-tubes. The
glassware was never left exposed to the air for longer periods than were absolutely
necessary.
To reduce the risk of contamination by dust the following method was used for all
weighings. The density vessel containing the liquid and sinker was stoppered and placed
in the water jacket. After 30 min, when the temperature of the liquid had reached
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798 DENSITIES OF M I X T U R E S

equilibrium, the stopper was removed from the density vessel, the Perspex lid closed
+
and the air stream turned on. The sinker fibre, fibre alone, then sinker fibre were +
weighed. The Perspex lid was kept closed as much as possible during the weighings.
MEASUREMENTS AT 25" C.-The weight of the sinker in vucuo and the volume of the
sinker were determined at the beginning and end of the series of measurements. The
solutions used were obtained by diluting High Test peroxide (unstabilized) supplied by
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Messrs. Laporte with triply-distilled water. Laboratory-distilled water was distilled


from a trace of potassium permanganate then again distilled in a Pyrex glass still. Im-
mediately after weighings had been made in a hydrogen peroxide solution, a sample of
the solution was removed for analysis. The analysis was carried out by titration with
potassium permanganate by the method recommended by Huckaba and Keyes 1 with
the following modifications.
The sample was transferred by means of a clean, dry Pyrex glass dropping tube to a
weighing bottle containing a few ml triply-distilled water and was weighed. The weight
of the sample chosen varied from about 0.3 g for a 90 % solution to about 13 g for a very
dilute solution. All glassware used in the analysis was carefully cleaned before use.
The solution in the weighing bottle was diluted to 100 ml with triply-distilled water.
50 ml of a sulphuric acid solution containing 50 ml concentrated sulphuric acid per litre
solution and 100 ml triply-distilled water were placed in a 250 ml beaker. Sufficient
potassium permanganate solution was added to impart a faint pink colour to the solution.
A 10-ml sample of the diluted hydrogen peroxide solution was then added and the titra-
tion carried out in the way recommended. The end-point was reached when the initial
pink colour was reproduced. Best agreement in a series of titrations was obtained when
the initial pink colour was only just detectable as it was almost impossibleto repeat exactly
a definite colour in such a large volume of solution. The light from a mercury lamp
was used to detect the pink colour. The lamp was fixed up with an adjustable shutter
alongside the titration beaker and the shutter opened during the initial tinting process
and at the end point determination. The end point was determined to 0.01 ml. The
10-ml pipette and 50-ml burette each had a standards certifkate and were rechecked
before use.
The potassium permanganate was standardized with sodium oxalate by the method
of Fowler and Bright.2 One sample of sodium oxalate was purified by Sorensen's 3
method and a second sample was kindly sent to us by the National Bureau of Standards :
the two samples gave good agreement.
The experimental results are given in table 1 (A).

TABLEI(A).-DENSITIES
OF H202 +H2O MIXTURES AT 25" C

% H202 b l w ) density g/cm3 % H 2 0 2 (wlw) density g/cm3


0.0 (0.9970) 49.88 1-1909
1.91 1-0036 53.48 1.2067
5.99 1.0179 55-08 1-2143
9.23 1.0295 59.68 1.2353
13.47 1.0452 62-55 1-2490
17-44 1.0597 64.88 1.2593
21.14 1,0737 68-97 1-2790
24-58 1.0868 73-15 1.2996
27-96 1-0996 73.66 1-3024
29-99 1-1078 76.66 1.3166
34.23 1.1244 80.64 1.3378
39-12 1.1450 84.97 1-3595
40-67 1-1515 89-68 1-3848
42.97 1,1610 89.78 1.3855
47.02 1.1785 89.89 1.3855

The experimental results were plotted on a large scale graph on which one division
corresponded to 0.0002 for density and 0-1 % for composition. The points can be
represented quite accurately by a smooth curve. At high concentrations of hydrogen
peroxide when the percentage error arising in the analysis is greatest, the deviation of the
points from the curve was never greater than 0-1 % hydrogen peroxide.
MEASUREMENTS AT 0", 10" AND 50" C.-The method described for measurements
at 2 5 C was used. No appreciable decomposition of a solution occurred during a
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MISS E A S T O N , MISS M I T C H E L L A N D W . F . K . W Y N N E - J O N E S 799


determination at 50" C. The mass in vucuo and the volume of a sinker at 25" C were
determined at intervals during the three series of measurements. The volume of the sinker
at 0", 10" and 50" C was calculated using the value 9.6 x 10-6 for the coefficient of cubical
expansion of Pyrex glass. Immediately after a weighing had been made in hydrogen
peroxide solution the density vessel was taken out of the water jacket, the sinker removed
and the solution rapidly brought to approximately 25" C. The density of the solution
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at 25" C was then determined and the concentration of peroxide read from the large scale
density composition graph.
The experimental results are given in tables 1 (B), (c) and (D).

TABLE~(B).-DENSITIES OF H202 +H2O MIXTURES AT 0"C


%H202 density % H202 density
(w/w) dcm3 (wlw) g/cm3
0.0 0-9999 55.69 1,2373
7.36 1*0291 65-07 1-2822
17-14 1.0690 74.96 1.3321
24.36 1.0987 83.27 1.3759
33.23 1.1370 91.55 1-4221
44.62 1.1860 96.65 1.4517

TABLE1 DENSITIES OF H202 +H2O MIXTURES AT 10" C


density %H202 density
slcm3 (w/w> glcm3
0.0 0.9998 55-15 1-2266
4.32 1.0150 60.24 1.2503
10.69 1.0394 65.32 1.2747
17.28 1.0652 70.69 1.3012
23-65 1*0906 77.04 1.3335
29.93 1.1163 80.2 1 1.3499
36.33 1-1432 86-77 1.3851
41-82 1.1668 89.00 1.3973
49-27 1.1997 94.25 1-4261
98.60 1.4515

TABLE1 (D).-DENSITIES OF H202 +H20 MIXTURES AT 50" C


% H202 density %H202 density
(wlw) glcm3 (wlw) glcm3
0.0 0.9880 47.07 1.1580
6.96 1.0106 57.21 1.2020
12.53 1*0289 59.60 1.2123
20.36 1.0564 66.22 1-2425
30.21 1.0914 74-37 1.2814
39.25 1-1267 86.53 1.3419

DENSITIES OF MIXTURES OF HYDROGEN PEROXIDE AND WATER AT 96" C.-The experi-


mental method for the determination of density has been described earlier. The only
difference in procedure was the method of controlling the temperature. The solution
was maintained at 96 f 0-15" C by surrounding the density vessel with water boiling under
reduced pressure.
The density vessel and water jacket are shown in fig. 2. The water was heated by an
electric hot plate controlled by a Sunvic regulator. A window was cut in the asbestos
lagging so that the contents of the density vessel could be observed during measurements.
The manostat was similar to that described by Simon.4 Solutions containing Laporte's
unstabilized High Test peroxide decomposed rapidly at 96C so it was necessary to use
stabilized material for the density measurements. Solutions were made with triply-
distilled water, each containing 81 mg zinc sulphate per litre. Some decomposition of
the stabilized solutions occurred at 96" C but no appreciable change in the concentration
occurred during a density determination.
It was clear from a few preliminary tests that the temperature at which the water in
the jacket was required to boil to maintain the peroxide solution at 96" C depended on
the concentration and rate of decomposition of the solution. The rate of evaporation
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800 DENSITIES OF MIXTURES

of the solution and the amount of condensation of liquid on the upper part of the density
vessel increased as the concentration of hydrogen peroxide in the solution decreased.
It was therefore necessary to determine
the manostat setting for each solution
under investigation. The following pro-
cedure was used. The electric hot plate
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was switched on and the whole apparatus


assembled. A thermometer was sus-
pended in the peroxide solution and a
rapid stream of cold water passed through
the condenser. Water at approximately
96" C was introduced into the water
jacket through tube A and the electric
hot plate clamped into position. The
pump was switched on and the manostat
regulated until the reading on the
thermometer became steady in the range
96 0.15 "C. The manometer reading
varied from 658 mm for approximately
90% (w/w) hydrogen peroxide to about
700 mm for very dilute solutions. The
C solutions were investigated in order of
decreasing concentration hydrogen per-
oxide. With a little practice we were able
to estimate fairly accurately the pressure
required for solutions in the concentration
range 90-40 % (w/w) hydrogen peroxide
and to adiust the manostat before the
FIG. 2. volume of solution had changed appreci-
A, Tube for filling water jacket; ably. For solutions containing less than
B, Liebig condenser ; C , asbestos lagging ; 40 % hydrogen Peroxide an approximate
D, rubber bung ; E, B34 socket; setting of the manostat was obtained,
F, density vessel mounted on B34 cone ; water was added to bring the volume of
G, electric hot plate. solution up to the required mark and
the final adjustment quickly made. The
volume of the sinker at 96" C was calculated from the volume at 25" C using the value
9.6 x 10-6 for the coefficient of cubical expansion of Pyrex glass.
The experimental results are given in table 2.
TABLE2.-DENSITIES OF H202 $- H2O MIXTURES AT 96"c
% HzO2 dcnsity % Hz02 density
(WlW) glcm3 (wlw) slcm3
0-0 0.96 15 52.55 1.1390
11.40 0-9950 60-65 1.1726
14-84 1 a0054 66.20 1.1952
26.80 1.0428 73.40 1.2299
37.97 1.0834 84.30 1.2788
45.03 1-1116 89-30 1.3038
ANALYSIS OF DATA.-At each experimental temperature the data have been fitted
by the method of least squares to cubic equations of the form
d= A + +
BW C W ~ D w ~ , +
where d is the density and w the weight fraction of hydrogen peroxide in the solution.
RESULTS
+ +
0" C, d = 0.9998 0.39939~ 0.01758~2 + 0.05470~3, (1)
+
10"C, d = 0.9997 0.36790~ 0.06208~2+ + 0.02954~3, (2)
+ +
25" C, d = 0.9970 0.34672~ 0 0 6 9 9 5 ~ 2 + 0.02885~3, (3)
+
50"C, d = 0.9880 0.31382~ 0.09402~2+ + 0*01910~3, (4)
+
96"C, d = 0.9612 0.27652~ 0.11956~2+ (5)
The agreement of the data with the equations is about 1 part in 5000 at all temperatures
except 96" C, where it is about 1 part in 1400.
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MISS E A S T O N , MISS M I T C H E L L A N D W . F . K . W Y N N E - J O N E S 801

DISCUSSION

The early values for the densities of mixtures of hydrogen peroxide and water
reported by Maass and Hatcher 5 are now considered to be too low as also are those
of Kubaschewski and Weber.6 More recent determinations have been made
by Huckaba and Keyes 7,8 and by Gigukre and Geoffrion.9 These workers
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carried out measurements at 0" C by a dilatometric method and Huckaba and


Keyes also measured the expansion of a few solutions over the range 0"-20" C .
For comparison of these results with our own we give in table 3 (A) the actual
results of Gigukre and Geoffrion together with interpolated values from Huckaba
and Keyes' results read from table 2 of their paper 7 and our own values calculated
from eqn. (1) above. There is good agreement between our results and those
of Huckaba and Keyes over the whole range of concentration but Giguere and
Geoffrion's values are consistently higher. Such a difference could. arise with
the more concentrated solutions if decomposition of the hydrogen peroxide
occurred between the density determination and the analysis of the solution.
The general agreement between Huckaba and Keyes' data and ours is further
illustrated by taking the expansions directly determined by Huckaba and Keyes
of five mixtures over the range 0-20" C . The densities of the five solutions at 20" C
thus calculated are compared in table 3 (B) with the values derived from our results
at 25" C using our own temperature coefficients.
TABLE3 (A)
density at 0" C g/cmJ
% H202
(wlw) Giguere Keyes this work
9-32 1.0377 1-0366 1.0372
10.21 1-0410 1-0402 1-0408
12.21 1-0493 1*0484 1-0489
18.32 1-0748 1-0735 1.0739
19.27 1.0783 1.0774 1.0778
29.54 1-1209 1.1206 1-1207
41-23 1-1722 1-1715 1.1713
49-87 1-2119 1.2104 1.2101
68.37 1-3006 1-2990 1-2986
69.05 1-3037 1.3024 1-3020
78-61 1.3535 1.3515 1.3512
79-63 1.3590 1.3569 1.3566
89.64 1.4136 1.4116 1.4113

TABLE3 (B)
density at 20" C
wt fraction a x 104 (0-20") u x 104 (10-250) -
HzOz Keyes (obs.) this work
Keyes this work
0.96877 7.759 7.674 1-4306 1-4303
0-78529 7-344 7.439 1.3316 1.3313
0.59083 6.656 6.817 1.2370 1.2364
0.39159 5.846 5.763 1.1490 1.1485
0.21525 4.326 4.278 1.0773 1.0775

1 Huckaba and Keyes, J. Amer. Chem. SOC.,1948, 70, 1642.


2 Fowler aad Bright, J. Res. Nat. Bur. Stand., 1935, 15, 497.
3 Sorensen, Kolthoff and Stenger, Volumetric Analysis (Interscience Publishers Inc.,
New York), 2nd rev. ed., 1944-47, vol. 2, p. 74.
4 Simon, Ber., 1927, 60, 568 ; Ber., 1928, 61, 2173.
5 Maass and Hatcher, J. Amer. Chem. SOC.,1920, 42, 2548.
6 Kubaschewski and Weber, 2.Elektrochem., 1950, 54, 200.
7 Huckaba and Keyes, J. Amer. Chem. SOC.,1948, 70,2578.
8 Huckaba and Keyes, J. Amer. Chem. SOC.,1950, 72, 5324.
9 Gigubre and Geoffrion, Can. J. Res. B, 1950, 28, 599.