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DEPARTMEXT OF CISEMISTRY OF MCGILLUNIVERSITY
THE PROPERTIES OF PURE HYDROGEN PEROXIDE. I.
BY 0. MAASSAND
Recei$ed September 25, 1920.
There are few chemicals which have found a greater variety of uses than hydrogen peroxide. Every year the literature becomes enriched with papers dealing with reactions in which hydrogen peroxide in dilute solution plays an important part. On the other hand, the properties, both physical and chemical, of pure hydrogen peroxide are for the greater part unknown and the accuracy of those properties which have been tabulated is subject to doubt. The present paper deals with the preparation of pure anhydrous hydrogen peroxide and the determination of of its properties. To treat hydrogen peroxide historically and describe its multitudinous reactions in dilute solution1 would fill several volumes and would not come within the scope of this paper. It will therefore be most convenient in the following account of the various steps in which hydrogen peroxide was purified and its properties investigated, to refer a t each stage to any previously published work which suggests similarity to that being discussed. What might be termed the "raw product" from which the pure hydrogen peroxide was to be derived consisted of a 3% solution prepared irom commercial barium peroxide in the ordinary way. The principal impurities were sodium sulfate, phosphoric, sulfuric and hydrochloric acids and traces of several inorganic salts. This 3% solution *as concentrated to 3 0 7 ~by means of the sulfuric acid concentrator' described in another paper, a yield of 95% being obtained. The details of various yields obtained under different conditions of temperature and pressme are of no particular scientific interest but may be made the subject of a separate paper in an industrial journal. Subsequent purification of the hydrogen peroxide from the 3oC& solution was effected in 3 stages: ( I ) distillation to remove non-volatile impurities; (2) conceiitration of the 307~ solution (now pure) to 90%; ( 3 ) separation of pure hydrogen peroxide out of this concentrated solution by fractional crystallization. The first stage required considerable development as the 30% solution was found to be very unstable. This was due to the fact that all the inpurities had been concentrated as well as the hydrogen peroxide. Generally, the decomposition a t room temperature was found to average K 7 ; per day so that, up to the moment when they were to be distilled, the solutions were kept a t oo, a t which temperature the rate of decomposiTars JOTJIWAI,, 42, zj71 ' ~ g z o ) .
PROPERTIES OF PURE HYDROGEN PBROXID$.
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 Geissler 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 .
to a spiral, F, and a receiver] G, both of which are placed in vessels filled with ice. The tubing H connecting the receiver G to the sulfuric acid pump is about one cm. in diameter, the height of 13 being the barometric height in terms of sulfuric acid. A manometer, E, indicates the pressure a t any moment. The distilling flask, B, with ground glass neck, has a volume of about 300 cc. and is heated by means of a water-bath. In the first experiments, 2 0 0 cc. of the 30% solution1 was placed directly in this flask a t one time. 'She apparatus was constructed wholly out of glass tubiiig The sulfuric acid pump works automatically, going through one cycle in less than one minute with the aid of a small electric pre-evacuator connected through the valve to J. The water-bath is heated to about 60' so that this is the maximum temperature reached by the hydrogen 0. Maass, THISJOURNAL, 41, 53 (1919).
A fair measure of success attended this innovation. Analysis of the distillate showed a 60% yield. examination of the gelatinous residue in the distilling flask showed the presence there of a. An attempt was made to increase the yield of hydrogen peroxide by what may be termed a vacuum steam distillation. at the temerature of the distillation and under a pressure of one cm. was heated continuously to a temperature of 70'. A vessel. vaporizes with the water and is condensed in the receiver. Three hours are required for the distillation of half a liter. the object being to displace the hydrogen peroxide. of mercury in spite of the oxygen liberated. MAASS AND W. Then a certain amount of decomposition takes place. Any oxygen liberated is in an active Corm and mercury or any other metallic substance is corroded and the oil of a rotary pump thickens--another reason why the sulfuric acid pump is a desirable one to use.2550 0 . I ) . being over goyc in many cases. as the pressure in the apparatus was below the vapor pressure of water. k HAkHGk peroxide solution during the distillation. Towards the last. It is here that the value of the sulfuric acid pump becomes evident for it is possible to keep the pressure below one cm. During the latter part of a distillation. For a while the distillations were carried out in the manner described above. It was found impossible to drive off this hydrogen peroxide without having to heat it to a temperature where vigorous decomposition resulted. the impurities are concentrated to such an extent that they are precipitated in the solid form along the sides of the distilling flask. the proper tap was opened slightly. A t first the distillation takes place without a great loss of hydrogen peroxide due to decomposition. A. fairly large amount of hydrogen peroxide. suspected o€ being held in the forin 01 hydrogen peroxide of crystallization by the sodium SUIfate. somewhat higher . The water entering the distilling flask was immediately vaporized. This temperature. The solution gradually becomes more concentrated. was connected to the distilling flask B in the manner shown in the diagram. It was found that the 40% loss was not due to decomposition alone. which. and the yields rose to 75%. The yield was increased considerably. the impurities concentrating more rapidly than the hydrogen peroxide. This trap (G in Fig. Furthermore. Consequently a stream of water vapor was bubbled through the solution.. A further improvement was made by heating the empty distilling flask. Thus the major portion of the distillate was kept cool during the greater part of the time of distillation. when the solution had become very concentrated. a thin-walled wash-bottle. to 65' and placing the hydrogen peroxide solution in A from which it was admitted into the heated flask drop by drop at the rate a t which it evaporated. it was found advisable to place a trap between distilling flask and the water condenser. filled with water.
This procedure removed the last impurity. 42. the whole apparatus was filled with chromic acid cleaning mixture by suction. but.than that in the distilling flask. a t no time during the distillation. prevented the condensation of any hydrogen peroxide. The cleaning solution was removed after a few hours and the ole apparatus flushed out with distilled water until it was certain that no trace of the cleaning mixture remained. In order to prevent this. Thus. as especially well-fitting joints had been chosen. it is possible to distil 30% impure peroxide solutions. h few further particulars of the precautions taken to insure the absolute puricy of the hydrogen peroxide solution may be in place. The leak from. The smaller of the z flasks in the sulfuric acid concentrator1 was reserved for the concentration of the pure solutions. The second stage in the process of reaching 100% hydrogen peroxide is carried out as follows. in those cases where the original peroxide solutions contained large amounts of chloride. . the outside was negligible. it was found that the distillate was now absolutely pure. The latter were immersed in the heating water to such an extent that the ground glass joints were below the surface. Previous to a distillation.571 (1920). The first stage in the purification of hydrogen peroxide may be summed up by saying that if the experimental methods described above are followed. The tap leading from . a small amount of hydrochloric acid was invariably present in the distillate. The function of the trap is of course to catch any small drops of liquid which might be carried along during the distillation. 2. this end of the tube was filed off and the peroxide forced out of the receiver by air pressure into the vessel in which it was to be stored. the distillate eing absolutely pure and corresponding to an 85% yield. was the peroxide brought into coritact with any material except glass. The bottom of Receiver G was connected to a glass tube as shown in the diagram. the slight quantity of water working through was also distilled over. This flask had been especially cleaned with a hot chromic acid solution and bad then been scrupulously washed out with distilled water.4 to the distilling Rask B (by means of which the speed of entry of the hydrogen peroxide was regulated) was not greased. the concentrated peroxide solution was made slightly alkaline with sodium hydroxide before submitting it to distillation. the end of the tube being sealed off before the distillation. but the absence of tap-grease made certain that no organic impurity would find its way into the distillate. although the yield was cut down considerably. A qualitative analysis of the distillate showed the absence of all nonvolatile impurities. After the distillation. The r H 1 3 JOURNAL. Sulfuric acid was also shown to be absent. or afterwards. T h e same applies to the ground glass joints fitting into the tops of Flasks B and C.
.3% yield when he concentrated 002 g. an inevitable loss of hydrogen peroxide due to evaporation. here is. between the relative vapor pressures of water and hydrogen peroxide. 27. the partial vapor pressure of the peroxide itself. Thus he obtained only a 28. of this solution corresponding to a 65% yield being obtained. apparently. the greater is the difference.2552 0. H.. 582 g. of 4. 79. relative to the water-vapor pressure. The lower the temperature. of 2 4 . shows in comparison what the sulfuric acid concentrator can do. Thus. yield of 65% a being obtained. Ahrle concentrated perhydrol (30% solution) to 85%. I % . so that no gain is made. and some 50 g. Apparently it is impossible in this way to dehydrate hydrogen peroxide completely. Ber.5 times the yield was obtained and the peroxide concentrated to a higher degree (91% as compared to 66%). The following example.5% peroxide t o 66. prakt. of this solution was cooled to a temperature where the hydrogen peroxide crystallized out. Around 987' the proportion of peroxide lost due t o evaporation approaches the amount of water driven off. J. therefore. It is not advisable to try to concentrate the peroxide above this point as the loss becomes enormous. a portion finds its way into the sulfuric acid together with the water vapor. 129 (1909). Wolffenstein. as compared t o Wolffenstein's solution which contained 36 g. 3307 (1894). however. concentration of pure hydrogen peroxide solutions can be carried out by means of the sulfuric concentrator without any loss whatever due to decomposition because concentrations can be rapidly carried out at low temperatures. The time required for the concentration in the example cited above was rs.) 2. attention was drawn to this factor in the description of the pump. the supernatant liquid was removed. starting with a much larger quantity of peroxide (a solution containing 141 g. which bears a similarity to a method employed by Ahrle2 for obtaining strong concentrated solutions. As the solution becomes more concentrated in hydrogen peroxide. There now remains a discussion of the last stage. 102 g. ~ 7 ~ hydrogen peroxide was Concentrated to ~ I . TNolff enstein reported fairly large losses when concentrations were carried out to a high percentage concentration of peroxide in the concentration of pure solutions. But this source of loss is also dependent on the temperature of concentration and therefore pressure. HATCHER. MAASS AND W. becomes appreciable and. e above is a typical example of the results obtained during this stage.6%.. taken a t random from our experiments. Chem. the * Ahrle. The 307' pure peroxide solutions are concentrated to goyG. the temperature of the solution remaining below 0 ' . At this stage it might be well to refer t o WoHensteinl1 who was the first to concentrate hydrogen peroxide by means of vacuum evaporation.
the supernatant liquid poured o the crystals and absorbed liquid transferred to another glass tube perforated by fine holes in the bottom. The solution was thus separated into 2 portions-one concentrated and the other dilute. THIS JOURNAL 41. 1. and the temperature of the cooling bath was lowered until half the solution had solidified. no further experiments were carried out by Hhrle with the hydrogen peroxide. and the crystals allowed to melt.l The latter was then inoculated with a crystal of hydrogen peroxide. crystals adhering to the side of the first test-tube having been melted by the warmth of the hand. was then removed from B and was suspended in a beaker. The latter was thus kept stirred. the solution being stirred vigorously during this procedure. namely. 2569 (1920). of solution was placed in a large tube which was itself placed in a cooling mixture in a Dewar flask. the preparation of Caro's acid. this precaution being necessary to prevent the solution from taking up moisture from the air during the time required for the crystals to melt.PROPERTIES OP PURE BYDROGBN FEROXfDl$. 2553 remaining crystals melted. Hrrzberg. W. . A continuous stream of dried air was sent through a glass tube of small diameter leading through its cooling mixture to the bottom of the solution. 1100g. The quantity remaining was taken as being pure. The crystals meanwhile were pressed down by means of a glass rod flattened out at the bottom. it is doubtful if the hydrogen peroxide obtained in the above cited investigation was abAfter many attempts to obtain pure hydrogen peroxide from the 90% solution by crystallization. The transference was effected in a few seconds. The temperature indicated by a thermometer was then regulated to be one degree below the freezing point of the so1ution. The whole apparatus previous to the admission of the crystals was cooled in an ice-bath. Maass and 0. Vessel A. One might have expected that the concentrated soluI See freezing-point curve. and probably was sufficiently so for the purpose for which it was made. 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. with the crystals. and they were then subjected again to this same process. The crystals were pulled out by a glass rod with a hook a t the end. and in view of the experiments to be described. Dried air entered the inner tube and carried the liquid adhering to the crystals into the outer jacket. Outside of the preparation of this acid. The first few drops were added to the liquid collected in B to which was also added the supernatant liquid poured off from the crystals. A larger tube constituted an outer jacket for the perforated tube to which suction was applied by means of a side arm. 0. The crystals were finally allowed to settle. the following technique was devised.
of S2Yo. 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. the crystallizations are not controlled with the exactitude which the diagram would indicate.q. of 85% are obtained. 50 g. HA'I'CHER. of 97% and 50 g. formed from the dry melted cijrstds. This is repeated with another TOO g.solution in yo H ~in z melted crystals % HSOL mother liquor in 86 9 81. it is distilled and then reconcentrated. Starting with 100 g. don. of &yoand 50 g. of 94%. of 90%) solution are obtained. the various solutions are united according to the scheme described above. of 94% and 50 g. a fresh portion of 90Yo is separated completely into 2 end products 1 s o 7 ~ &nd 8& In practise. o 907.9 94 .Q 93 . After a certain amount of this solution has been collected.3 92 o 93. MAASS AND W.Q gr [ 86. i~.o 88.. of 9770. of 90% solution gave so g. The 2 portions of 94% are also united and give 50 g. it i s possible t o discuss the process as a whole. 0 . would approach TOO%. . Any impurities which may have found their way into the hydrogen peroxide will accumulate in the 82% solution. 50 g.25S.9 82 . First. The 2 portions of 50 g.9 88 93 L I 92 o 95 96 8 98 7 95. sdution. but a variation takes place due to the varirttion in relative amount of crystal and solution. Thus 400 g. the time factor being taken into account.2 88 o s)I . but when carried out under the conditions described above. mrnber of results obtained may be worth while giving as showing the stepping up of the concentration o the solution. of course. of go%. of 90% solution. E. and by crystallization 50 g. which in the end results in the same thing. Ilowever. The limits of the various stages are not chosen in a haphazard maimer. After having obtained these solutions. 50 g. solution having increased in concentrathe tion from 90 to 949& This degree of eoncentration was still less without the precautions described above. 'The s t i ring of the solution during ~ crystal formation was essential. oi %yo and 150 g. the impure 370 sodtitions are concentrated to 307. the concentration was only of the order of 4700. 50 g. each of the 85% solution are united. T % WOO.9 A systematic fractional crystallization was devised to utilize all availf able stock to obtain the highest percentage.4 97 4 96 8 98 3 99 0 99. of 9 0 % ~and so on. I1 this concentration is carried further. of 100%~so g. but were chosen with the object of obtaining the optimum yield. Now that the various stages in the preparation of the anhydrous hydrogen peroxide have been described.
It pays to carry out the first concentration to just about 3oVo. 255% say to SO%. On the other hand. the distillation requiring about 3 hours. On the other hand. The need of great cleanliness is essential. 4 or j sets oi apparatus as described being required. centration. This giass. 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. The siirer test for chloride morks in the presence of excess of nitric acid. The barium test can be imsed for the detection of sulfuric acid. From the freezing-point curve it is evident that the concentration must be carried out to a t least 80% before the crystallization procedure will give any results a t all. it is essential to have as small a bulk as possible when it comes to the actual distillation. throughout the work. the time of distillation is increased and the decomposition during the distillation is tripled. 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. but gives perfect results in the case of pure aqueous solutions. be it the receiver in the still or the thermometer used during crystallization. The hydrogen peroxXe solutions are allowed to come in contact only with giass. The concentration of a liter of 3yo solution requires 3 hours. end the concentration in vacuo. a few words may be in place. 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. is treated with hot chromic acid solutions with subwquent washing with distilled water. The use of potassium permanganate is objectionable in the presence of foreign substances. the crystals taking a long time to melt completely. As regards the methods of analysis used. the impurities are concentrated to such an extent that a rapid decomposition sets in during the last part of the concentration. The product of 4 such concentrations is distilled a t one time. The strength of hydrogen peroxide was measured by means of potassium permanganate solutions. If concentration is stopped a t 107~ instead of 3070. The time for each crystallization may be put a t 4 hours. so that several crystallizations may be carried out a t once. The time required for the process is an important factor. . carefully standardized by means of several samples of potassium tetra-oxalate of known purity. and since it is the most cumbersome it is best to start crystallizing with solutions as highly concentrated as possible. hydrogen peroxide having no effect on the end-point up to 2 0 7 c con. the latter preventing the formation of silver oxide.PROPERTIES OF PURE HYDROGEN PEROXIDE. I.
the solution diluted to some 500 cc. his best sample. obtained under the same conditions as the conditions of standardization. The following percentages of hydrogen peroxide were obtained when the end product of all the crystallizations was analyzed: 1 0 0 .70°.oog070 g. prepared hydrogen peroxide by concentration alone (that is.0'. The *weighing bottle was washed out a number oi times. of permanganate solution corresponded to o. The work described so far may be summed up as follows. continued evaporation i n vacuo). one need only draw attention to the futility of attempting to prepare anhydrous ethyl alcohol or anhydrous sulfuric acid by distillation. One cc. Bruh1. Bruhl determined the refractive index. 0 2 ~ ~ 99. ~ 7 ~ peroxide. In view of what has been said it is probable that the end product obtained was purer than any previous preparation.2556 0. Freezing Point. Portions weighing between 0 . Apart from the great losses attending this method. were transferred to a carefully weighed weighing bottle. 99. 2 and 0.91%) 99. This was weighed to 0. showed 9 9 . and the values obtained by Brtihl will be referred to later on in comparison with those obtained by the authors.89y0. The experiments dealing with anhydrous hydrogen peroxide which will be described later on were carried out with a sample which had been obtained after many crystallizations as described above. These were the only properties of pure hydrogen peroxide known up to the present to which any reliability whatever could be attached. The permanganate solution was then added t o the end-point. Properties.3' higher. and a 50y0yield of pure hydrogen peroxide is possible. H. MAASS AND W. Starting with commercial 3Y0 hydrogen peroxide solutions) containing many impurities. The analysis of the final product. It may be stated here that it was the above sample which was used in the determination of the physical constants as will be described further on. . the contents diluted with water and then transferred into an Erlenmeyer flask.. --x. density and freezing point. Bey.-Bruhl had found that the freezing point of his peroxide was -2.1 mg. The value found by the authors was 0.5 g. The methods present several novel features. was carried out in this fashion. The determination was made by means of a Beckmann thermometer which was'directly immersed in some of the pure peroxide Briihl. namely. and the requisite amount of sulfuric acid added.. of hydrogen peroxide. 2854 (1895). it has been shown how the pure hydrogen peroxide can be isolated.. and hence the concentration could be determined t o one part in ~ O O O . HATCHER.90% and 99. 28. about 2 0 0 g.94%.l chiefly interested in determining its refractive index. it is doubtful whether complete separation from water based on a fractional distillation method is possible. he claimed.
463r I . I .PROPERTIES OP PURE HYDROGEN PEROXIDE. cc. 0 Maass and 0. thus making unnecessary any corrections. Temperature. J .55 8. Inserting these 2 values in the freezing-point curve.4617 1.4597 I .e723 10.4419 .257j g.1'. determined in a former piece of work.5294 10.13 . length of this capillary tube was found to correspond to a volume of 0. with an accuracy of one part in 20.4490 1 . It was therefore easy to calibrate the volume of one part in 10.4733 1.4674 I .000. Herzberg. The bulb could be easily filled with liquid by means of a glass tube drawn out into a fine capillary.30 19.l it will be seen that dt/dc decreases with increased concentration.-The density of liquid hydrogen peroxide was determined by the dilatometer method.3561 10. 2570 (1920).7y0 peroxide solution was also determined. 2557 placed in a test-tube.001075 on the I See graph. a temperature of -30' has been reached before the solid phase separated out.30 12.oo 5.38 -. 10. The freezing point of a 96.4774 1.4638 I . 1 0 I . The position of a meniscus between two millimeter marks was found by means of a microscope with a scale and cross hair in the eye-piece.3754. The proximity of the freezing point of hydrogen peroxide to the freezing point of water made the calibration of the Beckmann thermometer a simple matter.8. 2 3 -12.09627 cc. The bulb and stem were immersed in a glass-walled thermostat whose temperature could be rcgulated to 0.9.53 0 . .60 15. c. 2 ) shows the variation of the density with the temperature. and found to be -4. The reading of the meniscus was naturally taken while the bulb was immersed in the thermostat. ensity.85 -- -+ 0 .4716 I0.4295 f O .5814 The graph (Fig.6 . The total weight of the liquid in the bulb was 15. One cm.3973 10.80 .4379 1 0 . The calibration was carried out with water after the bulb had been well seasoned. The densities tabulated below were corrected to a vacuum. I O .454I 1.3436 10.4570 1. Volume.00'.4235 10.4705 I .90 10.4751 1. Hydrogen peroxide can be supercooled more readily than water .5476 10.2. the decrease in density per degree rise being o.3272 Density. W. Water was deemed preferable to mercury because of the exact similarity of its meniscus to that of hydrogen peroxide. THIS JOURNAL 42.20 3 .4928 I O .4465 1. was blown a t the end of a capillary tube which was graduated in mni. A bulb having a capacity of about I O cc.
determined at a much later date with freshly prepared samples of hydrogen peroxide. HA'J!CHER.-+A - i \._.2558 0. ._--l_-a bubble was visible.. The densities were determined at 2 temperatures.1.---1 7 ._ . --I . Temper dture 0 C Density 1 1 14 18 7 4584 3955 4262 4393 4371 I I I 19 6 20 4 It might be well to insert here the values for the densities of hydrogen peroxide-water rxixtures.4632 ' . 1. Rruhl determined the density of his hydrogen peroxide..I' was obI tained first. average. As was mentioned above. His value a t o o of I . . not I I the smallest sign of such . + J _ i -0 L-_ -3 Bruhl's values. and. -. o o and 18 O . The value at +o. a t 0 His other determinations are obviously inexact. A I \ 1 1 large number of the \" . H. . MAASS AND W. the method employed being the same as the m e described above._ _ _ \ +_I___ 4 density determinations I were made a t successive I __ 4-_ _ . w..__ __ __ __ I the other densities had I II I 1 been determined.__---In the first place.r ment.4j84 is the closest to those obtained above. The possible source of error which at once suggests itself is a slight decomposition during the course of the measure. the resulting bubrI I I bles of oxygen adhering ._ 1 lower temperatures and I I a slight dccornposition . the 5' IO' 0' t9" 0" ?ti* 7 2 0 temperature was readiEYlPERATiJRE C justed to the proximate Fig 2 As temperature -0.-___ .-.! _ _ A I '\= f- -I ~ 1 ~ .-.. after ..would result in a tem1 I i p e r a t u r e coefficient smaller than the t ~ u e one being iound.53 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.? I to the sides of the tube. It is evident that the temperature coefficient is very large when compared to that of water..
89 1.3955 ' 73.3839 1 .0010'. 3 these results are shown graphically.PROPERTIGS OE' PURE IIYDROGGN PI$ROXfDF$. The hydrogen peroxide in the dilatometer bulb was cooled until crystals formed.42 98.2465 3662 .0372 I 0. o formed in the liquid. A -.4144 I . This insures the complete solidification without strain of the hydrogen peroxide in the bulb.70 6x . the height to which the solid came in the capillary and the position of the meniscus of the liquid par- .00007 to that of the pure I 3 O xide o. .57 22.00043 7 .4442 a t 1 ' are the value for 8 the anhydrous peroxide. density of the solid determined as follows. and give the ianpression of being much e n s e r t h a n the l o o P F P C E N TAG[ H. - 1.3071 I I I 4404 o 000921 o 000980 0 .C.oorojo o . The bulb was kept in the freezing mixture for one hour.2270 I O. It is seen also how the temperature 1 4 0 coefficient increases uniformly from that of pure water o. 0 .00007 o .4596 1. Density. 0 0.4633 a t o o and 1. 9%.3235 1. 1552 I . 11202.165j 0. The actual Fig 3 . ensity of Solid 2 120 --Crystals of hydrogen peroxide sink to the hottom w h e n . 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.2404 I .000268 0. en Peroxide.zo I99987 I .OOOj73 0.99862 1.OO 10. liquid.86 90.' 4 56.000744 0.QO107.33 40.7 In Pig. These data are of value in checking up the value for the density of 100% hydrogen peroxide for a calculation shows that 1. 2559 Temperature coefficient ----180.081 j 1.0419 I .2610 I .0894 I .5. 0 . 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 freezing point of the peroxide.44 84.00081j .
At Q' the viscosity of hydrogen peroxide differs only slightly from temperature. Viscosity. HATCHE::R. although no measurements of viscosity b.01272 viscosity with the For purposes of he viscosity curve for water is plotted alongside that for hydrogen peroxide. c. MAASS AND w.. Density of solid.-The impression seems to prevail that highly concentrated solutions of hydrogen peroxide are thick. 'fhe mean 'temperature of this liquid portion being known.. peroxide. It was therefore ing to note the ed when the vishydrogen peroxide was measured with the aid of an Ostwald viscosimeter.01828a t o 0 and o.01456 0 .6434 I . The viscosities of liydrogen15" 20"peroxide-water mixtures were TEMPERATVRE C. From the values obtained. 0" 5" IO" densities of these mixtures had been determilzed. 1 0 12.OW47 0. 11.orgo7 a t 1 ' were the correct values of 1ooo/. also determined a t a later date Fig. of viscosity tabulated below are given in absolute ' units. f a C. The determinations were made ab initio at 2 temperatures of the freezing mixture.01828 0. and as its volume is also known by the position of the top of the solid in the capillary.20 0. Viscosity. tion in the capillary being carelully measured.45 1. +-. The weight of that portion of the hydrogen peroxide which is in the solid form (by far the largest portion) is then found by difference. Temperature o solid.ad been made. therefore.6439 There is. its weight can be calculated because the volume it occupies jn the capillary is known.2560 0.--Viscosity-temperature curves for with the samples with which ffle hydrogen peroxide and water. 8 . syrupy liquids. viscous. the density of the solid follows directly. -4 4 5 -7. it was seen that 0. a contraction of about I 1% on solidification. 4.-I Temperature.
f hzO.Rd32 has been shown to exist' but this corresponds to a 48.83 52.01'778 0 . Z.15 89. 256I 18". The molecular compound 2HzO. 5 shows these results graphically.01235 o.01204 0. I ace Tension. I.01740 .00 5. Viscosity. stance in the past was not in the absolute value of this constant.or762 0.01285 o . Certainly a study of binary mixtures 0019 does not seem to have established that a maximum or lninimum in the viscosity curve indicates the existence of a compound of the composition indicated. 00.PROPERTIE$ OP PURE HYDROGEN PEROXIDE. At a higher temperature.01066 o .k formamide2 is an example 2 of a system showing a similarity to the hydrogen-perI oxide-water curve at 0 ' . this maximum and minimum degenerate into discontinuities. .01gOc 0. 76.01292 0 . 0.98 22.01061 0 o .6% concentration.or300 o . 1' HerFberg.01758 0 .21 0. 0. It will be seen that at o o there is a marked minimum at 15% and a maximum a t 70%..oig3z 0 . dIz02. The v i s c o s i t y . 371 (19x1).62 68.concentration curve of zso-amyl alcohol. Drucker.05 44.or3oI . 42.-The principal interest attached ool-l i --_ -1 IO0 0 20 40 60 60 to the determination of the D'RCEYTAC.50 75.47 98 3 9 0.49 59.Oi805 0 .or846 o . i d z y ~ i k Chem. ]Recently Some doubt has been thrown on the validity of this conception.01909 0.or072 o.01734 0.01828 Fig.Or054 0.Oig29 0 . Z. Maass and 0 . 1 _ _ _ _ _ _ _ I _ 2 0.0~266 0.01157 0. surface tension of a subFig 5.01873 0. THIS 1.71 11.01876 0. 2570 (1910). but rather in its variation with the tempexatwe in order that some clue might be found as to the molecular complexity of the liquid molecules. JOURNAL.03 83. h _ I _ll__l %.01105 14.33 34.
i b i d . the association of hydrogen peroxide is therefore L__ '1' = 3. CoombsG THIS JOURNAL. j csn. 39.923.0 . C €1. the surface tension of water and its variation with the temperature is plotted alongside. 16j6 (1915) 1' 0 2 I.48. Clark. Rarkins. as far as could be judged by means of a microscope.6 .. \ I ____ _ _ 4 1 I j7 r---7--I I __ value €or water is 3. 2 ~ x . the association of hydrogen peroxide would then be given by the following equation 7 8 . 1 8 . B. The angle of contact which hydrogen peroxide makes is very small. _ _ _ _ l l - = 0. abid.l The wide arm of the tube was only 2 . 4630 . and G. 1848 (1917). 541 ( 1 9 x 7 ) .94. 8 W. 39. D. For purposes of comparison. Temperatur0 2 O C Density Surface tension in dynes * I I 1 4630 6 2 I1 0 4554 4512 448r 4434 13 9 I8 2 i 78 77 77 76 75 73 79 SI 47 91 The variations of suriace tension with the temperature are plotleg graphically (Fig. l'he surface tension of hydrogen peroxide was measured by means of the capillary rise method. The surface tension of hydrogen peroxide is therefore. and I I I __--1-_1-__1 ~ OQ 40 5' TFPPFRATURE o0 C 1 T W Richards and L. The similarity between the surface tensions of pure hydrogen peroxide and water has a certain significance in the light of recent work on surface tension by Langm u 9 and Harkinsn3 Evidently the peroxide and water molecules are orientated in exactly the same way a t the surface.j 3 (E)'j .58. Langmuir. Uavres I k . The T. I$. slightly greater than that of water and the association as calculated from the variation of surface tension with temperature is slightly less. 37. 2 ~ . HA'I'CI-IER.'I. 6). On the assumptions made by Ramsay and Shields.-- ----__ I - -\ \ '8 : . the angle is zero. MAASS AKD 1 % ' . €3. in diameter so it 'was considered best to calibrate the capillary by measuring the surface tension of water.2562 0 . -j I . an apparatus being used similiar to the one described by Richards.
. .67 As Fig.so 72.82 73. Its chemical .SI 73.38 78 . .67 74.73 75 *29 75.83 79 . It was therefore tkcided t o use the following method. . 0. . Specific Heat of Liquid 76 Hydrogen Peroxide.?i cept glass.58 56.55 34. 2563 from that point of view also it might have been predicted. El (Fig. . 2 '' . .14 44.91 12.06 59. .31 -4t 18O . As a means of checking up the surface tension of pure hydrogen peroxide. the surface tensions of various concentrations were measured a t 2 ternperatures.76 dynes a i o o and 75. Abulb. At 0 . Latent Heat of 77 ~~~~o~ of Hydrogen Pm-2 oxide.54 18. .49 75. . Specieat of Solid Hydrogen ersmide. that pure hydrogen peroxide would have a slightly greater surface tension then water. .66 77.27 60..00 75. I. ..u nature is sucli that it must 74 not be allowed to come in $ contact with anything ex.$ sented certain experimental $ difficulties. when their cornposition is taken into account.31 77.26 76. S.27 86.99 dynes a t I' obtained from the pure 100% peroxide. . of small Fig. 70 Surface tension (dynes). the surface tensions vary in a regular expected manner.. 7 -Surface tension curves for aqueous ~ 1 ~ 0 2 .a1 90 . .17 27.78 23.13 74..67 74.00 12. A.---The measurement 16 of the above constants of hydrogen peroxide p r e .. 7 2 ) waq sealed a t the end of a PERCENTAGE H2OZ long glass tube.31 59. 7 shows. . 0.22 73 .70 28.04 76. confirming the values of 78. . 8 .PROPERTIES OP PURE HYDROGEN PEROXIDE.. .22 76. O H2Oz.
the specific heat of ice came out to be a.19. and. 8. 1 . presented the deposition of moisture on B. When sufficient tiEe had elapsed for thermal equilibrium to set in. t' the initial and t the final temperature. I t was considered advisable not to seal the hydrogen peroxide into a bulb so that if by chance any decoziposition should occur. The constant k was determined in z separate experiments by going through the procedure described above with the bulb empty. by means of a long drawn-out capillary. which latter was placed in a constant tempera3 ture mixture. In determining the last value given above the hydrogen peroxide was carefully cooled down in order to pre- . dioxide-ether bath (-78. Evidently the experimental error is about 2Yc. the bulb was quickly. which is in fairly good agreement with the value 0.t') where s is the specific heat of the hydrogen peroxide.5841 0 The figures for the lowering of the temperature in the calorimeter are given in order that the accuracy of the method may be judged. The bulb and a definite portion of the stem was then cooled to a known temperature by placing it in a metal Tube R. Then finally to test the accuracy of the method a weighed quantity of water was frozen in the bulb and the latter placed iii a carbon Fig. This value of 12 was also determined by filling the bulb with a substance having a known specific heat (water).5 9480 0. E.520 5730 5697 o o t o 18 5 -32 o t o I8 0 356. the mean value coming out to be 2. of peroxide was transferred into the bulb and weighed accurately.transferred into the inner vessel of a Richards' adiabatic calorimeter and the temperature changes measured in the usual way. fit its mass. The values found for the specific heat of the liquid are given below + i Teinperature OC I iiibe Louwlni: of temperature in calorimeter. R and k a constant involving the specific heat of the glass bulb and the mass of glass immersed in the calorimeter.. If E-T i s the heat given by the calorimeter €3 = m ( t . Some phosphorus pentoxide placed a t E and separated by a gauze from the bulb.2564 0.i') h(1. Taking the latent heat of ice as being 80 calories. an explosion would be avoided.470 obtained by others for the specific heat of ice in that temperature range.460. All the values of k agreed to within a few per cent. diameter. some IO g. H. OC 0 0 0 Sprcific heal 0 o o to 18 j 3. MSBSS AND W.2 ") . HATCHER.
. diameter was rounded off a t the bottom and z sides were ground out of the walls making an angle 01 about * McIntosh and Maass..4636 16. .. in a number of experiments it was possible to determine both specific heat and latent heat by combining the results of these seveTal experiments. . Number.579).. -9. . 2565 vent it from freezing. there was employed an ether-bath described The specific heat of the solid and latent heat of fusion of hydrogen peroxide were determined by means of the same apparatus. 4.. As constant temperature-bath.. . 2. .7 “1. . long. . and the latent heat of fusion 74 calories. .579. a t which the frozen peroxide was kept.. . ..0 18. 5’ the specific heat: of the solid...... -30.... ..28 73.916/. 1’‘ the initial temperature a t which the i‘rozea hydrogen peroxide had been keot.. k the constant of the bulb (T . The method employed was the measurement of the “angle of least deviation. . 1..995 g. The specific heat of the liquid is 0.55 2...109 2.124 0. ...47 2. two values of each of the constants S‘ and L can be calculated from the experimental data..556 .87 3.2 4 .. c. t’ the melting point of hydrogen peroxide (--I .. . 2 . .iip. By combining Experiments I and 3 and Bxperimenks and 4. pure.-The refractive index of the pure hydrogen peroxide was determined last of all. .. c.ml. + f“.. c. . .909 0. 35. .) s the specific heat of the liquid (0. . . Lowering of temperature in calorimeter.” For this purpose a special hollow prism was made. The relation between the heat 1t-P given up by thc calorimeter and the various factors governing the absorption of this heat by the bulb and contents is given by the following expression : H = ms(t . 2. t the final temperature. .. S‘. 1 ... .. that of the solid o. The hydrogen peroxide was first of all frozen and then kept for a long time a t a constant temperature well below its freezing point.... THISJOURNAL.L‘’)j where m is the weight of hydrogen peroxide in the bulb (8. ...vns’(l’ . ..5 cm. efractive Jndex. . Analysis of the purity of the sample showed that it was g9. ... .87 2.07 16. .t ’ ) 4.0 16. A thick-walled glass tube about 3 cm..I 9).t ” ) k(t’ --.4767 L... . 536 (1913’. ..... . These last z values are probably correct to within 4y0. By varying this initial temperature. . . .. 74. . I. . --j7.5 3.. .PROPERTIES OF PURE HYDROGEN PEROXIDX3.
The interest in the refractive index lies principally in the fact that this physical property is both a. . . MAASS AND W. ?t2 Substance. . . . . OH is . . as a matter of fact. I . the density and n the refractive index. . . the property depends both on the atom and the nature of its linkages to other atoms. . . . . H. if hydrogen peroxide had the constitution given by HO . Pollowing Briihl's reasoning in determining the constitution of hydrogen peroxide.OH is 3. the molecular refractive power of a substance is calculated by means of the LorenzLorentz formula n2R--- d where R is the molecular refractive power. . . . j . . . Density.2566 0. 0. . . The values he obtained range from 1 . . The refractive index was one of the few measurements which Briihl undertook to make.4139 1. . . . .4403 Water. . . The accompanying diagram (Fig. H.050 R for hydroxyl. . d R. Hydrogen peroxide. . . I . . 4 ~ 0 5 to 1.G6j Hence. For purposes of comparison. . 5 7 O 54? 27' 54' 2 7 O 22 57 54. Prism angle.9973 1. . this measurement was really the sole object of his research. . . The value 1. . . . .715 R for hydrogen.4043 I . .715 Eriahl of coiirse obtained a lower value for R. HATCHER. . .4r38 Hydrogen peroxide. . . The refractive index of water was measured in order that t-he accuracy of the measurements might be tested. . 22 Angle of minimum deviation. . 60". .4069. Two plates of optical glass edges were cemented on the outside so that the hydrogen peroxide did not come in contact with the cement. . but using the figures obtained by the author : R for water. . .' j6"58%' 56' 58'/2' 53' 43/4r Water. . 24 . Solution of hydrogen peroxide 96. . 25 27" 2' 1 1. Hydrogen peroxide. .OH . . Refractive index. Sodium light was used throughout the measurements. . . . 9) gives an idea of the prism when viewed from the top and the front (plan and elevation). constitutive and an additive one for atoms.81%. . . . . . . . Temperature.4140 I . H is I 2 . indicating that his purest sample may have been only 98Yc a t the time of measurement. . . .3330 obtained i s in excellent agreement with the recognized value. Substance. . +z I nz HZ the molecular weight. 'C. .9OO Refractive index. . . That is. . . . hence the slight change in the prism angle.3330 3. . .3330 55'/2' The prism was taken apart and cleaned after the first 2 experiments described above had been made.
a small amount 01hydrogen peroxide ’cvas shaken up with a larger volume of ether without an appreciable visible change in the relative volumes. 4 r 483 (1900) . the pure hydrogen peroxide does not do so explosively. The crystals in contact with air take up moisture even a t a temperature of ---io”. Britl-al in his paper refers to his non-success in making use of this method OS coixentrat. I . so that a special apparatus is being kilt which will make it possible to measure the angles between 2 faces of a “growing” crystal. R is 2. n’ow. 3 Chem SOC. In this connection the interesting observatioii n as made by the authors thal apparently p r e hydrogen peroxide and anhv drous ether are only slightly soluble irr one another. Hydrogen peroxide also decom-poses when brought in contact with.h resulting decomposition. this fact rendering -&e direct measurement of the boiling point impossible uotil a suitable contairier has been iound. Pure hydrogen peroxide coming in contact with wood decomposes.PROPEKTBS OB PCRE Il’iDROGEN PJ3ROXIDE. the v a k e for the molecular refractive power of quadrivalent oxygen has beexi measured by M i s s I-Iomfrayl in a number of salts of pyrone where oxygen is supposed to be quadrivalent. Miss Konifray’s value €or quadrivalent o x y gen. The accuracy of this extrapolation is -i.-An attempt was made to determine the crystal form of hydrogen peroxide. 1443 ( r 9 9 j ) 87.ery doubtful atid the dielectric constant of the being measured.on.33. and a t high temperatures it apparently acts on glass M 2i. points to unsaturation. Miss HcmCray. In an experiment. Pure hydrogen peroxide dissolves variotls neutral salts readily. Thz impression seems to pres ail that hydrogen peroxide i s very soluble in ether and ether extraction has been used as a method of concentration. if this value is correct. c 1 [he presence of even a sim3 amount 01 acid in the hydrogen peroxide d causes this action to become so violent that the ~ o o catches fire.55 and. 2567 R Sor hydrogen peroxide would be 5. An apparatus has also pure hydrogen peroxide is n o ~ v been devised by means of which the conductivity of pure hydrogen peroxide and of solutions of salts in hydrogen peroxide can be measured. a sixall piece of metallic sodium caused an “intense” explosion when brought in contact with a few drops of pure hydrogen peroxide. The fact that the experimentai value is higher. However. Hence Briihl proposed the constitutional formula HO = OH in which there are 2 quadrivalent oxygen atoms. ’ CalJert. The dielectric constant for hydrogen peroxide has been extrapolated by Cals7ert2 from a \-aim determined for a 4570 solution. d n n chim p h y s . most metals. iscellaaeotss Facis &bout Anhydrous Psraxide. the molecular refractive poxver of hydrogen peroxide containing 2 quadrivalent oxygen atoms would be mu& larger than the experimental value obtained.
immediately after application. but the appakent stability of the anhydrous substance soon caused the precautions which were initially taken to be relaxed. are tabulated. Pure anhydrous hydrogen peroxide does not decompose when kept a t 0’.2568 0. dead tissue is destroyed and removed by the pure peroxide. that in spite of the apparent stability of the pure hydrogen perW oxide. A salt consisting of a strong base and weak acid. MAASS AND W. all precautions are well worth taking. but the skin had the appearance of being loose. . €1. As regards the decomposition of hydrogen peroxide solutions. or vice versa. ~ Q ever. N o blister was formed. compared to the corresponding ones of water. Other observers have mentioned the effect of strong hydrogen peroxide solutions on the skin. that is. hence. and a discussion of the probable con stitution of hydrogen peroxide had better be left until this investigation has been completed. An investigation of the chemical properties of anhydrous peroxide and of the physical properties indicated in the last few paragraphs is being carried out a t the present time. experience ha5 shown that pure aqueous solutions in a suitable container will keep indefinitely. It must be stated. such impurities before they start the decomposition. On the other hand. HATCHBR. in many cases. although. Decomposition is caused by foreign substances getting into the solution a d stronger solutions seem to be capable of destroying. pure hydrogen peroxide does not decompose and the function of anti-catalyzers consists solely in destroying or rendering catalyzers innocuous. The following observations were made when a drop of pure hydrogen peroxide was brought in contact with the skin of the hand. A violent decomposition of the peroxide occurred. In this paper the method of preparing absolute peroxide has been described and in conclusion.” A “neutral” salt such a$ chemically pure sodium chloride does not in itself cause the slightest decomposition. the peroxide’s properties so far detertnined. Anti-catalyzers were investigated and found to consist in every case of catalyzer-destroyers. causes decomposition to take place and the mechanism of many so-called catalyzers can be traced back to this cause. No pain a t all was felt although dilute solutiom give burns accompanied by the sensation of pricking needles But the most remarkable feature of all was that after 3 or 4 hours not a mark was left on the spot where the hydrogen peroxide had been applied. and the skin became absolutely white. but its presence s e e m to augment any decomposition caused by a second impurity. Strong solutions even had the reputation of being highly explosive. the stronger a solution is the better i t “keeps. the appearance of the skin was sickening. Apparectly the living tissue had not been hurt in the slightest.
. . . . .9167 z . . . . . . . . 0. These solutions were prepared by concentrating 3% hydrogen peroxide and puri€ying the resultant concentrated solution by means of a distillation. . Carbon dioxide ether under a vacuum was uyed a i frepLing misturc 1 1 this 1 case . . E ~ 11 1.470 Slirface tension 0 ' . .5 dynes . solution was obtained. In this way the freezing points a t various concentraPions were determined. . . . . and then the whole procedure repeated. . . g o MONTRZAL. . 1920. . . . was added. . . . . . The solution was then allowed to warm up slowly. . In order to obtain the freezing points of hydrogen peroxide-water mixtures a weighed amount of this 86% peroxide solution was placed in a test-tube. . .4633 Mean coefficient of expansion -10' to +zoo . . . 5 . . . . . . . . . .472 7 5 . the freezing point being taken as the teniperature a t which the last crystals melted under vigorous stirring. . . . Physical constant. . . . I . . In this way an 867. 11% Water. . o . O ~ ~ ~ This second paper deals solely with the freezing-point curve of solutions of hydrogen peroxide ar*d water. . . . . . . . . . .3 . .01778 I 3330 3. .KOXIDE.4139 Molecular refractive power (D). . . . . . A platinum thermometer. . . . reading to 0. . sufficient t o dilute the solution a few per cent. I . . . . . The solutions between the concentrations 4 0 % and 60% hydrogen peroxide had a tendency to supercool into a thick viscous mass. . . The tenperature was lowered by means of a suitable freezing mixture until crystals formed. .00000 0. .5t: 0. . . . . . . 0. . . . . . . O0 2569 Freezing point. . . . . . . .. . .PROPERTIES OF PVRG HYDROGET\' PE. . . .. . . . The solution was analyzed. . .614 Specific heat of liquid. . I-IERZBSKG Received September 25. . . . . . but when allowed t o stand a t a temperature of --go*' crystallization started after some time.715 [CO~TRIEUTION THE CI-ISMISTRY FROM DEPARTMGKT NLCGILLUNIVERSITY OF 1 E FROPEWTIES OF PURE HYDROGEN F E u 0 MAASS AND 0 . . . . . . an adequate amount of water. . . . . . . . . . . . . . --I .o 80 calories 0. . . . . .1 was immersed in it. . .70° Density of liquid a t 0 ' . W. . . . . . . I . . . o. . . . . . . . . . . .579 Latent heat of fusion. . . . . .99987 0. . . . . . . . . . . 7 dynes Association (Ramsay and Young) a t o '. . . . the final product may be looked upon as having Seen pure except for a trace of this acid ~7hichfound its way into the distillate. o . . .ooro7 Density of soiid. . . .48 Viscosity 0 ' . . the liquid in the meantime being qigorously stirred.. . . . . Hydrogen peroxide. . . . 74 calories Specific heat of solid. . CANADA. . . As the only volatile impurity contained by the original solution consisted of a trace of hydrochloric acid. All but a few of these were allowed to melt and then the temperature was slightly lowered until crystallization again set in. . 7 8 . . . . . . 3.01829 Refractive index (D) 2 2 '. . .
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