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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.
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
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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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TABLEI(A).-DENSITIES
OF H202 +H2O MIXTURES AT 25" C
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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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).
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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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
Published on 01 January 1952. Downloaded by Universittsbibliothek Bern on 15/09/2014 08:36:45.
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